1.ionic Equilibrium (1-26)
1.ionic Equilibrium (1-26)
1.ionic Equilibrium (1-26)
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.
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
[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
-
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).
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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(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
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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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.;
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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
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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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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.
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.
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IONIC EQUILIBRIUM JEE ADVANCED-VOL - III
(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
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:
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
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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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
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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);
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
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
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
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
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
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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
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
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
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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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
1
(14 4 6) = 6
2