CH15 Chemical Equilibrium

Chapter 15:
Chemical Equilibrium
Chemistry: The Molecular Nature
of Matter, 6E

Jespersen/Brady/Hyslop

Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E 2
Dynamic Equilibrium in Chemical
Systems
Chemical equilibrium exists when
Rates of forward and reverse reactions are equal
Reaction appears to stop
[reactants] and [products] don't change over
time
Remain constant
Both forward and reverse reaction never cease
Equilibrium signified by double arrows ( )
or equal sign (=)
Dynamic Equilibrium
N
2
O
4
2 NO
2

Initially forward reaction rapid
As some reacts +[N
2
O
4
] so rate forward +
Initially Reverse reaction slow
No products
As NO
2
forms
| Reverse rate
Ions collide more frequently as [ions] |
Eventually rate
forward
= rate
reverse

Equilibrium

Dynamic Equilibrium
Almost all systems come to equilibrium
Where equilibrium lies depends on system
Some systems equilibrium hard to detect
Essentially no reactants or no products present
(Fig. 15.1)
Reaction Reversibility
Closed system
Equilibrium can be
reached from either
direction
Independent of whether
it starts with reactants
or products
Always have the same
composition at
equilibrium under same
conditions

N
2
O
4
2 NO
2

For given overall system composition
Always reach same equilibrium concentrations
Whether equilibrium is approached from forward or
reverse direction
N
2
O
4
2 NO
2

Reactants
Products
Equilibrium
Equilibrium
Simple relationship among [reactants] and
[products] for any chemical system at
equilibrium
Called = mass action expression
Derived from thermodynamics
Forward reaction: A B Rate = k
f
[A]
Reverse reaction: A B Rate = k
r
[B]
At equilibrium: A B k
f
[A] = k
r
[B]
rate forward = rate reverse
rearranging:
constant
[A]
[B]
= =
r
f
k
k
k
f

k
r

Ex: H
2
(g) + I
2
(g) 2HI(g) 440C
Expt
#
Initial
Amts
Equilm
Amts
Equilm
[M]
I 1.00 mol H
2
0.222 mol H
2
0.0222 M H
2

10 L 1.00 mol I
2
0.222 mol I
2
0.0222 M I
2

0.00 mol HI 1.56 mol HI 0.156 M HI
II 0.00 mol H
2
0.350 mol H
2
0.0350 M H
2

10 L 0.100 mol I
2
0.450 mol I
2
0.0450 M I
2

3.50 mol HI 2.80 mol HI 0.280 M HI
Ex: H
2
(g) + I
2
(g) 2HI(g) 440C
Expt
#
Initial Amts Equilm
Amts
Equilm
[M]
III 0.0150 mol H
2
0.150 mol H
2
0.0150 M H
2

10 L 0.00 mol I
2
0.135 mol I
2
0.0135 M I
2

1.27 mol HI 1.00 mol HI 0.100 M HI
IV 0.00 mol H
2
0.442 mol H
2
0.0442 M H
2

10 L 0.00 mol I
2
0.442 mol I
2
0.0442 M I
2

4.00 mol HI 3.11 mol HI 0.311 M HI
Mass Action Expression (MAE)
Uses stoichiometric coefficients as exponent
for each reactant
For reaction: aA + bB cC + dD

Reaction quotient
Numerical value of mass action expression
Equals Q at any time, and
Equals K only when reaction is known to be at
equilibrium
b
a
d c
[B] [A]
[D] [C]
Q =
Mass Action Expression
= same for all data sets at equilibrium

] ][I [H
[HI]
Q
2 2
2
=
] ][I [H
[HI]
Q
2 2
2
=
4 . 49
) 0222 . 0 )( 0222 . 0 (
) 156 . 0 (
2
=
8 . 49
) 0450 . 0 )( 0350 . 0 (
) 280 . 0 (
2
=
4 . 49
) 0135 . 0 )( 0150 . 0 (
) 100 . 0 (
2
=
5 . 49
) 0442 . 0 )( 0442 . 0 (
) 311 . 0 (
2
=
Equilibrium Concentrations
(M)
Expt [H
2
] [I
2
] [HI]
I 0.0222 0.0222 0.156
II 0.0350 0.0450 0.280
III 0.0150 0.0135 0.100
IV 0.0442 0.0442 0.311
Average = 49.5
Equilibrium Law
For reaction at equilibrium write the following
Equilibrium Law (at 440 C)

Equilibrium constant = K
c
= constant at given T
Use K
c
since usually working with concentrations in
mol/L
For chemical equilibrium to exist in reaction
mixture, reaction quotient Q must be equal to
equilibrium constant, K
c

5 . 49
] ][I [H
[HI]
2 2
2
= =
c
K
Predicting Equilibrium Law
For general chemical reaction:
dD + eE fF + gG
Where D, E, F, and G represent chemical formulas
d, e, f, and g are coefficients

Mass action expression =

Note: Exponents in mass action expression
are stoichiometric coefficients in balanced
equation.
Equilibrium law is:
e d
g f
[E] [D]
[G] [F]
e d
g f
[E] [D]
[G] [F]
=
c
K
Predicting Equilibrium Law
Where only concentrations that satisfy this
equation are equilibrium concentrations
Numerator
Multiply [products] raised to their
stoichiometric coefficients
Denominator
Multiply [reactants] raised to their
stoichiometric coefficients

is scientists convention
d
f
c
K
] reactants [
] products [
=
Ex. Equilibrium Law
3 H
2
(g) + N
2
(g) 2 NH
3
(g)
K
c
= 4.26 x 10
8
at 25 C
What is equilibrium law?

8
2
3
2
2
3
10 26 . 4
] [N ] [H
] [NH
= =
c
K
Learning Check
Write mass action expressions for the following:
2 NO
2
(g) N
2
O
4
(g)

2CO (g) + O
2
(g) 2 CO
2
(g)

2
2
4 2
] [NO
] O [N
Q =
] [O [CO]
] [CO
Q
2
2
2
2
=
Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Your Turn!
Which of the following is the correct mass
action expression (MAE) for the reaction:
Cu
2+
(aq) + 4NH
3
(aq) [Cu(NH
3
)
4
2+
](aq)?
these of none D.
] ) [Cu(NH
] NH ][ [Cu
Q C.
] NH ][ [Cu
] ) [Cu(NH
Q B.
] NH ][ [Cu
] ) [Cu(NH
Q A.
2
4 3
4
3
2
3
2
2
4 3
4
3
2
2
4 3
+
+
+
+
+
+
=
=
=
17
Manipulating Equations for Chemical
Equilibria
Various operations can be performed on
equilibrium expressions
1. When direction of equation is reversed,
new equilibrium constant is reciprocal of
original

A + B C + D

C +D A + B
c
c
K
K
1
[C][D]
[A][B]
= =
'
[A][B]
[C][D]
=
c
K
Ex. Manipulating Equilibria 1
1. When direction of equation is reversed, new
equilibrium constant is reciprocal of original

3 H
2
(g) + N
2
(g) 2 NH
3
(g) at 25C

2 NH
3
(g) 3 H
2
(g) + N
2
(g) at 25C
9
8 2
3
2
3
2
10 35 . 2
10 26 . 4
1 1
] [NH
] [N ] [H

=
= = =
'
c
c
K
K
8
2
3
2
2
3
10 26 . 4
] [N ] [H
] [NH
= =
c
K
Manipulating Equilibria 2
2. When coefficients in equation are
multiplied by a factor, equilibrium
constant is raised to a power equal to that
factor.

A + B C + D

3A + 3B 3C + 3D
[A][B]
[C][D]
=
c
K
3
3 3
3 3
[A][B]
[C][D]
[A][B]
[C][D]
[A][B]
[C][D]
[B] [A]
[D] [C]
c c
K K = = =
' '
2. When coefficients in equation are multiplied by
factor, equilibrium constant is raised to power
equal to that factor
3 H
2
(g) + N
2
(g) 2 NH
3
(g) at 25C

multiply by 3
9 H
2
(g) + 3 N
2
(g) 6 NH
3
(g)

8
2
3
2
2
3
10 26 . 4
] [N ] [H
] [NH
= =
c
K
3
3
2
9
2
6
3
] [N ] [H
] [NH
c c
K K = =
' '
3. When chemical equilibria are added,
their equilibrium constants are
multiplied
A + B C + D

C + E F + G

A + B + E D + F + G
] ][ [
] ][ [
1
B A
D C
K
c
=
] ][ [
] ][ [
2
E C
G F
K
c
=
2 1 3
] ][ ][ [
] ][ ][ [
] ][ [
] ][ [
] ][ [
] ][ [
c c c
K K
E B A
G F D
E C
G F
B A
D C
K = = =
3. When chemical equilibria are added, their
equilibrium constants are multiplied

][CO] [NO
] ][CO [NO
] [NO
] [NO][NO
3
2 2
2
2
3

2 NO
2
(g) NO
3
(g) + NO(g)
NO
3
(g) + CO(g) NO
2
(g) + CO
2
(g)
NO
2
(g) + CO(g) NO(g) + CO
2
(g)
2
2
3
] [NO
] [NO][NO
1
=
c
K
][CO] [NO
] ][CO [NO
3
2 2
2
=
c
K
][CO] [NO
] [NO][CO
2
2
3
=
c
K
Therefore
3 2 1
c c c
K K K =
][CO] [NO
] [NO][CO
2
2
=
Learning Check
For: N
2
(g)

+ 3 H
2
(g)

2 NH
3
(g)

K
c
= 500 at a particular temperature.
What would be K
c
for following?
2 NH
3
(g)

N
2
(g)

+ 3 H
2
(g)

N
2
(g)

+ 3/2 H
2
(g)

NH
3
(g)

= = =
'
500
1 1
c
c
K
K
22.4
0.002
= = =
' '
500
2 1
c c
K K
Equilibrium Constant, K
c
Constant value equal to ratio of product
concentrations to reactant concentrations
raised to their respective exponents

Changes with temperature (vant Hoff
Equation)
Depends on solution concentrations
Assumes reactants and products are in
solution

d
f
c
K
] reactants [
] products [
=
Equilibrium Constant, K
p
Based on reactions in which substances are
gaseous
Assumes gas quantities are expressed in
atmospheres in mass action expression
Use partial pressures for each gas in place of
concentrations
Ex. N
2
(g)

+ 3 H
2
(g)

2 NH
3
(g)

3
H
N
2
NH
2
2
3
P P
P
=
P
K
How are K
p
and K
c
Related?

Start with Ideal Gas Law
PV=nRT
Rearranging gives

Substituting P/RT for molar concentration
into K
c
results in pressure-based formula
n = moles of gas in product moles of
gas in reactant
n
c
p
RT K K
A
= ) (
MRT RT
V
n
P = |
.
|
\
|
=
Learning Check
Consider the reaction: 2NO
2
(g) N
2
O
4
(g)
If K
p
= 0.480 for the reaction at 25C, what is
value of K
c
at same temperature?
An = n
products
n
reactants

= 1 2 = 1
n
c
p
(RT) K K =
1 n
p
c
) 298 0821 . 0 (
480 . 0
(RT)
K
K
A

= =
K
K
c
= 11.7

Your Turn!
Consider the reaction A(g) + 2B(g) 4C(g)
If the K
c
for the reaction is 0.99 at 25C, what
would be the K
p
?
A. 0.99
B. 2.0
C. 24.
D. 2400
E. None of these

n=(4 3)=1
K
p
= K
c
(RT)
n
K
p
= 0.99*(0.082057*298.15)
1

K
p
= 24
29
Homogeneous reaction/equilibrium
All reactants and products in same phase
Can mix freely
Heterogeneous reaction/equilibrium
Reactants and products in different phases
Cant mix freely
Solutions are expressed in M
Gases are expressed in M
Governed by K
c

Heterogeneous Equilibria
2NaHCO
3
(s) Na
2
CO
3
(s) + H
2
O(g) + CO
2
(g)
Equilibrium Law =

Can write in simpler form
For any pure liquid or solid, ratio of moles to
volume of substance (M) is constant
Ex. 1 mol NaHCO
3
occupies 38.9 cm
3

2 mol NaHCO
3
occupies 77.8 cm
3

2
) (
3
) (
2
) (
2
) (
3 2
] [
] ][ ][ [
s
g g s
NaHCO
CO O H CO Na
K =
M M 7 . 25
L 0.0389
NaHCO mol 1
3
= =
M M 7 . 25
L 0.0778
NaHCO mol 2
3
= =
Heterogeneous Equilibria
2NaHCO
3
(s) Na
2
CO
3
(s) + H
2
O(g) + CO
2
(g)
Ratio (n/V) or M of NaHCO
3
is constant (25.7 mol/L)
regardless of sample size
Likewise can show that molar concentration of
Na
2
CO
3
solid is constant regardless of sample size
So concentrations of pure solids and liquids
can be incorporated into equilibrium constant,
K
c

Equilibrium law for heterogeneous system written
without concentrations of pure solids or liquids

] CO ][ O H [
] NaHCO [
] CO Na [
) (
2
) (
2
2
) (
3
) (
3 2
g g
s
s
c
K K = =
Learning Check
Write equilibrium laws for the following:
Ag
+
(aq) + Cl
(aq) AgCl(s)

H
3
PO
4
(aq) + H
2
O() H
3
O
+
(aq) + H
2
PO
4
(aq)

] ][Cl [Ag
1
+
=
c
K
] PO [H
] PO ][H O [H
4 3
4 2 3
+
=
c
K
Your Turn!
Given the reaction:
3Ca
2+
(aq) + 2PO
4
3
(aq) Ca
3
(PO
4
)
2
(s)
What is the mass action expression?
2 3
4
3 2
2 3
4
3 2
2 4 3
2 3
4
3 2
2 4 3
2 3
4
3 2
] [PO ] [Ca
] 1 [
Q D.
] [PO ] [Ca
] ) (PO Ca [
Q C.
] 1 [
] [PO ] [Ca
Q B.
] ) PO ( [Ca
] PO [ ] [Ca
Q A.
+
+
+
+
=
=
=
=
34
Your Turn!
Given the reaction:
3Ca
2+
(aq) + 2PO
4
3
(aq) Ca
3
(PO
4
)
2
(s)
What is mass action expression

for the reverse
reaction?
2 3
4
3 2
2 3
4
3 2
2 4 3
2 3
4
3 2
2 4 3
2 3
4
3 2
] PO [ ] Ca [
] 1 [
Q D.
] PO [ ] Ca [
] ) (PO [Ca
Q C.
] 1 [
] PO [ ] Ca [
Q B.
] ) (PO [Ca
] PO [ ] Ca [
Q A.
+
+
+
+
=
=
=
=
35
Interpreting K
C

Large K (K>>1)
Means product rich mixture
Reaction goes far toward
completion
Ex.
2SO
2
(g) + O
2
(g) 2SO
3
(g)
K
c
= 7.0 10
25
at 25 C

1
10 0 . 7
] [O ] [SO
] [SO
25
2
2
2
2
3

= =
c
K
Interpreting K
C

Small K (K<<1)
Means reactant rich
mixture
Only very small amounts of
product formed
Ex.
H
2
(g) + Br
2
(g) 2HBr(g)
K
c
= 1.4 10
21
at 25 C

1
10 4 . 1
] ][Br [H
[HBr]
21
2 2
2
= =
c
K
Interpreting K
C
K ~ 1
Means product and
reactant concentrations
close to equal
Reaction goes only ~
halfway
Size of K gives measure of how
reaction proceeds

K >> 1 [products] >> [reactants]
K = 1 [products] = [reactants]
K << 1 [products] << [reactants]
Learning Check
Consider the reaction of 2NO
2
(g) N
2
O
4
(g)
If K
p
= 0.480 at 25C, does the reaction favor
product or reactant?
K is small (K < 1)
Reaction favors reactant
Since K is close to 1, significant amounts of
both reactant and product are present
Equilibrium Positions and Shifts
Equilibrium positions
Combination of concentrations that allow Q = K
Infinite number of possible equilibrium positions
Le Chteliers principle
System at equilibrium (Q = K) when upset by
disturbance (Q K) will shift to offset stress
System said to shift to right when
forward reaction is dominant (Q < K)
System said to shift to left when reverse
direction is dominant (Q > K)
Relationship Between Q and K
Q = K reaction at equilibrium
Q < K reactants products

Too many reactants
Must convert some reactant to product to move
reaction toward equilibrium
Q > K reactants products
Too many products
Must convert some product to reactant to move
reaction toward equilibrium
Examples of Le Chteliers Principle
Lets see how this works with changes in
1. Concentration
2. Pressure and volume
3. Temperature
4. Catalysts
5. Adding inert gas to system at constant
volume

1. Effect of Change in Concentration
Cu(H
2
O)
4
2+
(aq) + 4Cl
(aq) CuCl
4
2
(aq) + 4H
2
O
blue yellow
Equilibrium mixture is blue-green

Add excess Cl
(conc HCl)
Equilibrium shifts to products
Makes more yellow CuCl
4
2

Solution becomes green

4
) ( ) (
2
4 2
4
2
) (
2
4
] Cl ][ O) Cu(H [
] O H ][ CuCl [
aq aq
aq
c
K
+
=
4
) ( ) (
2
4 2
) (
2
4
4
2
] Cl ][ O) Cu(H [
] CuCl [
] O H [ aq aq
aq
c
c
K
K
+
= =
'
1. Effect of Change in Concentration
Cu(H
2
O)
4
2+
(aq) + 4Cl
(aq) CuCl
4
2
(aq) + 4H
2
O
blue yellow

Add Ag
+

Removes Cl
: Ag
+
(aq) + Cl
(aq)

AgCl(s)
Equilibrium shifts to reactants
Makes more blue Cu(H
2
O)
4
2+

Solution becomes bluer
Add H
2
O?
4
) ( ) (
2
4 2
) (
2
4
] Cl ][ O) Cu(H [
] CuCl [
aq aq
aq
c
K
+
=
Effect of Change in Concentration
2SO
2
(g) + O
2
(g) 2SO
3
(g)
K
c
= 2.4 x 10
-3
at 700
o
C
Which direction will the reaction move if
0.125 moles of O
2
is added to an equilibrium
mixture ?
A. Towards the products
B. Towards the reactants
C. No change will occur
46
Effect of Change in Concentration
When changing concentrations of reactants
or products
Equilibrium shifts to remove reactants or
products that have been added
Equilibrium shifts to replace reactants or
products that have been removed

Effect of Pressure and Volume Changes
Consider gaseous system at constant T and n
3H
2
(g) + N
2
(g) 2NH
3
(g)
If reduce volume (V)
Expect Pressure to increase (P)
To reduce pressure, look at each side of reaction
Which has less moles of gas
Reactants = 3 + 1 = 4 moles gas
Products = 2 moles gas
Reaction favors products (shifts to right)
3
H
N
2
NH
2
2
3
P P
P
K
P
=
Effect of P and V Changes
Consider gaseous system at constant T and n
Ex. H
2
(g) + I
2
(g) 2 HI(g)

If pressure is increased, what is the effect on
equilibrium?
n
reactant
= 1 + 1 = 2
n
product
= 2
Predict no change or shift in equilibrium
2 2
I H
2
HI
P P
P
K
P
=
2NaHSO
3
(s) NaSO
3
(s) + H
2
O(g) + SO
2
(g)

If you decrease volume of reaction, what is
the effect on equilibrium?
Reactants: no moles gas = all solids
Products: 2 moles gas
V, causes P
Reaction shifts to left (reactants), as this has
fewer moles of gas
2 2
SO O H
P P K
P
=
Reducing volume of gaseous reaction
mixture causes reaction to decrease number
of molecules of gas, if it can
Increasing pressure
Moderate pressure changes have negligible
effect on reactions involving only liquids
and/or solids
Substances are already almost incompressible
Changes in V, P and [X] effect position of
equilibrium (Q), but not K
Effect of Change in Temperature
Cu(H
2
O)
4
2+
(aq) + 4Cl
(aq) CuCl
4
2
(aq) + 4H
2
O
blue yellow
Reaction endothermic
Adding heat shifts equilibrium toward products
Cooling shifts equilibrium toward reactants
52
Ice
water
Boiling
water
Effect of Temperature Changes
H
2
O(s) H
2
O() AH =+6 kJ (at 0 C)
Energy + H
2
O(s) H
2
O()

Energy is reactant
Add heat, shift reaction right
3H
2
(g) + N
2
(g) 2NH
3
(g) AH
f
= 47.19 kJ
3 H
2
(g) + N
2
(g) 2 NH
3
(g) + energy

Energy is product
Add heat, shift reaction left
Effect of Temperature Changes
| T shifts reaction in direction that produces
endothermic (heat absorbing) change
+ T shifts reaction in direction that produces
exothermic (heat releasing) change
Changes in T change value of mass action
expression at equilibrium, so K changed
K depends on T
|T of exothermic reaction makes K smaller
More heat (product) forces equilibrium to reactants
|T of endothermic reaction makes K larger
More heat (reactant) forces equilibrium to products

Catalysts And Equilibrium
Catalyst lowers E
a

for both forward
and reverse
reaction

Change in E
a

affects rates k
r

and k
f
equally

Catalysts have no
effect on
equilibrium
Effect of Adding Inert Gas
Inert gas
One that does not react with components of
reaction
Ex. Argon, Helium, Neon, usually N
2

Adding inert gas to reaction at fixed V (n and
T), | P of all reactants and products
Since it doesnt react with anything
No change in concentrations of reactants or
products
No net effect on reaction
How to Use Le Chteliers Principle
1. Write mass action expression for reaction
2. Examine relationship between affected
concentration and Q (direct or indirect)
3. Compare Q to K
If change makes Q > K, shifts Left
If change makes Q < K, shifts Right
If change has no effect on Q, no shift expected
Learning Check:
Consider:
H
3
PO
4
(aq) + 3OH
(aq) 3H
2
O() + PO
4
3
(aq)

What will happen if PO
4
3
is removed?
Q is proportional to [PO
4
3
]
+ [PO
4
3
], + Q
Q < K equilibrium shifts to right
] PO H [ ] OH [
] PO [
Q
4 3
3
3
4
=
Learning Check:
The reaction
H
3
PO
4
(aq) + 3OH
(aq) 3H
2
O(aq) + PO
4
3
(aq)
is exothermic.
What will happen if system is cooled?
Since reaction is exothermic, heat is product
Heat is directly proportional to Q
+T, + Q
Q < K equilibrium shifts to right
heat
] PO H [ ] OH [
] PO [
Q
4 3
3
3
4
=
Your Turn!
The equilibrium between aqueous cobalt ion
and the chlorine ion is shown:
[Co(H
2
O)
6
]
2+
(aq) + 4Cl
(aq) [Co(Cl)
4
]
2
(aq) + 6H
2
O()
pink blue
It is noted that heating a pink sample causes it
to turn violet.
The reaction is:
A. endothermic
B. exothermic
C. cannot tell from the given
information
60
Your Turn!
The following are equilibrium constants for the
reaction of acids in water, K
a
. Which is the
most efficient reaction?
A. K
a
= 2.210
3

B. K
a
= 1.810
5
C. K
a
= 4.010
10
D. K
a
= 6.310
3
61
Equilibrium Calculations
For gaseous reactions, use either K
P
or K
C

For solution reactions, must use K
C

Either way, two basic categories of
calculations
1. Calculate K from known equilibrium
concentrations or partial pressures
2. Calculate one or more equilibrium
concentrations or partial pressures using
known K
P
or K
C
Calculating K
C
from Equilibrium
Concentrations
When all concentrations at equilibrium are
known
Use mass action expression to relate
concentrations to K
C
Two common types of calculations
A. Given equilibrium concentrations, calculate K
B. Given initial concentrations and one final
concentration
Calculate equilibrium concentration of
all other species
Then calculate K
Calculating K
C
Given Equilibrium
Concentrations
Ex. 1 N
2
O
4
(g) 2NO
2
(g)
If you place 0.0350 mol N
2
O
4
in 1 L flask at
equilibrium, what is K
C?

[N
2
O
4
]
eq
= 0.0292 M
[NO
2
]
eq
= 0.0116 M

] [
] [
4 2
2
2
O N
NO
K
c
=
] 0292 . 0 [
] 0116 . 0 [
2
=
c
K
K
C
= 4.61 10
3

Your Turn!
For the reaction: 2A(aq) + B(aq) 3C(aq)
the equilibrium concentrations are: A = 2.0 M,
B = 1.0 M and C = 3.0 M. What is the
expected value of K
c
at this temperature?
A. 14
B. 0.15
C. 1.5
D. 6.75
[B] [A]
[C]
2
3
=
c
K
[1.0] [2.0]
[3.0]
2
3
=
c
K
65
Calculating K
C
Given Initial Concentrations
and One Final Concentration
Ex. 2 2SO
2
(g) + O
2
(g) 2SO
3
(g)
1.000 mol SO
2
and 1.000 mol O
2
are placed in
a 1.000 L flask at 1000 K. At equilibrium
0.925 mol SO
3
has formed. Calculate K
C
for
this reaction.
1
st
calculate concentrations of each
Initial

Equilibrium

M
L
mol
O SO 00 . 1
00 . 1
00 . 1
] [ ] [
2 2
= = =
M
L
mol
SO 925 . 0
00 . 1
925 . 0
] [
3
= =
How to Solve:
Set up Concentration Table
Based on the following:
Changes in concentration must be in same ratio
as coefficients of balanced equation
Set up table under balanced chemical equation
Initial concentrations
Controlled by person running experiment
Changes in concentrations
Controlled by stoichiometry of reaction
Equilibrium concentrations
Equilibrium
Concentration
=
Initial
Concentration

Change in
Concentration
Next Set up Concentration Table
2SO
2
(g) + O
2
(g) 2SO
3
(g)
Initial Conc. (M) 1.000 1.000 0.000
Changes in Conc. (M)
Equilibrium Conc. (M)
[SO
2
] consumed = Amt of SO
3
formed
= [SO
3
] at equilibrium = 0.925 M
[O
2
] consumed = amt SO
3
formed
= 0.925/2 = 0.462 M
[SO
2
] at equilibrium = 1.000 0.975 = 0.075
[O
2
] at equilibrium = 1.00 0.462 = 0.538 M
0.925 0.462 +0.925
0.075
0.538
0.925
Ex. 2
Finally calculate K
C
at 1000 K

] [O ] [SO
] [SO
2
2
2
2
3
c
= K
] 538 . 0 [ ] 075 . 0 [
] 925 . 0 [
2
2
=
c
K
K
c
= 2.8 10
2
= 280

Summary of Concentration Table
Used for most equilibrium calculations (Ch
15, 17, and 18)
1. Equilibrium concentrations are only values
used in mass action expression
Values in last row of table
2. Initial value in table must be in units of
mol/L (M)
[X]
initial
= those present when reaction
prepared
No reaction occurs until everything is
mixed
Summary of Concentration Table
3. Changes in concentrations always occur in
same ratio as coefficients in balanced
equation
4. In change row be sure all [reactants]
change in same directions and all [products]
change in opposite direction.
If [reactant]
initial
= 0, its change must be + (|)
because [reactant]
final
= negative
If [reactants] +, all entries for reactants in change
row should have minus sign and all entries for
products should be positive
Calculate [X]
equilibrium
from K
c
and [X]
initial
When all concentrations but one are known
Use mass action expression to relate K
c

and known concentrations to obtain
missing concentrations
Ex. 3 CH
4
(g) + H
2
O(g) CO(g) + 3H
2
(g)
At 1500 C, K
c
= 5.67. An equilibrium
mixture of gases had the following
concentrations: [CH
4
] = 0.400 M and
[H
2
] = 0.800M and [CO] =0.300M.
What is [H
2
O] at equilibrium ?
Calculate [X]
equilibrium
from K
c
and [X]
initial
Ex. 3 CH
4
(g) + H
2
O(g) CO(g) + 3H
2
(g) K
c
= 5.67
[CH
4
] = 0.400 M; [H
2
] = 0.800M; [CO] =0.300M
What is [H
2
O] at equilibrium?
First, set up equilibrium

Next, plug in equilibrium concentrations and K
c

O] ][H [CH
] [CO][H
2 4
3
2
=
c
K
[H
2
O] = 0.0678 M
27 . 2
154 . 0
5.67) ( [0.400]
800] [0.300][0.
O] [H
3
2
= =
c
K ] [CH
] [CO][H
O] [H
4
3
2
2
=
Calculating [X]
Equilibrium
from K
c

When Initial Concentrations Are Given
Write equilibrium law/mass action expression
Set up Concentration table
Allow reaction to proceed as expected,
using x to represent change in
concentration
Substitute equilibrium terms from table into
mass action expression and solve
Calculate [X]
equilibrium
from [X]
initial
and K
C

Ex. 4 H
2
(g) + I
2
(g) 2HI(g) at 425 C
K
C
= 55.64
If one mole each of H
2
and I
2
are placed in a
0.500 L flask at 425 C, what are the
equilibrium concentrations of H
2
, I
2
and HI?
Step 1. Write Equilibrium Law

64 . 55
] ][ [
] [
2 2
2
= =
I H
HI
K
c
Ex. 4 Step 2. Concentration Table
Conc (M) H
2
(g) + I
2
(g) 2HI

(g)
Initial 2.00 2.00 0.000
Change
Equilm
Initial [H
2
] = [I
2
] = 1.00 mol/0.500L =2.00M
Amt of H
2
consumed = Amt of I
2
consumed = x
Amt of HI formed = 2x
x +2x x
+2x 2.00 x 2.00 x
2
2 2
) 00 . 2 (
) 2 (
) 00 . 2 )( 00 . 2 (
) 2 (
64 . 55
x
x
x x
x
=

=
Ex. 4 Step 3. Solve for x
Both sides are squared so we can take
square root of both sides to simplify
2
2
) 00 . 2 (
) 2 (
64 . 55
x
x
K
= =
) 00 . 2 (
2
459 . 7
x
x
=
x x 2 ) 00 . 2 ( 459 . 7 =
x x 2 459 . 7 918 . 14 =
58 . 1
459 . 9
918 . 14
= = x
x 459 . 9 918 . 14 =
Ex. 4 Step 4. Equilibrium Concentrations
Conc (M) H
2
(g) + I
2
(g) 2HI

(g)
Initial 2.00 2.00 0.00
Change
Equilm
[H
2
]
equil
= [I
2
]
equil
= 2.00 1.58 = 0.42 M
[HI]
equil
= 2x = 2(1.58) = 3.16
1.58 +3.16 1.58
+3.16 0.42 0.42
Calculate [X]
equilibrium
from [X]
initial
and K
C

Ex. 5 H
2
(g) + I
2
(g) 2HI(g) at 425 C
K
C
= 55.64
If one mole each of H
2
, I
2
and HI are placed
in a 0.500 L flask at 425 C, what are the
equilibrium concentrations of H
2
, I
2
and HI?
Now have product as well as reactants initially

64 . 55
] ][ [
] [
2 2
2
= =
I H
HI
K
c
Conc (M) H
2
(g) + I
2
(g) 2HI

(g)
Initial 2.00 2.00 2.00
Change
Equilm
x +2x x
2.00 + 2x 2.00 x 2.00 x
2
2 2
) 00 . 2 (
) 2 00 . 2 (
) 00 . 2 )( 00 . 2 (
) 2 00 . 2 (
64 . 55
x
x
x x
x
+
=

+
=
2
2
) 00 . 2 (
) 2 00 . 2 (
64 . 55
x
x
K
+
= =
) 00 . 2 (
2 00 . 2
459 . 7
x
x
+
=
x x 2 00 . 2 ) 00 . 2 ( 459 . 7 + =
x x 2 00 . 2 459 . 7 918 . 14 + =
37 . 1
459 . 9
918 . 12
= = x
x 459 . 9 918 . 12 =
[H
2
]
equil
= [I
2
]
equil
= 2.00 x =
2.00 1.37 = 0.63 M

[HI]
equil
= 2.00 + 2x
= 2.00 + 2(1.37)
= 2.00 + 2.74
= 4.74 M
Your Turn!
N
2
(g) + O
2
(g) 2NO(g)
K
c
= 0.0123 at 3900
o
C
If 0.25 moles of N
2
and O
2
are placed in a
250 mL container, what are the equilibrium
concentrations of all species ?
A. 0.0526 M, 0.947 M, 0.105 M
B. 0.947 M, 0.947 M, 0.105 M
C. 0.947 M 0.105 M, 0.0526 M
D. 0.105 M, 0.105 M, 0.947 M
82
Your Turn! - Solution

Conc (M) N
2
(g) +O
2
(g) 2NO

(g)
Initial 1.00 1.00 0.00
Change x x + 2x
Equil 1.00 x 1.00 x + 2x

83
2 2
2
2
0.250 mol
[N ] [O ] 1.00
0.250 L
(2 ) 2
0.0123 0.0123
1 (1 )
0.0526 [NO] = 2 = 0.105
M
x x
x x
x M x M
= = =
= =

=
Calculate [X]
equilibrium
from [X]
initial
and K
C

Ex. 6
CH
3
CO
2
H(aq) + C
2
H
5
OH(aq) CH
3
CO
2
C
2
H
5
(aq) +
acetic acid ethanol ethyl acetate H
2
O(l)
K
C
= 0.11
An aqueous solution of ethanol and acetic
acid, each with initial concentration of 0.810
M, is heated at 100 C. What are the
concentrations of acetic acid, ethanol and
ethyl acetate at equilibrium?
Ex. 6 Step 1. Write Equilibrium Law
Need to find equilibrium values that satisfy
this
Step 2: Set up concentration table using x
for unknown
Initial concentrations
Change in concentrations
Equilibrium concentrations
11 . 0
H] CO OH][CH H [C
] H C CO [CH
2 3 5 2
5 2 2 3
= =
c
K
(M) CH
3
CO
2
H(aq) + C
2
H
5
OH(aq)
CH
3
CO
2
C
2
H
5
(aq) + H
2
O(l)
I 0.810 0.810 0.000
C
E
Amt of CH
3
CO
2
H consumed = Amt of C
2
H
5
OH
consumed = x
Amt of CH
3
CO
2
C
2
H
5
formed = + x
[CH
3
CO
2
H]
eq
and [C
2
H
5
OH ] = 0.810 x
[CH
3
CO
2
C
2
H
5
] = x
x +x x
+x 0.810 x 0.810 x
) 810 0 )( 810 0 (
11 0
x . x .
x
.

=
Rearranging gives

Then put in form of quadratic equation
ax
2
+ bx

+ c = 0

Solution for quadratic equation given by

x x x = + ) 62 . 1 6561 . 0 ( 11 . 0
2
0 11 . 0 1782 . 0 07217 . 0
2
= + x x x
0 07217 . 0 1782 . 1 11 . 0
2
= + x x
a
ac b b
x
2
4
2

=
This gives two roots: x = 10.6 and x =
0.064
Only x = 0.064 is possible
x = 10.6 is >> 0.810 initial concentrations
0.810 10.6 = negative concentration,
which is impossible
) 11 . 0 ( 2
) 07217 . 0 )( 11 . 0 ( 4 ) 1782 . 1 ( ) 1782 . 1 (
2

= x
22 . 0
164 . 1 1782 . 1
22 . 0
) 032 . 0 ( ) 388 . 1 ( 1782 . 1
=

= x
Ex. 6 Step 4. Equilibrium Concentrations
(M) CH
3
CO
2
H(aq) + C
2
H
5
OH(aq)
CH
3
CO
2
C
2
H
5
(aq) + H
2
O(l)
I 0.810 0.810 0.000
C
E
[CH
3
CO
2
C
2
H
5
]
equil
= x = 0.064 M
[CH
3
CO
2
H]
equil
= [C
2
H
5
OH]
equil
= 0.810 M x
= 0.810 M 0.064 M
= 0.746 M
0.064 +0.064 0.064
+0.064 0.746 0.746
When K
C
is very small
Ex. 7 2H
2
O(g) 2H
2
(g) + O
2
(g)
At 1000 C, K
C
= 7.3 10
18

If the initial H
2
O concentration is 0.100M,
what will the H
2
concentration be at
equilibrium?

Calculate [X]
equilibrium
from [X]
initial
and K
C

18
2
2
2
2
2
10 3 . 7
O] [H
] [O ] [H

= =
c
K
Conc (M) 2H
2
O(g) 2H
2
(g) + O
2
(g)
Initial 0.100 0.00 0.00
Change
Equilm
2x +x +2x
+x +2x 0.100 2x
2
3
2
2
18
) 2 100 . 0 (
4
) 2 100 . 0 (
) 2 (
10 3 . 7
x
x
x
x x
=

Cubic equation tough to solve
Make approximation
K
C
very small, so x will be very small
Assume we can neglect x
must prove valid later
Assume (0.100 2x) ~ 0.100

Now our equilibrium expression simplifies to
Conc (M) 2H
2
O (g) 2H
2
(g) + O
2
(g)
Initial 0.100 0.00 0.00
Change
Equilm
2x +x +2x
+x +2x 0.100
010 . 0
4
) 100 . 0 (
) 2 (
10 3 . 7
3
2
2
18
x x x
= =

) 10 3 . 7 ( 010 . 0 4
18 3
= x
= 7.3 10
20

Now take cubic root

x is very small
0.100 2(2.610
7
) = 0.09999948
Which rounds to 0.100 (3 decimal places)
[H
2
] = 2x = 2(2.610
7
)
= 5.210
7
M

20
20
3
10 8 . 1
4
10 3 . 7

= x
7
3
20
10 6 . 2 10 8 . 1

= = x
Simplifications: When Can You
Ignore x in Binomial (C
i
x)?
If equilibrium law gives very complicated
mathematical problems
And if K is small
Change to reach equilibrium (x term) is also small
Compare initial concentration C
i
in binomial to
value of K

Use proof to show that dropped x term was
sufficiently small
05 . 0
term x dropped
?
i
>
C
400 >
K
C
i
Learning Check
For the reaction 2A(g) B(g)
given that K
p
= 3.510
16
at 25C, and we place 0.2
atm A into the container, what will be the pressure of B
at equilibrium?
2A B
I 0.2 0 atm
C 2x +x
E 0.2 2x x
2
NO
O N
P
P
Q
4 2
=
2
16
) 2 . 0 (
x
10 5 . 3 =

x = 1.410
17

[B]= 1.410
17
M
proof: 1.410
17
/0.2<0.05
right shifts K Q
0
) 2 . 0 (
0
Q
2
<
= =
0.2
95
Your Turn!
In the reaction shown, K = 1.8 10
5

HC
2
H
3
O
2
(aq) + H
2
O(l) H
3
O
+
(aq) + C
2
H
3
O
2
(aq)
If we start with 0.3M HC
2
H
3
O
2
, what will be the
equilibrium concentration of C
2
H
3
O
2

?
A. 0.3 M
B. 0.002 M
C. 0.04 M
D. 0.5 M

96
Calculating K
C
Given Initial Concentrations
and One Final Concentration
Ex. 2a
H
2
(g) + I
2
(g) 2HI(g) @ 450 C
Initially H
2
and I
2
concentrations are 0.200
mol each in 2.00L (= 0.100M); no HI is
present
At equilibrium, HI concentration is 0.160 M
Calculate K
C

To do this we need to know 3 sets of
concentrations: initial, change and
equilibrium

CH15 Chemical Equilibrium

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