Think.Pair.Share.: Propose the next clip.

University of San Agustin- Analytical

Chemistry
The Concepts of Chemical
Equilibria and the
Le Chatelier’s Principle
Unit 3

University of San Agustin- Analytical

Chemistry
Topic Outline
• Law of Mass Action
• Writing Chemical Equilibrium Expressions
• Types of Chemical Equilibria
• Equilibrium involving Gases
• Concept of Le Chatelier’s Principle

University of San Agustin- Analytical

Chemistry
Unit Objectives
1. Explain the law of Mass Action
2. Write the chemical equilibriua expression for a given
reversible balanced reaction
3. Distinguish a homogeneous equilibria from a
heterogeneous equilibria
4. Apply the Principle of Law of Mass Action and
mathematical concepts to solve problems in
expressing Kc and Kp
5. Explain the concept of Le Chatelier’s Principle
6. Apply the concepts of Le Cahtelier’s Principle and
mathematical concept to explain factors affceting
equilibria
University of San Agustin- Analytical
Chemistry
 The Law of Mass Action
• The rate of any chemical reaction is
proportional to the product of the masses of
the reacting substances, with each mass
raised to a power equal to the coefficient that
occurs in the chemical equation.
• formulated over the period 1864–79 by the
Norwegian scientists Cato M.
Guldberg and Peter Waage

University of San Agustin- Analytical

Chemistry
2E Chemical equilibrium
Many reactions never result in complete conversion of reactants to
products. They proceed to a state of chemical equilibrium in which
the ratio of concentrations of reactants and products is constant.

Equilibrium-constant expressions are algebraic equations that

describe the concentration relationships among reactants and
products at equilibrium.

The Equilibrium State

The final position of a chemical equilibrium is independent of the
route to the equilibrium state.
This relationship can be altered by applying stressors such as changes
in temperature, in pressure, or in total concentration of a reactant or
a product.

These effects can be predicted qualitatively by the Le Châtelier’s

principle. University of San Agustin- Analytical
Chemistry
This principle states that the position of chemical equilibrium always
shifts in a direction that tends to relieve the effect of an applied
stress.
Ex., an increase in temperature of a system alters the concentration
relationship in the direction that tends to absorb heat.

The mass-action effect is a shift in the position of an equilibrium

caused by adding one of the reactants or products to a system.

Equilibrium is a dynamic process.

At equilibrium, the amounts of reactants and products are constant
because the rates of the forward and reverse processes are exactly
the same.

Chemical thermodynamics is a branch of chemistry that concerns the

flow of heat and energy in chemical reactions. The position of a
chemical equilibrium is related to these energy changes.
University of San Agustin- Analytical
Chemistry
 Characteristics of a system at
equilibrium
• It involves different reactants and products
• The change is reversible and can be represented
by an equation with a double arrow
• It is dynamic, both opposing reactions are in full
operation at equal speed; reversible change occur
cautiously
• The equilibrium system is “closed” in the sense
that no substance can enter or leave the
immediate vicinity of equilibrium.
University of San Agustin- Analytical
Chemistry
 Types of Equilibrium Constants in Analytical Chemistry
TABLE 2-4

University of San Agustin- Analytical

Chemistry
Equilibrium-Constant Expressions

The influence of concentration or pressure on the position of a chemical

equilibrium is described in quantitative terms by means of an equilibrium-
constant expression.

They allow us to predict the direction and completeness of chemical

reactions.

An equilibrium-constant expression yields no information concerning the

rate of a reaction.

Some reactions have highly favorable equilibrium constants but are of little
analytical use because they are slow.

This limitation can often be overcome by the use of a catalyst.

University of San Agustin- Analytical
Chemistry
w moles of W react with x moles of X to form
y moles of Y and z moles of Z. wW  xX  yY  zZ

The equilibrium-constant expression becomes

K
Y  Z 
y z

W w X x
The square-bracketed terms are:
1. molar concentrations if they represent dissolved solutes.
2. partial pressures in atmospheres if they are gas-phase
reactants or products. [Z]z is replaced with pZ (partial pressure
of Z in atmosphere).
No term for Z is included in the equation if this species is a pure
solid, a pure liquid, or the solvent of a dilute solution.

K
Y
y

W  X 
w x
University of San Agustin- Analytical
Chemistry
The constant K in is a temperature-dependent
numerical quantity called the equilibrium constant.
By convention, the concentrations of the products, as
the equation is written, are always placed in the
numerator and the concentrations of the reactants are
always in the denominator.

The exact equilibrium-constant expression takes the

form: y z
aY a Z
K w x
aW a X
where aY, aZ, aW, and aX are the activities of species Y,
Z, W, and X.

University of San Agustin- Analytical

Chemistry
 Two types of Chemical Equilibria
1. Homogeneous equilibria- applies to reactions in which reacting species
are in the same phase.
N2O4(g)  2NO2(g)

The concentrations of reactants and products in gaseous

reactions can also be expressed in terms of their partial pressures.

Note: In general, Kc is not equal to Kp, since the partial pressure of reactants
and products are not equal to their concentrations expressed in mol/L.

2. Heterogeneous equilibria results from a reversible reaction involving

reactants and products that is in different phases.
CaCO3(s)  CaO(s) + CO2(g)

University of San Agustin- Analytical

Chemistry
 Practice: Write the expression for Kc and Kp if
applicable , for the following reversible reactions
at equilibrium.
1. 4 𝑁𝐻3(𝑔) + 7 𝑂2 𝑔 → 4 𝑁𝑂2 𝑔 + 6 𝐻2 𝑂(𝑔)
4 6
4
𝑁𝑂2 𝐻2 𝑂 6 𝑃𝑁𝑂2 𝑃𝐻2𝑂
𝐾𝑐 = 𝐾𝑝 = 4 7
𝑁𝐻3 4 𝑂2 7 𝑃𝑁𝐻3 𝑃𝑂2

2. 2HgO(s)  2Hg(l) + O2(g)

3. HCOOH (aq)  H+(aq) + HCOO-(aq)
4. H2O(g) + C(s)  CO(g) + H2(g)
5. 3O2(g)  2O3(g)
6. 2N2O5(g)  4NO (g) + O2(g)
2 Agustin-
University of San
Analytical Chemistry
Qualitative Problems
• Qualitatively, one may look at how far an equilibrium lies towards
the right or left of the equation. The magnitude of the equilibrium
constant gives one a general idea of whether the equilibrium favors
products or reactants.

• If the reactants are favored: The denominator term of the mass

action expression will be larger than the numerator term, and the
equilibrium constant will less than one. Kc < 1

• If the products are favored: The numerator term will be larger than
the denominator term, and the equilibrium constant will be greater
than one. Kc > 1

Examples : COCl2 (g)  CO(g) + Cl2(g) Keq = 2.2 x 10-10

(reactants are favored)

2NO2(g)  N2O4(g) Keq = 2.15 x 102

(products are favored)
University of San Agustin- Analytical Chemistry
Quantitative Problems
• Lets consider some quantitative problems dealing
with chemical equilibria. By examining the amounts
of reactants and products at equilibrium, one may
numerically see how an equilibrium favors either
reactants or products.
Example : CO(g) + 2H2(g)  CH3OH(g)
(0.0911) (0.0822) (0.00892)

• since the Keq value is >1, the equilibrium favors the

products University of San Agustin- Analytical
Chemistry
 Relationships Involving Equilibrium
Constants
Relationship of Kc to the Balanced Chemical Equation
– When we reverse an equation, we invert the value
of Kc.
– When we multiply the coefficients in a balanced
equation by a common factor, we raise the
equilibrium constant to the corresponding power.
– When we divide the coefficients in a balanced
equation by a common factor, we take the
corresponding root of the equilibrium constant.

University of San Agustin- Analytical

Chemistry
Practice: Calculating the values of K
1. The following equilibrium concentrations were observed for the
Haber process for the synthesis of ammonia at 127oC:
[NH3] = 3.1 x 10-2 M [N2] = 8.5 x 1-0-1 M [H2] = 3.1 x 10-3 M

a) Calculate the value of K at 127oC for this reaction.

b) Calculate the value of the equilibrium constant at 127oC for the

reaction
2NH3(g)  N2(g) + 3H2(g)

c) Calculate the value of the equilibrium constant at 127⁰C for the

reaction given by the equation
½ N2(g) + 3/2 H2(g)  NH3(g)

University of San Agustin- Analytical

Chemistry
 Equilibria Involving Gases: The Equilibrium Constant, Kp
Relationship between Kp and Kc

For the synthesis of ammonia reaction, equilibrium expression can

be written as Kc or Kp.
R = gas constant
= 0.08206
L∙atm/mol∙K
T = Temperature in
Kelvin
∆n = the difference
in the sums of
coefficients of
gaseous products
and reactants

Note: In general, Kp is not equal to Kc except in the special case in which n = 0.

University of San Agustin- Analytical
Chemistry
Practice Calculating the value of Kp
1. 2 SO2(g) + O2(g)  2 SO3(g) Kc = 2.8 x 102 at 1000 K
Calculate Kp.

2. For the reaction 2 NH3(g)  N2(g) + 3 H2(g) at 298 K,

Kc = 2.8 x 10-9
What is the value of Kp for this reaction?

3. At equilibrium in the following reaction at 60oC, the partial

pressures of the gases are found to be PHI = 3.65 x 10-3 atm
and PH2S = 9.96 x 10-1 atm. What is the value of Kp for the
reaction?
I2(s)of
H2S(g) +University 2HI(g)
San Agustin-
Chemistry
Analytical + S(s)
 THE REACTION QUOTIENT, Q: Predicting
the Direction of Net Change
• In general, equilibrium constant help us to predict the direction in which a
reaction mixture will proceed to achieve equilibrium and to calculate the
concentration of reactants and products has been reached.
• The reaction quotient, Q, is obtained by applying the law of mass action
using initial concentrations instead of equilibrium concentrations.
• For example, for the synthesis of ammonia:

• The expression for the reaction quotient is

Subscript zero, 0, indicates

initial concentrations
University of San Agustin- Analytical
Chemistry
 THE REACTION QUOTIENT, Q: Predicting the
Direction of Net Change
• To determine the direction in which the net reaction will proceed to
achieve equilibrium, we compare the value of Qc and Kc.

• Qc > Kc : The ratio of the initial concentrations of products to

reactants is too large. To reach equilibrium, products must be converted to
reactants. The system proceeds from right to left (Consuming products,
form reactants) to reach equilibrium.

• Qc = Kc : The initial concentrations are equilibrium concentrations.

The system is at equilibrium.

• Qc < Kc : The ration of the initial concentrations of products to

reactants is too small. To reach equilibrium, reactants must be converted
to products. The system proceeds from left to right (consuming reactants,
forming products) to reach equilibrium.
University of San Agustin- Analytical
Chemistry
 Practice: Calculating Qc and predicting the
direction of net change
1. For the reaction PCl5(g)  PCl3(g) + Cl2(g) Kc = 0.0454 at
261oC. If a vessel is filled with these gases such that the
initial concentrations are [PCl3] = 0.50 M, [Cl2] = 0.20 M and
[PCl5] = 4.50 M, in which direction will a net change occur?

2. 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
375oC. If the equilibrium constant (Kc) for the reaction
N2(g) + 3H2(g)  2NH3(g)
is 1.2 at this temperature, decide whether the system is at
equilibrium. If it is not, predict which way the net reaction
will proceed.

University of San Agustin- Analytical

Chemistry
 Altering Equilibrium Conditions:
Le Chatelier’s Principle
• If a stress is applied to a system in dynamic
equilibrium, the system changes to relieve the
stress.

• System stresses:
– Concentration of reactants or products
– Temperature
– Pressure

University of San Agustin- Analytical

Chemistry
 Effect of Concentration of Reactants

• Adding reactant shifts the reaction toward the

products. Why?
• Stress: Increasing reactants
• Relief: Decreasing reactants
• Shift: to the right (products)

H2O (l) + CO2 (g) H2CO3 (aq)

University of San Agustin- Analytical
Chemistry
 Effect of Concentration of Products

• Adding products shifts the reaction toward

the reactants. Why?
• Stress: Increasing products
• Relief: Decreasing products
• Shift: to the left (reactants)

H2O (l) + CO2 (g) H2CO3 (aq)

University of San Agustin- Analytical
Chemistry
 Practice
Arsenic can be extracted from its ores by first reacting the ore with oxygen (called
roasting) to form solid As4O6, which is then reduced using carbon:
As4O6(s) + 6C(s)  As4(g) + 6CO(g)
• Predict the direction of the shift of the equilibrium position in response to each of
the following changes in conditions. Chemistry : An Atoms first approach (Zumdahl, et.al.)

A. Addition of carbon monoxide

Towards the left

B. Addition of carbon
NO EEFECT (since C is solid)

C. Removal of tetraarsenic hexoxide

NO EEFECT (since As4O6 is solid)

D. Removal of gaseous arsenic

Towards the right
University of San Agustin- Analytical
Chemistry
 Effect of Temperature
• Increasing the temperature causes the
equilibrium to shift in the direction that
absorbs heat.
Stress: Increase in Temp
• Relief: Decrease in Temp
• Shift: Towards the left (endothermic reaction
is favored)

SO2 (g) + O2 (g) 2SO3 (g) + heat

University of San Agustin- Analytical

Chemistry
 Practice
• Example: For each of the following reactions, predict
the shift in equilibrium position that will occur as the
temperature of the system is decreased.
• N2(g) + O2(g) + heat  2NO(g)

Towards the left

• 2SO2(g) + O2(g)  2SO3(g) + heat

Towards the right University of San Agustin- Analytical

Chemistry
 Effect of Pressure
• Changes in pressure have little effect on the concentrations
of solids or liquids because they are only slightly
compressible.
• Changes in pressure do cause significant changes in
concentration of gases, however.
• Affects gases only.
• For unequal number of moles of reactants and products, if
pressure is increased, the equilibrium will shift to reduce the
number of particles. (towards the fewer number of moles)
• For equal number of moles of reactants and products, no
shift occurs.

PCl3(g) + 3NH3(g) P(NH2)3(g) + 3HCl(g)

4moles 4 moles
University of San Agustin- Analytical
Chemistry
 Practice: Effect of Pressure
2NO2 (g) N2O4 (g)
Stress: increasing the pressure
Relief: decreasing the pressure
Shift: to the right (side of less gaseous molecules)

Predict the shift in equilibrium position that will occur for each of the
following processes when the pressure is reduced.
1. The preparation of liquid phosphorus trichloride by the reaction
P4(s) + 6Cl2(g)  4PCl3(l)

Towards the left (more gas molecules)

2. The preparation of gaseous phosphorus pentachloride according
to the equation
PCl5(g)  PCl3(g) + Cl2(g)
Towards the right (more gas molecules)
University of San Agustin- Analytical
Chemistry
 Addition of a Catalyst
• Adding a catalyst to a system changes the rate of
the reaction, but this cannot shift the equilibrium
in favor of either products or reactants. Because a
catalyst affects the activation energy of both
forward and reverse reactions equally, it changes
both rate constants by the same factor, so their
ration, Kc, does not change.
• In summary, adding a catalyst to a reaction at
equilibrium has no effect; it changes neither Q
nor Kc.
University of San Agustin- Analytical
Chemistry
University of San Agustin- Analytical
Chemistry
 Seatwork
• Predict the shifts (effect) in the equilibrium position for
the reaction N2O4(g)  2NO2(g) Ho = +58 kJ
Change (stress) Shift/ Effect in Eq Position
Addition of N2O4(g)
Addition of NO2(g)
Removal of N2O4(g)
Removal of NO2(g)
Addition of He(g)
Decrease container volume
Increase container volume
Increase temperature
Decrease temperature University of San Agustin- Analytical
Chemistry