EQUILIBRIUM

Equilibrium
State of a process in which measurable properties like pressure,
temperature etc does not undergo any change with passage of time .

⇌
Types of equilibrium
1. Equilibrium in physical process
2. Equilibrium in chemical process
Liquid-vapour equilibria
Characteristics of liquid- vapour equilibrium
• Attained in a closed system.
• Attained at any temperature.
• Mass of vapour & liquid do not change.
• The pressure of the vapour doesn’t change as long as the
temperature remains constant.
• This pressure of the vapour is called equilibrium vapour
pressure of the liquid.
• It is a dynamic equilibrium where the processes of
evaporation & condensation take place at equal rates.
 Equilibrium involving dissolution of solid in liquid
In a saturated solution,a dynamic equilibrium exists between the solute
molecules in the solid state and in the solution

Rate of dissolution of sugar = Rate of crystallization of sugar

Mass of solid & concentration of solution do not change

 Dynamic nature of equilibrium :
Experiment:
saturated solution of non-radioactive sugar + radioactive sugar
Observation:
radioactivity is observed both in the solution and in the solid sugar
Inference/ explanation:
Initially there were no radioactive sugar molecules in the solution
but due to dynamic nature of equilibrium, there is exchange between the
radioactive and non-radioactive sugar molecules between the two phases
Equilibrium involving dissolution of gas in liquid

At a given pressure there is an equilibrium

between the molecules of solute in gaseous
state & those in solution.
Effect of pressure on the solubility of a gas in
a liquid is given by Henry’s Law:
mass of a gas dissolved in a suitable solvent is
proportional to pressure of the gas

CO2 (g) ⇄ CO2 (aq)

 General Characteristics Of Physical Equilibrium
• Observable properties of the system becomes constant
• Can be attained only in closed system
• Dynamic in nature –two opposing reactions takes place at equal rates
• Concentration of different substances becomes constant at constant temperature
 Concept of dynamic equilibrium
Let us consider a general chemical reaction
A+B ⇌ C+D
• Increase in concentration of C and D occurs
• Decrease in concentration of A and B occurs
• At particular instant, rate of forward reaction = backward reaction
The system is said to have attained equilibrium
At equilibrium:The concentration of reactants & products remain constant.
 Dynamic nature of chemical equilibrium

Experiment
Equilibrium in beaker1 N2 + H2 ⇌ NH3
Equilibrium in beaker2 N2 + D2 ⇌ ND3
Mix up the contents of beaker 1 and 2

Observation:
NH2D, NHD2 , ND3 and HD are also there in the beaker in addition to
the original contents of beaker 1 and 2

Conclusion:
Scrambling of H and D atoms in the molecules must result from a
continuation of the forward and reverse reactions in the mixture.
If the reaction had simply stopped when they reached
equilibrium, then there would have been no mixing of isotopes .
 Law of chemical equilibrium
At a given temperature
The ratio of the concentration of the product to the concentration of the
reactant raised to their respective stoichiometric coefficient in the balanced
chemical equation is constant.
For a reversible reaction
aA + bB ⇌ cC + dD
Kc=[C]c [D]d/[B]b[A]a
where Kc is equilibrium constant
 Equilibrium constant of some reactions:

N2(g) + 3H2(g) ⇌ 2NH3(g); Kc=[NH3]2/[N2][H2]3

PCl5(g) ⇌ PCl3(g) + Cl2(g); Kc= [PCl3][Cl2]/[PCl5]

CH4(g) + H2(g) ⇌ CO(g) + 3H2(g) Kc=[CO][H2] 3/[CH4][H2]

[
Magnitude of equilibrium constant
For the reaction H2+I2 ⇌ 2HI (i)
Kc=[H I]2/[H2 ][I2]

For the reverse reaction of (i) 2HI ⇌ H2+ I2

Kc’=[H2 ][I2 ]/[HI]2 =1/Kc
Multiply (i) by some coefficient
½ H2+ ½ I2 ⇌ HI
Kc”=[H I] /[H2 ]1/2[I2]1/2=Kc1/2

Chemical equation Equilibrium constant

aA+bB⇌ cC+dD K
cC+dD ⇌aA+bB K1 =1/K
naA+nbB⇌ ncC+ndD K2 =Kn
Example
0.500 mole of HI is introduced into a 1.00 litre sealed flask and heated to a certain temperature. Under
this condition HI decomposes to produce H2 and I2 until an equilibrium is established. An analysis of the
equilibrium mixture shows that 0.105 mole of HI has decomposed. Calculate the equilibrium
concentrations of H2, I2 and HI, and the equilibrium constant Kc for the reaction.
The reaction:H2(g) + I2(g) ⇌ 2HI(g)
————————————————————————————
H2(g) + I2(g) ⇌ 2HI(g)
————————————————————————————
Initial [ ],M: 0.000 0.000 0.500
Change[ ],M: +0.0525 +0.0525 -0.105
Equilibrium [ ], M 0.0525 0.0525 0.395
Kc =
Kc=(0.395)2/(0.0525)2=56.6
Types of equilibrium
 Homogeneous equilibria

 Heterogeneous equilibria
Homogeneous Equilibria
All the reactants and products are in the same phase

CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g)

CO(g) + H2O(g) ⇌ CO2(g) + H2(g)

Equilibrium Constant in Gaseous Systems

Δn = (number of moles of gaseous products)

– (number of moles of gaseous reactants)
in the balanced chemical equation
Example:
 Relationship between KP and Kc

1. 2NO2(g) ⇌ N2O4(g);
Kp = Kc (RT)-1

2. H2(g) + I2(g) ⇌ 2 HI(g);

Kp = Kc

3. N2(g) + 3H2(g) ⇌ 2 NH3(g);

Kp = Kc(RT)-2
Equilibrium constant expressions for heterogeneous System.
Equilibrium in a system having more than one phase

The molar concentration of a pure solid or liquid is considered to be constant

 Important Features Of Equilibrium Constant

 The equation for K is applicable only when concentration of reactants and products
have attained constant value (Equilibrium has been established).

 The value of K is independent of the initial concentration of reactants and products

 The value of K varies with change in temperature.

 The equilibrium constant for the reverse reaction is equal to the inverse of the
equilibrium constant for the forward reaction.
Features of equilibrium constant
 Applications of the equilibrium constant
 Predicting the Extent of a Reaction

a) If Kc > 103 : products dominate over reactants,

• If Kc is very large ,the reaction proceeds nearly to completion
b) Kc < 10—3 : reactants predominate over products
• If Kc is very small, the reaction proceeds rarely.

c) Kc is in the range of 10-3 to 103 :appreciable concentrations of both reactants and products
 Predicting the Direction of the Reaction:

Qc > Kc, the reaction will proceed in the backward direction.

Qc < Kc, the reaction will proceed in the forward direction
Qc = Kc, the reaction is at equilibrium, no net reaction takes place
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 Calculating equilibrium concentrations from Equilibrium constant value
Example:
3.00 mol of PCl5 kept in 1L closed reaction vessel was allowed to attain equilibrium
at 380K. Calculate composition of the mixture at equilibrium. Kc= 1.80
Relationship between Kc, Qc & ΔG

ΔG = ΔGo + RT ln Q.

At Equilibrium, ΔG = 0, & Q = K
So, ΔGo = --RT lnK
ΔGo = --2.303RT logK

 If ΔGo < 0, then log K is +ve making K >1. The reaction has proceeded in the
forward direction to such an extent that the products are predominant.
 If ΔGo > 0, then log K is --ve making K <1. The reaction has proceeded in the
backword direction to such an extent that the reactants are predominant.
 Factors affecting Equilibria

Le Chatelier principle
Change in any of the factors that determine
the equilibrium conditions of a system will
cause the system to change in such a manner
so as to reduce or to counteract the effect of
the change.

We will look at the effect of the following on Equilibrium

• Effect of Concentration Change

• Effect of Pressure Change
• Effect of Temperature Change
• Effect of Inert Gas Addition
• Effect of addition of catalyst
  Effect of Concentration Change
A+B ⇌ C+D

• If you increase the concentration of A or B(reactant)

• System will try to decrease the concentration of A or B

(as per Le Chatelier principle)

• How ? : By forming more product

• Equilibrium moves to the right(forward direction)

EFFECT OF CONCENTRATION
 Effect of concentration

Effect Direction of Intensity of colour

reaction
a)Addition of SCN- forward reaction Intensity of Red colour
increases
b)Addition of Fe3+ ions forward reaction Intensity of Red colour
increases
c)Addition of oxalate backward Intensity of Red colour
ion(decreases concentration decreases
of Fe3+ ions)
Fe 3+ + C2O42- → [Fe(C2O4)3] 3–
 Effect of Pressure change
When the pressure of a gaseous system at equilibrium is subjected to an
increase in pressure, the reaction will take place in a direction so as to
decrease the pressure & this happens when the no. of moles of gas
decreases
Increase in Pressure shifts the reaction to the
direction with lesser number of gaseous moles

Consider the reaction: PCl5(g) ⇌ PCl3(g )+Cl2(g);

• Forward reaction results in more gas molecules.

• If mixture is compressed, pressure increases
reverse reaction occurs to reduce pressure
• If mixture is allowed to expand ,pressure drops
forward reaction occurs to compensate the decrease in pressure
 Consider the following reactions:
1. CO(g) + H2O(g) ⇌ CO2(g) + H2(g);
2. H2(g) + Cl2(g) ⇌ 2HCl(g);

• Reactions have same number of gas molecules in reactants and products.

• Reducing or increasing the volume will cause equal effect on both sides
– no net reaction will occur.
• Equilibrium is not affected by change in pressure

2SO2(g) + O2(g) ⇌ 2SO3(g),

• The total moles of gas decreases as reaction proceeds in the forward direction.
• If pressure is increased by decreasing the volume (compression), a forward reaction occurs to
reduce the stress.
• Reactions that result in fewer moles of gas is favored high pressure .
Effect of addition of inert gas

 At constant volume
the pressure of the system increases but the partial pressures & molar concentrations of
the reactants & products do not change.
So the equilibrium remains undisturbed

 At constant pressure
decreases the partial pressure of the reacting species.
Equilibrium shifts in the direction having more number of gaseous moles
  Effect of Temperature change
 When the temperature of the system at equilibrium is increased (by giving
heat to the system), the reaction will proceed in the direction in which it will
use up the heat provided. That is, the reaction will proceed in the direction in
which it is endothermic
 Equilibrium constant changes with change in temperature
 The Equilibrium constant for an
• Endothermic reaction increases with increase in temperature
• Exothermic reaction decreases with increase in temperature
 Effect of temperature
  Effect of a Catalyst
o A catalyst increases the rate of the reaction by making available a lower energy
pathway for the reaction to occur.
o It increase the rate of the forward as well as reverse reaction, but does not
affect the position of equilibrium.
o Catalyst just helps to attain the equilibrium faster.
o The catalyst lowers the activation energy of both the forward as well as reverse
reaction by exactly the same amount.
 Summary of Lechatelier Principle
Change Effect on Effect on Kc
Equilibrium

Concentration Changes No Change

Pressure Changes (If difference in No Change

no.of moles on product
and reactant side)

Temperature Changes Changes

Catalyst No Change No Change

Determine whether the following reactions are favored at high or low temperature

1. 2SO2(g) + O2(g) ⇌ 2 SO3(g); ∆Ho = -180 kJ

2. CO(g) + H2O(g) ⇌ CO2(g) + H2(g) ∆ Ho = -46 kJ
3. CO(g) + Cl2(g) ⇌ COCl2(g); ∆Ho = 108kJ
4. N2O4(g) ⇌ 2 NO2(g); ∆Ho =+57 kJ
5. CO(g) + 2H2(g) ⇌ CH3OH(g); ∆Ho = -270 kJ

Determine whether the following reactions favour high pressure.

1. 2SO2(g) + O2(g) ⇌ 2 SO3(g)

2. PCl5(g) ⇌ PCl3(g) + Cl2(g)
3. CO(g) + 2H2(g) ⇌ CH3OH(g)
4. N2O4(g) ⇌ 2 NO2(g)
5. H2(g) + F2(g) ⇌ 2 HF(g)
 Chemical Equilibria in Industrial Processes
Production of Sulphuric Acid, H2SO4;
1. S8(s) + 8 O2(g)  8SO2(g)
2. 2SO2(g) + O2(g) ⇌ 2SO3(g); ∆ H=-198 kJ
3. SO3(g) + H2SO4(l)  H2S2O7(l)
4. H2S2O7(l) + H2O(l)  2H2SO4(l)
 The second reaction is exothermic and has high activation energy;
though thermodynamically favoured the reaction is very slow at low
temperature.
 At high temperature reaction goes faster, but the yield would be very low
 An optimum condition of temperature and pressure and catalyst is used. .
Chemical Equilibria in Industrial Processes
The production of ammonia by the Haber- process:
N2(g) + 3H2(g) ⇌ 2NH3(g); ∆ H = -92 kJ

This reaction is exothermic and very slow at low temperature.

Increasing the temperature will increase reaction rate, but will
lower the yield.

An optimum condition is achieved at moderate temperature of 250

to 300oC with catalyst added to increase the reaction rate.

Increasing the pressure will favour product formation.

Reaction favors low temperature and high pressure conditions
Chemical Equilibria in Industrial Processes

The production of hydrogen gas:

Reaction: CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g);

 This reaction is endothermic with ∆H = 206 kJ

 Increasing the reaction temperature will increase both the rate and the yield.
 This reaction is favored at high temperature and low pressure conditions
  Recapitulation
Factors affecting chemical equilibrium
 Concentration-increase in concentration of reactants or decrease in concentration of
products results in forward reaction
 When the temperature of the system at equilibrium is
1) decreased ,the reaction will proceed in the direction in which it is exothermic
2) increased ,the reaction will proceed in the direction in which it is endothermic
 When a gaseous system at equilibrium is subjected to an increase in pressure, the reaction
will take place in a direction so as to decrease the pressure & this happens when the no of
moles of gas decreases
 Catalyst will not effect the position of equilibrium. It speeds up both the forward and
backward reaction by same magnitude. So it just helps to attain the equilibrium faster.
 Addition of Inert gas at constant volume has no effect on the equilibrium.
 Addition of inert gas at constant pressure, decreases the partial pressure of the reacting
species. Equilibrium shifts in the direction having more number of gaseous moles
Try these
1. True/False. The degree of dissociation of PCl5 decreases with the increase of pressure.
2. True/False. The degree of dissociation of HI(g) can be determined using vapour density method.
3. True/False. The equilibrium constant can be related with the standard free energy change as ln KC =  G°/RT.
4. True/False. An endothermic reaction proceeds in the forward direction with decrease of temperature.
5. True/False. Favorable conditions for the NH3 formation are high pressure and low temperature.
6. True/False. For a reversible system at constant temperature, the value of KC increases if concentrations are changed at
equilibrium.
7. In a reaction, x moles of a reactant are decomposed out of ‘a’ moles, the degree of dissociation of reactant is  .
8. True/False. The dissociation of CaCO3 is suppressed at high pressure of CO2.
9. True/False. The apparent molecular weight of PCl5 on dissociation show lower value.
10. If the temperature of a system at equilibrium is increased, the equilibrium will shift in the direction where heat  .

Answers
1. True
2. False
3. True
4. False
5. True
6. False
7. x/a
8. True
9. True
10. absorbed