Classroom

Classreom, Pagt Na
PacdNa.
Date
Date

HNO4 >H t NOg

Cp-CyER

2t
t20
2+
PV nRT_J
doni Eauilibum NHyCe NHt 0

Rat toncart & bockoand axAagal

HcooH
toot into jot

Modiat weak Giaeemples

Serg
Electdt CGHs c00t Ht
(a=2470)/) C
Fa ctoz Aating Degpee af dixaoiatem (ooo)(0) Hy t ch

* Teopatuna

cyuilbaica Cenataal

CH CoDH
 Face No.
Classroom.

Dete / Date

Ostewad diltien laus:

forceak
oleetnalyla
HAa H
becaua

kop = 1 [PbJ' x 2[aj

1[s] x L[a]

A, B

Fadora alleting DoD Kap 2 2 s]x 20:12

Kop

Lo88
islublity
= 0.001 =
3
(0
279

27
 Classroom. Classroom
Pace No
Date
Dat

BalsOy ksp l0)ia

3= Lo-27
-69

-2

In02 M

Btfs- hetpo to Preunt

aud or bassM
added

f3 2X2X2. Neta
pH=7 Baic
2)? pH>T
Salt
s
ohen aid
Gddod in Aüdic
2 CH2 Coo H + NaoH CH, coONNa tH,o

V.V. NHu,o

added,Htittrg NHyDHtHebt
whn aud

goea to salt
ushen ud added
 HT= Cx2 kala
Fage No spm lojm [radassroom,
Page Na.
Date

Aidic
CHgccoH + ct,oNa
CH Coo H ta0H Hc00Na t H,0

LAl

+2HCQ Mac, t2H,O

Mao H),

BoH Bt oH

wohen

M4 (oM), +24 Mg t2H,0 TRor]

(hen has added

-ToH
Hlendnen Haubaleh

HA HtA
BA BT +A

poH =lag k - lng (Baa)

 k
1°C
Ciassrcom. Classroom
Pags No

Date/ Date

fastal Premur
Ke molgr oDCenlealos

-a-c -2:303x 2x 8-314 298

X x

:-534.

Con sta,daken an wnity

Pave nRT
uth g

2X ?14X298

Rote
Chnaial quilibkar
nas achon iRate odforward = Backward

t
Cuesy 2
 Pege
Classreom.
No.
Classroom
Page Na
Dat
Dats

ke[cO,ms
c0, PV= nRT
kp atn

INO,J nal/
TN,o3
kp latm

2
kp

aA
C)
t38t2c+E 9)

LAJ
Change this pastialp
into mola conc frm.
 Ciassrcom.
Classroom
Pace No.
Pags Na.
Date
oatt

SA SB
AU alkahs omtt

ke HaDtHAO
ME,AIl oxgacud

Ra (o)
hydoa

god RDH)

50X2
Sot So

SotSO
[oH] 6xlo

L- lo 6

022
 lonic Equilibria

Ostwald's Dilution Law

toweak electrolyte is known as Ostwald'sdilution au
The application of law of mass action
as follows :
be the weak electrolyte which ionises
Let AB
AB A +B
0 0
Initial conc.
C(1 -a) Ca Ca
Concentration at equilibrium

Hence according to law of mass action,

[A"I[BI
Ca ·Ca Ca?
K (1-a)
[AB] C(1- a)
() is very small as compared to1. Therefore
For very weak electrolyte, the degree
of ionisation

equal to 1. Thus we have,

(l- c) may be taken approximately
K =Ca?

Or

degree of dissociation of a weak electrolyte is inverseh

The aboverelationship implies that the

root of itsconcentration.
proportional to the square
As C = 1
mole/volume
...2

Then a =/KV
of weak electrolyte is direct
The above shows that the degree of dissociation
relationship
root of dilution volume.
proporional to the square 5%. In other cases, a may ba<
Note : (i) Theapproximation (1-a) ~lcan
be applied only if

calculated by applying solution of a quadratic. =

only to weak electrolytes
because for strong electrolytes, a I

(ii) This law is applicable

and Bases
Concepts of Acids
(1)Arrhenius Concept which dissociates to give H ions in aqueous
an acid is a substance
According to Arrhenius,
is the substance which dissociates to give OH ions in aqueoussolution.
solution while a base

e.g., HCI, HNO,, CH,COOH etc. are acids

 lonic Equilibria
161

where and a,are the degree of dissociations of two bases and K, and Ky, are the dissociation
constants of two bases.

lonic Product of Water

Water is a weak electrolyte and does not much
ionise in the pure state. It undergoes self
ionisation as follows :

H,0 (1) + H,0(|) H,0" (aq) + OH (aq)

According to law of mass action, we have

K= HOIOH1
(H,oj²
Or
Kx[H,0 =[H,0*][OH]
Since waterundergoes ionisation to a very smallextent, [H,0]may be regarded as constant, i.e.,
Kx (H,0j is constant, representedby Ky.Then,

Ky = [H,o*]
[OH]
Theconstant Ky is known as ionicproduct of water. Its value is equal to 1-008 x 10l mol L?
at 298 K. As the concentrations of H,0 and OH are equal,

[H,0*]= [OH]=J1-008 x 10-14

=lx 10 mol Ll
The ionisation of pure water increases with an increase in temperature.Therefore the
value of
Ky increases with increase in temperature.However it does not affect the relative concentrationsof
H,0* and OH ions.
pH Value
It is defined as the negative logarithm of theconcentration ofH,expressed in moles per litre.

pH=- logo[H"]=logio
bon [H*] 7
For neutral solution, pH =7 Acidic character
Basic charater
increases
For acidic solution [H]> 10', i.e., pH<7 increases

Neutral
For basic solution [H]<10, i.e., pH>7
The pH scale value lies between 0 to 14.

Note : 1. pH+ pOH =l4| at 25°C

2. With increase in temperature,as the
dissociation of H,O molecules increases, i.e. H"] and
[OH ]increase, so that ionicproduct
iat increases, pH decreases
increases
with increases of temperature.
with increase of temperature. Further as [H]
172 VATSAL ISC Handbook cof
Chemistry (Kl

Common lon Effect

The suppression of the degree of ionization weak electrolyte by the addition of

of

electrolyte having an ioncommon with the weak electrolyte is known as common ion cffect. strong

For example: The degree dissociation of NH,OH is suppressed by addition

of of
NH,Cth
produces common NH,ion.
NH,CI NH + CI

NH,OH NH +OH
[NHJ[OH]
K, =
[NH,OH)
As the concentrationof NH ion in solution ismore, in order to keep thevalue ofK,constany
NH ions combine with OH ions or the equilibrium shifts towards left. In this way, [NH,OH
increasesor its dissociation decreases.

Buffer Solutions

A buffer solution is a systemwhich maintains its pH value on addition of smallamounts of ac

or alkali or water.

Types of Buffer Solutions

1. Acidic Buffer :An acidic buffer is a mixture of weak acid and its salt with strong base for

example;a mixture containing one mole of CH,coOH and one mole of CH,COONa foms an
acidic buffer.

Action of Acidic Buffer

H" from combine with CH,C00
(i) Suppose few drops of acid are added, most of ions acid

ions (from CH,COONa in buffer) to form feebly ionised CH,CoOH molecules and pH valr

remains constant.
CH,CO0 +H CH,COOH
(From buffer)

Suppose few drops of NaOH are added to the above buffer,

(ii)
ions from NaOH OH art

neutralised by H
ions furnished by buffer to form feebly ionised water molecules. Hence negligible

change in pH value takes place.

Ht OH H,0
(From buffer) (From base)

As it a weak electrolyte it will not affect tht

(iii) Suppose buffer solution is diluted with water. is

pH value of buffer.
a equimolarmixture of weak base and its salt with strong acu
2.Basic Buffer :A basic buffer is

ofNH,CI.
For example : amixture of one mole of NH,OHand one mole
Action of Basic Buffer
with
combine
(1)Suppose a few drops of HCl are added to thebuffer. Here H ionsfrom acid
water. There is no change in pH.
OH ions of NHOH (of buffer) to form feebly ionised

H+ + OH H,0
(From acid) (From buffer)
 lonic Equilibria
173

(2) Suppose a few drops of NaOH are added to the buffer, OH ionsfrom NaOH combine with

NH ions of bufter to form weakly ionised NH,OH molecules.Hence there is no change in its pH
value.

NH OH NH,OH
(From buffer) (From base)

(3) Suppose the buffer is diluted with water. As water is weak electrolyte, it willnot affect the pH
value of the buffer.

pH of Buffer Solution
Henderson-HasselbalchEquation
(1) For acidicbuffer solutions
pH=pKa tlogio [Salt)
[Acid]
where pK =-log10 K
and K, =ionisation constant of acid.

[Conjugatebase]
or,
pH= pKa +logio
[Acid]
(2) For basic buffer solutions:
[Salt)
pOH=pky + logj0
[Base]

or, pH =14- pKy -log10 [Salt)

[Base]

where pK, =-log1o Ky

and Kh =Dissociationconstant of base

[Conjugateacid]
pH =14 -pKy -logo [Base]

Buffer capacity or Buffer Index

Number of moles added to l litre of the buffer
Buffer capacity = Change in pH
glig

SolubilityProduct (Ksp)
The product of molar concentrations of in the saturated solution at a given
ions (formed
t/ temperature)raised to the power equal number
times each ion occurs in the balanced
to the
Tect
chemical equation. It has a constant value for an electrolyte at a constant temperature.
For example :a saturated solution of sparingly soluble salt like AgCl maintains its equilibrium
with its ions as follows
nga
AgCl(s) Ag + Cr
Applying law of mass action,

K
ine [AgCl]

Or K [AgCl] Ag" [CI] =

174 VATSAL ISC Handbook of
Chemistry
As concentrationof a solid is always constant.

[Ag1[CI|=Kx Constant =Kp

whereKyp is known as solubility product.
Table 5.5: Solubility products of some common sparingly soluble salts at 298
Salt Salt
Kyp.
Kp
AgCl 1:8x 1010 CoS
1-9x1027
AgBr 5-0x10-13 ZnS
16x1024
AgI 8-3x10l7 NiS
4-7x105
PbClg 1·6× 105 MnS 2-5x10-13

Hg,Cl 1:3 x 10-18 Ca(OH), 5-5x 10-6

HgS 4x 10-53 CaCO, 2-8x109
PbS 8x 10-28 CaSO4 9.1x106
CuS 6-3 x 106 BaCO; 71x10-24
CdS 1·lx]0-28 BaSO4 lx10-10

Fe(OH)2 8-0x10l6 SrCO, 1·6x 10-l0

Fe(OH); 1·1x10-36 SrSO4 3-2x10-7

Cr(OH), 6-3 x1031 MgCO, 3 x10-8

Al(OH); 1·lx10-l6 Mg(OH)2 1·8×10-ll

lonic Product (1.P.)

the product of the concentrationof the ions of the electrolyte raised topower of thet
It is

in the balanced chemicalequation in solution at any concentration.

coefficients Its value varies with

change in concentration.
In the above case, we get [Ag"][CI]=Kp

The expression [AgI[CI ]is known as ionic product.

Differencesbetween solubility product (Ksp) and ionic product(I.P.)

(1) Ionic product term is applicable to all types of solutions may be saturated or unsaturat
but solubility product term is applied only to saturated solution.
(2)The solubility product of a salt is constant at a constant temperature but ionic prou

depends upon the concentration of ions in the solution.

Criteria for Precipitation of an electrolyte

()If lonic Product > Kgp, the solution is supersaturated and precipitation takes place.

(2) If Lonic Product < Kn, the solution isunsaturated and more of the solute can dissolve.

(3)If Lonic Product = Ksp,the solution is just saturated and no precipitation takes place.
 175
lonic Equilibria

Relationship between Solubility and Solublity Product

Suppose that the solubility of a sparingly soluble salt A,B, is s mol/L.

ABy yBX
S moles moles
XS ys moles
Thus [AY]=xs
and (B]=yx
Now

=[xs [ys'

=x°.s. y.s
Ksp =**. y'. sx + y
For example : Ag-CrO, 2Agt + Cro;
Here x =2, y =1
Ksp -22,1.g2 +1 =483

Application of Ksp in Qualitative Analysis

The concept of solubility product and common ion effect form the basis of the scheme forthe
analysis of basic radicals.

(1)Function of HCI in Group II

Cations of group II (Hg*, Cu,Bi,cat etc.) are precipitated in the form of their sulphides
by passing H,S in acidic medium. Here due to common ion effect, theconcentration of S- ion
decreases and ionic product [M²I[S ]
decreases. This value is sufficient to exceed the solubility

products of sulphidesof Gr II cations as they have very low value ofKgp:

H,S 2H + s²

HCI H +CI
(2) Function of NH 4Cl in Group Il

Cations like Alt, Fe+ or Cr* of GroupIII are precipitated as hydroxidesin alkaline medium.
NH,CI H, + CIr
NH,OH NH +OH
rod The addition of NH,CItothe solution containing NH,OH shifts the equilibria towards left and
OH ion concentration decreases due to common ion effect which in turn decreases the ionic

As the Kn value is low and this ionic productvalue

product. is sufficient to precipitate the cations of
Gr II.Thus NH,CI is added toavoid the precipitation of the hydroxides of the cations of other

groupsalong with the hydroxides of cations of second group.

176 VATSALIISC Handbook of
Chemistry
(3) Function of NH,OH in Group IV
Cations of Group IV(Zn*, Nit, Cot", Mn*} are precipitated assulphides
sby
passing
through their solution containing NH,OH.
H,S 2H* + $2

NH,OH NH + OH
H+
ions react with OH ionsto give water, due to which the equilibriumshifts s
1on towardsrig-
concentration increases. This increases ionic product and becomes sufficient
to excee
solubility product of sulphides of GrIV cations. In absence of NH,OH, S ion
concentration
suficientas Gr IV sulphideshave high
Ksp values.
(4) Function of NH,OH
in Group V
Cations of group V (Ba2, Cat, Sr) are precipitated by adding (NH),CO, to
form of
NH,0Hi
carbonates dueto
is
common ion effect, NH,OH suppresses the dissociation of
forthe
Mg+2 ion may be (NH)C0,
sufficient
precipitation of group V cations, otherwise
precipitated out
(NH),CO, usually contains large amount of NH,HCO, and cations of group V may
solution bicarbonates. In order
always added to it.
to convert NHHCO, to (NH),CO3, ammonium hydroxi
NHHCO, +NH,OH NH),CO,+H,0

UESTIONS
A. Fill in the blanks

1. Sodium acetate solution is

becauseof ....... . 2
2. The degree of dissociation (1999,
of a weak electrolyte ....... with dilution.
3. At 298 K, the value of K,
is ....

4. The conjugate acid of PO

5. For Fe(OH), salt, Kp ...a..,

6. The suppressionof dissociation of a

containing a .......ion electrolyte on addition of a electro
is called common ion effect.
7. CuSO, on salt hydrolysis forms .... solution.
8. Conjugate base of H,SO4 is ....
9. The conjugate base of HPO is

10. The pH of an aqueous solution of FeCl,is ...7.

11. Precipitation of a
compound takes place when ionic
product. product is than its solubi

12. Ammonium chloride solution is ....... because

of.