Chemical Engineering

Thermodynamics
Beijing University of Chemical Technology
Zhiping Liu
2016.9.2

The Scope of Thermodynamics

work

heat

Process

Laws
energy

State

 PVT
Volumetric Properties
of Pure Fluids

Questions
Liquid, Vapor/Gas, Fluid?
Phase behavior
Visualization
Any applications?

Phase Behavior of Pure Fluids

Critical Point f=0

Degree of Freedom
and Phase Rule
One phase
Saturated line
Iso{X}(T/p/V)
Triple point

PV diagram of pentane

PT and PV Diagrams

isotherm

Shrink on solidification

PT and PV Diagrams

Expand on solidification

T-V

Isopiestic
isobaric

Isochore in PV/PT Diagram

Exercise:

1 . PV EF,GH
2. V1 V2 ?

Saturated Vapor Pressure and

Clapeyon-Clausius Equation
Criteria for Phase Equilibrium
Gm

( )

Gm

p ( ) p ( )

( )

T ( ) T ( )

dGm ( ) dGm ( )
( )

( )

( )

Sm dT Vm dp S m dT Vm ( ) dp

dp tr S m

dT trVm
dp tr H m

dT T trVm

i ( ) i ( )

1. Phase Equilibrium
2. T-dependent
Ex: Solidification

VLE: liquid gas

Z : 1

Antoine

B
ln p A
T C
s

p tr H m
dp tr H m

dT T trVm RT 2 tr Z

vap H m
d ln p s

d (1/ T )
R

Be careful Unit
P Pa/mmHg/atm
T K/OC

Be careful applicable T range

Water @ NIST Webbook

http://webbook.nist.gov/cgi/cbook.cgi?ID=C7732185&Mask=4&Type=ANTOINE&Plot=on

I cant find the

coefficients!

Modeling PVT Behavior

What is EOS ?
(Equation of State)

f p, V , T 0
V=V(T,p)

p=p(T,V )

pV
Z
Z ( p, T )
RT
Compressibility Factor

Note: V is the specific volume (molar volume)

- would be Vm in other textbooks

Properties available in Experiments

P, V, T
The first derivatives
1 V

V T

1.
p

dV
dT dp
V

1 V

V p T
p

T V

Usage

2.

For liquids

3.

For ideal gases

4.

Unit / Typical ranges

Ideal Gas
Macroscopic
pV RT
Z 1

Microscopic (molecular scale)

1. No interactions
2. No volumes

1. Can ideal gases be liquefied/solidified

2. Real Gas Ideal Gas

Z of Real gases

Non-ideality
Molecule size and shape

Intermolecular forces
attraction vs. repulsion
( LJ Yukawa)

How are these interactions

relevant to EOS?

Describing Non-Ideality
Method I: Virial Equation
Z = Z(T,p)
p
p
'
Z 1 B (T )
C (T )
RT
RT
'

B (T ) C (T )
Z 1
2 L
V
V

1.
2.
3.
4.

Units of Virial coefficients

(B,C) (B,C,.)
Which one should I use ?...
How to obtain the coefficients?

B' B
C ' C B2
Ex.(op.)

Truncation of Virial Equation

p< 1MPa

pV
Bp
Z
1
RT
RT
RT
V
B
p

p< 5MPa

pV

B
Z
1
RT
V

B C
Z 1 2
V V

More terms are need in higher pressure

Note: not applicable in really high pressure

VLE

Source of
Virial coefficients
Handbook/Database
Correlated via pVT data
pV

B 1lim
1 V

0
V
RT

pV

C 1lim
1 V B V
V 0
RT

(2/4-4)
(2/4-5)
Temperature dependence of
Virial coefficients

Virial Coefficients of Ar

Ex.
Obtain B and C from PVT data of Ar.
1. PVT data via NIST webbook
2. Choose one temperature
3. Use eqns. 2/4-4 and 2/4-5 (P9)
4. Plot Z, (Z-1)V,((Z-1)V-B)V)~1/V
5. Fit: Excel/Origin/Matlab/Gnuplot

 2/4-1 SO2 431 K , Virial

B= 0.159 m3kmol-1 C=9.010-3 m6kmol-2

SO2 431 K 1 MPa
PV
B C

2
Virial
RT
V V

p=1106 Pa R=8.314103 m3 Pakmol-1K-1

B= 0.159 m3kmol-1 C=9.010-3 m6kmol-2 T=431 K

0.0279V3 V2 0.159 V 910-3=0

RT 8.314 103 431

V

3.58
6
p
110

m3kmol-1

1 .
2 .
3 .

Accuracy of Virial Equations

From: TABLE 4-4

Ranges of Conditions for Accurate Z
Values from Virial Equations Using
Methane Expressions from Setzmann
and Wagner (1991)
Reid RC, Prausnitz JM & Poling BE,
The Properties of Gases and Liquids 5th,
0071499997, 2001, McGraw Hill

Vapor
T/Tc>1.05; p/pc<5

Saturated Vapor

Virial coefficients and

Intermolecular forces

1
1
B(T ) f12 dR2 exp p ,12 / kT 1 .4 r 2 dr
2
2 0
1
C (T ) f12 f13 f 23dR2 dR3
3! V

Hard sphere
B=2/3d03=4v0
C=10v0

Pair potential

(r)

d0

Extended Virial equations

Benedict/Webb/Rubin (BWR) equation

BWRS equation

Martin-Hou equation

Homework

Z2: 2-19
SVN6: 3.50. What is the pressure in a 0.5 m3 vessel when it is charged
with 10 kg of carbon dioxide at 30 C?

Exercise

Due 20160930

Derive the relationship of the virial coefficients in two

forms of virial EOS
(SVN6, eqs. 3-11 and 3-12)

Obtain virial coefficients B and C via PVT data of

methane(CH4).
Tips:
1. PVT data via NIST webbook (http://webbook.nist.gov/chemistry/fluid/)
2. Choose one temperature
3. Use eqns. 2/4-4 and 2/4-5 (Z2, P9)
4. Plot Z, (Z-1)V,((Z-1)V-B)V)~1/V
5. Fit: Excel/Origin/Matlab/Gnuplot