Chemical Equilibrium

Chapter 15

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Chapter 15; Equilibrium
I. Dynamic Equilibrium
II. Equilibrium Constant; Kc and Kp
III. Homogenous vs. Heterogeneous
Equilibrium
IV. Calculation of K from Equilibrium
Concentrations

Chapter 15; Equilibrium
V. Predicting Reaction Direction for
Nonequilibria Mixtures
Reaction Quotient, Q
VI. Le Chatliers Principle
VII. Calculating Equilibrium Concentrations
from Initial Concentrations and K
Square Root
Quadratic Formula
Equilibrium is a state in which there are no observable
changes as time goes by.
Chemical equilibrium is achieved when:
the rates of the forward and reverse reactions are equal and
they are not zero.
the concentrations of the reactants and products remain
constant
Chemical equilibrium
N
2
O
4
(g)
14.1
2NO
2
(g)
N
2
O
4
(g) 2NO
2
(g)
Start with NO
2
Start with N
2
O
4
Start with NO
2
& N
2
O
4
equilibrium
equilibrium
equilibrium
14.1
Equilibrium favors the reactant side
14.1
constant
N
2
O
4
(g) 2NO
2
(g)
= 4.63 x 10
-3
K =
[NO
2
]
2

[N
2
O
4
]
aA + bB cC + dD
K =
[C]
c
[D]
d

[A]
a
[B]
b

K >> 1
K << 1
Lie to the right Favor products
Lie to the left Favor reactants
Equilibrium Will
14.1
Homogenous equilibrium applies to reactions in which all
reacting species are in the same phase.
N
2
O
4
(g) 2NO
2
(g)
K
c
=
[NO
2
]
2

[N
2
O
4
]
K
p
=
NO
2

P
2

N
2
O
4

P
In most cases
K
c
K
p

aA (g) + bB (g) cC (g) + dD (g)
14.2
K
p
= K
c
(RT)
Dn

Dn = moles of gaseous products moles of gaseous reactants
= (c + d) (a + b)
Heterogenous equilibrium applies to reactions in which
reactants and products are in different phases.
CaCO
3
(s) CaO (s) + CO
2
(g)
K
c
=

[CaO][CO
2
]
[CaCO
3
]
[CaCO
3
] = constant
[CaO] = constant
K
c
= [CO
2
] = K
c
x

[CaCO
3
]
[CaO]
K
p
= P
CO

2
The concentration of solids and pure liquids are not
included in the expression for the equilibrium constant.
14.2
P
CO

2
= K
p

CaCO
3
(s) CaO (s) + CO
2
(g)
P
CO

2
does not depend on the amount of CaCO
3
or CaO
14.2
Ways Different States of Matter
Can Appear in the Equilibrium
Constant, K
Molarity Partial Pressure
gas, (g) YES YES
aqueous, (aq) YES ---
liquid, (l) --- ---
solid, (s) --- ---
Writing Equilibrium Constant Expressions
The concentrations of the reacting species in the
condensed phase are expressed in M. In the gaseous
phase, the concentrations can be expressed in M or in atm.
The concentrations of pure solids, pure liquids and solvents
do not appear in the equilibrium constant expressions.
The equilibrium constant is a dimensionless quantity.
In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.
14.2
The equilibrium concentrations for the reaction between
carbon monoxide and molecular chlorine to form COCl
2
(g)
at 74
0
C are [CO] = 0.012 M, [Cl
2
] = 0.054 M, and [COCl
2
] =
0.14 M. Calculate the equilibrium constants K
c
and K
p
.
CO (g) + Cl
2
(g) COCl
2
(g)
K
c
=
[COCl
2
]
[CO][Cl
2
]
=
0.14
0.012 x 0.054
= 220
K
p
= K
c
(RT)
Dn

Dn = 1 2 = -1 R = 0.0821 T = 273 + 74 = 347 K
K
p
= 220 x (0.0821 x 347)
-1
= 7.7
14.2
The equilibrium constant K
p
for the reaction

is 158 at 1000K. What is the equilibrium pressure of O
2
if
the P
NO
= 0.400 atm and P
NO
= 0.270 atm?
2
2NO
2
(g) 2NO (g) + O
2
(g)
14.2
K
p
=
2
P
NO
P
O

2
P
NO

2
2
P
O

2
= K
p

P
NO

2
2
P
NO

2
P
O

2
= 158 x (0.400)
2
/(0.270)
2
= 347 atm
Predicting Reaction Direction
from a Nonequilibrium Mixture

Calculate Reaction Quotient, Q
The expression for Q is the same as K
BUT nonequilibrium concentrations
rather than equilibrium concentrations
are put into the expression
Compare the value of Q to K.

The reaction quotient (Q
c
) is calculated by substituting the
initial concentrations of the reactants and products into the
equilibrium constant (K
c
) expression.
IF
Q
c
> K
c
system proceeds from right to left to reach equilibrium
Q
c
= K
c
the system is at equilibrium
Q
c
< K
c
system proceeds from left to right to reach equilibrium
14.4
Le Chteliers Principle

1. System starts at equilibrium.
2. A change/stress is then made to system at
equilibrium.
Change in concentration
Change in volume
Change in pressure
Change in Temperature
Add Catalyst
3. System responds by shifting to reactant or
product side to restore equilibrium.

If an external stress is applied to a system at equilibrium, the
system adjusts in such a way that the stress is partially offset
as the system reaches a new equilibrium position.
Le Chteliers Principle
Changes in Concentration
N
2
(g) + 3H
2
(g) 2NH
3
(g)
Add
NH
3

Equilibrium
shifts left to
offset stress
14.5
Le Chteliers Principle
Changes in Concentration continued
Change Shifts the Equilibrium
Increase concentration of product(s) left
Decrease concentration of product(s) right
Decrease concentration of reactant(s)
Increase concentration of reactant(s) right
left
14.5
aA + bB cC + dD
Add Add Remove
Remove
Le Chatliers Principle
Removing SO
2
, O
2
Le Chatliers Principle (cont)
Le Chatliers Principle (cont)
Le Chatliers Principle (cont)
Le Chteliers Principle
Changes in Volume and Pressure
(Only a factor with gases)
A (g) + B (g) C (g)
Change Shifts the Equilibrium
Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Decrease volume
Increase volume Side with most moles of gas
Side with fewest moles of gas
14.5
Le Chteliers Principle

Chemistry; The Science
in Context;by Thomas
R. Gilbert, Rein V.
Kirss, and Geoffrey
Davies, Norton
Publisher, 2004, p 752
Le Chteliers Principle
Changes in Temperature
Only factor that can change value of K
Change Exothermic Rx
Increase temperature K decreases
Decrease temperature K increases
Endothermic Rx
K increases
K decreases
14.5
Le Chteliers Principle; Temperature Effect
Chemistry; The Science
in Context;by Thomas
R. Gilbert, Rein V.
Kirss, and Geoffrey
Davies, Norton
Publisher, 2004, p 764
Adding a Catalyst
does not change K
does not shift the position of an equilibrium system
system will reach equilibrium sooner
Le Chteliers Principle
uncatalyzed catalyzed
14.5
Catalyst lowers E
a
for both forward and reverse reactions.
Catalyst does not change equilibrium constant or shift equilibrium.
Le Chteliers Principle
Change Shift Equilibrium
Change Equilibrium
Constant
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no
14.5
Animation of Le Chateliers Principle
Calculating Equilibrium Concentrations
from K and Initial Concentrations
1. Balance chemical equation.
2. Determine Q to see which way reaction will proceed to get
to equilibrium
3. Define changes needed to get to equilibrium. Use x to
represent the change in concentration to get to equilibrium.
Determine expression for equilibrium concentration.
4. Write the expression for equilibrium constant, K.
5. Substitute expressions defined in step 3 into the equilibrium
constant (step 4).
6. Solve for x and plug value back to table made in step 3.
14.4
At 1280
0
C the equilibrium constant (K
c
) for the reaction


Is 1.1 x 10
-3
. If the initial concentrations are [Br
2
] = 0.063
M and [Br] = 0.012 M, calculate the concentrations of these
species at equilibrium.
Br
2
(g) 2Br (g)
Br
2
(g) 2Br (g)
Let x be the change in concentration of Br
2

Initial (M)
Change (M)
Equilibrium (M)
0.063 0.012
-x +2x
0.063 - x 0.012 + 2x
[Br]
2

[Br
2
]
K
c
= K
c
=
(0.012 + 2x)
2

0.063 - x
= 1.1 x 10
-3

Solve for x
14.4
K
c
=
(0.012 + 2x)
2

0.063 - x
= 1.1 x 10
-3

4x
2
+ 0.048x + 0.000144 = 0.0000693 0.0011x
4x
2
+ 0.0491x + 0.0000747 = 0
ax
2
+ bx + c =0
-b b
2
4ac

2a
x =
Br
2
(g) 2Br (g)
Initial (M)
Change (M)
Equilibrium (M)
0.063 0.012
-x +2x
0.063 - x 0.012 + 2x
x = -0.00178 x = -0.0105
At equilibrium, [Br] = 0.012 + 2x = -0.009 M or 0.00844 M
At equilibrium, [Br
2
] = 0.062 x = 0.0648 M
14.4