loqe 1

cn4P1k 4 lONlc ulLl8kluM

/ectro/yte:
^.,.. ... .. .. ... .. .. .. .. ... ~,..
.... , .. . ... .....
5tronq e/ectro/ytes:
. .. ... .. .,.. .. . .. . ..... .. .. .
... .. ,.. .... .. , .... . ... .,..
.., ~~. ~^.. ^^.. .
weok e/ectro/ytes:
. .. .. ... ,. -.. .,... . .. ... ..
,... .. . .. . ..... .. . ~,.. .... , , .. ,
.. , ....^^. ~ , ...
lonic so/ids:(odditiono/}
^.,.. ... .. .. .... .. .. ,.. ... .. ... ..
.. .. .. . . ,. .. .. . .. ... .. ,... .. .. ..
,... , . .. .... . . ~^.
P
2
C
na
+
Cl
-
(s)
na
+
(aq)
+ Cl
-
(aq)
ueqree of ionisotion:
. ,.. , .. .,.. .... . ,.. . , ....... : ,
...... .. .. . .. .,. ...... , . .... ...
lonic equi/ibrium:
. , ,.. .... , ... .. . , ...... . .... , ..
.. ..` .. ,.. . , ...... , ,.. . .. ... .
,........ . .... ... . .. ... ,........ .. .,..
5e/f ionisotion of woter.
:.... , ,.

.

.. .. ... .... . ,
... .. ,..... . ,.. ., ..... , .
xp/oin deqree of ionitotion. :( odditiono/}
lractlon ol substance lonlzed out ol the total dlssolved quantlty ol substance ls called degree ol
lonlzatlon.
When degree ol lonlsatlon ls multlplled by 100 lt glves percentage ol lonlzatlon. ercentage ol
lonlsatlon = degree ol dlssoclatlon 100
lor weak electrolyte the degree ol dlssoclatlon depends on concentratlon ol the solutlon and lt
lncreases wlth the dllutlon ol the solutlon. normally thelr degree ol lonlzatlon ls less than one.
ll 0.06 mole compounds ls dlssolved ln water and 0.03 mole ls lonlzed the degree ol lonlzatlon ls
0 . 0 3
0 . 5
0 . 0 6
=
uegree ol lonlzatlon lncreases wlth rlse ln temperature as lonlzatlon process ls endothermlc
reactlon.
xp/oin: uissociotion ond ionisotion. :( 4dditiono/}
Llectrolytes whlch produce lons ln aqueous solutlons are ol two klnds.
lonlc sollds have reversely charged lons as thelr constltuents. uurlng dlssolutlon ol lonlc sollds ln
water, lons are' not lormed but the lons whlch are held llrmly ln thelr posltlons ln the lattlce ol the
compound are set lree, as water ls polar solvent.
e. g. naCl
(s)
+ P
2
C na
+
(aq)
+ Cl
-
(aq)
1hough lonlc sollds are completely lonlsed, thelr concentrated solutlons contaln same lon palrs. e.g.
na
+
Cl
-
. lonlc palrs thus lormed do not conduct electrlclty as they are electrlcally neutral.
Some molecular compounds dlssoclate lnto lons when dlssolved ln water.
PCl + P
2
C

+

CP
3
CCCP
(l)
+ P
2
C

+

loqe 2
Compounds llke PCl, CP
3
CCCP etc have polar bond between two parts ol molecule produclng
posltlve and negatlve lons. When such compounds are dlssolved ln water, thelr polar bond breaks
to lorm lons.
1he process ln whlch lons are lormed lrom molecule ol compounds ls called lonlsatlon.
1hus lollowlng two processes occur ln concentrated strong electrolyte solutlons.
(l)A process produclng lons capable ol conductlng electrlc current ls descrlbed as dlssoclatlon.
(ll)1he term lonlzatlon lndlcates the lormatlon ol total lons l. e. lons capable ol and lncapable ol
conductlng electrlc current.
6ive: operotiono/ definitions of 4cid ond bose
8obert 8oyle, about three hundred years ago observed durlng acld base reactlon that lormatlon ol
salt takes place.
lollowlng are propertles ol aclds and bases.
Aclds are sour ln taste. Aclds turn blue lltmus red. Aclds evolve hydrogen gas durlng reactlon wlth
metals. 1hey are neutrallsed by alkall.
8ases are bltter ln taste, turn red lltmus blue and are neutrallzed by aclds
1helr llmltatlon ls that they cannot explaln why aclds are sour and bases are bltter. Pence,
operatlonal dellnltlons are called old dellnltlons.
1he modern dellnltlons used at present are called conceptual dellnltlons ln whlch Arrhenlus,
8ronsted-Lowry and Lewls dellnltlons ol acld base are lncluded.
xp/oin: 4rrhenious ocid bose theory with i//ustrotions, o/so qive its /imitotions. [l morks]
Arrhenlous proposed acld base theory durlng 1880-90. Accordlng to theory, substances whlch glve
lons when dlssolved ln water ls acld whlle substance whlch glve lons on dlssolutlon ln
water ls base.
Moreover lt was belleved that these compounds dlssoclate reverslbly lnto lons ln aqueous solutlons
and therelore, thelr aqueous solutlons showed electrlcal conductlvlty and chemlcal reactlvlty.
PA + P
2
C P
+
+ A
-
PCl + P
2
C P
+
+ Cl
-
Acld Acld
8CP + P
2
C 8
+
+ CP
-
naCP + P
2
C na
+
+ CP
-
8ase 8ase
1hus Arrhenlous attrlbuted propertles ol acld to P
+
and propertles ol bases to CP
-
lons.
Limitotions of 4rrhenius theory:
P
+
lon ls hlghly unstable and cannot exlst lndependently.
lonlc radlus ol P
+
lon ls very small 10
-13
meter so lt can readlly comblne wlth water (l.e. hydrated)
and lorm lons.
More over ln certaln bases though CP
-
ls not present even then they show propertles ol base, vlz.,
nP
3
.
Slmllarly compounds llke 8l
3
do not possess P
+
, even then they act as acld.
1hls concept can only be applled to aqueous solutlons because salt llke nP
4
Cl reacts as acld ln
solvent llke llquld nP
3
.
4dditiono/ points
Arrhenlous theory ls appllcable only to aqueous medla. PCl act as strong acld ln aqueous medla
dlssoclatlng nearly to completlon (100 -extent ). 8ut slnce lt dlssoclate very leebly ln glaclal acetlc
acld, lt act as weak acld ln acetlc acld medla. 1hus role ol solvent cannot be explalned by Arrhenlous
theory.
Acldlc nature ol CC
2
, SC
2
, SC
3
... etc. cannot be explalned by theory.
8aslc character ol nP
3,
na
2
CC
3,
k
2
CC
3
etc cannot be explalned by theory.
xp/oin: Lowry - 8ronsted ocid bose theory with i//ustrotion, o/so qive /imitotions.
Lowry -8ronsted have suggested more general dellnltlon lor acld and base ln 1923 known as proton
transler theory.
Accordlng to theory, acld ls one whlch donates proton whlle base accepts the proton durlng acld
base reactlon. 1hus acld-base reactlon ls a process ln whlch proton transler occurs.
loqe J
Acld loses proton durlng the reactlon. now, lts resldual part has tendency to regaln the proton
durlng reverse reactlon. 1hus accordlng to thls theory a reactlon between an acld and a base
produces a base and an acld respectlvely.
PA + P
2
C P
3
C
+
+ A
-
roton donor roton acceptor roton donor roton acceptor
Acld 8ase Acld 8ase
When PCl dlssolves ln water, lt lonlzes and P
+
ls set lree lrom PCl and P
+
lon ls accepted by a water
molecule. 1hus accordlng to Lowry - 8ronsted theory PCl ls acld and P
2
C ls base.
8ut when nP
3
ls added to P
2
C, nP
3
by acceptlng P
+
acts as base whlle P
2
C donatlng P
+
lon en[oy
acldlc lunctlon.
Acld + base con[ugate base + con[ugate acld
PCl
(g)
+ P
2
C
( ) a q
Cl

+
3
( ) aq
H O
+
Slmllarly lollowlng reactlons can be explaln.
2 ( ) l
H O
+
3 ( ) g
NH
( ) a q
OH

+
4( ) a q
NH
+
3 ( ) l
CH COOH
+
2 ( ) l
H O
3 ( ) a q
CH COO

+
3
( ) aq
H O
+
3( ) l
HNO
+
2 ( ) l
H O
3 ( ) a q
NO

+
3
( ) aq
H O
+
2 4( ) a q
H SO
+
2 ( ) l
H O
4( ) a q
HSO

+
3
( ) aq
H O
+
2 ( ) l
H O
+
2 ( ) l
H O
( ) aq
OH

+
3
( ) a q
H O
+
3 ( ) g
NH
+
3 ( ) g
NH
2( ) aq
NH

+
4( ) a q
NH
+
All the above reactlons are reverslble and produce acld-base. alrs ol acld and bases lormed lrom
each other by galn or loss ol proton are called con[ugate acld - base.
An acld produces a con[ugate base by glvlng up a proton and a base produces a con[ugate acld by
galnlng a proton.
Limitotions of Lowry-8ronsted theory:
1he dllllcultles are observed ln the study ol reactlons ln organlc chemlstry and complex salts. 8l
3
has no proton even then lt acts as an acld.
lollowlng acld base reactlons do not lnvolve transler ol proton and hence cannot be explalned on
the basls ol Lowry-8ronsted theory.
CaC
(S)
+ SC
3 (g)
CaSC
4
CaC
(S)
+ CC
2(g)
CaCC
3 (S)
8ase Acld Salt 8ase Acld Salt
Several reactlons ol acld-base type occur ln nature ln absence ol protlc solvents llke, water. ln these
acld - base reactlons proton transler ls not essentlal. 1hese types ol reactlons cannot be explalned
by Lowry -8ronsted prlnclple
4dditiono/ points
Accordlng to the theory, solvents are classllled lnto two groups.
rotlc solvents: 1hese solvents allow transler ol protons l. e. water, alcohol etc.
Aprotlc solvents: 1hese solvents do not allow transler ol protons. l. e. benzene, CCl
4
8elatlve acld base strength also can be dlscussed on the basls ol thls theory.
A strong acld has hlgh tendency to glve up the proton whlle a strong base has hlgher tendency to
accept proton. lor example acetlc acld on reactlon wlth water glves proton to water-and act as acld
whlle when lt react wlth PCl lt accepts proton lrom PCl to act as base
PCl
(l)
+ CP
3
CCCP
(l)
Cl
-
+ CP
3
CCCP
2
+
loqe 4
lt ls therelore posslble to have quantltatlve estlmatlon about the extent to whlch the reactants wlll
lorm products.
Powever ln order to compare the relatlve acld strength reactlons ol aclds are to carry out wlth
common base llke water. Slmllarly varlous bases are reacted wlth common acld llke water to
compare thelr relatlve strength.
ll an acld ls strong lts con[ugate base ls weak and ll a base ls strong lts con[ugate acld ls weak.
Slnce water react wlth strong acld as well as strong base, lt ls usually consldered as weak acld as
well as weak base and hence ls amphoterlc solvent.
Con[ugate acld: .. ,. . - :. .. . . .. ..
Con[ugate base: .. ,. . . ,. - :. .. . . ,. ..
., . .. .. ..
xp/oin: Lewis ocid bose theory with i//ustrotions.
1hls concept ls more generallzatlon ol Lowry - 8ronsted theory.
Arrhenlus theory was extended to non - aqueous solvents by Lowry - 8ronsted theory.
1he study ol electron conllguratlon ol all Lowry - 8ronsted bases revealed that each ol them had at
least one non bondlng electron palr whlch was used to lorm a bond wlth proton released by an
acld.
1he dellnltlons proposed by C. n. Lewls ln 1923 are appllcable ln protlc as well as non-protlc
solvents and equally appllcable to reactlons carrled out ln the absence ol solvents.
Lewls base: substance whlch can donate electron palr ls called lewls base.
{normally anlon or neutral molecules (electron rlch specles) whlch can donate an electron palr to
lorm a co-ordlnate bond are Lewls bases.} lor e.g. P
2
C, nP
3
, CP
-
, l
-
etc.
Lewls acld: substance whlch can accept electron palr ls called lewls acld.
{normally catlon or neutral mo1ecule whlch can accept one or more Llectron palrs to lorm a co-
ordlnate bond are Lewls acld.} lor e.g. AlCl
3
, Co
3+
, Mg
2+
1hus durlng acld base reactlon transler ol electron palrs takes place. Conslder lollowlng examples.
Acld 8ase roduct
P
+
+ :nP
3
4
NH
+
Cl
3
8 + :nP
3
Cl
3
8:nP
3
P
2
C + :nP
3
+ CP
-
Ag
+
+ 2Cn
-
[Ag (Cn)
2
]
-
4dditiono/ points:
rotons are consldered to be aclds by Lewls. P
+
lon ls electron dellclent specles requlrlng two
electrons (electron
water ls acld base reactlon accordlng to Lewls theory. P
+
lon produced by dlssoclatlon ol PCl when
dlssolved ln water, by galnlng non-bondlng electron palr possessed by P
2
C lorms hydronlum lon.
Pydratlon ol salt ls Lewls acld - base reactlon
naCl + P
2
C [na ( P
2
C )
6
]
+
+ [ Cl ( P
2
C)
6
]
-
1hese lons are known as hydrated lons (solvated lons). P
2
C molecules act as base ln the reactlon
wlth na
+
and as an acld wlth Cl
-
.
H N
H
H
H
+
H O H [ ]
H
+
] [H O H H
+
+
loqe 5
lormatlon ol complex lon ls Lewls acld base reactlon. Central metal lon belng electron dellclent
always act as Lewls acld whlle llgand by donatlng electron palr act as Lewls base.
Llgand: 8eactant specles capable ol donatlng electron palr and hence elther negatlvely charged lons
or electrlcal neutral molecule havlng non bondlng electron palr.
Lewis bose is o/woys Lowry - 8ronsted bose, but Lewis ocid is not o/woys Lowry -8ronsted ocid - xp/oin.
( All Lowry - 8ronsted acld base reactlons can be explalned by Lewls theory but all Lewls acld-base reactlons
cannot be explalned by Lowry -8ronsted theory )
1hls concept ls more generallzatlon ol Lowry - 8ronsted theory.
Arrhenlus theory was extended to non - aqueous solvents by Lowry - 8ronsted theory.
1he study ol electron conllguratlon ol all Lowry - 8ronsted bases revealed that each ol them had at
least one non bondlng electron palr whlch was used to lorm a bond wlth proton released by an
acld.
1he dellnltlons proposed by C. n. Lewls ln 1923 are appllcable ln protlc as well as non-protlc
solvents and equally appllcable to reactlons carrled out ln the absence ol solvents.
Lewls base: substance whlch can donate electron palr ls called lewls base.
{normally anlon or neutral molecules (electron rlch specles) whlch can donate an electron palr to
lorm a co-ordlnate bond are Lewls bases.} lor e.g. P
2
C, nP
3
, CP
-
, l
-
etc.
Lewls acld: substance whlch can accept electron palr ls called lewls acld.
{normally catlon or neutral mo1ecule whlch can accept one or more Llectron palrs to lorm a co-
ordlnate bond are Lewls acld.} lor e.g. AlCl
3
, Co
3+
, Mg
2+
1hus durlng acld base reactlon transler ol electron palrs takes place. Conslder lollowlng examples.
Lewls acld Lewls base roduct
SnCl
4
+ 2Cl
-
SnCl
6
-2
8l
3
+ l
-
8l
-
4
CC
2
+ P
2
C- P
2
CC
3
xp/oin woter is on omphoteric so/vent. [2 morks]
Water ls angular, polar, covalent molecule. lt ls capable ol donatlng as well as acceptlng proton.
PCl + P
2
C

+

base
nP
3
+ P
2
C

+

acld
Moreover lt undergo sell lonlzatlon
P
2
C + P
2
C

+

xp/oin se/f ionitotion of woter.
When sensltlve lnstruments are used to measure electrlcal conductlvlty ol water, lt ls lound that a
sample ol pure water conduct a small amount ol electrlclty l.e.0.03 10
- 6
mhoscm
-1
at 23

C
temperature.
1hls lndlcates that water has tendency to get lonlzed. lt dlssoclate sllghtly lnto

and

lons.
Autoprotlc solvents (usually amphoterlc solvents) undergo sell lonlzatlon (autoprotolysls) to lrom
lonlc specles. Autoprotolysls ls Lowry-8ronsted acld-base reactlon,
P
2
C

+

As water dlssoclates lnto

and

lons very sllghtly, there exlst an equlllbrlum between
unlonlzed water molecules and lons lormed as a result ol dlssoclatlon.
Lqulllbrlum constant can be calculated as under:
2
[ ][ ]
eq
H OH
K
H O
+
=
Welght ol 1000 ml pure water ls 1000 grams at 23 C temperature.
loqe 6
1000
55.5 /
. . 18 / 1.0
weight in grams grams
Molarity moles liter
Mol wt volumeinliter grams mole liter
= = =

1he dlssoclatlon ol pure water ls negllglble. 1herelore the concentratlon ol undlssoclated water at
23 C temperature ls 33.33 mole/llter, belng large quantlty ls consldered as constant.
1herelore, k
eq
33.3 = [ P
+
] [ CP
-
]
kw = [ P
+
] [ CP
-
] Pere kw ls lonlc product ol water.
Lxperlmental value ol kw ls 1.0 10
-14
at 23 C temperature As

and

are lormed wlth
1:1 ratlo

kw = [

] [

] = [

]
2
= [

]
2
now, kw = 1.0 10
-14

[

] =

= 10
-7
mole/llter
As concentratlon ol [

]and [

] ls equal ln water, water ls neutral.
Mention of temperoture is necessory o/onq with the vo/ue of kw: xp/oin.[1 morks]
value ol lonlc product ( kw) ol water 23 C ls 1.0 10
-14
. now, dlssoclatlon ol water belng
endothermlc reactlon, the lncrease ln temperature, dlsturbs the equlllbrlum establlshed between
undlssoclated water molecules and lons lormed by dlssoclatlon ol water, shlltlng lt ln lorward
dlrectlon. 1hls causes an lncrease ln [

] and [

] and hence, lncrease ln value ol kw.
So lt ls necessary to mentlon temperature along wlth value ol kw.
whot is effect of temperoture on vo/ue of kw ? .[1 morks]
Water undergoes sell lonlzatlon ln very small quantlty. kw= [

] [

].=10
-14
kw ls lonlc product ol water wlth 10
-14
value at 23 C temperature. As dlssoclatlon ol water ls an
endothermlc reactlon the lncrease ln temperature lncreases the concentratlons ol

as well as

lons.
1hus lncrease ln temperature lncrease the value ol kw.
why woter is neutro/? .[1 morks]
Water ls amphoterlc solvent, undergo autoprotolysls. uurlng lts sell lonlzatlon, lt dlssoclates lnto

and

2
H O

+

ulssoclatlon ol waler at 23 C temperature ls negllglble.
As

and

are lormed ln 1:1 mole ratlo, sell lonlzatlon ol water glves,[

] =

=10
-7
mole / llter uue to equal concentratlons ol

and

lons, water ls neutral.
xp/oin: pn -pOn sco/e.
ll we express the concentratlon ol hydronlum lon

ln molarlty then values llke 10
-12
to10
-2
are posslble. lt ls dllllcult to express these values on slmple graph paper.{ob[}
Pence, sclentlst Sorensen lound a scale whlch ls called pP scale. Accordlng to hlm pP = -
log
10

.
1he values10
-12
to10
-2
shown above can be converted to +12 to +2 ll calculated on the basls ol thls
relatlon and plottlng ol graph can be easy.
1he dellnltlon ol pP can be glven llke thls, , , .... . . .. .... . .
r. , . .... , .. ..... ...
Accordlng to thermodynamlcs, actlvlty ls more proper word lnstead ol concentratlon but ln dllute
solutlons actlvlty and concentratlon can be consldered to be the same. now as seen earller a
solutlon contalnlng 10
-7
M

and

ls neutral.
uellnatlon - , . ..... . . r , .,. , .... ,

.. ..
.... .. .. ,.. .... . .. , , . .....
C8
. .. .... . . r ,

.. .... .. .... . .. , , .
.....
uellnatlon - pCP : . ..... . . r , .,. , .... ,

..
.... .. .. ,.. .... . .. , , . .....
C8
loqe 7
. .. .... . . r ,

.. .... .. .... . .. , ,
. .....
Pence pP = - log
10

= - log
10
7
10

M = 7
and lor acldlc solutlon

>
7
10

M, pP < 7
Slmllarly, lor baslc solutlon

<
7
10

M, pP > 7.
5ome importont points to remember for pn sco/e
1he pP scale ls appllcable only to dlluted aqueous solutlon havlng maxlmum concentratlon ol

. lon 1 M.
1he concentratlon ol

. lons and

lon ln pure water at 23
0
C are 10
-7
mole/llter each.
1herelore lor pure water at 23
0
C pP = - log
10
[

]= - log
10
10
-7
= 7.0

pP+pCP=7+7=14.0
now, kw lor pure water at 23
0
C = 1.0 10
-14

pkw = pP + pCP = 14.0
ln case ol pure water or a neutral solutlons, pP = pCP = 7.0
ll an aqueous solutlon ls acldlc, pP < 7.0
ll an aqueous solutlon ls baslc, pP > 7.0
Logarlthm ol [ P
+
] have no unlt, so pP has no unlt.
ln case ol pure water as well as neutral solutlons, [ P
+
]=[ CP
-
] =1.0 x 10
-7
M so pP = pCP = 7.0
xp/oin for o// oqueous so/ution pn + pOn =14 (for understondinq on/y}
Suppose an acld solutlon has 1.0 M

. lon concentratlon (1M PCl, PCl belng strong acld
dlssoclates completely) lts pP = 0.
Another acld solutlon havlng 0.1 M

. lon concentratlon wlll have pP = 1.0 C8 pCP = 13.0
Whlle base solutlon havlng 1.0 M CP
-
concentratlon wlll have pCP=0.0 C8 pP = 13.0.1herelore pP
range lor aqueous solutlon ls 0.0 to 14.0 and pCP range lor same solutlon ls 14.0 to 0.0.
ll concentratlon ol strong acld exceeds 1.0 M, pP value would be negatlve accordlng to dellnltlon.
lor the base solutlon havlng concentratlon ol CP
-
more than 1.0 M , pP value exceeds 14.0. lo sucb
coses pn scole ls oot oppllcoble.
pP scale ls appllcable only lor dlluted aqueous solutlons havlng concentratlon ol or lons
less than 1.0 M. When an acld C8 base ls strong, lt ls almost completely lonlzed ln aqueous solutlon.
1herelore the concentratlon ol

lon lor a strong acld solutlon and concentratlon ol
lons lor a strong base solutlon ls consldered the same as per the concentratlon ol glven strong acld
C8 base.
xp/oin the concentrotion of

in oqueous monobosic so/ution of o stronq ocid is equo/ to the
concentrotion of on ocid:
Monobaslc acld release one proton when dlssolved ln water. Strong acld undergo complete
lonlzatlon. 1hus 1.0 mole strong mono baslc acld releases 1.0 mole protons whlch lnteract wlth
water to lorm

lons.
6ive odvontoqes of pn sco/e.
( l ) Wlth the help ol pP scale, small concentratlon values ol

and

can be
magnllled.
( ll ) Wlth the help ol pP scale, extent ol acld-base tltratlon can be demonstrated graphlcally.
( lll) Wlth the help ol pP scale, uselul range ol acld-base lndlcators can be explalned.
whot is the decreose in concentrotion of

ions when pn decreoses by 1 unit?
When pP decreases by 1 unlt, the concentratlon ol

lons becomes ten tlmes the lnltlal
concentratlon.
why is pn sco/e is not usefu/ to express

when concentrotion of so/ution is hiqh?
pP scale ls not appllcable to hlghly concentrated solutlons due to lollowlng reasons:
( l ) lor concentratlons ol

lons greater than 1.0 M, pP values are less than zero. l.e.
negatlve. Pence concentratlon ol

ln solutlons wlth hlgh molarlty cannot be calculated.
loqe 8
lon palrs are also lormed as a result ol lonlsatlon. uue to proxlmlty, ol lons solutlons behave non
ldeally.
1hus, to determlne pP ol the solutlon, lt ls necessary to known the actlvlty ol

lons ln
concentrated solutlons l. e. solutlons wlth hlgh molarlty
xp/oin: lonisotion of weok ocid ond bose.[lmorks]
Weak electrolytes llke CP
3
CCCP, nP
3
etc. lonlse only sllghtly ln thelr aqueous solutlons.
As water ls polar solvent, the polar bonds present ln the compound break and the atom havlng
hlgher electro negatlvlty acqulres negatlve charge whlle the atom havlng lower electronegatlvlty
acqulres posltlve charge lormlng negatlve and posltlve lons respectlvely.
1here exlsts equlllbrlum between lons and unlonlsed molecules ln aqueous solutlons ol weak
electrolytes.
nP
3
+ P
2
C nP
+
(aq)
+

CP
3
CCCP
(aq)
+ P
2
C
(l)
CP
3
CCC
-
(aq)
+

Lqulllbrlum constant lor weak acld equlllbrlum system ls relerred as ka whlle that ol weak base
system ls kb
xp/oin: uerivotion of equotion for ko
When weak acld dlssolves ln water, dllllcultles arlse to compute

. lon concentratlon as lt
lonlze leebly.
1he concentratlon ol

. lons ln lts aqueous solutlon ls much less than the lnltlal
concentratl0n ol the solutlon.
1he lonlsatlon constant ol weak acld can be calculated as under.
Suppose a weak acld PA ls dlssolved ln water. Let C ls the lnltlal concentratlon ol glven weak acld ln
terms ol mole/llter.
1he lollowlng equlllbrlum exlsts ln the aqueous solutlon.
3
( )
2 ( ) ( )
aq
HA H O
aq aq
H O A
+
+ +
lnltlal concentratlon C 0 0
uegree ol lonlsatlon ls o
Concentratlon at eq
m
C(1-o) oC oC
Lqulllbrum constant lor above reactlon can be wrltten as
3
2
[ ][ ]
[ ][ ]
e
H O A
K
HA H O
+
=
2
[ ][ ]
[ (1 )][ ]
e
c c
K
c H O

As water ls weak electrolyte so lts sell lonlzatlon can be lgnored hence [P

2
C] ls almost constant (
large quantlty), ke [ P
2
C] ls constant can be replaced by ka .
2
[ ][ ]
[ ]
[ (1 )]
e
c c
K H O Ka
c

= =

[ ][ ]
(1 )
c c
Ka
c

1herelore
2
(1 )
Ka
c

now, degree ol dlssoclatlon ol weak acld ls very less, hence lts concentratlon at equlllbrlum ls
almost equals to lts lnltlal concentratlon [PA] = c.
now
2
(1 )
Ka
c

as degree ol dlssoclatlon ls very less lor weak aclds 1-o = 1

Ka
c
=
1he unlt ol ka wlll be molllt
-1
. value ol ka ls dlrectly proportlonal to the temperature.
As the values ol ka depend on

the values ol k, wlll be dlllerent lor dlllerent aclds
Lesser the value ol ka, weaker wlll be the acld. 1he value ol ka wlll be constant at dellnlte
temperature.
4dditiono/ points:
lor weak aclds pka = - log
10
ka
loqe 9
now
3
[ ] [ ] H O A
Ka
c
+
= ll sell lonlzatlon ol water ls lgnored than [P
3
C
+
] = [ A
-
] so ka can be wrltten as

2
3
[ ] H O
Ka
c
+
=
2
3
[ ] . H O Ka c
+
=
3
[ ] . H O Ka c
+
=
1he comparlson ol ka values ol dlllerent aclds ls the measure ol the relatlve strength ol those aclds.
lor chloro acetlc acld (Cl CP
2
CCCP), ka ls 1.33 10
-3
whlle ka ol CP
3
CCCP ls 1.73 10
-3
. Plgher
value ol ka ol chloro acetlc acld than acetlc acld suggests hlgher acld strength ol Cl CP
2
CCCP than
CP
3
CCCP.
xp/oin: uerivotion of weok bose dissociotion constont kb.
When weak base dlssolves ln water, dllllcultles arlse to compute CP
-
lon concentratlon as lt lonlses
leebly.
1he concentratlon ol

lons ln lts aqueous solutlon ls much less than the lnltlal concentratlon
ol the solutlon.
1he lonlsatlon constant ol weak base can be calculated as under.
A weak base nP
3
ls dlssolved ln water. Let C ls the lnltlal concentratlon ol glven weak base, ln terms
ol mole/llter ol solutlon. At 23C lollowlng equllbrlum occurs.
2 4( ) ( ) 3 aq a q
NH H O NH OH
+
+ +
lnltlal concentratlon C 0 0
uegree ol lonlsatlon ls o
Concentratlon at eq
m
C(1-o) oC oC
4
3 2
[ ][ ]
[ ][ ]
e
NH OH
K
NH H O
+
=
2
[ ][ ]
[ (1 )][ ]
e
c c
K
c H O

As water ls weak electrolyte so lts sell lonlzatlon can be lgnored hence [ P

2
C] ls almost constant
(large quantlty) so ke [ P
2
C] ls constant can be replaced by kb.
2
[ ][ ]
[ ]
[ (1 )]
e
c c
K H O K
c
b

= =

now, dlssoclatlon ol weak base ls very less, hence concentratlon ol ammonla at equlllbrlum almost
equals to lts lnltlal concentratlon C.
[ ][ ]
(1 )
c c
K
c
b

so
2
(1 )
K
b
c

now, degree ol dlssoclatlon ol weak acld ls very less, hence lts concentratlon at equlllbrlum ls
almost equals to lts lnltlal concentratlon [PA] = c.
now
2
(1 )
K
b
c

as degree ol dlssoclatlon ls very less lor weak bases 1-o = 1

K
c
b
=
As sell lonlsatlon ol water ls lgnored so concentratlon ol
4
[ ] [ ] NH OH
+
=
2
[ ]
b
OH
K
c

=
2
[ ] . OH K c
b

= [ ] .
b
OH K c

=
kb ls lonlsatlon constant ol weak base. lts measurement ls ln terms ol mole/llter. value ol kb
lncreases wlth lncrease ln temperature. 8alse ln temperature lavours lonlzatlon and hence along
wlth kb temperature also must be lndlcated.
1he comparlson ol kb values lor dlllerent weak bases ls the measure ol the relatlve strength ol
these bases.
1he value ol kb lor CP
3
nP
2
( 3.0 10
-4
) ls greater than the value ol kb ol nP
3
(1.7410
-3
) lndlcatlng
methyl amlne ls stronger base than ammonla.
xp/oin re/otion between ko ond kb for poir of conjuqote ocid ond bose [2 morks]
loqe 10
As seen earller the values ol ka and kb show the strength ol acld and base respectlvely. ln
relerence to con[ugate acld base, every acld has con[ugate base and every base has con[ugate acld,
vlz.
4( ) 2 ( ) 3( ) 3 ( ) aq l aq aq
NH H O NH H O
+ +
+ +
Acld-1 base-1 base-2 acld-2
1he value ol ka lor the reactlon wlll be
3 3
4
[ ] [ ]
[ ]
a
NH H O
K
NH
+
+
=
3( ) 3 ( ) 4( ) 2 ( ) aq aq aq l
NH H O NH H O
+ +
+ +
4
3
[ ] [ ]
[ ]
b
NH OH
K
NH
+
= Cn addlng the above reactlons,
( )
( )
4( ) 2 ( ) 3( ) 3 ( )
3( ) 3 ( ) 4( )
2 ( ) 3 ( )
2
l
l
aq l aq aq
aq aq aq
l aq
NH H O NH H O
NH H O NH OH
H O H O OH
+ +
+ +
+
+ +
+ +
+
3 3 4
4 3
[ ] [ ] [ ] [ ]
[ ] [ ]
a b
NH H O NH OH
K K
NH NH
+ +
+
=
3
[ ][ ]
a b
K K H O OH
+
=
1bus fot polt of coojuqote oclJ ooJ bose
a b w
K K K =
Pence, lt can be concluded that the constant lor the net reactlon ls the product ol the equlllbrlum
constant, ol two or more reactlons lnvolved ln lt.
ll we know lonlsatlon constant ol con[ugate acld or base, then the lonlsatlon constant ol thelr
con[ugate base or acld can be known wlth the belp of kw.
pka + pkb = 14 pkb = 14 - pka ot - log kb = 14 + log ka
Descr|be d|ssoc|at|on constants of d|bas|c or po|ybas|c (d|prot|c or po|yprot|c) ac|ds {2 marks}
Sulphurlc acld, oxallc acld etc. are dlbaslc aclds and phosphorlc acld, cltrlc acld are trlbaslc aclds.
1helr dlssoclatlon constants are two ka
1
and ka
2
lor dlbaslc and three ka
1
, ka
2
, ooJka
J
lor trlbaslc
aclds respectlvely.
Suppose, dlbaslc weak acld ls expressed as P
2
A, then lts dlssoclatlon wlll occur ln the lollowlng two
steps and correspondlng k
1
and k
2
wlll be obtalned. lor trlbaslc acld dlssoclatlon tokes ploce ln
three steps and correspondlng ka
1
, ka
2
, and ka
J
wlll be obtalned.
2 ( ) 2 ( ) ( ) 3 ( ) aq l aq aq
H A H O HA H O
+
+ +
3
1
2
[ ] [ ]
[ ]
a
HA H O
K
H A
+
=
2
( ) 2 ( ) ( ) 3 ( ) aq l aq aq
HA H O A H O
+
+ +
2
3
2
[ ] [ ]
[ ]
a
A H O
K
HA
+

=
lor dlbaslc acld overall dlssoclatlon constant k
a
= ka
1
ka
2
xp/oin foctors 4ffectinq 5trenqth of 4cid : [2 morks]
lrom the study ol dlssoclatlon constant, pP value etc., lt ls lound that thelr values are dlllerent lor
varlous aclds. 1he reason lor thls ls that [P
3
C
+
] avallable can be more or less. ll the acld ls strong, lts
value ol ka wlll be hlgh and the value ol pP wlll be low.
1be Jlssoclotloo of oclJ wlll JepeoJ oo stteoqtb of oclJ ooJ tbe polotlty of n-A booJ.
As the strength ol P-A bond decreases, the energy requlred lor breaklng that bond wlll decrease
and PA wlll be stronger. When dlllerence between electro negatlvltles ol A and 8 wlll lncrease,
apparently lonlzatlon wlll occur and wlll be easy to break the structure ol the bond. Pence, acldlty
wlll lncrease.
loqe 11
Cn comparlng the elements ol the same group ol perlodlc table, the strength ol P-A bond wlll be
more lmportant lactor than polar nature. As we go down ln the group the slze ol A wlll lncrease and
so strength ol P-A bond wlll decrease and hence acld strength wlll lncrease. lor example ln group
17 elements lncreaslng order ol acldlc strength ls Pl << PCl << P8r << Pl.
lor thls reason, P
2
S ls stronger acld than P
2
C.
ln the elements ol the same perlod ol perlodlc table, the polarlty ol P-A bond wlll determlne the
strength ol acld. As the electronegatlvlty ol A lncreases, the strength ol acld wlll lncrease.
lor example ln the second perlod elements lncreaslng order ln acld strength ls CP
4
<<nP
3
<< P
2
C <<
Pl.
xp/oin: nydro/ysis.
Water ls dlssoclated to a very small extent lnto
( ) a q
H
+
and

lons.
2 ( ) ( ) ( ) l aq a q
H O H OH
+
+
ln pure water concentratlon ol
( ) a q
H
+
and

lons are equal. ure water ls neutral.
A salt ls produced by neutrallzatlon ol acld and base. We may expect that the solutlons ol salt are
neutral.
8ut ln reallty, lt ls lound that on dlssolutlon ol salt lnto water, lt remalns neutral or ln some cases, lt
turns acldlc or baslc.
1he phenomenon ol lnteractlon ol catlons and anlons ol the salt wlth
( ) a q
H
+
and

lons
lurnlshed by water ls known as salt hydrolysls.
1hus, we can say that hydrolysls ls reverse reactlon than neutrallzatlon. lor convenlent study ol
hydrolysls, salt are classllled lnto dlllerent categorles.
xp/oin 5o/t of stronq ocid ond stronq bose ore neutro/[2morks]
1hls group lncludes salts llke naCl, kCl , nanC
2
na
2
SC
4
etc. Let us conslder the hydrolysls ol salt kCl
lonlsatlon ol salt kCl lurnlshes k
+
and Cl
-
lons.
lt's hydrolysls ls as under
( ) aq
KCl +
2 ( ) l
H O
( ) aq
K
+
+
( ) aq
Cl

+
( ) a q
H
+
+

ln above reactlon strong acld ( PCl ) and strong base ( kCP ) are produced. As both are completely
lonlsed, number ol
( ) a q
H
+
lons as well as

lons ln solutlon are equal.
1herelore, the aqueous solutlon ol kCl l.e. salt ol strong acld and strong base ls neutral.
xp/oin 5o/t of stronq ocid ond weok bose ore ocidic in noture. [2morks]
1hls group lncludes salts llke CuSC
4
nP
4
Cl ZnCl
2
. Al (nC
3
)
3
leCl
3
...etc.
Conslder the salt leCl
3
.When leCl
3
ls dlssolved ln water, lt lonlses
3
( ) aq
Fe
+
and
( ) aq
Cl

lons.
1hese lons react wlth water ln order to hydrolyse.
3
FeCl
3
( ) aq
Fe
+
+
( ) aq
Cl

3( ) aq
FeCl +
2 ( ) l
H O
3
( ) aq
Fe
+
+
( ) aq
Cl

lonlzatlon
3
( ) aq
Fe
+
+ 3
2 ( ) l
H O
3( )
( )
aq
Fe OH + 3
( ) a q
H
+
hydrolysls
uurlng hydrolysls ol leCl
3
a weak base le(CP)
3
and strong acldlc lon
( ) a q
H
+
are produced. 1he
base ls weak and dlssoclates very leebly. 1hus concentratlon ol
( ) a q
H
+
lons ls ln excess compared
to
( ) a q
OH

lons ln the solutlon. Solutlon ls therelore acldlc.

Actually when weak base ls lormed durlng the process hydrolysls lt dlsturbs the equlllbrlum
establlshed between water and lts lons.
loqe 12
When the net reactlon agaln reaches the equlllbrlum, the concentratlon ol
( ) a q
H
+
lons exceeds
the concentratlon ol

maklng the solutlon acldlc.
1he equlllbrlum constant ol hydrolysls reactlon ls known as hydrolysls constant
w
h
b
K
K
K
= Where, k
h
= hydrolysls constant k
w
= lonlc product ol water k
b
= lonlsatlon constant ol weak base lormed by
hydrolysls ol salt.
xp/oin so/t of weok ocid ond stronq bose ore bosic in noture. [2morks]
1hls group lncludes salts llke CP
3
CCCna, naCn, na
2
CC
3,
k
2
CC
3
... etc. Let us conslder the sall
CP
3
CCCna (sodlum acetate).
3 2 ( ) 3 ( ) ( ) l aq aq
CH COONa H O CH COO Na
+
+ + lonlzatlon
3 ( ) 2 ( ) 3 ( ) ( ) aq l aq aq
CH COO H O CH COOH OH

+ + hydrolysls
ln the hydrolysls ol CP
3
CCCna a weak acld CP
3
CCCP and a strong baslc lon

are produced.
1he acld ls weak and hence lonlses very leebly. 1herelore as compared to
( ) a q
H
+
lons the

lons are ln excess and hence the solutlon show baslc property.
Actually when weak acld ls lormed durlng the process hydrolysls, lt dlsturbs the equlllbrlum
establlshed between water and lts lons.
When the net reactlon agaln reaches equlllbrlum, the concentratlon ol

lons exceeds the
concentratlon ol
( ) a q
H
+
lons.
1hls makes the solutlon to exhlblt baslc property. 1he equlllbrlum constant ol hydrolysls reactlon ls
known as hydrolysls constant
w
h
a
K
K
K
= Where, k
h
= hydrolysls constant k
w
= lonlc product ol water
k
a
= lonlsatlon constant ol weak acld lormed by hydrolysls ol salt. Solutlon ol CP
3
CCCna ls baslc ln
nature
5o/t of weok bose ond weok ocid.
1hls group lncludes salts llke ( nP
4
)
2
CC
3,
( nP
4
)
2
C
2
C
4
, CP
3
CCCnP
4
etc.on dlssolutlon ln water, these
salts produce acld as well as base ol weak strength.
2
4 2 3( ) 2 ( ) 4 2 3
( ) 2 2
aq l
NH CO H O NH OH H CO + +
uurlng hydrolysls ol above klnd ol salt, both acld and base produced are weak dlssoclatlon leebly.
1hus nature ol the solutlon depends upon the extent ol dlssoclatlon ol acld and base.
lor e. g. solutlon ol (nP
4
)
2
CC
3
ls baslc, ammonlum oxalate ( nP
4
)
2
C
2
0
4
shows acldlc nature whlle
CP
3
CCCnP
4
shows neutral solutlon character.
ln such salts nature ol solutlon depends on the strength ol weak acld and base.
ll acld ls strong than the base then the solutlon ls acldlc. Whlle ll base ls strong than acld then the
solutlon ls baslc ln nature.
lor such salts hydrolysls constant
.
w
h
a b
K
K
K K
=
Lxplaln calculatlon ol pP lor salt ol strong base and weak acld.
CP
3
CCCna ls a salt ol strong base and weak acld. lt wlll lonlsed as lollows.
3 2 ( ) 3 ( ) ( ) l aq aq
CH COONa H O CH COO Na
+
+ + lonlzatlon

3
CH COONa hydrollsed as lollows.
3 ( ) 2 ( ) 3 ( ) ( ) aq l aq aq
CH COO H O CH COOH OH

+ +
Pydrolysls constant lor sodlum acetate ls
3
3
[ ][ ]
[ ]
h
CH COOH OH
K
CH COO

= ________(1)
ln aqueous solutlon water has lollowlng equllbrla.
loqe 1J
2 ( ) ( ) ( ) l aq aq
H O H OH
+
+



________(2)
lor weak acld acetlc acld
3 3
3
[ ][ ]
[ ]
a
CH COO H O
K
CH COOH
+
= __________(3)
Cn multlplylng equatlon 1 and 3 and dlvldlng them by 2 glves
1
h a
w
K K
K

=
w
h
a
K
K
K
=
As sell lonlsatlon ol water ls lgnored so concentratlon ol CP
-
lon ls due to hydrolysls ol salt only. So
concentratlon ol
3
[ ] [ ] CH COO OH

= .
2
3
[ ]
[ ]
w
h
a
K OH
K
K
CH COO

= =
ll the orlglnal concentratlon ol the salt ls c M then at equlllbrlum
2
[ ]
w
h
a
K OH
K
K c

= =
[ ] .
W
a
K
OH c
K

= now lrom the value ol [CP

-
] pCP can be calculated.
Slmllarly lor the salt ol strong acld and weak base llke nP
4
Cl
3
[ ] .
W
b
K
H O c
K
+
= where c ls lnltlal
concentratlon ol salt ol strong acld and weak base.
Summery for hydro|ys|s
Salt k
h
h(degree ol
hydrolysls)
pP
Strong acld
and weak
base
2
3
[ ]
w
h
b
K H O
K
K c
+
= =
w
h
a
K
h K
K c
= =
pP = -Z[logk
w
- logk
b
+logc]
pP = Z[pk
w
-pk
b
-logc]
Strong base
and weak
acld
2
[ ]
w
h
a
K OH
K
K c

= =
w
h
b
K
h K
K c
= =
pP = -Z[logk
w
+ logk
a
-logc]
pP = Z[pk
w
+ pk
a
-logc]
weak acld
and weak
base
w
h
a b
K
K
K K
=

w
h
a b
K
h K
K K
= =

pP = -Z[logk
a
+ logk
w
-
logk
b
]
pP = Z[pk
w
+ pk
a
-pk
b
]
c ls the lnltlal concentratlon ol varlous salts
xp/oin effect of common ion on ionisotion constont of weok ocid ond bose [2morks]
let us toke tbe exomple of weok oclJ, ocetlc oclJ (cn
J
cOOn)
3 ( ) 2 ( ) 3 ( ) 3 ( ) aq l aq
CH COOH H O CH COO H O
aq

+ +
+
3
[ ] [ ]
[ ]
a
AC H O
K
HAc
+
=
Pere PAc and Ac
-
are the short lorms ol CP
3
CCCP and CP
3
CCC
-
lon.
ll salt CP
3
CCCna or PCl added to the solutlon ol PAc then equlllbrlum get dlsturbed.
ll PCl ls added, wlll lncrease and ll CP
3
CCCna ls added, [Ac
-
] wlll lncrease.
Pence, accordlng to Le Chateller's prlnclple, the equlllbrlum wlll make negllglble change and wlll
keep the same value ol equlllbrlum constant.
1hls means that the equlllbrlum wlll be shllted towards lelt and concentratlon ol PAc wlll lncrease
l.e. the amount ol undlssoclated acld wlll lncrease and there wlll be decrease ln and hence,
there wlll be lncrease ln pP.
loqe 14
8y addltlon ol PCl due to lncrease ln slmllar result wlll be obtalned. 1hls ellect ls known as
ellect ol common lon ellect on dlssoclatlon constant ol acld.
ln the same way, ln the case ol lonlsatlon ol weak base nP
3
, ll we lncrease

by addlng salt
llke nP
4
Cl then, accordlng to Le Chateller's prlnclple, as

lncreases the equlllbrlum wlll
shllt towards lelt and hence, undlssoclated nP
3
wlll lncrease, l.e.

wlll decrease. As a
result, pP wlll lncrease.
ln short due to common lon ellect degree ol dlssoclatlon ol weak acld and weak base decreases.
now substances are c|ass|f|ed on the bas|s of so|ub|||ty?[2 marks]
We have studled earller that lonlc substances llke naCP are hlghly soluble ln water. lt absorbs
molsture lrom the alr and dlssolves. Whlle covalent compounds llke Lll are less soluble ln water
and ooo-loolc compounds llke CdS are almost lnsoluble ln water. Pence, substances can be dlvlded
lnto three types:
1ype 1 : Soluble : 1he substances whose solublllty ln water ls more than 0.1M. e.g. naCl, PCl, naCP
1ype 2 : lnsoluble : 1he substances whose solublllty ls very less ln water. e.g. CdS, bS
1ype : 3 Sparlngly soluble : 1he substances whose solublllty ls less than 0.01M e.g. AgCl, 8aSC
4
,
bSC
4
On whot foctor so/ubi/ity of so/t depends?[2morks]
1he basls ol solublllty ls on the lattlce enthalpy and hydratlon enthalpy ol the substance. ll
hydratlon enthalpy ls more than lattlce enthalpy, the substance wlll be soluble ln water.
1he second thlng ls that polar substance dlssolves ln polar solvents and non-polar substance
dlssolves ln non-polar solvents. e.g. olar substance llke naCl ls soluble ln polar solvent llke water
and nonpolar substance llke naphthalene can dlssolve ln non-polar solvent llke benzene.
Sparlngly soluble substances are soluble ln less proportlon and so possess equlllbrlum and whatever
substance ls dlssolved, lt completely gets lonlsed. We shall study the equlllbrlum constant ol
sparlngly soluble salt and ellect ol common lon on lts solublllty.
uefine: 5oturoted so/ution, unsoturoted so/ution ond 5upersoturoted so/ution.{foi infoimation]
( | ) Saturated so|ut|on:
Solutlon ln whlch no more solute can be dlssolved at a glven temperature ls called saturated
solutlon.
( || ) Unsaturated so|ut|on:
Solutlon contalnlng a lower concentratlon ol solute than the concentratlon ol saturated solutlon ls
called unsaturated solutlon.
( |||) Supersaturated so|ut|on:
Solutlon contalnlng more than the equlllbrlum concentratlon ol solute (can be prepared by ralslng
the temperature) lt ls unstable ln presence ol excess solute.
whot is 5o/ubi/ity of so/t?
. ..... ... , . ... . . .. .. ,. ... , .. ..
,. . ,.. . ...... , . ..
. . . .... , . .. . . .... . .. . ...... , ..
, . .... , . . .... . . .. .r .- ^ .,.. . .
. .. ,... .... .. (uellnatlon).
Solublllty product ls consldered only ln case ol sparlngly soluble salts llke AgCl, CuS, Al(CP)
3
etc.
usually we say that these salts are lnsoluble, but theoretlcally these salts are extremely llttle soluble
salts l. e. sparlngly soluble.
xp/oin: 5o/ubi/ity product expression.
1he solublllty product expresslon ls the product ol the molar concentratlons ol the lons ln saturated
solutlon ol salt, havlng an exponent equal to the stolchlometrlc coelllclent ol that lon ln the
balanced equatlon
ln a saturated solutlon ol sparlngly soluble salts lonlsed part ls remaln ln equlllbrlum wlth
undlssolved solld substance.
5o/ubi/ity product { ksp) expression for 84 type so/ts
Lqulllbrlum system
loqe 15
( ) 2 ( ) ( ) ( ) s l aq aq
BA H O B A
+
+ +
Let solublllty ol salt ls SM SM SM SM
( ) ( )
( )
[ ][ ]
[ ]
aq aq
e
s
B A
K
BA
+
=
now as 8A ls the sparlngly soluble salt [
( ) s
BA ] consldered constant so
k
e
[
( ) s
BA ] = k
sp
constant
( ) ( )
[ ][ ]
e aq aq
K B A
+
=
2
.
sp
K S S S = =
sp
S K =
Slmllarly lt can be derlved lor any 8A type salt such as AgCl, ZnS and CuS etc.
5o/ubi/ity product { k
sp
) expression for 84
2
or 8
2
4 type so/ts
Lqulllbrlum system -
2
2( ) 2 ( ) ( ) ( )
2
s l aq aq
BA H O B A
+
+ +
Let solublllty ol salt ls S M. SM SM 2SM
2 2
( ) ( )
2( )
[ ][ ]
[ ]
aq aq
e
s
B A
K
BA
+
=
now as 8A
2
ls the sparlngly soluble salt [
2( ) s
BA ] consldered constant so k
e
[
2( ) s
BA ] = k
sp
constant
2 2
2( ) ( ) ( )
[ ] [ ][ ]
e s aq aq
K BA B A
+
=
2 2
( ) ( )
[ ][ ]
sp aq aq
K B A
+
=
2
( ) (2 )
sp
K S S =
3
4
sp
K S =
3
1
4
sp
S K = or
1
3
4
S
sp
K
=
|
|
' .
Lquatlon lor the relatlonshlp between solublllty and k
sp
lor 8A
2
type ol salt.
n.w.: uerive re/otionship between so/ubi/ity ond k
sp
for 4
2
8
l
type of sporinq/y so/ub/e so/ts such os 8i
2
5
l
,
4s
2
5
l,
le
2
5
l
.
6ive conditions for precipitotion of so/t.
ll ln a glven solutlon, lonlc product ls less than the solublllty product more lons can be added to
make solutlon saturated. 1hus when l ls less than that ol k
sp
solutlon ol glven sparlngly soluble salt
ls unsaturated. Cn addltlon ol more lons, number ol lons present ln solutlon wlll make lonlc product
greater than solublllty product to preclpltate excess lonlc. 1hus lor the sparlngly soluble salt,
lonlc product ( l ) = solublllty product ( k
sp
), then glven ls saturated solutlon.
lonlc product ( l ) < solublllty product (k
sp
), then glven ls unsaturated solutlon
lonlc product ( l ) > solublllty product (k
sp
), excess lons wlll be preclpltated ln solutlon.
6ive informotion obout so/ubi/ity of so/ts.(for informotion on/y}
An experlmental result glves lollowlng lnlormatlon about solublllty's ol salts.
All salts ol na
+
, k
+
and are soluble ln water.
All nltrates are soluble ln water.
All compound lormed wlth P
+
lons are soluble ln water.
All sulphate except bSC
4,
CaSC
4,
8aSC
4,
SrSC
4,
Ag
2
SC
4
are soluble ln water.
All chlorldes except AgCl. PgCl
2
, bCl
2
and Cu
2
Cl
2
are soluble ln water.
Sulphldes ol alkall metals and alkallne earth metals are soluble ln water. sulphldes ol other metals
are sparlngly soluble.
loqe 16
Pydroxldes ol alkall metals, 8a(CP)
2
etc are soluble ln water.
Carbonates, phosphates and sulphates ol alkall metals are water soluble.
uerive the so/ubi/ity product expression for fo//owinq: {xercise)
( l ) A8
3
/ A
3
8 ( ll ) A
2
8
3
/ A
3
8
2
type ol salts.
xp/oin: common ion ffect.
. ... , . , .... , . . ... , .. .. ...
... .. . .. ... .. ,,.
When aqueous solutlon ol electrolyte havlng one ol the lon same (common) ls added to the
solutlon ol another electrolyte, concentratlon ol common lon lncreases conslderably ln the mlxture.
lncreased concentratlon ol common lon lavours reverse reactlon ol dlssoclatlon ol another
electrolyte so degree ol dlssoclatlon ol another electrolyte decreases.
Above phenomenon takes place accordlng to Le Chateller's prlnclple. 1he reverse process ls
lavoured to reach the new state ol equlllbrlum.
When aqueous solutlon ol MA (stronger) electrolyte ls added to aqueous solutlon ol 8A (weaker)
electrolyte, A
-
lon belng common lts concentratlon lncreases ln the mlxture.
MA ls stronger electrolyte than 8A l. e. MA has hlgher tendency to remaln ln dlssoclated state than
8A.
1hls wlll dlsturb the equlllbrlum establlshed ln 8A system. lncreased concentratlon ol A
-
lons wlll
lavours the reverse reactlon ol dlssoclatlon ol 8A locteosloq tbe cooceottotloo of uoJlssocloteJ 8A,
accordlng to Le Chateller's prlnclple.
2 ( ) ( ) ( ) l aq aq
BA H O B A
+
+ +
2 ( ) ( ) ( ) l aq aq
MA H O M A
+
+ +
lncreased concentratlon ol undlssoclated 8A decreases the concentratlon ol
( ) aq
B
+
lons ln the
mlxture whlch ls uncommon lon ol weaker electrolyte.
lo//owinq i//ustrotions c/orify the concept of common ion effect.
(|)lf we odd o drop of pheno/phtho/ein to o so/ution of Nn
4
On o deep red co/our is deve/oped. On oddition
of o pinch of ommonium ch/oride to this so/ution, the co/our becomes foint. why?
nP
4
CP ls weak base lts aqueous solutlon has the lollowlng equlllbrlum establlshed.
4 2 ( )
4( )
aq
aq
NH OH H O NH OH
+
+ +
now, nP
4
Cl ls a stronger electrolyte than nP
4
CP. When dlssolved ln water, lt dlssoclates to a
greater extent. Aqueous solutlon ol nP
4
Cl ls also the example ol equlllbrlum system.
4 2 4( ) ( ) aq aq
NH Cl H O NH Cl
+
+ +
When aqueous nP
4
Cl ls added to aqueous solutlon ol nP
4
CP, slnce nP
4
Cl dlssoclates to a greater
extent, lt lncreases the concentratlon ol
4( ) aq
NH
+
lons to a greater extent ln the mlxture.
lncreased concentratlon ol
4( ) aq
NH
+
lons ln the mlxture dlsturbs the nP4CP equlllbrlum system.
Accordlng to La Chateller's prlnclple lncreased concentratlon ol
4( ) aq
NH
+
lons wlll lavours the
reverse reactlon ol dlssoclatlon ol nP
4
CP lncreaslng the concentratlon ol undlssoclated nP
4
CP.
lncreased concentratlon ol undlssoclated nP
4
CP decreases the concentratlon ol
( ) aq
OH

(un
common lon ol weaker electrolyte). Wlth decrease ln the concentratlon ol
( ) aq
OH

lon colour ol
phenolphthaleln becomes lalnt.
{ ii ) 5i/ver ch/oride { 4qc/ ) is sporinq/y so/ub/e so/t. 1he fo//owinq equi/ibrium exist in o soturoted so/ution
of 4qc/ os under:
2 ( ) ( ) ( ) ( ) l aq aq
AgCl H O Ag Cl
s
+
+ +
loqe 17
When small quantlty ol aqueous naCl solutlon ls added to above equlllbrlum system, concentratlon
ol

lons lncreases conslderably ln the mlxture whlch lavours the reverse reactlon ol dlssoclatlon ol
AgCl.
1hls lncreases the concentratlon ol undlssoclated AgCl or ln other words, addltlon ol naCl to
saturated solutlon ol AgCl, preclpltates AgCl.
1hus solublllty ol AgCl decreases on addltlon ol naCl solutlon.
{ iii ) 5odium ch/oride is stronq e/ectro/yte. ln its soturoted so/ution there exists equi/ibrium between ions
ond undissocioted so/t.
2 ( ) ( ) ( ) l aq aq
NaCl H O Na Cl
+
+ +
When concentrated PCl ls added to above solutlon the same belng stronger electrolyte dlssoclates
to greater extent lncreaslng the concentratlon ol

lons ln mlxture whlch ls one ol the common
lon.
lncreased concentratlon ol

lons lavours reverse reactlon ol dlssoclatlon ol naCl.
1hus lt lncreases the amount ol undlssoclated naCl l. e. addltlon ol PCl to saturated solutlon ol
naCl preclpltates naCl.
6ive opp/icotions of common ion effect in quo/itotive ono/ysis.[ 4 marks]
Precipitotion of ll
nd
qroup cotions.
Aqueous solutlon ol PCl ls added belore addltlon ol P
2
S
(aq)
to preclpltate catlon ol second group.
Aqueous solutlon ol P
2
S ls an lmportant qualltatlve reagent. Cn lts dlssoclatlon ln water lt glves
and

lons.
Sulphlde lon thus released preclpltates Cu
+2
,Mn
+2
Zn
+2
Cd
+2
etc lons.
When aqueous PCl ls added to aqueous P
2
S solutlon whlch ls ln equlllbrlum concentratlon ol
lons lncreases to large extent slnce PCl ls stronger electrolyte than P
2
S.
2
2 2 ( ) 3 ( ) ( ) l aq aq
H S H O H O S
+
+ +
2 ( ) 3 ( ) ( ) l aq aq
HCl H O H O Cl
+
+ + +
lncreased concentratlon ol lons lavours reverse reactlon ol dlssoclatlon ol P
2
S lncreaslng the
concentratlon ol undlssoclated P
2
S.
1hls lowers the concentratlon ol

lons ln the mlxture (common lon ellect ).
uue to thls lowered concentratlon ol sulphlde lons only 2
nd
group catlons wlll glve the preclpltate
whlle catlons ol 3
rd
8 does not glves ppt.
lo//owinq co/cu/otion wi// c/orify the concept(for informotion on/y}
now ksp MnS = 1.0 x 10
-18
whlle that ol CuS = 4.0 x 10
-38
.
now ll Cu
+2
, Cd
+2
etc lons are present ln the aqueous solutlon, thelr product ol lonlc concentratlons
wlth

lons exceed thelr ksp values l. e. ll glven aqueous solutlon has

as well

lonlc
product ol CuS lncreases than lts ksp to preclpltate CuS. ksp MnS ls hlgher than lonlc product ol lt
and hence lower concentratlon ol

wlll not be able to preclpltates MnS.
Cu
+2
, Cd
+2
, Pg
+2
, b
+2
etc have very low ksp whlch can be preclpltated by lower quantlty ol

lons.
Above catlons are classllled .ln second group ol analytlcal classlllcatlon. 1hus aqueous solutlon ol
PCl ls added belore addltlon ol P
2
S to preclpltate catlon ol second group.
Precipitotion of lll
rd
4qroup cotions.
nP
3
ls weak base when dlssolved ln water, lt glves

lons as under:
3 2 ( ) 4( ) ( ) l aq aq
NH H O NH OH
+
+ +
1hough dlssoclatlon ol nP
4
CP ls leeble, ll releases smaller quantlty ol

lons ln the solutlon.
1hls smaller quantlty ol

lons ls sulllclently large to preclpltate le
+2
, Al
+3
Cr
+3
,Zn
+2
, Mn
+2
, nl
+2
, Co
+2
or Mg
+2
lrom thelr aqueous solutlons ln lorm ol thelr hydroxlde preclpltates.
1he product ol concentratlon ol lon wlth concentratlon ol

lons present ln the solutlon (lonlc
product) overcome the ksp values ol thelr hydroxlde preclpltates the glven salt.
loqe 18
ll aqueous solutlon ol ammonla ls added ln lorm ol nP
4
Cl, due to common lon ellect, concentratlon
ol CP
-
lon decreases.
4 2 ( ) 4( ) ( ) l aq aq
NH Cl H O NH Cl
+
+ +
nP
4
Cl ls stronger electrolyte dlssoclatlng to hlgher extent ln the mlxture compared to degree ol
dlssoclatlon ol nP
4
CP.
uue to hlgher degree ol dlssoclatlon ol nP
4
Cl, concentratlon ol

lons lncreases ln the
mlxture whlch ls common lon.
lncreased concentratlon ol

lon wlll lavours the reverse reactlon ol dlssoclatlon ol nP
4
CP
accordlng to Le Chateller's prlnclple. 1hls lncreases the concentratlon ol undlssoclated nP
4
CP
decreaslng the concentratlon ol

lons ln the mlxture.
Wlth lower concentratlon ol

lons, lonlc product ol only Al(CP )
3
le(CP)
3
lncreases than thelr
k
sp
. Slnce k
sp
ol Zn(CP)
2,
Mn(CP)
2
, Mg(CP)
2
.etc. are hlgher these catlons cannot be preclpltated by
nP
4
CP ln presence ol nP
4
Cl.
Pence, nP
4
Cl ls added belore addltlon ol nP
4
CP to preclpltate lllA group ln qualltatlve analysls.
lndicote Lewis ocid ond bose in [No {n
2
O )

,[co{cN)

]
-l
,[crl

]
-2
,[Ni{c/)
4
]
- 2
, [4q {Nn
l
)
2
]
+
, 8l
4
-
.
lewls oclJ. No
-1
, co
-J
, ct
-4
, Nl
-2
, Aq
-
, 8l
J
-
lewls oclJ. n
2
O, cN
-1
, l
-1
, cl
-1
, :Nn
J
, l
-1
6ive conjuqote ocid of
ncOOn,
2
4
HPO

, nl , cn
J
Nn
2
, cn
J
On, c
6
n
5
cOOn, cN
-
.
2
3
CO

,
1
4
HSO
2
4
SO

ncO
-2
,
1
3
NO

, ncOO
-1
,
1
2 2 4
H C O

,
1
3
HSO

,
2
3
SO

.
(AJJltloo of ptotoo l. e. n
-1
to obove teoctoots qlve coojuqote oclJ. )
6ive conjuqote bose.

1
4
HSO

, cn
J
cOOn, n
J
O
-
, Nn
J
,
4
NH
+
, c
6
n
5
On,
2
4
HPO

n
2
5
(kemovol of ptotoo l.e. n
-1
to obove teoctoots qlve coojuqote bose)
Def|ne buffer so|ut|on and d|scuss ac|d|c and bas|c buffer.
~ ..,, .... . . ... ..... . pn ,.. .. . .,. . ... , ...
... , . .. Ok
. .... ... . .. .. pn . ..... .. . ... , ... ... ,
. . .. ..,, .....
1he pP ol the llulds llke blood ln our body and urlne ls almost constant. ll there ls change ln thls pP,
lt allects blochemlcal reactlon ln the body. 1he pP ol chemlcal and blochemlcal reactlons ln our
body are constant, vlz. the pP ol human sallva ls 6.4.
8uller solutlons can be acldlc or baslc. ll pka ol weak acld and pkb ol weak base are known, buller
solutlons ol known pP can be prepared. 8uller solutlons can be ol three types as lollows :
(l)Acldlc buller solutlon (ll) baslc buller solutlon (lll) neutral buller solutlon.
4cidic buffer
~ ..,, .... ,, . .... .... , , . . . . .. . . ..
,.. ,,.. ... . .. .... . .. .. ..,, .....
lot exomple cn
J
cOOn - cn
J
cOONo ls oclJlc buffet.
8osic buffer
~ ..,, .... ,, . .... .... , , . . . . .. . . ..
,.. ,,.. ... . .. .... . .. .. ..,, .....
lor example nP
4
CP + nP
4
Cl ls baslc buller.
Neuttol buffet solutloo .
~.. ..,, .... . . ,, . ....... , , . . , ..
8uller solutlon ol known pP can be prepared by uslng the lollowlng Penderson-Paschelback
equatlon.
loqe 19
lor acldlc solutlons
[ ]
log
[ ]
a
salt
pH pK
acid
= +
where [acld] ls concentratlon a weak acld and lts
dlssoclatlon constant ls k, and [salt] ls concentratlon ol the salt ol thls weak acld wlth strong base.
lor baslc solutlons
[ ]
log
[ ]
b
salt
pOH pK
base
= +
A solutlon ol a strong acld (e.g.PCl) or a strong base (e.g.naCP) ol reasonable concentratlon (~
0.1M) acts as a buller, pP ol such solutlon do not change on mlnor addltlon ol acld or base.
8uller solutlons are used to malntaln pP values durlng chemlcal reactlons ol lndustrlal or
blochemlcal lmportance. 8lood acts as a buller ln human body.