The Concept of Equilibrium

Chemical equilibrium occurs when a

reaction and its reverse reaction proceed at
the same rate.
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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.

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 A System at Equilibrium

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

Since, in a system at equilibrium, both

the forward and reverse reactions are
being carried out, we write its equation
with a double arrow.

N2O4 (g) 2 NO2 (g)

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 The
Equilibrium
Constant
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 The Equilibrium Constant

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

• Rate Law:
Rate = kf [N2O4]

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 The Equilibrium Constant

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

• Rate Law:
Rate = kr [NO2]2

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 The Equilibrium Constant

• Therefore, at equilibrium
Ratef = Rater
kf [N2O4] = kr [NO2]2
• Rewriting this, it becomes
kf [NO2]2
=
kr [N2O4]

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 The Equilibrium Constant

The ratio of the rate constants is a

constant at that temperature, and the
expression becomes
kf [NO2]2
Keq = =
kr [N2O4]

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 The Equilibrium Constant

• Consider the generalized reaction

aA + bB cC + dD

• The equilibrium expression for this

reaction would be
[C]c[D]d
Kc =
[A]a[B]b
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 The Equilibrium Constant

Since pressure is proportional to

concentration for gases in a closed
system, the equilibrium expression can
also be written
(PCc) (PDd)
Kp =
(PAa) (PBb)

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Relationship Between Kc and Kp
• From the Ideal Gas Law we know that
PV = nRT
• Rearranging it, we get

n
P= RT
V

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 Relationship Between Kc and Kp
Plugging this into the expression for Kp
for each substance, the relationship
between Kc and Kp becomes

Kp = Kc (RT)n
where
n = (moles of gaseous product) - (moles of gaseous reactant)

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 What is Kp in terms of Kc for
the following reaction ?
2 NO(g) + O2(g) 2 NO2(g)

1. Kp = KcRT
2. Kp = Kc/RT
3. Kp = KcR/T
4. Kp = K c
5. Kp = Kc/(RT)2
Equilibrium Can Be Reached from
Either Direction

As you can see, the ratio of [NO2]2 to [N2O4] remains

constant at this temperature no matter what the initial
concentrations of NO2 and N2O4 are.

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Equilibrium Can Be Reached from
Either Direction
This is the data from
the last two trials from
the table on the
previous slide.

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Equilibrium Can Be Reached from
Either Direction

It doesn’t matter whether we start with N2 and

H2 or whether we start with NH3: we will have
the same proportions of all three substances
at equilibrium.

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What Does the Value of K Mean?
• If K>>1, the reaction is
product-favored;
product predominates
at equilibrium.

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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.

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Manipulating Equilibrium Constants
The equilibrium constant of a reaction in
the reverse reaction is the reciprocal of
the equilibrium constant of the forward
reaction.
[NO2]2
N2O4 (g) 2 NO2 (g) Kc = = 0.212 at 100 C
[N2O4]
[N2O4]
2 NO2 (g) N2O4 (g) Kc = 2 = 4.72 at 100 C
[NO2]

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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.
[NO2]2
N2O4(g) 2 NO2(g) Kc = = 0.212 at 100 C
[N2O4]

[NO2]4
2 N2O4(g) 4 NO2(g) Kc = [N O ]2 = (0.212)2 at 100 C
2 4

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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.

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Heterogeneous
Equilibrium

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The Concentrations of Solids and
Liquids Are Essentially Constant

Both can be obtained by multiplying the

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

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The Concentrations of Solids and
Liquids Are Essentially Constant

Therefore, the concentrations of solids

and liquids do not appear in the
equilibrium expression.

PbCl2 (s) Pb2+ (aq) + 2 Cl-(aq)

Kc = [Pb2+] [Cl-]2

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CaCO3 (s) CO2 (g) + CaO(s)
As long as some CaCO3 or CaO remain in
the system, the amount of CO2 above the
solid will remain the same.

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What is the correct equilibrium
constant expression for the
reaction:
P4(s) + 6 Cl2(g) 4 PCl3(l)
Equilibrium
Calculations

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 An Equilibrium Problem
A closed system initially containing 1.000
x 10-3 M H2 and 2.000 x 10-3 M I2 at
448 C is allowed to reach
equilibrium. Analysis of the equilibrium
mixture shows that the concentration of
HI is 1.87 x 10-3 M. Calculate Kc at 448
C for the reaction taking place, which is
H2 (g) + I2 (s) 2 HI (g)

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 What Do We Know?

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

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

Change

At equilibrium 1.87 x 10-3

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 [HI] Increases by 1.87 x 10-3 M

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

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

Change +1.87 x 10-3

At equilibrium 1.87 x 10-3

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

[H2], M [I2], M [HI], 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 equilibrium 1.87 x 10-3

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

[H2], M [I2], M [HI], 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 equilibrium 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

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…and, therefore, the equilibrium constant.

[HI]2
Kc =
[H2] [I2]
(1.87 x 10-3)2
=
(6.5 x 10-5)(1.065 x 10-3)
= 51

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 The Reaction Quotient (Q)

• Q gives the same ratio the equilibrium

expression gives, but for a system that is
not at equilibrium.
• To calculate Q, one substitutes the initial
concentrations on reactants and products
into the equilibrium expression.

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 If Q = K,
the system is at equilibrium.

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

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

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Free Energy and Equilibrium

Under any conditions, standard or

nonstandard, the free energy change
can be found this way:

G = G + RT lnQ

(Under standard conditions, all concentrations are 1 M,

so Q = 1 and lnQ = 0; the last term drops out.)

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 Free Energy and Equilibrium

• At equilibrium, Q = K, and G = 0.
• The equation becomes
0 = G + RT lnK
• Rearranging, this becomes
G = RT lnK
or, -G
K = e RT

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Le Châtelier’s
Principle

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 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.”

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 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.

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The Haber Process

If H2 is added to the
system, N2 will be
consumed and the
two reagents will
form more NH3.

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The Haber Process

This apparatus
helps push the
equilibrium to the
right by removing
the ammonia (NH3)
from the system as
a liquid.

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 The Effect of Changes in
Temperature
Co(H2O)62+(aq) + 4 Cl-(aq) CoCl42- (aq) + 6 H2O (l)

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Which accurately reflects the changes in concentration that
will occur if O2 is added to disturb the equilibrium?

2 NO(g) + O2(g) 2 NO2(g)

[NO] [O2] [NO]

1. Increase Increase Increase
2. Increase Increase Decrease
3. Decrease Decrease Decrease
4. Decrease Decrease Increase
5. Decrease Increase Increase
 Which of the following will result in an equilibrium shift
to the right?

PCl3(g) + Cl2(g) PCl5(g) H° = –87.9 kJ/mol

1. Increase temperature/increase volume

2. Increase temperature/decrease volume
3. Decrease temperature/increase volume
4. Decrease temperature/decrease volume
5. None of the above

PCl5
Catalysts

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Catalysts

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

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Catalysts

When one uses a

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

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