CHAPTER 11

CHEMICAL EQUILIBRIUM

CONCEPT MAP

LEARNING COMPETENCIES
 To describe reversible reactions
 To explain Chemical Equilibrium in terms of reaction rates of the forward and the
reverse reaction.
 Calculate Equilibrium Constant and the pressure or concentration of reactants or
products in an equilibrium mixture.
 To state the Le Chatelier’s principle and apply qualitatively to describe the effect
of changes in pressure, concentration and temperature on a system at equilibrium.

CHEMICAL EQUILIBRIUM
A reaction is in chemical equilibrium when the rate of the forward reaction equals
the rate of the reverse reaction. Consider these examples to understand more regarding
the equilibrium:
Example no.1:
In the bottle there is carbon dioxide (CO2) dissolved in the liquid (H2O). There is
also CO2 gas in the space between the liquid and the cap. There is a constant movement
of CO2 from the liquid to the gas phase, and from the gas phase into the liquid. However,
if you look at the bottle there does not appear to be any change. The system is in
equilibrium.
 CO2 (g) + H2O (l) ⇌ H2CO3
Hemoglobin is a macromolecule that transports oxygen around our bodies. Without
it we would not survive. The hemoglobin has to be able to take up oxygen, but also to
release it and this is done through changes in the chemical equilibrium of this reaction in
different places in our bodies.
Hemoglobin + 4O2(g) ⇌ Hemoglobin (O2)4

Equilibrium Constant Kc, Chemical Equilibrium is the state in which the reactants
and products have no net change over time. This is when the forward and reverse
reactions occur at equal rates. This state of equilibrium can be described by the equilibrium
constant, K. To determine the amount of each compound that will be present at equilibrium
you must know the Equilibrium Constant. To determine the equilibrium constant you must
consider the chemical reaction written in the form:
aA + bB ⇌ cC + dD
Using the Law of mass action, Forward reaction rate = k+ [A]a[B]b and
Backward reaction rate = k– [C]c[D]d.
k+ [A]a[B]b = k– [C]c[D]d
We have, Kc = k+ / k– Kc = [ A ]a·[ B ]b / [C ]c·[ D ]d.
Example no. 2:
The value of R is .08206 L atm. mol-1 K-1. T represents the temperature in Kelvin
(K) at which the equilibrium reaction takes place. To find Δngas, simply subtract the sum
of the coefficients of the reactants from the sum of the coefficients of the products. For the
following balanced chemical reaction:

CH3OH (g) ⇌ CO (g) +2H2 (g)(4)

The value of Δngas is (1 +2)-1 = 2.
Knowing the Kc value for the above reaction is 14.5 and the temperature at
equilibrium is 483K, we can find KP.
KP = (14.5)(.08206 ∗ 483)2 = 22778.50877

Equilibrium Constant & Gibbs Free energy, If we know the standard state free
energy change, DeltaGo, for a chemical process at some temperature T, we can calculate
the equilibrium constant for the process at that temperature using the relationship between
DeltaGo and K.

Rearrangement gives,

In this equation:
R = 8.314 J mol-1 K-1 or 0.008314 kJ mol-1 K-1.
T is the temperature on the Kelvin scale.

Because ΔH° and ΔS° determine the magnitude of ΔG° and because K is a
measure of the ratio of the concentrations of products to the concentrations of reactants,
we should be able to express K in terms of ΔG° and vice versa. "Free Energy", ΔG is equal
to the maximum amount of work a system can perform on its surroundings while
undergoing a spontaneous change.
ΔG=VΔP−SΔT
If a reaction is carried out at constant temperature (ΔT = 0), then equation
simplifies to; ΔG = VΔP.
Under normal conditions, the pressure dependence of free energy is not important
for solids and liquids because of their small molar volumes. For reactions that involve
gases, however, the effect of pressure on free energy is very important.
Assuming ideal gas behaviour, we can replace the V by nRT/P (where n is the
number of moles of gas and R is the ideal gas constant) and express ΔG in terms of the
initial and final pressures (Pi and Pf, respectively):

ΔG° is −32.7 kJ/mol of N2 for the reaction

N2(g)+3H2(g)⇌2NH3(g)

This calculation was for the reaction under standard conditions—that is, with all
gases present at a partial pressure of 1 atm and a temperature of 25°C. Calculate ΔG for
the same reaction under the following nonstandard conditions:

PN2 = 2.00 atm,

PH2 = 7.00 atm,
PNH3 = 0.021 atm,
and T = 100°C.
Does the reaction favour products or reactants?
Given: balanced chemical equation, partial pressure of each species, temperature, and
ΔG°
Asked for: whether products or reactants are favoured.

Strategy:
Using the values given, calculate Q.
Substitute the values of ΔG° and Q to obtain ΔG for the reaction under nonstandard
conditions.

Solution:

The relationship between ΔG° and ΔG are under nonstandard conditions.

Substituting the partial pressures given, we can calculate Q:

Substituting the values of ΔG° and Q.

 Because ΔG < 0 and Q < 1.0, the reaction is spontaneous to the right as
written, so products are favoured over reactants.

Le Chatelier’s Principle
If a dynamic equilibrium is disturbed by changing the conditions, the position
of equilibrium moves to counteract the change.
Using Le Chatelier's Principle with a change of concentration. Suppose you have an
equilibrium established between four substances A, B, C and D.

What would happen if you changed the conditions by increasing the concentration
of A?
According to Le Chatelier, the position of equilibrium will move in such a way
as to counteract the change. That means that the position of equilibrium will move so that
the concentration of A decreases again - by reacting it with B and turning it into C + D.
The position of equilibrium moves to the right.

This is a useful way of converting the maximum possible amount of B into C

and D. You might use it if, for example, B was a relatively expensive material whereas A
was cheap and plentiful.

What would happen if you changed the conditions by decreasing the concentration
of A?
According to Le Chatelier, the position of equilibrium will move so that the
concentration of A increases again. That means that more C and D will react to replace
the A that has been removed. The position of equilibrium moves to the left.
 This is what essentially happens if you remove one of the products of the
reaction as soon as it is formed. If, for example, you removed C as soon as it was formed,
the position of equilibrium would move to the right to replace it. If you kept on removing it,
the equilibrium position would keep on moving rightwards - turning this into a one-way
reaction.

Using Le Chatelier's Principle with a change of pressure

This only applies to reactions involving gases:

What would happen if you changed the conditions by increasing the pressure?
According to Le Chatelier, the position of equilibrium will move in such a way
as to counteract the change. That means that the position of equilibrium will move so that
the pressure is reduced again.

Pressure is caused by gas molecules hitting the sides of their container. The
more molecules you have in the container, the higher the pressure will be. The system
can reduce the pressure by reacting in such a way as to produce fewer molecules.
In this case, there are 3 molecules on the left-hand side of the equation, but only 2 on the
right. By forming more C and D, the system causes the pressure to reduce.
Increasing the pressure on a gas reaction shifts the position of equilibrium towards the
side with fewer molecules.

What would happen if you changed the conditions by decreasing the pressure?
The equilibrium will move in such a way that the pressure increases again. It
can do that by producing more molecules. In this case, the position of equilibrium will move
towards the left-hand side of the reaction.

What happens if there are the same number of molecules on both sides of the
equilibrium reaction?
 In this case, increasing the pressure has no effect whatsoever on the position
of the equilibrium. Because you have the same numbers of molecules on both sides, the
equilibrium can't move in any way that will reduce the pressure again.

Using Le Chatelier's Principle with a change of temperature

For this, you need to know whether heat is given out or absorbed during the
reaction. Assume that our forward reaction is exothermic (heat is evolved):

This shows that 250 kJ is evolved (hence the negative sign) when 1 mole of A
reacts completely with 2 moles of B. For reversible reactions, the value is always given as
if the reaction was one-way in the forward direction. The back reaction (the conversion of
C and D into A and B) would be endothermic by exactly the same amount.

What would happen if you changed the conditions by increasing the temperature?
According to Le Chatelier, the position of equilibrium will move in such a way
as to counteract the change. That means that the position of equilibrium will move so that
the temperature is reduced again.
Suppose the system is in equilibrium at 300°C, and you increase the
temperature to 500°C. How can the reaction counteract the change you have made? How
can it cool itself down again?
To cool down, it needs to absorb the extra heat that you have just put in. In the
case we are looking at, the back reaction absorbs heat. The position of equilibrium
therefore moves to the left. The new equilibrium mixture contains more A and B, and less
C and D.

If you were aiming to make as much C and D as possible, increasing the

temperature on a reversible reaction where the forward reaction is exothermic isn't a good
idea!
What would happen if you changed the conditions by decreasing the temperature?
The equilibrium will move in such a way that the temperature increases again.
Suppose the system is in equilibrium at 500°C and you reduce the temperature to 400°C.
The reaction will tend to heat itself up again to return to the original temperature. It can do
that by favouring the exothermic reaction. The position of equilibrium will move to the right.
More A and B are converted into C and D at the lower temperature.

HIGHLIGHTS/ SUMMARY

 Equilibrium reactions are reversible chemical reactions by using the

"equilibrium arrow" ⇋
 Forward reaction goes to completion: A + B → C+D
 Reverse reaction goes to completion: C + D → A+B
 Reaction at equilibrium:(forward and reverse reactions
 occurring simultaneously) A + B ⇋ C+D
 At equilibrium (dynamic equilibrium): rate of the forward reaction = rate of
the reverse reaction
 At equilibrium the concentration of reactants does not change with time.
 At equilibrium the concentration of products does not change with time.
 Catalysts increase the rate of both the forward and reverse reactions.
 Catalysts DO NOT affect the position of equilibrium.
 Heating (temperature increase) increases the rate of both the forward and
reverse reactions. Heating DOES affect the position of equilibrium.
 Only closed systems can reach equilibrium.
 An open system in which either reactants or products are being removed
cannot reach equilibrium.

 For a system that has reached equilibrium and is then disturbed (perturbed),
Le Chatelier's Principle predicts the position of the equilibrium after the
disturbance (perturbation).
 Disturbances (perturbations) include changes in:
(i) temperature
(ii) concentration
(iv) volume of gases
(v) gas pressure
 Increasing the temperature of a system in dynamic equilibrium favours the
endothermic reaction. The system counteracts the change you have made by
absorbing the extra heat.
 Decreasing the temperature of a system in dynamic equilibrium favours the
exothermic reaction. The system counteracts the change you have made by
producing more heat.
CHAPTER ASSESSMENT
Direction: Read the questions below carefully. Choose the best answer.

1. It is the state in which the rate of the forward reaction is equal the rate of
the backward reaction.
a. Thermodynamics
b. Chemical Equilibrium
c. Thermochemistry
d. Chemical Kinetics
2. What do we call a reaction that is a major class in chemical reactions,
commonly referred as burning?
a. Entropy
b. Enthalpy
c. Combustion
d. None of the above
3. What is the formula of forward reaction rate?
a. k+/k-
b. k- [C]c[D]d
c. k+ [A]a[B]b
d. ΔH – TΔS
4. What is the equilibrium reaction in which all the reactants and products are
in the same phase?
a. Heterogeneous Equilibria
b. Homogenous Equilibria
c. Both a and b
d. None of the above
5. What is the formula for the equilibrium constant?
a. Kc = ΔH – TΔS
b. Kc = k- [C]c[D]d
c. Kc = k+ [A]a[B]b
d. Kc = k+/k-
6. What is the formula of backward reaction rate?
a. Kc = ΔH – TΔS
b. Kc = k- [C]c[D]d
c. Kc = k+ [A]a[B]b
d. Kc = k+/k-
7. What equation shows how to attain a Reaction Quotient?
a. Qc = [N2] [H2]3 / [NH3]2
b. Qc = k- [C]c[D]d
c. Qc = k+ [A]a[B]b
d. Qc = k+/k-
8. What does Le Chatelier’s Principle states?
 a. It states that if a concentration of a substance increases, the
system reacts toward the direction of the reaction that produces it.
b. It states that if the concentration of a substance decreases, the
system reacts toward the direction of the reaction that produces it.
c. It states that when a system is at an equilibrium it is subjected to a
stress that causes the equilibrium to be disturbed, the system will
adjust so as to relieve the stress.
d. None of the above.
9. What are the two types of Equilibrium?
a. Homogenous and Heterozygous Entropy
b. Heterogeneous and Homogenous Equilibria
c. Neither A nor B is correct.
d. A and B is correct.
10. Where can we determine the concentrations of reactants and products at
equilibrium?
a. Equilibrium Constant and Gibbs Free Energy
b. Equilibrium Constant
c. Homozygous and Heterozygous Equilibria
d. Le Chatelier’s Principle
 CHAPTER 11

CHEMICAL EQUILIBRIUM

KEY TO CORRECTION
1. It is the state in which the rate of the forward reaction is equal the rate of
the backward reaction.
a. Thermodynamics
b. Chemical Equilibrium
c. Thermochemistry
d. Chemical Kinetics
2. What do we call a reaction that is a major class in chemical reactions,
commonly referred as burning?
a. Entropy
b. Enthalpy
c. Combustion
d. None of the above
3. What is the formula of forward reaction rate?
a. k+/k-
b. k- [C]c[D]d
c. k+ [A]a[B]b
d. ΔH – TΔS
4. What is the equilibrium reaction in which all the reactants and products are
in the same phase?
a. Heterogeneous Equilibria
b. Homogenous Equilibria
c. Both a and b
d. None of the above
5. What is the formula for the equilibrium constant?
a. Kc = ΔH – TΔS
b. Kc = k- [C]c[D]d
c. Kc = k+ [A]a[B]b
d. Kc = k+/k-
6. What is the formula of backward reaction rate?
a. Kc = ΔH – TΔS
b. Kc = k- [C]c[D]d
c. Kc = k+ [A]a[B]b
d. Kc = k+/k-
7. What equation shows how to attain a Reaction Quotient?
a. Qc = [N2] [H2]3 / [NH3]2
b. Qc = k- [C]c[D]d
c. Qc = k+ [A]a[B]b
 d. Qc = k+/k-

8. What does Le Chatelier’s Principle states?

a. It states that if a concentration of a substance increases, the
system reacts toward the direction of the reaction that produces it.
b. It states that if the concentration of a substance decreases, the
system reacts toward the direction of the reaction that produces it.
c. It states that when a system is at an equilibrium it is subjected
to a stress that causes the equilibrium to be disturbed, the
system will adjust so as to relieve the stress.
d. None of the above.
9. What are the two types of Equilibrium?
a. Homogenous and Heterozygous Entropy
b. Heterogeneous and Homogenous Equilibria
c. Neither A nor B is correct.
d. A and B is correct.
10. Where can we determine the concentrations of reactants and products at
equilibrium?
a. Equilibrium Constant and Gibbs Free Energy
b. Equilibrium Constant
c. Homozygous and Heterozygous Equilibria
d. Le Chatelier’s Principle
REFERENCES

Clark, J. (2013, April). LE CHATELIER'S PRINCIPLE. Retrieved March 9, 2019, from

https://www.chemguide.co.uk/physical/equilibria/lechatelier.html?fbclid=IwAR

1aB_93PXuDiamyEHqPmPXK_2BS8ijLhoEi4rxXMUgjkvlWCcVJh76hlqA

https://www.ausetute.com.au/equilibrium.html

Petrucci, R., Harwood, W., Herring, F., Madura, J., General Chemistry, 9th ed., Pearson,

New Jersey, 2007

Robinson, William R. Nurrenbern, Susan C. “Equilibrium.” Journal of Chemical

Education 2 Feb. 2010 from http://dlib.jce.divched.org/SPT--

Qui...ss=equilibrium

Libretexts. (2019, February 23). Characteristics Of The Equilibrium State. Retrieved from

https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry

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