W'T-1OH J1xto

Jaun-gau
Kohna4tcholfa)
ENGINEERING CHEMIS TAY

f o m

Acdic (H1> 1OH Alkaine (OH 1>00) awang

10 10 10 10 10 10 10 10 10 1010 10 10 10 Hdbufer
+ cgCooNq
4 h o

N R e

Frul

MaldilyacIORG Maldly alkaline +KOH

CHhCooH
Neutral
ure water
)
Flg. 5. pH scale

Reversing the signs throughout, we get:

-log [H]-log (OH]= 14.

(4)
sothat pH+ pOH14
10 BUFFER SOLUTIONS
twhen snial aniount of acid or
A butfer solution is one which maintains a
fairly constant pH, even
alkali is added to it, A buffer may be :

obtained by mixing a weak acid with a salt of the sanme acid, eg

Acidic buffer,
H,COOH+ CHCOONa, or
salt of the same weak base, 3
tweak base with a
uki) BrsIc butfer, made by mixing a

NH,OH+ NH,C. from acetic acid and sodium acetate

acidic buffer can be made
Acidic buffers A simple
(Feebly ionised)
CH,COOH H+CH,CO0
dim
CHaCOONa CH,COO + Na Highly ionised)
e r

the acetate ions so-produced suppress the ionisation of the

As sodium acetate is fully-10nised, n0.ecules and more acetate tons
than
coniains more untonised
acetic acid
nuxture
acetic acId, so that the
the added acid) react with
aWhena tew drops of an acid are added to
it, the i jons (from
unionised acetic acid, 1.e,
Cxcess acetate 1ons to
foim teebiy

H' CH,COOH
CH,COO +
rOmadded acid) tNearly uniunised)
(O1 buffer)

the OH (of the

the other hand, Naci) are added,
when a tew drops oftoa base (say H0
(6 en excess acetic acid molecules
and acetate i1ons, 1.e,
produCe
base) combines with
H,O + CH,COO
CH,COOH OH veariy unionised)
(Of buffer) Eom added base)
sodium acetate
small amount of acid or alkali to the butfer solution of
Thus, additior of a
extent.
to any appreciable
and acetic acid does not alter the pi o the mixture

CoTTUAADNdi
Teau d tho
AHdod aud
OY ne
Note-
Wak ais or k
 FLECTROCHEMIS TRY

Basic ersA mixture of ammonium hydroxide and

class.
ammonium chlor
chloride provades an
exampie oT tis
NH,OH NH+OH
NHCI NH +CI (Feebly ionised)
The NH ions, from the
fully-1onised NL,CI, suppress the (Highly ionised
re contains nmore NH,Oi molecuies and more ionisation NH,OH, so that the
of
tons NH, than
(a) When a few
drops ot base
(say NaOH) in-ammönium-aydroxide alone
base) combine with exCess INH added to it, the OH ions
are
1ons to torm
nearly unionised NH,OH. (from the added
NH OH
(From buffer) (From added base) NH,OH
(b) On the other
hand, when (Nearly unionised)
with excess few drops of acid
a
ammonium
hydroxide (say HC) are added, the
water molecules. H
to form
nearly unionised ions combine
NH,OH H
acid) NH;
+
(From added H,O
Thus, we see that (F'ractically unionised)
addition of a small amount of OH or H ions
ammonium
hydroxide and ammonium
chloride
to the buffer solution ot
mixtate does not alter the H'
concentration or
pH of the
pH of acidic
buffer: The dissociation of a weak acid HA is
expressed as:

HAH+ A BA 8 A
whence
K,-A CCnmon 10n 1
or
HAJ to fhoono ALCmon
[H=KHA cuiouau en H
where K is S RChoRd
dissocintion constant of acid.
But for preparing a buffer, a highly ionized salt
entirely n the tonic torm, Le., of acid, BA is added to it. The salt is thus

BA B+ A
and the high concentration of A jons (supplied in this way) stppresses the ionization of weak acid,
HA, so that it can be assumed that all the A ions have come fronm the salt itself, ie,

From () and (in),

[AJ=[BA
we get:
[H'1=K,A-K
BA
Taking logarithm and reversing the sign, we get

pH=-log K, log Salt -log K, Salt

+lE [Acid]
-

Salt pK,
pH=- logA,+ lo8 tAcid [Salt . 0)
+108Acid
1Acid
This is often termed as Henderson-Hasselbatch equation.
 Pt ot basic ENGINEERING CHEMISTRY
buffer: The dissociation of a weak base BOH is
BOH=B+OH represerntec a

Whence
K OH
[BOH
OH=K, UO
where K, is the
dissociation constant of the base.B' (Giv)

DtOr
thus
entirely inpreparing buffer solution,
the ionic form, it., highly ionised salt of buse, BA is added
a
to it. Ihe sat 1s

and
BA B' +A
this
high concentration of B
BOH, so that it can be ions, thus-supplied, suppresses the ionization of the weak Dase,
assumed that all B ions have come
from the salt itseiy, 1e,
From (p) and (®), BT=[BA]
we
get: .)
OH= BOH
BA
Taking logarithm and reversing the sign, we get
log[OH]=-log K,-log Base
Sal-log
Salt K, +log Base
pOfH=-log Ky+ lo8 Base
Salt ISaltl
[Acid]
A1 SOLUBILITY PRODUCT
Consider the saturated solution a
of sparingly soluble binary dectrolyte, AB. There
cquilibria simultaneously between undissolved
solid, dissolved (but exist troo
ions, i. unionised) molecules and free
2
AB AB
(Undissolved solid) A+B
(Dissalsd,
fnionisodi
but (lons in
Applying the law of mass dorused solution)
action, it follows that
so
ATEK, . IAB)J
(AB), wrdmdwed SoLe
.On
multiplying, we get
LA 1B JB)l_AB-K,xK
TCAB) TCAB),I (AB),
But the concentration of solid AB is
constant, so that:
where constant K
1A J[B]=a constant =Ky
is
known as the solubility product ot AB.

t
 Y ELECTROCHEMISTRY
In general, for an
electrolyte, A, B, which ionises as:
A, B XA +yB
the solubility product is given by :

io)
where [A] and [B 1are the ionic 0)
of an
electrolyte may be defined as "the concentrations in saturated a
s
(expressed in mole per litre) im its naximum product of solution. Thus, solubility product
of times the ion occuTS solution, twhen each ionic the concentrations of its constituent ipns
example, for:
the1n
concentration
equation representing the solution term being raised to the
ofl molecule number
of the electrolyte". For
e,
AgCrO 2Ag+Cro
the solubility product,
pAg' ICo1
Relation between
lyte, AB, which solubility and solubility product: Consider
dissociates at: the
general form of electro-

AB, x[) +y[B"]

yS
Let S mole/litre be the
solubility of the electrolyte, then concentration
A=x.Smole/L and [B]=y.Smole/L
sLA"*[B1
For
K,=[S (ySy=x.ysy (0)
example, in case of
BaCl, Ba
+2C1;x=1 and y=2
K1.2.si*2=4 S.
Application of solubility products: From the relation:

it
is héar that:
(a) a solution in twhich ionic
product [A FIB Y5 iess than K, the solutiom
more A, B, can be dissofved in it ;
is
unsaturated and
(6)a solution in tuhich ionic product [A TIB Tsequal to K, is just
saturated, and
()ifanything is done to the solution twhich tends to muake [A T [B Tgreater than then solid
A,B, will be precipitated. Kp,
ELECTROCHEMISTRY
Thus
C1 +AgNO AgCIL+ NO,
K,CrO +2 AgNO, Ag,CrO+2 KNO,
(dh excess) (Brick-t
12 COMMON-ION EFFECT
h edecrease in
ionization of a weak electrolyte by the addition of a strong electrolyte,
cotmton twtth the
weak
electrolyte, known as common-1on etfect.
is having an ion
Consider the
equilibrium existing in solution of a weak binary electrolyte, D
AB A+B
On (Feeble ionized)
applying law of mass action, we get :

K
then, due
Now, if to this solution strong electrolyte AC
a
to the
ionization of
(or BD), having a common A (or B ), 1S adaea,
AC,
AC A+C
the
concentration of A
will be increased. In order (Highlyionized)
decrease and that of AB
will increase. In other
to
keep K constant, the concentration ot B Will
degree of dissociation of AB will be words, more AB molecules will be tormed, iE, me
suppressed
Applications of
analysis, the ionisation common-ion effect: () In analytical chemistry : In lI
of weak acid, HS group ot
qualitative
HS 2H+S
1s
depressed by the (Feebly ionized)
presence ot strong acid, HCL, having a common ion, H

HCI H+CI
Due to the
depressed degree of dissociation of HS, (Highly ionized)
twhich the concentration of S* ions produced
causes the is
precipitation of sulphide of I group cations only.
low,
Simiarly, in l
group, the ionization of weak base,
NH,OH,

is
NH,OH NH +OH (Feebly ionized)
depressed by the prior addition NH,CI, which furnishes
ion, NH.
a
high concentration of common

NH,CI NH +C (Highly ionized)

Due to this low dissociation of NHOH, the OH concentration is quite low. This low
concentration is OH io
sufficient only to precipitate hydroxides of AP, Cr and Fe*.
Solved Exam1ples

. f the resistance
1.Specific conductivity of N/50 KCl solution at 25°C is
an
0.0002765 mhos cm
Example cell constant ?
(Anna, May 95)
of cell containing this solution is 500 ohms, what is the
Solution. cond. () Cell constant / Resistance
Sp. =

Cell constant = Sp. cond. x Resistance

= 0.0002765 ohm cmx 500 ohm =0.138 cm

Examplé 2. conductor cell has two parallel plates of 1.25 cmt' area placed at 10.50 ge apart, when filled with
be 2.0 x 10 ohms. Calculate the cell constant
and the specific
a Solution of an electrolyte, the resistance was
found to

conductance of the solution. (S. V., Sept. 97)

Solution. Cell constant =1/A =

10.50 cm/1.25 cm' = 8.4 cm

Sp. cond. (K) Cell constant/Resistance =1/AR

=

=
10.50 cm/1.25 cm x 2.0x 10 ohm =
4.2 x
10 ohm cm
Example3.A 001 N-KCI solution shorus a resistance 225 ohms in a condtuctivity cell. The specific conductivity
of 0.01 N-KCI solntion at the temperature of Experiment is 0.00141 mho/cm. If a 0.02N solution ofan acid shousa
resistance of 80 ohms in the same cell,find the specific and equivalent conductance of the acid. (DDIT, May 99)
 es X UD
SFCemuk C

S ECTROCHEMISTRY
edueBna
solution,
cell constant,
P
cOnd.XResis

001N KCI
values for
Using
oution. 0.3173 cm
=0.00141 ohm 'cm 'x225 ohm=
acid solution
cond. ( ) of 0.02N cm
Sp. x
10 ohm
Cell constant 0.3175 am -3.966
soln.
80 ohm
Resistance of acid

Eq. cond. of 0.02N acid solution,

1,00 x 3.966 X 10 ohm cm- 198.28 ohmcm eq

S000XK_
0.02 eq cm at 298 K. Iis
10'N acetic acid is 48.15 ohm cm eq
Kamplhe eguiralent
conductance of 1.028 x
dissolution of constart acettc acu.
orauctance at infinite dilution is 390.6 ohm cn eg.Calculate the (Bangalore, Aug. 97)
ie
Solution. Degree of dissolution of acetic acid,

ACHCOOH)48.15 ohm cm eq=0.1233 or 12.33o.

A (CHCOOH) 390.6 ohm cm eq
 txample 8. ENGINEERING CHEMISTRY
Cnleulate the pllof 0.01N solution of
Solution. O1 lin
0.01N
NaO11. C%) (MD, Dec. 99, Mav 2K)
NaOH= 0.01 N=10 N
H in 0.01N NaOH
H 10110
1N
lence, plt=-log 10 *=-1-12]=12.0
Example9alculate the pH of: (a) 0.0001 M HCI
solution, (b) 0.04 M
dissocintio in ench
case HMO solution, a5s
(MD, Dec. 98)
Solution. (o) pti=- log
[H '1=- log 000D--F
(6) [H= 1x1014 1012
OH 004
H 10-12log 4x 10-12.602.
Exampl 10,Calculate the pH of 0.002 NNH,OH having 2.3% dissociation PT, June 04)
CH)= T = C
Solution. (OH J=0.002 x (2.3/100) =0.000046 mol L

10
H 0.0000462174 x10mol 1
Hence, pH=-log 2.174 x 10=(-08373 + 10.07)=9.6627.

xple en solution of propionic acid is half neutralized

a toith NaOH, the pH equals 4.87. What is the
(MD, May 01)
dissociatiern constant of
acid?
5.13 1.34 X 10
Solution. H]= Antilog (-pl)= Antilog (-487)= Antilog
=

Now CalsCOOH CH;COO+ H

Initial
/2 C/2 C/2
Half-neutralire
[HT=C/2=134 x 10 O
fence,
ICHCO01HT_ (C/2)X(C2c/2=134 x10 ACHt AcpNa
a[CH,COOH] (C/)

mixed with 50 mL of 0.2 M sodiun acetate solution. What will be the

Example12.50 mL of 0.2 acetic acid are
10 (DDIT, Dec. 99)
pH of the muature 7 K, 1.85 x =

Solution. 1otal volume of solution = 100 ml, so [Acid= 0.1 M and [Sod. acetatel =0.1 Ako 9XD2

pH-- log K, +log Salt log1.8 x10 log1

Acia -0.

-log 1.85 +5+0=-0,2672 +5.0=4.732

Examplé13,/30 mL of 0.1p M NaOH is added

to 100 ml. of 0.1p M solution of acetic acid. Calculate pH of the
(Dibrugarh, May 99)
buffer solulion. (K, for CH,COOH= 1.8 10)
x

Solution. NaOH + CH,COOH CH3 COONa + H,O

30 ml.0.1 M NaOH+30 ml. 0.1 M CHJCOOH 3 0 ml.CHCOONa +30 ml. H,O

Total volume of solution

=
(100+30) ml, = 130 ml.
Volume of 0.1 MCH,COOH left unreacted = (100-30) ml = 70 m

CNaot)
30XO)(H)
AcDNa

-[Naai) 30 X Ol)
13D
ACOH 1oD xO)1
e. butley
ALD Nq+ AcOy
 ppl dra F .
Y / ELECTROCHEMISTRY
M/130
70x0.1 M/130:[CH4COONa]= 30 x0.1
S XCH,COOH] =
ICH,COONa}/|CH,COOH|= 30/70
[CHOONa-log 1.8 10A log 70
plH--log K+1O8 (CH,COOH]
-0,2553+5]+0.0682=A.8129.=4. 33
is added to one litre of a 5outon containing
ete Example 14. What is the pBH of the solution when 0.2 mole of HCl 0
OfCHCOOH and acetate ion. Assume total volume as one litre. K, of CHgCOOt= .0
8) c
(Dibrugarh, July 01)
Solution. H (of HC)+CH,COO
Initiat
( CH5COOH
1M 1M
On adding HCI 0.8 M 12M

pi=-log Natig CH,COO.-log

CH COOH 1.9x 10 +log 8
04) =4.7447+0.1761 = 4.9208.
xple 15. The
25° C solubility of AgCI in zonter at 25 C is 0.00179 gL. Calcuilate its solubility product at
(PT, Dec.2K)
Solution.
Solubility, =0.00179 g/L=0.00179/170 mol/L 1.053 x 10 mol/
S =

Solubility product of AgC1, Kp=[]'[1]'|S]' =S

=(1.053 x10= 1.1087 x 10 mol L
Example 16. The solubility product of CaF2 in water 18°C is 3.45 x 10". Calculate the
Uiter. solubility of CaF2 1t
(T, Dec. 97)
Solution.
Caf Ca +2F
Ksy for CaF=1'x2 (5)-4S

3.45x 10-4S
solubility, S= (3.45 x
10"/4molL'=2.05 x 10 mal I
 ENGINEERING CHEMISTRY ELEC
WCalculate pH of 0.005 M Ca(OfHy assuming complete dissociation. (Nagarjuna, July 97)
solution. [(OH1-2x [Ca(OHl
:1 mol ofCa(OH}» gives 2 mol of OH1|
=2
x0005=10 mol L

[H]= 1x10 14
TOH 10210mol L
Hence, pH=-log [H']=- log 10 "--12] 12.0 acid?

Example 20. Calculate the pH of a 1.0 x 10 M-HCI soltion. (MD, Jan. 2K; Andhra, June 97)
oution. Ihe FH3O ion are produced from: () the acid dissolved, and (i) the ionizaton ot wa
Initial
An the solutions of 10 M or greater, the ionization of water is repressed and negigibite, Chang
solutions,less than 10 M, both sources of H ions (acid and water) are to be considere Equill
HCI (aq), a strong acid, ionízes almost completeiy.
HCI(aq) H' (ag)+CI
1.0x10M
(aq
10x 10 M
the Jonuzanon
M of H' ions. Consider
NOW, we start with a solution containing initially 1.0 x 10
H,O. Let x= (OH ] at equilibrium.
(CHS
H,O) H(aq) + OH (ag)
Reaction:
- 1.0x 10 0.00
Initial concn. (M)
CH
Change (M)
(1.0x 1070 +)
Equilib. concn. (M)

But KH][OH"]= 1.0x10

(1.0x 10+ 2) x=1.0x 10
( 1 . 0 x 10 )x-1.0x10=0 Inita
-(1.0x10)+Va.0x 10+4010x10-95x 10*M Chan

x 2()
Eqilit
107= 10.5x10
IH ]=(1.0x 107 10 +9.5
+ x)=1.0 x x

pH=-log lHJ=-log
10.5
10 6.98. x

?
M NaOH solution
pH 1.0x 10
ionization
21. What is the contribution of
OH ions from the
Example so the
NaOH is tery dilute, s01LZAtio1 of tuater.
Solution. Since the solution of dissolted, arnd (u)
the
from : (9 the base
considered. Thus, OH are produced
of water is also
OH
NaOH Na
1.0x10 M
1.0x 107 M ionization of
Consider the
M of OH.
solution containing intially
1.0x
10
Now we start with a

equilibrium. Then
:

H2O0. Let x=[HJat

HO) H(ag) OH (aq)
Reaction 1.0x 10
Initial concn. (M) FX

M) (1.0x 10+)
Change
Equiib cotnich. (

Ka=[H 1 [OH]=
1.0x 10 HSy 2H Sop Equl
But
10+x)x=1.0x 10
(x) (1.0x O1 2x0:
O2

Sy
Joa H
)
pH o 1 - 0:33 +I

pt1 04
 THence,
percentage ionization ()= (t/0.1) x 1.00=(1.3x 10 M/0.1 M) x 100= 1.3%.
Example25)Find the pH of buffer solution of 0.2 mole of acetic acid per litre and 0.10 mole of soudtut aeet
per litre. The dissociation constant of acetic acid is 1.8 (DDIT, July 96)
10 x
Solution. From Henderson-Hasselbatch
equation, the pH of acidic butter
-loyK, +logcid-log 18 x 107 +log 02/
=-log 1.8+5.0+log 0.5=-0.2553+5.0-0.3010=4.4737.
Example26.Taiculate the amount of NH3 and NH,CI requirei to prepare a buferof pH 9.0, uen lhe totni
coRcentrationm
ofbitfering reagents is O.6 mol L (pK, for NH3= 4.7)
the concentration of NHg (base)
Douion.Let concentration of NH,CI be mol Lso
r

(G.6-x) mol L

For basic buffer: g+log =14- pH

pOi=pAytog [Base]
or 0.3=lo8(6.6-og 2
14-9=4.7+ 1o8 (0.6-)
0.6-x
2or x=0.4
and [NHs] 0.2 mol L"
Hence [NH,CI)=0.4 mol L =

solution be
1lhat in tin uil of 1 M salution of atic acid ? What volume must one litre of tlhis
 ENGINEERING CHEMISTRY

cell
constant
? Give its units.
t is
the area of the electrode.
the the ratio
tatio of the distan
of the distance between the parallel plates of the cell and
Kns.1 1s
of a weak
the eltect of dilution (decreasing concentration) on the molar conductivity
ohat is

yte
A n s i t hmcreases,

5,ftow is molar conductivity related to molarity?

1,000xK
Ans. AmMolarity
and molar conductivities.
Give the relationship between equivalent
Ans.
AmNormality
Aq Molarity

efine is Kohlrausch's law ? of 1onic conduc

At infinite dilution, the molar conductance of an electrolyte is equal to the sum
Ans.
ances of
cajons and anions at infinite dilution. ?
is the effect of temperature on molar conductivity
8What because at a higher temperature,
Ans. imcreastng the temperature, the molar conductivity increases,
On
the ioniç mpbilities increase.
a wenk electrolyte vary with concentration ?
How does molar conductivity of
Ans. It increases steadily with dilution.
with dilution ?
191ow does molar conductivity of a
strong electrolyte vary
but with dilution.
Ans. it increases only slightly, linearly and normality ?
is specific conductance related to equivalent conductivity
Ho
Ans. Eq. conductance
(A)=P.Cond. (K) x1,000
Normality

12Xhy does the cquivalent conáactivity

of a weak electrolyte increases with dilution ?
(Bangalore, July 95, Aug. 95, April 97)
 ELECTROCHEMISTRY
pecitic conductance decreases with dilution ; while the equivalent conductance increases
reason, (Bangolore, Aug. 9
namely ot
Ans. When an solution is diluted, two things
electrolytic happens, degree disociation
increases, but the total volume increases. The number of ions per cm' decreases, because the etrect of inreased
voune in decreasing the number of ions cm outweighs the minor increase in conductnice win increase of
ciuton. On the other hand, equivalent conductance increases, because the total number ot10ns per gram
equivalent increases with dilution, due to increased degree of 1onization
Define specific conductance and equivalent conductance (Bharathiar, Nov. 97)

Ans, specific conductance is the conductivity of 1 cm' of solution; whereas equivalent conductance is the
conductance of the all the ions
present in 1 gram equivalent of the electrolyte in the solutionata ga udsm
17, Give the
relationship between equivalent and molar conductance
Ans. AmNormality
Molarity 1,000 K 1,000*
M Molarity Normality
does the
HOw
50.ution?
molar conductance of a strong electrolyte vary sloruly with
its conccaitrato
Ans. Molar
conductance of a
strong electrolyte is always high and it increases only slightly, but
witn hneary
anuton, and soon
reaching the maximum value, known molar conductance at tnfinite
as
i O w does molar conductivity of a tweak electrolyte vary with its concerntration solution aluttort.
Ans.
Molar conductance of a weak electrolyte is very low and it increases steadily with
decrease inconcentration). dilution (or
Write
5. an
expression to relate molar conductivity of
Ans. Degree of dissociation () at
an
electrolyte to its degree of dissociation.
given dilution
Molar conductivity at the given dilution (A
Molar conductivity of the same electrolyte at infinite dilution (Am)
21. How is the unit of molar
conductivity arrived at ?
Ans. AjKX Vol. of soln. in cm
containing 1 mole of the electrolyte
n i t s of Am =ohm cm x cm mol=ohm cm mol

rlow are specific conductance and equivalentconductance related ?

Als, Eq. conductance (A)=P.cOnd. (8)x 1,000
Normality of solution
23. A bottle marked is pH=5. Does it contains a very weak acid?
Ans. The bottle can contain either a weak acid or a very dilute solution of a strong acid, like
HCI/F2S04/HNO3. 1he pH alone does not tel us whethera solution contains a strong or weak acid (or base)

since pH depends only on the concentration of H ions.

of water at 65°C ?
b What is
possible pH pure
Ans. Less than 7, since the concentration of H ions in water at 65°C is more than 10 mol L
)
25. What is the effect of dilution on pH of an acidic solution ?
Ans. pH imcreases toward 7.
26. What is the pOH of pure water at 25C
ly
Ans. pOH=14- pH =14-7=7.
 ENGINEERING CHEMISTRY El

are the unis of dissociation constant ?

7 What

nol.e, K,C1,COO) gCO0 (a9)l[H'(an)]

Ans. CHCOOH aq)]
mol Lx mol +lmol L
nol L.
107
28. What chemicals would you use to make a buffer of pH: () 5, (n)
Ans. ) CH,COOH +CH,COONa, (i) NH,OH+ NH,CI.
mol L CH,COOH and

29.pK, value for acetic acid is 4.75. What is the pH of a buffer containing 0.1
0.1 mol L. CH,COONa ?

Ans. 4.75. ?
iodide, Pbl,
30/What are the units of solubility product of lead
Ans. Kp-Pb"]UF= [mol L" ] [mol Lf=mol'L and
of CHSCOOH
in a buffer solution consisting
31. What is the major source of CH,CO0 (a9)
CH COONa ?
solution.
of CHCOONa in aqueous
Ans. The complete ionization electrolyte
of ionization for strong
a

32. What would be the value of degree

?
solution of KOH
Ans. Nearly 1. the other a
buffer solution,
two solutions of pH 9.0, one a solutions by
33. How would you test the pH of the resulting
to a sample
from each, and test little trom 9.0;
that of
dil. HCI
Ans. Add a few drops buffer solution will change very
of the
solution. The pH
or indicator
using pH paper (in) CH3COON
decrense significantly.
will solution, (i) NaOHsekution,
KOH solution dilution on pH value of : ) HCI
is effect of
3What
solution?
decreases, (in)
remains nearly
same.
H number of sodtium in
increases, (i7) the transport
Als. pH: (0 sodium
chloride the
same as

number of sodium in
35. 1s transport ionic
Give reason. the co-ion. Since the speeds (or
sodium sulphate ? relative to that of
ion is a term not equnl
number of an
ions in NaCl is
Ans. No. Transport the transport
number of Na
are not identical, so
ions
CI jons and SOg
mobility) of
number of Na ions in Na,SO of transport
number ?
to the transport
determination
the
small current during in-turn causes change in
do we use a very etfects. This
35. Why thermal and resulting
diffusion

minimise
Ans. In order to number
a r o n d the
two clectrodes. 0.5. What is the transport
concentration oniy anions of an electrolyte is
cations and
The ratio of the speeds of
37.
?
this efectrolyte
of cation in dilution
HA at infinite
Ans. 0.333. conductivity of
acid HA is 0.8. If equivalent dilution ?
number of H ions in infinite
ions at
38. Transport ionic
conductance of H
is the value of
eqwhat
is 350 ohm cm
Ans. 280ohm cm eq water,
hydrolysis
of salt.
or a n i o n s or both) with
39. Define 1ons of salt (cations
reaction of
chemical of
Ans. It is the

degree of hydrolysis.
attained.
40. Define has been
when equilibrium
fraction of the
salt hydrolysed
Ans. The
standard Vll

the ion concentrations.

2.303RT
a t 298 K.
of
Calculate
the value F
Pfoblem:
F= 96500 coulombs mol ,
know
K and we
Here T= 298 ,

Ans:
mol'
R=8.314 joule K

the value of the quantity,

Hence molx 298 K
2.303x8.314
Joule K
2.303RT
96500 coulombs mol
0.059 volt. [Since, volt Xcoulomb =joule
cell,
Calculate the EMF of the
Problem:
Cu(s)
CuSso,(0.001M)|
Zn(s) ZnSO,(0.IM)| |
cell is 1.103 volt at 25°C.
when E of this

cell, the cell reaction is

Ans: For the given
+ Cu
Zn +CuSO, ZnS0,

ZnSO, ]ICu
Hence reaction quotient Zn][CuSO,]
aboe
to the
of electron transfered
corresponding
and the two moles

cell reaction, 1.e., n =2

is given by the Nernst equation

The EMF (E) of the cell
RT ZnS0, ]ICu]
Ecelell nF Zn]ICuSO,]
sACTAONHEMISTRY 139

inc and copper are in solid pure state, it is assumed that active
S Zn and Cu are unit, 1.e.. 1Zn] =|Cu] = l and given: [ZnSOJ=
a s so f 2
= 0,00IM
[CUSO,]
a 1M.
Hence E l 1 . 1 0 3 - o.05 108 (0.1x01
10
001)
= 1.103-0.059 =1.044 volt.
S i n g l e Electrode Potential

Since the reaction involved in a galvanic cell is the combination of

ruo half cell reactions atwoerecrodes, tne
cell
potential is the resultant
t
E, and E, be the reduction of
potentials the
f the electrode potenttals. to the international
rwo electrodes, the
Cett potental
eea dccording
convention would be

EelE, -E
The reduction potential of a redox couple is a measure of its tendency
w gain electron in a redox reaction. Since oxidation is the reverse process
ofreduction, the values of reduction potential with opposite sign give
ot a redox couple.
the oxidation potential
Thus it may be stated that the electrode potential is the tendency
ofan electrode in a half cell to lose or gain electrons, whereas EMF of
a cell is a measure of relative oxidizing and reducing power of the
electrodes of the cell.

Problem: Calculate standard EMF of the cell

Zn Zn(IM)|
|Fe:(IM),Fe*(IM)|Pt
Given that, E2/z=-0.761 volt and EpFe =0.771 volt at 298K.
Ans: Eel =E Ey EfpE212
-
=

= 0.771-(-0.76) = 1.532 volt

 zero.
IS taken as
MULTIPLE CHOICE QUESTIONS

is negative, it ima
Q. 1.If AG for a given cell reaction
implies
that
is negative
(a) E.M.F of the cell

E.M.F of the cell

is positive
(b)
Cell reaction is feasible
(c)
(d) both (b) and (©)
constant is
Q.2. Cell
(a) l/a
(b) alc
(d) None of these
(C) al
conductance is
Q.3Ahe unit of molar
(a) Ohm. cm. mol D Ohmcm mol

(C) Ohm cm mol (d) None of these

is
Q. 4.Unit of ionic mobility
(a) cm volt sec (b) cm. volt 'sec
 147
gLECTROCHEMISTRY

(d) None of the

above

(c) cm.
volt. sec
is called
at the junction of two electrolytes
The potential
potential
liquid junction potential
half cell
(a) potental (d) standard
reduction potential
oxidation
c) standard
involved in the calomel electrode is
metal ion
o.6. The

(a) C a * (6) Hg
(d) Pb2*
Hs3

is reversible with respect

to
electrode
calomel
0.7.The
(b) Hg2*
a) Hg
(d) None of the above
(c) CI and each
has eletrodes 0.6 cm apart
conductivity cell
0.8.A cell const is
em. The
area 0.8 sq.
isof
(g0-75cm (b) 1-00cm
(c) 1-25cm
(d) 15cm
has electrodes I apart and each
em
conductivity cell
Q.9JA filled with a KCI solution containing
50
is of area 2cm. When
resistance of 7.25 ohm only. The equivalent
KCllitre, its
gm
conductance of the cell is

(a) 100-00 oh m cm *eqv

b) 102-76ohm emeqv
(C) 106-7 ohm.cm.eqv
None of the above
current
correct statement for a galvanic cell when
Q. 10. The
s drawn is

(a) EMF remains unaltered

(b) EMFsuddenly inereases

(C) EMFdecreases and finally falls to zero

(d) EMF increases

 8 ENGINEERING CHEMMST
conductance is
Q.WUnit of specific
Ya) ohm-l em-l
(b) ohm cm-

(C) ohm Cm
(d) ohm em.

Q. 12. The relation amongSpecntC conductanceuctance (R), condu

constant is
ance (4) and cell

(a) A=R a (b) AR

(d) AR=ab
C)A=R
The correct order of 1onic conductance of alkol!
Q13. met
ions
<Fr*
Na <K <Rb' <CS"
Fr"
(6) Na'> K> Rb"> CS">
<Fr"
()Na<K<Cs <Rb
() Na> K >Cs'> Rb> Fr
units is correctly matched?
Q.14. Which of the following
(a) Unit of conductance
mho cm-
conductanceohm-lcm2 eqv-t
(6) Units of equivalent
(c) Unit of ionic mobility emv-i-S-
(d) All of these
solution of KCI will have the
Q. 15. Which of the following
value of equívalent conductance ?
same

(a) 0.01 NN (6) 0.005 M

(c) 1.0 M (d) 0.05 M.

16. The unit of ionic mobility is

Q.
(a) cm-2r-is-l (6) cm2r-ls-
(c) cm-2 rs-l (d) cm2r-2s-l,
ELECTROCHEMISTRY
149

a salt bridge is used

an electrochemical process,
o./17 In
maintain electroneutrality in cach solution surrounding the
a To
electrocles

(b) As an oxidising agent

(c) As reducing agent
As a colour indicator
(d)
water is
18. The pH of 10-8M solution of HCI in
Q.
(b)-8
(a) 8
(d) Between 6-7
(c) Between 7-8

Exercise