February, 1966] The Complex Formation between Iron(III) and Salicylic Acid 227

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN VOL. 39 227-232 (1966)

A Spectrophotometric Study of the Complex Formation between Iron(III)

and Salicylic Acid

By Kin'ya OGAWA and Nobuko TOBE

Hitachi Research Laboratory, Hitachi, Ltd., Hitachi, Ibaraki

(Received April 8, 1965)

A spectrophotometric study of the complex formation between iron(III) and salicylic acid was
carried out over the pH range up to 6; further, an attempt was made to test the applicability of
salicylic acid as a reagent for the spectrophotometric determination of iron(III) in the presence
of iron(II). The absorption maxima of the mixture of iron(III) and salicylic acid are found at
530mμ independently of the pH between 0.7 to 2.5, while they shift to shorter wavelength when

the pH rises above 3. The isosbestic point occurs at 550mμ between pH values from 3 to 6. It was

concluded that three complex species, Fe(Sa)+, Fe(Sa)2-, and Fe(Sa)33-, are formed successively
in acid solutions; their stability constants were determined to be:
 228 Kin'ya OGAWA and Nobuko TOBE [Vol. 39, No. 2

where Sa2- denotes the salicylate anion, C6H4(O-)(COO-). If the pH of the solution is adjusted
from 2 to 3 and if absorbancy measurements are made at 515 to 500mμ, salicylic acid can be used

as a reagent for determining iron(III) in the presence of iron(II). The optimum concentration of
iron(III) is 2 to 12p.p.m.; iron(II) does not interfere, even at a concentration of 100p.p.m.

Salicylic acid has been known as a reagent1) mixture of iron(III) and salicylic acid at different
for determining iron(III), since it gives characteristic pH values. The absorption maxima are found
colors with iron(III). The initial investigation at 530mμ, independently of the pH values when

of the nature of the complex formation between those values are between 0.7 to 2.5, while they
iron(III) and salicylic acid was undertaken by shift to a shorter wavelength when the pH rises
Babko,2,3) who demonstrated the formation of
more than one complex in an aqueous solution.
Afterward, Agren4) determined the equilibrium
constants for the complex-forming reaction.
The present authors were interested in the color
variations, from violet through red to yellow with
a rise on the pH values, which had been noted in
earlier analytical studies.5,6) For the present
paper, therefore, the color-forming reaction between
iron(III) and salicylic acid was studied spectro-
photometrically, and, further, an attempt was
made to test the applicability of salicylic acid as a
reagent for the spectrophotometric determination
Fig. 1. Absorption curves. Solutions were 1.83
of iron(III) in the presence of iron(II).
×10-4M in iron(III) and 7.3×10-3M (for dot-
ted line) or 1.45×10-2M (for full line) in

Experimental salicylic acid.

Curve 1, at pH 0.74; 2, at pH 1.71; 3, at pH
Reagents. -The iron(III), iron(II) and buffer 2.45; 4, at pH 3.20; 5, at pH 3.63; 6, at pH
solutions were prepared in manners described previ- 4.04; 7, at pH 4.60; 8, at pH 5.30
ously.7) A solution of salicylic acid was prepared by
dissolving a commercial product, C6H4(OH)(COOH), above 3. The isosbestic point occurs at 550mμ
in ethanol. at pH values between 3 and 6. This behavior
Apparatus. -The two spectrophotometers and the suggests that only one complex is formed in a
pH meter used in the present work were the same as
those described previously.7) strongly acid solution between pH 0.7 and 2.5,
Procedure. -The volume of the iron(III) solution but that the formation of more than one complex
was calculated and the pH was adjusted to the required may be involved in a weakly acid solution between
value by adding a buffer solution. After the calculated pH 3 and 6.
volume of the salicylic acid solution had been added, The Effects of the Molar Ratio of Salicylic
the whole was diluted to the proper volume and allowed Acid to Iron(III). -The relations between the
to stand for two hours. The absorbancy was observed absorbancy and the molar ratio of salicylic acid
in a part of the resulting solution, and/or, if necessary,
the absorption curve over the range from 400 to 600mμ

was recorded, while the pH was measured for the other

part. Preliminary experiments showed that the solu-
tions reached an equilibrium within two hours and
showed no measurable variation thereafter for periods of
less than twenty-four hours.

Results and Discussion

The Effects of pH on the Absorption Curve.

-Figure 1 shows the absorption curves for the

1) F. J. Welcher, "Organic Analytical Reagents Vol. II," D.

van Nostrand Co., New York (1947), p. 118. Fig. 2. Relations between absorbancy and CSa/
2) A. K. Babko, J. Gen. Chem. (U.S.S.R.), 15, 745 (1945); CFe. Solutions were 1.83×10-4M in iron(III)
Chem. Abstr., 40, 7041 (1946).
3) A. K. Babko, J. Gen. Chem. (U.S.S.R.), 15, 758 (1945); and 0.05M in total monochloroacetate (curves
Chem. Abstr., 40, 7042 (1946). 1 and 2) or 0.05M in total acetate (curves 3, 4
4) A. Agren, Acta Chem. Stand., 8, 1059(1954); Chem. Abstr., and 5).
49, 2929 (1955). Curve,1, at pH 2.04 for 530mμ; 2, at pH 2.81
5) J. P. Mehlig, Ind. Eng. Chem. Anal. Ed., 10, 136 (1938).
6) R. O. Scott, Aualyst, 66, 142 (1941). for 515mμ; 3, at pH 3.51 for 490mμ; 4, at

7) K. Ogawa and N. Tobe, This Bulletin, 39, 223 (1966). pH 4.58 for 480mμ; 5, at pH 5.96 for 475mμ
February, 1966] The Complex Formation between Iron(III) and Salicylic Acid 229

to iron(III) in their mixture were obtained at competes with hydrogen ions in taking away
different pH values. The results are shown in salicylate anions.
Fig. 2. There is neither a sharp break nor a The Stability Constant of the Complex. -
leveling-off to a constant absorbancy at any pH The method described by McConell and Davidson9)
value for ratios up to as high as ten moles of salicylic was used for determining the stability constants
acid to one mole of iron(III); this shows that the of the complexes. Since there are three complex
colored complexes are appreciably dissociated and species in the acid solution, the reaction for the
that, hence, a large excess of salicylic acid over complex formation may be written in general in
iron (III) is required to bring the reaction to comple- terms of the following successive steps:
tion.
Fe3++Sa2-Fe(Sa)+ (1)
The Composition of the Complex. -The
compositions of the complexes were determined by Fe(Sa)++Sa2-Fe(Sa)2- (2)
applying the continuous variation method.8) Fe(Sa)2-+Sa2-Fe(Sa)33- (3)
Figure 3 shows the results obtained at different
where Sa2- denotes the salicylate anion, C6H4(O-)-
pH values by plotting Y, the difference between
the observed absorbancy and that which would (COO-). The corresponding equilibrium con-
stants are, then;
be obtained if no reaction had taken place, against
the ratio of the total concentration of salicylic
(4)
acid, CSa, to the sum of the total concentration
of iron(III) and that of salicylic acid, CFe+CSa.
The maximum value of Y in curve 1 occurs at a (5)
ratio of 0.5, indicating that salicylic acid combines
with iron(III) in a molar ratio of 1 to 1. In each
of the curves from 2 to 5 the maximum of Y is (6)
found in the neighborhood of a ratio of 0.7, while When salicylic acid is present in a large excess
in curve 6 it is found at a ratio of about 0.75. over iron(III), the concentration of the salicylic
This indicates that complex species in which salicylic acid combining with iron(III) is negligible com-
acid combines with iron(III) in molar ratios of
two to one and/or three to one are formed in addition pared with its total concentration. Therefore,
Eqs. 4, 5, and 6 are converted into the following:
to the 1 to 1 complex, and that the molar ratio of
salicylic acid to iron(III) in the complex increases K1=
with the rising pH values. This behavior is
interpreted as taking place because iron(III)

(7)

(8)

(9)

where CFe and CSa represent the total concentra-

tions of iron(III) and of salicylic acid respectively,
and

(10)

where k1 and k2 are the first and the second acid

dissociation constants of salicylic acid. The ab-
Fig. 3. Relations between Y and CSa/(CFe+CSa) sorptions of both iron(III) and salicylic acid in
in the application of continuous variation method. the solution are so weak that they are negligible
Solutions were 4.57×10-4M (curves 1 to 5) or
9.13×10-1M (curves 6) in CFe+CSa and 0.05M
compared with the absorption of the complexes
over the range from 450 to 600mμ. Therefore,
in total monochloroacetate (curve 1) or 0.05M
in total acetate (curves 2 to 6). the observed absorbancy, As, may be expressed as:

Curve 1, at pH 2.70 for 520mμ; 2, at pH 3.33

for 505mμ; 3, at pH 3.80 for 500mμ; 4, at

pH 4.02 for 485mμ; 5, at pH 4.80 for 480mμ; (11)

6, at pH 5.94 for 475mμ
where ε1, ε2, and ε3 represent the molar absorbancy

8) A. E. Martell and M. Calvin, "Chemistry of the Metal 9) H. McConell and N. Davidson, J. Am. Chem. Soc., 72,
Chelate Compounds," Prentice-Hall, New York (1952), p. 28. 3164 (1950).
 230 Kin'ya OGAWA and Nobuko TOBE [Vol. 39, No. 2

indexes of Fe(Sa)+, Fe(Sa)2-, and Fe(Sa)33- re-

spectively.
From Eqs. 7, 8, 9, and 11 the following equation
is derived:

(12)

where:

(13) Fig. 4. Plots of CFe/As vs. F1, keeping CFe at

1.83×10-4M and varying CSa from 2.0×10-3

and where β is the overall stability constant of
to 1.45×10-2M in 0.05M of total monochloro-
the complex, which is expressed in general as βn=
acetate.
II Kn. In Eqs. 12 and 13, CFe and CSa have known Curve 1, at pH 2.04 for 530mμ; 2, at pH 2.81
values; As is an observed quantity, and ε1, ε2, for 530mμ; 3, at pH 2.81 for 550mμ; 4, at
K1 and β2 can be obtained from subsequent equa- pH 2.81 for 480mμ; 5, at pH 2.81 for 460mμ.
tions. If a suitable condition is chosen, the plotting

of CFe/As against F3 gives a straight line, the slope

of which is 1/ε3β3. The molar absorbancy index,

ε3, can be estimated from the intercept at F3=0,

which is obtained by extrapolation. In all subse-

quent equations, as in this, CFe/Asis plotted against
F terms, and the desired constants are obtained
from the slopes and the intercepts of the straight
lines.
If a condition is now selected where the reaction
for the complex formation is represented as the
two successive steps of reactions 1 and 2, [Fe(Sa)33-] Fig. 5. Plots of CFe/As vs. F2 at pH 3.51, keep-

becomes zero, and, from Eqs. 7, 8 and 11, it follows ing CFe at 1.83×10-4M and varying CSa from

that: 7.3×10-3 to 3.62×10-2M in 0.05M of total

acetate.
Curve 1, for 460mμ; 2, for 480mμ.
(14)

where:

(15)

Equations 14 and 15 permit the determination

of both ε2 and β2, which are necessary for Eq. 13.

If a condition can be found where only a 1 to 1

complex is formed, both [Fe(Sa)2-] and [Fe(Sa)33-]
become zero, and, from Eqs. 7 and 11, there comes
the following equation:
Fig. 6. Plots of CFe/As vs. F3 at pH 5.96 for 480
mμ, keeping GFe at 1.83×10-4M and varying
(16)
CSa from 3.6×10-3 to 2.90×10-2M in 0.05M
of total acetate.
where F1=φ/CSa, which permits the determinal

tion of both ε1 and K1, necessary for Eq. 14.

First, in order to determine the K1 value, plots In Table I are tabulated the results of the cal-
of Eq. 16 were applied to the data at pH 2.04 and culation of the desired constants from Figs. 4, 5
2.81; the results are shown in Fig. 4. Next, and 6. The values of the first and the second acid
plots of Eq. 14 were applied to the data at pH dissociation constants of salicylic acid used in these
3.51 in order to determine β2; the results are given calculations were those described in the literature.10)
in Fig, 5. Finally, β3 was determincd from the The logarithmic values of the stability constants
results of the application of Eq. 12 to the data at calculated above are given in Table II, where they
pH 5.96, as is shown in Fig. 6.
are also compared with those determined by
 February, 1966] The Complex Formation between Iron(III) and Salicylic Acid 231

TABLE I. CALCULATION OF STABILITY CONSTANTS

Calculation of K1 from Fig. 4

Calculation of β2 from Fig. 5

Calculation of β3 from Fig. 6

TABLE II. LOGARITHMIC VALUES OF OVERALL STABILITY CONSTANTS

* The two abbreviations , "sp." and "pol." mean "spectrophotometric" and " polarographic"
respectively.

Agren.4,10) The present va-ues of log K1 and log The Spectrophotometric Determination of
β2 agree reasonable well those obtained by Agren, Iron(III) in the Presence of Iron(II). -Calibra-
while there are considerable discrepancies between tion Curves-The calibration curves prepared for
them in the two values of log β3. These discrep- different pH values with a series of solutions con-
ancies may be due to the difference in ionic strength taining up to 10p.p.m. of iron(III) are shown in
and temperature, and also to some unknown factor Fig. 7. A linear or nearly linear relation is found
such as the influence of buffer components in the between the absorbancy and the concentration of
equilibria. iron(III) at each pH value.
The Effects of Iron(II). -As is shown in Table
III, the determination of iron(III) at pH 2.80

TABLE III. SPECTROPHOTOMETRIC DETERMINATIONS

OF IRON(III) BY SALICYLICACIDIN THE PRESENCE
OF IRON(II)*

Fig. 7. Calibration curves. Solutions were 0.036

M in salicylic acid and 0.5M in total monochloro-
acetate (curve 1) or 0.5M in total acetate (curves
2 to 4).
Curve 1, at pH 2.80 for 515mμ; 2, at pH 3.50
for 490mμ; 3, at pH 4.50 for 480mμ; 4, at

pH 6.00 for 475mμ * The amount of iron(III) taken in each case

10) J. Bjerrum, G. Schwarzenbach and L. G. Sillen, "Stability was 8.16p.p.m. Solutions were 0.036M in
Constants, Part I: Organic Ligands," The Chemical Society, salicylic acid and 0.5M in total monochloro-
London (1956), p. 53. acetate or total acetate.
232 [Vol. 39, No. 2

and 3.70 has a positive error of a few percentage

points because of the presence of iron(II). At
pH 4.50, the sensitivity is greater, but even small
Also, it has been ascertained that salicylic acid can
quantities of iron(II) produce a large positive error.
be used as a reagent for determining iron(III) in
the presence of iron(II) if the spectrophotometric
Summary measurements are made in the pH range from 2
A spectrophotometric study of the complex for- to 3.
mation between iron(III) and salicylic acid has
been carried out over the pH range up to 6. Three The authors wish to express their deep gratitude
complex species, Fe(Sa)+, Fe(Sa)2-, and Fe(Sa)33-, to Professor Soichiro Musha of the University of
have been concluded to be formed in acid solutions, Osaka Prefecture for his interest, as well as to As-
and their stability constants have been determined sistant Professor Makoto Munemori for his helpful
to be: discussions. Thanks are due also to Dr. Takeshi
Nakatogawa and Dr. Natsuki Kawashima of the
Hitachi Research Laboratory, Hitachi, Ltd., for
their guidance and encouragement throughout
this work.