PARTIAL MOLAR GIBB’S FREE ENERGY

• The chemical potential , denoted by the symbol µ, is widely used

thermodynamic property. It is used as an index of chemical
equilibrium in the same manner as temperature and pressure are
used as indicates of thermal and mechanical equilibrium. The
potential µi of component i in a solution in the same as its partial
molar free energy in the solution, Ḡi . That is, chemical potential of a
component i in a solution can be defined as
 G t  …………………………(1)
µi  G i   
 ni T , P ,ni
• The total free energy G t of a solution is a function of temperature,
pressure, temperature and number of moles of various
components.
G t  f ( P, T , n1 , n2 ,......, ni ,.....) ………………………….(2)

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 PARTIAL MOLAR GIBB’S FREE ENERGY
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• The total differential dG t is

 G t   G t   G t 
dG  
t
 dP    dT    …………………......(3)
 P T , N  T  P, N  ni  T , P , n j i

• Then using Eq. 1

 G t   G t  ………………….(4)
dG  
t
 dP    dT   µi dni
 P T , N  T  P,N

• We have shown that for a closed system, when there is no change

in the amount of various constituents,
dG  VdP  SdT………………………………………..(5)

• Considering the total properties of the system,

dG t  V t dP  S t dT……………………………………………(6)

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 PARTIAL MOLAR GIBB’S FREE ENERGY
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• From which follows that

 G   G 
  S ,  ………………………………………(7)
t t
  T 
t
 P   V
t

  P,N  T , N

• Equation 4 can be written as

……………………………………(8)
dG t  V t dP  S t dT   µi dni
• This is the fundamental relationship for change in the free energy of
a solution. At constant temperature, pressure, the change in the
free energy is due entirely to the changes in the number of moles
and is given by
dG   µ dn ………..…………………………………….(9)
t
T ,P i i

• By reasoning analogous to that used in the derivation of G   n M t

i i

we have, at constant temperature and pressure,

G   µ n …………………………………………………..(10)
t
i i
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 PARTIAL MOLAR GIBB’S FREE ENERGY
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• For a binary solution, the molar free energy of solution is
G  x1µ1  x 2µ2 ……………………………………..(11)
• The chemical potential of component is thus seen to be
contribution of that component to be Gibbs free energy of the
solution. The chemical potential is an important property of
solution extensively used in the study of phase and chemical
equilibria.

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 EFFECT OF TEMPERATURE AND PRESSURE ON
CHEMICAL POTENTIAL
• Effect of temperature: consider Eq. 1 and Eq. 7 with respect to
temperature. Then
 µ   G 2 t
i
 T   ………………………………(12)
T * n
P, N i

• Differentiating Eq. 7 with respect to ni, We get

 S 
t
 G 2 t

 n 
i
 
T * n
………………………………..(13) i
P ,T , n j

• Equation 12 & 13 imply, that

 µ   S  t
i
 T       S …………………………..(14)
 n 
i
P, N i P ,T , n j

• Where S is the partial molar entropy of the component i in the

i

solution . This result, through gives the variation of chemical

potential with temperature, can be put in a more useful form.
G  H  TS , G  H  TS , µ  H  TS
i i i i i i

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 EFFECT OF TEMPERATURE AND PRESSURE ON
CHEMICAL POTENTIAL
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• We can write
µi  H i ……………………………………………….(15)
 Si 
T
• We know that
 (µi / T )  T (µi / T )  µi ……………………………….(16)
 T  
P, N T2

• Substituting Eq. 14 and 15 into the above equation, we get,

  (µ / T ) 
i

H ……………………………………….(17)
i
 T  T 2
P, N

• Equation 17 predicts the effect of temperature of chemical

potential.

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 EFFECT OF TEMPERATURE AND PRESSURE ON
CHEMICAL POTENTIAL
Continue.

• EFFECT OF PRESSURE: equation 1 and 5 are further differentiated

to develop equations that predict of pressure of chemical potential.
Differentiating Eq. 1 with respect to pressure, we obtain
 µ   G 2 t
i
 P  
P * n
……………………………….(18)
T ,N i

• Differentiating Eq. 5 with respect to ni,

2
G t
 V  t
   V …………………………….(19)
P * n  n 
i
i i P ,T , n j i

• Compare Eq. 18 with 19

 µ  i
 P   V ………………………………………..(20)
i
T ,N

• The rate of change of chemical potential with pressure is thus equal

to the partial molar volume of the constituent.

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 FUGACITY

• The concept of fugacity was introduced by G.N. Lewis (1901) and is

widely used in solution thermodynamics to represent the behaviour
of real gases. The name fugacity is derived from the Latin for
fleetness' or the 'escaping tendency'. It has been used extensively
in the study of phase and chemical reaction equilibria involving
gases at high pressures. Though the ‘fugacity' is mainly applied to
mixtures, the present discussion is limited to pure gases.
• For an infinite, simal reversible change occurring in the system
under isothermal conditions, Eq. dG  SdT  VdP reduces
to
dG  VdP

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 FUGACITY
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• For one mole of an ideal gas V in the above equation may be

replaced by RT/P, so that
dP
G  RT  RTd (ln P) ………………………….(1)
P

• Equation (1) is applicable only to ideal gases. If, however, we

represent the influence of pressure on Gibbs free energy of real
gases by a similar relationship, then the true pressure in the above
equation should be replaced by an 'effective' pressure, which we
call fugacity f of the gas. The following equation, thus, provides the
partial definition of fugacity.
dG  RTd (ln P ) …………………………..(2)

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 FUGACITY
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• Equation 2 is satisfied by all gases whether ideal or real. Integration

of this equations gives:
G  RT ln f  C ……………………………….(3)
• Where C is a constant of integration that depend upon the
temperature and nature of the gas Fugacity has the same
dimension as pressure, usually atm. Or bar

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 FUGACITY AND FUGACITY COEFFICIENT: PURE
SPECIES
 
• As evident from Eq. i  i  ......  i the chemical potential µi


provides the fundamental criterion for phase equilibria. This is true

as well for chemical-reaction equilibria.
• However, it exhibits characteristics which discourage its use. The
Gibbs energy, and hence µi, is defined in relation to the internal
energy and entropy, both primitive quantities for which absolute
values are unknown. As a result, absolute values for pi do not exist.
• Moreover, Eq. iig  (T )  RT ln yi P shows that for an ideal-gas
mixture µi approaches negative infinity when either P or yi
approaches zero. This is in fact true for any gas.

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 FUGACITY AND FUGACITY COEFFICIENT: PURE
SPECIES
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• While these characteristics do not preclude the use of chemical
potentials, the application of equilibrium criteria is facilitated by
introduction of the fugacity, a quantity that takes the place of µi but
which does not exhibit its less desirable characteristics.
• The origin of the fugacity concept resides in Eq. Gi  (T )  RT ln P
ig

, valid only for pure species i in the ideal-gas state. For a real fluid,
we write an analogous equation:
Gi  (T )  RT ln f i ………………………………….(1)
• in which pressure P is replaced by a new property f, with units of
pressure. This equation provides a partial definition of fi ,the
fugacity of pure species i.

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 FUGACITY AND FUGACITY COEFFICIENT: PURE
Continue.
SPECIES
• Subtraction of Eq. (1 1.27) from Eq. (1 1.30), both written for the
same T and P, gives:
fi
Gi  Giig  RT ln
P
• According to the definition of Eq. (6.41), G  G is the residual Gibbs
i i
ig

energy, GiR . The dimensionless ratio f i/ P is another new property,

the fugacity coefficient, given the symbol φi. Thus,
G  RT ln  ……………………………………(2)
i
R
i

• Where  
i
fi………………………………………………………….(3)
P
• The definition of fugacity is completed by setting the ideal-gas-state
fugacity of pure species i equal to its pressure:
f  P …………………………………………(4)
i
ig

• Thus for the special case of an ideal gas, G  0 ,i  1 , and Eq. G  (T )  RT ln P
i
R
i
ig

is recovered from Eq. 1.

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 FUGACITY AND FUGACITY COEFFICIENT: PURE
SPECIES
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• The identification of ln i with G R

i / RT by Eq. 2 allows
R P
G dP
  ( Z  1) .....(const.T )
Eq. RT 0
P P
to be rewritten:
dP
ln i   ( Z i  1)
(const. T)……………………..(5)
0
P
• Fugacity coefficients (and therefore fugacities) for pure gases are
evaluated by this equation from P V T data or from a volume-
explicit equation of state. For example, when the compressibility
factor is given by Eq. Z  PV
RT
 1
B
V
,
Bii P
( Z i  1) 
RT
• Because the second virial coefficient Bii is a function of temperature
only for a pure species, substitution into Eq. 5 gives:
P
Bii dP
(const. T)
RT 0 P
ln i 
• Whence. ln i  Bii P ……………………………………………………(6)
RT

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 FUGACITY AND FUGACITY COEFFICIENT: PURE
SPECIES
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• Evaluation of fugacity coefficients through cubic equations of state

(e.g., the van der Waals, Redlich/Kwong, Soave/Redlich/Kwong, and
Peng/Robinson equations) follows directly from combination of Eqs.
R
2 and G  Z  1  ln( Z   )  qI :
RT
ln i  Zi  1  ln( Zi  i )  qi I i ……………………………..(7)

• where βi is given by Eq.    TP ; qi, by Eq. q  T(T ) ; and Ii, by

r r

Eq. I  1 ln  Z    , all written for pure species i.

r r

o r  Z 

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