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Rule (1)
A
B

A+2 + 2e G1 = 0.2kcal ....(i)


B+2 + 2e G2 = +0.4 kcal ....(ii)

According to the rule of spontaneity, reaction (i) is


spontaneous but reaction (ii) is non-spontaneous. To
gain full cell reaction, we convert non-spontaneous
reaction into spontaneous reaction.
Same : A
A+2 + 2e;
B;
Change : B+2 + 2e

G1 = 0.2kcal
G2 = 0.4 kcal

A + B+2
A+2 + B Grxn
Grxn = G1 + G2 = (0.2kcal) + (0.4 kcal)
= 0.6 kcal

To Calculate Emf of reaction


G = nFE

E = G/nF

Rule (2)
If both half cell reactions are non-spontaneous, then
we convert more non-spontaneous reaction into
spontaneous reaction to gain full cell reaction.
A
A+2 + 2e G1 = +0.2 kcal ....(i)
B
B+2 + 2e G2 = +0.5 kcal ....(ii)
Reaction (i) is less non-spontaneous and reaction (ii) is
more non-spontaneous.
Change : B+2 + 2e
Same :

B
+2

A + 2e

B+2 + A

G2 = 0.5 kcal
G1 = +0.2 kcal

B + A+2 Grxn

Grxn = G1 + G2 = (0.5) + (0.2) kcal = 0.3 kcal


* Spontaneity from G

4
3
Non-spontaneoity
increases
2
1
G = 0 (Rxn is at equilibrium)
0
1
Spontaneoity
2
increases
3
4
Greater the positive value (+ve) of free energy
greater will be non-spontaneity.
Greater the negative value (ve) greater will be
spontaneity

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RULE TO SOLVE PROBLEM OF ELECTROCHEMISTRY

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Knowledge of thermodynamics, reaction quotient and


redox reaction are very important for solving the problem
of electrochemistry

Rule (3)
If both half cell reactions are spontaneous then we
conv ert less spontaneous reaction into nonspontaneous reaction.
A
A+2 + 2e G1 = 0.5 kcal (more spontaneous)
B
B+2 + 2e G2 = 0.2 kcal (less spontaneous)
Same :
A
A+2 + 2e
+2
Change : B + 2e
B
A + B+2

G1 = 0.5 kcal
G2 = +0.2 kcal

B + A+2 Grxn

G rxn = 0.5 kcal + 0.2 kcal = 0.3 kcal


Rule (4)
A

A+2 + 2e G1 = 0.2 kcal ...(i)

B+2 + 2e G2 = +0.5 kcal...(ii)

If G given in the half cells then spontaneity of the


reaction not determined by G. We convert G into
G by following equation.
G = G + RT ln Q
If Q = 1 , then G = G
G1 = G1 + RT ln [A+2] .......(i)
G2 = G2 + RT ln [B+2] .......(ii)
Rule (5)
If emf of the half cell given in the problem then we predict
the spontaneity of reaction by emf.
G = nFE
* Spontaneity from E
4
3
Spontaneoity
increases
2
1
0
E = 0 (Rxn is at equilibrium)
1
Non - spontaneoity
2
increases
3
4

Greater the reduction potential greater will be


ease of reduction. Greater the oxidation potential greater
will be ease of oxidation.
Rule (6)
A
B
Same :

A+2 + 2e Eo.p = 0.2 Volt (non-spontaneous)


B+2 + 2e Eo.p = +0.5 Volt (Spontaneous)
B

Change: A+2 + 2e
B + A+2

B+2 + 2e

EO.P.. = +0.5 Volt

ER.P.. = +0.2 Volt

B+2 +A

Ecell

Ecell = EO.P + ER.P = 0.5 + 0.2 = 0.7 Volt

A+2 + 2e EO.P. = +0.5 Volt (more spontaneous)


B+2 + 2e EO.P.. = +0.3 Volt (Less spontaneous)

Same : A
A+2 + 2e
+2
Change: B + 2e
B
A + B+2

EO.P. = +0.5 Volt


ER.P. = 0.3 Volt

B + A+2 Ecell

Ecell = EO.P. + ER.P. = +0.5 0.3 Volt = +0.2 Volt


Rule (8)
A
B

A+2 + 2e EO.P. = 0.5 Volt (more spontaneous)


B+2 + 2e EO.P.. = 0.2 Volt (Less spontaneous)

Same : B
B+2 + 2e
+2
Change: A + 2e
A
A + B+2

EO.P. = 0.2 Volt


ER.P. = +0.5 Volt

B + A+2 Ecell

Ecell = EO.P. + ER.P. = 0.2 + 0.5 Volt = +0.3 Volt


Rule (9)
A+2 + 2e EO.P. = +0.5 Volt.....(i)
B+2 + 2e EO.P.. = 0.2 Volt.....(ii)

A
B

Spontaneity of reaction not determined by standard emf


it is determined by following equation.

E O .P . = E O.P . (0.0592 n )log[A +2 ]


E O .P . = E

O .P .

+2

(0.0592 n )log[B ]

Greater the O.P. greater will be ease of oxidation.

HIT AND TRIAL METHOD


We determined spontaneity of reaction by E value,
however it is not correct. These are two possible result
one is correct and other is incorrect. If Emf of the cell is
+ve then our result is correct, but Emf of the cell is ve,
then our result is incorrect, to gain correct result we
convert oxidation half cell into reduction half cell and
reduction half cell into oxidation half cell.
Rule for converting oxidation half cell into
reduction half cell and vice-versa
*

+2

A + 2e EO.P. = 0.2 Volt

If you want to gain reduction half cell then


+2

A + 2e
*

A ER.P.. = +0.2 Volt


B+2 + 2e EO.P.. = +0.5 Volt

If you want to gain reduction half cell then


B+2 + 2e

B ER.P.. = 0.5 Volt

Rule (10) :
A
A+2 + 2e EO.P. = 0.2 Volt
B+2 + 2e
B ER.P.. = 0.5 Volt
Ecell = ?

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A
B

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Rule (7)

To calculate Ecell we convert all the half cell reactions


are in same type (either oxidation half or reduction half)
(i) Convert both reaction into oxidation half
A
A+2 + 2e EO.P. = 0.2 Volt
B
B+2 + 2e EO.P.. = 0.5 Volt
(ii) Convert both reaction into reduction half cell
A+2 + 2e
A ER.P.. = 0.2 Volt
B+2 + 2e
B ER.P.. = 0.5 Volt
B
B+2 + 2e
A
A+2 + 2e

Same :
Change :

B+2 + A

ER.P. = 0.5 Volt


EO.P. = +0.2 Volt

A+2 + B Ecell = 0.7 Volt

Rule (11) :
For following type half cell reaction hybrid reaction
quotients (mixture of Qp and Qc) used in place of Qc or
Qp

H2
2H+ + 2e (no. of electron used = 2)

Q Hybrid =

H+ + 1e (no. of electron used = 1)

1/2H2

Q Hybrid =

[H + ]
(PH 2 )1/2

2Cl (no. of electron used = 2)

Cl2 + 2e

Q Hybrid =

[H + ]2 mol / litre
(PH 2 ) atm

[Cl ]2
(PCl 2 )

Cl

Cl2 + 1e

Q Hybrid =

(no. of electron used = 1)

(PCl 2 )1/2
[Cl ]

Rule(12) :
Emf is mass or mole independent property (intensive
property), but free energy is mass or mole dependent
property (Extensive property)
H2
1/2H2

2H+ + 2e;
+

H + 1e;

EO.P.. = x volt, G = 2Fx


EO.P.. = x volt, G = Fx

Emf of the reaction not depends on stoichiometry coeff.


Example :
2X+ 3y
5A
Ecell = x volt
X+ y
A
Ecell = x volt
Rule (13) :
If reaction is spontaneous in forward direction then nonspontaneous in reverse direction and vice-versa.
Magnitude of Emf and G are same but sign is reverse.
A
A+2 + 2e;
+2
A + 2e
A

EO.P. = X volt , G = 2FX


G = +2 FX, G = nFE
G = nFER.P.

ER.P. = G/nF =2FX / 2F = X volt

+2

B +A

A +B

Ecell = E1 + E2

If we proceed this problem by G then.


A
A+2 + 2e
G1 = 2FE1
+2
B + 2e
B
G2 = 2FE2
B+2 + A

A+2 + B

Grxn = G1 + G2

2FEcell = 2FE1 2FE2


Ecell = E1 + E2

If no. of electron involved and apparent in


reaction then reaction is half cell. But if no. of electron
involved but not apparent in the reaction then reaction
is full cell reaction.
Example:

Fe
Fe+3 + 3e oxidation half cell, n=3

Fe+3 + 1e
Fe+2 reduction half cell, n= 1

2Fe+3 + 3I
2Fe+2 +I3 full cell rxn, n=2

MnO4 + 4H+ +3e


2H2O+MnO2
reduction half cell, n = 3

Fe+2
Fe+3 + 1e oxidation half cell, n=1

If two half cell reaction having different no. of


electron provide full cell reaction then we also add Emf
for simplicity.
Example :
2 (A
A+3 +3e) E1, G1 = 6FE1
3 ( B+2 + 2e
B) E2, G2 = 6FE2
2A + 3B+2

2A+3 +3B, Grxn = 6FE3

Grxn = G1 + G2 = 6FE1 6FE2 = 6FE3


E3 = E1 + E2
Rule (15) :
If two half cell produces third half cell then we should
not added Emf directly. To calculate emf of third half
cell we add G,
A
A+3 + 3e ;
E1, G1 = 3FE1
+2
B + 2e
B;
E2, G2 = 2FE2
A + B+2

A+3 + B + 1e

E3 E1 + E2

G3 = G1 + G2 1FE3 = 3FE1+ (2FE2)


E3 = 3E1 + 2E2
Rule (16) :
For writing shorthand notation or cell representation of
electrochemical cell following conventions are used.
A
A+2 + 2e
+2
B + 2e
B

EO.P = 0.5 volt


ER.P = 0.2 volt

A + B+2

Ecell = 0.7 volt

B + A+2

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+2

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Rule (14) :
If two half cell (no. of electron same or different)
produces full cell reaction then for simplicity we add
directly emf of half cell not G. Addition of G gives
same result but process is lengthy.
A
A+2 + 2e
E1
+2
B + 2e
B
E2

This electrochemical cell represented as follows.

A | A +2 || B +2 | B
[C ]

[C ]

1
1424
3

2 24
14
3

L .H .S .

R .H .S .

Note :
(a)

Oxidation half cell always represented in L.H.S


and reduction half cell always represented in
R.H.S.

(b)

Single vertical line placed in L.H.S denote


anode and R.H.S denote cathode

(c)

Cathode is known as +ve terminal but anode is


known as ve terminal in electrolytic cell.

(d)

C1 denotes concentration of A+2 and C2 denotes


concentration of B+2.

(e)

Reaction quotient of this representation is:

Q=

[ A +2 ][B ]
[ A ][B +2 ]

(f)

Flow of electron takes place from left to right


(anode to cathode), but flow of current takes
place from right to left (cathode to anode)

(g)

No. of electron involved = 2

(h)

Ecell for this representation calculated as follows


0
E cell = E cell

0.0592
logQ
2

CONCEPT OF SPONTANEITY
For the complete study of reaction knowledge of
thermodynamics and chemical kinetics are essential.
Thermodynamics tell us about spontaneity of
reaction (Reaction is spontaneous or not). Chemical
kinetics tells us about the rate of reaction (Reaction is
fast or slow). Spontaneity of the reaction is determined
by thermodynamic parameter like G, S (universe) and
value of emf (For oxidation, Reduction or Redox
Reaction)
Entropy Change (S)
Entropy is thermodynamic state quantity that is measure
of randomness or disorder of the molecule of the
system.
Explanation of entropy on the basis of probability
left
bulb
no. of molecule
A (1 molecule)
A,B (2 molecules)
A,B,C....(n molecules)
6.023 1023

right
bulb
relative prob. of finding all
molecules in left bulb
PA = = ()1
PAB = PAPB = ()2
PABC...... = ()n
23
23
()6.023 10 = 26.023 10

Example :
Melting of ice at 10C. S universe = +ve
Melting of ice at 0C
S universe = 0
Melting of ice at 10C S universe = ve
For spontaneous process :
Ssystem + Ssurrounding = Suniverse
(+ve or, ve) (+ve or ve)

(always +ve)

G = H T S .................. (1)

G = Free energy, H = Heat enthalpy


S = Change in entropy
Eq. (1) is multiplied by (1/T)
G
H T Ssys
H

=
+ Ssys
T
T
T
T

G
H

= Ssurro + Ssys = Suniverse Q


= Ssurro
T
T

G = T Suniverse V .V .I

Consider The melting of Ice


H2O (s) + heat H2O (l)
H = 6.03 103 J/mol
S system = 22.1 J/K mol
Condition (1) melting of ice at 10C (Below M.P.)
Temp = 263 K;
H = 6.03 103
S system = 22.1 J/K
S surro = H/T =6.03 103 / 263 = 22.9 J/K S
universe = S sys + S surro = 22.122.9 = 0.8 J/K
S universe is ve hence process is not spontaneous
G = Suniverse T = ( 0.8) 263 = 2.1 102 J
G is +ve hence process is nonspontaneous.
we can calculate G from eq. G = H T S also,
G = 6.03 103 263 22.1 = 2.1 102 J

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System

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PA = Probability of finding molecule A


PB = Probability of finding molecule B
PA PB = Probability of finding molecule A and B at
the same time
In probability
denotes AND
+ denotes OR
From above example, it is clear that as no of molecules
increases probability (chance) of finding of molecule at
the one place decrease.
According to 2nd law of thermodynamics entropy of
universe always increase in spontaneous process.
Surrounding : The rest part of the universe other than
the system is called surrounding.

Condition (2) melting of ice at 0C (at M.P.)


Temp = 273 K;
H = 6.03 103
G = H TS = 6.03 103 263 22.1 = 0
G =0 (process is at equilibrium)
Suniverse = Ssystem + Ssurro
= 22.1 (6.03 103 /273) = 0
Condition (2) melting of ice at 10C (above M.P.)
Temp = 283 K;
H = 6.03 103
G = H TS = 6.03 103 263 22.1
= 2.2 102 Joule
Process is spontaneous.
Q : By which statement we can say confirmly process
is spontaneous.
(a) S system is +ve
(f) S universe is ve
(b) S system is ve
(g) G is +ve
(c) S surro is +ve
(h) G is ve
(d) S surro is ve
(i)
EMF is +ve
(e) S universe is +ve
(j)
EMF is ve
Ans: (e), (h) and (i)
* Relation of G with emf is G = nFE
* Relation of G with Suniverse is G = TSuniverse
Conditions for Spontaneity
condition

Suniverse

EMF

Spontaneous
reaction

ve

+ ve

+ ve

Non-spontaneous
reaction

+ve

ve

ve

Reaction is at
equilibrium

THERMODYNAMIC EQUILIBRIA
(a)

On the basis of free energy


G = G + RT lnQ (Q may be Qp and Qc)
At equilibrium condition Q = 0, G = 0
G = RT lnK (K may be Kp or Kc)
ln K =

G 0

RT

G 0
K = anti ln

RT

( G

/RT

K =e
Equilibrium constant (Kp or Kc) can be
calculated by above equation.

ln K =

0
S reaction
K = anti ln

0
S reaction

K = e ( S reaction /R )

(c)

Equilibrium constant (Kp or Kc) can be


calculated by above equation.
On the basis of electromotive force f or
Oxidation, Reduction and Redox reaction.
G = G + RT ln Q
........(1)
also, G = nFE and, G = nFE
eq. (1) can be also written as
nFE = nFE + RT ln Q........(2)
eq. (2) is divided by nF

E =E0

RT
ln Q
nF

At 25C this equation changes into

E =E0

0.0592

ln Q

At equilibrium, Q = K and E = 0.

REACTION QUOTIENT
W hen reactants and products of a given
chemical reaction are mixed it is useful to know whether
the mixture is at equilibrium, and if not, in which direction
the system will shift to reach equilibrium.
If the concentration of one of the reactants or
product is zero, the system will shift in the direction that
produces the missing component. However, if all the
initial concentrations are non zero, it is more difficult to
determine the direction of the move toward equilibrium.
To determine the shift in such case, we use the reaction
quotient (Q). The reaction quotient is obtained by
applying the law of mass action, using initial
concentrations instead of equilibrium concentration.
Reaction quotient in the term of pressure known
as Qp and reaction quotient in the term of concentration
known as QC .

N2 (g ) + 3H2 (g )
2NH3 (g )
Qc =

(PNH3 )2
[NH3 ]2
=
and
Q
P
[N2 ][H2 ]3
(PN2 )(PH2 )3

Qc and Qp is defined at any concentration and at any


pressure respectively.

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On the basis of entropy


S reaction = S reaction RlnQ
At equilibrium Q = K, S reaction = 0
S reaction = R lnK

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(b)

If at any time Q < K, the forward reaction must occur to


a greater extent than the reverse reaction for equilibrium
to be established. This is because numerator of Q is
too small and the denominator is too large.
Reducing the denominator and increasing the
numerator requires forward reaction until equilibrium is
established.
If Q > K, the reverse reaction must occur to
greater extent than the forward reaction for equilibrium
to be reached. When Q = K, the system is at equilibrium,
so no further net reaction occurs.
Conclusion:
Q < K Forward reaction predominates
until equilibrium is established.
Q = K System is at equilibrium.
Q > K Reverse reaction predominates
until equilibrium is established.
Prob. 1 For the synthesis of ammonia at 500C, the
equilibrium constant is 6.0 102 L2/mol2. Predict the
direction in which the system will shift to reach
equilibrium in each of following case. Reaction for

synthesis of NH3 is N2 (g ) + 3H2 (g )


2NH3 (g )
[NH3]0 = 1 103 M,
[H2]0 = 2 103 M
[NH3]0 = 2 104 M,
[H2]0 = 3.54 101 M

(a)
(b)
Ans:

[N2]0 = 1 105 M
[N2]0 = 1.5 105 M

(a) QC = 1.2 107 L2/mol2


QC > KC Hence back reaction predominates.
(b) QC = 6.0 102 L2/mol2
QC = KCReaction is at equilibrium.

Your Problem in chemistry


N o w a da y s , m o st l y
students suffer trouble and
fear in vital topic like Acid
Base Titration, Indicator,
Double Indicator, Redox
Titration, Ionic Equilibria,
Electrochemistry,
Thermodynamics, Chemical
Equilibria and Chemical Kinetics. Our main
motto to relate all topic with highly advanced,
accurate and easy concept. Problem asked in
Exam like C.B.S.E. (Mains), B.C.E.C.E.
(Mains), AIEEE and IIT are not chapter wise
problem but concept based problem.

-Shailendra Kumar

MAIN OBJECTIVES

1.

CONCEPTOFMILLIEQIVALENT.
wt
eq.wt
wt 1000
No of milliequivalent =
eq.wt
wt 1000
No of meq
N=
=
V(ml)
eq.wt V(ml)
No of equivalent =

No of meq = N V(ml)
wt , No of milli mol = wt 1000
No of mol = mol.wt
mol.wt
No of milli mol = M V(ml)
CONVERSION FACTOR
M V.F (Valence Factor) = N
No of mol V.F = No of eq.
No of milli mol V.F = No of meq.
No of eq = mol.wt
V.F
+

3Y

X2Y3 (By Meq Method)


Changed

Milliequivalent X + Y
befor reaction 10
6
Milliequivalent
after reaction

2X

No need of
balanced equation
X2Y3
0 (Suppose)
6

Meq of X Reacted = 6
Meq of Y Reacted = 6
Meq of X2Y3 formed = 6
During reaction equal meq of reactant reacted and equal
meq of product formed.
Species
V.F
K+
1
SO42
2
Al+3
3
Ca+2
2
CaSO4
2

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Ionic Equilibria

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New Concepts of

1.
2.
3.
4.
5.
6.
7.
8.
9.

Concept of Milliequivalent.
Auto ionisation of pure water.
PH Calculation of strong acid
and strong base.
PH Calculation of weak acid and
weak base.
PH Calculation of weak acid and
weak base in the present of its salt.
Common Ion effect.
Buffer Solution.
Salt hydrolysis.
Solubility Product Principle
H2SO4
AlCl3
Al2(SO4)3
COOH
2H O
COOH 2
K2SO4 Al2(SO4)3 24H2O

2
3
6
2
8

When 4.9 gm of H2SO4 mixed with 4 gm of


2
NaOH. What is the
(a) Wt of NaOH reacted.
(b) Wt of H2SO4 reacted.
(c) Mol of Na2SO4 formed.
H2SO4 + NaOH
Na2SO4 + H2O
Meq befor 4.9 1000 4 1000
0
0
reaction
40
49

(100)

(100)

100

100

Meq after
0
0
reaction
(a) Wt of NaOH completely reacted in this reaction,
Hence wt of NaOH reacted is 4 gm.
(b) H2SO4 completely reacted in this reaction, hence wt
of H2SO4 reacted is 4.9 gm.
(c) No of meq of Na2SO4 formed is 100
100
No of milli mol of Na2SO4 =
2
No of milli mol of Na2SO4 = 50
No of mol of Na2SO4 = 50 103
= 5 102 mol
Dilution
means addition of solvent (generally H2O)
During dilution, wt of solute remains constant
Mol.wt of solute

Mol of solute

Milli mol of solute


No of millimol = M V(ml)
During dilution MV = constant
M1V1 = M2V2
or
N1V1 = N2V2

During dilution millimol of solute remains


constant.

2.
(a)

AUTO IONISATION OF PURE WATER


H+ + OH

H2O
or
H2O + H2O
K ionization =

H3O + OH
[H+] [OH]
[H2O]

K ionization [H2O] = [H+] [OH]


Kw = [H+] [OH]
1 1014 = [H+] [OH]

3.

PH CALCULATION OF STRONG ACID AND


STRONG BASE
Actual Method for PH Calculation.
Calculate PH for 1 102 M HCl
H2O
H+
+ OH
x
HCl
H+ + Cl
102
Common ion effect

Kw = [H+] [OH]
Kw = (x + 102)x
1 1014 = (x + 102)x
After solving quardatic equation value of H+ provided by H2O is very less in comparison to H+ provided by
HCl, Hence H+ provided by H2O is neglected.
Hence [H+] = 102
PH = 2

In pure water molarity of [H+] is 107 M but in acidic


medium value of H+ provided by H2O is less than 106 M due
to common ion effect, But in rough calculation we also take
molarity of [H+] is 106 M in acidic solution.

If [H+] produced by acid is less than 106 M or equal


to 106 M then [H+] produced by H2O is not neglected.

If [H+] produced by acid is greater than 106 M then


[H ] produced by H2O is neglected.
+

[H+] [OH] = Kw = 1014 (At 25 C)


taking log both side.
log [H+] [OH] = Kw
PH + POH = PKw = 14

Strong acid (like HCl, HNO3, H2SO4 etc) and strong


base (like NaOH, Ca(OH)2 , Mg(OH)2 etc) are completely
dissociated.
Meq of S.A = Meq of H+
Meq of S.B = Meq of OH
Calculate Molarity of H+ and Normality of H+ in
2
1 M H2SO4
Neglected

H2SO4
2 H + SO42
100% dissociated
H2SO4
H+ + SO42
0
0 Let volume
Meq befor D. 1 2 V
of solution
(2V)
is V(ml)
Meq after D.
0
2V
2V
2V
Normality of H+ = V
Meq of H+ = 2V
Millimol of H+ = 2V (V.F = 1)
=2
2V
+
[H ] =
= 2
V
Molarity of H+ = Normality of H+

Value of Kw = 1 1014 at 25 C
Ionisation or Dissociation of H2O is Endothermic
reaction. Hence if temp is increased value of Kw
also increase.
Value of Kw at 25 C is 1 1014 .
Kw is known as ionic product of water.
(b)
PH scale (014) valid for Kw (value equal to
1 1014 )
(c) Q. At certain temp (temp greater than 25 C) Value
of kw is 1 1013 What is its neutral point and what
is its PH scale.
Solution :
PH scale ( 013)
Its neutral point is 6.5
Kw = [H+] [OH]
1 1013 = x.x
x2 = 1 1013
x = 1 106.5 = [H+] = [OH]
Hence PH at neutral point is 6.5
(d)
[H+] [OH] solution is Neutral
[H+] > [OH] solution is Acidic
[H+] < [OH] solution is Basic

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Calculate wt of AgCl formed when 200 ml of 5 N


HCl reacted with 1.7 gm AgNO3
Solution : Write unbalanced reaction
AgNO3 + HCl AgCl + HNO3
Milliequivalent 1.7 1000 200 5
0
0
befor reaction
170
(1000)
(10)
Milliequivalent
10
10
990
0
after reaction
Meq of AgCl formed = 10
wt 1000 =10
143.5
Wt = 1.435 gm

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Molarity of H+ and Normality of H+ is equal, and


meq of H+ and millimol of H+ is equal because valence
factor is 1.
Molarity of OH = Normality of OH (V.F =1)

Meq of OH
= Millimol of OH (V.F =1)
Meq of strong acid = Meq of H =Millimol of H

N V(ml)
N V(ml)
M V(ml)
Normality of strong acid=Normality of H+ =Molarity of H+
Conclusion : If we want to calculate PH of strong acid then

Calculate PH of 0.5 102 M Ca (OH)2 .


Normality of Ca (OH)2 = Molarity of (OH)
0.5 102 2 = [OH]
1 102 = [OH]
POH = 2, PH = 12

PH = log 1.11
300

Calculate PH of 102 M HCl.


PH = 2 But this is not true, practically PH of this
solution is near to zero.
Calculate PH of 1M HCl.
2
PH = 0 this solution is most acidic. Greater the
[H+] greater will be acidity and lesser will be PH.

Calculate the [Cl ], [Na+], [H+], [OH] and PH of


resulting solution obtained by mixing 50 ml of 0.6 N HCl
and 50 ml of 0.3 NaOH.
HCl + NaOH NaCl + H2O
Meq befor
30
15
0
0
reaction
Meq after
15
0
15
15
reaction
Meq of HCl = 15
Meq of H+ = 15
15
[H+] = 100 = .15
PH = log [H+] = log 0.15
PH = 0.8239
[OH] [H+] = 1 1014
14
[OH] = 1 10
= 6.6 1014 M
0.15
Meq of Cl = meq of Cl provided by NaCl + meq of Cl
provided by HCl.
= 15
+
15
Meq of Cl = 30
30
Millimol of [Cl] = 100 = 0.3 M
Meq of Na+ = meq of Na provided by NaCl
= meq of NaCl
Millimol Na+ = 15
[Na+] = 15
100 = 0.15 M
4.

PH CALCULATION OF WEAK BASE AND


WEAK ACID.
BOH
weak base
Before
C
dissociation

B+
0

After
dissociation

CC
Kb =

[B+] [OH]
=
[BOH]

OH

C . C
C (1 )

Kb = C2 (If is very less)


(1) 1
=

Kb
C

[OH] = C = C

Kb = Kbc
C

[OH] = (Kbc)
POH = log[OH]
= log(Kbc)
(1)
(2)
(3)

POH = (PKb log c) V.V.I


[OH] = Kbc = C
= Kb
C
For weak base

Dissociation constant of weak base

Note : If PH of more concentrated acid is less than 0 (ve)


then PH of this concentrated acid is taken as zero.

Calculate PH of the solution when 100 ml of 1


10 M HCl, 100 ml of 1 104 M HNO3 and 100 ml of 1
102 N H2SO4 mixed.
Solution :
Meq of H+ = meq of H+ provided by HCl + meq H+provided
by HNO3 + meq of H+ provided by H2SO4
+
Meq of H = meq of HCl + meq of HNO3 + meq of H2SO4
100 103 + 100 104 + 100 102
millimol of H+ =0.1 + 0.01 + 1
300 M = 1.11
M = 1.11
300
PH is determined by equation

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Calculate PH 100 ml of 1 102 M H2SO4 .


Solution : PH of the solution independent on volume. It
depends upon normality of acid.
Method (1)
Normality of H2SO4 = Normality of H = Molarity of H+
1 102 2 = Molarity of [H+]
2 102 = Molarity of H+
PH = 2 log2
Method (2)
Meq of H2SO4 = Millimol of H+
100 102 2 = 100 [H+]
[H+] = 2 102
PH = 2 log2

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we convert molarity acid into normality of acid, which is directly equal to molarity of H+
2
Calculate PH of 1 102 M H2SO4 .
Molarity of H2SO4 = 1 102 M
Normality of H2SO4 = 2 102 N
Normality of H+
= 2 102
+
Molarity of H = 2 102
PH = log [H+]
PH = log (2 102)

5.
PH CALCULATION OF WEAK ACID AND
WEAK BASE IN THE PRESENCE OF ITS SALT.

Example 1: If we want to calculate PH of CH3 C OH


O
(C ) in the presence of CH COONa (C )
2

Na

100%

O
C1
CH3 CO+
O
O

O
C1
H

B.D
C1
A.D
O
CH3COOH

CH3COO +

CH3 COONa

B.D

C2

A.D

C2 C2

C2

O
C2

Ka =

Ka =

[C1+C2] [C2]
C2 C2

[H+] = Ka. [C2 C2]


[C1 + C2]
PH = PKa + log

[C1+ C2]
[C2 C2]

Value of C2 is very very less,


hence [C1+ C2] = C1 and [C2 C2] = C2
C1
PH = PKa + log
C2
[salt]
This equation is
PH = PKa + log

[acid]
not 100% correct
Example 2 : If we want to calculate PH of NH4OH (C2) in
the presence of NH4Cl (C1)

10

C1
O
NH4OH

B.D

C2

A.D

C2 C2

C2

C2

O
C1
NH4+

O
C1
+OH

Dissociation of NH4OH is
depressed due to NH4Cl
Kb =

[NH4+][OH]
[NH4OH]

Kb =

[C2 + C1][OH]
[C2 C2]

[OH] = Kb

[C2 + C1][C2]
[C2 C2]

[C2 C2]
[C1 + C2]

POH = PKb + log


POH = PKb + log

POH = PKb + log

[C1+ C2]
[C2 C2]
[C1]
[C2]
[salt]
This equation is
[base]
not 100% correct

Method for PH Calculation of Following Reaction


Condition 1.
NaOH + CH3CH
CH3CNa + H2O
Meq.B.R 10
5 O
0 O
0
(Suppose)
Meq.A.R 5
0
5
5
If strong acid or strong base present in solution
after reaction then PH is calculated by strong acid or strong
base. Concentration of salt not considered.

O
[CH3CO][H+]
=
[CH3COH]
O
[C1+C2] [H+]
[C2 C2]

100%

+Cl

B.D
A.D

Due to common ion


dissociation of CH3COOH is
depressed

NH4

Calculate PH of
(a) 0.002 N acitic acid having 2.3% dissociation.
(b) 0.002 N NH4OH having 2.3% dissociation.
+
(a) [H ] = 2 103 2.3 = 4.6 105 M
100
PH = 5 log 4.6 = 4.3372
2.3
(b) [OH] = C = 2 102 100
= 4.6 105 M
POH = 4.3372
PH = 9.6627

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For weak acid

NH4Cl

PH = (PKa log c)
[H+] = C = KaC
= Ka
C

Condition 2.
NaOH + CH3COOH
CH3COONa + H2O
Meq.B.R 10
10
0
0
(Suppose)
Meq.A.R 0
0
10
10
If solution contains only salt [CH3COONa] then
PH calculate by salt hydrolysis.
Condition 3.
NaOH + CH3 COOH
Meq.B.R 5
10

CH3COONa + H2O
0
0

Meq.A.R 0
5
5
5
If solution contains weak acid and its salt then PH
is calculated by.

Calculation of PH in the reaction NH4OH with HCl


Condition 1.
NH4OH + HCl
NH4Cl + H2O
5
0
0
Meq.B.R 10
0
5
5
Meq.A.R 5
Solution contains weak base and its salt.
POH = PKb + log

[salt]
[base]

Condition 2.
NH4OH + HCl
NH4Cl + H2O
Meq.B.R 5
10
0
0
Meq.A.R 0
5
5
5
PH is calculated by HCl (strong acid)
Condition 3.
NH4OH + HCl
NH4Cl + H2O
Meq.B.R 5
5
0
0
Meq.A.R 0
0
5
5
PH is calculated by salt hydrolysis (NH4Cl)

Calculate PH of the following mixtures, given that


Ka = 1.8 105 and Kb = 1.8 105

50 ml of 0.10 M NaOH + 50 ml of 0.05 M CH3COOH


(a)
(b)
50 ml of 0.05 M NaOH + 50 ml of 0.10 M CH3COOH
(c)
50 ml of 0.10 M NaOH + 50 ml of 0.10 M CH3COOH
(d)
50 ml of 0.10 M NH4OH + 50 ml of 0.05 M HCl
(e)
50 ml of 0.05 M NH4OH + 50 ml of 0.05 M HCl
(f)
50 ml of 0.10 M NH4OH + 50 ml of 0.10 M HCl
Solution : (a)
NaOH + CH3 COOH
CH3COONa + H2O
Millimol. 500.1
500.05
0
0
B.R

Millimol.
2.5
0
2.5
2.5
A.R
Solution after reaction contain strong base (NaOH)
Hence PH determined by NaOH
Meq of NaOH = 2.5
N of NaOH = 2.5 = 2.5 102 M
100
[OH] = 2.5 102
POH = 1.6021
PH = 12.3979
(b)
NaOH + CH3 COOH
CH3COONa + H2O
5
0
0
Meq.B.R 2.5
2.5
2.5
Meq.A.R 0
Solution after reaction contains weak acid and its
salt, Hence PH determined by the equation
[salt]
PH = PKa + log
[acid]

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[salt]
[acid]

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PH =PKa + log

11

PH = log Ka + log

[CH3 COONa]
[CH3 COOH]

2.5
[CH3COONa] = 100
= 4.74 + log

2.5/100 , [CH COOH] = 2.5


3
100
2.5/100

PH = 4.74
(c)
NaOH + CH3 COOH
5
Meq.B.R 5

CH3COONa + H2O
0
0

Meq.A.R 0
0
5
5
If solution contains salt after reaction then PH determined by salt hydrolysis. Salt hydrolysis discused latter.
Problem (d), (e) and (f) do yourself.
Hints :
(d) PH determined by buffer equation.
(e) PH determined by strong acid (HCl)
(f) PH determined by salt hydrolysis (NH4Cl)
6 & 7. BUFFER SOLUTION AND COMMON ION
EFFECT BUFFER SOLUTION AND COMMON
Buffer solution: solution which possess reserve acidic nature or alkaline nature or solution which resist change in PH
due to dilution or addition of small quantity of acid or alkali
are known as buffer solution.
Example of acidic Buffer
A weak acid + its salt (CH3COOH + CH3COONa)
Basic Buffer
A weak base + its salt (NH4OH + NH4Cl)
Equation acidic buffer is
[salt]
PH = PKa + log
[acid]
Equation for basic buffer is
[salt]
PH = PKa + log
[acid]
2
Calculate change in PH ( PH ) which 0.01 mol
NaOH added into.
(a) 1.0 litre pure water
(b) 1 litre of 0.10M CH3COOH
(c) 1litre solution 0.10 M CH3COOH and 0.10M CH3COONa
(a)
In pure water, [H+] = [OH] = 107
Hence PH1 = 7
After addition of .01 mol of NaOH
[NaOH] = 0.01 = 0.01
1
[OH] = 1 102
POH = 2, PH2 = 12
PH = PH2 PH1 = 127 = 5
NaOH reacts with acetic acid.
NaOH + CH3 COOH
CH3COONa + H2O
Mol.B.R 0.01
0.10
0
0
Mol.A.R 0
(0.010.01)
0.01
0.01
0.09
Solution contains weak acid and its salt, Hence

(b)

= 4.74 + log

0.10
0.10

PH1 = 4.74
PH after addition of NaOH
CH3COONa + H2O
CH3COOH + NaOH
0.10
0.01
0.10
Mol.B.R
(0.10 + 0.01)
[salt]
PH2 = PKa + log
[acid]
0.11
PH2 = 4.74 + log
0.09
0.11
PH = PH2 PH1 = log
= 0.087
0.09
Conclusion : After addition of NaOH PH is very less in
buffer solution (mixture of weak acid and its salt).
Preparation of Buffer
Mol.A.R

(0.100.01) 0

I.

Acidic Buffer
(a) Mixing weak acid and its salt.
(b) Exess weak acid acid and strong base
CH3COOH + NaOH
CH3COONa + H2O
Meq.B.R 10
5
0
0
0
5
5
Meq.A.R 5
(c) Exess basic salt + HCl
CH3COONa + HCl
NaCl + CH3COOH
Meq.B.R 10
2
0
0
0
8
8
Meq.A.R 8

II.

10

Best Buffer (most sensitive buffer)


PH range of acidic buffer
PH = PKa + log [salt]
[acid]

12

PH = PKa 1
In the same manner POH of range of basic buffer
[salt]
POH = PKb + log
[base]
POH = PKb 1
2
A physician or lab technician want to prepare buffer
solution having PH = 5 using CH3COOH and CH3COONa.
What will be ratio of [CH3COONa]
[CH3COOH]
(PKa of CH3COOH is 4.74)
PH = PKa + log [salt]
[acid]
[CH3COONa]
5.0 = 7.74 + log
[CH3COOH]
[CH3COONa]
[CH3COOH] = 0.26
[CH3COONa]
= anti log 0.26 = 1.8
[CH3COOH]

log

Note:
Buffer has maximum capicity when its acid has
its PKa as close as possible to the target PH.
A physician want to prepare buffer solution hav2
ing PH = 5 using weak acid and its salt, which of the following weak acid and its salt would be a good choice.
Acid
Salt
PKa
(a)
H3PO4
H2PO42
2.12
(b)
HCOOH
HCO2
3.74
(c)
CH3COOH
CH3COO
4.75
(d)
H2PO42
HPO42
7.21
Ans = c

What mass of sodium acetate (CH 3 COO


Na.3H2O,M.W = 136) and what volume of concentrated
acetic acid (17.45 M) should be used to prepare 0.50 L of a
buffer solution at PH = 5.0 that is 0.150 M overall ?
Mass of sodium acetate (hydrated) = 6.6 gm
Volume of Acetic acid = 1.5 ml
8.

SALT HYDROLYSIS

Concept Suppose you want to calculate PH of sodium acetate (basic salt) of certain concentration (c)
O
O
CH3CONa
CH3CO + Na (Any salt is
100%
100%
C
0
0 dissociated)
B.D
0
C
C
A.D
anionic hydroysis taken place.
CH3COO + H2O
CH3COOH + OH
C
0
0
B.R
A.R CC
C
C
CH3COO (Acetate ion) bevaves as weak base

[salt]
[acid] 0.1

[salt]
[acid]

ratio vary 0.1 to 10

PH = PKa + log

[salt]
[acid]

Basic Buffer
(a) Mixing weak base and its salt
NH4OH + NH4Cl
(b) Exess NH4Cl + HCl
(c) Exess NHaCl + NaOH
PH range of buffer solution

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(c)

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[salt]
[acid]
PH2 = 4.74 + log 0.01
0.09
PH2 = 3.78
PH of 0.1 M CH3COOH is
PH1 1/2 (PKa log C)
PH1 = 1/2 (4.74 + 1) = 2.87,
PH = PH2 PH1 = 3.78 2.87
PH = 0.91
PH1 = PKa + log [salt]
[acid]
PH2 = PKa + log

PKb (CH3COO) = 10 log 5.6


= 9.25
POH of weak base is denoted by equation
POH = 1/2 (PKb log c)
POH = 1/2 (PKb (CH3COO)log c)

Generally is replaced by h (degree of hydration)


and Kb of CH3 CO is replaced by KH (Hydrolysis constant)
O
MISCONCEPT

Conjugate base of weak acid is strong. It is not


true. Conjugate base of weak acid is also weak.
Example : Ka of CH3COOH is 1.8 105 (W.A)
Ka of CH3CO is 5.6 1010 (W.B)
O
Conjugate acid of weak base is strong

It is not correct.
Conjugate acid of weak base is also weak.
Example : Kb of NH4OH is 1.8 105 (W.B)
Kb of NH4+ is 5.6 1010 (W.A)
NH4OH + H+
NH4+ + H2O
[NH4OH][H+][OH]
[NH4+][OH]
1.0 1014
Kw
=
+ =
1.8 105
Ka(NH4 )

Ka (NH4+) =

Ka [NH4+] = 5.6 1010


This concept is useful for the solution of problem
of salt hydrolysis.

Weaker the acid stronger its conjugate base .


Weak Acid
Ka
Cunjugate
Kb
Base
HX
1 103
X
1 1011
HY
1 104
Y
1 1010
HZ
1 105
Z
1 109
Weaker the acid
stronger its conjugate base
Weaker the base stronger its conjugate acid.

Calculate for 0.01 N solution of sodium acetate.


(a) Hydrolysis constant
(b) Degree of Hydrolysis
(c) PH (Ka = 1.8 105)

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Kb(CH3COO) = 5.6 1010


Kb of (CH3CO) Acetate ion denotes, it is weak base
O

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[CH3COOH][OH][H+]
[CH3COO][H+]
Kw
1 1014
Kb(CH3COO) = Ka(CH COOH) =
1.8 105
3
Kb(CH3COO) =

13

Solution :
Kw
(a) Kb (CH3COO) = KH = Ka(CH COOH)
3
1 1014
=
1.8 105
= 5.6 1010
Kb(CH3COO)
=
C

(b) h =

5.6 1010
0.01

= 2.3 104
(c) POH = 1/2 (PKb log c)
= 1/2 (PKb(CH3COO) log c)
= 1/2 (9.25 log 0.01)
= 1/2 (9.25 + 2)
= 5.625
PH = 8.375

Calculate the hydrolysis constant of the salt containing NO2 ions.


Given Ka for HNO2 = 4.5 1010
Solution :
Kw
1014
=
= 2.2 105
KH =
Ka
5.6 1010

2
What is PH of 0.5 M aqueous NaCN solution PKb
of CN = 4.70.
NaCN
Na + CN
CN + H2O
HCN + OH
Kb (CN) =

[HCN] [OH]
[CN]

POH = 1/2 (PKb log c)


POH = 1/2 (4.70 log 0.5)
POH = 2.5
PH = 11.5

Calculate the percentage hydrolysis in 0.003 M a


queous solution of NaOCN.
Ka for HOCN = 3.33 104
h=

Kb (OCN)
C

KH
=
C
=

Kw
1014
=
Ka (HOCN)C
3.33 104 0.003

h = 104, % hydrolysis = 102 %


Hydrolysis of Acidic salt (like NH4Cl)
B.D
A.D

NH4Cl
C
0

NH4+ + H2O
Befor hydrolysis C
After hydrolyCCh
sis

NH4+ + Cl
0
0
C
C
NH4OH + H+
0
0
Ch
Ch

Kw
Kb(NH4OH)
1 1014
Ka(NH4+) =
= 5.6 1010
1.8 105
=

NH4+ behaves as weak acid.


PH of the weak acid is calculated by the equation.
PH = 1/2 (PKa log c)
Ka (NH4+) = 5.6 1010
PKa (NH4+) = 10 log 5.6
PKa(NH4+) = 9.25

Calculate the PH of 0.1 M NH4Cl.


KbNH4OH = 1.8 105
PH = 1/2 (PKa log c)
= 1/2 (9.25 log 0.1) = 1/2 (10.25)
PH = 5.12

Kw = Kb (X) Ka(Hx)
taking log both side
PKw = PKb + PKa
14 = PKb + PKa

A certain buffer solution contains equal concentration of X and Hx. Kb for X is 1010. Calculate PH of
buffer.
Kb for X = 1010
Kw 1 1014
Kb for Hx = Kb =
= 1 104
1.0 1010
PKa for Hx = 4
[salt]
PH = PKa + log
[acid]
PH = 4
SOLUBILITY PRODUCT PRINCIPLE

Most compounds dissolve in water to some extent


and many are so slightly soluble that they are called
Insoluble

14

Compounds that dissolve in water to the extent of


0.02 mole per litre or more are classified as soluble.

Slightly soluble compounds are important in many


natural phenomenon. Our bones and teeth are mostly calcium
phosphate Ca3(PO4)2 a slightly soluble compound.

Tooth decay involves solubility, when food lodges


between the teeth, acids form that dissolve enamel, which
contain a mineral called hydroxyapatite (Ca5(PO4)3OH).
Tooth decay can be reduced by treating teeth with fluoride.
Fluoride replaces the hydroxide to hydroxyapatite to produce
the corresponding fluorapatite Ca5(PO4)3 F and CaF2, both
of which are less soluble in acid than original enamel.
SOLUBILITY PRODUCT CONSTANT
Suppose we add one gram of solid BaSO4 to 1.0
litre of water at 25C and stir untill the solution is saturated
very littile BaSO4 dissolves only 0.0025 gm of BaSO4
dissolves in 1.0 liter of water, no matter how much more
BaSO4 is added. Hence BaSO4 is known as slightly soluble
compound.
BaSO4(s) + H2O
BaSO4(aq)
Ba+2(aq) + SO42(aq)

Note : Hydrolysis of Na and Cl not taken place because


it comes from strong base and strong acid.
Ka for strong acid is very large.
So Kb of Cl is very-very small, Hence hydrolysis

of Cl not takes place. Value of Kb for strong base is very


large, so, Ka of Na+ is very low, Hence hydrolysis of Na+ not
takes place.
If Hx is weak acid (Ka) then value of conjugate
acid (X) is Kb then.
Kw
Kb (x) =
Ka (Hx)

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[NH4OH][H+][OH]
[NH4+][OH]

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Ka (NH4+ ) = KH =

100 % (generally)

Minimize
BaSO4(s) + H2O
K=

Ba+2(aq) + SO42(aq)

[Ba+2]eq [SO42]eq
BaSO4(s)
eq denotes equilibrium

K BaSO4(s) = [Ba+2]eq [SO42]eq


Ksp = [Ba+2]eq [SO42]eq
In equilibrium that involve slightly soluble
compound in water, the equilibrium constant is called a
solubility product constant (Ksp). The activity of solid BaSO4
is one. Hence the concentration of solid is not included in
the equilibrium constant expression.
Other Example :
CaF2
Ca+2(aq) + 2F (aq)
Ksp = [Ca+2] [F]2 = 4S3
Bi2S3(s)
2Bi+3(aq) + 3S2(aq)
Ksp = [Bi+3]2 [S2]3 = 108 S5
MyXz(s)
yM+2(aq) + Zxy(aq)
+2 y
Ksp = [M ] [ Xy]z = (Sy)y x (Sz)z
MgNH4PO4(s)
Mg+2(aq) + NH4+(aq) + PO43(aq)
+2
Ksp = [Mg ] [NH4+] [PO43] = S3
Molar Solubility :- Molar solubility of a compound is the
number of mole that dessolve to give one litre of saturated
solution. It is generally respresented by S.

We frequently use statements such as The solution


contains 0.0025 gm of dissolved BaSO4. Which means
0.0025 gm of solid BaSO4 dissolves to give a solution that

Ksp

1.1 105 M 1.1 105 M

Ksp = (1.1 105 ) (1.1 105 )


= 1.2 1010

Reaction Quotient in precipitation Reation

No necessarily
at equilibrium

Qsp
Q Qc

Qp

Qsp
K Qc

Qp

used in chemical
equilibrium

used in ionic
equilibrium
used in
chemical
equilibrium

Necessarily at
equilibrium.

Qsp also known as ion product.


Forward process is favored. No
precipitation occure, more solic can
dissolve.
Qsp = Ksp Solution is just saturated, reaction is at
equilibrium
Qsp > Ksp Reverse process is favored, precipitation
occures.
Question : If 100 mL of 0.00075 M Na2SO4 and 50.0 mL of
0.015 M BaCl2 solution are mixed, will a precipitate form ?
Ksp of BaSO4 is 1.1 1010
0.015 50 2
[Ba+2] =
= 5 103 M
2 150
100 0.00075 2
[SO42] =
= 5 104 M
150 2
If

Qsp < Ksp

Qsp = 2.5 106


Qsp > Ksp
Solid BaSO4 precipitated untill [Ba+2] [SO42] just
equal to Ksp of BaSO4
Common Ion Effect in solubility Calculation :
Example : The molar solubility of MgF2 is 1.2 103 M in
pure water at 25C. Calculate the molar solubility of MgF2
is 0.10 M NaF.
MgF2(s) + H2O
Mg+2 + 2F
+2
2
Ksp = [Mg ] [F ] = S. (2S)2 = 4S3
= 4 (1.2 103)3
= 6.4 109

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After dissociation
at equilibrium

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= 1.1 105 M
BaSO4(s)
Ba+2(aq) + SO42(aq)
Before
5
0
0
dissociation 1.1 10 M

NaF

15

H2O + MgF2(s)
S

Na+ + F
Due to common
0.1
100%
reaction
ion
+2

Mg (aq) + 2F (aq) shifted towards


left
+S
+2S

contains equal number of Ba+2 and SO42 ions.


Question : 1.0 liter of saturated BaSO4 solution contains
0.0025 gm of dissolved BaSO4. Calculate the solubility
product constant for BaSO4 .
Solution :
2.5 103
Molar solubility (s) =
M
233

Ksp = (S) (2S + 0.1)2,


(2S + 0.1) = 0.1
6.4 109 = (0.1)2 S
Neglected
S = 6.4 109 102
= 6.4 107 M
Hence solubility of MgF2 is decreased in NaF in
comparision to pure water due to common ion (F) which is
provided by NaF.
Relative Solubilities
A salts Ksp value gives as information about its
solubility. They are two possible cases :
(1)
The salts being compared produce the same number
of ions. For Example,
Consider :
AgI (s)
Ksp = 1.5 1016
CuI (s)
Ksp = 5.0 1012
CaSO4
Ksp = 6.1 105
2
Ksp = S
S = Ksp = Solubility
In this case we compare the solubilities for these
solid by comparing the Ksp values :
CaSO4 (s) > CuI(s) > AgI (s)
Most soluble
largest Ksp

Least soluble
smallest Ksp

The salts being compared produce different


numbers of ions. For Example,
Consider :
CuS (s)
Ksp = 8.5 1045
Ag2S (s)
Ksp = 1.6 1049
Bi2S3(s)
Ksp = 1.1 1073
These salt prodeces different numbers of ions when
they dissolve. The Ksp values connot be compared directly
to determine relative solubility.
Relative solubility measured by above mentioned
Rule
*
Remember that relative solubility can be predicted
by comparing Ksp value only for salts that produce the same
total numbre of ions.
For CuS
For Bi2S3
(2)

S2 = Ksp
S = Ksp
For :
Ag2S
4S3 = Ksp
1
Ksp /3
S= 4

108 S5 = Ksp
1
Ksp /5
S = 108

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