CHEMICAL EQUILIBRIUM

Dr. Zalilawati MR
§ Equilibrium is a state in which there are no
observable changes as time goes by.
§ Chemical equilibrium (CE) is achieved when:
ü the rates
of the forward and reverse reactions
are equal
ü the concentrations of the reactants and products
remain constant

Physical equilibrium
H2O (l) H2O (g)

Chemical equilibrium
N2O4 (g) 2NO2 (g)
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 THE CONCEPT OF EQUILIBRIUM
§ Chemical equilibrium (CE) is the point at which the
rate of the forward reaction is equal to the rate of the
reverse reaction.
§ point where all concentrations are constant.

A B
§ The double arrow implies the process is dynamic.
§ As the reaction progresses;
ü [A] decreases to a constant.
ü [B] increases from zero to a constant.
ü When [A] and [B] are constant, equilibrium is
achieved.
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 Rate of sale of
cookies
=
Rate of replacing
cookies
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E.g; Colorless frozen N2O4, at RT, decomposes to brown NO2:

• As the substance warms it begins to decompose:

N2O4(g) ® 2NO2(g)

ü Using the collision model:

ü At the beginning of the reaction, there is no NO2 so the
reverse reaction (2NO2(g) ® N2O4(g)) does not occur.
ü as the amount of NO2 builds up, there is a chance that
two NO2 molecules will collide to form N2O4.
• When enough NO2 is formed, it can react to form N2O4:

2NO2(g) ® N2O4(g)

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• at some time, the color stops changing and there
are a mixture of N2O4 and NO2.
• At equilibrium, as much N2O4 reacts to form NO2
as NO2 reacts to re-form N2O4

N2O4(g) 2NO2(g)
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 LAW OF MASS ACTION
§ Law of Mass Action : For a reversible reaction at
equilibrium and constant temperature, a certain
ratio of reactant and product concentrations has a
constant value (K).

ü The Equilibrium Constant (K) = A number

equal to the ratio of the equilibrium
concentrations of products to the equilibrium
concentrations of reactants each raised to the
power of its stoichiometric coefficient.

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 TWO COMMON WAYS OF DESCRIBING
EQUILIBRIUM CONSTANT (K):
Kc = Concentration of substances in the
reaction are known.

Kp = Units of partial pressure are used

instead of concentration.
- used when the reactants and products are in
the gaseous state.

* Solids (s) and liquids (l) are left out of equilibrium

expressions because their concentrations do not
change during chemical reactions.

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 THE EQUILIBRIUM CONSTANT

• For a general reaction, the equilibrium

constant expression is;
aA + bB(g) pP + qQ

where Kc is the equilibrium law.

Kc =
[P] [Q]
p q

[A] [B]
a b

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 N2O4 (g) 2NO2 (g)

[NO2]2
K= = 4.63 x 10-3
[N2O4]

aA + bB cC + dD

[C]c[D]d
K= Law of Mass Action
[A]a[B]b

Equilibrium Will
K >> 1 Lie to the right => Favor products
K << 1 Lie to the left => Favor reactants
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 TWO TYPES OF EQUILIBRIUM
1. HOMOGENEOUS EQUILIBRIUM
ü Homogenous equilibrium applies to reactions in
which all reacting species are in the same phase.

aA (g) + bB (g) pP(g) + qQ (g)

Kp = Kc(RT)∆n R = 0.0821 L atm mol-1 K-1

∆n = moles of gaseous products – moles of gaseous reactants

= (p + q) – (a + b)

Kc =
[P ] p [Q]q Pp P PqQ
Kp = In most cases
[A]a [B]b Kc ¹ Kp
PaA PBb 13
e.g. Homogeneous Equilibrium

CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)

[CH3COO-][H3O+]
Kc = [H2O] = liquid = constant
[CH3COOH][H2O]

[CH3COO-][H3O+]
Kc =
[CH3COOH]

General practice not to include units for the

equilibrium constant.

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 The equilibrium concentrations for the reaction between carbon
monoxide and molecular chlorine to form COCl2 (g) at 740C
are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M.
Calculate the equilibrium constants Kc and Kp.

CO (g) + Cl2 (g) COCl2 (g)

[COCl2] 0.14
Kc = = = 220
[CO][Cl2] 0.012 x 0.054

Kp = Kc(RT)Dn

Dn = 1 – 2 = -1 R = 0.0821 T = 273 + 74 = 347 K

Kp = 220 x (0.0821 x 347)-1 = 7.7

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The equilibrium constant Kp for the reaction is 158 at 1000K.

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

What is the pressure of O2 if the PNO = 0.400 atm and PNO2 =
0.270 atm?
2
PNO PO 2
Kp = 2
PNO 2

2
PNO
PO 2 = Kp 2
2
PNO

PO 2 = 158 x (0.400)2/(0.270)2 = 347 atm

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 2. HETEROGENOUS EQUILIBRIUM
ü Heterogenous equilibrium applies to reactions in
which reactants and products are in different
phases.

CaCO3 (s) CaO (s) + CO2 (g)

[CaO][CO2] [CaCO3] = constant

Kc‘ =
[CaCO3] [CaO] = constant

Kc = [CO2] Kp = PCO
2

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.
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 CaCO3 (s) CaO (s) + CO2 (g)

PCO 2 = Kp

PCO does not depend on the amount of CaCO3 or CaO

2

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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 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, the
balanced equation and the temperature must be specified.
• If a reaction can be expressed as a sum of two or more
reactions
üthe equilibrium constant for the overall reaction is given
by the product of the equilibrium constants of the
individual reactions.
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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.

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 *the moles into a 10.32 L vessel stuff ... calculate molarity.
Starting concentration of HI: 2.5 mol/10.32 L = 0.242 M

2 HI H2 + I2
Initial: 0.242 M 0 0
Change: -2x +x +x
Equil: 0.242-2x x x

[ H 2 ][ I 2 ] [ x][ x] x2 -3
Keq = Keq = = = 1.26 x10
[ HI ]2 [0.242 - 2 x]2 [0.242 - 2 x]2

What we are asked for here is the equilibrium concentration of H2 = x.

So, we need to solve this for x.
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And yes, it’s a quadratic equation => Do a bit of rearranging:
x2 -3
= 1.26 x10
[0.242 - 2 x]2

x 2 = 1.26 x10 -3 [0.242 - 2 x]2

= 1.26 x10 -3 [0.0586 - 0.968 x + 4 x 2 ]
= 7.38 x10 -5 - 1.22 x10 -3 x + 5.04 x10 -3 x 2

0.995 x 2 + 1.22 x10 -3 x - 7.38 x10 -5 = 0

- b ± b 2 - 4ac Since we are using this to

x= model a real, physical system,
2a we reject the negative root.
x = 0.00802 or –0.00925 The [H2] at equil. is 0.00802 M.
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A 3:1 starting mixture of hydrogen, H2, and Nitrogen, N2
comes to equilibrium at 500 °C. The mixture at equilibrium
is 3.506% NH3, 96.143% N2, and 0.3506% H2 by volume.
The total pressure in the reaction vessel was 50.0 atm. What
is the value of Kp and Kc for the reaction?

N2 + 3H2 2NH3
Hint: Use Dalton’s Law of partial pressures to determine the
partial pressure of each component in the reaction.
PA = XA PT Since we know we have 100%,
Partial Pressure = (% of substance /100 X total pressure)

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 P NH3 = 0.03506 x 50.0 atm = 1.75 atm
P N2 = 0.96143 x 50.0 atm = 48.1 atm
P H2 = 0.003506 x 50.0 atm = 0.175 atm

(P NH3)2 (1.75)2
Kp = = = 11.9
(P N2) (P H2)3 (48.1) (0.175)3
Δn
K p = K c (RT ) ( )1
Dn
Kc = Kp RT

( )
1 -2
Kc = Kp = 4.79 x 104
0.0821 x 773
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 MASS ACTION EXPRESSION
§ The relationship between concentration can be predicted from
the balance equation of the reaction by calculating the
numerical value of mass action expression (= reaction quotient
(Qc))

dD + eE D fF
[F ] f
Qc =
[D ]d [E ]e
ü The reaction quotient (Qc) is calculated by substituting
the initial concentrations of the reactants and products
into the equilibrium constant (Kc) expression.

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IF
• Qc > Kc => system will proceed from right to left to reach
equilibrium
• Qc = Kc => system is at equilibrium
• Qc < Kc => system will proceed from left to right to reach
equilibrium

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 N2(g)+ 3H2(g) D 2 NH3(g)
[NH 3 ]02
Qc =
[N 2 ]0 [H 2 ]30 Kc= 0.65

Qc =
(1.83 x 10 )
-4 2
= 0.611
(0.0711)(9.17 x 10 )-3 3

Qc is smaller than Kc.

Not at equilibrium; too much reactants.
Net Rx goes left to right.
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 LE CHÂTELIER’S PRINCIPLE
§ If an external stress is applied to a system at equilibrium,
the system will readjust to minimize the stress applied as
the system reaches a new equilibrium position.

Change Equilibrium
Change Shift Equilibrium Constant

Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no
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Le Châtelier’s Principle
1. Changes in Concentration

Remove
Add Remove
Add

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left
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1. Changes in Concentration

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

Equilibrium
shifts left to Add
minimize NH3
stress

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Le Châtelier’s Principle
2. Changes in Volume and Pressure

A (g) + B (g) C (g)

Change Shifts the Equilibrium

Increase pressure Side with fewest moles of gas
(= conc. increase)
Decrease volume Side with fewest moles of gas
Decrease pressure Side with most moles of gas
(= conc. decrease)
Increase volume
(= conc. decrease) Side with most moles of gas
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Le Châtelier’s Principle
3. Changes in Temperature

Change Exothermic Rx Endothermic Rx

Increase temperature K decreases K increases
Decrease temperature K increases K decreases

colder hotter
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14.5
Le Châtelier’s Principle
4. Adding a Catalyst
§ does not change K -> does not shift the position of an
equilibrium system
ü Catalyst does not change equilibrium constant or
shift equilibrium.

uncatalyzed catalyzed

§ the system will reach equilibrium sooner

ü Catalyst lowers Ea for both forward and reverse
reactions. 34
14.5
LE CHÂTELIER’S PRINCIPLE

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14.5
 N2O4(g)D 2NO2(g) DHº=56.9KJ
When the above reaction is at equilibrium:
What is the effect of ­ pressure by;
§ ¯ volume? Shift to left.
§ ­ N2O4? Shift to right. Amount of NO2 will increase
§ ¯ Temperature? favor exothermic reaction.
§ Adding catalyst? No change, catalysts only help
increase the rate at which
equilibrium is reached.

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