SPECTROPHOTOMETRIC

DETERMINATION
EQUILIBRIUM CONSTANT OF A REACTION

OF

THE

F.G. QUEZON1 AND F.D. GARCIA1

1

DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING

UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: JANUARY
INSTRUCTORS NAME: IRINA

16 2013
DIANE CASTANOS

ABSTRACT
The objective of the experiment, Spectrophotometric Determination of the
Equilibrium Constant, is to calculate the equilibrium constant of a reaction based on
the absorbance values measured by a UV-Vis Spectrophotometer. The main working
equation behind it is Beer-Lamberts law which directly relates the analyte molar
concentration and measured absorbance. Standard solutions of varying amounts of
Fe3+ were placed in the cuvette to have its absorbance determined. After obtaining
a regression line, the same was done for the unknown solutions, and the regression
line and absorbance values were used to compute the concentrations of products
and reactants at equilibrium to obtain the equilibrium constant. The value 324.791
was obtained as the experimental K eq value and this was found to have a more or less 16%
percent difference from the literature value.

INTRODUCTION
Spectrophotometry is a method
to measure how much a chemical
substance absorbs light by measuring
the intensity of light that passes
through the sample solution. It
determines the concentration of an
unknown solution by using the atoms
ability to absorb radiant energy. One
of its uses is in determination of the
equilibrium constant of a reaction.
The experiment made use of
FeCl3 and KSCN. Both solutions are
colorless in contrast to the red orange
[FeSCN]2+ complex. The balanced
reaction for this equation is shown
below.
Fe3+(aq) + SCN-(aq) [FeSCN]2+(aq) (1)
A UV-Vis Spectrophotometer is
used in the experiment to measure the

absorbance of the solution. Then the

Beer-Lamberts equation is used to
compute for molar concentration of
[FeSCN]2+. Below is the Beer-Lamberts
equation:
A = bc (2)
where A = absorbance

=
molar
absorptivity
coefficient
b = path length in cm
c = analyte molar concentration
It could also be treated as a linear
equation in the form of y=mx + b
where y=A, m=b, c=x and the y
intercept b is equal to zero, though in
computations, a non-zero y-intercept
would
be
present
because
of
experimental errors.
For the computation of the
equilibrium constant of the unknown
1

based on their absorbance, the

equation for Kc is used.
Kc = [[FeSCN]2+] . (3)
[Fe3+][SCN-]
The purpose of this experiment
is to show the direct relationship
between a substances absorbance
value and its concentration. Another is
to
show
the
usage
of
a
spectrophotometer and how it can be
used to determine a solutions
concentration
and
equilibrium
constant.

of the standard solutions, rinsing the

cuvette 3 times with the solution to be
used
before
filling
it
for
the
determination of the absorbance.
When it came to the unknown
solutions, the spectrophotometer was
autozeroed again before determining
the absorbance of the blank solution
and the procedure was repeated.
After tabulating the results, the
absorbance values of the standard
solutions were plotted against the
concentration of Fe3+. The r2 value was
computed and also the values for the
slope and y-intercept. The slope and yintercept values are used to write the
equation of the regression line.
The absorbance values of the
unknown solutions were plugged in y
in the equation and the value of x was
solved. The x values are the
equilibrium concentrations of the
[FeSCN]2+ in the unknown solution.
After determining this, the ICE table
was
used
to
determine
the
concentration of the reactants and the
equilibrium constant Keq. Since there
are 3 unknown solutions, the results
for their Keq are averaged and the
mean was compared to the theoretical
value. The percent difference was then
computed.

METHODOLOGY
The first part of the experiment
was the preparation of the stock
solutions. The solutions prepared are
500ml 0.10 M HCl from 12.1 M HCl,
and from this, 50 ml 0.20 M KSCN, 50
ml 0.20 M FeCl3 are prepared. Then
100ml of 0.002 M KSCN was prepared
from 0.20 M KSCN and 50ml of 0.002
M FeCl3 was prepared from the 0.20 M
FeCl3 stock solution.
After that was the preparation
of the standard solutions and unknown
solutions. In the standard solutions,
0.20 M KSCN was kept constant at 1.0
ml in all test tubes. In the blank, no
FeCl3 was added. In test tubes 1 to 5,
0.002 M FeCl3 was added in 0.1, 0.25,
0.5, 1.0, and 2.0 mL respectively. The
0.10 M HCl was used to dilute all
standard solutions to 10 ml. The same
process was done for the preparation
of unknown solutions. The KSCN was
kept constant at 0.002 M and 5.0 mL.
The blank contained no FeCl 3 but test
tubes 1 to 3 contained 3.0, 4.0, and
5.0 mL of 0.002 M FeCl 3 respectively.
Again, 0.10 M HCl was used to dilute
the solution to 10 mL.
The standard solutions were
used first. After the spectrophotometer
was autozeroed, the cuvette was
rinsed with water, and then with the
blank solution. It was placed in the
sample holder and its absorbance was
determined. This was repeated for all

RESULTS AND DISCUSSIONS

In an acidic solution, Fe3+ reacts
with SCN- to produce the red orange
complex [FeSCN]2+. The reagents are
colorless which ensures a large
contrast between the product and
reactants. Instead of water, 0.10 M HCl
was used to dilute the solution
because the water would react with
Fe3+ to form [Fe(H2O)6]3+. The chemical
reaction for the hydrolysis of Fe 3+ is
shown below:
Fe3+(aq) + 6H2O(l) [Fe(H2O)6]3+ (4)
The presence of this complex
causes the violet color of Fe 3+ salt
solutions.
The spectrophotometer
would give a different value for
2

all reactants other than Fe 3+ which is

the one whose absorbance is to be
determined. The spectrophotometer is
calibrated by determining that ions
other than Fe3+ is negligible and
should not be factored by the machine
in the determination of the value of
absorbance. This is done by autozeroing the device at the blank
solution which contains all reactants
other than Fe3+.
KSCN is added in excess so that
FeCl3 would become the limiting
reagent. Because of the one is to one
ratio of Fe3+ to [FeSCN]2+, their
concentrations would be equal. Their
absorbance values would also be
equal thus these data could now be
used to obtain the equation for the
regression line of the data. Since the
blank was declared to have zero
absorbance, the absorbance values
obtained for the rest of the standards
are already the corrected values.

absorbance because different colors

absorb different wavelengths of light.
The plot for the wavelength
versus concentration is shown below:
A
b
wavelength
s
o
r
b
a
n
c
e

Figure
1.
Wavelength

analytical

wavelength

Absorbance

vs.

Here we can see that the highest

absorbance value gives us the
analytical wavelength. And since
absorbance is directly proportional to
concentration, this means that the
analytical wavelength is at the highest
concentration
of
the
solutions
measured which is why the solution
with the highest concentration should
be used to determine the analytical
wavelength.
The analytical wavelength of
[FeSCN]2+ is 466 nm. This means that
this is the wavelength of light
absorbed by the solution. If we check
the color wheel we see that the range
of wavelength of the color blue is 440490 nm. Its complement is the color
orange which happens to be the color
of the solutions used, meaning that
blue is the color absorbed and its
complement, orange, is the one that is
reflected.
Measurement of the
solutions absorbance at the analytical
wavelength gives the most precise
results because absorbance per unit
concentration is greatest at the
analytical wavelength.
The blank solution is necessary
for the calibration. The blank contains

Figure
2.
2+
[FeSCN]

Absorbance

vs.

The slope of this curve is

1221.544 while the y-intercept is
-0.01892 and the r2 value is
0.997127468. Therefore the equation
of the regression line for this is
y=1221.544x 0.01892. The slope is
equal to b, and if we take b to be 1
cm, we can calculate the value of
which
is
equal
to
1221.544.
Theoretically, the value should be
3550/Mcm. There is a percent
difference
of
65.69%.
For the unknown solutions,
0.002M of KSCN was used instead of
3

0.2 M that used for the calibration.

This is done so that there would be
equal concentrations of KSCN and
FeCl3 in varying amounts, and the
molarity of the product would not be
determined by the Fe3+ all of the time.
Another blank solution must be used
because of the changes in molarity of
the KSCN. The spectrophotometer
must be auto-zeroed at the blank
solution with 0.002 M KSCN. Similar to
the standard solutions, the values of
absorbance for the unknown solutions
do not need to be corrected anymore
since the device was already autozeroed at the blank solution.
Table
1.
absorbance

[FeSCN]2+eq

and

Absorban
ce

[FeSCN]2+e

Unknown 1

0.143

0.000133

Unknown 2

0.185

0.000167

Unknown 3

0.234

0.000207

Solution

The equation y=1221.544x

0.01892 is used where y is the
absorbance and x is the [FeSCN]2+eq.
The absorbance values are obtained
through
the
experiment
and
[FeSCN]2+eq is solved. Then the ICE
table was used to calculate the
concentrations of the SCN- and Fe3+ in
the equilibrium state. These values are
then used to compute for Keq.

Table
2.
Concentrations

Equilibrium

Solution

[Fe3+] eq

[SCN-] eq

Keq

Unknown
1

0.00046
7

0.00086
7

328.
5

Unknown
2

0.00063
3

0.00083
3

316.
7

Unknown
3

0.00079
3

0.00079
3

329.
2

Based on the calculations, an

average Keq value of 324.791 is
obtained. Compared to the literature
value that ranges from 140 to 280,
there is a 16% percent difference. This
is a considerably small value, thus it
can be concluded that the experiment
is a success.
REFERENCES
[1]UC
Davis
Chem
Wiki.http://chemwiki.
ucdavis.edu/Physical_Chemistry
/Kinetics/Reaction_Rates/Experi
mental_Determination_of_Kinetc
s/Spectrophotometry (accessed
Jan 19, 2013).

The three values obtained for Keq was

then averaged. The result is 324.8.
The range of the literature value is
140-280 and based on computations,
there is a percent difference of 15.997
or 16%. The percent error might be
because of the following errors:

[2]Davidson
College
Chemistry
Resources.
http://www.chm.davidson.edu/v
ce/spectrophotometry/Spectrop
hotometry.html (accessed Jan
20, 2013).

Table 3. Possible Sources of Errors

Error
touching clear side of
the cuvette
equipment failure
failing to auto-zero
the
spectrophotometer
air bubbles in the
cuvette
improper preparation
of reagents
calculation error

Type

[3] Institute of Chemistry. General

Chemistry II Laboratory Manual.
University of the PhilippinesDiliman.

gross error
gross error
systematic
error
indetermina
te error

[4] ChemEd University of Wisconsin

Madison.
http://chemed.chem.wisc.edu/c
hempaths/GenChemTextbook/Transition-Metal-Ionsin-Aqueous-Solutions-1055.html
(accessed Jan 20, 2013).

gross error
gross error

CONCLUSION
AND
RECOMMENDATION
In the experiment, a UV-Vis
Spectrophotometer
was
used
to
determine the equilibrium constant of
a reaction. It made use of the BeerLamberts law that directly related the
absorbance value with the molar
concentration of the analyte. The
regression line of y = 1221.544x
0.01892 is obtained with a linearity
coefficient of 0.997127648.

[5]

Weber
State
University.
http://faculty.
weber.edu/nokazaki/Comparativ
e%20Animal
%20Physiology/Laboratory/Spec
trophotometry04-1.pdf
(accessed Jan 20, 2013).

[6] Flexible Learning Tool Boxes. http://

toolboxes.flexiblelearning.net.au
/demosites/series5/508/laborato
5

ry/studynotes/snAnalyWaveleng
th.htm (accessed Jan 20, 2013).

(0.000467)(0.000867)
= 328.485

CALCULATIONS
Preparation of stock solutions:
Table A.
Standard 1
0.002(0.1) = M2 (10)
M2 = 0.00002M
Standard 2
0.002(0.25) = M2 (10)
M2 = 0.00005M
Standard 3
0.002(0.5) = M2 (10)
M2 = 0.0001M
Standard 4
0.002(1) = M2 (10)
M2 = 0.0002M
Standard 5
0.002(2) = M2 (10)
M2 = 0.0004M

Unknown 2
0.185 = 1221.544x 0.01892
x = 0.000166936

Table B.
Unknown 1
0.002(3) = M2 (10)
M2 = 0.0006M
Unknown 2
0.002(4) = M2(10)
M2 = 0.0008
Unknown 3
0.002(5) = M2(10)
M2 = 0.001

Unknown 3
0.234 = 1221.544x 0.01892
x = 0.000207049

Fe3+(aq) +
0.0008
-x
0.0008-x

[Fe3+] = 0.0008-0.000167 = 0.000633

[SCN-] = 0.001 0.000167 =
0.000833

Fe
+
0.0006
-x
0.0006-x

Kc =

[Fe3+] = 0.0010-0.000207 = 0.000793

[SCN-] = 0.001 0.000207 =
0.000793

(aq)

Kc =
2+
(aq)

Average Keq
= (328.485 + 316.714 + 329.173)
3
= 324. 791
% difference
= |(280-324.791)| x
280
= 15.997% or 16%

2+

[[FeSCN] ] .
[Fe3+][SCN-]
0.000133

[[FeSCN]2+] .
[Fe3+][SCN-]
0.000207
(0.000793)(0.000793)
= 329.173

Kc =

[Fe3+] = 0.0006-0.000133 = 0.000467

[SCN-] = 0.001 0.000133 =
0.000867

Kc =

Fe3+(aq) +
SCN-(aq) [FeSCN]2+(aq)
0.001
0.001
-x
-x
+x
0.001-x
0.0001-x
0.000207

SCN
[FeSCN]
0.001
-x
+x
0.001-x
0.000133

Kc =

[[FeSCN]2+] .
[Fe3+][SCN-]
0.000167
(0.000833)(0.000633)
= 316.714

Kc =

Table C.
Unknown 1
0.143 = 1221.544x 0.01892
x = 0.000132553
3+
(aq)

SCN-(aq) [FeSCN]2+(aq)
0.001
-x
+x
0.0001-x
0.000167

100