SMJC 2243

Chemical Engineering Thermodynamics

2018/2019-2

Thermodynamic Properties of
Fluids

Norhuda Abdul Manaf

Malaysia – Japan International Institute of Technology
(MJIIT)

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 SMJC 2243 - 2015/2016 - 2

Teaching Schedule
Week 1 Introduction to Chemical Engineering Thermodynamics
PIC: Prof Tsuji
Week 2 Volumetric Properties of Pure Fluids
PIC: Prof Tsuji
Week 3 Heat Effects – Part 1
PIC: Dr Huda
Week 4 Heat Effects – Part 2
PIC: Dr Huda
Week 5 Volumetric Properties of Pure Fluids (cont)
PIC: Prof Tsuji
Week 6 Thermodynamics Properties of Fluids
PIC: Dr Huda
Week 7 Solution Thermodynamics: Theory
PIC: Dr Huda
Week 8 Test 1 (25/3/2019)

2
 SMJC 2243
Chemical Engineering Thermodynamics
2018/2019-2

Thermodynamic Properties of
Fluids

Norhuda Abdul Manaf

Malaysia – Japan International Institute of Technology
(MJIIT)

3
 SMJC 2243 - 2015/2016 - 2

Topic Outcome
Week Topic Topic Outcomes
6 Thermodynamic Properties of Fluids It is expected that students are able
to:
• Introduction to thermodynamic
properties • Derive and apply the relation of the
canonical parameters (e.g. T and P)
• Fundamental property relations for and thermodynamic properties (e.g. H,
homogeneous phases U, S, and G).

• Residual properties • Estimate the entropy and enthalpy for

• Equation of state the real fluid using residual properties.
• Generalized correlation
• Table and Diagram of • Calculate the thermodynamic
Thermodynamic Properties properties of the system at the
specified conditions.
• Heterogeneous phase – Two phases
system

• Thermodynamic properties from

thermodynamic tables and diagrams.

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 SMJC 2243 - 2015/2016 - 2

Scope of Lecture

Introduction to thermodynamic properties

Fundamental property relations for

homogeneous phases

Residual properties

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 SMJC 2243 - 2015/2016 - 2

Process Design Analysis

IN SYSTEM OUT

PROPERTY CALCULATION

To find volume, V, we are completely prepared, whether it is ideal

gas, non-ideal gas or liquid.

But for other properties such as H, S, U, we have no idea what is

the pressure and volume functions especially for non-ideal gas.

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 SMJC 2243 - 2015/2016 - 2

Thermodynamic Properties

As such, we need to develop just such relations so that

calculations can be carried out.

We have numerically calculated the main thermodynamics

properties such as P, V, T.

Now we are going to calculate enthalpy, H and entropy, S from PVT

and heat-capacity data using 1ST and 2ND LAW property relations.

And develop generalized correlations which provide estimates of

property values in the absence of experimental information.

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 SMJC 2243 - 2015/2016 - 2

1st Law of Thermodynamic

Energy can neither be created nor destroyed. It can only

change forms.

In any process, the total energy of the universe remains the

same.

For a thermodynamic cycle the net heat supplied to the

system equals the net work done by the system.

8
 2nd Law of Thermodynamic

The entropy, S of an isolated system not in equilibrium will

tend to increase over time, approaching a maximum value at
equilibrium.

Q
S 
T

9
Property Relations for
Homogeneous Phases

10
 Other Thermodynamic Properties

PRIMARY THERMODYNAMIC properties are given as: P, V,

T, U and S.

OTHER THERMODYNAMIC properties arise only by

definition using the relation of these primary properties:

Enthalpy: H ≡ U + PV Chap. 2

Helmholtz Energy: A ≡ U – TS

Gibbs Energy: G ≡ H – TS

Note: P, pressure; V, volume ;T, temperature; U, internal energy; S, entropy

11
 Consider the Following System
• Closed system

• Homogenous
→ i.e. single phase and no change in composition e.g. Air

• Initial condition P1 and T1

• Final condition P2 and T2

1st Law (Energy Balance) for closed system,

dnU  dQ  dW

12
 Property Relations
1st law for closed system of dnU  dQ  dW Previous slide
n moles
A special reversible process

dnU  dQrev dWrev

From definition of entropy → Chap.5

dWrev  PdnV dQrev  TdnS

dnU  TdnSPdnV 

It can be applied to any process in a closed system (not necessarily

reversible process).

The change occurs between equilibrium states.

13
 Property Relations (cont.)
We know H ≡ U + PV

Differentiate these properties (H, A and G)

dnH  dnU PdnV  nVdP

Substitute for dnU
dnU  TdnS PdnV 

dnH  TdnSPdnV dPnV  nVd

dnH  TdnS nVdP

14
 Property Relations (cont.)
For other equations (A ≡ U – TS and G ≡ H –TS)

dnA   dnU TdnS nSdT dnG  dnH TdnS nSdT

Substitute for dnU Substitute for dnH

dnA   TdnS PdnV  TdnS nSdT dnG  TdnS nV dP  TdnS nSdT

dnA   PdnV  nSdT dnG  nV dP  nSdT

15
 Summary: Property Relations
For n = 1

dU  TdS PdV dA  PdV SdT

dH  TdS  VdP dG  VdP SdT

These are called fundamental property relations (FPR) → for

homogenous fluid of constant composition.

Notice that the FPR for Gibbs Energy is a function of commonly

measured variable P and T

G = G (T, P)
Note: The unit for TS and PV is energy unit
16
 Maxwell’s Equations

The thermodynamic properties can be expressed by equation for

each of these equations which called as MAXWELL’S EQUATIONS

 T    P   P    S 

V
      
 S  S  V  T V  V T

 T   V   V    S 
       
 P S  S P  T P  P T

Useful for evaluation of thermodynamic properties from

experimental data.

17
 Application of FPRs & Maxwell’s Eqn.
Need to know, how H and S vary with T and P

Use in the derivation of the general Q  dHP

equation H
Q  H 
CP   
H HT,P dT  dT P

Substitute
 H   H 
dH    dT    dP
 T P P T

H
dH  C PdT    dP
Energy balance
 P  T
Q W  dU dEk  dEp
From FPR
QPdV dU
dH  TdS  VdP
Q  dUPdV Note: For constant pressure, dH = dU + dpV = dU + PdV + VdP

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 Enthalpy as Function of T & P
Differentiate wrt. P at constant T
 H   V   V
   T 
 P T  T T
 H   S   P 
   T   V 
 P  T  T  T  P  T Substitute into

H
dH  CPdT    dP
 P T

 H   T S 
    V
 P T  T T  V 
dH  CPdT  V  T  dP
  T P 
From Maxwell’s equation,

 V    S 
    This general equation for H is in
 T P  P  T term of measure variable P, V, T
Note: wrt, with respect to

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 Entropy as Function of T & P
Derive general equation for S  S   Cp
 
 T P T

S  ST,P
From Maxwell’s equation,

dS  
S   S  Substitute
 V   S 
 dT   dP     
 T P  P  T T
 P P
 T

From FPR,

dH  TdS  VdP dT  V 
dS  C P   dP
T  T P
 H   T S   V P   T S 
         Cp This general equation for S is in
 P T  T P  T P  T P term of measure variable P, V, T

20
 Internal Energy as Function of P
Internal energy is given by equation U = H - PV

Differentiate →the pressure dependence of the internal energy,

 U    H  P V 
      V
 P T  P T  P T
Replace

 H   V 
   V  T 
 P T  T P

 U   V  P  V 
   T   
 P T  T P  P T

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 Summary: H, S f(T, P) & U f(P)
S   S 
dH  
H   H  dP
 dT    dS    dT   dP
 T P  P  T  T P  P  T

dH  TdS VdP  S   V    S 
   CP    
 T P  T P  P T
 H   V 
   T   V
 P T  T T dT  V 
dS  CP    dP
 H   H   T S  T  T P
   CP    
 T P  T P  T P
H  U PV
 H   V 
   V  T 
 P T  T P
 H   U   P V   V
 V    S       
     P P
T  T P
 T
 T P  T  T

 V   U   V   V 
dH  C P dT  V  T   dP    T   P 
  T P   P T  T P  P T
Note: H, enthalpy; S, entropy; U, internal energy
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 Application of General Equation H & S
For system with Ideal gas

RT  V   R
PV  RT V  
P  T P P

Substitute

 V  dT  V 
dH  C PdT  V  T  dP
Previous
dS  CP    dP
  T P  T  T P equation

dT dP
Enthalpy dH  C dT
ig ig dS  C
ig
R
ig
P Entropy
P T P
Note: superscript “ig” denotes an ideal-gas value

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 Application of General Equation H &S(Cont.)
Alternative forms for liquids

From Maxwell’s equation & the definition of volume expansivity

 H   V   S   V 
   V  T   1 β T V       β V
 P T  T P   P  T  T P
Substitu te Substitute
  V   dS  CP
dT  V 
   dP
dH  CPdT  V  T  dP
 T
 P  T  T P

for incompressible fluid

dH  CPdT  1βT VdP

dT
Enthalpy dS  CP βVdP Entropy
T

For liquids not near critical point the volume itself is very small , as
are ß and κ .Thus at most conditions P has little effect on the
properties of liquid.
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 Internal Energy & Entropy as f(T, V)
T & V often serve as more convenient independent variables than
do T & P.

S S
U
dU    dT  
U 
 dV dS    dT    dV
 T  V  V  T  T  V  V  T

 U   U   T S   U   T S   S    P 
  CV     P        
 T  V  V  T  V  T  T  V  T  V  V  T  T  V

 S 
dU  CVdT   T  P dV
  V T 
 S   P   S   C V
      
 V  T  T  V  T  V T

 P  dT  P 
dU  CVdT  T  P dV dS  C V   dV
  T  V  T  T  V

These are general equations relating the U and S of homogeneous

fluids of constant composition to T & V.
25
 Alternative Forms for Liquids

 P  dT  P 
dU  CVdT  T  P dV dS  C V   dV
  T  V T  T V


A change of state a constant V becomes :

 P   β
 
 T  V κ

β dT β
dU  C V dT  T PdV dS  C V  dV
 κ  T κ

26
 Gibbs Energy as a Generating Function
Thermodynamic property of great potential
G  GP,T dG  VdP- SdT
utility

d  dG  dT2

G 1 G
 RT  RT RT

G  H TS dG  VdP SdT

d   dP  dT2
G V H d G  G RTdP  G RT dT
 RT  RT RT  RT   P  T  T P

V G RT G RT

 T
H
 
RT  P T  T  G/RT = g(T, P)
RT P

27
 Remaining Properties

When G/RT is known as a function of T and P , V/RT and H / RT

follow by simple differentiation.

The remaining properties are given by defining equations

S H G U H PV
   
R RT RT RT RT RT

The Gibbs energy when given as a function of T & P therefore serves

as a generating function for the other thermodynamic properties.

28
Residual Properties

32
 Generic Residual Properties
The definition for generic residual property,

Residual property = Real property – Ideal gas property

M is molar value of any

M  MM
R ig
extensive thermodynamic
property e.g. V , U , H , S , or G
E.g.

HR  HH ig SR  S Sig GR  GG ig

To calculate H or H2 – H1, we shall use the HYPOTHETICAL PATH.

Note: V, volume ; U, internal energy; H, enthalpy; S, entropy; G, Gibbs energy

33
 Hypothetical Path
Consider,

H  H1  H2  H3

H  H1  Hig  H
2 3


H  H1ig H1  CPig  H
T2  T1  H2  Hig2 

H HR  Cig
1 P H
T2  T1H R2

H  CigP
H
T2  T1  HR2  H1R
Need to figure out how
to determine HR

Note: <Cpig>H, mean heat capacity and is given in Chap. 4

34
 Gibbs Free Energy
To determine HR, let us start with the Gibbs Free Energy,

G  GT,P

Divide by RT and differentiate,

d  dG  d    dG 
G 1 G 1 1 G
dT2
 RT  RT R  
T RT RT

Substitute FPR for dG  VdP SdT

d  dVdP  SdT

G 1 H TS dT  V dP  S dT  H dT  S dT
 RT  RT RT2 RT RT RT2 RT

d   dP  dT2
G V H
Note: FPR, fundamental property relations  RT  RT RT

35
 Residual Gibbs Energy
Let’s us do for residual Gibbs  GR  V R HR
energy d  dP  dT
 RT  RT RT 2

GR  GG ig

Divide by RT & differentiate, Apply criterion of exactness

 GR 
d
 G
  d
 Gig  
V R   GR RT   HR  GR RT
  d     T  
 RT   RT   RT  RT  P T RT  T  P

Apply equation Rearrange and integrate from ideal

gas (P = 0) to arbitrary P (actual P)
d  dP  dT2
G V H
 RT  RT RT
 GR 
act.
VR

P

G R
 V V  ig
HH  ig
d 
 RT 

0 RT
dP
d  dP  dT ig

 RT  RT RT2
36
 Residual Properties
GR P VR V Vig
 0  0 dP   dP Substitute into
RT RT RT
HR  
  GR RT 
 T  
RT
 T P
GR  ZRT RT 1
    dP
RT  P P  RT
HR  Z  dP
P
 T   
GR Z1dP RT 0
 T P P
RT  P

Similarly from

Differentiate wrt. T at const. P SR HR GR

 
R RT RT

d GR /RT 
   Z/P   1/P dP
dT  T P  T P SR P  Z  dP dP
  Z 1
P
 T   
1 Z Z dP R 0 T
 P P 0 P
      
P  T P  T P P
Hence, need data either PVT or
Note: wrt, with respect to correlation for Z to solve HR & SR
37
 Enthalpy for Real Gas
Consider,

HR  HH ig
T T
H  H   C H
ig
0
ig
P
R
H  H  H   CPig
ig ig ig
0
T0 T0

H  H0ig  CigP
H
T T0 H R Note: here the reference
state is ideal gas at T0, P0.

H = H2 – H1 is calculate as follows,

H1 Hig  Cig T  T  H R
0 P 1 0 1
H2  Hig  Cig
0 P T2 T 0H R2

H H2 H1  CPig

H
T2  T1  HR2  HR1

38
 Entropy for Real Gas
Similarly,

SR  S Sig
T
dT P
S S   C
ig
0  Rln  SRig
P
T
T P0
0

P
S  Sig0 RMCPST0,T;A,B,C,D T  T0 Rln  SR
P0

S  Sig  Cig ln
T2
Rln 2  S 2 S 1
P R R
0 P S
T1 P1

   2 D   1  1  
C ig 
 R A  BT0 CT0  2 2 
   Chap. 5
P
S    T0  2    ln  
  
39
Summary: H & S from Residual Properties
 ig T ig   P  Z  dP 
H  H H  H0   CP    RT 2   
ig R

 T0   0
 T P P 

 Z  dP 

 Hig0  R ICPHT0,T;A,B,C,D RT  2
P
  
 0
 T P P 


 Hig0  C Pig T  T0  RT2   
  Z 
P dP 
 T P P 


H 0

 P  Z  dP 

Hig0  R MCPHT0,T;A,B,C,D T T0   RT 2    
 0
 T P P 

 ig T ig dT P   P  Z  dP dP 
  Z1 
P
S  S  S  S0   C P
ig R
 Rln  R  T   
0 T
 T0
T P0    P P 0 P 

   
 Sig0 RICPH T0,T;A,B,C,D  Rln P  R  T  Z  dP  Z 1 dP 
P P

 P0  
0  T P P 0 P 

 T P  P  Z  dP dP 
 0 Z 1 
P
 Sig0  CigP ln  Rln  R  T   
0 T

S T0 P0    P P P 

   
 Sig0 RMCPS T0,T;A,B,C,D T  T0 ln T  Rln P  R  T  Z  dP  Z 1 dP 
P P

 T0 P0  
0  T P P 0 P 

40
Residual Properties by
Equations of State

44
 HR & SR by EoS
HR P  Z  dP SR P  Z  dP dP
  Z 1
P
 T     T   
RT 0
 T P P R 0 T
 P P 0 P

Requires an equation which can be directly solve for Z(or V) = f(P, T)

Residual Residual
properties from properties by
the virial EoS cubic EoS

Calculation of residual properties for gases or vapors through use

of virial equations and cubic EoS.
Note: EoS, equation of state

45
 2-Term Virial EoS
BP
2-term virial equation Z 1 
GR Z1dP RT GR BP


RT P RT RT

BP
Z 1 
H R
 Z  dP RT HR P   BP   dP
 T 0  1
P
 T    
RT 0
 T P P RT  T  RT  P P

HR P  P  1 dB B 
 T     2 
RT 0
 R  T dT T  P

HR P  B dB 
RT  R T  dT
 

SR HR GR SR P dB
  
R RT RT RT R dT
Note: EoS, equation of state
46
 Alternative Form

Alternative form for PV = ZRT Note also that ρ → 0 when P → 0,

ρ  Z  dρ
P  ZRT GR
 T     Z 1
RT 0  T 
ρ ρ

dP  RT Z dρ  ρdZ

Combination with P = ZρRT

dP dρ dZ HR
   Z  dρ
ρ
P ρ Z  T     Z 1
RT  ρ ρ
0 T

Substitution for dP /P
SR ρ Z  dρ ρ dρ
G R
ρ dρ  lnZ  T      Z1
  Z 1  Z 1 lnZ RT 0 T
 ρ ρ 0 ρ
RT 0 ρ
Integral is evaluated at constant
47
 3-Term Virial EoS

Z 1 Bρ  Cρ2 P  ZRT

GR

Z1dP GR 3
 2Bρ  Cρ2 lnZ
RT P RT 2

HR P  Z  dP HR  B dB   C 1 dC  2 
 T     T    ρ  T  ρ 
RT 0
 T P P RT  T dT   2 dT  

SR HR GR SR  B dB  1  C dC  2 
 
RT
 lnZ  T    ρ   ρ 
R RT RT  T dT  2  T dT  

Application – useful for gases up to moderate P

Requires data for both the 2nd & 3rd virialcoefficients.

Note: EoS, equation of state 48 Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 HR & SR by Cubic EoS
aT
q
RT aT bRT 1 ρb
P  Z q
V b V  εbV  σb 1ρb 1 ερb1σρb

ρ dρ
H R
 dlnαTr    Z 1  ln1 ρb qI
 Z 1  1qI
0 ρ
RT bP
 dlnTr  β
 Z  dρ
ρ dq
0  T ρ ρ   dT I
RT
SR dlnαTr 
 lnZβ qI
R dlnTr
ρ dρb
R
I 0 1 ερb1 σρb (Const. T)
 Z 1 lnZ  β qI
G
RT

Case I : ε ≠ σ Case II : ε = σ
Note: We first have to solve for Z, using
1  Z  σβ β eqn. 3.52 for vapor phase and 3.56 for a
I  σ εln  Z εβ  I
  z εβ liquid phase

Note: EoS, equation of state 49

 Example 2

Find values for the residual enthalpy HR and the residual entropy SR for
n-butane gas at 500 K and 50 bar as given by Redlich/Kwong equation.

Ans: Tutorial 2, Z = 0.695, HR = –2.303  103 J/mol, SR = –5.461 J/mol.K; Tutorial3, Z = 0.774, HR = –3.751  103 J/mol, SR = – 4.795
J/mol.K; Tutorial 4, Z = 0.691, HR = –4.985  103 J/mol, SR = –7.422 J/mol.K.
50
 OUTDOOR TUTORIAL CLASS

ONLY APPLICABLE FOR SECTION 2

(TUESDAY)

Time: 4 – 7 pm
Venue: Free-location
Instruction: T questions will be posted in e-learning
Attendance: Group work –COMPULSARY (- 50%)
Submission: 12.3.2019 by 7.00 pm
 Generalized Property
Correlations for Gases

51
 The Lee/ Kesler Correlation
P  Pc Pr T  Tc Tr HR Pr  Z 
HR P  Z  dP  dPr
 T    Tr2  

RT 0 T
 P P
RT
c
0
 Tr Pr Pr

SR ρ  Z  dρ ρ dρ
 T     Z1 SR  Z  dPr  Z 1 dPr
0
Pr P
 Tr 
r

R 0 T
 ρ ρ ρ
 Tr P Pr
0
R 0 Pr
r

Z  Z 0  Z1

HR  Pr  Z0  dP   Pr  Z1  
 Tr  
2  r
  ω Tr  
2  dPr 
RTc 

0
 Tr Pr Pr   0
 Tr Pr Pr 

Pr   Pr 
 dP
SR  Z0  dP  Z 1

  0 Tr    Z 0 1 r  ω  Tr    Z1 r
R   Tr P r  Pr   Tr Pr  Pr
0


HR 
HR SR SR0 SR
0 1
HR 1
 ω  HRB(TR, PR,OMEGA)  ω  SRB(TR, PR,OMEGA)
RTc RT c RTc R R R
Note: (HR)0/RTC, (HR)1/RTC, (SR)0/R, (SR)1/R → Tables E.5 – E.12

52
 Generalized 2nd Virial Coefficient
Pr Pr
Z  1B 0 ωB1
Tr Tr

Differentiate

0 d1/Tr  d1/Tr 
 Z    dB0  1     dB1  1 
   Pr     B   ωPr   B 1 
T  dT T   
 r  Pr   r  r  dTr    r  r 
dT T dTr 

 Z    dB0  1  B0    dB1  1  B1 
   Pr      2   ωPr     2 
   
 Tr  Pr   dTr  Tr  Tr    dTr  Tr  Tr 

Substitute into HR Pr  Z   Z  dPr

 Tr2    dPr SR dP
  Z1 r

Pr Pr
 T
RT  Tr Pr Pr  Tr Pr Pr
r 0
c
0 R 0 Pr

HR P  B
0
B0   B1 B1  SR  B0 B1 
 
Pr
 Tr     ω    T
2 r

RTc  T r Tr   T r Tr   Tr
r 0
0 R Tr 

53
 Generalized 2nd Virial Coefficient

B, B0 & B1 are f(T) only, the terms in parenthesis are constants

→integrate at const. T

HR  0 dB 0  1 dB 1   SR  dB0 dB1 
 Pr B  Tr  ωB  T r   P r  ω 
RTc  dTr  dTr  R  r
dT dTr

HRB(TR, PR,OMEGA) SRB(TR, PR,OMEGA)

Where,

0.422
B  0.083  1.6 dB0 0.675
0

Tr dTr Tr2.6

0.172 dB1 0.722

B  0.139  4.2
1

Tr dTr Tr5.2

54
 Z, HR & SR for Gas Mixtures
Z  Z0  Z1

HR HR 0 
H 
R 1
SR SR 0 
SR 
1
 ω  ω
RT RT RT R R R
c c c

Where,

ω  y iωi Tpc   y i Tc i Ppc   y iPc i

i i i

T P
Tpr  Ppr  Pseudoreduced parameters
Tpc Ppc

(HR)0/RTC, (HR)1/RTC, (SR)0/R, (SR)1/R refer to Tables E.5 – E.12

Z0 & Z1 refer to Tables E.1 – E.4

55
Re-do Example 6.9

56
Phase Equilibrium for System
with Pure Substance

58
 Introduction
A phase transition (e.g. melting, vaporization, or sublimation) at const.
T & P occurs whenever the phase boundaries (refer PT diagram) is
crossed.
→ Molar/ specific values of the extensive thermodynamic properties
change abruptly.

Thus the molar/ specific vol. of sat. liq. is very different from the
molar/ specific vol. of sat. vap. at the same T & P.
→ True as well for U, H and S.

Molar/ specific volume Gibbs energy for pure substance

→ Does not change

For 2 phases  &  of pure species

Gα  Gβ coexisting at equilibrium

59
 Two Phase Systems

Consider the following system For this system

• Initial cond.: sat. liq., T, P, Gl, Ul GT,P, nl, nv 

• Final cond.: sat. vap., T, P, Gv, Uv
nG   nG 
dnG    dT    dP
 T P,nl ,n v  P  T,nl ,n v
From FPR
nG   nG 
  l 
dn l
  v  dnv
dnG  ndG  nVdP  SdT  0  n  T,P,n v  n  T,P,nl

Also look at the following equilibrium For const. T and P

system

• Closed system dnG  Gldnl  G v dn v

• 2-phase in equilibrium (VLE) at T,
P, nl, nv

Note: FPR, fundamental property relations ; VLE, vapor liquid eq6u0ilibrium

 Two Phase Systems (cont)

Where we define partial molar Substitute

property as,
 
dnG   G l  G v dnl  0
 nG   nG 
Gl   l 
Gv   v 
 n  T,P,nv  n  T,P,nl

This is the phase equilibrium

Since this is pure substance G G
l v criteria (or VLE criteria) for
pure substance
Gl  G l Gv  G v
Check (steam table at Tsat = 100 C)

From mole balance Gv  Hv  TSv

nv
n  n n
l v t  2676  373.15(7.3 554)  68.6kJ/kg

dnl  dnv  dnt nl Gl  Hl  TSl

dnl  dnv Note: closed system  419.1  373.15(1.3 069)  68.6kJ/kg

61
 Clapeyron Equation

Consider system A in equilibrium at dPsat ΔSlv


dT ΔVlv
• Sat cond. 1, T1, P1, Gl1, Gv1
• Sat cond. 2, T2, P2, Gl2, Gv2
From FPR
dH  TdS  VdP
From equilibrium criteria
For vaporization
of pure substance
Gl1  Gv1 Gl2  Gv2
Hlv  TSlv  0
From equilibrium criteria (2 -1)

Gl2 Gl1  Gv2 G v1

dG  dG dPsat Hlv

l v

dT TVlv Clapeyron eqn.

VldPsat S ldT  V vdPsat S vdT
62
 Clausius/Clapeyron Equation
The equation could also be written as follows,

dlnPsat Hlv
 Clapeyron eqn.
d1/T  RZlv

At low P, Vv = RT/Psat , for

ideal gas and also Vl <<Vv
Clapeyron becomes,
dPsat ΔHvap
 Clausius/Clapeyron eqn.
sat
dT RT/P
Or
dPsat /Psat ΔHvap dlnPsat
 and H vap
 R
d1/T 
sat
dT/T R

To solve this equation, we only need either VAPOR PRESSURE

DATA or EQUATION RELATING VAPOR.
63
 Vap. P (Psat) vs. Boiling Point T (Tsat)

Antoine equation – gives a rough approximation of the vapor-pressure

relation for the entire T range from triple point to the critical point.

B
lnPsat  A 
TC

Wagner equation – vapor pressure data over wide T range

A  B 1.5  C 3 D 6
lnP sat

1 
r

  1 Tr
Note: See Table B.2 for the constant →A, B, C, and D

64
 Lee/ Kesler Correlations

lnPrsat Tr   lnPr0 Tr  ωlnPr1Tr 

Where

6.09648 1.28862lnT  0.169347T 6

lnPr0 Tr  5.92714  r
r
Tr

15.6875 13.4721lnT  0.43577T 6

lnPr1Tr   15.2518  r
r
Tr

Reduce vapor P corresponding Reduce normal boiling point

to 1 standard atm.

ω
lnPrsat 
lnPr0 Tr

lnP T 
n n
1
r rn

This correlations was developed for non-polar liquids (water

insoluble)
65
 Two-Phase Liquid/Vapor System
When a system consists of sat.-liquid and sat.-vapor phases
coexisting in equilibrium, the total value of any extensive property of
the 2-phase system is the sum of the total properties of the phases:

Alternative form
 
M  1 x v Ml  x vMv M  Ml  x v Mlv
M represents V, U, H, S, etc.
E.g. V = (1 – xv)Vv + xvVv

xl & xv represent the mole fractions of the total system that are liquids
& vapor.

xv is also known as quality, that is the mass fraction of vapor in the

system.

67
 Thermodynamic Diagrams
Show relationship of thermodynamic variables (T, P, V, H, S) on the
graph for a particular substance.

E.g.
• T S diagram, P H diagram, P V diagram, H T diagram
• H S diagram (known as Mollier Diagram)

Useful for analysis of thermodynamic processes as the paths of

processes are easily traced and visualized.

69
 P H Diagram

Note: PH diagrams for CH4 and tetrafluoroethane →App. G

70
T S Diagram

71
 Mollier Diagram

Note: Mollier diagram for steam on the inside book cover (Ref.: Smith et al. (2001). Introduction to Chemical Engineering
Thermodynamics. 6th Ed. McGraw Hill, New York).
72
 QUIZ

Propane gas at 1 bar and 35 C is compressed to a final state of 135 bar

195 C. Estimate the molar volume of the propane in the final state
and the enthalpy and entropy changes for the process. In its initial
state, propane may be assumed as an ideal gas.

73 Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Tables of Thermodynamics
Properties

74
 Thermodynamic Tables
Enable us to read values of thermodynamic properties accurately.

Usually requires interpolation (as well as extrapolation).

E.g.

• Ammonia Table, Freon Table, Methane Table, Propane Table

• Saturated Table (T vs. P, Vsat. liq., Vlv, Vsat. vap., Usat. liq., Ulv, Usat.
vap., Hsat. liq., Hlv, Hsat. vap., Ssat. liq., Slv, Ssat. vap..
• Superheated Table (P and T vs. V, U, H, S →e.g. App. F)
• Compressed Liquid Table.

After completion of Chap 3, 4 and 6, you should be well equipped to

develop thermodynamic table of pure substance.

75
 SMJC 2243 - 2015/2016 - 2

Thank You

Special Thanks to Dr Mohd Asmadi Bin Mohammed Yussuf, FKT UTM.

77