Chapter 6

One in five of the worlds people lives on
less than $1(USD) a day!

Poverty is not just a matter of a lack of material wealth
the ability to buy food, say, or basic farming tools.
People do not get access to medicine or healthcare,
so their years of healthy life are diminished.
Every day, one in five of the worlds population some
800 million people go hungry.
Two billion people suffer from chronic malnutrition.
Eighteen million die each year from hungerrelated
diseases.
Around half of the deaths of children under five (about
10 million each year) are associated with malnutrition.
The average Japanese woman can expect to live to
up to 84 years old.
The average Botswanan will reach just 39 years old.
In India, rather than staying at school or receiving training,
children are sent out to work.
There are 44 million child laborers in India.
More than 70 per cent of the worlds population have
never heard a dial tone.
In Africa, only one in four owns a radio, and
one in 40 owns a telephone. Less than 1 per cent of the
total population 800 million has a computer.
The average Americans spends 46 per cent of their time
accessing information.
In 2003, the US spent $396 billion (USD) on its military.
Every hour of every day, the world spends more than
$90 million (USD) on its military.
Every cow in the European Union is subsidized by
$2.50(USD). Thats more than 75 per cent of Africans
to live on.
For the money the EU spends protecting its farmers,
each of the EUs 21 million cow could go
roundtheworld trip once a year.
America spends $10 billion (USD) on pornography
every year the same amount it spends on foreign aid.
Nearly 26 million people voted in the 2001 British
General Election. More than 32 million voted were cast
in the first season of Pop Idol.
In 2003, 15 million Americans had some form of plastic
surgery.
This figure includes cosmetic surgery, like nose reshaping,
breast augmentation and liposuction; reconstructive
surgery, such as scar and tumor removal; and
nonsurgical procedures, like laser hair removal and
cellulite treatment.
Distribution of wealth across the worlds people is unequal.
In 1960, the percapita gross domestic product (GDP) of
the richest twenty countries was eighteen times that of
the poorest twenty.
In 1995, this gap had increased to 37 times.
Today (2004), the worlds richest 1 per cent receive as much
income as the poorest 57 percent.
For less than 1 per cent of
the income of the wealthiest
countries each year, the
worst effects of poverty could
be greatly diminished.
The world today has not
reached its EQUILIBRIUM.
Lets struggle to achieve it for BETTER WORLD.
Source:
50 FACTS THAT SHOULD CHANGE THE WORLD
Jessica Williams, 2004, Icon Books Ltd.
CHEMICAL EQUILIBRIUM
6.1 Dynamic Equilibrium

At the end of the lesson, students should be able to:
i) Explain (a) reversible reaction,
(b)dynamic equilibrium and
(c)law of mass action
ii) State the characteristics of a system in
equilibrium
iii. Explain the change of concentration of reactant
and products based on the curve of
concentration againts time for reversible
reaction. LESSON DURATION: 1 hour
a)NON-REVERSIBLE REACTION
Few chemical reactions proceed in only one

direction:
A + B C + D
Example:
UV
CH4 + Cl2 CH3Cl + HCl
Reactions proceed in only one direction

The reaction proceeds toward the formation
of product
REVERSIBLE REACTION
But, most chemical reactions are reversible,
at least to some extent
A B
reactant product
Forward reaction: reaction proceeds from
left to right
Backward reaction: reaction proceeds from
right to left
Reversible reaction: reactions which take
place in both forward and reverse directions
= indicates reversible reaction

REVERSIBLE REACTION
A B
reactant product
In a reversible reaction, initially the

reaction proceeds toward the formation of
products
As soon as some product molecules
formed, the reverse process begins to
take place
Reactant molecules are formed from
product molecules
REVERSIBLE REACTION
Consider the following reversible reaction:

A B
The graph of the concentration of A and

B against time:
[A] decrease with time
[B]
[B]
[B] increase with time
After time, t1, [A] and [B]
[A] remains unchanged
The system is in the state of
t1
equilibrium
The equilibrium is a
dynamic equilibrium
Means that after t1, the
[B]
reaction did not stop
But, the rate of forward
[A] reaction = rate of reverse
reaction
t1 There is no net change in
[A] and [B]
EQUILIBRIUM
A state in which there are no observable

changes as time goes by.
Two types:
physical equilibrium
chemical equilibrium
PHYSICAL EQUILIBRIUM
Physical change
H2O(l) H2O(g)
Number of H2O molecules

leaving
= Number of H2O molecules
returning to liquid phase
Most chemical reactions are reversible.

N2O4(g) 2NO2(g)
colorless brown
ratefwd = raterev
When we introduce some N2O4(l) into a sealed flask

kept at 100oC, a change occurs immediately.
The liquid vaporizes (bp = 21oC) and the gas begins

to turn pale brown.
The color slowly darkens, but after a few moments,

no further color change can be seen.
b)DYNAMIC EQUILIBRIUM
Reactant and product concentrations stop

changing because the forward and reverse
rates have become equal.
ratefwd = raterev
At equilibrium,
N2O4 molecules decompose
as fast as
NO2 molecules combine
N2O4(g) 2NO2(g)
A: Start
B: Mixture becomes pale brown
N2O4 decompose to reddish brown NO2
C: Mixture reaches final color

reaction reaches equilibrium
D: Concentrations (and color) remain constant
N2O4(g) 2NO2(g)
At equilibrium,
Rate of forward reaction: N2O4(g) 2NO2(g)
= Rate of reverse reaction: 2NO2(g) N2O4(g)
[N2O4(g)] and [NO2(g)] remain constant
But!
[N2O4(g)] [NO2(g)]
c) LAW OF CHEMICAL EQUILIBRIUM
Also known as law of mass action.
At a given temperature, a chemical system

reaches a state in which particular ratio of
reactant and product concentrations has
a constant value.
For a particular system and temperature, the

same equilibrium state is attained regardless
of how the reaction is run.
Cato Maximilian Guldberg (1839 1902). Norwegian chemist and Mathematician.
Peter Waage (1833 1900). Norwegian chemist.
LAW OF CHEMICAL EQUILIBRIUM
Consider this general reaction equation:
aA + bB cC + dD
At equilibrium: [ C ]c [ D ]d = K
[ A ]a [ B ] b
Where:
a, b, c and d: stoichiometric coefficients for the reacting
species A, B, C and D
K = Equilibrium constant, [ ] = concentration
aA + bB cC + dD [C]c [D]d
K =
[A]a [B]b
REACTANTS PRODUCTS
By convention,
substances on the left reactants
substances on the right products
cC + dD aA + bB [A]a [B]b
K =
[C]c [D]d
REACTANTS PRODUCTS
EQUILIBRIUM CONSTANT (K)
N2O4(g) 2NO2(g)
[NO2]2
K=
[N2O4]
aA + bB cC + dD
[C]c [D]d
K =
[A]a [B]b
[C]c [D]d
aA + bB cC + dD K =
[A]a [B]b
Magnitude of K indicates how far a reaction proceeds
toward product at a given temperature.
Large K Equilibrium will:

lie forward (to the right).
favour products.
reaction goes to completion.
2CO(g) + O2(g) 2CO2(g) K = 2.2 x 1022

[C]c [D]d
aA + bB cC + dD K =
[A]a [B]b
Small K Equilibrium will:

lie reverse (to the left).
favour reactants.
almost no reaction.
N2(g) + O2(g) 2NO(g) K = 1 x 1030

[C]c [D]d
aA + bB cC + dD K =
[A]a [B]b
Intermediate K At equilibrium:
significant amounts of both
reactant and product
2BrCl(g) Br2(g) + Cl2(g) K=5

EXERCISE - 1 5.1
Which of the following reactions will tend to

proceed farthest toward completion?
a) H2(g) + Br2(g) 2HBr(g) KC = 7.9 x 1018
b) 2NO(g) N2(g) + O2(g) KC = 2.1 x 1030
c) 2BrCl Br2 + Cl2(in CCl4 solution) KC = 0.145

ii)CHARACTERISTICS OF A SYSTEM IN
EQUILIBRIUM
i. Reactant and product concentrations

are constant over time.
ii. Forward reaction rate = reverse reaction

rate
iii. The reaction quotient (Q) = The

equilibrium constant (K)
Q=K
(Will be discuss later in Topic 6.2)
N2O4(g) 2NO2(g)
equilibrium
equilibrium
equilibrium
Start with NO2 Start with N2O4 Start with NO2 & N2O4
Even though equilibrium is reached in

all cases, the equilibrium concentrations
of NO2 and N2O4 are not the same.
constant
N2O4(g) 2NO2(g)
N2O4(g) 2NO2(g)
[NO2 ]2 [NO2]2
K= = 4.63 x 10-3 The ratio [N O ] are constant
[N2O4] 2 4
K equilibrium constant
END OF
SLIDE SHOW
6.2 Equilibrium Constants (Part I)

(a) Define homogeneous and heterogeneous equilibria.

(b) Deduce and write expressions for equilibrium constants
in terms of concentration, Kc and partial pressure, Kp for
homogeneous and heterogeneous systems.
(c) Derive and use the equation, Kp = Kc (RT)n.
LESSON DURATION: 1 hour

HOMOGENEOUS EQUILIBRIUM
Products and reactants are in the same phase.
N2O4(g) 2NO2(g)
2SO2(g) + O2(g) 2SO3(g)
CH3COOH(aq) CH3COO(aq) + H+(aq)

WRITING KC EXPRESSIONS
aA(g) + bB(g) cC(g) + dD(g)
[C]c [D]d
KC = Subscript C in KC =
[A]a [B]b concentrations of the
reacting species
N2O4(g) 2NO2(g)
[NO2]2
KC =
[N2O4]
CH3COOH(aq) CH3COO(aq) + H+(aq)

[CH3COO] [H+]
KC =
[CH3COOH]
Note: Unit of concentration = M (mol L-1)

WRITING Kp EXPRESSIONS
PCc PDd P = equilibrium partial
KP = pressure of the gas
PAa PBb
N2O4(g) 2NO2(g)
P2
KP = NO2
Note:
P Equilibrium constant
N2O4
N2(g) + 3H2(g) 2NH3(g) expression (KC or KP)
also called
P2 Equilibrium law
KP = NH3
expression
P x P3
N2 H2
Note: Unit of pressure = atm.
WRITING Kp AND Kc EXPRESSIONS
PV = nRT
So
P n
P = n RT or =
V RT V
At constant temperature,
pressure is directly proportional to molar
concentration (n/V).
The equilibrium constant for reaction

involved gases, can be expressed based
on concentrations (KC) and pressures (KP).
The equilibrium constant (KC and KP)
is a dimensionless (no unit) quantity.
PCl3(g) + Cl2(g) PCl5(g)
KC = 1.67 (at 500K)
KP = 4.07 x 102 (at 500K)

KC = 1.67 (at 500K)
KP = 4.07 x 102 (at 500K)
In quoting a value for the KP or KC, you MUST

specify the balanced equation (including the phase
of each reactant/product) and the temperature.
EXERCISE - 1
Write expressions for KC, and KP if applicable,
for the following reversible reactions at
equilibrium:
Note: balance the equations first.
a) HF(aq) H+(aq) + F(aq)
b) NO(g) + O2(g) NO2(g)
c) N2O5(g) NO2(g) + O2(g)
d) C3H8(g) + O2(g) CO2(g) + H2O(g)
e) NH3(g) + O2(g) NO(g) + H2O(g)

f) NO(g) N2O(g) + NO2(g)
EXAMPLE - 1 ANS:
The following equilibrium process has been

studied at 230oC:
2NO(g) + O2(g) 2NO2(g)
In one experiment the concentration of the
reacting species at equilibrium are found to be
[NO] = 0.0542 M, [O2] = 0.127 M, and
[NO2] = 15.5 M. Calculate the equilibrium constant (KC)
of the reaction at this temperature.
[NO2] (15.5)2
Kc = = = 6.44 x 105
[NO]2[O2] (0.0542)2 x 0.127
EXERCISE - 2
Consider the following equilibrium process at
700oC:
2H2(g) + S2(g) 2H2S(g)
Analysis shows that at equilibrium, there are
2.50 mol of H2,1.35 x 105 mol of S2, and
8.70 mol of H2S present in a 12.0L flask.
Calculate the equilibrium constant KC for
the reaction.
ANS:
1.08 x 107
EXERCISE - 3
At a certain temperature, KC = 1.8 x 104 for
the reaction
N2(g) + 3H2(g) 2NH3(g)
If the equilibrium concentrations of N2 and NH3
are 0.015 M and 2.00 M, respectively,
what is the equilibrium concentrations of H2?
ANS:
0.25 M
EXERCISE - 4
In a study of the conversion of methane to other
fuels, a chemical engineer mixes gaseous CH4
and H2O in a 0.32L flask at 1200 K.
At equilibrium, the flask contains 0.26 mol of CO,
0.091 mol of H2, and 0.041 mol of CH4.
What is [H2O] at equilibrium?
KC = 0.26 for the equation
CH4(g) + H2O(g) CO(g) + 3H2(g)
ANS:
0.53 M
EXERCISE - 5
Equilibrium is established at 25oC in the
reaction
N2O4(g) 2NO2(g) KC = 4.61 x 103
If [NO2] = 0.0236 M in a 2.26L flask,
how many grams of N2O4 are also present?
ANS:
25.2 g
EXAMPLE - 2
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
ANS: Kp = 2
PNO 2
2
PNO 2
PO 2 = Kp
2
PNO
PO 2 = 158 x (0.400)2/(0.270)2 = 346.8 atm

EXERCISE - 6
The equilibrium constant KP for the decomposition
of phosphorus pentachloride to phosphorus
trichloride and molecule chlorine
PCl5(g) PCl3(g) + Cl2(g)
is found to be 1.05 at 250oC. If the equilibrium
partial pressure of PCl5 and PCl3 are 0.875 atm and
0.463 atm, respectively, what is the equilibrium
partial pressure of Cl2 at 250oC.
ANS:
1.98 atm
EXERCISE - 7
For the Haber process,
N2(g) + 3H2(g) 2NH3(g)
KP = 1.45 x 105 at 500oC.
In an equilibrium mixture of the three gases at
500oC, the partial pressure of H2 is 0.928 atm
and that of N2 is 0.432 atm.
What is the partial pressure of NH3 in this
equilibrium?
ANS:
2.24 x 103 atm
The value of KC and KP depend on how the
equilibrium equation is written and balanced.
N2O4(g) 2NO2(g) (at 25oC)

[NO2]2
KC = = 4.63 x 103
[N2O4]
2NO2(g) N2O4(g) (at 25oC)

[N2O4]
KC = = 216
[NO2]2
The value of KC and KP depend on how the
equilibrium equation is written and balanced.
N2O4(g) 2NO2(g) (at 25oC)

[NO2]2
KC = = 4.63 x 103
[N2O4]
1
2 N2O4(g) NO2(g) (at 25oC)
[NO2]
KC = = 0.0680
[N2O4]1/2
EXERCISE - 8
For the ammoniaformation reaction,
N2(g) + 3H2(g) 2NH3(g)
KC = 2.4 x 103 at 1000 K. If we change the
coefficients of this equation, what are the values
of KC for the following balanced equations?
1 N (g) + H (g) 2 NH (g)

a) 3 2 2
3 3
1 N (g) + 3 H (g)
b) NH3(g)
2 2 2
2
EXERCISE - 9
At 25oC, KC = 7.0 x 1025 for the reaction:
2SO2(g) + O2(g) 2SO3(g)
What is the value of KC for the reaction:
1
SO3(g) SO2(g) + O2(g)
2
HETEROGENEOUS EQUILIBRIUM
Reactants and products are in different phases.
CaCO3(s) CaO(s) + CO2(g)
[CaO][CO2] [CaCO3] = constant

KC = [CaO] = constant
[CaCO3]
KC = [CO2] KP = PCO 2
The concentration of pure solids, pure liquids

and solvents do not appear in the equilibrium
constant expression.
A pure solid always has the same concentration at
a given temperature same number of moles per liter
of the solid.
Just as it has same density at any given temperature.
Same reason applies to pure liquid.
PCO 2 = KP
PCO 2 does not depend on the amount of CaCO3 or CaO.

EXAMPLE - 3 ANS:
Write equilibrium constant expression for

KC and KP for the formation of nickel
tetracarbonyl, which is used to separate nickel
from other impurities:
Ni(s) + 4CO(g) Ni(CO)4(g)
[Ni(CO)4]
KC = P
[CO]4 KP = Ni(CO)4
P4
CO
EXERCISE - 10
Balance each of the following equations and
write its equilibrium constant expression,
KC and KP:
a) Na2O2(s) + CO2(g) Na2CO3(s) + O2(g)
b) H2O(l) H2O(g)
c) NH4Cl(s) NH3(g) + HCl(g)
d) H2O(l) + SO3(g) H2SO4(aq)
e) KNO3(s) KNO2(s) + O2(g)
f) S8(s) + F2(g) SF6(g)

EXERCISE - 11
Balance each of the following equations and
write its equilibrium constant expression,
KC and KP:
a) NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
b) SnO2(s) + H2(g) Sn(s) + H2O(g)
c) H2SO4(l) + SO3(g) H2S2O7(l)
d) AgCl(s) Ag+(aq) + Cl(aq)
e) CO2(s) CO2(g)
c) N2O5(s) NO2(g) + O2(g)
EXAMPLE - 4 ANS:
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 for the reaction?
KP = P P = 0.265 x 0.265 = 0.0702

NH3H2S
EXERCISE - 12
At equilibrium in the following reaction at 60oC,
the partial pressure of the gases are found to be
PHI = 3.65 x 103 atm and PH S =2
0.996 atm.
What is the value of KP for the reaction?
H2S(g) + I2(s) 2HI(g) + S(s)
EXERCISE - 13
At equilibrium, the pressure of reacting mixture
is 0.105 atm at 350oC.
Calculate KP for this reaction.
RELATION BETWEEN Kp AND Kc
In most cases
KC KP

[C]c [D]d PCc PDd
KC = KP =
[A]a [B]b PAa PBb
KP = KC(RT)n But, how do we derive

this equation?
n = moles of gaseous products = (c + d) (a + b)
moles of gaseous reactants
Derivation of equation: KP = KC(RT)n
Let us consider the following equilibrium in gas phase:
The equilibrium constant KC: The expression for KP:

[C]c [D]d PCc PDd
KC = KP =
[A]a [B]b PAa PBb
Assuming the gases behave as ideal gases: PV = nRT
PA = nA RT PB = nB RT PC = nC RT PD = nD RT
V V V V
= [A]RT = [B]RT = [C]RT = [D]RT
Derivation of equation: KP = KC(RT)n
PA = nA RT PB = nB RT PC = nC RT PD = nD RT
V V V V
= [A]RT = [B]RT = [C]RT = [D]RT
*Notice that, nA/V, nB/V, nC/V and nD/V have units mol L-1 and been
replaced by [A], [B], [C] and [D]
By substituting these relations into the expression of KP:
PCc PDd [C]c [D]d
KP = = x (RT)(c + d)(a + b)
PAa PBb [A]a [B]b
c d = KC(RT)n
= ([C]RT) x ([D]RT )
([A]RT)a x ([B]RTb) n = moles of gaseous products -
moles of gaseous reactants
Relationship between KP and KC can also be
written as KP = KC(0.0821T)n
R = 0.0821 L atm mol-1 K-1
If n = 0: KP = KC(0.0821T)0
KP = KC
Example: H2(g) + Br2(g) 2HBr(g)

EXERCISE - 15
Show how you can get the following equation:
KP = KC(RT)n
Hints:
[C]c [D]d PCc PDd
KC = KP =
[A]a [B]b PAa PBb
PV = nRT
EXAMPLE - 5 ANS:
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)
[COCl2] 0.14
KC = = = 216
[CO][Cl2] 0.012 x 0.054
KP = KC(RT)n
n = 1 2 = 1 R = 0.0821 T = 273 + 74 = 347 K
KP = 216 x (0.0821 x 347)-1 = 7.58
EXERCISE - 15
Determine ngas for each of the following
reactions:
a) 2KClO3(s) 2KCl(s) + 3O2(g)
b) 2PbO(s) + O2(g) 2PbO2(s)
c) I2(s) + 3XeF2(s) 2IF3(s) + 3Xe(g)
d) MgCO3(s) MgO(s) + CO2(g)
e) 2H2(g) + O2(g) 2H2O(l)
f) HNO3(l) + ClF(g) ClONO2(g) + HF(g)
EXERCISE - 16
Calculate KC for the following equilibria:
a) CO(g) + Cl2(g) COCl2(g)
KP = 3.9 x 102 at 1000K
b) S2(g) + C(s) CS2(g)
KP = 28.5 at 500K
c) H2(g) + I2(g) 2HI(g)
KP = 49 at 730K
d) 2SO2(g) + O2(g) 2SO3(g)
KP = 2.5 X 1010 at 500K
EXERCISE - 17
Calculate KP for the following equilibria:
a) N2O4(g) 2NO2(g)
KC = 6.1 x 103 at 298K
b) N2(g) + 3H2(g) 2NH3(g)
KC = 2.4 X 103 at 1000K
c) H2(g) + CO2(g) H2O(g) + CO(g)
KC = 0.77 at 1020K
d) 3O2(g) 2O3(g)
KC = 1.8 X 1056 at 570K
EXERCISE - 18
Nitric oxide, oxygen, and nitrogen react by the
following equation:
2NO(g) N2(g) + O2(g)
KC = 2.3 x 1030 at 298K.
In the atmosphere, PO = 0.209 atm and
2
PN 2 = 0.781 atm.
What is the partial pressure of NO in the
air we breath?
EXERCISE - 19
For which of the following reactions does
KP = KC ?
a) 2H2(g) + C2H2(g) C2H6(g)
b) N2(g) + O2(g) 2NO(g)
c) 2NO(g) + O2(g) 2NO2(g)
END OF
SLIDE SHOW
6.2 Equilibrium Constants (Part II)

(a) Calculate Kc, Kp or the quantities of species present at

equilibrium.
(b) Define and determine the degree of dissociation, .
LESSON DURATION: 2 hours

EQUILIBRIUM PROBLEMS
Two types:
Equilibrium quantities ( concentrations ,

partial pressure ) are given
Solve for KC or KP
Initial quantities ( initial concentrations ,

initial partial pressure ) and KP or KC are
given
Solve for equilibrium quantities

( concentrations , partial pressure )
USING A REACTION (ICE) TABLE
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.
EXAMPLE - 1
At a certain temperature, a mixture of H2 and I2
was prepared by placing 0.200 mol of H2 and
0.200 mol of I2 into a 2.00 L flask. After a period of
time the equilibrium
H2(g) + I2(g) 2HI(g)
was established.
At equilibrium, the concentration of I2
concentration had dropped to 0.020 M.
What is the value of KC for this reaction
at this temperature?
EXAMPLE - 1 ANS:
H2(g) + I2(g) 2HI(g)

Initial (M) 0.200 mol 0.200 mol 0.000
2.00 L 2.00 L
= 0.100 = 0.100
Change (M) x x + 2x
Equilibrium (M) 0.100 x 0.100 x 0.000 + 2x
= 0.020 = 2x
So, x = 0.100 0.020
= 0.080
[I2] = 0.020 M
[HI] = 2x0.080 M
[H2] = (0.100 0.080) M
= 0.160 M
= 0.020 M
EXAMPLE - 1 ANS:
H2(g) + I2(g) HI(g)
[H2] = 0.020 M [I2] = 0.020 M [I2] = 0.160 M
[HI]2
KC =
[H2] [I2]
(0.160)2
=
0.020 x 0.020
= 64.0
EXAMPLE - 2
The atmospheric oxidation of nitric oxide,
2NO(g) + O2(g) 2NO2(g)
was studied at 184oC with pressure of 1.000 atm of
NO and 1.000 atm of O2.
At equilibrium, PO = 0.506 atm.
2
Calculate KP.
EXAMPLE - 2 ANS:
2NO(g) + O2(g) 2NO2(g)
Initial (atm) 1.000 1.000 0.000
Change (atm) 2x x + 2x
Equilibrium (atm) 1.000 2x 1.000 x 0.000 + 2x
= 0.506 = 2x
So, x = 1.000 0.506
= 0.494
PNO = (1.000 2x0.494) atm PNO = 2x0.494 atm

2
= 0.012 atm = 0.988 atm
PO = 0.506 atm
2
EXAMPLE - 2 ANS:
2NO(g) + O2(g) 2NO2(g)
PNO = 0.012 atm PO = 0.506 atm PNO = 0.988 atm

2 2
2
PNO 2
Kp = 2
PNO PO
2
(0.988)2
=
(0.012)2 x 0.506
= 1.34 x 104
EXAMPLE - 3
At 1280oC the equilibrium constant (Kc) for the
reaction
Br2(g) 2Br(g)
is 1.1 x 103. If the initial concentrations are [Br2] =
0.063 M and [Br] = 0.012 M, calculate the
concentrations of these species at equilibrium.
ANS: 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
EXAMPLE - 8 ANS:
Br2(g) 2Br(g)
Initial (M) 0.063 0.012
Change (M) x + 2x
[Br]2 (0.012 + 2x)2

Kc = Kc = = 1.1 x 103
[Br2] 0.063 x
Solve for x
EXAMPLE - 3 ANS:
Br2(g) 2Br(g)
Initial (M) 0.063 0.012
Change (M) x + 2x
(0.012 + 2x)2 given

Kc = = 1.1 x 103
0.063 x
4x2 + 0.048x + 0.000144 = 0.0000693 0.0011x
4x2 + 0.0491x + 0.0000747 = 0
-b b2 4ac
ax2 + bx + c =0 x=
2a
x = 0.0105 x = 0.00178
EXAMPLE - 3 ANS:
Determine chemically meaningful x value

Br2(g) 2Br(g)
Initial (M) 0.063 0.012
Change (M) x + 2x
(x = 0.0105) = 0.0705 = 0.009
(x = 0.00178) = 0.0648 = 0.00844 correct

Note: Only one x value makes sense chemically!
At equilibrium, [Br] = 0.00844 M
[Br2] = 0.0648 M
EXERCISE - 1
At particular temperature, suppose that the
initial temperatures of H2, I2, and HI are
0.00623 M, 0.00414 M and 0.0224 M.
H2(g) + I2(g) 2HI(g)
Calculate the concentrations of these species
([H2], [I2], [HI]) at equilibrium.
ANS:
[H2] = 0.00467 M
[I2] = 0.00258 M
[HI] = 0.0255 M
EXERCISE - 2
At 1280oC the equilibrium constant (KC) for
the reaction
Br2(g) 2Br(g)
is 1.1 x 103. If the initial concentrations are
[Br2] = 6.3 x 102 M and [Br] = 1.2 x 102 M.
Calculate the concentrations of these species
at equilibrium.
ANS:
[Br2] = 0.065 M
[Br] = 8.4 x 103 M
EXERCISE - 3
Consider the following equilibrium process at
686oC:
CO2(g) + H2(g) CO(g) + H2O(g)
The equilibrium concentrations of the reacting

species are [CO] = 0.050 M, [H2] = 0.045 M, ANS:
[CO2] = 0.086 M, and [H2O] = 0.040 M. a) KC = 0.52
o
b) [CO2] = 0.48 M
a) Calculate KC for the reaction at 686 C.
[H2] = 0.020 M
b) If we add CO2 to increase its concentration [CO] = 0.075 M
to 0.50 M, what will be the concentrations of [H2O] = 0.065 M
all gases be when equilibrium is
reestablished?
EXERCISE - 4
In a particular experiment, it was found that
when O2(g) and CO(g) were mixed and reacted
according to the equation
2CO(g) + O2(g) 2CO2(g)
The O2 concentration decreased by 0.030 M
when the reaction reached equilibrium.
How had the concentrations of CO and CO2
changed?
ANS:
[CO] decreased by 0.060 M
[CO2] increased by 0.060 M
EXERCISE - 5
The reaction
CO(g) + H2O(g) CO2(g) + H2(g)
has KC = 4.06 at 500oC. If 0.100 mol of CO and
0.100 mol of H2O(g) are placed in a 1.00 liter
reaction vessel at this temperature, what are the
concentration of the reactants and products
when the system reaches equilibrium?
ANS:
[CO] = 0.033 M
[H2O] = 0.033 M
[CO2] = 0.0668 M
[H2] = 0.0668 M
EQULIBRIUM CALCULATIONS
WHEN KC IS VERY SMALL
The concentration change (x) can often be
neglected.
[A]initial x = [A]equilibrium [A]initial
Note: You must check that the assumption is

justified or not.
x
x 100 < 5% Assumption is OK
CHECK: [A]initial
5% rule
x Assumption is NOT OK
x 100 > 5%
[A]initial Use quadratic formula
EXAMPLE - 4 ANS:
Phosgene is a potent chemical warfare agent that is

now outlawed by international agreement. It
decomposes by the reaction
COCl2(g) CO(g) + Cl2(g)
KC = 8.3 x 104 (at 360oC)
Calculate [CO], [Cl2], and [COCl2], when the
following amounts of phosgene decompose
and reach equilibrium in a 10L flask:
a) 5.000 mol of COCl2
b) 0.100 mol of COCl2

EXAMPLE - 4 ANS:
a) COCl2(g) CO(g) + Cl2(g)
Initial (M) 5.000 mol 0.000 0.000

10.0 L
= 0.500
Change (M) x +x +x
Equilibrium (M) 0.500 x x x
[CO][Cl2] x2
KC = [COCl ] KC = = 8.3 x 104
2 (0.500 x)
Solve for x
EXAMPLE - 4 ANS:
[CO][Cl2]
KC = [COCl ] x2
2 KC = = 8.3 x 104
(0.500 x)
Solve for x
KC is very small
Assume x very small, 0.500 x 0.500
x2 Checking the assumption:

KC = = 8.3 x 104
0.500
2.0 x 102
x 100 = 4 % (< 5%)
x2 = 8.3 x 104 x 0.500
0.500
x = 2.0 x 102 OK!
EXAMPLE - 4 ANS:
COCl2(g) CO(g) + Cl2(g)
Initial (M) = 0.500 0.000 0.000

Change (M) x +x +x
( x = 2.0 x 102 )
[CO] = 2.0 x 102 M [Cl2] = 2.0 x 102 M
[COCl2] = (0.500 2.0 x 102) M

= 0.480 M
EXAMPLE - 4 ANS:
b) COCl2(g) CO(g) + Cl2(g)
Initial (M) 0.100 mol 0.000 0.000

10.0 L
= 0.010
Change (M) x +x +x
[CO][Cl2] x2
KC = [COCl ] KC = = 8.3 x 104
2 (0.010 x)
Solve for x
EXAMPLE - 4 ANS:
[CO][Cl2]
KC = [COCl ] x2
2 KC = = 8.3 x 104
(0.010 x)
Solve for x
Kc is very small
Assume x very small, 0.010 x 0.010
x2 Checking the assumption:

KC = = 8.3 x 104
0.010
2.9 x 103
x 100 = 29 % (> 5%)
x2 = 8.3 x 104 x 0.010
0.010
x = 2.9 x 103 NOT OK!
EXAMPLE - 4 ANS:
[CO][Cl2]
KC = [COCl ] x2
2 KC = = 8.3 x 104
(0.010 x)
Solve for x using quadratic formula
x2 + (8.3 x 104)x 8.3 x 106 = 0 Do it yourself
x = 2.5 x 103 (the only meaningful value of x)
[CO] = 2.5 x 103 M [Cl2] = 2.5 x 103 M
[COCl2] = (0.010 2.5 x 103) M

= 7.5 x 103 M
DEGREE OF DISSOCIATION,
Dissociation reaction: a molecule is broken down into

smaller molecules, atoms or ions
EXAMPL PCl5 (g) PCl3 (g) + Cl2 (g)

E:
Fraction or the percentage of molecules that dissociate
is called degree of dissociation,
= 1 or 100% if complete dissociation occurs
If incomplete = [ ]changes
X 100%
dissociation occurs: [ ]initial
THERMAL DISSOCIATION
A reversible reaction brought about by the

application of heat
When cool, the products bond again to give the
original compound
Example: PCl5, N2O4 and NH4Cl
PCl5 (g) PCl3 (g) + Cl2 (g)
N2O4(g) 2NO2(g)
NH4Cl(g) NH3 (g) + HCl (g)

EXAMPLE 5
The concentration of H+ ion measured for HCOOH
0.5 M is 8.9 x 10-3 M. what is the degree of
dissociation of the compound?
Answer:
HCOOH(aq) H+(aq) + HCOO-
Initial [ ] 0.5 0 0
Changes -8.9 x 10-3 +8.9 x 10-3 +8.9 x 10-3
Eq [ ] 0.4911 8.9 x 10-3 8.9 x 10-3

EXAMPLE 5 - ANSWER
= [ ] changes
[ ] initial
= 8.9 x 10-3
0.5
= 0.02
EXAMPLE - 6
The degree of dissociation of dinitrogen

tetroxide at 250 C and 1 atm is 0.15. Calculate
the degree of dissociation at 250 C and 5 atm.
ANS: EXAMPLE - 6
According to Daltons law of partial pressure:
Partial pressure of NO2 = 0.3/1.15 x 1atm = 0.261 atm
Partial pressure of N2O4 = 0.85/1.15 x 1atm = 0.739 atm
PNO22
KP =
PN2O4
0.2612
KP =
0.739
= 9.21 x 10-2 atm
ANS: EXAMPLE - 11
N2O4(g) 2NO2(g)
Initial (mol) 1 0
Changes -0.15 +0.15
Equilibrium 1-0.15 = 0.85 2(0.15) =

(mol) 0.30
Total number of moles after dissociation

= 0.85 + 0.30
= 1.15 mol
ANS:
EXAMPLE - 6
Let the degree of dissociation, at 5 atm = x
N2O4(g) 2NO2(g)
Initial (mol) 1 0
Changes -x +x
Equilibrium 1- x 2x
(mol)
ANS: EXAMPLE - 6
2x
PNO2 = (5 atm)
1 x + 2x
1x
PN2O4 = (5 atm)
1 x + 2x
( 2x / 1 + x )2 (52) = 9.21 X 10-2

KP =
( 1 x / 1 + x ) (5) Only 6.8% of dinitrogen
x = 0.068 tetroxide dissociates at 250 C
and 5 atm
EXERCISE - 6 6.2
At a pressure of 4.4 x 105 Pa and a temperature of 150

C, phosphorus pentachloride is 25% dissociated.
Calculate the partial pressure
equilibrium constant for this reaction.
ANS:
Kp = 2.9 x 104 Pa
END OF
SLIDE SHOW
6.2 Equilibrium Constants (Part III)

At the end of the lesson, students should be able
to:
Deduce the expression for reaction quotient, Q and

predict the direction of net reaction by comparing
the values of Q and Keq.
LESSON DURATION: 1 hour

REACTION QUOTIENT (Q)
Calculated by substituting the initial
concentrations (or pressures) of the reactants
and products into KC or KP expression.
[C]c [D]d [A], [B], [C], [D] :

KC = equilibrium
[A]a [B]b
concentrations
[C]c [D]d [A], [B], [C], [D] :

QC = any (initial)
[A]a [B]b
concentrations
COMPARING Q AND K
Suppose you know the value of KC at any given

temperature of the reaction.
How do you know if the reaction has reached

equilibrium?
If it hasnt, how do you know in which direction it

is progressing to reach equilibrium?
Compare the value of KC and QC.

By comparing the value of Q with K, it is possible to
decide the direction of the
system in order to achieve equilibrium.
Q>K The ratio of initial concentration of products to

reactants is too large. To reach equilibrium,
products must be converted to reactants. The
system proceeds from right to left.
Q=K The initial concentrations are equilibrium
concentration. The system is already at
equilibrium.
Q<K The ratio of 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.
COMPARING Q AND K
aA(g) + bB(g) cC(g) + dD(g) [C]c [D]d

Q=
[A]a [B]b
Q < K
Denominator (reactants) is large relative to
numerator (products)
To reach equilibrium, Q = K:
the products must increase, reactants decrease.
If Q < K, reactants products
The reaction will progress to the right (more

product forms) until equilibrium is reached.
COMPARING Q AND K

Q=
[A]a [B]b
Q > K
Denominator (reactants) is small relative to

numerator (products)
To reach equilibrium, Q = K:
the products must decrease, reactants increase.
If Q > K, reactants products
The reaction will progress to the left (more

reactant forms) until equilibrium is reached.
COMPARING Q AND K

Q=
[A]a [B]b
Q = K
When the reactant and product concentrations

(or pressures) has attained their equilibrium
values.
If Q = K, reactants products
No further net change.

Q < K Q = K Q > K
Before equilibrium is reached, the concentration are
changing continuously, so Q K.
N2O4(g) 2NO2(g)
Once equilibrium is reached and any time thereafter,

Q = K.
Example 10 : EXAMPLE - 1
At 375C, the initial concentrations of N2, H2 and NH3
are 0.0711 M , 9.17 x 10-3 M and 1.83x10-4 M
respectively.
If the equilibrium constant (Kc) for the reaction is 1.2

at this temperature, decide whether the system is at
equilibrium. If it is not, predict which way will the
reaction proceed.
3H2(g) + N2(g) 2NH3(g)

ANS:
EXAMPLE - 1
Qc = [ NH3 ]2
[ N2 ][ H2 ]3
= ( 1.83 x 10-4)2
(0.0711)(9.17 x 10-3)3
= 0.611 M-2
Qc < Kc, the system is not at equilibrium
The net result will be an increase in the

concentration of NH3 and a decrease in the
concentrations of N2 and H2
The net reaction will proceed from left to right

until equilibrium is reached.
EXAMPLE - 2
KC for the formation of nitrosyl chloride, an
orangeyellow compound, from nitric oxide
and molecular chlorine
2NO(g) + Cl2(g) 2NOCl(g)
is 6.5 x 104 at 35oC. In certain experiment,
2.0 x 102 mole of NO, 8.3 x 103 mole of Cl2,
and 6.8 moles of NOCl are mixed in a 2.0L
flask.
In which direction will the system proceed to
reach equilibrium?
ANS:
EXAMPLE - 2
KC = 6.5 x 104
[NOCl]2
QC =
[NO]2 [Cl2]
Initial concentrations: 2.0 x 102 mol

[NO] =
2.0 L
6.8 mol = 0.01 M
[NOCl2] =
2.0 L
8.3 x 103 mol
[Cl2] =
= 3.4 M 2.0 L
= 0.0042 M
ANS:
EXAMPLE - 2
KC = 6.5 x 104 Initial concentrations:
[NOCl2]= 3.4 M
[NOCl]2
QC = [NO] = 0.01 M
[NO]2 [Cl2]
[Cl2] = 0.0042 M
3.42
=
0.012 x 0.0042 Numerator (products)
= 2.75 x 107 is larger than
QC > KC denominator (reactants)
(2.75 x 107) (6.5 x 104)
The reaction is not at equilibrium and
will proceed to the left until QC = KC.
Summary of
the steps
involved in
solving
equilibrium
problems
EXERCISE - 1
State three criteria that characterize a chemical
system that characterize a chemical system at
equilibrium.
EXERCISE - 2
State the reaction N2O4(g) 2NO2(g),
KC = 0.21 at 100oC. At a point during the reaction,
[N2O4] = 0.12 M and [NO2] = 0.55 M.
Is the reaction at equilibrium?
If not, in which direction is it progressing?
EXERCISE - 3
At the start of a reaction, there are 0.249 mol N2,
3.21 x 102 mol H2, and 6.42 x 104 mol NH3
in a 3.50L reaction vessel at 375oC.
If KC for the reaction
N2(g) + 3H2(g) 2NH3(g)
is 1.2 at this temperature, decide whether the
system is at equilibrium.
If not, predict which way the net reaction will
proceed. ANS:
QC < KC
The reaction is not at equilibrium.
It will proceed to the right until QC = KC.
EXERCISE - 4
For the synthesis of ammonia
N2(g) + 3H2(g) 2NH3(g)
KC at 375oC is 1.2. Starting with [H2] = 0.76 M,
[N2] = 0.60 M, [NH3] = 0.48 M, which gases will
increased in concentration and which will have
decreased in concentration when the mixture
comes to equilibrium?
ANS:
[NH3] will increase.
[N2] and [H2] will decrease.
EXERCISE - 5
At 425oC, KP = 4.18 x 109 for the reaction
2HBr(g) H2(g) + Br2(g)
In one experiment, 0.20 atm of HBr(g), 0.010 atm
of H2(g), and 0.010 atm of Br2(g) are introduced
into a container.
Is the system at equilibrium?
If not, in which direction will it proceed?
ANS:
QP > KP
It will proceed to the left until QC = KC.
EXERCISE - 6
At 100oC, KP = 60.6 for the reaction
2NOBr(g) 2NO(g) + Br2(g)
In a given temperature, 0.10 atm of each
component is placed in a container.
Is the reaction at equilibrium?
If not, in which direction will it proceed?
ANS:
QP < KP
It will proceed to the right until QC = KC.
END OF
SLIDE SHOW
6.3 Le Chateliers Principle

a) State Le Chateliers principle
b) Explain the effect of the following factors on a system at
equilibrium by using Le Chateliers principle:
i. Concentration of reacting species

ii. Pressure and volume (include the addition of
inert gas at constant pressure and at constant
volume)
iii. Temperature
LESSON DURATION: 1
iv. catalyst hour
LE CHTELIERS PRINCIPLE
When a chemical system is disturbed, it reattains

equilibrium by undergoing a net reaction that
reduces the effect of the disturbance.
Three common disturbances:
Change in concentration
Change in pressure
(caused by change in volume)
Change in temperature
net reaction = shift in the equilibrium position of
the system to either right or left
Henry Louis Le Chtelier (1850 1936). French chemist.
LE CHTELIERS PRINCIPLE
N2(g) + 3H2(g) 2NH3(g) a chemical system
Add NH3
Original equilibrium: Q=K
Disturbance: Add NH3

[NH3] increase
QK
Reduce Disturbance: reduce increase of [NH3]
net reaction proceeds to the left

New equilibrium: Q=K
Original New
equilibrium equilibrium
The disturbance (addition of

NH3) is reduced but
not eliminated.
The Effect of Added Cl2 on PCl3Cl2PCl5 System
0.163 0.163 0.637
Original New initial New

equilibrium (just after Cl2 added) equilibrium
[PCl5] 0.600 M 0.600 M 0.637 M

[Cl2] 0.125 M 0.200 M 0.163 M
[PCl3] 0.200 M 0.200 M 0.163 M
CHANGES IN CONCENTRATION
If the concentration increases, the system

reacts to consume some of it.
PCl3(g) + Cl2(g) PCl5(g) [PCl5]

QC =
[PCl3][Cl2]
add Cl2
Qc < KC (not at equilibrium)
System will reduce the disturbance (increase of [Cl2]) by:

proceeding to the right
Consuming some additional Cl2
[PCl5] increase
[PCl3] decrease
[PCl5] 0.600 M 0.600 M 0.637 M

[Cl2] 0.125 M 0.200 M 0.163 M
[PCl3] 0.200 M 0.200 M 0.163 M
At the new equilibrium: PCl3(g) + Cl2(g) PCl5(g)

[PCl5] is higher than its original concentration.
[Cl2] is higher than its original concentration but lower

than the concentration just after the Cl2 added
(disturbance is reduced but not eliminated).
[PCl3] is lower than its original concentration because

some reacted with the added Cl2.
[PCl5] 0.600 M 0.600 M 0.637 M

[Cl2] 0.125 M 0.200 M 0.163 M
[PCl3] 0.200 M 0.200 M 0.163 M

KC =
[PCl3][Cl2]
At the original equilibrium:
0.600
KC = = 24.0 At a given temperature,
(0.200)(0.125)
KC does not change with
At the new equilibrium: a change in concentration.
0.637
KC = = 24.0
(0.163)(0.163)
CHANGES IN CONCENTRATION
If the concentration decreases, the system
reacts to produce some of it.
remove PCl3
QC =
[PCl3][Cl2]
Qc > KC (not at equilibrium)

System will reduce the disturbance (decrease of [PCl3]):
proceeding to the left
[PCl3] and [Cl2] increase
[PCl5] decrease
EXERCISE - 1
To improve air quality and obtain a useful product,
sulphur is often removed from coal and natural
gas by treating the fuel contaminant hydrogen
sulphide with O2:
2H2S(g) + O2(g) 2S(s) + H2O(g)
What happen to
a) [H2O] if O2 is added?
b) [H2S] if O2 is added?
SULPHUR
c) [O2] if H2S is removed?
d) [H2S] if sulfur is added?
CHANGES IN PRESSURE (VOLUME)
Only involve systems with gaseous components.
Liquids and solids are nearly incompressible.
Pressure changes can occur in 3 ways:
Changing concentration of a gaseous

component.
Adding inert gas.
Changing the volume of the

reaction vessel. a cylinderpiston
assembly

2 mol gas 1 mol gas
Disturbance: volume decrease
gas pressure immediately increases.
Qc KC (not at equilibrium)
System will reduce the disturbance
Reduce number of gas molecules
proceeding to the right
[PCl3] and [Cl2] decrease
[PCl5] increase

2 mol gas 1 mol gas
Disturbance: volume increase
gas pressure immediately decreases.
Qc KC (not at equilibrium)
Increase number of gas molecules
proceeding to the left
[PCl5] decrease
Changes Shifts in the Equilibrium
Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas

EXERCISE - 2
What effect does an increase in pressure have on
each of the following systems at equilibrium?
The temperature is kept constant and in each
case, the reactants are in a cylinder fitted with
a movable piston.
a) A(s) 2B(s)
b) 2A(l) B(l)
c) A(s) B(g)
d) A(g) B(g)
e) A(g) 2B(g)
EXERCISE - 3
Predict the effect of increasing the container
volume on the amounts of each reactant and
product in the following:
a) F2(g) 2F(g)
b) 2CH4(g) C2H2(g) + 3H2(g)
c) CH3OH(l) CH3OH(g)
d) CH4(g) + NH3(g) HCN(g) + 3H2(g)
EXERCISE - 4
Predict the effect of decreasing the container
volume on the amounts of each reactant and
product in the following:
a) H2(g) + Cl2(g) 2HCl(g)
b) 2H2(g) + O2(g) 2H2O(l)
c) C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l)
d) 4NH3(g) + 3O2(g) 2N2(g) + 6H2O(g)
EXERCISE - 5
Consider the following equilibrium systems:
a) 2PbS(s) + 3O2(g) 2PbO(s) + 2SO2(g)
b) PCl5(g) PCl3(g) + Cl2(g)
c) H2(g) + CO2(g) H2O(g) + CO(g)
d) 2NOCl(g) 2NO(g) + Cl2(g)
Predict the direction of the net reaction in each

case as a result of increasing the pressure
(decreasing volume) on the system at
constant temperature.
EXERCISE - 6
How would you change the volume of each of
the following reaction to increase the yield of
the products?
a) CaCO3(s) CaO(s) + CO2(g)
b) S(s) + 3F2(g) SF6(g)
c) Cl2(g) + I2(g) 2ICl(g)
EXERCISE - 7
How would you change the pressure (via a
volume change) the following reaction to
decrease the yield of the products?
a) 2SO2(g) + O2(g) 2SO3g)
b) 4NH3(g) + 3O2(g) 4NO(g) + 6H2O(g)
c) CaC2O4(g) CaCO3(s) + CO(g)
EXERCISE - 8
How would you adjust the volume of the reaction
vessel in order to maximize product yield in the
following reactions?
a) Fe3O4(s) + 4H2(g) 3Fe(s) + 4H2O(g)
b) 2C(s) + O2(g) 2CO(g)
c) Na2O2(s) 2Na(l) + O2(g)
d) C2H2(g) + 2H2(g) C2H6(g)
ADDITION OF INERT GAS
The total pressure of an equilibrium system can be

changed without changing its volume by adding
an inert gas.
However, adding an inert gas has no effect on the
equilibrium position
The effect of the addition of an inert gas to the
equilibrium system can be studied based on these
two conditions:
I. At constant pressure
II. At constant volume
THE EFFECT OF THE ADDITION OF
INERT GAS ON EQUILIBRIUM
i) At constant pressure:
* The partial pressures for the gases in the system

are lowered
The net effect is as though the gases at
* equilibrium are subjected to a lower total
pressure
According to Le Chateliers principle, addition
* of a noble gas favours the direction that
increases the number of moles of gas
AT CONSTANT PRESSURE
2 mol gas Add noble gas 1 mol gas
Disturbance: addition of inert gas
Total gas pressure decreases.

By increasing the number of gas molecules
proceeding to the left (less products will be produced)
[PCl5] decrease
Equilibrium favours the reactants
2H2O(g) 2H2(g) + O2(g)
2 mol gas Add noble gas 3 mol gas
Total gas pressure decreases.

By increasing the number of gas molecules
proceeding to the right (more products produced)
[H2] and [O2] increase
[H2O] decrease
Equilibrium favours the products
H2(g) + I2(g) 2HI(g)
2 mol gas
2 mol gas Add noble gas
The equilibrium position is not affected
Number of moles of reactants and products

are the same
THE EFFECT OF A NOBLE GAS
ON EQUILIBRIUM
ii) At constant volume:

The total number of gaseous molecules
increases
The total pressure of the equilibrium system
increases
However, the partial pressures of each of
the gases in the equilibrium system remains
unchanged
From Daltons law:
PA = partial pressure of any
PA = nA (RT/V) gas, A
Adding inert gas at constant volume does not
change any of the quantities on the right side of
the above equation
So, PA remains constant
Therefore, addition of inert gas at constant
volume has no effect on the equilibrium position
and the composition of the equilibrium mixture
CHANGES IN TEMPERATURE
Only temperature changes can alter K.
PCl3(g) + Cl2(g) PCl5(g) H = 111 kJ
forward reaction is exothermic (heat

released)
PCl3(g) + Cl2(g) PCl5(g) + heat H = 111 kJ

Exothermic heat released
PCl5(g) + heat PCl3(g) + Cl2(g) H = +111 kJ
Endothermic heat absorbed

Exothermic heat released heat released
PCl3(g) + Cl2(g) PCl5(g) + heat H = 111 kJ
Disturbance: rise in temperature

adds heat to the system
exothermic reaction is not favorable
Disturbance: drop in temperature
removes heat from the system
exothermic reaction is favorable

Endothermic heat absorbed
PCl5(g) + heat PCl3(g) + Cl2(g) H = +111 kJ
absorbed heat
Disturbance: rise in temperature
adds heat to the system
endothermic reaction is favorable
Disturbance: drop in temperature
removes heat from the system
exothermic reaction is not favorable

(exothermic)
PCl3(g) + Cl2(g) PCl5(g) H = 111 kJ

(endothermic)
[PCl5]
KC =
[PCl3][Cl2]
Changes Net reaction Exothermic
Increase temperature Left K decreases

Decrease temperature Right K increases
Temperature decrease favors an

exothermic reaction.
(endothermic)
SO2(g) S(s) + O2(g) H = 178 kJ

(exothermic)
[O2]
KC =
[SO2]
Changes Net reaction Endothermic

Increase temperature Right K increases
Decrease temperature Left K decreases
Temperature increase favors an

endothermic reaction.
EXERCISE - 9
How does an increase in temperature affect
the equilibrium concentration of the underlined
substance and the value of K:
a) CaO(s) + H2O(l) Ca(OH)2(g) H = 82 kJ
b) CaCO3(g) CaO(s) + CO2(g) H = 178 kJ
c) C(s) + 2H2(g) CH4(g) H = 75 kJ
d) N2(g) + O2(g) 2NO(g) H = 181 kJ
e) P4(s) + 10Cl2(g) 4PCl5(g) H 1528 KJ
EXERCISE - 10
Predict the effect of increasing the temperature
on the amounts of products in the following
reactions:
a) CO(g) + 2H2(g) CH3OH(g) H = 90.7 kJ
b) C(s) + H2O(g) CO(g) + H2(g) H = 131 kJ
c) 2NO2(g) 2NO(g) + O2(g) (endothermic)
d) 2C(s) + O2(g) 2CO(g) (exothermic)
EXERCISE - 11
Predict the effect of decreasing the temperature
on the amounts of products in the following
reactions:
a) C2H2(g) + H2O(g) CH3CHO(g) H = 151 kJ
b) CH3CH2OH(l) + O2(g) CH3CO2H(l)
+ H2O(g) H = 451 kJ
a) 2C2H4(g) + O2(g) 2CH3CHO(g) (exothermic)
b) N2O4(g) 2NO2(g) (endothermic)
EFFECT OF CATALYST
Catalyst speeds up a reaction.

by providing alternative mechanism with
lower activation energy.
Increasing forward and reverse rates to
the same extent.
Shorten the time taken to reach equilibrium.
BUT, REMEMBER
Catalyst has no effect on the equilibrium
position and value of KC.
uncatalyzed catalyzed
Catalyst lowers activation energy, Ea

for both forward and reverse reactions.
EXERCISE - 12 5.1
In the uncatalyzed reaction

N2O4(g) 2NO2(g)
the pressure of the of the gases at equilibrium
are PN O= 0.377 atm and P NO = 1.5 atm at 100oC.
2 4 2
What would happen to these pressures if a
catalyst to the mixture ?
uncatalyzed catalyzed
Change Equilibrium
Changes Shift Equilibrium Constant (value of K )
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no
EXERCISE 13
Consider the following equilibrium process
between dinitrogen tetrafluoride (N2F4) and
nitrogen difluoride (NF2):
N2F4(g) 2NF2(g) H = 38.5 kJ
Predict the changes in equilibrium if
a) the reaction mixture is heated
b) NF2 gas is removed
c) the pressure decrease
d) inert gas, such as He, is added
EXERCISE - 14
Consider the equilibrium between molecular
oxygen and ozone
3O2(g) 2O3(g) H = 284kJ
What would be the effect of
a) increasing pressure by decreasing volume
b) increasing pressure by adding O2
c) decreasing the temperature
d) adding a catalyst
EXERCISE - 15
Heating solid sodium bicarbonate in a closed
vessel establishes the following equilibrium:
2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g)
What would happen to the equilibrium position if
a) some of the CO2 were removed
b) some solid Na2CO3 were removed
c) some solid NaHCO3 were removed
EXERCISE - 16
Consider the following equilibrium process:
PCl5(g) PCl3(s) + Cl2(g) H = 92.5 kJ
Predict the direction of the shift in equilibrium
when
a) the temperature is raised
b) more chlorine gas is added
c) some PCl3 is removed
d) pressure on the gases is increased
e) a catalyst is added to the reaction mixture
EXERCISE - 17
Consider the following equilibrium reaction in a
closed container:
What happen if
a) the volume is increased
b) some CaO is added
c) some CO2 is added
d) a few drops of a NaOH solution are added
e) a few drops of a HCl solution is added
f) temperature is increased
Note: Decomposition reactions are endothermic.
EXERCISE 18
Consider this equilibrium system
CO(g) + Fe3O4(s) CO2(g) + 3FeO(s)
How does the equilibrium position shift if:
a) CO is added
b) Solid NaOH is added
c) Fe3O4 is added
d) Dry ice is added at
constant temperature
DRY ICE (CO2(s))

EXERCISE 19
Sodium bicarbonate undergoes thermal
decomposition according to the reaction
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
How does the equilibrium position shift as a
results of each of the following disturbances:
a) 0.20 atm of argon gas is added
b) NaHCO3(s) is added
c) Mg(ClO4) is added as a drying agent to
remove water
d) Dry ice is added at constant temperature
SYNTHESIS OF AMMONIA:
HABER PROCESS
Nitrogen can be found in many essential natural and

synthetic compounds
Richest source of nitrogen: atmosphere (4 of every 5
molecules are N2)
However, due to the low reactivity of N2, the supply of
usable nitrogen has become limited
Nitrogen atom is very difficult to fix (combine with
other atoms) due to the strong triple bond that holds the
two N atoms together
HABER PROCESS
Nearly 13% of nitrogen fixation on earth is
accomplished industrially through the Haber
process for the formation of ammonia from its
elements:
N2(s) + 3H2(g) 2NH3(g) H = 91.8 kJ
The process was developed by Frizt Haber (German

chemist) in 1913
Over 80% of this ammonia is used in fertilizer

applications
APPLICATION OF EQUILIBRIUM
PRINCIPLES IN THE HABER PROCESS
To make an industrial process economically
worthwhile
N2(s) + 3H2(g) 2NH3(g) H = 91.8 kJ
Three ways to maximize the yield of ammonia:
Decrease [NH3]
Decrease volume (increase pressure)
Decrease temperature
Application of Le Chateliers principle

N2(s) + 3H2(g) 2NH3(g) H = 91.8 kJ
Decrease [NH3]
Product: Ammonia
By removing ammonia, the system will
produce more in continual drive to reattain
equilibrium
The equilibrium will shift to the right
N2(s) + 3H2(g) 2NH3(g) H = 91.8 kJ
4 mol of gas 2 mol of gas
Decrease volume (increase pressure)

4 mol of gas reacts to form 2 mol of gas
Decreasing the volume will shift the
equilibrium towards fewer moles of gas
Produces more ammonia
N2(s) + 3H2(g) 2NH3(g) H = 91.8 kJ
Decrease temperature
Formation of ammonia is
exothermic
Decreasing temperature
(removing heat) will shift the
equilibrium to the right
KC will increase
However, ammonia forms slowly at low temperature
that the process become uneconomical.
High pressure and continuous removal are used

to increase yield, but the temperature is raised
to moderate level and a catalyst is used to
increase the rate.
In Haber process, low temperature will increase the
yield of ammonia, but the rate of reaction will be too
slow
IDEAL CONDITIONS:
Temperature: 450 C - 500 C (to optimize yield and rate)
Catalyst: Iron (to speed up the reaction)
Promoter: Aluminium oxide (to increase catalysts
efficiency)
Pressure: Between 200 1000 atm (to save cost)
KEY STAGES IN THE HABER PROCESS
FOR SYNTHESIZING AMMONIA
EXERCISE - 20
Lime (CaO) used primarily in the manufacture of
steel, glass, and highquality paper. It is produced
in an endothermic reaction by thermal
decomposition of limestone:
How would control reaction conditions to produce
the maximum amount of lime?
EXERCISE - 21
The oxidation of SO2 to SO3 is an important
industrial reactions because it is the key in
sulfuric acid production:
1
SO2(g) + O2 SO3(g) H = 99.2 kJ
2
a) What qualitative combination of T and P
maximizes SO3 yield?
b) How does addition of O2 affect Q? K?
c) Suggest a reason catalysis is used in the
manufacture of H2SO4?
END OF
SLIDE SHOW

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6.1 Dynamic Equilibrium

Few chemical reactions proceed in only one

Reactions proceed in only one direction

= indicates reversible reaction

In a reversible reaction, initially the

Consider the following reversible reaction:

The graph of the concentration of A and

A state in which there are no observable

Number of H2O molecules

Most chemical reactions are reversible.

When we introduce some N2O4(l) into a sealed flask

The liquid vaporizes (bp = 21oC) and the gas begins

The color slowly darkens, but after a few moments,

Reactant and product concentrations stop

C: Mixture reaches final color

Also known as law of mass action.

At a given temperature, a chemical system

For a particular system and temperature, the

Consider this general reaction equation:

Large K Equilibrium will:

2CO(g) + O2(g) 2CO2(g) K = 2.2 x 1022

Small K Equilibrium will:

N2(g) + O2(g) 2NO(g) K = 1 x 1030

2BrCl(g) Br2(g) + Cl2(g) K=5

Which of the following reactions will tend to

a) H2(g) + Br2(g) 2HBr(g) KC = 7.9 x 1018

b) 2NO(g) N2(g) + O2(g) KC = 2.1 x 1030

c) 2BrCl Br2 + Cl2(in CCl4 solution) KC = 0.145

i. Reactant and product concentrations

ii. Forward reaction rate = reverse reaction

iii. The reaction quotient (Q) = The

Even though equilibrium is reached in

6.2 Equilibrium Constants (Part I)

(a) Define homogeneous and heterogeneous equilibria.

LESSON DURATION: 1 hour

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

CH3COOH(aq) CH3COO(aq) + H+(aq)

CH3COOH(aq) CH3COO(aq) + H+(aq)

Note: Unit of concentration = M (mol L-1)

The equilibrium constant for reaction

PCl3(g) + Cl2(g) PCl5(g)

KC = 1.67 (at 500K)

KP = 4.07 x 102 (at 500K)

KC = 1.67 (at 500K)

KP = 4.07 x 102 (at 500K)

In quoting a value for the KP or KC, you MUST

d) C3H8(g) + O2(g) CO2(g) + H2O(g)

e) NH3(g) + O2(g) NO(g) + H2O(g)

The following equilibrium process has been

PO 2 = 158 x (0.400)2/(0.270)2 = 346.8 atm

N2O4(g) 2NO2(g) (at 25oC)

2NO2(g) N2O4(g) (at 25oC)

N2O4(g) 2NO2(g) (at 25oC)

1 N (g) + H (g) 2 NH (g)

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

[CaO][CO2] [CaCO3] = constant

The concentration of pure solids, pure liquids

PCO 2 does not depend on the amount of CaCO3 or CaO.

Write equilibrium constant expression for

c) NH4Cl(s) NH3(g) + HCl(g)

d) H2O(l) + SO3(g) H2SO4(aq)