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Chemical Equilibrium

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

The Gibbs energy minimum


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The description of equilibrium


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How equilibria respond to pressure


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How response of equilibira to temperature


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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

Not yet sure that the equilibrium composition


is independent of the pressure, and its effect
depends on how the pressure is applied.

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Alternatively,
reaction
A 2B
aB2
K
aA
pB2

p A p
Le Chateliers priciples states that:

A system at equilibrium, when subjected to a


disturbance, responds in a way that tends to
minimize the effect of the disturbance

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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

According to Le Chateliers principle:

Exothermic reactions : increased temp favours the reactants


Endothermic reactions : increased temp favours the products

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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

The standard enthalpy of a certain reaction is approximately constant at +125


kJ/mol from 800 K up to 1500 K. The standard reaction Gibbs energy is +22
kJ/mol at 1120 K. Estimate the temperature at which the equilibrium constant
become greater than 1.

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