alsowhere ofThe mersed

Example 17
Solution: tration ficients
and havewe 698
The the 18.24 3. 2. 1. 25°C, At Thus, For
includes potential silver M
Calculate
Calculate volt] Replacing
oxidation emf ions Calculate emf
fan
afaz concentration of in
ions a the
moving
of wire solution transport to
the Given NUMERICAL emfof be
the set electrode. the the the at activitiesthe of
junctionoccurs up voltage emf emf 25°C. What positive,
cell
across that, such
POTENTIAL
JUNCTION at
LIQUID of and of of number
Cd|CdSO4(m Chemistry
Physical
and is the In
generated the the the The 0.05 is a
the C the cell a
potential thusjunction the concentration
following other = two
reduction 0.5 molar EMF must
boundary not other PROBLEMS
PRACTICE
FOR PROBLEM ofcan
electrolytesby
in E solutions
M, ions.
ina a = concentration of be be
(6j). only of =0.01, solution
half, concentration
C, greater
potential cell 0.0591 a calculated E
a cell =
concentration
the isthe silver at 0.05 are =
25°Cy=0.383) consisting
of L
sumcalled two log ON 21_RT F than F RT
wire connected F the
solutions in 0.1 M be
(Ez) of cell M C As and In a1 In
I liquid dipswhich CONCENTRATION calculated In molarifies
ofthe concentration
|| at of the
into CdSO4(m 25°C. zinc 0.0591 the cell
the
junction
oxidation one 2 cell by
because electrodes, other
electrode 0.01 a
consisting
half log involves salt if and
=
MAgNO,
consists 1.00, of in we
potential. of its
0.05 0.5 bridge. a know coefficients
activity
potential one solution
where the y=0.042)|Cd ions Zn,
of 0.02955
volt = of
solution. immersed
tot difference a at zinc molarities,
1 Zn
reduction (E.) M 25°C. of
AgNO, CELLS
in
ions, electrodes,
0.5
of [Ans. 0.0307
[Ans.
volt] a
solution molar
the in 0.02955
[Ans. n activity
occurs, solution
0.1182 = ions,the of
electrode the ...(18.64) ...(18.63)
2
speeds of concen one
volu) and 0.01
coef
bu im
a

trolyte
tion
Expressionpotential
transference: is
However, In
And Sum
electrolyte
then The other
Hence, If But Subtracting such
Also,
knowwe the the of
Hence, emf words,
the
activity of
sum asthe
for
Eq. twO KCI.
Eq. the
of almost type
Eq. Liquid the
(18.67) thelectrode
ecell If of emf
(18.68) coefficient (18.65) we
considered two reducedjunction
Junction assume of
becomes, electrode reactions the
may (mHt)2 from
(YH)) E= E H, (1 to cell
of E, employed
be E an = =Eq. 2r_RT + m) zero. that
above E) atPotential
the is
written - =y ion my E-(Ej 21_RT potentials, gives
(2t- 2tRT
_ F (18.66), = |HCI(4,):
RT -
2t-1 +=I,1 (az) H In K* E-
and is and -In is F RT F such most
-1,)n in m, given E jons E
taken(myt)) In In
- + (Refer Yi72 m2
the =t+ 1)- In (4+)h=
E;) we E
+ a +
"Y2 i.e. Consider case. commonly and E,
form mRT Y2
m, to get by HCI(4)|H(1
>H(a)
Yi E, CI Ej +
RT
(- 2 be =m t the
equal E, move Electrochemistry-ll
the emf
RT (18.64)]Eq.
1) F RTgivenby, is is
= to following almostof the
+(-) In atm)
m m,
Yi
Y2
m, the the salt
Y1
mean cell with
bridge
concentration wicelltn canequal
activity containingbe
simplyspeed,
coefficient
taken the an
...(18.66) ..(18.65) junc elee 699
...(18.67)
...(18.68) as
of
the
 700 Physical Chemistry
o
only can the activities of Electrochemistry-l|I 701
Thus, we find that the liquid junction potential depends not between the the two
also depends upon the difference two
solutions constituting the junction but
numbers of the electrolyte. When t 14 then E, =0. In case of an electrolyte for which t_>t, E, transport is 0.3524 Vat 25°C and that the standard electrode notential ofAg-AgClis 0.2224 Vat25°C.
electrolyte
will be positive and thus E will be greater than E + E, by E,. In case of an for which Solution: For the given cell,
I<l4, E; will be negative and hence, E will be less than E, + E2 by E;. 2 RT
-In m =
Ecel t
EAgAgCIE
DETERMINATION OF ACTIVITY AND ACTIVITY Ecell +
2x 2.303 RT
log m = EAg/AgCl -
2x 2.303 RT
log Y+
18.25 COEFFICIENT FROM EMF MEASUREMENT
Putting T= 298 K,R= 8.314 JK- mol- and F =96500 C, this equation becomes
n order to know the activity ofa solution corresponding to the given molarity, we must measure Ecell + 0.01183 log m - EAgagCI-0.1183 log Y+
the activity coefficient of the electrolyte in the given solution. To understand the method for thie Substituting Ecell =0.3524 V, EàeAoCI = 0.2224 V
determination, consider the example of the determination of activity coeffñcient of hydrochlori and m =0.1 mol kgl
acid. For this purpose, consider the following chemical cell without transference:
we obtain
H,(1 atm) | HC1(activity = a), AgCl(s)| Ag 0.3524 +0.1183 log 0.1 =0.2224 -0.1183 log Y
It consists of hydrogen and silver-silver chloride electrodes in hydrochloric acid as the electro.
lyte. As the two electrodes are reversible with respect to the ions of the electrolyte, they may be -0.3524 + 0.2224 +0.1183 =-0.0989
log Y+ =
immersed directly in the acid to give a cell with no liquid junction. The cell reaction is given by 0.1183
the equation =0.796

-H,(1 atm) + AgCl(s) ’ Ag(s) + H(aH)+ CI (a) APPLICATIONSOF EMF MEASUREMENTS

18.26
and the emf of the cell is given by
RT 1. To Determine the Transport Number of lons For a cell with transference
Ecell EA/AgCI - n G- cr
H;(l atm)|HCl(a): HCl(a)|H2(1 atm)
RT the emf is given by,
= EAglAgci In a
...(18.69) E=LRT ...(18.71)
where a is the activity of HCl as a whole. F a,
As the activity (a) of HCl at any molarity m is transport
expression a = mYt, substituting this value in Eq.related to the mean activity coefficient Y+ by the knowing the activities of the two solutions, the
By measuring the emf of the cell and
(18.69), we get, number of the anion (t_)can be calculated.
The emf of
RT
of Sparingly Soluble Salts
Ecel =EAgAgCI - In my 2. Determine the Solubility and Solubility Product
a concentration cell is given by
Ecell =EaAeCI - 2RT In m
2 RT
-In Y E= RTC2
n
..(18.72)
F
2 RT solutions, that in
In m = EAg/AgCI - 2 RT the concentration of ions in one of the sparingly soluble
Ecell +
F In Y ...(18.70) Thus, knowing the emf of the cell and in another beaker is that of the
F calculated. If the second solution completed dis
All the quantities on the the order can be solubility assuming that the substance is
left-hand side of this equation are determined salt, its ionic concentration is equal to its
calculate Y, the value of ExgAgC1 is needed. To experimentally. 10 The following
determine EÀg/AgC|, the quantity t 2RT In m sociated.
solubility of the sparingly soluble salt, AgCI.
is plotted against m and the result is Ecell Suppose it is required to find the
measured.
F
extrapolated to m=0. When m=0, y, =1. cellis set up and its emf is
(18.70) EAg/AgCI= Ecel + 2 FRT In m i.e. equal to the value of therefore, from E4 |N/10 KCIsolutionÀg
Example 18
the ordinate. As Nv10 AgNO, solution Saturated NH,NOs Saturated with Agc
Calculate the mean ionic activity solution taken in one beaker
25°C given that the emf of the cell coefficient of 0.1 molar hvdrochloric acia at silver electrode in N/100 AgNO3
This cell is prepared by dipping a in N/10 KCl solution in another beaker to which 1 or 2 drons
electrode
H,(l atm) /HCl(a), AgCl(s) |Ag and dippinganother silver
 702 Physical Chemistry Electrochemistry-lI 703
of AgNO, solution are added, forming AgCl which is enough to make the solution saturated with
containing saturated NH,NO, sob C= 1.040 x 10 g ea/litre = 1.040 x 10× 143.5 g/litre
AgC1. The two beakers are then connected by a salt bridge or C =1.49x 10 g/litre
Calculations The cell., as described above, is a concentration cell having higher concentratiox 3. To Calculate Starndard FreeEnerqy Change and Equilibrium Constant of a Given ke
Ag ions in the left-handelectrode and lower concentration of Ag' ions in the
right-hand electroi action Electrical energy produced in the cell is equal to the decrease in free energy accompany
concent
(produced by dissociation of AgCl), By convention, we write the electrode with higher
ing the cell reaction.
-AG= nFE ..(18.73)
tion of ions on the right-hand side. i.e.
solution| where AG is the change in free energy accompanying the reaction, n is the number of the moles
N/10KCI solution saturated |N/10 AgNO, of electrons transferred in the cell reaction, F is one faraday (= 96500 columns), E
is the emf of
Aglsaturated with AgCi|NH,NO,|[Ag"]=0.01 |Ag the cell.
If the reactants and products are taken in the standard state, we can write
[Ag*]=C(say) -AGO = nFEO ...(18.74)
The emf of this cell at 25°C is given by Knowing the values of E°, the value of AG° can be calculated.
equilibrium constant K according
For a reversible reaction in equilibrium, AG° is related to the
0.01
E= 0.0597 log
to the equation ...(18.75)
From this equation, the value ofC can be calculated. Thus, in the solution ofAgCl in N/10 KCI. AGO =-RT In K=-2.303 RTlog K
T.
[Ag"] = Cgram equivalents/litre Thus, knowing AG, K can be calculated at the given temperature
following cell at 25°C.
As AgCl dissolves to a very smallextent, the CI ions produced from AgCl are negligible as Example 20 Calculate the free-energy change of the
compared to that produced from KCI. Therefore, in the solution of AgCl in N/10 KCI, S,/ Sn' (a = 0.6)|| Pb(a = 0.3)| Pb
[CT]= [KCI] = 0.1 Standard emf of the cell is 0.014 volt.
The solubility product (K,) of AgCl is, therefore, be given by the equation, Solution: The cell reaction can be written as
Sn + Pb*’ Sn² + Pb
K, =[Ag'][Ci
Cx0.1 Here, n=2
this cell at 25°C is given by
If the solubility of AgCl is s moles/litre then By Nernst equation, the emf of
0.0591 0.0591
[Ag] = [CI] = s gram equivalents/litre E= F°
ap
K, -[Ag[cI]=sxs =s 0.0591 0.6 0.0051 volt
S = = 0.014 - log 0.3
n

Knowing the value of K,, the value of s can be calculated. AG can be obtained as
follows:
0.0051joules
AG =-nFE =-2 x 96500 >x
Example 19 Consider the cell =-984.3 joules
Ag|0.005 MAgNO,|| KNO; (salt) ||AgCl (salt) |Ag concentration cell without transfer
of the lons The emf of a
4.To Determine the Valency
salt bridge ...(18.76)
Ifthe emfof the cell at 25°C is 0.1585 volt, calculate the solubility ofAgCl at this ence is given by RT
temperature. E=
n a nF
Solution: Solubility of AgCl in water is very small; therefore, the concentration ofAg ions in other quantities, n
involved. Thus, knowing all
AgCl solution will be very small as compared to that of Ag ions in 0.005 the valency of the ion
AgNO, Solution. O In this expression, n is
writing the electrode with higher concentration of Ag ions on the right-hand for a very long time. was
side, we have can be calculated. which remained doubtful
example. the valency of mercurous ions, cell:
Ag|AgCl (salt) ||KNO0;(salt) | 0.005 M For following
AgN0,| Ag by setting up the nitrate solution |Hg
Let Cbe the concentration ofAg' ions in the left-hand determined by this method, solution ||N/2 mercurous
electrode of the above concentration ce He|N/20mercurous nitrate
Substituting the values in the equation of emf of concentration cell. we have
C, 1/2 10
C /20
0.1585 = 0.591 0.005 Here,
Eq. (18.75) at 25°C. we get
1
log
Writing the values of the various constants in
which gives E= 0.0591 log
log C = log 0.0005 - 2.6819 n

-3.301 2.6819 =-5.9829 = 6.0171

 704 Physical Chemistry

Putting = 10i.e.. log C; = log 10= 1, we get Electrochemistry-lll 705

C The potential developed is measured
0.0591 aoainst a hvdrogen electrode or
hydrogen electrode is 0.6996 V at 25°C. calomel electrode. Ihe
E = emf with respect to a standard
The emf of the above cell was found to be 0.0295 volt
Hence, 0.0591 0.0591
n=
E 0.0295 Solution of
H0
Thus, the valency of mercurous ion is 2 and it is H 1ons

trate, by Hg, (NO;);. represented as HgT and its salts, such as ni

18.27 DIFFERENT TYPES OF ELECTRODES Pt strip

IN PRACTICAL USE -0

Quinhydrone
Hydrogen bond
1. Dipping Calomel Electrode The Pt
is now commercially available as a calomel electrode Fig. 18.24 Quinhydrone electrode
used by simply dipping the tip of the self-contained
unit. It is 3. Glass The Electrode A commonly used secondary standard
of another electrode whose emf is to electrode in the solution electrode is the glass electrode. Its emf is determined by coupling with
be determined. Ag wire
This type of electrode is often a Standard Calomel Electrode (SCE). The glass electrode provides one
mel electrode (Fig. 18.23). This referred
as the dipping calo of the easiest methods for measuring the pH of a given solution.
saves us from the cumber A glass electrode (Fig. 18.25) consists of a glass tube having a thin -1 M HCI
some method of preparing the calomel. Hg walled bulb at the lower end. The bulb contains 1 M HCI solution. A
The mercury and the calomel Hg,Cl,
row central tube by aporous (Hg,Cl,)
are held in a nar silver wire coated with silver chloride (or a simple Pt wire) is sealed
into the glass tube at its lower end. The lower end of the silver wire dips
wire dips into the mercury. Thecottonwool plug. A platinum
KCl saturated solution con
Porous plug
into the hydrochloric acid, forming silver-silver chloride electrode.
tained in the electrode makes contact with Saturated KCI
the other The glass electrode may be represented as,
solution through a sintered glass disc. This disc electrode Sintered Ag, AgCI| 1M HCI|H (Test solution)
a 'salt bridge' functions as glass disc When placed in a solution, the potential of the glass electrode de Thin-walled
between the two electrode solutions. Thus, a Fig. 18.23 Adipping calomel
galvanic cell is set up and its emf is measured with the electrode pends onthe H ion concentration of the solution. The potential devel glass bulb
of a voltmeter. help ops across the glass membrane as a result of a concentration
difference
Fig. 18.,25 Glass electrode
2. Quinhydrone Electrode It is a of H ions on the two sides of the membrane. This happens much in the
redox widely used secondary standard electrode. It same way as the emf of a concentration cell develops.
reaction between quinone (Q) and involves the The potential of aglass electrode can be determined against a standard calomel
electrode (SCE).
hydroquinone (QH).
OH
DETERMINATION OF pH OR H CONCENTRATION
18.28 OF A SOLUTION BY EMF MEASUREMENT
2H 2e
set up a cell Voltmeter
The basic principle of the method is to that its po
such
in which one of the electrodes is concentration in Salt bridge
OH tential depends upon the H ionand the other elec H,+
Quinone examination
the solution under Knowing the emf of
Or Simply Hydroquinone trode is a reference electrode.potential of reference
the
Q+ 2H + 2e the constituted cell and potential of the elec Pt
The hydroquinone half-cell QH, electrode, we can calculate the under examination
quinhydrone at a definite Hion consists of a platinum strip immersed in a saturated solution
trode containing theconcentrationusing the Nernst
1M HCI Unknown

which gives equimolar amounts concentration (Fig. solution 0 solution

of quinone and 18.24). Quinhydrone is a molecular compou and then the H ion electrodes whose potentials Fig. 18.26 Determination of pH with hydrogen
cell may be represented as Pt/QH,, Q.H hydroquinone in solution. The quinhydrone ha equation. The various concentration are hydro
electrode
depend upon the H ion
 706 Physical Chemistry

gen electrode, quinhydrone electrode, and glass electrode. Using these electrodes Electrochemistry-ll 707
erence calomel electrode, the various methods of determination ofpH are briefly against the ref.
1.Using Hydrogen Electrode
described
The electrode reaction, written as reduction reaction, is below:
RT [QH,]
2 -In [QJ[HP
H+e H, (l atm) [n =2 for the above
reaction]
Potential of this electrode is given by, [QH,]
RT
Quinhydrone is an equimolar mixture of Qand QH,. Taking [Q]=[QH;l and puting [Q]
-In [H"](Nernst equation) 1. in the above equation, we get
EHt, H, EH*, H,
= Eyt H, +0.0591 log [H"] at 25°C RT
RT in(H"]
=0.0591 log [H"] 2F[H
[as E, H,=0)
-0.0591 pH [as -log [H]=pH) =Egt 2.303F XK log [H'1= E + 0.0591lg [H"] at 25°C
A standard hydrogen electrode is coupled with another hydrogen electrode which
solution of unknown pH (Fig. 18.26). In both half-cells, hydrogen contains the = E-0.0591 pH
gas is used at I atm pressure
and 25°C. The emf
of the cell The standard electrode potential (E) of the quinhydrone electrode has been found to be 0.6996
volt. Hence, we may write
Pt|Hz(1 atm) | H"(1 M)|| H(unknown) | H,(1 atm) |Pt. Eo =0.6996 0.0591 pH
is found out from
experiment.
The emf of the cell, Ecell, is given by, When the quinhydrone is combined with calomel electrode, oxidation takes place at the calobe
the cell may
mel electrode and reduction at the quinhydrone electrode. Hence, by convention,
Ecell ERHS - ELHS.
The left-hand electrode is the standard hydrogen written as,
electrode and its emf is zero. Thus,
Ecell =ERHS - EL.HS -0.0591 pH Hg|Hg,Ch(s)| KCl(saturated) ||H'(unknown conc.)| QlQH,|Pt
The emf of this cell is given by,
or
pH = -Ecel potential of the LHS electrode]
0.0591 E- (Electrode potential of RHS electrode] -[Electrode
-0.0591 pH
2. Using the Quinhydrone Electrode = (0.6996 -0.0591 pH) - 0.2415 = 0,4581
amounts of quinone (CçH,0,) and hydroquinone Quinhydrone is a compound which contains equimolar 0.4581 E
trode is based upon the fact that quinone is (CçH,0,). The working of the quinhydrone elec pH 0.0591
reduced to hydroquinone ions. cell is measured potentiometrically, from which the pH of the solution can
1.e. The emf (E) of the
CoH,0, + 2e CaH,03 be calculated.
Quinone Hydroquinone ion solutions of
The hydroquinone ions combine
reversibly with the H" ions to form hydroquinone. 3. Using Glass Electrode If two
are present on the two sides of the
CGH,0, +2H' =CoH,0, different pH
established across the
The overall reaction is glass surface, a potential is depends upon
glass membráne whose magnitude
Calomel
C;H,0, +2H +2e CH,0, two solutions. For clectrode

Quinone Calomcl the difference in the pH of the on one sideof P

Hydroquinone clectrode of a glass, if

a particular variety solution of fixed pH value is
If quinone is represented by Q then
hydroquinone the glass surface, a across the glass Hg
can be represented by QH,. Therefore, the above placed, the potential developed
upon the pH of the Hg,Cl;
reaction may be written as membrane will depend only the other
Hg placed in contact with Saturated
other solution, thus Pt
)+ 2H+2e QH, surface. The assembly KCT
Hg, Cl, side of the glass 18.28) IM HCI Sintered
glass clectrode (Fig.
Platinum
If a platinum wire is dipped into a solution con clectrode obtained is called glass disc
taining H ions and a pinch of a quinhydrone (i.e. Saturated variety of glass (usually Solution of
KCI Atube of specialwhich has low melting point unknown pH
Q+QH) is added, it acts as a reversible electrode. soda glass)is taken standard
Sintered Solution of
Fig. 18.28 A glass electrode coupled with
(Fig. 18.27). The reaction, as writen above, is a re glass disc unknown pH
andhioh electrical conductivity. At tne cnd Ofthin calomel electrode
glass bulb having a very
saturated with
duction reaction. Applying the Nernst equation, the quinhydrone this tube is blown a
electrode potential of the above electrode is given by ig. 18.27 Quinhydrone electrode coupled wiln
standard calomel electrode
 tion, dationCalomel
ductionelectrodeUsing 4. are
vantages
Advantages concentration as
E-The (d) (c) (b) (a) as calomel inside
glass
is
where,
the EG a
is electrode wall. 708
the Combining (18.78),
FromEq. where emfThe of deternmined
To platinum
emfof
|Electrode takes solutions.theThey They
agents. They Theymentioned
0.2415- cell at determine This
is of electrode
coupled
P.may the place can are are are glass Eç
this calomel of potential wire is
(-0.059l H,(1 or this
fconstant of is this
a filled
potential cell be at be not not easybelow: Using
the bulb. the
poisoned
usedaffected electrodes
result a KCl is
atm)|written Electrode
the When a easily. to as
solution electrode cell
is electrode. with use. usualvalue of with
dipped
Glass
Tosolution the Chemistry
Physical
given hydrogen for Glass will a
pH) H(unknown a with depending
determine
of as calomel very by electrode
be and of of glasssolution
into
RHS= by oxidising over
Electrodes Eq. potential pH
0.2415 used. the known
the Hence,
elcctrode small of electrode, the
electrode|
pH other (18.77),
Ec- emf an the upon EG of
relation electrode, pH Experimental | solution,constant
+ conc.) quantities or of unknown of pH value = =
by electrodes E naturetheof
E-0.24150.0591 hydrogen reducing = we Eç E-
the Eç-EG the value. Eg-0.059 as Eç+0.0591
0.0591 conven and The E;-0.0591
E-
Eç+ E
symbol get resulting of prepared the pH.
0.0591 = calomel
|Electrode re oxi of ad Ec- solution, E,
pH other To
solution for
| Fig.
solution E pH1 make
Test electrode a og
labove, end
KCl Pt H, pH cell particular glass glassandthe
18.29 the [H'] at ofthe
potential(saturated) | is
Calomel
measured. glass is
which electrical
hydrogen
electrode
unknown A
whose electrode 25°Cgiven
calomel
of electrode the by is
LHS Hg,Cl, | The electrode, pH
attached
value of the contact
electrode
electrode] cell 1s equation
(s) depends combined solutionthe to
with
|Hg may the a
glass
coupled Sintered
disc SaturatedKCIHg,Cl, Hg terminal this
represented value
...(18.79) upon
...(18,78) ...(18.77) sole:
with
taken
of
win the the F

Solution:
(Electrode Exampleculated
18.29).
(Fig.
But Ecell f Thus,
one In 2. 1. the
3. The =
18.29
of all Pt, potential, Pt,
by=[Electrode emnf measuring
0.0591.os
What The Oxidation Determine the Ecalomel potential 21
thetypes H,(1 emf The
emf H,(1 Nernst of
this Consider
solutions of is Pt, of emf
the atm) the
- the
of atm)|H" determine
the EH,H, cell
titrations (g)(1 the potential
H,pH equation, potential of Pi/Hz(g. of
pH|solution cell the the is emf
is of cell (a of the
givencalomel 0.50 (E)
POTENTIOMETRIC
TITRATIONS thate m)]H" of =)|| the the -0.0591 or cell
taken like
pH of we volt atm) l of
solution PROBLEMS
normal Normalsolution unknown PRACTICEFOR RHS cell the
in of
En',H, have electrode at|H"
acid-base
the (a=?)|H(a the cell
around calomel =celpH pH En, electrode] given is 25°C. (x
titration given
calomel 25°CpH|atHg,Clh(s) = = H, potentiometrically,
molar)
Ealomel0.0591 = what
is
Ecalomel by, 0.281
titrations, the 0.6Ecel346l V solution, 0.0591
=0.01)|H,(1electrode=-0.2800 electrode from - would ||
flask left-hand - [Electrode KCl
the calomel Pell log - volt
andredox KCI(s)|Hg [H] Ecel at be(0.1 Electrochemistry-ll
followingelectrode 25°C.) the M)
the electrode? atm), = potential pH the
titrations, 2.303RT pH-0.0591 |Hg;CI;/Hg pH
other V of
Pt data: potential0.366 is the of
The at 0.281
0.50 or the
solution 25°C 0.0591 pH x
at- of
volt. LHS molar solution
precipitation value 25°C SCE [as
is clectrode]
is of0.861 Ignoring pH acid
= being
added 2.303 0,0591 -3.71 cancalbe
volt [H'|lo]g solution?
2.098]
[Ans.+0.242 the
titrations,
to 12.[Ans.
568] RTIF 709
[Ans. junction
it
from at volt.
25°C 6.0]
the etc..
 indicates against obtained.(Frome the the
thresponding volume amounts er
cell (Fig. A drogen
in The HCl potentiometric1.under:
titrations.
Titrations
carriedoutchanging
steepness end the calomel the keepelectrode up burette. ion 710
Fig. solutions amounts burette it. Acid-Base
is Each
noted 18.30). This acid acid end titration in in
18.32 e
thpoint. on th e
the of (say electrode type point the
volume solution is electrode, As
end (say electrode orchanging.titration
reversible
Vol. titration
toNaOH after containing
Titration
weak
base to show
In ofare the 0.l NaOH of is a
of this Titrations flask,
alkali
point such the very be titration reached result,
equivalence added. each ml l
(quinhydrone
curve of curve curve, or ml
solution titrated
is a the flask,
added
(Fig. the case, adilute, is If flask
of
addition. even or the then taken
A
using sudden emf (or the with
or beaker) thChemistry
e Physical
a alkali is 0.5 NaOH is its
weak 18.32). less e
thcurve against
in discussed the electrode,
of respectkeeps
concentration
we or less) is
mlcombined Suppose this change electrode
Equivalence point
volume reaction the
acid point plot weak
used. marked added or a on
ofThe near solution at beaker principle
glass NaOH cell is to
and can the emf a coupled changing.
the thetime) to a
separately in thus this
The acids of is will potential
value
slope and NaOH
be type isend the with solution. orandsolution complete.
are ion
maximum is keep set of
Fig. or shown then
itfound. and
beaker hydrogen
fitted the a called when with up is some
of bases is point. will If
18.33 hy of as on set an
Fe+ Fe
electrodeStandard
calomel difficult
the solution plotted then calomel a in
I0ns
However, in The first over Stirrer
Apparatus
K,Cr,07
with curve
of are Fig. in gas) Fig.
voltmeter
Electronic
the involved, used against emf very electrode. inthe 18.30
to th e is
18.31
curveAEIAVlocate when of beaker
small set
for cor larg Potentiometric
potentiometric is the the up
sol
NaOH
Fig.
18.31 Plot atm
H
at
vol solution Acid bridge
Salt potentiometer
Vacuum-tube
of titration
titration K,Cr,0,
solution of.
emfof
MagnetiC electrode
Platinum solution
added
Volume N
stirrer

of the of
added. I
Fe cell HCl
Equivalence
of vs. point vs
Calomel
electrode
NaOH NaOH

thensolution
NaCl iswith(Fig.lution is 3. solution bethe ing similartotionplatinum Titrations
(Fig.solution. Redox 2.
it centration
tration,solution, tion
ions till electrode Precipitation determined
to procedure Similarly,
a
clectrode be of
suppresses the We Fig. solution determined
solution, 18.35). the is l8.33).
results
are KCI Calomel standard K;Cr;0;
end get titrated
taken in wire The
18.35 calomel thatof
decreases Further still fixed place A
of
point, depends
into similar a The in remains can Fe is
the present the over against as solution solution, burette ferrous
against
Ag Potentiometric aselectrode. a
Titrations in ofacid-base inserted
the emf electrode, beaker
ionisation Electronic
in the
K,Cr,0,
very addition when ions upon voltmeter
whichprecipitation curve silver the ofthe case the containingsulphate Suppose
solution a
and NaCl of be the
into
slightly. all thein the case beaker
the estimated
same. KMnO4. titrations.
of the asnitrate
titration A
thussolution. of
solution emf
concentration
of are solution cell Suppose
a it.
NaCl Ag in of burette and formed,silver Fe' The
of solution The
AgClobtained acid-base solution of acid-base is K,CrO,.
t he
ions of noted. after potentiometrically
cquivalence We
NaCl AgCl solution
due Ag sodium containing wire The titration. K,Cr;0,
a (Fig. cellclectrode
thus solution shall along
of due are ions electrode
AgNO; The every isnitrate
silver
is so solution is of
= of chloride solutionNaCI Silver titrations combined then
inserted 18.34). noted.
common-ion has
precipitated. keeps titration take ferrous
with
Na' Ag" to toAg' end
addition thus
the ofAgNO; point
+ + nothe on
form ions point KMnO4
Rest The formed is dilute
(Fig. into fixed sulphate
CI C1 effect decreasing because
ionisation NaCT will
AgCl in is of it of us end Electrochemistry-Ill
effect on At the Fig. Cell Potenti 18.36). point over H,SO, is
Fig. combined
the this (which solution. the 18.36 is
and of with 18.34 the to
is is
Agstage, electrode Vol thenbeaker taken titrated
againstbe
as the for
the is Potentiometric of Vol
iaon AgCl sparingly
a The NaCI AgNO, of
Potentiometric of determined with
result
concentration very
addition FeK,Cr;0, and into
potential and added ions calomel
the
thatsmall addition after a
AgNO3 Equivalence with added
has soluble).
of point Equivalence beaker
titration pont in
every
Ag' amount of titration
K,Cr,07
gone NaCl of clectrode
a KCr;0;
ion manner
except The NaCl the curve add1 and 711
concen intosolution curve
of silver a
that the Ag con solu
 Corrosion
attack boundaries. material,sclective
4.ticular orwherecorrosion
3.liqujds 2.
Exfoliation only
Interqranular Erosion chemical corrosion
form thein
cally
corrosion
WhenCorrosion Types
1. ofclude Rust
carbonates, Surfuce
etc.,is The
has the Galvanic Rusting 712
corrodingslightly
character and decrease connected (b) (a)
18.30
which
a which material, is electrochemical series two tarnishing is process Advantages
rather Corrosion
the the action is hydrated required.
colour, is
change.ForThese
and of
shows
attacked. mechanical
removal called different of the acid-base
laminated
starts and medium. in Corrosioncan
of
Corrosion and ion metal of titrations
especially and the
of of
Selectiveon attacking galvanic be ferric is slow
clectrode soluble
Zn volume exposed metals silver, corrosion.
called potentiometric
clean a This This of It Less
attackedanodenoble
is dry the
resulting titration,
’Zn? oxide, CoRROSION eating useful
veryare are Chemistry
appearance the
rubbing is or most
Physical
sensitive caused This green
may type only protective corrosion corrosion.of (e.g.
Leaching undergoes to wet,
surface potential Intergranular 2e+ a away
metal an isFe,O3xH,0.
coating common into priorno
be of at action by Fig. baad zinc the
electrolyte,chemical titrations:
due
corrosion grain to the 18.38 n the of
and and productstakes
and most in
more corrosion surface Electronic
current corrosion. In on the
to combined of + + formation
example knowledge case
Exfoliation
whole boundaries, Positiveion the
spreads the corrosion solids Volatile current Zn2* Zn place copper) or copper,Other netal
corrosion, common of
precipitationanodic is film. are electrochemical. the
layers due attack, over as due to coloured
effect oxide formed Suchmetal are bronze,
examples of of of
below to a corrosion. the
than but occurs a layer result form compounds
of and the exists type
ahigherelectr1 the solutions
it. leaving metal of (Fig. uni pH
materialselective that
of fact turbulent of etc. in
If of of attack range
certain of andalong surface. protected Morc
cathodenoble
is 18.38).
differs that the Fig. such where
in
are 15 the corrosivegrain
18.37 of
leaching grain flow
from compounds graingrain The as
atmospheric
gases ch
whiinternal
orroded.
boundaries
interiors of the has
humans.Corrosion oxtdes,
boundaries major the
pitling IS centre liquid gases, biggest
proved indicators l
indicator
The a cause sulphides
in at inpossesses vapour
subsurface enemies to
attack that the the untouc and be of
conta 1OT fail.
Oy onemetals On
the grain P and the
o of of

undergroundsibleother Soil 5. row as

from usually
in
9. tion oftive 8. and Corrosion.
products, biological
7. result,
localtains ganisms with 6. the nonsusceptible
takes
and cessformation ment Service.
10.Corrosion. stresses anodic
residual Soil (c) (c) (a) italuminum
Thisalloys. Selective
In cavities Pitting Crevice Microbiological
Bacteria, fungi,
algae, percentage paths, yields
copper-zinc
Stress-corrosion lack or Content for
hence, of Waterline are such ofpinholes, filmn concentration Content Acidity Corrosion typc recognised
place and without is corrosion soil
cold and on of
crack 1orming a
oxygen necessary. aroundCorrosion Corrosion
0, called corrosion ofporous leaching alloys
acts in
of Forcases.
the larger
oxvgen working melal a of of of of corrOSion
a stress in in oxygen organic
electrolytes the alloys
as is Corrosion
steel pits microbiological particles iS structures, from
the soil Corrosion anodic
corrosive cathodic which thepaint
mucha at gradients Corrosion purely metal(parting) and
cathodic The
corrosion metal Cracking and species include Is can a
concentration tank and specificPitting concentration and matter flaky
coatings, It diatoms, ctc.,are involves
areas with the
less is arclectrochemical
e of be
Corrosive environmental cavities the
quenching, a of various by most avoided
containingWaterline under areas. metal twhich
he poor
is or
there to
points.
corrosion the in local dissolved classed Corrosion soils with the
area. in following: in common blistered
occur, Stress etc. corrosion. removal
the is crevice. cells sizes.
arc rcspect mechanical
is a
(Fig. cells. agents stress relatively It corrosion by
It as cmbedded very localiscd
watercorrosion welding,corrosion metal. is is is heat
surface.
l3.39). presence a ar esalts,
capable aerobic caused in
It arebecomesS stresses localised usually usually The Microorganisms content
(d) (b) important to example. of
developed character. present(f) Moisture the reatment
one
along has highly Piting
unattached and gases, clectrochermical properties.
thermal nicroorganisms of or by Physical in more This
T
generally of on is due attributed is the This of
he aresults more anaerobic
forming the th e
area line tensile
specific the duecorrosionaccelerated acids, in and tvpe
to usually on The cathodic
soil. case typeElectrochemistry-ll
metal the properties elements
anodic to and the metabolic This proper of
above just been from stress treatment the breakdown etc., texture The of ofcorrosion
and tomicroorganisms.
caused surfacerespectively.
bencath that gives this various watercorrosion,
arcas corrosion
can
thobserved
e differential combined attack, changes on can alloying in
selective. and and or
cause corrosion activity of of be an
waterline tends rise by the develop
the th e mains, at
a due leading factors the remedied alloy. is
level a specific resulting
to of indirt surface occurring is known
cracking soil soil highly
that to to effect the cracking acidity of electric
cables and metal
aeration results deposits, to Such various in is De-zincification
increase applied that
maximum
is of corrosive formation microbiological of an
deterrnined by to
highlywater. of in sur1ace. undesirable take
the of in ions
environment a are alongnar the
leading
resultingstatic in the film
loads formationthe the corrosion and micro-or respon use place 713
because the
oxygenated corrosion of crevice of
environ rate during tensile smal!forma protec asmain by
to from a
the of
ac
 3. rust:of ofthe the The
writtenas 2. electrochemical
are tively
These The Thus,
H,Oreaction, In extentasThe 1. Theformation
example Waterline
18.31 attached 714
Multiplying This surface
of
dissolve The theory
electrons contact following Consequently, free
H-atoms present carbonic
CO,
the acts water
in of of 18.39
Fig.
form Waterline Fe*+
iron sites
with as water, the CO, of of
corrosion corrosionto anodic
Eq. rusting the 2 Poorly
rust
onlost
is H,
an0+
CO, metal
vapours steps acidity.
(18.81) react converted the where the acid and cells sides it
OH Fe part
’
by electrolyte i.e. on is oxygenated
’ Fe*
t4eO,4H
t ELECTROCHEMICAL
are is
with surface iron dissolved and is O, on onthe ofcan Fe corroded
the carbonic of is not (OH)2 + Chemistry
Physical
by Fe>Fe" covered involved the iron. also 2e
oxygen are water from the basis be ships. corroded.
and 4 of intoabove solution H,CO, > surface surface This caused corrosion
CO, explained
+O,>2H,0 i 4H thetakenferrous
H,CO, ionise acid with the
adding H+e
to>H
metal. up reaction in of
form and H,0 (H,CO,). air. the oftheory the
marine
shipsHowever,
in
by of the of occurs (proteced)
(Fe) oxygen, + = to Thus, formation
the the
formation
catoxygenated
hodiHiparc tghly
2H,0 to water. Thus, the 2e the solution explains by
Eq. takes H2HSmall cell. metal metal. taking just
H
ions. (Eoxid the
+ little
underneath
(Eed (18.82), Hions place iron OH +
ions =0.44 CO THEORY
=1.23 produced undergoes andcorrosion
the are act
the
V)
complete converted as V)
anodes. Fig. accelerated takesmeniscus
by oxidation
the 18.40 Anode
OF
Corrosion
cell conduction)
(electron conduction)
(ionic
Current
flow
place 4H
dissociation
into CORROSION and H,0
reduction As Current
flow +
Corrosion by the O, ’
H-atoms. a as when
resultfollows: Cathode marine water 4e’ + H"
the +
reaction OH
of cell leot 2H,0
H3of plants water
the
...(18.80)
. (18.83) . ma(1y 8.82) . .(18.81) auu is
D whio rel,.

placed
(c) in
Pure (e) (d) faster vacuum. encecorroded.
(b) ily Factors
(a) for
It 4.
PresenceStrainsPresence Presence Reactivity Thefurther may be
metals of Ferric current
oxide The there ItAdding The The
in rusting may
saline gases Responsible ferrous is sites
dissolved
do in rusting.noted oxide be
a in equations
of of likeofAir of
phenomenon faster the where
not Metals water mentioned
Impurities Electrolyte the then ions
SO, It, that miniature oxygen
corrode. and (FezO3
xH,0) formed
and the
than Metal
More for thus, the H,0+4e’4OHO,+ O;+ undergoes
Corrosion and Rust greater
(18.80)above
Moisture rust 4H"+ here 2Fe may
in CO> Corrosion mayreduces
pure 4Fe+ react cell reactions
+and
Presence Electrolytes does or 4e corrosion that Ot take
in
be ’ Cathode hydration and,
takes water. O:g Fe,0,
xH,0 t with
if
(18.83),
active
represented the not Fig.
air Air 2H,0 O, up
O, hence,water 4H"
life stick 18.41 the takeelectrons
+
ofplace enhance and
to
+ by
impurities 4H,0dissolved the contains -> theplace H,0
increase moisture metals of to form enhances
anCorrosion Iron overall +
rapidly sea 2Fe directly
the diagrammaticallyarticle. the
having rust, act 4e
surface. > side.
the process xH,0 >
HydratedFe,O, oxygen
2Fe,0, the some reaction + as40H >
in at accelerate of 2H,0,cathodes. to
Electrochemistry-lll
rate iron Anode process
metals bends, high Fe dissolved form
of It ’ ferric or
of peelsoff Fe?*
droplet
Water +oxygen Ecll of
oxidation 8H the OH
enhance
scratchescorrosion.corrosion. the +
oxide of
2e miniature ions
corrosion (rust)
(aq) corrosion.salts, 1.67 =
shown exposing from
potential it V as
the
and Iron tollows:
For the helps cell
in This
does
chances cutsexample,phenomenon. Fig. air will
fresh
values to
explains in
in not 18.41. form the be
of the iron
rust flow
corrosion. iron are surface ferric 715
metal. why
when Pres read oI
rusts
 d 4 a

a
1

magnesium, through as
pears Electrical
ironnectedto 4.
the (d) (c) of
3. tective corrosion.
further
(b) (a) By the The 2. carbonate,
fromnised torms inThemetalImetal it
active due
object Using evenconsumed
The allow The point dioxide. alkaline contact wil Preterence With tingthus,which plies 1. Somethe of 716
cuts by The tExternal
he By automobile iron layer Sacrificial 18.32
a
oxidationthe to electroplating film a is
often protect the toxidised.
he preventscovering
zinc acts more off iron iron
applying Anti-rust protective is
metal
air iron layermetal
of sheets zinc
ZnCO;. with of nearly passage
or the surface surface and can medium used into to more
and as iron zinc and
active
Cathodic supply develops surface Coating moisture, metlhods
cathode
is moisture be a engines to for
the ions iron The theProtection
active the
aluminium
present. prevented. film phosphate Zn(OH)), on theexposed io ns ofand more
Solutions
prevents lustreinvisible
their
lose protecting iron iron
with is is the
process
buttime,
of metal oxygen ofcoated coatedcracks.coated is of from converts for
and
Protection
its tin, to oil and oxvgen surface
surface
so active form surface (electropositive) Chemi
Physicsaltry
the on long the
which
The metal (greater zinc, with react with It orradiators.
availability which thin preventMETHODS
Sacrificial ion
and with keepsgrease isiron rusting. more
as itself metallosing
metalions. more noncorroding with a
the These
layer and called of with
water
etc., phosphate
a iron. causes of with
iron it
are oxidation point the on but carbon iron, It active loses
is intoelectrons a of
used active
The The or iron of
to galvanisation. a todoespresent layer OF
called to bysurface. iron the These ofare on more than
protection corrosion
the which phosphate
hydrogen alkaline
and protect the basic react. not metal clectrons
ionic
for iron iron dipping
give surface
surface diox1de,
coming and ron. of
sacrificial metal
potential) metals solutions galva
object iron zinc active allowthere, state. metal PREVENTION
protectingobject prevents
a The gets in are
acts tough it n get Tl.
surface. the
to iron such protected theof ions. Flg. explaincd
anodes. remains lol as
either are
be adherent
as the iron 18.42
iron anode. article Phosphate
used
protected nickel, action form tools
directly below: OF
objects to phosphorus
sulphur/magnesium. used
iron
the
processing
ironsmiths skill
corrosion
It The
protected The the
in insoluble
moisture, and alkaline
solutions
preventchromate speaks
chromium,
emolten of Delhi CORROSION
deposits achieved
from anode from
or air, machinery,
rusting
form as moisture, rusting of in offor iron
film oxygen iron.
rusting and e
aluminu an contans
pillarthe
the bythe thpillar
metal. which insoluble If last
the of isextraction is
ancient high has
etc.,
graduallycorrosioan believed
This and rusting iron free 1600
IS
out ot wire. is doco withsto
caroo Indiat level years
disap Tie cot agan parts pro from tha ang
ot e

after
some OverallSolution:
time. reaction
two Solution:Example
electrode, anode plete
At AtExample nals, the
Example electrode
cells:Solution:
Example cathode wireCathodic
(b) (a) electrode reversible storage
as
Zn(s)Cd(s)/ concentration
24 keeps 23 illustrated
22protection
25 The At tanks,
|Zr|Fe,Ca||H potentials on the
Why Taking
cellWrite
Write
voltmeter etc.
increasing zinc given
in is Fig.
Mg Magnesium
(anode)
|H(g)|Pt down cannot the
down Pieces reaction
Anode
of
become electrode, below: Fig. often ’
Fe/P! 18.43
Cu" example Pi, the 18.43. Mg Mg
the draws employed of
voltmeter a while Hz(g) H;(g)reactions
cellcurrent equal. ion 2AgCl(s) magnesium Electrical +
2e
concentration | Electrode
reaction thatkeeps of
2AgCl(s)
+ HCl(aq)
Hence, of surfacc
Earth
be Daniel taking protection
in
from +
Hz(g)
used copper on 2e reactions are the
and the decreasing.
Eçell cell, || O, O,
of ’
’ ’KCl(aq), place protection
buried (cathode)
pipe
Iron
to of + +
expression cell, electrode underground 2H,0 4H"
measure
becomes Znexplain 2Ags) Ag(s) 2H
e
at aralong + Electrochemistry-IlII
thereby (aq) the + 4e
keeps +AgCl(s) given of 4e
As ’ Soil
why ’
+ 2CI + separate
for the equalkeeps a 2HCI(aq) the iron 2H,0
2e alongside iron 40H
changing
the emfof result, on the (aq) Ag. pipelinepipes
on
increasing
to pipes
emf decreasing emfof electrodes
zero.electrode
a buried
of cell?
the the inand
the the
following emf while connected in
til cell andfigure. moist
of potential
the ultimately at drops in
the the soil,
to 717
reversible cell. of
copper to com it ca
zero by
the zinc