CHAPTER 2

THERMODYNAMICS PROPERTIES OF FLUIDS

1 EQUATIONS OF STATE FOR PURE FLUIDS

PROPERTIES (EOS)
1.1

Introduction

- GREAT
MANY
APPLICATIONS
THERMODYNAMICS
CONCERNED
WITH
BEHAVIOUR OF FLUIDS (LIQUIDS- GASES).

OF
THE

- 1ST AND 2ND LAW PERMIT TO CALCULATE HEAT

AND WORK ASSOCIATED WITH VARIOUS TYPES OF
PROCESSES INVOLVING FLUIDS.
- THIS REQUIRES THE PROVISION OF DATA WHICH IS
NEEDED TO EVALUATE THE
CHANGES IN
THERMODYNAMIC
PROPERTY
DURING
THE
PROCESS.
- DATA IS IN THE FORM P.V.T AND THERMAL DATA
(CP, CV)
1.2

P. V. T. DATA

- PURE FLUID IS IN AN EQUILIBRIUM STATE WHEN

TWO INTENSIVE VARIABLES ARE FIXED AND THEN
ALL PROPERTIES ARE UNIFORM THROUGHOUT.
- THERE
EXIST
SEVERAL
THERMODYNAMIC
DIAGRAMS WHICH CONTAIN THE INTENSIVE
PROPERTIES OF A PURE FLUID

- OFTEN P.V.T ARE FITTED TO ALGERBRAIC

EQUATIONS CALLED EQUATION OF STATE.
- ADVANTAGES OF E.O.S ARE DATA REDUCTION AND
EASE OF CALCULATIONS.
- - EQUATION OF STATE MAY BE SOLVED FOR ANY
ONE OF THE 3 QUANTITIES (P.V.T)
EXAMPLE

V= f ( P,T)
V
V
dV =
dT +
dP
T P
P T

1.3

EQUATIONS OF STATE

A) VIRIAL EQUATIONS OF STATE

I)

IDEAL GAS

PV= RT
(VALID AT LOW DENSITY AND LOW
PRESSURES)
DEFINE COMPRESSIBILITY FACTOR Z
Z= PV/RT
Z= 1 FOR AN IDEAL GAS.

- II) REAL GAS

- EQUATIONS FOR PV
- POWER SERIES OF P
PV = a + bP + cP2

PV
a
bP cP 2
=
+
+
RT RT RT RT

Z= 1+BP+CP2
a=RT

B= b/RT

C=c/RT

- Explicit in P CUBIC IN VOLUME

Z=

PV
B C
= 1 + + 2 + ...
RT
V V
P=

RT RTB RTC
+ 2 + 3 + ...
V
V
V

B,C, ARE VIRIAL COEFFICIENTS

- EQUATIONS ARE USED MAILY FOR LOW
TEMPERATURES PROCESSES.
- EQUATIONS FORM THE BASIC FOR A GOOD
NUMBER OF VLE CORRELATIONS

B) CUBIC EQUATIONS OF STATE

- ACCURATE DESCRIPTION OF P V T BEHAVIOR OF
FLUIDS ( WIDE RANGE OF T AND P)
- CUBIC EQUATIONS ARE SIMPLE CAPABLE OF
REPRESENTING BOTH LIQUID AND VAPOR
GENERAL FORM
P=

RT
a (T )

V b (V + b)(V + b)

a(T), b: PROPERTIES OF THE FLUID

,
: RELATION PARAMETERS.

VAN DER WALLS EOS (1873)

a(T)= a = CONSTANT
, = 0
P=

RT
a
2
V b V

a/V2 : ATTRACTIVE FORCES BETWEEN MOLECULES

(INTER MOLECULAR FORCES)
b: CORRECTIVE FORCE FOR THE VOLUME OCCUPIED
FOR AN IDEAL GAS: a=0

b=0

EVALUATION OF a AND b REQUIRES THE SOLUTION OF

THE FOLLOWING DERIVATIVES EQUATIONS
2P
2 = 0
V

=0
V T

AT CRITICAL CONDITIONS
A= 27R2TC/64PC

b= RTC/8PC

- Tc and Pc ARE KNOWN FOR MOST GASES

-REDLICH KWONG EOS

IN THIS CASE =0
P=

AND

=1

RT
a(T )

V b (V + b)

A= 0.4248R2 TC2.5/Pc
PENG ROBINSON
P=

RT
a(T )
2
V b (V + 2bV b 2 )

BEALTIE BRIDGEMAN EOS

P=

RT
C '
A
1
V +B 2
2
3
V VT
V

V=Molar Volume m3/mol

A= Ao( 1- a/V)

B=Bo(-b/V)

-BENEDICT WEBB RUBIN (BWR) EOS

P=

C 1
RT
BRT a
a
+ B0 RT A0 02 2 +
+ ...... +
3
V
T V
V
V

-EQUATIONS PALYED GREAT ROLE IN DETERMINING

THERMODYNAMIC
PROPERTIES
AND
PHASE
EQUILIBRIUM OF LIGHT HYDROCARBONS AND THEIR
MIXTURES.

1.4 GENERALISED CORRELATIONS

Theorem of corresponding State

-states that all fluids, when compared at the same
reduced temperature and reduced pressure, have
approximately the same compressibility factor.
Reduced temperature Tr= T/Tc
Reduced pressure Pr= P/Pc

The most popular parameter is the acentric factor,

introduced by Pitzer and defined as:
= 1.0 (log10 Pr SAT ) TR =0.7

=ACCENTRIC FACTOR
CAN BE DEFINED FOR ANY FLUIDS FOR TC, PC
TC, PC AND Vc are listed in Appendix

Generalized correlations for gases

Pitzer correlations for the compressibility factor

PITZER PROPOSED A CORRELATION

Z= Zo + Z1
Where Z0 and Z1 are functions of both Tr and Pr. So,
this equation is a simple linear relation between Z and
for given Tr and Pr.
When =0, the case for the simple fluids, Z0 becomes
identical with Z

The Pitzer form correlation developed by Lee and

Kesler found greatest use.

Generalized correlations for gases

The basis for this is the simplest form of the virial
equation:
Z= Zo + Z1

Pitzer and co. proposed a second correlation r

Zo= 1 + Bo Pr/Tr
Z1 = B1 Pr/Tr
1st order LEE KESSLER

Z= 1+ BP/RT = 1 + (BPc/RTc)(Pr/Tr) = 1+ BPr/Tr

B '' =

BPC
RTC

-PITZER PROPOSED A SECOND VIRIAL CORRELATION

Z = 1 + B0

PR
P
+ B 1 R
TR
TR

Ie
Zo= 1 +BoPr/Tr
Z1= B1Pr/Tr

B 0 = 0.083

0.422
TR1.6

B 1 = 0.139

0.172
TR4.2

PROPERTIES RELATIONS FOR HOMOGENEOUS

PHASES

- FOR A CLOSED SYSTEM WITH n MOLES

d(nU) =dQ + dW
dW=-Pd(nS)
dQ=Td(nS)
-CLOSED SYSTEM REVERSIBLE PROCESS

d(nU)= Td(nS)- Pd(nV)

RELATION CONSIDERS PROPERTY SYSTEMS (S,T,V,P)
-ADDITIONAL PROPERTY CAN BE DEFINED
H= U+ PV
A= U- TS

ENTHALPY
HELMOTZ ENERGY

G= H-TS GIBBS ENERGY

UPON MULTIPLYING BY n moles

d(nU)= Td(nS)- Pd(nV)

nH= nU+ nPV
d(nH) = d(nU) + d(nPV)
d(nH) = d(nU) + Pd(nV) + Vd(nP)
d(nU)= Td(nS)- Pd(nV)
d(nH) = Td(nS) + nVd(P)

d(H) = Td(S) + Vd(P)

d(nA)= d(nU)- TnS
d(nA)= d(nU)- Td(nS)- nSdT
d(nA)= -Pd(nV)- nSdT
SIMILARLY
d(nG)= nVdP- nSdT

FOR ONE MOLE

d(U)= Td(S)- Pd(V)

d(H) = Td(S) + Vd(P)
d(A)= -Pd(V)- SdT

d(G)= VdP- SdT

- IN GENERAL IF F IS A FUNDCTION OF (x, y) F(x,y)

THEN THE TOTAL DIFFERENTIAL OF F IS DEFINED AS
FOLLOWS,
F
F
dF =
dX +
dY
X Y
Y X

dF= MdX + NdY

M= ( F/ X)Y

N= (F/ Y)X

FURTHER DIFFERENTIATION
(M/Y)X = 2F/XY
(N/X)y = 2F/XY
- ORDER OF DIFFERENTIATION IS A MIXED SECOND
DERIVATIVE
(M/Y)X = (N/X)y
- APPLYING THIS PRINCIPLE ON THE PREVIOUS
EQUATIONS
d(U)= - Pd(V) + Td(S)
= MdX + NdY

(M/Y)X = (N/X)y
THEN
FOR U

(-P/S)V = (T/V)S

SIMILARLY FOR THE OTHER EQUATIONS ( H, A, G) WE

CAN OBTAIN

FOR U

-(P/S)V = (T/V)S

FOR H

(T/P)S = (V/S)P

FOR A

(P/T)V = (S/V)T

FOR G

(V/T)P = -(S/P)T

- THESE EQUATIONS ARE KNOWN AS MAXWELLS

EQUATIONS
- THERE ARE THE BASIS FOR DERIVATIVES OF A
LARGE NUMBER OF OTHER EQUATIONS RELATING
THERMODYNAMICS PROPERTIES.

EXAMPLE;
CONSIDER THE FOLLOWING EQUATION
- I)

d(H) = Td(S) + Vd(P)

(H/ P)T = T(S/P)T +V

SINCE (V/T)P = -(S/P)T FROM MAXWELL EQUATION

THEN
(H/ P)T = (S/P)T +V= - (V/T)P +V
- II) CONSIDER H(P, T) THEN
H = (H/ T)P dT + (H/P)T dP
NOW
AND

(H/ T)P= Cp
(H/ P)T = (S/P)T +V
H = Cp dT +(T(S/P)T +V)dP

SINCE FROM MAXWELL EQS (V/T)P = -(S/P)T

Then
H = Cp dT +(T(V- (V/T)P)dP
IF S(P,T) THEN
S = (S/T)P dT + (S/P)T dP
SIMILARLY IT CAN BE PROVEN THAT
If S(P ,T) THEN
S = Cp dT/T - (V/T)P)Dp

3 GIBBS ENERGY GENERATING FUNCTION

G= G(P, T)
dG= VdP SdT
DIVIDING BY RT
d(G/RT)= 1/R d(G/T) = 1/R ( dG/T GdT/T2)
d(G/RT)= VdP SdT
G= H -TS
H TS )dT 1
G VdP SdT
d
(
=

T
T2
RT
R
SdT HdT SdT
G V
d
dP

+
=
TR
TR
RT 2
RT RT

HdT
G V
d
dP
=
RT 2
RT RT

G
RT

G
RT

V
=

RT
T

H
=
2

RT
P

H
RT
= T
RT
T

4 RESIDUAL PROPERTIES
- THERE ARE NO CONVENIENT EXPERIMENTAL
METHOD FOR DETERMING NUMERICAL VALUES OF
G AND G/RT
- DEFINE RESIDUAL PROPERTIES
GR = G - GIg
G= ACTUAL GIBBS ENERGY
GIg = IDEAL GAS VALUE OF GIBBS ENERGY
OTHER PROPERTIES
VR = V - VIg
VR = V - RT/P
V =ZRT/P
VR = RT/P ( Z-1)
IN GENERAL
MR = M - MIg

- M= MOLAR VALUE OF ANY EXTENSIVE THERMODYNAMIC

PROPERTIES

HdT
G V
d
dP
=
RT 2
RT RT

 G IG
d
RT

V IG
H IG dT
=
dP
RT 2
RT

G R
RT

V R

RT

G R

HR

RT
= T

RT
T

GR = HR - TSR
SR/ R = HR/RT - GR/RT
AT T= CONSTANT

( )

G R
V R
dP

=
RT
RT

( )

GR

=
RT

V R

dP
RT

VR = V - VIg

( )

GR

=
RT

V V IG

RT

dP

( )

GR
dP

= ( Z 1)
P
RT
G R

HR

RT
= T

RT
T

HR
Z dP
= T

RT
T P P