CHEMICAL

EQUILIBRIUM
Reversible Reactions
◦ Chemical reactions that do not proceed to just one
direction or proceed essentially to completion

What happens in a reversible

reaction?
• In reversible reactions, the reactants are not completely
converted into products and some of the products may be
converted back into reactants.
How do we distinguish an irreversible
reaction from a reversible reaction in a
chemical equation?
◦ Unlike in irreversible reactions where a single headed arrow is used,
reversible reactions use a double headed arrow to indicate that the
forward and backward reactions are occurring simultaneously. In
general terms, a reversible reaction may be represented as follows:
aA + bB ↔ cC + dD
where the lowercase letters represent the stoichiometric coefficients of
the reactants and products.
Chemical Equilibrium
What can you say about
the number of cars
inside San Francisco if
the rate at which cars
enter the city is also the
same as the rate at
which the cars leave the
city through the Golden
Gate Bridge?
Chemical Equilibrium
 Chemical Equilibrium
◦ In a reversible reaction, when the
reactants start to form the products,
the products would then start to
reform the reactants. The two
opposing processes happen at
different rates but a certain point in
the reaction will be reached where the
rates of the forward and backward
reactions are the same (marked by
the broken line in Figure 2). This is
the state of chemical equilibrium.
Chemical Equilibrium
Chemical Equilibrium
◦ In a state of chemical equilibrium, since the
rate of product formation is equal to the rate
of the reformation of the reactants, then the
concentrations of the reactants and
products remain becomes constant.
◦ The state of chemical equilibrium is a
highly dynamic state. This means that
though there are no change in the
composition of the reaction mixture and no
visible changes taking place, the particles
are continuously reacting. Also, a system
at chemical equilibrium can be easily
disturbed by changes in the reaction
conditions.
The Law of Mass Action Expression/
Equilibrium Constant Expression
The relationship between the concentrations of the reactants and products may be
expressed using the law of mass action expression/equilibrium constant expression. For
the general equilibrium reaction:

the law of mass action expression is written as

where the [ ] is the concentration expressed in molarity and Keq is the equilibrium
constant. If molar concentrations are used, Keq may also be referred to as Kc. The law
of mass action is basically the ratio of the concentrations of the products raised
to their respective stoichiometric coefficients to that of the reactants.
Equilibrium Constants for
Homogeneous Gaseous Equilibria
◦ Equilibrium constants for homogeneous gaseous equilibria may
also be expressed in terms of partial pressures. The expression is
written in much the same way as described, only that the partial
pressure is raised to the coefficient instead of the molar
concentration.
Equilibrium Constants for
Heterogenous Equilibria
◦ For equilibrium reactions where the reactants and products
are in different phases (heterogeneous equilibria), pure
solids and pure liquids are excluded in writing
equilibrium constant expressions. For example, consider
the reaction:
Why do we omit pure solids and pure liquids
in the equilibrium constant expression?
◦ When the mass of a certain pure solid substance is
doubled, its volume is also doubled. Therefore, when
the mass and volume is related to get the concentration,
a constant value is obtained. Only reactants and
products whose concentration varies during a
chemical reaction are included in the expression.
Equilibrium Constant, K
◦ The equilibrium constant, K, is the numerical value that
is obtained when equilibrium concentrations are
substituted to the equilibrium constant expression. The
value of K may vary from very large to very small values.
This value provides an idea of the relative concentrations
of the reactants and products in an equilibrium mixture.
Equilibrium Constant, K
◦ How can the value of the equilibrium constant be used
to determine the relative composition of the reaction
mixture at equilibrium?
Consider the reaction for the production of phosgene
(COCl2), a toxic gas used in the manufacture of certain
polymers and insecticides, at 100°C:
Equilibrium Constant, K
Sample Problem:
Gaseous hydrogen iodide is placed in a closed container at
425°C, where it partially decomposes to hydrogen and
iodine: 2 HI(g)↔ H2(g) + I2(g). At equilibrium, it is found
that [HI] = 3.53 × 10–3 M, [H2] = 4.79 × 10–4 M and [I2]
=4.79 × 10–4 M. What is the value of Kc at this
temperature?
Equilibrium Constant, K
In general,
◦ If K >> 1 (large K value), the equilibrium lies to the right and the
products predominate in the equilibrium mixture.
◦ If K << 1 (small K value), the equilibrium lies to the left and the
reactants predominate in the equilibrium mixture.
Reaction Quotient
◦ It is the value obtained when product and reactant concentrations or
partial pressures at any point of the reaction is plugged in the
equilibrium constant expression.
◦ It is calculated in the same way as K. Thus for a general
equilibrium reaction
The reaction quotient can be expressed as or
Reaction Quotient
What is the significance of the reaction quotient?
The reaction quotient may be used to determine if a
particular reaction is at equilibrium, and if not, in
which direction the reaction will proceed to attain the
equilibrium.
Reaction Quotient
What is the significance of the reaction quotient?

Consider the following example:

The Kc value for the reaction at 472°C is 0.105. Suppose a mixture of 2.00 mol
of H2, 1.00 mol of N2 and 2.00 mol of NH3 is placed on a sealed 1.00-L
container.

Since the Qc ≠ Kc, then the given mixture is not in equilibrium.

Equilibrium Constant vs. Reaction
Quotient
In what direction will the reaction proceed in order to
attain the equilibrium?
In general:
If K = Q , then the system is already at equilibrium;
If K < Q, the products dominate the reaction mixture
so the products must react to form the reactants;
reaction proceeds in the backward direction until
equilibrium is attained;
If K > Q, the reactants dominate the reaction mixture
so the reactants must react to form the products;
reaction proceeds in the forward direction until
equilibrium is attained.
Write the equilibrium constant expression, Kc,
for the following reactions. Indicate also if the
equilibrium is homogeneous or heterogeneous.
For the following reactions at equilibrium, identify
which between the reactants and products is dominant.
 A. Calculating K when all equilibrium
concentrations/partial pressures are known
Example A.1:
A mixture of hydrogen and nitrogen in a reaction vessel is allowed to
attain equilibrium at 472 °C. The equilibrium mixture of gases was
analyzed and found to contain 7.38 atm H2, 2.46 atm N2 and 0.166
atm NH3. From these data, calculate the equilibrium constant Kp for
the reaction:
 A. Calculating K when all equilibrium
concentrations/partial pressures are known
Example A.2:
An aqueous solution of acetic acid is found to have the
following concentrations at 25 °C: [CH3COOH] = 1.65 ×
10–2M; [H3O+] = 5.44 × 10–4 M; and [CH3COO–] = 5.44
× 10–4 M. Calculate the equilibrium constant Kc for the
ionization of acetic acid at 25 °C. The reaction is:
 A. Calculating K when all equilibrium
concentrations/partial pressures are known

Example A4. Methanol (CH3OH) is produced commercially

by the catalyzed reaction of carbon monoxide and
hydrogen: CO(g) + 2 H2(g) ↔ CH3OH(g). An equilibrium
mixture in a 2.00-L vessel is found to contain 0.0406 mol
CH3OH, 0.170 mol CO and 0.302 mol H2 at 500 K.
Calculate Kc at this temperature.
 B. Calculating K from initial and
equilibrium concentrations/partial pressures
In most cases, what is known to the experimenter is the equilibrium
constant at a certain temperature and the initial concentrations or
partial pressures of the species present. This means that equilibrium
quantities must be determined before calculating for K. This can be
done by treating the change as a variable where the stoichiometric
coefficients from the balanced equation can be used to denote the
relationship between the changes in the concentration/partial
pressure of the reactants and products.
 B. Calculating K from initial and
equilibrium concentrations/partial pressures

Example B1:
A closed system initially containing 1.000 × 10–3 M H2 and
2.000 × 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 × 10–3 M. Calculate Kc at
448 °C for the reaction taking place which is
 B. Calculating K from initial and
equilibrium concentrations/partial pressures

Example B2:
Sulfur trioxide decomposes at high temperature in a sealed container
according to the reaction

Initially, the vessel is charged at 1000 K with SO3(g) at a partial

pressure of 0.500 atm. At equilibrium the SO3 partial pressure is
0.200 atm. Calculate the value of Kp at 1000 K.
 B. Calculating K from initial and
equilibrium concentrations/partial pressures

Example B3. A mixture of 0.100 mol of NO, 0.050 mol of

H2 and 0.10 mol of H2O is placed in a 1.0-L vessel at 300
K. The following equilibrium is established:
2 NO(g) + 2 H2(g) ↔ N2(g) + 2 H2O(g).
At equilibrium [NO] = 0.062 M. Calculate the equilibrium
concentrations of H2, N2 and H2O and Kc.
 B. Calculating K from initial and
equilibrium concentrations/partial pressures

Example B4. A mixture of 1.374 g of H2 (MM = 2.016

g/mol) and 70.31 g of Br2 (MM = 70.9 g/mol) is heated in a
2.00-L vessel at 700 K. These substances react as follows:
H2(g) + Br2(g) ↔ 2 HBr(g). At equilibrium, the vessel is
found to contain 0.566 g of H2. Calculate the equilibrium
concentrations of H2, Br2 and HBr and Kc.
 B. Calculating K from initial and
equilibrium concentrations/partial pressures
Example B5. A mixture of 0.2000 mol of CO2, 0.1000 mol of H2 and
0.1600 mol of H2O is placed in a 2.000-L vessel at 226 °C. The
following equilibrium is established: CO2(g) + H2(g) CO(g) + H2O(g).
a. Calculate the initial partial pressures of CO2, H2 and H2O.
b. At equilibrium, PH2O = 3.51atm . Calculate the equilibrium partial
pressures of CO2, H2 and CO.
c. Calculate Kp for the reaction.
 B. Calculating K from initial and
equilibrium concentrations/partial pressures

Example B6. A flask is charged with 1.500 atm of N2O4(g)

and 1.00 atm NO2(g) at 25 °C, and the following equilibrium
is achieved: N2O4(g) 2NO2(g). After equilibrium is reached,
the partial pressure of NO2 is 0.512 atm.
a. What is the equilibrium partial pressure of N2O4?
b. Calculate the value of Kp for the reaction.
 B. Calculating K from initial and
equilibrium concentrations/partial pressures

Example B7. At 900 K, the following reaction has Kp =

0.345: 2 SO2(g) + O2(g) 2 SO3(g). In an equilibrium
mixture,
the partial pressure of SO2 and O2 are 0.135 atm and 0.455
atm, respectively. What is the equilibrium partial pressure of
SO3 in the mixture?
 Calculating equilibrium concentrations
/partial pressures from initial
concentrations/partial pressures and K
values
Example C1
For the equilibrium Br2(g) + Cl2(g) ↔ 2 BrCl(g), the
equilibrium constant Kp is 7.0 at 400 K. If a cylinder is
charged with BrCl(g) at an initial pressure of 1.00 atm and
the system is allowed to come to equilibrium, what is the
equilibrium partial pressure of BrCl?
 Calculating equilibrium concentrations
/partial pressures from initial
concentrations/partial pressures and K
values
Example C2
For the reaction I2(g) + Br2(g) ↔ 2 IBr(g), Kc = 280 at 150
°C. Suppose that 0.500 mol IBr in a 2.00-L flask is allowed
to reach equilibrium at 150 °C. What are the equilibrium
concentrations of IBr, I2 and Br2?
 Calculating equilibrium concentrations
/partial pressures from initial
concentrations/partial pressures and K
values
Example C3.
When 1.50 mol CO2 and 1.50 mol H2 are placed in a 3.00-
L container at 395 °C, the following reaction occurs:
CO2(g) + H2(g) ↔ CO(g) + H2O(g). If Kc = 0.802, what
are the concentrations of each substance in the equilibrium
mixture?
 Calculating equilibrium concentrations
/partial pressures from initial
concentrations/partial pressures and K
values
Example C4:
The reaction 2 NO(g) N2(g) + O2(g) has a Kc value of 2400
at 2000 K. If 0.850 M each of N2 and O2 are initially
present in a 3.00-L vessel, calculate the equilibrium
concentrations of NO, N2, and O2.
 Calculating equilibrium concentrations
/partial pressures from initial
concentrations/partial pressures and K
values
Example C5:
Chloromethane, CH3Cl, which has been used as a refrigerant and a
local anesthetic, can be made from the following reaction: CH3OH(g)
+ HCl(g) ↔ CH3Cl(g) + H2O(g); Kp = 5.9 × 10^3. If enough
methanol and hydrogen monochloride are added to a container at 120
°C to yield an initial pressure of 0.75 atm for each, what will be the
equilibrium pressures of all the reactants and products?
Le Chatelier’s Principle
◦ Systems at chemical equilibrium may be disturbed by the changes in various
experimental conditions. The effect of any change in these conditions to a
system at chemical equilibrium can be described by the LE CHATELIER’S
PRINCIPLE.
◦ Le Chatelier’s Principle states that if a stress (changes in reaction
conditions) is applied to a system in equilibrium, then the systems adjust
in order to reduce the effect of the stress applied.
◦ The stress that may affect a system at chemical equilibrium include changes in
the concentration of either products or reactants, changes in temperature
and changes in pressure for gaseous equilibria.
Le Chatelier’s Principle
EFFECT OF CHANGING THE CONCENTRATION
OF REACTANTS OR PRODUCTS
Addition of the concentration of the reactants will shift the reaction forward thus
forming more products.
Addition of the concentration of the products will shift the reaction backward
thus reforming the reactants.
In the context of the Le Chatelier’s principle, the stress referred here is the
change in concentration. When the concentration of either a reactant or a
product is increased, the equilibrium shifts into the direction that would
consume that added component. If the concentration is decreased, then the
equilibrium shifts into the direction that replenishes the lost component.
Le Chatelier’s Principle
EFFECT OF CHANGING THE TEMPERATURE
When the temperature is increased, the reaction which consumes the applied
heat is favored i.e. the reaction which is endothermic. When the temperature is
decreased, the reaction which produces heat is favored i.e. the reaction which is
exothermic.
Another way of interpreting the results is to treat heat as either a reactant or
product. When heat is added, equilibrium shifts to the reaction that consumes it.
The same generalization on the effect of changes in concentration is applied.
Le Chatelier’s Principle
EFFECT OF CHANGING THE PRESSURE (OR VOLUME)
ON GASEOUS EQUILIBRIA
For gaseous equilibria, changes in pressure due to changes in the volume of the container
affect chemical equilibrium. When the pressure is increased (by decreasing the volume of
the container), the system adjusts by reducing the total pressure exerted by the gas particles
present. This can be done by shifting the equilibrium towards the formation of a lesser
number of gas particles which may be predicted using a balanced chemical equation.
When the volume of the container is increased, then the total pressure is decreased. When
this happens, the equilibrium shifts to the direction that would. produce more gas particles,
The total pressure of the gaseous reaction may also be increased by adding an inert gas
which is not involved in the equilibrium reaction. There will be a change in the total pressure
but not the partial pressures of the gases. This will therefore not affect the value of the
equilibrium constant and will not cause a shift of the equilibrium.
APPLICATION OF THE LE
CHATELIER’S PRINCIPLE
◦ Practitioners of chemistry in the industry find Le Chatelier’s principle of great
importance especially in the manufacturing of many products. For a more
efficient production process, they formulate ways by which product yield can
be maximized and waste generation can be minimized. This can be done by
examining the effects of changing the reaction conditions such as temperature,
pressure and concentrations of the substances involved on the yield of the
process.
 APPLICATION OF THE LE
CHATELIER’S PRINCIPLE
◦ For example, when Fritz Haber
developed the process of producing
ammonia, NH3, from N2 and H2,
according to the reaction:
N2(g) + 3H2(g)↔ 2NH3(g)
he tried to vary the pressure and
temperature conditions to determine
what conditions will maximize the
yield of ammonia.
 APPLICATION OF THE LE
CHATELIER’S PRINCIPLE
◦ Another way by which the yield of
ammonia can be maximized is to
continuously remove the ammonia
product from the equilibrium
mixture. This can be done by
condensing the gas in to a liquid
form and withdrawing it from the
reaction. In this way, the equilibrium
will shift to the right favoring the
formation of more ammonia. (Figure
2)
 Equilibrium Reaction Keq Stress Applied Effect Equilibrium
expression shift

H2(g) + Cl2(g) ↔ 2HCl(g) Decreasing the _________ in the

pressure number of moles of
HCl(g)
Fe3O4(s) + 4H2(g) + heat ↔ 3 Fe(s) + Increasing the _________ in the
4H2O(g) temperature volume of water vapor
collected
2NO(g) + O2(g) ↔ 2NO2(g) + heat Addition of _________ in the
helium number of moles of
NO
H2CO3(aq) ↔ CO2(aq) + H2O(l) Removal of CO2 _________ in the
amount of H2CO3
Increasing the _________ in the
temperature amount of O2

Increasing the _________ in the

4NH3(g) + 5O2(g) ↔ NO(g) + 6H2O(g) + volume of the amount of H2O
heat container
Removing O2 _________ in the
amount of NH3