Chapter 3 Chemical Equilibrium

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Copyright © 2022 Saint Mary’s University, Bayombong, Nueva Vizcaya

Chemical
Equilibrium
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Topic Overview
• Concept of Chemical Equilibrium
• Ways of Expressing Equilibrium Constants
• Homogeneous Equilibria
• Heterogeneous Equilibria
• Multiple Equilibria
• Magnitude of Chemical Equilibrium
Copyright © 2022 Saint Mary’s University, Bayombong, Nueva Vizcaya 3

Topic Overview
• Equilibrium Constant
• Predicting the Direction of a Reaction
• Calculating Equilibrium Concentrations
• Factors that Affect Chemical Equilibrium
• Le Chatelier’s Principle
• Changes in Concentrations
• Changes in Volume and Pressure
• Changes in Temperature
• The Effect of a Catalyst

Chemical Equilibrium
• In principle, every chemical reaction is reversible ...
capable of moving in the forward or backward
direction.
2 H2 + O2 2 H2O
• Some reactions are easily reversible ...

Some are not so easy ...

• Looks at the extent of a chemical reaction.
• In stoichiometry we talk about theoretical yields,

and the many reasons actual yields may be lower.
• Another critical reason actual yields may be lower

is the reversibility of chemical reactions: some
reactions may produce only 70% of the product
you may calculate they ought to produce.

Chemical Reaction
• chemical change that involves the interaction
between the electrons of substances in their
atomic, molecular, or ionic structures

Types of Chemical reactions
Reversible Reaction – the products are capable of forming the
original substances or reactants; it does not go into completion
A + B ⇄ C + D

Types of Chemical reactions
Irreversible Reaction - the products are not capable of forming the
original substances or reactants; it goes to completion.
A + B → C + D

Equilibrium is a state in which there are no observable changes as
time goes by.
➢Vaporization of water
remains constant
➢Dynamic equilibrium
a balanced condition in
which the rates of
opposing processes are
equal
Evaporation of
water
Evaporation ⇄ Condensation
Chemical equilibrium is achieved when:
• the rates of the forward and reverse reactions are equal
• the concentrations of the reactants and products remain
constant
• the attainment of equilibrium is not immediate and often
requires an extended period
Physical equilibrium
H2O (l) H2O (g)
Chemical equilibrium
N2O4 (g) 2NO2 (g)

• There is still activity at the molecular level because
constant conversion between the reactant molecules
and product molecules continues to occur
• Dynamic situation

✓ occurs when a reaction and its reverse

reaction proceed at the same rate.
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.
A System at Equilibrium
Once equilibrium
is achieved, the
amount of each
reactant and
product remains
constant.
N2O4 (g) 2NO2 (g)
Ratef = Rater
kf [N2O4] = kr [NO2]2
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N2O4 (g) 2NO2 (g)
equilibrium
equilibrium
equilibrium
Start with NO2 Start with N2O4 Start with NO2 & N2O4

constant

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
N2O4 (g) 2 NO2 (g)

The Equilibrium Constant
• Forward reaction:
N2O4 (g) ⎯⎯→ 2 NO2 (g)
• Rate law:
Rate = kf [N2O4]

• Reverse reaction:
2 NO2 (g) ⎯⎯→ N2O4 (g)
• Rate law:
Rate = kr [NO2]2

• Therefore, at equilibrium
Ratef = Rater
kf [N2O4] = kr [NO2]2
• Rewriting this, it becomes
kf [NO2]2
=
kr [N2O4]
The ratio of the rate constants is a
constant at that temperature, and the
expression becomes
kf [NO2]2
Keq = =
kr [N2O4]

• To generalize this expression, consider
the reaction
aA + bB cC + dD
• The equilibrium expression for this reaction
would be Law of Mass Action
[C]c[D]d Cato Guldenberg
Kc = and
[A]a[B]b Peter Waage
• Relates the concentrations of reactants and products at equilibrium in terms of

equilibrium constant.

N2O4 (g) 2NO2 (g)
[NO2]2
Kc= = 4.63 x 10-3
[N2O4]
aA + bB cC + dD
[C]c[D]d
Kc = Law of Mass Action
[A]a[B]b
• The equilibrium constant of a reaction can be expressed as a ratio of the rate

constants of the forward and reverse reactions.

Ways of Expressing
Equilibrium Constants
• To use equilibrium constants, you must
know how to express them in terms o f
reactant and product concentrations.
• Guide: Law of Mass Action
• Concentrations of the reactants and
products can be expressed in several types
of units
• Reacting species are not always in the
same phase

[C]c[D]d
Sample Exercise Kc =
[A]a[B]b
Write the equilibrium expression for Kc for the
following reactions.
1. 2O3 (g) ⇄ 3O2 (g)
2. 2NO (g) + Cl2 (g) ⇄ 2NOCl (g)
3. H2 (g) + I2 (g) ⇄ 2HI (g)
4. N2 (g) + 3H2 (g) ⇄ 2NH3(g)
5. CO (g) + Cl2 (g) ⇄ COCl2 (g)

Homogenous equilibrium applies to reactions in which all reacting
species are in the same phase.
N2O4 (g) 2NO2 (g)
2
PNO
[NO2 ]2 2
Kc = Kp =
[N2O4] PN O
2 4
In most cases
Kc  Kp
aA (g) + bB (g) cC (g) + dD (g)
Kp = Kc(RT)Dn
Kc = Kp: Dn = 0
Because pressure is proportional to
concentration for gases in a closed system,
the equilibrium expression can also be
written
(PC)c (PD)d
Kp =
(PA)a (PB)b

Relationship between Kc and Kp
• From the ideal gas law we know that
PV = nRT
• Rearranging it, we get
n
P= RT
V
PV = MRT PV = [A]RT
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)Dn Kp = Kc (0.0821 T)Dn

Where
Dn = (moles of gaseous product) − (moles of gaseous reactant)
= (c + d) – (a + b)
Example:
1. In the synthesis of ammonia from nitrogen and
hydrogen, Kc = 9.60 at 300oC:
N2 (g) + 3H2 (g) ⇄ 2NH3(g)
Calculate Kp for this reaction at this temperature.
General practice not to include units for the equilibrium

constant.

(PC)c (PD)d
Sample Exercise Kp =
(PA)a (PB)b
• Write the equilibrium expression for Kp
for the following reactions.
1. 2O3 (g) ⇄ 3O2 (g)
2. 2NO (g) + Cl2 (g) ⇄ 2NOCl (g)

(PC)c (PD)d
Sample Exercise Kp =
(PA)a (PB)b
• Write the equilibrium expression for Kp
for the following reactions.
3. H2 (g) + I2 (g) ⇄ 2HI (g)
4. N2 (g) + 3H2 (g) ⇄ 2NH3(g)
5. CO (g) + Cl2 (g) ⇄ COCl2 (g)

Sample Exercise
2. For the equilibrium 2SO3 (g) ⇄ 2SO2 (g) + O2 (g) at a
temperature of 1000 K, Kc has the value 4.08 x 10-3.
Calculate the value for Kp.
ANS: Kp = 0.335

Homogeneous Equilibrium
CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)
[CH3COO-][H3O+]
Kc‘ = [H2O] = constant
[CH3COOH][H2O]
[CH3COO-][H3O+]
Kc = = Kc‘[H2O]
[CH3COOH]

N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)
[NO2]2 [N2O4] 1
Kc = = 4.63 x 10-3 K ‘=c = = 216
[N2O4] [NO2]2 Kc
When the equation for a reversible reaction is

written in the opposite direction, the equilibrium
constant becomes the reciprocal of the original
equilibrium constant.

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 = [CaO] = constant
[CaCO3]
[CaCO3]
Kc = [CO2] = Kc‘ x Kp = PCO 2
[CaO]
The concentration of solids and pure liquids are not included in
the expression for the equilibrium constant.
Molar concentration of a pure solid (or a pure liquid) is a

constant at a given temperature; it does not depend on the
quantity of the substance present.
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.
PCO2 = Kp
PCO 2 does not depend on the amount of CaCO3 or CaO
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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

Multiple Equilibria
• a state in which the product molecules in
one equilibrium system are involved in a
second equilibrium process.
• if a reaction can be expressed as the

sum of 2 or more reactions, the product
of the equilibrium constants of the
individual reactions gives the equilibrium
constant for the reaction.

[C][D] [E][F]
A+B C+D Kc‘ Kc‘ = Kc‘‘=
[A][B] [C][D]
C+D E+F K‘c‘
[E][F]
A+B E+F Kc Kc =
[A][B]
Kc = Kc‘ x K‘c‘
If a reaction can be expressed as the sum of two

or more reactions, the equilibrium constant for
the overall reaction is given by the product of the
equilibrium constants of the individual reactions.

Exercises: The Equilibrium
Expression
Write the expressions Kc and Kp if applicable for the
following reversible reactions at equilibrium:
1. N2 (g) + 3H2(g) 2NH3 (g)

2. HF (aq) + H2O (l) H3O+ (aq) + F- (aq)
3. 2NO (g) + O2 (g) 2NO2 (g)
4. 2H2S (g) + 3 O2 (g) 2 H2O (l) + 2SO2 (g)
5. CH3COOH (aq) + C2H5OH (aq) CH3COOC2H5 (aq)
+ H2O (l)
Write the equilibrium
expressions
• Write the expressions Kc, and Kp if applicable for the
following reversible reactions at equilibrium:
6. (NH4)2Se (s) 2NH3 (g) + H2Se (g)

7. AgCl (s) Ag+ (aq) + Cl- (aq)
8. P4 (s) + 6Cl2(g) 4PCl3 (l)

Write the equilibrium
expression

Writing Equilibrium Constant Expressions
1. 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.
2. The concentrations of pure solids, pure liquids and solvents
do not appear in the equilibrium constant expressions.
3. The equilibrium constant is a dimensionless quantity.
4. In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.
5. If a reaction can be expressed as a sum of two or more
reactions, the equilibrium constant for the overall reaction is
given by the product of the equilibrium constants of the
individual reactions.

Magnitude of Chemical Equilibrium
• Kc value depends on the nature of the reaction
and on the temperature
• At constant T, the magnitude of Kc varies greatly

from one reaction to another
• Value of Kc tells us the relative quantities of the

reactants and products formed at equilibrium and
the yield of the reaction
What Does the Value of K Mean?
• If Kc >> 1 (>10), the
reaction is product-
favored; product
predominates at
equilibrium.
• If Kc << 1 (<10), the

reaction is reactant-
favored; reactant
predominates at
equilibrium.
What Does the Value of K
Mean?
If Kc is neither very large nor very small compared with 1,
then the quantities of reactants and products present at
equilibrium will be comparable

[C]c[D]d
Kc = a b aA + bB cC + dD
[A] [B]
Equilibrium Will
K >> 1 Lie to the right Favor products
K << 1 Lie to the left Favor reactants

Problems
1. Consider the following system at 2300 oC:
2 O3 (g) ⇄3 O2 (g) Kc = 2.54 x 1012 , where will the
reaction proceed? If [O2] = 0.500 M at
equilibrium, then what is [O3]?

Problems
Cl2 (g) ⇄ Cl (g) + Cl (g) Kc = 1.4 x 10-38 , where will the
reaction proceed? If [Cl2] = 0.76 M at equilibrium, then what
is [Cl]?

Problems
CO (g) + H2O (g) ⇄ H2 (g) + CO2(g) Kc = 5.10, if [CO] =
0.200 M, [H2O] = 0.400 M and [H2] = 0.300 M at
equilibrium, then [CO2] =?

Chemical kinetics and
[C]c[D]d
Kc =
[A]a[B]b
• Quantity is always constant at a given
temperature regardless of the variations
in individual equilibrium concentrations
Why?
Chemical Kinetics and Chemical Equilibrium
kf ratef = kf [A][B]2
A + 2B AB2
kr rater = kr [AB2]
Equilibrium
ratef = rater
kf [A][B]2 = kr [AB2]
kf [AB2]
= Kc =
kr [A][B]2
Because rate constants are temperature-
dependent, it follows that the equilibrium constant
must also change with temperature.
Chemical kinetics and
Chemical equilibrium
• From the chemical kinetics viewpoint, the equilibrium
constant of a reaction can be expressed as a ratio of the
rate constants of of the forward and reverse reactions
• This analysis explains why equilibrium constant is a

constant and why its value changes with temperature

Calculating Equilibrium
Constants

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)

Phosgene, COCl2
• colorless gas gained infamy as a chemical
weapon during World War I
• valued industrial reagent and building block
in synthesis of pharmaceuticals and
other organic compounds
• [low]: odor resembles freshly cut hay or
grass
• named from the Greek words 'phos' (light)
and genesis (birth)

The equilibrium constant Kp for the reaction
2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure of O2 if the
PNO = 0.400 atm and PNO = 0.270 atm?
2
2
PNO PO 2
Kp = 2
PNO 2
PO 2
2
PNO 2
PO 2 = Kp
2
PNO

Consider the following equilibrium at 295 K:
NH4HS (s) NH3 (g) + H2S (g)
The partial pressure of each gas is 0.265 atm. Calculate Kp and
Kc for the reaction?
Kp = PNH PH S = 0.265 x 0.265 = 0.0702

3 2
Dn = 2 – 0 = 2
T = 295 K

What does the K c tell us?
• Equilibrium constant for a given reaction can be
calculated from known equilibrium concentrations
• Once we know the value of Kc, we can use
[C]c[D]d
Kc =
[A]a[B]b
to calculate unknown equilibrium concentrations
• Kc is constant only if the T does not change

What does the Kc tell us?
• Helps us to predict the direction in which a reaction
mixture will proceed to achieve equilibrium
• Helps us to calculate the concentration of reactants and

products once equilibrium has been reached

The Reaction Quotient (Q)
a number equal to the ratio of product concentration to
reactant concentration raised to the power of its
stoichiometric coefficients at some point other than
equilibrium
The reaction quotient (Qc) is calculated by substituting the

initial concentrations of the reactants and products into the
equilibrium constant (Kc) expression.

The Reaction Quotient (Qc)
IF
• Qc > Kc system proceeds from right to left to reach equilibrium
• Qc = Kc the system is at equilibrium
• Qc < Kc system proceeds from left to right to reach equilibrium

If Qc > Kc,
there is too much product and the equilibrium
shifts to the left.

If Qc = Kc,
the system is at equilibrium.

If Qc < Kc,
there is too much reactant, and the equilibrium
shifts to the right.

If Qc < Keq, shift to If Qc > Keq, shift to
right (toward product) left (toward reactant)
Predicting the Direction of a
Reaction
The equilibrium constant Kc for the reaction:
H2 (g) + I2 (g) ↔ 2HI (g)
is 54.3 at 430 oC. Suppose that in a certain
experiment, 0.243 mol of H2; 0.146 mol of I2;
and 1.98 mol of HI were placed in a 1.00 L
container at 430 oC, will there be a net reaction
to form from H2 and I2 or more HI?

At the start of a reaction, there are 0.249 mol N2, 3.21 x 10-2 mol
H2, and 6.42 x 10-4 mol NH3 in a 3.50 L reaction vessel at 200 oC.
If the equilibrium constant (Kc) for the reaction
N2 (g) + 3H2 (g) ↔ 2NH3 (g)
is 0.65 at this temperature; decide whether the system is at
equilibrium, if it is not, predict which way the net reaction will
proceed.

The equilibrium constant Kc for the reaction:
2NO (g) + Cl2 (g) ↔ 2NOCl (g)
is 6.50 x 104 at 35 oC. In a certain experiment,
2.00 x 10-2 mol of NO, 8.30 x 10-3 mol of Cl2 and
6.80 mol of NOCl are mixed in a 2.0 L flask. In
which direction will the system proceed to reach
equilibrium? What is the Kp of the reaction at
this temperature?
Kp = 2.57 x 103
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.

Calculating Equilibrium
Concentrations
A B Kc = 24.0 at a certain T
[A] = 0.850 mol/L
Calculate [A] and [B] at equilibrium
A B
Initial (M) 0.850 M 0M

Change (M) -x +x
Equilibrium (M) 0.850 – x x

At 12800C the equilibrium constant (Kc) for the reaction
Br2 (g) 2Br (g)
Is 1.1 x 10-3. If the initial concentrations are [Br2] = 0.063 M and
[Br] = 0.012 M, calculate the concentrations of these species at
equilibrium.
Let x be the change in concentration of Br2

Br2 (g) 2Br (g)
Initial (M) 0.063 0.012
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x
[Br]2 (0.012 + 2x)2

Kc = Kc = = 1.1 x 10-3 Solve for x
[Br2] 0.063 - x
A mixture of 0.500 mol H2 and 0.500 mol I2 was placed in a
1.00 L stainless steel flask at 430 oC, calculate the
concentrations of H2, I2 and HI at equilibrium. The
equilibrium constant Kc for the reaction
H2 (g) + I2 (g) ↔ 2HI (g) is 54.3 at this temperature.
H2 (g) + I2 (g) ↔ 2HI (g)
Initial (M) 0.500 0.500 0.000

Change(M) -x -x + 2x
Equilibrium (M) (0.500 – x) (0.500 – x) + 2x
Kc = [HI]2 / [H2] [I2] Kc = (2x)2 / (0.500 – x) (0.500 – x)

Factors that Affect Chemical
Equilibrium
• Le Chatelier’s Principle
• Changes in Concentrations
• Changes in Volume and Pressure
• Changes in Temperature
• The Effect of a Catalyst

Le Châtelier’s Principle
An Equilibrium Law

“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.”
Henry Louis Le Chatelier

(French industrial chemist)
• If an external stress is applied to a system at equilibrium, the
system adjusts itself in such a way that the stress is partially
offset
• Applied to make qualitative predictions about the response of a

system at equilibrium to various changes in external conditions
• Adding or removing a reactant or product
• Changing the pressure
• Changing the temperature
• Adding a catalyst

• A system at equilibrium is in dynamic state

• Forward and reverse processes are
occurring at equal rates
• The system is in a state of balance

• An alteration in the conditions of the system may disturb
the state of balance
• If this occurs, the equilibrium shifts until a new state of
balance is attained
• States that the shift will be in the direction that
minimizes or reduces the effect of the change

Changes in Reactant or
Product Concentrations
• If a chemical system is at equilibrium and

we add a substance (either a reactant or a
product), the reaction will shift so as to
reestablish equilibrium by consuming part
of the added substance
• Conversely, removal of a substance will

result in the reaction moving in the
direction that forms more of the substance
Changes in Concentration
Remove Remove
Add 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
Changes in Reactant or Product Concentrations
N2 (g) + 3H2 (g) 2NH3 (g)
Equilibrium
Add
shifts left to
NH3
offset stress

Effects of Volume and Pressure Changes
• If a system is at equilibrium and its V is decreased,

thereby increasing its total P, LCP indicates that the
system will respond by shifting its equilibrium position to
reduce the P
• A system can reduce its P by reducing the total number

of gas molecules; fewer molecules of gas exert a lower
pressure

Effects of Volume and
Pressure Changes
• Thus at constant T, reducing the V of a gaseous
equilibrium mixture causes the shift in the direction that
reduces the number of moles of gas
• Conversely, increasing the volume causes a shift in the

direction that produces more gaseous molecules

Changes in Volume and Pressure
A (g) + B (g) C (g)
Change Shifts the Equilibrium

Increase pressure Side with fewer moles of gas
Decrease pressure Side with more moles of gas
Increase volume Side with more moles of gas
Decrease volume Side with fewer moles of gas
For reactions in which there is no change in the number of moles of

gases, a pressure (or a volume) change has no effect on the position of
equilibrium.
Effect of temperature changes
• Changes in concentration or total pressure cause shifts
in equilibrium without changing the value of the
equilibrium constant
• In contrast, almost every equilibrium constant changes

in value as the temperature changes

How can we explain the dependence of equilibrium
on temperature?
• By applying LCP
• Treat heat as if it were a chemical reagent:
• Endothermic rxn : reactants + heat products
(ΔH > 0)
• Exothermic rxn: reactants products + heat
(ΔH < 0):
• When the T is increased, the equilibrium shifts in the
direction that absorbs heat.
• When the T is decreased, the equilibrium shifts in the
direction that releases heat.

Changes in Temperature
• Exothermic rxn: reactants products + heat
• Heat is absorbed as products are converted into reactants,
so equilibrium shifts to the left and Kc decreases
• Exothermic: increasing T, decrease in Kc
• Endothermic rxn: reactants + heat products

• Heat is absorbed as reactant are converted into products, so
equilibrium shifts to the right and Kc increases
• Endothermic: increasing T, increase in Kc

• Cooling a reaction has the opposite effect of
heating it
• As we lower the T, the equilibrium shifts to the
side that produces heat
• Thus cooling an endothermic reaction shifts
the equilibrium to the left, decreasing Kc
• Endothermic rxn: reactants + heat
products
• Cooling an exothermic reaction shifts the

equilibrium to the right, increasing Kc
• Exothermic rxn: reactants products +
heat

N2O4 (g) ⎯⎯→ 2 NO2 (g) DHo = 58.0 kJ (endothermic)
2 NO2 (g) ⎯⎯→ N2O4 (g) DHo = -58.0 kJ (exothermic)
N2O4 (g) ↔ 2 NO2 (g) ; net heat effect = 0
What happens if the system is heated at constant volume?

2 NO2 (g) ⎯⎯→ N2O4 (g) DHo = -58.0 kJ (exothermic)
Change Exothermic Rxn Shifts the Equilibrium

Increase temperature Kc decreases left
Decrease temperature Kc increases right
colder hotter
N2O4 (g) ⎯⎯→ 2 NO2 (g) DHo = 58.0 kJ (endothermic)
Change Endothermic Rxn Shifts the Equilibrium

Increase temperature Kc increases right
Decrease temperature Kc decreases left
colder hotter
Adding a Catalyst
• does not change Kc
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner
uncatalyzed catalyzed
Catalyst lowers Ea for both forward and reverse reactions.
Catalyst does not change equilibrium constant or shift equilibrium.

Summary
Change Equilibrium
Change Shift Equilibrium Constant
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no

Haber – Bosch Process
• In developing the process for making
ammonia from N2 and H2, Haber sought
the factors that might be varied to
increase the yield of NH3
• Using the values of the equilibrium

constant at various T, he calculated the
equilibrium amounts of NH3 formed
under a variety of conditions

Haber’s research focus: catalyst

Chemistry in action

Life at high altitude and
hemoglobin production
• physiology is affected by environmental conditions
• consequences of sudden change in altitude
• can cause headache, nausea, unusual fatigue and
other discomforts
• symptoms of hypoxia, a deficiency in the amount of
oxygen reaching body tissues
• in serious cases, the victim may slip into coma and
die if not treated quickly

Life at high altitude
• A person living at high altitude for weeks or months
gradually recovers from altitude sickness and
becomes acclimatized to the low oxygen content in
the atmosphere, able to function normally
• Mountaineers need weeks or even months to

become acclimatized before scaling summits such
as Mt. Everest

Hemoglobin production
• The combination of oxygen with the hemoglobin
(Hb) molecule, which carries oxygen through the
blood, is a complex reaction
• HbO2 (oxyhemoglobin)
• hemoglobin-oxygen complex that actually
transports oxygen to tissue

Applying LCP
• At an altitude of 3 km the partial pressure of oxygen is

only about 0.14 atm, compared with 0.2 atm at sea level
• According to LCP, a decrease in oxygen concentration
will shift the equilibrium from right to left
• This change depletes oxyhemoglobin, causing hypoxia

Applying LCP
• Given enough time, the body can cope with this
adversity by producing more hemoglobin molecules
• The equilibrium will then gradually shift again from left
to right, favoring the formation of oxyhemoglobin
• The increase in hemoglobin production proceeds slowly,
requiring two or three weeks to develop
• Full capacity may require several years to develop
• Studies show that long-time residents of high altitude
areas have high hemoglobin levels in their blood –
sometimes as much as 50% more than individual living
at sea level

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Example
Consider the following equilibrium process:
N2F4 ⇄ 2 NF2 (g) Δ Ho = +38.5 kJ
Predict the changes in the equilibrium if
• The reacting mixture is heated at constant volume,
• NF2 gas is removed from the reacting mixture at constant
temperature and volume,
• The pressure of the reacting mixture is decreased at constant
temperature, and
• An inert gas, such as H2 gas (catalyst) is added to the reacting
mixture at constant volume and temperature.
131
Example
Consider the equilibrium:

3O2(g) ⇄ 2O3(g) Δ Ho = +284kJ
What would be the effect of

• increasing the pressure on the system by decreasing the
volume,
• increasing the pressure by adding O2 to the system,
• decreasing the temperature, and
• adding a catalyst.
132
Summary
• dynamic equilibria between phases (physical equilibria) and
between reacting substances (chemical equilibria)
• physical equilibria – equilibria between 2 phases of the same
substance
• For the general chemical reaction
aA + bB cC + dD
the concentrations of reactants and products at equilibrium are
related by the equilibrium constant expression
[C]c[D]d
Kc =
[A]a[B]b
Summary
• Equilibrium constant may also be expressed
in terms of the equilibrium partial pressures
of gases as Kp
• Homogeneous equilibrium
• Heterogeneous equilibrium
• Multiple equilibrium
• Concentrations of pure solids, pure liquids
are constant and do not appear in the
equilibrium constant expression of a reaction

Summary
• Reaction quotient (Q) has the same form as the
equilibrium constant expression
• Qc > Kc – reaction proceeds from R to L to
achieve equilibrium
• Qc < Kc - reaction proceeds from L to R to
achieve equilibrium
• Le Chatelier’s principle – if an external stress is
applied to a system at chemical equilibrium, the
system will adjust to partially offset the stress

Summary
• Only change in T changes the value of Kc
• Changes in conc’n, P or V may change the

equilibrium conc’n of reactants and products
• Addition of catalysts hastens the attainment

of equilibrium but does not affect the
equilibrium concentrations of reactants and
products

Chapter 3 Chemical Equilibrium

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Chapter 3 Chemical Equilibrium

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• Some reactions are easily reversible ...

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• Looks at the extent of a chemical reaction.

• In stoichiometry we talk about theoretical yields,

• Another critical reason actual yields may be lower

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H2O (l) H2O (g)

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✓ occurs when a reaction and its reverse

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N2O4 (g) 2 NO2 (g)

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• Rewriting this, it becomes

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• Relates the concentrations of reactants and products at equilibrium in terms of

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• The equilibrium constant of a reaction can be expressed as a ratio of the rate

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Kp = Kc (RT)Dn Kp = Kc (0.0821 T)Dn

General practice not to include units for the equilibrium

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1. 2O3 (g) ⇄ 3O2 (g)

2. 2NO (g) + Cl2 (g) ⇄ 2NOCl (g)

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4. N2 (g) + 3H2 (g) ⇄ 2NH3(g)

5. CO (g) + Cl2 (g) ⇄ COCl2 (g)

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When the equation for a reversible reaction is

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

[CaO][CO2] [CaCO3] = constant

Molar concentration of a pure solid (or a pure liquid) is a

PbCl2 (s) Pb2+ (aq) + 2 Cl−(aq)

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• if a reaction can be expressed as the

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If a reaction can be expressed as the sum of two

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

6. (NH4)2Se (s) 2NH3 (g) + H2Se (g)

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• At constant T, the magnitude of Kc varies greatly

• Value of Kc tells us the relative quantities of the

• If Kc << 1 (<10), the

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