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05.Chemical Equilibrium 83-92

05.Chemical Equilibrium 83-92

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1
5. CHEMICAL EQUILIBRIUM
Synopsis:
Based on the direction of their occurrence Chemical reactions are two types.
 
Irreversible reactions:
in these reactions
 
reactants are converted into products and products cannot beconverted into reactants.
There are unidirectional as they occur in one direction. i.e. Reactants
products.
These are denoted by single arrow mark.
These reactions almost go for completion i.e. reactants are almost completely convert into products.
Precipitation – ionic reactions, explosive reactions, strong acid – strong base neutralisation reactions,combustion- reactions are irreversible.Eg :1) 2KClO
3(s)
2KCl
(s)
+ 3O
2(g)
 2) NH
4
NO
2(s)
 
N
2(g) 
+ 2H
2
O
(g) 
3) C
2
H
5
OH
(l)
3O
2(g)
 
2CO
2(g)
+ 3H
2
O
(g)
4) 2Mg
(s)
+ O
2(g)
 
2MgO
(s)
 5) HCl
(aq) 
+ NaOH
(aq)
 
NaCl
(aq)
+ H
2
O
(l)
 6) H
2(g)
+ F
2(g)
 
2HF
(g)
 7) H
2(g)
+ Cl
2(g)
 
2HCl
(g)
Reversible reactions :
A reaction is said to be reversible, if both the forward and the backward reactions are taking placesimultaneously under the given experimental conditions.
Reactants giving rise to products is known as forward reaction.
Products giving rise to reactants is known as reverse reaction (or) backward reaction.
Reversible reactions are represented by writing a pair of half headed – arrows pointing in opposite directionsin between the reactants and products.Reactants products
A reverse reaction does not go to completion.
Most of the reversible reactions are carried in the closed vessels.Eg : 1) H
2(g)
+ I
2(g)
 
2HI
(g)
2) PCl
5(g)
 
PCl
3(g)
+ Cl
2(g)
3) 2NO
2(g)
 
N
2
O
4(g)-
4) N
2(g)
+ O
2(g)
 
2NO
(g)
 5) 2SO
2(g)
+ O
2(g)
 
2SO
3(g)
 6) CaCO
3(s)
 
CaO
(s)
+ CO
2(g)
 7) CH
3
COOH
(l)
+ C
2
H
5
OH
(l)
 
CH
3
COOC
2
H
5(l)
H
2
O
(l)
 
Equilibrium State :
The stage or state at which the rate of forward reaction is equal to the rate of the reverse reaction in areversible reaction is known as the equilibrium stage or state.
The chemical equilibrium is considered as dynamic equilibrium because the forward and the reverse reactions
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Chemical Equilibrium 
2
continue to take place simultaneously at this stage also.
Equilibrium is established ini) a reversible reaction ii) in a closed vessel
In the beginning in a reversible reaction the rate of forward reaction is more since the concentration ofreactants is more.
As time proceeds the rate of forward reaction decreases as the concentrations of reactants decreases.
In the beginning in a reversible reaction the rate of backward reaction is absolutely zero because theconcentration of products is zero.
AS time proceeds the rate of backward reaction increases since the concentrations of products also increases.
At one stage the rate of forward reaction becomes equal to rate of backward reaction and no further changeoccurs in the concentration of reactions or products.
At equilibrium, the concentration of reactants and products may not be equal but they remain constant.
Characteristics of chemical equilibrium :
The rate of the forward reaction is equal to the rate of the reverse reaction.
The concentrations of the reactants and the products remain unchanged with time.
The observable properties such as pressure, concentration, density, colour also remain unchanged with time.
The attainment of chemical equilibrium can be recognised by the constancy in some macroscopic potterieslike pressure, concentration, density, color etc.
The equilibrium is dynamic in nature. Both the forward reaction and the reverse reaction continue to take placesimultaneously with equal rates.
A catalyst does not alter the state of equilibrium or the composition of the chemical substances of the reactionat the equilibrium. It only speeds up the attainment of the equilibrium.
Chemical equilibrium can be established from either side of the reversible reaction.
Chemical equilibrium can be homogeneous or heterogeneous and also ionic or molecular.
The factors such as pressure, concentration temperature presence of inert gas influence the position of theequilibrium.
At equilibrium, the value of Gibbs free energy change (
Δ
G) is zero (
Δ
G = 0).
At equilibrium,
Δ
S is maximum.
The equilibrium does not tell us how long it takes for a reaction to attain equilibrium.
Once equilibrium is reached, it continues forever until the conditions like pressure, temperature, concentrationetc, are altered.
At equilibrium the concentration of reactants may be equal or less or more than the concentration of products.
Law of mass action :
This laws stated by C.M. Guldberg and P. Wage in 1863.
This law gives the relation between the rate of a reaction and the concentration of the reactants.
The rate of a chemical reaction at a temperature at any instant is proportional to the product of the activemasses of the reactants.
This law is applicable to all reactions i.e. reversible and irreversible occurring in the gas phase or in the liquidphase.
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Chemical Equilibrium 
3
aA + bB
cC + dD, the equilibrium constant.
[ ] [ ][ ] [ ]
badcbfc
BADCkkk
==
 K
f
= forward reaction rate constant.K
b
= backward reaction rate constant.
The equilibrium constanttstanreacofionconcentrattheofproduct productsofionconcentrattheofproduct k
c
=
 
Partial pressure of the gas = mole fraction of gas
×
total pressure.
bBaAdDcCbfp
p.pp.pkkK
==
 
 tstanreacofpressurespartialofproduct productsofpressurespatialofprodct K
p
=
 k
c
= equilibrium constant in terms of molar concentration.k
p
=equilibrium constant in terms of partial pressure.Active mass =litresinvolumemolesof.no  Active mass is considered for gas or liquid.
The active mass of a solid is unity whatever may be its mass.
Types of chemical equilibrium:
Based on the physical states of substances equilibrium is of two types.
1) Homogeneous equilibrium
: All the reactants and products are present in same physical state. i.e samephase.Eg :1) 2SO
2(g)
+ O
2
2SO
3(g)
2) N
2(g)
+ 3H
2(g)
2NH
3(g)
3) CH
3
COOC
2
H
5(l)
+ H
2
O
(l)
CH
3
COOH
(l)
+ C
2
H
5
OH
(l) 
4) CH
3
COOH
(l)
CH
3
COO
 – (l)
+ H
+(l)
2) Heterogeneous equilibrium
: Reactants and products are in different physical states or different phase.Eg : 1) CaCO
3(s)
CaO
(s)
+ CO
2(g)
2) NH
4
HS
(s)
NH
3(g)
+ H
2
S
(g)
3) Fe
(s)
+ 4H
2
O
(g)
Fe
3
O
4(s)
+ 4H
2(g)
Relationship between k
p
and k
c
:k
p
= k
c
(RT)
Δ
n
R = gas constant, T = absolute temperature
Δ
n = change in number of moles= n
P
- n
R
(no.of moles of gaseous products – no.of moles of gaseous reactants )case (i) if n
P
= n
R
,
Δ
n = 0, k
p
= k
c
Eg. H
2
+ I
2
2HI(ii) if n
P
> n
R,
 
Δ
n = +ve, k
p
> k
c
 
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