TKM-307

Termodinamika Teknik Kimia I

2 - PVT Behavior of Fluid, Equation of State

P T Diagram Pv
Diagram
T-v Diagram
 Equation of State
For the regions of the diagram where a single phase exist:
f (P, V, T) 0
This means an equation of state exist relating P, V, T. An EOS may
be solved for any one of the three quantities as a function of the
other two, viz.: V = V(T,P) V V
dV dT dP
T P P T
1 V
Volume expansivity:
V T P
1 V
Isothermal compressibility:
V P T
dV
dT dP
V
 Example

For liquid acetone at 20oC & 1 bar:

= 1.487 x 10-3 oC-1 = 62 x x 10-6 bar-1 V= 1.287 cm3g-1
For aceton, find:
P
a. The value of T
V
b. The pressure generated by heating at constant V from
20oC & 1 bar to 30oC
c. The change in volume for a change from 20oC & 1 bar to
0oC & 10 bar.
 Problem 3.1

Express the volume expansivity and isothermal

compressibility as functions of density and
its partial derivatives.

The isothermal compressibility coefficient () of

water at 50oC and 1 bar is 44.18 x 10-6 bar-1. To
what pressure must water be compressed at
50oC to change its density by 1%? Assume that
is independent of P.
 Problem 3.2 & 3.3

Generally, volume expansivity and isothermal compressibility

depend on T and P.
Prove that

P T T P

The Tait equation for liquids is written for an isotherm as:

AP
V V0 1
B P
where V is specific or molar volume, Vo is the hypothetical
molar or specific volume at P = 0 and A & B are positive
constant. Find an expression for the isothermal
compressibility consistent with this equation.
 Problem 3.4

For liquid water the isothermal compressibility is

given by: c

V ( P b)
where c & b are functions of temperature only.
If 1 kg of water is compressed isothermally &
reversibly from 1 bar to 500 bar at 60oC, how
much work is required?
At 60oC, b=2700 bar and c = 0.125 cm3 g-1
 Problem 3.5

Calculate the reversible work done in

compressing 1 ft3 of mercury at a constant
temperature of 32oF from 1 atm to 3000 atm.
The isothermal compressibility of mercury at
32oF is:

/atm-1 = 3.9 x 10-6 0.1 x 10-9 P (atm)

 Problem 3.6

Five kilograms of liquid carbon tetrachloride undergo

a mechanically reversible, isobaric change of state
at 1 bar during which the temperature change
from 0oC to 20oC. Determine Vt, W, Q, and Ut

The properties for liquid carbon tetrachloride at 1 bar

& ooC may be assumed independent of
temperature:
= 1.2 x 10-3 K-1
Cp = 0.84 kJ kg-1 K-1
= 1590 kg m-3
 Problem 3.7

A substance for which is a constant undergo a

mechanically reversible process from initial state
(P1,V1) to final state (P2,V2), where V is molar
volume.
a. Starting with the definition of , show that the
path of the process is described by
V A(T) exp( P)

b. Determine an exact expression which gives the

isothermal work done on 1 mol of this constant-
substance
P v Diagram
 Virial EOS & Ideal Gas

Virial expansion: PV RT (1 B' P C' P 2 D' P3 ...

B C D
Alternative form: PV RT (1 2 3 ...
V V V
PV
Compressibility factor Z
RT

For ideal gas: Z = 1, thus PV RT

 The Ideal Gas

The internal energy of a real gas is a function of pressure and

temperature.

This pressure dependency is the result of forces between the

molecules.

In an ideal gas, such forces does not exist. No energy would be

required to alter the average intermolecular distance, and
therefore no energy would be required to bring about volume
& pressure changes in an ideal gas at constant temperature.
In other word, the internal energy of an ideal gas is a function
of temperature only.
U U (T )
 Implied Property Relations for an Ideal
Gas

U dU
CV CV (T)
T V dT

H U PV U(T) RT
Thus H is also a funcion of temperature only
H dH
CP CP (T)
T P dT
dH
CP C P (T ) C v (T ) R
dT
 Isothermal Process
Closed System, Ideal Gas, Mechanically Reversible

U 0 PV = constant

H 0

RT V2 P1
W PdV dV RT ln RT ln
V V1 P2

QW
 Isobaric Process
Closed System, Ideal Gas, Mechanically Reversible

U CV dT TV-1 = constant

H CP dT

W PdV P dV P (V2 V1 ) R (T2 T1 )

Q H
 Isochoric (Constant V) Process
Closed System, Ideal Gas, Mechanically Reversible

U CV dT TP-1 = constant

H CP dT

W PdV 0

Q U
 Adiabatic Process
Closed System, Ideal Gas, Mechanically Reversible

Q 0 dQ 0 R
RT T2 V1 Cv
dW P dV C v dT 0 P dV C v dT dV
V T1 V2
dU C v dT R
RT T2 P2 CP

W PdV C v dT P d
P

T1 P1
U C V dT
CP
P2 V1 Cv
H C P dT TV 1
cons tan t
P1 V2
1

TP cons tan t
CP
PV con tan t
CV
 Polytropic Process
Closed System, Ideal Gas, Mechanically Reversible

Polytropic process can be considered as general

form of process. 1
TV cons tan t
1
TP
cons tan t
PV con tan t

Isobaric process :=0

Isothermal process :=1
Adiabatic process :=
Isochoric process :=
 Example 3.2

Air is compressed from an initial condition of 1 bar & 25oC to a final

state of 5 bar & 25oC by three different mechanically reversible
processes in a closed system:
a. Heating at constant volume followed by cooling at constant
pressure
b. Isothermal compression
c. Adiabatic compression followed by cooling at constant volume.
Assume air to be an ideal gas with the constant heat capacities: CV =
5/2 R, CP = 7/2 R.

Sketch the process in a PV diagram & calculate the work required,

heat transferred, and the changes in internal energy & entalphy of
the air for each processes
 Example 3.3

An ideal gas undergoes the following sequence of

mechanically reversible processes in a closed system:
a. From an initial state of 70oC & 1 bar, it is compressed
adiabatically to 150oC
b. It is then cooled from 150oC to 70oC at constant pressure
c. Finally, it is expanded isothermally to its original state

Sketch the process in a PV diagram & calculate W, Q, U,

and H for each of the three processes and for the entire
cycle.

Take CV = 3/2 R and CP = 5/2R

 Problem 3.8

One mole of an ideal gas with CV = 5/2 R, CP = 7/2

R expands from P1 = 8 bar & T1 = 600 K to P2 =
1 bar by each of the following path:
(a) Constant volume
(b) Contant temperature
(c) Adiabatically
Assuming mechanical reversibility, calculate W, Q,
U, and H for each of the three processes.
Sketch each path in a single PV diagram
 Problem 3.9

An ideal gas initially at 600 K & 10 bar undergoes a four-step

mechanically reversible cycle in a closed system. In step
1-2 pressure decreases isothermally to 3 bar; in step 2-3
pressure decreases at constant volume to 2 bar; in step 3-
4 volume decreases at constant pressure; and in step 4-1
the gas returns adiabatically to its initial step.
a. Sketch the cycle on a PV diagram
b. Determine (where unknown) both T & P for states 1, 2, 3,
and 4
c. Calculate W, Q, U, and H for each step of the cycle

Data: CV = 5/2 R, CP = 7/2 R

 Problem 3.10

An ideal gas, CV = 3/2 R & CP = 5/2 R is changed from P1 = 1 bar &

Vt1 = 12 m3 to P2 = 12 bar & Vt2 = 1 m3 by the following
mechanically reversible processes:
a. Isothermal compression
b. Adiabatic compression followed by cooling at constant pressure
c. Adiabatic compression followed by cooling at constant volume
d. Heating at constant volume followed by cooling at constant
pressure
e. Cooling at constant pressure followed by heating at constant
volume

Calculate W, Q, Ut, and Ht for each of these processes, and sketch

the paths of all processes on a single PV diagram
 Example 3.4

A 400 gram mass of nitrogen at 27oC is held in a vertical cylinder by a

frictionless piston. The weight of the piston makes the pressure of
the nitrogen 0.35 bar higher than that of the surroundings
atmosphere, which is at 1 bar & 27oC. Thus the nitrogen is initially at
a pressure of 1.35 bar, and is in mechanical & thermal equilibrium
with its surroundings. Consider the following sequence of process:

a. The apparatus is immersed in an ice/water bath and is allowed to

come to equilibrium
b. A variable force is slowly applied to the piston so that the nitrogen
is compressed reversibly at the constant temperature of 0oC until
the gas volume reaches one-half the value at the end of step a. At
this point the piston is held in place by latches.
 Example 3.4 (cont)

c. The apparatus is removed from ice/water bath and comes

to thermal equilibrium with the surrounding atmosphere at
27oC
d. The latches are removed, and the apparatus is allowed to
return to complete equilibrium with its surroundings

Sketch the entire cycle on a PV diagram, and calculate Q, W,

U & H for the nitrogen for each step of the cycle.
Nitrogen may be considered an ideal gas for which CV = 5/2
R and CP = 7/2 R
 Cubic Equation of State:
van der Waals Equation (1873)
2
RT a 27 R 2 TC
P 2 a
Vb V 64 PC

1 RTC
b
8 PC

3 RTC
VC
8 PC

PC VC 3
ZC
R TC 8
 Theorem of Corresponding State;
Accentric Factor
All fluids, when compared at the same reduced
temperature & reduced pressure, have approximately
the same compressibility factor, and all deviate from
ideal gas behavior to about the same degree
T P
Tr Pr
TC PC

Accentric Factor
1.0 log Pr
sat
Tr 0.7
(Pitzer)
Critical Constants & Accentric Factors:
Paraffins

-6 3. -1
Tc/K Pc/bar Vc/10 m mol Zc
Critical Constants & Accentric Factors:
Olefin & Miscellaneous Organics

-6 3. -1
Tc/K Pc/bar Vc/10 m mol Zc
Critical Constants & Accentric Factors:
Miscellaneous Organic Compounds

-6 3. -1
Tc/K Pc/bar Vc/10 m mol Zc
Critical Constants & Accentric Factors:
Elementary Gases

-6 3. -1
Tc/K Pc/bar Vc/10 m mol Zc
Critical Constants & Accentric Factors:
Miscellaneous Inorganic Compounds

-6 3. -1
Tc/K Pc/bar Vc/10 m mol Zc
 Cubic Equation of State:
Redlich/Kwong Equation (1949)
RT a (T )
P
V b V ( V b)

2 2
R 2 TC 2
1 2 R TC
a (T) (Tr ) 0.42748 Tr
PC PC

RTC RTC
b 0.08664
PC PC

PC VC 1
ZC
R TC 3
 Cubic Equation of State:
Soave/Redlich/Kwong Equation (1972)
RT a (T )
P
V b V ( V b)
2 2
R 2 TC R 2 TC
a (T) (Tr , ) 0.42748 (Tr , )
PC PC

(Tr , ) 1 (0.480 1.574 0.176 2 ) (1 Tr )
1/ 2
2

RTC RTC
b 0.08664
PC PC

PC VC 1
ZC
R TC 3
 Cubic Equation of State:
Peng - Robinson Equation (1976)
RT a (T )
P
V b V ( V b)
2 2
R 2 TC R 2 TC
a (T) (Tr , ) 0.45724 (Tr , )
PC PC

(Tr , ) 1 (0.37464 1.54226 0.26992 2 ) (1 Tr )
1/ 2
2

RTC RTC
b 0.07779
PC PC
PC VC
ZC 0.30740
R TC
 Example 3.8

Given that the vapor pressure of n-butane at 350 K & 9.4573

bar, find the molar volumes of saturated vapor and
saturated liquid n-butane at these conditions as given by:
a. Van der Waals
b. Redlich/Kwong
c. Soave/Redlich/Kwong
d. Peng-Robinson
 Application of The Virial Equations
At low to moderate pressure, it is common to use truncated virial
equation: PV BP
Z 1
RT RT
At pressure above the range of applicability of the above eqn, the
appropriate form is: PV B C
Z 1
RT V V2

Benedict/Webb/Rubin equation:
RT B0 RT A0 C0 / T 2 bRT a a c
P 1 exp 2
V V 2
V 3
V 6
VT V
3 2 2
V
and its modifications are inspired by volume expansion virial eqn
and are used in the petroleum & natural gas industries for light
hydrocarbons.
 Example 3.7

Reported values for the virial coefficients of isopropanol

vapor at 200oC are:
B = -388 cm3 mol-1 C = -26000 cm6 mol-2

Calculate V and Z for isopropanol at 200oC & 10 bar by:

a. The ideal gas equation
b. Two term truncated pressure expansion virial
equation
c. Three term truncated volume expansion virial
equation
 Pitzer Correlation for
the Second Virial Coefficient

BP BPC Pr
Z 1 1
RT RTC Tr
BPC
B0 B1
RTC

0.422
B 0.083 1.6
0

Tr

0.172
B 0.139 4.2
1

Tr
 Generalized Correlations 4 Gases:
Pitzer type:Lee -Kessler Z Z 0
Z1

Tr

Z0

Pr
 Generalized Correlations 4 Gases:
Pitzer type:Lee -Kessler
Z Z0 Z1

Tr

Z0

Pr
 Generalized Correlations 4 Gases: Z Z0 Z1
Pitzer type:Lee -Kessler

Tr

Z1

Pr
 Generalized Correlations 4 Gases:
Pitzer type:Lee -Kessler Z Z 0
Z1

Tr

Z1

Pr
 Real Gas, EOS

Calculate Z and V for steam at 250oC and 1,800 kPa by the

following:
a. Ideal gas equation
b. Truncated virial equation with the following
experimental values of virial coefficient:
B = -152.5 cm3 mol-1 C = -5,800 cm6 mol-2
c. Pitzer correlation for virial equation
d. Pitzer-type correlation of Lee Kessler
e. Steam table
f. van der Waals equation
g. Redlich/Kwong equation
h. Soave/Redlich/Kwong equation
i. Peng-Robinson Equation
Correlation for Liquids: Rackett Equation

(1 Tr ) 0.2857
V sat
VC ZC
 Correlation for Liquids:
Lydersen, Greenkorn & Hougen
 Problem 3.45

A 30 m3 tank contains 14 m3 of liquid n-butane in

equilibrium with its vapor at 25oC. Estimate the
total mass of n-butane in the tank. The vapor
pressure if n-butane at the given temperature is
2.43 bar.