Complexation of Iron(III) by Salicylic Acid

(following V. D. Athawale and Parul Mathur, Reference 1.)

The weak acid 2-hydroxybenzoic acid, traditionally known as
salicylic acid, complexes iron in solution.
2-6
The concentration
of the iron complex may be measured spectrophotometrically.
In acid, a violet complex is formed. At neutral pH, a different
dark-red complex forms, and in basic solution the complex that
forms is orange.
2
This experiment will be conducted at a single
low pH.
nHSA
-
(aq) + Fe
3+
(aq) Fe(SA)
n
3-2n
(aq) + nH
+
(aq) (1)
The complexing species is the monoanion HSA
-
, salicylic acid after loss of its carboxylic proton
but before ionization of the phenolic proton. The number of ligands per complex is n, which will
be determined in this experiment. The stability of the complex is measured by the equilibrium
constant, K
n
.
K
n
= a(Fe(SA)
n
3-2n
) a(H
+
)
n
/ { a(Fe
3+
) a(HSA
-
)
n
} (2)
where a(x) stands for the activity of species x. For example, a(H
+
) stands for the activity of H
+
.
In this experiment, a(H
+
) is determined directly from pH measurement. Recall that
pH = -log
10
a(H
+
) (3)
The activities of Fe
3+
, HSA
-
and Fe(SA)
n
3-2n
equal their molar concentrations times their
activity coefficients. The activity coefficients will be calculated from the Debye-Huckel limiting
law.
7
a(Fe
3+
) =
Fe
[Fe
3+
] , a(HSA
-
)=
HSA
[HSA
-
] and a(Fe(SA)
n
3-2n
) =
FeSA
[Fe(SA)
n
3-2n
] (4)
Where log
10
(
x
) = -A z
x
2
I
1/2
(5)
where z
x
is the charge of species x
A = 0.509 at 25
o
C
and I is the ionic strength of the solution
FeSA 1
The experiment is arranged so that the ionic strength equals the concentration of NaClO
4
, which
is present specifically to control the ionic strength.
The complex obeys Beers law:
A = c [Fe(SA)
n
3-2n
] (6)
Where A is the absorbance, c is the molar absorptivity and is the optical path length. We will
use 1-cm cuvettes so the numerical value of is unity. The value of c will be determined as part
of this experiment.
The spectrophotometer is equipped with a thermostatted cell holder. Measuring absorbances at
different temperatures allows one to calculate K
n
as a function of temperature. The enthalpy and
entropy of formation can then be calculated from the intercept and slope of a graph of ln(K
n
)
versus (1/T), as predicted from an integrated form of the vant Hoff equation. (Reference 7,
Silbey, Alberty and Bawendi, eqn 5.41, page 146)
ln(K
n
) = (AS
o
/R) (AH
o
/R) (1/T) (7)
We will not study the temperature dependence of the reaction in Fall 2004 but will simply use the
water bath to maintain 25
o
C.
Jobs Method of Continuous Variation (derivation)
We will use Jobs method to determine the value of n. Here follows an analysis of the
equilibrium constant expression showing that n equals c
S
/c
Fe
at the highest absorbance, where c
S
is the formal concentration of salicylic acid (i.e., before complexation) and c
Fe
is formal
concentration of iron(III). The method of continuous variation uses a series of solutions that have
the same total concentration c.
c c
S
+c
Fe
(8)
Let P stand for the complex, the product of the reaction
Fe
3+
+ nS P + nH
+
(10)
Approximating activities by concentrations, the equilibrium constant expression is
n 3
n
n
][S] [Fe
] [P][H
K
+
+
= (11)
FeSA 2
(We will use equation 2, not equation 11 to calculate K
n
from experimental data.) By
stoichiometry, [Fe
3+
] = c
Fe
[P] and [S] = c
S
n[P]. Substitute these expressions into the
equilibrium constant expression. Define x c
Fe
/c and x
P
=[P]/c. The resulting expression is
x
P
= K
n
(c/[H
+
])
n
(x x
P
) (1-x nx
P
)
n
(12)
One may differentiate x
P
with respect to x and then set dx
P
/dx=0 to find the maximum product
as a function of the initial fraction iron. The result is
x = 1/(n+1) for maximum x
P
(13)
Because absorbance is proportional to complex concentration, and so to x
P
, the value of x that
gives maximum absorbance is also x=1/(n+1). From x one finds that c
B
/c
A
= n at maximum
absorbance.
Reagents
All solutions contain 0.0020 M HCl and 0.010M NaClO
4
, the latter to maintain constant
ionic strength. Note for Fall 2004: [NaClO
4
] = 0.10 M rather than 0.010 M.
- 0.0020 M HCl and 0.010M NaClO
4
- 0.0020 M Iron(III) ammonium sulfate
- 0.0020 M salicylic acid
- Saturated solution of salicylic acid
Supplies
- graduated 5-mL pipet
- pipet bulb
- 10 test tubes with stoppers
- pH meter
FeSA 3
Procedure
Find the wavelength of maximum absorbance
Use pipets to prepare a 1:1 mixture of the Iron(III) and Salicylic Acid solutions.
Record the absorption spectrum.
Note
max
and use that wavelength for all further absorption measurements.
Determine the mole ratio of the complex.
Prepare in stoppered test tubes a series of nine mixtures of the 0.0020 M Iron(III) and the
0.0020 M salicylic acid solutions, plus 5.0 mL HCl solution.
mixture 1 2 3 4 5 6 7 8 9
mL Iron(III) 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
mL salicylic acid 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
mL 0.002 M HCl 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
Measure the absorbance of each mixture. Plot absorbance versus [Fe
3+
]. Absorbance should
be highest for the stoichiometric mixture, where [salicylic acid]/[Fe
3+
] = n. Determine the
formula of the complex (i.e., the value of n). Round n to the nearest integer and use that
value in all further calculations.
Note the concentrations of iron and salicylic acid and the absorbance of the solution that
gives maximum absorbance. These values will be used later to calculate the equilibrium
constant. Use the pH meter to measure the pH of the solution. The activity of H
+
is the
negative of the base-10 logarithm of pH.
Determine the molar absorptivity c of the complex.
Pipette out 1.0, 2.0, 3.0 and 4.0 mL of 0.0020M Iron(III) solution into four stoppered test
tubes. To each tube add 5.0 mL of saturated salicylic acid solution and enough 0.0020 M
HCl solution to bring the total volume to 10.0 mL. Measure the absorbance of each solution.
Plot absorbance versus [Fe
3+
]. (Because the salicylic acid is in excess, it assumed that the
concentration of iron equals the concentration of the complex.) Calculate c by linear
regression.
Determine the stability constant K
n
.
Use the iron and salicylic acid concentrations and the absorbance from the Jobs-method
solution that gave the highest absorbance. Calculate the concentration of the complex from
its absorbance and molar absorptivity. Use the Debye-Huckel limiting law to calculate the
activity coefficients of charged species other than H
+
. Recall that you measured the activity
of H
+
earlier. Calculate the equilibrium constant K
n
using equation 2.
FeSA 4
Make up two additional solutions that have the same ratio of salicylic acid to iron, c
S
/c
Fe
=n,
but different total concentration c. The ionic strength and pH should be the same in all three
solutions. Measure the absorbances of the two new solutions and calculate K
n
from each
one.
Use your three values of K
n
to calculate K
n
(the mean) and its uncertainty.
Compare your K
n
to a literature value. The articles by M.V. Park, for example, are in the
UMD library annex and the Chemical Society books are on the fourth floor.
References
1. Athawale, V.D.; Mathur, Parul Experimental Physical Chemistry; New Age International:
New Delhi; 2001; pages 258-261.
2. Gabor, P.; Szasz, G. Magyar Kemiai Folyoirat, 1986, 92(11-12), pages 495-498. In
Hungarian. Abstract in English is CAN 108:83038.
3. Briner, G.P. Stability of metal complexes with salicylic acid and related substances, Nature,
1958 (4637), pages 741-742. Briners K
1
is for reaction with dianonic salicylate. To convert
it to the present K
1
, multiply Briners K
1
K
a2
. Bringer gives pKa
2
=13.61.
4. D. D. Perrin, Stability of metal complexes with salicylic acid and related substances, Nature,
1958, 182, 741-742.
5. Park, M.V. Complexes of ferric ion with salicylic acid and related substances, Nature, 1963
(4864), page 283.
6. Park, M. V. Complex formation between Iron(III) and some substituted salicylic acids, J.
Chem. Soc. (A) Inorg., Phys., Theoretical, 1966, 816-820.
7. Silbey, R. J.; Alberty, R. A. and Bawendi, M. G. Physical Chemistry, 4th ed; John Wiley &
Sons, Inc.: New York; 2005; page 229.
8. Saini, G.; Mentasti, E. Kinetics of formation of the monosalicylato complex of Iron(III),
Inorganica Chimica Acta, 1970, 4(4), pages 585-588. Note that Saini and Mentasti used a
higher ionic strength, 1M.
9. Stability Constants of Metal-Ion Complexes; Sillen, L. G., Martell, A.E., eds.; Special
Publication No. 17; The Chemical Society: London, 1964, pp. 533-534. Our logK equals
their K
1
for Fe
3+
K
1
for H
+
. I.e., think of Fe
3+
as displacing H
+
from the singly ionized
salicylic acid anion. UMD library QD503.S54.
10. Stability Constants Supplement No. 1; Sillen, L. G., Martell, A.E., Hogfeldt, E., and Smith,
R. M., eds.; Special Publication No. 25; The Chemical Society: London, 1971, page 483.
UMD library QD503.S54.
FeSA 5