ELECTROCHEMI

STRY
Tabl
eofCont
ent
s
ELECTROCHEMI
STRY Or
gani
zer 1
RedoxReact
ions 2
Oxi
dat
ionNumber
s 2
Di
spl
acementReact
ions 5
TheEl
ect
rochemi
calCel
l 7
El
ect
rochemi
cal
Hal
f-
Cel
l. 7
TheEl
ect
rochemi
cal
Cel
l
. 7
St
andar
dEl
ect
rodePot
ent
ial
s 9
UsesofEl
ect
rochemi
cal
Cel
l
s 14
El
ect
rol
ysi
s 16
Pr
eferenti
al Di
schar
ge of I
ons Dur
ing
El
ectr
olysi
s 16
Quant
it
ati
veTr
eat
mentofEl
ect
rol
ysi
s 22
Appl
i
cat
ionsofEl
ect
rol
ysi
s 23

Obj
ect
ives
Byt
heendoft
het
opi
cthel
ear
nershoul
dbeabl
eto:
(
a)Expl
ainr
educt
ionandoxi
dat
ioni
nter
msofgai
nandl
ossofel
ect
rons.
(
b)Det
erminechangesinoxidati
onnumbertokeept rackoft
hemov
ementofel
ect
ronsi
n
r
edoxreact
ionsandwri
tebalancedr
edoxequat
ions.
(
c)Descr
ibetheel
ect
rochemi
calcel
landexpl
aini
tswor
kingi
nter
msofel
ect
ront
ransf
er
pr
ocess.
(
d)Dr
awcel
ldi
agr
amsusi
ngcor
rectcel
lnot
ati
ons.
(
e)Usedi
spl
acementr
eact
ionst
ocompar
ereduci
ngandoxi
disi
ngpowerofi
ons.
(
f)Cal
cul
atet
heel
ect
romot
ivef
orceofacel
lgi
venst
andar
del
ect
rodepot
ent
ial
s.
(
g)St
atetherol
eofwat
erdur
ingel
ect
rol
ysi
sandexpl
aint
hef
act
orsaf
fect
ingpr
efer
ent
ial
di
schar
geofi
ons.
(
h)Rel
atethequant
it
yofchar
gepassedtotheamountofsubst
ancel
i
ber
atedatt
heel
ect
rodes
andexplai
nsomeappl
icat
ionsofel
ect
rol
ysi
s.
2 Phy
sical
Chemi
str
y

ELECTROCHEMI
STRY
El
ect
rochemistryi
sthestudyofhowchemicalr
eact
ionspr
oduceel
ect
ri
calener
gyandi
ntur
nhow
el
ect
ri
calenergycauseschemi
calr
eact
ions.
Thesechemi
cal
react
ionsi
nvol
vet
ransf
erofel
ect
rons.

RedoxReact
ions
Aredoxreacti
onisoneinwhichr
educti
onandoxi
dat
ionpr
ocessesoccursi
mul
taneousl
y.Redox
r
eacti
onsinvol
veel
ect
rongai
nandelect
ronl
oss.
Gai
nofel
ect
ronsi
sar
educt
ionpr
ocess.Thespeci
est
hatgai
nsel
ect
ronsi
sanoxi
disi
ngagent
.
Lossofel
ect
ronsi
sanoxi
dat
ionpr
ocess.Thespeci
est
hatl
osesel
ect
ronsi
sar
educi
ngagent
.

Thereacti
onbetweeni r
onfi
ll
ingsandcopper(
II)sul
phat
esolut
ioncanbeusedtoill
ust
ratear
edox
react
ion.Whenironf i
li
ngsareaddedtoasol uti
onofcopper(
II)sul
phat
e,abrownsolidwhi
chis
coppermetalisformed.Thecol ourofthesoluti
onchangesfrom bl
uetoli
ght-
greenduetothe
formati
onofir
on(II
)ionsint
hesoluti
on.
2+ 2+
Fe(
s)+Cu (
aq) Fe (
aq)+Cu(
s)

Thereacti
onbetweenir
onandcopper
(II
)ionsi
nvolv
est ransf
erofel
ectr
onsfrom t
heir
onat
omsto
copper(
II
)ions.Thereacti
oncanbeusedt okeept rackoft hetr
ansferofel
ectr
onsdur
ingt
he
react
ionasil
lust
rat
edbythefol
l
owi
ngionichal
fequati
ons
2+
Fe(
s) Fe (
aq)+2e–
2+ –
Cu (
aq)+2e Cu(
s)

Int
hefi
rsthalfequati
on,i
ronat
omsl
oseel
ect
rons(
get
soxi
dized)andf
ormi
ron(
II
)ions.I
ronat
oms
act
sasar educingagent
.
I
nthesecondhal fequat
ioncopper(I
I)i
onsgai
nel
ect
rons(
get
sreduced)t
ofor
m copperat
oms.
Thecopper(
II
)ionsisanoxidi
singagent
.
Oxi
dat
ionNumber
s
Anoxi
dat
ionnumberi
stheappar
entchar
get
hatanel
ementhasi
nacompoundort
hechar
geonan
i
on.
Oxi
dat
ionnumberi
swr
it
tenwi
tht
hepl
us(
+)ormi
nus(
–)si
gni
nfr
ont
.,i
e+2or–3.
Theknowl edgeofoxi
dati
onnumber
shel
psonet okeeptr
ackofel
ect
ronmov
ement
sinr
edox
react
ionandtounder
standt
henami
ngofi
nor
gani
ccompounds.

Rul
esofAssi
gni
ngOxi
dat
ionNumber
s
1.Theoxidat
ionnumberofanuncombi
nedelementi
szer
o(0)
,e.
g.,i
nmol
ecul
es,O2,Cl
2,H2,t
he
oxi
dat
ionnumberofall
theat
omsiszero.
2.Thechargeonani
oncont
aini
ngoneel
ementi
sequalt
otheoxi
dat
ionnumberoft
hatel
ement
.
Forexample,
on Na+ S2- Mg2+ N3– O2– H+
I
Oxi
dat
ionnumber +1 -
2 +2 –3 –2 +1
 STRY 3
ELECTROCHEMI
3.Oxi
dati
onnumberofhy
drogeni
nal
lcompoundst
hatcont
aini
tis+1excepti
nmet
alhy
dri
des
wher
eitis–1.
Compound HCl H2O HF NaH MgH2
Oxi
dat
ionnumber +1 +1 +1 –1 –1
4.Oxi
dat
ionnumberofoxy
geninal
lcompoundst
hatcont
aini
tis–2,
excepti
nper
oxi
deswher
eit
i
s–1andOF2whereiti
s+2.
Compound H2O CuO H2O2 OF2
Oxi
dat
ionnumber –2 –2 –1 +2
5.I
ncompounds,
thesum oft
heoxi
dat
ionnumber
sofal
lconst
it
uentat
omsi
sequal
tozer
o,e.
g.,
Compound H2O Na2O2 NaCl
Oxi
dat
ionnumber 2(
+1)–2=0 2(
+1)+2(
–1)=0 (
+1)+(
–1)=0
6.I
nionscont
aini
ngmorethanoneel
ement
,theov
eral
lchar
gei
sequal
tot
hesum oft
heoxi
dat
ion
number
softheconst
it
uentel
ements.
+ 2–
NH4 OH– SO4
–3+4(
+1)=+1 –2+(
+1)=–1 +6+4(
–2)=–2

Whentheoxidat
ionnumberofanel
ementinacompoundori
oni
snotknown,
iti
scal
cul
atedf
rom
t
hoseofothersbyusi
ngrul
e5and6r espect
ivel
y.

Someel
ement
shav
evar
iabl
eoxi
dat
ionnumber
.Agoodexampl
eisni
tr
ogen.
Speci
es Oxi
dat
ionnumber Speci
es Oxi
dat
ionnumber
–
NO3 +5 N2O +1
NO2 +4 N2 0
NO +2 NH3,
NH4,
Mg3N2 –3

Exampl
e1
Whati
stheoxi
dat
ionnumberofsul
phuri
nsul
phur
icaci
d,H2SO4?
Thesum ofoxi dati
onnumbersinH2SO4=0(Rul
e5)
2(Oxidati
onnumberofH)+( Oxi
dati
onnumberofS)+4( Oxi
dati
onnumberofO)=0
2(+1)+oxi dationnumberofS+–8=0
(+2)+oxidationnumberofS+4( –2)=0
Oxidat
ionnumberofS=+6
Therefor
etheoxi dat
ionnumberofsul
phuri
nSulphur
ic(
VI)aci
dis+6

Exampl
e2
Det
ermi
net
heoxi
dat
i nMnO4–
onnumberofmanganesei
Thesum ofoxidati nMnO4– =–1(
onnumberi Rul
e6)
(Oxidati
onnumberofMn)+4( Oxi
dat
ionnumberofO)=1
Oxidati
onnumberofMn+4( –2)=–1
Oxidati
onnumberofMn+( –8)=–1
Oxidati
onnumberofmanganese=+7
Therefore,
theoxi
dati
onnumberofmanganeseinMnO4– i
s+7
4 Phy
sical
Chemi
str
y
Useofoxi
dat
ionnumber
s
ngcompounds.
1.Nami
Oxi
dat
ionnumbersar
eusedf
orassi
gni
ngnamest
ocompoundsofel
ement
swhi
chhav
emor
ethan
oneoxi
dat
ionnumber
.
Forexampl
e,copperhastwooxi
dationnumbers+1and+2.Compoundscont ai
ningcopperwit
han
oxi
dati
onnumberof+1ar eref
erredtoascopper(I)compounds.Thosecompoundscont ai
ning
copperwi
thaoxidat
ionnumberof+2arecall
edcopper(
II
)compounds.
Theoxidati
onstat
eofanelementi
nacompoundi
sal
way
sdenot
edbyaRomannumberwr
it
teni
n
bracket
s,asshownint
hetablebel
ow.
Subst
ance Oxi
dat
ionnumberof
: I
UPACname
CuSO4 Cu(
+2) Copper
(I
I)sul
phat
e
CuCl Cu(
+1) Copper
(I
)chl
ori
de
FeS Fe(
+2) I
ron(
II
)sul
phi
de
H2SO3 S(
+4) Sul
phur
ic(
IV)aci
d
H2SO4 S(
+6) Sul
phur
ic(
VI)aci
d
K2Cr
2O7 Cr(
+6) Pot
assi
um di
chr
omat
e(VI
)
KMnO4 Mn(
+7) Pot
assi
um manganat
e(VI
I)
CO C(
+2) Car
bon(
II
)oxi
de
CO2 C(
+4) Car
bon(
IV)oxi
de
SO2 S(
+4) Sul
phur
(I
V)oxi
de
SO3 S(
+6) Sul
phur
(VI
)oxi
de

2.Keepi
ngt
rackofel
ect
ronmov
ementi
nredoxr
eact
ions.
Knowl
edgeofoxidat
ionnumberhelpsindeter
miningwhetherareact
ioni
sar
edoxoneornot
.It
al
sohel
psindet
erminingwhi
chsubstancehasbeenoxi
disedorr
educed.
Oxi
dati
oninv
olv
esi
ncr
easei
noxi
dat
ionnumberwhi
ler
educt
ioni
nvol
vesdecr
easei
noxi
dat
ion
number.
Consi
dert
hef
oll
owi
ngr
eact
ionbet
weenaci
dif
iedi
ron(
II
)sul
phat
eandhy
drogenper
oxi
de.

2FeSO4(
aq)+H2O2(
aq)+H2SO4(
aq) 2Fe2(
SO4)
3(aq)+2H2O(
l)

I
nthereact
ionabov
e,i
ron(I
I)i
onsareconver
tedtoi
ron(
II
I)i
ons,t
hust
heox
idat
ionnumberofi
ron
i
ncr
easesfr
om +2to+3.Suchachangeisanoxi
dati
on.
Ontheotherhandtheoxygenfr
om thehy
drogenperox
ideunder
goesar educt
ionbyhav
ingi
ts
oxi
dat
ionnumberdecr
easefr
om –1t
o–2onf or
mingthewatermol
ecul
es.
Theabov
eisi
l
lust
rat
edusi
ngani
oni
cequat
iont
hus,

Ot
herExampl
esofRedoxReact
ions
1.React
ionofamet
alandwat
er

Sodi
um under
goesoxi
dat
ionbecausei
tsoxi
dat
ionnumberi
ncr
easesf
rom 0t
o+1.Hy
drogen
 STRY 5
ELECTROCHEMI
under
goesr
educt
ionsi
ncei
tsox
idat
ionnumberdecr
easesf
rom +1t
o0.
2.React
ionofamet
alandanaci
d

Magnesi
um undergoesox i
dat
ionandi tsoxi
dati
onnumberi ncreasesfr
om 0to+2whi
l
ethe
hy
drogenioni
sreduced.Theoxidat
ionnumberofhydr
ogendecreasesfr
om +1t
o0.

Di
spl
acementReact
ions
Adispl
acementreacti
ont akespl
acewhenamorer
eact
iveel
ementt
akest
hepl
aceofanot
her
el
ementwhichi
sl essreacti
veinacompound.

Reduci
ngpowerofmet
als.
Metalshi
gheri
nther
eact
ivi
tyser
iesdi
spl
acef
rom sol
uti
onst
hosemet
alswhi
char
eloweri
nthe
ser
ies.
Forex ampl
e,whenmagnesi um isr eactedwi
thcopper(I
I)sul
phatesolut
ion,abrownsolidwhichis
coppermetalisformed.Thecolouroft hesol
uti
onchangesf r
om bluetocolour
less.Thi
sisbecause
thebluecopper(II
)ionsint
hesol utionaredi
splacedbymagnesium ionswhichar ecol
ourl
ess.The
i
onichalfequati
onsf ort
hefor
mat ionofmagnesi um i
onsandcoppermet alar
e:
2+ –
Mg(
s) Mg (
aq)+2e (
oxi
dat
ionst
ep)
2+
Cu (
aq)+2e– Cu(
s)(
reduct
ionst
ep)

Whent
het
woi
oni
chal
fequat
ionsar
ecombi
ned,
thef
oll
owi
ngov
eral
li
oni
cequat
ioni
sobt
ained:
2+ 2+
Mg(
s)+Cu (
aq) Mg (
aq)+Cu(
s)

Theoxi
dat
ionnumberofmagnesium i
ncr
easesfr
om 0to+2whi
l
ethatofcopperdecr
easesf
rom
+2to0.Magnesi
um i
soxi
disedandCopperisr
educed.
Displ
acementreact
ionsar
etheref
orer
edoxreact
ions.Themor
ereact
ivemet
al(
Magnesi
um)i
sthe
reduci
ngagentwhil
ecopper(
II
)ionsar
etheoxidi
singagent
.
Themor er
eact
iveel
ement
ssuchassodi
um andcal
cium l
oset
hei
rel
ect
ronsr
eadi
l
yandar
est
rong
reduci
ngagent
s.
Thelessreact
ivemet
alssuchasl
eadandcopperl
oseel
ect
ronsl
essr
eadi
l
yandar
eweakr
educi
ng
agents.
Theor
derofr
educi
ngpoweri
s:
Pot
assi
um St
rongestr
educi
ngagent
Sodi
um
Cal
ci
um
Magnesi
um
Al
umi
nium Decr
easi
ngr
educi
ngpower
Zi
nc
I
ron
Lead
Copper
Si
l
ver Weakestr
educi
ngagent
6 Phy
sical
Chemi
str
y

Ot
herDi
spl
acementReact
ions
1)Al
umi
nium di
spl
acescopperf
rom asol
uti
onofcopper
(I
I)i
ons.
3+
Oxi
dat
ionst
ep; 2Al
(s) 2Al (aq)+6e–
Reduct
ionst
ep; 3Cu3+(
aq)+6e– 3Cu(
s)
2+ 3+
2Al
(s)+3Cu (
aq) Al (aq)+3Cu(
s)

2)Coppermet
aldi
spl
acedf
rom asol
uti
onbysi
lv
eri
ons.
Oxi
dat
ionst
ep; Cu(
s) Cu2+(
aq)+2e–
Reduct
ionst
ep; 2Ag+(
aq)+2e– 2Ag(
s)
+
Cu(
s)+2Ag(
aq) Cu2+(
aq)+2Ag(
s)

Oxi
dizi
ngPowerofHal
ogens.
Hal
ogenshav
eat
endencyt
oacceptel
ect
ronsandar
ether
efor
est
rongoxi
disi
ngagent
s.
Amongthehalogensf
luori
neisthest
rongestoxidi
si
ngagent
.Howev
er,
inmostr
eact
ions,
chl
ori
ne
i
sthemostcommonhal ogenusedasanox i
disi
ngagent
.
Themor
ereact
ivehal
ogensoxi
disest
hel
essr
eact
ivehal
ogensandv
icev
ersa.
Forexampl
e,Chl
ori
nedi
spl
acesbr
omi
neandi
odi
nef
rom t
hei
rsol
uti
ons.
– –
Oxi
dat
ionst
ep2Br(
aq) Br(
l)+2e
– –
Reduct
ionst
epCl
2+2e 2Cl(
aq)

Theoxidat
ionnumberofbromineincreasesfrom –1to0whil
ethatofchlor
inedecr
easefr
om 0to
–1.Br
omi neisoxi
disedwhil
echlori
nei sreduced.Chl
ori
nei
stheoxidi
singagentandthebromi
de
i
onisthereduci
ngagent.

Thei
oni
cequat
ionf
ort
hedi
spl
acementofi
odi
nebychl
ori
nei
s:
– –
Cl
2(
g)+2I(aq) 2Cl(aq)+I
2(
s)

Theoxi
dat
ionnumberofi
odineincr
easesfr
om –1t
o0andt
hatofchl
ori
nedecr
easesf
rom 0t
o–1.
I
odinei
soxidi
sedwhil
echl
orineisr
educed.

Theabov ereactionsshow t
hatchl
ori
nehasagr eat
ertendencytoacceptelect
ronsthanboth
bromineandiodine.Chl
ori
net
akesel
ectr
onsf
rom t
hebromideandiodi
deionsf
ormingbromineand
i
odinerespect
ively.
Si
mil
arl
y,br
omineismorereacti
vethaniodineandt akesel
ect
ronsf
rom i
odideions.Bromi
nehasa
hi
ghert
endencyt
oacceptelect
ronsthaniodine.Theioni
cequati
onf
orthereact
ionis:
–
Br
2(l
)+2I(aq) 2Br–(
aq)+I
2(s)

Theoxi
dat
ionnumberofbr
omi
nedecr
easesf
rom 0t
o–1andt
hatofi
odi
nei
ncr
easesf
rom –1t
o
0.
Thegr
eat
ert
het
endencyofanel
ementt
oacceptel
ect
rons,
thehi
gheri
sit
soxi
disi
ngpower
.
Amongt
hehal
ogensconsi
der
ed,
chl
ori
nei
sthest
rongestox
idi
singagent
.
Theor
derofoxi
disi
ngpoweri
s;
 STRY 7
ELECTROCHEMI
Chl
ori
ne
Br
omi
ne Decr
easi
ngoxi
disi
ngpower
I
odi
ne

TheEl
ect
rochemi
calCel
l
Anelectr
ochemi calcel
lisadev
icet
hatgener
atesapot
ent
ialdi
ff
erencebet
weenel
ect
rodesusi
ng
chemicalreact
ions.
El
ect
rochemi
cal
Hal
f-
Cel
l
Anelectr
ochemicalhalf-
cellisformedbydippinga
metalrod(elect
rode)inanaqueoussol uti
onofi ts
i
ons,wheresomeofi tssurfaceatomsloseelect
rons
andgointosolut
ionasions.Thelostel
ect
ronsremain
onthemetalsurf
ace.
Met
alat
omssol
uti
on Met
ali
onsi
nsol
uti
on
n+ –
M(
s) M (
aq)+ne

Themet alroddev el
opsanegati
vechar
geandt his
at
tractstheionsbackagai
n,someoft
heionsaccept
el
ectronsfr
om therodandfor
m at
omsoncemore.
n+ –
M (
aq)+ne M(
s)

Ast henegati
vechargeonthesur f
aceoft
her odbuil
dsup, t
herateatwhichtheionscombinewith
electr
onsincr
easesuntilev
ent ual
l
yiti
sequalt otherateatwhichmet alat
omsl oseelect
ronsto
form posi
ti
veions.Att
hispointanequi
l
ibr
ium isest
abli
shed.Theequat
ionfortheequi
li
brium i
s:

Met
alat
oms Met
ali
ons
n+ –
M(
s) M (
aq)+ne

A pot
ent
ialdi
ff
erencei
scr
eat
edbet
weent
hemet
alr
odandt
heposi
ti
vel
ychar
gedi
onsi
nthe
sol
uti
on.
Theconcent
rat
ionofel
ect
ronsont
hemet
alr
odi
smeasur
edbyaquant
it
ycal
l
edt
heel
ect
rode
pot
enti
al.
Thehalf-
cel
lcanberepresentedas:met al|met alion.Thevert
icalli
nerepresentsthephase
boundar
ywhereapot
ent
ialdif
ferencedev
elops.Forexample,azi
nchalf
-cel
li
srepresentedas;

Zn( Zn2+(
s)| aq)

Thetendencyofmet
alst
ofor
mionswheni
ncont
actwi
tht
hei
rionsdi
ff
ersf
rom onemet
alt
o
anot
her.

TheEl
ect
rochemi
cal
Cel
l
.
Anelect
rochemicalcel
lisobtai
nedwhent hehal
f-
cell
softwodiff
erentmetalsar
econnect
edto
for
m acomplet
ecellsothatt
hediff
erencebet
weenthepot
enti
aloft
hehalfcel
lscanbemeasur
ed.
Theel ectr
odesoft hetwohal f
-cel
lsareconnect edbymetall
icwireswhilethesol
uti
onsare
connectedthroughasal
t-
bri
dge.
Thesal t
-br
idgeisint
heform ofafil
terpapersoakedinasat
uratedsolut
ionofpot
assi
um ni
tr
ate
orsodium nitr
ate.
8 Phy
sical
Chemi
str
y
Thesal
tschosenf
orasal
t-
bri
dgemustnotr
eactwi
thei
theroft
hesal
tsol
uti
onsi
nthehal
fcel
ls.
El
ectronsfl
ow al
ongt hewir
ef r
om the
el
ectrodewit
hahigherconcent
rati
onof
el
ectronstotheelect
rodewit
hal ower
concentr
ati
onofel
ectr
ons.
The difference bet
ween the elect
rode
potenti
alsoft hetwoelect
rodesiscall
ed
the el
ect romoti
veforce (
e.m.f.
)oft he
cel
l.Thee. m.
f.i
smeasuredinvolt
susing
avoltmet er.
Funct
ionsoft
heSal
tBr
idge
Thef
unct
ionsoft
hesal
t-
bri
dgear
e:
 Compl
etet
heci
rcui
tbymaki
ngcont
actbet
weent
het
wosol
uti
ons(
elect
rol
ytes)
.
 Maint
ainsbalanceofchar
gesi
nelect
rol
ytesbypr
ovi
dingi
onst
orepl
acet
hosei
onst
hatar
e
useduporthosethatar
efor
med.
Rel
ati
vet
endencyofmet
alst
oIoni
ze.

Thetendencyofmet al
stofor
mi onswhenincontactwit
ht hei
rionsdif
fer
sfr
om onemetalto
anot
her.Thispr
opertycanbeusedtoobtai
nelect
rochemicalcel
ls,f
orexampl
ethezi
nc-
copper
el
ectr
ochemicalcel
lshownbel
ow.

Whenacopper -copperi
onshalf
-cell
,Cu(s)|Cu2+(
aq)i
sconnect
edt
oazi
nc-
zinci
onshal
f-
cel
l,
Zn(
s)
2+
|Zn ( aq)
,thef
oll
owingobser
vationsaremade:
(
i)Thez
incr
odi
nthezi
nc-
zinci
onshal
f-
cel
lwear
sout
.
(
ii
)Thei ntensi
tyofthebluecolourofcopper(I
I)sulphatesolut
iondecr
easesandr
ed-
brown
deposi
tsappearont
hecopperrodi
nthecopper-
copperionshalf
-cel
l
.
(
ii
i)Av
olt
ageof1.
10Vi
sregi
ster
edbyt
hev
olt
met
er.
Int s)|Zn2+||Cu2+|Cu(
heZn( s)cel
l
,thef
oll
owi
ngequat
ionsr
epr
esentwhathappensi
nthet
wohal
f
cel
l
s:
Zi
ncel
ect
rode(
anode)

Zn(
s) Zn2+(
aq)+2e–

Copperel
ect
rode(
cat
hode)

Cu2+(
aq)+2e– Cu(
s)

I
ntheZn(
s)|Zn2+(
aq)hal
f-
cel
ltheoxi
dat
ionnumberofzi
nci
ncr
easesf
rom 0t
o+2.

I
ntheCu(
s)|Cu2+(
aq)hal
f-
cel
ltheoxi
dat
ionnumberofcopperdecr
easesf
rom +2t
o0.
 STRY 9
ELECTROCHEMI

Theanodeisdefi
nedast heelect
rodeatwhi
choxi
dat
iont
akespl
acewhi
l
ethecat
hodei
sthe
el
ect
rodeatwhi
chreduct
iontakesplace.
Oxi
dat
ionoccur
satt
heZn(
s)|Zn2+(
aq)hal
f-
cel
lwher
eel
ect
ronsar
erel
eased.
Reduct
iont
akespl
aceatt
heCu(
s)|Cu2+(
aq)wher
eel
ect
ronsar
egai
ned.
Thesereact
ionsshowt
hatthezincel
ect
rodehasahi ghertendencyt
ofor
mionst
hant
hecopper
el
ectr
odewhent hemet
alsar
eplacedi
nsolut
ionsoft
heirions.
Thezincelectr
odehasahigheraccumul
ati
onofelect
ronsandismor
enegat
ivecompar
edt
othe
copperel
ectrodewhi
chhasaloweraccumulat
ionofel
ectr
ons.
Ther
efor
e,t
hezi
nct
ermi
nali
srel
ati
vel
ymor
eNEGATI
VEwi
thr
espectt
othecoppert
ermi
nal
.
When thetwo hal
fcel
lsareconnect
ed,el
ect
ronsf
low FROM t
he zi
nc t
ermi
nalt
hrough t
he
connect
ingwi
reTOthecoppert
ermi
nal
.
El
ect
ronsl
ostbyt
hezi
ncel
ect
rodear
egai
nedbyt
hecopper
(I
I)i
ons.
Whent hetwoi
oni
chal
fequat
ionsar
ecombi
ned,t
hei
oni
cequat
ionf
ort
heel
ect
rochemi
calcel
lis
obt
ained.
2+ 2+
Zn (
s)+Cu(
aq) Zn (
aq)+Cu(
s)
Theionicequat
ionandt
hee.
m.f
.oft
heel
ect
rochemi
calcel
lcanbesummedupi
nwhati
scal
l
eda
cel
lnotati
on.
2+ 2+
Zn(s)|Zn2 (aq)||Cu (
aq)|Cu(s) E=+1.10V
Thesi
ngl
ev er
ti
calli
ner epresentsphaseboundari
esinthehal
f-
cel
l
swhil
ethet
wov
ert
icalpar
all
el
l
inesr
epr
esentthesalt
-bridge.
Thehal
f-
cel
linwhichel
ectr
onsar
ereleased(oxi
dat
iont
akespl
ace)i
sal
way
sont
hel
eft
–hand
2+
si
deoft
hecelldi
agram,
i.
e.,
Zn(
s)|Zn ( aq)
.

El
ect
ronsf
lowFROM t
hel
efthandhal
f-
cel
lTOt
her
ighthandhal
f-
cel
l
.

St
andar
dEl
ect
rodePot
ent
ial
s

Thest
andardel
ect
rodepotent
ialofanyelement|el
ementionshal
f-
cel
list
akenast
hedi
ff
erence
bet
weenit
spotent
ialandt
hatofhydrogen|hydr
ogenionshal
f-
cel
l.
Thechosenstandardel
ect
rodeishydrogenandisusual
l
yr ef
err
edtoasthest
andar
dhy
drogenhal
f
cel
l.Bei
ngtherefer
enceel
ectr
ode,i
tisassignedanel
ectr
odepotent
ial0.
00V.
Thest
andar
dcondi
ti
onsf
ormeasur
ingel
ect
rodepot
ent
ialar
e:
(
i) Temper
atur
eof25°
C.
(
ii
)Al
lsol
uti
onshav
eaconcent
rat
ionof1mol
eperl
i
tre(
1M)
.
(
ii
i)Pr
essur
eof1at
mospher
e.
Pl
ati
nisedplatinum el
ect
rodei
susedast
heel
ect
rodewhent
hehal
f-
cel
ldoesnoti
ncl
udeamet
al,
+
e.
g.,
H2(g)|H( aq).
Thepl
ati
nisedpl
ati
num el
ect
rodehast
hreef
unct
ions:
(
i)I
tact
sasani
ner
tmet
alconnect
iont
ot H+(
heH| aq)sy
stem.
(
ii
)Itpr
ovi
desasur
facear
eaonwhi
chdi
ssoci
ati
onofhy
drogenmol
ecul
escant
akepl
ace,
i.
e.,

g)→ 2H+(
H2( aq)+2e–

(
ii
i)I
tser
vesasanel
ect
ri
cal
conduct
ort
otheext
ernal
cir
cui
t.
10 Phy
sical
Chemi
str
y
Thehy drogenel ectr
odeconsi st
sofani nertplat
inum
elect
rode whi ch isi mmersed in a 1.0 mole perli
tre
+
solut
ionofhy drogeni ons,
H Hy drogengasisbubbledon
the platinum electr
ode whi ch i
s dipped i
n a sol
ution
containing1M hy drogenions.

½H2(
g) H+(
aq)+e–

Thest
andar
dhy
drogenhal
f-
cel
li
spr
esent
edas:

Pt
(s)
,H2( H+(
g)| aq)
.

Whil
ethest
andar
del
ect
rodepot
ent
ial
,Ef
ort
hisr
efer
encehal
f-
cel
lwhi
chi
szer
ocanber
epr
esent
ed
as:

½H2(
g) H+(
aq)+e– E=0.
00V
Thestandar
del ect
rodepot ent
ialdi
fferencei
sthepotent
ialdi
ff
erencef
oracellcompr
isi
nga
par
ti
cularel
ementi n cont
actwi t
h onemol arsol
uti
on ofit
sionsand thest
andar
d hy
drogen
θ
el
ectr
ode.I
tisdenotedbythesymbol,E.
I
fanel ementhasagr eatert endencyt o
l
oseel ect
ronsthanhydrogen,theelectr
ode
potenti
alofi t
s half
-cel
lis negat i
ve with
respecttothehydr
ogenhalf-cel
l.(e.
g.,zi
nc)
Theioni
chal
fequat
ionsforther
eact
ions
occur
ri
ngatt
heel
ect
rodeare:

Zn(
s) aq)+2e– Eθ=0.
Zn2+( 76V

2H+(
aq)+2e– g)Eθ=0.
H2( 00V

Theov
eral
li
oni
cequat
ioni
s:

s)+2H+(
Zn( aq) Zn2+( g)Eθ=–0.
aq)+H2( 76V
– +
Simil
arl
y,i
faF|F( aq)hal
f-
cel
lisconnect
ed wi t
ht hePt(
s)H(
g)|H (
aq)hal
f-
cel
l
,thee.
m.f
.
regi
ster
edfort
hecel
li
s+2.87V.Thehal
f-
cel
lreact
ionisasf
oll
ows:

g)+2e–
F2( 2F–(
aq)

H2(
g) 2H+(
aq)+2e–

Theov
eral
li
oni
cequat
ionbei
ng:

H2(
g)+F2(
g) 2F–( aq)Eθ=+2.
aq)+2H+( 87V

Ontheotherhand,ift
hetendencyofanelect
rodetoloseel
ect
ronsisl
owerthanthehydrogen
el
ectr
ode,t
heelect
rodeisposi
ti
vewit
hrespecttohy
drogenel
ect
rodeandit
spotent
iali
sposit
ive,
e.
g.,
copper
.
Standar
delect
rodepotent
ialsar
esometi
mesr
efer
redt
oasst
andar
dreduct
ionpot
ent
ialbecause
theyrel
atet
othereduct
ionreact
ions.
Thet abl
eofst andar
del ect
rodepotent i
alsforsomeelementsisarr
angedsothatt
hest
rongest
oxi
disingagent,fl
uori
ne,whi chhast hemostposi t
iveval
uef orE°i
satthetopofthel
i
st.The
+
weakestoxidi
singagent,
lit
hium i
ons,Li, wi
ththemostnegat
iveval
ueofE°i
satt
hebott
om.
Si
mil
arl
y,f
luor
idei
onsi
stheweakestr
educi
ngagentwhi
l
eli
thi
um i
sthest
rongestr
educi
ngagent
.
 STRY 11
ELECTROCHEMI

UsesofSt
andar
dEl
ect
rodePot
ent
ial
s
St
andar
del
ect
rodepot
ent
ial
sar
eusedi
n:
(
i) Compar
ingt
heoxi
disi
ngandr
educi
ngpower
sofsubst
ances.
(
ii
) Det
ermi
ningt
hee.
m.f
.ofacel
l
.
(
ii
i) Pr
edi
cti
ngwhet
herornotar
eact
ionwi
l
ltakepl
ace.

Compar
ingOxi
disi
ngandReduci
ngPower
Li
thium withEθ =– 3.
04V hast hehighestt
endencytoloseel ectronsandt her
efor
ei ti
st he
θ
str
ongestreduci
ngagent.Themorenegativ
etheE valuet
hegr eaterthereduci
ngpower .Li
thi
um
hast hel
eastt
endencyt
oacceptel
ect
ronshenceiti
stheweakestoxidisingagent
.

Fl
uori
newithEθ of+2. 87V hast hehighesttendencyt oacceptel ectr
onsandt herefor
et he
st
rongestoxidi
sing agent
.The mor e posi
ti
vet he Eθ val
ue,the greaterthe oxi
disi
ng power.
Conver
sel
y,f
luori
neistheweakestr
educingagentsinceithastheleastt
endencytoloseelectr
ons.

Usi
ngSt
andar
dEl
ect
rodePot
ent
ial
stocal
cul
atet
hee.
m.fofaCel
l
Thee. m.fofacelli
sobt
ainedbychangi
ngthesi
gnoftheelect
rodepot
enti
alofthehalf
-cel
lthat
undergoesoxidat
ionandthenaddi
ngt otheel
ectr
odepotenti
alofthehal
f-cel
lthatunder
goes
reducti
on.
Eθcell=Ereduction–Eoxidation
Ereductioni
stheel
ect
rodepot
ent
ial
oft
hehal
f-
cel
lthatunder
goesr
educt
ion.
Eoxidationi
stheel
ect
rodepot
ent
ial
oft
hehal
f-
cel
lthatunder
goesoxi
dat
ion.
12 Phy
sical
Chemi
str
y
Exampl
e1
Ther
educt
ionpot
ent
ial
sofMg(
s)|Mg2+( s)|Zn2+(
aq)andZn( aq)hal
f-
cel
lsar
e:

Mg2+(
aq)+2e– s)Eθ=–2.
Mg( 37V

Zn2+(
aq)+2e– s)Eθ=–0.
Zn( 76V

Usi
ngt
heel
ect
rodepot
ent
ial
s,answert
hef
oll
owi
ngquest
ions.
(
i) Wr
it
eani
oni
cequat
ionf
oracel
lmadebycombi
ningt
het
wohal
fcel
l
s.
(
ii
)Cal
cul
atet
hee.
m.f
.oft
hecel
lfor
medi
npar
t(i
).
(
ii
i)Wr
it
ethecel
lnot
ati
onf
ort
hecel
l.
Sol
uti
on
(
i) Sincetheel
ectr
odepot ent
ialofmagnesium i
smorenegativ
e,magnesium isthestr
onger
reduci
ngagent.Zi
ncunder goesreducti
onwhi l
emagnesi
um isoxi
dised.ThesignoftheEθ
valueofMgchangesf rom negat
ivetoposit
ive.
2+ –
Mg(s) Mg ( aq)+2e +2.37V
2+
Zn ( aq)+2e Zn(
s) –0.
76V
Mg(s)+Zn2+(
aq) Mg2+(aq)+Zn(s) +1.61V
(
ii
) Thee.m.f
.ofthecelli
sobtai
nedbychangi ngthesignoftheelect
rodepot
ent
ialof
magnesi
um andaddingthem,i.
e.+2.37V+( –0.76)=+1. 61V.
(
ii
i) Mg(s)|Mg2+(
aq)||Zn2+(
aq)|Zn(s)Eθcell=+1.61V

Exampl
e2
Cal
cul
atet
hee.
m.f
.fort
heel
ect
rochemi
calcel
lrepr
esent
edbel
ow:
3+ 2+
Al
(s)|Al(
aq)||Zn (
aq)|Zn(
s)
Gi
vent
hat
:
3+ –
Al(
aq)+3e Al
(s) E°=–1.
66V
2+ –
Zn (
aq)+2e Zn(
s) E°=–0.
76V

Sol
uti
on
3+
Al
(s) Al (aq)+3e– +0.
66V

Zn2+(
aq)+2e– Zn(
s) –0.
76V

Tocombi net hetwohal fequat ions,thenumberofel ect

ronsshoul
dbeequal.Todot hi
s,we
mul ti
plythefi
rstequat ionby2andt hesecondequat
ionby3.Theelect
rodepot
enti
alsremai
nthe
same.Thi sisbecauset hevol t
agedoesnotdependont henumberofelectr
onsf
lowi
ng.
3+
2A( s) 2Al (aq)+6e– +1.66V
2+ –
3Zn ( aq)+6e 3Zn(s) –0.76V
2+ 3+
2Al (s)+3Zn ( aq) 2Al( aq)+3Zn( s) +0.90V
Or
Eθcell =EθR.H.S–EθL.H.S
=–0. 76V–( –1.66V)
=–0. 76V+1. 66V
=+0. 90V

Exampl
e3
 STRY 13
ELECTROCHEMI
Uset
hecel
lrepr
esent
ati
onbel
owt
oanswert
hequest
iont
hatf
oll
ows
Cu(
s)|Cu2+(
aq)||Ag+(
aq)||
Ag(
s) Eθcell=+0.
46V
Gi
vent
hatt
heEv
al orAg+(
uef aq)|Ag(
s)i
s+0.
80V,
cal
cul
at heEθv
et aluef
orCu( Cu2+(
s)| aq)
.

Sol
uti
on
EθCell=EθR.H.S–EθL.H.S
Subst it
ut ing
0.46V=0. 180V–EL.H.S
0.46V–0. 80V=–EL.H.S
–0. 34=–EL.H.S
θ
EL.H.S=+0. 34V

Exampl
e4
Usethestandar
delectr
odepotent
ial
sforelementsA,B,C,DandEgiv
enbel
ow t
oanswert
he
quest
ionst
hatfol
low.Thel
ett
ersdonotrepr
esentact
ualsy
mbol
sofel
ement
s.
Eθ(
vol
ts)
2+ –
A(
aq)+2e A(
s) –2.
37
2+ –
B(
aq)+2e B(
s) –0.
76
+ –
C(
aq)+e ½C2(
g) 0.
00
2+
D(
aq)+2e D2(
s) +0.
34
– –
½E2(
g)+e E(
aq) +1.
36

(
i) Whati
stheEθv
alueoft
hest
rongestoxi
disi
ngagent
?Expl
ain.
Answer
:+1.
36mostposi
ti
ve.
(
ii
)Whi chtwooft
heabov eel
ement
swoul
dpr
oducet
hel
argeste.
m.forpot
ent
ialdi
ff
erencei
nan
el
ectr
ochemi
calcel
lExpl
ain.
θ θ
:AandE,
Answer theel
ement
swi
tht
hemostposi
ti
veE andt
hemostnegat
iveE.
(
ii
i)Whatwoul
dbet
hei
nit
ialpot
ent
ialdi
ff
erenceoft
hecel
lchoseni
n(i
i)abov
e?
Answer
:
E.
m.fofcel
l=Ereduction–Roxidation
=1.
36–( –2.
37)
=1.
36V+2. 37V
=+3. 73V
(
vi)Wr
it
ethecel
lrepr
esent
ati
onf
ort
heel
ect
rochemi
cal
cel
lfor
med.
Answer
: s)|A2+(
A( g)|E–(
aq)||E2( aq)
,PtEθ=3.
73V

Usi
ngst
andar
dEl
ect
rodepot
ent
ialt
opr
edi
cti
taReduct
ionwi
llt
akepl
ace
Pr
evi
ousl
yitwasest
abl
i
shedt educesCu2+
hatZnr

Zn(
s) Zn2+(
aq)+2e +0.
76V
2+ –
Cu +2e Cu(
s) +0.
34V
2+ 2+
Zn(
s)+Cu (
aq) Zn (
aq)+Cu(
s) +1.
10V
Thecellpotent
ialore.
m.f
.,+1.
10Vi
sposi
ti
veshowi
ngt
her
eact
iont
akespl
ace.Thee.
m.f
.fort
he
rev
ersereacti
on:
14 Phy
sical
Chemi
str
y
s)+Zn2+(
Cu( aq) Cu2+(
aq)+Zn( sEθ=–1.
s)i 10V
Thenegat
ivevaluei
mpliesthatthereact
ioni
sunl
i
kel
yt ooccur.I
ngeneralr
eact
ionswi
thanov
eral
l
posi
ti
vee.
m. fcantakeplace;whil
ethosewit
hnegat
ive:e.
m.f.cannot
.

Exampl
e
Pr
edi
ctwhet
herar
eact
ionwi
lloccurbet
weeni
odi
neandchl
ori
dei
ons.

aq)+2e– aq)Eθ=+1.
–
I
2( 2I ( 36V

aq)2e– aq)Eθ=+1.
–
Cl
2( 2Cl( 51V

Sol
uti
on
Addi
ngthei
oni
chal
fequat
ions;
Iaq)+2e–
2(
–
2I(aq) Eθ=+1.
36V
2Cl
(aq) Cl
2(
aq)+2e Eθ=–1.
51V
– –
I
2(
aq)+2Cl(aq) 2I(aq)+Cl
2(
g) Eθ=–0.
15V
Theover
allEθ oft
hecel
lisnegat
ive.Ther
efor
e,i
odi
necannotdi
spl
acechl
ori
nef
rom achl
ori
de
sol
uti
on.

UsesofEl
ect
rochemi
cal
Cel
l
s
El
ect
rochemi
cal
cel
l
sar
eusedasasour
ceofener
gy.
Dr
yCel
ls
Drycell
sareused in awider angeofel ect
ri
calappli
ancessuch asr adi
os,watches,cl
ocks,
fl
ashl
i
ghtsandelect
ri
cbell
s.Thedr ycell
sarecheapandconv eni
enttousebecausetheycontai
n
t
heelect
rol
ytei
nform ofapast
eratherthanali
qui
dtheref
orecannotspi
ll
orleak.
Anexampl
eofadr
ycel
li
stheLe’
Clanchecel
lshownbel
ow.
I
tconsist
sofazi nccanwhichfor
msthe
negat
ivetermi
nalandagr
aphit
erodwhi
ch
i
sthepositi
vet
erminal
.
Thegr aphiterodi
ssurroundedbyapast eof
ammoni um chlor
ideandzi ncchlori
de,and
powder edmanganese( IV)oxidemi xedwi t
h
carbon.Thepowderi ncreasesthesur f
ace
areaoft hepositi
veter
mi nal.
Thef unctionofmanganese( I
V)oxideistooxidi
sethehydr
ogenpr
oducedattheelectr
odetowater
thusprev enti
nganybubbl esfr
om coatingthecar
bonter
minalwhi
chwouldreduceitseff
ici
ency
.
Att
henegat
ivet
ermi
nal
:

Zn(
s) Zn2+(
aq)+2e–

Att
heposi
ti
vet
ermi
nal
,ammoni
um i
onsar
econv
ert
edt
oammoni
aandhy
drogengases

2NH4+(
aq)+2e– 2NH3(
g)+H2(
g)

Thegasesproduceddonotescapebutarei
mmediat
elyusedupi
notherr
eact
ions.Thehydr
ogen
i
soxidi
sedtowat erbyt
hemanganese(I
V)oxi
de.Ammoniafor
msacomplexwi
ththezincchl
ori
de
i
nthepaste.
Asimpl
edrycel
l canproduceapot
enti
alof1.5V.
Dryammonium chlor
idedoesnotconductanelect
ri
ccur
renthenceapast
e,whi
chi
sanel
ect
rol
yte
i
sused.
Suchacel
liscal
l
edapr
imar
ycel
lbecauseoncet
hecel
lisusedt
osuppl
yener
gyt
hechemi
cal
s
 STRY 15
ELECTROCHEMI
ar
eusedupandt
her
efor
ethecel
lhast
obedi
scar
ded(
itcannotber
echar
ged)
.

Somecell
scanber eusedaf
terbei
ngrechar
ged.Thesear
ecal
l
edsecondar
ycel
l
s.Thel
eadaci
d
accumul
atori
sthemostcommonsecondarycel
ls.
Accumul
ator
s
Themai nfeatur
esofal ead-aci
daccumul
atorar
etheleadplat
ewhi chisthenegat
iveter
minaland
thelead(VI)oxi
deplatewhichistheposi
ti
veter
minal
.Bothoftheseelect
rodesdi
pintoanaqueous
soluti
onofsulphur
ic(
VI)acid.
Att
henegat
ivet
ermi
nal
,l
eadat
omsl
oseel
ect
ronst
ofor
mlead(
II
)ions.

Pb(
s) Pb2+(
aq)+2e–

Attheposi
ti
vet
ermi
nal
,lead(
IV)oxi
der
eact
swi
thhy
drogeni
onsi
nsul
phur
ic(
VI)aci
dfor
ming
l
ead(I
I)I
ons:
+ – 2+
PbO2(
s)+4H (
aq)+2e Pb (
aq)+2H2O(
l)

Thel
ead(I
I)i
onsformedreactinstant
lywi
tht
hesul
phat
eionst
ofor
mlead(
II
)sul
phat
ewhi
chi
s
i
nsol
ubl
eandadher
estotheelectr
odes.
2+ 2–
Pb (
aq)+SO4 (
aq) PbSO4(
s)

Thenetr
eact
iont
hatt
akespl
acei
s:

As the batt
ery di
schar
ges,lead and l
ead(
IV)oxi
de ar
e depl
eted and the concentrat
ion of
sulphur
ic(
VI)aci
ddecreases.
Sincethedensit
yoft heaqueoussoluti
ondependsontheconcentr
ationofsul phuri
c(VI
)acid,
measurementofi t
sdensit
ycanbeusedasmeansoftel
li
nghowfarthebatteryi
sdi schar
ged.
Duri
ngrechargi
ngoft
hebat
ter
y,t
heel
ect
roder
eact
ionsshownar
erev
ersedsoast
orest
orei
ts
or
igi
nal
reactant
s:

FuelCel
ls
Fuelcell
sar eel
ectr
ochemicalcel
l
swhich conver
tthechemi
calener
gyofaf
ueldi
rect
lyt
o
el
ectr
icalener
gysuchasthehydr
ogenox
ygencell
shownbel
ow.

At the negat
ive t
erminal
,hydrogen reacts wit
h
hydroxi
de i
ons toform water and el
ectrons ar
e
rel
eased.

g)+4OH–(
2H2( aq) 4H2O(
l)+4e–

Attheposit
iveter
minal
,oxygen and wat
eracqui
re
el
ectr
onst
oform hy
droxi
dei
ons.

O2(
g)+H2O(
l)+4e–(
aq) 4OH(
aq)

Theov
eral
lreact
ioni
nthehy
drogen|
oxy
gencel
li
s

2H2(
g)+O2(
g) 2H2O(
l)

Thecellgoesonpr
oduci
ngelect
ri
ci
tyasl
ongashy
drogenandox
ygenar
efedi
ntoi
t,sot
hati
tdoes
notbecomeexhaustedl
ikeapri
marycel
l
.
16 Phy
sical
Chemi
str
y
Thef
uel
cel
lunl
i
keasecondar
ycel
ldoesnotst
oreener
gy.
Theel
ectr
ode,othert
hancompl
eti
ngt
heci
rcui
tal
socat
aly
sest
her
eact
ionswhi
chi
ncr
easet
he
out
putofthecel
l.

El
ect
rol
ysi
s
Elect
rol
ysi
sist
heprocessi
nwhi
chel
ect
ri
calener
gyi
susedt
ocausenon-
spont
aneouschemi
cal
react
ionst
ooccur
.
I
ntheser
eact
ions,
thesubst
anceunder
goeschemi
cal
decomposi
ti
on.

Pr
efer
ent
ial
Dischar
geofI
onsDur
ingEl
ect
rol
ysi
s
I
nt heaqueoussoluti
on,t
herearemor ethantwoionssi
ncewateral
soionises.Duri
ngelect
roly
sis,
onlyoneoftheanionsandoneoft hecationscanbedi
schar
ged.Pref
erenti
aldischar
getherefor
e
takespl
ace,accor
dingtothefact
orsdiscussedbel
ow.

Fact
orsAf
fect
ingPr
efer
ent
ialDi
schar
geDur
ingEl
ect
rol
ysi
s
1.Theconcent
rat
ionoft
heel
ect
rol
yte
Acat
ionorani
onwhoseconcent
rat
ioni
shi
ghi
spr
efer
ent
ial
l
ydi
schar
gedi
fthei
onsar
ecl
osei
n
t
heel
ectr
ochemical
ser
ies.
2.Thepr
oductobt
ainedatt
heel
ect
rodedependsont
henat
ureofel
ect
rodeused.
3.Posi
ti
oni
ntheEl
ect
rochemi
calSer
ies
The ease ofreducti
on ofcati
ons and oxi
dation ani
ons depends on t
hei
rpositi
on inthe
el
ect
rochemicalseri
es.Thecat
ionshighint
heser i
esrequi
remoreenergytobereduced.Ani
ons
hi
ghintheseri
esrequiremoreenergytobeoxi
dised.
 STRY 17
ELECTROCHEMI
1. El
ect
rol
ysi
sofdi
lut
esodi
um chl
ori
de

Sodi
um chl or
idesol
utioncontai
nssodium
+ –
i
ons (Na)and chl or
ide i
ons (Cl)f r
om
+
sodi
um chl or
ide,hydr
ogen ions (
H )and
hydr
oxi
dei ons(OH–)fr
om water.

Whenanel ectr
iccurr
entispassedthrough
–
the solut
ion, chl
ori
de i ons (Cl) and
hydr
oxideions(OH–)migr
atetotheanode.
Hy dr
oxidei
ons(Eθ=+0.04V)hav
eagreat
er
tendencytoloseel
ect
ronscomparedt
othe
chlori
dei Eθ=+1.
ons.( 36V).

React
ionatAnode
– –
4OH (
aq) 4OH(
aq)+4e Theanionwit
hal owEθ
4OH(
aq) 2H2O(
l)+O2(
g) val
ueispref
erenti
all
y
di
schar
ged.
Ov
eral
l;
– –
4OH (
aq) 2H2O(
l)+O2(
g)+4e

Sodi
um ions(Na+)andhydrogeni
ons(H+)migr
atet
othecat
hodebuthydr
ogenions(Eθ=0.
00volt
s)
arepr
eferent
ial
lydischar
gedbecausetheyhaveagreat
ert
endencyt
ogainelect
ronsthansodi
um
θ
i
ons(E =–2. 71volts)
.

React
ionsatCat
hode
+ Thecat
ionswithahigher
4H (
aq)+4e 4H(
aq) θ
E hasahighertendency
4H(
aq) 2H2(
g) t
ogainelect
rons.

Ov
eral
l;

4H+(
aq)+4e– 2H2(
g)
Elect
roly
sisofdil
utesodium chl
ori
deevolv
esoxygengasattheanodeandhy dr
ogengasatthe
cathode.Thisi s essent
ial
l
yt he el
ect
rol
ysi
s ofwatersi
nce oxygen and hy
drogen ar
ethe
consti
tuentsofwater
.

2. El
ect
rol
ysi
sofconcent
rat
edsodi
um chl
ori
desol
uti
on(
Bri
ne)
Bri
neisconcent
ratedsodi
um chlor
idesolut
ion.
Thesol
uti
onther
eforecont
ainst
hesamei onsas
di
lut
esodi
um chl
ori
de.
Whenanel ectr
iccur r
entispassedthroughbrine,
–
chl
oridei
ons(Cl)andhy droxi
deions
( –
OH )migrat
etot heanode.Thechlori
deions( Eθ
= + 1.36 volt
s)ar e pref
erent
ial
ly di
scharged
becauseoftheirrelat
ivel
yhighconcentr
ati
ons.
18 Phy
sical
Chemi
str
y
React
ionatAnode
–
2Cl(aq) 2Cl
(g)+2e–

2Cl
(g) Cl
2(
g)

Ov
eral
l;
–
2Cl(aq) Cl
2(g)+2e–

Sodi
um i Na+)andhy
ons( drogeni H+)mi
ons( grat
etot
hecat
hode.
Atthecathodes,sodi
um ionsarenotpref
erent
iall
ydischar
gedinspi
teoft
hei
rhighconcent
rati
on.
Thisi
sbecauset hetendencyofhydr
ogenions( Eθ =0.
000vol
ts)t
ogainel
ect
ronsismuchhi gher
thanthatofsodium i
ons(Eθ=–2.71vol
ts)
.
Ther
efor
e,hy
drogeni
onsar
epr
efer
ent
ial
l
ydi
schar
ged.

React
ionsatCat
hode
+ –
2H (
aq)+2e 2H(
g)

2H(
g) H2(
g)

Ov
eral
l
;
+ –
2H (
aq)+2e H2(
g)
–
Thedischargeofhydrogenionsl
eadstoanincreaseinhy
droxi
de(OH )i
onsconcent
rat
ionandthe
soluti
onbecomesal kali
ne.
Ast heelectr
oly
sisprocesscont
inues,t
heconcentr
ati
onofchl
ori
deionsdecr
easesandevent
uall
y
hydroxidei
onsar eoxidi
sedtowaterandoxygengas.

3. El
ect
rol
ysi
sofdi
lut
esul
phur
ic(
VI)aci
d.

Dil
utesul phuri
c(VI
)aci
dcontai
nssulphat
e
2– – +
(SO4 ) ,
hy dr
oxide(OH )andhy
drogen(H)
i
ons.
When an el ect
ric current i
s passed
thr
ough t he dil
ute acid,sulphat
e and
hydroxi
dei onsmigratetotheanodewhil
e
thehydrogenionsmi grat
etothecat
hode.

Reactionatanode
Thehy droxi
dei Eθ =+0.
ons( 40volt
s)areprefer
ent
ial
lydi
schargedbecauset
heyhav
eagr
eat
er
tendencytoloseel
ectr
onst
hansulphat
eions(Eθ=+2.01vol
ts)
.

4OH–(
aq) aq)+e–
4OH(

4OH(
aq) 2H2O(
l)+O2(
g)

Ov
eral
l
;

4OH–(
aq) 2H2O(
l g)+4e–
)+O2(

React
ionatCat
hode

4H+(
aq)+4e– 4H(
g)
 STRY 19
ELECTROCHEMI
4H(
g) 2H2(
g)

Ov
eral
l;

4H+(
aq)+4e– 2H2(
g)
Thef ourelectr
onslostbyhy dr
ox i
deionst ofor
m onemol eofoxygenmol ecul
esar
egainedbythe
fourhy drogenionst of or
mt womol esofhy drogenmol ecul
es.Forev er
ymoleofox ygengas
producedatt heanodet womolesofhy drogenareformedatthecathode.
Thev olumeofhy drogenisther
eforetwicethatofoxygen.
Theamountofwat erint heelectr
olyt
edecr easesast heelect
rolysi
sprocesscont
inues.Thi
s
causesani ncreaseintheconcentrat
ionoft heaci
d.

4. El
ect
rol
ysi
sofaqueousmagnesi
um sul
phat
e
The i ons present i
n magnesi um sulphate
soluti
onaremagnesi Mg2+)
um ( ,sulphat
e(SO42–)
,
+ –
hydrogen(H )andhydr
oxide(
OH ) .
Whenanelectr
iccurr
entispassedthroughthe
sol
uti
on,hy
droxi
deions(Eθ =+0.40v ol
ts)and
sul
phatei
ons(Eθ =+2.01volt
s)migratetothe
anode.
Hydroxide i
ons are prefer
ential
ly di
schar
ged
because of thei
r greater tendency tolose
el
ectrons.

React
ionatAnode
– –
4OH (
aq) 4OH(
aq)+4e

4OH(
aq) 2H2O(
l)+O2(
g)

Ov
eral
l;
–
4OH (
aq) 2H2O(
l)+O2(
g)+4e

Bot
hmagnesi Eθ=–2.
um ( 38v
olt
s)andhy
drogeni Eθ=0.
ons( 00v
olt
s)mi
grat
etot
hecat
hode.
Hy
drogeni
onsar
epr
efer
ent
ial
l
ydi
schar
gedbecauseoft
hei
rgr
eat
ert
endencyt
ogai
nel
ect
rons.
React
ionsatCat
hode

4H+(
aq)+4e– 4H(
g)

4H(
g) 2H2(
g)

Ov
eral
l;

4H+(
aq)+4e– 2H2(
g)
Iti
sobser
vedt
hatthevol
umeofoxy gengaspr
oducedatt
heanodeandhy
drogengasatt
he
cat
hodear
eint
herati
osof1:
2respect
ivel
y.

5. El
ect
rol
ysi
sofcopper
(I
I)sul
phat
esol
uti
onusi
ngdi
ff
erentel
ect
rodes.

(
a)Usi
ngi
ner
tel
ect
rodes(
car
bonorpl
ati
num)
Copper
(I
I)sul
phat
esolut
ioncont
ainscopper
(I
I Cu2+)
)( ,Sul
phat
e(SO42–)
,hy
drogeni H+)
ons( ,and
hydr
oxi
de(OH–)i
ons.
20 Phy
sical
Chemi
str
y
When t he sol
uti
on is el ectr
olysed using carbon or
plat
inum el
ectr
odes,sulphateions( Eθ=+2.01v ol
ts)and
θ
hydroxi
deions( E= 0.20 v olt
s)mi gr
atetot heanode
θ
whil
et hecopper(
II
)(E=+0. 34v olt
s)andhy drogenions
(Eθ=0.00volt
s)migratetot hecathode.

React
ionsatAnode
Thehy dr
oxi
de ionshave a gr
eatertendencytolose
el
ectr
onsandtheref
orear
eprefer
enti
all
ydischar
ged.

4OH–(
aq) aq)+4e–
4OH(

4OH(
aq) 2H2O(
l)+O2(
g)

Ov
eral
l;

4OH(
aq) 2H2O(
l g)+4e–
)+O2(

React
ionsatCat
hode
Thecopper(
II)i
onshavegreat
ertendencytogai
nelect
ronst
hatthehy
drogeni
onsandisther
efor
e
pref
erent
ial
lydi
schar
ged.Theatomsar edeposi
tedont
hecathodeasr
ed-br
owncoat
ing.
Asar
esul
t,t
hemassoft
hecat
hodei
ncr
easeswhi
l
ethatoft
heanoder
emai
nst
hesame.
2+
Cu (
aq)+2e Cu(
s)
Theconcentr
ati
onofcopper(
II
)ionsinsolut
iondecreasesandthebluecol
ourofthecopper
(I
I)
sul
phat
esoluti
onbecomespal
eandf i
nall
ycol
ourl
ess.
Hydr
ogenionsaccumul
atei
nthesoluti
onsandtheref
orethesol
uti
onbecomesaci
dic.

(
b)Usi
ngcopperel
ect
rodes
Whencopperel
ectr
odesareusedintheelectr
olysi
sofcopper
(I
I)sul
phat
esol
uti
on,
themassoft
he
anodedecr
eases,
whil
ethatofthecathodeincreases.
Sul
phateandhydr
oxi
deionsmigrat
etotheanode,butnoneoft
hem i
sdi
schar
ged;i
nst
eadt
he
copperanodei
sgr
adual
l
yoxidi
sedandgoesi
ntosol
uti
on.

Cu(
s) Cu2+(
aq)+2e

Thi
sexplai
nsthelossi
nmassoft
heanode.Lessener
gyi
sneededf
ort
hecopperanodet
olose
el
ect
ronsthanhy
droxi
deions.
Hydr
ogenandcopper(I
I)i
onsmi gr
atetothecathodewherecopper
(I
I)i
onsar
epr
efer
ent
ial
l
y
di
schar
gedbecauset
heyhavegr
eatert
endencyt
oacceptel
ect
rons.

Cu2+(
aq)+2e Cu(
s)

Thecat
hodei
sthuscoat
edwi
thar
ed-
browndeposi
tofcoppermet
al.
Theamountofcopperoxidi
sedattheanodeisequaltot
heamountofcopperdeposi
tedonthe
cat
hodeandtheref
oretheconcent
rati
onofcopper
(I
I)i
onsint
hesol
uti
onremainsthesame.The
col
ouroft
hebluesolut
iondoesnotfade.
Carbonorpl
ati
num el
ect
rodesall
owpassageofanel
ect
ri
ccur
renti
ntoandoutoft
heel
ect
rol
yte
wit
houtweari
ngoutsuchelect
rodes.
 STRY 21
ELECTROCHEMI
Summar
yofEl
ect
rol
ysi
s
1.El
ect
rol
yte:
dil
utesodi
um chl
ori
de
I
ons Pr
esent
Cat
ions Ani
ons
+ + –
Sodi
um,
Na(
aq)andhy
drogenH (
aq)i
ons. Chl
ori
deCl(
aq)andhy
droxdeOH–(
i aq)i
ons.
Hydrogen,H+( aq)ions di
schar
ged atthe Hydroxi OH–)
de ( (
aq)discharged atthe anode,
cat
hode, becausesodium i
sabovehy
drogen becausehydrogen i
onsr equi
red l
essenergyto
–
i
nelectro-chemical
seri
es. di
scharget
hanchlori
deCl( aq)i
ons.
Hy
drogengasev
olv
ed. Oxy
gengasev
olv
ed.

2.El
ect
rol
yte:
Bri
ne(
Concent
rat
edSodi
um chl
ori
de)
I
ons Pr
esent
Cat
ions Ani
ons
+ + – –
Sodi
um,
Na(
aq)andhy
drogenH (
aq)i
ons. Chl
ori
deCl(
aq)andhy
droxi
deOH (
aq)i
ons
+ –
Hydrogen,H ( aq) i
on discharged atthe Hydroxi
de (OH )(
aq)discharged att he anode,
cat
hode, becausesodium isabovehydr
ogen becausehydrogenionsrequiredl essener
gy.To
–
i
nelectro-chemical
series. di
scharget
hanchlori
deCl( aq)ions.
Hy
drogengasev
olv
ed. Chl
ori
negasev
olv
ed.

3.El
ect
rol
yte:
dil
utesul
phur
icaci
d
I
ons Pr
esent
Cat
ions Ani
ons
+ 2– –
Hy
drogen,
H(aq) Sul
phat
e,SO (
4aq)andhy
droxi
de,
OH (
aq)
+ –
Hy dr
ogen,H (aq)i
onsdi
schar
gedatthe Hydroxi
de (OH )
(aq) discharged at the anode,
cathode,becausenoothercati
onsare because hydr
oxyli ons requir
e less ener
gy to
present. di
scharget
hansulphatei
ons.
Hy
drogengasev
olv
ed. Ox
ygengasev
olv
ed.

4.El
ect
rol
yte:
Magnesi
um sul
phat
e
I
ons Pr
esent
Cat
ions Ani
ons
2+ 2–
Magnesi
um,
Mg (
aq)andhy
drogen,
H+(
aq) Sul
phat
e,SO (
aq)andHy
4 droxdeOH–(
i aq)
i
ons. i
ons.
Hydrogen i
ons dischar
ges at t
he cat
hode, Hydr
oxi
de ions discharged at t
he anode
becausemagnesium isabov
ehydrogeni
nthe becausehydroxi
deionsr equi
rel
essener
gyto
el
ectro-
chemi
calseri
es. di
schar
get
hansulphateions.
Hy
drogengasev
olv
ed. Ox
ygengasev
olv
ed.

5.El
ect
rol
yte:
Copper
(I
I)sul
phat
e El
ect
rode: Car
bonr
ods
I
ons Pr
esent

Cat
ions Ani
ons
2+( + 2–(
Copper
,Cu aq)andHy
drogenH (
aq)i
ons. Sul
phat
e,SO aq)andHy
4 droxi
deOH–(
aq)i
ons.
Copper i
ons di
schar
ged at t
he cat
hode, Hy
droxi
dei
onsdi
schar
gedatt
heanodebecause
22 Phy
sical
Chemi
str
y
because copperis bel
ow hy
drogen i
nthe hydroxi
dei onsrequi
rel
essener
gyt
odi
schar
ged
el
ectro-
chemicalser
ies. thansulphateions.
Col
ourofsol
uti
onev
ent
ual
l
yfades. Oxy
gengasev
olv
ed.

6.El
ect
rol
yte:
copper
(I
I)sul
phat
e El
ect
rode: Car
bon
I
ons Pr
esent
Cat
ions Ani
ons
2+ + 2–
Copper
,Cu (
aq)andHy
drogenH (
aq)i
ons. Sul
phat
e,SO 4 (
aq)andHy
drox
ideOH– (
aq)i
ons.
Copperionsdischargedatthecat
hode,because No i on dischar
ged atthe anode inst
ead the
copperisbel
ow hy drogeni
ntheel
ectr
o-chemical el
ectrode di
ssol
ves,and goes i
nto sol
uti
on as
seri
es. copper(I
I)i
ons.
Col
ourofsol
uti
ondoesnotf
ades.

Quant
it
ati
veTr
eat
mentofEl
ect
rol
ysi
s
Anelect
ri
ccur r
enti
smeasur edi
namper es.Thequant
it
yofelect
ri
ccharge(
Q)i
smeasuredin
coul
ombs(C).
 Acoul ombisthequanti
tyofel
ect
ri
cit
ypassedwhenacurrent(I
)ofoneamperef
lowsfora
t
ime(t
)ofonesecond.

Therel
ationshi
pbet weent hemassofsubst ancepr oducedandthequanti
tyofel
ect
ri
cit
ypassedis
thebasi
sofFar aday’
sLaw ofel ect
rol
ysi
swhi chst at
esthatthemassofasubst anceproduced
duri
ngelectrol
ysisisdir
ectlyproport
ionalt
ot hequantit
yofelect
ri
cit
ypassed.
Thequant i
tyofelectr
ici
tycarr
iedbyonemol eofelectr
onsisaconstantcal
ledaFar
aday(F)andis
equi
val
entt o96,487coulombs.

 1Far
adayi
sequiv
alenttoonemoleofel
ectr
ons.Thenumberofel
ect
ronsr
equi
redt
odeposi
t
agi
veni
onisequi
valentt
othechar
geontheion.

Wor
kedExampl
es
1.Whatmassofcopperwouldbedepositedont hecathodewhenast
eadycur
rentofone
amper
efl
owsf
or30mi nut
esthr
oughcopper(
II
)sulphat
esolut
ion?
–1
(
Cu=63.
5)Far
adayconst
ant=96,
487Cmol )
Sol
uti
on
React ionatthecat hode
2+
Cu ( aq)+2e Cu(s)
Onemol eofCui onsrequir
ed2mol esofelect
rons.
Quant ityofelectr
icit
y(Q)=1×30×60coul ombs.
1mol eofelectronscarri
esachar geof96,
487coul ombs.
2mol esofelect r
onswillcarry2×96,
487coulombs.
2×96, 487coul ombsdeposi t63.
5gofcopperatt hecat
hode.
Theref ore1×30×60coul ombsdeposits:

2.Whatv
olumeofoxy
genwi
llbel
iber
atedatt
heanodewhenacur
rentof3amper
esi
spassed
 STRY 23
ELECTROCHEMI
t
hroughmagnesi
um sul
phat
esol
uti
onf
or45mi
nut
esand30seconds?
(
Mol
argasv
olumeatr
.t
.p.=24.
0li
tr
es,
Far
adayconst
ant=96,
500coul
ombs)
.
Sol
uti
on
Reactionequati
onattheanode
–
4OH ( aq) 2H2O(l
)+O2(g)+4e
1mol eofelectr
onscarry96,
500coulombs.
4mol esofelectr
onscarry4×96,500coulombs.
4×96, 500coulombsliber
ate24lit
resofoxygen.

3×(
45×60)+30)coul
ombswi
l
lli
ber
ate
=0.
50922lit
res.
3.I
n an exper
imentto el
ectrol
yse copper(I
I)sulphate sol
uti
on usi
ng copperelect
rodes,0.2
amper
eswer epassedthroughthesol ut
ionf or1,930seconds.Themassofcoppercat hode
i
ncr
easedfrom 6.
35to6.478g.Findthechar geonacopperi on.(
1Faraday=96,500coulombs,
Cu=64).
Sol
uti
on
Massofcopperdeposi
ted=(6.
478–6.350)g=0.
128g
Quant
it
yofelect
ri
cit
ypassed=0.2×1,
930=386C
0.
128gcopperwasdepositedby386C

64gofcopperwouldbedeposi
tedby C=193, 000C
1moleofcopperatoms(Mass64g)requi
re193,
000C
NumberofFaraday
srequi
redtodeposi
t64gofcopperatcathodei
sther
efor
e

Appl
i
cat
ionsofEl
ect
rol
ysi
s
Ext
racti
onofReacti
veElements
El
ectr
olysi
sisusedintheext
racti
onofr
eact
iveel
ement
ssuchassodi
um,magnesi
um,al
umi
num
andchlori
ne.

El
ectroplat
ing
Thi
si stheprocessofusingelect
ri
cit
ytocoatonemet
alwi
thanot
her.Thi
sisdonetoprotectsome
metalsfrom corrosi
on.Elect
ropl
ati
ngisalsodonet
omakeanar t
icl
elookatt
ract
ive.Goldplat
ed
watches,si
lverut
ensil
sarecommoni t
ems.

Sacr
ifi
cialmetal(
cathodi
cprotecti
on)
I
ron orst eelstr
uct
ures are pr
otect
ed f
rom cor
rosi
on t
hrough sacr
if
ici
alpr
otect
ion ei
therby
gal
vanisi
ngorcathodicpr
otecti
on.

Cathodicprotecti
on
Corrosi
oni nvolv
eslossofelect
ronsbyanel ementt ofor
mions.Ifitisalessreacti
vemet ali
tis
connectedt oamor ereacti
vemetalbyaconduct orwhentheconditi
onsforcausingcor
rosionare
present,t
hemor ereact
ivemetalioni
sesatt heexpensesoft
hel essreact
ive.Themorer eact
ive
met ali
ssacrifi
cedandthemethodi ssacr
if
ici
alpr
otecti
on.
24 Phy
sical
Chemi
str
y
Galvani
sing
Whent hegalv
anisedsurfacei
sscratchedandi
roni
sexposed,
zincpassesint
osol
uti
onaszi
nci
ons
2+
r
atherthanFe i ons.Thi
sispossi
blebecausezi
nci
seasil
yoxi
disedthanir
on.

Puri
fi
cati
onofMetals
Copperandotherl
essr eact
ivemet al
sarepur
if
iedbyel ect
rol
ysi
s.Thei
mpur
emet alismadet he
anodeandpur
emet althecathode.Theel
ect
rol
ytecont
ainsthecati
onoft
hemetal
sbeingpur
if
ied.

Manufact
ureofSodi
um Hy
droxi
deandChl
ori
nef
rom El
ect
rol
ysi
sofConcent
rat
edSodi
um
Chl
ori
de(Bri
ne)
Sodi
um hy dr
ox i
de and
chl
ori
ne are
manufactured by t he
el
ectr
olysis of brine by
use of mer cury cell
,
shownal ongsi
de.

Theel
ect
rol
ytei
nthemer
curycel
li
saconcentrat
edsol
uti
onofsodi
um chl
ori
de(Br
ine)
.Theanode
i
nthecel
lismadeofcarbonortit
ani
um becauset
heydonotreactwit
hchlor
inegas.Whi
lethe
cat
hodei
samov i
ngfi
l
m ofmercur
y.

–
Whenanel ectr
iccur r
entispassedthroughconcentr
atedsodium chl
ori
desolut
ion,chl
ori
de(Cl)
i
onsandhy droxide(OH–)ionsmi gr
atet otheanode.Chlor
ideionsarepref
erenti
all
ydischar
ged
becauseofthei
rr el
ati
vel
yhighconcentrati
on.
–
2Cl(aq) 2Cl
(g)+2e–

2Cl
(g) Cl
2(
g)

Bothsodi Na+)i
um ( onsandhy drogen(H+)i
onsmigrat
etothecat
hode(movingf
il
m ofmercur
y).
Hydrogenionsarenotdi schargedbecauseoftheov er
-pot
ent
ial(
excesspower)r
equi
red t
o
di
schargeit
.Sodi
um ionsareprefer
ent
ial
lydi
schar
gedinst
ead.

2Na+(
aq)+2e– 2Na(
l)

Thesodi
um at
omsf
ormeddi
ssol
vei
nthehotmer
cur
ytof
orm sodi
um amal
gam (
NaHg)

Na(
l)+Hg(
l) NaHg(
l)

Thesodium amalgam ispassedthr

oughatroughint hecellthatcont
ainsdist
il
ledwater.The
sodi
um int heamal gam t
henreact
swithwatertof orm asol ut
ionofsodium hydroxi
deand
hydrogengas.Hydrogenispumpedouttot
her equi
redplace,whil
emer cur
yisregenerat
edand
recy
cled.
 STRY 25
ELECTROCHEMI
2NaHg(
l)+2H2O(
l) 2NaOH(
aq)+2Hg(
l)+H2(
g)
Thesodium hy
droxi
deobt
ainedt
hiswayisaboutfi
ft
ypercentpure.Pur
esodi
um hy
droxi
deis
obtai
nedbyevaporat
ingt
hewaterintheaqueoussodi
um hy
droxi
desoluti
ont
ogetpell
etsor
fl
akes.
Theprocessi
sexpensi
veduet
othehi
ghcostofmer
cur
yandt
hesaf
etymeasur
esappl
i
edsi
nce
mercuryi
spoi
sonous.

Rev
iewExer
cises
1. 2006Q15P1
St
udythest
andar
dreduct
ionpot
ent
ial
giv
enandanswert
hequest
ionst
hatf
oll
ow.(
The
26 Phy
sical
Chemi
str
y
l
ett
ersar
enott heactualsymbolsoftheelements).
θ
E( v
olts)
2+ -
M ( aq)+2e → M( s) - 0.
76
2+ -
N ( aq)+2e → N( s) - 2.
37
+ -
P( aq)+e → P( s) +0.80
2+ -
Q ( aq)+2e → Q( s):- 0.
14
(
a)Thest andar dreduct
ionpotenti
alforFe2+(
aq)is- 0.
44v
olt
s.Sel
ectt
heel
ementwhi
ch
woul
dbestpr ot
ectir
onfrom rust
ing. (1mark)
(
b)Cal
cul
at heEѲ v
et aluef
ort
hecel
lrepr
esent
edasM(
s)/M2+( /P+(
aq)/ /
aq)P(
s).
(
2
mar
ks)

2. 2006Q1P2
(a)Whati
sanel
ect
rol
yte? (
1mar
k)

(
b)St
atehowt
hef ol
lowi
ngsubstancesconductel
ect
ri
cit
y.
(i
) Moltencal
cium chl
ori
de. (
1mar
k)
(i
i) Graphi
te. (
1mar
k)

(
c)Thediagr
am bel
owshowsasetupt
hatwasusedt
oel
ect
rol
yseaqueousmagnesi
um
sul
phate.

(
i) Onthedi
agr
am above,
usi
nganarrow,
showthedi
rect
ionofflowofelect
rons.
(1mar k)
(
ii
) I
denti
fyt
hesyr
ingei
nwhichhy
drogengaswoul
dbecollect
ed.Expl
ain
(1mar k)

(
d)Expl
ainwhytheconcent
rat
ionofmagnesi
um sul
phat
ewasf
oundt
ohav
eincr
easedatthe
endoftheexper
iment. (2marks)

(
e)Duri
ngt heel
ectrol
ysi
s,acurr
entof0.
72Awaspassedthroughtheelect
rol
ytef
or15
minutes.Cal
culatet
hevolumeofgasproducedatt
heanode.(1Far
aday=96500
coul
ombs; molargasvolumeis24000cm3atroom t
emperat
ure)
. (4marks)

3. 2006Q2bP2
Usether
eductionpot
enti
alsgiv
enbelowtoexplai
nwhyasol
uti
oncont
aini
ngcopperi
ons
shoul
dnotbest or
edi
nacont ai
nermadeofzinc.
2+ - θ
Zn ( aq)+2e→Zn( s)
;E =-0.
76V
 STRY 27
ELECTROCHEMI
2+ θ
Cu (
aq)+2e→Cu(
s);
E =+0.
34V
(
2mar
ks)
4. 2007Q7P1
(a)Usethei nfor
mati
ongivenbel
owt odrawalabell
eddiagr
am ofanel
ect
rochemi
cal
cel
l
t
hatcanbeconst ruct
edtomeasuretheel
ectr
omot i
veforcebet
weenGandJ. (2mar
ks)
2+ - θ
G ( aq)+2e → G( s)
;E =-0.74V
Eθ=-
2+ -
J ( aq)+2e → J( s); 0.
14V

(
b)Cal
cul
at heEθv
et aluef
ort
hecel
lconst
ruct
edi
n(a)abov
e. (
1mar
k)

5. 2007Q21P1
(a) Whenbri
neiselect
roly
zedusinginertel
ect
rodes,chl
ori
negasi
sli
ber
atedatt
he
anodei
nst
eadofox ygen.Expl
ainthi
sobservat
ion.
(2mar
ks)
(b) Nametheproductfor
medatt hecathode. (1mar
k)

6. 2007Q28P1
Duri
ngtheelectrol
ysisofaqueoussi
lvernit
rat
e,acurrentof5.
0Awaspassedt hr
oughthe
el
ectrol
ysi
sf or3hours.
(a) Wr i
tet
heequationforr
eactionwhichtookplaceattheanode. (
1mark)
(b) Calcul
atethemassofsilv
erdeposited(Ag=108; 1F=96500C)(2marks)

7. 2008Q19P1
Sel
ectal
etterwhichr
epresent
samonoat
omi
cgas.
θ
E( Volt
s)
2+ -
Zn ( aq)+2e→Zn( s) -0.76
2+ -
Pb ( aq)+2e →Pb( s) -0.13
+
Ag (aq)+2e →Ag( s) +0. 80
2+ -
Cu ( aq)+2e→Cu( s) +0. 30

(
a) Wr i
tethecel
lrepresentat
ionfortheel
ect
rochemi
cal
cel
lthatwoul
dgivethe
hi
ghestE (1mark)
(
b) Stateandexplai
nt heobservati
onsmadewhenacopperrodispl
acedinabeaker
contai
ningsi
lvernitr
atesoluti
on. (2marks)

8. 2008Q21
Thedi
agram bel
owrepresent
sanex
per
imentt
hatwassetupt
oinv
est
igat
emov
ementof
i
onsduri
ngelect
rol
ysi
s.
28 Phy
sical
Chemi
str
y

Whentheci
rcui
twascompl eted,i
twasnoticedt
hatabluecolourspr
eadt
owar
dst
heri
ght.
(a)Expl
aint
hisobserv
ation (2marks)
(b)Writ
etheequati
onfort hereact
iont
hatoccur
redattheanode. (1mark)

9. 2008Q6P2
Thediagr
am bel
owr
epr
esent
sasetupt
hatcanbeusedt
oel
ect
rol
yzeaqueouscopper(
II
)
sul
phate.

(
a)(
i)Descr
ibehowoxy
gengasi
spr
oduceddur
ingt
heel
ect
rol
ysi
s.
(
2mar
ks)
(
ii
)Expl
ainwhycopperel
ect
rodesar
enotsui
tabl
efort
hisel
ect
rol
ysi
s.
(
2mar
ks)

(
b)I
mpur ecopperi spuri
fiedbyanel ectr
olyt
icprocess
(i)Nameoneor efrom whi chcopperisobtained (
1mark)
(ii
)Wr itetheequationforthereactionthatoccuratt
hecat hodeduri
ngthe
puri
ficat
ionofcopper . (
1mark)
(ii
i
)Inanex peri
mentt oelectr
oplateacopperspoonwi thsil
ver,
acurrentof0.5Awas
passedf or18mi nutes.Cal
culatetheamountofsilverdeposit
edont hespoon(n
=96500coul ombs, Ag=108) (3mar ks)
(iv
)Gi vetwor easonswhysomemet al
sareelectr
opl
ated (
2marks)

10. 2009Q7P1
Whenal
umini
um oxi
dewaselect
rol
ysed,1800kgofalumini
um metal
wasobt
ained.
(a) Wri
teanequat
ionf
orthefor
mat i
onofaluminium met
al. (
1mar
k)
(b) Cal
cul
atet
hequanti
tyofel
ectr
ici
tyinfar
adaysused.(
Al=27) (
2mar
ks)
 STRY 29
ELECTROCHEMI
11. 2009Q10P1
Hydrogenandoxygencanbeobt ainedbyel
ect
rol
ysi
sofaci
dif
iedwater
.Usingequat
ionsfor
thereact
ionsatt
heelect
rodes,
ex plai
nwhythevol
umeofhydrogenobt
ainedist
wicethatof
oxygen. (2marks)

12. 2009Q12P1
Thestandardr educti
onpotent
ial
soft wohalfcel
lsare:
Eθ=0.
+
Ag ( aq)+e →Ag( s) 80V
- - θ
2H2O( l
)+2e→H2( g)+2OH (aq); E =0.83V
Drawalabelleddi agr
am ofanelectr
ochemicalcel
lthatcanbeconst
ruct
edusi
ngt
hetwohal
f
cell
s. (
3marks)

13. 2009Q3P2
Theset
-upbel
ow(
fi
gur
e2)wasusedt
oel
ect
rol
yseabr
omi
deofmet
alD,
DBr
2

(
a)Wr
itet
heequati
onf
ort
her
eact
ionatt
he:
(i
) Cat
hode (
1mark)
(i
i
) Anode (1mar
k)

(
b)Theel
ect
rodesusedi
ntheexper
imentwer
emadeofcarbonandmet
alDwhichoft
he
twoel
ect
rodeswasusedastheanode?Gi
vear
eason. (2marks)

(
c)Gi
vear
easonwhyt
hisexper
imenti
scar
ri
edi
naf
umecupboar
d. (
1mar
k)

(
d)Whenacur
rentof0.
4Ai
spassedf
or90mi n,
2.3gofmetalDwer
edeposi
ted.
(i
)Descri
behowtheamountDdeposi
tedwasdeter
mined. (
3mar
ks)

(
ii
)Cal
cul
atet
her
elat
iveat
omi
cmassofmet
alD.(
1Far
aday
=96500coul
ombs)
(
3marks)

14. 2010Q7P1
Compl etethet
ablebel
owbywr i
ti
ngt
heproductf
ormedatt
heel
ect
rodesdur
ingt
he
elect
rolysi
softheel
ectr
oly
tesgi
veni
nthetabl
e.
(3mar ks)
El
ect
rol
yte Pr
oductatanode Pr
oductatcat
hode
Aqueoussodium sul
phat
e(½mar
k) (
½mar
k)
usi
nginer
telect
rodes
30 Phy
sical
Chemi
str
y

Aqueouscopper(
II
) (
1mar
k) (
1mar
k)
sul
phateusi
ngcopper
el
ectr
odes.

15. 2010Q19P1
Thehal
fequati
onsinv
olvedi
nacel
lare:
:Eθ=-0.
-
2H2O(l)+2e → H2( g)+2OH-(
aq) 83V
Eθ=+0.
- -
O2(g)+2H2O( l
)+4e→ 4OH( aq)
: 40V

(
a)Wr
it
etheov
eral
lequat
ionf
ort
heel
ect
rochemi
cal
cel
l
. (
1mar
k)

(
b)Cal
cul
atet
hee.
m.f
.gener
atedbyabat
ter
yconsi
sti
ngoft
encel
l
s.
(
1mar
k)
(
c)St
ateoneenv
ironmentadv
ant
ageofusi
ngt
hesecel
l
sinspacecr
aft
s. (
1mar
k)

16. 2010Q1P2
(a)Whi
choneofthefol
l
owingcompounds;urea,ammonia,sugarandcopper(
II
)chl
ori
de
wi
ll
conductanel
ect
ri
ccurr
entwhendissolvedi
nwater?Givereasons. (2marks)

(
b)Thediagram bel
owshowsanel
ect
rochemi
cal
cel
l
.St
udyi
tandanswert
hequest
ions
thatf
oll
ows.

Gi
venthefoll
owing;
Fe2+( aq)+2e→ Fe( s)
;Eθ=-0. 44V
2+ θ
Zn ( aq)+2e→ Zn( s)
;E =-0. 76V
(
i)Showont hediagr am usinganarrow, thedirecti
onoff l
owofelectr
ons
(1mark)
(
ii
)Namet wosubst ancest hatareusedt ofil
lthepar tl
abell
edL
(2marks)
(
c)Inanex per
imentt oelect
ropl ateironwithsil
ver,acurrentof0. 5amper eswaspassed
throughasol utionofsilv
erni trat
ef oronehour .
(i)Givetwor easonswhyi tisnecessar ytoelectr
oplateironwi t
hsilv
er. (
2mar ks)

(
ii
)Cal cul
atet
hemassofsi
l
vert
hatwasdeposi
tedoni
ron(
Ag=108,
1Far
aday=96,
500
coulombs) (
3marks)

17. 2011Q12P1,
2016Q15P1
 STRY 31
ELECTROCHEMI
Sodi
um hy
droxidecanbeprepar
edbyt hefol
l
owi
ngmethods;
IandI
I.
col
dwat
er
I
.Sodi
um metal→Sodi um hy
droxide+Hy
drogen

I
I.Concentr edP
at →r
ocessA
Sodi
um hy
droxi
de+Chl
ori
ne+Hy
drogen
sodium chlor
ide

(
a) Nameonepr
ecaut
iont
hatneedst
obet
akeni
nmet
hodI
. (
1mar
k)

(
b) Gi
vet
henameofpr
ocessA. (
1mar
k)

(
c) Gi
veoneuseofsodi
um hy
droxi
de. (
1mar
k)

18. 2011Q2P2
Theset-
upbel
owwasusedbyast udentt
oinv
est
igatet
hepr oduct
sfor
medwhenaqueous
copper(
II
)chl
ori
dewasel
ect
rol
ysedusingcar
bonelect
rodes.

(
a)(i
)Wr it
etheequationforthereact
iont hatt
akesplaceatthecathode. (1mark)
(
ii
)Nameanddescr i
beachemi caltestfort
hepr oducti
nit
ial
l
yformedatt heanodewhen
ahighl
yconcent r
atedsolut
ionofcopper( I
I)chlor
idei
select
roly
sed.
(3marks)
(
ii
i)Howwouldt hemassoft heanodechangei fthecarbonanodewasr eplacedwit
h
coppermetal?Explai
n. (2mar ks)

(
b)0.6gofmet
alBweredepositedwhenacurrentof0.
45Awaspassedthr
oughan
el
ectr
oly
tef
or72minutes.Deter
minet
hechar geont
heionofmetal
B.(Rel
ati
veat
omic
massofB=59,1Faraday=96500coul ombs) (3marks)

(
c)Theel
ect rodepotent
ial
sforcadmium andzi
ncaregi
venbel
ow:
2+ - θ
Cd ( aq)+2e⇌ Cd( s)
; E =-0.4V
2+ θ
Zn ( aq)+2e⇌ Zn( s)
; E =-0.76V
Explai
nwhyi tisnotadvi
sabl
etostoreasol
uti
onofcadmium ni
tr
atei
nacont
ainer
madeofz i
nc. (
2mar ks)
32 Phy
sical
Chemi
str
y

19. 2012Q15P1
Bel
owisarepr
esent
ati
onofanel
ect
rochemi
cal
cel
l
.
s)/Pb2+(
Pb( /Ag+(
aq)/ aq)/Ag(
s)
a)Whatdoes/
( /repr
esent
? (
1mar
k)

(
b)Gi
vent
hef
oll
owi
ng:
EθV
Pb2+(aq)+2e-→ Pb( s); -0.13
+ -
Ag (aq)+e → Ag( s); -0.
80
Cal
cul
atet
heE. M.Foftheel
ect
rochemical
cell. (
2mar
ks)

20. 2012Q28P1
Theapparatusshownint
hediagr
am bel
owwereusedtoi
nvesti
gatethepr
oduct
sfor
medwhen
concent
ratedsodi
um chl
ori
dewasel
ectr
oly
sedusi
nginer
telect
rodes.

(
a)Wr
it
etheequat
ionf
ort
her
eact
iont
hatt
akespl
aceatel
ect
rodeA. (
1mar
k)

(
b)I
ftheconcentr
atedsodium chl
ori
dewasrepl
acedwi
thdi
l
utesodi
um chl
ori
de,
whatpr
oduct
woul
dbef ormedatelectr
odeA?Explai
n. (2marks)

21. 2012Q5P2
(a)Thesetupbelowwasusedtoinvest
igatetheproduct
sf or
medattheelectr
odesduri
ng
el
ectr
olysi
sofaqueousmagnesi
um sulphateusingi
nertel
ect
rodes.Useittoanswert
he
quest
ionsthatf
oll
ow.
 STRY 33
ELECTROCHEMI

(
i)Dur i
ngtheelectrol
ysi
s,hydrogengaswasf or
medatelectr
odeY.I dent
if
ytheanode.
Gi
vear easonforyouranswer . (2mar ks)
(
ii
)Wr i
tetheequationforthereacti
onwhichtakespl
aceatelect
rodeX
(1mar k)
(
ii
i)Whyistheconcent r
ati
onofmagnesi um sul
phat
eexpectedtoincreaseduri
ng
el
ectr
olysi
s? (2mar ks)
(
iv)Whatwillbeobservedifr
edandbl ueli
tmuspapersweredippedintothesolut
ion
af
terel
ectrol
ysi
s? (2mar ks)

(
b)Duri
ngelect r
olysisofmagnesium sulphate,
acurrentof0.
3awaspassedf
or30mi
nutes.
Cal
culat
et hev olumeofgaspr oducedatt heanode
(Mol
argasv olume=24dm3; 1faraday=96,500C) (
3marks)
(
c)St
atetwoappl i
cationsofelect
rolysi
s (
1mark)

22. 2013Q6P1
(a)Astudentel
ectr
opl
atedaspoonwi
thcoppermet
al.Wr
it
eanequat
ionf
ort
heprocess
t
hattookplaceatt
hecathode. (
1mar k)

(
b)Cal
cul
atet
het
imeinminutesrequi
redt
odeposi
t1.
184gofcopperi
facur
rentof2
amper
eswasused.(
1Faraday=96500coul
ombs,Cu=63.
5). (
2marks)

23. 2013Q4P2, 2016Q4P2.

(a)Thesetbelowcanbeusedt
opr
oducesodi
um hy
droxi
debyel
ect
rol
yzi
ngbr
ine
34 Phy
sical
Chemi
str
y

(
i)Identi
fygasY. (1mark)
(
ii
)Describehowaqueoussodi um hy
droxi
deisfor
medi
ntheabov
eset-up.
(2marks)
(
ii
i)Oneoftheusesofsodium hydroxi
deisi
nthemanuf
act
uri
ngofsoaps.St
ateoneother
useofsodi
um hydr
oxide. (1mark)

(
b)St
udyt
hei
nfor
mat
iongi
veni
nthet
abl
ebel
owandanswert
hequest
iont
hatf
oll
ows

θ
Hal
freact
ion El
ect
rodepot
ent
ial
E(V)
D2+(aq)+2e- → D( s) -
0.13
+ -
E( aq)+e → E(s) +0.80
-
F(aq)+e → Faq +0.68
2+ ¬
G( aq)+2e → G( s) -
2.87
2+ -
H( aq)+2e→H( s) +0.34
+ -
J( aq)+e →J(s) -
2.71
(
i)Constructanelectrochemicalcel
lthatwil
lpr
oducet hel ar
geste.
m.f (3marks)
(
ii
)Calcul
atetheemfoft hecellconst
ructedi
n(i
)abov e (2marks)
+
(
ii
i)Whyisitnotadvisabletostoreasoluti
oncontai
ningE i onsinacont
ainermadeof
H? (2marks)

24. 2014Q24P1
(a)Astudentelect
rol
yzeddilut
esodium chlor
idesol
uti
onusinginer
tcar
bonel
ect
rodes.
Namet heproduct
sat:
i) Anode:
ii
) Cathode: (
2mar ks)
(b)Ift
heex per
imentwasr epeat
edusingconcentrat
edsodium chl
ori
dei
nst
eadofdil
ute
sodium chl
ori
desolut
ion,writ
ethehalfequati
onattheanode. (1mar k)

25. 2015Q11P1
Dil
utesul
phur
ic(VI
)aci
dwaselect
rol
ysedusi
ngpl
ati
num elect
rodes.
Namet hepr
oductf
ormedatt
heanodeandgiveareasonforyouranswer
.(2mar
ks)
 STRY 35
ELECTROCHEMI
26. 2015Q18P1
Studythestandar delectrodepotent
ial
sinthetablebelowandanswerthequest
ionsthat
fol
low.
Eθ(v ol
ts)
2+ -
Cu ( aq)+2e → Cu( s) +0. 34
2+ -
Mg ( aq)+2e→Mg( s); -2.38
+ -
Ag ( aq)+e →Ag( s)
; +0- 80
2+ -
Ca ( aq)+2e →Ca( s); -2-
87
(a)Whichoft hemet al
si sthestr
ongestr
educingagent ? (
1mar k)
(b)Whatobser vati
onswi ll
bemadei fasil
vercoinwasdr oppedi
ntoanaqueoussolut
ionof
copper(II
)sul phate?Ex pl
ain. (
2mar ks)

27. 2015Q4P2
(a)Thedi
agr
am bel
owr
epr
esent
sadr
ycel
l
.Usei
ttoanswert
hequest
ionst
hatf
oll
ows.

(
i)Whi chofthel et
ter
sr epr
esent
;
I
. Car bonel ectr
ode? (
1mar
k)
II
. Theel ectr
olyt
e? (
1mar
k)
(
ii
)Oneoft hesubst ancesusedinadrycel
li
smanganese(I
V)oxi
de.
Stat
etwor olesofmanganese( I
V)oxi
deint
hedr
ycell
s. (
2mar
ks)

(
b)Bel
owissimpl
if
iedel
ect
rol
yti
ccel
lusedf
orpur
if
icat
ionofcopper
.St
udyi
tandanswer
t
hequest
ionst
hatfol
l
ows.

(
i)I denti
fythecathode. (
1mark)
(
ii
)Wr it
etheequat i
onforthereact
ionattheanode. (
1mark)
(
ii
i)Whatnamei sgiventoL? (
1mark)
(
iv)Acurrentof0.6AwaspassedThr oughtheel
ect
rol
ytef
or2hour
s.Det
ermi
net
he
amountofcopperdeposi t
ed.
36 Phy
sical
Chemi
str
y
(Cu=63.
5;1Far
aday=96,500coul
ombs) (
3mar
ks)
(
v)Stat
etwousesofcoppermetal (
1mar
k)

28. 2017P1Q3.
Thedi
agr
am i
nFi
gur
e1showsasect
ionofadr
ycel
l
.St
udyi
tandanswert
hequest
ionst
hat
f
oll
ow.

(
a)Namet hepartlabel
ledB. (
1mar
k)
(
b)Thepartlabel
ledAi sapast
e.Giv
ear easonwhyi
tisnotusedi
ndr
yfor
m. (
1mar
k)
(
c)Whatisthepur poseofthezi
nccont
ainer? (
1mar
k)

29. 2017P1Q22.
(a)Whatisaninertel
ectr
ode? (1mar
k)
(b)St
atetheproductsfor
medwhenbr
inei
sel
ect
rol
ysedusi
ngi
ner
tel
ect
rodes.
Anode:……………. (
1mark)
Cathode:…………... (
1mark)

30. 2017P2Q2(b)
(
b)Copper(
II)sul
phat
esol
uti
onwasel
ect
rol
ysedusi
ngt
hesetupi
nFi
gur
e1.

(
i)Statet
heobserv
ati
onsmadedur i
ngelect
roly
sis. (
1½marks)
(
ii
)Wr i
tet
heequati
onfort
hereact
ionthatoccursattheanode. (
1mar
k)
(
ii
i)St
atet
heexpect
edchangeinpHoft heel
ectrol
yteaft
erelect
rol
ysi
s. (
½mar
k)
 STRY 37
ELECTROCHEMI
(
c)Theexper
imentwasrepeat
edusi
ngcopperel
ectr
odesi
nst
eadofcar
bonel
ect
rodes.
Descr
ibet
heobserv
ationsmadeateachel
ect
rode. (1mark)

(
d)Electr
oplat
ingi
sani mportantindust ri
alpr
ocess.
(
i)Whati smeantbyel ectropl
ating. (1mark)
(
ii)Stat
ethepurposeofel ectr
oplating. (1mark)
(
iii
)Duri
ngelect
roplat
ingofani ronspoon, acurr
entof0.
6ampereswaspassedthr
ough
aqueoussil
vernit
ratesoluti
onf or11/2hours.Cal
cul
atet
hemassofsi
lvert
hatwas
deposi
tedonthespoon. (3marks)
-
1
(Ag=108.0;1F=96, 500Cmol)

31. 2018P1Q16.
Metal
sXandYhavestandardel
ect
rodepot
ent
ial
sof-0.
13Vand-
0.76Vr
espect
ivel
y.The
metal
swer
econnect
edtof or
m acel
lasshowninFi
gure4.

(
a)Namethepar
tlabell
edZ. (
1mar
k)
(
b)St
ateonef
uncti
onoft hepartlabel
l
edZ. (
1mar
k)
(
c)Cal
cul
atet
hee.m.f.ofthecell
. (1mar
k)

32. 2018P2Q3(c)
Usethest
andar
del
ect
rodepot
ent
ial
sinTabl
e2t
oanswert
hequest
ionst
hatf
oll
ow.

(
i)Wr itethehal
f-cellr
epresent at
ionfortheelementwhoseelectr
odepotenti
ali
sfor
hy drogen. (
1mark)
(
ii
)Ar rangetheelement sinor derofreducingpower,
start
ingwit
ht heweakestr
educi
ng
agent . (1mark)
(
ii
i)I.Selecttwohal fcel
lswhi chcombi netogiveacellwit
htheleaste.
m.f.
(
1mark)
II.Calcul
atethee. m.fofthehal fcel
lsidenti
fi
edi
n( i
i
i)I
. (1mark)
38 Phy
sical
Chemi
str
y

33. 2019P1Q19.
GiventhattheEθofCu(s)
/Cu2+(
aq)i
s+0.34Vandthat0fZn(
s)Zn2+(
/ aq)i
s -0.
76V,
drawa
l
abelleddiagr
am ofzi
ncandcopperelect
rochemi
calcel
l.
(
3mar
ks)

34. 2019P2Q6.
(
a)Whatismeantbyst
andardel
ectrodepotent
ial
ofanel
ement? (
1mark)
(
b)Usethest
andardel
ect
rodepotenti
alsgi
venbelowt
oanswerthequest
ionst
hatf
oll
ow.

(
i)Statewhetheracidi
fedMnO-4canox
i i
diseM2+.Giveareason. (
2mar
ks)
(
ii
)Selecttwohalf
-cell
swhichwhencombi nedwillgiv
ethehigheste.
m.f
. (
1mar
k)
(
ii
i)Wri
tethecel
lrepresent
ati
onforthecel
l f
ormedi nb(i
i)
. (
1mar
k)
θ
(
iv)Cal
culat
etheE v al
ueforthecel
lfor
medi nb( i
i
i). (
1mar
k)

(
c)Amassof1. 24gofadi
val
entmetalwasdeposi
tedwhenacurr
entof6Awaspassed
thr
oughasoluti
onofametalsul
phat
efor12minutes.Det
ermi
nether
elat
iveat
omicmass
ofthemetal.
-
1
(1Faraday=96,
500Cmol ) (3marks)

(
d)St
atet
woappl
i
cat
ionsofel
ect
rol
ysi
s. (
1mar
k)