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Chemical Equillibrium INTRODUCTION 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 represents the state of a process in which the properties like temperature, pressure, 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. Some common physical equilibria are: Solid Liquid Liquid Gas Gas Solution Generally, a chemical equilibrium is represented as aA + bB xX + yY Where A, B are reactants and X, Y are products. Note: The double arrow between the left hand part and right hand part shows that changes is 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.

EQUILIBRIUM IN PHYSICAL PROCESS 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 (i) 3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g) (ii) CaCO3(s) CaO(s) + CO2(g) (iii) 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 anirreversible reaction.

Examples are: (i) (ii) Note: If any of the product will be removed from the system, reversible reaction will become irreversible one.
CONCEPT OF CHEMICAL EQUILIBRIUM Let we have a general reversible reaction, A at time t = 0 a0 + B b0 C 0 + D 0

AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(g) 2M(g) + O2(g) 2MgO(s)

as time will pass, A and B will be converted to C and D. As soon as C and D will be formed, reaction will start in back direction also. A time will come when rate of decomposition of A and B will be equal to the rate of formation of A & B, i.e. the rate of forward reaction will be equal to the rate of reverse reaction. At this stage the reaction is said to be in a state of Chemical Equilibrium. If we see variation of reactants and products with time on graph we will be having following graph. When the equilibrium is reacted, the concentration of reactant as well as product remains constant. At this stage reaction seems to be stopped but in actual the reaction is going in forward as well as reverse direction with same rate and hence this equilibrium is called as dynamic equilibrium. Alt text: Dynamic equilibrium Characteristics of Chemical Equilibrium The equilibrium is dynamic i.e. the reaction continues in both forward and reverse directions. The rate of forward reaction equals to the rate of reverse reaction. The observable properties of the system such as pressure, concentration, density remains invariant with time. The chemical equilibrium can be approached from either side. A catalyst can hasten the approach of equilibrium but does not alter the state of equilibrium. Types of Equilibria There are mainly two types of equilibria:

(a)

Homogeneous: Equilibrium is said to be homogeneous if reactants and products are in same phase. H2(g) + I2(g) 2HI(g) N2(g) + 3H2(g) 2NH3(g) N2O4(g) 2NO2(g) CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)

(b)

Heterogeneous: Equilibrium is said to be heterogeneous if reactants and products are in different phases CaCO3(s) CaO(s) + CO2(g) NH4HS(s) NH3(g) + H2S(g) NH2CO2NH4(s) 2NH3(g) + CO2(g)

Note: To write the equilibrium constant expression, the concentration of pure liquid and pure solid assumed to be unity, as the concentration of such substances remain constant, i.e., concentration = mole/litre density

Solved example 1. For the gaseous reaction: C2H2 + D2O C2D2 + H2O, H is 530 cal. At 25C, KP = 0.82. Calculate how much C2D2 will be formed if 1 mole of C2H2 and 2 moles of D2O are put together at a total pressure of 1 atm at 100C? Sol. Firstly calculate KP at 100C by using equation log (Kp)100oC/(Kp)25oC = H/2.303R (T2-T1/T1T2) On solving we get, (KP)100C = 0.98 C2H2 Initial mole 1 At eq. mole 1 0.98 = 2/(1-)(2-) 0.02 + 2.94 1.96 = 0 On solving we get, = 0.75 + D2 O 2 2 C2D2 0 + H2O 0

Solved example 2. An equilibrium mixture at 300K contains N2O4 and NO2 at 0.28 and 1.1 atm respectively. If the volume of container is doubled, calculate the new equilibrium pressure of two gases. Sol. N2O4(g) 2NO2(g) 0.28 1.1 Kp = (1.1)2/0.28 = 4.32 atm When volume is doubled pressure will reduced to half N2O4(g) 2NO2(g) (0.28/2 p) (1.1/2 + 2p)

Kp = (1.1/2+2p)2/(0.28/2p) = 4.32 p = 0.045 p(N2O4) = 0.14 0.045 = 0.095 p(NO2) = 0.55 0.045 = 0.64 atm Solved example 3. At 540K, 0.10 mole of PCl 5 are heated in a 8 litre flask. The pressure of the equilibrium mixture is found to be 1 atm. Calculate the Kpfor the reaction. Sol. PCl5 PCl3 + Cl2 0.1

Total no. of moles = 0.1 + + = 0.1 + Now, P = nRT/V 1 = (0.1+)0.082540/8 (0.1 + ) = 0.180 = 0.08 So, Kp = (pPCl3 pCl2)/(pPCl5) = (p/0.1+)(p/0.1+)/(0.1)/(0.1+)p = 2p/(0.1+)(0.1) = 0.00641/0.180.02 = 1.78 atm Solved example 4. In a mixture of N2 and H2 initially in a mole ratio of 1:3 at 30 atm and 300oC, the percentage of ammonia by volume under the equilibrium is 17.8. Calculate the equilibrium constant (KP) of the mixture, for the reaction N2(g) + 3H2(g) 2NH3(g) Sol. Let the initial moles of N2 and H2 be 1 and 3 respectively (this assumption is valid as KP will not depend on the exact no. of moles of N2 and H2. One can even start with x and 3x). Alternatively N2(g) + 3H2(g) 2NH3

Initial At eqb.

1 1-x

3 3-3x

0 2x

Since % by volume of a NH3 gas is same as % by mole, 2x/42x = 0.178 x = 40.178/(2+20.178) = 0.302 Mole fraction of H2 at equilibrium = 33x/42x = 0.6165 Mole fraction of N2 at equilibrium = 1 - 0.6165 - 0.178 = 0.2055 KP = (XNH3PT)2/(XN2PT)(XH2PT)3 = (0.17830)2/(0.205530)(0.616530)3 = 7.31 10-4 atm2 Solved example 5. The density of an equilibrium mixture of N2O4 and NO2 at 1 atm. and 348 K is 1.84 g dm-3. Calculate the equilibrium constant of the reaction, N2O4(g) 2NO2(g). Sol. Let us assume that we start with C moles of N2O4(g) initially. N2O4(g) 2NO2(g) Initial At equilibrium C C(1-) 0 2C

Where is the degree of dissociation of N2O4(g) Since = Total moles at equilibrium/Total moles initially = Vapour density initial/Vapour density at equilibrium Initial vapour density = 92/2 = 46 C(1+)/C = 46/d Since vapour density and actual density are related by the equation, V.D. = RT/2P = 1.840.082348/2 = 26.25 1 + = 46/26.25 = 1.752 = 0.752 Kp = (2C/C(1+) PT)2/C(1-)/C(1+) PT = (20.75/1.7521)2/0.248/1.752

= 5.2 atm Solved example 6. At temperature T, a compound AB2(g) dissociates according to the reaction 2AB2(g) 2AB(g) + B2(g) with a degree of dissociation x, which is small compared with unity. Deduce the expression for x in terms of the equilibrium constant, Kp and the total pressure P. Sol. Let the initial pressure of AB2(g) be P1 2AB2(g) 2AB(g) + B2(g) P1(1-x) P1x P1x/2

The total pressure is = P1 (1+x/2) P1 ( x<< 1) P1 = P So, KP = (Px)2Px/2/[P(1-x)]2 Px3/2 x = 32Kp/P LAW OF MASS ACTION 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. aA + bB cC + dD 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. Illustration 1. equilibria Calculate the partial pressure of each component in the following

N2(g) + 3H2(g) 2NH3(g) Solution: at t = 0 at equilibrium N2(g) a ax + 3H2(g) b b 3x 2NH3(g) 0 2x

ntotal = a x + b 3x + 2x = (a + b 2x) Partial pressure: PN2 = nN2/nT PT = (ax)/(a+b2x)PT PH2 = nH2/nT PT = (b3x)/(a+b2x)PT PNH3 = nNH3/nT PT = 2x/(a+b2x)PT Law of Chemical Equilibrium According to this law, the ratio of product of concentration of products to the product of concentration of reactants, with each concentration term is raised to the power by its coefficient in overall balanced chemical equation, is a constant quantity at a given temperature and it is called equilibrium constant. Derivation of law of chemical equilibrium

Let us consider for the following equilibrium aA + bB cC + dD then, from Law of mass action rate of forward reaction r1 [A]a [B]b or r1 = Ka [A]a [B]b and rate of reverse reaction r2 [C]c [D]d r2 = K2 [C]c [D]d at equilibrium, r1 = r2 K1 [A]a[B]b = K2 [C]c[D]d K1/K2 = [C]c[D]d/[A]a[B]b Kc = K1/K2, an equilibrium constant in terms of active masses of reacting species. the reaction SO2Cl2 at t = 0 at equilibrium equilibrium conc. container) So, So, a a-x ax/V SO2 0 x x/V + Cl2 0 x x/V (V is volume of

[SO2Cl2] = ax/V; [SO2] = x/V = [Cl2] Kc = (x/V)(x/V)/(ax/V) = x2/(ax)V Kc = x2/(ax)V

HARACTERISTICS OF EQUILIBRIUM CONSTANT (Kc) (i) Kc for a particular reaction at given temperature has a constant value. (ii) Value of Kc always depends on nature of reactants and the temperature, but independent of presence of catalyst or, of inert material. (iii) Its value is always independent of the initial concentration of reactants as well as the products. (iv) The value of Kc indicates the proportion of products/product formed at equilibrium. Large Kc value means large proportions of product. (v) When the reaction is reversed, equilibrium constant for reverse reaction will also be inversed. K'c = 1/Kc

Let us have A+BC+D Kc = [C][D]/[A][B] By reversing the reaction, C+DA+B K'c = [A][B]/[C][D]=1/Kc (vi) If the coefficients of reactants of products are halved or, doubled then accordingly, value of K'c will change. A+BC+D Kc = [C][D]/[A][B] for 2A + 2B 2C + 2D K'c = [C]2[D]2/[A]2[B]2 = {[C][D]/[A][B]}2 = K2c (vii) When a number of equilibrium reactions are added, the equilibrium constant, for overall reaction is the product of equilibrium constants of respective reactions. N2(g) + O2(g) 2NO; N2O(g) N2(g) + 1/2O2(g); N2O(g) + 1/2O2(g) 2NO(g); K1 = [NO]2/[N2][O2] K2 = [N2][O2]1/2/[N2O] K3 = [NO]2/[N2O][O2]1/2

K3/K2 = [NO]2/[N2O][O2]1/2 [N2O]/[N2][O2]1/2 = [NO]2/[N2][O2] = K1 i.e. K3/K2 = K1 Equilibrium constant in terms of partial pressures Let us consider a general reaction aA + bB cC + dD PA PB PC PD

From law of mass action r1 (Pa)a (PB)b r1 = K1(PA)a(PB)b r2 (Pc)c (PD)d r2 = K2(PC)c(PD)d at equilibrium

r1 = r2 or K1 (PA)a (PB)b = K2(PC)c(PD)d K1/K2 = (PC)a(PD)d/(PA)a(PB)b Kp = K1/K2 = (PC)a(PD)d/(PA)a(PB)b

RELATION BETWEEN KP AND KC

For a general equation,

aA + bB

cC + dD

Where, a , b, c and d are coefficients of the reacting substance

Kp = (PC) (OD) / (PA) (PB)

From gas equation

PV = nRT

=> P = n/V RT

So,

PA = [A]RT PB = [B]RT

PC = [C]RT; PD = [D]RT

Hence,

Kp = ([C]RT) .([D]RT) / ([A]RT) / ([B]RT)

or, Kp = [C] [D] / [A] [B] (RT)

[(c+d) (a+b)]

Where ng = {(c + d) (a + b)} = change in the numbers of gaseous moles.

Hence,

Kp = Kc.(RT)

n g

When

n = 0; Kp = Kc

n > 0; Kp > Kc

n < 0;

Kp < Kc

Note:

Similarly we can find equilibrium constant (Kx) interms of mole fraction and can find out its relation with Kp and Kc.

Illustration . At 27C Kp value for reaction is 0.1 atm, calculate its Kc value.

Solution:

KP = Kc(RT)

Dn

n = 1

Kc = KP / RT = 0.1 / 0.82 300 = 4 10

-3

Illustration . Solid NH4I dissociates according to the reaction at 400 K NH4I(s) NH3(g) + HI(g) ; Kp = 16 atm. In presence of catalyst HI dissociates in H2 and I2 as 2HI H2 + I2. If partial pressure of H2 at this temp is 1 atm in the container when both the equilibrium exist simultaneously, calculate Kp value of second equilibrium (for the dissociation of HI).

Solution:

NH4I(s)

NH3 (g) + HI (g)

KP1 = 16

2HI

H2 +

I2

P-x

x/2 . x/2

KP2 = ?

Here x/2 = 1 atm

x = 2 atm

P(P -2) = 16

P = 5.1

Illustration . A vessel at 1000 K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted into CO on addition of graphite. What is the value of Kp if the total pressure at equilibrium is 0.8 atm?

Solution:

CO2(g)

C(s)

>

2CO(g)

0.5

2n

or, 0.5-n

0.5+n = 0.8

n = 0.3

Kp = (20.3) / (0.50.3) = 1.8 atm

Illustration . Given that the equilibrium constant for the reaction, H 2(g) + I2(g) Calculate the equilibrium constant for the reaction.

2HI(g) is 50 at 700K.

HI(g)

1/2 H2(g) + 1/2 l2(g)

Solution:

We have H2(g) + I2(g)

2HI(g)

Kc = [Hl] / [H2][l2] = 50

The new equilibria is

HI(g)

[H2]1/2[l2]1/2 / [Hl] = 1/Kc

= 1/ 50 = 2 / 10 = 0.141

Illustration . One mole of N2 is mixed with 3 moles of H2 in a 4 litre container. If 25% of N2 is converted into NH3 by the following reaction N2(g) + 3H2(g) = 0.08231). 2NH3(g). Calculate Kc and Kp of the reaction. (Temperature = 227C and R

Solution:

We have N2(g) + 3H2(g)

2NH3(g)

Percentage N2 reacted, 25%

x = 0.25

Now, (a x) = 1 0.25 = 0.75

b 3x = 3 0.75 = 2.25

= 1.48 10

L mol

Now, Kp = Kc . (RT)

= 1.48 10

[0.0821] (227 + 273)

1.48 10

/ {0.082 (500)}

= 8.78 10

RELATION BETWEEN KP AND KC

For a general equation,

aA + bB

cC + dD

Where, a , b, c and d are coefficients of the reacting substance

Kp = (PC) (OD) / (PA) (PB)

From gas equation

PV = nRT

=> P = n/V RT

So,

PA = [A]RT PB = [B]RT

PC = [C]RT; PD = [D]RT

Hence,

Kp = ([C]RT) .([D]RT) / ([A]RT) / ([B]RT)

or, Kp = [C] [D] / [A] [B] (RT)

[(c+d) (a+b)]

Where ng = {(c + d) (a + b)} = change in the numbers of gaseous moles.

Hence,

Kp = Kc.(RT)

n g

When

n = 0; Kp = Kc

n > 0; Kp > Kc

n < 0;

Kp < Kc

Note:

Similarly we can find equilibrium constant (Kx) interms of mole fraction and can find out its relation with Kp and Kc.

Illustration . At 27C Kp value for reaction is 0.1 atm, calculate its Kc value.

Solution:

KP = Kc(RT)

Dn

n = 1

Kc = KP / RT = 0.1 / 0.82 300 = 4 10

-3

Illustration . Solid NH4I dissociates according to the reaction at 400 K NH4I(s) NH3(g) + HI(g) ; Kp = 16 atm. In presence of catalyst HI dissociates in H2 and I2 as 2HI H2 + I2. If partial pressure of H2 at this temp is 1 atm in the container when both the equilibrium exist simultaneously, calculate Kp value of second equilibrium (for the dissociation of HI).

Solution:

NH4I(s)

NH3 (g) + HI (g)

KP1 = 16

2HI

H2 +

I2

P-x

x/2 . x/2

KP2 = ?

Here x/2 = 1 atm

x = 2 atm

P(P -2) = 16

P = 5.1

Illustration . A vessel at 1000 K contains CO2 with a pressure of 0.5 atm. Some of the CO2 is converted into CO on addition of graphite. What is the value of Kp if the total pressure at equilibrium is 0.8 atm?

Solution:

CO2(g)

C(s)

>

2CO(g)

0.5

2n

or, 0.5-n

0.5+n = 0.8

n = 0.3

Kp = (20.3) / (0.50.3) = 1.8 atm

Illustration . Given that the equilibrium constant for the reaction, H 2(g) + I2(g) Calculate the equilibrium constant for the reaction.

2HI(g) is 50 at 700K.

HI(g)

1/2 H2(g) + 1/2 l2(g)

Solution:

We have H2(g) + I2(g)

2HI(g)

Kc = [Hl] / [H2][l2] = 50

The new equilibria is

HI(g)

[H2]1/2[l2]1/2 / [Hl] = 1/Kc

= 1/ 50 = 2 / 10 = 0.141

Illustration . One mole of N2 is mixed with 3 moles of H2 in a 4 litre container. If 25% of N2 is converted into NH3 by the following reaction N2(g) + 3H2(g) = 0.08231). 2NH3(g). Calculate Kc and Kp of the reaction. (Temperature = 227C and R

Solution:

We have N2(g) + 3H2(g)

2NH3(g)

Percentage N2 reacted, 25%

x = 0.25

Now, (a x) = 1 0.25 = 0.75

b 3x = 3 0.75 = 2.25

= 1.48 10

L mol

Now, Kp = Kc . (RT)

= 1.48 10

[0.0821] (227 + 273)

1.48 10

/ {0.082 (500)}

= 8.78 10

SIGNIFICANCE OF THE MAGNITUDE OF EQUILIBRIUM CONSTANT

(i) so.

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

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

(iii) 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 o 0.035 atm at 400 C, when the partial pressures are expressed in atmosphere. Calculate Kc for the reaction,

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

Solution:

KP = KC (RT)

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 mol l

-4

-1

KC for the reverse reaction would be 1/KC

KC = 1/6.34210

= 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 n n (KC) or (KP) 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 1000 C is 0.4. If CO(g) at a o pressure of 1 atm and excess FeO(s) are placed in a container at 1000 C, 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.

Illustration . At 800 K a reaction mixture contained 0.5 mole of SO2, 0.12 mole of O2 and 5 mole of SO3 at equilibrium. Kc for the equilibrium 2SO2 + O2 2SO3 is 833 lit/ mole. If the volume of the container is

1 litre, calculate how much O2 is to be added at this equilibrium in order to get 5.2 moles of SO 3 at the same temperature.

Solution: Suppose x mole of O2 is added by which equilibrium shifts to right hand side and y mole of O2 changes to SO3.

The new equilibrium concentration may be

2 SO2 +

O2

2SO3

Moles at I equilibrium

0.5

0.12

II equilibrium

(0.5-2y)

(0.12+x-y)

(5+2y)

5 + 2y = 5.2

y = 0.1

Kc = = 833

Substituting y = 0.1 (V = 1 lit) We get x = 0.34 mole

THE REACTION QUOTIENT Q

Consider the equilibrium

PCl5 (g)

PCl3(g) + Cl2 (g)

At equilibrium [Cl2].[PCl3] / [PCl5] = KC. 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

Illustration . For the reaction : A(aq)+ B(aq) C(aq)+D(aq) , the net rate of consumption of B at 25C and at any time 't' is as given below

d/[b]/ dt = {410 [A] [B] 1.3310 [C] [D]} mol L min

-4

-5

-1

-1

Predict whether the reaction will be spontaneous in the direction as written in reaction mixture -1 in which each A, B, C and D is having a concentration of 1 mol L ?

Solution:

K = K1/K2

= 4 10

/ 1.33 10

= 30

Q = [C][D] / [A][B]

=11/11=1<K

Since Q < K, so the above reaction is spontaneous in the forward direction.

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.

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 Cl2, 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.

(i) 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.

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

(iii) 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.

(iv) 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 Concentration

Let us have a general reaction,

aA + bB

cC + dD

at a given temperature, the equilibrium constant,

Kc = [C] [D] / [A] [B]

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

then, Kc = [] [] / [] []

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.

Temperature Effect

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,

Kr = Af ee

/RT

And for the reverse reaction,

It can be seen that

For any reaction, H = Eaf Ear

R = Reactant, P = Product

From the equation, logK2/K1 = H / 2.303R (1/T1 1/T2) it is clear that


o

(a) If H is +ve (endothermic), an increase in temperature (T 2 > T1) will make K2 > K1, i.e., the reaction goes more towards the forward direction and vice-versa.
o

(b) If H is -ve (exothermic), an increase in temperature (T 2 > T1), will make K2 < K1 i.e., the reaction goes in the reverse direction.
o

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

(ii) 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.

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

Solved 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.

Solved example . The equilibrium constant KP for the reaction N2(g) + 3H2(g) 2NH3(g) is 1.6 -4 -2 o o 10 atm at 400 C. What will be the equilibrium constant at 500 C 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

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 P
n

= QP / P

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

Case C:

When n = +ve Kp = QP P
n

and, effect will be opposite to that of Case B

EFFECT OF CATALYST ON EQUILIBRIUM

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.

Effect on equilibrium due to the addition of inert gases

Following are the cases, where this effect in different manner.

Case A:

When n = 0 and total volume change at equilibrium remain constant.

So, addition of inert gases will increase the number of moles in the mixture but partial pressure of each component remains constant. Hence equilibrium remains unaffected.

Case B:

When n = +ve and VT 0

The total volume will increase with addition of inert gases. This will shift the equilibrium in forward direction.

Case C:

When n = ve and VT 0

In this case, the addition of inert gases will increase the total volume and the reaction will shift in reverse direction.

Dependence of KP or Kc on Temperature

With the increase of temperature, equilibrium favours forward reaction in case of an endothermic (H > 0) reaction while it favours backward reaction in the case of an exothermic (H < 0) reaction.

Sample problem . For the equilibrium

NH4I(g)

NH3(g) + HI(g)

H = +ve

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 10 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 10

= 25.14 / 2.330 2 10

[773 673 / 773 673]

=> KP2/1.46 10

atm

KP2 = p02 = 1.46 10

atm

Since, PV = nRT

1.46 10

2 = n 0.0821 773

n = 1.46 10

/ 0.0821 773 = = 4.60 10

-7

Let G be the difference in free energy of the reaction when all the reactants and products are in the standard state and Kc or, Kp be the thermodynamic equilibrium constant of the reaction. Both related to each other at temperature T by the following relation.

G = 2.303 RT logKc and G = 2.303 RT log Kp(in case of ideal gases)

Now, we know that thermodynamically,

G = H TDS

here H is standard enthalpy of reaction, and S is standard entropy change

(i)

When G = 0, then, Kc = 1

(ii) When, G > 0, i.e. +ve, then Kc < 1, in this case reverse reaction is feasible showing thereby a less concentration of products at equilibrium rate.

(iii) When G < 0, i.e. -ve, then, Kc > 1; In this case, forward reaction is feasible showing thereby a large concentrations of product at equilibrium state.

Sample problem.

A system is in equilibrium as

PCl5 + Heat > PCl3 + Cl2

Why does the temperature of the system decreases, when PCl3 are being removed from the equilibrium mixture at constant volume?

Solution: When PCl3 are being removed from the system, the reaction moved to the right. This consumed heat and therefore, temperature is decreased.

Sample problem. NO and Br2 at initial partial pressures of 98.4 and 41.3 torr, respectively, were allowed to react at 300K. At equilibrium the total pressure was 110.5 torr.

Calculate the value of the equilibrium constant and the standard free energy change at 300K for the reaction 2NO(g) + Br2(g) 2NOBr(g).

Solution:

2NO(g) + Br2(g) 2NOBr(g)

Initial pressure

98.4

41.3

At eqlbm.

98.4-x

41.3 - x/2

The total pressure at equilibrium is 110.5 torr.

98.4-x + 41.3- x/2 + x = 110.5

x = 58.4 torr

Now, 1 atm = 760.4 torr,

x = 7.68 10 atm.

-2

pNOBr = 7.68 10 atm ;

-2

pNO = 98.4-x = 40 torr = 5.26 10 atm.

-2

pBr2 = 41.3 x/2 = 12.1 torr = 1.59 10 atm.

-2

G = -2.303 RT log K = -2.303 (1.99) (300) (log 134)

= -2.92 k cal = -12.2 kJ.

[If R is used as 1.99 cal/mol K, then G will be in cal. If R is used as 8.314 J/mol K, n then G will be in Joules. But KP must always be in (atm) .]
o

Dependence of Degree of Dissociation on Density Measurements

The degree of dissociation of a substance is defined as the fraction of its molecules dissociating at a given time. The following is the method of calculating the degree of dissociation of a gas using vapour densities. This method is valid only for reactions whose KP exist, i.e., reactions having at least one gas and having no solution.

Since PV = nRT

PV = w/M nRT 0

M = wRT / PV = RT / P

VD = RT / 2P

Since P = NRT / V

VD = RT / 2nRT V = V / 2n

For a reaction at equilibrium V is a constant and is a constant. vapour Density 1/n

= Total moles at equulibrium / Initial total moles = vapour density intial / vapour ensity at equilibrium = D/d = M/m

(molecular weight = 2 V.D)

Here M = molecular weight initial

m = molecular weight at equilibrium

Let us take a reaction

PCl5 Initial moles At eqb. C C(1-)

PCl3 0 C

+ Cl2 0 C

= C(1+) / C = D/d;

1 + = D/d = M/m

Knowing D and d, can be calculated and so for M and m.

Sample problem. When PCl5 is heated it dissociates into PCl3 and Cl2. The density of the gas mixture o o o o at 200 C and at 250 C is 70.2 and 57.9 respectively. Find the degree of dissociation at 200 C and 250 C.

Solution:

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

We are given the vapour densities at equilibrium at 200 C and 250 C.

The initial vapour density will be the same at both the temperatures as

it would be MPCl5 / 2.

Initial vapour density = (31 + 5 35.5) / 2 = 104.25

Vapour density at equilibrium at 200 C = 70.2

Total moles at equilibrium / Total moles initial = 1 + = Vapour density initial / Vapour density at equilibium

= 104.25 / 70.2 = 1.485

a = 0.485

At 250 C,

1 + = 104.25 / 57.9 = 1.8

a = 0.8

Sample problem. the mixture.

The degree of dissociation of PCl5 is 60%, then find out the observed molar mass of

Solution: Initially moles At eqm.

PCl5(g) 1 1

PCl3(g) + Cl2(g) 0 0

Where = degree of dissociation = 0.6

Total moles at equilibrium = 1 + a = observed mole

observed moles / Theoretica moles = molecular weight theoertical / molecular weight observed

=> 1 + a = 206.5 / molecular weight observed

=> molecular weight observed = 206.5 / 1 + a = 206.5 / 1.6 = 129.06

Exercise .

Vapour density of N2O4 which dissociates according to the equilibrium N 2O4(g) 2NO2(g) is 25.67 at 100C and a pressure of 1 atm. Calculate the degree of dissociation and K p for the reaction.

Exercise .

How much PCl5 must be added to a one litre vessel at 250 C in order to obtain a concentration of 0.1 mole of Cl2? Kc for PCl5 > PCl3 + Cl2 is 0.0414 mol/litre. Exercise 1.

Calculate the equilibrium pressure of each reactant of given reaction with the help of following data.

A+B

C+D

Initial pressure of A and B are 6 atm and 5 atm. The equilibrium pressure of C and D are 2 atm in each case.

Exercise 2 .

The equilibrium constant for the reaction

PCl5(g) PCl3(g) + Cl2(g) is 2.4 10 . Determine the equilibrium constant for the reverse reaction at same temperature.

Exercise 3

At 21.5C and a total pressure of 0.0787 atm, N2O4 is 48.3% dissociated into NO2. Calculate Kp and Kc for the reaction.

N2O4(g)

2NO2(g)

Exercise 4 .

(i) Write the expression for Kp and Kc for the following reactions.

N2 + 3H2

2NH3

(ii) Find out the heterogeneous equilibrium from the following reaction

(A) CaCO3 (s)

CaO(s) + CO2 (g)

(B) H2(g) + I2(g)

2HI (g)

Exercis 5

What is the value of equilibrium constant for the following reaction

If A

K1 = 2

K2 = 5

K3 = 3

Exercise 6.

In an equilibrium A + B > C + D; A and B are mixed in a vessel at temperature T. The initial concentration of A was twice the initial concentration of B. After the equilibrium has established, concentration of C was thrice the equilibrium concentration of B. Calculate K c.

Exercise .7

Ammonium hydrogen sulphide dissociates as follows

NH4HS(s) NH3(g) + H2S(g)

If solid NH4HS is placed in an evacuated flask at certain temperature it will dissociate until the total pressure is 600 torr.

(a) Calculate the value of equilibrium constant for the dissociation reaction

(b) Additional NH3 is introduced into the equilibrium mixture without changing the temperature until partial pressure of NH3 is 750 torr, what is the partial pressure of H2S under these conditions? What is the total pressure in the flask?

Exercise .8

At 700 K hydrogen and bromine react to form hydrogen bromide. The value of equilibrium 8 constant for this reaction is 5 10 . Calculate the amount of H2, Br2 and HBr at equilibrium if a mixture of 0.6 mole of H2 and 0.2 mole of Br2 is heated to 700 K.

Exercise 9

The equilibrium constant is 0.403 at 1000K for the process

FeO(s) + CO(g)

Fe(s)+ CO2)g)

A steam of pure CO is passed over powdered FeO at 1000K until equilibrium is reached. What is the mole fraction of CO in the gas stream leaving the reaction zone?

Exercise 10 .

N2 + 3H2

2NH3;

H = negative

What are the conditions of temperature and pressure favorable for this reaction?

Exercise 11: Equilibrium constant Kp for the reaction 3/2 H2(g) + 1/2 N2(g) NH3(g) are 0.0266 and 0.0129 at 310C and 400C respectively. Calculate the heat of formation of gaseous ammonia. Standard Free Energy Change of a Reaction and its Equilibrium Constant

Exercise 12.

What is the value of R if value of G is in?

(i) Joules

(ii) Calories

Exercise 13.

N2O4 is 25% dissociated at 27C and 1 atm pressure.

Calculate (i) Kp and (ii) the percentage dissociation at 0.1 atm and 27C.

ANSWERS TO EXERCISES

Exercise 1:

A > 4 atm

B > 3 atm

Exercise 2:

4.16 10

Exercise 3:

Kp = 0.0956 atm

Kc = 3.96 10

mole/lit

Exercise 4: (i) Kc = [NH3] / [N2] [H2]

Kp =

(ii) (A) is a heterogeneous equilibrium.

Exercise 5: K = 30

Exercise 6: 1.8

Exercise 7: (a) (b) 0.155 atm


2

119.32 torr, 869.32 torr

Exercise 8: 0.4, 0, 0.4

Exercise 9: 0.713

Exercise 10: Low temperature, high pressure and high concentration of N2 and H2.

Exercise 11. 12140 cals

Exercise 12: (i) (ii) 8.314 J mole K 2 cal mole K


-1 -1 -1 -1

Exercise 13: (i) (ii) 0.266 atm 93.27%

MISCELLANEOUS EXERCISES

Exercise 1: For an equilibrium, the rate constant for the forward and the backward reaction are -4 -5 2.38 10 and 8.15 10 respectively. Calculate the equilibrium constant for the reaction.

Exercise 2: In an experiment starting with 1 mole C2H5OH, 1 mole CH3COOH and 1 mole of water, the equilibrium mixture on analysis shows that 54.3% of the acid is esterified. Calculated K c.

Exercise 3: From the values of the equilibrium constants, indicate in which case, does the reaction -10 10 5 go farthest to completion: K1 = 10 , K2 = 10 , K3 = 10 .

Exercise 4:

The value of the equilibrium constant is less than zero. What does it indicate?

Exercise 5: Would you expect equilibrium constant for the reaction l2(g) decrease as temperature increases? Assign reason.

2l(g) to increase or

Exercise 6:

Acetic acid is highly soluble in water but still a weak electrolyte. Why?

Exercise 7: equilibria?

Which of the following reactions involve homogenous and which involve heterogenous

(a) 2N2O(g)

2N2 (g) + O2 (g)

(b) 2NO3(g)

N2 (g) + 3H2 (g)

(c) 2Cu(NO3)2(s)

2CuO(s) + 4O2 (g) + O2(g)

(d) CH3COOC2H5(l) + H2O(l)

CH3COOH (l) + C2H5OH(l)

(e) Fe

3+

(aq) + 3OH (aq)

Fe (OH)3(s)

Exercise 8: For the reaction, CH3(g) + 2H2S(g) CS2(g) + 4H2(g) at 1173 K, the magnitude of Kc is 3.6. For each of the following composition, decide whether the reaction mixture is at equilibrium. If not, decide to which direction the reaction should go?

Exercise 9: Kp for the reaction H2(g) + l2(g) 2Hl(g) at 460C is 49. If the partial pressure of H2 and I2 is 0.5 atm respectively, determine the partial pressure of each gas in the equilibrium mixture.

Exercise 10: 0.16 g N2H4 (hydrazine) are dissolved in water and the total volume is made upto 500 mL. -6 Calculate the percentage of N2H4 that has reacted with water in solution. The Kb for N2H4is 4.0 10 M.

ANSWERS TO MISCELLANEOUS EXERCISES

Exercise 1:

2.92

Exercise 2:

Kc = 4.012

Exercise 3: High value of equilibrium constant (K) means that the molar concentration of the products is quite large. In other words, the reaction has proceeded to a large extent in the forward 10 direction before attaining the equilibrium. Thus for K2 = 10 , the forward reaction has proceeded maximum before attaining the equilibrium.

Exercise 4: This indicates that the forward reaction has proceeded only to a small extent before the equilibrium is attained.

Exercise 5: In the forward reaction, energy is needed to bring about the dissociation of I2(g) molecules. This means that the forward reaction is endothermic in nature. The increase in temperature will favour the forward reaction. Therefore, the equilibrium constant will increase with rise in temperature.

Exercise 6: The strength of the electrolyte does not depend upon its amount present in solution but on its ionization in solution. Since acetic acid is a weak acid (organic acid), it is ionized only to small extent. Therefore, it is a weak electrolyte.

Exercise 7:

Homogenous equilibria : (a), (b) (d) Heterogenous equilibria : (c) and (e)

Exercise 8:

(a) Backward direction (b) Backward direction

Exercise 9:

Partial pressure of H2 (g) = 0.112 atm Partial pressure of I2(g) = 0.112 atm Partial pressure of HI (g) = 0.776 atm

Exercise 10: 2.0%

Objective:

Prob 1.

Reaction between iron and steam is reversible if it is carried out

3Fe + 4H2O > Fe3O4 + 4H2

(A) at constant T

(B) at constant P

(C) in an open vessel

(D) in a closed vessel

Sol.

In open vessel H2 gas will escape.

(D)

Prob 2.

For the reaction

PCl4(g) + Cl2(g) > PCl5(g)

The value of Kc at 250C is 26. The value of Kp at this temperature will be

(A) 0.61

(B)

0.57

(C) 0.83

(D)

0.46

Sol.

Kc = Kc (RT)

= 26 (0.082 523)

= 0.61

(A)

Prob 3. In a reversible reaction, two substances are in equilibrium. If the concentration of each one is doubled, the equilibrium constant will be

(A) Reduced to half, its original value

(B) becomes (original)/4

(C) doubled

(D) constant

Sol.

Kcor Kp do not depend on concentration, but only on temperature.

(D)

Prob 4.

The equilibrium constant for the reaction,

N2(g) + O2(g) > 2NO is 4 10

at 2000 K

In presence of a catalyst, equilibrium is attained ten times faster. Therefore, the equilibrium constant, in presence of the catalyst at 2000K is

(A) 40 10

(B)

4 10

(C) 4 10

(D)

difficulty to compute

Sol.

Equilibrium is constant at constant temperature for a reaction

(B)

Prob 5.

64g of HI are present in a 2 litre vessel. The active mass of HI is:

(A) 0.5

(B) 0.25

(C) 1

(D) none

Sol.

Molecular mass of HI = 128

HI] = [Hl] = 64/128 1/2 = 0.25

(B)

Prob 6.

For which of the following Kp may be equal to 0.5 atm

(A) 2HI

H2 + I 2

(B)

PCl5

PCl3 + Cl2

(C) N2 + 3H2

2NH3

(D)

2NO2

N2O4

Sol.

For Kp = 0.5 atm

n = 1 (since the unit is atm)

and PCl5

PCl3 + Cl2

n = 1

(B)

Prob 7. The vapour density of undecomposed N2O4 is 46. When heated, vapour density decreases to 24.5 due to its dissociation to NO2. The % dissociation of N2O4 at the final temperature is

(A) 80

(B)

60

(C) 40

(D)

70

Sol.

N2O4

2NO2

at initial

at equilibrium

46 / 25.4 = 1 + /1

1.8 = 1 + => = 0.8 or 80%

(A)

Prob 8.

If pressure is applied to the following equilibrium, liquid

vapours the boiling point of liquid

(A) will increase

(B)

will decrease

(C) may increase or decrease

(D)

will not change

Sol. Boiling point of a liquid is the temperature at which vapour pressure became equal to atm pressure. If the pressure is applied to the above equilibrium the reaction will go to the backward direction, i.e. vapour pressure decrease hence the boiling point increase.

(A)

Prob 9.

For the reaction

A(g) + B(g) 3C(g) at 250C, a 3 litre vessel contains 1, 2, 4 mole of A, B and C respectively. If KC for the reaction is 10, the reaction will proceed in

(A) Forward direction

(B)

Backward direction

(C) In either direction

(D)

In equilibrium

Sol.

Q = [C] / [A][B] = 4 3 3 / 3 1 2 = 10.66

[C] = 4/3

[A] = 1/3 => [B] = (2/3)

KC = 10, and Q > KC

reaction will proceed in backward direction

(B)

Prob 10. If CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(l) Kp = 1.086 0 10 atm at 25C. The efflorescent nature of CuSO4.5H2O can be noticed when vapour pressure of H2O in atmosphere is

(A) > 7.29 mm

(B)

< 7.92 mm

(C) > 7.92 mm

(D)

None

Sol.

An efflorescent salt is one that loses H 2O to atmosphere.

For the reaction

CuSO4.5H2O(s)

CuSO4.3H2O(s) + 2H2O(l)

Kp = ( PH2O ) = 1.086 10

PH2O = 1.042 10

atm = 7.92 mm

If PH2O at 25C < 7.92 mm only then, reaction will proceed in forward direction.

\ (B)

SOLVED PROBLEMS

Subjective:

Board Type Questions

Prob 1. At 444C, 15g mole of hydrogen are mixed with 5.2g mole of I2 vapour. When equilibrium was established, 10g mole of HI was formed. Calculate the equilibrium constant for the reaction.

Sol.

H2(g) + l2(g) a ax b bx

2Hl 0 2x

So,

= 4x / (ax) (bx) = 4 5 / 10 0.2 = 50

Prob 2.

The degree of dissociation is 0.4 at 400K and 1 atm for the gaseous reaction

PCl5

PCl3 + Cl2

Assuming ideal behaviour of all the gases, calculate the density of equilibrium mixture at 400K and 1 atm pressure.

(Atomic mass of P = 31 and Cl = 35.5)

Sol.

PCl5

PCl3 + Cl2

at t = 0

at eqm.

1 0.4

0.4

0.4

Total no. of moles after dissociation = 0.6 + 0.4 + 0.4

Now, V = nRT / P = 1.4 0.082 400 / 1 = 45.92 litres

So, density = Molecular weight / Volume = 208.5 / 45.92 = 4.54 / litre

Prob 3. When 3.06g of solid NH4HS is introduced into a 2 litre evacuated flask at 27C, 30% of the solid decomposed into gaseous ammonia and hydrogen sulphide.

(i) Calculate Kc for reaction at 27C.

(ii) What would happen to the equilibrium when more solid NH4HS is introduced into the flask?

Sol.

Moles of NH4HS introduced into flask = 3.06 / 51 = 0.08

NH4HS(s)

NH3(g) + H2S (g)

0.06 (1 x)

0.06x

0.06x

as x = 30%, so, x = 0.3

So, 0.06 0.7

0.060.3 0

0.6 0.3

So, Kc = [NH3][H2S]

0.018 0.018 = 3.24 10

Addition of NH4HS(s) does not change position of equilibrium.

Prob 4. Determine Kc for the reaction N2(g) + O2(g) + Br2(g) > NOBr(g) from the following o information (at 298 K)

Kc = 2.4 10 for 2NO(g) > N2(g) + O2(g) ;

30

K'c = 1.4 for NO(g) + Br2(g) > NOBr(g)

Sol.

N2(g) + O2(g) > 2NO (g)

Kc = 1/Kc = 1/2.4 10

30

(i) N2(g) + O2(g ) NO(g)

Kc =

//

(ii) NO(g) + Br2(g) NOBr(g) = 1.4.

(i) + (ii) gives the net reaction:

Prob 5. The heat of reaction at constant volume for an endothermic reaction in equilibrium is 1200 cal more than at constant pressure at 300K. Calculate the ratio of equilibrium constant K pand Kc.

Sol.

Given that E H = 1200 cal

Also we have

nRT = 1200

or n = 1200 / 2 300 = 2 (R = 2calK

mol )

Now, Kp = Kc (RT)

Kp = Kc (0.0281 300) = 1.648 10

IIT Level Question

Prob 6. Anhydrous CaCl2 is often used as dessicant. In presence of excess of CaCl2, the amount of 85 water taken up is governed by Kp = 1.28 10 for the following reaction at room temperature, CaCl2(s) + 6H2O(g) CaCl2.6H2O(s)

What is the equilibrium pressure of water in a closed vessel that contains CaCl 2(s)?

Sol.

CaCl2(s) + 6H2O(g) CaCl2.6H2O(s)

Prob 7.

NO2(g) NO(g) + 1/2O2(g)

Consider the above equilibrium where one mole of NO2 is placed in a vessel and allowed to come to equilibrium at a total pressure of 1 atm. Experimental analysis shows that

Temperature
PNO / PNO2

700K 0.872

800K 2.50

(a) Calculate Kp at 700K and 800K

(b) Calculate G

Sol.

(a)

NO2(g)

NO(g) + 1/2 O2(g)

at t = 0 1 mole

t eq.

1 2x

2x

partial (12x/1+x)PT

(2x / 1+x) PT (x/1+x)PT

at equilibrium pressure.

Given that

PNO / PNO2 = 0.872 at 700K

=> (2x/1+x)PT / (2x/1+x) PT = 0.872

=> 2x / 1 2x = 0.872

=> x = 0.2329

PO2 = x / 1 + x PT = 0.1889

KPt = PNO / PNO2 (PO2)

x/2

= = 0.372 atm

1/2

= 0.872 (0.1889)

1/2

= 0.372 atm

1/2

Similarly KB2 can be calculated

(b) G = RTlogKp

= 2.303 8.314 700log 0.379

= 5.65kJ/mol

Prob 8.

At 25C and 1 atm, N2O4 dissociates by the reaction

N2O4(g)

2NO2(g)

If it is 35% dissociated at given condition, find

(i) The percent dissociation at same temperature if total pressure is 0.2 atm.

(ii) The percent dissociation (at same temperature) in a 80g of N 2O4 confined to a 7 litre vessel.

(iii) What volume of above mixture will diffuse if 20 ml of pure O 2 diffuses in 10 minutes at same temperature and pressure?

Sol. t equilibrium Partial pressure at equilibrium 1a

N2O4(g) 2a

2NO2(g)

[1 / 1 + ] PT [2/1+]PT

= 4(0.35) / 1 (0.35) 1 = 0.56 atm

(i) KP = 4 / 1 P

0.56 = 4 / 1 0.2

Solving, = 0.64

% dissociation = 64%

(ii) Since

KP = Kc (RT)

Here n = 1

Kc = Kc / RT = 0.56 / 0.0821 298 = 0.0228 mole/litre

Kc = 4 / (1)V where x = no. of moles of N2O4(g) = 80/92

Neglecting with respect to 1

i.e. 1 a ~ 1

Kc = 4 / V

0.0228 = 4 80 / 92 / 7 = = 0.2142

% dissociation = 21.42%

Let V(ml) volume of mixture diffused in Now, from Grahams law of diffusion.

Prob 9. Solid NH4I on rapid heating in a closed vessel at 357C develops a constant pressure of 275 mm of Hg owing to the partial decomposition of NH4I into NH3 and HI but the pressure gradually increases further (when excess solid residually remains in the vessel) owing to the dissociation of HI. Calculate the final pressure developed under equilibrium.

NH4I(s)

NH3(g) + HI(g)

2HI(g)

H2(g) + I2(g)

Kc = 0.015 at 357C

Sol.

P = 275/760 = 0.3618 atm

= 0.181 atm

Kp = (0.181) = 0.033 atm

NH4I(s)

NH3(g)

HI(g)

(0.181 + p)

(0.181 + p p') Kp = 3.3 10

atm

2HI(g)

H2(g)

I2(g)

(0.181 + p p')

p'/2

p'/2

Kp = 0.015

0.033 = (0.018 p) (0.181 + p p')

0.015 = pr2/4(0.181 + p p) => p' = 0.04 atm

p = 0.026 atm

total pressure = 2(0.181 + p) = 0.414

= 314.64 mm Hg

Prob 1. The enthalpies of two reaction are H1 and H2 (both positive) with H2 >H1. If the temperature of reacting system is increased from T1 to T2, predict which of the following alternatives is correct?

Sol. As the temperature of reacting system is increased the equilibrium constant of reaction is also increased for endothermic reactions so for two reactions on increasing the temperature by equal amounts

K'1 / K1 < K'2 / K2

Hence, (C) is correct.

Prob 2. At a certain temperature 2 moles of carbonmonoxide and 3 moles of chlorine were allowed to reach equilibrium according to the reaction CO + Cl2 > COCl2 in a 5 lit vessel. At equilibrium if one mole of CO is present then equilibrium constant for the reaction is:

(A) 2

(B) 2.5

(C) 3.0

(D) 4

Sol.

CO

+ Cl2

> COCl2

At t = 0

At equilibrium

(21)

(31)

Concentrations (V = 5 lit)

1/5

2/5

1/5

Hence, (B) is correct.

Prob 3.

The reaction: 3O2 2O3, H = + 69,000 calories is favoured by:

(A) high temperature and low pressure

(B)

high temperature and high pressure

(C) low temperature and high pressure

(D) low temperature and low pressure

Sol. According to Le Chatalier principle formation of ozone is favoured by high temperature (endothermic reaction) and high pressure.

Hence, (B) is correct.

Prob4. The equilibrium constant at 323C is 1000. What would be its value in the presence of a catalyst in the forward reaction?

A+B

C + D + 38 Kcal

(A) 1000 concentration of catalyst

(B) 1000

(C) 1000 / concentration of catalyst

(D) impossible to tell

Sol.

The equilibrium constant varies only with temperature. At constant temperature it will not vary.

Hence, (B) is correct.

Prob 5.

Which of the following reactions represent a heterogenous equilibrium?

(A) H2(g) + l1 (g)

2Hl(g)

(B) CaCO3(s)

CaO(s) + CO2(g)

(C) N2O4(g)

2NO2(g)

(D) O3(g)

3O2(g)

Sol.

In heterogenous equilibrium, physical state of all the reactants and products are not same.

Hence, (B) is correct.

True/False

Prob 6. For a reversible system at constant temperature the value of Kc increase if the concentration are changed at equilibrium.

Sol.

False

Prob 7.

The apparent molecular weight if PCl5 on dissociation shows lower value.

Sol.

True

Prob 8. The value of Kc for the reaction 2SO2 + O2 > 2SO3 will increase if the volume of reaction vessel is increased.

Sol.

False

Fill in the Blanks

Prob9.

Free energy change at equilibrium is ..

Sol.

Zero

Prob 10. The equilibrium constant is . of velocity constant of forward and backward reactions.

Sol.

Ratio