Ms Asnida Yanti Ani

A117-P (Al-Farabi 3)
Faculty of Applied Science
UiTM (Perlis)

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At the end of the topic, students should be able to :

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INTRODUCTIONTO CHEMICAL EQUILIBRIUM
Chemical change
 Chemical change occurs when the atoms that make up one or more
substances rearrange themselves in such a way that new substances are
formed.
 Sub stances which decrease in quantity = reactants
 Substances which increase in quantity = products
 A given chemical reaction system is defined by a balanced net chemical
equation which is conventionally written as

REACTANTS PRODUCTS

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INTRODUCTIONTO CHEMICAL EQUILIBRIUM
Few chemical reactions proceed in only one direction
 The reaction continues until one or more of the reactants are
completely used up in the reaction.
 When this happens, the reaction stop. An example is the
reaction is between magnesium carbonate and dilute
sulphuric acid.
MgCO3 (s) + H2SO4 → MgSO4 (aq) + CO2 (g) + H2O (l)

Some of the chemical reaction proceed in two direction which

is called as “ reversible reaction”.

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 INTRODUCTION
TO CHEMICAL EQUILIBRIUM

In principle, every chemical reaction is reversible ... capable

of moving in the forward or backward direction.

2 H2 + O2 2 H2O

Some reactions are easily reversible ...

Some not so easy ...

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The Concept of Equilibrium
 At the start of a reversible process, the reaction proceeds toward the
formation of products.

 As soon as some products molecules are formed, the reverse process-that is,
the formation of reactant molecules from product molecules-begins to take
place

 when the rates of the forward and reverse reactions are equal and the
concentrations of the reactants and products remain constant with time,
chemical equilibrium is reached.

 Double headed arrow sign ( ) in the equation is used to indicate that

the reaction is reversible

REACTANTS PRODUCTS
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The important characteristic of chemical equilibrium are:
The properties ( i.e concentration) of the reactant and products
become constant at equilibrium and remain unchanged.
The equilibrium can be approached from either direction i.e
starting with pure reactant or pure products, provided enough
time is allowed.
The chemical equilibrium is dynamic in nature. After the
equilibrium achieved, the reaction does not stop. Forward and
reversed reaction occur at equal rate (the system is in a state of
dynamic equilibrium)

* Static equilibrium –after achieved equilibrium, the reaction stop.

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 The reaction proceeding from the left to the right is called the forward
reaction, while the reaction proceeding from right to the left is called
the reverse reaction/backward reaction

 There are two kinds of molecular equilibrium:

(a) Homogeneous molecular equilibrium
- systems where all the components are in the
same physical state
- eg: N2O4 (g) 2NO2 (g)

(b) Heterogeneous molecular equilibrium

-systems where at least one component is a different
physical state as the other components in the system
- eg: CaCO3 (s) CaO (s) + CO2 (g)

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 EQUILIBRIUM EXPRESSION FOR A REACTION
A. EQUILIBRIUM CONSTANT, Kc

 The general equation for a reversible reaction is given by:

aA + bB cC + dD
 At equilibrium in the above reaction; Important !!!!!
only species in either the gas or
the equilibrium constant, Kc = [C]c[D]d aqueous phases are included in
[A]a[B]b this expression because the
concentrations for liquids and
solids cannot change
 Hence the value and units of Kc depend on how the chemical equation is written.
aA + bB cC + dD

 Kc = eq. constant for forward reactionK

c
 K ’c = eq. constant for reverse reaction
K ’c

Kc = _1_
K ’c
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Exercise:
 Eg: 2HI (g) H2 (g) + I2 (g)
given that [HI] = 1.750 M
[H2] = 1.125 M
[I2] = 0.125 M

Calculate the value of Kc for:

a) forward reaction
Kc = [I2] [H2] = 0.125 M x 1.125 M = 0.046
[HI]2 1.750 2 M2

b) reverse reaction
K ‘c = 1 = 1 = 21.7
Kc 0.046

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B. EQUILIBRIUM CONSTANT IN TERM OF PRESSURE, Kp

 Kp is the equilibrium constant in terms of partial pressures. It can only

be applied to gas reaction.
aA (g) + bB (g) cC (g) + dD (g)
 For the above gas reaction, at equilibrium,
(PC)c.(PD)d = a constant, Kp
(PA)a.(PB)b

Where PA = partial pressure of gas A, etc.

PA = number of moles of gas A X total pressure

total number of moles of all gases

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 Example :
The equilibrium constant Kp for the decomposition of phosphorus pentachloride
to phosphorus trichloride and molecular chlorine is found to be 1.05 at 250oC. If
the equilibrium partial pressure of PCI5 and PCI3 are 0.875 atm and 0.463 atm,
respectively, what is the equilibrium partial pressure of CI2 at 250oC?

PCI 5(g) PCI 3(g) + CI2 (g)

 Solutions:
First, write Kp in terms of the partial pressures of the reacting species:
Kp = P PCI 3 P CI2
P PCI 5

Knowing the partial pressures, we write

1.05 = (0.463) (PCI2 )

(0.875)
so, PCI2 = (1.05) (0.875) = 1.98 atm
(0.463)

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 For gases; PV = nRT
P = (n/V) RT
Relating Kc and Kp
P = (concentration) RT
PA = [ A ] RT, so………. PB = [ B ] RT,
PC = [ C ] RT, and so on…

aA(g) + bB(g) cC(g) + dD(g)

KP = [PC]c[PD]d = ([C] RT)c ([D] RT)d
[PA]a[PB]b ([A] RT)a ([B] RT)b

=[C]c[D]d (RT) (c+d) –(a+b)

[A]a[B]b

Kp = Kc (RT) ∆n
∆n = (moles of gases products)-( moles of gases reactants)
T = temperature (in K)
R = gas constant (0.0821 L atm/Kmol)

Substituting Kc
into the equation for Kp

Kc = [C]c[D]d
[A]a[B]b

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 Example :
For the reaction
N 2(g) + 3H 2(g) 2NH 3(g)
Kp is 4.3 X 10-4 at 375oC. Calculate Kc for the reaction.

 Solutions:
From equation Kp = Kc (0.0821T) n we write:
Kc = Kp
(0.0821T) n
Because T = 375 + 273 = 648K and n = 2-4 = -2, we have

Kc = 4.3 X 10-4
(0.0821 X 648) -2
= 1.2

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Exercise
Methanol (CH3OH) is manufactured industrially by
the reaction

CO(g) + 2H2(g) ↔ CH3OH

 
The equilibrium constant (KC) for the reaction is 10.5
at 220 °C. What is the value of KP at this temperature?

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Answer:
R = 0.0821
T = 220 + 273 = 493 K
∆n = (moles product) – (moles reactant)
= 1 – (1 + 2) = -2

KP = KC (RT) ∆n
= 10.5 (0.0821 x 493) -2
= 10.5 ( 1 / (0.0821 x 493)2)
= 6.41 x 10-3

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The Reaction Quotient,(Q)
 The Reaction Quotient, (Q) is a mass action expression just like the
equilibrium constant (K) except it is for a reaction at conditions NOT
at equilibrium.
 The reaction quotient is used to determine which direction a system
will shift to reach equilibrium
aA(g) + bB(g) cC(g) + dD(g)

Q = [C]c[D]d Where [A], [B], [C], and [D] are molarities

[A]a[B]b at any time.

 Calculate Q and compare it to K

 (Q=K) : the system is already at equlibrium so it will not shift in either
direction
 (Q>K) : the system will shift to the left (some products will be
converted to reactants)
 (Q<K): the system will shift to the right (some reactants will be
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EXERCISE:
2SO2 (g) + O2(g) 2SO3 (g)
At a particular temperature, Kc = 100. If 1 mol of SO2, 2 mol of O2 and 8
mol of SO3 are placed in a 10 L flask, in which direction will the
reaction proceed?
Solution:

Q= [SO3]2 = (0.8 )2__ = 320

[SO2]2[O2] (o.1)2 (o.2)

Since Q>K,the numerator is too large, reaction goes

backward, from right to left until Q =K at equilibrium.

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 CALCULATION OF EQUILIBRIUM CONSTANT

(Kc AND Kp)

 General procedure for solving equilibrium problems:
 Write the equation for the chemical reaction
 Determine equilibrium concentration
 Write the equilibrium constant expression
 Substitute and solve
 Calculating Equilibrium Concentrations:
To find the concentration which characterize an equilibrium, it is best
to proceed through the “ Start or Initial, Change, Equilibrium” (ICE
process). This implies starting with the:
 initial concentrations (I)
 determining the change (C)
 using K to find the equilibrium concentration (E)

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Consider
2NH3 (g)  3H2 (g) + N2 (g)

5.0 mol NH3 are introduced into 5.0L reactor vessel in

which it partially dissociate at high temperature. At
equilibrium at particular temperature, 1.0 mol of
ammonia remains. Calculate the concentration of N2
in the reaction. (3 marks)

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 LE CHATELIER’S PRINCIPLE
 Le Chatelier’s Principle allows us to predict the effects of changes
 Temperature
 Pressure
 Concentration
 Catalyst
on a system at equilibrium. It states that if a system at equilibrium
experiences a change, the system will shift its equilibrium to try to
compensate for the change

(a) Changing in Concentrations (only gas & aqueous)

 If you lower the concentration or remove some of a species, the

system will shift to produce more of that species
 If you increase the concentration or add some of a species, the
system will shift to produce less of that species

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 Example:

 H2 (g) + I2 (g) 2HI(g)

(i) If [H2] , [I2] , equilibrium will shift to the right (more products)
(Reactants)

[HI] , equilibrium will shift to the left (more reactants)

(Products)

If you increase the concentration or add some of a species, the

system will shift to produce less of that species

 (ii) [HI] , equilibrium will shift to the right (more products)

[H2] and [I2] , equilibrium will shift to the left (more reactants)

If you lower the concentration or remove some of a species, the

system will shift to produce more of that species

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(b) Changing the volume / pressure (only gases)

 Increasing the volume has the same effects as decreasing the

pressure and vice versa
 When you increase the pressure, the system will shift to the least
number of gas molecules are formed because the more gas
molecules there are, the more collisions there are.
 These collisions and the presence of gas molecules are what cause
the pressure to increase
 When you decrease the pressure, the system will shift to the highest
number of gas molecules are produced

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(c) Changing temperature

 For every reaction which can go forwards and backwards,

one direction is endothermic and the other is
exothermic

 A reaction is endothermic if it takes heat from its

surroundings

 A reaction is exothermic if it gives heat to the

surroundings

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Exothermic
N2(g) + 3H 2(g) 2NH 3(g) H = -92.4 kJ

can be write
N 2(g) + 3H 2(g) 2NH 3(g) + 92.4 kJ
N 2(g) + 3H 2(g) 2NH 3(g) + temperature

If T , equilibrium will shift to the left (more reactants)

If you increase the concentration or add some of a species, the
system will shift to produce less of that species

If T , equilibrium will shift to the right (more product,NH3)

If you lower the concentration or remove some of a species, the
system will shift to produce more of that species

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Endothermic
2NH 3(g) N 2(g) + 3H 2(g) H = +92.4 kJ

can be write
 92.4 kJ + 2NH3(g) N2(g) + 3H2(g)
temperature + 2NH3(g) N2(g) + 3H2(g)

If T , equilibrium will shift to the right (more product, NH3)

If you increase the concentration or add some of a species, the
system will shift to produce less of that species

If T , equilibrium will shift to the left (more reactants)

If you lower the concentration or remove some of a species, the
system will shift to produce more of that species

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For exothermic – T - equilibrium will shift to the left
- Kc

For endothermic – T - equilibrium will shift to the

right
- Kc

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(d) Using catalyst

 A catalyst increases the speed in which a reaction takes place

 However, catalyst never has any effect on the equilibrium

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 Summary of Factors That May Effect the Equilibrium Position

 We have considered four ways to affect a reacting system at

equilibrium. It is important to remember that, of the four
 only a change in temperature changes the value of the
equilibrium constant
 changes in concentration, pressure, and volume can change the
equilibrium constant as long as the temperature does not
change
 a catalyst can help establish equilibrium faster, but it has no
effect on the equilibrium constant or on the equilibrium
concentrations of the reacting species

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