General Chemistry

Chemical Equilibrium

Dr.rer.nat. Muhammad Saleh, M.Sc

Ternate, 1 November 2021

Content

1.Introduction
2.Equilibrium constant
3.Relationship involving equilibrium constant
4.Equilibrium at homogen and heterogen
system
5.Le Chatelier principle
6.Catalyst and Equilibrium

Muhammad Saleh
1.Intoduction
Chemical Equilibrium—The concept

●
Equilibrium is a state in which there are no observable changes
as time goes by.
●
Chemical equilibrium is achieved when:
a)the rates of the forward and reverse reactions are equal and
b)the concentrations of the reactants and products remain

N2O4 (g) 2NO2 (g)

Muhammad Saleh
 1.Intoduction
Chemical Equilibrium—Law of mass action

Uses stoichiometric coefficients as exponent for each reactant

For reaction: aA + bB cC + dD

[C]c[D]d
Q=
[A]a[B]b
Reaction quotient
– Numerical value of mass action expression
– Equals “Q” at any time, and
– Equals “K” only when reaction is known to be at equilibrium
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
Muhammad Saleh
1.Intoduction
Chemical Equilibrium—Law of mass action

Start with NO2 Start with N2O4 Start with NO2 & N2O4

Muhammad Saleh
 1.Intoduction
Chemical Equilibrium—Law of mass action

[NO2]2
N2O4 (g) 2NO2 (g) K= = 4.63 x 10-3 Law of Mass Action
[N2O4]

Copyright © The McGraw-Hill Companies, Inc.  Permission required for reproduction or display. Muhammad Saleh
 1.Intoduction
Chemical Equilibrium—Learning check

Which of the following is the correct mass action expression (MAE)

for the reaction:
Cu2+(aq) + 4NH3(aq) [Cu(NH3)42+](aq)?

Muhammad Saleh
 1.Intoduction
Chemical Equilibrium—Manipulating the eq.

1. When direction of equation is reversed, new equilibrium constant is

reciprocal of original

A+B C+D

C +D A+B

3 H2(g) + N2(g) 2 NH3(g) at 25°C

2 NH3(g) 3 H2(g) + N2(g) at 25°C

Muhammad Saleh
 1.Intoduction
Chemical Equilibrium—Manipulating the eq.

2. When coefficients in equation are multiplied by a factor, equilibrium

constant is raised to a power equal to that factor.
A+B C+D

3A + 3B 3C + 3D

3 H2(g) + N2(g) 2 NH3(g) at 25°C

9 H2(g) + 3N2(g) 6 NH3(g) at 25°C

Muhammad Saleh
 1.Intoduction
Chemical Equilibrium—Manipulating the eq.

3. When chemical equilibria are added, their equilibrium constants are

multiplied
A+B C+D

C+E F+G

A+B+E D+F+G

Muhammad Saleh
 1.Intoduction
Chemical Equilibrium—Manipulating the eq.

2 NO2(g) NO3(g) + NO(g) [NO][NO 3 ]

K c1 
[NO 2 ] 2
NO3(g) + CO(g) NO2(g) + CO2(g) [NO 2 ][CO 2 ]
K c2 
[NO 3 ][CO]
NO2(g) + CO(g) NO(g) + CO2(g) [NO][CO 2 ]
K c3 
[NO 2 ][CO]

K c1 K c 2 K c 3

Muhammad Saleh
 1.Intoduction
Chemical Equilibrium—Learning check

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

Kc = 500 at a particular temperature.

What would be Kc for following?

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

½ N2(g) + 3/2 H2(g) NH3(g)

Muhammad Saleh
Content

1.Introduction
2.Equilibrium constant
3.Relationship involving equilibrium constant
4.Equilibrium at homogen and heterogen
system
5.Le Chatelier principle
6.Catalyst and Equilibrium

Muhammad Saleh
 2.Equilibrium Constant
Das Wichtige

Equilibrium constant indicates the extent to which a reaction will

proceed, which gives us the idea of where the equilibrium lies.

Muhammad Saleh
 2.Equilibrium Constant
Concentration (Kc) vs Pressure (Kp)

Concentration equilibrium constant, Kc is the constant value equal to

ratio of product concentrations to reactant concentrations raised to
their respective exponents (gas, aq).

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

Note:
●
Changes with temperature (van’t Hoff Equation)
●
Depends on solution concentrations
●
Assumes reactants and products are in solution

Muhammad Saleh
 2.Equilibrium Constant
Concentration (Kc) vs Pressure (Kp)

Pressure equilibrium constant, Kp is the constant value equal to ratio

of partial pressure of reaction. It is used to express the relationship
between product pressures and reactant pressures (gas).

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

Note:
●
only be used with gases since aqueous solutions do not have
partial pressure.
●
Expressed in atmosphere
●
Use partial pressures for each gas in place of concentrations

Muhammad Saleh
 2.Equilibrium Constant
Kc and Kp--- The relations

Start with Ideal Gas Law

PV=nRT

Start with Ideal Gas Law

Substituting P/RT for molar concentration into Kc results in pressure-

based formula

∆n = moles of gas in product – moles of gas in reactant

Muhammad Saleh
 2.Equilibrium Constant
Kc and Kp--- The relations

Start with Ideal Gas Law

PV=nRT

Start with Ideal Gas Law

Muhammad Saleh
2.Equilibrium Constant
Kc and Kp--- The relations

Muhammad Saleh
2.Equilibrium Constant
Kc and Kp--- The relations

Muhammad Saleh
 2.Equilibrium Constant
Kc and Kp--- Learning check

Consider the reaction: 2NO2(g) N2O4(g)

If Kp = 0.480 for the reaction at 25°C, what is value of Kc at same
temperature?
Ans:
n = nproducts – nreactants = 1 – 2 = –1

Muhammad Saleh
 2.Equilibrium Constant
Kc and Kp--- Learning check

Consider the reaction A(g) + 2B(g) 4C(g)

If the Kc for the reaction is 0.99 at 25ºC, what would be the Kp?
Ans:
a) 0.99
b) 2.0
c) 24.
d) 2400
e) None of these

Muhammad Saleh
 2.Equilibrium Constant
Kc and Kp--- Learning check

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.
Ans:

Muhammad Saleh
 2.Equilibrium Constant
Kc and Kp--- Learning check

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?
Ans:

Muhammad Saleh
Content

1.Introduction
2.Equilibrium constant
3.Relationship involving equilibrium constant
4.Equilibrium at homogen and heterogen
system
5.Le Chatelier principle
6.Catalyst and Equilibrium

Muhammad Saleh
 3.Relation inv. K
Equilibrium concentration

Previous examples are the cases in which the equilibrium

concentrations were known. In the lab/world application, we only
know the initial and final concentrations.

Ex:
2SO2(g) + O2(g) 2SO3(g)
1 mol SO2 and 1 mol O2 are placed in a 1 L flask at 1000 K. At
equilibrium 0.925 mol SO3 has formed. Calculate KC for this reaction.
Initial concentrations
Controlled by person running experiment
Changes in concentrations
Controlled by stoichiometry of reaction
Equilibrium concentrations
Equilibrium Initial Change in
Concentration = Concentration –- Concentration Muhammad Saleh
3.Relation inv. K
Equilibrium concentration

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

Initial Conc. (M) 1 1 0
Changes in Conc. (M) -2x -x +2x
Equilibrium Conc. (M) 1-2x 1-x 2x
0.075 0.537 0.925

Solve for x: 2x = 0.925 ; x = 0.925/2 = 0.4625

Kc = 280

Muhammad Saleh
 3.Relation inv. K
Equilibrium concentration – Learning Check

Consider the reaction:

2IBr(g) Br2(g) + I2(g)

6.5 moles of iodine monobromide is placed in a closed 1.0 L

container at 1500C. At equilibrium, the concentration of Br2 is
measured to be 0.50 mol/L

a) what are the concentrations of I2 and Ibr at equilibrium ?

b) what is the value of K for this reaction at the same temperature ?

Muhammad Saleh
3.Relation inv. K
Equilibrium concentration – Learning Check

2IBr(g)) + Br2(g) + I2(g)

Initial Conc. (M) 6.5 0 0
Changes in Conc. (M) -2x +x +x
Equilibrium Conc. (M) 6.5-2x x x
5.5 0.5 0.5
Solve for x: x = [Br2] at eq = 0.5
b) Kc = 8.3 x 10-3

Muhammad Saleh
 3.Relation inv. K
Equilibrium concentration – Learning Check

Determine the eq. Cons. if the Initial & K were known

Ex:
A 0.250 M sample of COBr2 gas decomposes into CO and Br2. If K is
equal to 0.190, what is the concentration of each species as
equilibrium ?

Muhammad Saleh
 3.Relation inv. K
Equilibrium concentration – Learning Check

Determine the eq. Cons. if the Initial & K were known

Ex:
A 0.250 M sample of COBr2 gas decomposes into CO and Br2. If K is
equal to 0.190, what is the concentration of each species as
equilibrium ?

COBr2(g) CO(g) + Br2(g)

Initial Conc. (M) 0.250 0 0
Changes in Conc. (M) -x +x +x
Equilibrium Conc. (M) 0.250-x x x

Find the x using quadratic formula

0.190 = x2/ [0.250 – x] == x2 + 0.190x – 0.0475 =0

Muhammad Saleh
 3.Relation inv. K
Equilibrium concentration – Learning Check

Determine the eq. Cons. if the Initial & K were known (If x both plus)
Ex:
If 2.0 M of H2 gas and 3.0 M of I2 gas are placed in the same vessel,
what Is th concentration of each gas at equilibrium ? K = 25.0

H2(g) + I2(g) 2HI(g)

Initial Conc. (M) 2.0 3,0 0
Changes in Conc. (M) -x -x +2x
Equilibrium Conc. (M) 2.0-x 3.0-x 2x

Find x using

25.0 = 4x2/[6.0-5.0x+x2] == -21x2 + 125x -150 = 0

Muhammad Saleh
 3.Relation inv. K
Equilibrium concentration – Learning Check

Determine the eq. Cons. if the Initial & K were known (The
assumption)
Ex:
N2(g) + O2(g) 2NO(g)

If 0.5 mol of N2 gas and 0.860 mol of O2 gas are placed in the same
vessel with volume of 2.00 L, what Is th concentration of each gas at
equilibrium ? K = 4.1 x 10-4
N2(g) + O2(g) 2NO(g)
Initial Conc. (M) 0.250 0.430 0
Changes in Conc. (M) -x -x +2x
Equilibrium Conc. (M) 0.250-x 0.430-x 2x

Look that the K is so small

Muhammad Saleh
Content

1.Introduction
2.Equilibrium constant
3.Relationship involving equilibrium constant
4.Equilibrium at homogen and heterogen
system
5.Le Chatelier principle
6.Catalyst and Equilibrium

Muhammad Saleh
 4.Eq. At Homo/Heter Sys.
Concepts

Equilibrium constant expressions do not contain concentration terms

for solid or liquid phases of a single component (that is, pure solids
or liquids).

Muhammad Saleh
 4.Eq. At Homo/Heter Sys.
Notes

Homogeneous reaction/equilibrium
●
All reactants and products in same phase
●
Can mix freely

Heterogeneous reaction/equilibrium
●
Reactants and products in different phases
●
Can’t mix freely
●
Solutions are expressed in M
●
Gases are expressed in M
● Governed by K
c

Muhammad Saleh
 4.Eq. At Homo/Heter Sys.
Learning Check

Write equilibrium laws for the following:

Ag+(aq) + Cl–(aq) AgCl(s)

1
Kc 
[Ag ][Cl ]
 

H3PO4(aq) + H2O(ℓ) H3O+(aq) + H2PO4–(aq)

 
[H 3O ][H 2PO4 ]
Kc 
[H 3PO4]

Muhammad Saleh
 4.Eq. At Homo/Heter Sys.
Learning Check

Write equilibrium laws for the following:

Ag+(aq) + Cl–(aq) AgCl(s)

1
Kc 
[Ag ][Cl ]
 

H3PO4(aq) + H2O(ℓ) H3O+(aq) + H2PO4–(aq)

 
[H 3O ][H 2PO4 ]
Kc 
[H 3PO4]

Muhammad Saleh
Content

1.Introduction
2.Equilibrium constant
3.Relationship involving equilibrium constant
4.Equilibrium at homogen and heterogen
system
5.Le Chatelier principle
6.Catalyst and Equilibrium

Muhammad Saleh
 5.Le Chatelier Principle
Introductions

If an external stress is applied to a system at equilibrium,

the system adjusts in such a way that the stress is partially
offset as the system reaches a new equilibrium position.

External sress
●
Concentration
●
Pressure and volume
●
Temperature
●
Catalysts
●
Adding inert gas to system at constant volume

Muhammad Saleh
5.Le Chatelier Principle
Change in concentration

Muhammad Saleh