FORMATON OF GALVANC CELL

O A Battery: A system which converts chemical energy into electrical energy

More correctly, a battery is an eIectrochemicaI ceII.
O aIvanic CeIIs convert the energy from spontaneous chemical reactions into electricity.
O IectroIytic CeIIs use electricity to drive non-spontaneous chemical reactions.


Galvanic cell
O A aIvanic ceII, or VoItaic ceII, named after LulCl CALvAnl, or ALLSSAnu8C vCL1A respectively,
is an ELECTRO CHEMCAL CELL that derives electrical energy from CPLMlCAL 8LAC1lCn taking
place within the cell. t generally consists of two different metals connected by a SAL1 88luCL, or
individual half-cells separated by a porous membrane.
O Volta was the inventor of the vCL1AlC lLL, the first LLLC18lCAL 8A11L8?. n common usage, the
word "battery" has come to include a single Galvanic cell, but a battery properly consists of
multiple cells.
Description
A Galvanic cell consists of two PALl CLLL. n its simplest form, each half-cell consists of a metal
and a solution of a salt of the metal. The salt solution contains a CATON of the metal and
an AnlCn to balance the charge on the cation. n essence, the half-cell contains the metal in
two CxluA1lCn S1A1LS and the chemical reaction in the half-cell is an CxluA1lCn
8LuuC1lCn (redox) reaction, written symbolically in reduction direction as
M
3
(oxidized species) 3 e
~
M (reduced species)
n a galvanic cell one metal is able to reduce the cation of the other and, conversely, the other
cation can oxidize the first metal. The two half-cells must be physically separated so that the
solutions do not mix together. A SAL1 88luCL or porous plate is used to separate the two solutions
yet keep the respective charges of the solutions from separating, which would stop the chemical
reactions.
The number of electrons transferred in both directions must be the same, so the two half-cells are
combined to give the whole-cell electrochemical reaction. For two metals A and B:
A
3
3 e
~
A
B
2
2 e
~
B
2 A 3 B
2
3 B 2 A
3


1hls ls noL Lhe full worklng as anlons musL also be Lransferred from one halfcell Lo Lhe oLher
When a meLal ln one halfcell ls oxldlzed anlons musL be Lransferred lnLo LhaL halfcell Lo
balance Lhe elecLrlcal charge of Lhe caLlon produced 1he anlons are released from Lhe oLher
halfcell where a caLlon ls reduced Lo Lhe meLalllc sLaLe 1hus Lhe salL brldge or porous
membrane serves boLh Lo keep Lhe soluLlons aparL and Lo allow Lhe flow of anlons ln Lhe
dlrecLlon opposlLe Lo Lhe flow of elecLrons ln Lhe wlre connecLlng Lhe elecLrodes
1he volLage of Lhe Calvanlc cell ls Lhe sum of Lhe volLages of Lhe Lwo halfcells lL ls measured by
connecLlng a vCL1ML1L8 Lo Lhe Lwo elecLrodes 1he volLmeLer has very hlgh 8LSlS1AnCL so
Lhe currenL flow ls effecLlvely negllglble When a devlce such as an elecLrlc moLor ls aLLached Lo
Lhe elecLrodes a currenL flows and redox reacLlons occur ln boLh halfcells 1hls wlll conLlnue
unLll Lhe concenLraLlon of Lhe caLlons LhaL are belng reduced goes Lo zero
lor Lhe uAnlLL CLLL deplcLed ln Lhe flgure Lhe Lwo meLals are ZlnC and CCL8 and Lhe Lwo
salLs are SuLPA1LS of Lhe respecLlve meLal Zlnc ls Lhe oxldlzed meLal so when a devlce ls
connecLed Lo Lhe elecLrodes Lhe elecLrochemlcal reacLlon ls
Zn + Cu
2+
Zn
2+
+ Cu
1he zlnc elecLrode ls dlssolved and copper ls deposlLed on Lhe copper elecLrode (as copper lons
become reduced Lo copper meLal) 8y deflnlLlon Lhe CA1PCuL ls Lhe elecLrode where reducLlon
(galn of elecLrons) Lakes place so Lhe copper elecLrode ls Lhe caLhode 1he caLhode
aLLracLs caLlons so has a negaLlve charge when currenL ls dlscharglng ln Lhls case copper ls Lhe
caLhode and zlnc Lhe anode
Calvanlc cells are Lyplcally used as a source of elecLrlcal power 8y Lhelr naLure Lhey
produce ul8LC1 Cu88Ln1 lor example a LLAuAClu conLalns a number of galvanlc cells 1he
Lwo elecLrodes are effecLlvely lead and lead oxlde

Cell volLage
1he sLandard elecLrlcal poLenLlal of a cell can be deLermlned by use of a S1AnuA8u C1Ln1lAL
1A8LL for Lhe Lwo PALl CLLLS lnvolved 1he flrsL sLep ls Lo ldenLlfy Lhe Lwo meLals reacLlng ln
Lhe cell 1hen one looks up LheS1AnuA8u LLLC18CuL C1Ln1lAL

ln vCL1S for each of Lhe

Lwo PALl 8LAC1lCnS 1he sLandard poLenLlal for Lhe cell ls equal Lo Lhe more poslLlve

value
mlnus Lhe more negaLlve

value
lor example ln Lhe flgure above Lhe soluLlons are CuSC
4
and ZnSC
4
Lach soluLlon has a
correspondlng meLal sLrlp ln lL and a SAL1 88luCL or porous dlsk connecLlng Lhe Lwo soluLlons
and allowlng SC
4
2-
lons Lo flow freely beLween Lhe copper and zlnc soluLlons ln order Lo
calculaLe Lhe sLandard poLenLlal one looks up copper and zlncs half reacLlons and flnds
Cu
2+
+ 2 e-
Cu L

+34 v
Zn
2+
+ 2 e-
Zn L

-76 v
1hus Lhe overall reacLlon ls
Cu
2+
+ Zn Cu + Zn
2+

1he sLandard poLenLlal for Lhe reacLlon ls Lhen +34 v - (-76 v) 11 v 1he polarlLy of Lhe
cell ls deLermlned as follows Zlnc meLal ls more sLrongly reduclng Lhan copper meLal as shown
by Lhe facL LhaL Lhe sLandard (reducLlon) poLenLlal for zlnc ls more negaLlve Lhan LhaL of copper
1hus zlnc meLal wlll lose elecLrons Lo copper lons and develop a poslLlve elecLrlcal charge
1he LCulLl88luM CCnS1An1 for Lhe cell ls glven by
ln knlL

$81
where ls LhelA8AuA? CCnS1An1 ls Lhe CAS CCnS1An1 and @ ls Lhe LemperaLure
ln kLLvlnS lor Lhe uanlell cell ls approxlmaLely equal Lo 131
37
1hus aL equlllbrlum a few
elecLrons are Lransferred enough Lo cause Lhe elecLrodes Lo be charged
AcLual halfcell poLenLlals musL be calculaLed by uslng Lhe nL8nS1 LCuA1lCn as Lhe soluLes are
unllkely Lo be ln Lhelr sLandard sLaLes
L
PALlCLLL
L

81$nllnC
where ; ls Lhe 8LAC1lCn CuC1lLn1 1hls slmpllfles L
L
PALlCLLL
L

+23381$nlLCC
1
LM
n+

where ,
+
ls Lhe AC1lvl1? of Lhe meLal lon ln soluLlon 1he meLal elecLrode ls ln lLs sLandard
sLaLe so by deflnlLlon has unlL acLlvlLy ln pracLlce concenLraLlon ls used ln place of acLlvlLy 1he
poLenLlal of Lhe whole cell ls obLalned by comblnlng Lhe poLenLlals for Lhe Lwo halfcells so lL
depends on Lhe concenLraLlons of boLh dlssolved meLal lons
1he value of 233$ ls 198431
-3
v$k so aL 23 C (29813 k) Lhe halfcell poLenLlal wlll
change by '3 lf Lhe concenLraLlon of a meLal lon ls lncreased or decreased by a facLor
of 1

1hese calculaLlons are based on Lhe assumpLlon LhaL all chemlcal reacLlons are ln LCulLl88luM
When a currenL flows ln Lhe clrculL equlllbrlum condlLlons are noL achleved and Lhe cell
poLenLlal wlll usually be reduced by varlous mechanlsms such as Lhe developmenL of CvL8
C1Ln1lALS Also slnce chemlcal reacLlons occur when Lhe cell ls produclng power Lhe
elecLrolyLe concenLraLlons change and Lhe cell volLage ls reduced A consequence of Lhe
LemperaLure dependency of sLandard poLenLlals ls LhaL Lhe volLage produced by a galvanlc cell ls
also LemperaLure dependenL
Calvanlc corroslon
Ga|van|c corros|on ls a process LhaL degrades meLals LLLC18CCPLMlCALL?
1hls CC88CSlCn occurs when Lwo dlsslmllar meLals are placed ln conLacL wlLh each oLher ln Lhe
presence of an LLLC18CL?1L such as salL waLer formlng a galvanlc cell A cell can also be
formed lf Lhe same meLal ls exposed Lo Lwo dlfferenL concenLraLlons of elecLrolyLe 1he resulLlng
elecLrochemlcal poLenLlal Lhen develops an elecLrlc currenL LhaL elecLrolyLlcally dlssolves Lhe less
noble maLerlal
ALCA1lCnS Cl CALvAnlC CLLL
1ln a nlckelcadmlum baLLery Lhe reacLlons actua||y look llke Lhls
CxldaLlon
Cd(s) + 2 CP

(aq) Cd(CP)
2
(s) + 2 e

8educLlon
2nlC(CP)(s) + 2 P
2
C(l) + 2 e

2nl(CP)
2
(s) + 2 CP (aq)
neL
Cd(s) + 2nlC(CP)(s) + 2 P
2
C(l) Cd(CP)
2
(s) + 2nl(CP)
2
(s)
noLe 1he number of reacLlons and Lhe number of elecLrons hasn'L changed buL we're mote
completely descrlblng Lhe physlcal and chemlcal form of Lhe elecLrode componenLs
1he cell conLalns a pasLe of naCP Lhls provldes Lhe CP

lons needed for Lhe reacLlon whlle

also provldlng a medlum Lo pass charge (elecLrolyLe)
1he anode conslsLs of solld meLal whlch ls Lransformed lnLo cadmlum hydroxlde
1he caLhode conslsLs of nl
3+
lons ln a nlC(CP) pasLe whlch are Lransformed lnLo nlckel hydroxlde


lL ls caus Lhe producLs of Lhe reacLlon are sollds LhaL Lhe nlCd baLLery can be recharged
1he solld hydroxldes are sLlcky cllng Lo Lhe lnnards of Lhe baLLery and remaln ln place
lf currenL ls applled Lhe reacLlon can be drlven backwards!


ln a nlckelcadmlum baLLery we can recharge Lhe baLLery by applylng an elecLrlcal currenL from
anoLher source
Cd(s) + 2nlC(CP)(s) + 2 P
2
C(l) Cd(CP)
2
(s) + 2nl(CP)
2
(s)
8uL mosL baLLerles we use arn't rechargeable
2 1he Alkallne 8aLLery
8llllons upon bllllons of alkallne baLLerles are used each year
1hey are descrlbed by slze and shape AAA Lo u
Larger baLLerles have more sLuff" and Lhus can run longer
8uL Lhey all have Lhe same volLage because Lhey're all based on Lhe same elecLrochemlcal cell
CxldaLlon
Zn(s) + 2 CP

(aq) Zn(CP)
2
(s) + 2 e

8educLlon
2 MnC
2
(s) + P
2
C(l) + 2 e

Mn
2
C
3
(s) + 2 CP

(aq)
neL
Zn(s) + 2 MnC
2
(s) + P
2
C(l) Zn(CP)
2
(s) + Mn
2
C
3
(s)
3 1he LeadAcld 8aLLery
b(s) + bC
2
(s) + P
2
SC
4
(aq) 2 bSC
4
(s) + 2 P
2
C(l)
1he caLhode ls made of meLalllc lead and Lhe anode of lead dloxlde
1he elecLrolyLe ls sulfurlc acld
1hls reacLlon Loo ls reverslble
1he lead sulfaLe producL cllngs Lo Lhe elecLrodes so applled exLernal volLage can reverse Lhe
reacLlon


Leadacld baLLerles are referred Lo as sLorage baLLerles" because Lhls chargedlscharge cycle ls
so rellable
1hese baLLerles were used ln every auLomoblle unLll qulLe recenLly
1he baLLery ls dlscharged ln order Lo sLarL Lhe englne
Cnce Lhe englne ls runnlng and burnlng gasollne lL Lurns an alLernaLor whlch recharges Lhe
baLLery
1hls process can conLlnue for up Lo 3 years of normal drlvlng
AfLer LhaL Llme enough of Lhe lead sulfaLe producL has been shaken off Lhe plaLes LhaL lL can no
longer recharge


Leadacld baLLerles are also used ln envlronmenLs where vehlcles cannoL emlL combusLlon
producLs
lndoor forkllfLs golf carLs handlcapped carLs ln alrporLs wheelchalrs eLc
Powever lead ls an envlronmenLal concern!
Pow do we dlspose of Lhe mllllons and mllllons of baLLerles whlch dle each year?
1here ls a very succesful recycllng program ln Lhe uS 97 of spenL baLLerles are recycled
8uL envlronmenLally healLhler opLlons are under lnvesLlgaLlon