Beruflich Dokumente
Kultur Dokumente
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
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
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
T or F
PHASE EQUILIBRIUM
∂V
V i =
∂ni p ,T ,n j
= f (T, p, composition )
VT , P = V A n A + VB nB + ...
For one phase system G = f (T, p, n1, n2, ....)
∂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
L7 – Page 9 D Dhara
∂G i
dG = Vdp − SdT + ∑ dni
i =1 ∂ni T, P, n ≠ n
j i
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
∂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
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
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