Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
ADVISORY
BOARD
Engineering
E.
B. D R E W ,
SM.
K.
M.
WATSON,
Ph.D.
D.SC.
CHEMICAL PROCESS
PRINCIPLES
A COMBINED VOLUME CONSISTING OF
OLAF A. HOUGEN
AND
KENNETH M. WATSON
PROFESSORS OP CHEMICAL ENGINEERINC
UNIVERSITY OF WISCONSIN
NEV YORK
J O H N WILEY & SONS, INC.
CHAPMAN AND HALL, LIMITED
LONDON
M
}o&i'^
PART I
COPYRIGHT, 1943
BY
OLAF A . HODGEN
AND
KENNETH M . WATSON
PART II
COPYBIGHT, 1947
BY
OLAF A . HOTJGEN
AND
KENNETH M . WATSON
PART III
COPTBIGHT, 1947
BY
OLAF A . HonoEN
AND
KENNETH M . WATSON
PREFACE
" In the following pages certain industrially important principles of chemistry and physics have been selected for detailed study. The significance
of each principle is intensively developed and its applicability and limitations
scrutinized." Thus reads the preface to the first edition of Industrial Chemical
Calculations, the precursor of this book. The present book continues to give
intensive quantitative training in the practical applications of the principles
of physical chemistry to the solution of complicated industrial problems and
in methods of predicting missing physicochemical data from generalized
principles. In addition, through recent developments in thermodynamics
and kinetics, these principles have been integrated into procedures for process
design and analysis with the objective of arriving at optimum economic
results from a minimum of pilot-plant or test data. The title Chemical Process
Principles has been selected to emphasize the importance of this approach to
process design and operation.
The design of a chemical process involves three types of problems, which
although closely interrelated depend on quite different technical principles.
The first group of problems is encountered in the preparation of the material
and energy balances of the process and the establishment of the duties to be
performed by the various items of equipment. The second type of problem
is the determination of the process specifications of the equipment necessary
to perform these duties. Under the third classification are the problems of
equipment and materials selection, mechanical design, and the integration
of the various units into a coordinated plot plan.
These three types may be designated as process, unit-operation, and plant. design problems, respectively. In the design of a plant these problems cannot
be segregated and each treated individually without consideration of the
others. However, in spite of this interdependence in application the three
types may advantageously be segregated for study and development because
of the different principles involved. Process problems are primarily chemical
and physicochemical in nature; unit-operation problems are for the most
part physical; the plant-design problems are to a large extent mechanical.
In this book only process problems of a chemical and physicochemical
nature are treated, and it has been attempted to avoid overlapping into the
fields of unit operations and plant design. The first part deals primarily
with the applications of general physical chemistry, thermophysics, thermochemistry, and the first law of thermodynamics. Generalized procedures
for estimating vapor pressures, critical constants, and heats of vaporization
have been elaborated. New methods are presented for dealing with equilibrium problems in extraction, adsorption, dissolution, and crystallization.
The construction and use of enthalpy-concentration charts have been extended
to complex systems. The treatment of material balances has been elaborated
to include the effects of recycling, by-passing, changes of inventory, and
accumulation of inerts.
vi
PREFACE
In the second part the fundamental principles of thermodynamics are presented with particular attention to generalized methods. The applications
of these principles to problems in the compression and expansion of fluids,
power generation, and refrigeration are discussed. However, it is not attempted to treat the mechanical or equipment problems of such operations.
Considerable attention is devoted to the thermodynamics of solutions
with particular emphasis on generalized methods for dealing with deviations
from ideal behavior. These principles are applied to the calculation of equilibrium compositions in both physical and chemical processes.
Because of the general absence of complete data for the solution of process
problems a chapter is devoted to the new methods of estimating thermodynamic properties by statistical calculations. This treatment is restricted to
simple methods of practical value.
All these principles are combined in the solution of the ultimate problem
of the kinetics of industrial reactions. Quantitative treatment of these
problems is difficult, and designs generally have been based on extensive
pilot-plant operations carried out by a trial-and-error procedure on successively larger scales. However, recent developments of the theory of absolute
reaction rates have led to a thermodynamic approach to kinetic problems
which is of considerable value in clarifying the subject and reducing it to the
point of practical applicability. These principles are developed and their
apphcation discussed for homogeneous, heterogeneous, and catalytic systems.
Particular attention is given to the interpretation of pilot-plant data. Economic considerations are emphasized and problems are included in estabhshing
optimum conditions of operation.
In covering so broad a range of subjects, widely varying comprehensibility
is encountered. It has been attempted to arrange the material in the order
of progressive difficulty. Where the book is used for college instruction in
chemical engineering the material of the first part is suitable for second- and
third-year undergraduate work. A portion of the second part is suitable
for third- or fourth-year undergraduate work; the remainder is of graduate
level. To assist in using the book for undergraduate courses in thermodynamics and kinetics those sections of Part II which are recommended for such
survey courses are marked. This material has been selected and arranged
to give continuity in a preliminary treatment which can serve as a foundation
for advanced studies, either by the individual or in courses of graduate level.
The authors wish to acknowledge gratefully the assistance of Professor
R. A. Ragatz in the revision of Chapters I and VI, and the suggestions of Professors Joseph Hirschfelder, R. J. Altpeter, K. A. Kobe, and Dr. Paul Bender.
OLAF A. HOUQEN
KENNETH M . WATSON
MADISON, WISCONSIN
August, 194s
CONTENTS
Page
PREFACE .
TABLE OF SYMBOLS
ix
PART
MATERIAL
AND
ENERGY
BALANCES
Chapter
STOICHIOMETRIC PRINCIPLES
II
27
III
VAPOR PRESSURES
53
IV/
89
Ill
V
Vr/
MATERIAL BALANCES
167
THERMOPHYSICS
201
THERMOCHEMISTRY
249
323
YJy
viy/
383
PART
II
THERMODYNAMICS
XI
479
XIII
. . . .
538
XIV
THERMODYNAMICS OF SOLUTIONS
XII
XV
XVI
XVII
THERMODYNAMIC PRINCIPLES .
.
.
.
.
. '
437
595
PHYSICAL EQUILIBRIUM
644
CHEMICAL EQUILIBRIUM
691
vii
756
viii
CONTENTS
PART
KINETICS
AND
III
CATALYSIS
Chapter
XVIII
XIX
XX
XXI
XII
Page
805
HOMOGENEOUS REACTIONS
CATALYTIC REACTIONS
902
973
1007
1049
APPENDIX
jcvii
AUTHOR INDEX
xxiii
SUBJECT INDEX
xxvii
TABLE OF SYMBOLS
A
A
A
A
a
Om
ttp
ttv
B
B
B
C
C
c
c
c
c.
c.
c.
c
c
c
Cp
Cv
d
D
DAB
Dp
D',
,
d
E
E
E^
area
atomic weight
component A
total work function
activity
external surface per unit mass
external surface per particle
external surface per unit volume
component B
constant of Calingaert-Davis equation
thickness of effective^ film
component C
concentration per unit volume
degrees centigrade
number of components
over-all rate constant
heat capacity at constant pressure
heat capacity at constant volume
Sutherland constant
concentration of adsorbed molecules per unit mass of
catalyst
specific heat
velocity of light
molal heat capacity at constant pressure
molal heat capacity at constant volume
surface concentration of adsorbed molecules per unit
catalyst area
diameter
diffusivity of A and B
effective particle diameter equal to diameter of sphere
having the same external surface area as particle
effective diameter equal to diameter of sphere having
same area per unit volume as particle
differential operator
energy in general
energy of activation, Arrhenius equation
effectiveness factor of catalysis
TABLE OF SYMBOLS
c
F
F
F
F,
Fi
S
/
/
Q
6
0
o
5
LQ
(g)
9
ffo
H
H
H
He
Hi
HH
Fp
H,
HH
Hr
Ht
AH
AHc
AHf
AHr
A/^
H
H
AH
ft
h
I
I
I
Ti(i
specific gravity
< ~- ,
^^.
free energy per mole
,, '.
^Y
partial molal free energy
,^^.,_
^
change in free energy "
j -'6
gaseous state
. >., ,,,',
,.- v^
degeneracy
-^ - n^i
standard gravitational constant, 32.174 (ft/sec)/sec
enthalpy
Henry's constant
..
/ v-*!
humidity
.
<
height of catalytic unit
#
y
height of mass-transfer unit
-i
height of heat-transfer unit
^'
height equivalent to a theoretical plate
percentage humidity
height of reactor unit
,<
relative humidity
;
height of transfer unit
change in enthalpy
,,;. - /
,,
heat of combustion
.
/
heat of formation
, :>,
/
|i|
heat of reaction
' ,
standard enthalpy of activation
'\..(\
enthalpy per mole
rpartial molal enthalpy
partial molal enthalpy change
Planck's constant
heat-transmission coefficient
inert component
integration constant
moment of inertia
TABLE OF SYMBOLS
J
/
jt
i.-jis^ii . , , t . '
'' K ' " ' "
K
^^'' ' ;*; '
:
K
K
Ka
Ke
Kg
Kj,
Kp
K'
It
k
ft
kj^
k'ji
kg
kj^
k'
L
L
Lfi
L'
I
Ip
l
(1)
]n
1(^
M
Mm
m
m
m
N
N
Nt
xi
Jacobian function
mechanical equivalent of heat
mass-transfer factor in
fluid
film
n
heat-transfer factor in fluid
film
"-l
characterization factor
degrees Kelvin
'
distribution coefficient
''- xtl-nH
,j
equifibrium constant
;i
y
vaporization equilibrium constant '
^
equilibrium constant for adsorption
^
equilibrium constant, concentration units
over-all mass-transfer coefficient, pressure units
over-all mass-transfer coefficient, fiquid concentration
units
equilibrium constant, pressure units
irt?
surface equilibrium constant
i
M,^'
forward-reaction velocity constant ^
tj,"'
thermal conductivity
"'
?>
Boltzmann constant
r ,!',- .s
?,
adsorption velocity constant
'
?*
desorption velocity constant
'S^
?*
mass-transfer coeflScient, gas film ' 'p\.
mass-transfer coefficient, liquid film
^^
reverse-reaction velocity constant
ai*
mass velocity of fiquid per unit area
'?*A
total molal adsorption sites per unit mass
molal mass velocity of liquid per unit area
active centers per unit area of catalyst
length
heat of pressure change at constant pressure
heat of expansion at constant temperature
liquid state
natural logarithm
'''
"' ^3
logarithm to base 10
"
'''
it
molecular weight
' >'
M
mean molecular weight
>M '
"i
mass
>'
^
slope of equilibrium curve dy*/dx
^J
Thiele modulus
Avogadro number 6.023(1023)
-'^
mole fraction
number of transfer units
ai
TABLE OP SYMBOLS
No
Nj^
n
P
Pf
Q
Q
q
g,
R
R
r
r,^
r,nA
r^
S
8
S
8
Sp
Sr
(S
AiS*
8
8
(B)
T
t
V
U
V
u
V
V
Vf
V
w
w
We
radius
rate of reaction or transfer of A per unit area
rate of reaction or transfer of A per unit mass
rate of reaction or transfer of A per unit volume
component S
cross section
entropy
humid heat
percentage saturation
relative saturation
* .
i
space velocity
entropy of activation
molal entropy
number of equidistant active sites adjacent to each
other
solid state ,
absolute temperature, degrees Rankine or Kelvin
temperature, F or C
internal energy
,
; ;;;
over-all heat-transfer coefficient
/
^j
internal energy per mole
,;;
velocity
molecular volume in Gilliland equation
volume
volume of reactor
volume per mole
ri
weight
work done by system
work of expansion done by system
TABLE OF SYMBOLS
to/
w.
X^
X
X
.
y
y*
z
zz
z
xiil
., '
Nj,,
Beynold's number
DQ
iVp,
Prandtl number
r- '
Nst
Stanton number
7777
Nsc,
Schmidt number
*=?-
rS
A
a
B
b
C
c
D
D
e
f
f
f
G
H
L
L
SUBSCEIPTS
' component A
air
> 1
_
'"
' component B
'
>-i' , .\
normal boiling point '
. . * , .;,-:
component C
. 1 ..1
critical state
< ' ~^
component D
>'
dense arrangement '
expansion
" "
electrical and radiant
, x.-, (
formation
fusion
' '' ' "
=
gas or vapor
" ''. . - ' ''
isenthalpic
hquid
'^
loose arrangement
'jv-x. *?f i. j .
xiv
TABLE OF SYMBOLS
p
R
r
r
S
S
s
s
T
t
t
V
V
(a)
a
a
a
a
(/3)
(3
7
(7)
A
S
S
d
c >.
T)
0
K
A
X
X
X/
H
11
V
V
: '
G E E B K SYMBOLS
crystal form
coefficient of compressibility
proportionality factor for diffusioA
relative volatility
thermal diffusivity
=.'.-....,-'.
crystal form
^
coefficient of volumetric expansioA ;
activity coefficient
crystal form
finite change of a property; positive value indicates an
increase
- .
change in moles per mole of r e a c t ^ t
deformation vibration
partial differential operator
' .~ i
,{
energy per molecule
,
*efficiency
fraction of total sites covered
ratio of heat capacities
heat of vaporization
heat of vaporization per mole
wave length
heat of fusion per mole
chemical potential
viscosity
frequency
fugacity coefficient of gas
TABLE OF SYMBOLS
V
V
V
a
a
V
P
PB
Pp
Pc
S
<r
a
T
4>
<f>
t
n u m b e r of ions
^
n u m b e r of molecules
valence or stretching vibration
expansion factor of liquid
wave number
"total pressure of mixture, used where necessary to
distinguish from p
,.
density
%,
bulk density
4"
particle density
t r u e solid density
:, summation
surface tension
symmetry number
>
. :
time
activity coefficient
n u m b e r of phases
SUPERSCRIPTS
*,
*
ideal behavior
equilibrium state
o
A,
standard state
pseudo state
leverse rate
standard state of activation
XV
CHAPTER I
STOICHIOMETRIC PRINCIPLES
The principal objective to be gained in the study of this book is the
ability to reason accurately and concisely in the application of the
principles of physics and chemistry to the solution of industrial problems.
It is necessary that each fundamental principle be thoroughly understood, not superficially memorized. However, even though a knowledge
of scientific principles is possessed, special training is required to solve
the more complex industrial problems. There is a great difference
between the mere possession of tools and the ability to handle them
skilfully.
Direct and logical methods for the combination and application of
certain principles of chemistry and physics are described in the text and
indicated by the solution of illustrative problems. These illustrations
should be carefully, studied and each individual operation justified.
However, it is not intended that these illustrations should serve as forms
for the solution of other problems by mere substitution of data. Their
function is to indicate the organized type of reasoning which will lead to
the most direct and clear solutions. In order to test the understanding
of principles and to develop the ability of organized, analytical reasoning, practice in the actual solution of typical problems is indispensable. The problems selected represent, wherever possible, reasonable
conditions of actual industrial practice.
Conservation of Mass. A system refers to a substance or a group of
substances under consideration and a process to the changes taking
place within that system. Thus, hydrogen, oxygen, and water may
constitute a system, and the combustion of hydrogen to form water,
the process. A system may be a mass of material contained within
a single vessel and completely isolated from the surroundings, it may
include the mass of material in this vessel and its association with the
surroundings, or it may include all the mass and energy included in a
complex chemical process contained in many vessels and connecting lines
and in association with the surroundings. In an isolated system the
boundaries of the system are limited by a mass of material and its
energy content is completely detached from all other matter and
energy. Within e given isolated system the mass of the system remains
constant regardless of the changes taking place within the system.
This statement is known as the law of conservation of mxiss and is the
basis of the so-called material balance of a process.
I
STOICHIOMETRIC PRINCIPLES
[CHAP. I
CHAP." I]
When the atoms of the elements unite to form a particular compound, it is observed that the compound, when carefully purified, has a
fixed and definite composition rather than a variable and indefinite
composition. For example, when various samples of carefully purified
sodium chloride are analyzed, they all are found to contain 60.6 per
cent chlorine and 39.4 per cent sodium. Since the sodium chloride is
composed of sodium atoms, each of which has the same mass, and of
chlorine atoms, each of which has the same mass (but a mass that is
different from the mass of the sodium atoms), it is concluded that in
the compound sodium chloride the atoms of sodium and chlorine have
combined according to some fixed and definite integral ratio.
By making a careful study of the relative weights by which the
chemical elements unite to form various compounds, it has been possible to compute the relative weights of the atoms. Work of this type
occupied the attention of many of the early leaders in chemical research
and has continued to the present day. This work has resulted in the
famihar table of international atomic weights, which is still subject to
periodic revision and refinement. In this table, the numbers, which
are known as atomic weights, give the relative weights of the atoms of
the various chemical elements, all referred to the arbitrarily assigned
value of exactly 16 for the oxygen f tom.
A large amount of work has been done to determine the composition
of chemical compounds. As a result of this work, the composition of a
great variety of chemical compounds can now be expressed by formulas
which indicate the elements that comprise the compound and the
relative number of the atoms of the various elements present.
It should be pointed out that the formula of the compound as ordinarily written does not necessarily indicate the exact nature of the
atomic aggregates that comprise the compound. For example, the
formula for water is written as H2O, which indicates that when hydrogen
and oxygen unite to form water, the union of the atoms is in the ratio
of 2 atoms of hydrogen to 1 atom of oxygen. If this compound exists
as steam, there are two atoms of hydrogen permanently united to one
atom of oxygen, forming a simple aggregate termed a molecule. Each
molecule is in a st^te of random motion and has no permanent association with other similar molecules to form aggregates of larger size.
However, when this same substance is condensed to the liquid state,
there is good evidence to indicate that the individual molecules become
associated, to form aggregates of larger size, (Il20)j:, x being a
variable quantity. With respect to solid substances, it may be said
that the formula as written merely indicates the relative number of
atoms present in the compound and has no further significance. For
example, the formula for cellulose is written CeHioOe, but it should not
STOICHIOMETRIC PRINCIPLES
[CHAP.
CHAP. I]
!/
Molecular Weights:
H2O
FeaOi
H2
'.....,11.,, ..
55.84
1.008
16.00
The respective relative weights of the reactants and products maybe determined by multiplying the respective atomic or molecular
weights by the coefficients that precede the formulas of the reaction
equation. These figures may conveniently be inserted directly below
the reaction equation, thus:
3Fe
' *:-' -(i .;
(3X55.84)
167.52
4H2O
-* FesOi +
(4X18.02)
72.08
231.5
231.5
4H2
(4X2.016)
8.064
Thus, 167.52 parts by weight of iron react with 72.08 parts by weight
of steam, to form 231.5 parts by weight of the magnetic oxide of iron
and 8.064 parts by weight of hydrogen. By the use of these relative
weights it is possible to work out the particular weights desired in a
given problem. For example, if it is required to compute the weight
of iron and of steam required to produce 100 pounds of hydrogen, and
the weight of the resulting oxide of iron formed, the procedure would
be as follows:
Reactants:
Weight of iron = 100 X (167.52/8.064)
Weight of steam = 100 X (72.08/8.064)
Total
Products:
Weight of iron oxide = 100 X (231.5/8.064)
Weight of hydrogen
Total
2075 lb
894 Jb
2969 lb
'.
2869 lb
100 lb
2969 lb
Volume Relations in Chemical Reactions. A correctly written reaction equation will indicate not only the relative weights involved in a
chemical reaction, but also the relative volumes of those reactants and
products which are in the gaseous state. The coefficients preceding
the molecular formulas of the gaseous reactants and products indicate
the relative volumes of the different substances. Thus, for the reaction
under consideration, for every 4 volumes of steam, 4 volumes of hy-
STOICHIOMETRIC PRINCIPLES
[CHAP.
drogen are produced, when both materials are reduced to the same
temperature and pressure. This volumetric relation follows from
Avogadro's law, which states that equal volumes of gas at the same
conditions of temperature and pressure contain the same number of
molecules, regardless of the nature of the gas. That being the case,
and since 4 molecules of steam produce 4 molecules of hydrogen, it maybe concluded that 4 volumes of steam will produce 4 volumes of hydrogen. It cannot be emphasized too strongly that this volumetric
relation holds only for ideally gaseous substances, and must never be
applied to liquid or to solid substances.
The Gram-Atom and the Pound-Atom. The numbers appearing in
a table of atomic weights give the relative weights of the atoms of the
various elements. It therefore follows that if masses of different elements are taken in such proportion that they bear the same ratio to one
another as do the respective atomic weight numbers, these masses will
contain the same number of atoms. For example, if 35.46 grams of
chlonae, which has sa atomic wei^t oi 35.46, are. takea, and if 55.84
grams of iron, which has an atomic weight of 55.84, are taken, there
will be exactly the same number of chlorine atoms as of iron atoms in
these respective masses of material.
'
The mass in grams of a given element which is equal numerically to its
atomic weight is termed a gram-atom. Similarly, the mass in pounds of
a given element that is numerically equal to its atoinic weight is termed
a pound-atom. From these definitions, the following equations may be
written:
Gram-atoms of an elementary substance = -:rAtomic weight
Grams of an elementary substance = Gram-atoms X Atomic weight
Pound-atoms of an elementary substance =
r^
:
Atomic weight
Pounds of an elementary substance = Polind-atoins X Atomic weight
The actual number of atoms in one gram-atom' of an elementary substance has been determined by several methods, the average result being
6.023 X 10^1 This numbel^ known as the Avogadi-o number, is of considerable theoretical importance.
The Gram-Mole and the Pound-Mole. It has been pointed out that
the formula of a chemical compound indicates the relative numbers and
the kinds of atoms that unite to form a compound. For example, the
formula NaCl indicates that sodium and chlorine atoms are present in
CHAP. I]
Mass in grams
Molecular weight
,
,
,
, ,
Pound-moles oi a substance =
Mass in pounds
^
Molecular weight
Pounds of a substance = Pound-moles X Molecular weight
STOICHIOMETRIC PRINCIPLES
[CHAP.
Accordingly, with respect to the reaction equation previously discussed, it may be said that 167.52 grams of iron (3 gram-atoms) will
form 4 gram-moles of hydrogen, which will, when brought to standard
conditions, occupy a volume of 4 X 22.4 Uters, or 89.6 liters. Or, if
Enghsh units are to be used, it may be said that 167.52 pounds of iron
(3 pound-atoms) will form 4 pound-moles of hydrogen, which will
occupy a volume of 4 X 359 cubic feet (1436 cubic feet) at standard
conditions.
. . ? T. .,^^r,';.! iY>'/';.r^-'''>
Illustration 1. A cylinder contains 25 lb of liquid chlorine. What volume in
cubic feet will the chlorine occupy if it is released and brought to standard conditions?
Basis of Calculation: 25 lb of chlorine.
Liquid chlorine, when vaporized, forma a gas composed of diatomic molecules, CI2.
Molecular weight of chlorine gas = (2 X 35.46)
Lb-moles of chlorine gas = (25/70.92)
70.92
0.3525
'
44.06
22.32
985 grams
'CHAP.
I]
Equation:
B<, .1.
Basis of Calculation:
~,-.--i
Fe
!'':'
H20
''""'"'"'*'"
. ,
FesOi
Hj
' '55.84
18.02
fX
or
or
or
'
231.5
2.016
49.6
37.2
2075
49.6
894
12.4
2870
2969
lb-moles
lb-atoms
lb
lb-moles
1b
lb-moles
1b
lb
2970 1b
,;,,,
- M .
17,820 cu ft
In this simple problem the full value of the molal method of calculation is not apparent; as a matter of fact, the method seems somewhat
more involved than the solution which was presented earUer in this
section, and which was based on the simple rules of ratio and proportion.
It is in the more complex problems pertaining to industrial operations
that the full benefits of the molal method of calculation are realized.
10
STOICHIOMETRIC PRINCIPLES
[CHIP. I
Excess Reactants, In most chemical reactions carried out in industry, the quantities of reactants supplied usually are not in the exact
proportions demanded by the reaction equation. It is generally desirable that some of the reacting materials be present in excess of the
amounts theoretically required for combination with the others. Under
such conditions the products obtained will contain some of the uncombined reactants. The quantiti,es of the desired compounds which are
formed in the reaction will be determined by the quantity of the limiting
reactant, that is, the material which is not present in excess of that
required to combine with any of the other reacting materials. The
amount by which any reactant is present in excess of that required to
combine with the hmiting reactant is usually expressed as its percentage
excess. The percentage excess of any reactant is defined as the percentage ratio of the excess to the amount theoretically required for combination with the limiting reactant.
The definition of the amount of reactant theoretically required is sometimes arbitrarily established to comply with particular requirements.
For example, in combustion calculations, the fuel itself may contain
some oxygen, and the normal procedure in such instances is to give a
figure for percentage of excess oxygen supplied by the air which is based
on the net oxygen demand, which is the total oxygen demanded for complete oxidation of the combustible components, minus the oxygen in the
fuel.
Degree of Completion. Even though certain of the reacting materials
may be present in excess, many industrial reactions do not proceed to the
extent which would result from the complete reaction of the limiting
material. Such partial completion may result from the estabUshment
of an equilibrium in the reacting mass or from insufficient time or opportunity for completion to the theoretically possible equilibrium. The
degree of completion of a reaction is ordinarily expressed as the percentage
of the limiting reacting material which is converted or decomposed into
other products. In processes in which two or more successive reactions
of the same materials take place, the degree of completion of each step
may be separately expressed.
In those instances where excess reactants ^re present and the degree
of completion is 100%, the material leaving the process will contain not
only the direct products of the chemical reaction but also the excess
reactants. In those instances where the degree of completion is below
100%, the material leaving the process will contain some of each of the
reactants as well as the direct products of the chemical reactions that
took place.
CHAP. I]
BASIS OF CALCULATION
11
BASIS OF CALCtTLATION
12
STOICHIOMETRIC PRINCIPLES
[CHAP. I
;,i -i.
Various methods are possible for expressing the composition of mixtures and solutions. The different methods that are in common use
may be illustrated by considering a binary system, composed of components which will be designated as A and B. The following symbols
will be used in this discussion:
m = total weight of the system.
rriA and m^ = the respective weights of components A and B.
MA and MB = the respective molecular weights of components A
and B, if they are compounds.
AA and As = the respective atomic weights of components A and B,
if they are elementary substances.
y = volume of the system, at a particular temperature and
,, ,
, ],,
pressure. ^,|.^.. ; .,^,,, ,^j,j,.
^ .
Si VA and VB = the respective pure component volumes of components
A and B. The pure component volume is defined as
the volume occupied by a particular component if it
,_,,, ,.. - .
is separated from the mixture, and brought to the
same temperature and pressure as the original
mixture.
Weight Per Cent. The weight percentage of each component is
found by dividing its respective weight by the total wdght of the system,
and then multiplying by 100: . , ^ ,
. nrs
Weight per cent of A = X 100
m
This method of expressing compositions is very commonly employed
for solid systems, and also for liquid systems. -It is not used commonly
for gaseous systems. Percentage figures applying to a sohd or to a
liquid system may be assumed to be in weight per cent, if there is no
definite specification to the contrary. One advantage of expressing
composition on the basis of weight per cent is that the composition values
CHAP
>
1]
13
-m
14
STOICHIOMETRIC PRINCIPLES
[QnAP. I
in the system. By multiplying the mole fraction by 100, the mole per
cent of A in the system is obtained. Thus,
Mole fraction of A =
,;,
MA/MA + VIB/MB
J
The summation of all the mole percentages for a given system totals
exactly 100. The composition of a system expressed in mole per cent
will not vary with the temperature, assuming there is no loss of material
from the system, and that no chemical reactions or associations occur.
Illustration 4. An aqueous solution contains 40% Na2C03 by weight.
the composition in mole per cent.
Expre^
H2O = 18.02
0.377 gm-moles
3.33 gm-moles
3.71 gm-moles
CeHe = 78.1
3200 gm
5860 gm
9060 gm
In the case of ideal gases, the composition in mole per cent is exactly
the same as the composition in volumetric per cent. This deduction
follows from a consideration of Avogadro's law. It should be emphasized
that this relation holds only for gases, and does not apply to liquid or to
solid systems.
'
CHAP. I]
15
Illustration 6. A natural gas has the following composition, all figures being in '
volumetric per cent:
Methane, CH4
Ethane, C2H6
Nitrogen, N2
Calculate:
(a)
(6)
(c)
(d)
.;.--
.-.
83.5%
12.5%
4.0%
100.0%
-..... .
Part (a) It has been pointed out that for gaseous substances, the composition
in mole per cent is identical with the composition in volumetric per cent. Accordingly, the above figures give the respective mole per cents directly, with no calculation.
Part (6) Calculation of Composition in Weight Per Cent.
Basis of Calculation: 100 lb-moles of gas.
Molecular
Lb-Moles Weight
Weight in Pounds
CH4
83.5
16.03
83.5 X 16.03 = 1339
C2H6
12.5
30.05
12.5 X 30.05 = 376
N2
4.0
28.02
4.0 X 28.02 = J 1 2
100.0
1827
,- ^
Weight
(1339/1827)
(376/1827)
(112/1827)
'-^
Per Cent
X 100 = 73.3
X 100 = 20.6
X 100 = 6.1
100.0
Part (c) The molecular weight of a gas is numerically the same as the weight in
pounds of one pound-mole. Therefore, the molecular weight equals 1827/100, or
18.27.
Part (d) Density at Standard Conditions, as lb per cu ft.
'
ymAlAx) + (mB/Afl)
Atomic per cent of A = Atomic fraction X 100
16
STOICHIOMETRIC PRINCIPLES
(CHAP. I
CHAP. I]
(a)
(6)
(c)
(d)
(e)
(/)
D E N S I T Y A N D S P E C I F I C GRAVITY
, .
The volumetric per cent of water.
'm*,^ '
:>
The composition in mole per cent.
The composition in atomic per cent.
The molahty.
. . . .
Pounds NaCl per pound H2O. t^>;>t . H.;';;Ui,K\,i'4r :.:IJ - -ri. . ,
Basis of Calculation:
1000 cc of solution.
'
17
1148
3.93
50.9
54.8
gm
gm-moles
gm-moles
gm-moles
20.0
80.0
100.0
(6) Volumetric Per Cent W a t e r :
,
,
Density of pure water at 20C = 0.998 gm/cc
- -'*"'-^
Volume of pure water = 918/0.998 = 920 cc
Volumetric per cent of water = (920/1000) X 100 = 92.0
(c) Composition in Mole Per Cent:
Mole per cent NaCl = (3.93/54.8) X 100 =
Mole per cent HjO = (50.9/54.8) X 100 =
I
;.
"^'>,
":,
7.17
92.8
Atomic
Atomic
Atomic
Atomic
per
per
per
per
"
100.0
.|
.N^
Total
'
.;
|
|
., ,
|^ .
3.93
3.93
101.8
50.9
160.6
cent
cent
cent
cent
of
of
of
of
sodium
chlorine
hydrogen
oxygen
= (3.93/160.6) X
= (3.93/160.6) X
= (101.8/160.6) X
= (50.9/160.6) X
100
100
100
100
=
=
=
=
2.45
2.45
63.4
31.7
100.0
>'
, ,
,,,iyrj
.'.,r;.
18
STOICHIOMETRIC PRINCIPLES
[CHAP. I
The specific gravity of a solid or liquid is the ratio of its density to the
density of water at some specified reference temperature. The temperatures corresponding to a value of specific gravity are generally symbolized
by a fraction, the numerator of which is the temperature of the liquid in
question, and the denominator, the temperature of the water whidh
serves as the reference. Thus the term sp. gr. 70/60F indicates the
specific gravity of a hquid at 70F referred to water at 60F, or the
ratio of the density of the Hquid at 70F to that of water at 60F. It
is apparent that if specific gravities are referred to water at 4C (39.2F)
they will be numerically equal to densities in grams per cubic centimeter.
Concentration, ft NaCl by Weight
Concentration, grams NaCl
per 100 cc. of Solution
1.24
0.96
0
10
15
20
25
30
35
CHAP. I]
19
140
Degrees Baume =
130
145
20
STOICHIOMETRIC PRINCIPLES
[CHAP. I
'
CHAP.
I]
TRIANGULAR PLOTS
21
22
STOICHIOMETRIC PRINCIPLES
[CHAP. I
JQ
= 45.8% C^HiBr,
This point lies on line hB and will be seen to correspond to a specific volume of 0.62
at 12.5% C7H8 and 41.7% CCU.
CHAP. I]
CONVERSION OF UNITS
23
page 438. A few simple rules will be given for guidance where calculation of conversion factors becomes necessary.
Most scientific units may be expressed in terms of simple dimensions,
such as length, weight, time, temperature, and heat. In conversion
the unit is first expressed in terms of its simplest dimensions combined
with the known numerical or symboHc value of the unit. Thus, the
viscosity of a liquid is n grams per second-centimeter. In the English
system the value will be expressed in pounds per second-foot. Each
of the dimensions is replaced separately by the dimensions of the desired
system together with its corresponding conversion factor. Thus, since
1 gram = 0.002204 lb and 1 cm = 0.0328 ft
grams
0.002204 lb
lb
fi -rTrT^^^^^^"^^!?
~' 0.0670/i
(sec) (cm) = '^
1 (sec) 0.0328 (ft)
'^ (sec) (ft)
Similarly a pressure of 1 atmosphere =
14.7 lb
(in.)2 ""
since
. i^..
"
grams
(cm)^
(atm) (ft)'
' '^ (lb-mole)R
24
'
[CHAP. I
(c) How many grams of barium chloride are equivalent to 5.0 grams of sodium
chloride?
(d) How many grams of sodium sulfate are necessary for the precipitation of
the barium of 5.0 grams of barium chloride?
(e) How many grams of sodium sulfate have been added to barium chloride if
5.0 grams of barium sulfate are precipitated?
(/) How many pounds of sodium sulfate are equivalent to 5.0 pounds of
sodium chloride?
(g) How many pounds of barium sulfate are precipitated by 5.0 pounds of
barliim chloride?
(h) How many pounds of barium sulfate are precipitated by 5.0 pounds of
sodium sulfate?
(t) How many pounds of barium sulfate are equivalent to 5.0 pounds of sodium
chloride?
2. How many grams of chromic sulfide will be formed from 0.718 grams of chromic
oxide according to the equation:
2Crj08 + 3CS2 = 2Cr5S, + 3COs
3. How much charcoal is required to reduce 1.5 pounds of arsenic trioadel
AsjOa + 30 = 3CO + 2As
4. Oxygen is prepared according to the equation 2KCIO3 = 2KC1 + SOs. What
is the yield of oxygen when 7.07 grams of potassium chlorate are decomposed? How
many grams of potassium chlorate must be decomposed to liberate 2.0 grams of
oxygen?
6. Sulfur dioxide may be produced by the reaction:
,
Cu + 2H2S04 = CuSOi + 2H2O + SOj
' "
(a) How much copper, and (6) how much 94% H2S04 must be used to Obtain
32 pounds of sulfur dioxide?
6. A limestone analyzes CaCOa 93.12%, MgCOa 5.38%, and insoluble matter
1.50%.
(o) How_ many pounds of calcium oxide could be obtained from 5 tons of the
limestone?
(6) How many pounds of carbon dioxide are given off per pound of this limestone?
7. How much superphosphate fertilizer can be made from one ton of calcium
phosphate, 93.5% pure? The reaction is
Cas(P04)2 + 2H2S04 = 2CaS04 + CaHiCPO,),
8. How much potassium chlorate must be taken to produce the same amount of
oxygen as will be produced by 1.5 grams of mercuric exide?
9. Regarding ammonium phosphomolybdate, (NH4)3p04-12MoOs'3H20, as made
up of the radicals NHj, H2O, PjOs and M0O3, what is the percentage composition of
the molecule with respect to these radicals?
10. How many pounds of salt are required to make 1500 pounds of salt cake
(NajSO*)? How many pounds of Glauber's salt (Na2SO4'10H2O) will this amount
of salt cake make?
,
/
'
PROBLEMS
CHAP. I]
* % "Hw(i4<
''ffe
25
HCl
HjSOi
HNO3
NH4NO3
ZnBrs
CdClj
MgCU
CaBrj
SrClj
LiCl
KQ
Composition of Solution
Weight % HCl = 30
mole % H28O4 = 36.8
lb HNOa/lb H2O = 1.704
lb-mole NHiNOs/lb H2O = 0.01250
gm ZnBrj/lOO ml of solution at 20C
gm CdClj/lOO ml of solution a t 80C
gm-mole M g C U / l of solution at 20C
lb CaBrj/U. S. gal at 68F (20C) =
lb-mole SrClj/U. S. gal at 68F (20C)
molality = 10.13
normality = 2.70
= 130.0
= 68.3
= 3.99
4.03
= 0.02575
20C
80C
1.149
1.681
1.382
1.226
2.002
1.575
1.269
1.381
1.396
1,179
1.118
1.115
1.625
1.296
1.187
1.924
1.519
1.245
1.343
1.368
1.158
1.088
26
STOICHIOMETRIC PRINCIPLES
[CHAP. I
17. An aqueous solution of sodium chloride contains 28 grams of NaCl per 100 cc
of solution at 20C. Express the concentration of this solution in the following
terms, using data from Fig. 1.
(a) Percentage NaCl by weight.
(6) Mole fraction of NaCl.
(c) Pound-moles of NaCl per 1000 pounds of water (molality).
(d) Pound-moles of NaCl per U. S. gallon of solution at 0C.
18. It is desired to prepare a solution of sodium chloride in water, having a molality
of 2.00. Calculate the weight of sodium chloride which should l5e placed in a 1000-ec
volumetric flask in order that the desired concentration will be obtained by subsequently filling the flask with water, keeping the temperature of the solution at 30C.
19. For the operation of a refrigeration plant it is desired to prepare a solution of
sodium chloride containing 20% by weight of the anhydrous salt.
(a) Calculate the weight of sodium chloride which should be added to one
gallon of water at 30C in order to prepare this solution.
(6) Calculate the volume of solution formed per gallon of water used, keeping
the temperature at 30 C.
20. (o) A solution has a gravity of 80 Twaddell. Calculate its specific gravity
and its gravity in degrees Baum^.
(b) An oil has a specific gravity at 60/60F of 0.651. Calculate its gravjty in
degrees API and degrees Baum6.
21. Make the following conversion of units:
(a) An energy of 8 ft-lb to kilogram-meters.
(6) An acceleration of 32.2 - - to - .
(sec)2
(sec)2
(c) A pressure of 100 mm of Hg to inches of water.
, ,s r^,
,
, . .
,.,
Btu
kcal
(d) Thermal conductivity of k (hr)rF)(ft)
to -(hr)(C)(m)'
, , n^
^ ,
82.06 (atm) (cm)' ^
Btu
(e) The gas constant R, from (g-mole)(K) - to (lb-mole) (R)
CHAPTER II
BEHAVIOR OF IDEAL GASES
In the preceding chapter consideration was given to problems
pertaining to the transformation of matter from one physical or chemical
state to another. It has been pointed out that matter is essentially
indestructible despite all the transformations it may undergo and that
the mass of a given system remains unaltered. However, in order to
complete the quantitative study of a system it is necessary to consider
one other property.
The properties of a moving ball, a swinging pendulum, or a rotating
flywheel are different from those of the same objects at rest. The differences lie in the motion of the bodies and in the ability of the moving
objects to perform work, which is defined as the action of a force moving
under restraint through a distance. Likewise, the properties of a redhot metal bar are different from those of the same bar when cold. The
red-hot bar produces effects on the eye and the touch very different from
those of the cold bar. The essential property or physicochemical concept
necessary to complete the quantitative description of matter is termed
energy.
Energy. All matter and the properties of matter are manifestations
of energy. Energy is the capacity of matter to perform work and to
affect the senses. For example, the motions of bodies cited above,
the warming of an object by solar radiation, and the change in composition of a storage battery when it generates electricity are all manifestations of energy. Energy is distributed throughout the universe in a
variety of forms, all of which may be directly or indirectly converted
into one another.
Under the classification of -potential energy are included all forms of
energy not associated with motion but resulting from the position and
arrangement of matter. The energy possessed by an elevated weight,
a compressed spring, a charged storage battery, a tank of gasohne, or
a lump of coal are examples of potential energy. Similarly, potential
energy is stored within an atom as the result of forces of attraction
among its subatomic parts. Thus potential energy can be further
classified as external potential energy, which is inherent in matter as a,
result of its position relative to the earth, or as internal potential energy,
which resides within the structure of matter.
27
28
[CHAP. II
/
/
jI
/'
CHAP. II]
29
where
y=
V =
m =
u =
number
volume
mass of
average
' This derivation may hp found in simplified form in any good physics or physical
chemistry text or in more rigorous form in the more advanced books deaUng with
kinetic theory.
30
[CHAP. II
From the definition of the molal units of quantity it was pointed out
that one mole of a substance will contain a definite number of single molecules, the same for all substances. Then
v = nN
(2)
where
^
n = number of moles in volume V
N = number of molecules in a mole, a universal constant equal to 6.023 X 10^' for the gram-mole
(3)
(4)
pV = nRT
(5)
where
i2 =
T =
V=
n =
V =
a proportionality factor
absolute temperature
volume of one mole'of gas
number of moles of gas
volume of n moles of gas
^
.
Rearranging (4)
K-f
"
CHAP. II]
31
| u . = ijr
(7)
lmu^-lT
. (8)
or
32
[CHAP.
II
(9)
(10)
CHAP. II]
38
From Equation (11) it is seen that R represents two-thirds of the translational kinetic energy possessed by one mole per degree of absolute
temperature. The numerical value of R has been carefully determined
and may be expressed in any desired energy units. Following are values
corresponding to various systems of units:
UNITS OF PBBSSURE
UNITS OF VOLUME
'
82.06
>
18,510
10.71
. 0.729
When substances exist in the gaseous state two general types of problems arise in determining the relationships between weight, pressure,
temperature, and volume. The first type is that in which are involved
only the last three variables pressure, temperature, and volume.
For example, a specified volume of gas is initially at a specified temperature and pressure. The conditions are changed, two of the variables
in the final state being specified, and it is desired to calculate the third.
For such calculations it is not required to know the weight of the gas.
The second, more general type of problem involves the weight of the gas.
A specified weight of substance exists in the gaseous state under conditions, two of which are specified and the third is to be calculated. Or,
conversely, it is desired to calculate the weight of a given quantity of
gas existing at specified conditions of temperature, pressure, and volume.
Problems of the first type, in which weights are not involved, may be
readily solved by means of the proportionality indicated by the gas law.
Equation (5) may be applied to n moles of gas at conditions pi, Vi, Ti
and also at conditions p2, V2, T2.
piVi = nRTi
P2V2 = nRTi
Combining:
>
34
[CHAP. II
quirement being that the units in both initial and final states be the same.
Equation (5) is in form to permit direct solution of problems of the
second type, in which are involved both weights and volumes of gases.
With weights expressed in molal units the equation may be solved for
any one of the four variables if the other three are known. However,
this calculation requires a value of the constant R expressed in units to
correspond to those used in expressing the four variable quantities. So
many units of expression are in common use for each variable quantity
that a very large table of values of R would be required or.,else the variable quantities would have to be converted into standard units. Either
method is inconvenient.
It proves much more desirable to separate such calculations into two
steps. As a primary constant, the normal molal volume is used instead
of R. The normal molal volume is the volume occupied by one mole of a
gas at arbitrarily selected standard conditions, assuming that the ideal
gas law is obeyed. The normal molal volume at any one set of standard
conditions, if the validity of Equation (5) is assumed, must be a universal
constant, the same for all gases. The volume, at the standard conditions, of any weight of gas is the product of the number of moles present
and the normal molal volume. The general type of problem involving
weights and volumes at any desired conditions may then be solved in
two steps. In one, the differences between the properties of the gas at
standard conditions and at those specified in the problem are determined
by Equation (12). In the other step the relationship'between volume
at standard conditions and weight is determined by means of the normal molal volume constant.
Standard Conditions. An arbitrarily specified standard state of temperature and pressure serves two purposes. It establishes the normal'
molal volume constant required in the system of calculation described in
the preceding section. It also furnishes convenient specifications under
which quantities of gases may be compared when expressed in terms of
volumes. Some such specification is necessary because of the fact that
the volume of a gas depends not only on the quantity but on the temperature and pressure as well.
Several specifications of standard conditions are in more or less common use but the one most universally adopted is that of a temperature
of 0C and a pressure of one atmosphere. It is recommended that these
conditions be adopted as the standard for all calculations. Under these
conditions the normal molal volumes are as follows (the abbreviation
S.C. is used to designate the standard conditions):
Volume of 1 gram-mole S.C. = 22.41 liters
Volume of 1 pound-mole S.C. = 359 cubic feet
CHAP. II]
35
Temperature
0Centigrade
273Kelvin
32Fahrenheit
492Raiikine
'
Pressure
1 atmosphere
760 mm of mercury
29.92 in. of mercury
14.70 lb per sq in.
There are many substances which cannot actually exist in the gaseous
state at these specified conditions. For example, at a temperature of
0C water cannot exist in a stable gaseous form at a pressure greater
than 4.6 mm of mercury. Higher pressures cause condensation. Yet,
it is convenient to refer to the hypothetical volume occupied by water
vapor at standard conditions. In such a case the volume at standard
conditions indicates the hypothetical volume which would be occupied
by the substance if it could exist in the vapor state at these conditions
and if it obeyed the ideal gas law.
Gauge Pressure. All ordinary pressure gauges indicate the magnitude of pressure above or below that of the atmosphere. In order to
obtain the absolute pressure which must be used in the gas law, the pressure of the atmosphere must be added to the gaiige pressure. The
average atmospheric pressure at sea level is 14.70 pounds per square
inch or 29.92 inches of mercury.
Gas Densities and Specific Gravities. The density of a gas is ordinarily expressed as the weight in grams of one Hter or the weight in
pounds of one cubic foot. Unless otherwise specified the volumes are at
the standard conditions of 0C and a pressure of 1.0 atmosphere. On
this basis air has a normal density of 1.293 grams per hter or of 0.0807
pound per cubic foot.
The specific gravity of a gas is usually defined as the ratio of its density
to that of air at the same conditions of temperature and pressure.
The gas law expresses the relationship between four properties of a
gas: mass, volume, pressure, and temperature. In order to calculate
any one of these properties the others must be known or specified. Four
different types of problems arise, classified according to the property
being sought. The following illustrations show the application of the
recommended method of calculation to each of these types of problems.
For establishment of correct ratios to account for the effects of pressure and temperature a simple rule may be followed which offers less
opportunity for error than attempting to recall Equation (12). The
ratio of pressures or temperatures should he greater than unity when the
36
[CHAP. II
Ti
TO^F = 530Raiikine.
7 Aft
f^Qft
492
QftQ
Vi
CHAP. II}
GASEOUS MIXTURES
37
Dissociating Gases. Certain chemical compounds when in the gaseous state apparently do not even approximately follow the relationships deduced above. The tendency of hydrogen fluoride to associate
into large molecules was mentioned in Chapter I. Ammonium chloride,
nitrogen peroxide, and phosphorus pentachloride exhibit an abnormality
. opposite in effect which has been definitely proved to result from dissociation of the molecules into mixtures containing two or more other
compounds. Ammonium chloride molecules in the vapor state separate
into molecules of hydrogen chloride and ammonia:
NH4CI = NHs-f-HCl
Thus gaseous ammonium chloride is not a pure gas but a mixture of three
gases, NH4CI, HCl, and NH3. By decomposition, two gas particles are
produced from one, and the pressure or volume of the gas increases above
that which would exist had no decomposition taken place. For this
reason, when one gram-mole of ammonium chloride is vaporized the
volume occupied will be much greater than that indicated by Equation
(5). However, when proper account is taken of the fact that in the
gaseous state there is actually more than one gram-mole present, it is
found that the ideal gas law applies. Conversely, from the apparent
deviation from the gas law the percentage of dissociation can be calculated if the chemical reaction involved is known.
Illustration 5. When heated to 100C and 720 mm pressure 17.2 grams of NjOi
gas occupy a volume of 11,450 cc. Assuming that the ideal gas law applies, calculate the percentage dissociation of N2O4 to NO2.
17.2
Gram-moles of N2O4 initially present = - = 0.187
; ' '-J
(
GASEOUS MIXTURES
n
'
38
[CHAP II
CHAP.
II]
39
will be shown later that each of these laws is correct where conditions
are such that the mixture and each of the components obey the ideal
gas law.
Where small molal volumes are encountered, such that the ideal gas
law does not apply either Dalton's or Amagat's law may apply, but
both laws apply simultaneously only for ideal gases. Under such conditions pressures may not be additive, because the introduction of
additional molecules into a gas-filled container may appreciably affect
the pressure exerted by those already there. The presence of new
molecules will reduce the space available for the free motion of those
originally present and will exert attractive forces on them. Similarly,
if quantities of two gases at the same pressure are allowed to mix at
that same pressure, the like molecules of each gas will be separated by
greater distances and will be in the presence of unhke molecules, which
condition may alter the order of attractive forces existing between them.
As a result, the volume of the mixture may be quite different from the
sum of the original volumes. These same effects are present but
negligible under conditions of large molal volumes and wide separation
of molecules.
Where conditions are such that the ideal gas law is applicable:
;
VA
where
= ^
(15)
y^.:\ ''..': ~
=.
^ . >..
V = total volume of mixture
n^ = number of moles of component A in mixture
)-^
(16)
^ \
P = NAP
"
(17)
+ nB + nc
The quantity NA = nA/{nA + UB + nc + ) is the mole fraction of
component A. Equation (17) then signifies that, where the ideal gas law
may be applied, the partial pressure of a component of a mixture is equal
to the product of the total pressure and the mole fraction of that component.
UA
40
[CHAr. II
Where conditions are such that the ideal gas law is applicable
"*'''
V^A = riART
(18)
P F B = UBRT
(19)
7B H
) = {nA + nB+
)RT
(20)
Combining Equations (18) and (19) with Amagat's law (Equation 14),
V
.: ^.
nA + nB + --^
^^^^
or
(22)
VA = NAV
Equation (22) signifies that, where the ideal gas law may be applied,
the pure-component volume of a component of a gaseous mixture is equal
to the product of the total volume and the mole fraction of that component.
From Equations (16) and (20) it is evident thtit when the ideal gas
law is valid both Amagat's and Dalton's laws apply, that is, both purecomponent volumes and partial pressures are additive.
Average Molecular Weight of a Gaseous Mixture. A certain group
of components of a mixture of gases may in many cases pass through a
process without being changed in composition or weight. For example,
in a drying process, dry air merely serves as a carrier for the vapor being
removed and undergoes no change in composition or in weight. It is
frequently convenient to treat such a mixture as though it were a single
gas and assign to it an average molecular weight which may be used for
calculation of its weight and volume relationships. Such an fiverage
molecular weight has no physical significance from the standpoint of the
molecular theory and is of no value if any component of the mixture
takes part in a reaction or is altered in relative quantity. The average
molecular weight is calculated by adopting a unit molal quantity of the
mixture as the basis of calculation. The weight of this molal quantity
is then calculated and will represent the average molecular v;eight. By
this method the average molecular weight of air is found to be 29.0.
Illustration 6. Calculate the average molecular weight of a flue gas having the
following composition by volume:
CO,
O,..
N,
13.1%
7.7%0
79.2%0
100.0%
CHAP. II]
41
5.76 grams
2.46 grams
22.18 grams
30.40 grams, which is the aver-
0.0555 lb-mole
0.0278 lb-mole
0.0833 lb-mole
'
29.9 cu ft
29 92 X 303
Volume at 29 in. Hg, 30C = 29.9 X ^
7 = 34.2 cu ft
29.0 X273
^.^^,,
Density at 29 in. Hg, 30C = 0.0292 lb per cu ft
.'
6.72 grams
22.10 grams
28.82 grams
22.41 liters
42
[CHAP. IJ.
24.8 liters
28 82
Denaty = ' = 1.162 grams per liter (741 mm Hg, 70F)
The actual density of the atmosphere is slightly higher owing to the
presence of about 1 per cent of argon which is classed as nitrogen in the
above problem. The mixture of nitrogen and inert gases in the atmosphere may be termed atmospheric nitrogen. The average molecular
weight of this mixture is 28.2.
^ . '
,
,.
,1
-.
I ;
,-,__.
\.,
43
48.3%
4.4%
8.3%
39.0%
100.0%
(o) Calculate the volume of gases leaving the evaporator per 100 cu ft entering.
(6) Calculate the weight of water evaporated per 100 cu ft of gas entering.
Solution:
'
N2
O2
COj
0.792 gram-mole
0.072 gram-mole
0.136 gram-mole
Total volume (743 mm Hg, 200C) calculated from Equations (14) and (20):
p = 743/760 or 0.978 atm
- \ ' '
T = 473K
iJ = 82.1 cc atm per "K
~.
.-,
'
1.75 cu ft
44
[CHAP. II
2 : 2 ? ^ ^
::
1.811b
1.40
Pure-component Volume Method. Where the ideal gas law m a y
be applied, t h e above m e t h o d of calculation is unnecessarily tedious.
I n this case the solution m a y be carried o u t without conversion to molal
or weight units b y appHcation of pure-component volumes. T h e total
volume of any ideal mixture m a y be obtained by adding together t h e
pure-component volumes of its components. Similarly, t h e removal
of a component from a mixture will decrease the t o t a l volume b y its
pure-component volume. C a r e m u s t be t a k e n in t h e use of this method
t h a t all volumes which are added together are expressed at the same
conditions of temperature and pressure.
A process involving changes in
t e m p e r a t u r e a n d pressure as well as composition is best considered as
t a k i n g place in two steps: first, t h e change in composition a t t h e initial
conditions of t e m p e r a t u r e a n d pressure; and second, the change in
volume of t h e resultant mixture to correspond to t h e final conditions of
t e m p e r a t u r e and pressure. Again t h e entire calculation m u s t be based
on a definite q u a n t i t y of a component which passes through t h e process
without change in q u a n t i t y . This procedure is indicated in t h e following illustration:
rr, , /.^
Illustration 10. In the manufacture of hydrochloric acid a gas is obtained which
contains 25% HCl and 75% air by volume. This gas is passed through an absorption system in which 98% of the HCl is removed. The gas enters the system at a
temperature of 120F and a pressure of 743 mm of Hg and leaves at a temperature
of 80F and a pressure of 738 mm of Hg.
(o) Calculate the volume of gas leaving per 100 cu ft entering the absorption
apparatus.
(6) Calculate the percentage composition by volume of the gases leaving the absorption apparatus.
(c) Calculate the weight of HCl removed per 100 cu ft of gas entering the absorption apparatus.
,
, ,:
,,
.. /
,
Solution:
Basis: 100 cu ft of entering gas (743 mm Hg, 120F) containing 75 cu ft of air
which will be unchanged in quantity.
Pure-component vol. of HCl
25 cu ft
Pure-component vol. of HCl absorbed
24.5 cu ft
Pure-component vol. of HCl remaining. . ..'
0.50 cu ft
Vol. of gas remaining:
75 + 0.50
75.5 cu ft (743 mm, 120F)
Vol. of gas leaving:
743 540
75-5 X r r r X ;
70.8 cu ft (738 mm 80F)
738 580
CHAP. II]
i .
45
0.66%
99.34%
743 492
Vol. at S.C. of HCl absorbed = 24.5 X X
20.3 cu ft
2.07 lb
.,
: '-.:,
681 mm Hg
742.5 mm Hg
100 cu ft
681
540
Actual volume of inert gases leaving = 100 X zrr-;; X -r~ = 92.5 cu ft. This
742.5 535
is also the total volume of gases leaving (743 mm Hg, 80F).
The actual volumes of chlorine entering and leaving are also 100 and 92.5 cu ft,
respectively.
59 X 492
Volume at S.C. of chlorine entering = 100
- . . . . 7.14 cu ft
760 X 635
0 5 X 492
Volume at S.C. of chlorine leaving = 92.5
0.055 cu ft
760 X 540
6-
46
, , ,,,
ICHAP. II
7.08 cu ft
1.40 lb
In a great many chemical and metallurgical reactions gases are present, either in the reacting materials or in the products or in both. Quantities of gases are ordinarily expressed in volume units because of the
fact that the common methods of measurement give results directly on
this basis. The general types of reaction calculations must, therefore,
include the complications introduced by the expression of gaseous quantities and compositions in volume units.
In Chapter I methods are demonstrated for the solution of reaction
calculations through the use of molal units for the expression of quantities
of reactants and products. Where this is the scheme of calculation,
the introduction of volumetric data adds but few comphcations. By
the use of the normal molal volume constants combined with the proportions of the ideal gas law it is easy to convert from molal to volume
units, and the reverse. The methods of conversion have been explained
in the preceding sections.
The same general methods of solution are followed" as were described
in Chapter I. All quantities of active materials, whether gaseous,
solid, or liquid, are expressed in molal units and the calculation carried
out on this basis. Results are thus obtained in molal units which may
readily be converted to volumes at any desired conditions. The most
convenient choice of a quantity of material to serve as the basis of
calculation is determined by the manner of presentation of the data.
In general, if the data regarding the basic material are in weight units,
a unit weight is the best basis of calculation. If the data are in volume
units, a unit molal quantity is ordinarily the most desirable basis.
Illustration 12. Nitric acid is produced in the Ostwald process by the oxidation
of ammonia with air. In the first step of the process ammonia and air are mixed
together and passed over a catalyst at a temperature of 700C. The following reaction takes place:
4NH3 + 5O2 = 6H2O + 4NO
The gases from this process are passed into towers where they are cooled and the
oxidation completed according to the following theoretical reactions:
2NO +O2
= 2NO2
CHAP. II]
GASES I N C H E M I C A L R E A C T I O N S
47
The NO liberated is in part reoxidized and forms more nitric acid in successive
repetitions of the above reactions. The ammonia and air enter the process at a
temperature of 20C and a pressure of 755 mm Hg. The air is present in such proportion t h a t the oxygen will be 2 0 % in excess of that required for complete oxidation
of the ammonia to nitric acid and water. The gases leave the catalyzer at a pressure
of 743 mm of H g and a temperature of 700C.
(a) Calculate the volume of air to be used per 100 cu ft of ammonia entering the
process.
(b) Calculate the percentage composition by volume of the gases entering the
catalyzer.
(c) Calculate the percentage composition by volume of the gases leaving the catalyzer, assuming that the degree of completion of the reaction is 8 5 % and t h a t no other
decompositions take place.
(d) Calculate the volume of gases leaving the catalyzer per 100 cu ft of ammonia
entering the process.
(e) Calculate the weight of nitric acid produced per 100 cu ft of ammonia entering
the process, assuming t h a t 9 0 % of the nitric oxide entering the tower is oxidized to
nitric acid.
Basis of Calculation:
(a)
O2 required
2.0 lb-moles
2.4 lb-moles
Air supplied =
2.4
0.210
11.42 lb-moles
Therefore:
4440 X 100
= 1142 cu ft
388
9.02 lb-moles
=2.4/12.42
N2
= 9.02/12.42
^ ....-I
8.0%
19.3%
72.7%
; -'y-"-
: '-'^A-^-'-^'
100.0%
48
(c)
[CHAP. II
Composition by volume:
NO
H2O
NH3
O2
N2
=
=
=
=
=
0.85/12.64
1.275/12.64
0.15/12.64
1.34/12.64
9.02/12.64
6.7%
10.1%
1.2%
10.6%
71.4%
0.258 lb-mole
4270 cu ft
3.26 lb-moles
1170 cu ft
0.219 lb-mole
0.197 lb-mole
12.4 lb
Range of Applicability of the Ideal Gas Law. The ideal gas law is
applicable only at conditions of low pressure and high temperature
corresponding to large molal volumes. At conditions resulting in small
molal volumes the simple kinetic theory breaks down and volumes
calculated from the ideal law tend to be too large. In extreme cases the
calculated volume may be five times too great, an error of 400 per cent.
If an error of 1 per cent is permissible the ideal gas law may be used
for diatomic gases where gram-molal volumes are as low as 5 liters
(80 cubic feet per pound-mole) and for gases of more complex molecular
structure such as carbon dioxide, acetylene, ammonia, and the lighter
hydrocarbon vapors, where gram-molal volumes exceed 20 liters (320
cubic feet per pound-mole).
The actual behavior of gases under high-pressure conditions is dis-
C H A P . II]
PROBLEMS
49
'
Calculate the number of hours of service which can be derived from 1.0 lb of carbide
in an acetylene lamp burning 2 cu ft of gas per hour at a temperature of 75F and a
pressure of 743 mm of Hg.
6. A natural gas has the following composition by volume:
'
s .'
CH4
N2
H2
O2
94.1%
3.0%
1.9%
1.0%
100.0%
This gas is piped from the well at a temperature of 20''C and a pressure of 30 lb
per sq in. I t may be assumed t h a t the ideal gas law is applicable. :
(a) Calculate the partial pressure of the oxygen.
(b) Calculate the pure-component volume of nitrogen per 100 cu ft of gas.
(c) Calculate the density of the mixture in pounds per cubic foot at the existing
conditions.
7. A gas mixture contains 0.274 lb-mole of HCl, 0.337 lb-mole of nitrogen, and 0.089
lb-mole of oxygen. Calculate the volume occupied by this mixture and its density in
pounds per cubic foot at a pressure of 40 lb per sq in. and a temperature of 30G.
8. A chimney gas has the following composition by volume:
'' - '
> ''
CO2
CO
O2
N2
10.5%
1.1%
7.7%
80.7%
'
'
50
B E H A V I O R O F I D E A L GASES
[CHAP. U
67%
28%
5%
. C H A P . II]
PROBLEMS
51
1.1%
8.2%
10.0%
80.7%
(a) Calculate the volume of the gas at 350F and 29.2 in. of Hg formed per
pound of sulfur burned.
(6) Calculate the percentage excess oxygen supplied for the combustion above
that required for complete oxidation to SO3.
(c) From the above gas analysis calculate the percentage composition b y volume
of the air used in the combustion.
(d) Calculate the volume of air at 70F and 29.2 in. of H g supplied for the combustion per pound of sulfur burned.
16. A furnace is to be designed to burn coke at the rate of 200 lb per hour.
coke has the following composition:
Carbon
Ash
The
89.1%
10.9%
The grate efficiency of the furnace is such t h a t 9 0 % of the carbon present in the coke
charged is burned. Air is supplied in 3 0 % excess of that required for the complete
combustion of all the carbon charged. It may be assumed that 9 7 % of the carbon
burned is oxidized to the dioxide, the remainder forming monoxide.
1
(o) Calculate the composition, by volume, of the flue gases leaving the furnace.
(b) If the flue gases leave the furnace at a temperature of 550F and a pressure
of 743 mm Hg, calculate the rate of flow of gases, in cubic feet per minute,
for which the stack must be designed.
16. Coke containing 87.2% carbon and 12.8% ash is burned on a grate. It is
found that 6 % of the carbon in the coke charged is lost with the refuse. The composition by volume of the stack gases from the furnace is as follows:
CO2
CO
O2
N2
12.0%
0.2%
8.8%
79.0%
(o) Calculate the volume of gases, at 540F and 29.3 in. of H g pressure, formed
per pound of coke charged.
(6) Calculate the per cent of excess air supplied above t h a t required for complete oxidation of the carbon charged.
(c) Calculate the degree of completion of the oxidation, to the dioxide, of the
carbon burned.
(d) Calculate the volume of air, at 70F and 29.3 in. Hg, supplied per pound of
coke charged.
62
[CHAP. II
17. In the fixation of nitrogen by the arc process, air is passed through a magnetically flattened electric arc. Some of the nitrogen is oxidized to NO, which on cooling
oxidizes to NO2. Of the NO2 formed, 66% will be associated to N2O4 at 26C.
The gases are then passed into water-washed absorption towers where nitric acid is
formed by the following reaction:
H2O -I- 3NO2 = NO -1- 2HNO3
The NO liberated in this reaction wjU be reoxidized in part and form more nitric acid.
In the operation of such a plant it is found possible to produce gases from the arc
furnace in which the nitric oxide is 2% by volume, while hot. The gases are cooled
to 26C at a pressure of 750 mm of Hg before entering the absorption apparatus,
(o) Calculate the complete analysis by volume of the hot gases leaving the furnace assuming that the air enteringthe furnace was of average atmospheric
composition.
(b) Calculate the partial pressures of the NO2 and N2O4 in the gas entering the
absorption apparatus.
(c) Calculate the weight of HNO3 formed per 1000 cu ft of gas entering the
absorption system if the conversion to nitric acid of the combined nitrogen
in the furnace gases is 85% complete.
CHAPTER III
VAPOR PRESSURES
Liquefaction and the Liquid State. Molecules in the gaseous state of
aggregation exhibit two opposing tendencies. The translational kinetic
energy possessed by each molecule represents a continual, random motion which tends to separate the molecules from one another and to
cause them to be uniformly distributed throughout the entire available
space. On the other hand, the attractive forces between the molecules
tend to draw them together into a concentrated mass, not necessarily
occupying the entire space which is available.
The first tendency, that of dispersion, is dependent entirely on the
temperature. An increase in the temperature will increase the translational kinetic energy of each molecule and will therefore give it an increased ability to overcome the forces tending to draw it toward other
molecules. The second tendency, that of aggregation, is determined by
the magnitudes and nature of the attractive forces between the molecules and by their proximity to one another. These intermolecular
attractive forces are believed to be of such a
nature that they increase to definite maxima
as the distances between molecules are
diminished. This behavior is shown in
Fig. 3, in which are plotted attractive
forces as ordinates and distances of separation between two molecules as abscissas.
The greatest attractive force between the
two molecules exists when they are sepa- FIG. 3. Attractive force between molecules.
rated by a relatively small distance 82- If
the distance of separation is diminished below Sj, the attractive force
rapidly decreases and will reach high negative values corresponding to
repulsion. At a distance of separation Si the attractive force becomes
zero, corresponding to a position of equilibrium. If unaffected by other
forces, molecules will group themselves together, separated from one
another by distances equal to Su Any attempt made to crowd them
closer together will meet with repulsive forces. In order to separate
them by a distance greater than S2 it would be necessary to overcome
the maximum attractive force by heating or expansion.
When a gas is isothermally compressed and the distances of separation
between the molecules are decreased, the attractive forces increase
53
64
VAPOR PRESSURES
[CHAP III
= Pr = p/Pe
= y, = v/vc
CHAP. Ill]
VAPORIZATION
55
Under conditions of equal reduced pressure and equal reduced temperature, substances are said to be in corresponding states. It will be
later shown that many properties of gases and liquids, for example,
the compressibilities of different gases, are nearly the same at corresponding states, that is, at equal reduced conditions.
Vaporization. As pointed out above, the liquid state results when
conditions are such that the potential energies of attraction between
molecules exceed their kinetic energies of translation. These conditions
are brought about when the temperature of a substance is lowered,
decreasing the kinetic energies of translation, or when the molecules are
crowded close together, increasing the energies of attraction. On the
basis of this theory the surface of a liquid may be pictured as a layer of
molecules, each of which is bound to the molecules below it by the
attractive forces among them. One of the surface molecules may be
removed only by overcoming the attractive forces holding it to the
others. This is possible if the molecule is given sufficient translational
kinetic energy to overcome the maximum potential energy of attraction
and to enable it to move past the point of maximum attraction. Once
it has passed this distance of maximum attraction, the molecule is free
to move away from the surface under the effect of its translational
energy and to become a gas molecule.
In the simple kinetic-theory mechanisms which have been discussed,
it is frequently assumed that all molecules of a substance at a given
temperature are endowed with the same kinetic energies and move at
the same speeds. Actually it has been demonstrated that this is not
the case and that molecular speeds and energies vary over wide ranges
above and below the average values. In every liquid and gas there are
always highly energized molecules moving at speeds much higher than
the average. When such a molecule comes to the surface of a liquid,
with its velocity directed away from the main body, it may have sufficient energy to break away completely from the forces tending to hold
it to the surface. This phenomenon of the breaking away of highly
energized molecules takes place from every exposed liquid surface. As
a result, molecules of the liquid continually tend to assume the gaseous or vapor state. This phenomenon is termed vaporization or
euaporation.
When a liquid evaporates into a space of limited dimensions the space
will become filled with the vapor which is formed. As vaporization
proceeds, the number of molecules in the vapor state will increase and
cause an increase in the pressure exerted by the vapor. It will be recalled that the pressure exerted by a gas or vapor is due to the impacts
of its component molecules against the confining surfaces. Since the
56
VAPOR PRESSURES
[CHAP. I l l
original liquid surface forms one of the walls confijiing the vapor, there
will be a continual series of impacts against it by the molecules in the
vapor state. The number of such impacts will be dependent on or will
determine the pressure exerted by the vapor. However, when one of
these gaseous molecules strikes the liquid surface it comes under the
influence of the attractive forces of the densely aggregated liquid molecules and will be held there, forming a part of the liquid once more.
This phenomenon, the reverse of vaporization, is known as condensation.
The rate of condensation is determined by the number of molecules
striking the liquid surface per unit time, which in turn is determined by
the pressure or density of the vapor. It follows that when a liquid
evaporates into a limited space, two opposing processes are in operation.
The process of vaporization tends to change the liquid to the gaseous
state. The process of condensation tends to change the gas which is
formed by vaporization back into the liquid state. The rate of condensation is increased as vaporization proceeds and the pressure of the vapor
increases. If sufficient liquid is present, the pressure of the vapor must
ultimately reach such a value that the rate of condensation will equal
the rate of vaporization. When this condition is reached, a dynamic
equilibrium is estabhshed and the pressure of the vapor will remain unchanged, since the formation of new vapor is compensated by condensation. If the pressure of the vapor is changed in either direction from this
equilibrium value it will adjust itself and return to the equilibrium conditions owing to the increase or decrease in the rate of condensation
which results from the pressure change. The pressure exerted by the
vapor at such equilibrium conditions is termed the vapor pressure of the
liquid. All materials exhibit definite vapor pressures of greater or less
degree at all temperatures.
The magnitude of the equilibrium vapor pressure is in no way dependent on the amounts of liquid and vapor as long as any free liquid surface is present. This results from both the rate of loss and the rate of
gain of molecules by the liquid being directly proportional to the area
exposed to the vapor. At the equilibrium conditions when both rates
are the same, a change in the area of the surface exposed will not affect
the conditions in the vapor phase.
The nature of the liquid is the most important factor determining the
magnitude of the equilibrium vapor pressure. Since all molecules are
endowed with the same kinetic energies of translation at any specified
temperature, the vapor pressure must be entirely dependent on the magnitudes of the maximum potential energies of attraction which must be
overcome in vaporization. These potential energies are determined by
the intermolecular attractive forces. Thus, if a substance has high
CHAP. Ill]
'
BOILING POINT
57
58
VAPOR PRESSURES
[CHAP. I l l
contact between the liquid and bubbles of vapor. The rising bubbles
also break up the normal surface into more or less of a froth. The vapor
once liberated from the liquid is at a higher pressure than the gas in
which it finds itself and will immediately expand and flow away from the
surface. These factors all contribute to make vaporization of a liquid
relatively very rapid when boiling takes place. When the total pressure
is such that boiling does not take place, vaporization will nevertheless
continue, but at a slower rate, as long as the vapor pressure of the liquid
exceeds the partial pressure of its vapor above the surface.
The temperature at which the equilibrium vapor pressure of a liquid
equals the total pressure on the surface is known as the boiling point.
The boiling point is dependent on the total pressure, increasing with an
increase in pressure. Theoretically, any Uquid may be made to boil at
any desired temperature by sufficiently altering the total pressure
on its surface. The temperature at which a liquid boils when under
a total pressure of 1.0 atmosphere is termed the normal boiling point.
This is the temperature at which the equilibrium vapor pressure equals
760 millimeters of mercury or 1.0 atmosphere.
Vapor Pressures of Solids. SoUd substances possess a tendency to
disperse directly into the vapor state and to exert a vapor pressure just
as do liquids. The transition of a solid directly into the gaseous state is
termed sublimation, a process entirely analogous to the vapotization of a
liquid. . A f amifiar example of sublimation is the disappearance of snow
in sub-zero weather.
A solid exerts an equilibrium vapor pressure just as a liquid does; this
is a function of the nature of the material and its temperature. Sublimation will take place whenever the partial pressure of the vapor in
contact with a solid surface is less than the equifibrium vapor pressure
of the solid. Conversely, if the equifibrium vapor pressure of the solid
is exceeded by the partial pressure of its vapor, condensation directly
from the gaseous to the solid state will result.
At the melting point the vapor pressures of a substance in the solid
and liquid states are equal. At temperatm'es above the melting gpint
the solid state cannot exist. However, by careful cooling a liquid can
be caused to exist in an unstable, supercooled state at temperatures
below its melting point. The vapor pressures of supercooled liquids
are always greater than those of the solid state at the same temperature,
and the liquid tends to change to the solid.
The vapor pressures of solids, evea at their melting points, are generally small. However, in some cases these values become large and of
considerable importance. For example, at its melting point of 114.5C
iodine crystals exert a vapor pressure of 90 millimeters of mercury.
CHAP. Ill]
59
(1)
where
p = vapor pressure
T = absolute temperature
A = heat of vaporization at temperature T
Vg = volume of gas
Vi = volume of liquid
,
'
60
VAPOR PRESSURES
[CHAP.
Ill
vapor state at the same temperature. The heat of vaporization decreases as pressure increases, becoming zero a;t the critical point. This
property is fully discussed in subsequent chapters. Values of the
heats of vaporization at the normal boihng point of many compounds
are listed in Tables XI and X I I I , pages 234-237.
By neglecting the volume of liquid and assuming the applicability
of the ideal gas law the above relation reduces to the Clausius-Clapeyron
equation:
dp
UT
or
^---l
where
R = gas law constant
or
>
log f = ^ 7 ^ ^ ^ - - - j
' po
2.303J? '
(4)
,._
74.
6850 calories per gram-mole.
1.99 calories per gram-mole per K.
273K.
185 mm Hg.
CHAP. Ill]
when
VAPOR-PRESSURE PLOTS
T = 293K (20C)
61
,
' - 2.30
^ X^ [ k - i ] ='''' ^-^^ - -^^^^3^ = -^^*
' ^ 185
when
: ^ -2.36
185
T = 308K (35C)
p = 437at20C
62
VAPOR PRESSURES
TABLE I
[CitAP. I l l
*^
English units
Pressure of aqueous vapor over ice in 10~' inches of Hg from 144 to 32F
Temp F
-140
-130
-120
-110
-100
-90
-80
-70
-60
-50
-40
-30
-20
-10
-0
0
10
20
30
0.0
0.00095
0.00276
0.00728
0.0190
0.0463
0.106
0.236
0.496
1.02
2.00
3.80
7,047
12.64
22.13
37.72
37.72
62.95
102.8
164.6
2.tf
0.00075
0.00224
0.00595
0.01,57
0.0387
0.0902
0.202
0.429
0.882
1.76
3.37
6,268
11.26
19.80
33.94
41.85
69.65 .
113.1
180.3
4.0
0.00063
0.00181
0.00492
0,0132
0.0325
0.0764
0.171
0.370
0.764
1.53
2.91
5.539
10.06
17.72
30.55
46.42
76,77
124,4
6.0
0.00146
0.00409
0.0111
0.0274
0.0646
0,146
0,318
0,663
1,33
2.59
4.882
8.902
15.83
27.48
51.46
84.65
136.6
8.0
0.00118
0.00339
0,00906
0.0228
0.0543
0.125
0,275
0,575
1.16
2.29
4.315
7,906
14,17
24,65 .
56.93
93.35
150.0
0.0
2.0
0
10
20
30
40
60
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
0.07091
0.1097
0.1664
0.2478
0.3626
0.5218
0.7392
1.0321
1.4216
1.9325
2.5955
3.4458
4.5251
5.8812
7.569
9.652
12.199
15.291
19.014
23,467
28.755
0.07760
0.1193
0.1803
0.2677
0.3906
0.5601
0.7912
1.1016
1.5131
2.0519
2.7494
3.6420
4.7725
6.1903
7.952
10.122
12.772
15.982
19.843
24,455
29,922
4,0
6,0
8.0
0,05402
0,08461
0,1299
0,1955
0,2891
0,4203
0,600'9
0,8462
1,1750
1,6097
2,1776
2,9111
3,8475
5,0314
6,5132
8,351
10,611
13,366 ^
16,699
20,703
25,475
0,05929
0,09228
0,1411
0,2118
0,3120
0.4620
0.6442
0.9046
1.2527
1.7117
2.3099
3.0806
4.0629
5.3022
6.850
8.767
11.120
13.983
17.443
21.593
26.531
0.06480
0,1007
0,1532
0,2292
0,3364
0.4858
0.6903
0.9666
1,3347
1,8192
2,4491
3.2589
4,2887
5.5852
7.202
9.200
11.649
14.625
18". 214
22.515
27.625
CHAP.
Ill]
'
63
TABLE I ~ (Continued)
Pressure of aqueous vapor over water in Ib/sq in. for temperatures 210-705.4F
Temp "F
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
620
530
540
550
560
570
580
590
600
610
620
630
640
650
660
670
680
690
700
0.0
2.0
4.0
6.0
8.0
14.123
17.186
20.780
24.969
29.825
35.429
41.858
49.203
57.556
67.013
77.68
89.66
103.06
118.01
134.63
153.04
173.37
195.77
220.37
247.31
276.75
308.83
343.72
. 381.69
422.6
466.9
514.7
666.1
621.4
680.8
744.3
812.4
885.0
962.6
1045.2
1133.1
1226.5
1325.8
1431.2
1642.9
1661.2
1786.6
1919.3
2059.7
2208.2
2366.4
2531.8
2708.1
2896.1
3093.7
14.696
17.861
21.667
25.884
30.884
36.646
43.252
60.790
69.356
69.046
79.96
92.22
106.92
121.20
138.16
156.95
177.68
200.60
225.56
252.9
282.9
315.5
351.1
389.7
431.2
476.2
524.6
576.9
632.9
693.2
757.6
826.6
900.1
978.7
1062.3
1151.3
1245.8
1346.4
1463.0
1566.2
1686.0
1812.3
1947.0
2088.8
2239.2
2398.1
2566.0
2745.0
2934.0
3134.9
15.289
18.657
22.379
26.827
31.973
37.897
44.682
52.418
61.201
71.127
82.30
94.84
108.85
124.46
141.77
160.93
182.07
206.33
230.85
258.8
289.2
322.3
368.5
397.7
439.8
485.6
534.7
687.8
644.6
706.8
770.9
840.8
916.3
995.0
1079.6
1169.7
1265.3
1367.2
1475.0
1589.4
1710.7
1838.6
1974.5
2118.0
2270.1
2431.0
2601.0
2782.0
2973.6
3176.7
15.901
19.275
23.217
27.798
33.093
39.182
46.150
64.088
63.091
73.259
84.70
97.52
111.84
127.77
146.46
165.00
186.55
210.25
236.24
264.7
296.7
329.4
366.1
405.8
448.7
496.2
644.9
689.9
666.6
718.6
784.6
855.2
930.9
1011.5
1097.2
1188.5
1285.1
1388.1
1497.4
1613.2
1735.6
1865.2
2002.7
2147.7
2301.4
2464.2
2636.4
2819.1
3013.2
3206.2*
16.533
20.016
24.080
28.797
34.245
40.502
47.657
55.800
66.028
76.442
87.15
100.26
114.89
131.17
149.21
169.15
191.12
215.26
241.73
270.6
302.2
336.6
374.0
414.2
457.7
504.8
555.4
610.1
668.7
731.4
798.1
870.0
946.6
1028.2
1115.1
1207.4
1305.3
1409.6
1520.0
1637.1
1761.0
1892.1
2031.1
2178.0
2333.3
2498.1
2672.1
2867.0
3063.2
64
VAPOR PRESSURES
>
[CHAP. I l l
CHAP. Ill]
65
stance has the same vapor pressure. Diihring lines of sodium hydroxide
solutions are plotted in Fig. 6, page 83, using water as the reference
substance. Each of these lines relates the temperature of the designated
solution to the temperature at which water exerts the same vapor pressure. Vapor-pressure data for water appear in Table I.
Equal Temperature Reference Substance Plots. If Equation (2) is
divided by a similar equation for a reference substance at the same temperature the following expression is obtained where the primed quantities
indicate the reference substance:^
dlnp
dlnp'
_ X
X'
^ ^
Integrating,'
*
X
logp = ~\ogp'
+ C
(6)
VAPOR PRESSURES
[CHAP.
Ill
11
5
a. o
E ft
^ ^
g
o
M
ft*
CHAP. Ill]
67
where
p = vapor pressure
T = temperature, K
A, B empirical constants
68
VAPOR PRESSURES
[CHAP. I l l
mately 2450 mm of Hg, the estimated vapor pressure at 100C. The experimentally
observed value is 2430 mm of Hg.
Illustration 3. The vapor pressure of normal butyl alcohol at 40C is 18.6 mm
of Hg. Estimate the temperature at which the vapor pressure is 760 mm of Hg,
the normal boiling point.
Solution: The experimental value of the vapor pressure at 40C is represented
by a point on Fig. 4. A straight line is drawn from this point to the point of convergence of the alcohol group. This point of convergence is located by extending
the curves for methyl and propyl alcohols. The abscissa of the point at which this
hue crosses the 760-mm ordinate is about 117C. The experimentally observed
boiling point of normal butyl.alcohol is 117.7C.
69
CHAP. Ill]
,._
___
""7"*
y
[_
(T
to ,a molal
vapor volume of 22.4 liters
A
Tff-
is-ra
, .
rr,
A'-
.r
^^
fr?
y
40-
'
r
J
"5
^s.
^'
_c>n
.'
.^
-i
_x
100
-''
200
^^
.^
>
I
- __-500
300
In
FIG. 6
400
T e
600
xi-700 _i800
;900
4.2
(8)
where:
Tc = critical temperature (K).
Te = the temperature (K) at which the substance is in equilibrium with its saturated vapor in a concentration of
1.0 gram-mole in 22.4 liters.
M = molecular weight.
pB = density of the liquid in grams per cubic centimeter at its
normal boiling point. By means of Fig. 109, Chapter XII,
PB can be estimated from density measurements at other
temperatures.
The temperature Te is a function of the normal boiling point of the substance. In Fig. 5, a curve is plotted relating (Te T^) to Ts, where
70
VAPOR PRESSURES
[CHAP.
Ill
' *"
'
,.
_ ,
- (9)'
.
Vc = critical volume, cc per gram-mole
P = parachor
(10)
CHAP. Ill]
where
71
M = molecular weight
a = surface tension, dynes per cm
pi = density of liquid, grams per cu cm
Pg = density of gas, grams per cu cm
C
H
N
P
0
S
F
CI
Br
1
4.8
17.1
12.5
37.7
20.0
48.2
25.7
54.3
68.0
91.0
Triple bond
,.;
Double bond
3-membered ring
4-membered ring
5-membered ring
6-membered ring
Gain esters
46.6
23.2
16.7
11.6
8.5
6.1
60.0
S. Sugden, The Parachor and Valency, Rutledge and Sons, London, 1930.
mission.
For a few simple molecules, such ae CO, CO2, SO3, the results of Table II
are not accurate. For water and diphenyl Equation (9) does not apply.
Otherwise, for a group of one hundred compounds selected at random
the deviation never exceeded 5% from experimental values. Equation
(9) is also appUcable to associated liquids, the parachor being based
upon the structure of the nonassociated liquid.
For the critical temperature, Equation (8) is preferable for nonpolar
compounds. For polar substances or where the liquid density is not
known the following empirical formulas have been developed by Meissner
and Redding:
For compounds boiling below 235K and for all elements.
Tc = 1.70TB
2.0
(11)
where
66 -
IIF
(12)
(13)
72
VAPOR PRESSURES
[CHAP.
Ill
where
r = ratio of noncyclic carbon atoms to the total number of carbon
atoms in the compound
(c) Other compounds (boiling above 235K, containing no aromatics, no naphthenes, no halogens, and no sulfur):
^
.M,-.
To = 1.027^5 + 159
'
(14)
20.87,
e-)
"
With the exception of water, maximum errors of 15 per cent are encountered and the majority of the results are within 10% of the experimental values.
Meissner and Redding discuss a method of using the preceding equations when the normal boiling point is unknown but a vapor-pressure
and a liquid density value are available at some other temperature.
Illustration 5. Estimate the critical properties of triethylamine (C3H6)3N, normal boiling point 362.5K.
Molecular weight
=101.1
Parachor: Prom Table II
"
Cs
Hl5
6 X 4.8 = 28.8
15 X 17.1 = 256.5
1 X 12.5 = 12.5
297.8
CHAP. Ill]
73
,;'i !?;; vf
, ^
+ B - e-aocr.-w^
(16)
t "i
Methane
Ethane
Ethylene
Propane
n-Octane
Water
Methyl alcohol
Diethyl ether
Acetone
Ammonia
Methylamine
Hydrogen cyanide.. .
Methyl chloride
Carbon tetrachloride.
Acetic acid
TABLE Ila
\
j
\~--
'
VAPOR-PBESSUBB CONSTANTS
logio p in mm of H g
A
p,
2.3383
2.5728
2.5463
2.6606
3.2316
3.1423
3.5876
2.9726
3.0644
2.9207
2.9589
3.2044
2.7195
2.J989
3.3908
6.8800
7.1411
7.1269
7.1819
7.5034
8.3610
8.3642
7.4039
7.6173
7.8519
7.7066
7.7761
7.4185
7.3329
8.0291
0.000
0.088
0.098
0.125
0.236
0.163
0.243
0.204
0.180
0.163
0.239
0.000
0.052
0.158
0.138
34,810
37,090
38,080
33,210
18,700
165,470
59,790
27,000
35,720
85,350
55,940
37,300
50,010
34,200
43,480
"
.
TTS.
190.7
305.5
282.8
370.0
569.4
647.2
513.2
467.0
508.2
406.1
430.1
456.7
416.4
556.3
594.8
' B. W. Gamson and K. M. Watson, presented before Petroleum Div., Am. Chem.
Soc, Pittsburgh meeting, Sept., 1943. To be published Nat. Petr. News, 1944.
74
VAPOR PRESSURES
[CHAP.
HI
Since th,e exponential correction term is found to be negligible at reduced temperatures above 0.8, B == log p^ + A, and Equation (16)
may be written:
't.
log p, = Z ^ ^ I Z I Z L ) _ e-20(T,-
(17)
Jr
700
^600
6'
g400
0.3 o
I
3
o
O
300
0.2 f
200
0.1 >
too2
6 7 8 9 10
Number of Carbon Atoms, n
40
0.0
50
CHAP. Ill]
75
(18)
(19)
TABLE lib
Acids
Alcohols
Aldehydes
Amines, primary
"
secondary
Aromatic hydrocarbons (monocyclic)
Esters
Ethers
Halogenated paraffins, mono
Ketones
Naphthenes
Nitriles
Phenols
Olefins, mono
Ap Ib/sq in.
c
300
0
480
0
250
0(?)
69
1.3
80
0
830
3.0
60
-1.6
0
0
47
1.0
180
0
970
0
0
0
1360
-3.0
63
0
A6
0.05
0.22
0.0(?)
0.12
0.12
0.02
0.09
0.04
0.08
0.05
-0.03
0.02
0.0(?)
0.01
Illustration 6. The normal boiling point of n-propyl amine is 48.7C and its
critical temperature 223.8C. Estimate the critical pressure and the vapor pressure
at a temperature of 0C.
b' = 0.133
c= -1.3
A6=0.12
76
VAPOR PRESSURES
[CHAP. Ill
14.7
p. = = 0.0216
TB =
= 0.549
'
'
'
>',-j;iv,'
-2.9703(1 - 0.549)
log pr =
Two liquids which are immiscible in each other can exist together only '
in nonhomogeneous mixtures. In such systems, where intimate mixing is maintained, an exposed liquid surface will consist of areas of each
of the component liquids. Each of these components will vaporize at
the surface and tend to establish an equilibrium value of the partial
pressure of its vapor above the surface. As has been pointed out the
equilibrium vapor pressure of a hquid is independent of the relative
proportions of liquid and vapor, but is determined by the temperature
and the nature of the liquid. I t follows from kinetic theory that the
equilibrium vapor pressure of a liquid should be the same, whether it
exists alone or as a part of a mixture, if a free surface of the pure liquid
is exposed. In a nonhomogeneous mixture of immiscible liquids the
vaporization and condensation of each component takes place at the
respective surfaces of tjie pure liquids, independently of the natures or
CHAP. Ill]
77
P.p. C(,H^
390 mm
650 mm
460 mm
"
610 mm
' >
520 mm
v.p. HS
150 mm
235 mm
190 mm
215 mm
225 mm
Total v.p.
540 mm
785 mm
650 mm
725 mm
745 mm
78
VAPOR PRESSURES
[CHAP. I l l
The boiling point of the mixture will, therefore, be 69C. This result could be
obtained graphically by plotting a curve relating temperature to total vapor pressure.
Basis: 1 lb-mole of mixed vapor.
520
Benzene= - = 0.70 lb-mole or 0.70 X 78 =
745
Water = 0.30 lb-mole or
5.4
Steam per pound of benzene = =
oo
55 lb
5.4 lb
0.099 lb
0.0098 lb
181b
1840 lb
CHAP.
Ill]
79
3.58 lb
17.7 lb
4.95 lb
33.1 lb
15.4 lb
0.465 lb
80
.!''
VAPOR PRESSURES
^Uln'i/
[CHAP. I l l
SOLUTIONS
-PA
VA = PA\
where
]^
r; ^
"":
+ nB + nc^
\WA
= ^J^PA
)-A^A
(20)
CHAP. Ill]
81
1340 mm Hg
560 mm Hg
210 mm Hg
82
VAPOR P R E S S U R E S
Basis:
[CHAP. I l l
100 lb of solution:
-..:
35
. '
Benzene = 35 lb or =
78
40
Toluene = 40 lb or =
:. ::
0.449 lb-mole
0.435 lb-mole
25
o-Xylene = 25 lb or - =
106
0.236 lb-mole
Total = lOOlb or
1.120 lb-mole
Vapor pressures:
-J* "
0.449
Benzene = 1340 X = 1340 X 0.401 =
536 mm Hg
0.435
Toluene = 660 X = 560 X 0.388 =
217 mm Hg
44 mm Hg
Total =
*.
797 mm Hg
Liquid
40.1%
38.8%
21.1%
100.0%
Vapor
536/797 = 67.3%
217/797= 27.2%
44/797 =
5.5%
100.0%
'
CHAP.
83
NONVOLATILE SOLUTES
Ill]
60
~1
40
lY
>
10
;15
t" 20
-20
20
40
60
80
100
Temperature of NaOH Solutions, C
120
84
VAPOR PRESSURES
[CHAP.
Ill
This type of plot has the advantage over the Diihring plot of permitting
estimation of thermal data from the slopes of the vapor pressure lines
and Equation (6), and may or may not give closer approximation to
straight Une relationships, depending on the particular system involved.
The difference between the boiling point of a solution and that of the
pure solvent is termed the boiling-point elevation of the solution. It
will be noted that the lines of Fig. 6 diverge but slightly at the higher
temperatures. It follows that the boiling-point elevation of a solution
of sodium hydroxide is practically independent of temperature or pres-
1000
800
30
20
50
40
60
Temperature C
70
80 90 100 110 120 130140150160170180
T
1
<"
1
1
1
1
1
600
400
'
I/I
/ 1
/\
1 1
1 /
i/i
L^^l
-3 200
1 1T
]/i 1A
i/i
1
?^ 1
100
80
60
/
40
y^*
0<
I
>
FIG.
'A
A ?l / ! *
1
1
7.
40
1
1
t
1A
/
20
\/\
1
1
1
1
1/
1
1
1 / \
/
1 /I 1
/i
[I
1/1 1
1 / ^' 1
1/ 1
/
10
10
A1
<*
1
4
\M A 1
/ ' 1
1A
60 80100
200
400 600 8001000
Vapor Pressure of Water in mm Hg
1 . 1
i
1 '/i
2000
1
1
1
1
1
Chem.,
CHAP. Ill]
where
PROBLEMS
86
For an ideal solution the factor k will equal the mole fraction of the solvent and will be independent of temperature or pressure. For nonideal solutions k may differ widely from the mole fraction but in many
cases it will be practically independent of temperature or pressure for a
solution of a given composition. The factor k is sometimes termed the
relative vapor pressure of a solution. The value of k for a solution may be
obtained by a single determination of boiling point. Equation (21)
may then be used to estimate the vapor pressures at other temperatures.
Illustration 11. An aqueous solution of sodium chloride contains 5 gram-moles of
NaCl per 1000 g of water. The normal boiUng point of this solution is 106 C.
Estimate its vapor pressure at 25C. ;
' ,', .
Mole fraction of water = ( 1
V
From Table I, po at 106C =
Po at 25C =
) = 1 - 0.0826 = 0.9174
55.5 + 6 /
940. mm of Hg
23.5 mm of Hg
760
fc
= =0.81
. . , , , :
940
Vapor pressure of solution at 25C = 23.5 X 0.81 = 19.0 mm Hg
Experimentally observed value =
18.97 mm Hg
VAPOR PRESSURES
86
[CHAP.
Ill
Temperature Range
-30C to24C
-38C to Critical Temp.
0C
to 46.3C
-34.6C to 30C
0C
to 50C
10C
to 60C
26C
to 80C
10C
to 70C
35C
to 80C
34.6C to 120C
-24.0C to 40C
Pressure Units
atm
atm
mm Hg
abn,
atm
mm Hg
mm Hg
mm Hg
mm Hg
atm
atm
CHAP.
PROBLEMS
Ill]
87
4. Use the Cox chart (Fig. 4) to determine the boihng point at 2000 mm Hg of one
of the following substances. Use the vapor pressure data that are given below to
establish the line on the Cox chart.
Ethyl Acetate
0C 24.2 mm Hg
160C 8.349 atm
Ethyl Formate
0C 72.4 mm Hg
200C 28.0 atm
Sulfur
250C 12 mm Hg
444.6C 760.0 mm Hg
5. The boiling point of benzene is 80C and its liquid density at the boihng point is
0.80 gram per cc. Estimate its critical temperature both by Equation (8) and Equations (11) to (14).
6. In the following tabulation, the normal boiling point, critical temperature, and
liquid density at the normal boiling point are given for several hydrocarbons. For
one of the materials assigned from this list, calculate the critical temperature, using
Equation (8) and Fig. 5. A comparison of this computed value with the experimental value will ^ve an indication of the accuracy that may be expected by this method.
Hydrocarbon
n-Butane i
n-Pentane
n-Hexane
n-Heptane
n-Octane
Cyclohexane
Normal
Boiling Point
C
-0.3
36.1
69.0
98.4
125.8
80.8
Critical
Temperature
C
153
197
235
267
296
281
Liquid Density
at Normal
Boihng Point
0.605 g/cc
0.610
0.613
0.613
0.611
0.719
7. Using equations (9) to (15) calculate the critical properties of the following
compounds and compare them with the tabulated experimental values:
Compound
Acetone
Acetic acid
Ammonia
Chlorobenzene
Trifluorotrichloroethane
Ethyl alcohol
TB^
329.0
391.0
239.6
405.0
322.0
351.0
rcK
508.2
594.8
405.6
632.2
487.0
516.3
p^ atm
47.0
57.2
111.5
44.6
34.0
63.1
Vc cc/gr mole
216.5
171.0
72.5
308.0
167.0
8. Using the data of Fig. 5a and Table lib calculate the necessary data and plot
vapor pressure curves extending from 0.01 lb per sq in. to the critical point for the
following substances. Plot the curves on five cycle semi-logarithmic paper, using
vapor pressures as ordinates on the logarithmic scale and temperatures in F as
(a) Decane {U = 347C) {is = 174C)
(6) Toluene [U = 320.6C) ((B = 110.8C)
(c) Propyl ethyl ether . = 227.4C) (<B = 64C)
9. Using the data of Fig. 4 estimate the temperature required for the distillation of
hexadecane (C16H34) at a pressure of 750 mm Hg in the presence of liquid water.
Calculate the weight of steam evolved per pound of hexadecane distilled.
88
VAPOR PRESSURES
[CHAP. I l l
10. A fuel gas has the following analysis by volume (in the third column are the
normal boiling points of the pure components):
^ ''
' <;-i|
,'iH
f,!3,,;
Components
Ethane (CsHj)
Propane (CsHs)
Isobutane (C4H10)
Normal butane (C4H10)..,.
Pentanes (C6H12)
Percentage
4.0
38.0 v
8.0
44.0
6.0
,:
100.0
"
Boiling Point
-88C
-"
-44C
.,:,; 0
-10C
. ?;
0C
-1-30C (average)
.3
'""
It is proposed to liquefy this gas for sale in cylinders and tank cars.
(o) Calculate the vapor pressure of the liquid at 30C and the composition of the
vapor evolved. (The vapor pressures may be estimated from Fig. 4 and
the normal boiUng points.)
(fc) Calculate the vapor pressure of the liquid at 30C if all the ethane were
removed.
11. Assuming that benzene (CsHe) and chlorobenzene (CeHsCl) form ideal solutions, plot curves relating total and partial vapor pressures to mole percentages of
benzene in the solution at temperatures of 90, 100, 110, and 120C. Also plot the
curves relating total vapor pressure to the mole percentage of benzene in the vapor
at 90 and 120G. The normal boiling point of benzene is 79.6C. Following are
other vapor pressure data:
Vapor Pressure mm Hg
Temperature
s\
90C
100
110
120
132.1
Chlorobenzene
208
293
403
542
760
Benzene
1013
1340
1744
2235
2965
12. From the curves of Problem 11, plot the isobaric boiling-point curves of benzene-chlorobenzene solutions under a pressure of 760 mm of Hg. The points on both
the liquid and vapor curves corresponding to temperatures of 90, 100, 110, and
120C should be used in establishing the curves.
13. An aqueous solution of NaNOs containing 10 gram moles of solute per 1000 g
of water boils at a temperature of 108.7C under a pressure of 760 mm of Hg. Assuming that the relative vapor pressure of the solution is independent of temperature,
calculate the v^ipor pressure of the solution at 30C and the boiling-point elevation
produced at this pressure.
14. Obtaining the necessary data from the section on " Boiling Points of Mixtures "
of Volume III of the International Critical Tables, plot the isobaric boihng-point
curves for the system acetic acid (CH3COOH) and water under a pressure of 760 mm
of Hg. Both the Uquid and vapor composition curves should be plotted using percentages of water by weight as abscissas and temperatures in degrees Centigrade
as ordinatea.
'
.: ,
> CHAPTER IV
HUMIDITY AND SATURATION
When a gas or a gaseous mixture remains in contact with a Uquid surface, it will acquire vapor from the Uquid until the partial pressure of
the vapor in the gas mixture equals the vapor pressure of the liquid at
its existing temperature. When the vapor concentration reaches this
equilibrium value the gas is said to be saturated with the vapor. It is
not possible for the gas to contain a greater stable concentration of vapor,
because as soon as the vapor pressure of the liquid is exceeded by the
partial pressure of the vapor condensation takes place. The vapor
content of a saturated gas is determined entirely by the vapor pressure
of the liquid and may be predicted directly from vapor-pressure data.
The pure-component volume of the vapor in a saturated gas may be
calculated from the relationships derived in Chapter II. Thus, if the
ideal gas law is applicable:
V,=
V^
V
(1)
where
'
From Equation (1) the percentage composition by volume of a vaporsaturated gas may be calculated. When the ideal gas law is applicable,
the composition by volume of a vapor-saturated gas is independent of
the nature of the gas but is dependent on the nature and temperature of
the liquid and on the total pressure. The composition by weight varies
with the natures of both the gas and the liquid, the temperature, and
the total pressure.
For certain types of engineering problems it is convenient to use
special methods of expression for the vapor content of a gas. The weight
of vapor per unit volume of vapor-gas mixture, the weight of vapor per
unit weight of vapor-free gas, and the moles of vapor per mole of vaporfree gas are three common and useful methods of expression. When a gas
89
90
[CHAP. IV
0.593 cu ft
59.3%
40.7%
43.9 lb
11.4 lb
55.3 lb
79.4%
20.6%
393 cu ft
43.9
Weight of ether per cubic foot = - =
ovo
0.112 lb
This result is independent of the total pressure. For example, an increase in the
total pressure would decrease the volume per mole of mixture but would correspondingly decrease the weight of vapor per mole of mixture.
(d) Basis: Same as (&).
43.9
Weight of vapor per pound nitrogen = =
3.85 lb
CHAP. IV]
PARTIAL SATURATION
91
= 1.455
(2)
where
Pa = partial pressure of vapor actually present
p, = partial pressure at saturation
Jt:,^
Ua
(3)
92
[CHAP. IV
where
Ua = moles of vapor per mole of vapor-free gas actually present
Ua = moles of vapor per mole of vapor-free gas at saturation
from Dalton's law,
'
, .
na
Pa
, ns
Ps
=
and - =
1
P - Pa
1 p - Pa
M l ' - ' - ,
'
,^^
(i)
or
, ,
,.
\
hence
n^^pa/y-pA
n^
p, \p - Pa/
. , : <
,
Sp = Sr (?^^^)
\P - Pa/
_ ,.
p = total pressure
, \;
(6)
where
, ' ,'
24.8%
0.248
0.752
0.329
52.9%
,.,,,
CHAP. IV]
93
130 mm of Hg
From the vapor-pressure data for water it is found that this pressure corresponds
to a temperature of 57C.
. .
"-'"'{v^J
\P - Pa/
. iH.
<"
94
[CHAP. IV
^
Illustration 4, A mixture of benzene vapor and air contains 10.1% benzene by
volume.
(a) Calculate the dew point of the mixture when at a temperature of 25C and a
pressure of 760 mm of Hg.
(6) Calculate the dew point when the mixture is at a temperature of 30C and a
pressure of 750 mm of Hg.
(c) Calculate the dew point when the mixture is at a temperature of 30C and a
pressure of 700 mm of Hg.
Solution:
(a) Partial pressure of benzene = 0.101 X 750 =
75.7 mm Hg
From the vapor pressure data for benzene, Fig. 4, it is found that this pressure corresponds to a temperature of 20.0C, the dew point.
(6) Partial pressure of benzene
75.7 mm
Dew point
20.0C
(c) Partial pressure of benzene = 0.101 X 700
70.7 mm Hg
The temperature corresponding to a vapor pressure of 70.7 mm of Hg is found to be
18.7C. From these results it is seen that the dew point does not depend on the
temperature but does vary with the total pressure.
VAPORIZATION PROCESSES
CHAP. IV]
VAPORIZATION PROCESSES
95
and that dissipated in various ways is of great significance. The calculation of such an energy balance is greatly simplified if the quantities of all
materials concerned are expressed in molal or weight units rather than
in volumes. These units have the advantage of expressing quantity
independent of change of temperature and pressure. The same desirability of weight or molal units arises when relationships are derived for
the design of vaporization equipment. For these reasons it has become
customary to express all data in either weight or molal units where thermal calculations are to be made or where design relationships are to be
used. The molal units are preferable. From data expressed in molal
units, volumes at any desired conditions may be readily obtained.
It will be noted that in any mixture following the ideal gas law the
ratio of the number of moles of vapor to the number of moles of vapor-free
gas is equal to the ratio of the partial pressure of the vapor to the partial
pressure of the vapor-free gas. Accordingly, vapor concentration in
moles of vapor per mole of vapor-free gas is obtained by dividing the partial pressure of the vapor by the partial pressure of the vapor-free gas.
Illustration 5. It is proposed to recover acetone, which is used as a solvent in an
extraction process, by evaporation into a stream of nitrogen. The nitrogen enters
the evaporator at a temperature of 30C containing acetone such that its dew point
is 10C. It leaves at a temperature of 25C with a dew point of 20C. The barometric pressure is constant at 750 mm of Hg.
(a) Calculate the vapor concentrations of the gases entering and leaving the evaporator, expressed in moles of vapor per mole of vapor-free gas.
(6) Calculate the moles of acetone evaporated per mole of vapor-free gas passing
through the evaporator.
(c) Calculate the weight of acetone evaporated per 1000 cu ft of gases entering
the evaporator.
(d) Calculate the volume of gases leaving the evaporator per 1000 cu ft entering.
Solution: The vapor pressure of acetone is:
116 mm of Hg at ICC
185 mm of Hg at 20C
(a) Entering gases:
"
Partial pressure of acetone
Partial pressure of nitrogen = 750
Moles of acetone per mole of nitrogen
Leaving gases:
Partial pressure of acetone
Partial pressure of nitrogen = 750
Moles of acetone per mole of nitrogen
(b) Basis: 1.0 lb-mole of nitrogen.
Acetone leaving the process
Acetone entering the process
Acetone evaporated
' ,__ .
116
= 116/634...
116 mm of Hg
634 mm of Hg
0.183
185
= 185/565...
185 mm of Hg
565 mm of Hg
0.328
0.328 lb-mole
0.183 lb-mole
0.145 lb-mole
96
[CHAP. IV
< , ,;;
,;.
1.183 lb-moles
477 cu ft
58
8.4 lb
17.6 lb
1.328 lb-moles
'
;=; s
CONDENSATION
CHAP. IV]
CONDENSATION
97
14.0 mm of Hg
0.0190
9.2 mm of Hg
1810 mm of Hg
'
0.0051
736 mm of Hg
736 273
Partial volume of dry air at S.C. = 1000 X ; X = 903 cu ft
2.52 Ib-molea
0.0478 lb-mole
0.0128
0.630 lb
2.53 Ib-moIea
760
283
Final volume of wet air = 2.63 X 369 X r r X r r 1810 273
396 cu ft
''
at 30C = 282.7 mm of Hg
at 25C = 229.2 mm of Hg
at 5C = 89.1 mm of Hg
.'
...
.- ,
,
98
[CHAP. IV
229.2 mm of Hg
0.306 lb-mole
0.694 lb-mole
0.0306 lb-mole
0.725 lb-mole
89.1 mm
. -,
4.22%
40.8 lb per sq in.
^
When a liquid evaporates into a large volume of gas at the same temperature, if no heat is supplied from an external source the liquid will be
cooled as a result of the heat removed from it to supply the relatively
large demand of the latent heat of vaporization. If the body of liquid
has a large surface area in proportion to its mass, its temperature will
quickly drop to an equilibrium value. This equihbrium temperature
which is assumed by the evaporating liquid will be such that heat will
be transferred to it from the warmer gas at a rate which is just adequate
to supply the necessary latent heat for the vaporization. The equilibi
rium temperature of a liquid when vaporizing into a gas is termed the
wet-bulb temperature and is always less than the actual dry-bulb temperature of the gas into which evaporation is taking place. If the gas is
saturated there is neither vaporization nor depression of the wet-bulb
temperature. It is therefore possible to use the depression of the wetbulb temperature as a measure of the degree of unsaturation of the mixture of gas and vapor.
Although, by the evaluation of the required equations or charts, it is
possible to extend wet- and dry-bulb thermometry to the determihation
of concentrations of different types of vapors, the only systems for which
the method has been extensively used are those involving water vapor.
This special appUcation of wet- and dry-bulb thermometry is termed
hygrometry or psychrometry. The United States Weather Bureau has
worked out extensive psychrometric tables and charts from which
humidities of air may be obtained with accuracy. For engineering
purposes humidity charts have been developed which permit the determination of the humidities of any of the common gases from wet- and
dry-bulb thermometric data. The limitation of these charts is that
each chart is applicable only to systems which exist under a single, specified
CHAP. IV]
99
100
'
[CHAP. IV
the dry gas composition. These lines permit appUcation of the chart
to mixtures of all the common gases.
A line on the chart which is parallel to the temperature axis represents
a change of temperature without change in molal humidity. This fact
0.34
11
^^g
^ ^ 1 ^ ^ )
0.32
1/ 1
0.30
45i
0.28
0.26
^c ,
^'-
024
19,400
^ ^
19,200
- - - - := - 19,000
~-L
4.
18,800 Ji
140j
f" >Sf
&LU
0.22
-i/^' /
ft
3S1
18,600 h
1
fh
18,400
18,200 .
0.20
p
I 0.18
a
18,000^
o
130y
' '
125>
3 0.16
17.800 X
17,600
120.
0.14
17.400 .
115.
0.12
17,200
110
^70/* ~60-^
105, /90V
0.10
36
20
ir~
^1
2.5 ?b
17.000
LOO,
0.08
0.06
^x
fca<
0.04
1 ^
0.02 p
0.00
80
90
100
110
120
130
140
ISO 160
Temperature,"?
170
180
0.00
^ ^ on
190
200
210
may be used for estimation of the dew point of a mixture whose properties are represented by an estabhshed point on the chart. A line is projected through this point, parallel to the temperature axis, to the saturation curve A. The abscissa of the intersection of this line with the
saturation curve is the dew point of the mixture.
/ / /
/ /
9'
20
30
40
50
Pressure
X
60
70
80
TempratureF
90
100
uo
120
fcii'
FIG. 9. Molal humidity chart (low temperature range). To use either Fig. 8 or
9 in obtaining the pounds of water per pound of dry air multiply molal humidity,
ordinates of the charts, by 18/29 or 0.62.
101
102
[CHAP.
IV
1.037 lb-moles
CHAP.
IV]
103
25
26
27
28
29
30
Absolute Pressure, Inches of Mercury
104
[CHAP. IV
Illustration 9a. At 26.42 in. Hg the dry-bulb temperature of air is 150F and
its wet-bulb temperature is 120F. Obtain the correct humidity from the charts.
From Fig. 8, molal humidity
=0.116
From Fig. 9a, molal humidity correction = .020
Corrected molal humidity
/
.136
'
'
i "
CHAP. IV]
PROBLEMS
105
106
[CHAP. IV
CHAP. IV]
PROBLEMS
107
108
[CHAP. IV
19. Air at 25C, 740 mm of mercury, and 65% relative humidity is compressed to
10 atm.
(a) To what temperature must the gas-vapor mixture be cooled if 90% of the
water is to be condensed?
(6) On the basis of 1 cu ft of original air, what will be the volume of the gasvapor mixture at 10 atmospheres after cooling to the final temperature?
In working out the following problems, the humidity charts in Figures 8 and 9 are to he
used as jar as possible. The use of the large-scale chart in Figure 9 is preferable within
its range. Unless otherwise specified the pressure is assumed to be one atmosphere.
20. Air at atmospheric pressure has a wet-bulb temperature of 62F and a dry-bulb
temperature of 78F.
(o) Estimate the percentage saturation, molal humidity, and the dew point.
(b) Calculate the weight of water contained in 100 cu ft of the air.
21. Hydrogen is saturated with water vapor at atmospheric pressure and a temperature of 90F. The wet gas is passed through a cooler in which its temperature is
reduced to 45F and a part of the water vapor condensed. The gas after leaving the
cooler is heated to a temperature of 70F.
(a) Estimate the weight of water condensed in the cooler per pound of moisturefree hydrogen.
(6) Estimate the percentage humidity, wet-bulb temperature, and molal
humidity of the gas in its final conditions.
22. It is desired to maintain the air entering a building at a constant temperature
of 75F and a percentage humidity of 40%. This is accomplished by passing the air
through a series of water sprays in which it is cooled and saturated with water.
The air leaving the spray chamber is then heated to 75F.
(a) Assume that the water and air leave the spray chamber at the same temperature. What is the temperature of the water leaving?
(6) Estimate the water content of the air in the building in pounds of water per
pound of dry air.
(c) If the air entering the spray chamber has a temperature of 90F and a percentage humidity of 65%, how much water will be evaporated or condensed in the spray chamber per pound of moisture-free air?
23. In a direct-fired evaporator the hot combustion gases are passed over the surface of the evaporating liquid. The gases leaving the evaporator have a dry-bulb
temperature of 190F and a wet-bulb temperature of 145F. The dry combustion
gases contain 11% COj. Estimate the percentage saturation of the gases leaving the
evaporator, their molal humidity, and their dew point.
24. An air-conditioning system takes warm summer air at 95F, 85% humidity,
and 760 mm of mercury. This air is passed through a cold-water spray, and emerges
saturated. The air is then heated to 70F.
(a) If it is required that the final percentage humidity be 35%, what must be
the temperature of the air emerging from the spray?
(6) On the basis of 1000 cu ft of entering air, calculate the weight of water
condensed by the spray.
26. Cold winter air at 20F, 760 mm pressure, and 70% humidity is conditioned by
passing through a bank of steam-heated coils, through a water spray, and finally
through a second set of steam-heated coils. In passing through the first bank of
CHAP. IV]
'
PROBLEMS
109
steam-heated coils, the air is heated to 75F. The water supphed to the spraychamber is adjusted to the wet-bulb temperature of the air admitted to the chamber,
hence the humidifying unit may be assumed to operate adiabatically. It is required
that the air emerging from the conditioning unit be at 70F and 35 % humidity.
(o) What should be the temperature of the water supplied to the spray chamber?
(b) In order to secure air at the required final conditions, what must be the
percentage humidity of the air emerging from the spray chamber?
(c) What is the dry-bulb temperature of the air emerging from the spray
chamber?
(d) On the basis of 1 cu ft of outside air, calculate the volume at each step of the
process,
(e) Calculate the pounds of water evaporated per cubic foot of original air.
26. At the top of a chimney the flue gas from a gas-fired furnace has a temperature
of 180F and a wet-bulb temperature of ISST. The composition of the moisturefree flue gas is as follows:
1
:
CO2
O2
N,
14.1%
6.0%
79.9%
100.0%
(a) If the temperature of the gases in the stack were reduced to 90P, calculate
the weight of water in pounds which would be condensed per pound-mole
of dry gas.
(fe) The gas burned in the furnace is estimated to contain 7% CH4, 27% CO,
and 3% CO2 by volume; it does not contain any carbon compounds other
than these. The gas is burned at a rate of 4000 cu ft per 24 hours measured at a temperature of 65F, saturated with water vapor. Estimate the
weight of water condensed in the chimney per day under the conditions
of part (a).
27. A fuel gas has the following analysis:
Carbon dioxide
Ethylene
Benzene
Oxygen
Hydrogen
Carbon monoxide..
Paraffins
Nitrogen
CO2
C2H4
CsHs
O2
H2
CO
C1.20H4.40
Nj
<
=
3.2%
= 6 . 1
= 1 . 0
=
0.8
=
40.2
=33.1
=
10.2
= 5 . 4
100,0%
^. ^
', ;
|
Assume that this gas is metered at 65F, 100% saturation, and is burned with air
supplied at 70F, 1 atm pressure, and 60% humidity. Assume 20% excess air is
supplied and that combustion is complete.
(a) What is the dew point of the stack gases?
(b) If the gases leave the stack at 190F, what is the wet-btiib temperature?
(c) If the gases are cooled to 85F before leaving the chimney, how many
pounds of condensate drain down the chimney on the basis of 100 cu ft
of fuel gas metered?
no
[CHAP. IV
28. Air at 185F and a dew point of 40F is supplied to a dryer, which operates
under adiabatic conditions.
(o) What is the minimum temperature to which the air wiU cool in the dryer?
(6) What is the maximum evaporation in pounds that can be obtained on the
basis of 1000 cu ft of entering air?
(c) If maximum evaporation is obtained, what will be the volume of the emerging air on the basis of 1000 cu ft of entering air?
29. Air enters a dryer at a temperatiire of 240F with a dew point of 55F. The
dryer may be assumed to approach adiabatic vaporization in its operation, all the
heat being supplied by the air. If the air leaves the dryer saturated with water
vapor, how much water can be evaporated per 1000 cu ft of entering wet air?
30. A dryer for the drying of textiles may be assumed to operate adiabatically.
The air enters the dryer at a temperature of 160F with a dew point of 68F. It is
found that 0.82 lb of water is evaporated per 1000 cu ft of wet air entering the dryer.
Estimate the percentage saturation and temperature of the air leaving the dryer.
CHAPTER V
SOLUBILITY AND SORPTION
Industrial problems involving phase equilibria among solids, liquids,
and gases involve all the mutual equilibrium relations among these
three phases, such as the dissolution of a solid by a hquid, the crystallization of a solid from a liquid, the absorption and desorption of gases
by liquids, the distribution of a solute between immiscible liquids, and
the adsorption and desorption of gases by solids.
j
'
112
[CHAP. V
as crystallization. As dissolution proceeds, the concentration of dispersed particles is increased, resulting in an increased osmotic pressure
and a greater rate of crystallization. When the solute concentration
becomes sufficiently high, the rate of crystallization will equal the rate
of dissolution, and a dynamic equilibrium will be established, the concentration of the solution then remaining constant. This equilibrium
is analogous to that between a liquid and its vapor. Under these conditions the solution is said to be saturated with the solute and is incapable
of dissolving greater quantities of that particular solute.
The concentration of solute in a saturated solution is termed the solubility of the solute in the solvent. Solubilities are dependent on the
nature of the solute, the nature of the solvent, and the existing temperature. Pressure also has a small effect on solubility, which ordinarily
may be neglected. This effect is such that, in a solution whose volume
is less than the sum of the volumes of its components in their pure states,
solubility is increased by an increase in pressure. In the opposite case,
in which the total volume is increased in the formation of a solution,
an increase in pressure lowers the solubility.
The simple generalizations which apply to equilibria between liquids
and vapor-gas mixtures are not applicable to liquid solutions. Little
is known regarding the relationships between solubilities and the specific
properties of the solute and solvent. The properties of each.particular
system must be individually determined by experimental means, and it
is impossible to predict quantitatively the behavior of one system from
that of another. This results from the fact that what may be termed
the solution pressure of a solid is entirely dependent on the nature of the
solvent with which it is in contact. In many cases it is impossible to
predict, even qualitatively, the effect of temperature on solubility.
Solubilities of Solids Which Do Not Form Compounds with the Solvent. In general, where no true chemical compounds are formed between a solute and solvent, the solubility increases with increasing
temperature. The solubility curves of such systems resemble vaporpressure curves in general form. In Fig. 10 are plotted the solubility
data of a typical system, naphthalene in benzene.
Curve EB of Fig. 10 represents the conditions of temperature and
concentration which correspond to saturation with naphthalene, of a
solution of naphthalene in benzene. A solution whose concentration
and temperature fix a point on this curve will remain in dynamic equilibrium with solid crystals of naphthalene. If the temperature is lowered
or the concentration increased by the removal of solvent, naphthalene
crystals will be formed in the solution. The area to the right of curve
EB represents conditions of homogeneous, partially saturated solutions.
CHAP.
113
SOLUBILITIES OF SOLIDS
V]
The area between curves EB and ED represents conditions of nonhomogeneous mixtures of crystals of pure naphthalene in solutions of
naphthalene in benzene. If a solution whose concentration and temperature are represented by point xi is cooled without change in composition, its conditions will vary along the dotted line parallel to the
temperature axis. The temperature at which this dotted line intersects the solubility curve EB is the temperature at which pure naphthalene will begin to crystallize from the solution. As the temperature
is reduced further, more naphthalene will crystallize and the remaining
saturated solution will diminish in concentration, its condition always
100
80
Solid CloHg
+Soli ition
3 (S
-to ^40
*i
U
3 m
S
Home geneo us
So ution
-10
'1'/
(Solid C j H
L + Solution
A
20
30
Temperature C
40
60
represented by a point on curve EB. When the temperature corresponding to line CED is reached the system will consist of pure
naphthalene crystals and a saturated solution whose concentration
corresponds to point E. Further decrease in temperature will cause
this remaining solution to solidify to a mixture of crystals of pure
benzene and pure naphthalene. The line CED represents the completion of solidification, and the area to the left of it corresponds to completely solid systems of naphthalene and benzene crystals.
The point E is termed the eutectic point, and the corresponding temperature and composition are, respectively, the eutectic temperature and
the eutectic composition. If a solution of eutectic composition is cooled
it will undergo no change until reaching the eutectic temperature, when
it will completely solidify without further change in temperature. A
114
[CHAP. V
115
CHAP. V]
100
'
"s g
'
'
-',
.
10'
"
SolidFeCl3-2H20
+ Solution \
8 V
L-
- > ^ ^
SolidFeCl3-2.5H20
6 + Solution Y-^ HjJ.
F
4 5J)^--^Solid Fe (Jlj 3.5 tl2U
p413
+ Solution
70
/If
'y
o 'S
90
1\
>
60
60 2
3 j / c
^ f ~ S o l i d FeCla-eHjO
1
+ Solution
4_
--Ice+FeCla-eHp
c
0)
1
1
1
1
\
f^ 4 0
'S
B__.'
a)
S,20
0)
Ice+Solution
0 1
-60
''
1
-40
^v
1
-20
1 A
1
1
,
0
20
Temperature "C
:
40
60
,
80
116
[CHAP.
CHAP.
V]
117
118
[CHAP. V
504-NajSOi-lOHjO
10 HjO
+ ctic -
+ Solution
v\o W^*i
^SMS'-
.-^
^C'
E
^i
: ^
t.
Homogeneous Solution
G Ice
.
_Eute ctici 3
A~lce +Solution
ill
jr
20
30
Temperature C
40
50
60
CHAP.
V]
119
concentration of the saturated solution increases along curve BC. Normally this increase would continue until a congruent point was reached.
However, at a temperature of 32.384C, Na2SO4-10H2O becomes unstable and is decomposed into Na2S04 and water. The solubility of
the anhydrous Na2S04 as indicated by curve CD diminishes with
increasing temperature. Points on this curve represent conditions of
equilibrium between crystals of anhydrous Na2S04 and saturated solutions. A solution whose conditions are represented by point Xi will
become saturated if either heated or cooled sufficiently. If cooled,
crystals of Na2SO4-10H2O will form when the conditions of curve BC
are reached. If heated, crystals of anhydrous Na2S04 will form at the
temperature corresponding to composition Xi on curve CD.
The significance of the areas of Fig. 12 is similar to that of the other
diagrams which have been discussed. The area of the small triangle to
the left of line AB represents a region of equilibrium between crystals
of pure ice and saturated solution. Area BC4^ is a region of equilibrium
between crystals of pure Na2SO4-10H2O and saturated solution. The
area to the left of line B2 represents a solid mixture of crystals of ice
and Na2SO4-10H2O. Line C4S indicates the transition temperature at
which the decahydrate decomposes to form the anhydrous salt. Line
S24 indicates the composition of the pure decahydrate, Na2SO4-10H2O.
The area to the right of curve 54CD represents conditions of equilibria
between crystals of pure Na2S04 and saturated solutions. The area
above and to the left of curves 3^4^ is a region of entirely solid mixtures
of Na2S04 and Na2SO4-10H2O. Line 45 therefore represents a temperature of complete solidification.
Many systems which form several solvates show solubility relationships both with and without congruent points and transition points in
the same system. For example, zinc chloride forms five hydrates.
Four of these hydrates decompose, as does Na2SO4-10H2O, exhibiting
transition points before congruent concentrations are reached. The
fifth hydrate, ZnCl2-2.5H20, exhibits a true congruent point, as do the
hydrates of ferric chloride. The significance of such solubility relationships may be understood from the principles discussed in the preceding
sections.
Effect of Particle Size on Solubility. The solution pressure and solubility of a solid is affected by its particle size in a manner entirely analogous to the effect of particle size on vapor pressure. The solubility of
a substance is increased with increase in its degree of subdivision. This
increasing solubility with diminishing particle size is demonstrated by
the behavior of crystals which are in equihbrium with their saturated
solutions. Where such an equilibrium exists the total amounts of solid
120
[CHAP. V
and liquid must remain unchanged. However, the equilibrium is dynamic, resulting from equality between the rates of dissolution and
crystallization. As a result of the effect of particle size on solubihty,
the small crystals in such a solution will possess higher solution pressures
than the large ones and will tend to disappear with corresponding increase in size of the large crystals. This growth of large crystals at the
expense of the small ones in a saturated solution is a familiar phenomenon of considerable industrial importance. For the same reasons,
an irregular crystalline mass will change its shape in a saturated solution. The sharp comers and points will exert higher sol'ution pressures
than the plane surfaces and will disappear, building up the plane surfaces and tending to produce a regular shape. Like vapor pressures,
solubilities are not noticeably affected by particle size until submicroscopic dimensions are approached.
Supersaturation. Just as spontaneous condensation of a vapor is
made difficult because of the high vapor pressure of small drops, spontaneous crystallization is interfered with by the high solubihty of small
crystals. In order to produce spontaneous crystaUization the concentration of a solution must be sufficiently high that the small crystalline
nuclei which are formed by simultaneous molecular or ionic impacts do
not immediately redissolve. Such a concentration will be much greater
than that which is in equihbrium with large crystals of the same sohd.
Once crystaUization is started and nuclei are formed it will continue and
the nuclei will grow until the normal equilibrium conditions are reached.
For these reasons it is relatively easy to obtain solutions whose concentrations are higher than the values normally corresponding to saturation. Such solutions are supersaturated with respect to large crystals
but are only partially saturated with respect to the tiny nuclei which
tend to form in them. Supersaturated solutions may be formed by
careful exclusion of all crystalline particles of solute and by slow changes
in temperature or concentration without agitation.
Because of the phenomenon of supersaturation, it is possible to extend
the curves of solubility diagrams, such as Fig. 12 into regions where the
equilibria which they represent would not normally be stable. The
dotted curves of Fig. 12 represent such equilibria which have been
experimentally observed in supersaturated solutions of this system.
Such equiUbria are termed meiastable and possess the continual tendency
to revert to the normal, stable state corresponding to their conditions
of temperature and concentration.
The dotted curve GE of Fig. 12 represents the metastable equilibrium
between crystals of Na2S04-7H20 and its saturated solutions. .If a
solution at conditions Xi is carefully cooled, normal crystallization of
CHAP. V]
DISSOLUTION
121
Na2SO4-10H2O may be prevented and a supersaturated solution produced at conditions x'\. If cooling is continued the crystallization of
Na2S04-7H20 may be induced at a temperature corresponding to composition X\ on curve GE. A supersaturated solution at conditions x'y is
capable of dissolving Na2S04-7H20 and is unsaturated with respect to
this compound. On the other hand, its conditions are unstable, and
any disturbance such as agitation, a sudden temperature change, or the
introduction of a crystal of Na2SO4-10H2O, will cause it to assume its
normal equilibrium conditions with the crystallization of Na2SO4-10H2O.
Metastable equilibria are of little industrial significance, but supersaturation is very commonly encountered. It may be produced in two
ways. By the exclusion of all particles of solid solute the formation of
crystalline nuclei may be entirely prevented as described above. Another type of supersaturation may result from sudden changes of the
conditions of a saturated solution even though crystallization has
started and crystalline solute is present. This results from the fact
that crystallization, especially in certain types of viscous solutions, is a
slow process. Sudden cooling of such a solution will produce temporary
conditions of supersaturation simply because the system is slow in adjusting itself to its equilibrium conditions. Agitation of the solution
will hasten this adjustment.
In the majority of crystallization operations it is desirable to avoid
supersaturation. Supersaturation of the type resulting from the absence of crystalline nuclei is prevented by seeding saturated solutions
with crystals of solute. Spontaneous nucleus formation is also favored
by the presence of rough, adsorbent surfaces. The crystallization of
sugar on pieces of string to form rock candy and the scratching of the
wall of a beaker to cause crystallization of an analytical precipitate are
famiUar illustrations of this principle. Supersaturation due to slow
crystallization rates is avoided by using correspondingly slow rates of
change of the conditions which promote supersaturation and in some
cases by agitation.
DISSOLUTION
Problems arise in which it is required to calculate the amount of solute
which can be dissolved in a specified quantity of solvent or solution, or,
conversely, the quantity of solvent required to dissolve a given amount
of solute to produce a solution of specified degree of saturation. Where
solvates are not formed in the system such calculations introduce no
new difficulties. From the solubility data is determined the quantity
of solute which may be dissolved in a unit quantity of solvent to form
122
SOLUBILITY A N D S O R P T I O N
[OHAP. V
1000 lb of water.
358 lb
26.4%
Where the substance to be dissolved is a solvated compound the problem is complicated by the fact that both solute and solvent are added
to the solution. Such calculations are carried out by equating the total
quantities of solute entering and leaving the process. Algebraic expressions are formed for the sum of the quantity of solute to be dissolved plus that originally present in the solution, and for the quantity
of solute in the final solution. Since the total quantity of solute must
be constant, these two expressions are equal and may be equated and
solved. This method is demonstrated in the following illustration:
Illustration 2. After a crystaUization process a solution of calcium chloride in
water contains 62 lb of CaCU per 100 lb of water. Calculate the weight of this
solution necessary to dissolve 250 lb of CaCl2-6H20 at a temperature of 25C. Solubility a t 26C == 7.38 lb-moles of CaCl2 per 1000 lb of H2O.
Basis: x = weight of water in the required quantity of solution.
250
CaCl2-6H20 to be dissolved = =
1.14 lb-moles
Total CaCl2 entering process = 1.14 -f-
= 1.14 + ' - - l b - m o l e s
J-XiXlUU
100
Total water entering process = x + (1.14 X 6 X 18) = x + 123 lb
X -I- 123
7.38
lb-moles
1000
1 :
CRYSTALLIZATION
CHAP. V]
123
Equating:
'"
1.14+ 0-^^^^ =
100
1140 + 5.59a: =
1.79a; =
x =
7.38^ + ^'^
1000
7.38s + 9 0 8
232
1301b
Total weigl
CRYSTALLIZATION
124
[CHAP.
^
* '
, f \ .
x = 81 lb
81
(c) Percentage jdeld = = 16.5%
490
*'
'
' ''
./
/
<
1.96 lb-moles
1.18 lb-moles
From the solubility data of NaHCOs it is found that a saturated solution containing 1.18 lb-moles per 1000 lb of HjO has a temperature of 23C. The solution
must be cooled to this temperature to produce the specified percentage yield.
CHAP.
V]
CRYSTALLIZATION
125
870 lb
130 lb
230 lb
26.4 lb
103.6 lb
79.7%
ioU
100 grams
9.1%
1.07 gram-moles
909 grams
173 grams
736 grams
126
[CHAP.
(1)
y - Vi
._.
or
^ =
.
(2)
W
y^- yi
If separation results from evaporation of a weight wi of pure component B, the material balance of component A becomes
yW = y\Wi-\r yi{W - w^ - w-i)
'
CHAP. V]
127
= 60.0%
,
=
' "
Final solution
(1000 - a;) (0.683)
Crystals
0.600x
Illustration 9. A solution of sodium sulfate in water is saturated at a temperature of 40C. Calculate the weight of crystals and the percentage yield obtained
by cooling 100 lb of this solution to a temperature of 6C.
From Fig. 12 it is seen that at a temperature of 5C the decahydrate will be the
stable crystalline form. The solubilities read from Fig. 12 are as follows:
at40C:32.6%Na2SO4
at 5C: 5.75% NajSOi.
Basis: 100 lb of original solution, saturated at 40C.
Percentage Na2S04 in Na2SO4-10H2O crystals =
142
= 44.1%
142 + 180
' , , .
Final solution
0.057(100 - x)
Crystals
0.441x
322
Weight of NazSOi-lOHjO in original solution = 3 2 . 6 = 74 lb
142
69.5
.
.
Percentage yield = -- = 94%
128
[CHAP.
CHAP. V]
FRACTIONAL CRYSTALLIZATION
129
ticular case under consideration. For salts which are ionized in solution the following qualitative generalization applies: Where the same
ion is formed from each of two ionized solute compounds, the solubility of each compoimd is diminished by the presence of the other.
For example, the solubility of NaCl in water may be diminished by the
addition of another solute which forms the chloride ion. This principle
is applied in the crystallization of pure NaCl by bubbling HCl into concentrated brine. Similarly, the solubility of NaCl in water is reduced
by the addition of sodium hydroxide. This accounts for the recovery
of nearly pure caustic soda by evaporation of cathode liquor in the
electrolysis of sodium chloride.
The mutual solubility relationships in complex systems are of great
importance in many industrial processes. Soluble substances frequently may be purified or separated from other substances by properly conducted fractional crystallization processes. In such processes
conditions are so adjusted that only certain of the total group of solutes
will crystallize, the others remaining in solution. For the production
of very pure materials it is frequently necessary to employ several
successive fractional crystallizations. In such a scheme of recrystallization the crystal yield from one step is redissolved in a pure solvent
and again fractionally crystallized to produce further purification.
Complete data have been developed for solubilities in many complex
systems. The presentation and use by such data for more complicated
cases are beyond the scope of a general discussion of industrial calculations. In an excellent monograph^ by Blasdale the scientific principles
involved in such problems are thoroughly discussed. Data for many
systems are included in the International Critical Tables.
In Fig. 13 are the solubihty data of Caspari^ for the system of sodium
sulfate and sodium carbonate in water, presented in an isometric,
three-coordinate diagram. A diagram of this type permits visualization
of the relationship existing in such systems of only three components.
The solubility data determine a series of surfaces which, with the axial
planes, form an irregular-shaped enclosure in space. Any conditions of
concentration and temperature which fix a point lying within this enclosure correspond to a homogeneous solution. Points lying outside
the enclosure represent conditions under which at least one solid substance' is present. The surfaces themselves represent conditions of
equilibria between the indicated solids and saturated solutions. The
line formed by the intersection of two of these surfaces represents con W. G. Blasdale, Equilibria in Saturated Salt Solutions, Chemical Catalog Co.,
New York (1927).
2 W. A. Caspari, J. Chem. Soc, 125, 2381 (1924).
, .
130
[CHAP.
a.
_
P I G . 13.
0 G 10
20
30
40
50'
Grams Na,CO, per 100 Grams H,0
Solubility of sodium carbonate-sodium sulfate in water.
CHAP. V]
FRACTIONAL CRYSTALLIZATION
131
small amounts of Na2SO4-10H2O in solid solution, crystals of Na2S04IOH2O containing small amounts of NaaCOs-lOHaO in solid solution,
and liquid solution containing both Na2S04 and Na2C03.
At the higher temperatures the system is complicated by the decomposition of the hydrates and by the formation of a stable double salt of
definite composition, 2Na2S04-Na2C03. The surface RQSTVU represents equilibria between pure crystals of this double salt and hquid
solutions. The other surfaces and lines of the diagram may be interpreted in a similar manner from the composition of the equilibrium solid
which is marked on each surface.
An isometric diagram such as Fig. 13, though valuable as an aid to
visualization, is not suitable as a basis for quantitative calculations.
Data for calculation purposes are better presented as a family of isothermal solubility curves on a triangular diagram as shown in Fig. 14.
The coordinate scales represent weight percentages of Na2S04, Na2C03
and H2O respectively. Each line of Fig. 14 represents the solubility
relationships at one indicated temperature. By interpolation between
these lines solubilities at any desired temperature may be obtained.
Points along curve AB represent conditions of saturation with both
solutes. The curves running upward to the left from this curve represent solutions which are saturated with sodium carbonate but only
partially saturated with sodium sulfate. Similarly, the curves running
upward to the right represent saturation with sodium sulfate. The
hydrates, NajSOi-lOH^O (44.1% NasSOi) and NasCOa-lOHaO (37.1%
Na2C03), are represented by points C and D, respectively.
Point Xi on Fig. 14 represents a composition which at a temperature
of 25C corresponds to a solution saturated with respect to sodium
carbonate but unsaturated with respect to sodium sulfate. If such a
(Solution is cooled, pure Na2CO3-10H2O will crystallize and the composition of the residual solution will change along the dotted line Dxi. At
a temperature of 22.5C, corresponding to the intersection of this
dotted line with curve AB, the remaining solution will become saturated with both sodium carbonate and sulfate. Further cooUng will
result in crystallization of both decahydrates in crystals of the solid
solutions which were previously discussed. The concentration of the
residual solution will then diminish along curve AB. If cooling were
stopped at 22.5C a jdeld of pure Na2CO3-10H2O crystals would be
obtained, and a separation of one solute from the other would result.
Point Xi on Fig. 14 represents a composition which at a temperature of
25C corresponds to a solution unsaturated with respect to both solutes.
If water is evaporated from such a solution at a temperature of 25C
the concentration of each solute will be increased. Since the relative
132
[CHAP. V
Weight % NajSO,
F I G . 14.
CHAP. V]
FRACTIONAL CRYSTALLIZATION
133
= 7.64%
~ 131
21
NasCO,
= 16.02%
~ 131
H2O
= 76.34%
(o) Upon cooling, NajCOa-lOHzO will crystallize out along line aD, giving a composition at 17.5C corresponding to point b.
NaaSOi =
,'
8.5%
NajCOa = 13.8%
'
6.2%
NajCOs = 10.0%
H2O
= 83.8%
134
[CHAP. V
a; = 251 grams
2/ =, 79 grams
';*
s = 35.2 lb
CHAP. V]
FRACTIONAL CRYSTALLIZATION
135
Illustration 12. A solution contains 19.8% NaaCOa and 5.9% Na2S04 by weight.
Calculate the weight and composition of crystals formed from 100 lb of this solution
when
(a) 10 lb of water is evaporated and the solution cooled to 20C.
(6) 20 lb of water is evaporated and the solution cooled to 20C.
Basis: 100 lb of solution.
(a) The residue after evaporation consists of
19.8
- = 22% Na^COa
yu
^ = 6.55% NaaSOi
This composition corresponds to h on Fig. 14. Upon cooling, Na2CO3-10H2O
win crystalhze out along line Dh reaching at 20C a composition corresponding to
point i, 9.4% NazSOi and 15.3% NajCOs.
Let a; = lb NaaCOs-lOHjO crystaUized.
i
Then
'
90(0.22) = x(0.371) + (90 - a;)(0.1S3)
or
X = 27.51b.
= 24.8% Na^CO,
|^=
7.4%Na,S04
At 20C the solution becomes saturated with respect to both solutes, corresponding
to a composition of 14.8% Na2C03 and 11.4% Na2S04.
Let X = lb NajCOs-lOHaO crystallized,
2/ = lb Na2SO4-10H2O crystallized.
*"
136
[CHAP. V
-'
-,.
.
"
,-
' ^ v ,
CHAP. V]
137
10
20
30
40
50
CaClj
6H2O
60
70
CaCl2
4HjO
FIG. 15. Vapor pressure and relative humidity over calcium chloride solutions.
but any tendency to condense water on the tetrahydrate is immediately
followed by hexahydrate formation with a vapor pressure equal to that
of the system. In the area cdjh, crystals of tetrahydrate are in equihbrium with a saturated solution of tetrahydrate. The horizontal lines
represent vapor pressures of the saturated solutions of tetrahydrate. In
area delm, crystals of dihydrate are in equilibrium with a saturated solution of dihydrate. The horizontal vapor pressure lines represent the
vapor pressure of the saturated solution at various temperatures. In
138
[CHAP.
the area gjmn two solid phases of tetrahydrate and dihydrate are present.
The horizontal Unas represent the vapor pressure of the tetrahydrate at
various temperatures. The vapor pressure of the dihydrate is lower but
the tendency for water to condense on the dihydrate is reversed by formation of the tetrahydrate with vapor pressure equal to that of the
system.
_
,
ABEA
ahcf
fckg
cdjh
delm
gjmn
In using the calcium-chloride-water system in a drying and regenerating cycle, during the drying stage the vapor pressure of water in the gas
to be dried must exceed the equilibrium value of the system and in
regeneration the vapor pressure of water in the hot air blown through
must be less than the equilibrium vapor pressure of the system.
Regeneration of calcium chloride from solution is frequently not considered feasible because of the relative cheapness of the salt.
I t will be observed that in using a homogeneous solution of CaCU
below 40F the lowest relative humidity obtainable is 4 5 % whereas
above 90F the lowest attainable is 19%.
Illustration 13. Ninety pounds of anhydrous CaCU is placed in a room of 90,000 cu
ft capacity. The air is initially at 80F and 90% relative humidity. Estimate the
conditions of air and desiccant when equilibrium has been attained at 80 F, assuming
a pressure of I.O atmosphere.
It wiU be estimated that enough water is removed to liquefy the CaCU, leaving a
saturated solution of hexahydrate and air at a relative humidity read from Fig. 15 as
27%. This assumption wUl be verified by the calculations.
Weight of dry air in room
Initial humidity lb/lb
Final humidity
Water removed = 6560(0.0198 - 0.0061)
= 6560 lb
=0.0198
= 0.0061
= 89.9 lb.
CHAP. Y]
DISTRIBUTION
139
0.000932
0.00225
0.01
0.02
0.05
0.10
0.18
2.23
1.45
0.705
0.505
0.320
0.240
0.187
140
[CHAP. V
Effect of Temperature. The effect of temperature on the distribution coefficient is generally small if the temperature coefficients of solubility are approximately equal in the two phases. Specific data are
necessary in order to predict the effects of a temperature change. For
many industrial calculations the effects of temperature changes of only a
few degrees may be disregarded.
Distribution Calculations. The distribution of a solute between two
immiscible hquids is of considerable industrial importance in the separation and purification of organic compounds. Ordinarily one liquid
will be water or an aqueous solution and the other some immiscible
organic solvent. Equilibrium concentrations of a solute in such systems
may be varied by the addition of a second solute which is soluble in only
one of the liquids. The addition of such a solute is, in effect, a change
in the nature of one of the liquids.
From values of distribution coefficients equilibrium conditions are
readily calculated.
Illustration 14. Picric acid exists in aqueous solution at 17C in the presence of
small amounts of inorganic impurities whose effects on its solubility may be neglected.
The picric acid is to be extracted with benzene in which the inorganic materials are
insoluble.
(a) If the aqueous solution contains 0.20 gram-mole of picric acid per liter, calculate the volume of benzene with which 1 Uter of the solution must be extracted in
order to form a benzene solution containing 0.02 gram-mole of picric acid per liter.
(Neglect the difference between the volume of a solution and that of the pure solvent.)
(b) Calculate the percentage recovery of picric acid from the aqueous solution.
Basis: 1 liter of original aqueous solution.
Picric acid =
0.20 gram-mole
From Table III, K = 0.505 in final system =
CB/CA
Benzene required = -- =
CHAP. V]
DISTRIBUTION CALCULATIONS
141
0.10 - xi 0.5
Xi = 0.033
The distribution coefiicient corresponding to this concentration is taken from the
data of Table III as a second approximation.
K2 = 0.39
X2
= 0.39
0.10 - X2
X2 = 0.028
As a third approximation:
K3 = 0.42 (corresponding to CB = 0.028)
_^1_=0.42
0.10 - X3
X3 = 0.029
This result may be taken as the final concentration of picric acid in the benzene solution. If greater accuracy is desired, more approximations should be carried out.
Picric acid in final benzene solution =
Kcric acid in final aqueous solution =
0.029 gram-mole
0.071 gram-mole
142
V
[CHAP.
~;d_
r*'*^^^^
10
/)
Upper U er
0
30
40
Tempewtiire.'C
'
CHAP. V]
143
144
[CHAP. V
two phases into which a mixture of composition x separates are proportional to the lengths of the line segments da; and ex. Thus, the weight
fraction of the upper-layer solution is equal to segment ex divided by
segment de.
In order to define completely the solubility and equilibrium relationships of such a ternary system, a family of tie-lines such as fg and hi
must be drawn in, linking together the compositions of conjugate solutions on the solubility curves. Tie-lines lying higher in the diagram than
hi would be progressively shorter until at point c-the length of the tieIso-CsHjOH
A
k60
\
<&/
/(Upper Layer \
\ fd
/Jk/
Y \/
*/ Y
HjO
Vi. / \
,^y
k50
i.4o\
\sj \ Lower
Sf)\ vC^ Layer
\/
-JAX/XX
)/ ^lAtve^-.
<?
A/
<>
/ \ '7\
S"
<?
CaCl
line becomes zero. This point is termed the critical solution point or
plait point, at which the compositions of the upper and lower layers of the
two-phase system become equal.
The locations of all tie-lines can be defined without confusing the diagram by constructing them through use of curve ac, termed the conjiirgate line. This line is the locus of the points of intersection of lines
drawn through conjugate compositions points parallel to the base and
right side of the diagram respectively. Thus, point j is located as the
intersection of lines dj and ej. Conversely, point j defines the location of
tie-line de. In a similar manner any other tie-lines on the diagram may
be located from the conjugate line.
It will be noted that for this system the critical solution point does not
CHAP. V]
145
so
45
Mole %
40
2 35
ll
30
/
/
10
15
20
25
30
35
Isopropyl Alcohol in Lower Layer
40
45
Fia. 18. Equilibrium distribution of isopropyl alcohol in water and tetrachlorethylene at 77F in weight per cent. From Bergelin, Lockhart, and Brown, Trans. Am.
Inst. Chem. Eng., 39, 173 (1943).
146
[CHAP.
147
HENRY'S LAW
CHAP. V]
1
H Pi
(5)
V
\
\
\
\
0.05
25
IJ
\ "^
4
2.0
0.04 >
0;
0.03
^^s
OfV.
Ai
0.02
1.0
0.5
0.01
nno
20
40
60
Temperaturt, C
100
148
(CHAP.
for hydrogen sulfide and carbon dioxide will lead to considerable error if
used for pressures above about 1 atmosphere.
' " = ,
Xllustration 16. Calculate the volume of oxygen, in cubic inches, which may be
dissolved in 10 lb of water at a temperature of 20C and under an oxygen pressure
of 1 atmosphere.
,'
Solution:
From Fig. 19, for oxygen and water at 20C, 1/ff =
Mole fraction of Oj = 760 X 0.033 X lO"' =
Mole fraction of water =
..Y'^^--'
0.033 X lO"'
25.1 X lO"'
1.00
ADSORPTION OF GASES
CHAP. V]
149
X
O
3!
g I.O
2
C3
/'
0,
oC
v^ *"
g.
X
mc
'
1 0.5
2
w
t
1000
2000
3000
4000
F I G . 20.
150
[CHAP. V
CHAP. V]
EQUILIBRIUM ADSORPTION
151
'
(6)
152
[CHAP. V
where
Hr = relative humidity
We = equihbrium moisture content, pounds per 100 pounds of
commercially dry gel
Pa = partial pressure of water vapor in air
p, = vapor pressure of pure water at temperature of air
40
/\
35
'
-30
Q
& 25
S
,11
^20
IS
yvn
10
-IX
x_
20
I.
II.
III.
IV.
V.
Silica gel.
Leather, chrome tanned.
Wool, worsted.
Activated alumina.
Viscose
40
60
Percentage Relative Humidity
VI.
VII.
VIII.
IX.
X.
80
lOO
Cotton cloth.
Sulfite pulp, fresh, unbleached.
Bond paper.
Cellulose acetate silk, fibrous.
KaoUn (Florida).
ADSORPTION ISOTHERMS
CHAP. V]
153
65
X 100 = 9.1%
Equihbrium moisture content is of importance in the drying of materials which exhibit adsorptive characteristics. It is evident that water
will not evaporate from an adsorbent sohd into a gas the relative humidity of which is higher than that corresponding to the equilibrium moisture content of the solid. Thus, the equilibrium moisture content represents the minimum moisture content to which a material can be dried
by a gas of a given relative Humidity. Continued passage of gas will not
result in further dr3dng even though the gas is far from normal saturation
with water.
rv,-Pressure,, mm of Hg
0
10
15
20
25
<
ii--
e
O
2
2
Q.
T3
<
jii
^
/ o
>-T"
'
a
"^
10
20
30
40
50
60_
19
1,11, III,-Pressure, cm of Hg
154
[CHAP.
1 + ap
where
w = the mass adsorbed per unit weight of adsorbent
p = the partial pressure of the adsorbate in the gas phase
o = a constant
In many cases the adsorption isotherm is satisfactorily represented by
the empirical equation proposed by FreundUcb:
w
fcp"
'*
^)
where
h and n = empirical constants
Curve III is typical of the adsorption of a vapor below its critical
temperature at pressures in the region of the normal vapor saturation
pressure. When the pressure of the vapor is sufficiently increased to
equal the normal vapor pressure of benzene at the existing temperature
the vapor becomes saturated and normal condensation to the liquid
state results. The quantity of Hquid in equilibrium with a unit weight
of solid at this pressure may then become infinite.
In Fig. 23 the isotherms of benzene vapor adsorbed on activated
charcoal from the data of CooHdge^ are shown. The adsorbed quantity,
X, in milliliters of vapor, measured at standard conditions, adsorbed per
gram of gas-free or " outgassed " charcoal are plotted as ordinates.
Logarithms of the pressures of benzene vapor in millimeters of mercury
are plotted as abscissas. The logarithmic scale i^ desirable because of
the wide range of pressures required. The characteristic shape of these
curves when plotted in linear coordinates is indicated by Curve III of
Fig. 22. The coconut charcoal used in the experiments on which
Fig. 23 is based had been outgassed by heating to 550C at reduced
pressure.
/ . Am. Chem. Soc. 46, 596 (1924).
155
ADSORPTION ISOTHERMS
CHAP. V]
I t will be noted from Fig. 23 that, like the systems of Curves III and
IV of Fig. 22, when the pressure is sufficiently increased to equal the normal vapor pressures of benzene at the existing temperature, the vapor
becomes saturated and normal condensation to the Uquid state results.
,
^ ^ ^
^/^
^'i^
^^
4>^
riC.
<^
-I
^^
4.
^^
~^
- A - ^
>^
^ ^ ^
/.
.^
/.
/.
-/
-7
^^ /^
y J4 K4 z
^^
^
^
/
<^/KJy^ ^^ -/^ ^
vC ^v
y
> ^
^ " * "
o-_-
. " ^
_---=
3
'^
^ ^
.7
^^ ^^ -""^ ^^ ^"^ ^
^-^^__.^-''^
^^
^---''^
^-^"^
^'^
-
^/
2 ^ 1^/
V -Xy ^ / /
/Z
/
^
Z I'v'^ ^^ _ ^^
/'^ J T^/
* / T^/ 7
7
_^'
C T -,
y ^
' ^
^^ '^^^
^-^
^^
~J_"
zW- TT^ /^
-0
^='*"---,;"
^Z
/^
" y
-^JL
_
Solid
(/'
/_
1 11
. " ^
-^^
^ /
-^
_-- _ 1
.1
-{-_--3
Log,P (millimeters)
The data of Fig. 23 are rigorously applicable only to the particular charcoal for which they were determined. The quantity adsorbed is dependent on the source of charcoal, the method of its preparation, and its
subsequent treatment. The same limitation applies to adsorption data
for other materials.
Illustration 18. (a) Estimate the number of pounds of benzene which may be
absorbed by 1 lb of the activated charcoal of Fig. 23 from a gas mixture at 20C in
which the partial pressure of benzene is 30 mm of Hg.
(b) Calculate the percentage of the adsorbed vapor of part (a) which would be
recovered by passing superheated steam at a pressure of 5 lb per sq in. and a temperature of 200C through the adsorbent until the partial pressure of benzene in the
steam leaving is reduced to 10.0 mm of Hg.
(c) Calculate the residual partial pressure of benzene in a gas mixture treated
with the freshly stripped charcoal of part (6) at a temperature of 20C.
SohUion: From Fig. 23,
(o) CcHe adsorbed at 20C, 30 mm of Hg =
110 cc per g
" 7;^r:^ X '^^ = 0.382 g per g or lb per lb
. , , ,,
156
[CHAP. V
22 cc per g
90 cc per g
82%
CHAP. V]
PREFERENTIAL ADSORPTION
157
158
[CHAP. V
Waals adsorption, a gas of high molecular weight, high critical temperature, and low volatility is adsorbed in prefeJ^nce to a gas of low molecular weight, low critical temperature, and high volatility. Such a preferentially adsorbed gas or vapor will displace other gases which have
already been adsorbed. The chemical nature of the gas also plays an
20
40
60
80
Per Cent Relative Humidity
CHAP.
PREFERENTIAL ADSORPTION
V]
159
10.0
40
l..,,...l..,
80
60
11
8.0
, l...^l
Temperature, "F
100
120
140
160
y\
i/' 1 / i
1 11-
6.0
! 'i
! i ! i 'AXo x1 'X ' 1/ 1 1/ 11 1I' 1' 1l/K
4.0
, Jr X y
!/
' mvyy
2.0
l/i
I 1.0
S 0.8
I 0.6
0.4
/ \ /
- i 1 ^f%C
\/\
\ \
1 * '
'<?/''
<?/1
; 1 1 ; : i ; ; ; i; i
'
'
111
0.2
0.1
!/
'I
'
J .06
'
1
i ! 1-oy '
'
1
'
'
'
'
' ( ^
.01
0.1
\A \
0.2
..II
0.4
'
'
'
'
'
'
'
* 1 *
1 1 : 1 1 : ! ;
1 1 li i 1 1 ii t 11 I I I ;
20
40 60
100
Vapor Pressure of Water, Inches of Hg
11 / L _
0.6
1.0
II
II
II
10
s = slope ol line.
F I G . 26.
V a p o r p r e s s u r e of w a t e r a d s o r b e d o n silica gel. -
160
[CHAP. V
tents of silica gel and activated alumina compared with various solic' and
liquid chemical desiccants. It will be observed that the solid desiccants
compare unfavorably with the liquid desiccants in adsorption capacity.
However, both silica gel and activated alumina are capable of drying air
to much lower dew points than homogeneous solutions of hthium chloride
or calcium chloride.
Cox Chart for Adsorbents. A useful way of presenting the vaporpressure relations of adsorbed water is by means of the Cox chart wherein
for the same temperature the vapor pressure of adsorbed water is plotted
against the vapor pressure of pure water for lines of constant moisture
content. Straight lines generally result on a logarithmic plot, as shown
in Fig. 26 for silica gel. The relative humidity at any temperature and
composition is obtained directly from the ratio p/ps, where Ps is the vapor
pressure of pure water. This chart is also useful in estimating heats of
adsorption as discussed in Chapter VIII.
It should be noted that all the discussion in this chapter is restricted
to equihbrium conditions. Calculation of rates of sorption requires
consideration of particle size, diffusion, rates of gas flow and other
factors.
/
;>i
PROBLEMS
1. From the International Critical Tables, Vol. IV, plot a curve relating the solubility of sodium carbonate in water to temperature. Plot solubilities as ordinates,
expressed in percentage by weights of NasCOs, and temperature as abscissas, expressed in degrees Centigrade, up to 60C. On the same axes plot the freezing-point
curve of the solution, or the solubility curve of ice in sodium carbonate, locating the
eutectic point of the system.
2. From the data of Figs. 10, 11, and 12 and Problem 1, tabulate in order the successive effects produced by the following changes:
(a) A solution of naphthalene in benzene is cooled from 20 to 10C. The
solution contains 0.6 gram-mole of naphthalene per 1000 grams of benzene.
(6) A solution of sodium carbonate in water is cooled from 40 to ~5C. The
solution contains 4.6 gram-moles of NaaCOa per 1000 grams of water.
(c) A mixture of aqueous sodium sulphate solution and crystals is heated from
10 to 60C. The original mixture contains 3.3 gram-moles of NazSOi,
per 1000 grams of water.
(d) Pure crystals of Na2SO4-10H2O are heated from 20 to 40C.
(e) A solution of FeCh in water is cooled from 20 to 60C. The solution
contains 2.5 gram-moles of FeCU per 1000 grams of water.
(/) A solution of FeCU is evaporated at a temperature of 34C. The original
solution contains 5 gram-moles of FeCls per 1000 grams of water, and it is
evaporated to a concentration of 25 gram-moles of FeCh per lOOQ grams
of water.
(g) An aqueous solution of FeCls is cooled from 45 to 10C. The solution contains 18 gram-moles of FeCls per 1000 grams of water.
'
CHAP. V]
PROBLEMS
161
162
[CHAP. V
13. A dilute solution of Na2C03 and water weighs 2000 lb, and contains 5%
Na2C03. It is required that 95% of the NaaCOa be recovered as the decahydrate.
The lowest temperature that can be obtained is 5C. Specify tRe process to be
employed for securing the degree of recovery required. Present calculations with
respect to the quantitative relations involved in the process specified.
By means of a sketch, indicate how the solubility chart was used in solving the
problem.
280
240
200
^
-
s
^120
80
o-
40
"
2
1
0
,
0.5
1.0
1.5
Pounds HjO per Pound Li CI
\.l. . ,2.0
CHAP. V]
PROBLEMS
163
final temperature and the yield of crystals per 100 lb of original solution, using the
data of Fig. 14.
17. It is desired to crystallize a maximum amount of pure Na2CO3-10H2O from
the solution of Problem 11 by evaporating water at a temperature of 25C. Calculate the quantity of water which must be evaporated and the yield of crystals produced per 100 lb of original solution.
18. A solution contains 25 grams of Na2S04 and 4.0 grams of NaaCOs per 100
grams of water. From 100 lb of this solution 20 lb of water is evaporated and the
residual solution cooled to 20C. Calciilate the weight and composition of the
crystals formed in the process.
19. Calculate the weight of water which must be evaporated from 100 lb of the
solution of Problem 18 in order to crystallize 70% of the Na2S04 as the pure decahydrate at a temperature of 15C.
20. A solution has the following initial composition:
Na2SO4-10H2O = 80 parts by weight
Na2CO3-10H2O = 60 parts by weight
Solvent water = 100 parts by weight
The solution is at 50C, and weighs 2500 lb. If this solution is cooled to 5C:
(a) At what temperature does crystallization start? What phase crystallizes
out first?
(b) At what temperature will a second crystalline phase start to separate?
What is its composition?
(c) Calculate the maximum weight of pure crystals that can be obtained in the
first stage of crystallization, when but one solid phase is separating.
(d) Calculate the respective weights of the two sohd phases that separate
during the second stage of crystallization.
(e) With respect to the residual mother liquid at 5C, report its total weight,
and the weight of each of the three components that were present in the
original solution.
By means of a sketch, show how Fig. 14 was used in solving the problem.
21. A solution has the following initial composition:
Na2SO4-10H2O = 40 parts by weight
Na2CO3-10H2O = 40 parts by weight
Solvent water = 100 parts by weight
The solution originally weighs 1500 lb. If evaporation is carried out at 25C:
(o) How much water must be evaporated before crystallization starts?
(6) What is the first solid to crystallize from the solution? How much of this
pure crystalline material can be removed before a second solid starts to
separate?
(c) How much water must be removed by evaporation before a second crystalUne phase starts to form? What is the nature of this second crystaUine phase?
By means of a sketch, show how Fig. 14 was used in solving the problem.
22. A solution has the following initial composition:
Na2SO4-10H2O = 10 parts by weight
Na2CO3-10H2O = 200 parts by weight
Solvent water = 100 parts by weight
164
[CHAP. V
The solution weighs 2500 lb. It is required that 80% of the NaaCOs-lOHzO be
recovered in pure form. The lowest temperature that can be obtained is 15C.
How many pounds of water must be removed by evaporation if 80% recovery is obtained on cooling to 15C?
By means of a sketch, show how Fig. 14 was used in solving the problem.
i;.i
23. A solution has the following initial composition:
>'
'^ isif,
NajSOi-lOHjO = 80 parts by weight
NajCOj-lOHjO = 10 parts by weight
Solvent water = 100 parts by weight
''
' -?^
';.':.'y
The solution weighs 1600 lb. Compare the maximum yield of NajSOj-lOHjO
obtainable by each of the following three processes:
(o) Cooling to 10C.
'" : : '
(b) Evaporation at a constant temperature of 25C.
(c) Evaporation of a limited amount of water at 25C, followed by cooling to
ioc.
^^,
By means of a sketch, indicate how Fig. 14 was used in solving the problem.
24. The residual liquor from a crystallizing operation has the following composition :
Na2SO4-10H2O = 10 parts by weight
,
,
Na2CO3-10H2O = 60 parts by weight
, .
Na2S04
= 1.25%
Na2C03
= 10.50%
Insoluble matter = 88.25%
' ,
"'
";
(a) What is the minimum weight of the residual liquor required to dissolve the
soluble matter present in 1000 lb of the solid mass, assuming that the
leaching operation is carried out at 25C?
(6) If the hquor obtained from the leaching operation is subsequently cooled,
what is the maximum possible percentage recovery of pure NajCOs?
By means of a sketch, show how Fig. 14 was used in connection with the solution
of this problem.
25. From the data of International Critical Tables plot a solubihty chart similar
to Fig. 14 for the system NaNOaNaCl^H20. Include the solubility isotherms of
15.6, 60, and 100C.
26. A mixture of NaNOs and NaCl is leached with water at 100C to form a
solution which is saturated with both salts. From the chart of Problem 25, calculate
the weight and composition of the crystals formed by cooUng 100 lb of this solution
to 15.6C.
27. A solution of picric acid in benzene contains 30 grams of picric acid per liter.
Calculate the quantity of water with which 1 gallon of this solution at 18C must be
shaken in order to reduce the picric acid concentration to 4.0 grams per liter in the
benzene pha^e.
28. One gallon of an aqueous solution of picric acid containing 0.15 lb of picric acid
is shaken with 2 gallons of benzene. Calculate the poimds of picric acid in each solute
after the treatment.
. ,,F
,; >
CHAP. V]
PROBLEMS
165
29. A mixture of phenol and water contains 45% phenol by weight. Calculate
the weight fractions of upper and lower layers formed by this mixture at a temperature of 45C.
30. Calculate the weight fractions and compositions of the upper and lower layers
of a mixture of 30% water, 20% isopropyl alcohol, and 50% tetrachlorethylene at a
temperature of 77F.
31. Assuming the applicability of Henry's law, calculate the percentage CO2 by
weight which may be dissolved in water at a temperature of 20 C in contact with gas
in which the partial pressure of CO2 is 450 mm of Hg.
32. Assuming the applicability of Henry's law, calculate the partial pressure of
HaS above an aqueous solution at 30C which contains 3.0 grams of H2S per 1000
grams of water.
33. Calculate the volume in cubic feet of NH3 gas under a pressure of 1 atmosphere
and at a temperature of 20C which can be dissolved in 1 gal of water at the same
temperature.
34. An aqueous solution of ammonia at 10C is in equilibrium with ammonia gas
having a partial pressure of 500 mm of Hg.
(a) Calculate the percentage ammonia, by weight, in the solution.
(b) Calculate the partial pressure of the ammonia in this solution if it were
warmed to a temperatiKe of 40C.
36. Assuming that equilibrium quantities of adsorbate are determined only by the
relative saturation of the adsorbate vapor, estimate the quantity of SO2 adsorbed by
the silica gel of Fig. 22 at a temperature of 10C from a gas mixture in which the
partial pressure of SO2 is 150 mm of Hg.
36. Activated charcoal similar to that of Fig. 23 is to be used for the removal of
benzene vapors from a mixture of gases at 20C and a pressure of 1 atmosphere.
The relative saturation of the gases with benzene is 83%.
(a) Calculate the maximum weight of benzene which may be adsorbed per
pound of charcoal.
(6) The adsorbed benzene is to be removed by stripping with superheated steam
at a temperature of 180C. Calculate the final partial pressiu-e to which
the benzene in the steam leaving the stripper must be reduced in order to
remove 90% of the adsorbed benzene.
(c) If the adsorbent is so used that the benzene-bearing gases always come into
equilibrium with freshly stripped charcoal of part b before leaving the
process, calculate the loss of benzene in these treated gases, expressed as
percentage of the total benzene entering the process.
37. Fifty pounds of unsized cotton cloth containing 20% total moisture are hung
in a room of 4000-cu-ft capacity. The initial air is at a temperature of 100F,
at a relative humidity of 20%, and a barometric pressure of 29.92 in. of mercury.
The air is kept at 100F with no fresh air admitted and no air vented. Neglect
the space occupied by the contents of room.
(a) Calculate the moistvu-e content of the cloth and the relative humidity of the
air at equilibrium.
(6) Calculate the equilibrium moisture content of the cloth and the corresponding relative humidity of the air if 100 lb of wet cloth instead of 50 lb are
hung in the same room.
(c) What is the final pressure in the room under part (a)?
166
[CHAP. V
38. Air at atmospheric pressure is to be dried at 80F from 70% to 10% relative
humidity by mixing with silica gel, initially dry, and at 80F. What is the final
equilibrium moisture content of the gel, assuming'a constant temperature of 80F?
39. If air were to be dried to a dew point of 0F what would be the equilibrium
water contents of the following desiccants assuming exit temperature of air and
desiccant to be 70F.?
:
activated alumina
:
silica gel
J
.
!
:
glycerin
.
,
sulfuric acid
calcium chloride solution (avoid crystallization)
v ,
lithium chloride solution (avoid crystallization) ,
'
... . r
triethylene glycol
'
.:;
40. How would it be possible to dry air to a dew point 0F with a homogeneous
LiCl solution?
CHAPTER VI
MATERIAL BALANCES
A material balance of an industrial process is an exact accounting of
all the materials which enter, leave, accumulate, or are depleted in the
course of a given time interval of operation. The material balance is
thus an expression of the law of conservation of mass in accounting
terms. If direct measurements were made of the weight and composition of each stream entering or leaving a process during a given time
interval and of the change in material inventory in the system during
that time interval, no calculations would be required. Usually this is
impracticable, and therefore calculations are indispensable.
The generaJ principle of material baknce caJcuktions is to establish
a number of independent equations equal to the number of unknowns of
composition and mass. For example, if two streams enter a process and
one stream leaves, with no change in inventory in the system during
the time interval, the mass and composition of each stream completely
establishes the material balance. For calculating the complete material balance the greatest number of unknowns permissible is three,
selected among six possible items. Variations in solving the problem will
depend upon the particular items which are unknown, whether they be
of composition or mass, or of streams entering or leaving. The following
principles serve as guides to direct the course of calculations.
1. If no chemical reaction is involved, nothing is gained by establishing
material balances for the several chemical elements present. In such
processes, material balances should be based upon the chemical compounds rather than elements, or of components of fixed composition even
if not pure chemical compounds.
2. If chemical reactions occur, it becomes necessary to develop material balances based upon chemical elements, or upon radicals, compounds,
or substances which are not altered, decomposed, or formed in the
process.
3. For processes wherein no chemical reactions occur, use of weight
units such as grams or pounds is desirable. For processes in which
chemical reactions occur, it is desirable to utiUze the gram-mole or
pound-mole, or the gram-atom or pound-atom.
4. The number of unknown quantities to be calculated cannot exceed
the number of independent material balances available; otherwise, the
problem is indeterminate.
167
168
MATERIAL BALANCES
[CHAP. VI
CHAP. VI]
Overall balance:
'
. ; ..
x + y +z = 1000
169
!'
(a)
HiSOt balance:
0.57a; + 0.93?/ = 1000 X 0.60 = 600
(b)
(c)
HNOs balance:
Equations (a), (b), and (c) may be solved simultaneously.
Eliminating 2 from (a) and (c):
270 -0.23a; ,
'
'
0.90
+y+-
=' ^
-^'"'H''
' '
--
_ . . . <
(d)
From (b)
I
\
"
From (a)
, . z = 1000 - 390 - 418 = 192 lb
These results may be verified by a material balance of the water in the process:
Water entering = (418 X 0.20) + (390 X 0.07) + (192 X 0.10) = 130 lb
Since the final solution contains 13% H2O, this result verifies the calculations.
170
MATERIAL BALANCES
[CHAP. VI
transformation. The limiting reactant should be selected. The quantity of each reacting material may then be specified in terms of the percentage excess it forms of that theoretically required. The calculation
is then completed on the basis of the limiting reactant which is present
in a unit quantity of the reactants. The amounts of the new products
formed in the reaction are determined from the degree of completion.
The unconsumed reactants and inert materials pass into the product
unchanged.
Illustration 2. A producer gas made from coke has the following composition by
volume:
'
CO
28.0%
CO2
3.5
* ., ' i^?
O2
0.5
. |P"w
Ns
68.0
^ ^
100.0%
This gas is burned with such a quantity of air that the oxygen from the air is 20%
in excess of the net oxygen required for complete combustion. If the combustion
is 98% complete, calculate the weight and composition in volumetric per cent of the
gaseous products formed per 100 lb of gas burned.
Discussion. The carbon monoxide is the limiting reactant, while the oxygen is
the excess reactant. The amount of oxygen supphed by the air is expressed as the
percentage in excess of the net oxygen demand, this latter term referring to the total
oxygen required for complete combustion, minus that present in the fuel. Since the
composition of the fuel is known on a molal basis, it is most convenient to choose
100 lb-moles of the fuel gas as the basis of calculation, and at the close of the solution
to convert the results over to the basis of 100 lb ot gas burned.
28.0
44.0
32.0
28.2
28.0
3.5
0.5
68.0
100.0
Weight in Pounds
2 8 . 0 X 2 8 . 0 = 7841b
3 . 5 X 4 4 . 0 = 1541b
0 . 5 X 3 2 . 0 = 161b
68.0 X 28.2 = 19171b
28721b
Oxygen Balance:
O2 required to combine with all CO present 1/2 X 28.0 = . .
O2 in the producer gas
Net O2 demand = 14.0 - 0.5
O2 supphed by air = 13.5 X 1.20
1^ O2 actually used = 0.98 X 28.0 X 1/2
fi : O2 in products = 16.2 + 0.5 - 13.7
or 3.0 X 32
14.0 lb-moles
0.5 lb-mole
13.5 lb-moles
16.2 lb-moles
13.7 lb-moles
3.0 lb-moles
96.0 lb
"^ f
CHAP. VI]
171
Carbon Balance
C in fuel gas = 28.0 + 3.5
C in CO of products of combustion = 0.02 X 28.0
C in CO2 of products of combustion = 31.5 0.56
Carbon monoxide in products
or 0.56 X 28
Carbon dioxide in products
,
or 30.94 X 44
31.5 lb-atoms
0.56 lb-atom
30.94 lb-atoms
0.56 lb-mole
15.7 lb
30.94 lb-moles
1359 lb
Nitrogen Balance
N2 in producer gas
N2 from air = 79/21 X 16.2
Nz in products = 68.0 -|- 60.9
or 128.9 X 28.2
68.0 lb-moles
60.9 lb-moles
128.9 lb-moles
3637 lb
CO2
O2
CO
N2
=
=
=
=
(30.9/163.4)
(3.0/163.4)
(0.56/163.4)
(128.9/163.4)
X 100
X 100
X 100
X 100
'
5108 lb
1781b
i
163.4 lb-moles
Mole or
Volumetric
%
18.92
1.84
0.34
78.9
100.00
13.48%
0.28
0.61
10.36
75.27
100.00%
172
MATERIAL BALANCES
[CHAP. VI
(c) The reacting material which is present in excess, and its percentage excess.
(d) The degree of completion of the reaction.
Discussion. The problem as stated cannot be solved before additional data are
obt^ned. The needed additional information is either the analysis of the lime or the
analysis of the alkaline liquor.
If the analysis of the lime were determined, the problem could be solved by the
following steps: (1) By using calcium as a tie-substance the weight of hme would
be determined. (S) An overall material balance would estabhsh the weight of alkaline hquor. (3) By a carbon balance, the weight of Na2C03 in the alkaline liquor
would be computed. (4) By using sodium as a tie-substance the weight of
NaOH in the alkaline liquor would be calculated. (6) The weight of water in the
alkahne hquor would be determined by difference.
If the analysis of the alkahne hquor were determined instead, the problem would
be solved according to the following procedure: (1) By using sodium as a tiesubstance the total weight of the alkaline liquor would be calculated. (^) An overall material balance would establish the weight of lime. .{3) By means of a carbon
balance, the weight of CaCOa in the lime would be determined. (4) A calcium
balance would give the weight of active CaO [free CaO plus the CaO in the Ca(0H)2]
in the lime. (5) The weight of free CaO and the weight of Ca(0H)2 in the lime
could then be computed from the available values for the weight of lime, the weight
of CaCOs, and the weight of active CaO.
From the foregoing, it is apparent that it is only a matter of convenience whether
the Ume or the alkaline liquor is analyzed. The normal choice would be to analyze
the alkaline liquor, because the analysis is rapid and accurate.
An analysis of the alkaline liquor used in the process gave the following results:
NaOH
NajCOa
H20
0,594%
14.88 %
84.53 %
100.00 %
0.00594
0.1488
0.8453
1.0000
0.000140
0.001404
NasCOs = 106.0
CaCO, = 100.1
H2O = 18.02
Lb-Atoms
,,T
Na
0.000149
0.002808
Lb-Atoms
r^
C
0.002957
0.001404
0.001404
CHAP. V I ]
13.48
0.28
0.61
10.36
75.27
0.1347
0.00377
0.00575
0.2590
100.00
Sodium Balance
Lb-Atoms
ri
Ca
0.1347
0.0038
0.1385
173
Lb-Atoms
T
Na
Lb-Atoms
^
C
0.1347
0.0115
0.2590
0.00575
0.2705
0.1405
'
0.2705 lb-atom
0.002957 lb-atom
91.50 lb
i
100.00 lb
91.50 lb
8.50 lb
Carbon Balance
Object: To evaluate the weight of CaCOs in the lime.
C in causticized mass =
0.1405 lb-atom
C in NasCOs = 91.50 X 0.001404 =
0.1285 lb-atom
C in CaCOs = 0.1405 - 0.1285 =
0.0120 lb-atom
Weight of CaCOs = 0.0120 X 100.1 =
1.20 lb
Calcium Balance
Object- To determine the active CaO [that present in the Ca(0H)2 plus the free
CaO] in the lime.
Ca in the causticized mass = Ca in the lime = .
0.1385 lb-atom
Ca present as CaCOa in the lime (see carbon
balance) =
0.0120 lb-atom
Ca present in Ca(OH)2 and in free CaO =
0.1385 - 0.0120 =
0.1265 lb-atom
Overall Balance of Constituents in the Lime
Object: To determine free CaO and Ca(0H)2 in the lime
Total weight of hme charged =
8.50 lb
Weight of CaCOs (see carbon balance) = . .. .
1.20 lb
Weight of CaO + Ca(0H)2 = 8.50 - 1.20 =
7.30 lb
Weight of total active CaO = 0.1265 X 56.1 =
7.10 lb
H2O present in the Ca(0H)2 = 7.30 - 7.10 =
0.20 lb
Ca(0H)2 in lime = 0.20 X (74.1/18.02) = . . .
0.82 lb
Weight of free CaO = 7.30 - 0.82 =
6.48 lb
174
MATERIAL BALANCES
Results
(a) Weight of lime =
Analysis of lime
4'....
[CHAP. VI
8.50 lb
PerCent
14.1
9.6
76.3
100.0
(6) Weight of alkaline liquor
91.45 lb
Analysis of alkaline liquor was determined experimentally.
(c) Determination of Excess Reactant.
Total active CaO =
0.1265 lb-mole
NajCOs in liquor = 91.50 X 0.001404 =
0.1285 lb-mole
CaCOs
Ca(0H)2
CaO
Lb
1.20
0.82
6 ^
8.50
CHAP. VI]
PROCESSES INVOLVING C H E M I C A L R E A C T I O N S
175
" Salt cake " prepared by such a process was found to have the following composition:
NajSO,
91.48%
NaHS04
4.79%
NaCI
1.98%
H^O
1.35%
HCI
0.40%
100.00%
T h e salt used in t h e process is dry, and m a y be assumed to be 100% NaCl.
(o) Calculate the degree of completion of the first reaction and the degree of completion of the conversion to Na2S04 of the salt charged.
(6) On the basis of 1000 lb of salt charged, calculate the weight of acid added, the
weight of salt cake formed and the weight and composition of the gases driven off.
Discussion.
The logical choice of a basis of calculation is 1000 lb of salt, since the
results are wanted on that basis.
The solution of part (6) is accomphshed through a series of material balances. I t
will be noted t h a t sodium serves as a tie-substance between the salt cake and the
salt charged, and that sulfur serves as a tie-substance between the salt cake and the
aqueous acid. Accordingly, the problem may be solved by the following successive
steps: (1) A sodium balance establishes the weight of salt cake. (2) A sulfur
balance serves to determine the weight of aqueous acid used. (3) A chlorine balance
estabhshes the weight of HCI driven off in the gases. (4) A water balance determines the weight of H2O in the gases driven off.
Basis of Calculation:
Molecular Weights
NaCl
= 58.5
H2SO4 = 98.1
NasSOi = 142.1
HCI = 36.46
NaHSOi = 120.1
...
17.08 lb-moles
0.9148
NaHSOi
0.0479
NaCl
0.0198
0.00764 lb-mole
1 lb.
Ti, A/r 1
Lb-Moles
0.9148
= 0.00644
Lb-Atoms
^^
Lb-Atoms
g
0.01288
0.00644
= 0.000398
0.000398
0.000398
0.0198
T^TT" = 0.000338
0.000338
0.0479
Lb-Atoms
^j
0.000338
00.0
H2O
0.0135
HCI
0.0040
1.0000
0.0040
- = 0.000110
36.46
0.000110
0.01362
0.00684
0,000448
176
MATERIAL BALANCES
[CHAP. VI
Part (o) can be worked out by focusing attention on the salt cake. Since no H2SO4
is present in the product, the first reaction went to completion.
Total Na present
NainNajSOi
Conversion of NaCl to Na2S04 =
(0.01288/0.01362) X 100
0.01362 lb-atom
0.01288 lb-atom
94.5%
Sodium Balance
Object: To determine the weight of salt cake.
Na in 1000 lb salt charged
Na in 1 lb salt cake
Weight of salt cake = 17.08/0.01362
17.08 lb-atoms
0.01362 lb-atom
1253 lb
Sulfur Balance
Object: To determine the weight of aqueous acid used.
S in salt cake = 1253 X 0.00684
S in 1 lb of aqueous acid
Weight of aqueous acid = 8.58/0.00764
8.58 lb-atoms
0.00764 lb-atom
1123 lb
Water Balance
',
281 lb
17 lb
264 lb
Chlorine Balance
Object: To determine the weight of HCl in gas evolved.
CI in salt charged
CI in salt cake = 1253 X 0.000448
CI in HCl driven off = 17.08 - 0.56
Weight HCl in gases = 16.52 X 36.46
*
17.O8 lb-atoms
0.56 lb-atom
16.52 lb-atoms
603 lb
Lb
603
264
867
Per Cent
69.6
39.4
100.0
.. ;,
Overall Balance
Object: To check the accuracy of the calculations.
Total weight of reactants = 1000 -|- 1123
Total weight of products = 1253 -f 867
sit* (?
2123 lb
2120 lb
CHAP. VI]
177
178
MATERIAL BALANCES
[CHAP. VI
III. The sludge pumped from each tank contains c pounds of solvent
per pound of insoluble solid. The concentration of soluble material in
the solution is expressed as pounds per pound of solvent, and is designated as X in tank I, y in tank II, and z in tank III.
A material balance of the solute for each tank is as follows:
Output
Input
First
tank
Slurry
Sludge
cmix
Clear solution
(TOS cm,-i)x
Second
tank
Clear solution
may
Sludge
amy
(2)
Third
tank
Clear solution
msz
Sludge
cmiz
(3)
Overall
balance
Clear solution
Solid
0
^ TOi =
' -
fill + ym%
(1)
Sludge residue
Clear solution product
cm2Z
(TOS cm2)x
+
(4)
.,i.i
*,
Substituting these values in Equations (1), (2), (3), and (4) for a balance of sodium
carbonate, there results
First tank
Second tank
Third tank
Overall balance
SOOOa
30002/
3000z
SOOOz
'
CHAP. VI]
179
'
x = 0.139
y == 0.039
s = 0.009
180
MATERIAL BALANCES
[CHAP. VI
m2=n-7 tons
mi=12.6 tons
\y
\y
\ /
Barometric
Condenser
s tons
'w^
. Fresh B r i n e ^ ^ ^
29 tons
200 i?
26* NaCl
Condensate
mi-12.6 tons
Condensate
EVAPORATOR I
EVAPORATOR H
Condensate
m2=11.7 tons
EVAPORATOR III
Condensate m^
and Condensing
Water
II
III
250F
229F
10" drop
12.6 tons
29.0
2.15
214F
187F
12" drop
11.7 tons
27.9
173F
137F
8" drop
27.0
It is desired to calculate the tons of NaCl crystallized in each evaporator and the
tons of water evaporated from evaporator III.
CHAP. VI]
181
Solution:
In each effect the brine solution is saturated, with a density which may be obtained
from Fig. 1, page 18. The depletion of brine in each evaporator is not only that
corresponding to the drop in liquid level but also that displaced by the salt crystallizing out and accumulating in the hopper. For each ton of salt crystallizing out
-- tons of brine are displaced, where 2.15 is the Specific gravity of the salt crystals
2.15
and G is that of the brine solution. For example, in the first evaporator,
G
2.15
1.140
= 0.53
2.150
where
J
:
.29.0
1.140
X
10
4.30
0.53x
1,25 + 0.164x
3.05 + 0.376X
12.6
II
III
27.9
27.0
1.145
1.150
z
y
12
8
5.18
3.46
0.532?/
0.5352
1.45 + 0.149y 0.935 + 0.1452
3.73 + 0.3832/ 2.52 + 0.3902
11.7
W3
(b)
(d)
182
MATERIAL BALANCES
[CHAP. VI
From salt and water balances for each evaporator the following are obtained:
Evaporator I
Salt
if
1.25 + 0.154X + 0.26(29) = x + 0.29r
Water
(e)
Evaporator II
^t
(g)
Water
(h)
Evaporator III
Salt
(i)
a)
From (b)
MATERIAL BALANCE
Input
Tone
29.00
(a) Bnne
Depletion Items
(a) Brine in I
i''
'
4.30 + 0.53a; =
4 . 3 0 + (0.53) (3.91) == 6.37
(b) Brine in II
5.18 - 0.532?/ =
5.18 - (0.532) (4.82) = 7.75
(c) Brine in III
3.46 + 0.5352 =
3.46+ (0.635) (4.38)
Output
(a) Water from I
Tons
12.60
11.70
11.47
3.91
5.80
48.92
4.82
4.38
48.88
RECYCLING OPERATIONS
CHAP. VI]
RECYCLING OPERATIONS
183
.,
184
MATERIAL BALANCES
[CHAP. VI
i'
^1 - W2*= r(l - y)iH, -Ho)
';'
. ;"^ ' p j ;
Once-through balance:
'.*:;;
Wi - W2 = riH2 - Hi)
; '
"
" *ig^'
where
Wi = moisture content of stock entering, pound per pound dry stock
Wi = moisture content of stock leaving, pound per pound dry stock
Hi = humidity of air leaving, pound per pound dry air
Hi = humidity of air entering dryer, pound per pound dry air
' ^''
Ho = humidity of fresh air supply, pound per pound dry air
From Equations (1) and (2)
'
'
iH2-Ho)y
''
= Hi-Ho
'
' '
-"'
(3)
!.
i;. ...
^, j " , ^^ ;.!.
Based on these data it is desired to design a plant to produce 100,000 pounds per
day of propylene in a mixture of 98.8% purity. The flow diagram of the proposed
process is shown in Fig. 31.
>.. .
CHAP.
VI]
RECYCLING OPERATIONS
185
Fresh propane feed, mixed with propane recycle stock is fed to a heater from
which it is discharged to a catalytic reactor operating under such conditions as to
produce the same conversion of propane as was obtained in the laboratory experiment.
The reactor effluent gases are cooled and compressed to a suitable pressure for separation of the light gases. This separation is accomplished by absorption of the propane
aiid propylene, together with small amounts of the lighter gases, in a cooled absorption oil which is circulated through an absorption tower. The " fat oil " from the
bottom of the absorber is pumped to a stripping tower where by application of heat
at the bottom of the tower the dissolved gases are distilled away from the oil which is
then cooled and recirculated to the absorber.
f^^ Propylene
186
MATERIAL BALANCES
[CHAP. VI
(6) The process period in minutes required in building a carbon deposit equal to
2% by weight of the catalyst.
M
(c) An overall material balance.
(d) A once-through material balance.
(e) Ultimate yield of recovered propylene expressed as mole percentage of propane
in fresh feed.
(/) Once-through yield of propylene made in reactor expressed as mole percentage
of total propane entering reactor.
{g) Recycle ratio, weight units.
{h) Total feed ratio, weight units.
' . ' i . \ ' , , i-ii.
*%
,
Preliminary Calculations
. ^.; .
,'"
1
Gas Formed by Decomposition of Propane
'
.*'i;~..
!
Basis: 1 lb-mole of gas.
Lb-Moles
Propane CaHs
Propylene CsHe
Hydrogen Hj
Ethylene C2H4
Ethane C2HS
Methane CH4
0.445
0.213
0.254
0.003
0.053
0.032
1.000
Mole Wt
44.09
42.08 .
2.016
28.05
30.07
16.04
Lb
19.62
8.96
0.512
0.084
1.594
0.513
31.28
Lb-Atoms
C
1.335
0.639
0.006
0.106
0.032
2.118
Lb-Atoms
H
3.560
1.278
0.508
0.012
0.318
0.128
5.804
8.000
= 1.378
5.804
lb-moles.
Process Design Calculations
Basis of design: 1 hour of operation.
^ , .
,
,
100,000
,,
Production rate of pure propylene = = 4167 Ib/hr
or
= 99.03 Ib-moles/hr
42.08
Evaluation of Unknown Stream Weights
Let X = lb-moles recycle
y = lb-moles fresh feed
z = lb-moles light gases
Combined feed
Propane = y + 0.9791x lb-moles
Propylene = 0.02095a; lb-moles
Gases leaving reactor
Gases formed from the
propane entering
= 1.378(2/ + 0.97913;)
= 1.378?/-F 1.349a; lb-moles
CHAP.
187
RECYCLING OPERATIONS
VI]
Propylene passing
through unchanged
Total gas leaving
Propane leaving
Propylene leaving
.:.
= 0.0209SX lb-moles
= 1.378?/ + 1.370a;
= (1.3782/-|-1.349x) (0.445)
= 0.6132/ + 0.600a; lb-moles
= 0.213(1.3782/ + 1.349x) + 0.02095a;
= 0.29352/ + 0.3083a; lb-moles
MATERIAL BALANCES
(lb-moles)
Leaving Reactor
Recycle
Propane Balance
Propylene Balance
0.29352/ + 0.3083X
Total
1.3782/ + 1.370X
Product
Light Gases
99.03
+
(0.00476) -l-O.Ollz
0.9855
0.02095X -t-99.03
+ 0.007z
99.03
+z
+ 0.9855
0.011? =
0.478
= ^^-^
Solving:
X = 210.8 lb-moles recycle
2/= 134.2 lb-moles fresh feed
,,, ,
(0.445) (469.3)
=
(0.213) (469.3) + 4 . 4 =
(0.254) (469.3)
=
(0.003) (469.3)
(0.053) (469.3)
(0.032) (469.3)
208.8
104.4
119.3
1.4
24.9
15.0
= 4.42
Mole Wt
44.09
42.08
2.016
28.05
30.07
16.04
473.8
lVrnlp/nln.T Tvp.ic,M,
_ 1^'S68 _ ^R1.38
473.8
Lb
9,206
4,393
240
39.2
749
241
14,868
188
MATERIAL BALANCES
Light Gases
,
^<!i
;..;:
Lb-Moles
1.792
1.140
119.3
1.4
15.0
,,.... ,.
Mole Wt
44.09
42.08
2.016
28.05
16.04
Lb
79.0
48.0
240.6
39.2
240.6
30.07
718.7
23.9
In light gases
[CHAP. VI
23.9
162.5
1,366.0
!,.i-\
Moleciilar weightt ==
= 8 .41
162.5
Recycle
CjHs (0.9791) (210.8)
C3H6 (0.02095) (210.8)
Lb-Moles
206.4
4.42
Mole Wt
44.09
42.08
210.8
,;
9,286
Molecular weight = r r r r = 44.05
210.0
Lb
9,100
186
-
9,286
Product
C3H,
M229
=4,167 lb
24
(0.007) (4,217) = 29.5 lb
(0.005) (4,217) = 21.11b
CsHs
CjHe
Fresh Feed
(134.2) (44.09)
Carbon Deposit
j . \
=5,917 lb
Propane to reactor
134.2 + 206.4 = 340.6 lb-moles
C in propane
= (3) (340.6) (12)
= 12,262 lb
C in gases formed from propane = (1.378) (340.6) (2.118) (12) = 11,929 lb
C deposited on catalyst
333 lb
Required Results:
(o) Amount of carbon deposited on catalyst, as weight per cent of the propane
fed to the reactor.
333
Caxbon deposit = ^ ; ^ j ^ ^ P ^ = 2.22%
RE(:)YCLING
CHAP. VI]
OPERATIONS
189
= 210.8 + 134.2 =
345.0
4.1
Weight of catalyst
= (84.2) (54)
Carbon tolerance
= (0.02) (4,647)
Rate of carbon deposition =
Volume of catalyst
= 1'"'
Process period
(c) Overall Material Balance
345 lb moles/hr
84.2 cu ft
= 4,5471b
= 90.91b
=
3331b/hr
=
16.4 min
^ if-' ,
';
Inpvi
Fresh feed
Output
%
'>.
6,917 lb
;,.,,
Light gases
Product
Carbon deposit
Total
1,366 lb
4,217
333
5,916
Input
Fresh feed
Recycle
Total
'<
Total
V " ]
5,917 lb
9,286
15,203
15,203 lb
1,366 lb
4,217
333
9,286 ' '
15,202
,; :,
15,202 lb
Propylene in product
'"
Propane feed
'-
99 03
Per cent yield = ^ (100) = 73.8%
11
Outprd
Light gases
Product
Carbon deposit
Recycle
5,916 lb
i , , ' f-
99.03 lb moles
134.2 lb moles
'
' .
'
190
MATERIAL BALANCES
[CHAP. VI
9,286 lb
5,900 lb
15,186 1b
'= 2.57
5,917
'
"
'
.
"*
'
CHAP. VI]
191
tion limit of argon in the reactor is assumed to be 5 parts to 100 parts of Nz and Hj
by volume. Estimate the fraction of recycle which must be continually purged.
Fresh Feed
100 lb. moles Nj+H.
0.2 lb. moles Argon
lvww\l
Reactoi
Condenser
1
NHjUquid
Recycle i lb. moles Nj+Hj
i..i V
I -\
>>|
^
:\
':_
y Bled stream
y lb. moles Nj+Hj
MATERIAL BALANCES
192
[CHAP.
VI
In the actual operation of a high pressure plant the unavoidable leakage generally
is sufficient to keep argon in the reactor below the toleration limit so that no special
provision need be applied for venting part of the recycle to prevent accumulation.
1.0
/
/
^ J
o 1
SI
91 1
1
8/
to 1
1
m 1
"3 1
u f
(5/
<N 1
41
to /
c 1
SI
0} 1
a> f
"5/
CO 1
o 1
Ho
10
j/
/
/
20
30
50
TO
FIG. 33. Fraction of moisture removed from air by a bed of silica gel.
CHAP. VI]
BY-PASSING STREAMS
193
humidity is obtained in the final air mixture if part of the air is dehumidified to a low moisture content and then mixed with the unconditioned
air to produce the desired mixture. The fraction of the entering humidity remaining in the air after drying in beds of silica gel of various thicknesses is shown in Fig. 33 plotted against the product of p^w where
w the total pounds of dry air passed through gel per
square foot of cross-section
Ps the vapor pressure of water in atmospheres at
the temperature of the bed
W = GT = Upr
where
G =
T=
p=
u =
:> ;
It will be observed that the humidity of the air leaving the gel is by
no means constant. For an extended period of time, as indicated by the
abscissas, the air leaves with nearly no humidity, then it rises abruptly
as more air is passed through. The bed behaves as though a wedge of
water of the shape of the curves shown in Fig. 33 were advancing through
the bed; at first the advancing wedge is nearly imperceptible, then
suddenly the full wedge appears.
niustration 9. 1000 cu ft of air per minute at 8SF, 70% relative humidity is to
be conditioned to a relative humidity of 30% and kept at 85F, using a stationary
bed of silica gel 12 in. thick and 4 ft in diameter. To maintain the relative humidity
constant at 30%, part of the air is by-passed around the dryer and mixed with the
part which is dried. Constant humidity in the final air mixture is controlled automatically by a damper regulating the fraction of air to be by-passed. This is accomplished by a constant wet-bulb controller. Assuming isothermal operation,
(a) Construct a plot showing the fraction of air to be by-passed against time.
(b) Calculate the time of operation before regeneration becomes necessary.
Area of bed = - = 12.52 sq ft
4
1000 492
Total rate of air flow = -- X X 0.9716 X 29 = 70.9 lb per min (dry
oOu
o4o
basis)
70.9
Rate of air flow per sq ft of bed = : = 5.66 lb per min (dry basis)
12.52
ffo = initial humidity = 0.0182
Hi = desired humidity = 0.0077
H = humidity leaving dryer
194
MATERIAL BALANCES
[CHAP. VI
= 0.0077
0.0077 - H
0.0182 - H
(a)
'
p.w
H/Ho
(Fig.
33)
Aw
interval
interval Aw
0.423
960
169.6
0.00032
0.413
105
18.6
0,00128
0,379
99
17.5
0,00291
0.313
90
15.9
0,00519
0.193
76
13.4
0.00708
0.055
25
4.4
0
0.035
0.105
0.215
61,5
32.5
0.355
24.0
33.5
0.423
824
188
206
222
235
0,00646
800
0,0077
min
170
0,00392
739
10
0,00191
677
61.5
30.0
AT
-X
0.000637
616
61,5
27.5
Aw
1
554
61.5
25.0
0
554.0
22.5
239
2 AT = 239 m in
CHAP. VI]
PROBLEMS
Aw
195
'
and is tabulated in Column 8.
The
time interval AT corresponding to the air interval Aw is obtained bydividing items in Column 8 by 5.66; these are tabulated in Column 9.
The total time elapsed is obtained from a summation of items in column
9, T = SAT, and tabulated in Column 10.
A plot of X against T gives the desired schedule for by-passing air. For
the first 170 minutes, 42% of the air is by-passed, after which time the
by-pass is gradually decreased to no by-pass, according to schedule, until
a total of 239 minutes has elapsed. The silica gel must then be
regenerated.
PROBLEMS
196
MATERIAL BALANCES
[CHAP. VI
5. The waste acid from a nitrating process contains 21% HNO3, 55% H2SO4,
and 24% H2O by weight. This acid is to be concentrated to contain,28% HNO3
and 62% H2SO4 by the addition of concentrated sulfuric acid containing 93%
H2SO4 and concentrated nitric acid containing 90% HNO3. Calculate the weights
of waste and concentrated acids which must be combined to obtain 1000 lb of the
desired mixture.
6. In the manufacture of straw pulp for the production of a cheap straw-board
paper, a certain amount of lime is carried into the beaters with the cooked pulp. It
is proposed to neutralize this lime with commercial sulfuric acid, containing 77%
H2SO4 by weight.
In a beater containing 2500 gal of pulp it is found that there is a lime concentration equivalent to 0.45 gram of CaO per liter.
(a) Calculate the number of pound-moles of lime present in the beater.
(6) Calculate the number of pound-moles and pounds of H2SO4 which must be
added to the beater in order to provide an excess of 1.0% above that
required to neutralize the lime.
(c) Calculate the weight of commercial acid which must be added to the beater
for the conditions of 6.
(d) Calculate the weight of calcium sulfate formed in the beater.
7. Phosphorus is prepared by heating in the electric furnace a thoroughly mixed
mass of calcium phosphate, sand, and charcoal. It may be assumed that in a certain
charge the following conditions exist: the amount of silica used is 10% in excess of
that theoretically required to combine with the calcium to form the silicate; the
charcoal is present in 40% excess of that required to combine, as carbon monoxide,
with the oxygen which would accompany all the phosphorus as the pentoxide.
(a) Calculate the percentage composition of the original charge.
(6) Calculate the number of pounds of phosphorus obtained per 100 lb of charge,
assuming that the decomposition of the phosphate iby the silica is 90%
*
complete and that the reduction of the liberated oxide of phosphorus, by
the carbon, is 70% complete.
8. A coal containing 81% total carbon and 6% unoxidized hydrogen is burned in
air.
(a) If air is used 30% in excess of that theoretically required, calculate the number of pounds of air used per pound of coal burned.
(b) Calculate the composition, by weight, of the gases leaving the furnace,
assuming complete combustion.
9. In the Deacon process for the manufacture of chlorine, a dry mixture of hydrochloric acid gas and air is passed over a heated catalyst which promotes oxidation of
the acid. Air is used in 30% excess of that theoretically required.
(o) Calculate the weight of air supplied per pound of acid.
(b) Calculate the composition, by weight, of the gas entering the reaction
chamber.
(c) Assuming that 60% of the acid is oxidized in the process, calculate the composition, by weight, of the gases leaving the chamber.
10. In order to obtain barium in a form which may be put into solution, the natural
sulfate, barytes, is fused with sodium carbonate, A quantity of bar3rtes, containing
only pure barium sulfate and infusible matter, is fused with an excess of pure, anhydrous soda ash. Upon analysis of the fusion mass it is found to contain 11.3%
CHAP. VI]
PROBLEMS
197
barium sulfate, 27.7% sodium sulfate, and 20.35% sodium carbonate. The remainder is barium carbonate and infusible matter.
(a) Calculate the percentage completion of the conversion of the barium sulfate to the carbonate and the complete analysis of the fusion mass.
(&) Calculate the composition of the original barytes.
(c) Calculate the percentage excess in which the sodium carbonate was used
above the amount theoretically required for reaction with all the barium
sulfate.
11. In the manufacture of sulfuric acid by the contact process iron pyrites, FeSj,
is burned in dry air, the iron being oxidized to Fe203. The sulfur dioxide thus
formed is further oxidized to the trioxide by conducting the gases mixed with air over
a catalytic mass of platinum-black at a suitable temperature. It will be assumed
that in the operation sufficient air is supplied to the pyrites burner that the oxygen
shall be 40% in excess of that required if all the sulfur actually burned were oxidized
to the trioxide. Of the pyrites charged, 15% is lost by falling through the grate with
the " cinder " and is not burned.
(a) Calculate the weight of air to be used per 100 lb of pyrites charged.
(6) In the burner and a " contact shaft " connected with it, 40% of the sulfur
burned is oonvertfed to the trioxide. Calilatethecompo&itioa,byweight,
of the gases leaving the contact shaft.
(c) By means of the platinum catalytic mass, 96% of the sulfur dioxide remaining in the gases leaving the contact shaft is converted to the trioxide.
Calculate the total weight of SO3 formed per 100 lb of pyrites charged.
(d) Assuming that all gases from the contact shaft are passed through the
catalyzer, calculate the composition by weight of the resulting gaseous
products.
(e) Calculate the overall degree of completion of the conversion of the sulfur in
the pyrites charged to SO3 in the final products.
12. In the LeBlanc soda process the first step is carried out according to the
following reaction:
2NaCl -1- H2SO4 = NaCl + NaHSO, -|- HCl
The acid used has a specific gravity of 58Baum6, containing 74.4% H2SO4. It is
supplied in 2% excess of that theoretically required for the above reaction.
(a) Calculate the weight of acid suppHed per 100 lb of salt charged.
(6) Assume that the reaction goes to completion, all the acid forming bisulfate,
and that in the process 85% of the HCl formed and 20% of the water
present are removed. Calculate the weights of HCl and water removed
per 100 lb of salt charged,
(c) Assuming the conditions of part (b), calculate the percentage composition
of the remaining salt mixture.
13. In the common process for the manufacture of nitric acid,, sodium nitrate is
treated with aqueous sulfuric acid containing 95% H2SO4 by weight. In order that
the resulting " niter cake " may be fluid, it is desirable to use sufficient acid so that
there will be 34% H2SO4 by weight in the final cake. This excess H2SO4 will actually'
be in combination with the Na2S04 in the cake, forming NaHS04, although for purposes of calculation it may be considered as free acid. It may be assumed that the
cake will contain 1.5% water, by weight, and that the reaction will go to completion,
198
M A T E R I A L BALANCES
[CHAP VI
Assume t h a t the sodium
(o) Calculate the weight and percentage composition of the niter cake formed per
100 lb of sodium nitrate charged.
(6) Calculate the weight of aqueous acid to be used per 100 lb of sodium nitrate,
(c) Calculate the weights of nitric acid and water vapor distilled from the niter
cake, per 100 lb of NaNOa charged.
14. Pure carbon dioxide may be prepared by treating limestone with aqueous sulfuric acid. The limestone used in such a process contained calcium carbonate and
magnesium carbonate, the remainder being inert, insoluble materials. The acid used
contained 12% H2SO4 by weight. The residue from the process had the following
composition:
CaS04
8.56% "
MgSOi
6.23%
;HiiSOi
1.05%
,
Inerts
0.53%
CO2
0.12%
.
^
Water
84.51%
During t h e process the mass was warmed and carbon dioxide and water vapor
removed.
(a) Calculate the analysis of the limestone used.
(6) Calculate the percentage of excess acid used.
(c) Calculate the weight and analysis of the material distilled from the reaction
mass per 1000 lb of limestone treated.
16. Barium carbonate is commercially important as a basis for the manufacture
of other barium compounds. In its manufacture, barium sulfide is first prepared
by heating the natural sulfate, barytes, with carbon. The barium sulfide is extracted
from this mass with water and the solution treated with sodium carbonate to precipitate the carbonate of barium.
In the operation of such a process it is found t h a t the solution of bariimi sulfide
formed contains also some calcium sulfide, originating from impurities in the barytes. T h e solution is treated with sodium carbonate and the precipitated mass of
calcium and barium carbonates is filtered off. It is found that 16.45 lb of dry precipitate are removed from each 100 lb of filtrate collected. The analysis of the precipitate is:
CaCOa..'
9.9%
BaCOs
90.1%
'
The analysis of the filtrate is found to be:
NazS
NaaCOa
H20
6.85%
2.25%
90.90%
',
The sodium carbonate for the precipitation was added in the form of anhydrous soda
ash which contained calcium carbonate as an impurity.
(a) Determine the percentage excess sodium carbonate used above t h a t required
to precipitate the BaS and CaS.
(6) Calculate the composition of the original solution of barium and calcium
sulfides. {Note: Barium sulfide is actually decomposed in solution, existing as the compound OHBaSH-5H20. However, in this reaction the
CHAP. VI]
PROBLEMS
199
#1 Tower
Net overhead
9,240
#2 Tower
Net overhead
6,390
98.5
1.5
1.0
98.6
0.5
#2 Tower
Bottoms
10,800
0.7
99.3
200
MATERIAL BALANCES
[CHAP. VI
During the period the Uquid levels in the accumulator sections of the plant varied, as
shown by level indicators measuring the heights of the levels above arbitrary fixed
points. The hquid volume, corrected to 60F of the accumulator sections per inch
of height and the initial and final levels were as follows:
Corrected liquid
Initial
Final level
vol. gal/in.
level, in.
in.
24
#1 Tower Reflux Accumulator
36
68
46
#1 Tower Bottom Accumulator i
#2 Tower Reflux Accumulator
86
W
3$
52
M
#2 Tower Bottom Accumulator
IS
Benzene
J Condenser No. 2
^y
Tower No. 1 Q
<=s Reflux
^ ^ Accumulator
^
No. 2
_ ^Toluene
1X1*-
_j^^jJCylenes
Tower No. 2
.
(a) The volume and composition of the feed during the twelve hour operating
period.
(b) The rate of flow from the bottom of Tower #1.
(c) The rate of production of distillate and bottoms from each tower assuming
the hquid levels had been maintained constant for the same rate of feed.
22. Stock containing 1.562 pounds of water per pound of dry stock is to be dried to
0.099 pound. For each pound of stock (dry basis) 52.5 pounds of dry air pass
through the dryer, leaving at, a humidity of 0.0525. The fresh air is supplied at a
humidity of 0.0152.
,
(o) Calculate the fraction of air recirculated.
(b) If the size of dryer required is inversely proportional to the average wet-bulb
depression of the air in the dryer, calculate the relative size of dryers required
with and without recirculation when operated at a constant temperatxire of
140F.
23. It is required to condition 1000 cu ft of air per minute from 70F and 80%
relative humidity to a constant value of 10% relative humidity by means of a stationary bed of silica gel. Part of the stream may be by-passed and a damper regulator
automatically controlled to maintain a constant wet-bulb temperature in the final air
mixture. The air velocity through the bed shall not exceed 100 ft per minute (total
cross section basis) and the time cycle, before regeneration is necessary, shall be 3
hours. Assume isothermal operation. Calculate the diameter and thickness of bed
required.
CHAPTER VII
THERMOPHYSICS
In Chapter II, the general concepts of energy, temperature, and heat
were introduced under the broad classification of potential and kinetic
energies. Both these forms were subclassified into external forms determined by the position and motion of a mass of matter relative to the
earth or other masses of matter and into internal forms determined by
the inherent composition, structure, and state of matter itself, independent of its external position or motion as a whole.
Internal Energy. The internal energy of a substance is defined as
the total quantity of energy which it possesses by virtue of the presence,
relative positions, and movements of its component molecules, atoms,
and subatomic units. A part of this energy is contributed by the translational motion of the separate molecules and is particularly significant
in gases where translational motion is nearly unrestricted in contrast
to the situation in liquids and solids. Internal energy also includes the
rotational motion of molecules and of groups of atoms which are free to
rotate within the molecules. It includes the energy of vibration between the atoms of a molecule and the motion of electrons within the
atoms. These kinetic portions of the total internal energy are determined by the temperature of the substance and by its molecular structure. The remainder of the internal energy is present as potential energy
resulting from the attractive and repulsive forces acting between molecules, atoms, electrons, and nuclei. This portion of the internal energy
is determined by molecular and atomic structures and by the proximity
of the molecules and atoms to one another. At the absolute zero of
temperature all translational energy disappears but a great reservoir of
potential energy and a small amount of vibrational energy remains.
The total internal energy of a substance is unknown but the amount
relative to some selected temperature and state can be accurately determined. The crystalline state or hypothetical gaseous state at absolute
zero temperature are commonly used as references for scientific studies,
whereas engineering calculations are based upon a variety of reference
conditions arbitrarily selected.
Energy in Transition; Heat and Work, In reviewing the several
forms of energy previously referred to, it will be noted that some are
capable of storage, unchanged in form. Thus, the potential energy of
201
202
THERMOPHYSICS
[CHAP. VII
CHAP. VII]
ENERGY UNITS
203
level. This pound force will accelerate a mass of one pound at a rate
of 32.17 feet per second per second. An alternate unit of force is the
poundal, which is defined as the force which will accelerate a mass of
one pound at a rate of one foot per second per second. Thus, a force
of one pound is equal to 32.17 poundals. The foot-pound is the work
done by a force of one pound acting through a distance of one foot
and the Joot-poundal is the work done by a force of one poundal acting
through a distance of one foot.
Since heat is a form of energy it may also be expressed in ergs, joules,
or foot-pounds. However, in problems dealing with the production,
generation, and transfer of heat it is customary to use special units of
energy called heat units. These units are expressed in various terms
depending upon which temperature scale and system of weights are
employed. The smallest heat unit is the calorie, which is the amount
of heat required to increase the temperature of one gram of water from
15 to 16C. One calorie is equivalent to 4.185 X 10' ergs. It will be
recognized that the calorie is an arbitrary unit expressed in terms of
the thermal capacity of water and is not based upon the cgs system of
measurements. A calorie has also been defined as one-hundredth of the
amount of heat required to increase the temperature of one gram of
water from 0 to 100C. This latter unit, called the mean calorie, is no
longer in use. The mean calorie is 0.017 per cent larger than the 15
calorie. The calorie is also rigorously defined directly in electrical
energy units as S^-Q international watt-hour.
In industrial calculations it is always convenient to use heat units
larger than the calorie, such as the kilocalorie, British thermal unit, or
Centigrade heat unit.
The kilocalorie is equal to 1000 calories, or it is
the amoimt of heat absorbed in increasing the temperature of one kilogram of water from 15 to 16C. When measurements are made in English units, employing pounds and the Fahrenheit temperature scale, the
British thermal unit or Btu is used. This unit is the quantity of heat
absorbed in increasing the temperature of one pound of water from 60
to 61F. One Btu is mechanically equivalent to 778 foot-pounds of
energy. Industries of the United States have often been willing to
adopt the Centigrade temperature scale but have refused to abandon
the English system of weights. This condition has given rise to a hybrid
heat unit known as the Centigrade heat unit, or Chu, which is the
amount of heat absorbed in increasing the temperature of one pound of
water from 15 to 16C. The numerical values of heats of formation
and reaction, as explained later, are the same when expressed in either
kilocalorie per kilogram or Centigrade heat units per pound. For these
reasons the Centigrade heat unit has received some favorable acceptance.
204
THERMOPHYSICS
[CHAP. VII
In the Appendix are factors for the conversion from one system of units
to another.
Energy Balances. In accordance with the principle of conservation
of energy, also called the first law of thermodynamics, and referred to in
Chapter II, page 28, energy is indestructible and the total amount of
energy entering any system must be exactly equal to that leaving plus
any accumulation of energy within the system. A mathematical or
numerical expression of this principle is termed an energy balance, which
in conjunction with a material balance is of primary importance in problems of process design and operation.
In estabhshing a general energy balance for any process, it is convenient to use as a basis a unit time of operation, for example, one hour for
a continuous operation and one cycle for a batch or intermittent operation. It is necessary to distinguish between a flow process, which is
one in which streams of materials continually enter and leave the system,
and a non-flow process, which is intermittent in character and in which
no continuous streams of material enter or leave the system during the
course of operation. An ideal flow process is also characterized by
steady states of flow, temperatures, and compositions at any point in
the process in contrast to the changing conditions of composition in a
batch or non-flow process.
In an energy balance the inputs are equated to the outputs plus the
accumulation of energy inventory within the system over the unit period
of time in a flow process, or for a given cycle of operation for the nonflow process. The separate forms of energy are conveniently classified as follows, neglecting electrostatic and magnetic energies, which
are ordinarily small:
o. Internal energy, designated by the symbol U per unit mass or mil
for mass m.
b. The energy added in forcing a stream of materials into the system
under the restraint of pressure. This flow work is equal to mpV, where
p is pressure of the system and V is the volume per unit mass. A similar
flow-work term is involved in forcing a stream of materials from the
system. These terms appear only in the energy balance of a flow
process.
c. The external potential energies of all materials entering and leaving
the system. External potential energy is expressed relative to an arbitrarily selected datum plane and is equal to mZ, where Z is the height of
its center of gravity above the datum plane.
d. The kinetic energies of all streams entering or leaving the system.
The kinetic energy of a single stream is equal to ^u^, where u is its
average linear velocity, and energy is expressed in ergs, joules, or foot-
CHAP. VII]
ENERGY BALANCES
205
Expressed in foot-
+ ZmiZi + ^m,E,
+ q
^gc
+ Zm^E^^ + w + AE
(1)
206
THERMOPHYSICS
[CHAP. VII
course of operation, the flow work, kinetic energy, and potential energy
terms of the streams do not appear. For such a non-flow process where
surface energy is negligible the general equation reduces to
q = w + AE
(2)
where
1712112 + rrhZi + m2
rriiUi - rriiZi
)
(3)
2gc
2gc /
where the prime values all refer to the properties of the inventory, with
subscript 1 referring to initial conditions and subscript B to final conditions. The kinetic energy term in a non-flow process results from agitation or stirring.
For a non-flow process at constant volume, no work and no potential
energy changes are involved, and if the kinetic and surface energy
terms are absent or negligible, Equation (1) becomes
.
q = "^.i^^U^ JlrriiUi
(4)
(5)
Where work is performed only as a result of expansion against the constant pressure p
w = "EmipVi Y^mipVi
(6)
(7)
(8)
(9)
CHAP. VII]
ENTHALPY
207
Enthalpy. In the energy equations for both flow and non-flow processes it will be seen that the term (C7 + pV) repeatedly occurs. It is
convenient to designate this term by the name enthalpy^ and by the
symbol H, thus
H = U + pV
(10)
In a flow system the term pV represents flow energy but in a non-flow
system it merely represents the product of pressure and volume, having
the units of energy but not representing energy.
In a non-flow process proceeding at constant pressure and without
generation of electrical energy the heat added is seen from Equation (7)
to be equal to the increase in enthalpy of the system, or
In a flow system where the kinetic energy and potential energy terms
are negligible the heat added is equal to the gain in enthalpy plus the
work done, including both electrical and mechanical work, or
? i
q= YlrriiHi Y^miHi -\-w
(11)
Where the work done is negligible in relative magnitude, the heat
added is equal to the gain in enthalpy, or
To smnmarize: For most industrial flow processes, such as the operation of boilers, blast furnaces, chemical reactors, or distillation equipment, the kinetic energy, potential energy, and work terms are negligible
or cancel out and the heat added is equal to the increase in enthalpy.
Similarly, in non-flow processes at constant pressure where work other
than that of expansion is negligible, the heat added is equal to the
increase in enthalpy. However, where work, kinetic, or potential
energies are not negligible, or in non-flow processes at constant volume,
the increase in enthalpy is not equal to the heat added. The distinction between increases of enthalpy and additions of heat must be kept
constantly in mind.
Like internal energy, absolute values of enthalpy for any substance
are unknown but accurate values can be determined relative to some
arbitrarily selected reference state. The temperature, form of aggregation, and pressure of the reference state must be definitely specified.
The values so reported are relative enthalpies. For a gas the reference
state of zero enthalpy is usually taken at 32F and one atmosphere
pressure, and for steam as liquid water at 32F under its own vapor
' This word was coined by Kammerling Onnes (1909), who purposely placed the
accent on the second syllable to distinguish it in speech from the commonly associated
term, entropy.
,
' <; . ; i
208
THERMOPHYSICS
[CHAP.
VII
Hydrogen
I Condenser
Reactor
A'
m[^ initial
ml final
T
CoDdensate
'"2d
64
High
Pressure
Absorber
AE"
m "jj initial
mZ. final
Compressor
Turbine
Compressor
Heater
Water
-< Steam
CHAP. VII]
H E A T BALANCE
209
in contact with a catalyst the CO is converted to CO2. The products from the
reactor are cooled, with resultant condensation of water vapor, compressed further,
and passed into an absorber where CO2 is dissolved in water at high pressure. Hydrogen gas is delivered at high pressure in a nearly pure state. The high pressure
carbon dioxide solution generates power in a turbine and the CO2 gas and water
are thereby released at atmospheric pressure, and separated.
The following symbols are used to designate the various streams. All mass
and energy units correspond to the period of time selected.
mio = mass of water gas entering reactor
'i\ -,
mib = mass of steam entering reactor
rriie = mass of water entering absorber
m2a = mass of hydrogen stream leaving absorber
7712!. = mass of CO2 stream leaving turbine
mic = mass of water leaving turbine
'
mid = mass of water leaving condenser
niia = initial inventory in reactor
m^a = final inventory in reactor
mjj, = initial inventory in absorber
><
m!tt, = final inventory in absorber
wia = net work delivered to water gas in compression
wib = net work delivered to absorber gases in compression
Wic = net work delivered to water in pumping to absorber
+u)2a = work delivered to turbine by solution leaving absorber
Qia = heat added in heating gas mixture entering reactor
qia = heat removed from gas stream leaving reactor by condenser
^ g, = heat lost by radiation from all parts of plant
AE' = change in energy content of mass in reactor over period of run
AE" = change in energy content of mass in absorber over period of run
The markings to U, p, V, u, Z all correspond to those used above.
Applying these conditions to the general equation (1)
'^niiUi
-.
J^niiUi
y--~miu\
miaula
2gc
^mtul
m2aula
2gc
mibulb
2gc
mai&>
2gc
micu\c
2gc
.,..;
'"'''.
miculc
2g^
(a)
'
(b)
"' '
(c)
'
(d)
. ,.,'a:rf
(e)
miduld
2gc
(g)
"^rniZi
(h)
g = gi.. + gaa + gr
'
(i)
(j)
AE = A E ' + A E "
(A-.^v
, - ,-r,v.!-
(k)
210
A'
THERMOPHYSICS
= ni, (u[a + P L F L + ~
[CHAP. VII
+ PJ^F;^ + ^
Zja)
2;J )
(1)
(m)
In general the inventory of both mass and energy remains constant, the kinetic
energy terms are negligible, the potential energy terms cancel, and the equation
reduces to
Smiffi + g = Sm2-H'2 + w
' ' ,
, '
It should be noted that the work terms refer to the net work energy added to the
system or supplied to the turbine and as a result of mechanical inefficiencies do not
correspond to the work required to drive the pumps and compressors or to that
generated by the turbine. The heat developed as a result of these inefficiencies
has been neglected. In chemical processing the work terms are usually negligible'
in the total energy balance although they may be of major importance in cost.
HEAT CAPACITY OF GASES
where
C = heat capacity
dq = heat added to produce a temperature change, dT
If a system is heated in such a manner that its volume remains constant,
dq = dU. The heat capacity under these conditions of constant
volume is expressed by
CHAP. VII]
211
_nR
Thus,
Then, the heat capacity at constant pressure, Cj,, of one mole of an ideal
gas is represented by
+ R = c^ + R
(16)
or
Cp = Cv + R
(17)
where Cp and c are the molal heat capacities at constant pressure and
volume, respectively.
The heat capacity of a substance which expands with rise in temperature is always greater when heated under a constant pressure than
when heated under constant volume by the heat equivalent of the external work done in expansion. For an ideal gas the molal heat capacities
under the two different conditions differ by the magnitude of the constant, R. The numerical value of R is 1.99 calories per gram-mole per
degree Kelvin, or 1.99 Btu per pound-mole per degree Rankine.
For an ideal monatomic gas, such as helium, at a low pressure, it may
be assumed that, as a result of the simple molecular structure, the only
form of internal energy is the translational kinetic energy of the molecules. The translational kinetic energy per mole of gas may be obtained
from Equation 3, Chapter II, page 30, and is equal to the internal
energy V in this particular case. Thus,
J7 = ^nu^
= %RT
(18)
(19)
212
THERMOPHYSICS
calories.
[CHAP. VII
.-^-l-m
(20)
For all gases, other than monatomic gases, the molal heat capacity at
constant volume is greater than 3.0. For a multatomic gas an increase
in enthalpy is used not only in imparting additional translational kinetic
energy, as evidenced by an increase in temperature and an increasing
velocity of translation, but also to impart increased energies of rotation
and vibration of the molecular and submolecular units.
, . '.i ,
TABLE IV
TRUE MOLAL HEAT CAPACITIES OP GASES
ec
0
H2
D2
N2
02
CO
NO
H2O
7.98
CO2
8.61
SO2
Air
9.31
6.94
CHj
C2H1 C2H2
1000
6.96
6.99
7.01
7.03
7.06
7.12
7.20
7.28
7.38
7.49
6.98
7.01
7.06
7.16
7.27
7.39
7.52
7.67
7.81
7.94
6.98
7.05
7.16
7.31
7.47
7.63
7.78
7.91
8.03
8.14
7,13
7.37
7.61
7,84
8,02
8.18
8.31
8.41
8.50
8.60
7.00
7.09
7.23
7.40
7.57
7.75
7.90
8.03
8.15
8.24
6.99
7.10
7.24
7.40
7.57
7.72
7.87
7.99
8.10
8.21
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
7.59
7.69
7.80
7.89
7.98
8.08
8.16
8.24
8.32
8.38
8.06
8.16
8.26
8.34
8.43
8.51
8.58
8.64
8.71
8.76
8.24
8.32
8.38
8.44
8.49
8.54
8.59
8.63
8.66
8.70
8.66
8.73
8.79
8,85
8,90
8,96
9,01
9,08
9,14
9.19
8.33
8.41
8,47
8,53
8,57
8,62
8,66
8,69
8,72
8.75
8.48
8.55
8.61
8.65
8.69
8.73
8.77
8.80
8.82
8.85
10.84
11.08
11.31
11.52
11.71
11.88
12.04
12.19
12.33
12.45
13.74
13,87
13,98
.14,07
14,15
14,22
14,28
14,33
14,38
14.42
13.34
13.41
13.46
13.51
13.56
13.59
13.62
13.65
13.67
13.69
8.29
8,37
8,43
8,49
8,54
8,59
8,64
8.68
8,72
8,77
2100
2200
2300
2400
2500
2600
2700
2800
2900
3000
Mol. wt.
8.45
8.51
8.57
8.62
8.68
8.73
8.78
8.83
8,88
8,93
2,02
8.82
8.87
8.91
8.96
9.00
9.04
9.08
9.11
9.14
9.16
4,03
8.73
8.76
8.78
8,80
8,83
8,84
8,86
8.88
8.89
8.90
28,03
9.24
9.29
9.34
9.39
9.43
9,47
9,51
9,55
9,59
9,62
32,00
8.78
8,81
8,83
8,85
8,87
8,89
8,90
8,91
8,92
8,93
28,00
8.87
8.89
8.91
8.93
8.95
8.9B
8.98
8,99
9.01
9.02
30.01
12.57
12.68
12.78
12,87
12,95
13,02
13,08
13,14
13,18
13,23
18,02
14.46
14.49
14,52
14.54
14.57
14,59
14,61
14,63
14.64
14,66
44,00
13.70 8,80
13.72 8,83
13.73 8,86
13.74 8,89
13.76 8,92
13.77 8,94
13.77 8,96
13.78 8,98
13,79 9,00
13,79 9,02
64,07 28,964 16,03 28.04 26.03
100
200
300
400
500
600
700
800
900
9.40
10.70
12.15
13.40
14,60
15,65
16,60
17,40
18,23
18,93
12.42
14.74
16.73
18.42
19.90
21,17
22,30
23,30
24,17
24,94
11.76
12.98
13.71
14.39
15.01
15.55
16.04
16,49
16,90
17.26
/,-
CHAP.
213
VII]
12
//
^
^o^
B 10
//,
9
& 9
3-
KW
"co^
"Sj
VVi
600
1000
1500
2000
2500
Temperature, F,
3000
3500
4000
4500
Empirical Equations for Molal Heat Capacities. Rigorous heat capacity equations such as the Planck-Einstein equation based upon
spectroscopic data and statistical mechanics are too complicated for
engineering use. Many empirical equations have been proposed to
represent the experimental data, the most useful form of which is of the
quadratic type,
Cp = a + bT + cT^
(21)
The constants a, b, and c were established by W. C. M. Bryant from
the best data available up to 1933, and are recorded in Table V for a
number of common gases. The constants for oxygen, nitric oxide, and
air have been recalculated from the more recent data of Justi and Liider.
The values for sulfur trioxide were calculated from vibration frequencies
214
= ' THERMOPHYSICS
[CHAP. VII
'
tAir
H,
Nt
to.
CO
tNO
Ha
H20
H2S
S02
HCN
COj
COS
CSj
NH3
C2H2
JSOs
Maximum Deviation
0 to 1800C
1.0%
1.6
1.2
1.5
1.2
<2.0
6.27
6.88
6.30
6.13
6.25
6.17
b X 10'
2.09
0.066
1.819
2.99
2.091
2.60
cXW
-0.459
+0.279
-0.345
-0.806
-0.459
-0.66
6.64
6.89
6.48
8 12
7.01
0.959
3.283
5.558
6.825
6.600
-0.057
-0.343
-1.204
-2.103
-1.642
2.0
1.0
<2.0
2.0
<3.0
6.85
8.32
9.76
5.92
8.28
8.533
7.224
6.102
8.963
10.501
-2.475
-2.146
-1.894
-1.764
-2.644
<3.0
2.0
2.0
<1.0
2.0
8.20
10.236
-3.156
Effect of Pressure on the Heat Capacity of Gases. The heat capacities of gases are not greatly affected by small variations in pressure at
low pressures. However, at low temperatures, heat capacities increase
rapidly with increase in pressure and become infinite at the critical
point. The effects of high pressures on heat capacities are discussed
in detail in Chapter XII. As the temperature is increased above the
critical, the effect of pressure upon heat capacity gradually diminishes.
Special Units for Heat Capacity of Gases. Industrial gases are usually measured by volume, in cubic feet or cubic meters. From the
equations given above for the molal heat capacities of gas, values may
be'readily calculated for any other units of weight or volume, such as
CHAP. VII]
215
kilocalories per kilogram, kilocalories per cubic meter, Btu per pound,
and Btu per cubic foot.
Whenever heat capacities are based on unit volumes, the basic quantity of gas involved is that contained in a unit volume measured at
standard conditions of temperature and pressure and not at the existing
conditions. The heat capacity per unit volume refers to the heat
capacity of a definite and constant mass of gas, regardless of its temperature and pressure. For example, the heat capacity per cubic
meter of oxygen at 1000C signifies the heat capacity at 1000C of
the weight of gas contained in 1 cubic meter a t standard conditions, oi* of
1.44 kilograms of oxygen. It does not signifiy the heat capacity of the
oxygen contained in 1 cubic meter of gas at the given temperature and
pressure. This distinction must always be kept in mind in speaking of
the heat-capacities of unit volumes of gases at various temperatures.
In the fuel gas industries an unusual unit of gas quantity is employed
as the standard. This unit is the quantity of gas contained in 1000
cubic feet, measured at a pressure of 30 inches of mercury, a temperature
of 60F, and saturated with water vapor. This volume of gas corresponds to 2.597 pound-moles of dry gas containing 0.046 pound-mole
of water vapor, or 2.643 pound-moles of the mixture. The heat capacity
of the mass of gas equivalent to 1000 cubic feet as measured in the gas
industry at 30 inches of mercury, saturated, and at 60F can be obtained
by multiplying the molal heat capacity of that gas, expressed in Btu per
pound-mole per degree Fahrenheit, by the factor 2.643.
Mean Heat Capacities of Gases. The heat capacity equations given
in Table V represent the values of heat capacities at any temperature,
TK. In heating a gas from one temperature to another it is desirable
to know the mean or average heat capacity over that temperature
range. The total heat required in heating the gas can then be readily
calculated by simply multiplying the number of moles of gas by the
mean molal heat capacity and by the temperature rise. This method
is easier than employing direct integration of the heat capacity formulas for each problem. For gases of the air group where the temperature coefficient is nearly constant, and over short temperature
ranges for other gases, accurate results may be obtained by simply
employing the heat capacity at the average temperature as the mean
heat capacity. Even for a gas such as carbon dioxide, whose temperature coefficient of heat capacity changes markedly with temperature,
the heat capacity at 500O is only 0.6 per cent higher than the correct
mean value over the temperature range from 0 to 1000C.
The mean heat capacity over any given temperature range may be
216
THERMOPHYSICS
[CHAP.
VII
calculated by integrating the general equation for true values over the
desired temperature range as follows:
^
f
Mean Cp =
CpdT
'J Ti
^^ _ ^^
{a + bT + cT^)dT
" Ti
T2-
T,
(22)
TABLE VI
H2
D2
N2
O2
CO
NO
18
100
200
300
400
500
600
700
800
900
1000
6.86
6.92
6.95
6.97
6.98
6.99
7.02
7.04
7.07
7.10
7.13
6.97
6.97
6.98
6.99
7.02
7.06
7,10
7,15
7.21
7.28
7.33
6.96
6.97
7.00
7.04
7.09
7.15
7,21
7,28
7.36
7.43
7.50
7.00
7.06
7.16
7.28
7.40
7.51
7.61
7.70
7.79
7.87
7.94
6.96
6.97
7.00
7.06
7.12
7.20
7.28
7.35
7.44
7.51
7.58
7.16
7.16
7.17
7.22
7.31
7.39
7.47
7.55
7.63
7.71
7.77
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
7.16
7.21
7.25
7.29
7.33
7.37
7.41
7.46
7.50
7.54
7.41
7.46
7.52
7.57
7.63
7.67
7.73
7.78
7.83
7.88
7,57
7,63
7,68
7,74
7,79
7,83
7.87
7.92
7.95
7.99
8.00
8.08
8.13
8.18
8.22
8.25
8.27
8.34
8.39
8.43
7.65
7.71
7.77
7.82
7.85
7.91
7.95
7.99
8.03
8.06
2100
2200
2300
2400
2500
2600
2700
2800
2900
3000
7.58
7.63
7.67
7.71
7.75
7.79
7.82
7.86
7.90
7.93
7.93
7.96
8.00
8.04
8.08
8.11
8.14
8,18
8.21
8.24
8.02
8.06
8.09
8.11
8.15
8.18
8.20
8.23
8.26
8.27
8.46
8.49
8.53
8.57
8.60
8.64
8.66
8.69
8.73
8.77
8.10
8.13
8.16
8.19
8.22
8.24
8.26
8.28
8.31
8.33
Mol. wt.
CO2
SO2
Air
CH4
C2H4 C2H2
7.99
8.04
8.13
8.23
8.35
8.49
8.62
8.76
8.91
9.06
9.20
8.70
9.25
9.73
10.14
10.48
10.83
11.11
11.35
11.57
11.76
11.94
9.38
9.81
10.22
10.59
10.91
11.18
11.42
11.62
11.79
11.95
12.08
6.94
6.96
7.01
7.06
7.14
7.21
7.28
7.35
7.43
7.60
7.57
8.30
8.73
9.48
10.20
10.88
11.53
12.15
12.74
13.28
13.79
14.27
10.20
11.45
12.64
13.73
14.76
15.69
16.52
17.26
18.07
18.62
19.24
7.84
7.90
7.95
8.00
8.04
8.09
8.13
8.16
8.20
8.23
9.34
9.47
9.60
9.74
9.86
9.98
10.11
10.22
10.32
10.43
12.11
12.25
12.37
12.50
12.61
12.71
12.80
12,88
12.96
13.03
12.20
12.29
12.39
12.46
12.53
12.60
12.65
12.71
12.74
12.80
7.63
7.69
7.74
7.79
7.85
7.89
7.93
7.97
8.00
8.04
8.27
8.30
8.32
8.35
8.37
8.39
S.41
8.43
8.45
8.46
10.54
10.63
10.73
10.81
10.89
10.98
11.05
11.13
11.20
11.25
13.10
13.17
13.23
13.27
13.33
13.37
13.42
13.46
13.51
13.55
12.84
12.88
12.92
12.96
12.98
13.01
13.03
13.06
13.09
13.12
8.07
8.09
8.13
8.15
8.19
8.21
8.24
8.26
8.28
8.30
H2O
10.25
11.12
11.79
12.36
12.81
13.21
13.58
13.90
14.22
14.49
14.75
'
tj
''-
2.02 4.03 28.03 32.00 28.00 30.01 18.02 44.00 64.07 28.96 16.03 28.04 26.03
CHAP.
217
VII]
The available data for the mean heat capacity of gases over the
temperature range from 18C to tC are tabulated in Table VI for
temperature intervals of 100C from 0C to 3000C from the data of
Justi and Liider.^ These data are also plotted in Fig. 37 for the temperature range 65 to iF. This particular range has been selected because
the lower temperature corresponds to the reference temperature of
thermochemical data.
13
/
V
&}
12
^
^ ^
A,0
//^
/
1/
7
3^
=J^
N2
"HT
0
500
1000
,,
1500
2000
2500
Temperature, *F.
30OO
3600
4000
4500
According to the law of Petit and Dulong the atomic heat capacities
of the crystalline solid elements are constant and equal to 6.2 calories
per gram-atom. This rule applies satisfactorily to all elements having
atomic weights above 40 when applied to constant volume conditions
at room temperatures. From kinetic theory, Boltzmann showed that
the atomic heat capacity of the elements at constant volume reaches a
maximum value of ZB = 5.97 calories per degree. The atomic heat
3 Forsch. Gebiete Ingenieurw., 6, 211 (1935).
218
THERMOPHYSICS
00
[CH-AP.
VII
KOPP'S RULE
CHAP. VII]
219
fjPs..-.
M8,^=
^S^o
^
.260
^ 9
.200
-'-^P'
/ /
3!^
fTo
ov
^ZoO__
C<iO_-
.150
SnOj__
.100
PbO
.060
800
lOOO
1200
1400
Degrees Kelvin
P, 5.4; S, 5.4; all others, 6.2. This rule should be used only where
experimental values are lacking. Since the heat capacities of soUds
increase with temperature it is obvious that the above empirical rule is
inexact. In general, the heat capacities of compounds are higher in the
liquid than in the solid state. At the melting point the two heat capacities are nearly the same.
The heat capacity of a heterogeneous mixture is a simple additive
property, the total heat capacity being equal to the sum of the heat
220
THERMOPHYSICS
[CBAI-.
VII
" T
" '
.300
3^)^::^^-
Ca2^
CaSi03
CaFj..,-^
X
U.200
c^^ ^ ^ 1 ^ 1 .
//,
100
ir
. _ 1
200
400
600
800
1000
1200
140O
Temperature," Kelvin
FIG. 40. Specific heats of some calcium compounds.
CHAP.
221
VII]
TABLE VII
HEAT CAPACITIES OP SOLID SUBSTANCES
Compounds
Formula
fC
Aluminum sulfate
Aluminum sulfate
Ammonium chloride
Antimony trisulfide
(stibnite)
Arsenious oxide
AU(S04)3
Al2(S04)3-17H20
NH4CI
SbaSa
Barium carbonate
BaCOs
,
f
"
'
AS2O3
' t
Barium chloride
BaClj
Barium sulfate
BaSO,
Cadmium sulfide
CdS
Cadmium sulfate
Calcium carbonate
CdSOi-SHjO
CaCOa
Calcium chloride
Calcium chloride
Calcium fluoride
CaClj
CaCla-GHjO
CaFs
-i-
'
"
'
* ,
'
' -
'<'',
. -i' ^ . , S
Calcium sulfate
CaS04
Calcium sulfate
CaS04-2H20
Chromium oxide
CrjOa
Copper sulfate
Copper sulfate
Copper sulfate
Copper sulfate
Ferrous carbonate
Ferrous sulfate
Lead carbonate '
Lead chloride
CUSO4
CuSOi-HjO
CuSOi-SHjO
CuS04-5H20
FeCOs
FeSOi
PbCOs
PbCla
i!
Lead nitrate
Lead sulfate
Magnesium chloride
Magnesium sulfate
Magnesium sulfate
Magnesium sulfate
Magnesium sulfate
Manganese dioxide
PbCNOs),
PbS04
MgCU
MgS04
MgS04-H20
MgS04-6H20
MgS04-7H20
Mn02
60
34
0
0
100
0
40
0
100
400
800
0
100
0
1000
0
60
0
0
200
400
61
0
0
40
80
0
400
0
60
0
50
0
0
9
0
54
46
32
0
200
400
45
45
48
61
9
9
12
0
Cp
0.184
0.363
0.357
0.0830
0.0884
0.117
0.122
0.100
0.110
0.123
0.130
0.0853
0.0945
0.1112
0.1448
0.0881
0.0924
0.1950
0.182
0.230
0.270
0.164
0.321
0.204
0.212
0.216
0.1691
0.2275
0.2650
0.198
0.168
0.188
0.148
0.1717
0.2280
0.2560
0.193
0,167
0.080
0.0649
0.0704
0.0800
0.1150
0.0838
0.193
0.222
0.239
0.349
0.361
0.152
222
THERMOPHYSICS
[CHAP. VII
Substance
Manganic oxide
Manganous oxide
Mercuric chloride
Mercuric sulfide
Mercurous chloride
Nickel sulfide
MnjOa
MnO
HgCU
HgS
HgCl
NiS
Potassium chlorate
KClOa
Potassium chloride
KCl
'
..( ; : '
Potassium chromate
Potassium dichromate
KzCrOi
KjCrjO,
Potassium sulfate
Potassium nitrate
K2SQ4
KNO3
Silver chloride
AgCl
Silver nitrate
Sodium borate
Sodium borate (borax)
Sodium carbonate
Sodium chloride
AgN03
NajBiOr
NajBiOjlOHaO
Na^COs
NaCl
; '
Sodium nitrate
NaNOs
Sodium sulfate
Na^SO*
Water
H2O
>
(Ice)
rc
Cp
68
58
0
0
0
0
100
200
0
200
0
200
400
46
0
400
0
0
200
300
0
200
500
60
46
35
46
0
100
40C
,600
0
100
250
0
100
-40
0
0.162
0.168
0.0640
0.0506
0.0499
0.116
0.128
0.138
0.1910
0.2960
0.1626
0.1725
0.1790
0.1864
0.178
0.236
0.1760
0.2140
0.267
0.292
0.0848
0.0974
0.101
0.146
0.234
0.386
0.266
0.204
0.217
0.229
0.236
0.2478
0.294
0.358
0.202
0.220
0.435
0.492
Organic Compounds
Cyanamide
Oxalic acid
CH2N2
C2H204-2HsO
Tartaric acid
Picric acid
CHeOe-HjO
C6H3N3O7
Nitrobenzene
Benzene
Benzoic acid
Naphthalene
CeHsNOj
Anthracene
Palmitic acid
Stearic acid
C14H10
C16H32O2
Cl8H3602
CsHfi
C7H60a
CioHs
20
0
100
0
0
100
20
0
20
0
100
50
0
15
0.648
0.338
0.416
0.308
0.240
0.297
0.349
0.376
0.287
0.281
0.392
0.308
0.382
0.399
223
SPECIFIC HEATS
CHAP. V I I ]
Specific Heat
Cals/g C
Substance
Alumina
Alundum
Asbestos
Asphalt
Bakelite
Brickwork
Carbon
Concrete
Cryolite
Diamond
Fire clay brick
Fluorspar
Glass (crown)
(flint)
(pyrex)
(silicate)
(wool)
Graphite
Granite
Gypsum
Limestone
Litharge
Marble
Magnesia
Magnesite-brick
Pyrites (copper)
(iron)
'
Quartz
Sand
Silica
Steel
0,2
0.274
0.186
0.25
0.22
0.3 to 0.4
Approx. 0.2
0.168
0.314
0.387
0.204
0.32
0.186
0.242
0.17
0.224
0.26 to 0.37
0.35
0.45
0.265
0.359
0.403
0.156
0.219
0.253
0.147
0.198
0.298
0.21
0.16 to 0.20
0.117
0.20
1 0.188 to 0.204
0,24 to 0.26
0.157
0.165
0.390
0.20
0.269
0.217
0.055
0.21
0.234
0.188
0.222
0.195
0.131
0.136
0.17
0.28
0.191
0.316
0.12
Temperature Range
C
100
1500
100
26-76
40-892
56-1450
: . '
40
200
21-400
21-800
21-1300
70-312
72-1472
16-55
100
1500
30
0-100
0-700
26-76
56-1450
20-100
16-46
18
100
1500
100
1500
19-50
15-98
0
350
* From Chemical Engineers' Handbook, John H. Perry, McGraw-Hill Book Company, Inc. (1941),
with permiaaion.
,
.
,
224
THERMOPHYSICS
[CHAP.
VII
^CHJC
.95
:ooH
CHN Os
.90
'/r^.so.
.85
I. .80
.75
.70
0
PIG. 4 1 .
1.0
20
40
60
80
100 120 140 160
Moles of Water per Mole of Compound
Specific h e a t s of a q u e o u s s o l u t i o n s of a c i d s a t 2 0 C .
- n 1-^==:
.95
LiOH^
NaOH-y^
.90
" ^
,<K
Ja^CO1
CO3
.85
.80
.75
180 200
ri
/~'
:0H
.70
20
40
60
80
100
120
140
160
180
200
CHAP. VII]
H E A T CAPACITIES O F L I Q U I D S A N D SOLUTIONS
1.0
NaCl
.95
NH
.90
J
7
It
1
/ /
a
a .85
s
i..80
0
FiQ. 43.
I.O
^KCl
-Bad
-CaCl
^//
'
.70
y ^ .
<^
/
.75
L%
/
''
20
.95
(NH4:
.90
.85
NasS
c:
.80
.75
Y/
/A
Xcu 304
>04
MgS
.70
20
40
60
80
100
120
140
160
180 200
1.0 r
Na NOr^
.95
N H,NO 3 ^ ^ - ^ ^
-^^i (NO3
.90
-Cu( TO3)2
.85
.80
A^ P b ( ^03)2
.75
' t
.70
/
0
FiQ. 46.
20
225
226
THERMOPHYSICS
[CHAP. VII
TABLE VIII
HEAT CAPACITIES OF LIQUIDS
Data from International Critical Tables unless otherwise indicated.
s= heatcapacity, calories per gram per C at tC.
o = temperature coefficient in equation: Cp
+ at,
applying over the indicated temperature range
Liquid
Mercury
Formula
fC
Hg
0
60
100
200
280
0
15
100
200
300
-20
'
Water*
..
Sulfur dioxide
Sulfuric acid
Ammonia
H2O
SO2
H2SO4
NH3
Silicon tetrachloride
Sodium nitrate
Carbon tetrachloride
Carbon disulfide
Chloroform
Formic acid
Methyl alcohol
SiCU
NaNOs
CCI4
CS2
CHCI3
CH2O2
CH4O
Acetic acid
E t h y l alcohol
C2H4O2
CaHeO
Glycol
AUyl alcohol
C2H6O2
CsHsO
Acetone
Propane
Propyl alcohol
CsHeO
CsHs
CsHsO
Glycerol
CsHsOs
E t h y l acetate
n-Butane
Ether
C4H8O2
C4H10
C4H10O
Isopentane
CiHu
Cp
''Po
Temp. Range
0.0335
0.0330
0.0329
0.0329
0.0332
1.008
1.000
1.006
1.061
1.155
0.3130
' %.
y^
0.318 0.00028
0.339 0.00038
-40
0
60
100
12 to 50
350
20
11 t o 140
10 t o 45
1.051
1.098
1.215
1.479
0.200
0.430
0.201 0.198 0.000031
0 to 70
0.235 0.000246 - 1 0 0 t o + 1 5 0
15 0.226 0.221 0.000330 - 3 0 to + 6 0
0 0.496
0.000709
40 t o 140
0 0.566
40 0.616
0.468 0.000929
0 t o 80
-50
0.473
0 0.535
25 0.580
50 0,652
100 0.824
150 1.053
0 0.544 0.544 0.001194 - 2 0 t o + 2 0 0
0 0.3860
21 to 96 0.665
0.506 0.000764 - 3 0 t o + 6 0
0 0.576 0.576 0.001505 - 3 0 t o + 2 0
-50
0.456
0 0.525
+50
0.654
-50
0.485
0 0.540
+50
0.598
+100
0.668
20 0.478
/
0 0.550 0.550 0.00191
- 1 5 to +20
0 0.529
/.
30 0.548
120 0.802
0 0.512
8 0.526
CHAP.
TABLE
Liquid
227
LATENT HEAT
VII]
Formula
Nitrobenzene
CeHsNOj
Benzene
CeHe
Aniline
CeHiN
ra-Hexane
Toluene
CeHu
CyHs
n-Heptane
C7H16
CioHjj
C16H34
CisHaeOa
CiaHio
fC
VII]
(Continued)
Cj,
Cpo
10 0.358
50 0.329
120 0.393
5 0.389
20 0.406
60 0.444
90 0.473
0 0.478
50 0.521
100 0.547
20 to 100 0.600
0 0.386
50 0.421
100 0.470
0 t o 5 0 0.507
30 0.518 0.476 0.00142
0 t o 5 0 0.502
0 t o 5 0 0.496
75 to 137 0.650
0.300 0.00120
Temp. Range
30 to 80
80 to 300
* Forrest, Brugmann, and Cummings, Ind. Eng. Chem. 23, 340 (1931).
228
THERMOPHYSICS
[CHAP.
VII
HEATS OF FUSION*
Ae
Al
Cu
Fe*
Na
Ni
Pb
s
Sn
Zn
X/
tf
x//r/
2800
2340
2660
3660
629
4280
H60
300
1600
1660
961
657
1083
1535
98
1450
327
115
232
419
23
2.5
2.0
1.5
1.7
2.5
1.9
0 8
3.2
2.4
Compounds
X/
H2O
SbgOa
CO2
CaCl2
NaOH
,
NaCl
Carbon tetrachloride.
Methyl alcohol
Acetic acid
Ethyl alcohol
Benzene
Aniline
Naphthalene
Diphenyl
Stearic acid
*See also Fig. 89, page 414-
1,435
5,950
2,000
6,040
1,600
7,210
640
525
2,690
1,150
2,370
1,950
4,550
4,020
13,500
0.0
640
- 56.2
774
318
804
- 24
- 97
16.6
-114
6.4
- 7.0
80
71
CHAP.
HEAT OP VAPORIZATION
VII]
229
'
-i
TABLE X
'
.-
HEATS OF TRANSITION
X,
Sulfur:
rhombic > monoclinic
Iron (electrolytic) (see also Fig. 90,
page 419):
a >/3
S>-v
Manganese:
a->^
Nickel:
Tin:
white * gray
7,0
tt
114-151C
363
313
106
770
910
1400
1325
1070-1130
78
320-330
630
HEAT OF VAPORIZATION
230
THERMOPHYSICS
[CHAP. V H
Thus,
'K = v{vg-
vi) /
'
(23)
where
iy
'
'
Thus
T^^
'
^^'
/ "r
'^
(25)
CHAP. VII]
HEATS OF VAPORIZATION
231
where
X = heat of vaporization in calories per gram-mole at
Tg = normal boiUng point in degrees Kelvin.
TsK
Another expression for dp/dT may be .obtained by differentiating Equation (III-7), page 67. Thus,
dp __
pB
dT~ (T - 43)2
/
^^^^
Combining Equations (28) and (27) for the normal boiling point,
X, = 0 . 9 5 f l B ^ ^ r ^ y
(29)
232
THERMOPHYSICS
[CHAP. VII
However, with accurate vapor pressure data, better results are obtained
by selecting two values relatively close to; the normal boiling point.
Thus,
B = __JE2ZL___
(-1
(30)
')
\Ti - 43
T2- 4 3 /
Equation (29) may be used with fair accuracy for estimating heats of
vaporization at low pressures other than one atmosphere by substituting
the proper boiling points for Ti,. However^ it is recommended that its
application be limited to estimating values at the normal boiling point.
Values at other temperatures may then be obtained by the empirical
method described later.
Illustration 2. Ethyl alcohol has a normal boihng point at 78.3C and a vapor
pressure of 15.61 atmospheres at 170C. Estimate the molal heat of vaporization at
its normal boiling point.
From Equation (30),
-r"/
^ 7
j^l5^
1
, \351.3-43
From Equation (29)
'
,,- ; , ,
,
, ' ,
r-T-3720
443-43/
_
'
/
/
r?-
CHAP. VII]
233
Thus,
,/TydT'
X= X ' y
(31)
where
X = heat of vaporization at temperature T and vapor pressure p
X' = heat of vaporization of reference substance at pressure p
and temperature T'
dT'
'
r;- = slope of Diihring Une ' '
Q/J.
Xi" \ i -
TrYTJ
(32)
' - ^'
THERMOPHYSICS
234
[CHAP.
VII
TABLE XI
HEATS OF VAPORIZATION AND CRITICAL CONSTANTS*
'
Substance
Air
Ammonia
Argon
Bromine
Carbon dioxide
X
Carbon disulfide
Carbon monoxide
Carbon oxysulfide
Carbon tetrachloride
Chlorine
D ichlorodifluorome thane
(Freon 12)
Dichloromonofluoromethane (F-21)
Helium
Hydrogen
Hydrogen bromide
Hydrogen chloride
Hydrogen cyanide
Hydrogen fluoride
Hydrogen iodide
Hydrogen sulfide
Mercury
Nitric oxide
/"
Nitrogen
.
Nitrous oxide
"*
Oxygen
i
Phosgene
t
Silicon tetrafluoride
'
Sulfur
_
.
Sulfur dioxide
Sulfur trioxide
Trichloromonofluoromethane (F-11)
Water
tC
5,581
1,690
7,420
6,030
-33.4
-185.8
68.0
-78.4
1,444
4,423
7,280
4,878
4,888
-191.5
-60.2
77
-34.1
-29.8
22
216
4,210
3,860
6,027
7,460
8.9
-268.4
-252.7
-66.7
-85.0
25.7
33.3
4,463
13,980
3,307
1,336
3,950
1,629
-60.3
361
-161,7
-195.8
-88.5
-183.0
6,130
20,200
5,960
10,190
-94.8
444.6
-5.0
44.8
23.6
100.0
9,729
tc
Pc
-140.7
132.4
-122
302
31.1
273.0
-139.0
105.0
283.1
144.0
111.5
37.2
111.5
48.0
178.6
-267.9
-239.9
90.0
61.4
183.5
230.2
161.0
100.4
>1550
-94,0
-147.1
36.5
-118.8
182.0
-1.5
1,040
157.2
218.3
198.0
374.0
73.0
76.0
35.0
61.0
45.0
76.1
39.56
61.0
2.26 .
12.8
84.0
81.6
50.0
82.0
88.9
>200
65.0
33,5
71.7
49.7
66,0
50.0
77.7
83.6
43,2
217.7
* Chemical Engineers* Handbook, John H. Perry, McGraw-Hill Book Company, Inc. (1941), with
permission.
This equation permits estimation of the heat of vaporization of any substance at any temperature if its critical temperature and the heat of
vaporization at some one temperature are known. In combination with
the methods described in the p r e ^ u s sections for estimating heats of
vaporization sa low pressures it is possible to predict data at all conditions up to the critical with errors generally less than 5%.
Illustration 3. The latent heat of vaporization of ethyl alcohol is experimentally
found to be 204 calories per gram at its normal boiling point of 78C. Its critical
CHAP.
VII]
235
ri - cssoi'-^'
Xj = 204 L _ Q ggql
= 140 cal per gram
Reduced Reference Substance Plot. D. H. Gordon' has pointed out
that the limitations of the conventional reference substance plots for the
estimation of heats of vaporization may be greatly minimized by basing
the reference substance plot on equal reditced conditions. The most
convenient form is a logarithmic plot of vapor pressures of the substance
in question and of the reference substance at equal reduced temperatures.
It is found that this method of plotting yields good approximations to
linear curves for a wide variety of substances, both polar and nonpolar
over wide ranges of conditions up to the critical.
Since T = TrTc, the Clausius-Clapeyron equation (page 60) may be
written in terms of reduced temperatures:
or
,
X = s.^X'
(35)
The
The term Sr is the slope of the hne resulting when the logarithm of the
vapor pressure of the given substance is plotted against the logarithm
of the vapor pressure of a reference substance at the same reduced
temperature.
Values of Sr -^i are given in Table X I I I for various refrigerants with
c
water as the reference substance. In Table XII are given the heats of
vaporization of water in Btu per pound-mole at various values of reduced
temperature, Tr, and the corresponding vapor pressures.
' Univ. of Wis. Ph.D. Thesis (1942).
:
236
THERMOPHYSICS
[CHAP. VII
TABLE XII ^
MoLAL HEATS OF VAPORIZATION AND VAPOR PRESSURES OF WATER
Tc = 1165.4R
Tr
0.423
0.44
0.46
0.48
0.60
.
;;
0.52
0.54
0.56
0.58
0.60
19,370
19,170
18,940
18,700
18,460
0.092
0.198
0.446
0.934
1.824
. I*"V
:;' .
18,210
17,960
17,770
17,440
17,170
3.365
5.896
9.871
15.871
24.613
16,880
16,590
16,280
15,950
15,600
36.959
54.006
76.785
106.65
145.08
0.72
0.74
0.76
0.78
0.80
15,230
14,840
14,420
13,980
13,490
193.68
254.1
328.3
418.4
526.1
0.82
0.84
0.86
0.88
0.90
12,970
12,400
11,770
11,070
10,290
0.91
0.92
0.93
0.94
0.95
0.96
0.97
0.98
0.99
1.00
9,684
9,401
8,907
8,365
7,774
7,103
6,336
5,393
4,143
0
0.62
0.64
0.66
0.68
0.70
'"
'
654.2
804.5
980.3
1184.7
1419.3
1548.7
1688.4
1836.0
1995.6
2164.3
2346.1
2538.6
2746.8
2967.5
3206.2
CHAP. VII]
237
TABLE XIII
HEAT OF VAPORIZATION FACTORS AND CRITICAL TEMPERATURES OP REFRIGERANTS*
Refrigerant
Formula
Sr
Ammonia
;
Benzene
Butyl alcohol
Carbon dioxide
Carbon disulfide
Carbon tetrachloride
Chlorine
Chlorobenzene
Chloroform
Ethane
Ethyl alcohol
Ethyl chloride
E t h y l ether
Freon 11
Freon 12
Freon 21
Freon 113 .
Isobutane
Methane
Methyl alcohol
Methyl chloride
n-Butane
Nitrogen dioxide
n-Propyl alcohol
Propane
Sulfur dioxide
Toluene
NHa
CeHe
C4H9OH
CO2
CS2
CCL
CI2
CeHsCl
CHCI3
C2H6
C2H5OH
C2H5C1
(C2H5)20
CCljF
OOlg-T 2
CHCI2F
CadsFs
C4H10
CH4
CH3OH
CH3C1
C4H10
NO2
nC3H70H
CgHg
SO2
CrHg
0.933
0.923
1.327
0.872
0.839
0.869
0.776
0.933
0.916
0.810
1.280
0.885
0.952
0.897
0.869
0.891
0.962
0.879
0.716
1.179
0.845
0.897
0.851
1.303
0.851
0.949
0.956
Critical Temp.
op
270.4
551.3
548.6
88.43
523.0
541.6
295.0
678.6
505.0
89.8
469.6
369.0
380.8
388.4
232.7
353.3
417.4
273.0
-116.5
464.0
289.4
307.0
97.7
506.8
206.2
315.0
609.1
0.584
0.800
1.149
0.410
0.707
0.746
0 502
0.912
0.749
0.382
1.022
0.644
0.687
0.652
0.516
0.621
0.724
0.551
0.211
0.936
0.543
0.591
0.417
1.083
0.486
0.631
0.877
238
or
THERMOPHYSICS
[CHAP. VII
3977
- r ^ = 32.8 Btu per pound
This is in agreement with published data.
'
CHAP. VII]
EVALUATION OF ENTHALPY
The mean specific heat of water between 32F and 281P is 1.006. The mean
heat capacity of water vapor between 281F and 350F at a pressure of 50 lb per
sq in. is 9.2 Btu per lb-mole per F. The latent heat of vaporization of water at
281 F is 926.0 Btu per lb.
.'
Enthalpy of liquid water at 281F =
(281 - 32) 1.006 =
Heat of vaporization at 281F
9 20
Superheat of vapor = (350 - 281) =
18
Enthalpy
Extensive steam tables have been compiled giving the enthalpies and
other properties of steam under widely varying conditions, for both
saturated and superheated vapors. In calculating these tables it is
necessary to take into account the variation of the heat capacity with
pressure, as discussed in Chapter XII. Tables and charts of enthalpies
have been worked out for a number of substances for which frequent
thermal calculations are made in engineering practice.
Calculations of enthalpy often include several changes of state. For
example, in calculating the enthalpy of zinc vapor at 1000C and atmospheric pressure, relative to the solid at standard conditions, it is
necessary to include the sensible enthalpy of the soUd metal at the
melting point, the latent heat of fusion, the heat absorbed in heating the
liquid from the melting point to the normal boiling point, the latent
heat of vaporization, arid the heat absorbed in heating the zinc vapor
from the boiling point up to 1000C at constant pressure.
Illustration 6. Calculate the enthalpy of zinc vapor at 1000C and atmospheric
pressure, relative to the solid at 0C. Zinc melts at 419C and boils under atmospheric pressure at 907C.
The mean heat capacities of the soUd and liquid may be estimated from Fig. 38,
page 218.
Mean specific heat of solid, 0=0 to 419''C =
Mean specific heat of liquid, 419''C to QOT'C =
0.105
0.109
From Table IX, page 228, the heat of fusion is 1660 calories per gram-atom.
The heat of vaporization at the normal boiling point may be estimated from
Equation (25)
...
, X/1180 = 8.75 -I- 4.571 log 1180 = 22.80
X = 26,900 calories per gram-mole
Since zinc vapor is monatomic its molal heat capacity at constant pressure is constant and equal to 4.97 calories per gram-mole
Heat absorbed by solid = 0.105(419 0) =
^
.,
1660
.
Heat of fusion =
=
65.4
240
THERMOPHYSICS
,
. .
26,900
Heat of vaporization =
=
[CHAP. V H
i>...
00.4
4.97
Heat absorbed by vapor = -^- (1000 907) = ..
7 calories per gram
65.4
Total enthalpy....;
541 calories per gram
^^
= 0.0215 pound of water per pound of dry air. This corresponds to a dew point of
79F.
From Fig. 36, the mean molal heat capacity of water vapor between 79F and
100F is 8.02 and that of air between 32F and 100F is 6.95.
CHAB. Y I I ]
HUMID HEAT
CAPACITY OF
AIR
241
The heat of vaporization at 79F may be estimated from Fig. 8 as 18,840 Btu
per pound-mole or 1046 Btu per pound.
6.95
Sensible enthalpy of air = (100 - 32) - =
Sensible enthalpy of liquid water = (79 - 32)0.0215 = ..
Latent heat of water = 1046 X 0.0215 =
Superheat of water vapor = (100 - 79) X 0.0215 X
8-02
-- =
18
Total enthalpy
'
16.3 Btu
1.0 Btu
22.5 Btu
0.2 Btu
40.0 Btu per lb
of dry air
Humid Heat Capacity of Air. It has been pointed out that when
dealing with humid air it is convenient to use 1 pound or 1 pound-mole
of dry air as the basis of calculations, regardless of the humidity of
the air. In problems dealing with the heating or cooling of air where
no change in moisture content takes place the total change in enthalpy
is equal to the sum of the change in the sensible enthalpy of the dry
air and the change in sensible enthalpy of the water vapor. For example, in heating 1 pound of dry air associated with H pounds of water
vapor from h to U degrees Fahrenheit, the total heat, q, required is
given by the equation,
' '
where
q = CUti -k)+H
(C^) ik - h)
'^ -.;i j-.-iv! : ',./;,> w
(36)
;:,.-:,
q = S{t2-ti)
(37)
where
^j
(38)
The combined heat capacity, S, is termed the humid heat capacity of the
air. Over the low temperature range from 30 to 180F the mean heat
capacity of dry air is 0.240 Btu per pound and that of water vapor is
0.446 Btu per pound, from Fig. 36. Accordingly the humid heat
242
'
THERMOPHYSICS
[CHAP. VII
capacity of air when expressed in Btu per pound of air per degree Fahrenheit is given by the equation,
0;,
,S = 0.240 + 0.446Zf
,(39)
When air is cooled by the adiabatic vaporization of water into it, sensible heat is
derived from the humid air to supply the heat necessary in vaporizing the^ water at
the wet-bulb temperature and in heating the evolved vapor to the existing dry-bulb
temperature. Since the total enthalpy of the system remains constant, the heat
lost by the humid air must equal that gained by the water in vaporization and superheating. This equality may be expressed mathematically for the evaporation of
AH moles of water into humid air containing 1 mole of dry air. Thus,
dB.{\ + Cp(< - <)] = - S d <
,'
(40)
where,
H = molal humidity
X = molal heat of vaporization at temperature <
Cpw = mean molal heat capacity of water vapor
I = dry-bulb temperature
t = temperature of adiabatic evaporation
(S = mean molal humid heat capacity of air
Assuming that the wet-bulb temperature remains constant, as humidification proceeds the final dry-bulb temperature reached by the entire weight of air will be the
wet-bulb temperature i^, corresponding to saturation and a humidity i7. In the
temperature range from 32 to 200F the molal heat capacities of air and water
vapor may be taken from Fig. 36 as constant at 6.95 and 8.04, respectively. Then,
from Equation (38), <S = 6.95 -(- 8.04ff. Substituting these values in Equation (40),
and rearranging,
^ ^ _ =
^^
6.95 4-8.045
X-I-8.04( - i;)
Integrating between the limits B., i and H, t,
or
(41)
^ '
1 , 6.95 + 8.04ff
1 ,
X
-. . = 8.04
--: InX: -t- 8.04 ( - )
8.04 In6.95-(-8.04ff
6.95X -1- 8.04Xff -1- 8.04 ( - ) (6.95 -{ 8.04ff) = 6.95X -f- 8.04Xff
(ff - ff)X ,
'=6.95+8.04g+'"
/
/
(*2)
CHAP. VII]
243
+ 9.3x + 8.04/?
(43)
^ ^
244
THERMOPHYSICS
[CHAP.
VII
ture lines are given a slight slope to allow for the increase in heat capacity
of air and water vapor with temperature and thus avoid curvature in
the constant enthalpy lines.
Barometer
20
P I G . 46.
30
40
60
60
70
80
90
Dry Bulb Temperature P
CHAP. VII]
PROBLEMS
246
humid air is nearly equal to that of the system and hence the slope of
the constant enthalpy lines is nearly equal to that of the constant wetbulb lines. The constant enthalpy lines instead of wet-bulb temperature lines have the advantage that the humidity lines are nearly independent of atmospheric pressure and may be used directly in establishing
heat requirements in air-conditioning problems. In Fig. 46 wet-bulb
temperature Unes have been constructed for 70F and for 40F. It will
be observed that the wet-bulb temperature lines have nearly the same
slope as the enthalpy lines, and become more nearly the same as the
temperature is lowered. It will also be observed that the location of a
given wet-bulb temperature Une depends upon the atmospheric pressure.
The slopes of these particular lines were obtained from Equation (42);
other lines can be drawn in similarly or the slopes may be estimated
from the existing 40 and 70F wet-bulb temperature lines.
PROBLEMS
1. (a) From the data of Table V, page 214, calculate the mean heat capacity of
.' one of the following gases; oxygen, hydrogen, water vapor, sulfur
dioxide, ammonia:
{1) In kilocals per kilogram per degree Centigrade from 0 to fC.
(^) In Chu per pound per degree Centigrade from 0 to tC.
(S) In kilocals per cubic meter per degree Centigrade from 0 to tC.
(,4) In kilocals per kilogram per degree Centigrade from 1000 to 2000C.
(5) In Btu per pound-mole per degree Fahrenheit from 32 to iF.
!' = \ (6) In Btu per cubic foot per degree Fahrenheit from 32 to iF.
(7) In Btu per pound per degree Fahrenheit from 1000 to 2000F.
(b) Calculate the heat capacity of the assigned gas in kilocals per kilogram per
degree Centigrade at 1500C.
'.
. ,
2. From the experimental data for the molal heat capacities of oxygen at various
temperatures derive the constants in the following types of empirical equations over
the temperature range from 0C to 1500C:
>. > ^ i
c = a +bT + cT^
"
".
b e
'
'.'
' '
b e
,, ,
' Cp = a +7= +
.'...
. ,.-. -^..; i^ ^ V -'^-K^:-:
VT
T
. s;'
3. Calculate the amount of heat given off when 1 cu m of air (standard conditions) cools from 500 to 100C at a constant pressure of 1 atmosphere, assuming
the heat capacity formula of Table V, page 214, to be valid over this temperature
range.
,., ,,
246
THERMOPHYSICS
[CHAP. VII
;'
:, , ; , ; , -
'.
CHAP. VII]
PROBLEMS
247
14. Utilizing the thermal data for diphenyl, (CeHe-CeHs) tabulated below, estimate
the following:
(a)
(b)
(c)
(d)
Critical temperature.
Boiling point at 25 lb per sq in.
Heat of vaporization at 25 lb per sq in., as Btu per lb.
Enthalpy of 1 lb oi saturated diphenyl vapor at 25 Ib/sq in. relative to solid
diphenyl at 32F.
248
THERMOPHYSICS
[CHAP. V I I
19. Obtaining the latent heat data from t h e steam tables, calculate the enthalpy,
in B t u per pound relative to the liquid at 32F, of steam at a temperature of 500"?
superheated 200''F above its saturation point.
20. Calculate the enthalpy in Btu per pound relative t o 32F, of pure molten
iron at a temperature of 2 8 5 0 ^ . I n heating iron from 32F to its melting point it
vmdeTgoes three transformations, from a t o |3, from. j3 t o 7, and from 7 t o 8 forms.
21. Using the latent heat data calculated in Problem 14, calculate the enthalpy
in Btu per pound relative to the solid at 32F, of saturated diphenyl vapors under a
pressure of 40 lb per sq in.
22. Calculate the enthalpy in Btu per pound of dry air relative t o air and liquid
water at 32F, of humid air at a temperature of 150F, a pressure of 1 atmosphere, and
a percentage humidity of 4 0 % .
23. Humid air at a pressure of 1 atmosphere has a dry-bulb temperature of 180F
and a wet-bulb temperature of 120F. This air is cooled t o a dry-bulb temperature
of 115F. Calculate the heat evolved, in Btu per pound of dry air.
24. Hot gases are passing through a chimney at a rate of 1200 eu ft per minute,
measured at the existing conditions of 600C and a pressure of 740 mm of Hg. The ^'"' v
gases have t h e following composition by volume on the dry basis:
- ''~^-^.
CO2
N2
O2
12%
80%
8%
Vi: ;:
;*'!
;v.A.
The dew point of the gases is 50C and they contain 20 grams of carbon soot per
cubic meter measured at the chimney conditions. Calculate the enthalpy of t h e
material passing through the chimney per minute, in B t u relative to gases, solid
carbon, and liquid water a t 18C.
,
CHAPTER VIII
'
. THERMOCHEMISTRY
'
(1)
...
g-Ai/
(2)
: , . : . , ^ , : - - , ,,....
g = At/
-,.;:., ^ 5 .
(3)
250
THERMOCHEMISTEY
[CHAP. V I I I
CHAP. VIII]
251
252
THERMOCHEMISTRY
(CHAP. VIII
With the aid of the above symbols the states of a chemical reaction
are indicated by the following:
Zn(s) + 2HCl(m = 1.0) = ZnCUCm = 0.5) + HzCff, 1.0 atm)
AHii = 35,900 calories per gram-mole
This equation designates the changes occurring in the reaction described
in the preceding section.
Heat of Formation. The heat of formation of a chemical compound
is a special case of the standard heat of a chemical reaction wherein the
reactants are the necessary elements and the compound in question is
the only product formed. Heats of formation are always expressed
with reference to a standard state. The molal heat of formation of a
compound represents, unless otherwise stated, the heat of reaction,
A H / , when 1 mole of the compound is formed from the elements in a
reaction beginning and ending at 18C and at a pressure of 1 atmosphere
with the reacting elements originally in the states of aggregation which
are stable at these conditions of temperature and pressure. The heat
of formation of a compound is positive when its formation from the
elements is accompanied by an increase in enthalpy. A compound
whose heat of formation is negative is termed an exothermic compound.
If the heat of formation is positive it is called an endothermic compound.
For example, the molal heat of formation of liquid water is 68,320
calories per gram-mole. This means that when 2.016 grams of hydrogen
gas combine with 16 grams of oxygen at a temperature of 18C and a
pressure of 1 atmosphere to form 18.016 grams of liquid water at the
same temperature, the heat given off to the surroundings is 68,320 calories and the enthalpy of the system is decreased by 68,320 calories. It is
obvious that this reaction will not proceed at a constant temperature
but during its progress will be at a very high temperature, and the product formed will be temporarily in the vapor state. However, upon
cooling to 18C this sensible and latent heat appearing temporarily in
the system itself is evolved and included in the heat of formation. If
water vapor were the fioial product at 18C the heat of formation would
be numerically less by an amount equal to the heat of vaporization of
water at 18C. The heat of vaporization of water at 18C is 10,565
calories per gram-mole. Therefore the heat of formation of water vapor
at 18C is -68,320 -|- 10,565 = -57,755 calories per gram-mole.
The basic thermochemical data of inorganic compounds are always
presented in terms of standard heats of formation. In the International
Critical Tables, Vol. V, page 169, are extensive tables giving the heats
of formation of a great variety of inorganic compounds, both in pure
states and in solutions of varying concentrations.
253
HEAT OF FORMATION
CHAP. VIII]
TABLE XIV
HEATS OF FORMATION AND SOLUTION
,,
=
=
=
=
crystalline state
solid
liquid
gas
dil
a>
ppt
amorph
State
Heat of
Formation
I
c
ppt
c
c
sillimanite
arnorph
amorph
c
c
0
I
dil
c
c
-117.4
-166.8
-304,9
-80.0
-380.0
-623.7
-979.0
-944.0
-1804.0
-770.0
-11.0
-16.07
-223.4
-202.8
-74.95
-87.67
-87.13
-266.6
-281.46
-244.64
-165.4
-230.0
-35.7
-214,9
-154.0
-217.9
-357.6
-290.8
-290.7
-176.6
-205.28
-349.0
-225.9
-133.0
-162.4
-363.0
-349.4
-111.2
AH/
Compound
Acetic acid
A l u m i n u m cliloride
Aluminum hydroxide
Aluminum nitride
A l u m i n u m oxide
A l u m i n u m silicate
A l u m i n u m disilicate
A l u m i n u m disilicate
T r i a l u m i n u m disilicate
A l u m i n u m sulfate
Ammonia
Ammonia
Ammonium carbonate
Ammonium bicarbonate
A m m o n i u m chloride
Ammonium hydroxide
Ammonium nitrate
Ammonium oxalate
A m m o n i u m sulfate
A m m o n i u m acid sulfate
A n t i m o n y trioxide
Antimony pentoxide
A n t i m o n y sidfide
Arsenic acid
A t s e n i c trioxide
Arsenic p e n t o x i d e
Barium acetate
Barium carbonate
Barium carbonate
B a r i u m chlorate
B a r i u m chloride
B a r i u m chloride
Barium hydroxide
B a r i u m oxide
B a r i u m peroxide
B a r i u m silicate
B a r i u m sulfate
B a r i u m sulfide
Formula
CH3COOH
AICI3
A1(0H)3
AIN
AI2OS
AkOs-SiOa
Al203-2Si02
Al203'2Si02-2H20
3Al203-2SiOa
Al2(S04)j
NH3
NHs
(NH4)2CO,
NH4HCO3
NH4CI
NH4OH
NH4NO3
(NH4)2C204
(NH4)2S04
NH4HS04
Sb203
SbaOs
Sb2S3
H3ASO4
A820j
AsjOs
Ba(C2H302)2
BaC03
BaCOs
BaCC103)2
BaCl2
BaCl2-2H20
Ba(0H)2
BaO
Ba02
BaSiOs
BaS04
-:
BaS
c
c
c
c
c
c
c
c
octahedral
c
c
ppt
c
c
c
c
c
c
c
glass
ppt
c
Moles
of
Water
Heat of
Solution
200
600
-0.345
-77.9
CD
-1.26
-8,35
-3.28
200
200
400
00
400
400
800
00
CO
CO
CO
CO
CO
CO
CO
CO
400
CO
00
133
AH,
+6.81
+3.818
+6.47
+7.90
+2.38
-0.56
-0.6
+2.0
+0,4
+7.5
-6.0
-5.75
+6.74
-2.45
+4.80
-11.78
-36.1
+5,24
-7.16
THERMOCHEMISTRY
254
[CHAP. VIII
Compound
B i s m u t h oxide
B o r i c acid
B o r o n oxide
B r o m i n e chloride
C a d m i u m chloride
C a d m i u m oxide
C a d m i u m sulfate
C a d m i u m sulfide
Calcium acetate
Calcium aluminate
Calcium aluminate
Calcium aluminate
C a l c i u m a l u m i n u m silicate
C a l c i u m a l u m i n u m silicate
Calcium carbide
Calcium carbonate
Calcium carbonate
C a l c i u m chloride
C a l c i u m chloride
C a l c i u m fluoride
Calcium hydroxide
Calcium nitrate
Calcium oxalate
C a l c i u m oxide
Calcium phosphate
C a l c i u m silicate
C a l c i u m silicate
C a l c i u m sulfate
C a l c i u m sulfide
C a r b o n )9-graphite
Diamond
Gas carbon
C h a r c o a l (Ha tree)
Coke
Sugar carbon
Carbon monoxide
C a r b o n dioxide
C a r b o n disulfide
C a r b o n disulfide
Carbon tetrachloride
Carbon tetrachloride
C h l o r i c acid
C h r o m i u m chloride(ic)
C h r o m i u m chloride (ous)
C h r o m i u m oxide
C h r o m i u m oxide
C h r o m i u m trioxidc
C o b a l t oxide
C o b a l t Oxide
C o b a l t sulfide
Copper acetate
Copper carbonate
C o p p e r chloride
C o p p e r chloride
C o p p e r oxide
C o p p e r oxide
C o p p e r sulfate
Formula
BiaOs
HsBOs
BrCI
CdCla
CdO
CdSOj
CdS
Ca(C2H302)2
CaO-AbOa
2CaO-Al203
SCaO-AkOs
3CaO-Al203-2Si03
CaO-Al203-6Si02
CaC2
CaCOa
CaCOs
CaCl2
CaCl2-6H20
CaF2
Ca(0H)2
Ca(N03)2
CaC204
CaO
Ca3(P04)2
CaO-Si02
2CaO-Si02
CaS04
CaS
C
C
C
C
C
C
CO
CO2
CS2
CS2
CCI4
CCI4
HCIO3
CrCl,
CrCU
Cr203
Cr203
CrOs
CoO
C03O4 .
CoS
Cu(C2H302)2
CuCOs
CuCl2
CuCl
CuO
CU2O
CUSO4
State
H e a t of
Formation
c
c
c
g
c
c
c
c
-137.1
-251.6
-279.9
+3.07
-93.0
-65.2
-222.22
-34.6
-357.6
-620.0
-857.0
-1098.0
-1292.0
-3287.0
-14.1
-287.8
-289.3
-190.6
-623.45
-290.2
-236.0
-224.04
-329.7
-151.7
-983.0
-377.9
-432.0
-340.4
-113.4
0
+ .22
+1.72
+2.22
+2.6
+2.389
-26.620
-94.03
+22.44
+15.84
-25.7
-33.6
-20.8
-143.0
-103.1
-273.0
-266.2
-139.3
-57.6
-196.5
-22.3
-216.4
-141.4
-53.4
-34.3
-38.5
-42.5
-184.7
glass
glass
glass
c
c
c
vvt
calcite
c
c
PPt
c
c
PVt
c
c
glass
glass
c
c
c
c
amorph
amorph
amorph
amorph.
a
g
a
I
Q
I
dil
c
c
c
amorph
c
c
c
ppt
c
ppt
c
c
c
c
c
JMoles
of
Water
AHa
H e a t of
Solution
+5.4
-7.3
400
-3.06
400
-10.69
CO
CO
CO
0=
CO
400
CO
CO
CO
sat.
Bat.
CO
CO
-7.64
-18.517
+9.05
-3.06
-3.94
-19.0
-6.14
-6.4
-2.76
-4.76
-40.0
-18.6
80
-2.5
CO
-2.4
800
-11.2
800
-15.94
CHAP. VIII]
HEAT OF FORMATION
255
Compound
C o p p e r sulfide
C o p p e r sulfide
Copper nitrate
Cyanogen
H y d r o b r o m i c acid
H y d r o c h l o r i c acid
H y d r o c y a n i c acid
Hydrofluoric acid
H y d r i o d i c acid
H y d r o g e n oxide
H y d r o g e n oside
Hydrogen peroxide
H y d r o g e n sulfide
Iron acetate
Iron carbonate
I r o n chloride
Iron hydroxide
I r o n oxide
;
I r o n oxide
i
I r o n oxide ,
I r o n silicate
I r o n sulfate
I r o n sulfate
I r o n sulfide
I r o n sulfide
Lead acetate
Lead carbonate
L e a d chloride
Lead nitrate
L e a d oxide
L e a d peroxide
Lead suboxide
L e a d sesquioxide
L e a d sulfate
L e a d sulfide
L i t h i u m chloride
Lithium hydroxide
Magnesium carbonate
M a g n e s i u m chloride
Magnesium hydroxide
M a g n e s i u m oxide
M a g n e s i u m silicate
M a g n e s i u m sulfate
Manganese carbonate
M a n g a n e s e chloride
M a n g a n e s e oxide
M a n g a n e s e oxide
M a n g a n e s e dioxide
M a n g a n e s e dioxide
M a n g a n e s e silicate
M a n g a n e s e silicate
M a n g a n e s e sulfate
M a n g a n e s e sulfide
M a n g a n e s e sulfide
Mercury acetate
M e r c u r y chloride
M e r c u r y chloride
Formula
CuS
CU2S
Cu(N03)2
C2N2
HBr
HCl
HCN
HF
HI
H2O
H2O
,
H2O2
H2S
Fe(C2Hs02)ii
FeCOs
FeCls
Fe(OH)s
Fe203
FeO
Fe304
FeO-Si02
Fe2(S04)j
FeS04
FeS
FeS2
Pb(C2Hs02)2
PbCOs
PbCb
Pb(N03)2
PbO
Pb02
Pb20
Pb304
PbS04
PbS
,LiCl
LiOH
MgCOj
MgCl2
Mg(0H)2
MgO
MgSiOj
MgS04
MnCOj
MnCl2
MnO
Mn304
MnOj
MnOj
MnO-SiOa
MnO-SiOa
MnS04
.
MnS
MnS
Hg(C2H302)2
HgCl2
Hg2Cl2
State
H e a t of
Formation
c
c
c
0
-11.6
-18.97
-73.1
+71.4
-8.65
-22.06
+30.90
-71.0
+5.91
-57.801
-6S.320
-45.2
-5.3
-355.8
-172.6
-96.4
-197.3
-198.5
-64.3
-266.90
-273.50
-653.20
-221.30
-23.1
-35.5
-233.4
-167.8
-85.71
-106.89
-52.46
-65.0
-51.3
-172.4
-218.5
-22.3
-97.65
-116.55
-267. S
-153.3
-218.7
-146.1
-347.5
-304.95
-207.50
-112.70
-96.6
-345.0
-123.0
-115.6
-301.3
-292.8
-251.2
-47.0
-59.7
-197.1
-53.4
-63.15
a
a
e
1
g
a
I
I
g
dil
c
c
ppt
c
c
magnetite
c
dil
c
c
pyrites
c
c
c
c
c
c
c
c
c
ppt
c
c
c
c
ppt
amorph (?)
c
c
ppt
c
c
c
c
amorph
c
glass
c
ppt
c
c
c
ppt
Moles
of
Water
AHe
H e a t of
Solution
200
-10.3
7.0
20.02
17.627
-6.8
4.7
19.28
m
CO
100
600
GO
200
CQ
0.46
4.6
1000
31.7
400
14.68
400
-1.40
CO
+3.41
+7.61
400
CO
00
8.665
4.738
800
35.92
400
20.30
400
16.0
400
13.8
CO
CO
+4.0
+3.3
256
THERMOCHEMISTRY
[CHAP. VIII
Compound
Mercury
nitrate
Mercury nitrate
M e r c u r y oxide
M e r c u r y oxide
M e r c u r y sulfate
M e r c u r y sulfate
M e r c u r y sulfide
Mercury thiocyanate
M o l y b d e n u m dioxide
M o l y b d e n u m trioxide
Nickel c y a n i d e
Nickel hydroxide
Nickel h y d r o x i d e
Nickel oxide
Nickel sulfide
N i c k e l sulfate
N i t r o g e n oxide
N i t r o g e n oxide
N i t r o g e n oxide
Nitrogen pentoxide
Nitrogen pentoxide
Nitrogen tetroxide
N i t r o g e n trioxide
N i t r i c acid
Oxalic a c i d
Oxalic acid
P e r c h l o r i c acid
P e r m a n g a n i c acid
P h o s p h o r i c acid ( m e t a )
P h o s p h o r i c acid (ortho)
P h o s p h o r i c acid <pyro)
P h o s p h o r o u s acid ( h y p o )
P h o s p h o r o u s acid (ortho)
P h o s p h o r o u s trichloride
Phosphorous pentoxide
P l a t i n u m chloride
P l a t i n u m chloride
Potassium acetate
Potassium carbonate
P o t a s s i u m chlorate
P o t a s s i u m chloride
Potassium chromate
Potassium cyanide
Potassium dichromate
P o t a s s i u m fluoride
P o t a s s i u m oxide
P o t a s s i u m sulfate
P o t a s s i u m sulfide
P o t a s s i u m sulfite
P o t a s s i u m thiosulfate
Potassium hydroxide
Potassium nitrate
Potassium permanganate
Selenium oxide
Silicon c a r b i d e
Silicon t e t r a c h l o r i d e
Silicon t e t r a c h l o r i d e
Formula
HeCNOsh
Hg2(NOs)2-2H20
HgO
HgjO
HgSOi
Hg2S0i
HgS
Hg(CNS)2
M0O2
MoO,
Ni(CN)2
Ni(OH)j
Ni(OH)2
NiO
NiS
NiSOj
NO
NjO
NjO
N2O6
N2O5
N2O4
N2O,
HNO3
HjCzOi-SHaO
H2C2O4
HCIO4
HMn04
HPO3
HsP04
HiP20r
H3PO2
H3PO3
PCI3
P2O6
PtCU
PtCl
KC2H302
K2CO3
KCiOj
KCl
K2Cr04
KCN
K2Cr207
KF
K2O
K2S04
K2S
K2SO3
KiSiOrHsO
KOH
KNO3
KMn04
Se02
SiC
SiCU
SiCl4
State
dil
c
c
c
c
c
amorph
c
c
c
c
ppi
ppt
c
ppt
dil
9
g
I
9
c
9
g
I
c
c
I
da
c
I
I
I
I
9
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
I
H e a t of
Formation
-56.6
-206.5
-21,6
-21.6
-166.6
-176.5
-11.0
+52.4
-130.0
-176.5
+232.4
-163.2
-129.S
-58.4
-20.4
-231.1
+21.6
+19.65
+18.72
+0.6
-13.1
+3.06
+20.0
-41.66
-339. S
-197.2
-19.35
-122.3
-224.8
-300.85
-529.4
-139.0
-225.86
-70.0
-360.0
-62.6
-17.0
-174.23
-274.24
-91.33
-104.361
-333.4
-28.3
-488.5
-134.51
-86.2
-342.66
121.5
-267.7
-270.5
-102.02
-118.093
-192.9
-56.36
-27.8
-150.1
-142.5
Moles
of
Water
AB,
H e a t of
Solution
'
'
'
a,
400
-29.8
-18.61
CO
-7.53
+8.58
+2.3
-20.3
300
300
500
CO
400
03
450
CO
CO
400
400
CO
CO
2185
200
1600
400
300
a
CO
CO
<o
CO
CO
400
2000
-9.8
-5.31
-10.2
-2.41
-2.94
-19.4
-3.404
-6.63
+10.31
+4.404
+4.87
+3.0
+17,81
-3.86
-75,00
+6.32
+10.96
-1.8
+4.5
-12.91
+8.633
+10.4
+0.93
CHAP. VIII]
257
HEAT OF FORMATION
TABLE 'KlY Continued
AH/
Compound
Silicon dioxide
Silver b r o m i d e
Silver chloride
Silver n i t r a t e
Silver sulfide
Sodium acetate
Sodium arsenate
Sodium tetraborate
S o d i u m boraK
Sodium bromide
Sodium carbonate
Sodium carbonate
Sodium bicarbonate
Sodium chlorate
S o d i u m chloride
Sodium cyanide
S o d i u m fluoride
Sodium hydroxide
S o d i u m iodide
Sodium nitrate
Sodium oxalate
S o d i u m oxide
Sodium triphosphate
Sodium diphosphate
Sodium monophosphate
Sodium phosphite
Sodium selenate
S o d i u m selenide
S o d i u m sulfate
S o d i u m sulfate
Sodium bisulfate
S o d i u m sulfide
S o d i u m sulfide
S o d i u m sulfite
S o d i u m bisulfite
S o d i u m silicate
S o d i u m silicofluoride
Sulfur dioxide
Sulfur trioxide
Sulfuric acid
T e l l u r i u m oxide
T i n chloride(ic)
T i n chloride(ous)
T i n oxide(ic)
T i n oxideCous)
T i t a n i u m oxide
T i t a n i u m oxide
T u n g s t e n oxide
V a n a d i u m oxide
Zinc a c e t a t e
Zinc c a r b o n a t e
Zinc chloride
Zinc h y d r o x i d e
Zinc oxide
Zinc s u l f a t e ' ;:;';
;;.
Zinc sulfide
Z i r c o n i u m oxide
Formula
SiOa
AgBr
AgCl
AgNOj
'
Ag2S
NaC2H302
NasASOi
Na2B407
Na2B4O7'10H2O
NaBr
Na2C03
Na2CO3'10H2O
NaHCOs
NaClOa
NaCl
NaCN
NaP
NaOH
Nal
NaNOs
Na2C204
Na20
Na3P04
Na2HP04
NaH2P04
Na2HP03
Na2Se04
Na2Se
Na2S04
Na2SO4-10H2O
NaHS04
Na2S
Na2S-4iH20
Na2S03
NaHSOa
Na2Si03
Na2SiF6
SO2
SO3
H2SO4
Te02
SnCU
SnCl2
SnOj
SnO
Ti02
Ti02
WO2
V2O6
ZnCCjHsOjJa
ZnCOs
ZnCl2
Zn(0H)2
ZnO
ZnS04 . vr'i
ZnS
Zr02
State
H e a t of
Formation
quartz
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
dil
c
c
c
c
c
c
c
c
c
dil
glass
c
-203.34
-23.81
-30.30
-29.4
-5.5
-171.12
-366.0
-742.6
-1453.1
-86.73
-269.67
-975.26
-226.2
-83.6
-98.33
-22.73
-135.95
-101.96
-69.28
-111.72
-314.3
-99.45
-457.0
-414.85
-364.64
-335.33
-254.0
-59.1
-330.48
-1033.20
-269.04
-89.8
-417.54
-261.2
-206.5
-374,0
-669.0
-70.92
-93.90
-193.75
-77.58
-127.4
-81.1
-138.1
-67.7
-214.1
-218.0
-130.5
-437.0
-260.2
-193.1
-99.55
-153.5
-83.5
-233.4
-44.0
-253.0
'
g
I
c
I
c
c
c
amorph
c
c
c
c
ppt
c
amorph
c
c
c
glass
Moles
of
Water
CO
200
400
500
900
1600
200
400
400
1800
03
CO
200
(X>
CO
200
00
600
CO
800
800
800
CO
440
CO
400
800
400
1000
800
660
2000
ASa
H e a t of
Solution
+14.0
+5.44
-3.935
-15.65
-10.0
+25.85
+0.601
-5.63
+ 16.39
+4.1
+5.37
+1.164
+0.37
+0.271
-10.179
-1,562
+5.051
+4.12
-66.4
-14.0
-5.41
-9.30
-7.3
-18.8
-0.28
+18.9
-1.74
-15.16
+5.0
-2.7
200
200
+10.0
-8.56
-53.58
-22.05
+0.9
-29.9
-0.4
400
-9.8
400
-15.72
400
-18.55
CO
CO
CO
258
THERMOCHEMISTRY
[CHAP VIII
CHAP. VIII]
LAWS OF THERMOCHEMISTRY
259
A H / = -94,030 calories
(4)
(5)
(6)
260
THERMOCHEMISTRY
[CHAP. VHl
All thermochemical equations may be treated in this manner and combined with each other according to the rules of algebra. In this way it is
possible to use the principle of Hess effectively in calculating the heat of
a reaction for a complicated series of reactions. The heat of formation
of any compound may be calculated if the heat of any one reaction into
which it enters is known together with the heat of formation of each of
the other compounds present in the reaction.
For example, it is practically impossible to measure directly the heats
of formation of the hydrocarbons. However, a hydrocarbon may be
oxidized completely to carbon dioxide and water and this heat of reaction measured. The heat of formation of the hydrocarbon may then be
calculated from the heats of formation of the other compounds present
in the reaction, namely, carbon dioxide and water. Thus,
CBiig) + 202(5) = C02(g) + 2B.iO{l);
C(|3) -H 02(3) = COiig);
2H2(3)-|-02((7) = 2H2O(0;
(8)
'
(10)
CHAP. VIII]
261
.-.
(U)
262
THERMOCHEMISTRY
[CHAP.
VHI
TABLE XV
STANDARD HEATS OP CoMBitsTioN*
Reference conditions: 18C, 1 atmosphere pressure
AHS = heat of combustion in kilocalories per gram-mole
Multiply values by 1000 to obtain kilocalories per kilogram-mole and by 1800 to
obtain Btu per pound-mole.
^ Ahhreviations
s = Solid
I = liquid
g = gaseous
Hydrocarbons
Final Products: COJC?), HaO^).
Compound
Carbon (graphite)
Carbon (coke)
Carbon monoxide
Hydrogen
Methane
Acetylene
Ethylene
Ethane
AUylene
Propylene
Trimethylene
Propane
Isobutylene
Isobutane
-Butane
Amylene
Cyclopentane
Isopentane
n-Pentane
Benzene
Hexalene
Cyclohexane
n-Hexane
Toluene
Cycloheptane
n-Heptane
o-Xylene
?re-Xylene
p-Xylene
n-Ootane
Mesitylene
Naphthalene
Deoane
Diphenyl
Anthracene
Phenanthrene
Hexadecane
Formula
C
C
CO
H.
/
CH4
C2H2
CjH^
C2H6
CsHj
CaHfi
.;
CgHfl
CsHs
C4H8
C4H10
CiHio
CsHio
CsHio
CiHii
CsHia
CeHs
CeHij
CeHu
CCHH
CyHg
C7H14
C7H16
i
'
CsHio
CsHio
CsHio
CsHis
C9H12
CioHs
C10H22
Cl2Hl0
C14H10
C14H10
Cl6H34
state
Heat of
Combustion
3 = AH
s
s
9
9
g
g
9
g
g
g
9
9
9
9
g
I
I
9
9
I
I
I
I
I
I
I
I
I
I
I
I
s
I
s
s
s
s
-94.030
-96.630
-67.410
-68.320
-212.805
-310.61
-337.26
-372.83
-464.78
-492.01
-496.80
-630.62
-646.20
-683.37
-688.00
-811.75
-783.60
-843.40
-845.33
-782.00
-963.90
-940.00
-1002.40
-934.20
-1087.30
-1150.77
-1090.90
-1090.90
-1087.10
-1306.8
-1242.80
-1231.6
-1619.4
-1493.30
-1684.75
-1674.95
-2556.1
* Values up to n-pentane taken from F. D. Rossini, Bureau of Standards Journal of Research. Other
values on this page taken from M. P. Doss, Physical Constants of Principal Hydrocarbons Texas Co.
(1942), with permission. Values on following pages taken from International Critical Tables, Vol. V,
162 (1929)."
CHAP. VIII]
263
TABLE XV Continued
Alcohols
Final Products:
COi{g), H20(i).
Compound
Methyl alcohol
E t h y l alcohol
Glycol
Allyl alcohol
n-Propyl alcohol
Isopropyl alcohol
Glycerol
n-Butyl alcohol
Amyl alcohol
Methyl-diethyl carbinol
Formula
State
CH4O
CiHeO
Heat of
Combustion
-170.9
-328.0
-281.9
-442.4
-482.0
-474.8
-397.0
-639.0
-787.0
-927,0
C2H6O2
CsH.O
C3H8O
CsHsO
CsHsOs
C4H10O
CsHnO
C6H140
Acids
Final Products: CO^ig), mOQ).
Formic
;
Oxalic
Acetic
Acetic anhydride
Glycolic
Propionic
'
Lactic
'
d-Tartaric
n-Butyric
Citric (anhydrous)
Benzoic
o-Phthahe
Phthalio anhydride
o-Toluic
Palmitic
Stearolic
,
'
Elaidic
Oleic
,^ ^ .
Stearic
CH2O2
C2H2O4
C2H4O2
C4H6O3
C2H4O3
C3H6O2
CsHeOs
C4H6O6
C4H8O2
CeHsOr
C7H6O2
C8H6O4
C8H4O3
C8H8O2
C16H32O2
C18H32O2
C18H34O2
C18H34O2
C18H36O2
I
s
I
I
s
I
s
s
I
s
s
s
s
s
s
s
s
I
s
-62.80
-60.15
-208.00
-431.90
-166.60
-365.00
-326.00
-275.10
-620.00
-474.50
-771.84
-771.00
-781.50
-928.90
-2380.00
-2629.00
-2664.00
-2669.00
-2698.00
CeHijOe
C6H12O6
O12H22O11
C12H22O11
s
s
s
s
-673.0
-675.0
-1350.8
-1349.6
Calories
per gram
-4179
-4110
-4181
-4496
264
THERMOCHEMISTRY
[CHAP. VIII
TABLE XY Continued
Other CHO Compouiids
Final Products: C0i(g),'H.20{I).
Compound
Formaldehyde
Acetaldehyde
Acetone
Methyl acetate
Ethyl acetate
E t h y l acetate
Diethyl ether
Diethyl ketone
Phenol
Pyrogallol
Amyl acetate
Camphor
Heat of
Combustion
Formula
State
CH2O
C2H4O
CsHeO
C3H6O2
C4H8O2
C4H8O2
C4H1 oO
CjHi oO
CeHeO
CeHfiOs
C7H14O2
CioHicO
9
g
I
g
9
I
I
I
s
s
I
s
-134.0
-280.5
-427.0
-397.7
-544.4
-538.5
-651.7
-736.0
-732.0
-639.0
-1040.0
-1411.0
s
9
I
I
s
s
s
I
s
s
I
s
I
-152.0
-260.0
-678.6
-660.0
-664.0
-620.0
-703.2
-739.0
-689.0
-766.0
-812.0
-821.0
-1428.0
9
I
9
I
0
s
9
9
-90.08
-82.18
-96.25
-89.20
-164.00
-171.00
-271.00
-321.80
9
I
9
9
g
-130.5
-246.6
-297.6
-455.6
-452.0
Nitrogen Compounds
Final Products: CO2, NzCff), HjOCOUrea
Cyanogen
Trimethylamine
Pyridine
(1, 3, 5) Trinitrobenzene
(2, 4, 6) Trinitrophenol
o-Dinitrobenzene
Nitrobenzene
o-Nitrophenol
o-Nitroaniline
Aniline
(2, 4, 6) Trinitrotoluene
Nicotine
CH4N2O
C2N2
C3H9N
CsHsN
CeHsNsOe
CeHsNsOT
C6H4N2O4
CeHsNOj
CeHsNOs
CsHeNjOi!
CsHvN
C7H5N306
C10H14N2
Halogen Compounds
ecu
CCI4
CHCI3
CHCI3
CH3CI
C2H3CIO2
C2H4CI2
CjHsCl
Sulfur Compounds
Final Products: CO2, SOiig). HzOCOCarbonyl sulfide
Carbon disulfide
Methyl mercaptan
Dimethyl sulfide
Ethyl mercaptan
COS
CS2
CH4S
C2H6S
CgHeS
'
'
'
CHAP.
VIII]
265
(12)
(13)
(14)
(-68,320)
= -48,521 cal
Thus the heat of formation of CHCl3(sf) is 48,521 calories per grammole.
In this manner a general equation may be derived for use in calculating
the heat of formation of a compound CaHiBrcCldFel/NgO^iSi from its heat
of combustion. If AHC is the heat of combustion of this compound
corresponding to the final products, C02(sf), H2O(0, Br(Z), 012(9^),
HF(ag), I(s), N2(gi), S02(sf), and AH/ its heat of formation, then,
AH/ = - A H C - 94,030a - 34,1606 - 41,540e - 70,920i
(16)
266
THERMOCHEMISTRY
[CHAP. V H I
*
'
>.:
Affis = Hr Ha H6
(-11,000)
/
'
CaCaCs),
AH/ =
H20(Z),
AH/ =
Ca(0H)2(s), AH/ =
-14,100 cal = Ha
-68,320 cal = Ht
-236,000 cal = H,
-,
.,
The heat of formation of acetylene CiH.2{g), is calculated from the heat of combustion
data of Table XV by means of Equation (17)
CiHiig),
CHAP. VIII]
267
Calculation of the Standard Heat of Reaction from Heats of Combustion. For a reaction between organic compounds the basic ttiermochemical data are generally available in the form of standard heats of
combustion. The standard heat of reaction where organic compounds
are involved can be conveniently calculated by using directly the standard heats of combustion instead of standard heats of formation. An
energy balance is again employed, but in this case the standard reference
state is not the elements but the products of combustion at 18C and
1 atmosphere pressure and in the state of aggregation specified by the
heat of combustion data. For example, the enthalpy of methane relative
to its products of combustion, gaseous CO2 and liquid H^O, is equal to
the negative value of its standard heat of combustion, or +212,790
calories per gram-mole. Therefore, in any equation involving combustible materials the formula of a compound may be replaced by its
enthalpy relative to its products of combustion. The enthalpy of the
products minus the enthalpy of the reactants is then equal to the standard heat of reaction, or the standard heat of combustion of the reactants
minus the standard heat of combustion of the products is equal to the
standard heat of reaction.
Illustration 4. Calculate the standard heat of reaction, AHr, of the following:
CJitOnU)
+ CH3COOH(0 = C2H600CCHa(i) + UiOil)
(ethyl alcohol)
(acetic acid)
(ethyl acetate)
From Table XV heats of combustion are as follows:
r
;;
CjHeOH
AH. = -328,000 cal = -Ha
CH3COOH
AH. = -208,000 cal = - H J
CjHsOOCCH, AH, = -538,500 cal = -Hr
268
THERMOCHEMISTRY
[CHAP. VIII
Since the heat of reaction is the difference between the enthalpies of the products and
the reactants,
Afl^is = Hr - Ha - Hi = 638,600 - 328,000 - 208,000 = 2500 cal
!.::,:.
(18)
The heat of reaction, AHr, may be calculated from the respective heats
CHAP. VIII]
269
Thus,
NaCUag); AH/ =
H2O(0;AH/=
-97,166 cal = H,
-68,320 cal = H .
,../,,.- '
(-39,687)
Heats of neutralization may be determined by direct calorimetric measurements in series of solutions of finite concentrations and these results
extrapolated to correspond to infinite dilution. Following are heats of
neutralization based, at least in part, on such measurements:
HCl(ag) + LiOH(a5) = LiCl(ag) + H2O;
A ^ = -13,660
AH = -13,660
(19)
.' - ^:
(20)
270
THERMOCHEMISTRY
[CHAP. VIE
AH = 0
-i^v
(21)
AH = 0
(22) .
From this viewpoint it is evident that mixing such systems actually produces no change^ the initial and final solutions consisting of the same
four ions. It is only upon concentration of the solution and reassociation of the ions that the metathesis leads to a definite change in the
nature of the system.
The experimentally observed fact that dilute solutions of neutral salts
of strong acids and bases may be mixed without thermal effect is termed
the thermoneutrality of salt solutions.
'j
Heats of Formation of Ions. Equation (20) represents the formation
/
of one mole of water from the combination of hydrogen and hydroxyl '
ions. The average value of this heat of reaction has been determined as / /
13,660 calories per gram-mole. The heat of formation of water from / gaseous oxygen and hydrogen is given in Table XIV as 68,320 calories
per gram-mole.
H2(5) + iOiig) = n^OQ);
OR'iaq)
+ E+iaq) = n^Oil);
(a)
(b)
CHAP. VIII]
271
AH/ = 0
= OJI'{aq);
A H / = -54,660 cal
(23)
hydroxyl
By arbihydrogen
Thus, by
(24)
(25)
On this basis the relative heats of formation of the other ions of highly
dissociated acids and bases may be calculated. For example, from Table
XIV, the heat of formation of NaOH(ag) is 112,139 calories per grammole. Since sodium hydroxide is completely dissociated into sodium and hydroxyl ions when in dilute solution, the formation of 1 mole of
NaOH (aq) from the elements is, in actual effect, the formation of 1 mole
of sodium and 1 mole of hydroxyl ions. Thus,
(26)
Na(s) = Na+;
(27)
Therefore, the heat of formation of the sodium ion is 57,479 calories per
gram-mole. In a similar manner the heats of formation of other ions
may be calculated, based on the assignment of a value of zero to hydrogen. Heats of formation of a few common ions, taken from the data of
Bichowsky and Rossini,^ are given in Table XVI.
The heat of formation in dilute aqueous solution of any compound
which is completely dissociated under these conditions is equal to the
sum of the heats of formation of its ions. From the data of Table XVI
the heats of formation of such compounds may be predicted.
niustration 6. Calculate, from the data of Table XVI, the heat of formation of
barium chloride in dilute solution.
Since BaCU may be assumed to be completely disassociated in dilute solution its
heat of formation in dilute solution is equal to the sum of the heats of formation of
^ Thermochemistry of Chemical Substances, Reinhold Publishing Co. (1936). With
permission.
'
THERMOCHEMISTRY
272
[CHAP. V I H
TABLE XVI
HEATS OF FORMATION OF IGNS
Formula
A1+++
NH4+
Ba++
Ca++
H+
Fe++
Fe+++
Li+
Mg++
Mn++
Mn+++
K+
Na+
Zn++
AH/
-126.3
-31v455
-128.36
-129.74
0
-20.6
-9.3
-66.628
-110.23
-49.2
-25.0 .
-60.27
-67.479
-36.3
Ion
Formula
AH/
Acetate
Bicarbonate
Bisulfate
Bisulfite
Bromide
Carbonate
Chloride
Fluoride
Hydroxide
Iodide
Nitrite
Nitrate
Phosphate
Sulfate
Sulfite
CH3COOHCOr
HSOr
HSOs"
Br"
-117.506
-164.6
-213.3
-149.0
-28.67
-160.3
-39.687
-78.20
-54.66
-13.37
-25.3
> -49.19
-297.6
-215.8
-148.5
CO3-
cr
F"
OH'
r
Nor
NO3po,
sor"
SO3"
one barium ion and two chlorine ions. From Table XVI,
4,
'
]'
'
* '
CHAP. VIII]
THERMOCHEMISTRY OF SOLUTIONS
273
Heats of Gaseous Dissociation. At high temperatures the elementary gases are known to dissociate into their atomic states with absorption of great amounts of energy. Upon cooUng, these monatomic gases
rapidly recombine to form the original elementary gas. From an industrial standpoint, the most interesting phenomenon of this type is the
dissociation of normal gaseous hydrogen, 'Hiig), to form a monatomic
gas, H (fif). Such molecular dissociations in the gaseous state are accompanied by large absorptions of energy. Conversely, the reassociation
of the dissociated products is accompanied by a great evolution of energy.
In Table XVII are data for the heats of reaction of several gaseous
dissociations.
'
-' vTABLE XVII
HEATS
OF GASEOUS DISSOCIATION
'.vT'
= 0(g);
iH^Cs) = H(s);
hO,{g}
*
i^.y-
:',:-:[::
I'
.; 1 i
; .
,;>^.'
'
iN,(3) = N(g);
iCh(g) = CI(9);
ih(g) = Kff);
AHI8 =
59,100 cal
AHI8 =
AHIS =
51,900 cal
85,100 cal
AHI8 =
28,900 cal
AHI8 =
18,140 cal
THERMOCHEMISTRY OF SOLUTIONS
274
THERMOCHEMISTRY
[CHAP. VIII
and upon the initial and final concentrations of the solution. The
numerical value of the heat effect, therefore, requires an exact and
complete statement of all reference conditions.
Standard Integral Heats of Solution. Arbitrarily the standard
integral heat of solution is defined as the change in enthalpy of the system
when one mole of solute is dissolved in ni moles of solvent with the
temperature maintained at IS^C and the pressure at one atmosphere.
The numerical value of the integral heat of solution depends upon the
value of ni. As successive equal increments of solvent are added to a
given mass of solute the heat evolved with each addition progressively
diminishes until a high dilution is attained, usually about 100 or 200
moles of solvent per mole of solute, following which no further heat effect
is perceptible. The integral heat of solution approaches a maximum
numerical value at infinite dilution. This hmiting value is termed the
integral heat of solution at infinite dilution.
In Figs. 47 through 51 are presented the standard integral heats of
solution of common acids, bases, and salts in water. Integral heats of
solution are determined calorimetrically by measuring the heat of
solution of a solute in enough solvent to form a relatively concentrated
solution. The heat of dilution accompanying the addition of solvent to
this concentrated solution is then measured. The heat of solution at any
desired concentration is obtained by adding, algebraically, the observed heats of solution and dilution.
It is evident that the integral heat of solution as defijied above is the
enthalpy of the solution containing 1.0 mole of solute, relative to the
pure components at the same temperature and pressure. Thus, the
enthalpy of a solution relative to any selected reference state is expressed
by
H, = niHi + naHs -f- naAHji
(28)
where
- ,
.
H, = enthalpy of ni + ns moles of solution of components 1 and 2
Hi, Ha = molal enthalpies of pure components 1 and 2 at the temperature of the solution
AH,; = integral heat of solution of component 2
t, <'-,
CHAP. VIII]
-20,000
275
; ^
-HBr-
-^
/ / ,^ ^
// / /
(// ' / '
/
.
f
8,000
-HCIv
-^
f/
12,000
M- I
^"1
Hjbu.
HN O j
o
I
- 4,000
H,PO,
~H
UH, (JOO H
>aa
-14,000
.KOH
-12,000
N aUl
-10,000
"=)-
/ *
1 -8,000
1-1
L\
I<COJ
Na,C03
-6,000
- 4,000
-2,000
/
\\i'
\\\
/
/
0~
iOFi
10
20
30
40
50
THERMOCHEMISTRY
276
-20,000
[CHAP. VIII
o
^ -15,000
CaCh
E
n
ZnCI:
&-10,000
/-
S -6,000
a.
BaCij'
NaCl=1
+5,000
NH.Cl-s,
20
KCl ^il
40
60
80
Moles of Water per Mole of Compound
lOO
1
MgSO.
-20,000
s.
S
ZnS04
-15,000
1
JusO<
Mn SO4''
fe
o -10,000
%
a.
-5,000
"=
'
N aiS04
^ NH4)! SO4
1 5 000
K2SO, ^
20
40
60
100
-15,000
1 1
Cu(N03)2
j ; -10,000
o
s
E
-5,000
8'
^^
+5,000
(NO3;
Na N O J V
N H . N O 4?
KNOs
+10,000
0
20
40
60
80
100
C H A P . VIII]
H E A T O F SOLUTION O F H Y D R A T E S
277
'
AH, = - 1 3 , 6 0 0 cal
'"
Since the same amount of water appears on both sides of the reaction its heat of formation does not appear in the equation.
(6) From Fig. 47,
;
<
.,.../,,,.
' '';
HSSOJCWI = 20);
j
!
HzSOiCm = 5 ) ; A H , = - 1 3 , 6 0 0 c a l = / T r
HjSOiCni = 5) + I5H2O = HjSOiCni = 20)
AH,8 = Hr - Ha = - 1 7 , 2 0 0 - ( - 1 3 , 6 0 0 )
AH18 = - 3 6 0 0 cal
A H . = - 1 7 , 2 0 0 cal = Ha
:
.J
.
,
Heat of Solution of Hydrates. If a solute forms a hydrate, the standard heat of solution of the hydrate is the difference between the heat of
solution of the anhydrous substance and its heat of hydration. The
heat of hydration is calculated from the data of Table XIV as the difference between the heat of formation of the hydrated compound and the
sum of the heats of formation of the anhydrous substance and of the
water of hydration.
Illustration 8. Calculate the standard heat of solution of CaCl2-6H20 to form a
solution containing 10 moles of water per mole of CaCU.
From Table X I V ,
'*'*"
CaClj;
AH/ = -190,600 = Ha
H2O;
CaCl2-6H20;
AH/ = - 6 8 , 3 2 0 = H6
A H / = -623,450 = H .
or
lit-ikiJ
or
This heat of reaction represents the molal enthalpy of CaCl2-6H20 relative t o CaClj
and H2O at 18C. The enthalpy of CaCl2(ni = 10) relative to the same reference
substances and state is obtained from Fig. 49,
CaCl2(rai = 10);
278
THERMOCHEMISTRY
[CHAP.
VIII
ENTHALPY-CONCENTRATION CHARTS
CHAP. VIII]
279
= 134
Xo
60
40
v\
v^
\ \
20 \
0
-20
\\
Ai
\ \
W
\ \
iW
\\^
-40
\
I-60
w-80
O
-100
<
I.-120
a
<0"-140
-160
-180
-200
MVv\
\
\\
\ \
\
^^ \
N^i^
V ^^
\ \ \
>^
\
\ ^^^
K\
^
140F
-220
120F
-240
100F
80F
60F
32F
-300
20
30
Weight Per Cent HCl
50
280
THERMOCHEMISTRY
[CHAP. V I I I
In the enthalpy-concentration diagrams for the systems sulfuric acidwater, and calcium chloride-water, Figs. 53 and 54, steep sloping lines are
shown in the two-phase region of vapor and solution. These lines represent the enthalpy of the entire system in Btu per pound, including the
liquid and vapor phases for isothermal conditions at one atmosphere
/
40
60
Percentage HjSO,
FIG,
80
100
pressure and meet the saturation curves at the normal boiling points of
the solutions. In the absence of other gases no vapor phase exists
when the total vapor pressure of the system is less than one atmosphere.
For the illustrated temperature-concentration range of the sulfuric acid
system the vapors are essentially pure water. Thus, a point on the
\
/
/ /
/ '
CHAP. VIII]
ENTHALPY-CONCENTRATION CHARTS
281
ao
40
60
Percentage of Calcium Chloride
282
THERMOCHEMISTRY
[CHAP.
VIII
taining 48% H2SO4. The enthalpy of the mixture is the sum of the
enthalpy of the saturated solution at 250F which is 8 Btu per lb plus
the enthalpy of the superheated water vapor which from the steam
tables is 1169 Btu per lb. The enthalpy of 1.0 lb of mixture is then
(.06) (1169) + (.94) (8.0) = 78 Btu per lb. In this manner the enthalpies of other mixtures were calculated and the constant temperature
lines established in the two-phase regions of both Pigs. 53 and 54.
Since both enthalpies and masses are additive in the formation of
mixtures it follows from the principles of the energy and material balances that the properties of a mixture of two solutions or mixtures
must lie on a straight tie-line connecting the properties of the original
solutions or mixtures on the enthalpy-concentration chart.
If the vapor phase consists of two components, the composition of the
vapor in equilibrium with the liquid solution at its normal boiling point
must be known in establishing the vapor lines and the composition of
both phases.
Illustration 11. One pound of pure H2SO4 at 150F is mixed vrith one pound
of 20% H2SO4 solution initially at 200F. Calculate the temperature of adiabatie
mixing and the water evaporated.
From a material balance the resultant mixture contains 60% H2SO4 based upon
the combined liquid and vapor phases. By constructing a tie-line de connecting
the enthalpies of the two initial solutions and noting its intersection with the 60%
abscissa it will be seen that the resultant enthalpy per pound of mixture is 58 Btu.
The temperature of the mixture is 300F and the corresponding hquid phase has a
composition of 63% H2SO4 with a boiling point of SOOT.
The mass of water evaporated, y, (neglecting the small amount of H2SO4 in the
vapor phase) can Be calculated from either a material or energy balance. From a
material balance,
0.80 = y + 0.37 (2 - y)
y = 0.095 lb water vapor
From an energy balance in which enthalpies at a constant pressure are equated,
Enthalpy
Enthalpy
Enthalpy
Enthalpy
of
of
of
of
1 lb H2SO4 at 150F
1 lb 20% H2SO4 at 200F
water vapor at 300F and 1 atm
63% solution at 300F
116 = 2/(1194) + (2 - 2/)
y = 0.095 lb water vapor
= 40 Btu
= 76 Btu
= 1194 Btu per lb
=
1 Btu per lb
'
Maicimum Temperature in Mixing Solutions. The maximum temperature attainable in mixing two solutions of the same components but
of different temperatures and concentrations may be readily obtained
from an enthalpy-concentration diagram by constructing a tie-line con-
CHAP. VIII]
SOLID-LIQUID SYSTEMS
283
284
THERMOCHEMISTRY
[CHAP.
VIII
'
'"^
Partial Properties. In deahng with the extensive properties of solutions it is convenient to consider separately the contribution attributable
to each component present. For example, the total volume of a solution represents the sum of the contributions of all of the components
present. In ideal systems, such as a gas at low pressure, these contributions may be the same as the properties of the pure components
existing separately at the temperature and pressure of the solution.
However, in many systems this additivity of properties does not exist and
the volume of a solution may be quite different from the sum of the pure
component volumes. That portion of the total volume of a solution
which is attributable to the presence of a particular component is termed
CHAP. VIII]
PARTIAL PROPERTIES
285
the partial volume of that component. Other partial extensive properties may be similarly defined such as partial enthalpy and partial heat
capacity.
The partial volume of a component in a solution of given composition
may be experimentally determined by adding a unit mass of the pure
component to a quantity of solution so large that only an infinitesimal
or negligible change in composition results. The increase in total volume
under these conditions is termed the partial specific volume of the component added and in nonideal solutions may differ considerably from
the specific volume of the pure component. The partial volume of that
component in the solution is then the product of the partial specific
volume and the mass of the component present. Similarly, the partial
molal volume of the component may be determined as the increase in
volume resulting from the addition of one mole of the component to a
quantity of solution so large that no appreciable change in composition
results.
If the composition of the solution is varied to approach 100% of the
component under consideration it is evident that the partial specific
volume must approach the specific volume of the pure component.
Thus, in nonideal solutions the partial properties vary as functions of the
composition. The concept and use of partial properties have been
developed by Lewis and RandalP whose general methods are followed in
this discussion.
Mathematically, the partial molal volume of a component of a solution may be defined as
\oni/p,T,ni,n3---
where
V = partial molal volume of component 1
V = total volume of solution
nx = moles of component 1
__
The partial form of the derivative indicates the requirement of constancy
of all intensive properties such as temperature, pressure, and composition. Thus, Equation (29) is merely the formal expression of the result of
the experimental measurement, described above, of the change in volume
per mole of component added at conditions of constant composition,
temperature, and pressure.
Where M is a single valued, continuous function of several independent
variables x, y, z, the total differential of u can be expressed in terms of its
' G. N. Lewis and M. Randall, Thermodynamics, McGraw-Hill Book Co. (1923).
286
THERMOCHEMISTRY
[CHAP.
VIII
i|--d..(^)<ix+(f)d,
dy
^,..
m^''
(31)
If the composition of the solution and its temperature and pressure are
held constant, the partial molal volumes of Equation (28) are constant
and the equation may be integrated:
V = Villi + Vjnz + Vzn -\
(32)
Thus, the total volume of a solution is equal to the sum of the partial
volumes of the components.
Equation (32) may be differentiated to obtain another useful relationship of partial properties. Thus
dV Vidrii + Tiidvi + V2dn2 + n2dv2 + Vadna + n^iiVi +
Combining Equations (31) and (33):
nidvi + n2dv2 + nsdvj + = 0
(33)
(34)
This equation relates the changes in the partial molal volume of one
component to changes in the partial molal volumes of the others.
i
CHAP. VIII]
287
Equations (29) to (34) were developed for volumes because of the ease
with which this property may be visualized. However, by parallel
reasoning similar equations may be developed relating any extensive
property to the contributions of the separate components. Thus, the
heat capacity of a solution is equal to the sum of the partial heat capacities of its components, derived by an equation similar to (32). Similarly,
the total molal enthalpy of a solution is equal to the sum of the products
of the partial enthalpies of the components times their mole fractions,
or the total enthalpy per gram is equal to the sum of the products of the
partial enthalpies per gram times the weight fractions.
It is evident that partial molal volumes or partial specific volumes or
any of the other partial extensive properties per mole or unit weight of
component are themselves intensive properties, independent of the mass
of solution under consideration but varying as functions of composition
as well as temperature and pressure.
Partial Enthalpies. For the establishment of energy balances the
enthalpy of a solution may be calculated either from integral heat of
solution data and the enthalpies of its pure components according to
Equation (28), or directly as the sum of the partial enthalpies of the
components. Thus,
H, = niHi -f n2H2 +
W2AHS,-2
= niiii + n2H2
(35)
The latter method is frequently the more convenient and more nearly
accurate, particularly where small changes in composition are involved.
For this reason it is desirable to derive partial from total enthalpy data.
Lewis and Randall* present several methods of calculating partial
properties, two of which are illustrated by determining in one case
partial enthalpies per pound and in the other partial molal enthalpies
of components in solutions. The same procedures are involved in calculating any other partial extensive properties such as volumes or heat
capacities.
Method of Tangent Slope. If the total enthalpy of a solution is
plotted as ordinates against the moles of solute, component 2, per fixed
quantity of all other components, it follows from an equation similar to
Equation (29) that the partial molal enthalpy of component 2 is represented by the slope of this curve. If the solution is binary the partial
molal enthalpy of the solvent component then may be calculated from
an equation similar to (31).
For most accurate results covering the entire range of composition
of a binary solution two such plots should be constructed, one covering the concentration range of solute from 0 to 50% on the basis of
* Thermodynamics, p. 36, McGraw-Hill Book Co. (1923).
288
THERMOCHEMISTRY
[CHAP. VIII
one mole or unit weight of solute and the other covering the concentration range of solvent from 0 to 50% construc;ted on the basis of one mole
or unit weight of solvent.
Illustration 13. From the following data for the heats evolved when water and
glycerin are mixed to form 1 gram of solution, calculate the partial enthalpies at
1&C of -water aad glycerin, per gram of each component, at each of the designated
concentrations. Plot curves relating the partial enthalpies of glycerin and of water
to percentage of glycerin by weight. As the reference state of zero enthalpy use the
pure components at 18C, the temperature of the solutions.
Solution:
Method
of Tangent
Percentage
AH^ = H
Glycerin
by Weight
10
20
30
40
60
60
70
80
90
Aff, I =
w' =
w" =
H' =
B" =
H' =
H" =
-1.91
-3.21
-3.90
-4.60
-4.50
-4.21
-3.70
-2.61
-1.79
Slope.
.,,,.
w'
H'
111
250
429
668
1000
-2120
-4020
-6560
-7500
-9000
H"
w"
1000
668
429
250
111
-9000
-7000
-5290
-3660
-1990
, :'
,j
,.,
H'
R"
-13.5
-10.6
-8.1
-6.2
-4.2
-2.65
-1.7
-0.8
-0.4
-0.6
-1.4
-2.1
-3.4
-4.8
-6.5
-8.3
-11.4
-14.3
The values of H', the enthalpy of solution per 1000 grams of water, are obtained
by multiplying the heat of solution, per gram of solution, by the number of grams of
the solution (w' + 1000). For a 40% solution of glycerin
H' = (668 + 1000) (-4.50) = -7500 calories
Values of w' are plotted as abscissas and values of H' as ordinates in Fig. 56. The
slope of a tangent to this curve is the partial enthalpy per gram, of glycerin H' in
a solution of concentration corresponding to the abscissa of the point of tangency.
For a 40% solution;
,
.T/
-9600 + 3400
Slope of tangent
H'
- ' = -6.2
1000
The corresponding values of H", the partial enthalpy of water, are calculated
from the following equation, which is similar to (35):
(wi +W2)H = wiH' + wM"
CHAP. VIII]
280
-10,000r
-10,000
C -8000
a^
I i
<S ^ -400O
429 H"
" 8
1-2000
1000 H'
1
400
600
800
1000
w'=Grams of Glycerin
pr 1000 Grams of Water
FIG.
200
400
600
800
u;"= Grains of Water
per 1000 Grams of Glycerin
1000
The concept of partial enthalpies may be clearly visualized by inspection of Fig. 56.
Point a represents the total enthalpy of a solution containing 668 grams of glycerin
and 1000 grams of water. This total enthalpy is the sum of the partial enthalpy of
the 668 grams of glycerin, equal to o 6 on the diagram, plus the partial enthalpy
of the 1000 grams of water, equal to b.
It will be noted that at the higher concentrations of glycerin the slope of the curve
of Fig. 56 becomes small and it is difficult to determine a value of H' from it with
sufficient accuracy to permit a reliable calculation of H". For this reason it is
inadvisable to use this curve in the range of concentrations above 50% glycerin.
In this range more accurate graphical results may be obtained by plotting total
enthalpies for solutions containing 1000 grams of glycerin against the weight of
water dissolved. From this curve values of H" are determined directly. The corresponding values of H' are calculated from Equation (35). In Fig. 57 values of
w", the grams of water per ICKX) grams of glycerin, are plotted as abscissas against
H", the total enthalpy per 1000 grams of glycerin. The slope of a tangent to this
curve is the partial enthalpy of water per gram in a solution of concentration corresponding to the abscissa at the point of tangency. For a solution containing 70%
glycerin:
_
-10,000 + 1700
Slope of tangent = H" =
= 8.3 calories
1000
From Equation (35), on the basis of 100 grams of solution:
_,
lOOif
wiH"
-370 - (-8.3 X 30)
-1.7
H' =
Wl
IDl
70
In Fig. 57 point a represents the total enthalpy of a solution containing 429 grams
of water and 1000 grams of glycerin. This total is the sum of the partial enthalpy of
the water, equal to o b plus the partial enthalpy of the glycerin, equal to b.
290
THERMOCHEMISTRY
[CHAP. VIII
' (36)
rii + 712
AT, = -
^ ^
'
(37)
n i -H ^ 2
In Fig. 58, Curve III, values of enthalpy H in Btu per pound mole of
solution are plotted against mole fraction N-i of the solute. A tangent
is drawn to Curve III at point E corresponding to a mole fraction of
Ni equal to C. This tangent intercepts the ordinate A''2 = 0 at point A
and the ordinate iV2 = 1 at point F. Ordinate OB represents the value
of H at a mole fraction Ni=C.
The slope of the tangent at JS is equal to
da
OA = OB - AB = n - Ni-iTT
(38)
Variation in the mole fraction of solute, N^, may be produced by addition or removal of solvent, keeping nz constant. Differentiating Equation (36) with respect to n\ keeping ni. constant,
,
^^
TT
rfni
CHAP. VIII]
291
(40)
(wi + rii)^
-80,000
-70,000
\
Hi
XsOj
-60,000
R. /
HjO/
-60,000
/
1
0,-40,000
\p
-^
-30,000
-20,000
EL*
-10,000
y
\
0.2
04
06
0.8
1.0
H
m
(41)
NidHin, + nz)
NJI
riidni
n%
(42)
292
THERMOCHEMISTRY
[CHAP. VIII
' dH
H = dni
(43)
dni
which by definition is the partial molal enthalpy of component 1. Similarly, it may be shown that
i
/ I
0 F = H2 -^^ r : f
j' ""'
(46)
/
/
/
y,
Hirn<Jm-='?
/
CHAP. VIII]
HEAT OP WETTING
298
Oleum
176
21
197.5
2.202
-4.68
1.185
-35.10
Weak Acid
Pounds SO3
19
Pounds H2O
81
Pounds total
,, . i.s
100
Pound moles SO3
0.238
Partial molal enthalpy, SO3 X 10-' --6677..11
Pound moles H2O
4.50
Partial molal enthalpy of H2O X 10"'-0.14
)--0.14
Strong Acid
195
102
297.5
2.44
-35.82
5.686
-7.16
From an energy balance of the process using partial enthalpies the following
results are obtained.
Weak Acid
Olgum
^rj
SO3
H2O
SO3
H^O
'
+ 0 . 2 3 8 ( - 6 7 . 1 ) + 4 . 5 0 ( - 0 . 1 4 ) + 2 . 2 0 2 ( - 4 . 6 8 ) + 1.185(-35.10)
^^
Strong Acid
S02
H20
= 2.440(-35.82) + 5 . 6 8 6 ( - 7 . 1 6 )
I
or
HEAT OF WETTING
294
THERMOCHEMISTRY
[CHAP. VIII
TABLE XVIII
Experiments at 12 to IS^C.
Data from International Critical Tables, Vol. V, page 142.
Unit: calories per gram of the dry material.
Liquid
H2O (water)
CH3OH (methyl alcohol)
CSHSOH (ethyl alcohol)
. CsHnOH (amyl alcohol)
CH3COOH (acetic acid)
CH3COCH3 (acetone)
CJHSOCSHS (ether)
CeHe (benzene)
CCI4 (carbon tetrachloride)
CS2 (carbon disulfide)
CsHia, CeHu (pentane, hexane)
AH
Clay
AH
Amorphous
Silica
AH
Starch
AH
Sugar
Charcoal
-12.6
-11.0
-10.8
-10.0
-9.3
-8.0
-5.8
-5.8
-1.8
-1.7
-1.2
-15.3
-15.3
-14.7
-13.5
-13.5
-13.5
-8.4
-8.1
-8.1
-3.6
-3.1
-20.4
-5.6
-4.9
-7.0
-3.0-^.0
-2.0
-2.2
-1.2
-1.7
-0.5
-0.3
-3.9
-11.5
-6.8
-5.6
-6.0
-3.6
-1.2
-4.2
-1.6
-4.0
-0.4
HEAT OF WETTING
CHAP. VIII]
295
O.IO
0.20
0.30
0.40
0.50
(46)
0.60
> .
where
,
H = total enthalpy of wetted gel, Btu per pound of wet gel
AH = integral heat of wetting, Btu per pound of commercially dry
gel
El = partial enthalpy of gel, Btu per pound of commercially dry gel
Hi = partial enthalpy of water, Btu per pound of water
Wi = pounds of water per pound of commercially dry gel
Wi = pounds of dry gel equals unity
Hi, Hi = enthalpy of pure water and dry gel, respectively, at the temperature of the system, in Btu per pound. Both values are
given as zero in Fig. 60.
V . Am. Ckem. Soc. 59, 1548 (1937).
THERMOCHEMISTRY
296
[CHAP. VIII
It will be observed that the value of //a is 400 Btu per pound of
water when adsorbed upon dry gel but rapidly falls off when the water
content rises, reaching zero at 40% water (commercially dry basis). The
value of Hi changes in a reverse manner being zero for dry gel and
becoming equal to the integral heat of wetting at a water content of
40% (commercially dry basis). In commercially dry silica gel approxi-X60
p _
400
-140
-\
120
300
-iraft-.
- \
(S-100
J'80
*s
1
200 S
\HJ
B< - 6 0
AH^^^
(-;
AH
CQ
^H,
100
-40
-20
i^^
-6
FiQ. 60.
-i
5
10
20
30
40
Percentage Water Content (Comniercially Dry Basis)
1._..
50
Integral and differential heats of wetting of silica gel. From Ewing and
Bauer, Jour. Am. Chem. Soc, 69, 1548 (1937).
mately 5% of water of constitution is present. This water of constitution is always present in active gel and represents the minimum content
after regeneration. If this last trace of water were removed the gel would
lose its capacity for adsorption. It is also of interest to note that the
removal of this form of water as liquid would result in evolution of heat
-, rather than in absorption of heat, as indicated by that portion of the
$ AH curve of Fig. 60 below zero useful water content.
CHAP. V I I I ]
HEAT OF ADSORPTION
297
Illustration 15. One hundred pounds of commercially dry silica gel are wetted
with water from a 6% to a 20% content (commercially dry basis). Estimate the
heat evolved from (a) integral and (b) differential heat of wetting data.
(a) From integral heat of wetting data (Fig. 60) the enthalpy change is equal to
100[-46 - (-18)] = -2800 Btu
(b) Prom the partial enthalpy data (Fig. 60) the enthalpy change is equal to
100[-26 + 0.20(-100)] - 100[-5 + 0.05(-260)] = -2800Btu
Therefore, the heat evolved is 2800 Btu.
HEAT OF ADSORPTION
In Chapter V two types of gas adsorption on sohd surfaces are discussed, that caused by van der Waals forces and that by activated
adsorption. These two types are also characterized by differences in
their heats of adsorption. The heat of adsorption of a gas caused by
van der Waals forces of attraction and capillarity is the sum of the heat
of normal condensation plus the heat of wetting. In activated adsorption the gas is adsorbed by formation of a surface compound at temperatures even above the critical temperature of the gas. The corresponding
heat of adsorption greatly exceeds that of normal condensation. The
difference between heat of adsorption and heat of normal condensation
represents the heat of wetting in van der Waals adsorption and the heat
of formation of a surface compound in activated adsorption.
Data on heats of adsorption are presented either as integral or as
differential values. The integral heat of adsorption is the change in
enthalpy per unit weight of adsorbed gas when adsorbed on gas-free or
" out-gassed " adsorbent to form a definite concentration of adsorbate.
The integral heat of adsorption varies with the concentration of the
adsorbate, in general diminishing with an increase in concentration.
The differential heat of adsorption of a gas is the change in enthalpy
when a unit quantity of the gas is adsorbed by a relatively large quantity
of adsorbent on which a definite concentration of the adsorbed gas al-^
ready exists. The differential heat of adsorption is also a function of
concentration, diminishing with an increase in concentration. As complete saturation of an adsorbent is approached the differential heat of
adsorption approaches that of normal condensation. In activated
298
THERMOCHEMISTRY
[CHAP. VIII
I"
s
y ^d
I
'^-15,000
-w.ooo -
11
v^
^.
^ -n.oooU1
\ ^ ^
\ \ <
9000-
a ,s
VII
] - 7000
<
" \ *-^ /
>-.
1
-5000L.
40
80
120
160
200
240
280
320
360 40O
Experimental measurements have been made of the heats of adsorption of many of the more common gases on the important adsorbents
such as charcoal, silica gel, and various solid catalysts. In Fig. 61 are
values of differential heats of adsorption in calories per gram-mole adsorbed at 0C, plotted against concentrations in cubic centimeters of
adsorbed gas, measured at standard conditions of 0C and 760 mm of
mercury, per gram of adsorbent. Similar data for other systems may
be found in the International Critical Tables (Vol. V, page 139).
lUustration 16. An adsorber for the removal of water vapor from air contains
250 lb of silica gel on which is initially adsorbed 28.0 lb of water. Calculate the
CHAP. VIII]
299
heat evolved per pound of water adsorbed at this concentration, assuming that the
characteristics of the gel are similar to that on which the data of Fig. 61 are based.
28
Sohition: Concentration of H2O in gel = - = 0.112 gram per gram of gel.
0.112
or
X 22,400 = 139 cc per gram of gel
18
From Fig. 61
AH^ = 12,500 calories per gram-mole
or
-22,500 Btu per lb-mole
'
, "
. . . .
, , ,
22,500
Heat evolved per pound of water adsorbed = = 1250 Btu
18
(47)
a in p
where at the equal temperatures for each system
X = normal heat of condensation
Xi = heat of adsorption
p = normal vapor pressure of the condensed vapor
pi = actual equilibrium pressure of the adsorbed vapor
Enthalpies of Adsorbed Systems. The enthalpy diagram of a sohdadsorbed gas or solid-Uquid system has special advantages in problems
dealing with adsorption. In Fig. 62 the enthalpy of the silica gelwater system is shown at various temperatures and compositions relative to dry silica gel at 32F and liquid water at 32F. For convenience,
the abscissas represent pounds of water per pound of commercially
dry gel. In constructing this chart the 70F isotherm was derived first
since heats of wetting are known at this temperature. Thus,
(iU2 + l ) ^ ' = ^ 1 + H2W2 + AHu,
where
Wi
Hi
H2
AHV,
=
=
=
=
(48)
300
THERMOCHEMISTRY
[CHAP. VIII
if = if70+ / C'dt
(49)
10
20
30
40
50
Water Content of Gel (CommerciaUy Dry Basis)
(Pounds of water per 100 pounds of dry gel)
FIG. 62. Enthalpy of silica gel-water system per pound of commercially dry gel.
(Reference state: Commercially dry gel and liquid water at 32F.)
Illustration 17. Calculate the heat to be removed when 100 lb of air (dry basis)
at 70F and 0.010 humidity are dried to a final humidity of 0.001 at 70F and 1 atmosphere pressure starting with 10 pounds of dry gel at 70T. The average temperature
of the gel is initially at 70F and finally at 80F.
jo-^il
CHAP. VIII] INCOMPLETE AND SUCCESSIVE REACTIONS
301
From Fig. 46 the heat removed from the air = 100(27.7 - 18) = 970 Btu
From Fig. 62 the heat removed from the gel = 10[6 - (-14)] = 200 Btu
,: .
.
' ,;i7
Total heat removed = 1170Btu
INCOMPLETE AND SUCCESSIVE REACTIONS
In the preceding sections consideration was given to the thermal
effects accompanying chemical reactions which went to completion and
in which the reactants were present in stoichiometric proportions.
In industrial processes excess reactants are nearly always present and
the reactions are seldom complete.
Frequently the chemical transformations of the same reactant proceed in successive steps or in divergent stages, and the quantities of
different products which are formed bear no stoichiometric relationship
to one another. For example, in the combustion of carbon, both carbon
monoxide and carbon dioxide are formed in variable proportions which
depend upon the conditions of the reaction. In such reactions the
standard heat of reaction is calculated by exactly the same general procedure followed when all materials are present in stoichiometric proportions, namely by^subtracting the heats of formation of the quantities
of reactants which actually react from the heats of formation of the
products actually formed. Or the heats of combustion of the products
actually formed are subtracted from the heats of combustion of the
reactants transformed to give the standard heat of reaction.
Illustration 18. In the production of metallic manganese, 10 kg of manganese
oxide, MjiiOi, are heated in an electric furnace with 3.0 kg of amorphous carbon
(coke). The resulting products are found to contain 4.8 kg of manganese metal
and 2.6 kg of manganous oxide, MnO, as slag. The remainder of the products
consists of unconverted charge and carbon monoxide gas. Calculate the standard
heat of reaction of this process for the entire furnace charge.
Solution:
Initial MnaOi = 10.0 kg or 10/229 =
0.0437 kg-mole
Initial C = 3.0 kg or 3.0/12 =
0.250 kg-atom
Mn formed = 4.8 kg or 4.8/55 =
0.0874 kg-atom
JVInO formed = 2.6 kg or 2.6/71 =
0.0366 kg-mole
Unconverted IMnsOi = 0.0437
'
^-^
= ...,
0.0024 kg-mole
0.1286 kg-atom
0.1286 kg-mole
0.1214 kg-mole
302
THERMOCHEMISTRY
[CHAP. VIII
Material balance
Materials leaving
Mn
4.8 kg
MnO
2.6 kg
MnaOj = 0.0024 X 229 =
0.65 kg
13.0 kg
CO
= 0.1286 X 28 =
3.6 kg
;^
C
= 0.1214 X 12 =
1.45 kg
^
13.00 kg
Materials entering
Mn304
10.0 kg
C
3.0 kg
Total
;
Heats of formation of active reaotants (data from Table XIV, page 253)
MnaOi = -345,000(0.0437 - 0.0024) =
C (coke) = +2600(0.250 - 0.1214) =
Total
-14,200 kcal
+335 kcal
-13,865 kcal
-3530 kcal
-3430 kcal
0 kcal
-6,960 kcal
'
,:
In Chapters II and VII it was pointed out that the internal energy
and enthalpy of an ideal gas are dependent only on temperature and
independent of pressure. Moreover, changes in pressure have negligible effects on the internal energy contents and enthalpies of solids
and liquids.
Therefore, the heat of reaction at constant pressure is independent of the
pressure provided that in a reaction where gases are involved these gases
behave ideally, and provided that when liquids or solids are present the
changes in volume of the condensed phases are negligible.
Where these assumptions are not justified the effect of pressure on
heat of reaction must be calculated from an energy balance, taking into
account the effects of pressure on enthalpy by methods described later.
Reactions at Constant Volume. From the above section it follows
that the changes in enthalpy and internal energy accompanying a
chemical reaction are the same whether the reaction proceeds under
conditions of constant pressure or under conditions of constant volume
provided the gases present behave ideally. If a reaction proceeds in a
calorimeter at 18C at constant volume the heat evolved q can be
measured and is equal to the loss in internal energy.
-q,=
-AU,
(50)
If there is no change in the product pV during the reaction then the loss
CHAP. VIIIJ
303
in enthalpy will also equal the heat evolved. If, however, the reaction
proceeds with an increase in number of gaseous moles then there will
be an increase in p F equal to V Ap at constant volume. The change
in enthalpy then becomes:
AH = AU + VAp
or
AH = qr, + VAp
(51)
(52)
AH = q,+AnRT
(53)
(54)
304
THERMOCHEMISTRY
[CHAP. VIII
AHT
+ dAH =
AHT
+ dHp
(55)
where
dHs and dHp are the changes in enthalpies of the reactants and
. .^.
products, respectively, corresponding to temperature
change dT
Where no latent heat changes are involved, that is, where there are no
changes in phase of reactants or products,
dHs = CpdT
and
'
dHp = C'jdT
where
.,
(56)
'
(57)
Cp and C'p are the heat capacities of the reactants and products, respectively
,,
,
Equation (55) becomes
dAH-^
where
. '
(58)
>
j I
(59)
(60)
CHAP. VIII]
. 305
each heat capacity tenri in Equation (59) may be replaced by an empirical equation of type (60). Then,
ACp = Aa + AbT + ^cT^'
(61)
where
'
(62)
A6 = nrhr + ris&s
tibbb ricbc
(63)
nifii ndCc -
(64)
AO =
TlrOr +
'
(65)
AH = ZH'p "',
ZHB
=q
"
--
"^
(66)
^HR
H'p = H^ + AHis
-, ,'
(67)
f
306
THERMOCHEMISTRY
[CHAP. VIII
where
Hp = enthalpy of the product, referred td its standard state at 18C
AHii = standard heat of reaction
Combining (66) and (67)
AH = E ^ p + EAJTis - J:HR
(68)
'
/
-67,410 kcal (kg-moles)
0.5 kg-mole
0.95 kg-mole
4.52 kg-moles
3.57 kg-moles
0.45 kg-mole
Air:
_ /
Cp(18 - 500C) = 7.20
*
Enthalpy = (7.2) (4.52) (500 - 18) = 16,690 kcal
'
'
CHAP. VIII]
307
N,:
Cp(18 - 1000C) = 7.92
,
Enthalpy = (3.67) (7.92) (1000 - 18) = 27,750 kcal
Y,Hp = 11,670 + 3510 + 27,750 = 42,930 kcal
From Equation (68)
Aff = 42,930 - 67,410 - 16,960 = -41,440 kcal
Since the reaction proceeds at constant pressure the enthalpy change is equal to the
heat absorbed, or there is an evolution of heat of 41,440 kcal.
308
THERMOCHEMISTRY
[CHAP. VIII
output items. In such processes enthalpy changes equal heat absorptions or evolutions and may be entered in the energy balance as such.
Standard heats of reaction are input items if they are negative, representing a contribution of heat to the process and output items if positive.
The overall enthalpy changes of the process are entered as output heat
items if negative and as input- items if positive.
Since energy balances of this type are entirely valid for the specified
types of processes, all forms of energy may be properly included along
with the work, heat, and enthalpy items. Where potential, kinetic,
and surface energies are not negligible, input and output items are
entered as part of the general balance.
Illustration 21. From the results of Illustration 20 prepare an energy balance for
the combustion process under consideration.
..,
Since this is a flow process, enthalpies may be included in the energy balance and '.^^
enthalpy changes are equal to heat absorptions and liberations.
Input
Enthalpy of CO
1,270 kcal
Enthalpy of Air
15,690
Standard Reaction
Heat Added
67,410
84,370 kcal
Output
Enthalpy of CO2 11,670 kcal
Enthalpy of O2
3,510
Enthalpy of Nj
27,750
Heat Evolved
41,440
84,370 kcal
:.
TEMPERATURE OF REACTION
CHAP. VIII]
ADIABATIC REACTIONS
30&
H = nf
CpdT + n\
(69)
"291
where
X = sum of the molal latent enthalpy changes in heating from
291K to TK at constant pressure
Expressing the molal heat capacity, Cp, as a quadratic function of temperature, Cp = a + bT + cT^,
T
H = nf
{a + bT + cT') dT + n\
(70)
Integrating:
'
H = n\aT-i-ibT'
L
+ ^cT'\
'+nX
J291
(71)
*
22 gram-moles
104.8 gram-moles
82.8 gram-moles
11.0 gram-moles
8.0 gram-moles
f?
8.0 gram-moles
11.0 gram-moles
82.8 gram-moles
Total
101.8 gram-moles
" ~
310
THERMOCHEMISTRY
SO3 formed in converter = 8.0 X 0.8 =
O2 consumed in converter = 6.4/2 =
.^ ..
[CHAP. VIII
6.4 gram-moles
3.2 gram-moles
6.4 gram-moles
1.6 gram-moles
7.8 gram-moles
82.8 gram-moles
98.6 gram-moles
H ' ^ ,
v""^
r
0.00299 _
2
H = 7.S\ 6.13(T - 291) H
( P - 291 )
0.806
31
(10-^)(T' - 291 )
0.001819 _
{P - 291 )
0.345
3 1
(10-^){T' - 291 )
_ 9.53(io-6)(J'3 _ 291')
SO,:
H = 1.6r8.12(T - 291) -^ ^ ^ ^ (!P - 29l') - ?^ (10-)(r - 2 9 l ' ) l
= 13.0(r - 291) + 0.00546(r2 - 291") - 1.122(10-8)(T' _ 5^')
CHAP. V I I I ]
NON-ADIABATIC
REACTIONS
311
SO3:
r
0.01024
2
H = 6.4 8.20(7 - 291) +
(T^ - 291 )
3.166
31
(10-)(r' - 291 )
.
T = 865K, or 592C
'
02=
N2 =
SO2 =
SO3 =
7.60
7.20
11.40
12.46 (Table V, page 214)
312
THERMOCHEMISTRY
[CHAP. VIII
;..
4.0 gram-moles
Oj supplied = 0.5 X 2 =
1.0 gram-mole
3.76 gram-moles
7.76 gram-moles
'
9.76 gram-moles
I
Combustion products:
CO2 formed =
O2 remaining = 1.0 0.5 =
N2 =
Enthalpy of products, ^Hp
1.0 gram-mole :
0.5 gram-mole
7.76 gram-moles
(referred to 18C)
'
CO2:
/
/'
0.008533 _
2
H = 1.0 6.86(r - 291) +
(T^ - 291 )
2.475
. ,,
s "1
(lO-'Xr^ - 291 )
Oi
H = 0.6[e.l3iT
- 291) + ' - ^
(T' - 9 1 V ^
(lO-Xr^ - 2 9 l ' ) ]
N .1'
H = 7.76[6.30(r - 291) + ^ ^
(P -2^)-
(10-)(r' - 29l')]
CHAP. VIII]
313
Adding:
JI^H, = 58.80(T - 291) + 0.01207(7^ - 291^) - 1.851 (10-)(r5 - 29i')
Hp = S8.80!r + 0.0120772 - 1.851 X lO-^T^ - 18,095
Since Y^HB = 0 and Aff = 0, from Equation (68), J^Hp = -", ^Hin
or
, ,
,,
, . ,.
.. -
CO, = 11.81
Os = 7.89
Nj = 7.45
Then,
or
=
=
=
=
7,450
7,800
57,100
72,350
.
;:,',;
' ^''
:.,
'
',
^ :< '
Using the values of AH291 and the equation for ^Hp from Illustration 23,
67,410 + 72,350 = 58.80r + 0.012077' - 1.851 X lO'^T^ - 18,095
68.80T + 0.0120772 - 1.851 X IQ-^T^ = 157,855
Solving this equation, .! ; i ;;
:>'a>;.:i
T = 2078K (1805C)
In Table XXII, page 340, are values of the maximum theoretical flame
temperatures of various hydrocarbon gases when burned with air at 18C.
Actual Flame Temperatures. A theoretical flame temperature is
always higher than can be obtained by actual combustion under the
specified conditions. There is always loss of heat from the flame, and
it is impossible to obtain complete combustion reactions at high temperatures. The partial completion of these reactions results from the
314
THERMOCHEMISTRY
[CHAP. V H I
'
'
'
PROBLEMS
''
' "
'-;
- /
1. Calculate the heat of formation, in calories per gram-mole, of SOsig) from the
following experimental data on standard heats of reaction:
PbO(s) + S(s) + iOiig) = PbSOiCs); Aff = -165,500calories (gram-moles)
PbO(s) -I- H2SO4-5H2O(0 = PbS04(s) -|- GHjOy); AH = -23,300 calories /
SOsCs) 4-6H2O(0 = HjSOi-SHjOG); AH = -41,100 calories
/
2. From heat of formation data, calculate the standard heats of reaction of the
following, in kcal per kilogram-mole:
'
,
(a) SOJCS) + iOiig) -f H,0(l) = HiSO,(l).
(b) CaCOals) = CaO(s) + C02(ff).
'/.^m.C;iem.Soc., 53, 869 (1931).
CHAP. VIII]
(c)
(d)
(e)
(J)
(?)
(h)
(t)
(j)
(k)
(I)
(m)
(n)
(0)
(p)
PROBLEMS
315
:.
;.
-,
v,
..
Note: The heat of combustion data given in the table for halogen compounds are
based on having all chlorine converted into HCl(ag), by hydrolysis. Accordingly,
the actual reaction to be considered is one of the combined oxidation and hydrolysis.
For CCI4 it is all hydrolysis and no oxidation.
4. Calculate the standard heats of reaction of the following reactions, expressed in
calories per gram-mole:
(a) (C00H)2(s) = H C O O H a ) + C 0 2 ( g ) .
(oxalic acid)
(formic acid)
(b) C2H50H(i) +02(^) = CH3C00H(i) + H2O(0.
/
'
(ethyl alcohol)
(acetic acid)
(c) 2CH3Cl(s) + Zn(s) = CJi,(,g) + ZnCl2(s).
/
(methyl chloride)
(ethane)
. (d) 3C2H2(s) = C6H6(0.
,
r _
(acetylene) (benzene)
- (e) (CH3COO)2Ca(s) = CH3COCH3(Z) + CaC03(s).
(calcium acetate)
(acetone)
Cf) CH30H(Z) + iO,(.g) = HCHO(s) + H2O(0.
(methyl alcohol)
(formaldehyde)
:
(g) 2C2H5C1(0 +2Na(s) = C4Hio(g) + 2NaCI(8)
(ethyl chloride)
(n-butane)
(fc) C2H2(g) + H2O(0 = CH3CH0(g)
(acetylene)
(acetaldehyde)
,',! .
316
THERMOCHEMISTRY
[CHAP. VIII
CHAP. VIII]
PROBLEMS
317
16. Two sulfuric acid solutions of 10% and 80% concentrations are to be mixed
under adiabatic conditions. If the stronger solution is gradually added to the
weaker, what is the maximum temperature attained when initial solutions are at 18C?
By means of a sketch, show how Fig. 53 was used in the solution of this problem.
17. Calculate the heat evolved when 5 lb HCl gas at 80F are dissolved in 20 lb
of 10% HCl at 60F, to form a solution at 60F (Fig. 52).
18. Calculate the resultant temperature when 10 lb of water at 120F are added
to 10 lb of 40% HCl at 60F (Fig. 52).
19. Calculate the heat required to concentrate 40 lb of 5% HCl at 120F to 8 lb
of 20% HCl at 120F with the vapors leaving at 120F (Fig. 52).
20. Calculate the final temperature when 100% H2SO4 at 60P is diluted with a
solution containing 10% H2SO4 at 100F to form a solution containing 50% HzSOj
(Fig. 53).
21. In the following table aie values of the standard integral heats of solution, AH
in calories per gram-mole, of liquid acetic acid in water to form solutions containing
m moles of water per mole of acid. (From International Critical Tables, Vol. V,
page 159.)
m
^H.
AH.
m
+ 24
0.25
+ 70
sioo
+126
- 13
0.58
6.19
1.11
+149
'
30.00
- 92
1.42
+149 ': '
63.3
-107
1.95
+ 130
(a) Using the method of tangent slope, calculate the differential molal heat of
solution of acetic acid in a solution containing 15% acetic acid by weight.
(6) Using the method of tangent intercepts, calculate the differential molal
heats of solution of acetic acid and of water in a solution containing
50% acetic acid by weight.
22. From the data of Problem 21 calctilate the heat, in Btu, evolved when 10 lb
of acetic acid are added to 1000 lb of a solution containing 50% acetic acid by weight.
Perform the calculation both from integral heat of solution data and from differential
heat of solution data derived in Problem 21.
23. From the integral heat of solution data of Problem 21 calculate the heat, in
calories, which is evolved at 18C when 1 liter of aqueous acetic acid containing 75%
acid by weight is diluted to 2 liters by the addition of water.
24. The heats of mixing, in calories per gram-mole of solution, of carbon tetrachloride (CCI4) and aniline (C6H6NH2) at 25C are given in the following table.
(From the International Critical Tables, Vol. V, page 155.)
e fraction
Mole fraction
AH
AH
CCI4
CCI4
0.6215
0.0942
288
98
0.7175
270
0.1848
169
, 0.7888
246
0.3005
237
0.4152
282
. ',
0.8627
188
0.9092
149
0.4827
291
0.5504
298
(a) Calculate the integral and differential molal heats of solution of each component in a solution containing 50% CCI4 by weight.
(6) Calculate the heat evolved, in Btu, when 1 lb of aniline is added to a
large quantity of solution containing 40% CCI4 by weight.
318
THERMOCHEMISTRY
[CHAP. V I I I
26. (a) For one of the binary systems from the following list, determine the differential heat of solution of each component at each of the ooncentrations listed.
From International Critical Tables, Vol. V
Carbon Tetrachloride
Benzene
Veight %
CCI4
AH
10
0.301
20
0.598
30
0.816
40
0.963
50
1.030
60
1.030
70
0.912
80
0.699
90
0.452
t = 18C
Carbon Disulfide
Acetone
Weight %
AH
CS2
10
5.78 .
20
11.80
/
16.45
30
40
19.92
50
20.93
60
20.80
17.62
70
80
16.15
90
10.80
t = 16C
Chloroform
Acetone
Weight %
CHCU
AH
10
- 4.77
20
- 9.83
30
-14.31
40
-19.38
50
-23.27
60
-25.53
-25.07
70
80
-21.55
90
-13.56
t = 14C
(1 joule = 0.2389 calorie.)
(b) Prepare a plot showing the differential heats of solution (calories per gram
of component) and the heats of mixing (calories per gram of solution)
as a function of the composition, expressed as weight per cent.
(c) Calculate the integral molal heat of solution of each component for "a solution containing 50 weight per cent of each component.
(d) Calculate the Btu evolved when 1 lb of the first-named component is
dissolved in a large volume of solution containing 60% by weight of the
first-named component.
26. Activated charcoal is used for the recovery of benzene (CeHe) vapors from a
nuxture of inert gases. Calculate the heat evolved, in Btu, per pound of benzene
absorbed on a large quantity of charcoal at 0C, when the charcoal contains 0.25 lb of
benzene per pound of charcoal.
27. Calculate the heat evolved, in Btu, when 1 lb of SO2 gas is adsorbed on 6.0 lb
of outgassed silica gel at 0C.
28. Estimate the heat evolved, in Btu, in completely wetting 10 lb of dried clay
with water.
29. Silica gel contains 12% H2O by weight. Calculate the heat, in calories, evolved
when 2.0 kg of this material at 0C are completely wetted with water.
30. Calculate the heat evolved, expressed in Btu, when 100 lb of silica gel (commercially dry basis) adsorbs 25 lb of water at 70''F.
31. Using the data in Table XVIII and Fig. 59, calculate the heat of complete
wetting, expressed in Btu, for the following solids when completely wetted with the
liquid specified.
(o) 100 lb of dry starch, wetted with water.
(6) 100 lb of dry clay, wetted with ethyl alcohol.
(c) 100 lb of animal charcoal containing 8% water when wetted completely
with water.
\
CHAP. VIII]
PROBLEMS
319
320
THERMOCHEMISTRY
[CHAP. VIII
charge and as exit for the product. The opening for admitting the charge also serves
as a vent for the escape of the gas formed by the reaction between the magnetite and
the reducing agent. On the basis of laboratory tests, it is anticipated that 95% of
the iron will be reduced to the metallic state, with the remainder being reduced to
FeO. The reduckig agent to be used is a metallurgical coke containing 85% carbon
and 16% ash, the latter being largely Si02. The coke is to be charged 300%
in excess of the theoretical demand for complete reduction. The solid discharged is
thus a mixture of Pe, FeO, unused coke and Si02 from the ore and from the coke used
up in the reduction process. The gas escaping from the retort will be practically pure
CO, formed by the reaction between the magnetite and the coke.
Analyses
Coke: Carbon = 86%
Ore: FesOi = 90%
Ash
= 15%
SiOs = 10%
Temperatures
Entering ore = 200C
Entering coke = 200C
Leaving solids = 950C
Leaving gas = 960C
Specific heats
PesO*:
0 C . . . 0.151
100C . . . 0.179
200C . . . 0.203
.
300C . . . 0.222
- - >
'
;
."'
v-w
,^
Calculate the material balance for the process, on the basis of 2000 lb of metallic
iron produced.
Estimate the heat requirements for the process, as Btu per 2000 lb of metallic iron
produced.
40. By the combustion at constant volume of 2.0 grams of 'H.2{g) to form liquid
water at 17C, 67.45 kcal are evolved. Calculate the quantity of heat which would
be evolved were the reaction conducted under a constant pressure at 17C.
41. When 1.0 gram of naphthalene (CioHs) is burned in a bomb calorimeter, the
water formed being condensed, 9621 calories are evolved at 18C. Calculate the heat
of combustion at constant pressure and 18C, the water vapor remaining uncondensed.
42. A fuel oil analyzes 80% C and 20% Ha by weight. The standard heat of
combustion of this oil is determined in an oxygen bomb calorimeter. Calculate the
correction that must be applied to get the heat of reaction at constant pressure.
Which is the greater, the heat of reaction at constant pressure, or the heat of reaction
at constant volume?
43. Calculate the actual heat of reaction in cal per g-mole for each of the following reactions. Reactants and products are at a constant pressure of 1 atm. The
temperature of each reactant and product is as indicated. Assume the mean specific
heat of NaHSOi (0 to 250C) to be 0.23 and NajSOi (0 to 600C) to be 0.26.
S02(s) + iOaCs) -> SO,(ff)
450C
460C
460C
NaHS04(s) + NaCl(s) -^ Na^SOiCs) + HClfe)
.250C
30C
600C
300C
SiOiis) + 3C (coke) - SiC(s) + 2C0(g)
18C
18C
1800C 1200C
2NaCl(s) + SO^Csf) + iO,(g) + U^Oig) 400C
400'C
400C
400C
Na2S04(s) + 2HC1(9)
400C
400C
.;. / /
/ /
/
/.
CHAP. VIII]
PROBLEMS
321
44. Derive a general equation for each of the following reactions which will express
the heat of reaction as a function of temperature, with the reactants and products
at the same temperature. Base all equations on the assumption that HjO is in the
vapor state.
CO(s)
+iO,{g)-.CO,{g)
. HsO (?) + CO ig) ^ H2 (s) + COj (ff)
N^to) +3Hs,(?)^2NH3(<7)
SOsCff) +i02(ff)-S03(ff)
HaCff)
+a(ff)->2HCl(ff)
46. Sulfur dioxide gas is oxidized in 100% excess air with 80% conversion to SO3.
The gases enter the converter at 400C and leave at 450C. How many kcal are absorbed in the heat interchanger of the converter per kilogram-mole of SO2 introduced?
46. Calculate the heat of neutralization in calories per gram-mole of NaOH (wi = 5)
with HCl(ni = 7) at 25C where rii = moles H2O per mole of solute.
47. A bed of petroleum coke (pure carbon) weighing 3000 kg, at an initial temperature of 1300C, has saturated steam at 100C blown through it until the temperature of the bed of coke has fallen to 1000C. The average temperature of the gases
leaving the generator is 1000C. The analysis of the gas produced is CO2, 3.10%;
CO, 45.36%; H2, 51.53% by volume, dry basis. How many kilograms of steam
are blown through the bed of coke to reduce the temperature to 1000C? Neglect
loss of heat by radiation and assume that no steam passes through the process
undecomposed.
48. In Problem 47,20% of the steam passes through the coke undecomposed. How
much steam is blown through the bed of coke to reduce its temperature to 1000C?
Neglect loss of heat by radiation.
49. Steam at 200C, 50 superheat, is blown through a bed of coke initially at
1200C. The gases leave at an average temperature of 800C with the following
composition by volume on the dry basis:
Hs
53.5%
, .
CO
39.7%
COs
'
6.8%
100.0%
Of the steam introduced 30% passes through undecomposed. Calculate the heat
of reaction in kcal per kilogram-mole of steam introduced. Mean specific heat of
coke (0 to 1200C) = 0.35.
50. Calculate the number of Btu required to calcine completely 100 lb of limestone
containing 80% CaCOs, 11% MgCOa, and 9% H2O. The lime is withdrawn at
1650F and the gases leave at 400F. The limestone is charged at 70F.
61. Limestone, pure CaCOa, is calcined in a continuous vertical kUn by the combustion of producer gas in direct contact with the charge. The gaseous products
of combustion and calcination rise vertically through the descending charge. The
limestone is charged at 18C and the calcined lime is withdrawn at 900C. The
producer gas enters at 600C and is burned with the theoretically required amount
of air at 18C. The gaseous products leave at 200C. The analysis of the producer
gas by volume is as follows:
CO,
9.21%
Oa
1.62%
CO
13.60%
N,
75.57%
100.00%
322
THERMOCHEMISTRY
[CHAP. VIII
Calculate the number of cubic meters (0C, 760 mm Hg) of producer gas, required
to burn 100 kg of limestone, neglecting heat losses and the moisture contents of the
air and producer gas.
52. A fuel gas of the following composition at 1600F is burned in a copper melting
furnace with 25% excess air at 65F.
CH4
Hi
CO
COj
Ns
O2
>
40%
40%
4%
3%
11%
2%
100%
The copper is charged at 65P and poured at 2000F. The gaseous products leave
the furnace at an average temperature of 1000F. How much copper is melted by
burning 4000 cu ft (32F; 29.92 in. Hg; dry) of the above gas, assuming that the
heat lost by radiation is 50,000 Btu and neglecting the moisture contents of the
fuel gas and air?
63. One thousand cubic meters of gas, measured at standard conditions (0C, 760
mm and dry), containing 20 grams of ammonia per cubic meter (as measured above)
are passed into an ammonia absorption tower at a temperature of 40C, saturated
with water vapor, and at a total pressure of 740 mm. The gas is passed upward
countercurrent to a descending stream of water which absorbs 95% of the incoming
ammonia. The gas leaves the tower at 38C, saturated with water vapor. Six
hundred kilograms of water enter the top of the tower at 20C. What is the temperature of the solution leaving the tower, neglecting heat losses? Assume the mean
molal heat capacity of moisture-free, ammonia-free gas to be 7.2.
54. Pure HCl gas comes from a Mannheim furnace at 300C. This gas is cooled
to 60C in a silica coil and is then completely absorbed by passing it countercurrent
to a stream of aqueous hydrochloric acid in a series of CeUarius vessels and absorption towers. The unabsorbed gas from the last CeUarius vessel enters the first
absorption tower at 40C. Fresh water is introduced in the last absorption tower
at 15C and leaves the first absorption tower at 30C containing 31.45% HCl (20 B6
ac'd). This acid is introduced into the last CeUarius vessel and leaves the first
vessel at 30C containing 35.21% HCl (22 B6 acid). There are produced in this
system 9000 lb of 22 B6 acid in 10 hours. Calculate separately the heat removed
in the cooling coU, CeUarius vessels, and absorption towers, neglecting the presence of
water vapor in the gas stream and assuming complete absorption of HCl.
CHAPTER IX
FUELS AND COMBUSTION
Because of the universal use of the combustion of fuels for the generation of heat and power, special techniques and methods have been
developed for establishing the material and energy balances of such
processes. Each problem should be pursued independently and as
rigorously as the available experimental data permit, using the chemical
principles involved and not empirical equations.
Heating Values of Fuels. The most important property of a fuel is
its heating value, which is numerically equal to its standard heat of combustion but of opposite sign. This property is usually determined by
direct experimental measurements, although methods are also given for
its estimation.
The major products of complete combustion from practically all fuels
are carbon dioxide and water. Two methods of expressing heating
values are in common use, differing in the state selected for the water
present in the system after combustion. The total heating valiie of a
fuel is the heat evolved in its complete combustion under constant
pressure at a temperature of 18C when all the water formed and originally present as liquid in the fuel is condensed to the liquid state. The
net heating value is similarly defined except that the final state of the
water in the system after combustion is taken as vapor at 18C. The
total heating value is also termed the " higher " or " gross " heating
value; the net is often termed the " lower " heating value. The net
heating value is obtained from the total heating value by subtracting the
latent heat of vaporization at 18C of the water formed and vaporized
in the combustion.
Coke and Carbon. The combustible constituents of cokes and
charcoals are practically pure carbon. The heating value of such a
fuel may be predicted with accuracy suflacient for most purposes by
simply multiplying its carbon content by the heating value per unit
weight of carbon.
In Table XIV of Chapter VIII, page 253, it will be noted that heats of
formation of carbon compounds are based on a value of zero assigned
to the heat of formation of P graphite. On this basis various other
forms of elementary carbon have positive heats of formation. Several
323
324
[CHAP. IX
types of " amorphous " carbon are included in the table, each having a
different heat of formation. These differences arise in part from differences in allotropic forms and in the surface energy of carbon in different
states of subdivision and porosity, and in part from the presence of
hydrocarbon compounds of high molecular weights and low hydrogen
contents.
The heats of combustion of the various forms of amorphous carbon
differ by the same amounts as do their heats of formation. For combustion calculations the value of the heat of combustion of carbon is
taken as 96,630 calories per gram-atom or 14,495 Btu per pound.
This value is the difference between the heat of formation of carbon
dioxide and that of carbon in coke, given in Table XIV, page 253, or
-96,630 = -94,030 - 2600.
9.61
9.19
66.60
3.25
0.49
1.42
9.44
100.00
Proximate
Moisture
Ash
Volatile matter
Fixed carbon
'
9.61
9.37
30.68
60.34
,
'
f
- /
j
100 00
/
/.
/
CHAP.
IX]
COAL ANALYSES
325
carried out only when necessary to serve as a basis for energy and material balance calculations. However, the suKur content is of particular
interest, and determination of this element frequently accompanies the
proximate analysis.
In both schemes of analysis " moisture " represents the loss in weight
on heating the finely divided coal at 105C for one hour. The material
termed " ash " in the proximate analysis is the residue from complete
oxidation of the coal at a high temperature in air. This quantity is
needed for calculating the quantity of refuse formed in the ordinary
combustion of the coal. However, the ash determined in this manner
does not accurately represent the mineral content of the original coal
because of the changes which take place during combustion. An
important mineral component of many coals is iron pyrites, FeS2.
In combustion this is oxidized to form Fe203, which is weighed in the
residual ash, and SO2 gas. In the oxidation of pyrites 4 gram-atoms
(128 grams) of sulfur are replaced by 3 gram-atoms (48 grams) of
oxygen, a loss in weight equal to | times the weight of pjTitic sulfur
present. Thus, in order to determine the actual mineral content of the
coal, including the pyritic sulfur, it is necessary to add to the ash-asweighed, a correction equal to f of the pyritic sulfur content. To
determine the actual mineral content, not including the pyritic sulfur,
a correction equal to | of the pyritic sulfur must be subtracted from
the ash-as-weighed. Other less important corrections may also be
applied to the ash. Unless otherwise designated, " ash " refers to ashas-weighed.
To obtain the ultimate analysis, direct determinations are made of
carbon, sulfur, nitrogen, and hydrogen by the usual analytical methods. The moisture and ash are determined by the standardized procedures of the proximate analysis. The percentage oxygen content is
then taken as the difference between 100 and the sum of the percentages
of carbon, hydrogen, sulfur, nitrogen, and corrected sulfur-free ash.
It is recommended that, for this calculation, the corrected ash be estimated by assuming that all sulfur in the coal is present in the pyritic
form. On this basis,
% corrected ash = % ash-as-weighed | ( % S) =
% mineral content % S
where % S = percentage sulfur content of coal. This correction
represents only an approximation, since not all sulfur is pyritic and
other changes in the mineral constituents may take place in combustion.
More refined methods for estimating oxygen content are not ordinarily
justified.
326
[CHAP. IX
TABLE XIX
RANK OP COALS
Rank
Anthracite
Semi-anthracite
Semi-bituminous
Bituminous
/
'
Fuel Ratio
between 10 and 60
between 6 and 10
between 3 and 7
between | and 3
Fuels of lower rank than bituminous, namely, sub-bituminous and lignite, may have fuel ratios within the bituminous range but are characterized by higher water or oxygen contents.
The classification of coals on the basis of fuel ratio is not entirely satisfactory for many purposes. Several other methods^ have been developed which give more nearly exact differentiation.
Heating Value of Coal. The total heating value of a coal may be
determined by direct calorimetric measurement and is usually expressed
in Btu per pound. The net heating value is obtained by subtracting
from the total heating value the heat of vaporization at 18C of the
' U. S. Bureau of Mines, Bulletin 123. With permission.
' Haslam and Russell, Fv^ and Their Combustion, McGraw-Hill Book Co.
(1926).
5^' -
CHAP. IX]
327
water present in the coal and that fonned by the oxidation of the available hydrogen. Thus,
Net H.V. = Total H.V. - 9 X H X 1056
(1)
Heat of Combustion
14,495 Btu per pound
61,000 Btu per pound
51,550 Btu per pound
6,770 Btu per pound
Then,
Total H.V. = 14,495C + 61,000Ha + 5770S
(2)
where
H.V. = heating value, Btu per pound
C, Ho, S = weight fractions of carbon, available hydrogen, and
sulfur, respectively
Equation (2) is known as Dulong's formula. It is not theoretically
sound because it neglects the heats of formation of the compounds of
328
[CHAP. IX
Rank
Coke
Anthracite
Semi-bituminous
Bituminous
Sub-bituminous
Lignite
H.V.'
14,495
16,100
17,400
17,900
17,600
17,100
H^
0.0
0.029
0.049
0.054
0.045
0.037
.r"
From the data of Table XX, the heating value of the bituminous coal
whose analysis was given on page 324 would be predicted as 17,900
X 0.666 = 11,920 Btu per pound, in error by only 1.7 per cent as com' E . A. Uehling, Heat Loss Analysis, McGraw-Hill Book Co. (1929). With per^ mission.
,
..-:
CHAP. IX]
CHARACTERIZATION OF PETROLEUM
329
PETROLEUM
330
[CHAP. IX
. ^=V
where
. ^ ^^ - - ,i
: ^'\
/.
,
, ,-
12.2-12.5
11.8-12.0
11.0-11.5
11.5-11.8
10.5-11.5
10.0-11.0
9.8-11.0
'
CHAP. IX]
CHARACTERIZATION OF PETROLEUM
331
tion between the curves of Fig. 63. In this figure, API gravities are
plotted as ordinates and average boiling points as abscissas with lines
of constant K from Equation (3). The relationship between specific
gravity and degrees API is shown by Fig. B in the Appendix.
It has also been found that a fair empirical correlation exists between
. .' .
332
[CHAP.
IX
1^
N, 1
1000
800
14
1^
\ 5
\
O 80 ~
IS.^
- 4 -lobo-
^.
IV
\ 1980
1
1
00
-\
=fe
T 4
^\ 4 ' 4
4^
-
1 8 -
t
fc
j ^
'i
1.0
.8
\1
\i
4" V^
4 \ ^ rj:
\ \^ 4
S^ 40
S 10
kS,
i
lioo-
3V
K \^
\
\
.\
VT
V\
> -
\600
V\
ftv
500
^40(
^
N
^ s \
Characterization Factor
-5
-^V
V (JO
100
N ^
1 .5 12.0 1 2.5
to the boiling point from only viscosity and gravity data. This relationship is particularly useful for heavy stocks on which boiling point
data can be obtained only under high vacuum. However, because of
the large change in viscosity with a slight change in the gravity of heavy
stocks, boiling points estimated in this way may be considerably in
error, sometimes as much as 50F for the heavier residues. Similar
charts were developed on the basis of viscosities at other temperatures.*
8 Watson, Nelson, and Murphy, Ind. Eng. Chem., 27, 1460 (1935).
CHAP.
CRITICAL
IX]
333
PROPERTIES
S
y^^
;^^y--^
S12
&
&
oo-
,,?
^
,oa?
^i)^S^H ^
e<
<?f'
'y^
=
y\y^
^
y
: ^
^
^
> ^
if'1
10.0
.
F I G . 65.
10.5
11.0
11.5
Characterization Factor K
12.0
334
[CHAP.
IX
0.9
/'
\0
y^
^ ^
^ ^ ^ ^
ND K C
.^^
^A
^5/
A
^- ^
^,
^
^
^
40O
11
12
500
600
Temperature ' F
13
1000
FIG. 66. Specific heat of liquid petroleum oils where K = 11.8 (midcontinent stocks). For other stocks multiply by correction factor.
CHAP.
IX]
335
,
^ 4
I"
Aj.
AV
:A.<i
pt*
" 0.5
US'.??
doi
' c^^*"
0.4
0.2
100
20O
30O
400
600
600
700
800
Temperature "F
900
1000 1100
Specific Heats of the Vapor State. At temperatures below atmospheric the molal heat capacities of complex gas molecules approach a
constant value of 7.95 whereas at high temperatures the curves expressing heat capacity as a function of temperature become concave downward. Since this complicated form of relationship is difficult to express
in a single equation, Fallon and Watson* proposed the use of the following two forms of equations:
For temperatures from 50 to 1400F:
Cp = a -I- b r -1- cT^
For temperatures from - 3 0 0 to -f200F (never above 200F):
cp = 7.95 -I- uT
where T is in R and Cj, is the molal heat capacity.
'Holcomb and Brown, Ind. Eng. Chem., 34, 590 (1942).
With permission.
336
[CHAP. IX
.,.
-^ABLE XXI
For 50 to 1400F,
Cp = a + bT + cP
6 XIO'
- c X 10^
3.42
2.71
1.38
1.97
041
2.25
2.30
3.14
-1.56
9.91
16.20
23.25
27.69
35.95
45.40
45.78
55.85
8.26
1.28
2.80
4.27
5.25
6.97
8.83
8.89
10.98
1.72
6.4
8.13
6.20
2.57
3.97
0.93
0.93
3.9
X 10-"
X 10-"
XlO-5
X 10-3
X 10-3
X 10-2
X 10-2
X 10-2
4.00
3.85
1.79
1.26
1.25
1.19
1.19
1.0
CHAP.
337
HEAT OF COMBUSTION
IX]
\^^
X^
s*
\o
^
if ^"''-%
B
\ /
^
120
t>'h
.V*
,n^
R!Jl^
i,?0-
>
>A
CO
"Sioo
>1?
-?!.
(J
' - .
100
200
300
400
*)
80
.i
v < % ^0
500
600
700
Average Boiling Point,P
f>"
vi
h-^
800
900
1000
{Note:
(a)
(b)
(c)
(d)
(e)
(/)
338
[CHAI". IX
-20,400
1
^12.0
/^.11.9
-20,200
11.8
^11.7
1
11.6
11.5
-19,800
^11.4
m
^
U^3^f
v// 2:1^1
.r
^u
1
6
11-3 V
-19,600
S -19,400
0.9
= -19,200
.8"~
CO
1U.7
; -19,000
10.6
/
-18,800
-18,600
.-
0.2
.10
inr
-18,400
-18,200
-18,000
V
-17300
-17,600
//
10
20
30
40
60
60
70
A P I Gravity
The standard basis which has been adopted for the expression of the
total heating value of a fuel gas is the number of Btu evolved when one
cubic foot of the gas, at a temperature of 60F, a pressure of 30 inches
of mercury, and saturated with water vapor, is burned with air at the
same temperature, and the products cooled to 60F, the water formed
in the combustion being condensed to the liquid state. Since gas is
rarely burned under these standard conditions of temperature and
pressure, the heating-value per standard cubic foot is not a convenient
unit for calculations. However, the unit is widely used as a basis for
specifications and legal standards.
CHAP.
IX]
FUEL GAS
339
(5)
340
[CHAP. IX
TABLE XXII
HEATING VALUES AND FLAME TEMPERATURES OP GASES
H.V. = total heating value, Btu per standard cubic foot, measured at 60F, 30 inches
of Hg and saturated with water vapor (assuming ideal gas behavior)
Maximum Flame Temperatures
with Air at 18C
Gas
Formula
H.V.
Carbon monoxide
Hydrogen
Paraffins:
Methane
Ethane
Propane
n-Butane
n-Pentane
Olefins:
Ethylene
Propylene
Butylene
Amylene
Acetylene
Aromatics:
Benzene
Toluene
Mesitylene
Naphthalene
Theoretical
(assuming
complete
combustion)
Calculated*
(allowing tor Actual*
equilibrium
conditions)
2440C
2200
CO
H^
315
319
CH4
994
1741
2478
3212
3947
1980
2150
2300
2080
2090
1918C
1949 .
1967
1973
1575
2297
3017
3814
1544
2240
2200
2200
2180
2072
2050
2033
3686
4399
5845
5795
2240
2240
2240
C2H6
C3H8
C4H10
C6H12
C2H4
CsHe
C4H8
CsHio
C2H2
CeHo
CeHfiCHg
C6H3(CH3)3
CiiHg
1880C
1895
1925
1900
>-
,^'=i-'
1975
1935
1930
* Jones, Lewis, Friauf and Perrott, J . ilm. CAem. Soc, US, 869 (1931).
If the analysis of a gas is carried out carefully, its heating value may
ordinarily be predicted by means of these equations with an error of
less than 2 per cent. Larger errors arise if large quantities of acetylene
are present in the gas.
niustration 2. A city gas has the following composition by volume:
CO2
2.6%
C2 73H4 72 (unsaturateds)
8.4%
O2'.
0.7%
H2
39.9%
CO
32.9%
Ci 14H4 28 (paraffins)
10.1%
N2
5.4%
100.0%
CHAP. IX]
I N C O M P L E T E COMBUSTION OF F U E L S
341
(a) Calculate the theoretical number of moles of oxygen which must be suppUed
for the combustion of 1 mole of the gas.
(6) Calculate the heating value of the gas in calories per gram-mole and Btu per
standard cubic foot.
Solution:
(a) Basis: 100 gram-moles of gas.
Oxygen required for:
E
f^
,,
.
32.8
19.95
16.45
22.3
Total
9L5
'
'
''"
27,250 cal
22,180 cal
36,100 cal
23,730 cal
109,260 cal
, , ,. ,
109,260 X 1.8
Btu per standard cubic foot =
5^7"^
~ ^-I^O385.5
'
CO2
CO
12.4%
1.2%
O2
N2
5.4%
81.0%
100.0%
, ,
..
342
[CHAP. IX
Calculate the standard heat of reaction in Btu per pound of coal burned.
Basis: 1.0 lb-mole of flue gas.
**"'
C in CO2 = 0.124 lb-atom or
C in CO = 0.012 lb-atom or
Total carbon = 1.49 -|- 0.14 =
Coal burned = 1.63 + 0.681 =
Heating value of cpal = 2.39 X 12,180 =
Heat of combustion of Cb = 0.012(-67,410 X 1.8) =
Standard heat of reaction = -29,100 (-1460) =
-27.640 Btu or - 27,640 -r- 2.39 =
1.49 lb
0.14 lb
1.63 lb
2.39 lb
29,100 Btu
-1460 Btu
-11,660 Btu
per lb of coal
CHAP. IX]
343
INPUT ITEMS
Group 1. The enthalpy, both sensible and latent, of each material entering the
process.
Group 2. Where fuel is used primarily as a source of heat or in the production
of fuel gases, the total heating value of the fuel.
Group 3. The heat evolved at IS^C in the formation of each final product from
the initial reaetants when such heat effects are exothermic. Where a fuel is used
and its total heating value is included as an input item the products formed from
the fuel by combustion or reaction of the fuel with the charge are not considered
in this group.
Group 4. All energy supplied directly to the process from external sources in the
forms of heat, electrical or radiant energy or work.
OUTPUT ITEMS
344
[CHAP.
IX
CHAP. IX]
COMBUSTION OF FUELS
345
Because of the fact that in many combustion processes water will not
be condensed from the products of combustion, even if they are cooled
to 18C, it is sometimes considered that the thermal efficiency of the
apparatus should be based on the net heating Value of the fuel. The
total heat input is then obtained by considering only the net heating
value of the fuel, plus all the sensible heat supplied. A thermal efficiency on this basis is termed the thermal efficiency based on the net
heating value. This method of expression has as its principal advantage
the fact that the percentage efficiencies are higher and appear more
encouraging. However, it is undesirable because combustion apparatus
is available which is capable of recovering some of the latent heat of the
water vapor from the gaseous products. On this basis of expression
such apparatus might have an efficiency above 100 per cent. The
thermal efficiency based on total heating value is a better general criterion for Judging the operation of a combustion process.
Percentage efficiency is also dependent on the quantity of heat which
is designated as effectively utilized. Various interpretations frequently
may be made of this quantity. For example, a furnace and steam boiler
unit used in domestic heating might be considered as effectively utilizing only the heat represented by the enthalpy of the steam produced.
On the other hand, it might be logical to include as effective heat the
radiation from the furnace itself which is used in heating the room in
which it is situated. The efficiency of the unit might be expressed on
either basis.
A gas producer or water gas generator produces a combustible gas at
a relatively high temperature. If the gas can be utiUzed while hot its
sensible enthalpy as well as its heating value should be included in
the effectively utilized heat of the producer unit. The efficiency of the
unit on this basis is termed the hot thermal efficiency. If the gas must
be cooled before use its sensible heat is not useful and only the heating
value can be classed as heat effectively utilized in the producer. The
efficiency on this basis is termed the cold thermal efficiency.
COMBUSTION OF FUELS
346
[CHAP. IX
CHAP. IX]
347
to devise methods of circumventing these limitations. Extensive information can often be built up from but few data, and complete material
and energy balances established from a few temperature measurements,
the proximate analysis of coal, and an Orsat analysis of gas.
The various calculations which follow illustrate the modifications in
procedure necessary to make the best use of data available and also to
deal with the special variations in combustion processes represented in
four special cases:
Case
0.
b.
c.
d.
of fuel charged.
;
of dry air supplied.
of moisture in air supplied.
of dry gaseous products.
of water vapor in gaseous products.
of refuse.
348
[CHAP. IX
Ultimate analysis
Carbon
Available hydrogen
Nitrogen
Combined water
Free moisture
Ash
Total
65.93%
3.50%
1.30%
6.31%
4.38%
18.58%
100.00%
<
/
,>i
:,
Ash content =
Carbon content
Average temperature
Mean specific heat from 65 t o 255F
(Estimated from Fig. 39, page 219)
87.4%
12.6%
255F
0.23
h.'J
"
1. Orsat analysis
Carbon dioxide
Oxygen
Carbon monoxide
Nitrogen
Total
Average temperature
'...
Data on Air
Average dry-bulb temperature
Average wet-bulb temperature
Average barometric pressure = 29.08 in. Hg
11.66%
6.52%
0.04%
81.78%
100.00%
488F
',
73.0F
59.4F
'
j
/
/
98.3%
Calculate the material and energy balances for the entire plant.
MATERIAL BALANCE
'
/ /
.
^' I .
jr
193F
1,038,400 lb
fired.
/
-
:*
Where the refuse is not weighed directly its weight can be readily calculated from
its ash content and that of the coal. The following method is correct where mineral
sulfides are not present in the coal.
.
'
/
'
CHAP. IX]
349
18.58 lb
0.8740 lb
=
21.2 lb
A direct measurement of the weight of gaseous products from a combustion process is seldom made because of the many difficulties involved.
Pitot tubes measure inaccurately because of the low velocities encountered in chimneys and flues. Orifice and Venturi meters are similarly
unreliable because of low-pressure drops encountered and because soot
accumulates in the openings. Electric flow meters read inaccurately
if the composition of the gas varies with respect to carbon dioxide or
water vapor. In any case the direct measurement of gas streams is
made extremely difficult because of variation in temperature and velocity
across each section of the stream. Any accurate measurement must
give a correct integrated value of velocity and temperature over the
entire cross section. Because of these uncertainties and troubles it
becomes easier and more nearly accurate to calculate the weight of
gaseous products from the stoichiometric relationships of combustion.
The complete analysis of the gaseous products includes the percentages
of carbon dioxide, carbon monoxide, oxygen, methane, ethane, hydrogen,
and nitrogen present. Moisture content is not revealed in the usual
gas analysis because the entire analysis is conducted with the gas sample
saturated with water vapor at a constant temperature and pressure.
The general rule is recommended that the weight of dry gaseous products should be calculated from a carbon balance. A carbon balance is
selected as the basis of this calculation for two reasons. In the first
place, carbon is determined with a higher degree of precision in both fuel
and gaseous products than any other elenaent present. Secondly,
carbon is the chief constituent in both fuel and gaseous products so that
a slight error in its determination will not be magnified in subsequent
calculations. To calculate the weight of gaseous products from a
material balance of any other element would invite many additional
sources of error. For example, the hydrogen balance would be out of
the question because of the many sources of hydrogen, its relatively low
percentage content, its several outlets, and its various methods of combination.
Carbon Balance
Carbon gasified. Basis: 100 lb coal fired.
Carbon in coal = 100 X 0.6593 =
Carbon in refuse = 21.2 X 0.1260 =
Carbon entering stack gases =
350
[CHAP. IX
0.1166 lb-atom
0.0004 lb-atom
0.1170 lb-atom
231.5
0.660
94.2
1041
1367
lb
lb
lb
lb
lb
IH
;''
30.3
Direct measurement of the weight or volume of air used in combustion is accompanied by the same difficulties as the direct measurement
of gaseous products. Furthermore, air is usually drawn through the
grate by chimney draft so that there is no need for confining the supply
of air in ducts and there is no opportunity for direct measurement of
its flow.
The dry air used in combustion consists of oxygen and inert gases,
chiefly nitrogen. These inert gases also include argon and traces of
rare gases, but because of the small amount present it is customary to
include all the inert gases as nitrogen and assign a molecular weight of
28.2 to atmospheric " nitrogen." ^^ This nitrogen passes through the
furnace unchanged and appears entirely in the gaseous products. Any
nitrogen present in the fuel burned will also appear in the flue gases.
The nitrogen in ordinary solid and liquid fuels burned will usually be
negligible or very small. , However, in the combustion of gases a considerable portion of the nitrogen appearing in the flue gases may come
from the gaseous fuel.
The composition of dry air may ordinarily be taken as constant, containing 21.0 per cent oxygen and 79.0 per cent nitrogen by volume, the
nitrogen content including the argon present. Under certain conditions
the air used in combustion may contain appreciable amounts of carbon dioxide, making a separate gas analysis of the air valuable. The
moisture content of air is subject to extreme variations depending upon
weather conditions so that a separate determination of the moisture
content of air is invariably necessary.
Because of the constancy of composition of dry air it is possible to cal12 The molecular weight of atmospheric " nitrogen " is taken as 28.2 because of the
argon associated with it.
i
.
v - i
!
CHAP. IX]
351
culate readily the weight of air used in a combustion process from a knowledge of the nitrogen content of the gaseous products and of the fuel used.
Accordingly, the general rule is expressed that the weight of dry air
actually used in combustion process is calculated from a nitrogen balance.
The chief objection to the use of the nitrogen balance basis is that in
gas analysis, errors resulting from unabsorbed components accumulate
on the nitrogen determination which is always found by difference.
Nitrogen Balance. Basis: 100 lb coal fired.
Nitrogen in gaseous products =
Nitrogen from coal = 1.30/28.0 =
Nitrogen from air =
Dry air supplied = 36.85/0.79 =
or 46.6 X 29 =
36.90 lb-moles
0.0464 lb-mole
36.85 lb-moles
46.6 lb-moles
1354 lb
It will be noted that the nitrogen content of the coal might be neglected without introducing a serious error.
4. Weight of Moisture in Air.
The weight of moisture per mole of dry air depends upon the temperature, pressure, and relative humidity of the air. From the dew point
the partial pressure of the water vapor is determined, and the moisture
content of the air may be calculated by the methods explained in Chapter IV.
Dry-bulb temperature =
Wet-bulb temperature =
From Fig. 9, the molal humidity of the air is 0.012
Water suppUed with air = 46.6 X 0.012 =
5. Total Volume of Wet Air Introduced.
"
73.0F
69.4F
0.559 lb-mole
47.2 lb-moles
18,870 cu ft
352
[CHAP. IX -
The Orsat apparatus used for analyzing the stack gases does not
determine hydrogen or hydrocarbon gases. However, in an efficiently
operated boiler furnace, hydrogen and hydrocarbons are present only in
small quantities. It is therefore assumed that all the hydrogen intro- '
duced into the system leaves as water in the stack gases.
Hydrogen in H2O of stack gases =
2.892 lb-moles
From Table I, this partial pressure is seen to correspond to a dew point of 36C or
97F.
7. Total Volume of Gaseous Products.
'
'
48.0 lb-moles
34,150 cu ft
Input
Coal
Dry air (46.6 lb-moles)...
HjO in air (0.559 lb-mole)
Total
/,
Output
1001b
1354 lb
10.05 lb
14641b
21.2 lb
1367 lb
52.1 lb
14401b
CARBON BALANCE
In coal
Total
65.931b
65.931b
In gases
In refuse
63,261b
2.67 lb
65.93 lb
CHAP.
SUMMARY
IX]
OF M A T E R I A L
353
BALANCES
NITROGEN BALANCE
1040 lb
1.30 lb
1041 lb
I n stack gases
(36.90 lb-moles).
1 i*
Total
10411b
1041 lb
Coal 100 lb
'
: [f
1
1
.
JsTCSfil'
>
Refuse 21.2 lb
.' 1 u
' '
HYDROGEN BALANCE
1.127 lb
0.708 lb
"
5.83 lb
. . ... .
0.491 lb
;; '-vi.
3.50 lb
5.83 lb
i.:!(,- . , 1
:)!
Total
..
5.83 lb
..
18.58 lb
ASH BALANCE
18.58 lb
OXYGEI <r BALANCE
5.61 lb
3.89 lb
313.5 lb
8.95 lb
3321b
In CO 2 of stack gases
5.26 X 32
In O2 of stack gases
2.94 X 32
In CO of stack gases
0.01804/2 X32
In H2O of stack gases
2.892/2 X32
Total
168.5 lb
94.2 1b
0.289 lb
46.3 lb
3091b
354
[CHAP. IX
It will be seen that there is a deficit of 24 lb or 1.6 per cent on the output side of the overall material balance. This discrepancy falls entirely
on the oxygen balance since no direct calculations were made from this
basis. The oxygen content of the fuel is obtained by difference, so that
all errors in any other determination of the coal analysis accumulate
algebraically upon this value. In this particular case the deficit of 24
pounds in the overall material balance indicates that the content of the
carbon in the coal, or the content of the carbon monoxide or carbon
dioxide in the gas, is low.
Other errors or omissions in chemical analysis will be reflected in the
material balance. For example, the oxygen content of the air supply
might be less than 21.0 %, and some carbon dioxide might enter with
the air and would escape consideration unless a special analysis of the
air were made. The presence of any suspended tar or soot in the
gaseous products might introduce a serious error in the overall material
balance.
8. Theoretical Amount of Air Required for Combustion.
\i
The weight of air theoretically required for complete combustion depends upon the chemical composition of the fuel and the stoichiometric
relations involved in combustion. Since the one element in common for
all combustion reactions is oxygen, the weight of air required for combustion must be calculated from an oxygen balance. The oxygen already
in the fuel is assumed to be in combination with hydrogen. Hence
only the available hydrogen of the fuel is considered in calculating its
oxygen requirement.
,
,!.,..
Per Cent Excess Air
Basis: 100 lb coal fired.
' ,
OXYGEN BALANCE
Since it is conventional to utilize total rather than net heating values in energy
balances the reference state for all water involved in the process is the liquid state;
the enthalpies of reactants and products are evaluated on this basis.
' j
CHAP. IX]
355
1,167,000 Btu
0 Btu
2,590 Btu
'
Oviput
38,850 Btu
2,190 Btu
3. Enthalpy of refuse.
Weight of refuse = 21.2 lb
. ;:
Enthalpy = 21.2 X 0.23 X (255-66) =
1,090 Btu
;,>,;,.
COj
CO
O2
Nj
= 5.-26
= 0.018
= 2.94
=36.90
(9.94)
(7.03)
(7.22)
(7.02)
(488
(488
(488
(488
65)
65)
65)
65)
= 22,120 Btu
=
50 Btu
= 8,990 Btu
= 109,600 Btu
1,665
53,960
9^290
64,920
Btu
Btu
Btu
Btu
356
.'
'
[CHAP. IX
;
X 100 = 873 lb
42,450 Btu
Btu
Percent
1,167,000
98.9
0
0
2,590
0.2
1.
2.
3.
4.
10,570
1,180,160
0.9
100.0
38,860
2,190
1,090
140,660
69,920
890,000
42,450
1,180,160
3.3
0.2
0.1
11.9
5.5
75.4
3.6
100.0
Energy Output
1.
2.
3.
4.
5.
6.
7.
- /
, ,.
76.3%
^^"^^^
CHAP.
COMBUSTION CALCULATIONS
IX]
367
'a
Enthalpy of
Dty Air 0.2% "
1
- .
-"
tif
.S
,,]
:'i ill y
^<
Enthalpy of
Water Vapor
in Air 0.9%
Heating Value
of Refuse
3.3%
Heating Value of
CO in Stack Gas
0.2%
Enthalpy of
Refuse
ai%
Enthalpy of
Dry Stack Gas
11.9%
Enthalpy of
ater Vapor iin
Water
Gas
StackI Gas
5.5%
Undetermined
Losses
3.6%
Heat Used in
Generating
Steam
75.4%
^
,
3
V
100.0%
FiQ. 7 1 .
358
[CHAP.
IX
hydrogen content of the fuel by empirical methods such as those illustrated on page 328 for coal, page 334 for gases, and Fig. 65, page 333
for oils. The calciUations are then carried out as in the preceding
illustration.
In the preceding illustration the nitrogen content of the coal was
known. In making a complete ultimate analysis it is necessary to determine this element in ordei: that the oxygen content may be obtained
by difference. However, from the results of the previous illustration it
is apparent that the nitrogen in the coal might be neglected altogether,
assuming all nitrogen in the flue gases to have come from the air. No
appreciable error will result from neglecting this nitrogen except in
determining the oxygen or combined water content of the coal by difference. For this calculation it is ordinarily sufficient to assume a nitrogen
content of 1.7 per cent of the combustible in the coal. This assumption
will ordinarily not be in error by more than 0.3 per cent of the weight of
the combustible except in the case of anthracite coals." Greater refinement is not justified because of the uncertainty of the sampling of the
coal and of other data on which the material balance is based.
Illustration 5. Coal-Fired Boiler Furnace. A furnace is fired with a bituminous
material coal having the following proximate analysis:
Moisture
2.9%
. Volatile matter
33.8%
Fixed carbon
53.1%
Ash
10.2%
,^ <. _ _
* ' 100.0%
The ultimate analysis is known only in part and includes (as-received basis):
Sulfur
1.1%
Carbon
73.8%
The dry refuse from the furnace has the following composition:
Volatile matter
3.1%
__ "
Fixed carbon
18.0%
' >'
Ash
78.9%
*'
100.0%
The Orsat analysis of the flue gases is as follows:
/
Carbon dioxide
12.1%
Carbon monoxide
0.2%
Oxygen
7.2%
Nitrogen
80.5%
100.0%
CHAP. IX]
369
steam at a gauge pressure of 100 lb per sq in., quality 98%, at a rate of 790 lb of
steam or water per 100 lb of coal charged.
Compute complete material and energy balances, the volumes of air and flue gases
per 100 lb of coal charged, and the percentage excess air used.
MATERIAL BALANCE
5.94 lb-atom
0.121 lb-mole
0.002 lb-mole
0.123 lb-atom
48.3 lb-moles
360
[CHAP. IX
= 48.3 X 0.121 =
=48.3X0.002=
=48.3X0.072=
= 48.3 X 0.805 =
Total =
5.85
0.096
3.48
38.87
lb-moles
lb-moles
lb-moles
lb-moles
or. X 44 = . . . .
or X28 = . . . .
or X32 = . . . .
or X28.2 = . .
48.30 lb-moles or
2581b
3 1b
1111b
1097 lb
14691b
. .|,,.-
N2 in flue gases =
38.87 lb-moles
38 87
Dry air supplied = '- =
0.79
or 4 9 . 2 X 2 9 =
From Fig. 9:
:
49.2 lb-moles
14301b
-^
,:
, s':
0.59 lb-mole
10.6 lb
49.8 lb-moles
14401b
19,450 cu ft
: :;:
,,
,,
9.38 lb-moles
0.94 lb-mole
3.79 lb
The hydrogen burned may be taken as the available hydrogen of the coal, neglecting
the small hydrogen content of the uncoked combustible in the refuse.
6. Complete ultimate analysis of coal. The unknown items of the tiltimate analysis are combined water and nitrogen. As pointed out on page 358, the nitrogen
content may be assumed to be 1.7 X 0.87 = 1.4%. The combined water may then
be determined as the difference between 100 and the sum of the percentages of moisture, carbon, hydrogen, sulphur, nitrogen, and corrected ash.
Corrected ash = 10.2 - 3/8(1.1) =
Combined H2O = 100 - (2.9 -|- 73.8 + 3.8 + 1.1 + 1-4
+ 9.8) =
9.8%
7.2%
CHAP. IX]
361
2.9%
73.8%
3.8%
1.1%
1.4%
9.8%
7.2%
100.0%
=
18
H2O formed from H =
Total =
0.59 lb-mole
0.56 lb-mole
1.88 lb-moles
3.03 lb-moles
or 55 lb
51.33 lb-moles
29.19 in. of Hg
39,200 cu ft
.'
Inpvi
Coal
Dry air (49.2 lb-moles)
Water vapor in air (0.69 lb-mole)
Total
100 lb
1430 lb
10 lb
1540 lb
Output
Dry flue gases (48.3 lb-moles)
Refuse
Water vapor in flue gas (3.03 lb-moles)
Total
1469 lb
13 lb
55 lb
1537 lb
6.15 lb-moles
1.88 lb-moles
7.09
Air theoretically required = - ^ =
33.8 lb-moles
49.2 lb-moles
7.09 lb-moles
362
[CHAP. IX
0-2
7.2--^=.
7.1 lb-moles
Os actually consumed =
14.3 lb-moles
7.1
Percentage excess oxygen = percentage excess air = = 49.6.
14.0
This percentage excess is based on the oxygen required for all combustible substances which were actually burned.
Feed Water
Steam
BoUer
7901b
7901b
Ck>al
BoUcr
Furnace
1001b
,,
Refiise
- L
13jQlb
/
FIG. 72. Material balance of a boiler furnace (Illustration 5).
E N E R G Y BALANCE
The energy balance of this problem is calculated exactly as in Illustration 4, estimating the heating value of the coal by the empirical method discussed on page 328.
Effect of Sulfur in Coal. In the prece(iing illustrations the combustion of the suUur in the coal has been neglected. This does not
introduce appreciable error if the sulfur content is low, 1 per cent or
less. It is difficult to take into account the combustion of the sulfur
by any rigorous method because of the uncertainty of the forms in which
it is present in the coal and the difficulty of determining its distribution
in the combustion products. A considerable part of the sulfur which is
//
CHAP.
IX]
363
present in the coal in a combustible or available form will appear as sulfur dioxide in the flue gases. The remainder will be present in the refuse.
The ordinary scheme of flue gas analysis by the Orsat apparatus, in
which the gas sample is confined over water, does not permit determination of sulfur dioxide. Because of the high solubihty of sulfur dioxide
in water (about thirty times that of carbon dioxide) the bulk of the SO2
will be absorbed in the water of the sampling apparatus and burette.
Any SO2 which is not removed in this manner will be absorbed and
reported as CO2. The reported analysis will ordinarily represent approximately the composition of the S02-free gases. Methods are available by-which separate determination may be made of the SO2, but this
is not ordinarily feasible for performance tests of combustion equipment.
Neglect of the combustion of sulfur in calculations of the type carried out in Illustration 4, in which the oxygen balance is not used,
does not introduce any serious error, even if the sulfur content is relar
tively high. The calculated total weight of dry flue gases will be low
by approximately the weight of SO2 formed. This error is usually negligible. However, in the method of calculation of Illustration 5, in
which the net hydrogen in the coal is calculated from an oxygen balance,
the errors resulting from neglect of combustion of sulfur may be more
serious. In this type of calculation it is assumed that all free oxygen
not accounted for as CO2, CO, or free oxygen in the flue gas was utiUzed
in the oxidation of the net hydrogen of the coal. This assumption
neglects the oxygen consumed in oxidation of sulfur. As a result the
net hydrogen content calculated by this method will be too high, and
the combined water content, calculated by difference, will be too low.
These errors are particularly high when the sulfur is originally present
as iron pyrites, FeS2, in which case oxygen is consumed in the oxidation
of both the sulfur and the iron. However, because of the relatively
high atomic weight of sulfur it is permissible to neglect these errors
in dealing with coals containing less than 1 per cent of sulfur.
The probable errors involved in neglecting the combustion of the
suHur may be estimated for a typical case by consideration of the data
of Illustration 5. The coal contained 1.1 per cent sulfur. The maximum error would result if all the sulfur were in the form of iron pyrites.
In this case, for each pound-atom of suKur present 11/8 pound-moles
of oxygen would be consumed in producing SO2 and Fe203. On the
basis of 100 pounds of coal charged 0.048 pound-mole of oxygen would
be required for combustion of the sulfur of the coal. Introducing this
value into the oxygen balance on page 360 will reduce the unaccountedfor oxygen, used in oxidizing hydrogen, from 0.94 to 0.89 pound-mole.
The calculated net hydrogen is correspondingly reduced from 3.8 to
3.6 pounds and the combined water content is increased from 7.2 to
364
[CHAP.
IX
7.4 pounds. These errors are not serious and in addition represent
maximum errors because actually not all the gulfur will be in the pjTitic
form and furthermore it will not be completely burned.
Case 3. Method of Calculation Where Sulfur Is High and the
Carbon and Hydrogen Contents of the Coal Are Unknown. Where
sulfur contents of more than about 1 per cent are encountered it is not
ordinarily desirable to use the oxygen balance for computing the net
hydrogen content of the coal. In order to develop an accurate oxygen
balance it would be necessary to have data on the forms in which the
sulfur occurred in the coal and on the sulfur content of the refuse.
Without such data the net hydrogen content is better determined
analytically or estimated by the empirical method of Uehling, discussed
on page 328. This latter method may also be used to estimate the total
carbon in the coal from a determination of the heating value.
' ^
If the sulfur content of a coal is so high that sulfur dioxide constitutes a considerable part of the flue gas it is necessary to obtain data
from which the amount of sulfur actually burned may be calculated.
A determination of either the sulfur in the refuse or of the SO2 in the
flue gases will supply this information. The former determination is
more easily carried out. It may then be assumed that the ordinary flue
gas analysis yields the composition of the S02-free gases and the total
quantity of gases computed on this basis. Direct determination of the
S02 content of the flue gases is more reliable but frequently unwarranted.
In calculating an energy balance involving a coal of high sulfur content
a sulfur correction should be applied to the heating value directly
determined in the oxygen bomb calorimeter. This correction results
from the fact that in the calorimeter the available sulfur is burned
almost entirely to SO3 whereas in ordinary combustion the major part
of it will form SO2. The correction may be taken as 1000 calories per
gram of sulfur, to be subtracted from the observed heating value.
Case 4. Gas Producers. In the operation of a gas producer, a fuel
gas of low calorific value is produced by blowing air, usually accompanied
by steam, through a deep incandescent bed of fuel. Carbon monoxide
and carbon dioxide are formed by partial combustion of the fuel. Hydrogen and the oxides of carbon are formed from the reduction of water,
and volatile combustible matter is distilled from the coal without combustion.
Effect of Soot and Tar. In many combustion processes the gases
contain carbon suspended in the form of soot and tar. These forms of
carbon do not appear in an ordinary volumetric gas analysis but must
be determined separately by absorption or retention on a weighed filter.
The tar can then be separated and analyzed for its hydrogen content
CHAP. IX]
GAS PRODUCERS
365
although this precision is not usually warranted. It is ordinarily sufficient to assume that the combustible of the suspended tar analyzes 90
per cent carbon and 10 per cent hydrogen and that the combustible of
the soot consists of 100 per cent carbon. Frequently refuse also appears
suspended in the gaseous products so that the ash content of the suspended material should also be measured.
In addition to the tar and soot suspended in the gases a gradual accumulation of these products settles in the flues. The slight correction
necessary for this is usually made by measuring the deposition over a
long period of time, for example, over the usual time interval elapsed
between successive cleanings of the flues. The tar deposit is removed
and weighed and, since the tons of fuel distilled during the time interval is known, a rough approximation can be obtained for the carbon
deposited per unit weight of coal charged.
The following illustration of gas producer operation is of value in
that consideration is given to the tar and soot suspended in the producer
gas and also to the Uve steam which is passed into the producer. The
problem is of added interest in that all experimental data were collected
with unusual care. Analyses of gas and coal and measurements of
temperatures were made at regular intervals over several days of operation and data carefully weighted to give average results. These data
were taken in part from a report by C. B. Harrop."
Dlustration 6. Air is supplied to a gas producer at 75F with a percentage humidity of 75% and a barometric pressure of 29.75 in. of Hg. Coal weighing 70,900
lb and having a gross heating value of 11,910 Btu per lb is charged into the producer. Tar weighing 591 lb is deposited in the flues prior to the point of gas sampling and contains 93% carbon and 7% hydrogen.
j The water vapor, suspended tar, and soot in the gases were determined experimentally by withdrawing samples of the gas through an absorption train. The results
are expressed in grains per cubic toot of wet, hot gas measured at 1075F and 29.75
in. of Hg.
Water vapor
3.43 grains per cu ft
Suspended tar
3.31 grains per cu ft
Suspended soot
1.52 grains per cu ft
It is assumed that the suspended tar is 90% carbon and 10% hydfogen and that
the soot is 100% carbon.
Saturated steam at a gauge pressure of 25.3 lb per sq in. is introduced at the bottom of the fuel bed.
Analysis of coal as charged:
Carbon
66.31% Nitrogen...
1.52%, Sulfur
1.44%
Available hydrogen 3.53% Total water 23.16% Corrected ash
4.04%
Total
100.00%
Ash (as weighed)
4.58%
" J . Am. Ceramic Soc, 1, 35 (1918).
: , ^ ^ .-..n;'~
366
Analysis of refuse:
Moisture
[CHAP.
Ash
Total
IX
95.82%
100.00%
13.65%
53.24%
100.00%
The gases leave the flue at 1075F and 29.75 in. of Hg. The refuse leaves the producer at 350F and rnay be assumed to have a specific heat of 0.22. The mean specific heat of the tar and soot between 75F and 1075F may be assumed to be 0.32.
The heating value of the suspended tar was found to be 16,000 Btu per lb, and that
of the deposited tar 15,500 Btu per lb.
Calculate complete material and energy balances for the operation of this gas
producer.
Solution: Since a majority of the details of this problem are similar to those of
Illustration 4, full explanations of all steps will not be repeated. A flow chart of
this process is shown in Fig. 73.
Coal
100 lb.
Dry Gas
(14.18 Pound Moles)
HjO Vapor
(0.45 Pound Mole)
Tar Deposited
Tar Suspended
Soot Suspended
'
Dry Air
8.1 lb.
0.811).
7.81b.
3.6 !b.
3.9 lb.
Steam
8.61b.
r Refuse
4.81b.
CHAP. IX]
367
Carbon in clean gases. Basis: 1.0 lb-mole of dry, tar- and soot-free gas.
C in CO2 =
0.0712 lb-atom
C in CO =
0.2185 lb-atom
C in CHi =
0.0325 lb-atom
Total =
0.3222 lb-atom
Water, tar and soot in gas. Basis: 1000 cu ft of wet gases at 1075F and 29.75
in. of Hg.
>, ,
,
,
1000
Moles of total gas =
=
0.888 lb-mole
looo
J9.9J
.
,
,
3.31 X 1000
Tarpermoleofdrygas.^Q^^^^gg^g=
0.0272 lb-mole
0.8608 lb-mole
0.0316 lb-mole
0.5501b
1.52 X 1000
TT^r:::; =
0.252 lb
7000 X 0.8608
Total carbon in gases. Basis: 1.0 lb-mole of dry, clean gas.
C in clean gases =
0.3222 lb-atom
C in tar = 0.550 X 0.9 = 0.495 lb or
0.0412 lb-atom
C in soot = 0.252 lb or
0.0210 lb-atom
Soot per mole of dry gas
Total
0.3844 lb-atom
7.8 lb
3.6 lb
378.8 lb
368
[CHAP. IX
f - '
Output
7.56 lb-moles
005 lb-mole
7.50 lb-moles
9.48 lb-moles
275 lb
0.023
0.218 lb-mole
3.91b
9.70 lb-moles
278.9 1b
A?,
''-'
591
Hj m deposited tar = - X 0.07 = 0.0585 lb =
709
Free Hj in gas =
H2 in CHi in gas = 0.46 X 2 =
H2 in H2O in gas =
H2 in suspended tar =
Total output of Hj =
'r
0.029 lb-mole
1.94 lb-mole
0.92 lb-mole
0.45 lb-mole
0.39 lb-mole
3.73 lb-moles
Input
Net H2 in coal = 3.53/2.02 =
H2 in water in coal = 23.16/18 =
H2 in water iikair =
Total input in addition to steam =
H2 from steam = 3.73 - 3.25 =
Steam introduced = 0.48 lb-mole or
1.75 lb-moles
1.28 lb-moles
0.22 lb-mole
3.25 lb-moles
0.48 lb-mole
'
8.64 lb
"
Input
Output
Coal
100 lb
Dry air (9.48 lb-moles)... 275 lb
Water in air (0.22 lb-mole)
3.91b
Steam (0.48 lb-mole)
8.61b
Refuse
4.8 lb
Tar deposited
0.83 lb
Soot suspended
3.6 lb
Tar suspended
7.8 lb
Dry clean gas (14.18 lb-moles) 359.3 lb
Water in gas (0.45 lb-moles).
8.1 lb
Total
384.431b
Total
387.5 lb
The slight discrepancy in the totals of the material balance results from inaccuracies
of the data and neglect of the sulfur content of the coal. The material balance is
also summarized in Fig. 73.
CHAP. IX]
369
3,800 cu ft
16,500 cu ft
ENERGY BALANCE
794,000 Btu
125,000 Btu
52,100 Btu
2,100 Btu
12,900 Btu
3,650 Btu
250 Btu
370
[CHAP.
12,360 Btu
290 Btu
1,111,240 Btu
93,560 Btu
1,191,000 Btu
0 Btu
0 Btu
9,700 Btu
4,100 Btu
1,204,800 Btu
98.9%
0%
0%
0.8%
0.3%
100.0%
V'
t8.9%
0.8% Enthalpy
of Steam
0.3% Enthalpy
of H,0 Vapo>
In'Air
"
^
v:::
0.2%
1.0%
I Heating Value of
Suspended Tar
10.4%
3 Heating Value of
Suspended Soot
4.3%
Heating Value of
DTy Broduccr Gas
66.0%
0.2%
0.1%
9.0%
3
Total Enthalpy of H , 0 Vapor
'Radiation Loss
Total
1.0%
7.8%
100.0%
IX
CHAP. IX]
371
Oidput
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
794,000 Btu
125,000 Btu
52,100 Btu
2,100 Btu
12,900 Btu
108,590 Btu
3,900 Btu
12,360 Btu
290 Btu
93,560 Btu
66.0%
10.4%
4.3%
0.2%
1.0%
9.0%
0.3%
1.0%
0.0%
7.8%
1,204,800 Btu
100.0%
'
'
THERMAL EFFICIENCY
Cold gas. The effectively utilized energy includes only the heating value of the
dry, clean gas.
^^ .
794,000
^
,
Efficiency =
'
= 66%
./
^ 1,204,800
Hot gas. The effectively utilized energy includes the total sensible enthalpy of all
materials in the gases and also the heating value of the suspended tar and soot.
Sensible enthalpy of dry, clean gases =
108,590 Btu
Sensible enthalpy of water vapor in gases = 12,360 (0.45
X 18,870) =
3,870 Btu
Sensible enthalpy of suspended tar and soot =
3,650 Btu
' Heating value of dry, clean gas =
794,000 Btu
Heating value of tar and soot =
177,100 Btu
Effectively utilized energy =
1,087,210 Btu
372
[CHAP.
IX
Fig. 75 there may be obtained directly the pounds of air used and the
pound-moles of wet flue gas produced and the carbon dioxide content of
the dry flue gas on the basis of 1 pound of combustible in oil, coal, gas,
or coke.
CHAP. IX]
PROBLEMS
373
PROBLEMS
1, A Kentucky coal has the following analysis:
Ultimate analysis of combustible
Proximate analysis as received
corrected ash-free moisture-free basis
Moisture
2.97%
C
84.39%
Ash (uncorrected)
2.94%
Net hydrogen
4.81%
Volatile matter
37.75%
N
2.00%
Fixed carbon
56.34%
S
1.02%
Combined H20
7.78%
100.00%
100.00%
The combustible referred to above includes those portions of coal as received which
are not classified as moisture or corrected ash.
Determine, on the " as received " basis:
(a) The rank of this coal.
(5) The total heating value by Dulong's formula.
. ;
(c) The total heating value by Uehling's method.
' ' " "'"''' ' ' (d) The estimated available hydrogen content by Uehling's method.
(e) The net heating value by Uehling's method.
(/) Ultimate analysis (as received, corrected ash).
2. In the following table are the analyses of several typical coals, as given in Bureau
of Mines Report of Investigations, No. 3296, " Classification Chart of Tjrpical Coals
of the United States." Both the ultimate and proximate analyses are on the " as
received " basis, and the hydrogen given in the ultimate analysis includes the hydrogen of the free moisture in the coal.
Proximate Analysis
Moisture
Volatile Matter
Fixed Carbon
Ash (uncorrected)
Ultimate Analysis
Carbon
, Hydrogen
Nitrogen
Sulfur
Heating Value
Btu/lb
No. 1
No. 2
No. 3
No. 4
No. 5
4.3%
3.0
82.6
10.1
2.0%
9.6
77.8
10.6
2.2%
21.1
66.2
10.5
10.6%
36.4
42.4
10.6
42.6%
24.7
27.0
6.7
82.5%
2.0
0.6
0.5
79.5%
3.7
0.9
0.6
76.1%
4.8
1.2
2.6
62.8%
5.6
1.2
3.3
37.3%
7.3
0.5
0.6
12,650
13,520
13,530
11,300
6,260
No. 1 Anthracite
No. 2 Semi-anthracite
No. 3 Medium volatile bituminous
374
[CHAP. IX
(b) Calculate total heating value by Dulong's formula. Compare the result
with the experimental value.
(c) Calculate the total heating value by Uehling's method. Compare the result
with the experimental value.
{d) Assuming that the proximate analysis and heating value alone are available,
calculate the per cent of carbon and of available hydrogen by Uehling's method.
(e) Calculate the net heating value.
3. A gas has the following composition by volume:
;
53.6%
1.6%
16.9%
24.3%
.*. 3.6%
The heating value of this gas is 1898 Btu per standard cubic foot. Calculate the
percentages of C2H4 and CeHe in the gas.
4. Calculate the maximum theoretical flame temperature in degree Centigrade
when the following gas is burned with the theoretical amount of dry air starting with
air and gas at 18C:
CO
Hj
O,
CO2
N2
30%
15%
1%
5%
_49%
100%
5. Calculate the theoretical flame temperature when the above gas is burned with
100% excess air.
6. Calculate the theoretical flame temperature of the above-mentioned gas when
burned with the theoretical amount of air and when both gas and air are preheated to
500C before combustion.
7. Calculate the theoretical flame temperatm'e of the above gas when burned with
the theoretical amount of air, the combustion of both CO and H2 proceeding to only
80% completion. The gas and air are initially at 18C.
8. A fuel gas has the following analysis:
- /
Carbon dioxide
Ethylene
Benzene
Oxygen
Hydrogen
Carbon monoxideMethane
Ethane
Nitrogen
3.0%
5.8%
0.8%
0.9%
38.8%
35.2%
9.5%
0.7%
5.3%
100.0%
'
,
C H A P . IX]
PROBLEMS
375
Calculate the theoretical flame temperature if this dry fuel gas is burned with the
theoretical amount of dry air. Gas and air are supplied at 18C. Assume that combustion is complete. Use 1 g-mole of the dry fuel gas as the basis of calculation.
9. For the fuel gas whose analysis is given in Problem 8, calculate the theoretical
flame temperature if the dry gas is burned with the theoretical amount of dry air.
T h e gas is supplied a t 1&C, b u t the air is preheated t o 700C. Assume t h a t combustion is complete. Use 1 g-mole of the dry fuel gas as the basis of calculation.
10. For the fuel gas whose analysis is given in Problem 8, calculate the theoretical
flame temperature if t h e gas is burned with 100 % excess air. T h e gas and air both are
dry and are supplied a t 18C. Assume t h a t combustion is complete. Use 1 g-mole
of the dry fuel gas as the basis of calculation.
11. The dry fuel gas whose analysis is given in Problem 8 is burned with the
theoretical amount of dry air. Both air and gas are supplied at 18C. If carbon
monoxide and hydrogen burn to 8 0 % completion, what is the theoretical flame temperature? Assume t h a t the combustion of the gases other than CO and H2 is complete. Use 1 g-mole of the dry fuel gas as the basis of calculation.
12. Four thousand (4000) kilograms of coke at an initial temperature of 1400C
has 360 kg of steam blown through it, forming 448 kg CO, 88 kg CO2, and 40 kg H2
at an average temperature of 1000C. The steam is supplied a t 120C, saturated.
The radiation loss is 100,000 kcal. Calculate the final temperature of the bed of coke.
13. A fuel gas has the following composition by volume:
:
>
CO2
2.1%
O2
0.5%
C2.BH4.2 (illuminants)
CO
_,,::
H2
C1.2H4.4 (paraffins)
Nj...
7.0%
33.8%
40.6%
11.2%
4.8%
100.0%
(a) Calculate the analysis of the flue gases formed by burning this gas with 3 0 %
excess air, assuming that all combustible components are burned to
CO2 and H2O.
(b) Calculate the heating value in Btu per standard cubic foot.
14. A fuel oil has a specific gravity of 0.91 and a viscosity of 28 Saybolt Furol
seconds at 122F. Estimate the characterization factor, average molecular weight,
average boiling point, hydrogen content, specific heat at 150F, and heating value
of this oil:
15. A petroleum fraction has a specific gravity (60/60F) of 0.88. When tested in
a Saybolt Universal viscometer a t 122F, a reading of 68 seconds was obtained. Using
the charts in the text, report the following values:
(a)
(6)
(c)
(d)
(e)
(/)
ig)
Characterization factor.
Average molecular weight.
Average boihng point.
Hydrogen content.
Specific heat of the hquid oil at 200P.
Specific heat of the vapor at 800F.
Heating value.
376
F U E L S A N D COMBUSTION
[CHAP. I X
4.71%
69.80%
1.42%
7.83%
6.73%
9.51%
6950 koal per kg
' '
''
This coal is gasified in a gas producer using air a t 20C saturated with water vapor.
No additional steam or water is admitted into,^;he producer. The barometric pressure is 740 mm. The resulting gas has the following composition:
:
Hj
; CO
N2
'
CHi
,.;.,.;,.,., H. CO2
O2
0.5%
21.2%
64.5%
5.8%
6.2%
1.8%
- : ...
/-t
'H
- .'. .Ui
During a
' ,
) /
(a) Calculate complete material and energy balances of this gas producer on the
basis of 100 kg of coal as charged.
(b) Calculate the thermal efficiency on both the hot and cold bases.
(c) Calculate the total volume of gases leaving the producer
(d) Calculate the heating value of the producer gas in Btu per cubic foot measured a t 60F, 30 in. of Hg, saturated with water vapor.
17. A gas producer is charged with bituminous coal having the following composition :
Proximate analysis:
-^
'
Moisture
' Volatile matter
,;
Fixed carbon
'
Ash
2.70%
25.77%
62.87%
8.66%
100.00%
Ultimate analysis:
Moisture
Carbon
Net hydrogen
Nitrogen
Sulfur
Corrected ash
Combined H2O
Total heating value = 13,944 Btu per lb.
* - '
;
[/.,,
-
2.70%
78.55%
4.13%
1.58%
0.69%
8.40%
3.95%
100.00%
'f
-^
CHAP. I X ]
PROBLEMS
377
t ,
,
,
.'
.
. :
CO
H2
CH4
C2H4..;
CO2
N2
25.0%
22.0%
3.6%
2.8%
9.2%
37.4%
100.0%
50.34%
30.68%
9.61%
9.37%
' ^*'
,
.
378
[CHAP. IX
12.2%
0.2%
7.0%
80.6%
100.0%
Calculate:
(a) Total material and energy balances for this process based on 100 lb of coal
charged, neglecting the combustion of sulfur. The heat losses and the
heat efEectively utilized may be considered to^ither as a single item of heat
output.
(6) Percentage excess air used in combustion, based on that required for complete combustion of all coal charged.
(c) The dew point of the flue gases.
(d) The actual volumes in cubic feet at the given condition of temperature,
humidity and pressure of the flue gases and air supply, per 100 lb of coal
charged.
19, A bituminous coal is burned in a boiler furnace with air at 85F, 90% percentage humidity. The barometric pressure is 29.20 in. of Hg. The furnace gases
leave at 572F. The refuse leaves the furnace moisture-free at 520F and when
analyzed contains 22.3% moisture, 12.3% volatile matter and 41.4% fixed carbon.
The mean specific heat of the refuse is 0.23. The proximate analysis of the coal is:
Fixed carbon
56.34%
Volatile matter
37.75%
Moisture
2.97%
Ash
2.94%
A partial ultimate analysis on the corrected ash- and moisture-free basis is:
Carbon
84.43%
Nitrogen
2.00%
Sulfur
'.
0.82%
The total heating value of the coal is 14,139 Btu per lb. Dry, saturated steam
at a gauge pressure of 150 lb per sq in. is produced at the rate of 780 lb per 100 lb
of coal charged. Water is fed into the boiler at 72F. The Orsat analysis of the flue
gas is:
.
^
CDs
w=
C.
'
12.0%
CO
1.2%
O2
6.2%
N,
80.6%
100.0%
Calculate:
(a) The net hydrogen content of the coal from an oxygen balance, neglecting
combustion of sulfur.
(6) The complete ultimate analysis of the coal.
(c) The complete material balance of the process, based on 100 lb of coal charged.
(d) The complete energy balance of the furnace, based on 100 lb of coal charged.
(e) The thermal efficiencies of the furnace and boiler, based on the total and on
the net heating values.
(J) The percentage excess air used, based on the total combustible charged.
CHAP. IX]
PROBLEMS
379
20. A heat at interchanger, used for heating the oil in a circulating hot oil heatihg
system, is fired with coal having the following proximate analysis:
Moisture
- Volatile matter
Fixed carbon
Ash
;.
12.38%
36.88%
37.50%
13.24%
100.00%
The heating value of the coal is 10,361 Btu per lb, and its sulfur content is 5.1%.
The coal is burned with air at a temperature of 70F and a percentage humidity of
60%. The barometric pressure is 29.3 in. of Hg.
The refuse from the furnace is discharged at a temperature of 600F and contains
16% fixed carbon and 84% ash. The sulfur content of the refuse is 7.8%. Its
specific heat may be taken as 0.23.
The flue gases leave the furnace at a temperature of 850F and have the following
composition by volume, on the siilfur- and moisture-free basis.
.
:^ ; , CO2
* ' : ' 1 CO
'i '*' O2
N2
11.50%
0.17%
7.51%
80.82%
100.00%
The oil is circulated at a rate of 3800 lb per 100 lb of coal charged and is heated
from 1S5F to 464F. The mean specific heat of the oil in this temperature range
is 0.55. Calculate;
(o) The complete ultimate analysis of the coal as estimated from the rank and
heating value.
(6) The complete material and energy balances of the interchanger, based on
100 lb of coal charged.
(c) The complete analysis, by volume, of the wet flue gases leaving the interchanger.
(d) The percentage excess air, based on the combustible actually burned.
(e) The volume of wet flue gases leaving the interchanger.
(/) The thermal efficiencies of the interchanger, based on both the total and net
heating values.
21. A brick kiln, of an intermittent type, is fired with 10,420 lb-moles of dry
producer gas. The weight of green ware is 410,000 lb containing 0.52% mechanical
water and 3.02% chemically combined water. The gas enters the kiln at 1220F
and a pressure of 29.65 in. of Hg, and contains 10 grains of tar (90% C, 10% H)
per cu ft measured at a pressure of 29.65 in. of Hg, 100F, and saturated with water
vapor. The dew point of the producer gas is 100F.
During the water-smoking period mechanical water is vaporized and leaves the
kiln at 300F, and the chemically combined water leaves at 400F. During watersmoking the saturation temperature of the gases is 160F. The flue gas leaves at
an average temperature of 720F. The average temperature of the ware at the end
of the burn is 2100F, and its specific heat is 0.23. The producer gas is burned with
air at 75F, 90% percentage humidity, and a pressure of 29.65 in. of Hg. The average
380
[CHAP. I X
*
25.00%
22.00%
3.60%
2.80%
9.20%
37.40%
100.00%
Flue gas
CO2
CO
Ha
O2
N2
y...
12.20%
0.16%
0.14%
7.10%
80.40%
100.00%
Calculate the material balance of the combustion process, the energy balance of the
entire unit, and the thermal efficiency. The heat absorbed by the kiln structure may
be included with the other undetermined heat losses as a single item.
22. Limestone is burned in a continuous vertical kiln which is heated by coal burned
on an external grate located beside the bottom of the kiln shaft. The limestone is
charged at the top of the shaft a t atmospheric temperature and gradually descends
in contact with a rising stream of the fiue gases from the grate. The burned lime is
discharged from the botton\of the shaft at a temperature of 950F. The flue gases,
mixed with all gases and vapors evolved by the charge, leave the top of the shaft a t
560F. For each 100 lb of coal burned, 161 lb of burned Ume are produced. The
limestone charged has the following composition:
'*
CaO
MgO
CO2
AI2O3
Si02
H20
51.0%
2.0%
42.2%
1.5%
1.2%
2.1%
100.0%
.
''
-,^'
' ' '
10.69%
66.62%
3.18%
1.57%
1.91%
6.41%
9.62%
100.00%
The total heating value of the coal is 11,805 Btu per lb.
following composition by volume:
CO2
N2
O2
. Vj
,,,:,
The coal is burned with air at a temperature of 70F having a humidity of 80 per
cent. The barometric pressure is 29.4 in. of Hg.
T h e refuse from the grate contains 4.2% fixed carbon and 95.8% ash. I t s sulfur
content is 3 . 1 % .
CHAP. IX]
PKOBLEMS
381
It may be assumed that in the burning process all CO2 and water are driven from
the limestone. The heat of wetting of granular limestone is neghgible. It may be
assumed that the sulfur burned forms SO2 which is further oxidized and absorbed
by the hme to form CaS04. The mean specific heat of the burned hme is 0.21.
Calculate the complete energy and material balances of the grate and kiln on the
basis of 100 lb of coal fired.
Calculate the thermal efficiency of the process, considering the effectively utilized
heat to be consumed in the decomposition of the hmestone.
23. A 12-hour test was conducted on a steam-generating plant with four of the
boilers in operation. The data for the 12 hour test are as follows:
Proximate analysis of coal
Moisture
4.38%
Fixed carbon
48,98%
Volatile matter
29.93%
Ash (uncorrected)
16.71%
100.00%
Half of the sulfur of the coal appears in the volatile matter.
Ultimate analysis of coal
Carbon
65.93%
Combined water
6.31%
Available hydrogen
3.50%
Free moisture
4.38%
Nitrogen
1.30%
Ash (corrected,
Sulfur
2.99%
sulfur free)
15.59% "
100.00%
Heating value of coal as fired (total)
11,670 Btu per lb
Weight of coal
fired
119,000 lb
Temperature of coal
65F
Proximate analysis of refuse
Moisture
4.77%
Volatile matter
2.08%
. ^
Flue gas
CO2
11.66%
O2
6.52%
Fixed carbon
Ash (uncorrected)
CO
N2
12.51%
80.64%
100.00%
0.04%
81.78%
100.00%
Temperature
Ai|
Dry-bulb temperature
Wet-bulb temperature
Barometer
Steam.
Feed water
Water evaporated
Steam pressure
Quality
488F
. '.
'
_
73F
59.4F
29.08 in. Hg
193F
1,038,400 lb
137.4 lb per sq in. gauge
98.3%
Calculate the complete material and energy balances for this steam-generating
plant.
24. Calculate the complete energy balances for Illustration 5.
382
[CHAP. IX
26. A steam superheater is to be designed to heat 10,000 pounds per hour of low
pressure process steam from 250F to 700F. The fuel is a residual cracked oil having
an API gravity of 8.6 and a viscosity of 200 Saybolt Furol Seconds at 122F. The
design bases are as foUows:
^^
Percentage excess air
40
Air temperature "F
70
Relative humidity of air
60
Stack temperature F
600
Assuming a radiation loss of 5% of the beating value of the fuel burned, calculate
complete material and energy balances for 1.0 hour of the combustion operation and
the thermal efficiency based on the total heating value of the fuel. Fig. 75 may be
used for establishing the material balance of the combustion.
CHAPTER X
CHEMICAL, METALLURGICAL, AND PETROLEUM
PROCESSES
The methods applied in calculating material and energy balances are
alike in principle for all industrial processes, differing only in detail.
Three illustrative material and energy balances are presented in this
chapter, representing the procedure applicable to chemical processes
in general. Typical illustrations in the chemical, metallurgical, and
petroleum industries have been selected. The chemical and metallurgical illustrations summarize the principles involved in dealing with
complex chemical reactions -where the intermediate courses of the
reactions are unknown. The petroleum process illustrates the use of
an energy balance to establish a material balance and the principles of
recycling to increase yield and effect temperature control. The chemical
and metallurgical processes illustrate the analysis of experimental data
from existing plants while the petroleum process is presented as a
problem in the design of a new plant.
CHAMBER SULFURIC ACID PLANT
384
80
1.8
/
-
60
><=
ST
40
-n.
20
^"^
<
'
40
60
Per Cent flaSOi
1.0
100
CHAP.
X]
M A T E R I A L BALANCE O F E N T I R E
385
PLANT
the Glover tower 1 6 % of the SO2 in the gas is converted to H2SO4. There are sprayed
into the top of the Glover tower, per 100 kg of moisture-free pyrites charged:
182 kg of aqueous sulfuric acid at 25C from the chambers, containing
64.0% H2SO4 and 3 6 % H2O.
680 kg of mixed acid at 25C from the Gay-Lussac tower, containing 7 7 %
H2SO4, 2 2 . 1 % H2O, and 0.885% N2O3.
1.31 kg of aqueous nitric acid a t 25C, containing 3 6 % HNO3 and 6 4 % H2O.
Acid leaves the bottom of the Glover tower, free from oxides of nitrogen, at a temperature of 125C, and containing 78.0% H2SO4 and 22%, H2O. This acid is cooled
to 25C, part of it is returned to the top of the Gay-Lussac tower, and the remainder
is withdrawn as the final product of the plant. The gases leaving the Glover tower
are passed through a series of four chambers and finally enter the Gay-Lussac tower,
at 40C. Spray water is introduced at the tops of the various chambers at 18C.
The acid formed in the chambers is withdrawn from the first chamber at 68C, containing 64.0% H2SO4. This acid is cooled to 25C and all fed into the top of the
Glover tower. P a r t of the Glover acid after cooling to 25C is returned to the top
of the Gay-Lussac tower. The Gay-Lussac acid leaves the bottom of the tower a t
27C and is all fed to the top of the Glover tower at 25C. The spent gases leave
the top of the Gay-Lussac tower at 30C. The flow chart of the entire process is
shown diagrammatically in Fig. 77.
HNO3 1.31 Ke
jpent Gases ^
" 4 2 3 Kg *"
(14.82 Kg Moles)
Input
Dry ore
Moisture in air
Moisture in ore
Nitric acid
D r y air
Spray water
Oiitput
Acid produced
Dry spent
Cinder
102 kg
0.78%
FejOs formed = -
0-721 kg-mole
1.442 kg-moles
0.085 kg-mole
16.95 kg-moles
U.UoO
92.2 kg
54.4 kg
389.8 kg
636.4 kg
13.81 kg-moles
17.5 kg-moles
506 kg
J
/
/
4. Weight of water vapor in dry air. The air supply enters at 18C, 49% percentage humidity, and 750 mm pressure. From Fig. 9 the molal humidity is 0.0101.
Water vapor in air = 0.0101 X 17.5 =
or 0.176 X 18 =
0.176 kg-mole
3.16 kg
CHAP. X]
387
6. H2SO1 produced in system. Sulfuric acid is formed only in the Glover tower
and in the chambers.
SO2 entering Glover tower =
1.44 kg-moles
SO2 converted to acid in Glover tower = 1.44
X 0.16 =
0.230 kg-mole
H2SO4 formed in Glover tower = 0.230 X 98.1 =
22.6 kg
H2SO4 in acid from chambers = 182 X 0.64 = . 116.5 kg
Total H2SO4 formed =
139.1 kg
or = 139.1/98 =
1.42 kg-moles
Total product of aqueous acid, 78% H2SO4 =
139.1/0.78 =
178 kg
6. Weight of spray water in chambers.
Water Balance:
Output
The small amount of water vapor in the gases from the Gay-Lussac tower may be
neglected. On this basis all water leaves the process in the 78% acid product.
H2O used in forming H2S04 = 1.42 kg-moles
or 1.42 X 18 =
25.5 kg
H2O in aqueous acid = 178 X 0.22 =
39.0 kg
Total H2O output =
64.5 kg
Input
H2O in ore = 102 X 0.02 =
H2O in air =
H2O from aqueous nitric acid = 1.31 X 0.64 =
2.04 kg
3.16 kg
0.84 kg
It is assumed that the HNO3 introduced is completely decomposed into HjO, NO, and O2.
HNO3 introduced = 1.31 X 0.36 = 0.47 kg or
0.47/63 = 0.0075 kg-mole
H2O formed from HNO3 = 0.0075/2 = 0.0037 kgmole or =
0.067 kg
Total H2O input accoimted for =
6.11 kg
Water supplied by sprays = 64.5 6.1 =
58.4 kg
7. Gases leaving Gay-Lussac tower. The gases leaving the acid plant consist of
SO2, O2, and N2 from the burner and the oxides of nitrogen which are supphed by
the nitric acid and lost from the system. Most of the SO2 and a corresponding
amount of oxygen are removed from the burner gases to form H2SO4. It is assumed
that no water vapor leaves the Gay-Lussac tower because of the great affinity of
strong, cold sulfuric acid for water.
SO2 from burner =
1.441 kg moles
SO2 forming HaSOi =
1.42 kg-moles
SO2 in gases leaving =
O2 in burner gases =
O2 used in oxidizing SOj = 1.42/2 =
O2 from burner in gases leaving =
N2 in gases from burner =
HNO3 decomposed =
0.021 kg-mole =
1.70 kg-moles
0.71 kg-mole
1.34 kg
^ ^^ ,
,,.,,,,
0.021 kg-mole
0.995 kg-mole
0.0075 kg-mole
13.81 kg-moles
Total
1.3
31.9
0.22
389.8
kg-moles
14.82
kg
kg
kg
kg
423.2 kg
Output ,
>
' .,HsO
Dry pjTites
100.0 kg
H2O in pyrites
2.04 kg
Dry air (17.42 kg-moles) 506.00 kg
H2O in air (0.176 kg-mole)
3.16 kg
Nitric acid
1.31 kg
Spray water
68.4 kg
Total
Cinder
71.2 kg
Spent gases (14.82 kgmoles)
423.2 kg
Acid (78% HzSOi).... 178.0 kg
Total
670.9 kg
fS'S.i
672.4 kg
mi
Air 506 Kg
(17.42 kg Moles)
HiO 3.16 Kg
(0.175 Kg Mole)
,5^
Dry Gas
SO,
0,
N,
''
636.4 Kg ^
1.441 Moles
1.695 Moles
13.81 Moles
Water Vapor
5.2 Kg
(0.294 Kg Mole)
;.
/
= .!./
FIG.
IKHIfeii;! y.
'
Cinders 71.2 Kg
", /
78. Material balance of pyrites bm-ner.
MATERIAL BALANCE OF BURNER
Input
Dry ore
Moisture in ore
Dry air (17.42 kg-moles)
Moisture in air
Total
,1'
Ouipvi
100 kg
2.04 kg
606. kg
3.16 kg
611.2 kg
Cinder
71.2 kg
Dry gases
536.4 kg
Water vapor (3.16 +
2.04) =
5.2 kg
Total
612.8 kg
.'d
CHAP. X]
389
The energy balance of the burner includes the heat of combustion of FeSs to FesOa
and SO2 and the enthalpy of the water vapor in the air as the only important sources
of heat. The energy output is distributed as sensible enthalpy of the outgoing cinders and dry gases and as enthalpy of outgoing water vapor. The heat losses include
radiation from the dust chamber and flues up to the entrance of the Glover tower
where the temperature of the burner gases, 450C, was measured.
1. Heat evolved in the combustion of pjrites.
The reaction involved in the combustion of pyrites and the corresponding standard
heat of reaction are as follows:
iI
.*
"
I
QOQ OCA
= 148,200 kcal
i?
Mean heat capacities between 18C and 450C taken from Table VI, page 216.
SO2 = (1.44) (11.02) = 15.8
-J.';.;. Q^ = (1.70) (7.45) = 12.6
,
,
'
aawo
, v^^
\
.; ,iKMt.in
! J "
Li
,?
'
I, . 1
Inptit
148,200 kcal
1,850 kcal
150,050 kcal
98.8%
1.2%
100.0%
Enthalpy of cinder =
Enthalpy of dry burner gas =
Enthalpy of water vapor in gases =
Heat losses (by difierence) =
Total output =
^
.\
4,900 kcal
64,700 kcal
4,110 kcal
86,340 kcal
150,050 kcal
3.3%
36.5%
2.7%
57.5%
100.0%
-t
Total
*\Sensible Enthalpy
in Cinders
'^
Total Enthalpy of
Water Vapor
3.3*
yw^r*
2.7*
Sensible Enthalpy in
Dry Burner Gas 36.S*
CHAP. X]
391
Because of the high concentration of SO2 in the Glover tower, the decomposition of
this nitrosyl-sulfuric acid is complete, forming sulfuric acid according to the equation
2H2O + 2NO2SO2OH + SO2 = 3H2SO4 + 2N0
The second reaction proceeds much more rapidly than the first in moles per unit volume of space, chiefly because it is a reaction which proceeds in the liquid phase. The
high concentration in the liquid state permits a more rapid rate of reaction, other
conditions being the same. The final concentration of the Glover acid takes place
at the hottest zone near the bottom of the tower and the acid finally leaves as 78%
H2SO4.
The input of the material balance includes the gases from the burner, the chamber
acid, the make-up nitric acid introduced, and the Gay-Lussac acid. The output
includes the Glover acid and the gases leaving to enter the chambers.
Input to Glover Tower
Basis: 100 kg of moisture-free pyrites charged.
1. Dry biu:ner gases = 16.95 kg-moles =
636.4
2. Water vapor in burner gases = 0.29 kg-mole =
5.2
; 3. Chamber acid (64% HaSOi; 36% H2O) =
182
4. Nitric acid (36% HNO3) =
1.31
5. Gay-Lussac acid (77% H2SO4; 22.1% HjO; and 0.885%
. ' N.2O3) =
580
Total input
1304.9
kg
kg
kg
kg
kg
kg
Oidput
1. Weight of Glover acid. The H2SO4 leaving the Glover tower in 78% acid includes that from the chamber and Gay-Lussac acids and that formed by conversion
of SO2 to H2SO4 in the tower already calculated to be 0.230 kg-mole.
116.4 kg
446 kg
22.6 kg
585.0 kg
750 kg
2. Weight of dry gases leaving the Glover tower. The weight and composition of
the dry burner gases in passing through the Glover tower is changed owing to the
disappearance of some SO2 and the corresponding amount of oxygen in the formation
of SO3 and to the evolution of NO and O2 due to the decomposition of nitric acid and
the release of the oxides of nitrogen from the Gay-Lussac acid.
Dry burner gases entering tower:
SO2 =
02=
N2 =
Total =
SO2 converted to H2SO4 in tower =
SO2 leaving tower = 1.44 - 0.230 =
,
O2 used in forming SO3 = 0.230/2 =
Os remaining from burner gases == 1.70 0.115 =
1.44 kg-moles
1.70 kg-moles
13.81 kg-moles
16.95 kg-moles
0.230 kg-mole
1.21 kg-moles
0.115 kg-mole
1.58 kg-moles
0.0075 kg-mole
0.0056 kg-mole
0.0075 kg-mole
0.0037 kg-mole
IJ.T'.
,5.)->
0.0675 kg-mole
0.0338
0.1350
1.62
0.143
kg-mole
kg-mole
kg-moles
kg-mole
,
77.5 kg
51.8 kg
4.29 kg
390.0 kg
523.6 kg
523.6 kg
3. Water vapor in the gases leaving the Glover tower. The weight of water vapor
in the gases leaving the Glover tower is calculated on the basis of a water balance.
Water enters as vapor in the gases, as water in the Gay-Lussac and chamber acids
and associated with the nitric acid as HNO3 and as water. The 0.230 kg-mole of
H2SO4 formed in the tower requires 0.230 kg-mole of H2O or 4.15 kg. The 78% acid
leaving requires (750) (0.22) = 165 kg water.
The 1.31 kg of 36% nitric acid charged yields upon dehydration and decomposition
0.84-1-0.07 = 0.91 kg H2O.
Water Balance:
.,
<
-,
i
Input
In gas (0.289 kg-mole) =
In chamber acid (182) (0.36) =
In Gay-Lussac acid 580 X 0.221 =
From nitric acid =
Total
6.2 kg
65.5 kg
129.0 kg
0.9 kg
200.6 kg
Output
In78%acid
In formation of H2SO4
In water vapor (by difference)
Total
165.0 kg
4.1 kg
31.5 kg
200.6 kg
.,! ,, ^,r;
31.5 kg
1.75 kg-moles
ID.78
,, ;,. ? ^)
'\
CHAP. X]
393
536.4
5.2
182.0
1.31
580.0
1304.9
kg
kg
kg
kg
kg
kg
Output
Dry gases =
Water vapor =
Glover acid (78% H2SO4) =
Total =
523.6 kg
31.5 kg
750.0 kg
1305.1 kg
HJSO*
760 Kg (787o)
Product
To Gay Lussac
178Kg
572Kg
394
mediate formation of nitrosyl-sulfuric acid. However, the net effect is the same
as though the reaction proceeded as follows:
SOj(sf) + iOiig) + HjOCO = RSOi
iJIie + (-70,920) + 0 + (-68,320) = -193,760
Affis = -54,510 kcal
/ :
. f
-20,000
-16,000
s
e
\AHJ
VlH
-10,000
-6.000
AHj^
20
40
60
Per Cent Hj SO,
80
100
CHAP. X]
395
culated from integral heat of solution data by the method discussed on page 274.
The heat evolved is the difference between the total heat evolved in forming each of
the entering acid solutions from H2SO4 and H2O and that evolved in forming the solution leaving from H2SO4 and H2O. These thermal effects may be calculated from
the integral heat of solution data plotted in Fig. 81, page 394. This curve was plotted
from data of the International Critical Tables, Vol. V, with permission.
Molal integral heats of solution of H2SO4:
>
64% H2SO4 = . . . .
77.7% H2SO4 = ..
78%H2S04 = . . .
, , .
, ,
,
,
182 X 0.64
Heat of solution of chamber acid =
X 11,800
98
= 14,000 kcal
= 39,700 kcal
^ X 8700
= 53,700 kcal'
750 X 0 78
^ X 8600 = 51,300 kcal
98
Heat absorbed in concentration of acid = 53,700 51,300
= -f-2400 keaJ
Heat of solution of Glover acid leaving =
The net heat absorbed in concentration is 2400 calories, which should be placed on
the output side of the energy balance. The large amount of heat required for the
concentration of chamber acid is offset by the heat evolved when the HaSO* formed
in the tower is dissolved.
3. Heat absorbed in release and decomposition of N2O3 from Gay-Lussac acid.
The oxides of nitrogen enter the Glover tower as recovered nitrosyl-sulfuric acid
from the Gay-Lussac tower and as make-up nitric acid. The Gay-Lussac acid may
be considered to consist of 0.0677 kg-mole of N2O3 dissolved in 129 kg (7.15 kg-moles)
of water. This concentration corresponds to 106 moles of water per mole of N2O3.
The thermal effects in the evolution of the N2O3 from solution and its decomposition
may be calculated from the following thermochemical data:
Formula
'initt
State
W>IG
NO
NsOs
NO2
N2O4
N2O6
HNO,
9
gQ
9
9
9
I
Heat 0/ Formation
'"ZZZUZZ"
kcal per kg-mole
-1-21,600
-f 20,000
20,000
-f
-1-8,030
-1-3,060 '
-f600
-41,660
-41,660
Moles
JZ'^L
of
Water
Heat of
Solution,
kcal
100
-28,900
6.22
-7,000
396
imation. However, in view of the relatively small heat effects involved these approximations seem justified.
>
1> ' -i i <>,1
NjOs = 2N0 + i02
'
AHB
'
.'
'
= 23,200 kcal
Vtl-V
>'
,',.,;.(,-
= 29,100 kcal
52 kcal
218 kcal
270 kcal
12
',.'J 1 1 [ 1 1 1
- r^
Cp = Total
r> i Heat
' l T j Capacity,
in
*cal/gi
f u ./ Cn~Ttrrr
= ;^ = = = -
^s__-__rr
_r _
:~
~ - ^ CV^ :
V-
==5==:F:::::E::::::iE:
^^Pi
fJ -
^^
*N j ^
E 0.8
__ _
'
-"*^s.
^ ^
^5>^
_L_-
i.^
^r
-^v^^
CD
1 i ~
_C_
:i:
A
-ju
:!-~>^
^ - __ _ s^
St--^
i t __-_ :- tI
^ ^ ^
*
*-
a
g
o
^^
^'^
ae
^-*^
Cp2
s ^
"^^
K
^^
Zm
*"*
1
''
""
o.ot 1111.1.11 11.1-1,1111111 111 U 11:___:
0.
20,
go
40
50
60
;:_,_;___;;__;::
70
go
90
Percent H>SO
Pra. 82. Partial and total heat capacities of aqueous solutions of
sulfuric acid a t 20Cj
100
V
CHAP. X]
397
6. Heat input in burner gases. This has already been calculated as the heat
output of the burner, page 390, =
58,810 kcal
6. Enthalpy of chamber acid.
Specific heat (from Fig. 82) =
Enthalpy = 182 X 0.50 X ( 2 5 - 1 8 ) =
0.60
640 kcal
0.45
1830 kcal
This calculation neglects the effect of the oxides of nitrogen on the heat capacity
of the Gay-Lussac acid.
8. Enthalpy of nitric acid. Prom Fig. 41, page 224, the specific heat of 36%
nitric acid is 0.70.
Enthalpy = 1.31 X 0.70(25 - 18) =
7 kcal
(1.21) (9.76)
(13.81)(6.97)
(0.14) (7.16)
(1.62) (7.05)
= 11.8
= 96.4
= 1.0
= 11.4
120.6
..".',..
is,,,
' " '""'
" \
-.-j "
8810 kcal
19,500 kcal
2310 kcal
54,700 kcal
4,110 kcal
640 kcal
1,830 kcal
7 kcal
12,530 kcal
73,817 kcal
74.0%
5.6%
0.9%
2.5%
0.0%
17.0%
100.0%
8,810 kcal
19,500 kcal
2,310 kcal
2,400 kcal
270 kcal
11.9%
26.4%
3.1%
3.3%
0.4%
3,530 kcal
33,000 kcal
3,997 kcal
73,817 kcal
4.8%
44.7%
5.4%
100.0%
5.6T
Enthalpy of
Water Vapor
Enthalpy in
Chamber Acid
2 . 5 ^ Sensible Enthalpy
in Gay Lussac Acid
0.0?&
100.0%
Sensible Enthalpy _
in Nitric Acid
Total
>5^_,Heat of
Concentration of H2SO4
*c
3.3?^
Total Enthalpy in
Water Vapor 26.49!>
Release and De'
composition of No O3
from G.L. Acid
4&f,
^ Concentration and Decomposition of HNO3
0.456
1 Sensible Enthalpy
J
in Dry Gas
11.9*
_ Enthalpy of Acid
leaving Cooler
3.1*
Heat Absorbed in
Cooling of Acid
44.7*
^
5.4*
J Radiation
Total
100.0*
CHAP. X]
399
It will be seen that over one-half of the available energy in the Glover tower
is absorbed by the concentrated acid. This acid must be cooled before it can be
used for absorption of gases in the Gay-Lussac tower and before storage. The cooling of this acid represents one of the difficult problems in acid manufacture, in the
development of a heat interchanger which will withstand hot concentrated sulfuric
acid and at the same time permit a rapid transfer of heat.
MATERIAL BALANCE OF CHAMBERS
It would be proper to consider the material and energy balances of each chamber
separately, but to avoid needless repetition all four chambers will be considered as
a unit. In the chambers, H2O, SO2, and O2 are removed from the gases to form
HzSO*.
Basis: 100 kg of dry pyrites charged.
H2SO4 formed in chambers = 116.5 kg or 1.19 kg-moles.
Oas Entering
SO2
1.21 kg-moles
O2
1.62 kg-moles
NO
0.143 kg-mole
N2
13.81 kg-moles
H2O
1.75 kg-moles
Total =
Gas Removed
1.19 kg-moles
0.595 kg-mole
1.19 kg-moles
15.00 kg-moles
Water vapor leaving. The water entering with the gases and from the sprays is
used in the formation of H2S04 and dilution of the H2SO4 to form the chamber acid.
Water input
H2O from gases =
H2O from sprays =
Total =
'.
Water output
H2O to form H2SO4 = 1.19 X 18 =
H2O in chamber acid = 182 X 0.36 =
Output accounted for =
H2O in gases leaving = 89.9 - 86.9 =
or 3.0/18 =
Moles of dry gases leaving =
MoM humidity = 0.167/15.0 =
Dew point (Fig. 9) =
31.5 kg
68.4 kg
89I9 kg
21.4 kg
65.5 kg
86.9 kg
.^
3.0 kg
*.. 0.167 kg-mole
15.0 kg-moles
0.011
46F or 8C
400
C H E M I C A L , M E T A L L U R G I C A L , P E T R O L E U M PROCESSES [CHAP. X
ENERGY BALANCE OF CHAMBERS
The first reaction proceeding in the chambers is. a gaseous reaction between the
SO2, H2O, O2, and NO gases in contact with the water spray forming nitrosyl-sulfuric
acid.
2SO2 + 2NO + IJO2 + H2O -* 2NO2SO2OH
\: .ia hai'.hhk
This reaction is favored by high concentrations of SO2 and NO. The acid spray is
swept against the side walls of the chamber where the spray is condensed owing to
cooUng, and by dilution with water H2SO4 is formed with the release of the oxides
of nitrogen, .jj ^,,j
..,,
. ,
'^'^^s*^
-M-^^'S -.
The first of these reactions proceeds in the liquid phase and is favored by a high concentration of water brought in by the spray and condensed upon the side walls.
Water Sprayed
58.4 Kg
O/i.
r
Dry Gas 428.4 Kg
SO2 0.021 X; Mole
Oj 1.025 Kg Mole
N, 13.810 Kg Moles
NO O.I4SKgMole
^
Water Vapor 3.0 Kg
0.167 Kg Mole
Acid 182.0 Kg
F I G . 84.
();H
r!.:/i ntj' OS
tOrfl
In calculating the heat evolved in the chamber reactions only the final, net effects
need be considered. It will be assumed t h a t the oxides of nitrogen ultimately leave
the chambers in the same form in which they entered, NO. This assumption is not
exact because some oxidation of NO to N2O3 probably takes place at the relatively
low temperatures of the last chamber. The ultimate effects of the reactions in the
chambers are then the production of H2SO4 from SO2, O2, and H2O and the dissolution of this acid to form an aqueous solution containing 6 4 % H2SO4.
Reference temperature: 18C.
Basis: 100 kg of dry pyrites charged.
T!'!(<
64,870 kcal
2. H e a t evolved in dissolving H2SO4. Integral heat of solution (Fig. 81) a t a concentration of 6 4 % H2SO4 = 11,800 kcal per kg-mole.
Heat evolved in dissolution = 11,800 X 1.19 =
14,050 kcal
jog If
CHAP. X]
401
3. Enthalpy of dry gases and water vapor entering. This has already been calculated as part of the heat output of the Glover tower =
28,310 kcal
4. Enthalpy of spray water. Since the spray water enters at the reference temperature, 18C, its enthalpy is equal to
0 kcal
5. Enthalpy of dry gases leaving.
Mean heat capacities between 18C and 40C taken from Table VI, page 216.
'"
',
SO2
O2
N2
NO
I
(0.021)0.49)
(1.025) (7.02)
(13.81) (6.97)
(0.14)(7.16)
Total
= 0.2
= 7.2
= 96.4
= 1.0
= 104.8
.
.;
'^o^ate
,_.
'
1790 kcal
7. Heat absorbed in cooling the acid leaving. Heat capacity (Fig. 82) of acid
containing 64% H2SO4 = 0.50 kcal per kg per C.
Enthalpy = 0.50 X 182(68 - 25) =
3920 kcal
640 kcal
Inrivi
^
-l
;w
...
8,810 kcal
19,500 kcaJ
0 kcal
64,870 kcal
14,050 kcal
107,230 kcal
8.2%
18.2%
0%
60.5%
13.1 %
100.0%
2,310 kcal
1,790 kcal
640 kcal
3,920 kcal
98,570 kcal
107,230 kcal
2.2%
1.7%
0.6%
3.7%
91.8%
100.0%
Ouiyvii
Enthalpy of dry gases leaving
Enthalpy of water vapor in gases
Enthalpy of acid leaving the cooler
Heat absorbed by cooler
Heat loss from chambers (by difference)
Total
Formation of HjSO^
&2
Enthalpy oJ
|
Dry Gaa '
13.1^
Dissolution
of H , S O ,
18.2?> Enthalpy of
Water Vapor
I00.0?6
Total
sV
^^
, Enthalpy of
Dry Gae
2.2*
. Enthalpy of
'
Water Vapor
1.7*
1 Heat Removed in
Cooling A d d
3.7*
. Enthalpy of A d d
after Cooling
0.6*
Radiation Loss
Total
913*
100.0*
CHAP. X]
403
O2 in gases leaving:
NO oxidized to N2O3 = 0.143 - 0.008 =
0.135 kg-mole
O2 consumed = 0.135/4 =
0.034 kg-moIe
O2 leaving = 1.025 - 0.034 = 0.991 kg-mole = . 31.7 kg
Summary of Material Balance of Gay-Lussac Tower.
Input
SO2 (0.021 kg-mole)
O2 (1.025 kg-moles)
N2 (13.81 kg-moles)
NO (0.143 kg-mole)
H2O (0.167 kg-mole)
Glover acid
Total
1.3 kg
32.8 kg
390.0 kg
4.3 kg
3.0 kg
572.0 kg
1003.4 kg
Output
SO2 (0.021 kg-mole)
O2 (0.991 kg-mole)
N2 (13.81 kg-moles)
Acid leaving
NO (0.008 kg-mole)
Total
1.3 kg
31.7 kg
390.0 kg
580.0 kg
0.2 kg
1003.2 kg
572 Kg
Dry Ga8
423 K g ^
m
SO, 0.021 Kg Mole
Ot 0.991 Kg Mole
Ni 13.810 Kg Moles
KO 0.008 Kg Mole
DiyCas
SOt
Oi
N,
NO
428.4 Kg
FIG.
Acid SeOKg
86. Material balance of Gay-Lussac tower.
620 kcal
1760 kcal
4100 kcal
Enthalpy = (103.2) ( 3 0 - 1 8 ) =
= 0.2
= 6.9
= 96.1
= 0.0
ao
Sir-
-!
.'.; . . . .
1240 kcal
620 kcal
tH^:
t m
">
Sensible Enthalpy
in Glover Acid
">
'K
!'>>/'(
ts*E -I
Sensible Enthalpy to
Gases Leaving 12.6%
1 Heat Removed in
CooUng Acid
6.2%
Enthalpy of Acid
after Cooling 18.6%
-Radiation Loss 635%
Total
100.0%
1830 kcal
CHAP. X]
405
2310 kcal
1790 kcal
1760 kcal
1570 kcal
1960 kcal
520 kcal
9910 kcal
23.3%
18.1%
17.7%
15.9%
19.8%
S.2%
100.0%
1240 kcal
520 kcal
1830 kcal
6320 kcal
9910 kcal
12.5%
5-2%
18.5%
63.8%
100.0%
Out-put
Enthalpy of gases leaving =
Heat absorbed in cooling acid =
Enthalpy of acid leaving cooler =
Heat loss (by difference) =
Total =
This energy balance is shown diagrammatically in Fig. 87.
SUMMARIZED ENERGY BALANCE FOR ENTIRE PLANT
1.
2.
3.
4.
5.
6.
7.
Input
61.2%
0.8%
5-2%
0.0%
26.8%
5.8%
0.2%
100.0%
Outpitt
1. Enthalpy of cinder
4,900 kcal
2. Net heat absorbed in concentrating acid in Glover
tower
2,400 kcal
3. Concentration and decomposition of nitric acid. . . .
270 kcal
4. Radiation losses from burners
86,340 kcal
Radiation losses from Glover tower
3,997 kcal
Radiation losses from chamber
98,570 kcal
Radiation losses from Gay-Lussac tower
6,320 kcal
5. Cooling of Glover acid
33,000 kcal
Cooling of chamber acid
3,920 kcal
Cooling of Gay-Lussac acid
520 kcal
6. Enthalpy of acid product 178(0.44)(25-18)
650 kcal
7. Enthalpy of spent gases leaving Gay-Lussac tower
1,240 kcal
Total
242,027 kcal
2.0%
1.0%'
0.1%
36.7%
1-7%
40.8%
2.6%
13.6%
1.6%
0.2%
0.2%
0.6%
100.0%
0.2%
2.0%
1.0%
y*^*^
0.1%
1.7%
ii-
Radiation from
^
Gay Lussac Tower 2.6%
) Cooling Glover Acid
' Cooling Chamber Acid
.'
.:
13.6*
1.6%
A blast furnace is essentially a huge gas producer where, in conjunction with the partial combustion and distillation of a carbonaceous fuel,
the reduction of ore and the formation of slag occur simultaneously.
The charge, consisting of iron ore, coke, and Hmestone in proper proportions, is fed into the top of the blast furnace. Preheated air, preferably
free from water vapor, is blown through the tuyeres near the bottom of
the furnace into the descending stream of solids. This results in combustion of the coke to carbon dioxide. The carbon dioxide gas in the
presence of excess coke is reduced at the high prevailing temperature to
CHAP. X]
407 "
charge is distilled off near the top of the furnace and escapes into the
blast furnace gas without reduction.
^
The slag contains all the lime, magnesia, alumina, and alkalies originally present in the ore and flux, together with most of the silica and some
ferrous and manganous oxides. The exact mineralogical compositions
of ore, flux, and slag are usually not known completely, so that some
uncertainty exists concerning the exact thermal energy involved in reduction and chemical transformations. The molten pig iron contains, in
addition to iron, some carbon present as cementite and lesser amounts
of silicon and manganese,
cooling, the cementite partly decomposes
into graphite and iron.
In order to establish the energy balance of a blast furnace it is necessary to know the masses and chemical compositions of the ore, flux,
dust, and pig iron, and the analysis of the dry blast-furnace gas. The
masses of slag, air, and water vapor can then be calculated.
The material balance includes:
-i
Input
.
Iron ore
,
Flux
,
I . , ,.
Coke
,
,,
,;.,;,;,. pfMr
,; ,^j
Output
Dry gases ,
Water vapor in gases
Pig iron
Dust
^. ,
,< ,.
-.i
, . ;
Slag
54.93%
8.48%
9.58%
4.97%
3.00%
1.83%
4.92%
4.48%
7.81%
100.00%
.^
86.89%
3.13%,
0.45%
0.51%
7.00%
2.00%
100.00%
/:
CHAP. X]
78.38%
13.99%
0.53%
3.90%
3.20%
100.00%
409
3.12%
1.52%
2.22%
93.14%
100.00%
The total heating value of the charcoal is 7035 kcal per kg.
The clean gas produced has the following composition by volume on the moisture
free basis:
CO2
..?....
12.62%
CO
;
25.56%
CHi
0.69%
' ' '
Hs
1.34%
N2
59.79%
:'!' '
100.00%
- = ' - < The ore, flux, and charcoal are charged to the furnace at an average temperature
of 18C. The air blast is dried and enters the tuyeres at a temperature of 300C
and moisture-free.
The gases leave the furnace at a temperature of 173C and contain only negligible
quantities of dust.
The slag and pig iron are poured at an average temperature of 1360C.
In order to cool the outside of the bosh of the furnace and thereby protect the refractories frorn excessive heating, water is circulated in a pipe passing around the
circumference of the bosh. On the basis of 100 kg of pig iron produced 576 kg of
water are circulated and heated through a temperature rise of 13C.
Calculate the complete material and energy balances of this furnace.
..,.!..,.i..v-J
t " i (V
MATERIAL BALANCE
-) v
410
tion is somewhat inexact because it is kn/ ym that a part of the iron exists as metaUic
particles included in the slag.
Sufficient siUca is reduced to metallic silicon to supply the siHcon content of the
pig iron. The remainder combines with the basic oxides to form silicates in the slag.
The MnaOi of the ore is in part reduced to metaUio manganese, supplying that present in the pig iron. The remainder of the manganese is assumed to enter the slag
as MnO, forming silicates.
The oxygen given up in the reduction of the oxides of iron, silicon, and manganese
will be present in the gases as CO, CO2 or II2O. The gases also contain the CO2
and H2O of the ore.
Basis: 100 kg of pig iron produced.
Distribution of Fe203 and FeO:
/
1 1 fi s?
0.732 kg-mole
0.2516 kg-mole
rt; %
y*-'*'
1.7155 kg-atoms
1.669 kg-atoms
0.0465 kg-atom
3.33 kg
1.223
0.023
1.20
38.4
kg-moles
kg-mole
kg-moles
kg
' '-
0.174 kg-mole
'
0.054 kg-atom
0.120 kg-atom
7.2 kg
1.7 kg
Distribution of MusOi:
MnaOi in ore = 21,2.7 X 0.0497 = 10.57 kg or ^ = 0,0462 kg-mole
228.8
Mn in ore = 0.0462 X 3 =
0.1386 kg-atom
/
2.22
/'
Mn into pig iron = 2.22 kg or =
0.0405 kg-atom ;
54.9
/
Mn into slag =
0.0981 kg-atom
MnO into slag = 0.0981 kg-mole or 0.0981 X 70.9 = . .
6.95 kg
,;:
Oxygen in MnsOi of ore = 2 X 0.0462 =
0.0924 kg-mole
Oxygen in MnO of slag = X 0.0981 =
0.0491 kg-mole :
Oxygen into gases =
0.0433 kg-mole
or 0.0433 X 32 =
. 1.38 kg
/
/
/
/
'
CHAP. X]
411
0.529 kg-mole
93.14 kg
2.22 kg
1.52 kg
-
Feb =
T
SiOz =
MnO =
CaO = 212.7 X 0.0958 =
AI2O3 = 212.7 X 0.0300 =
MgO = 212.7 X 0.0183 =
3.33
7.2
6.96
20.4
6.4
3.9
kg
kg
kg
kg
kg
kg
Into gases:
62.0 kg
4.54 kg
1.06 kg
'212.6 kg
Distribution of Flux Materials. Since it has been assumed in the preceding calculations that all the iron, manganese, and silicon of the pig iron were derived from the
ore materials, all the materials of the flux must pass into the slag or the gases. The
silica, lime, and alumina enter the slag unchanged. It will be assumed that the ferric
oxide is reduced to FeO and enters the slag in this form. The oxygen evolved in the
reduction of the iron oxide and the water present in the flux enter the gases.
Basis: 100 kg of pig iron produced.
Distribution of iron oxide:
FeaOs in flux = 13.9 X 0.0390 = 0.542 kg or
FeO into slag = 2 X 0.0034 = 0.0068 kg-mole or
O2 into gases = i X 0.0034 = 0.0017 kg-mole or
0.0034 kg-mole
0.49 kg
0.05 kg
Distribution of water:
H2O in flux = 13.9 X 0.0320 = 0.445 kg or
H2 into gases = 0.0247 kg-mole or
O2 into gases = i X 0.0247 = 0.0123 kg-mole or
0.0247 kg-mole
0.05 kg
0.39 kg
10.90
1.95
0.07
0.49
kg
kg
kg
kg
. ,0 )
Into gases:
'
0 = 0.05+0.39=
H=
'
Total =
0.44 kg
0.05 kg
13.90 kg
u^, ,|
,. ,;\-v
,"',
'-'.'''
'
Distribution of Charcoal. The carbon in the pig iron will be assumed to be derived
from the charcoal. The ash enters the slag while the remainder of the charcoal
constituents passes into the gases.
Distribution of water.
' '
: '
" v s .
.;.,
H2O in charcoal = IIO.O X 0.0700 = 7.70 kg or
H2 into gases = 0.428 kg-mole or
O2 into gases = 0.214 kg-mole or
i .
3.12 kg
Into gases:
M- >
'
'
'
'
'
92.44 kg
1.36 kg
10.32 kg
0.56 kg
' "
Into slag:
I
= Tf
Ash = 110.0 X 0.02 =
2.20 kg
Total =
110,00 kg
Weight and Composition of Slag. Since it may be assumed that the slag contains
only materials derived from the ore, flux, and charcoal, its total weight and composition may be obtained by adding together the weights of materials entering the slag
from these three sources. Actually these materials are in the slag in the form of
complex compounds.
Component
FeO = 3.33 -f-0.49
SiOj = 7.2 + 10.90
MnO =
CaO = 20.4 + 0.07
AI2O3 = 6.4 -1- 1.95
MgO =
Ash =
Total =
Weight, kg
3.82
=... .
= . . . 18.10
6.95
= . . . 20.47
8.35
=... .
3.90
.
2.20
63.79 kg
Percentage
6.0
28.4
10.9
32.1
13.1
6.1
3.4
100.0%
Kg equivalents
0.106
, , 0.602
.,,
0.196
/
,, 0.730
0.246
*
0.194
CHAP. X]
413
0.57
0.57
1.14
0.66
kg
kg
kg
kg-mole
11.9 kg
17.66 kg
5.76 kg
0.320 kg-mole
Output
212.7 kg
13.9 kg
110.0 kg
456.0 kg
792.6 kg
Slag
63.8 kg
Dry gas (20.78 kgmoles)
617.8 kg
Water vapor in gas
(0.66 kg-mole). .
11.9 kg
Pig iron
100.0 kg
Total
793.5 kg
Charcoal llO^) Kg
Flux
13.9 Kg 1
Or 212.7 Kg
Air 456 Kg
(16.72 Moles)
CHAP. X]
415
oxides by carbon and by carbon monoxide, and the reduction of water to carbon
monoxide, hydrogen, and carbon dioxide. However, in any chemical process the
total change in energy is dependent only upon the initial and final states of chemical
constitution, temperature, pressure, and state of aggregation and is independent of
any intermediate state. Hence, in calculating the energy balance of a blast furnace,
the numerous intermediate reactions involved need not be considered. It is sufficient
to know the temperature, state of aggregation, and composition of each material
charged and each product formed, without knowing how the various components of
the products are actually produced.
The oxides of calcium, magnesium, and aluminum pass through the furnace apparently unchanged so that the heats of formation of these oxides need not be considered,
but the state of the oxide is much different in the slag from that in the ore or flux.
For example, in the ore, the oxides of iron and manganese exist as oxides but in the
slag as silicates, so that the net heat effect accompanjdng the formation of silicates from the oxides should be considered. However, accurate calculation of this
quantity requires data which are not ordinarily available.
The energy balance is calculated with a reference temperature of 18C, based on
100 kg of pig iron produced.
1. Heat absorbed in reduction of iron oxides at 18C. The heat absorbed is
obtained by subtracting the total heat of formation of the reactants from that of the
products. Iron oxides enter the process in both the ore and the flux. The necessary heat of formation data are obtained from Table XIV, page 253.
^ ,
Reactants
v
,
Kg-moles
FejOa
FeO
0.735
0.2515
nr 1 J IT J t
Molal Heat of
_
,.
Formation
-198,500
- 64,300
Total =
i
Products
Fe
FeO
Oxygen
Total Heal of
r,
.
Formation,
, ,
'
kcal
-145,900
- 16,170
-162,070 kcal
1.669
0.0533
1.25
0
-64,300
0
-3,430
0.0462
345,000
Products
Mn
MnO
Oxygen
0.0405
0.0981
0.0433
0
-96,500
0
'
4-168,640 kcal
Total Heat of
Formation,
j? , ,-, '
kcal
-15,940 kcal
-9470 kcal
4-6,470 kcal
416
'
Si02 reduced
Products
Si
O
IT
,
Kg-moles
0.054
Kg-atom
0.05*
0.054
>T . 7 rr 1 t
Molal Heat of
_
^.
Formation
-203,340
-".'"i-tlwT
. m
Total Heal of
^. '
Formation,
, , '
kcal
- 1 0 , 9 8 0 kcal
'0
0
i>
'
^'
+10,980 kcal
0.378 kg-mole
Kg-moles
0.364 kg-mole
0.097 kg-mole
0.364 kg-mole
0.014 kg-mole
0.083 kg-mole
M 7 1 Tf
f
^.
Formation
CaCOs
0.364
-289,500
MgCOs
0.014
-268,000
'
, ;:, : :
i -'
'^'' ''-'''''
-3,750
-109,150 kcal
'' \
s ,'^ .,
0.378
0.364
0.014
-94,030
-151,700
-146,100
,,
' .iff.)
Total Heat of
Formation,
,
, , '
kcal
-105,400
Total =
Products
C0
CaO
MgO
' '
- '
' s ,
t*>itJMnH
- 3 5 , 5 4 0 kcal
- 5 5 , 2 2 0 kcal
- 2 , 0 4 0 kcal
Total =
Heat evolved in calcination = - 9 2 , 8 0 0 -|- 109,150 =
- 9 2 , 8 0 0 kcal
+16,350 kcal
6. Heat evolved in the partial combustion of charcoal. The purpose of introducing charcoal into the charge is to furnish heat for all endothermic reactions involved in
reduction, to supply heat for producing the slag and pig iron in a molten state, and to
supply carbon for the reduction of the various metaDic oxides of the ore. The charcoil is not burned completely to carbon dioxide and water vapor, and its total heating
value is not rendered available in the blast furnace. The actual products resulting
from the partial combustion of the charcoal include carbon dioxide, water vapor,
carbon monoxide, methane, and hydrogen in the outgoing gases and graphite in the
solidified pig iron.
Since the heats of formation of the materials making up the charcoal are not known
it is necessary to calculate the heat evolved in its partial combustion from standard
heat of combustion data. As pointed out in Chapter V I I I , page 267, the heat evolved
CHAP. X]
417
in a reaction is the difference between the sum of the heats of combustion of the
products and that of the reactants. The actual reaotants entering into the combustion of the charcoal include carbon dioxide, water vapor, and oxygen from both
the air and the ore. However, the heats of combustion of these materials are
zero, and they need not be considered in calculating the heat of reaction.
Heat of combustion of charcoal = 110.0 X -7035 =
Product
CO
CH,
Hj
Graphite =
Kg-moles
Molal Heat of
^ i ^.
Combustion
5.30
0.14
0.28
0.26
-67,410
-212,805
-68,320
-94,030
Total =
-773,850 kcal
Total Heat of
Combustion,
, ,
kcal
-357,300
-29,790
-19,130
-24,450
-430,670 kcal
)ijt ^- ,
343,180 kcal
6. Heat evolved in formation of slag. Blast-furnace slags consist of complex mixtmes of silicates and aluminates of calcium, magnesium, iron, and manganese. In
order to calculate the heat of reaction accompanying the formation of a slag it would
be necessary to determine the complete mineralogical composition of the ore, flux, and
slag, together with the heats of formation of all the compounds present. Such data
are rarely available, and it is ordinarily necessary to neglect the heat evolved in forming the slag from the oxides. It would not be expected that this thermal effect is
large. The formation of the monosilicate of calcium, manganese, iron, or magnesium
from Si02 and the respective oxide is in every case accompanied by an evolution
of heat. On the other hand, the formation of dicaleium silicate is accompanied
by an absorption of heat. These effects will frequently tend to compensate each
other.
/:
" ; . ! ; ? ,
-ill
1-1
'XM!
v J i i : ;
l i
:./.
: '
-I!
'
.,.--:,
,...,
-H"-' Enthalpy of air = 15.72 X 7.06(300 - 18) =
31,300 kcal
23,290 kcal
12. Enthalpy of pig iron. The average enthalpy of molten pig iron from blast
furnaces has also been determined by S. Umino.' Although the composition of the
pig iron used in his experiments is not identical with the one under discussion, nevertheless the compositions are sufficiently alike to justify use of the same values of
enthalpy. At a pouring temperature of 1360C this enthalpy is 300 kcal per kg and
includes the sensible enthalpy of the solid and liquid states, the latent heat of fusion,
and the heat evolved in the separation and decomposition of cementite, FeaC, from
solution in the iron.
Total enthalpy of pig iron = 100 X 300 =
30,000 kcal
7,490 kcal
,
Input
343,180 kcal
31,300 kcal
374,480 kcal
91.6%
8.4%
100.0%
/ /
'/
/
CHAP. X]
419
1 1
Open Hearth Slags -
400
//
800
A4
M.P^
200
y^
f*ureIro 1
J^i
W
100
200
400
1000
1200
1400
1600
00
300
34.50
1.58
0.29
40.92
3.90
trace
0.98
2.24
15.48
2.80
niion of Slags
^urnace Slags
2
3
34.22
37.26
0.82
0.74
0,20
0.84
43.15 41,80
1.80
4.56
trace
trace
0.11
0.90
1.88
1.82
15.60
13.15
2.97
2.94
Heat
Heat
Heat
Heat
SiOj
FeO
FeiOa
CaO
MgO
P
S
MnO
AI2O3
Apparent ep. gr. 20C
Composition of Pig Iron
C = 4.31%
Si = 1.11%
Mn = 0.63%
P = 0.12%
S = 0.022%
Cu = 0 . 2 1 %
of
of
of
of
Open
4
18.20
13.45
2,40
42,63
9.14
0.33
0.54
6.97
5.00
3.46
Hearth Slags
5
6
18,28 20,28
10.27
10.47
3.63
2.50
43.56
44.20
11,84
10.47
0.25
0,25
0.45
0.40
6.60
6.60
4.68
4.79
3,56
3.12
FiQ. 90. Enthalpies of iron and slags, referred to 18C. Data taken from S.
Umino, Soence iJepte. T6hoku Imp. Univ., 17, 985 (1928) for slag; 16, 675 (1927)
for pig iron; 18, 91 (1929) for pure iron.
158,640 kcal
6,470 kcal
10,980 kcal
16,350 kcal
23,640 kcal
7,790 kcal
23,290 kcal
30,000 kcal
7,490 kcal
89,830 kcal
42.4%
1.7%
2.9%
4.4%
6.3%
2.1%
6.2%
8.0%
2.0%
24.0%
374,480 kcal
100.0%
Total
IPal/'infitmn of Carbonatcs
U%
3 Reduction of SiOtto Si
2.9*
3.Redaction of Mnj04
1.7%
6.3*
2.1*
6.2*
8.0*
2.0*
3 Heat Removed by
Cooling Water
- Losses Unaccounted for
24.0*
Total
100.0*
CHAP. X]
421
In a so-called " vapor phase cracking " process a clean, well fractionated gas oil cut from petroleum, containing no material of gasoline
boiling range, may be decomposed to form gasoline and gas by heating
in the tubes of a furnace designed to provide the necessary reaction tune
at elevated temperatures. In order to arrest the reaction and minimize
coke formation, the hot vapor mixture of gas, gasoline, oil, and tar from
the heater is " quenched " by a relatively cool stream of oU. The resulting mixture passes to an evaporator where further cooling and rough
fractionation is accomphshed by means of a reflux stream of cool oil
sprayed in at the top of the vessel. The quantity of reflux is regulated
to obtain such a temperature in the evaporator as to produce the desired
quality of " tar " which is withdrawn from the bottom of the evaporator
and generally sold as heavy fuel oil.
The vapors from the evaporator pass to a fractionating tower the
lower section of which is utilized for preheating the fresh charge by
direct heat exchange. This tower is operated to produce well fractionated gasoUne and gas as the overhead product. All partially decomposed
feed in the boiling range between gasoline and the tar is condensed as
a bottom product. This " recycle stock " mixes in the bottom section
of the tower with the fresh feed to form the " combined feed," part of
which is charged to the furnace, part used for quenching the hot vapors
leaving the furnace, and part used as a reflux in the evaporator. It
may be assumed that the mixture leaving the furnace is completely
vaporized and that negligible condensation is produced by the quench.
It may also be assumed that all the oil used for quench and reflux is
vaporized under the conditions of the evaporator forming no tar.
Illustration 3. The flow diagram of such a process is shown in Fig. 92, on which
are indicated significant temperatures and characteristics of the streams. The
furnace is of the gas-fired type, provided with both radiant and convection heating
sections. An air preheater transfers heat from the stack gases to the air used for
combustion.
The gas used for heating the furnace is supplied at 65 F and has the following
composition by volume:
CH,
CaHe
CO
Hj
Nj
14.6%
77.3
1.2
6.1
0.8
The temperatures shown on the flow diagram are either arbitrarily set as bases
for design or are derived from previous pilot plant or commercial experience indicating the temperatures necessary for the desired reaction rates and separations.
Pilot plant tests indicate that when cracking a gas oil having a gravity of 29API
61.0%
24.5
.
"
It may be assumed that the operation is conducted with 100% material recovery
and that the yield of gas is determined by difference.
Fractionating
Tower
290 F.
J-Crondenser^j^^.j 2 sp-S
4
Gas Separator
Gasoline
C><h*-58API
U.9 K.
Fresh Feed
29 API Gas Oil
U.8K.
CHAP. X]
423
assumed that they are sufficiently low that all enthalpies may be taken as at atmospheric pressure.
In calculating the enthalpies of mixtures, heats of mixing in both gas and liquid
phases may be neglected and also the effect of pressure upon enthalpies and upon the
heat of cracking. It should be noted that the characterization factors and degrees
API are additive on a weight basis.
The following information is required: All flow rates should be expressed in
pounds per hour and in barrels per day (at 60F) for the hquids and in cubic feet
(at 60F, 30 inches Hg, saturated) per hour for the gas. Heat rates should be
expressed in Btu per hour.
(a)
(6)
(c)
(d)
(e)
(/)
(g)
(h)
(i)
(j)
(k)
(0
SOLUTION
For ready reference the physical and thermal properties of the various petroleum
fractions are tabulated in Tables A and B. The characterization factors and degrees
API of a mixture are additive properties on a weight basis. The average molecular
weights and boiling points are obtained from values of API and K by use of Fig. 63.
Latent heats of vaporization are calculated from Equation (32), Chapter VII,
page 233. The mean specific heats of liquids and vapors are obtained from Figs.
66 and 67. Enthalpies at various temperatures are then calculated from the above
data using 65F as the reference temperature.
All calculations are based upon 1 hour of operation.
TABLE A
PHYSICAL PROPERTIES or OIL FRACTIONS
Gasoline
Tar
Fresh Feed
Recycle
Gas
Combined Feed
(calculated)
"API
58.0
2.0
29.0
19.0
11.9
10.2
11.8
10.7
22.1
G
60/60
0.747
1.06
0.88
0.940
1.22 (air)
11.04
0.922
Av Molecular Av Boiling
Weight
Point F
109
320
300
220
240
800
675
560
.240
585
424
TABLE B
THEHMAL PEOPEETIBS OF OIL FRACTIONS
Mean
H e a t of Specific H e a t
Boiling
Vaporiof Liquids
Point
zation
(65 to tF)
F
Btu/lb
fF
Op
Gasoline
.-u-i
134.8
240
95
240
0,475
0.518
150
745
800
U.377
0.620
0.528
>.U
":<>
Tar
.1
Mean
Specific H e a t
of Vapors
(240'' to fF)
fF
tV
fF
Btu/lb
290
710
800
1000
0.464
0.574
0.596
0.640
95(0
240(0
240 (y)
290 (w)
710
800
1000
14.3
90,7
225.5
248.7
495.2
559.0
711.7
(800F to tF)
800 0.620
1000 0.660
150(0
745(0
800(0
800(6)
1000(tf)
43,4
353.6
388.1
488.1
620.3
95
290
710
800
1000
13.3
112.1
392.3
463.0
631.3
800
100
(65F
95
290
710
800
1000
Gas
Presh Feed
675
Combined
Feed
585
Recycle
560
88
200
0.464
300
540
585
0.462
0.523
0.634
560
0.519
104.4
110.6
Enthalpies
65 F reference
to f F )
0.444
0.498
0.608
0,630
0,676
200
(585F t o fF)
710 0.610
800 0.630
710
800
1000
0.586
0.605
0.644
200(0
62.6
300(0
540(0
585(0
685 (w)
710 (t))
800 (w)
108.6
248.4
277.7
382.1
458.5
517.4
560(0
256.9
367.5
455.3
512.7
650.7
560(D)
710 ()
800 ()
1000(f)
CHAP. X]
425
1. Rates of Production. Rates of production are calculated from the yield statement, as follows:
Charge
Tar
Gas
Gasoline
Bbl/day
6000
1225
3050
Gal/hr
8750
5340
2145
Sp. gravity
0.882
0.747
1.06
Lb/hr
64,290
33,210
18,930
12,150
M cu ft/day
3230
. ,.,
....
2. Flow rate of combined feed to furnace.
Of the combined feed entering the furnace 22% by weight is converted into gas
plus gasoline.
Gas plus gasoline, lb per hour = (33,210 + 12,150) = 45,360
45,360
Combined feed to furnace, lb per hour = "TZT = 206,170
Recycle stock produced in furnace, lb per hour = 206,170
(33,210 + 18,930 + 12,150) = 141,880
....
3. Properties of combined feed.
i<Jt .f .
'
Recycle Stock
' Gravity, "API
19
Characterization Factor K
10.7
Lb per hour
141,880
%bywgt
68.8
Fresh Feed
29
11.8
64,290
31.2
''.s'*
111,318,600
162,531,200
..r
61,212,600 Btu
7,670,000 Btu
23,636,600
11,742,300
92,269,300
27,214,000
162,531,200
426
6. Weight of combined feed used for quenching hot vapors from furnace.
The energy balance about the quench point is shown diagrammatically in Fig. 93.
The required quantity of quench is fixed by this balance.
Heat Effluent
lOw'F.
i
(206,170 lb )H,
Evaporator Feed
-800r.
(206,170 Ha+x Hi
J Ha
300F
"
' '
Input
Enthalpy of vapors at 1000F =
Enthalpy of quench at 300F =
Total =
135,317,200 Btu
'
108.6a:
135,317,200 + 108.6x
Output
','.
Vpeflux
Combined Feed
Reflux
^Ib.
300" F.
Vapors
800 F.
Tar745F.
'
,'
CHAP. X]
427
143,059,600
,
108.6;/
143,059,600 + lOS.Qy
Output
Enthalpy
Enthalpy
Enthalpy
Enthalpy
Enthalpy
Enthalpy
Total =
125,249,800 + 458.45?/
^,
2/ = 50,906 l b .
~ Gas=12,140 lb.
290 F.
Gasolineit33,2101b.
RenuxatgS'P.
2 lb. Gasoline
Feed at 200*p.
64,2901b.
4,766,300 B t u
16,468,800
64,636,400
56,022,600
4,022,600
14.25z
-
145,916,700 + 14.25Z
1,361,400 Btu
8,267,700 + 248.65?
81,573,700
91,192,800 + 248.66Z
CH,
CjHj
CO
H,
N,
Moles
Mol
Wt
Lb
14.6
77.3
1.2
6.1
0.8
16
30
28
2
28
2.34
23.19
0.34
0.12
0.22
26.21
.-^^
0,
CO2
required
lblb-moles moles
H2O
lbmoles
29.2
270.66
0.6
3.05
14.6
164.6
1.2
29.2
231.9
303.40
170.4
6.1
267.2
Heating
Value Heating value X
Btu per mole fraction
lb-mole
383,040
671,090
121,340
122,980
55,930
518,160
1,460
7,510
583,060
Btu per lb-mole
ofr,>l
Total moles air supplied per 100 moles fuel = 1877 lb-moles
Molal humidity, lb moles water per lb mole dry gas (Fig. 9) = 0.022
Water from air = (0.022)(1877) lb-moles = 41.3 lb-moles
Products of combustion:
Carbon dioxide
Water = 267.2 + 41.3
Oxygen = 394.4 - 303.40
Nitrogen = 0.8 + 1483
170.4 lb-moles
308.6
91.0
1483.8
2063.7 lb-moles
CHAP. X]
429
Enthalpy
Btu/lb-mole
19,190
21,820
18,500 + 8.30i
23,490
The temperature of the gases from the furnace is determined by an energy balance
of the air preheater, illustrated in Fig. 96. As a first approximation it may be
assumed that the temperature drop of the gases in the preheater approximately equals
the temperature rise of the air. Mean heat capacities are based on this assumed
temperature which may be corrected by a second approximation if the energy balance
shows it to be seriously in error.
Stack Gases < |
600F.
'
|"*Air 80 F.
-Air 400 P.
tF.
= 7,925
18.57( - 65)
25.6<
6.82 - 65)
105.35(( - 65)
130.74(i - 65) + 25.6
58,483 + 156.34^
Output
Enthalpy of waste gases leaving (at 600F)
CO2 = (1.704) (600 - 65) (10.1) = 9,207
H2O = (3.085) (23,490)
= 72,466
O2 = (0.910) (600 - 65) (7.3) = 3,554
N2 = (14.838) (600 - 65) (7.1) = 56,362
Enthalpy of air at 400F
Air
= (18.77) (400 - 65) (7.0) = 44,015
Water vapor = (0.413) (21,820)
= 9,011
Total
= 194,615 Btu/lb-mole of flue gaa
j^
Stack Gases-"^
600?.
>AAAA/
WVNA/^
- Vapors
at 1000 F.
/\AA/V*-
FuelGasat60F.
w lb. Moles
Ifillw Btu
7,925i Btu
+ 51,212,600
583,060; Btu
592,956K) + 51,212,600 Btu/hr
Output
Enthalpy of vapors at lOOCF
135,317,200
Enthalpy of waste gases
Heat absorbed in cracking
27,214,000
Heat losses = (0.05) (583,060)u)
Total =
162,531,200 +
From the energy balance,
592,956u) + 51,212,600 = 162,531,200 + 170,662w
141,509)
29,153u)
170,662)
422,294K) = 111,318,600
'
H.
'
C H A P . X]
PROBLEMS
431
7,784,420 B t u / h r
54,723,730
1,199,690
63,707,840
5,873,200
17,086,000
86,667,040 B t u / h r
6373 gpm
587
1709
8669 gpm
PROBLEMS
1. In a plant for the manufacture of sulfuric acid by the chamber process pyrites
is burned in a shelf burner. The gases from the burner enter t h e Glover tower
a t 480C and leave this tower at 105C, entering the first chamber. The gases leave
the last chamber a t 42C and finally leave the Gay-Lussac tower at 21C. On the
basis of 100 kg of pyrites, as charged, there are charged into the Glover tower, 175
kg of chamber acid, 65.2% HzSOi (51.8B6) at 30C; 610 kg of Gay-Lussac acid
at 23C, and 1.30 kg of 4 0 % nitric acid at 20C. The Gay-Lussac acid contains
78.0% H28O4 (60.0B6), 0.984% N2O3 in solution, and 21.0% H2O.
The analyses of the pyrites, cinder, and the moisture-free gases leaving the burner
are as follows:
FeSj
SiOz
H2O
Pyrites
90.00%
4.80%
5.20%
100.00%
FcjOs
FeS2
SO3
Si02
Cinder
89.80%
1.65%,
1.93%
6.62%
100.00%
The pyrites is charged to the burner at 20C. The air enters at 20C, under a
barometric pressure of 722 mm of Hg and with a percentage humidity of 40%. The
cinder is withdrawn a t 320C.
For each 100 kg of pyrites as charged, 768 kg of acid containing 79.4% H2SO4 leave
the Glover tower at 100C and are cooled to 23C. The chamber acid leaves the
first chamber at 65C and is cooled to 30C before entering the Glover tower. The
acid leaves the Gay-Lussac tower at 30C and is cooled to 23C for recirculation.
The spray water enters the chambers at 20C.
432
From the Row chart and assumptions of Illustration 1, calculate individual material
and energy balances, on the basis of 100 kg of pyrites as fired, of:
(o)
(b)
(c)
(d)
(e)
The burner.
The Glover tovirer.
The chambers.
The Gay-Lussac tower.
The entire plant.
2. The charge delivered to a blast furnace, on the basis of 1000 lb of pig iron, consists of 1810 lb of ore, 361 lb of Umestone, and 892 lb of coke. The analyses of
various components of the charge are as follows:
Ore (1810 lb)
Fe^Oa
FeO
MnaOi
AI2O3
Si02
H2O
62.10%
19.07%
2.12%
2.89%
8.62%
5.20%
CaO
MgO
SiOz
AI2O3
Fe^Os
CO2
H2O
100.00%
51.12%
2.10%
2.89%
4.12%
0.52%
35.05%
4.20%
Carbon
Hydrogen
FeaOa
Si02
CaO
MgO
S
H2O
100.00%
88.20%
2.00%
2.10%
1.98%
2.32%
1.10%
0.20%
2.10%
100.00%
The total heating value of the coke is 14,200 Btu per lb.
On the basis of 1000 lb of pig iron produced, 51 lb of dust are collected from the
gases leaving the furnace. The analyses of the products are as follows:
Pig iron (1000 lb)
Fe
Si
Mn
S
C
92.28%
2.10%
1.38%
0.03%
4.21%
FeO
C
CaO
SiOj
83.2%
10.1%
3.1%
3.6%
CH4
CO2
CO
H2
O2
N2
100.0%
100.00%
0.80%
12.10%
29.30%
2.12%
0.20%
65.48%
100.00%
The surrounding air is at 70F, 40% percentage humidity and a barometric pressure of 29.2 in. of Hg. This air is heated and supplied to the tuyeres at 850F.
The ore, flux, and coke are charged at an average temperature of 65F.
The gases leave the furnace at a temperature of 422F. The molten slag and pig
iron are tapped from the furnace at a temperature of 2500F. The sensible enthalpy
of the flue dust is negligible.
Calculate the complete material and energy balances of this furnace, using the assumptions of Illustration 2.
3. In producing 1 ton (2000 pounds) of steel in an open-hearth furnace the following charge was supplied:
/,
Hot metal from blast furnace (2400F)
Cold scrap iron
Limestone (95.5% CaCO,, 4.5% H2O)
Iron ore (94% FeiO,, 6% HjO)
Fuel oil
814 pounds
1250 pounds
118 pounds
56 pounds
28.2 gallons
CHAP. X]
PROBLEMS
433
Air was supplied to the regenerators at 80F, 60% relative humidity, atmospheric
pressure. The air (85% of total supply) was preheated to 2000F in the regenerators.
The hot gaseous products of combustion left the hearth at 2860F, entered the regenerators at 2560F and entered the stack at 1000F. The average analysis of the flue
gases measured over the nine hour run was as follows:
CO2 = 17.0%
O2 = 0.8%
N2 = 82.2%
100.0%
Carbon
Silicon
Manganese
Phosphorus
Iron
Hot Metal
4.25%
1.92
0.32
0.65
92.86
Cold Scrap
0.15%
0.50
0.02
0.065
99.20
Steel
0.15%
0.25
0.02
0.02
99.56
The steel and slag were poured at 2800F. From experience it is known that 15%
of the air used in the furnace leaks in through the doors and brickwork of the hearth.
The fuel oil had the following properties:
Characterization factor
API gravity
11.1
12.0 '
The following information is desired on the basis of 1 ton of steel produced: (Use
80F as basis of enthalpies.)
1.
2.
3.
4.
5.
6.
7.
8.
9.
Gasoline
Fresli Charge
60F
,
,
"
_
-
Heavy
Light
Gas Oil Gas Oil
'
/
PROBLEMS
435
The hydrocarbon products from the processing reactor pass to a primary fractionating column in which a heavy gas oil fraction is removed as bottoms. The overhead
from this column passes to a secondary fractionating column in which well fractionated gasohne and gases are the overhead products. The bottoms, a light gas oil, is in
part recycled to the cracking process, in part used to reflux the primary column, and
in part withdrawn as final product.
Laboratory tests indicate that at the operating temperatures indicated in Fig. 97a
the following products and yield are obtained from the indicated charging stock:
^.
, _
Charge
Gasoline
Light Gas Oil
Heavy Gas Oil
API
30
60
32
25
K
11.9
12.0
11.4
11.5
% by volume
of charge
100
49
24
18
Hydrogen
Methane
Ethylene
Ethane
Propylene
Propane
In accordance with the process information given above, develop the following
design factors and evaluate complete material and energy balances for a plant to
charge 10,000 barrels (42 gal.) per day. Base the balances on one hour of operation
and express rates in barrels per day and pounds per horn- for liquids and pounds per
hour and thousands of cubic feet per day for gases. Heat losses may be neglected
except from the furnace.
(o) The production rates of all net hydrocarbon products and the catalyst deposit.
(6) The rates and properties of the combined feed to the heater and the light gas
oil recycle stream.
(k) The rate at which air must be supplied in order that reactivation may be com-,
pleted in the time of the process period. It may be assumed that the oxygen of the
air is 100% utiUzed, going to carbon dioxide and water under the catalytic combus- ,r,
tion conditions.
\.^
(i) The rate at which heat must be removed by the circulating salt from a reactor
under reactivation, neglecting changes in the enthalpy of the catalyst bed.
(m) The rate at which salt must be circulated through a reactivating reactor heat
exchanger. The heat capacity of the molten salt may be taken as 0.25 Btu per pound
per F.
(re) The temperature of the salt entering the waste heat boiler.
(o) The quantity of steam generated in the waste heat boiler, in M lb per hr.
,! J
CHAPTER XI
THERMODYNAMIC PRINCIPLES
438
THERMODYNAMIC PRINCIPLES
[CHAP. XI
CHAP. XI]
439
440
THERMODYNAMIC PRINCIPLES
[CHAP. XI
,^
;"
.'
.!?''
i'.'
CHAP. XI]
ENTROPY
441
pressure. The same is true for other intrinsic properties such as internal
energy and enthalpy.
Since entropy is a measure of unavailabihty of total energy, it follows
that the entropy of a system is increased by the degradation into heat of
any higher form of energy which it possesses. This is illustrated by
consideration of an isolated system comprising an inelastic weight
suspended above a rigid plate. If the weight is allowed to fall, the total
energy content of the system is unchanged, but the potential energy of
the weight is converted into heat as a result of the inelastic impact on the
plate. The temperature of both the weight and the plate are correspondingly increased by the absorption of this heat in the form of
internal energy. The process of dropping the weight has not changed the
energy content of the system but has degraded it to a less available form
and is therefore accompanied by an increase in entropy. Similarly, if a
rotating flywheel is stopped by a brake, kinetic energy is degraded into
heat, and the entropy of the system is increased. However, if the flywheel were stopped in a reversible manner by means of a frictirnless
transmission which sets another flywheel in motion, there would be no
degradation of energy and no change in entropy.
In both of these illustrative systems an increase in entropy results
from the addition of heat to the system through the degradation of a
higher form of energy. However, since entropy is an intrinsic property
of the matter of the system not influenced by the elevation of the weight
or the movement of the flywheel, it follows that the entropy of a system is
increased by the addition of heat through any mechanism or from any source.
Thus, heat might be added to the system containing the elevated weight
and the rigid plate increasing the total energy content of the system
until a temperature is reached which is equal to that attained after the
weight has been permitted to fall in the system when isolated. Since
entropy is independent of the position of the weight and the plate, the
final entropies of the system are equal, and the increases in entropy
accompanying these two processes are also equal, although heat is added
to the system by the degradation of its own energy in one case and by
increase in its total energy content in the other.
It is evident that the amount of heat added to a system is a partial
measure of the magnitude of its increase in entropy. However, the
quantity of heat added is not the sole measure of increase in entropy.
The unavailabihty of energy and the entropy of an isolated system are
increased by the transfer of heat within the system to a region of lower
temperature. Similarly, the addition of heat to a system at a low
temperature results in a greater degradation of energy than at a high
temperature. It follows that the increase in entropy accompanying the
442
THERMODYNAMIC PRINCIPLES
[CHAP.
XI
dS =
where (S = entropy.
~ /
' -
(1)
; ^
The primed differential symbol d' is used for indicating incremental quantities of
heat and work. In contrast to the other terms in the energy equation, neither heat
nor work are properties of the system, nor can they in general be expressed as a function of the state of the system. An infinitesimal change in a property such as volume
can be expressed as dV which is an exact differential with respect to the state of the
system. However, since neither q nor w are properties an increment of either is
referred to as an inexact differential.
li.v
CHAP. XI]
ENTROPY
443
(2)
444
THERMODYNAMIC PRINCIPLES
[CHAP.
XI
'
CHAP. XI]
CHANGE OF ENTROPY
445
'
'
'
>;
.;'.'"I'J',;
AS = I; = i ^ = 7.23 cal/(g-mole)rK)
i
toy
The heat of vaporization of ethyl alcohol at atmospheric pressure is 9400 cal per
g-mole at a normal boiling point of 351K. Hence, the increase in entropy in vaporization is
.
^ ^.
^ iO^i-t.Mn^u -or--!qf;'V-;
AS = I; = ^
It may be observed that the units of entropy are the same as for heat
capacity.
When heat is added with a resultant temperature rise, the increase in
entropy must be calculated by integration of Equation (1) over the
required temperature range, thus
'
= r
1/273
f^
\
.(
+ 0.008533 - 2.475(10^)r'jdr
/
1273
2 475
= 6.85ln-- + 0.008533(1273 - 273) - - (10-)[(1273) - (273)']
= 17.16 cal/(g-mole) (K)
..-,.'
s.
(3)
446
THERMODYNAMIC PRINCIPLES
[CHAP.
XI
^'
G = H - TS
(4)
AG = AH - TAS
(5)
q = AU + We + Wf
' -it-.,,-
.,"'
. ,
.'
. ^:
(5a)
CHAP.
XI]
FREE ENERGY
where
. -
447
,,, i,.,^
.. '
'
'-,.
,
.:
(7)
,
. ' :
(8)
: .-:
(9)
448
THERMODYNAMIC PRINCIPLES
[CHAP.
XI
From the first law, for a reversible nonflow process at constant temperature,
AU = q-w=TAS-w
(10)
AA = W = {We + Wf)
'.
(11)
CHAP. X I ]
CRITERIA OF EQUILIBRIUM
449
450
THERMODYNAMIC PRINCIPLES
[CHAP. XI
mal extent shall be reversible since any irreversible change would result
in a displacement which would destroy the Original equilibrium. As was
previously pointed out, reversible processes are accompanied by no
change in total entropy of the combined system and its surroundings,
whereas every spontaneous process is accompanied by an increase in
total entropy. Thus, a universal thermodynamic criterion of equilibrium is that for any change which takes place the total entropy of the
system and its surroundings shall be constant. In a completely isolated
system the entropy of the system itself is constant at equilibrium. From
Equation (1), defining entropy, it follows that where heat is added to a
system in which all changes of state are reversible, d'q = T dS, where S is
the entropy of the system itself, not including its surroundings. This
expression may also be taken as a criterion of reversibility and equilibrium. Since for all irreversible changes of state dS > d'q/T, if any incremental addition of heat to the system is accompanied by an entropy
increase equal to and not greater than d'q/T, all thermodynamic processes
within the system must be reversible, and it follows that the system is in
equilibrium.
A system is in stable equilibrium if after a finite displacement it
spontaneously returns to its original state when the displacing force is
returned to its original value. A round pencil lying in the bottom of a
cylindrical trough is a mechanical example of this type of equilibrium.
If, however, this pencil is carefully balanced on its sharpened point, it
will be in a state of unstable equilibrium such that finite displacement
does not lead to a spontaneous return to its original conditions. Thermodynamically, a system is in unstable equilibrium if, although any
infinitesimal change is accompanied by no change in the total entropy of
the system and its surroundings, a finite displacement involves an increase
in total entropy. For example, a finite displacement of the pencil
balanced upon its point results in an irreversible process whereby heat is
developed and the entropy of the pencil and its surroundings increases.
In a system in stable equilibrium no finite change can be accompanied
by an increase in total entropy. Thus, at stable equilibrium, for any
change resulting from a temporarily applied extraneous force, not associated with the system or its normal surroundings,
dSi= 0,
ASt^
(12)
ASt > 0
(13)
CHAP. XI]
CRITERIA OF EQUILIBRIUM
451
dV = 0
and
{dU),y = -d'Wf
(14)
(15)
452
THERMODYNAMIC PRINCIPLES
[CHAP.
XI
+ d'wf
(16)
= 0
' " ; - ) ;
(17)
(18)
.,
,
/
(19)
; .^
(20)
It follows that at conditions of equilibrium restrained to constant temperature and pressure it is a criterion of equilibrium that
{dG)Tp = -d'wf
or if no useful work can.be performed
(21)
(d(?)rp = 0 ' ,
(22)
CHAP. XI]
THERMODYNAMIC RELATIONSHIPS
453
454
THERMODYNAMIC PRINCIPLES
[CHAP. XI
(23)
(24)
(25)
(26)
SdT
CHAP. XI]
455
(27)
dH = TdS+Vdp
(28)
dA = -SdT
- pdV
(29)
Vdp
(30)
dG = -SdT+
du = (f)
dx + (f)
\dx;y,^...
dy + (f)
\dy/x,z...
dz + ...
(31)
\^Z/x,y...
The properties of a substance fulfill the requirements of u, and Equation (31) can be extended mathematically to include any number of
variables. The value of the integral of du between any two conditions A
and B of a relationship represented by Equation (31) is dependent only
upon the location of these two points and is independent of the path
followed between the two states. For a case involving only three variables, this situation is evident from consideration of !Fig. 55 (page 286).
Thus,
du =
UB
UA
= j{x, y)
(32)
456
THERMODYNAMIC PRINCIPLES
[CHAP.
XI
dx\dy):,
.^^
or
- ^ = ^ ^
''
(34)
dy dx
dx dy
If more than two independent variables are involved, a relationship
similar to Equation (33) may be \yritten with respect to any pair of
independent variables. Any exact differential equation must satisfy the
relations of Equation (33).
For example, if du is expressed by the relation
du = Mdx + Ndy +Pdz
(35)
\dy/J
\dz/y^
d^u
dxdy
{'dN\
\dx )y
^ /dP\
^ fu_
\dx A
dxdz
d^u
dxdy
^^
/dN\
\dz)y'
\ dy A
_ /dP\
_ _a2M_
\dy J^" dydz
du = (~ ) dx + (~)
\dx Jy
" /
dy
^ '
'
(39)
\dx/y
\dy/x
the condition is imposed that the property u is constant, the equation
becomes
or
W " ~ \^x)y/
\dy}^
^^^^
CHAP. XI]
MAXWELL RELATIONS
457
Equations (37), (38), (41), and (42) represent mathematical principles commonly used in the development of thermodynamic relations.
Maxwell Relations. Since Equation (27) is an exact equation of the
form of (31) the relationships of Equations (37) and (38) permit the
derivation of a differential equation relating the coefficients T and p as
shown in Equation (43). Similar equations result from equating the
partial derivatives of the coefficients of Equations (28), (29), and (30).
Thus,
Equations (43), (44), (45), and (46) are termed the Maxwell relations.
Equation (45) is the basis of the familiar Clapeyron equation. For
the vaporization of a liquid the restriction of constant volume may
be omitted, because the vapor pressure is independent of volume.
Since vaporization is a reversible process at constant temperature,
(a5/aF)r = A / r A 7 and
^ = _A_ = ^
.
dr
T AF
^__
(47)
r(F - Fi)
^ '
using the reference conditions, p = 173 lb per sq in. abs, t = 185F, S = 1.300, and
V = 2.20 cu ft
'
THERMODYNAMIC PRINCIPLES
458
AtS
1.24
, 200
1.28
T
At F = 2.20
= 1.300
(
165.2
174.4
183.0
185.0
191.3
199.2
206.9
V
2.461
2.339
2.229
2,200
2.132
2.043
1.960
S = entropy
1.32 1.36
1.40
190
180 h
1190
S=1.S
y=2.2 0 ^
t
114.8
145.1
186.3
186.0
208.0
240.3
283.1
S1.2466
1.2705
1.2935
1.3000
1.3154
1.3388
1.3575
P
150
160
170
173
180
"l90
200
[CHAP. XI
P
150
160
170
173
180
190
200
160 - 210
= -83.3.
2.50 - 1.90
g-iso
(50)
\dp)s
\dp/T
(49)
(51)
(52)
/dif
\dS/pt / p
(53)
(54)
(fa=-
(55)
CHAP. XI]
459
/dU\
/dH\
/dU\
/dA\
By again partially differentiating the four basic differential energyfunction equations with respect to the coefficient terms, another set of
eight relations results:
* '
Cp = {-]
(68)
C' = (-I
(69)
\dVjT
(70)
(71)
460
THERMODYNAMIC PRINCIPLES
[CHAP. XI
Combining (72) and (73) with Equations (68), (69), (70), and (71) gives
KdV/r
T\dV/T
h=T[^^)
^ ^
'
(78)
and
I* = p
'
/ *
CHAP. XI]
461
Substituting the values of Equations (74-77) into (72) and (73) yields
; V
rfS = ^ c i r + | d p
(82)
dS = ^dT
(83)
+ ^~dV
If Equation (82) is applied to conditions of constant entropy and Equation (80) is substituted
\y p
Vp
:*
^^^^
(86)
462
THERMODYNAMIC PRINCIPLES
[CHAP.
XI
/dp\
^^
/T
'
(92)
\dT/p
'"
(tX=-KS);
Similarly, from (83) and (81),
^ <?)
/
mi-"]
(95)
a-(a(
CHAP. XI]
463
,H.C.4T +
[^T(^1+V].dp
(98)
/dH\
^^
( ^ .
= "
^ /dV\
""'
One of the most important relations expresses the variation in freeenergy change with change in temperature at constant pressure. From
Equation (5),
AG
AH
^^
T\dT
)p
(102)
KdT/p
By Equation (62),
(103)
combining (102) and (103) gives
] - _^
(104)
Illustration 4. From van der Waals' equation of state calculate the increase in
Cp of COj where the pressure is increased from 1 to 100 atm at 100C. The van der
Waals equation is
(p + ^ ) ( _ 6 ) = /jr
where
v = molal volume
a,b = van der Waals' constants, characteristic of the gas
(a)
464
THERMODYNAMIC PRINCIPLES
[CHAP. XI
R -'
_ ^ , 2ob
( dT/p ~
KerOp
/
. '
^"^
^^^
''"'--J^ H^J/^
Equation (e) is solved by substitution of (d) and graphical integration where,
a = 3.60(10);
Volume V is first obtained from Equation (a) at various values of p. Equations (c)
and (d) are then solved in turn at various values of p.
p
atm
cc
\dTjp
Varv
00
00
30,690
2,985
1,150
530
320
213
82.7
8.55
3.65
2.09
1.67
1.56
0
0.64
0.734
0.931
1.52
2.8
5.07
0
1
10
2&
60
75
100
From graphical integration,
Cp C =
where
a
V \dp
JT
From this relation calculate C, for mercury, where at 0C, /3 = 0.00018 per C,.
a = 0.000 003 9 per atm, Cp = 0.0333 cal/(g) (C), and the density = 13.596 g per
cc. From (90),
/
Cv
-xr
aV
/^
CHAP. XI]
465
Shaw's Method of Derivation. The usual procedure in making thermod3Tiamic transformations to arrive at a usable or desirable relation is
time-consuming and often results in circuitous procedures which return
to the starting point. A. N. Shaw^ has devised a means of circumventing
these difficulties and arriving at the desired result in a systematic manner.
This method employs a system of abbreviated mathematical notations
termed Jacobians. A Jacobian is a determinant, the elements of which
are partial derivatives.
It will be recalled that the solution of simultaneous algebraic equations
can "be accompTis'hed'by the use oi determinants. ? o r example, consider
the two simultaneous equations:
aix + biy = ci
(105)
(106)
aid UiCi
aib2 aibi
ai6i
O262
(107)
aiCi
a2C2
y = aibi
a2&2
The lower determinant in each case is the principal determinant con2 A. N. Shaw, Phil. Trans. Roy. Soc. A, 334, 299-328 (1935).
THERMODYNAMIC PRINCIPLES
466
[CHAP. XI
/dx\
(dy\
/dy\
\dJs
V/3A
\da)s V/SA
Va/SA \da)s
^^^^^
where x and y are two dependent variables and a and /? are any two independent variables of which x and y are functions. For example, x might
be enthalpy; y, entropy; a, temperature; and |3, pressure. The values
of a and jS may equal x and y. The foregoing Jacobian is also written in
d(x, y)
the form J(a;, y) where J{x, y) =
Where this abbreviated notad{a, /3)
J(x, y)
2.
3.
d{x, x)
d{y, x) _ d(y, x) _
a(a, /3)
d% a)
dix, y)
m)
-J{y,x)
or
J{y, z)
J{x, z)
(110)
J{x, x) =Q
J{z, y)
J(z, x)
(111)
J{y, z)
J{z, x)
J(z, V)
J{x, z)
(112)
CHAP. XI]
467
(113)
J{x, a) _ MJ{y,
a)
NJ{z,
a)
JiP,S) =c
[
:_
(116)
' J(P, T) = I
J{T, S) = Jip, V) = b
The proof of this last relationship is derived by writing Equation (43)
in Jacobian form in accordance with Equation (112), thus,
.
or
^ ( y , 'S) _
J{V,S)
j(p, V) ^ jjp, V)
JiS,V)
JiV,S)
J{T, S) = J{p, V)
'
(118)
THERMODYNAMIC PRINCIPLES^
468
[CHAP.
-o
>
s
1 1
Si
8
Si.
=0
fa.
>
CO
a,
.* 1 .o +
E.H
&^
CO
E^
?i.
EH
=0
1
o
ft.
;^
1
e
EH
es
1
1
i - a.
'S
^r
s
+
+
n.
<X5 fX3
&H
++
St-. ^1
^ ^
rO
1-5
t)
++
S1
a.
'l><
XI
i-:i
CO
J5
fi,
1 ^
52 +
EH
ts
rf3
^a.
l-^
;^
1^ 1 ^ 1
1 + 1
8
ft.
CO
1 ta
0 ~o
Co
^
+
Vi
^ + +a,
CO 8
ft.
2
^
S2
1a.^a.
:^ 1
E^ 1 1 1 ^PS
tM t s
a.
1
tt!
e-i
in
<
<
!? 1
El
a,
'^
o
(/
s
f5
fl.
a.
a.
+e
^ ^
1 +
1'
si1 1
1
s
a.
a.
EN
a.
8
ft.
EH
<
h
e
55,
1
1
t-
1
W5
fr-
-o
e 8
1 1
s
1
+8
1
a.
Sl.
tt3
;3
a.
1
E^
,_^
1 s
Si
e^ to to
&I
5H
f i aa ., CQ
^ ^ 3 ^ U*
II
11 II II II
XI
CHAP. XI]
469
-TJ{p,
V) + VJ{p, T) (119)
J{A, V) __ J{A, V)
~ j(v, T) ~
/dA\
VarA
470
THERMODYNAMIC PRINCIPLES
[CHAP.
XI
(122)
'
(125)
/ ,
(127)
-
or
+ ac - In = 0
- .
(128)
TJ{V, pW{p, T)
J(T, pyj{V, T)
(-a)(-0
T
al
-Ti-b)H
(-O'a
b'T
al
1
'
(b)
/i ,
/
.(c)
(d)
471
The Jacobians c and 6 each include one of the independent variables and may be
expanded directly into a partial derivative in terms of p and T. However,
n = J(V, S) contains neither of the independent variables. It is therefore desirable
to eliminate this quantity by means of Equation (128). Thus,
Tc
Tel
Tn-Vb~
^^
^'^'
Since p and T are the independent variables, this last equation becomes, by
(109),
/dp\
\d{p, T))\d{p,
'ff
, /dip, Toy
T)J
The like terms in (d) are canceled, and the remaining Jacobians written as partial
derivatives according to Equation (112):
(dp\
^
KdVjH
\dTjp
KdTjp ^
Since
(e)
KdpJAdTjp
KdTjp
/dS\
C
( ;;: ) = v ' Equation (e) reduces to
\dl/p
1
Cdp\
^
Cp
, ,
., ,
/SwN
R
For 1 mole of an ideal gas I -; ) = ;
\dTjp
V
hence,
\SVJH
(f)
/ av\
II =
Vp/r
KS--"
V
P
(g)
Equation (g) is in agreement with the requirement that for an ideal gas H is a function
of temperature only. For this requirement
\dv/H
\dv/T
472
THERMODYNAMIC PRINCIPLES
[CHAP.
XI
thermodynamic problems. A brief selection of these more useful relations is presented in Table XXIV.
.'
TABLE XXIV
TBEBMODYNAMIC RELATIONS
Equation Number
in Text
)ns
Differential Energy Functions
(a) dU = TdS
-pdV
(27)
'
'%
(28)
+ Vdp
(30)
Maxwell Relations
'>(a--(S)K
(43)
(44)
(45)
*'(a--(i-a
(46)
(56)
(57)
(58)
Energy-Function Derivatives
(59)
(74)
(75)(80)
(76)
Thermal-Capacity Relations
(77) (81)
(82)
CHAP. X I J
473
(cmL)
Equation Number
in Text
(83)
(r) dS = - ^ r - + - j T -
^'-<'--KS);(a=-
(90)
(91)
<>(t),=-(s;).
(93)
M(S^). = K I * ) ,
Effect of p, V, T on f/, H, and G
(-)(a = Kf?).-
(94)
'"-'
(96)
(^)(S).^^^
(97)
<^)(f).(a
(99)
(^)(ii) =(^^
(100)
474
THERMODYNAMIC PRINCIPLES
[CHAP.
XI
Since Equation (129) relates p, V, and T, it may be termed a thermodynamic equation of state. If this equation is apphed to an ideal gas,
for which (d[//rfF)r = 0
(130)='
Differentiation of the ideal-gas law gives
or
Since Equations (130) and (131) are identical, it follows that the
thermodynamic and the ideal-gas temperature scales are similar functions, both having the same zero point.
Thermodynamic Properties of an Ideal Gas. As previously mentioned, the properties of an ideal gas are defined by the requirements that
the pVT relations are exactly expressed by the equation pv = RT and
that the internal energy is dependent only upon temperature and is
independent of pressure and volume. Equations whose applicability is
restricted to ideal gases are designated by asterisks (*) following the
equation numbers. Similarly an asterisk following any thermodynamic
symbol indicates restriction to the ideal-gaseous state.
By differentiation of the ideal-gas law, it follows that
or
m
\dT/v
^ ^ ^ l
and p )
V
T
\dv/T
^ - ^ and
V
(132)*
jv!mw:<qw(ft^v-ni.;- :':
(^\
\dT/p
= ? = ;
p
T
(133)*
\ '
', :
dT + [^)^dv
^ V
" .;;;
(135)
- pi dV
(136)
//
475
/dp\
For an ideal gas P = T I-] , and Equation (136) becomes for 1 mole
\dl /v
dv = c^dT
(137)*
or
,
^>
u = /
c,dT + Vo
(138)*
+ RdT
= (c, + R) dT
(139)*
or
c,dT + RT + n<i
(140)*
e/O
= -V
".'
(141)="
P
Combining (141) with (q) of Table XXIV gives
ds = Cpd In T R d \n p
or
'
As =
f 'c^dlnT
- R]n(142)*
Jr,
pi
It is evident that Equation (142) cannot be directly integrated with
lower limits of either T = 0 or p = 0, since the integral of each term at
these limits becomes negative infinity. In order to evaluate directly the
entropy of an actual gas in the ideal state from heat-capacity measurements it is necessary to start \vith the crystalline solid at a temperature
near the absolute zero, heat it to its fusion point and then to its boiling
point T' under a pressure p' sufficiently low that ideal-gas behavior is
obtained. The entropy s' of the saturated vapor at this temperature
and pressure is calculated from the low-temperature heat capacities of
the crystalline and liquid state and the heats of fusion and vaporization.
Equation (142) is then integrated from this limit. Thus,
CpdlnT
+ s'
(143)*
p
A perfect gas may be defined as one which behaves ideally at all conditions and hence is incapable of condensation to either a liquid or a soHd
JT'
- R\n-,
476
THERMODYNAMIC PRINCIPLES
[CHAP. XI
phase. It follows that for the internal energy of such a gas to be independent of volume at all conditions of pressure and temperature it can
possess only translational energy of motion and its heat capacity must be
independent of temperature as well as of pressure, as shown by Equation (VII-19), page 211. Thus, for a perfect gas, c = fi2 and Cp = %R,
whereas the heat capacity of what has been termed an ideal gas may
vary with temperature. It is evident that no substance fulfills the properties of a perfect gas but that perfect behavior is approached by monatomic gases at low pressures.
For a perfect gas, Equation (142) may be integrated as follows:
s = #filnr-i?lnp + 6
(144)*
i'
i
" I
'
AG* = AH* - TasJ -|- TiS? = 279.6 - 23 234 + 23 700 = 746
.i
PROBLEMS
'
CHAP. X I ]
PROBLEMS
477
= 0.113 lb/(sqin.)rR)
\dv/T
<^' .
.
&l
(t\
(P)
xdv/r
/aT\
\dp/T
(o)
Cp Cv
Ip
(?)
8. For a van der Waals gas (see Illustration 4, page 463), evaluate the following
coefficients:
\dp/s
( - ) i in terms of G and p.
\dp /S
478
THERMODYNAMIC PRINCIPLES
[CHAP. XI.
(:dTJp
11. From Table XXIII derive equations for the following quantities in terms of the
indicated variables:
%
Quantities
Variables
(a
(iX
o.
S,p
-S
^:'
4, r
<* Q .
S,T
=-T\
(b) (Cp - CJ
/'dp\
(ST.
Vary J, VaF/r
W/F
wA
13. Calculate the values of As, Au, AH, AA, and AG when 1 lb-mole of Ha gas at
77F and 1 atin is heated and compressed to 500F and 100 atm. The initial absolute
entropy of hydrogen is 31.23 Btu/(lb-raole) (R). Assume ideal behavior.
14. From the relationships of problem 8 and *rable XXIV, calculate the following
changes in the properties of 1 lb-mole of CO2 gas when the pressure is increased isothermally from 1.0 to 100 atm at 100C. a = 3.60 (lO^) (atm)(ce)V(g-mole)2;
6 = 42.8 cc per g-mole.
(a) AH,
(6) Au, .
(c) As,
(d) ACp,
(e) Ac,.
CHAPTER X I I
THERMODYNAMIC PROPERTIES OF FLUIDS
The ideal-gas law permits satisfactory calculations of pressurevolume-temperature relationships at low pressures where the volumes
per mole are relatively large and the distances between molecules great or
where the temperatures are relatively high. However, under conditions
of small molal volumes, corresponding to high pressures, the errors in
assuming ideal-gas behavior may be as great as 500 per cent.
Actual Behavior of Gases. Several hundred equations of state have
been proposed to express the pVT relationship of gases, but none has
been found universally satisfactory, and most are applicable only to a
single gas over a limited range of temperatures and pressures. The
most generally satisfactory equation of state is that of Beattie and
Bridgman wherein the various constants must be determined uniquely
for each gas. The van der Waals equation is presented because of its
value in giving an elementary understanding of the reasons for departure
of gases from ideal behavior and because of its support of the theory of
corresponding states which serves as the basis of 'the most useful generalized graphical method. However, the van der Waals equation is less
accurate than the generaUzed graphical method, and its application is
rarely warranted.
The actual pVT relationships of carbon dioxide are shown graphically
in Fig. 99. Each curve represents the relationship between the pressure
and the molal volume of carbon dioxide at the indicated temperature.
The critical point is indicated by C. The double-crosshatched area
represents the region of the liquid state. The plain area is the region of a
homogeneous fluid state which at low pressures is recognized as a gas but
at high pressures has continuity with the liquid. The single-crosshatched area represents a region in which both the liquid and gaseous
states are present in equilibrium with each other. Thus, following along
the 21.5C experimental isothermal line from right to left, an increasing
pressure is required to cause a reduction in volume until the saturation
curve CB is reached. At this point the attractive forces between the
molecules become sufficiently greafto start condensation. The volume
may then be diminished without further increase in pressure until the
curve CA is reached. This curve represents the completion of condensation into the relatively incompressible liquid state. A further decrease
in volume must be accompanied by a large increase in pressure.
479
480
T H E R M O D Y N A M I C P R O P E R T I E S OF F L U I D S
[CHAP. X I I
Isotherms of CO2
Experimental
Van der Waals
Simple Gas Law
100
200
Molal Volume, cc. per gram mol
F I G . 99.
CHAP.
481
XII]
TABLE
XXV
cc \^
1;
g-mole/
6 =
cc
g-mole
Argon
Acetylene
Air
Ammonia
Carbon dioxide
Carbon monoxide.
Chlorine
Ethylene
Hydrogen chloride
Hydrogen
Methane
Methyl chloride...
Nitrogen
Oxygen
Sulfur dioxide
Water
35 X 10"
37 X 10"
33 X 106
19 X 106
60 X 10"
46 X lO"
6.50 X 10
4.48 X 10"
3.65 X 10"
0.245 X 10'
2.25 X 10"
7.50 X 10"
1,347 X 10'
1.36 X 10
6.80 X 10<i
5.48 X 10
32.3
51.2
36.6
37.3
42.8
39.4
56.2
57.2
40.8
26.6
42.8
65.1
38.6
31,9
57.2
30,6
tc
Pc
-122
36
-140
132
31
-139
144
48
62
37,2
111.5
73,0
35
76.1
60.9
81.6
12.8
45.8
65.8
33,5
49,7
77.7
51
-239
-82
143,
-147
-118,8
157.2
374
217,7
0,531
0,231
75,2
113
0,235
0,460
0.311
0,573
0.22
0.42
0,0310
0,162
0.37
0,3110
0,430
0,52
0,4
72,4
95.5
90.0
124
127
87
64.5
99
137
90
74
123
45
^ -,72
or p' = p + -
482
('<i)<'
[CHAP.
XII
h) = tiVmw^ = RT
(1)
This is the equation of van der Waals, which represents the general
form of the pressure-volume relationships of a gas, even when compressed
to the region of liquefaction. Although this equation is an improvement
over the ideal-gas law, its numerical results represent only a fair approximation where molal volumes are small. The factors a and h, characteristic of each gas, are termed the van der Waals constants. In the first
two columns of Table XXV are listed values of a and h corresponding to
pressure in atmospheres, volumes per gram-mole in cubic centimeters,
and temperatures in degrees Kelvin.
Beattie-Bridgman Equation of State. One of the most widely used
equations of state is that of Beattie and Bridgman. 1-2
pv
where
a, 6, 4o, /?o, c =
V=
p =
T =
.B =
This equation contains five constants which must be determined for each
particular system. The methods for evaluating the constants are discussed by Beattie and Bridgman in the papers cited and also by Deming
and Shupe.^
In Table XXVI are values of the constants of Equation (2) for several
common gases. In the ranges of temperature and molal volume indicated
in Table XXVI, the equation was found to jdeld an average deviation
of only 0.18 per cent from the accepted experimental values.
Equation (2) and the constants of Table XXVI may be used to calculate accurately pressure, volume, temperature relationships over wide
ranges of conditions. Such an equation is of value for the extrapolation
of limited experimental data and for highly precise interpolation between
observed values. I t is also valuable in thermodynamic calculations
U. Am. Chem. Soc, 49, 1665 (1927).
2 J. Am. Chem. Soc, 60, 3133 (1928).
5 / . Am. Chem. Soc, 52, 1382 (1930); 53, 843, 860 (1931).
483
TABLE XXVI
BEATTIE-BRIDGMAN CONSTANTS
Gas
He
H2
N2
Oz
Air
CO2
CH4
Ao
J5O
0.004
0.0216 0.05984 0.01400 0 . 0
0.1975 - 0 . 0 0 5 0 6 0.02096 - 0 . 0 4 3 5 9 0.0504
4.20
1.3445 0.02617 0.05046 - 0 . 0 0 6 9 1
1.4911 0.02562 0.04624 0.004208 4 . 8 0
4.34
1.3012 0.01931 0.04611 - 0 . 0 1 1 0 1
5.0065 0.07132 0.10476 0.07235 66.00
12.83
2.2769 0.01855 0.05587 - 0 . 0 1 5 8 7
Temperature
Range, C
X 10< 400 to - 2 5 2
X 10" 200 t o - 2 4 4
X 10^ 400 to - 1 4 9
X 10" 100 to - 1 1 7
X 10" 200 to - 1 4 5
X 10" 100 t o 0
X 10" 200 t o 0
Minimum V
cc/-g
mole
100
100
180
110
125
180
166
I t s use
An empirical equation of
state with eight constants has been formulated by Benedict, Webb, and
Rubin* for the lighter hydrocarbons from the experimental data for methane, ethane, propane, and n-butane; thus, if d is density, ^(-moles/liter.
p = RTd + (BORT
+ cd'
AO -
(1 + yd')
y2
Y2) d' + ( ^ ^ ^ -
)^' + ^'
-yd?
(2a)
TABLE XXVII
CONSTANTS OF THE BENEDICT-WEBB-RUBIN EQUATION OF STATE
Units: Atmospheres, Liters, Gram-Moles, Degrees Kelvin; R = 0.08207.
Bo
Ao
Co 10-8
b
c 10-8
Methane
Ethane
Propane
n-Butane
0.0426000
1.85500
0.0225700
0.00338004
0.0494000
0.00254500
0.0060000
0.000124359
0.0627724
4.15556
0.179592
0.0111220
0.345160
0.0327670
0.0118000
0.000243389
0.0973130
6.87225
0.508256
0.0225000
0.947700
0.129000
0.0220000
0.000607175
0.124361
10.0847
0.992830
0.0399983
1.88231
0.316400
0.0340000
0.00110132
484
[CHAP. XII
Values of the constants for these four gases are recorded in Table XXVII.
This equation holds within 0.34 per cent, eySn at gas densities twice the
critical value.
COMPRESSIBILITY FACTOR
'
(3)
PiVi
ziTi
P2V2
Z2T2
(4)
',
CHAP.
485
COMPRESSIBILITY FACTOR
XII]
1.05 " -
_-__
.. _
_ _ _ _
- - "r-r"7"r- - - -
11 ]"!"
"
1.00
^s^M==^---'^^=^^^-"-"---fc.-:i
-~=^^S-?;8-^i;---^^-^i-;;J^-
0.95
^s'^
^^ ^ ^f
S'*'!.^"^'^''-*."*'" ^^.
^.*."^"*-'^"*-.
"" ^
s"^*""^
'-.. *"'.
~"~
"^-^
'"=^^ '^^^
^ ^^_
0.90
"
__
"^1:*
'>!__
'^
*'^
__^
"|_j
"^^
^-^_
^'^
^.^
^"-^
"'-
""s
Jnl r^~~--
50 C
~h"l~^i.L
R(\<> C~^
*
^^
"""
""li
*'i_
*S
111U-y
'~25C.'
III
LI
"-^
""^^
'^V
""'TTT
** V
nn^
"^^
S,
v
^ j^
0.75
100 C . ^
1 1 1 1
0.70
\
20
30
40
50
^ -- ^
r^^
"' .
"^ V
10
r *1
Ij-kkl
60
70
*'^.
80
90
B = ^
100
Pressure, Atmospheres
i.os -
1 U 1
110
1.00 -
_J_
!
c.
1 f
, + - 1
- - " [ i '
"
'
"
"
L '
>o c.
.,'
i\n
'
/ JrX
1
1 AAo
n oc
A QA
i
f1
- --
/
0.70 _
0
250
500
750
1000
1250
1500
iL
qi
1 12000
1 2250
1750
2500
486
Initial conditions:
,
pi
Vi
Ti
zi
=
=
=
=
30 atm
j /
1.0 cu ft
50C =323K
1.001
[CHAP. XII
. '.
-j-i--
''
%'','
"* .
Final conditions:
Pa = 60 atm
Ti = -50C = 2 2 3 K '
22 = 0.930
VlPlTiZ^
ViTiZi
/ 3 0 \ / 2 2 3 \ /0.930\
Illustration 2. Calculate the pressure in pounds per square inch to which nitrogen
must be compressed in order that 1.0 kg at 60C may be contained in a cylinder having a volume of 10 liters.
Prom Fig. 100 it is found that e,, the compressibiUty factor of nitrogen at standard
conditions, is equal to 0.999. The volume of 1.0 kg or 35.7 g-moles of nitrogen at
standard conditions is then (0.999) (35.7) (22.41) or 801 liters.
Final conditions:
V = molal volume = 10/35.7 = 0.28 liter
T = 323K
2 = 1.015 (from Fig. 101)
^
'
From Equation (4):
*
PiT^.7'2Z2 \ , ^ / 8 0 1 \ / 3 2 3 \ /1.015\
. .
.;,,,.;,..;
^ ^, ^ ,^
Illustration 3. A steel cylinder having a volume of 5 liters contains 400 g of nitrogen. Calculate the temperature to which the cylinder may be heated without the
pressure exceeding 50 atm.
'
\
"
,
'
. .!
'
,--.
(50)(350) ^
(82.1) (0.945)
//
/
/
A large amount of experimental work has been carried out on the more
common and industrially important gases. In the International Critical
Tables are experimental data for many gases and extensive references to
the literature.
^naicKVmm'fi^ ' ..
-^X
"
'
'
COMPRESSIBILITY FACTOR
CHAP. X I I ]
487
1,00
0.95
.0
10
20
30
40
50
60
70
8.0
90
100
Pressure, Atmospheres
z = z,{pV)
273
(5)
M
Ps22.41
(6)
where M is the molecular weight and Ps is the density in grams per liter
at 0C and 1 atm pressure.
The compressibility factor of all gases is unity when the pressure is
zero. Thus, values of Zg may also be obtained by plotting the values of
pVagainst p at 0C and extrapolating the graph top = 0. Then
PsV^
Zs
POVQ
(7)
488
[CHAP.
XII
(7a)
(8)
where the subscript r indicates the reduced and c the critical properties.
This similarity in the behavior of a substance at equal values of reduced
temperature and pressure is referred to as the theory of corresponding
states and forms the basis of the generahzed procedure described in the
following pages for establishing the deviations of thermodynamic properties from ideal behavior. The van der Waals and other equations of
state may be shown to be consistent with and to support this theory.
If the theory of corresponding states were rigorous, a single equation
of state would suffice for all gases if expressed in terms of reduced properties instead of in absolute values. In Fig. 103 are plotted values of
compressibility factors as a function of reduced temperature and reduced
pressure. This chart was derived as an average of data reported in the
literature for carbon dioxide, nitrogen, hydrogen, ammonia, methane,
propane, and pentane, and is not in rigorous agreement with all the data
on any one of these substances. However, these discrepancies, which
result from the fact that the theory of corresponding states is only an
approximation, are small enough so that for many purposes the chart
may be taken as applicable to all pure gases. It then constitutes a con-
CHAP. XII]
11
-;
489
rAi
-IIN
^^ V ^
o
-V ^
CO
v|\ \\
&^^' \\
-1
*tO00,-lrH
^\^
v\\\
^
'
oc
//
//
i\
CO
11
a
o
A\ i
1
1
0)
i
2
9
m
m
V
u
(LI
ip
.-H
O
^
'
00
!:
o
\ \\
' \ ^^
1 \ 4^N^"^
1
? 1 \\
T \^
1
l\
O
(U
2
CO
E
T3
\N
^- c
'1
/r-i
5
^
U
3
T3
U5
11 1
/<z
/ c
\a
'/
J11
o
1 i
I'l '/r^
/
00
CO
U
P
o
III
W
CO
00
<0
o
o
iH
e,^
r*
CO
I/
to
\i
>
-00
1 "
Tt
CO
490
[CHAP. XII
pr = p/ivc + 8)
(9)
40+460
-116.5+460
^ ,
,
1000 + 14.7
Reduced pressure =
673
'
1
1.40
= 1.51
= 0.84
= 16.00
'
10-1
^'^^^^*^'
"""" (in.)Hlb-mole)(R)
'
hence
nzRT
P
- (-'L
j
; . .
CHAP. XII]
491
0 982
Initial pr == == 0.0293
OO.O
296
Initial Tr =
= 2.35
' 126 '
Initial z == 1.00
';
1
'
4i
'
Final Tr =
'
''':* il -'V.' ^ A .
163
= 1.29
126 '
Pi
Final pr =
' 33.5
;,,
PlFl
zj\
pzVi
Z2T3
.,
'
(0.982) (100)
P^d)
1.00 / 2 9 6 \
Z2 V163/
pc = 24.6 atm
27
; ; ' '
^' = ^
= 1-^0
^ = T5^
.
molecular weight = 114
(27)(0.20)=?^^
114
845
845
0.825
z = T ~ \Q26Tr ~ Tr
To solve the problem graphically 2 is plotted in Fig. 104 against Tr for a value of
p, = 1.10 from Fig. 103. On the same scale is plotted the equation 2 = -^
Where these two curves intersect, 2 = 0.72 and Tr = 1.15.
Hence T = 1025r, = (1025) (1.15) = 1180R or 720F.
492
[CHAP.
XII
The generalized compressibility-factor correlation offers the most convenient method available for estimating pVT relationships whenever
critical-temperature and critical-pressure values are available. Several
remarkable properties in the behavior of gases are shown by Fig. 103.
The compressibility factor is less than unity for all values of Tr below 2 at
reduced pressures below 8. In this range actual gases are more compressible than ideal. At vaiues of pr above 8 the compressibility factor
of all gases exceeds unity regardless of temperature. In this range all
V'^.^J
NO.6
1.4
1.6
Tr
FIG. 104. Graphical Solution for Tr.
gases are less compressible than the ideal. At a value of p^ = 8, at all
values of Tr the compressibihty factor is approximately unity. The
greatest deviation from ideal behavior occurs near the critical state where
the gas becomes almost five times as compressible as in the ideal state.
Care should be exercised to avoid use of gaseous compressibility factors
at pressures higher than the vapor pressure at reduced temperatures less
than 1.0. Such conditions produce liquefaction to which Fig. 103 is not
appHcable.
Based upon the generalized chart for compressibility factors corresponding charts have been constructed for deviation from ideal behavior
of other thermodynamic properties such as enthalpy, entropy, heat
capacity, and the Joule-Thomson effect.
Effect of Pressure on Enthalpy of Gases. It has been shown that the
enthalpy of an ideal gas is independent of pressure and a function only of
temperature. However, at elevated pressures all actual gases deviate
from ideal behavior and enthalpy changes with change in pressure,
particularly in the region of the critical point.
CHAP. XII]
EFFECT OF PRESSURE
493
The enthalpy of a real gas relative to the enthalpy of an ideal gas when
both are at the same temperature may be obtained by integration of
Equation (y) of Table XXIV, between the limits of the existing pressure
and zero pressure where all gases behave ideally and the enthalpy
becomes independent of pressure. Thus,
(10)
'
(a=-:hKa]
<-
/dK\
KdVr/TPc
1 ^ _ RTm/
dz\
PrVcTAdTr/^
^^
494
10
9
8
1.
--41
--1.
1.
-1
" U
7
W
\
lO
1'
^ /
5 5*
OS
>
\
_4
V
^
t,i 5
h
'A
11
XII
[CHAP.
2.0^^
2.6.^
3. 0^
"6 0N
-2
]
-3
N,
v..-.>
\
^ \
-4
0.1
6 8 10
20
'<f'U-'! it
\47l
(15)
470/
1.0
0.37
1.05
0.28
1.1
0.25
1.2
1.3
1.4
0.20 0.18 0.16
1.5
0.15
1.6
0.14
CHAP.
EFFECT OF PRESSURE
XIII
495
1 1 1 1
383 14wC
i_
\ '
\ ^
\ \
1
11 \ V
J] y \ ^
11
JLIv*'^-
^t>h
^. <?
^N
^f\
2\l
A'N^
i s
- 2 s 1 i c
" ^71
VC=
> V
to
Si a 2
\\ \
1 11 1
c"
5 1 " ft fe ^
-
^
0
^3
K
_
rS
"-r
"-
ft
^
>>
ft
^ ^ s ^ s -^
^
/^s^
"
s? a, ai
'>\
:tg
1 ^
x
?6-p
(
"o.
O
1-5
' j n ~
^^
-*??
3 d
?!
^ f i Ci
0
'<?
^cK
\,^ ^
^-'r?
^
>'.
0
U
0
0
fc
t:^
D.
a1
0
00
0
0
D
0
0
o.
<.'?,^*3
(^
^
%' , 0
^
0
0
'
1
r>
<'p-0
IS
10
(ao)(aio'-3)/(F3-s)HtH
^C
-t^
11
\ ^
K
0
T-<
0
1^
496
[CHAP.
XII
..
V""**^:*
H* H
''
C^dT
/dV\
!
.
{^\clp
//
(18)
CHAP.
XII]
497
(19)
/dv\*
^ R
(21)
Equation (22) may be integrated if {dv/dT)p is evaluated from an equation or from Fig. 103. Thus, from Equation (3),
/dv\
zR
RT/dz\
S^)T
= B
(I - z) d In pr + RTr '
{ ^
d In p,
(25)
(l-z)dlnpr
+ ^-f-^
(26)
V*
- N :R
- -rJ
rA- 1-
T
X
'"'
\
i\
Nj
[CHAP. XII
L.^
k. 4
\ \
^^
V
^
\^;H
\
^--^
96 *(\
s^>.
06-n,
V
^^lL
^')
s
w
ffl
g
0)
CO
at
%>>
I I I
-d
P
1 "s -s
-s
d
ft
(S
t,
S*
r^
P<
1'
4)
A I A " A 'k
E-i
PH
ti
?^ m m
IN
O
^^ T)'
AV
V j ^ K^
^ > <ss\
"^
^ -s 1 i
Tj
b
e
o
^ 1
.0,
Ti
<U
rJ
-3
t^ ;\
"c
9- r^
t-t
\S
<u Oo
tS
TS
0)
pj
sV
-5?-'
y-\
p
p
Or
'T 0
?.
7,
O^
^ y^
'^o
-%. -
I'^v
%>
O
00
.4
(3o)(91oi-3)/(l=-3)'"'t*si[s)
s-
/ /
CHAP. XII]
499
4 = 6.85 + (8.533)(10-=')r -
{2A75){W-')T'
In cases such as this where relatively small temperature changes are involved, a satisfactory solution may be obtained by assuming the heat capacity to be its value at the
average temperature. Prom Equation (XI-142) at constant temperature,
sj, - Sp = - B In
or
SUOO'C, 100 atm) = 53.19 - 1.99 In 100 = 44.00
From Fig. 107, at values of Tr = 1.23 and pr = 1.37,
s* - s = 1.50
hence,
s = 44.00 - 1.50 = 42.50, the entropy of the actual gas at 100C and 100 atm.
Effect of Pressure upon Cp. The heat capacity at constant pressure
of any substance is represented by the following differential equation:
and
V;
, ^,
500
[CHAP.
XII
;;
(29)
0.01
0.02 0.03
0.06 0.1
0.2 0.3 0.5 0.81.0
2
Reduced pressure, p^
FIG. 108. Molal Heat Capacity Correction for Gases.
3 4 56 7
Since for an ideal gas (dW/dT^)p = 0, the heat capacity of any gas is
independent of pressure at low pressures and Cpo = C*.
CHAP. XII]
JOULETHOMSON EFFECT
601
at constant pressure can also be expressed in terms of the compressibilityfactor. Writing Equation (3) in terms of reduced temperature and
pressure and differentiating, gives
C%)T
= - Tr J ' e dpr
(32)
0.0
(33)
or
602
[CHAP.
XII
<'''-''=rc'.[''(5^),^"']*
Combining (36) and (10) gives
'
(T
T)
i ,; ^ v
= ^ ^ * ' ~ "pl)rCav8) ( H * -
Hp2)r(aYg)
. _,
Cp(a.vg)
where Cj,(avg) is the average molal heat capacity over the range of temperature and pressure involved. Equation (37) is useful only for moderate
changes in temperature. For other cases a rigorous integration of Equation (36) is necessary. Problems involving estimation of such temperature changes are most conveniently solved from temperature-enthalpy
charts.
THE LIQUID STATE
All the exact thermodynamic relations developed in the preceding
sections for the gaseous state are equally applicable to the liquid state
and may be used for the calculation of thermodynamic properties and
their variations. Thus, from data relating the volume of a liquid to
pressure and temperature together with heat capacity data, it is possible
to calculate the effects of pressure and temperature on enthalpy, entropy,
and heat capacity by the same methods used for the gaseous state.
At reduced temperatures below 0.8 the molal volumes of liquids are
small and change little with pressure. As a result, the effects of pressure
on the enthalpy, entropy, and heat capacity of liquids are small and
frequently may be neglected. However, at high pressures, particularly
at temperatures approaching the critical, such effects become large and
must be carefully evaluated.
Generalized Liquid Densities. It was pointed out by Watson'^ that
the compressibility and thermal expansion data of a variety of liquids
which were investigated can be satisfactorily represented by the following relation:
.
,
-or
V = (vicoi)/w
iK. M. Watson, 7nd. BJnjr. C/im., 35, 398 (1943).
^' ;
(38)
. .. ::. I.
(39)
CHAP. Xll]
where
0.14 r
503
"^^
J*'^'^-*.
0.13
'-=5^^;
0.12
N^
^
^
0.11
^
^
0.10
0.0
g 0.09
I 0.08
: ^
^
T) -
' r
0.07
3.8 V\
0 94
1.0
0.06
0.05
0.04
0.4
Critical point
.044->
1^
0.7
0.8
0.9
Reduced Temperature
FIG. 109. Thermal Expansion and Compression of Liquids.
0.5
0.6
1.0
504
[CHAP. XII
20
1.0
0.568
0.0159
0.127
.243.1
63.1
1.0
1.0
0.044
180
100
0.878
1.59
0.0984
The value of pc reported in the International Critical Tables is 0.275 g per cc.
(40)
At the
(41)
CHAP. XII]
505
Paraffins:
(t>iwi) = 1.88 + 2Mnc;
cc per g-mole
(42)
where
nc = number of carbon atoms
The observed densities for the normal paraffins above tetradecane tend
to be lower than calculated from Equation (42), but it is believed that
these deviations may result from the fact that the densities were measured close to the melting points. On this basis densities calculated from
the equation should be more reliable for high-temperature applications
than those based on the experimental values.
It was found that the density data of other hydrocarbon series may be
represented by similar equations in which the addition of a CH2 group is
accompanied by an increase of 2.44 cc per g-mole in the value of (^iwi).
Thus,
Mono-olefins:
(?;iwi) = 1.1 -f- 2Mnc
(43)
Monocyclic aromatics:
(yiwi) = - 3 . 0 -1- 2.44nc
(44)
(45)
whei3 a and m are constants characteristic of the series. For the hydrocarbons m is equal to zero. For other series it may have a finite value,
either positive or negative. Thus, for the alcohols, both normal and
isomeric,
(wicoi) = 2.89 + 2.44nc - 1.23 log nc
(46)
506
M'<'
rp ^
0.0838 Tr.
0.1745 - (?;iaji)/y
i;'r;
[CHAP. XII
^^yj
where
V = the molal volume at temperature T under conditions such that Equation (40) is apphcable
'
Equation (47) may be used to estimate the critical temperature from
density data when the boiUng point is unknown. The boihng point
may then be estimated from the relationships between boiling and
critical points in Chapter III.
. ; ,ii,;
By means of Equation (III-9), page 70, it is possible to calculate the
critical volume from no data other than the structural formula. This
value may be substituted in Equation (41) and (vxcoi) evaluated. Then
the critical temperature may be calculated from Equation (47) if a single
liquid-density measurement is available. In this manner it is possible to
estimate densities at all conditions and, m t h the relationships of Chapter III, boiling points and vapor pressures from only the structural formula and one liquid-density measurement.
These* methods for estimating physicochemical properties are of
particular importance in dealing with unstable materials under conditions
which preclude direct measurements. However, it must be recognized
that all such methods are approximations to be used only in the absence
of more reliable data. In many cases several alternate relationships
may be used for estimating a property. In the present state of the data
it is best to compare the various methods with what direct measurements
are available on the compound in question and similar compounds, and
in this way select the most consistent and logical value for each particular
problem. The relative reliability of the various methods is to a large
extent dependent upon the type of fundamental data available.
Pressure Correction to Enthalpy of Liquids. Combination of Equation (38) ^\^th (XI-99) written in terms of reduced temperature and
pressure gives
> > , /.''
i(^) ,l-,.,(!i)=-fl-T,(i)l
Vc\dVr/T
\dTr/p
Pi Leo
(48)
\dTr/pJ
-^(fl..-).= r p + ^ ( ^ ) l * . = * (49)
CHAP. XII]
507
where Hep = enthalpy at temperature T and the critical pressure PcThe value of (aco/6r)p is obtained by graphically differentiating Fig. 109.
The results of the integration of Equation (49) are plotted against
reduced temperature and pressure in Fig. 110.
!
TABLE XXVIII
PHYSICAL PROPERTIES OF NORMAL PARAFFINS
2 -^^^ , 3
4
5
6
7
8
9
Pf
C
AUyma
Name
1 Methane
2 Ethane
3 Propane
4 Butane
5 Pentane
6 Hexane
7 Heptane
8 Octane
9 Nonane
10 Decane
12 Dodecane
14 Tetradecane
16 Hexadecane
18 Octadecane
20 Eioosane
25 Pentacosane
30 Triacontane
. 3 5 Pentatriacontane
40 Tetracontane
45 I Pentatetracontane
Mol.
Wgt.
16.04
30.07
44.09
58.12
72.15
86.17
100.20
114.22
128.25
142.28
170.32
198.38
226.43
254.48
282.54
352.67
422.80
492.93
563.06
633.19
TBR
201.2
331.8
416.2
491.1
557
615.7
669
718
763
805
881
948
1007
1060
1105
1210
1305
1385
1465
1540
lb per
rcRsgiri.
343 673
550 717
666 642
766 544
847 482
915 433
972 394
1025 362
1073 332
1114 308
1185 272
1248 244
1300 221
1343 202
1380 187
156
1545 133
1610 120
1675 108
1740 100
pl/Wi,
10
tiWi,
g per
cc per
cc
g-mole
3.679
4.36
4.429
6.81
4.803
9.18
5.002
11.62
5.128
14.07
5.216
16.52
6.285
18.96
5.340
21.39
6.382
23.83
5.414
26.28
6.459
31.20
6.483
36.18
5.48
*41.3
"5.49
46.3
'5.5
'51.
5.5
*64.
*5.5
^76.
S.S
SS.
3.3
103,
5.4
'118.
h
0.000
0.088
0.125
0.166
0.190
0.209
0.224
0.236
0.248
0.258
0.275
0.289
0.300
0.308
0.315
0.329
0.339
0.347
0.353
0.338
A
2.338
2.573
2.661
2.767
2.887
2.994
3.124
3.232
3.298
3.407
3.637
3.818
4.006
4.195
4.403
4.834
5.169
5.580
6.011
6.358
11
B
lb per
eqin.
5.166
5.428
5.468
5.502
5.570
5.631
5.719
5.790
5.819
5.896
6.071
6.205
6.350
6.500
6.675
7.027
7.293
7.660
8.045
8.358
Tc =
Pc =
Tn =
Pr, =
672.2R
643.3 lb per sq in. = 92,600 lb per sq ft
530/672.2 = 0.788
200/643.3 = 0.311
508
130
3
Reduced Pressure
FIG. 110. Enthalpy Correction for Liquids
[CHAP. XII
509
pn = 0.813
Hi = 102.3
pr, = 2.34
H,)T
= 20
20
^^--^-^--(0.00323)(778)^^-^^"P^'-^'^
Pressure Correction to Entropy of Liquids. Combination of Equation (38) with (h) Table XXIV written in terms of reduced temperature
gives
(50)
p. KdpJT
To \
dTr
)p
TcPl
dTr
^(&,-s),=+rife)dp.
(51)
where Sep entropy at temperature T and the critical pressure Pc. The
results of this integration are plotted against reduced temperature and
pressure in Fig. 111.
" B. H. Sage, W. N. Lacey and J. G. Schaafsma, Ind. Eng. Chem., 26, 1218 (1934).
510
1.0
FIG.
Ill
2.0
3.0
Reduced Pressure
Entropy Correction for Liquids.
[CHAP. XII
5.0
.msjBt^m-
cPi
(Cpc
^i
(53)
CHAP.
511
800
2.0
3.0
4.0
Reduced Pressure
PIG. 112. Heat-Capacity Correction for Liquids.
5.0
the critical pressure. A generalized evaluation of Equation (53) is obtained by differentiating Fig. 110. The results are plotted in Fig. 112.
By the general procedure of Illustration 10, Fig. 112 may be used to
estimate the change in heat capacity at constant pressure accompanying
any change in pressure at constant temperature.
Heat Capacity of a Saturated Liquid or Saturated Vapor. When the
temperature of a liquid at its boiling point is increased while saturation
is maintained, an accompanying increase in pressure results. The heat
capacity of such a saturated liquid involves the enthalpy change resulting from both the temperature and pressure changes. Thus, from Equation (XI-39),
512
[CHAP.
XII
(f).=a.-(a(^).
or
RTU
dz\
'.
,^^, ^
(56c)
CHAP. X I I ]
513
40
2
.
3
Reduced Pressure
FIG. 113. Differential Effect of Pressure upon the Enthalpy of Liquids.
The constant B may be evaluated from the boiling point and critical
data using Equation (VII-30), page 232. More nearly accurate values
of (dp/dT)s are obtained by differentiating Equation (III-16), page 73.
By the use of Fig. 113 in combination with Equation (57) the heat
capacity at constant pressure of a saturated liquid is calculated from a
_known value of the heat capacity of the saturated liquid. The heat
capacity at any other pressure is then calculated by means of Fig. 112.
This procedure is demonstrated in Illustration 12.
Heat Capacity of a Saturated Liquid from Cp of Its Ideal Gas. Data
on the heat capacities of liquids, particularly at temperatures other than
atmospheric are scanty and frequently unreliable. However, generalizations of statistical data discussed in Chapter XVI permit the estimation of heat capacities of ideal gases over wide temperature ranges.
A thermodjTiamic relation exists between the heat capacity of the ideal
gas and the heat capacity of the saturated liquid involving the heat of
vaporization and the effect of pressure on the enthalpy of the gas. From
this relation in generalized form together with Figs. 112 and 113 the heat
514
[CHAP.
XII
(59)
',,--'.( c . . - c > = - -
^^r
' ,
.'
(60)
''-.
. .,< '"'[-
[djii* - H,g)l
ra(H*-H^-|
, .-!
/dp\
^^^^
i- ( aK\
1 1 d{YL*
TAdTj
TX
Hs(?j I
dTr
r ' . r . ^ -.,; ;
i.
-p^m.'-)
T.
PcT,
n '^^(\^ T?T> I
;^
V 2 / I Trb)-^-^^
T ,\-0.38
\ n - 4 3 >'
'
0.^
.-
( 1 --
r^)0.62
(63)
/
( y
CHAP. X I I ]
where
515
70
50
40
30
Tl
20
11
-A
10
I
I
bo
o
I,
bO
7
5
4
S
//MYA/M
2
1,0
col
0,7
0.5
0.4
0.3
'/'ff
%
c
^ J^,
Yy
leduced tennperatui e
0.2
0.1
0.0004
0.0010.002
516
[CHAP. XII
K 7/ /
OJ_
c3 1
CO
i f^f
--^
c5
11
/
/
=>>;^^///
eo-V^
11 r
11
f/
^
%
i^i,
1
1
1
41
1 ^ "1/
03
o
d
>o
o
^^
0)
a
oo
so^*a>" >-.
t^ aS3
c3 J- t3J
(U
lO g<
t- h
o c
T3
a
W
1-2
^
o
^^W,
cd
otf
c3'
+->
S-3
^/
B
^
lih
lO
lO
to
oo
t;
A<
o
to
-a>
s
0)
iH
as
iCl
>flv
fi
o
f-H
rH
rt
I*.
8
o
00 C- 50 lO
(H ) Olom-3) / aBo-3)^( A ^ ) i
(ffiH)e' I
CHAP. XII]
517
,
p, = 43.7;atm;
Tt, = 228.6K
L228.6 - 43
373.4 - 43j
1600
8.62
1600
p, = 23.5 atm;
p, = 23.5/43.7 = 0.54
r . = 336/373.4 = 0.90;
Tr^ = 0.613
/228.6\2 (l-0.613)-<''
= -(0.361)(1.987)(1600) ( J
-^^3^^=-10.450cal/(g-mole)(OK)
From Fig. 114,
1 /a(H* - H ) \
~\
dTr )
=25.5cal/(g-moIe)(K)
\dTj,
_
(23.5) (1600)
-
- = 0.438 atm per K
(336 - 43)2
^
/'
/
= 2 8 + 2 5 , 5 - 4 1 . 1 = 12.4
%;
'",^\
518
T H E R M O D Y N A M I C PROPERTIES OF FLUIDS
[CHAP. X I I
(6) From the data of Illustration 11, PI/MI = 299 lb per cu ft or 4.8 g per cc.
Fig. 113,
!
' S
''' '
1 /SHN
From
(7.8) (44)
The factor 41.3 converts the energy units from cc-atm to calories while 44 is the
molecular weight of the gas. From Equation (56) and the value of (dp/dT), previously determined, (cp - C,)T = (l.73)(0.438) = 0.755oal/(g-mole)(K).
Cj, = 31.2 + 0.755 = 32.0, the heat capacity at constant pressure of the saturated
liquid at 63C
(c) F r o m F i g . 112,
. . - - - - ; :'- - 'r''^.V -...:i :,. -" ;/, :-.^:'U)UA
,..-
,
_
(c,,
c)
^-y
Cpc = 32.0 2.9 = 29, the molal heat capacity of the liquid at 63C and 43.7 atm.
{d) At 200 atm, pr = 4.58.
From Fig. 112,
,
^'"^
,
''''
';'
Cp = 29.1 - 4.8 = 24.3, the molal heat capacity of the liquid at 63C and 200 atm.
DETERMINATION OF THERMODYNAMIC DATA
Per Cent
15
30
CHAP. XII]
THERMODYNAMIC PROPERTIES
519
Per Cent
In the range of T", = 1.0 to 3.0 and p, = 0 to 10 with York and Weber's
correction
Nonideality correction for entropy of gas, Fig. 107
Pressure correction for heat capacity, Fig. 108
Expansion factors of liquids, Fig. 109
Pressure correction to enthalpy of liquids. Fig. 110
Pressure correction to entropy of hquids, Fig. I l l
Pressure correction to heat capacity of hquids, Fig. 112
Difference between heat capacity at constant pressure and heat capacity of
saturated liquid. Fig. 113 and Equation (56)
Difference between heat capacity of saturated liquid and ideal gas. Figs.
114^115 and Equation (62), in range Tr = 0.55 - 0.96
5
30
30
5
25
15
20
35
25
520
[CHAP. XII
CHAP. XII]
521
^
+ ClQgT + DT
(64)
This equation was found to deviate less than 0.3 per cent from the data.
It is more convenient and more accurate than the generaKzed Equation (III-16), page 73, which contains only three constants but is difficult
to evaluate from data.
The heat-capacity data were represented by Equation (VII-21),
page 213. Similar equations were used for liquid densities over limited
ranges.
The pVT data for the vapors were expressed by the Beattie-Bridgman
Equation (2). The constants were evaluated by Benning and McHarness^^ by the method of Buffington and Gilkey^^ which assumes that c is
zero and thus considerably simplifies the operations. This simplified
form is accurate where pT isometrics are linear.
V 1
THERMODYNAMIC CHARTS AND TABLES
For substances which are frequently used over wide ranges of temperature and pressure in both liquid and vapor phases, it is convenient to
prepare tables giving values of the important properties over this entire
range. Such tables are particularly indispensable for fluids used in
power generation and refrigeration. It is also common practice to present such information graphically in the form of charts. Since all the
properties of a pure component may be defined in terms of two independent properties, it is possible on a chart with two co-ordinate scales to
construct contour lines for all related'properties. For example, on a
chart with temperature and entropy as co-ordinates, it is possible to
construct additional contour lines for pressure, enthalpy, free energy,
specific heat, and other properties. This procedure is limited by the
confusion resulting from reading values from a multiplicity of intersecting hues. Tables have the advantage of permitting great accuracy
in the reproduction of values, whereas charts are more compact and aid
in visualizing the effects of changes.
The familiar steam tables have undergone extension and refinement
with the result that thermodynamic properties are now known with a
high degree of precision over wide ranges of temperatures and pressure
for the saturated vapor and Hquid, the superheated vapor, and the
compressed liquid. Data for saturated vapors are generally tabulated
in terms of the corresponding temperatures or pressures, whereas for the
22 R. M. Buffington and W. K. Gilkey, Ind. Eng. Chem., 23, 254 (1931).
522
[CHAP.
XII
Pressure-volume.
"--i..'
Temperature-enthalpy.
'
' ' ' ''
, '
Temperature-entropy
'"(i^, L
Enthalpy-entropy (MoUier chart). "
' ' ''
Auxiliary lines may be drawn on each of these charts to show the other
three properties or any other related property. Each chart has special
advantages for certain applications, as is discussed in succeeding chapters, although each chart may be constructed to include all the data of
the others. With known values of absolute entropies, it is also possible
to construct additional charts and tables giving values of free energy
and the total work function. Internal energy can be obtained from
values of enthalpy, pressure, and volume.,
A representative series of diagrams for ammonia is presented in
Figs. 116-119 plotted from tables based on direct experimental data^* up
to 300 lb per sq in. and extended by generalizations above that pressure
as indicated in broken lines. Since ammonia is extensively used as a
refrigerant, values of the enthalpy and entropy are arbitrarily assigned
zero values at the saturated-hquid state at 40F. The absolute
entropy of hquid ammonia at this state is 1.207 Btu/(lb)(R).
The general shape and appearance of Figs. 116-119 are characteristic
of such diagrams for substances of low molecular weight and low molalheat capacity. The other common refrigerants and water are represented by diagrams of similar appearance.
Diagrams from Generalizations. Since few thermodynamic data are
available for compounds of high molecular weight, it is generally necessary to resort to the generalized relations in order to develop diagrams for
such substances. Such a series of diagrams for benzene is shown in
*'J. H. Keenan and F. G. Keyes, " Thermodynamic Properties of Steam," John
Wiley & Sons, New York (1936).
" Natl. Bur. Standards U. S. Circ. 142 (1923). ,. . .,, ,. ,-. ,;,,:,. . ,..,,.:.,. -' ,
CHAP. X U ]
523
"
/^
4\'
i^N*/<^
,Ji
7 r- / /
'^^J
'
^^MM' ^ / ^
'^^" ,>
y
^ ^
^
/
^5^ ^',.
^
^/
/ /
^
S
/ /
* y /
y
/
.^
^' ' /
g
y
I'^S^^ . / ** ,
CO
^t
<!
J yy^j
JT ^
'
4
/'r
'J' '
/
J
''
/if
lit'
HJ-'V
S^fcT
'
S 0 1.'
'
;, LL . y
'
kXX-v-'
'
I' 1
1^2 ~
d,
/
0
'
'
<
, A0
v
-'
'Ut-^^ti ^
. ' ''
g-IC44^ ^ ,
i-trr-
5E..^__!
'S
~'~'I..
'a
f.'""
I P9:}B J ^iBc;
~"
+3
u
O
O
O
I!
oo
oo
OOO
t-l
o
o
o
o
c>
o
CO
o
o
(M
OOO
o o
ooo^o
Tj< CO
(M
1-i
00 ;P
, '
N g
4ll-
o
O
1
^' a^
'-+{'-'
.'1 ^i.A
.'V^
^W^'
/
y/ji^ Y ' /
^^ t\d
^ : /
03
CD
P.
CO
C<1
-<
-100
-50
60
100
[CHAP.
XII
400
450
Figs. 120-122. As a minimum requirement direct data must be available for the normal boiling point, the specific gravity of the Uquid, and
the chemical structure. The heat capacity of the vapor may be estimated by the generaUzed methods discussed in Chapter XVII. The
critical temperature and pressure and the complete vapor-pressuretemperature relation may be approximated by the methods of Chapter III and the heat of vaporization by the methods of Chapter VII.
In the case of benzene, these data were available from direct experimental
measurements and accordingly were used in preference to estimated
values.
In developing a series of diagrams it is convenient first to establish
enthalpy as a function of temperature for a series of constant pressures.
Enthalpies are generally referred to the saturated liquid at an arbitrary
temperature, in this case 60F. The enthalpy of the saturated vapor
at the reference state is first calculated by correcting the normal heat of
vaporization for temperature by means of Equation (VII-32), page 233.
The enthalpy of the vapor at this temperature and zero pressure is
CHAP. X I I ]
^o'?
525
526
[CHAP. XII
CHAP.
XII]
100
527
200
300
400
500
600
Temperature, t F.
FIG. 120. Enthalpy-Temperature Chart for Benzene,
700
800
^
-b^^
\ /
/
600
p=600J
o = 40(
/^
.m
^^
..A-*'^
\^^
200
a&^ ^
i p=30 3 ^ ^ ^^
7 ^ %m-
V""^'
Critical p oint-;
\v- -200-
^
Ib/sq in. al
w^
\
= 14.7-
?
y*
/to
%
N *v 11
%
\
O.B
0.6
0.7
0.8
0.9
S, Btu/(lb)rR)
PIG. 121. Temperature-Entropy Chart for Benzene.
1.0
1.1
528
100
0.70
0.80
0,85 ,
0.90
S, Entropy Btu/(lb) (R)
FIG. 122. Enthalpy-Entropy Chart for Benzene.
[CHAP. XII
CHAP. XII]
529
530
[CHAP.
XII
at
,-
.
177F (637R)(354K)
5 5 r F (1011R)(561K)
704 lb per sq in. (47 9 atm)
'
0.874 g per cc at 77F
78.04
-i< f '
'i
j
j
/
'
%v.
^
2.8096
\ r
e-M(r,H!.i88) nim Hg
CHAP. XII]
531
n - 43 "" r . - 43
520
354 - 43 ~ 561 - 43
637
^' = H I = -^^^'
/
( n ) . = = 0.631
\2
/354\2
or
8230
z-TT (1.8) = 190 Btu per lb
78.04
190
At the low pressure of 1.15 lb per sq in., ideal behavior may be assumed, and these
values may be taken as representing the ideal state.
(o) At 49lF and 1.15 (lb)/{sq in.), if we assume ideal behavior;
1
/"gsi
H* = 190 + /
[-5.70 + (54.14)(lO-^D - (13.41)(10-)T2] dT
78.04 J520
= 338 Btu per lb
1
S* = 0.896 + r r ^
/95i r _ 5 70
"I
^ ^ + (54.14) (10"^) - (13.41) (10-)r dT
78.041/520
L i
= 1.095
(5) At i91F, 200 lb per sq in.:
Tr =
951
= 0.94;
1011
'
H* - H
From Fig. 105, ^
= 0.91;
1c
200 ,
pr = = 0.284
'^
704
920
H * - H = 920 or = 11.8 Btu per lb.
7o.U4
532
[CHAP. XII
1.987 470
S* = 1.095 - In - = 1.095 - 0.152 = 0.943
78.04
1.15
S = 0.943 - 0.036 = 0.907
(d) Saturated liquid at 491F:
X = 85 Btu per lb
#
ASx = =0.089
951
ff = 298 - 85 = 213
<S = 0.907 - 0.089 = 0.818
Tr = 0.94
(He - H) = - 6 . 0
Pc W
For benzene:
,
pi
= 6.71 g per cc
-l- = ( ^
Pcoji
(47.9)
CHAP. XII]
INTERNAL ENERGY
533
Hence,
o
- 1 . 9 Btu per lb
iPc
^
'
'
47.9
=
'
'
'
'
'
Tr = 0.94;
pr = 4.26
= 12.5
12.5
He - H = - = 2.16 cal per g or 3.9 Btu per lb
58
H = Hi-
From Fig. I l l ,
(Se-S)=
48
aiPe
S = Se-
The completed enthalpy-temperature, temperature-entropy and enthalpy-entropy charts for benzene, constructed from points calculated by the methods shovra
in this illustration, are shown in Figs. 120, 121, and 122.
534
[CHAP. XII
AU = AH ~ AipV)
(65)
(66)
Similarly, by definition,
,..,.,,..,
AG = AH~A{TS)
/:
(67)
" '^'
(68)
As was pointed out in Chapter XI, it is evident that a knowledge of absolute values of entropy is necessary for the determination of free-energy .
changes in all except isothermal operations.
'
Combination of Equation (65) with the definition of the total work
function gives
, ,'!' ; ' "'> ^
AA^
AH - A{pV) - A(TS)
, \
(69)
^
(70)
Illustration 14. The absolute entropy of liquid water at 25C (77F) is 16.75 entropy units per mole. Calculate the internal energy, free energy, and total work
function, in Btu per lb of saturated water vapor at an absolute pressure of 125 lb per
sq in., relative to the saturated liquid at 32F. Use the enthalpy and entropy data of
the steam tables, and assume the heat capacity of liquid water between 32F and
77F to be constant at 1.0 Btu per lb per F, and neglect the effect of pressure on the
entropy of the saturated liquid in this range.
Solution: The absolute entropy of the reference state is calculated from Equation (17):
^
'
"
'<'"'"
CHAP. XII]
PROBLEMS
535
536
[CHAP. XII
/
, /
/^:
/
The vapor pressure may be obtained from Equation (III-16), page 73, which is
most conveniently used by plotting a curve relating vapor pressure on a logarithmic
scale to temperature on a uniform or reciprocal scale.
20. For methane gas at 122F and 1000 lb per sq in. abs, calculate the values of
CHAP.
537
PROBLEMS
XII]
U, H, S, Cp,G, and A, per pound mole relative to the actual gas a t 32F and 1 a t m
pressure by the generalized method and also by the Benedict-Webb-Rubin equation
of state. The absolute molal entropy of methane gas in the ideal state at 32F and
1 a t m pressure is 44.5 Btu/(lb-mole) (R). The other necessary data are contained
in Table X X I , page 336, and X X V I I , page 483.
21. Benning and McHarness" determined the following constants for dichlorofluoromethane CHCI2F (molecular weight 102.9): In Equation (2),
A =
Bo =
c =
p =
V =
20.54
0.286
0
atmospheres
liters per gram-mole
a
6
R
T
= -0.179
= 0.497
= 0.08206
degrees Kelvin
In Equation (64),
A = 38.2974
C = -13.0295
p = atmospberes
B = -2367.41
D = 0.0071731
T = degrees Kelvin
t degrees centigrade
CHAPTER X I I I
EXPANSION AND COMPRESSION OF FLUIDS
The most useful form of energy into which it is generally desirable to
convert other forms is the mechanical work of motion as represented by a
rotating shaft or a moving piston. Mechanical work is defined as the
energy which is transferred by the effect of a force acting through a distance and is equal to the product of that force times the distance of
action. Thus, when a fluid which is confined under pressure undergoes
a change in volume, work is done as the result of the force of pressure
moving through the distance corresponding to the volume change.
Similarly, a flowing fluid may perform work through changes in volume,
elevation, or external kinetic energy.
As pointed out in Chapter VII, work is a form of energy which is
incapable of storage as such but is in transition from one form of stored
energy to another. Mechanical energy in this transitory form is termed
shaft work, as distinguished from the electrical and other forms of work
which may be included in the work term of a complete energy balance.
Shaft work is capable of transmission as such and may pass from one part
of a system to another through either solid media such as shafts, pistons,
gears, and belts or through fluid media such as hydraulic or pneumatic
couplings and drives. However, no transmission device is perfect, and
some work is always lost by degradation to a lower form of energy, made
manifest as heat resulting from friction.
Differential Energy Balance. In Chapter VII a general energy
balance was estabhshed for a complex chemical process involving several
interconnected systems. By applying this energy equation to an infinitesimal change in the energy of a single system of constant mass m and
constant composition, the following differential form results,
d{pV) +d[-)+
(1)
where the energy terms represent in order, flow work, external kinetic
energy, potential energy, surface energy, internal energy, heat added
from the surroundings, and work done upon the surroundings. The
work term d'w, in general, includes all possible forms of work, such as
638
CHAP. X I I I ]
539
. ,,
r2
or
w, (nonflow)
'
" ^ = I
pdV
/')G\;
(4)
- d[-]-
d{mZ) - d(mE^)
(5)
540
[CHAP.
XIII
(flow) = -J
Vdp
(6)
(J)
-)^=-V
or
-(A4).= j ^
{vdV)r
= {WS)T (nonflow)
(k)
(J)
(7)
(k)
(8)
(9)
(10)
reversible
expansion
reversible
expansion
CHAP. XIII]
541
From Equations (7-10) it is evident that the work of reversible expansion of a fluid under isothermal or isentropic conditions may be determined either by a pressure-volume integration or as the change of the
appropriate energy function. The pV integration must follow the
actual reversible path of the change, whereas the thermodynamic
energy fimctions are state properties which are independent of path and
are completely defined by the reference properties. Either method of
calculating work may be employed with thermodynamic data based on
either experimental measurements or generalized correlations. The
choice of the method is determined by the type of data available. However, in general, it is more convenient to evaluate the thermodynamic
energy functions at the terminal states of the system than to carry out
integrations from equations of state.
Isothermal Nonflow Expansion. For the reversible isothermal expansion of any fluid imder nonflow conditions, from Equation (7) and
the definitions of the thermodynamic energy functions
"
'
- *
pdv='
-vdp=
-RT^
(12)*
P
Substitution of (12) in (11) and integration give
(wf)r (nonflow) = - f l r I n -
(13)*
pi
-vdp
+ RTdz=
-RTz
RTdz'jlS)
or
{W,)T (nonflow) = -RT
zdlnp+
RT{Zi - zi)
(16)
542
[CHAP.
XIII
"*'^ '
"
+RT{z,-z^)
(17)
-)
.-;
Tc
To
+RT{Z2-Zi)
(18)
+TAS
(19)
, (20)*
Thus for an ideal gas the work of reversible isothermal expansion is the
same for flow as for nonflow conditions. This results from the fact that
at constant temperature the change in flow work is zero for an ideal gas,
or d{pV) = 0.
CHAP. XIII]
(flow) = -RT
543
or
zdlnp
(21)
- . [ (Hr-HO_(Hr^-|
^^^
Pi
2
(6) For actiuil-behavior nonflow conditions the value of I z d In p in Equation (16)
is obtained by plotting values of z against values of log p and integrating over the
limits log 50 to log 1. The necessary data, read from Fig. 103 at a reduced temperature of 1.11 for reduced pressures from 0.0197 (1.0 atm) to 0.983 (50 atm) are tabulated as follows:
log p
p (atm)
z
P'
0.0
1.00
0.0196
1.0
0.707
0.98
5.09
0.1
1.008
0.96
10.18
0.2
1.118
0.94
15.27
0.3
20.36
1.304
0.90
0.4
1.406
0.87
25.45
0.5
30.54
1.484
0.84
0.6
1.552
35.63
0.805
0.7
1.610
0.77
40.72
0.8
1.681
0.73
45.81
0.9
1.699
0.71
0.982
50.0
The area under this curve is determined to be 1.59. Then, substitution in Equation (16) gives
w, = (1.987) (564) [(2.303) (1.59) + (1.00-0.71)] = 4440 Btu
This problem can be solved without graphical integration by means of Equation (18).
, : . ^ . , , v > -G. , ; . , , , : . . , , ; , ; , . . , : .
,; -.
544
[CHAP. XIII
CHAP. XIII]
545
iP dV)s = - ( A t / ) s = [ - A ^ + A(,pV)]s
(23)
pdv=
-vdp
+ RdT = -ctdT
(25)*
Eliminating v from (25) and rearranging and combining with Equation (XI-134), page 474, gives
.^
-^dp=-{c:
+ R/-^=-c*/-^
(26)*
Where moderate temperature changes are involved, it is generally satisfactory to assume a constant mean value of (c*)m at the arithmetic mean
temperature. Then Equation (26) is integrated to give
ii!ln(^)=(c:).ln(g)
or
.,
(27)^
;(28)*
T2
r^^VsL
'
(>r)s (nonflow) =
{C*)UT.
(29)*
It should be noted that (Cj,)^ and (Cj,)m are different averages which
result from differential equations involving dlnT and dT, respectively.
546
[CHAP.
XIII
Equations (28), (29), and (30) are frequently written in terms of K, tlie
ratio of the heat capacities at constant pressure and constant volume.
For an ideal gas,
c*
ct + R
u;n !:;M P
(31) *
Cn R
c
Combination of (31) with (28), (29), a n d (30), respectively, gives
T,= TJ^)
:/':':
(32)*
t-1
(,.*) ( n o n f l o w ) = - ^ [ l - ^ ) " ]
(33) *
(35)
s* - si* = f \ldhxT
- R\n-
. (36)"
where c,;, the molal heat capacity for ideal behavior, is a function of
temperature only.
Combination of (35) and (36) gives
/
^'
cld\n
r.
P2
T - R\n - {4 - Ss) -1- (sf - Si) = 0
Pi
(37)
CHAP. X I I I ]
I S E N T R O P I C N O N F L O W EXPANSION
547
The integral of Equation (37) is evaluated analytically from the empirical heat-capacity equation for the ideal gas. The equation is then
solved for the final temperature corresponding to a specified final pressure
and initial state. This is best done by assuming a series of final temperatures and plotting the corresponding values of the left-hand side of
the equation. For ideal gases the two (s* s) terms become zero.
Once the initial and final states are defined the reversible work is
calculated directly from Equation (23) from the terminal enthalpy and
pV values.
If condensation occurs during the expansion, Equation (37) is applicable only until conditions of saturation are reached. A final temperature calculation from Equation (37) which is lower than the boiling point
at the final pressure is proof of condensation and establishes the correct
final temperature as the boiling point under the final pressure.
Where a chart of the thermodynamic properties of the system is
available, the final temperature is obtained directly by the following:
X2\
X2
S2, - Y)^
^' ~ (^ ~ ^2)
(38)
or
A s = S2 -
Si = (S2* -
Si*) -
(S*, -
S2s) + (sj* -
Si)
- (1 - X2) ^ = 0
(39)
where S2, is the entropy per mole of the saturated vapor and X2 is the
molal heat of vaporization at temperature T2 which is calculated by the
methods of Chapter VII. Equation (39) may be solved for quality X2 by
use of Equation (36), Fig. 107, and the temperature of condensation
corresponding to the final pressure p^.
Once the final quahty is evaluated, the work is calculated from the
enthalpy and pV changes of Equation (23). The enthalpies and
volumes of the saturated hquid and vapor are separately evaluated by
the methods previously demonstrated. If the generalized correlations
are used, the complete expression for the shaft work per mole is as follows:
(..)s(nonflow) = f \ U T - T. [
^ ^ ^ ]
+ (l - x,)CK2 + P2V2)
(40)
I
548
[CHAP.
XIII
Vdv=
-AH =. - J^cldT
(41)*
- Rd]iip= - 4d]nT
, ^ , (42)* '
j
^ 1
(^.%(flow) = ^ [ l - ^ ) " ]
(44)*
For an actual gas under flow conditions the procedure is similar to that
followed in the isentropic nonflow case. Equations (35-39) are all
directly applicable to the flow case since they express the condition of
constant entropy. Thus, it may be concluded that for anyfluidthe
temperature changes in isentropic expansion are the same forflowand
nonflow processes.
If the final temperature is known, values of w, follow from Equa-,
tion (10). Thus, if the generalized correlations are used, the work per
mole is expressed by
(w,)s (flow) = fj>,
dT - r . [
-Hx
H*- H,
r J
+ (1 - Xi)\2 (45)
CHAP. XIII]
ISENTROPIC EXPANSION
549
When Equations (23) and (41) are compared, it is evident that the
work in isentropic flow expansion is greater than that of a nonflow operation by the amount of A(pF).
Illustration 3. Calculate the work of isentropic expansion of 1 lb-mole of ethylene
gas when expanded from an initial pressure of 60 atm and 564R to a final pressure of
1 atm under nonflow and flow conditions.
For nonflow conditions assuming ideal behavior, an equation for the heat capacity of
ethylene, at zero pressure in the temperature range below 200F is given in Table XXI,
page 336.
4 = 7.95 + 8.13 X 10-"(r)'-
Combining this equation with Equation (26) and integrating gives
C^' r7.95
I
- ^ + 8.13(10-")(r)ii-85 \dT = R In = 7.95
564 L -i
J
50
+ 2.11(10-")[(r2)5-85 - (564)=-8=^]
This equation is solved graphically for Ti giving T2 = 234R. The reversible work
of expansion is obtained by combination of Equations (23) and (25) with the heatcapacity equation:
(^234
/504
CvdT = \
564
[7.95 + 8.13(10^")(D'-ss _ n] dT
1/234
(w*) s(flow) = /
/234
I
564
1.11
50
0.982
2.3
1.55
0.71
2
304
0.598
1.0
0.0196
0.39
0.64
0.98
The molal heat of vaporization at 1 atm is estimated from the available experimental data as 6200 Btu per lb-mole. From Equation (36),
s* _ s,* = 7.95 In ^
'
304
\
550
[CHAP. XIII
The terms in Equation (40) may be evaluated individually, the volume of the liquid
being neglected. Thus,
"
'
/564
304
'304
Hi
VL* H2^
(1 - x ) X = (0.15)(6200) = 930
'
, -
I ' .'
. =,
'
',
, .
f,',.
;
T
CHAP. XIII]
JOULE-THOMSON EXPANSION
661
FREE EXPANSION
The unrestrained expansion of a gas is known as free expansion.
Under conditions of no restraint no work is done, and under adiabatic
conditions no heat is added. Free expansion under flow conditions is
commonly known as throttling or as the Joule-Thomson effect referred
to in Chapter X I I .
The Joule-Thomson effect is measured experimentally by expanding
the gas slowly and in steady flow through a well insulated porous plug;
in this way potential work is lost, and no heat is allowed to enter or leave
the system through the walls. The fluid flows reversibly into and out
of the process, but the expansion step is completely irreversible. Since
no heat is added or lost, the process takes place imder conditions of constant enthalpy, according to Equation (VII-11), page 207. However a
change in internal energy results if any change in flow energy pV occurs.
For an ideal gas, since enthalpy is independent of pressure, no change
in temperature occurs in free expansion imder either nonflow or flow
conditions, and values of AH, A(pV), and AU are zero. However, an
increase in entropy results which is equal to J? In P2/P1 by Equation (XI-142), and the values of A A and AG are each equal to T AS.
For nonideal gases, the temperature change in Joule-Thomson expansion is of great experimental and practical value. Such data are used for
establishing the deviations from ideal behavior of real gases, particularly
the effects of pressure on enthalpy and entropy. Free expansion under
flow conditions is made use of industrially in the cooling and liquefaction
of gases.
'
, : '.
Free expansion under nonflow conditions, known as the Maxwell
effect, is of little practical value. Because of the small heat capacity of a
gas compared with that of the vessel, adiabatic conditions cannot be
approached, and experimental measurements are of uncertain accuracy.
In the foregoing discussion it was assumed that kinetic energy changes
were negligible as is generally the case. Where this is not true, the
general energy-balance equation including kinetic-energy changes must
be employed. Changes in both internal energy and temperature may
result from the free expansion of an ideal gas at high velocities in either a
flow or nonflow system.
Joule-Thomson Expansion. The Joule-Thomson coefficient is given
by Equation (XII-35), page 501. Temperature changes in free expansion
where only small changes are involved and where the heat capacity may
be taken as constant may be calculated from Equation (XII-37).
Where large temperature changes are involved, these calculations are
more conveniently carried out through differences in state properties.
552
[CHAP.
XIII
AH = ' . ; . r - r . [ s J ^ - ! ^ ] = o
(46)
Equation (46) may be solved by assuming values of T2 until the conditions of the equation are satisfied by graphical or trial methods.
If condensation occurs during the expansion, the final temperature
will be the boiling point at the final pressure. Equation (46) must be
modified to include the enthalpies of the liquid and vapor phases and
the quality X2. Thus,
AH = C U T
T . [ 5 ^
_ 5 t ^ ]
_ (1 _ , , ) x ,
= 0
(47)
where X2 is the heat of vaporization at the final conditions and H2s is the
enthalpy per mole of the saturated vapor at state 2. Equation (47) may
be solved for xa since the final temperature T2 is known.
After the final temperature T2 is evaluated, the changes in the other
state properties follow. Thus,
.-.
A{vv) = XiZiRTi + (1 - xi)p2VLi - ZiRTi
(48)
JT,
,
Au =
AH
-^(l~x,)
(49)
AA = ziRTi
(50)
,,
. ;.
'
- . <51)
;
(52)/
CHAP. XIII]
MAXWELL EXPANSION
553
Thus, from an
T . ( ^ )
^ + T . ( ^ ^
(53)
The final temperature T'2 may be evaluated from Equation (53), and
the other state properties may be calculated from Equations (48-52).
Maxwell Expansion. As previously pointed out, adiabatic free expansion under nonflow conditions is characterized by constant internal
energy. Thus,
^
AU = 0 = AH - A{pV)
(54)
Equation (54) may be expressed in terms of generalized corrections and
ideal behavior to give, in the absence of condensation,
A. = f
t dT - T. (
+ r . ( 5 ^ ) - Z.RT.
+ ziRTi = 0 (55)
Tri = 1.11
p,i = 0.982;
zi = 0.71
H^ - Hi = 1218
s* - Si = 1.55
7,2=0.905;
pr2 = 0.0196
554
0.0196
HJ - HJ -
[CHAP. XIII
(0.1) (508) = 33
U.Uo
The term 0.0196/0.03 represents the hnear factor for pressures which are off the
chart. Atpr = .03; (H* - a)/T^ = 0.10. From the data of Illustration (3),
' /^460
'
564
\
r^^ r7.95
'
\-i;r + (8.13)10-"r2-85 \dT -Rln
= 6.45
564 L r
J
50
Substituting in Equation (49), yields
Hence,
."!
r*ma,'
-<i>i.
-(H^
- H2) +
(H*
HJ
= - 3 3 + 1218
' '
,.
'
EXPANSION OF ETHYLENE
CHAP. XIIIl
o o o o o o
i> r^ lo >o t^ t CO CO 0 5 OS CO CO
^T" ^ ^ ^ ^ ^f^ ' ' ^ ^ ^
I1 Ii
o o
o
o
o
o
lOiO
.(
T 7 7
11
o o o o o o
r>-1> CO ^ t ^ 1>"
c o c o OS c : ^ ^ ^
<1
1 1 ;:^;^ 1 1
O O o "^O O O
i > . i>-,1 >(i> t ^
CO CO CD CD CO ^7
<
555
o o
o o
Tt< - I *
11
oco
00 00
ccco
1 1 22 1 1 11
o
o>
o
o>
CO
03
CO
C33
CO
1
CO
OS
OS
1-^
00
00
03
<
n
m
t.
V.
o o
o o
o o
cnro
o o g g o o
<]
<N (N
1 1
COCO
<
COCO
00 00
11
coco
toco
O O O C D O O
I?
(jQ
II
coco
coco
So
IN
g"
t^lr^cooi _
cococoo>
Oi
o o
^ J ^ o o o o
coo
00 C
coo
CO
(N
lO
00
00
o
1
o
1
o
o
o
o
11
o
T3
CO
(N
10
TtH
00
00
CO
CO
CO
OS
1>
CO
IN
o o
lOiO
o o
coco
m
<l
(D
00
tl-l
^
p.
o
^
-yl
+
C5 a;
o w
rt "-i
IS
CO
Ol OS lO l O O l C i
^
^
^ | > , | > ^
^
lt I* ^
r-H
T^
^^
;D
o '
aa
oj o ft S
ir
^ !>>
S&^-s S
C3
I
.a
JS
oo
00
I1
CO CD
inio
CO
CO
o
OS
IN
(N
N
CO
CO
00
03 05
o o d o o o
^ P ^ ^ ^ ^ '^T' ^ ^
r-> CO O CO CO O
t-^ ,-1
o
o
003
^ i N co-*mco
/
556
HJ - Hz = 33
[CHAP. XIII
-^
i/564
B In -
50
'
- ;
'
CYCLIC PROCESSES
CHAP. XIII]
557
On the other hand, in a steam-power plant the change may be continually recirculated through a series of operations such as feed-water
heating, evaporation, superheating, expansion, and condensation. Such
a cycle is essentially composed of flow operations but may involve component nonflow steps such as the expansion of steam in a reciprocating
engine.
Nonflow cyclic operations repeated on the same mass of substance
have no present practical applications but are of great value in establishing the theoretical behavior of cyclic processes in general.
Reversible Cycles. A cycHc process which is wholly reversible must
of necessity be composed of individual steps each of which is in itself
reversible. This requires that at no point in the cycle may there be
degradation of higher forms of energy to heat through mechanical or
fluid friction, nor may there be any other irreversible steps such as free
expansion of a fluid or the transfer of heat under a finite temperature
difference.
The concept of reversibihty as discussed in Chapter X I requires that a
reversible cycle may be operated in either a forward or a reverse direction and must return to any given initial state without change in any of
the state properties of the system. Thus, it follows that in any reversible
cycle the algebraic sum of the changes in any state property for all steps
must be equal to zero. Thus, for any reversible cycle,
HAS
/V'-
The Camot Cycle. It has been previously stated that the maximum
shaft work accomplished as a result of any change in state of a fluid is
obtained when the change takes place reversibly without friction or
turbulence. The Carnot engine has been conceived as a hypothetical
device which represents this maximum achievement in a cyclic process
and hence is used as a standard in evaluating the efficiency and performance of all actual mechanical cycles for transforming heat energy
into mechanical energy.
In the Carnot engine, a gas is contained in a cylinder equipped with a
frictionless piston connected to a frictionless receiver of mechanical
energy. The cylinder walls and piston are impervious to heat, but the
cylinder head is interchangeable alternately to an impervious or to a
highly conducting plate. In the first stage of the cycle, that of isothermal expansion, heat is supplied to the gas through the conducting
cylinder head from a source of heat maintained at a constant temperature
Ti and flows into the fluid as a result of an infinitesimal temperature
drop. The gas is allowed to expand isothermally and reversibly with an
558
[CHAP.
XIII
influx of heat equal to gi. The reversible work of expansion from state a
to state b ia I p dV.
The first stage is followed by a reversible adiabatic or isentropic
expansion which is accompUshed theoretically by attaching the nonconducting head to the cylinder and permitting expansion to continue.
Work of adiabatic expansion is performed at the expense of the internal
energy of the fluid and in expanding from state h to state c is equal to
/ p dV.
pdV.
Since by completing the cycle the fluid is returned to its original state,
its net internal energy change is zero. The same is true of all other point
properties. Since no heat was received or lost during either adiabatic
change, it follows from the law of conservation of energy that the net
work done, Wnet, must equal qi + q-i. This is equal to the difference
between the amount of heat received from the reservoir at temperature
Ti and the amount rejected to the receiver at temperature T2. Thus,
w^net = vdV
+ vdV
+ pdV
+ vdV
- / '
' -
\ dV = qi+ q,
(57)
(58)
CHAP. XIIIl
559
21
Ti
Tg
(59)
The ratio Wnet/gi expressed by Equation (59) is termed the thermodynamic efficiency of he cycle. It will be recognized that an efficiency of
100 per cent can be realized only when the temperature of the receiver is
at absolute zero.
The operation and efficiency of the Carnot cycle is shown graphically
by straight lines on the temperature-entropy diagram, Fig. 123. During the first stage, the reversible isothermal expansion at temperature Ti is
'
represented by the horizontal line ab;
the heat removed from the source is
represented by the area SaObSb or TiAS.
" a/l.V
During the second stage, the reversible
adiabatic expansion is represented by
9i
'\
the vertical line be with no change in
/ .
entropy and with no heat added. In
/ d
c \
1 Jthe third stage, heat is rejected at Ti
-92
along horizontal line cd and is represented by area Sa dcSb or T2 ASi. In
1
1
1
1
the last stage the adiabatic compression
Sa
moves along a vertical line da of constant
entropy and with no heat rejected. The
FIG. 123. The Carnot Cycle.
net work done Wnet is represented by
area abed equal to gi + q^. The thermodynamic efficiency of the cycle
may be visualized as the ratio of area abed to area abcSbSad.
The Carnot cycle also may be operated by starting with a saturated
liquid and vaporizing it during the first stage. This condition is indicated on Fig. 123 by the curved line which represents the temperatureentropy relationship of the saturated vapor and liquid of the working
fluid. On such a vapor cycle two phases exist in the cylinder at all
points except a where the system is completely liquefied and b where it is
completely vaporized. Other methods of operation might involve
varying degrees of hquefaction at the various points of the cycle, but in
all cases the energy transformations are expressed by Equations (57-59).
The concept of the Carnot eng'ne permits visualization of the significance of the Carnot principle and the second law of thermodynamics.
The Carnot principle involves two basic conclusions which follow directly
from Equations (56-59) and the second law of thermodynamics.
560
[CHAP.
XIII
?2
T2
=
(60)
CHAP. XIII]
POWER-PLANT CYCLES
561
, Pump
6 a
Condenser
c' of
by
/r
\d
e \
pm
h 5
Pi
P,
1
1
b'a'
d'
562
[CHAP. X H I
= (pa - Pb)Vf
<61)
where v/ is the average specific volume of the feed. The work of pumping
is represented on the pV diagram as the area mban. If the pumping
operation is a reversible process, and changes in kinetic and potential
energy are negligible, the work done upon the fluid is also equal to the
increase in enthalpy, or
-wi = Hi-Ha ,: , (62)
In the second stage the water is heated along line bed, becomes saturated at point c and temperature Ti and then vaporizes at constant
temperature Ti and pressure pi to form saturated vapor at d. The TS
diagram shows the wide departure from isentropic conditions in heating
the liquid from Ti to Ti, as represented by the slope of the line be and the
area bee'. The gain in enthalpy is represented by Hd Hb on the HS
diagram. If kinetic-energy terms are neglected, the heat supplied is
equal to Hd Hb or I T dS, which is represented on the TS diagram
by the area SiobcdeSi.
Thus,
>
qi = Hd-Hb= f'TdS
'
. (63)
"
CHAP. XIII]
POWER-PLANT CYCLES
563
equal to the heat absorbed less the heat rejected if kinetic energy changes
are negligible. Thus,
np2
'
Vdp-
{pi-
(64)
The net work done during the cycle is represented by (Hd He)
(Hb Ha) on the HS diagram, by the area abde on the pV diagram and
by the area abcde on the TS diagram.
The ideal thermodynamic efficiency of the Rankine cycle is represented by
Waei 9l + Qi
(Hd - H,) - (HI, - Ha)
(65)
;
2i
2i
. Hd Hb
or, if pump work is neglected,
,
"'net
Hd - He
qi
Hd Ha
(66)
areas (A + B)
cycle as
; , r^ i ^x *
'
area (A + B + D + C)
The efficiency of the Rankine cycle can be increased by increasing the
temperature and pressure of the saturated steam supply or by lowering
the temperature at which condensation takes place. For the same
temperature change it is evident from Fig. 126b that a decrease in the
condensation temperature is more effective than an increase in the
temperature of the saturated steam. Increased efficiency obtained by
lowering the temperature of condensation is limited by the temperature
of the cooling-water supply. For boilers operating at the same pressure,
greater efficiency can be expected from this source in cold than in hot
564
[CHAP.
XIII
\d
r,--
r^
II 9\\
iri
B
IL
Si S4S3S2
( a ) Camot and Eankine Cycles
T
Ts
T.
'I
7;.
T2
-/-n
-/
S4=
/!
/1
Sy
(6) Effect of Increasing High
Pressure and Decreasing
Lew Pressure
^ "a
3 ,Q
-i
III m^
S2S3S4 g
Si
S3S2
(/)Effect of using
Process Steam
CHAP. XIII]
HEAT EXCHANGERS
565
566
[CHAP.
XIII
(Cp)m In - ^ The net gain in entropy is the algebraic sum of the two
-'2
changes or
/ T^ \
Hi H2
(67a)
Engine efficiencies vary widely with size and design, ranging from as
high as 80 per cent for large well-designed turbines and reciprocating
engines down to 30 per cent or less for small units of inferior design.
CHAP. XIII]
56?
150
164.7
365.9
1195.6
338.4
1.562
0.523
0.0182
From Equations (38) and (39), the nomenclature of Fig. 125 is used,
Sd - S. = 0 = 1.562 - [1.757* + (1 - x)(0.312)l = 0
" /.
X = 0.865, the quality after expansion
H. = (1150.4)(0.865) + (180.1)(0.135) = 1019.5 Btu per lb
From Equation (61), w , ,; :
; . ; ; :
568
[CHAP. XIII
^ =
= 0.173 or the ideal thermodynamic efficiency is
g,
1195.6-(180.1 +0.465)
or
365.9 + 460
The ideal work obtained from the steam in the engine is given by Equation (10),
(u).),(flow) = 1195.6 - 1019.5 = 176.1 Btu per lb.
2545
Ideal water rate of engine = r z r r = 14.6 lb per hp-hr
Thus, if the design of the engine were such as to result in an engine efficiency of 60 per
cent the over-all thermodynamic efficiency would be 10.4 per cent, and the actual
water rate of the engine 24.2 lb per hp-hr.
COMPBESSIOI^ 0 GASES
/
- /
CHAP. XIII]
lAe
Pj d
TI
\ ,
Isothermal
VIsentropic
IsentropiC
\ *<;*^rntercooling
\ f
(2) ,.
" ^s^^Isentropic
I
y
(a)
'"'~
569
e
Intercoolins
K -^Z
' l*-Isentropie
yj ^
'p'j^
I >.
\y^
K-lsentropic
r^Isothermal
X
g, n
(6)
FIG. 127. Compression of Gases.
LIL
m
-(w.)s = jT Ydv^
m{ul ul)
= {H2 - H,)s +
2gc
(68)
miul Ml)
570
[CHAP.
XIII
of the streams. The impact pressure is equal to mv^llg^ which corre- '
spends to the complete conversion of kinetic to -pY flow energy without
performance of work. Combined static and impact pressures are
measured directly by an impact-pressure gauge.
In Fig. 127 are diagrams showing the thermodynamic changes accompanying various types of compression between fixed suction and discharge pressures. The ideal>work of compression is represented by the
area to the left of the compression curve on the pV diagram. Thus, for
isentropic compression the ideal work corresponds to area abed. For
isothermal compression the corresponding work requirement is represented by area abed. It is evident that isothermal operation is highly
advantageous as regards power consumption. In general, it is attempted
to design compressors to approach ideal isothermal operation at the lowest feasible temperature. In this way power requirements are reduced ' .
by expenditures for cooling. The optimum design is that corresponding -;-''
to minimum over-all costs of compression and coohng.
Single-stage Compressors. Large-size compressors and fans ordinarily approximate adiabatic operation and would behave in accordance
with Equation (68) if the operation were reversible. However, irreversibility results from fluid friction and turbulence as well as from mechanical
friction in the equipment, both of which increase the work requirement.
Fluid friction also increases the final temperature of the fluid above the
value calculated from Equation (68). The departure of the operation
from ideal reversibility is expressed by an isentropic compression efficiency
factor tjs which is defined as the percentage ratio of the ideal work
requirement, calculated from Equation (68) for the pressure increase
obtained, to the total shaft work input to the compressor. Thus,
. ,, .
[Mi ni)s
vs =
-\
,, , ,,
,.
^'
X 100
(70)
ws (total)
where H^ is the enthalpy of the discharged gas at the calculated temperature resulting from isentropic compression. Inasmuch as work of compression is a minimum in a reversible isothermal operation, another index
of performance, termed the isothermal compression efficiency, TIT is also
used.
'/
work of reversible isothermal compression
VT total shaft-work input to the compressor
((?2 ~ Gi)r -\-
m(u2 ul)
ws (total)
-^
- ;. : :
(71)
- (
CHAP. XIII]
RECIPROCATING COMPRESSORS
571
The over-all efficiency includes compression efficiency and the effectiveness of the cooling system in approaching isothermal operation.
Compression efficiencies of commercial machines range from 40 to 65
per cent for fans and from 65 to 85 per cent for turbocompressors. The
power required for a specified compression duty is determined by calculating the work per unit quantity of fluid from Equation (68) and multiplying by the rate of flow per unit time. If the work is in foot-pounds
per pound-mole and the flow in poimd-moles per minute, the result is
divided by 33,000 to obtain the required horsepower.
Reciprocating Compressors. As previously pointed out, an ideal
reciprocating compressor would operate on the cycle abed of the pV
diagram of Fig. 127 if the compression were isentropic. In such a case,
the work requirement would be expressed by Equation (68). Actual
compressors of industrial sizes closely approximate adiabatic operation
but deviate from reversibility as a result of fluid and mechanical friction. A further compUcation is introduced by the necessity of providing
a certain clearance volume between the cylinder head and the piston at its
extreme position. This clearance volume is represented by dj in Fig. 127.
At the end of the stroke the clearance volume is filled with compressed
gas which expands to k, reducing the effective suction volume to kb.
The volumetric efficiency -QV is defined as the percentage ratio of the
volume of gas, measured at pi, actually taken into the cylinder during the
suction stroke to the volumetric displacement of the piston. The volumetric efficiency determines the capacity of a machine for a specified
duty while the compression efficiency determines the total work input
required per imit quantity of gas compressed. The total power required
for a machine of given displacement operating between specified pressiu-es
is increased by increased volumetric efficiency and reduced by increased
compression efficiency.
Compression efficiencies are reduced by mechanical friction and by the
pressure drops through the suction and discharge valves. As a result of
these pressure drops the actual suction pressure is somewhat below pi
and the discharge pressure above pt, as indicated by the dotted lines
between ah and je on Fig. 127. The increased work resulting from the
throttling through valves represents a major loss, and proper design of
valve openings is of great importance. Compression efficiencies are
increased by any cooling of the gas during compression which will cause
the operation to approach isothermal conditions, as indicated in the pV
diagram of Fig. 127. Cylinders of small compressors are frequently
water-cooled, but water jackets are not highly effective on large machines
because of the small ratio of surface to volume. In some designs cooling
water is injected into the gas during compression.
:^,, ,
572
[CHAP.
XIII
Actual horsepower
Piston displacement
97.8
= zr = 129 hp
800
= -- = 940 cu ft per mm
.-
0.80
Multistage Compression. Because of mechanical difficulties associated with high ratios of discharge to suction pressure a single-stage recip* R. York, Jr.,/nd. 7jiff. CAew., 34, 355 (1942).
'
CHAP. XIIIJ
MULTISTAGE COMPRESSION
673
2(-l)
p'
'
t-1
= ipiPi) '
p' = V^2
(73)*
574
[CHAP. XIII
^' = ^ = JS^
: Pi
\Pi
. ' " -^
; h,.
(74)*
Thus, for best operation, each stage should have the same compression
ratio, equal to the square root of the over-all compression ratio. Where
s stages are employed it may be demonstrated similarly that optimum
results are obtained when the compression ratio in each stage is equal to
.,*,
;,<3
CHAP. XIII]
REFRIGERATION
675
pressor. This is evident from the TS diagram for ammonia, Fig. 118.
Adiabatic compression of the saturated vapor results in superheating.
However, gases of high molal heat capacity behave quite differently, as
may be seen from the TS diagram for benzene in Fig. 121. If saturated benzene vapor at 100F is isentropically compressed, it is first
superheated, and then at a pressure of 655 lb per sq in. it becomes saturated, and condensation begins. Formation of condensate in compressors is frequently hazardous, and great care must be exercised in designing
compression systems for vapors of this type. Formation of condensate
in the intercoolers of multistage compressors is common when vapor
mixtures are being compressed, and faciUties for its separation from the
uncondensed gas passing to the next stage are readily provided.
REFRIGERATION
The purpose of refrigeration is to produce a region of temperature
below that of the atmosphere. The over-all result is the extraction of
heat from the low-temperature region and its rejection at the higher
temperature of the surroundings or of the available coohng medium.
Thus, in effect a refrigeration machine is a heat pump performing the
reverse function of an engine. Refrigeration is of constantly increasing
importance in the preservation of foods, in air conditioning, and in
chemical engineering operations where low temperatures are required for
the control of reactions, the condensation of vapors, or the crystalUzation
of solids.
Two general types of refrigeration cycles are in common use. Both
depend upon the attainment of a cold region by the vaporization of a
refrigerant fluid from an evaporator at a low temperature and pressure.
In compression refrigeration, shown diagrammatically in Fig. 129,
mechanical energy is used to compress the vapor leaving the evaporator
so that the heat absorbed at the low temperature of the evaporator may
be rejected at the temperature level of the condenser. A refrigerant
fluid is employed to absorb heat at low pressure and temperature and is
then compressed to a higher pressure and temperature where it gives off
heat, usually with condensation. Expansion to the lower pressure and
temperature completes the cycle. This latter is usually free expansion;
isentropic expansion has rarely proved feasible.
In absorption refrigeration, shown diagrammatically in Fig. 131, heat
which is absorbed at a low temperature and pressure is rejected at an
intermediate temperature and high pressure after its temperature level
has been increased by addition of heat from a high-temperature source
such as the combustion of a gas. In this scheme no mechanical energy is
576
[CHAP.
XIII
required except in some systems for pumping the liquid absorbent, and
the refrigerant is compressed from the low pressure at which it absorbs
heat to the high pressure at which it rejects heat through intermediate
absorption or adsorption at a low-pressure level. The refrigerant is
released from the absorbent or adsorbent at a high pressure through the
addition of heat from the high-temperature source. This method has the
advantage of minimizing or eliminating moving mechanical parts and
may effectively utilize low-pressure exhaust steam or fuel gas as the
source of heat.
Compression Refrigeration. A Carnot engine operating in reverse
represents an ideal reversible refrigeration cycle. The TS diagram of
At
-I1
T2
/ b
/
'
Condenser P-i
/W\AWW\A^
id
\A 1
i '^ i \
1
SB
SC
Pi Storage
Ti
Compressor
- W
Expansion
Evaporator ^2
MA/WWW^
T
?2
FIG. 128. Eeverse Carnot Cycle. FIG. 129. Vapor Compression Refrigeration.
such a cycle operating with saturated vapor is shown in Fig. 128. A
quantity of heat ga is absorbed in increasing the quahty of the vapor at
temperature T2 along be. Isentropic compression along cd raises the
temperature to Ti where a quantity of heat qi is rejected through condensation of the vapor along da. The liquid is isentropically expanded
and partially vaporized along ab to temperature T2 thus completing the
cycle.
As was developed in consideration of the Carnot engine, page 557, the
net work done by the system is the difference between the heats absorbed
at the higher and lower-temperature levels, and Equations (58) and (59)
are directly applicable to the reverse cycle operating as a heat pump.
However, in this case both Ws and Sh Sc are negative. It follows that / /
the amount of heat rejected at the high temperature is greater than that
absorbed at the low temperature by the amount of the work done on the
system.
For comparing the performance of refrigeration machines a coefficient
of performance is used as an index. This is defined as the ratio of the
CHAP. XIII]
COMPRESSION REFRIGERATION
577
heat absorbed in the evaporator to the work done on the fluid. Thus,
from Equation (59) the coefficient of performance
TiAS2
(77)
where AS2 = <Sic St- According to the Carnot principle, the coefficient
of performance of any reversible refrigeration machine operating between
temperatures Ti and Tj is expressed by Equation (77), regardless of the
nature of the refrigerant or the steps of the cycle.
578
"
[CHAP.
XIII
Evaporation
Ha = Ht
(78)
Hb + q^ = He
(79)
Ho w, = Hd
(80)
S ,
Compression
Since qi in going from d to a is negative,
Cooling and condensation
Hd = Ha. qi
(81)
(82)
The ideal coefficient of performance then becomes, from .(78), (79), and
(82),
=f ^ "
Wa
(83)
Hd He
where Ws represents the net work done on the fluid and not the total
work input to the compressor.
The coefficient of performance may be visualized from the TS diagram
of Fig. 130 in which the double-crosshatched area represents q-i. and the
single-crosshatched area represents w,. The coefficient of performance
is the ratio of these two areas. It is evident that the coefficient of
performance would be greatly improved if the free expansion along ah
were replaced with isentropic expansion in an engine, the work from
which would be transmitted to the compressor. This scheme is rarely
used because of mechanical complications.
In developing Equation (83) it was assumed that the compression step
is isentropic; actually some heat is generally absorbed in the piping
CHAP. X I I I ]
COMPRESSION REFRIGERATION
679
580 .
[CHAP. XIII
with a compression efficiency for the compressor of 85 per cent and a volumetric
efficiency of 75 per cent.
, , '
^
Calculate
(a) The pounds of propane circulated per hour.
(6) The heat removed in the condenser, Btu per hour.
(c) The power required to drive the compressor.
(d) Volumetric displacement of compressor, cubic feet per minut.
(e) The coefficient of performance.
.
In the absence of tables or charts on the thermodynamic properties of the refrigerant, this problem can be solved by the following generalized procedure.
Basis of calculations: 1 lb-mole of propane circulated
Let
Ha = enthalpy of liquid propane at 100F
From
From
From
From
Fig. 103:
Fig. 107:
Fig. 106:
Table XIII:
..,
.
Condenser
/
p = 13.69 atm
/
T = 660R
' .
Pr = 0.318
r . == 0.840
2 = 0.78
-S* - S = 1.75 Btu/(lb-mole) (R)
{H* - H) jTe = 1.8
X = 6040 Btu per lb-mole
Evaporator
4.83 atm
490R
0.113
0.735
0.91
1.10
0.88
7250
Trd = 0.85
= 1.62
prd = 0.318
{Ht ~ Hd) ITc = 1.7
(a)
CHAP. XIII]
ABSORPTION REFRIGERATION
681
i H t - m ^ - T . \ ^ - ^ ^ - ^ J ^ ^ ]
560
i/see
/666
Heat absorbed in evaporator = (50) (60) (200) = 600,000 Btu per hour
600,000
(a) Propane circulation rate =
=111 lb-moles per hr or 4890 lb
i ZsM l o O ^
per hr
(b) Heat transfer duty of condenser = (111) (8072 - 1852) = 691,000 Btu per hr
Ideal work of compression = 111(822) = 91,300 Btu per hr
91 300
(c) Power to drive compressor = ,^^,'^
. , , = 42.2 H.P. at 85 per cent com(0.85) (2545)
pression efficiency
490 1
Volumetric intake = (111)(359) - (0.91) = 7650 cu ft per hr
(492) 4.83
(d) Piston displacement of compressor at 75 per cent volumetric efficiency =
7650
(60) (0.75)
582
[CHAP.
XIII
reduce the amount of weak liquor circulated per unit mass of ammonia
absorbed, it is necessary to cool the absorbent close to the temperature
of the available cooHng water and to provide intermediate cooling surface
in the absorber.
The strong ammonia liquor on its way from the absorber to the stripper
is passed through a heat exchanger where it is heated coimtercurrently
by the hot weak liquor on its way from the stripper to the absorber.
The weak liquor after cooling in the heat exchanger enters the top of the
absorber. The strong liquor is fed to the stripping column where heat is
added by means of a reboiler to evaporate the ammonia. The vapors
Condenser
r#2
Cooline
water
Evaporator,,
ti
Accumulate
^Steam
Reboiler
q^
- :- -
Heat Ezchanser
CHAP. X I I I ]
ABSORPTION REFRIGERATION
583
maintained for condensation and for evaporation. Circulation is maintained by thermal convection induced by the still, and absorption proceeds by the partial-pressure gradient of the refrigerant from vapor to
liquid phase. Descriptions of such units which are used largely in household refrigeration are given by Keenan.'
The problems of design and analysis of absorption refrigeration
systems involve a series of energy balances embracing the entire cycle
and each of its parts. Thus, for the over-all process, with reference to
Fig. 131, if changes in kinetic, potential, and surface energies are
neglected,
q2 + q, + qi + qa- w, = 0
(84)
where
Energy balances for individual steps involve only enthalpy and heat
terms except where the pump is included. Thus, for example, for the
stripper,
msHs + maHa + q, = msHs + mJIs
(85)
where wis is the mass of the stream 5 in Fig. 131, and Hi is the corresponding enthalpy per unit mass. The other symbols have similar
significance.
Since mixtures of varying concentrations are involved throughout the
cycle, energy balances are most readily evaluated by means of an
enthalpy-concentration chart, such as described in Chapter VIII.
Fig. 132 is such a chart for the enthalpies of the ammonia-water system
at various pressures and temperatures and for all compositions and
phases. Enthalpies are based upon 1 lb of the fluid and are referred to
Uquid ammonia at 40F and to liquid water at 32F, each at its respective vapor pressure at these temperatures. This chart is a modification
of one prepared by Bosnjakovic* by the methods described in Chapters VII and XIV.
The lowest group of lines on the chart represents the enthalpies of
various sohd phases of ice and ammonia with the indicated eutectic and
congruent points. The next lowest group of curves represents the
enthalpies of saturated solutions over the entire range of composition for
various temperatures and pressure. The third group from the bottom is
' " Technische Thermodynamik II," Theo. Steinkopf, Dresden and Leipzig (1935).
0.1
0.2
0.3
0.4
0.5
0.6
0.7
ConcentrationWeight Fraction NH3
[CHAP. XIII
0.8
0.9
1.0
CHAP. XIII]
ABSORPTION REFRIGERATION
585
586
[CHAP. XlII
Solution: The material and energy balances are established simultaneously from
the data of Fig 132, starting with the evaporator. These calculations are summarized in Table A where the streams are identified by the numbers of Fig 131.
The results in this table are reported in more significant figures than are justified by
the accuracy of the data in order that the numerical accuracy of the calculations may
be readily verified by over-aU balances.
(1) The pressure of stream (1) is read from Fig. 132 as 210 lb per sq in.; the equilibrium pressure of liquid containing 99.5 per cent NHa at 100F.
(2) The pressure of stream (2) is the equilibrium pressure of saturated vapor containing 99.5 per cent NH3 at 30F, which is read from Fig. 132 by a trial-and-error
procedure. A trial value of the equilibrium pressure is assumed, and a horizontal
Mne is followed from the point representing saturated vapor at this pressure and
99.5 per cent NH3 over to the corresponding construction line. A vertical line is
followed downward from this point to the 30F hne of the saturated Uquid curves, and
the corresponding equilibrium pressure is read. This second approximation pressure
is used to repeat the operation until consistent pressures are obtained. In this manner it is found that the evaporator pressure is approximately 45 lb per sq in. and that
the liquid in equilibrium with the vapor leaving the evaporator contains 77 per cent
NH,.
TABLE A
MATERIAL AND ENERGY BALANCES OF
AMMONIA ABSORPTION REFRIGERATION PLANT
Stream
1
2
3
4
5
6
7
8
9
NH3
Per Cent
byWgt
99.5
99.5
40.0
40.0
40.0
20.0
20.0
99.5
99.5
<F
100
30
100
100+
217
290
120
110
100
H
Abs Pressure,
lb per sq in. Btu per lb
210
152
640
45
45
-5
210
-4.4
210
128.8
210
220
42
45
210
650
210
152
>
/
U) per hr
1229.5
1229.5
4887.3
4887.3
4887.3
3657.8
3657.8
1844.3
614.8
Btu per hr
186,880
786,880
-24,440
-21,660
629,432
804,720
153,628
1,198,800
93,450
The rate of stream (2) is fixed by the heat-transfer duty of the evaporator and the
differences in specific enthalpies of streams (1) and (2). Thus,
nil = (50)(200)(60)/(640 - 152) = 1229.5 lb per hr
^" ''"
(3) The ammonia content of the strong liquor is 95 per cent of the equilibrium
concentration at 100F and 45 lb per sq in., which is read from Fig 131. Thus,
NH3 in stream (3) = 0.95 X 42 = 40 per cent. It may be assumed that the enthalpy
of a liquid which is not completely saturated with NH3 is the same as that of a saturated solution of the same NH3 content and at the same temperature. On this basis
H, = - 5 Btu per lb
The rate of stream (3) is determined by the over-all material balance and the
ammonia balance of the absorber. Since from the over-all material balance m? =
m, - 1229.5,
O.4OOT3 = (ms - 1229.5)0.20 -|- (1229.5) (0.995)
ms = 4,887.3
rm = 3,657.8
i
CHAP. X I I I ]
ABSORPTION REFRIGERATION
587
(4) The work done by the pump is calculated from. Equfl.tion (61) The data of
the International Critical Tables indicate a density of approximately 0.86 for a
solution at these conditions.
( 2 1 0 - 4 5 ) (144) (4887.3)
-"" = ^
(eSik^)
- = 2,160.000 ft-lb per hr
= 2,780 Btu per hr
2 160 OflO
Power input to fhiid = -^:'= 1.09 hydraulic hp
^
(60) (33,000)
^
^
In order to determine the power required for the pump drive, the hydraulic horsepower must be divided by the fractional efficiency of the pumps.
Enthalpy increase of the fluid in the pump
2780
= 0.57 Btu per lb
4887.3
(5) The temperature of the feed to the stripper is determined by an energy balance
around the heat exchanger. The quantity of stream (7) is determined and its
enthalpy may be evaluated from the specified temperature of 120F. The temperature of stream (6) is the equiUbrium temperature of a solution containing 20 per cent
NHs at a pressure of 210 lb per sq in., which is read from Fig. 132 as 290F with an
enthalpy of 220 Btu per lb. The enthalpy of stream (5) is then calculated from the
specific enthalpies of Table A and the energy-balance equation niilli = nitHi +
mjlt
VlyHTOT
,1./., n
*' '
' ^- '
588
[CHAP. XIII
(7) The steam used for heating the reboiler must be at a temperature of 300F
which corresponds to an absolute pressure of 67 lb per sq in. or a gauge pressure of 62
lb per sq in. If it is assumed that the condensate is withdrawn at 300F, heat to the
reboiler per pound of steam is the heat of vaporization which from the steam table is
910 Btu per lb.
1,280,638 , , ,
^
Reboiler steam rate = = 1407 lb per hr.
If the results of Illustrations (8) and (9) are compared, it is seen that with the
particular specifications employed identical refrigeration duties are performed by a
44.3-hp mechanical drive in the one case and by 1,407 lb per hr of 52-lb steam in the
other. If the heating steam were used to operate the drive of the compression machine an engine with a steam rate of 34 lb. per hp-hr would be required. This corresponds to an engine efficiency of 65 per cent if the exhaust is at atmospheric pressure.
The heat to coofing water in the absorption cycle is (1.96)10 Btu per hr as compared
to (0.696)10^ in the compression machine. This difference in cooUng-water requirement is greatly reduced if a steam drive with a condenser is used for the compressor.
It may be concluded that the relative desirability of compression and absorption
refrigeration cycles is largely dependent upon particular local conditions. The
absorption operation is favored by the availabihty of low-cost exhaust steam for
heating the reboiler. The choice of a refrigeration cycle thus involves consideration
of the entire power-steam balance of the plant. As previously mentioned, many
modifications of the absorption cycle are possible in order to adapt it to local conditions.
Other binary systems have been used for absorption refrigeration, but
the ammonia-water is the most common. The chief difficulty in the
development of other binary systems is in the selection of an absorbent of
high absorption capacity and ease of separation, and one that is nontoxic, noncorrosive, and not decomposed by prolonged use at the stripper
temperatures.
Refrigeration cycles based upon the adsorption of refrigerant vapors
upon solid adsorbents have been used to a limited extent and may
develop to greater importance. Such schemes operate on an intermittent cycle, adsorbing vapors at low temperature and pressure in one
chamber, while another chamber is evolving previously adsorbed vapors
at a higher temperature and pressure. Adsorbents of high capacity
such as sihca gel, activated alumina, or charcoal may be used with a
variety of fluids. The disadvantages of these methods are the'intermittent nature of the operation and the difficulty of transferring heat to
a solid material. The thermodynamic problems of adsorption refrigeration may be handled by the same general principles as demonstrated
here for the absorption systems. It is desirable to develop an enthalpycomposition'chart for the adsorbed system to facilitate calculations.
Such a chart is shown in Fig. 62, page 300, for water vapor on silica gel.
CHAP. XIII]
589
Multistage compressor
and intercoolers
9
A
Expansion valve
[ Liquid
FIG. 133. Low-Temperature Liquefaction of Gases.
to precool by means of conventional refrigeration. The lower temperatures required for liquefaction are then produced by the self-cooling
cycle shown diagrammatically in Fig. 133.
The gas to be liquefied enters the system at temperature Ti and pressure pi and is combined with recycled gas which drops the temperature
slightly to T2. The gas is then compressed to ps with an increase in
temperature. Multistage compression is generally employed with rejection of heat gi in the intercoolers. The compressed gas is cooled at the
interstages with water or a cooling fluid circulated by a conventional
refrigeration system. The compressed gas is passed to a heat exchanger
where it is cooled by a return flow of the same gas after its expansion.
The cold compressed gas is then expanded to a lower pressure with a
corresponding drop in temperature. This expansion may be carried out
590
[CHAP.
XIII
isentropically, and the power developed may be used in the compressor >.
drive or for other purposes. This scheme is termed the Claude process.
More commonly, however, the simple Linde process involving free
expansion through a throttling valve is used, even though the temperature drop is much less, and no work is recovered. The cold expanded
mixture of liquid and gas passes to a separator where the liquid is
collected and the uncondensed gas is returned to the heat exchanger and
thence to the compressor inlet, completing the cycle.
The design or performance of a gas-liquefaction plant may be developed without difficulty from principles already demonstrated. With
reference to the stream numbers of Fig. 133, it is desirable to base the
design on specified values of pi, ps, ps, Ti, T3, and T?. Energy balances
involving x, the fraction of the compressed stream which is liquefied,
may then be estabUshed. Thus, if free expansion is used and changes of f
kinetic and potential energy and the exchange of heat with the surround- *
ings are neglected,
Hs = xHs + (1 - x)Hj
(86)
Since Hi is fixed by the saturation conditions at ps. Equation (86)
may be solved directly for x. Evaluation of x permits establishment of a
complete material balance to correspond to the specified rate of production of liquid. The intermediate temperatures and the heat-transfer and
compression duties are then readily calculated. If absorption of heat
from the surroundings is appreciable, these items should be included in
the energy balance.
It is evident that the Linde process is apphcable only to gases which cool in free expansion. With reference to Fig. 105, it is seen that free
expansion cooling is not obtained at reduced temperatures above 6.
Hence, for example, in order to liquefy hydrogen, it is necessary to precool to 100K before the Linde process may be employed.
i
VAPOR-RECOMPRESSION EVAPORATION
The evaporation of water from nonvolatile solutes or suspensions is
generally accomplished by multiple-effect evaporators, such as illustrated in Fig. 29, page 180. In this scheme several pounds of water may
be evaporated by the use of 1 lb of heating steam, depending upon the
number of effects used. A somewhat similar result can be produced in
more compact and simple equipment by the use of the vapor-recompression cycle, as shown diagrammatically in Fig. 134.
A dilute solution at a temperature Ti is charged to the evaporator containing the boiling concentrated solution at temperature T2 and pressure
/
I'i
CHAP. XIII]
VAPOR-RECOMPRESSION EVAPORATION
591
Pi. As a result of the elevation of the boiling point of the solution over
that of pure water, the vapors evolved are superheated. These vapors
are isentropically compressed to pt, the pressure of the fresh steam
supply, and combined with this supply to the evaporator. Condensate
is withdrawn substantially at the saturation temperature of the heating
steam. Concentrated solution is continuously withdrawn from the
bottom of the evaporator to maintain a constant liquid level and concentration.
By this method it is possible to evaporate several pounds of water per
pound of steam supply through the addition of a relatively small amount
V a p o r p., Tj
<D
r'n-T"^ Compressor
-Ws
" Compressed
Feed
vapors
M_
Saturated
steam
Condensate
Concentrated Bolution
(87)
592
[CHAP. XIII
is then obtained directly from Equation (87) and the ratio of evaporation
to steam mi/mi may be calculated.
This scheme of evaporation is of interest where power costs are low and
fuel costs high. Such a situation might exist in the vicinity of large
hydroelectric-power developments.
-
'
'
^-
\ -
. '
..
.:.
PROBLEMS
1. Calculate from the changes in the energy functions, the v/ork done, the heat
added, and the changes in T, v, s, u, H, A, and o in the reversible expansion to 1 atm
by each of the following methods of 1 lb-mole of chlorine originally at an absolute
pressure of 500 lb per sq in. and 250F. The initial absolute entropy of chlorine
is 48.76 Btu/(lb-mole)(R). Carry out these calculations (I) assuming ideal behav-'
ior, (II) taking into account deviations from ideal behavior by the generalized correlation. Express work in foot-pounds and the energy functions in Btu.
(o) Nonfiow isothermal.
,'
(b) Flow isothermal.
;,
(c) Nonflow isentropioi
, '
' j
(d) Flow isentropic.
(e) Maxwell expansion (irreversible).
(/) Joule-Thomson expansion (irreversible).
*
The physical properties of chlorine are as follows*.
/
c* = 8.28 + O.OOOSir Btu/(lb-mole) (R)
[T = R]6
2. Repeat the calculations of parts oil and bll of problem 1 by graphical integration of the pV changes based on the generalized compressibility-factor correlation.
3. Propane at an absolute pressure of 200 lb per sq in. and 120F is expanded
through a valve to an absolute pressure of 39 lb per sq in. Using the generalized
thermodynamic correlations and the vapor-pressure equation from Table Ila, page 73,
calculate the temperature on the downstream side of the valve arid the quaUty or
degrees of superheat of the vapor above saturation before and after expansion.
4. The expansion referred to in problem 3 might also be carried out isentropically
in an engine. Calculate the temperature and degrees of superheat or quality after
expansion in this manner and the ideal work performed per pound-mole.
5. A Rankine-cycle power plant generates dry saturated steam at a gauge pressure
of 400 lb per sq in. which is isentropically expanded through engines to an exhaust
gauge pressure of 10 lb per sq in. for use in process heating. It may be assumed that
the condensate is returned to the boilers at its saturation temperature under the
exhaust pressure by an isentropic pump.
(a) By means of the data of the steam tables, determine the number of pounds of
dry saturated low-pressure steam available for process heating per 100 lb of highpressure steam generated.
^ K. K. Kelley, U. S. Bur. Mines. Bull. 371 (1934).
CHAP. XIII]
PROBLEMS
593
(6) Calculate the ideal thermodynamic efficiency of the cycle. Compare this
result to the Carnot efficiency.
(c) Calculate the ideal water rate of the engine.
6. Determine the effect on the results of problem 5 of superheating the steam 100F.
7. A pump is driven by a steam engine which deUvers 20 hp and operates on dry
saturated steam at 400 lb gauge pressure and exhausts at an absolute pressure of
2.0 lb per sq in. The engine efficiency is 70 per cent. Using data from the steam
tables, calculate the pounds per hour of steam required and the heat-transfer duty of
the condenser in Btu per hr. Compare the ideal steam rate of the engine with that of
problem 5c.
8. A single-stage compressor is required to compress 450 cu ft per min of CO2
measured at 60F and 14.5 lb per sq in. abs from an absolute pressure of 5 lb per sq in.
and 80F to an absolute pressure of 20 lb per sq in. Assuming isentropic compression,
calculate the horsepower required to drive the compressor, the required piston displacement in cubic feet per minute and the discharge temperature, assuming a volumetric efficiency of 77 per cent and a compression efficiency of 83 per cent.
9. The compression duty of problem 8 might also be handled by a two-stage
machine with intercooling to 80P. Calculate the horsepower required to drive the
compressor in this operation and the discharge temperature, assuming the efficiencies
given in problem 8.
10. Anhydrous HCl {ta = -85C; tc = 51.4C; p = 81.6 atm) at an absolute
pressure of 30 lb per sq in. and 80F is to be compressed to 450 lb per sq in. abs at a
rate of 100 cu ft per min measured at 60F and 14.5 lb per sq in. A two-stage machine is to be used with intercooling to 80F. The compression efficiency based on
isentropic compression in each stage is 80 per cent and the volumetric efficiency
65 per cent. The heat capacity of HCl in the ideal state is given in Table V. The
intermediate suction pressure may be calculated from Equation (73).
Assuming isentropic compression in each stage, calculate:
(o) The horsepower required.
(6) The required piston displacement, cubic feet per minute each stage.
(c) The discharge temperature.
11. A compressor having a 75 per cent mechanical efficiency is to compress 1.5
lb-moles of ammonia per minute from an absolute pressure of 15 lb per sq in. and
100F to 200 lb per sq in. abs. . The operation is to be in two stages, each of which
may be assumed to be isentropic with intercooling to 115F. By use of Pigs. 116-119
calculate the power required to drive the compressor when designed for the optimum
intermediate pressure. Calculate the discharge temperature from each stage and the
heat-transfer duty of the intercooler, and compare the optimum intermediate pressure
with that calculated from Equation (73).
12 (o). The refrigeration duty of Illustration 8 is to be performed by a plant using
ammonia as the refrigerant, and with the same temperature levels. Assuming the
same compressor efficiencies, calculate the power input, piston displacement, coefficient of performance, and heat input to the condenser for the ammonia machine.
Compare these values and also the operating temperatures and pressures with those
of the propane system.
(fc) Repeat the design for an evaporator temperature of 0F.
13. Design an ammonia-water absorption refrigeration plant for the conditions
specified in Illustration 9 except that the evaporator temperature is to be maintained
at 0F and the reflux ratio increased to 0.9 because of the more dilute solutions
handled. Compare the heat-transfer duties, circulation rates, and steam requirement
with those of Illustration 9.
594
[CHAP. XIII
CHAPTER XIV
THERMODYNAMICS OF SOLUTIONS
The thermodynamic principles which are developed in previous chapters are applied in Chapters X I I and X I I I to problems involving essentially pure substances. The general relations of Chapter XI are in no
way restricted to pure substances and may be validly applied to solutions and mixtures of all types. Such apphcations are comphcated by
the introduction of composition as an added variable.
ii COMPRESSIBILITY OF GASEOUS MIXTURES
The laws of additive pressures and of additive volumes discussed in
Chapter II, page 37, when considered separately, do not necessarily
imply ideal gases. In general, these laws apply with much greater accuracy than the ideal-gas law and are reasonably satisfactory even where
pressures are moderately high. As previously pointed out, either Dalton's or Amagat's law may hold for actual gases, but together they hold
rigidly only for ideal gases. Which of these laws gives the better approximation depends upon the conditions and the nature of the gaseous
mixture. For example, for mixtures of argon and ethylene Dalton's law
of additive pressures is the more nearly accurate; for mixtures of nitrogen and hydrogen the law of additive volumes holds better.
Mean Compressibility Factors. A simple empirical equation of state
for a mixture of gases may be written in a form similar to Equation (XII-3), thus,
U ..* r, :r^
where
p = total pressure of mixture
I,
'
Equation (1) permits calculation of the pressure, temperature, and volume relationships of gaseous mixtures of known compositions if the mean
compressibility factors are known. The mean compressibility factor is
595
596
THERMODYNAMICS OF SOLUTIONS
[CHAP.
XIV
^
/ /
)<A
1/
W
/
/
^1 ^
i?
/
./ 1
/^
E
S
/.
A
//
/ V
''
^/
A ^
4'
^,
0.9
200
\
400
600
800
1000
Pressure, Atmospheres
CHAP. XIV]
597
(2)
*'m
n
where
ZA = compressibility factor of component A at the temperature
and total pressure of the mixture
This equation permits the approximate calculation of the mean compressibility factor of a mixture, at any conditions of temperature and
pressure, from the compressibility factors of the component gases at the
^ .<;
^
1.9
,}cnr
^ 0 ,
,1.7
~~^^=^
"^ = 5 -
A00
1"
"-
600
fin
1.3
300
-
1.1
"^ = ^
=^ ^
?,00
rT=-
^
^n.
100
-6 0 -
0.9
20
40
60
100
same conditions. The dotted lines on Fig. 136 represent the results obtained by the appHcation of Equation (2) to the mixtures of hydrogen
and nitrogen at the conditions investigated. It may be noted that for
this system the validity of Amagat's law is satisfactory, the maximum
error being of the order of 2.5 per cent.
Equations (1) and (2) may be used in conjunction with compressibility
data on the pure components obtained either by direct measurement or
from Fig. 103. This procedure yields fairly satisfactory results where
the compressibility factor of none of the individual components is smaller
598
THERMODYNAMICS OP SOLUTIONS
[CHAP. XIV
than 0.5. Serious errors result if the conditions of the mixture are close
to the critical points of any of the components. This method involves
questionable extrapolations of Fig. 103 for components whose liquidvapor pressure at the temperature of the mixture is less than the total
pressure of the mixture.
, .; ,;,,.-,f .o ,/);>ni ; ? ' ; . i ^ , . .
Illustration 1. A gaseous mixture containing 6 lb of methane and 4 lb of ethylene
is compressed to 30 atm at 100F. Calculate the volume occupied by the compressed
gas.
Basis: 10 lb of mixture:
-i.t
Methane
Ethylene
Pound-moles of gas
0.374
.
0.143
Critical temperature, R
343
510
Critical pressure, atm
45.8
50.9 i
Reduced temperature
560/343 = 1.63
560/510=1.10
,*,
Reduced pressure
30/45.8 = 0.654
30/50.9 = 0.59
.5
Compressibihty factor (Fig. 103)
0.95
0.83
.....^ , ^
, .^
(0.95) (0.374)+ (0.83) (0.143) , ^
Mean compressibihty factor of mixture =
= 0.916
0.517
(0.916)(0.517)(359)( ^ ^ ) ( ] = 6.46 cu ft
\492A30/
'
"/
I -
1, 1
= ^NVAO
B^=
l^NBo
'
"^
where
-=
f
'- ' - '
' "
Ami, o-m, etc. = average constants for the mixture
^Ny/A~o, ^Na, etc. = summations of the products of the mole fractions
times the indicated functions of the constants
of each of the component gases
/
ta-
CHAP. XIV]
599
Second type
/ / / /
L
3-
^^^^/ X
^^^>/First
Liquid
c'B
/
/
y
Vapor and
liquid
/ %^
y
Ay/
Isometric lines
Vapor
Temperature
*FIG. 137. Critical Phenomena of Mixtures.
,,. ;.
: ; < ! , ; !
The sloping straight hnes on Fig. 137 are lines of constant volume
for the single-component system and are termed isochors or isometrics.
It has been found that for most substances the isometrics are approximately straight, represented by the equation,
p = mT-b
''
(3)
where m and b are constants dependent on the volume and the substance
under consideration.
Curve BDECFGH represents what is termed the border curve of a mix-
600
THERMODYNAMICS OF SOLUTIONS
[C&AP. XIV
ture having the same average volatility as that of the pure compound
represented by line AC, but made up of two or more substances of different volatilities. The area enclosed by the border curve represents a
two-phase region in which both hquid and vapor are present in equilibriiun. Line BDE represents conditions of initial vaporization, to the
left of which is the region of complete liquefaction termed the bubblepoint line. Line HGF termed the dew-point line represents conditions
of initial condensation below which is a region of complete vaporization.
Point C represents the critical point of the mixture. This critical
point does not necessarily correspond to a maximum temperature at
which the hquid phase can exist as in the case with a pure component,
but rather the particular point on the border-line curve where the vapor
and hquid phases become indistinguishable, or where the bubble-point
and dew-point lines meet. In general, both the critical temperature and
the critical pressure of a mixture are higher than those of a pure compound having the same average volatility.
|
It may be noted that the dew-point line passes through a maximum
temperature at F. Thus, in the case of a mixture," tiquid may exist at a
temperature higher than the critical temperature. This maximum temperature F on the border curve is termed the critical-condensation temperature. Similarly, in the case of many mixtures the bubble-point
line passes through a point of maximum pressure E, higher than the
critical pressure. The areas FJCM and EKCL represent regions of
retrograde condensation. If the mixture at the condition of point 1 is
compressed at constant temperature, a more dense phase appears at
point G on the dew-point line. As the pressure is further increased, the
quantity of this more dense phase increases to a maximum at point J
and then diminishes, disappearing entirely when point M is reached.
This type of retrograde condensation occurring in area FJCM is called
the first type. If the liquid mixture at conditions of point 3 is heated
at constant pressure, a less dense phase appears at point D on the bubblepoint line, reaches a maximum at point K, and then diminishes, disappearing entirely at point L. The type of retrograde condensation which
occurs in area EKCL is called the second type.
,
The entire area outside the border curve is a region of homogeneous
fluid in which no phase separations occur. Moving clockwise in the
region about the border curve, the liquid phase merges imperceptibly
into the vapor phase.
Retrograde condensation is of particular interest in petroleum production. When natural gas is withdra\vn from high-pressure wells, liquid gasohne condenses upon release of pressure. The residual gas may
then be recompressed and recycled to the underground oil-bearing for-
lo^ff
CHAP. X I V ]
601
uoo
100
200
300
400
Temperature, F.
500
600
602
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
600
400
s^
&
\r
'
" '
.300
V\ V
Hi
&200
S
100
\
^J(^
'^?x--
'*--*
^
-100
100
40
60
80
Mole Per Cent Ethane
Fia. 139. Temperature-Composition Diagrams for Mixtures of Ethane and
n-Heptane at Various Pressures.
w.
20
If the envelope curve were of such shape that it approached point Ct,
with a positive slope, it would indicate the existence of mixtures having
critical temperatures higher than that of the higher boiUng component.
These mixtures would have critical points lying in a clockwise direction
beyond the corresponding points E and F, both of which would be on
//
/ '
CHAP. XIV]
603
v...J,
20
40
60
80
Liquid, Mole Per Cent Ethane
100
604
THERMODYNAMICS OP SOLUTIONS
[CHAP. XIV
CHAP. X I V ]
605
sure being used. However, it must be emphasized that this method applies only to the vapor phase and breaks down at conditions within the
border curve of the mixture. The pseudocritical point itself is located
in this region.
Illustration 2. Calculate the volume occupied by l i b of a mixture of 59.9 mole
per cent ethylene and 40.1 per cent argon at a temperature of 25C and a pressure
of 100 atm.
Critical temperature, C
Critical pressure, atm
Molecular weight
Ethylene
9.7
50.9
28
Argon
122
48
39.9
When two miscible liquids at the same temperature are mixed together,
the resulting solution may exhibit ideal behavior, that is, possess properties which are additive functions of the properties of the pure components. Thus, the volume and enthalpy of the solution may be the exact
sum of the volumes and enthalpies of the components. In this case the
density of the solution is the sum of the products of the densities of the
components multiplied by their respective volumetric fractions, and the
specific heat of the solution is the sum of the products of the specific
heats of the components multipUed by their respective weight fractions.
606
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
+ ^
PBO
+ ---
(4)
PCO
+
PAIUAO
PBiO^Ba
(5)
PCi^Ca
' B . W. Gamson and K. M. Watson, Nail. Petroleum News, Tech. Sec, 36, fl554
(Aug. 2, 1944). Also "Process Engineering Data," National Petroleum Publishing
Company, Cleveland (1944).
CHAP. XIV]
607
where
)\
PAi
PBI
hI
(6)
PCi
F =where
The expansion factor w' of the solution is derived from Fig. 109 by expressing T and p in pseudoreduced units based on the pseudocritical
properties of the mixture.
Similarly, in molal units,
^, ^ t ^ ^ J_ [-(y^^^)^^^ ^
CO
(VI^OBNB
+ iviw,)cNc + ]
(8)
CO
608
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
n-
Np,
lb per
sq in.
10.6
86.1
555.3
652.0
fiwi
A'Ci'iui)
cc per
g-mole
4.36
6.81
9.18
cc per
g-mole
0.07
0.82
7.96
= 8.85
{ViUiY
NM
16.04
30.07
44.09
0.24
3.60
38.06
Afavg = 41.90
r; =560/647.2 = 0.865
V, = 300/652 = 0.460
a' (Fig. 109) = 0.096
^"Z'_
'
i
'
CHAP. XIV]
609
.^^^ _
610
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
where A' = pseudo heat of vaporization of the mixture at pseudoreduced temperature T'r
hiA, XftB = molal heats of vaporization of components A, B, ' at their
normal boiling points
TrbATrbB = Teduced temperatures of the normal boiling points of components A, B, based on their individual true critical
temperatures
T'r = pseudoreduced temperature of the mixture
In view of the other approximations involved, it is generally satisfactory to assume, for the calculation of liquid enthalpies, that the pseudoreduced vapor pressure at which condensation of the mixture is assumed
CHAP. XIV]
611
.
10
iitf
.-,u-..>.r:l
+5
s
8
^^;=
7
m
O
t^\^
jp'Xla/j'
I>3
I
-5
6
6^ ^
ah"
' ^ ^
P^T...
"^"v..^
^ 1 ^
'c'p'^s'T
-10-J:
//
/
'
-F
^^^'
-15 15?
^
-1"
{s*-s,\ P,T
ss^"^
= ^
0.65
-20
FIG. 141. Enthalpy and Entropy Corrections of Gases and Liquids for Saturation
at Various Reduced Temperatures.
The enthalpy HL of the liquid mixture comprising ut moles at temperature t and pressure p is then
612
'
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
__
XT
^ i
PSETTDOREDUCED V A P O R PRESSURES
Tr
0.60
0.65
0.70
0.75
0.80
V'r
0.0110
0.027
0.057
0.109
0.189
0.85
0.90
0.92
0,94
0.95
v'r
0.310
0.478
0.561
0.655
0.699
Tr
0.96
0.97
0.98
0.99
0.995
1.000
v'r
0.759
0.815
0.873
0.935
0.990
1.000
As previously pointed out, it is possible for liquids to exist at temperatures above the pseudocritical temperature of the mixture. Where
only a single phase is present, such liquids may be treated as a highly
compressed gas to which Fig. 106 is applicable. The enthalpy of the
Hquid is then
^
,.,
r
HL = H*-n,n(^~^)
where
_,
(11)
/
' Illustration 4. Calculate the enthalpy of the mixture of Illustration 3 when completely vaporized (o) at a pressure of 175 lb per sq in. and 100F and (6) when existing as a liquid at 100F and 300 lb per sq in. Express the enthalpies in Btu per
pound relative to the ideal gaseous state at 60F.
CHAP. XIV]
613
^ = - ^ = 0.865
647.2
CH4
C2H6
CsHs
'
N
0.015
0.120
0.865
Xi cal
per
g-mole
2,218
3,515
4,493
,-|'..
\b
nR
201.2
331.8
416.2
'
TIR
343
550
666
-
Tri
0.587
0.603
0.625
'1
1-TA
0.413
0.397
0.375
Nh,
(1 - r,i,)-^ (1 - rrt,)-!
3,100
46.5
5,000
600
6,530
5650
/-', = - 2 . 2 ;
614
THERMODYNAMICS OF SOLUTIONS
'
[CHAP. XIV
ENTROPIES OF SOLUTIONS
Problems involving the expansion or compression of a mixture may be
handled directly by the methods developed in Chapter X I I I if the thermodynamic properties of the mixture can be calculated. Volumes and
enthalpies may be obtained by the methods demonstrated in the preceding sections and entropies are calculated by a procedure parallel to
that developed for enthalpies. If pseudoreduced terms are employed,
Figs. 107 and 111 are applicable to mixtures. Thus, the entropy of a
gaseous mixture is obtained by subtracting the correction of Fig. 107
from the entropy which it would possess were it an ideal gas at the temperature and pressure of the mixture. Similarly, the entropy of a
pseudosaturated liquid mixture is obtained by subtracting a pseudo
entropy of vaporization from the entropy of the pseudosaturated vapor.
On the assumption of a pseudoreduced vapor pressure corresponding
to a given pseudoreduced temperature as given in Table XXIX, unique
values of (s*-Ss)p r for the gaseous ^ a t e and (Scp-Ss)?- for the
liquid state have been calculated and are plotted in Fig. 141. The
values of {S*-SS)J,,T for the gaseous state give the corrections in entropy
per mole in going from ideal conditions to conditions of the pseudosaturated vapor at the same temperature and pressure.
Because of the entropy changes which accompany the formation of
even ideal solutions, entropies of mixtures of fixed composition are most,
conveniently expressed relative to the mixture at some reference state
rather than relative to the pure components.
i,;
CHAP. XIV]
CHEMICAL POTENTIALS
616
/s,ni,n2...\0ni/v,
S, n 2 . . . \ o n 2 / s , F, m...
= P and I r )
= T when reversible
(13)
(14)
It may be noted from Equation (14) that a change in the total internal
energy of a system is the sum of the changes of a number of energy
terms, each of which comprises ah intensive and an extensive factor.
Thus, for mechanical work of expansion pressure is the intensive and
volume the extensive factor. Similarly temperature is the intensive
factor of heat energy and entropy the extensive factor. Since ni and 112
are extensive factors, it follows that (fii)v,s and (fi2)v,s represent intensive factors of energy associated with the masses of components 1,
2 in solution and hence, like temperature and pressure, may be designated as potentials.
Expressions similar to Equation (14) may be developed for the other
three energy functions. Thus, for reversible changes
dH = TdS+Vdp+
dA=-SdT-pdV+
dG = -SdT+Vdp+
(Mi)s,^c^ni+ {,x,)s.^dn,+ -
(fiih. rdni+ (fi^h. rdm-l
(Mi)r, p dm + (^2)7-. pdn2+
(15)
(16)
(17)
616
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
and
,.= f?)
(21)
J'-E) f?A)
\dnjv,s,n2...
\oni/s,p,m...
/dG\
= (
=Gi
\dni/T,v, n2..
(22)
As previously pointed out m is the intensive factor of the internal energy associated with the mass of component 1, but it may be defined in
terms of any of the energy functions by Equa^on (22). This intensive
property is designated as the chemical potential. From the definition of
partial molal quantities (page 285) and Equation (22), it is evident that
the chemical potential of a component is equal to its partial molal free energy.
The other partial derivatives in Equation (22) are equal to the chemical
potential but are not partial molal quantities in the restriction of constant temperature and pressure.
If a closed system consisting of several phases, each of which is an
open system, is at equilibrium, its properties as a whole must satisfy the
criteria established on page 449. Thus, if the conditions of restraint are
constant temperature and pressure, at equilibrium, dG = 0, ii no means
of performing useful work is present. Also, any change in the free energy
of the system must equal the sum of the corresponding changes of its
parts. If the properties of the different individual phases of the system
are identified by prime markings and the different components of the
various phases by subscripts, from Equation (17),
dG=i-S'
dT+V
dp + ti[ dn[ + ^'^ dn'^ + )
'.;
-\-i-S" dT-^V" dp + ^[' dn{' -I-M2' dn',' + )
//
-1- ( - S ' " dT+V"
dp + n[" dn[" + M2" dn'," + . . . ) + ..-. (23)
At equilibrium under conditions of constant temperature and pressure
dG = 0,dT = 0, dp = 0, and
(jx'i dn'i + ix'i'dn['+ ix'i" dn'i" ]
)
+ (ni dn'2 + Ma' dn'/ + Ms" dn'^" + .) + = 0
(24)
CHAP. XIV]
CHEMICAL POTENTIALS
617
= 0 and
etc.
(25)
Ml
Ml
l,_"'\
M2 = M2' = M2,
(26)
i-i . - , : . . ,
618
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
V,
c^(?' = f ( 7 ' , p , M i , M 2 , - - - ) = 0
aG"=^f"(T,p,^^,t,2,---)-0
;
'
.;
"
*
'
(27)
where
'
F = degrees of freedom " /
/ ';
C = number of components
(t> = number of phases
Equation (27) is the famous phase rule of Gibbs, developed in 1875.
The foregoing derivation follows that presented by Keenan^";
As an example of the application of the rule, the equilibrium among
the liquid, vapor, and solid states may be considered. Thus, if only a
pure Uquid, for example water, is in equilibrium with its vapor, C = 1,
<^ = 2, and F = 1; one intensive property, either temperature or pressure,
J. H. Keenan, "Thermodynamics," John Wiley & Sons, New York C1941).
CHAP. XIV]
FUGACITY
619
but not both may be freely varied. If, however, ice is also present in
the system, C = 1, <^ = 3, and F = 0. Under such conditions no conditions can be varied and the specification of three phases fixes both temperature and pressure. If instead of pure water a binary solution of
water and alcohol is in equihbrium with its vapor, C = 2, <i> = 2, and
F = 2. Thus, two properties may be freely varied in such a system.
For example, both temperature and pressure may be varied freely over
restricted ranges with corresponding changes in composition of the
phases, but all three variables cannot be independently varied. A specified composition and temperature fixes the corresponding pressure.
When used in connection with the phase rule, the number of components is the least number of independently variable chemical substances
from which the system in all its variations can be produced. Elsewhere
in this text the term component is not used in this restricted sense.
FUGACITY
The concept of the chemical potential is of value in establishing the
fundamental thermodynamic requirements which must be satisfied by
a complex system when equilibrium is reached. Since at equilibrium
the chemical potentials of a component must be equal in all phases in
which it can occur, differences in the chemical potentials must be equalized by redistribution of the component as a system approaches equihbrium. If the chemical potential is high in one phase and low in another
material escapes from the first to the second phase until equality is
reached. Thus, the chemical potential may be considered as a measure
of what may be termed the escaping tendency.
Since the chemical potential is a measure of the escaping tendency,
it follows that any other property which is a unique function of the chemical potential is also a measure of the escaping tendency. Such a function,
termed the fugacity, was so defined by Lewis" as to simplify the
mathematical relationships of the equilibrium. By definition,
{d^A = dGA = RTd\nJA)T
(28)
where
/A = fugacity of component A at temperature T
HA = chemical potential of component A at temperature T
GA = partial molal free energy of component A at temperature T
From this definition it follows that in any system which is restrained to
a constant temperature at equilibrium the fugacities of any component must
he equal in all phases in which it appears. For a pure component the par" G. N. Lewis, Proc. Am. Acad. Arts, Sd., 37, 49 (1901).
'
' '
620
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
tial molal free energy GI is equal to the molal free energy G and Equation (28) reduces to
,
(dG = RTd In f)T
(29)
Equations (28) and (29) do not serve to define the numerical values of/
but do establish the changes in / which correspond to specified changes
in G or G at constant temperature.
From Equation (k), Table XXIV, page 472,
\dp/T
Combining this with Equation (29) gives
'
/ a In A ^ _ v _
\ ap
IT
I
(30)
RT
zRT/p.
T^^^'
[d \n f=^zd In P)T
(31)
From Equation (31) it is evident that for an ideal gas, where 2 = 1.0
the fugacity is proportional to the pressure. The definition of fugacity
is completed, and numerical values are assigned to it by arbitrarily setting the fugacity of an ideal gas equal to its pressure. Thus fugacity
has the units of pressure and is numerically equal to pressure in the ideai
gaseous state. Under other conditions pressures and fugacities are not
equal, and fugacity is sometimes referred to as a corrected or thermodynamic pressure. However, from the definition it is evident that the
corrections involved are a function of free-energy changes and the fugacity is useful only for equihbrium calculations where free-energy
changes are the criterion.
Fugacities of Pure Gases. An expression for the fugacity of a gas at
any conditions is obtained by rearranging Equation (31) in terms of the
ratio of fugacity to pressure f/p which by definition is equal to 1.0 at
zero pressure where ideal behavior is realized. Thus
s , ,;
/
d\nf/p
= zdlnp
d\ap=
{z--l)d\np
(321 /
/ -
CHAP.
621
relationship of Fig. 103. Various investigators have carried out this integration which is conveniently presented by plotting the ratio of fugacity to pressure (//p) against reduced temperature and pressure. This
ratio / / p = V will be termed the fugacity coefficient and is equal to unity
where the ideal-gas law is vaUd. This ratio is frequently termed the
"activity coefficient," but it is believed preferable to reserve this latter
term for expressing relationships between fugacities and composition in
solutions.
Average values of the fugacity coefficients of gases are plotted in
Fig. 142.'-^ This chart was derived from the same data on which
Fig. 103 was based. For many purposes these charts may be taken as
appHcable to all gases. The errors involved are generally less than
10 per cent.
The fugacity of any gas or vapor at specified conditions is readily obtained when its critical temperature and pressure are known.
Illustration 5. Calculate the fugacity of methane at 122F and 1000 lb per
sq in. abs.
From Table XXVIII, Tc = 343R and p, = 673 lb per sq in.
^ , ,
.
122 + 460 ,
Reduced temperature =
= 1.70
s
;
343
Reduced pressure = -VT# = 1-49
. :.*
Fugacity coefficient (Fig. 142) = 0.94
'
Fugacity = (1000) (0.94) = 940 lb per sq in.
Fugacities of Pure Liquids and Solids. From the basic concept of
fugacity as a measure of escaping tendency, it follows that the fugacity
of a liquid or solid must be equal to that of its vapor in equilibrium with
it. Thus, when a liquid is in equilibrium m t h its pure vapor, the fugacity of the liquid is determined by calculating the fugacity of the vapor
at the equilibrium temperature and pressure.
Illustration 6. Calculate the fugacity of liquid benzene in equilibrium with its
pure vapor, at a temperature of 428F. The critical temperature of benzene is 550F,
and its critical pressure is 700 lb per sq in. The vapor pressure at 428F is 281 lb
per sq in.
Reduced temperature =
= 0.88
650 + 460
Reduced pressure = 281/700 = 0.40
Fugacity coefficient (Fig. 142) = 0.79
Fugacity of vapor = fugacity of liquid = (281) (0.79) = 222 lb per sq in.
The fugacity of the liquid state is a function of total pressure as expressed
by Equation (30). This equation may be integrated by expressing v as
" B. W. Gamson and K. M. Watson, Natl. Petroleum News, Tech. Sec, 36, /J623
(September 6, 1944). Also "Process Engineering Data," National Petroleum FubUshing Company, Cleveland (1944).
622
l O CO
CO
THERMODYNAMICS OF SOLUTIONS
d/S
CO
CO
lO
Tl>
[CHAP. XIV
CO
o
o o
o
o
u 'luaioijjaoQ iIq.tDBSi\j
623
where
/ff = fugacity at total pressure ir
/p = fugacity at normal vapor pressure P
Equation (30) permits calculation of the fugacities of liquids at any
total pressure but the integrated form, Equation (34), is useful only at
reduced temperatures below 0.9.
Illustration 7. Calculate the fugacity of liquid benzene at 428F if the liquid is
in an atmosphere of hydrogen such that the total gauge pressure is 2000 lb per sq in.
The average density of liquid benzene at these conditions is 0.63 g per cc.
f=
= 1.98 cu ft per lb-mole
(0.63) (62.4)
^
Substitution in Equation (34), gives
Xnl^=
1.98(2015-281) ^
222 (10.71) (428+ 460)
log/,r/222 = (0.361)(0.434) = 0.157 or /,,/222 = 1.43
f^ = the fugacity at 2015 lb per sq in. = (1.43) (222) = 318 lb per sq in.
dT A
624
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
(f)r(fa4*-l-(m
^
'"
Combining (37) with Equation (XI-4) and (1) of Table XXIV, gives
^ain/\
H*-H
(where
/
H = molal enthalpy at an elevated pressure p and temperature T
H* = molal enthalpy at the same temperature T but at a pressure sufficiently low so that the gas behaves ideally
The quantity H* H may be obtained from the generalized correlation
of Fig. 105 or may be calculated from compressibility data by the methods developed in Chapter X I I . Charts such as Figs. 117 or 120 or
thermodynamic tables permit direct evaluation of H* H for either the
liquid or vapor state as a function of temperature and pressure.
Fugacities in Solutions. The partial molal extensive thermodynamic
properties of a component in solution are related to each other by expressions parallel to those developed for pure substances in Chapter XI.
For example, by Equation (XI-4), page 446, for any system,
G = H-TS
(39)
\dn2/T,p,m...
\dn2J T,p,m'...
Each of the derivatives of Equation (40) represents a partial molal quantity. Therefore,
G2 = S 2 - r s 2
(41)
G2Ha
,,
TT-
r'-":
i (43)
CHAP. XIV]
FUGACITIES IN SOLUTIONS
625
dp JT RT
^^^
Combining (28) and (43) in the manner used in developing (38), gives
/aln/zN
H|-H
(45)
\ dT ) ~ RT^
In using Equation (45) care must be taken that the partial molal enthalpy H2 is expressed with respect to the same reference state as the
molal enthalpy of the ideal gas, H | .
Equations (28), (44), and (45) permit calculations of the fugacities of
components in solutions from a variety of data such as vaporization,
solubility, or distribution equilibrium measurements. For example,
the fugacity of a pure solid at a specified temperature may be determined from its vapor pressure, and this value is equal to the fugacity
of the solid as a solute in any saturated solution at this same temperature.
The variation with temperature and pressure of the fugacity in solution
can then be calculated by means of Equations (44) and (45), if partial
volume and enthalpy data are available.
If Equation VIII-34 is written for free energies, at constant temperature and pressure,
rii dGi +112 dSi + ws doz -f = 0
(46)
=Q
(47)
NJ^\
+NJ'^\\NJ'^
\5iV2A.p
V^Wr.p
+... = 0
VaWr,/
(48)
^'
'
626
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
(51)
where
' ^''^'''"^'
'''''"'' ' ''-''"> ;4HVV ...v .
/ j = fugacity of component 2 in the solution
/ j = fugacity of pure component 2 at the temperature fnd pressure of
the solution
.
,
,
N2 = mole fraction of component 2
.
I 'i
! !->
.'
'i
Lewis and RandalP' define the ideal solution solely by Equation (51)
and point out that all other properties attributed to ideal solutions such
as additivity of volumes and enthalpies follow from this definition.
For gaseous mixtures at low pressures Equation (51) is equivalent to
Dalton's law while for liquid solutions whose vapors are ideal gases it is
equivalent to Raoult's law. However, at conditions resulting in large
deviations from ideal-gas behavior, fugacities are not equal to partial
pressures, and Equation (51) may be looked upon as an improved statement of Dalton's and Raoult's laws which is generally applicable over
a much wider range of conditions.
The assumption that gases form ideal solutions is of a much higher
order of accuracy than the ideal-gas law and may be applied with accuracy satisfactory for many purposes to gaseous mixtures at pseudoreduced pressures less than 0.8. If the pseudoreduced temperature is low,
of the order of 1.0 or less, difficulty is encountered in handling the highboiling components of the mixture, which, if they existed alone at the
temperature and pressure of the mixture, would be liquefied. In such
cases the term f'2 of Equation (51) may be estimated from the brokenline extrapolations of the curves of Fig. 142 into the two-phase region.
Thus, hypothetical fugacity coefficients for the pure gases atf pressures
above their vapor pressures are obtained. This procedure is not satisfactory where extended extrapolation is required. For mixtures at
higher temperatures, above the critical temperatures of all components,
the assumption of ideal solutions is more satisfactory and may be extended to higher pressure ranges.
j
! . /
Illustration 8.
mole per cent:
17
35
48
106
/
'
. "'
Assuming an ideal gaseous solution, calculate from Fig. 142 the fugacity of each
CHAP. XIV]
STANDARD STATES
627
component when the mixture is at an absolute pressure of 300 lb per sq in. and a
temperature of 100F.
Solution:
Tin (Table XXVII)
Pc lb per sq in. (Table XXVII)
Tr
Pr
;- (Fig. 142)
/ ' = 3001'
,' ,
/ = A7'
Methane
343
673
1.63
0.446
0.98
294
50.0
Ethane
550
717
1.02
0.418
0.87
261
91.5
Propane
666
642
0.84
0.466
0.73
219
105
ACTIVITY
-(fX
<=^)
where
a = activity
/ = fugacity in the given state
f = fugacity in the standard state at the same temperature
Combining Equations (28) and (52) gives
i
RTlna = G-G
(53)
where
G = partial molal free energy in given state at temperature T
G = partial molal free energy in the standard state at the same
temperature T
The concept of activity is particularly useful in dealing with liquid
solutions. For example, if the standard state of a component which is
in solution is taken as the pure component at the temperature and pressure of the solution, the activity becomes a function of the concentration
or fraction of the component in the solution. Thus, the activity provides
a basis for the thermodynamic expression of concentrations or compositions in terms directly related to free energy by Equation (53).
Standard States. The choice of the standard state necessary to complete the definition of activity is arbitrary since it affects only the numerical magnitude of the function and not its relationship to other prop
628
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
erties. It is, however, desirable to select standard states such that the
resulting numerical scales will be convenient and correspond to common
expressions of composition in ideal systems. Different standard states
may be selected for the same substance for use in different types of relationships, the choice being dictated by convenience. It is important
however that the standard state of each component be kept the same
throughout any one series o relationships or calculations. It is evident
that the numerical value of activity is without significance unless the standard state is specified.
The following standard states have been found convenient for certain
types of calculations and are in more or less general use.
Components of Gaseous Mixtures, (a) It is frequently convenient to
define the standard state as the state of unit fugacity, orf 1.0. With
this choice of standard state the activity of a gaseous component is equal
to its fugacity and has the same numerical value. In mixtures of
ideal gases the activity of each component is equal to its partial pressure.
(6) In other cases it is more convenient to define the standard state
as the pure component at the temperature and the pressure of the mixture. With this choice of standard state the activities become equal to
the mole fractions in mixtures which form ideal solutions. It may be
noted that with this definition the standard state changes with change
in pressure whereas standard state (a) is independent of the pressure of
the system.
Pure Liquids and Solids. When a liquid or solid is involved in a
process in its pure state, it is customary to designate its activity as
unity under a specified pressure. Three choices have been used in the
specification of the pressure of the standard state.
(a) The pure component under a pressure of 1.0 atm is widely used
as the standard state for nonvolatile substances.
(6) For volatile substances whose vapor pressures exceed 1.0 atm it
is convenient to define the standard state as the pure substance under
its own vapor pressure.
(c) In certain calculations it is convenient to define the standard state
as the pure substance under the pressure of the system. With this
definition the standard state varies with change in pressure whereas
states (a) and (b) are independent of pressure.
Components in Nonelectrolytic Solutions. The standard state for either
a solid or liquid component in a nonelectrolytic solution may be taken
as the pure component in either the solid or liquid state under one of the
three pressure designations enumerated in the preceding paragraph.
Pressure designations (a) and (6) have the advantage of defining the
standard state independent of pressure. Use of designation (c) leads
CHAP. XIV]
STANDARD STATES
629
= 1.0
(54)
It may be experimentally demonstrated that as infinite dilution is approached the fugacity of a solute becomes proportional to its mole
fraction,
f2 = KN2
as N2>-0
or
(7^7)
=K
(55)
Combining (52), (54), and (55) for an infinitely dilute solution gives
or
!*
'.
/^' =
fc2
(66)
630
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
as
ni2>-0
(57)
as m2-0
or
(^\
fcj'
(58)
Combining (52), (57), and (58) for an infinitely dilute solution gives
..a^'=m2=A = _ ^
or Jl" = K'
(59)
CHAP. XIV]
ACTIVITY COEFFICIENTS
631
volved or approximated, these relationships between activities are directly translatable into ordinary compositions. If ideal behavior cannot
be assumed, it is necessary to introduce an empirical factor which relates
activity to composition. This factor is termed the activity coefficient y,
which is the ratio of activity to a numerical expression of composition.
The numerical value of the activity coefficient is dependent both upon
the standard state of the activity and upon the units of expression of
composition. Both of these factors may be arbitrarily selected, and the
activity coefficient has no significance unless both are specified.
The most commonly used activity coefficients relate activities to mole
fractions or molalities. The following symbols are used for the three
coefficients of most importance in dealing with systems at low pressures.
* ''^
'"'
72 = a^/Ni
y2 = a'JN2
T2' = 027^2
,
'
''
^,
(60)
(61)
(62)
where
02 = activity of component 2 referred to the pure component
a'2 = activity of component 2 referred to infinite dilution where
02 = N2
a'2' = activity of component 2 referred to infinite dilution where
a'2' = m2
632
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
these expressions are fixed by the concentration of the state of unit activity or of unit activity coefficient, respectively, even though the fugacity
is unknown. Since a = f/f, Equation (47) may be written for changes
in activity due to changes in composition at constant temperature and
pressure.
'>
Nidlnai
+ N2d\na2 + Nsdlnas-i
= 0
(63)
.yif'i};;
dlnai
where
x -
(64)
'
+ Nidlnyi+N2d\nN2+N2dlny2-\
= 0
= 0
NidlnNi
+ N2dlnN2
+ N3dlnNs-i
Nidlnyi
+ N2dlny2 + Nadlny3-{
'/'
/
(65)
, ^~ ^, !
, :|
= 0
= 0
(66)
(67)
(
2ldlny,+
C
w!
f2
A/2
;., .
(68)
CHAP. XIV]
ACTIVITY COEFFICIENTS
consideration.
633
Thus,
In as = /
dlnai+
d In as -|
(70)
f, = a,fl = a'JV=a','fl"
(71)
It is thus evident that the ratio of activities relative to different standard states is given by the ratio of the fugacities of the standard states
according to Equation (72) and that these conversion factors are constant over the entire range of concentrations.
A further relation between activities in aqueous solutions results from
consideration of the infinitely dilute solution where, since 1000 g of
water is equivalent to 55.51 g-moles, it follows that,
^
(73)
(^i.=r^"
. ^
<'
=fl"
/ r = 55.51/2"
(75)
-'
(76)
634
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
(77)
For mole fractions of zero and unity the following values are obtained-.
' "
. .
02
ai.
oj'
72
72
. :i- y'i
AtiV2 = 0
0
0
0
2.60
1-0
1-0 ^z-.-,:;
AtiVa=1.0(m2 = 00)
1.0
0.384
V 21.35
^ 1.0
0.384
0
f .^
> - ?:
.^
(77a)
Illustration 9. From the data for the vapor pressure of water above sugar
(C12H22O11) solutions taken from the International Critical Tables and summarized
in Table XXX, calculate the corresponding
(o) Fugacities of the water in solution.
(6) Activitiesffliand activity coefficients 71 of the water referred to pure liquid water.
(c) Activities 02 and activity coefficient 72 of the sugar referred to the pure sohd.
(d) Activities 02 and activity coefficients 72 of the sugar referred to mole fractions
at infinite dilution.
(e) Activities oj' and activity coefficients 72' of the sugar referred to molaUty
at infinite dilution.
FIGS. 143O and 6. Comparison of Activities and Activity CoefBcients for Different
Standard States.
' 6 3 5
636
THERMODYNAMICS OF SOLUTIONS
[CHAP.
XIV
TABLE XXX
ACTlVITy OF ^^ A T E K
Mole Fractions
Mohdity C i j H j j O i i H2O
m
Ni
iVi
0
0
1.0
0.00180 0.99820
0.1
0.00715 0.99285
0.4
0.01770 0.98230
1.0
0.03478 0.96522
2.0
0.05127 0.94873
3.0
0.06722 0.93278
4.0
0.08263 0.91737
5.0
6.0
0.09755 0.90245
6.18 (Sat) 0.10018 0.89982
I N SUGAR SOLUTIONS AT
Vapor
pressure
mmHg
Pi
23.756
23.714
23.585
23.302
22.762
22.166
21.521
20.846
20.20
20.08
ffli
1.0
0.99823
0.99280
0.98089
0.95816
0.93307
0.90592
0.87750
0.85031
0.84526
71
1.0
1.0000
0.99995
0.99856
0.99269
0.98349
0.97120
0.95654
0.94222
0.93937
25C
log 71
0
0.0000
-0.00002
-0.00063
-0.00319
-0.00723
-0.01269
-0.01930
-0.02585
-0.02716
Ni/Ni
00
554.56
138.86
55.497
27.752
18.505
13.877
11.102
9.251
8.9820
Solution: (a) At the low pressures involved it may be assumed that the fugacities
of the water vapor/i are equal to partial pressures pi.
(6) T?he activities Oi of the water
'70 n
1
1
\
1
I
1
1 in the solution are obtained by dividing j)i by 23.756 the vapor pres60
sure and fugacity of the pure water
at 25''C which is chosen as the
50
standard state. At the low pressures
involved the pressure designation of
40
the standard state is of no conse^1
quence since pressures of this order
N,230
have a neghgible effect on the fugacity of the liquid. The activity co20
efficients 71 are equal to ai/Ni.
(c) The activity coefficients of
10
the sugar 72 are determined by
-^6| ^6 I -'14 I A^ I A,
graphical integration of Equation
(68). Values of -log 71 and Ni/Ni
8
12 16 20 24 28
from Table XXX are plotted in Fig.
-log (TiXlO"')
144. Since the fugacity of the sugar
in the saturated solution is equal to
FIG. 144. Evaluation of the Activity Coeffithat of the pure solid, the activity
cients of Sucrose
02 of the sugar in the saturated solution is 1.0 referred to the pure solid. The corresponding activity coefficient 72 =
l.O/ATj = 9.9820 where Ni/Ni = 8.9820. These values fix the lower limit of the integral which may be written
rNi/N2 Ni
I
log 72 = - I
- d log 71 + log 9.9820
^8.9820 AT
>/8.9820 Ni
The incremiptal evaluation of the integral is indicated in Fig. 144, and the resultant
values of 72 are given in Table XXXI. Corresponding values of a^ are obtained by
multiplying A'^2 by 72.
(d) In Fig. 145 values of 72 are plotted as ordinates on a logarithmic scale against
y ..
IONIC ACTIVITIES
CHAP. XIV]
637
Ni and the resulting curve extrapolated to N2 = 0. Values of oj and ai' are then
calculated from Equation (72). The corresponding activity coefficients are by definition yi = ai/Ni and 72' =a^'/m. These results are summarized in Table XXXI
and Fig. 145.
TABLE XXXI
ACTIVITIES OF SUGAR IN AQUEOUS SOLUTIONS AT 2 5 C
N^
0
0.1
0.4
1.0
2.0
3.0
4.0
6.0
6.0
0.00180
0.00715
0.01770
0.03478
0.05127
0.06722
0.08263
0.09755
6.18 0.10018
72
3.2800
3.2899
3.3696
3.8539
4.7222
5.7860
7.0175
8.3880
9.7225
9.9820
72
ai'
1.000
0
0.00592 0.00180 1.000
0.1000
0.02409 0.00734 1.027
0.4074
0.06821 0.02080 1.175
1.155
0.16424 0.0501
1.400
2.779
1.764
0.29665 0.0904
5.020
2.139
0.47172 0.1438
7.983
2.557 11.730
0.69310 0.2113
2.964 16.05
0.94843 0.2899
3.043 16.92
1.00000 0.3049
az
02
72
1.000
1.000
1.019
1.155
1.390
1.673
1.996
2.346
2.675
2.738
From inspection of Fig. 145 it is evident that the activity coefficients 72 and yi
are widely different in numerical values but are related by a constant factor. The
coefficient 72' approaches 72 at low
10 r
concentrations but is not related to
9
the other two coefficients by a con8stant factor.
7It may be noted that the graphical
integration shown in ,Fig. 144 becomes uncertain at low concentrations .where Ni/Nt
approaches
infinity. Special graphical methods T2
have been developed by Lewis and
Randall" to circumvent this diffiyj^
culty and permit accurate integra^72"
tions with zero concentration as one
limit.
__^J
Although determination of
0
0.02
0.04
0.06
0.08
0.10
activities and activity coefHcients from vapor-pressure data FIG. 145. Activity Coefficients of Sucrose
is most direct, in principle the
in Aqueous Solutions at 25 C.
results are frequently less accurate than those obtained by other methods involving different types of
equilibrium.
Lewis and Randall'^* discuss in detail the evaluation of activity coefficients from data on solubilities, distribution coefficients, freezing points,
boiling points, and electromotive-force measurements.
Ionic Activities. The expression of activities in solution of electrol5rtes
is complicated by the dissociation of the components into ions. Tbia
638
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
JUi
n\
55.51
'- d log oi
d log ai =
n2V2
(79)
m-iVi,
'-
a, = kia^r-
= ^^
(80)
- \kK
I"*
-^
(80a)
(81)
CHAP. XIV]
IONIC ACTIVITIES
where
639
Wj = stoichiometric molality
For example, calcium chloride dissociates into one positive and two negative ions or v+ = 1, ><_ = 2, v^ = 3, and m^2 = m2(4)*.
The standard state for the expression of the activities of electrolytes
is so chosen that 0*2 = w2 as infinite dilution is approached. Thus,
j_
'
(82)
""''fl
"
7.2 = ^
. . . . . . ^ . \:
(83)
m^2
;
:
:
I t is evident that 72 = 1.0 at zero concentration.
For the expression of the apparent molecular activities of electrolytes,
a special standard state is commonly selected in order that the following
relationship shall be valid.
V'i
(84)
7 2 " =
mi
"'-
(85)
It should be noted that this definition of standard state does not require
that 7 2 " be imity at infinite dilution.
By combination of Equations (81), (82), and (84) mean ionic activities
may be determined from vapor-pressure measurements which permit
calculation of the apparent molecular activity 02 referred to the pure
component or some other convenient state. Thus,
/ '
fc27=.2=^^-
mi
;.
(86)
> U-^iiiHth
where
'. - "
h = ^^
'-Y
(87)
Values of /c272 from Equation (86) are plotted against m2 and extrapolated to zero molality where by definition 72 = 1-0. This intercept is
equal to ki from which values of 72 at all concentrations may be cal-
THERMODYNAMICS OF SOLUTIONS
640
[CHAP. XIV
T2^
'2
1.0
,0.8
'^\
l'i
CO
.2
3|
01
ID"-
30.
So.
do.
0)1
=3
ml
Ml
<fa 2/111 1 _ ^ ^
0.1
0.08
0.06
0.05
0.04
0.03
0.02
0.01
6
3
4
5
Molality, rrii
'. '
FIG. 146. Activity Coefficients of Aqueous Sodium Chloride Solutions at 25C.
(88)
It is evident from Equations (88) and (89) that both 72"and 72 must
approach zero at zero concentration where 7*2 = 1.0 and m2 = 0. The
CHAP. XIV]
PROBLEMS
641
relationship between the various activity coefficients is shown graphically in Fig. 146 for NaCl in water at 100C. Values of 02 and 72 referred to pure NaCl(s) may be calculated from vapor-pressure data by
the method of Illustration 9. In accordance with Equation (86) the
quantity \ailm2 is plotted against rui and extrapolated to ma = 0.
The value of fca is equal to this intercept, since 7^2 = 1-0. The corresponding values of 7 2 " are obtained from Equation (88). This method
is presented to clarify the relationships between the various standard
states and activity coefficients. Actually it is not a practical means of
evaluating activity coefficients with a high degree of accuracy because
of the difficulty of obtaining precise vapor-pressure data for very dilute
solutions. More accurate experimental methods are discussed in detail
by Lewis and Randall.'^
PROBLEMS
1. A mixture of hydrocarbon gases has the following composition in mole per cent:
CH4
CaHe
CsHg
nC4Hio
nCsHij
38.38
7.56
7.05
11.29
35.72
100.00
Calculate the density of this mixture in pounds per cubic foot in the gaseous state
at a temperature of 200F and an absolute pressure of 400 lb per sq in.
2. Calculate the density in grams per cubic centimeter of the mixture of problem 1 in the liquid state at a temperature of 100F and an absolute pressure of
1300 lb per sq in,
3. Calculate the enthalpy in Btu per pound of the mixture of problem 1 in the
gaseous state at the specified conditions. As the reference state of zero enthalpy
use the ideal gaseous state at 60F for the propane and lighter constituents. For
butane and the heavier constituents use the saturated liquid state at 60F as the
reference. It may be assumed that the enthalpies of the components are additive
under these reference conditions. Heats of vaporization of the three light gases are
given in Illustration 4. Doss' recommends the following values in calories per gram
at the normal boiling point: n-butane 92.0; n-pentane 85.5.
4. Calculate the enthalpy in Btu per pound of the mixture in the liquid state
at the conditions of problem 2, using the reference states specified in problem 3.
5. From the data of Table XXVIII and Fig. 142 calculate the fugacity in pounds
per square inch of pure ethane gas at a temperature of 200F and an absolute pressure
of 1500 lb per sq in.
6. Calculate the fugacities of the following gases;
(a) Air at GOT and 100 atm.
(b) Ammonia at 80C and 40 atm.
{<) Carbon dioxide at 150F and a gauge pressure of 2,000 lb per sq in.
7. Calculate the fugacity of the Uquid ethylene in contact with its saturated
vapor at 0C and 40.6 atm.
642
THERMODYNAMICS OF SOLUTIONS
[CHAP. XIV
100 5
1.52
1.49
1.46
1.45
1.43
R--
(Po - v)
mPo
0.7
1.5
4.0
5.0
6.0
100 B
3.25
3.62
4.46
4.67
4.82
m
7
9
11
17
20
100 J?
4.91
5.00
4.89
4.25
3.85
13. The following data from the International Critical Tables show the partial
pressures in milhmeters of Hg of toluene and acetic acid in solutions at a temperature of 69.94C:
CHAP.
XIV]
PROBLEMS
Pi (toluene)
0
54.8
84.8
101.9
117.8
130.7
137.6
145.2
155.7
167.3
176.2
186.1
193.5
202
643
Pz (acetic acid)
136
120.5
110.8
103.0
95.7
88.2
83.7
78.2
69.3
57.8
46.5
30.5
17.2
0
Calculate the activity coefficients 71, 72 from these data. Plot the activity coefficients as ordinates on a logarithmic scale against the mole per cent toluene on a
uniform scale and check these cui'ves for consistency with the Gibbs-Duhem equation
at compositions of 10, 30, 50, 70, and 90 per cent toluene.
CHAPTER XV
,j PHYSICAL EQUILIBRIUM
The concepts of fugacity and activity are of particular value in problems of equilibrium in both physical and chemical processes. Where
only pure components or ideal solutions are involved, such problems are
readily solved by apphcations of the principles developed in the preceding chapters. If a system under consideration involves a nonideal solution, the evaluation of the activity coefficients of the components is
frequently the most difficult problem. Some direct experimental data
combined with empirical or semiempirical relationships are generally
necessary.
VAPOR-LIQUID EQUILIBRIUM
^^^
where
7i = activity coefficient of component 1
Ci = activity of component 1 in solution referred to the pure
component
/ i = fugacity of component 1 in solution
fl = fugacity of pure component 1 at the temperature and pressure of the solution
If it is assumed that the vapors form an ideal solution, the fugacity / i
of Equation (1) is readily calculated as in Illustration 8 (Chapter XIV)
from the composition, temperature, and pressure of the vapor in equilibrium with the solution. The fugacity of the standard state is calculated
from the vapor pressure of the pure compound and the total pressure
of the solution by the method of Illustration 7, page 623. In this manner, if sufficient data are available, activity coefficients may be evaluated
in any given system as a function of composition, temperature, and total
pressure. The results may be verified for thermodynamic consistency
644
CHAP. XV]
VAPOR-LIQUID EQUILIBRIUM
645
^, = _ ^ = .^i!l
(2)
where
PHYSICAL EQUILIBRIUM
646
[CHAP. XV
'
.-/
I'
V
4)
0
t/
;^
?>..
^s^JV
7
HI
\X
^
" ^
1.0
0.9
0.8:
0.7
0.6
'
>>
1^^ ^ ^
f5f^
^
0.5 *\ . ^ ^
0.4
0.3
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
a;=Mole Fraction of Lower Boiling Component (*)
1
:_ Liquid
T:
;A Phase
T>I
^
in
''
CHAP. XV]
647
0.
I
^a /
o
U
\\
'/o
^x ^^
i>
o>0,
.2-S
8 0,
S.
o 0,
IL 0,
fy
if
i i-A VA
/^
^
a
>
r /,A
/y^
/
0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
i=Mole Fraction of Lower Boiling Component
(*) in Liquid Phase
Fro. 148. Vapor-Liquid Equilibria of Typical Binary Systems.
the system forming an azeotrope of maximum boiling point the activity
coefficients are less than unity. This behavior is general for many nonideal systems. Activity coefficients greater than 1.0 are much the more
common.
If the effects of the small variations in temperature are neglected, the
slopes of the curves of Fig. 147 for any system at constant temperature
and low pressure are related to each other -by Equation (XIV-69), and
if one curve is known the other is readily calculated. For the prediction
of both activity curves from a minimum of experimental data a general
relation between activity coefficients and mole fraction is necessary.
Free Energy of Mixing. Thermodynamically consistent expressions
for the activity coefficients of components in solutions are most con-
648
PHYSICAL EQUILIBRIUM
[CHAP. XV
veniently derived by consideration of the free-energy changes accompanying the formation of a solution from its components in their standard states. This free-energy change of mixiri^ MXM is given by the
following general equation where the standard state is taken as the pure
120 r
0 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 O.QO 1.00
a;=Mole Fraction of Lower Boiling Component (*)
in Liquid Phase
FIG. 149. Saturation Temperatures of Typical Binary Systems at l.OAtm Pressure,
components at the pressure and temperature of the system:
AGjif = SniGi SriiGi,
where
_
_
_
,
SwiGj = niGi-|-?i2G2 + WaGs-|- = G
2niGi = riiGl + n^Gl + U^GI -\
(3)
./'
Combining (3), (XIV-53) and (XIV-60) and using Xi for mole fraction
instead of Ni for the liquid phase gives
A(?M = RT^Ui In Xi + RTSm In ji
where
Ui In Xi = n-i In Xi -\- n^ In x^ + wa In xs -|-
w
M^
(4)
CHAP.
XV]
649
For an ideal solution all activity coefficients are equal to unity and the
term RTllrn In ji reduces to zero. This term is designated by Scatchard
and Hamer' as the excess free energy G^ of the solution. Thus, the free
energy G of any solution may be written as
G = -SniGl + RTl;ni hi Xi + G'^
(5)
where
G^ = RT'Srii In yi = the excess free energy
The chemical potential of any component is obtained by differentiating
Equation (5), thus for component 1,
dSnilnXi
dG^
,
Mi = G, = Gl + i ? r ^ +
(6)
dni
dn
The expansion of the second term combined with the principle of
Equation (XIV-66) gives
RT^-
'=RT\liixi
+ ni-^
+ n,---^
+ --- \ =
RTlnxi{7)
Then,
;
'.
ixi = Gi = Gl + RTlnxi+-
(8)
dni
By comparison of Equations (8) and (XIV-53) it may be seen that
RT\ny,
=- dni
(9)
Similarly,
/2rinT. =
(10)
+ ^ihiiZiZh^iZiaihii
RTiSqiXi)
where
Xi = mole fraction of component i
Qi = effective molal volume of component i
' *
Zi = effective volume fraction of component i
' G. Scatchard and W. J. Hamer, / . Am. Chem. Soc, 57, 1805 (1935).
K. Wohl, Trans. Am. Inst. Chem. Engrs. 42, 215-250 (1946).
(11)
650
PHYSICAL EQUILIBRIUM
[CHAP. XV
Subscripts i, h, j , I each m a y correspond to any component of t h e mixture in the terms of the indicated summations.
Uih etc. = empirical constants corresponding t o t h e indicated groups
of components in the summations.
Equation (11) is designated a, four-suffix empirical equation as characterized by the last term. T h e first summation term m a y be considered
as indicating the effect on t h e excess free energy of the interactions between unlike molecules of t h e components in pairs. T h e second term
indicates the contributions from interactions of groups of three molecules while the third takes into account interactions of groups of four.
If the last summation is omitted t h e remainder is a three-suffix equation,
whereas if the last two terms are omitted it becomes a two-suffix equation. E a c h additional summation introduces added constants to permit
improved representation of increasingly complex relationships.
E a c h summation in E q u a t i o n (11) represents the sum of all possible
combinations of molecules in unlike groups of the indicated size. Thus,
in a mixture of components 1, 2, 3, , component 1 is first t a k e n as i,
and all possible groups are expanded by successively designating each
component of the mixture as h, j , and I. For example, for a ternary
system the second summation is expanded to 24 t e r m s as follows for all
possible triple combinations among two and three unlike species.
liihiZi^hZiaihj = ZiZiZ^aiu -\- ZiZiz^ani -{- ZiZi^iUm + ZiZ^iam
-\- ZiZ'^iai23-\- ZiZsgiai3i-{- ZiZ3Z2au2-{- ziZ3Z3au3-\- z^iZittin
.
-^ ZiZiZ2a2u-\- z^iZ3a2i3-\- Z2Z^ia2ii-\- Zi?^za22s-\- Zi^aZiUisi
-\- Z2ZdZ2(t23i + 22^3230233 + Zs^l^ 1^311 + Z^lZiUsu "H 232123^313
-|- 2322210321 + 2322220322 "f" 2322230323 + 232321O33I "f 2323220332 (12)
Since the order of multiplication is immaterial, t e r m s such as 2122O112
and 2i222iai2i are identical a n d m a y be grouped together. T h u s , E q u a tion (12) reduces to seven t e r m s :
/
,. , .
; ,A.
.,
(13)
(14)
2l:
, ?2
93
Qi
CHAP. XVJ
651
(15)
and
. :
22=
.
a;i + X2 + X3-\
21
3i
Activity Coefl5cients in Binary Systems. For a binary system of
components 1 and 2, a three-suffix equation of the form of (11) may be
expanded as follows:
RTiqiXi + q^Xi)
(16)
(18)
(19)
Then
V^
;vuV\
RT
-'IXI + ^^XXIZLI-)B'
+ Z2A'~\
(20)
The term In 71 may be evaluated by partial differentiation of Equation (20) with respect to wi in accordance with the relationship of Equation (9). This is done by first replacing x and z by n by means of the
following relations:
Qi
rii
xi = , ;
X2 = ;
ni + n2
ni + n2
zi =
ni + ^^2
gi
a;i-|-a;2 = 1.0;
22
(21)
n, + ^-^ n^
91
2i-|-Z2=1.0
= G^
ni + n2
^p
nln2B'+ninl(-) A'
\qi/
I n i + -712)
\
gi
/
(22)
652
PHYSICAL EQUILIBRIUM
Upon differentiation
B = 2.303B',
^^"
2.303dni{RT)
nl(^^y[-n,A+2n.B(^^ynA{f)]
= log 71 = -^^^^
7
rri
=
^ ^ ^ ^ (23)
I I IM - V l =
[CHAP. XV
:^ ,
(24)
A \ ^
(25)
(26)
(27)
A V ]
BV]
(28)
(29)
In these equations 2 represents the volume fraction based on the volumes of the pure components and is the true volume fraction if volume
changes in mixing are negligible.
If it- is assumed that 51/52 = A/B Equations (24) and (25) reduce to
' M. Margules, Sitzber. Akad. Wiss. Wien. Math, naturw. Klasse, II, 104,
78 (1895).
* H. C. Carlson and A. P. Colburn, Ind. Eng. Chem., 34, 581 (1942).
G. Scatchard, Chem. Rev., 8, 321 (1931).
6 G. Scatchard and S. S. Prentiss, J. Am. Chem. Soc, 56, 1486 (1934).
' G. Scatchard and W. J. Hamer, J. Am. Chem. Soc., 57, 1805 (1935).
1243\
i
'
CHAP. XV]
653
(30)
(|xx + x.J
log y, = Bzl =
^ -
(.x+fx.y
(31)
Differentiation proves that Equations (24-31) satisfy the general relation of Equation (XIV-69). The constants A and B are characteristic
of each particular system. In the van Laar equations (30) and (31)
it is evident that A is the terminal value of log 71, where xi = 0, and B
is the terminal value of log 72, where X2 = 0.
Equations (24-31) are basically restricted to conditions of constant
temperature. However, as previously pointed out, little error is generally encountered in applying them to activity coefficients at constant
pressure in close boiling systems.
If the validity of the van Laar Equations (30) and (31) is accepted,
determination of 71 and 72 at a single known composition permits evaluation of A and B and calculation of the complete 7 curves. Measurement of a single set of equilibrium liquid and vapor compositions, together with knowledge of the vapor pressures of the pure components,
suffices for calculation of 71 and 72 from Equation (2). Where an azeotrope is formed the composition of only one phase need be measured
since the liquid and vapor compositions are the same. By rearrangement of Equations (30) and (31) the constants A and B are obtainec?
directly.
A = log7Jl + ^ - ^ T
L
(32)
a;ilog7iJ
=iog7.ri+^r
(33)
L
Xi log 72J
Illustration 1. The azeotrope of the ethanol-benzene system has a composition
of 44.8 mole per cent ethanol with a boiUng point of 68.24C at 760 mm Hg. At
68.24C the vapor pressure of pure benzene is 517 mm Hg, and that of ethanol is
506 mm Hg. Calculate the van Laar constants for the system, and evaluate the
activity coefficients for a solution containing 10 mole per cent ethanol.
Solution: Ethanol is designated as component 1. At the azeotropic composition,
from Equation (32), since y = x,
71 = fSt = 1-502;
log7i = 0.177
y,^m
= lA7;
log 72 = 0.167
8 J. J. van Laar, Z. phys. Chem., 72, 723 (1910).
J. J. van Laar, Z. phys. Chem., 185, 35 (1929).
664
PHYSICAL EQUILIBRIUM
[CHAP. XV
'
B = 0.577
For a solution containing 10 per cent ethanol, from Equations (30) and (31),
(0.830) (0.90)^
r(0.830)(0.10) ^^p-l^
L
I,.,...
0.577
log 72 = 0.0109;
, , = 4.14
72=1.026
:.,,,,;,,:.,..,
:!^ (
By this procedure the activity coefficients of the entire range of compositions may
be calculated.
It was pointed out by Carlson and Colbum^ that the van Laar constants may be evaluated without any liquid-vapor equilibrium composition data if a series of isothermal vapor-pressure or isobaric boiling-point
measurements are available for solutions of known, composition over the
entire composition range. It is frequently desirable to work from such
data because of the difficulty of securing a reliable analysis of vapor
mixtures and the ease of making up liquid solutions of a desired composition. Since, in Equation (2),
PI
/ V .,;
Lim 7i =
p*
- ^
, , (34)
'
'
-.
(35)
Similarly,
Lim 72 =
X2=0
r*-x^P\
, '
(36)
Xir2
655
zene at these temperatures. Calculate the van Laar constants from these data,
assuming the activity coefficients to be independent of temperature.
Solution: The values of apparent 71 and 72 shown in Table XXXII are calculated
from Equations (36) and (36) and plotted in Fig. 150 against xi. Extrapolating the
71 curve to ii = 0 gives the value of 71 = 5.7 01 A = log 71 = 0.756. Similarly,
72 is determined to be 4.06 by extrapolating the 72 curve to Xi = 1.0 and B = log 72
= 0.608. These constants are in fair agreement with those derived from the
azeotrope composition.
TABLE XXXII
BOILING POINTS (DF ETHANOL-BENZENE SOLUTIONS AT 750 MM HG
Mole Fraction
Ethanol Benzene
Xl
0.0
0.04
0.11
0.28
0.43
0.61
0.80
0.89
0.94
1.00
Data from
Xi
Bniling
Point
<BC
79.7
1.0
75.2
0.96
70.8
0.89
0.72
68.3
67.8
0.57
68.3
0.39
70.1
0.20
72.4
0.11
74.4
0.06
78.1
0.0
"International
Vapor Pressure of
Appar- Apparent 72
Pure Components
ent 7:
Mm of Hg at ta'C
Ethanol Pi Benzene P2
804 mm
750 mm
1.00
671
648
4.74
1.16
560
562
4.07
1.38
507
618
2.66
1.63
497
609
2.16
1.84
507
618
1.77
2.18
645
549
1.47
2.86
698
592
1.285
3.33
650
632
1.165
3.64
750
711
1.00
True
True
71
72
5.70
4.20
3.66
2.11
1.58
1.22
1.05
1.02
1.00
1.00
1.00
1.00
1.05
1.16
1.34
1.84
2.64
3.14
3.58
4.06
656
PHYSICAL EQUILIBRIUM
[CHAP. XV
the azeotrope generally furnishes the best basis if the azeotrope is in the
middle of the composition range, between xt = 0.25 and zi = 0.75. If
the azeotrope composition is outside this range, boiUng-point or vaporpressure data provide a better basis.
Once the activity coefficients of a system are established Equation (2)
permits calculation of equilibrium compositions and vapor-pressure and
6
Vl
.p
X
J^
.2 3
o
^WW
*0
0.2
0.4
0.6
0.8
1.0
a;pmole fraction of ethanol
FIG. 150. Apparent and True Activity Coefficients of the Ethanol-Benzene
System at 750 mm Hg.
boiling-point curves at low pressures where the ideal-gas law may be
assumed. For a binary system of components 1 and 2,
m
m
2/1 =
PI
^t7i/
Pi
x,Phi+{l-x,)Ph2
x^
\
(39)
Equations (38) and (39) permit direct calculation of isothermal vaporpressure and Vapor-liquid composition curves. For deriving the more
CHAP. XV]
657
L ^ ^ = o.99
' ,
PJ 548
From Equations (30) and (31), the values of A and B from Illustration (1) give
71 = 2.19;
72 = 1.18
By substitution in Equation (39), a first approximation of 2/1 is obtained:
. ^
^ * = ^^'"^^"'"'=(0.28) ( 2 . 1 9 ) - = ' ' ' " ' " ^ ^
This vapor pressure corresponds to a temperature of 68.4C, the corrected boiling
point. At this temperature P* = 520 mm: Pf/PJ = | | = 0.978. Substitution in
Equation (39) gives
0.706
.,,
2/1 =
= 0.413
'
^
1.706
In this manner complete boiling-point and liquid-vapor composition curves may be
derived. The differences between the values calculated in this manner from the
data of Table XXXII are attributable to the inadequacy of the van Laar equation
and the uncertainty of experimental data of this type.
Partially Miscible Liquids. As the chemical dissimilarity of the components of a solution increases, the deviations from unity of the activity
coefficients increase until finally miscibility is incomplete and two liquid
phases result. This behavior is illustrated by the aqueous solutions of
the alcohols. The ethanol-water system shows considerable deviation
658
PHYSICAL EQUILIBRIUM
[CHAP.
XV
from ideal behavior with activity coefficients greater than 1.0. The
water-n-propanol system has higher activity coefficients but complete
miscibility at its normal boiling points. The water-butanol system
has still higher activity coefficients and is only partially miscible at its
normal boiling temperatures.
. ix :';/:;>;
- rfb
The properties of the water-butanol system at atmospheric pressure
are showii in Figs. 147, 148, and 149. It may be noted that two liquid
phases exist in the composition range from a to 6 corresponding to 66
to 98 mole per cent water. Between these limits the fugacity of each
component is constant and equal in the two phases. As a result the
boiling point is constant, and the vapor evolved is of constant composition c. The apparent activity coefficients in this range are inversely
proportional to the mole fractions based on the combined phases.
Although the vapor evolved from any liquid mixture of composition
between a and b is of constant composition c, the liquid and vapor
compositions are equal only at point c, which may be termed the heteroazeotropic composition. However, in each of the individual phases the
activity and composition are constant as indicated in Fig. 147. Since
the fugacities in the two phases are equal at equilibrium, in the region of
the two liquid phases,
i/i = a[n'
(40)
where the primed quantities represent one liquid phase and the unpriraed
the other. Since the standard state is the pure liquid component,
/t=/rand
,.. :^r^.--^
^
XiTi =
XJTI
or -^ =
(41)
A=
X2/\\0gX2/X2/
x'l 2xix[ log x[/xi
X'i
'4: Hi:
(42)
L_Z
(-fi) (-
(43)
CHAP. XV]
TERNARY SYSTEMS
G59
I t was found that the van Laar equation with constants derived from
Uquid-solubility data in this manner did not accurately represent activity
coefficients in solutions far removed from the two-phase region. For
example, for the water-re-butanol system the constant A based on liquid
solubility was found to be 0.334, whereas that based on vapor-composition
data in the dilute range is 0.61. Similarly, 5 is 1.60 from solubility and
1.34 from vapor compositions. Equations (42) and (43) are useful principally as a means of obtaining rough approximations for activity coefficients where no vapor-composition data are available.
As the chemical dissimilarity of the components of a system increases,
the deviation of the activity coefficients from unity increases and the
range of mutual solubility decreases. This effect corresponds to lengthening the horizontal portions between a and h on the curves of Figs. 147,
148, and 149. As complete immiscibility is approached, point a approaches zero, point b approaches 100 per cent composition, and the activity coefficients and vtn Laar constants become very large. To serve
as a rough guide to the relative magnitudes of the activity coefficients
corresponding to various degrees of miscibility Colburn" prepared
Table XXXIII from Equations (42) and (43) for symmetrical systems
in which the mutual solubilities of the two components are equal.
,
TABLE XXXIII
'
il]'-:
Solubility Limits
Van Laar Constants
7 at
7 at
X, Mole Fraction
A and B
s=0
x = x,
0.5
0.875 . - i ,,;;7;6.' v l ^ i.i
0.2
1.0
6.0
lao
'
0.1
1.2
15.8
9
0.05
1.43
2b
0.02
'i ' '
1.77
' '
! ' ! ' ''
to-
:'. -
0.01
>;
2.03
106
....ilT
94
Ternary Systems. Few reliable data are available from which activity
coefficients in ternary systems can be calculated. The general problem
of the correlation of activity coefficients in such systems has been reviewed by Wohl^ who has developed a series of equations analogous to
those for binary systems which have already been discussed. The accuracy of any of these equations depends to a large extent on the number
of experimentally determined constants involved. The most useful form
requiring minimum data is probably the ternary van Laar equation
which involves only six constants, all of which can be evaluated from
data on the three individual binary systems. The ternary van Laar
" A. P. Colburn, private communication (1942).
. , - , , , - ; . ; , .
660
PHYSICAL EQUILIBRIUM
[CHAP.
XV
..x,.,(^)V.iA...(fe-;)'
' :
log Ti =
a;2X3-;^
'
-.
( Ai-2 + ^1-3Aa-a-;
Ai_2Ai_3\
/ _^
V
^3-1/
A2_,
4l_2
la-iV
.4l_3/
In equation (44) the constants ^i_2 and A2_i correspond to the van
Laar constants A and B of the binary system of components 1 and 2.
Similar equations for log 72 and log 73 are obtained by changing the subscripts on all terms in Equation (44) in accordance with the following
schedule of rotation:
Subscript in Equation (44) for
log 71
1
2
3
log 73
* .
Thus, in the equation for log 72, Xi of Equation (44) becomes x^; x^ becomes 0:3; X3 becomes :ci; and 41_2 becomes 42-3 etc. Similarly, in the
equation for log 73, Xs becomes X2, and A1-2 becomes A^^i.
By means of Equation (44) complete activity coefficient relationships
may be estimated from the coefficients of the three binary systems which
in turn may be approximated from the binary liquid-solubility data by
Equations (42) and (43). Colburn^i tested this general method on the
methyl cyclohexane-n-heptane-aniline system and found good agreement with ternary solubility data. However, it is impossible to predict
the errors which may be encountered in other systems.
The most generalized equation for ternary systems recommended by
Wohl is the four-suffix form and involves 14 constants, 11 of which may
be evaluated from data on the three binary systems.
Knowledge of the activity coefficients in a ternary system permits calculation of the distribution of any one of the components between the two
liquid phases in a region of partial miscibility by means of Equation (41)
which is valid for any component regardless of the number of others
661
\ dT J^ \ dT )^ \ dT A
K - Hi) - (Ht - Hj)
RT^
(li-H?)
RT^
(45)
The quantity HI-H" is the partial molal enthalpy relative to the pure
components at the temperature of the solution or the differential heat
of solution. If Hi-Hi is positive, y is reduced by an increase in temperature. Carlson and Colburn^ observed that in general if the activity
coefficients of a system are greater than 1.0 the heat of solution is negative, whereas if the coefficients are less than 1.0 the heat of solution is
positive. Thus, in either case increasing the temperature causes the
activity coefficients to approach 1.0. Conversely, lowering the temperature tends to increase deviation from ideal behavior, and many systems miscible at high temperatures separate into two phases at low
temperatures.
Use of Equation (45) for calculating the effects of temperature is complicated by the fact that values of (1 Hi) vary considerably with temperature and are rarely known over any extensive range.
An approximate method for estimating the effect of temperature on
activity coefficients is obtained by extension of a method suggested^by
Carlson and Colburn for estimating the effect of temperature on azeotrope
composition. It is assumed that the ratio of the activity coefficients
7 I / T 2 is independent of temperature at a given composition. It follows
from Equation (2) that at the azeotropic composition where Zi = yi,
Pi
P\
(46)
PHYSICAL EQUILIBRIUM
662
[CHAP. XV
L2
20
Temperature, "C
40
60
80
100
1
\
<
1.0
t \\
0.8
p*
\
TiV
0.6
0.4
100
20
60
40
80
Mole Per Cent Ethyl Acetate
Fio. 151. Effect of Temperature on the Composition of the Ethyl
Acetate-Ethyl Alcohol Azeotrope.
48 mole per cent ethyl acetate. In Table XXXIV are values estimated^
in this manner compared with the experimental measurements of
Merriman.i^
The total pressures P^ corresponding to the various azeotrope compositions and temperatures may be approximated by the following empirical equation,
P.=
where
P^(a;iPi + X2F2)
{x\P\ + x^PD
,.^
(47)
663
activity coefficient and vapor-liquid composition curves may be estimated over limited ranges of temperatures or pressures. This method
has not been sufficiently explored to permit estimation of the errors
which may be encountered.
-
TABLE XXXIV
mperarc, C
ia7
40.5
^3
71.8
83.1
91.4
P*/P*
0.598
0.725
0.827
0.921
0.994
1.049
664
PHYSICAL EQUILIBRIUM
[CHAP.
XV
= <^2/i
\Jl)v
(50)
I
where
'
'
(ai)s = activity of component 1 in the vapor phase
t/i = mole fraction of component 1 in the vapor phase
0V1 = activity coefficient of component 1 in the vapor phase '
The activity coefficient <i>^ is dependent on the properties of both component 1 and the other components with which it is mixed and also upon
the temperature and pressure. Under conditions of moderate pressures
and elevated temperatures gaseous solutions tend to be ideal if the components are not too widely different in properties. In such cases 4>^
may be taken as 1.0. Maximum deviations from 1.0 occur in the region
of the critical point of the solution.
In the hquid phase the relationship between activity and mole fraction
is complicated by the two types of deviation from the laws of ideal solutions which are discussed on page 609. Because of the widely different
contributing causes and relationships it is convenient to consider these
two types of deviation separately and assign an activity coefficient lo
express each. Thus,
{ax)L = <i>Li'i\Xi
^,j
(51)
where
(oi)i = activity of component 1 in the liquid phase
<t>Li = activity coefficient of component 1 in the liquid phase which
takes into account deviations from the laws of ideal solutions resulting from differences in molecular size or volatility
7i = activity coefficient of component 1 in the liquid state which
takes into account deviations from the laws of ideal solutions resulting from differences in molecular or chemical
type
Xi = mole fraction of component 1 in the liquid phase
CHAP. XV]
665
= Ki
(52)
It was suggested by Gamson and Watson'^ that the ratio of the mole
fractions in the vapor and liquid phases be termed the vaporization
ratio K'l of component 1. It is evident from Equation (52) that the
vaporization ratio is equal to the thermodynamic equilibrium constant
only in ideal solutions where the activity coefficients are each equal
to 1.0.
Equation (52) provides a sound basis for calculations involving vaporliquid equilibria. In many cases it is satisfactory to assume that the
coefficients (f>Li and 0i are unity, and, as previously pointed out,
7 i = 1.0 for all ideal systems. Under other conditions it is necessary
to evaluate the coefficients as functions of the properties of the component and the system, either from experimental data or generalized
methods of calculation.
At low temperatures and pressures where Dalton's law and the idealgas law are applicable CJ>L and 4>v become unity and Equation (52) reduces to
K^i = = liKi = - Xi
(53;
G66
PHYSICAL EQUILIBRIUM
"'<
[CHAP.
XV
of the pure components under real conditions. However, these arbitraryextrapolations in no way interfere Avith the fundamental validity of
Equations (49) and (52). If the method of extrapolation is changed,
the values of Ki are affected, but corresponding changes result in the
activity coefficients so that it is only necessary that the values of (t>n,
4>Li, Ti; 3'Dd Ki all be referred to consistently defined standard states.
The concept of the vaporization equilibrium constant was introduced
by Souders, Selheimer and Brown" who expressed it by/ the following
equation resulting from combination of Equations (XIV-34) and (49)
with the definition of the fugacity coefficient:
'
VmJT - P i )
^ , = (Z? = ^!-L^!_
(54)
CHAP. XV]
667
' y')
03
^dc^'d/f
668
PHYSICAL EQUILIBRIUM
[CHAP.
XV
'"~
(55)
where (wiui) is the product of the molal liquid volume and w from Fig. 109
at any selected conditions. By comparison of Equation (55) with
(XII-39), page 502, it is seen that the term (5.7 -|- S.OTr) corresponds to
1/co for the hypothetical incompressible liquid reference state. This'
value is a linear extrapolation of l/w from the absolute zero and thus
defines the liquid standard state as having a constant volumetric coefficient of expansion equal to that of the real liquid at the absolute zero.
At low reduced temperatures values of Vm calculated from Equation (55)
differ little from actual molal volumes. As the critical point is approached Vm is smaller than the actual molal volume except at high
pressures.
;
.
. .,
CHAP. XV]
669
,
^^^)
where
'
l o g P i = - + B-e-2(Xrr-6)=
(57)
Equations (54), (56), and (57) together with Figs. 142 and 152 completely
define the fugacities of the Uquid and vapor reference states and the
equilibrium constant in an arbitrary but logical manner which is definite,
reproducible, and apphcable to any material at any conditions.
Illustration 4. Calculate the vaporization equilibrium constant of methyl chloride at 200F and an absolute pressure of 600 lb per sq in. The density of liquid
methyl chloride is 0.920 g per cc at 18C, the critical temperature is 750R, the
critical pressure 967 lb per sq in., and the molecular weight 50.5.
Solution: At 200 .and 600 lb per sq in., Tr = 660/750 = 0.880; p, = 600/967
= 0.620
At 18C (64.4F), Tr = 524.4/750 = 0.699
From Fig. 142, w = 0.68; (/), = (0.68) (600) = 408 lb per sq in.
From Fig. 109 at 18G, ui = 0.1146
(viui) = (50.5) (0.1146)/(0.920) = 6.290 cc per g-mole = 0.1007 cu ft per lb-mole
From Table Ila, page 73:
log Pi = - ^ ^ ^ ^ -I- 7.4185 - c- 20(0.880 - 0.062)2
^
0.880
= -3.0903 + 7.4185-10-5.95=4.3282
Pi = 21,290 mm or 21,290/51.70 = 412 lb per sq in.
At 412 lb per sq in., Pr = 412/967 = 0.426
From Fig. 142, >.p = 0.77
Substitution in Equation (56) gives
log i n . = log 412 + log 0.77 + (0-1007)[5-7 + (3.0)(0.880)][600-412]
iogu;i
B
-r 6
-r
(2.303) (10.71) (660)
= 2.6149 - 0.1135 + 0.0097 = 2.5111
( D t = 324.41bpersqin.
From Equation (54),
K = 324.4/408 = 0.795
In this manner charts may be developed which express the vaporization equiUbrium constant of a specific compound as a function of temperature and pressure. Series of such charts have been developed by
several investigators for many of the lower-boiling hydrocarbons. An
alternate method of graphical presentation which is convenient when
working with mixtures of homologs of a single series is to restrict each
PHYSICAL EQUILIBRIUM
-300
-200
-100
0
100
200
300
Normal Boiling Point, F
[CHAP. XV
400
500 .
600
FIG. 153. Vaporization Equilibrium Constants of Hydrocarbons. (Absolute Pressure n = 100 lb per square inch.)
chart to a constant pressure and plot curves each of which^ expresses the
equilibrium constant of a particular compound as a function of temperature at the pressure of the chart. With this scheme a series of charts
each corresponding to a different pressure is required.
Another method of presenting equilibrium-constant data for an ho-
-100
0
100
200
300
Normal Boiling Point, P
FIG. 154. Vaporization Equilibrium Constants of Hydrocarbons,
sure n = 200 lb per square inch.)
-300
-200
671
600
(Absolute Pres-
mologous series is shown in Figs. 153 and 154 for the paraffin hydrocarbons. These charts were calculated by Equations (54) and (56)
from the data of Table XXVIII. Although based on the data for paraffins they may be used for olefins with little error. The products of KTT
in pounds per square inch are plotted as ordinates with the normal boil-
672
PHYSICAL EQUILIBRIUM
[CHAP.
XV
ing points of the homologs as abscissas. Each curve on the chart corresponds to a constant temperature, an(i the chart is restricted to a
constant total pressure x. It will be noted that for the low-boiling compounds there is little difference between the values of Kir at 100 and 200 lb
per sq in., from Figs. 153 and 154, respectively. For such compounds
in the moderate-pressure range the problem of interpolating between
charts to obtain values of >K at some intermediate pressure is simpUfied
by plotting Kir rather than K. In the high-pressure range or for highboiling compounds K-ir varies with pressure more than K, and it is preferable to plot K directly. The choice of the method of plotting i^a matter
of convenience dependent upon the type of problem. Kirkbride^^ has
developed a method of simplifying dew-point and bubble-point calculations by plotting all equilibrium constants relative to those of ethane at
the same temperature and pressure. Because of insensitivity of these
relative equilibrium constants to temperature and pressure this method
reduces the labor of trial-and-error calculations.
Bubble-Point Equilibria. A liquid at its bubble point must be in
equilibrium with the first trace of vapor formed. In a mixture of components 1, 2, 3 the mole fractions in the combined phases of the total
mixture are represented by zi, Zi, Zz, -, respectively. The mole fractions in vapor phase are yi, 1/2, ya, , and in the hquid phase xi, Xa,
Xi, . Under all conditions
Zl + 22 + 2 3 + - - - = 1.0
^. yi + y2 + y3+--- = 1.0
f^xi + X2 + xs+--- = 1.0
(58)
(59)
(60)
When the mixture is at its bubble point Xi = zi, X2 = zi, etc. Also, by
Equation (52), t/i = K{x\, y-i = ^^'2X2, etc. Combining these relationships with Equation (59), at the bubble point, gives
KUi + X^Z2 + -f:;33+'-- = 1.0
or
SK'z = 1.0
and
"V
(61)
If the vaporization coefficients K' are known for all components as functions of temperature and pressure. Equation (61) permits complete calculation of bubble-point conditions by a trial-and-error procedure.
If it is desired to calculate the bubble-point pressure of a mixture at a
specified temperature, a pressure is assumed as a first approximation.
Corresponding values of K[, K'^, X3 or K'^^K, KW Kiv are determined, and the left-hand side of Equation (61) is evaluated. If the
summation equals 1.0 the assumed pressure is correct. If not, other
values are assumed, and the corresponding summations are plotted as a
1' C. G. Kirkbride, Petroleum Refiner, 24, 99 (1945).
CHAP. XV]
PARTIAL VAPORIZATION
673
= w*
(62)
Z2
23
^ + ^ + ^
l(|,)=1.0
or
+ = 1-0
and
(63)
^z()'1.0
7
Zi
^ ;:..,
_,--'-,:,,
TiPt
Z2
T2P2
r-
(64)
Z3
TsP;
.^
..
'
(66)
,'
= Fzx
'
(66)
F /
zi
674
PHYSICAL EQUILIBRIUM
Since
X1 + X2 + X3 +
-+f
[CHAP. XV
lix=\.0
_ F
" F
(68)
(69)
yi =
and
1 + VK'
V
F
(70)
yx =
(72)
['/(-^)]
Equation (72) may be used with little error even if the summation does
not exactly equal V/F. Corresponding values of Xi are then obtained
from Equation (66).
^ '
Fz,-Vy,
A , F \
V
(73)
Xi =
If Equation (68) is used for the summation, values of x are obtained directly by an expression similar to Equation (72). It is evident that in a
partially vaporized mixture at equilibrium the vapor phase exists at its
dew point while the liquid phase exists at its bubble point.
Illustration 5. A hydrocarbon mixture contains 25 mole per cent propane, 40 per
cent n-butane, and 36 per cent n-pentane. Calculate the bubble-point temperature,
CHAP. XV]
PARTIAL VAPORIZATION
675
the dew-point temperature, and the temperature of 45 mole per cent vaporization
at an absolute pressure of 200 lb per sq in. Also, calculate the compositions of the
vapor formed at the bubble point, of the liquid formed at the dew point, and of the
hquid and vapor resulting from 45 mole per cent vaporization. It may be assumed
that ideal solutions are formed.
Solution: (a) Bubble-Point Temperature and Vapor Composition. Values of K,
which are assumed equal to K', are obtained from Fig. 154 for substitution in Equation (61).
Assumed Temperature,
Component
z
CBHS
C4H10
CsHij
0.25
0.40
0.35
,:^ .: .
KV
374
164
74
180F
K'
K'z
1.87 0.468
0.82 0.328
0.37 0.130
200F
X V K'
K'z
420 2.10 0.525
196 0.98 0.392
92 0.46 0.161
0.926
1.078
1.00
220F
K'
462 2.31
226 1.13
110 0.55
X'T
K'z
0.578
0.452
0.193
2/
0.496
0.359
0.145
1.223
1.000
240
z
Component
CaHs
0.25
C4H11)
0.40
CBHU
0.35
K'rr K'
z/K'
462 2.31 0.108
226 1.13 0.354
110 0.55 0.637
1.00
1.099
260
K'
z/K'
510 2.50 0.100
254 1.27 0.315
132 0.66 0.531
K'17 K'
z/K'
546 2.72 0.092
290 1.45 0.276
156 0.78 0.449
X
0.104
0.329
0.567
0.946
0.817
1.000
K'T
Graphical interpolation fixes the temperature at which SZ/z = 1.0 at 233F. A good
approximation to the hquid composition is obtained by calculating (zi/Kd/Zz/K' at
230 and 240 and interpolating.
(c) Temperature and Composition of 45 Per Cent Vaporization.
V/F = 0.45
From Equation (71), L/V = 1/0.45 - 1.0 = 1.22
or
y/L=
0.82
<
220F
240F
z
K'
2.31
1.13
0.55
l+L/VK' l+L/VK'
1.528
0.164
2.080
0.192
3.220
0.109
0.465
z
K'
2.50
1.27
0.66
l+L/VK' l+L/VK'
1.488
0.168
1.961
0.204
2.850
0.123
0.495
676
PHYSICAL EQUILIBRIUM
[CHAP.
XV
values calculated from Equation (72) at 200 and 220P. Corresponding values of z
are calculated from Equation (73).
J
Component z
y
1.822! 0.821/
x
CsHg
0.25 0.358 0.455 0.294 0.161
C4H10 0.40 0.413 0.728 0.339 0.389
CsHij 0.35 0.229 0.637 0.187 0.450
;;
LQO 1.000
1.000
, . ;
Activity Coefficients. In Illustration 5 it is assumed that all activity
coefficients are equal to 1.0 and that the vaporization coefficients are
equal to the equilibrium constants. This assumption is satisfactory for
many calculations for ideal systems at moderate pressures if the components are not widely different in properties. In working with nonideal
systems under similar conditions it is satisfactory to assume that <i>L and
<j>v are unity. Values of 7 may be derived by the methods described in
the preceding sections. At elevated pressures where the ideal-gas law
is not valid, the following relation is used in preference to Equation (2).
71 = ; ^
XiKi
^ "
I
'
(74)
At high pressures, approaching the critical of the mixture, the assumption that <^L and 0 are unity is unsatisfactory for both ideal and nonicj^eal
systems. Serious errors are also encountered at moderate pressures for
components widely different in volatility from the average of the mixture. An example is methane dissolved at moderate pressure in absorption oil. Much effort has been directed toward the evaluation of
these corrections, but no entirely satisfactory and general method has
yet been developed.
On the basis of the pseudocritical concept Gamson and Watson'' developed general methods for calculating fugacities in both the liquid and
vapor states at all cohditions. The accuracy of these methods is limited
by the lack of sound definitions of the pseudocritical properties and by
the inaccuracies inherent in the generalized compressibility-factor relationship. These difficulties require the introduction of empirical correction factors which bring the calculated results into fair agreement with
the available data over wide ranges of conditions. The method of calculation is too tedious to be of practical value in the direct calculation
of vapor-liquid equilibria but may be used to derive values of 0^ and <^
from Equations (50) and (51) which for a particular system can be related graphically to the properties and conditions of the respective phases.
Graphical correlation of (^L and 0, either from experimental data or
from the generalized method of calculation of Gamson and Watson, is
CHAP. XV]
677
complicated by the large number of variables entering into the relationships. The most important are:
(a) Tci/T'c = the ratio of the critical temperature of the component to
the pseudocritical temperature of the Tphase under consideration
(6)
Pr = the pseudoreduced pressure of the phase under consideration
(c)
T'T = the pseudoreduced temperature of the phase under consideration
For a system composed of homologs, <^ and ^z, may be expressed in terms
of only these three variables over limited ranges of variation of the average properties of the mixtures. In order to obtain more general relationships additional variables must be considered, even when dealing
with homologs.
Consideration of the activity coefficients considerably complicates
vaporization calculations. Since the activity coefficients are functions
of the properties of the individual phases, it is necessary to assume trial
phase compositions, and then evaluate approximate activity coefficients
and vaporization coefficients. The phase compositions are then calculated and corrected by a repetition of the procedure.
SOLUBILITY
TW"'^'^
(75)
678
PHYSICAL EQUILIBRIUM
[CHAP. XV
where
S2, 72 = the mole fraction and activitjr coefficient of component 2
in the solid phase
Xi, 72i = the mole fraction and activity coefficient of component 2
in the liquid phase
(Jl)s = fugacity of component 2 in the solid state at the temperature and pressure of the system
(JI)L = fugacity of component 2 in the hypothetical liquid state at
the temperature and pressure of the system
Ki = solubility constant of component 2, referred to the pure
component
An expression for the solubility constant as a function of temperature
is obtained by combining Equations (XIV-38) and' (75):
^
(76)
R\T
Yj---
RTT
(^^)
where
V = molal heat of fusion of component 2
T temperature of the system
= melting point of component 2
Similarly, the effect of pressure upon the solubility equilibrium constant is obtained by combining Equations (XIV-30) and (75) to give
dp l~
RT
(^^)
i"g^--^'""^;"^^"(x-p.)
(7^)
where
v,2 = molal volume of the pure solid solute at the temperature and
pressure of the system
flu = molal volume of the hypothetiqal Hquid solute at the temperature and pressure of the system
Pm = equilibrium pressure corresponding to melting point T
CHAP. XV]
679
These results are in fair agreement with the observed value of 4,550.
The fair agreement between the heats of fusion calculated at the two
temperatures of Illustration 6 indicates that the solutions of benzene in
naphthalene closely approximate ideal behavior. In other systems,involving less similar components much larger discrepancies can be expected and the activity coefficients of Equation (75) must be evaluated
for satisfactory results. These deviations in a number of systems are
discussed by Hildebrand."
680
PHYSICAL EQUILIBRIUM
[CHAP.
XV
For solutes having melting points far. removed from the temperature
of the system or for electrolytes whicn dissociate into ions in solution,
it is not advantageous to use the hypothetical standard state of Equation (75) for the hquid phase. A more convenient convention is to express the activity of the solute in the liquid referred to the infinitely
dilute solution at the pressure of the system. As is mentioned on page 629
this convention corresponds to the selection of a hypothetical standard
state the fugacity of which is the value which would exist if the solution
behaved ideally at unit mole fraction (or unit molality) as it does at zero
concentration. The enthalpy and volume of this hypothetical standard
state are therefore equal to the partial molal enthalpy and volume, respectively, at zero concentration. The activities in the solid phase are
best referred to the pure solid at the pressure of the system as the standard state. On this basis the solubility of a solid is expressed by
_
7^7- - --
23
J2L
A2
(.SU)
S272J
where
Si, T23 = mole fraction and activity coefficient of component 2 in
the solid phase
2^2, 72 L = mole fraction and activity coefficient of component 2 in
the given solution
jla = fugacity of the pure solid at the temperature and pressure
of the system
y^L = fugacity of the hypothetical standard state for the liquid
phase referred to infinite dilution
K'i = solubility equilibrium constant of component 2 referred to
infinite dilution
The eifect of temperature on the solubility constant is given by an
equation expressing the effect of temperature on the fugacities of ^the
standard states. From Equations (XIV-45).and (80),
(d\nK',\
V- dT A
JBli^-nl,)
RT^~
^^^'
where
H2i = partial molal enthalpy of component 2 at infinite dilution at
the temperature and pressure of the system
Has = mo}al enthalpy of component 2 in the solid state at the temperature and pressure of the system
The quantity Elf^ nla is the differential heat of solution at infinite
dilution.
Similarly, by combining Equations (XrV-44) and (80) the effect of
CHAP. XV]
SOLUBILITY OF GASES
681
/d\nK'2\
\ dp
ivlL-vl.)
^g^^
)T
where
^2L = partial molal volume at infinite dilution at the temperature
and pressure of the solution
vis = molal volume of the pure solid at the temperature and pressure of the system
I t may be noted from Equation (81) that the solubiUty of a solid is
increased by increased temperature if its differential heat of solution is
positive, corresponding to absorption of heat in dissolution. Similarly,
the solubility is increased by increase in pressure if the partial molal
volume in dilute solution is less than the volume of the solid.
The practical value of Equations (80-82) is restricted by the great
variations >vith concentration of the activity coefficients in liquid solutions. Except in dilute solutions these coefficients must be evaluated
from empirical data which are seldom available.
Equations (80-82) are directly applicable to electrolytes with activities expressed in either molecular or ionic terms. However, the use of
mean ionic activities and molalities for these materials has the advantage
that the activity coefficients approach unity in dilute solutions, as demonstrated in Fig. 145, whereas the molecular activity coefficients become
very small.
Solubility of Gases. The solubility in a hquid of a gas, either in the
pure state or from a mixture, is expressed thermodynamicaUy by Equation (49). If the temperature of the system is below or not greatly above
the critical temperature of the gas, the standard state for the gaseous
component in the liquid phase is conveniently taken as the pure component in a hypothetical incompressible liquid state at the temperature
and pressure of the system, exactly as described for handling vaporliquid equilibria. If it is assumed that ideal solutions are formed in the
gaseous phase and the standard state for the gaseous phase is taken as
the state of unit fugacity. Equation (49) combined with (51) reduces to
- {Ji)!' - J^2
(83)
a;272<P2z,
where
TT = total pressure of the system
V2w = fugacity coefficient of pure gaseous component 2 at the
temperature and pressure of the system
72, <^2t = activity coefficients in the liquid state as defined by Equation (51), page 664
682
PHYSICAL EQUILIBRIUM
[CHAP.
XV
Comparison of Equation (83) with (V-5), page 147, in which the partial pressure p2 is equal to iry^ results in a thermodynamic expression for
Henry's constant H2. Thus
,
m =
(84)
Equations (83) and (84) ihay be used to predict what may be termed
ideal solubilities if 72 and <^2t are assumed to be unity; v^rr is derived
from Fig. 142, and (JDL is calculated from Equation (56). As pointed
out by Hildebrand," this method gives fair results in systems not involving highly polar materials if the temperature is below the critical
temperature of the gas. At higher temperatures the calculation of (fl)L
becomes uncertain. Arbitrary specification of (f^i in such ranges requires consideration of corresponding values of (^21, which must be based
on experimental data. Such data are necessary in any case for the prediction of 72 in systems involving high polarity or chemical reaction and
association.
Illustration 7. Calculate the ideal solubility of chlorine in carbon tetrachloride at
a pressure of 1.0 atm and a temperature of 0C. The density of hquid chlorine is
1.561 g per cc at -34.6C. The vapor pressure at O'C is 3.65 atm. Tc is 417K and
Pc is 76.1 atm.
Solution: At -34.6C,
From Pig. 109,
Tr = 238.6/417 = 0.571
wi = 0.1266
It may be noted that with this definition of the standard state in the
liquid-phase gas solubility calculations are identical with the vaporliquid equilibrium calculation demonstrated in preceding sections.
For systems involving gases far above their critical temperatures or
where dissociation or chemical reaction is involved, the standard state
used in Equation (83) for the liquid phase loses its advantage. It is
CHAP. XV]
SOLUBILITY OF GASES
683
^ " = ( / r ) x = 2f^
(85)
where 72L, {JI')L and K'2 all correspona to activities referred to infinite
dilution. For such systems the single coefficient (72) i may be used to
take into account all types of deviation from ideality. In dilute solutions or when deaUng with nonpolar nonreacting solutes it is frequently
satisfactory to assume that (72 )L is unity. With this assumption a
single experimental solubility value serves to determine K'^. The variation of the solubility constant with temperature is derived from Equation (XIV-45)
\r^T~),
Rf^
^^^)
where
H2G = enthalpy of component 2 in the ideal gaseous state at temperature T
H2i = partial molal enthalpy of component 2 in solution at infinite
dilution at the temperature and pressure of the system
The effect of pressure on K'2 is derived from Equation (XIV-44),
/d In K'A ^
...
si
')
where
VIL partial molal volume of component 2 in the liquid phase at
infinite dilution
Equation (86) may be used to calculate the effect of temperature on
solubility from heat-of-dissolution data or conversely to calculate the
differential heat of dissolution at infinite dilution (H2ff H2L) from
solubility data at two temperatures if the ideal solution behavior is
approximated.
Illustration 8. At a partial pressure of 1.0 atm pure CO2 is in equilibrium with
'aqueous solutions containing 0.096 mole per cent CO2 at 10C and 0.0294 mole per
cent CO2 at 60C.
(a) Assuming the solution to behave ideally, calculate the mole fraction of CO2 in
an aqueous solution saturated with CO2 at 60C and 100 atm. The effect of pressure
on K'^ may be neglected.
(6) Calculate the average differential heat of dissolution of CO2 in water at infinite
dilution in the range of 10-60C.
Soluiidh:
(a) For COa,
Tc = 304.3K;
p = 73.0 atm
684
PHYSICAL EQUILIBRIUM
[CHAP. XV
At 60C, 1 atm,
Tr = 1.10;
p, = 0.014
From Fig. 142,
v = 0.995 *
Substitution in Equation (85), if it is assumed that 72L = 1.0, gives
X2 = (1.0) (0.995)/(0.000294) = 3380
At 60C, 100 atm,
T, = 1.10;
Vr = 1.37;
vi, = 0.63
From Equation (85),
,
X2 = (100)(0.63)/3380 = 0.0186 or 1.86 per cent
(6) At 10C, and 1.0 atm,
Tr = 0.93;
p , = 0.014;
v = 0.995
Ki = (1.0)(0.995)/(0.00096) = 1036
Substitution in Equation (86), after integration, gives
(Hfe - 3 . ) = - [(1.99)(2.303) log | | ] / ( ^
- ^ )
= 4,431 calperg-mole
The differential heat of dissolution of the ideal gas at infinite dilution is therefore
4,431 cal per g-mole.
The experimentally observed mole percentage of CO2 in water at 60 and 100 atm
is approximately 1.8 per cent.'' Assumption of Henry's law in this case would predict a value of 2,94 per cent, an error of over 60 per cent as compared to an error
of less than 5 per cent for Equation (85). The good agreement with Equation (85)
indicates that the activity coefficients in the hquid phase are substantially unity
as assumed, in spite of the chemical reaction occurring between carbon dioxide and
water and the accompanying ionization. This may be interpreted as indicating that
only a small fraction of the dissolved CO2 reacts with the water. Where higher solute concentrations or more extensive reactions are involved, the assumption of ideal
behavior may lead to large errors which require evaluation of the activity coefScientS,
The solubiUty of gases with accompanying chemical reaction is discussed in Chapter XVI, page 742.
Gas-Solid Adsorption Equilibria. Equilibrium conditions in adsorption of gases on solids are discussed in Chapter V, pages 149-160, and
the enthalpy of such systems in Chapter VIII, pages 297-300. From
Equation (VIII-48),
(M)2 + 1)H = Hi + H2W2 + AH = Hi + W2H2
or
where
AH = Hi~Hi+
(88)
(89)
'
(90)
CHAP. XV]
685
Since the differential heat of adsorption varies with the mass adsorbed,
the total heat of adsorption in adsorbing a mass W2 of gas is obtained byintegration, thus
U!2
AH2 dw2
(91)
From Equation (g) page 472, applied to gas adsorption under conditions
of constant composition,
/3AS\
^ /dp\
(93)
If the partial molal volume of the adsorbed gas is neglected and idealgas behavior is assumed,
/dlnp\
H2-H2, = -RTnnp = R f-\
(94)
and
Illustration 9. In the adsorption of NO2 gas by silica gel the following equilibrium isotherm equations were derived from the experimental work of Foster:"
At 16C,
W2 = 0.330 pi'''
At25C,
Wi = 0.115 p\'^
At 35 C,
where
W2 = 0.022 pi
pi = partial pressure of NO2 in millimeters of Hg
W2 = grams of NO2 adsorbed per 100 g of siUca gel
Calculate the differential heat of adsorption per gram-mole of NO2 when Wi = 5.0.
From a cross-plot of In p against 1/T at w^ = 5.0,
/
d\np\
\S|
From Equation (94),
AH2 = H2 - H25 = -3760(1.987) = -7490 cal per g-mole NO2
" Gordon Poster, Ph.D. thesis, University of Wisconsin (1944).
686
PHYSICAL EQUILIBRIUM
[CHAP. XV
To obtain the integral heat of solution of 5 g of NO2 on 100 g of silica gel it is necessary to obtain the differential heat of solutionjor different values of Wi from 0
to 5 and then integrate according to Equation (95).
MINIMUM WORK AND ENTROPY OF SEPARATION
+ ncGc + )
(W^GA + WSGB + WcG? -\
) = Wf (96)
Combining (53) and (96),
AG = RT(nA In aA+ns In as+ nc In ac-{
) = Wf
(97)
or
{UAGA
UBGE
) = -Wf (98)
Where all activities are referred to the pure components, Equation (98)
represents the free energy of 'formation of the solution from its components, each in its specified standard state.
"^
CHAP. X V ]
ENTROPY OF DISSOLUTION
687
Illustration 10. From the data of Fig. 146, calculate the minimum useful work
required to separate 100 lb of a 1.0 molal solution of sodium chloride at 100C
into pure water and solid salt at the same temperature and pressure.
Solution:
Basis: 100 lb of solution.
Per cent NaCl by weight =
Lb-moles NaCl
=
Lb-moles H2O
=
Mole fraction NaCl
=
Mole fraction H2O
=
From Fig; 146,
^NaCl= 0-593 ^
"NaCi ^ (0-0177) (0.593) = 0.0105
(58.5/1058.5)100
5.52/58.5
94.48/18
0.0945/6.35
0.9823
=
=
=
=
5.52
0.0945
5.26
0.0177
7H,O = 0.9832
" H J O " (0.9823) (0.9832) = 0.964
Entropy of Dissolution. The entropy changes which accompany dissolution may be calculated from the enthalpy and free-energy changes
by Equation (XI-5). Thus,
AH-AG
A'S =
J,
(99)
In'Equation (99), AH is the integral heat of solution and AG the free
energy of solution calculated from Equation (98). For ideal solutions
AH = 0 and the activity coefficients of Equation (98) become unity.
Illustration 11. Calculate the minimum useful work and entropy change of separation of 1 lb-mole of air at 65F and 1.0 atm pressure into oxygen and nitrogen each
at the temperature and pressure of the mixture.
Solution: For air at the given conditions mole fractions may be substituted for
activities referred to the pure components at the temperature and pressure of the
solution. From Equation (98),
AG = (1.99) (525) (2.303) [(0.21) log 0.21 -1- (0.79) log 0.79] = -540 Btu
Therefore, the free-energy change of separation is 540 Btu per lb-mole of air, which
is the minimum work of separation done on the system, or w/ = 540 for the separation process.
From Equation (99), for the separation process,
AS =
AG
=
T
540
= 1.03 entropy units
525
688
PHYSICAL EQUILIBRIUM
[CHAP. XV
PROBLEMS
1. The system toluene-acetic acid forms an azeotrope containing 62.7 mole per
cent toluene and having a minimum boiling point of 105.4:C at 760 mm Hg. The
vapor-pressure data from the International Critical Tables are as follows:
fC
70
80
90
100
110
120
Normal boiling point, C
'
Toluene
202.4
289.7
404.6
557.2
110.7
Acetic Acid
136.0
202.3
293.7
417.1
580.8
794.0
118.5
Calculate the van Laar constants A and B for this system, and plot n and yi as
ordinates on a logarithmic scale against the mole fraction of toluene (component 1)
on a uniform scale, neglecting the association of acetic acid in the vapor phase.
2. The following data on the vapor pressures in millimeters of Hg of carbontetrachloride-ethyl-alcohol solutions are from the International Critical Tables:
Weight Per
Cent e c u 34.8C
103
0
122
10.23
142
20.02
156
27.13
39.06
179
43.87
187
48.86
193
66C
462
520
576
614
677
700
716
Weight Per
Cent CCI4 34.8C
58.25
206
71.68
220
76.69
223
84.25
226
92.98
225
97.43
221
98.6
SIS
99.9
187
100.0
173
66C
752
782
789
788
780
741
717
693
544
From these evaluate the van Laar constants for the system at 34.8C and 66C.
3. From the results of problem 2 calculate vapor compositions corresponding to
Uquid compositions of 10, 20, 30, 40, 50, 60, 70, 80 and 90 mole per cent CCU SH,
pressures of 760 and 200 mm of Hg. Plot these results as y-x diagrams similar to
Fig. 148. Assume that the activity coefficients are independent of temperature over
the hmited ranges involved. The vapor pressures of the pure component are as
follows:
VAPOE PKBSSTJEBS, MM OF Hg
iC
20
25
30
35
40
45
'50
CCI4 C2H5OH
91
43.9
114.5
59.0
143.0
78.8
176.2
103;7
136.3
215.8
262.5
174.0
222.2
317.1
ec
55
60
65
70
75
80
Normal boiling point, C
CCI4
379.3
450.8
530.9
622.3
CjHsOH
280.6
352.7
448.8
542.5
666.1
843
812.6
76.75
78.32
CHAP. XV]
PROBLEMS
689
690
PHYSICAL EQUILIBRIUM
[CHAP. XV
Propane
Isobutane
7i-Butane
Isopentane
n-Pentane
23
67
10
Bottoms
2
46
15
37
100
100
(a) Calculate the pressure at which the column must operate in order to condense
completely the overhead product at 120F.
(6) Assuming that the overhead product vapors are in equilibrium with the liquid
on the top plate of the column, calculate the temperature of the overhead vapors
and the composition of the liquid on the top plate when operating at the pressure
of part (a).
.
(c) Calculate the temperature of the liquid leaving the reboiler. of the column
under the pressure of part (a), assuming equilibrium conditions to exist in the reboiler. Also calculate the composition of the vapors leaving the reboiler.
10. The heat of fusion of a-naphthylamine (CioHsN) at its melting point of 49C
is 3,150 cal per g-mole. Calculate the solubility at 30C, assuming ideal behavior.
11. Calculate the ideal solubility of hydrogen cyanide gas in acetonitrile at a temperature of 100C and a partial pressure of 5 atm. The density of liquid hydrogen
cyanide is 0.699 at 20C. The vapor pressures at 100C are 9.2 and 1.89 atm.
respectively.
12. Calculate the ideal solubility of chlorine in carbon tetrachloride at a partial
pressure of 10 atm and a temperature of 100C. The vapor pressures at 100C
are 37.6 and 1.92 atm. respectively.
13. The solubiUty of carbon monoxide in benzene at 20C under a partial pressure
of 1 atm is reported^ as 0.1533 cc of gas measured at 0C and 1 atm, per cc of liquid
benzene. Assuming that the activity coefficients are unity, calculate the solubility
in mole per cent at 20C and 50 atm. Neglect the vapor pressure of benzene.
14. The following data for the solubility of carbon dioxide at a partial pressure of
1 atm in methyl alcohol are reported'' in cubic centimeters of gas measured at 0C
and 1 atm per cc of hquid.
fC
Solubility
15
4.366
20
3.918
25
3.515
(a) Assuming that ideal solutions are formed, calculate the average differential
heats of dissolution of CO 2 in methyl alcohol in the temperature ranges of 15-20
and 20-25C. Neglect the vapor pressure of alcohol.
(6) Prom the results of part (a), calculate the solubility at a temperature of SS'C
and a pressure of 100 atm.
15. Calculate the minimum total work in Btu in separating 100 lb of a solution
at 80F containing 30 mole per cent benzene, 25 per cent toluene and 45 per cent
xylene into the three pure components. Also calculate the entropy change per pound
of solution.
16. Calculate the minimum work and the entropy change in separating 100 lb of
a 2-molal aqueous solution of sucrose into its components at 26C. Compare this
^ result with the heat required to vaporize the water at the same temperature.
where
AG = rG^ + sG^-{
bm-cG^
AG = rGij -|- sGs -1
bGB cGc
5 = partial molal free energy
691
(2)
(3)
692
CHEMICAL EQUILIBRIUM
[CHAP.
XVI
b(GB-QB)~c(Gc-Gh)
(4)
hRT In as - cRT In ac
(
At equilibrium, AG. = 0, and
ttR al A
-T^
(5)
'
\al
(6)
a---J
-AG
AH
AS
j ^ ^ ^ o ^ ^ - ^ ^ - ^ - ^
(7)
fljB a c
where AG, AH, and AS are the changes in free energy, enthalpy, and
entropy, respectively, which accompany the stoichiometric reaction with
all reactants and products in their standard states.
From Equation (7) it is evident that the equilibrium constant is entirely determined by the temperature and the free-energy change which
would accompany the reaction of the indicated numbers of moles if each
reactant were initially in its standard state and each product finally in
its standard state of unit activity at the temperature of the system. This
free-energy change AG" is termed the standard free-energy change of the
reaction. The standard free-energy change depends upon the temperature, the definition of the standard state of each component, and the
number of moles entering into the stoichiometric equation under consideration. Accordingly, the mmierical value of an equihbrium constant
is without significance unless it is accompanied by specification of these
three factors.
The effect on the equilibrium constant of the form of the stoichiometric equation is illustrated by consideration of the synthesis of
ammonia. This reaction may be designated as
N2 + 3H2 = 2NH3
The corresponding equilibrium constant is then
CHAP. XVI]
693
and
K = ,
aL
;
AHI
694
CHEMICAL EQUILIBRIUM
[CHAP. XVI
CHAP. XVI]
695
Effect of Temperature on AG and K. A general differential relationship between AG and temperature is expressed by Equation (XI-104).
Combination of this wdth Equation (6) yields a similar expression for the
effect of temperature on the equilibrium constant. Thus
/a I n / A _ ^H_
dT ) ~ T^
(9)
(10)
AhT
AcT^ Ad
^ " 2 2 ^
dD
696
CHEMICAL EQUILIBRIUM
[CHAP. XVI
CHAP.
XVI]
697
(12)
~dT
JTI
(13)
CHEMICAL EQUILIBRIUM
698
[CHAP.
XVI
"^300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, K
(Revision of chart from Parks and Huffman, " Free Energies of Some Organic Compounds,"
with permission of the Heinhold Publishing Corporation.)
Experimental Free-Energy Data. Four common methods are available for determining standard free energies of formation and the standard free-energy change of a chemical reaction.
1. For reactions which proceed reversibly in a galvanic cell at constant
pressure and temperature, the free-energy change can be obtained directly from measurements of electric energy generated.
2. The standard free-energy change may be calculated from measurements of temperature, pressure, and composition of each phase in a
system at equilibrium by means of Equation (6).
3. The standard change in free energy can be obtained directly from
measurements of AH and AS by the equation-AG = AH-TAS.
CHAP. XVI]
699
700
CHEMICAL EQUILIBRIUM
[CHAP.
XVI
can be judged directly by numerical values rather than by the comparison of different equations which appear in as many forms as there
are empirical heat-capacity equations for the separate components. The
relative agreement of several forms of equations can be judged only by
repetition of calculations and usually not by inspection.
The standard heat of formation of a compound relative to the elements,
all in their standard state of unit activities at any temperature level, is
expressed by the following equation:
(AH?)J. = [(H^ - nl) + {An})o]a - S ( H ? - H^)^
where
(AH/)r =
Hr =
Ho =
(AH/)O =
standard
enthalpy
enthalpy
standard
(14)
(15)
The standard free energy of formation of a compound at a temperature T from the elements at the same temperature is expressed by an
equation similar to (14).
Similarly, the standard free-energy change and standard heat of reaction of any reaction at any temperature may be expressed in terms
of heats of formation at the absolute zero. Thus,
A H ; = S [ ( H ; - Ho) + (AH?)o]i> - 2[(H? - HS) + (AH})O]
(17)
/AG\
....
\T)T'
_ jGr - Hg
I T
(AH;)O-|
JG^-Hg
+ T jp~\
(AH?)o1
T + ~ r J
^ ^
\o^tf.
CHAP. XVI]
701
TABLE XXXV
STANDAED MOLAL ENTROPIES AT 298. 1K
(cal)/(g-mole)(K)
Standard States:
Gases: The ideal-gaseous state at 1 atm
Liquids: The liquid state at 1 atm
Solids: The solid state at 1 atm
Aqueous Solutions: The hypothetical ideal 1.0 molal solution in which o/m = 1.0
INORGANIC COMPOUNDS
Al(8)
Al (g)
A1+++ (aq)
Sb(s)
Sb(g)
Sb, (g)
SbjOa (s)
SbiO, (g)
6.75
39.31
-76
10.5
43.07
60.9
29.4
102
Aluminum
AI2O3
AljSiOe (Sillimanite)
12.5
27.0
Antimony
SbaO, (s)
SbiOs (s)
SbjSs (s)
SbCl3 (g)
SbCl, (s)
30.4
29.9
39.6
80.9
44.8
Argon
A(g)
As(s)
A8(g)
As2 (g)
AS4 (g)
AS2O3 (s)
AS4O6 (g)
36.99
8.4
41.62
67.3
69
25.6
101
Arsenic
AszOs (s)
AsCla (g)
AsCla (1)
AsF3 (g)
AsFa a)
25.2
78.2
55.8
69.2
50.1
Barium
B a F j (s)
BaCOs (s) (Witherite)
Ba(N03)2 (s)
BaS04 (s)
Ba(g)
Ba+j+ (aq)
BaO (s)
BaO (g)
BaCU 2H2O (s)
40.67
2.3
16.8
56.0
48.5
Be(s)
Be(g)
2.28
32.56
Bi(s)
Bi(g)
13.6
44.68
65.4
Bismuth
BijOa (S)
BiCls (g)
BiCls (s)
36.2
86.5
45.8
1.7
36.66
76.7
Boron
BCI3 (g)
B F , (g)
B i C (s)
68.6
61.1
6.47
BU(g)
B(s)
B(g)
BBra (g)
Beryllium
BeO (s)
BeO(g)
23.0
26.8
51.1
31.6
3.37
47.2
702
CHEMICAL EQUILIBRIUM
[CHAP. XVI
36.7
58.63
41.81
Br- (aq)
BrCl (g)
BrOr (aq)
Cadmium
19.7
57.4
38.5s
12.3
CdCU (s)
31.2
CdSg)
40:07
Cd(OH).(s)
CdCO, (s)
CdS04(s)
CdSO.-H.O(s)
CdSO.-8/3H,0(s)
25.2
31.3
39.7
57.5-
Cd-^(aq)
CdO(s)
Cdoi)
Cdsg
-15.6
13.1
46.9
IV
Calcium
Ca (s)
Ca(g)
Ca++(m)
CaOC)
CaO g
P_o fg^
Q^Y^ls)
CaHj (8)
9.95
37.0
-11.4
9-5
52.3
13.5
16.4
Ga(OH)j (s)
CaCOa (s) (Calcite)
CaCOa (s) (Aragonite)
CaC.O.-H.O(s)
Ca3(P0,).(s)(a)
CaSiOa (s) (WoUastonite)
CaSOi (s) (Natural Anhydrite)
17.4
22.2
21.2
37.4
57.6
19.6
25.5
9-9
Carbon
C (Graphite)
C (Diamond)
CO (e)
1.360.585
37.77
47.89
47.32
CF^ (g)
COCU
CH4
CN (g)
C2N2 (g)
Z%
51.08
CNBr(g)
CS(g)
50.3
CNCKg)
CS.a
36.2
CNI(g)
OS, (a)
cost)
CBr.fe)
CCU(g)
e c u (1)
56.84
55.37
85.5
74.2
52.2
C(g)
CU(g)
C1(g)
01-(iq)
CUO(g)
CIO2 (g)
Cr(8)
Cr(g)
CrjOs (s)
53.31
39.47
13.5
63.7
59.6
5.68
41.64
19.4
62.7
67.2
44.5
48.42
57.9
56.4
_5-3
CO3- (aq)
HCOr(aq)
H.CO, (aq)
CN (aq)
CsOr (aq)
Chlorine
-1^-"
22.2
45.1
25
-
ClO-(aq)
ClOr(aq)
ClOr(aq)
ClOr(aq)
Chromium
CrCU(8)
CrCl3(s)
CrOr (aq)
10.0
24.1
39-4
43.6
27.7
31.0
19-5
CHAP. XVl]
703
6.8
42.89
C0CI2 (S)
25.4
Copper
Cu (s)
Cu(g)
Cu^ (g)
Cu++ (aq)
CusO (s)
CuO (s)
CujS (s)
CuiS (s) (CovelUte)
CuCOs (s)
7.97
39.75
58.9
-26.5
,24.1
10.4
28.9
15.9
17.7
CuBr (s)
CuBr (g)
CuCl (s)
CuCl (g)
C u F (g)
C u l (s)
C u l (g)
C u H (g)
CUSO4 (S)
22.8
59.9
20.8
57.3
54.9
23.1
61.6
46.9
25.3
Fluorine
F2(g)
F(g)
48.58
37.93
He
30.13
- (aq)
F2O (g)
-2.3
58.95
Helium
Hydrogen
H2
D,
H(g)
H+ (aq)
H2O (1)
H2O (g)
D2O (1)
D^OCg)
31.23
34.62
27.40
0
16.75
45.13
18.08
47.38
49.15
47.48
44.66
41.53
49.36
26.96
48.23
Iodine
rt
12(8)
12(g)
1(g)
I - (aq)
IBr(g)
H2S (g)
H B r (g)
H C l (g)
HF(g)
HI(g)
H C N a)
HCN:(g)
27.9
62.29
43.19
25.3
61.84
I B r (s)
ICl(g)
ICI3 (S)
lOi" (aq)
33.0
59.11
41.1
28.0
Iron
Fe(8)
Fe(g)
Fe++ (aq)
Fe+++ (aq)
FeO (s)
FejOs (s)
Fea04 (s)
6.47
43.12
-25.9
-61.0
13.4
21.5
35.0
FeS (s)
FeSj (s) (Pyrite)
FeCU (s)
F e , C (s)
FeCOs (s) (Siderite)
FeiN
16.1
12.7
29.4
24.2
22.2
37.4
CHEMICAL EQUILIBRIUM
[CHAP XVI
704
TABLE XXXV {Cmtinued)
Lead
Pb(s)
Pb(g)
Pb++ (aq)
PbO (s) (YeUow)
PbO(g)
PbOj (s)
Li(8)
Li(g)
Lij (g)
Li+ (aq)
LiCl (g)
LijCOj
Mg(s)
Mg (.g)
Mg^Maq)
MgO (s)
MgO (g)
Mn(s)
Mn (g)
MnO (s)
MnO(g)
MnOj (s)
MnOr (aq)
HgO)
Hg(g)
Hg2 l,aqj
HgBr (s)
HgCl (s)
Mo (s)
Mo (g)
\
Ne(g)
Ni (8)
Ni (g)
NiO (8)
Pb304 (S)
15.49
41.90
3.9
16.6
16.6
5t.4
^'-^
18.3
PbS (s)
PbS (g)
PbCU
^^^^ (s)
PbCU (g)
'PbSOi (s)
lAthium
6.70
33.15
47.0
4.7
49.9
21.5
LiF (s)
Lil (g)
LiH (s)
LiH (g)
LiOH (s)
Magnesium
Mg(0H)2 (s)
7.77
MgCOs (s) (Magnesite)
35.51
ivigoiws (s)
v>j
MgSiOs
-_3q1i. 66
26.55
^1,
M,S04(s)
MgS04 (s)
50.7
Manganese
7.61
41.50
14.4
54.0
^-g
13.9
^ ^
46.7
MnjOs (s)
Mn304 (s)
MnS (s)
MnCU (s)
MnCOa (Rhodochrosite)
MnCOa (Rhodochrosite)
ivrnP,
MnC
Mercury
18.5
41.8
17.7
16.6
17.6
26.4
23.5
HgBra (g)
HgBrj (s)
HgCU (g)
xigvia (s)
vn;
HgCU
Hgla (g)
H g l j (s)
HgjSOi (s)
50.5
21.8
61.2
32.6
75.9
^^-^^
9.7
56.5
5.9
40.8
12.8
15.09
15.7
15.4
on
2
22.9
35.5
18.7
25.9
^"-^
74.7
38.9
70.4
34.6
707
48.0
Molybdenum
6.83
43.47
M0S2 (s)
M0S3 (s)
15.0
15.9
Neon
34.96
Nickel
7 12
43 53
n r,
^-^
NiClj (s)
Ni(C0)4 (g)
25.6
97
CHAP. XVI]
705
NOBr (g)
45.79
36.62
62.58
50.34
57.47
72.7
36.6
82
65.2
0^(8)
0(g)
03(g)
49.03
38.48
57.1
P(g)
P4(g)
P (s) (White)
P(g)
PBra (g)
PCI3 (g)
PCI, (1)
PCl6 is)
62.1
66.8
10.6
38.99
83.4
74.7
52.2
87.7
K(s)
K(g)
K,(g)
K+ (aq)
KBr (s)
KBr (g)
KCl^(s)
15.2
38.30
59.5
24.2
22.6
60.4
19.76
Si(s)
Si(g)
SiOz (Quartz)
SiCU (g)
SiCU 0)
SiF4(g)
4.50
40.13
10.1
79.2
57.3
68.0
Ag(s)
Ag(g)
Ag+ (aq)
AgiO (s)
AgaS (a)
AgBr (s)
10.20
41.33
17.54
29.1
35.0
25.60
N2(g)
N(g)
NsOfe)
NO(g)
^ O , (g)
N^Oi (g)
N2O5 (S)
N2O6 Gg)
Nitrogen
NOCl (g)
NH3 (g)
NH4CI (S)
NH4HCO3 (S)
NH4HS {%)
NH4OH (aq)
NHi" (aq)
NO7 (aq)
NOr (aq)
HNO3 (liq)
Oxygen
OH(g)
OH- (aq)
Phosphorus
PCls (s)
PF3 (g)
PH3 (g)
PN(g)
H3PO4 (aq)
HiPOr (aq)
HPOr (aq)
POf (aq)
Potassium
KCl (g)
KF(g)
' KI (s)
KH(g)
KCIO3 (S)
KNO3 (S)
KSOi. (s)
Silicon
Si02 (Cristobalite)
SiOa (Tridymite)
SiOj (Glass)
SiH4 (g)
SiC (s)
SisNi (s)
Silver
AgBr (g)
AgCl (g)
AgCl (s)
AgNOa (S)
AgsSOi (s)
Ag(NH3)r (aq)
63.0
46.03
31.8
28.3
27.1
42.8
26.4
29.9
35.0
37.19
43.9
-2.49
40.8
64.2
50.35
50.44
44.0
28.0
-2.3
-45
57.7
56.7
24.1
47.3
34 2
31.8
44.8
10.35
10.5
11.2
48.7
3.95
22.8
62.1
59.8
23.0
33.7
47.9
57.8
706
CHEMICAL EQUILIBRIUM
[CHAP.
XVI
12.2
36.72
54.9
14.0
17 ,
58.1
17.3
55.5
13.1
53.8
60.0
NaH (g)
NaOH (s)
NajCOs (s)
NaHCOs (s)
NaNO, (s)
NaiSiOi (s)
NajSiOs (s)
NasSijOs (s)
NaiiSOi (s)
n&sOi 10H2O (s)
NaK
45.0
14.2
32.5
24.4
27.8
46.8
27.2
39.4
35.7
140.5
68.6
Sulfur
7.62
7.78
40.1
54.41
92
109
53.07
59.24
63.8
SOs (1)
SFe (g)
H2S (aq)
HS- (aq)
H2SO3 (aqi
HSOr (aq)
SOT (aq)
HSOr (aq)
SOf (aq)
Sn (white)
Sn (gray)
SnO (s)
Sn02 (s)
12.3
10.7
13.5
12i5
Sn(g)
Sn++ (aq)
SnCU (g)
SnCU (l)
Ti(s)
Ti(g)
TiOj (Rutile)
6.6
43.07
12.4
S (rh)
S (mono)
S(g)
S^Cg)
S6(g)
SsCg)
SO(g)
BO, (g)
SO, (g)
31.7
69.6
29.4
14.9
54.7
32.6
3
30.6
4.4
Tin
40.24
-4.9
87.2
62.1
Titanium
TiCU (g)
Ticu a)
84.4
60.4
Vajiadium
V(s)
V(g)
V2O3 (S)
7.0
43.55
23.5
V2O4 (S)
V2O5 (S)
24.5
31.3
Zinc
Zn (s)
Zn(g)
Zn++ (aq)
ZnO (s)
ZnO (g)
ZnS (s)
9.95
38.46
-25.7
10.4
54.1
13.8
ZnBrj (s)
ZnCU (s)
Znlj (s)
ZnCOa (Smithsonite)
' ZnSOt (s)
33.0
25.9
38.5
19.7
30.7
Zirconium'
Zr(8)
9.5
Zr(g)
43.33
CHAP.
XVI]
707
Propylene
65.06 28
Propane
64.69 28
56.79 21
Cyclopropane
Dimethyl acetylene
67.93 33
Dimethyl acetylene (1)
46.63 33
Isobutene
71.28 28
73.58 28
cis-2-Butene
72.98 28
frons-2-Butene
75.38 28
1-Butene
Butane
74.21 28
Butane (1)
55.2 28
70.51 28
Isobutane
52.09 28
Isobutane (1)
Trimethylethylene
79.7 18
Pentane
83.23 28
2-Methyl hexane
99.48 28
59.4 26
Methyl cyclohexane (1)
2, 2, 3-Trimethyl butane
92.31 28
76.44 29
Toluene
62.40 29
Toluene (1)
67.1 26
Ethyl cyclopentane (1)
110.69 28
n-Octane
101.35 28
2, 2, 4-Trimethyl pentane
2, 2, 3, 3-Tetramethyl butane 94.05 28
84.50 29
o-Xylene
68.80 29
o-Xylene (1)
86.60 29
m-Xylene
60.42 29
jn-Xylene (1)
84.27 29
p-Xylene
59.20 29
p-Xylene (1)
82.07 11
Styrene
Styrene (1)
Ethyl benzene (1)
Nonane (1)
Mesitylene
n-Butyl benzene (1)
Neopentane
Isopentane
Cyclopentane
Cyclopentane (1)
-Hexane
2-Methyl pentane
2-Methyl pentane (1)
2, 2-Dimethyl butane
2, 2-Dimethyl butane
2, 3-Dimethyl butane
3-MethyI pentane
Benzene
Benzene (1)
Cyclohexane
Cyclohexane (1)
Methyl cyclopentane 0)
n-Heptane
Naphthalene (s)
Decane (1)
|3-Methyl naphthalene (s)
Duodecane
Diphenyl (s)
n-Heptyl cyclohexane (1)
Anthracene (s)
Phenanthrene (s)
Pyrene (s)
ji-Dodecyclohexane (1)
1, 3, 6-Triphenyl benzene (s)
2-Methyl 2-butene
3-Methyl 1-butene
2-Methyl 1-butene
Alcohols
Methyl alcohol (g)
Ethyl aclohol (g)
Ethyl alcohol (1)
Isopropyl alcohol (1)
Isopropyl alcohol (g)
CHO Compounds
Formaldehyde (g)
Acetone (g)
Acetone 0)
Dimethyl ether (g)
Dimethyl ether (1)
57.72
66.39
38.4
43.0
73.4
13
2
31
31
31
S' Ref.
56.78 11
61.3 26
94.0 26
92.34 29
76.9 26
73.23 28
82.03 28
70.70 4
48.87 4
92.45 28
90.15 28
69.9 28
85.75 28
64.4 28
86.49 28
89.96 28
64.39 29
41.49 29
71.41 6
49.3
6
59.3 26
101.57 28
39.9 26
102.7 26
48.8 26
16
147
49.2 26
106.8 26
49.6 26
50.6 26
51.4 26
147.5 26
87.9 26
82.8 10
82.0 10
81.0 10
52.42
72.7
47.9
63.72
44.98
32
31
31
19
19
708
CHEMICAL
EQUILIBRIUM
TABLE XXXV
Halogen
(Continued)
Compounds
Chlorofomi (g)
Methylene chloride (g)
MethyL chloride (g)
Methyl chloride (1)
Fluorotrichloromethane (g)
Fluorotrichloromethane (1)
Ethylene dichloride (1)
Ethylene dichloride (g)
Phosgene (g)
Nitrogen
S Re}.
70.82 32
64.68 32
65.94 23
36.74 23
74.07 25
63.92 25
49.84 27
72.74 27
67.24 32
A.cids
Formic (g) (monomer)
Formic (g) (dimer)
Acetic acid (g)
Lactic acid (s)
Hippurio acid (s)
60.0
83.1
70.1
34.30
67.2
12
12
12
15
14
Carbohydrates
1-Sorbose (s)
/3-Maltose monohydrate (s)
a-Lactose monohydrate (s)
/3-Lactose (s)
a-d-Galactose (g)
52.8
99.8
99.1
92.3
49.1
17
1
1
1
17
[CHAP. X V I
Compounds
S Bef.
Methylamine (g)
Methylamine (1)
Dimethylamine (g)
Dimethylamine (1)
Methyl cyanide (g)
Methyl isocyanide (g)
Bromoform (g)
Methylene bromide (g)
Methyl bromide (g)
Ethylene dibromide (1)
Ethylene dibromide (g)
Methyl fluoride (g)
Methyl iodide (g)
67.73 5
35.90 5
65.24 3
43.58 3
68.02 9
68.70 9
79.14 32
70.16 7
58.74 8
53.37 27
79.37 27
53.30 7
60.85 7
Sulfur Compounds
Methyl mercaptan (g)
61.02 30
Dimethyl sulfide (g)
68.28 24
Dimethyl sulfide (1)
46.94 24
EEFERENCES
1. ANDERSON, A. G., and G. STEGEMAN, / . Am. Chem. Soc, 63, 2120 (1941).
61,1539-43
(1939).
4. ASTON, J. G., H . L. F I N K , and S. C. SCHUMANN, / . Am. Chem. Soc,
65, 341-6
(1943).
5. ASTON, J. G., C. W; SILLER, a n d G. H . MBSSEBLY, J. Am.
1743-51 (1937).
6. ASTON, J. G., G. J. SZASZ, and H . L. F I N K , J. Am. Chem. Soc, 65, 1135-9 (1943).
7.
8.
9.
10.
11. GuTTMAN, L., E . F . WESTHUM, J R . , and K. S. PITZER, / . Am. Chem. Soc, 65,
1246-7 (1943).
12. HALFORD, J. O., J. Chem. Phys., 10, 582-4^(1942).
13. HALFORD, J . O., and B. PECHERER, J. Chem. Phys., 6, 671-5 (1938).
14., HUFFMAN, H . M . , / . Am. Chem. Soc, 63, 688-9 (1941).
C H A P . XVI]
709
62, 297-9
(1940).
16. HuGGiNS, M . L., / . Chem. Phys., 8, 181 (1940).
17. JACK, G . W . , and G. STEGEMAN, / . Am. Chem. Soc, 63, 2120 (1941).
(1941).
20. KisTiAKOwsKY, G. B., and W. W. R I C E , / . Chem. Phys., 8, 610-18 (1940).
21.'LiNNETr, J. W., J. Chem. Phys., 6, 700 (1938).
22._LINNETT, J. W., and W. H . AVEEY, / . Chem. Phys., 6, 690 (1938).
23. MESSEELY, G . H . , and J. G. ASTON, J. Am. Chem. Soc., 62, 886-90 (1940).
2 4 . ~ O S B O B N E , D . W . , R . N . DOESCHEE, a n d D . M . YOST, / . Am. Chem. Soc,
64, 165
(1942).
25. OsBOENB, D . W., C. S. GAENEE, R . N . DOESCHEE, and D . M . Yost, J.
26.
27.
28.
29.
Am.
Chem. Soc,
64.
165-9 (1942).
31. SCHUMANN, S . C . , and J . G. ASTON, / . Chem. Phys., 6, 485-8 (1938).
32. STEVENSON, D . P., and J. Y. BEACH, / . Chem. Phys., 6, 25-9, 108 (1938).
33. Y O S T , D . M . , D . W . OSBORNE, and C. S. G A E N E E , / . Am.'fihem.
Soc,
63, 3492-6
(1941).
(19)
G j r = ( G r - H o ) + (AH?)o
(20)
where
H/r and G/T = the relative enthalpy and relative free energy, respectively, of the compound at temperature T referred
t)o the elements at 0K
> J. G. Aston, Chem. Rev., 27, 63 (1940).
710
CHEMICAL EQUILIBRIUM
[CHAP.
XVI
TABLE XXXVI
/GJ.-H5\
cal/(g-inoIe)C'K)
298.1.
r, K
Methane
36.42
Ethane
45.25
Ethylene
44.05
Propane
52.83
Propylene
54.3
n-Butane
58.54
Butene-1
62.0
as-2-butene
60.0
</-ans-2-butene
59.4
isobutane
56.14
isobutene
57.0
n-Pentane
64.19
2-Methyl butane
64.70
Tetramethylmethane1 56.28
n-Hexane
69.86
2-Methyl pentane
69.7
3-Methyl pentane 69.7
2,2-Dimethyl butane 66.0
2,3-Dimethyl butane 66.3
Acetylene
40.01
Graphite
0.545
Hydrogen H j (g)
24.436
HjO (g)
37.191
CO
40.364
CO2
43.578
0,
42.081
N2
38.834
NH,
NO
42.985
..400.
38.82
48.20
46.70
66.62
67.6
63.56
66.3
64.3
63.7
60.85
61.6
70.32
70.40
61.87
77.12
kcalper
g-mole
-15.96
-16.48
14.51
-19.44
8.68
- 23.25
6.49
3.65
2.70
- 24.52
1.64
-27.03
-28.45
-31.07
- 31.06
-32.2
-32.0
-34.6
-34.0
64.34
0
0
- 57.108
-27.18
-93.949
0
0
21.579
CHAP. XVI]
711
TABLE XXXVII
B'J. ;
B.I FOR THE IDEAL-GASEOUS STATE AT" 1 ATM
298.1
. 8 0 0 . . . .1000.. .1500
2.397
11.4
21.4
8.3
2.865
12.78 18.37 34.56
2.59
16.87* 24.64*
2.41
3.535 5.59
8.08 11.06 17.91 25.92 48.77
3.20
6.36* 10.14* 14.49* 24.75* 36.62*
4.66
7.43 10.77 14.63 23.68 34.13 63.74
' 4.29
7.08 ' 10.46 14.39 23.50 34.00 64.00
3.99
4.06
4.06
4.25
5.68
9.12
13.26 18.04 29.21 42.08 78.42
5.17
8.63 12.84 17.70 28.98 41.91 78.69
5.05
8.56
12.84 17.81 29.37 42.54 79.50
6.71 10.83 15.77 21.46 34.76 50.04 93.10
21.1 .
6.07
49.9
6.04
21.1
50.1
5.87
20.9
50.2
6.020
21.3
50.3
0.251 0.51
0.83
1.20
2.07
3.07
6.0
2.023 2.731 3.430 4.128 5.537 6.966 10.696
2.365 3.190 4.019 4.874 6.669 8.583 13.89
2.073 2.784 3.490 4.209 5.701 7.258 11.363
2.240 3.197 4.227 6.328 7.697 10.233 17.02
2.069 2.789 , 3.524 4.280 5.855 7.499 11.77
2.074 2.772 3.485 4.188 5.672 7.230 11.220
N2
2.193 2.900 3.670 4.344 5.872 7.460 11.610
NO
*CalcuIated from data of Table XXI, page 336.
Because of its smaller variation with temperature it is convenient to
tabulate values of G}T/T.
In these terms Equations (17) and (18) reduce to
Am = S(H;7-)P - 2(H/r)ij
(21)
r, "K
Methane
Ethane
Ethylene
Acetylene
Propane
Propylene
n-Butane
isobutane
1-Butene
cts-2-butene
trans-2-buiene
isobutene
n-Pentane
2-Methyl butane
Tetramethyl methane
n-Hexane
2-Methyl pentane
3-Methyl pentane
2, 2-Dimethyl butane
2, 3-Dimethyl butane
Graphite
Hydrogen, Hj (g)
Water, H^O (g)
CO
CO2
O2
-i.<|.X-<fX
T
\ i /P
(22)
CHEMICAL EQUILIBRIUM
712
[CHAP.
XVI
+3
/
'^''^ Oi#^"
+2
t< +1
3 0
Hi+S2^252^
p/
S5
-1
^:*^
^/
-^^Q*^
-2
l-Oi'*
-3
4-CO
200
400
600
800
1000 1200 1400
Temperature, "Kelvin
1600
1800
2000
=-(f).
(23)
CHAP. XVI]
713
Illustration 4. From the data of Tables XXXVI and XXXVII calculate the
values of AH/ and hG}/T for the formation of isobutene from the elements at
298'. 1K
4 C ( s ) + 4 H 2 ( g ) - - > C4H8(g)
From Tables XXXVI and XXXVII
J-
/ 298.1
iC^HsCg)
H2(g)
-57.0
-24.436
-0.545
.0
2.023
0
0.251
1.64
4.25
(AH;)O
(HJ> H 0)298.1
C(s)
>
propylene at 800K.
From Table XXXVI at 8 0 0 %
3H8(g)
H2(g)
(^")
69.00
-31.204
(AH;)O
19.440
17.910
5.537
C3H6(g)
-68.3
8.580
24.750
<
714
CHEMICAL EQUILIBRIUM
[CHAP. XVI
EQUILIBRIUM COMPOSITIONS
B. F. Dodge* has aptly discussed the fe&ibility of a chemical reaction
thus:
"The statement is sometimes made that a given reaction is thermodynamically impossible. This is a loose statement which has no
meaning in the absence oj qualifying statements. For example, any
reaction, starting with pure reactants uncontaminated by any of the
products, will have a tendency to proceed to some extent even though
this may be only infinitesirfial. Thus, the reaction
H20(g) = H2(g) + K)2(g)
proceeds to some extent at 25''C, and we can even calculate with considerable assurance the percentage of water vapor that would be decomposed. From the accurately known value of AG of_, this reaction
at 25C the equilibrium constant is about 1 X 10"*, and the extent of
decomposition is infinitesimally small but definite,"
"From the value of the standard free-energy change for any reaction
we can form an opinion about the feasibility of the reaction without
further calculation. Thus, if AG = 0 at a given temperature, then
K = I, and it is obvious that the reaction must proceed to a considerable extent before equilibrium is reached. The situation becomes less
favorable as AG increases in the positive direction but there is no definite value that one can choose as clearly indicating that the reaction is
not feasible from th'e standpoint of industrial operation. At 600K the
AG for the methanol synthesis reaction is +11,000 calories per grammole, and yet the reaction is certainly feasible at this temperature. In
this case the imfavorable free energy change for the standard state is
partially overcome by utilizing high pressure to displace the equilibrium.
Other means can also be used such as changing the ratio of reactants or
removing one of the reaction products."
"For the purpose of Ascertaining quickly and only approximately if any
given reaction is proinising at a given temperature, the following rough
classification may be useful:
AG < 0
Reaction is promising
AG > 0 but < +10,000 Reaction is of doubtful promise but warrants
further study
AG > +10,000
Very unfavorable, would be feasible only under
unusual circumstances
It should be understood that these are only approximate criteria that
are useful in preliminary exploratory Work."
" B. F. Dodge, Trans. Am. Inst. Chem. Engrs., 34, 640 (1938). '
CHAP. XVI]
GASEOUS SYSTEMS
715
(yRNRyiysNs)'
(yaNBYiycNcy-
N'^Ns---_-^yiyc---
(24)
Gaseous Systems. 'As previously mentioned, in a system which involves only gaseous components which behave as approximately ideal
solutions, it is convenient to choose as the standard state the component
gases each at unit fugacity expressed in atmospheres. This state is
hypothetical at temperatures where saturation pressures are below unit
fugacity. With this definition, the activity of component B in ideal
solutions of gases is
aB=fB = Nsfs,, = NBVBITT!(25)
where
/BIT, VBn = the fugacity and fugacity coefficient, respectively, of pure
component B at the temperature and total pressure x
of the system
Combining (25) and (7) gives
^ = (N}m^\(tliy+'^-''-^-c---
Viviiva y w ^ /
(26)
,
,
, ""^
,
7
nB + nc+- +nB + ns + \- - + 711
(27)
^^ = ^ 1 4 ^
VBVC
(28)
716
CHEMICAL EQUILIBRIUM
[CHAP. XVI
[nine
"L^B+ncH
-\-nB-\-na+
-<! + )
(29)
+ni]
7.8%
10.8%
81.4%
100.0%
This gaseous mixture is passed into a converter where in the presence of a catalyst
the SO2 is oxidized to SO3. The temperature in the converter is maintained at
500C and the pressure at 760 mm of Hg. Calculate the composition of the gases
leaving the converter, assuming that equilibrium conditions are reached. It may
be assumed that the fugacity coefficients and hence Kv are equal to unity.
Solution:
Basis: 100 Ib-moles of the original mixture.
SO.(g)+iO.(g)=S03(g)
From Fig. 156, at 500C (773''K), log K = 1.93;
K = 85
TT = 1.0 atm
Limiting reactant = SO2
Let X = equilibrium conversion of SO2. Composition of equilibrium mixture:
502 = 7.8 - 7.8r lb-moles = ngoj
503 = 7.8x = ngo^
O2 = 10.8 - 7.8 f - ) Ib-molea = no.
N2 = 81.4 lb-moles = n
From Equation (29):
Na
\
=K
(a)
CHAP. XVI]
GASEOUS SYSTEMS
717
"
*^
Thissame procedure may be followed to calculate the degree of completion in any system at conditions for which the necessary data are
available. By repeating the calculations of Illustration 6 to correspond
to other conditions of temperature and pressure, the effects of varying
these conditions may be quantitatively predicted.
Under conditions oi high pressure the fugacity coefficients cannot be
neglected, but the general method of solution is the same. Values of Kv
may be calculated directly from fugacity coefBcients of the individual
components obtained from Fig. 142. Where a number of calculations
are to be made for a particular system of reaetants and products a chart
may be prepared relating Kv to temperature and total pressure. Figure 156a is such a chart for the ammonia-synthesis system where
^
Kv
''NH,
2 y2
N2 Ha
CHEMICAL EQUILIBRIUM
718
[CHAP.
XVI
"NHa
4 A
and
1.0
tLy"
0.8
TNES
'MJ
Ha
0.6
^
0.4
0.2
500'
450
^ * > x ^
400 "K
100
200
300
400
600
600
700
Pressures in Atmospheres
800
900
1000
or
L(l-i)d
\{2-x))
X = 0.589
The percentage conversion of Nz to NHs is hence 58.9 per cent, and the composition
of the equihbrium mixture in mole per cent is
Ni = 14.6 per cent
Ha = 43.8 per cent
NH3 = 41,6 per cent
{nBy{ncY-~ K\_
TT
Equa(30)
CHAP. XVI]
EQUILIBRIUM CONVERSION
719
CHEMICAL EQUILIBRIUM
720
[CHAP.
XVI
amounts of these compounds which are formed by the reaction in proceeding to equilibrium conditions. Therefore, the addition of reaction
products to the initial reaction system reduces the equilibrium conversion
of any reactant.
Equilibrium-Conversion Charts. Where numerous calculations are to
be made of equilibrium composition corresponding to various conditions
of temperature and pressure for a reacting system of constant initial
composition it is frequently convenient to prepare charts expressing the
equilibrium degree of completion as a function of temperature and pressure. Such a chart obviates the necessity of frequent repetitions of
tedious graphical solutions of the type of Illustration 6.
Even in a complicated system the data for an equilibrium-conversion
chart may be readily calculated by arbitrarily selecting a series of values
of conversion. From Equation (29) the equilibrium constant is calculated corresponding to each of these selected degrees of completion
and to a selected constant pressure. The temperature corresponding to
each equilibrium constant may then be obtained from Fig. 156. These
results are plotted, temperatures being used as abscissas and fractional
conversion as ordinates. By repeating these calculations to correspond
to other selected pressures a complete chart may be constructed. These
calculations are best tabulated. In the following illustration t^is method
is applied to the system discussed in Illustration 6.
Illustration 8. For the reacting system discussed in Illustration 6, calculate and
plot curves relating the equilibrium conversion to temperature at pressures of 1.0
and 2.0 atm, respectively, assuming K, = 1.0.
TABLE A
1.0-X
3.9x
0.50
i 0.70
0.90
.0.95
0.98
0.5
0.30
0.10
0.05
0.02
1.95
2.73 '
3.51
3.70
3.82
98.0
97.3
96.5
96.3
96.2
[(5)/(4)]^
(l)/(2)
KM^
3.33
3.47
3.64
3.68
3.71
1.0
2.33
9.0
19.0
49.0
3.33
8.09
32.8
70.1
181
CHAP.
EQUILIBRIUM-CONVERSION CHARTS
XVI]
721
then obtained from Fig. 156. The calculations are summarized in Tables A and B.
In the column headings the numbers in parentheses represent the results contained
in the columns bearing these numbers.
TABLE B
X = 1.0
logK
X ,^^
3.33
8.09
32.8
70.1
181
0.5
0.7
0.9
0.95
0.98
x = 2.0
0.523
0.908
1.516
1.846
2.258
rK
logX
T'K
978
910
822
782
737
2.35
5.71
23.2
49.5
128
0.371
0.757
1.366
1.695
2.107
1005
935
841
800
752
^^
%
90
gg80
#7
S
.3^70
/
& 60
/l f
m
50
400
450
500
i/ ^
hT
jF
>
sA^ \E
700
750
800
722
CHEMICAL EQUILIBRIUM
[CHAP.
XVI
Where the standard state for solids and liquids is taken at atmospheric
pressure or at low equilibrium vapor pressures, the activitieb of pure
liquids and pure solids may be taken as unity at all moderate pressures,
and the composition of the gaseous phase at equilibrium will not be affected by the presence of the solid or liquid. However, at high pressures
the activities of pure solids and liquids are affected by pressure, and the
composition of the gaseous phase at equilibrium is affected by the presence of the liquid or solid. When solid or liquid solutions are formed
the activities of the components in solid or liquid solutions are no longer
unity even at moderate pressures, and the equilibrium composition of the
gas is greatly affected by the presence of the solid or liquid phase. In
such cases the activities in the solid or Uquid solutions are expressed in
terms of mole fractions and activity coefficients as discussed in Chapter XIV.
Illustration 9. Ferrous oxide, FeO, is reduced to metallic iron by passing a mixture
of 20 per cent CO and 80 per cent N2 over it at a temperature of 1000C under a
pressure of 1 atm. Assuming that equilibrium is reached, calculate the weight of
metalUc iron produced per 1000 cu ft of gas admitted measured at 1 atm and 1000C.
Fugacity coefficients may be assumed equal to unity. The reaction taking place is
as follows:
FeO (s) + CO (g) ^ Fe (s) + COj (g)
At 1000C the value of K for thig reaction is 0.403.
Basis: 1.0 lb-mole of entering gas.
Since the activities of FeO and Fe equal 1.0, Equation (31) may be arranged in
the form of (29). Then
/^CoA
\ c o / "CO + "COs +
"NJ
K or = it
"CO
CHAP. XVI]
723
x = 0.287
= 1.9 lb
Pressures of Decomposition and Vaporization. Many solid compounds decompose to yield another solid and a gas as in the calcination
of calcium carbonate to form lime and carbon dioxide. Such decompositions will proceed only when the activity of the gaseous product in
contact with the sohd is less than the equilibrium value determined by
the temperature and the nature of the reaction.
A solid decomposition reaction may be represented by the following
equation:
65 (s) ^ ri?(s)-f sS (g)
(32)
The activities of the solids are approximately unity at moderate pressures so that as long as any of compounds B and R are present Equation (7) may be applied to this reaction as follows:
K = a% = e ^ = e ^
(33)
At low pressures, where the activity of a gas may be taken as equal to its
partial pressure, a*s = Ps and
724
CHEMICAL EQUILIBRIUM
[CHAP. XVI
Cp = 10.00 + (4.84)(.IQ-^T
for CaCOa:
108 000
^
0(Y7 AAA
199,600
^
Ad
^ 1
+ --<'-'<-'>-3(S-)
or
Is = 55.31 and ASjooo = 35.90
From Equation (34),
,
^
I f
-41,924
35.90]
, .
log Ps =
= 1.316
2.303 L(1.987) (1000) 1.987J
^
or
p, = 0.0483 atm at lOOO^'K
At a decomposition pressure of 1 atm, from Equation (34) AG^ = 0. The corresponding temperature T is calculated from Equation (11);
.
AGT = 7H + (Aa -I,)T
Equations (23) and (34) are directly applicable to the equilibrium between a pure solid or liquid and its vapor. In this case AG, Aff, AS
K. K. Kelley, " High-Temperature Specific Heat Equations for Inorganic Substances," V.S. Bur. Mines Bull, 371 (1934).
CHAP. XVI]
725
.^298
?^
= 0.225
(4.57) (3000)
K = Pv= 1.68
726
CHEMICAL EQUILIBRIUM
[CHAP. XVI
Temperature >
Isothermal equilibrium
,vxtve
Temperature^
Exothermic Reaction
Endothermic Reaction
FIG. 158. Equilibrium Conversion in Exottiermic and Endotliermic Reactions for
Isothermal and Adiabatic Operations.
page 308. The values on this curve are independent of pressure if it is
assumed that enthalpies are independent of pressure. However, a new
curve must be plotted to correspond to each change in the initial temperatures of any of the reactants.
In reactions proceeding adiabatically the characteristic behaviors of
exothermic and endothermic reactions are shown diagrammatically in
Fig. 158. In exothermic reactions the equilibrium conversion decreases
with increase in temperature whereas the temperature steadily rises as
the reaction proceeds. The adiabatic reaction obviously cannot proceed
beyond the intersection of these two lines. In endothermic reactions
the reverse is true: the equilibrium degree of conversion is favored by a
rise in temperature whereas the temperature falls as the reaction proceeds. It may be noted that isothermal operation leads to a higher
equilibrium conversion in either an, endothermic or exothermic reaction.
Illustration 12. ^ The mixture of 7.8 per cent SO2, 10.8 per cent O2, and 81.4 per
cent N2 discussed in Illustrations 6 and 8 enters^the converter at a temperature of
400C. Calculate the equilibrium temperature attained in the converter, assuming
that it is thermally insulated so that the heat loss is negligible.
CHAP. X V I ]
A D I A B A T I C REACTION TEMPERATURES
727
Solution:
Basis: 100 g-moles of the original gaseous mixture.
Reference temperature: 18C.
Let
X = degree of completion
From the heat-of-formation data, Table XIV, page 257,
AH = (-93,900) - (-70,920) = -22,980 cal per g-mole
SO2 converted = 7.8i g-moles
Total standard heat of reaction = (7.8x) (22,980) = 179,240a; cal
Enthalpy of Reactants: Mean heat capacity between 18 and 400C is obtained
from Table VI, page 216.
SO2 = (10.91) (7.8) (400 - 18) = 32,510
02>= (7.40) (10.8) (400 - 18) = 30,530
N2 = (7.09) (81.4) (400 - 18) = 220,460
Enthalpy of reactants = 283,500
Enthalpy of Products Relative to 18C:
f
AH=
ncj, dT;
T is in K
^291
728
CHEMICAL EQUILIBRIUM
[CHAP. XVI
f
method demonstrated in Illustration 13. Such a chart may be constructed in a similar manner to'apply to any system for which the ,
necessary data are available. From Fig. 157 the equilibrium temperature and degree of completion corresponding to any selected adiabatic ,
operating conditions may be readily estimated. For example, if the reacting gases enter the converter at a temperature of 375C and a pressure
of 1.5 atm, an equilibrium ^temperature of 585C and a degree of completion of 87 per cent will be attained.
If a reaction cannot be assumed to proceed under adiabatic conditions,
a chart of the type of Fig. 157 can be constructed which takes into account the loss of heat from the reacting system. Such losses in no way
affect the E curves. However, the heat losses, expressed as a function
of the temperature of the system, must be included in the energy-balance
equation from which the data for the F curves are calculated.
Equilibriiim-Reaction Temperatures at High Pressures. When reactions proceed at high pressures, the method described for obtaining the
equilibrium-reaction temperature should be modified to take into consideration the effect of pressure upon enthalpies, heat capacities, and
activities of the component gases. For example, if a 1:3 mixture of
nitrogen and hydrogen enters a catalytic reaction chamber at 400C and
reacts adiabatically to' equilibrium at 300 atm, the temperature leaving
will be 590C with a corresponding percentage conversion of nitrogen to
ammonia of 25 per cent. If the results were calculated with the effect
of pressure upon heat capacities and activities neglected, the calculated
results would be 600C with a corresponding conversion of 21 per cent.
The smaller temperature rise under actual conditions is due to the increased heat capacity of ammonia at 300 atm, and the increased percentage conversion is due to the decrease in activities of ammonia as^.
compared to nitrogen and hydrogen.
Equilibrium-reaction temperatures are readily calculated by the general methods already demonstrated if ideal solutions are formed. This /
condition is generally satisfactorily approximated where all reactants and
products are well above their critical temperatures. For other cases involving reactions at conditions in the vicinity of the critical point of the
mixture, the precise methods for estimating activities described in Chapter XIV must be used.
Illustration 13. It is desired to calculate the equilibrium percentage conversion
of SO2 to SO3 and the corresponding temperature when the system described in Illustration 12 reacts adiabatically at 100 atm and the entering temperature is 400C.
The equilibrium-temperature line E, corresponding to 100 atm, is constructed as
in Illustration 8 except that the deviation of K, from unity is calculated from Fig. 142
as in Illustration 7. The adiabatic heating line "F is constructed by the method employed in Illustration 12, except that allowance is made for the effect of the pressure
CHAP. XVI]
729
of 100 atm upon the enthalpies of the entering and reacting mixtures. These corrections are obtained from Fig. 106. The procedure is as foUows:
The critical constants of the component gases are:
S02
Ns
O2
SO3
TlK
430.2
125.9
154.2
491.3
Pcsim
77.7
33.5
49.7
83.6
For the entering gas, which contains 7.8 per cent SO2, 81.4 per cent N2, 10.8 per
cent O2:
Pseudocritical temperature = 0.078(430.2) + 0.814(125.9) + 0.108(154.2) = 152K
Pseudocritical pressure = 0.078(77.7) + 0.814(33.5) + 0.108(49.7) = 38.6 atm
Pseudoreduced temperature, T^ =
= 4.40
Pseudoreduced pressure, Pr =
= 2.59
38.6
~ " =0
To
The effect of the elevated pressure on the enthalpy at 400C is negligible. When
the gas has been heated adiabatically by reaction to equilibrium, the approximate
conversion is 96% at 631 C.
The corresponding composition is
502 = 7.8(1 - 0.96)
N2
7 05 moles
7.3%
'
The correction of enthalpy for pressure may be shown by Fig. 106 to be negligible
and the adiabatic line at 100 atm coincides with the adiabatic line for 1 atm.
EQUILIBRIUM OF SIMULTANEOUS REACTIONS
730
CHEMICAL EQUILIBRIUM
[CHAP.
XVI
(AH;)O
(AQ7r)4oo
K
n-Pmtane
Isopentane
Neopentane
-70.32
-70.40
-61.87
-28.450
-3.63
6.21
-31.070
-1.65
2.30
-27.030
0
1
CHAP.
COMPLEX REACTIONS
XVl]
731
427
600
IF. D . Eossini, E . J. R. Presaen and K. S. Pitzer, J. Nat.
Bureau of Standards, 27, 629 (1941), with permission!
bB + cC:?rR + sS
(2)
bB +
(3)
cC +
rR:^tT+uU
sS^vV
2bB + 2cC = tT + uU + vV
\nUcJ
/ ^ \ ( r + .)-(6 + 0
^A0
(35)
732
where
CHEMICAL EQUILIBRIUM
'Sn
= nB-\-nc-VnB-\-ns-\-nT
[CHAP.
XVI
+ nu-\-nv + ni
i
AGl = -RT\nKi
AGl^-RThiKi
AGl=-RT\nK^
(38)
(89)
(40)'
Ki = KiK^Ki
(42)
-=(tF)-'(ir"""'''
<-'
CHAP. XVI]
COMPLEX REACTIONS
733
of independent reactions which must be considered in equilibrium calculations is equal to the least number of equations which includes every reactant
and product which is present to an appreciable extent in the equilibrium
mixture including all phases.
For simultaneous solution of the equilibrium equations a definite quantity of the initial system is selected as a basis, and the number of moles
converted by each reaction in proceeding to equilibrium is designated
as an algebraic unknown. For example, in the system considered above
an equilibrium calculation may be based on 100 moles of the initial reactants. The number of moles of B converted by reaction (1) in going
to equihbrium may b6 designated as x. Similarly, y may represent the
moles of B converted by reaction (2), and z the moles of C converted by
reaction (3). The number of moles of all components in Equations (35),
(36), and (37) may be expressed in terms of these three variables x, y,
and z, which are then evaluated by simultaneous solution. The solution
may reqiire a graphical or trial-and-error procedure where the equations
are complex.
These principles are well illustrated by consideration of the catalytic
process for the production of hydrogen and carbon monoxide by the reaction of steam and methane at high temperatures. This process is extensively used for obtaining both pure hydrogen and mixtures of hydrogen and carbon monoxide for use in synthesis. A thermodynamic
analysis of the operation involved was presented by Dodge. ^ The kinetic
mechanism of a catalytic reaction of this type may involve several intermediate steps which are of importance in determining the rate of reaction, as discussed in Chapter XVIII. However, a sound thermodynamic
treatment is possible without consideration or knowledge of the true
mechanism."" It may be assumed that the principal reaction proceeds
in two stages with intermediate formation and removal of carbon.
Thus, these reactions with the corresponding equilibrium constants at
600C from the data of Tables XV and XXXV are as follows:
(1)
CH4 = C + 2H2;
Ki =
(2)
C-|-H20 = CO-t-H2;
K^^-
-^^2.1Z
iar,r) (flp )
- = 0.269
%.o
(3)'
K, = ' V ^ = 0.574
In order that no carbon may appear in the equilibrium mixture represented by these three reactions it is necessary that sufficient steam be
734
CHEMICAL EQUILIBRIUM
[CHAP.
XVI
At eoo^c
(4)
(5)
(6)
(7)
(8)
K4 =
Ki =
K, =
K, =
Kg =
2.21
8.14
4.95(10-1')
1.12(10-12)
5.51(10-)
At equilibrium,
Moles CH4 = 1 - X
Moles H2O =
5-x-y
Moles CO = x y
Moles H2 = 3a; + 2/
Moles CO2 = y
Total moles = 6 + 2a;
CHAP. XVI]
COMPLEX REACTIONS
r(x-.)(3. + .)Mr_i^r
Reaction (4):
735
^^^^^
L(l-x)(5-a:-!/)JL6 + 2xJ
r (.)(3x + .)
1,;,^,,.,,
L(a;-'!/)(5-x-y)J
These two equations are solved by assuming several values of x and calculating
the corresponding values of y from each equation. Because of the comphcated forms
of the individual equations the solutions are best carried out graphically. The values
of y from each equation are plotted against the assumed values of x. The intersection of these two curves gives the correct solution of the two equations. Thus
X = 0.9124
y = 0.633
Equilibrium, Mixture:
HjO
CO
H,
COj
Total
Moles
l-y = 0.0876
-x-y
= 3.4546
x-y = 0.2794
Sx + y = 3.3702
y = 0.6330
6 + 2x = 7.8248
^
= 63.4> (,K, = 8.U)
"CO
It follows from these ratios that with 5 moles of steam per mole of methane no carbon
is present at equihbrium. This calculation is repeated for steam ratios of 2 and 1.25.
The corresponding values of Oco'^H2/''H20 ^^^ plotted in Fig. 160, from which the minimum steam ratio is determined as 1.38. The limiting steam ratio can be calculated
directly from reactions (1) and (4), which embrace all components including carbon.
736
CHEMICAL EQUILIBRIUM
[CHAP.
XVI
CHAP. XVI]
METALLURGICAL REACTIONS
737
738
CHEMICAL EQUILIBRIUM
[CHAP. XVI
tions of temperature by means of the data of Tables V, XIV, and XXXV, together
with the data of Kelley*-' on the heat capacities and heats of vaporization:
For reaction (1),
iSGl = -RT In Ki = 49265 - 70.50r + 5.83T In T - 2.496(10-3)7"'
+ 0.336(lb-<')r3-5:^i?^
For reaction (2),
(a)
X = lb-moles of CO produced
K,=l(lr.i)
'
(e)
x(3 +x)
K, =
~
(3-(-x)(l-x)
(d)
Moles
1.0
0.977
0.012
1.989
Partial Pressure
0.603 atm
0.491
0.006
1.000
For each lb-atom of carbon consumed, 0.503/0.497 or 1.012 lb-atoms of zinc are produced, or 5.51 lb of zinc are formed per lb of carbon consumed.
(c) Minimum Temperature for Producing Liquid Zinc. If operating conditions are
* K. K. Kelley, "The Free Energies of Vaporization and Vapor Pressures of Inorganic Substances," U.S. Bur. Mines Bull., 383 (1935).
CHAP.
XVI]
METALLURGICAL REACTIONS
739
such that Uquid zinc may be produced directly at equilibrium conditions, the vaporization equilibrium of zinc must be considered as a simultaneous reaction. Thus
Zn (1) ^ Zn (g)
(4)
The equilibrium constant for this vaporization is equal to the vapor pressure of the
liquid zinc if ideal behavior is assumed, or Kt = P^n- 1 ^'g- 162 are plotted vapor
pressures as a function of temperature taken from the data of Maier.'
1200
1300
1400
1500
Temperature, K
FIG. 162. Equilibrium Conditions in the Reduction of Zinc Oxide.
The minimum temperature at which hquid zinc can be produced occurs when the
partial pressure of the zinc vapor is just equal to the vapor pressure of molten zinc.
This corresponds to the dew point of zinc vapor. The partial pressure of zinc vapor
P2n ^t different reduction temperatures is calculated by the method of part (b) and
tabulated in column 6 of Table A. In column 7 are the vapor pressures Pgn f liquid
zinc. The partial pressure of zinc vapor p^n ^<1 ^^^ vapor pressure of molten zinc
Pgn are plotted against temperature in Fig. 162. The intersection point A of these
740
CHEMICAL EQUILIBRIUM
[CHAP. XVI
two curves indicates that the minimum temperature at which molten zinc can occur
is 1292K, where the partial pressure of zinc vapor is 2.8 atm and the total pressure
is 5.6 atm. However, under these conditions a negligible amount of zinc is formed,
and higher temperatures and pressures must be employed to obtain appreciable yields
of the liquid.
TABLE A
COMPLETE VAPOHIZATION OP ZINC ASSUMED
<
yK
1100
1200
1300
1400
Ki
0.001666
0.009014
0.03853
0.1300
1500
0.3740
'
K,
Pzn ^^'
16.35
70.8
255.3
760.4
1940
X
0.980
0.978
0.976
0.976
TT Atm
0.322
1.607
6.31
20.01
0.973
54.25
PZn ^<
0.162
0.808
3.174
10.07
27.31
= Ki
0.43
1.20
3.06
6.33
12.2
^^
(i)
2y
These values are substituted in Equation (16) with the assumption that partial pressures are equal to activities.
Reaction (1),
ir =
Reaction (2),
= ^t
(J)
= Kj
(k)
CHAP. XVI]
741
(m)
P3
2/Xi(Pz + 2X1)
= K2
(n)
p3
or
(o)
{Pz^ + 2Xi)XiK2
From Equation (o) y is evaluated directly for any selected temperature which
fixes the values of Pgni ^i> ^^'^ ^2. The corresponding compositions and total pressures are evaluated from Equations (m) and (i). These results are tabulated in
Table B together with the percentages of the total zinc formed which is present in
the liquid state.
TABLE B
THE PRESENCE OP LIQUID ZINC CONSIDEBED
TemperaKt
ture K
1290
0.0339
1353
0.074
1400
0.1300
1500
0.3740
K,
Pzn
226
464
760.4
1940
2.80
4.6
6.33
12.2
1.00
0.603
0.390
0.192
0.976
0.970
0.961
0.941
Per Cent
Liquid Tin
100(1-^)
5.555
0
12.1
39.7
22.2
61.0
83.9
80.8
5r
The values of ir in Table B are plotted in Fig. 162 for comparison with those of
Table A which were based on the assumption of complete vaporization. From inspection of Fig. 162, 50 per cent liquefaction of zinc wiU occur at 1373K, 16.3 atm
pressure.
It is evident that the direct production of liquid zinc in yields approaching complete recovery would require operating conditions which cannot be attained with the
structural materials at present available.
EQUILIBRIA IN LIQUID SOLUTIONS
T h e fundamental thermodynamic principles of equilibrium are universally applicable, and Equation (6) is rigorous for reactions involving
liquid or solid solutions of all types. However, the application of
thermodynamic methods t o such systems has not been particularly
fruitful because of the complex relationships frequently existing between aativities and concentrations. This situation is illustrated b y
t h e activity coefficients developed in Chapter X I V for N a C l in aqueous
solutions. W h e n more t h a n one solute is involved, as is commonly t h e
case where reactions occur in solution, the complexity of the relationships is compounded to such a n extent as t o render the methods of little
742
CHEMICAL EQUILIBRIUM
[CHAP. XVI
(45)
(1)
MeCOs (8) = MeCOs (aq)
(2)
MeCOs (aq) = Me+ + + c o r "
(3)
MeCO, (s) + H2O = Me++ + OH" -|- H C O r
(4)
MeCOs (s) + H2CO8 (aq) = Me++ -|- 2HC0r
(5)
MeCOs (s) + 2H2O = Me(0H)2 (s) + H2CO3 (aq)
' K. K. Kelley and C. T. Anderson, "Contributions to the Data on Theoretical
Metallurgy; IV Metal Carbonates-Correlation and Applications of Thermodynamic
Properties," U.S. Bur. Mines Bull, 384 (1935).
CHAP. XVI]
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
SOLUBILITY OF CARBONATES
743
744
CHEMICAL EQUILIBRIUM
[CHAP.
XVI
the equilibrium of reactions (16) and (10) and is the maximum pressure
which can be in equihbrium with a solution which is in equihbrium with
MeC03(s). Higher CO2 pressures will result in disappearance of the
solid carbonate and formation of solutions whose compositions are fixed
by the CO2 pressure and the equihbria of reactions (2) and (8-14).
In dealing with the sparingly soluble carbonates the situation is simplified by the fact that th^ salts are completely dissociated in solution.
Thus, reactions (1) and (2), (6) and (7), and (13) and (14) maybe combined into single reactions and the dissolved salts, MeCOs, Me(0H)2,
and Me(HC03)2, disregarded. Furthermore, the solid forms of the acid
carbonates of the metals which form sparingly soluble carbonates are
not known to exist, and reactions (13) to (15) need not be considered.
Additional simplification results from the fact that in dilute solutioils
the activity of water is constant and equal to 1.0.
The equilibrium constant of a reaction in dilute solution is determined
from, its standard enthalpy and entropy changes. In working With
dilute aqueous solutions it is customary to express compositions in
terms of molalities and to select the standard state such that ajm = 1 . 0
where m = 0. The standard enthalpy change in dilute solution is obtained from Tables XIV, XV, and XVI. The standard entropy change
is determined from Table XXXV. I t may be noted that values of zero
are arbitrarily assigned to the heat of formation and the entropy of the
hydrogen ion in dilute solution. The corresponding free-energy change
of formation is then 4,655 cal per g-mole at 298.1K. All other ionic
heats of formation and entropies are thus expressed relative to the hydrogen ion since the individual absolute values are unknown.
Illustration 17.
298K:
CHA-f. XVI]
SOLUBILITY OF CARBONATES
745
equilibrium measurements and heat of reaction data. When such entropies are used for the reverse operation of calculating the equilibrium
constant, exactly the same heat-of-reaction data must be used. This
fact results in some confusion in the use of the heats of formation of
H20(l) and COaCg) from Table XIV. The values in this table are recent determinations by Rossini which differ slightly from the values reported by Bichowsky and Rossini. However, the entropies of the ions
and aqueous compounds in Table XXXV are all based on the original
Bichowsky and Rossini values of 68.37 and 94.23 for the heats of
formation of H20(l) and C02(g), respectively. Accordingly, these values
should be used for tl^e calculation of equilibrium constants in aqueous
solutions rather than the more accurate values of Table XIV.
The equilibrium composition of a system involving ions is calculated
by the procedure demonstrated in the preceding sections dealing with
complex reactions. In order to define the equilibriimi, it is desirable to
consider the smallest number of reactions which include all reactants
and products present at equilibrium. An algebraic equation relates the
concentrations of the components of each reaction to its equilibrium constant. An additional algebraic equation expresses the electrical neutrality of the solution, that is, the equality of the positive and negative
charges of all of the ions. A further equation which may prove useful
expresses the material balance of the dissolution. The equilibrium composition is evaluated by simultaneous solution of these equations.
Illustration 18. Calculate the complete compositioa of the solution obtained when
precipitated calcium carbonate is dissolved in water in contact with an atmosphere
containing a partial pressure of CO2 of 3 X 10~^ atm.
Solution: It may be assumed that the specified partial pressure of CO2 is above
that of the invariant point and that the system at equihbrium contains CaCOa (s),
Ca-^, CO3, HCO3-, H+, OH", and H2CO3 (aq). There are therefore six unknown
compositions to be evaluated, which requires five independent equihbrium equations
in addition to the equation of electrical neutrahty. The material-balance equation
cannot be used in this case, because CO2 may be gained or lost during the dissolution.
Although other selections are possible, it is convenient to consider the following
reactions for the estabhshment of the equilibrium equations. The corresponding
equiUbrium constants are calculated by the method of Illustration 17.
22^298
(a)
(b)
f ] l | ^
31.7 = - f M _ ^
liiKj'Ji
(e)
HCOr = H+ + CO3- -
(aq;
746
CHEMICAL EQUILIBRIUM
[CHAP. XVI
The equation of electrical neutrality may be written as follows if the chemical formulas are used to denote molahties:
(f)
These values may be substituted in Equation (f), resulting in an equation which contains only y as an unknown. Thus,
(3^64)00-) ^ (8.8)(10->5) ^ 3^_g^, _^ ^^^ ^ ^_^^^^^_^^^
y^
y
This equation is solved graphically or by trial and error.
y = HCO3- = (7.1) (10-^) g-mole per 1000 g H2O
'
The concentrations of the other ions are evaluated from the equations relating them
to y. Thus
H+ = (1.2)(10-) g-moIe per 1000 g H2O
OH- = (4.4)(10-) g-mole per 1000 g H2O
C O r - = (7.9)(10-) g-mole per 1000 g H2O
Ca++ = (3.7) (10-*) g-mole per 1000 g HjO
The. procedure of Illustration 18 may be repeated for other CO2 pressures and curves plotted relating the composition of the solution to the
equilibrium partial pressure of CO2 above it. Such curves for the solubility of CaCOs in water are shown in Fig. 163. It may be noted that
the concentration of the calcium ion passes through a minimum and -is
increased by either increasing or decreasing the CO2 pressure from this
point. As the CO2 pressure is increased, carbon dioxide is absorbed by
the solution, but as the pressure is reduced CO2 is evolved and the concentration of the 0 H ~ ion increases until solid Ca(0H)2 is formed. The
appearance of the added phase results in an invariant point at which the
composition of the solution and the partial pressure of the CO2 are fixed
as long as both solid phases are present. The conditions at the invariant
point are established by the following equation in conjunction with those
of Illustration 18:
(g)
CHAP. XVI]
747
SOLUBILITY OF CARBONATES
If calcium carbonate is dissolved in pure water in a closed liquid system which permits no gain or loss of carbon dioxide, an equilibrium partial pressure of CO 2 is established which is determined by the equations
of Illustration 18 together with the following material-balance equation
in which the formulas indicate molalities:
(h)
-14
0
-13- -12 -10 - 8 - 6 - 4 - 2
Logjo CO2 Partial Pressure, Atmospheres
+2
748
CHEMICAL EQUILIBRIUM
[CHAP.
XVI
Assuming that activities are equal to mole fractions, calculate the standard free^
energy change of the reaction at each temperature and the average values for the heatof-reaction and entropy change over this temperature range.
2. From the data of Tables V, XIV, and XXXV derive equations relating AG/T
to temperature for the following reactions:
(a)
(b)
(c)
C (s) + H2O = H2 + CO
(d)
CO2 -f C = 2 CO
CHAP. XVI]
PROBLEMS
749
The atomic heat capacity of graphitic carbon,^" related to TK, is 2.673 + 0.0026177
- 116,900/72.
3. From the liquid-state values in Table XXXV estimate the entropies in the
ideal-gaseous state at 298.1K for the following compounds:
nc
174
(a) n-Decane
(b) n-Butyl benzene
(o) n-Heptyl cyclohexane
180
223
In the absence of data on the physical properties of these compounds use Equations (III-16) and (III-l) for estimating vapor pressures at 298.1K and heats of
vaporization at the normal boiling points and Equation (VII-32) for the effect of
temperature on heat of vaporization. Critical temperatures should be estimated by
Equation (III-8), critical pressures by. (III-18), and liquid densities by Equation
(XII-38).
i. From the data of Tables XXXVI and XXXVII calculate the equilibrium constants and heats of reaction of the following teactions at temperatures of 298,600,800,
and 1000K:
(a)
(b)
(c)
6. The following values of (H HQ) for the ideal-gaseous state were calculated
by Pitzer and Scott," and the corresponding heats of vaporization at the normal boiling point and critical temperatures are from the International Critical Tables. From
the data of Tables XVI and XXXVII calculate the values of (AH/)o the heat of
formation at 0K in the ideal-gaseous state for each of these compounds. The difference between the heats of combustion at 291 K and 298K may be neglected as
less than the probable errors of the measuremeiits.
( H Ho)298kcal
(a) Benzene
(b) Toluene
(c) Ortho-xylene
per g-mole
3.415
4.314
5.604
XB
cal per g
94.4
86.5
82.8
nc
80.1
111
144.5
T'cC
289
321
358.3
750
CHEMICAL EQUILIBRIUM
[CHAP. XVI
(c)
(d)
C3H8 - C3H6 + Ha
(27.16){\(i-^)T^
n-Hexane"
4 = 4.296 -|- 118.661 X lO-^r - (42.13)(10-)7'2
10. Propane may be dehydrogenated catalytically to form propylene. From the
data of Table XXXVI develop curves relating the percentage of propane dehydrogenated at equilibrium to temperature in the range of 800-1200F and at pressures
of 0.5, 1.0, and 2.0 atm.
11. Water and chlorine react at elevated temperatures according to the following
equation:
4CI2 (g) -1- iH^O (g) = HCl (g) -f 4O2 (g)
Using the data of Tables V, XIV, and XXXV and the heat-capacity equation of
problem XIII-1, page 692,
(a) Calculate an equation for AG/T for this reaction.
1(6) Calculate the composition of the equilibrium mixture at SOOC starting with
equal volumes of chlorine and water and assuming that Kv 1.0.
(c) Repeat the calculation of part (6) for a pressure of 100 atm, evaluating Kp from
Fig. 142 and the critical data of Table XI, page 234.
12. Sulfur dioxide is reduced by hydrogen according to the following equation:
3H2 (g) + SO2 (g) = H2S (g) + 2H2O (g),
(a) From the data of Tables V, XIV, and XXXV derive an equation for the standard free-energy change of this reaction.
(6) Calculate the equilibrium composition of the. mixture obtained at 1200C and
atmospheric pressure, starting with three parts of hydrogen and one part of SO2.
(c) Repeat the calculation of part (6) at 100 atm, using Fig. 142 and the critical
data from Table XI, page 234,
13. Methyl alcohol is synthesized by passing a mixture of CO and H2 over a catalyst according to the following equation:
CO (g) + 2H2 (g) = CH3OH (g)
" J. W. Andersen, G. H. Beyer, and K. M. Watson, Natl. Petroleum News, Tech.
Sec, 36, fl476 (July 5, 1944). Also "Process Engineering Data," National Petroleum
Publishing Company, Cleveland (1944).
'3 H. M. Spencer and G. N. Flannagan, J. Am. Chem. Soc, 64, 2511 (1942).
CHAP. XVI]
PROBLEMS
751
From the data of Tables V, XV, and XXXV calculate the composition of the equilibrium mixture obtained at a temperature of 300C and a pressure of 240 atm, start^
ing with two parts of H2 and one part of CO, assuming that only this reaction takes
place. The critical temperature of CH3OH is 240C and the critical pressure 79 atm.
The heat capacity is given by the following equation (Chapter XVII, page 801) with
r in K:
. ' ''
Cp = 5.72 + (24.85) (10-3)r - (8.167)(10-*)r2
14. Methyl alcohol is oxidized by air to formaldehyde at 550C in a catalyst
chamber at atmospheric pressure. Calculate the percentage yield of formaldehyde
using the theoretical air supply and assuming no further oxidation.
CH3OH (g) + iO, (g) ^ HCHO (g) + H2O (g)
Entropy and heat-of-reaction data are given in Tables XXXV and XV. Heat capacities may be taken from Table V and problem 12 and the following equation for
HCHO12 with T in K:
Cp = 4.50 + (13.95) (10-5) r - (3.73) (10^)^2
15. In the Birkeland-Eyde process the nitrogen of the atmosphere is oxidized in
a long flaming electric arc:
1N2 + 4O2 = NO
Assuming that only this reaction takes place, calculate the percentage conversion"of
nitrogen to NO in air of average atmospheric composition at a pressure of 1.0 atm
and at temperatures of, respectively, 2000K and 3000K.
16. Carbon dioxide is reduced by graphite according to the equation:
C (graphite) + CO2 (g) = 2C0 (g)
Assuming that equiUbrium is attained, calculate the degree of completion of the reduction of pure CO2 under the following conditions, using the data of Table XXXVII:
(a) A temperature of 1000K and a pressure of 1.0 atm, assuming Kv = 1.0
(6) A temperature of 1500K and a pressure of 1.0 atm, assummg Kv 1.0
(c) A temperature of 1000K and a pressure of 100 atm
17. A mixture of 79 per cent N2 and 21 per cent CO2 by volume is passed over
hot carbon (graphite) at a temperature of 1000K and a pressure of 1.0 atm. Using
the data of Table XXXVI calculate the equilibrium composition of the gases, and
compare this result with that of part (a) of problem 16.
18. Carbon monoxide is burned with pure oxygen'in the theoretically required
proportions. Calculate the degrees of completion of the oxidation if equilibrium is
attained at temperatures of, respectively, 1000K and SOOO'K, under a pressure of
1.0 atm. Evaluate iiG/T at 3000K by extending the data of Tables XXXVI and
XXXVII from 1500K through graphical integration of the heat capacities of
Table IV, page 2^2.
19. Water gas leaves a generator containing 51.1 per cent H2, 2.3 per cent CO2,
and 46.6 per cent CO by volume on the dry basis. Ten per cent of the steam which
was introduced into the bottom of the generator passed through the bed of hot coke
without decomposition and is present in the gases. This gaseous mixture is passed
into a reaction chamber under a pressure of 1.0 atm in contact with a catalyst of
chromium oxide and allowed to attain equiUbrium at a temperature of 700K (423C).
Calculate the equilibrium composition of the gaseous mixture, using the data of
Fig. 156.
752
CHEMICAL EQUILIBRIUM
[CHAP. XVI
20. One volume of the initial wet water gas described in problem 19 is mixed with
three volumes of additional water vapor. THis mixture is passed into the reaction
chamber operated at the conditions described in problem 19 and allowed to reach
equilibrium.
(a) Calculate the equilibrium composition of the gaseous mixture.
(b) Calculate the composition of the residual gas if the CO2 and H2O are removed
from the gaseous mixture of, part (a) after equihbrium is attained.
21. The hydrate of sodium carbonate decomposes according to the following
equation:
Na2C03 H2O (s) = NaaCOa (s) + H2O (g)
The equilibrium pressure in atmospheres of water vapor in this reaction is given by
the following equation:
log p = 7.944 - 3000.0/rK
/
Derive an expression for the standard free-energy change of this reaction.
22. Zinc oxide is reduced with carbon monpxide, under a pressure of 1.0 atm according to the following reaction:
ZnO (s) + CO (g) = Zn (g) + CO2 (g)
Calculate the degree of completion of the oxidation of CO at atmospheric pressure
under the following different conditions, assuming that equilibrium conditions are
attained and that ZnO is always present:
(a) At a temperature of 1000C, using pure CO
(b) At a temperature of 1500C, using pure CO
(c) At a temperature of 1000C, using a mixture of 27.5 per cent CO, 4.3 per cent
CO2, and 68.2 per cent N2 by volume
(d) At a temperature of 1500C, using a mixture of 27.5 per cent CO, 4.3 per cent
CO2, and 68.2 per cent N2 by volume
23. Sodium bicarbonate is calcined according to the following equation:
2NaHC03 (s) = Na2C03 (s) + H2O (g) + CO2 (g)
Calculate the pressure of the equimolecular mixture of H2O and CO2 in equilibrium
with NaHCOa at a temperature of 100C.
24. (a) Calculate the boiling point of aluminum at atmospheric pressure from the
following data:'
G-H;
G-Hg
TemperaT
T
ture, K
Cos I
Solid or Liquid
298.1
-33.766
-3.13
1000
-40.217
-9.09
2000
-43.762
-14.64
2100
-44.009
-15.01
2200
-44.245
-15.37
2300
-44.470
-15.71
2400
-44.681
-16.04
The value of AHJ for vaporization is 66.920 kcal per g-atom,
(b) Calculate the vapor pressure at 200G''K.
25. Considering each of the following reactions:
Sec,,
Publishu
" H . M.
CHAP. XVII
PROBLEMS
753
Tabulate the effects of the following changes upon (a) the velocity of reaction (moles
transformed per unit time per unit volume), (6) the equilibrium degree of completion,
and (c) the actual degree of completion obtained in a specified time interval:
(1)
(2)
(3)
(4)
(5)
Increase of temperature
Increase of pressure
Provision of a positive catalyst
Dilution with an inert gas
Agitation of the reacting system
Temperature, C
150C
150C
200C
200C
30. From the data of Table XXXVII calculate the composition of the equilibrium
mixture of the five isomeric hexanes at a temperature of 600K. Calculate the heat
of reaction in converting pure normal hexane to the equilibrium mixture in the idealgaseous state at this teiSperature.
31. When propane is pyrolyzed the following reactions take place:
CsHg > CsHe -|- Hj
CgHa > C2H4 -f- CHi
Assuming that only these two reactions occur, calculate from the data of Table
XXXVI the composition of the equilibrium mixture formed by heating propane
at 1400F and 1 atm.
32. Propane also decomposes to form carbon and hydrogen at high temperatures.
Calculate the composition of the equilibrium mixture of probleni 29 if this reaction
is considered.
774
THERMODYNAMIC PB^ERTIES
[CHAP.
XVII
In T
(26)
^1
RlnQ
0
r,d}n_Q
dlnT
(27)
(28)
However, the most general statement of the third law of thermodynamics derived by statistical mechanics states that the entropy of a substance at the absolute zero is equal to R times the logarithm of the statistical
weight of the ground energy level, or si = R In go. For substances in the
crystalline state at 0K the statistical weight of the ground level is generally unity, leading to the more common statement of the third law.
Equation (28) then becomes
s'L = R\nQ + R-^
29)
d In 1
Combining Equations (24) and (29) gives expressions for the m contributions to G and A, thus,
(G - H)
= - f t In Q =
(A-HIU
,,
(30)
d In T
RT
RTQ
^ '
CHAPTER XVII .
THERMODYNAMIC PROPERTIES FROM MOLECULAR .
' STRUCTURE
The application of thermodynamic principles is in many cases hampered by lack of data which are sufficiently reliable to be useful for engineering design. The accuracy with which standard free energies mustf
be known is evident from consideration of the error AK, in the equiUbrium constant which corresponds to an error A(AG) in the standard freeenergy change. Thus, from Equation (XVI-6) at constant temperature,
-AiAG) = RTln(^+l\
(1)
757
Where reasonably reliable entropy and heat-capacity data are available or can be estimated by the procedures outlined in this chapter, a
complete expression for the equilibrium constant which is satisfactory
for many purposes may be developed from a single experimental measurement of the compositions at equilibrium under conditions not far removed from the range of interest. The standard heat of reaction i^
is calculated from Equation (XVI-7) from the kno\vn entropy and equilibrium constant. Equilibrium constants at other conditions may then
be calculated from Equations (XVI-6) and (XVI-11). In this manner a
value of AH is obtained which is consistent with the value of /^S in the
expression for the equilibrium constant, and moderate errors in the entropies used will not seriously affect equilibrium calculations over a
limited range of conditions.
EMPIRICAL CORRELATION OF ENTROPIES
Methods o"8^forreIating the entropies of inorganic compounds are reviewed by Wenner,^ who points out that the entropies of similar compounds in the solid state vary with molecular weight in accordance
with the following equation:
s, = A\ogM + B
(2)
where
s = molal entropy
M = molecular weight
A, B = constants characteristic of the type of compound
On this basis a group of similar compounds should yield a straight line
when molecular weight is plotted on a logarithmic scale against entropy
on a uniform scale. Data on two compounds serve to establish such a
line, or the constants of Equation (2), from which entropies of similar
materials may be estimated.
Wenner found that the points for individual compounds in each group
fall fairly well on a straight line for each of the following groups of metallic compounds in the solid state: Me02, MeO, MeS, MeNOa, and metallic
haUdes, MeX and MeX2. A further generalization pointed out is that
the addition of 1 mole of H2O to a soHd compound causes an entropy
increase of 10 units in forming a crystalline hydrate, 8.2 in forming an
inorganic base from its oxide, and 7 units in forming an organic acid
from its corresponding anhydride.
In the gaseous state Wenner shows that molal entropies vary with
molecular weight according to the equation:
logs(g)=Alogilf-l-B
(3)
* R. R. Wenner, " Thermochemical Calculations," McGraw-Hill Book Company
(1941).
758
THERMODYNAMIC PROPERTIES
[CHAP. XVII
Various methods for empirically correlating heats of formation, entropies, and heat capacities of organic compounds were reviewed by
Andersen, Beyer, and Watson^.who proposed a scheme whereby these
properties for the ideal-gaseous state are resolved into contributions
attributable to atomic groups. From the restllting tables the properties
of complex molecules are readily estimated by summation of the contributions of their component groups. The corresponding properties in
the liquid and nonideal-gaseous states may then be calculated by the
methods of Chapter XII.
The molal values for the ideal-gaseous state of heats of formation at
25C, entropies at 25C, and 1 atm, and the constants a, b, and c of the
three-term heat-capacity equation (VII-21), page 213, were resolved
into group contributions on the following basis:
Each compound is considered as composed "of- a basic group which is
modified by the substitution of other groups for atoms comprising it.
For example, all paraffin hydrocarbons may be considered as derived
from methane by successive substitution of CH3 groups'for hydrogen
atoms. Similarly, any secondary amine can be considered as derived
from the base group NH(CH3)2. The contributions of nine base groups
are given in Table XXXIX.
The contributions resulting from the primary substitution of a methyl
group for a hydrogen atom in any one of the base groups is given in
Table XL. In the cases of benzene, naphthalene, and cyclopentane, the
base group contains several carbon atoms, and successive substitutions
on different carbon atoms involve different contributions depending upon
the number and position of the substituted groups. For the naphthenes
the terms ortho, meta, and para are taken as indicating a minimum separation of the two substituted groups by respectively 0, 1, and 2 intermediate carbon atoms in the ring. The heat-capacity coefficients, a, b,
^ J. W. Andersen, G. H. Beyer, and K.^M. Watson, Nat'l Petroleum News, Tech.
Sec., 36, fi476 (July 5,1944). Also " Process Engineering Data," National Petroleum
Publishing Company, Cleveland (1944).
CHAP. XVII]
775
R'T^Q
-li.
^ ZjE^gie
RTQ
RT^
d\nQ
R'T^Q
RQ^
)\dT)
_ /d In QV
dlnT
\d In Tj
^ '
From Equations (31) and (32) it is seen tliat all the derivatives of the
partition function which are required for the evaluation of thermodynamic properties can be calculated from two summations of all significant
energy levels, one SjBigfiC ^^ and the other Sifif giC '^. For simple molecules the individual energy levels can be evaluated by application of
Equation (6) to spectroscopically determined frequencies of emission or
absorption.
Illustration 7. T h e development and application of these methods for calculating
thermodynamic properties is outhnod by Kelley'", who developed the following calculation of the thermodynamic properties of nickel vapor in the state of an ideal gas
a t 298K and 1 atm. This is an entirely hypothetical state in which nickel vapor
cannot exist but is legitimately used as a reference from which values for actual
states may be derived by the temperature and pressure relations developed in Chapters X I and X I I .
Nickel vapor, Ni (g), is a monatomio gas possessing only translational and electronic-energy contributions. In Table A the spectroscopic notations for the various
levels of electronic energy are given in column 1 and the corresponding frequencies
in terms of wave numbers and statistical weights, derived from the spectrum, in
columns 2 and 3, respectively. The molal energy levels in column 4 are calculated
from Equation (6) in calories per gram-mole. The three summations required for
calculation of thermodynamic properties are given in columns 5, 6, and 7. The
electronic contributions to the thermodynamic functions are calculated directly from
these summations. Thus, from Equations (20), (31), and (32), and Table A,
Q = 11.690
d In Q
1753
= 0.2532
d\nT
(1.987) (298.1) (11.69)
dMnQ
1,533,000
-0.2532 -(0.2532)2 = 0.0565
rf(lnr)2
(1.987)^298.1)2(11.69)
TABLE A
1
State
^Ti
3r.3
3n.
Fa
3D,
%a
0)
9i
Ei
0.0
204.82
879.82
1332.15
1713.11
2216.55
9
7
6
7
3
5
0
585.27
2513.98
3806.62
4895.21
6333.79
B
ff-ie
e
RT
9.0000
2.6058
0.0717
0.0113
0.0008
0.0001
Q = 11.690
QiEie
7
RT
0
1525.1
180.3
43.0
3.9
0.6
1753
giE\e~'Sf
0
892,610
453,200
164,060
18,500
4,551
1,533,000
CHAP. XVII]
GROUP CONTRIBUTIONS
759
b(lO')
c(,W)
Ideal Gas at T'K
AH;298.I (g)
Swa.i (g)
Group
cal/(g-mole) (K)
Methane
Cyclopentane
Benzene
Naphthalene
Methylamine
Dimethylamine
Tfknethylamine
Dimethyl ether
Fonnamide
-17.9
-21.4
18.1
35.4
-7.1
-7.8
-10.9
-46.0
-49.5
44.5
70.7
64.4
80.7
57.7
65.2
3.42
2.62
0.23
3.15
4.02
3.92
3.93
6.42
6.51
%
63.7
17.85
82.67
77.83
109.40
30.72
48.31
65.85
39.64
25.18
-4.16
-24.72
-27.16
-34.79
-8.70
-14.09
-19.48
-11.45
-7.47
TABLE XL
CONTBIBUTIONS OF PRIMARY C H 3 SUBSTITUTION GROUPS REPLACING H T D B O G E N
A(AH;298.I) (g)
Base Group
1. Methane
-2.2
2 Cyclopentane
(o) Enlargement of ring 9.3
(b) First substitution 5.2
(c) Second substitution:
ortho
-12.2
meta
8.4
para
7.1
(d) Third substitution - 7 . 0
3. Benzene and naphthalene
(a) First substitution 4.5
(6) Second substitution:
ortho
6.3
meta
6.5
para
8.0
(c) Third substitution
(sym)
4. Methylamine
5.7
5. Dimethylamine
6.3
6. Trimethylamine
4.1
7. Fonnamide
Substitution on C atom 9.0
AS29S.1 (g)
Aa
Ab(lO') Ac(10)
Ideal Gas at fK
10.4
-2.04
24.00
-9.67
0.7
11.5
-1.04
-0.07
19.30
18.57
-5.79
-5.77
-0.24
16.56
-5.05
12.0
0.36
17.65
-5.88
8.1
9.2
7.8
5.20
1.72
1.28
6.02
14.18
14.57
1.18
-3.76
-3.98
8.0
'~~ .
0.57
16.61
-5.19
-0.10
17.52
-5.35
6.11
-1.75
4.75
7G0
THERMODYNAMIC PROPERTIES
[CHAP. XVll
CH3
-i
IHj
CH
I
1
I
Two special secondary substitutions are defined in Table XLI for use
in calculating the properties of esters and ethers. One is the substitution
of a methyl group for the hydrogen of a carboxyl group to form a methyl
ester. The other is the substitution of a methyl group for one of the
hydrogens of a methyl ester or ether to form an ethyl ester or ether. If
additional substitutions are made on this same carbon atom, the contributions are evaluated from the corresponding values of A and B based
on the type numbers of the carbon atoms involved.
In Table XLII are the contributions resulting from the substitution
of multiple bonds for single bonds between two carbon atoms of types A
and B, respectively. An additional contribution must be added for each
pair of conjugated double bonds formed by such substitutions.
In Table XLIII are the incremental contributions resulting from the
substitution of various groups for one or two methyl groups. Thus, if
a methyl group is replaced by an OH group the contribution to the heat
of formation is 32.7. If two methyl groups are replaced by an oxygen
atom to form an aldehyde the contribution is 12.9. It may be noted
that the phenyl group is included in Table XLIII in addition to being
designated as a base group in Table XXXIX. This substitution contribution is used in calculating the properties of complex compounds in
which several base groups are combined, as, for example, in polybasic
aromatic acids.
The contributions to heats of formation resulting from substitution of
chlorine for methyl groups vary with the number of substitutions made
on a single carbon atom. Corresponding variations were not found for
the contributions to entropy or heat capacity or for the substitution of
the other halogens. As noted in the table a correction must be apphed
to t^e entropies calculated for the halogenated methanes. In general
GROUP CONTRIBUTIONS
CHAP. XVII]
761
TABLE XLI
SECONDARY METHYL SUBSTITUTIONS REPL.ACING HYDROGEN
A(AH;)J9S.I
A
1
1
1
1
1
2
2
2
2
2
3
3
3
3
3
1
B
kcal
1
2
3
4
5
1
2
3
4
6
1
2
3
4
5
0in ester
or ether
Substitution of H
ofOHgrou pto form
ester
(g)
perg-mole
-4.5
-5.2
-5.5
-5.0
-6.1
-6.6
-6.8
-6.8>
-5.1
-5.8
-8.1
-8.0
-6.9
-5.7
-9.2
AS298.1 (g)
cal/(g-mole) (K)
9.8
9.2
9.5
11.0
10.0
5.8
7.0
6.3
6.0
2.7
2.7
4.8
6.8
1.7
1.3
A6(103)
Ideal Gas at
-0.97
22.86
18.47
1.11
1.00
19.88
17.12
1.39
0.10
17.18
17.60
1.89
1.52
19.95
1.01
19.69
2.52
16.11
17.42
0.01
-0.96
27.47
-1.19
28.77
-3.27
30.96
-0.14
24.57
0.42
16.20
Aa
Ac(10)
T'K
-8.75
-6.85
-8.03
-5.88
-5.20
-6.21
-8.57
-7.83
-5.88
-5.33
-12.38
-12.71
-14.06
-10.27
-4.68
-7.0
14.4
-0.01
17.58
-5.33
+9.5
16.7
0.44
16.63
-4.95
TABLE XLII
MULTIPLE-BOND CONTRIBUTIONS REPLACING SINGLE BONDS
A
1
1
1
2
2
2
2
3
Type oj
Bond
=
=
=
=
=
=
=
=
A ( A H ; ) 2 9 8 . 1 (g)
AS^gS.! (g)
B
Iccal per g-mole cal/ (g-mole) (K)
-2.1
1
32.8
2
0.8
30.0
2.2
28.2
3
2
28.0
-0.9
2 cis
-0.6
28.4
-1.2
2 ttans
27.5
1.6
26.7
3
3
,25.5
-10.4
-6.8
-7.8
-6.3
-4.3
Ac(106)
Ab(lO')
Ideal Gas at TK
1.33
-12.69
-1-4.77
1.56
-14.87
-f5.57
0.63
-23.65
-f-13.10
0.40
-18.87
-f9.89
0.40
-18.87
-t-9.89
0.40
-18.87
4-9.89
+13.10
0.63
-23.65
-4.63
-17.84
+11.88
Aa
Approximately
5.58
-31.19
6.42
-36.41
4.66
-36.10
zero
+11.19
+14,53
+15.28
Approximately zero
762
THERMODYNAMIC PROPERTIES
[CHAP. XVII
TABLE XLIII
SUBSTITUTION G B O U P CONTRIBUTIONS REPLACING CHa1 G R O U P
A(AH/)29a.i (g)
AS298.1 (g)
Aa
cal/(g-mole)(K)
Ab(lO')
Ac(10)
Ideal Gas at TK
2.6
3.17
-14.86
2.0
4.0
6.3
3.64
-19.53
-13.92
10.36
4.53
2.19
-18.85
6.26
2.81
2.24
2.73
3.61
6.02
8.50
4.07
-0.79
1.26
-19.41
-23.61
-17.37
-55.72
-66.08
-15.07
-24.96
53.63
-7.32
6.33
11.79
4.09
22.72
30.21
7.94
12.37
-19.21
2.23
3.0t
-i.ot
5.0t
-12.3
-2.4
15.4
5.2
21.7
-4.8
5.59
t Add 1.0 to the calculated entropy contributions of halides for methyl derivatives;
for example, methyl chloride = 44.4 (base) + 10.4 (primary CH3) 0.0 (CI substitution) + 1.0.
CHAP. XVII]
GROUP CONTRIBUTIONS
763
2
2
2
-6.8
-6.8
-8.0
56.6
The value found by Rossini and co-workers^ is 56.2 kcal per g-mole.
Side methyl'groups
The value of AH/298, i calculated from the heat of combustion listed by Kharasch* is
147.1 kcal per g-mole.
Illustration 3. Approximate the entropy of 2,2,3,3-tetramethyl butane
(a) Base group (methane)
Table XXXIX
44.5
Primary CH3
Table XL
10.4
Secondary CH3 substitutions replacing hydrogen
Table XLI
A
Secondary CH3 groups in 4 C chain
1:
9.8
9.2
2
3
3
4
7.0
6.3
5.8
1.7
94.7
Table XXXIX
Table XL
Table XLI
44.5
10.4
B
1
2
THERMODYNAMIC PROPERTIES
764
[CHAP. XVll
B
1
2
2
2
4
4
II
9.8
9.2
7.0
2
4.8
3
Side methyl groups counterclockwise
6.0
i2
1.7
'3
93.4
The average result for the entropy of 2,2,3,3-tetramethyl butane is 94.05 cal/
(g-mole) (K) which is in agreement with the value found by Pitzer.'
Illustration 4. Approximate the entropy of 1,2-dibromoethane.
Secondary CH3 groups in 4 C chain
Table XLI
Table XLIII
Table XLIII
44.5
10.4
9.8
9.2
3.0
3.0
79.9
5 C chain (Table
XLI)
Side methyl groups
A6(102)
AcClO")
3.42
-2.04
17.85
24.00
-4.16
-9.67
A
1
1
1
B
1
2
2
-0.97
1.11
1.11
22.86
18.47
18.47
-8.75
-6.85
-6.85
2
2
2
3
Hiooo H29S.1
1.52
19.95
-8.57
1.01
19.69
-7.83
-52.68
5.16
141.29
-1000
=I
(5.16 + 141.29(10-=)r . ,52.68(10-)r2) d r
-'298.1
lO.L
r
niooo
= 5.16? + 70.64(10-')7'2 _ (17M){10-^)T'
= 60,890 cal per g-mole
Pitzer' reports a value of 50,550 cal per g-mole.
Extensive comparisons with the data from the literature lead Andersen, Beyer, and Watson to conclude that in general molal heats of formation and entropies calculated by the "group-contribution method differ
from the better experimental values by less than 4.0 kcal and 2.0 entropy
units, respectively. Calculated heat capacities appear to be within
5 per cent of the accepted values, although serious discrepancies exist
between the experimental values of different investigators. In many
CHAP. XVII]
STATISTICAL METHODS
765
cases, particularly for heats of formation, it is believed that the calculated valuQS may be preferable to the experimental.
The contributions in Tables X X X I X to XLIII in some cases are based
on data of questionable accuracy and will be subject to revision as better
experimental values become available. This method of calculation may
be extended to other Series of compounds if data are available to establish the necessary base-group contribution. In many cases the properties of such base groups may "be estimated by the theoretical methods
described in the following sections. Properties of higher homologs or
derivatives .may then be estimated from the group contributions. It is
believed that this procedure in many cases is more reliable than direct
application of the simplified forms of statistical calculations to the
complex molecules.
Heats of formation and heat capacities estimated from group contributions are sufficiently accurate for use in energy balances except
where heats of reaction are very small or must be known with unusual
accuracy. Equilibrium constants based on the estimated entropies and
heats of formation are satisfactory for predicting the feasibility of a reaction but not for accurate calculation of equilibrium compositions.
For accurate equilibrium constants the estimated entropy and heatcapacity data are best combined, as previously outlined, with a measured equilibrium constant to establish a consistent heat of reaction.
STATISTICAL METHODS
766
THERMODYNAMIC PROPERTIES
[CHAP.
XVII
development presented represents an amplification of the outline published by Kelley'" with an extensive bibliography of current literature.
Molecular Energy of an Ideal Gas. The internal energy of a molecule
is present in kinetic and potential forms resulting from the motion and
attractive forces of the molecule and its parts., These .forms of energy
may be classified in the following five groups:
1. Energy of translation of the molecule as a whole designated as Vt
per mole or et per molecule. This form of energy was discussed in Chapter I I and is equal to (3/2)i?r per mole or {3/2){RT/N) = (3/2)fer per
molecule where N is the Avogadro number and k is termed the Boltzmann constant.
2. External rotational energy resulting from rotation of the molecule
as a whole, designated as Vr or e,. Just as in the rotation of large bodies,
such rotational energy may be resolved into components about each of
three perpendicular axes passing through the center of gravity of the
molecule and is a function of the frequency of rotation and the moments
of inertia about these three axes.
3. Internal rotational energy resulting from the rotation of groups of
atoms in the molecule with respect to other groups in the same molecule
and designated as Ur' or e,-. A simple example is the ethane molecule
in which one CH3 group rotates with respect to the other about the
C-C bond. Significant internal rotational energy is believed to result
only from the rotation of groups of atoms, not single atoms, about singlevalence bonds. It is a function of the, moments of inertia of the rotating
groups about the axis of rotation, the frequency of rotation, and any attractive forces between the rotating groups which hinder rotation. Rotation which occurs without such restrictive forces is termed free rotation,
and, if significant attractive forces are encountered, it is termed hindered
rotation. For example, in the ethane molecule as a CH3 group rotates
about the C-C bond, at three points in each revolution its hydrogen
atoms attain minimum distances from the hydrogen atoms of the other
CH3 group. At these three positions the restrictive force hindering rotation is a maximum. The energy required to rotate such a group from
a position of minimum restrictive force to a position of maximum force
is termed the potential barrier restricting rotation and is expressed in
molal energy units. The energy associated with hindered rotation is
less than the energy of free rotation of the same group by an amount
depending on the magnitude of the potential barrier and the number of
times it is encountered per revolution. In complicated molecules ro" K . K. Kelley, "Contributions to theData of Theoretical Metallurgy; IX The
Entropies of Inorganic Substances," Revision (1940) of Data and Methods of Calculation, U.S. Bur. Mines Bull., 434.
CHAP. XVIl]
767
768
THERMODYNAMIC PROPERTIES
[CHAP. XVII
and rotational freedom, two degrees of vibrational bond-stretching freedom, and one degree of bend-bending freedom.
The degrees of freedom of a molecule exclusive of its translational
freedom are termed its internal degrees of freedom, which include all freedoms for external and internal rotation, bond stretching, ^nd bond
bending. From the foregoing discussion it is evident that any molecule
possesses 3n 3 internal degrees of freedom.
If only the degrees of freedom for internal rotation and vibration are
considered, for a linear molecule,
Ur- + n + ns = 3w 5
(i)
_
nr' = degrees of freedom for internal rotation
n = degrees of freedom for stretching vibration
ns = degrees of freedom for bending vibration
(5)
' .
CHAP. XVII]
TRANSLATIONAL CONTRIBUTIONS
769
where
e = energy per quantum, ergs per molecule
h = Planck's constant = (6.624)(IQ-^') erg sec
V = frequency, reciprocal seconds
c = velocity of light = (2.99776) (10i) cm per sec
X = wave length, cm
CO = wave number, 1/X = reciprocal cm
Because of their convenient numerical magnitude, wave nimibers w
are commonly used to designate the frequency or wave length of radiation. Wave numbers are often referred to as frequencies, whereas actually the wave number has the dimension of reciprocal centimeters. The
distinction between wave numbers w and true frequencies v should be
carefully noted.
From Equation (6) it is evident that changes between widely separated
energy levels emit or absorb radiation of high frequency and wave number or short wave length. By spectroscopic measurement of the frequency of emitted or absorbed radiation it is possible to evaluate the
various levels of molecular and atomic energy. Thus, the large energy
changes resulting from shifts of electrons correspond to radiation of short
wave length in the ultraviolet or visible regions of the spectrum. The
radiation of medium wave length corresponding to changes in vibrational energy is in the visibleor infrared region, while the frequencies of
rotational energy changes are detected by Raman spectra.
Translational Contributions to Thermodynamic Properties. In the
development of relationships between molecular energies and thermodynamic properties it is convenient to consider separately the contributions resialting from the various forms of internal energy. It has been
pointed out that the total internal energy of a gas is the sum of the individual contributions resulting from the five forms of internal energy.
Since entropy is an extensive property, determined by energy content
and its availability, the total entropy can also be expressed as the sum
of the entropy contributions resulting from the five forms of internal
energy. Similar summations represent the total enthalpy, free energy,
and total work function. Derived properties such as the heat capacities
can also be expressed as summations of the contributions due to each
form of energy.
It was pointed out in Chapter II that the pressure and volume relations of an ideal gas are completely determined by the translational energy of its molecules. I t was also shown in Chapter XI that, although
the internal energy of an ideal gas is dependent only upon temperature,
its entropy is a function of pressure or volume as well as temperature.
770
THERMODYNAMIC PROPERTIES
[CHAP. XVII
It follows that for an ideal gas the variation of entropy and othfer thermodynamic properties with pressure and .volume result solely from translational contributions and that contributions from the other four forms of
energy are independent of pressure or volume. For this reason it is convenient to develop separately all translational contributions to the
thermodynamic properties.
The translational contribution to internal energy is given by Equation (II-7), page 31, as
v1 = f i j r
(8)
Combination of Equations (XI 134, 137, 139), page 475, with.Equation (8) gives
clt = i B
(9)
c;, = 1/2
^
(10)
Hi = fiJT
(11)'
These are the properties of a perfect monatomic gas which possesses only
translational energy. As was pointed out in Chapter XI, the absolute
entropy of such a gas cannot be arrived at by simple integration of the
thermodynamic relations because of the indeterminant lower limits encountered at the absolute zero. However, the translational, contributions to entropy have Seen derived by statistical methods and are expressed by the Sackur-Tetrode equation which has been verified by
experimental measurements on monatomic gases.
s1 = | f i l n M - | - f i 2 h i r - Z i : h i p - 2 . 2 9 8
or at 298.1''K and 1 atm,
^
(12)
(14)
(15)
'
(16)
(\7)
CHAP. XVll]
1. Heat Capacities:
771
For a perfect gas the heat capacities c and Cp are independent of the temperature.
2. Interned Energy: From Equation (8), u j = 2.980T
3. Enthalpy: From Equation (11), B, = 4.966r
- Rlnl
til
Ht
8,
888.4
1480.7
36.315
-31.349
298.16K
2483.1
1489.9
38.882
500K
-33.916
2979.8
4966.3
1000K
42.325
-37.359
All t h e preceding values are expressed in caI/(g-mole)(K).
A?
T
-33.336
-35.903
-39.346
The Partition Function. One mole of an ideal gas comprising N molecules contains individual molecules possessing many varying energy
levels, which result from various combinations of different levels in the
several degrees of freedom other than translation. Of the N molecules,
NNa may have an energy level a, NNb an energy level h, and so on,
where Na, Nh, represent the fractions of the total number of molecules having energy levels o, &, . Then
N = NNa + NNb + NNo+
2NNi
(17a)
+ NcEc + = U? + XNiEi
(18)
772
THERMODYNAMIC PROPERTIES
[CHAP. XVII
(19)
where
(20)
CHAP. X V I I ]
773
,
_
\
)
(21)
dT
Combining (21) and (22) gives
(22)
RT''
(24)
+ R^^M.
(25)
774
THERMODYNAMIC PROPERTIES
[CHAP.
XVll
(26)
(27)
0
(28)
However, the most general statement of the third law of thermodynamics derived by statistical mechanics states that the entropy of a substance at the absolute zero is equal to R times the logarithm of the statistical
weight of the ground energy level, or si = R In go- For substances in the
crystalline state at 0K the statistical weight of the ground level is generally unity, leading to the more common statement of the third law.
Equation (28) then becomes
s^^BlnQ+R^^
(29)
aln r
,
Combining Equations (24) and (29) gives expressions for the m contributions to G and A, thus,
(G-Hg),^_^^^^^(A-^Hg).
^^^^
3.
dhiT
RTQ
^^
CHAP. X V I I ]
775
^iE^gie
d(ln Ty
'^^
R^T^Q
^iEfgiC
RTQ
R^T^Q
RQ^
)\dT)
mi
dhiT
From Equations (31) and (32) it is seen that all the derivatives of the
partition function which are required for the evaluation of thermodynamic properties can be calculated from two summations of all significant
energy levels, one 'ZnEiQie ^ ^ and the other "LiElgie r. For simple molecules the individual energy levels can be evaluated by appUcation of
Equation (6) to spectroscopically determined frequencies of emission or
absorption.
Illustration 7. The development and application of these methods for calculating
thermodynamic properties, is outlined by Kelley^", who developed the following calculation of the thermodynamic properties of nickel vapor in the state of an ideal gas
at 298K and 1 atm. This is an entirely hypothetical state in which nickel vapor
cannot exist but is legitimately used as a reference from which values for actual
states may be derived by the temperature and pressure relations developed in Chapters XI and XII.
Nickel vapor, Ni (g), is a monatomic gas possessing only translational and electronic-energy contributions. In Table A the spectroscopic notations for the various
levels of electronic energy are given in column 1 and the corresponding frequencies
in terms of wave numbers and statistical weights, derived from the spectrum, in
columns 2 and 3, respectively. The molal energy levels in column 4 are calculated
from Equation (6) in calories per gram-mole. The three summations required for
calculation of thermodynamic' properties are given in columns 5, 6, and 7. The
electronic contributions to the thermodynamic functions are calculated directly from
these sumlmations.. Thus, from Equations (20), (31), and (32), and Table A,
Q = 11.690
d In 0
1753
= 0.2532
dhiT
(1.987) (298.1) (ll.e
d2 In Q
1,533,000
-0.2532 -(0.2532)2 = 0.0565
d(hi TY (1.987)^298.1)^11-69)
TABLE A
1
State
^y^
3n3
3ns
3^3
3ni
3F,
Cl)
9i
Ei
9,je BT
QiEiB RT
0.0
204.82
879.82
1332.15
1713.11
2216.65
9
7
5
7
3
5
0
585.27
2513.98
3806.62
4895.21
6333.79
9.0000
2.6058
0.0717
0.0113
0.0008
0.0001
Q = 11.690
0
1525.1
180.3
43.0
3.9
0.6
1753
7
giE\e~RT
0
892,610
453,200
164,060
18,500
4,551
1,533,000
776
THERMODYNAMIC PROPERTIES
[CHAP XVIi
\^igHe'"^)\l^igH&~'^)\^ig.ie~'^)
(33)
CHAP. XVII]
EXTERNAL ROTATION
777
or
Q=(Qr)(Qr')(Q.)(Qa)(a)
(34)
ST' -{- SI
-\- S^-\- 8%
(35)
(36)
778
THERMODYNAMIC PROPERTIES
(CHAP.
XVII
or
In Qr = In IT - ' I n a + 88.39
dlnQr
dHnQr
(37)
(39)
HS),
= RT
(40)
(41)
( ^ - ^ )
= - ^ a n IT + In a + 88.39)
. (42)
where
I = moment of inertia for rotation about the center of gravity in
the plane of the line through the atoms (gr)(cm^)
k = Boltzmann constant = (1.3805)(10-") erg/(molecule)(K)
h = Planck's constant = (6.624) (IQ-^^ (erg) (sec)
T = degrees Kelvin
<T = the symmetry number
The symmetry number is defined as the number of different positions
into which the molecule can be rotated with identical appearance from
every point of view. Thus, a diatomic molecule composed of like atoms
can be rotated into two positions of identical appearance and therefore
has a symmetry number a = 2. However, if the atoms are dissimilar,
cr=l.
The symmetry number a of complex nonlinear molecules may vary
widely with the configuration of the molecule. Many such molecules
are unsymmetrical and in such cases o- = 1.0. However, for H2O,
(T = 2; for NH3, 0- = 3; for C2H4, <T = 4; for CH4, a = 12; for CaHe,
(T = 6; and for CeHe, a = 12. Symmetry numbers are most easily established by inspection of three-dimensional molecular models.
By a similar analysis it has been shown that at temperatures above
CHAP. XVII]
EXTERNAL ROTATION
779
a
or
hi Q, = f In T +
+ iili]
In (IJyL) - In (7 + 133.18
d l n Q , 3 dHnQr
= 0
d In r
2 ' d(ln r)2
(44)
(45)
From these relations the contributions of external rotation to the thermodynamic properties of nonlinear molecules are obtained, thus:
Equations (24) and (45):
{V-Kl)r=iRT=iB-Hl)r
(46)
-(47)
(48)
780
THERMODYNAMIC PROPERTIES
[CHAP.
XVll
Xi, yt, Zi, where i designates a particular atom. Then the product of
the three principal moments of inertia is equal to a determinant:
A-D-E
B-F = ABC - AF^ - CD^ - 2DEF - BE^
IJyh = -D
-E-F
C
m
(S.-miZi)^
m
(50)
m
D = S,-miXi2/i
(Sim<Xi)(Simi2/i)
m
' = S.-miXiZi
(S,-mia;i)(S,-mi2i)
m
F = ^iMiyiZi
(Sm,-j/.)(S,-w-<z,)
m
ilf = SiWij = mass per molecule
For convenience in calculating it is customary to express interatomic
distances in Angstrom units equal to 10~^ centimeter and to use grams
per mole M as the unit of atomic mass instead of grams per molecule m.
If the moment of inertia calculated in these units is designated as I',
'
T'
6.023(102)(10)2
(6.023)(W)
^ '
and
I'xl'l'z
E In J . = i? In 7; - 181.96
(53)
R In 7 . 7 / . = Z2 In 7;7i7^ - 545.87
(54)
(55)
(56)
781
EXTERNAL ROTATION
CHAP. XVII]
(57)
(58)
The data necessary for estimating the interatomic distances and bond
angles required for calculating values of / ' are summarized in Table
XLIV for many of the atoms in the more common configuration. In
column I are values of covalent radii recommended by Hirschfelder'^
from the electron diffraction measurements of Pauling^' and others. I t
is assumed that internuclear distances are the sum of the two covalent
bond radii. Thus the internuclear separation for C-H bond is always
0.30A + 0.77A=1.07A.
TABLE XLIV
ATOMIC COVALENT RADII AND BOND ANGLES
3. Triple-bond carbon
4. Benzene carbon
III. Oxygen
1. Single-bond oxygen
Bond
111
o/
=0
108 1108
/ N \
108
Planar
120
\N^
120^120
^' J. O. Hirschfelder, private communication (1942).
" L . PauUng, Proc. Nat. Acad. Sci. U.S., 18, 293 (1932).
782
THERMODYNAMIC PROPERTIES
[CHAP. XVII
Bond
0.55 A (double bond)
0.70 A (single bond)
4. Cyanide nitrogen 0.65 A
CovalerU Radius
3. Isonitrile nitrogen
V. Sulfur
1. Single-bond sulfur
1.04 A
2. Double-bond sulfur
3. Sulfate sulfur
0.95 A
0.95 A (double bond)
1.04 A (single bond)
Sodium
Chlorine
Bromine
Iodine
1.81 A
0.99 A
1.14A
1.33 A
105
s/
=S
Tetrahedral angles
lOS'lUOS"
108^ 1 K.'ios"
VI.
VII.
fill.
IX.
The angles between the bonds are given in the last column of Table
XLIV. These data permit construction of molecular diagrams or models
from which values of / ' are calculated by application of Equation (50).
Illustration 8. Calculate the rotational contribution to the entropy of NaCl (g)
at 298.1K and 1.0 atm.
Solution: From Table XLIV the interatomic distance, d = 1.81 + 0.99 = 2.80 A.
The moment of inertia / ' of a diatomic molecule is calculated as follows:
Let xi, Xi = distances from center of gravity of atoms 1 and 2 of
masses mi and mj, respectively
d = distance between atomic centers
d = Xi + X2 = 2.80
(a)
r = miXi + mixl
(b)
(c)
Combination of Equations (a), (b), and (c), and elimination of xi and xa gives
mim^'
(23) (35.5) (2.80)^ , .
1 =
=
= 109.O
(mi + mi)
(23 -|- 35.5)
Substitution in Equation (55), since a- = 1, gives
s; = 4.575 (log 109.5 + log 298.1) - 4.39 = 16.25
Illustration 9. Calculate the rotational contribution to the entropy of ethylene,
HjC = CH2 at 25C and 1.0 atm pressure.
Solution: Reference to Table XLIV shows that the bonds of a double-bond carbon
atom are in one plane; therefore the molecular model of ethylene may be represented
by a two-dimensional diagram with interatomic spacings, as shown in Fig. 164, and
EXTERNAL ROTATION
CHAP. XVII]
783
the center of gravity located midway between the carbon atoms. The co-ordinates
of the atoms are, then,
H':
Zi = Q
12 = - 1 . 2 7 A;
y% = - 0 . 8 9 A;
22 = 0
B?
H<
X3 = +1.27 A;
2/3 = +0.89 A;
Z3 = 0
i 4 = +1.27 A;
Ci;
Xi = - 0 . 6 7 A;
2/1 = - 0 . 8 9 A;
2/6 = 0;
Z6 = 0
C:
X6 = +0.67 A;
^6 = 0;
Z6 = 0
24 = 0
By using these co-ordinates the product of the moments of inertia could be obtained
from Equation (50). Since, the origin is located at the center of gravity, however,
if is simpler merely to sum up the moments of inertia of each of the atoms about
each axis. Thus:
7x' = 4(1.008)(0.89)2 = 3.19
ly = 4(1.008)(1.27)2 + 2(12.00) (0.67)2 = 6.61 + 10.78 = 17.29
/; = 4(1.008) [(0.89)2 + (1.27)2] + 2(12.00) (0.67)^ = 9.70 + 10.78 = 20.48
It may be noted as a general rule that when
y
aU atoms lie in the plane of the x, y axes
784
THERMODYNAMIC PROPERTIES
[CHAP. X V I I
Solution: The first step in dealing with an unsymmetrical molecule is the construe-
tion of a diagram or model to serve as a guide in determining the co-ordinates of the
atoms. A diagram for methyl alcohol is shown in Fig. 165 in three projected views
using values from Table XLIV. For convenience the carbon atom is placed at the
origin and the molecule and its parts so oriented that as many atoms as possible lie
in the xy plane. The molecule could equally well be drawn with other relative positions of orientation of the oxygen with respect to the carbon atom, but the product
of the three moments of inertia is neghgibly affected by such changes. The interatomic distances from Table XLIV are C-H = 1.07; C-0 = 1.43, ^and O-H = 0.96.
From the geometry of the diagram the co-ordinates of the atoms are calculated as
follows:
ff: x = -1.07sinl8
= -0.331;
H': X = -0.331;
H': X =
H*: 3; =
=
0: 2 =
-0.331;
1.43 4-0.96 sin 21
1.77;
1.43;
i / = - 1 . 0 7 sin 72
=-1.018;
y = 1.018 sin 30
= 0.509;
y = 0.509;
?/ = 0.96 sin 69
= 0.894;
y = 0;
41 = 0
z = -1.018 sin 60
= -0.88
g = 0.88
z= 0
2=0
These co-ordinates and the corresponding atomic weights M are substituted in Equation (50):
Summations
IP
ff
IP
H
O
Sum
W
H
H
H*
O
Sum
M{y^ + z^)
1.0446
1.0453
1.0453
0.8092
00
3.9444
M(xy)
+0.3397
-0.1698
-0.1698
+1.6022
0
1.6023
My
-1.0261
-f0.5131
+0.6131
+0.9032
0.0
0.9033
M(x^ + y^)
1.1551
0.3716
0.3716
3.9815
32.7184
38.5982
Mz
0
-0.8890
-1-0.8890
0
0
0
Mxz
'o
+0.2943
-0.2943
0
_0
0
-
Mx
-0.3336
-0.3336
-0.3336
+1.7882
+22.8800
23.6674
M(x^ + z^)
0.1105
0.8946
0.8946
3.1723
32.7184
37.7904
Myz
0
-0.4515
+0.4515
0
_0
0
? (0.9033)2 = 3.9189
32.042
B = 37.7904
i (23.6674)2 = 20.3088
32.042
C = 38.5982 - i ^ (23.6674)2 _ _ ! _ (0.9033)'' = 21.0911
D = 1.6023
S=0-0=0
^=0-0=0
7^/;/; = ABC - CD' = 1660
CHAP. XVII]
EXTERNAL ROTATION
785
Complex molecules in general are most conveniently treated by preparing an accurate large-scale diagram similar, to Fig. 165, using pro-
786
THERMODYNAMIC PROPERTIES
[CHAP.
XVII
^'
hivT"
^^^^
Q, =
2.7934[(/redr)(10^^)]*
Jl
(60)
HAP. XVII]
INTERNAL ROTATION
787
where
/red = the reduced moment of inertia of the internal rotation
Nh = the symmetry number of the internal rotation, the number of
points of maximum attraction existing per revolution between
the atoms of the rotating groups.
For example, in the ethane molecule at three positions in each revolution the hydrogen atoms of one group reach points of minimum separation from those of the other. Hencef for this rotation Nh = 3.
. The reduced moment of inertia of one group about another is given
by the following expression if the axis of the internal rotation coincides
with one of the principal axes of the molecule as a whole.
lied
IA IB
^5l^--tae,
(66)
(66)
788
THERMODYNAMIC PROPERTIES
[CHAP.
XVll
TABLE XLV
IN
0.0
0.10
0.20
0.30
0.40
0.50
0.9934
1.1822
1.3513
1.5011
1.6324
1.7460
1.9607
2.0934
2.1657
2.1971
2.2030
2.1944
2.1788
2.1607
2.1261
2.0984
2.0781
2.0634
2.0526
2.0382
2.0292
2.0229
2.0182
2.0147
0.993
1.106
1.249
1.374
1.482
1.576
1.753
1.854
1.900
1.909
1.893
1.864
1.829
1.794
1.727
1.670
1.623
1.583
1.548
1.492
1.441
1.401
1.363
1.329
0.993
;.050
1.151
1.251
1.340
1.418
1.561
1.636
1.662
1.651
1.621
1.577
1.529
1.481
1.392
1.315
1.251
1.196
1.147
1.067
0.997
0.937
0.886
0.841
0.993
1.022
1.073
1.138
1.211
1.275
1.385
1.440
1.448
1.426
1.382
1.329
1.273
1.218
1.115
1.029
0.955
0.892
0.838
0.745
0.672
0.613
0.561
0.516
0.993
1.008
1.036
1.072
1.114
1.155
1.230
1.265
1.260
1.224
1.176
1.121
1.061
1.002
0.893
0.802
0.725
0.661
0.608
0.519
0.450
0.394
0.347
0.307
0.993
1.000
1.015
1.030
1.048
1.065
1.103
1.120
1.104
1.060
1.006
0.947
0.884
0.824
0.714
0.624
0.549
0.488
0.437
0.356
0.295
0.249
0.211
0.181
0.60
0.70
0.80
VH/RT
0.0
0.2
0.4
0.6
0.8
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
12.0
14.0
16.0
18.0
20.0
0.92
0.88
0.82
0.73
0.67
0.56
0.482
0.418
0.363
0.319
0.244
0.195
0.157
0.128
0.105
0.59
0.47
0.38
0.31
0.269
0.231
0.169
0.128
0.099
0.077
0.061
0.31
0.25
0.20
0.17
0.116
0.084
0.063
0.047
0.036
(H-Hg).>
Sr'
(67)
INTERNAL ROTATION
CHAP. XVII]
789
TABLE XLVI
INTERNAL ROTATIONAL CONTRIBUTIONS TO ENTROPY, cal/(K)(g-mole)
^
1 - - C s / 0.0
0.10
1/Q/
VH/RJ
0.0
0.2
0,4
0.6
0.8
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
12.0
14.0
16.0
18.0
20.0
8,')
Of!}
0.20 0.30
^
0,30
0]
0.40
0.50
0.60
0.70
1.45
1.34
1.22
1.10
0.97
0.79
0.665
0.664
0.482
0.418
0.315
0.247
0.196
0.158
0.129
0.81
0.63
0.50
0.41
0.348
0,295
0,212
0,158
0,120
0,093
0.073
0.0000
0.0049
0.0198
0.0440
0.0771
0.1185
0.2527
0.4182
0.6001
0.7856
0.9660
1.1356
1.2918
1.4339
1.6781
1.8783
2.0447
2.1864
2.3095
2.5155
2.6847
2.8289
2.9545
3.0659
0.000
0.004
0.018
0.043
0.077
0.117
0.250
0.415
0.594
0.777
0.957
1.126
1.280
1.421
1.662
1.860
2.024
2.163
2.284
2.485
2.650
2.788
2.910
3.017
0.000
0.004
0.018
0.040
0.072
0.112
0.242
0.402
0.577
0.757
0.929
1.094
1.244
1.380
1.616
1.807
1.962
2.095
2.208
2.394
2.547
2.674
2.781
2.872
0.000
3.386 2.814 2.371
0.004
3.382 2.811 2.369
3.370 2.801 2.359
0.016
0.039
3.347 2.780 2.340
0.068
3.318 2.750 2.315
0.107
3.279 2.714 2.279
3.156 2.600 2.173
0.230
0.382
3.004 2.458 2.048
2.836 2.303 1.907
0.550
0.719
2.667 2.138 1.756
0.886
2.500 1.978 1.610
1.043
2.343 1.834 1.475
2.199 1.698 1.348
1.187
2.068 1.579 1.233
1.318
1.542
1.844 1.370 1.040
1.721
1.665 1.204 0.891
1.867
1.519 1.071 0.770
1.989
1.397'0.962 0.674
2.091
1.295 0.872 0.596
2.261
1.125 0.728 0.476.
2.392 0.994 0.620 0.388
2,496
0.890 0.533 0.322
2,585
0.801 0.464 0.270
2.659
0.727 0.405 0.228
>0.80
0.39
0.31
0.25
0.21
0.143
0.102
0.075
0.056
0.042
In general the barriers are greater for large atoms. Approximation for
specific groupings can be estimated from analogy to those of Table
XLVIII.
Where long chains are involved, as in the higher normal paraffins and
their derivatives, the rotational contributions of the intermediate groups
are difficult to evaluate, and the entire problem is complicated by the
effect of internal rotation on the external-rotational contributions. Improved methods for handhng this problem have been proposed by Crawford'* and Pitzer,'^ but in the present state of development these schemes
require a high degree of judgment or are too tedious for general application. For the present the most practical procedure for developing data
for a new compound is to work out in detail the lowest, or better the next
to the lowest, homolog with the best possible assumptions as to potential
18 B. L. Crawford, / . Chem. Phys., 8, 273 (1940).
1' K. S. Pitzer, Chem. Rev., 27, 39 (1940).
790
THERMODYNAMIC PROPERTIES
[CHAP. XVll
TABLE XLVII
INTEENAL ROTATIONAL CONTRIBUTIONS TO HEAT CAPACITY, cal/(K) (g-mole)
0.10
0.20
0.00
0.30
0.40
0.50
0.60
0.80
0.70
Vh/til
0.0
0.2
0.4
0.6
0.8
1.0
1.5
2.0
2.6
3.0
3.5
4.0
4.5
5.0
6.0
7.0
8.0
9.0
10.0
12.0
14.0
16.0
18.0
20.0
0.9934
0.993
1.0033
1.003
1.032
1.0326
1.0799
1.079
1.1433
1,141
1.2201
1.217
1.444
1.4506
1.687
1.6975
1.9211
1.908
2.082
2.0986
2.204
2.2223
2.2986
2.276
2.312
2.3354
2.3443
2.318
2.3155
2.283
2.2647
2.228
2.2157
2.174
2.130
2.1759
2.1454 . 2.094
2.1050
2.043
2.0810
2.009
2.0654
1.983
2.0544
1.961
2.0462
1.944
0.993
1.001
1.028
1.073
1.133
1.206
1.423
1.655
1.866
2.033
2.146
2.213
2.238
2.241
2.192
2.126
2.058
1.999
1.951
1.877
1.814
1.764
1.717
1.678
0.993
0.999
1.024
1.065
1.121
1.190
1.391
1.606
1.801
1.952
2.054
2.110
2.129
2.120
2.059
1.973
1.888
1.808
1.745
1.636
1.546
1.468
1.397
1.333
0.993
0.998
1.019
1.056
1.106
1.169
1.348
1.541
1.717
1.846
1.934
1.980
1.990
1.972
1.893
1.787
1.684
1.587
1.507
1.365
1.254
1.156
1.070
0.991
0.99
1.00
1.02
1.05
1.09
1.14
1.30
1.469
1.623
1.738
1.803
1.834
1.832
1.808
1.711
1.588
1.468
1.362
1.262
1.107
0.978
0.873
0.780
0.701
1.7
1.7
1.69
1.67
1.62
1.51
1.394
1.260
1.149
1.047
0.877
0.744
0.639
0.549
0.477
1.4
1.33
1.21
1.07
0.955
0.853
0.683
0.555
0.457
0.378
0.316
1.0
0.91
0.79
0.68
0.519
0.408
0.321
0.256
0.207
TABLE XLVIII
POTENTIAL, B A R R I E R S H I N D E R I N G INTERNAL, ROTATION
Group A
CHs
CH3
CH3
CHa
CH,
CH3
GHs
CH3
CH3
OH
OH
OH
Group B
CHs
CH2CII3
CH(CH3)ii
C(CH3)3
C = C CH3
CH2OH
C0(CH3)
NH(CH3)
0CH3
-CH3
CH2CH3
--GH(CH3)2
F A I eal
per g-ioaole
3150
3300
3870 ,
4540
0
3000
1000
3460
3100
2700
10,000
5000
CHAP. XVII!
VIBRATIONAL CONTRIBUTIONS
791
"--'''"
-'
Equation (61),
VhHA^*)V
- = ^
NH
+ -
^methyl
^OH
mi
MQt
n/Kr
298.16
500
1000
17.267
22.361
31.623
0.602
0.465
0.329
4.56
2.72
1.36
298.16
500
1000
0.74
1.14
1.31
(Gj,
- Ho),/
e;,
cr.
1.08
1.97
3.02
1.67
1.72
1.32
0.34
0.83
1.71
(H3,-H;),,
221
570
1310
792
THERMODYNAMIC PROPERTIES
[CHAP.
XVII
X = 1.4384w7r,
d.ln Q
d^ In Q
a; V
d(lnT)2 ( e ^ ~ l ) 2
(69)
e^-1
(70)
(7*1)
( c ; ) . = (c). = 5 ! S - ^ ^
(e^ 1)''
(72)
hi(l - e--)
(^)r
flSbi(l-e-)
(73)
(74)
CHAP. XVII]
VIBRATIONAL CONTRIBUTIONS
793
freedom. These fundamental frequencies and the corresponding statistical weights are determined from spectroscopic data or may be estimated from generalized bond assignments, as discussed in the following
section. To facilitate solution of Equations (71-74) extensive tables
have been prepared relating the various so-called Einstein fimctions to x.
In Table XLIX are values of the vibrational contributions to heat capacity, enthalpy, and free energy expressed as functions of JjT.
This
table originally developed by H. L. Johnston^' and revised by Schumann and Schwartz, 22 is more convenient to use than tables of the
Einstein functions but has the disadvantage of being dependent on the
values of the physical'constants. Contributions to the entropy are obtained from these tables by means of the equation:
1
2
3
4
5
6
7
8
WaveNo.jia
3683
2978
2845
1477
1455
1340
1034
1030
Statistical Wgt., g
1
2
1
2
1
2
1
1
298.16
12.352
9.988
9.542
4.954
4.880
4.494
3.469
3.455
500
7.366
5.956
5.690
2.954
2.910
2.680
2,068
2.060
1000
3.683
2.978
2.845
1.477
1.455
1.340
1.034
1.030
Calculate the contributions of vibration to the heat capacity, enthalpy, entropy, and
free energy in the ideal-gaseous state at 1 atm and 298.16, 500, and 1000K.
The contribution corresponding to each vibrational degree of freedoi\j is read from
Table XLIX and multiplied by the corresponding statistical weights. Thus, at
298.16K,
(^).
-(^l
{c)
1
0.00000
2
0.00004
3
0.00003
4
0.02342
0.00330
0.166
5
0.01282
0.00183
'
0.090
6
0.04120
0.00636
0.264
7
0.06920
0.01386
0.346
8
0.07030
0.01413
0.350
S
0.21701 '
0.03948
1.216
^ E. B. Wilson, Jr., Chem. Rev., 27, 17 (1940).
*" S. C. Schumann and M. L. Schwartz; Taylor and Glasstone, " Treatise on
Physical Chemistry," Vol. I, D. Van Nostrand Co., New York (1942) with permission.
794
THERMODYNAMIC PROPERTIES
[CHAP. XVII
TABLE i L I X
VIBRATIONAL CONTRIBUTIONS TO THERMODYNAMIC PROPERTIES I
cal/(K)(g-mo]e)
(J/T)
(H-HS
(G-H;)
>
W/T)
1.9834
1.9827
1.9819
1.9810
1.9801
1.8473
1.8338
1.8203
1.8068
1.7935
3.9942
. 3.8186
3.6596
3.5143
3.3807
0.15
0.16
0.17
0.18
0.19
1.9791
1.9780
1.9768
1.9756
1.9744
1.7801
1.7670
1.7538
1.7407
1.7276
3.2572
3.1428
3.0361
2.9362
2.8424
0.20
0.21
0.22
0.23
0.24
1.9731
1.9717
1.9703
1.9687
1.9671
1.7147
1.7018
1.6890
1.6763
1.6636
0.25
0.26
0.27
0.28
0.29
1.9655
1.9638
1.9620
1.9601
1.9583
0.30
0.31
0.32
0.33
0.34
(O-H;)
T
0.10
0.11
0.12
0.13
0.14
(H-HD
1.9188
1.9159
1.9128
1.9097
1.9066
1.4128
1.4016
1.3904
1.3793
1.3682
1.4726
1.4416
1.4117
1.3826
1.3543
0.50
0.51
0.52
0.53
0.54
1.9033
1.9001
1.8966
1.8933
1.8898
1.3573
1.3464
1.3354
1.3248
1.3140
1.3267
1.3001
1.2741
1.2488
1.2242
2.7542
2.6710
2.5920
2.5142
2.4662
0.55
0.56
0.57
0.58
0.59
1.8863
1.8827
1.8791
1.8754
1.8718
1.3034
1.2929
1.2823
1.2719
1.2616
1.2001
1.1766
1.1539
1.1316
1.1099
1.6510
1.6384
1.6260
1.6135
1.6012
2.3786
2.3140
2.2525
2.1935
2.1372
0.60
0.61
0.62
0.63
0.64 .
1.8680
1.8641
1.8602
1.8562
1.8522
1.2513
1.2411
1.2308
1.2207
1.2107
1.0887
1.0681
1.0481
1.0284
1.0093
1.9563
1.9542
1.9521
1.9500
1.9478
1.5889
1.5767
1.5645
1.5525
1.5404
2.0831
2.0311
1.9813
1.9333
1.8872
0.65
0.66
0;67
0.68
0.69
1.8481
1.8441
1.8398
1.8357
1.83i5
1.2007
1.1908
1.1810
1.1711
1.1614
0.35
0.36
0.37
0.38
0.39
1.9454
1.9430
1.9406
1.9381
1.9356
1.5285
1.5167
1.5048
1.4931
1.4814
1.8427
1.7998
1.7584
1.7185
1.6799
0.70
0.71
0.72
0.73
0.74
1.8272
1.8227
1.8184
1.8140
1.8093
1.1517
1.1420
1.1325
1.1230
1.1135
0.9033
0.8870
0.8713
0.8557
0.8405
0.40
0.41
0.42
0.43
0.44
1.9330
1.9303
1.9275
1.9247
1.9218
1.4698
1.4583
1.4468
1.4354
1.4240
1.6425
1.6063
1.5713
1.5374
1.5045
0.75
0.76
0.77
0.78
0.79
1.8047
1.8002
1.7955
1.7908
1.7863
1.1041
1.0948
1.0856
1.0764
1.0674
0.8256
0.8110
0.7968
0.7828
0.7692
0.45
0.46
0.47
0.48
0.49
0.9905
0.9722
0.9545
0.9370
0.920*
CHAP. X V I I ]
VIBRATIONAL CONTRIBUTIONS
795
(co'/r)
(H-Ho)
(G-H;)
(f^'/T)
(H-H)
(O-HS)
0.80
0.81
0.82
0.83
0.84
1.7813
1.7765
1.7716
1.7667
1.7618
1.0582
1.0492
1.0403
1.0314
1.0226
0.7558
0.7437
0.7299
0.7174
0.7052
1.20
1.21
1.22
1.23
1.24
1.5592
1.5531
1.5468
1.5406
1.5343
0.7427
0.7359
0.7292
0.7225
0.7159
0.3894
0.3832
0.3773
0.3713
0.3656
0.85
0.86
0.87
0.88
0.89
1.7568
1.7517
1.7466
1.7415
1.7364
1.0138
1.0050
0.9964
0.9878
0.9793
0.6931
0.6812
0.6697
0.6583
0.6473
1.25
1.26
1^27
1.28
1.29
1.5281
1.6217
1.6156
1.5091
1.5030
0.7093
0.7027
0.6963
0.6898
0.6834
0.3598
0.3542
0.3486
0.3432
0.3379
0.90
0.91
0.92
0.93
0.94
1.7312
1.7259
1.7206
1.7154
1.7099
0.9708
0.9620
0.9541
0.9458
0.9377
0.6363
0.6256
0.6151
0.6049
0.5948
1.30
1.31
1.32
1.33
1.34
1.4966
1.4902
1.4839
1.4774
1.4710
0.6771
0.6708
0.6646
0.6585
0.6523
0.3326
0.3275
0.3225
0.3175
0.3126
0.95
0.96
0.97
0.98
0.99
1.7045
1.6991
1.6935
1.6882
1.6826
0.9295
0.9212
0.9132
0.9051
0.8971
0.6848
0.6751
0.5657
0.5563
0.5471
1.35
1.36
1.37
1.38
1.39
1.4646
1.4583
1.4520
1.4455
1.4390
0.6462
0.6402
0.6342
0.6283
0.6223
0.3078
0.3030
0.2983
0.2937
0.2893
1.00
1.01
1.02
1.03
1.04
1.6770
1.6714
1.6668
1.6601
1.6544
0.8893
0.8815
0.8737
0.8659
0.8582
0.5382
0.5294
0.5208
0.6123
0.5040
1.4324
1.40
1.41
1.4259
1.42 1.4194
1.4129
1.43
1.44
1.4065
0.2848
0.2804
0.2761
0.2719
0.2677
1.05
1.06
1.07
1.08
1.09
1.6487
1.6429
1.6371
l.iB312
1.6254
0.8507
0.8430
0.8355
0.8281
0.8207
0.4959
0.4877
0.4800
0.4722
0.4647
1.45
1.46
1.47
1.48
1.49
1.3999
1.3934
1.3868
1.3802
1.3736
0.6164
0.6107
0.6049
0.5998
0.5935
0.5879
0.5823
0.5768
0.5713
0.6658
1.10
1.11
1.12
1.13
1.14
1.6196
1.6137
1.6077
1.6017
1.5957
0.8133
0.8060
0.7988
0.7916_
0.7845
0.4572
0.4499
0.4426
0.4357
0.4287
1.50
1.51
1.52
1.53
1.54
1.3671
1.3605
1.3538
1.3473
1.3406
0.5604
0.5550
0.5493
0.5445
0.5392
0.2441
0.2404
0.2367
0.2332
0.2297
1.15
1.16
1.17
1.18
1.19
1.5897
1.5837
1.5776
1.5715
1.5653
0.7774
0.7703
0.7634
0.7564
0.7495
0.4218
0.4151
0.4086
0.4021
0.3957
1.55
1.56
1.57
1.58
1.59
1.3340
1.3274
1.3208
1.3143
1.3077
" 0.5340
0.5288
0.5238
0.5187
0.5138
0.2262
0.2227
0.2193
0.2161
0.2129
0.2636
0.2595
0.2556
0.2518
0.2471
THERMODYNAMIC PROPERTIES
796
[CHAP. XVII
(H-Ho)
_ (g-Ho)
(Q-H;)
(,/y)
wm
0.5039
0.4988
0.4942
0.4893
.:S5
o:S
5s E E
JE E
E =
;.^
0.,3
0.IS02
a;
0573
0035^6
\T-,
1S
0S
oS
0.2659
0.08084
\fS,
S
oafs
0:35
.nni
0 TS
0:1093
niR79
2.26
2.28
2^0
0.8799
0.8682
0 8570
0.2605
0.2551
0.2497
0.07850
0.07622
0.07402
;r,l
VZ
0S
Sz
0;8455
0.2145
0.07189
;-S
S'S
aS
0:^S S.2295
0.535
1.1625
nAi77
0.4177
0:4135
01551
u.iooi
0.1528
2.40
^2.42
-1"
0.8000
. _,
0.7885
0.06395
nriROif!
^^^^^ -^?^^
1-;S S:S
S:S
VZ
2.46 S S
tZ =
S
0:05859
0:20. 0.05690
i:i363
1-1298
0.3972
0.3932
0.1440
0.418
2.50
2.52
0.7453
0.7346
0.2017
0 197^
0.05526
^^^^,^^
M S
2: 6
S7135
0.1891
0.050^5
;-;;o2
,,038
ssfe
0.3777
0:1356
0..1336
2.58
2.60
0.7031
0.6928
0.1850
0.1810 "
0.04919
0.04778
iS
oS
2S
S:6?25
0:i732
0.04507
^Tc
S
nffiS
0.f627
'T^
nfo
^^^^
0?S
0 3?18
n.fi
0 1278
S
r^\nAn
01222
oSS
0 187
2 66
0.6625
2.68 , 0.6527
o7n
0 6429
272
06332
' 2 74
0.6236
2 76
0 6140
0.1695
0.1656
0.1622
0.1587
0.1553
0.1519
0.04379
0.04253
0.04131
0.04014
0.03901
0.03788
IS
0.nS
0.1483
0.03679
IS s i S -s = s s:=
77
0.6046
0.2246
. n,o
CHAP. XVII]
797
VIBRATIONAL CONTRIBUTIONS
(H-H3
(G-HS)
WIT)
(H-HO)
(Q-Ho)
T
c^'IT)
2.80
2.82
2.84
2.862.88
0.5953
0.5862
0.5771
0.5680
0.5591
0,1454
0,1422
0,1391
0,1361
0,1331 ,
0.03572
0.03471
0.03371
0,03275
0,03181
5.00 0.0775
5.10 0.0697
5.20 0.0628
5.30 0.0563
5.40 0.0506
0.01074
0.00948
0.00836
0.00740
0.00652
0,00150
0,001290
0,001116
0,000965
0,000837
2.90
2.92
2.94
2.96
2.98
0.5502
0.5417
0.5331
0.5246
0.5163
0.1301
0.1272
0.1244
0.1216
0.1189
0.03089
0.03003
0,02917
0,02834
0.02752
5.50 0.0454
5.60 0.0409
5.70 0.0367
6,80 0.0330
5.90 0,0295
0.00575
0.00507
0.00447
0.00393
0.00347
0.000727
0.000629
0.000545
0.000472
0.000409
3.00
3.05
3.10
3.15
3.20
0.5080
0.4876
0.4680
0.4489
0.4305
0,1162
0,1099
0,1038
0,0981
0.0927
0.02673
0,02486
0,02311
0,02150
0,02000
6.00
6.10
6.20
6.30
6.40
0,0265
0,0236
0,021^
0,0189
0,0169
0.00305
0.00269
0.00236
0.00208
0.00183
0.000353
0.000306
0.000266
0.000231
0.000200
3.25
3.30
3.35
3.40
3.45
0.4127 , 0.0875
0.0826
0.3956
0,0780
0.3787
0,0736
0.3627
0.0696
0.3471
0,01861
0,01731
0,01608
0,01498
0,01393
6.50
6.60
6.70
6.80
6.90
0,0151
0,0134
0,0120
0.0107
0.00960
0.00161
0,00142
0.00125
0.00110
0.000962
0.000173
0.000151
0.000131
0.000114
0.0000993
3.50
3.55
3.60
3.65
3.70
0.3323
0.3177
0.3038
0.2903
0.2775
0,0656
0,0619
0,0584
0,0550
0.0519
0,01297
0,01207
0,01124
0.01045
0,00972
7.00 0.00852
7.10 0.0075&
7.20 0.00674
7.30 0.00600
7.40 0,00534
0.000845
0.000742
0.000651
0.000571
0.000502
0.0000865
0.Q0Q075Q
0.0000651
0.0000565
0,0000491
3.75
3.80
3.85
3.90
3.95
0.2651
0.2532
0.2417
0.2307
0.2201
0.0489
0,0461
0,0435
0.0410
0,0387
- 0.009040.00842
0,00783
0,00729
0,00678
0,00474
0.00423
0.00376
0.00332
0.00298
0.000441
0.0003868
0.0003497
0.0002979
0.0002618
0,0000427
0,0000369
0,0000320
0,0000278
0,0000241
4,00
4.10
4.20
4.30
4.40
0,2099
0.1907
0.1732
0,1571
0.1424
0,0364
0,0322
0.0286
0.0253
0.0225
0,00631
0,00547
0.00473
0.00409
0,00354
8.00 0.00265
8.10 0.00234
8.20 0.00208
8.30 0.00185
8.40 0.00164
0.0002292
0.0002008
0.0001759
0.0001542
0.0001352
0,0000209
0,0000181
0.0000156
0.0000135
0.0000117
4.50
4.60
4.70
4.80
4.90
0.1286
0.1166
0.1054
0.0952
0.0859
0.0200
0.0176
0.0156
0.0138
0.0122
0,00306
0.00285
0.00230
0.00199
0.00173
8.50 0.00145
8.60 0.00129
8.70 0.00113
8.80 0.00101
8.90 0.00089
0.0001187
0.0001038
0,0000908
0,0000795
0,0000896
0.0000101
0.0000088
0.0000077
0.0000067
0.0000058
- 7.50
7.60
7.70
7.80
7.90
798
THEEMODYNAMIC PROPERTIES
[CHAP. XVII
,m^
(o>'/T)
9.00
9.10
9.20
9.30
9.40
(H
c
0.000792
0.000701
0.000620
0.000549
0.000486
-H)
^
0.0000610
0.0000535
0.0000466
0.0000408
0.0000357
(O - H )
T
0.0000050
0.0000043
0.0000037
0.0000032
0.0000028
WIT)
9.50
9.60
9.70
9.80
9.90
10.00
0.000431
0.000380
0.000335
0.000297
0.000262
0.000232
(H-H;)
(G-H;)
0.0000312
0.0000273
0.0000239
0.0000209
0.0000184
0.0000161
0.0000024
0.0000021
0.0000018
0.0000016
0.0000014
0.0000012
The
Generalized Bond Frequencies, Useful approximations to the vibrational contributions may be obtained by assuming that a particular type
of bond possesses two characteristic fundamental frequencies, which are
independent of the nature of the molecule in which the bond occurs.
Generalized average values of the stretching and bending frequencies
may be arrived at on this basis from compounds for which spectroscopic
data are available. This general procedure was developed by Bennewitz and Rossner^* and modified by Dobratz.^^ A complication arises
from the fact that there are generally more degrees of freedom than are
accounted for by assuming two vibrational degrees per bond. Dobratz
proposed the following equation for handling this problem for calculating
heat capacities of nonlinear molecules,
/;3w 6 rir- 2gi'
jS(giCi )
(76)
where
CM = total vibrational contribution to the heat capacity
2gi = total number of bonds in the molecule
c^ = contribution to the heat capacity from the stretching vibrations of bond i
c = contribution to the heat capacity from the bending of bond i
n = number of atoms in the molecule
rir' = number of single bonds about which internal rotation of
groups can take place
" Bennewitz and Rossner, Z. physikChem., 393, 126 (1938).
" C. J. Dobratz, Ind. Eng. Chem., 33, 769 (1941).
CHAP. XVll]
799
Equation (76) assumes that all degrees of freedom not accounted for
by internal rotation, stretching or bending, make the same average contribution to the heat capacity as do the recognize#bending contributions.
This same assumption can be made for calculating the contributions to
the other thermodynamic properties and equations developed similar
to (76).
In Table L are the fimdamental frequencies of various bonds expressed
in wave numbers, as recommended by Bennewitz and Rossner^* and
modified by Stull and Mayfield^ for hydrocarbons.
TABLE L
FUNDAMENTAL BOND FHEQUENCT ASSIGNMENTS
Bond
C^H (aliphatic)
CC (aliphatic)
C = C (aliphatic sym.)
C ^ C (aliphatic unsym.)
C ^ C (aliphatic)
CH (aromatic)
GC (aromatic)
C = C (aromatic)
CI
CBr
CCI
CF
C-S
Stretch- Deformaing ul
tion u'^
2914
1247
989
390
1618
599
1664
421
2215
333
3045
1318
989
390
1618
844
500
260
280
560
650
330
1050
530
650
330
Bond
C==S
SS
SH
CN
C=N
NN
NH
N0
N=0
C0
C=0
0H
Stretch- Deformaing al
tion w'g
1050
530
500
260
2570
,1050
990
390
1620
845
990
390
2920
1320
1030
205
1700
390
1030
205
1700
390
3420
1160
^-hqiCsi
(77)
800
THERMODYNAMIC PROPERTIES
250
300
350 400
500
600 700 800 9001000
Temperature, K
[CHAP. X V I I
1600
lo^lf
CHAP. XVII]
801
Solution: The frequencies of the bonds are obtained from Table L, and the corresponding contributions to heat capacity at 298,lK^are read from Fig. 166:
Bond
CH
C0
0H
3<
3
1
1
"^
OJj
2914
1030
3420
1247
205
1150
- ^<&;(298.1)
giC5j(298.1)
0.000
0.346
0.000
0.529
1.833
0.240
0.346
2.602
Thus:
c;
12.4
16.1
22.4
802
THERMODYNAMIC PROPERTIES
[CHAP. XVII
TABLE LI
Translation
External rotation
Internal rotation
Vibration
Total
(H - HS)
298.1''K
1481
888
221
65
2655
Translation
External rotation
Internal rotation
Vibration
Total
500K
2483
1490
570
685
5228
lOOCK
4966
2980.
1310
5220
14476
4.97
2.98
1.72
5.04
14.71
4.97
2.98
1.32
12.38
21.65
38.883
20.482
1.97
1.76
63.095
42.326
22.647
3.02
7.75.
75.643
-33.916
-17.502
-0.820
-0.390
-62.628
-37.359
-19.667
-1.700
-2.530
-61.156
4.97
2.98
1.67
1.22
10.84
S
Translation
External rotation
Internal rotation
Vibration
Total
Translation
External rotation
Internal rotation
Vibration
Total
36.316
18.941
1.080
0.257
66.594
(G - H;)/r
-31.349
-15.961
-0.339
-0.040
-47.689
u\,
2914
2914
2914
1030
3420
1247
1247
1247
205
1150
Stretching-
T
9.78 4.18 0.0000
9.78 4.18 o.oboo
9.78 4.18 0.0000
3.45 0.688 0.0696
11.48 3.86 0.0000
T
0.0000
0.0000
0.0000
0.0139
0.0000
->- -<-
-Bending-
S = 0.0835
The vibrational contribution, by an equation similar to (76), is then
sL(298.i) = 0.0835-t- (6/6) (2.2404) = 2.772
22404
CHAP. XVll]
803
Comparing this value with that of 0.257 in Table LI indicates an error of 2.515 in
the total entropy as a result of the use of the generalized bond-frequency assignments.
(2!^=(5!^_(s*_s)
(79)
804
THERMODYNAMIC PROPERTIES
[CHAP. XVII
PROBLEMS
1. Estimate from the group contributions of Tables XXXIX-XLIII the heat of
formation, entropies, and heat-capacity equations for the following compounds in
the ideal-gaseous state:
(a) Isoprene (2-methyl-l, 3-butadiene)
(6) Meta di-isopropyl benzene
(c) Iso butyronitrile
(d) Diphenyl
(e) o-Nitrobenzoic acid
2. The boiling point of isobutyro nitrite is 108C, and its liquid density at 20C
is 0.773 g per oc. From the result of problem Ic and the generalizations of Chapters III, VII, and'XII calculate the entropy and heat of formation of hquid isobutyro
nitrile at 25C under its vapor pressure.
3. From the covalent radii and bond angles of Table XLIV and the generalized
bond frequencies of Table L, calculate values of s, (H HO), (a nl)/T, and
Cp at temperatures of 298.16, 500, and 1000K for dimethyl sulfide.
4. From the bond-frequency assignments of Table L derive three-term equations
for the heat capacity at constant pressure in the range 298-1500K for the following
compounds in the ideal-gaseous state:
(a) CCI3F
(c) Dimethyl amine
CHAPTER XVIII
HOMOGENEOUS REACTIONS
The economy of cnemical manufacture depends largely upon establishing high rates of production of desired products and minimizing the
production of undesired by-products. Thermodynamic principles may
permit selection of conditions which will result in favorable production
if equilibrium is reached but give no clue as to the rates at which the
various reactions occur. Thus, the displacement of a system from
equilibrium conditions may be considered as a potential which may
cause a reaction to proceed if other conditions are favorable. This displacement is analogous to an electric voltage which may cause,a flow of
electricity. However, the rate of current flow is dependent on the conductance of the system as well as on the voltage. Similarly, reaction
rates depend on the kinetic properties of the system as well as on the
driving potential. Quantitative knowledge of these kinetic properties
is desirable in the design and intelligent operation of a chemical process.
Industrial processes rarely reach equihbrium and in general are desired
to proceed toward only a partial equilibrium among the many reactions
possible in a complex system. In many cases if complete equilibrium
were reached undesirable by-products would predominate. However,
by proper selection of conditions the rate of formation of such byproducts may be suppressed and good yields of the desired product
obtained at conditions far removed from complete equilibrium. It is
thus evident that the kinetic properties of a system may determine not
only the size and capacity of process equipment but the yields and
qualities of the products as well. All three factors are of vital economic
significance.
Classification of Reactions. Chemical reactions may be classified as
homogeneous if only one phase is involved or heterogeneous if more than
one phase actively participates in the reaction. Where catalytic surfaces are present, a reaction may proceed simultaneously by a homogeneous mechanism in the main body of the fluid and by a heterogeneous
mechanism at the catalytic surfaces. In many cases even the walls of a
reactor exert catalytic effects to such an extent that the rates of presumably homogeneous reactions are found to vary with the ratio of
surface to volume.
A further classification is as flow and nonflow or batch processes. Both
805
806
HOMOGENEOUS REACTIONS
[CHAP. X V I I I
(1)
(2)
where
^u> * = unidirectional rates of reaction in moles of a particular
compound formed or consumed per unit volume of
reacting system per unit time
k, k' = the reaction velocity constants
OA, CIB' ' = activities of components A and B, etc.
The net rate of the reaction as written is then
r = r-
(3)
A t equilibrium, where r = 0,
aual
CHAP. XVIII]
ORDER OF REACTION
807
and the nature of the reaction. Thus, Equations (1) and (2) serve to
define the reaction velocity constants k and k' which must be recognized
as inherently different from the classical reaction velocity constants of
chemical kinetics. Because many of the early laboratory studies were
carried out under conditions of constant volume it was convenient to
define reaction rates as rates of change of concentration expressed in
moles per unit volume. Since concentrations are changed by change of
volume as well as by reaction, the rate of change of concentration is a
proper expression for rate of reaction only in a system of constant volume.
Similarly, the classical law of mass action was formulated in terms of
concentrations, and kinetic equations were developed to relate rate of
change of concentration to the concentrations of the reactants. As
commonly written, such equations are restricted to conditions of constant volume, and the reaction velocity constants so defined have different dimensions and significance from those of Equations (1) and (2).
The relationships between reaction velocity constants expressed in terms
of activities and those in terms of concentrations are discussed on
page 820.
The order of the forward reaction is equal to the sum of the exponents
a, 6, c of Equation (1). This sum is equal to 1.0 for a first-order
reaction, 2.0 for a second-order reaction, and 3.0 for a third-order reaction. In reactions of simple order the exponents of the activity terms iij
the fundamental rate equation are equal to the minimum number of
reactant molecules which must simultaneously combine in order to
effect the reaction. This minimum number of combining molecules is
termed the molecularity of the reaction. For reactions of simple order
the order is equal to molecularity. Thus, a simple first-order reaction is
unimolecular, and a simple second-order reaction is bimolecular.
I t is important to recognize that the exponents a, h, c in Equation (1)
and r and s in Equation (2) correspond to the number and kind of molecules which actually simultaneously combine and do not necessarily correspond to the molecular proportions used iri the stoichiometric equation
representing the over-all reaction. For example, the synthesis of methanol
from carbon monoxide and hydrogen is represented by the stoichiometric
equation CO + 2H2 > CH3OH. However, it is probable that in a
homogeneous reaction the alcohol results from secondary hydrogenation
of formaldehyde which is formed as a primary product. Similarly, the
combustion of a gas such as benzene actually proceeds by a succession
of low-order reactions and never by the mechanism suggested by stoichiometry. Thus, Equations (1) and (2) are applicable only to individual chemical steps in one direction and not to over-all stoichiometric
results. In this respect kinetic equations differ from thermodynamic
808
HOMOGENEOUS REACTIONS
[CHAP. XVIII
(6)
where
o , aA, and as = activities of the activated complex and reactants A and B, respectively
K^ = the equilibrium constant between the reactants and the activated complex
By statistical mechanics it was developed by Eyring that in the
majority of cases the rate of decomposition of the activated complex
^ S. Glasstone, K. J. Laidler, and H. Eyring, " The Theory of Rate Processes,"
McGraw-Hill Book Company, New York (1941).
CHAP. X V I I I ]
809
and, therefore, the rate of the reaction, is given by the following equation,
r. = ^c'
where
(7)
In dealing with liquid systems or with gases which do not form ideal
solutions, the standard state for the expression of activities is conveniently taken as that of the pure components at the temperature and
pressure of the system:
a* = y^N^ = Y^cW
(8)
7*. = activity coefficient of the activated complex
Combining Equations (7) and (8), with this choice of standard states
gives
k r g^
' = -h- U
'.
(9)
yhm
When ideal solutions of gases are dealt with, where it is convenient to
select as the standard state the pure components at the temperature of
the system and a unit fugacity of 1 atm,
a} =
KW*
(10)
and'
where
'=sS?
v* = fugacity coefficient of the activated complex
Zm = mean compressibility factor of the mixture
w total pressure, atmospheres
R' = gas law constant in units consistent with ir,
Vm, and T
''^'
810
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
a*
k r K^
_a}
k K^
alal ~ hR' z^
^ ^^
I t is evident from Equations (14) and (15) that for a given reaction the
values of k and K^ are dependent upon the choice of the standard state.
Thus the k and K^ of Equation (15) are numerically different from those
of Equation (14) and must be used with care to maintain a consistent
choice of standard state.
Equations (14) and (15) express the reaction velocity constant in
thermodynamic terms involving K^ the equilibrium constant relating
the activated complex and the reactants. Thus, by evaluation of the
thermodynamic properties of the activated complex and the reactants
the rate of a reaction is established. Since K^ is a true equilibrium constant expressing the ratio of the activities of products to reactants, it
may be expressed in terms of the standard free-energy change in forming the activated complex. Thus,
K* = e - BT = e - B r + - r
(16)
where AG*, AH^, A(S* = the free energy, enthalpy, and entropy changes,
respectively, accompanying the formation of the activated complex from
the reactants all in their standard states. It should be noted that K
is dimensionless only for first-order reactions. Combining Equations
(16) and (14), for liquid systems yields
kr
k = --r-e--Sf
4Ht ASt
^ ^
+ -R-
(17)
hy*Vm
. AH* , ASt
CHAP. X Villi
811
(a) k = . - p - - - , e
(0.08206)
35.00
1.987
ioor/,-.\
u x
//i-j.
^,
This constant, expressing the rate of formation of butene, is compared by Glasstone, Laidler, and Eyring with an experimental value of k" = 0.0374 liter/(atm) (hr)
for the rate of conversion of ethylene. The units of this constant result from the
expression of reaction rate in terms of the rate of reduction of pressure in atmospheres
per hour as the reaction proceeds at constant temperature in a system of constant
volume. Thus, if ideal-gas behavior is assumed, rj/ = A;"p^ atm per hr. This
rate r J,' is related by the ideal-gas law to r the rate in moles/ (liter) (hr). Thus, since
n/V = p/R'T, r = r'u/R'T and k = k"/R'T.
Since 2 moles of ethylene are
converted to 1 mole of butene, the experimental value offc"is converted to the units
of the preceding illustration by the following expression:
; ^ - * = (673)(0.08206K3600)(2) = '-'^''''^
g-mole/(Uter)(sec)(atm)
812
HOMOGENEOUS REACTIONS
[CHAP. X V I I I
(19)
(20)
Equations (19) and (20) are ordinarily used only where rate data are
translated to a widely different temperature range, as, for example, if
low-temperature rate data in a forward reaction are combined with
thermodynamic data in order to estimate rates of the reverse reaction at
high temperature. For rate equations in either temperature range AS^
and AH^ may be taken as constant at average values.
If the Eyring equation is used for the interpretation of experimental
data it is necessary that rate measurements be available at two temperatures in order to evaluate AJtf* and AS^. If AS^ can be approximated
by theoretical calculations, rate measurements at one temperature
suffice to evaluate reaction rates at other temperatures. By application
of the statistical methods developed in Chapter XVI, values of AS* can
be estimated which in many cases are probably as accurate as the average
experimental data. Eyring and co-workers^ have also devefoped
theoretical methods for estimating AH^, but these are uncertain for
engineering application at present.
According to the Eyring theory an activated complex must be formed
for the reverse reaction which has the same thermodynamic properties
as that formed in the forward reaction. Since the forward complex is in
equilibrium with reactants and the reverse complex is in equilibrium
with the products it follows that the actual over-all rates are determined
by the rate of conversion of one complex to the other. Since these two
complexes are identical in thermodjmamic properties and differ only in
the direction in which they are decomposing, it is customary to use but
one symbol for both. Thus if Equation (17) is apphed to the reverse
reaction and the reverse properties are designated with primes, there
results,
fr' = - 7 - T ^ - = r r - ^
''''
'^
(21)
CHAP. XVIII]
813
(22)
(23)
(24)
For the reaction AC| may be taken as 1.0 cal per "K per g-mole of Nj formed.
The fugacity coefficients and compressibility factors may be assumed to be unity.
Calculate:
(a) The values of AH* and AS* at the average experimental temperature of
1572K.
814
HOMOGENEOUS REACTIONS
[CHAP. X V I I I
= -1-96658
Afl*
AS'
+
= -2.52288
4.576(1525)
4.576
AS* = -20.323
291
AS" = - 5 8 6 +
r ^
J298
AG"
:- = 2.47421
4.576r
K = 298
From Equations (23) and (24),
AH*' = AH* - AH" = 65,270 - (-43,327) = 108.597
AS*' = AS* - AS = -20.788 - (-6.009) = -14.779
From Equation (18),
65,270
A; = (2.540)(10")e B(2500)
= 14.346
20 788,
_^^^
CHAP. X V I I I ]
ARRHENIUS
108,597
EQUATION
815
14.779
0.0477
(25)
816
HOMOGENEOUS REACTIONS
"
[CHAP.
XVIII
hv ZmR
in which
JANA
r = kyA = JCJANA
nt
7^ = activity coefficient of component A
UA = moles of reactant A present in the system under
consideration
ni = total number of moles in the system under consideration
(27)
For gaseous reactions in ideal solutions and where activities are unity
at unit fugacity, a^ - VVA1!^A = WAinA/nt), and x = (zmntB'T)/V.
Substituting in Equation (26) gives
kvAUATT
r = ^
hvAZmR'TUA
,,
(28)
For ideal gases VA and Zm are unity, and Equation (28) becomes
*
kuAT* ' * hR'TuA
r = ^
= kvA = ^
.,^
(29)*
CHAP.
XVIII]
817
,
,
dnA
or in a batch system where r = and T = time
Var
- ^
= kR'Tn^
(30)*
Integration gives
In=
kR'Tr
(31)*
UA
(32)
Where activities are unity at unit mole fraction Equation (32) becomes
kyAnAyariB
r =
.,
(33)
JcVAVB(ZmR'T)^AnB
knAnB{Tr*Y
J * *
kjR'T'PnAnB
KJIAVB
^T;
C^SJ
n,
V
From Equation (35) it is evident that in mixtures of ideal gases the
rate of a second-order reaction is proportional to the square of the
pressure or inversely proportional to the square of the volume of the
system.
For third-order reactions of the type A -{ B -{ C^R
the rate of
the forward reaction is expressed by
r = kaAttBac
(36)
Where activities are unity at unit mole fraction the rate equation
becomes
kjAnAyBnBycnc
,__.
r =
3
(37)
818
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
r =
kvAfsvcnAnsncTT^
kvAVRVciZmR'TYnAUBnc
,.
zr,
(38)
r* = ^ ^ ^ ^ = lvA% = ^^^^^^^^"-"^
(39)*
- f kiQAaB
(40)
As developed in Chapter XVI, all reactions are to some degree reversible, and if conditions are such that the rate of the reverse reaction is
important its effect must be included in the over-all rate equation.
Thus, if we consider a reversible first-order reaction of the type
A'^R,
the net rate of reaction of A is expressed by
r ^kaA
k'aa
where
k' = reaction velocity constant of the reverse reaction
(41)
CHAP. X V I I I ]
819
where
K equilibrium constant
Combining Equations (41) and (42) gives
r = A-(a^-^)
(43)
(44)
820
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
"
where
CA = HA/V = concentration of A, moles per unit volume
kc = reaction velocity constant in concentration units
(45)
CHAP.
821
(46)
Combining (45) and (46) with this reference state for activities and
using consistent units throughout gives
h = Hyly%7y)---(v^y^''-
(47)
For ideal solutions of gases where activities are taken as unity at unit
fugacity, Equation (1) becomes
r = H''A.CA.n''BCB)\''cCcy (zJi'T)-^'
(48)
Combining (45) and (48), for gases in ideal soluijon, and using consistent units throughout yields
h = kvlvlvl (zJi'TY+^'
(49)
Equations (47) and (49) relate the two reaction velocity constants k
and kc and may be used to calculate one from tho other. Equilibrium
constants in concentration units corresponding to k^ are also in use to
some extent. Thus,
^ifis ' ' '
J^^ = ^T~.-f'
(50)
a b c
CAOBPC '
(51)
T7s
(52)
VRVS
In many cases it may be assumed that ideal conditions exist, and the
values of y, v, and z in Equations (46-52) may be taken as unity.
The widespread use of concentration units in kinetic relationship has
resulted from the fact that many laboratory rate measurements have
been made at conditions of substantially constant volume. Under these
conditions data are determined directly in concentration units, and the
resulting rate equations are more simply integrated than if activities are
employed. It is convenient to use rate equations in concentration units
822
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
for the analysis of such laboratory data at constant volume. Thermodynamic reaction velocity constants may then be calculated from
Equations (46-52).
In dealing with gaseous-reaction-rate data in concentration units the
normal molal volume is frequently used as a unit of volume. Thus, in
the metric system concentrations and rates are expressed in terms of
gram-moles per 22.41 liters. Concentrations in these units are numerically equal to pound-moles per 359 cu ft. If pressures are expressed in
atmospheres, the values of the gas-law constant R' is 1/273 in (atm)
(22.41 liters)/(K)(g-mole) or 1/492 in (atm)(359 cu ft)/(R)(lb-mole).
The normal molal volume may be used exactly like any other unit of
volume, but careful designation of units is necessary to avoid confusion.
I t is a good plan to verify the dimensional consistency of any rate equation by writing it in terms of the units employed and making sure that
all cancel.
Illustration 3. A second-order reaction in a system of ideal gases at a temperature
of 910K has a reaction velocity constant kc = 70 liters/(g-mole) (sec). Calculate
the reaction velocity constant fc in g-moles/(liter) (atm)* (hr).
Solviion: From Equation (49), if kc is converted to consistent time units,
fc(3600)
(70) (3600)
,,
g-moles
fc = (B'T)2
,,, = [(0.08206)
,,
,(910)]2
,,. = 45 (liter)
(atm)2(hr)
Equations (1) and (45) express the instantaneous rate at which a reac-'
tion proceeds as a function of the conditions in the system for a particular
infinitesimal interval of time dr in a batch process or for an infinitesimal
increment of volume dV in a flow process. As the reaction proceeds
these conditions change with time in a batch process and with distance
traveled in a flow process; as a result the rate of reaction continually
changes. In order to evaluate the effects produced during a finite
interval of time or in a finite flow reactor it is necessary to integrate the
instantaneous rate equations with due consideration of the changes of all
variables.
Nonflow Reactions. It is convenient to express the results of a reaction in terms of the extent of conversion of the limiting reactant A.
The conversion XA is defined as the moles of A transformed per unit mass
of original reactor charge or feed. Thus,
nA = riiio - ZA
driA = dxA
(53)
(54)
CHAP. XVIIl]
NONFLOW REACTIONS
823
where n^Oj-riA = the number of moles of A per unit mass of reacting system initially and at any time r, respectively.
From the definition of reaction rate, in a batch process,
- + ^
(.5,
where r = moles of A converted per unit time per unit volume of reactor
occupied by the reacting system
Vc = volume occupied by the reacting system per unit mass
The integration of Equation (55) requires complete expression of both
r and F as functions of XA- The instantaneous rate of reaction r is
related to XA through the differential rate equations of the preceding
section.
For a batch or nonflow reaction Equation (55) is integrated directly
to obtain the time r required for a specified extent of conversion XAThus,
r^dxA
(56)
Jo Vcr
If the reaction is restrained to constant volume and temperature the
integration of Equation (56) is readily carried out for reactions of simple
order in systems which form ideal solutions. For a first-order reaction
in an ideal-liquid system in which the reverse reaction is negligible the
rate is expressed by Equation (27) which may be combined with Equations (47) and (56). Thus,
r^A
Jo
dXATlj
VMUAO
^
XA)
r^'A
JO
dXA
JC/JIAO -
.
XA)
(58)
UAO
XA
824
HOMOGENEOUS REACTIONS
[CHAP. X V I I I
TABLE LII
HOMOGENEOUS REACTION R A T E S AT CONSTANT VOLUME
FOK
VcdT
Unidirectional
Readions
1 ,
T = - In
UAO
, ,
(a)
-W--
hriAa
(Ao XA)
Second Order: A + B yP
Ve
) UBO)
rrefio(AO XA)~\
\,nAo{nBa XA)J
Third Order: 3A - ^ vP
r
Third Order:
{^\
'\ y j
'
_ ^ ^
^ ~ 2hn\,
r 2nAo
-XAI
L(nxo - XA^J
^'^^
2A+B-^vP
, n\nB
r = kc r;r":
Vl '
yl
\
XA
,
T
;
' = kc(,nBti ^nAo)LnAo{nAo
XA) +' n^o 2WB
,
In
rnAoiuBi, -^XA)!
-.
^
L TlBo (JIAO XA) J
, .
(e)
UAnBric
1' '^O
y i
V
T
where A
^ r ^ 1
'^^''
, ^ 1
g
, ^ 1
o 1
Kc L - A C n ^ o XA
A B nsa XA B U rico XAJ
= TIBO UAD;
= nao nco;
Reversible
/n
C = nco TIAO
Reactions
First Order: A *^ R
kc (
ncN
r = - ( n . - - j ;
Kc
, r
r = ^ ^ ^ . . - ^ In \_^^^^^ _ ^^^ _ ^^^ ^ ^^^J
(g)
825
NONFLOW REACTIONS
CHAP. XVIII]
For various types of second-order and mixed second-first order reversible reactions
T may be expressed by Equation (h). The constants o, 6, c, and q are defined in each
case.
q = iac 6^
where
3 < 0;
T= -
\-Evi-R
a KcnAoriBo VCURO
(>)
b = KcTiBo KcnAo Vc
(J)
2A*^B
a = VeKcnAo waowso
6 = VcKc nsa WHO
c = -I
a - KCIIAI
VeURU
(k)
h = 2XciAo ~
0)
c =Z.
Second Order:
A+B^R+S
A+B^2R
a = KcUAonBo WBOWSO
(m)
nso
c = Kc - 1
24 ? K + iSr
J.
or^
6 = -iKcUAD
c = Kc
'*'"'
(o)
a = ifcriAoiBo i l o
6 = KCUM KcUm ~ 4n.Bo
c = iiTo - 4
2A?=i2i?
a = X^o " B O
h = 2KcnAii 2nBo
c = X, - 1
(n)
(P)
. 1
826
HOMOGENEOUS REACTIONS
[CHAP. XVIII
(o) Let njLo = kg-moles of SO2CI2 initially present in the constant volume of
reacting system
XA = kg-moles of SO2CI2 transformed in time r
From Equation (a), Table LII,
1 ,
T = In-
fo
nAo
nAo XA
0.00132
WAO - XA
1 - = 0.9612
7140
XA = 0.9
/95,500\ / 0 . 9 \
CHAP. XVIII]
NONFLOW REACTIONS
827
k,
0.0001482
kc
0.000677
kc = 0.0001482 liter/(g-mole) (min)
TiAQ = 1.151 g-mole per Uter
nBo*= 48.76 g-mole per liter
TlRO =
nso
XA
Vc
o
6
=
=
=
=
=
0
g-moles ester converted
1.0 Uter
KcnAoriBo - JiBonso = (0.2189) (1.151) (48.76) = 12.29 (g-moles) V (liter)*
-KcUA'i - KCUBO - WBo - nso = (0.218g;(-1.151 - 48.76) = -10.93
g-moles per Uter
c = Z - 1 = -0.7811
g = 4ac - 6 = (4) (12.29) (-0.7811) - (10.93)^ = 157.9 (g-moles)V(Uter)'
Vg = 12.57 g-moles per liter
Substituting in Equation (h) gives
(0.2189) [2.303 T
/2(-0.7811)a:A - 10.93 - 12.58\
~ 0.0001482 [12.57 L ^ V2(-0.781 Izx) - 10.93 -t- 12.58/
/ ( - 1 0 . 9 3 + 12.58)\11
\ ( - 1 0 . 9 3 - 12.58)/Jj
^ (-1.562x4 + 1.65)
or
2.712XA = 1.099
XA = 0.405
Percentage conversion of ester = (0.405/1.151)(100) = 35.2 per cent
(6) At equiUbrium:
^- =0.219
(1.151 -x^)(48.76 -XA)
XA = 1.04
Percentage conversion = (1.04/1.151) (100) =90.5 per cent
828
HOMOGENEOUS REACTIONS
[CHAP. XVIII
(c) If the reverse reaction and removal of water are neglected, the differential
rate equation may be written as (driA) KTIA) = (Jcnadr) / (Vc) or
dxA
knBodr
UAO XA
VC
Integrating yields
,
UAO
kUBoT
In
, riAo XA
VC
1 151
In
^
= (48.76) (0.0001482) (60)
(1.151 XA)
XA = 0.405 g-moles
/0.405\
Percentage conversion = I
1(100) = 35.2 per cent
From the results of parts (a) and (c) of Illustration 6 it may be noted
that little error is involved in assuming that the reaction follows a firstorder mechanism. This results from the fact that the water is present
in such great excess that changes in its activity or concentration are
negligible. Reactions of higher order under conditions which permit
their treatment as first order are termed pseudo-first-order reactions.
Many systems of industrial importance are of this type and may be
handled with satisfactory accuracy on the basis of assumed pseudo
mechanism. This procedure frequently results in considerable simphfication of calculations but must be used with great care and recognition
of the possible errors involved.
Simultaneous Reactions. The simplest case of simultaneous reactions is that of an irreversible first-order reaction in which the reactant A
simultaneously reacts in two ways. Thus,
(1)
(2)
A-^R
A-^S
The over-all rate of decomposition of A is the sum of the rates of the two
reactions which may be considered separately. If yA and ZA represent
the moles of A decomposed per unit mass of feed by reactions 1 and 2,
respectively, and XA = VA + ZA, from Equation (45),
dyA = kciiuAo yA - ZA) dr
dzA = kciiuAo yA ZA) dr
dxA = dyA + dzA = (^ci + A-c2)(nAo x^ dr
(59)
(60)
(61)
XA
or
2/A =
' 2i 4_ 1
A-ci
.,
(62)
CHAP. XVIII]
CONSECUTIVE REACTIONS
829
^ = (r4-)ln-^^^
(63)
~d7
dns
(65)
= koitiR kcinA
17 =
kciUB
(66)
-
(67)
where UA, n^, ns = moles o{ A,R, and S present per unit mass of original
charge
An expression for UA in terms of T and UAO, is obtained by rearranging
Equation "(a) of Table LII. Thus:
UA = n^oe"*"''
(68)
Substituting (68) in (66) gives
- ^
(XT -
= h^riB - hiTiA^-'"'^
(69)
830
HOMOGENEOUS REACTIONS
[CHAP.
XVIIl
(71)
If the reactions considered are reversible to a significant extent, Equation (64) is written
ka
id
A^R^S
(72)
- =
- -^j
UT
(73)
Kcl/
ns\
ns\
,.,[nR-yjc..[nA--^
= riB \kci + ^
) - -^
riAkoi
(74)
,^^
d^'UA
~d!T2
+ ^nA
duA
dr
kcl / ,
Kci\
, kci\
KciJ
, kcikci
KciKci
(76)
From Equation (73), JIB may be expressed in terms of n^, and, from a
material balance,
ns = riAo riB- riA
(77)
' I. S. and E. S. Sokolnikoff, " Higher Mathematics for Engineers and Physicists,"
McGraw-Hill Book Company (1934).
' T. K. Sherwood and C. E. Reed, " Applied Mathematics in Chemical Engineering," McGraw-Hill Book Company (1939).
CHAP. XVIII1
CONSECUTIVE REACTIONS
831
UAo = 0
(78)
(79)
AcliVc2 C'2
Kci-
JC2 =
-02
A =
-^1 +
V^f- -4:E2
2
-^x-
Vfi!- ~4E2
E, = ka (l +
^)+^"^0+^; )
Ei
Although the reaction under consideration is of a simple type, Equation (79) is complex and difficult to apply. For the more complicated
combinatiqns of higher-order consecutive and simultaneous reactions
which are commonly encountered in industrial operations analytical
integration may not be possible or practicable. For these problems,
which are generally complicated by varying reaction conditions, graphical or trial integration procedures are preferable, as discussed in following sections.
832
HOMOGENEOUS REACTIONS
[CHAP. XVIII
CHAP.
XVIII]
FLOW REACTIONS
833
(82)
where,
Tfit = total moles of reacting system per unit mass in the section dVr
nA moles of reactant A per unit mass of reacting system in the section dVr
Before the integration can be completed nt and UA must be expressed as
functions of XA. If 5 is the increase in the number of moles in the reacting
system per mole of reactant A converted.
nt-
nail
\\
-\
(83)
-] = no(l + (^A)
nno/
o/
where
no = total moles of initial feed per unit mass, or the reciprocal of
the average molecular weight of the feed
5 = increase in the number of moles of the system per mole of A
converted = [(r + s ) (a + 6 )]/ for the general reaction of Equation (5)
CO = 5/no, a constant for a particular system
Combining (53), (82), and (83), gives
Vr _
r
no
r^A (1 +
irkvA^o
MA)
{nAa ^A)
-UXA + (1 + unAo) hi
(85)
834
HOMOGENEOUS REACTIONS
(CHAP. XVIII
Flow Reaclions
aA + bB = rR + sS
r = moles of component A converted per unit time per unit volume
riA = moles of A unconverted per unit mass of feed
no = moles of feed per unit mass of feed
( = moles of reacting system per unit mass of feed = 'no(l + USA)
Vr = volume of reactor occupied by reacting system
,F = feed rate, mass per unit time
riAo, nao, nso, nso = moles of components A, B, R, S, respectively, per unit mass of
entering feed
XA = moles of A converted per unit mass of feed
A = nAQ
XA
a
S
0) =
no
k = reaction velocity constant
K = equilibrium constant
jT = total pressure
General rate equation:
dVr
Irreversible Reaclions
First Order: A~*vR;
5 =v 1
rii
fcir
"Ao XAJ
^^fXH.A
fcff* L
+J - - ^
^+Mln(^^^)+iVln(-^^^)l (b)
nAo(nAo XA)
\n^o XA/
\nBo XAJA
CHAP. XVIII]
FLOW REACTIONS
835
v-2
5 = -
Case 1. 2A -^vB;
H = 0,^
J ~ (1 + uriAo)^
M = 2M (I + uriAo)
AT = 0
Case 2. A+B-^vR
(o)
.= ' - 2
fl' = co2
J =0
^j
(I + con^o)'
(d)
^40 ~ n s o
(1 + UHBo)'
XA
HXA+J
k%^ L
+ M'In'
flAnfjlAO XA)
+ OIn
UcO
\-P
<r
Case 1. ZA-*vR
S=
+ A'^ In
riAo XA
nBo <TXA
xx(2n^o XA)'\
(e)
=1
r - 3 H = -a,
iV = 0
3 1
/ = -3&)(1 + wn^o)* Q = 0
Case2. 24+B->'if;
r-3
'r=h
Ar = -
H = -2a.'
2(1 +2anBo)'
(2B0 UAH)'
..(=?f=)l
, I
(f)
2(1 + iiUAoY
Q=0
2nBi> UAO
Af =
P = 0
(2nBti
Case 3. A + B + C -^ vR;
"^ ~ \
w!
/
When n^o = nao, use Equation (g).
TlAor
6 = - 3
(g)
836
HOMOGENEOUS
REACTIONS
[CHAP. X V I I I
(1 + wnso)'
(UAO nso) (jiBo nco)
N =
H = -co'
(1 + tonco)'
=0
M =
(h)
(1 +<inAo)'
(n^o ~- nBoJinAo nco)
P = 0
Reversible Reactions
First Order: A^R
(w = 0)
Vr _
F '
where
Kno
,
P
-In
(1 + K)k7r '" P -XA
(i)
KnAo nna
P =
1 +^
Mixed First and Second Orders: T h e constants o, 6, c, and g are defined in each case,
g = 52 _ 4oc,
and
g < 0
General Case.
= = -7
s^ + 17 In (
V -?
L(2cx4 + 6 + V - 2 ) (6 -
V-g)J
Forg<0
?7 =
Casel,
;T-5- )
Kn\
/
= fc I
\
.
;
n'.
(k)
a = irTiKonso KnanAn
6& = XXo(l
n o ( l oinAo)
0)1
+ 7r(nso + nso)
C = KlMo + X
(1)
-r )
Km/
aa
b6
c
noJifio
WoWfio
iiTrnxoiBo
KirnAonBo
=
=
Kir
{UAO
+
= KTriuAo + UBD) + ni)(l + omBo)
= wwo ^^
XTT
(m)
A^2R
r = fc (
\ni
Case 4.
_ (1 + 6t7)
4 + B <= B
.J
Case's.
y = ^
c
2c2
A-^R-^B
n,
Case 2.
ca(bo> 2c)
- )
Kn\J
a = noTiso Kim^o
6 = ax'im^o
lAo ++ n o ( i + wn^o)
c = ^oirio Kir
(n)
2.4 ?= B
= k ( ^
(o)
CHAP. XVIII]
FLOW REACTIONS
837
Second Order: (w = 0). The solution is given by equations (i) and (k). To determine the constants a, b, c, use the negatives of the values of a, b, c given in Table LII
for the similai cases as follows:
A +B :^B + S
A +Bi2R
2A^B
+S
2A ^ 2R
Equations
Equations
Equations
Equations
(m) of LII
(n) of LII
(o) of LII
(p) of LII
or use the solution (h) of LII directly, with +.he values of a, b, c given by equations
(m), (n), (o), or (p), Table LII, and with r in (h) replaced by ^ and kc = k (R'T)'.
s
in
= = - = 1.35
no 0.741
838
HOMOGENEOUS REACTIONS
XA = (0.9) (0.741) = 0.667;
S = 1.0;
on
'
1 + uriAo = 2.0;
ICHAP. XVIII
UXA = 0.9
"^
0.741
= 10
Substituting,
Vr
F
0.741
[-0.9 + 2.0 In 10] = 27,100 (cu ft)(hr)/100 lb
(0.1015) (10-') (1)
n^, = n/^ =
(a) At equiUbrium:
Kc =
(g,) (nxt)
nh
= T7,
TT = 0.0167
4(1 - xy
X = 0.205
(fe) At 80 per cent of equilibrium conversion, x = (0.8) (0.205) = 0.164. This
reaction is a reversible second-order reaction of the type represented by Equation (o),
Table LII.
riAo = 1.0; a = KcJi^o = 0.0167;
c = Kc - i =- -0.2333
CHAP.
njjo
= 0;
nso = 0;
V^
SPACE Vl
xvin]
6 = 2KcnAo = -0.0334;
6' = 0.001166
)CITY
839
T
666
^ ' = 2^3 = i7-3 = 2 - ^ (^^^^"
'']
per lb-mole
Vj = 5.954
y
From Equation (h), Table LII, if T is replaced by ^
Vr ^ VjKc 2.303
L\2ca; + b + V-q/\b-
V^/J
Vr ^ (5.954)(0.0167) (2.303)
r / 2 ( - 0 . 2 3 3 3 ) (0.164) - 0.0334 - 0.1294\
F
(0.000588)
(0.1294) ^L\2(-0.2333) (0.164) - 0 . 0 3 3 4 + 0 . 1 2 9 4 /
,
/ - 0 . 0 3 3 4 + 0.1294\1
\ - 0 . 0 3 3 4 - 0.1294/J
=[(3010)(0.86) = 2590(359cu ft)(min)/lb-mole
Vr = (2590) (0.0333) = 86.2(359 cu ft) or 30,900 cu ft
Similarly, at 90 per cent of equilibrium conversion, z = 0.185.
y , = 36,500 cu ft
(c) Netrateof production of iodine in pounds per hour per cubic foot:
.
(2) (126.9) (0.164)
For 80 per cent conversion
"
= 0.00135 Qb I,)/(lir)(cu ft)
oU,9(X)
840
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
(87)
where
F = feed rate in pound-moles or gram-moles per hour
Vr = reactor volume in 359 cu ft or 22.4 Uters
REACTIONS OF COMPLEX ORDER
As is pointed out on page 819, reactions which from their stoichiometric equations might be expected to be of simple order frequently
yield rate equations of complex order. Although it is believed that any
reaction of complex order can be expressed in terms of a succession of
reactions of simple order, the resulting'expressions are frequently so
complex that it becomes expedient to employ empirical rate equations.
Such empirical equations may be used satisfactorily where the reverse
reaction is negligible and equilibriiun is not a consideration.
An empirical rate equation of complex order for an irreversible reaction is developed frpm experimental data by graphical differentiation of
curves relating conversion to time or volume. The resulting reaction
rates are then empirically related to activities or concentrations. Such
rate equations may be applied to problems of reactor design by the same
procedures used for reactions of simple order.
Where reverse reactions and equilibria are involved, the problem is
much more difficult. If it is attempted to develop empirical equations of
complex order for both the forward and reverse reactions, their forms
must be such as to satisfy the thermodynamic requirements of equilibrium. It is difficult to accompHsh this result by a purely empirical
procedure, and it is preferable to develop a form of equation based on a
CHAP. XVIII]
841
_ -
Br2
^2Br
(4)
(6)
842
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
These three reactions constitute a chain in which atomic bromine isconsumed in reaction (4) and a corresponding amount is produced in
reaction (6). Since there is no net consumption of atomic bromine it is
reasonable to assume that equilibrium is maintained in reaction (2).
Then, if the chemical symbols are taken as representing concentrations,
' Br = VKciBr,
(88)
where
Kc2 ~ the equiUbrium constant of reaction (2)
If only reactions (2), (4), and (8) are significant, the rates of (4) and (6)
must be equal, and r the over-all rate of formation of HBr is equal to 2r4
or 2r6, where
n = rate of removal of H2 by reaction (4)
n = rate of removal of Br2 by reaction (6)
Treating (4) and (6) as reactions of simple order, gives
n = /c4(Br)(H2) - A-'4(HBr)(H)
re = A-o6(H)(Br2) fr6(HBr)(Br)
(89)
(90)
where ^c4 and k^ are the forward and kU and ^^ the reverse reaction
velocity constants of reactions (4) and (6), respectively. Since the two
rates are equal, Equations (89) and (90) may be equated and combined with Equation (88).
A-c4VKe2Br2(H2) - /f^(HBr)(H)
= ^.6(H)(Br2) - kiyK,2BT2(HBt)
(91)
^ ^
CHAP. XVIII]
CHAIN REACTIONS
843
844
HOMOGENEOUS REACTIONS
[CHAP. X V m
plausible mechanisms until one is found which is in satisfactory agreement with the data. The selection of "probable mechanisms may be
effectively guided by the theory of absolute-reaction rates. ^
Convincing proof of the existence of free radicals has been furnished
by various experimental methods, and the chain-reaction theory is
supported by the action of inhibitors which greatly reduce the rate of a
reaction even though present in minute amounts. For example, small
traces of nitric oxide are found to reduce markedly the rate of decomposition of ethyl ether. According to the chain-reaction theory such an
inhibitor functions by reducing the concentration of free radicals in the
system. An inhibitor initially present in a reaction may be consumed
by irreversible reactions and finally disappear. Such a situation furnishes the explanation of the frequently observed induction period
during which a reaction proceeds at an abnormally low rate and then
abruptly increases to its normal value. Similarly, there is evidence that
the rate of chain reactions can be increased by the presence of small
amounts of accelerators which serve to increase the free-radical concentrations.
Another experimentally observed phenomenon which supports the
chain mechanism is the retarding effect of solid surfaces on many normally homogeneous reactions. It is frequently found that the rate of
reaction is increased merely by enlarging the reactor with a resultant
reduction of solid surface per unit volume. This effect is explained by
the adsorption of free radicals on thei solid surfaces which reduces the
effective free-radical concentration in the homogeneous phase.
INTERPRETATION OF LABORATORY RESULTS
The laboratory and pilot plant data on which reactor designs must be
based are in general of three types:
1. Measurements of composition as a function of time in a batch
reactor of constant volume at a substantially constant temperature.
2. Measurements of composition as a function of feed rate to a flow
reactor of constant volume operated at constant pressure and substantially constant temperature.
3. Measurements of composition as a function of time in a variablevolume batch reactor operated at constant temperature and substantially constant pressure.
The third type of data is much less common than the other two, and
the experimental technique is more difficult. A variable-volume reactor
generally depends on varying the level of a confining liquid such as a
molten metal in order to maintain constant pressure. This method is
CHAP. XVIII]
COMPLEX REACTIONS
845
846
HOMOGENEOUS REACTIONS
[CHAP. X V I I I
T h e individual rates are then correlated with t h e corresponding concentrations or activities t o determine t h e proper rate equations. T h i s
procedure is demonstrated in t h e following illustration:
Illustration 9. Diphenyl is produced by the pyroiytic dehydrogenation of benzene
according to tlie reaction:
(1)
2CeH6 ?^ C,2H, + Hj
Reliable rate data are not available on these reactions, but the following approximate
data, based on estimates prepared by L, S. Kassell, were presented by Murphy, Lamb,
and Watson'.
In a laboratory investigation of the pyrolysis of benzene to diphenyl, liquid benzene
is vaporized, heated rapidly to the desired reaction temperature, and fed continuously through a reactor tube which is maintained at constant temperature and
pressure. Under experimental conditions no appreciable decomposition occurs in the
preheater. The reactor tube is 37.5 in. long and 0.5 in. in diameter. The product is
withdrawn continuously from the reactor and cooled rapidly to condense the vapor
and to avoid further decomposition, and the liquid product is analyzed for benzene,
diphenyl, and higher polybenzenes which are assumed to be tripbenyls.
.
The compositions of the liquid product for different feed rates are tabulated in
Table A for experiments run at 1265F and 1 atm and for one run at 1400F and 1 atm.
From these data it is desired to develop complete reaction-rate equations.
Basis of Interpretation. Reaction rates are expressed in pound-moles per hour per
359 cu ft of reactor volume and feed rates F in pound-moles per hour. On this basis,
F IVr = Sv in accordance with Equation (87). The following symbols are used to
denote the compounds involved: B = benzene, CeHe; D = diphenyl, C12H10; and
T = triphenyl, CisHu.
,
Yr = volume of reactor =
37.5ir
, = 0.004263 cu ft
Since the density of liquid benzene at 60F is 879 g per liter, if F' is the feed rate in
liters per hour.
p =
and
S . = (-:?^^^^2(35?)=2089F'reciprocal hr
0.004263
The complete composition of the product from each experimental run is calculated
from the stoichiometry of the reactions. A typical calculation based on 100 lb of
liquid products, is shown in Table B.
' G. B. Murphy, G. G. Lamb, and K. M. Watson, Trans. Am. Inst. Chem. Engrs,
34, 429 (1938).
PYROLYSIS OF BENZENE
CHAP. XVIII]
847
TABLE A
PYROLYSIS OF BENZKNE AT 1 ATM PRBSSUBB
F' = feed rate of liquid benzene in liters per hour (measured at 60F)
Percentage Composition of Liquid Product by Weight
F'
Per cent B
0.846
0.423
0.282
0.212
0.14^
0.121
0.106
0.0282
0.0141
83.0
70.8
62.5
56.8
50.3
48.6
47.4
44.7
44.7
Per cent D
Per cent T
At 1265F
14.6
22.4
26.2
27.8
29.2
29.4
29.4
29.4
29.4
2.4
6.8
11.3
15.4
20.5
22.0
23.2
25.9
25.9
13.7
2.0
At 1400F
2.75
84.3
TABLE B
COMPLETE ANALYSIS OP REACTION PRODUCTS
Diphenyl
154.2
14.6'
Triphenyl Hydrogen
230.3
2.016
2.4
Total-
100
0.0947
0.01042
....
1.16782
0.1894
0.0947
0.03126
0.02084
....
1.28336
0.11554
0.0738
no
0.0081
riT
0.0900
UH
1.000
tit
848
HOMOGENEOUS REACTIONS
1.0 r
1 ...
[CHAP. XVIII
0.9
0.4
gO.7
f 0.6
y'
y ^ n r
yC
Wr+Mu
0.3
0.443^
WH
01
M
0.2
D.322 -<-
^0.3
II
8 0.2
^^^-^..^^B
.sS
0.1476*
.^0.087 i
Ui
0.1
0 r-t""^
0
10
20
0.1
S'a
nv'
30
40
50
60
ixlO*
S.
FIG. 168. Pyrolysis of Benzene.
TABLE C
SUMMARY OF COMPOSITIONS OF TOTAL PRODUCTS
F'
Sv
F
n
At 1265F
0.846 1766
0.423
883
0.282
688
0.212
442.5
0.141
294.5
0.121
252.7
0.106
221.2
0.0282
68.9
0.0141
29.47
llSviW)
5.63
11.32
16.97
22.62
34.0
39.7
45.2
169.7
339.3
UB
0.828
0.704
0.622
0.665
0.499
0.482
TlT
no
0.0737
0.113
0.1322
0.1400
0.1468
0.1477
tlT
0.00812
0.02297
0.03815
0.0519
0.0691
0.0740
o.4ro 0.1477 0.0781
0.443 0.1476 0.0870
0.443 0.1476 0.0870
njcf
no + nr
0.0900
0.1590
0.2085
0.2440
0.2847
0.2960
0.3040
0.3220
0.3220
0.099
0.169
0.224
0.270
0.320
0.337
0.346
0.370
0.371
CHAP. XVIII]
PYROLYSIS OF B E N Z E N E
849
At 1400F
2.75
5750
d{llS,}
n\
dnD2
rj =
dns
ri + rj
~d{llSr)
dno
(c)
Ti
(^^
5 ( 1 7 ^ = -'= + 2
driT
where
ri, rj = rates of reactions ( l ) a n d (2), respectively, lb-moles/(hr) (359cuft)
ki, ki = reaction velocity constants of reactions (1) and (2), lb-moles/(hr)(atm)*
(359 cu ft)
Sv = gas space velocity at 32F and 1 a t m (1 /hr)
UB, no = moles of benzene and diphenyl, respectively, per mole of feed
nt = total moles per mole of feed = UB + TID + nr + UH
a- = total pressure, atmospheres
Ki, Ki = equilibrium constants of reactions (1) and (2), respectively
Values of
(0.1476) (0.3220)
(0.443)^
-''''
nTfin
^ - = ; ^ -
(0.0870) (0.3220)
(0H43) (0.1476) - - ^ ^ ^
(S)
(^)
T h e reaction velocity constants fci and ki may now be obtained from Equations (a)
and (b) where ni the total number of moles of reacting system per mole of feed is constant and equal to 1.0. For example, for a space velocity of 883 reciprocal hr from
Equation (a),
fci
(146.4)
850
HOMOGENEOUS REACTIONS
[CHAP. XVIII
(28.5)'
r = lb-mole/(359 cu ft)(hr)
k = lb-moles/(359 cu ft)(hr)(atm)2
s.
llSr(.W)
1766
883
588
442.5
294.5
252.7
221.7
58.9
44.25
5.63
11.32
16.97
22.62
34.0
39.7
45.2
169.7
226.2
Ti
100.0
44,70
20.20
9.30
3.18
0.962
0
0
0
22.1
28.5
26.2
22.0
10.1
8.1
0.6
0
0
ri
244.2
146.4
93.6
62.60
26.36
18.12
1.20
0
0
Average
ki
k2
370
347
342
351
342
350
338
372
400
411
442
370
406
430
348
404
The constancy of the reaction velocity constants in Table D confirms the assumption that the reactions are consistently of the second order. A more conclusive test
would be to operate the reaction under widely different pressures and redetermine the
reaction velocity constants. These constants are unaffected by pressure if the proper
rate equations are used and deviations from ideal-gas behavior are considered.
Comparison of the composition of the products in Table C obtained in the single
run at 1400F and a space velocity of 5750 with the curves of Fig. 168 indicates that
at 1265F this same composition is obtained at a space velocity of 1815. Since the
conversion is small, this indicates that the rates of the forward reactions are equally
accelerated by increase in temperature. With this assumption the rates of the forward reactions at 1400F are 5750 /1815 or 3.16 times faster than at 1265F. Thus, at
1400F (1033K),
fci = (3.16) (348) = 1100 lb-moles/(359cu ft) (hr)(atm)
ki = (3.16) (404) ^ 1276 lb-moles/(359 cu ft) (hr) (atm)
The enthalpies of activation AHi, of the two forward reactions ase equal with the
assumption made and may be calculated from Equation (18). Thus,
CHAP. XVIII]
PYROLYSIS OF BENZENE
denoted hy A, k = - j e
851
V Zm
30190
' -I
Jfcivfa^ = (2.68)(10')e ^
-6597
-6597
kiP^Zm= (3.11)(10)(10)
TABLE E
THERMODYNAMIC PEOPEBTIES
S298.2
(6) (10')
(C)(10)
31.23
64.39
98.1
128.2
AS298.2
6.88
0.23
-0.20
1.74
Aa
0.066
77.83
149.11
214.33
A6(10')
0.279
-27.16
-52.25
-73.65
Ac(10)
Reaction (1) 2B = D + H
0.55
Reaction (2) B-{-D = r + ff - 3 . 0 6
6.22
8.69
Hydrogen (g)
Benzene (g)
Diphenyl (g)
Triphenyl (g)
-6.48
-12.54
-h2.35
-t-6.04
852
HOMOGENEOUS REACTIONS
[CHAP. X V I H "
From these results the constants Ijj in Equation (XVI-11) are evaluated.
(1) /j? = 958[3.82 - (6.22 + 33.05) + (6.22) (In 958) - (3.24) (958) (10"')
+ (0.39)(958)ni0")] = 3363 cal per g-mole
(2) IR = 958[1.69 - (8.59 + 48.53) + (8.59) (In 958) - (6.27) (958) (lO"')
+ (1.01) (958)2(10-')] = 1475 cal per g-molo
The standard heats of reaction at 298K may be calculated from (XVI-9):
(1) Aff298 F= 3363 + (6.22) (298.2) - (3.24)(298.2)'(10-^) + (0.78)(298.2)(10-)
= 4950 cal per g-mole
(2) Affjss = -1475 + (8.69) (298.2) - (6.27) (298.2)^(10-') + (2.01) (298.2)'
(10-) = 580 cal per g-mole
The available calorimetric data indicate a heat of reaction at 298K of 7,250 cal
per g-mole for reaction (1). This is in poor agreement with the value previously
calculated from the estimated entropy change and equilibrium data although the
difference is only 0.15 per cent of the heat of combustion of diphenyl. The discrepancy may result from errors in any of the three sets of data involved. Such
inconsistencies are constantly encountered in the present state of development of
thermodynamic data and must be rationalized as well as possible. In this ease the
discrepancy in heats of reaction will not seriously affect the equilibrium or kinetic
calculations over the temperature range of interest, and the calculated values will be
used to maintain consistency with Ihe equilibrium measurements. In the design of
the reactor, to which heat must be supplied for the endothermic reaction, the calorimetric heat of reaction may be used to insure a more conservative design.
An alternate procedure would be to accept the calorimetric and estimated heats of
reaction at 298K and the heat-capacity equations and calculate the standard entropy
changes from the equilibrium measurements. In, general, however, as a result of
spectroscopic and statistical methods, absolute entropy data are more reliable than
calorimetric heats of reaction.
The equilibrium constants are expressed by the following equations obtained by
substituting the calculated values of IH, IS, Aa, A6, and Ac in Equations (XVI-11
and 23).
-4.576 log Ki =
3363
+ 39.27 - (14.32) (log T) + (3.24) (lO"')? - (0.39)(10-)T
(i)
8597
(10) ^ phn^
[(,,,). l(!^i:^]
(k)
CHAP. XVIII]
COMPLEX REACTIONS
ft =
(3.11) (10)V r .
w
,
6897
y{nBVB){nDVD)
(10) ^ ;.*2nJ
(nr.>r)(nHVg)1
^^
J
853
Q,)
854
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
(94)
riA
nt
nBHsir
n^K
where
^1 = reaction velocity constant of reaction (1)
x^i = moles of component A converted by reaction (1) per mole of
feed
nA,nB,ns = moles of components A, B, and S present in there acting
system per mole of feed
nt = total moles of reacting system per mole of feed
Each of the quantities in the integral of Equation (94) may be evaluated for each experimental point. A curve is then plotted relating
XAI as abscissas to l/{nA/nt riRnsT^/'n^t^) as ordinates. The area
under this curve between x^i = 0 and any selected experimental value
of a;^i is equal to the product of the reaction velocity constant and the
value of -KVT/P corresponding to that value of XAI- In this manner a
series of values of ki is established which may be averaged.
This same method of evaluation may be applied to reactions of higher
order, regardless of the complexity of the system if the conversion
attributable to the reaction and the numbers of moles of all reactants
and products actually present in the system are known for a series of
runs at different values of Vr/F on the same feed at a constant temperature and pressure.
Illustration 10. Interpretation of Chain-Reaction Data. In Table A are data on
the chain reaction involved m the hydrogenation of bromine gas which have been
selected from the experimental work of Bodenstein and Lind.' All experiments were
conducted at constant volume. An independent analysis of these data is reported
by Pease.'"
Bodenstein and Lind, Z. Physik. Chem., 5J, 168 (1907).
w R. N. Pease, " Equilibrium and Kinetics of Gas Reactions," Princeton University Press (1942).
HYDROG^NATION OP BROMINE
CHAP. XVIII]
ioioioiooioioo
a.
tOOOOrt<0500i-l
t003(N5DOC0>0tD
OOT-irt<N(NC<IN
CO
o o o o o o o o
< N - * c O 0 0 O O O ' f
OOtSlMt^OO'^O
3a
'^
t-lNCC-^COOO'-HM
o
D3
OT-<r-i(N(N(NC<IN.
a.
o o o o o o o o o
_
l O O O O O O O O O
1
I
1i fI It CO ' ^
M r~,
00^<OM'OC0r-lt
IMa00OC<3Ot>.i-iTj(
odidoddiodid)
o
O Q O O O
*S55oc^.oow
I-H (M M
O
O
CO *
t o OJ
lomomioeocoM
Q
^
(N <N CO * t o C3
oeoootoifliNio-*
O
tOt-Or-HCOCOINO
rt(N-*iotOt^OTj<
O O O O O O ' - i ' - i
dddddddd
M
855
856
HOMOGENEOUS REACTIONS
[CHAP. X V I H
In each run the initial concentrations a and b expressed in gram-moles per 22.4
liters were as follows:
For H2,
o = 0.5637 '
For Br2, b = 0.2947
In Table A, T indicates time in minutes and x is the gram-moles of Hj or Brj reacted
per 22.4 liters.
The mechanism of this chain reaction is discussed on page 842. In terms of the
initial concentrations o and 6 add the conversion x, Equation (93) may be written to
express the reaction rate as follows,
^r = u = Ti = kctvKci'Vb
x{a x) kci{2x)
fertVg^V6~^(2x)"|
kU2x) + k,,(b - x)
(a)
Brj(g)
7650
58.63
8.58 + (0.30) (lO"')?
Br(g)
26,880
41.81
4.97
H2(g)
0
31.23
6 . 8 8 + (0.066)(10-')r-f- (0.279)(10-)r2
HBr(g)
-8,650
47.48
6.30 + (1.819)(10-')r - (3.45)(10-)T2
H(g)
51,900
27.40
4.97
From these data the thermodynamic changes and equilibrium constants accompanying the individual reaction steps are calculated as follows:
(1)
H2(g)+Br2(g)-^2HBr(g)
AHr = -24,234 - 2.867 + (1.636) (lO-')?^ - (0.323) (IQ-^)?'
AST = 20.462 - 2.86 In r + (3.272) (lO-')r - (0.485) (lO-')?^
r , K 298.1
AH" -24,950
AS"
5.10
AG"
Ki
Kci
(2)
!r,K 298.1
AH" 46,110
AS" 24.99
(\G
K,
Kci
(4)
Run I
498.8
-25,244
.4.21
-27,394
1.004(10'^)
1.004(1012)
Run II
Run III
550.6
524.5
-26,331
-25,367
4.13
4.07
-27,608
-27,498
2.876(10")
9.106(101)
2.876(10")
9.106(101)
Br2(g)->2Br(g)
AHT = 45,718 + 1 . 3 6 r - 0.00015r2
AST = 17.33 + 1.36 In r - o.ooosr
Run I
Run II
Run III
550.6
498.8
524.5
46,421
46,359
46,390
25.63
25.69
25.74
33,575
32,900
32,249
1.951(10-15)
1.96(10-")
1.579(10-")
1.068(10-")
1.02(10-")
7.835(10-")
Hs + Brfc;HBr + H
Run IV
574.4
-25,399
4.01
-27,701
3.51(101)
3.51(101)
Run IV
674.4,
46,444
25.799
31,640
9.03(10-")
4.29(10-")
CHAP. XVIII]
HYDROGENATION OF BROMINE
857
Kt
Run I
498.8
16,374
1.84
15,456
1.692(10-')
Run II
524.5
16,377
1.852
15,406
3.8(10-')
Run III
550.6
16,382
1.860
15,358
8.006(10-')
BwnlV
574.4
16,393
1.863
15,322
1.512(10-)
Kct
1.692(10-')
3.8(10-')
8.006(10-')
1.512(10-)
r, K
AH"
AS"
298.1
16,370
1.84
AG
(6)
K,
JKCS
Bun I
498.8
-41,668
2.36
-42,845
5.902(10)
5.902(1018)
Run I I
524.5
-41,709
2.284
-42,907
7.08(10")
7.08(10")
Run III
550.6
-41,722
2.208
-42,938
1.108(10")
1.108(10")
Run TV
574.4
-41,786
2.15
-43,020
2.38(10")
2.38(10")
With these thermodynamic constants the rate data are analyzed by the following
scheme which is demonstrated for Run I at 498.8K.
1000
2000
3000
Time=minutes
FIG. 169. Hydrogenation of Bromine.
4000
The gram-moles of hydrogen consumed x are plotted against time T in Fig. 169.
Prom this plot on a large scale values of reaction rates rt were obtained by graphical
differentiation and plotted on a logarithmic scale against time in Fig. 170. By extension of this plot to T = 0 the value of u = kci'vKa'Vba = 1,95(10-') is obtained
directly, since at zero time the second term of Equation (a) disappears and the value
of X is zero. Since K^, a, and b are known, the value of kc4 is obtained.
1.95(10-5)
''-' = (3.27) (10-) (0.542) (0.5637) = '-^^^^'"'^
'
858
HOMOGENEOUS REACTIONS
[CHAP. XVIII
^
rikei(2x)
h,VK^^Vb
fc.4(2x)2V^vT^
(b)
Values offee6 are calculated from Equation (b) for different times of reaction and
tabulated in Table C. It may be observed that there is no definite trend in the calculated values of kce- The average value ig taken as
kU = 1.753 (10-)
kct = k'cf Kce = 1.763(10-8) (5.90) (10") = 1.035(10")
2
1000
2000
6000
dx /r,
The calculated values for Run I are plotted in Pig. 169 and show agreement with
experimental data.
In ordSr to establish the validity of Equation (a) at other temperatures, the reaction velocity constants were similarly established for three other runs. The results
are summarized in Table D.
.In Fig. 172 these reaction velocity constants are plotted on a logarithmic scale
against 1 /T. It may be observed that nearly linear plots are obtained with maximum
deviations for Run II. From the lin^ of Fig. 171 values of the enthalpy and entropy
of activation of Equation (18) were calculated.
The following results were obtained:
(4)
Hj + Br ?s HBr + H
AH* = 17,720;
AS* = -9.035
CHAP. X V I I I ]
HYDROGENATION OF BROMINE
y-^ ^
859
r~l T-i Ci ^ T^
l3 t ^ C^ t * 05
r)( CO
Co
O ^ " 5 05 CO
O O O O i - i O i - H i - l
>n CO
tj-
'-IO3r-CC0<n-.^t
oocico-^tdrrt
coost^-^i(oi>co
COIN<M<N(N(MiHrH
coot^ioeo^HOi-^
^coeO(N(NlM(N'-i'-'
OtO5(NO-*Oo
(N-*^COt>tO>g
_COU5000lM-*gO
<=>000.-irH'-ilNl
O
O
O ,_
M S^
d o o d o ' o o o
p
CO
i>t-Thcn^iN'n(Nco
I>
cot^cOINlNOO'iCO
USTJICOIN'HOOICDN
d d d d d d d o d
I
*(N'-'OOiOOt-COO>
u5U5iiOiCTj<Tt(TtHrt<CO
1 d d d d d d d o o
H
t^t--*0!'-i<NiOlNCO
inooiveocoi-ii-iiM-*
rot^to'OTjtcoc^oi'o
e
,_( lO -^ 05 t^ CD 00
C2 <N O m C rH
"-So t~
d d i': 00 i-H I N i-^
i-H r l 1-1 (M rq cvi
II
-4
lON'^lM'NOOeO'H
OiOOt^tOiO'^COi-l
oeoootoic(NiO'<j(
5Dt>-Oi-lCOCO(MO
O O C > O O O i - i i - l
d d d o d d o o
o o o o o o o o o
OOiONOI^iOCDO
i-i N CO CO * CO ca
860
HOMOGENEOUS REACTIONS
(6)
H(g) + B r , ( g ) - > H B r ( g ) + B r ( g )
Afl* = 7200;
AS' ..= 5.24
[CHAP. X V I I I
TABLE D
SUMMARY OF REACTION VELOCITT CONSTANTS
Run I
498.8
1.955(10')
Lisaaoio)
kcs
kct
1.035(10")
1.753(10-8)
'
Bun II
524.5
5.77(10')
1.52(10i)
1.035(10")
1.46(10^)
Run III
550.6
1.037(10*)
1.28(101)
2.29(10")
2.085(10-)
Run IV
574: A
2.39(10*)
1.58(10")
3.106(10")
1.305(10-5)
From these values of AH* and AS* and the equilibrium constants values of conversion at various times of reaction were calculated for all four runs and plotted in
Fig. 169. It may be seen that the calculated values are in close agreement with
experimental data for all runs except Run
II. It is possible that there was some experimental irregularity in this run.
The values of AH^ calculated by this
analysis are in only fair agreement with the
experimental and calculated values cited by
Glasstone, Laidler, and Eyring for the same
reactions.
Product Distribution and Selectivity. In complex systems the overall effect may be the result of many
primary, secondary, and tertiary reactions. .Since these individual reactions may exhibit^different responses to
variations in temperature, pressure,
and composition, their combined results frequently present a complex
pattern of relationships which can be
rationalized only by being resolved
into the contributions attributable to
individual reaction steps.
In presenting data on such systems
0.0018
0.0020
0.0016
1
it is convenient to designate as conyogversion the decomposition or disFIG. 171 Effect of Temperature on appearance of the key or limiting
the HBr Reaction Velocity Constants. reactant. Thus, percentage conversion is the percentage of the key reactant in the feed which is converted into other products. A tabulation of number of moles of each
CHAP. XVIII]
861
20 80 40 50 60 70
Per Cent Propane Converted
80
90
Fia. 172. Distribution of Products from the Pyrolysia of Propane, (at 725C and
1 atm pressure).
862
HOMOGENEOUS REACTIONS
{CHAP.
XVIII
C3H8?:iH2+C3H6
CaHg ?=i CH4 + C3H4
2C3H8 ^ CjHe + CsHs + CH4
2C3H8 ^ C2H6 + C4H10
k = Ae
(1)
^^;
AH" .AS"
T = degrees Kelvin
A = (3.0158)10";
E. = 66,500
A = (3.6745)101*;
E = 66,000
Jes of nronjiTifi^
A = (9.989)10";
E = 60,000;
AHISOOT = 30,605;
ASISOO^F = 32.85
CHAP. XVIII]
(4)
PYROLYSIS O F P R O P A N E
863
(5)
C H e + H s - CHi + C2H4
r = t j T ^ S ^ ; (moles of propylene)
n<
(6)
A = (2.746)10";
A = (4.78)10";
AHuooT
= 34,316;
A>Si3oor
A = (9.83) 10;
/ = 63,000
= 32.12
C H s + H2 ^ CH4 + CsHe
J. =
(10)
E = 63,000
CsHs ^ C2H4 + H2
r = kir
["n^H. _ n c a " a ^ 1 . (jj^^jgg ^f ethane);
L nt
n,K
J
(9)
E =56,000
(8)
E = 38,000
(7)
A = (5.266)10';
fcJ"'';
n<
(moles of butylene);
A = (4.743)10";
E = 67,000
A = (9.34)10;
E = 35,000
For example, the apparent rate of pyrolysis of butenes as a secondaryreaction in the pyrolysis of propane may follow a rate equation which
would not be applicable to the pyrolysis of pure butenes. Ultimately it
is to be hoped that a practical method can be devised for handling such
systems by fundamental reactions involving free radicals similar to those
of Illustration 10.
By consideration of the reactions of Table LIV it is possible to predict
the conversion and product distribution obtained when propane is
pyrolyzed under specified conditions and thus to arrive at optimum procedures. Myers and Watson demonstrated this method by carryiag out
a design study on a large-scale tubular reactor operating with widely
varying temperatures and pressures.
864
HOMOGENEOUS REACTIONS
[CHAP. XVIII
CHAP. XVIII]
ADIABATIC REACTORS
865
predict it is desirable to develop a design on both bases and select a conservative intermediate value.
Case 1. Progressive Changes. For a simple reaction where the course
can be represented by a differential equation involving only one variable
conversion term XA, a direct method of reactor design results from combination of the rate equation with an equation relating temperatures to
conversion, such as is developed in Illustration 22 of Chapter VIII,
page 309. Such an equation expresses the temperature at any point in
an adiabatic reactor as a fimction of the conversion XA- Thus:
T =
UXA)
(95)
The rate of the typical reaction, A -{- B = R + S, is given by Equation (44) in which k and K are functions of temperature represented by
Equations (18) and (22), respectively. Thus:
^
A- = MT)
(96)
K = MT)
(97)
By combination of Equations (95), (96), and (97) with the rate equation
it is possible to calculate the reaction rate r corresponding to any selected
conversion XA for a particular system at fixed initial conditions. The
temperature is first calculated from Equation (95) and the velocity and
equilibrium constants from (96) and (97). From a series of such calculations corresponding to different values of XA a curve may be plotted
relating 1/r as ordinates to XA- From Equation (81) it is evident that
the area under this curve between XAO and XA is equal to Vr/F for a flow
system. A s>imilar integration for obtaining time of reaction in a batch
system is made by plotting l/rVc against XA and determining the area
under the curve in accordance with Equation (56). Where a large
pressure drop occurs through the reactor the general method of integration discussed on page 880 is followed.
Case 2. Uniform Reactor Conditions. If conditions of extreme turbulence exist in a reactor the average composition and temperature of the
material in the reactor must be the same as those of the product discharged from it. For any selected over-all conversion the outlet temperature is calculated from Equation (95). This temperature fixes the
average reaction velocity constant and equihbrium constant for the
entire reactor. The average rate of reaction per unit volume of reactor is
then calculated directly from Equation (44) the composition of the
product being employed. The required reactor volume is then equal to
F{XA - XAo)/r.
Illustration 11. The decomposition of phosphine is afirst-orderreaction which
proceeds according to the following stoichiometric equation:
4PH3(g)-^P4(g)+6H2(g)
(a)
866
HOMOGENEOUS REACTIONS
[CHAP. XVIII
In the International Critical Tables the reaction velocity constant of this reaction is
expressed by the following empirical equation with temperature in degrees Kelvin
and time in seconds:
log kc =
+ 2 log r + 12.130
(b)
cp = 5.9 + 0.0096r
Cj, = 6.70 + 0.00637 '
cp = 6.88 + 0.066(10-')r + 0.279(10-)T2
The following energy balance may be written on the basis of 1 mole of phosphine fed
where x is the moles of phosphine decomposed.
45
_I
nT
(5.9 + 0.00967) dT
/291
+ 1.5x /
/291
+ (1 - x) /
(c)
/291
t/29]
(d)
945
900
800
700
600
500
400
0.5917
0.7787
0.9799
0.0742
0.2432
0.4145
CHAP. X V I I I ]
DECOMPOSITION OF PHOSPHINE
867
0
0.1
0.2
0.3
0.4
0.5
U^
885
37.19
1.422
826 , 3.654(10-^)
6.832(10-^)
768
708 4.603(10-)
652
0.6
0.7
0.8
0.9
1.0
T
596
542
489
440
394
fe(l/hr)
2.627(10-")
1.469(10-")
1.913(10-18)
3.133(10-")
5.598(10-")
1.667(10-8)
The total pound-moles of product per pound-mole of feed for any degree of conversion X is equal to (1 + 0.75x4), and the volume Vm of product in cubic feet per
pound-mole of feed is given as
359
f = (1 + 0.75x4) T
(e)
FdxA
From Equations (47) and (80), r = r-~
aVr
F = (500)/(34.12) = 14.65 Ib-mMes per hr
273 Jo
c(l XA)
JO
KC
For an adiaba^c reactor without longitudinal turbulence, Equation (f) is evaluated
19.32 IY(x)
from a plot of -;
against x, as shown in Fig. 173. For selected values of x,
k
f(x)
values of T and kc are obtained from Table A, and values of T are calculated from
kEquation (f). The total reactor volume required for a given degree of conversion is
obtained by summation of the volumes for small Ax increments from 0 to x. The
volume required for any degree of conversion is plotted in Fig. 174.
(b) Adiabatic Reactor with Uniform Mixing. If uniform conditions prevail in the
reactor because of mixing, the differential form of the rate equation can be used to
calculate F , directly. Thus, from Equation (f) it follows that,
Values of T and kc are obtained from Table A, and the corresponding values of V,
from Equation (g) are plotted in Fig. 174.
(c) Isothermal Conditions. Where the reaction proceeds isothermally at 945K the
reaction velocity constant is 37.19 per hr, and Equation (f) may be integrated
directly to give
Vr = 504[-0.75x - 1.75 In (1 - x)]
(h)
In Fig. 174 values of Vr are plotted for various degrees of conversion under the three
stated conditions of operation. Comparison of the curves of Fig. 174 shows the
excessive size of reactor required for the adiabatic operation of this particular endothermic reaction as compared with constant temperature operation. It is evident
that longitudinal mixing in an adiabatic reactor for an endothermic reaction is
unfavorable.
868
HOMOGENEOUS REACTIONS
[CHAP. XVIII
0.1
0.2
0.3
0.4
0.5
a;, fractional conversion
0.6
0.7
CHAP. XVIII]
VISCOSITY
869
I
Pressure Drop. The calculation of pressure drops in reactors is
frequently a difficult problem, particularly if a change of phase occurs in
the reactor; For tubular reactors in which gases are flowing at relatively high velocities pressure drops are satisfactorily represented by the
following equation:
dp _ 0^235 / w
77;;^
L
dL~
-"^
(98)
where
dp/dL = pressure drop per foot of equivalent pipe length, pounds per
square inch
D = internal diameter, inches
w = mass rate of flow, pounds per hour
fi = viscosity, micropoises
p = density, pounds per cubic foot
Equation (98) is derived from the general Fanning equation which is
treated at length in the standard texts on unit operation and fluid flow.
The general equation should be used in deahng with problems involving
the flow of Kquids or of gases at low velocities.
The problem of pressure drops of gases flowing through beds of granular materials is treated in detail in Chapter X X I , page 1015.
Viscosity. Viscosity is a measure of the resistance to flow offered by
a fluid in straight line or laminar motion without turbulence. It may be
visualized as resulting from the friction of infinitesimally thin layers of
fluid moving over each other. The force required to maintain such relative motion is proportional to the area of contact between the layers and
the relative velocity of movement. Thus, viscosity is defined as the
force per unit area which is required to maintain a unit velocity gradient,
or
H = F/(A){du/dx)
(99)
870
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
where
fi =
7^ =
A =
u =
X=
(du/dx) =
viscosity
force in the direction of flow
area of surface in relative motion
velocity of flow
distance, perpendicular to the direction of flow
velocity gradient
VISCOSITY
CHAP. XVIII]
871
WW \
\U\\ \^^\ \
\Ss
m^
^^ \\
^^ \ \ \
\\\^^\
\\\ \\\\ \ \
10
vv
\ \ ^ s\V
\\
\ >
\\ \\\ ^A\ s \
A^
Vi \ ^ '
\
\\\^ sV \
^\\ v\N^ \ C\ , \ \
'm
s\ ^ \ \
^w
\i^\S\
5
4
\^^V
W1^w
0.7
2
0.8
1W
\^
\ \
\ ' ^"^ ^ < . ^
1 0
\^^
\> \
v^l \\
\
.
c5
o1
Poo
0.8
tv ^/
^
\
^ ^-6
6^
fck^
1^^^
v^
w
^
i ^ ^
\ s?'
?'\
0.6
f
,^
^,
<
M
\v
0<
- J : ; 1.-
-^' ^
U*y
r
^ '^. ?J
'^i ^ ;>'
''/&
diy
l4
"^
i?t\^
cPX;
0.5
0.4
0.2
0.3
^^
^^
0.2
5 6
0.8 1.0
2.0
3
4
Reduced Temperature, T^ = T/r^
Fia. 175. Generalized Reduced Viscosities.
10
Hquid or the gas at any known reduced temperature and pressure. The
viscosity at any other temperature and pressure may then be calculated
from the equation:
i-.r.i^s
fi = Hriic
(100;
872
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
where
iir = reduced viscosity read from Fig. 175
lie = viscosity at the critical point
In using Fig. 175 in conjunction with experimental viscosity data it is
desirable to calculate the value of Hc used in Equation (100) from data at
conditions as close as possible to the range of interest. Thus, although
it is possible to estimate the viscosity of a gas from a measurement on
the liquid, more reliable results are obtained if calculations for the gas
phase are based on gas-phase data wherever possible. The critical
viscosities of various substances based on experimental data for the
indicated phase are summarized in Table LV.
If no direct viscosity data are available, useful approximations may be
calculated from the Uquid density or structueal parachor together with
molecular weight and critical temperature by the following equation:".
jUc = 61.6 . , | = 7.70
rr- = 7.70 rri
(101)
(fc)'
(uiwi)*
{My
where nc = critical viscosity in micropoises
M molecular weight
Tc = critical temperature, degrees Kelvin
Vc = critical volume, cubic centimeters per gram-mole
(fiwi) = product 6i expansion factor (Fig. 109) and mblal volume,
cubic centimeters per gram-mole
(pi/i) = liquid density in grams per cubic centimeter divided by
the expansion factor
A similar expression, based oh a knowledge of molecular weight, critical temperature, and critical pressure was derived from an equation
proposed by Licht and Stechert.'^
.. = 7 . 7 0 % ^
(102)
Uyehara and Watson found both Equations (101) and (102) to be in good
agreement with over 50 compounds on which data are available. In
general the errors were less than 10 per cent. Exceptions are water,
hydrogen, helium, and bromine. Equation (101) was found to be more
reliable for complex molecules for which good Uquid-density data are
available, whereas Equation (102) giveis better results for the light gases.
" W. Licht, Jr., and D. G. Stechert, /. Phys. Chem., 48, 23-47 (1944).
873
VISCOSITY
CHAP. X V I I I ]
TABLE LV
CEITICAL ViscosmES
lie = micropoises
Phase
Acetic acid
g
Acetone
g
Acetylene
g
Air
g
Ammonia
. g
Argon
g
Benzene
g
7i-Butane
g
g
Carbon dioxide
g
Carbon disulfide
g
Carbon monoxide . . .
g
Carbon tetrachloride .
g
Chlorine
g
Chloroform
g
Cyclohexane
g
Diethylamine
g
Ethane
g
Ethyl acetate
g
Ethyl alcohol
g
Ethyl chloride
g
Ethyl ether
g
Ethyl formate
g
Ethyl propionate
g
Ethylene
g
Helium
1
n-Heptane
n-Hexane
Hydrogen
Hydrogen chloride . . .
Hydrogen cyanide . . .
g
g
g
g
Mo
376
285
237
193
309
264
312
239
343
404
190
413
420
410
284
276
210
299
334
345
268
282
284
215
25 .4
254
248
34
353
316
Zso-Butane
Zso-Butene
Zso-butyl alcohol...
7so-butyl formate .
/so-pentane
/so-propyl alcohol..
Krypton
Methane
Methyl acetate . . . .
Methyl alcohol
Methyl chloride . . .
Methyl propionate
Naphthalene
Neon
Nitric oxide
Nitrogen
Nitrous oxide
n-Nonane
n-Octane
Oxygen
n-Pentane
Phosphine
Propane
Propyl alcohol....
Propyl formate . . .
Propylene
Sulfur dioxide . . . .
Toluene
Water
Xenon
Phase
g
g
1
g
g
g
g
g
g
g
g
g
1
g
g
g
g
1
1
g
g
g
g
g
g
g
g
g
g
g
fc
239
250
319
310
240
297
396
159
307
375
338
301
340
156
258
180
332
265
259
250
238
274
228
298
296
233
411
306
495
490
Pc = 41.6 atm
ilf = 92
Solution:
Tr = (293.2)/(593.8) = 0.494
From Equation XII-40,
01 = 0.1745 - (0.0838) (0.494) = 0.1331
pi/wi = (0.866)/(0.1331) = 6.506
From%quation (101),
(593.8)* (6.506)1 _
874
HOMOGENEOUS REACTIONS
[CHAP. XVIII
CHAP. X V I I I ]
NONADIABATIC REACTORS
875
Mokeular
Weight
te'C
tcC
Pc atm
n (gas) at (fC)
(10~* poise)
Benzene
78
79.6
288.5
47.7
123(212.5C)
Diphenyl
154
255
,,'
,.
Diphenyl
Benzene
230
427
,,
,,
Hydrogen
2.0
-252.7
-239.9
12.8
88.2(23C)
S^hition: The specifications of the problems fix the temperature and pressure at the
outlet of the reactor and the temperature and conversion at the inlet of the preheater.
The inlet pressure is unknown. Since the enthalpies of activation of the forward
reactions are approximately equal, and there is no change in the number of moles in
876
HOMOGENEOUS REACTIONS
[CHAP. XVIII
either reaction, the distribution of the products is little affected by changes in either
reaction temperature or pressure. For this reason the conversion at the reactor outlet may be closely approximated from the specification of the ratio of diphenyl to
triphenyl in the product.
' A design of this type requires a trial-and-error procedure in which the graphical
integration may be started from either end of the reactor. Thus, a first approxima1000
4_
600
^
/C;
100
" ^
50
kyz'
10
5
1.0
0.5
Kz =
KA,
- ^
0.1
0.05
0.01
700
800
900
1300
1400
FIG. 176. Reaction Velocity and Equilibrium Constants of the Diphenyl Reaction
tion to the inlet pressure may be assumed, and temperature, pressure, and conversion through the preheater and reactor may be evaluated on this basis. If the
calculated outlet pressure, corresponding to the desired conversion, does not agree
with the specified value, the integration must be repeated with a new trial inlet
pressure. Two or three trials of this type generally serve to estabhsh the correct
conditions throughout.
An alternate procedure is to start the integration from the outlet of the reactor, and
integrate back toward the inlet. In this method it is necessary to assume a trial
value of the conversion at the outlet of the preheater. On this basis the conversion,
temperature, and pressure throughout the preheater are calculated. If the calculated
conversion at the inlet of the preheater does not agree with the specified value, the
DIPHENYL REACTOR
CHAP. XVIII]
877
calculation must be repeated with an adjusted trial value of the conversion at the
outlet of the preheater.
The choice between these two procedures is determined largely by personal preference and the conditions of a particular problem. If pressure drop is relatively small
and unimportant, the first procedure based on an assumed inlet pressure is generally
^ 150
-22,000
90
140
-21,000
80
- 130
-20,000
xuu
120
3
M
u"60
-19,000-0
S1
-0
110 "I--18,000 %
<N
w
a>
S4-> 50
oK!
1 0 0 ^ -17,000 n
cUA
^^^^^
0
4J
P^
u
a
90 (3
-16,000 (
0
0
M
%
ei
- 80 -15,000 J
O 40
<v '
W
3 30
c.^-<^>-^
/^-JK'^'^
<5
20
y/y
10 ^
'
1
200
1
400
C'p\ H2
1
1
'1
600
800
1000
Temperature, F.
1200
- 70
--14,000
60
-13,000
50
1400
-12,000
878
HOMOGENEOUS REACTIONS
[CHAP. XVIII
T R
Pc lb per sq in.
iJLc poise (10-8)
Benzene
1011
701
324
Diphenyl
1458
461
317
Triphenyl
1895
385
326
Hydrogen
59.9
188
35
Diphenyl
Triphenyl
From Fig. 168 may be read the complete composition of the reacting system corresponding to this product composition if the reaction proceeded isothermally at 1265F.
In the plant the average reaction temperature will bo lower than 1250F which will
slightly increase the proportion of triphenyl formed with a given conversion of benzene. This qualitative trend results from the fact that, although the enthalpies of
activation of the two forward reactions are taken as equal, the equilibrium constant
of the first reaction is increased more by an increase in temperature than is that of the
second reaction. Accordingly, increased temperature favors'the first reaction, and
the design will be based on a conversion of benzene slightly lower than that corresponding to the desired product composition at 1265F. This is accomplished by
assuming 12.8 per cent diphenyl in the reactor-outlet mixture instead of the 13.2 per
cent indicated by Fig. 168. The proportions of the other components are adjusted to
conform to the specified product composition and the stoiohiometry of the reactions.
Thus, nB 2hT + nz>.
Weight of product, lb per hr
= 35,000/24 = 1,458
Weight of reactor feed, lb per hr
= (1458) /(0.2526 + 0.1086) = 4,036
Molal reactor feed rate F lb-moles per hr ='4036/78.1 = 51.68
It is convenient to consider integral numbers of tubes in carrying out the reactor
CHAP. XVIII]
DIPHENYL REACTOR
879
Design Basis
Mole
Weight
Per Cent
PerCerU
62.2
Benzene
63.36
63.36
13.2
Diphenyl
12.80
25.26
Triphenyl
3.8
3.68
10.86
Hydrogen
20.8
20.16
0.52
100.0
100.0
100.0
design. In these calculations expressions for the values of Ap, AVr A(1/<S) and
AA, the heated surface area, per tube are required.
Equivalent length of tube, feet, = 10 + (50) (2) /12 = 18.33. From Equation (98),
=
where
2'
T
p
/i'
AF,, (359 cu ft) per tube
A(l/S,) per tube
AA sq ft, per tube
'
(a)
The calculations for the first trial analysis of the reactor and the preheater, working
back from the reactor outlet, are summarized in Table C. In order to develop a
basis for estimating the changes in conditions per tube, the first reaction section considered comprises only the outlet tube. In this analysis the tubes are numbered
back from the outlet.
In lines 5-10 are entered the specified reactor-outlet conditions based on 1.0 lbmole of feed while in lines 11-16 are estimated average conditions in the section. The
average composition is arrived at by first estimating average values of no and nr.
Then nn = 2nr + no, and ns is determined by difference.
On the basis of the estimated average composition, the pseudocritical temperature, pressure, and viscosity and the corresponding pseudoreduced temperature and
pressure are calculated. Values of the compressibility factor, z , {Cp ~ c'p), and M' are
read from Figs. 103, 108, and 175. Ideal molal heat capacities and heats of reaction
at the average temperature of the section are obtained from Fig. 177. Heat-capacity
yalues are not required in the reactor section where there is no change in temperature.
Values of kvh and K are read from Fig. 176. At the moderate pressures of this
process the fugacity coefficients of both the activated complex and the reactants and
products may be neglected. On this basis the reaction rates are calculated from the
following equations:
fci^V(7r) =
ri =
n=
z'
A;2>'V(ir)2r
nrnffl
880
HOMOGENEOUS REACTIONS
[CHAP. XVIII
Ml IS,) = (AV)KF)
Ani = - [ ( n + r2)][A(l/S.)]
AB = [r,/2-r-2][A(l/S)]
Anr =r2A(l/S)
An^=[(r,/2)+rd[A(l/S.)]
(d)
(e)
(f)
(g)
The incremental conversions calculated from these equations are subtracted from
the corresponding numbers of moles at the outlet of the section in order to obtain the
compositions at the inlet, which are entered in the next column as the outlet conditions of the next section. The estimated average conditions of the section are
compared with these inlet and outlet values, and if any of the estimated values are
badly in error the calculation is repeated.
The heat of reaction per mole of feed of each of the reactions is calculated in
lines 44 and 45. In the reactor section where there is no change in temperature the
sum of these heats of reaction times F the molal feed rate equals q the heat absorbed
per hour in the section. Where there is a temperature change,
q = F[{AHO (|) (-Ans - Any) + (AH,) (Anr) + c'^AT]
(h)
(i)
Cp
The pressure drop in the section is calculated from Equation (a). Thus, for the first
section,
(0.02622) (1710) ,,,
, ,
Ap = ^
"
(208)''-= = 4.1
Based on the conversion and pressure drop in the first tube, the average conditions
in the section comprising the next five tubes are estimated, it being remembered that
the rate of conversion is markedly affected by the increase in pressure. The conversion and pressure drop,in these tubes are then calculated, and the same procedure is
repeated for another section of five tubes.
It may be noted that in the first 11 tubes of the reactor the mole fraction of benzene
is increased from 0.83 to 0.86. Since the reaction rates are high in tubes 7-11 it is
evident that another section of five tubes at the constant temperature of 1250P
would account for substantially all of the desired conversion, leaving none to be
accomphshed in the preheater. Accordingly, it will be assumed that tube 11 is the
last tube of the reactor section and that following tubes are heated at a uniform rate
of 10,000 Btu /(sq ft) (hr). On this basis calculations are carried out for tube 12 and
then for the section comprising tubes 13-15. The results of these' calculations are
summarized as they are carried out in Fig. 178 in which conditions at the tube outlets
are plotted against tube numbers. The cuhres representing these first calculations
for tubes 12-15 are shown by broken lines. It may be noted that these broken lines
for the moles of diphenyl and triphenyl are rapidly approaching zero at temperatures
CHAP. X V I I I ]
DIPHENYL REACTOR
881
far above the specified temperature at the inlet to the preheater. This situation
indicates that the number of tubes assumed for the reactor section is too large.
As a second approximation, it is assumed that only six tubes are required for the
reactor section. On this basis the changes in tubes 7-9 are recalculated to correspond
to the heat-input rate of 10,000 Btu/(sq ft)(hr) specified for the preheater section.
These calculations are repeated, as indicated in Table C and Fig. 178 for successive
sections of 3, 3, 5, 5, and 10 tubes until the conditions at the inlet of tube 35 or the
0.16
40
30
20
10
0
Tube Numbers from Reactor Outlet Tube 1
FIG. 178. Conditions at Tube Outlets of the Diphcnyl Reactor and Preheater.
outlet of tube 36 are evaluated. It may be noted that at these conditions the rates of
reaction are very low and that the number of moles of diphenyl is close to zero while a
shght negative conversion to triphenyl is indicated. These differences from zero
are less than the probable errors of the calculations and indicate that the assumption
of six tubes for the reactoCpection is satisfactory.
By extrapolating the temperature curve of Fig. 178 to 700F the specified inlet
temperature, it is seen that a total of 36 tubes is required. Thirty of these tubes are
used in the preheater and six in the reactor sections. Extrapolation of the pressure
curve indicates a pressure of 96 lb per sq in. at the inlet of tube 36 which is the inlet
of the preheater.
The fortuitous choice of six tubes tor the reactor section made further calculation
unnecessary. If five or seven tubes had been assumed for this section, the corresponding calculated conversions at the preheater inlet would have been, respectively,
882
HOMOGENEOUS REACTIONS
[CHAP. XVIII
iOt*iO OS 1-H CO
A : :
^TjJo) o
ci<S3ai o
o
<005t
'-
OMO
^aOOi
CO -i
ifS -i
O O
O O
to
CO
O
O
O ' - ' b - O to CO
d di ci ii
CJtOOO O O
ddSo
dodo
Biiii
'"J'^
'^
t ^ CO ' ^
- : 2 ' - ' ^ c
CIOSO t-( <M U5
- " - " t * 1-) O i-t
dddd
dddd
"^
d d d d ' ^
^liiii
III
d6do
dddd
o d d d " ^
oo>
^cooo
*? . H U J O O
S*3
c^oso
o
05 - c o
NOiCO
d d <6 <D
d odd
Qoocq
S <6 <6 d
ill
ill
dddd
oddd
i\ i i fiSg^gpS : : : : : : ^^^1^^
o o o
f f l 11|
dddd
dddd
dddd
dddd
'^
CiOi
C0P5
11
II
11;^
if.e S
S2"
g 3 3 O.
IgiJ
Hi
l aWgflj
'S ^::
^_
mifff
'.ffl ** ^ ^ ' i ^ l i , O
eel
l|i
?S
CHAP. XVIII]
883
greater or less than zero. In this case the final design could have been arrived at by
repeating the calculations, starting from the preheater inlet with a pressure assumption based on the first calculations.
The problem of Illustration 11 is solved by a relatively compUcated procedure
which insures accurate results if reasonably small increments are considered. In
many cases this degree of accuracy may be greater than justified, and many simplifications are possible, particularly for the preliminary designs necessary to explore
various ranges of operating conditions. After experience is gained in such calculations, it is possible to estimate average conditions in succeeding sections with such
accuracy that corrections are rarely required.
884
HOMOGENEOUS REACTIONS
[CHAP. XVIII
helpful in reducing the size of the reactor but introduces added costs of
pumping and increases the cost per unit volume of the reactor. In
order to determine the optimum pressure, designs are worked out for a
series of pressures, and the costs are evaluated. In general, such
economic optimum conditions are not critical, and operations can be
carried on over a wide range of conditions with little change in costs.
For this reason it is not ne'cessary that the optimum be evaluated with a
high order of accuracy. The general effects of the individual operating
variables are as follows:
Temperature. In general the highest possible operating temperature
is the most economical for endothermic reactions or for any operation in
which reverse reactions are negligible. For exothermic reactions which
approach equilibrium the problem is more complicated. In such case
increasing the temperature increases the rate of reaction but at the same
time makes the equilibrium composition less favorable. As a result a
definite optimum temperature exists which for a specified space velocity
and pressure will result in maximum conversion. Calculations of such'
optimum temperatures for catalytic systems are discussed on pages 1020
to 1028.
Pressure. Increased pressure increases the production rate or conversion of any reactor if reverse reactions are negligible. Where a
decrease .in number of moles accompanies the reaction, increased pressure also favors the equihbrium composition. However, where an
increase in the number of moles is involved, an optimum pressure will
result in maximum conversion if equilibrium is approached. This effect
is similar to that of temperature.
(Space Velocity. In a reactor operating at fixed temperature and
pressure the extent of conversion is determined by the space velocity in a
flow process or the time in a batch process. Reduction of space velocity
increases conversion and reduces costs of recycling. On the other
hand, the cost of the reactor is increased and frequently an increased
formation of undesirable by-products results in a poorer ultimate jaeld
of desired products.
Equivalent Reactor Volume. In experimental operations it is frequently difficult to maintain a constant temperature throughout a flow
reactor or during the entire cycle of operation of a batch reactor. The
rigorous interpretation of such, data becomes comphcated if large temperature differences are involved, particularly where reverse reactions are
significant. For this reason it is important that isothermal conditions be
approximated as closely as possible.
Where relatively small temperature differences exist in a flow reactor
, satisfactory results can be obtained by calculating the equivalent volume
CHAP. XVIII]
885
of the reactor which at a constant reference temperature Ti, would produce the same conversion as the actual reactor with its varying temperatures. In order to calculate such an equivalent reactor volume Vh, it is
necessary to assume an approximate value of the average enthalpy of
activation A ^ ^ of the reactions taking place. If an intermediate reference temperature is selected somewhat lower than the maximum temperature, the value of the calculated equivalent volimie is not greatly
affected by moderate errors in Aff^. Where experimental data at two
different temperature levels are available, the equivalent reactor volimies
at the two reference temperatures are calculated from a trial or assumed
value of A^J,. Rate equations may then be developed by treating these
data as though they were obtained in isothermal reactors operating at the
reference temperatures, and a corrected value of A/?|, is then calculated.
If the assumed values were grossly in error the calculation is repeated.
The same principles^jnay be followed in calculating the equivalent
time of reaction in a batch process.-*. From Equation (55) the time drb
required at reference temperature Tb t o produce the conversion dxA
resulting from time dr at the existing temperature T is given by the
following equation
dn = dT{h/h)
(104)
where h and hh are the reaction velocity constants at the existing and the
reference temperatures, respectively. Similarly, from Equation (80)
for a flow process,
d{Vr/F)b = d{Vr/F)(k/h)
(105)
Combining (104) and (105) with (18) and neglecting deviations from
ideal-gas behavior gives
dn = dr Le
vr nJ j
d(Vr/F)i = d{Vr/F) le
Vr TJ]
(i06)
(IO7)
R KT Ti)dr
(108)
{VrIF)i=
/ e-~BrKT-Yj
d{Vr/F)
(109)
t/0
886
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
1 \
(110)
where
k = effective average reaction velocity constant corresponding to the
range of fractional conversions from 0 to x
ko = effective initial reaction velocity constant for the unconverted
charge
a = a proportionality factor depending upon the characteristics of the
charge
Equation (110) is frequently satisfactory only over moderate ranges of
conversion. Where high conversions are involved the following alternate form,
k = /fo/(l -i a'x)
' (111)
may give better correlations.
CHAP. XVIII]
SEVERITY FACTORS
g87
Combining Equations (110) and (84), taking n^o as 1.0 and assuming
VA = 1.0 gives
r^r,
dVr
C- (1 + wa;) dx
/
hT-^
,,
,,/
r
(112)
Jo
rioF Jo (1 - ax)(l x)
^
If it is assumed that the fugacity coefficient of the activated complex v^
is constant, ko may be expressed in terms of (^-0)6, the initial reaction
velocity constant at the reference conditions of temperature Tb and
pressure TB where the compressibility factor of the feed is z^. Thus,
from Equation (18) written for the two temperatures,
ko= {ko)b-^e~~ir\.T-rJ
(113)
Combining (113) and (112) and evaluating the second integral, we have
{ko)b I
Jo
e
z'
KT
n/noF
= -a(l
J T^ a) 1" ^1 - ^) - T(1T
^ l a)
' ^ (1 - ^) = (^0)/.
*
(114)
1 \
888
HOMOGENEOUS REACTIONS
2
3
4
6
6
Volume of Reactor, Vr
[CHAP. XVIII
1.0
/ ^
=0
02
0.4
T/r
; ^ ^
nj__
01=2.0
,0.2
10
12
14
CHAP. XVIII]
889
ing stock only partially vaporized. Under such conditions the compressibility factor z' is equal to pv/RT for the entire two-phase mixture
and accordingly may vary widely with the degree of vaporization.
The severity factor may be employed as a basic factor for the correlation of conversions, yields, product distributions, and qualities in complex reacting systems. The relationship between the severity factor and
conversion x may be obtained by evaluating the integral on the right side
of Equation (112). In this manner a family of curves may be constructed such as is shown in Fig. 180. Each curve corresponds to a
different class of feed stocks for which values of co and a are specified.
Where Equation (114)'is not applicable, curves relating conversion to the
severity factor may be empirically evaluated.
Similar severity factors may be defined and used for semiempirical
correlations of rate and yield data in reaction systems which do not
approximate first-order behavior. Such factors will generally involve a
pressure term with an empirically determined exponent.
PREDICTION OF ENTROPY AND ENTHALPY OF ACTIVATION
890
HOMOGENEOUS REACTIONS
[CHAP.
XVIII
S' = ^ ^ ^
- 10
(115)
CHAP. X V I I I ]
891
S^-SA
(116)
AS* = S^-SB
(117)
(118)
AS* = 0
(119)
= SA-
SB-SS^
-AS
(120)
This rule is based on the finding of Daniels^^ who pointed out that the
frequency factor kT/h at 300K is equal to 0.63(10i'). From a survey of
28 of the most reliable unimolecular reactions Daniels^^ found that for
82 per cent the value of - e R ranged from lO^^ to 10" at 300K,
h
indicating that AS* was very small.
Reactions Bimolecular in Both Directions. When two molecules form
an activated complex which decomposes to form two other molecules
without the formation or destruction of a ring, it may be assmmed that
for complex molecules the external rotational contribution to the entropy
of the complex is equal to the sum of the rotational contributions of the
reactants. On this basis the entropy changes accompanying the formation of the complex result from changes in the translational contributions and the vibrational and internal rotational contributions. The
changes in the translational contributions are readily calculated from
Equation (XVII-12), and it will be assumed that the formation of the
892
HOMOGENEOUS REACTIONS
[CHAP. XVIIl
Si' =
SA+SB
Similarly,
>SL = 5ij + & + | / 2 In ^ r ^ - - 22.0
(122)
where
Mx, MA, MB = molecular weights oi X^, A, B
Si = {Sh + Sh)/2
(123)
(124)
(125)
CHAP. XVIII]
ENTHALPY OF ACTIVATION
893
AB:^A+B
Aff* = AH
(126)
AH*' = 0
(127)
AB + CD:^AC + BD
TABLE LVI
APPROXIMATE BOND ENERGIES^'
CH
CC
CBr
CI
CC
92
79
58
44
77
C=G
C=C
HH
0H
NH
122
200
102
113
96
= N N = 33
C 0 82
C = 0 188
BrBr 45
0.28{EAB
ECD)
when
AH is negative
(128)
(129)
A+BC^AB
+C
0.05EBC
when
AH < 0
(130)
(131)
These rules give results in fair agreement with the relatively few reliable
experimental data which are available.
Illustration 14. Estimate the entropy of activation AS* in concentration, units
of the formation of HI from gaseous hydrogen and iodine at a temperature of 298K.
894
HOMOGENEOUS REACTIONS
[CHAP. X V I I I
Solution: The entropies of the reactants and products at 298K and 1 atm are
obtained from Table XXXV, page 701.
Sm = 31.23
Mm = 2.0
Sij = 62.29
iWij, = 254
SHI = 49.36
Mm = 128
Hj + Ij ? (2HI)* 5=i 2HI
F r o m E q u a t i o n (122),
^
S^zi = 31.23 + 62.29 + 2.98 In ( - S T T )
- 22.0 = 69.5
\(2)(254)/
>SL = (2) (49.36) + 2.98 In ( T ^ ) - 22.0 = 64.3
S^x = (69.5 + 64.3)/2 = 66.9
A<S{298'>Ki = 66.9 - 31.23 - 62.29 = - 2 6 . 6
Glasstone, Laidler, and Eyring^ report a value of AS^ (300K) =
20.3 for t h e reaction of Illustration 14. I n this case t h e simple rule
for estimating t h e entropy of activation led t o a n error of 6.3 units. F o r
more complex molecules this error might be reduced somewhat by improved additivity of t h e rotational contribution, b u t it should be recognized t h a t rules of this t y p e m a y lead t o errors of t e n entropy units or
more for simple reactions a n d are n o t applicable t o t h e over-all results of
chain reactions.
PROBLEMS
1. Calculate the reaction velocity constants from the following data of Schumacher"^' for the designated unimolecular reactions, assuming ideal behavior. Express rates in g-moles /(liter) (sec) with activities in atmospheres.
T
(a) Decomposition of dimethyl ether, CH3OCH3
(6) Decomposition of methyl
azide, CH3N3
(c) Decomposition of tetramethyl silicane Si (CHs)^
(d) Decomposition of azo
methane CH3N NCH,
AH^
KCal Iper G-Mole
AS*
{Entropy Units)
780K
56.95
2.5
500K
42.5
8.2
950K
76.9
2.2
600K
48.8
10.8
Calculate the percentage error resulting from assuming that AS* = 0 in each of
the afore-mentioned cases.
2. The kinetic and thermodynamic behavior of a reaction of the type A + B =
B -f S in an ideal-gaseous system is expressed by the following data:
Reaction velocity constants:
fc450F = 0.0061 g-mole/(liter) (atm^) (see)
fcsoo-F = 0.0239 g-mole/(liter) (atm^) (sec)
" H. J. Schumacher, " Chemische Gasreaktionen," T. Steinkopf (1938).
CHAP. X V I I I ]
PROBLEMS
895
The standard enthalpy and entropy changes may be assumed to be constant over the
temperature range of interest.
AH" = 8,400 cal per g-mole
AS = -2.31 cal per (g-mole) (K)
(o) Derive an equation for the reaction velocity constant of the forward reaction
as a function of temperature.
(b) Evaluate AH* and AS*.
(c) Evaluate an expression for the reaction velocity constant of the reverse reaction as a function of temperature.
3. The rate of a reaction is reported as 2.46(10"^) lb-mole/(hr) (cu ft). Express
the rate in
(a) Molecules/(cu cm) (sec).
(6) G-moles/(Uter)(sec).
4. In the rate equation,
r = kA
kc = 0.0031 at 700K
where
HOMOGENEOUS REACTIONS
896
[CHAP. XVIII
of 40 per cent by volume and NaOH equivalent to 0.04 normality. The density of
the bath may be taken as 1.0.
The percentage available oxygen content refers to the volume of oxygen gas at
1 atm, 0C., which may be liberated from the hydrogen peroxide expressed as a percentage of the volume of the liquid. For a period of 1 hr at 60C calculate:
(o) The percentage decomposition of hydrogen peroxide.
(6) The grams of H2O2 decomposed.
11. Five hundred grams of phosphine gas are heated in a tube at 672C., 1 atm
pressure, for 200 sec. Dissociation proceeds according to the reaction, 4PHj(g)
PiCg) + SHjCg), and is of the first order. The reverse reaction is negligible. The
reaction velocity constant kc per sec is expressed as a function of temperature according to the following equation given by the International Critical Tables:
logiofcc=
18963
+ 2 logio T + 12.130 where T i in degree Kelvin.
T
Calculate:
(a) The grams of phosphorus formed.
(b) The time required to decompose 95 per cent of the phosphine at a temperature
of 672C.
12. The saponification of ethyl acetate by alkalies in aqueous solution is a relatively rapid reaction; the reverse reaction is negligible. For a second-order reaction
the reaction velocity constant is given by the International Critical Tables where the
initial normality of caustic soda is 0.05, as
logio kc =
1780
+ 0.00754r + 5.83
where kc is the reaction velocity constant in liter / (g-mole) (min) and T is in degrees
Kelvin. Calculate the time required to saponify 98 per cent of the ester at 40C
when the initial concentration of ethyl acetate is 2.0 g per liter, and the initial normality of NaOH is 0.05.
13. The decomposition of nitrous oxide proceeds as a second-order reaction,
2N2O > 2N2 + O2. The reverse reaction is negligible. At 895''C, the International
Critical Tables give the value of % as 977 (cc) (g-mole) /sec. Calculate the time
required to decompose 90 per cent of the N2O at 895C:
(o) When the volume is kept constant, initial pressure 1 atm.
(6) When the pressure is kept constant at 1 atm.
14. One hundred grams of acrolein are treated with 120 g of 1,3-butadiene in a
5-liter vessel to form 1, 2, 3, 6-tetrahydrobenzaldehyde. The weights of the aldehyde formed in various time intervals are given herewith for constant temperatures
Grams
Grams
of
of
of
150C
43
73
90
109
111
100
200
300
400
500
Grams
250C
45
63
83
96
113
1
2
3
4
5
CHAP. XVIII]
PROBLEMS
897
150, 200, and 250''C, respectively. Evaluate the reaction velocity constants for this
reaction and the enthalpy of activation, AH^.
15. From the work of Cain and NicoU^" the following rate data were obtained on
the decomposition of diazobenzene chloride in aqueous solution at 50C:
C6H5N2CI -> CeHsCl + N2
The initial concentration of the diazo salt in solution is 10 g per liter, and the sample
chosen liberates 58.3 cc of nitrogen at 60C and atmospheric pressure when completely decomposed. Calculate the reaction velocity constant kc for the first-order
reaction:
Time (min)
12
14
18
20
22
24
26
30
50.35
20
0.00166
30
0.00678
40
0.0210
50
0.0688
60
0.251
120
240
360
480
0.0359
0.0632
0.0811
0.0957
840
1020
1320
1680
0.1227
0.1308
0.1389
0.1442
898
HOMOGENEOUS REACTIONS
[CHAP. XVIIl
h = 7.8(10')e" ^
(1/sec)
Calculate the volume of the flow reactor required to produce 65 per cent decomposition in a feed of methyl acetoxypropionate flowing at 650 lb per hr at a pressure of
4 atm and a temperature of 1100F.
22. The viscosity of liquid benzene at 40C and atmospheric pressure is given by
the International Critical Tables as 0.492 centipoise. Estimate the viscosity of the
liquid at 70C. Estimate the viscosity of the vapor at 300C and 3 atm pressure.
23. The viscosity of CO2 gas is given by the International Critical Tables as
0.0167 centipoise at 40C and 1 atm pressure. From Fig. 175 estimate the viscosity
of CO2 gas at 500C and 6 atm pressure.
24. Estimate the viscosity of propyl butyrate vapors at a temperature of 250C
and a pressure of 1.0 atm from the following data:
Molecular weight
Critical temperature, C
Liquid density, 15C, g per cc
130
327
0.879
25. From the following data, estimate the viscosity of pyridine vapors at a
temperature of 450C and a pressure of 30 atm.:
Molecular weight
Critical temperature, C
Critical pressure, atm
79
344
60
26. The International Critical Tables give the viscosity of H2 as 0.0084 centipoise
and of NH3 gas as 0.0092 centipoise at 0C and 1 atm pressure. Estimate the viscosity of a gas mixture containing 20 per cent Hj and 80 per cent NH3 at 12C and
22 W. P. Ratchford and C. H. Fisher, Ind. Eng. Chem., 37, 382 (1945).
CHAP. XVIII]
PROBLEMS
899
1 atm. Compare this result with the International Critical Tables value of 0.0104
centipoise for this mixture.
27. Vapors of sulfuryl chloride at 200F and 1.2 atm are fed to a l^-inoh reactor
tube at a rate of 418 lb per hr. The reactor tube is heated at a rate of 5,000 Btu/
(hr) (sq ft) based on the internal area. At elevated temperatures the SO2CI2 decomposes by a first-order reaction to form SO2 + CI2. It is desired to produce 98 per cent
decomposition of the SO2CI2 fed. The pressure drop in the reactor and the effect of
the reverse reaction may be neglected. From the following data calculate the length
of reactor tube required, and plot a curve relating temperature to tube length:
Dimensions of tube:
Nominal size
Inside diameter
.
Outside diameter
Inside cross-sectional area
Surface per foot of length
Inside
Outside
IJ in.
1.334 in.
1.50 in.
1.398 sq in.
0.3491 sq ft
0.3925 sq ft
kc = (6.427) 10"e
(1/sec)
The heats of formation are reported by the U.S. Bureau of Mines Bulhtin 406
(1937).
Components
SO2CI2
SO2
CI2
AH (formation) (gas) 298Kj
cal/g-mole
-82,040
-70,920
0
Molecular weight
135
64
71
For the molal heat capacity of Cl2(g), Spencer and Justice''^ give
Cp = 7.5755 + (2.4244)(10-3)r - (0.965)(10-)r2; Tin K
No data are available for the heat capacity of sulfuryl chloride at high temperatures.
The following approximate equation is estimated from low-temperature data by the
methods of Chapter X^VI and may be used in the range from 300 to 900K:
Cp = 13.00 + (24.0) (10-') r - (14.4)(10-)r2
28. Calculate the volume of the adiabatic reactor operating at a pressure of 1.2 atm
with an outlet temperature of 7 5 0 ^ which would be required to produce a conversion
of 49 per cent in the reaction of Problem 27, neglecting decomposition in the preheater
and assuming:
(a) Uniformity of temperature as a result of mixing in the reactor.
(6) A progressive temperature change with neghgible longitudinal mixing in the
reactor.
Develop an equation expressing temperatures throughout the reactor as a function
of conversion.
29. It is desired to design a tubular heater and reactor for the pyrolysis of propane
to produce a mixture of ethylene and propylene. Substantially pure propane is to
D . F. Smith, J. Am. Chem. Soc, 47, 1862 (1925).
" H. M. Spencer and J. L. Justice, J. Am. Chem. Sac., 56,2311 (1934).
900
HOMOGENEOUS REACTIONS
[CHAP. XVIII
lo^ll
CHAP. X V I I I ]
PROBLEMS
901
tubes are as follows. The tubes are numbered from the inlet of t
of the heater.
Tube No.,
Furnace Inlet
10
20
30
40
50
60
66
Reaction chamber
Temperature, op
. 730
795
840
875
905
922
942
950
875
Pressure, Lb 3
630
615
595
570
640
500
448
400
400
The cracking of this charging stock is found to produce 2.9 moles of products per
mole of net charge converted. The reaction may be assumed to approximate a firstorder reaction in accordance with Equation (111). At a temperature of 900F the
initial-reaction velocity constant in concentration units (kc) is 0.0015 (1 /sec), and
the enthalpy of activation is 55,000 cal/(g-mole). The value of a in Equation (111)
is 1.6. Neglecting changes in the compressibility factor of the feed, calculate:
(a) The severity factors in (equivalent cu ft) (hr) /lb-mole of the heater and the
reaction chamber using a base temperature of 900F with pressures in atmospheres.
(6) The relationship between severity factor and conversion x:
(c) The conversion produced in the heater alone and in the heater plus the reaction
chamber.
31. Estimate the value of AS* in the formation of NOCl(g) from NO(g) and
Cl2(g) at 298.1K. The absolute molal entropies at 298.rK and 1 atin are as
follows:
NOCKg), s" = 63.00
NO(g), s = 50.34
Cl2(g), s = 53.31
CHAPTER XIX
CATALYTIC REACTIONS
By definition, a catalyst is a substance which influences the rate of a
reaction but is not one of the original reactants or final products. The
catalyst must participate in intermediate steps in such a manner as to
facilitate the over-all course of the reaction. In terms of the theory of
absolute reaction rates the function of the catalyst is to reduce the
positive free-energy change accompanying the formation of the activated complex. This may be brought about by the substitution of a
sequence of steps, each having a low free energy of activation for a single
step involving a high free energy of activation in the uncatalyzed
reaction.
,
Although a catalyst may greatly alter the free-energy changes accompanying intermediate steps of a reaction, the over-all free-energy change
is not so influenced but is dependent only upon the initial state of the
reactants and the final state of'the products. Thus, although the catalyst may change the rate of reaction it cannot influence the over-all freeenergy change and, hence, the equilibrium conditions approached,
except as it may influence the nature of the terminal reactants and
products. SimUarly, a catalyst is unable to cause any reaction to proceed under conditions not in agreement with the principles of thermodynamics. For example, by means of a catalyst it is possible to accelerate the low-temperature combustion of hydrogen with oxygen to form
water. However, it is impossible for a catalyst to restore such a system
to its original state by reversing the reaction at the same conditions.
It follows from thermodynamic principles and the theory of absolutereaction rates that if a catalyst increases the rate of reaction in the forward direction a corresponding increase is produced in the rate of the
reverse reaction. Thus, the net rate of change of the system in either
direction is increased, but it is always in the direction of thermodynamic
equilibrium.
It is believed that in general catalysts function through forming definite intermediate compoimds with the reactants. The high degree of
specificity of chemical combination is in agreement with the selectivity
exhibited by catalysts in accelerating certain reactions in preference to
others. This selective behavior is illustrated by the influence of different catalysts upon the decomposition of ethyl alcohol. In the presence
902
CHAP. XIX]
SOLID CATALYSTS
903
(1)
AUOJ
CsHsOH ^ CH3CHO + H2
(2)
Cu
2C2H6OH ^
(C2H5)20 + H2O
(3)
A10.
904
CATALYTIC REACTIONS
[CHAP. XIX
CHAP.
XIX]
SOLID CATALYSTS
905
906
CATALYTIC REACTIONS
[CHAP. XIX
CHAP. X I X ]
MECHANISMS OF REACTIONS
907
908
CATALYTIC REACTIONS
[CHAP. XIX
ACTIVATED ADSORPTION
In Chapter VII, page 149, it is pointed out that there are two types of
adsorption, one referred to as van der Waals or physical adsorption and
the other as activated adsorption or chemisorption. In the van der Waals
type, adsorption results from physical-attractive forces similar to those
causing the condensation lof a vapor. Chemisorption, as the name
implies, is believed to involve definite electron bonds corresponding to
the formation of a chemical compound between the adsorbate and the
surface. Like a chemical reaction, chemisorption is a highly specific
phenomenon depending upon the chemical natures of the adsorbate and
adsorbent.
The concept of chemisorption was introduced by Taylor in 1930.
Since that time much attention has been devoted to it in the literature as
summarized by Taylor,' and Glasstone, Laidler, and Eyring.* I t is
currently believed that activated adsorption occurs only on specific
active centers which, as previously pointed out, may represent only a
small fraction of the total surface. On this basis the maximmn capacity
of a surface for a specific chemisorption is frequently much less than the
amount of adsorbate required to form a monomolecular layer. By
van der Waals adsorption it is possible to adsorb much larger quantities
which form layers several molecules in thickness or result in capillary
condensation.
Because of the larger energy changes involved in the formation of
valence bonds the enthalpy changes accompanying chemisorption are
generally highly negative, in the range of 10 to 100 kcal per g-mole.
The enthalpy change of van der Waals adsorption is of the same order as
the heat of condensation, in the range of 5 to 10 kcal per g-mole.
I t follows that the effect of temperature in diminishing the quantity of
adsorbate at equilibrium is greater for activated than for van der Waals
adsorption.
The most significant difference between van der Waals and activated
adsorption is in the rate at which equilibrium is approached. Activated adsorption, as the name implies, requires a definite energy of acti-vation which corresponds to relatively slow rates of adsorption. These
rates are greatly affected by changes in temperature, just as is the case
of any chemical reaction.
Although van der Waals adsorption may be considered as requiring an
activation energy' its value is so low that in general it may be assumed
that equilibrium is reached instantly at the interface and that observed
8 " Theory of Rate Processes," Glasstone, Laidler, and Eyring, McGraw-Hill Book
Company, New York (1941).
CHAP.
XIX]
ACTIVATED ADSORPTION
909
910
CATALYTIC REACTIONS
[CHAP. XIX
at low temperatures, large quantities of adsorbate, low heats of adsorption, and a relatively low degree of specificity. Activated adsorption on
the other hand is characterized by low rates and high energies of activation, low quantities of adsorbate, high heats of adsorption, and a high
degree of specificity.
Chemisorption Rates and' Equilibria. In the development of rate
equations for simple activated adsorption, it may be assumed that a
unit area of surface offers L' active centers on which adsorption,may
occur and that all of these centers behave similarly. The rate of adsorption per unit area of a component A from a fluid in contact with the surface is then proportional to its activity UAI in the fluid at the interface
and to the concentration c^ of vacant active centers per unit area of surface. Since the actual surface area of porous materials is generally
unknown, it is convenient to express reaction rates in moles formed per
unit time per imit mass of solid having a surface area am. It is also convenient to express the number of active centers per unit mass in molal
rather than molecular units. Thus L, the nmnber of molal active centers
per imit mass is equal to L'um/N where N is the Avogadro number.
Similarly the concentration of vacant active centers may be expressed
in molal imits per imit mass and designated as Cj. On this basis,
rA = kAaAiCi
(4)
where TA = rate of adsorption of A, moles per unit time per imit mass
kA = adsorption velocity constant of A
CiAi = activity of A in the fluid at the interface, in concentration
units
Ci = molal concentration of vacant active centers per unit mass
Since chemisorption is a reversible phenomenon, component A is also
desorbed from the surface at a rate proportional to the concentration of
adsorbed molecules on the surface. Thus,
T'A = KCA
(5)
TCACA
(6)
- ^ 4 f = K.
where KA = adsorption-equilibrium constant of A.
(7)
CHAP. XIX]
911
If (6) and (7) are combined, an expression is obtained for the net rate
of adsorption where all sites are equally accessible.
r = fc^ (aAiCi - ^ )
= kACiiuAi - al,-)
. (7a)
(7b)
(CA
CB
+ ct )
'
(8)
(9)
912
CATALYTIC REACTIONS
[CHAP. XIX
.*
The theory of absolute-reaction rates is applicable to chemisorption in
the same manner as to homogeneous reactions. It is assumed that
chemisorption takes place through the formation of an activated complex
with the active center. Thus, if I represents an active center the
adsorption of A is represented by
A + l:^Al^ = Al
If it is assumed that the activities of the adsorbed constituents are equal
to their molal concentrations per unit mass of adsorbent, the reaction
velocity constant of this reaction per unit mass of adsorbent is,
= -7- ^
(12)
n
where Ai?i and A<Si = the enthalpy and entropy of activation of the
adsorption reaction.
Similarly, for desorption,
KA
_AH^'
AS^
kl=^e ^ ^ " ^
(13)
^''
'^
= e ^^
(14)
CHAP. XIX]
913
r = kAfiA^iCi^ ^'ASPAA
(15)
-^r^
(16)
(18)
Combining (15), (16), and (18) yields
T = (fc^aflAjiCj
k^^r)
(19)
At equilibrium,
CAI
aA^iCi
kAji-A
jT
(20)
liAi
CA = CA.1 =
Ci^aA^iK^i
(21)
914
CATALYTIC REACTIONS
[CHAP. XIX
If A is adsorbed with dissociation from a mixture also containing components B and I, an expression similar to Equation (11) may be developed for adsorption-equilibrium conditions:
c^ =
^aA,iK,,L
1 + Va^jii^Aj + ttBiKs + aiiKx +
^22)
(22a)
* .
"
where a^^i is the activity of component A 2 at the interface in equilibrium
with the adsorbed molecules.
The fraction of available single sites Bi can be expressed in terms of the
number of moles adsorbed per unit mass, thus:
;-' = 1 - ^ ^ = e ,
(22b)
(22c)
CHAP. XIX]
SURFACE REACTIONS
915
916
CATALYTIC REACTIONS
[CHAP. XIX
(23)
C'AB = J, CAC'B
(24)
r = liCAi = kyCACt
(25)
(26)
If products R and S are formed, the net rate of the forward reaction on
CHAP.
XIX]
917
(27)
(28)
A+B^R
In the general case the system will include inert components in the fluid
phase represented by 7. . . .
The net rate of the forward reaction is the difference between the
rates of the forward and reverse reactions which are represented by
Equations (26) and (25), respectively. Thus,
r = {kcACB - k'cRCi)
(29)
LI
n'
(3")
CA = J^AdAiCi r/kj^
Similar expressions may be written for the other reactant and product
adsorptions, and substituted in Equation (29):
r = fc (KAaAiCi -jTji^BaBiCi -rr)
- k' \KnaBiCi + ^ j c J
(31)
918
CATALYTIC REACTIONS
[CHAP. XIX
CB
CB +
Ci )
kg
k'J
(32)
Combining Equations (31) and (32) yields a complete expression for the
rate of reaction in terms only of activities in the fluid at the interface and
the constants of the system. If the constants were all evaluated, the
equation could be solved graphically for the rate at specified conditions.
However, in general tljis complete equation involving the rates of all
adsorption steps as well as the rate of the surface reaction is so cumbersome as to be of little value.
As previously mentioned, in many cases it is satisfactory to assume
that the rate is controlled by a single slow step and that all other steps
are so fast that equilibrium may be assumed. The slow step may be
either the surface reaction or the adsorption of any one reactant or the
desorption of any product. Simplified useful equations may be developed on this basis.
Monomolecular Reactions. Two mechanisms may be postulated for
reversible surface reactions which are monomolecular in both directions,
such as isomerization reactions. The reaction might proceed through an
adsorbed molecule, acquiring sufficient energy to cause it to react and
form a product molecule (all the time confined to a single active center).
In the other mechanism an adsorbed molecule becomes sufficiently
energized to form a complex with an adjacent active center, which then
decomposes to form an adsorbed product molecule.
If the first mechanism is followed-, the rate of reaction is proportional
to the concentration of adsorbed reactant molecules:
r = kcA
(33)
A:tR
CHAP. XIX]
MONOMOLECULAR REACTIONS
919
Surface Reaction Controlling. If the surface reaction is rate-controlling, it is assumed that all adsorption steps are in equiHbrium, and the
surface concentration terms in Equation (33) may be replaced by
Equations ( U ) :
MECHANISM 1
_
'
^^
{
l + a^,K^ + au^u + a,J^,--X^'^^
TT - ^ 5 i ^ \
K' )
(QA\
^^^^
(35)
kLKA
/
l + aAiKA + aRiKR + aiiKi-'-V'''
MECHANISM
_ ORA
K)
^^^^
(11) gives
ICSLKA
ORA
(37)
(38)
920
CATALYTIC REACTIONS
[CHAP. XIX
aRiCiKA
,__,
^AL
/
1 + aEiKA/K + as,KB + aiiKi -y^'
_ OgA
K)
^ '
If it is assumed that the reaction takes place between adjacently adsorbed molecules, it is necessary that the monomolecular reverse reaction follow the mechanism expressed by Equation (25). By the same
procedures followed in the preceding section, the following rate equations are developed:
Surface Reaction Controlling
ksLKAKs
r = (1 + ttAiKA + ttBiKs + aBiKR + aiiKr --y
12
X (aAiaBi - Y)
(42)
CHAP.
XIX]
921
Adsorption of A Controlling
UAL
y =
1 + aBiKa +
^ , / + aBiKu + anKi H
Adsorption of R Controlling
kuLK
r
1 + ttAi^A + as^B
+ aAidBiK-RK- + auKi + . . .
xLiaBi-^)
(44)
In Equation (42) the initial rate of the reaction is increased by increased activity oi component B; in Equation (43) increasing the
activity of B reduces the initial rate where the activity of R is zero.
Thus, it is characteristic of a bimolecular reaction in which the rate is
controlled by the adsorption of a reactant that the initial rate is reduced
by increased activity of the other reactant.
In Equation (44) the over-all equilibrium constant of the reaction
appears in both the numerator and denominator of the multiplying
fraction. Under conditions favorable for the forward reaction where
K is large, the rate becomes independent of the activity of the product
and may approach ICKL/KR, independent of the activities of both reactants and product.
If the reaction on the surface occurs between an adsorbed A molecule
and an unadsorbed B molecule in the fluid phase, the rate is proportional to the product of the surface concentration of A and the interfacial
fluid activity of B. Equations similar to (42), (43), and (44) result,
except that the adsorption-equilibrium constant of B does not appear.
If the surface reaction is controlling, the term s does not appear, and the
denominator group enters as the first power instead of the square.
Reactions Bimolecular in Both Directions. Reactions of this type are
represented by the following equation:
A+B^R+S
By extension of the methods demonstrated in the foregoing, the following
rate equations may be derived, if the surface reaction is assumed to take
place between adjacently adsorbed molecules:
922
CATALYTIC REACTIONS
[CHAP. XIX
^
j
(45)
Adsorption of A Controlling
UAL
r =
1 -\
'^
] (46)
Adsorption of R Controlling
kRLK
r =
1 + ttAiKA + asiKs +
h asiKs + anKi +
asi
/aAjaBi __ ORA
X \P asi
^ - ^
K)
(47)
CHAP. XIX]
EFFECT OF DISSOCIATION
923
(48)
ci =
1 H
-=z
VttBiK
CRCS
ciaRiKnasiKs
ciamasiKA
= ^ ^
=
=^
cisK'
V^^^K'
VasiK
.^,
(49)
(50)
h VasiKs
O-RidSiKA
j=^
VasiK
(51)
When Equations (51) and (46) are compared, if the component whose
adsorption rate is controlling is not dissociated, the rate equations are
924
CATALYTIC REACTIONS
[CHAP. XIX
CBK'
' =
1 -\
aRiasiVEl
' '
UBiK
^^^^
+ asiKa + aBiKa + asiKs + anKi ^
aBvK
^' ^'
This equation is quite different in form from Equation (46), and it is also
dependent on the mechanism assumed for the adsorption and dissociation
of A. By assuming a different mechanism (6), an equation can be
obtained in which the initial rate is proportional to the one-half power
of the activity of A instead of the first power of Equation (54).
If reactant A is dissociated into two chemisorbed half molecules, both
of which enter into the reaction, a still different series of equations
results. If reactant B is adsorbed without dissociation, the surface
reaction in this case involves three active centers. Thus,
2 ( U ) + 5 4- 3Z = 72 -1- S -t- 3J
(55)
CHAP. XIX]
925
Yi
v^^)
s(s - l)kA r , . ,
cncscil
Y^
]^B{C\AY - - ^ J
(57)
r =
.
(1 H- VaAiKA + aBiKa + amKii + asiKs + aAiKiY
[aAiUBi
(58)
Since the surface reaction and the adsorption of B, R, and S are assumed
to maintain equilibrium,
, . CRCSCI aAiasiCJKRKs amds^KA
{cur = ^ =
F~F7~ =
IP
ci = L cA \j-^^~^jr^
,,
(60)
or
ci = .
1 + J
(61)
^' ^' ^ + OBiKs + OBiKR + asiKs + auKi
926
CATALYTIC REACTIONS
[CHAP. XIX
r =
! 1 + \ / " ~ F ^ + (^BiKa + aBiKs + asiKs + anKi
lo.Ai
If the adsorption of B, R, or S is contrpUing, the rate equations are similar in form to Equations (46) and (47), except that in the denominator
group the product of the activity times the adsorption-equihbrium constant of the dissociated molecules is raised to the one-half power.
POISONS
The term " poison " has been loosely used to denote any material
which retards the rate of a catalytic reaction. Thus, the products of the
reaction are sometimes referred to as poisons because increasing their
concentration reduces the rate. However, it is beheved more logical to
eliminate all reactants and products from classification as poisons and
reserve the term for other components which retard the reaction by
reducing the number of active centers available for the reactants. Such
poisons may be classified as either temporary or permanent.
From inspection of the rate equations it is evident that any inert component / which is adsorbed on the active centers promoting the reaction
serves as a poison; the extent of the retardation depends on the concentration of the inert and its adsorption-equilibrium constant. If the
adsorption of the, inert is reversible with a moderate equilibriimi constant, the poisoning effect quickly reaches a constant value which is
temporary and is eliminated by removal of the component from the
reactant fluid. Thus, the nitrogen in air might serve as a temporary
poison in a catalj^tic oxidation. The effects of such inerts are included
in the rate equations.
Another type of poisoning frequently encountered results from the
permanent substantially irreversible adsorption of components present
in small quantities in the reactant fluid. The effect of this type of
poisoning is progressively to reduce L', the number of active centers per
imit area, as the catalyst continues in service. The frequently observed loss of activity of a catalyst in service may result from poisoning
of this type, from structural changes affecting the area and L, or from
physically coating the active surface with a solid or semisolid material
either present in the reactants or formed by secondary reactions. In
high-temperature organic reactions, catalysts are frequently coated
with high-molecular-weight compounds approaching pure carbon in
composition.
CHAP. XIX]
CONVERSION EQUATIONS
927
(63)
Integration yields
F
(So pj
f Jo r
(64)
928
CATALYTIC REACTIONS
[CHAP. XIX
(65)
CJo
cJo
l/K)x\
[1 - (1 + 1/K)z]
^ '
Integration gives
W
C(l + IIKY
In
(67)
CHAP. XIX]
CONVERSION EQUATIONS
929
o = (1 + \/K);
a =
(I/TT
1
I
+ KAn^ 4- Km:);
P=
{KR
(a)
KA)\
Dual-Site Mechanism:
w\F J
\a
a^
a^ JxuAo-
ax)
2a
a^
^'
where
a = l + l/K;
A'^R
^ =- (KB - KA)
where
a = l+T/K;
= (I/TT + KA); P= aZ-^ + Ks +
" >
Ks-KA))
(c)
930
CATALYTIC REACTIONS
[CHAP. XIX
Dual^Site Mechanism with a diluent / present in such large proportions that the
change in the number of total moles is negligible:
v\F J ~ \2a2
a/
\
riAo
)
a
//3'(1 +2re^oa) _ g , . V j (2ai + 1 + 7 ) ( 1 - 7 )
\
20'
o
/ 7 '^(2ax + l - 7 ) ( 1 + T )
where
a = It IK;
a = (I/TT + K^n^o + X^/n/)
0=^ {KR + KS4 + B ? 2R
Ki);
(d)
7 = V4nAoa + 1
1 r
27 L
o = (1 - 4/X);
e = [Kii-
2a0no , j 3 2 n ? ( 2 - a ) 1 , ( o x - n o - 7) ( - n o + 7)
a
a2
J
(ax-no+ 7)(-no-7)
^^'
{KA + X B ) / 2 ] ;
7 = VnS -
ar^
Nomenclatuie
a = constant, defined for each equation
C = combined proportionality factor in the differential rate equation
written in terms of activities referred to unit fugacity
F = feed rate, moles per unit time
K = over-all thermodynamic equilibrium constant of the gas-phase reaction
KA, KB, etc. = adsorption-equihbrium constants of components A, B, etc.
nxo = moles of A originally present per mole of feed
n/ = moles of inert component /, per mole of feed
W = mass of catalyst in the reactor
> ft 7 = constants, defined for each equation
ir = total pressure in units used for expressing fugacity in the differential
rate equation
CATALYST FOULING AITO DEACTIVATION
CHAP. XIX]
931
932
CATALYTIC REACTIONS
[CHAP. XIX
CHAP.
FOULING FACTORS
XIX]
933
^
Y>
k^-^-
^>
. " ^ A
^S.
^V
^ ^
\'--*^^*V^
-968 F. '^
***'^
S^^>.1020F. "~ -932 F.
0)
glO _
M 9
g 6
Z'860F.--
^ ; ' ^ 6 8 F.
788 "F.
2 --
.F
100
1020F.
1
1 \
I
1 1
200
300
400
BOO
Process period T (min)
FIG. 182. Effect of Process Period upon the Production of Toluene.
(Pressure = 31.5 atmospheres: W/F = 66.)
934
CATALYTIC REACTIONS
[CHAP. X I X
(68)
There is evidence that toluene is also simultaneously produced by disproportionation of xylene to form trimethyl benzene and toluene. However, for the restricted case of a feed of equimolal proportions Johanson
and Watson assumed that the over-all rate of production of toluene
could be expressed by the empirical evaluation of the rate equation of
reaction (68). On this basis it was found that the average conversion
data over wide ranges of conditions were fairly well represented by the
following basic rate equation:
r =
(I +
^^''^'''^ ~ / - ^
OAKA + GBKB + UBKB
(QQ)
+ Biry
CHAP.
ACTIVITY FACTORS
XIX]
935
In Figs. 183, 184, and 185 are average conversions calculated by integration of Equation (69) to show the effects of varying pressure, space
velocity, and temperature, respectively, at process-period lengths T of 0,
40
30-
.."^
^^^
^T^BO
9. ^
T=300
10
II
10
15
20
25.
PressTire TT, Atm
30
35
FIG. 183. Effect of Pressure on the Production of Toluene from an Equimolal Mixture of Benzene and Xylene. WjV = 66; temperature = 932 F.)
50, and 300 min. It may be noted that the length of the process period
is an important variable which must be carefully considered in the engineering analysis of such a process.
The methods followed in evaluating the constants of Equation (69)
are discussed on page 938.
50
40-
.^v^'^
&
o
^/J^--^
3 0 ~-"
20 %
a
ft-10
<i>
3
& ^
II 0
FiQ. 184.
.^^-
-^'-
20
40
60 80
100 120
W/F^Mss.s. Catalyst) (Hr) / (Mole Feed)
140
936
CATALYTIC REACTIONS
[CHAP.
XIX
a change in the catalyst due either to changed preparation or to deactivation in use may markedly change both the'adsorption-equilibrium constants and the over-all rate factor. In this event all constants must be
re-evaluated at different levels of catalyst activity in order to maintain a
800
900
1000
Temperature, F
FIG.
(71)
It is evident that the factor L, will appear,as a multipHer in any integrated-conversion equation of the type shown in Table LVII. Thus,
if the same conversion is produced by catalysts of different activities
they must operate at different space velocities, and, under these
conditions,
(72)
If catalyst 1 of Equation (72) is adopted as an arbitrary standard of comparison and assigned an activity factor of 1.0, the activity factor of any
other catalyst of generally similar type may be determined by experimentally evaluating the conversion produced at a selected space velocity. If the conversion produced by the standard catalyst at the same
conditions is known, the activity factor is calculated directly from
Equation (72).
CHAP.
XIX]
937
Ordinarily catalyst activities are compared at standardized test conditions. Frequently activity ratings have been based on merely a ratio
of the conversions obtained in such a test. Such a scale may give a distorted picture of the relative activities as indicated by Fig. 186 in which
conversion x is plotted against W/F for a standard catalyst. A catalyst
producing a conversion represented by point B has an activity factor
equal to the ratio of the abscissas at point C to that at B. Similarly, a
W/F
FIG. 186. Catalyst Activity Factors.
where
p BT
"^ R
* = TW
7* = activity coefficient of the activated complex
Vm = molal volume of the activated complex.
(74)
938
CATALYTIC REACTIONS
[CHAP. XIX
ah
and this equation may be written
e '
r = (1 + aAiKA + aBiKs + auiKR + asiKs + anKi -\
( aAittBi
Y
aRiasi\
,__ .
(75a)
CHAP. XIX]
939
ment of the Gaussian law of error which leads to the conclusion that the
most probable value of a quantity which is derived from a number of
experimental observations of equal absolute precision is that value from
which the sum of the sqvnres of the deviations of the individual measurements is a minimum. The derivation of this " principle of least
squares " may be found in standard mathematical texts which deal with
probabihty.
The principle of least squares is particularly valuable for evaluating
equations which can be written in a form which is Unear with respect
to each unknown constant. This general form isl
.
y = a + bxi + cxc
(76)
(77)
+Dl
= minimum
(78)
Since SZ)^ is a function of the unknowns a, b, c- its minimum corresponds to a zero value for the derivative of SZ)^ with respect to each of
the unknowns. Thus, with respect to a,
da
-[-f--^---^-]-
(79)
-yi
a +
bX6 +
CXcn +.
2/n) =
(80)
-Xiiyi
do
-\
aXbn + bx^tn +
CXcnXbn +
XbnVn) = 0
(81)
940
CATALYTIC REACTIONS
[CHAP.
XIX
(82)
(83)
(84)
Service Time.,
days, T
0
7
14
21
28
35
42
49
56
252
Activity Factor,
T
39
40
38
38
35
38
37
35
337
0
49
196
441
784
1225
1764
2401
3136
9996
TLr
0
280
632
798
980
1330
1654
1715
2072
9261
(a)
(b)
(c)
(d)
(e)
CHAP.
XIX]
941
b = -0.05952
10
20
30
40
60
Catalyst Service, r (Days)
60
.,
(85)
KAB
(86)
(1 + KA^Y
1
942
CATALYTIC REACTIONS
[CHAP. XIX
b=
-AH
, and Xi = \/T.
The
CHAP.
XIX]
943
changes or, better, derived from the logarithmic mean of the differences
between the activities at the inlet and the outlet for the reactants. The
mean activity of a product R may be taken as Ofl, minus the log mean
value of {uRe o) at the terminal conditions where age is the activity of
R when the reaction proceeds to equiUbrium. This use of log mean
activities is merely an improved approximation which in general is not
satisfactory except where concentration changes are small.
The adfeorption-equihbrium constants which appear in the rate equations theoretically might be independently determined by adsorption
measurements on the individual components. Such measurements may
prove to be a valuable adjimct to direct catalytic rate measurements but
are open to question because of the interaction effects and variability of
active centers previously mentioned. Until these relations are better
understood, these constants in the rate equations are best determined
in the specific reaction under study by making rate measurements over a
wide range of concentrations.
To minimize tedious algebraic solutions of simultaneous equations, it is
desirable in complex systems to determine the effective average value of
the absorption-equihbrium constant of each component by a constanttemperature series of at least three differential rate measurements in
which the activity of that component is varied over a wide range while
the activities of all other components are held constant. A convenient
procedure is to make an initial run with the activity of each component
at approximately the middle of the range of interest. Additional series
of two runs each are then made in which the activity of each component
is varied from a minimum value in one to a maximum in the other while
the activities of all other components are held constant. This procedure
may require two or more trials at some of the conditions with interpolation in order to obtain satisfactory constancy of the grouped activities
but is not difficult with a flexible differential-reactor apparatus which
permits wide variation in feed rates and depths of catalyst bed.
Once the adsorption-equilibrium constants are all evaluated, each
single rate measurement permits calculation of the over-all rate constant C. These methods are demonstrated in the following illustration.
Illustration 2. Mixed iso-octenes, commercially known as codimer, are hydrogenated in the vapor phase to the corresponding iso-octanes according to the following reaction:
CsHiaCg) + HaCg) ^ CsHisCg)
The reaction as it takes place on a supported nickel catalyst was studied in a pilot
plant which was operated with a small bed of catalyst to approximate differential
conditions. The experimental data are tabulated in Table A. These data were
obtained when the catalyst was used at sufficiently high mass velocity that diffusional
944
CATALYTIC REACTIONS
[CHAP.
XIX
gradients were shown to be negligible, and the activities at the surfaces of the catalyst
pellets may be assumed equal to those in the fluid stream. From these data it is
desired to determine the probable mechanism of the reaction and to evaluate the constants of the corresponding rate equations. These experimental data and their interpretation are taken from the work of Tsehernitz, Bornstein, Beckmann, and Hougen."
The experimental procedure was planned to estabhsh the effect of the average
partial pressures of each component while holding the average partial pressures of the
other two components nearly constant. However, the exact attainment of such conditions is not practical, since this would predicate advance knowledge of the exact
effect of all the variables controlling the reaction rates.
In the operation of the experimental plant the rate of Uquidflowwas measured from
.
TABLE A
EXPBBIMENTAI. D A T A
Temperature = 200C
Run
Id
3c
3d
10a
11a
lid
lie
12ab
14a
14b
25a
28b
1.09
3.50
3.49
3.51
1.51
1.50
1.50
1.105
3.52
3.51
2.50
2.10
PB
0.482
2.459
2.450
0.477
0.514
0.473
0.470
0.104
0.450
0.409
0.484
0.357
average values
Pa
0.100
0.527
0.530
0.494
0.540
0.552
0.558
0.562
2.840
2.810
1.075
1.590
Temperature =
-- 275C
average values
Pv
0.102
0.518
0.517
2.770
2.800
0.562
0.506
0.556
0.540
0.462
0.485
0.511
0.776
PS
0.508
0.515
0.515
2.538
0.455
0.473
0.473
0.440
0.230
0.289
0.942
0.153
r
lb-mole /
ab)(hr)
0.00353
0.0250
0.0320
0.00553
0.00870
0.01392
0.00960
0.00514
0.01920
0.0206
0.0131
0.0186
f
lb-mole /
T
Run
PH
Ob)(hr)
PS
0.478
2a
1.105
0.525
0.00298
4d
3.520
2.505
0.497
0.0389
4e
3.500
2.500
0.485
0.0450
0.425
5b
3.510
0.310
0.0206
3.500
0.433
5d
0.270
0.0185
1.104
0.489
6bc
0.051
0.0180
7b
1.500
0.546
0.446
0.0103
7cd
1.500
0.469
0.475
0.01215
8bc
1.109
0.100
0.464
0.00705
9a
3.500
0.422i
2.615
0.00824
9b
3.610
0.467
2.555
0.00734
26ab
2.500
1.495
0.495
0.0319
29ab
1.222
2.100
0.103
0.0435
*' J, Tsehernitz, S. Bornstein, R. B. Beckmann, and O. A. Hougen, Trans. Am.
Inst:Chem. Engrs., 42, 883-903 (1946).
CHAP.
HYDROGENATION OF CODIMER
XIX)
945
Temperature = 325C
Run
15a
16a
17b
17c
17e
18a
19b
19c
19d
20ab
21a
24a
27a
30a
30b
3.50
1.10
1.50
1^50
1.50
1.10
3.50
3.50
3.50
1.10
3.51
2.50
2.50
2.10
2.10
PH
0.500
0.482
0.501
0.475
0.476
0.101
2.335
2.540
2.405
0.489
0.480
0.555
0.599
0.438
0.478
average values
Pa
Ps
2.735
0.270
0.660
0.062
0.533
0.466
0.653
0.471
0.656
0.478
0.548
0.451
0.550
0.610
0.452
0.510
0.624
0.572
0.098
0.513
0.480
2.550
0.299
1.645
0.996
0.907
1.523
0.136
1.480
0.144
lb-mole/
ab)(hr)
0.0201
0.0U4
0.0134
0.00946
0.00871
0.0025
0.0338
0.0286
0.0297
0.0044
0.01106
0.00533
0.01885
0.01414
0.0159
the volume and density of the outgoing liquid, the outgoing hydrogen by a displacement meter, and the degree of conversion from the index of refraction of the ingoing
and outgoing liquids. The composition of the liquid was related to the refractive
index by previous calibration pf known samples analyzed for unsaturates primarily
by hydrogen absorption and secondarily by standard chemical analysis by the
bromine method. The following ranges of variables were investigated: pressures
from 1.0 to 3.5 atm, temperatures from 200 to 325C, and feed compositions from 10
to 90 mole per cent of each component. The five different feed stocks used were
previously purified by steam distillation to separate polymers and by passing through
a bed of nickel catalyst in the absence of hydrogen to remove sulfur. Temperatures
above 350C could not be investigated because of catalyst disintegration. The calculations involved in a specific run are illustrated herewith.
Blank tests were made in the pilot plant in the absence of the catalyst to determine
the extent of the uncatalyzed reaction. This was not detectable at 200C and 275C.
At 325C a slight reaction took place amounting to 1 to 5 per cent of the catalyzed
reaction depending upon feed composition. This correction was made to establish the
rate of the catalytic reaction at 325C.
RUN 3C:
946
CATALYTIC REACTIONS
[CHAP. XIX
Liquid leaving =
lb-moles
Entering
per hr
Unsaturates = (0.541) (0.01671) =0.00904
Saturates
= (0.459) (0.01671) =0.00767
Hydrogen = 0.03905 + 0.00109 = 0.04014
Total
0.05685
Mole
Per Cent
15.90
13.49
70.61
100.0
Partial
Pressures, atm
0.557
0.472
2.471
3.500
Leaving
Unsaturates = 0.00904 - 0.00109 = 0.00795
Saturates
= 0.00767 + 0.00109 = 0.00876
Hydrogen =
0.03905
Total
0.05576
14.26
15.71
70.03
100.0
0.499
0.550
2.451
3.500
1^
Since the change in composition is small, the arithmetic average partial'. pressures may
be taken. Thus,
Pv = 0.628
PS = 0.511
PH = 2.461
X = 3.500
Cross-sectional area of bed (1.05 in. diameter) = 0.00601 sq ft
Enteringflowrate = 0.00905(112) -1-0.00770(114) +0.0401(2) = 1.972 lb per hr
1 972
G = mass velocity = ^^~l
= 328 lb/(hr) (sq ft)
At this mass velocity and reaction rate r, the transverse partial-pressure gradients due
to mass transfer are negligible.
Gaseous space velocity of entering feed = '
latm)/(cuft)(hr)
Over-All Equilibrium Constant. Before the mechanism of this reaction was
studied, thermodynamic calculations were made to determine the reversibility of the
reaction within the experimental range of pressures and temperatures. The equilibrium degrees of conversion in the hydrogenation of codimer are plotted against temperature for various total pressiu'es in Fig. 188. These data were calculated from the
standard free-energy equation based upon the hydrogenation of 2,4,4-trimethyl
pentene-1:
ACTT = -RT
CHAP.
947
HYDROGENATION OP CODIMER
XIX]
I 0.8
m
I 0.6
a
6 0.4
\ * 3
Y.
.2 0.2
0.0
S.V
700
900
1100
1300
Temperature, K
1500
948
CATALYTIC REACTIONS
[CHAP XIX
1
= - (1 + KHVH + Ks^pa) = a + fvn + cpa
+ bpa
r
(d) Surface reaction controlling:
R = ^/
=^
\l r
yjct
+ Ksps) = o +fV^
+ cps
UKHKXJ
+ Kvpu)
= a +fV^
+ bpt.
+ bpu + cps
III. Reaction between codimer in the gas phase and molecularly adsorbed hydrogen:
(t) Adsorption of hydrogen controUing:
fi = = i ( 1 + Ksps) = a + cps
r
a
(j) Desorption of hydrogenated codimer controlling:
R = ^^^ = ^ ( 1
+ KHPH)
= a +fpB
PHPU
r
CHAP. XIX]
? HYDROGENATION OF CODIMER
949
IV. Reaction of codimer in the gas phase and atomically adsorbed hydrogen:
(0 Adsorption of hydrogen controlling:
=^/? = ^^^
{m) Desorption of hydrogenated codimer controlling:
R = mSR = - ^ (1 + y/KaVH) = a + / \ ^
r
octiit
/ ^
(1 + VKJIPH
+ Ksps) = a+fV^
+ cps
VHVU
= ^
UKH
B = ^ = a
PHPJ/
Interpretation of Data. The constants of the equations for the various proposed
mechanisms were evaluated by the method of least squares. The four constants,
a, h, c, and / were evaluated for each mechanism. It is a requirement of the theory
upon which these equations are based that all constants must have positive or zero
values. As an illustration, the method of evaluating the constants for mechanism d
are given for the 12 runs made at 200C.
The four simultaneous equations for evaluating the four constants by the method
of least squares are as follows, where K =
an
+
aSpH +
o2pc7 +
o2ps +
and n = 12.
fcSpu + c2ps
+ /2pH
= 2/2
VLp'HPu + cSpHPs + /2p/7
= 2p^B
&Spu + cZpups + f^PuPH - ^PuR
bXpspu + cSp%
+ fipsPH = SpsB
(b)
(c)
(d)
(e)
CATALYTIC REACTIONS
950
CO CD
i n NCO r ^
IN IN
ffd
00
^
O
05
in
03
(N
"5
00
05
IN
11
'H O
CO
CO
C<3
IM
t to
*
O
in
<N
O
O
IN
t^
CO
N
c^
CD
to o
o oo o
lO
1^
IN
C^
t3
.-1 M
iO
N
^'C
at
CO
IN
^
T-H
CD
(N
*
*
o o o
to
O
00
S
t 1-1 1 >
O
IN
Ol o
o
00
IN
IN
I
C5
t~
o
IN
>-<
w
to
N
CO
c^
to in
IN O
CO
05
> Ml
CO -H
CO
O
CO
in
CO
t CD
m
o O
>-i - H
Oi
o
IN
cq
^
W
CO CO
IN
IN
I N C<)
CO
O
rt
O
m
CO t ^ - * b O CO CO CO
CO I-H C I - - l
O
CD O i i n T j i
CO CO CO t C5 i n 0 0 0 0
i-i
O O
00
o o o o o
CO
in
CO
t^
O
CO
O
CO
I-H
*
CO
C
O
in
CO
rH
05
TjH 0 0 CD 11 CO T-^
in
m CD i n 0 0
^ H CO c:2 i n CO
O 0 0 1-1 i n
CO CO CO
1-1
00
to
o o
CO
i-H
CO
to
to
IN
O 00
CO CO CO
^ CO O
O
<-< T j i CO i n
CO
CD
CO t ^
05
CD
to
1>
^
^ -( ?^^
o o oo
?!g
[CHAP. X I X
n>
IN
00 00
CD -l
in
CO i n
CO t ~
CD CO m
to
03
CD i n
C3
M
1-1
i-H
lO
O IN
* *
T_t
i n CO
00 t -
1-1
CO i n
&
^
t-
00
CO 1-1
f-i
'(I
i n 00
CD CO
CO
t ~ 1-H
CO
CD i n
in
cn o
CO CO
o
CO
S5.
o
o
/-^
2
o
O
.3
^
CO
m o o
CO i n
IN
O
C<1 CO
o o o
o o o
<
b
a.
w
sa.
>3
c=5
CO
in
in
o
o
o
r^
m
CO
c
CO
-I
O
to
05
O
O
^
in
O
O
O O
CO
03
1
O
O O
O 05
CO
o T)l
in o
t^
t - o
T t l TJH T1 T j l M l
IN
00
Tti
Ci
in
Tji
O r^
i n r^
- ^ 'ti
IN
IN o
o o o
00
O
in
in
^-1
in
i n no
^H
in in
lO
in
Tti
CO CO o
> lr~ T h
Ttl T j l - *
o oo o
o
O
rH
t N
in
o
Ml
in
CO
in
in
O IN
o *
CO m
in
-*
o o o
o
'^
O
1 CO
T 3 oii
CO o
CO 1-1 CD
o
CO 0 0
CO 1-H 1-1
O
O
O
in
en T )
T-i
^
00
*
t^
in
CO
C5
CI
1-1
OS
CO
in
i i
tH
CO
in
t^
O o
in
T * 1-1 w
CO 0 0 o
o
as
in
00
t 1-1
o O
CO CO
1-1
1-1
CO
rH
O -a
i-H CO
x>
*
la
XI
00 CI
i n CD
in in
o O
o C2 C?
CO 0 0 *
CO CO 0 3
O
CHAP. X I X ]
HYDROGENATION OF CODIMER
~
u
O
K
tt
oj
*"
00
00
CD CO
* o
i n lO
00 O
t^
>*
>-< 0 0
"^
00
a.
^ (N o n*
ta
o
<
(a.
f[
^<3
lO
f-H
CO
i-H
I1
CO o o
O 1-1 N
J?
TH
<3S
*
O
o o o o
-I
Ol
(N
( M T-l
CO l O
M (N
rt O
O
CO
O .-1
CO 0 0
CO r H
lO
CO
O i n
l O CO
CO
CO
CD
t
oi
CD ( N CO
0 0 CO CO
CO
00
CO CO CO
CD
-*
!>.
t *
CD t i r j o
CD C
i-i T H
O O
T-i 0 >
-I
i >
r-1
l o CO ( N
T-l
(M
CO
*
o
CO
111
O
03
O
CO o
C d CO
" - I 1-1
o o o o o
on o o m
>n CO CO CO
O
TjH
-*
1*
-H ^i
45,
CO
CD
O
CO
o II
U3
eq
o o o o o o
1
1
1
o
a <N
CD CO
*
OS l O
CO CO
" 1
CD O
C 3 CO ^
O CO CD
rt
O
CO o i
CO CO
951
CO
* CO
in
CO 0 0
w CO
in
00
rH
*
00
1-1 O
0 0 rjH
lO
t -
t^
l > i n
i n
i-< 0 5
l O TjH
O
^
CD
CO CO CO
1-1
CO Tt< I N CO
r f i t < 0 CD
O * CO CO
(M I N
o o
CO *
CO 1-1
o en
00
in
in
i n
a.
ft?
a
a
B5
%
J^
C32 0 0 O
CD 0 2 t 0 0 CD ( N
i-i
CO CO CO ( M
CD l O
m CO
r H OS
1-1 1-1
i-t
^ lO
(N O
00
CO 0 5
8
2
0 3 1-1 0 3
CO CO CO CO
<N I N
r-l
00
O
lO
o
<*<
1
t>
cd
o
00 t~CO CO XO
t^
0 T)(
N
e<i N
05
M<
TJH
TH
"B
oq
t^
00
IM IN
0 0 - ^ CO
CO CO CD
CO 1 > CO
O
i >
t - 1 CO
a s t - - i * CO 0 0
^ lO
O Tfl " *
--I
^H
O
N
Oi
CO I N
CO l > CO
CO * m
CD
IN M
0 3 1 ^ CO 0 0
CO CO I N U 5
CO C ^ I N ^
(N IN (N O
r-1
-(
o o
CJ 1 3
o5
T3 o
I-*
I-H
CO
t >
i >
CO
CO
i n
00
O CO
IN
00
i n
CD
O
i-l
IM
t>.
o o o O O
^ 00
CO ^
CO CO
IM ( N
00
00
i n
o o
m o
1-1 b - CO
I N C<1 CO
- ^
1-1 1 - 1
00 O
IN
>-H
r~t
CO
IN
C^
N
*
00
CD
CO
O
I-I
CO
00
1-1
1-1
05
i n
i n
1 *
CO
*
i n
O
CO
<ii
o o o o o m
J3
N
iJH
d
* i n
N
^
00
CO
II
H
952
CATALYTIC REACTIONS
[CHAP. XIX
(j)
(k)
(1)
JPHPI
(m)
The accuracy of this equation for any particular experiniental run is established by
comparing calculated with experimental values by the standard deviation squared,
5\ where S is the difference between calculated and experimental 1 values of R. The'
percentage deviation of individual runs is given as 1003 /R where R is the experimental
value. These values are recorded in the last three columns of Table C. It may be
observed that the average percentage deviation for individual runs is 8.4 per cent;
the experimental accuracy of individual runs is no better than this because of the small
changes in composition obtained in the small catalyst beds. Runs'lla and 12ab show
large deviations. Greater degrees of .conversion can be obtained by using larger beds,
but this introduces even greater errors due to uncertainties in average values of
temperatures and partial pressures.
,
Evaluation of Constants in the Rate Equations. The experimental values of a, 6, c,
and/for the accepted mechanism d are recorded in Table G for th^ three temperature
levels and plotted in Fig. 188a on log constant-reciproqal temperature co-ordinates.
CHAP.
XIX]
HYDROGENATION OF CODIMER
953
Since the several constants a, b, c, and/ are each products and quotients of adsorptionequilibrium constants and one reaction velocity constant as shown in Equation (d)
of Table B, they would be expected to plot as nearly straight lines on log constantreciprocal temperature plots. In this respect it may be observed that the values of a
and b plot well, / plots fairly well, but c plots poorly. The best straight lines on this
logarithmic reciprocal plot were established by the method of least squares for each
constant. The corrected values obtained from the straight lines are recorded in
Table G for the three temperature levels.
TABLE D
CONSTANTS FOR VARIOUS MECHANISMS AT 2 0 0 C
Mechanism
a
h
c
d
e
9
h
i
64.6
- 1 9 . 4 12.1
44.0
35.4 14.8
-101
44.0 117
2.76
1.53
1.01
6.64 - 1 . 3 1
0.89
66.9
36.5
15.6
42.4 114
-115
0.736
0.781 1.29
64.6 - 1 9 . 4
12.1
-101
44.0
k
I
-101
5.64
44.0 117
-1.31
0.89
-116
42.4
1.74
-101
-101
1.50
0 95
44.0 117
44.0 117
P
5
r
44.0
-101
36.4
44.0
117
114
14.8
117
/
16.3
-22.6
24.3
1.13
2.73
-61.8
45.0
1.09
16.3
f should be 0
b should be 0
c should be 0
Acceptable
/ should be 0
b should be 0
c should be 0
Acceptable
h should be 0
/ should be 0
24.3
6 should be 0
c should be 0
24.3
6 should be 0
2.73
b should be 0
/ should be 0
45.0
& should be 0
c should be 0
2.46
6 should be 0
24.3
/ should be 0
24.3
c should be 0
/ should be 0
- 2 2 . 6 , & should be 0
/ should be 0
24.3
6 should be 0
c should be 0
/ should be 0
6 should be +
f should be +
a should be +
b should be +
/ should be +
a should be +
a should be +
a should be +
a should be +
a should be +
a should be +
CATALYTIC REACTIONS
954
[CHAP.
XIX
Aff
AS
(o)
Provided the catalyst activity remains unaltered with change in temperature the constants AH and AS correspond to the effective enthalpy and entropy changes, respectively, in activated adsorption; otherwise they are empirical only.
TABLE E
CONSTANTS FOB VAEIOUS MECHANISMS AT 2 7 5 C
Mech-
anism
a
b
c
d
e
9
h
i
63.0 - 1 9 . 0
2.87
1.0
31.3
8.01 - 2 1 . 0
41.8
3.98
18.9
4.45
5.97
2.84
0.494
0.687
1.60
7.12 - 1 . 6 1
0.370
0.810
13.0
67.4
15.4
-31.7
-311
22.2
7.65
40.8
1.74
0.644
0.606 0.216
63.0 - 1 9 . 0
2.87
1.0
3.98
18.9
4.45
5.97
k
I
3.98
7.12
18.9
-1.61
4.45
0.370
5.97
0.810
22.2
7.65
1.60
18.9
18.9
0.500
4.45
4.45
41.8
8.01
18.9
4.95
m
n
0
-311
2.12
3.98
3.98
40.8
1.53
5.97
5.97
9
5
r
31.3
3.98
-21.0
5.97
The term effective is used here to distinguish the values of AH and A<S effective in
catalysis from those values obtained by separate adsorption of the pure component
gases in the absence of a catalytic reaction. The values of AH and AS for each component are recorded in Table G.
The rate constant a is made up of the surface-reaction velocity constant k arid the
CHAP.
XIX]
HYDROGENATION OF CODIMER
956
Mechanism
a
b
c
d
e
f
9
h
i
11.7
63.0 - 2 3 . 3
2.35
54.0
33.8
-8.35 -10.7
20.1
0.623
8.11
9.97
3.75
1.60
0.039
0.697
0.108
1.77
7.01 - 1 . 6 4
124
26.7 - 1 1 . 4 - 8 4 . 1
2.29
20.2
0.376 17.3
0.593
0.010
0.598
2.17
63.0 - 2 3 . 3
11.7
2.35
9.96
20.1
0.623
8.11
k
I
9.96
7.01
20.1
-1.64
0.623
0.108
8.11
1.77
2.29
20.2
0.376
3.00
9.96
9.96
1.61
20.1
20.1
0.0114
0.623
0.623
V
9
r
53.9
9.96
33.8
20.1
-8.35
0.623
17.3
1.60
8.11
8.11
-10.7
8.11
6 should be +
c should be +
/ should be +
h should be +
c should be +
/ should be +
c should be +
vated complex, AH^ = 1740, and B could be taken as the entropy of activation,
A(S* = 2.82. The low value of AH* and the positive value of AS* are both consistent
with the properties of an effective catalyst such as the one under investigation. It
should be noted that if the catalyst activity does not remain constant with temperature change the adsorption values of &.H and AS for different gases become empirical
constants and do not correspond to the true enthalpies and entropies of adsorption.
CATALYTIC REACTIONS
956
~o
"
1
0.8
0.6
[CHAP.
/ -
>
_a-
C j /
0.4
0.2
0.1
J,
- /
0.08
0.06
0.04
XIX
0.0016
0.0018
0.0020
1/TK,
0.0022
^]
, 3110
940
13,700
In Xs = + RT
,
8.49
3.08
30.96
R
(q)
1740 , 2.82
CHAP.
XIX]
HYDROGENATION OF CODIMER
957
i/rK
o.ooso
0.0022
TABLE G
SUMMABT OP T H E B M O D V N A M I C CONSTANT,
a
6
c
/
(experimental)
(experimental)
(experimental)
(experimental)
o
6
c
/
(corrected)
(corrected)
(corrected)
(corrected)
a = Ek
Kv
Ka
Kn
KsKrj
t
200C
2.764
1.526
1.010
1.129
275C
2.84
1.60
0.494
0.687
t
325C
3.763
1.603
0.0393
0.697
2.64
1.53
1.29
1.01
3.14
1.58
0.203
0.774
3.43
1.61
0.0762
0.653
0.644
0.580
0.489
0.383
0.222
0.143
0.830
0.603
0.0646
0.246
0.123
0.102
0.954
0.469
0.0222
0.190
0.0891
0.0850
-940
-13,700
ASjj = - 3 . 0 8
ASa = -30.46
A^H =
-3110
1740
+ AHy = -2310
AHB
-8.49
2.82
+ ASjj = - 8 . 7 6
A*SH
A -
A +
B =
B+ASs
958
CATALYTIC REACTIONS
[CHAP. XIX
effect of temperature on the reaction among the molecules remaining adsorbed. This
retardation of a reaction rate with increase in temperature is characteristic of many
reactions which are catalyzed by solid surfaces. At low-temperature ranges an
increase in temperature causes an increase in reaction rate owing to increased activation, whereas at high-temperature mnges the reaction is slow due to decreased adsorption of the reactants.
The general methods denionstrated in Illustration 2 are also applicable to moderately complex reacting systems in which several simultaneous and successive reactions may occur. It is only necessary that all
products be clearly defined compounds which can be introduced into feed
mixtures to simulate in the differential reactor conditions at various
points of an integral reactor. The rates of the individual reactions are
calculated from stoichiometric balances, and the rate equations are
evaluated from the variation of these rates with varying activities of the
components of the system.
Integral-Conversion Data. Wherever the precision of chemical
analysis permits its use, the direct measurement of differential-reaction
rates, as discussed in the preceding section, is the most satisfactory
method for studying the kinetics of a not too complex system of catalytic
reactions. However, there are many cases where the differential reactor
is not satisfactory, due either to the inaccuracy of the available analytical
methods or to the formation of complex products of side reactions which
are not readily reproduced as components in the synthetic feed to a
differential reactor. Under such circumstances it is necessary to work
with integral-conversion data where large changes in composition are
produced with low space velocities.
Differential rates can be obtained by plotting conversion x against
W/F for a series of runs on a feed of given composition processed at
constant temperature and pressure. If the diffusion of components to
and from the catalyst particles is of importance, W/F is preferably
varied by W being changed instead of F. From Equation (63) it is
evident that the slope of such a curve is equal to r, the differential
reaction rate. Thus a differential reaction rate may be determined
either by a single run in a differential reactor or by a series of runs in an
integral reactor. Once the differential rates are established, the method
of analysis is the same as that discussed in the preceding section.
As pointed out in Chapter XVIII, pages 853-4, the evaluation of the
constants in a differential-rate equation by graphically differentiating
integral-conversion curves, although theoretically sound, is generally
subject to large errors, depending on the procedure followed in drawing
the curves and estabUshing the slopes. For this reason it is necessary
CHAP. XIX]
INTEGRAL-CONVERSION DATA
959
to average a number of determinations corresponding to different conversions in order to obtain constants which satisfactorily represent the
data. After such average values are determined, they are used to
calculate an integral-conversion curve from Equation (64) for comparison with the experimentally determined conversions. This integration is readily carried out by plotting from the experimental data the
activities of the various components of the system as functions of WIF.
From these curves and the rate constants being tested reaction rates r
are calculated, and a curve is plotted relating r as ordinates to WjF.
The area under this curve between zero and any value of WiF gives
the calculated conversion. The constants of the rate equation are
adjusted by successive trials until satisfactory agreement is obtained
between the experimental conversions and those calculated by integration. This method is tedious but may be appUed to very complex systems.
The constants of a rate equation may be calculated by the direct application of an integral-conversion equation of the type shown in Table
LVII if only a single reaction is involved or if the over-all results of more
than one reaction may be treated as equivalent to a single reaction.
The curves in Fig. 184 relate conversion to catalyst/feed ratio W/F, for
the catalytic production of toluene from benzene plus xylene. For complete and direct evaluation of the rate equation such curves should be
available at series of different temperatures, pressures, and feed compositions. However, where minimum data are available and the system
is sufficiently simple to permit use of an integral-conversion equation
it may be possible to evaluate the constants of the equation from merely
three sets of curves such as Figs. 183, 184, and 185 in which pressure,
space velocity, and temperature are independently varied. This procedure was followed by Johanson and Watson, who assiuned that
Equation (69) may be used to express the rate of production of toluene
from an equimolal "feed even though some toluene results from disproportionation of xylene as well as its reaction with benzene. This equation form was selected on the basis of the shape of the pressure relationship shown in Fig. 183. It may be noted that at low pressures the
conversion is greatly increased by increase in pressure, whereas at high
pressures further increase has little effect. Since thermodynamic data
indicate that equilibrium is not approached at the high-pressure conditions, it was concluded that this form of variation is consistent with
control of the reaction rate by a surface reaction involving dual active
centers. The rate of such a reaction is proportional to the concentration of adjacently adsorbed xylene and benzene molecules and is
960
CATALYTIC REACTIONS
[CHAP. XIX
expressed by Equation (69), including the fouling factor. At low pressures the denominator is substantially constant at 1.0, and the rate is
proportional to the square of the pressure. At high pressures the
denominator becomes proportional to the square of the pressure and the
rate becomes independent of pressure.
The constants in Equation (69) were evaluated for a pure feed by use
of the integrated form. Equation (e) of Table LVII. Consideration was
first given to the data of Figs. 182 and 183 for short process periods where
T = 0 and the fouling factor BT is zero. As a first approximation it was
assumed that because of the chemical and physical similarity of the
reactants and products KR = {KA + KB)/2.
With this assumption
/3 of Equation (e) becomes zero, leaving the following simplified equation :
C /W\
=> , ( a x - l - 7 ) ( - l + 7 )
(ax-l + 7)(-l-7)
(88)
or
KAB/VC.
v^ ^^s^
(89)
(90)
CHAP. XIX]
951
By combining (88), (89), and (90) an equation is obtained which contains only two unknown constants, be and AHAB- These are evaluated
by applying the equation to a high-temperature and to a low-temperature
point on the T = 0 curve of Fig. 185. The resulting two equations are
simultaneously solved by assuming values of be and calculating the corresponding values of AHAB from each equation. The intersection of the
two curves relating AHAB to h evaluates the constants.
The fouling factor terms of Equation (69) enter into both a and ^ of
Equation (e), Table LVII. Values of UT* at 932F are obtained by estimating the initial reaction rates where a; = 0 by measuring the slopes of
the curves of Fig. 184 at the origin. Where a; = 0, Equation (69)
reduces to the following:
r
ro-
c
^ = ^,
(91)
: F + KAB + MrJ
The constants u and h are readily calculated from values of ro for different values of T. Since an unguided graphical determination of slope at
the origin is difficult, better results are obtained by calculating ro for
r = 0 from the known constants C and KAB and then assuming that the
values of ro are proportional to the values of x read from the curves
where W/F = 10. This same method is used for evaluating u at the
lowest temperature of Fig. 185, it being assumed that at the low conversions involved the initial rates of reaction are proportional to conversion. It is assumed that 6 is independent of temperature and that u
is related to temperature by an equation of the form of (89).
Values of v and c are obtained by solving Equation (e) of Table LVII
for (8 at different values of r at each of two temperatures where high
conversions are obtained. In this manner all of the constants are evaluated as functions of temperature as summarized in Table LVIII.
This method of evaluating a rate equation has the advantage of permitting accurate determination of constants from a minimum of experimental data. However, the integrated-conversion equations are almost
invariably of such complex form that the calculations are very tedious.
A high order of numerical accuracy with 6 to 8 significant figures is necessary in most of this work, because the result is generally a small difference between two large logarithmic terms of opposite sign.
Empirical Conversion Plots. Simplified approximate correlations of
kinetic data which have no sound theoretical bases are dangerous and
must be used with constant consideration of the assumptions and possible errors involved, particularly in extrapolating away from the ranges
962
CATALYTIC REACTIONS
[CHAP. XIX
TABLE L V m
RATE-EQUATION CONSTANTS
]^ _
g(682.3/flr)+C1.539/)
C = 7.56 e ^^
(mole)/(piass of catalyst) (hr) (atm)^
K^=KB=KJ,=
^CS,000/flr)-(0.54/B)
(1/atm)
-16,691
u
= 131 e "^
l/(atm) (min)"-^^
6 = 0.63
-23,149
V = 9820 e "^
l/(atm) (min)
c = 1.0
= ^ ( l - | )
(92)
CHAP.
XIX]
0.60 0.50
1 A
u.ou
0.40
0.30
1 y
/
//
0..45
0.40
"
0.S6
/
/
/
/
/
0.10
'/
//
^7
/ / /
/ //
/ //
/ / /
65
60
/ / AS"
50 ..r.
45 1
40 u
X "^^^
fo^o 1-1
55
//W
j\
^pO.25
0.00
/V/
'c / / / ^
0.30
0.20
963
>ci
35 O
/ /
30
25
20
0A5
0.10
" /
11
r 15
\ .
0.05
noo
20
40
1
1
60
80
W/F
1
100
1
120
10
6
140
1 P^A
dx
_ 1
!_
(93)
XA/X*)
964
CATALYTIC REACTIONS
[CHAP. XIX
0.40
0.50
w' '
\
\ ^ ^
0.60
0.70
A1
'
0.80
>"
'
0.90
1.0
I ;
^^^''"^
98
95
90
80
70
65
" 60
55
50
45
2.0
S.Oh
/^ \
^NC
^>.. >
^ \.
^ < ^
,4.0
X >
40
\\
35
\A
iJ 6.0
\ \
\ \
\
\
7 . 0 --
8.0 -
9.0-
10
0.0
I .
0.4
I
0.8
1.2
1.6
\
^\ '- ^.
~
\
X
V*
30
-^25
v,^N
2.0
2.4
2.8
(F/W) X 10^
FIG. 191. Linear Co-ordinates for Pseudo-First-Order Kinetics (High Conversion
Range).
at C. A truly first-order reaction plotted in this manner will yield
straight lines, the slopes of which are proportional to the reaction velocity constant. Figure 191 is useful for the high-conversion low-spacevelocity range, because all curves must extrapolate to XA/X\ = 1.0
where the space velocity is zero. Figure 190 is useful for the low-conversion high-space-velocity range where all curves converge at zero
conversion and zero W/F or reciprocal space velocity.
These charts may be used for empirically plotting either the ratios of
CHAP. XIX]
COMPLEX REACTIONS
965
CATALYTIC REACTIONS
[CHAP. X I X
At the high temperatures used these reactions take place to an appreciable extent by pyrolysis in the homogeneous phase as well as by catalysis.
In addition, the following reactions occur by both pyrolytic and catalytic
mechanisms:
(o) The dealkylation or cracking of butane to form methane, ethane,
ethylene, and propylene.
^
(b) The dealkylation of butenes to form methane, ethane, propane,
ethylene, propylene, and carbon.
(c) The dimerization of butadiene to form 4-vinyl cyclohexene-1.
(d) The decomposition of butadiene to form hydrogen, methane,
ethylene, acetylene, and carbon.
A complete kinetic analysis of this system should include measurements of the rates of all of these reactions, both catalyzed and uncatalyzed. The uncatalyzed reactions are evaluated by replacing the catalyst bed by a noncatalytic material such as fused quartz. The effects of
catalytic reactions are then segregated by subtracting from the over-all
results those which may be attributed to pyrolysis. In this maimer, by
working first with the reactions of the terminal products and then of the
CHAP. XIX]
COMPLEX REACTIONS
967
(a)
(b)
(c)
C4H10
C4H10
C4H8
: C4H8 + H2
: O.IC4H8 + O.IH2 + 1 . 8 (dealkylation products)
i O.IH2 + 1 . 8 (dealkylation products)
Although the data were not conclusive, it was indicated that the rate of
the principal reaction (a) is controlled by a surface reaction between
adsorbed butane molecules and adjacent vacant active centers. On this
basis the following equations were developed.
,/
""'
(1 + PAKA
VRPS\
PBsKns)'
(94)
where rma =
C =
K =
KA =
KBS =
18 073
^"^^^ = l575r-^-^^^^
(^^^
" R. H. Dodd and K. M. Watson, Trans. Am. Inst. Chem. Engrs., 42,263 (1946).
Also " Principles of Reactor Design," National Petroleum Publishing Company,
Cleveland (1946).
968
CATALYTIC REACTIONS
[CHAP.
20,092
log ^ = i j ^ - 5 - 0 2 7 3
XIX
(97)
log X = ^ ^
+6.7532
(98)
4.575r
The cracking reactions (b) and (c) were assumed to follow the following
equation:
Tnib = kpA)
Tmc = k-pB
(99)
where
Tmb and fmo = rates of reactions (b) and (c), respectively, moles/(mass of
catalyst) (hr)
VA, PR = partial pressures of butane and butene, respectively
k = apparent reaction velocity constant
(100)
Space Velocity=(V)/(y) (Hr)
400
200
80
100
120
140
40
60
160
Grams of Catalyst
W^
F
G-Mole of n-Butane Fed per Hour
120
180
200
CHAP.
COMPLEX REACTIONS
XIX]
969
ure demonstrated in Chapter XVIII which is equally applicable to con
ditions of varying temperature and pressure. In Fig. 192 it may be
seen that the yield of butenes per mole of butane fed tends to pass
through a maximum as space velocity is reduced. This maximum
shifts mth temperature and pressure in a complex fashion. Similarly
in Fig. 193 it is seen that the selectivity of the operation follows a comph100
20
30
40
50
Per Cent Conversion
60
TO
970
CATALYTIC REACTIONS
[CHAP. XIX
PROBLEMS
b (43)
c (44)
d (45)
e (46)
/ (47)
Dj^G/n
332
493
595
734
809
914
j
0.0636
0.0538
0.0536
0.0482
0.0453
0.0476
'
D/J/n
970
1160
1371
1555
1655
1858
CHAP. XIX]
PROBLEMS
971
catalyst has a bulk density of 45 lb per cu ft. In order to investigate the kinetics of
the reaction pilot plant runs were made at the conditions summarized in Table A
In all cases the process periods were so short that fouling of the catalyst may be
neglected. The equihbnum constant of the reaction at this temperature may be
taken a^ 3.5. Assummg that the rate equation is of the form of Equation (69):
J. =
CjaAaB - a%/K)
(1 + UAKA + GBKB + UBKR) 2 '
Toluene,
Mole Per Cent
4.5
8.3
12.5
6.6
8.6
4.4
Pressure,
lb per sq in.
315
315
465
465
465
465
Si,
1/hr
3.0
6.0
6.0
3.0
1.0
0.5
Toltiene,
Mole Per Cent
10.7
5.6
5.9
11.0
26.5
35.0
972
CATALYTIC REACTIONS
0.34
[CHAP. XIX
W/F
(lb catalyst) Qir)/lb-mole butane
1.0
3.2
8.1
11.5
16
32
*
The equilibrium constant of the dehydrogenation reaction at this temperature may be
taken as 0.2 atm.
(a) Plot these data on charts of the type of Pigs. 190 and 191.
(6) Determine the error which would result in estimating the conversion where
W/F = 5 and 30, respectively, by assuming that this complex reaction follows a
conversion-space-velocity relationship of a pseudo-first-order form based on the
experimental point at 25 per cent conversion.
9. Assuming the apphcabiUty of Equations (94-100) calculate the initial selectivity
obtained at zero conversion in the dehydrogenation of n-butane to butene at the
following conditions of temperature and pressure.
(o) 3.0 atm, llOCF
(&) 1.0 atm, 1100F
(c) 0.3 atm, 1100F
CHAPTER X X
MASS AND H E A T ' T R A N S F E R IN CATALYTIC BEDS
The reaction rate equations developed in the preceding chapter all
involve activities or partial pressures of the reacting components at the
stirface of the catalyst. As previously pointed out, these interfacial
activities may be significantly different from the average activities of the
main fluid stream because of the gradients required for the diffusion of
reactants toward and products away from the interface. These activity
differences due to diffusion may be neglected under conditions of relatively slow reaction rates combined with favorable conditions for mass
transfer such as result from high velocities of flow and from small particles. In general, the calculation of heterogeneous reaction rates should
include evaluation of the diffusional gradients of the system.
A further complication in heterogeneous catalytic rate calculations is
introduced by heat transfer. Since the actual reaction occurs on the
surface, the heat of reaction is absorbed or released at this point, and
temperature differences exist between the reaction surface and the fluid.
Where thermal effects are large, the control of temperature by suitable
heat-transfer arrangements becomes the most important problem of
reactor design.
Since the transfer of mass and heat are closely related phenomena of
great importance in heterogeneous reactions, these principles are
developed concurrently in considerable detail.
Laminar and Turbulent Flow. It has been experimentally demonstrated that when a fluid flows at low velocities over the surface of a solid
or the interface of another immiscible fluid, the flow tends to be laminar.
At the interface the velocity relative to the other phase is substantially
zero while at increasing distances from the interface the velocity progressively increases. In effect the fluid may be considered as composed
of thin layers which follow the contours of the surface without mixing
with the adjacent layers except as mingling results from molecular diffusion. Even in laminar motion the flow is not necessarily linear but
follows the contours of the restraining surfaces as though a bundle of silk
filaments or ribbons were being pulled over the surface, each maintaining
its same relative position, regardless of the irregularity of the path. In
fluids flowing around bends in pipes laminar flow may take a spiral path
not conforming to the shape of the bend. Laminar flow is also referred
to as viscous or streamline.
973
974
[CHAP. XX
CHAP. XX]
DIFFUSION
g^g
DIFFUSION
If two gases A and B at the same pressure are initially separated into
two adjoining compartments, removal of the partition will initiate transfer of component A into B and B into A by diffusion. The theory of
diffusion in gases is based chiefly on kinetic theory and was developed
principally by MaxwelP and Stefan.^ A summarized discussion is presented by Sherwood/ and a more extensive development is given by
Jeans.^
According to the classical kinetic theory of gases the diffusion of component A in a gaseous mixture of components A and B results from a
driving force which is equal to the partial pressure or concentration
gradient dpA/dL which exists at any instant in the direction of diffusion. This driving force is expended in overcoming a resistance to
diffusion which is proportional to the product of the concentration of the
gases. Mathematically,
TT = dABCACBiUA UB) = UAB -TJ-
{UA UB)
(1)
VAPB ,
,.
also
TAJJT
UA = rAaVA =
(3)
PA
where r^o = the molal rate of diffusion of 4 , in moles per unit time per
unit of cross-sectional area of diffusional path.
VA = molal volume of component A.
Substituting (3) in (2)
dpA
ClAB ,
--dL=W
^''^' - ''^'^
^^^
976
[CHAP. XX
VA -^VB=^
(5)
T^
(6)
PA
dVA
Tf-
.-.
(7)
OiABir aiJ
CART,
l-Aa =
{RTy dCA
ABT
,_,
-TTah
(8)
Equation (8) forms the basis for the definition of the coefficient of diffusion DAB of components A and B.
dpA
...
r.-r..--D = - _
dCA
(9)
DAB
OiABTT-
CHAP. XX]
977
fixed interface, both UB and TB become zero, and Equation (4) becomes
dp A dps aABPBrAa RT
-dL^lL^-RT-^Dl^P^'^"
(11)
DABTT
Pf =
PBI
; r - = KPB2 PBi)im
._^
(13)
-CT:)
Since pB2 PBI = PA\ PA2, Equation (12) may also be written
(15)
978
[CHAP. XX
aJ-i
-UAB
JJAR
^AI
The terms ui and ri do not appear since there is no net diffusion of inert
gas.
Because of the uncertainty of the proportionaUty factors a and the
corresponding diffusivities in mixtures of several components and
because of the comphcations resulting in attempting to apply different
values for each binary pair, an average diffusivity DAm will be used to
replace the separate values recorded in Equation (16). The average
value of the diffusion coefficient will be taken as the weighted mean of
the values for each pair. Thus, for component A,
(1 - NA) DAm = NBDAB
+ NBDAR
+ NSDAS
+ NIDAI
(17)
Tsa = - f - j TAa
(18)
Substituting Equation (18) in (16) and replacing each diffusion coefficient with the average value DAm gives
TT dpA
(^ ' "~ s ) l
-RTdL^K'J''^'"'^'''-^'''-^'"''''
^v
J ^'')
RT
dpA
(a -\-h r i\
RT V + PASA)
where
S^ =
^ ^
^
a
CHAP. XX]
979
/ff + PASA \
.-,,
RTBQ
where
(x + SAPA) -
p/ =
(TT +
SAPAJ)
,,
(23)
'
(24)
Similarly, for S
P/ = [IT - SsP.lim
where
8s =
(25)
r + s--- a&
Where the ratio of (ir + 5^pA)/(ir + SAPAI) is small, for example, less
than 1.2, the arithmetic mean is in close agreement with the logarithmic
mean and may be used for most purposes.
For equimolal diffusion it may be recognized from Equation (24) that
Pf = TT and Equation (22) reduces to the form of Equation (9). For the
diffusion of only one component in the presence of a stagnant gas 5^ in
Equation (23) is equal to 1, and the value of pf becomes that given by
Equation (13).
Equations (22) and (23) also can be applied where multicomponent
diffusion takes place without stoichiometric relations. For example, in
the countercurrent adsorption of one gas and desorption of another the
constants a and s may be taken as the actual molal rates of adsorption
and desorption, respectively, and the ratio (s a)/a may assume any
value. Equation (15) indicates that for a given concentration gradient
the rate of diffusion of A is favored by the presence of another component
diffusing in the same direction and retarded by another component diffusing in the opposite direction. Approximate relative values of a and s
may be obtained in such a case by calculating the rate at which each
component would diffuse under the conditions of the system if the other
980
were absent.
tration:
[CHAP.
XX
^'-
The values of p/ are obtained from Equations (24) and (25) by using for a and s the
values of TAH and rsa calculated for the individual diffusion of the components in
binary systems.
For anamonia: VA = 0.006;
pxi = 0
(a - s)/o = (0.00655 - 0.11251)/(0.00655) = -16.18
IT - VA{p, - s)/a = 0.2 + (0.006) (16.18) = 0.2971
p/ = (0.2971 - 0.2)/2.3026 log (0.2971/0.2) = 0.2454
For water: v^i = 0.0727;
PA = 0
(s - a)ls = (0.11251 - 0.00655)/0.11251 = 0.94178
T - PAi{.s - a)/s = 0.2 - (0.0727) (0.94178) = 0.13153
Pf = (0.2 - 0.13153)/2.3026 log (0.2/0.13153) = 0.1634
The rates of diffusion of the two components in the presence of each other are obtained
by substitution in Equation (22):
CHAP. XX]
981
For ammonia:
TAaRTBa = (1.148) (0.2/0.2454) (0.006) = 0.00561
For water:
rsJtTBa = (1.249) (0.2/0.1634) (-0.0727) = -0.1111
By use of the more rigorous equations developed by Gilliland, Sherwood calculated
values of 0.0057 and 0.1116 for these rates. The results of neglecting the effect of
the diffusion of one gas in calculating the rate of diffusion of the other are summarized
as follows for this illustration:
TAaRTBa (ammonia)
rsaffirBo (water)
Considering
Counterdiffusion
' 0.00561
-0.1111
Negkding
Cwnterdiffusion
0.00655
-0.1125
Percentage
Error
+16.7
+1.3
- ^
(26)
where
rAa = rateof diffusion of A, moles/(area) (time)
CA = concentration in moles per unit volume
DAB = diffusion coefficient
Since
CA =
where
XA = mole fraction
Vm = average molal volume of solution
Equation (26) becomes
DAB
rAa=
dxA
-TT-
,^
(27)
Vm dL
(XA - aiAi)
,,
(28)
(29)
982
[CHAP.
XX
(30)
7 - = ^~{ti-
ti)
(31)
(32)
where fcg =
(33)
CHAP. XX]
TRANSFER COEFFICIENTS
983
For the calculation of mass and heat transfer it is necessary that the
transfer coefficients kg, fc^, hg, and hj, be empirically correlated in terms
of the determining variables. These variables include the physical
properties and conditions of the system which determine the diffusivities
and thermal conductivity as well as the conditions of flow which determine the effective film thickness. In order to facilitate the plotting of
experimental data for widely varying systems and conditions Colburn^
and Chilton^ combined dimensionless groups of the variables to define
what they termed a mass-transfer factor jd and a heat-transfer factor jh-
'^-
Hmn
where
Jd = <!> ( - ^ j ;
j^ = <^' (^
(36)
where
(f) and (j)' denote unique functions for a particular mechanical
system of flow
= A. P. Colbum, Trans. Am. Inst. Chem. Engrs., 29,174 (1933).
; T. H. Chilton and A. P. Colbum, Ind. Eng. Chem., 26,1183 (1935).
984
D =
G =
n =
{DG/ix) =
[CHAP. XX
Chilton and Colburn pointejl out that <j) and <^' are numerically similar
and that as an approximation for turbulent flow in a circular cylinder
jd may be taken as equal to jh and to / / 2 where / is the friction factor of
the Fanning equation. These analogies lead to serious errors in other
cases, and correlations based on measurements of the separate phenomena of interest are required.
Although the J transfer factors are most convenient for the correlation
of experimental data they are somewhat cumbersome in application to
process design and analysis problems. The basic transfer coefiicients
kg and hg are more convenient to use but have the disadvantage of varying over wide ranges with changes in mass velocity G, the film pressure
factor pf, and the specific heat Cp. For convenience of application in
packed towers and granular beds Chilton and Colbm-n^ developed a
method of expressing the mass- and heat-transfer characteristics of a
system in terms of the height of a transfer unit Ha or ff/,. As its name
implies, the height of a transfer unit has the dimension of length and is a
measure of the height of packing or bed required for a specified transfer
service. Accordingly it must vary inversely with the corresponding
transfer coeSicient. The physical significance of the transfer unit is
developed on page 991. By definition,
ri
Hdo = ;
(37)
koMrnP/av
Sw = ^
(38)
where
Hig = height of gas-film mass-transfer unit
H},g = height of gas-film heat-transfer unit
a = interfacial area per unit volume of packing or bed
Similar definitions may be applied to Uquid films.
By combining (34) with (37) and (35) with (38); .
1/
u \t
JdSplJAm.//
G
KgMmVt
CHAP. XX]
TRANSFER COEFFICIENTS
l(C,^\^
935
GC,
Rates of heat and mass transfer in gases flowing through beds of uniformly sized granular solids were investigated by Gamson, Thodos, and
Hougen' and by Wilke and Hougen.^" These investigators correlated
heat and mass-transfer factors jh and jd against a modified Reynolds
number in which the diameter term is taken as the diameter of a sphere
which has the same surface area as an average particle in the bed.
Thus,
^
Dp = Vap/ir
(41)
where
Up = average surface area per particle
For cylinders of height and diameter each equal to D, Equation (41)
reduces to
Dp = DVh5
(42)
For spherical particles of diameter D or for cylinders whose height and
diameter are each equal to D the surface area per unit volume is represented by the following equation:
6p,
6(1 - F.)
where
Pb = bulk density of catalyst bed, mass/volume
Pp = actual density of catalyst particle, mass/volume
Fe = fraction of external void volume in catalyst bed
On this basis, Gamson, Thodos, and Hougen developed the following
expression for j ^ and jd in the range of Reynolds numbers above 350:
jd = 0.99(Z>p(?/M)-o-"]
\
yA = 1.06(DpG/M)^-J
(44)
(DpG/fi) > 350
(45)
\
J , =1.95(Dp(?/M)^-5iJ
(46)
' B. W. Gamson, G. Thodos, and 0 . A. Hougen, Trans. Am. Inst. Chem. Engrs.,
39, 1(1943).
1 C. R. Wilke and O. A. Hougen, Trans. Am. Inst. Chem. Engrs., 41, 445 (1945).
986
[CHAP.
XX
where
G = mass velocity of flow based on the total cross-sectional area
of the bed
Dp = effective diameter of particle from Equation (41)
No significance is attached to the value of D^G/ix at 350. The massand heat-transfer factors form a smooth and continuous curve over the
entire range of values, but for convenience the relationship may be
expressed on logarithmic paper by two straight lines which intersect at
350.
For convenience in use, the relationships expressed by Equations (45)
and (46) are combined with Equation (39) and plotted in Fig. 194 which
shows values of a^aa as a function of the modified Reynolds and the
Schmidt numbers. Values of {aMha/i-07) may also be read as ordinates
from the chart by substituting the Prandtl number for the Schmidt
number.
Equations (44-47) and Fig. 194 are based on data for the vaporization
of water from completely wetted spherical and cyhndrical particles of
various materials ranging in diameter from 0.09 to 0.74 in. It is beUeved, however, that they may be applied to general problems of mass
and heat transfer in gaseous systems at widely varying conditions if
reliable values for the various physical constants are available.
No similar data are as yet available for heat and mass transfer in
liquids flowing through granular beds. It seems reasonable to expect
that relationships of the form of Equations (44) to (47) should represent
this case, and in lieu of direct data it may be assumed that these equations are applicable to the liquid state.
. For the calculation of diffusional pressure and temperature differences,
from transfer unit data, Equations (39) and (40) may be combined with
(32) and (33). Thus, if ApA = PAt PA, it follows that,
ApA. = - ! - = " TT
Tn
(.(^"Hjo)
(48)
^ ^ iflvHm)
(49)
fliCrCp
where
TA = rate of reaction or mass transfer of A per imit mass of catalyst
qm = rate of heat transfer per unit mass of catalyst
Om = particle area per imit mass of Qatalyst
a = particle area per unit volume of catalyst bed = CUPB
AHA heat of reaction per mole of A reacted
CHAP.
TRANSFER COEFFICIENTS
XX]
t-w^m ^^55
i t 4 X y i J >5
^3-4l t ^
- ^^^i
-
\
\
^<A\
w
^V'
i W^
-^
7j
- \\
L \
1.
\ \ ^
^^_
^_
t\ c\
/.
_ /
_.:: \ ^
<
\
^
Ok
P
rl\
\ '\
A
^ *
\ \ '^^ ^ c ^ J . -
^)
L_
'y
"^
^^
\vN\
a.
\^ \
Q
a
1
1
o '^V
//
'
-v/
1
JX
___ IL
00
s^
"
1IN
1"^
C
O
13
03
t2
rm
^fe
00
U>
"=
c5 c5
00
C0
^AA ^^
^s^s_S \^; ^
*
o
c>
25
o
=5
CO
a
03
^^ \
\^'^
^^ f:x^~\S
.
tA ^
V ^\
\ ^ V - t A ^ ^'\
01
-a
o
Iw.-
CO
' \\ ^ \ \
\ \^\ ^
ji:
f^
o
iKiliil:
!t
L VVV
1
1
//
1
\ A
'V
03
S >>
\>V
^v
'/
<u
. S
Ijiiii:
^v^^N
t ^ o^ 3
t - A ^ S \ !VV
SS A
li
ru
Pi ^^^\
V ^ > \ !5V
1
^-
O
3
ll^^issisil-
n ^^
r-l
5|lbHI||:
A' \ N
3
0
^f
tI
f|||5^2i|-
v_
G
?
02
-nlZ/i
^Ao\ (
\
I V JA
3
C
\ " 1
T V V \w ? ^ ^ J
^
^^
* e-j6_|5 X-\ \S5
L_
-CS
\ \
35
\ \
3
\ ;
\
-J'
k;
\Y^
\^;\* A
'
^ -ti
-t"^
jt
V^O
v\-
O^
^o-
\\\V
jr
-J7^
- %
:;i'
* ^
T\\\\
\aV
987
[CHAP. XX
PHYSICAL CONSTANTS
In order to use Fig. 194 or Equations (45-47) for the evaluation of
transfer data it is necessary tliat the physical constants p, Cp, n, DAm,
and k be known for the system. Generalized methods for estimating
the first three constants in the absence of experimental data are discussed in Chapters XII, XVII, and XVIII, respectively.
Diffusion Coefficient. The diffusion coefficient DAB for the interdiffusion of two gases, A and B, may be estimated from the following
empirical relationship developed by GilUland:''
3
T'
D AB
0.0043 ;
/ 1
1
r - M r r + TT
(50)
MB
DAB = diffusion coefficient,T^ivl+viyyMA
cmVsec.
T = temperature, degrees Kelvin
MA, MB = molecular weights of A and B
TT = total pressure, atmospheres
VA, VB = molecular volumes of A and B which may be taken from
Table LIX for simple gases or estimated as the sum of the
indicated atomic volumes for complex molecules
TABLE L I X
ATOMIC VOLUMES FOB COMPLEX MOLECULES
Bromine
Carbon
Chlorine
Hydrogen
Iodine
Nitrogen, double-bonded
In primary amines
In secondary amines
In aromatic compounds deduct:
For benzene ring
For naphthalene ring
27.0
14.8
24.6
3.7
37.0
15.6
10.5
12.0
Oxygen in:
Aldehydes and ketones
Methyl esters
Methyl ethers
Higher esters and ethers
Acids
Sulfur
7.4
9.1
9.9
11.0
12.0
25.6
NHa
H2O
H2S
COS
CI2
Brj
Is
25.8
18 9
32.9
51.5
48.4
63.2
71 5
15
30
NO
23.6
NjO
36.4
" E. R. Gilliland, Ind. Eng. Chem., 26, 681 (1934).
" J . H. Arnold, Ind. Eng. Chem., 22, 1091 (1930).
f
Ciap. XX]
THERMAL CONDUCTIVITY
ggQ
D = 0.0043
Na
CO2, SO2
Ethylene
H28
Methane
H2O
2 1 2 ^ AND 1 ATM
k
0.74
0.78
0.80
0.83
0.77
0.79
0.78
\k J
0.818
0.848
0.862
0.883
0.840
0.855
0.848
990
[CHAP.
XX
Also, since XA =
TIAO
nA and
PA
= Wx5r/(1 +
^^^B^_P^^^^
TT
IT
^ASA),
(64)
CHAP. X X J
991
where the subscript o denotes the properties of the feed. Combining (53)
and (54) and rearranging gives
G _ G /TT + PAO8A\ ^ / g \ / I + PAo5A/Tr\
Mm " Mmo \^ + VASA )
\MJ
\l
+ VA5A/^ )
'
(PA - VAij
\ 1 + VA-^A/Tt/
GO- + PAOSAM
dp A
MmoTrkaAO-v
(PA
(56)
- PAi^{l + VA^AHY
Replacing G/Mmo by its value from Equation (55) and introducing the
film pressure factor pj in both the numerator and denominator results in
a z = - - ^ - ^
(57)
r\
_,
^^f
(58).
992
XX
change in the gas stream which is equal to the average driving force.
With this concept Equation (58) may be written as
/
(59)
Zi Zi {Hda)a.ve^da
where
^ T -.J)
VfdyA
(60)
yA = mole fraction of A
Vf = Vsl'^ = log mean of (1 + j/^S^) and (1 + yAi^A)
where
z._z..-(2.)
r-^=fl^
(61)
7 - m
dpA
r^A,i
^'A^_dpA_^
'PA,
PA
'^PA, ApA
'
PAi
(62)
(63)
(p-Ap^iy(p,-Ap.i)
ApA =
-PA
iT^PB + A p A ^ '
(64)
993
In the general case Equation (64) may be solved graphically for ApA
to correspond to selected values of PA, and the corresponding values of
PB, PB, and ps which are determined by the stoichiometry of the system.
The errors involved in use of Equation (64) are generally negligible if
K is large but may become serious where gases of widely different characteristics are involved. In such cases the more rigorous stepwise integration discussed in the following section should be used.
Where Pf or yf do not vary greatly they may be assumed to be constant
at the arithmetic mean of the terminal values. Then, for cases where
yAi = 0, Equation (60) reduces to
Ar
f \
rvM^dyA_^
^vAi
(1 + VASAjyA
r2Mi(l+2/425^)1 .__,
LyA2{i +
VAISAJJ
lUusttation 3. A mixture of 38 mole per cent propylene and 62 mole per cent propane is charged to a vapor-phase catalytic polymerization reactor at a temperature of
450F and an absolute pressure of 225 lb per sq in. The polymerization reaction is
substantially unidirectional and produces a mixture of olefins having an average
molecular weight of 105, an average boiling point of 220F, and a specific gravity of
0.71 at 60F. The catalyst is in the form of -j- X -j-in. cylinders with 50 per cent
external voids. Assuming that the catalytic activity is so great that the concentration of propylene is zero at the interface, calculate the space velocity (per hour)
required for 98 per cent polymerization of the propylene at a mass velocity of 200
lb/(hr)(sqft).
The effects of variations in pressure throughout the reactor may be neglected.
Solution: The reaction under consideration is represented stoichiometrically by the
equation:
2.5C3II6 <=i Gi.iH.is
t
Leaving
Propylene 0.76 mole; 1.0%
Propane
62.00 moles; 79.8%
Polymer
14.90 moles; 19.2%
The temperature of the stream leaving the reactor may be calculated by the
methods of Chapter VIII. However since temperature has relatively little effect on
diffusional rates an approximate calculation is satisfactory in which the heat of reaction is assumed independent of temperature and the specific heat of the reactant
stream taken as constant at that of the feed. The standard heat of reaction may be
estimated from the group contributions of Table XL, page 759, if the polymer is asBimied to have the properties of an equimolal mixture of 2,3-dimethyl butene-l and
2,3,3,4-tetramethyl pentene-1.
38 moles
62 moles
Heats of formation
Propylene
2,3-dimethyl butene-l
2,3,3,4-tetramethyl pentene-l
994
[CHAP-: X X
"F
OF
CoMPONEliTS
Propane
Propylene
Critical temperature
658 (ICT)
Tc'R
666 (Table XXVII)
Critical pressure Pc,
661 (ICT)
lb per sq in.
642 (Table XXVII)
8.17 (Fig. 109)
coiKi ccper g-mole
9.18 (Table XXVII)
Critical viscosity fic,
micropoises
(Equation
230
XVIII-105)
224
42
Molecular weight
44
Molecular volume
66.6
(Table LIX)
74.0
Polymer
984 (Eq. III-14)
390 (Eq. III-15)
19.23 (Fig. 109)
259
105
166.5
Entering
Pseudocritical properties
Temperature, T'cR
Pressure, p'c, lb per sq in.
Viscosity, /c, micropoises
Pseudoreduced properties
Temperature, T'r
Pressure, pr
Viscosity (Fig. 175), nj
Viscosity, micropoises
Viscosity, lb/(hr)(ft)
Compressibility factor (Fig. 103)
Molecular weight
Density, lb per cu ft
663.5
650
230
1.371
0.35
0.63
144.8
0.0346
0.975
43.3
1.02
Leaving
727
593
233
1.78
0.380
0.80
186.
0.045
1.0
55.8
0.905
CHAP. XX]
995
Entering
Diffusion coefficients, Equation (50) (sq ft per lir)
DAB (propylene-propane)
0.0392
DAC (propylene-polymer)
0.0247
DAm [Equation (17)]
0.0392
Schmidt number, tt /pDAm
0.875
Reynolds number DpG/;u
147
ji [Equation (46)]
0.142
o.Hdff [Equation (39)1
6.4
Leaving
0.0665
0.0419
0.0618
0.787
113
0.163
5.3
(r - a)/a = (1 - 2.5)/2.5 = - 0 . 6
1.0 - 0.772
. /T 1.0 \
For the low concentration of the outlet gas the arithmetic mean is satisfactory:
(2//)2 = (1.0 + 0.994)/2 = 0.997
(^/)avg = (0.881 + 0.997)/2 = 0.939.
; , , , = 0.939 l n l # M : ^ l = 3.66
L(o.o
1.01) (0.772) J
The thickness of the bed is obtained by Equation (59):
Zj - Zi = (3.66)(0.0405) = 0.148 ft or 1.78 in.
The hourly space velocity, based on total gas at 60F and 30 in. Hg (saturated) is
obtained by consideration of 1 sq ft of bed:
^ (200)(385.5) ^
(43.3) (0.148)
'
It is evident that a perfect catalyst under these conditions would result in very high
reaction rates.
DIFFUSION IN POROUS CATALYSTS
996
[CHAP.
XX
Commercial catalysts are manufactured in the forms of spheres, cylinders, irregular granules, and hollow cylinders. In the so-called fluid
catalyst system the solid is suspended as a fine powder in a gas stream
and thereby displays maximum exterior surface and effectiveness. In a
stationary bed the pellets or granules are rarely used in sizes much less
than i in. in height and diameter because of excessive pressure drops,
manufacturing difficulties, and the fact that further reduction in size
frequently results in httle gain in effectiveness.
The availability of the interior of the pellet for catalysis depends upon
size, shape, and permeability of the pore structure. For high effectiveness it is required that the pores and capillaries be of large and reasonably uniform cross section and be interconnected with the external surface of the pellet. The effectiveness of the interior surface also depends
upon the rate and nature of the reaction. A given pellet is relatively
less effective for a gaseous reaction which proceeds at a high rate with an
increase in number of gaseous moles than for one proceeding at a low
rate with a decrease in moles and is also influenced by the effects of activated adsorption and the rapidity of the reverse reaction.
In considering the properties of a catalyst bed the external void space
which surrounds the pellets should be distinguished from the internal
voids within the particles. This distinction is established from the
measurements of three densities, bulk density PB expressed as mass per
unit volume of bed; particle density pp, mass per unit volume of particle:
and solid density pc, mass per unit volume of solid free from all voids,
external and internal. For many catalysts the particle density is conveniently determined by displacement of mercury while the solid density
is measured by hehum displacement. The external void fraction of the
bed is given by the relation,
Fe = 1 - -
(66)
Pp
(67)
CHAP. XX]
997
ness factor of the particle. A general equation for the rate of a reaction
catalyzed by a porous solid may be written in the following form,
rA = CAai = E^JAai
(68)
where
TA = reaction rate per unit mass
C = observed over-all rate factor of the reaction
AOi = driving force of the reaction in terms of activities at the external
surfaces of the particle
EA = effectiveness factor
J = the rate factor of the catalytic reaction which when multiplied by
the driving force Aa,- gives the rate of reaction per unit mass of
catalyst if the driving force is uniform throughout
For example, in Equation (XIX-36) the driving force, Aai is equal to
(uAi asi/K) while the rate factor J is equal to (kLKA)/(l + aAiKA +
ctRiKB + aiiKj ) For other mechanisms corresponding values for
Afflj and J can be obtained directly from the rate equations developed
previously.
With an effectiveness factor of 1.0 the reaction rate at all interior
surfaces is the same as that at the exterior surfaces. It is evident that
this situation is approached when (1) the particle size is small, (2) the
pores are large and well interconnected, (3) the rate factor of the reaction
is relatively low, (4) the diffusion coefficients of reactants and products
are high. The relations among these factors were developed by Thiele'*
by analyses of several simple cases which with the aid of reasonable
simplifying assumptions could be treated mathematically. Thiele
found that in the cases studied for a first-order reaction in which the rate
is proportional to the first power of the concentration at the interface the
effectiveness factor is a function of a modulus which is defined as follows:
s^=/(mr)=/hr\-7r
"42Wci)J
where
niT = Thiele modulus = -^x
~^
2 \cDv
Dp
c
Dv
k
=
=
=
=
(69)
(70)
where a' and h' are empirical constants, characteristic of the system
Fi ~ fraction internal voids from Equation (67)
0.5
0.81.0
2.0
Thiele found that for the several simple cases studied the effectiveness
factor is related to the modulus by curves which do not differ greatly in
general form. As an empirical approximation it was suggested that the
curve derived by Thiele for spherical particles be assumed applicable in
all cases and that D'J, be taken as the diameter of a sphere having the same
surface area per unit volume as the particle in question. This curve is
plotted in Fig. 195. I t will be noted that at low values of the modulus
J)
CHAP. XX]
999
the effectiveness factor approaches 1.0 indicating that the entire internal
surface is reacting at a uniform rate. At high values of the modulus the
effectiveness factor approaches inverse proportionaUty to the first power
of the modulus. In this range the internal area is ineffective, and the
reaction occurs only on the gross exterior surface of the particle. At lowvalues of the modulus the reaction rate per unit mass of solid is independent of particle size, whereas in the high modulus range the rate is
inversely proportional to the particle diameter.
The effective particle size D^ for the Thiele modulus must be clearly
distinguished from the effective particle size Dp used for mass-transfer
correlations and defined by Equation (41). By definition,
^.^G7,^6.(l-F.)^_^
fflp
where Vp =
Cj, =
Fe =
a =
dm =
Pp =
a I,
(71)
ClmPp
1000
[CHAP. X X \
0.0
0.1
0.2
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1
0.0304
123
231
200
0.0364
250
0.0458
2
0.00425
124
231
0.0710
0.0765
(o) Calculate the effectiveness factor and modulus of each catalyst size at the two
temperatures.
(b) Evaluate the constants of Equation (70) for this catalyst.
CHAP. X X ]
DIFFUSION
IN
POROUS CAT'ALYSTS
(^.O'
0.826
0.825
D'/(Fi)^
Temperature, G
0.0368
200
0.513
0.00514
250
0.606
0.139
0.139
EAI/EA2
niTilmTi
n/ra
1001
X h" cylin.
iP'vi){Fi,)^
rriTi (Fig. 196)
4.8
3.7
0.615
0.669
0.60
(Fig. 195)
0.50
0.98
EA^ (Fig. 195)
0.96
(6) Substituting in Equation (70) for catalyst size 1 gives
rriTi
EAI
(2.303) (473)
V
log 3.7 = log o' + log 0.0368 +
(2.303) (523)
a' = 8.57;
6' = 1290
(c) For 1 " X 5 " cylinders:
D ; = 5:^ = 0.0418 ft
Fi = 0.40
Dp
0.0418
^/i
-v^oiio
= 0.053
1290
It is frequently experimentally difficult to duplicate exactly the conditions of operation in a differential reactor when itiaking comparisons of
two different catalyst sizes by the procedure outlined in Illustration 4.
Close duplication is desirable because of the irregularities generally
encountered in kinetic relationships, but the effects of small variations in
compositions or activities may be eliminated if a rate equation is available which is apphcable to one size of catalyst. Thus, from Equation (68), where variations in / are negligible,
EAI ^ ri(Aai)2
(72)
EAi r2(Aai)i
1002
'
[CHAP. XX
CHAP.
XX]
LONGITUDINAL DIFFUSION
1003
RTiv + PA^Ajnt dZ
Jo
where
F = feed rate, mass per unit time, per unit cross-sectional area
nA,nAo = moles of A per unit mass of feed at section Z and at the inlet,
respectively
Tit = total number of moles per unit mass of feed
DAm = mean diffusion coefficient of A in the stream at position Z
SA = {r + s a b)/a .
TA = rateof reaction of A, moles/(mass of catalyst) (time)
PB = bulk density of catalyst bed
A second relationship may be established by means of a material
balance for component A in an elementary volume dZ.
1004
= Fn^ ^ ^ . f
[CHAP.
XX
(74)
rT-(3^ + 3^^^)
(^5)
The difference between (74) and (75) is the rate of reaction of A in the
element.
i2r(x + pA8A)nt \ dZ^ I
Integration of Equation (76) is difficult because it is a second-order
equation which requires two sets of boundary conditions to define a
unique solution. These boundary conditions are fixed by the inlet and
outlet conditions of the reactor at which discontinuities may be considered to exist both as regards reaction and diffusion. Progressive step-,
wise integration is not possible because conditions in even the first element of volume at the reactor inlet are dependent on the gradients
throughout the entire bed. This becomes evident by consideration of
the extreme case in which diffusion is so relatively rapid that the gradients throughout the bed are negligible except at the inlet. In this situation the conditions at the outlet may be assumed'to prevail throughout
the entire bed, as was done in Illustration 11 of Chapter XVIII, page 862.
The general problem of longitudinal diffusion has been analyzed by
Hulburt'^ who developed integrated expressions for simplified cases.
Even where these expressions are applicable their usefulness is limited by
uncertainty as to the proper value of the diffusion coefficient. It is
evident that the effective or apparent coefficient for diffusion in a stream
flowing through a granular bed is quite different from that determined
from static conditions in the absence of a granular soUd.
In general, the mass velocities in commercial scale reactors with fixed
catalyst beds are such that longitudinal diffusion is neghgible. In the
corresponding pilot-plant operations it may be a serious factor which
should be carefully considered. Since the effects are difficult to analyze
or to translate to large-scale operations it is desirable if possible to design
the pilot plant .so that they are neghgible. This requires a catalyst bed
sufficiently deep to minimize the gradients dn^ldZ.
Fortunately the
problem is not serious in an experimental differential reactor in which
only small incremental conversions are produced. Even though large
concentration gradients are established in such a reactor their effect is
H. M. Hulburt, Ini. Eng. Chem., 36,1012 (1944); 37,1063 (1945).
CHAP. X X ]
F L U I D I Z E D CATALYST BEDS
lOQS
small because the outlet composition differs but little from that at the
inlet.
For a small experimental reactor of the integral type where large overall conversions are produced the design may be verified by applying
Equation (73) to a small section at the inlet of the reactor.
-FAn^
= rAPBAZ -
-
(77)
RTir + 'PA^A)nt AZ
I t is first assumed that diffusion is negligible, and An^ is calculated by
omitting the last term of Equation (77). The last term is then evaluated
with this value of AUA And the diffusion coefficient from Equations (17)
and (50). If the last term is negligible in comparison with the second,
longitudinal diffusion may be neglected. This calculation should be
made for the reactant or product having the largest coefficient of
diffusion.
Fliiidized Catalyst Beds. In the so-called " fluid " catalytic process^^
the catalyst is carried upward as a fine powder into a large reactor vessel
where a relatively dense fluidized bed of catalyst and reactants is maintained in a state of turbulence. Because of the limited velocity of flow
which is permissible without excessive carry-over of catalyst the reactor
beds are generally relatively short in comparison to their diameters. As
a result of the turbulence inherent to the fluidized bed and this low ratio
of length to diameter it is probable that the composition throughout the
bed is approximately uniform, corresponding to the outlet conditions.
This situation is comparable to that which would exist in a fixed bed
operating at an extremely low mass velocity.
It is evident from the results of Illustration 11 of Chapter XVIII that
this longitudinal mixing is undesirable in that a larger reactor or catalyst
bed is required for a given conversion. A still more serious disadvantage
is that longitudinal mixing may greatly increase the extent of secondary
reactions because of the fact that the high concentration of products
which exists at the outlet also prevails throughout the entire bed. As a
result it would be expected that a fluidized catalyst bed will generally
produce a lower conversion and a poorer selectivity than a fixed bed
operated with the same weight of catalyst in the reactor per unit feed
rate. This disadvantage may be in part offset by the higher effectiveness factor of -the finely divided catalyst. However, the fluidized bed
has the further disadvantage of a larger fraction of void volume which
increases the extent of uncatalyzed side reactions in the homogeneous
phase.
E. V. Murphee, C. L. Brown, E. J. Gohr, E. C. Jahnig, H. Z. Martin, C. W.
Tyson, Trans. Am. Inst. Chem. Engrs., 41, 19 (1945).
1006
[CHAP. XX
(6) COr-02;
(c) CO2N,
(d) Estimate the diffusion coefficient of CO2 in a gas mixture containing 15 per
cent CO2,1 per cent CO, 80 per cent N2, and 4 per cent O2, at 500C and atmospheric
pressure.
2. Estimate the diffusion coefficients of n-butane, n-butene, and hydrogen in a
stream of n-butane, 10 per cent of which has been dehydrogenated to n-butene and
hydrogen at a temperature of 1075F and a gauge pressure of 10 lb per sq in.
3. Estimate the value of -pf for the following reactions under the specified conditions:
(a) For the transfer of CO2 in the reaction of CO2 with carbon at atmospheric
pressure with a main fluid composition of 15.3 per cent CO2, 7.7 per cent CO, and
77 per cent N2, where the partial pressure of CO2 at the interface is zero.
(b) The same as (a) for a composition 1.7 per cent CO2, 30.5 per cent CO, and
67.8 per cent N2.
(c) The same over a reactor where terminal conditions correspond to (a) and (6)
(d) In the adiabatic evaporation of water in a stream of air at atmospheric pressure, 100F and 50 per cent humidity.
4. A bed of cyhndrical clay pellets having 39 per cent void volume is dried by
through circulation of air. The surface area of the pellets per cu ft is 82.8 sq ft, and
their equivalent diameter is 0.0542 ft. The air enters the bed at 0.985 atm, 160F,
wet bulb, 115F, and a mass velocity of 1720 lb /(sq ft) (hr).
" R. H. Newton, G. S. Dunham, and T. P. Simpson, Trans. Am. Inst. Chem.
Engrs., 41, 215 (1945).
CHAP. XX]
PROBLEMS
1007
Calculate the rate of drying at the inlet conditions expressed in lb/(hr)(cu ft) of
bed during the so-called " constant-rate " period when the particles may be considered as coated with liquid water.
6. Ammonia is produced at a rateof 7240 g per liter of catalyst per hour at 300 atm
and 380C, in a 1: 3 molal mixture of Ns and H2 entering a bed of a granular iron
catalyst. The gas flows through the catalyst at a rate of 600 lb /(sq ft) (hr). The
effective particle diameter Dp is 0.028 ft and the external surface area of the particles is
145 sq ft per cu ft. Estimate the temperature and partial pressure of nitrogen at the
surface of the catalyst.
6. Normal butane is dehydrogenated by passing it through a catalyst bed contained in vertical tubes 2.5 in. in internal diameter and 12 ft long. The depth of the
catalyst bed is 11 ft. The catalyst particles are -g-" X -f" cylinders arranged with
38 per cent void volume in Ihe bed which has a bulk density of 52 lb per cu ft. The
gaseous hourly space velocity is 1400 at standard conditions of 60F and 29.5 in. Hg.
Neglecting the effect of secondary reactions and pyrolytic side reactions and assuming the applicabihty of Equation (XIX-94-98), calculate the partial pressures and
temperature of the butane, butenes, and hydrogen at the surface of the catalyst
pellets at the point in the reactor where a conversion of 10 per cent is produced at a gas
temperature of 1075F and a gauge pressure of 10 lb per sq in. The results of problesm 2 axe applicable to tiiis problem.
Estimate the percentage error resulting from neglect of heat^ and mass-transfer
effects under these conditions.
7. In the dryer described in problem 4 it is desired that the air shall leave the bed
during the constant rate period with a percentage saturation of 90 per cent. Assuming that steady-state conditions are maintained and neglecting the heat capacity of
the bed and the pressure drop through it, calculate:
(o) The temperature of the air leaving the bed.
(6) The height of a transfer unit at the average conditions of the bed.
(c) The number of transfer units required for the specified vaporization of
water.
(d) The depth of the bed.
8. The bulk density of PB of a catalyst bed, determined by direct weighing is
0.64 g per cc. The density of the bed with the external void spaces filled with
mercury is 5.46 g per cc. When the catalyst bed is evacuated and filled with helium
it is found that 0.756 milliliter of the gas is required per cc of bed at a pressure of
1.0 atm and a temperature of 74F. Calculate:
(o) The fraction external voids.
(6) The pellet density pp.
(c) The true density of the catalytic solid Pc.
(d) The fraction of internal void volume.
9. .Butane is dehydrogenated at a high space velocity in a short catalyst bed to
determine the effectiveness factor of the catalyst. The rates of reaction in the experimental reactor with a constant mass of catalyst were as follows with different sizes of
catalyst in the form of cylinders whose heights and diameters are equal:
Diameter, ID.
'
0.125
0.250
Internal Vmd
Fraction Fi
0.51
0.40
^U050P
AU100F
2.68
1.90
5.52
3.41
1008
'
[CHAP. XX
(a) Calculate the apparent modulus and effectiveness factor of each catalyst size
at each temperature.
(b) Estimate the effectiveness factor of a catalyst having a diameter of 0.080 in.
and'36 per cent internal voids at a temperature of 1100F.
10. An experimental reactor for the hydrogenation of butene codimer is operated
isothermally at a temperature of 300F, a pressure of 100 lb per sq in. and a liquid
hourly space velocity of 0.5 at 6QF. The feed is pure codimer with hydrogen in
10 per cent excess of that required for complete saturation. The depth of the catalyst bed is 14 in. From Equation (77) estimate the relative importance of longitudinal diffusion in this reactor.
11. Normal butane is dehydrogenated in a catalyst bed having the properties of
that described in problem 6. The operation is substantially isothermal at a temperature of 1060F and a pressure of 1.0 atm. Integration of Equations
(XIX-94-100) for these conditions as shown in Figs. 192 and 193 indicates that with
an hourly WIF of 30 a conversion of 39 per cent and a selectivity of 89 per cent is
obtained. The moles of products per mole of butane charged are as follows: Butenes,
0.346; hydrogen 0.39; dealkylation products, 0.09.
Assuming that the operation is carried out at the same temperature and pressure
in a fluidized bed of the same catalyst in which the same fraction of void volume is
maintained, calculate the W IF ratio and the product distribution corresponding to
39 per cent conversion, if Equations (XIX-94-100) are applicable.
(Actually the fraction of void volume in the fluidized bed would be considerably
greater than in the fixed bed. However, Equations (XIX-94-100) do not properly
separate uncatalyzed from catalyzed reactions and for this reason are restricted to a
substantially constant fraction of void volume.)
CHAPTER "XXI
CATALYTIC REACTOR DESIGN
The ultimate objective in the process design of a catalytic reactor is to
arrive at the arrangement which will result in the most economical construction and operation. In general, the economic considerations are
most complex and involve careful balancing of the yields and product
distribution of the process against the capital costs of the plant and the
operating costs represented by labor, utilities, and maintenance requirements. However, in any event, the first requisite for the inteUigent
selection of a plant design is the abihty to predict the results which will
be obtained with any specific arrangement proposed for study. These
predictions must be based on the best possible interpretation of laboratory, pilot-plant, and any available commercial-scale data. In general,
these data are best correlated as semiempirical rate equations and effective transfer coefficients, as discussed in the preceding sections. It is
seldom practicable or possible to develop complete kinetic data prior to
the design of a plant, and the engineer is forced to improvise and extrapolate fragmentary data to conditions far outside the range of his past
experience. It is in such cases that sound fundamental principles are of
the greatest value in breaking down the available information into component effects and contributions of such simplicity that their individual
trends can be estimated with fair assurance.
After working correlations between operating conditions and results
are established thedesign of the plant resolves itself into a series of systematically planned " case studies." A set of operating and design conditions which appears attractive is selected, and the complete results of
the proposed operation are calculated in order to estabhsh the ultimate
cost of the desired product. This procedure is then repeated for another
case in which operating conditions or design factors are varied in the
direction expected to reduce costs. The optimum design leading to the
lowest costs is arrived at by consideration of the results of the entire
series of cases. It is within the scope of this treatment to consider only
the problem of predicting the conversions, product distributions, and
complete operating conditions resulting from any primary reactor specifications which are selected for study.
1009
1010
[CHAP. XXI
(1)
/AHAApA\/H,o\.^/jA/AH^ApA/C,,.Yf
\jJ\C,pfM,n/\ k J
\C^PSMJ\H^A)
M Y
\PDAJ
^^
By means of Equations (XX-48 and 49) the temperature and the partial
pressure of each component are calculated at the surface of the cal^lyst
particle. A second approximation to the rate of reaction is then calculated on the basis of these pressures and temperature. The evaluation
CHAP.
XXII
^Q^.
GC
^^
1012
where
[CHAP. XXI
CHAP.
XXI]
1013
The ratio of derivatives in Equation (5) serves to improve the approximation where owing to adsorption effect the reaction rate is little
influenced by conversion. If the mass transfer effects are large, trialand-error corrections should be estabhshed at several conversions.
The mass of catalyst per unit feed rate which is required for a specified
conversion XA is obtained by determining the area imder the curve relating 1/rA to XA, as indicated in the upper section of Fig. 197.
THE REACTOR UNIT CONCEPT
For simple reacting'systems at constant temperature and pressure,
analytical integration of Equation (XIX-64) may be expanded to include
mass-transfer effects. In the case of a reaction which is unimolecular in
both directions, represented hjA^R,
there is frequently a range of conditions over which the effects of the adsorption terms in the denominator
of Equation (XIX-36) are negligible and the rate equation may be
written as
TA^^C
\vAi - - ^ j = C
PA
+ APA
-g
(6)
(7)
--(--i)-ie('4)
<)
-p
KACIV
NBO
TT
KACIV
XA\
(9)
1014
[CHAP. XXI
ICT{1 + 1/K)M^B
M^fc^Tra J
rNAo - NRO/K - xi(l +
\.NAO-NBO/K-X,{1
l/K)-\
+ 1/K)\
where
Z =
S =
Mmo =
PB =
G =
It may be noted that the second term in the brackets of Equation (11)
is the height of a transfer unit for the mass transfer of A as defined by
Equation (XX-37), neglecting changes in Mm- The other term in the
brackets also has the dimension of length and is determined largely by the
catalytic rate constant C, the mass velocity G, and the pressure x. A
term of this general form has been designated by Hurt' as the height of a
catalytic unit He, while the entire term in brackets is termed the height of a
reactor unit Hn. Then by analogy to Equations (XX-58-59), times the
logarithmic term of Equation (11) represents the number of reactor units
NB required for the specified degree of conversion. Thus,
Z={H,
+ Ha)NR =HRNB
(12)
where
He = height of a catalji;ic unit = (j/[Cx(l + l/K)MncPB]
Hd = height of a transfer unit
NB = number of reactor units = (1 + i/K)
r-
CHAP.
XXI]
1015
(13)
where
hn = " coefficient of poisoning " by product B
TpB = partial pressure of R
The coefficient fcfl may be empirically correlated as a function of temperature.
It is evident that simplified treatments involving approximate Hnear
relationships of this type may lead to large errors in some cases if they
are apphed to combinations of conditions not included in the range on
which the empirical evaluations of the heights of the catalytic units and
the coefficients are based. The assumptions involved are similar to
those on which Figs. 190 and 191 are based. For this reason considerable
discretion is necessary in their use. For general problems of reactor
design which involve important variations in temperature and total
pressure httle saving in labor is effected as compared to more rigorous
methods.
PRESSURE DROP IN GRANULAR BEDS
Extensive studies which have been carried out on the pressure drops of
fluids flowing through conduits of uniform cross section are reviewed in
detail in the standard texts on unit operations and hydraulics. These
1016
[CHAP. XXI
2/(?2
gj)p
(14)
where
p = pressure in head of fluid
Z = length of path of flow
/ = dimensionless friction factor
G = mass velocity per unit cross-sectional area
p = density, mass per unit volume
g^ = standard gravitational constant = 32.2 ft/(sec)*
D = diameter for circular pipes = 4mA for noncircular conduits
m* = hydraulic radius = (cross-sectional area)/(perimeter)
The friction factor / is correlated as a function of the dimensionless
Reynolds number Nse which is defined as imkOf/j, or for circular pipes
DG/fi. The relationship between / and NRS varies somewhat with the
character of the surface but is approximately represented by the following equations^ for flow in conduits:
NB.
< 2100;
/ = 16/NB,
/ = 0.00307 + O-lSQiVif^
(16)
(16)
Equation (XVIII-98), page 869, is a modified form of the Fanning equation applicable in the region of Reynolds numbers above 100,000.
For flow through granular beds the Fanning equation may be modified
to incorporate terms for the effective free cross-sectional area which is
available for flow and the effective hydraulic radius of the path between
the particles. This problem was studied by Oman and Watson' who
pointed out the importance of the type of arrangement of the particles in
the bed. If the bed is formed by adding particles at so slow a rate that
each comes to rest before another falls on top of it, minimum bridging
occurs and a high bulk density results. A bed formed in this manner is
referred to as being in random dense arrangement. The opposite extreme
termed random loose arrangement is obtained by simultaneously dumping
all the particles of the bed into position. A stable arrangement results
which shows no appreciable change in density with vibration. However,
the bulk density may be as much as 20 per cent less than that of a random
2 T. B. Drew, E. C. Koo, and W. H. McAdams, Trans. Am. Inst. Chem. Engrs.,
28, 56 (1932).
^ A. O. Oman and K. M. Watson, Natl. Petroleum News, Tech. Sec. 36, B795
(November 1, 1944). Also " Process Engineering Data," National Petroleum Publishing Company, Cleveland (1944).
CHAP.
XXI]
1017
(1 -
PB/PP)
p = density of fluid
pp = average density of solid particles
PB apparent bulk density of the granular bed
The recommended relationship between fo and the modified Reynolds
number Nsep is approximately represented by the following two equations,
fo = 2.60(iVflJ--'
(18)
fo = 1.23(iVfiep)-<'-"
(19)
1018
[CHAP. XXI
Kpg.Ft'
where
(20)
(21)
o. = 6.6iNP(l - Fe9
(22)
(1 +
^-P
S^XA)RT
(23)
CHAP.
XXI]
1019
where
XA, = moles of A converted per mole of feed
8A = increase in number of moles per mole of A converted
Combining (23) with (17) and integrating gives
Vl - P^ = ^ 1 ^ r (1 + ^lxA)TdZ
(24)
Equation (24) frequently must be used by successive trials. A preliminary relationship of conversion, temperature, and bed depth is calculated as indicated in Fig. 197, an approximate pressure distribution being
assumed. A corrected pressure distribution is then calculated by graphical integration of Equation (24). This revised pressure curve may then
be used for an improved relationship between bed depth and conversion.
It is sometimes desired to carry out an operation to produce a specified
conversion with a specified pressure drop through the reactor. If masstransfer effects are not large an approximate space velocity for the
required conversion may be obtained by an integration" of the type of
Fig. 197 with an assumed pressure distribution curve. It is then necessary to calculate the bed depth Zi which corresponds to the required space
velocity and the specified pressure drop. The relation between mass
velocity and space velocity is as follows
G = S,pfZi
(25)
where p/ is the density of the feed at the standard conditions for the
expression of space velocity.
Combination of Equations (23) and (25) with (17) and (18) and integration gives, for modified Reynolds numbers less than 150,
{S.Pfy-K'Rt^''''Jv
{i+dAXA)T
^^'
Equation (26) corresponds to a fixed space velocity with mass velocities varying in accordance with Equation (25). It is not applicable to
calculations of the pressure drop distribution in a bed in which the mass
velocity is constant. In the use of Equation (26) approximate relationships between p, XA and T may be assumed for the first integration. An
improved pressure distribution relationship may then be calculated by
Equation (24) and used as a basis for a new relationship between bed
depth and conversion by an integration of the type of Fig. 197. A few
trials of this type will establish all factors within the accuracy ordinarily
justified by the data.
1020
[CHAP. XXI
CHAP.
XXI]
1021
(1 + VpioiKoi+
; PisOzVpich
Piso^KsozV I
^ J
where
r = reaction rate, lb-moles SO2 oxidized/(hr) (lb catalyst)
T degrees Kelvin at catalyst surface
PiSOa PiOsi Piso, = the respective partial pressures of the active components
at the catalyst surface, atmospheres
20,360
23.0
16,800
17.51
Kso, = e fi^
K = the over-all gas-phase equilibrium constant (Fig. 156)
The gas mixture specified in Illustration XVI-6, page 716, enters the reaction at a
temperature of 400C, 1.0 atm, and a mass velocity of 600 lb /(hr) (sq ft). The catalyst is in the form of | " X f" cylindrical pellets of such porosity that it may be
assumed that the effectiveness factor is 1.0 and that the foregoing rate equation is
applicable. The bed is in random dense arrangement with a void fraction of 0.35
* 0. A. Uyehara and K. M. Watson, Ind. Eng. Chem., 35,541 (1943).
1022
[CHAP. X X I
and a bulk density of 50 lb per cu ft. At the conditions of the reactor inlet it is
desired to calculate:
(a) The rate of conversion of SO2 in lb-moles/(hr) (lb).
(6) The temperature of the catalyst pellets.
(c) The pressure drop per inch of bed depth.
0.01
I
O
M
a 0.001
1
I
a
T
0.0001
0.00001
1200
800
900
1000
Gas Temperature, K
FIG. 198 Effect of Temperature and Conversion on the Rate of Catalytic Oxidation of
Sulfur Dioxide. (Composition of Entering Gas, 7.8%S02, 10.8%Oj, 81.4%Nj).
G = 6001b/(hr)(sqft)
700
(i) The rise in temperature of the gas stream/inch of bed depth at entrance
conditions.
Solution: As a first approximation the rate of reaction is calculated with the
assumption that the partial pressures and temperature at the interface are the same as
CHAP. XXI]
1023
KQ, = 38.46;
16,800
4.575 log Kso, = - ^ - 17.51;
VK^
= 6.20
Kso, = 42.46
C = 9.663
^
[1 + 6.20\/0.108 + 42.46(0)]"
= 0.0268
For calculating the partial pressure and temperature differences across the gas film
the physical properties of the system must be evaluated. The properties of the pure
components are summarized in Table A. The critical viscosity of SO3 was calculated
from Equation (XVIII-102).
TABLE A
Component
M
Tc, K
Pc atm
jic, micropoises
SO,
64
430.3
77.7
411
0,
32
154.3
49.7
250
SO3
80
491.4
83.6
469
N
28
126.0
33.5
180
= 0.0259
00. o4
Osoi-o. = ;
i
r;* /;;;; + :;;; = Q.Zm sq cm per sec
[(47.8)* + (25.6)if\80 32
1024
[CHAP. XXI
Similarly*
flso3-N2 = 0.362
>sOs-so, = 0.244
I>so.-o. = 0.385
i^sos-Nj = 0.383
D02-N, = 0.525
The mean diffusivity of each diffusing component in the mixture is calculated
from Equation (XX-17) and converted to square feet per hour by the factor 3.88.
Dao^ = (0.108) (0.366) + (0.814) (0.362) + (0.078) (0.244)
= 0.354 cmVsec or 1.37 sq ftperhr
(0.108) (0.385) + (0.814) (0.383)
,,
Dso,m =
( 1 - 0 078)
"
^ ^ ^ ^ ^ ""^ ^^'^ ^ * P ^ ' ^
(0.078) (0.385) + (0.814) (0.525)
. , , , ,
00^=-^
(1 - 0 108)
^
=0-511cmVsecorl.98sqftperhr
(0.078) (0.383) + (0.108) (0.525)
r>N^ = -^^
_Q8i4)
,
,,
= 0-463 cm= /sec or 1.80 sq ft per hr
The corresponding Schmidt numbers follow directly from the mean diffusivity of each
component together with the average viscosity and density of the mixture. The
effective diameter for the modified Reynolds number for mass and heat transfer is
calculated from Equation (XX-42) and the transfer factors from Equations
(XX-46-47).
Dp = (I) V T S = 0.458 in. or 0.0383 ft
0.0740
0.830
7.74
CHAP. XXI]
1025
7.70
HM = - = 0.0616 ft
Thenj
The values of arHdo and Hag for the diffusion of the individual components are calculated from Equations (XX-39) and summarized in Table B.
TABLE B
-
li
SO,
S02
02
N2
OeHda
\pDAmJ
1.334
1.272
1.041
1.116
pDAm
1.54
1.435
1.062
1.19
Hda
13.50
12.90
10.50
11.30
0.1080
0.103
0.084
0.0905
Since the mole fractions of all the diffusing components are small the values of p/
are satisfactorily approximated by the arithmetic mean rather than the logarithmic
mean of Equation (XX-25). From the stoichiometry of the reaction,
Ssoj = - 0 . 5
So, = - 1 . 0
Sso, = - 0 . 5
In the first approximation p/soj may be taken as 1.0 and the factors for SO2 and O2
based on the main stream partial pressures. Thus
.
The partial pressure differences for each component may be calculated from Equation (XX-48) using the rate arrived at by neglect of diffusion. Thus, since G/ilf =
600/31.23 = 19.18,
Apso, =
^
Apso. = -
rPi)?)/so.g,i3o.M-
(0.0268) (50) (0.961) (0.103)
^^^^
^
= ^^^
= -0.00693
rPBPfo,Hao,M
^p = - - w ^
(^)Wm
^^^
= --^2'^
CJ^mPiHia
,32=0
'
1026
[CHAP. XXI
The second approximation to the temperature of the catalyst is then 673.1 + 13.2 =
686.3K. The constants of the rate equation at this temperature are
C = 12.13;
VK^
K = 660;
= 5.35;
Kso, = 33.19
AHsoi = -23,860;
Cp = 7.76
=
=
=
=
0.0088
-0.0081
-0.0031
15.3
piso,
pisoi
pi02
Ti
=
=
=
=
0.0088
0.0699
0.1049
688.4K
a,ii
600
2(0.745)(600)^(125)
^ 37.2 ib/(sq ft) (ft)
(32.2) (0.0354) (0.35)'-'(3600)2
'* ^ -"'"-'
27 2
^
= 0.0158 lb/(sq in.) (in.)
The temperature rise at the inlet of the reactor is calculated from Equation (4):
dt
dZ
> TAAHAPB
GCr,
-0.0312(-23,858)(50)
7.74
( 6 0 0 ) (12)
CHAP. XXI]
1027
sional gradients of the products may be neglected. In many cases variations in the film pressure factor pf may be neglected, and in dilute systems
it may be assumed to equal the total pressure.
The result of Illustration ! represents one point on Fig. 198. Other
points corresponding to other conditions of temperature and conversion
may be calculated in the same
10 I
i
1
1i^-'
r\
manner. The effects of ignor10% conversion
y
>
uncorrected for mass yr
^ing the diffusional and temperascd heat transfer
ture difference corrections in
such calculations are shown
graphically in Fig. 199. The
solid^line curves in this figure
correspond to those of Fig. 198.
The broken-line curves are the
results obtained if the indicated
corrections are neglected. It
may be noted that the corrections are very important where
the rates are high, but become
insignificant at low rates.
Illustration 1 may also be considered as the initial step of a
700
900
progressive integration for the
Temperature," K
design of an adiabatic reactor.
By similar calculations apphed PIG. 199. Effect of Mass and Heat-Transfer
Gradients on the Rate of Catalytic Oxidation
tr succeeding increments of
of Sulfur Dioxide.
reactor volume the variation
of composition, pressure, and temperature may be predicted. If
change in total pressure is negligible the curve representing the adiabatic
operation of a reactor may be plotted on Fig. 198 from the adiabatic
.heating Hues of Fig. 157, page 721. Such a curve is plotted for the
reactor of Illustration 1. It may be noted that the rate of reaction rises
to a maximum at approximately 30 per cent conversion and falls toward
zero at approximately 80 per cent.
It is evident from Fig. 198 that if high conversions are to be reached
some means of cooling the reactor must be provided. One scheme is to
use two reactors, of which the first is adiabatic and the second is provided with cooling coils so arranged that the temperature may be controlled to follow the curve of maximum rate. For example, the first
reactor with the initial conditions of Illustration 1 might be designed to
produce a conversion of 52 per cent, where the adiabatic operation curve
of Fig. 198 intersects the maximum rate curve. Controlled cooling in
1028
[CHAP. XXI
the second reactor will permit operation to high conversions along the
maximum rate curve. The amount of catalyst required per unit of feed
WIF is readily calculated by graphical integration of Equation (XIX-64).
Values of 1/r read from Fig. 198 are plotted against x to correspond to the
selected scheme of temperature control.
An alternate scheme which simplifies the mechanical problems of
reactor construction and the replacement of catalyst is the use of a series
of adiabatic reactors with controlled intercoolers. For example, as indicated on Fig. 198, the adiabatic operation might be continued to 70 per
cent conversion with Httle loss in rate. An intercooler might then be
used to cool to 400C before entering a second adiabatic reactor which
would produce a conversion of 95 per cent operating along the indicated
cvu^e. By using more reactors and intercoolers a closer approach to
maximum rate operation and higher conversions may be obtained.
MULTISTAGE OPERATION
There are frequently advantages to be gained in carrying out a reaction in two or more reactors or " stages," In the preceding section the
use of multiple reactors simply as a means of temperature control is discussed. In such operations there is no addition or removal of reactants
or products between reactors, and the series of reactors may be considered as constituting only a single stage of operation.
True multistage operation may be of either a concurrent or countercurrent type. Concurrent multistage operation is advantageous for
polymolecular reactions in which one reactant undergoes undesirable
side reactions if it is permitted to exist in high concentrations. For
example, in the catalytic alkylation of butane'with butenes to produce
isomeric octanes the alkylation reaction is accompanied by undesirable
polymerization of the olefins. Such side reactions are effectively controlled by successive introductions of the olefin into the isobutane stream
so that at no point is there a high concentration of olefins which will
produce a high polymerization rate. Multiple-point introduction of a
reactant in this manner may be practiced in a series of reactors or by
providing multiple-feed points in a single reactor, but in either case it
may Jse considered as a concurrent multistage operation.
Prediction of the operating results of concurrent multistage reactor
systems involves no new principles if rate equations are available for all
important reactions. Calculations' are started from the reactor inlet
and carried through the successive stages, each addition of reactants
being taken into account.
Where it is desired to produce a high degree of completion of a poly-
MULTISTAGE OPERATION
CHAP. XXl]
1029
W B O % W^O^BOWJ'
3:
ITo
o
ni
nMUBan,! riBinii
ITo
1.
TTi
si
K
TCBIW,
1^
fii%' Separator
>
B0M,
\-^
R.11
Single Stage
WBO%
To
Separator
WAIMJJI ""
II
Wj'
I
71,'
Two Stage
Counter Flow
'
1030
[CHAP. XXI
Counterflow
(Infinite
Stages)
Two Stages
Single Stage
First
Second
nA
IIAOXA
nAUXA
riAi X'A
UAOXA
UB
WflOXA
riBiXA
nBOXA
nB
nt
nito+XA
n^o+JiBo+JiEo
+n[+ni'XA
nBi=nBoXAi
WBO+XA
UBI+XA
WAo+nBz+riBo
+ni+n'i-XA
tlAl nAOXAl
nRi=nBo+XAi
n^l+rtBO + Jlfil
+ni+n'[-x'A
nBl+XA
nso+XA
nAa+nBi-\-nRo
+ni+nj+XA
nBi = nBaXAi
XAl=nAOXAl
Overall
balances
UBi^flBtlXAZ
nAi=nAitXAi
1
XA^
If the pressure drops in the reactors do not significantly affect the reaction rates the amounts of catalyst required in the reactors of a two-stage
system are readily calculated by either analytical or graphical integration of/Equation (XIX-64) in combination with the reaction rate equations and the material balances of Table LXI. For specified values of
XAi. and X'AI, the mole fractions of the rea'ctants in each reactor are expressed as functions of the conversions XA and X'A. The corresponding
activities are then calculated and the integrations completed by the usual
methods, thus determining the amount of catalyst required in each
reactor. Variations in temperature and pressure in each of the reactors
may be taken into account if the inlet conditions are known. If no
compressor is used between the stages on the gas stream the pressure at
the inlet to the first reactor must be determined by a trial-and-error
procedure in which pressure drops are first assumed and then verified by
the reactor integration.
This same procedure may be repeated for different values of x^i at a
CHAP. XXI]
1031
1032
[CHAP. XXI
CHAP. XXI]
1033
bed is used as a heat reservoir to store up heat from the exothermic regeneration period. This heat is then given up to the reactants in the subsequent process period. Good temperature control is possible by this
method, but the cycle of operation must be short, and a perfect heat
balance must be maintained between the regeneration and process
periods.
The design problems in the first three types of systems may be handled
by the principles developed in the preceding sections. Where pressure
changes are significant the progressive stepwise procedure described on
pages 875 to 883 permits simultaneous development of temperature, pressure, and conversion relationships in any adiabatic reactor. If pressure
changes are negligible direct graphical integration as indicated in
Fig. 197 estabUshes both conversions and temperatures throughout the
reactor. This operation is direct and simple where a chart is available
which expresses reaction rate as a function of both temperature and conversion. Integrations for adiabatic reactors are readily carried out from
adiabatic operating lines plotted on such a chart.
The problems of lateral heat transfer in the fourth type of reactor are
discussed in the following sections. The heat-transfer and temperaturedistribution problems of the last two types of reactors involve specialized
data or procedures which are not yet generally available.
LATERAL HEAT TRANSFER
1034
[CHAP. XXI
Ix
%i
dqi = GC^dX
(27)
(28),
dq,=
(29)
-hdZ^
CHAP. XXI]
dqs = ~kdZ
dqz =
1035
dX
VAPB^HA dX dZ
(31)
where
G = mass velocity
Cp = mean heat capacity per unit mass of fliiid
k = effective lateral thermal conductivity of the catalyst-bed
fluid system
TA = rate of reaction, moles of A per unit mass of catalyst
AHA = heat of reaction per mole of A
PB = bulk density of catalyst bed
The energy balance is expressed by
dqi + ofg'2 + dqi = dqi + dq^^
(32)
where
(33)
A = k/GCp
B=
TAPBAHA
uCj,
(34)
2-KX
dX
(35)
1036
-fc(^)2.ZrfZ
dqs, =
-k -^
[CHAP. XXI
(36)
L 2x(X + dX) dZ
(37)
dX
dqi = - rAPBAHA2TX dX dZ
(38)
(39)
)x
\P-VA)\RT)
\_dx^
m\
(41)
Use of Equation (41) is made difficult by uncertainty as to the proper effective diffusivity D^m to be used for a fluid
moving through the voids of a catalyst bed.
Double Stepwise Integration. Grossman^ has presented a double stepwise method of integrating Equations (33) ai\d (40) which is based upon
the use of small but finite increments. The equations are written in incremental notation as follows:
For thin slabs:
AJ,
For cylindrical reactors:
AJ.
AAZ
{Axy
"^^^-{AU) + B AZ
(42)
G--f")
(43)
(Axy
+ BAZ
where Aji denotes the change of temperature in the longitudinal incremental distance AZ and AJ, denotes the change of temperature in the
lateral or radial distance AX.
i
^
' L. A. Grossman, Trans. Am'. Inst. Chem. Engrs., 42, 535 (1946).
CHAP, XXI]
1037
yy
*n, * + l
i B'LZ 1
B
u
.'-''
y' X
y^
tn.k
S
H
*n-l. *
In (n1)
In n
In (w+1)
1038
[CHAP. XXI
(Axy
(45)
2A
0.86
0.30-
0.25
0.20-
t-
0.15-
0.10
0.05
200
240
A.A + B AZ
(46)
(47)
CHAP.
XXI]
1039
(48)
The longitudinal dimension of the reactor is divided into k small increments AZ whose lengths are not necessarily equal but.are related to the
0.0038
200
240
440
(49)
Ax< = K W i . k - tn-i, k)
(50)
(51)
+BAZ
(62)
For cylinders:
\zt h]
2I ^<n+l.
5
Aji=
* + 'n-l, k 2i, * + 5~ (Wl. k
tn-1, k) I + BAZ
(53)
1040
[CHAP. XXI
7000
6000
6000
014000-
8000
2000
1000
FIG.
\
spending to the lateral position X of each of the selected increments AX.
However, the longitudinal temperature increments so calculated do not
correspond to uniform increments in, AZ,' and Equation (45) must be
successively used to establish the value of Z corresponding to each
temperature.
CHAP. XXI]
1041
PN = RP-RN = SO (i + ^)-RN
\2
4n/
J_ '
4w
,^.
(55)
(.tn+1, k < n - l . k) I
(56)
or
PN = (Wl. ft - <n-l. *) ( 2 + i;^) ~ (* * ~ *"-! *)
=
tn+1, k +
in-1,
k 2 i , k -\-
Comparison of Equations (56) and (54) shows that point Q on Fig. 204
may be established by graphically locating point P and adding the temperature increment B AZ = PQ. Since the value of B should be based
on the average temperature and conversion over the increment AZ it may
be necessary to evaluate it by successive trials, if the changes per increment are large. The change in conversion is expressed by a combination
of Equations (44) and (45). '
r^PB(AX)^^
^^^^ =
2AF
E. Schmidt, Beitr. Tech. Mechanik und Tech. Physik, pp. 179-89 (1924).
" E. Schmidt, Forsch. Gehiete Ingenieur-w., 13,177-84 (1942).
^^^)
1042
[CHAP. XXI
This procedure is repeated for each increment across the reactor, thus
establishing a temperature-distribution curve corresponding to the
longitudinal increment fc + 1. The corresponding AZ values are calculated from Equation (46) to permit a plot of Z against temperature and
conversion for each radial position.
It is readily demonstrated that Equation (52) may be solved by a
graphical procedure similar to that of Fig. 204, except that the abscissas
are increment numbers n plotted on a uniform scale instead of In (n).
At the center of either a slab or a cyhndrical reactor where n = 0 the
temperature i(ft+i)(=o) at a value of Z corresponding to increment (k + 1)
is approximated by adding the proper mean value of B AZ to the temperature <4(_i). For obtaining the value of <(A+i)(n=i) in a cylindrical
reactor the appropriate value of B AZ is added to the value of iA(=2).
This is equivalent to making line 0PM of Fig. 204 horizontal from In (2)
to negative infinity in order to locate point P where n = 1.
This method of calculation neglects lateral mixing of the fluid flowing
through the bed as well as all diffusion or, mixing in a longitudinal direction. It is also assumed that the mass velocity is uniform across the
entire cross section of the reactor. Although these assumptions are not
rigorous it is probable that the error they contribute is small in comparison to the uncertainty of the effective thermal conductivity k.
Illustration 2. In a hydrogenation operation an olefinic vapor is charged to a
cataljrtic reactor with 1.2 moles of hydrogen per mole of olefin. The mixture enters
the reactor at 200C and 5 atm at such a mass velocity that partial pressure and
temperature differences between the fluid stream and the catalyst are negligible. The
effective thermal conductivity k of the gas-solid systeni is estimated to be 0.5 Btu /
(hr) (ft) (F). The catalyst is contained in cylindrical tubes having an internal diameter of 1.25 in. The walls of the tube are surrounded by boiling water at a temperature
of 200C. It is desired to calculate the temperature and conversion gradients
throughout a representative tube.
From the catalytic rate equation the rates of reaction in pound-moles of olefin
reacted per hour per pound of catalyst were calculated at various temperatures and
conversions and plotted in Fig. 205. It may be noted that this reaction rate passes
through a maximum as temperature is increased. This retardation of the reaction
rate occurs at temperatures far below that at which the reverse reactive becomes
appreciable.
Based on the rate relationships of Fig. 205, the thermochemistry of the reaction,
and the physical properties of the system, the values of A and B in Equations (33)
and (40) were calculated at various temperatures and conversions and plotted in
Figs. (206) and (207), respectively. The effect of conversion on A is negligible.
The feed rate and catalyst-bed density are such that Equation (57) becomes
31.8 (AX) VA
ASXA =
;;
(a)
CHAP.
XXI]
1043
The method of graphical calculation based on Equation (63) and Fig. 204 is
demonstrated in Fig. 208 for the increments k = 1, 2, and 7, corresponding to five
equally spaced radial positions extending from the center of the tube where n = 0
to the wall where n = 6. The lines used in the calculations for the longitudinal increments fc = 3, 4, 5, and 6 are omitted from Fig. 208 for simplification, although it is
ln(2-AX)
ln{l-AX)
- Radial Positions
ln(3-AX)
ln(5-AX)
ln{i-AX)
-
(0.0104)2
2A
A^A =
54.1 (10-6)
A
0.00344 TA
(b)
(o)
1044
[CHAP. XXI
At the reactor inlet Z = (i,k 0,f = 200, and XA = 0 for all radial positions. Over
the interval from fc = 0 to fc = 1 a mean temperature of 211C and a mean conversion
of 0.026 are assumed for a first trial calculation at all radial positions except at the wall
(n = 5) where t is kept constant at 200O and a mean conversion of 0.019 is assumed.
Values of TA, A, and B are read from Figs. 205-207 for these conditions.
TA
A
B
AXA, Equation (a)
AZ, Equation (b)
BAZ
'
n = 0, 1, 2, 3, 4
0.078
' 0.00522
2140
0.0514
0.0103
22.3
n = 5
0.055
0.00528
1500
0.0358
0.0103
The temperatures at fc = 1 are hence 200 + 22.3 = 222.3C for all radial positions
except at the surface which is at 200C, and conversions are 0.051 for all radial positions except at the surface which is 0.036. The mean temperatures for all positions except the surface are 211 in agreement with the assumed value, and the mean
conversion is 0.025 at all positions except at the surface which is 0.019, both in agreement with the assumed values; the calculated values are hence correct. These calculations are summarized in Table A.
Similar calculations are repeated for the second increment of AZ from fc = 1 to
fc = 2. Since values of temperature at fc = 1 and radial positions n = 1, 2, 3, and 4
are the same A^t = B AZ in the first three radial positions. At the radial positions 4
and 5 the temperatures are determined by adding values of B AZ from Table A to the
points determined by the intersections of the lines on Fig. 208. These calculations
are repeated for succeeding increments as indicated in Table A and Fig, 208.
Values of temperature and conversion for given radial positions in Table A are
plotted against longitudinal distance Z in Fig. 209. In this figure the mean and adiabatic lines as well as all radial lines are shown for both temperature and conversion.
The mean values of t and XA were obtained by graphical integration from 0 to X^
from a cross-plot of the six radial positions against X":
The foregoing procedure may seem extremely laborious, especially in securing
agreement between assumed and calculated mean values of temperature and conversion; however, the first trial values can be made satisfactory after the first few
increments of AZ have been passed by plotting (and XA againstfcand extrapolating to
the next half interval of AZ. The greatest difficulty occurs, where the temperature
gradients begin to reverse in direction as shown in the range of fc = 6.
Unexpectedly high radial temperature gradients are shown in Fig. 209. The mean
temperature line occurs at a radial position of about 0.7 of the radius and a mean
conversion at a radial position of about 0.5. It is particularly interesting to note that
the maximum conversion occurs at a radial position of 0.8 rather than at the center of
the tube.
In this analysis no allowance was made for radial diffusion of gases, and the value of
thermal conductivity is uncertain. The method can be extended to include diffusion
effects. At present there are no published data on either thermal conductivity or
diffusion of fluid streams flowing through granular solids. Much experimental work
is needed in this field.
CHAP. XXI]
1045
.00 0.04 0.08 0.12 0.16 0.20 0.24 0.28 0.32 0.36
Z=Feet
FIG. 209. Conversion and Temperature Gradients in a Cylindrical Reactor.
1046
[CHAP.
XXI
TABLE A
CAIICULATION OF TEMPERATURE AND CONVERSION GRADIENTS IN A
CYLINDRICAL REACTOR
Radial
Positions
tv,
(.trial)
Itrid)
&Z
rA
BUZ
(trial) AxA
(calc^)(.cak.)
= Otol
Center 0
211
1
200
200
200
200
Surface 5
200
200
211
0.026
211
0.026
211
0.026
211
0.026
211
200
0.026
0.019
251
0.125
251
0.125
251
0.125
59.0 0.146
251
0.0103
0,135 37.2 0.092
235
0.057
0.037 0.0103 200
0.125
0
0.025 0.00522 0.0103 2140
211
0
0.025 0.00522 0.0103 2140
211
0
0.025 0.00522 0.0103 2140
211
0
211
0
& = 1 to2
Center 0
251
1
222
222
222
222
0.0103
0.125 0.00493 0.0110 5350
0.210
59.0 0.146
0,0103
0.051
0.125 0.00493 0.0110 5350
251
0.210
59.0 0.146
0.051
0.0103
0.125 0.00493 0.0110 5350
251
0.051
235
0.036
200
0.0103
0.051
251
Surface 5
0.051
222
0.210
0.097
0.054
= 2 to 3
Center 0
1
2
3
4
Surface 5
0.197
0.197
0 197
0.197
0.143
0.073
281
281
281
281
24r
200
0.0213
0.0213
0.0213
0.0213
0.0210
0.0206
* =6to7
Center 0
0.480
380'
37r
374'
352"
303
0.52
0.049
0.56
0.182
382'
0.515
13.5 0.040
375'
0.618
351
0.660 '
0.0567
0.00433 0.0125 1450
0.555
301
0.504
0.0583
0.533
351
382'
0.0584
0.499
375
200'
950
0.491
382
Surfaces
0.0590
0.503 0.00417 0.0130
384
0.0547
0.695 0.00458 0.0118 2550
0.198 0.00528 0.0103 1450
0.106
0.050
29.7 0.0792
301
0.0325 0.0516 200
0.595
0.198
CHAP.
PROBLEMS
XXI]
1047
ft = 7 t o 8
Center 0
1
2
3
i
Surface 5
389
38r
375
351
299
200
0.528
0.525
0.539
0.687
0.644
0.214
0.0720
0.0714
0.0712
0.0692
0.0665
0.0618
PROBLEMS
1. The nickel catalyst of Illustration 2, Chapter XIX, is to be used for the hydrogenation of butene codimer in 4 single-stage isothermal reactor operating at a gauge
pressure of 150 lb per sq in. Pure hydrogen is fed in 40 per cent excess of that
required for complete reaction, the remainder being recycled. Neglecting mass and
heat-transfer effects and pwessure drop, calculate by graphical integration the weight
of catalyst which must be supplied per pound-mole of codimer fed per hour in order to
produce 99.8 per cent hydrogenation at an inlet temperature of:
(o) 250F.
(6) 350F.
The reverse reaction may be neglected.
2. Repeat problem 1 for an adiabatic reactor in which hydrogenated product is
recycled for temperature control in the ratio of two moles of hydrogenated product
per mole of codimer feed. Hydrogen is supplied in 40 per cent excess of that
required to hydrogenate the olefins in the feed. It is desired that the total product shall be 99.8 per cent hydrogenated codimer. Determine the catalyst-feed
ratio for the following inlet temperatures:
(a) 275F
(6) 300F
3. Hurti found that the oxidation of a gas containing 7.8 per cent SO2, 10.8 per
cent O2 and 81.4 per cent N2 over a catalyst in the form of | " X | " pellets is represented by the following equation for the height of a reactor unit HB in inches,
HB = [1+ h(.Psoz)]iHi + He)
where HD height of a transfer unit at average conditions, inches,
pso, = average partial pressure of SO3, atm.
1^22-16.89
He = e ^
(in.) = height of a catalytic unit at a mass velocity of
600 lb / (sq ft) (hr) and a pressure of 1.0 atm
'"'"
fci = e
-5.84
(1 /atm)
Calculate the depth of the catalyst bed required to produce 95 per cent oxidation
of the SO2 in an isothermal reactor operating at a temperature of 450C and 1.8 atm
with a mass velocity of 500 lb/(hr)(sq ft). The pressure drop in the bed may be
neglected, and the average height of a transfer unit may be calculated by consideration
of the diffusion of only SO2, if zero concentration is assumed at the interface.
1048
[CHAP. XXI
'4. A catalyst in the form of ^ " X x%" cylinders is found to pack with a void fraction of 0.345 in random dense arrangement. A mixture of 10 mole per cent butene2
with 90 per cent steam is passed at a mass velocity of 620 lb/(sq ft) (hr) through the
bed at an inlet temperature'of 1200F and an absolute pressure of 24 lb per sq in.
(o) Calculate the pressure drop in pounds per square inch per foot of bed depth at
the inlet conditions if the bed is packed in a dense arrangement.
(5) Repeat the calculation of part (a) for a bed in a loose arrangement having void
fraction of 0.42.
.
6. Calculate the pressure drop in pounds per square inch per foot of bed depth at
the inlet conditions of the reactor of problem 5 of Chapter XX if the bed is in random
dense arrangement with a 36 per cent void volume.
6. Calculate the pressure drop in pounds per square inch per foot of bed depth in
the reactor of problem 6 of Chapter XX if the catalyst when in dense arrangement has
36 per cent void volume.
7. It is proposed to dehydrogenate w-butane to produce 35 per cent conversion in a
catalytic reactor operating at a temperature of 1050F with an absolute pressure of
200 mm of Hg at the outlet and an inlet pressure of 375-425 mm of Hg. It is known
that under these conditions considerable yields of butadiene are obtained, but this
secondary reaction and the accompanying pyrolysis may be neglected and the reaction assumed to follow Equations (XIX-94-98). The catalyst bed has the same
density and void volume as that of problem 6, Chapter XX. '
(a) Assuming isothermal operation and neglecting mass-transfer effects, determine
the space velocity required by a graphical integration of the type of Fig. 197, based on
an assumed pressure distribution.
(6) Calculate the depth of bed corresponding to the specified pressures and the
space velocity of part (o).
(c) Based on the bed depth and mass velocity of parts (o) and (6), calculate the
pressure distribution in the reactor.
{d) Correct the space velocity calculated in part (a) by a second integration based
on the corrected pressure distribution of part (c). If a large correction is involved,
parts (b) and (c) should be repeated.
8. Consider the reactor of problem 2 which corresponds to an inlet temperature of 275F as built in the form of a vertical cylindrical bed 10 ft in depth. The
pellet density of the catalyst is 3.5 g per cc, and it is placed in the bed in a random
dense arrangement with 36.5 per cent void volume. Retaining this bed depth and with
the mass velocity fixed by these conditions, develop a corrected determination of
catalyst-feed ratio which takes into account the effects of heat and mass transfer, and
pressure drop.
The pressure drop per foot of bed depth may be calculated for both the inlet and
outlet conditions of compositon and temperature, if a mean gauge pressure of 150
lb per sq in. is assumed. The total pressure drop may then be based on an average of
these two values. From the inlet and outlet pressures calculated on this basis construct an approximate curve which relates pressure to bed depth and conversion and
conforms,to the calculated pressure drop per unit length at the inlet and outlet.
The rate of reaction based on correct interfacial partial pressures and temperatures
should be calculated at the inlet conditions and at the conditions corresponding to
approximately' the maximum rate encountered in the reactor. From these points a
complete corrected rate curve is estimated by the principle of Equation (5).
9. Calculate the rate of reaction for the system'of Illustration 1 and Pig. 198 at a
temperature of 825K and a conversion of 70 per cent.
CHAP. XXI]
PROBLEMS
1049
10. From the data of Fig. 198 plot curves relating conversion to the catalystfeed ratio W IF in lb / (lb-mole) (hr) for reactors operating under the following conditions:
(a) Temperature control to produce maximum rate at all conversions.
(6) Adiabatic operation from 0 to 52 per cent conversion with an inlet temperature
of 673K followed by temperature control to maintain maximum rate at higher
conversions.
(c) Isothermal operation at 750K.
(d) Single-stage adiabatic operation with an inlet temperature of 673K.
(e) Two-stage adiabatic operation with an intercooler. The inlet temperature for
the first stage is 673K, whereas that for the second stage is 700K with a conversion
of 70 per cent.
11. If the catalyst of probleni 10 has a bulk density of 52 lb per cu ft and is arranged
in a bed having a random dense arrangement with 36 per cent void volume, calculate
the dimensions of the vertical cylindrical beds required for the two-stage operation of
part (e) with an ultimate conversion of 95 per cent. Calculate the pressure drop
through each bed.
12. It is desired to hydrogenate butene codimer over the nickel catalyst of Illustration 2 of Chapter XIX at a gauge pressure of 100 per sq in. and a temperature of
350F. The catalyst is placed in small-diameter tubes which are surrounded by
boiling water held under a suitable pressure for temperature control. The operation
may be treated as isothermal, and pressure drops, diffusional gradients, and temperature differences between the catalyst and vapors may be neglected.
The liquid charge is 100 per cent butene codimer while the source of hydrogen is a
methane-hydrogen mixture containing 80 mole per cent H2. It is desired to produce
99.8 per cent saturation of the codimer with an excess of hydrogen of 5 per cent above
that required for complete saturation.
Calculate the weight of catalyst for a codimer feed rate of 1 bbl (42 gal) per hr in
each of the following systems:
(o) A single-stage reactor.
(6) A hypothetical counterflow or infinite-stage operation.
(c) A two-stage counterflow operation, if complete separation of the hydrogen and
methane from the hquid in the separators is assumed. Calculate the weights of
catalyst in each stage and the combined weight with conversions of 20, 40, 60, and
80 per cent in the first stage. Graphically estimate the optimum first-stage conversion, and compare the corresponding minimum quantity of catalyst with the results
of parts (o) and (6).
13. Normal butane is to be dehydrogenated in the reactor described in problem 6
of Chapter XX. Assuming that tl^e catalyst bed is at a uniform temperature of
1075F throughout, calculate by a stepwise integration from Equations (XIX-94-100)
the conversion and selectivity resulting from the operation with an inlet temperature
of 1075F and an inlet gauge pressure of 20 lb per sq in. The effects of mass and
heat transfer between the-fluid and the catalyst particles may be neglected.
14. It is desired to investigate the possibiUty of dehydrogenating butane in a threestage adiabatic reactor with interheaters between the stages. Each stage is to produce 10 per cent conversion of the butane in the original feed. * The temperature at
the inlet to each stage is to be maintained at 1125F. The gauge pressures at the
inlets to the reactors are, respectively, 23, 13, and 3 lb per sq in. Neglecting the
effects of mass and heat transfer and assuming applicability of Equations (XIX-94100), calculate the catalyst-feed ratio, W /F, for each stage and the conversion-
1050
[CHAP. XXI
selectivity relationships throughout. The density and void volume of the catalyst
bed are the same as those specified in problem 6 of Chapter XX.
15. The catalyst tubes of problem 13 are surrounded by circulating flue gas which
may be assumed to maintain the tube walls at a temperature of 1100F. By a stepwise graphical integration establish the radial and longitudinal temperature and conversion distributions throughout the bed. Also calculate the average product distribution and pressure in the fluid stream as a function of longitudinal position,
assuming uniform flow distribution. The effective thermal conductivity of the bed
may be taken as 0.9.
16. It is proposed to place the catalyst of problem 7 in an envelope type'of heat
exchanger so arranged that the catalyst is in the form of vertical flat slabs 1 in. in
thickness. The retaining walls are maintained at 1075F, the temperature of the
entering butane, by a circulating fluid. Using the space velocity and bed depth
finally determined in problem 7, calculate by a stepwise integration the lateral and
longitudinal distribution of temperature and conversion. Also calculate the longitudinal variation of the average conversion and product distribution of the fluid
stream. The effective thermal conductivity of the bed may be taken as 0.9.
CHAPTER X X I I
UNCATALYZED HETEROGENEOUS REACTIONS
Many of the catalytic reactions discussed in Chapter XIX are
properly classified as heterogeneous, because more than one phase
participates. However, in such catalytic reactions the initial reactants
and final products are present in a single phase, and the net result is the
same as though a homogeneous reaction had occurred. Uncatalyzed
heterogeneous reactions are characterized by the presence of initial
reactants or final products in more than one phase. Such a reacting
system may include a gas phase and several distinct liquid or soKd
phases. For example, in the blast furnace, there may be present in one
zone a system of gas, molten metal, molten slag, soHd carbon, and several
solid oxides, all participating in a complex series of reactions.
Many organic processes involve heterogeneous reactions of various
types. The nitration and sulfonation of hydrocarbons are frequently
carried out in Mquid systems comprising two phases, one of which is predominantly acid and the other organic. The reaction products may be
distributed between both phases. Alternately, these same reactions
may be carried out in a homogeneous vapor phase or in a two-phase liquid
and vapor system. The principles goveriiing a reaction vary widely
with the conditions under which it is conducted, and there is little logic
in designating such a process as a " unit " for study on the basis of its
reactants or products.
It is evident from the variety of types of heterogeneous reactions that
many different mechanisms are possible. The actual reaction may occur
in a homogeneous phase, on a solid surface, or at an interface separating
two liquid phases or a gas and a liquid phase. In any case, however, a
problem of mass transfer of reacting materials from one phase to another
phase or to an interface is involved. The rates of these mass-transfer
steps are governed by the principles discussed in Chapter XX. The
net rate of reaction is then determined by the rate of the chemical
change itself, by the rates of mass transfer, and in some cases by rates of
adsorption on solid surfaces. Thus, as in the case of heterogeneous catalytic reactions, the rate is controlled by a series of steps, each of which may
be considered as offering resistance to the progress resulting from the
existing driving forces.
Two-phase uncatalyzed reactions are conveniently grouped in the
following classifications:
1051
1052
[CHAP. XXII
^ ^ )
(1)
^^~)
(^)
where a = activity
r = moles of A transformed per unit time per unit volume of an
individual phase
k = reaction velocity constant
K = reaction equihbrium constant
Subscripts A,B,R,S refer to components A,B,R, and S
Subscripts a, b refer to phases a and b, respectively
If the agitation of the system is sufficient to maintain equilibrium distribution, the activity of each component in the phase in which it is less
soluble may be expressed in terms of its activity in the phase in which it is
more soluble. Thus, if i? is more soluble in the a phase and S more soluble in the b phase,
[
ajtb = KRCRa',
O-Sa = KsdSb
(3)
J
1054
pressed as the product of the mole fraction and the corresponding activity
coefficient.
Ta =
Ka{ XAayAaXBbyBbl^B
(4)
, /
xnayBaXsbyshKRK
n = Kb ixAayAo.XBbyBJ<-Ab
I
(5)
The over-all rate of reaction is the sum of the reactions in the two phases.
Thus,
r = XAayAaVBbyBb(VakaKB
VbkbKA)
fVakJCs^VbkbKn\
XRayRaXsbysb
r=
,1
(6)
in* = - ; ^ + ^
(8)
In appljring Equation (7) the mutual solubiUty of the phases may be neglected and
XAa based on the total HNO3, H2SO4, and H2O content of the system while xsb is based
on the total benzene plus nitrobenzene.
The data of McKinley and White indicate that for the mononitration of toluene the
activity coefficient of the toluene 76 may be taken as unity over a wide range of conditions. It was also found that K' = 0, indicating that the reaction taking place in
the organic phase is negUgible. With these terms evaluated, rate data at a constant
temperature may be used for empirical evaluation of the relative activity cofficients
of the nitric acid yAaThe measurements of Lewis and Suen on the mononitration of benzene indicate
that the activity coefficient of the benzene jBb is increased by increased concentration
of both nitrobenzene in the organic phase and nitric acid in the acid phase. An independent analysis of these data indicates that they are approximately represented by
the following empirical expression for ysb over a range of nitric acid concentrations
from 2 to 10 mole per cent.
7B!, = 1 -I- 62a;Aaa:s/l+*^^'''
(9)
where xsb = mole fraction of nitrobenzene in the organic phase
XAa = mole fraction of nitric acid in the acid phase
Equation (9) is of uncertain accuracy for high nitric acid concentrations.
Values of jAa, the relative activity coefficient of the nitric acid in the acid phase,
were evaluated from the measurements of both groups of investigators'- ' and are
plotted as a function of the acid-phase composition in Pig. 210. An arbitrary numerical scale has been assigned to these vMues. It should be noted that these coefficients
express the activity of the particular form of nitric acid which is effective in the
nitration reaction. This active form of nitric acid is beheved to be a " dehydrated "
or " pseudo " nitric acid, and the activity coefficients of this material do not necessarily bear any simple relationship to activity coefficients of HNO3 as calculated from
vapor pressure measurements by the methods of Chapter XIV. Great reliance should
not be placed on the data of Fig. 210 in the regions where the broken Unes indicate
extrapolation of the experimental data.
1056
[CHAP. XXII
With the assumption that the relative activity coefficients of Fig. 210 are ipdependent of temperature, the other constants of Equations (7) and (8) for the nvononitration of benzene and toluene in the temperature range from 15 to 50C are as
follows:
Benzene
ysb
K'
E cal per g-mole
A (rates in g-moles per hr
per liter of combined phases)
5
1 +
0.14
14,000
Toluene
1.0
0
14,000
26.22
27.58
40
Q2xAa{xsi.)^^+'^'''">
10
15
20 25 30 35
Per Cent H2 SO4
40
46
#30
cf 25,
-^*20
10
15
45
HNO,
HjS04
HsO
CHAP. XXII]
NITRATION OF BENZENE
1057
This'acid is mixed with benzene to provide 2.5 per cent excess HNGj above that
required to complete the formation of nitrobenzene. The densities of mixed nitratmg acids are plotted in Fig, 211.
(a) Assuming that the acid and be^ene are mixed together and maintained with
adequate agitation at 35C, calculate the minimum time required to obtain 99.5 per
cent conversion to nitrobenzene.
(6) Calculate the volume of the reactor required for a capacity of 10,000 lb per day
of nitrobenzene, allowing 2 hr for charging and discharging the reactor,
HNO3 (1.502)
(1.00)
(1.835)
= -P
(10)
1058
[CHAP. XXII
The corresponding values of 7x0 are obtained from Fig. 210. Values of TBI, are calculated from Equation (9). Reaction rates r are then obtained by substitution in
Equation (7) with the assumption that the term (F, + VtK') is constant at the
arithmetic average of the initial and final values. This assumption neglects the small
variations in volume accompanying the reaction as a result of changes in densities or
miscibility. Sample calculations of the initial and final rates are as follows:
Basis: 100 g-moles benzene chained requires 100 g-moles HNO3 or 6320 g
HNO3 charged = 1.025(6320) = 6478 g
fi4-7S
= 19,948 g
O.o25o
From Fig. 211, density = 1.75
19,900
Acid volume = - = 11.39 liters
1750
Density of benzene = 0.879
7800
Volume of benzene =
= 8.87 liters
879
= 0.662
20.26
Total initial volume = 11.39 + 8.87
= 20.26 liters
Vt = 11.39
0.438
Initiallyfc(7a + K'Vb) = 29.08[0.562 + 0.14(0.438)] = 18.13
As the reaction proceeds the nitrobenzene formed dissolves in the benzene phase
and is but slightly soluble in the acid phase at 99.5 per cent conversion.
Vi = volume of benzene + volume of nitrobenzene
^^
^' =
^5^
= '"-'^""''''
In acid phase:
H2S04 = (19,948) (0.596)
= 11,900 g.
H N 0 3 = 6478 - (99.5) (63.2)
190 g
H20
= (19,948) (0.0786) + 99.5(18) = 3,358 g
15,448 g
77.05% wt
1.23
21.72
100.00
Acid volume =
9.11
19.28
= 0.473
0.527
-i- TT'V.I =
18.13 + 15.901
= 17 m
NITRATION OF BENZENE
CHAP. XXII]
1059
The reaction rates are calculated by substituting this average value ol'
k(Va + K'Vb) in Equation (7).
Initially xsb = 1.0;
XAa 0.33;
xsb = 0
From Fig. 210, since the mole fraction of H2SO4 is 0.39, jAa = 33
From Equation (9), jsb = I + (62)(0.33)(0)i+()(=3) = i.O
From Equation (7), r = (17.01) (0.33) (33) (1)(1) = 185.3
Finally, XBb = 0.005;
XA<, = 0.0097;
xsb = 0.995 -
From Fig. 210, corresponding to 39 mole per cent H2S04, 740 = 140
From Equation (9), ysb = 1.0 + (62)(0.0097)(0.995)i+Wn = 1.60
From (7), r = (17.01) (0.0097) (140) (0.005) (1.60) = 0.184
TABLE A
NITRATION OF BENZENE
XBb
XAa
TAa
0
5
10
15
20
25
30
35
'40
43
60
55
60
65
70
75
80
85
90
95
96
97
98
99
99.1
99.2
99.3
99.4
99.5
a
Q2xAa ]I
100X51
1.0
0.95
0.90
0.85
0.80
0.75
0.70
0.65
0.60
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15.
0.10
0.05
0.04
0.03
0.02
0.01
0.009
0.008
0.007
0.006
0.005
0.33
33
0.3139
33.5
0.2978
34
0.2817
34.5
0.2656
35.5
0.2495
37
0.2334
38.5
0.2173
39.5
0.2012
40.1
0.1851
41.5
0.1690
42.8
0.1529
44.4
0.1368
47
0.1207
49
0.1046
51
0.0885
56
0.0724
57
0.0563
64
0.0402
72
0.0241
86
0.0209
90.5
0.0177
96
0.0145 110
0.0113 120
0.01094 125
0.0106 128
0.0103 132
0.0100 138
0.0097 140
20.46
19.46
18.46
17.47
16.47
15.47
14.47
13.47
12.47
11.48
10.48
9.48
8.48
7.48
6.49
5.49
4.49
3.49
2.49
1.49
1.30
1.10
0.90
0.70
0.678
0.657
0.639
0.620
0.601
p.
+ 40XAa
14.20
13.56
12.91
12.27
11.62
10.98
10.34
9.69
9.05
8.40
7.76
7.12
6.47
5.83
5.18
4.54
3.90
3.25
2.61
1.96
1.84
1.71
1.58
1.45
1.438
1.424
1.412
1.400'
1.388
r
JBb
1 + axsb
1.0
185.3
170
155
140.5
128.5
118
107
1.0
94.9
82.4
1.003
1.017
73.0
1.048
61.5
69.0
1.135
1.311
67.4
1.607
56.5
2.02
65.0
2.49
52.5
40.4
2.88
3.06
28.1
2.89
14.25
2.35
4.15
2.21
2.84
2.04
1.77
1.872
1.016
1.690
0.389
1.669
0.35
1.65
0.305
1.633
0.265
1.614
0:.227
1.597
0.184
1/r
0.0054
0.00588
0.00645
0.00711
0.00778
0.00848
0.00935
0.01054
0.01213
0.01370
0.01626
0.01695
0.01742
0.01770
0.01816
0.01904
0.0248
0.0356
0.0702
0.241
0.352
0.565
0.985
2.57
2.86
3.28
3.77
4.41
5.44
1060
[CHAP. X X U
0.08
8.5
0.07
I 3.0
|0.D6
2.5
^0.05
M
6
,
|o.04
6.>
t.0.03
1.0
0.02
0.5
0.01
-Ts6
7 8
\
\
1^T
1.4 5 liter-1ir
"5^
0.00
9 10
10 20 30 40 60 60 70 80 90 100
CHAP. XXII]
CONTACTOR EFFICIENCY
106I
that under the specified conditions the reactor volume required for continuous operation is over ten times that for the batch operation. However, the cost per unit volume of continuous reactor is relatively low
because of the low maximum rate of release of heat of reaction. The
cooling system for the batch reactor must be designed to handle the high
rates of heat Uberation at the start of the cycle where the reaction rate per
unit volume is as much as 1000 times as great as in the continuous reactor. The continuous reactoi- thus has the advantage of permitting precise control of temperature with only a small fraction of the cooling
surface required in the batch operation. In the actual operation of
batch equipment of thi^ type the high initial heat release is partially
controlled by gradual addition of the reactants to retard the rate of
reaction.
The large reactor volume required in a single-stage continuous operar
tion may be avoided by using multiple stages in counterflow. In such an
operation the hydrocarbon is charged to the first reactor where it is contacted with partially spent acid from the second reactor. The efHuent
from the first reactor is passed through a separator from which the waste
acid is discarded and the hydrocarbon phase charged to the second contactor. The total reactor volume is progressively reduced by this type
of multiple staging, and the optimum number of stages is determined by
an economic analysis. A phase separator is required for each stage. A
disadvantage of multiple-stage operation in the nitration of aromatics
is an increased tendency toward secondary reactions forming di- and
frinitro compounds.
Contactor Efficiency. Where agitation is not thorough, the distribution equilibria represented by Equation (3) may no.t be assumed. Thus,
the actual activity of A in the b phase is less than the equilibrium value,
KAdAa by an amount which is a function of the rate of reaction in the b
phase, the over-all transfer coefiicient of component A from the a to the b
phase, and the extent of the interfacial area. Since relatively high concentrations of A and R exist in the a phase it may be assumed that the
mass transfer of these components is controlled by a diffusional film at
the interface in the b phase. Then
ttAb = KAttAa I
(11)
KAO^V
1062
[CHAP.
XXII
An expression similar to Equation (11) may be written for anb and substituted in Equation (5).
or
nil
1-
\ = h[ KAttAaaBb
j ;
(13)
It may be noted that the right-hand side of Equation (13) is the same as
that of Equation (2). Accordingly, the rate of reaction in this phafee
may be written as
n = EA
iaAaasbKA
^^-)
(14)
where Ecb is the contactor efficiency for the 6-phase reaction defined as
follows:
1
Ed, =
^^(e^+ax^)
A similar expression may be written for the contactor efficiency for the
a-phase reaction. The contactor efficiency is increased by improved agitation which'increases the transfer coefficients and interfacial area and is
reduced by an increase in the reaction velocity constant or increases in the
activities of the nondiffusing reactants or products. For the empirical
evaluation of the contactor efficiency it is convenient to write Equation (15) in terms of diffusion film thickness 4>b and diffusion coefficients
DAV, and Dsm- Thus, since, in accordance with Equation (XX-26), page
981,
_,
(a,A aAi)
TA = l>Am
Pi
,
,
= KA (.a-A
it follows t h a t
,
KA
and
Ecb =
DAM
=
<p5
V
aAi),
CHAP.
XXII]
1063
where
DAM DRm = over-all diffusion coefficients of A and R from phase o to 6
<j}i = effective diffusional film thickness in phase b
ttv = interfacial area, per unit total volume
The reaction velocity constants and activity coefficients of Equation (16) may be evaluated from rate measurements under conditions of
extreme agitation where E^ = 1.0. Then, if the relative values of the
diffusion coefficients are estimated by the methods outhned in Chapter XX, the ratio <^6/a may be evaluated as a function of the power
expended in agitation from a series of rate measurements at varying
degrees of agitation. If the rate of reaction is important in both phases
such tests must be repeated with different phase ratios in order to determine independently the contactor efficiencies for the two phases.
GAS-SOLID REACTIONS
Reactions between a gas and a solid may form either a gaseous or a
solid product or both. If a soHd product is formed three phases participate in the reaction and the mechanism is somewhat uncertain, but
probably involves the formation of an activated complex involving both
solid phases at a point of mutual contact between all three phases.
If only gaseous products are formed at least three mechanisms are
possible..
1. The solid may sublime and the actual reaction occur in the homogeneous vapor phase.
2. A sufficiently energized gaseous-reactant molecule reacts upon
impact with an active cefnter on the soHd surface to form a chemisorbed
product molecule which is then desorbed. Only one active center is
involved in this reaction, and if more than one product gas is formed
only one is chemisorbed while the others are evolved directly with the
gas phase.
3. The reactant gas is chemisorbed on the solid surface and then reacts
with an adjacent active center to form chemisorbed product molecules
which are then desorbed. Two adjacent active centers are involved in
this mechanism, and if two product molecules are formed each may be
chemisorbed on a separate site.
Reactions, with Gaseous Products. A common general case is represented by the following equation:
A{s) + B{g)^R{g) + S{g)
(17)
Rate expressions which are developed for this general reaction are
readily modified to apply to the less complicated cases where the two
1064
[CHAP.
XXII
(18)
where
Am = interfacial area, per unit mass of solid
ksA, ksA = velocity constants for the sublimation and condensation of A
aAi, asi = activities in the gas phase at the interface of components A,
B, etc.
Kg = gas-phase-reaction equilibrium constant
When equilibrium is reached between the solid and gas phases,
{aAi)e - ^ = KSA
(19)
ksA
where KSA is the sublimation equilibrium constant of A which is equal to
its vapor pressure where the ideal-gas law is applicable. Combining
(18) and (19) gives
r = AmkAs(l
\
- ^ ^ )
KsAKgaBi/
(20)
CHAP.
XXII]
1065
nize that the activity of a very small aggregation of a solid is higher than
the normal value of an extended surface. For this reason a condition of
high supersaturation may exist in the gas phase if no solid phase is
initially present. Once condensation of the solid is initiated by the
formation of condensed nucleii these small particles will grow as the
reaction proceeds.
Absorption Mechanism. There is evidence that in many gas-soUd
reactions one or more of the gaseous components is chemisorbed on the
solid surface and the reaction actually occurs on the surface. Thus the
reaction of Equation (17) might proceed in the forward direction by
chemisorption of B on the surface of A followed by reaction to form
chemisorbed molecules of R and S which are then desorbed. Since the
rates of such activated phenomena differ widely it is general for one step
of a sequence of this type to be so slow that equilibrium may be assumed
in the others. The rate of the reaction is then controlled by the slow
step which may be any one of the four.
Where two adsorbed product molecules are formed it is probable that
the forward reaction occurs by an adsorbed B molecule reacting with
an adjacent vacant adsorption center of the sohd reactant A. The
reaction rate is then expressed by
r = A, ,(A-CBC{ k'c'nc's) = AJc
{C'BC'I
(21)
where
r = rate of reaction per unit mass of solid
Am = interfacial area per unit mass of solid
CB, CE, CS = concentration of adsorbed B, R, S molecules per
unit area
c^ = concentration of vacant reaction sites per unit area
k, k' = velocity constants of forward and reverse surface reactions, respectively
K' = surface-reaction equilibrium constant = CRCS/CBC'I
If the surface reaction is the slow rate-determining step surface concentrations in Equation (21) are the adsorption-equilibrium values
expressed by Equations (XIX-10 and 11), page 911. Combining these
equations yields
A^iL'Yk
{a,,Ks-''-^^P^) (22)
1066
[CHAP.
XXII
(^-^
= ^
\ ttBi /
=K
(23)
KRKS
A^L'^Ksh
(1 + QBiKB + amKn + asiKs + ai
aBiasi\
.,,
G^'^^'S)
r = AJCB loBiCi - ^ j
(25)
(27)
Cj =
(28)
CHAP. X X I I ]
1067
amasA
,_.
1068
[CHAP. X X n
Mass-Transfer Effects. In the rate equations developed in the preceding section the activities are in all cases those existing at the interfaces. The interfacial activities of the gaseous components differ from
the activities in the main gas stream as a result of the gradients required
to cause diffusion to and from the interface. These activity differences
may be calculated from the mass-transfer relationships developed in
Chapter XX.
As in the case of catalytic reactions the importance of mass-transfer
effects varies widely. In many systems where the chemical rates are low
and mass velocities are high the mass-transfer resistances may be neglected. Since mass-transfer rates are little affected by temperature it is
possible for the over-all rate of a reaction to be controlled entirely by
chemical steps at low temperatures and by mass transfer at high temperatures where the chemical rates are relatively high. In such a case
the temperature coefficient of the over-all reaction rate diminishes as
temperature is increased, and where mass-transfer resistances are dominant, temperature has little effect on rate of reaction.
Illustration 2. Extensive tests on the combustion in air of coke on grates' indicate
that at the high temperatures encountered the rate of the reaction is primarily limited
by mass transfer. Although the experimental errors in the work were large, the data
obtained are in general consistent with the following mechanism:
1. Oxygen diffuses from the air stream to the surface of the coke particle where it
reacts to form CO or CO2. It may be assumed that at the high temperatures involved
the chemical reactions on the surface are so fast that chemical equilibrium is maintained among C, CO, CO2, and O2. Reference to Fig. 156, page 712, shows that at
temperatures above 1300K the equilibrium concentrations of both CO2 and O2 are
substantially zero.
2. Carbon monoxide diffuses from the interface into the gas stream where if oxygen
is present it is ojcidized to carbon dioxide in a homogeneous gas-phase reaction:(i
2C0 + O2 f i 2CO2
3. As the carbon dioxide content of the gas stream is built up by steps 1 and 2,
COj diffuses to the interface where it is reduced to CO in a-surfaoe reaction;
C02(g) + C ( s ) ^ 2 C 0
In a deep fuel bed this reaction continues after all oxygen is consumed, and the final
products approach an equiUbrium composition containing substantially no CO2.
On the basis of the assumption of equilibrium at the high-temperature interface,
the rates of steps 1 and 3 are controlled entirely by diffusion and may be calculated
from the data of Fig. 194. Step 2 is a homogeneous reaction which has been studied
by Haslam* with the conclusion that it approximates a third-order mechanism in
accordance with the stoichiometric equation. Measurements of spontaneous ignition
temperatures by Falk* indicate that the rate of reaction is increased by a factor of
5 Kreisinger, Ovitz, and Augustine, U. S. Bur. Mines Tech. Paper 137 (1916).
* R. T. Haslam, Ind. Eng. Chem., 15, 679 (1923).
s K. G. Falk, / . Am. Chem., Soc, 29, 1536 (1907).
CHAP. XXII]
MASS-TRANSFER EFFECTS
1069
42,000
^
+ 24.74414
log fc =
9179.7
~ + 10.7462
or
(31)
where T = degrees Kelvin
Because of the experimental errors inherent in combustion measurements, the data
of Kreisinger, Ovitz, and Augustine show inconsistencies when single runs are compared with each other. A better picture of the combustion process is obtained by
considering the average results of a series of similar runs. In one series air was
passed at rates varying from 380 to 756 lb/(sq ft) (hr). The average rate for the
series was approximately 600 lb /(sq ft) (hr). The temperatures in the lower sections
of the fuel beds averaged approximately 2600F. In each test coke which was sized
between 1|- and 1-in. screens was continuously fed to the top of the fuel bed, and the
grates were kept clean and free from all but a thin layer of ash. On the basis of
Equations (30) and (31) and the mass-transfer relationships of Chapter XX it is
desired to calculate the composition of the gas phase throughout the fuel bed in this
series of runs.
Solution: In order to calculate mass-transfer rates some assumptions are necessary
regarding the particle sizes in the bed. Actually the particle size diminishes from a
maximum at the top to a minimum at the bottom. However, as the size is reduced,
the particle becomes coated with ash which increases the resistance to mass transfer,
tending to offset the effect of reduced particle size. Accordingly, it will be assumed
that the particle sizS is constant at the size of the coke fed. If it is assumed that the
particles are approximately spherical and pack with a void space of 50 per cent, the
superficial surface area a per cu ft of bed, is calculated as follows:
/1.25V ^
Volume per particle = I "T^" J -^
~ (0.59) (10"') cu ft
/1.25\2
"= I "T^ J '^
Area per cu ft
~ (3.4) (10~') sq ft
1070
[CHAP. XXII
TABLE A
n
rt
J-j
n + rj
2r2 Ti
2(ri + ra - n)
Incremental changes, lb-moles per hr
AO2
-0.183
ACO2
0.028
AGO
0.310
Gas leaving section, lb-moles per br
Oj
4.167
0.028
CO2
0.310
CO
16.350
Ns
20.855
Total
Composition of gas leaving, mole per cent
0,
20.00
0.13
CO2
CO
1.49
0.205
0.001
0.007
0.195
0.007
0.016
0.176
0.021
0.0195
8.20
1.11
0.04
9.31
2.18
14.26
7.80
5.65
0.25
13.35
10.85
5.00
7.05
7.45
0.76
14.50
14.14
0.72
-0.194
0.043
0.297
-0.278
0.226
0.104
-0.301 '
0.294
0.015
4,156
0.043
0.297
16.350
20.846
3.878
0.269
0.401
16.350
20.898
3.577r
0.563
0.416
16.350
20.906
20.00
0.20
1.42
18.52
1.29
1.92
17.1
2.69
1.99
CHAP. XXII]
MASS-TRANSFER EFFECTS
1071
0.003
0.164
0.070
0.0013
0.155
0.089
6.53
7.60
1.34
14.13
13.86
0.54
0.32
3.09
6.02
3.41
0.16
6.50
0.12
1.63
5.95
1.83
-2.69
8.88
0.05
1.14
5.61
1.19
-3.33
9.04
-0.295
0.291
0.011
-0.142
0.006
0.270
-0.076
-0.112
0.370
3.282
0.854
0.427
16.350
20.913
0.122
3.533
1.381
16.360
21.386
15.7
4.08
2.04
0.67
16.60
6.49
8.0-9.0
0.0832
1
9-10
0.0832
1
......
0.144
0.110
0.128
0.140
0.108
0.166
0.096
0.184
5.21
4.65
3.90
3.46
-5.21
10.42
-4.65
9.30
-3.90
7.80
-3.46
6.92 .
-0.050
-0.138
0.375
-0.216
0.435
-0.386
0.772
-0.319
0.637
-0.282
0.665
0.046
3.421
1.751
16.360
21.568
-0.004
3.283
2.126
16.360
21.755
3.067
2.661
16.350
21.978
2.681
3.333
16.360
22.364
2.362
3.970
16.350
22.682
2.080
4.635
16.360
22.966
0.21
15.90
8.16
15.0
9.8
14.0
11.6
12.0
14.9
10.4
17.5
9.1
19.8
ture at 600'55 is 5.86, whereas the bed temperature of 2600F corresponds to a reduced
temperature of 12.9. Extrapolating Fig. 175 yields
or
The components whose diffusion limits the rate of combustion are Oj and COj.
Since nitrogen represents a large proportion of the gas stream, a good approximation
may be obtained by assuming that these components are each diffusing in an atmos-.
phere of nitrogen. On this basis the diffusion coefficients are calculated from Equation XX-50), page 988.
For oxygen, at 2600F (1700K):
(0.0043) (1700)?
Uv
[(25.6)* + (31.2)^]22 ^ 3 2 ^ 2 8
1072
[CHAP. XXII
For COj:
(0.0043) (1700)
.ip-^44^28
[(34)3 4- (31.2)3]"
= 1.77 sq cm per sec or (3.88) (1.77) = 6.9 sq ft per hr
In order to obtain a^Hdo from Fig. 194, page 987, the dimensionless groups DpG/ix
and nlpDv must be evaluated. On tlie assumption of spherical particles,
Dp = 1.25/12 =0.104 ft.
DpG (0.104) (652)
^^^
~
=
0.14
= ^^
C
For O2:
M
0.14
=
= 1 36
pD (0.0128) (8.02)
For CO,:
= 1.58
M _
0.14
pD, ~ (0.0128) (6.9)
From Fig. 194 or Equations (XX 39 and 44),
For O2: a^Hdo = 15.7;
Hda = 15.7/28.8 = 0.545 ft
For CO2: a^Hda = 17.3;
Hda = 17.3/28.8 = 0.600 ft
The value of p/ for the diffusion may be calculated from Equation (XX-23),
page 979. Since the variation of (T + SPA) is small the arithmeticmean may be used.
It is assumed that PA is zero at the interface for both O2 and CO2 while in the main
gas stream it will vary from zero to 0.21. Since S 1.0, p/ varies from 1.0 to 1.105.
An average value of 1.05 may be used.
By substituting in Equation (XX-48), page 986, the rates of diffusion of O2 and CO2
are obtained on the basis of 1 cu ft of fuel bed.
For O2 (step 1 of the combustion process):
_
ApG
_
652po2
_.
lb-moles O2
'"'
MVfHdo ~ (28.5) (1.05) (0.545) " ^ ' ^"^ (cu ft) (hr)
For CO2 (step 3 of the combustion process):
,652pco2
lb-moles CO2
'"' ~ (28.5) (1.05) (0.600) ~ ' ^^"^ (cuft)(hr)
where the partial pressures are expressed in atmospheres.
The reaction velocity constant of the gas-phase oxidation of CO is given by Equation (31).
9179 7
log fc = - - ^ -f 10.7462 = 5.3464
k = 0.222 (10')
Since the bed is assumed to contain 60 per cent voids, the rate of step 2, the gas-phase
reaction, per cubic foot of bed is given by the equation:
1
r2 = 0.111 (10)Hpco)npo.) ^ ^ ^ ^ ^ ^
(cu ft) (hr)
MASS-TRANSFER EFFECTS
CHAP. XXII]
1073
On the basis of the assumptions established these three rate equations may be
applied to an incremental section of bed having a volume Aw to determine the rates of
disappearance of O2 and formation of CO and CO2. Thus:
Disappearance of oxygen = AO2 = {n + ri)&.v lb-moles per hr
Formation of CO2
Formation of CO
24
I20
\
^
C(3 2 /
;i2
o
8
4
0
0
UU
10
3
4
5 6
7
8
Distance from Grate, In.
FIG. 213. Composition of Gas in the Combustion of Coke on a Grate.
2
1074
[CHAP. XXII
CHAP. X X I I ]
WATER SOFTENING
1075
sodium in the exchanger. The rate equations consistent with this theory
and experimental evidence are as follows:
dp
Forward reaction rate: ri = = Jciuv^
(32)
9T
dp
= k2(yq)'^
or
r = kiuv'^ k^iyq)^
(33)
(34)
h
2.86
2.29
1.91
1.62
1076
[CHAP.
XXII
the following differential calcium balance can be set up for the interval
of time dr.
.PwVfdu
Gd- ( -d^) = pdx[ dr) + TTT T" "^ dr
(35)
\\ dx
dx JJ '^ \dT
\dr JJ
10
W dT
The last term in this equation represents the change in calcimn content in
the water in the free space of the bed which is negligible compared to the
total amount of water passed through. Neglecting this term and simplifying gives
^^
where p =
Pw =
G =
Vf =
or
dp
or
OT
(37)
(38)
(39)
buv^
b = fci
Gr
For the usual boundary conditions that the entering water has a constant
composition with time, and that the initial composition of the exchanger
is uniform, Swain* has developed the following solution to Equation (39):
ln2 + z = l n s + s r
vo
u
1+2
i +i
s
1+
(40)
CHAP. XXII]
WATER SOFTENING
1077
where
Wpkivh
r = -avlx =
- ~
Cr
(41)
s = but^VoT = kiUoVar
2 =
1
V
A detailed study of the application of these equations to water softening shows the surprising results that, when hard water which enters free
of sodium flows through a bed of exchanger, the reverse rate is nearly
negligible under condition of steady fluid flow, and the exchanger becomes completely spent before chemical equilibrium is attained.
To expedite calculations, performance charts have been constructed
from Equation (40) expressing the effects of all variables in terms of the
dimensionless groups, r, s, s/r and U/UQ.
In Fig. 214 u/uo is plotted against s/r for constant values of r. In
Fig. 215, values of r are plotted against s for such conditions that the
residual hardness of the water leaving the bed is seven parts of calcium
carbonate per milHon parts of water.
Illustration 3. It is desired to estimate the residual hardness of water after
steady operation of a softener for 16 hr, with water flowing through a bed 3 ft thick at
a rate of 4 gal per sq ft per min. The initial hardness of the water corresponds to
300 parts calcium carbonate per million parts of water, which is equal to 6.0 lb equivalents of calcium ion per million lb of water. The initial replaceable sodium content
of the exchanger is equivalent to 25,000 grains of calcium carbonate per cu ft. The
density of the mineral is 28 lb per cu ft, and the grain size is 14 to 20 mesh. Under
these conditions:
p = 28 lb per cu ft
X = 3.0 ft
ki = 1.91 per min
O = (4) (8.33) = 33.32 lb/(sq ft) (min)
= I '
)I
1 ( 1 = 0.00255 lb equivalent Na per lb exchanger
\ 100 / \ 7 0 0 0 / \ 2 8 /
Uo = 6.0 lb equivalents Ca ion per million lb water
T = (16) (60) = 960 min
Vo
31.3
= 28.1
1078
ICHAP. XXII
CHAP. XXII]
1079
0,14
z = 0.62
1+^
u
1 +
1.0356
= 0.397
2.61
40
35
30
-25
20
4-^^^
15
10
5
0
0
25
30 35 40 45
s
FIG. 215. Performance Chart for Softening Water to a Residual Hardness of
7 Parts per Million.
10
15
20
In this manner, values of residual hardness can be calculated for any time, thickness of bed, rate of water flow, cation-exchange capacity of exchanger, and reaction
velocity constant.
1080
[CHAP. XXII
The water softened by 3 cu ft of mineral during this period is 844(4) = 3376 gal;
the calcium carbonate is
(3376)(8.34)(300-7)
. . ,. ^ ^ ^
= 8.24 lb CaCOs
or 19,200 grains of CaCOs are remoyed per cu ft of exchanger. The water softened by
1 cu ft of mineral under the aforementioned conditions is (4) (844) /3 = 1130 gal.
= 0.0233
Mo
y = 846 min
s
0.79
From Fig. 214, the*intersection of s/r = 0.79 with u/u^= 0.0233 gives an r value
of 32.
'
rG:
(32) (33.32)
'
Thinj
Jc,
^^"^
"'
lO^pvi,
10(28)(0.00255)'(3)
T Q.=>
^'^^
The mathematical treatment and performance chart of cation exchangers can be extended to similar heterogeneous reactions in a batch process
where one atom or ion in the fluid phase reacts with two atoms or active
spots in the solid.
GAS ADSORPTION
CHAP. XXII]
GAS ADSORPTION
logl
Gydr=G[y
+ (^^
dZ^r + PB dZ ^ ^ ) dr
+ PGFe(~)dTdZ
(44)
where
6 = mass velocity of adsorbate-free fluid, lb/(sq ft) (hr)
PB = bulk density of solid, lb per cu ft
pa = density of gas, lb per cu ft
Fe = external void fraction of bed
T = time, hr
w = adsorbate content of solid, lb per lb of solid (adsorbate-free
basis)
y = adsorbate content of fluid stream, lb per lb of fluid
Z = distance in bed measured in direction of flow, ft
The adsorbate is designated as component A.
The first term in Equation (44) represents the mass of component A
entering the section in time dr, the second term the mass leaving the
section, the third the change in the mass of component A present in the
solid portion of the elementary volume, and the fourth term the change
in the content of component A in the fluid portion of the elementary
volume all in the element of time dr.
Equation (44) reduces to
In a steady-flow process the last term of Equation (45) becomes negligible if the fluid content of the bed is negligible compared with the volume
' 0. A. Hougen and W. R. Marshall, Jr., Chem. Eng. Progress 43,197 (1^47). This
mathematical development was originally prepared by these authors in a report by
O. A. Hougen and F. W. Dodge entitled, "Drying of Gases," prepared for NDRC of
OSRD, June 30, 1941 and now declassified for distribution through the Office of
Technical Services, PB 2301, U.S. Department of Commerce (1946).
1082
[CHAP.
XXU
In this case,
In gas adsorption where mass transfer through a gas film is the controlling factor, the rate of adsorption of component A can be expressed as
follows:
TA = Kaa^ipA - pf)
(48)
where
TA = lb-moles A adsorbed/(cu ft) (hr)
PA = partial pressure of A in main gas stream, atmospheres
PA = partial pressure of A in equilibrium with the adsorbate
content of the solid, atmospheres
a = external area of solid particles, sq ft per cu ft
Kg = mass-transfer coefficient as defined by Equation (48)
For ideal-gas behavior, by Dalton's law,
_z_ = yp
IT - p
where
(49)
MA
IT = total pressure
Ma = molecular weight of gas (adsorbate-f ree basis)
MA = molecular weight of adsorbate gas A
= Xca, ^ ir(2/ - / )
(50)
'^
(51)
m.A
Equation (51) may also be written in terms of the height of transfer unit
Rio, Equation (XX-37), page 984. Thus, for dilute gases where p/ = ir.
The changes in adsorbate content of the adsorbent and of the gas may
be expressed in terms of the rate of adsorption given by Equation (52).
Thus, for" the solid adsorbent, expressing rate in pounds rather than in
pound moles,
^ (2/-/)
(53)
H,do
CHAP.
1083
(56)
and
(S)+^(S)=-<-^
where
|3 =
G
paHdo
paPe
1
a =
The development of Equations (55) and (56) is restricted to ideal-gas
behavior and low concentrations for which Equation (50) is satisfactory.
In the general case the temperature in the bed may vary and y* bears a
complex relationship to w. Under these conditions an analytical solution is not available, and it is necessary to resort to the tedious graphical
method discussed on page 1094.
Isothermal Adsorption with Linear Equilibrium. For the restricted
case of isothermal adsorption analytical integration of Equations (55)
and (56) is possible if it may be assumed that y*, the equihbrium adsorbate content of the gas, is proportional to w the adsorbate content of the
soUd. This situation is approximated in many systems. Thus,
y* = cw + a
(58)
1084
[CHAP.
XXII
ble, and Equations (55) and (56) may be combined with (58) and written
as follows:
(") = '(!-)
(-)
where
.
b = 0c
-(I)
aiy - cw)
(60)
2/0 -
*
*
2/0
2/0
*
w
- Wo
Wo W*
f*ciZ
e-2 Joi2iVh^)d{aZ)
(61)
f,br
'
e-*^ J"o(2i\4Z6^)d(6T)
(62)
CHAP. XXll]
1085
Mesh Size
2-4
4-6
6-8
8-10
10-12
12-14
14-20
20-28
D ft
0.0220
0.0128
0.00909
0.00634
0.00576
0.00446
0.00320
0.00226
sq ft per cu ft
117
202
284
407
448
576
805
1140
J
1086
SuiuieniaJ uofq.DBai= .
[CHAP. XXII
CHAP. XXII]
1087
p* _ 1.82u;p,
or
(65)
0.2
0.4
0.6
0.8
1.0
1.2
1.4
bT
P*=V^=1.62/
(66)
1088
_:
CO
^
(M
^
00500t-tD
r - l O O O O
-^^
O
CO
o
(M
O
> =
="
o o d d o o- d
o*
O O i O O t - CO W3
1^
O
ov
[CHAP. XXII
C5
CKAP. XXII]
DRYING OF AIR
1089
1.82
where
c = 1.122pj,
For the special case of isothermal adsorption of water vapor on silica
gel, from Equations (57) and (63),
= 0.703aJ^j
From Equations (57), (63), and (67),
(68)
(69)
Illustration 6. Air is blown through a bed of initially dry silica gel, 1 ft in thickness. The air enters at 80F and 80 per cent relative humidity (J/O = 0.0179) at a
linear velocity of 100 ft per min based on the total cross section. The gel is 6-8 mesh
in size with a l)ulk density, pg of 39 lb per cu ft. It is assumed that isothermal conditions are maintained by means of cooling coils in the bed. The following data are
desired:
(a)
(b)
(c)
(d)
The humidity of the air leaving the bed at the end of 2 hr.
The average humidity of the air leaving the bed over a period of 2 hr.
The moisture distribution in the bed at the end of 2 hr.
The average moisture content of the bed at the end of 2 hr.
87.4
'
^ "
1090
[CHAP. XXII
= 0.34
2/0
y = (0.94)(0.0179) = 0.0061
(6) To determine the average humidity of the air leaving the bod it is necessary to
integrate the outlet humidity over the 2-hr period, Values of y at different times are
calculated as in part (a) and tabulated as follows:
niin
0
20
40
60
80
100
120
br
0
2.9
6.8
8.74
11.6
14.5
17.4
2/2/0
0
0
0.003
0.016
0.065
0.185
0.340
y
0
0
0.00005
0.00029
0.00116
0.00331
0.0061
i! 0.005
<
^0.004
-3
'E 0.003
s
W
0
0.2
0.4
0.6
0.8
1.0
aZ
w/wo
0
4.1
8.2
12.3
10.4
20.5
1.00
1.00
0.92
0.78
0.57
0.30
0.44
0.44
0.405
0.344
0.25
0.132
CHAP. .XXII]
1091
cf)'
0.0825
1
= 0.703O,
H.
= (0.703) (202) (0.0825) = 11.8
In order to evaluate 6 it is necessary to calculate c of Equations (58) and (59). Since
tromEquation (50) and since t = 1.67p*/p., andp* = 2/*x(29/78), = wpjl.67
y*
p. (78)
= 1.60p./^
w
7r(29)(1.67)
Then, from Equations (57) and (59):
1.60g?.' ^ (1.60) (7.5) (0.125)
~ PBH^GT
br = (0.455) (60)
y
0.455/min
(39)(l/n.8)a)
= 27.2
2/0
1092
[CHAP. XXII
26 r y
9R
9A
/ I
/
/
/
23
22
1
'1
/ /
1 1/
/ /
/ /
21
90
1R
/ /
17 -
!_ J
1 '1
Ifl
IK _
L lA
//
'
1 1 1I
'^i'^1
O AO
/ 1 *
11
1 1k
J~
r<
Q
Q
^ /
->
7 ^j
7
^
JT
/ / y '^
^y'^y%<
0 ^
^' >
9^^ = : ^
9
1
% ^i^-
'
3 4 5 6 8 10
20 80 40 60
aZ
100
_...
1000
1093
zaZ
w/wo (from Rg. 217)
w
Top
0
0
1.0
0.120
Bottom
3.22
38.0
0.079
0.0095
Middle
1.61
19.0
0.83
0.099
.a
M
4^
at
,^L0
0.6
L0
QI
6
6
10
8
-aZFia. 220. Rate of Composition Change of a Fluid Stream Leaving a Bed of a
Grajiular Adsorbent (At Low Values of aZ).
0
1094
[CHAP. XXII
y__
yo
0.1
0.3
0.5
0.7
Time,
min
11.2
21.4
31.2
42.4
dhgy
d log T
1.80
1.66
1.32
0.86
aZ
6.0
7.1
7.4
6.0
a, ft
3.0
3.65
3.7
3.0
Avg = 3.4
IT
1.9
4.6
6.8
7.4
h, min
0.170
0.215
0.218
0.175
Avg = 0.195
Isothermal Adsorption with Complex Equilibrium. Where the relationship between the equilibrium adsorbate content of the adsorbent and
that of the gas is not linear, or where the gas in the void of the bed is not
negligible in comparison with the amount flowing through, the assumptions on which Equations (61) and (62) and Figs. 216-220 are based may
lead to serious errors. In the former case it is necessary to resort to
graphical integration of Equations (55) and (56).
By a change in variables the form of Equations (55) and (56) can be
simplified to eliminate all constant terms and one partial derivative.
The time variable r is modified to allow for the time elapse from entrance
to a position Z in the bed. As the front of a gas stream which enters the
bed moves to a position Z units distant from the inlet, the time increased
by the time required to reach that position. This time elapse can be
calculated from the average linear velocity through the voids of the bed.
Since the average fraction of free cross-sectional area is equal to the
fraction of void volume, the average linear velocity is equal to G/paFe,
and the time elapsed in advancing from the entrance to position Z is
PaFeZ/G or yZ. The modified time variable then becomes T yZ. By
this expedient one partial derivative and the constant y are eliminated.
The remaining constants a and P can then be eliminated by defining the
1095
(70)
yZ)
(71)
From Equation (70) it is evident that, when Z is zero, u is zero, and, from
Equation (71), when T = yZ, v is equal to zero.
Since w and y are functions of Z and T, they are also functions of u
and V and from Equation (XI-31):
dw = I ) du + l- ) dv
\du/.o
\dv/u
(72)
dy^CAdu + Mdv
(73)
Then
/dw\
/dw\ /du\
W / z "" \du), XdrJz
(dy\
_(dy\
\dz),
(dy\
(du\
/dw\ /dv\
\d^)u W z
,(dy\
W . WA
_ /dy\
/du\
/dv\
\dv)\dz).
/dy\
/dv\
(74)
(76)
(76)
^
From Equation (71):
m.-"
(77)
(JX-O
(78)
/ '\ \
(11=-^
(a-
(79)
(80)
By substituting Equations (80), (78), and (55) into (74), there results
(S).=<-''-'
(81)
1096
[CHAP. XXIl
By substituting Equations (79), (80) into (75) and (76), and combining
with Equation (56), there results
(|^)__ = -(2/-2/*)
(82)
(g). = -&.-:>
(^:)^ = (.:-.r,
- m
where mean values are taken over the interval Av. The relationship
between y* and w is obtained from isothermal equilibrium-adsorption
measurements which may be expressed graphically for any system.
The graphical solution for isothermal adsorption follows in three stejis.
The adsorbate content of the gas stream as a function of time must he
known at Z = 0 and hence at M = 0. The adsorbate content of the bed
must be known when T = 0. Since the initial adsorbate content of the
bed at any location is unchanged during the lapse of time yZ, the time
required in passing to location Z, it follows from Equation (72) that the
adsorbate content of the bed is the same at t; = 0 as when r = 0.
The first step of the solution is to establish the adsorbate content of the
gas at zero value of i; as a function of M; the second step is to establish the
adsorbate content of the bed at zero value of u, as a function of i;. In
the third step all other values of y and w are obtained for successive increments of Aw and Ai;.
In designating values of w, y, and y* at different intervals of distance and periods of time double subscripts are used, the first subscript
designates increments of u and the second increments of v. Thus, the
symbol 2/01 indicates the value of y at 0 AM and 1 Au, the symbol w^
indicates the value of lu at 1 Aw and 2 A?;.
The general objective is shown in Fig. 221, where values of y, if', and w
are plotted against increments of w for different intervals of v. The
mean values over the interval Aw are represented as y^, J/^ and Wm, and
" L. V. Grossman, Trans. Am. Inst. Chem. Engrs., 42, 535, (1946).
CHAP. XXII]
1097
the mean values over the interval Au by the period values y^, y*^ and w'.
The circled points represent the initial given conditions.
Ste'p I. In Fig. 222, the initial distribution of A in the bed is known
and plotted against Au. The corresponding values of y* are obtained
from adsorption-equilibrium data. The composition of the entering gas
stream is known and designated as 2/00 and in this case is taken as constant with y at w = 0. From the value of Wm at |Aw, the corresponding
value of y* is obtained from adsorption-equilibrium data. From this
point a horizontal line is projected of unit value in u to point B. For
example, if Au = 0.2 the length of the horizontal line is 5AM. A straight
line is then drawn connecting 2/00 with B. The intersection of this line
Given
Stepn
2Au
with the lAw line gives the desired value of 2/10, and y^ is its intersection
with the AM/2 vertical line. The validity of this procedure is evident
from the geometry of Fig. 222, where, from the relationship of similar
triangles,
2/00 2/10
Ay
(85)
Au
1
Au
in agreement with Equations (83).
Successive values of 2/20, ^so. . are obtained in a similar manner with
successive increments of Au.
For the special case where the solid is initially adsorbate-free,2/* = 0
at t; = 0, and Equation (82) is integrated to give
In - = M (at t) = 0)
y
(86)
1098
[CHAP. XXII
1
< Unity m -
<
/c
1/
'"oj
Way
"''my/
y'Jl
0A
Av_
2
lAs
2A
ity of this procedure is evident from the geometry of Fig. 223, where,
from the relations of similar triangles,
Woi Woo
t/,
Ay
Aw
Au
(87)
0 yo mW^
(where = 0)
(88)
CHAP.
XXIIl
1099
Step III. With the estabUshment of the boundary conditions for both
gas and solid the concentration of both gas and solid for succeeding increments not at zero values of either M or v is obtained by a combination of
the methods illustrated, in Figs 222, and 223, and shown in Figs. 224,
and 225. For example, the next point to establish is Wn and yn.
On Fig. 224, values of yoi and Wai and on Fig. 225 values of yw and Wio
are located from previous steps I and II, respectively. The values of yn
and Wn are established on each chart by the respective methods used in
Figs. 221 and 222. Adjustments of the two figures must be made
according to their geometry until points yn and Wn agree on both charts.
A mechanical device fulfilling the geometry of the two figures may be
used to adjust the two figures readily. It is required in Fig. 224 that the
linkage of lines pivots on yoi and Woi, that Wm and ?/* are in equilibrium
and are free to move along the vertical Aw/2, and that line y*B is horizontal and of unit length in u. Points yn and Wn are free to move along
the vertical IAM. It is required in Fig. 225 that the linkage of lines
pivots on 2/10 and Wio, that w^ and yl, are in equilibrium and are free to
move along the vertical Ay/2, that Une yl,C is horizontal and of unit
length in v and that Unes Wio, Wn, and y*J,C are parallel.
It should be noted that this graphical method was developed for
dimensionless time and distance parameters. However, the solution
arrived at for a specific system and boundary conditions is a general
solution for other variable conditions of operation.
Unsteady Heat Transmission in Granular Beds. As originally
developed by Schumann^" and Furnas" charts similar to Figs. 216 and
217 were used for calculating temperature changes in both gas stream
and bed where heat was transferred between a flowing gas and a stationary granular bed in the absence of heat effects due to chemical reactions
and where constant values of heat-transfer coefficients and thermal
properties could be assumed. To use these charts for heat transmission
the following replacements of symbols should be made.
Substitute,
t To
to To
y
yo
T -To
w_
to To
Wo
Ua. / 1
- =
UpLr
rlho
for
(89)
a
1100
where
[CHAP. XXII
t = temperature of gas
to = temperature of gas entering
T = temperature of solid
To = initial temperature of solid
^
U = over-all heat transmission coefEcient, per unit area
Hho = over-all height of heat-transfer unit
Cp = specific heat of gas
Cs = specific heat of solid
= habits - g
(90)
CHAP.
XXUl
NONISOTHERMAL REACTIONS
HQl
AHn
(91)
where
Cg = specific heat of fluid
P(5 = density of fluid
tg = temperature of fluid
is = temperature of solid
Cs = specific heat of solid
Z = distance irom the inlet of the bed
h = heat-transmission coefficient per unit area of solid
CB = external area of solid per unit volume
G = mass velocity of fluid stream, mass/(area) (time)
r = rate of reaction, adsorption, or desorption, moles of A converted, adsorbed, or desorbed per unit time per unit mass
of solid
AH = heat of reaction per mole of reactant A
Pb = bulk density of solid bed
Ft = external void fraction of solid bed
Let
httv
Cspb
hUv
CQPBF,
G
HHPQF,
ana.-*-'-'
O.=-'-+
rAH
-F-
(94)
r/-k.{r-'-fz)
(95)
(56)
1102
[CHAP.
XXII
where
(lOD
CHAP. XXII]
1103
is and the mean values over the interval Av' as < and ti . The
circled points represent the initial given conditions.
Step I. In Fig. 227 the initial known temperature of the bed'is
plotted against AM'. The temperature of the entering gas stream is
known and designated as taoo- The first step is to establish the temperature of the gas stream as it first progresses through the bed (at ' = 0).
The establishment of the first point toio is indicated in Fig. 227. From
the mean temperature of the solid ts at the interval Au'/2 a horizontal
line is projected of unit length in terms of u' to point B. (If AM' = 0.1,
then the length of the horizontal line is 10 AM') . A straight luie is drawn
connecting B with ieoo- The intersection of this line with the lAu' line
Stepll
AM'
tso ~ ig
tsa ~ taa
u',
(at v' = 0)
(103)
1104
[CHAP. XXII
+ m =
tso
Av'
(104)
CHAP.
XXII]
GENERAL CASE
1105
and are both free to move along the vertical Av/2, that line CD is horizontal and of unit length in v'. Succeeding values of gas and solid temperature are obtained in a similar manner.
General Case. The procedure illustrated in Figs. 227-230 required
knowledge of the reaction rate r at all points in the reactor. In the
general case r is a function of conversion and composition as well as of
temperature. Under such conditions it is necessary to evaluate simultaneously the distribution of conversion and composition along with
temperature as the stepmse procedure is carried out. This involves
combination of equations of the form of (83) and (84) for the evaluation
of conversions with ^Equations (99) and (100) for temperature. The
simultaneous solution of the four equations is carried out by a stepwise
procedure similar to that used for either pair individually but complicated by the necessity of additional successive approximations which
result from the fact that the temperature changes and conversion changes
in any increment are interdependent.
A common example is in the adiabatic adsorption of a gas by a station' ary bed. The rate of adsorption is a function of the adsorbate content
of both the gas and the solid as well as of the temperature of each and
can be determined experimentally and expressed graphically for even
the most complex cases. Similarly, the differential heat of adsorption is
a function of temperature and the adsorbate content of the adsorbent
which may be expressed in either graphical or analytical form. From
these two relationships working charts may be prepared which for a
specific problem relates B^ of Equation (101) to temperature and the
adsorbate content of both the gas and the adsorbent. A similar procedure may be followed for a chemical reaction whose rate equation and
thermochemistry are known.
The evaluation of the complete distributions of temperature, reactants, and products as functions of time and position is a straightforward
but tedious operation following the patterns previously described. In
this operation the increments of time and distance used in establishing
temperature variations must be related to the time and distance increments used in establishing variations in composit/on. For simplification the increments of u and v should be related as follows:
AM'
and
= -
AM
= fi
Ay' = ^ Av = ^ ^
AM
Av
(105)
(106)
1106
[CHAP. XXll
PROBLEMS
1. It is desired to design a plant for the production of 15,000 lb der day of mononitrotoluene from toluene. A design study is to be made on the basis of a fresh mixed
acid of the following composition in mole per cent:
HNOj
H2SO1
H2O
45
30
25
100
It is desired to produce" a conversion of 99.0 per cent with an excess of 3 per cent
HNOs above that theoretically required.
(o) Using the data of Illustration 1, calculate the minimum reactor volume
required in a batch operation at 30C in which 2 hr are required for charging and
emptying the reactor.
(6) Calculate the reactor volume required for a single-stage continuous operation
under the conditions of part (a),.
(c) Calculate the volumes of the reactor required for a two-stage counterflow
operation in which 50 per cent of the total conversion is produced in each reactor.
Neglect the formation of di- and trinitro compounds.
(d) Calculate the reactor volume required if the process is carried out in a twostage counterflow operation with reactors of equal size.
2. For the reaction represented by Equation (17) derive rate equations corresponding to the following mechanisms:
(o) Reaction between an adsorbed B molecule and an adjacent active center with
the rate of desorption of product B as the rate-determining step.(b) Reaction on a single active center between gaseous B and solid A to form a
chemisorbed R molecule and a gaseous S molecule. The rate-controlling step is the
surface reaction.
3. Using the data and assumptions of Illustration 2, develop curves similar to those
of Fig. 213 for combustion of the coke with an air rate of 150 lb/(sq ft) (hr) at an
average temperature of 2400F. Compare these results with Fig. 213.
4. Hard water is softened at a rate of 20 gal per min in an exchanger bed 2 sq ft
in area and 2 ft thick. The initial hardness of the water is equivalent to 200 parts of
calcium carbonate per milhon parts of water. The exchanger has an initial replaceable sodium content equivalent to 28,000 grains of calcium carbonate per cu ft. The
density of the mineral is 30 lb per cu ft, grain size 20-28 mesh, and with a value of k
equal to 2.29.
(a) Calculate with and without use of Fig. 214, the residual hardness of the water
after 5 hr of steady flow.
(b) Plot the residual hardness of water against time for a period of 24 hr by use of
Fig. 214.
(c) Calculate with and without the use of Fig. 215 the time required to reach a
residual hardness of seven parts per milUon and the gallons of water softened.
6. In a cation exchanger water is softened at the rate of 3 gal per sq ft per min in a
bed 4 ft thick, having a density of 30 lb per cu ft and an exchange capacity of 20,000
grains of calcium carbonate per cu ft. The water has an initial hardness of 200 parts
equivalent calcium carbonate per million. After operation for 8 hr, the water leaving
has a residual hardness of 12.8 parts per million of calcium carbonate.
CHAP. XXII]
PROBLEMS
1107
(o) Calculate the value of the reaction velocity constant ki as defined by Equation
(32).
(6) Plot the residual hardness against time over a period of 16 hr.
6. Air at 70F and 90 per cent relative humidity is passed isothermally through a
bed of 2-4 mesh activated alumina 2 ft in thickness at a velocity of 50 ft per min
(based upon total cross section of bed).
The bed is initially free of moisture. An average value of the adsorption equilibrium ratio m over the entire relative humidity range is 0.20.* The following properties of the bed are assumed: PB = 50 lb per cu ft, Dp = 0.0216 ft,' a, = 181 sq ft per
cu ft 50 per cent external void space. Calculate, over a drying period of 4 hr and
at the end of 1, 2 and 4 hr,
(o) The humidity of the air leaving the bed.
(6) The average humidity of the air leaving the bed.
(c) The moisture content gradient in the bed.
(d) The average moisture content of the bed.
(e) The total water adsorbed by a bed 10 sq ft in area.
7. Air at 80F and '80 per cent relative humidity is passed through a bed of silica
gel 6.8 mesh, 12 in. thick, at an entering rate of 136 ft per min based on total cross
section. The drying of the air takes place isothermally. The bulk density of the gel
is 39 lb per cu ft,'and the value of m is 0.55.* At the end of 1 hr the relative humidity
of the air leaving is 10 per cent. Calculate the value of Hda^ for the bed.
8. Benzene vapor present to the extent of 1.0 per cent by volume in hydrogen is to
be removed by passing the gas mixture downward through a bed of silica gel at 80F
and 2 atm pressure at a linear velocity of 200 ft per min (based on total cross section).
It is desired to operate for a period of 90 min with a minimum benzene recovery from
the gas of 90 per cent. The silica gel is 2-4 mesh, with a bulk density of 39 lb per cu ft,
and witt the following estimated properties, Dp = 0.0220 ft, a = 117 sq ft per cu ft.
The adsorption-equilibrium factor m for benzene on silica gel is 1.67.* Over the 1.5
hr period calculate:
(a) The depth of bed required.
(6) The concentration gradient of benzene in the bed.
(c) The total benzene removed by a bed 8 sq ft in area.
* In problems 6, 7, and 8, m is defined by the relation w = mp*/p, as used in
Equation (65).
APPENDIX
ATOMIC WEIGHTS OF THE MORE COMMON ELEMENTS
Aluminum
Antimony
Argon
Arsenic
Barium
Bismuth
Boron
Bromine
Cadmium
Calcium
Carbon
Chlorine
Chrotjiium
Cobalt
Copper
Fluorine
Gold
Helium
Hydrogen
Iodine
Iron
Lead
Lithium
Magnesium
Al
Sb
A '
As
Ba
Bi
B
Br
Cd
Ca
C
CI
Cr
Co
Cu
F
Au
He
H
I
Fe
Pb
Li
Mg
26.97
121.76
39.944
74.91
137.36
209.00
10.82
79.916
112.41
40.08
12.010
35.457
52.01
58.94
63.57
19.00
197.2
4.003
1.008
126.92
55.85
207.21
6.940
24.32
Manganese
Mercury
Molybdenum
Neon
Nickel
Nitrogen
Oxygen
Phosphorus
Platinum
Potassium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Tellurium
Tin
Titanium
Tungsten
Uranium
Vanadium
Zinc
Zirconium
Mn
Hg
Mo
Ne
Ni
N
0
P
Pt
K
Se
Si
Ag
Na
Sr
S
Te
Sn
Ti
W
U
V
Zn
Zr
54.93
200.61
95.95
20.183
58.69
14.008
16.000
30.98
195.23
39.096
78.96
28.06
107.880
22.997
87.63
32.08
127.61
118.70
47.90
183.92
238.07
50.95
65.38
91.22
xviii
APPENDIX
CONVEKSION FACTORS AND CONSTANTS
Analysis of Air
29
28.2
Physical Constants
The Gas Law Constant R
R
R
R
R
= 1.987
= 82.06
= 10.71
= 0.729
(calories)/(g-mole)C'K)
(cu cm)(atm)/(g-mole)(K)
(Ib/sq in.)(cu ft)/(lb-mole) (R)
(atm)(cuft)/(lb-mole)(R)
Calorie
Btu
Joule
Foot-pound
Kilogram-meter
Liter-atmos
IChu
Calories
Btu
Joules
Footpounds
Kilogrammeters
1
252
0.2389
0.3240
2.343
24.21
453.6
3.968 X 10-'
1
9.482X10-4
1.286X10-3
9.298 X 10-'
9.607X10-2
1.8
4.185
1055
1
1.356
9.806
101.32
1899
3.087
777.9
0.73756
1
7.2327
74.733
1400
0.4267
107.5
0.1019
0.13826
1
10.333
193.5
Liter-atm
Cuftatm
Footpoundals
Horsepower
hours
4.130 X 10-2
10.41
9.869 X 1 0 - '
1.3381X10-2
9.678 X 10-2
1
13.74
1.459 X 1 0 - '
0.3676
3.485 XlO-4
4.7253 X 10-*
3.4177 X 10-5
3.5319X10-2
0.6617
99.31
25030
23.73
32.174
232.7
2403.8
45054
1.5591 X 10-
3.929 X 10-4
3.725 X 1 0 - '
6.0505 X 10-'
3.6529 Xl0-<
3.7734X10-5
7.072 XlO-4
* From Perkins, iTitroduciion to General Thermodynamicit John Wiley & Sons. Inc., Publishere, with
permission.
APPENDIX
xix
Length
1 inch
1 micron
1 Angstrom unit
2.540 centimeters
10~* meter
10""" meter
Mass
1
1
1
1
1
1
poimd*
pound*
poimd*
ton (short)
grata
kilogram
16 ounces*
7000 grains
453.6 grams
2000 pounds*
15.43 grains
2.205 pounds*
* Avoirdupois.
Mathematical Constants
e
IT
In N
1
1
1
1
1
2.7183
3.1416
2.303 log N
.'
kilowatt
kilowatt
horsepower
watt
watt
Power
56.92 British thermal units per minute
1.341 horsepower
550 foot-pounds per second
44.24 foot-pounds per minute
14.34 calories per minute
Pressure
Degrees P
Degrees K
Degrees R
1.8 (degrees C) + 32
degrees C + 273.15
degrees F -1- 459.7
Volume
1 cubic inch
1 Uter
1 cubic foot
1 cubic meter
1 cubic meter
1 U. S. gallon
1 U. S. gallon
1 U. S. gallon
1 British gallon
1 cubic foot
1 liter
1 U. S. fluid ounce
APPENDIX
160-j;
460-j:
-70
iBo-j:
-240
440-:
-:
-825
420-j
"
1500-j
1450-|
750-^ 400
J
130-j
400-=
- |-800
726-j
J 7-200
|-50
: ^775
^380
380-j
1400-j
^750
700-j
360 - :
110-4
1350 ^ 7 2 5
-^360
j - 180
675-;
-: ^ 4 0
1300-j ^700
1
1250 675 .
840 - j
100-4
650-j
3 2 0 - i f-160
90-i
JsoH L
TO-i
--
be
[-120
60-j ^ 1 0
240-i
,4 625
i-0
20'
1150-;
E-300
1100-j
675
1060-^
^280
475-
140-^ 6 0
t-220
:
^525
950500
900-
:
:^475
: 1-240
4 5 0 - I:
:0- i-
^550
1000-:
180
^600
I
650-]
600 ^ 2 6 0
160-
^625
z.
200
10
:
o
peso's
i
^1200-;
625-5 -_
\'&)
XO-
&
^320
^100
80
600
220
*0-
i-340
U
-:
575-;
260-t
60-i
u.
SL
1-140
280-j
^20
t5
1*300-1 -
-875
-850
1550-::
775-j
-: - 2 2 0
140: 60
120-4
1600-::
800 :
420
8 5 0 - 1^450
800-t.425
APPENDIX
10-
1.16
1.00
0.99
12-
1.15
0.84
-8 1.14
-7-6-
r-1.13
-5-
16-
1.12
1.11
38
0.97
40
0.96
42-
0.95
44 - t-0.81
0.94
48-
22-
*"
u.
(0
1.06
3
241
+-
<
Q 28
' 1.06
30
- 1.04
32 ^
1.03
- 0.91 ,
-0.90 ,
4
S
91
10
^0.78
S 52a.'
< 54 -
0.77-
tj)
-0.89 '
56 -
0.88
58-
0.87
60-
0.86
62-
0.76'
0.75
1^0.74
0.73
34 - ^
0.85
71 1.02
8
1.01
0.79
^'60-
1.08-5
3
E-1.07
0.92
. 1.09 .
h-
0.80
-0.93
1.10
.-2-
0.82
46-
20-
-3-
0.98
0.83
14-
18-
-4-
0.85
36
36
6466-
0.72
68 -
0.71
0.84
38
0.83
1.00
40 f-
700.70
APPENDIX
xxu
2500.0Zt-10000
2000.0-
2300020000-
lOOO.O I -5000
15000-^
-4000
-3000
500.0400,0 300.0 ~
200.0-
i5o;o 100.0-
-2000
-1500
8000-
-4000
6000-
-3000
-1000
-750
40OO-
-500
3000-
-1600
2000-
-1000
-800
-300
-2000
1600-
-200 I
-150 I
3 30.0c
<3
-100 S
3 20.0 -
-90 I s
1 15.0- -> s
>
-70
9.0-
-6000
-6000
lOOOO-
50.0S 40.0-
10.0-
-8000
-400
75.0-
-10000
&
I
fe-60 I
-55
8.0 50
7.06.0-
45
5.0
4.0
40
g 1000-^
-600
-500
=-400
800
600-^
.i
400-
-300 I
-200 f
1 300E
2
-150
-80
15010080-
-60
-50
-40
6050-
-30
6.06.5 5.04.5
4.0-
-60 Sc
t
I",
-50,g_
o
-40 I
-35
-30 1
-25 ^
;=;;20 ,
lE-18
40-20
20-3
i.o-i ^ 1 6
0.9 4
0.8 - i
0.7 -4
3.0-
Z4-
120
110
- 100
-90
80
-70
o
200-
30-
RO7.0 -
r- 12
0.6 -1 1-10
-35
10r^'^
O.S> = - 8
AUTHOR INDEX
Part I, pages 1-436
Ahlberg, 1086
Alvarado, 903
Amagat, 38, 695
Andersen, 758, 764
Anderson, A. G., 708
Anderson, C. T., 742, 748
Anzelius, 1084
Arnold, 988, 989
Asbury, 933
Aston, 708, 709, 788
Augustine, 1068, 1069
Avery, 709
Avogadro, 28
Badger, 783
Barker, 790
Bartlett, 596
Bauer, 295
Beach, 709
Beattie, 482, 598
Beckmann, 944, 947
Benedict, 483
Bennewitz, 798, 799
Benning, 520
BergeUn, 143, 144, 145
Berkman, 903
Beyer, 758, 764
Bichowsky, 253, 2?, 292, 745, 866
Blasdale, 129
Blodgett, 905
Bodenstein, 854, 897
Boltzmann, 217
Borden, 790
Bornstein, 944
Borsook, 709
Bosnjakovic, 281, 683
Bourland, 708
Bridgman, 482
Brown, 931, 1005
Brugmann, 227
Brunauer, 915
Bryant, 213
Buffington, 521
Cain, 897
Calingaert, 67, 512
Falk, 1068
Fallon, 336, 339
Edgell, 708
Edmister, 494
Egan, 708
Egloff, 903
Eidinoff, 708
Ellis, 709
Emmett, 157, 904
Eucken, 990
Ewell, 708
Ewing, 295
Eyring, 765, 808, 815, 894, 895, 908, 912
XXIV
AUTHOR INDEX
Fink, 708
Fischer, 898
Forest, 227
Forster, 708
Foster, 685
Fowler, 765
Freundlich, 154
Friauf, 314
FroUch, 861
Furnas, lOSJ^
Gamson, 73, 604, 606, 621, 665, 676, 985
Garner, 709
Gibbs, 618, 625
Gilkey, 521
Gilliland, 677, 981, 988
Glasstone, 793, 808, 815, 894, 895, 908,
912
Glockler, 708
Gohr, 9S1, 1032
Goodman, 243
Gordon, 235, 238
Grossman, 10S6, IO4I, 1095, 1100
Grosvenor, 93
Guggenheim, 765
Guldberg, 68
Guttman, 708
Gwin, 786, 787
Halford, 708
Hamer, 649
Hardy, 708
Harrop, 365
Hart, lOU, 1015, 1021
Haslam, 326, 1068
Hatta, 99
Henry, 146
Hermann, 292
Herzfeld, 843
Hess, 259
Hildebrand, 679, 682
Hirschfelder, 779, 781, 866, 892, 893
Holcomb, 335
Hougen, 157, 906, 944, 985, 1075, 1080,
1084, 1086
Huffman,'697, 708
Huggins, 709
Hulburt, 1004
Jack, 709
Jahnig, 1005, 1032
Jeans, 975
Johanson, 933, 934, 959
Johnston, 793
Jones, 314
Justi, 212, 216, 217
Justice, 899
Kaltenbach, 303
Kassel, 709, 790, 1031
Katz, 601, 673
Kay, 601, 604
Keenan, 444, 522, 567, 583, 618, 915
KeUey, 692, 724, 738, 742, 748, 766, 775,
790
Kemp, 708
Kennedy, 709
Keyes, 522, 667
Kharasch, 763
Kiefer, 567
Kimball, 765
Kkchhoff, 304
Kirkbride, 672
Kistyakowsky, 230, 231, 709
Koo, 1016
Kopp, 219
Kreisinger, 1068, 1069
Kurata, 601
Lacey, 509, 517
Laidler, 808, 816, 894, 895, 908, 912 "
Lamb, 846
Langmuir, 905
Laplace, 269
Lavoisier, 259
Lewis, G. N., 285, 287, 314, 619, 623,
626, 637, 641
Lewis, W. K., 1064, 1056
Licht, 872
Lind, 854, 897
Linnett, 709
Lockhart, 143, 144, 145
Love, 916
Luder, 212, 216, 217
Maier, 737
Margules, 652
Markwood, 520
Marshall, 1080, 1084, 1086
Martin, 931, 1005, 1032
Masson, 605
Maxwell, 457, 975, 990
Mayer, J., 765
Mayer, M., 765
Mayfield, 799
McAdams, 974, 989, 990, 1016
McCabe, 278
McHarness, 520
McKinley, IO64, 1055
Meissner, 70, 236
Merriman, 662
Messerly, 708, 709
Morgen, 292
Morrell, 903
Murphree, 931, 932, 1005, 1032
AUTHOR INDEX
Murphy, 330, 332, 846
Myers, 8S3, 861
Nelson, 330, 332, 493
Newton, 490, 931, 1006, 103S
NicoU, 897
Oman, 1016, 1017
Onnes, 207
Osborne, 709
Othmer, 65, 83, 84, 145
Ovitz, 1068, 1069
Parks, 697, 709, 949
PauUng, 765, 781
Pease, 841, 854
Pecherer, 708
Perkins, 438
Perrott, 314
Perry, 223
Petit, 217
Pitzer, 708, 709, 712, 763, 786, 787, 789,
949, 960
Prentiss, 652
Prosen, 712
Randall, 285, 287, 623, 626, 637, 641
Raoult, 80, 626
Ratchford, 898
Reed, 830
Reiser, 853
Rice, F. O., 843
Rice, W. W., 709
Rossini, 253, 262, 271, 292, 712, 745,
868, 943
Rossner, 798, 799
Rubin, 483
Russell, H., 709
Russell, R. P., 326, 93S
Sage, 509, 517
Sagenkahn, 709
Scatchard, 649, 652
Schaafsma, 509
Schmidt, 1041
Schneider, 861
Schoenborn, 655
Schumacher, 894
Schumann, S. C, 708, 793
Schumann, T. E. S., 1084
Schwartz, 793
Scott, 709, 949, 960
Selheimer, 666
Setler, 708
Shaw, 462, 465
Sherwood, 830, 974, 980, 981
ShiUing, 655
Shimp, 931
XXV
Shupe, 482
Simpson, 931, 1006, 1032
Smith, D. F., 899
Smith, R. L., 333, 490, 601, 604
Smith, W. J., 620
Sokolnikoff, E. S., 830, 1084
Sokolnikoff, I. S., 830,1084
Senders, 666
Spencer, 899
Stfiohert, 87S
Stefan, 975
Stegeman, 708, 709
Stevenson, 709
Stuart, 667
Stull, 799
Suen, 1054, 1055
Sugden, 71
Swain, 1075, 1076
Szasz, 708
Taylor, 793, 904, 908
Thiele, 997, 998
Thodos, 985
Tobias, 145
Tolman, 765
Trouton, 230
Tsohernitz, 944
Tyson, 931, 1006, 1032
Uehling, 321, 328, 329
Umino, 418, 419
Uyehara, 870, 1021
van der Waals, 463, 480
van Laar, 653, 664, 660
Vaughan, 895 '
Walter, 766
Watson, K. M., 68, 73,231,233,330,331,
332, 333, 334, 336, 339, 490, 493,
501, 602, 604, 604, 606, 621, 665,
676, 758, 764, 846, 853, 861, 870,
906, 933, 934, 959, 1016, 1017,
1021
Webb, 483
Weber, 494
Webster, 617
Wenner, 224, 228, 757
Westrum, 708
White, 1054
Wilke, 985
Wilson, 766, 793
Wohl, 649, 652, 669, 660
York, 494, 572
Yost, 709
Zemansky, 202
SUBJECT INDEX
Part I, pages 1-436
Absolute pressure, 35
Absolute reaction rates, 808
Absolute zero, 31
Absorption, 146
Absorption refrigeration, 575, 681-588
Accelerators, S44
Accumulation of inventory, 179-180
Acetone-chloroform, activity coefficients
of, 645-647
saturation temperature of, 648
Acids, specific heats of, 224
Activated adsorption, 150, 908-910
Activated alumina, 158, 902, 905
Activated charcoal, 153, 155, 905
Activated complex, 808
Activation, energy of, 816, 908
enthalpy of, 810, 955
prediction of, 889
entropy of, 810, 956
prediction of, 889
Active centers, 904, 910
equidistant, 913
fraction occupied, 913
fraction unoccupied, 913
Activity, 627-641, 715, 911, 1010
Activity coefficients, 630-641, 676, 715,
1055
apparent, 656
effect, of chemical type on, 664
of molecular size on, 664
of temperature on, 661
in acetone-chloroform system, 645647 ,
in aqueous sodium chloride solutions,
640
in benzene-toluene system, 645-647
in binary systems, 651-659
in different standard states, 635
in isopropyl ether-isopropyl alcohol
system, 645-647
in sucrose solutions, 636-637
in symmetrical systems, 659
in water-w-butanol system, 645-647
ionic, 637-638
of mixed acids, 1056
XXVUl
SUBJECT INDEX
SUBJECT INDEX
Butene production, 968
Butenes, dealkylation of, 966
By-passing fluid streams, 193
Calcium balance, 1076
Calcium carbonate, solubility of, 747
Calcium chloride, as a desiccant, 158
solutions of, 137
enthalpy of, 281
relative humidity of, 137
vapor pressure of, 137
Calorie, 203
"Calorimetry, low temperature, 699
Capillary condensation, 150
Carbon, amorphous, 324
heat of combustion of, 262, 323
Carbonaceous deposit, 1032
residue, 1100
Carbonates, solubility of, 742-748
Carbon balance, 349
Carbon dioxide, pVT relations of, 479480
solubility of, 683
Carnot cycle, 667-560
reverse, 576
Carnot principle, 559-560
Catalyst, 902
activity factor of, 936-937
deactivation of, 930
diffusion in, 995-1002
fouling of, 9S0, 1008
life test of, 940
porosity of, 907
probable life of, 940
reactivation of, 932
regeneration of, 904, 931, 1008
selectivity of, 903, 1006
sintering of, 906
structure of, 907
Catalyst bed, cooling, 931
fluidized, 1005
Catalyst deposit, 930
removal of, 931
Catalyst requirement, 1031
Catalysts, in cylindrical tubes, 1035
in thin slabs, 1034
. shape of, 996
solid, 906
supported, 905
unsupported, 905
Catalytic alkylation, 1028
Catalytic beds, heat transfer in, 97S
mass transfer in, 973
Catalytic conversion equation, 929
Catalytic cracking, 433-436
Catalytic decomposition of alcohol, 90S
XXIX
XXX
SUBJECT INDEX
SUBJECT
Copper, heat of vaporization calculation, 72B
vapor-pressure calculation, 725
Corresponding states, theory of, 488
Cotton, equilibrium moisture content of,
152
Countercurrent heat exchange, 566
Countercurrent processing, 177
Counterdiffusion, 982
Covalent radii, atomic, 781-782
Cox chart, 65-66, 160
Cracking, catalytic, 433-i36
of butane, 966
of petroleum, 421
process of, 931
Cracking reactions, 967
Criteria, of complex equilibria, 614-619
of equilibrium, 449-453
Critical composition of solution, 143
Critical-condensation temperature, 600
Critical constants, of gases, 481
table, 234, 237
of paraffins, 74
Critical density, 54
estimation of, 604
Critical phenomena, of gaseous mixtures, 599-605
Critical point, for mixtures, 600
pseudo-, 604-605
Critical pressure, 54, 72-73
and vapor pressure, 234, 237
of paraffins, 507
Critical properties, estimation of, 68, 504
Critical state, 54
Critical temperature, 54, 71
estimation from boiling point, 69
of paraffins, 507
of petroleum, 70, 73, 333
oi refrigerants, 237
of solution, 143
Critical velo^-'ty, 974
Critical volume, 70
estimation of, 604
Crystallization, 111-112, 123
fractional, 128
kinetic theory of, 111-112
with no solvates, 123
with solvates, 126
Cycle, Carnot, 557-560
reverse, 576
power-plant, 560-668
llankine, 561-565
improvements on, 564-565
refrigeration, 576-579
reversible, 567
Cychc processes, 666-592
INDEX
XXXI
xxxu
SUBJECT INDEX
volumetric, 571
of engine, 566
thermodynamic, 569
for Carnot cycle, 559
for Rankine cycle, 563
Electrolytes, activities in, 638
dissociation in, 638
Electron diffraction, 777
patterns of, 902
<
Electronic energy, 767
Electron microscope, 904
Elements, specific heats of, 218
Empirical conversion plots, 961-962
Endothermic compounds, 252
Endothermic reactions, 251
Energy, 27
availability of, 438-444
thermal, 560
conservation of, 28
degradation of, 438-444
external potential, 27
free, 446-448
internal, 201, 448
of activation, 816, 908
of rotation, 766
of translation, 766
of vibration, 767
potential, 27
Energy balance, 95-204
differential, 538
enthalpy terms in, 307-308
input items, 307-308
of acid chambers, 400
of a process for the production of
hydrogen, diagram, 208
of blast furnace, 414-420
of chemical processes, 204-206
of coal-fired boiler furnace, 348-356
of combustion processes, 342-344,355356, 369-371
of gas producer, 369-371
of Gay-Lussac tower, 403
of Glover tower, 393
of intermittent processes, 369-371
of metallur^cal processes, 406-408,
414-420
of pyrites burner, 389
of sulfuric acid plant, 405-406
SUBJECT INDEX
Energy functions, 448-449, 453
change in isothermal nonflowprooesses,
448-449, 540
differential, 454-455, 472
partial derivatives of, 458-469, 472
relation to pressure, volume, and
temperature, 462-463, 473
shaft work from, 448-449, 540
Energy levels, 768
Energy units, 202-203
conversion of, 438
Engine, Carnot, 557-660
efficiency of, 566
performance of, 567
Enthalpy, 207, 448, 711
as a criterion of equilibrium, 462
charts, 244, 291
composition diagrams, 279-281, 300
of air-water vapor, 243-245 .
of ammonia-water, 584
of calcium chloride solutions, 281
of hydrochloric acid, 279
of silica gel, 300
of sulfuric acid, 280
evaluation of, 238-239
internal contributions to, 788
of activation, 810, 965
prediction of, 889
of adsorbed systems, 299-300
of an ideal gas, 475
of benzene, chart, 527
of calcium chloride, chart, 281
of gaseous mixtures, 609
of gases, effect of pressure, 492-496
of humid air, 240, 243-245
of iron, 419 , ,
of liquids, effect of pressure, 606-509
of silica gel, chart, 300
of solutions, 609-613
of sulfuric acid, chart, 280
of water vapor, 344
relation to pressure, volume, and
temperature, 463, 473
relative, 207, 709
Enthalpy pressure correction, for gases,
492-i96
chart, 494-496
differential at constant pressure, 516
differential at constant temperature,
616
for liquids, 506-609
chart, 608
differentia], 612-613
for saturated fluids, 611
Entropy, 440-446
as a criterion of equilibrium, 450
XXXlll
XXXIV
SUBJECT INDEX
SUBJECT INDEX
Fluid catalytic cracking process, 931
Fluidized catalyst bed, 1005
Fluidized reactor, 1032
Fluidized state, 931
Fluids, expansion and compression of,
638-592
thermodynamic properties of, 479-535
Fltix, in blast furnace, 411
Fouling, 932
factors of, 932-9S4, 959, 961
of catalyst, 930, 1006
Fractional crystallization, 128
Fraction of moisture removed in bed of
silica gel, 192
Free energy, 446-447
as a criterion of equilibrium, 452-453
change, effect of temperature at constant pressure, 463, 473
data, presentation of, 699
measurement of, 698
of activation, 902
of formation of hydrocarbons, 698
of mixing, 647-651
relative, 709
Free expansion, 439, 442, 551-656
adiabatic, 601, 561-563
flow, 501, 551-663
nonflow, 563-656
Free radicals, 843
Free rotation, 766
Freezing-point curve, 114
Freon, 234, 237
Frequencies of vibration, 769
Frequency factor, 816
*
Freundlich isotherm, 154
Friction factor, 1016
Fuel gas, 338
heating value of, 338
table, 340
hypothetical composition of, 339
Fuels, 323
combustion of, 338
chart, 372
energy balance of, 342
heating value of, 327-328, 340
heat of incomplete combustion of, 341
material balance of, 342
Fugacities, 715
at equilibrium, 619
in ideal solutions, 626
in solution, 621
of gases, 619, 667
of pure liquids and solids, 621
related to partial molal free energies,
'625
Fugacity, 619-627
XXXV
XXXVl
SUBJECT INDEX
SUBJECT INDEX
Heat, of reaction, 249-252
at constant volume, 302
calculation of, 266-268
effect of pressure on, 302-303
effect of temperature on, 803
standard, 250
under changing pressures and volumes, 302
of sofution, 253-257, 273-282
charts, 276-276
differential, 291-293
integral, 274
of hydrates, 277
of sulfuric acid, chart, 275
tables, 253-257
of transition, 229, 419
table, 229, 419
of vaporization, 229-238, 337
at critical temperature, 233
at normal boiUng point, 230
effect of pressure on, 232-238
effect of temperature on, 233
from Clapeyron equation, 230
from empirical vapor-pressure equations, 231
from Kistyakowsky equation, 230
from reduced reference plots, 235
from reference substance plots, 232
from Trouton's rule, 230
of hydrocarbons and petroleum
fractions, 336-337
of refrigerants, 237
of wetting, 293
differential, 294-297
integral, 294-297
table, 294
units, 203
with water, figure, 295
Heat capacity, 210-212
at constant pressure, 211-217, 459,472
at constant volume, 210, 459, 472
atomic, 217
differences of, 461, 473-474
effect, of pressure on, 214, 462, 472
of temperature on, 213
of volume on, 462, 472
English units of, 213-217
equations, English units, 213
metric units, 214
internal rotational contributions to,
790
mean values, English units, 214-217
metric units of, 216
metric units of, 214
of gases, pressure correction to, 499601
xxxvu
XXXVUl
SUBJECT INDEX
SUBJECT INDEX
Isentropio compression efficiency, work
of expansion, flow, 540, 548-550
nonflow, 540, 545-547
Isochors, 599
Isolated system, 1, 437
Isomerization of pentanes, 730
Isomerization reaction, 913, 1013
Isometrics, 599
Iso-octane, hydrogenation of, 9 ^
Isopropyl alcohol in water, equilibrium
distribution of, chart, 145
Isopropyl ether-isopropyl alcohol, activity coefficients, 645-647
saturation temperature >of, 642
Isothermal adsorption, 1083
with complex equilibrium, 1094
Isothermal compression efficiency, 570
Isothermal solubility curve, 143
Isothermal work of expansion, flow, 540,
542-544
nonflow, 540-542
Isotherms, adsorption of, 151-155
chart, 153
of carbon dioxide, 480
j factor, 983, 987
Jacobians, 465-471
properties of, 466
table of values of, 468
use of, in deriving relations, 469-471
Joule-Thomson effect, 501
Joule-Thomson expansion, 551-563
Kaolin, 152
Kelvin temperature scale, 32
1. eselguhr, 906
Kilocalorie, 203
Kinematic viscosity, 870
Kinetic energy, external, 28
internal, 28
molecular, 28
Kinetics, 437
of combustion, 1068-1073
Kinetic theory, 28
extension of, 31
of adsorption, 149-150
of capillary condensation, 150
of condensation, 56
of dissolution, 111-112
of distribution, 139
of gases, 28-32
of Uquids, 53-54
of solubiUty, 111-112
of gases, 146-149
of translation, 30
of vaporization, 55-57
XXXIX
xl
SUBJECT INDEX
SUBJECT INDEX
Nitration, of aromatics, 1054-1058
of benzene, 1054-1060
Nitric acid, heat capacity of, chart, 224
Nitric oxide, decomposition of, 813
Nitrogen, and hydrogen, compressibility
of, 596-697
atmospheric, 42
compressibility factors of, 484-487
Nitrogen balance, 351
Nitrogen peroxide, adsorption of, 685
Nitrous oxide, decomposition of, 8S8
Nonadiabatic reactions, 311
Noneleotrolytes, solubility of, 677
Nonelectrolytic solution, standard state,
724
Nonflow processes, 204,1081
reactions of, 822
shaft work in, 539
isentropic, 540, 545-647
isothermal, 640-542
Nonideal system, 606, 608-609
Nonisothermal reactions, unsteady state,
1100-1105
Nonlinear molecules, 768
Nonpolar compounds, 68
critical temperature of, 68, 71-76
Nonvolatile solute, 82
Normal molal volume, 34
at standard conditions, 484
Number, of reactor units, 1014
of transfer units, 991
Olefins, hydrogenation of, 1043
Open system, 437
Optimum intermediate pressure for
multistage compression, 673-574
Optimum reactor design, 883
Order, complex, 840
of reaction, 806
complex, 819
Ore. in blast furnace, 409
Oscillators, 792
Osmotic pressure. 111
Outgassed carbon, 154-155
Over-all reaction rate, 1054
Oxides, specific heats of, 219
Oxygen balance, limitations of, 354
in coal, 354
Paper, 152
Parachor, 70-71
Paraffins, boiling points, 607
critical constants of, 74-75
heating values of, 338
physical properties of, 507
vapor-pressure constants of, 144
xli
xlii
SUBJECT INDEX
SUBJECT INDEX
xliii
xliv
SUBJECT INDEX
Relative saturation, 91
Relative volatility, 657
Retrograde condensation, 600-601
Reverse Carnot cycle, 576
Reverse reactions, 818
Reversibility, 438-440
of adsorption, 156
of gaseous adsorption, 146
Reversible cycle, 557
Reversible process, 438-439, 447
Reynolds number, 986, 987, 1016-1017
Rotational energy, 766
Sackur-Tetrode equation, 770
Salting out, 123
Saturated liquid, heat capacity of, 511513
from Cp of its ideal gas, 513-518
Saturated solutions, 112
Saturated vapor, 57, 89
heat capacity of, 511-513
Saturation, partial, 91
percentage of, 91, 114
temperature of, 121
of binary systems, 648
Schmidt number, 986-987
Secondary methyl substitutions, 761
Second law of thermodynamics, 439
Seeding, 211
Selectivity, 860, 98, 1020
of catalyst, 903, 1006
Separation, entropy of, 686
work of, 686
Severity factors, 885
Shaft work, 538
from energy functions, 540
in flow processes, 539
isentropic, 540, 548-550
isothermal, 640, 542-544
in nonflow processes, 539
isentropic, 540, 545-547
isothermal, 540-542
Shaw's method of derivation, 465-471
Silica-alumina catalyst, 9S3
Silica gel, 158, 906
adsorption by, 1089-1091, 1094
enthalpy of, 300
equilibrium moisture content of, 152,
158, 1088
heat of wetting, 296
partial, 299
vapor pressure of, 159
Silk, 152
Simultaneous equations, solution of, 737
Simultaneous reactions, 818, 828
equilibrium of, 729
SUBJECT INDEX
Solutions, thermochemistry of, 273-274
thermodynamics of, 596-641
vapor pressures of, 84, 136
Solvates, 115
Solvent, 111
Soot and tar in combustion, 364-371
Sorption, 111
Space velocity, 839, 928, 964, lOOZ, 1006
Spatial arrangement, 9S7
Specific gravity, 17
see also Densities
of gases, 35
of liquids, 17-22
of petroleum, 330-331
Specific heat, see also Heat capacity
of acids in aqueous solutions, 224
of bases, 224
of calcium compounds, 220
of chlorides, 225
of coke, chart, 218
of elements, charts, 218
of hydrocarbon gases, figure, 335
of nitrates, 225 \
of oxides, chart, 210
of petroleum, liquid, chart, 334
vapor, 335
of sulfates, 225
Specificity of catalyst, 902
Spectroscopic data, 791, 793
Spectroscopic notations, 775
Spontaneoul*process, 439
Stable equihbrium, 460
Stagnant film, 976
Standard conditions, 34
Standard free energy, 693-713
change of, 692, 694
effect of temperature upon, 695
Standard heat, of combustion, 260-266
of formation, 252-258
of reaction, 249
Standard states, 627
for gases in liquid solution, 630
for pure liquids and solids, 628
in gaseous mixtures, 628
in infinite dilution, 629
in nonelectrolytio solution, 628
Statistical methods, 765-798
Statistical weight, 772, 793
Steady-flow process, 1081
Steam, minimum ratio, to methane, 736
process, 665
superheated, vaporization with, 78
Steam power-plant cycles, 660-568
Steam rate, 667
Stepwise countercurrent extraction, 177
procedure for, 1010-1011
xlv
xlvi
SUBJECT INDEX
SUBJECT
INDEX
xivu
xlviii
SUBJECT INDEX