07 Chemical Equilibrium Formula Sheets Quizrr

CHEMICAL EQUILIBRIUM
IRREVERSIBLE AND REVERSIBLE REACTION
Irreversible Reaction
The chemical reaction which proceed in such a way that reactants are completely converted into products i.e. the
reactions which move in one direction are called Irreversible Reaction.
e.g. H2SO 4  2NaOH 
 Na 2SO4  2H2 O
Reversible Reaction
The chemical reactions which proceed in both the direction and do not reach to completion are known as reversible
reaction.
e.g. ˆˆˆˆˆ
3Fe  4H 2 O ‡ˆˆˆˆ †
Forward
ˆ Fe3 O4  H 2
Re verse
State of Chemical Equilibrium

Chemical equilibrium is that state at which both forward and backward reaction occurs at the same rate.
Thus at equilibrium state,
Rate of forward reaction = Rate of backward reaction.
Ra t e
of f
Rate orw
ard
Equilibrium state
rd
wa
a ck
b n
o f tio
te ac
Ra re
Time
Characteristics of equilibrium state
(1) Equilibrium is dynamic in nature.
(2) At constant temperature, certain properties such as pressure, concentration, density or colour becomes
constant.
(3) Equilibrium Can be attained from either side i.e. from the side of reactants or products.
ˆˆ† H 2  I 2
2HI ‡ˆˆ
ˆˆ† 2HI
or H 2  I 2 ‡ˆˆ
(4) Catalyst does not change the equilibrium state but it helps in attaining it rapidly.
Homogeneous and Heterogeneous Equilibrium
Homogenous Reaction : The reversible reaction in which all the reactants and the products are in same
physical state.
e.g. (a) ˆˆ† 2HI(g)

H 2 (g)  I 2 (g) ‡ˆˆ
O
||
(b) ˆˆ† H 3C  C  O  C 2 H 5 (l )  H 2 O(l )
H3 C  COOH(l )  C 2 H 5 OH(l ) ‡ˆˆ
[1]
[2]
Heterogenous Reaction :
The reversible reaction in which more than one phase is present.
ˆˆ† CaO(s)  CO 2 (g)
CaCO3 (s) ‡ˆˆ
LAW OF CHEMICAL EQUILIBRIUM AND EQUILIBRIUM CONSTANT

Let the reversible reaction may be represented as
ˆˆ† C  D
A  B ‡ˆˆ
(forward rate) rf = kf [A] [B]
(backward rate) rb = kb [C] [D]
where kf and kb are forward and backward rate constants respectively.
At equilibrium rf  rb
k f [A][B]  k b [C][D]
k f [C][D]
K 
k b [A][B]
 Hence the equilibrium constant of a reversible reaction is the ratio of the velocity constants of the forward
and the backward reaction and is denoted by K.
PROPERTIES OF EQUILIBRIUM CONSTANT

(a) It does not depend on initial concentration, because product will be formed in more amount when concentration
of the ractants is increased, since the value of K remains constant.
(b) The value of K is constant at a fixed temperature but on increasing the temperature, value of K will change
because concentration of reactants and products undergoing chemical reaction increases on increasing
temperature.
(c) When the value of ‘KC’ is more than 1.0 then product is formed in greater amount, i.e. forward reaction is
faster but when it is less than 1.0 the product is formed in lower amount, i.e. backward reaction is faster.
(d) Value of KC remains unaffected by the presence of catalyst, because catalyst has equal effect on the rates
of forward and backward reactions.
(e) If the same reaction is brought to equilibrium by two different methods the values of equilibrium constant will
be different under the two conditions.
ˆˆ† 2NH3  K1
(1) N 2  3H 2 ‡ˆˆ
[NH 3 ]2
K1 
[N 2 ][H 2 ]3
1 3 ˆˆ†
N 2  H 2 ‡ˆˆ NH3  K 2
2 2
[NH3 ]
K2  3
Therefore K 2  K1
[N 2 ]1/ 2 [H 2 ] 2
(2) ˆˆ† C  D  K1
A  B ‡ˆˆ
ˆˆ† A  B  K 2
and for, C  D ‡ˆˆ
1
Than K 2  K
1
[3]
RELATIONSHIP BETWEEN KP AND KC

n g
K p  K c (RT)
n = no. of moles of gaseous product – no. of moles of gaseous reactant

Three cases may arise
1st Case : when n g  0
Kp  KC
IInd Case : when n g  0  n g   ve 
Kp  KC
IIIrd Case : when n g  0  n g   ve 

Kp  KC
APPLICATION OF LAW OF MASS ACTION ON HOMOGENOUS EQUILIBRIUM
(a) (1) ˆˆ† 2HI(g)

H 2 (g)  I 2 (g) ‡ˆˆ
Assuming that ‘a’ mole of H2 reacts with ‘b’ mole of I2 in a closed container of ‘V’ litre. At equilibrium ‘x’
mole of H2 reacts with ‘x’ mole I2 to form ‘2x’ mole of HI.
H2 + I2 ˆˆ†
‡ˆˆ 2HI
a b 0 ......Number of initial molecules
(a–x) (b–x) 2x ......Molecules at equlibrium
ax bx 2x
......Active mass at equilibrium
V V V
4x 2
KC 
(a  x)(b  x)
Calculation of Kp :
H2 + I2 ˆˆ† 2HI
‡ˆˆ
a b 0 ----- Number of initial mole
(a–x) (b–x) 2x ----- Mole at equilibrium
Number of total mole in the reaction at equilibrium = a – x + b – x + 2x = a + b
(PHI )2
Kp 
(PH 2 )(PI2 )
4x 2
KP 
(a  x)(b  x)
Therefore, Kc  Kp
Pressure does not appear in the equation of Kp. Therefore such a reaction does not depend on pressure.
LE CHATELIER’S PRINCIPLE
If a system at equilibrium is subjected to a change the equilibrium shifts in that direction where the effect of the
brought change is nullified.
[4]
(1) Change of Concentration : In general, in a chemical equilibrium, increasing the concentrations of reactants
results in shifting the equilibrium in favour of product and vice-versa.
(2) Change of pressure : It can effect the equilibrium when n  0 .An increase in pressure to a system at
equilibrium, favours the reaction in that direction on where less number of moles of gases are formed and vice-
versa.
(3) Change in Temperature
(a) Endothermic Reaction
ˆˆ† PCl3 (g)  Cl 2 (g)
PCl5 (g) ‡ˆˆ
Increase in temperature will shift the reaction towards right i.e product side.
(b) Exothermic Reaction
ˆˆ† 2NH 3 (g) ; H   ve
N 2 (g)  3H 2 (g) ‡ˆˆ
Increase in temperature will shift the reaction towards left.
EQUILIBRIUM CONSTANT AND ITS UNIT

Equilibrium constant can be dimensional if the standard state of the substance is not considered. In that case,
ng
Unit of KC = (Mol / L) n and Unit of Kp = (bar or atm)
In modern days we express equilibrium constants as dimensionless quantities by specifying the standard state of
the reaction and product.
Example :
The standard state for pure gas is 1 bar and now the partial pressures are measured with respect to this standard.
2bar
Thus a pressure of 2bar in terms of this standard state is equal to ,  2 a dimensionless number..
1bar

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CHEMICAL EQUILIBRIUM

IRREVERSIBLE AND REVERSIBLE REACTION

State of Chemical Equilibrium

e.g. (a) ˆˆ† 2HI(g)

LAW OF CHEMICAL EQUILIBRIUM AND EQUILIBRIUM CONSTANT

PROPERTIES OF EQUILIBRIUM CONSTANT

RELATIONSHIP BETWEEN KP AND KC

n = no. of moles of gaseous product – no. of moles of gaseous reactant

IInd Case : when n g  0  n g   ve 

IIIrd Case : when n g  0  n g   ve 

APPLICATION OF LAW OF MASS ACTION ON HOMOGENOUS EQUILIBRIUM

(a) (1) ˆˆ† 2HI(g)

EQUILIBRIUM CONSTANT AND ITS UNIT

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