Written By

Department of Pharmacy
University of Rajshahi
Rajshahi-6205, Bangladesh
 401
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.JC)\~ £~h~~1) . . 27... . . .
Amperomctrlc Titrations

t:f.'l Iutroductlon
Polarography can be. med ns the basis of ampcroutctric titration method comparable with the
poten1io111ct1J~ the co11ih,1ct.?me1ric, nud the photo11\CirlC-l11ethodf"~!.!T.~~g111ctric titrati~ns, t.he y()hage
applied across the indicatorelectrode end the reference electrode is kept.co\1$l.a11t nnd,the diffusion curre.tl'l.
(\Vhich is equal ii) Hiilillug i;\;rrcni~!csi4ual· ~-~~cnt) passing thro~lgh fue. c_ell is n~easured and plotted .~g~~st
Ilic ~olun~c of the .rcagcn!: ~d<lc't',~ . , . . i
._ From polnrographic ·icch11iq11e, it is known that current is lndcpcudcnt of applied voltage impressed it.
!?~~ !•ron droppir1~ m~miry c!:ci.l?dc or any 0 thcr electrode, ffo~v; if \~.e_ t_?.ke .an_cxfi:ss or suJ>polli11g electrolyte,
0 11'-t
the factors affecting the 11111,rtmg current rs the rate of diffusion of electroactive material from the bulk of 1. J)
Q :\'(\e\r;'.A: jh~ ~,0J~11i~· _ -to die'.cltS·i·:~?d,~. ~u_1.Ja~~,·r.,lii.s i~ because .: the migrat.io 11 current is _elim ..ina. tc·<l· ur.'.dcr; such
0
I
'
condition Thus, d1ffus1on current 1s proportional to the concentration of electro active-material 111 the
··r~F0r:
i k
solutiorv f by any mc1h0,cl.':some or the el~t~g-active material is removed by interaction ''t'.il~ :111y_rca_8ent,
lhe,~~!.f:fus@i~~~-t _\vi 11. ii~ffi.ta )_ly -~~~~~~~~.~,fJ1 i$Jo,r_m~_!J1~-~~!~~~cl.!~~~~jalb~sis_ .of an1pc r;o_~1f ~f i,C,ti Ira !i~11s,
dtff
-~le!!~~~ _[r~ll1__ 11~1pe~e, tl1~. unu _or cu_~nt.r. ~~. t~c
n
us1on_ curr~nt 1~-¥ec~usc;- of polarisation'a_t a micro

Ma J
. clec~d.:•. ~~1_:_1~~hmquc .!s: also_ known _as ~0Ja~~mct~1c. ~.rJ:~t~rograp~1c 11_1ra~1on. !i _ , .. _.
. . The a~I?.~r.oine. 'iri.c tuclhod is cons~d~r.ed to be mor~ accurate than th~,pol~rographic n17.ll~o~. p,e~~u.s.~
• It 1s less de .e.~1~e~~--.u '.~11 t~1.e charactcr 1Sll~s o~ the cap1~la~y a1:d the supportmg elcctrol te'. ~

ur
0

Amperomclnc ~ml conductornetrlc utrauons are similar 111 the respect that the data (or each ar] .i+oJ.::i Af>\P. t.1
ollected well away froin.thc equivalence point. Therefore, the reactious thnl n.rc relatively incompl . ete can -~~ Lo.,n_ ro ttu.
~ e employed. · ·
· ;•
_ ·· ·. · . •
N · Calomnt
Electrode
, .
•
D_ropplng Eloctrode
Q tr.N::1 • 'lW.. tf.., 11 & ?
-J:..}2 Apparatus Used f~rAmpero~nclric Tltrntlons
a n
The equipment used in ~he case ofamperometirc li!rations i_s
· · ·

r
simple. Although it may),~ same 11s used for polarogrnphy, several

Im
si111pJifications arc possible. The titrations may be performed either
with the clroppinr, 1imc111y electrode or with rotating platinum electrode.
For dropping 111r1c111y ck-ctrodc, the usual polnrograplilc equipment is
Vollag9
Control

.
used with cells uiodifiedto allow the addition of titrating reagent

d
(Fig. i7.I). . .. ·. . . Fig. 27.1

MCaloruel clcctroclblsusr.d as a reference cle~lroclc. The galvanometer measures the current and the
series of rheostat may be used for changing the sensitivity of the galvanometer.' In order to cany out the
amperomctric titrations, the voltage applied to the indicator electrode and the reference electrode is kept
constant, The sensitive ralyanomcter indicates the, value of diffusion current after. each addition of the
··t;trant. 1.t is to be noted tiiai'gencrally the potential of a reference electrode will lie in the permissible range,
so that it is necessary ·~1iiy to short-circuit the indicator electrode through a suitable current measuring
instrument to a 1cfcrcnct.-clec1roclc of rcl:itively large area. Some of suitable reference electrodes arc givcn \
in 1'able 27. L · . ' .

...
hit,
Q__... ~6W t ~, \.,,, ·~ o.-......f£U. esow.r..P

·-"'------~·,.,,;:..

1 / 6
 Atnperotnetrlc Titratlons . 2.53.S

· Table 27.1 Elrclrode potr~'tlal' In vollt or rtftrtncc elcct(odet ua fun~·ilon .. of ltmp,rahlre In •c

Temperature O.IM · -, Saturated I.OM
Calomel Calomcl .Ag/Ag~I,.
10 OJJ62 0.2S28 0.2314
15 QJJ60 0.2508 0.1286
20 o:nsii 0.2476 0.2256

.
2S 0.3JS.6 0.2444 0.2223
30 O .. HS3 0.2417 0.2190
40 O.JJ.15 0.2379 0.2131
C~ 50 O.JJ 15 0.2J08 0.2045
~0- Oi'i~: ·-'--~~~~----~-~~-'-~~~~~~ '.:·
Jf1"" ~• 1.Jnslcad of dropping mercury electrode, a roJaliiig (Jlalinum ._ 6 rnm Glnss Tubing ,.
"
~ ,.?'::>.Q"'\'· :;:1icro-ekc1rodc can be used. 111e faller possesses ihc following . n~nrJn Inward to '
..._'>l"' \J ~ adv-anlagcs over the ·droppiug mercury electrode : Prcv.cnl Ilg lrom
e
...-
<0('. o
~· \) IF.\ ·
'l!J It is simple to construcj.
·
,
being Thrownout ;I!
~ ¥ .·. I @~
0.,tQ.-(\..a...
_,/" @ ft jm:r~RSCi lhe worl<:lbJe range 011 the positive voJl~gc side # .
upto 0.9V. 'Tims it canbe used at positive potentials whereas" ~ . '
the mercury cl.:ctro'dc tn:ay not be used.
~· Y
@!!)
·
The technique is nidre. sensith;e because the rotation of the 5
electrode increases the.value of <liffusioi1 currc much as ~
(-.
ig Reservoir

( '~) . 20 time the value~·raph ··>· . M'~ '/!.

&i- 'f.i!!~~~~~~::!

ik
1 ro~1-u ... c..:r ,..,·v.e . ·
· The rotating plat in ·. -cl~cl'. n ror uce y H.A. Halo In Stem lor
Laitinen and LM. ~ohhnffiri 1941. II consists of glass tube of about M;iklnr1 Eloctrlcal .

n
• I 5-20 cm i11 lcnglh ·a1id 6 nuil in diarnc'rer•. A sho1t ,lcnglh of platinum
wire extends 5-10 mm froih rf1e wall qflh~ glass tube (Fig. 27.2). The
a
Conlact wlt!1 I lg Reservoir

electrode is mounted in the sh:iO ofa motor and rota led al a constant
speed of about 600 rota.tio~1s per minute, M "'+f ..,5.10 mm

amperomeu ic tit1atio11~ is shown in Fig. 27.3.

u r
A simple rot:itoi'y platinum electrode arrangement used in Plntlnum wlro

N
[n arnperomctric titrations removal of oxygen is llCCCSSa1y,~'f ~·'"'"'""

I n
ie electrolysis is carried 0:111 at an E.M.F. al which oxygen would.

r a
ave a diffusion current ... Removal of oxygen is done by bubbling
urified nitrogen be fore. the commc. nee.men! of the tiu ation and fo.r
bout I minute after each addition of the titrant,
t,,
Fig. 27.2

Imor
. ; .
{'>.3 Technlque or A111pcrp111c!ric Tilrat'lons .
Gal~anometor
The technique auipcromctr ic titrations may

d . be illustrated by considering the ti.lralion of a

reducible ion, like Pbu. Lead ions belngreduciblc at Mercury Contacl

M the cathode, give a diffi1~ion current whereas the

sulphate ion being non-reducible shows no diffusion
<curreru. The concentration of the reducible Pbl+
Salt Brid e .

ions is steadily decreased ~s the so,> ions removes

some of the electro-al 1i1 c l'b1• ions; A polarogram
. of a solution con!~i11.i11t: lt'ad ions is represented by Calomef Ccll
curve A in fig. 27.'1.
If the voltage is l;cjlt constant al any value of
fig. 27.3
,,,. diffusion current plateau, the limiting current value

:~az+ 1iiiiiiiiii
I m·-·.·~------~-
Rt+W~Jt: -~- ~·-~
·-~·· ..;;,
· · ~....;,:..:.-=--------~

2 / 6
 Amperometric Titrtuions
2.536
will be reprcscutcd hy ;11 con espondiug lo C0, the initial conccutration of lead ions. At this sla~c the titrant
exhibits 110 diffusion CUI rent at the applied E.M.F. . ....

A
- (,
c
O>
~I
i B
o'
u c
'8 12.
0
~ /3
u.
Residual Curront
I, I -

0 --0.4 -0.6 -1.2 -1.6 -2.0

Ee vs SCE·
Fig. 27.4

Th" curve A in fig.-27.4 represents the current i0 of the solution of lead ion's before 'th~'nddition ·
or any sulphate ions. The_ curve labelled D represents the current 11 after the addition of_ son?c,~ulpha_te .
ions to the lead Ions. Similarly the curves C nnd D represent 'the currents i2 and iJ which cofffspoild to' -
further additions of sulphate ions. Finally 1. is the point at which the lead ions have completely r~actcd,
At this stage the only ctu rent flowing is n rcsldual current and its value is characteristic of the sllppor1i1lg
electrolyte." _ --. ,'<): _ · · , - , < • - , ' _

following infcicl)ces can be drawn from Fig. 27.4.

The
(l) The decrease -in q1(i~:i1t with decrease in the concentration forms the ~
8
I k. _
basisofa~lpcronicki~titratioris.'-· ----. - -~ ·,Ji•_ - _
@ The volt:ige on '1i1~;'11ta!.~ail-?r
yolt3[lC 'curve illustrates the voltag~: :~ ,,
region which may bt,§p1ilicd inthe case of titration of lead ions-with 2 _, .. , ·-" .. , 09·:-. n~-~olnl · _
n i .
@
Ma
sulphate ions·amJi_do_lne_tr_ically. The range -0.S-volr is selected out 5 _ . · ·.-······ .
of the range ..:o.6 - to s1.2 ·volt to'r this titration. / . . · \) \ __
- Vol. of Tilranl Addod
'Now if we plot Ilic diffusion current against the 'volume of the titrant,
the type of curve which we with get is shown in Fig. 27.5.
u r
The intersection' ~f ,the extrapolated portions gives the end point. When the titrated ion is
Fig. 27.5

N
reducible and titrant is reducible, the ampcrornetric curve will be of the type shown in Fig. 21-:p.;
.
11011

a n - '

r
Im
M d. wl
po
tiu'
ck

tw1

for
" inv
Uni

3 / 6 _J
 2.~37
Arnperometr/c Titration:

and then in~reases as the lead ions are removed from the solution and then increases 'after the end ~oint
because of the increase in concentration of dichromate ions. A similar type of curve was also obtained,
when molybdenum was titrai~d against lead nitrate at a constant voltage of -0.8 V, by Aylward.

c
CJ
t:
:)

o
·j
s
?:"'
'1

0
,\\-c\.O;-Q~v ~..,_.(\ 12-.,..c:L P·o:~\- "~,
~~r: . U mo- ~·.or,;;,::;t::><)- ~,;:~'."""
~~.~~w{::~~6 ~.:(2~·'.< .-·
varum_o 01 _ri1;i~~~~'si>1uiiori 11.ililiiCI '
, .. Flg.27.~.
,.
':

.•.:·:!\
~ '·:· \ • :; r

•,..;
,.)'
~
'

. Redox titrations can ~ls:obc carried 0111 by arnpcromctric method. In an oxidation 'rcdu~tfo1I sysfeih,
where both oxidisingand rcdll~ing agents give diffusion current, the titration curve obtained is of the type
shown in Fig; 27.8.. · · . ' · ·
In the case of ferric JoJ1s til~at~d against titranous ions, the diffusion 1;ur:rent dccr~~-s~;)iii.fart}f\vith
the addition o~ titrant (Tihiqns) t<i the Jerrie ions unti] it attains the zero value ~! lhc ~nd poi1it l1.t this
point ferric ioris_havc·complcicly reacted. When more ti_trant is added, aflerthe end poini, :idiffusioi1 current
i k
caused by the oxi<latioi1-0C(ifr~llous'io11sis set up.-A ~Jiang~,!~_siiipe caused by t~e differciltc iii- diffusion
n
gives the end point. · .. ';+/( Jn ...... :.,-, , .,.., ->·, , - .. ·.. _. . Ma
coefficients Wusii?l_ly C\'i<l.c.11t ~s the lines cross the zero a1ti~·,,·p1~ ,pomt ofj1,1ie(s~ciio!1 of ihe two lines
: .. -; .·

r
Cc:mi;i ·. titrat.i~ns ir;~·~i'v.ing nc:utraHzati~~ and ·C~11;plc~,i~rt'f9i'nl'a'ti~;~--Ji~y·c'·~tso9c_ep1sUt:cc:~sfully
carric_cfout l>y:~:uhphomdtic 3m:thod. )'{cuberger has mo~ilic<l__ihe ampcr~lnctiic-n1ctl1?ci fof-'tliTstudy of.
u
studies. · ·
. . · N
precipitation 'rc'ai:tions. ile has' used reagents like dim~t)iylglyo~ime,' salicyaldoxime de. for such type of
· · · · ' .;c ,.

n
'

· Laitiner, Jenning~ ai\,1 l•arks have titrated iodide, bromide and chloride at a less negative potential,

r a
been use in these titrations the indicator reaction is 1I1e. deposition of silver from a quo-silver ioi1s. Micro-
molecular solutions of cadmium against E.o:r.A.-tiayc(bccn studied ampcromcrrically byNickelley a;1d

Im
Cooke in 1956. · ·
' .. :<> 1~.~_".._-.'/e.

\ '· 27.4 Dead slop'and-Pol11tl\icd10-d;.-... _,...._ [' "-/ ...,-

d . . Qr:, ' <"':'::'. ·. r:

Ti1ra1.io11s ,,;ilh lwo I11~icalo~'1f1ec:1rode
-,
. .: > i'"" < . . ·.•·. •· . ·..·
M
· JJ1!~,1_cphn.iqu~ is a ,;1,o~ifii:~tio11 of the Classical amperometric iitration. lniS.fiie'tfiOd is applicable t;·;ily..
when the Oxidatioh-reductiorfs'y-stcm is involved before and afier tli.e end .. .. , ..;,
poillt.In t!1is method two sin1ilar plitinum elcttrodes arc immcrscd)Q· the , .
· ·
a.
1i1ratioi(t~.p1···n1e'n a small "and constant voltage ls' appli_c~ to these l\yo ·
electrodes," · · - '· '·:.~ ." · - , · · ... ' · ·. ·
'1,~'Fl~Arcrn1Clric 1iti:ufoo··apparatus with Ilic two elc:~~~d~s'd(~;i:1~ ir~ .· .• -
two different vessels and linked through a salt bridge is shown in Fig. 27.9 ..
.r
The am~unt. of o~icliml form reduced al the cathode _is equal to ,that __ .... _ -
formed by ox1da11011 of lite reduced fonn al the anode, when the reactant '------1 G ,__ _
involves a reversible system. At this stage with electrodes are depolarized
uulil either the oxidized or the reduced member has been consumed by the Fig. 27.9
I - -..:..,_
\:~·
-~

---- I

4 / 6 - .,,, J
 2.5)8.

titrant. AflCJ the end p;1i111: 011iy one clccuodc remains dcpo\~1izcd as if the
titrant docs 1101 involve a reversible system. Thus the current becomes zero ~ ~-

. J . ~"'·
or vc1y close to zero ut the cud point and this shoots up as shown in Fig. G
27.10. c
The 111c1!1od W~' introduced by c.w.
Foulk and A.T. Bawden in 1926, ]
under the name "deod ,,p(11 end point". The reverse of this type of end point 0 ······E;:Ki~i ... ;.
is called "kick of]" nnd resembles n reversed Lshaped ampcromctric curve.
Vol. ol 1 ilranl Added
Amperornctric methods with two cleclr~des have not been- full)' exploited Fig. 27.10
amt there arc few oxidation-reduction systems to which this encl-point
technique could he ripplfcd with advantage. Most of these 'titrations involve iodine. llo~vcvcr, a few
titrations with reagents such as bromine, +3 titanium and +4 cerium have been reported. An important use
is in the tination of water' with Karl Fischer reagent. . .
111c principal ndvantagc of the two electrodes is its simplicity.

, fos"0-tlva~~t~ci}of_j\11i;lc;~o111ctri~..111rations . . .
'7 .:-·n;~sc
below:
titratious have a number of advantages over other methods, therefore some of ~hese are given
: .·. . · ·
~ The apparatus used is simple and the. characteristics or electrodes arc less important.
"'® Tile 11ieth~d in~-l~1tl~e, therefore, Iewer disturbing factors arc prevalent. .·
v@ The aecurncy 15 -ii11:hcr than In polarokraphy and tho error-In the .deierminaticu or the end point
depends on the #~lfity of the studenr; 2 - - . . .: · : .. ··
!teed no! be J<riown provided it rernains comtant throughout the experiment.
The temperature·
.
The range an.l ti'1t
' - . - - 7 - . . .

i k
sensitivity of .the tcchnlque are more· than conductometric or' potentiometric
of
titrations. In reality, the amperornetric methods arc best for the detcrmi11ntion
n
traces of elements

Ma
with good precision. The concentrations ranging from 0.1 to 0.0001 M and even in certain cases to
0.000,001 M can be measuredaccurately, .
v@ It is not heccssnry to have capillary characteristics of the dropping electrode.
ve r
It is llQ.! 11cccssa1 y lo maintain constaut current throughout the titration ..
\ (viii) Iris i-:Um11eriafwhcthcr
N u
the r~ac_tion which occurs during the titration is reversible or irrevcrsibl~.
M J!•e clcpohri~l11g~""~trmce' which ~n~not be deten1;lnc<1 very accurately by polarography, can be

a n
s11cccssfullydcicri1ii11ed by amperornetric titrations, For such substances, a suitable titrant is selected
which g~vcs n diffuslon current: Moreover some other sy11e111§ which .do no! possess measurable

r
equilibrhuu p11tei11.,iills can be estimated emperomeulcnlly, An intcrestiug c*arpple Is that magnesium

Im
which docs 1101 J:iV~ the diffusion current CUrVC, can be determined by using 8-hydroxyquinoline
which gives n · reduction curve. · - ·_ ' -. · . - , ,_
v@ These titratious, iaii, be carried out~ because the end. point is found graphically. ·
'®
v@ d . The presence of (6tcign salts docs not interfere, instead these arJ as supponiug electrolytes.

@M
.!Jilut.e soluti~ns -cac.thc titrated will! high degree of accuracy. · ·
~be method is on~, of the few methods .wltlch arc generally applicable lo precipitation tilI?tions.

27.6 l?fs·a_dyantagcs of Ainpcromc~ricTitrations

''iris~ite of large ntfrt1ber ~f advantages as discussed ·c~rlier, the amperomctirc titrations possess U1e
. following disadvautages: ·
~ . ~1accu~.* 1cs1dh ar~ sometime~ ~brained because of't~~scipital_i@. ·, · . .
@ The foreign substances which do not interfere: in the arnpcromclric titration should not be present
in larP,cr concentrations than the substance to. be titrated. In their prcsc;nce, the relative c~t
b~.· '

5 / 6
 I

I ..
I IS 2.539
I • ' ' ' - - -_ .

l . · · ·
I

I
"~· .>
~
. <!J.1 Applknlloi" ~.r
<D .··~·he ~;;,1,~ri;;;·;ch_ic.·
precipitate
Ai11petom'e~r!~!~~s < ·.. .

;ml poi;11••hns been_ mostly 7on~11ed to t.ilrati~ns•. in wl1.ich _a slighily soluble:

rs the reaction product • .:>OlllC selected apphcqllons are listed 111 Fable 27.2.
. .
Tuble :27.2 t Sortie Prrclpltatlon Tltratlons I •11ploylng the Amprromctrlc End Point

Electrode R_<"ngr11t Substonce Determined

Dropping K2Cr04 1 Pb2', Da1•
mercury l'h{NOJ)2 ; so,», Moo/-; F-, c1-
f:-hydro.~y<111inoli1• .• M1:2•, Zn1+, Cui+ . .
Cupffcrron I Cu2', Fe:•
l>imi:1liylgl)'oxii'111: 'j\Jjl• -.
I . ·-
K/'c{CN)6 . • Zi1H
Ror~linit plaii11111·11 AgN01.. ·.. . . .· ' cl-, Br-, 1-, cN-

.ven
'4 Ampcron::I~~
for following
clectn?dcs are liriding impor1a111 ;1pplications as ~1tlcr~dctcclorsi1
the elution of clec:l111:i_cliVC: SU stances, . ·' . . '·•
i
·'
GD Twin silvct mlcrcelectrodc- ha~e b~e.;1
C:ll•j>loycd for en;J.point'dc!ccrioh in whi~h silver ion is a
precipitant. for example, in the lilralion of silver ion with 3 standard solution Of chloride ion, CUITClllS
proportional ~?)hemetal ion concentration would result from the reactions":
ioint Cathode, ·: Ag+.~ c -.-.Ag
i k
Anode Ag -·-· Ag++ e
n
Ma
.With th~ ~(fceth;c removnl 11f silver ion by the analytical reaction; cathodic polarisation would occur
ictric and the eurrc1~t would approach zero at. the _end point. · ·
ucuts
...

£\--- (~ .~' \'C>

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u r ~41e1Dw~~
-~•·· ~-d.0~

~6.~ru_, N -~G.n..:.. pc~"''·

°""""It.. ~cl·

..;© i\-
a n
~<!)\- ~
1'~

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•

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"'®· ~.r··~
d .
@ --ta·· · ·t<EA=v ~
M w l'/-t1

i,

t .

MUHA MOD MRAN NQOR

-mant. 1111heY1her.:0:n
"'

6 / 6