Chemical Equilibrium: Chemistry

CHEMISTRY
MICRO-XI
CHEMICAL EQUILIBRIUM
" A SPECIALLY DESIGNED KIT FOR LEARNING."
THE KEY  Basic principles of subjects. An outline of the

topics to be discussed in class lectures.
THE ATLAS  Basic layout of subject. A route map correlating
different subtopics in coherent manner.
EXERCISE I  A collection of good problems.
EXERCISE II  Test your objective skill.
QUESTION BANK  Test your objective skill.
EXERCISE III  A collection of previous years JEE problems.
PHYSICAL CHEMISTRY N.A. (SODIUM SIR)
THE KEY
CHEMICAL EQUILIBRIUM
Most of the chemical reaction do not go to completion in a closed system and attain a state of equilibrium.
Equilibrium is said to have reached in a physical or chemical system when rate of forward and reverse
processes are equal. At equilibrium macroscopic properties of the system like concentration, Pressure ect.
become constant at constant temperature.
State of chemical equilibrium is characterised by equilibrium constant. Equilibrium constant have constant
value at a given temperature.
UNDERSTANDING EQUILIBRIUM
There are two approaches to understand nature of equilibrium. One stems from kinetics as developed by
Guldberg and Wagge (1863). The other approach comes from thermodynaics. Equilibrium criteria is explained
on the basis of thermodynamic function like H, S and G.
According to kinetic approaches -The state of equilibrium is characterised by equal rate of forward and
backward process.
For Chemical equilibrium Rate of forward reaction = Rate of backward reaction.
For Physical equilibrium Rate of forward process = Rate of backward process
IMPORTANT CHARACTERISTIC OF EQUILIBRIUM
(i) Equilibrium is possible only in closed system.
(ii) The rate of forward process at equilibrium is equal to rate of backward process.
(iii) All measurable properties of system remain constant over time.
(iv) When equilibriums is attained for a physical process, it is characterised by constant value of one of its parameter.
(v) The constant value of these parameters indicate extent to which equilibria is shifted in forward direction.
(vi) Both, Kinetic and Thermodynamics theories can be invoked to understand the extent to which a reaction
proceed to forward direction. e.g. If extent of reaction is too large for forward direction (equilibrium is tilted
heavily to forward direction) than
(a) Specific rate of forward reaction >>> specific rate of backward reaction
(b) Product is thermodynamically very stable as compared to reactant.
(c) Gibb's function of product is vary small as compared to Gibb's function of reactant.
LAW OF CHEMICAL EQUILIBRIUM OR MASS ACTION (By Guldberg and Waage)
A general equation for a reversible reaction may be written
mA + nB xC + yD
rate of reaction in inforward direction(rf) [A]m [B]m ; rf = kf [A]m [B]m
rate of reaction in inforward direction(rb) [C]x [D]y ; rb = kb [C]x [D]y
At equilibrium, rf = rb
[ C] x [ D ] y
Keq or Kc = where Kc = kf / kb
[A ]m [B]m
where we use [ ] to indicate "molar concentration."
CONCENTRATION Vs TIME GRAPH FOR HABER PROCESS
N2(g) + 3H2(g) 2NH3(g)
Starting with pure H2 and N2 as reaction proceeds in forward direction. Ammonia is formed. At initially conc.
of H2 and N2 drops and attain a steady value at equilibrium. On the others hand conc. of NH3 increases and
at equilibrium attains a constant value.
Join with code VIBRANTLIVE for 10% discount on your subscription. [2]
Concentration time graphs for Concentration time graph for H2 + I2 2HI
N2 + 3H2 2NH3

HOMOGENEOUS CHEMICAL EQUILIBRIA
A homogeneous equilibrium is equilibrium with in a single phase i.e. when physical state of all the reactants
and product are same.
LIQUID PHASE HOMOGENEOUS EQUILIBRIUM
Example : (i) I2 (aq) + I– (aq) I3– (aq)
(ii) Hg 22 (aq) + NO3 (aq) + 3H3O+(aq) 2Hg2+ (aq) + HNO2(aq) +4H2O(l)
(iii) NH3(aq) + H2O (l) NH4+(aq) + OH– (aq)

Eq. constants for
[ I 3 (aq )]
(i) KC =
[ I 2 (aq )][ I  (aq )]
[Hg 2 ]2 [HNO 2 ]
(ii) KC =
[Hg 22 ][ NO3 ][H 3O  ]3
[ NH 4  (aq)][OH  (aq )]
(iii) KC =
[ NH 3 (aq )]
The subscrit 'C' denoting active masses of solute expressed in terms of molar concentration.
HOMOGENEOUS EQUILIBRIA IN GASES
Example : (i) C2H6(g) C2H4(g) + H2(g)

(ii) 3O2(g) 2O3(g)
(iii) C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g)
Equilibrium constant expression for then are
[C 2H4 ][H2 ] (PC2H4 )(PH2 )

(i) KC = [C 2H6 ] ; KP = (PC2H6 )
[ ] represents concentration PC2H 4 & other are partial pressure at equilibrium

in mol/ litre at equilibrium
3
[O3 ]2 PO2 3 [CO 2 ]2 [H 2O]4 PCO ·P 4
2 H 2O
(ii) KC = ; KP = (iii) KC = ; KP =
[O 2 ]3 PO3 2 [C3H 8 ][O 2 ]5 PC3H8 ·PO5 2
Note : Equilibrium constant for gaseous homogeneous equilibrium can be expressed in two ways KP and KC. This
means value of equilibrium constant depends upon choice of standard state in which concentration of reactant's
and product are expressed.
HETROGENEOUS EQUILIBRIA
If reactants and product are found in two or more phases, the equilibria describing them is called hetrogeneous
equilibrium.
Example: (i) PbCl2(s) Pb2+(aq) + 2Cl– (aq)
(ii) CaO(s) + CO2(g) CaCO3(s)
(iii) Br2 (l) Br2(g)
Equilibrium expression for them can be written as
(i) K = [Pb2+(aq)][Cl–(aq)]2
1 1
(ii) KP = ; KC =
PCO [CO 2 (g )]
2
(iii) KP = PBr (g) ; KC = [Br2(g)]

2
Note : We should calculate the value of K from the activities of the reactants and products rather than from their
concentrations. However, the activity of a dilute solute is usefully approximated by its molar concentration, so
we will use concentrations as approximated by its pressure (in atmospheres), so we use pressures for gases.
However, we also can use molar concentrations of gases in our equilibrium calculations, because the molar
concentration of a gas is directly proportional to its pressure. The activity of a pure solid or pure liquid is 1, and
the activity of a solvent in a dilute solution is close to 1. It is because as pure solids and liquid took part in
reaction, their concentration (or density) remain constant. Thus these species (solids, liquids, and solvents)
are omitted from reactions quotients and equilibrium calculations.
UNIT OF EQUILIBRIUM CONSTANT
We have already noted that the value of an equilibrium constant has meaning only when we give the
corresponding balanced chemical equation. Its value changes for the new equation obtained by multiplying
or dividing the original equation by a number. The value for equilibrium constant, KC is calculate substituting
the concentration in mol/L and for KP by substituting partial pressure in Pa, kPa, etc. in atm. Thus, units of
equilibrium constant will turn out to be units based on molarity or pressure, unless the sum of the exponents
in the numerator is equal to the sum of the exponents in the denominator. Thus for the reaction:
H2(g) + I2(g) 2HI, KC and KP do not have any unit
N2(g) + 3H2(g) 2 NH3 , KC has unit (mol/L)–2 and KP has unit bar–2 or
N2O4 (g) 2NO2, KC has unit mol / L and KP has unit bar
However, these days we express equilibrium constants in dimensionless quantities by specifying the standard
state of the reactants and the products. The standard state for pure gas is 1 bar and now the partial pressure
are measured with respect to this standard. Thus a pressure of 2 bar in term of this standard state is equal
to 2 bar / 1 bar = 2, a dimensionless number. Similarly for a solute the standard state; C0, is 1 molar solution
and all concentrations are measured with respect to it. The numerical value of equilibrium constant depends
on the standard state chosen.
APPLICATION OF EQUILIBRIUM CONSTANT
Before we consider the applications of equilibrium constants, let us consider its important features:
(I) The expression for equilibrium constant, K is applicable only when concentrations of the reactants and
products have attained their equilibrium values and do not change with time.
(II) The value of equilibrium constant is independent of initial concentration of the reactants and product. Equilibrium
constant has one unique value for a particular reaction represented by a balanced equation at a given
temperature.
(III) The equilibrium constant, K for a reaction is related to the equilibrium constant of the corresponding reaction
whose equation is obtained by multiplying or dividing the equation for the original reaction by a small integer.
Now we will consider some applications of equilibrium constant and use it to answer question like:
(i) predicting the extent of a reaction on the basis of its magnitude.
(ii) predicting the direction of the reaction, and
(iii) calculating equilibrium concentration.
Predicting the extent of a reaction

The magnitude of equilibrium constant is very useful especially in reactions of industrial importance. An
equilibrium constant tells us whether we can expect a reaction mixture to contain a high or low concentration
of product(s) at equilibrium. (It is important to note that an equilibrium constant tells us nothing about the rate
at which equilibrium is reached). In the expression of KC, product of the concentrations of products is written
in numerator and the product of the concentrations of reactants is written in denominator. High value of
equilibrium constant indicates that product(s) concentration is high and its low value indicates that
concentration of the product(s) in equilibrium mixture is low.
For reaction, H2 (g) + Br2(g) 2HBr(g), the value of
(PHBr ) 2
 KC = KP =
(PH )(PBr ) = 5.4 × 10
18
2 2
The large value of equilibrium constant indicates that concentration of the product, HBr is very high and
reaction goes nearly to completion.
Similarly, equilibrium constant for the reaction H2(g) + Cl2(g) 2HCl(g) at 300 K is very high and reaction
goes virtually to completion.
[ HCl ]2
KC = = 4.0 × 1031
[ H 2 ][ Cl 2 ]
Thus, large value of KP or KC (larger than about 103), favour the products strongly. For intermedicate values
of K (approximately in the range of 10–3 to 103), the concentrations of reactants and products are comparable.
Small values of equilibrium constant (smaller than 10–3), favour the reactants strongly.
At 298 K for reaction, N2(g) + O2(g) 2NO(g)
[ NO ]2
KC = = 4.8 × 10–31
[ N 2 ][ O 2 ]
The very small value of KC implies that reactants N2 and O2 will be the predominant species in the reaction
mixture at equilibrium.
Predicting the direction of the reaction.
 The equilibrium constant is also used to find in which direction reaction mixture of reactants and products will
proceed. For this purpose, we calculate the reaction quotient, Q. The reaction quotient is defined in the same
way as the equilibrium constant ( with molar concentrations to give QC, or with partial pressure to give QP) at
any stage of reaction. For a general reaction:
aA + bB cC + dD
[C]c [D]d
QC =
[A]a [B]b
Then, if QC > Kc , the reaction will proceed in the direction of reactants (reverse reaction).
if QC < Kc, the reaction will move in the direction of the products
if QC = Kc, the reaction mixture is at equilibrium.
In the reaction, H2(g) + I2(g) 2Hl(g), if the molar concentrations of H2 , I2 and HI are 0.1 mol L–1
respectively at 783 K, then reaction quotient at this stage of the reaction is
[ HI]2 ( 0 .4 ) 2
QC = = = 8
[H 2 ][ I 2 ] (0.1)(0.2)
KC for this reaction at 783 K is 46 and we find that QC < KC. The reaction, therefore, will move to right i.e.
more H 2 (g) and I 2 (g) will react to form more HI (g) and their concentration will decrease till
QC = KC.
FACTOR'S AFFECTING EQUILIBRIA
EFFECT OF CHANGE IN CONCENTRATION ON EQUILIBRIUM

A chemical system at equilibrium can be shifted out of equilibrium by adding or removing one more of
reactants or products. Shifting out of equilibrium doesn't mean that value of equilibrium constant change.
Any alteration of concentration of reactant or product will disturb the equilibrium and concentration of reactant
and product one readjust to one again attain equilibrium concentration.
In other word, as we add or remove reactant (or product) the ratio of equilibrium concentration become 'Q'
(reaction quotient) and depending upon.
Q < K : equilibrium will shift in forward direction.
Q >K : equilibrium will shift in backward direction.
Example : Fe3+ (aq) + SCN– (aq) Fe (SCN)2+(aq)
[Fe(SCN)2 ]
(i) adding Fe3 or SCN– will more = Q less then KC and equilibria will shift in forward direction.
[Fe3 ][SCN  ]
(ii) Removing Fe(SCN)2+will have same effect
(iii) Adding Fe(SCN)2+from outside source in equilibrium mixture will have effect of increasing 'Q' hence reaction
shift in backward direction.
EFFECT OF CHANGE IN PRESSURE

Sometimes we can change the position of equilibrium by changing the pressure on a system. However,
changes in pressure have a measurable effect only in system where gases are involved – and then only when
the chemical reaction produces a change in the total number of gas molecules in the system.
As we increase the pressure of a gaseous system at equilibrium, either by decreasing the volume of the
system or by adding more of the equilibrium mixture, we introduce a stress by increasing the number of
molecules per unit of volume. In accordance with Le Chatelier's principle, a chemical reaction that reduces
the total number of molecules per unit of volume will be favored because this relieves the stress. The reverse
reaction would be favoured by a decrease in pressure.
Consider what happens when we increase the pressure on a system in which NO, O2 and NO2 are in
equilibrium.
Example : 2NO(g) + O2 (g) 2NO2(g)
The formation of additional amounts of NO2 decreases the total number of molecules in the system, because
each time two molecules of NO2 form, a total of three molecules of NO and O2 react. This reduces the total
pressure exerted by the system and reduces, but does not completely relieve, the stress of the increased
pressure. On the other hand, a decrease in the pressure on the system favors decomposition of NO2 into NO
and O2 which tends to restore the pressure.
Let us now consider the reaction
N2(g) + O2 (g) 2NO(g)
Because there is no change in the total number of molecules in the system during reaction, a change in
pressure does not favor either formation or decomposition of gaseous nitric oxide.
EFFECT OF CHANGE IN TEMPERATURE ON EQUILIBRIUM
Changing concentration or pressure upsets an equilibrium because the reaction quotient is shifted away
from the equilibrium value. Changing the temperature of a system at equilibrium has a different effect: A
change in temperature changes the value of the equilibrium constant. However, we can predict the effect of
the temperature change by treating it as a stress on the system and applying Le Chatelier's principle. When
hydrogen reacts with gaseous iodine, energy is released as heat is evolved.
H2(g) + I2(g) 2I(g) H = – 9.4 kJ (exothermic)

Because this reaction is exothermic, we can write it with heat as a product.
H2(g) + I2(g) 2HI(g) + 9.4 kJ
Increasing the temperature of the reaction increases the amount of energy present. Thus, increasing the
temperature has the effect of increasing the amount of one of the products of this reaction. The reaction shifts
to the left to relieve the stress, and there is an increase in the concentration of H2 and I2 and a reduction in
the concentration of HI. When we change the temperature of a system at equilibrium, the equilibrium constant
for the reaction changes. Lowering the temperature in the HI system increases the equilibrium constant from
50.0 at 400°C to 67.5 at 357°C. At equilibrium at the lower temperature, the concentration of HI has increased
and the concentrations of H2 and I2 have decreased. Raising the temperature decreases the value of the
equilibrium constant from 67.5 at 357°C to 50.0 at 400°C.
EFFECT OF TEMPERATURE : VAN'T HOFF EQUATION
d(nK ) H  d(nK ) H 
(a) = (b) =  .
dT RT 2 dT1  R
 K 2  H  1 1 
Integrated form ln   =  T  T 
K
 1 R  1 2
 A THERMODYNAMIC RELATIONSHIP :
When reaction takes place at non standard state
G = Gº + RTlnQ .
At equilibrium G = 0 , Q = K
Gº = – RTlnK
EFFECT OF CATALYST ON EQUILIBRIUM
A catalyst has no effect on the value of an equilibrium constant or on equilibrium concentrations. The catalyst
merely increase the rates of both the forward and the reverse reactions to the same extent so that equilibrium
is reached more rapidly.
All of these effects change in concentration or pressure, change in temperature, and the effect of a catalyst
on a chemical equilibrium play a role in the industrial synthesis of ammonia from nitrogen and hydrogen
according to the equation.
N2 + 3H2 2NH3
One way to increase the yield of ammonia is to increase the pressure on the system in which N2, H2 and NH3
are in equilibrium or are coming to equilibrium.
N2 (g) 3H2(g) 2NH3(g)
The formation of additional amounts of ammonia reduces the total pressure exerted by the system and
somewhat reduces the stress of the increased pressure.
Although increasing the pressure of a mixture of N2 , H2 and NH3 increase the yield ammonia, at low
temperatures the rate of formation of ammonia is slow. At room temperature, for example, the reaction is so
slow that if we prepared a mixture of N2 and H2, no detectable amount of ammonia would form during our
lifetime. Attempts to increase the rate of the reaction by increasing the temperature are counterproductive.
The formation of ammonia from hydrogen and nitrogen is an exothermic process:
N2(g) + 3H2(g) 2NH3(g) H = – 92.2 kJ
Thus increasing the temperature to increase the rate lowers the yield. If we lower the temperature to shift the
equilibrium to the right to favour the formation of more ammonia, equilibrium is reached more slowly because
of the large decrease of reaction rate with decreasing temperature.
Part of the rate of formation lost by operating at lower temperatures can be recovered by using a catalyst to
increase the reaction rate. Iron powder is one catalyst used. However, as we have seen, a catalyst serves
equally well to increase the rate of a reverse reaction in this case, the decomposition of ammonia into its
constituent elements. Thus the net effect of the iron catalyst on the reaction is to cause equilibrium to be
reached more rapidly.
PHYSICAL EQUILIBRIUM
Only physical changes are involved.
Example : Physical equilibria. Solid liquid equilibria
Solid liquid
Example: H2O (s) H2O(l) : 273 K & 1 atm P..
Solid ice and liquid can coexist at 273 K and 1 atm. Solid form is said to be in equilibrium with liquid form. At
equilibrium, if heat exchanged from surrounding is zero, amount of solid ice and liquid water will remain
unchanged. However it must be noted that, the process of conversion of ice into water and vica-versa-never
ceases. At equilibrium
Net rate of conversion of ice into water = Net rate of conversion of water into ice.
OTHER EXAMPLES OF PHYSICAL EQUILIBRIA
The liquid - vapour equilibria :
(i) Example : H2O (l) H2O (g) 373 K ; 1 atm pressure.
Equilibrium is characterized by constant value of vapour pressure of H2O (l) at 373 K (= 1 atm)
Net rate of condensation of H2O (g) = net rate of evaporation of H2O (l)
(ii) Sugar (s) sugar (aq)
This is example of dissolution equilibria. Equilibrium is characterised by constant molar concentration of
sugar at specified temperature. At equilibrium, the solution of sugar in aqueous solution is called saturated
solution.
(iii) The dissolution of gas in liquid.
Example CO2 (g) + H2O CO2(aq)
The concentration of gas in liquid is proportional to the pressure of gas over the liquid.
Process Characteristic constant
H2O (l) H2O (g) PH constant at given temperature

2O
H2O (s) H2O (l) PH constant at given temperature

2O
solute (s) solute (soln) concentration of solute is constant at given temperature

X (g) X (aq) [X(aq)] [X(g)] = constant at given temperature
THE ATLAS
EQUILIBRIUM
Types of equilibria
Physical Equilibrium Chemical Equilibrium

1. Solid - Liquid 1. Law of mass action
2. Liquid- gas 2. Equilibrium constant KP and KC
3. Solid - Liquid - gas 3. Significance of equilibrium constant
4. Solubility of Solute in solution 4. Reaction quotient
5. Solubility of gas in solution 5. Homogeneous equilibria
(a) degree of dissociation from vapour

density measurement.
(b) relation between KP and KC
6. Heterogeneous equilibrium
7. Temperature dependent of equilibrium
constant
8. Kinetics & equilibrium constant
Application of equilibrium constant Le Chatelier's principle

(i) Pridicting extent of reaction Effect of following factor's on equilibrium
(ii) Pridicting direction of change (i) no. of moles
(iii)Calculation of equilibrium concentration (ii) Pressure and volume
(iii) temperature
(iv) catalyst & inert gas
Temperature dependence - Von't Hoff's equation

Understanding equilibrium
(i) From kinetic's approach (Guldberg & Wagge approach)
(ii) From thermodynamics approach –Criteria for
equilibrium in terms of Gibb's function
EXERCISE I
Reaction quotient and equilibrium constant
1. The initial concentrations or pressure of reactants and products are given for each of the following systems.
Calculate the reaction quotient and determine the directions in which each system will shift to reach equilibrium.
(a) 2NH3 (g) N2 (g) + 3H2 (g) K = 17
[NH3] = 0.20 M ; [N2] = 1.00 M ; [H2] = 1.00 M
(b) 2NH3 (g) N2 (g) + 3H2 (g) Kp = 6.8 × 104 atm2
Initial pressure : NH3 = 3.0 atm ; N2 = 2.0 atm ; H2 = 1.0 atm
(c) 2SO3(g) 2SO2 (g) + O2 (g) K = 0.230 atm
[SO3] = 0.00 M ; [SO2] = 1.00 M ; [O2] = 1.00 M
(d) 2SO3(g) 2SO2 (g) + O2 (g) Kp = 16.5 atm
Initial pressure : SO3 = 1.0 atm ; SO2 = 1.0 atm ; O2 = 1.0 atm
(e) 2NO(g) + Cl2 (g) 2NOCl (g) K = 4.6 × 104
[NO] = 1.00 M ; [Cl2] = 1.00 M ; [NOCl] = 0 M
2. Among the solubility rules is the statement that all chlorides are soluble except Hg2Cl2, AgCl, PbCl2, and CuCl.
(a) Write the expression for the equilibrium constant for the reaction represented by the equation.
AgCl (s) Ag+(aq) + Cl– (aq)
Is K greater than 1, less than 1, or about equal to 1? Explain your answer
(b) Write the expression for the equilibrium constant for the reaction represented by the equation
Pb2+ (aq) + 2Cl– (aq) PbCl2 (s)
Is K greater than 1, less than 1, or about equal to 1? Explain your answer.
3. Among the solubility rules is the statement that carbonates, phosphates, borates, arsenates, and arsenites,
except those of the ammonium ion and the alkali metals are insoluble.
(a) Write the expression for the equilibrium constant for the reaction represented by the equation
CaCO3 (s) Ca2+ (aq) + CO32– (aq)
Is K greater than 1, less than 1, or about equal to 1? Explain your answer
(b) Write the expression for the equilibrium constant for the reaction represented by the equation.
3Ba2+ (aq) + 2PO43– (aq) Ba3(PO4)2 (s)
Is K greater than 1, less than 1, or about equal to 1? Explain your answer.
4. Benzene is one of the compounds used as octane enhancers in unleaded gasoline. It is manufactured by the
catalytic conversion of acetylene to benzene.
3C2H2  C6H6
Would this reaction be most useful commercially if K were about 0.01, about 1, or about 10? Explain your
answer.
5. Show the complete chemical equation and the net ionic equation for the reaction represented by the equation
KI (aq) + I2 (aq) KI3 (aq)
give the same expression for the reaction quotient. KI3 is composed of the ions K+ and I3–.
Using the equilibrium constant
6. Which of the following reactions goes almost all the way to completion, and which proceeds hardly at all?
(a) N2(g) + O2(g) 2NO (g) ; Kc = 2.7 × 10–18
(b) 2NO(g) + O2(g) 2NO2 (g) ; Kc = 6.0 × 1013
7. For which of the following reactions will the equilibrium mixture contain an appreciable concentration of both
reactants and products?
(a) Cl2(g) 2Cl (g) ; Kc = 6.4 × 10–39
(b) Cl2(g) + 2NO (g) 2NOCl (g) ; Kc = 3.7 × 108
(c) Cl2(g) + 2NO2 (g) 2NO2Cl (g) ; Kc = 1.8
8. The value of Kc for the reaction 3O2 (g) 2O3 (g) is 1.7 × 10–56 at 25°C. Do you expect pure air at 25°C
to contain much O3 (ozone) when O2 and O3 are in equilibrium? If the equilibrium concentration of O2 in air at
25°C is 8 × 10–3 M, what is the equilibrium concentration of O3?
9. At 1400 K, Kc = 2.5 × 10–3 for the reaction CH4 (g) + 2H2S CS2(g) + 4H2(g). A 10.0 L reaction vessel at
1400 K contains 2.0 mol of CH4, 3.0 mol of CS2, 3.0 mol of H2 and 4.0 mol of H2S. Is the reaction mixture at
equilibrium? If not, in which direction does the reaction proceed to reach equilibrium?
10. The first step in the industrial synthesis of hydrogen is the reaction of steam and methane to give water gas,
a mixture of carbon monoxide and hydrogen.
H2O (g) + CH4(g) CO (g) + 3H2(g) Kc = 4.7 at 1400 K
A mixture of reactants and product at 1400 K contains 0.035 M H2O, 0.050M CH4, 0.15 M CO, and 0.20 M
H2. In which direction does the reaction proceed to reach equilibrium?
11. An equilibrium mixture of N2, H2, and NH3 at 700 K contains 0.036 M N2 and 0.15 M H2. At this temperature, Kc
for the reaction N2(g) + 3H2(g) 2NH3(g) is 0.29. What is the concentration of NH3?
12. The air pollutant NO is produced in automobile engines from the high temperature reaction
N2(g) + O2(g) 2NO (g) ; Kc = 1.6 × 10–3 at 2300 K. If the initial concentrations of N2 and O2 at 2300 K
are both 1.40 M, what are the concentrations of NO, N2, and O2 when the reaction mixture reaches equilibrium?
13. At a certain temperature, the reaction PCl5(g) PCl3(g) + Cl2(g) has an equilibrium constant
–2
Kc = 6 ×10 . Calculate the equilibrium concentrations of PCl5, PCl3 and Cl2 if only PCl5 is present initially,
at a concentration of 0.2 M.
14. At 700 K, Kp = 0.2 for the reaction ClF3 (g) ClF (g) + F2(g). Calculate the equilibrium partial pressure of

ClF3, ClF, and F2 if only ClF3 is present initially, at a partial pressure of 1.5 atm.
Homogeneous equilibria degree of dissociation, vapour density and equilibrium constant

15. The degree of dissociation of N2O4 into NO2 at 1.5 atmosphere and 40°C is 0.25. Calculate its
Kp at 40°C.Also report degree of dissociation at 10 atmospheric pressure at same temperature.
16. At 46°C, Kp for the reaction N2O4(g) 2NO2(g) is 0.667 atm. Compute the percent dissociation of N2O4

at 46° C at a total pressure of 380 Torr .
17. When 36.8g N2O4 (g) is introduced into a 1.0-litre flask at 27°C. The following equilibrium reaction
occurs : N2O4 (g) 2NO2 (g) ; Kp = 0.1642 atm.
(a) Calculate Kc of the equilibrium reaction.
(b) What are the number of moles of N2O4 and NO2 at equilibrium?
(c) What is the total gas pressure in the flask at equilibrium?
(d) What is the percent dissociation of N2O4?
18. At some temperature and under a pressure of 4 atm , PCl5 is 10% dissociated . Calculate the pressure
at which PCl5 will be 20% dissociated , temperature remaining same.
19. In a mixture of N2 and H2 in the ratio of 1:3 at 64 atmospheric pressure and 300°C, the percentage of
ammonia under equlibrium is 33.33 by volume. Calculate the equilibrium constant of the reaction using the
equation. N2(g) + 3H2(g) 2NH3(g).
20. The system N2O4 2 NO2 maintained in a closed vessel at 60º C & a pressure of 5 atm has an average

(i.e. observed) molecular weight of 69, calculate Kp. At what pressure at the same
temperature would the observed molecular weight be (230/3) ?
21. In the esterfication C2H5OH (l) + CH3COOH (l) CH3COOC2H5 (l) + H2O (l) an equimolar mixture of

alcohol and acid taken initially yields under equilibrium, the water with mole fraction = 0.333. Calculate the
equilibrium constant.
22. At a certain temperature, KC for the reaction 3C2H2(g) C6H6(g) is 4. If the equilibrium concentration of
C2H2 is 0.5 mole/litre, what is the concentration of C6H6 ?
23. For the reaction
CO2(g) + H2(g) CO(g) + H2O(g)
the value of KC at 552ºC is 0.137. If 5 moles of CO2, 5.0 moles of H2, 1.0 moles of CO and 1.0 mole of H2O
are initially present, what are the actual concentrations of CO2, H2, CO and H2O at equilibrium ?
Hetrogeneous equilibrium
24. Solid Ammonium carbamate dissociates as: NH2 COONH4 (s) 2NH3(g) + CO2(g). In a closed
vessel solid ammonium carbamate is in equilibrium with its dissociation products. At equilibrium, ammonia
is added such that the partial pressure of NH3 at new equilibrium now equals the original total pressure.
Calculate the ratio of total pressure at new equilibrium to that of original total pressure.
25. A sample of CaCO3(s) is introduced into a sealed container of volume 0.821 litre & heated to 1000K until
equilibrium is reached. The equilibrium constant for the reaction CaCO3(s) CaO(s) + CO2(g) is
4 × 102 atm at this temperature. Calculate the mass of CaO present at equilibrium.
26. Anhydrous calcium chloride is often used as a dessicant. In the presence of excess of CaCl2,, the amount
of the water taken up is governed by Kp = 6.4 × 1085 for the following reaction at room temperature,
CaCl2(s) + 6H2O(g) CaCl2 .6H2O(s) . What is the equilibrium vapour pressure of water in a closed vessel
that contains CaCl2(s) ?
27. 20.0 grams of CaCO3(s) were placed in a closed vessel, heated & maintained at 727º C under
equilibrium CaCO3(s) CaO(s) + CO2(g) and it is found that 75 % of CaCO3 was decomposed. What is
the value of Kp ? The volume of the container was 15 litres.
28. For the reaction I2(g) 2I(g), KC = 3.92 × 10–6 at 727ºC. Let 1 mole of I2 be injected into a 2 litre glass

box at 727ºC. What will be the concentrations of I2 and I when the equilibrium is attained ?
Changes in concentration at equilibrium Le Chatelier's principle
29. Suggest four ways in which the concentration of hydrazine, N2H4, could be increased in an equilibrium
described by the equation
N2 (g) + 2H2 (g) N2H4 (g) H = 95 kJ
30. How will an increase in temperature affect each of the following equilibria? An increase in pressure?
(a) 2NH3 (g) N2 (g) + 3H2 (g) H = 92 kJ
(b) N2 (g) + O2 (g) 2NO (g) H = 181 kJ
(c) 2O3 (g) 3O2 (g) H = – 285 kJ
(d) CaO (s) + CO2 (g) CaCO3 (s) H = – 176 kJ
31. (a) Methanol, a liquid fuel that could possibly replace gasoline, can be prepared from water gas and additional
hydrogen at high temperature and pressure in the presence of a suitable catalyst. Write the expression for
the equilibrium constant for the reversible reaction.
2H2 (g) + CO (g) CH3OH (g) H = – 90.2 kJ
(b) Assume that equilibrium has been established and predict how the concentration of H2, CO and CH3OH will differ
at a new equilibrium if (1) more H2 is added. (2) CO is removed. (3) CH3OH is added. (4) the pressure on the
system is increased. (5) the temperature of the system is increased. (6) more catalyst is added.
32. (a) Water gas, a mixture of H2 and CO, is an important industrial fuel produced by the reaction of steam with red-
hot coke, essentially pure carbon. Write the expression for the equilibrium constant for the reversible reaction.
C(s) + H2O (g)  CO (g) + H2 (g) H = 131.30 kJ
(b) Assume that equilibrium has been established and predict how the concentration of each reactant and
product will differ at a new equilibrium if (1) more C is added. (2) H2O is removed. (3) CO is added.
(4) the pressure on the system is increased. (5) the temperature of the system is increased.
33. Suggest two ways in which the equilibrium concentration of Ag+ can be reduced in a solution of Na+,
Cl–, Ag+ and NO3–, in contact with solid AgCl.
Na+ (aq) + Cl– (aq) + Ag+ (aq) + NO3– (aq) AgCl (s) + Na+ (aq) + NO3– (aq) H = –65.9 kJ
Kinetics and equilibrium constant

34. Which of the following relative values of kf and kr results in an equilibrium mixture that contains large amounts
of reactants and small amounts of product?
(a) kf > kr (b) kf = kr (c) kf < kr
35. Consider the gas-phase hydration of hexafluoroacetone, (CF3)2CO:
kf
(CF3)2CO (g) + H2O (g) (CF3)2C(OH)2 (g)
kr
At 76°C, the forward and reverse rate constants are kf = 0.13 M–1s–1 and kr = 6.02 × 10–4s–1. What is the
value of the equilibrium constant Kc?
36. Consider the reaction of chloromethane with OH– in aqueous solution
kf
CH3Cl (aq) + OH– (aq) CH3OH (aq) + Cl– (aq)
kr
At 25°C, the rate constant for the forward reaction is 6 × 10–6 M–1s–1, and the equilibrium constant Kc is
1 × 1016. Calculate the rate constant for the reverse reaction at 25°C.
37. The progress of the reaction
A nB with time, is presented in figure. Determine
(i) the value of n.
(ii) the equilibrium constant K.
(iii) the initial rate of conversion of A.
Temperature dependence of equilibrium constant

38. Listed in the table are forward and reverse rate constants for the reaction 2NO (g) N2(g) +O2(g)
Temperature (K) kf (M–1s–1) kr (M–1s–1)
1400 0.29 1.1 × 10–6
1500 1.3 1.4 × 10–5
Is the reaction endothermic or exothermic? Explain in terms of kinetics.
39. The equilibrium constant Kp for the reaction PCl5(g) PCl3(g) + Cl2(g) is 3.81 × 102 at 600 K and

2.69 × 103 at 700 K. Calculate rH.
Temperature dependence of equilibrium constant

40. Rate of disappearance of the reactant A at two different temperature is given by A B
 d[A]
= (2×10–2 S–1) [A] – 4 × 10–3 S–1[B] ; 300K
dt
 d[A ]
= (4×10–2 S–1) [A] –16 × 10–4 [B] ; 400K
dt
Calculate heat of reaction in the given temperature range. When equilibrium is set up.
41. The KP for reaction A + B C + D is1.34 at 60°C and 6.64 at 100°C. Calculate H° for the reaction over

this range of temperature?
Equilibrium expressions and equilibrium constants

42. If Kc = 7.5 × 10–9 at 1000 K for the reaction N2 (g) + O2 (g) 2NO (g), what is Kc at 1000 K for the reaction
2NO (g) N2 (g) + O2 (g)?
43. An equilibrium mixture of PCl5, PCl3 and Cl2 at a certain temperature contains 8.3 × 10–3 M PCl5,
1.5 × 10–2 M PCl3, and 3.2 × 10–2 M Cl2. Calculate the equilibrium constant Kc for the reaction
PCl5 (g) PCl3 (g) + Cl2 (g).
44. A sample of HI (9.30 × 10–3 mol) was placed in an empty 2.00 L container at 1000 K. After equilibrium was
reached, the concentration of I2 was 6.29 × 10–4 M. Calculate the value of Kc at 1000 K for the reaction
H2 (g) + I2 (g) 2HI (g).
45. The vapour pressure of water at 25°C is 0.0313 atm. Calculate the values of Kp and Kc at 25°C for the
equilibrium H2O (l) H2O (g).
EXERCISE II
1. 2 moles of A & 3 moles of B are mixed in 1 litre vessel and the reaction is carried at 400°C according to the
equation; A + B 2 C. The equilibrium constant of the reaction is 4. Find the number of moles of C at
equilibrium.
2. 2 NOBr (g) 2 NO (g) + Br2 (g). If nitrosyl bromide (NOBr) is 33.33% dissociated at 25° C & a total
pressure of 0.28 atm . Calculate Kp for the dissociation at this temperature.
3. At 227°C , the following equilibrium is established :
H2(g) + S(s) H2S(g) Kp = 7 × 102
If 0.2 mol of hydrogen and 1.0 mol of sulphur are heated to 227°C in a 1.0 litre vessel, what will
be the partial pressure of H2S at equilibrium?
4. The equilibrium constant for the reaction is 10 at 900°C S2(g) + C(s) CS2(g) . Calculate the pressure of
two gases at equilibrium, when 1.42 atm of S2 and excess of C(s) come to equilibrium.
5. A mixture of 2 moles of CH4 & 34 gms of H2S was placed in an evacuated container, which was then heated
to & maintained at 727º C. W hen equilibrium was established in the gaseous reaction
CH4 + 2 H2S CS2 + 4 H2 the total pressure in the container was 1 atm & the partial pressure of
hydrogen was 0.2 atm. What was the volume of the container ?
6. PCl5 dissociates according to the reaction PCl5 PCl3(g) + Cl2(g) . At 523 K, Kp = 1.78 atm. Find the
density of the equilibrium mixture at a total pressure of 1 atm .
7. The following data for the equilibrium composition of the reaction
2Na(g) Na2(g)
at 1.013 MPa pressure and 1482.53 K have been obtained.
mass % Na (monomer gas) = 71.3
mass % Na2 (dimer gas) = 28.7
Calculate the equilibrium constant Kp (in MPa–1)
8. A mixture of hydrogen & iodine in the mole ratio 1.5 : 1 is maintained at 450º C. After the attainment of
equilibrium H2(g) + I2(g) 2 HI(g), it is found on analysis that the mole ratio of I2 to HI is 1 : 18. Calculate
the equilibrium constant & the number of moles of each species present under equilibrium, if initially,
127 grams of iodine were taken.
9. In a closed container nitrogen and hydrogen mixture initially in a mole ratio of 1:4 reached equilibrium. It is
found that the half hydrogen is converted to ammonia. If the original pressure was 180 atm, what will be the
partial pressure of ammonia at equilibrium. (There is no change in temperature)
10. The equilibrium constant for the reaction CO(g) + H2O(g) CO2(g) + H2(g) is 8.0 at 450º C & 1atm

pressure . The initial concentration of water gas [CO & H2 in equimolar ratio] & steam are 2 moles & 5 moles
respectively. Find the number of moles of CO, H2, CO2 & H2O (vapour) at equilibrium.
11. SO3 decomposes at a temperature of 1000 K and at a total pressure of 1.642 atm. At equilibrium, the
density of mixture is found to be 1.28 g/l in a vessel of 90 literes. Find the degree of dissociation of SO3 for
SO3  SO2 + 1/2O2.
12. Consider the equilibrium: P(g) + 2Q(g) R(g). When the reaction is carried out at a certain temperature,
the equilibrium concentration of P and Q are 3M and 4M respectively. When the volume of the vessel is
doubled and the equilibrium is allowed to be reestablished, the concentration of Q is found to be 3M. Find (A)
Kc (B) concentration of R at two equilibrium stages.
13. A saturated solution of iodine in water contains 0.3 g I2 / L. More than this can dissolve in a KI solution
because of the following equilibrium : I2(aq) + I (aq) I 
3 aq. A 0.10 M KI solution (0.10 M I) actually
dissolves 13 g of iodine/L, part of which is converted to I3. Assuming that the concentration of I2 in all
saturated solutions is the same, calculate the equilibrium constant for the above reaction. What is the
effect of adding water to a clear saturated of I2 in the KI solution ?
14. The equilibrium pXyloquinone + methylene white pXylohydroquinone + methylene blue may be

studied convinently by observing the difference in color methylene white and methylene blue. One mmol of
methylene blue was added to 1L of solution that was 0.24 M in pXylohydroquinone and 0.012 M in
pXyloquinone. It was then found that 4% of the added methylene blue was reduced to methylene white.
What is the equilibrium constant of the above reaction? The equation is balanced with one mole each of
4 substances.
15. A certain gas A polymerizes to a small extent at a given temperature & pressure, nA A

An . Show that the
gas obeys the approx. equation
PV  (n  1)K c 
 1 
A 
whereK c  n &V is the volume of the conatiner..
n 1 
RT  V 
 A n
Assume that initially one mole of A was taken in the container.
16. 103 mol of CuSO4.5H2O is introduced in a 2.0 L vessel maintained at a constant temperature of 27°C containing
moist air at relative humidity of 12.5%. What is the final molar composition of solid mixture?
For CuSO4.5H2O(s) CuSO4(s) + 5H2O(g), Kp(atm) = 10–10. Take vapor pressure of water at 27°C as 30.4 torrs.
17. Two solids X and Y disssociate into gaseous products at a certain temperature as follows:
X(s) A(g) + C(g), and Y(s) B(g) + C(g). At a given temperature, pressure over excess
solid X is 40 mm and total pressure over solid Y is 60 mm. Calculate:
(a) the values of Kp for two reactions (in mm2)
(b) the ratio of moles of A and B in the vapour state over a mixture of X and Y.
(c) the total pressure of gases over a mixture of X and Y.
18. When 1 mole of A(g) is introduced in a closed rigid 1 litre vessel maintained at constant temperature the
following equilibria are established.
A (g) B(g) + C(g) : K C1
C (g) D(g) + B(g) : K C2
K C2 [C]eq 1
The pressure at equilibrium is twice the initial pressure. Calculate the value of K if [B] =
C1 eq 5
QUESTION BANK
1. Consider following reactions in equilibrium with equilibrium concentration 0.01 M of every species
(I) PCl5 (g) PCl3(g) + Cl2(g) (II) 2HI(g) H2(g) + I2 (g) (III) N2(g) + 3H2(g) 2NH3(g)
Extent of the reactions taking place is:
(A) I > II > III (B) I < II < III (C) II < III < I (D) III < I < II
2. The equilibrium constant for the given reaction :
1
SO3(g) SO2(g) + O (g) ; Kc = 4 × 10–2
2 2
The value of Kc for the reaction :
2SO2(g) + O2(g) 2SO3(g), will be
(A) 625 (B) 25 (C) 1/625 (D) none of these
3. For the following gases equilibrium. N2O4 (g) 2NO2 (g)

Kp is found to be equal to Kc. This is attained when
(A) 0°C (B) 273 K (C) 1 K (D) 12.19 K
4. 1 mole N2 and 3 mol H2 are placed in a closed container at a pressure of 4 atm. The pressure falls to 3 atm
at the same temperature when the following equilibrium is attained.
N2(g) + 3H2(g) 2NH3(g). The equilibrium constant KP for dissociation of NH3 is:
1 0.5  (1.5) 3 3 3
(A) × (1.5)3 atm–2 (B) 0.5 ×(1.5)3 atm2 (C) atm2 (D) atm–2
0 .5 3 3 0.5  (1.5) 3
5. For the reaction 3 A (g) + B (g) 2 C (g) at a given temperature , Kc = 9.0 . What must be the volume
of the flask, if a mixture of 2.0 mol each of A , B and C exist in equilibrium?
(A) 6L (B) 9L (C) 36 L (D) None of these
6. Sulfide ion in alkaline solution reacts with solid sulfur to form polysulfide ions having formulas
S22, S32, S42 and so on. The equilibrium constant for the formation of S22 is 12 ( K1) & for the formation of
S32 is 132 (K2 ), both from S and S2.What is the equilibrium constant for the formation of S32 from S22
and S?
(A) 11 (B) 12 (C) 132 (D) None of these
7. A definite amount of solid NH4 HS is placed in a flask already containing ammonia gas at a certain temperature
and 0.50 atm pressure. NH4HS decomposes to give NH3 and H2S and at equilibrium total pressure in flask is
0.84 atm. The equilibrium constant for the reaction is :
(A) 0.30 (B) 0.18 (C) 0.17 (D) 0.11
8. One mole of N2O4 (g) at 300 K is left in a closed container under one atm . It is heated to 600 K when
20 % by mass of N2O4 (g) decomposes to NO2 (g) . The resultant pressure is :
(A) 1.2 atm (B) 2.4 atm (C) 2.0 atm (D) 1.0 atm
9. For the reaction : 2Hl (g) H2(g) + I2(g), the degree of dissociated () of Hl(g) is related to equilibrium
constant KP by the expression
1 2 Kp 1  2K p 2K p 2 Kp
(A) (B) (C) (D)
2 2 1  2K p 1 2 Kp
10. In a system, the equilibrium reaction :
2NH3(g) N2(g) + 3H2(g)
was studied starting with NH3 and Ne(inert gas). It is found that at 10 atm and 700 K, the equilibrium gaseous
mixture contains 10 mole % each of NH3(g) and Ne(g). Calculate KP (in atm2)
11. The vapour density of N2O4 at a certain temperature is 30. What is the % dissociation of N2O4 at this
temperature?
(A) 53.3% (B) 106.6% (C) 26.7% (D) None
12. Densities of diamond and graphite are 3.5 and 2.3 gm/mL.
C (diamond) C (graphite) rH = –1.9 kJ/mole
favourable conditions for formation of diamond are
(A) high pressure and low temperature (B) low pressure and high temperature
(C) high pressure and high temperature (D) low pressure and low temperature
13. A vessel of 250 litre was filled with 0.01 mole of Sb2S3 and 0.01 mole of H2 to attain the equilibrium at 440°C
as Sb2S3 (s) + 3H2 (g) 2Sb (s) + 3H2S(g).
After equilibrium H2S formed was analysed by dissolving it in water and treating with excess of Pb2+ to give
1.195 g of PbS (Molecular weight = 239) precipitate.
What is value of Kc of the reaction at 440°C?
14. The equilibrium constant for the reaction CO(g) + H2O(g) CO2(g) + H2(g) is 3 at 500 K. In a 2 litre vessel

60 g of water gas [equimolar mixture of CO(g) and H2(g)] and 90 g of steam is initially taken. What is the
concentration of H2(g) at equilibrium (mole/L)?
(A) 1.75 (B) 3.5 (C) 1.5 (D) 0.75
15. At 87°C, the following equilibrium is established
H2(g) + S(s) H2S(g) Kp = 7 × 10–2
If 0.50 mole of hydrogen and 1.0 mole of sulfur are heated to 87°C in 1.0 L vessel, what will be the partial
pressure of H2S at equilibrium?
(A) 0.966 atm (B) 1.38 atm (C) 0.0327 (D) 9.66 atm
16. At certain temperature (T) for the gas phase reaction
2H2O(g) + 2Cl2(g) 4HCl(g) + O2(g) Kp = 12 × 108 atm
If Cl2, HCl & O2 are mixed in such a manner that the partial pressure of each is 2 atm and the mixture is
brough into contact with excess of liquid water. What would be approximate partial pressure of Cl2 when
equilibrium is attained at temperature (T)?
[Given: Vapour pressure of water is 380 mm Hg at temperature (T)]
(A) 3.6 × 10–5 atm (B) 10–4 atm
(C) 3.6 × 10–3 atm (D) 0.01 atm
17. At 675 K, H2(g) and CO2(g) react to form CO(g) and H2O(g), Kp for the reaction is 0.16.
If a mixture of 0.25 mole of H2(g) and 0.25 mol of CO2 is heated at 675 K, mole % of CO(g) in equilibrium
mixture is :
(A) 7.14 (B) 14.28 (C) 28.57 (D) 33.33
18. In which of the following reactions, increase in the pressure at constant temperature does not affect the
moles at equilibrium:
1
(A) 2NH3(g) N2(g) + 3H2(g) (B) C(g) + O (g) CO(g)
2 2
1
(C) H2(g) + O (g) H2O(g) (D) H2(g) + I2(g) 2HI(g)
2 2
19. Change in volume of the system does not alter the number of moles in which of the following equilibrium
(A) N2(g) + O2(g) 2NO(g) (B) PCl5(g) PCl3(g) + Cl2(g)
(C) N2(g) + 3H2(g) 2NH3(g) (D) SO2Cl2(g) SO2(g) + Cl2(g)
20. The conditions favourable for the reaction :
2SO2(g) + O2(g) 2SO3(g) ; H° = – 198 kJ
are :
(A) low temperature, high pressure (B) any value of T and P
(C) low temperature, and low pressure (D) high temperature and high pressure
21. The equilibrium constants K P and K P for the reactions

1 2
X 2Y and Z P + Q, respectively are in the ratio of 1 : 9, If the degree of dissociation of X and Z be equal
then the ratio of total pressures at these equilibria is :
(A) 1 : 36 (B) 1 : 1 (C) 1 : 3 (D) 1 : 9
22. When N2O5 is heated at temperature T, it dissociated as N2O5 N2O3 + O2, Kc = 2.5. At the same time

N2O3 also decomposes as : N2O3 N2O + O2. If initially 4.0 moles of N2O5 are taken in 1.0 litre flask and
allowed to attain equilibrium, concentration of O2 was formed to be 2.5 M. Equilibrium concentration of N2O
is
(A) 1.0 (B) 1.5 (C) 2.166 (D) 0.334
23. The equilibrium constant for the following reaction’s have been measured at 823°C.
CoO (s) + H2(g) Co(s) + H2O (g) ; K = 67
CoO (s) + CO(g) Co(s) + CO2 (g) ; K = 490
The value of equilibrium constant of the reaction following reaction is
2CO2(g) + 2H2(g) 2CO(g) + 2H2O (g)
2
490 67  67 
(A) (B) (C) 490 × 67 (D)  
67 490  490 
24. The following equilibrium are given :
N2 + 3H2 2NH3 ...K1
N2 + O2 2NO ...K2
1
H2 + O H2O ...K3
2 2
The equilibrium constant of the reaction
5
2NH3 + O 2NO + 3H2O, in terms of K1, K2 and K3 is
2 2
(A) K K K (B) K 1K 32 K 2 (C) K 2K 33 K1 (D) K1K2K3

1 2 3
25. In the following reaction : 3A (g) + B (g) 2C (g) + D (g) initial mol of B is double of A. At equilibrium mol
of A and C are equal. Hence % conversion of B is
(A) 10% (B) 20% (C) 40% (D) 5%
26. The equilibrium constant for the reaction
A(g) + 2B(g) C(g)
is 0.25 dm6mol–2. In a volume of 5 dm3, what amount of A must be mixed with 4 mol of B to yield 1 mol of C
at equilibrium.
(A) 3 moles (B) 24 moles
(C) 26 moles (D) None of these
Paragraph for Questions Nos. 27 to 30

In a 7.0 L evacuated chamber , 0.50 mol H2 and 0.50 mol I2 react at 427°C .
H2(g) + I2(g) 2HI(g) . At the given temperature, KC=49 for the reaction.
27. What is the value of Kp ?
(A) 7 (B) 49 (C) 24.5 (D) None
28. What is the total pressure (atm) in the chamber?
(A) 83.14 (B) 831.4 (C) 8.21 (D) None
29. How many moles of the iodine remain unreacted at equilibrium?
(A) 0.388 (B) 0.112 (C) 0.25 (D) 0.125
30. What is the partial pressure (atm) of HI in the equilibrium mixture?
(A) 6.385 (B) 12.77 (C) 40.768 (D) 646.58
Paragraph for Questions Nos. 31 to 33

Equilibrium constants are given (in atm) for the following reactions at 0° C:
SrCl2 6H2O(s) SrCl2  2H2O (s) + 4H2O(g) Kp = 5 × 1012
Na2HPO4  12 H2O(s) Na2HPO4  7 H2O (s) + 5H2 O(g) Kp = 2.43 × 1013
Na2SO4 10 H2O(s) Na2SO4 (s) + 10 H2O (g) Kp = 1.024 × 1027
The vapor pressure of water at 0°C is 4.56 torr.
31. Which is the most effective drying agent at 0°C?
(A) SrCl2  2H2O (B) Na2HPO47 H2O
(C) Na2SO4 (D) all equally
32. At what relative humidities will Na2SO4 10 H2O be efflorescent (release moisture) when exposed to air at
0°C?
(A) above 33.33% (B) below 33.33 %
(C) above 66.66% (D) below 66.66%
33. At what relative humidities will Na2SO4 be deliquescent (i.e. absorb moisture) when exposed to the air at 0°C?
(A) above 33.33% (B) below 33.33 %
(C) above 66.66% (D) below 66.66%
Assertion-Reason
Questions given below consist of two statements each printed as Assertion (A) and Reason (R); while
answering these questions you are required to choose any one of the following four responses:
(A) if both (A) and (R) are true and (R) is the correct explanation of (A)
(B) if both (A) and (R) are true but (R) is not correct explanation of (A)
(C) if (A) is true but (R) is false
(D) if (A) is false and (R) is true
34. Assertion : In a close system, number of reacting species may not be in state of equilibrium (Material,

thermal and Mechanical) for long time
Reason : Either of the two rate of reaction (forward or backward) is very slow.
35. Statement -1 : Total number of moles in a closed system at new equilibrium is less than the old equilibrium
if some amount of a substance is removed from a system
(consider a reaction A(g) B(g) at equilibrium)
Statement -2 : The number of moles of the substance which is removed, is partially compensated as the
system reached to new equilibrium.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is false, statement-2 is true.
(D) Statement-1 is true, statement-2 is false.
More than one may be correct

36. For the gas phase reaction, C2H4 + H2 C2H6 (H = –32.7 kcal), carried out in a closed vessel, the
equilibrium moles of C2H4 can be increased by
(A) increasing the temperature (B) decreasing the pressure
(C) removing some H2 (D) adding some C2H6
37. Consider the equilibrium HgO(s) + 4I– (aq) + H2O () HgI42– (aq) + 2OH– (aq), which changes will

decrease the equilibrium concentration of HgI42–
(A) Addition of 0.1 M HI (aq) (B) Addition of HgO (s)
(C) Additon of H2O () (D) Addition of KOH (aq)
38. For the reaction PCl5(g) PCl3(g) + Cl2(g), the forward reaction at constant temperature is favoured by

(A) introducing an inert gas at constant volume
(B) introducing chlorine gas at constant volume
(C) introducing an inert gas at constant pressure
(D) introducing PCl5 at constant volume.
39. The equilibrium SO2Cl2(g) SO2(g) + Cl2(g) is attained at 25°C in a closed rigid container and an inert

gas, helium is introduced. Which of the following statements is/are correct.
(A) concentrations of SO2, Cl2 and SO2Cl2 do not change
(B) more chlorine is formed
(C) concentration of SO2 is reduced
(D) more SO2Cl2 is formed
40. When NaNO3(s) is heated in a closed vessel, oxygen is liberated and NaNO2(s) is left behind. At equilibrium
(A) addition of NaNO2 favours reverse reaction
(B) addition of NaNO3 favours forward reaction
(C) increasing temperature favours forward reaction
(D) increasing pressure favours reverse reaction
41. Following two equilibrium is simultaneously established in a container
PCl5(g) PCl3(g) + Cl2(g)
CO(g) + Cl2(g) COCl2(g)
If some Ni(s) is introduced in the container forming Ni (CO)4 (g) then at new equilibrium
(A) PCl3 concentration will increase (B) PCl3 concentration will decrease
(C) Cl2 concentration will remain same (D) CO concentration will remain same
42. Decrease in the pressure for the following equilibria : H2O(s) H2O (l) result in the :

(A) formation of more H2O (s) (B) formation of more H2O(l)
(C) increase in melting point of H2O (s) (D) decrease in melting point of H2O (s)
43. Phase diagram of CO2 is shown as following Based on above find the correct statement(s)
73
Solid Liquid
67
P (atm)
5
1 Gas
195 217 298 304

T(K)
(A) 298K is the normal boiling point of liquid CO2
(B) At 1 atm & 190 K CO2 will exist as gas.
(C) CO2(s) will sublime above 195K under normal atmospheric pressure
(D) Melting point & boiling point of CO2 will increase on increasing pressure
Match the column :

44. Column I Column II
(A) KP < KC (P) N2(g) + 3H2(g) 2NH3(g)
(B) Introduction of inert gas at (Q) PCl5(g) PCl3(g) + Cl2(g)
constant pressure will decrease
the concentration of reactants
(C) KP has dimension (R) 2NO2(g) N2O4(g)
(S) NH3(g) + HI(g) NH4I(s)
45. Match the Column
Column I Column II
(A) Addition of water in (P) Equilibrium shifts in forward direction
A(aq) + H2O() B(aq) + C(aq)
(B) Addition of inert gas at constant pressure in (Q) Equilibrium shifts in backward direction

1
SO2(g) + O2(g) SO3(g)
2
(C) Pressure decreases and moles of N2 increases in (R) Equilibrium remains unaffected
N2(g) + 2O2(g) 2NO2(g)
(S) Theoretically we can not predict
46. For the reaction A(s) + B(g) 2C(g) + D(g) ; Kp = Kc (RT)y . Find the value of y..
47. From the following graphical representation, what is the value of ( + + ) in following equilibrium reaction?
A(g) + B(g) C(g)
2M
Concentration
1M [A]
0.5M [B]
0.25M [C]
0
Time
48. Calculate the value of Keq for the reaction Zn(s) + 2H+(aq) Zn2+(aq) + H2(g).

Where concentration of [H+] = 0.1 M ; [Zn2+] = 0.01 M and PH2 (g) = 2 atm.
49. For the equilibrium CuSO4 . 5H2O(s) CuSO4 . 3H2O(s) + 2H2O(g) Kp = 2.25 × 10–4 atm2 and vapour

pressure of water is 22.8 torr at 298 K. If % relative humidity is z, then find the value of z/10.
50. N2O4 at 2 atm is introduced in a 12 rigid vessel at 300 K. Temperature is increased to 600 K, due to which
50% of N2O4 dissociates into NO2. Calculate the final pressure (in atm) of the system.
EXERCISE III
1. For the reversible reaction, N2(g) + 3H2(g) 2NH3(g) at 500ºC, the value of Kp is 1.44 × 10–5 when partial
pressure is measured in atmospheres. The corresponding value of Kc, with concentration in mole litre–1, is
1.44  10 –5 1.44  10 –5 1.44  10 –5 1.44  10 –5

(A) (B) (C) (D)
(0.082  500) – 2 (8.314  773) – 2 (0.082  773)2 (0.082  773) – 2
[JEE 2000]
2. When two reactants, A and B are mixed to give products C and D, the reaction quotient Q, at the initial
stages of the reaction
(A) is zero (B) decreases with time
(C) is independent of time (D) increases with time [JEE 2000]
3. When 3.06 g of solid NH4HS is introduced into a two litre evacuated flask at 27°C, 30% of the solid decomposes
into gaseous ammonia and hydrogen sulphide. [JEE 2000]
(i) Calculate KC & KP for the reaction at 27°C.
(ii) What would happen to the equilibrium when more solid NH4HS is introduced into the flask?
4. At constant temperatue, the equilibrium constant (Kp) for the decomposition reaction N2O4 2NO2 is
expressed by Kp = (4x2P) / (1 – x2), where P = pressure, x = extent of decomposition. Which one of the
following statements is true? [JEE 2001]
(A) Kp increases with increase of P (B) Kp increases with increase of x
(C) Kp increases with decrease of x (D) Kp remains constant with change in P and x
5. Consider the following equilibrium in a closed container : N2O4 2NO2. At a fixed temperature, the
volume of the reaqctions container is halved. For this change, which of the following statements holds true
regarding the equilibrium constant (Kp) and degree of dissociation ()?
(A) neither Kp nor  changes (B) both Kp and  change [JEE 2002]
(C) Kp changes, but  does not change (D) Kp does not change, but  changes
6. The thermal dissociation equilibrium of CaCO3(s) is studied under different conditions.
CaCO3(s) CaO(s) + CO2(g) [IIT-JEE-2013]
For this equilibrium, the correct statement(s) is(are)
(A) H is dependent on T (B) K is independent of the initial amount of CaCO3
(C) K is dependent on the pressure of CO2 at a given T (D) H is independent of the catalyst, if any
1
7. For the reaction SO2(g) + O SO3(g)' if KP = KC(RT)x where the symbols have usual meaning then
2 2(g)
the value of x is : (assuming ideality) [IIT-JEE-Mains-2014]
1 1
(A)  (B) (C) 1 (D) –1
2 2
8. The standard Gibbs energy change at 300 K for the reaction 2A B + C is 2494.2 J. At a given time,
1 1
the composition of the reaction mixture is [A]  , [B] = 2 and [C]  . The reaction proceeds in the :
2 2
[R = 8.314 J/K mol, e = 2.718] [JEE Mains 2015]
(A) Reverse direction because Q < Kc (B) Forward direction because Q > Kc
(C) Reverse direction because Q > Kc (D) Forward direction because Q < Kc
9. The % yield of ammonia as a function of time in the reaction [JEE Advance 2015]

N2(g) + 3H2(g)  2NH3(g), H < 0
At (P, T1) is given below,
%yield
time
If the reaction is conducted at (P, T2), with T2 > T1, the %yield of ammonia as a function of time is represented
by
T1
T2
T2
%yield
%yield
T1
(A) (B)
time time
T1 T2
T2 T1
%yield
%yield
(C) (D)
time time
10. The equilibrium constant at 298 K for a reaction A + B C + D is 100. If the initial concentration of all the

four species were 1 M each, then equilibrium concentration of D (in mol L–1) will be : [JEE Mains 2016]
(A) 0.182 (B) 0.818 (C) 1.818 (D) 1.182
11. Which of the following lines correctly show the temperature dependence of equilibrium constant, K, for an
exothermic reaction? [IIT Main-2018]
ln K A
B
.... 1
(0,0) ....... T(K)
....
....
....
....
C
D
(A) A and D (B) A and B (C) B and C (D) C and D
12. At a certain temperature in a 5 L vessel, 2 moles of carbon monoxide and 3 moles of chlorine were allowed
to reach equilibrium according to the reaction, [IIT Main online-2018]
CO(g) + Cl2(g) COCl2(g)
At equilibrium, if one mole of CO is present then equilibrium constant (Kc) for the reaction is :
(A) 2 (B) 2.5 (C) 3 (D) 4
13. In which of the following reactions, an increase in the volume of the container will favour the formation of
products ? [IIT Main online-2018]
(A) 2NO2(g) 2NO(g) + O2 (g) (B) H2(g) + I2(g) 2HI(g)
(C) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(l) (D) 3O2(g) 2O3(g)
14. The gas phase reaction 2NO2(g)  N2O4(g) is an exothermic reaction. The decomposition of N2O4, in
equilibrium mixture of NO2(g) and N2O4(g), can be increased by [IIT Main online-2018]
(A) increasing the pressure (B) addition of an inert gas at constant pressure
(C) lowering the temperature (D) addition of an inert gas at constant volume
15. The INCORRECT match in the following is : [IIT Main online-2019]

(A)G0 < 0, K > 1 (B) G0 > 0, K < 1 (C) G0 = 0, K = 1 (D) G0 < 0, K < 1
16. For the following reactions, equilibrium constants are given : [IIT Main online-2019]
52
S(s) + O2(g) SO2(g) K1 = 10
2S(s) + 3O2(g) 2SO3(g) K2 = 10129
The equilibrium constant for the reaction,
2SO2(g) + O2(g) 2SO3(g) is :
(A) 1025 (B) 1077 (C) 10154 (D) 10181
17. For the reaction, [IIT Main online-2019]

2 SO2(g) + O2(g) 2 SO3(g),
–1
H = –57.2 kJ mol and
Kc = 1.7 × 1016.
Which of the following statment is INCORRECT ?
(A) The equilibrium will shift in forward direction as the pressure increases.
(B) The addition of inert gas at constant volume will not affect the equilibrium constant.
(C) The equilibrium constant decreases as the temperature increases.
(D) The equilibrium constant is large suggestive of reaction going to completion and so no catalyst is required.
18. In which one of the following equilibria, KP  Kc ? [IIT Main online-2019]

(A) 2NO(g) N2(g) + O2(g) (B) NO2(g) + SO2(g) NO(g) + SO3(g)
(C) 2HI(g) H2(g) + I2(g) (D) 2C(s) + O2(g) 2CO(g)
19. Consider the following reversible chemical reactions : [IIT Main online-2019]

K

1
A 2 (g)  B2 (g)  2AB(g) ... (i)
K

2
 3A 2 (g)  3B2 (g) ... (ii)
6AB(g) 
The relation between K1 and K2 is :
1
(A) K1K 2  (B) K2 = K1–3 (C) K2 = K13 (D) K1K2 = 3
3
20. The values of Kp / KC for the following reactions at 300 K are respectively : [IIT Main online-2019]

(At 300 K, RT = 24.62 dm3 atm mol–1)
N2(g) + O2(g) 2NO(g)
N2O4 (g) 2NO2(g)
N2(g) + 3H2(g) 2NH3(g)
(A) 1,24.62 dm mol–1, 1.65 × 10–3 dm–6 atm–2 mol2
3
(B) 1,24.62 dm3 atm mol–1, 606.0 dm6 atm2 mol–2
(C) 1,4.1 × 10–2 dm–3 atm–1 mol, 606 dm6 atm2 mol–2
(D) 24.62 dm3 atm mol–1, 606.0 dm6 atm2 mol–2, 1.65 × 10–3 dm–6 atm–2 mol2
21. 5.1 g NH4SH is introduced in 3.0 L evacuated flask at 327ºC, 30% of the solid NH4SH decomposed to NH3
and H2S as gases. The Kp of the reaction at 327ºC is (R = 0.082 L atm mol–1 K–1, Molar mass of S = 32 g
mol–1, molar mass of N = 14 g mol–1) [IIT Main online-2019]
(A) 0.242 atm2 (B) 4.9 × 10–3 atm2 (C) 1 × 10–4 atm2 (D) 0.242 × 10–4 atm2
22. Consider the reaction N2(g) + 3H2(g) 2NH3(g) [IIT Main online-2019]
The equilibrium constant of the above reaction is Kp. If pure ammonia is left to dissociate, the partial pressure
of ammonia at equilibrium is given by (Assume that pNH3  ptotal at equilibrium)
33 / 2 K p1/ 2P2 K p1/ 2 P2 K p1/ 2 P2 33 / 2 K p1/ 2P2

(A) (B) (C) (D)
4 16 4 16
23. Two solids dissociate as follows [IIT Main online-2019]

A(s) B(g)+ C(g) ; Kp1 = x atm2
D(s) C(g) + E(g) ; Kp2 = y atm2
The total pressure when both the solids dissociate simultaneously is :
(A) x2 + y2 atm (B) x  y atm (C) (x + y) atm (D) 2  

x  y atm
K
24. In a chemical reaction, A + 2B 2C + D, the initial concentration of B was 1.5 times of the concentration
of A, but the equilibrium concentrations of A and B were found to be equal. The equilibrium constant(K) for the
aforesaid chemical reaction is : [IIT Main online-2019]
1
(A) 16 (B) (C) 1 (D) 4
4
25. For the following reaction, the equilibrium constant Kc at 298 K is 1.6 × 1017.
Fe2+ (aq) + S2– (aq) FeS(s)
When equal volumes of 0.06M Fe2+(aq) and 0.2 M S2–(aq) solutions are mixed, the equilibrium concentration
of Fe2+(aq) is found to be Y × 10–17 M. The value of Y is _______. [JEE Advanced 2019]
ANSWER KEY
EXERCISE I
Q.1 (a) 25, shifts left, (b) 0.22, shifts right, (c) , shifts left, (d) 1, shifts right, (e) 0, shift right
Q.2 (a) K = [Ag+][Cl–] is less than 1. AgCl is insoluble thus the concentration of ions are much less than 1 M
(b) K = 1/[Pb2+][Cl–] 2 is greater than one because PbCl2 is insoluble and formation of the solid will reduce the
concentration of ions to a low level
Q.4 K about 10 Q.6 (a) incomplete (b) almost complete
Q.7 c Q.8 ~ 9× 10–32 mol/L
Q.9 The reaction is not an equilibrium because Qc > Kc. The reaction will proceed from right to left to reach
equilibrium
Q.11 5.9 × 10–3 M Q.12 [NO] = 0.055 M, [N2] = [O2] = 1.37 M
Q.13 [PCl3] = [Cl2] = 0.084 M, [PCl5] = 0.116M Q.14 PCIF = PF2 = 0.457 atm, PClF3 = 1.043 atm
Q.15 KP = 0.4, a ~ 0.1 Q.16 50%

Q.17 ( a) 6.667 × 10 –3 m ol L –1 ; ( b) n ( N 2 O 4 ) = 0.374 m ol; n ( NO 2 ) = 0.052 m ol ;
(c) 10.49 atm (d) 6.44 %
Q.18 0.97 atm Q.19 KP = 1.3 × 10-3 atm -2
Q.20 Kp= 2.5 atm, P = 15 atm Q.21 K = 4 Q.22 0.5 moles/litre
Q.23 [CO] = [H2O] = 1.62 M, [CO2] = [H2] = 4.38 M Q.24 31/27 Q.25 22.4 mg
Q.26 PH 2O = 5 × 1015 atm Q.27 0.821 atm Q.28 [I]= 1.4 × 10–3 M ; [I2] = 0.499 M
Q.29 add N2, add H2, increase the pressure , heat the reaction
Q.30 (a) shift right, shift left, (b) shift right, no effect, (c) shift left, shift left, (d) shift left, shift right
Q.31 (a) K = [CH3OH]/[H2]2[CO] ,
(b) 1. [H2] increase, [CO] decrease, [CH3OH] increase ; 2. [H2] increase, [CO] decrease, [CH3OH] decrease
; 3. [H2] increase, [CO] increase, [CH3OH] increase ; 4. [H2] increase, [CO] increase, [CH3OH] increase ; 5.
[H2] increase, [CO] increase, [CH3OH] decrease ; 6. no change
Q.32 (a) K = [CO][H2]/[H2O] ;
(b) in each of the following cases the mass of carbon will change, but its concentration (activity) will not
change. 1. [H2O] no change, [CO] no change, [H2] no change ; 2. [H2O] decrease, [CO] decrease, [H2]
decrease ; 3. [H2O] increase, [CO] increase, [H2] decrease; 4. [H2O] increase, [CO] increase, [H2] increase;
5. [H2O] decrease , [CO] increase , [H2] increase
Q.33 Add NaCl or some other salt that produces Cl– in the solution. Cool the solution.
Q.34 C Q.35 216 Q.36 6 × 10–22
Q.37 (i) 2; (ii) 1.2 mol/L; (iii) 0.1 moles/hr
Q.38 kr increase more than kf, this means that Ea (reverse) is greater than Ea (forward). The reaction is exothermic
when Ea (reverse) > Ea (forward).
Q.40 16.06 kJ Q.41 41.3 kJ / mol Q.42 1.3 × 108 Q.43 0.058
Q.44 29.0 Q.45 Kp = 0.0313 atm, Kc = 1.28 × 10–3
EXERCISE II
Q.1 2.4 mole Q.2 Kp = 0.01 atm Q.3 0.537 atm
Q.4 PCS = 1.29 atm, PS2 = 0.129 atm Q.5 273.66 L

2
Q.6 2.7 g / lit Q.7 pNa = 0.843 M Pa; pNa = 0.170 M Pa; Kp =0.239

2
Q.8 Kc=54, nHI=0.9 mol, nI2= 0.05 mol, nH2 = 0.3 mol
Q.9 48 atm Q.10 nCO2 = 0.943, nH2 = 1.943, nCO = 0.057, nH2Og= 4.057
Q.11  = 0.5 Q.12 Kc = 1/12, [R] = 4 (initial), = 1.5 (final)
Q.13 K=846.66, backward reaction is favoured Q.14 Kc = 480 Q.15 To be proved
Q.16 CuSO4.5H2O = 9.188 × 104 mol, CuSO4 = 8.12 × 105 moles
Q.17 (a) 400mm 2, 900mm 2 (b) 4: 9, (c) 72.15 mm Hg Q.18 4
QUESTION BANK
Q.1 B Q.2 A Q.3 D Q.4 B Q.5 A
Q.6 A Q.7 D Q.8 B Q.9 D Q.10 A
Q.11 A Q.12 C Q.13 A Q.14 A Q.15 A
Q.16 C Q.17 B Q.18 D Q.19 A Q.20 A
Q.21 A Q.22 D Q.23 D Q.24 C Q.25 A
Q.26 C Q.27 B Q.28 C Q.29 B Q.30 A
Q.31 A Q.32 B Q.33 A Q.34 A Q.35 B
Q.36 A,B,C,D Q.37 C,D Q.38 C,D Q.39 A Q.40 C,D
Q.41 B Q.42 A,C Q.43 C,D
Q.44 (A) P,R,S (B) P,Q,R,S (C) P,Q,R,S Q.45 A  P; B  Q; C  S;
Q.46 2 Q.47 7 Q.48 2 Q.49 5 Q.50 6
EXERCISE III
Q.1 D Q.2 D
Q.3 (i) Kc= 8.1 × 10–5 mol2 L–2 ; Kp = 4.91 × 10–2 atm 2 (ii) No effect; Q.4 D Q.5 D

Q.6 A, B, D Q.7 A Q.8 C Q.9 B Q.10 C 11. B 12. B
13. A 14. B 15. D 16. A 17. D 18. D 19. B
20. A 21. A 22. D 23. D 24. D 25. 8.93 (8.70 – 9.10)

Chemical Equilibrium: Chemistry

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Chemical Equilibrium: Chemistry

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CHEMISTRY

" A SPECIALLY DESIGNED KIT FOR LEARNING."

THE KEY  Basic principles of subjects. An outline of the

IMPORTANT CHARACTERISTIC OF EQUILIBRIUM

HOMOGENEOUS CHEMICAL EQUILIBRIA

(ii) Hg 22 (aq) + NO3 (aq) + 3H3O+(aq) 2Hg2+ (aq) + HNO2(aq) +4H2O(l)

(iii) NH3(aq) + H2O (l) NH4+(aq) + OH– (aq)

HOMOGENEOUS EQUILIBRIA IN GASES

Example : (i) C2H6(g) C2H4(g) + H2(g)

[C 2H4 ][H2 ] (PC2H4 )(PH2 )

[ ] represents concentration PC2H 4 & other are partial pressure at equilibrium

(iii) KP = PBr (g) ; KC = [Br2(g)]

UNIT OF EQUILIBRIUM CONSTANT

Predicting the extent of a reaction

FACTOR'S AFFECTING EQUILIBRIA

EFFECT OF CHANGE IN CONCENTRATION ON EQUILIBRIUM

EFFECT OF CHANGE IN PRESSURE

H2(g) + I2(g) 2I(g) H = – 9.4 kJ (exothermic)

EFFECT OF TEMPERATURE : VAN'T HOFF EQUATION

Process Characteristic constant

H2O (l) H2O (g) PH constant at given temperature

H2O (s) H2O (l) PH constant at given temperature

solute (s) solute (soln) concentration of solute is constant at given temperature

Physical Equilibrium Chemical Equilibrium

(a) degree of dissociation from vapour

Application of equilibrium constant Le Chatelier's principle

Temperature dependence - Von't Hoff's equation

14. At 700 K, Kp = 0.2 for the reaction ClF3 (g) ClF (g) + F2(g). Calculate the equilibrium partial pressure of

Homogeneous equilibria degree of dissociation, vapour density and equilibrium constant

16. At 46°C, Kp for the reaction N2O4(g) 2NO2(g) is 0.667 atm. Compute the percent dissociation of N2O4

20. The system N2O4 2 NO2 maintained in a closed vessel at 60º C & a pressure of 5 atm has an average

21. In the esterfication C2H5OH (l) + CH3COOH (l) CH3COOC2H5 (l) + H2O (l) an equimolar mixture of

28. For the reaction I2(g) 2I(g), KC = 3.92 × 10–6 at 727ºC. Let 1 mole of I2 be injected into a 2 litre glass

Kinetics and equilibrium constant

Temperature dependence of equilibrium constant

39. The equilibrium constant Kp for the reaction PCl5(g) PCl3(g) + Cl2(g) is 3.81 × 102 at 600 K and

Temperature dependence of equilibrium constant

41. The KP for reaction A + B C + D is1.34 at 60°C and 6.64 at 100°C. Calculate H° for the reaction over

Equilibrium expressions and equilibrium constants

10. The equilibrium constant for the reaction CO(g) + H2O(g) CO2(g) + H2(g) is 8.0 at 450º C & 1atm

14. The equilibrium pXyloquinone + methylene white pXylohydroquinone + methylene blue may be

15. A certain gas A polymerizes to a small extent at a given temperature & pressure, nA A

3. For the following gases equilibrium. N2O4 (g) 2NO2 (g)

14. The equilibrium constant for the reaction CO(g) + H2O(g) CO2(g) + H2(g) is 3 at 500 K. In a 2 litre vessel

21. The equilibrium constants K P and K P for the reactions

22. When N2O5 is heated at temperature T, it dissociated as N2O5 N2O3 + O2, Kc = 2.5. At the same time

(A) K K K (B) K 1K 32 K 2 (C) K 2K 33 K1 (D) K1K2K3

Paragraph for Questions Nos. 27 to 30

Paragraph for Questions Nos. 31 to 33

34. Assertion : In a close system, number of reacting species may not be in state of equilibrium (Material,

More than one may be correct

37. Consider the equilibrium HgO(s) + 4I– (aq) + H2O () HgI42– (aq) + 2OH– (aq), which changes will

38. For the reaction PCl5(g) PCl3(g) + Cl2(g), the forward reaction at constant temperature is favoured by

39. The equilibrium SO2Cl2(g) SO2(g) + Cl2(g) is attained at 25°C in a closed rigid container and an inert

42. Decrease in the pressure for the following equilibria : H2O(s) H2O (l) result in the :

195 217 298 304

Match the column :

(B) Addition of inert gas at constant pressure in (Q) Equilibrium shifts in backward direction

48. Calculate the value of Keq for the reaction Zn(s) + 2H+(aq) Zn2+(aq) + H2(g).

49. For the equilibrium CuSO4 . 5H2O(s) CuSO4 . 3H2O(s) + 2H2O(g) Kp = 2.25 × 10–4 atm2 and vapour

1.44  10 –5 1.44  10 –5 1.44  10 –5 1.44  10 –5

9. The % yield of ammonia as a function of time in the reaction [JEE Advance 2015]

10. The equilibrium constant at 298 K for a reaction A + B C + D is 100. If the initial concentration of all the