CHEMICAL EQUILIBRIUM PART-1

It is an experimental fact that most of the process including chemical reactions, when carried out in a closed
vessel, do not go to completion. They proceed to some extent leaving considerable amounts of reactants &
products. When such stage is reached in a reaction, it is said that the reaction has attained the state of
equilibrium. Equilibrium can be defined as a state at which both the opposite processes take place with equal
rate.

Equilibrium represents the state of a process in which the properties like temperature, pressure, and
concentration etc of the system do not show any change with passage of time. In all processes which attain
equilibrium, two opposing processes are involved. Equilibrium is attained when the rates of the two opposing
processes become equal. If the opposing processes involve only physical changes, the equilibrium is
called Physical Equilibrium. If the opposing processes are chemical reactions, the equilibrium is called Chemical
Equilibrium.

We will discuss about chemical and ionic equilibrium involving acid, base and salts in more detail under following
topics

Physical Equilibrium

?Physical equilibrium can be defined as the equilibrium in physical processes.

The different types of physical Equilibrium are briefly described

below

(a) Solid liquid Equilibrium

The equilibrium that exist between ice and water is an example of solid liquid equilibrium. In a close system,
at 0oC ice and water attain equilibrium. At that point rate of melting of ice is equal to rate of freezing of
water. The equilibrium is represented as

H2O(s) H2O(l)

(b) Liquid Gas Equilibrium

Evaporation of water in a closed vessel is an example of liquid gas equilibrium. Where rate of evaporation is
equal to rate of condensation. The equilibrium is represented as

H2O(l) H2O(g)
(c) Solid Solution Equilibrium

If you add more and more salt in water taken in a container of a glass and stirred with a glass rod, after
dissolving of some amount. You will find out no further salt is going to the solution and it settles down at the
bottom. The solution is now said to be saturated and in a state of equilibrium. At this stage, many molecule of
salt from the undissolved salt go into the solution (dissolution) and same amount of dissolved salt are deposited
back (Precipitation). Thus, at equilibrium rate of dissolution is equal to rate of precipitation.

Salt(Solid) Salt(in solution)

(d) Gas Solution equilibrium

Dissolution of a gas in a liquid under pressure in a closed vessel established a gas liquid equilibrium. The best
example of this type of equilibrium is cold drink bottles. The equilibrium that exists with in the bottle is

CO2(g) CO2(in solution)

Equilibrium in Chemical Process (Reversible and Irreversible Reactions)

A reaction in which not only the reactants react to form the products under certain conditions but also the
products react to form reactants under the same conditions is called a reversible reaction.

Examples are

1. 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)

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

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

If a reaction cannot take place in the reverse direction, i.e. the products formed do not react to give back the
reactants under the same condition it is called an irreversible reaction.

Examples are:

1. AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(g)

2. 2M(g) + O2(g) 2MgO(s)

Note: If any of the products will be removed from the system, reversible reaction will become irreversible one.

Generally, a chemical equilibrium is represented as

Where A, B are reactants and C, D are products.

Note:

The double arrow between the left hand part and right hand part shows that changes are taking place in both
the directions.

On the basis of extent of reaction, before equilibrium is attained chemical reactions may be classified into
three categories.
(a) Those reactions which proceed to almost completion.

(b) Those reactions which proceed to almost only upto little extent.

(c) Those reactions which proceed to such an extent, that the concentrations of reactants and products at
equilibrium are comparable.

The equilibrium state is dynamic and not static in nature. A reaction is said to have attained equilibrium when
the rate of forward reaction equals that of backward reaction

If all the reactants and products of any reaction under equilibrium are in same physical state, it is called
a homogeneous equilibrium?. For example,

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

Here, all the reactants and products are in same phase

Heterogeneous equilibrium? is that type of equilibrium in which ?the state of one or more of the reacting
species may differ i.e. all the reactants and products are not in same physical state.
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(l)?
Here, reactant is solid while in product all the solid, liquid and gaseous matter states are present.

Ionic Equilibrium

Chemical reactions mostly take place in solutions. Solution chemistry plays a very significant role in chemistry.
All chemical substances are made up of either polar units (called ions) or non-polar units. The activity of these
entities is more evident and pronounced in solution. The behaviour of these substances depends upon their
nature and conditions of the medium in which they are added. It is therefore necessary to understand the
principles that govern their behaviour in solution.

This type of equilibrium is observed in substances that undergo ionization easily, or in polar substances in which
ionization can be induced. Ionic and polar substances are more easily soluble in polar solvents because of the
ease of ionization taking place in the solvent medium. With the dissolution of ionic and polar substances in the
solvent, these solutions become rich in mobile charge carriers (ions) and thus can conduct electricity.
Substances, which are capable of conducting electricity are called as electrolytes while those substances which
are non-conducting are called as non-electrolytes.

Characteristics of Equilibrium State

i) It can be attained only if the reversible reaction is carried out in closed vessel.

ii) It can be attained from either side of the reaction.

iii) A catalyst can hasten the approach of equilibrium but does not alter the state of equilibrium.

iv) It is dynamic in nature i.e. reaction does not stop but both forward and backward reactions take place at
equal rate.

v) Change of pressure, concentration or temperature favours one of the reactions (forward or backward)
resulting in shift of equilibrium point in one direction.

Introduction of Law of Mass Action and Equilibrium Constant

Guldberg and Waage

established a relationship between rate of chemical reaction and the concentration of the reactants or, with
their partial pressure in the form of law of mass action. According to this law,

The rate at which a substance reacts is directly proportional to its active mass and rate of a chemical reaction
is directly proportional to product of active masses of reactants each raised to a power equal to corresponding
stoichiometric coefficient appearing in the balanced chemical equation.

rate of reaction [A]a.[B]b

rate of reaction = K[A]a[B]b

where K is rate constant or velocity constant of the reaction at that temperature.

Unit of rate constant (K) = [moles/lit]1n time1 (where n is order of reaction.)

Note:

For unit concentration of reactants rate of the reaction is equal to rate constant or specific reaction rate.

At equilibrium the rate of both forward and backward reactions become equal and after achieving equilibria,
the concentration of reactants and products remains constant as shown in figure.

Note:

Active mass is the molar concentration of the reacting substances actually participating in the reaction.

Hence,

Active mass = number of moles/volume in litres

Active mass of solid is taken as unity.

Also, Active mass of reactant (a) = Conc. activity coefficient

i.e. a = Molarity f for dilute solution f = 1

Applying Law of mass action for general reversible reaction

aA + bB cC + dD

Rate of forward reaction [A]a[B]b

or Rf = Kf [A]b [B]b

Similarly for backward reaction

Rb = Kb[C]c [D]d

At equilibrium Kf[A]a[B]b = Kb[C]c[D]d

The above equation is known as equilibrium equation and Kc is known as equilibrium constant.
The subscript c indicates that Kc is expressed in concentrations of mol L1
At a given temperature, the product of concentrations of the reaction products raised to the respective
stoichiometric coefficient in the balanced 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
the Equilibrium Law or Law of Chemical Equilibrium.

Equilibrium constant for the reverse reaction is the inverse of the equilibrium constant for the reaction in the
forward direction.

Equilibrium Constant In terms of Partial Pressures (Kp)

For reactions involving gases, it is more convenient to express the equilibrium constant in terms of partial
pressure.

The ideal gas equation is written as,

Where c or n/v is concentration expressed in mol/m3 (mol/L3) & R= 0.0831 bar litre/mol K.

This indicates that at constant temperature, pressure of any gas is directly proportional to its concentration.

For reaction in equilibrium,

We can write,

Using Ideal Gas Equation we get,

PA = CART = [A] RT

PB = CBRT= [B] RT

Pc = CCRT = [C] RT

Pd = CDRT= [D] RT

Substituting the above values we get,

where ?n = (number of moles of gaseous products) (number of moles of gaseous reactants) in the balanced
chemical equation. The above given equation represents relationship between kc and kp.

Equilibrium Constant of a reaction involving Condensed Phase: The expression for the equilibrium constant of
a reaction involving condensed phase (solid or liquid) and gaseous state is obtained by considering the
concentrations or partial pressures of only the gaseous species. The concentration of condensed phases being
constant are merged with the equilibrium constant.

Some facts about equilibrium constant

a) A very large value of KC or KP signifies that the forward reaction, as written, goes to completion or very
nearly so.

b) A very small numerical value of KC or KP signifies that the forward reaction, as written, does not go to any
significant extent.

c) A reaction is most likely to reach a state of equilibrium in which both reactants and products are present if
numerical value of KC or KP is neither very large nor very small.

d) The equilibrium constant of a forward reaction and that of its backward reaction are reciprocal of each
other.

e) If a chemical equation is multiplied by certain factor, its equilibrium constant must be raised to a power
equal to that factor in order to obtain the equilibrium constant for the new reaction.
The Reaction Quotient Q

Consider the equilibrium

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

At equilibrium

When the reaction is not at equilibrium this ratio is called QC i.e., QC is the general term used for the above
given ratio at any instant of time. And at equilibrium QC becomes KC.

Similarly, PCl2 PPCl2 / PPCl2 is called QP and at equilibrium it becomes KP.

If the reaction is at equilibrium, Q = Kc

A net reaction proceeds from left to right (forward direction) if Q < KC.

A net reaction proceeds from right to left (the reverse direction) if Q >Kc

Illustration: For the reaction,

A(g) + B(g) 2C(g) at 25C, in a 2 litre vessel contains 1, 2, 3 moles of respectively. Predict the direction of
the reaction if

(a) Kc for the reaction is 3

(b) Kc for the reaction is 6

(c) Kc for the reaction is 4.5

Solution:

A(g) + B(g) 2C(g)

Reaction quotient

Q=

(a) Q > Kc,therefore backward reaction will be followed

(b) Q > Kc The forward reaction is followed

(c) Q = Kc The reaction is at equilibrium

Significance of the Magnitude of Equilibrium Constant

A very large value of KC or KP signifies that the forward reaction goes to completion or very nearly so.

A very small value of KC or KP signifies that the forward reaction does not occur to any significant
extent.

A reaction is most likely to reach a state of equilibrium in which both reactants and products are
present if the numerical value of Kc or KP is neither very large nor very small.

Units of Equilibrium Constant

As we have learned that numerical value of equilibrium constant is a function of stoichiometric coefficient used
for any balanced chemical equation.

But, what will happen in the size of units of equilibrium constant when the stoichiometric coefficient of the
reaction changes? (If sum of the exponent for product is not equal to reactant side sum)

So for the sake of simplicity in the units of Kp for Kc the relative molarity or pressure of reactants and
products are used with respect to standard condition.

(For solution standard state 1 mole/litre and for gas standard pressure = 1 atm)

Now the resulting equilibrium constant becomes unitless by using relative molarity and pressure.

Illustration . The value of Kp for the reaction 2H2O(g) + 2Cl2(g) 4HCl(g) + O2(g) is 0.035 atm at 400oC, when
the partial pressures are expressed in atmosphere. Calculate K c for the reaction,
1/2O2(g) + 2HCl(g) > Cl2(g) + H2O(g)

Solution:

KP = KC (RT)n

n = moles of product - moles of reactants = 5 - 4 = 1

R = 0.082 L atm/mol K,

T = 400 + 273 = 673 K

0.035 = KC (0.082 673)

KC = 6.342 10-4 mol l-1

KC for the reverse reaction would be 1/KC

KC = 1/6.342104 = 1576.8 (mol l-1)-1

When a reaction is multiplied by any number n (integer or a fraction) the K'C or K'pbecomes (KC)n or (KP)n of the
original reaction.

KC for 1/2 O2(g) + 2HCl(g) > Cl2(g) + H2O(g)

is 1576.8 = 39.7 (mol.l-1)-

Illustration . Kp for the equilibrium, FeO(s) + CO(g) Fe(s) + CO2(g) at 1000oC is 0.4. If CO(g) at a pressure of 1
atm and excess FeO(s) are placed in a container at 1000oC, what are the pressures of CO(g) and CO2(g) when
equilibrium is attained?

Solution: Assuming ideal gas behaviour, partial pressures are proportional to the no. of moles present. Since
moles of CO2 formed equals moles of CO consumed, the drop in partial pressure of CO will equal the partial
pressure of CO2 produced. Let the partial pressure of CO2 at equilibrium be x atm. Then, partial pressure of
CO will be (1 - x) atm.

Since K = pCO2 / pco = x / 1 x = 0.4 => x = 0.286

Hence PCO = 1-x = 0.714 atm.

Introduction to Le Chateliers Principle

 When an equilibrium is
subjected to either a change in concentration, temperature or, in external pressure, the equilibrium will shift in
that direction where the effects caused by these changes are nullified.

Refer to the following Video for Le Chateliers Principle

This can be understood by the following example. Overall we can also predict the direction of equilibrium by
keeping in mind following theoretical assumption.

PCl5 > PCl3 + Cl2

Let us assume that we have this reaction at equilibrium and the moles of Cl 2, PCl3 and PCl5 at equilibrium are a, b
and c respectively, and the total pressure be P T.

Since

PT = (a+b+c) RT / V

KP = abRT / cV

Now if d moles of PCl3 is added to the system, the value of Q would be, a(b+d)RT / cV

We can see that this is more than KP. So the system would move reverse to attain equilibrium.

If we increase the volume of the system, the Q becomes abRT / cV' where V' > V. Q becomes less, and the
system would move forward to attain equilibrium.

If we add a noble gas at constant pressure, it amounts to increasing the volume of the system and therefore
the reaction moves forward.

If we add the noble gas at constant volume, the expression of Q remains as Q = abRT / cV and the system
continues to be in equilibrium. Nothing happens.
Therefore for using Le-Chatliers principle, convert the expression of KP and KC into basic terms and then see
the effect of various changes.

Effect of Change of Concentration on Equilibrium

Let us have a general reaction,

aA + bB cC + dD

at a given temperature, the equilibrium constant,

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

again if , , and are the number of mole of A, B, C and D are at equilibrium

then, Kc = []c[]d / []a[]b

If any of product will be added, to keep the Kc constant, concentration of reactants will increase i.e. the
reaction will move in reverse direction. Similarly if any change or disturbance in reactant side will be done,
change in products concentration will take place to minimise the effect.

Effect of Chenage of Temperature on Equilibrium

The effect of change in temperature on an equilibrium cannot be immediately seen because on changing
temperature the equilibrium constant itself changes. So first we must find out as to how the equilibrium
constant changes with temperature.

For the forward reaction, according to the Arrhenius equation,

And for the reverse reaction,

R = Reactant, P = Product
It can be seen that

For any reaction, H = Eaf Ear

From the equation,

logK2/K1 = Ho / 2.303R (1/T1 1/T2) it is clear that

(a) If Ho is +ve (endothermic), an increase in temperature (T2 > T1) will make K2 > K1, i.e., the reaction goes
more towards the forward direction and vice-versa.

(b) If Ho is -ve (exothermic), an increase in temperature (T2 > T1), will make K2 < K1 i.e., the reaction goes in
the reverse direction.

Increase in temperature will shift the reaction towards left in case of exothermic reactions and right in
endothermic reactions.

Increase of pressure (decrease in volume) will shift the reaction to the side having fewer moles of the gas;
while decreases of pressure (increase in volume) will shift the reaction to the side having more moles of the
gas.

If no gases are involved in the reaction higher pressure favours the reaction to shift towards higher density
solid or liquid.

Refer to the following Video for Arrhenius equation

Example . Under what conditions will the following reactions go in the forward direction?

(i) N2(g)+ 3H2(g) 2NH3(g) + 23 k cal.

(ii) 2SO2(g) + O2(g) 2SO3(g) + 45 k cal.

(iii) N2(g) + O2(g) 2NO(g) - 43.2 k cal.

(iv) 2NO(g) + O2(g) 2NO2(g) + 27.8 k cal.

(v) C(s) + H2O(g) CO2(g) + H2(g) + X k cal.

(vi) PCl5(g) PCl3(g) + Cl2(g)- X k cal.

(vii) N2O4(g) 2NO2(g) - 14 k cal.

Solution:
(i) Low T, High P, excess of N2 and H2.

(ii) Low T, High P, excess of SO2 and O2.

(iii) High T, any P, excess of N2 and O2

(iv) Low T, High P, excess of NO and O2

(v) Low T, Low P, excess of C and H2O

(vi) High T, Low P, excess of PCl5

(vii) High T, Low P, excess of N2O4.

Example: The equilibrium constant KP for the reaction N2(g) + 3H2(g) 2NH3(g) is 1.6 10-4atm-2 at 400oC.
What will be the equilibrium constant at 500oC if heat of the reaction in this temperature range is-25.14 k cal?

Solution: Equilibrium constants at different temperature and heat of the reaction are related by the

equation,

log KP2 = 25140 / 2.303 2 [773 673 / 773 673] + log 1.64 10-4

log KP2 = 4.835

KP2 = 1.462 105 atm2

Effect of Change of Pressure on Equilibrium

The effect of change of pressure on chemical equilibrium can be done by the formula.

Kp = QP P(n)

Case A: When n = 0

Kp = Qp

And equilibria is independent of pressure.

Case B: When n = ve

Kp = QP Pn = QP / Pn

Here with increase in external pressure, will shift the equilibrium towards forward direction to maintain K p.
Similarly, decrease in pressure will shift the equilibrium in the reverse direction.

Case C: When n = +ve

Kp = QP Pn and, effect will be opposite to that of Case B

Effect of Addition of Inert Gases to a Reaction at Equilibrium

1. Addition at constant pressure

Let us take a general reaction

aA + bB cC + dD

We know,

Where,

nC nD, nA, nB denotes the no. of moles of respective components and P T is the total pressure and n = total no.
of moles of reactants and products.

Now, rearranging,

Where n = (c + d) (a + b)

Now, n can be = 0, < 0 or > 0

Lets take each case separately.

a) n = 0 : No effect

b) n = +ve : Addition of inert gas increases the n i.e. is decreased and so is . So

products have to increase and reactants have to decrease to maintain constancy of Kp. So the equilibrium moves
forward.

c) n = ve In this case decreases but increases. So products have to decrease and

reactants have to increase to maintain constancy of Kp. So the equilibrium moves backward.

2. Addition at Constant Volume : Since at constant volume, the pressure increases with addition of inert gas

and at the same time n also increases, they almost counter balance each other. So can be safely
approximated as constant. Thus addition of inert gas has no effect at constant volume.
Effect of Catalyst on Equilibrium

Catalysts are the substances which alter the rate of a reaction without themselves getting consumed in the
reaction. Since the catalyst is associated with forward as well as reverse direction reaction. So, at equilibrium,
rate of forward reaction will be equal to rate of reverse reaction and hence catalyst effect will be same on
both forward as well as reverse. Hence catalyst never effect the point of equilibrium but it reduces the time to
attain the equilibrium.

Example: What will be the effect on the equilibrium constant on increasing the temperature.
Solution: Since the forward reaction is endothermic, so increasing the temperature, the forward reaction is
favoured. Thereby the equilibrium constant will increase.

Sample problem Kp for the reaction 2BaO2(s) 2BaO(s) + O2(g) is 1.6 104 atm, at 400C. Heat of reaction is
25.14 kcal. What will be the no. of moles of O2 gas produced at 500C temperature, if it is carried in 2 litre
reaction vessel?

Solution: We know that

log LP2/KP1 = H / 2.303R [1/T1 1/T2]

log KP2/1.6 104 = 25.14 / 2.330 2 103 [773 673 / 773 673]

=> KP2/1.46 105 atm

KP2 = p02 = 1.46 105 atm

Since, PV = nRT

1.46 105 2 = n 0.0821 773

n = 1.46 105 / 0.0821 773 = = 4.60 10-7