Chemistry, The Central Science, 10th edition

Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten

Chapter 15
Chemical Equilibrium

Equilibrium
 The Concept of Equilibrium

• Consider colorless frozen N O . At room temperature, it decomposes to brown NO :

2 4 2
N O (g)  2NO (g).
2 4 2

• At some time, the color stops changing and we have a mixture of N O and NO .
2 4 2
• Chemical equilibrium is the point at which the concentrations of all species are constant.

Equilibrium
• The point at which the rate of decomposition:

N O (g)  2NO (g)

2 4 2
equals the rate of dimerization:

2NO (g)  N O (g).

2 2 4
is dynamic equilibrium.

• The equilibrium is dynamic because the reaction has not stopped: the opposing rates are equal.

• Consider frozen N O : only white solid is present.

2 4
On the microscopic level, only N O
2 4
molecules are present.

Equilibrium
 The Concept of Equilibrium

Chemical equilibrium occurs when a reaction and its reverse reaction

proceed at the same rate.

Equilibrium
• As the substance warms it begins to decompose:

N O (g)  2NO (g)

2 4 2

• A mixture of N O (initially present) and NO (initially formed) appears light brown.

2 4 2

• When enough NO is formed, it can react to form N O :

2 2 4
2NO (g)  N O (g).
2 2 4

Equilibrium
• At equilibrium, as much N O reacts to form NO as NO reacts to re-form N O :
2 4 2 2 2 4

• N O (g)
The double arrow implies the 2process
4 is dynamic. 2NO2(g)
• Consider

Forward reaction: A  B Rate = k [A]

f
Reverse reaction: B  A Rate = k [B]
r

• At equilibrium k [A] = k [B].

f r

Equilibrium
• For an equilibrium we write
A B
• As the reaction progresses

– [A] decreases to a constant,

– [B] increases from zero to a constant.

– When [A] and [B] are constant, equilibrium is achieved.

• Alternatively:

– k [A] decreases to a constant,

f

– k [B] increases from zero to a constant.

r

– When k [A] = k [B] equilibrium is achieved.

f r

Equilibrium
The Concept of Equilibrium
• As a system approaches equilibrium,

both the forward and reverse reactions

are occurring.

• At equilibrium, the forward and reverse

reactions are proceeding at the same

rate.

Equilibrium
 A System at Equilibrium

Once equilibrium is
achieved, the amount
of each reactant and
product remains
constant.

Equilibrium
Equilibrium
 Depicting Equilibrium

In a system at equilibrium, both the

forward and reverse reactions are being
carried out; as a result, we write its
equation with a double arrow
N O 2 NO
2 4 (g) 2 (g)

Equilibrium
 The Equilibrium Constant

• Forward reaction:
N2O4 (g)  2 NO2 (g)

• Rate law:
Rate = kf [N2O4]

Equilibrium
 The Equilibrium Constant

• Reverse reaction:
2 NO2 (g)  N2O4 (g)

• Rate law:
Rate = kr [NO2]2

Equilibrium
 The Equilibrium Constant
• Therefore, at equilibrium

Ratef = Rater

kf [N2O4] = kr [NO2]2

• Rewriting this, it becomes

k [NO ]2
f = 2
k [N O ]
r 2 4 Equilibrium
 The Equilibrium Constant

The ratio of the rate constants is a

constant at that temperature, and the
expression becomes
k [NO ]2
K = f = 2
eq k [N O ]
r 2 4

Equilibrium
 The
Equilibrium
Constant
Equilibrium
 The Equilibrium Constant

• To generalize this expression, consider

the reaction
aA + bB cC + dD

• The equilibrium expression for this reaction would be

[C]c[D]d
K =
c [A]a[B]b Equilibrium
 Law of mass action
• Equilibrium constant expression
• It depends on the reaction stoichiometry
and NOT on its mechanism.
• We can not tell the reaction mechanism
from the Equilibrium Expression
• Always products on the numerator
• Always reactants in the denominator

Equilibrium
 What Are the Equilibrium
Expressions for These Equilibria?

Equilibrium
 The Equilibrium Constant

Because pressure is proportional to

concentration for gases in a closed
system, the equilibrium expression can
also be written
(P )c (P )d
K = C D
p (P )a (P )b
A B

Equilibrium
Relationship between Kc and Kp
• From the ideal gas law we know that
PV = nRT

• Rearranging it, we get

n
P= RT
V

Equilibrium
Relationship between Kc and Kp
Plugging this into the expression for Kp
for each substance, the relationship
between Kc and Kp becomes
K = K (RT)n
p c

Where

n = (moles of gaseous product) − (moles of gaseous reactant)

Equilibrium
Equilibrium Can Be Reached from
Either Direction

As you can see, the ratio of [NO ]2 to [N O ] remains constant at this temperature no
2 2 4
matter what the initial concentrations of NO and N O are.
2 2 4

Equilibrium
Equilibrium Can Be Reached from
Either Direction
This is the data from the last two trials

from the table on the previous slide.

Equilibrium
Equilibrium Can Be Reached from
Either Direction

It does not matter whether we start with N and H or whether we start with
2 2
NH . We will have the same proportions of all three substances at equilibrium.
3

Equilibrium
What Does the Value of K Mean?
• If K >> 1, the reaction is product-

favored; product predominates at

equilibrium.

Equilibrium
What Does the Value of K Mean?
• If K >> 1, the reaction is product-

favored; product predominates at

equilibrium.

• If K << 1, the reaction is reactant-favored;

reactant predominates at equilibrium.

Equilibrium
 January 11

• Manipulating Equilibrium Constants

• Heterogeneous equilibrium
• Equilibrium calculations RICE!!!
• HW 23, 27 to 41 RED

Equilibrium
Manipulating Equilibrium Constants
The equilibrium constant of a reaction in
the reverse reaction is the reciprocal of
the equilibrium constant of the forward
reaction.
[NO ]2
N O (g) 2 NO (g) K = 2 = 0.212 at 100C
2 4 2 c [N O ]
2 4
[N O ] 1
2 NO (g) N O (g) K = 2 4 =
2 2 4 c [NO ]2 0.212
2

= 4.72 at 100C

Equilibrium
Manipulating Equilibrium Constants
The equilibrium constant of a reaction that has
been multiplied by a number is the equilibrium
constant raised to a power that is equal to that
number.
[NO ]2
N O (g) 2 NO (g) K = 2 = 0.212 at 100C
2 4 2 c [N O ]
2 4

[NO ]4
2 N O (g) 4 NO (g) K = 2 = (0.212)2 at 100C
2 4 2 c [N O ]2
2 4

Equilibrium
Manipulating Equilibrium Constants

The equilibrium constant for a net

reaction made up of two or more steps
is the product of the equilibrium
constants for the individual steps.

Equilibrium
Heterogeneous
Equilibrium
Equilibrium
The Concentrations of Solids and
Liquids Are Essentially Constant

Both can be obtained by dividing the

density of the substance by its molar
mass—and both of these are constants
at constant temperature.

Equilibrium
The Concentrations of Solids and
Liquids Are Essentially Constant

Therefore, the concentrations of solids

and liquids do not appear in the
equilibrium expression

PbCl Pb2+ + 2 Cl−

2 (s) (aq) (aq)

K = [Pb2+] [Cl−]2
c

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

As long as some CaCO3 or CaO remain in the

system, the amount of CO2 above the solid will
remain the same.

Equilibrium
 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.

Equilibrium

• If a reaction can be expressed as a sum of two or more reactions, 14.2

 Calculating Equilibrium Concentrations

1. Express the equilibrium concentrations of all species in terms of the

initial concentrations and a single unknown x, which represents the

change in concentration.

2. Write the equilibrium constant expression in terms of the equilibrium

concentrations. Knowing the value of the equilibrium constant,

solve for x.

3. Having solved for x, calculate the equilibrium concentrations of all

species. Equilibrium

14.4
Equilibrium
Calculations
Equilibrium
 Equilibrium Calculations

A closed system initially containing

1.000 x 10−3 M H2 and 2.000 x 10−3 M Cl2
At 448C is allowed to reach equilibrium. Analysis
of the equilibrium mixture shows that the
concentration of HCl is 1.87 x 10−3 M. Calculate Kc
at 448C for the reaction taking place, which is

H + Cl 2 HCl
2 (g) 2 (g) (g) Equilibrium
 What Do We Know?

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change

At 1.87 x 10-3
equilibrium

Equilibrium
 [HCl] Increases by 1.87 x 10-3 M

[H2], M [Cl2], M [HCl], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change +1.87 x 10-3

At 1.87 x 10-3
equilibrium

Equilibrium
 Stoichiometry tells us [H2] and [I2]
decrease by half as much

[H2], M [Cl2], M [HCl], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

At 1.87 x 10-3
equilibrium

Equilibrium
 We can now calculate the equilibrium
concentrations of all three compounds…

[H2], M [Cl2], M [HCl], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

At 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

equilibrium

Equilibrium
…and, therefore, the equilibrium constant

[HCl]2
K =
c [H ] [Cl ]
2 2

(1.87 x 10-3)2
=
(6.5 x 10-5)(1.065 x 10-3)

= 51

Equilibrium
 Example 2

• The kp for the formation of ammonia is

1.45 x 10 -5 at 500 0C . In an equilibrium
mixture of the 3 gases at 500 0C the
partial pressure of H2 is .928 atm and
for N2 is .432 atm. Find the partial
pressure for NH3 at equilibrium.
• Find Kc from the value of Kp
Equilibrium
• 1.45 x 10 -5

Equilibrium
 January 14

• Predicting the direction of a reaction

• Le Chatelier’s Principle
• HW Page 660
Q 1, 4, 5, 6, 7,
• Le Chatelier’s Principle 51, 53, 55

Equilibrium
 Reaction of the day

• Sodium chloride solution reacts with

silver nitrate

Equilibrium
 Demo

• Add NH3 to test tube and observe

• A complex ion forms

Equilibrium
 COMPLEX IONS

• Transition metal ion with attached ligands

• Ligands are lewis bases with lone pairs of
electrons.
• A lewis base is a substance that has an
unshared pair of electrons in its structure
• H2O (aqua)
• NH3 (ammine)
• Cl- (chloro)
• CN- (cyano)
• OH- (hydroxo)
Equilibrium
 Lewis acid

• Lewis acid - Electron pair acceptor

• Lewis bases – electron pair donor

• Number of ligands attached to the

central metal ion are the coordination
number of a metal. Often is 2 times the
charge of the ion.
Equilibrium
 Transition elements

• Use d-electrons.
• When the transition element has completely
filled d sublevel it forms white compounds
and give colorless solutions.
• The greater the equilibrium constant of the
formation of the complex the more stable the
complex is.
• Bring reaction book for tomorrow!!!!
Equilibrium
 The Reaction Quotient (Q)

• To calculate Q, one substitutes the

initial concentrations on reactants and
products into the equilibrium
expression.
• Q gives the same ratio the equilibrium
expression gives, but for a system that
is not at equilibrium.
Equilibrium
 If Q = K,
the system is at equilibrium.

Equilibrium
 If Q > K,
there is too much product and the equilibrium shifts to the left.

Equilibrium
 If Q < K,
there is too much reactant, and the equilibrium shifts to the right.

Equilibrium
• A 50.0 L reaction vessel contains 1.00
mol of N2, 3.00 mol of H2 and 0.00 mol
of NH3. Will more ammonia be formed
or it will dissociate when the mixture
goes to equilibrium at 400 0 C?
• Kc is 0.500 at 4000C

Equilibrium
 Strategy to solve problem

• Convert #mol to molarity!!!

• Replace values in Qc
• Use the notes from last slides to decide!

• Qc= 23.1
Equilibrium
Le Châtelier’s
Principle
Equilibrium
 Le Châtelier’s Principle

“If a system at equilibrium is disturbed by

a change in temperature, pressure, or the
concentration of one of the components,
the system will shift its equilibrium
position so as to counteract the effect of
the disturbance.”

Equilibrium
 Change in concentration

• Adding reactants to the system will shift

the equilibrium to the products.
• The system will try to remove what was
added by using it to form more
products.
• As reactants are used up (and their
concentration decrease) the, product
concentrations increase.
Equilibrium
• Adding a reactant or product shifts the equilibrium away from the increase.

• Removing a reactant or product shifts the equilibrium towards the decrease.

• To optimize the amount of product at equilibrium, we need to flood the reaction vessel with

reactant and continuously remove product (Le Châtelier).

• We illustrate the concept with the industrial preparation of ammonia.

Equilibrium
 Effects of Volume and Pressure Changes

• As volume is decreased pressure increases.

• Le Châtelier’s Principle: if pressure is increased the system will shift to

counteract the increase (will decrease the pressure).

• That is, the system shifts to remove gases and decrease pressure.

• An increase in pressure favors the direction that has fewer moles of gas.

• In a reaction with the same number of product and reactant moles of gas, pressure has no effect.

Equilibrium
 Effects of Volume and Pressure Changes

N2O4(g) 2NO2(g)
• An increase in pressure (by decreasing the volume) favors the formation of colorless N O .
2 4
• The instant the pressure increases, the system is not at equilibrium and the concentration of both

gases has increased.

• The system moves to reduce the number moles of gas (i.e. the forward reaction is favored).

• A new equilibrium is established in which the mixture is lighter because colorless N O is

2 4
favored.

Equilibrium
• Increasing total pressure by adding an inert gas has no effect on the partial pressures of reactants

and products, therefore it has no effect on the equilibrium.

Effect of Temperature Changes

• The equilibrium constant is temperature dependent.

• For an endothermic reaction, H > 0 and heat can be considered as a reactant.

• For an exothermic reaction, H < 0 and heat can be considered as a product.

Equilibrium
• Adding heat (i.e. heating the vessel), favors the reaction that removes heat.

• An increase in temperature always favors the endothermic reaction! The system will react

absorbing heat and lowering the temperature.

• Removing heat (i.e. cooling the vessel), favors the reaction that releases heat (and increases the

temperature)

• A decrease in temperature will favor the exothermic reaction. The system will respond by releasing

heat.

Equilibrium
 The Effect of Changes in
Temperature
Co(H O) 2+ + 4 Cl - CoCl 2- +6H O
2 6 (aq) (aq) 4 (aq) 2 (l)

Equilibrium
 Cr(H2O)62+(aq) + 4Cl-(aq) CoCl42-(aq) + 6H2O(l)
The forward reaction is endothermic. Heat is a reactant

DH > 0.

– Co(H O) 2+ is pale pink and CoCl 2- is blue.

2 6 4
– If a light purple room temperature equilibrium mixture is placed in a beaker of warm water, the mixture turns

deep blue.

– Since H > 0 (endothermic), adding heat favors the forward reaction, i.e. the formation of blue CoCl 2-.
4

Equilibrium
– If the room temperature equilibrium mixture is placed in a beaker of ice water, the mixture turns bright pink.

– Removing heat favors the reaction that produces heat, and since H > 0 the reverse reaction which is the

formation of pink Co(H O) 2+ will be favored.

2 6

Equilibrium
 Le Châtelier’s Principle

The Effect of Catalysis

• A catalyst lowers the activation energy barrier for the reaction.

• Therefore, a catalyst will decrease the time taken to reach equilibrium.

• A catalyst does not effect the composition of the equilibrium mixture.

Equilibrium
Catalysts increase the rate of both the
forward and reverse reactions.

Equilibrium
 Equilibrium is achieved faster, but the
equilibrium composition remains unaltered.

Equilibrium
N2 (g) + 3 H2 (g) 2 NH3 (g) ΔH
<0
How can we maximize the amount
of ammonia produced in the
Haber process, shown above?

Equilibrium
 The Haber Process
The transformation of nitrogen and hydrogen into ammonia
(NH3) is of tremendous significance in agriculture, where
ammonia-based fertilizers are of utmost importance.

Equilibrium
The Haber Process

If H is added to the system, N will

2 2
be consumed and the two reagents

will form more NH .

3

Equilibrium
The Haber Process

This apparatus helps push the

equilibrium to the right by removing

the ammonia (NH ) from the

3
system as a liquid.

Equilibrium
• N and H are pumped into a chamber.
2 2
• The pre-heated gases are passed through a heating coil to the catalyst bed.

• The catalyst bed is kept at 460 - 550 C under high pressure.

• The product gas stream (containing N , H and NH ) is passed over a cooler to a refrigeration
2 2 3
unit.

• In the refrigeration unit, ammonia liquefies not N or H .

2 2

Equilibrium
• The unreacted nitrogen and hydrogen are recycled with the new N and H feed gas.
2 2

• The equilibrium amount of ammonia is optimized because the product (NH ) is continually
3
removed and the reactants (N and H ) are continually being added.
2 2

Equilibrium
 H2O (g) + CO (g) H2 (g) + CO2 (g)
• Assume equilibrium conditions:
– [H2O] = 1.00M [H2] = 0.20M
– [CO] = 0.50 [CO2] = 0.70M
• What will happen if:
– [CO] is changed to 0.70M?
– [H2] is changed to 0.05M

Equilibrium
 SO3 (g) SO2 (g) + 1/2 O2 (g)
• ΔH = +98.9 kJ
• Determine the effect of each of the following on
the equilibrium (direction of shift)
• What happens to the concentration of SO3 after
each of the changes?
A) Addition of pure oxygen gas.
B) Compression at Constant Temperature
C) Addition of Argon gas
D) Decrease temperature
E) Remove sulfur dioxide gas Equilibrium

F) Addition of a catalyst
 Calculating Equilibrium Concentrations

• The same steps used to calculate equilibrium constants are used.

• K is given.

• Generally, we do not have a number for the change in concentration line.

• Therefore, we need to assume that x mol/L of a species is produced (or used).

• The equilibrium concentrations are given as algebraic expressions.

• We solve for x, and plug it into the equilibrium concentration expressions.

Equilibrium
Example 2 NO2 (g) N2O4 (g) Kc = 0.75
If the initial concentration of NO2 is 0.50 M and the
initial concentration of N2O4 is 0.90 M, what will
the equilibrium concentrations be?

If the initial concentration of N2O4 is 1.00 M (no

NO2 present), what will the equilibrium
concentrations be? Equilibrium
Example
H2 (g) + FeO (s) H2O (g) + Fe (s)
Kc = 5.20
If the initial concentration of H2 is 0.50 M and the
initial concentration of H2O is 6.50 M, what will
the equilibrium concentrations be?

If the initial concentration of H2 is 1.00 M (no

H2O present), what will the equilibrium Equilibrium

concentrations be?
C(s) + H2O (g) <CO (g) + H2 (g)

• At 800 C the Keq=14.1

• a) What are the eq partial pressures of each
gas in the equilibrium mixture at this
temperature if we start with solid carbon and
0.100 mol of H2O in a 1.00 L vessel

Equilibrium
• B) What is the minimum amount of
required to achieve equilibrium under
these conditions?

Equilibrium
• c) What is the total pressure in the
vessel at equilibrium?

Equilibrium
• http://biology.clc.uc.edu/fankhauser/Lab
s/Microbiology/Growth_Curve/Spectrop
hotometer.htm

Equilibrium