Thermodynamic Properties of

Fluids
Unit I
 Unit Objectives
• Classify the thermodynamic properties into Reference, Energy
and Derived properties
• Understand the significance of Helmholtz free energy and
Gibbs free energy as representation of maximum work and
net useful work
• Derive relations like the Maxwell equations and Clayperon
equation relating the measureable and unmeasureable
thermodynamic quantities and the dependence amongst one
another
• Understand the utility of thermodynamic diagrams
 Classification of
Thermodynamic Properties
• Reference Properties
• Energy Properties
• Derived Properties
 Reference Properties
• Primary Properties used to define the state of
a system
• They have absolute values
• Eg:
– Temperature
– Pressure
– Volume
– Entropy
– composition
 Energy Properties
• Extensive properties
• Can be measured relative with some reference
state
• Eg:
– Internal energy (U)
– Enthalpy (H)
– Helmholtz free energy (A)
– Gibbs free energy (G)
 Derived Properties
• These are the partial derivatives of energy
properties
• Eg:
– Specific heat
– Coeff. Of expansion ()
– Joule Thomson coeff. ()
– Coefficient of compressibility (K)
Helmholtz free energy (A)
(Work Function)

A = U – TS
 Significance
• Work function is the measure of maximum
obtainable work

• Prove the above statement

 Gibbs Free Energy (G)
G = H – TS

• State function
• Extensive Property
• Widely used to study phase and chemical
equilibria
 Significance
• Gibbs free energy measures the net useful
work

Prove the above statement

Fundamental property relations
dU = T dS – P dV

dH = T dS – V dP

dA = -S dT – P dV

dG = -SdT + V dP
 Fundamental Property Relations
• Derive the fundamental property relations
from the first law and second law of
thermodynamics
Relation among the variables

U = f (S, V)
H = f (S, P)

A = f (T, V)
G = f (T, P)
Maxwell Equations

 T   P 
    
 V  S  S V
 T   V 
   
 P  S  S  P
 P   S 
    
 T V  V T
 V   S 
    
 T  P  P T
 Derivations
• Derive the Maxwell equations from
fundamental property relations
 Importance of Maxwell Equations
• Helpful in replacing immeasurable quantities
appearing in thermodynamic equations by
measurable equations
 Measuring entropy with
Maxwell relations
• S = S (P, T)
• S = S (T, V)
• S = S (P, V)

Six partial derivatives are obtained among

which some can be related to measurable
quantities like Cp and Cv
 Significance:
Partial derivative of entropy with temperature

 S  CP
  
 T  P T
 S  CV
  
 T V T
 Significance
 T   P 
    
 V  S  S 
or
 S   T 
    
 P V  V  S
 S 
i.e.  is equal to - ve slope of V vs T for reversible
 P V
adiabatic process
 Mnemonic diagram
• Sides are energy properties
• Corners are canonical variables or A
energy properties V T

• Differentials are obtained from

variables adjacent to the energy
property
• Coefficients are obtained from the U
G
variables that are diametrically
opposite to these variables

• Sign Convention
• If the arrow points away from the S P
canonical variable, coefficient is H
positive
 Mnemonic diagram
for Maxwell Equations
• Partial derivatives formed by canonical
variables  T 
 
 V 

• The suffix is the variable that is diametrically

opposite to the first variable i.e ‘S’
 T 
 
 V  S
 Mnemonic diagram
for Maxwell Equations
• The other derivative is obtained from the
opposite side of the square
 P 
 
 S V

• Direction of the arrow is towards T and away

from P. Hence, the negative sign

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

dP H

dT TV
 Clayperon Equation
• Predicts the dependence of equilibrium
pressure on temperature when two phases of
a given substance co-exist
• Applicable to any closed, homogeneous or
heterogeneous system in equilibrium with an
external pressure
• Can be used to calculate the heat of
vaporization, if the variation of vapour
pressure with temperature is known
 Clausius Clayperon Equation
• If the temperature is not too near the critical
point, the volume of the liquid is small in
comparison with the volume of the vapour.
• Hence, the volume change accompanying
vaporization, V = VG – VL is approximately
equal to VG, the molar volume of vapour
 Clausius Clayperon Equation
• The Clayperon equation becomes

dP H

dT TVG
 Clausius Clayperon Equation
• Since vapour pressure is small, the vapour is
assumed to behave as ideal gas i.e. VG = RT/PS
dP S S H
P 2
dT RT
• Integrating
d H
ln P 
S

dT RT 2
• This is Clausius Clapeyron equation
 Clausius Clayperon Equation
• Assuming that the heat of vaporization
remains constant in the temperature range T1
to T2, on integration we get,

P S
H  1 1 
ln 2

S
  
P1 R  T1 T2 
 Fugacity
• Introduced by G.N.Lewis
• Used to represent the behaviour of real gases
• It is the ‘pressure’ for real gases
• In Latin, it means, ‘fleetness’ or ‘escaping
tendency’
Consider dG = -SdT + VdP
For a reversible change under isothermal
conditions
dG = VdP
= (RT/P)dP
dG = RT d(ln P)
 Fugacity
• In order to represent the influence of pressure on
Gibbs free energy of real gases, the pressure has to
replaced by an effective pressure which is called the
fugacity
dG = RT d(ln f)
G = RT ln f + C
Where,
C is a constant of integration and it depends on the nature and
temperature of gas
• Units of ‘f’ are same as that of pressure
 Fugacity
Let G1 and G2 be the free energies of a gas in
two states and f1 and f2 be the corresponding
fugacities
G = G2 – G1 = RT ln (f2/f1)
For an ideal gas,
G = G2 – G1 = RT ln (P2/P1)

f 2 P2

f1 P1
 Fugacity
• For real gases, as pressure is reduced to zero,
behaviour of gas approaches ideal

f
Lim  1
P 0 P

f
 1 as P  0
P
 Fugacity Coefficient ()

Fugacity

Pressure

•It is a dimensionless quantity

•Depends on the nature of the gas, pressure and temperature

 Fugacity
G – Go = RT ln (f/fo)
Now fo = Po and f = P
G – Go = RT ln (P / Po)
= RT ln (P / Po) + RT ln 
= Go + RT ln (P / Po) + RT ln 

Free energy of real gas = Free energy of ideal gas + Intermolecular interaction

Note: Standard state for a real gas is a hypothetical state in which the gas is at a
pressure P0 where it behaves perfectly
 Gibbs Helmholtz Equation
• It provides the effect of temperature on Gibbs
free energy
Consider,
dG = - SdT + VdP
At constant pressure
 G 
   S
 T  P
 Gibbs Helmholtz Equation
 G 
• Derivative of G/T is
  
  G  T  T   G
T    P
 T  T2
 

  
 G
T 
 TS  G
 T  T2
 

  
 G
T H
 2
 T  T
 P
• This is the Gibbs Helmholtz equation
Effect of temperature on fugacity

  ln f  Ho H
  
  T P RT 2
Methods of Determination of Fugacity
• Using Compressibility Factor (Z)
• Using Generalized Charts
• Using Residual Volumes
• Using Equation of State
• Using values of enthalpy and entropy
• Approximate method of estimation
 Using Compressibility Factor (Z)
• Plot (Z-1)/P vs P to evaluate the integral

f P  Z 1 
ln    dP
P 0 P 
 Using Generalized Charts
• Plot fugacity coefficient against reduced
pressure (Pr) for various constant temperature
values to give generalized fugacity chart

Tr = 2
f Pr  Z  1  
ln    dPr
P 0  Pr  Tr = 1

Pr
 Using Residual Volume
• Residual volume  is defined as the difference
between the volume and the volume occupied
by one mole of an ideal gas at the same
temperature and pressure

RT
 V 
P
 Using Residual Volume
P
f 1
ln 
P RT 0  dP
• To find f, the residual volume derived from
experimentally determined values of molar
volumes at different temperatures are plotted
against P.
• Area under the curve gives the value of the
integral
 Using Residual Volume

f
P

Area  ln   dP
/RT
P 0 RT

P
 Using Equation of State
P
f 1
ln o 
f 
RT P o
VdP

If V is expressed as a function of P the above

integral can be evaluated.
Approximate Method of Estimation
2
VP
f 
RT
V is the molar volume
 Fugacity of Solids and Liquids

ln
f
f
sat

V
RT
PP S


PS = Saturation Pressure of gas

fsat = saturation fugacity
V = molar volume