SPECTROPHOTOMETRIC DETERMINATION OF THE

EQUILIBRIUM CONSTANT OF A REACTION

A.F. BELEN1, M.N MANALO 1, C.S. D E CASTRO 1, K.R. SANTOS1, M.R.
ARAMBULO 1, M.P. ORBON1, B.P. MANZANO1, M. RAMOS1, K.D. RUBIO 1 AND
D.A. MONGE2
1
DEPARTMENT OF MINING, M ETALLURGICAL , AND MATERIALS ENGINEERING, C OLLEGE OF
ENGINEERING
2
NATIONAL INSTITUTE OF PHYSICS , C OLLEGE OF S CIENCE
UNIVERSITY OF THE PHILIPPINES , DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: SEPTEMBER 22, 2016
INSTRUCTORS NAME: MAE FAJICULAY

ABSTRACT
The experiment was made to determine the equilibrium constant of the reaction
with the use of spectrophotometry and the application of Beer-Lamberts Law
that gives the relationship of the amount of light the solution can absorb and its
concentration. iron(III) thiocyanate, Fe(SCN)2+, complex was used in the
experiment. Using the calibrated single beam UV-Vis spectrophotometer the
absorbance of Fe(SCN)2+ was measured then plotted into a graph against the
concentration of the solution. The equation of the graph obtained is y=4838.3x
0.0724, where the slope is the molar absorptivity coefficient and the y-intercept
is the error; these two was used in calculating the concentrations of Fe 3+, SCN-,
and Fe(SCN)2+ at equilibrium. Keq was obtained using the concentrations at
equilibrium and is equal to 199.64 which has a 44.67% error compared to the
theoretical Keq which is 138. According to the results, the absorbance of light and
concentration of solution has a direct relationship. Based on the error, the
experiment is a failure. It was recommended to use a more diluted solution using
more pure reagents, to do the experiment in a consistent ambient temperature
and to handle the UV-Vis spectrophotometer in a greater accuracy or use a
double beam UV-Vis spectrophotometer.
INTRODUCTION
In a state of balance or equilibrium the rate of forward reaction is equal to the
rate of the reverse reaction.[1] The reaction of iron(III), Fe 3+, and thiocyanate,
SCN-, forming iron(III) thiocyanate, Fe(SCN)2+, which is shown in equation (1) was
observed in this experiment. The blood-red complex observed is because of the
chromophore (a molecule that has a capability to absorbs light resulting in a
coloration of a compound[6]) Fe(SCN)2+.
Fe3+(aq) + SCN-(aq)

FeSCN2+(aq)

(1)

The ratio of the products and reactants is called the equilibrium constant
expression and its numerical value is the equilibrium constant, K eq.[3] The
magnitude of Keq is equal indicates how far the reaction proceeds to product. [5]
The equilibrium constant expression for the Keq of the reaction in equation (1) is:
1

2+
Fe(SCN )

3+
Fe
Keq=

SCN

(2)

A spectrophotometer was used in the experiment. It is compose of two

instruments, one is spectrometer which produces light and photometer which
measures the intensity of the light.[4] There are two kinds of spectrophotometer;
one is single beam spectrophotometer that should be calibrated first using the
standard solution before measuring the absorbance of light, and double beam
spectrophotometer which has two sample holder, one for the standard solution
and the other is for the solution that will be observed. The single beam
spectrophotometer was used in the experiment.
According to Beer-Lamberts Law, the absorbance of light is proportional to the
number of molecules it interacts with, and the higher the concentration of the
solution the higher the molecules that will interact with light meaning the
absorbance of light is proportional to the concentration of the solution. [7] And with
this, using the absorbance of light measured in the spectrophotometer at a given
wavelength concentration of the complex ca be computed.
The analytical wavelength, max, used in the experiment is 466 nanometers. It is
the wavelength at which the sample has a maximum absorbance.
A not so diluted solution should be used because and incredibly dilute solution, it
is hard to see if it is colored at all and may cause a very low absorbance. [7]
A=bc

(3)

Equation (3) is the Beer-Lamberts Law where A is the absorbance, is the molar
absorptivity coefficient in M-1cm-1, b is the path length in cm and c is the molar
concentration of analyte in M.
The calibration curve that was obtained by plotting the absorbance of the
solution against its concentration has a relationship with the Beer-Lamberts Law.
y=mx+b

(4)

Where y is the absorbance, A, m is the molar absorptivity coefficient, , x is the

concentration of analyte, c, and b as the error. The path length used in the
calculations is 1cm so it wont affect the results.

By using equation (3) and (4) the concentrations of Fe 3+, SCN-, and Fe(SCN)2+ at
equilibrium will be calculated then it will be plugged in to equation (2) to solve
for Keq of the solution.
The experiment was made to determine the equilibrium constant of the reaction
with the use of spectrophotometry and the application of Beer-Lamberts Law
that gives the relationship of the amount of light the solution can absorb and its
concentration.
CONCLUSION AND RECOMMENDATION
As the concentration of the solution increases the absorbance of light increases
too. It can be said that the two has a direct proportionality. It was also stated in
Beer-Lamberts Law (Equation (3)).
The equation of the best fit line obtained was y=4838.3x-0.0724 and has a
linear regression, r2, 0.9896 which is not too far from the ideal values. But, when
the Keq was solved from the ratio of the products and reactants of the unknown
solutions, the value obtained was 199.64 and has a percent error of 44.67%
compared to the theoretical value, 138[2].
The experimental values was too far from the literature values which caused by
some experimental mistakes. The results can be improved by diluting the
solutions more, having a more pure reagents that will be used in the solution
preparation, conducting the experiment in a constant ambient temperature,
handling the apparatus properly specially the cuvette, and using double beam
spectrophotometer instead of single beam spectrophotometer.
REFERENCES
[1]
Brown, T., et. al. Chemistry: The Central Science 13th Ed.; Pearson Education,
Inc.: Canada, 2015; pp. 628.
[2]
Day & Underwood. Quantitative Analysis; Prentice-Hall: New Jersey, 1958; pp.
181.
[3]
Petrucci, R., et. al. General Chemistry: Principles and Modern Applications, 10th
Ed.; Pearson, Inc.: Canada, 2011; pp. 658.
[4]
Principles of Spectrophotometry.
http://www.ruf.rice.edu/~bioslabs/methods/protein/spectrophotometer.html
(accessed Sept 22, 2016)
[5]
Silberberg, M. Chemistry: The Molecular Nature of Matter and Change, 5 th Ed.;
The McGraw-Hill Companies: New York, 2009; pp. 741.
[6]
Some biological chromophores.
http://omlc.org/classroom/ece532/class3/chromophores.html (accessed Sept 28,
2016)
[7]
The Beer-Lambert Law.
http://www.chemguide.co.uk/analysis/uvvisible/beerlambert.html (accessed Sept
28, 2016)

APPENDIX
A. Calibration Curve
MiVi=M2V2
M2= (M1Vi)/V2
[Fe3+]initial=[Fe3+]stock(V)stock/(V)total

(5)
(6)
(7)

Note: Every solution has an [Fe3+]stock of 0.002M and a Vtotal of 10mL.

Sample calculation for S1: [Fe3+]initial=(0.002M)(0.10mL)/(10mL)=2x10-5
Table 1. Vstock, and [Fe3+]initial of the standard solutions
Solution
Vstock, mL
[Fe3+]initial, M
S1
0.10
2x10-5
S2
0.20
4x10-5
S3
0.50
1x10-4
S4
1.00
2x10-4
S5
2.00
4x10-4
Note: Since Fe3+ is the limiting reagent it means that it has the same
concentration as the Fe(SCN)2+.
Graph Absorbance vs [Fe(SCN)2+] to get the calibration curve.

f(x) = 4838.31x - 0.07

R = 0.99

Figure 1. Absorbance vs. [Fe(SCN)2+] graph.

B. Absorbance of Unknown Solutions
Used equation (7) again but with different V stock.
Table 3. Vstock, and [Fe3+]initial of the unknown solutions
Solution
Vstock of [Fe3+],
[Fe3+]initial, M
Vstock of
[SCN-]initial, M
mL
[SCN ], mL
-4
U1
3.0
6x10
5.0
1.0x10-3
U2
4.0
8x10-4
5.0
1.0x10-3
-3
U3
5.0
1x10
5.0
1.0x10-3
C. Equilibrium Constant Determination, Keq
A=bc
y = 4838.3x - 0.0724

(3)
(7)

Where:
y= absorbance (A)
m= 4838.3 M-1cm-1 ()
x= [Fe(SCN)2+]eq =c
b= 1cm
x=

y + 0.0724
4838.3

Sample calculation of U1: [Fe(SCN) 2+]eq=

(8)

0.383+ 0.0724
= 9.41x10-5
4838.3

Table 3. Absorbance and [Fe(SCN)2+]eq of unknown solutions

Solution
Absorbance
[Fe(SCN)2+]eq, M
U1
0.383
9.41x10-5
U2
0.510
1.20x10-4

U3

0.617

[Fe3+], M
[Fe3+]initial
-x
[Fe3+]initial-x

Initial
Change
Equilibrium

1.42x10-4

[SCN-], M
[SCN-]initial
-x
[SCN-]initial-x

[Fe(SCN)2+], M
0
+x
x

x= [Fe(SCN)2+]eq
[Fe3+]eq= [Fe3+]initial-x
[SCN-]eq= [SCN-]initial-x

(9)
(10)

Sample calculations for U1: [Fe3+]eq= (6x10-4)-( 9.41x10-5)= 5.06x10-4

[SCN-]eq= (1x10-3)-( 9.41x10-5)= 9.06x10-4
Table 4. [Fe3+]eq and [SCN-]eq of unknown solutions
Solution
[Fe3+]eq
[SCN-]eq
U1
5.06x10-4
9.06x10-4
-4
U2
6.80x10
8.80x10-4
-4
U3
8.58x10
8.58x10-4

2+
Fe(SCN )

3+
Fe
Keq=

SCN

(2)

9.41 x 105

Sample calculations for U1: Keq= (5.06 x 104)(9.06 x 104) =205.26

Table 5. Keq of unknown solutions

Solution
Keq
U1
205.26
U2
200.53
U3
192.89
KeqAVE =

205.26+ 200.53+192.89
=199.64
3

%error =

theoreticalexperimental

x 100
theoretical

44.67%

138199.64
138 =