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POTENTIOMETRY CHAPTER

UNIT5
2

A
srLLABUS :

M
Electrochemical cell, consuchon ond
asd working of refence
(standard ydroqen . siler chlovide elechrode and Calomel elecrode)

qloss elochrode)
ad indicator electrodes ( metal elechrodes ard

R
melhods to dejervine ehd point of potentiomeric

A
tration and opplicahions.

H
Potertiomery:
. techrique whae potutial of an elecrode is ysed
It is
P
to Measure the Concavtrahion of onalte /solution.
potential ie.
Rosicall, it t measurement Of
OF elechode
LL

using electrochcal cels


dìfferences in voltagk befueen the electrod b

Principle :
E

bosed on the principle that in this we (masuve the


W

dopends
elecvode potential, dea ohich is the OF

refrenco and indicator electrodes.


poteutal diffunu voltagk bs
. Thls Nent fquation.
E

measured ajculated by
elechrode potentialis

R

2303 RT lag Elechode poterial


k fuilibrium constant for
k:
A

the half- cel) recfion as


ushere, equlibrium law.
C

€: stondard redvchion potential


R G0s onstant
kelvin temperature
T: in the balf reachons
n=NO. Of elecvans ttansferred
faraday of Eechnicty
f=
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ELECTROCHEMICAL CELL

Thesa thoco cells whch the physical /chemal


COnverts

A
enerqy into electrical enerqy helpsn
and helpsin themeasurement
of clectode potential.

M
• 1F helps in the generation of voltoge)Cie. electromotive forceJ
ent
and Current bu usin9 chenicl reochonc

R
fach electrochermjal cell is omposed of to half-cells.

A
Voltmeker

electrode
Salt bridqe (Ke)
H elecrode
P
Oridgti -depo ition of copper

fnode -Cathode (4)


LL

(-) Ruducian
Half-cell tHalf- col|
ZnsOy
Cyt+so
E

• Flectro chemi a
cells, also known dielectric or galvaniC cell.


W

At anode
+ 2e Oxidahion Loss of elechron]

.
E

At ahode.
( Reducion Gajn of electron:]
R

Salt bridqe elecrical confact Made behueen botn


A

- cells.
the half
-
it majntain te jonic disbalanca ondneutralisa i
C

COmplek th cirwit

Nac) Na+
+
a,kg k+

Fcell = festferensa t Eindiaor + Ejunetiae: ectomotive focs


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Electtodes
They are moinly USAd
to measUYe the voltagR theye

A
ae majnly two types Of elecvodes USAd in potenfiomtny

0 Reference lstand ard electrode

M
stardad hydroqen
Silver cNoride elecrode

R
alomel electrode

2) IndiCalor electrode

A
Metal elecrode
Glass electrode
t
- H
P
O Referenco electrode Thesa aie thos electrode which haue

known elecrode potential


LL

oIt is complelely independent of concentroion of


analyk solution

for the detemiration analyt


of the anayk by
E

maintaining the fixed potential.


W

-Nomal
sfondard tydroqen Electode (SHEJ NHE
a
IF ontajns qlass tube with a platinumwire sealed within
E

plainum foil Coatd with pt. block to Increa sa surfaco area.


R

• This as
at platinom electrode.

whjch mmersed in IM HCU to th qas E


A

Salt budq
majntain tne conc of H* lons. pt wtre
C

The tHydrogen (H) qas in pure


fom js Cortinvousl bubbled in IM HO
Bubblei of
the acdjc solution at T- 298k qas
and pRSSUre = Lam. pt fol Coajed

• It is atachd with aother half cell with analyk so1k

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hen t 0ct

A
QH* + 2e (oxidation]

When

M
(reduchon)

R
- Silver
) Silver CWoride electrode

A
as
USed in pH maters
te internal rekerenco electode.
Constwchiarn:

|f conojns a silver wire Coaled with

H
Ag4 (siver chloride)
P
• The electrode Ag wire
is immersed in solution oF
potassiom chloride [kc] having JM OF
T ion.
LL

• It is tepresented as
-Ag oire
COvered wilh
E

a reachion blw -Ikc/Agel so14



there is tq (civer mal )
W

and Agcu (ilver hloride) porous junchin Jtit

Aq +
AgI
Agd t e
or Ag +e Aq6)
E
R

() Calomel electrode

offen employed as secordory sfadard reference electrode.


A

It
,
pt. wjre
•A plainUM jre immersed in liquid muUry
i
C

is covered with olomel (i.t. Hq2(44) to salt


with 1M saturaed solution

The to is fled bidqt Saturated
OF potasum chlortde (ke). kei so

which kq solution ic
The narow alass tube in
con Connect thiy Hqai,) Hg.
illed hs a Salt bridg wCh
electvodo t0 diffesent
elecrodeS. -rcuny
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It Can be represented as:

A
Worling teochions for half- cell of calomel electrode is

M
Hqt
2+
20 24
Hq2 +(2e
2H9

R
2 Indicaor Etectrodes : -

A
These USed in pair with refeene electrode and
connected with voltmeter.

H
.•
It is USed to detming the Concentration of analyk in
the sample solution.
P
() Metay elecvode -PH
LL

Tt qenerae elechric (potential) as a result of redoxX

reachion on the Surfaca Of metal.


• Plainum or qold melals are Used in indiao electrode.
E

wires to /pH
) Glass tectode
W

Muer

he me0sUre ment Of pH for ay


qiven solution bo done easily
E

Can

USing a qlass elechrode.


R


It indudes thn- walled bulb a kl soluthia

electhad
a qloss
he bottom and tubi at top. iglAgcl
A

• The bulb is Alled wilh 0-)M HU


elecrode
C


4 silver (Ag) wie, (overed with Agd is
present af the louwer end oF qlass tube. 0.] M HCJ


It is tepre sentcd as :
thnwalled
Aq, Ag4 IM HQ H* (TEST SÔUTION)
glas tub
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TpoteNTIOMETER

It is instrument which is Used in poteniomhry

A
|t consists of:
References
0 Hectrodes

M
Indicator
2) Vessels

(0) TitraHon burette

R
9 Magntic stirer PH METER Bunettc

A
Sfandond so"
Referenca elecvode

Indicakor
elecrode H
P
LL

Sample /tes
Solution

Mogntie stirrer
E
W

0 Electtodes Tt Conains both referena and indicaot.


Vessels Tt contains
Tt Sample/ analyk solution, whoosa
E

CoNcenfrahin to ba
be msured..
R

(?) TitatHon byret It conjajns standard 0lution whjch is

Used for itraion.


A

.
If is redox titration. tn end point pH=?
C

Magnuhic stirrer It incEACLA the reaction


9
Hl t NaOH

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End Point Dection


The erd point or the equivalent point an be iocated

A
using various mthods.
.There is a Aharp change in elecroe potertial
potetial when

M
equivalenxe point (end point) is reochsd.

of ttant
• End point should be reOchd ar) tqval quartity

R
and titrand.

A
) pH MasUremet In this, pH meter to Masue
is vLed

H
the pH Of solution, throvqhout th titratin.
•A shap/ siqificant (mp) change in pH Can be th
P
, cprially in add- basa titrahion.
endpoint of tic
LL

) Graphical mthods t involves plotting the potential

difference (voltage) aqcinst ths volumu of titrant


addd.
Y-axis
E

SMmooth aurve |s
•A
drauw Toining al th End léquivalexe
W

poins
. Voltage
point
The endpoint coresponds emt
E

to ctee pes} (higlu -axis


X

the volun of tittant


R

Magvtude ) slope on t qraph.


A

(m) Aid -Base Tittation In this, te endpoint is dekced


Ustng pH mukr. th
p
at equivalenca
C

poin is close to
(v) Rodox the end pout is detem nud by montoing
Changu (voltage du to tho ttansfer
in thu of
eletvons buen the anayk and ittant.
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O Complexomutric tittauons :" n thu, the endpoint is typically


deectedusing indicators or
electrodes Sensitive

A
fo mtal ons

M
APPUcATION S

R
USed in clirical chestvy for th analyss oF

A
electvoty ts SUch Na, k, Ca, H and ( and dissolved

qasu SUch

• Vsed for th
H
determnatjan of (erdpoint)of an ad bas
P
itrotion
ervivonmuntal chunisty for analyí oF CN,
LL

N, NOg, ln oater and waste water.


USed in
aqriultu foe anlycis of NH,I,a,NO3, k,
E

soils, plat mateials, feuilizurs ek..


W

It alto Uced in food processing deportuntr in


E

-
8alt confenf in daiy pOducs
R

Ca in dairy products and but


k in
fuut guicA
A

-
f in dinkina wars and ofha dinks
C

NO
ad NO2 in mat presentive.
Also USAd in assay of NaboZpam and oth sulpha dgs.

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