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IONIC EQUILIBRIUM JEE ADVANCED-VOL - III

IONIC EQUILIBRIUM
SYNOPSIS CH4 (10-58) < NH3 (10-35) < H2O (10-14)< HF (10-4)
Basicity constant is decreasing therefore, the
* Relative Strength of Inorganic Acids acidic character is increasing
* Hydracids of the elements of the same (CH 4 NH 3 H 2O HF) .
period: As we know, if the charge is spread * Hydracids of the elements of the same
over larger volume then, charge density is small group:
and basic character of the ion is also small In each Group : from top to bottom
because of the ability of ion to attract a proton Atomic size of the central atom is increasing.
becomes less and hence acidic strength of Volume available for the negative charge is
conjugate acid increases. increasing
Now, consider the hydracids of 2nd Charge density is decreasing
period CH4, NH3, H2O, HF. We find that, from Basicity of the ions is decreasing
left to right Acidity of conjugate acids is increasing
Size of central atom over which the negative Acidity constant is increasing
charge is present is decreasing Basicity constant is decreasing
The volume of central atom overlapped by Therefore; order of acidic character can be also
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hydrogen is 3/4th, 2/3rd, and 1 explained as following along with the above
respectively. reasons
a) VII A group (Halogens) - HF < HCl < HBr <
H HI
(Due to decreasing bond energy of H - X bond).
b) VI A group - H2O < H2S < H2Se < H2Te
C N O F (Due to decreasing trend in electron donor ability
H H H H H
of OH-, HS-, HSe-, HTe- ions).
c) V A group - NH3 < PH3 < AsH3 < BiH3
CH3 NH2 OH F (Due to decreasing order of electron density).
Increasing volume available to electron d) IV A group - CH4 < SiH4 < GeH4 < SnH4 <
Increasing electron delocalisation
Decreasing electron density PbH4
Decreasing bascity
(Due to decreasing order of electronegativity.)
e) III A group - BH3 < AlH3 < GaH3 < InH3 <
Volume available for negative charge is TlH3
increasing in the conjugate bases (Due to decreasing order of electronegativity.)
(CH 3 NH 3 OH F ) , therefore, charge * Among hydrides of elements with same
density of the conjugate bases is decreasing electronegativity, acidic strength increases with
Basicity of the conjugate bases is decreasing size of the central atom e.g. CH 4 H 2S HI .
and acidity of the acids is increasing * The ability of Borontrihalides to act as Lewis acid
Stability of conjugate bases is increasing increases in the order of BF3 < BCl3 < BBr3 <
(CH 3 NH 3 OH F ) BI3 due to decreasing order of strength of
Acid dissociation constant is increasing bond.

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JEE ADVANCED-VOL - III IONIC EQUILIBRIUM
c) HPO3 < HNO3
X X d) H3AsO4 < H3PO4.
Among above; acidity increases from left to right
B X B X Due to:
Decreasing size of the central atom
X X
Increasing order of the electro negativity
Increasing order of pull of electron of O-X
* Acids that require only one electron pair to bond towards X.
complete an outer shell are stronger than those Resulting into increasing positive character on
requiring two. Thus GaCl3 > ZnCl2. oxygen.
* Oxyacids Ultimately, increasing order of release of H+.
* Oxyacids with same central atom at different * The strength of oxyacids increases from left to
oxidation state: Among oxyacids of the same right across a period e.g. -
central atom having general formula. (HO)m ZOn H2SiO4 < H3PO4 < H2SO4 < HClO4,
Where Z = central atom Which is attributable to increase in
m = no of oxygen atoms attached to z and electronegativity of the central atom,
attached to H. * Hydrated metal ions: Under favourable
n = No of oxygen atoms attached to z but not conditions, one or more protons may dissociate
attached to H. to form the coordinated aqua groups.
Acidic strength increases with increasing
[M(H 2 O)6 ]n H 2 O
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oxidation no e.g.-
( Hydrated metal ion )
1 3 5 7
a) HO Cl HO Cl O HO Cl O 2 HO Cl O 3
very weak weak M(H 2O)5 OH
n 1
H 3O
strong very strong

For hydrated metal ion or aqua acids, acidity


They give OCl, OClO, OClO2 , OClO3 anions increases with the increase of positive charge of
after removal of a proton. The species which have the central metal ion and with decreasing ionic
more than one oxygen atom show resonance. radius.
We see that from left to right, acidic strength [Fe(H2O)6]3+ > [Fe(H2O)6]2+.
increases Exceptions are some times seen due to the effect
Due to : of covalent bonding.
More the no. of oxygen atoms, more the [Fe(OH 2 )6 ]2 [Fe(OH 2 )6 ]3
resonance.
Volume available for the negative charge is [Al(OH 2 )6 ]3 [Hg(OH 2 )6 ]2
increasing * Oxyacids of Phosphorous
Charge density is decreasing
H 3 PO2 H 3 PO3 H 3 PO4
Basicity of the anion is decreasing
Acidity of the conjugate acid is increasing.
4 6
Relative Strength of Inorganic Bases
b) H 2 SO3 H 2 SO 4
* In Period: The basicity of the compound
3 5
c) H NO 2 H NO3 decreases from left to right along a period e.g.:
* Oxyacids with different central atom of same NH3 H 2O HF
oxidation state and same configuration. Due to:
a) HOI < HOBr < HOCl a) Increase in the electronegativity of the atom
b) HIO4 < HBrO4 < HClO4 holding the electron pair(s)
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IONIC EQUILIBRIUM JEE ADVANCED-VOL - III
b) Decrease in the availability of electron pair(s) H O+
HA + H2O(l) 3
+ A-
for sharing with the proton.
* In group: The basicity of a compound decreases C1(1 - 1) C 1 1 + C2 2 C1 1
from top to bottom in a group e.g. : H O+
HB + H2O(l) + B-
3
a) F > Cl > Br > I
b) O2 > S2 C2(1 - 2) (C1 1 + C2 2) C2 2
c) NH3 > PH3 > AsH3 > SbH3 > BiH3.
Due to: [H 3O ][A ] [C11 C2 2 ][C11 ]
a) Increase in the size of atom holding the K a[HA]
[HA] C1 (1 1 )
unshared electron pair(s).
b) Decrease in the availability of electrons.
* Presence of negative charge on the atom holding [H 3O ][B ] [C11 C2 2 ][C2 2 ]
the electron pair(s) increases the basicity while K a[ HB]
[HB] [C2 (1 2 )]
presence of positive charge decreases basicity
e.g. H O H OH H3 O
pH log[H ] log[C11 C 2 2 ] = -
* Alkali and Alkaline Hydroxides: Basic nature
increases on going down the group e.g. log K a C1 K a C2
1 2

a) LiOH < NaOH < KOH < RbOH < CsOH


where K a = Ka(HA) and K a = Ka(HA)
b) Be(OH)2 < Mg(OH)2 < Ca(OH)2 < Sr(OH)2 1 2
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< Ba(OH)2. (C) pH of a dibasic Acids and Polyprotic Acid


pH OF THE MIXTURES : Let's take the e.g. of a dibasic acid H 2A.
(A) pH for the mixture of Weak Acid and Strong Assuming both dissociation is weak. Let the initial
Acid conc. of H2A is C and 1 and 2 be degree of
Let strong acid be HB whose conc. is C1 dissociation for first and second dissociation.
HB +
H + B
- HA-
H2A + H+
0 C1 C 1 C(1 - 1) C 1 (1 - 2) C 1 + C 1 2
and weak acid whose concentration is C2 and

HA- H+ + A2
degree of dissociation of
HA = H+ + A C 1 (1 - 2) C 1 + C 1 2 C 1 2.
C2(1- ) C2 C2
[HA ][H ]
Total (H+) conc. = C1 + C2 Ka1
pH = - log [C1 + C2 ] [H 2 A]

[C1 (1 2 )][C1 C1 2 ]
(B) pH calculation of solution of a mixture of two Ka1
C(1 1 )
weak Monobasic Acids in water
Let two weak acids be HA and HB and their [H ][A ] [C1 C1 2 ][C1 2 ]
conc. are C1 and C2, 1 is the degree of Ka 2
[HA ] [C1 (1 2 )]
dissociation of HA in presence of HB (due to
After solving for 1 and 2. We can calculate
common ion effect) and 2 be degree of the H+ conc.
dissociation of HB in presence of HA. [H+] = C 1 + C 1 2
In aqueous solution of HA and HB following pH = - log [C 1 + C 1 2]
equilibrium exists.
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JEE ADVANCED-VOL - III IONIC EQUILIBRIUM
(D) pH of mixture of acids water, they dissociated almost completely into
Let one litre of an acidic solution of pH = 2 be cation or anions. If anion interacts with water it
mixed with two litre of other acidic solution of is called as anionic hydrolysis.
pH = 3. The resultant pH of the mixture can be A + H2O HA + OH
-

evaluated in the following way. Akaline solution (pH increases).


Sample 1 If cation intereacts with water it is called as
Sample 2 cationic hydrolysis.
pH = 2 B+ + 2H2O +
B(OH) + H3O A c i d i c
pH = 3
solution (pH lowers down).
[H+] = 10-2 M
"The phenomenon of the interaction of anions and
[H+] = 10-3 M
cations of the salt with H+ and OH- ions furnished
V = 1 litre
by water yielding acidic or alkaline solution is
V = 2 litre
known as salt hydrolysis.
M1V1 + M2V2 = MR(V1 + V2)
For the study of hydrolysis, salts are divided into
10-2 1 + 10-3 2 = MR(1 + 2)
four groups.
12 103 * 1) Hydrolysis of salt of strong Acid and weak
MR
3 base: NH4Cl is a salt of weak base (NH4OH)
and strong acid (HCl). After hydrolysis resultant
4 103 M R (Here, MR = Resultant molarity) solution will be acidic due to presence of strong
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pH R log[4 10 3 ] 2.3980 acid HCl.


NH 4 OH HCl
NH 4 Cl H 2 O
pKa and pKb for a conjugate acid-base pair
For an acid HX NH 4OH H Cl
NH 4 Cl H 2 O
H X
HX NH 4 OH H
NH 4 H 2O
(acidic)

[H ][X ]
Ka ............... (A) [NH 4OH][H ]
[HX] Kh
[NH 4 ]
For conjugate base X of acid HX
* Relation between K h , K b and K w :
HX OH
X H 2O
NH 4 OH
NH 4OH

[HX][OH ]
Kb ..................... (B)
[X ] [NH 4 ][OH ]
Kb (A)
By eqs. (A) and (B), [NH 4OH]
K a K b [H ][OH ] K w H OH
H 2O
or pK a pK b pK w 14
K w [H ][OH ] (B)
Note : 1. Stronger is acid, weaker is its conjugate base.
Dividing (B) by (A)
2. Higher is the value of pK a of an acid, lower
Kw [H ][OH ]
is acid strength and higher is basic [NH 4OH]
strength of its conjugate base. K b [NH 4 ][OH ]
* Hydrolysis of Salts Kw
Salts are strong electrolytes when dissolved in Kh
Kb
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IONIC EQUILIBRIUM JEE ADVANCED-VOL - III
* Degree of hydrolysis
H2O
H OH

NH 4 OH
NH 4 H 2 O
C(1 h) Ch Ch K w [H ][OH ] (B)
Dividing equation (B) (A)
Ch . Ch
Kh Ch 2 (1 - h 1)
C(1 h) Kw [H ][OH ][CH3COOH] [OH ][CH3COOH]
Kh
Ka [CH3COO ][H ] [CH3COO ]
Kh
h * Degree of Hydrolysis
C
CH 3COOH OH
CH 3COO H 2 O()
Kw t=0 C 0 0
h
K bC t=t C(1 - h) Ch Ch
Ch . Ch
Kw Kh Ch 2
[H ] Ch C C(1 h)
KbC
if h is smaller than 0.1 then, (1 - h) = 1.
Kw C Kh
[H ] h
Kb C
Taking -log10 both side
Kw
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1 h
pH [pK w pK b log C] KaC
2
[ [OH ] Ch
1 1
pH 7 pK b log C
2 2 Kw Kw C
[OH ] C
* 2) Hydrolysis of salt of weak acid and strong Ka C Ka
base: CH 3COONa is a salt of weak acid
(CH3COOH) and strong base (NaOH). After Kw Ka Ka K w
hydrolysis resultant solution will be basic due to [H3O ] Kw
[OH ] Kw C C
presence of strong base (NaOH).
Taking -log both sides
CH 3COOH NaOH
CH 3COONa H 2 O()
1 1 1
log[H ] log K w log K a log C
CHCOO
3


Na H2O()

CHCOOH
3 Na OH 2 2 2
1
[pK w pK a log C]
2
[CH 3COOH][OH ]
Kh 1 1
[CH 3COO ] pH = 7 pK a log C
2 2
Relation between, K h , Kw and Ka pH will be more than 7, hence resultant solution
will be basic in nature.
CH 3COO H
CH 3COOH 3) Hydrolysis of salt of Weak Acid and Weak
Base: Let's take the salt CH3COONH4 made
[CH 3COO ][H ]
Ka (A) of salt of weak acid (CH3COOH) and Weak
[CH 3COOH] base (NH4OH).

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JEE ADVANCED-VOL - III IONIC EQUILIBRIUM

CH 3COOH NH 4 OH
CH 3COONH 4 H 2 O neglect the acetate ion coming from CH 3COOH

CH 3COOH NH 4 OH
Therefore CH3COOH
CH3COO H

CH 3COO NH 4 H 2O
C C(1 )
[CH 3COOH][NH 4OH]
Kh
[CH 3COO ][NH 4 ] C(1 )[H ]
Ka
C
Relation B/w, K h , K w , K a & K b
[H ]
CH 3COO H
CH 3COOH Ka (1- 1)

[CH 3COO ][H ] Kw K w Ka
Ka [H ] K a K a
[CH 3COOH] Ka Kb Kb
(A)
This expression is independent of conc.of the salt.
NH 4 OH
NH 4 OH i) if Ka = Kb, pH = 7 solution will be neutral
ii) if Ka > Kb, pH < 7, acidic solution
[NH 4 ][OH ] iii) if Ka < Kb then pH > 7, alkaline solution
Kb
[NH 4OH] In the hydrolysis of salt of weak acid and a weak
(B) base such as NH4CN, CH3COONH4. Both the
H OH ions are hydrolysed, if we assume K a K b ,
H 2 O
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then the hydrolysis of the cation and anion of the


K w [H ][OH ] salt occur approximately to equal extent for a
(C) salt which has K a K b , it would be expected
Kw [H ][OH ] [CH 3COOH][NH 4 OH] at the first glance that CN ions hydrolysed to

Ka K b [CH 3COO ][H ][NH 4 ][OH ] a much greater extent than NH 4 ions. However,,
Kw the hydrolysis of CN- ions produced OH- ions
Kh according to the equation.
Ka Kb
* Degree of Hydrolysis HCN OH
CN H 2 O
CH3COOH NH4OH
CH3COO NH4 H2O which can react with NH 4 ions as
t=0 C C 0 0
NH 4OH
OH NH 4
t = t C(1 - h) C(1 - h) Ch Ch
This latter reaction causes equilibrium in the form
reaction to be displaced to the right. Because
Ch . Ch h2 OH- ions are removed from the solution. Also
Kh
C(1 h)C(1 h) (1 h)2 the production of OH- by the former reaction
if h 0.1, 1 h 1 displaces the latter reaction to the right. Therefore
the hydrolysis of one ion drags the hydrolysis of
h Kw the other ion along so that both the hydrolysis

1 h Ka K h are fairly extensive not too far in extent from each
other so it is fairly safe to assume that [HCN] =
The acetic acid formed would partially
[NH4OH], even in the case of the salt where
decompose to give CH 3COO and H . But
Ka K b .
because of common ion effect (that is, due to the
* Buffer capacity or Buffer Index
unhydrolysed CH 3COO ) it is possible to
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IONIC EQUILIBRIUM JEE ADVANCED-VOL - III

Buffer capacity of a solution is defined in terms


pK a log 0.1 pH pK a log10 10
of buffer index which is the change in the
concentration of Buffer acid (or base) required (pKa 1) pH (pKa 1)
for change of it's pH value by one, keeping (Csalt Outside this range the Buffer capacity is too small
+ Cacid) or (Cbase + Csalt) constant. to be of any practical application.
Let there be a buffer solution of volume 1 litre * Acid-base Indicators
with `x' mole of acid and `S' moles of `salt'. An acid & base indicator is a substance which
S changes it's colour within limits with variation in
pH = pKa + log10 pH of the solution to which it is added.
x S
Indicators, in general are either organic weak
1 S acids or weak bases with a characteristics of
pH pK a log e
2.303 x S having different colours in the ionized and
(pH) 1 1 1 unionized form e.g. phenolphthalein is a weak
acid (ionized form is pink and unionized form is
S 2.303 S x S

colourless).
(pH) 1 x S S Acidic Indicator Action (e.g. HPh)
HPh (Phenolpthalein) is a colourless weak acid
S 2.303 S(x S)
H Ph
HPh
Colourless (Pink)
S S(x S)
2.303
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(pH) x [H ][Ph ]
K In
Maximum value of Buffer Index [HPh]
S(x S) If the solution is acidic, the H+ by the acid
B.I = 2.303
x increases and since Kin is constant and it does
not depend upon the concentration so HPh also
d 1 increases means equilibrium will shift towards left
(B.I) = 2.303 (x 2S)
dS x means solution remain colourless. By addition of
for maximum value of Buffer index alkali, OH- will be furnished and that OH- will
d combines with H+ of HPh to form water and
(B.I) = 0 equilibrium will moves towards right and
dS
therefore solution becomes pink. Thus HPh
After solving S = x/2
appears colourless in acidic and pink in alkaline
[Salt] S x/2 solution pH range of HPh is (8.3 -10).
Thus 1
[Acid] x S x x / 2
[In ]
Hence max. value of Buffer index occurs when, pH pK In log
[HIn]
[Salt]
1 The colour of the indicator changes from colour
[Acid] A to colour B at a particular point known as end
* Buffer Range point of indicator. At this point [HIn] [In ]
It is difficult to give an exact limit upto which a
buffer can be used it is generally accepted that a means pH pK In (at this point half of indicator
solution has useful buffer capacity provided that is in the acid form and half in the form of its
the value of [Salt]/[Acid] lie within the range of conjugate form.
10 to 0.1.Hence from Henderson equation
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JEE ADVANCED-VOL - III IONIC EQUILIBRIUM
* Indicator (Basic) action of MeOH (Methyl [In ]
Orange) ii) at pH = pK in 1 Mean [HIn] 10
When MeOH is dissolved in water and
undergoes dissociation to a small extent. The Percentage of ionization of indicator is
undissociated [In ] 10 [HIn]
100% 100%
molecules are yellow while dissociated Me+ are
[I n ] [HIn] 10 [HIn] [HIn]
red in colour.
1000
Me OH
MeOH 91%
yellow red colourless 11
If the solution is acidic, the H+ furnished by the Thus most of the indicator is present in the ionized
acid combines with OH- ions furnished by the form I n and solution gets the characteristic
indicators to form undissociated water. This shifts colour. In fact pH = pKin + 1 is the minimum pH
the equilibrium towards right giving red coloured upto which the solution has a distinct characteristic
solution. Therefore in acid solution, this indicator
colour of I n . At pH greater than this value, more
gives red colour. In the presence of alkali, OH-
increases and due to common ion effect the of the indicator is present in the ionized form.
dissociation of MeOH supress means equilibrium Thus at
will shifts towards left. Hence the solution in pH pK in 1 , the solution has a colour
alkaline medium remains yellow in colour.
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characteristics of I n .
Colour of solution depends upon relative amount
Ostwald's Theory
of ionized form to unionized form
According to this theory:
(ratio of Me+/ MeOH).
a) The colour change is due to ionization of the acid-
In general pH range of indicator lies between base indicator. The unionized form has different colour
pK in 1 to pK in 1 than the ionized form.
b) The ionization of the indicator is largely affected in
i) pH = pK in 1 acids and bases as it is either a weak acid or a weak
base. In case, the indicator is a weak acid, its ionization
I n
Means 0.1 10% is very much low in acids due to common H+ ions while
[HIn] it is fairly ionized in alkalies. Similarly if the indicator is
Percentage ionization of indicator would be a weak base, its ionization is large in acids and low in
alkalies due to common OH- ions.
In 0.10 HI n Considering two important indicators phenolphthalein

100% 100%
[I n ] [HI n ] 0.10 HIn (HI n ) (a weak acid) and methyl orange (a weak base),
Ostwald theory can be illustrated as follows:
1
= 100 9.1%
11 Phenolphthalein: It can be represented as HPh. It
Infact, pH = pKin - 1 is the maximum pH upto ionizes in solution to a small extent as:
which the solution has a distinct colour H Ph
HPh
Colourless Pink
characteristic of HIn. At pH smaller than this
value, more of the indicator is present in the [H ][Ph ]
unionized form. Applying law of mass action, K
[HPh]
Thus at pH pKin -1, the solution has a colour The undissociated molecules of phenolphthalein are
characteristic of HIn. colourless while Ph- ions are pink in colour. In presence

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IONIC EQUILIBRIUM JEE ADVANCED-VOL - III
of an acid, the ionization of HPh is practically negligible This theory also explains the reason why phenolphthalein
as the equilibrium shifts to left hand side due to high is not a suitable indicator for titrating a weak base against
concentration of H+ ions. Thus, the solution would strong acid. The OH- ions furnished by a weak base
remain colourless. On addition of alkali, hydrogen ions are not sufficient to shift the equilibrium towards right
are removed by OH- ions in the form of water molecules hand side considerably, i.e., pH is not reached to 8.3.
and the equilibrium shifts to right hand side. Thus, the Thus, the solution does not attain pink colour. Similarly,
concentration of Ph- ions increases in solution and they it can be explained why methyl orange is not a suitable
impart pink colour to the solution. indicator for the titration of weak acid with strong base.
Quinonoid Theory: According to this theory:
H 3O In
HIn H2O
`Acid form' `Baseform' a) The acid-base indicators exist in two tautomeric
forms having different structures. Two forms are in
Conjuage acid-base pair equilibrium. One form is termed benzenoid form and
the other quinonoid form.
[In ][H 3 O]
K In ;
[HIn]

K In Ionization constant of indicator,, b) The two forms have different colours. The colour
[HIn] change is due to the interconversion of one tautomeric
[H 3 O] K In form into other.
[In ]
c) One form mainly exists in acidic medium and the
pH = - log10 [H 3 O] = other in alkaline medium.
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Thus, during titration the medium changes from


[HIn]
- log10 [Kin] - log10 acidic to alkaline or vice-versa. The change in pH
[In ] converts one tautomeric form into other and thus, the
colour change occurs.
[In ]
pH = pKIn + log10 Phenolphthalein has benzenoid form in acidic
[HIn] medium and thus, it is colourless while it has quinonoid
(Handerson equation for indicator) form in alkaline medium which has pink colour.
At equivalence point; [In ] [HIn] and pH = pKIn
Methyl orange: It is a weak base and can be OH O

represented as MeOH. It is ionized in solution to give C


OH


C
H
Me+ and OH- ions. O
OH OH
Me OH

C COO
MeOH
Yellow Re d
O
Applying law of mass action
[Me ][OH ] Methyl orange has quinonoid form in acidic solution
K and benzenoid form in alkaline solution. The colour of
[MeOH]
benzenoid form is yellow while that of quinonoid form
In presence of an acid, OH- ions are removed in the is red.
form of water molecules and the above equilibrium shifts
to right hand side. Thus, sufficient Me+ ions are produced CH 3

N
which impart red colour to the solution. On addition of O 3S NH N
CH 3
alkali, the concentration of OH- ions increases in the Quinonoid form Acidic solution (red)
solution and the equilibrium shifts to left hand side (due
OH
-

to common ion effect), i.e., the ionization of MeOH is H


CH 3

practically negligible. Thus, the solution acquires the


O 3S N N N
CH 3
colour of unionized methyl orange molecules, i.e., yellow.
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JEE ADVANCED-VOL - III IONIC EQUILIBRIUM
* Solubility and solubility Product ii) Solubility of AgCl in a solution that is
A solution which remain in contact with excess having 0.1M in AgNO3:
of the solute is said to be saturated. The amount AgCI would dissolve and finally reach saturation.
of a solute, dissolved in a given volume of a AgCl(s) Ag+(aq) + Cl-(aq)
solvent (in 1 litre) to form a saturated solution at The KSP of AgCl is approximately 10-10 . If AgCl
a given temperature, it termed as the solubility of were to be dissolved in water (pure), its solubility
the solute in the solvent at that temperature. would have been 10-5M (previous section).In the
Molar Solubility: No. of moles of solute dissolved presence of 0.1 M AgNO3 its solubility will
in per litre of solution decrease due to common ion effect. This means
Solubility Product: In a saturated solution of a that [Ag+] from AgCl would be less than 10-5
salt, there exists a dynamic equilibrium b/w the M . Hence, we can ignore the contribution
excess of the solute and ions furnished by that of Ag+ from AgCl.
parts of the solute which has gone in solution. If the solubility of AgCl is x moles /L in the
The solubility product of a sparingly soluble salt presence of 0.1 M AgNO3, then
is given as product of the conc. of the ions raised [Ag+] = 0.1 M, [Cl-] = x M
to the power equal to the no. of times the ion K SP
x = = 10-9 moles / l
occur in the equation after the dissociation of the 0.1
electrolyte. iii) Solubility of CH3COOAg(salt of weak acid
and strong base) in water:
xAy+ + yBx
AxBy
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CH 3COOAg dissolves and reaches


saturation.Since it is a salt of weak acid and
K sp [A y ]x [Bx ]y strong base, it would hydrolyse. If the solubility
Let the solubility of AxBy is S then of the salt is x moles /then
K sp [xS]x [yS]y
x y xy
CH 3COO aq Ag aq
CH 3COOAg s
K sp x .y [S ]
At eq : x-y x
The principle of solubility product is applicable
for sparingly soluble salt.
CH3COO aq H2O
CH3COOH aq OH

x-y y y
Calculation of Solubilities of Salts -
where y is the amount of CH3COO ion that is
We shall now discuss the solubilities types of salts hydrolysed.
under various conditins. (x - y) x = KSP
i) Solubilities of AgCl(salt of a strong acid and
y2 K
strong base) in Water : w
(x y) K a
AgCl would disolve in water as,
Knowing the values of KSP and Ka, solubility of
AgCI (S) Ag+ (aq) +Cl- (aq) the salt can be calculated.
At saturation point, iv) Solubility of CH3COOAg (salt of a weak
AgCI(s) Ag+ (aq) +Cl- (aq) acid and strong base) in an acid buffer of
pH = 4 (assuming that the buffer does not
If the solubility of the salt is x moles/ lit.
have any common ion by CH3COOAg):
[ Ag+] = xM, [Cl ] = xM CH 3 COOAg would dissolve and reach
x2 = KSP equilibrium. It would then be hydrolysed.If the
x = K SP solubility of the salt is x M in this solution ,then
At eq.;
10 Narayana Junior Colleges
IONIC EQUILIBRIUM JEE ADVANCED-VOL - III

CH 3COO aq Ag aq
CH 3COOAg s Knowing Ksp and Kf , the solubility can be
calculated. The common ion presence in the
x - y x
-
solution decrease the solubility of a given
CH3COO (aq) + H2O CH3COOH (aq) + OH- compound e.g. The solubility of BaSO4 in Na2
x- y y 10-10 SO4 solution is smaller than that in an aqueous
Since the solution is a buffer, the pH will be solution .
maintained. Common-ion Effect on Solubility
(x - y) x = KSP The common ion presence in the solution
y2 K decrease the solubility of a given compound e.g.
w
(x y) K a The solubility of BaSO4 in Na2SO4 solution is
smaller than that in an aqueous solution.
knowing KSP and K a, the solubility can be
Consider saturated solution of AgCl. If a salt
calculated.
having either of the ion common to AgCl say KCl
v) Solubilty of CH3COOAg in an buffer solution of
is added to it, then
pH =9:
Following the same logic as give in the earlier Ag Cl
AgCl(s) aq.
section,
K Cl
KCl(s) aq.
CH3COOAg(s) CH3COO- (aq) + Ag+ (aq)
At eq : x- y x For AgCl K SP [Ag ][Cl ]
-
CH3COO (aq) + H2O CH3COOH + OH- [Cl ] Increases in solution due to presence of
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At eq : x- y y 10-5
KCl and thus to have K SP constant, [Ag ]
where x M is the solubility of the salt and y the
extent to which it is hydrolysed. will decrease or AgCl will precipitate out from
( x - y) x = Ksp
solution, i.e., solubility of AgCl will decrease with
increasing concentration of KCl in solution.
y '' 105 K w
Let 0.1 M KCl(aq.) solution with AgCl(aq.) . If
(x '' y '') K a
solubility of AgCl is s mol litre-1, then,
Knowing K sp and K a, the solubility can be
calculated. For AgCl K SP [Ag ][Cl ]
KSP s(s 0.1)
vi) Solubility of AgCl in an aqueous solution
containing NH3. is being small in comparison to 0.1 and thus may
Let the amount of NH3 initially be a M. If the be neglected therefore,
solubility of the salt is x moles /L, then K SP
+ -
K SP s 0.1 or s AgCl where s is
AgCI (s) Ag (aq) + Cl (aq) 0.1
x-y x solubility of AgCl in presence of 0.1 M KClaq.
+
Ag (aq) + 2NH3 (aq) [Ag(NH3)2]+(aq) * Ionic Product
x-y a - 2y y For a solution of a salt at a specified
Where y is the amount of Ag+ which has reacted concentration, the product of the concentration
with NH3. of the ions, each raised to the proper power, is
(x -y ) x = Ksp called as the ionic product for a saturated solution
y in equilibrium with excess of solid, the ionic
Kf product is equal to solubility product.
(x y)(a 2y)2
( formation constant of [Ag(NH3)2]+ At equilibrium, ionic product = solubility product
Narayana Junior Colleges 11
JEE ADVANCED-VOL - III IONIC EQUILIBRIUM
If ionic product is less than solubility product it i) Solubility of a salt of weak acid and strong
means solution is unsaturated and more salt can base in Basic Buffer suppresses than pure water
be dissolve in it. due to common ion effect. But in acidic buffer
If ionic product is greater than solubility it means solution soubility increase than pure water.
solution is holding more salt than it can dissolve ii) Solubility of salt of weak acid and weak base
in therefore precipitation starts and continues till, in pure water: Let the solubility of salt be S, and
ionic product becomes equal to Ksp. y mol/litre is the amount of salt getting hydrolysed.
Preferential Precipitation of Salts


CH3COONH4 CH3COO- + NH 4 (A)
Frequently, a solution contains more than one ion
capable of forming a ppt. with another ion which S-y S-y
is added to the solution. e.g., in a solution
CH3COO - + NH 4 + H 2O
CH 3COOH +
containing Cl , Br and I , if Ag+ ions are
NH4OH
added then out of the three, the least soluble silver
S-y S-y y y ... (B)
salt is ppt first. If the addition of Ag+ ions is
continued, eventually a stage is reached when K sp (S y)(S y) (S y) 2
the next lesser soluble salt starts ppt along with Due to hydrolysis of salt from equation (B)
the least soluble salt and so on. If the [CH 3COOH][NH 4OH] y.y
stoichiometry of the ppted salts is the same, then Kh

[CH 3COO ][NH 4 ] (S y)(S y)
the salt with the minimum Ksp or minimum
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solubility will ppted first followed by higher Ksp. 2


y
If the stoichiometry of the ppted salts is not the Kh
same, then with Ksp alone, we can't predict which S y
ion will ppted first. e.g. a solution containing Cl- and we also know that
and CrO 42 both of these ions form ppt with Kw
Kh
Ag+ though the Ksp (AgCl) > Ksp (Ag2CrO4). Ka Kb
Yet it is AgCl (less soluble) which ppted first when Solubility of a salt of weak acid and weak
Ag+ ions added to the solution. In order to predict base in acidic buffer
which ion (Cl- or CrO 42 ) ppt first. We have to Let the solubility of salt be S and y be the amount
of weak acid being formed.
calculate the conc. of Ag+ ion needed to start
ppt through the Ksp and given conc. of Cl- and CH COO- + NH 4
CH3COONH4 3

CrO 42 , if the conc. of Ag+ ions needed to start S-y y


- +
CH3COO + H CH3COOH (B)
the ppt of CrO 42 is larger than that of Cl-. Hence
S - y (from Acidic Buffer) y
as AgNO3 is added to the solution, the minimum
of the two conc. of Ag+ to start the ppt will be K sp [CH3COO ][NH 4 ] = [S - y] [y] = y [S - y]
reached first and thus the corresponding ion (Cl- for equation (B)
in this case) will be ppted in preference to the 1 [CH3COOH] y
other. During the course of ppt conc. of Cl- Ka
Ka(CH3COOH) [CH3COO ][H ] (S y)(H )

decreases and conc. of Ag+ increases when its's


conc. become equals to the conc. required (of Solubility of CH3COONH4 in acidic buffer would
Ag+) for . At this stages the whole of Cl- ions be higher than in pure water
have been ppted the addition of more of AgNO3 Solubility of a salt of weak acid and weak
causes the ppt of both the ions together. base in basic buffer
12 Narayana Junior Colleges
IONIC EQUILIBRIUM JEE ADVANCED-VOL - III

CH COO- + NH 4
Similarly CH3COONH4 3

y S-y

NH 4 OH NH4OH
S-y (from buffer) y
K sp (CH3COONH4 ) [CH3COO ][NH 4 ]
K sp y(S y)
(ii) Weak acid and strong base: p H curve
1 [NH 4 OH] y
Kb of weak acid (say CH 3COOH or oxalic
Kb [NH 4 ][OH ] (S y)[OH ]

acid) and strong base (say NaOH) is
The solubility of CH 3COONH 4 in basic buffer
would be higher than pure water.

* Acid- Base Titrations:


In acid-base titrations, pH of solution changes
as the reaction prooceeds and if pH of solution
is plotted against volume of tirant, the curves
obtained are known as titration curves or
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neuttralization curves or pH curve. Generally,


they are S-shaped if base is being used as titrant.
Titration curves are useful in detection of end
point and around the equivalence point, titration
vertical over the approximate pH range 7 to11.
curve remains almost vertical. It indicates that
So, phenolphthalein is the suitable indicator
initially pH changes very slowly but change is for such a titration.
rapid near equivalence point. After equivalence
(iii) Strong acid and weak base: pH curve
point again pH change becomes slow.
The extension of vertical zone gives idea about of strong acid (say Hcl or H 2 SO4 or HNO3 )
pH range and correct choices of the indicators. with a weak base say NH 4OH is vertical
For a particular titration, the indicator should
be so selected that it changes its changes its over the pH range of 4 to 7. So, the
colour within vertical distance of the curve. indica tors methyl red and methyl orange
are suitable for such a titration.
(i) Strong acid and strong base: p H curve
of strong acid (say HCl)and strong base base
(say NaOH) is vertical over almost the
p H range 4-10. So, the indicators
phenolphtthalein ( p H range 8.3 to 10.5),
methyl red ( p H range 4.4 - 6.5) and methyl
orange ( p H range 3.2 - 4.5) are suitable for
such a titration.

Narayana Junior Colleges 13


JEE ADVANCED-VOL - III IONIC EQUILIBRIUM
(iv) Weak aicd and weak base: pH curve
of weak acid and weak base indiactes that LEVEL-IV
there is no vertical part and hence, no suitable
indicator can be used for such a titration. SINGLE ANSWER QUESTIONS

1. A solution contains 0.1 M H2S and 0.3 M


HCl. Calculate the conc. of S2- and HS-
ions in solution. Given K a1 and K a 2 for
H2S are 10-7 and 1.3 10-13 respectively..
(A) 1.44 10 19 ,3.3 10 7
(B) 1.44 10 20 ,3.3 10 8
(C) 1.44 10 22 ,3.3 10 3
(D) 1.44 10 18 ,3.3 10 5
2. An aqueous solution of metal bromide MBr2
(v) Titration of diacidic base (sodium car (0.05M) is saturated with H2S. The minimum
bonate) with strong acid. pH at which MS will ppt. will be
pH curve of sodium carbonate with HCl Ksp for (MS) = 6 10-21
shown two inflection points. First inflection point Concentration of saturated H2S = 0.1
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Ka1(H2S) = 1 10-7
pH 8.5 indicates conversion of carbonate Ka2(H2S) = 1.3 10-13
into bicarbonate. (A) 0.982 (B) 0.0983
Na2CO3 HCl NaHCO3 NaCl (C) 1.96 (D) 2.96
As the inflection point lies in the pH range 8 3. A solution of 0.1 M is Cl and 10-4 M
to 10, phenolphthalein can be used to indicate CrO 24 . If solid AgNO3 is gradually added
the above conversion. The second inflection
to this solution, what will be the
point pH 4.3 indicates the following reac concentration of Cl when Ag2CrO4 begins
tion: to precipitate?
NaHCO3 HCl NaCl CO2 H 2O (Ksp (AgCl) = 10-10M2, Ksp (Ag2CrO4) =
As the point lies between 3 to 5, methyl or 10-12 M3)
ange can be used. A) 10-6 M B) 10-4 M C) 10-5 M D) 10-9 M
4. One litre of a buffer solution containing 0.02
mol of propanoic acid and some sodium
propanoate has pH = 4.75. What will be the
pH if 0.01 mol of hydrogen chloride is
dissolved in the above buffer solution ?
[Dissociation constant of propanoic acid at
250C is [1.34 10-5. ]
(A) 4.11 (B) 2.11 (C) 0.11 (D) 3.11
5. A weak base (BOH) with Kb = 10-5 is titrated
with a strong acid, HCl. At 3/4th of the
equivalence point, pH of the solution is:
(A) 5 + log3 (B) 14 - 5 - log3
(C) 14 - 5 + log3 (D) 9.523.
14 Narayana Junior Colleges
IONIC EQUILIBRIUM JEE ADVANCED-VOL - III

6. pKa (CH3COOH) is 4.74. x mol of lead 11. K a for the reaction


acetate and 0.1 mol of acetic acid in one L F e 3 aq H 2 O l F e O H
2
aq H 3O aq
solution make a solution of pH = 5.04.
is 6.5 103 , what is the
Hence, x is :
maximum pH value which could be used so that
(A) 0.2 (B) 0.05 (C) 0.1 (D) 0.02. at least 80% of the total iron (III) in a dilute
7. The K sp of Mg(OH)2 is 8.9 10-12 at 25C. solution exists as Fe3 ?
If the pH of solution is adjusted to 9.0. How a) 2.0 b) 2.4 c) 2.8 d) 1.6
much Mg2+ ion will be precipitated as 12. The pH of 0.1M solution of the following
Mg(OH)2 from a 0.1M MgCl2 solution at salts increases in the order.
25C? Assume that MgCl2 is completely a) NaCl NH 4Cl NaCN HCI
dissociated. b) HCI NH 4CI NaCI NaCN
(A) 0.011 (B) 0.089 (C) 0.11 (D) 0.89
c) NaCN NH 4CI NaCI HCI
8. Two buffers, (X) and (Y) of pH 4.0 and 6.0
respectively are prepared from acid HA and d) HCI NaCI NaCN NH 4CI
the salt NaA. Both the buffers are 0.50 M 13. The following pH range where the indicator
in HA. What would be the pH of the solution shows change in colour are given
i. 4 9.7 ii. 7.46 10.0 iii. 6.5 4
obtained by mixing equal volumes of the two
which of the above pH range represent titration of
buffers ? (KHA = 1.0 10-5). I. Strong acid/strong base (SA/SB)
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(A) 4.7033 (B) 5.7033 II. Weak acid/ strong base (WA/SB)
(C) 6.7033 (D) 8.7033 III. weak base/strong acid (WA/SA)
9. 0.1 mole of CH3NH2 (Kb = 5 10-4) is mixed a. i I , ii II , iii III
with 0.08 mole of HCl and diluted to one litre.
b) iii I , ii II , i III
What will be the H in the solution. (IIT
c. ii I , iii II , i III
JEE 2005)
d) i I , iii II , ii III
(A) 8 10-2 M (B) 8 10-11 M
14. What will be the pH of an aqueous solution
(C) 8 10-15 M (D) 8 10-5 M
of 1.0 M ammonium formate?
10. If equal volumes of BaCl2 and NaF solutions Given :- pK a 3.8 and pK b 4.8
are mixed which of these combination will A) 7.5 B) 3.4 C) 6.5 D) 10.2
not give a precipitate? 15. The percentage of hydrolysis of a salt of
weak acid (HA) and weak base (BOH) in its
K sp of BaF2 1.7 107 0.1 M solution is found to be 10 %. If the
molarity of the solution is 0.05 M. the
A) 103 BaCl and 2 102 M NaF percentage hydrolysis of the salt should be
2
A) 5% B) 10%
B) 103 M BaCl and 1.5 102 M NaF C) 20% D) None of these
2 16. 0.1 M formic acid solution is titrated against
0.1 M NaOH solution . What would be the
C) 1.5 102 M BaCl and 10 2 M NaF difference in pH between 1/5 and 4/5 stages
2
of neutralization of acid?
D) 2 102 M BaCl and 2 102 M NaF A) 2 log B) 2 log 1/5
2 C) log 1/3 D) 2 log 4

Narayana Junior Colleges 15


JEE ADVANCED-VOL - III IONIC EQUILIBRIUM
17. The pH of a solution containing 0.4 M
HCO32 is:

Ka H 2CO3 4 107 ; K a HCO3 4 1011


1 2
A) 10.4 B) 10.1 C) 6.1 D) 10.7
C)
18. The pH of the resultant solution of 20 ml of
0.1 M H3 PO4 and 20 mL of 0.1 M Na3 PO4 is
A) pK a1 log 2 B) pK a1

pK a1 pKa2
C) pK a2 D)
2
19. In a saturated solution of AgCl, NaCl is
added gradually, The concentration of Ag+
D)
is plotted against the concentration of Cl .
The graph appears as:

20. During the titration of a weak diprotic acid


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H 2 A against a strong base NaOH , the


pH of the solution at half way to the first
equivalent point and at the first equivalent
A) point are given respectively by :
A) pK a1 and pK a1 pK a2

pK a1 pK a2
B) K a1 c and
2
pK a1 pK a2
C) pKa1 and
2
D) pK a1 and pK a2
21. Find the no.of moles of NH 4Cl required to
B)
prevent Mg OH 2 from precipitating in a
litre of solution which contains 0.02 mole of
NH 3 and 0.001 mole of Mg2+ ions
Given :
K b NH 3 10 5 ; K SP Mg OH 2 10 11

A) 104 B) 2 103
C) 0.02 D) 0.1

16 Narayana Junior Colleges


IONIC EQUILIBRIUM JEE ADVANCED-VOL - III

22. A 1.025 g sample containing a weak acid HX 28. If first dissociation of X OH 3 is 100%
mol.wt. 82 is dissolved in 60 ml . water where as second dissociation is 50% and
and titrated with 0.25 M NaOH. When half third dissociation is negligible then the pH
of the acid was neutralized the pH was found of 4 103 M X OH 3 is:
to be 5.0 and at the equivalence point the
pH is 9.0 . Calculate weight percentage of A) 11.78 B) 10.78 C) 2.5 D) 2.22
HX in sample 29. H3 A is a weak triprotic acid
A) 50% B) 75% C) 80% D) 60 %
23. 50 m L of 0.05 M Na2CO3 is titrated against K a1 105 m K a2 109 , K a3 1013
0.1 M HCl . On adding 40 ml of HCl , pH of What is the value of pX of 0.1 M H 3 A (aq.)
the solution will be solution? where pX= - log X and
H 2CO3 : pK a1 6.35, pK a2 10.33 A3
X
log 3 0.477, log 2 0.30 HA2
A) 6.35 B) 6.526 C) 8.34 D) 6.173
24. Equilibrium constants of A) 7 B) 8 C) 9 D) 10
T2 O T or 1 H 3 is an isotope of 1H 1 30. A solution is 0.10 M in Ba NO3 2 and 0.10
and H 2O are different at 298 K. Let at 298 K M in Sr NO3 2 . If solid Na2CrO4 is added
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pure T2O has pT (like pH) is 7.62.The pT of a


solution prepared by adding 10 ml, of 0.2 M to the solution, what is Ba 2 , when
TCl to 15 ml of 0.25 M NaOT is:
SrCrO4 beigns to precipitate?
A) 2- log 7 B) 14+ log7
C) 13.24 - log 7 D) 13.24 + log 7 K sp BaC rO 4 1.2 10 10 ; K sp SrCrO 4 3.5 10 5

25. To what volume, a soution of 10 litre of 0.5 A) 7.4 107 B) 2.0 10 7


M CH 3COOH k a 10 5
be diluted in C) 6.110 7 D) 3.4 10 7
order to double the hydroxide ion 31. A solution is 0.01 M in KI and 0.1 M in KCl.
concentration: If solid KI is added to the solution, what is
A) 20 L B) 30 L C) 40 L D) 50 L
the I when AgCl begins to precipitate?
26. 20 ml of 0.1 M weak acid HA ka 10 5
is
mixed with solution of 10 ml of 0.3 M HCl K sp AgI 1.5 10 16 ; K sp AgCl 1.8 10 10
and 10 ml of 0.1 M NaOH. Find the value of
A) 3.5 107 B) 6.1 10 8



A / HA A in the resulting
C) 2.2 10 7 D) 8.3 10 8
solution: 32. What is the minimum pH required to prevent
A) 2 10 4 B) 2 105 C) 2 103 D) 0.05 the precipitation of ZnS in a solution that is
27. Calculate the ratio of HCOO and F in a 0.01 M ZnCl2 and saturated with 0.10 M
mixture of 0.2 M HCOOH ka 2 104 H2 S ?

and 0.1 M HF k a 6.6 10 4 : [Given : K sp 1021 , K a1 ka2 1020 ]


A) 1 : 6.6 B) 1 : 3.3 A) 0 B) 1 C) 2 D) 4
C) 2 : 3.3 D) 3.3 : 2
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JEE ADVANCED-VOL - III IONIC EQUILIBRIUM

38. If K a1 , K a2 and K a3 be the first , second and


MULTIPLE ANSWER QUESTIONS
third ionization constnat of H 3 PO4
33. Which of the following statement are true
for a solution saturated with AgCl and AgBr. respectively and K a1 K a2 K a3 which
If their solubilities in mol lit-1 in separate is / are correct:
solutions are x and y respectively.
(A) [Ag+] = [Br-] + [Cl-] A) H ka1 H 3 PO4
(B) [Cl-] > [Br-]
B) H HPO4
2
(C) [Br-] > y
(D) [Ag+] = x + y
34. 10 mL of N/20 NaOH solution is mixed with C) K a2 HPO42 D) K a2 HPO42
20 ml N/20 HC1 solution. The resulting 39. Which of the following mixtures can act as a
solution will: buffer?
(A) turn phenolphthalein solution pink A) NaOH +HCOONa (1: 1 molar ratio)
(B) turn blue litmus red
B) HCOOH +NaOH(2 : 1 molar ratio)
(C) turn methyl orange red
(D) [H+]>[OH-] C) NH 4Cl NaOH (2 : 1 molar ratio)
35. Choose the correct statement/s : D) HCOOH + NaOH (1:1 molar ratio)
a) pH of acidic buffer solution decreases if more
salt is added COMPREHENSION TYPE QUESTIONS
b) pH of acidic solution increases if more salt is
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added
Paragraph -I
c) pH of basic buffer decreases if more salt is
added The solution which consumes [H+] or [OH-] or
d) pH of basic buffer increases if more salt is both simultaneously from externally added base
added in order to give negligible change in pH, is
known as buffer solution. In general, the solution
36. If you have a saturated solution of CaF2 ,
resists the change in pH.
then
Buffer solution does not mean that there does
1/3
A) Ca 2 k sp / 4 not occur a pH change at all. It implies the pH
change occurs but in negligible amount. There
B) 2 Ca 2 F are two types of buffer-
C) Ca 2 2 F (i) Acidic buffer : it is a mixture of weak acid
and its slat with strong base.
D) Ca 2 K sp (ii) Basic buffer : it is a mixture of weak base and
37. If concentration of two weak acides are its salt with strong acid.
C1 and C2 mol / L and degree of ionization 40. Which of the following mixture will be a
buffer solution when dissolved in 500 mL of
are 1 and 2 respectively then their water ?
relative strength can be compared by: (A) 0.200 mol of aniline and 0.200 mol of HCl
H (B) 0.200 mol of aniline and 0.400 mol of NaOH
1 1 (C) 0.200 mol of NaCl and 0.100 mol of HCl
A) H B)
2 2 (D) 0.200 mol of aniline and 0.100 mol of HCl
41. pH of 0.01 M (NH 4) 2SO 4 and 0.02 M
C11 K a1 C1
NH 4OH buffer (pKa of NH4+ = 9.26) is
C) C D) k C
2 2 a2 2 (A) 4.74 + log2 (B) 4.74 - log 2
(C) 4.74 + log 1 (D) 9.26 + log 1
18 Narayana Junior Colleges
IONIC EQUILIBRIUM JEE ADVANCED-VOL - III
42. To prepare a buffer of pH 8.26, amount of 45. For a sparingly soluble salt Ap Bq the
(NH4)2SO4 to be added into 500 mL of 0.01
M NH4OH solution [pKa (NH4+) = 9.26} relationship of its solubility product LS
(A) 0.05 mol (B) 0.025 mol
(C) 0.01 mol (D) 0.005 mol with its solubility S is
Paragraph -II
If a sparingly soluble salt is placed in water, after (A) LS S p q . p p .q q (B) LS S p q . p q .q p
some time an equilibrium is established when the pq
rate of dissolution of ions from the solid equals (C) LS S pq . p p .q q (D) LS S pq . pq
the rate of precipitation of ions from the saturated 46. Slaked lime, Ca(OH)2 is used extensively
solution at a particular temperature. Thus, a in sewage treatment. What is the maximum
dynamic equilibrium exists between the pH that can be established in Ca(OH)2(aq.)
undissociated solid species and the dissolved
ionic species in a saturated solution at a particular Ca(OH)2(s) 2+
Ca (aq) + 2OH (aq);

temperature. For example, in AgCl, we have Ksp = 5.5 10-6


the following equilibrium : (A) 1.66 (B) 12.34 (C) 7 (D) 14
AgCl (aq) Ag+ (aq) + Cl (aq.) Paragraph -III
The equilibrium constant Acidity or alkalinity of a solution depend upon
the concentration of hydrogen ion relative to that
Ag Cl
K eq of hydroxyl ions. The product of hydrogen ion
AgCl & hydroxyl ion concentration is given by
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Keq [AgCl] = [Ag+] [Cl-] Kw = [H+] [OH-]


Ksp(AgCl) = [Ag+] [Cl-] the value of which depends only on the
[AgCl] is constant temperature & not on the individual ionic
If there would not have been a saturated solution, concentration. If the concentration of hydrogen
then from equation (A), Keq. [AgCl] Ksp, but ions exceeds that of the hydroxyl ions, the solution
Keq. [AgCl] = QAgCl, where Q is ionic product.
is said to be acidic; whereas, if concentration of
It implies that for a saturated solution,
Q = Ksp hydroxyl ion exceeds that of the hydrogen ions,
Ksp is temperature dependent. the solution is said to be alkaline. The pH
When Q < Ksp, then the solution is unsaturated corresponding to the acidic and alkaline solutions
and there will be no precipitate formation. at 25C will be less than and greater than seven,
When Q = Ksp, then solution will be saturated, espectively. To confirm the above facts 0.5 M
no ppt. will be formed CH3COOH is taken for the experiments.
when Q > Ksp, the solution will be supersaturated [Given : Ka of acetic acid = 1.8 10-5]
and there will be formation of precipitate. 47. pH of the solution will be -
43. pH of a saturated solution of Ba(OH)2 is 12. (A) 2.52 (B) 2.22
Hence Ksp of Ba(OH)2 is:
(C) 5 (D) 3.92
(A) 5 10-7 M3 (B) 5 10-4 M2
(C) 1 10 M-6 3
(D) 4 10-6 M3 48. If pH of the solution is doubled, what will be
44. A solution is a mixture of 0.05 M NaCl and the concentration of acetic acid -
0.05 M NaI. The concentration of iodide (A) 1.8 10-5 M (B) 1.0 M
ion in the solution when AgCl just starts (C) 4.6 10 M 6 (D) 1.25 10-3 M
precipitating is equal to: 49. To what volume at 25 C must 1 dm 3 of this
(Ksp AgCl = 1 10-10 M2; Ksp AgI = 4 10-16
solution be diluted in order to double the pH
M2)
(A) 4 10-6 M (B) 2 10-8 M (A) 3.37 104 dm3 (B) 2.34 102 dm3
(C) 2 10 M-7
(D) 8 10-15 M (C) 1.68 104 dm3 (D) 3.18 103 dm3

Narayana Junior Colleges 19


JEE ADVANCED-VOL - III IONIC EQUILIBRIUM

Paragraph -IV 53. Calculate the pH of a solution made by


In qualitative analysis, cations of group II as well adding 0.01 mole of HCl in100 ml.of a
as group IV precipitated in the form of sulphides. solution which is 0.2 M in
Due to low value of Ksp of group II sulphides,
group reagent is H2S in presence of dil. HCl and NH 3 pKb 4.74 and 0.3 M in NH 4 :
due to high value of Ksp of group IV sulphides, A) 5.34 B) 8.66
group reagent is H2S in presence of NH4OH and
C) 7.46 D) None of these
NH4Cl.
In a 0.1M H2S solution, Sn2+, Cd2+ and Ni2+ ions 54. Use ful buffer range of weak acid
are present in equimolar concentration (0.1 M). HA ka 105 is :
Given: Ka1(H2S) = 10-7, Ka2(H2S) = 10-14,
K sp (SnS) = 8 10 -29 K sp (CdS) = 10 -28 , A) 5 to 7 B) 4 to 6
Ksp(NiS) =3 10-21 C) 3 to 5 D) None of these
50. At what pH precipitate of NiS will form - 55. Select corect statement :
(A) 12.76 (B) 7 A) When we add small amount of NaOH in
(C) 1.24 (D) 4 acidic buffer solution,pOH of solution is
51. Which of the following sulphide is more
increases
soluble in pure water-
(A) CdS (B) NiS B) When we add small amount of NaOH in basic
(C) SnS (D) all have equal solubility buffer solution, pH of solution is
Paragraph -V increases
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Solution of an acid and its anion (that is.its C) When we add small amount of water in acidic
conjugate base ) or of a base and its common buffer solution ,pH of solution is
cation are buffered.When we add a small amount decreases
of acid or base to any one of them, the pH of
solution changes very little.pH of butter solution D) When 100 ml of 0.2 M CH 3COOH react
can be computed as for acidic buffer : with 200 ml of 0.1 M NaOH buffer solution
Conjugate base is formed
pH pK a log
Acid
MATRIX MATCHING QUESTIONS
for basic buffer :

pOH pK b log
Conjugate base 56. Consider a buffer of CH3COOH and CH3
Base COONa of maximum buffer-capacity and
It is generally accepted that a solution has useful match the following :
buffer capacity (pH change resisting power) Column I
provided that the value of [ salt or conjugate base]/ (A) For maximum buffer capacity
[acid] for acidic buffer lies within the range of (B) Adding equal number of moles of
1:10 toi 10: 1. Buffer capacity is max.
When[conjugate base ]= [acid] CH3COOH and CH 3COONa
52. One litre of an aqueous solution contain 0.15 (C) Diluting buffer 10 times
mole of CH 3COOH pK a 4.8 and 0.15 (D) Adding some NaOH to buffer
Column II
mole of CH 3COONa .After the addition of (p) No change in pH
0.05 mole of solid NaOH to this solution, the (q) pH > pKa
pH will be:
(r) pH = pKa
A) 4.5 B) 4.8 C) 5.1 D) 5.4
(s) pOH = pKb
20 Narayana Junior Colleges
IONIC EQUILIBRIUM JEE ADVANCED-VOL - III

57. Match the following .


Column- I LEVEL - IV
Sparingly soluble salt of weak acid KEY
Ratio of solubilities of salt in buffer and in 01. B 02.A 03.A 04.A 05.B
A) Ratio of solubility of a salt MCN in a 06.C 07.A 08.B 09.B 10.C
B) Ratio of solubility of a salt MCN in a 11.D 12.B 13.A 14.C 15.B
C) Ratio of solubility of a salt MCN in buffer 16.D 17.B 18.C 19.C 20.C
D) Ratio of solubility of AgCI in 0.1 M HCI 21.B 22.C 23.D 24.D 25.C
26.A 27.C 28.A 29.D 30.D
E) Ratio of solubility of Al OH 3 in 31.D 32.B
0.1 M HCI and 0.2M NaOH. 33.A,B,C 34.B,C,D 35.B,C 36. A,B
Column-II 37.A,C 38.A,C 39.B,C 40.D
41.D 42.B 43.A 44.C 45.A
p) 4 buffer of pH = 3. K a 10 3 / 3 and 46.B 47.A 48.C 49.A 50.C
51.B 52.C 53.B 54.B 55.B
solubility in H 2O is
56. A r , s; B r; C p; D q,
q) 2 buffer of pH = 4, K a 10 4 / 7 and 57. Aq; B p;C s; D q; E r
58.6 59.5 60.5 61.2
solubility in H 2O is
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HINTS - LEVEL - IV
r) 8 of pH = 5 K a 10 5 / 8 and solubility

in H 2O is 1. H HS ; ka 10 7
H 2 S 1

s) 3 and 0.2 M H S 2 ; ka 1.3 1013


HS 2

INTEGER TYPE QUESTIONS HCl H Cl


due to common ion effect the dissociation of H 2 S
58. What will be pH of the solution of the salt of
weak acid and weak base? is suppressed and the H in solution is due
-6 -4
(Kb = 1 10 and Ka = 1 10 )
H HS
59. Conjugate base of [Al(H2O)6]+3is k
to HCl. a1
Al (H2O)x(OH)y, the value of x/y is, H2S
60. The mixture of 10 ml 0.5 N CH3COOH and
10 ml of 0.25 M NaOH , having pH = 5,
0.3 HS
10 7 H from HCl 0.3
then find the value of pKa? 0.1
61. Among these mixture 107 0.1
(i) 50 ml of N/10 HCl + 50 ml of N/10 NaOH HS 3.3 108 M
0.3
(ii) 55 ml of N/10 HCl + 45 ml of N/10 NaOH
(iii) 75 ml of N/10 HCl + 25 ml of N/10 NaOH H S2
(iv) 30 ml of N/5 ml HCl + 70 ml of N/5 NaOH ka2
HS
For how many of the above mixutres pH lies
0.3 S2
between 1 to 7 1.31013
further 3.3108
S 1.31013 3.3108 /0.03 1.431020 M
2

Narayana Junior Colleges 21


JEE ADVANCED-VOL - III IONIC EQUILIBRIUM

2. given
salt
We get 4.75 = -log(1.34 10-5) + log acid
MBr2 aq M 2 2 Br

MBr2 g

MBr2 H 2 S MS 2 HBr
salt
which gives 4.75 = 4.87 + log
0.02M
K sp of MS M 2 s 2
Salt 0.76 or [salt] = 1.52 10-2 M
or
6 10 21
0.05 S
2 0.02 M

S 2 1.2 10 19 M Hence, Amount of sodium propanoate to be


added = 1.52 10-2 mol
thus MS will be precipitated if H2S provides 1.2 The addition of 0.01 mol of hydrogen chloride
x 10-19M ions of S-2 convert the equivalent amount of sodium
propanoate into propanoic acid .
2 H S 2 5. Let the initial no. of equivalents of
now for H2S H 2 S
BOH be x BOH + HCl BCl + H2O
2
H S 2 Initial equivalent x 3/4x
ka1 ka2 0 0
H2S
3x x
At 3/4th eqv. pt. x 0
2 4 4
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H 1.2 10 19
10 7 1.3 10 13 3 3
0.1 x x
4 4
H 1.04 101 [salt] 3x 4
pOH = pK b log 5 log
[Base] 4 x
p H 0.9826
pH = 14 - 5 - log 3 = 8.523
3. [Ag+] required for precipitation of AgCl
salt
ksp AgCl 6. pH = pKa + log acid

Ag 10 9

Cl
CH 3 COO 2 Pb
[Ag+] required for precipitation of Ag2CrO4 5.04 = 4.74 + log
CH 3COOH
ksp Ag 2 CrO 4 10 12
Ag 10 4 n CH3COO x
CrO 24 10 14 2
Pb

n CH COO 2x
At this point, the concentration of Cl- ion in the 3
solution can be calculated from Ksp (AgCl) n CH3COOH 0.1
10
ksp(AgCl) 10
Cl
4 106 M 2x
Ag 10 5.04 = 4.74 + log 0.1
4. Using the expression
2x
salt 0.3 = log
0.1
pH = pKa + log acid
2x
2=
0.1
x = 0.1
22 Narayana Junior Colleges
IONIC EQUILIBRIUM JEE ADVANCED-VOL - III

7. Ksp [Mg(OH)2] = 8.9 10-12 9. CH 3NH2 + HCl


CH3NH3+ Cl-
0.1 0.08 0
pH = 9 Intialmoles
[H+] = 10-9 0.02 0 0.08
moles after mixing As it is a basic buffer, so
OH 10 5 0.08
p(OH ) pK b log log5 104 log 4
0.02
2
Ksp = Mg 2 OH = 3.30 + 0.602 = 3.902
pH = 14 - p(OH) = 14 - 3.902 = 10.09
2 [H+] = 7.99 10-11 M = 8 10-11
8.9 10-12 = Mg 2 105 1
14. pH
2
pK w pK a pKb
Mg 2 8.9 10 2 0.089
15. is not dependent on concentration in this case
Conc. of Mg2+ precipitated = 0.1 - 0.089 = 0.011 CO32
mol/Lt. 17. pH pK a log

2 CO3
8. pH of buffer is given by :
Salt 21.
pH = - log Ka + log Acid
K SP 1011
OH 104
Mg 2 103
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Salt
Case I : 4 = - log 1.0 10-5 + log 0.5

pOH pK b log
NH 4Cl
or [Salt] = 0.1 0.5 = 0.05 M NH 3
Salt 22. When half of acid is neutralized pH pK a
Case II : 6 = - log 1.0 10-5 + log
0.5
23. CO32 H HCO3
Salt Initial milli moles 50 0.05 40 0.1 -
log 0.5 = 1
Final milli moles __ 1.5 2.5
[Salt] = 10 0.5 = 5 M
Now the two buffer [(I. NaA = 0.05M and HA HCO3 H H 2CO3
= 0.5 M) and (II. NaA = 5M and HA = 0.5M)] Initial milli moles 2.5 1.5 ___
are mixed in equal proportion. Final milli moles 1 __ 1.5
Thus, new conc. of NaA is mixed buffer = HCO3
0.05 V 5 V 5.05 pH pK a1 log 6.173
= H 2CO3
2V 2
New conc. of HA in mixed buffer = 24. TCl NaOT NaCl T2O
Initial 2 3.75
0.5 V 0.5 V milli-moles
0.5M
2V milli -moles of remaining NaOT = 1.75
5.05/ 2 1.75
OT 7 10 2 moles
Thus, pH = - log (1.0 10-5) + log
0.5 25
pOT = 2- log 7
pH = 5 + 0.7033 = 5.7033.
pT = 15.24 =2 +log 7
= 13.24 + log 7
Narayana Junior Colleges 23
JEE ADVANCED-VOL - III IONIC EQUILIBRIUM
3
25. is very less so H K a C 3 10 x K a HCOOH C1

y K a HF C2
3 103
Now H 1.5 103
2 HCOO x

1.5 10 3
ka .C2 F y

C2 0.125 2 104 0.2 2


milli-moles acid remians constant 4

6.6 10 0.1 3.3
C1V1 C2V2 28. First dissociation
10 0.5 0.125 V2 X OH 3 X OH OH
2

V2 40 litre Second dissociaztion:


2
10 0.3 10 0.1 X OH 2 X OH OH
26. H 0.05
10 10 20
Total OH 4 10 3 2 103 6 10 3
20 0.1
HA 0.05 pOH = 3 log 6 2.22
20 20
pH 11.78
HA H A
29. is negligible w.r.t. 1
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0.05 - x 0.05+x x
Due to common ion effect neglect x w.r.t. 0.05 H mainly from first step

Ka
0.05 x .x x H K a C 105 0.1 103
0.05 x
H A3 103 A3
x 105 ka 3 13
10
HA2 HA2
A x

HA A x 0.05

A3
X 1010 ;
HA2
x 105
2 104 pX = 10
0.05 5 102
30. K sp SrCrO4 Sr 2 CrO42
27. HCOOH(aq.)+ H 2O l HCOO aq.

C1 x x H 3O aq.
3.5 105
CrO42 3.5 104
0.1
HF aq. H 2O l F (aq.) H 3O aq.
K sp BaCrO4 Ba 2 CrO42
C2 y y x+y
is very les for both acid so CrO42 CrO42 from SrCrO4
total

y x y 1.2 1010
K a HF Ba 2 3.4 107
C2 3.5 10 4

24 Narayana Junior Colleges


IONIC EQUILIBRIUM JEE ADVANCED-VOL - III

31. After mixing Ag 0.2 M ; NH 3 1M 43. Ba 2 2OH 1


. Ba OH 2
Due to very high value of K f ; Ag mainly S 2S
3
converted into complex k sp 4s

Ag aq. 2 NH 3 aq. Ag NH 3 2 aq.



p H of Ba OH 2 12 OH 102
Initial concentration 0.2 1 2s 102
At equilibrium x 0.6
102
0.2 s 5 103

2
Ag NH 3 2 aq. Ag NH 3 aq. NH 3 aq. k sp 4s 3 5 107 m3
At equilibrium 0.2 -y y
0.6 + y 44.
Ag Cl 1010 m 2 .
0.2
0.6 1010
Ag
1

y 0 .6

0 .1
; y A g N H 3 3 .3 3 1 0 5 M 0.05
K f2 0 .2 104
Ag I 4 1016 m 2

32. K sp Zn2 S 2
4 1016 m 2
I 2 107 M
1021
Ag
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S 2 1019
0.01
2 Ap Bq pA qB
H S 2 45.
for K a1 . K a2 pS qS
H2S
Let solubility be s mol / lt .
2
H 1019 P q
20
10 H 0.1 Thus K sp A B
0.1
p q
or pH= 1 pS qS
34. 10 ml + 20 ml p q
N/20 NaOH N/20 ml HCl p p .q q S .
1 1 Ca 2 2OH
Ca OH 2
milli eq. = 10
20 2 46.
S 2S
1
milli equ. = 20 1
20 k sp 4s 3 ; ksp 5.5 106
solution also turns methyl orange rad
[H +] > [OH - ] ksp 5.5 106
S 3 3
then (B) (C) (D) are correct 4 4
40. For the formation of Buffer solution meq of weak
base > meq of strong acid. 3 1.375 106 1.119 102
41. Use Hendersons equation.
x OH 2 s 2.2238 102
42. 5.74 = 4.74 + log , calculating x = 0.02,
5 10 3
hence [(NH4)2SO4] required = 0.01 p OH log 2.2238 102 1.6529
p H 12.34

Narayana Junior Colleges 25


JEE ADVANCED-VOL - III IONIC EQUILIBRIUM

47. H ka c 59.
3
Al H 2O 6 Al H 2O 5 OH H

ka 1.8105
60. 10 ml of 0.5 N CH3COOH
c 5101M mill equ. = 10 0.5 = 5
H 1.8105 5101 9106 3103 10 ml of 0.25 N NaOH
Milli eq. = 0.25 10 = 2.5
pH 2.52 On adding 2.5 CH3COOH
2.5 CH3COONa
48. P H 5.04 It is doubled 2.5
pH = pKa + log
2.5
H 9.120 106
pH = pka + log 1
pka = 5
H K a .C

C 4.6 106 .
49. M1V1 M 2V2
Amount of water to be added V2 V1 .

3 1021
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50. k sp Nis 3 1021 S 2


0.1

H HS 1 ka 107
H 2 S 1

H S 2 ka 10 14
HS 1 2

H S 2
k a2
HS 1

2 20
H 3 1 0
k a 1 .k a 2 1 0 2 1
0 .1

1
H pH 1.2388
300

51. since ksp of NiS is greater then the remaining


then NiS is more soluble
1
58. pH= (14 pK a pK b )
2

1
(14 4 6) = 6
2

26 Narayana Junior Colleges

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