Unit-3

Oxioaion hall eatton :Zhs

Electnochermisdy Doduion hal hlachon uias) t’Zha+
2e (At anocte)
2eCu)
2

(At cathade
Overall 0action Zn(5) +
t is the study of chemical energy Cvo elecdnica) Cuas)>Zntogt Cus)
enegy nd how one Can be convetec indo anothe Cell ephes endaton
called electonochemistsy.
Eien Ecatksde - Eansde
tlectaochemical cell Fe 0.34v -(-o.16 v) =1.1v
halvani cell (o) votta'e cell
The clevice in which chemital enengy is onverted Flou o e Oyoltmet
into electaical enengy i caleol electochemical cel.
Salt bridoge
Daniell cel
Zn nad is placed in Znsoy Soluhon (Mola) and Cy
Sod is placecl in 1 molas Cu soy Solution,
|Zn od and Cu god Connected by metallie wihe
thaugh voltimete and swith.
Two hal cells cne connected by salt bmidge. IM Zhsoy Solvion IM Cusou Solvhon

Obsevatong Standasd Hydaen Eletoode Sme)

Concentaton of 2n* incoe ases and Concentsaton of ) Constnction and wning
Cuzt decheases. i)Neat Jabelled diaggram
Weight 2n sad deoeases and weight of cu d ) Hal! cell heaction
ineases. extehna!
cell 9epnesentaton
Zn god to Cu hod wshen
Cuasent potentodis
klos krom Cu hocd to Zn aol, less vi) Concennatn of ioy is one mala.
Hhan l,|V

Applicaton Salt bnidge JtndaA sedvcian potental (Stndasd electhoce

maintins electnical neuthality in tws hals cells. poenta) is measued by SHE,
It prevent the aceumation o chaonges in the
halk cells.
3t omple tes the electaial cincwit. Constucion
Consists of aPt wine: Seatedin a
gass tbe
Salt bonidge a U-shaped alas tube tled with Ond pt wie is attached to ptoi9):d1)N
qell caled Ontaininq kcl on) k Nog
t fol is Coated with finely? dividedt blazky
(o) NnyNg (on)Ncl lo h) ge lo 4i ne is Sunounded by a cylindnieal qlassjacket
17 and cl ase almost same. dipped in
toit is
Mobiity inlet ot the top aud pt
|hauing an
 O. 76N20
IM HCI Soluion. | z zE-0.76v
unent
Yass pune and dy Ha gas at Tan phe ss ore into 2nrod
the !nmolas HC| soluon though an inlet.
the surface of he Sat bnidqe
Ihe H gas ge t absobed
Pt foil.
The absonbed H, is in Contact with the Ht ions pt wihe
IM H solohon
Standad electhde potentel o SHE iS taken as pt toil

Halk cell neacHon IM Znoy |M HCI

lba HeG) 2 Hag)t 2e
pt wie
Half cel 9epresentation
Pts), Ha(9, lbas) /H*(i) Deteminaton e SRe os Cu electorde using SHE
|M HU
culcu electode
soluion Cu nd is placed in IM Cu5o4 Solution which acts as a
heducion halk cell.
Deteminaton o SRe Zn electsode uwing sHE SHE' acts as oxidation hall celt.
Zn/2n electrode. Both electnodes ahe Connected by a metallic wine
SHE is the eleence elect r ode. throuah voltmete and switch.
Zn od is placed in IM 2hsot soluion, shich 'act as Voltmete indiates dineion o low of cuorent towads
an oxida tion hall cell. 32
hydgen electnode.
SHE acts as Se duction hall cel. Oxidation half eacton: H24)>ZHa)+ 2¬
Both electnodes Connected byia me tullic wihe Redvtion hall heacion:Cutaayt 2¬’Cus)
thaouch votmeten and switeh. Overall cell eacton:Ha(9) t(ua)’2Hayt (uG)
Voltmetesindicotes diecion of low ot Cusent Cell ne presentaton
towasds Zint. ptlHa)lIHaglleuaylcus
Oidaion hall gne achon : Zn)Zna4)t 2e tei Ecalk ode Eanode
Redvction halh geaction ?2Has)t 2e Ha(9) Salt bidee

Cell ephesentation t Eeu o.34 (at bo)

foil
 tlectohemical Seies
Ihe aoorcungement of elements in the ondes,
M*ag) t ne

decheasing Co) inc heasing SRp valves is Callecd he En

|where, Im 2tlecthode potenial
potential atot ay
any
electnohemical Seies. ¬rm Standad ele ctnode potential. contenthaton.
R=3.314J mor, T:298k
Appkcations f-fosaday 96,500c mar'
1.fo compatre the elaive stneh of o ducing and nno, of electons involved in eachon.
tne powe
oxidising pouwen
Eg: fr-has highest SR ( 2.81)Strong oxidising Qgent.
EmIm tmm-9.059.loq
Li-has lowest sep G3.05y)>Stong Sreduing aget. Zn)+ Cu tay 2naa)t Cu()
Keduing pouwer o6 metal od
SRp
tcen= Ean - 9.os9,
n
log 2Ccug
2a1 (or
Oxidising poue o hon- neta ed sRP
2 To ompae heactvity of metals
Keactvity of metal o I
SRP Eo.16) 40.3u)hh Cell sepreS entaton
Nig/Niasll AgelAgt9
Znsoy t Cu No eachon Cell neachon
3 p9edict whether metoal Can libeate Ha fromm NiG) t 2Agaa)Ni (ayt 2Ags)
Nenst equation
(As]
Cu t Hesoy No H is ibeated
prediet feasibilkhy o reactionsnio P'oblems
Eceu=tve (Spontaneous heatt o n ) ; o b s
Ecen -Ve (hNonsportaneouse heáchon)a l s 1. Calculate Ecel, Ecer f the tolloing cell seacthon
s.|To paedict the pehodvets o elec tsolssge s
Ecula 0.34v; Emtlmg -2. 31V.
olCell 9eacton
H,Zer0 Mg) +Cu a)sos) t Cut)
trel( Etothode - Eanode
Nenst equation
Ecell o.34 -(-2.3)
SHE is used to calealate see (Concenthation zl mala)
Nenst equation is used to calaulate electaode potentl Ecen = 2.71v
metal at uny Concentatn
 Relation between equlibni um Constant
Neost eqyation Daniell cell k and Eiet
Eceu Eceu - 0.059, loMg
2 Zns) t Cu'aa)
Ecel = 2.|- 0.05 9 log to ten :E a - 0.059, log (z-]
2
2

tceu -2.( -0.024S x log lo At eauilt brium, Eceno; k=[2.

Ecen= 2. 68V
2.
0Ecen-O,059, log ke
Calulate emf of Cell 2

Ni(S)+ 2Ag* (0.002 M)’N"(o.60 M) +2Ag ) Ecen 0.059. logke

hiven that Ecelr =1.05v..Tntext 3.5
S Ecen ler - 0.0S9. loqNi log ke Eceln Xn
0.059
tai l. os -o.0245. lo 16xto
(2xi6 Relaton between Ari and Ecell
) oil4
hibbs enengy ob 9eacthon = Arh=-nfeel
Ayhe-2.3038T logke
Wmau- Ara
Eur21.05 - 0.024 s.loq 4+ +log
Ecelllo5 -0.135 Problems
tcelo.q15V
3. Calalate the poten thial
|Calulate the equikbnium constnt of the neachon
hydrogen electode in contact Cus)t 2AGes) ’ Cutay t 2Ag ()
with a solution whose pH is Io, Intext 3.4dore1
Ecen0.46v, Example 3.2
tcell0.05qv log ke0.y6v oY)
2
2
objec tive log Fe o.46Vx2 1S.6
Enth1=- 0.059.log tntw,-0.0 S9 xpH 0.054 v
2 (169) pH z-log(H)
ke3.46 x\S
2

tHtH O.059 xz. los (w

(H-anklog-1)
he standad elehode potential for Daniell cel is l. tv,
Ertik,=0. os9 x(-10. lo9 io) Calculate the stndad hibbs energy ben the neachon.
tulu,=-0.5qV
Zn(s)t (u tan) ’2naat Cus) éxample 3.3
Orh=-nf Ecell
 3
Conductance (G)
he propenty of substance to allow
allo tlow
Aya 212275mo Units:: ohi'
Ari-2|2.27 kJmo ()mho Siemens(s)>S.L. unit
Condvc tivity () kapo)
3. lhe cell in which the tollowing heacion OCcUNs:
2feaa) t 2lay ’2feasy t Iaig has bcen =0. 236 Vat 29k
ondvctance of lcm' on) im'
electolytie solbton.
Calcuate the standad hibbs enerqy and the eqwlib
Cons tant of the cell eac ton Intext 3.6 Unitsohm'm (on) S i'
Solli) Ara=-nfEcel
Orh-2xq65oocmor'xo. 36V s Molan Condutance (Am) (Lamhda)
Ara-45548cV (ondue tance of Imolas electnolyte solokon.
Srn-4SS48J
Orn-4S.58kJ *mkxo00
M
Amkxv
)lg ke=cenxn Units:S Cmmolr
0.054
log ke o. 236 x2 Cell constant (a)
0.059
The otio o distane between to electnodes()
Ound ahea of hoss- Secton (A)
kezantilog (3)
A

Condutance o Electalyic Soluhor

Resistance (a)
Note 3. JAmx000
A M
The pmopenty of substance to stop flow of cutent.
tUnits!ohm(n) A
kcET- 2021, 2022, 2013
a tnea
P-2 xA J.M -20I, 2014, 201|
ot Goss-sechion AliMS - 2018
t- Resis Hviy 2 k I NEET 2016

k
2. Resistivity (0) rho) R A

Units ohm m ’ S.I. Unit

of electhlyte Solvton.
 Paoblems 0.|M kI Solohion 0.02M kc Solution
Res2o
1.The hesistance of a condt vity cell Continin9. k-l.29S m k=G |.29 Cm!
O.0OM kcl soluhon at 298 k is 1500n, hat is the S23N
Cell constunt it conduc tivity of o.00IM kcl Solukon at G*-Rxk k= 2.48 x\5's Cm
248k is 0.[46x( S cm! tx.3.4 G*(0o oha xl.L5K15cm
Sol R=ISoo. G1.24Cm
k=0.l46x (3's Cm! AmkX\000
Cell constant (a
k=axG* Am 248x13 x1000
O.02

Am12YS Cm'ml

G*=0.19Cm' Ehect of dilution

LConduetance
2. |he Condctivity o.20M Soluhon of kc| at 298k is On dilvion, intenachon between ions deLneases. So,
0.024 8 Scn! alu late its molar concctivity. Ex. 3.& Condvtance inheases.
Sol Mo.2M
k-0.048 S Cm
Am?
Condue huty
On diluhon,number oh ions pes unit volume dereases.
Amk xI030 So, Conductivity decreases.
M

AmO.0248 Xl000 o 3. Molan conductivi hy

On diluton, volume ot soluion lontaining tmal of ele cthl
Am=24.& -e incneases, So, male conducivity incheases.
O.2

Molaity Dilu kon

2. Resistance f a conductvity cell sled with o.l mol kci kci o.|M0.Lm
Soluton is lo0n, D6 the esistance of the same cell G Mone Less
when illecd with 0.02 mol k solohon is 520n, Calwlate le ss Mone
the conduchvity and mo lan Condvctivity of 0.02 mal AmMohe Less
kcl soluton, he conductvity of O mol k Sobtkon is
I.29S/m, Example .3.4
A
 Ekfet af diukon gn mala condyetvity Conducivity of electnolyte is equal to the Sum of
Strong electaolyte As%’l00y) limi hing
molan conducivity oh cations and anions
On diution, fhesnÇ.I is a Small incease in molasn present in electolyte,
Conductivity.
Limi ting malan conductng is the molan coriduihvity
at infinite dilokon (Concentna ton, Co)
Limi tng modao conduc thvity is determined by Debye Apph cotion o kohlausch la
- Huctel -Onjagai equaton. imihng molan conduchvity et weat electmolyte
The constant A' depends type of electnlyte. tAim(cHycoONa) t A^im(H)-Nm(Nac)
Some electnoytes of Some compounds ae given by
) Naci - ) Am(wHy ci) + ^im(nao) - ^m (Nac)
i) Caci, (2-)
Note
COmpasing Debye- Huckel-Onsagan equaton wth neo A >CHgcoo (Aetate), AcH »CHg(oow
equa tions We obtain a g h a g h , t
2
Deggree s dissociatan weat electsolyte
where, m is malas conductvity at ay
Nlope =-A Concenthaton
Am
kct
3. Dissociation canstant oh weak electaolyte
aloM
2 Weak electrolyte (s loo)
On diluion, theshe is a Nesy lage inchease in molas Solubi kity et Spasningy sloble salt
Conductivity. Agcl, Baso4 ’white ppt
Km kX \000
Solubility
Am
Phoblems
-cH3cooH
1.he molon conduetvity f o.0s mol methan' aid is
46.( Scm mor al ulate its deanee of dissocation andl
kohlaausch law di ssouation constant, hiven 2 )=349.6s Cmt ml and
Acconding fo fohlsousch las, the imi tng madas ^ Hc)= S4.6S Cm mo! In text 3.4
Sol Given Faraday's lau
2(H)=349.65 Cm mol when Scame amont of eeeticity is passed thoogh
d:kenent electnoyt Solokon, the amount
ASm46.1S Cmnor Substance Nbeated (ony deposited is dihecty
phopontional to equivelent weight.
Nm=(s.6 +3u9.6)s cm'mol WeE
Nmifoy.2S Cm' hot
dAm- 46.15Cmt mol W
0,(|yo

HoOH(a) HCoo (as) t Hta) Note

W=2Q
WZ[t
clt-)
where, Ci is intal concentation and G is equi libaum
concentaion q6,500 46,500)
ka= f- atomic mass
[Htoo] ChargeCalt
ka9.025maxo.l|4) Eg: Nat
((- 0.1) E=23 E= t = 20
ka3.249X(6 mol !.
0.286 faradayChasge of imal of elect hons
ka=3.61x\omolL -6.022 x(3x(,6olx
6,500C mo
2. Am to Nacl, HCI and Nae are 126.4, 425.9 and a1.0S Cm t : Na 4eNea
mol espech vely. Calculate N fon HAc, Ence use 3.2 (mo) (mo)
239
Mno,t SeMnt
NmHA)=42s.4 491.0-(26.4) Scmt mor (+1) (+2)
Am(HA)=340.5.5 Cmt mol
Prcblems
faraday's lan
lhe amount of substance ibeated (09) deposi ted is 1. A soluton of Cuso, is electnalysed for ominutes with a
dinecthy ropon honal to uanthy of electaiity Cussent f l.Sampenes. What is the mas of copper
passed thnough electolyte solu ton, de posited at the athode?¬ xoimple 3.10
WoQ)We2Q t-omin =l0x G0=600s
z-flectnochemital equvelent) Q=it-1.5 x600=9000
 Aqueous Naf
Cuat2eCus)
2f-2x 96,4 87t to deposit imol (0) 639 of Cu OH
fos 900c, the mass of Cu deposited 2H+ 2e’H2(RlN) at cathodo)
63 x40o
=0.243 89 2H,001t4H+ 4e (o/N) (at anode)
2x96,481
(or)
2. A soluhon of Ni(No, is electaolysed be tween pla tinu yOH ’2H2otOzt he
GDilute. Cusoy
electnodes wing
|20 minutes, What
a curent of
mass of N is
samperes boSh
depo sited at the so
Cafhode Ex. 3./5
NrNo), ’Ni 2(No) Cuttt 2elu (RN) (at Cathode
N2eNi 4O 01+2Hy0+ 4e (o/) (at anode)
Qnf= 2f =2Xq6, Soo =(.43 xlo
L)-S8. 19 x 60ooc- ix t Battenies
1.43x 1o The eletnochemical cell used to genehate electhicity
WEl.8259 are called batteies.
Battenies are o 2types:
Phodv t af electndysis 9 Phimeay battesy (or) cel.
Deposihon of ions ) Se conday batey (or) cell.
Ags cu'> t> z-ts cats Nat Pnimasy bottesy
I. Molten Nac 1he batteuy whih Cannot be heused (or hechasged
Not +eNa (Rin) (at cathode) is Called
Pimay battey.
2c*’c+2e lo/n) (at anode) Ea: Dry celt (lec lanche ce), menuy cell.
2. Aqueous Nacl
Nat
Dry cell
it is USed in thansis tns, clocks, Memotes, toth lhghts,
2H*+2e’Ha (kln) at cathode) toys, etc
|2c,+ 2e (on) at anode) Anode:Zn containen.
3.Conc.Cuso Cathode:aphite (Coanbon) hod Sussounded by powdenel
Mno, and cabon,
H OH
tlectnolyte :NHcl +Zncls
Cut2e-u
2
ein) (at cathod e) At ande: Zn Znt+e
2s0, So +2e (o/) (at anode) At Cathade:MnoztN +eMnofo) +NH x2
(Ha 5zo)(Peoxo disulphuoie aid) Ovenall Zn+2Mno, t 2 NHZht 2 MnoloH+2NH
 NH3 pocluced in the heac kon foms Complex Duaing changing (od hechay
with Z" to give At anode i PbsJ,(5) +2ePb(s) +5o4( )
Cell potential- I.2 to I.Sv, At cathode Pbsou(s)+ 2H0) -> Pbo, )+ sotasyt tHias,) t 2e
Ovenall eacton: 2Pbsos)t 2H,of) ’ Pbs) + Pbz(5) + 2H, so,(aq)
Menuy cell (Button cel)
t is used in hecoing aids, watche s, ete. Nickel - CadmiUm cel
Anode:Zn-Hg (Zine amalgam) It has lasqe l:be Cnd mone expenstve than lead
Cathode:Hgo+ Canbon storage battey.
Electrolyte:kon +Zno it is lighten and Smalle.
At ande:Zn(H)+2 oH Znot H,o t 2e Anode: cd CadmiUm)
At cathade i Hqot Ho +2¬ Hg t 20H Cathode: Nio
Ovenall heaction :Zn(Hg) + Hqo ’ Zno+ Hg Électnotyte:koH
At anode :Cds)t 20H(a4) ’Cdots) +Hao(c) + 2e
Seconcdany kaiteny
he batteouy which can be chaged by passing
At cathode: 2N (oH), (5) + 2¬’2Ni(o (5) +20H(ag)
Overall heac ton: Cd)+ 2N:(oH),(5)(do(s) + 2 Ni (oH)S) f Hyo)
Cunnent in opposite dinection ase called Seconday batb
They Can be nechanged on) reused.
tg: Lead Stoage battey, Nickel-Cadmium cel,
fuel cell
Galvanie cells which Convet chemical eergy to
Lead Stomage bottery eletnical enengy by the com bus ton of buels ike
Ha,CHy, CHy0H et, are Called tuel cells.
Ît is Usel in automobiles., inveatos.
Eg:H,-O, cello
Anode: Lead (Pb)
A qnid o leal pacted with binally divided Sponqy leag
Cathode: Pbo, ydagen-Oxygen tuel cell
,
it was used fo pnoviding electnical power in the
A gnid of leal packed with Pbo) Apolla Space prognamme (Rockets):
tlectnolyte: a. Haso, (18% by mass) H and J are bubbled thorough ponous Canbon
At Cunocde Pbs) +soe(a)’ Pbso, () t 2e
At cathode: pbo, (s)+ Soylaa) + electnodes into concentnated aqueouS NaOH (oy koH
4Haa)t+2e>Pbsoy(s) +2H2 )
Ovenall eacton: Pblst Pbos5) +2H,Soylaa)>2.Pb soy(5) t 2Ho(C)
Soluton, Catalysts like bnely divided pt (ov) P me tal are
inconpohated into the electnodes fon ineasing the
Duaing using (or) dischanging (od in the operatin of hate o! eletrode eachons
leac stomage battey (or) when uent is dhawn At anode 2H9)t 4oas)4Hao) t 4e
fom it. A{ cathale: O(a) + 2Ha0)+4e OH
On choaing the batty, the uaion is se vesed and Oveall heacin: 2H4)t O(9)’He)
Pbso(5) On ande and Cathode is Conveted intoik
Pb and Pboy, he Spe tve ly.
 Advantages o fuel cel chemical bke bs
bi's phenol, altalin phosphates.
phenol, alkalines
)Fuel cells cre polluion free.
70, electiity
i) They Cie
highly esicient. Fuel cellsabout
prodvce Sauthca paatechsa
with hespective an e66icienty o 1non is hotected by coving ath a laye o
tkic'ency o theumal plant is about uo. moe active me tal ike Zn,MgSn etc.
tü) Fuel cells un continuously as long as the heactant
1he covening of ihon with zinc is called
ne supplied.c Galvenisation.
Hio
Zinc corodes itselk but Saves the object.
Anale lathsde 4)
Aqueous electnolyte (koH)

Coosion
The poless of slow heating up of the metal
|Sace by the gases (o) nd waten vapous poieen
in ain due to.fohmaton o compounds such as
Oxides,Sulphides, Casbonate is icailecd Coroosion:
Eg: Rus ting of Inon Fes0,Huo), aonishing o{ sitver
(Ag), deve lopment ot geen Coating on Coppeh an
bronge
Kusing as Shon
RustHycboted fes9ic oxide (feso3.x Htao)
The tesous ions ae funther oxicd; sed by atmasphee
O to fee ions which cameout as hust in the
tonm of hyatecd fernic oxide (Feao,. XHLo).ihsh
Hfet O,t4Hyo'2fe07t 8H'ag
feyOg tMH20feo3.xHyo.

Pyevenive methods coNO SiOn

Bargie method
bonien is placed between inon and atmosphenic
ain by coatng the sunsace with paints, some