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7.12 BUFFER SOLUTIONS
Many body fluids e.g., blood or urine have definite pH and any deviation in their pH indicates
malfunctioning of the body. The control of pH is also very important in many chemical and
biochemical processes. Many medical and cosmetic formulations require that these be kept and
administered at a particular pH. The solutions which resist change in pH on dilution or with the
addition of small amounts of acid or alkali are called Buffer Solutions. Buffer solutions of known
pH can be prepared from the knowledge of pKa of the acid or pKb of base and by controlling the
ratio of the salt and acid or salt and base. A mixture of acetic acid and sodium acetate acts as
buffer solution around pH 4.75 and a mixture of ammonium chloride and ammonium hydroxide
acts as a buffer around pH 9.25. You will learn more about buffer solutions in higher classes.
7.13 SOLUBILITY EQUILIBRIA OF SPARINGLY SOLUBLE SALTS
We have already known that the solubility of ionic solids in water varies a great deal. Some of
these (like calcium chloride) are so soluble that they are hygroscopic in nature and even absorb
water vapour from atmosphere. Others (such as lithium fluoride) have so little solubility that th
are commonly termed as insoluble. The solubility depends on a number of factors important
amongst which are the lattice enthalpy of the salt and the solvation enthalpy of the ions in a
solution. For a salt to dissolve in a solvent the strong forces of attraction between its ions (lattic
enthalpy) must be overcome by the ion-solvent interactions. The solvation enthalpy of ions is
referred to in terms of solvation which is always negative i.e. energy is released in the process
solvation. The amount of solvation enthalpy depends on the nature of the solvent. In case of a
non-polar (covalent) solvent, solvation enthalpy is small and hence, not sufficient to overcome
lattice enthalpy of the salt. Consequently, the salt does not dissolve in non-polar solvent. As a
general rule , for a salt to be able to dissolve in a particular solvent its solvation enthalpy must
be greater than its lattice enthalpy so that the latter may be overcome by former. Each salt has
its characteristic solubility which depends on temperature. We classify salts on the basis of thei
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NCERT Class XI Chemistry Chapter 7 Equilibrium (Part 2) | AglaSem... file:///C:/Users/Sony/Desktop/geochem.htm
solubility in the following three categories.
Category I Soluble Solubility > 0.1M
Category II Slightly Soluble 0.01M<Solubility< 0.1M
Category III Sparingly Soluble Solubility < 0.01M
We shall now consider the equilibrium between the sparingly soluble ionic salt and its saturated
aqueous solution.
7.13.1 Solubility Product Constant
Let us now have a solid like barium sulphate in contact with its saturated aqueous solution. The
equilibrium between the undisolved solid and the ions in a saturated solution can be represente
by the equation:
The equilibrium constant is given by the equation:
K = {[Ba2+][SO42-]} / [BaSO4]
For a pure solid substance the concentration remains constant and we can write
Ksp = K[BaSO4] = [Ba2+][SO42-]

(7.39)
We call Ksp the solubility product constant or simply solubility product. The experimental value
Ksp in above equation at 298K is 1.1 x 10-10. This means that for solid barium sulphate in
equilibrium with its saturated solution, the product of the concentrations of barium and sulphat
ions is equal to its solubility product constant. The concentrations of the two ions will be equal t
the molar solubility of the barium sulphate. If molar solubility is S, then
1.1 x 10-10 = (S)(S) = S2 or S = 1.05 x 10-5.
Thus, molar solubility of barium sulphate will be equal to 1.05 x 10-5 mol L-1.
A salt may give on dissociation two or more than two anions and cations carrying different
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charges. For example, consider a salt like zirconium phosphate of molecular formula
(Zr4+)3(PO43-)4. It dissociates into 3 zirconium cations of charge +4 and 4 phosphate anions of
charge -3. If the molar solubility of zirconium phosphate is S, then it can be seen from the
stoichiometry of the compound that
[Zr4+] = 3S and [PO43-] = 4S
and Ksp = (3S)3 (4S)4 = 6912 (S)7
or S = {Ksp / (33 x 44)}1/7 = (Ksp / 6912)1/7
A solid salt of the general formula Mxp+ Xyq- with molar solubility S in equilibrium with its
saturated solution may be represented by the equation:
(where X x p+ = y x q)
And its solubility product constant is given by:
Ksp = [Mp+]x[Xq- ]y = (xS)x(yS)y -(7.40)
= xx . yy . S(x + y)
S(x + y) = Ksp / xx . yy
S = (Ksp / xx . y y)1 / x + y (7.41)
The term Ksp in equation is given by Qsp (section 7.6.2) when the concentration of one or more
species is not the concentration under equilibrium. Obviously under equilibrium conditions Ksp =
Qsp but otherwise it gives the direction of the processes of precipitation or dissolution. The
solubility product constants of a number of common salts at 298K are given in Table 7.9.
Table 7.9 The Solubility Product Constants, Ksp of Some Common Ionic Salts at 298K.
Problem 7.26
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Calculate the solubility of A2X3 in pure water, assuming that neither kind of ion reacts with wate
The solubility product of A2X3, Ksp = 1.1 x 10-23.
Solution
A2X3 2A3+ + 3X2-
Ksp = [A3+]2 [X2-]3 = 1.1 x 10-23
If S = solubility of A2X3, then
[A3+] = 2S; [X2] = 3S
therefore, Ksp = (2S)2(3S)3 = 108S5 = 1.1 x 10-23
thus, S5 = 1 x 10-25
S = 1.0 x 10-5 mol/L.
Problem 7.27
The values of Ksp of two sparingly soluble salts Ni(OH)2 and AgCN are 2.0 x 10-15 and 6 x
0-17 respectively. Which salt is more soluble? Explain.
Solution
Ksp = [Ag+][CN] = 6 x 10-17
Ksp = [Ni2+][OH]2= 2 x 10-15
Let [Ag+] = S1, then [CN] = S1
Let [Ni2+] = S2, then [OH] = 2S2
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S12 = 6 x 10-17 , S1 = 7.8 x 10-9
(S2)(2S2)2 = 2 x 10-15, S2 = 0.58 x10-4
Ni(OH)2 is more soluble than AgCN.
7.13.2 Common Ion Effect on Solubility of Ionic Salts
It is expected from Le Chateliers principle that if we increase the concentration of any one of th
ions, it should combine with the ion of its opposite charge and some of the salt will be
precipitated till once again Ksp = Qsp. Similarly, if the concentration of one of the ions is
decreased, more salt will dissolve to increase the concentration of both the ions till once again
Ksp = Qsp. This is applicable even to soluble salts like sodium chloride except that due to higher
concentrations of the ions, we use their activities instead of their molarities in the expression fo
Qsp. Thus if we take a saturated solution of sodium chloride and pass HCl gas through it, then
sodium chloride is precipitated due to increased concentration (activity) of chloride ion available
from the dissociation of HCl. Sodium chloride thus obtained is of very high purity and we can ge
rid of impurities like sodium and magnesium sulphates. The common ion effect is also used for
almost complete precipitation of a particular ion as its sparingly soluble salt, with very low valu
of solubility product for gravimetric estimation. Thus we can precipitate silver ion as silver
chloride, ferric ion as its hydroxide (or hydrated ferric oxide) and barium ion as its sulphate for
quantitative estimations.
Problem 7.28
Calculate the molar solubility of Ni(OH)2 in 0.10 M NaOH. The ionic product of Ni(OH)2 is 2.0 x
10-15.
Solution
Let the solubility of Ni(OH)2 be equal to S. Dissolution of S mol/L of Ni(OH)2 provides S mol/L o
Ni2+ and 2S mol/L of OH, but the total concentration of OH = (0.10 + 2S) mol/L because the
solution already contains 0.10 mol/L of OH from NaOH.
Ksp = 2.0 x 10-15 = [Ni2+] [OH]2
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= (S) (0.10 + 2S)2
As Ksp is small, 2S << 0.10, thus, (0.10 + 2S) 0.10
Hence,
2.0 x 10-15 = S (0.10)2
S = 2.0 x 10-13 M = [Ni2+]
The solubility of salts of weak acids like phosphates increases at lower pH. This is because at
lower pH the concentration of the anion decreases due to its protonation. This in turn increase
the solubility of the salt so that Ksp = Qsp. We have to satisfy two equilibria simultaneously i.e.,
Ksp = [M+] [X],
Ka = [H+(aq)][X(aq)]/[HX(aq)]
Taking inverse of both side and adding 1 we get
[HX]/[X] + 1 = [H+]/Ka + 1
([HX]+[H])/[X] = ([H+] + Ka)/Ka
Now, again taking inverse, we get
[X] / {[X] + [HX]} = f = Ka / (Ka + [H+]) and it can be seen that f decreases as pH
decreases. If S is the solubility of the salt at a given pH then
Ksp = [S] [f S] = S2 {Ka / (Ka + [H+])} and
S = {Ksp ([H+] + Ka ) /Ka }1/2 (7.42)
Thus solubility S increases with increase in [H+] or decrease in pH.
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SUMMARY
When the number of molecules leaving the liquid to vapour equals the number of molecules
returning to the liquid from vapour, equilibrium is said to be attained and is dynamic in nature.
Equilibrium can be established for both physical and chemical processes and at this stage rate o
forward and reverse reactions are equal. Equilibrium constant, Kc is expressed as the
concentration of products divided by reactants, each term raised to the stoichiometric coefficien
For reaction,
Equilibrium constant has constant value at a fixed temperature and at this stage all the
macroscopic properties such as concentration, pressure, etc. become constant. For a gaseous
reaction equilibrium constant is expressed as Kp and is written by replacing concentration terms
by partial pressures in Kc expression. The direction of reaction can be predicted by reaction
quotient Qc which is equal to Kc at equilibrium. Le Chateliers principle states that the change in
any factor such as temperature, pressure, concentration, etc. will cause the equilibrium to shift
such a direction so as to reduce or counteract the effect of the change. It can be used to study
the effect of various factors such as temperature, concentration, pressure, catalyst and inert
gases on the direction of equilibrium and to control the yield of products by controlling these
factors.Catalyst does not effect the equilibrium composition of a reaction mixture but increases
the rate of chemical reaction by making available a new lower energy pathway for conversion o
reactants to products and vice-versa.
All substances that conduct electricity in aqueous solutions are called electrolytes. Acids, bases
and salts are electrolytes and the conduction of electricity by their aqueous solutions is due to
anions and cations produced by the dissociation or ionization of electrolytes in aqueous solution
The strong electrolytes are completely dissociated. In weak electrolytes there is equilibrium
between the ions and the unionized electrolyte molecules. According to Arrhenius, acids give
hydrogen ions while bases produce hydroxyl ions in their aqueous solutions. Brnsted-Lowry on
the other hand, defined an acid as a proton donor and a base as a proton acceptor. When a
Brnsted-Lowry acid reacts with a base, it produces its conjugate base and a conjugate acid
corresponding to the base with which it reacts. Thus a conjugate pair of acid-base differs only b
one proton. Lewis further generalised the definition of an acid as an electron pair acceptor and
base as an electron pair donor. The expressions for ionization (equilibrium) constants of weak
acids (Ka) and weak bases (Kb) are developed using Arrhenius definition. The degree of ionizati
and its dependence on concentration and common ion are discussed. The pH scale (pH =
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-log[H+]) for the hydrogen ion concentration (activity) has been introduced and extended to
other quantities (pOH = log[OH]) ; pKa = -log[Ka] ; pKb = -log[Kb]; and pKw = -log[Kw] etc.
The ionization of water has been considered and we note that the equation: pH + pOH = pKw is
always satisfied. The salts of strong acid and weak base, weak acid and strong base, and weak
acid and weak base undergo hydrolysis in aqueous solution.The definition of buffer solutions, an
their importance are discussed briefly. The solubility equilibrium of sparingly soluble salts is
discussed and the equilibrium constant is introduced as solubility product constant (Ksp). Its
relationship with solubility of the salt is established. The conditions of precipitation of the salt
from their solutions or their dissolution in water are worked out. The role of common ion and th
solubility of sparingly soluble salts is also discussed.
SUGGESTED ACTIVITIES FOR STUDENTS REGARDING THIS UNIT
(a) The student may use pH paper in determining the pH of fresh juices of various vegetables
and fruits, soft drinks, body fluids and also that of water samples available.
(b) The pH paper may also be used to determine the pH of different salt solutions and from tha
he/she may determine if these are formed from strong/weak acids and bases.
(c) They may prepare some buffer solutions by mixing the solutions of sodium acetate and acet
acid and determine their pH using pH paper.
(d) They may be provided with different indicators to observe their colours in solutions of varyi
pH.
(e) They may perform some acid-base titrations using indicators.
(f) They may observe common ion effect on the solubility of sparingly soluble salts.
(g) If pH meter is available in their school, they may measure the pH with it and compare the
results obtained with that of the pH paper.
EXERCISES
7.1 A liquid is in equilibrium with its vapour in a sealed container at a fixed temperature. The
volume of the container is suddenly increased.
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a) What is the initial effect of the change on vapour pressure?
b) How do rates of evaporation and condensation change initially?
c) What happens when equilibrium is restored finally and what will be the final vapour pressure
7.2 What is Kc for the following equilibrium when the equilibrium concentration of each substan
is: [SO2]= 0.60M, [O2] = 0.82M and [SO3] = 1.90M ?
7.3 At a certain temperature and total pressure of 105Pa, iodine vapour contains 40% by volum
of I atoms
Calculate Kp for the equilibrium.
7.4 Write the expression for the equilibrium constant, Kc for each of the following reactions:
7.5 Find out the value of Kc for each of the following equilibria from the value of Kp:
7.6 For the following equilibrium, Kc= 6.3 x 1014 at 1000 K
Both the forward and reverse reactions in the equilibrium are elementary bimolecular reactions
What is Kc, for the reverse reaction?
7.7 Explain why pure liquids and solids can be ignored while writing the equilibrium constant
expression?
7.8 Reaction between N2 and O2- takes place as follows:
If a mixture of 0.482 mol N2 and 0.933 mol of O2 is placed in a 10 L reaction vessel and allowe
to form N2O at a temperature for which Kc= 2.0 x 10-37, determine the composition of
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equilibrium mixture.
7.9 Nitric oxide reacts with Br2 and gives nitrosyl bromide as per reaction given below:
When 0.087 mol of NO and 0.0437 mol of Br2 are mixed in a closed container at constant
temperature, 0.0518 mol of NOBr is obtained at equilibrium. Calculate equilibrium amount of N
and Br2 .
7.10 At 450K, Kp= 2.0 x 1010/bar for the given reaction at equilibrium.
What is Kc at this temperature ?
7.11 A sample of HI(g) is placed in flask at a pressure of 0.2 atm. At equilibrium the partial
pressure of HI(g) is 0.04 atm. What is Kp for the given equilibrium ? below:
7.12 A mixture of 1.57 mol of N2, 1.92 mol of H2 and 8.13 mol of NH3 is introduced into a 20 L
reaction vessel at 500 K. At this temperature, the equilibrium constant, Kc for the reaction
is 1.7 x 102. Is the reaction mixture at equilibrium? If not, what is the direction of the net
reaction?
7.13 The equilibrium constant expression for a gas reaction is,
Kc = [ NH3 ]4[ O2]5/[ NO]4 [H2O]6
Write the balanced chemical equation corresponding to this expression.
7.14 One mole of H2O and one mole of CO are taken in 10 L vessel and heated to 725 K. At
equilibrium 40% of water (by mass) reacts with CO according to the equation,
Calculate the equilibrium constant for the reaction.
7.15 At 700 K, equilibrium constant for the reaction:
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is 54.8. If 0.5 mol L-1 of HI(g) is present at equilibrium at 700 K, what are the concentration of
H2(g) and I2(g) assuming that we initially started with HI(g) and allowed it to reach equilibrium
at 700K?
7.16 What is the equilibrium concentration of each of the substances in the
equilibrium when the initial concentration of ICl was 0.78 M ?
7.17 Kp = 0.04 atm at 899 K for the equilibrium shown below. What is the equilibrium
concentration of C2H6 when it is placed in a flask at 4.0 atm pressure and allowed to come to
equilibrium?
7.18 Ethyl acetate is formed by the reaction between ethanol and acetic acid and the equilibriu
is represented as:
(i) Write the concentration ratio (reaction quotient), Qc, for this reaction (note: water is not in
excess and is not a solvent in this reaction)
(ii) At 293 K, if one starts with 1.00 mol of acetic acid and 0.18 mol of ethanol, there is 0.171
mol of ethyl acetate in the final equilibrium mixture. Calculate the equilibrium constant.
(iii) Starting with 0.5 mol of ethanol and 1.0 mol of acetic acid and maintaining it at 293 K, 0.2
mol of ethyl acetate is found after sometime. Has equilibrium been reached?
7.19 A sample of pure PCl5 was introduced into an evacuated vessel at 473 K. After equilibrium
was attained, concentration of PCl5 was found to be 0.5 x 10-1 mol L-1. If value of Kc is 8.3 x
10-3, what are the concentrations of PCl3 and Cl2 at equilibrium?
7.20 One of the reaction that takes place in producing steel from iron ore is the reduction of
iron(II) oxide by carbon monoxide to give iron metal and CO2.
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What are the equilibrium partial pressures of CO and CO2 at 1050 K if the initial partial pressure
are: pCO= 1.4 atm and 2 CO p = 0.80 atm?
7.21 Equilibrium constant, Kc for the reaction
at 500 K is 0.061
At a particular time, the analysis shows that composition of the reaction mixture is 3.0 mol
L-1 N2, 2.0 mol L-1 H2 and 0.5 mol L-1 NH3. Is the reaction at equilibrium? If not in which
direction does the reaction tend to proceed to reach equilibrium?
7.22 Bromine monochloride, BrCl decomposes into bromine and chlorine and reaches the
equilibrium:
for which Kc= 32 at 500 K. If initially pure BrCl is present at a concentration of 3.3 x 10-3mol L-
what is its molar concentration in the mixture at equilibrium?
7.23 At 1127 K and 1 atm pressure, a gaseous mixture of CO and CO2 in equilibrium with soild
carbon has 90.55% CO by mass
Calculate Kc for this reaction at the above temperature.
7.24 Calculate a) G and b) the equilibrium constant for the formation of NO2 from NO and
O2 at 298K
where fG (NO2) = 52.0 kJ/mol
fG (NO) = 87.0 kJ/mol
fG (O2) = 0 kJ/mol
7.25 Does the number of moles of reaction products increase, decrease or remain same when
each of the following equilibria is subjected to a decrease in pressure by increasing the volume?
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7.26 Which of the following reactions will get affected by increasing the pressure? Also, mention
whether change will cause the reaction to go into forward or backward direction.
7.27 The equilibrium constant for the following reaction is 1.6 x 105 at 1024K
Find the equilibrium pressure of all gases if 10.0 bar of HBr is introduced into a sealed containe
at 1024K.
7.28 Dihydrogen gas is obtained from natural gas by partial oxidation with steam as per followi
endothermic reaction:
(a) Write as expression for Kp for the above reaction.
(b) How will the values of Kp and composition of equilibrium mixture be affected by
(i) increasing the pressure
(ii) increasing the temperature
(iii) using a catalyst ?
7.29 Describe the effect of :
a) addition of H2
b) addition of CH3OH
c) removal of CO
d) removal of CH3OH
on the equilibrium of the reaction:
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7.30 At 473 K, equilibrium constant Kc for decomposition of phosphorus pentachloride, PCl5 is 8

x 10-3. If decomposition is depicted as,
a) write an expression for Kc for the reaction.
b) what is the value of Kc for the reverse reaction at the same temperature ?
c) what would be the effect on Kc if (i) more PCl5 is added (ii) pressure is increased (iii) the
temperature is increased ?
7.31 Dihydrogen gas used in Habers process is produced by reacting methane from natural gas
with high temperature steam. The first stage of two stage reaction involves the formation of CO
and H2. In second stage, CO formed in first stage is reacted with more steam in water gas shift
reaction,
If a reaction vessel at 400C is charged with an equimolar mixture of CO and steam such that
pCO = pH2O = 4.0 bar, what will be the partial pressure of H2 at equilibrium? Kp= 10.1 at 400C
7.32 Predict which of the following reaction will have appreciable concentration of reactants and
products:
7.33 The value of Kc for the reaction
is 2.0 x 10-50 at 25C. If the equilibrium concentration of O2 in air at 25C is 1.6 x 10-2, what i
the concentration of O3?
7.34 The reaction,
is at equilibrium at 1300 K in a 1L flask. It also contain 0.30 mol of CO, 0.10 mol of H2 and 0.0
mol of H2O and an unknown amount of CH4 in the flask. Determine the concentration of CH4 in
the mixture. The equilibrium constant, Kc for the reaction at the given temperature is 3.90.
7.35 What is meant by the conjugate acid-base pair? Find the conjugate acid/base for the
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following species:
HNO2, CN, HClO4, F, OH, CO32-, and S2
7.36 Which of the followings are Lewis acids? H2O, BF3, H+, and NH4+
7.37 What will be the conjugate bases for the Brnsted acids: HF, H2SO4 and HCO3?
7.38 Write the conjugate acids for the following Brnsted bases: NH2, NH3 and HCOO.
7.39 The species: H2O, HCO3, HSO4 and NH3 can act both as Brnsted acids and bases. For
each case give the corresponding conjugate acid and base.
7.40 Classify the following species into Lewis acids and Lewis bases and show how these act as
Lewis acid/base: (a) OH (b) F (c) H+ (d) BCl3 .
7.41 The concentration of hydrogen ion in a sample of soft drink is 3.8 x 10-3 M. what is its pH?
7.42 The pH of a sample of vinegar is 3.76. Calculate the concentration of hydrogen ion in it.
7.43 The ionization constant of HF, HCOOH and HCN at 298K are 6.8 x 10-4 ,1.8 x 10-4and 4.8
10-9 respectively. Calculate the ionization constants of the corresponding conjugate base.
7.44 The ionization constant of phenol is 1.0 x 10-10. What is the concentration of phenolate ion
in 0.05 M solution of phenol? What will be its degree of ionization if the solution is also 0.01M in
sodium phenolate?
7.45 The first ionization constant of H2S is 9.1 x 10-8. Calculate the concentration of HSion in i
0.1M solution. How will this concentration be affected if the solution is 0.1M in HCl also ? If the
second dissociation constant of H2S is 1.2 x 10-13, calculate the concentration of S2- under both
conditions.
7.46 The ionization constant of acetic acid is 1.74 x 10-5. Calculate the degree of dissociation of
acetic acid in its 0.05 M solution. Calculate the concentration of acetate ion in the solution and
pH.
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7.47 It has been found that the pH of a 0.01M solution of an organic acid is 4.15. Calculate the
concentration of the anion, the ionization constant of the acid and its pKa.
7.48 Assuming complete dissociation, calculate the pH of the following solutions:
(a) 0.003 M HCl (b) 0.005 M NaOH (c) 0.002 M HBr (d) 0.002 M KOH
7.49 Calculate the pH of the following solutions:
a) 2 g of TlOH dissolved in water to give 2 litre of solution.
b) 0.3 g of Ca(OH)2 dissolved in water to give 500 mL of solution.
c) 0.3 g of NaOH dissolved in water to give 200 mL of solution.
d) 1mL of 13.6 M HCl is diluted with water to give 1 litre of solution.
7.50 The degree of ionization of a 0.1M bromoacetic acid solution is 0.132. Calculate the pH of
the solution and the pKa of bromoacetic acid.
7.51 The pH of 0.005M codeine (C18H21NO3) solution is 9.95. Calculate its ionization constant
and pKb.
7.52 What is the pH of 0.001M aniline solution ? The ionization constant of aniline can be taken
from Table 7.7. Calculate the degree of ionization of aniline in the solution. Also calculate the
ionization constant of the conjugate acid of aniline.
7.53 Calculate the degree of ionization of 0.05M acetic acid if its pKa value is 4.74. How is the
degree of dissociation affected when its solution also contains
(a) 0.01M (b) 0.1M in HCl ?
7.54 The ionization constant of dimethylamine is 5.4 x 10-4. Calculate its degree of ionization in
its 0.02M solution. What percentage of dimethylamine is ionized if the solution is also 0.1M in
NaOH?
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7.55 Calculate the hydrogen ion concentration in the following biological fluids whose pH are
given below:
(a) Human muscle-fluid, 6.83 (b) Human stomach fluid, 1.2
(c) Human blood, 7.38 (d) Human saliva, 6.4.
7.56 The pH of milk, black coffee, tomato juice, lemon juice and egg white are 6.8, 5.0, 4.2, 2.
and 7.8 respectively. Calculate corresponding hydrogen ion concentration in each.
7.57 If 0.561 g of KOH is dissolved in water to give 200 mL of solution at 298 K. Calculate the
concentrations of potassium, hydrogen and hydroxyl ions. What is its pH?
7.58 The solubility of Sr(OH)2 at 298 K is 19.23 g/L of solution. Calculate the concentrations of
strontium and hydroxyl ions and the pH of the solution.
7.59 The ionization constant of propanoic acid is 1.32 x 10-5. Calculate the degree of ionization
the acid in its 0.05M solution and also its pH. What will be its degree of ionization if the solution
is 0.01M in HCl also?
7.60 The pH of 0.1M solution of cyanic acid (HCNO) is 2.34. Calculate the ionization constant of
the acid and its degree of ionization in the solution.
7.61 The ionization constant of nitrous acid is 4.5 x 10-4. Calculate the pH of 0.04 M sodium
nitrite solution and also its degree of hydrolysis.
7.62 A 0.02M solution of pyridinium hydrochloride has pH = 3.44. Calculate the ionization
constant of pyridine.
7.63 Predict if the solutions of the following salts are neutral, acidic or basic:
NaCl, KBr, NaCN, NH4NO3, NaNO2 and KF
7.64 The ionization constant of chloroacetic acid is 1.35 x 10-3. What will be the pH of 0.1M acid
and its 0.1M sodium salt solution?
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7.65 Ionic product of water at 310 K is 2.7 x 10-14. What is the pH of neutral water at this
temperature?
7.66 Calculate the pH of the resultant mixtures:
a) 10 mL of 0.2M Ca(OH)2 + 25 mL of 0.1M HCl
b) 10 mL of 0.01M H2SO4 + 10 mL of 0.01M Ca(OH)2
c) 10 mL of 0.1M H2SO4 + 10 mL of 0.1M KOH
7.67 Determine the solubilities of silver chromate, barium chromate, ferric hydroxide, lead
chloride and mercurous iodide at 298K from their solubility product constants given in Table 7.9
Determine also the molarities of individual ions.
7.68 The solubility product constant of Ag2CrO4 and AgBr are 1.1 x 10-12 and 5.0 x
10-13respectively. Calculate the ratio of the molarities of their saturated solutions.
7.69 Equal volumes of 0.002 M solutions of sodium iodate and cupric chlorate are mixed
together. Will it lead to precipitation of copper iodate? (For cupric iodate Ksp = 7.4 x 10-8 ).
7.70 The ionization constant f benzoic acid is 6.46 x 10-5 and Ksp for silver benzoate is 2.5 x
10-13. How many times is silver benzoate more soluble in a buffer of pH 3.19 compared to its
solubility in pure water?
7.71 What is the maximum concentration of equimolar solutions of ferrous sulphate and sodium
sulphide so that when mixed in equal volumes, there is no precipitation of iron sulphide? (For
iron sulphide, Ksp = 6.3 x 10-18).
7.72 What is the minimum volume of water required to dissolve 1g of calcium sulphate at 298 K
(For calcium sulphate, Ksp is 9.1 x 10-6).
7.73 The concentration of sulphide ion in 0.1M HCl solution saturated with hydrogen sulphide is
1.0 x 10-19 M. If 10 mL of this is added to 5 mL of 0.04 M solution of the following: FeSO4,
MnCl2, ZnCl2 and CdCl2. in which of these solutions precipitation will take place?
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Answer to Some Selected Problems
7.2 12.237 molL1
7.3 2.67 x 104
7.5 (i) 4.4 x 104 (ii) 1.90
7.6 1.59 x 1015
7.8 [N2] = 0.0482 molL1, [O2] = 0.0933 molL1, [N2O] = 6.6 x 1021 molL1
7.9 0.0352mol of NO and 0.0178mol of Br2
7.10 7.47 x 1011 M1
7.11 4.0
7.12 Qc = 2.379 x 103. No, reaction is not at equilibrium.
7.14 0.44
7.15 0.068 molL1 each of H2 and I2
7.16 [I2] = [Cl2] = 0.21 M, [ICl] = 0.36 M
7.17 [C2H6]eq = 3.62 atm
7.18 (i) [CH3COOC2H5][H2O] / [CH3COOH][C2H5OH]
(ii) 22.9 (iii) value of Qc is less than Kc therefore equilibrium is not attained.
7.19 0.02molL1 for both.
7.20 [PCO] = 1.739atm, [PCO2] = 0.461atm.
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7.21 No, the reaction proceeds to form more products.
7.22 3 x 104 molL1
7.23 6.46
7.24 a) 35.0kJ, b) 1.365 x 106
7.27 [PH2]eq = [PBr2]eq = 2.5 x 102bar, [PHBr] = 10.0 bar
7.30 b) 120.48
7.31 [H2]eq = 0.96 bar
7.33 2.86 x 1028 M
7.34 5.85 x 102
7.35 NO2, HCN, ClO4, HF, H2O, HCO3, HS
7.36 BF3, H+, NH4+
7.37 F, HSO4, CO32
7.38 NH3, NH4+, HCOOH
7.41 2.42
7.42 1.7 x 104M
7.43 F= 1.5 x 1011, HCOO= 5.6 x 1011, CN= 2.08 x 106
7.44 [phenolate ion]= 2.2 x 106, pH= 5.65, = 4.47 x 105. pH of 0.01M sodium phenolate
solution= 9.30.
7.45 [HS]= 9.54 x 105, in 0.1M HCl [HS] = 9.1 x 108M, [S2]= 1.2 x 1013M, in 0.1M HCl
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[S2]= 1.09 x 1019M
7.46 [Ac]= 0.00093, pH= 3.03
7.47 [A] = 7.08 x105M, Ka= 5.08 x 107, pKa= 6.29
7.48 a) 2.52 b) 11.70 c) 2.70 d) 11.30
7.49 a) 11.65 b) 12.21 c) 12.57 c) 1.87
7.50 pH = 1.88, pKa = 2.70
7.51 Kb = 1.6 x 106, pKb = 5.8
7.52 = 6.53 x 104, Ka = 2.34 x 105
7.53 a) 0.0018 b) 0.00018
7.54 = 0.0054
7.55 a) 1.48 x 107M, b) 0.063 c) 4.17 x 108M d) 3.98 x 107
7.56 a) 1.5 x 107M, b) 105M, c) 6.31 x 105M d) 6.31 x 103M
7.57 [K+] = [OH] = 0.05M, [H+] = 2.0 x 1013M
7.58 [Sr2+] = 0.1581M, [OH] = 0.3162M , pH = 13.50
7.59 = 1.63 x 102, pH = 3.09. In presence of 0.01M HCl, = 1.32 x 103
7.60 Ka = 2.09 x 104 and degree of ionization = 0.0457
7.61 pH = 7.97. Degree of hydrolysis = 2.36 x 105
7.62 Kb = 1.5 x 109
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7.63 NaCl, KBr solutions are neutral, NaCN, NaNO2 and KF solutions are basic and
NH4NO3 solution is acidic.
7.64 (a) pH of acid solution= 1.94 (b) its salt solution= 2.87
7.65 pH = 6.78
7.66 a) 11.2 b) 7.00 c) 3.00
7.67 Silver chromate S= 0.65 x 104M; Molarity of Ag+ = 1.30 x 104M

Molarity of CrO42 = 0.65 x 104M; Barium Chromate S = 1.1 x 105M;
Molarity of Ba2+ and CrO42 each is 1.1 x 105M; Ferric Hydroxide S = 1.39 x 1010M;
Molarity of Fe3+ = 1.39 x 1010M; Molarity of [OH] = 4.17 x 1010M
Lead Chloride S = 1.59 x 102M; Molarity of Pb2+ = 1.59 x 102M
Molarity of Cl = 3.18 x 102M; Mercurous Iodide S = 2.24 x 1010M;
Molarity of Hg22+ = 2.24 x 1010M and molarity of I = 4.48 x 1010M
7.68 Silver chromate is more soluble and the ratio of their molarities = 91.9
7.69 No precipitate
7.70 Silver benzoate is 3.317 times more soluble at lower pH
7.71 The highest molarity for the solution is 2.5 x 109M
7.72 2.46 litre of water
7.73 Precipitation will take place in cadmium chloride solution
I. Multiple Choice Questions (Type-I)
1. We know that the relationship between Kc and Kp is
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Kp = Kc(RT)n
What would be the value of n for the reaction
(i) 1
(ii) 0.5
(iii) 1.5
(iv) 2
2. For the reaction
, the standard free energy is G > 0. The equilibrium constant (K ) would be __________.
(i) K = 0
(ii) K > 1
(iii) K = 1
(iv) K < 1
3. Which of the following is not a general characteristic of equilibria involving
physical processes?
(i) Equilibrium is possible only in a closed system at a given temperature.
(ii) All measurable properties of the system remain constant.
(iii) All the physical processes stop at equilibrium.
(iv) The opposing processes occur at the same rate and there is dynamic but stable condition.
4. PCl5, PCl3 and Cl2 are at equilibrium at 500K in a closed container and their concentrations a
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0.8 103 mol L1, 1.2 103 mol L1 and 1.2 103 mol L1respectively. The value of Kc for
the reaction
will be
(i) 1.8 103 mol L1
(ii) 1.8 103
(iii) 1.8 103 L mol1
(iv) 0.55 104
5. Which of the following statements is incorrect?
(i) In equilibrium mixture of ice and water kept in perfectly insulated flask mass of ice and wate
does not change with time.
(ii) The intensity of red colour increases when oxalic acid is added to a solution containing iron
(III) nitrate and potassium thiocyanate.
(iii) On addition of catalyst the equilibrium constant value is not affected.
(iv) Equilibrium constant for a reaction with negative H value decreases
as the temperature increases.
6. When hydrochloric acid is added to cobalt nitrate solution at room temperature, the following
reaction takes place and the reaction mixture becomes blue. On cooling the mixture it becomes
pink. On the basis of this information mark the correct answer.
(i) H > 0 for the reaction
(ii) H < 0 for the reaction
(iii) H = 0 for the reaction
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(iv) The sign of H cannot be predicted on the basis of this information.
7. The pH of neutral water at 25C is 7.0. As the temperature increases, ionisation
of water increases, however, the concentration of H+ ions and OH ions are equal. What will be
the pH of pure water at 60C?
(i) Equal to 7.0
(ii) Greater than 7.0
(iii) Less than 7.0
(iv) Equal to zero
8. The ionisation constant of an acid, Ka, is the measure of strength of an acid. The Kavalues of
acetic acid, hypochlorous acid and formic acid are 1.74 105, 3.0 108 and 1.8
104 respectively. Which of the following orders of pH of 0.1 mol dm3 solutions of these acids i
correct?
(i) acetic acid > hypochlorous acid > formic acid
(ii) hypochlorous acid > acetic acid > formic acid
(iii) formic acid > hypochlorous acid > acetic acid
(iv) formic acid > acetic acid > hypochlorous acid
9. Ka1 , Ka2 and Ka3 are the respective ionisation constants for the following reactions.
The correct relationship between Ka1 , Ka2 and Ka3 is
(i) Ka3 = Ka1 Ka2
(ii) Ka3 = Ka1 + Ka2
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(iii) Ka3 = Ka1 Ka2
(iv) Ka3 = Ka1 / Ka2
10. Acidity of BF3 can be explained on the basis of which of the following concepts?
(i) Arrhenius concept
(ii) Bronsted Lowry concept
(iii) Lewis concept
(iv) Bronsted Lowry as well as Lewis concept.
11. Which of the following will produce a buffer solution when mixed in equal
volumes?
(i) 0.1 mol dm3 NH4OH and 0.1 mol dm3 HCl
(ii) 0.05 mol dm3 NH4OH and 0.1 mol dm3 HCl
(iii) 0.1 mol dm3 NH4OH and 0.05 mol dm3 HCl
(iv) 0.1 mol dm3 CH4COONa and 0.1 mol dm3 NaOH
12. In which of the following solvents is silver chloride most soluble?
(i) 0.1 mol dm3 AgNO3 solution
(ii) 0.1 mol dm3 HCl solution
(iii) H2O
(iv) Aqueous ammonia
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13. What will be the value of pH of 0.01 mol dm3 CH3COOH (Ka = 1.74 105 )?
(i) 3.4
(ii) 3.6
(iii) 3.9
(iv) 3.0
14. Ka for CH3COOH is 1.8 105 and K b for NH4OH is 1.8 105 . The pH of ammonium
acetate will be
(i) 7.005
(ii) 4.75
(iii) 7.0
(iv) Between 6 and 7
15. Which of the following options will be correct for the stage of half completion
of the reaction
(i) G = 0
(ii) G > 0
(iii) G < 0
(iv) G = RT ln2
16. On increasing the pressure, in which direction will the gas phase reaction
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proceed to re-establish equilibrium, is predicted by applying the Le Chateliers
principle. Consider the reaction.
Which of the following is correct, if the total pressure at which the equilibrium
is established, is increased without changing the temperature?
(i) K will remain same
(ii) K will decrease
(iii) K will increase
(iv) K will increase initially and decrease when pressure is very high
17. What will be the correct order of vapour pressure of water, acetone and ether
at 30C. Given that among these compounds, water has maximum boiling point and ether has
minimum boiling point?
(i) Water < ether < acetone
(ii) Water < acetone < ether
(iii) Ether < acetone < water
(iv) Acetone < ether < water
18. At 500 K, equilibrium constant, Kc , for the following reaction is 5.
What would be the equilibrium constant Kc for the reaction
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(i) 0.04
(ii) 0.4
(iii) 25
(iv) 2.5
19. In which of the following reactions, the equilibrium remains unaffected on
addition of small amount of argon at constant volume?
(iv) The equilibrium will remain unaffected in all the three cases.
II. Multiple Choice Questions (Type-II)
In the following questions two or more options may be correct.
20. For the reaction
, the value of K is 50 at 400 K and 1700 at 500 K. Which of the following options is correct?
(i) The reaction is endothermic
(ii) The reaction is exothermic
(iii) If NO2 (g) and N2O4 (g) are mixed at 400 K at partial pressures 20 bar and 2 bar
respectively, more N2O4 (g) will be formed.
(iv) The entropy of the system increases.
21. At a particular temperature and atmospheric pressure, the solid and liquid
phases of a pure substance can exist in equilibrium. Which of the following term defines this
temperature?
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(i) Normal melting point
(ii) Equilibrium temperature
(iii) Boiling point
(iv) Freezing point
III. Short Answer Type
22. The ionisation of hydrochloric in water is given below:
Label two conjugate acid-base pairs in this ionisation.
23. The aqueous solution of sugar does not conduct electricity. However, when
sodium chloride is added to water, it conducts electricity. How will you explain
this statement on the basis of ionisation and how is it affected by concentration
of sodium chloride?
24. BF3 does not have proton but still acts as an acid and reacts with NH3. Why is it so? What
type of bond is formed between the two?
25. Ionisation constant of a weak base MOH, is given by the expression
Values of ionisation constant of some weak bases at a particular temperature are given below:
Base Dimethylamine Urea Pyridine Ammonia
K b 5.4 104 1.3 1014 1.77 109 1.77 105
Arrange the bases in decreasing order of the extent of their ionisation at equilibrium. Which of
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the above base is the strongest?
26. Conjugate acid of a weak base is always stronger. What will be the decreasing
order of basic strength of the following conjugate bases?
OH, RO , CH3COO , Cl
27. Arrange the following in increasing order of pH.
KNO3(aq), CH3COONa (aq), NH3Cl (aq), C6H5COONH4(aq)
28. The value of Kc for the reaction
is 1 104
At a given time, the composition of reaction mixture is
[HI] = 2 105 mol, [H2] = 1 105 mol and [I2] = 1 105 mol
In which direction will the reaction proceed?
29. On the basis of the equation pH = log [H+], the pH of 108 mol dm3 solution of HCl shoul
be 8. However, it is observed to be less than 7.0. Explain the reason.
30. pH of a solution of a strong acid is 5.0. What will be the pH of the solution
obtained after diluting the given solution a 100 times?
31. A sparingly soluble salt gets precipitated only when the product of
concentration of its ions in the solution (Qsp) becomes greater than its solubility product. If the
solubility of BaSO4 in water is 8 104 mol dm3. Calculate its solubility in 0.01 mol dm3 of
H2SO4.
32. pH of 0.08 mol dm3 HOCl solution is 2.85. Calculate its ionisation constant.
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33. Calculate the pH of a solution formed by mixing equal volumes of two solutions
A and B of a strong acid having pH = 6 and pH = 4 respectively.
34. The solubility product of Al (OH)3 is 2.7 1011. Calculate its solubility in gL1 and also find
out pH of this solution. (Atomic mass of Al = 27 u).
35. Calculate the volume of water required to dissolve 0.1 g lead (II) chloride to
get a saturated solution. (Ksp of PbCl2 = 3.2 108 , atomic mass of Pb = 207 u).
36. A reaction between ammonia and boron trifluoride is given below:
: NH3 + BF3 H3N:BF3
Identify the acid and base in this reaction. Which theory explains it? What is
the hybridisation of B and N in the reactants?
37. Following data is given for the reaction: CaCO3 (s) &rightarrow; CaO (s) + CO2(g)
fH[CaO(s)] = 635.1 kJ mol1
fH[CO2(g)] = 393.5 kJ mol1
fH[CaCO3(s)] = 1206.9 kJ mol1
Predict the effect of temperature on the equilibrium constant of the above reaction.
IV. Matching Type
38. Match the following equilibria with the corresponding condition
39. For the reaction :
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Equilibrium constant Kc = [NH3]2/[N2][H2]3
Some reactions are written below in Column I and their equilibrium constants in terms of Kc are
written in Column II. Match the following reactions with the
corresponding equilibrium constant
40. Match standard free energy of the reaction with the corresponding equilibrium constant
(i) G > 0 (a) K>1
(ii) G < 0 (b) K=1
(iii) G = 0 (c) K=0
(d) K<1
41. Match the following species with the corresponding conjugate acid
Species Conjugate acid
(i) NH3 (a) CO32
(ii) HCO3 (b) NH4+
(iii) H2 O (c) H3O+
(iv) HSO4 (d) H2SO4
(e) H2CO3
42. Match the following graphical variation with their description
43. Match Column (I) with Column (II).
Column I Column II
(i) Equilibrium (a) G > 0, K < 1
(ii) Spontaneous reaction (b) G = 0
(iii) Non spontaneous reaction (c) G = 0
(d) G < 0, K > 1
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V. Assertion and Reason Type
In the following questions a statement of Assertion (A) followed by a statement
of Reason (R) is given. Choose the correct option out of the choices given
below each question.
44. Assertion (A) : Increasing order of acidity of hydrogen halides is HF < HCl < HBr < HI
Reason (R) : While comparing acids formed by the elements belonging to the same group of
periodic table, HA bond strength is a more important factor in determining acidity of an acid
than the polar nature of the bond.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.
45. Assertion (A) : A solution containing a mixture of acetic acid and sodium
acetate maintains a constant value of pH on addition of small amounts of acid or alkali.
Reason (R) : A solution containing a mixture of acetic acid and sodium acetate acts as a buffer
solution around pH 4.75.
(i) Both A and R are true and R is correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
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46. Assertion (A): The ionisation of hydrogen sulphide in water is low in the
presence of hydrochloric acid.
Reason (R) : Hydrogen sulphide is a weak acid.
(ii) Both A and R are true but R is not correct explanation of A.
(iii) A is true but R is false
(iv) Both A and R are false
47. Assertion (A): For any chemical reaction at a particular temperature, the equilibrium consta
is fixed and is a characteristic property.
Reason (R) : Equilibrium constant is independent of temperature.
48. Assertion (A) : Aqueous solution of ammonium carbonate is basic.
Reason (R) : Acidic/basic nature of a salt solution of a salt of weak acid and weak base depends
on Ka and Kb value of the acid and the base forming it.
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49. Assertion (A): An aqueous solution of ammonium acetate can act as a buffer.
Reason (R) : Acetic acid is a weak acid and NH4OH is a weak base.
(iii) A is false but R is true.
50. Assertion (A): In the dissociation of PCl5 at constant pressure and temperature addition of
helium at equilibrium increases the dissociation of PCl5.
Reason (R) : Helium removes Cl2 from the field of action.
VI. Long Answer Type
51. How can you predict the following stages of a reaction by comparing the value of Kcand Qc?
(i) Net reaction proceeds in the forward direction.
(ii) Net reaction proceeds in the backward direction.
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(iii) No net reaction occurs.
52. On the basis of Le Chatelier principle explain how temperature and pressure can be adjuste
to increase the yield of ammonia in the following reaction.
What will be the effect of addition of argon to the above reaction mixture at constant volume?
53. A sparingly soluble salt having general formula p qx Axp+Byq and molar solubility S is in
equilibrium with its saturated solution. Derive a relationship between the solubility and solubilit
product for such salt.
54. Write a relation between G and Q and define the meaning of each term and answer the
following :
(a) Why a reaction proceeds forward when Q < K and no net reaction occurs when Q = K.
(b) Explain the effect of increase in pressure in terms of reaction quotient Q.for the reaction :
ANSWERS
I. Multiple Choice Questions (Type-I)
1. (iv) 2. (iv) 3. (iii) 4. (ii) 5. (ii) 6. (i) 7. (iii) 8. (iv) 9. (i) 10. (ii
11. (iii) 12. (iv) 13. (i) 14. (iii)
15. (i) G = 0
Justification : G = RT lnK
At the stage of half completion of reaction [A] = [B], Therefore, K = 1.
Thus, G = 0
16. (i), Justification: According to Le-Chateliers principle, at constant temperature, the

equilibrium composition will change but K will remain same.
17. (ii) 18. (i) 19. (iv)
II. Multiple Choice Questions (Type-II)
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20. (i), (iii) and (iv)

Justification :
(i) K increases with increase in temperature.
(iii) Q > K, Therefore, reaction proceeds in the backward direction.
(iv) n > 0, Therefore, S > 0.
21. (i) and (iv)
III. Short Answer Type
22.
HCl Cl
acid conjugate base
H2O H3O+
base conjugate acid
23.
Sugar does not ionise in water but NaCl ionises completely in water and produces Na+and
Cl ions.
Conductance increases with increase in concentration of salt due to release of more ions.
24. BF3 acts as a Lewis acid as it is electron deficient compound and coordinate bond is formed
as given below :
H3N : BF3
25. Order of extent of ionisation at equilibrium is as follows :

Dimethylamine > Ammonia > Pyridine > Urea
Since dimethylamine will ionise to the maximum extent it is the strongest base out of the fou
given bases.
26. RO > OH > CH3COO > Cl

27. NH4Cl < C6H5COONH4 < KNO3 < CH3COONa
28. At a given time the reaction quotient Q for the reaction will be given by the expression.
Q = [H2][I2]/[HI]2
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= 1 105 1 105/(2 x 105)2 = 1/4

= 0.25 = 2.5 101
As the value of reaction quotient is greater than the value of Kc i.e. 1 104 the reaction will
proceed in the reverse direction.
29. Concentration of 108 mol dm3 indicates that the solution is very dilute. Hence, the
contribution of H3O+ concentration from water is significant and should also be included for the
calculation of pH.
30. (i) pH = 5
[H+] = 105 mol L1
On 100 times dilution
[H+] = 107 mol L1
On calculating the pH using the equation pH = log [H+], value of pH comes out to be 7. It is
not possible. This indicates that solution is very
dilute. Hence,
Total hydrogen ion concentration = [H+]
= [Contribution of H3O+ ion concentration of acid ] + [ Contribution of H3O+ ion concentration o
water ]
= 107 + 107.
pH = 2 107 = 7 log 2 = 7 0.3010 = 6.6990
31.
Ksp for BaSO4 in water = [Ba2+] [SO42] = (S) (S) = S2

But S = 8 104 mol dm3
Ksp = (8104)2 = 64 108 .. (1)
The expression for Ksp in the presence of sulphuric acid will be as follows :
Ksp = (S) (S + 0.01) . (2)
Since value of Ksp will not change in the presence of sulphuric acid, therefore from (1) and (2)
(S) (S + 0.01) = 64 108
S2 + 0.01 S = 64 108
S2 + 0.01 S 64 108 = 0
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32. pH of HOCl = 2.85

But, pH = log [H+]
2.85 = log [H+]
[H+] = 1.413 103
For weak mono basic acid [H+] =
Ka = [H+]2/C = (1.413 x 103)2/0.08

= 24.957 106 = 2.4957 105
33.
pH of Solution A = 6
Therefore, concentration of [H+] ion in solution A = 106 mol L1
pH of Solution B = 4
Therefore, Concentration of [H+] ion concentration of solution B = 104 mol L1
On mixing one litre of each solution, total volume = 1L + 1L = 2L
Amount of H+ ions in 1L of Solution A= Concentration volume V
= 106 mol 1L
Amount of H+ ions in 1L of solution B = 104 mol 1L
Total amount of H+ ions in the solution formed by mixing solutions A and B is (106 mol +
104 mol)
This amount is present in 2L solution.
Total [H+] = 104(1 + 0.01)/2 = 1 .01 x 104/2 mol L1 = 1 .01 x 104/2 mol L1
= 0.5 104 mol L1
= 5 105 mol L1
pH = log [H+] = log (5 105)

= [log 5 + ( 5 log 10)]
= log 5 + 5
= 5 log 5
= 5 0.6990
= 4.3010 = 4.3
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34. Let S be the solubility of Al(OH)3.
Ksp = [Al3+] [OH]3 = (S) (3S)3 = 27 S4

S4 = Ksp/27 = 27 1011/27 x 10 = 1 1012
S = 1 103 mol L1
(i) Solubility of Al(OH)3

Molar mass of Al (OH)3 is 78 g. Therefore,
Solubility of Al (OH)3 in g L1 = 1 103 78 g L1 = 78 103 g L1 = 7.8 102 g L1
(ii) pH of the solution

S = 1103 mol L1
[OH ] = 3S = 31103 = 3 103
pOH = 3 log 3
pH = 14 pOH = 11 + log 3 = 11.4771
35. Ksp of PbCl2 = 3.2 108

Let S be the solubility of PbCl2.
Ksp = [Pb2+] [Cl]2 = (S) (2S)2 = 4S3

Ksp = 4S3
S3 = Ksp/4 = 3.2 x 108/4 mol L1 = 8 109 mol L1
Molar mass of PbCl2 = 278

Solubility of PbCl2 in g L1= 2 103 278 g L1
= 556 103 g L1
= 0.556 g L1
To get saturated solution, 0.556 g of PbCl2 is dissolved in 1 L water.
0.1 g PbCl2 is dissolved in 0 .1/0 .556 L = 0.1798 L water.
To make a saturated solution, dissolution of 0.1 g PbCl2 in 0.1798 L 0.2 L of water will be
required.
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37. rH = fH[CaO(s)] + fH [CO2(g)] fH [CaCO3(s)]

rH = 178.3 kJ mol1
The reaction is endothermic. Hence, according to Le-Chateliers principle, reaction will proceed
forward direction on increasing temperature.
IV. Matching Type
38. (i) (b) (ii) (d) (iii) (c) (iv) (a)

39. (i) (d) (ii) (c) (iii) (b)
40. (i) (d) (ii) (a) (iii) (b)
41. (i) (b) (ii) (e) (iii) (c) (iv) (d)
42. (i) (c) (ii) (a) (iii) (b)
43. (i) (b) and (c) (ii) (d) (iii) (a)
V. Assertion and Reason Type
44. (i) 45. (i) 46. (ii) 47.(iii) 48. (i) 49. (iii) 50. (iv)
VI. Long Answer Type
51. (i) Qc < Kc

(ii) Qc > Kc
(iii) Qc = Kc
where, Qc is reaction quotient in terms of concentration and Kc is equilibrium constant.
53.
S moles of AxBy dissolve to give xS moles of Ap+ and y S moles of Bq.]
54. G = G + RTlnQ
G = Change in free energy as the reaction proceeds
G = Standard free energy change
Q = Reaction quotient
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R = Gas constant
T = Absolute temperature
Since G = RT lnK
G = RT lnK + RT lnQ = RT ln Q/K
If Q < K, G will be negative. Reaction proceeds in the forward direction.

If Q = K, G = 0, no net reaction.
[Hint: Next relate Q with concentration of CO, H2, CH4 and H2O in view of reduced volume
(increased pressure). Show that Q < K and hence the reaction proceeds in forward direction.]
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NCERT Class XI Chemistry Chapter 7 Equilibrium (Part 2) | AglaSem... file:///C:/Users/Sony/Desktop/geochem.

Click Here for part 1

7.12 BUFFER SOLUTIONS

7.13 SOLUBILITY EQUILIBRIA OF SPARINGLY SOLUBLE SALTS

solubility in the following three categories.

Category I Soluble Solubility > 0.1M

Category II Slightly Soluble 0.01M<Solubility< 0.1M

Category III Sparingly Soluble Solubility < 0.01M

7.13.1 Solubility Product Constant

The equilibrium constant is given by the equation:

Ksp = K[BaSO4] = [Ba2+][SO42-]

1.1 x 10-10 = (S)(S) = S2 or S = 1.05 x 10-5.

[Zr4+] = 3S and [PO43-] = 4S

and Ksp = (3S)3 (4S)4 = 6912 (S)7

or S = {Ksp / (33 x 44)}1/7 = (Ksp / 6912)1/7

And its solubility product constant is given by:

Ksp = [Mp+]x[Xq- ]y = (xS)x(yS)y -(7.40)

S = (Ksp / xx . y y)1 / x + y (7.41)

A2X3 2A3+ + 3X2-

Ksp = [A3+]2 [X2-]3 = 1.1 x 10-23

If S = solubility of A2X3, then

[A3+] = 2S; [X2] = 3S

therefore, Ksp = (2S)2(3S)3 = 108S5 = 1.1 x 10-23

S = 1.0 x 10-5 mol/L.

Ksp = [Ag+][CN] = 6 x 10-17

Ksp = [Ni2+][OH]2= 2 x 10-15

Let [Ag+] = S1, then [CN] = S1

Let [Ni2+] = S2, then [OH] = 2S2

S12 = 6 x 10-17 , S1 = 7.8 x 10-9

(S2)(2S2)2 = 2 x 10-15, S2 = 0.58 x10-4

Ni(OH)2 is more soluble than AgCN.

7.13.2 Common Ion Effect on Solubility of Ionic Salts

Ksp = 2.0 x 10-15 = [Ni2+] [OH]2

= (S) (0.10 + 2S)2

As Ksp is small, 2S << 0.10, thus, (0.10 + 2S) 0.10

2.0 x 10-15 = S (0.10)2

S = 2.0 x 10-13 M = [Ni2+]

Ksp = [M+] [X],

Taking inverse of both side and adding 1 we get

([HX]+[H])/[X] = ([H+] + Ka)/Ka

Now, again taking inverse, we get

Ksp = [S] [f S] = S2 {Ka / (Ka + [H+])} and

S = {Ksp ([H+] + Ka ) /Ka }1/2 (7.42)

Thus solubility S increases with increase in [H+] or decrease in pH.

SUGGESTED ACTIVITIES FOR STUDENTS REGARDING THIS UNIT

(e) They may perform some acid-base titrations using indicators.

a) What is the initial effect of the change on vapour pressure?

b) How do rates of evaporation and condensation change initially?

Calculate Kp for the equilibrium.

7.6 For the following equilibrium, Kc= 6.3 x 1014 at 1000 K

7.8 Reaction between N2 and O2- takes place as follows:

What is Kc at this temperature ?

7.13 The equilibrium constant expression for a gas reaction is,

Kc = [ NH3 ]4[ O2]5/[ NO]4 [H2O]6

Write the balanced chemical equation corresponding to this expression.

Calculate the equilibrium constant for the reaction.

7.15 At 700 K, equilibrium constant for the reaction:

7.16 What is the equilibrium concentration of each of the substances in the

equilibrium when the initial concentration of ICl was 0.78 M ?

7.21 Equilibrium constant, Kc for the reaction

Calculate Kc for this reaction at the above temperature.

where fG (NO2) = 52.0 kJ/mol

fG (NO) = 87.0 kJ/mol

(a) Write as expression for Kp for the above reaction.