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Syarat-syarat Umum
Kesetimbangan
1. U = U(S,V) untuk setimbang dU = 0,
spontan <0
2. H = H(S,P) untuk setimbang dH = 0,
spontan <0
3. A = A(T,V) untuk setimbang dA = 0,
spontan dA <0
4. G = G(T,P) untuk setimbang dG=0,
spontan dG<0
Equilibrium
Material Equilibrium
1. Chemical Equilibrium
2. Phase Equilibrium
Thermal Equilibrium
Mechanical Equilibrium
Chemical Equilibrium
Reaction
N2O4 (g) 2NO2(g)
Initial
Equilibrium
A
Chemical Equilibrium
Develop the concept of chemical
potential
Chemical potential used to account
for the equilibrium composition of
chemical reaction
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Outline
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The Gibbs energy minimum
Corresponds to chemical reactions
A
B
d of A turns into B
dnA = -d
dnB = +d
G
r G
p ,T
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dG A dn A B dnB
A d B d
B A d
dG
B A
d p ,T
That is
rG B A
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Extent of reaction
Extent of Reaction = Besarnya reaksi
= derajat reaksi
= koordinat reaksi
aA+ bB cC +dD
dA dB di
d
A B i
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Exergonic and endergonic
reaction
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The description of
equilibrium
Perfect gas equilibria
G
r B A
B RT ln p B A RT ln p A
pB
r G RT ln pB
pA Q
pA
At equilibrium rG=0
0 r G RT ln K
RT ln K r G
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Example
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At the specified stage of the reaction
At equilibrium
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CO2 can be treated as a perfect gas
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Calculate the equilibrium constant for the ammonia synthesis reaction at 298 K
and show how K is related to the partial pressures of the species at equilibrium
when the overall pressure is low enough for the gases to be treated as perfect.
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The relation between equilibrium constants
Reaction A B C D
aC a D aj j xj
Equilibrium constant K or
a A aB bj
aj j
b
C D xC xD C D bC bD
So, K or K
A B x A xB A B bA bB
K K x K Kb
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The response of equilibria to the conditions
Response to pressure
0 r G RT ln K
RT ln K r G
therefore
K
0 K is independent of pressure
p T
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Alternatively,
reaction
A 2B
aB2
K
aA
pB2
p A p
Le Chateliers priciples states that:
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A 2B
Initial amount n 0
Change n 2n
At equilibrium 1 n 2n
xA
1 n
1
1 n 2n 1
2n 2
xB
1 n 2n 1
pB2 xB2 p 2 4 2 p p
K
pA p xA p p 1 2
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4 2 p p
K
1 2
K K 2 4 2 p p
K K 2 4 2 p p
K
2
K 4 p p
1
K 2
K 4 p p
p increase
decrease
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Predicting the effect of compression
There are ammonia synthesis at equilibrium.
3H 2 N 2 2 NH 3
Decreasing number of gas molecules.
So, Le Chateliers principle predicts that an increase in pressure will favour
the product. The equilibrium constant is
2 2 2
p 2
NH 3 p x 2
NH 3 p p
2
Kx p
K
pN2 p 3
H2 x N 2 xH3 2 p 4 p2
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The response of equilibria to the conditions
Response to temperature
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The vant Hoff equation
r G
ln K
RT
Differentiation of two side
d ln K
1 d r G T
d r G T
r H
dT R dT dT T2
d ln K r H d 1 T 1
2 or dT T 2 d 1 T
dT RT 2 dT T
d ln K r H
d 1 T R
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The value of K at different temperatures
d ln K r H
d 1 T R
r H
d ln K d 1 T
R
r H
d 1 T
1 T2
ln K 2 ln K1
R 1 T1
r H 1 1
ln K 2 ln K1
R T2 T1
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Estimate the equilibrium constant for the synthesis of ammonia at 500 K
from its value at 298 K (6.1 x 105). rH = 2fH(NH3,g) = -92.2 kJ/mol.
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Practise
For the equilibrium, N2O4(g) 2NO2(g), the degree of dissociation, c , at 298 K is
0.201 at 1.00 bar total pressure. Calculate
(a)rG at this temperature.
(b) K
(c)rG
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