Chemical

Equilibrium
Chapter 14

Textbook Chapters to
Cover
14.2
14.3
14.4
14.5

The Concept of Dynamic Equilibrium

The Expression of the Equilibrium Constant
The Equilibrium Constant K
Calculating the Equilibrium Constant from
Measured Quantities
14.6 The Reaction Quotient: Predicting the
Direction of Change
14.7 Find Equilibrium Constants
14.8 Le Chateliers Principle: How a System at
Equilibrium Responds to Disturbances
3

Dynamic Equilibrium
Dynamic equilibrium occurs
when the forward rate and
the reverse rate of the
reaction are equal.
Concentrations (or partial
pressures) no longer
change over time.

Equilibrium & Reaction

Rates
generic equilibrium
forward reaction: A B

Rate = kf[A]

reverse reaction: A B

Rate = kr[B]

At equilibrium,
Rearranging,

kf[A] = kr[B]

B k f
K eq
A k r

N.B. Keq changes with T, not with concentration

At equilibrium, the concentrations of reactants
and products no longer change, but they are
not necessarily equal to one another.
5

The Equilibrium
Constant

The Equilibrium Constant

Concentration-based equilibrium constant, K c
Pressure-based equilibrium constant, KP
Relation between Kc and KP
Solids & liquids in equilibrium
We will not cover activities (you will see

activities in more advanced chemistry

courses.)

Conc-Based Equilib.
Constant
For generic reaction
with A, B, C, and D in the aqueous or gas phase

Concentration-based equilibrium constant, K c

is:

[C]c [D]d
Kc
[A]a [B]b

[ ] indicates conc at equilibrium in mol L-1

Keq ratio always has products over reactants
8

Pressure-Based Equilib.
Constant
KP used for gas-phase reactions
Equilibrium partial pressures (bar) instead of

mol/L
e.g. 2NO2(g)

PN2 O4
KP
2
(P
)
NO2
N2O4(g)

Examples

2
[Fe(SCN)
]
3+

2+
Fe (aq) + SCN (aq) Fe(SCN) (aq) K c
[Fe3 ][SCN - ]
(PNH 3 ) 2
N2(g) + 3H2(g)
2NH3(g)
KP
(PN 2 )(PH 2 ) 3

K >> 1 implies that products are favoured

E.g. H2(g) + Br2(g) 2 HBr(g) K = 1.9 x 1019 at 25 C

K << 1 implies that reactants are favoured

E.g. N2(g) + O2(g) 2 NO(g)

K = 4.1 x 10-31 at 25 C

10

10

LC: Equilibrium Constants

Select the appropriate definition for the
equilibrium constant of the following
reaction:
4 HCl(g) +2 O2(g)
2 Cl2(g) + 2 H2O(g)
2
A.

C.

KP =

KP =

(PCl 2 ) (PH 2O )
4

(PHCl ) (PO 2B.

)
(PCl 2 )(PH 2O )
(PHCl )(PO 2 ) D.

KP =

KP =

2(PCl 2 ) 2(PH 2O )
4(PHCl )(PO 2 )

2(PCl 2 ) 2 2(PH 2O ) 2
4(PHCl ) 4 (PO 2 )
11

11

Form, value and units

In your textbook, Kc and KP are written with

units:
N2(g)+3H2(g)

2NH3(g) K P

(PNH3 ) 2

(PN 2 )(PH 2 ) 3

K P 4.23 10 3 bar 2
The unitless thermodynamic equilibrium

constant, K (which is based on activities rather

than concentrations/pressures), is formally
unitless.
(We will not discuss activities in this class)

12

12

Form, value and units

In CHY102, we will use unitless Kc or KP. The

units are understood from the stoichiometry of

the reaction.
Example: NH3 synthesis at 573 K (PNH ) 2
3
K

4
.
23

10
N2(g)+3H2(g)
2NH3(g) P
3
3

NH3(g)

KP

N2(g)+3H2(g)

KP

/2N2(g)+ /2H2(g)

2NH3(g)

(PN 2 )(PH 2 )
(PNH 3 )
1
2

(PN 2 ) (PH 2 )
(PN 2 )(PH 2 ) 3
(PNH 3 )

3
2

6.5 10 2

236
13

13

Relating Kc and KP
Example: 2NO2(g)

PN2 O4
KP
(PNO2 )2

N2O4(g)
and

[N 2O 4 ]
Kc
[NO2 ]2

Numerically different
Mathematically and physically related
(Assuming the gases behave ideally)

14

14

Relating Kc and KP
For an ideal gas, molarity (n/V) pressure (P):

n/V = P/RT
2NO2(g)
N2O4(g)

n N 2 O4

PN 2 O4

[N 2 O 4 ]
V
RT

Kc =
2
2
2

[NO 2 ]
NO2 V
NO2 RT

2
PN O
PN2 O4
RT

RT = K RT

2
2
P
(PNO )
(PNO2 )
RT
2

15

15

Relationship Between KP
and Kc
In general, Kc and KP are related by:
KP = Kc (RT)n
n is diff. betw. moles of gas-phase products

and reactants in the stoichiometric equation:

n = ngas products - ngas reactants

2 NO2(g) N2O4(g)
In the previous example,
n = 1 - 2 = -1
KP = Kc(RT)-1
OR Kc = KP(RT)
16

16

Example
The reaction of N2 and H2 forms ammonia, NH3:
N2(g) + 3H2(g)

2NH3(g)

At 600 K, KP is 4.388 x 10-3. Assuming all gases

behave ideally, calculate Kc.
KP = Kc(RT)n where n = 2 - (1 + 3) = -2
Kc = KP(RT)-n = KP(RT)2
Kc = 4.388 x 10-3[(0.08314)(600)]2 = 10.9
NOTE: Use R=0.08314 Lbarmol-1 K-1
Units are mol/L and bar

17

17

LC: Kp and Kc
CS2(g) + 4H2(g)

CH4(g) + 2H2S(g)

The value of Kc for the above reaction is 0.28 at

900C. Assuming all gases behave ideally, what
is Kp at this temperature?
(0C = 273.15K; R= 0.08314 L bar mol -1 K-1)
A. 5.110-5
B. 2.910-5
C. 0.28
D. 2.6103
18

18

LC: Kp and Kc
Answer: B
T = 900 + 273.15 = 1173.15
n = (2+1)- (1+4) = -2
Kp = 0.28 (0.08314 1173.15)-2
= 2.910-5

19

19

Solids and Liquids

Pure solids and liquids are ignored in Keq
Conc. of a pure solid is solid/Msolid = a constant

Only gases and substances in solution are

included
+
AgCl(s)
Ag
(aq)
+
Cl
(aq)

K SP
[Ag ][Cl ] [Ag ][Cl ]
*
K

[AgCl]
const.
const.

KSP = K*const. = [Ag+][Cl-]

20

20

Example
What are the equilibrium constant expressions
for the following reactions?

H2(g)+CO2(g)
[CO]
Kc
[CO 2 ][H 2 ]
CaCO3(s)
K c [CO 2 ]

H2O(l)+CO(g)
PCO
orK P
PCO2 PH 2
CaO(s)+CO2(g)
orK P PCO2
21

21

Important note
Presence of solids and liquids necessary for

equilibrium!
e.g.,

CaCO3(s)

CaO(s)+CO2(g)

K c [CO 2 ] & K P PCO2

although Keq includes only CO2, equilibrium

requires coexistence of all three components

22

22

Calculations in
Equilibrium
Constant

23

Calculations in
Equilibrium
Using an ICE table:
Calculate Kc or KP given certain initial and
equilibrium concentrations or pressures.
Calculate equilibrium concentrations or
pressures given Kc or KP and the initial
concentrations or pressures.

24

Calculations in
Equilibrium
Write an ICE chart beneath the chemical reaction with

rows for the initial (I), change (C), and equilibrium (E)
concentrations or pressures.
Tabulate all known values of concentrations or pressures.
If values of I and E are known for a given species,
calculate C for that species.
If values of E are unknown for any species, use +/- x for
the value of C.
Use the stoichiometry of the reaction to calculate values
of C (possibly in terms of x) for all other species.
Calculate values of E (possibly in terms of x) for all
species and use them in the Kc or KP equilibrium
expression.
25
Solve the question.

Example
3.00 mol of N2(g) and 4.00 mol of O2(g) are
introduced into a sealed, 2.00-L reaction vessel
and heated to 2000 K. After the system
reaches equilibrium, the concentration of NO(g)
is 0.038 mol/L. What are Kc and KP for the
reaction below?
1

/2N2(g)

/2O2(g)

NO(g)

26

/2 N2 (g)

/2 O2 (g)

NO (g)

1.50

2.00

-0.019

-0.019

+0.038

1.481

1.981

0.038

Kc

[NO]

0.038

= 0.022
1.481
the
1.981
a given
Use
If
Write
values
thean
ICE
of
I
and
chart
E
beneath
are
of
known
the
reaction
for
chemical
to (e.g.
reaction.
Calculate
Convert
initial
values
moles
of
E
to
for
concentrations
all
species
and
use
N2
[Nstoichiometry
]
[O
]
2
2
calculate
species,
them
in the
calculate
values
Kc equilibrium
ofCC
for
forthat
all expression.
other
species.
species.
3.00 mol,
2.00
L);
tabulate
all
known
values.
KP = Kcx(RT)n = Kcx(RT)0 = 0.022
1
2

1
2

1
2

1
2

27

Example
For the reaction reaction below Kc=4.84x10-4 at
2000 K. If 5.00 bar of NO are introduced to a
reaction vessel initially, what will be the
equilibrium partial pressures of N2, O2, and NO?

N2 (g)

O2 (g)

2 NO (g)

Answer:
First convert Kc to KP
KP = Kcx(RT)n = Kc = 4.84x10-4

28

N2 (g)

O2 (g)

2 NO (g)

5.00

+x

+x

- 2x

5.00 - 2x

If
Use
values
the
of
Iknown
and
E beneath
arein
ofunknown
thethe
reaction
toallcalculate
Tabulate
Calculate
Write
anstoichiometry
all
ICE
values
chart
of
values.
E
terms
ofchemical
xforforany
reaction.
species.
species,
values ofuse
C in
+/-terms
x forof
thex value
for allofother
C. species.
29

Use values of E in terms of x in the KP equilib.

expression:
(PNO )2
4

KP

PN2 PO2

4.84 10

5.00 2x 2

4.84 10 4

x2
5.00 2x
4

4.84 10
x
5.00
x
4 2.4728
2 4.84 10

At equilibrium: PNO = 0.054 bar; PN2 = 2.47 bar;

PO2 = 2.47 bar
30

A more complicated
example...
N2(g) + O2(g)
2NO(g)
For the above reaction KP=4.8410-4 at 2000 K.
If 0.050 bar of NO, 2.00 bar of N2 and 8.00 bar
of O2 are introduced to the reaction vessel
initially, what will be the equilib. partial
pressures of N2, O2, and NO?

31

31

Two complications here

N2 (g)

O2 (g)

2 NO (g)

2.00

8.00

0.050

+x or x?

+x or x?

2x or +2x?

E
Will the reaction proceed towards NO (+2x),

or will NO be consumed (-2x)? How do we

know?
Resulting quadratic equation is more

32

32

The Reaction Quotient, Q

...is a quantity that helps determine whether a

reaction will proceed towards products or

reactants.
Q is constructed in same way as the K eq, but
concs used in Q are initial concs, not equilib.
concs.
If Q > Keq then rxn proceeds towards reactants
If Q < Keq then rxn proceeds towards products
If Q = Keq then rxn is already at equilibrium
33

33

34

34

Back to the example

Initial values: PNO = 0.050 bar; PN2 = 2.00 bar;
PO2 = 8.00 bar 2
2

(PNO,i )
0.050
Q

1.56 10 4
PN2 ,i PO2 ,i 2.008.00

Q < KP (4.8410-4) so rxn proceed towards

products
Say, PNO,i = 0.100 bar, PN2 = 2.00 bar, PO2 = 8.00
bar
Then Q = 6.2510-4 rxn proceeds towards
reactants
35
35

N2 (g)

O2 (g)

2 NO (g)

2.00

8.00

0.050

-x

-x

+ 2x

2.00 -x

8.00 - x

0.050 + 2x

0.050 2 x
KP
4.84 10 4
2.00 x 8.00 x

(4.00 K P ) x 2 (10K P 0.2) x (0.0025 16K P ) 0

36

Solution
Using the quadratic formula

b b 2 4ac
x
2a

with a = 3.999516
b = 0.20484
c = -5.24410-3

The roots are x = +0.0187 and -0.0700

37

37

Quadratic equation
Keq calculations will often require the use of

the quadratic equation -- RELEARN IT!

One of the roots is usually unphysical
e.g. x = -0.070 in the previous example yields
PNO = -0.090 bar
Quadratic formula song:
http://www.youtube.com/watch?v=IvXgFLV2gOk

38

38

Quadratic equation
Using the physical root, x = 0.0187, we find

that:
PNO = 0.050 + 2(0.0187) = 0.087 bar
PN2 = 2.00 - 0.0187 = 1.98 bar
PO2 = 8.00 - 0.0187 = 7.98 bar

Check your answer:

Plug the values found back into the KP
expression
ANSWER: 4.8310-4
39

39

Avoiding quadratics
Expression for KP (slide 36)

0.050 2x 2
KP
4.84 10 4
2.00 x 8.00 x
KP << 1, so x is small
2.00-x 2.00 and 8.00-x 8.00, so eqn simplifies:
2

0.050 2 x
KP
2.00 8.00

4.84 10 4

But beware: at end of calc, check that x << 2

If assumption fails, go back to quadratic equation
40

40

Le Chteliers
Principle
If a system at chemical equilibrium is disturbed by a
sudden change in temperature, pressure, or
composition, the system will re-establish equilibrium
in a way that will counteract the effects of the
disturbance.

41

41

Composition Changes
Adding or removing a product or reactant

to/from a system at equilibrium will disturb

the equilibrium
Equilibrium shifts to reduce change in
composition

42

42

P-V Changes
P-V changes are

counteracted by
changing the
number moles
of gas-phase
species in a
reaction vessel

43

43

LC: Pressure Change

Consider the following equilibria.

2NO2(g)
I.
II. N2(g)+3H2(g)
III. PCl5(g)

N2O4(g)
2NH3(g)
PCl3(g)+Cl2(g)

Will these equilibria shift towards reactants or products

or no change when the volume of the reaction vessel is
increased?
A. I. products; II. reactants; III. no change
B. I. reactants; II. products; III. products
C. I. products; II. products; III. reactants
D. I. reactants; II. reactants; III. products
44

44

Pressure & volume

changes
Le Chteliers Principle is explained by Q
e.g. When V is decreased by half, will the

equilibrium shift towards products or 2

( PNO2 )
reactants?
K
PN 2O4
N2O4(g)
2NO2(g)

2P
Q
NO 2

Halving volume doubles pressure 2PN 2O 4

2K

Which way will equilibrium shift?

45

45

LC: Pressure Changes

The following reaction is at equilibrium in a

rigid container:
N2(g)+3H2(g)
2NH3(g)
Which way will the equilibrium shift (towards
reactants OR towards products OR no change)
if:
H2 is removed from the reaction vessel?
NH3 is added to the reaction vessel?
Ar is added to the reaction vessel?

46

Answers: Pressure
Changes
The following reaction is at equilibrium in a

rigid container:
N2(g)+3H2(g)
2NH3(g)
Which way will the equilibrium shift (towards
reactants OR towards products OR no change)
if:
H2 is removed from the reaction vessel?

Reactants
NH3 is added to the reaction vessel?
Reactants
Ar is added to the reaction vessel?

No

47

Temperature changes
Change value of Keq
Energy can be thought of as a product or

reactant
Endothermic: Reactants + Heat Products
Exothermic: Reactants Products + Heat
Temperature increase drives
endothermic reactions towards products
exothermic reactions towards reactants

48

48

LC: Speed Round Part 1

Will the stress cause the equilibrium to shift towards
reactants or products, or will it have no effect?
Co(H2O)62+(aq) + 4Cl-(aq)
CoCl42-(aq) + 6H2O(l)
H > 0
Stress: Decrease temperature
A. Reactants
B. Products
C. No Change

49

49

LC: Speed Round Part 2

Will the stress cause the equilibrium to shift
towards reactants or products, or will it have no
effect?
PCl5(g)
PCl3(g) + Cl2(g)
H > 0

Stress: Increase Volume

A. Reactants
B. Products
C. No Change
50

50

LC: Speed Round Part 3

Will the stress cause the equilibrium to shift
towards reactants or products, or produce no
change?
N2(g) + 3H2(g)
2NH3(g)
H < 0

Stress: Increase pressure by adding helium

A. Reactants
B. Products
C. No Change
51

51

Examples
Will the stress cause the equilibrium to shift
towards reactants or products?

Co(H2O)62+(aq)+4Cl(aq)
CoCl42(aq)+6H2O(l)

H > 0
crease temperatureReactant

PCl5(g)
PCl3(g)+Cl2(g)
H > 0
rease volume..Product
H < 0
N2(g)+3H2(g)
2NH3(g)

crease pressure by adding helium.No chang

52

52

Summary
Dynamic equilibrium is established when

forward & reverse rates are equal

Keq constructed from gas and solution-phase
only
Q constructed from non-equilib
concentrations
compare with K to decide which way rxn

proceeds

Equilib calcs best handled with ICE table

re-learn quadratic equation!
LeChateliers principle predicts shift in

53

53

Suggested exercises
Review questions 2-20.
Problems by topic 21, 23, 25, 27, 29, 31, 33,

35, 39, 43, 45, 47, 51, 53, 57, 61, 63, 65, 67,
81, 87, 99, 101.
Note: answers to all odd-numbered problems

are found in Appendix III.

54