Chapter 13 Notes

Chapter 13
Chemical Equilibrium

Chemistry, 4th Edition

McMurry/Fay
Mr. Kevin A. Boudreaux
Angelo State University
www.angelo.edu/faculty/kboudrea

Chemical Equilibrium
Kinetics tells us how quickly a chemical reaction
takes place; equilibrium tells us how much there will
be when the reaction is done.
Most chemical reactions proceed until they reach a
state of chemical equilibrium, in which the
concentrations of the reactants and products no
longer change.
Many chemical reactions proceed in both a
forward and reverse direction.
When the rate in the forward direction equals the
rate in the reverse direction, the concentrations of
the products and any remaining reactants remains
constant.

2
Chapter 13 Notes

The Equilibrium
State
3

Equilibrium Concentrations
If we look at the concentrations of N2O4 and NO2 in
the following experiments, we see that after a period
of time the concentrations of both reactants and
products no longer change (at equilibrium):
N2O4(g, colorless) h 2NO2(g, brown)

The reaction starts out as completely N2O4, and

gradually some brown NO2 forms. As the number
of N2O4s decreases, the forward reaction slows
down. The backward direction, however, speeds up
as more NO2 is produced. Eventually, the two rates
are equal, and no further reaction takes place.
Movie
(1st half) 4
Chapter 13 Notes

Equilibrium Concentrations
There is still stuff happening at the molecular level;
but the change in one direction equals exactly the
change in the opposite direction we have a
dynamic equilibrium.

Figure 13.1 5

Reversible Reactions
This (apparent) cessation of chemical activity results
from the fact that all reactions are reversible.
As the reaction proceeds, the rate of the forward
reaction decreases, while that of the reverse reaction
increases, until the two are equal (Fig. 13.2).
The same equilibrium state could be reached by
starting with NO2 instead of N2O4.
To indicate an equilibrium reaction, we use two half-

h
arrows, one pointing in each direction:

All chemical reactions are in principle reversible;

irreversible reactions are those that proceed nearly to
completion, so that the final equilibrium mixture
contains almost entirely products.
6
Chapter 13 Notes

Rates of Forward and Reverse Reactions

Figure 13.2 7

The Law of Chemical Equilibrium

ratefwd = raterev kfwd [NO 2 ]2
K = =
kfwd[N2O4] = krev[NO2]2 k rev [N 2 O 4 ]
Law of chemical equilibrium or law of mass
action at a given temperature, a chemical system
reaches a state in which a particular ratio of reactant
and product concentration terms has is a constant.
For a particular system and temperature, the same
equilibrium state is reached no matter what the
starting concentrations are:

8
Chapter 13 Notes

The Equilibrium Constant, Kc

For any general reversible reaction
aA + bB h cC + dD
we can define an equilibrium constant, Kc, using
the following equilibrium equation:
Equilibrium equation: [C]c [D]d Products
Kc =
Equilibrium constant [A]a [B]b Reactants
Equilibrium constant expression

No matter what the individual equilibrium

concentrations may be for a particular experiment,
the equilibrium constant for a reaction at a
particular temperature is always the same.
We will write values of Kc as unitless numbers.
9

Examples: Equilibrium Constants

1. Write the equilibrium equation for the following
reactions. (sim to WE 13.1)
a. N2(g) + H2(g) h NH3(g) [unbalanced]
b. C3H8(g) + O2(g) h CO2(g) + H2O(g) [unbal.]
c. 2H2(g) + O2(g) h 2H2O(g)
d. PCl3(g) + Cl2(g) h PCl5(g)
e. PCl5(g) h PCl3(g) + Cl2(g)
2. Given the following reaction and Kc,
N2(g) + 3H2(g) h 2NH3(g); Kc = 2.410-3 at 1000K
calculate the value of Kc for the following eqns.:
a. 2NH3(g) h N2(g) + 3H2(g)
b. NH3(g) h 1/2N2(g) + 3/2H2(g)
10
Chapter 13 Notes

The Equilibrium Constant, Kp

The equilibrium constant obtained when all species
are present at their equilibrium partial pressures is
Kp, the equilibrium constant based on pressures.
2NO(g) + O2(g) h 2NO2(g)
2
PNO
Kp = 2
2

PNO PO 2
Kp and Kc are related by the following equation:
ngas
K p = K c ( RT )
ngas = moles of gas product - moles of gas reactants
and R is the gas constant (0.0821 L atm K-1 mol-1).
When there is no change in the number of moles of
gas, ngas = 0, and Kp = Kc.
11

Heterogeneous Equilibria
Homogeneous equilibrium all reactants and
products are in the same phase.
Heterogeneous equilibrium more than one phase
exists in a reaction mixture. (One or more of the
components is a liquid or solid.)
CaCO3(s) h CaO(s) + CO2(g); Kc = ?
A pure solid always has the same concentration at a
given temperature, and its volume does not change
much.
Since were only concerned with quantities that are
changing, we eliminate the terms for pure liquids
and solids from the reaction quotient:
Kc = [CO2] Kp = PCO2
12
Chapter 13 Notes

Examples: Kp, Heterogeneous Equilibria

3. Calculate Kc for the following reaction: (sim. to
WE 13.6)
CaCO3(s) h CaO(s) + CO2(g); Kp = 2.110-4 at 1000K

4. Write equilibrium laws for the following

heterogeneous reactions. (sim. to WE 13.7)
a. CaO(s) + SO2(g) h CaSO3(s)
b. 2Hg(l) + Cl2(g) h Hg2Cl2(s)
c. NH3(g) + HCl(g) h NH4Cl(s)
d. Ag2CrO4(s) h 2Ag+(aq) + CrO42(aq)
e. 2NaHCO3(s) h Na2CO3(s) + H2O(g) + CO2(g)
13

14
Chapter 13 Notes

Using the
Equilibrium
Constant
15

Judging the Extent of Reaction

The numerical value of the equilibrium constant
indicates the extent to which reactants are converted
to products:

K >> 103 Little reactant left at equilibrium

(reaction goes to completion)
K << 10-3 Very little product formed
Significant amounts of both
K ~ 10-3 - 103 reactant and product present at
equilibrium.

Figure 13.4 16
Chapter 13 Notes

Predicting the Direction of Reaction

At conditions other than equilibrium, the equilibrium
constant expression can be evaluated to obtain a
value called the reaction quotient, Qc:
aA + bB h cC + dD
[C]c [D]d
Qc =
[A]a [B]b
The numerical value of Qc changes during the course
of the reaction until the system reaches equilibrium.
At this point, there is no further change in the
reaction and
Q = K (at equilibrium)

17

Predicting the Direction of Reaction

By comparing the value of Q at a particular time
with the value of K, it is possible to determine if the
reaction has reached equilibrium, or if not, which
direction it is progressing.

Q < K The netreactants

reaction goes to the right:
products
Q > K The netreactants
reaction goes to the left:
products
No net reaction occurs; the reaction
Q = K is at equilibrium:
reactants h products

18
Chapter 13 Notes

Predicting the Direction of Reaction

Figure 13.5 19

Manipulating Q and K Expressions

If all of the coefficients in a balanced equation are
multiplied by a number, each term in the Q or K
expression must be raised to that power.
The reaction quotient (or K) for a reverse reaction is
the reciprocal of the reaction quotient (or K) for the
forward reaction. (This is equivalent to multiplying
the equation by -1 and using -1 as an exponent).
Qc(rev) = 1 / Qc(fwd)
For a reaction which is the sum of two or more
reactions, the overall reaction quotient (or K) is the
product of the expressions for Q or K for the steps:
Qoverall = Q1 Q2 Q3
Koverall = K1 K2 K3
20
Chapter 13 Notes

Examples: Using the Equilibrium Constant

5. Which of the following reactions will tend to
proceed farthest toward completion?
a. H2(g) + Br2(g) h 2HBr(g); Kc = 1.4 10-21
b. 2NO(g) h N2(g) + O2(g); Kc = 2.1 1030
c. 2BrCl h Br2 + Cl2; Kc = 0.145

6. For the reaction N2O4(g) h 2NO2(g), Kc = 0.21 at

100C. At a point during the reaction, [N2O4] =
0.12 M and [NO2] = 0.55 M. Is the reaction at
equilibrium, and if not, in what direction is it
progressing? (sim. to WE 13.8)

21

Examples: Minding Your Ks and Qs

7. For the reaction
CO(g) + H2O(g) h CO2(g) + H2(g)
Kc = 4.06 at 500C. If [CO] = 0.0331 M, [H2O] =
0.0331 M, [CO2] = 0.0667 M, and [H2] = 0.0667 M,
what direction will the reaction progress in? (sim.
to WE 13.8)

8. At 25C, the following reactions have the

equilibrium constants shown:
2CO(g) + O2(g) h 2CO2(g); Kc1 = 3.3 1091
2H2(g) + O2(g) h 2H2O(g); Kc2 = 9.1 1080
Use these data to calculate Kc for the reaction
CO(g) + H2O(g) h CO2(g) + H2(g)
22
Chapter 13 Notes

Equilibrium
Calculations
23

How To Solve Equilibrium Problems

Most equilibrium problems can be grouped into two
types:
Equilibrium quantities (concentrations or partial
pressures) are known, and the value of Kc or Kp
must be determined.
Initial quantities and the value of K are known,
and the equilibrium concentrations must be
determined.
Many of these types of problems require the use of
an reaction table, which will be illustrated in the
following examples. (An outline for working these
types of problems is given in Figure 13.5.)

24
Chapter 13 Notes

How To Solve Equilibrium Problems

Figure 13.5 25

Examples: Equilibrium Problems

9. Calculating Kc from Equilibrium Concentrations
At a certain temperature, a mixture of H2 and I2 was
prepared by placing 0.200 mol of H2 and 0.200 mol
of I2 into a 2.00 liter flask. After a period of time
the equilibrium
H2(g) + I2(g) h 2HI(g)
was established. The purple color of the I2 vapor
was used to monitor the reaction, and from the
decreased intensity of the purple color it was
determined that, at equilibrium, the I2 concentration
had dropped to 0.020 mol/L. What is the value of
Kc for this reaction at this temperature?

26
Chapter 13 Notes

Examples: Equilibrium Problems

10. Calculating Kc from Equilibrium Concentrations
A student placed 0.200 mol of PCl3(g) and 0.100
mol of Cl2(g) into a 1.00 L container at 250C.
After the reaction
PCl3(g) + Cl2(g) h PCl5(g)
came to equilibrium it was found that the flask
contained 0.120 mol of PCl3. What were the initial
and equilibrium concentrations of the reactants and
products? What is the value of Kc for this reaction
at this temperature?

27

Examples: Equilibrium Problems

11. Determining an Equilibrium Concentration from Kc
and some Equilibrium Concentrations
In a study of the conversion of methane to other
fuels, a chemical engineer mixes gaseous CH4 and
H2O in a 0.32 L flask at 1200 K. At equilibrium,
the flask contains 0.26 mol CO, 0.091 mol H2, and
0.041 mol CH4. What is [H2O] at equilibrium? Kc
= 0.26 for this reaction.
CH4(g) + H2O(g) h CO(g) + 3H2(g)

28
Chapter 13 Notes

Examples: Equilibrium Problems

12. Using Kc to Calculate Equilibrium Concentrations
The equilibrium constant Kc for the reaction of H2
with I2 is 57.0 at 700 K:
H2(g) + I2(g) h 2HI(g); Kc = 57.0 at 700K
If 1.00 mol of H2 is allowed to react with 1.00 mol
of I2 in a 10.0 L reaction vessel at 700 K, what are
the concentrations of H2, I2, and HI at equilibrium?
(WE 13.9)

29

Examples: Equilibrium Problems

13. Using Kc to Calculate Equilibrium Concentrations
The reaction
CO(g) + H2O(g) h CO2(g) + H2(g)
has Kc = 4.06 at 500C. If 0.100 mol of CO and
0.100 mol of H2O(g) are placed in a 1.00 L reaction
vessel at this temperature, what are the
concentrations of the reactants and products when
the system reaches equilibrium? (sim to WE 13.9)

30
Chapter 13 Notes

Examples: Equilibrium Problems

14. Using Kc to Calculate Equilibrium Concentrations
At a certain temperature Kc = 4.50 for the reaction
N2O4(g) h 2NO2(g)
If 0.300 mol of N2O4 is placed into a 2.00 L
container at this temperature, what will be the
equilibrium concentrations of both gases? (sim to
WE 13.10)

31

Examples: Equilibrium Problems

15. Using Kp to Calculate Equilibrium Concentrations
One reaction that occurs in producing steel from
iron ore is the reduction of iron(II) oxide by carbon
monoxide to give iron metal and carbon dioxide.
The equilibrium constant Kp for the reaction at 1000
K is 0.259.
FeO(s) + CO(g) h Fe(s) + CO2(g); Kp=0.259 at 1000 K
What are the equilibrium partial pressures of CO
and CO2 at 1000 K if the initial partial pressures are
PCO = 1.000 atm and PCO2 = 0.500 atm? (WE
13.11)

32
Chapter 13 Notes

Examples: Equilibrium Problems

16. Simplifying Equilibrium Calculations for Reactions
with Small Kc
Hydrogen, a potential fuel, is found in great
abundance in water. Before the hydrogen can be
used as a fuel, however, it must be separated from
the oxygen; the water must be split into H2 and O2.
One possibility is thermal decomposition, but this
requires very high temperatures. Even at 1000C,
Kc = 7.3 10-18 for the reaction
2H2O(g) h 2H2(g) + O2(g)
If at 1000C the H2O concentration in a reaction
vessel is set initially at 0.100 M, what will the H2
concentration be when the reaction reaches
equilibrium?

33

Examples: Equilibrium Problems

17. Simplifying Equilibrium Calculations for Reactions
with Small Kc
In air at 25C and 1 atm, the N2 concentration is
0.033 M and the O2 concentration is 0.00810 M.
The reaction
N2(g) + O2(g) h 2NO(g)
has Kc = 4.8 10-31 at 25C. Taking the N2 and O2
concentrations given above as initial values,
calculate the equilibrium NO concentration that
should exist in our atmosphere from this reaction at
25C.

34
Chapter 13 Notes

Disturbing the
Equilibrium:
Le Chteliers
Principle
35

Le Chteliers Principle
There are a number of parameters that can be
adjusted in order to maximize the yield of products in
a chemical reaction:
the concentration of the reactants or products.
the pressure and the volume.
the temperature.
The effect that changing any of these parameters has
on a reaction can be qualitatively predicted using a
principle first described by Henri-Louis Le Chtelier:

Le Chteliers If a stress is applied to a reaction

Principle mixture at equilibrium, net reaction
occurs in the direction that relieves
the stress.
36
Chapter 13 Notes

Le Chteliers Principle
Stress in this context means a change in
concentration, pressure, volume, or temperature that
disturbs the original equilibrium.
Reaction then occurs until a new state of
equilibrium is reached; the direction that the
reaction takes is one that reduces the stress.
The system, when disturbed, changes in a way
that reduces the disturbance, and attains a new
equilibrium.

MOV: Le Chteliers Principle 37

Disturbing the Equilibrium Concentration

A + B h C + D
Changing concentration:
If the concentration of a substance increases, the
equilibrium shifts to consume some of it.
If the concentration of a substance decreases, the
equilibrium shifts to produce some of it.
In terms of reactants and products:
The equilibrium position shifts to the right if a
reactant is added or a product is removed.
The equilibrium position shifts to the left if a
reactant is removed or a product is added.

Movie
(2nd half) 38
Chapter 13 Notes

Disturbing the Equilibrium Concentration

Figure 13.8 39

Disturbing the Equilibrium Volume/Pressure

Changing pressure by changing volume: From
Boyles Law, we know that changing the volume of
a reaction that involves gases changes the pressure:
Decreasing the volume of a system increases the
pressure, and favors the side of the reaction with
the smaller number of moles of gas.
Increasing the volume of a system decreases the
pressure, and favors the side of the reaction with
the larger number of moles of gas.
If the two sides have the same number of moles
of gas, changing the volume has no effect.
Adding an inert gas increases the pressure, but
does not change the partial pressure of any of the
species, and does not affect the equilibrium.
MOV: N2O4NO2 Equilibrium 40
Chapter 13 Notes

Disturbing the Equilibrium Temperature

The value of Kc is not affected by changing
concentration, pressure, or volume. Changing the
temperature does change the value of Kc:

Figure 13.12
41

Disturbing the Equilibrium Temperature

Changing temperature:
Raising temperature increases Kc if Hrxn > 0
Raising temperature decreases Kc if Hrxn < 0

Its easier if you think about where heat is located:

Exothermic: A + B h C + D + heat
adding heat (increasing temp.) drives the reaction
to the left, while removing heat (decreasing
temp.) drives the reaction to the right.
Endothermic: A + B + heat h C + D
adding heat (increasing temp.) drives the reaction
to the right, while removing heat (decreasing
temp.) drives the reaction to the left.
42
Chapter 13 Notes

Disturbing the Equilibrium Catalysts

Adding a catalyst:
The rates of the forward and reverse reactions
speed up by the same amount (Fig. 13.14).
A catalyst shortens the time a system needs to
reach equilibrium, but has no effect on the
position of the equilibrium.

Figure 13.14 43

Chemical Equilibrium and Kinetics

The relative values of the rate constants for the
forward and the reverse reactions determine the
composition of the equilibrium mixture:
When kf is much larger than kr, Kc is very large
and the reaction goes to completion; the reaction
is essentially irreversible.
When kr is much larger than kf, Kc is very small
and the reaction does not produce much product.
When kr is comparable to kf, Kc has a value near
1, and significant amounts of both reactants and
products are present at equilibrium.
Addition of a catalyst increases kr and kf, by the
same amount, and does not affect the equilibrium
composition.
44
Chapter 13 Notes

Examples: Le Chteliers Principle

18. (sim. to WE 13.12-13.14) The reaction
N2O4(g) h 2NO2(g)
is endothermic, with H = +56.9 kJ. How will the
amount of NO2 at equilibrium be affected by:
a. adding N2O4
b. increasing the volume of the container
c. raising the temperature
d. adding a catalyst to the system?
e. Which of these changes will alter the value of Kc?

45

Examples: Le Chteliers Principle

19. (WE 13.12) The reaction of iron(III) oxide with
carbon monoxide occurs in a blast furnace when iron
ore is reduced to iron metal:
Fe2O3(s) + 3CO(g) h 2Fe(l) + 3CO2(g)
Use Le Chteliers principle to predict the direction
of net reaction when an equilibrium mixutre is
disturbed by:
a. removing CO2
b. removing CO
c. adding CO
d. adding Fe2O3
e. decreasing the volume of the container
46
Chapter 13 Notes

Examples: Le Chteliers Principle

20. Does the number of moles of reaction products
increase, decrease, or remain the same when each of
the following equilibria is subjected to a decrease in
pressure by increasing the volume?

a. PCl5(g) h PCl3(g) + Cl2(g)

b. H2(g) + I2(g) h 2HI(g)

c. C(s) + H2O(g) h CO(g) + H2(g)

d. CaO(s) + CO2(g) h CaCO3(s)

e. 3Fe(s) + 4H2O(g) h Fe3O4(s) + 4H2(g)

47

Examples: Le Chteliers Principle

21. How would you change the volume of each of the
following reactions to increase the yield of the
products?
a. CaCO3(s) h CaO(s) + CO2(g)
b. S(s) + 3F2(g) h SF6(g)
c. Cl2(g) + I2(g) h 2ICl(g)

22. How would an increase in temperature affect the

equilibrium concentration of the underlined
substance and Kc for the following reactions?
a. CaO(s) + H2O(l) h Ca(OH)2(aq); H = -82 kJ
b. CaCO3(s) h CaO(s) + CO2(g); H = +178 kJ
c. SO2(g) h S(s) + O2(g); H = +297 kJ
48
Chapter 13 Notes

Example: The Haber Synthesis of Ammonia

Nitrogen is a vital element in many essential natural
and synthetic compounds. Eighty percent of the air
we breathe is nitrogen, but N2 is very unreactive.
Natural nitrogen fixation of unusable N2 to
usable ammonia, NH3, occurs in bacteria on the
root nodules of leguminous plants (peas, beans),
and in lightning.
Industrially, nitrogen is converted to ammonia by
the Haber process (Fritz Haber, 1913):
N2(g) + 3H2(g) h 2NH3(g); Hrxn = -91.8 kJ
Over 80% of the 110 million tons of ammonia
produced each year is used in fertilizers.
How would we maximize the yield of NH3 using Le
Chteliers Principle?
49

The Haber Synthesis of Ammonia

Figure 13.7

50
Chapter 13 Notes

Key Concept Summary

51

The End
52