Advance Chemical

Engineering Thermodynamics
Instructor: Dr Gunjan Agrahari
Days: Monday, Wednesday, Thursday
Time: 2:00 pm – 3:00 pm
Ideal Gas Mixture Model
Concept
• Molecular Basis
• approximately correct at low pressures
• simple analysis
• We know for ideal gas (pure):

RT
V
P
Concept
• For ideal gas (mixture), the relationship holds but we use partial
molar volume:

ig    nV  
ig
   nRT / P  
Vi     
 ni T , P ,n  ni T , P ,n j
j

  n  RT
  RT / P    
 ni T , P ,n j P
Concept
• This shows that for ideal gas mixture at given T and P, partial molar
volume = pure species molar volume = mixture volume!

ig    nV  
ig
   nRT / P  
Vi     
 ni T , P ,n  ni T , P ,n j
j

  n  RT
  RT / P    
 ni T , P ,n j P
Concept
• Partial Pressure:

yi RT
pi  ig  yi P
V

• Partial pressure is different from partial molar properties! (how)

Concept
• In ideal gas mixtures constituent species retain their individual private
property

• Gibb’s Theorem: A partial molar propert (not volume) of a constituent

species in ideal gas mixture is equal to corresponding molar property
• The species would also be in ideal gas state when in pure state
• The species would b at its ‘partial pressure’
ig
M (T , P)  M (T , pi )
i i
ig
Concept
• Enthalpy: since it is independent of pressure (for ideal gas)

ig
H (T , P)  H (T , pi )  H (T , P)
i i
ig
i
ig

ig
or H  H
i i
ig

• Similarly for internal energy

Concept
• Entropy: since it is not independent of pressure (for ideal gas)

dS   Rd (ln P )
i
ig

• at constant temperature

• If we integrate the above equation from pi to P

Concept

• we get
P
S (T , P)  S (T , pi )   R (ln )
i
ig
i
ig

pi
P
  R (ln )  Rln( yi )
yi P

S (T , pi )  S (T , P)  Rln( yi )
i
ig
i
ig
Concept

• by definition of partial molar property we have

ig
M (T , P)  M (T , pi )
i i
ig

ig
S (T , P)  S (T , pi )
i i
ig
Concept

• therefore we can write

S (T , pi )  S (T , P)  Rln( yi )
i
ig
i
ig

ig
S (T , P )
i
Concept

• therefore we can write

ig
S (T , P)  S (T , P)  R(ln yi )
i i
ig

ig
S  S  R ln yi
i i
ig
Concept

• Similarly we can write for partial molar Gibbs Energy

ig ig ig
G  H T S
i i i
Concept

• or

G  H  TS  RT ln  yi 
ig ig ig
i i i
Concept

• or

  G  H iig  TSiig  RT ln  yi 
ig ig
i i

 G  RT ln  yi 
i
ig
Phase Equilibrium

• Summability relations

H   yi H
ig
i
ig

S   yi S  R  yi ln yi
ig
i
ig

i i

G   yi G  RT  yi ln yi
ig
i
ig

i i
Phase Equilibrium
Gibb’s Duhem equation

• What is the importance of GD equation?

• It places a restriction on simultaneous variations in T, P and chemical potential

• Also we note that there are m+1 independent variables (out of m+2)

SdT  VdP   ni d i  0
i
Phase Equilibrium
Phase rule

• If there are m species, then m+1 independent variables in one phase (m-1+2)

• total number of phases is π, therefore total independent variables are π(m+1)

• If these phases are in internal equilibrium then, an independent phase equilibrium equation can be
written for one pair of phases for one species

• Thus number of independent equations are (π-1)(m+2); [for each composition and for T, and P]

• Therefore number of degrees of freedom are [(total number of independent variables) – (total
number of independent equations)]

• F = π(m+1) – (π-1)(m+2) = πm+ π- πm+m-2π+2 = 2- π+m

Phase Equilibrium
Chemical potential

• Further we write GD equation for single phase:

d i   SdT  VdP
• We can integrate it from a reference T P to a state

T P
i (T , P)  i (T , P )   SdT   VdP
R R

TR PR

unknown value!!
Phase Equilibrium
Chemical potential

• Further we write GD equation for single phase:

• This can complicate mathematical analysis, if reference state values of chemical potential are not
known – reference states are called as “Standard State”

T P
i (T , P)  i (T , P )   SdT   VdP
R R

TR PR

unknown value!!
Phase Equilibrium
Chemical potential

• We have to choose our standard sate so that we can assign values to it in terms of measurable
quantities

T P
i (T , P)  i (T R , P R )   SdT   VdP
TR PR
 Phase Equilibrium
• Look at the below equation again

d i   SdT  VdP

• We can develop some ‘simple’ relation using this equation

• At constant temperature, we can write:

 i 
  V
 P T
 Phase Equilibrium
• Further, for ideal gas

 i  RT
  V 
 P T P

• Integrate the above equation

P
i  0  RT ln 0
P
 Phase Equilibrium
• Thus we get the ‘difference in potential’ as the ‘ratio of pressures’

• This simplifies calculations

• For real fluids the above equations is rewritten as

fi
i  0  RT ln 0
fi
 Phase Equilibrium
• This equation or relation is given by Lewis who defined f for isothermal change in chemical potential
for a component i in the system

• This system can be any matter – solid, liquid, gas, real or ideal, in pure state, or mixed

fi
i  0  RT ln 0
fi
 Phase Equilibrium
• Fugacity Coefficient

fi
i 
P
 Phase Equilibrium
• Since, at constant T

dG  Vi dP  RTd ln P
i
ig ig

G  f (T )  RT ln P
i
ig

Gi  f (T )  RT ln f i
 Phase Equilibrium
• Therefore, at constant T

fi
Gi  G  RT ln
i
ig

P
 Phase Equilibrium
• or

Gi  G  G  RT ln i
i
ig
i
R

Residual Gibbs Energy Fugacity Coefficient

fi
i 
P
 Phase Equilibrium
• The equation applies to all pure species in any phase or in any real, ideal condition

Gi  G  G  RT ln i
i
ig
i
R

Residual Gibbs Energy Fugacity Coefficient

fi
i 
P
Phase Equilibrium
• Further

R
Gi
 ln i
RT
Phase Equilibrium
• Taking limits to zero pressure

Lim R Lim
G
P0  P  0 ln i  0
i

RT
Lim
fi
P  0 ln  0
P
Phase Equilibrium
• Therefore

Lim Lim
fi
P  0 i  P  0  1
P
Phase Equilibrium
• Therefore

P
dP
ln i   ( Z i  1)
0
P
Phase Equilibrium
• because

RT
V  V V  V 
R ig

P
RT
  Z  1
P