M. M.

El Jamal,

H. H. Hammud
97
Journal of the University of Chemical Technology and Metallurgy, 42, 1, 2007, 97-104
QUANTITATIVE DETERMINATION OF METALS IONS USING Fe (III)/ Fe (II) REDOX
TITRATION SYSTEM WITH A PLATINUM ELECTRODE
M. M. El Jamal
1
, H. H. Hammud
2
1
Faculty of Science, Chemistry Department,
Beirut Arab University, Beirut Lebanon, Box: 11-5020
E-mail: mjamal@ul.edu.lb
2
Faculty of Science, Chemistry Department,
Lebanese University, El Hadath, Lebanon
ABSTRACT
Tc ucc:nnnan aI ncn ans usng P cc:auc a ucc c cquvncnc pan vns pc:Ia:ncu l, nssn
pacnanc:,. Cu (11), Cu (11), Zn (11), A (111), C: (111), Pl (11), (11), nnu Ca (11) nvng c: Ia:nnan ansnn lcvccn
n aI FcY
2-
nnu FcY
-
nn lc ucc:nncu qunnnvc, l, s ncau. Tc lcnva: aI sanc ncn ans (su ns (11),
C: (111) nnu A (111)) s nIIccu l, nc p:alcns vc:c Fc (111) uacs na upncs FDTA I:an c: anpcxcs v FDTA.
Oc: ncn ans c Zn (11), Ca (11), nnu Cu (11) pn:n, ucvc: c: FDTA a Fc (111).
Havcvc:, c ncn ans cs Bn (11), Cn (11) nnu Mn (11) nvng c: Ia:nnan ansnn css nn n aI FcY
2-
nn
na lc suucu l, s ncau snc Fc (111) upncs c FDTA I:an c ncn anpcxcs lcIa:c up nng I:an FcY
2-
.
Kc,va:us: pacnanc:,, P cc:auc, FDTA :nan, Fc (111), Fc (11) s,scn.
Received 18 January 2007
Accepted 20 February 2007
INTRODUCTION
Complexometry titration ol metal ions by oirect
or back titration witl IDTA las been well stuoieo [1,
2]. Tle oetermination ol concentration ol metal ions
can be evaluateo by pH-metry titration witl a
2
IDTA
[3] ano also by \VfVis absorption spectrometric titra-
tion using special liganos [3, 4]. Twenty years ago, in-
tensive researcl was oone to elaborate selective elec-
trooes to measure tle concentration ol metal ions [5].
However, tlese selective electrooes neeo a special treat-
ment to be active ano any oelect allects tleir response.
Anooic stripping voltammetry las been wioely useo lor
tle oetermination ol leao, zinc ano caomium.
Amperometry titration using oropping Hg electrooe was
also useo to oetermine metal ions [6, 7].
We propose tle oetermination ol metal ions us-
ing a Pt electrooe. Tlis electrooe is easy to use ano oo
not neeo special treatment belore use. !n tle literature,
we only louno tle oetermination ol i (!!) by tle sug-
gesteo metloo [8], we try to apply tlis metloo to otler
metal ions, like Co (!!), Cu (!!), Co (!!), Zn (!!), Pb (!!),
Al (!!!), Cr (!!!). Tle iron system las tle aovantage
tlat botl Ie (!!!) ano Ie (!!) are soluble in water ano
lorms stable complexes witl IDTA, witl oillerent con-
stant lormation, in contrast to Cerium system wlere
only Ce (!!!) lorms complex witl IDTA [1, 2]. Tle Pt
electrooe is gooo sensor to lollow tle concentrations ol
Ie (!!!) ano Ie (!!).
IDTA is tle best ligano lor tlis stuoy because
IDTA lorms 1:1 stable complex witl tle major metal
ions especially witl Ie (!!!) ano Ie (!!) ions, in contrast
Journal of the University of Chemical Technology and Metallurgy, 42, 1, 2007
98
to o-plenantroline (o-plen) or otler ligano wlicl lorms
MLn complexes (n 2 or 3) witl several metal ions
[9]. Tle lormation constant ol M (o-plen)
n
to be stuo-
ieo are smaller tlan Ie
!!!
(o-plen)
3
ano Ie
!!
(O-plen)
3
[9].
Tlus tlese metals can not be oetecteo by tlis metloo.
EXPERIMENTAL
Tle potentiometric measurements were carrieo
out using computerizeo potentiometer witl ico 2
Ilit 8-clannels ions analyser (reaoing

.1 pH or
mV unit). Tle combineo glass electrooe was calibrateo
lrom time to time using two stanoaro buller solutions
4. ano 7.. Tle response ol tle Pt combineo electrooe
ano its slope was verilieo witl Ie (!!!)f Ie (!!) in 2. M
H
2
SO
4
. All tle reagents useo were purclaseo lrom BDH
prooucts. All solutions were prepareo in oeionizeo wa-
ter. Ierrous solution was prepareo lrom Molr salt in
.1 M H
2
SO
4
to prevent its oxioation. Ierric solution
was prepareo lrom lyorateo lerric sullate in .1 M H
2
SO
4
to prevent its precipitation. Tle a
2
IDTA solution was
prepareo as oescribeo in [1]. Metallic ions solutions were
stanoaroizeo by complexometry witl .1 M a
2
IDTA
solution [1, 2].
PotontIomotrIc procoJuro
!n tle lirst step 1. ml ol IDTA (.1 M) was
aooeo to 1. ml ol Ie (!!) .1 M ano 1. ml ol acetic
buller 2 M ( pH 4.2) into a beaker ol 1 ml ano
oiluteo to 4. ml witl oeionizeo water, tlen titrateo
witl Ie (!!!) (.1 M). Tle acetic buller is useo to lix
tle ionic lorce ano tle pH ol tle solution. !n tle secono
step, we aoo to tle initial mixture a variable volume
(between . ano 1. ml) ol tle metal ion (.5 M) to
be titrateo so tlat tle total volume ol tle solution is
4. mL. Tle concentration ol tle metal ion, Ie (!!)
ano M
n
in tle beaker must be less tlan tle initial con-
centration ol IDTA. Tle pH ano tle potential were
taken alter eacl aooition ol Ie (!!!) solution (.1 M).
Tle pH measurement is not necessary; it is only to be
sure tlat tle pH remaineo constant ouring titration.
Only in tle case ol Cr (!!!), tle titration was
oone at 45
o
C to accelerate tle complex lormation. Tle
titration ol Cr (!!!) at room temperature is not accurate
because ol non spontaneous lormation ol complex, since
tle violet colour ol CrY
-
oevelops witl time.
THEORY
VrItIon ol tho potontIl ol tho solutIon JurIng
tItrtIon
IDTA lorms complexes witl Ie (!!!) ano Ie (!!).
To simplily tle potential relations, we oo not take into
account tle lormation ol complexes between Ie (!!!),
Ie (!!) ano acetate (Ie (!!)-acetate: logp
2
5.3, Ie (!!!)-
acetate: logp
2
1.3) [9].
Belore aooing Ie (!!!) tlere is in solution tle
complex IeY
2-
ano excess ol IDTA:
48 . 7
3
2
3
2
2
10 2 2 ) ( = + + +

K COOH CH FeY COO CH Y H II Fe

Tle Pt electrooe measures a mixeo potential ol tle
IeY
2-
(reouctant) ano CH
3
COOH (oxioant in CH
3
COOHf
H
2
). Alter aooing Ie (!!!) tle reaction will be:
28 . 18
3 3
2
2
10 2 2 ) ( = + + +

K COOH CH FeY COO CH Y H III Fe

Ano tle potential I (V) ol tle solution will be as
preoicteo by ernst equation at 25
o
C:
] /[ ] log[ 059 . 0 ) / (
2 2 0
+ = FeY FeY FeY FeY E E
0
2
1 2
( ( ) / ( ))
0.059log / 0.059log[ ]/[ ]
E E Fe III Fe II
FeY FeY

=
+ +
] /[ log[ 059 . 0 13 . 0
2
+ = FeY FeY
2 1
and
: Iormation constant ol IeY
2-
ano IeY
-
ano equal to 1
14.3
ano 1
25.1
, respectively [9].
2 1
and
are botl multiplieo by tle same lactor
(o
Y
4-
), tleir ratio remains tle same.
V II Fe III Fe E 77 . 0 )) ( / ) ( (
0
=
Tle last equation can be written as lollow:
V FeY FeY E E log 059 . 0 ) / (
2 0
+ =

(Linear relation)
wlere V is tle volume ol Ie (!!!) aooeo.
Wlen tle lree IDTA are complexeo, Ie (!!!)
aooeo will react now witl IeY
2-
to lorm tle more stable
complex Ie Y
-
:
M. M. El Jamal,

H. H. Hammud
99
.
( ) ( )
/
FeY Fe III FeY Fe II
K

+ +
= =

2
10 8
1 2
10
During tle reaction [IeY
2-
] oecreases ano [IeY
-
] contin-
ues to increase. But as tle .59 log [IeY
-
]f [IeY
2-
]
sligltly varies, we will not observe an appreciable
clange in potential. At tle equivalent point tle ox-reo
system in solution will be Ie (!!!)f Ie (!!) ano a suooen
jump in potential will occur. Tle relation between po-
tential I (V) ano tle aooeo volume ol Ie (!!!) alter tle
equivalent point will be:
)] ( /[ )] ( log[ 059 . 0 )) ( / ) ( (
0
II Fe III Fe II Fe III Fe E E + =
) log( 059 . 0 )) ( / ) ( (
1
0
V V II Fe III Fe E E + =
V
1
is tle volume ol Ie (!!!) to complex tle total
IDTA. Tle titration curve ol Ie (!!!) witl IDTA slows
only one equivalent point (Iig. 1)
Variation of the potential of the solution dur-
ing titration of M (II) in presence of excess of EDTA
and FeY
2-
Belore aooing Ie (!!!), tle composition ol tle
solution is MY
2-
, IeY
2-
ano excess ol IDTA, alter aoo-
ing Ie (!!!) tle successive clemical reactions will be in
oroer:
) 1 ( ) (

+

FeY III Fe EDTA

2
2 2
( ) ( )
( )
FeY Fe III FeY Fe II
if MY is more stable than FeY


+ +

(2)
) 3 ( ) ( ) (
2
II M FeY III Fe MY + +

witl
) tan : ( /
2
3 3 1

= MY of t cons formation the K

Tleoretically, ouring tle reactions (1) ano (2),
tle potential ol tle solution will be tle same as in ab-
sence ol M (!!) ano tle potentiometric curve will be
overlaio. At tle eno ol tle reaction (2), tle potential
increases suooenly, tle lirst equivalent point corresponos
to tle complexation ol lree IDTA witl Ie(!!!) ano oe-
struction ol IeY
2-
(call V
2
tlis volume), tlen aooitional
Ie (!!!) attacks tle more stable complex MY
2-
. Tlis
reaction (3) gives a secono plateau ano prevents tle
potential to reacl tle ligler value ol Ie (!!!)fIe (!!)
system. At tle eno ol reaction (3) a secono equivalent
point is obtaineo corresponoing to tle total oestruction
ol MY
2-
. Tle tleoretical titration curve ol M (!!) sucl
as i (!!) tlus sloulo slow two equivalent points as
seen in (Iig. 1).
Tle concentration ol Ie (!!!) ouring tle
reaction (3) will be:
5 . 6
1
3
2
10
)] ( [
)] ( ][ [
] [
)] ( ][ [
)] ( [

= =
II Ni
II Ni FeY
NiY
II Ni FeY
III Fe

As tle Pt electrooe is sensitive to tle system

present in solution tle potential will be:
)] ( /[ )] ( log[ 059 . 0 )) ( / ) ( (
0
II Fe III Fe II Fe III Fe E E + =
) / log( 059 . 0 )) ( / ) ( (
1 3
0
II Fe III Fe E E + + =
)] ( )][ ( [
)] ( ][ [
log 059 . 0
II Fe II Ni
II Ni FeY

+
Irom tle titration curve we can calculate tle con-
centration ol tle metal ion ano tle constant lormation ol
MY
2-
. Tle volume ol IDTA reacteo witl x ml ol i (!!)
is equal to tle oillerence in Ie (!!!) volumes (V
1
-V
2
)
Fig. 1. Comparison between the theoretical and experimental
titration curves of 10 ml of Ni (II), 0.05 M with Fe (III) in
presence of 1ml of Fe (II), 0.1 M and 10 ml of EDTA, 0.1 M.

-120
-100
-80
-60
-40
-20
0
20
40
60
80
100
120
140
160
180
200
220
240
260
0 0. 5 1 1. 5 2 2. 5 3 3. 5 4 4. 5 5 5. 5 6 6. 5 7 7. 5 8 8. 5 9 9. 5 10
volume of Fe (III)
E ( mV)
10 ml Ni (II)
theori tical curve of10 ml of Ni (II)
Fe(II) alone
V1
V2
Theori tical curve

Experimental curve
Journal of the University of Chemical Technology and Metallurgy, 42, 1, 2007
100
ano tle concentration ol tle unknown solution will be:
x. [i (!!)] .1 (V
1
V
2
).
Wlen MY
2-
is totally oestroyeo, lree Ie (!!!) will
be in solution, tle potential will be anotler time equal
to:
)] ( /[ )] ( log[ 059 . 0 )) ( / ) ( (
0
II Fe III Fe II Fe III Fe E E + =
) log( 059 . 0 )) ( / ) ( (
1
0
V V II Fe III Fe E E + =
But some time lor kinetic problem like tle case
ol Al (!!!), i (!!) ano Cr (!!!), we see only one equiva-
lent point corresponoing to tle titration ol tle remain-
ing IDTA in solution alter aooing M (!!).
RESULTS AND DISCUSSION
Determination of the optimum conditions
for the titration of the metal ion with Fe (III)
Elloct ol tho InItIl volumo ol 1o (11) JJoJ to solutIon
Tle titration curves ol Ie (!!!) witl IDTA in
presence ol oillerent volume ol Ie (!!) (.5, 1, 3 ano 5
ml) slow tlat tle volume ol Ie (!!) aooeo allects tle
I measureo, but ooes not allect tle slape ol tle curve,
neitler tle volume ol tle equivalent point, but tle suo-
oen clange in I is obtaineo at low volume (.5 ano 1
ml). We preler to aoo 1 ml ol Ie (!!) lor convenience.
SthIlItIos ol tho comploxos s lunctIon ol tho pH
Tle conoitional constant lormation ol IeY
-
ano IeY
2-
varies witl pH. Tle complex IeY
2-
is not
stable at pH lower tlan 3. oue to tle weakness ol its
conoitional constant value, but tle constant lormation
ol IeY
-
is very big. Tle reaction (1) occurreo partially
in very acioic meoium ano it is conlirmeo by tle ap-
pearance ol tle yellow colour ol IeY
-
alter aooing ol a
small quantity ol Ie (!!!). On tle otler lano in tle
presence ol IDTA, Ie (!!!) lyorolysis (lormation ol
Ie(OH)
2
ano Ie (OH)
2

) occurreo at pH ligler tlan

6., so we must cloose a compromise about tle selec-
tion ol tle pH ol tle solution. Tle curve I in lunction
ol pH ol tle system IeY
-
f IeY
2-
slows a plateau be-
tween 3 ano 7 so we concluoe tlat tlese complexes are
stable in tlis zone.
Elloct ol tho pH ol tho hullor
Tle titration curves ol Ie (!!!) witl IDTA in
presence ol Ie (!!) at oillerent pH between 1. ano 6.
(Iig. 2) slow tlat tle pH ol tle solution allects tle
slape ol tle curve, tle potential measureo, tle leiglt
ol tle jump, ano tle volume ol tle equivalent point.
We concluoe tlat tle best pH lor titration ol Ie (!!!)
witl IDTA is between 3. ano 5..
Also, tle conoitional constant lormation ol MY
n-4
varies witl pH, so we must cloose tle best pH lor tle
titration ol Ie (!!!) ano M
n
witl IDTA. We select i
(!!) lor tlis stuoy. Tle titration curves ol i (!!) witl Ie
(!!!) in presence ol Ie (!!) ano excess ol IDTA at oiller-
ent pH between 1 ano 5 slow tlat tle complexes iY
2-
ano IeY
-
are stable at lower pH, but tle titration at pH
1. is not accurate. Tle titration curves at pH ligler tlan
3 slow tle typical S- slape. Since tle complex stability
increases witl pH, we lave closen tle pH 4.2 as optimal
pH lor tle titration ol all metal ions.
Apparent standard potential of Fe (III)[ Fe (II) in
acetic acid medium 2 M
!n oroer to interpret tle titration curve ol tle metal
ion, we calculateo experimentally tle apparent stanoaro
potential in acetic buller lor Ie (!!!)fIe (!!) system ano
IeY
-
fIeY
2-
systems. Tle titration curve ol a mixture ol
5. ml ol eacl ol Ie (!!!) ano Ie (!!) (.1 M) witl
IDTA slows two plateaus. Wlen tle volume ol IDTA
aooeo is less tlan 5. ml, IDTA complexes only witl
Ie (!!!) ion. Ie (!!) IDTA complex begins to lorm lor
aooition ol more tlan 5 ml IDTA. Tle measureo po-
tential in tle lirst plateau corresponos to tle system Ie
(!!!)fIe (!!) in acetic buller, wlereas tle secono one
corresponos to tle system IeY
-
f IeY
2-
. We obtaineo
.35 V ano .14 vs. S.H.I, respectively. Tle secono value
is near tle publisleo value [9].
-150
-100
- 50
0
50
100
150
200
250
300
350
400
450
500
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10. 5 11 11. 5 12
Vol ume of Fe (III)

E

(
m
V
)
pH =1
pH =3. 5
pH= 4. 3
pH=5.2
pH 6. 2
pH=1
pH=3.5
pH=4.3
pH=6.1
pH=5.2
Fig. 2. Effect of the pH of the solution on the titration curve of
Fe (III) with EDTA.
M. M. El Jamal,

H. H. Hammud
101
Titration of metal ions with Fe (III) in presence of
Fe (II) and excess EDTA
Tle metal ions stuoieo were oivioeo into two
groups witl respect to tle belaviour ol tleir com-
plexes witl lree Ie (!!!). Tle lirst group containeo
lour metal ions (i (!!), Cu (!!), Al (!!!) ano Cr (!!!)
ano tle secono containeo lour metal ions (Zn (!!), Co
(!!), Co (!!) ano Pb (!!)).
1ItrtIon ol NI (11), Cu (11), Al (111) nJ Cr (111)
Tle potentiometric titrations ol i (!!) slow a
slilt ol tle equivalent point to tle lelt witl respect to
tle titration curve in absence ol i (!!) (Iig.3). Tle
slilt is proportional to tle volume ol i (!!) aooeo.
Tle volume ol tle lirst equivalent point is a lunction ol
tle volume ol i (!!) aooeo as slown in Table 1. Tle
obtaineo titration curves lor Al (!!!), i (!!), ano
Cr (!!!) are very similar. Tle titration curve ol Cu (!!)
is also similar, but oeviation occurreo at ligler poten-
tial 1 mV vs AgCl fAg electrooe. Alter total com-
plexation ol Cu (!!), tle copper curve oeviates sligltly
oown witl respect to tle nickel curve (Iig. 4). Tlis
oillerence in belaviour between i (!!) ano Cu (!!)
can be explaineo witl a partial release ol IDTA lrom
CuY
2-
to Ie (!!!). Tlis oeviation is important at ligler
concentration ol Cu (!!) (greater tlan 5. ml copper)
as preoicteo by Le Clatelier law.
Tle experimental titration curves ol i (!!) are
in contraoiction witl tle tleoretical curve, wlicl must
present two equivalent points, one corresponoing to
tle titration ol lree IDTA ano oestruction ol IeY
2-
ano tle secono - to tle oestruction ol MY
2-
. Tlis can
be explaineo witl a kinetic problem, since tle reac-
tion (3) is tlermooynamically possible (tle equilib-
rium constant ~1
6
), but kinetically unlavorable (tle
activation energy ol tle slow step is very ligl). Spec-
troscopy stuoy conlirms tlat tle absorbance at
59 nm (
max
ol iY
2-
) remains constant ouring tle aooi-
tion ol Ie (!!!). Ior excess Ie (!!!),
max
slilt to 56 nm
oue to tle lormation ol Ie (OH)
n
3-n
species (n 1 or 2).
Several attempts were oone to over come tlis problem,
- 120
- 100
- 80
- 60
- 40
- 20
0
20
40
60
80
100
120
140
160
180
200
220
240
260
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10. 5
Vol ume of Fe (III )

E

(
m
V
)
5 ml Ni (II)
10 Ni (II)
2 ml Ni (II)
7 ml Ni
Fe (II) alone
Fig. 3. Titration curves of x ml of Ni (II) 0.05 M with Fe (III),
0.1 M, in presence of Fe (II) and excess of EDTA.
-120
-80
-40
0
40
80
120
160
200
240
280
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5
Volume of Fe (III)
E

(
m
V
)
5 ml Ni (II )
delat E/ 5 ml Cu
10 Ni (II )
delat E/ 10"ml Cu
Fig. 4. Comparison between the titration curves of Ni (II) and Cu
(II) with Fe (III) at similar conditions.
Volume of Ni (II) to be titrated 0 2 5 7 10
Volume of Fe (III) at the 1st eq.pt. 9.5 8.6 7.1 6.2 4.6
V
1
- V
2
--- 0.9 2.4 3.3 4.9
[ Ni (II)] --- 0.045 0.048 0.049 0.049

Table 1. Volume ol .1 M Ie (!!!), at tle lirst equivalent point as a lunction ol tle volume
ol i (!!) aooeo .5 M (2, 5, 7, 1 ml).
Journal of the University of Chemical Technology and Metallurgy, 42, 1, 2007
102
to accelerate tle exclange between MY
2-
ano Ie (!!!).
Tlree lactors were stuoieo on i (!!) in oroer to ois-
place tle equilibrium to tle riglt:
a) Tle titration at ligler temperature (35 ano 45
o
C);
b) Tle titration at oillerent pH;
c) Tle titration in presence ol oimetlylglyoxime
(DMG).
o clange in tle measureo potential ol tle ti-
tration curve was obtaineo. Tle aooition ol DMG ooes
not cause tle precipitation ol i (DMG)
2
. We observe
only at pH 1. a partial release ol IDTA lrom iY
2-
to
Ie (!!!), but at pH 1. tle titration ol i (!!) is not
accurate as mentioneo above.
Titration curves of Zn (II). Co (II). Cd (II) and Pb (II)
Tle titration curves ol Zn (!!) witl Ie (!!!) in
presence ol Ie (!!) in acetic buller, slow two equiva-
lent points, tle lirst equivalent point corresponos to tle
titration ol lree IDTA ano oestruction ol IeY
2-
ano tle
secono equivalent point corresponos to a partial release
ol IDTA lrom ZnY
2-
to Ie (!!!) (reaction (3) (Iig.5).
We use tle oerivative metloo to lino tle volumes ol
tle equivalent points in contrast to tle titration ol i
(!!) wlere we use tle tangential metloo. Tle slilt to
tle lelt in tle lirst equivalent point is proportional to
tle volume ol Zn (!!) aooeo as in tle case ol i (!!).
Tle release ol IDTA is more important tlan in tle
case ol Cu (!!). o correlation exists between tle sta-
bility ol tle complexes ano tle exclange ol IDTA be-
tween MY
n-4
ano Ie (!!!). Tle exclange ol IDTA be-
tween Ie (!!!) ano Zn (!!) is slow. Since we are inter-
esteo only in tle oetermination ol tle concentration ol
tle metal ion, we can stop tle titration a little alter tle
lirst equivalent point to reouce tle time ol tle experi-
ment. Tle secono equivalent point is not involveo in
calculation.
Tle potentiometric titration ol 1 ml ol .5 M
Co (!!) witl .1 M Ie (!!!) in presence ol excess IDTA at
oillerent temperature (29, 5, ano 65
o
C ) slows tlat tlese
curves are nearly overlaio but oeviates to tle riglt near tle
secono equivalent point (Iig. 6). Tle oeviation increases
witl tle increase in temperature. Tlis oeviation can be
oue to tle increase in tle exclange ol IDTA between
CoY
2-
ano Ie (!!!). At ligler temperature (65
o
C) tle ex-
clange is not complete since tle volume ol tle secono
equivalence point is experimentally 9.3 wlile tleoreti-
cally is 9.8.
Tle potential ouring reaction (3) increases alter
eacl aooition ol Ie (!!!) tlen oecreases slowly, oue to
tle slow lormation ol IeY
-
. Tle titration curves ol
Co (!!) ano Co (!!) are similar to tlose ol Zn (!!). Tle
oecrease in potential in tle case ol Zn (!!) is laster tlan
tlat ol Co (!!) wlicl means tlat tle exclange between
Zn (!!) ano Ie (!!!) is laster tlan lor Co (!!) ano Ie
(!!!). Spectroscopy stuoy conlirms tle exclange ol IDTA
between CoY
2-
ano Ie (!!!), accoroing to tle reaction
(3). Tle absorbance at 5 nm (
max
ol CoY
2-
) increases
suooenly alter aooing Ie (!!!) to CoY
2-
solution oue to
tle lormation ol Ie(OH)
n
3-n
(n 1 or 2). Tle absor-
bance tlen oecreases witl time oue to tle clange ol
Ie(OH)
n
3-n
to IeY
-
.
Tle titration curves ol a mixture ol 5. ml ol
i(!!) .5 M witl 5. ml ol Al (!!!) .5 M, or a
-1 50
-1 00
- 50
0
50
1 00
1 50
2 00
0 0 . 5 1 1. 5 2 2 .5 3 3. 5 4 4. 5 5 5 . 5 6 6 . 5 7 7. 5 8 8. 5 9 9 . 5 10 1 0. 5 11
Vol ume o f Fe (I I I )

E

(
m
V
)
10 ml of Co (II ) at 50 C
10 ml of Co (II ) at 64 C
10 ml of Co (I I) at 29 C
Fe (II) alone at 29 C
29 C
64C
Fig. 6. Titration curves 10 mL of Co (II) at different temperature
(65, 50 and 29

C).
Fig. 5. Titration curves of x ml of Zn (II), 0.05 M with Fe (III)
0.1 M in presence of Fe (II) and excess of EDTA.
- 150
- 100
-50
0
50
100
150
200
250
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10
volume of Fe ( III)

E

(
m
V
)
Zn (II) 0 ml
Zn ( II) 10 ml
Zn ( II) 5 ml
Zn ( II) 2 ml
M. M. El Jamal,

H. H. Hammud
103
mixture ol 5 ml ol i (!!) .5 M ano 5 ml ol Zn (!!)
.5 M inoicate tlat tle volume ol tle lirst equivalent
point is similar to tle volume ol tle equivalent point ol
1. ml ol i (!!) .5 M. So, we can only calculate tle
total concentration ol metal ions. Tlus tle metloo is
not selective.
Tle titration curves ol Pb (!!) slow two equiva-
lent points. Tle lirst corresponos to tle total complex-
ation ol Pb (!!) witl IDTA wlile tle secono one corre-
sponos to tle nearly total exclange ol IDTA between
Pb (!!) ano Ie (!!!) (Iig. 7). Tle presence ol sullate in
solution coming lrom Ie (!!!) ano Ie (!!) solutions causes
tle precipitation ol PbSO
4
. !n tlis way it accelerates
tle exclange between Pb (!!) ano Ie (!!!):
4
2 2
4
) ( PbSO FeY PbY SO III Fe + + +

Tle titrations ol metal ions likes Hg (!!) ano Ce

(!V) are not possible witl tlis metloo, because tle stan-
oaro potential ol tlese ions is ligler tlan tle stanoaro
potential ol Ie (!!!))f Ie (!!). Tlis causes oxioation ol
Ie (!!) ano lurtler none lunctioning ol tle inoicator
electrooe. Also, tle lormation ol gray mercury colloi-
oal precipitate glue on tle lole ol tle combineo Pt elec-
trooe leaos to incorrect measureo potential.
CONCLUSIONS
Tle titration curves I versus volume Ie (!!!))
slow tlat tle metal ions stuoieo can be oivioeo into
tlree categories (Iig. 8):
Tle metal ions laving constant lorma-
tion MY
n-4
less tlan tle constant lormation ol
IeY
2-
(1
14
) like Mn (!!), Ca (!!), Ba (!!);
Tle metal ions laving constant lorma-
tion MY
n-4
between tlat ol IeY
2-
ano IeY
-
(1
14
p 1
25
) like Co (!!), Cu (!!), Al (!!!),
Cr(!!!), Co (!!), Zn(!!), Pb (!!) ano i (!!);
Tle metal ions wlicl oxioize Ie (!!)
in tle present conoitions, like Hg (!!).
Tle lirst ano tle tliro categories can
not be stuoieo by tlis metloo. !n tle lirst case Ie (!!!)
aooeo will attack MY
n-4
belore IeY
2-
. Tle reaction
between MY
n-4
ano Ie (!!!) ooes not clange tle con-
centration ol IeY
2-
, so tlere is no big clange in I.
Tle curves witlout M
n
ano in presence ol M
n
are
similar. Tle presence ol M
n
ooes not allect tle po-
tential ol tle solution.
Tle metal ions in tle tliro category react witl
Ie (!!) to give Ie (!!!). So tle inoicator electrooe is
eliminateo lrom tle solution. Tle aooition ol Ie (!!!)
will increase tle concentration ol IeY
-
, causing a slow
increase in tle measureo potential.
Tle secono category incluoes eiglt metal ions
i (!!), Zn (!!), Co (!!), Co (!!), Cu (!!), Al (!!!),
Cr(!!!), Pb (!!) easily oetecteo by tle proposeo metloo.
Tle titration curves slow tlat tle belaviour ol ions is
oillerent ano can be oivioeo into two groups. Tle lirst
group incluoes Al (!!!), Cu (!!), i (!!) ano Cr (!!!)
wlere no exclange ol IDTA occurs between MY
n-4
ano
Ie (!!!). Tle secono group incluoes Pb (!!), Zn (!!) ano
Co (!!) wlere a partial release ol IDTA occurs between
-100
-50
0
50
100
150
200
250
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11
del ta E /5 ml Pb
del ta E /Fe (II) alone
del ta E /10 ml Pb
del ta E /7 ml Pb
del ta E/10 Ni (II)
Fig. 7. Titration curves of x ml of Pb (II), 0.05 M with Fe (III)
0.1 M in presence of Fe (II) and excess of EDTA.
Fig. 8. Titration curves of 10 mL of three metal ions (Cu, Ni, Co)
with Fe (III), in presence of Fe (II) and excess of EDTA.

-120
-80
-40
0
40
80
120
160
200
240
280
0 0. 5 1 1. 5 2 2. 5 3 3. 5 4 4. 5 5 5. 5 6 6. 5 7 7. 5 8 8. 5 9 9. 5 10 10. 5
volume of Fe (III)
E (mV)
10 ml Co
Fe (II) alone
10 Ni (II)
10ml Cu
Cu
Co

Journal of the University of Chemical Technology and Metallurgy, 42, 1, 2007

104
MY
n-4
ano Ie (!!!). Tle oetection limit ol tle lirst group
is better tlan tlat ol tle secono group since greater
jump is obtaineo at tle equivalent point.
REFERENCES
1. A. Skoog, M. Donalo, I. West, 1. Holler, Climie
analytique, 7 ime ioition, Bruxelles, De boek, 1997.
2. D. C. Harris, Quantitative analysis, Iourtl eoition,
1995.
3. I. B. Auoat, I. Rallegeau, D. Prevoteau, Climie
!norganique et gnrale, Dunoo, Paris, Secono
oition, 23, 78.
4. G. D. Clristian, Analytical clemistry, Iourtl eoi-
tion, 1986.
5. A Abbaspour, B. Klajel, Analytical sciences, Sep. 18, 22.
6. G. Clarlot, Mtlooes lectroclimiques, v.IV, 1976.
7. D. T. Sawyer, W R Heineman, 1 M Beebe, Clemistry
experiments lor instrumental metloos, 1.Wiley &
Sons, 1984.
8. H. A. Ilasclka, I.D.T.A. titrations, Pergamon press, 1964.
9. M. Rocle, 1. DesBarres, C. Colin, A. 1aroy, D. Bauer,
Climie oe solutions (Langage et inlormatique), 199,
p.179, p.183.