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Chemical Equilibrium
Recommended Problems
Learning Objectives : ALL
Self--Assessment and Review Q : All
Self
2010
Chemical Equilibrium
Defined: the state reached by a rxn mixture when
the rates of the forward and reverse rxns are equal.
constant!
2010
2010
2010
Equilibrium Constant - Kc
Since at equilibrium all concentrations are
constant a mathematical expression can be
written describing the relationship.
Kc =
[Product][Product]
[Reactant][Reactant]
aA + bB cC + dD
Kc =
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[C]c [D]d
[A]a [B]b
Generalized
reaction equation.
Generalized equilibrium
constant expression.
5
Kc =
[[CH4] [H
[ 2O]]
[CO] [H2]3
CO(g) + 3H2(g)
Initial
1.00 mol
-x
Change
Equilibrium
3.00 mol
-3x
CH4(g) + H2O(g)
0
+x
+x
+x
x= 0.387 mol
1.00 - x
3.00 - 3x
1.00 - .387 3.00-3.387
0.613 mol 1.839 mol .387 mol .387 mol
10.0 L
10.0 L
10.0 L
10.0 L
[CH4] [H2O]
.0387 x .0387 = 3.93 = K
=
c
[CO] [H2]3
.0613 x .18393
At 927C
2010
7
Kc =
Kp
PV = nRT Implies:
n/V = P/RT
but,
n/V = M
molarity
Kp =
PCH4 PH2O
PCO PH23
So M = P/RT
PCH4 PH2O
1
2
P
P
(RT)
RT RT
CH4
H2O
Kc =
= Kc =
3
3
1
PCO PH2
PCO PH2
(RT)4
RT (RT)3
Kc = Kp(RT)2
2010
(RT)2
Kp
Kp = Kc(RT)-2
n
Kp = Kc(RT)
CO(g) + 3H2(g) CH4(g) + H2O(g)
Where n = (final moles gas - initial moles gas)
n = (Product gas moles - Reactant gas moles)
Homogeneous:
E ilib i Heterogeneous:
Equilibria
equilibrium involving
reactants and
reactants and product
products in several
in the same phase.
phases.
C(s) + H2O(g) CO(g) + H2(g) But, what is the [C(s)] = ?
Kc =
[CO(g)] [H2(g)]
[C(s)] [H2O(g)]
Kp = Kc(RT)n
2010
10
Kp =
Kc =
PCH4 PH2S2
PCS2 PH24
Kc = [NH3]2 [CO2]
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Interpreting Kc and Kp
Qualitative interpretation:
interpretation
a) Kc >> 1
Products
b) Kc << 1
c)) Kc 1
Equilibrium
q
mixture contains
significant quantities of both
reactants and products.
Reactants
Quantitative interpretation:
Predicting the direction of a Rxn
Reaction Quotient, Q : an expression of the same form
as Kc or Kp, but whose [ ]s are NOT at equilibrium.
2010
The [ ]s represent instantaneous or snapshot values.
12
Reaction Quotient Qc
Qc =
Methanation rxn
[CH4]i [H2O]i
[CO]i [H2]i3
Evaluation of Qc values:
a) Qc > Kc
b) Qc < Kc
c) Qc = Kc
Reaction is at Equilibrium!13
Reaction Quotient: Qc
Qc =
[CH4]i [H2O]i
[CO]i [H2]i3
Qc = Kc
Q c < Kc
Qc > Kc
2010
14
Kc298K = 8.0x1035
Kc =
Kc =
[SO3]2
[SO2]2 [O2]
Let x = unknown [ ]
So x = [O2],
S
] 2x
2 = [SO2]
1.0 M2
1.0
= 8.0x1035 =
(2x)2 x
4x3
x3 = 3.125x10-37
And x =
x = 6.8x10-13 M = [O2]
2010
1.0
x3
= 3.2x1036
3.125 x10 37
[SO2] = 1.4x10-12 M
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[N2O4]
(2x)2
N2O4(g) 2NO2(g)
0.100 - x
4x2
Initial 0.100
0
0 100 M
0.36 =
0.100 - x
Change
-x
+2x
0.036 - 0.36x = 4x2
0.100
x
+2x
Equilib
0 = 4x2 + 0.36x - 0.036
a = 4 b = .36 c = -.036
x = -0.15 or x = 0.060
for quadratic formula 2x = 2 x .060 = .12M = [NO2]
2010
16
0.100 - 0.060 = 0.040 = [N2O4]
Kc =
0.100 M 0.400 M
-X
-3X
.100
X
.400
- 3X
Equilib
+X
+X
+X
+X
Change
[CH4] [H2O]
[CO] [H2]3
Kc =
Kc =
Kc1200K = 3.92
3 92
Now what?
XX
X2
=
= 3.92
3
(.100-X)(.400-3X)
(.100-X)(.400-3X)3
2010
17
LeChateliers Principle:
Principle
Changing Reaction Conditions
Defined:
When conditions are changed for a chemical system
at equilibrium, the system responds by altering
equilibrium [ ]s until equilibrium is re-established.
NOTE: Kc is unchanged
g for [ ] and ppressure
changes (gas rxns, which is same as [ ]).
Kc IS changed for Temp. changes
Changes to Reactant/Product [ ]
A + B C + D
[C]i [D]i
[C] [D]
Qc =
Kc =
[A]i [B]i
[A] [B]
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18
PV = nRT
so...
M = n/V = P/RT
2010
Kc =
[C] [D]
[A] [B]
Thus, if pressure is
increased or volume
decreased, concentration
is increased for a gas. 19
Qc =
[C]i [D]i
[A]i [B]i
20
Kp =
PCH4 PH2O
PCO PH23
Qp =
PCH4i PH2Oi
PCOi PH2i3
Suppose
pp
we double the ppressure for the rxn. Which direction
will this push the rxn?
Qp =
So Qp =
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2PCH42PH2O
2PCO (2PH2)
Kp
4
OR Qp< Kp
4 K
Kp
p =
16
4
So, which way
does the rxn
proceed?
21
1. Pressure increase:
increase
n < 0
n > 0
Favored
Products
Reactants
2. Pressure decrease:
decrease
n < 0
n > 0
Reactants
Products
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3 N2(g)
3.
2( ) + 3H2(g)
2( ) 2NH3(g)
3( )
Effect of decreasing pressure?
Effect of removing NH3 from rxn vessel?
Kc400C = .000805
a. If we remove CO from the rxn vessel does Kc
increase or decrease?
b.2010If CO removed is Qc < or > Kc?
23
Temperature and Kc
2CO2 2CO + O2
= -206.2 kJ/mol
Temp.
Kc
298 K
4.9x1027
800
1.38x105
1000
2.54x102
1200
3.92
= +566 kJ/mol
Temp.
Kc
1500 K
2.21x10-10
2000
1.79x10-5
2500
1 56x10-2
1.56
3000
1.61
3500
15.8
st
Why in the 1 rxn does Kc as Temp and in the
2nd Kc as T ?
1. Exothermic: heat is a product - Add product, rxn
2. Endothermic: heat is a reactant - add reactant, rxn 24
Catalysts and Kc
Catalyst:
a substance that changes the activation energy of
reaction by providing an alternate reaction pathway.
The catalyst is not consumed in the reaction.
Usually catalysts speed up the reaction rate since Ea
is reduced.
25
13_17
20
No Cl present
E a (uncatalyzed reaction)
10
Enerrgy (kJ)
E a (catalyzed reaction)
Cl + O 3 + O
0
ClO + O 2 + O
Cl + O 2 + O 2
400
2010
Copyright
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Progress of reaction
13-17
298 K
2H2O(g)
Kc is unchanged
2H2(g) + O2(g)
2010
Pt
298 K
Kc is still unchanged
2H2O(g)
= -242 kJ/mol
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