SPECTROPHOTOMETRIC DETERMINATION OF THE

EQUILIBRIUM CONSTANT OF A REACTION /

EXPERIMENT 5
S. M. R. B AUTISTA
DEPARTMENT OF M INING, METALLURGICAL AND M ATERIAL ENGINEERING, C OLLEGE OF
ENGINEERING
UNIVERSITY OF THE PHILIPPINES , DILIMAN , QUEZON C ITY , PHILIPPINES
DATE PERFORMED: JANUARY 14, 2014
INSTRUCTOR S NAME: MR. JOHN HERO SALVADOR

ABSTRACT
This experiment focuses on the formation of the complex [FeSCN] 2+
from the reaction of Fe3+ and SCN-. Its objectives are to determine the Equilibrium
Constant, Keq, the ratio of the concentration of the products and the reactants, using
Spectrophotometry and Beer-Lamberts Law. Spectrophotometry is the use of
radiation which is absorbed by the molecule to determine many molecular
properties like color. The absorbance acquired from the standard solutions was
applied to the Beer-Lamberts Law which was used to determine the molar
absorptivity of the complex [FeSCN] 2+ thus giving way for the calculation of the
equilibrium concentration of the reactants and the products of the unknown
solution, allowing for the computation of the Equilibrium Constant which turned out
to be 383.65 which has 56.89% deviance from the literature value of 890 . This
large difference may be caused by experimental errors such as impurities of
reagents, improper laboratory technique for using the spectrophotometer,
instrumental flaws or human errors.

INTRODUCTION
A reaction is considered to be in
Chemical Equilibrium if it is a
reversible reaction, that of which the
rate of the forward reaction is the
same or equal to the rate of the
backward reaction. This ratio of the
products to reactants at equilibrium is
given by the equilibrium constant - K.

K is determined by using
concentration and order of
products and dividing it by
concentration and order of
reactants. Given the reaction:

aA+ bB<= cC+ dD

the
the
the
the

[C] [ D]eq
K eq = eqa
b
[ A ]eq [ B]eq
The reagents in this reaction
consist of Iron (III) ion which reacts
with Thiocyanate ion to produce Iron
(III) cyanato complex. This reaction is
represented by:

2+

FeSCN (aq )
<=

3++ SCN (aq )

Fe(aq)
The product produced is a
blood- red complex that absorbs light
in the visible region that enables us to
use Spectroscopy.
Spectroscopy is the study of
interaction
between
Matter
and
Electromagnetic
Radiation.
This
experiment is performed using UV-Vis
Spectrophotometer which uses light in
the Visible and Ultraviolet ranges. This
radiation is absorbed by the molecule
which excites electrons from one
energy level to a higher energy level.
This is the condition on which
Molecular Electronic Transition occurs.
The energy change that comes with
this transition gives information about
the structure of a molecule and
determines
many
molecular
properties, like color, which is caused
by the chromophore.
Using a spectrophotometer, the
absorbance of [FeSCN]2+ is measured
at
different
concentrations.
The
absorbance is then put into BeerLamberts Law,

A= bC
where in, is the Molar Absorptivity
(M-1 cm-1) which is the proportionality
constant that has a specific value for
each absorbing species at a given
wavelength , b is the Pathlength
(cm) which is the distance across the
solution
in
centimeters
and
is
dependent upon the size of the
cuvette. C is the Concentration (M)
which is the concentration of the
absorbing species in moles of solute
per liter of solution. This will be used
to find the concentration of [FeSCN] 2+
and as aide to determine the
Equilibrium Constant of the reaction.
The
objectives
of
this
experiment are to prepare solutions
quantitatively,
to
employ
BeerLamberts Law, to identify the
components of a spectrophotometer,
to relate the color of the solution to
the analytical wavelength of the
chromophore,
to
employ
spectrophotometry in determining the
equilibrium
concentration
of
a
chromophore, to calculate Keq for the
formation of [FeSCN]2+, and to write a
formal report.

METHODOLOGY
This experiment was divided
into three parts. For Part1, Solution
Preparation, the group prepared the
stock solutions. They diluted 8.26 mL
of Concentrated HCl to 991.74 mL of
distilled water to form 1000 mL of 0.1
M HCl. Using the 1000 mL of 0.1 M
HCl, they prepared the following
solutions: 50 mL of 0.2 M KSCN by
diluting 0.9718 g of KSCN with 20mL
of 0.1 M HCl into a 50-mL beaker. After

which, they transferred the solution

into a 50-mL volumetric flask. The
solution was then diluted to mark with
0.1 M HCl, 100 mL of 0.002 M KSCN by
transferring 1.00 mL of 0.2 M KSCN
into a 100-mL volumetric flask which
was then diluted to mark with 0.1 M
HCl, 50 mL of 0.2 M FeCl 3 by diluting
1.622 g of FeCl3 with 20mL of 0.1 M
HCl into a 50-mL beaker. After which,
they transferred the solution into a 50mL volumetric flask. The solution was
then diluted to mark with 0.1 M HCl,
and 100 mL of 0.002 M FeCl3 by
transferring 1.00 mL of 0.2 M FeCl3
into a 100-mL volumetric flask which
was then diluted to mark with 0.1 M
HCl,
The group then prepared the
Standard Solutions by preparing the
following solutions in 6-inch test tubes.
The units are all in mL.
Table 1: Components of Standard
Solutions
Solution 0.002
0.20
0.10 M
M
M
HCl
FeCl3
KSCN
Blank
0.00
1.00
9.00
Standard
0.10
1.00
8.90
1
Standard
0.25
1.00
8.75
2
Standard
0.50
1.00
8.50
3
Standard
1.00
1.00
8.00
4
Standard
2.00
1.00
7.00
5
Afterwards, they prepared the
Unknown Solutions by preparing the

following solutions in 6-inch test tubes.

The units are all in mL.
Table 2: Components
Solutions
Solution
0.002
M
FeCL3
Blank
0.0
Unknown
3.0
1
Unknown
4.0
2
Unknown
5.0
3

of Unknown

0.002
M
KSCN
5.0
5.0

0.10
M HCl
5.0
2.0

5.0

1.0

5.0

0.0

Part 2 is the calibration of the

UV-Vis Spectrophotometer. The group
rinsed the cuvette three times with
distilled water followed by the blank
solution. Then they properly placed
the cuvette in the sample holder
inside the spectrophotometer. Since
the spectrophotometer used is singlebeam, they performed Autozero. They
used Standard 5 to measure the
wavelength of maximum absorption.
They used this value for the rest of the
readings.
Then they removed the cuvette,
discarded the solution and rinsed it
again three times with distilled water.
Afterwards, they rinsed it with
Standard 1, discarded the rinse and
filled the cuvette with Standard 1.
They placed the cuvette inside the
spectrophotometer and recorded the
absorbance. Then the cuvette was
removed and the solution was
disposed. They repeated the above
steps for Standards 2 to 5.

For Part 3, they used the

unknown solutions to aide in the
determination of the Equilibrium
Constant
for
the
Formation
of
2+
[FeSCN] . They performed the same
steps as above for all the unknown
solutions using the same wavelength
but different blank solutions.

RESULTS AND DISCUSSION

Water is normally used in
diluting a solute since it is considered
as the universal solvent. However, in
this experiment 0.10 M HCl was used
because the reaction of Iron (II)) ion
with water forms iron hydroxide, which
is insoluble in water:

the reading for the absorbance of the

solution will not only be given by
[FeSCN]2+ but also with Fe(OH)3.
For the determination of the
analytical wavelength, the solution
with highest concentration must be
used because it is where the strongest
or maximum absorption occurs. In the
experiment the analytical wavelength
garnered was 465 nm at 1.006
absorption. The color of the solution
was observed to be near the red
region so the analytical wavelength is
found in the blue region which was the
complementary of the color red
because what passes through a
colored solution is the spectrum of
light complementary to the spectrum
of the absorbed light.

OH 3(s )+ 3 H (aq)
3++3 H 2 O(l) <= Fe
Fe(aq)
Or

+
2++ H
H 2 0 5 ( OH )
Fe
3+<=
H 2 0 6
Fe

To avoid the precipitation of iron (III)

hydroxide, a reddish orange crystalline
precipitate which is a highly insoluble
compound, it is necessary to add the
excess HCl because the formation of
iron (III) hydroxide will be a hindrance
to
the
formation
of
[FeSCN]2+.
Moreover if this hydrolysis takes place

Figure 1: Light Spectrum

The analytical wavelength must
be used to measure the absorbance
because it is where the molecule is
most sensitive which gives accurate
measurements.
In the calibration, the blank
solutions served as the basis of the
absorbance of the standards and the
unknowns. It was leveled to zero to
make up for the absorbance of the
cuvette and the SCN- that was left in

the solution. The limiting reactant of

the solution is Fe3+. To ensure that all
of it will react to form [FeSCN]2+,
excess SCN- was added to the solution,
giving possibility to find for the best fit
line when performing linear regression
of the Concentration vs. Absorbance.
After
calibrating
the
spectrophoto-meter, Standards 1 to 5
were put to test and each of its
absorbance were recorded.
Table 3: Calibration Curve
St
[Fe3+]int [SCN-]i [Fe(SCN)]2+
eq
d
nt
1
0.0000
0.02
0.00002
2
2
0.0000
0.02
0.00005
5
3
0.0001
0.02
0.00010
0
4
0.0002
0.02
0.00020
0
5
0.0004
0.02
0.00040
0

Abs
0.04
3
0.09
2
0.21
4
0.46
9
0.98
3

The concentration of [FeSCN]2+

and the absorbance recorded were
plotted in a graph in which the
concentration will be the x-coordinate
ad the absorbance for the ycoordinate.
1.5
1
Absorbance 0.5

f(x) = 2507.49x - 0.03

R = 1

0
0 0 0 0 0 0 0 0 0 0
Concentration (M)

Figure
2:
Absorbance

Concentration

vs.

The equation of the best fit line

is y = 2507.5x 0.026. This type of
equation is also shown by the BeerLamberts Law which means that the
slope, 2507.5 L/molcm is the molar
absorptivity or of [FeSCN]2+ the
difference of 0.026 can be neglected
since the R2 (0.999) value of the curve
is really close to 1 the R2 of a line.
Using the Beers Law and the
maximum absorbance which is 1.006
at 465 nm, the calculated theoretical
molar absorptivity is 2515L/molcm.
The actual molar absorptivity is close
to the theoretical molar absorptivity
with a 0.29% error.
After the determination of the
absorbance for the standard solutions,
the spectrophotometer was again
calibrated for the testing of the
unknown. Another blank solution was
used because there is a difference
between the standard solutions and
the unknown solutions. In the standard
solutions, 0.20 M KSCN was used while
in the unknown solutions 0.002 M
KSCN was used. The reason for this is
to isolate the absorbance reading to
that of [FeSCN]2+ alone because in
diluted form , SCN- and Fe3+ have small
absorbance. This will give results that
will follow the calibration curve.
By solving mathematically using
the Beer-Lamberts Law and the
equation of the best fit curve, the
concentration of [FeSCN]2+ for each
solution was acquired. This will also be
the equilibrium concentration for
[FeSCN]2+.

Table 4: Unknown Solutions

Un [Fe3+]int [SCN-]i [[FeSCN]2+]
eq
k
nt
1
0.000
0.001 0.000148
6
2
0.000
0.001 0.000189
8
3
0.001
0.001 0.000229
0

Abs
0.34
6
0.44
9
0.54
8

Given the data on Table 4, the

equilibrium concentration for Fe3+ and
SCN- were calculated respectively
using the ICE table.

2+
FeSCN (aq )
<=
3++ SCN (aq )
Fe(aq)
[Fe3+]int
[SCN-]int
-x
-x
3+]
[Fe int
[SCN-]int
-x
-x
Figure 2: ICE Table
I
C
E

0
+x
x

eq

2
3

0.00045
2
0.00061
1
0.00077
1

0.00085
2
0.00081
1
0.00077
1

0.000148
0.000189
0.000229

The data on Table 5

substituted to the expression:

Table 6: Equilibrium Constant

Unknown
Keq
1
384.3118
2
381.4167
3
385.2359
Average
383.6548
The theoretical value of Keq for
[FeSCN]2+ is 890. Given the data in
Table 6, it shows that there is a large
discrepancy between the actual and
theoretical
equilibrium
constant
values. It exhibits 56.89% of error.
The error could have arisen from:

Table 5: Equilibrium Concentration

Unk
[Fe3+]eq
[SCN-]eq [[FeSCN]2+]
1

2+

SCN

3+
F e

SC N

Fe

K eq=

were

Table 8: Sources of Error

Error
Type of Error
Impurity of the
Determinate Error
reagents.
Systematic Error
The outside of the Determinate Error
cuvette was not
wiped thoroughly. Gross Error
The unfrosted
Determinate Error
part of the
-Gross Error
cuvette was
touched.
Inconsistent
Indeterminate
Ambient
Error
Temperature
Improper rinsing
Determinate Error
of the cuvette
-Gross Error
Dilution of the
Determinate Error

test samples
- Systematic
present
Error
inaccuracy.
Poor Pipetting
Determinate Error
Techniques
Gross Error
Presence of Stray
Indeterminate
Light
Error
Inconsistency with Determinate Error
the amount of
Systematic Error
solution placed in
the cuvette.
CONCLUSION AND
RECOMMENDATION
This experiment was performed
using
a
single
beam
spectrophotometer to determine the
absorbance of [FeSCN]2+ in different
concentrations. By plotting the values
of
the
standard
solutions
concentration
vs.
its
respective
absorbance
and
applying
linear
regression, the equation of the
calibration curve was found to be y =
2507.5x 0.026 with a linearity
coefficient of R2 of 0.999 which shows
that the calibration is valid because it
is close to the ideal value which is 1.
By application of Beer-Lamberts Law,
the concentration of the unknown
solution was determined. The use of
the ICE table enabled the calculation
of the equilibrium concentrations of
the products and the reactants thus
gave way to the computation of the
equilibrium constant of the unknown
solutions. However the Keq acquired in
this experiment, which is 383.65 is far
from the theoretical Keq which is 890. It
exhibits 56.89% error.
In
order
to
prevent
discrepancies when it comes to the
data, the sources of error found in

Table 8 must be avoided or at least

minimized to acquire more accurate
data.
REFERENCES
[1] Petrucci R. H., Herring G. F.,
Madura, J. D., Bissonnette, C., General
Chemistry: Principles and Modern
Applications. Pearson Canada Inc.,
Toronto, Canada. 2007
[2] Fazil, M. A. B., Factors affecting
Rate of Reaction.
International
Baccalaureate Organization, Geneva,
Switzerland. 2005
[3] Chemical Equilibria. Retrieved on
January
19,
2014
from
http://pages.towson.edu-/ladon/cheme
q.html
[4] Reiser T., Advance Placement
Chemistry. Retrieved on January 19,
2014
from
http://www.scienceteacherprogram.org
/chemistry/Tehilla98.html

[6] Capriola A., Determining the

Equilibrium Constant of a Reaction using
Spectrophotometry. Retrieved on January
19,
2014
from
http://adamcap.com/schoolwork/determining-an-equilibriumconstant-using-spectrophotometry/

[7]

Ibale

J.,

Spectrophotometric
Determination of the Equilibrium
Constant of a Reaction. Retrieved on
January
20,
2014
from
http://www.scribd.com/doc/122364270/Formal-Report-Experiment-5-RDR

APPENDIX
Calculations:
A. Calibration Curve:
Finding the initial moles of the reactants and products:

M 1 V 1=M 2 V 2
M 1=

M2 V 2
V1

*Since Fe3+ is the limiting reactant: [Fe3+] = [[FeSCN]2+]

2+
0.002 M ( 0.1 ml )
FeSCN =
=0.00002 M
Standard 1:
10 ml

2+
0.002 M ( 0.25 ml )
FeSCN =
=0.00005 M
Standard 2:
10 ml

2+
0.002 M ( 0.5 ml )
FeSCN =
=0.00010 M
Standard 3:
10 ml

2+
0.002 M ( 1.0 ml )
FeSCN =
=0.00020 M
Standard 4:
10 ml

2+
( 2.0 ml )
0.002
M
FeSCN =
=0.00040 M
Standard 5:
10 ml

[SCN-]
*Standard 1 to 5 has the same molarity because they have the same volumes.


( 1.0 ml )
0.002
M

=0.02 M
Standard 1-5: SC N =
10 ml

B. Absorbance of Unknown Solutions

M 1 V 1=M 2 V 2
M 1=

3+

Fe

M2 V 2
V1

int

3+
F e
Unknown 1:

3+
F e
Unknown 2:

3+
F e
Unknown 3:

SCN

int

*Standard 1 to 5 has the same molarity because they have the same volumes.

SCN
Unknowns 1-3:

C. Molar Absorptivity

Actual:
A=bC
y=2507.5x 0.026
= 2507.5 cm-1M-1
Theoretical:

A ( max)
bC

max=1.00 6
C = 0.0004 M, Most concentrated solution

1.006
=2515 c m1 M 1
( 1 cm ) (0.0004 M )

Percent Error:

x 100
theoretical
%error=

actualtheoretical

2507.52515 x 100 =0.29

2515
error =
D. Equilibrium Constant Determination
Calibration Curve:
A=bC
y=2507.5x 0.026
where
y= A (Absorbance)
b= 1 cm
= 2507.5
C= [[FeSCN]2+]eq

C=

y + 0.026
2507.5

[[FeSCN]2+]:
Unknown 1:

C=

0.346+0.026
=0.000148 M
2507.5

Unknown 2:
Unknown 3:

C=

0.449+ 0.026
=0.000189 M
2507.5

C=

0.548+0.026
=0.000229 M
2507.5

2+
FeSCN (aq )
<=
3++ SCN (aq )
Fe(aq)
I
C
E

[Fe3+]int
-x
[Fe3+]int
-x

[SCN-]int
-x
[SCN-]int
-x

0
+x
x

X = [[FeSCN]2+]eq
[Fe3+]eq = [Fe3+]int - [[FeSCN]2+]eq
[SCN-]eq = [SCN-]int - [[FeSCN]2+]eq

=0.0006 M 0.000148 M =0.000452 M

Unknown 1:

3+
F e

=0.0008 M 0.000189 M =0.000611 M

Unknown 2:

3+
F e

=0.0010 M0.000229 M=0.000771 M

Unknown 3:

3+
F e

=0.0010 M 0.000148 M =0.000852 M

Unknown 1:

SC N

 =0.0010 M 0.000189 M =0.000811 M

SC N

Unknown 2:

=0.0010 M0.000229 M=0.000771 M

SC N

Unknown 3:

Equilibrium Constant:
2+

SCN

3+
F e

SC N

Fe

K eq=

Unknown 1:

K eq =

0.000148 M
=384.3118
( 0.000452 M ) (0.000852 M )

Unknown 2:

K eq =

0.000189 M
=381.4167
( 0.000611 M ) (0.000811 M )

Unknown 3:

K eq =

0.000229 M
=385.2395
( 0.000771 M ) (0.000771 M )

Actual:
Keq average = 383.6548
Theoretical:

Keq = 890
Percent Error:

x 100
theoretical
%error=

actualtheoretical

383.6548890 x 100 =56.89

890
error =