1

lonic Egquilibria

They have conductivity smaller than that of strong

lonic Equilibrium electrolytes. Their value of degree of dissociation is
in the reactions
lonic equilibrium is the study ofequilibrium much smaller than one i.e., a << 1. An equilibrium
where formation of ions take place in aqueous solution. is set up in case of partially ionised weak electrolytes
between ions and unionised electrolyte.
Concepts of acids and bases
Arrhenius concept:Arrhenius acid furnishes hydrogen e.g, NH,OH(ag) NH4(a0) +O (ag)

ions in aqueous solution, e,g., HCI. Degree (): The fraction oftotal number of
of ionisation
Arrhenius base fumishes hydroxyl ions
in aqueous molecules dissociated into ions at a particular temperature
of dissociation.
solution, eg., NaOH. is known as degree of ionisation or degree
acid donates a It is denoted by a.
Brönsted-Lowry concept : Brönsted Number of moles dissociated
proton, eg, HCI.
Brönsted base accepts a proton, e,g., NH3. Total number of moles
the pairs of and it
Conjugate acid base pairs:
- These are
Degree of ionisation depends on temperature
acids and bases which differ by a proton, e.g., increases with increase in temperature.

Conjugate acid conjugate base lonisation of weak electrolytes

+H
bases depend acid HA in water,
Relative strengths of conjugate acids or
For the dissociation ofa weak monobasic
to donate a proton or to accept a
represented by the equation:
upon their tendency
proton.
HA + H 0 H , 0 " +A
Lewis concept: Lewis acid accepts a pair ofelectrons, Applying the law of chemical equilibrium,
eg, BF3. K H4") [: H,OH]
Lewis base donates a pair of electrons, eg., NH3.
[HA]
constant.
where Ka is called acid dissociation
Electrolytes measure of its acid
or melted, it The value of Ka for a particular acid is a
When an ionic compound is dissolved in water
is known as ionisation strength or acidity.
gets split into its ions. This process large for a strong
ions have either positive or The value of acid dissociation constant is
or dissociation. Since the
the aqueous solution or molten state of acid while it is small for a weak acid.
negative charge,
such compounds can conduct electricity.
or melt conduct Ostwald's dilution law
A compound whose aqueous solution
whereas non-electrolyte According to Ostwald's dilution law for weak electrolytes
electricity is known as electrolyte, nor melt the degree of dissociation is inversely proportional to the
solution
is the compound whose neither aqueous
conducts electricity. 1
square root of concentration i.e., a * or, a C
Strong and weak electrolytes: Electrolytes which VC
dissociate almost completely into ions in aqueous
a"
and Aa,
For two weak acids of dissociation constants Ka,
solution are known as strong electrolytes, e.g., NaCl, the same concentration
conductors
HC1, NaOH, H2SO4, etc. They are very good
dissociation nearly
of electricity. They have degree of
one i.e., a l .
Whereas those electrolytes which dissociate only where and az are the respective degrees of dissoc1auo
known as
partially into ions in aqueous solution are of the two acids.
etc.
weak electrolytes, e.g, CH3COOH, NHOH,
o n i cE q u i l i b r i a
147
the
is very small,
of ionisation of
water
isationc o n s t a n t s of weak acids and bases degree
Since the taken
water may be practically
concentration of unionised
ider the dissociation of a weak acid HA as, we have
Let us consider
as constant. Th
HA H'+A Kx [H,O] = [H,O"] [OH]
00 K x Constant = [H3O"J[OHJ
C
Co Ca
A= C(-) K=[H,Oj[OH] the dissociation
At lagm H :Ca H] [OH] where K is called
A ionic product of
water.
ofacid, K,
=
constant
more commonly the
$Ociation
Dissoc
[HA C(-0) Constant or
water is the product
of the
Thus, ionic product of ions in water
Co Concentrations of hydrogen
ions and hydroxyl
or any aqueous solution at a given
temperature.
(1-a) At
The value of K,, is a constant at given
a temperature.
dissociation of a weak base BOH as water,
for the mol L. In pure
298 K the value is about 1 10-1
x
Simila
BOH B" +OH is equal to the
concentrations
the concentrations of H" ions
NOH Ca2
constant
of base,K, =
of OH ions.
pissociation [BOH] (1-0) [H,0]=[OH]= 1 x 10 mol L
to the pure
neutral. If we add acid
constant for polyprotic acids and bases Theretore, pure water is
nissociation decreases. If we add
water the [H] increases and [OH]
involve number of steps to ionise completely,
These acids a base, [OH] increases
and [H] will correspondingly
of steps is equal to the number of replaceable ionic product Ky is always
here number each become very small. But the
The value of ionization constant of The value of K
hudrogen atoms. a constant at a
constant temperature.
and constant e.g., increases with increase in temperature.
is definite
step
H,PO H" +H,PO
pH-Scale
H,PO H +HPO0 Sorensen in 1909, suggested a new
term for expressing

ion known as pH or pH
HPO H +PO the concentration of hydrogen
solution is defined as the negative
dissociation constant (K) is given as scale. The pH of a
in moles per litre.
The overall concentration
K=Kj x K2 x K3 logarithm of the H,0 ion as
Mathematically it can be expressed
where, K> K2 > Kz
bases
weak acids and weak pH -loglH,OT or lo8H.O1
Relative strength of
weak acid HA, which undergoes
Let us consider a
K,
neutral solution at x 10 298
hydrolysis as For[HO]=[OH]=1 mol L-
HA +H,O A+H0 pH-log[H,0]=-log(1 x 10) =7
At 1=0 C different values of [H30D1
Coa Co In a similar way, by substituting
At 'qm C(l-a)
can be seen that,
for acidic solution
in the above relation it solution
solution pH> 7, and for neutral
[H,07-Ca= C= K_C pH7, for basic
p H = 7. -
different weak acids the acidic and basic
fvalue ofK, Ka, and C, C, for two of two The pH scale is used to express
the relative strength which is represented as
areknown, we can compare character ofsolutions
10-° 10-0 10rl 10-12 10-3 10-14
weak acids.
H,o* 10°10- 102 10-3 1010 10-6 10-10-$
H,0 CL pH 0 1 2 3 456 7 89 10 11 12 13 14

Relative strength
of acids C
K, VC Increasing acidity
Neutral
Increasing basicity
of the
solution is the negative logarithm
of
Dimilarly for two different weak bases
The pH a
of hydrogen ions.
concentration (in moles per litre)

OH pH log[H']
If pH value of a
solution is 7, it is neutral, if pH
value is

OH C less than 7, the

solution is acidic and if it is
more than 7, the

solution is alkaline.
lonic product of water
selfionisation to solutions of acids and bases
rWater 1 a weak electrolyte and undergoes pH of aqueous concentration
a small extent as which hydrogen ion
An aqueous solution in acidic.
mole per litre is said to be
+H,Ou H,O"(ag)+OH () is greater than I 10
x
concentration
Theulnbrium constant for the ionisation of water is in which hydrogen ion
An aqueous solution
ion concentration is greater than)
is less than (i.e,. hydroxyl
K 0"][OH"] mole is said to be alkaline.
perlitre
1x 10
H,O
 MtG Chapterwise WB JEE
EXPLORER
148
Salts of strong acid and strong base:
Buffer solutions Examples: KCI, NaCl, K2S04, NazSO4, KNO, NaNO,,ctctc.
in its ph Consider the hydrolysis of NaCIl,
A butfer solution is one which can resist change
NaOH + HCI
base. NaCl + H20>
value on the addition of an acid or
to resist alternation in its pH or, Na + CI+H,0> Na" +
OH + H' + C
The capacity of a solution Thus, such salts only ionise and do not hydrolyse. It ic
value is known as its buffer capacity.
same acid witha that
with a salt of the obvious from the above reactions
A weak acid together is neutral.
strong base is
called acidic buffer. [H']= [OH ] i.e., solution base:
+ CH,COONa Salts of weak acid and strong
eg. CH,COOH
A weak base and its salt with a strong
acid is called basic
Examples: CH,COONa, NazPO4, KCO3, Na,CO, etc,
buffer. e g NH,OH + NH,CI. Consider the hydrolysis of CH3C0ONa,
+ NaOH
Buffer action: The ability the buffer solution to
of CH,COONa + H,O CH,COOH + Na' +OH
value on the addition of + Na* + H,0CH3COOH
resist the changes in the pH or, CH,CO0
base is called buffer action. H,0=CH,COOH +OH
small amounts of acid or i.e., CH,C00 +
since anion reacts
salt is known
.Henderson'sequation: pH =pk, +log [acid] Such salts undergo anionic hydrolysis
withwater to basic solution.
give
calculation of
as equation and enables the
Henderson's
Hydrolysis constant, K,
K
solutions made by mixing known Ka
pH values of buffer
concentrations of a weak acid and its
salt. and K, is dissociation
where, K is ionic product of water
constant of weak acid.
Acid-base titrations and indicators
added
K
Aplot of pH against the volume of beingthe solution
Degree ofhydrolysis, h o r K, xC
is known as pH curve or titration curve.
An acid-base indicator is an organic dye
that signals the and, pH = [pk, + pk, + log C]
end-point by a visual change in colour. ofstrong acid and weak base: etc.
Salts
A suitable indicator for a given titration may
be defined
as possible that lies Examples: NH,CI, CuSO4, CaCl2,.AlCl3,
as one which has a narrow pH range
BA+H,O BOH + HA
on the upright part of the titration
curve. Strong acid
entirely Salt Weak base
are suitable
Both methyl orange and phenolphthalein +A +H,0 BOH + H +A
indicators for strong acids and strong bases titrations.
or
B
and i.e., B" + H,0 BOH +H
The pH range of methyl orange is (3.1 -

4.4)
These salts undergo cationic hydrolysis since cation reacts
phenolphthalein is (8.3- 10.0).
with water to give acidic solution.
For a weak acid-strong base titration, phenolphthalein is a

suitable indicator while methyl orange is not. Hydrolysis constant, K, = A

Methyl orange and methyl red are suitable indicators for
strong acid/weak base titrations. where Kw is ionic product of water and K, is dissociation

Indicator Colour at Transition pH Colour at constant of weak base.

low pH range high
(approximate) pH
Blue
Degree of hydrolysis, h o r K, xC
Bromophenol blue Yellow 2.8-4.6
Methyl orange Yellow 3.1-4.4 Yellow and, pH = pk, - pK, - log C]
Bromocresol green Yellow 3.8-5.4 Blue
Methyl red Red 4.2-6.3 Yellow Salts of weak acid and weak base:
Bromocresol purple Yellow 5.2-6.8 Purple Examples :CH,COONH4, AIPO4, (NH,),CO3, etc.
Bromothymol blue Yellow 6.0-7.6 Blue
Phenol red Yellow 6.8-8.4 Red BA+
Salt
HO BOH+HA
Weak acid
Weak base
Thymol blue Yellow 8.0-9.6 Blue
Phenolphthalein Colourless 8.3-10.0 Pink or, B* +A +HO BOH+ HA
Alizarin yellow Yellow 10.1 12.0 Orange-red These salts involve both cationic and anionic hydrolysis
to give almost neutral solution since both acid and base
Hydrolysis of salts produced are weak.
Salt hydrolysis is a process in which a salt reacts with water K
Hydrolysis constant, Kh =-

to give acid and the corresponding base. Kx K

BA + H,0 > HA + BOH where, K,= lonic product of water
Salt Water Acid Base Ka = Dissociation constant of weak acid

Hydrolysis is the reverse of neutralisation. Kp= Dissociation constant of weak base

lonic Equilibria 149
pAgC[Ag']|CT]=Sa T:CAgCI(6)|
Degree
of drolysis. h =

VK, or h =

The above equilibrium constant is known as solubility

product, i.e. (Ksp)AgC
Ipk,
+
pk, -

PA,1 soluble salt and if A,B,(ag) 1s

and. p?H= IT
A Bts) is a sparingly
completcly dissociated in its aqueous solution, then
A By( ) x A\a) + y Bag)
solubility and Solubility products xS yS
The solubility ($) of a substance in a solvent is the (K)A, B= (x S)* x ( Sy = xy"s**y . (1)
..

concentration in solution.
the saturated
where S is solubility of A, B, in moles/litre.
Molar solubility is detined as the number of moles of If the degree of dissociation of A, B, (ag) is C, then
litre (L) of the solution.
the substance per s**y a*t (ii)
(spA,B, =x* xy' x x

Whenever the product of concentrations of ions of a
Substance present in solution exceeds the solubility
nroduct ofthat substance. the substance gets precipitated.
. The compound with the lower solubility product gets
If the salt is made from strong acid and strong base, e.g,
AgCl, Ag2SO4 etc., a =1.
If any information regarding o is not given in the question
directly or indirectly, then consider o 1.
=

precipitated in preference.
. Silver iodide has lower solubility product than silver Common ion effect
chloride. and so the former gets precipitated in The dissociation of a weak acid or a
suppression of the
preference to the later. weak base the addition
on of an electrolyte containing its
.When a saturated solution of a sparingly soluble salt,
own ion is called common ion effect.
say AgCl is
in contact with its solid phase, then the
following equilibrium is established.
CH,COOH CH,CO0 +H*
If acetate ions in the form of sodium acetate are added
the left
AgCL AgClag)Ag (ag)tag) to the solution, the equilibrium will shift towards
in its aqueous solution is dissociation of
Let the solubility of AgC forming more unionized acetic acid or the
S(M) and degree of dissociation of AgClag) is a, then acetic acid will be reduced much. The dissociation of acetic
asper following equilibrium: acid will also be reduced if H ions are added in the form
AgCl Ag(ag)+C
Sa Sa
ag) of HCl.

WB JEE WORKOUT
solubility of Mg,(PO4) is S mol L
The
The
CATEGORY 1:Single Option CorrectType (1 Mark)5.
solubility product is given by the ss
relation
solution? (a) S (b) 36 S3 (c) 6 (d) 108 S°
.Which of the following would be an acidic
concentration of When equal volumes of the following sollutions
are
(a) Solution having hydrogen ion 6.
will
10 M mixed, precipitation of AgCl ( Ks= 1:8x10)
ion concentration of occur only with
(6) Solution having hydrogen CI
10-13 M (a) 10 M Ag" and 10* M
CI
C) Solution having hydrogen ion concentration of (b) 10 M Ag" and 10- M
CI
10 M (c) 10 MAg" and 10° M
(d) 10-0 MAg and 10-0
M CI
a) Solution having hydrogen ion concentration of
dissociation of
10 M 7. Ostwald dilution law is applicable to the
(a) ammonium hydroxide (b) sulphuric acid
A solution of NaClI in contact with atmosphere hassa (c) hydrochloric acid (d) sodium chloride.
pH of about
for the solubility
(a) 3.5 (b) 5 (c) 7 (d) 14 8. Which is the correct representation
v e n that K, for acetic acid as 1.8x 10 and K^ of product constant of Ag2Cr0,?
NHOH as 1.8 x 10 at 25°C, predict the nature of (a) [Ag1ICrO;] (b) [2Ag1ICrO
(c) [Ag']ICO] (d) [2Ag[CrO?]
dqueous solution of ammonium acetate.
(a) Acidic constituents one of the
(b) Basic 9. Ostwald dilution law"
"Arrhenius theory of electrolytic
)Slightly acidic or basic (d) Neutral postulates of the
dissociation". It is valid for
Ongst the following hydroxides, the one which
as the lowest value of K., at ordinary temperature (a) strong electrolytes
(about 25°C) is (b) weak electrolytes
(a) Mg(OH (c) both strong and weak electrolytes
(b) Ca(OH)
(c) Ba(OHh d Re(OHla (d) non-electrolytes.
 mtG Chapterwise WB JEE EXPLQORER
150
10. In the reaction, AgCl + KlKCI + Agl (a) The acid is too dilute.
when KI is added, the equilibrium is shifted towards (b) It is a strong acid.
right giving more Agl precipitate, because
(a) both AgCl and Agl are sparingly soluble
of hydronium ions.
It is weak acid.
concentralion
(c) It reacts with water to produce a high concent

(b) the Kp of Agl is lower than K,s, of AgCl (d) a

21. Why only Cd" gets precipitated as CdS and sohutlion

N
(c) the Ksp of Agl is higher than K, of AgCI as NiS when H2S is passed through an acidic sol.
(d) both AgCl and Agl have same solubility product.
containing Cd" and Ni2
and 5. The
11. pk values of two acids A and B are 4 (a) Solubility product
is less than that of
of CdS
strength of these two acids are related as (b) Enough Cd° are present in acidic medium
(a) acid.A is 10 times stronger than acid B (c) Nickel salt does not ionize in acidic medium
(b) strength of acid A: strength of acid B 4:5
=

(d) Solubility product changes in presence of an aCid,

(c) the strength of two acids cannot be compared 22. For anionic hydrolysis, pH is given by
(d) acid B is 10 times stronger than acid A.
solution of
Which one of the following is the buffer
12.
strong acidic nature?
()pH pk,- pk,-5logC
(a) HCOOH + HC00 (6) plH-p,+;pk, -s logC
(b) CH,COOH + CH,COO
(c) HC;04+C20f
(d) HBO +BO (pH pk,+ pk, + log c
13. An example of salt that will not hydrolyse is
(b) KCI
(a) NH,O () pHpK,+; pk, -;pk,
(c) CH;COONH, (d) CHCOOK.
14. The pH of pure water at 50°C is (K, = 13.26 at 50°C) 23. 0.001 mole of strong electrolyte Zn(OH), is presentin
(d) 6.63 200 mLof an aqueous solution. The pH of this solution
(a) 7.0 (b) 7.13 (c) 6.0
is
15. A white salt is readily soluble in water and gives a (b) 4 (c) 12 (d) 10
colourless solution with a pH of about 9. The salt (a) 2
24. A certain buffer solution contains equal concentration
would be
ofX and HX. The K, for HX is 10. The pH ofthe
a) (NH)CO3 (b) CH,C0ONa
(d) BaCl buffer is
(c) CHCOONH, 6 (d) 14
16. To an aqueous solution of Ag,CrO4 above its own (a) 5 (b)8 (c)
ions are added in the form of 25. The solubility products of Al(OH), and Zn{OH), ae
precipitate, CrO 8.5 x 10-23 and 1.8 x 10- respectively. If NH,OH
solution. This results in
is added to a solution containing Al" and Zn" ions,
(a) increase in concentration of Ag" ions
then substance precipitated first is
(b) decrease in concentration ofAg" ions
(c) increase in the value of solubility product (a) Al(OH)3 (b) Zn(OH
(d) decrease in the value of solubility product. (c) both simultaneously d) none of these.
17. The pH of blood does not appreciably change by a 26. The following equilibrium is established whe
small addition of acid or a base because blood hydrogen chloride is dissolved in acetic acid.
(a) serum protein present in blood acts as buffer HCI+CHCOOHC+CH,COOH
(b) contains iron as a part of the molecule The set that characterises the conjugate acid-basepar
(c) can be easily coagulated (a) (HCI, CH,COOH) and (CH,COOH, CI)
(d) has a very high pH. (b) (HCI, CH,COOH) and (CH,C00H, C)
18. The plH of a solution is increased from 3 to 6; its H () (CH,C0OH, HCI) and (Cl, CH,CoOH)
on concentration will be (d) (HCI, CI) and (CH,CoOH;, CH,COOH)
(a) reduced to half (b) doubled 27. Phenolphthalein does not act as an indicator10
(c) reduced by 1000 times titration between
(d) increased by 1000 times. (a) NaOH and CH,cOOH
19. pH of 0.01 M (NH4)>SO, and 0.02 M NH,OH buffer (b) H,C,0, and KMnO, sol
(c) NH,OH and HCI
(pK, of NH4 9.26) is
=

(a) 4.74 + log 2 (b) 4.74- log 2 (d) KOH and H,SO4
(c) 4.74 + log 1 (d) 9.26+ log 28. Hydrogen ion concentration ofasolution whosepH
p
20. 1 M solution of an acid has a pH of 5. Which of the zero, would be
is the most reasonable explanation for this (a) 2.0 g ion L (b) 1.0g ion L
following
acid? (c) 10 g ion L (d) 10-g ion L
l o n i cE q u i l i b r i a

151
ahich of the following would not change the plH of | 38. The solubility product of silver chromate be Kp» S
ch
29. HCl when added to the acid ?
10 cm of dilute water solubility is
pure (b) 20 cmn' of pure waler
(a) 5 cm of
1 0 cm of cone. HcI (d) 20 em' ofsame dil. HCI
(a) k,/8
siler nitrate solution is gradually added to an aqueous (C) K,14 (d) y , 2
30.
solution containing 0.0I M each of chloride, bromide
39. What is the maximum pH of a 0.1 M Mg" solution
nd iodide ions. The comect sequence in which the
3nd

is
from which Mg(OH) will not be precipitated
halides will be preeipitated K 1.2 x 10-?
(a) B r . C l T (b) T.C, Br (a) 11.02 (b) 8.40 (c) 6.42 (d) 9.04
(c)T.Br.CT (d) Br.C 40. The pH of a 0.1 N solution of NH CI is 5.4. What
CATEGORY 2: Single Option Correct Type (2 Marks) will the hydrolysis constant? (supposing degree of
hydrolysis as very small)
1. How many grams of sodium acetate are to be added to (a) 2.42 x 10-10 (b) 1.42 x 10-10
alitre of 0.4 M CH,COOH solution so that the [H'] of
10 g ion/L?
(c) 1.58 x 10 (d) 2.82 x 10
the resultant solution is 2
x
41. A sample of mixed alkali contains NaOH and NagCO3
(Given K, tor acetic acid
=
1.8 x
10) is titrated in the following two schemes.
(a) 3.502 g (b) 2.952 g (c) 4.252 g (d) 5.162 g mL of above mixture 8 mL of 0.1 N
1) 10 requires
and 740 mm pressure
at 25°C HCI by using phenolphthalein.
100 ml of HCI gas
was dissolved in 1 Lof water. What will be the pH of (1i) 10 mL of above mixture requires 10 mL 0.1 N
solution. HCI by using methyl orange.
(Given, vapour pressure of H,O at 25°C is 23.7 mm.) What will be the ratio of the weight of NaOH and
(a) 2.012 (b) 3.241 (c) 2.414 (d) 3.021 Na,COg in the sample mixture?
3. The pH of blood stream is maintained by a proper (a) 1.132:1(b) 2.412:1(c) 2.122:1(d) 3.142 1

balance of H-CO3 and NaHCO, concentrations. What 42. What will be the basicity of an acid, if 2 moles
volume of 5 M NaHC03 solution should be mixed of it requires 400 mL of 5N KOH for complete
with a 10 mL sample ofblood which is 2 M in H,COg, neutralisation?
in order to maintain a pH of 7.4? K, for H,CO, in (a) 1 (b) 2 (c) 3 (d) 4
bloodis 7.8x 10. 43. Solubility product of Mg(OH), at ordinary temperature
(a) 50.20 mL (b) 62.42 mL is 1.96 x 10-. pH of a saturated soln. of Mg(OH);
(c) 78.37 mL (d) 52.41 mL will be
4. When 1Lof a saturated solution of PbClh is evaporated (a) 10.53 (b) 8.47 () 6.94 (d) 3.47
to dryness, the residue is found to weigh 4.5 g. What 44. A weak acid of dissociation constant 10 is being
will be the K, for PbCl,? titrated with aqueous NaOH solution. The pH at the
(a) 1.70x 10 (b) 2.70 x 106 point of one-third neutralisation of the acid will be
c) 3.20x 10 (d) 1.80x 10-6 (a) 5+log 2-log 3 (b) 5-log 2
35. Three sparingly soluble salts MX, MX and MX, have (c) 5-log3 (d) 5-log6
the same solubility product. Their solubilities will be 45. A 100 mL 0.1 M solution of ammonium acetate is
in the order diluted by adding 100 mL of water. The pH of the
(a) MX MX> MX (b) MX > MX> MX resulting solution will be (pk, of acetic acid is nearly
(c) MX> MX,> MX (d) MX> MX> MXg. equal to pkK, of NH,OH)
5. It is found that 0.01 M solution of four sodium salts (a) 4.9 (b) 5.0 (c) 7.0 (d) 10.0
Na4, NaB, NaCand NaD have the following pH values CATEGORY 3:One or More than One Option
i) NaD = 10.0 (i) NaC=9.0
Correct Type (2 Marks)
(ii)Naß 8.0 (iv) NaA = 7.0

Which of the corresponding acids is strongest' 46. The concentration of sulphide ion in 0.1 M HCI
(a) NaA (b) Naß (c) NaC (d) NaD solution saturated with hydrogen sulphide is
h e concentration of [H] and concentration of [OHJ 1.0x 10 M. If 10 mL of this solution is added to
a 0.1 aqueous solution of 2% ionised weak acid is 5 mL of 0.04 M solution of FeSO4, MnCl, ZnCl2
onic product of water =] 107"]] and CdCl2, in which solutions precipitation will take
(a) 2 x 10S M place?
and 5 x
10 M
(Given K, for FeS = 6.3 x 105, MnS = 2.5 x 10-3,
(6) 1 10 M and 3 10 M
c) 0.02 10 M and 5 ZnS 1.6 x 10 and CdS = 8.0x 10.)
10 M
(d) 3 10
Mand 4 10 M (a) FeSO (b) MnCl, (c) ZnCh (d) CdCl
 mtG Chapterwise WB JEE EXPLORER
152
(c) Addition of 50 mlL of 0.002 M HCI
47. pH of which solution is not affected by dilution
(d) Addition of Mg
(a) 0.01 M CH,COONH
52. Which of the following statement(s) is (are) correc
(b) 0.01 M NaH,PO4
(c) 0.01 M NaCl The
(a) of 1.0 x 10 M solution of HCI is 8.
pH
(d) 0.01 MNaHCO3 The conjugate base of H,PO4 is HPO
(b)
48. Following is the titration 14 constant of water increases with
12
(c) Autoprotolysis
curve of CH,COOH Equivalence temperature.
10 K point
against NaOH added
***********

When solution of a monoprotic acid is

weak
pH6
(d) a
with phenolphthalein as titrated against a strong base, at half-neutralisation
the indicator. K{n value point pH = (1/2) pka.
of phenolphthalein is 53. Which of the following expressions is applicable to
4.0 x 10-10 0 10 20 30 40 50
Volume of NaOH added/mL the hydrolysis equilibrium?
Choose the incorrect statement.
It begins to change colour from the pH 9.4.
CN+H0 HCN+OH
(a)
(6) It begins to change colour from acid (colourless) 6) h- K
at pH 8.4 to the base form (reddish pink) at pH (a) KhK
10.4. ()pH=Pka[HCN] (d) [H"]= C
is suitable indicator for
(c) Phenolphthalein
CH,COOH-NaOH titration. 54. In 0.020 M carbonic acid solution,
(d) Phenolphthalein is a weak acid. (a) HCO is stronger acid than HCOg
49. Which of the following aqueous solutions will have a
(b) HCO,2H+CO5 =Ka,a
pH less than 7.0? (c)[HCO1=[Co3]
(a) NH,NO (b) NaOH (d) it can be said, Ka, >> Ky
(c) FeCl3 (d) NayPO
55. The acid dissociation constant for Al(H,0)*is
50. Buffer solution can be obtained by mixing aqueous
1.4 x 10. It suggests
solution of
(a) HO molecules in the hydrated cation are much
(a) CH COONa and excess HC1
stronger proton donors than free solvent water
(b) CH C0ONa and CH,COOH
(c) NaOH and NaCl molecules
(d) CHC0OH and excess NaOH. 6) ionisation; AlH,O) ay)Ala) +6H,0
51. Which ofthe following will decrease the pH ofa 50 mL
solution of 0.01 M HCI1?
(c)ionisation; Al(H,O) (er) + H,O H,0(
(a) Addition of 5 mL of 1 M HCI +[AIH,O),(OH)
(d) its pH might be more than 7.
(b) Addition of 50 mL of 0.01 M HCI

HINTS&
HINTS&SOLUTIONS
1. (c):When H > 10 M, the solution is cidic 9. b)
(pH< 7), therefore the solution having concentration of 10. (b):On adding KI, Agl precipitated. This means that
10 MpH=2) is acidic. Agl is less soluble than AgCl or K, of Agl is less than K
2. (c):NaCl is a salt of strong acid and strong base
therefore its solution will be neutral, ie, pH = 7.
ofAgCl.
AgCl +KI=KCI+ Agl
3. (d): As K, =Kp, the solution is neutral. 11. (a) :K, of A = 104

4. (d): Be(OH), has lowest solubility and hence lowest K, of B = 103

solubility product i.e., A is 10 times stronger than B.

5. (d): Mg,(PO)» 3Mg +2PO
2S
12. (a): HCOOH is the strongest among all the
acids.
give
S 3S
K=(35) (25 = 108 S
13. (b): KCl is a salt ofstrong acid and strong base, so 1
6. (a):After mixing, [Ag][Cr]> K,, only for (a). does not undergo hydrolysis.
7. (a): This law is applicable to the dissociation ofweak 14.
electrolyte and ammonium hydroxide is a weak electrolyte. (d): pH=pk, (for pure water)
8. (a):AgCr0,2Ag+CrO
pH-x13.26=6.63
Kp [Ag1 {C.O;1
l o n i cE q u i h i b r i a

153
b):
HCOONa is readily soluble in water and gives
15.
sicsolution
since it is: salt of weak acid and a strong base. 31. (b): pH =pk, + log Salt
2Ag +CrO [Base]
16. b): Ag:CTO4
of CrO ions will shit the equilibrium in -log (2 x
10 *) -log (1.8 10 )+ log[Salt)
= x

0.4
A0ard direction, theretore the conc. of Ag' decreases.
backward 3.699 = 4.74 + logat
17.
a): The buffer system present in blood is 0.4
HCO + NaHCO,.
18. (C):p. 3,. = 10:pH=6, [H']= 10
log Salt-1041 orara=0.091
0.4 04
is reduced by 10" times or, [Salt)= 3.6 x 102
Hence [H Amount of sodium acetate to be added = 3.6 x 104 x 82
19. (d): Is is an example of basic buffer for that 2.952 g (molar mass of CH,COONa =82)
p H = p +log5ase]
32. (c): Given, vapour pressure of water = 23.7 mm
(Salt 740-23.7atm
0.02
9.26+ 10g2x0.01 9.26+logl PHClay 760
= 0.9425 atm

100
20, (d): Strength of an acid increases as pH decreases = 0.1 L;T=25+273 =298 K
1000
from 6 to 1. Therefore,
a strongest acid have pH =
1 and
weakest acid have pB = 6. Therefore, an acid having PV_0.9425 x 0.1
Mole of HCI, i.e., "uc1
RT 0.0821x 298
weak acid.
pH 5 is a
n=3.85 x 10-3
21. (): The solubility product of CáS is less than that of Now, molarity of HC = no. of moles dissolved in 1 L of
the solubility product of nickel sulphide therefore CdS gets
solution
precipitated.
3.85 x 103
22. (C) (Vin litre)
23. (c): Zn(OH),=Zn*+20H [H]=3.85 x10 M
OH=0.001x2x00 pH - log [Hj=- log (3.85 x 10)
200
pH=2.414
[OH]= 1 x 10 mol L-
33. (c): Let us suppose the volume of NaHCO, mixed be
pOH=-log[OHJ=-log(1 x 10 )=+2 log 10
mL
pOH 2:pH +pOH 14
No. of moles ofNaHCO, in VmL of 5 M NaHCO3
pH+2-14= pH=12 5xV =
4. (b): For acidic buffer 0.005 V
1000
Salt
pH pk +log [Acid] No. of moles of H,CO, in 10 mL of 2M H,CO3

Salt [Acid 2x10 0.02

1000
pPH=pK,=- log K-log10=8 Now, from Henderson's equation,
25. (a): Since k, ofAl(OH)g is less than Kp of Zn(OH)
thus solubility Al(OH), of [Salt
is less than Zn(OH)2. Hence,
pH pK*iOgTAcid)
AIOH), will precipitate first.
26. (b): HC1=H+C 0.005 V
7.4=-log(7.8 x 10-7) +log
CH,COOH+H=CH,CoOH 0.005 V
0.02
1. (): Phenolphthalein is a weak acid it is not a suitable 7.4 6.1079+ log-
adicator for titrating a weak base like NH,OH against a 0.02
Srong acid like HCI because hydroxyl ion furnished by the
ak base at the end point of the titration are too less to
1.2921 = 0.005
log-
0.02
or 0.005 19.5929
0.02
Sit the equilibrium sufficiently towards the right to raise
pH to 8.3 and hence pink color does not appear at the
V 78.37 mL
end point. 34. (a): Let us suppose the solubility of PbCly be S mol/L
8.
(b): pH=-log PbClh Pb"+2C
29. d: [H] log I =0 or pH= -

Kp [Pb*|[CI]* =S* (25- 4s*

There is no change in pH on mixing two dil. HCI
OnS
30. (c)
of equal
concentration in any proportion.
Solubility = 4.5g/lit==1.62 x 10 mollit
278
for
AgCl, AgBr and Agl are 1.8x100, (Molar mass of PbCl, =278)
010-13 and 8.3 10-17 respectively. Lower the
x Ksp4 x (1.62 x 1023
hubility produ more easily it gets precipitated. or Asp1.70 x 10
 mte Chapterwise VWB JEE
EXPLOREO
154
(a):
42. Let the basicity of an acid is n.

35. (d): M,X 2M* + X, HA

2 S For complete neutralisation,

Kp=4sj or s =(K«,/4) eq. of acid eq. of base

=

=NX V(by definition

of eq. n no. of mole5
= *
MX M +X*. Ky» =s no.

2 xn=400x 10 n =1 x

or S2 (Kg,)2
MA M*+3X 43. (a): Mg(OH)2(s) Mg" +20H

Kyp=27s or s=(Ksp/27) [Mg1 [OH= 196x 10

Evidently, s> s1 > S3: Kp =

[Mg(OH),]
36. (a) : pH 10 (NaD) shows that the solution strongly
=
is
weak acid. xx (2x) = 1.96 x 10 (concentration of solidis unitv
basic i.e. NaD is a salt of strong base and
4x = 1.96 x 10
basic solution.
Similarly, pH 9 and pH 8 refer to
= =

solution is neutral i.e., 1/3

But pH =
7 (Na4) shows that the |1.96x 10-1\
base. =
Naf is a salt of strong acid and strong 4
10M
(a): [H']= Ca =0.1 0.02 =2
x x
37.
104
(As degree of dissociation 2%
= =
0.02) x=(4.9 10-2)3= 1.7x
x

1.7 10*
concentration =
2 x x
1014 So, OH
x 10-12 M 104
Hence. [OH]= -3*5
2x103 i.e., [OH=3.4 x

Now, pOH =-log [OH]

38. (c): Ag.CrO4 dissociates as
=- log [3.4 x 10]=4-0.531 =3.469
AgCrO 2Ag"+CrO pH 14-3.469= 10.531
K[AgH [CrOg] 44. (b): It forms a basic buffer.
Suppose solubility of Ag,CrO4 is S mol/litre then
the
sp(25) (S) =4S* [Salt]
So, pH pka +
los TAcid
S-K, /4
39. (d): When Ks, =Kip. precipitation does not occur. one-third neutralisation means
Mg*1[OH] = 1.2 x 10-1 [Acid]
[OH= 1.2x10-
0.1
= 1.09 x 10-3 pH=5+los| orplH-5-log 2
45. (c): Hydrolysis ofa salt of weak acid and weak base:
pOH=5-log 1.09 =4.96. 9.04 pH =
14 -4.96
40. (c):NH,CI is a salt of strong acid and weak base. pH =7+PK, -pk,)=7
[H]=Ch
pH log [HI=-log Ch=5.4 as pka pk;
Ch=3.98 x 1 0 46. (c, d): When Kip> Ksp precipitation takes place,as
3.98 x 10 10 mL of solution containing Sion is mixed with 5 mLof
h= =3.98 x 10
0.1 metal salt solution, after mixing

Now K -R =
h h<<1, 1-*-1] Isj=1.0x 10-1 x = 6.67 x 10-20
1-h 15
K , = =(3.98x 1052 = 15.8 x 10-10 =1.58 x 10 Fe*] [Mn*]= {Zn*]= [Cd*]
41. (a): Meq. of HCI for 10 mL of mixture using X0.04 = 1.33 x 10-M
phenolphthalein indicator = 8 x 0.1l = 0.8

Meq. of NaOH +Meq. of Na,CO - 0.8

lonic product for each of these will be =
[M"] [S°T|
2
(i) (1.33 x 10 (6.67 x 1020) = 8.87 x 104
As this value is greater than the solubility product of Zns an
Now Meq. of HCl used for 10 mL mixture using methyl1
orange as indicator = 10 x 0.1 = 1. Cds, therefore, ZnCl, and CdCl solutions wil be precipitale
Meq. of NaOH + Meq. of Na,CO = 1 whereas FeS and MnS is lesser than solubility prouu
.(ii)
By eqn. (i) and (ii), therefore precipitation does not take place in this case
Meq. of NaOH = 0.6 Meq. of Na,CO, = 0.4
47. b, d): In aqueous solution, a salt
(a,
weak base acts as a buffer solution. The
of weak acidanu
x1000 =0.6 x 1000 = 0.4 pH ofa buffer solu
40 106/2 do not change on dilution. Thus,
pH 0.01 M
of CH,COON
wt. of NaOH =0.024 wt. of Na,CO, = 0.0212 will not change on dilution. and NaHCO Hr
from
Ratio ofthe weight of Na@OHand Na,C0,= =1. 132: 1 Nati,PO, are amphiprotic anions. The pH of solun
0.0212 containing amphiprotic anions do not change on dilution.
lonic Equilibria
155
(a): pkn-log Ain log 4 9.4
10-
The value of ionic product of watcr (K,,) increases with
is the cquivalene point. pH colour ehange starts
Thus,it nerease in temperature. For half-ncutralisation of a weak
fhom
(pAn-1); and complete at (pt 1).
:NH,NO; and FeCl, are salts of strong acid and acid log salt
by a weak basc. phl =pk, + log
hase. which on hydrolysis produce acidic solution acid
i . pH< 7.0 Since salt) [acid],
=

pH =pka
53. (a, b, d)
b)

51. a): Additiom of 5 mL of I M HCI will decrease the S4. (a, b, d) : As H,CO undergoes dissociation in water
because only this will increase the H ion concentration it means K >>
pH.
in the solution.
K
HCO, is a very poor acid.
(b, c): pH of 1 x 10 M HCl will be less than
S5. (a, c): lonisation in (b) will not make it acid of
pH hes in the range 0-7.
hocause acidic pk= 14 x 10 as ionisation of water is involved with salt
H,PO+H0 HPO; +H,0* and K,> K
H,O+H,0 H,0 +OH pH ofsolution will always be less than7.

8
2013-2020
WB JEE Previous Years Questions
Dissolving NaCN in de-ionized water will result in a
CATEGORY 1:Single OptionCorrect Type (1 Mark)7 solution having
1. At 25°C, the solubility product of a salt of MX, type is (a) pH<7 (b) pH 7
3.2 x 10 in water. The solubility (in mol/L) of MX () pOH =7 (d) pH>7 (2017)
in water at the same temperature will be 3. Which of the following mixtures will have the lowest
(a) 1.2 x 103 (b) 2 x 103 pH at 298 K?
(c) 3.2 x 103 (d) 1.75 x 103
(2013) (a) 10 mL 0.05 N CHCOOH +5 mL 0.1 N NH,OH
(b) 5 mL 0.2 N NHCI+5 mL 0.2 N NH,OH
2 The different colours of litmus in acidic, neutral and
(c) 5 mL 0.1 N CH,COOH+
basic solutions are respectively 10 mL 0.05 N CH,COONa
(a) red, orange and blue (d) 5 mL 0.1 N CH,COOH + 5mL 0.1N NaOH
(b) blue. violet and red (2019)
(c) red, colourless and blue
d) red, violet and blue. (2013)CATEGORY2:Single Option Correct Type (2 Marks)
3. At 25°C. pH ofa 10* M aqueous KOH solution will be 9. 1x 10 mole of HCl is added to a buffer solution
(a) 6.0 (b) 7.02 (c) 8.02 (d) 9.02 made up of 0.01 M acetic acid and 0.01 M sodium
(2013) acetate. The final pH of the buffer will be (given, pk,
4. The pH of 10 M KOH solution will be of acetic acid is 4.75 at 25°C)
(a) 4 (b) 11 (c) 10.5 (d) 10 (a) 4.60 (6) 4.66 (c) 4.75 (d) 4.8
(2014) (2013)
SThe ratio of volumes of CH,COOH (N)to 0.1 10. A solution is saturated with SrCO3 and SrF2. The
CH,COONa 0.1 (N) required to prepare a buffer solution [CO]is found to be 1.2 x 10 M. The concentration
of pH 5.74 is (given: pk, of CH,COOH is 4.74) of F in the solution would be
(a) 10:1 (b) 5:1 (a) 3.7 x 10° M (b) 3.2 x 10 M
(c) 1:5 (d) 1: 10 (2015) (c) 5.1 x 10- M (d) 3.7 x 10M
The molar solubility (in mol L) ofa sparingly soluble Given: K(SrCO,) =
7.0 x
10, K(SrF2)
salt MX is 'S. The corresponding solubility product 7.9 x 10-10
1S (2020)
spS in terms of 'K, is given by the reaction
4 1/5 CATEGORY 3:One or More than One Option
(b) S- 256 Correct Type (2 Marks)
(c) S= (256 K, (d) S= (128 K,4 11. In which of the following mixed aqueous solutions
pH= pk at equilibrium?
(2016)
 mtG Chapterwise WB JEE
EXPI
156
(1) 100 mL of 0.1 M CH,COOH + 100 mLof
(4) 100 mL of 0.1 M CH,COOH + 100 ml.
L of
RLORE
0.1 M CH,COONa 0.A M
(a) (1) is corre (b) (2) 1s correct.
(2) 100 mlL of 0.1 M CH,COOH+50 mL of
0.1 M NaOH (c) (3) is correct.
(d) Both (1) and (2)
are correct.
(3) 100 mL of 0.1 M CH COOH +100 mL of (2016
0.1 M NaOOH

HINTS & SOLUTIONS

This solution will have lowest pH.

b): MN M' + 2X +H
1. 9. (b): CH,CO0
0.001
CH,C0OH
S 2S 0.01 0.01
0.01 0.001 0.01 +0.001
K=Sx (2s) =4s =0.009 = 0.011

4S =3.2 x 103
Salt) 4.75+ 0.009
log01 .0
-

S 3 2 x 1 0 %
pH pK +log[Acid
4 10. (d):SrCO3 Sr" +CO,
S= 2 x 10
StS2 S
(d)
KopSrCO [S*] [co,1
2

3. b): [OHJhotal =(10+107")M 7x 101=(S, +S,) (S)

pOH-log[10+10']=6.98 SrF2 S*+2F
. pH = 14-6.98 = 7.02
S +S2 2s
4 (d): KOH>K+OH
Ksp(SrF2)= [S"][F17
10M 10 M 7.9x 10-0=(S1 +S2)(25,)
[OH= 10M Dividing eqn. (1i) by eqn. (1), we get
pOH-Hogj0 [OH]=-Hogio(10-) =4 7.9x10-10
pH=14-4 10
7x10-x4 S
Activity ofsalt
5. (d):pH pka* l0g10 Activity of acid
=

1.2 x101.84x104
4
Concentrationx Volume(alt)
5.74 4.74 * 102 =3.68 x 10M
10810 oncentration x Volumetacid) F]= 2S =
2 x 1.84 x

[Concentrations given are same] 11. (a, b, d): Let us analyse each case:
of
1 log10sat Vyalt: acid10:1| (1) 100 mL of 0.1 M CH,COOH+ 1000.1mLMCH CooN=
Vacid [CH,COOH]=(100 x 0.1)
Vacid Vat =1:10 [CHCOONa] = (100 x 0.1)

6. (b):MX, M*"+4X The mixture is an acidic buffer.

S S 4S Using Henderson equation, we get
=256 $5
K MLX 1=S(4S)' [CH,COONa]
pH pK,+log
CH CoOH]
s- (100 x 0.1) pH= pk,+log!
7. (d): Hydrolysis of NaCN, pH p *10 (100x 0.1)
NaCN + H,0 NaOH + HCN (: logl=
Strong base Weak acid pH pK MN
100 mL of 0.1 M CH,COOH + 50 mL of0.I
Hence, the resulting solution will be basic; pH> 7. (2)
CH,COOH + NaOH CH,COONa + H,0
8. (c): CHCOOH +CH,COONa (50 x 0.1)
0
0.1 N, 5 mL 0.05 N, 10 mL (100x 0.1))
millimole millimole
0.5 0.5
millieq. 10 millimole = 5 millimole

pK,
[CH, COO] Remaining.
It is acidic buffer, pH
*(CH,COOH]
=

millimole 5 millimo
5 millimole 0 millimole S

pH= pk So, an acidic buffer is formed.

lonic Equilibria 157
salt] strong base will undergo hydrolysis (anionic hydrolysis)
pH p [acid and the pH will be determined as below.
5
pH =pK, +log pH =
pK pH=7+p, +5loge
So, pH # pK,
100 mL of 0.1 MNH3
log= log1 =0 (4) 100 mL of 0.1 M CH,COOH +
[CH,COOH] (100 x 0.1) 10
= =

of 0.1 M CH,COOH + 100 mL of 0.1 M [NH,] or [NH,OH] (100 0.1) 10x =

A100 mL
=

NaOH CHCOOH + NH,OH CHCoONH4 + H2O

CHCOOH+NaOH CH,COONa + H,O millimole
10
millimole
0

(100 x 0.1) (100 x 0.1) 0 0

0 10 10
millimole 0
millimole
= 10 millimole = 10 millimole
millimole millimole

0 10 10
pH=7+ (pK, - pK,)
millimole millimole

CH3COONa, which is a salt from weak acid and

Now. So, pH pK