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LECTURE

9
CY11001
AUTUMN 2014-15

Mareial Equilibrium

Department of Chemistry
Indian Institute of Technology
Kharagpur

L7 – Page 1 D Dhara
Combination of 1st and 2nd Law

A closed system (constant


composition / change in
composition reversibly), rev.
process, and only p-V work

7-8/2 D.Dhara
Recap: Entropy Change only p-V work, closed system
dqrev dU − wrev
dS = =
T T
 ∂U  Entropy Change in a
  dV + CV dT + pdV
 ∂V T Process for ideal gas with
=
T Cv and Cp independent of
1  ∂U  dT p temp, only p-V work,
=   dV + CV + dV closed system.
T  ∂V T T T
T2 V2
∆S = CV ln + nR ln
T1 V1

p1 T2
∆S = nR ln + C p ln
p2 T1

7-8/3 D.Dhara
Calculation of Entropy change for Phase Transition

Normal Transition point is Ttrs at 1 atm

qp = ∆H qtrs = ∆Htrs ∆Strs = ∆Htrs / Ttrs (reversible)

∆Strs (surr) = - qp / Ttrs = - ∆Htrs / Ttrs

Trouton’s Rule
A wide range of liquid give approx. the same standard
entropy of vaporization ~ 85 J K-1 mol-1

L7 – Page 4 D Dhara
dGP, T, no non p-V work ≤ 0 Criteria of spontaneity

Rev. process, closed system, no irreversible change in composition, only p-V


work

Does not apply


• When composition is changing due to exchange of matter with
surroundings (open system)
• Irreversible chemical reaction
• Irreversible inter-phase transport of matter
For every closed system capable of only P-V work at thermal and
mechanical eqm, material equilibrium is reached when G is minimized

T or F
PHASE EQUILIBRIUM
 ∂V 
V i =  
 ∂ni  p ,T ,n j

= f (T, p, composition )

For pure substance

V i = molar volume at that T, P

It can shown mathematically

VT , P = V A n A + VB nB + ...
For one phase system G = f (T, p, n1, n2, ....)

(T, p, n1, n2, ….) (T+dT, p+dp, n1+dn1, n2+dn2, ….)

 ∂G   ∂G   ∂G   ∂G   ∂G 
dG =   dp +   dT +   dn1 +   dn2 + ...... +   dni
 ∂P T, ni  ∂T  P, ni  ∂n1 T, P, n j ≠ n1  ∂n2 T, P, n j ≠ n2 ∂
 i T, P, n j ≠ ni
n

 ∂G  i One phase system,


dG = Vdp − SdT + ∑   dni in therm and mech. eqm. P-V work
i =1  ∂ni T, P, n ≠ n
j i only

L7 – Page 9 D Dhara
 ∂G  i
dG = Vdp − SdT + ∑   dni
i =1  ∂ni T, P, n ≠ n
j i

 ∂G  One phase Chemical Potential


µi =  

 ∂ni  P , T , nJ #i system µi = f (T , P, n1 , n2 , .....)

i One phase system,


dG = Vdp − SdT + ∑ µ dn i i in therm and mech. eqm. P-V work
i =1 only

i i P, T, one phase, in
dGP ,T = ∑ µ dn i i ∑µ i dni = 0 equilibrium, P-V
i =1 i =1 work only

For pure substance


µ (Chemical Potential) = Gm = G/n
GP ,T = µi ni
L7 – Page 10 D Dhara
 ∂U 
n
dU = TdS − PdV + ∑ µ dn
i =1
i i where, µ i =  
 ∂ni  S ,V ,n
J

 ∂H 
n
dH = TdS + VdP + ∑ µ dn
i =1
i i where, µ i =  
 ∂ni  S , P ,n
J

 ∂A 
n
dA = − SdT − PdV + ∑ µ dn
i =1
i i where, µ i =  
 ∂ni  T ,V ,n
J

 ∂G 
n
dG = − SdT + VdP + ∑ µ dn
i =1
i i where, µ i =  
 ∂ni  T , P ,n
J

Chemical Potential
L7 – Page 11 D Dhara
More than one phase
i One phase (α) system,
dG α = V α dp − S α dT + ∑ i i
µ α

i =1
dn α
in therm and mech. eqm. P-V
work only

Many phases
i
dG = ∑α dG = ∑ V dp − ∑ S dT + ∑∑ µiα dniα
α α α

α α α i =1

α  ∂G α 
µi =  α 
 ∂ni  p , T , nαj≠i

i
dG = Vdp − SdT + ∑∑ µ iα dniα therm and mech. eqm.
α i =1
P-V work only

L7 – Page 12 D Dhara
i
Therm. and mech. eqm.
dG = Vdp − SdT + ∑∑ µ iα dniα P-V work only
α i =1

dG = Vdp − SdT + µ wvap dnwvap + µ svap dnsvap + µ wsol dnwsol + µ ssol dnssol

i
At const T, p;
dGP ,T = ∑∑ µiα dniα
α i =1

Material equilibrium, at const T, p;

dG = 0
i

∑∑ i i = 0
α
µ α
dn α

i =1

L7 – Page 13 D Dhara
More on G At const. p & T
i One phase system,
dGP ,T = ∑ µ dn
i =1
i i
in therm and mech. eqm. P-V
work only

Let all the components is


changed by a factor f at constant
P, T i i

dni = fni − ni = (f-1 )ni


dGP ,T = ∑ µ dn + ∑ n dµ
i =1
i i
i =1
i i

As G is an extensive property At const. p & T

dG = fG − G = (f-1 )G
i

i
∑ n dµ
i =1
i i =0
(f-1 )G = ∑ µ (f-1 )n
i =1
i i

i
GP ,T = ∑µ n
i =1
i i
Gibbs-Duhem equations

L7 – Page 14 D Dhara