Unit-7

CHEMICAL EQUILIBRIUM-1
Many chemical reactions do not proceed to completion when they are carried out in a closed
container. An equilibrium is a condition in which there is no apparent change in the properties of the
system like concentration, pressure, lemperature etc. This condition is reached when two opposing
processes take place simultaneously at the same rate in opposite directions.

The equilibrium achieved in physical processes such as dissolution of salt, evaporation of water
etc is called physical equilihrium.

The equilibrium aehieved in chemical processes such as decomposition of calcium carbonate or

reaction between H, and I etc is called chemical equilibrium.

Eguilibrium in physical processes

Some common physical equilibria are
Solid |Liquid
Liquid a s
Solid Gas

Solid-Liguid Equilibrium
When a crystalline solid is heated, a temperature is reached at which both solid and liquid states
can co-exist at 1 atm pressure. This temperature is called normal melting point or normal freezing point rof
thesubstance. If a solid- liquid system at melting point is taken in a well-insulated container, then the solid
is in dynamic equilibrium with liquid.
For example, consider ice and water taken in a perfectly insulated thermos flask at 273K(melting
point ofice). It is noted that the temperature, as well as the masses of ice and water remain constant. This
represents a dynamic equilibrium between ice and water.
lce water

HOH,O
At equilibrium
Rate of melting= Rate of freezing
or No of molecules going from ice into water No of molecules of water going into ice.

Liquid-Gas equilibrium
When a liquid (say water) is placed in a closed evacuated container, the liquid evaporates, ie the
molecules of water leave the liquid phase and enter the vapour phase. A pressure is built up gradually
within the vessel due to the formation of water vapour. Soon vapour return to the liquid surface and
condense. After some time the rate of evaporation and condensation become equal and a state of dynamic
equilibrium exists.
At equilibrium
Rate o f evaporation = rate o f condensation

H,O H,0
The pressure exerted by the vapour in equilibrium with the liquid at a particular temperature is
called the vapour pressure of the liquid.

The vapour pressure ofa liquid is constant at a given temperature but it increases with increase in
temperature. It does not depend upon the amount of liquid or size ofthe vessel.
Solid-Vapour Equilibrium
Consider a small quantity of iodine placed in a closed vessel. Then iodine vapourises and the
vessel get filled with violet vapours and intensity of colour increases. After some time intensity of colour

becomes constant and at this stage cquilibrium is attained.

solud 2vapour
At this stage
Rate of conversion of iodine to iodine vapours = Rate of condensation of iodine vapours to iodine

Other examples are:

Camphorsoudy Camphor,apout)
NH,Cloid NHACTv3pou)
Eguilibrium involving dissolution of asolidin aliquid
But
When sugar is added to water, the crystals of sugar keep on going into water in the beginning.
afier some time no more of sugar dissolves.
solution. in a saturated
A solution in which no more solute can be dissolved is called a saturated
the solution becomes equal to the
solution, at constant temperature. the rate at which the molecules enter

rate at which the molecules leave the solution. Thus a saturated

solution corresponds to the state of
equilibrium.
At equilibrium
Rate of dissolution = Rate of precipitation

Sugar (solid) = Sugar (solution)

in given quantity of solvent is

The amount of solute required to prepare a saturated solution a

known as solubility of the solute. Solubility of a solid in any liquid depends upon temperature.

Equilibrium involvingdissolution of gases in liquids:

on temperature and
Gases are soluble in liquids. The gas in a liquid depends
solubility of a
between the dissolved and the undissolved gas in
gas
pressure. At a given pressure, there is an equilibrium in water at high pressure.
the gaseous phase.For example in soda water CO, is dissolved
At equilibrium
CO(gas)=CO2 (in solution)

Effect of pressure on the solubility of a gas in a liquid is given by Henrn'slaw.

This law states that:
The mass of u gas dissolved in a given mass ofa solvent. at a grien temperuture is directh

the pressure of the gas above the solvent.

proportional to
m
m = kp where 'm' is the mass and "p is the pressure of the gas.

in liquid decreases with increase in temperature.

The solubility of a yas a

Characteristies of physicalequilibrium
characteristics are sycommon to the stem at equilibrium.
For physical processes, the following closed
I. Equilibrium is possible only
in a system at a given temperature.
become constan:.
thc measurable properties of the sy stem
2. At equilibrium, balance betw een the twa
occur at the same rate and there is a dy namic
3. Both the opposing processes
opposite processes.
it is characterized by constant value of one of its
4.When equilibrium is attained for a physical process.
parameters at a given temperature.
in water. [CO;ay] is constant at a given temperature.
For example, for the dissolution of CO,
ICO: g»l
 5.The magnitude of such parameters indicates the extent to which the reaction has proceeded before
reaching equilibrium.
For exampe, greater value of [CO2(aq)] indicates. greater is the extent to which CO; dissolves in
water.

Equilibrium in chemical processes:

ReversibleThe
andreactions
Irreversibleinreactions
which the products do not react under any condition to give back reactants are

called irreversible reuctions.

..when a piece of sodium is dropped into water, a violent reaction takes place to form NaOH and H2 gas
2Na+2H,02NaOH + H2
I is not possible to carry oul the reverse of the above reaction under any known experimental conditions.
An irreversible reaction takes place only in one direction and proceeds almost to completion.
Other examples of irreversible reactions are
1) NaOH + HCI NaCl + H;0
2) AgNO, t NaCl AgCI +NaNO
and neutlralisation reactions are irreversible.
Usually precipitation
back reactants are called
The reactions in which products under suitable conditions react to give
reversible reactions.
of iron are
when steam is hot iron, hydrogen and magnetic oxide
passed over red
For example, and iron are
heated magnetic oxide of iron, steam
formed. On the other hand if hydrogen is passed over
the second reaction is called the backward
produced.The first reaction is called the forward reaction and
reaction.
3Fe + 4HO- Fe^O4 + 4H2 (Forward reaction)
Fe O +4H 3 F e +4H,0 (Backward reaction) two arrows pointing in opposite directions
A reversible reaction can be represented by putting
between the reactants and products.
3Fe + 4H0 Fe;04 + 4H2

Some more examples of reversible reactions are

(i) H2+ l#2H1
(ii) NO=2NO2
(ii) N2 + 3H,#2NH3
(iv) PCl PCl; + Cl.

Chemical equilibrium forward and backward

reactions are feasible. If such a
reaction is
In reversible reaction both
a Then a state of equilibrium is
closed vessel, then both the reactions occur simultaneously.
carried out in a
reactants are converted
into products.
established before whole of the

Consider a reversible reaction

A + B C +D

reaction
of the forward
beginning, the velocity because
In the
will be maximum. lt decreases gradually of the fallin
the
time velocity of
and B. At the same
..
concentration of A state is
Finally an equilibrium
backward reaction increases. reaction becomes
of the forward
reached when the velocity reaction. This
of the backward
Cxactly equal to the velocity
chemical eyuilibrium.
At this state,
cquilibrium state is call:d remain
reactants and
the products
he concentration of the of the
the measurable properties
conslant. Al equilibrium
noliceable change.
Syslem do not undergo any i.
 At cquilibrium both forward and backward reactions proceed at cqual rates. Therefore, chemical
equilibrium is dnanic innature.

Q. Prove that chenmical equilibrium is dynamic in nature

The dynamic nature of chemical equilibrium can be demonstrated in the synthesis of ammonia by
Haher's process. Ammonia is synthesized by treating N and H in known amounts at high temperature and
pressure. At equilibrium. the concentration of NH, and concentration un-reacted N2 and H renmain
unchanged.
In order to understand the dynamic nature of equilibrium, the synthesis of ammonia is carried out
with exactly same starting conditions but using D» (deuterium) in place of H2. The system attains
equilibrium with the same composition except that D> and ND, are present instead of H2 and NH;.
After equilibrium is reached, these two mixtures are mixed together and left for a while. When
later this mixture is analyzed, the concentration of ammonia is just the same as before. However when this
mixture is analyzed by a mass spectrometer. it is found that all deuterium containing forms of ammonia
(NH. NH,D, NHD2 and ND) and hydrogen (H2. HD and Da) are present. This is possible only by the
continuation of forward and backward reactions even after attaining the equilibrium. If the reaction had
stopped when they reached equilibrium, then there would have been no mixing of isotopes in this way.

Characteristics of Chemical equilibrium:

1. At equilibrium, the observable properties such as pressure, concentration, density, colour. etc of
the system remain unchanged.
2. It is dynamic in nature
3. The equilibrium can be approached from either direction.
4. The equilibrium can be attained only in a closed system.
s. A catalyst does not alter the equilibrium point. A catalyst increases the rate of forward as well as
backward reaction to the same extent. Therefore equilibriurm point is not altered. However, the

equilibrium is attained earlier.

6. At equilibrium, AG is equal to zero.

Law of mass action:

The law of mass action was put forward by Guldbertg and Waage. It gives the quatitative
relationship between rates of reaction and the concentration of the reacting species. The law states that. "the

rate of a chemical reaction is directly _proportional to the _product of the molar concentrations of the
coeflicient of that species
reactants with each concentrationterm raised to the power equal to the numerical
in the chemicalequation"
Consider the hypothetical reaction
A +B Products.
Rate of reaction, r o [A] [B]
R k[A] [B]
and K° is called rate constant.
Where [A] and [B] are the molar concentrations of A and B respectively,

For any general reaction

aA +bB- Products
Rate K[A' [B].

Lawof chemicalequilibrium simple mathematical expression for a

mass action it is possible to derive a
By applying law of
reversible reaction.
Consider a simple reversible reaction
A+B C+ D

According to law of mass action

Rate of forward reaction [A] [B]
 KIA]B] Where K is the rate constant for forward
reaction.
Rate of backward reaction |C]|D]
K [C]|D] Where Kb is the rate constant for the backward
reaction
At equilibrium
Rate of forward reaction =
Rate of backward reaction.
KrIA] (B] = K, [C] {DI

K LCILD
******
[A] [B]
Since Kand K, are constants. the ratio Kr/ Ky is also constant and is
represented by KKc.
Kf
Kc= C] (D]
Kb A] [B]
The constant 'Kc° is called
equilibrium constant.
For a general reaction of the
type
aA + bB cC +dD

Equilibrium constant Kc = IC D
[Al'[B
The above mathematical expression is known as
law of chemical equilibrium.
At a given temperature, the product of concentrations of the reaction products raised to the
respective stoichiometric coefficient in the batanced chemical equation divided by the product of
concentrations of the reactants raised to their individual stoichiometric coefficients has a constant value
This is known as law of chemical equilibrium.
For example, the equilibrium constant for the reaction
4NH+50, * 4NO- 6H2O is written as

Kc
[NOJ [H,Ooj
NH]' [O.

The concentration ratio,

ICI [DJ" is called concentration quotient and is denoted by Q.
[A [B]
Al equilibrium Q= Kc
IfQ< Kc; net forward reaction takes place
IfQ= Kc: the reaction is at equilibrium.
IfQ>Kc: Net backward reaction takes place.
----------*-*
constant for the reaction is the inverse of the equilibrium constant for the
Equilibrium reverse

reaction in the forward reaction.

Eg: For the reaction
H:(g) + 12(g)= 2HI(8)

Kc H:TLTHI x
X

Tlhe equilibrium constant for the reverse reaction, 21I(g)= H; (g) + 1 (g) at the same temperature is

K'c [H
HI[= /X = /Kc
|HI
Thus K'c = 1/Kc
But for the reaction
H2 + l HI

Kc"
[HI] [HI
H1T12 [H2L]
Kc

In general
aA + bB = cC +dD Eq: constant= Kc
Eq: constant K'c = 1/Kc
cC+dD a A + bB
naA +nbB= ncC + ndD Eq: constant K"c =
Kc"

Eguilibrium constant in gaseous systems

of the reactions in terms of molar concentrations of the reactants
and
The equilibrium constants the
Kc. But for reactions involving gases, it is more convenient to express
products is represented as
It is represented as Kp.
equilibrium constant in terms of partial pressure.
For the reaction,
aA + bB cC +dD.
the partial of A, B, C and D the equilibrium constant Kp is given by,
IfPa. P», P¢ and Po are pressures

[Pe [Po
KP PT[Pal
Relationship between kp and kc_

For the reaction aA + bB *cC +dD

Kc IDI [Pc Po
AT B Kp PAT IPs
For ideal gases
PV nRT
PV n/v RT
= CRT

Ps=CpRT, Pe
=

CcRT and Pp -CpRT

PACART,

ICCRTIICDRT"
Kp CRT"IC,RT
CCox (RT
ICAl TC
* (RT)cidj
-

(a-b

n
Kp Kc (RT)
reactants)
(Number of moles gaseous
of gaseous products)
-

Where An =( number of moles

If An =0, Kp = Kc

Kc.
positive value, Kp
>
IfAn has a
Kc.
negative value, Kp
<

IfAn has a

Units ofequilibrium constant: units when the number

of moles of products is equal to the
Kc has no
The equilibrium constant
number of moles of reactants.

6
 .C. n 0

.g. N.(g) O.(g)2NO(g)

INO mol 1."

IN.11O Imol 1."1|mol'
Here Kc has no unit.
Bul Ke has units when the number of mols of products is not cqual to the number of mols of reactants.

.g. N, (g) 3H, (g) 2NH(g)

INH mol 1.'
Kc 1 1mol
IN. 1H: mol 1'mol1
In general
"
Unit of Kc =

[molL'|
Atmosphere] "
Unit of Kp

Homogencous and heterogencousequilibria

The equilibria in which all the substances are in the same phase are known as homgeneous
equilibri
E.g. N2g+3H2g)=2NHug)
2S02 (p) + O2tp)= 2S01 (g)

CH-COOH +CaH,OH =CH;-COOC,Hs» H,O

The cquilibria in which the substances involved are present in different phases are called
heterogenevus equilibria
E.g CaCO ) = CaO )+ CO2p)
H,O ()=H,O
Ag taq Can) AgCl

Characteristics of equilibrium constant (K)

) The equilibrium constant has a definite value for every chemical reaction at a particular
temperature.
(2 The value of equilibrium constant is independent of initial concentrations of reacting species.
3) Equilibrium constant of the reverse reaction is inverse of the cquilibrium constant for the
forward reaction.
(4) The equilibrium constant is independent of the presence of catalyst.
(5) If the cquilibrium constant is expressed in terms of concentration. it has different units lor
different reactions.

Applications ofcquilibriumconstant1
() Predictingtheextentofa reuction:
The value of equilibrium constant gives the extent to which the reactants are converted into the
products.
Larger the value of K. greater is the extent to which the reactants are converted into products.
Smaller valueof Kindicates, only asmallfraction ofreactantsis convened into products.
irKe10'. produçts predominate over reactants.
If Kc 10, reactants predominate over
producis. If Ke is between 10 and 10', appreciable concentrations both reactants and products are present.

1
For example
2H-O(g)=2H: (s) + 0, (g)

K ---
[H O--------
= 135 x 10" at 1703K

The smaller value of K indicates that at equilibrium, only a small fraction of H,0 dissociates into H; and

O
But in the reaction
2CO(g)+O, (g)2C0, (g)
K
CO
**-***** =2.2 x 10 at 1000K

The large value of 'K' indicates that at equilibrium, the reaction is almost complete.

2)Relativestubilities ofreuctants and products:

The value of 'K' gives an idea about the relative stabilities of reactants and products. If value
of K is large the products are more stable. If °K' is smal, the reactants are more stable.

B) Predictingthedirection ofthereaction:
The equilibrium constant can also be used to predict the direction of a reaction. For this purpose
we calculate the reaction quotient, Q
For a general reaction
aA + bB c C + dD

The reaction quotient

[C[D
Q =

A |B
At any stage of the reaction we can calculate the reaction quotient Q.
Then IfQ>Kc. the reaction will proceed in the direction of reactants.
IfQ< Kc the reaction will proceedin the direction of the products.
IfQ= Kc. the reaction is already at equilibrium,

4) Calculating equilibrium concentratios

Once the value of the equilibrium constant of a reaction is known, the equilibrium concentrations

of various reactants and products can be calculated.

Problems: mol/L and 2 10'

(1) A H2, N and NH; with molar concentrations 3x10 mol/L,
mixture of 10 Ix x

the value of' Kc for reaction

mol/L respectively was prepared at 500K. At this temperature ,
Predict at this stage concentration of NH3 will increase or
N2 (g)+3H: (g)= 2NH; is 61.
decrease.
Cl,(g)
penta-chloride decomposes according to the equation PCls(g)= PCl(g)
+
(2) Phosphorus
Iml of PCl; is placed in a closed container of SL capacity and heated to 523K. What will be the

the equlibrium. Kc=1.80

composition of the mixture at
heated at 625 K to establish equilibrium
(3) 2 moles of PCI, were introduced in a 2 litre flask and
when 60% of PCl was dissociated into PCl; and Ch. Find the value of equilibrium constant.

At 700 K the equilibrium constant Kp, for the reaction

(4)
 2S0(g) 280:(g)+ O;(g)
is 1.8 x 10" kPa. What is the numerical value in moles per litre of Kc at the same temperature.
(5) For the reaction Na (g) + 3H, (g)* 2NH , the value of Kp is 3.6 x 10 at 500K. Calculate the
value of Ke for the reaction at the same
temperature.
(6) For the reaction N: (g) +3H, (g)* 2NH(g) , the value of Kp 41 at 400K. Find out the value of
Kp for each of the following reactions at the same temperature.
(a) 2NH:(g)=N, (g)+ 3H; (g) (b)2 N (g) +6H, (g) > 4NH(g)

Factors affecting equilibria- Le-Chatelier's Principle

The important factors which affect the state of equilibrium are: temperature, pressure and
concentration of reactants and products. The effect of these factors on equilibrium can be predicted be Le-
Chatelier's principle.

It states that "ifa system at equilibrium is subjected to a change in concentration, temperature ar

pressure, then the equilibrium shifis in the direction that tends to nullify the effect of the change." This is
applicable to all physical and chemical equilibria.

I. Effect of concentration change

According to Le-Chatelier s principle, when the concentration of any of the reactants or products
in a system at equilibrium is increased, the equilibrium will shift so as to reduce the concentration of the
added substance. Thus the addition of any one of the reactants will shift the equilibrium in a direction that
consumes the reactants., i.e., the forward reaction. On the other hand, if one of the products is added. the
equilibrium will shift in a direction that consumes products, i.e., the back ward reaction.

For example, consider the reaction

H2t 2H1
When a small amount of hydrogen is added to the system, the equilibrium will shift in the
direction which decreases the concentration of hydrogen. This is possible by shifting the equilibrium in the
forward direction. But when small amount of HI is added to the system. the equilibrium will shift in the
backward direction.

In general addition of any one of the reactants or removal of any one of the products will shift the
equilibrium in the forward direction. On the other hand the addition of any one of the products or removal
of any one of the reactants will shift the equilibrium in the backward direction.

Examples:
. In the equilibrium, Fe (aq) + SCN FesCN*" (ag)
Yellow colcourless deep red
Addition of ferric salt to the equilibrium, deepens the colour of the solution showing that there is
increase in the concentration of FeSCN"
2. Formation of ammonia
N2+ 3H 2 NH3
If at equilibrium, more H2 or N is added to the system, equilibrium shifts in the forward direction

resulting in the formation of ammonia.

2.Effect of change oftemperature

A chemical involves two opposing reactions. If one of the reactions is exothermic the
equilibrium
other must be endothermic.
For example,
Na +3H2 2 NH3: AH =-93.6 kJ.
while the backward reaction is endothermic.
In this reaction the forward reaction is exothermic
 Now if the temperature is increased, the system will reduce the temperature by
shifting the
the endothermic reactions are favoured by
equilibrium in the direction which absorbs heat. Therefore shifts in the direction
increase of temperature. Similarly, if the temperature is decreased, the equilibrium
which evolves heat. Therefore exothermic reactions are favoured by decrease of temperature.
So low temperature favours the formation of ammonia in the Haber process.

3,Effect of change of pressure

substances and
The change of pressure has effect only on those equilibria which involve gaseous when the
proceed with change in number of moles of the gases. According to Le-Chatelier's principle
pressure is increased, the equilibrium will shift in the direction so as to reduce the pressure. This is possible
by shifting the equilibrium in the direction which has smaller number of moles of gaseous molecules. ut
when the pressure is reduced, the equilibrium will shift in the direction which has more number of gaseous
molecules.
This can be explained with the help of the following examples.
AH = -93.6 kJ.
Consider the reaction Nate)+ 3Hxg 2 NH
Here the forward reaction is accompanied by a decrease in the number of moles of gaseous substances.
Hence increase of pressure favours forward reaction. On the other hand decrease of pressure favours the

backward reaction.

Consider the reaction PCls(g) PCls(g) + Ch(g)

Here the forward reaction is accompanied by increase in the number of moles and backward
reaction is accompanied by decrease in number of moles. Therefore, as the pressure is increased the
equilibrium shifts in the backward direction.

Now consider the reactions which do not involve any change in number of moles of gaseous substances.
1. Hz(g)+1k () 22HI (g)
2. Ng) +Oz (g) 2NO(g)
In such reactions pressure has no effect on equilibrium.

4.Effect ofvolumechange
Increase of pressure means decrease of volume of the system. So the effect of change of volume
will be exactly the reverse of that of pressure change.

5.Effect of catalyst
A catalyst does not affect equilibrium constant. It increases the rate of both forward and backward
reactions to the same extent. A catalyst has no effect on the equilibrium composition of a reaction mixture.
But it helps to attain the equilibrium quickly.
For example consider the manufacture of H2SO, by contact process.

1026
250 (8)+ O () 2SO(g) Kc 1.7x

Even though the value of Kc is high, the oxidation of SO, to sO, is very low. However in the presence of
platinum or vanadium pentoxide (V20s), the rate of reaction is high.

5.Effect of adding inert gases.

(a) When an inert gas is added to the system at equilibrium at constant volume, the total pressure of
the system will increase. But the partial pressures of the reactants and products will remain the
same. Hence addition of inert gas at constant volume has no effect.
(b) When inert gas is added to the system at equilibrium at constant pressure, then the total volume of
the system will increase. As a result the number of moles per unit volume of reactants and product
will decrease. Then the equilibrium will shift in a direction in which there is increase in the
number of moles.

10