CHEMICAL THERMODYNAMICS 2 PROPERTY RELATIONS FOR PURE FLUIDS

MODULE 4: THERMODYNAMIC PROPERTY RELATIONS FOR PURE FLUIDS

4.1 Aims
To present thermodynamic relations from which properties of pure fluids can be evaluated.

4.2 Learning outcomes

At the successful completion of this module, you should be able to:

1. Recognise and applying Maxwell equations in predicting properties of pure fluids.

2. Employ the different correlations in deriving property relations for fluids and in problem
solving.

3. Derive unknown properties of a pure fluid in single phase from other properties that can
be measured.

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4.3 Introduction
Thermodynamic data are best obtained from experiment. Pressure (P), Temperature (T), volume
(Vm) and mass of a fluid can be determined experimentally. The relationships between Cv, Cp
and temperatures can also be determined from experiments and from simple correlations.

However, there are some thermodynamic properties, which are not easily obtained
experimentally. Examples include internal energy (U), enthalpy (H), and entropy (S).
Tabulated data on U, H and S are obtained from correlations with properties that can easily be
measured. Such correlations have been derived from thermodynamic laws and principle of
energy conservation. Mathematical methods are very important tools in thermodynamics for
expressing relations between measured properties and derived properties.

The objective of this lecture is to present thermodynamic relations from which properties such as
internal energy, U, enthalpy, H, and entropy, S, of pure fluids can be evaluated.

Equations of state: These are essential for the calculation of properties. P-v-T properties are
commonly presented in form of:

1. Tabulated data (such as steam tables).

2. Graphs (such as: compressibility charts).
3. Analytical equations, using mathematical formulae (such as: ideal gas law, virial
equation, cubic equations)

Analytical or mathematical formulae are particularly very useful and convenient for expressing
relations between different properties.

4.4 Summary of Property relations for pure fluids in single phase

In this section we present a summary of mathematical formulae that are particularly useful and
convenient for expressing relations between different properties. We shall illustrate the
applications of these formulae with worked examples. (Details of the mathematics and
derivation of the equations are presented in the appendix at the end of this module).

(a) Summary of equations for differential of each thermodynamic property

Fundamental Fundamental property First partial differentials Maxwell Equations
properties relations [ Equation block “B”] [ Equation block “C”]
[Equation block “A”]
Internal energy, U
U=f(S,V) dU=TdS-PdV  V   S 
(i )     
 H   U   T P  P T
V   P   
Enthalpy, H  P  S  V  S  S   P 
 U   A 
(ii )    
H = f(S,P) dH=TdS+VdP T   S      V T  T V
 S V  T V
 V   T 
 H 
T 
 G 
S  
(iii )    
   S  P  P  S
Helmohltz free energy,  S  P  T  P
dA=-SdT-PdV  T   P 
A=f(T,V)  A   G 
P    V   (iv )     
 V T  P T  V S  S V

Gibbs Free energy, dG=VdP-SdT

G=f(T,P)
Note: For convenience, each category of differential has been referred to as “equation block.”

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(b) Summary of Specific heat relations

 S 
(i) CV  T   …………(b1)
 T  v
 S 
(ii) C P  T   ………………….. (b2)
 T  P
  P  
(iii) Internal energy and Cv: dU  CV dT  T    P dV …………. (b3)
  T V 
  V  
(iv) Enthalpy and Cp: dH  C P dT  V  T   dP ……………….. (b4)
  T  P 
C p dT  V 
(v) Entropy and Cp: dS    dP ……………………(b5)
T  T P

C dT  P 
(vi) Entropy and Cv: dS  V   dV ……………………….….(b6)
T  T  v

C P  V   P 
(vii) Ratio of specific heats:     …………………(b7)
CV  P T  V  S
  2V   P   P   V 
(viii) Specific heat differences: C p  Cv  T      T    …………(b8)
  V T  T V  T
 T  P  P
2

(c) Summary of important relations for liquid state

(i) isobaric thermal expansion:

1  V  1     V  V   
P            PV     ……….…(c1)
V  T  P   T  P  T P   T  P

(ii)Isothermal compressibility:
1  V  1     V   V   
T             T V    ………..(c2)
V  P T   P T  P T   P T
V 
(iii) ln 2    (T2  T1 )   P2  P1  ………………………………...(c3)
 V1 

Note: Isotherms for liquid phase are very steep and closely spaced. Consequently, both
 V  V
  (i.e. ) and   (i.e. ) are small. This is a characteristic behaviour of liquids
 P  T  T  P
outside the region of the critical point. Hence, liquids are said to be incompressible fluids
because  and  are very small (approximately zero). In practice, no real fluid is
incompressible because one cannot define a P-v-T equation for an incompressible fluid.

Definitions: (i)  (OR:  P)= coefficient of thermal expansion (0C-1)

(ii)  (OR:T)=coefficient of thermal compressibility (Pa-1)

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4.4.1 Explanation of the property relations equations

Equations in block “A” are the fundamental properties relations for pure fluids of constant
composition.
Equations in block “B” are first partial differential and are derived from equation block “A”.
Equations in block “C” are second partial differential and are derived from partial
differentiation of equations in block “B.”

The set of equations in block “C” is called Maxwell equations after James Maxwell who first
derived these relationships.
 The Maxwell equations form the basis for the derivation of many thermodynamic relations.

 The most useful relationship equations for enthalpy (H) and entropy (S) of a pure fluid are
expressed as functions of T and P.

 It is therefore, important to know how H and S vary with T and P. This information is
 S   H   S   h 
conveyed by the Maxwell equations:   ,   ,   , and  
 T  P  T  P  P  T  P  T
 Maxwell equations express the relationship between the primary thermodynamic properties.

 These equations are useful for calculating du and dh provided the equation of state
information is available.

 The summary of specific heat relations (b) and of important relations for liquid state (c) are
derived using Maxwell’s relations.

We shall now illustrate some applications of the different property relation equations.

4.5 Applications of these equations.

4.5.1 Application of Maxwell equations

 S 
Suppose   , a differential involving entropy, is required but data on entropy of the fluid are
 V  T
not readily available. One can obtain this differential from the following Maxwell equation:
 S   P   S   P 
     . The required derivative   can be obtained by simply evaluating  
 V  T  T  V  V  T  T  V
using available P-v-T data.

Worked example 1
S
Calculate   for water vapour at 2500C and Vm of 0.627 m3 kg-1. Use Redlich-Kwong
 V  T
equation of state and an appropriate Maxwell equation. Compare this with values from the
steam table.

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Solution:
S P
The required Maxwell relation is (From equation block “C”):     
 V T  T V
Assume: (1) the system is water at an equilibrium state.
P
(2) accurate values of the Maxwell relation:   for the required T and Vm, can be
  T V
determined from Redlich-Kwong (R-K) equation.
  1 
RT a RT aT  2 
R-K equation is: P
Vm  b
  

 1  Vm  b  V 2  bV
Vm2  bVm T  2  m m 
0.42878R 2Tc2.5 0.08664 RTc
where: a= and b=
Pc Pc

Step 1: partial differentiation of R-K equation:

 P  R a
   
 T V Vm  b   3 
2T  2 V m Vm  b 
 P 
Step 2: Calculate   from the differential.
 T  V
We need the critical constants to calculate “a” and “b” for water: Tc = 647.3K Pc =221.2 bar

0.08664RTc 0.08664x8.314x 647.3

Calculate “b”: b   2.108x10  5 m 3mol 1
Pc 221.2x10 5

0.42878R 2Tc2.5 0.42878x 8.3142 x647.32.5

Also, calculate “a”: a   14.28
Pc 221.2x105

Step 3: Convert Vm (m3 kg-1) to m3 mol-1 .

Molecular mass of water = 18 gmol-1 = 18 x10-3 kg mol-1

Vm (m3 mol-1 ) = 0.627 x18 x10-3 kg mol-1 =1.1286 x10-3 m3 mol-1 .

 P 
Step 4: Now calculate   :
 T  V

 P  R a
   
 T V Vm  b   3 
2T  2 V m Vm  b 
 P  8.314 14.28

 T
 
V   3
1.1286x10  2.108x10 - 6

1.
5 - 2 
2x 523 x1.1286x10 1.1286x10 - 2  2.108x10 - 6 
 743.12 JK 1m  3

P
Ans:    743.12 JK 1m  3
 T  V

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Comparison with values from steam table:

 From steam table, at a constant temperature of 2500C, we obtain values of entropy (S) and
specific volume v(m3 kg-1) as follow:

Vg(m3 kg-1) 1.601 1.199 0.7965 0.5953 0.4745

-1 -1
S (kJ kg K ) 7.843 7.708 7.517 7.379 7.271
 Plot a graph of S against Vg and draw the tangent to the curve at the point where V=
3 -1
0.627 m kg . Next obtain the slope, dv  T
ds of the tangent at this point. This is the required

value.

This step is illustrated in Figure 4.1.

7.9

7.8
Specific entropy (kJ kg-1 K-1)

7.7

7.6

7.5

7.4

7.3

7.2
0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7
Specific volume (m3 kg-1)

Figure 4.1: Graph of Entropy against specific volume, at a constant temperature of 250 0C.

From the graph, the slope of the tangent to the curve at Vm = 0.627 m3 kg-1 is:
7.24  7.7  0.46
  0.754 kJK 1m3  754 JK 1m  3
0.4  1.01  0.610

This result shows a difference of 1.4% between the calculated values using R-K equation, and
value obtained using the steam table. It also illustrates the accuracy of Maxwell’s equation for
estimating properties that cannot easily be measured or that are not readily available. To
improve this accuracy, we could use a more rigorous cubic equation such as Soave-Redlich-
Kwong OR Peng-Robinson (see Module 2).

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Worked example 2

Using the Redlich-Kwong equation of state, find an expression for changes in specific internal
energy of a gas between two states, at constant temperature, where the pressures are P1 and P2
respectively.

Solution

Using the relationship between dU and Cv [equation (b3)]:

  P  
dU  CV dT  T    P  dV ……… (we2.1)
  T V 
For an isothermal change, dT = 0
  P  
Therefore, the equation reduces to: dU  T    P  dV
  T V 

We need to solve this differential equation

Integrate:
u2 v2  
 P 
 dU   T    P  dV …… (we2.2)
u1 v1   T V 

RT aT 2
1 
R-K equation is: P 
Vm  b Vm2  bVm  .. (we2.3)
P
Differentiate to obtain an expression for  
 T V

 3 
P  R aT  2 
   

T V Vm  b 2 V 2  bV
m m  .......(we2.4)

P 
Substitute for P from (eqn. we2.3)and   from equation (we2.4) into equation (we2.2):
 T  T

v2 
aT  3 / 2  aT  3 / 2  
u 2  u1    
RT
 
RT
  dV
v1  Vm  b  2Vm Vm  b  Vm  b  Vm Vm  b  

u1
3aT  3 / 2  3a u1 1
 
u 2 2Vm Vm  b 
dV 
1   2
2T 2 u 2 Vm  bV m  
3a v 2 1
U 2  U 1  
2T
1
2
 v1
Vm Vm  b 
dVm ........(we2.5)

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The RHS can be integrated by using partial fractions, thus:

1 1 1 1 
   
Vm Vm  b  b Vm Vm  b  

Substitute this into equation (we2.5):

v2  
3a 1 1
 U 2  U1     dVm
 1  v Vm Vm  b  
1
2T  2 

3a   V2   V  b  3a V V  b  
ln   ln 2   ln  2 1
U 2  U1 
2T

1   V1
2 
  V1  b 
2T

1
2

V1 V2  b  

3a V V  b  
Answer The required expression is: U 2  U1  ln  2 1 
 1  V1 V2  b  
2bT  2 
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Worked Example 3

Acetone is kept at 200C and 1 bar. Given the following properties for acetone at this condition:
=1.487x10-3 0C-1,  = 62x10-6 bar and V= 1.287 cm3 g-1, calculate:

P
(a)  
 T V

(b) the corresponding pressure when the acetone is heated at constant volume to 300C,

(c) the corresponding volume change when the acetone is changed to 00C and 10 bar.

Solution
dV
From equation (C1):  dT  dP
V
 P 
(a)   implies constant volume, therefore, dV = 0
 T V

putting dV = 0 into equation (C1) gives: dT  dP

dP   1.487 x10  3
    bar 0 C 1
dT V   6
62x10

dP  1.487 x10  3
   24 bar 0C 1
dT V 62x10  6

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(b) To find the corresponding pressure when heated at constant volume to 30 0C.

At constant volume, dT  dP

 T2 P2
  dT    dP
 T P1
1

 P2  P1   T2  T1   2430  20  240 bar


P2 = P2+240 = 1+240 = 241 bar

(c) corresponding volume change when acetone is changed to 00C and 10 bar

Using equation C3:

dV
   dT    dP
V
V 
 ln 2    T2  T1    P2  P1 
 V1 

 V 
 ln 2   1.487x10  3 0  20  62x10 - 6 x10  1  0.0303
 1.287 
V2  1.287 exp 0.0303  1.249 cm 3 g 1

Ans. V2 =1.249 cm3g-1

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Tutorial

1. Express the following property variations in terms of measurable properties:

 H   U 
(i)  (ii)  
 P T  P T

2. At a pressure of 1 atmosphere, liquid water has a state of maximum density at about 4 0C. What can
 S 
be concluded about   at: (a) 30C (b) 40C and (c) 50C ?
 P  T
3. The differential of pressure obtained from a certain equation of state is given by one of the
following expressions. Determine the equation of state.

2V  b  V  b2 dT RT R
(i) dP  dV  (ii) dp  dV  dT
RT RT 2 V  b2 V  b

4. Using van der Waals equation of state and relevant Maxwell relation, calculate the derivative:
 S 
  for water vapour at a state fixed by a temperature of 240 0C and V of 0.465 m3 kg-1 . Check
 P  T
your answer with steam table data.

5. Using Redlich-Kwong equation of state and an appropriate specific heat relation, determine the
change in specific enthalpy for methane between 300K, 1 atmosphere and 400K and 200
atmospheres.

6. Using Redlich-Kwong equation of state and an appropriate specific heat relation, determine the final
temperature for an isentropic expansion of N2 from 400 K and 250 atmospheres, to 5 atmospheres.

7. for a gas obeying van der Waals equation of state:

 C 
a) show that:  v   0 (b) develop an expression for (Cp-Cv).
 V T
b x
8. A certain gas is described by the equation of state: PV  RT  P  where: b = constant,
 RT 
and x = f(Temp).
 P   x 
Derive an expression for isothermal compressibility, , and for   , in terms of T, P, x and  .
  T V  T 
9. A rigid vessel filled to half its volume with liquid nitrogen at its boiling point, is allowed to
warm to 250C. What pressure is developed in the vessel? Vm of nitrogen at its boiling point
is 34.7 cm-3 mol-1.

10. Use the data provided to determine (Cp – Cv) near 200C, for the following liquids :

Liquid Mol Wt.  (g cm-3)  (K-1)  ( bar-1)

Water 18.02 0.998 0.000207 49 x10-6
Acetone 58.08 0.7899 0.001487 100 x10-6
Chloroform 119.38 1.4832 0.001273 83 x10-6
Mercury 200.6 13.5939 0.00018186 3.95 x10-6

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APPENDIX TO MODULE 4

Derivation of the equations presented in this module

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Derivation of Property relations equations

We shall first revise the mathematics of exact differentials because this is a pre-requisite tool for
the topic presented in this module.

A4.1 Mathematics of exact differential of 2 independent variables

A. Consider: Z = f(x,y)

 Z   Z 
dZ    dx    dy
 x  y  y  x
Put: dZ=Mdx+ Ndy
where:
 Z   Z 
M   and N  
 x  y  y  x

d  Z  d  Z 
Also:     
dy  x  y dx  y  x

2 2
 Z  Z
  ................ (a)
yx xy

M N
i.e.  ................……….(b)
y x
Equation (a) and (b) express the necessary and sufficient conditions for exact differentials.

B. Other partial derivative relations:

If: Z = f(x,y), x = f(Z, y) and y=f(Z,x)

 x   y 
then:      1
 y  z x z

 y   Z   x 
       1
 Z  x  x  y  y  z

 Z   Z 
dZ    dx    dy -- (1)
 x  y  y  x
 x   x 
dx    dZ    dy --- (2)
 z  y  y  z
 y   y 
dy    dZ    dx -- (3)
 z  x  x  z

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Eliminating dy from (1) by substituting (3) into (1) gives:

 Z   Z   y   y  
dZ    dx      dZ    dx
 x  y  y  x  z  x  x  z 

 Z   Z   y   Z   y 
dZ    dx      dZ      dx
 x  y  y  x  z  x  y  x  x  z

  Z   y    Z   Z   y  
 dZ 1        dx        
  y   z    x  y  y  x  x  z 
 x x

Similarly, eliminating dz from (2) gives:

  y   y    
dx1        dZ  x    y   y  
  x   x    Z  y  x  Z  Z  x 
 Z Z 

A4.2 Application of exact differentials to thermodynamics

1st law of thermodynamics: U= Q - PV

 dU = dQ -PdV -VdP dQ = dU +PdV+VdP =dh

1st law for a closed system

dU = dQ - PdV
 dQ = dU + PdV ------- (4.1)

2nd law of thermodynamics for a closed system:

dQ
dS  for a reversible process
T
dQrev
dS   dQ  TdS ----- (4.2)
T

Combining equations (4.1) and (4.2) gives:

dU = TdS - PdV ---------- (4.3)

Enthalpy:

H = U + PV for isothermal reaction at constant pressure

dH = dU + PdV + VdP ---- (4.4)

substitute (3) into (4) gives:

dH = TdS + VdP ----- (4.5)

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Gibbs free energy: for a process at constant T and P:

Recap: Significance of Gibbs free energy, G:

(a) for a process at constant P and T, then: (G)T,P 0
(b) -(G) = maximum work at constant T and P (i.e. Wmaxi)

G = H - TS
dG = dH - TdS - SdT
substitute for dH from equation (5) gives:
dG = VdP - SdT -------- (4.6)

Helmohltz free energy: for a process at constant T and V:

A = Helmohltz free energy = U - TS
dA = dU - TdS – SdT
at constant T, then: dA = Du - TdS

substitute for dU from equation (3) gives:

dA = -PdV - SdT ---- (4.7)
Significance of Helmohltz free energy, A:

(a) Wmaxi = -(A)T, V = -(U-TS)

A4.3 Summary of equations for differential of each thermodynamic properties:

In presenting this summary, we shall categorise them into blocks of equations.

Summary of fundamental property relations

Equation block “A”

dU  TdS  PdV
dH  TdS  VdP
…………….. (block “A”)
dG  VdP  SdT
dA   PdV  SdT

Equations in block “A” are the fundamental property equations for pure fluid of constant
composition.

Mathematically, they are all of the form:

Z=f(x,y)
 Z   Z 
dZ    dx    dy
 x  y  y  x

Consider: U = f(S,V) ---- this follows from equation (4.3)

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

compare this with equation (4.3):

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 U   U 
 TdS    dS  T    …….. (4.8)
 S V  S V

 U 
Similarly:  P  …………….. (4.9)
 V  S

We can develop similar relationships between the differentials of equations in block “A” as
follow:

From equation (4.5): H = f(S,P)

 H   H 
dH    dS    dP
 S  P  P  S

 H   H 
T    and V   ………… (4.10)
 S  P  P  S

Similarly from equation (4.6): G = f(P,T)

G  G 
consequently, V    and S   ………….(4.11)
 P T  T  P

and from equation (7): A =f(V,T)

A   A 
consequently,   P    and S   ……………(4.12)
 V T  T V

A4.4 Summary of first partial differentials

Summary of equations 4.8 – 4.12

Equation block “B”

 H   U 
V   P   
 P  S  V  S
 U   A 
T   S   
 S V  T V
…………….. (block “B”)
 H   G 
T   S   
 S P  T  P
 A   G 
P    V  
 V  T  P  T

Equation block “B” presents the first partial differentials from equation block “A”

Another set of equations may be developed from equation block “B”, by taking the second
differential of the derivatives of the equations in block ”B”, as follow.

from equation block “B”:

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 U 
T  
 S V
---- (4.13)
 T   2U
  
 V  S SV

U 
but: P    …… from equation block “B”
 V  S
 P   2U
    --- (4.14)
 S V VS

Since the order of differentiation is immaterial for second derivative, then (4.13) = (4.14)

 T   P 
     ….……… (4.15)
 V S  S V

 T   2H
similarly from (block “B”):   
 P  S SP

 V   2H
  
 S  P PS

 V   T 
    …………..(4.16)
 S  P  P  S

 V   2G
also from block “B”:   
 T  P PT
 S   2G
and:   
 P  T TP

 V   S 
     …………. (4.17)
 T P  P T

 S   2A
Finally, from block “B”:   
 V T TV
 P   2A
  
 T V VT

 S   P 
    ……….. (4.18)
 V  T  T V

A summary of the set of 2nd partial differentials (equations 4.15–4.18) form equation block “C”:

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Maxwell equations

Summary of the second partial differentials are presented in equation block “C”

Equation block “C”

 V   S 
(i )     
 T P  P  T
 S   P 
(ii)    
 V  T  T  V
…(Block “C” - Maxwell equations)
 V   T 
(iii)    
  S  P  P  S
 T   P 
(iv)     
  V S  S  V

This set of equations is called Maxwell equations after James Maxwell who first derived these
relationships.

 The Maxwell equations form the basis for the derivation of many thermodynamic relations.

 The most useful relationship equations for enthalpy (H) and entropy (S) of a pure fluid are
expressed as functions of T and P.

 It is therefore, important to know how H and S vary with T and P. This information is
S  H   S   h 
conveyed by the Maxwell equations:   ,   ,   , and  
 T  P  T  P  P T  P T
 Maxwell equations express the relationship between the primary thermodynamic properties.

 These equations are useful for calculating du and dh provided the equation of state
information is available.

A4.5 Relations between specific heats (Cv and Cp), enthalpy (H) and internal energy (U)

From the 1st law of thermodynamics for a constant volume process: du =CvdT
 u 
 Cv   
 T  v

Applying differential mathematics:

 U   S   U   U   S 
  x    CV     
 S   T   T   S  v  T  v

U S 
From equation block “B”:    T   CV  T  
 S  v  T  v

Similarly, for a constant pressure process: dH = CpdT.

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 H   H   S   S 
 CP         T 
 T  P  S  P  T  P  T  P

 S 
CV  T   …………… (4.19)
 T  v

 S 
CP  T   ……………. (4.20)
 T  P

(i) enthalpy and Cp:

  V  
dH  C P dT  V  T    dP …….(4.21)
  T  P 
(ii) internal energy and Cv:

  P  
dU  CV dT  T    P  dV …….. (4.22)
  T V 

A4.6 Other relations from Maxwell’s equations

Entropy and specific heats

(a) Entropy and Cp

S = f(T,P)

 S   S 
 dS    dT    dP
 T  P  P T

S   S 
Using equation (4.20): C P  T 
Cp
    

 T P  T  P T

C p dT  S 
 dS     dP
T  P T

S V
From the Maxwell’s relation:     
 P T  T  P

C p dT  V 
 dS    dP ………. (4.23)
T  T  P

This equation expresses the relation between entropy and Cp. To use this equation, we
V
determine   from an equation of state.
 T  P

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(b) Entropy and Cv

S = f(T,V)

 S   S 
 dS    dT    dV
 T  v  V T

S   S 
Using equation (4.19): CV  T 
C
     v

 T v  T v T
 S   P 
and the Maxwell relation:     
 V T  T V

We obtain:

C dT  P 
dS  V   dV …………. (4.24)
T  T  v

P
Again, we can determine   from an equation of state.
 T  v

Other specific heat relations are presented in equations (4.25) and (4.26). Full derivations of
these may be found in any standard text on Chemical Engineering Thermodynamics (See list of
references in Module 1a).

A4.7 Ratio of specific heats

C P  V   P 
    ……. (4.25)
CV  P T  V  S

4.8.3 Specific heat differences

  2V   P   P   V 
C p  Cv  T     T   …. (4.26)
 T 2   V  
 T V  T  P
 P T

Full derivations of equations (4,25) and (4.26) may be found in any standard text on Chemical
Engineering Thermodynamics (See list of references in Module 1a).

Important deductions from specific heat differences, equation (4.26):

 V 
1. Since    0 (i.e. very small volumetric sensitivity to temperature) for liquids and solids,
 T  P
it follows that Cp-Cv 0. Therefore, one specific heat value is adequate for solid or liquid
state. Hence, tables generally give one value, which is really Cp.
2. As T0, Cp Cv (at very low temperatures).

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P
3. For all known fluids,    0 at all times. Consequently, (Cp-Cv) is positive,
 V T
Cp > Cv .

A4.6 Some important property characteristics of liquid state

V =f(T,P)
 V   V 
dV    dT    dP --- (4.27)
 T  P  P  T

Define:
(i) Volume expansivity (also called isobaric coefficient of thermal expansion),  (0C-1):
1  V  1   
      
V  T  P   T  P
………. (4.28)
 V  V   
   V    
 T  P   T  P

and
(ii) isothermal compressibility,  (Pa –1):

1  V  1   
      
V  P T   P T
………. (4.29)
 V  V   
   V   
 P  T   P T

Substitute these into (4.27) gives:

dV  VdT  VdP
dV ………. (4.30)
  dT  dP
V

Integrate to obtain:
V 
ln  2    (T2  T1 )   P2  P1  ……. (4.31)
 V1 

 V 
Isotherms for liquid phase are very steep and closely spaced. Consequently, both   (i.e. )
 P  T
 V 
and   (i.e. ) are small. This is a characteristic behaviour of liquids outside the region of
 T  P
the critical point. Hence, liquids are said to be incompressible fluids because  and  are very
small (approximately zero). In practice, no real fluids is incompressible because one cannot
define a P-v-T equation for an incompressible fluid.

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CHEMICAL THERMODYNAMICS 2 PROPERTY RELATIONS FOR PURE FLUIDS

Summary of Property relations for pure fluids in single phase

(a) Summary of equation blocks

Fundamental Fundamental property First partial differentials Maxwell Equations
properties relations [ Equation block “B” ] [ Equation block “C” ]
[Equation block “A” ]
Internal energy, U
U=f(S,V) dU=TdS-PdV
 H   U   V   S 
V   P    (i )     
Enthalpy, H  P  S  V  S  T P  P T
H = f(S,P) dH=TdS+VdP  U   A 
T   S     S   P 
 S V  T V (ii )    
 V T  T V
 H   G 
Helmohltz free energy, T   S   
 S  P  T  P  V   T 
A=f(T,V) dA=-SdT-PdV (iii )    
 A   G   S  P  P  S
P    V  
 V T  P T  T   P 
Gibbs Free energy, (iv )     
 V  S  S V
G=f(T,P) dG=VdP-SdT

(b) Summary of Specific heat relations

 S   S 
(i) CV  T   (ii) C P  T  
 T v  T P
  P  
(iii) Internal energy and Cv: dU  CV dT  T    P dV
T   V 
  V  
(iv) Enthalpy and Cp: dH  C P dT  V  T    dP
  T  P 
C p dT  V  C dT  P 
(v) Entropy and Cp: dS    dP (vi) Entropy and Cv: dS  V   dV
T  T  P T  T  v

C P  V   P 
(vii) Ratio of specific heats:    
CV  P T  V  S
  2V   P   P   V 
(viii) Specific heat differences: C p  Cv  T      T   
 2   V   T V  T P
 T  P T

(d) Summary of important relations for liquid state

1  V  1     V  V   
(i) isobaric thermal expansion:  P            PV    
V  T P   T  P  T P   T  P

1  V  1     V   V   
(ii)Isothermal compressibility:  T             T V   
V  P T   P T  P T   P T
V 
(iii) ln 2    (T2  T1 )   P2  P1 
 V1 
Definitions: (i)  (OR:  P)= coefficient of thermal expansion (0C-1)
(ii)  (OR:T)=coefficient of thermal compressibility (Pa-1)

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