CHEMCALEQULBRIUM

INTRODUCTION
Chemical reaction : Symboic representation of any chemical change in tems of reactants and products is
called chemical reaction.

Types of chemical reaction :

(a) On the basis of physical state
Homogeneous reactions
All reactants and products are in same phase.
N,g) + 3Hg’2NH)
Heterogeneous reactions
Reactants and products are in two or more phases.
Zn(s) + CO.g)’ZnOls) + COg
(b) On the basis of speed.
Fast reactions
Generally these reactions are ionic reactions.
HCI+ NaOH’ NaCl + H,0
Acid Base Salt Water
() Rate determination is almost impossible.
Slow reactions
Generally these reactions are molecular reactions.
H, +’2HI
(i Rate determination is possible.
(c) On the basis of heat
Exothermic reactions
() Heat is evolved in these type of chemical reactions.
R’P+x kcal
(i) Change in enthalpy. AH = ve
Endothermic reactions
Heat is absorbed in these type of chemical reactions.
R ’ P - x kcal
AH-(+) ve
On the basis of direction
Reversible reactions
() Chemical reaction in which products can be converted back into reactants.
N, + 3H, 2NH,
3Fe + 4H,0Fe,O, +4H,
H, +, 2HI
Proceed in forward as well as in backward direction.
(ii) Possible in cosed container.
(iv) These can attain equiibrium.
v) Reactants are never completely converted into products.
( Neutralisation reactions except of strong acid and strong base.

HCI + NH,OH: NH,CI +H,0

Ireversible reactions
Chemical reaction in which products cannot be converted back into reactants.
AgNO, + NaCI ’ AgCl + NaNO,
NaCl + H,So,’ NaHSO, +HC
Zn + H,So,’ Znso, +H,t
Proceed only in one direction (forward direction).
(üi Generally possible in open container.
(iv These do not attain equilibrium.
(v) Reactants are nearly completely converted into products.
a(vi)
Neutralisation reactions of strong acid and strong base.
HCI+ NaOH- ’ NaCl + H,0
EQUILIBRIUM :
loses its tendency for a change and all the properties associated with
mne state of equilibrium,system constant and do not vary without external
composition, etc become
yot ike pressure, temperature, which state of equilibrium isattained, it may be oftwo
stimulation. On the basis of nature of process in
types :
(A) Physical equilibrium (B) Chemical equilibrium

Equilibrium

Physical Equilibrium Chemical Equilibrium

Equilibrium in physical process is Equilibrium in chemical process
called équilibrium.physical
For example is called chemical equilibrium.
phase changes like
H,0() For example
HO(g); H,(g) + Clg) 2HI(g)
Solvation like
H,0
NaCl(s)= excess NaCl(aq)

Physical equilibrium:
Ifinasystem only physical state (phase) is changed and equilibrium is established, (i.e. there is no chemical
change), the equilibrium is calledphysical equilibrium. Ex :Fusion ofice, evaporation ofwater, dissolution
of salts,absorption of gases in liquid, etc.
Following are the types of common physical equilibria :
 Liquid-Vapour equilibria: In aclosed vessel, the vapours above the liquid are in equilibrium at
given temperature.
Ex. H,0() Ho(g)
(i) Solid-Liquid equilibria : This equilibriumcan be established only at melting point of solid. At this
stage solid and liquid phases exist simultaneously in equilibrium.
Ex H,O($) H,O() at melting point
Gi) Solid-Vapour equilibria :Let us now consider the systems where solids sublime to vapour
phase. If weplace solid iodine in a closed vessel, after sometime the vessel gets filled up with
violet vapour and the intensity of colour increases with time. After certain time the intensity
of colour becomes constant and at this stage equilibrium is attained. Hence solid iodíne sublimes
to give iodine vapour and the iodine vapour condenses to give solid iodine. The equilibrium
can be represented as,
,(solia) = , (vapour)
Other examples showing this kind of equilibrium are,
Camphor (solid) e.Camphor (vapour)
NH,CI (s0lid) NH,CI (vapour)

Chemical equilibriun:
Analogous to the physical systems, chemical reactions also attain a state of equilibrium. These reactions
can occur both in forward and backward directions. When the rates ofthe forward and reverse reactions
become equal, the concentrations of thereactants and the products become constant. This is the stage
of chemical equilibrium. This equilibrium consists of aforward reaction in which the reactants give
product(s) and reverse reaction in hich product(s) gives the original reactants.
We aways take forward direction if direction is not specified.
Invice-versa.
a reversible reaction if forward reaction is exothermnic then the backward reaction will be endothermic and
Rate of Reaction
The change in concentration of reactants or products in unit time is known as rate of the reaction.
()Change in concentration
Rate of reaction
time taken for the change
EQUILIBRIUM AND CHEMICAL PROCESS
(A) Chemical Equilibrium
The most important characteristic property of a reversible reaction is that it aways attains a state of
chemical equilibrium.
Consider a general reversible reaction in a closed vessel,

A+B C+D where, r, = rate of forward reaction

r, = rate of backward reaction
Initially reaction occurs in forward direction but as the concentration of products increases reaction also
starts in backward direction.
At acertain stage, rate of forward reaction becomes equal to the rate of backward reaction called
equilibrium state.
At equilibrium state : Rate of forward reaction (r) Rate of backward reaction r)

Rate of f
reaction oward
Equlibrium
state (, r)
Rate
ofbackward

aacion

Time taken to attain Time

equilibrium
(B) Characteristics of equilibrium :
The concentrations of the reactants and products do not change with time.
At this stage, number of moles of substances produced per second in the forward reaction is equal to
the number of moles of substances which disappear per second in the backward reaction.
Chemical equiibrium is dynamic in nature i.e. the reaction although appears to be stopped but
actually takes place in both the directions with the same speed.
Chemical equilibrium can be approached from both sides

2HI H, +, or H, +1 2HI
At equilibrium, each reactant and product has a constant concentration and this is independent of
the fact whether the reaction starts from forward direction or backward diredtion with the reactant
or with the product.
Equiibrium is not affected by the presence of catalyst. The catalyst only helps in attaining equilibrium
rapidly.
The measurable properties of the system like temperature, concentration, colour, density etc.
don't undergo any change with time at the chemical equilibrium conditions.
Homogeneous equiibrium is the equilibrium in which the reactants and products are in the same
phase.
H
CH,CO0 C,H,()+H,o() CH,COOH(() +C,H,OH(4)
Heterogeneous equilibrium is the equilibrium in which the reactants and products are in two or
more phases.

Zn(s) + CO,g) ZnOls) + COg)

LAW OF MASS ACTION
The law of mass action was given by Guldberg and Waage (1864).
It states that the rate of a chemical reaction is directly proportional to the product of active masses of the
reacting substances raised to a power equal to the stoichiometric coefficient in the balanced chemical
equation.
(A) Derivation of equilibrium constant :
Considera reversible homogeneous chemical reaction which has attained equilibrium state at a particular
temperature :

m,A +m,B n,C+ n,D

Let the active masses of A, B, Cand D be A] [B] [C] and [D] respectively at equilibrium.

According to law of mass action :

Rate of forward reaction

Rate of backward reaction (r,) [C (D

=k,[Af (B and = k[CP D
Where K, and K, are forward and backward rate or velocity constants respectively.
At equilibrium state

kilAf (BI =k,iCP D

k CD
ky ABf
K
(AB K
Kis knowm as equilibrium constant and has a definite value for every chemical reaction at particaular temperature.
The equilibrium constant at agiven temperature is the ratio of the rate constants of forward and backward
reactions,

Forms of K

Concentration Partial pressure

(KJ (K,)

For reaction m,A + m,B n,C + nD

K [CT D K, P" x(P,yr
(AT BT (P, x(P,
Unit of |= mol L! Unit of P= atm.