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What's Chemical Equilibrium
What's Chemical Equilibrium
What's Chemical Equilibrium
G system
0
Equilibrium S total
0 or G system
0
Kinetics:
Concept introduced by A. W. Williamson in 1851 during
study esterifications
Forward reaction rate = Reverse reaction rate
Equilibrium (at a specified temperature)
Reaction rates are not ceased when equilibrium is
reached.
Chemical equilibrium Dynamical equilibrium
Expression of Equilibrium Constant:
Considering a stoichiometric reaction: aA bB yY zZ
1 1
-1 -1
At equilibrium, r r
1 1
k1 Y Z
y z
a b Kc
k1 A B
1
Kc; Kp; Ksp
(B) The factors that affect equilibrium constant:
Temperature; Reacting species
Chemical Potential:
G U H A
n n n n
i
i T , P , ni n j i S , V , ni n j i S , P , ni n j i T , V , ni n j
i i
ideal solution
where (T , P)
*
i is the chemical potential of the pure substance
i when it is at the temperature T and pressure P.
xi is the mole fraction of substance i in the solution.
(B) Chemical potential for non-ideal solution:
For non-ideal solution, the chemical potential of substance i
is defined by:
( T , P ) ( T , P ) RT n a (definition of ai)
i i
*
i
ai is the activity.
Extent of reaction:
The degree of reaction progress
The ratio of the amount of any species produced/formed to
the its stoichiometric coefficient
2
e.g. A B Y Z
A B Y Z
n A n B
for reactants:
A B
nY n Z
for products:
Y Z
dG dn i i
i 1
G N
mole of reaction.
G 0 (forward reaction spontaneous)
T ,P
G 0 (backward reaction spontaneous)
T ,P
G 0 (equilibrium)
T ,P
3
The chemical potential of a species is expressed by,
( T , P ) ( T , P ) RT n a
i
*
i i
N N
At equilibrium, RT na 0
o
i i i i,eq
i 1 i 1
-RT n a
N
o i
i i i,eq
i 1 i 1
K a i 1
i
i,eq
i i r
i 1
.
Therefore, we can obtain
G RT n K
r
o
(A) Equilibri
um in pure gases:
Pi fi
a o ( ideal gas ) or a i
f
o ( real gas)
i
P
i i
P N
f
N
K P i
(ideal gas) or K P i
(real gas)
P i 1 o
eq
f i 1 o
eq
(B) Equilibri
um in pure condensed phases:
Substances that are pure liquids or solids contribute a factor nearly
equal to unity to the equilibrium constant expression. To a good
approximation, they can be omitted from it, i.e.
a 1i (pure liquid or solid)
(C) Equilibri
4
um in solution:
a x ( ideal solution )
i i or a m ( real solution)
i i i
a i eq a i i eq
i 1 i 1
n
PV nRT P RT = CRT
V
P P C C uY uZ uY uZ
C C RT K RT
uY uZ uA uB u
K P
Y
uA
Z
uB
Y
uA
Z
uB C
P P A B eq A B eq
RT
u
K K P C
P P y y Y Z Y Z
P K P
Y Z A B
K
Y Z Y Z
P P y y
P A B A B y
A B eq A B eq
K K P
P y
Ky is dependent on T and P.
Units:
Thermodynamic equilibrium constant is dimensionless, but
practical equilibrium constant is not.
Ex.1: A B Z
5
Z
1
A B ; K C
K
C
mole
liter
Ex. 2: A BY Z
K
Y Z
C
A B ; Kc is dimensionless
In general, K ( unit ) u
Ex.: A 2Z K C
A
G RT nK
0
1
0
C
Z
1 A Z K G RT nK
0 0
A
C 1
2 2 2 C
K K
1
; G 1 G 0
2 0
C C
2
2 1
B C
Ex.: A BC K 1C
A
B Y
C BY K 2C
C
B Y K
2
A 2B Y K K
C
A 1C 2C
6
From electromotive force: G zFE
0
2
2
P
1
2
PNO 4
2
K 2
P
1
P
1
2
PN O
2 4
P
1
Ex. The Gibbs energies of formation of NO2(g) and N2O4(g) are 51.3
kJ/mole and 102.0 kJ/mole, respectively, in the standard state,
(a) Calculate
Kp and Kc for the reaction N O 2 4( g )
2NO
2( g ) if the gas is ideal.
(b) Calculate
Kx at 1 bar pressure.
(c) At what
pressure is N2O4 50% dissociated?
(d) What is
7
if the standard state is 1 mole liter ?
G
0
600
n K 0
P
0 . 242 ;
RT 8 . 3145 298 . 15
K 0 .785 bar
0
P
K K RT K RT
u
P C C
0 . 785 10
0 5
KP
K
0
3 . 17 10 mole
2
C
RT 8 . 3145 298 . 15 liter
(b)
K K P
u
P y
K P y
KP
K y
0 .785
P
(c)
4
2
K P
P ; =0.5; Kp= 0.785 bar
1
2
4 0.5
2
(d)
G RT nK 8 . 3145 298 . 15 n 3 .17 10
0
C
2
joule
= 8555
mole
8
Sol: a CaCO3
1 and a CaO
1 K P
P CO2
Ex. At 1393K,
Fe O
2 3( S )
3CO ( g)
2Fe (S)
3CO 2( g ) K1=0.0467
2CO 2( g )
2CO ( g)
O 2( g ) K2 =1. 4 10 12
K 0 . 0467 1. 4 10
2 3
12
6 . 01 10 39
K P 3
O2
P 6 . 01 10
1
O2
39 3
1. 82 10 bar 13
P y
if 0 ; K isindependent of pressure
y
9
if 0 ; K is higher when pressureis higher
y
if 0 ; K isindependent of volume
y
K P y P P n
i i i
i
P i i
n n i
i i i
i
i i
i
i
K K
P n
n i
i
if 0 ; K isequal to K
n P
10
Effect of temperature on equilibrium:
G 0
H
0
G RT n K
o 0
P
G nK H
0 0 0
R P
T T T T
2
P P
nK H
0 0
T
RT
P
2 called the vant Hoff equation.
P
if H 0 0
(exothermic reaction), K 0
P decreases when T is
increasing equilibrium toward reactants
if H 0 0
(endothermic reaction), K 0
P increases when T is
increasing equilibrium toward products
if H 0
is independent of temperature, then
H S
0 0
n K 0
P
RT R
H S
0 0
(slope = R
and intercept = R
)
if H 0
is a function of temperature, i.e. C d eT fT
P
2
1 1
H ( T ) H 25C d T 298.15 1
0
e T
2
288.15 f 2
m m
2 T 298. 15
temperature.
11
if Ky instead of Kp: K K P
P y
nK
0
H
0
T RT
y
2
P
if Kc instead of Kp: RT
u
K K
P C
nK U
0 0
T
RT
2
P
Le Chatelier Principle:
When an independent variable of a system at equilibrium is
changed, the equilibrium shifts in the direction that tends to
reduce the effect of the change.
When total pressure is increased, the equilibrium shifts in
the direction to reduce the number of molecules.
An increase in temperature at constant pressure in a closed
system shifts the equilibrium in the direction in which the
system absorbs heat from the surroundings.
H2 : H O H 1 O H 57 . 8 Kcal
0
2 ( g) 2( g )
2 2( g ) r
mole
(a) will the
dissociation increase or decrease if the pressure is
reduced?
(b) will the
dissociation increase or decrease if argon gas is added,
12
holding the total pressure equal to 1 bar?
(c) will the
dissociation increase or decrease if the pressure is raised
by addition of argon at constant volume to the close
system?
(d) will the
dissociation increase or decrease if oxygen gas is added?
(e) will the
dissociation increase or decrease if temperature is raised?
Sol: (a) increase; (b) increase; (c) no change; (d) decrease;
(e) increase.
Coupling of reactions:
If two reactions exist in a chemical system, one of reaction
product is the reactant of another reaction. This is called the
coupling of reactions.
e.g. A + B = L + M K1 < 1
L+C=N+Q K2 > 1
A + B + C = M + N + Q K3 = K 1 K2 > 1
The importance of the coupling of reaction is to increase the
production rate of product M.
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