Electrocheemistry Chapter 3

BASIC
CONCEPTS
. Electrochemistry:
during a
Electrochemistry is the study of production of clectricity from the energy releascd
spontaneous chemical reaction and the use of electrical energy to bring about
chemical transformations. non-spontaneous
Ohm's Law: It states that the potential difference () across the
conductor is directly proportional to the
current () flowing through it. Mathematically.
Voc| or V= IR
where R is a constant called resistance of the conductor. Ohm's law is obeyed by both the metallic, as
well
as electrolytic conductors.
3. Resistance (R): It is the property of asubstance by which it obstructs the flow of clectric current through
it. The electrical resistance (R) of any object is directly proportional to is length () and inversely
proportional to its area of crOss-section (A).
Thus, R o« R=pA
A
where p (rho) is a constant of proportionality called specific resistance or resistivity.

p=R?
If l=lcm and A=lcm then R=p.
a conductor of 1 cm length with area of
Thus, resistivity may be defined as the resistance offered by
of the conductor.
cross-section equal to 1cm, i.e., it is the resistance of I cm'
cm
Units: p= R = ohm: = ohm cm
cm
Its SI unit is ohm metre (2 m).
case with which the electric
4. Conductance (G): It is the
reciprocal of resistance and may be defined as the
current flows through a conductor.
G=
R
Its SI unit is Siemen (S).
1S ohm (mho)
reciprocal of resistivity (p).
5. Conductivity (K): It is the
K=xeGx
pR A A

If l=lcm and A =lcm, then K=G. solution ofIcm

may be defined as the conductance of a
Hence, conductivityof an electrolytic solution
length with area of cross-section equal to l cm.
cm of the solution of an electrolyte.
Alternatively, it may be defined as the conductance of l
96 | Xam idea Chemistry-Xi.

Units: K= = ohm cm (S cm)

ohm cm

The Sl unit of conductivity is S m.

6. Factors Affecting Metallic Conductance
Electrical conductance through metal is called metallic or electronic
movement of electrons. It depends on: conductance and is due to
() The nature and structure of metal. he
(ii) The number of valence electrons per atom.
(ii) Temperature (it decreases with increase in
7. Factors Affecting temperature).
Electrolytic Conductance
Electrolyte: electrolyte is a
An
clectricity in dissolved or moltensubstance
that dissociates in solution to produce ions and
Examples: HCI, NaOH, KCI (Strong
state. hence conducts
CH, C OOH, electrolytes).
The conductance of NH,OH (Weak electrolytes).
The following factors electricity by ions present in the solutions is
called
a solution electrolytic
govern the flow of
electricity or ionic
(i) Nature of
electrolyte or interionic through of electrolyte. conductance
the freedom of
movement of ions andattractions: Lesser the solute-solute
(ü) Solvation of ons:
Larger the
higher will be the
conductance. interactions, greater will be
solvation and lower will be the magnitude solute-solvent
of
(üi) The nature of
solvent and
electrical conductance. interactions, greater is the extent of
viscosity its
and more will be the viscosity: Larger the
the electrical conductance. resistance offered by the solvent-solvent
solvent to flow interactions, larger will be the
(iv) of ions and
Temperature:
solvent-solvent
As the
temperature of
hence lesser will be
8
Difference between interactions decrease, electrolytic
which results in thesolution rises
S.No.
Metallic and Electrolytic solute-solute,
increase of electrolytic solute-solvent and
(i)
Metallic Conductance Conductance conductance.
Movement of elecrons is
responsible for conduction.
Movement ofElectrolytic Conductance
(ii
Does not involve
transfer of matter. ions is
(iii)
Decreases
vibrating with increase in Matter moves in the responsible for
form of ions. conduction.
electrons. which produce temperature as
kernels start
hinderance the flow of inIncreases with increase in
in
interionic attraction or temperature
increase in due to decrease
9.
Measurement Conductance: As we know, K=
The value of K
of
dissociation.
value of the could be known, if we R A

electrodes is resistance of the measure l, A and R. The

solution Conductcellivity
(Fig. 3.1). determined by using between two parallel
I
R,consists
of Wheatstone' bridge method
and the two fixed resistance R3 and R4, a
R,
-Detector
The bridge conductivity cell having the
detector.
is
balanced when no
Under thesc conditions, current passes unknownvariable resistance
resistance R.
RËR through the
R2 R4 R2 RR4 Fig. 3.1:
R3
Knowing the values of R,, R¡ and Ra Wheatstone Bridge
gives the the
conductance of the solution. resistance of the
solution, R, is
determined. The
arnidea reciprocal of R,
 Llectrocherm1sty 97
10.
Molar
Conductivity (^) : may be
defined as the conducting power of all the ions produced by
Assolving one gram mole of an clectrolyte placed between two laree clectrodes at one centimetre apart.
Mathematically,
KXI000
A,, =KxV, A,, =

where. V is the volume of solution in cm' containing | oram

concentration. mole of electrolyte and c is the molar
KX1000 S cm-!
Units: An
mol cmn-3
= ohm cm mol' or S cm² mol-!
1 Variation of Conductivity and Molar Conductivity with
Concentration:
Conductivity decreases with the decrease in concentration, this is because the number of ions per unit
volume that carry the current in the solution decreases on dilution.
Molar conductivity (^m=KX) increases with the decrease in concentration or increase in dilution. This
is because the total volume V of solution containing one mole of clectrolyte increases with increase in
dilution. It has been found that the decrease in Kon dilution of a solution is more than compensated by
increase in its volume

Graphical representation of the variation of A,, vs ve

400
mol-1)
cm²
Am(S CH,COOH (Weak electrolyte)

2004

KCI(Strongelectrolyte)

0 0.2 0.4
12|(mol/LJ1/2
Fig. 3.2: Am VS Vc for weak and strong electrolytes in aqueous solutions

concentration approaches
Limiting Moiar Conductivity (A, ):The value of molar conductivity when the
conductivity at infinite dilution.
zero is known as limiting molar conductivity or molar
of strong electrolyte by
It is possible to determine the molar conductivity at infinite dilution (A) in case
molar conductivity of weak
extrapolation of curve of A,m VS Vc (Fig. 3.2). On contrary, the value of
curve as the curve becomes
electrolyte at infinite dilution cannot be determined by extrapolation of the
zero.
almost parallel to y-axis when concentration approaches to
developed by Debye,
The mathematical relationship between Am and A, for strong electrolyte was
as
Huckel and Onsager. In simplified form the equation can be given

nature of
where A, is the molar conductivity at infinite dilution and b is a constant which depends on the
the solvent and temperature.

nidea
 12. Kohlrausch's Law:ltstaltes that thclmiting molar conduetivity ofan electrolyte can be represenled as t
clectrolvte.
contributions of the amion amd cation of the
sum of the individual
In general, if an clectrolte on dissociation gives v, cations and V anions then its liniting ma

conductivity is given by

calionS and anions, respectivelv

Here, and 2 re the limiting molar conductivities of
Applications of Koblrausch's Law:
infinite dilution: For
() Calculation of nolar conductivities of weak clectrolyte at example,
conductivity of acetic acid (weak acid) at infinite dilution can be obtained from the molar
molar conductivities at infinite dilution of strong clectrolytes like HCI, CH,COONa and NaC of
illustrated below.
knowledge
^mCH, CO0O) = CHcoo

CH,coo

^mCH, COOW=mCH C0ON t^m iC) -ANC)

(ii) Deternination of degree of dissociation of weak
eleetrolytes:
Degree of dissociation (a) =

(iüi) Determination of dissociation constant (K) of weak

electrolytes:
K=

also

(iv) I-AA AA-N)

Determination of solubility of sparingly soluble salts:
Kx\000 KxI000
molarity solubility Or, Solubility = KxI000
13. Electrochemical Cells:
Oita clectrochemical cell is a device inA
which chcmical energy of Voltmeter
reaction is converted into theclectrical
redox
ótccLsic al ¬ energy. The redox reaction is carricd
out in un indircet anner and the Anode
ye
decrease free cnergy during Salt bridge
chemical reaction appears as clectrical Cathode
+ve
energy.
The simplest
clectrochemical
Daniel ceil or Galvanic cell is Znso,
cell in which a (1M)
zine rod is placed in a
ions (say, ZnSO) in thesolution
of Zn2+
left
and a bar of coppcr metal is container Cu2 CuSOA
in a solution of Cu ions immersed
(1M)
(say. CI
in the right container. The (woCuSO.) Zne*
metzals
which act as electrodes are
connected Zn» Zr +2e
Aatnidea Fig. 3.3: A Cu'+2e
simple voltaic ,Cu
cel
by a metallic wire through a voltmeter. The two solutions are joined by an inverted U-tube contain1nz
semi-solid paste of cither KCI, KNO, or NH,CI in gelatin or agar-agar jelly. This arrangernent of U-tube is
called sal bridge (Fig. 3.3).

The overall cell reaction,

Zn(s)+ Cu"(aq) Zn(uq) +Cus)
can be split intotwo half cells. The deflection in th¹ voltmetcr indicates thc flow of current through the
external circuit. The conventional current flows through the outer circuit from copper metal to Zinc metal.,
which implies flow of clectrons from zinc to copper bar.
(a) At zinc electrode the metal undergoes oxidation and releases two electrons.
Zn(s
)’Zn"(aq)+ 2e (oxidation) ’5nds
Because oxidation is taking place, the electrode behaves as anode.
These clectrons travel through wire and reach the copper metal.
EEectrnction reduche pls:
Cu 2+ (aq) + 2e ’ Culs) (reduction)
(b)
The above reaction occurs at the copper electrode. Electronation takes place which is a reduction
->rodurtion
process and that Is why it acts as cathode.
As a result of the two half cell reactions, zinc metal dissolves in anode solution to form Zn ions.
while the Cu* ions are discharged at the cathode, by accepting two electrons and are deposited at
cathode. The electrical neutrality is maintained in two half cells using a salt bridge. The anions of the
chamber.
nert electrolyte in the salt bridge migrate to the anodic chamber and cations to the cathodic
rod loses weight. As a
As a result, as the reaction progresses, copper bar gains weight whereas zinc jons in solution are
consequence, the cell continues to function till either zinc metal or copper
consumcd fully.
and cathode becomes positive
Since electrons are released at anode, it acquires negative polarityobservation is against the usual
because it needs electrons for the eduction of +ve ions. This
electrolytic cell where anode
? is +ve and cathode is -ve.] novwa!
Salt Bridge and Its Functions
Acommonly used form of salt bridge consists of a
glass U-tube containing semi-solid paste of either
KCI, KNO, or NH,CI in gelatin or agar-agar jelly.
The electrolytes that are often used in salt bridge
are called inert electrolytes which are supposed:
anodic or cathodic chamber.
of the solutions present in
() not to interact chemically with either
(ii) not to interfere with overall cell reaction. same.
those electrolytes can be used as a salt bridge in which mobility of ions is almost the
(iii) only
122 Example, KCI, K, SO4,etc.
important functions:
A salt bridge carries out two
Thus, the circuit is completed.
(a) It allows only flow of ions through it.
(D It also maintains the electrical neutrality. notations are
Representation of an Electrochemical Cell: The following conventions or
Diagram or Daniel cell is
14. Cell
writing the cell diagram in accordance with IUPAC recommendations: The
applied for
represented as follows:
Zn(s)|Zn(C,)||Cu*C; )| Culs)
hand side.
hand side while cathode half cell on right
(a) Angde half cellis writen on the lef aqueous solution of its own ions.
metal from
(b) A single vertical line separates the
Zn(s)|Zn (aq); Cu2* (aq) | Cu(s)
Anodic chamber Cathodic chamber
passage of ions through it but prevents the
(c) Adouble vertical line represents salt bridge which allows the
mixing of two solutions.
of the corresponding ion.
(d) The molar concentration (C) is placed in brackets after the formula

Xaidea
 idea Chemisty-XIl
right of the cell. For example,
of the cellis writenontheextreme
(e) The value of EMF
Zuts)|Zn(IMI|Cu*(IM)|Cu EMF=+1.lV
() lf aninertelectrode like platinum is involvedin the construction of the cell, it may be witen alz,

bracket, say for example, when a zinc anode is connected to

the working clectrode in
electrode.
Zns)| Zn(C)J|H(C)|H, (P)
of Daniel Cell:
15. Reversibility
(a) Whenexternal voltageislessthan L.10 V, electrons flowfrom Zn to Cu but current flows 1from Cu
ie, in opposite direction. Zinc dissolves at anode andicopper deposits at cathode (see Fig. 34al)
e
(b) Whenexternal voltage applied is lessthan 1.10 Vandis increased slowl.,. it is observed that the te
continues to take place tillthe external voltage attains the value 1.10 V, When this is so., reaction

current flows [see Fig. 3.4(b)].

If the valueandof noextemal voltage exceeds the voltage of Daniel cell (1.10 V), the reaction takes plas: :
(c) altogether
electrolytic cell [see Fig. 3.4(c)).
opposite direction, i.e, the cell functions like an Een> 1.1V
Een <1.1 V Een =1.1 V

Anode OCathode Cathode |Anode

Current
|=0
+ve Current-Ve
-Cu Zn C Zn -Cu
Zn Salt Salt
-ve +ve
bridge bridge

ZnSO. CuSOA ZnSO. CuSO.

(a) (b) (c)
Fig. 3.4: Functioning of Daniel cell when external voltage E 0pposing the cell potential is applied
16. Electrode Potential: It may be defined as the tendency of an clement, when it is placed in contact with IS
own ions lo either lose or gain electrons and_in turn become positively or negatively charged.
The electrode potential will be named as oxidation or reduction potential depending upon
wheier
oxidation or reduction has taken place.
oxidation

M(s)
rcduction
M(aq) +ne
0 0 0 0 0 0 0 0 0

M(aq) + ne M(s)
Oxidation
Characteristics: Hat 298 K
la Both oxidation and reduction potentials are
equal in magnitude but 1bar
opposite in sign.
L The reucion potential shows an
increase with increasing concentration
and decrease with decreas1ng concentration of ions in a solution.
(e) Itis not a thermodynamiC property, So values of Eare not additive
17 Standard Hydrogen Electrode (SHE): It is a reference electrode and
1MHCI
Be reduction potential is arbitrarily assigned as
zero volt at all
temperature. Pt foil
A ctandard hydrogen electrode consists of a platinum
electrode coaled
h nlatinum black. The eiectrode is dipped in an acidic
solution Fig. 3.5: Standard or
Normal Hydrogen Electrode

arsideá
 Electrochemistry |101
bubbled
havingIM
concentration of H" ions. Pure hydrogen gas at I bar pressure is continuously
throughthe solution at a temperature of 298 K(Fig. 3.5).
hydrogen electrode can act both ways--as an anode or as a cathode.
The
Actingas anode Oxidation takes place,
H,(g) ’ 2H*(aq) + 2e
cathode - reduction takes place,
Acting as
2H"(aq) + 2e" H,(g)
Representation of SHE

PI(s) | H, (&) | H" (aq) (C = I M)

Potential (E"): It may be defined as the electrode potential of an electrode
Standard Electrode standard conditions
18. dotermined relative to standard hydrogen electrode under standard conditions. The
taken are:
each ion in the solution.
) 1M concentration of
of 298 K.
(i)A temperature
each gas. cells is called
(ii) Ibar pressure for The difference between the electrode potentials of two half
Potential or EMF of a Cell: drawn from the cell.
19. Cell
is known as electromotive force (EMF) of the cell if no current is
cell potential. It
Eell Erod (cathode) - Eovid (anode) = Ecathode -Enode
cathode on right, it follows therefore.
Since anode is put on left and
Egell = ER - EL
therefore
For a Daniel cell,
cu/Cu - Ezn1Zn
Eseli = E
= 0.34 V -(-0.76 V)
= 1.10 V
of ions.
Nernst Equation: It relates electrode potential with the concentration
20.
M"* (ag) + ne ’M(s)
For an electrode reaction,
written as
Nernst equation can be
[M]
CM*M = E°
M"*/M nF [M"]
2.303 RT 1
M"* /M nF
-log [M")
potential
where, Egn M = Electrode
= Standard electrode
potential
M* /M
R= 8.31 JK- mo-!
T= Temperature in Kelvin
n = No. of electrons
gained
(96500 C mol )
F=Faraday constant
Substituting the value of R and F. we get
0.0591 1 at 298 K
log
EM /M=y*/M [M"*1
0.0591
Or MM = E.
M/
+ log[M*"]. at 298 K
ions.
with the increase in the concentration of
Thus. the reduction potential increases

Xarnidea
 102 }Xam idea Chemistry-XI
reaction of the type:
For a general electrochemical
ne
ad +bB +C+ dD
Nernst equation can be given as
RT ICI'Dd
Eoel =Edl
nf [A1°Bj
Ecell =Eg
2303
RT log
ICI'D)
nf

Substituting the values of Rand Fwe get

00591,log (CI'(D at 298 K
n

21. Equilibrium Constant from Nernst Equation: For a Danicl cell, at

equilibrium
Egell =0=Edl 2.303 RT log Z
2F

Ell =2.303 RT
2F

But at equilibrium,

2.303 RT
Ecell log K
2F
2.303 x 8.314 x 298
0.0591
2x96500 log K,= log K
2
Poell =0.0591
In general,
log K or,
log K, =.
22. EMF and Gibbs 0.0591
Free Energy: The work done by a
energy reversible galvanic cel is equal to
decrease in its fre
IfMathematically, A,G =-nFEcel
concentration of all the reacting species is unity, then,
Ecel =Egell and we get,
calculate the equilibrium A,G°of =-nFEell
From A,G", we can
A,G° =-RT In K, constant a reaction,
23.
Concentelectratrolioynte Cells:
same If two
el cct rodes of the same
A,G° =-2303 RT log K,
cells are known ashaving different metal are dipped
concent ra tions and the
concentratiH,on| (c;)whileconcentreductratiioonn takescells.placeIn theseon thecells, oxidation separately into two solutions of üe
solutions are connected
takes through sait bridge, suCn
Hc) | Hc)|H; Cu | el ectrode with higherplace on the electrode with lower
Zn| Zn (c|Zn*)|Zn Cuc) Cuc) |Cu concentration (c,). For exampe
The EMF of
concentration cell at 298 Kis given by
Eocll =0.0591
24.
log, where c, > C
C
Electrolysolution
aqueous sis: The.orprocess of
lused statedecomposi
is calledltion of an
electrolysis of a substanceelisectrolysisel. ectbyrolyte when electric current is passed through is
The process of
governed Faraday's laws of
Aanidea clectrolysis.
 Faraday's first law of
Electoxchemstiy 0:3
(a)
The amount of any electrolysis
quantity of electricitysubstance
passing
deposited or liberated at the clectrode is
directly proportional o the
If w grams of the through the clectrolyte."
substance deposited on passing Qcoulombs of
or clectricity, then
w = Z x Ixt |: Q=Ixr|
where, Z is a constant of
deposited. proportionality known as electrochemical equivalent of the substance
Electrochemicalequivalent (Z): 1f I =1ampere and t=Isecond,
then
Thus, the electrochemical equivalence may be defined as the
passing one ampere of current for one second or by passingamount
of the substance deposited by
one coulomb of charge through he
electrolyte.
" IFaraday = Quantity of electricity carried by I mole of
(6.023 x 10 moll xl.6 x 10 C= 96472 C mol electrons.
96500 C mol)
If nmol of electrons are involved in an electrode
reaction, then
n x 96500 C of charge will deposit = Mg of the element
M
IC of charge will deposit = g of element
nx 96500
But I C of charge deposit mass of element = Zg
M E
Z=
nx 96500 96500
Atomic mass
where E is the equivalent mass of the elenment and is equal to of the clement.
Valency
Or E = 96500 × Z
" Equivalent mas: The mass of an element deposited by passing 96500 C of charge.
(6) Faraday's second law of electrolysis
"When same quantity of electricity is passed through different electrolytes, the amount of different
substances deposited at the electrodes is directly proportional to their equivalent masses."

Mathematically, WË_ E
W; E; Carbon rod
25. Commercial Cells (Batteries): Batteries are the electrochemical (cathode)
cells used commercially to generate electricity. "Any battery
consists of two or more than two galvanic cells connected in series
converted into
where the chemical energy of the redox reactions is
electricalenergy." There are mainly two types of batteries:
chargeable
(a) Primary cells (Batteries): These cells are not andafter
because the electrode reaction occurs only once
become deadand
the use over a period of time the cells
cannot be reused,
cell is the dry
The most familiar. example of this type of
which is
cell (known as Leclanche cell after its discoverer)
radios, calculators, etc. It
used commoniy in watches,
anode and the MnO, + Carbon biack
consists of a zinc container that also acts as Zinc cup
powdered (anode) +NH,Clpaste
cathode is acarbon (graphite) rod surrounded by
manganese dioxide and carbon. The space between the Flg. 3.6: The dry cell

electrodes is filled by a moist paste of NH,Cl and ZnCI,

(Fig. 3.6.

Xarnidea
 Zns) Zn+*
Anxi
MnO0H)+NH,
Cathie: Mn0, + NHð
l.S V.
Th ellhas a Mental of nearly of
the menury cell, consisting zin-neuY
AnthervN of primarn llis cathode. The clxtrolhte is a paste of KOH amalgam
and Zn0,
Nste of HgO and cartvn as the

Ande: ZnHg) + 2OH Zn0(s) +H,0+ 2e

20H
Cathxie: HgOs) +H,0+eH0+
1.35 V
The cell Mential is appximately
Cathode

remains onstant the ioni

as
-Anode
and
Qonentration of the solution is notchanged
during its lite.
(b) Secondary cells (Batteries)
Asooondary hattery is rNhargeable and can
be used again and again. It is recharged hy
passing cument through it from an external
soure. Most familiar example of secondary
cell is the lead storage battery commonly
used in automobiles and invertors. l
consists of a lead anode and a grid of lead Sulphuric Positive plates:
lead grids filled
packed with lead dioxide (PbO,) as cathode. acid solution
with PbO,
A 38% solution of H,S0, is used as an Fig. 3.7: The lead storage battery
electrolyte (Fig. 3.7).
The cell reactions when the battery is in use, are:
Anode: Po) +So (aq) PbSO,(9) + 2e
Cathode: PbO,(s) +So; (aq) +4H* aq) +2e ’ PbSO,(1) +2H,O)
The overall reaction is:
Pb(s) +PbO,(s) +2H,S0, (aq) ’ 2PbS0,(s) + 2H,0()
On recharging the cell, operated like an electrolytic cell the reaction is reversed and PbSO,() on
anode and cathode is converted into Pb and PbO,, respectively.
At anode: PbSO, + 2H,0 ’ PbO, + SO, + 4H* + 2e
At cathode: PbSO, + 2e ’ Pb + SO,
Another important sccondary cell is the nickel-cadmium cell which has longer life than the lead
storage cell but is costly. Here, the overall reaction during discharge of the battery is:
Cd(s) +2Ni(OH);() ’ CdO(s) +2Ni(O);(s) +H,0)
26. Fuel Cells: Fuel cells are those cells which produce Water
electrical energy directly from the combustion of fucls
such as hydrogen, carbon monoxide or methane. The
most successful fuel cell, H,-0, cell utilises the
reaction betwcen hydrogen and oxygen to produce (be)
water. Hydrogen and oxygen are bubbled through a
porous carbon elcctrode in the cell into concentrated Hoeo
aqueous sodium hydroxide. Catalysts are incorporated H2gas -Oz gas
into the clectrode (Fig. 3.8). The electrode reactions (be)
are: HOY

Fig. 3.8: Asimple H,-0, fuel cell

anidea
 Electochemisty 105
Anodicreaction: 2H,(g) +40H (aq) 4H,00+ 4e
Cathodic
reaction: 0;(g) +2H,0() +4e ’ 40H (ag)
Overallreaction: 2H,(g) +O,(&) ’ 2H,00)
Cells:
Advantages of Fuel
Itis a pollution-free device since no harmful products are formed.
Its efficiency is about 75% which is considerably higher than conventional cells.
cells are light in weight as compared to clectrical generators to produce corresponding3 quantity of
3. These
power.
I is a continuous source of energy ifthe supply of gases is maintained.
Corrosion: The process of sloW cating up of metals by gases and water vapours present Iin atmosphere due
27.
fornation of certain compounds like oxides, sulhides, carbonates, etc. is caled corrosion. Corrosion
ion is known as rusting. Chemically. rust is hydratedferric oxide, Fe,O,.H,0. Corrosion may be
Odered as an electrochemical phenomenon. According to electrochemical theory of rusting, the impure
race behaves like a smallelectrochemical cell in the presence of moisture containing oxygen or
nrhon dioxide. Such a cell is called corrosion cell or corrosion couple. In these miniature corrosion cells,
dissolved carbon dioxide
nure iron acts as anode, impure surface area acts as cathode and moisture having
electrolyte.
or oxygen acts as
solution as Fe jons leaving behind
AL anode, oxidation of iron atoms takes place. Thus, Fe atoms go into
electrons in the iron which are pushed into cathodic area.
Fe ’Fe++ 2e: Fe*/Fe = - 0.44 V ...(i)
are produced from H,CO, (formed due to
At cathode, the electrons are picked up byy the H" ions which
dissolution of CO, in moisture) or from H,0.
H,CO, 2H* + CO,
2H* + 2e 2H
area is
The H atoms, thus formed, reduces the dissolved oxygen as the net reaction at the cathodic
= 1.23 V ..(i)
2H + o, + 2e
2
H,0: E/o,/H,0
adding equations (i) and (i)
The overall reaction of the corrosion cell can be obtained by
Fe + H,0; E = L.67 V
Fe + 2H* +
o, 4H'aq) +O,
through water and come 2H,0
The ferrous ions so formed move Fe2' Fe?"
further oxidised by
at the surface where these are rust which is
atmospheric oxygen to ferric ions and form Fe,O3
hydrated ferric oxide (Fig. 3.9). Fe< Fe<

2Fe*+o, +2H,0Fe,0, + 4H"

Fig. 3.9: Corrosion
Fe,O3 +xH,0 ’ Fe,O; .xH,0
metal surface can be
28. Prevention of Corrosion: The methods:
following
protected against corrosion by the between iron and atmospheric oxygen, carbon
dioxide and
thin film is introduced
(a) Barrier protection: A adopted for depositing thin film on
metal surface:
moisture. The following methods are of grease.
surface with paint or a thin film
() By covering the non-corrosive metals such as nickel, chromium,
copper. etc.
iron with some
(ii) By electroplating electropositive metal than
protection: In this method, iron surface is covered with a more electropositive metal loses
(b) Sacrificial more
preference to iron. In such a situation the iron, hence the name sacrificial
iron which gets oxidised in metal is sacrificed at the cost of
electrons instead of iron and thus this galvanization.
is generally coated with zinc and this process is called
protection. Iron

Xarmideä
 c) Nletrical protetion: 1his is also acase of sacriticial motetion. This mtholis usal
of undergnvund water pis inn tans, ln this meth,the vpsl suutace ot
wmntingit oalck of sone awtive netal Isuch as magncsum, aluminium
lose
mne clatnysitve netal ats as anade and
cathxte This ncthvt, theeton, is also called
AeAVV by H'ns ofwaler at thesurtac of inn. Moecletusitive metal i ileanct aha
in the peves and nvis perixdal eplacenent.

I o n p l p

Anode Catlode

Flg. 3.10: Electical Potectlon

29, I'roducts of Electrlysis: 'nder the intluence of clectric curent though mellen eletolytey on bo.
aqucous solutions, ions move (owants opsicly chauged clectnes, Many tines the clewnde Mios
ditter.
For evample, the electnlysis of molten sulhum chloride yicls saliunm meal at the cathovle and chlngy
gas is livrated at the Anode,
Nacl(«) NaC
(olen stale)
Al anode,
Oxidation

Atcathode, Na(s) Reduction

However, when a cocentrated ucous solution of' sodiumchloride is clectolysed, | gas at cahode and
Cl, gas at anode ae obtaincd. This is bccause water is prelerably reduced at cathoe.
At cathod, 21,00) +2e llg)+ 20W («)
This hapcns because the standard rcduction potential of water is grcater thuu the sandad rcductin
potential of Na' ion.
Nax) 27| V
>ll;(e)+ 20W () a-0.83 V
AL anode, however, Ch gas is liberated becausc of over potential of oxVgen, In ft, (he
icuining solution
ater clectolysis yields solid NaOH on cvaporating. Thus,
A anode: 2CT(a)
Atcathode: 21,0)2 >ll)OW ()
2H.0)+ 2C|(ag) 2Na (u) ll,g)t(hg)20T(q) 2Na'(g)
(a) Eleetrolysis of dilute M,S04
During clectholysis of dilute , S0,.0hepoducts e ll; (g)ut code and O,(g)t amoude:

ALanode,. II,00)

At cathod, 2N'(ay) 2e

Kamidea
 Electrolysis of( aqueous Copper salphate using inert eiectrdes
(b) P
in this. copper is de

Atanode.
CuSO,(ag)(agi- s0;ag
H,0()0()- 2Hta)-.Ë=-13T
So; (aq)s0, -2.
E=-201
tor having low E. wouli be preferzbly
Cú`sed 2 node instea of S0:
At cathode. Cu ions have grezter reiucioa
potential, ooppenis deposted
Cu(ag) - 2e Cus).
2H,0() -22H,(z)-20H (a2.
1E CusO. is electrolysed between twO copper electrodes (actie electrodes, the Cuions
the cathode (negatively charged) and the following reaction
ischerge t
occurs:
Cu(ag)-2eCu(s)
Thus. copper metal is deposited at cathode. At the anode. copner is convertei into Cu ions with the
following change:
Cu(s)Cu(ag) - 2
Thus, copper is dissolved (oxidised) at anode and deposited (reducei) at cathae. This forms the basis of
an industrial process in which impure copper is converted into copper of high purity. The impure opper
is made an anode that dissolves on passing current and pure copper is deposited at
cathode.
(d) Electrolysis of aqueous sodium bromide. Like aqueous NaCl. the electrode products are Br () at
anode and H, (g) at cathode.
Conclusions: 1. Cathodic reaction will be one which has higher E value.
2. Anodic reaction will be one which has higher E° value or lower E,
rod value.

Important Formulae
1. R= =px Cell Constant

where, R= Resistance
A = Area of cross-section of the electrodes
p = Resistivity
2. K= 1 X cell constant
R

where, K= Conductivity or specific conductance

KX1000
3. An =
M
where, Am = Molar conductivity
M = Molarity of the solution.
A. A(A, B,) = xA(A*)+yA (B)
where, A, = Molar conductivity at infinite dilution, x and y are the number of cations and anions produced
by one fornula unit of the electrolyte on complete dissociation.

Xanidea
10s |Xam idea Chemistry-Xll

where, a = Degree of dissociation

=Molar conductivity at a given concentration
6. For a weak binary electrolyte AB
K=
ca? c(A;)
1-a

where, K = Dissociation constant

cell = Ecahode -Eanode

= ERicht -Eof
7. Nernst equations for a general electrode reaction:
M" + ne ’M
RT
E" IM = E°
"M*M -In [M]
nF [M"*]
2.303 RT
EMM =Ey nF
log
[M"*)
EMM = E0M"* /M 0.059 1
log at 298 K
[M "*]
8. Nernst equation for a general
electrochemical reaction:
ne
aA + bB
’cC+dD
Ecell = E°.
cell
RT (CID]
nF
[A1"(B]
Ecell = E°cell 2.303 RT (CI»(DI"
n
IA1°IB]
0.059
Eçell =Eell -log-[CI'|D) at 298 K

9. log K, =
0.0591 Ecell
where, K, = Equilibrium constant
10. A,G° = -nFEell
A,G°=-2.303RT log K,
where, A,G° = Standard Gibbs energy
li. Q=lxt of the reaction
where
Q= Quantity of charge in
|= Current in coulombs
amperes
I= Time in seconds
12. m =2x IxI
where m = Mass of the
substance deposited at the
Z= Electrochemical equivalent electrodes

anidea