Experiment 3

STABILITY CONSTANT OF A COMPLEX BY

SPECTROPHOTOMETRY
Aim To determine the stability constant and composition of Iron(II)salicylate complex by spectrophotometry and deduce the Gibbs energy for
the complex formation reaction.

RESULTS
Table 1: Absorbance of the Samples for the reaction of 0.0025 M Fe(NO 3)3
(in 0.020 M HNO3) with 0.0025 M HSal (in 0.020 M HNO3) at different
wavelengths.
Test
Tube

1
2
3
4
5
6
7
8
9
10
11

Volume
of
Reactant
Added (mL)
0.0025
0.0025
M
M
Fe(NOHSal
3 )3
5.0
0
4.5
0.5
4.0
1.0
3.5
1.5
3.0
2.0
2.5
2.5
2.0
3.0
1.5
3.5
1.0
4.0
0.5
4.5
0
5.0

Absorbance at Respective wavelengths

400 nm

450 nm

500 nm

525 nm

550 nm

600 nm

0.079
0.205
0.303
0.388
0.648
0.470
0.456
0.396
0.305
0.194
0.098

0.059
0.273
0.451
0.598
0.733
0.765
0.729
0.628
0.467
0.275
0.087

0.056
0.376
0.648
0.875
1.071
1.128
1.076
0.926
0.675
0.378
0.077

0.056
0.394
0.680
0.923
1.133
1.190
1.098
0.974
0.709
0.395
0.080

0.056
0.380
0.656
0.890
1.092
1.153
1.096
0.938
0.684
0.383
0.079

0.055
0.299
0.498
0.672
0.825
0.870
0.828
0.706
0.519
0.300
0.075

(
max
)
In table 1, the wavelength of maximum absorbance

is 525 nm.

Table 2: Absorbance of the standard solutions (samples 12-16) for the

reaction of 0.0025 M Fe(NO3)3 (in 0.020 M HNO3) with 0.0020 M HNO3 at
525 nm
Test
Tube

Volume of Reactant
Added (mL)
0.0025 M
0.020 M
Fe(NO3)3
HNO3

Absorba
nce

Corrected
Absorbance,
A ( max )

Page 1 of 11

12
13
14
15
16

2.0
1.6
1.2
0.8
0.4

3.0
3.4
3.8
4.2
4.6

1.404
1.188
1.940
0.649
0.357

1.334
1.116
1.866
0.5728
0.2789

Figure 1: Absorbance of samples at different Wavelengths.

Table 3: The initial concentrations of Fe(NO 3)3 and HSal and their molar
fractions for
Samples 1-11.
Sample #

[Fe(NO3)3]
/M

[HSal] /M

1
2
3
4
5
6
7
8
9
10
11

0.00250
0.00225
0.00200
0.00175
0.00150
0.00125
0.00100
0.000750
0.000500
0.000250
0

0
0.00250
0.000500
0.00750
0.00100
0.00125
0.00150
0.00175
0.00200
0.00225
0.00250

x (Fe(N
O3)3)
1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0

x (HSal)
0.00
0.10
0..20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
Page 2 of 11

Sample calculation for initial concentration and molar fraction:

For sample 2;
C1 V 1=C 2 V 2
NO 3

C2 V 2 (0.0025 M )(4.5 mL)

Fe ( 3 ]=
=
=0.00255 M
V1
(5.0 mL)
C1=

molar fraction ( x )=

n V 4.5
= =
=0.90
nT V T 5.0

x Fe(NO ) =0.90
3 3

Figure 2: Job's Plot of Absorbance vs Mole Fraction of Fe(NO3)3/Fe.

Page 3 of 11

Table 4: The corrected absorbance, ( max ) , for samples 1-11

Sample #

Absorbance

1
2
3
4
5
6
7
8
9
10
11

(525nm)
0.056
0.394
0.680
0.923
1.133
1.190
1.098
0.974
0.709
0.395
0.080

at

max

Corrected
A ( max )

Absorbance,

0
0.3356
0.6192
0.8598
1.0674
1.220
1.0276
0.9012
0.6338
0.3174
0

Sample calculation for A ( max ) , from equation (31):

( max )= ( max ) [ ( 1z ) M ,0 ( max ) + z L ,0 ( max ) ]
For sample 2:
Let reactants Fe(NO3)3 and HSal be M and L respectively and their volume
fractions be (1z ) and z respectively.
z=

volume of reactant 0.5 mL

=
=0.1
volume of solution 5.0 ml

( 1z )=

4.5 mL
=0.9
5.0 mL

( max ) =0.394[ ( 0.9 ) ( 0.056 ) + ( 0.1 ) ( 0.080 ) ]=0.3356

Table 5: Concentration of Fe3+ for samples (12-16).

Test
Tube

12
13
14
15

Volume of Reactant
Added (mL)
0.0025 M
0.020 M
Fe(NO3)3
HNO3
2.0
3.0
1.6
3.4
1.2
3.8
0.8
4.2

[Fe(NO3)3]/
M

0..00100
0.00080
0.00060
0.00040

[Fe3+]/
mM

1.0
0.8
0.6
0.4
Page 4 of 11

16

0.4

4.6

0.0020

0.2

Table 6: The equilibrium concentration of the complex, {Fe(Sal)(H 2O)4}3

in samples (2-10).
Sample number

Corrected
Absorbance,
A ( max )

Concentration of the
complex
/M

0.3356

2.52 104

0.6192

4.66 104

0.8598

4.64 104

1.0674

8.03 104

1.220

9.17 104

1.0276

7.73 104

0.9012

6.78 104

0.6338

4.77 104

10

0.3174

2.39 104

Concentration of the complex (sample calculation), for sample 2:

[{Fe(Sal)(H2O)4}3]

( max )
l ML
n

From figure 3, slope

l
( MLn )

[{Fe(Sal)(H2O)4}3]

3
1.33 mM-1 1.33 10 M-1

( max )
0.3356
=
=2.52 104 M
3
l ML
1.33 10
n

Table 7: The concentration of the uncomplexed of Fe(NO 3)3/Fe3+ and HSal

for samples (2-10).
Sample
#

[Fe(NO3)3]
/M

[HSal] /M

0.00225

0.00250

Uncomplexed
concentration
of Fe3+ /M
3
1.998 10

Uncomplexed
concentration
of HSal /M
3
2.25 10
Page 5 of 11

0.00200

0.000500

1.53 103

3.40 105

0.00175

0.00750

1.29 103

7.04 103

0.00150

0.00100

6.97 104

1.97 104

0.00125

0.00125

3.33 104

3.33 104

0.00100

0.00150

2.27 104

7.27 104

0.000750

0.00175

7.20 105

1.07 103

0.000500

0.00200

2.30 105

1.52 103

10

0.000250

0.00225

1.10 105

2.01 103

Table 8: The Equilibrium constant for the formation of {Fe(Sal)(H 2O)4}3

and its stability constant (K) in the samples (2-10).
Sampl
e#

Concentratio
n of the
complex
/M

Uncomplex
ed
concentrati
on of
Fe3+ /M
1.998 103

2.52 104

4.66 104

1.53 103

4.64 104

Uncomplex
ed
concentrat
ion of HSal
/M
2.25 103

KC

1.12

1055

3.40 105

179

168550

1.29 103

7.04 103

1.02

960

8.03 104

6.97 104

1.97 104

117

110169

9.17 104

3.33 104

3.33 104

165

155367

7.73 104

2.27 104

7.27 104

93.7

88230

6.78 104

7.20 105

1.07 103

176

165725

4.77 104

2.30 105

1.52 103

273

257062

10

2.39 104

1.10 105

2.01 103

216

203390

Page 6 of 11

Figure 3: Calibration Plot of Absorbance vs Concentration of Fe()salicylate complex.

Sample calculation for concentration of Fe3+:

For sample 12;
C1 V 1=C 2 V 2
Concentration of Fe(NO3)3 is equal to concentration of Fe3+ (stoichiometric
ratio 1:1)
3+

Fe

C1 =

Calculation for the value of n:

From figure 2 , z=0.50 ,using equation (10)
n=

z
0.50
=
=1
1z 10.50
Empirical formula of the complex: {Fe(Sal)(H2O)4}3
Page 7 of 11

Sample calculation for KC and K:

For sample 2:
+
H

Since the concentration of HNO3 used is 0.020 M and the reactants

used are in 0.020 M HNO3

At 25C, log10 Ka 2.974

K a=102.974=1.062 103

+
H

{ Fe ( H 2 O )6 }

3+
1
[ HSal]

3
{ Fe ( Sal ) ( H 2 O ) 4 }

K C =

K =K C . K a1 .. ( 30 )
K =

KC
1.12
=
=1055
K a 1.062 103

Meaningful

K =

K values,

K ( 3 ) + K ( 6 )+ K ( 8 )+ K (10) 168550+155367+ 165725+203390

=
=173258
4
4

K ' =173258
Page 8 of 11

The Gibbs energy:

G (T )=RTln K '

G ( 298.15 )=( 8.315 )( 298.15 ) ln ( 173258 )=29904

G ( 298.15 )=29.90

J mol-1

KJ mol-1

DISCUSSION
In this experiment the
determination

the

spectrophotometric

composition

and

the

method was

stability

constant

used to
of

the

iron(III) salicylate complex. From figure 2 (Job plot), we can see that at a
mole fraction of 0.5 Fe, there is a maximum of absorbance result. A mole
fraction of 0.5 means that there is an equal amount of moles of Fe
reacting with salicylate. This shows that the complex of iron and salicylate
is at a 1:1 ratio.
The value of n was calculated and found to be 1, thus the empirical
formula of the complex is {Fe(Sal)(H2O)4}3. The stability constant of the
complex was found to be
function at 298 K to be
value. The

173258

29.90

which gave the value for the Gibbs

KJ mol-1 which is very large negative

larger negative value for the Gibbs function implies that

the formation of the complex was spontaneous and that iron (III)
salicylate complex is very stable. Since the theory agrees with the
experiment, this shows the reliability of the method employed to
determine the stability constant and the Gibbs function of the iron
(III) salicylate complex.

CONCLUSION
The experiment shows that the reaction mechanics of the iron and
salicylate peaks at a 1:1 ratio. This also shows that this set up is the most
favourable in creating this complex. The empirical formula of the complex
was found to be {Fe(Sal)(H2O)4}3. The stability constant and the standard
Page 9 of 11

Gibbs function was found to be 173258

and 29.90

KJ mol-1 respectively.

Some errors in the part of the experiment are that there was some human
error in creating the mixes with different concentrations.

Answers to Questions
1. The value of hydrogen ion (H +) concentration that should be
used is 0.020 M. This value is considered to be constant since
the concentration of HNO3 that was added in all the solutions
was 0.020 M and the reactants used are in the 0.020 M of HNO 3,
thus this causes hydrogen ion to have a constant value of
concentration.

2. The Gibbs energy of formation in solution,

G (T ) , is

the

standard Gibbs energy for the formation of the complex from

its
elements
in
their
reference
states, i.e.
r G=Products f GReactants f G.
3. The donor centres on this ligand are on the oxygen of the
phenolic acid group and the other one is on the double
bonded oxygen of the carboxylic acid group , thus the ligand
is a bidentate ligand since it has two donor centres .The
structure would be more steric hindered thus only one ligand
will coordinate the iron ion.

CH3
O

Iron(II)-salicylate complex

Fe
:

Page 10 of 11

REFERENCES
1. Harris, Daniel C. Quantitative Chemical Analysis. 8th ed. New York:
W.H. Freeman, 2010.
2. P. W. Atkins and J. De Paula, 2006. Physical Chemistry. 9th Edition.
Chapter 7.

Page 11 of 11