Enthalpy-Concentration Charts.

Literature Survey and the Two

New Systems Isopropyl Alcohol-Water and Acetic Acid-Water

ROBERT LEMLICH, CHAD GOTTSCHLICH, AND RONALD HOKE'

Department of Chemical Engineering, University of Cincinnati, Cincinnati 21, Ohio

E nthalpy-concentration diagrams h a v e proved of con- T h e p r e s s u r e r a n g e s i n t h e t a b l e a r e given only for t h o s e

s i d e r a b l e v a l u e i n t h e solution of many problems, particularly
t h o s e involving mixing, c r y s t a l l i z a t i o n , and d i s t i l l a t i o n .
Unfortunately, however, t h e l a c k of c e r t a i n thermodynamic
d a t a together with t h e t e d i o u s nature of t h e work involved
i n constructing t h e s e c h a r t s , h a s limited their a v a i l a b i l i t y
t o comparatively few s y s t e m s . Accordingly, a s e a r c h of
t h e l i t e r a t u r e w a s conducted i n a n effort t o l o c a t e e x i s t i n g
c h a r t s . Diagrams for t w o new s y s t e m s were constructed.
SURVEY
T h e r e s u l t s of t h e s e a r c h , together with a summary of
pertinent information, a r e presented i n T a b l e I. Here 4 3
r e f e r e n c e s t o c h a r t s covering 25 different s y s t e m s a r e
l i s t e d . Where o n e chart i s c l e a r l y b a s e d on a n o t h e r , t h e
original r e f e r e n c e i s given, u n l e s s t h e l a t e r chart i n c l u d e s
a d d i t i o n a l data. C h a r t s for humid a i r , which c a n b e found
in conjunction with psychrometric c h a r t s in many p l a c e s ,
a r e omitted.
C h a r t s for most s y s t e m s l i s t e d in t h e t a b l e cover t h e
liquid p h a s e i n more or l e s s d e t a i l . However, t h e extent
of p h a s e equilibria shown v a r i e s c o n s i d e r a b l y from chart t o
chart. F o r liquid-vapor equilibrium i t r a n g e s from portions
of t h e bubble point l i n e a l o n e t o e x t e n s i v e t i e l i n e repre-
s e n t a t i o n s involving both bubble point and dew point l i n e s .
F o r solid-liquid equilibrium t h e variation r a n g e s from in-
complete freezing point l i n e s t o numerous complete iso-
therms i n t h e solid-liquid region.
1 P r e s e n t a d d r e s s , E s s o R e s e a r c h and Engineering Co., Linden, N. J.
_-
T a b l e I. Results of Literature Survey
s y s t e m s having c h a r t s showing vapor-liquid equilibrium.
F o r t h e liquid or s o l i d p h a s e , or equilibrium between t h e
two, t h e e f f e c t of p r e s s u r e i s , of c o u r s e , s m a l l .
Compositions a r e l i s t e d on a weight b a s i s in terms of
t h e f i r s t component. Mihere r e f e r e n c e s t o more than o n e
chart a r e indicated for a particular s y s t e m , t h e equilibrium
and r a n g e s l i s t e d a r e for t h e s e v e r a l c h a r t s a s a group.
ISOPROPYLALCOHOL-WATER
T h e general technique for constructing F i g u r e 1, t h e
enthalpy-concentration c h a r t for t h e s y s t e m isopropyl
alcohol-water, follows t h e method d e s c r i b e d by Dodge (27).
T h e datum level c h o s e n i s that of pure l i q u i d s a t 32'F.
E n t h a l p i e s i n t h e liquid region were computed from integral
h e a t of solution d a t a (25) a t 77"F., h e a t c a p a c i t y d a t a for
s o l u t i o n s of various concentration (19), h e a t c a p a c i t y d a t a
for pure isopropyl alcohol (21, 4 8 ) , and t h e h e a t c a p a c i t y
for pure water, which w a s t a k e n a s unity. T o compute t h e
e n t h a l p y of liquid at a n y particular concentration and
temperature, t h e enthalpy c h a n g e s of t h e pure components
from t h e datum t o 7 7 ° F . were added t o t h e h e a t of solution
a t 77'F. and t h e enthalpy c h a n g e of t h e mixture from
77°F. t o t h e temperature i n question. F r e e z i n g point d a t a
(30) made p o s s i b l e placement of t h e freezing point line.
Vapor-liquid equilibrium d a t a a t v a r i o u s p r e s s u r e s (61)
made p o s s i b l e placement of t h e bubble point l i n e s and,
together with s u b s e q u e n t enthalpy c a l c u l a t i o n s for t h e
vapor, t h e dew point l i n e s and c o n j u g a t e c u r v e s a s well.
T h e e n t h a l p i e s in t h e vapor region w e r e obtained by
-

P h a s e Equilibria Shown Range of Variables

Solid- Liquid- Solid- Solid- Temp., . Pressure, Composition,

NO. System References liquid vapor vapor solid O F . lb./sq. inch abs. wt. %
la Ammonia-(1/4N2 + 3/4H2) (6) X - 58 to 1292 14.2 to 8530 0 to 100
2 Ammonia-water ( 4 , 8, 1 3 ) X X X - I49 to 400 0.284 to 300 0 to 100
3 Benzene-toluene (3) X 50 to 231 14.7 0 to 100
4 Benzene-water (5) X 54 to 551 2.94 to 735 0 to 100
5 Calcium chloride-water (7, 27) X X X X -148 to 1436 2.84 to 28.4 0 to 100
6 Ethyl alcohol-water (11, 28, 4 4 , 52) X X - 2 2 to 302 1.47 to 14.7 0 to 100
7 Ethylene glycol-water (14) X 60 to 480 4.41 0 to 100
8 Ferrous sulfate-water (39) X X X X - 40 to 1186 14.7 0 to 100
9 Glycerol-water ( 5 7) X X X -220 to 320 14.7 0 to 100
to Hydrazine-water (57) X X -130 t o 482 14.7 0 t o 100
11 Hydrogen chloride-water (25, 5 9 ) X - 1 2 1 to 227 14.7 0 to 100
12 Hydrogen fluoride-water (58, 60) X 32 to 572 14.7 0 t o 100
13 Magnesium sulfate-water (50) X X 25 to 230 ... 0 to 50
14 Methanol-water (1, 52) X 32 to 400 5.80 to 14.7 0 to 100
15 Nitrogen-hydrogen (6) 3 2 to 1472 4270 0 to 100
16 Nitrogen-ox ygen (8,18) X -334 to 80 7.1 to 142 0 to 100
17 P o t a s s i u m hydroxide-water (45) X 32 to 932 1 . 4 7 to 296 0 t o 90
18 n-Propyl alcohol-water (52) X 32 to 212 5.80 to 14.7 0 to 100
19 S i l i c a gel-water (29) 32 to 270 ... 66.7 to 100
20 Sodium carbonate-water (5 7) X X X X 14 to 392 14.7 0 to 100
21 Sodium hydroxide-water ( 2 , 12, 1 6 , 2 2 , 56,57, 6 2 ) X X 32 to 900 ... 0 to 100
22 Sucrose-water (9,5 4 ) X X X 10 to 320 0.284 to 42.6 0 to 100
23 Sulfur trioxide-water (10, 23, 5 3 ) X X - 4 to 608 14.7 0 to 100
24 Sulfuric acid-water (26) X 32 to 550 14.7 0 to 100
25 Sulfuric acid-nitric acid-water (43) 32 ... 0 t o 100

a c h e m i c a 1 equilibria (ammonia s y n t h e s i s ) presented a s well.

32 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 2, NO. I

simply summing t h e e n t h a l p i e s of t h e pure c o m p o n e n t s a t
t h e given temperature. T h e very s m a l l h e a t of mixing of
t h e vapor w a s n e g l e c t e d and c a l c u l a t i o n b a s e d o n t h e well
known, g e n e r a l i z e d , e n t h a l p y c h a n g e - p r e s s u r e c h a r t (24)
s h o w e d t h e e f f e c t of p r e s s u r e o n vapor e n t h a l p y negligible
a t t h e s e pressures. Accordingly, t h e e n t h a l p y of pure
isopropyl a l c o h o l vapor w a s obtained by summing t h e
e n t h a l p y of s a t u r a t e d liquid isopropyl a l c o h o l a t t h e normal
boiling point, t h e normal l a t e n t h e a t of vaporization which
i s 160 c a l . per gram (34, 41, 49), and t h e enthalpy
c h a n g e of pure vapor ( 4 0 ) f r o m t h e normal boiling point t o
t h e temperature i n question. T h e e n t h a l p y of pure w a t e r
vapor w a s obtained from s t e a m t a b l e s (37).
A C E T I C ACID-WATER
T h e general method of c o n s t r u c t i n g F i g u r e 2 , t h e
enthalpy-concentration c h a r t for t h e a c e t i c acid-water
system, l i k e w i s e f o l l o w s t h e conventional method. T h e
datum l e v e l h e r e i s t h e pure components, liquid water and
s o l i d a c e t i c a c i d , a t 3 2 ° F . B y a method a n a l o g o u s to
t h a t u s e d for t h e previous diagram, e n t h a l p i e s i n t h e liquid
region w e r e computed by adding t o g e t h e r i n t h e r e q u i s i t e
proportions, t h e enthalpy of pure liquid w a t e r a t 65°F.
r e l a t i v e t o 3 2 " F . , t h e e n t h a l p y of pure liquid a c e t i c a c i d
at 65°F. r e l a t i v e t o t h e s o l i d a t 3 2 ' F . , t h e h e a t of solu-
tion a t 65°F. (36), and t h e e n t h a l p y of t h e s o l u t i o n a t t h e
g i v e n temperature r e l a t i v e t o 65 O F . computed from h e a t
c a p a c i t y d a t a for t h e s o l u t i o n (46). T h e e n t h a l p y of t h e
pure a c e t i c a c i d a t 65°F. w a s c a l c u l a t e d by summing t h e
e n t h a l p y of pure s o l i d a t i t s melting point of 6 2 ° F . r e l a t i v e
t o s o l i d a t 3 2 ° F . which w a s computed from h e a t c a p a c i t y
d a t a (31), t h e e n t h a l p y of pure liquid a t 65°F. r e l a t i v e t o
liquid a t 62°F. which w a s a l s o computed f r o m h e a t c a p a c i t y
d a t a (32), a n d t h e h e a t of fusion of pure liquid (33).
F r e e z i n g point d a t a (30) made p o s s i b l e l o c a t i o n of t h e
freezing point l i n e , w h i l e e n t h a l p y d a t a for i c e ( 3 7 , t h e
h e a t of fusion for water (52), and t h e corresponding d a t a
for a c e t i c a c i d mentioned above, made p o s s i b l e location of

0 IO 20 30 40 50 60 70 80 90 100
COMPOSITION,WT PERC ENT ISOPROPYL ALCOHOL
Figure 1. Enthalpy-concentration chart for isopropyl alcohol-wator
Application of conjugate curve a t 1 a h . illustrated by thin broken l i n e

1957 CHEMICAL AND ENGINEERING DATA SERIES 33

 COMPOSITION, WT. PERCENT ACETIC ACID
Figure 2. Enthalpy-concentration chart for acetic acid-water
Applic ttian of conlugate curve at 14.7 pounds per square inch absolute illustrated by thin broiien line

t h e l i n e a r isotherms i n t h e solid-liquid region. No s o l i d LITERATURE CITED

h y d r a t e s form (20, 38, 55).
Dew point and bubble point l i n e s , together with c o n j u g a t e
c u r v e s , were l o c a t e d by equilibrium d a t a (47). A s with t h e
f i r s t c h a r t , t h e h e a t of mixing i n t h e vapor p h a s e w a s
n e g l e c t e d and t h e e n t h a l p i e s i n t h e vapor region were
computed by summing t h e e n t h a l p i e s of t h e pure vapor
components. T h e e n t h a l p y of pure a c e t i c a c i d vapor w a s
computed by adding t h e e n t h a l p y of pure s a t u r a t e d liquid
t o t h e h e a t of vaporization a t t h a t temperature (35).
C a l c u l a t i o n showed t h a t a n y s u b s e q u e n t p r e s s u r e correction
applied t o t h e enthalpy of t h e a c e t i c a c i d vapor, b e c a u s e
of e i t h e r dimerization (32) or “ t r u e ” nonideality ( 2 4 ) , w a s
without significant effect on t h e e n t h a l p y of t h e vapor
mixture, b e i n g less than 1 B.t.u. per pound. A s before,
e n t h a l p i e s for s t e a m were taken from s t e a m t a b l e s .
ACKNOWLEDGMENT
T h e authors wish t o e x p r e s s t h e i r appreciation t o
William L i c h t for reviewing t h e manuscript, t o Kaparthi
Ramalingam for helping with some of t h e literature s e a r c h ,
and t o Roger Keith for inking t h e f i g u r e s .
(1) Ansell, L. S., Samuels, H., F r i s k e , W. C . , Chem. Eng. 58,
No. 4, 133 (1951).
(2) Badge:, W. L . , Ranchero J. T. “Introduction to Chemical
Engineering,” p. 204, McCrawiHill, New York, 1955.
(3) Ibid., p. 269.
(4) Ibid., p. 288.
(5) Bal’yan, S . V., J. Appl. Chern. (U.S.S.R.) 13, 1612 (1940).
(6) Bosnjakovic, F., Forsch. Gebiete Ingenieurw. 10, 256 (1939).
(7) Bosnjakovic, F., “Technische Therrnodynamik,” vol. 2,
p. 90, Steinkopf, L e i p z i g , 1937.
(8) Ibid., appended charts.
(9) Bosnjakovic, F., 2 . Ver. deut. Ing. E e i h . No. 6, 169 (1939).
(10) Broughton, D. B., Chem. M e t . Eng. 52, No. 4, 123 (1945).
(11) Brown, G. G., others, “Unit Operations,” p. 327, Wiley,
New York, 1950.
(12) Ibid., p. 487.
(13) [bid., p. 592.
(14) Chu, J. C., Yang, W. J., Ind. Eng. Chem. 42, 373 (1950).
(15) Dimmling, W.,L m g e , E . , Z. Elektrochem. 5 5 , 322 (1951).
(16) Dodge, B. F., “Chemical Engineering Thermodynamics,”
p. 398, McCraw-Hill, New York, 1944.
(17) Ibid., p. 399.
(18) Ibid., p. 402.
(19) Doroshevski;, A. G., J. R u s s . Phys.-Chem. SOC. 41, 958
(1910).
(20) Faucon, A., Ann. chirn. e t phys. 19 (8),70 (1910).

34 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 2, NO. I

(21)Ginnings, D. C., Corruccini, R. L . , Ind. Eng. Chem. 40, (43) McKinley, C., Brown, G. G., Chem. Met. Eng. 49, No. 5, 142
1990 (1948). (1942).
(22)Haltenberger, W., Jr., Ibid., 31, 783 (1939). (44) Merkel, F., Arch. Warmewirtsch. u. Dampfkesselw. 10, 13
(23) HedstFGm, B. 0. A , , T j u s , E., Chem.-Ing.-Tech. 24, 22 (1929).
(1952). (45)Merkel, F.,Z.Ver. deut. Ing. 72, 109 (1928).
(24)Hougen, 0. A., Watson, K. M., “Chemical P r o c e s s (46) Newmann, M. B.,2. physik. Chem. A158, 285 (1932).
P r i n c i p l e s , ” p. 495, Wiley, New York, 1947. (47) Othmer, D. F., Silvis, S. J., Spiel, A., I n d . Eng. Chem. 44,
(25) Hougen, 0.A., Watson, K. M., Ragatz, R. A., “Chemical 1864 (1952).
P r o c e s s Principles,” p. 324, Wiley, New York, 1954. (48) P a r k s , G. S., Kelley, K. K., J . A m . Chem. SOC. 47, 2089
(26)Ibid., p. 325. (1925).
(27)I b i d . , p. 326. (49)P a r k s , G. S., Nelson, W. K., J . P h y s . Chem. 32, 61 (1928).
(28) Ibid., p. 327. (50) Perry, J. H., “Chemical Engineers’ Handbook,” 3rd ed.,
(29) Ibid., p. 390. p. 1052, McGraw-Hill, New York, 1950.
(30) International C r i t i c a l T a b l e s , vol. 4, p. 262, McGraw-Hill, (51)Ibid., p. 1701.
New York, 1928. (52) P l e w e s , A. C.,others, Can. J. Technol. 32, 133 (1954).
(31)Ibid., vol. 5, p. 102. (53) R o s s , W. D., Chem. Eng. Progr. 48, 314 (1952).
(32)Ibid., p. 114 (54) Schiebl, K., “WZrmewirtschaft i n d e r Zuckerindustrie,”
(33) Ibid., p. 132. p. 166 and appended chart, Steinkopf, Dresden, 1939.
(34) Ibid., p. 137. (55) Senter, G . , P r o c . Chem. SOC.(London) 25, 292 (1909).
(35)Ibid., p. 138. (56) Standiford, F. C., Badger, W. L., Ind. Eng. Chem. 46, 2400
(36) I b i d . , p. 159. (1954).
(37) Keenan, J. H . , Keyes, F. G., “Thermodynamic P r o p e r t i e s of (57) Tyner, M., A.1.Ch.E. Ioumaf 1, 87 (1955).
Steam,” Wiley, New York, 1936. (58) Tyner, M., Chem. Eng. Progr. 45, 49 (1950).
(38)Kendall, J., Booge, J. E., Andrews, J. C . , J. Am. Chem. (59) Van Nuys, C. C., Trans. Am. Inst. Chem. Engrs. 39, 663
SOC. 39, 2303 (1917). (1943)
(39) Kobe, K. A , , Couch, E. J . , Jr., Ind. Eng. Chem. 46, 377 (60) Vogt, E. G., Ibid., 43, 39 (1947).
(1954). (61)Wilson, A , Simons, E. L,Ind. Eng. Chem. 44, 2214 (1952).
(40) Kobe, K. A., Harrison, R. H., and Pennington, R. E., (62) Wilson, H. R ,McCabe, W. L., Ibid., 34, 558 (1942).
Petroleum Refiner 30, No. 8, 119 (1951).
(41) Lange, N. A,, “Handbook of Chemistry,” 7th ed., Handbook Received for review February 3, 1956. Accepted June 13, 1956.
P u b l i s h e r s , Sandusky, Ohio, 1949. Division o f Industrial and Engineering Chemistry, 130th Meeting
(42) Levy, B., Davis, T. W., J . Am. Chem. SOC. 76, 3268 (1954). ACS, Atlantic C i t y , N. J . , September 1956.

Liquid-Liquid Equilibria for Alcohol -Sodium

Hyd roxide -Wa ter Sys tem s
A. L. MILLS AND FRED HUGHES
Manchester Oil Refinery Ltd., Traffard Park, Manchester, England

s o l u b i l i t y d a t a h a v e b e e n published for sodium hydroxide p r o c e s s i n g i t i s preferred that t h e two s t a g e s should t a k e

in a q u e o u s e t h y l a l c o h o l (2) and i n a q u e o u s isobutyl p l a c e concurrently. For e i t h e r p r o c e s s i n g system, i t i s a
alcohol ( I ) , but no d a t a were a v a i l a b l e for a q u e o u s isopropyl d i s t i n c t a d v a n t a g e if a homogeneous neutralizing-extracting
alcohol ( I . P . A . ) . Information o n t h e solubility of s t r o n g solution i s u s e d .
c a u s t i c s o d a s o l u t i o n s i n isopropyl alcohol arid in i n d u s t r i a l P r e l i n i n a r y e x p e r i m e n t s i n d i c a t e d that industrial methyl-
methylated spirit (1.lT.S.) w a s required for pilot plant neu- a t e d spirit and e t h y l alcohol b e h a v e differently a n d i t w a s
tralization experiments. I n d u s t r i a l methylated s p i r i t i s t h e decided therefore t o i n v e s t i g a t e t h e s y s t e m s for i n d u s t r i a l
commercial f o r m of ethyl alcohol a v a i l a b l e i n t h e United methylated s p i r i t and isopropyl alcohol a t 25 and 60 O C .
Kingdom.
On refining petroleum, particularly o n p r o c e s s i n g for MATERIALS
highly refined w h i t e o i l s by sulfonation, i t i s n e c e s s a r y t o
A s i t w a s e x p e c t e d t h a t information r e s u l t i n g from t h i s
extract o i l - s o l u b l e s u l f o n i c a c i d s from t h e s u l f o n a t e d o i l
project might b e a p p l i e d t o plant s c a l e p r o c e s s i n g , n o
and t o n e u t r a l i z e t o t h e corresponding sodium s a l t s . T h e attempt w a s made t o purify m a t e r i a l s which were of techni-
quality and e s p e c i a l l y t h e color of t h e by-product sodium cal quality a n d h a d t h e following properties.
petroleum s u l f o n a t e s a r e influenced b y t h e r e s i d e n c e time
of t h e sulfonic acid-oil reaction product, particularly if
Specific Gravity
t h e equipment i s mild s t e e l . For t h e two s y s t e m s of at 2o°C. Strength, Weight %
p r o c e s s i n g which may b e applied-centrifuge o r batch-it Aqueous c a u s t i c soda 1.4590 43.0
i s e s s e n t i a l t h a t , for t h e centrifuge p r o c e s s , neutralization I.M.S. 0.8064 94.2
and extraction proceed simultaneously, w h e r e a s for batch I.P.A. 0.7852 100.0

1957 CHEMICAL AND ENGINEERING DATA SERIES 35