Analytica Chimica Acta 442 (2001) 287293

Extended Gran method and its applicability for simultaneous

determination of Fe(II) and Fe(III)
Tadeusz Michaowski
a,
, Anna Baterowicz
a
, Alina Madej
b
, Jolanta Kochana
b
a
Faculty of Engineering and Chemical Technology, Technical University of Cracow, Krakw 31-155, Poland
b
Faculty of Chemistry, Jagiellonian University, Krakw 30-060, Poland
Received 13 March 2001; received in revised form 23 May 2001; accepted 30 May 2001
Abstract
A new extended Grans method is proposed and applied for simultaneous determination of iron (II and III) species by
potentiometric titration with potassiumpermanganate solution. Conditions for titrations providing unbiased results of analyses
were chosen on the basis of equilibrium analysis (simulated titration). 2001 Elsevier Science B.V. All rights reserved.
Keywords: Potentiometric titration; Iron speciation; Gran method
1. Introduction
Linearization procedures, known as the Grans (1st
and 2nd) methods [1,2], provide straight lines cor-
responding to volumes (V) of titrant added before
(V < V
eq
) or after (V > V
eq
) the equivalence vol-
ume (V
eq
); V
eq
is evaluated graphically. The results
thus obtained are loaded by a systematic error, how-
ever; the bias results from some approximations. In
the modied version [3,4], the bias is minimised and
V
eq
is evaluated according to least squares method.
The modication made enables, moreover, greater
portions of titrant to be applied and the effects re-
sulting from random errors due to volume V and
potential E (or pH) of the solution to be minimised. It
should be emphasised that the original and modied
Grans methods enable only one species in a mixture
to be determined, however. In contradiction to the
above, the new, extended Grans method enables two

Corresponding author. Tel.: +48-12-33-03-00;

fax: +48-12-33-33-74.
E-mail address: michalot@chemia.pk.edu.pl (T. Michaowski).
species, particularly soluble species of iron on its two
(+2 and +3) oxidation states, to be determined.
The paper concerns a potentiometric titration of
V
0
ml of the solution titrated (titrand) containing
Fe(II) (C
02
mol l
1
) +Fe(III) (C
03
mol l
1
) +H
2
SO
4
(C
a
) with Vml of Cmol l
1
KMnO
4
as the titrant. The
composition of the titrand can be affected by partial
oxidation of the iron(II) species by oxygen from the
air. The titration points (V
j
, E
j
) enter a part of the re-
lated titration curve, where E
j
= E(V
j
) is the poten-
tial measured at volume V = V
j
of the titrant added,
j = 1, . . . , N. The data thus obtained are then elab-
orated according to a new, extended Grans method.
2. Theoretical
In order to obtain the equation desired, one can
apply the relation
[Fe
2+
] +[FeOH
+
] +[FeSO
4
] (5[MnO
4

]
+4[MnO
4
2
] +[Mn
3+
] +[MnOH
2+
])
=
C
02
V
0
5CV
V
0
+V
(1)
0003-2670/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S0003- 2670( 01) 01172- 2
288 T. Michaowski et al. / Analytica Chimica Acta 442 (2001) 287293
as a modied form of the one derived in [5] from a
linear combination of electron and concentration bal-
ances. At low pH, affected by presence of H
2
SO
4
, the
related iron hydroxo-complexes can be omitted [4].
At values 0 < 0.2 for the fraction titrated ( =
CV/(C
02
V
0
)), Eq. (1) simplies to
[Fe
2+
]b
2
= C
02
V
0
1 5
V
0
+V
(2)
where b
2
= 1 + K
21
[SO
4
2
], [FeSO
4
] = K
21
[Fe
2+
]
[SO
4
2
]. From the simplied form of concentration
balance for iron, we have
[Fe
2+
](b
2
+f
23
b
3
) = (C
02
+C
03
)
V
0
V
0
+V
(3)
where b
3
= 1 + K
31
[SO
4
2
] + K
32
[SO
4
2
]
2
,
[FeSO
4
+
] = K
31
[Fe
3+
][SO
4
2
], [Fe(SO
4
)
2

] =
K
32
[Fe
3+
][SO
4
2
]
2
,
f
23
=
[Fe
3+
]
[Fe
2+
]
= 10
A(EE
0
)
(4)
and 1/A = ln
10
RT/F, where the terms are of
common signicance as in the Nernstian equation;
Fig. 1. Changes of ln(b
3
/b
2
) vs. V (ml) relationship found from simulated titrations with C = 0.02 mol l
1
KMnO
4
at indicated concentrations
(C) of H
2
SO
4
in the titrand; C
02
= 0.01 mol l
1
FeSO
4
, C
03
= 0.005 mol l
1
Fe
2
(SO
4
)
3
in the titrand, V
0
= 100 ml. The lines are plotted
on the basis of the data quoted in [4].
E
0
= 0.771 V is the standard potential of the re-
action Fe
3+
+ e

= Fe
2+
, log K
e
= AE
0
, K
e
=
[Fe
2+
][Fe
3+
]
1
[e

]
1
. This gives
E = E
0
a ln
b
3
b
2
+a ln(C
03
/C
02
+5) a ln(1 5) (5)
As stated in simulated titrations [5], the concentration
of SO
4
2
and then the term b
3
/b
2
remain practically
constant during a titration in the system considered,
especially at greater concentrations of sulphuric acid
in the titrand (see Fig. 1). This gives
E
i+1
E
i
= a
_
ln
C
03
/C
02
+5
i+1
C
03
/C
02
+5
i
+ln
1 5
i
1 5
i+1
_
(6)
where a RT/F and
C
03
/C
02
+5
i+1
C
03
/C
02
+5
i
=
C
03
/C
02
+5
i
+5
i+1
5
i
C
03
/C
02
+5
i
= 1 +
5(
i+1

i
)
C
03
/C
02
+5
i
= 1 +x
i
(7)
T. Michaowski et al. / Analytica Chimica Acta 442 (2001) 287293 289
1 5
i
1 5
i+1
=
1 +5(
i+1

i
)
1 5
i+1
= 1 +y
i
(8)
where
i
= CV
i
/(C
02
V
0
),
i+1
= CV
i+1
/(C
02
V
0
).
For |x| 1, ln(1 + x)

= x x
2
/2 = x(1 x/2)

=
x/(1 +x/2) we have [3,4,6], at x
i
1 and at y
i
1
ln(1 +x
i
)

=
x
i
1 +x
i
/2
=
5(
i+1

i
)
C
03
/C
02
+5(
i
+
i+1
)/2
(9)
ln(1 +y
i
)

=
y
i
1 +y
i
/2
=
5(
i+1

i
)
1 5(
i
+
i+1
)/2
(10)

i+1

i
E
i+1
E
i
=
1
5a(C
03
/C
02
+1)
[C
03
/C
02
+5(
i
+
i+1
)/2]
[1 5(
i
+
i+1
)/2] (11)
Denoting V

i
= (V
i
+ V
i+1
)/2 and rearranging the
terms, we have
u
i
=
V
i+1
V
i
E
i+1
E
i
= P +QV

i
R(V

i
)
2
+
i
(12)
where
P =
C
02
C
03
V
0
5aC(C
02
+C
03
)
, Q =
C
02
C
03
a(C
02
+C
03
)
,
R =
5C
a(C
02
+C
03
)V
0
(13)
and
i
is the difference between the u
i
value found
from measurements and the value u(V

i
) found at V =
V

i
from the model assumed. Then we calculate
P
R
=
_
V
0
5C
_
2
C
02
C
03
,
Q
R
=
V
0
5C
(C
02
C
03
)
(14)
C
02
=
5C
2V
0
_
_
_
_
Q
R
_
2
+4
P
R
_
1/2
+
Q
R
_
_
(15)
C
03
=
5C
2V
0
_
_
_
_
Q
R
_
2
+4
P
R
_
1/2

Q
R
_
_
(16)
One should note that the factor a in the formulae for
P, Q, R (Eq. (13)) does not enter the expressions for
P/R and Q/R (Eq. (14)). This means that the values
for C
02
and C
03
(Eqs. (15) and (16)) are not biased by
the a-value differing, to some extent, from the Nern-
stian value, RT/F, for electrodes commonly applied
in titrations [9]. This circumstance does not occur in
potentiometric titrations performed with the use of a
calibration graph or the standard addition method.
For C
03
= 0 (i.e. absence of iron(III)), C
02
= C
0
,
we have
E
i+1
E
i
= a
_
ln
_

i+1

i
_
+ln
_
1 5
i
1 5
i+1
__

i+1

i
=

i+1

i
+
i

i
= 1 +

i+1

i
= 1 +x
i
ln(1 +x
i
)

=
x
i
1 +(x
i
/2)
=

i+1

i
(
i
+
i+1
)/2
(at x
i
1) and nally (compare with [3,4]).
w
i
=
1
V

i
V
i+1
V
i
E
i+1
E
i
= P QV

i
+
i
(17)
where P = 1/a, Q = 5C/(aC
0
V
0
) and then
C
0
=
5C
V
0
P
Q
(18)
The values for P, Q and R (Eq. (13)) in Eq. (12) or P
and Q in Eq. (17) can be found according to the least
squares method. For example, P and Q in Eq. (17)
minimise the sum of squares
SS =
N1

i=1
(P QV

i
w
i
)
2
and then the P/Q value is calculated.
A compact form of the related formulae needed for
calculation of the concentrations of iron species with
use of Eq. (12) is obtained if equal portions of titrant,
V
i+1
V
i
= V, are added, i.e. V
i
= iV, i = 1,
. . . , N, V

i
= (2i +1)V/2 and
N1

i=1
(V

i
)
k
=
_
V
2
_
k
N1

i=1
(2i +1)
k
=
_
V
2
_
k
_
N

i=1
(2i 1)
k
1
_
290 T. Michaowski et al. / Analytica Chimica Acta 442 (2001) 287293
The following formulae are applicable here [10]:
N

i=1
(2i 1) = N
2
N

i=1
(2i 1)
2
=
1
3
N(4N
2
1)
N

i=1
(2i 1)
3
= N
2
(2N
2
1)
N

i=1
(2i 1)
4
=
1
15
N(4N
2
1)(12N
2
7)
P
R
=
_
V
2
_
2

N1
i=1
u
i

N1
i=1
(2i +1)

N1
i=1
(2i +1)
2

N1
i=1
(2i +1)u
i

N1
i=1
(2i +1)
2

N1
i=1
(2i +1)
3

N1
i=1
(2i +1)
2
u
i

N1
i=1
(2i +1)
3

N1
i=1
(2i +1)
4

N1
i=1
u
i

N1
i=1
(2i +1) N 1

N1
i=1
(2i +1)u
i

N1
i=1
(2i +1)
2

N1
i=1
(2i +1)

N1
i=1
(2i +1)
2
u
i

N1
i=1
(2i +1)
3

N1
i=1
(2i +1)
2

Q
R
=
_
V
2
_

N1
i=1
u
i
N 1

N1
i=1
(2i +1)
2

N1
i=1
(2i +1)u
i

N1
i=1
(2i +1)

N1
i=1
(2i +1)
3

N1
i=1
(2i +1)
2
u
i

N1
i=1
(2i +1)
2

N1
i=1
(2i +1)
4

N1
i=1
u
i

N1
i=1
(2i +1) N 1

N1
i=1
(2i +1)u
i

N1
i=1
(2i +1)
2

N1
i=1
(2i +1)

N1
i=1
(2i +1)
2
u
i

N1
i=1
(2i +1)
3

N1
i=1
(2i +1)
2

3. Some concerns
MnO
4

ions act as a strong multibasic agent against

H
+
ions,
8H
+
+MnO
4

+5e

= 4H
2
O +Mn
2+
The resulting growth of pH favours the dissociation
HSO
4

= H
+
+ SO
4
2
, pk
2
= 1.8. Addition of
KMnO
4
solution also increases the pH of the mixture
as a result of dilution and favours, simultaneously, the
dissociation of HSO
4

. SO
4
2
forms relatively strong
complexes (log K
31
= 4.18, log K
32
= 7.4) with Fe
3+
and weaker complexes: FeSO
4
(log K
21
= 2.3) and
MnSO
4
(log K
21
= 2.28) with Fe
2+
and Mn
2+
. A
relatively large excess of H
2
SO
4
(concentration C
a
)
is needed to prevent formation of MnO
2
precipitate
and the resulting break in stoichiometry (1:3 versus
1:5). All the complex phenomena in the system can be
followed in simulated quasistatic titrations made un-
der isothermal conditions (equilibriumanalysis) [58].
This way, some effects whose existence had previously
been only conjectured, can be stated. Particularly, it is
of crucial importance to follow the changes in SO
4
2
concentration affecting the ln(b
3
/b
2
) value in Eq. (5).
Transformation of Eq. (5) into Eq. (6) is then pos-
sible if the fraction b
3
/b
2
remains constant during
titration, i.e. it is independent on the variable .
In reality, slight changes in SO
4
2
concentration
occurred but they can be diminished under certain
conditions established on the basis of equilibrium
analysis.
There are two ways to resolve the problem. The rst
assumes addition of an appropriate quantity of H
2
SO
4
to the mixture titrated. Optionally, equal quantities of
the acid can be added during preparation of titrand and
titrant.
From Fig. 1 it results that
y = y
0
(1
1
V) (19)
T. Michaowski et al. / Analytica Chimica Acta 442 (2001) 287293 291
where y = y

= [SO
4
2
], y
0
= [SO
4
2
]
0
(i.e. y
0
refers to = 0), 0 <
1
1. Comparing the plots
given in Fig. 1a and applying the approximation ln(1+
x)

= x, we get
ln
_
b
3
b
2
_
= V (20)
where

= ln
_
K
32
y
2
0
+K
31
y
0
K
21
y
0
+1
_

=
_
2K
32
K
32
y
0
+K
31

K
21
K
21
y
0
+1
_
y
0

1
(21)
The linear relationship expressed by Eq. (20) is then
affected by the relation (19); Eq. (20) can be trans-
formed into the form
ln
_
b
3
b
2
_
= (22)
where = C
02
V
0
/C. Particularly, the relationships:
ln(b
3
/b
2
) = 7.3191 0.0017V and aln(b
3
/b
2
) =
a[7.3191 4.36 10
2
V] (mV) are found (at T =
298 K) for the curve plotted in Fig. 1 at C
a
= 1 mol l
1
H
2
SO
4
. This means that a change in potential affected
by the term a ln(b
3
/b
2
) in Eq. (5) equals 4.3610
2

4.5 0.2 mV within the V-interval 0, 4.5; this value

is comparable with precision (0.1 mV) of potential
measurements made there. One can then assume that
0 < 1 and 0 < 1.
The simulation procedure enables also the effects
of precision and accuracy to be followed in the system
in question; the round off or truncation of potential
and volume values can be applied for this purpose. It
is also necessary to provide a criterion that enables
the points (V
j
, E
j
), j = N + 1, . . . to be excluded
from the close vicinity of the equivalence point in the
calculations made there.
Another matter involved with Eq. (5) concerns a
reference electrode chosen for experimental titrations.
Replacing the reference electrode, with potential E

0
,
by another electrode, with potential E

0
, changes the
emf in the system with working and reference elec-
trodes by the value E
0
= E

0
E

0
. However, the
replacement of electromotive forces E
i
by E
i
E
0
(i = 1, . . . , N) does not lead to any disturbance in
results for the concentrations evaluated, as clearly fol-
lows from Eqs. (5) and (6).
4. Experimental
4.1. Materials and equipment
1. Solution of KMnO
4
(Cmol l
1
), obtained by dis-
solution of the preparation (pa, POCh Gliwice) and
standardised against sodium oxalate Na
2
C
2
O
4
(pa,
nach Srensen, Merck, Germany).
2. Stock solution of iron(II) was prepared by dis-
solving a suitable portion of ammonium iron(II)
sulphate hexahydrate, (NH
4
)
2
Fe(SO
4
)
2
6H
2
O (pa,
POCh Gliwice), in 1 mol l
1
H
2
SO
4
. Qualitative
(thiocyanate) tests made on the solution showed
only traces of Fe(III).
3. Stock solution of iron(III) was prepared from hy-
drated ammonium iron(II) sulphate NH
4
Fe(SO
4
)
2

12H
2
O is protruded (pa, POCh Gliwice).
4. Solution of H
2
SO
4
, prepared by dilution of the con-
centrated acid (pa, POCh Gliwice).
Water triply distilled from quartz and boiled to re-
move CO
2
and O
2
, was applied for preparation of
stock solutions, titrand and titrant. Solutions of Fe(II)
salts exhibit greater stability in the presence of greater
concentrations of H
2
SO
4
.
Concentrations of Fe(II) and Fe(III) in the corre-
sponding stock solutions were determined according
to the ZimmermannReinhardt method. Freshly pre-
pared and pre-determined Fe(II) solutions were ap-
plied in the titrations.
The method proposed was checked by results of
potentiometric titrations performed with an auto-
matic titrator (Mettler-Toledo DL 25) equipped with
a combined platinum ring electrode for redox titra-
tions (Mettler-Toledo DM140-S.C.). The parameters
P, Q and R in Eq. (12) were found according to the
least squares method (calculation sheets, Microsoft
Excel 97), and then C
02
and C
03
were calculated
from Eqs. (15) and (16). Typical titration curves,
within the V-region considered for calculations, are
collected in Fig. 2. Numbers ascribed to a curve are
compatible with the number of related data given in
Table 1.
In the procedure applied, the titrant (Cmol l
1
KMnO
4
) was added in equal increments, 0.1 ml,
into V
0
= 50 ml of the sample containing Fe(II)
(C

02
mol l
1
), Fe(III) (C

03
mol l
1
) and C
a
=
1 mol l
1
H
2
SO
4
; the titration was continued un-
292 T. Michaowski et al. / Analytica Chimica Acta 442 (2001) 287293
Fig. 2. The titration curves related to the data obtained in Table 1.
til the equivalence volume (V
eq
) was crossed. The
points (V
j
, E
j
) (j = 1, . . . , N) where V
j
<
V
eq
0.5 ml were taken for calculations. This lim-
iting condition satises the validity of approxima-
Table 1
Results of measurements obtained from titrations
a
No. C C

02
C

03
N 1 P Q R C
02
C
03
1 0.01972 0.005000 0.010000 21 23.8308 4.76751 1.81747 0.005015 0.010188
21 23.7817 4.56630 1.89413 0.005004 0.009758
21 23.8305 4.65846 1.86446 0.005005 0.009932
2 0.01975 0.005055 0.002487 21 13.0179 4.43191 3.83261 0.004926 0.002693
21 13.0021 4.35015 3.85994 0.004912 0.002683
21 14.2194 4.27450 4.26453 0.004737 0.002754
3 0.01972 0.010000 0.005000 45 23832.7 4866.0 1942.0 0.009807 0.004866
45 24194.5 4639.5 1908.0 0.009818 0.005023
45 24307.4 4586.2 1902.2 0.009817 0.005062
4 0.01975 0.010110 0 45 862.000 13482.9 2679.42 0.0100629 0.000125
45 913.204 13418.0 2670.76 0.0100552 0.000132
45 855.219 13521.6 2688.07 0.0100581 0.000123
a
C concentration (mol l
1
) of KMnO
4
solution; C

02
and C

03
values expected for Fe(II) and Fe(III) concentrations (mol l
1
); P, Q,
R coefcients in Eq. (14) found from experimental points (V
j
, E
j
), j = 1, . . . , N; C
02
and C
03
concentrations (mol l
1
) calculated
from Eqs. (15) and (16); V
0
= 50 ml; temperature ca. 20

C.
tions in Eq. (10). A similar restriction is also re-
quired in original [1,2] and modied [3,4] Grans
methods (both are considered as extrapolation
methods).
T. Michaowski et al. / Analytica Chimica Acta 442 (2001) 287293 293
4.2. Results and comments
The results collected in Table 1 testify in favour of
the method proposed. Generally, the results for C
02
are somewhat lower than C

02
and C
03
are somewhat
greater than C

03
established on the basis of prelimi-
nary measurements. However, the summary concen-
tration C
02
+ C
03
is nearly constant (within an error
ca. 1%) in all the series presented. This means that
Fe(II) was partially oxidised into Fe(III) by O
2
in the
solution titrated.
Speciation of iron in its two (+2 and +3) oxidation
degrees is of great importance in chemical analysis.
The newly developed method fulls some common
requirements for analytical methods, namely, (1

)
the manner of preparation of solutions is convenient,
(2

) the analysis is simple and cheap, (3

) the desired
data are obtained with sufcient accuracy and preci-
sion. The conditions of analyses chosen enable a drift
of analytical results to be avoided (see Eq. (22)). The
drift resulting from a change of SO
4
2
concentra-
tion during titration is minimised by use of a greater
concentration of H
2
SO
4
in the solution titrated.
References
[1] G. Gran, Acta Chem. Scand. 4 (1950) 559.
[2] G. Gran, Analyst 77 (1952) 661.
[3] T. Michaowski, Chem. Anal. 26 (1981) 799.
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[5] T. Michaowski, A. Lesiak, Chem. Anal. (Warsaw) 39 (1994)
623.
[6] T. Michaowski, J. Chem. Educ. 71 (1994) 560.
[7] T. Michaowski, A. Lesiak, J. Chem. Educ. 71 (1994) 632.
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41 (1996) 667.
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