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RSM79Ph-IIIECH1

1. IIT–JEE syllabus
Acids and Bases, pH, Common ion effect, Buffer solutions, Hydrolysis of salts and
Solubility Product.

2. Concepts of Acids and Bases


2.1 Arrhenius Concept

According to Arrhenius, an acid is a substance that contains hydrogen and releases


hydrogen ions (H+) in aqueous solution. A base is a substance that produces OH–(aq).

HCl(aq) 
 H(aq)  Cl
 
NaOH(aq) 
 H(aq)  OH(aq)

In aqueous solution NH3 forms NH4OH which furnishes OH–(aq), NH4OH NH4  OH

The strength of an acid is defined in terms of concentration of H+(aq) that is present in the
aqueous solution of a given concentration of the acid. Similarly the strength of a base
depends upon the relative concentration of OH–(aq) in aqueous solution of the base. In
neutralisation reaction, H-+ and OH– ions combine to form water.
 
H(aq)  OH(aq) 
 H2O

2.2 Bronsted Lowry’s Protonic Concept

Bronsted acid is a proton donor and Bronsted base is proton acceptor. The reaction of an
acid with a base involves the transfer of proton from the acid to the base. Acids and bases
exist in a solution in a state of dynamic equilibrium. The conjugate base of a Bronsted acid
(HA) is the base that is formed when the acid has donoted a proton. The conjugate acid of a
Bronsted base is the acid that is formed when the base has accepted a proton.

Conjugate pair

Acid(1)  Base(2) Acid(2)  Base(1)


Conjugate pair

CH3COOH H2O CH3COO  H3O


Acid(1) Base( 2 ) Base(1) Acid( 2 )

For a conjugate acid base pair HA – A– in aqueous solution.

HA H+ + A–; Ka
A– + H2O HA + OH– Kb
––––––––––––––––––––
on adding H2O H+ + OH–

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 Ka  Kb = [H+] [OH–] = Kw = 10–14 (at 25°C)


 logKa  ( logKb )   log104  pKa  pKb  14
(  logKa  pKa  logKb  pKb )

That is strong acid has weak conjugate base and weak acid has strong conjugate base and
also lower the pKa value, higher the acid strength and lower the base strength of conjugate
base.

2.3 Lewis Acids and Bases

Lewis acid is a species that is capable of accepting a pair of electrons to form covalent bond
and Lewis base is a substance that is capable of donating an electron pair to form a
covalent bond.

Some examples of Lewis acid: BF3, Cu2+, Fe3+, SO2, SnCl2


Some examples of Lewis bases: F–, NH3, CN–, OH– etc.

3. pH of Acids and Bases


Many properties of aqueous solutions depends on the concentration of H+ ions of the
solutions and therefore there is a need to express these concentrations in simple terms. For
this purpose we introduce the concept of pH.

pH = – log aH+ (Where aH+ is the activity of H+ ions).

Activity of H+ ions is the concentration of free H+ ions in a solution. By free, we mean those
that are at a large distance from the other ion so as not to experience its pull. We can infer
from this that in dilute solutions, the activity of an ion is same as its concentration since more
number of solvent molecules would separate the two ions. For concentrated solutions the
activity would be much less than the concentration itself.

Therefore, the earlier given expression of pH can be modified for dilute solutions as,
pH = – log [H+]. This assumption can only be made when the solution is very much dilute,
i.e, [H+]  1M. For higher concentration of H+ ions, one needs to calculate the activity
experimentally and then calculate the pH.

3.1 Strong Acids

Let us now see how to calculate the pH of a solution of a strong acid in water (it should be
noted that pH calculations are only made for aqueous solutions). Let the strong acid be HCl.
If we take 10–1M HCl, the [H+] would be 10–1 M, as HCl is a strong acid and would dissociate
completely. Therefore the pH would be,

pH = –log 10–1 = 1

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Concentration of HCl pH

10–1M 1

10–2M 2

10–3 M 3

10–4 M 4

10–5 M 5

10–6 M 6

10–7 M 7 (?)

We can see that for 10–7M of HCl we have some hesitation in talking about the pH. This is
because if we use our expression of pH, it works out to be 7 which is somehow associated
with neutrality. We shall now explain how to calculate the pH of 10–7M HCl. Before we do
this we shall discuss the dissociation of water.

3.2 Dissociation of Water and Ionic Product of Water

Water behaves as a weak acid (or weak base) as it weakly dissociates to give H+ ions
(or OH–).

H2O H+ + OH–

This weak dissociation of water makes it reach equilibrium with its ions.

K=
H OH 
 

H2O
The concentration of water before dissociation is 55.56 moles per liter. Since the
dissociation of water is so feeble that it can be assumed that the concentration of water at
equilibrium is almost the same. Therefore we can assume that [H2O] is a constant .

 K[H2O] = [H+] [OH–] = KC

We can see that the above expression is KC. In this topic we shall give special sub–scripts
for different types of KC ‘s. Hence the above expression's which is the product of the
concentrations of H+ and OH– is called the ionic product of water, represented as Kw. At
25°C the value of Kw is approximately equal to 10–14.

 [H+] [OH–] = 10–14 …(1)

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As water gives the same amount of H+ and OH– and if we represent the concentration of H+
as xM then the concentration of OH– will also be xM.

xx = 10–14

x2 = 10–14 …(2)

x = 10–7M …(3)

 pH = – log 10–7 = 7

Now we revert back to our original problem which is the calculation of pH of a solution, 10–7
M HCl.

When we add 10–7 M HCl in water, the [H+] from HCl would be10–7 M. But pH is the negative
logarithm of the total H+ ion concentration of a solution and not that part which comes from
only HCl ( you might wonder why we have changed our stand. This will become clear in a
short while). Therefore, we need to add the concentration of H+ ions coming from water also.
This can be done in two ways.

Method – I: We already know the concentration of H+ ions from pure water. It is 10–7M. So
all we need to do is to add the H+ ion concentration from water and that from HCl to get the
total H+ ion concentration.

 [H+]T = [H+]HCl + [H+]water


= 10–7M + 10–7M
= 2  10–7 M

 pH = – log [H+]T
= – log 2  10–7
= 6.6989

Though everything looks OK, there is a big mistake we have made. In Lesson 4 (Chemical
Equilibrium) we have learnt in Le–Chatlier’s Principle that when concentration of a reactant
or product is changed the reaction tends to go forward or reverse to finally reach equilibrium.
We can see that in this case by adding 10–7 M HCl to water, we are increasing the
concentration of H+ ions. This should make the reaction go in the reverse direction.
Therefore the above given method is incorrect.

Method – II: The statement given above that “the addition of an ion to an equilibrium, having
the same ion makes the equilibrium reaction move in a direction to consume that ion” is
called the common ion effect. This implies that water would dissociate less in the presence
of HCl. Let the amount to which water disassociates be x in the presence of 10–7 M HCl.

 H2O H+ + OH–
At equilibrium: x + 10–7 x
[H+] [OH–] = 10–14
 (x + 10–7) (x) = 10–14
Calculating for x, we get x = 0.618  10–7 M.

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One can clearly see the common ion effect in action. Water which was dissociating to give
10–7M H+ ions, has now experienced the common ion effect and has finally yielded 0.618 
10–7 M H+ ions.

Therefore, [H+]T = 10–7 + 0.618  10–7


= 1.618  10–7 M
pH = – log ( 1.618  10–7) = 6.7910

Now, lets answer the question as to why we take the H+ ions of water into account for
calculating the pH of 10–7 M HCl while we never considered it for calculating the pH of
10–6M, 10–5M, 10–4M, 10–3M, 10–2M and 10–1M HCl. It can be seen that the H+ ions from
water has decreased due to the common ion effect. Greater the of the common ion added,
greater will be the effect. Therefore for concentrations higher than 10–6M (and inclusive of
10–6M), the H+ from water will be even less than 0.618  10–7 M and would be so small in
comparison to the [H+] from HCl, that we can ignore the contribution from it. So, finally we
conclude that H+ ions of water needs to be considered only if an acid is present such that
[H+]acid < 10–6M.

Illustration 1: 1 mL of 10–5 M HCl solution is diluted to 1000 mL. Calculate the pH of the
resulting solution.

Solution: [H+] = [HCl] = 10–8M (after dilution)


Since this is lower than even the [H+] from dissociation of H2O so we must
consider water as the principal source of H+ ion and HCl as exerting
common ion effect on the dissociation of water.

H2O H + OH _
x 10  8 x
+ –
Kw = [H ] [OH ]
(10–8 + x)x = 10–14
(Kw = 10–14 at 25°C)  x2 + 10–8x – 10–14 = 0
 10 8  10 16  4  10 14
x = = 9.5125  10–8
2
[H+]= 9.5125  10–8 + 10–8 = 10.5125  10–8
pH = 6.9783

The same logic applies for bases also. The only difference is that for deciding whether we
should take the OH– ion from water or not, we should see whether [OH–] from the base is
less than 10–6 M or not.

3.3 Weak Acids

Let us take a weak acid (CH3COOH) and see how to calculate its pH. Let its initial
concentration be C moles / l.

CH3COOH CH3COO– + H+
Initial C 0 0
At eq. C(1–) C C

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 KC =
CH COO   H 
3
 

CH 3 COOH 
This equilibrium constant, KC is given a symbol Ka.

 Ka =

CH 3 COO  H 
=
 
C  C
=
C 2
CH 3 COOH  C1    1 
Generally for weak acids,  (degree of dissociation) is very much less than 1. Therefore,
Ka
Ka = C2   =
C
We can see that as concentration decreases,  increases.
[H+] = C = K a C

Illustration 2: Calculate pH of the following two solutions


i) 1 M CH3COOH, and
ii) 10–6M CH3COOH
Ka(CH3COOH) = 1.8  10–5

Solution: i) The concentration of CH3COOH being appreciable,  will be


negligible in comparison to unity and hence we may use the
approximation.
[H+] = K a  C  1.8  10 5  1
 pH = – log[H+] = – log (1.8  10–5]1/2 = 2.37

ii) We solve this problem by following two methods: one using


approximation and another without it so as to see the difference.

Method 1: Since [H+] due to a weak acid is given by


[H+] = K aC = 1.8  10 5  10 6 = 4.24  10–6
pH = 5.37

Though we seemed to have solved it correctly, there is an error that


we have made. This error can be highlighted by considering the pH of
10–6M HCl. We can see that the pH would be 6. Now, we know that
lesser pH implies higher concentration of H+ ions. So how can a weak
acid having the same concentration as a strong acid disassociate to
give the same concentration of H+ ions.

The mistake has occurred in the assumption that  is very much small
compared to 1. In fact by making this assumption the  that we
calculate is,

Ka 1.8  10 5
= = = 4.24
C 10  6

This value is not possible as  cannot be more than 1, ever.


Therefore, we calculate the pH without this assumption.

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C 2 10 6  2
Method 2: Ka = , 1.8  10–5 =
1  1 
Solving for ,  = 0.95
 [H+] = C = 0.95  10–6 = 9.5  10–7  pH = 6.02
Of course we need to take the [H+] from water also as [H+]acid < 10–6M.

 (x + 9.5  10–7 ) x = 10–14 (Where x is the amount to which water


dissociates in the presence of 10–6M CH3COOH).

x = 1.04  10–8
 [H+]T = 9.5  10–7 + 1.04  10–8
pH = 6.01

This illustration shows a need to know as to when is the assumption


that  is very small compared to 1, valid. This is done in the following
manner.

Ka
First of all calculate the value of  from the expression  =
C

If this value of  comes out to be less than or equal to 0.1, then the
assumption is valid. If the value of  is such that, >0.1, then the
assumption is not valid and one has to calculate  using the quadratic
expression.

4. Hydrolysis of Salts
Salts are the product of an acid and a base, other than water. Depending on the nature of
an acid or a base there can be four types of salts:

i) Salt of a weak acid and a strong base,


ii) Salt of a strong acid and a weak base,
iii) Salt of a weak acid and a weak base and
iv) Salt of a strong acid and a strong base.

We shall first look at what is hydrolysis and then find out how to calculate the pH due to it.

4.1 Salt of a Weak Acid and Strong Base

Let us take a certain amount of weak acid (CH3COOH) and add to it the same amount
(equivalents) of a strong base (NaOH). They will react to produce CH3COONa.

CH3COOH + NaOH  CH3COONa + H2O

CH3COONa being a strong electrolyte, completely dissociates into its constituent ions.

CH3COONa  CH3COO– + Na+

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Now, the ions produced would react with H2O. This process is called hydrolysis.

Na+ + CH3COO– + H2O CH3COOH + NaOH

We know that NaOH is a strong base and therefore it would be completely dissociated to
give Na+ and OH– ions.

 Na+ + CH3COO– + H2O CH3COOH + OH– + Na+

Canceling Na+ on both the sides,

 CH3COO– + H2O CH3COOH + OH–

We can note here that ions coming from strong bases do not get hydrolysed. We
should note here that the solution will be basic. This is because the amount of CH3COOH
produced and OH-– produced are equal. But CH3COOH will not completely dissociate to give
H+ ions. Therefore [OH–] ions will be greater than [H+] ions.

Since the reaction is at equilibrium,

CH3COOH OH  


KC =
 
CH 3 COO 

This equilibrium constant Kc is given a new symbol, Kh.

 Kh 
CH 3COOH  OH 
[CH 3COO  ]
If we multiply and divide the above equation by [H+] of the solution, then

Kh =
CH 3COOH OH H  = H OH 
 

[CH 3COO  ] [H ] [CH 3COO  ] [H ]


[CH 3COOH ]

 Kh =
Kw
 Kh =
CH 3COOH  OH = K w  
Ka [CH 3COO  ] Ka
CH3COO–+H2O CH3COOH + OH–
Initial: C 0 0
At eq: C(1–) C C
Where  is the degree of hydrolysis of CH3COO– ion.
C  C K
 = w
C1    Ka
If  is very much less than 1,
K Kw
C2 = w ,  =
Ka K aC

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Kw K wC
As [OH–] = C, [OH–] = C  
K aC Ka
Kw K wK a

[H+] =
OH   C
 K W  Ka 
or pH = – log [H+] = –log   = 1 pK W  1 pK a  1 log C
 C  2 2 2
 

Now, we will analyse the hydrolysis of this salt in detail. The reactions occurring were,

CH3COOH + NaOH  CH3COONa + H2O …(1)


CH3COONa  CH3COO– + Na+ …(2)
CH3COO– + H2O CH3COOH + OH– …(3)

If we look at the first reaction, we can see that NaOH will be fully ionized as Na + & OH– ions
and CH3COONa as CH3COO– & Na+ ions . Canceling Na+ from both the sides, the first
reaction looks like,

CH3COOH + OH–  CH3COO– + H2O … (4)

You can see clearly that reaction (4) and (3) are the reverse of each other. Therefore,
reaction (4) is also in equilibrium.

 CH3COOH + OH– CH3COO– + H2O … (5)

This actually puts us in a dilemma. If we look at reaction (5) [which is basically the reverse of
reaction (1)], we see that when CH3COOH reacts with OH– the reaction reaches equilibrium.
Now, there are two possibilities: (i) either acetic acid reacts with OH– and the reaction
reaches equilibrium or (ii) acetic acid reacts with OH– and the reaction completely goes to
produced CH3COO– which then gets hydrolyses (by going in the reverse direction) and
finally reaches equilibrium. On close scrutiny we would realize that the first possibility is
more realistic. It is not logical for a reaction to completely go to the right and then go reverse
to reach equilibrium. Now, if the first explanation is correct then we find that actually no
hydrolysis has taken place. What has happened is that the first reaction has not gone to
completion and has reached equilibrium.

Apart from this difference, both the explanation would give us the same result in terms of pH
calculation. For example, we can see that if a certain amount of CH3COOH reacts with the
same amount (equivalents) of OH– ions and the reaction reaches equilibrium, then equal
amounts (equivalents) of OH– ions and CH3COOH would be left over. This is a similar
situation which we encountered earlier in hydrolysis. We can see that this solution would be basic.

To conclude we can say that hydrolysis of a salt occurs only when the salt is dissolved in water.

Illustration 3: 100 mL 0.1 M CH3COOH is titrated with 0.1 NaOH solution. Calculate the pH
of the solution at the equivalence point. Given pKb (CH3COO–) = 9.26.

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Solution: The equivalence point will reach when 100 mL 0.1 M NaOH solution is
added
100 mL 0.1 M CH3COOH  10 milli mole CH3COOH
100 mL 0.1 M NaOH  10 millimole NaOH
10 millimole CH3COOH will react with 10 millimole NaOH to form 10
millimole salt (CH3COONa).
CH3COOH + NaOH  CH3COONa + H2O
10 millimole 10 millimole 0 (initially)
0 0 10 millimole (after
completion of
the reaction)
No. of mil lim ole 10
Molarity of salt solution = = = 0.05
Volume of solution (mL ) 200
The anion of the salt being a conjugate base of weak acid, the same must
be very strong and will undergo hydrolysis to furnish free OH– ions in
solution according to the equation.
CH3COO– + H2O CH3COOH + OH–
The pOH of the resulting alkaline solution can be given as
1
pOH = [pKw – pKa – logC]
2
1
= [14 – 4.74 – log0.05] = 5.28
2
 pH = 14 – 5.28 = 8.72
Note that pKa + pKb = pKw, so pKa = pKw – pKb = 14 – 9.26 = 4.74

4.2 Salt of a Weak Base and a Strong Acid

Let the acid be HCl and the base be NH4OH.


Therefore the salt would be NH4Cl.
NH4Cl completely dissociates into NH 4 and Cl– ions.

NH4Cl  NH 4 + Cl–

Cl– + NH 4 +H2O NH4OH + HCl


HCl being a strong acid dissociates completely to give H+ ions and Cl– ions.
 Cl– + NH 4 + H2O NH4OH + H+ + Cl–

NH 4 + H2O NH4OH + H+

We can see that the ion coming from the strong acid does not get hydrolysed. We had
previously seen that the ion coming from the strong base also does not get hydrolysed.
Hence, one can conclude that the salt of a strong acid and weak base does not get
hydrolysed.

In this hydrolysis, NH4OH and H+ are being produced. This implies that the solution is acidic.
To calculate pH,

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NH 4 + H2O NH4OH + H+
Initial: C 0 0
At eqb: C(1–) C C

Where  is the degree of hydrolysis of NH 4 .

Kh =
NH 4OHH 
[NH 4 ]
Multiplying and dividing by OH– and rearranging,

Kh =
  
NH 4 OH H OH   H  OH  = K w   
[NH 4 ] [OH  ] [NH 4 ] [OH  ] Kb
[NH 4 OH]
Kw
 Kh =
Kb
Now, substituting the concentrations,

Kh =
NH 4OHH   K w 
C  C C 2

[NH 4 ] Kb C1    1  
K
If   0.1, then, C2 = w
Kb
Kw
=
K bC
Kw K wC 1 1 1
Since [H+] = C, [H+] = C = or pH = pK W  pK b  log C
K bC Kb 2 2 2

4.3 Salt of a Weak Acid and Weak Base

Let the weak acid be CH3COOH and the weak base be NH4OH. Therefore, the salt is
CH3COONH4.

The salt completely dissociates.

CH3COONH4  CH3COO– + NH 4

The ions get hydrolysed according to the reaction.

CH3COO– + NH 4 + H2O NH4OH + CH3COOH


Initial : C C 0 0
At equilibrium: C(1–) C(1–) C C

Kh =
NH 4OHCH 3COOH 
[NH 4 ] [CH 3COO  ]

Multiplying and dividing by H+ & OH– and rearranging,

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Kh =
NH 4OHCH 3COOH  H OH   H OH 
 

Kw
 
[NH 4 ]  
[CH 3COO ] [H ] [OH ] 
[CH 3COO ] [H ] [NH 4 ]
[OH ] 
K aK b

[CH 3COOH ] [NH 4OH]
Kw
 Kh =
K aK b

Substituting the concentration terms,

Kh =
Kw

C  C

C 
2

2



Kw
K aK b C 1    C 1    C 1    2
1   2
1  K aK b

There is an important issue that needs clarification before we move on further. In this case,
we can see that both the ions (i.e, cation and anion) get hydrolysed to produce a weak acid
and a weak base (hence, we can’t predict whether the solution is acidic, basic or neutral).
We have considered the degree of hydrolysis of both the ions to be the same. Now we
present an explanation as to why this is incorrect and then state reasons for the validity of
this assumption.

Actually the hydrolysis reaction given earlier,

CH3COO– + NH 4 + H2O CH3COOH + NH4OH

is made up of the following three reactions,

CH3COO– + H2O CH3COOH + OH–


NH 4 + H2O NH4OH + H+
H+ + OH– H2O

If we add these three reactions, the net reaction is the one stated previously. This suggests
that both CH3COO– and NH 4 get hydrolysed independently and their hydrolysis depends on:
K K
(i) Their initial concentration and (ii) the value of Kh which is w for CH3COO– and w for
Ka Kb
NH 4 . Since both of the ions were produced from the same salt, their initial concentrations
K K
are same. Therefore unless and until the value of w and w or Ka and Kb is same, the
Ka Kb
degree of hydrolysis of the ions cannot be same.

To explain why this assumption is valid, we need to now look at the third reaction, i.e.,
combination of H+ and OH– ions. It is obvious that this reaction happens only because one
reaction produced H+ ion and the other produced OH– ions. We can also note that this
reaction causes both the hydrolysis reaction to occur more since their product ions are being
consumed. If you look at the solution of Exercise 1, you will notice that the equilibrium which
has smaller value of equilibrium constant is affected more by the common ion effect. For
the same reason if for any reason a reaction is made to occur to a greater extent by the
consumption of any one product ion, the reaction with the smaller value of equilibrium
constant tends to get affected more.

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Therefore, we conclude that firstly the hydrolysis of both the ions occurs more in the
presence of each other (due to the consumption of the product ions) than in each other’s
absence. Secondly the hydrolysis of the ion which occurs to a lesser extent (due to smaller
value of Kh) is affected more than the one whose Kh is greater. Hence we can see that the
degree of hydrolysis of both the ions would be close to each other when they are getting
hydrolysed in the presence of each other.

Now, to calculate the pH of this solution, we need to understand one more principle. Let us
assume that we have an aqueous solution of CH3COOH. Let us also assume that we do not
know whether CH3COO– and H+ are in the solution or not (even though H+ would be there
since the solution is aqueous). We can see that the Qa for the reaction

CH3COOH CH3COO– + H+ is zero (if we assume no CH3COO– or H+).

 Qa < Ka. The reaction would therefore move forward to reach equilibrium. The same is
true when CH3COO– and H+ are present without CH3COOH. Hence, we conclude that “Any
equilibrium that can exist (i.e., when all reactants and / or all products are present)
will exist (except when pure solids or liquids are not present, in which case this
statement will not be true)”.

As can be seen in the hydrolysis reaction,

CH3COO– + NH 4 + H2O NH4OH + CH3COOH,

CH3COOH is present in the solution. This implies that the equilibrium between CH3COOH,
CH3COO– and H+ can exist and therefore would exist.

CH3COOH CH3COO– + H+

In fact the equilibrium between NH4OH, NH 4 and OH– also exists.

Now, we calculate the pH of the solution as,

CH3COOH CH3COO– + H+

C C(1–)

Ka =
CH COO H  = C1  H   [H ] = K
3
  
+   
  
CH3COOH  C
a
 1  

 KW
Substituting as
1  K aK b

   Kw K wK a
[H+] = Ka   = Ka  =
 1   K aK b Kb
1 1 1
or pH = pK W  pK a  pK b
2 2 2

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5. Buffer Solutions
A buffer solution is a solution which resists a change in its pH when such a change is
caused by the addition of a small amount of acid or base. This does not mean that the pH of
the buffer solution does not change (we make this assumption while doing numerical
problems). It only means that the change in pH would be less than the pH that would have
changed for a solution that is not a buffer.

There are three types of buffer solutions:

i) weak acid–salt buffer


ii) weak base–salt buffer and
iii) salt buffer

5.1 Buffer of a Weak Acid and its Salt with a Strong Base

It is possible to prepare a buffer solution by the addition of a weak acid and a salt of the
acid with a strong base.

We shall explain the buffer action by the following example. Let us consider a buffer solution
made up of CH3COOH and CH3COONa. The weak acid dissociates to a very small extent
more so due to the common ion effect of its salt.

CH3COOH CH3COO– + H+
CH3COONa  CH3COO– + Na+

Now let us assume that a buffer solution contains 20 moles of CH3COOH and 20 moles of
CH3COONa. The salt being a strong electrolyte would completely dissociate while the acid
would be hardly dissociated. We assume that the amount of CH3COO– is 20 moles as the
contribution from CH3COOH would negligible. We also assume that the amount of
CH3COOH to be 20 moles as it would be very weakly dissociated. Therefore the solution
contains 20 moles of CH3COOH and 20 moles of CH3COO– ions.

Let us now add 10 moles of H+ ions to this solution. These 10 moles of H+ ions would react
with the 20 moles of CH3COO– ions to produce 10 moles of CH3COOH. (This is because the
reaction of CH3COOH to give CH3COO– ions and H+ ions has an equilibrium constant value
of approximately 10–5. Therefore, the reverse reaction, that is the reaction of CH3COO– ions
to combine with H+ ions to give CH3COOH would have an equilibrium constant of
approximately 105. So this reaction can be assumed to be complete). These 10 moles of
CH3COOH formed would ionize weakly because it is a weak acid. Moreover due to the
common ion effect of CH3COO– ion (10 moles, left over), it would ionize even less. So the
amount of H+ ion produced back is much less than the 10 moles that were added. So
effectively, 10 moles of H+ ions were consumed and an amount much less than that is
produced back which causes an insignificant change in pH of the buffer solution.

Let us add 10 moles of OH– ions to the same buffer solution containing 20 moles of
CH3COOH and 20 moles of CH3COO– ions. These 10 moles of OH– ions added would be
consumed by the 10 moles of CH3COOH to produce 10 moles of CH3COO– ions

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(CH3COOH + OH–  CH3COO– + H2O. This is because the reverse reaction is the
Kw
hydrolysis of CH3COO– ions which has an equilibrium constant of  10–9.
Ka
So the forward reaction’s equilibrium constant would be 10 , which implies that the reaction
9

is practically complete). The 10 moles of CH3COO– ions produced would be hydrolysed


weakly (due to a very low K value of 10–9). On top of that, the presence of 10 moles of
CH3COOH would further hamper the hydrolysis process and thereby the
OH– ion produced is much less than the amount that was added. This causes a
minor change in pH.

For a buffer to act as a good buffer the amount of CH3COOH and CH3COO– ion should be
high.

The pH of a buffer can be calculated as follows.

Since acetic acid is in equilibrium,

[H ] [CH 3COO  ]


= Ka
[CH 3COOH ]
[H ] [Conjugate base] [ Acid]
 = Ka  [H+] = Ka
[ Acid] [Conjugate base]
[ Acid]
 log [H+] = log Ka + log
[Conjugate base]
[Conjugate base] [Conjugate base]
– log [H+] = – log Ka + log  pH = pKa + log
[ Acid] [Acid]

This equation is called Henderson – Hasselbalch equation.

When a weak dibasic acid is taken then the pH at half neutralisation is given by a special
formula which is derived by balancing charge and mass of reactants and products. For
example, at half neutralisation of H2CO3 by NaOH, the pH is given by

pK a1  pK a 2
pH =
2
Where K a1 and K a 2 are 1st and 2nd dissociation constant of H2CO3.

5.2 Buffer of a Weak Base and its Salt with a Strong Acid

This combination works on the principle as stated in the previous section. If we take the
example of NH4OH and NH4Cl, then the OH– ion added would react with NH 4 (from the salt)
to produce NH4OH. The H+ ion added would react with NH4OH to produce NH 4 .

The Henderson – Hasselbalch equation appears as

[Conjugate base]
pOH = pKb + log
[Acid]

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Exercise 1: a) Calculate the pH after the addition of 90 ml and 100ml respectively of


0.1N NaOH to 100ml 0.1N CH3COOH (Given pKa for CH3COOH = 4.74)
b) What is pH of 1M CH3COOH solution? To what volume must one litre of
this solution be diluted so that the pH of resulting solution will be twice
the original value. Given : Ka = 1.8  10–5

Illustration 4: 100 mL 1 M CH3COOH is treated with 0.8 gm NaOH. Calculate pH of


solution. How much NaOH needs to be added further so as to increase its
pH to 4.74? Will the dilution of the mixture will change the pH of solution
(Ka = 1.8  10–5).

Solution: 100 mL 1M CH3COOH  100  1 i.e. 100 millimoles of CH3COOH

800
0.8 gm i.e. 800 mg NaOH  i.e. 20 millimoles of NaOH
40

20 millimoles NaOH will react with 20 millimoles CH3COOH leaving


behind 80 millimoles of free CH3COOH. The mixture will be thus, an acid
buffer mixture whose pH can be calculated using the equation.

[salt ]
pH = pKa + log
[acid]
20
= – log (1.8  10–5) + log
80
= 4.74 – 0.60 = 4.14

[salt ]
To make the pH of solution equal to 4.74, must be equal to 1. The
[acid]
acid present in the original acid solution is 100 millimoles. So we have to
50  40
add 50 millimoles i.e. g (=2g) of NaOH. Thus the amount of
1000
NaOH to be added further is 2 – 0.8 i.e. 1.2g.

[salt ]
Upon dilution the ratio and also pKa will remain unchanged and
[acid]
hence pH of solution will remain unchanged.

5.3 Indicators

Ostwald Theory of Indicator: An indicator, generally organic weak acids or weak bases, is
a substance which is used to determine the end point in a titration. They change their colour
within certain pH range. Generally, the colour change is due to shifting indicator equilibrium.

e.g. for phenolphthalein


HPh H  Ph
Colourless Pink

Shifting of this equilibrium from left to right produces pink colour.

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[H ][Ph ]
Indicator constant = [KIn ] 
[HPh]
[Ph ]
and pH = pKIn  log
[HPh]
At equivalence point [HPh] = [Ph–]

pH  pKIn or KIn  [H ]

Illustration 1: An acid type indicator HIn differs in colour from its conjugate base (I–n). Human
eye is sensitive to colour differences only when the ratio [[I n–]/[HIn] is greater
than 10 or smaller than 0.1. What should be the minimum change in the pH of
the solution to observe a complete colour change (Ka = 1.0  10–5)?

Solution: The two conditions when colour of indictor will be visible.


[In ]
pH  pKIn  log
[HIn ]
i) pH   log10 1 105  log10 (10)  6
ii) pH   log10 105  log10 (0.1)  4
Thus minimum change in pH = 6 – 4 = 2

5.4 Salt Buffer

The fundamental principle behind a buffer action is the fact that on adding an acid the
system consumes the H+ ion added to produce a weak acid and on adding a base, it
consume the OH– ion added to produce a weak base. This ensures that H+ or OH– ion
added is consumed and the weak acid or the weak base produced gives less H+ or OH– ion
as they are weak.

Based on this principle, a solution of a salt of a weak acid and weak base is also called as a
buffer. Let us take the example of CH3COONH4. It dissociates as,
CH3COONH4  CH3COO– + NH 4 . When H+ ion is added, CH3COO– ion consumes it to
give CH3COOH. When OH– ion is added, NH 4 ion consumes it to give NH4OH. Hence it
acts as a buffer.

K wK a
[H+] = (derived earlier).
Kb

6. Solubility and Solubility Product


Here we discuss the solubilities of ionic solutes. When a salt is dissolved in water, it
dissolves as the salt, AgCl (s)  AgCl(aq) and then the dissolved salt dissociates to give
the ions AgCl (aq)  Ag+ (aq) + Cl–(aq). After a certain amount of the salt has been
dissolved, the solution would become saturated with the salt. Now, if some more of the salt
is dissolved, the salt would dissolve to give ions while at the same time the ions would

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precipitate to give back the salt. This amount (moles) of the salt that has made the solution
saturated per liter of solution is called the solubility of the salt.

AgCl (s) Ag+(aq) + Cl– (aq)


[ Ag ] [Cl  ]
K =
[ AgC]
Since the concentration of AgCl, which is a solid, is constant,
 K[AgCl] = [Ag+] [Cl–] = KC

This KC is given the symbol, KSP. This means that a solution cannot have the product of the
concentration of Ag+ and Cl– to be more than KSP (called solubility product).

6.1 Calculation of Solubilities of Salts

We shall now discuss the solubilities of different types of salts under various conditions.

i) Solubilities of AgCl (salt of a strong acid and strong base) in water:

AgCl would dissolve in water as,


AgCl (s)  Ag+ (aq) + Cl– (aq)
At saturation point,
AgCl (s) Ag+(aq) + Cl– (aq)
If the solubility of the salt is x moles / l
 [Ag+] = xM, [Cl–] = xM  x2 =Ksp
x= K sp

ii) Solubility of AgCl in a solution that is having 0.1M in AgNO3:

AgCl would dissolve and finally reach saturation.

AgCl(s) Ag+(aq) + Cl– (aq)

The Ksp of AgCl is approximately 10–10 . If AgCl were to be dissolved in water (pure), its
solubility would have been 10–5M (previous section). In the presence of 0.1M AgNO3 its
solubility will decreases due to common ion effect. This means that [Ag +] from AgCl
would be less than 10–5 M. Hence, we can ignore the contribution
of Ag+ from AgCl.

If the solubility of AgCl is x  moles / l in the presence of 0.1M AgNO3, then

[Ag+] = 0.1M , [Cl–] = x  M

K sp
 x = = 10–9 moles / l
0 .1

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iii) Solubility of CH3COOAg (salt of weak acid and strong base) in water:

CH3COOAg dissolves and reaches saturation. Since it is a salt of weak acid and strong
base, it would hydrolyse. If the solubility of the salt is x moles/ l then

CH3COOAg (s) CH3COO– (aq) + Ag+ (aq)


At eqb: x –y x

CH3COO– (aq) + H2O CH3COOH (aq) + H+ (aq)


At eqb: x –y y y

Where y is the amount of CH3COO– ion that is hydrolysed.

 (x –y) x = Ksp
y2 K
= w
x  y  K a
Knowing the values of Ksp and Ka, solubility of the salt can be calculated.

iv) Solubility of CH3COOAg (salt of a weak acid and strong base) in an acid buffer of
pH = 4 (assuming that the buffer does not have any common ion by CH3COOAg):

CH3COOAg would dissolve and reach equilibrium. It would then be hydrolysed. If the
solubility of the salt is x  M in this solution, then

At eq.; CH3COOAg (s) CH3COO– (aq) + Ag+ (aq)


x –y x

CH3COO– (aq) + H+ CH3COOH (aq)


x – y 10–4 y

Since the solution is a buffer, the pH will be maintained.


( x  – y) x  = Ksp
y 1
=
10  x  y
4
Ka

Since in presence of basic buffer, the degree of hydrolysis will be suppressed by already
existing –OH ions, therefore the approximated formula which can be used is

X2 = K sp
 (CH3COOAg) (neglecting y)

Knowing Ksp and Ka, the solubility can be calculated.

v) Solubility of CH3COOAg in an buffer solution of pH = 9:

Following the same logic as give in the earlier section,

CH3COOAg (s) CH3COO– (aq) + Ag+ (aq)

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At eqb: x –y x 

CH3COO (aq) + H2O CH3COOH + OH–
At eqb: x  – y y 10–5

Where x M is the solubility of the salt and y the extent to which it is hydrolysed.

( x  – y) x  = Ksp

y  10 5 K
= w
( x  y) Ka

Knowing, Ksp and Ka, the solubility can be calculated.

vi) Solubility of AgCl in an aqueous solution containing NH3.

Let the amount of NH3 initially be ‘a’ M. If the solubility of the salt is x moles/ l, then

AgCl (s) Ag+ (aq) + Cl– (aq)


At eq: x –y x
Ag+(aq) + 2NH3 (aq) Ag(NH3)2+(aq)
x–y a–2y y

Where y is the amount of Ag+ which has reacted with NH3.

( x –y) x = Ksp
y
= Kf ( formation constant of Ag(NH3)2+)
x  y a  2y  2

Knowing Ksp and Kf , the solubility can be calculated.

6.2 Precipitation of salts

For a salt (sparingly soluble) when dissolved in water : AB A+ + B– at equilibrium


(saturation) Ksp = [A+] [B–]

When, we mix ions or if there be two or more ions in water, we define reaction coefficient
(Q), called as a ionic – product (IP) in this case, giving the products of ions in water (ions of
soluble salts and other common ions).

I.P. is product of ionic concentration due to ions already present in water or from a salt. I.P.
may be and may not be equal to Ksp. To illustrate it more clearly , consider a case when 500
ml of an 0.005 M solution of AgNO3 is added to 500 ml of 0.001 M solution KCl. Now in
solution (mixture), there are Ag+, NO 3 , K+ and Cl– ions. The concentration of [Ag+] = NO 3  
0.001
= 0.005 = 0.0025 M (equal volumes are mixed) and [K+] = [Cl–] =
2
= 0.0005 M as equal volumes of two solutions are mixed.

Now, we know that Ag+ will react with Cl– ions to form AgCl since:

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AgCl Ag+ + Cl– is a reversible reaction with a higher tendency towards left (solidifying
or precipitating).

Now, question is, whether AgCl will be formed or not (precipitation of Ag+ and Cl– as AgCl)
and if it formed, how much of it will be formed? For this we define some rules .

1. If ionic Product (IP)  Ksp ; precipitation takes place till I.P. equals Ksp

2. If Ionic Product  Ksp ; a precipitate will not be formed and the solution will be
unsaturated

3. If Ionic Product = Ksp ; a precipitate will not form an the solution is satuated in that salt.
(or we can say that solution is at a critical stage, when precipitation just begins, but
actually has not occurred yet in real sense).

In present case,

I.P. = [Ag+] [Cl–] = (0.0025) (0.0005) = 1.25  10–6

(Only for the salt which is sparing soluble not for KNO3)

Ionic Product  Ksp in this case (Ksp AgCl = 1.56  10–10)

Which mean precipitation takes place.

Exercise 2: a) The solubility of CaF2 in water at 20C is 15.6 mg per dm3. Calculate the
solubility product of CaF2.
b) The solubility of BaSO4 in water is 2.3  10–4 gm/100 mL. Calculate the
percentage loss in weight when 0.2 gm of BaSO 4 is washed with (a) 1lt
of water (b) 1lt of 0.01 NH2SO4.

Illustration 5: 20 mL 0.1 M solution of a dibasic acid H2XO3 (K1= 1  10–6) and K2 =1  10–11)
is titrated with 0.2 M NaOH solution. Calculate pH of solution when (a) 5 mL
and (b) 20 mL alkali had been added.

Solution: 20 mL 0.1 M H2XO3  2 millimole of H2XO3

a) When 5 mL 0.2 M NaOH i.e. 1 millimole of NaOH has been added,


1millimole of NaHXO3 will be formed and 1 millimole of H2XO3 will
remain free.

H2XO3 + NaOH  NaHXO3 + H2O


2 millimole 1 millimole 0 initially
1 millimole 0 10 millimole
when reaction
is complete.
The resulting mixture will be an acid buffer mixture whose pH is as
calculated below:
[salt ] 1
pH = pK1 + log = 6 + log = 6
[acid] 1

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b) 10 mL 0.2 M NaOH  2 millimole

2 millimole NaOH will react with 2 millimole H2XO3 to give 2 millimole


NaHXO3 ( an acid salt). It is a point of half neutralisation.

H2XO3 + NaOH  NaHXO3 + H2O


2 millimole 2 millimole 0
0 0 2 millimole

The resulting solution will be the solution of NaHXO3. HXO3– is an


amphiprotic anion i.e. it furnishes H+ ion in solution as an acid and
HXO3– ion being a conjugate base of weak acid is a strong base
which gets hydrolysed to give OH– ion in solution as

HXO3– H+ + XO32–
HXO3–+ H2O H2XO3 + OH–

Na+ ion is unhydrolysable. The pH of such a salt solution may be


calculated using the equation

pK1  pK 2 6  11
pH =  = 8.5
2 2

c) 20 mL 0.2 M NaOH  4 millimole

4 millimole NaOH will react with 2 millimole H2XO3 to give 2 millimole


Na2XO3. Thus it is the equivalence point of the titration.

XO32– being the conjugate base of a very-very weak acid HXO3– ion is
a very-very strong base and in aqueous solution it would get
hydrolysed to give free OH– ions in solution.

K w 10 14
XO32– + H2O HXO3– + OH–, Kh =   10  3
K 2 10 11

HXO3– being a conjugate base of weak acid H2XO3 is also a strong


base and will hydrolyse as

K w 10 14
HXO3– + H2O H2XO3 + OH–, Kh =  = 10–8
K1 10 6

The hydrolysis constant XO32– ion being for more greater than that of
HXO3–, it is wiseful to neglect the hydrolysis of HXO3– so as to simplify
the calculation. The pOH of the resulting solution can be calculated
using the formula of hydrolysis.

1
pOH = [pKw – pK2 – logC]
2

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2
Molarity of Na2XO3 solution (C) = = 0.05
40
1 1
 pOH = [14 – 11 – log 0.05] = [14 – 11 + 1.30] = 2.15
2 2
 pH = 14 – pOH = 14 – 2.15 = 11.85

Illustration 6: The solubility of the sulphide of a trivalent metal in water at 25°C is 20.0 mg
per dm3. Calculate its solubility in 0.5 M solution of Na2S assuming
complete dissociation of Na2S. (M = 52 and S = 32)

Solution: Molecular formula of metal sulphide = M2S3


Molecular weight of metal sulphide = 52  2 + 32  3 = 200
Solubility in mole per dm3
20  10 3
= = 10–4
200
M2S3(s) 2M3+ + 3S2–
2  10–4 3  10–4
Ksp = [M3+]2 [S–2]3 = (2  10–4)2 (3  10–4)3 = 1.08  10–18

0.5 M Na2S being completely dissociated will give 0.5 M S2– in solution.
The S2– ion will exert common ion effect on the solubility of M2S3 and
hence the solubility of M2S3 will decrease.

Let the solubility of M2S3 in 0.5 M Na2S is S mole per dm3


M2S3(s) 2M3+ + 3S2–
2S 3S + 0.5
Ksp will remain unchanged
(3S + 0.5)3 (2S)2 = 1.08  10–18
S being very small in comparison to 0.5, the above equation may be
simplified as
(0.5)3 (2S)2 = 1.08  10–18

1.08  10 18
S= = 1.47  10–9 mole per dm3
4  0.5  0.5  0.5

7. pH of Mixtures of Acids & Bases


Let us take x millimoles of acid (HA) and y millimoles of base (BOH). Note that acid is
monobasic and base is monoacidic.

a) Strong acid & Strong base

 If x = y; then complete neutralization takes place and we get x(=y) millimoles of salt
(BA) of strong acid and strong base which means no hydrolysis takes place and pH
of solution = 7.

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 If x  y; then there is an excess of strong acid and resulting solution is acidic with
millimoles of acid left in excess = x – y.

Now if V c.c. be the volume of mixture, then:


xy
M= . Now calculate pH using the equation pH = – log [H+]
V

 If x  y; then there excess of strong base and resulting solution is basic with
millimoles of base = y – x.

b) Strong base & weak acid

 If x = y; first of all neutralization takes place to give x(=y) millimoles of salt (BA). The
salt will now undergo hydrolysis to give an alkaline solution. Calculate pH by using
standard result:
1
pH = 7 + (pKa + log C); C is concentration expressed in M (mol/lt)
2

 If x  y; there is excess of weak acid whose millimoles = x – y and y millimoles of


salt is formed. This will give an acidic buffer solution. Calculate pH of buffer solution
using Henderson’s Equation.
[salt ] y
PH = pKa + log  pKa + log
[acid] xy

 If x  y; the solution in this case contains excess of strong base whose millimoles are
y – x.
yx
M= . Calculate pH.
V

c) Strong acid & Weak base

 If x = y; first of all complete neutralisation takes place to produce x(=y) millimoles of


salt (BA). The salt (BA) is of strong acid and weak base, hence hydrolysis takes
place to give an acidic solution. Calculate its pH by using standard result.
1
pH = 7 – (pKb + log C) ; C: is concentration of salt.
2

 If x  y; then solution contain excess of strong acid whose millimoles = x – y.


xy
M= . Calculate pH.
V

 If x  y; then there is an excess of weak base whose millimoles are y – x and


millimoles of salt (BA) are x. This will give a basic buffer solution. Calculate the pH by
using Henderson’s Equation.

[salt ] x
pH = 14 – pKb – log = 14 – pKb – log
[base] yx

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d) Weak acid & weak base

 If x = y; neutalisation takes place completely with the formation of x (=y) millimloles of


salt (BA) of weak acid and weak base. So hydrolysis takes place. Calculate the pH
by using:

1
pH = 7 + (pKa – pKb)
2

 If x y; then excess of weak acid (x – y) will remain with y millimoles of salt. This will
give an salt buffer with acidic pH.

 If x y; then excess of weak acid (y-x) and x millimoles of salt. This will give a salt
buffer with basic pH.

8. Solution to Exercises
Exercise 1: a) If 90 ml. Of .1N NaOH is added to 100 ml. Of .1N CH3COOH, acidic
buffer will form as

H3CCOOH + NaOH  H3COONa + H2


t=0 .01 eq. .009 eq. 0 0
.001 eq. 0 .009 eq.

[CH 3COO ]
pH = pKa + log
[CH 3COOH ]
9
= 4.74 + log = 4.74 + .9542 = 5.694
1

If 100 ml of 0.1N NaOH is added to 100 ml of 0.1N CH3COOH,


complete neutralisation takes place and the concentration of
H3COONa
0 .1
= M = .05M
2
1 1
Now, pH = 7 – pKa – log C
2 2
pH = 5.28

b) H3COOH + H2O H3COO– + H3O+


t=0 1M 0 0
-xM xM xM
——————————————————————————
t = teq (1-x)M x x
2 2
x x
Ka = 
1 x 1

x= K a = 4.2  10–3 = [H3O+]

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pH = – log [H3O+] = – log {4.2  10–3} = 3 – log 4.2 = 2.37

Now, let 1L of 1M ACOH solution be diluted to VL to double the pH


and the conc. of diluted solution be C.

H3COOH + H2O H3COO– + H3O+


t=0 C 0 0
– 1.8  10–5 1.8  10–5 1.8  10–5
——————————————————————
t=teq C– 1.8  10–5 1.8  10–5 1.8  10–5

New pH = 2  old pH
= 2  2.37 = 4.74
pH = – log [H3O+] = 4.74
 [H3O+] = 1.8  10–5
[CH 3COO  ]  [H3O ]
Ka =
[CH 3COOH ]
1.8  10 5  1.8  10 5
1.8  10–5 =
C  1.8  10  5
 C = 3.6  10–5 L
on dilution
M1V1 = M2V2
1M  1L = 3.6  10–5 L  V2
 V2 = 2.78  104 L

Exercise 2 a) Solubility in moles per dm3

=

15.6  10 3 
= 2.0  10–4
(78 g / mol )
Since CaF2 Ca2+ + 2F–
Therefore, [Ca2+] = 2.0  10–4
and [F–] = 2  2.0  10–4
Hence, solubility product
Ksp = [Ca2+] [F–]2 = (2.0 10–4) (4.0  10–4)2 = 32  10–12

b) i) Solubility is in general expressed in gm/lt,


so solubility of BaSO4 = 2.3  10–3 g /lt
Loss in weight of BaSO4 = amount of BaSO4 soluble
2.3  10 3
 %loss =  100 = 1.15%
.2
ii) Now 0.01 NH2SO4  0.01 NSO 24 ions
 0.005 M SO 24 ions
Now presence of SO 24 prior to washing BaSO4 will suppress the
solubility of BaSO4 (due to common ion effect). The suppression
will be governed by Ksp value of BaSO4. Sof first calculate Ksp of
BaSO4.

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Solubility of BaSO4 in fresh water = 2  10–3 g/lt


2.3  10 3
 = Mol/lt = 9.85  10–6 M
233 .4
 
Ksp = [Ba2+] SO 24 = (9.85  10–6)2 = 9.71  10–11
Now let x be solubility in mol/lt

 [Ba2+] in solution = x mol/lt and SO 24 in solution 
= (x + 0.005) mol/lt
 
Ionic product = [Ba2+] SO 24 = (x) (x + 0.005)
Ksp = Ionic Product at equilibrium (saturation)
 9.71  10–11 = (x) 9x + 0.005)  x2 + 0.005 x - 9.71  10–11 = 0
9.71 10 11
x= = 1.94  10–8 mol/lt = 1.94  10–8  233.4 g/lt
0.005
 4.53  10–6 gm of BaSO4 are washed away
4.53  10 6  100
 percentage loss = = 2.26  10–3%
0.2

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9. Solved Problems
9.1 Subjective

Problem 1: Calculate the concentration of fluoroacetic acid which is required to get [H+] =
1.50  10–3 M, Ka of acid = 2.6  10–3.

Solution: CH2FCOOH CH2FCOO + H+


C 0 0
C(1 – ) C C
 
[CH2FCOO ][H ] (C)(C) C2
Ka   
[CH2FCOOH] C(1  ) (1  )
C. 1.50  103  
 2.6  103   (C = 1.5  10–3)
(1  ) (1  )
  = 0.634
1.50  103
C = 1.5  10–3  C   2.37  103 M
0.634
As Ka is of the order of 10–3, hence  cannot be neglected with
respect to 1.

Problem 2: The pH of 0.05 M aqueous solution of diethyl amine is 12.0. Calculate K b.

Solution: Diethylamine is base and gives OH–


(C2H5)2NH + H2O C2H5NH2+ + OH–
C 0 0
C(1 – ) C C
[OH–] = C = 10–2 M (pH = 12, pOH = 2, [OH–] = 10–2]
 0.05   = 10–2
  = 0.2
C2 0.05  (0.2)2 0.05  0.04
Kb     2.5  103
(1  ) (1  0.2) 0.8
Kb  C cannot be used because
2

 = 0.2 and (1  ) = 0.8

Problem 3: Two buffers (X) and (Y) of pH 4.0 and 6.0 respectively are prepared from acid
HA and salt NaA. Both the buffers are 0.50 M in HA. What would be the pH of
the solution obtained by mixing equal volumes of the two buffers?
(KHA = 1.0  10–4).

[salt]
Solution: pH = pK a  log
[acid]
[A]
Case 1: 4 =  log1.0  105  log
[0.5]
[salt]
 log  1  [salt]  0.1 0.5  0.05M
0.5

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[salt]
Case 2: 6   log1.0  105  log
0.5
[salt]
 log  1 [salt]  10  0.5  5M
0.5
For buffer (i) [HA] = 0.5 M
[NaA] = 0.05M
For buffer (ii) HA] = 0.5 M
[NaA] = 5M
0.05  V  5  V 5.05
New concentration of NaA in mixed buffer = 
2V 2
0.5  V  0.5  V
New conc. of HA in mixed buffer =  0.5M
2V
(5.05 / 2)
 pH   log1.0  105  log  5  0.7033
0.5
 pH = 5.7033

Problem 4: A 500 mL sample of 0.0152 M Na2SO4(aq) is added to 50.0 mL of 0.0125 M


Ca(NO3)2(aq).
i) Should precipitation of Ca(SO4)(s) occur?
ii) Will precipitation of Ca2+ be complete?
2 2
CaSO4(s) Ca(aq)  SO4(aq) , Ksp = 9.1  10–6

Solution: i) The concentration of ions present after mixing


0.15  50
[SO24 ]   7.6  103 M
100
0.0125  50
[Ca2 ]   6.25  103 M
100
Ionic product, [Ca2+] [SO42–] = 6.25  103  7.6  103
= 4.7  105  K sp
As, ionic product [Ca2+] [SO42–] is greater than Ksp hence precipitation of
CA(SO4)(s) will occur.

ii) Let at eqm. [Ca2+] = x M


 [Ca2+] used = (6.25  103  x)M
[SO42 ] used  (6.25  103  x)M
[SO24 ]left  7.6  103  (6.25  103  x)  (1.35  103  x)M
2 
Ca(SO4 )(s) Ca(aq)  SO24(aq)
Initial 6.25  10–3M 7.6  10–3M
At eqm. x (1.35  10–3 + x)
[Ca2 ][SO24 ] = Ksp
 x(1.35  103  x)  9.1 106
 x2  1.35  103 x  9.1 106  0

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On solving x = 2.4  103 M


[Ca2 ]  2.4  103 M
2.4  103
% of calcium ion left in solution =  100  38.4%
6.25  103
Hence precipitation is incomplete.

Problem 5: Calculate for 0.50 M aqueous solution of sodium cyanide


a) Hydrolysis constant
b) Degree of hydrolysis
c) pH (pKb (CN–) = 4.40)

Solution: NaCN  H2O NaOH  HCN


Initial 1 0 0
Final (1 – h) h h
K w K w  Kb
KH   ( Ka  Kb  K w )
Ka Kw
KH  Kb  2  105 (pKb  4.70)
KH 2  105
b) h    6.3  103
C 0.5
c) [OH ]  c  h  0.5  6.3  103
 pOH 2.5
pH  11.5


Problem 6: Given Ag(NH3 )2 Ag  2NH3 , K c  6.2  108 and Ksp pf AgCl = 1.8  10–10
at 298K. Calculate the concentration of complex in 1.0 M aqueous ammonia.

 
Solution: Ag(NH3 )2(aq) Ag(aq)  2NH3(aq)
(a + b) 2a
 
AgCl(s) Ag  Cl(aq)
(aq)

(a + b) b
In case of simultaneous solubility Ag+ remains same in solution
(a  b)  2a
Kc  …(1)
[Ag(NH3 )2 ]
Ksp = (a + b)  b …(2)
From (i) and (ii)
Kc 2a

K sp [Ag(NH3 )2 ]  b
Given [NH3] = 2a = 1M also [Ag(NH3 )2 ]  [Cl ]  b because Ag+ obtained from
AgCl passes in Ag[NH3 )2 ] state
Kc 1
 
K sp b  b

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1.8  1010
 b2   0.2  102  b = 0.0539
6.2  108
or [Ag(NH3 )2 ]  0.0539

Problem 7: The average concentration of SO 2 in the atmosphere over a city on a certain


day is 10 ppm. When the average temperature is 298K. Given that the solubility
of SO2 in water at 298K is 1.3653 mol/litre and pKa of H2SO3 is 1.92, estimate the
pH of rain on that day.

Solution: Concentration of SO2 in air is 10 ppm. The concentration of SO2 in air being
substantial and since rain water is falling from enormously great height each
drop of rain water will get saturated with SO2 before it reaches earth

Thus [SO2] = [H2SO3] = 1.3653 mol/litre


SO2  H2O  H2SO3
H2SO3 2H  SO32
C 0 0
 x x
c  2  x
  2
x  x / 2 x3
2
K a  101.92   (x is veryvery small)
 x  2c
c  2 
 
 x  (1.3653  2  101.92 )1/ 3  [H ]
pH   log[H ]  0.49

Problem 8: 20 mL of a weak monobasic acid requires 30 mL 0.2 M NaOH for the end point.
The pH of solution upon addition of 12 mL 0.2 M NaOH during the titration was
found to be 6.2. Find pH of the stock solution of the weak monobasic acid.

Solution: 30 mL 0.2 M NaOH  30  0.2 i.e 6 millimoles NaOH

Weak acid being monobasic and NaOH being monoacidic, they will react
together in 1:1 molar proportion. Thus 20 mL solution of weak monobasic
acid will contain 6 millimole of that acid.

6
Molarity (C) of weak acid solution = = 0.3
20

When 12 mL 0.2 M NaOH i.e 12  0.2 (= 2.4) millimole of NaOH is added to


acid solution, 2.4 millimole of acid will react with 2.4 millimole of acid to form
2.4 millimole of sodium salt of the acid. The acid remaining unreacted will be
3.6 (= 6 – 2.4) millimole. The mixture will be an acid a buffer mixture, the pH
of which will be as given below.

[salt ]
pH = pKa + log
[acid]

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2 .4
6.2 = pKa + log
3 .6
 pKa = 6.2 + 0.176 = 6.376
[H+] = C = K a  C (neglecting  in comparison to unity)
1 1
pH = –log (KaC)1/2 = [pKa – logC] = [6.376 – log 0.3]
2 2
1
= [6.376 + 0.522] = 3.45
2

Problem 9: The pH 0.1 M aqueous solution of a 2° amine is 11 at 25°C. Calculate its Kb.


Solution: R2NH + H2O R 2 NH2 + OH–
Initial conc. 0.1 M Excess 0 0
Equilibrium conc. (0.1 – x)M Constant xM xM
pH + pOH = 14 (at 25°C)
pOH = 14 – 11 = 3
 [OH–] = 10–3M
Thus x = 10–3
The equilibrium constant of the above ionic equilibrium is base dissociation
constant (Kb) of the 2°–amine given as

[R NH2 ][OH  ] x2 10  3  10  3 10  6
Kb = 2   3
 = 1.01  10–5
[R2NH ] 0.1  x 0.1  10 0.099

Problem 10: 100 mL 1.0 M HA (Ka = 2.0  10–5) and 100 mL 0.1 M HCl are mixed together.
Find pH of the resulting mixture. What will be the effect of adding (a) 55.0 mL
1.0 M KOH solution is added and (b) 55.0 mL 2.0 M KOH solution, are added to
the above acid mixture?

Solution: Upon mixing 100 mL each of 1.0 M HA and 0.1 M HCl, the conc. of each
specie will be halved. HCl (a strong acid) will ionise completely and H+ ion
thus produced will exert common ion effect on the dissociation equilibrium of
HA, a weak acid as evident from its Ka.
HA H+ + A–
Initial conc. C 0 0
Equilibrium conc. C(1 – ) (C + 0.05) C
(C  0.05 )C
Ka =
C(1   )
 being very small due to common ion effect, may be neglected in
comparison to unity. Thus
Ka = (C + 0.05)
2.0  10–5 = (0.5 + 0.05)
0.05 2 + 0.05  – 2.0  10–6= 0
 = 3.998  10–5
[H+] = C + 0.05
pH = 1.3

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a) pH upon addition of 55.0 mL 1.0 M KOH:


Addition of 55.0 mL 1.0 M KOH means the addition of 55 millimole KOH.
10 millimole of this would first neutralise (100 mL 0.1 HCl) 10 millimole of
HCl, present in the mixture. Remaining 45 millimole of will react with 45
millimoles of weak acid present in the mixture forming 45 millimoles of
salt (KA). Total amount of weak acid present is 100 mL 1.0 M i.e. 100
millimole. Thus 55 millimole of weak acid will remain unreacted. The
[salt ] 45
resulting mixture will be an acid buffer mixture with  . The pH
[acid] 55
is, therefore, calculated as

[salt ] 45
pH = pKa + log = 6 + log = 5.91
[acid] 55

pH = 5.91 – 1.3 = 4.61

b) pH upon addition of 55 mL 2.0 M KOH:


55 mL 2.0 M KOH i.e. 110 millimoles KOH will neutralize both the acids
completely the total amount of which in the mixture is 110 millimoles. Also
since both the acids are monobasic and KOH is monoacidic so reaction
will occur in equimolecular proportion. Salt (NaA) formed will be 100
millimole.

The volume of solution = 255 mL


100
Molar conc. (C) of NaA in solution = = 0.392
255

The salt of weak acid with a strong base will hydrolyse to give free OH – in
solution rendering the solution alkaline. The pOH of the solution will,
therefore, be calculated using the formula of salt hydrolysis.

1
pOH = [pKw – pKa – logC]
2
1
= [14 – 6 – log 0.592]
2
1
= [14 – 6 + 0.406
2
= 4.203
pH = 14 – 4.203 = 9.79
pH = 9.79 – 1.3 = 8.49

Problem 11: Determine the number of moles of AgI which may be dissolved in 1 L of 1 M
CN– solution. Ksp for AgI and Kf for [Ag(CN)2]– are 1.2  10–7 M2 and
7.1  1019 M–2 respectively.

Solution: The relevant equilibrium with problem and the overall equilibrium is as given
below.

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AgI(s) Ag+ + I– Ksp = 1.2  10–7 M2


Ag+ + 2CN– [Ag(CN)2]– Kf = 7.1  1019 M–2
––––––––––––––––––––––––––––––––––––––––––––
AgI(s) + 2CN– [Ag(CN)2]– + I– K = 1.2  7.1  1012
Initilaly 1M 0 0 = 8.52  1012
At equilibrium (1 – 2x)M xM xM
–1
Where x is the solubility of AgI in mole L
x2
= 8.52  1012
(1  2x ) 2

x
 = 2.91  106
1  2x
 x = 2.91  106 – 5.82  106x
 x + 5.82  106x = 2.91  106
 5.82  106x = 2.91  106
2.91 10 6
 5.82  106x = 2.91  106  x = = 0.5
5.82  10 6
Another method:
Let the solubility of AgI be x moles/ lit
AgI(s) Ag+(aq) + I–(aq)
x x
Then Ag combines with CN– to produce Ag(CN)-2. Since Kf for the complex is
+

high, we can assume that almost all of Ag+ combines


AgCN 2

Ag+ + 2CN–
1–2 x x
x
Kf = 
[ Ag ] (1  2x ) 2
Moreover
[Ag+] [I–] = KSP

[Ag+] x = KSP
x x2
Kf = =
1  2 x 2 1  2 x  K SP
K SP 2

x
 x = 0.49 moles

Problem 12: A biochemical experiment is to be carried in NH 4OH – NH4Cl buffer mixture of


pH = 9.26. What volume of 2.0 M NH4Cl solution needs to be added to 20 mL 5.0
M NH4OH solution so as to maintain the pH at the above value.
Kb for NH4OH = 1.8  10–5

Solution: The mixture is a base buffer mixture for which the formula to be applied is
[salt ]
pOH = pKb + log
[acid]
pOH = 14 – pH = 14 – 9.26 = 4.74
pKb = – log (1.8  10–5) = 4.74

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Let V ml of 2M NH4Cl solution needs to be added.


[salt ] 2V
 
[acid] 20  5
Using the above formula
v v v
4.74 = 4.74 + log  log =0  = 1  v = 50
50 50 50
Thus 50 mL of 2 M NH4Cl will have to be added.

Problem 13: When 0.01 M solution of MnCl2 that has been adjusted to pH 3.0 with HCl, is
saturated with H2S (0.10 M), should MnS precipitate?
For H2S: Ka1 = 1.1  10–7
Ka2 = 1.00  10–14
Ksp(MnS) = 1.4  10–15

[H ]2 [S2  ]
Solution: Ka(H2S) = Ka1 Ka2 = = 1.1  10–7  1.0  10–14 = 1.1  10–21
[H2S]
Now, at pH = 3; [H ] = 10–3 M and small contribution of H+ ions from H2S can
+

be neglected.

10 3 [S2  ] = 1.1  10–21
0.10
or [S2–] = 1.1  10–16
Now, Ksp = [Mn2+] [S2–] = 1.4  10–15
And ionic product = (0.01) (1.1  10–16)
= 1.1  10–18 [0.01 (M) Mn2+ coming from 0.01 (M) Mn(NO3)2]
Since ionic product does not exceed the Ksp, no precipitation occurs

Problem 14: K1 and K2 of carbonic acid are 4.3  10–7 and 5.6  10–11 respectively. Calculate
the pH of 0.1 M Na2CO3 solution.

Solution: In solution Na2CO3 will be completely ionised and CO32– ion, a strong base for
being conjugate of very weak acid HCO3–, will hydrolyse to give free OH–- ion
in solution.

Kw 10 14
1. CO32– + H2O HCO3– + OH–, K h1   = 1.8 10–4
K 2 5.6  10 11
HCO3–, is also a strong base for being conjugate base of a weak acid,
H2CO3, will also hydrolyse to give free OH– ion in solution.

Kw 10 14
2. HCO3– + H2O H2CO3 + OH–, Kb =  7
= 2.8  10–8
K1 4.3  10
Where K h1 and K h 2 are the hydrolysis constants of CO32– and HCO3–
respectively.

Since K h1  K h2 , the second step hydrolysis can be neglected.


So considering only the 1st step hydrolysis equilibrium we have

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CO32– + H2O HCO3– + OH—


C excess 0 0
C(1 – h) constant Ch Ch
Ch  Ch h2
K h1 =  C  h2C ( h  1)
C(1  h) (1  h)
K h1
h=
C

[OH ] = Ch = K h1  C

= 1.8  10 14  0.1 = 4.24  10–3M


pOH = – log (4.24  10–3) = 2.37
 pOH = 14 – 2.37 = 11.62
Alternatively we may use the formula directly:
1
pOH = [pKw – pK2 – logC]
2
1
= [14 – 10.25 – log0.1]
2
1
= [14 – 10.25 + 1] = 2.37
2
 pH = 11.62

Problem 15: The solubility product of Ag2C2O4 at 25°C is 1.29  10–11 mole3L–3. A solution of
K2C2O4 containing 0.152 moles in 500 mL water is shaken at 25°C with excess
Ag2CO3 till the following equilibrium is reached.
Ag2CO3(s) + K2C2O4(aq) Ag2C2O4(s) + K2CO3(aq)
At equilibrium, the solutions contains 0.0358 mole of K 2CO3. Assuming the
degree of dissociation of K2C2O4 and K2CO3 to be equal, calculate the solubility
product of Ag2CO3.

Solution: Initial conc. of K2C2O4 solution = 0.152  2 = 0.304 M


Conc. of K2CO3 at equilibrium = 0.0358  2 = 0.0716 M
The equilibrium given in the problem is the overall of the two equilibria as
shown below:
Ag2CO3(s) 2Ag+ + CO32– Ksp = ?
1 1
2Ag+ + C2O42– Ag2C2O4(s) 
K sp 1.29  10 11
-––––––––––––––––––––––––––––––––––––––––––––––––––
K sp
Ag2CO3(s) + C2O42– Ag2C2O4(s) + CO32– K =
1.29  10 11
Initial conc. 0.304 M 0
(0.304 – 0.0716)M 0.0716 M
(Assuming complete dissociation of K2C2O4 and K2CO3 both)
K sp [CO 32 ] 0.0716
11
=

= = 0.308
1.29  10 [C 2 O 4 ] 0.304  0.0716
 Ksp(Ag2CO3) = 0.308  1.29  10–11 = 3.97  10–12 mole3 L–3

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9.2 Objective

Problem 1: In which of the following solvents will AgBr has highest solubility.
(A) 10–3M NaBr (B) 10–3M NH4OH
(C) Pure water (D) 10–3M HBr

Solution: AgBr forms soluble complex with NH4OH i.e. [Ag(NH3)2]Br.


 (B)

Problem 2 The Pkb value of ammonium hydroxide is 4.75. An aqueous solution of


ammonium hydroxide is treated with HCl. The pH of the solution at the point
where half of ammonium hydroxide has been neutralized will be
(A) 9.25 (B) 8.25
(C) 7.50 (D) 4.75

Solution: When NH4OH is half neutralized


[NH4OH] = [NH4Cl]
[salt]
pOH  pK b  log  pK b  4.75
[Base]
pH  14  4.75  9.25

Problem 3: The maximum pH of a solution which is 0.1 M in Mg2+ from which Mg(OH)2 is
not precipitated is
(A) 4.96 (B) 6.96
(C) 7.54 (D) 9.04
Given that Ksp for Mg(OH)2 = 1.2  10–11

Solution: Mg(OH)2 Mg2+ + 2OH–


K sp  [Mg2 ][OH ]2
 1.2  1011  0.1 [OH ]2  [OH ]  1.2  1010
[OH ]  1.1 105
1014
 [H ]   9.09  109 M
1.1 105
pH   log(9.09  1010 )  10  0.9586  9.04

Problem 4: The pKa of HCN is 9.30. The pH of a solution prepared by mixing 2.5 moles KCN
and 2.5 moles of HCN in water and making up the total volume of 500 mL is
(A) 9.30 (B) 7.30
(C) 10.30 (D) 8.30

Solution: As [salt] = [acid], pH = pKa = 9.30


(A)

Problem 5: Fear or excitement, generally cause one to breath rapidly and it results in the
decrease of concentration of CO2 in blood. In what way it will change pH of
blood.
(A) pH will increase (B) pH will decrease
(C) No change (D) pH will be 7

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Solution: Blood buffers do not allow a change in pH it contains serum protein which act
as buffer.
 (C)

Problem 6: The solubility of A2X3 is S mol dm–3. Its solubility product is


(A) 6s4 (B) 64s4
5
(C) 36s (D) 108s5

Solution: Ksp = [A3+]2 [X2–]3 = (2s)2 (3s3 = 108s5


 (D)

Problem 7: Kb for the hydrolysis of reaction


B+ + H2O BOH + H+ is 1.0  10–6. The hydrolysis constant of the
slat is
(A) 10–6 (B) 10–8
–8
(C) 10 (D) 10–9

K w 1014
Solution: For hydrolysis of B+, KH =  6
 108
K b 10
 (C)

Problem 8: If Kb for CN– at 25°C is 4.7 the pH of 0.5 M aqueous NaCN solution is
(A) 12 (B) 10
(C) 11.5 (D) 11

Solution: CN– + H2O  HCN + OH–


pKb = 4.7
 pKa = 9.3
Kh K wC 1014  0.5
[OH ]  Ch  C  K hC  
C Ka 109.3
 [OH ]  104.7  0.5
pOH  11.4
 (C)

Problem 9: In decinormal solution, CH3COOH is ionised to the extent of 1.3%. If log 1.3 =
0.11 what is the pH of the solution?
(A) 3.89 (B) 4.89
(C) 2.89 (D) 2.89

Solution: [H ]  C  0.1 0.013  1.3  103


pH   log(1.3  103 )  3  0.11  2.89
 (C)

Problem 10: The pH of the neutralisation point of 0.1 N ammonium hydroxide with
0.1 N HCl is
(A)6 (B) 7
(C) 9 (D) None of these

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Solution: NH4OH + HCl for NH4Cl which gives acidic solution with pH  7
 (A)

Problem 11: The maximum amount of BaSO4 precipitated on mixing BaCl2 (0.5M) with H2SO4
(1M) will correspond to
(A) 0.5M (B) 1.0M
(C) 1.5 M (D) 2.0 M

Solution: BaCl2 is the limiting reagent


 (A)

Problem 12: Ka for HCN is 5  10–10 at 25°C. For maintaining a constant pH of a the volume
of 5 M KCN solution required to be to 2 mL of 2 M HCN solution is
(A) 4 mL (B) 7.95 mL
(C) 2 mL (D) 9.3 mL

[salt]
Solution: pH  pK a  log
[acid]
[salt]
 9   log(5  105 )  log
[acid]
[salt]
  0.5
[acid]
Let volume of KCN to be added is = v
Total volume of HCN + KCN = (10 + v)
5V 10  2
[KCN]  , [HCN] 
(10  v) (10  v)
[salt] 5v /(10  v)
   0.5
[acid] 20 /(10  v)
v
  0.5  v  2cc
4
(C)

Problem 13: In which case pH will not change on dilution


(A) 0.01M CH3COONa + 0.01M CH3COOH buffer
(B) 0.01M CH3COONH4
(C) 0.01M NaH2PO4
(D) in all cases

Solution: Mixture of sodium acetate and acetic acid is a buffer of pH value equal to pKa
so its buffer capacity is very high and hence its pH will not change
significantly while CH3COONH4 is a salt of weak acid CH3COOH and weak
base NH4OH whose magnitude of Ka and Kb are equal. So its pH does not
depend upon concentration. Further more, NaH2PO4 is, in fact, a single solute
buffer
(D)

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Problem 14: M(OH)x has KSP 4  10–12 and solubility 10–4M. Then the value of x is
(A) 1 (B) 2
(C) 3 (D) –4

Solution: M(OH)x will ionize in the way


M(OH)x M+ x + x OH–
10 –4
x  10–4
 Ksp = [M+x] [OH–]x
 (10–4) (x  10–4)x = 4  10–12
by inspection we get this relation will hold good when x = 2
(B)

Problem 15: pH of a mixture of 1M benzoic acid (pKa = 4.20) and 1M C 6H5COONa is 4.5. In
300 ml buffer, benzoic acid is [log 2 = 0.3]
(A) 200 ml (B) 150 ml
(C) 100 ml (D) 50 ml

[Salt ]
Solution: pH = pKa + log
[ Acid]
[Salt ] [Salt ]
 4.5 = 4.2 + log = log = 0.3
[ Acid] [ Acid]
(since log 2 = 0.3)
[Salt ]
 =2
[ Acid]
Let V ml 1M C6H5 COOH solution and (300 – V) 1M C6H5COONa solution
be mixed together
[Acid] =
V  1 1000
 ;[Salt] =
300  V   1000
1000 300 1000 300
V 300  V
[Acid] = ; [Salt] =
300 300
300  V 300
 =2
V 300
= 300 – V = 2V  V = 100 ml
(C)

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10. Assignments
10.1 Subjective

LEVEL – I

1. How many mole of HCl will be required to prepare one litre of a buffer solution
containing HCN and NaCN of pH 8.5 using 0.01 mole of NaCN?

Ka(HCN) = 4.1  10–10

2. The Ksp for Ca(OH)2 at 25°C is 4.42  10–5. A 500 mL of saturated solution of
Ca(OH)2 is mixed with equal volume of 0.4 M NaOH. How much Ca(OH)2 in
milligrams is precipitated?

3. Calculate the pH at the equivalence point of the titration between 0.1M


CH3COOH (25 ml) with 0.05 M NaOH. Ka (CH3COOH) = 1.8  10–5.

4. Find the concentration of H+, HCO 3* and CO 3  , in a0.01M solution of carbonic acid
if the pH of this is 4.18
Ka1(H2CO3) = 4.45  10–7 and Ka2 = 4.69  10–11

5. Will Fe(OH)3(s) precipitate from a buffer solution prepared by mixing 0.5M


CH3COOH and 0.15M CH3COONa at 25°C, if solution contains 0.25M Fe3+?
KspFe(OH)3 = 4  10–38, Ka(CH3COOH) = 1.74  10–5.

6. Assuming the complete dissociation of HCl and the lead salt, calculate how much
HCl is added to 0.001M lead salt solution to just percent precipitation when saturated
with H2S. The concentration of H2S in its saturated solution is 0.1M
Ka (H2S) = 1.1  10–23
Ksp (PbS) = 3.4  10–28

7. Calculate the change in pH resulting from the addition of (a) 0.02 moles of dissolved
gaseous HCl and (b) 0.02 mole of dissolved NaOH to 1 litre buffer solution
containing 0.1 moles each of NH3 and NH4Cl.
Kb(NH3) = 1.8  10–5

8. How many grams of NH4Cl should be dissolved in 250 ml of water to have a solution
of pH 5.0? Kb for NH4OH is 1.8  10–5.

9. For 0.50 M aqueous solution of sodium cyanide, (pKb of CN– of 4.70), calculate (i)
hydrolysis constant, (ii) percentage hydrolysis and (iii) pH.

10. The solubility of Pb(OH)2 in water is 6.7  10–6M. Calculate the solubility of Pb(OH)2
in a buffer solution of pH 8.

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LEVEL – II

1. Calculate the amount of NH3 and NH4Cl required to prepare a buffer solution of pH
9.0, when total concentration of buffering reagents is 0.6 mol L–1. What will be the
effect of adding 2g NaOH in 500 mL of this buffer, on pH ?

pKb for NH3 = 4.7

2. 20 mL 1.0 M solution (pH = 3) of a weak monobasic acid is titrated with 0.5 N


solution of NaOH. Calculate pH of the solution when (a) 10 mL, (b) 20 mL and (c) 40
mL of NaOH solution have been added.

3. Calculate sulphide ion concentration in saturated H2S solution in water at 25°C when
the pH of the solution is 11. The molarity of saturated H2S solution in water is 0.1M
and K1, K2 for H2S are 5.7  10–8 and 1.2  10–15 at 25°C.

4. Two weak monobasic organic acids HA and HB have dissociation constants as 1.5 
10–5 and 1.8  10–5 respectively at 25°C. If 500 ml of 1 M solutions of each of these
two acids are mixed to produce 1 litre of mixed solution, what is the pH of the
resulting solution?

5. Calculate the pH of 0.1 M K3PO4 solution. K1, K2 and K3 of H3PO4 are 5.0  10–3,
2.5  10–8 and K3 = 1.0  10–12.

6. 25 mL of a weak base BOH was titrated with 0.5 M HCl. The pH of solution upon
addition of 10 mL acid was 8.6 and that upon addition of 25 mL acid was 8. Calculate
pH of the base solution when 0 mL acid has been added. Also calculate the pH at
the end point.

7. The Ksp of Mg(OH)2 is 8.9  10–12 at 25°C. If the pH of solution is adjusted to 9.0.
How much Mg2+ ion will be precipitated as Mg(OH)2 from a 0.1M MgCl2 solution at
25°C? Assume that MgCl2 is completely dissociated.

8. An aqueous solution contains 10% ammonia by mass and has density of


0.99 gm cm–3. Calculate hydroxyl and hydrogen ion concentration in this solution. Ka
for NH 4 = 5  10–10 M.

9. A solution of 0.010 M CdCl2 contians 0.010 (M) NH3. What conc. of +NH4 ion from
NH4Cl is necessary to prevent the precipitation of Cd(OH)2? (Ksp = 2  10–14 and Kb =
1.8  10–5)

10. An aqueous solution of aniline of conc. 0.24 M is prepared. What concentration of


sodium hydroxide is needed in this solution, so that anilium ion conc. remains at 1 
 

10–8 M. Ka  C6H5 NH3  = 2.4  10–5.
 

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10.2 Objective

LEVEL – I

1. An acidic indicator HIn (Kin = 10–6) ionises as HIn H+ + In–. The acid colour
predominates over the basic colour when HIn is at least 10 times more concentrated
than In– ion. On the other hand basic colour predominates over the acid colour when
the In– ion is at least 5 times more concentrated than HIn. Hence pH range of the
indicator is
(A) 5.0 – 6.7 (B) 7.0 – 8.7
(C) 5.3 – 7.0 (D) 7.0 – 8.1

2. The correct statement amongst the following is


(A) A strong electrolyte remains completely dissociated at all dilutions
(B) Upon dilution the degree of dissociation of a weak electrolyte and number of ions
per unit volume of its solution both increase.
(C) A strong electrolyte is completely ionised at all dilutions but not completely
dissociated.
(D) pH of solution of a weak acid decreases with dilution.

3. 4M solution of a weak monobasic acid (x% ionized and pH = 3.0) is diluted to 1 M by


adding water (distilled). Percentage ionisation and pH of solution after dilution will be
respectively.
(A) 2x and 2.7 (B) 0.25x and 3.3
(C) 0.5x and 2.7 (D) 2x and 3.3

4. pH of a buffer solution changes from 6.20 to 6.17 when 0.003 mole of acid is added
to 500 mL of the buffer. The buffer capacity of the system is, therefore
(A) 0.1 (B) 0.3
(C) 0.2 (D) 0.4

5. Ksp of CaSO4 is 2.4  10–5 at 25°C. In a solution containing Ca2+ ions the precipitation
of CaSO4 begins to occur when SO42– ion concentration in the solution is made just
to exceed the value of 4.8  10–3M. Hence concentration of Ca2+ ion in the
solution is
(A) 200 ppm (B) 40 ppm
(C) 400 ppm (D) 100 ppm

6. Correct statement regarding pure water amongst the following is


(A) It contains only single specie i.e. H2O molecules
(B) It contains three species: H2O (molecules), H+ and OH–
(C) It contains only two species H3O+ and OH–
(D) It contains three species H2O(molecules), H3O+ and OH–

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7. There is a solution which is one molar w.r.t. each M2+ and X3+ ions present in it. The
Ksp of M(OH)2 and X(OH)3 are 4.0  10–10 and 2.7  10–14 respectively . If NH4OH
solution is added gradually to the above solution which of the following will happen?
(A) Both M(OH)2 and X(OH)3 will precipitate together
(B) M(OH)2 will precipitate first.
(C) X(OH)3 will precipitate first
(D) None of these will precipitate with NH4OH solution

8. 20 mL of a weak acid HX is titrated against 0.1 M NaOH. At the point of half


equivalence the pH of solution is 5.7. Hence Ka of acid is
(A) 7.0  10–5 (B) 2.0  10–5
(C) 7.0  10–4
(D) 2.0  10–6

9. If an aqueous solution at 25°C has twice as many OH- as pure water its pOH will be
(A) 6.699 (B) 7.307
(C) 7 (D) 6.98

10. Solubility of AgCl in water, 0.01M CaCl2, 0.01M NaCl and 0.05M AgNO3 are S1, S2,
S3 and S4 respectively then.
(A) S1 > S2 > S3 > S4 (B) S1 > S3 > S2 > S4
(C) S1 > S2 = S3 > S4 (D) S1 > S3 > S4 < S2

11. pH of Ba(OH)2 solution is 12. Its solubility product is


(A) 10–6M3 (B) 4  10–6M3
(C) 0.5  10 M
–7 3
(D) 5  10–7M3

12. The hydrolysis constant for ZnCl2 will be


K K2
(A) Kh = w (B) K h  w
Kb Kb
K 2w Kb
(C) K h  (D) K h 
K b2 K 2w
Where Kb is effective dissociation constant of base Zn++

13. If the degree of ionization of water be 1.8  10-9 at 298K. Its ionization
constant will be
(A) 1.8  10-16 (B) 1 10-14
(C) 1  10 -16
(D) 1.67  10-14

14. When a solution of benzoic acid was titrated with NaOH the pH of the solution when
half the acid neutralized was 4.2. Dissociation constant of the acid is
(A) 6.31  10-5 (B) 3.2  10–5
(C) 8.7  10–8 (D) 6.42  10–4

15. 10-2 mole of NaOH was added to 10 litre of water. The pH will change by
(A) 4 (B) 3
(C) 11 (D) 7

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16. 0.1M solution of which of the following substances is most acidic


(A) NH4Cl (B) KCN
(C) AlCl3 (D) NaC2H3O2

17. The following reaction takes place in the body


CO2 + H2O H2CO3 H+ + HCO3–. If CO2 escapes from the system
(A) pH decreases (B) [H+] will decrease
(C) [H2CO3] remains the same (D)forward reaction will be promoted

18. The solubility of A2X5 is x mole dm-3. Its solubility product is


(A) 36x6 (B) 64 x 104x7
7
(C) 126 x (D)1.25 x 104x7

19. The solubility of CH3CO2Ag would be least amongst the following


solvents in
(A) acidic solution of pH = 3 (B) basic solution of pH = 8
(C) neutral solution of pH = 7 (D) pure water

20. If Kh (hydrolysis constant) for anilinium ion is 2.4 x 10-5M, then Kb for
aniline will be
(A) 4.1 x 1010 (B) 4.1 x 10-10
(C) 2.4 x 109 (D) 2.4 x 10-19

21. Acetic acid dissolved in ammonia will be


(A) Highly conducting (B) Less conducting
(C) Can’t say (D) More conducting than that in water

22. The equilibrium constant of the reaction:


A– + H2O HA + OH–
is 108 times more than ionic product of water at 25°C. Hence Ka of weak acid will be
(A) 10–8 (B) 10–6
–14
(C) 10 (D) None of these

23. If we plot 2 verses volume V we will get


(A) a straight line with slope value equal to Kdissociation
(B) a straight line with slope equal to Keq
(C) an exponential curve
(D) a parabola

24. Equal volumes of two solutions of a strong acid having pH 3 and pH 4 are mixed
together. The pH of the resulting solution will then be equal to
(A) 3.5 (B) 3.26
(C) 7 (D) 1.0

25. When equal volumes of following solution are mixed, precipitation of AgCl
(Ksp = 1.8 x 10-10) will occur only with
(A) 10-4M; Ag+ and 10-4M; Cl- (B)10-5M; Ag+ and 10-5M; Cl-
-6 + -6 -
(C) 10 M; Ag and 10 M; Cl (D)10-10M; Ag+ and 10-10M; Cl-

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26. Let Kw at 100°C be 5.5  10-13 M2. If an aqueous solution at this temperature has
pH = 6.2. Its nature will be
(A) acidic (B) alkaline
(C) neutral (D) can’t say

27. Dissociation constant of two acids HA & HB are respectively 4  10-10 & 1.8  10-5
whose pH value will be higher for a given molarity:
(A) HA (B) HB
(C) Both same (D) Can’t say

28. pH value of pure water at 0°C will be


(A) Greater than 7 (C) Less than 7
(C) 7 (D) All the three

29. The pH of a buffer is 6.745. When 0.01 mole of NaOH is added to 1 litre of it, the pH
changes to 6.832. Its buffer capacity is
(A) 0.187 (B) 0.0115
(C) 0.076 (D) 0.896

30. The aqueous solution of potash alum is acidic due to hydrolysis of


(A) K+ (B) Al3+
– –-
(C) SO4 (D) presence of acid in its crystal as impurity

LEVEL – II

LEVEL - II More than one choice

1. Which of the following is the correct expression of degree of dissociation for weak acid.
(Assume  is negligible w.r.t to unity).
Ka Kw  c
(A) (B)
c Ka
Kw 1
(C)  (D) Kb of conjugatebase  c
Kb of conjugatebase c

2. When equal volumes of the following solutions are mixed, precipitation of AgCl
(Ksp = 1.8 × 10–10) will occur only with
(A) 10–4 M [Ag+] and 10–4M[HCl] (B) 10–3 M[Ag+] and 10–3 M [Cl–]
(C) 10–6M [Ag+] and 10–6 M [Cl-–] (D) 10–2 M [Ag+] and 10–2M [Cl–].

3. Correct options for the following reaction is :-


NH3 + H2O NH4 + OH
+ 
(A) K a  NH4  + Kb (NH3) = 10-14 (B) Ka(NH+ )  Kb( NH3 )  1/ Kw
  4

(C) K a (NH4 )  Kb( NH3 )  Kw


+
(D) pKa( NH  ) + pK b( NH3 ) = 14
4

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4. pH of 0.03 M NaH2PO4
(A) Increases with dilution (B) decreases with dilutions
(C) does not depend upon concentration (D) changes with change in temperature

5. Which of the following statements is /are right


(A) The pH of 1  10-8 M solution of HCl is 8
(B) The conjugate also of H2 PO4 is
(C) auto protolysis constant of water increases with temperature
(D) when a solution of weak monoprtic acid is titrated against a strong base, at half
1
neutralization point pH = pK a
2
6. When a 2 M aqueous solution of CH3COOH is diluted with water. The change which may
occure is
(A) The concentration of H+ increases
(B) the degree of dissociation of Acid increases
(C) the value of ka increases
(D) the number of H+ ion increases
7. Which of the following statement are true for a solution saturated with AgCl and AgBr. If
their solubilities in mol lit-1 in separate solutions are x and y respectively.
(A) [Ag+] = [Br] + [Cl] (B) [Cl] > [Br]
(C) [Br] > y (D) [Ag+] = x + y

8. Pure NH3 is placed in a vessel at a temperature where its dissociation constant (K) is
appreciable, At equilibrium
(A) K does not change with pressure
(B) K does not change with [NH3]
(C) concentration of NH3 does not change with pressure
(D) concentration of Hydrogen in less than that of nitrogen.

9. Which of the following solution will have no effect on pH with dilution


(A) 0.1 M NaHS (B) 5 M H2CO3 + 5M NaHCO3
(C) 1 M CH3COONH4 (D) 1 M NH4Cl
10. Which of the following solution will have pH =13 assume complete dissociations
(A) 2g of NaOH in 500 ml solution (B) 100 ml of solution of 0.05 M Ca(OH)2
(C) 100 ml of solution of 0.1 N Ca(OH)2 (D) 4g of NaOH in 500 ml solution.

LEVEL - III Other Engg. Exams

1. A solution which is 10-3 M each in Mn2+, Fe2+, Zn2+ and Hg2+ is treated with 10-16 M sulphide
ion. If Ksp of MnS, FeS, ZnS and HgS and 10-5, 10-23, 10-20 and 10-54 respectively, which one
will precipitate first
(A) FeS (B) MgS
(C) HgS (D) ZnS

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2. Let the solubility of an aqueous solution of Mg(OH)2 be x then its ksp is


(A) 4x3 (B) 108 x5
4
(C) 27 x (D) 9x
3. The solubility product of BaSO4 at 250C is 1.0  10-9. What would be the concentration of
H2SO4 necessary to precipitate BaSO4 from a solution of 0.01 M Ba2+ ions
(A) 10-9 (B) 10-8
-7
(C) 10 (D) 10-6
4. Which of the following salts when dissolved in water will get hydrolysed
(A) NaCl (B) NH4Cl
(C) KCl (D) Na2SO4
5. Which is the correct alternative for hydrolysis constant of NH4CN
Kw Kw
(A) (B)
Ka K a  Kb
Kb Ka
(C) (D)
c Kb
6. The solubility of AgCl in 0.2 M NaCl solution (Ksp for AgCl = 1.20  10-10) is
(A) 0.2 M (B) 1.2  10-10 M
(C) 0.2  10-10 M (D) 6.0  10-10 M
7. The solubility product of Ag2CrO4 is 32  10-12. What is the concentration of CrO4 ions in
that solution
(A) 2  10-4 M (B) 16  10-4 M
(C) 8  10 M
-4
(D) 8  10-8 M
8. Hydrolysis constant for a salt of weak acid and weak base would be
Kw Kw
(A) K h  (B) K h 
Ka Kb
Kw
(C) K h  (D) none of these
K a Kb
9. A litre of solution is a saturated with AgCl. To this solution if 1.0  10-4 mole of solid NaCl is
added, what will be the [Ag+], assuming no volume change
(A) More (B) Less
(C) Equal (D) Zero
10. The pH of a 0.001 M NaOH will be
(A) 3 (B) 2
(C) 11 (D) 12

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LEVEL - IV

A Matrix-Match Type

p q r s
This section contains 2 questions. Each question contains statements given in two
column which have to be matched. Statements (A, B, C, D) in Column I have to be A p q r s

matched with statements (p, q, r, s) in Column II. The answers to these questions B p q r s
have to be appropriately bubbles as illustrated in the following example.
C p q r s
If the correct matches are A–p, A–s, B–q, B–r, C–p, C–q and D–s, then the
correctly bubbled 4 × 4 matrix should be as follows : D p q r s

1. Column (I) Column (II)


(A) 200 ml, 0.25 M NaOH + 300 ml, 0.1M CH3COOH  N V  NBVB 
(p) pH = - log  A A 
 VA  VB 
(B) 200 ml, 0.25 M CH3COOH + 250 ml, 0.2 M NaOH  Salt 
(q) pH = pka + log  
 Acid 
(C) 200 ml, 0.25 M CH3COOH + 300 ml, 0.1 M NaOH (r) pOH = -log[OH]
(D) 250 ml, 0.25 M HCl + 200 ml, 0.25 M NaOH 1 1
(s) pH = 7 + pK a  logC
2 2

2. Column (I) Column (II)


(A) aq. NaCl (saturated) (p) addition of AgNO3 decrease solubility
(B) aq. AgNO3 (saturated) (q) Addition of HCl increase solubility
(C) aq. Mg (OH)2 (saturated) (r) addition of HCl decrease solubility
(D) Saturated PbS solution (s) Addition of H2S decrease solubility.

B Linked Comprehension Type

Comprehension - I
If a sparingly soluble salt is placed in water, after some time an equilibrium is established when the
rate of dissolution of ions from the solid equals the rate of precipitation of ions from the saturated
solution at a particular temperature. Thus, a dynamic equilibrium exists between the undissociated
solid species and the dissolved ionic species in a saturated solution at a particular temperature.
For example, in AgCl, we have the following equilibrium :

AgCl (s) Ag+ (aq) + Cl (aq.)


The equilibrium constant
 Ag   Cl  
K eq  
 AgCl 
[AgCl] is constant
 Keq  [AgCl] = [Ag+] [Cl-]  Ksp(AgCl) = [Ag+] [Cl-]

If there would not have been a saturated solution, then from equation (1), Keq. [AgCl]  Ksp, but
Keq. [AgCl] = QAgCl, where Q is ionic product. It implies that for a saturated solution, Q = Ksp

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Ksp is temperature dependent.


When Q < Ksp, then the solution is unsaturated and then will be no precipitate.
When Q = Ksp, then solution will be saturated, no ppt.
when Q = Ksp, the solution will be supersaturated and there will be formation of precipitate.

1. pH of a saturated solution of Ba(OH)2 is 12. Hence Ksp of Ba(OH)2 is:


(A) 5  10-7 M3 (B) 5  10-4 M2
(C) 1  10-6 M3 (D) 4  10-6 M3

2. A solution is a mixture of 0.05 M NaCl and 0.05 M NaI. The concentration of iodide ion in
the solution when AgCl just starts precipitating is equal to:
(Ksp AgCl = 1  10-10 M2; Ksp AgI = 4  10-16 M2)
(A) 4  10-6 M (B) 2  10-8 M
(C) 2  10 M
-7
(D) 8  10-15 M

3. Silver iodide is used in cloud seeding to produce rain


AgI Ag+(aq) + I (aq); Ksp = 8.5  10-7. AgNO3 and KI are mixed to give
[Ag ] = 0.010 M; [I] = 0.015 M. Will AgI precipitate ?
+

(A) yes (B) no


(C) can’t say (D) this depends on  NO3  and [K+] as well

4. Slaked lime, Ca(OH)2 is used extensively in sewage treatment. What is the maximum pH
that can be established in Ca(OH)2(aq.)
Ca(OH)2(s) Ca2+ (aq) + 2OH (aq) ; Ksp = 5.5  10-6
(A) 1.66 (B) 12.34
(C) 7 (D) 14

Comprehension - II
Acidity or alkalinity of a solution depend upon the concentration of hydrogen ion relative to that of
hydroxyl ions. The product of hydrogen ion & hydroxyl ion concentration is given by
Kw = [H+] [OH–]
the value of which depends only on the temperature & not on the individual ionic concentration. If
the concentration of hydrogen ions exceeds that of the hydroxyl ions, the solution is said to be
acidic; whereas, if concentration of hydroxyl ion exceeds that of the hydrogen ions, the solution is
said to be alkaline. The pH corresponding to the acidic and alkaline solutions at 25ºC will be less
than and greater than seven, respectively. To confirm the above facts 0.5 M CH3COOH is taken for
the experiments.
[Given : Ka of acetic acid = 1.8 ×10–5]
5. Degree of dissociation of acetic acid is -
(A) 66 × 10–2 (B) 6 × 10–3
(C) 3 × 10–3 (D) 5 × 10–3
6. pH of the solution will be -
(A) 2.52 (B) 2.22
(C) 5 (D) 3.92
7. If pH of the solution is doubled, what will be the concentration of acetic acid -
(A) 1.8 × 10–5 M (B) 1.0 M

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(C) 1.374 × 10–5 M (D) 1.25 × 10–3 M

8. To what volume at 25º C must 1 dm3 of this solution be diluted in order to double the pH-
(A) 3.37 × 104 dm3 (B) 2.34 × 102 dm3
(C) 1.68 × 104 dm3 (D) 3.18 × 103 dm3

9. Now to increase the hydrogen ion concentration 100 dm3 of 0.1M HCl solution is added
to100 dm3 of 0.5 M acetic acid solution, then what will be the pH of the final solution -
(A) 6 (B) 1.3
(C) 3 (D) 1

Comprehension - III
In qualitative analysis, cations of group II as well as group IV precipitated in the form of sulphides.
Due to low value of Ksp of group II sulphides, group reagent is H2S in presence of dil. HCl and due
to high value of Ksp of group IV sulphides, group reagent is H2S in presence of NH4OH and NH4Cl.

In a 0.1M H2S solution, Sn2+, Cd2+ and Ni2+ ions are present in equimolar concentration (0.1 M).

Given:
K a1 Ka2(H2S) = 10-7, K a 2 (H2S) = 10–14
Ksp (SnS) = 8  10–29 Ksp (CdS) = 10–28,
Ksp (NiS) =3 × 10–21

10. If HCl solution is passed slowly then which sulphide will precipitate first -
(A) SnS (B) CdS
(C) NiS (D) none of these

11. At what pH precipitate of NiS will form -


(A) 12.76 (B) 7
(C) 1.24 (D) 4

12. Which of the following sulphide is more soluble in pure water-


(A) CdS (B) NiS
(C) SnS (D) all have equal solubility

13. If 0.1 M HCl is mixed in the solution containing only 0.1 M Cd2+ and saturated with H2S then
concentration of Cd2+ remains in the solution after CdS has precipitated -
(A) 8.2  10-8 (B) 8.2  10-9
(C) 5.6 10-7 (D) 5.6 10-8

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11. Hints for Subjective Problems


LEVEL – I

K w  Ka
1. Apply, [H ] 
c

[acid]
2. Apply, [H ]  K a
[salt]

 pK  pK b  logC 
8. Apply, pH   w 
 2 

LEVEL – II

[salt]
1. Apply, pOH  pK b  log
[base]

5. Anion of the salt being conjugate base of weak acid will hydrolyse in the following
steps:
K
PO34  H2O HPO24  OH Kh  w
K3
K
HPO24  H2O H2PO4  OH Kh  w
K2
K
H2PO4  H2O H3PO4  OH Kh  w
K1

7. As pH = 9, pOH = 5, [OH–] = 10–5M


[Mg2+] [OH–] = Ksp
8.9  1012
 [Mg2 ]  5 2
 8.9  102 M
[10 ]
thus proceed on further

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12. Answers
12.1 Subjective

LEVEL – I

1. 8.85  10–3M 2. 743.3 mg


3. 8.63 4. 6.73  10–6, 4.8  10–11
5. Q  Ksp the precipitate will form 6. 1.80
7. a) – 0.18 b) 0.1761 unit 8. 2.43g
9. 11.5 10. 1.2  10–3M

LEVEL – II

1. [NH4Cl] = 0.4 mole L–1, [NH3] = 0.2 mole L–1, pH = 0.3
2. a) pH = 5.523, b) pH = 6, c) pH = 9.77
3. 6.8  10–2 M 4. 2.392
5. pH = 12.5 6. pH = 11, pH = 4.239
7. 0.011 mole L–1 8. [OH–] = 0.0179, [H+] = 9.268  10–12M
9. 0.13 M 10. 10–2M

12.2 Objective

LEVEL – I

1. (A) 2. (C)
3. (D) 4. (C)
5. (A) 6. (D)
7. (B) 8. (D)
9. (A) 10. (B)
11. (D) 12. (B)
13. (D) 14. (A)
15. (A) 16. (A)
17. (B) 18. (D)
19. (B) 20. (B)
21. (D) 22. (A)
23. (A) 24. (B)
25. (A) 26. (B)
27. (A) 28. (A)
29. (B) 30. (B)

LEVEL – II
1. (A, C) 2. (A, B, D)
3. (C, D) 4. (C, D)
5. (B, C) 6. (B, D)
7. (A, D) 8. (A, B, C)
9. (A, B, C) 10. (A, B, C)

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LEVEL – III

1. (C) 2. (A)
3. (C) 4 (B)
5. (B) 6 (D)
7 (A) 8 (C)
9 (B) 10 (C)

LEVEL - IV

A B
Match the following Write-up
1. (A) – (r) 1. (A)
(B – (p), (r) 2. (C)
(C) – (q), (r) 3. (A)
(D) – (r), (s) 4. (B)
2. (A) – (r) 5. (B)
(B) – (p) 6. (A)
(C) – (q) 7. (C)
(D) – (s) 8. (A)
9. (B)
10. (A)
11. (C)
12. (B)
13. (A)

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