1
Chapter 6
Chemical Equilibrium
Reversible and irreversible reactions
A reaction that takes place in only one direction is called an irreversible reaction.
e.g. NaOH + HCl → NaCl + H2O
Reversible reactions are those which take place in both directions. i.e, here reactants combine to form
products and the products recombine to form reactants.
Eg: Haber process N2(g) + 3H2(g) ⇌ 2NH3(g)
The state of a chemical reaction when the concentration of reactants and products becomes constant and
do not change with time is called the state of equilibrium.
The Concept of Equilibrium
As a system approaches equilibrium, both the forward and reverse reactions are occurring hence it is called
dynamic equilibrium. At equilibrium, the forward and reverse reactions are proceeding at the same rate.
For a reversible reaction A + B ⇌ C + D,
.
EQUILIBRIUM IN PHYSICAL PROCESSES
1. Solid-Liquid Equilibrium
ICE ⇌ WATER
Ice and water kept in a perfectly insulated thermos flask at 273K and the atmospheric pressure are in
equilibrium state. The mass of ice and water do not change with time and the temperature remains
constant .
For any pure substance at atmospheric pressure, the temperature at which the solid and liquid phases
are at equilibrium is called the normal melting point or normal freezing point of the substance.
2. Liquid-Vapour Equilibrium
The equilibrium is attained when rate of evaporation becomes equal to rate of condensation.
H2O (l) ⇌ H2O(vap)
The temperature at which the vapour pressure of the liquid becomes equal to the atmospheric pressure is
called boiling point of the liquid
3. Solid – Vapour Equilibrium
When a solid sublimes to give its vapour and the vapour condenses to give solid at the same rate, this
equilibrium is attained. Eg;
1. I2(solid) ⇌ I2 (vapour)
2. Camphor (solid) ⇌ Camphor (vapour)
3. NH4Cl (solid) ⇌ NH4Cl (vapour)
pg. 1
2
Equilibrium Involving Dissolution of Solid or Gases in Liquids
Solids in liquids
When the rate of dissolution of solid becomes equal to rate of crystallisation of solid, solid-liquid
equilibrium is attained.
Gases in liquids
The solubility of a gas in liquid depends on nature of gas and liquid, temperature of liquid and pressure of
gas over the surface of the solution.
When temperature increases the solubility of a gas in a liquid decreases.
Henry’s law
The mass of a gas dissolved in a given mass of a solvent at any temperature is proportional to the
pressure of the gas above the solvent.
m p
m = KH p. KH is called Henry’s law constant
Why does a chilled soda water bottle fizz out when opened?
Soda water is a solution of CO2 in water dissolved at high pressure and low temperature. As soon as the
bottle is opened the pressure decreases and solubility of gas decreases, so some of the dissolved carbon
dioxide gas escapes rapidly with a fizz.
General Characteristics of Equilibria Involving Physical Processes.
Equilibrium is possible only in a closed system at a given temperature.
Both the opposing processes occur at the same rate so equilibrium is dynamic in nature.
All measurable properties of the system remain constant’.
For solid-liquid equilibrium, there is only one temperature (melting point) at 1 atm (1.013 bar) at which the
two phases can coexist.
For liquid-vapour equilibrium, the vapour pressure is constant at a given temperature.
For dissolution of solids in liquids, the solubility is constant at a given temperature.
For dissolution of gases in liquids, the concentration of a gas in liquid is proportional to the pressure
(concentration) of the gas over the liquid.
Characteristics of Chemical Equilibria.
Equilibrium is possible only in a closed system at a given temperature.
Chemical equilibrium is dynamic in nature.
At equilibrium the concentration of product and reactants does not change with time.
Equilibrium is not affected by the presence of catalyst
Why chemical equilibrium is said to be dynamic?
At equilibrium the reaction proceeds in such a way that the rate of formation of products from reactants
is equal to rate of formation of reactants from products.
pg. 2
3
LAW OF MASS ACTION
At constant temp and pressure ,the rate of a chemical reaction is directly proportional to the product of
molar concentration of the reactants.
For a reaction aA +bB ⇌ Product
Rate of reaction ∝ [A]a x [B]b
Rate =k [A]a[B]b. k= Rate constant
When [A] = [B] = 1, Rate = k
So Rate constant (k) = Rate
Rate constant of a reaction at a given temp is the rate of the reaction when the conc: of each of the
reactants is unity.
The Equilibrium Constant
Consider a reversible reaction: aA + bB ⇌ cC + dD
Rate of forward reaction Ratef = kf [A]a[B]b
Rate of backward reaction Rateb = kb[C]c[D]d
LAW OF CHEMICAL EQUILIBRIUM.
The Law of Chemical Equilibrium states that, for a reversible chemical reaction at constant temperature,
the ratio of the concentrations of the products to the concentrations of the reactants, each raised to the
power of their respective stoichiometric coefficients, is constant when the system has reached equilibrium.
The Equilibrium Constant in gaseous system.
Because pressure is proportional to concentration for gases in a closed system, the equilibrium expression
can also be written as
(PC)c (PD)d
Kp = PA ,PB,PC and PD are partial pressures of gases A,B,C and D
(PA)a (PB)b
b) i) Write the expression for equilibrium constant Kp for the following equilibrium.
2NOCl(g) ⇌ 2NO(g) + Cl2(g)
Kp = ( PNO)2.(PCl2)
( PNOCl)2
pg. 3
4
Q. Derive the relation between equilibrium constants Kc and Kp for a general reaction:
aA + bB ⇌ cC + dD at equilibrium.
Relationship between Kc and Kp
Δn = (no: of moles of gaseous product) − (no: of moles of gaseous reactant) ie: ∆n = nP(g) – nR(g)
Q.(a) Write the expression for the equilibrium constant for the general reaction:
aA + bB ⇌ cC + dD.
(b) Give the relation between Kp and Kc of a reaction in equilibrium.
Ans: (a) Kc = [C] c [D] d Or, Kp = (PC )c .(PD )d
[A] a [B] b (PA )a .(PB )b
∆n
(b) Kp = Kc(RT)
Features of equilibrium constants
1. The value of equilibrium constant is independent of initial concentrations of the reactants and
products.
2. Equilibrium constant is temperature dependent.
3. Independent of the presence of catalyst.
4. The equilibrium constant for the reverse reaction is equal to the inverse of the equilibrium constant for
the forward reaction.
pg. 4
5
EXAMPLE
Q. During a class room discussion one of your friends argues that equilibrium constant is not altered with
change in temperature. What is your view towards this argument? Justify.
Ans: a) This statement is wrong. The value of equilibrium constant depends on temperature. Based on the
value of ∆H, it may increase or decrease with temperature.
Q. Give the relation between Kp and Kc, for the reaction given below.
2NOCI (g) ⇌ 2NO(g) + Cl2(g)
Ans: Kp = Kc(RT)∆n
Here ∆n = nP(g) – nR(g) = 3 – 2 = 1
So, Kp = Kc.RT
Q. Differentiate between homogeneous and heterogeneous equilibria.
Homogeneous Equilibrium
Here the reactants and the products are in the same phase
Heterogeneous Equilibrium
The equilibrium reactions where reactants and products are in different phases are called heterogeneous
equilibrium reactions
Here molar conc of pure solids and liquids =1
Q. Write the equilibrium constant expression for Kc and Kp for the formation of nickel tetracarbonyl,
which is used to separate nickel from other impurities.
Ni (s) + 4CO(g) ⇌ Ni(CO)4(g)
Kc = [Ni(C0)4] Kp = P Ni(CO)4 SINCE [Ni] = constant and PNi = constant.
[CO]4 ( PCO)4
pg. 5
6
Q. Examine the chemical equilibrium, 4NH3(g) + 5O2(g) ⇌ 4NO(g) + 6H2O(l). Write the expression for
equilibrium constant (Kc) for the above equilibrium.
What happens to Kc, if the balanced equation is multiplied throughout by a factor of 2.
Ans: Kc = [NO]4 [H2O]6
[NH3] 4 [O2] 5
Kc = [NO]4 [H2O] = 1
4 5
[NH3] [O2]
If the balanced equation is multiplied throughout by 2, then Kc’ = Kc2.
Q. For the reaction, CaCO3(s) ⇌ CaO(s) + CO2(g)
a) Write down the expression for Kp.
b) What is the relation between Kp and Kc in the above reaction?
Ans: a) Kp= PCO2 since pCaCO3 & PCaO are constants
b) Here ∆n = nP(g) - nR(g) = 1 – 0 = 1.
So Kp = Kc.RT .
Q. Write the expression for equilibrium constant Kc for the following equilibrium.
CuSO4.5H2O(s) ⇌ CuSO4.3H2O(s) + 2H2O(g)
Ans: a) Kc = [CuSO4.3H2O][H2O]2
[CuSO4.5H2O]
Kc = [H2O]2 Since = [CuSO4.3H2O] = 1 [CuSO4.5H2O] = 1
27. a) Write an equation for equilibrium constant in terms of concentration (Kc) for the equilibrium
reaction given below. Ag2O(s) + 2HNO3(aq) ⇌ 2AgNO3(aq) + H2O(l)
Ans: a) Kc = [AgNO3] 2 [H2O]
[Ag2O][HNO3] 2
Kc = [AgNO3] 2 since [H2O] = 1 [Ag2O] = 1
2
[HNO3]
(a)Write the expression for equilibrium constant, Kc for the reaction
4NH3(g) + 5O2(g) ⇌ 4NO(g) + 6H2O(l)
b) What happens to the value of the equilibrium constant (Kc) when the above reaction is
reversed?
Ans: a) Kc = [NO]4 [H2O]6
[NH3] 4 [O2]5
Kc = [NO]4 since[H2O] = 1.
4 5
[NH3] [O2]
b) When the reaction is reversed, the new equilibrium constant (Kc’) = 1/Kc.
Q. The value of equilibrium constant is useful to predict the extent of reaction and the direction of
the reaction at a given stage. Explain.
APPLICATIONS OF EQUILIBRIUM CONSTANT
1. Predicting the extent of a reaction
The magnitude of Kc or Kp is directly proportional to the concentrations of products So high value of K
shows high concentration of products.
1. If Kc > 103, products predominates, reaction proceeds nearly to completion.
2. If Kc < 10–3, reactants predominates, and the reaction proceeds rarely.
3. If Kc is in the range of 10–3 to 103, appreciable concentrations of both reactants and products are
present.
pg. 6
7
2. Predicting the Direction of the Reaction
For this purpose, we calculate the reaction quotient Q. The reaction quotient, Q (Qc with molar
concentrations and QP with partial pressures) is defined in the same way as the equilibrium constant Kc
except that the concentrations in Qc are not necessarily equilibrium values.
For a general reaction:
REACTANT → PRODUCT PRODUCT→ REACTANT
If Qc > Kc, backward reaction proceeds (reverse reaction).
If Qc < Kc, the reaction will proceed in the direction of the products (forward reaction).
If Qc = Kc, the reaction is at equilibrium.
3. Calculate equilibrium concentrations
By knowing the value of equilibrium constant, we can calculate the equilibrium concentrations of
reactants and products.
Q. Equilibrium constant helps in predicting the direction in which a given reaction will proceed at any
stage.
a) In which one of the following conditions a chemical reaction proceeds in the forward direction?
a) QC < KC , b) QC > KC , c) QC = 1/KC , d) QC = - KC
Ans: a) QC < KC
Relationship between equilibrium constant(K), Reaction quotient(Q) and Gibbs energy(G).
• ΔG is negative, then the reaction is spontaneous.
• ΔG is positive, then reaction is considered non- spontaneous.
• ΔG is 0, reaction has achieved equilibrium.
ΔG = ΔG0 + RT ln Q .
At equilibrium, ΔG = 0 So Q=K
0= ΔG0 + RT lnK .
ΔG0 = -RT lnK . lnK = - ΔG0/RT. Taking antilog of both sides
ΔG0 = -2.303 RT logK.
pg. 7
8
Le Chatelier’s Principle
If a system at equilibrium is subjected to a change in concentration, temperature or pressure system
proceeds in that direction so as to reduce the effect of the change.
Effect of Concentration
CHANGE EFFECT
Reactant is added Favours forward reaction
Product is added Favours backward reaction
Reactant is removed Favours backward reaction
Product is removed Favours forward reaction
Effect of Pressure Change
When pressure is increased, the equilibrium shifts in the direction with lesser number of gaseous moles.
If the number of moles are same, there will be no effect on change of pressure.
When pressure is decreased, the equilibrium shifts in the direction with more number of gaseous moles.
Examples
1.CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)
On increasing pressure, more products are formed
2.N2(g) + 3H2(g) ⇌ 2NH3(g)
On increasing pressure, more products are formed
3.H2(g) + I2(g) ⇌ 2HI (g)
Pressure has no effect on this reaction
4.C(s) + CO2(g) ⇌ 2CO(g),
On increasing pressure, more reactants are formed
Effect of Temperature
When temperature is increased, the system shifts in the direction of endothermic reaction.
When temperature is decreased, the system shifts in the direction of exothermic reaction.
The Haber Process Exothermic
1. Effect of concentration
If N2 or H2 is added to system or NH3 is removed forward reaction occurs .
2. Effect of pressure
When pressure is increased, the equilibrium shifts in the direction with lesser number of gaseous moles. So
forward reaction occurs.
3. Effect of Temperature
Formation of NH3 is exothermic. So low temperature will favour the formation of ammonia. But if the
temperature is too low, there will be not enough activation energy for the reactants. So an optimum
temperature of 773K is used.
4. Effect of catalyst
Powdered iron catalyst and Molybdenum as promoter are used to attain equilibrium faster.
Low temperature, high pressure, excess of N2 & H2 , removal of NH3 and iron catalyst will favour the
formation of NH3.
pg. 8
9
Q. Predict the conditions to be applied to maximize the production of ammonia in the following reaction.
N2(g) + 3 H2(g) ⇌ 2 NH3(g); ∆H = -92.38 kJ/mol
Ans: Low temperature, high pressure, excess of N2 & H2 , removal of NH3 and iron catalyst will favour the
formation of NH3.
Q. Le-Chatlier’s principle makes a qualitative prediction about the change in conditions on equilibrium.
a) State Le-Chatlier’s principle.
b) N2(g) + O2(g) ⇌ 2NO(g). What is the effect of pressure on the above equilibrium.
Ans: Since the number of moles are same on both sides, there will be no effect on change of pressure.
Q. Explain the effect of pressure in the following equilibrium using Le Chatelier principle:
CO(g) + 3H2(g ) ⇌ CH4(g) + H2O (g)
Ans : As a result of forward reaction, the no. of moles of gaseous species decreases. So high pressure
favours the forward reaction.
Q. Explain the effects of temperature and pressure on the following equilibrium.
2NO2(g) ⇌ N2O4 (g) ; ∆H = -57.2 kJ mol –1
Ans: Effect of temperature: Here the forward reaction is exothermic. So low temperature favours this
process.
Effect of pressure: As a result of forward reaction, the no. of moles of gaseous species decreases. So
high pressure favours the forward reaction.
Q. Comment on the effect of increasing pressure in the reaction, 2SO3(g) ⇌ 2SO2(g) + O2(g)
Ans: Here the forward reaction results in increase in no. of moles of gaseous species. So low pressure
favours forward reaction.
ACIDS, BASES AND SALTS
Arrhenius Concept of Acids and Bases
Acids are substances that give hydrogen ions ( H+(aq) ) in aqueous solution.
Eg; HCl, H2SO4, CH3COOH, H2CO3 etc
Bases are substances that produce hydroxyl ions ( OH– (aq) ) in aqueous solution.
Eg; NaOH, KOH, NH4OH, Ca(OH)2 etc.
Limitations
1. Fails to explain the behaviour of acids and bases in non-aqueous solvents.
2. Cannot explain the acidic character of AlCl3, BF3 etc and the basic character of NH3, PH3 etc.
Q. a) Give the Arrhenius concept about acids and bases.
b) Give one example each for Arrhenius acid and base.
Ans: a) According to Arrhenius concept acids are substances which give hydrogen ion (H+ ) or hydronium ion
(H3O+ ) in aqueous solution and bases are substances which give hydroxyl ion (OH- ) in aqueous solution.
b) Eg for Arrhenius acid ; HCl, H2SO4,
Eg for Arrhenius base; NaOH, KOH,
The Brönsted-Lowry concept of Acids and Bases
According to Brönsted-Lowry theory, acid is a substance that is capable of donating a hydrogen ion H+
(proton donor) and bases are substances capable of accepting a hydrogen ion, H+ (proton acceptor).
Conjugate acid base pair --The acid-base pair that differs only by one proton is called a conjugate acid-
base pair.
pg. 9
10
Therefore, Cl– is called the conjugate base of an acid HCl and H3O+ is called conjugate acid of the base H2O.
If Brönsted acid is a strong acid then its conjugate base is a weak base and vice versa
A base formed from an acid by the loss of a proton is called a conjugate base
Conjugate Base = Acid – H+
An acid formed from a base by the gain of a proton is called conjugate acid
Conjugate Acid = Base + H+
AMPHOTERIC SUBSTANCE
Substances which can act both as an acid and a base are called amphoteric or amphiprotic substance. Eg;
H2O , NH3, HCO3-, HSO4- etc
14. H2O and NH3 can act both as Bronsted acids and bases. For each case give the corresponding conjugate
acid and conjugate base.
Ans: Conjugated acid = Base + H+ Conjugate base = Acid – H+
+ +
H2O + H -----> H3O . H2O -- H+ -----> OH–
NH3 + H+ -----> NH4+ . NH3 - H+ ------> NH2–
Q. The species HCO3 - and HSO4 - can act both as Bronsted acids and bases. Write the corresponding
conjugate acid and conjugate base of the above species.
Conjugate Acid = Base + H+ Conjugate Base = Acid – H+
- +
HCO3 + H --------->H2CO3 HCO3- – H+ ------------ > CO32-
HSO4- + H+--------->H2SO4 HSO4- – H+---------> SO 42-
4. The species that can form both conjugate acid and conjugate base among the following is:
(a) H2O (b) BF3 (c) HCl (d) CO2
Ans: (a) H2O
Q. What is conjugate acid – base pair? Illustrate with an example.
Ans: Acid - base pairs which are differed by a proton (H+ ) are called conjugate acid -base pair. Eg :Given
above.
Lewis Acids and Bases
Acid is a species which accepts electron pair and base is a species which donates an electron pair.
Electron deficient species like AlCl3, BF3, BCl3 etc
Lewis Acids
Positive charged species like (Co3+, Mg2+)
Electron rich species like H2O, NH3, R-OH, R-NH2 etc
Lewis Bases
Negative charged species like (OH– ,Cl--)
pg. 10
11
Q. An example of Lewis acid among the following is:
(a) HCl (b) NH3 (c) H2SO4 (d) BF3
Ans: (d) BF3
Q. Select the Lewis acid from the following: (NH3, OH- , BCl3, Cl- )
Ans: a) BCl3
Q. Give the Lewis concept of acids and bases with suitable example.
Ans: According to this concept, acids are electron pair acceptors and bases are electron pair donors.
Example for Lewis acids are BF3, AlCl3 etc.
Example for Lewis bases are NH3, H2O etc
Q. Classify the following into Lewis acid and Lewis base.
i) H2O ii) NH3 iii) AlCl3 iv) H+
Ans: Lewis base --- NH3 , H2O . Lewis acid ---- AlCl3 , H+
Q. According to Lewis theory, classify the following into acids and bases: H2O, NH3, AlCl3, OH-
Lewis acid is AlCl3
Lewis bases are NH3, H2O and OH-
IONIZATION OF ACIDS AND BASES
Strong acids
They are almost completely dissociated into their constituent ions in an aqueous medium.
Eg: HCl, HBr, HI, HNO3, H2SO4 ,HClO4
Strong bases
Strong bases are almost completely dissociated into ions in an aqueous medium giving hydroxyl ions, OH–
Eg: LiOH, NaOH, KOH, CsOH, Ba(OH)2
Ionic Product of Water
Q. What is ionic product of water?
Ionic product of water is defined as the product of the concentration of hydronium ion and hydroxide ion
at a constant temperature
Kw = [H3O+] [OH–]
The value of KW is 1 x 10-14 mol2/L2 at 250 C.
For pure water, [OH–] = [H+] = 1.0 x10–7 M.
Value of KW increases with increase in temperature.
The pH Scale
The pH of a solution is defined as the negative logarithm to base 10 of hydrogen ion concentration
expressed in mol/L.
pH = – log {[H+] / mol L–1}
= – log {[H3O+] / mol L–1}
pg. 11
12
• Acidic solution has pH < 7
• Basic solution has pH > 7
• Neutral solution has pH = 7
RELATION BETWEEN pH & pOH
pH = – log {[H+]}
similarly pOH = – log {[OH- ]}
pH + pOH = 14
Degree of dissociation (ionization) (α)
α = No of moles ionized
Total no; of moles dissolved
At a given temperature T, Ka is a measure of the strength of the acid HX i.e., larger the value of Ka, the
stronger is the acid
Ostwalds dilution law
For a weak electrolyte degree of dissociation is inversely proportional to the square root of
concentration.
Relation between Ka and Kb
For a conjugate acid base pair Ka . Kb = Kw
13. Weak acids are partially ionized in aqueous solutions. The ionization constants of some acids are given
below. Arrange the below acids in the increasing order of their acid strength.
Acid Ionisation constant (Ka)
Formic acid (HCOOH) 1.8 x 10-4
Hypochlorous acid (HOCl) 3.0 x 10-8
Nitrous acid (HNO2) 4.5 x 10-4
Hydrocyanic acid (HCN) 4.9 x 10-10
Ans: a) HCN < HOCl < HCOOH < HNO2 (As the value of Ka increases, acidity increases).
pg. 12
13
Di- and Polybasic Acids and Di- and Polyacidic Bases
Acids having more than one ionizable proton per molecule of the acid are known as polybasic or
polyprotic acids .eg; sulphuric acid, oxalic acid
H2SO4 → H+ + HSO4-
HSO4 - → H+ + SO4 2-
Factors Affecting Acid Strength
The extent of dissociation of an acid depends on the strength and polarity of the H-A bond.
When strength of H-A bond decreases, HA becomes a stronger acid.
When the H-A bond becomes more polar, cleavage of the bond becomes easier ,H-A is a strong acid.
For same group elements---H-A bond strength is considered.
When size of A increases H-A bond strength decreases & acid strength increases
HF << HCl << HBr << HI
For same row elements---H-A Bond polarity is considered.
When electronegativity of A increases, acid strength increases
CH4 < NH3 < H2O < HF
Q. Arrange the following in the increasing order of their acidic strength: HBr, HI, HF, HCl.
b) HF < HCl < HBr < HI
Q. Explain the term common ion effect with suitable example.
Common Ion Effect
The ionisation of a weak electrolyte is suppressed by the addition of a strong electrolyte which contains a
common ion . This effect is called common ion effect .
Eg 1. Addition of sodium acetate to acetic acid solution
Here
Concentration of CH3COO– increases and backward reaction occurs ie, dissociation of acetic acid is
suppressed .
Eg 2. Dissociation of ammonium hydroxide
When ammonium chloride is added to ammonium hydroxide solution , dissociation of NH4OH is
suppressed
Q. The dissociation of NH4OH is suppressed by the addition of NH4Cl. Name the principle applied here.
Q. When some sodium acetate is added to a solution of acetic acid, the concentration of unionized acetic
acid increases. What is the phenomenon involved? Substantiate.
Ans: Common ion effect. It is the suppression of the dissociation of a weak electrolyte by the addition of a
strong electrolyte containing a common ion.
Common Ion Effect on Solubility of Ionic Salts
If we take impure saturated solution of sodium chloride and pass HCl gas through it, then pure NaCl is
precipitated due to increased concentration of chloride ion available from the dissociation of HCl.
pg. 13
14
NaCl ⇌ Na+ + Cl-
HCl → H+ + Cl-
Sodium chloride thus obtained is of very high purity and we can get rid of impurities like sodium and
magnesium sulphates.
Classification of salts
Q. Explain the hydrolysis of different types of salts with the help of examples and comment on the pH of
the resulting solutions in each case.
SALT HYDROLYSIS
Addition of water to a salt resulting acidic or basic or neutral solution is known as salt hydrolysis.
NaCl + HOH → HCl + NaOH (neutral)
NH4Cl (aq) + HOH → NH4OH + HCl (acidic)
Salts of strong acid and strong base
Eg; NaCl
NaCl + HOH → HCl + NaOH
strong acid Strong base
HCl & NaOH are strong and are completely ionised and the nature of solution is neutral. pH is 7.
Salts of strong acid and weak base
Eg; NH4Cl
NH4Cl (aq) + HOH → NH4OH + HCl
weak base Strong acid
Ammonium hydroxide is a weak base and therefore remains almost unionised in solution. This results in
increase of H+ ion concentration in solution making the solution acidic. Thus, the pH of NH4Cl solution in
water is less than 7.
Salts of weak acid and strong base
E.g., CH3COONa.
CH3COONa(aq) + HOH(l) → CH3COOH(aq) + NaOH(aq)
weak acid Strong base
Acetic acid being a weak acid remains mainly unionised in solution. This results in increase of OH– ion
concentration in solution making it alkaline. The pH of such a solution is more than 7.
Salts of weak acid and weak base
Eg ; CH3COONH4
CH3COO NH4 + HOH →
CH3COOH + NH4OH
Weak acid weak base
CH3COOH and NH4OH, remain partially dissociated. pH of such solutions is determined by their pK values:
pKa = -logKa
pH = 7 + ½ (pKa – pKb) pKb = -logKb
pg. 14
15
Q. Predict the nature of solution produced by the hydrolysis of sodium acetate.
Ans: CH3COONa(aq) + HOH(l) → CH3COOH(aq) + NaOH(aq)
Weak acid Strong base .
Ans : sodium acetate is Basic
Q. An aqueous solution of NaCl is neutral, while that of CuCl2 is acidic. Why?
NaCl + HOH --------> NaOH + HCl
NaCl is a salt of strong acid HCl and strong base NaOH. So it is neutral.
CuCl2 +2HOH --------> Cu(OH)2 + 2HCl
But CuCl2 is a salt of strong acid HCl and weak base Cu(OH)2. So it is acidic.
Q. An aqueous solution of CuSO4 is acidic while that of Na2SO4 is neutral. Explain.
CuSO4 + 2HOH --------> H2SO4 + Cu(OH)2 Na2SO4 + 2HOH --------> 2NaOH + H2SO4
CuSO4 is a salt of strong acid and weak base. So it is acidic. While Na2SO4 is a salt of strong acid and strong
base. So it is neutral.
Q. Classify the following solutions into acidic, basic and neutral. NaCl, NH4NO3, NaCN, NaNO2
NaCl + HOH --------> NaOH + HCl NH4NO3 + HOH --------> HNO3 + NH4OH
NaCN + HOH --------> NaOH + HCN NaNO2 + HOH --------> NaOH + HNO2
Ans: a) NaCl – Neutral, NH4NO3 – Acidic, NaCN – Basic, NaNO2 – Basic
Q. The pH of a salt solution depends on the hydrolysis of its ions. Out of the following, which can produce
an acidic solution in water?
(CH3COONa, NH4Cl, CH3COONH4, NaCl)
Ans: NH4Cl
Q. The aqueous solutions of the ionic compounds NaCl, CH3COONa and NH4Cl show different pH.
Identify the acidic, basic and neutral solutions among these.
NaCl + HOH --------> NaOH + HCl NaCl is a salt of strong acid HCl and strong base NaOH .So the
solution is neutral.
NH4Cl + HOH --------> NH4OH + HCl. NH4Cl is a salt of strong acid HCl and weak base NH4OH. So it is acidic.
CH3COONa + HOH ------→ CH3COOH + NaOH . CH3COONa is a salt of weak acid CH3COOH and strong
base NaOH. So it is basic.
Q. Define buffer solution and write examples for acidic buffer and basic buffer.
BUFFER SOLUTIONS
The solutions which resist change in pH on dilution or with the addition of small amounts of acid or alkali
are called Buffer Solutions. They have a definite pH value. It may be of 2 types
Acid buffer & Basic buffer
A mixture of acetic acid and sodium acetate acts as acidic buffer solution around pH 4.75 and a mixture of
ammonium chloride and ammonium hydroxide acts as a basic buffer around pH 9.25.
Types of buffer solutions
Acidic buffer: A solution containing a weak acid and its salt with strong base is called an acidic buffer
solution.
eg. CH3COOH & CH3COONa, HCOOH & HCOONa, H2CO3 & K2CO3
Basic buffer: A solution containing a weak base and its salt with strong acid is the basic buffer solution.
eg. NH4OH & NH4Cl , NH4OH & NH4NO3
Neutral buffer: eg; Human blood
Q. pH of blood remains constant inspite of variety of foods and spices we eat. Give a reason.
Ans : Because of the presence of H2CO3/HCO3 – buffer system in the blood.
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pH of a Buffer solution – Henderson - Hasselbalch Equation
Consider an acidic buffer prepared by mixing a weak acid HA and its conjugate bas A-. The weak acid HA
ionises in water as:
HA + H2O ⇌ H3O + + A-
The dissociation constant of weak acid,
Ka = [H3O + ] [A- ] /[HA]
log Ka = log[H3O + ] + log[A- ] – log[HA]
Rearranging
-log[ H3O +] = -logKa + log[A- ] – log[HA]
Or,
pH = pKa + log[[A- ]/[HA]]
This equation is known as Henderson-Hasselbalch equation.
The equation can be written in general form as:
For an acid buffer,
pH = pKa + log[Salt]/[Acid]
For a basic buffer,
pOH = pKb + log[Salt]/[Base]
or,
pH = 14 – [pKb + log[Salt]/[Base]
Q. Write the Henderson – Hasselbalch equation for an acidic buffer. Calculate the pH of an acidic buffer
containing 0.1 M CH3COOH and 0.5 M CH3COONa. [Ka for CH3COOH is 1.8 x 10-6.
For an acidic buffer Henderson – Hasselbalch equation, pH = pKa + log[Salt]/[Acid]
Here [Acid] = 0.1M, [Salt] = 0.5M and Ka = 1.8 x 10-6
pKa = -log Ka = - log(1.8 x 10-6 ) = 5.7447
pH = pKa + log[Salt]/[Acid] = 5.7447 + log(0.5/0.1) = 6.444
SOLUBILITY AND SOLUBILITY PRODUCT
Solubility is defined as the maximum amount of solute dissolved in a particular amount of solvent to form a
saturated solution at a fixed temperature.
(s) Classification of salts based on solubility
Q. Salts can be classified into different categories on the basis of their solubility. a) Identify the solubility
range of sparingly soluble salts from the following:
(a) 0.01 M < solubility < 0.1 M, (b) solubility < 0.01 M, (c) solubility > 0.1 M) (d)None of these.
Ans : Solubility < 0.01M
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SOLUBILITY PRODUCT OF SPARINGLY SOLUBLE SALT
Solubility product of a sparingly soluble salt at a given temp is the product of ionic concentration in the
saturated solution.
Examples are given below
1. PbCl2 (s) ⇌ Pb2+ (aq) + 2 Cl− (aq)
Ksp = [Pb2+] [Cl−]2
2. AgCl (S) ⇌ Ag+ (aq) + Cl- (aq)
Ksp = [Ag ] [Cl−]
+
3. CaSO4 ⇌ Ca2+ + SO42-
Ksp = [Ca2+ ][SO4 2-]
4.(Zr)3 (PO4 )4 ⇌ 3Zr4+ + 4PO43-
Ksp = [Zr4+]3 [PO43-]4
Relation between solubility and solubility product
AXBY Type Salt
AB Type Salt Eg: AgCl, CaSO4 , BaSO4
KSP = xx.yY.S(x+ y) x = 1, y= 1
KSP = 11.11.S(1+ 1) KSP = S2
AB2 Type Salt Eg: PbCl2 AB3 Type Salt Eg: Fe(OH)3
KSP = xx.yy.S(x+ y) x = 1, y= 2 KSP = xx.yy.S(x+ y) (x = 1, y= 3)
KSP = 11.22.S(1+ 2) KSP = 4S3 KSP = 11.33.S(1+ 3) KSP = 27S4
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Q. Find the solubility product constant of Zirconium phosphate.
Ans : For (Zr)3 (PO4 )4 x = 3 & y = 4
Ksp = xx.yy.S(x+ y)
KSP = 33. 44. S(3+ 4)
KSP = 27 x 256 S7 = 6912S7
Extra Questions
Q. (a) What is homogeneous equilibria ? Give an example for it.
(b) Write the relationship between KP and KC for the reaction H2 (g) + I2 (g) ⇌ 2HI(g).
Ans: (a) It is an equilibrium process in which all the reactants and products are in same phase.
Eg; N2(g) + 3H2(g) ⇌ 2NH3(g)
(b) Kp = Kc(RT)∆n
∆n = 2-2 = 0
Kp = Kc(RT)0 So Kp = Kc
Q. In the reaction CO(g) + Cl2(g) ⇌ COCl2(g), what effect does increasing the concentration of Cl2 have on the
equilibrium position?
Ans: According to Le Chatelier's Principle, the system will respond by shifting the equilibrium to the
right, towards the production of more COCl2, to reduce the concentration of Cl2.
Q. What is the effect on the equilibrium position if a catalyst is added to the reaction 2SO2(g) + O2(g)⇌ 2SO3(g)?
Ans: Adding a catalyst does not change the position of the equilibrium.
Q. Given a buffer solution containing 0.1 M acetic acid (CH₃COOH) and 0.1 M sodium acetate (CH₃COONa),
calculate the pH of the buffer solution. Assume the Ka of acetic acid is 1.8×10−5.
Ka = 1.8×10−5 [Salt] = 0.1 M [Acid] = 0.1 M
pKa = −log(Ka) = −log(1.8×10−5) ≈ 4.74
pH = pKa + log[Salt]/[Acid]
pH = 4.74 + log(0.1/0.1)
pH = 4.74 + log(1) = 4.74. So, the pH of the buffer solution is 4.74.
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