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Chapter 14

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.

CO(g) + 3H2(g) CH4(g) + H2O(g)

The indicates that both the forward (left to


right) and reverse (right to left) reactions are
occurring simultaneously and rates are equal
equal.
In addition it implies that significant quantities of
all reactants AND products are present at
equilibrium.
Since rate of forward = rate of reverse then ALL
concentrations of both reactants AND products are

constant!
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Catalytic Methanation Reaction Approaches Equilibrium

CO + 3H2 CH4 + H2O

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Catalytic Methanation Reaction Approaches Equilibrium

CO + 3H2 CH4 + H2O

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Equilibrium Constant - Kc
Since at equilibrium all concentrations are
constant a mathematical expression can be
written describing the relationship.

Kc =

Each reactant and product


must be raised to its
coefficient power.

[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.
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Law of Mass Action


The value of Kc for a particular reaction at a
specific temperature is constant no matter what
starting reactant or product concentrations are.

CO(g) + 3H2(g) CH4(g) + H2O(g)

Kc =

[[CH4] [H
[ 2O]]
[CO] [H2]3

Suppose: we start with 1.00 mol CO and 3.00 mol H2 in


a 10.0L rxn vessel @ 927C.
At equilibrium, 0.387 mol H2O is present.
What is the molar composition of all materials?
And what is the value of Kc?
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Stoichiometry and Law of Mass Action


Moles

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
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Kc =

Equilibrium Constant for Gases:


The Ideal Gas Law:

Kp

PV = nRT Implies:
n/V = P/RT
but,
n/V = M
molarity

Therefore, in gas phase rxns we


can relate partial pressures and
molar concentrations.
CO(g) + 3H2(g) CH4(g) + H2O(g)

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

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Equilibrium Constant for Gases:


Kc = Kp

(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)]

For pure solids/liquids:


[ ] = 1, as long as some is
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present.

Where n = (final moles gas - initial moles gas)


n = (Product gas moles - Reactant gas moles)

Kp = Kc(RT)n

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Writing Kc and/or Kp expressions


1. CS2(g) + 4H2(g) CH4(g) + 2H2S(g)

Kp =
Kc =

PCH4 PH2S2
PCS2 PH24

2. Fe3+(aq) + 3OH-(aq) Fe(OH)3(s)


1
[Fe33+] [OH-]3
3. (NH4)2CO3(s) 2NH3(g) + CO2(g) + H2O(g)

Kp = PNH32 PCO2 PH2O

Kc = [NH3]2 [CO2]

4. (NH4)2CO3(s) 2NH3(aq) + CO2(aq) + H2O(l)

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Interpreting Kc and Kp
Qualitative interpretation:
interpretation
a) Kc >> 1

Equilibrium mixture is primarily

Products

b) Kc << 1

Equilibrium mixture is primarily...

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.
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The [ ]s represent instantaneous or snapshot values.
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Reaction Quotient Qc

CO(g) + 3H2(g) CH4(g) + H2O(g)

Qc =

Methanation rxn

i subscript refers to these [ ]s

[CH4]i [H2O]i
[CO]i [H2]i3

being taken at some instant


prior to equilibrium.

Evaluation of Qc values:

Reaction moves left


reactants products
so that Qc until = Kc

a) Qc > Kc
b) Qc < Kc

Reaction moves right


reactants products
so that Qc until = 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

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Using Kc to Determine Equilibrium [ ]s


2SO2(g) + O2(g) 2SO3(g)

Kc298K = 8.0x1035

Suppose at equilibrium [SO3] = 1.0 M and [SO2] = 2[O2]


What is [SO2] & [O2] =? Write the equilibrium expression.

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]
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1.0

x3

= 3.2x1036

3.125 x10 37
[SO2] = 1.4x10-12 M
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Equilibrium Problem involving a quadratic in x


If a 1.00 L flask initially contains
Kc100C = 0.36
0.100 mol N2O4, what will be [NO2]
[NO2]2
at equilibrium? Write the equilibrium expression.
Kc =

[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]
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0.100 - 0.060 = 0.040 = [N2O4]
Kc =

Equilibrium Problem involving a quartic in x


CO(g) + 3H2(g) CH4(g) + H2O(g)
Initial

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

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Roots at: X = .052 and X =.295


X < .100

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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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The Concentration of a Gas at a Given Temperature

PV = nRT

so...

M = n/V = P/RT
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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

1. Removal of reactant(s): [reactant] , Qc > Kc


Reaction driven?
2. Addition of product(s): [product] , Qc > Kc
Reaction driven?
3. Addition of reactant(s): [reactant] , Qc < Kc
Reaction driven?
4. Removal of product(s): [product] , Qc < Kc
Reaction driven?
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Pressure Effects in Gas Phase Rxns


CO(g) + 3H2(g) CH4(g) + H2O(g)
Pressure for all species increases equally - initially:

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?
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Pressure Effects in Gas Phase Rxns


The coefficients, that is n or change in moles of gas,
are the key to predicting effect of pressure changes.

n = (Product gas moles - Reactant gas moles)

1. Pressure increase:
increase

n < 0
n > 0

Favored
Products
Reactants

Press re increase: the reaction moves


Pressure
mo es the direction that
will decrease moles of gas/pressure.

2. Pressure decrease:
decrease

n < 0
n > 0

Reactants
Products

Pressure decrease: the reaction moves the direction that


will increase moles of gas/pressure.
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Some Sample Problems

1. CaCO3(s) CaO(s) + CO2(g)

Which direction if pressure is increased?


If we add CaCO3 what will happen?
NOTHING!

2. 2H2(g) + O2(g) 2H2O(g)


Give 2 or more ways to increase the yield of H2O

3 N2(g)
3.
2( ) + 3H2(g)
2( ) 2NH3(g)
3( )
Effect of decreasing pressure?
Effect of removing NH3 from rxn vessel?

4. COCl2(g) CO(g) + Cl2(g)

Kc400C = .000805
a. If we remove CO from the rxn vessel does Kc

increase or decrease?
b.2010If CO removed is Qc < or > Kc?

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Temperature and Kc

CO + 3H2 CH4 + H2O

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.

Kc IS NOT changed by the presence of a


catalyst.
Equilibrium [ ]s ARE NOT changed.
Equilibrium is reached faster.
Catalysts reduce Ea for BOTH rxn directions
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Comparison of Activation Energies in the Uncatalyzed


and Catalyzed Decompositions of Ozone

13_17

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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
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Copyright

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Progress of reaction

13-17

Houghton Mifflin Company. All rights reserved

Catalysts and Rate vs. Kc


2H2(g) + O2(g) 2H2O(g)
= 242 kJ/mol
@ combustion temp. rxn powers shuttle to orbit.
2H2(g) + O2(g) ~1200 K
2H2O(g)
= - 242 kJ/mol

@ room temp. nothing happens in rxn.


2H2(g) + O2(g)

298 K

2H2O(g)

Kc is unchanged

Add a Pt catalyst ...

2H2(g) + O2(g)
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Pt
298 K

Kc is still unchanged

2H2O(g)

= -242 kJ/mol
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