DATE PERRFORMED: JANUARY 04, 2010

SPECTROPHOTOMETRIC DETERMINATION OF THE

EQUILIBRIUM CONSTANT OF A REACTION

VERGARA, ANGELICA R.
NATIONAL INSTITUTE OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES

ABSTRACT

Spectrophotometry can be an effective method of determining the equilibrium constant of a reaction, one example is with the system
Fe3+(aq) + SCN1-(aq) <-----> Fe(SCN)2+(aq), that is used in this experiment. In here, the relation between absorbance and system’s
concentration is studied in order to have Keq Standard solutions of various concentrations of FeCl 3, KSCN, and HCl that are tested in
spectrophotometer for absorptivity are used to come up with the calibration curve that will be used for the obtaining Keq. The best-fit line y =
3247.5x + 0.637 is formed with domain, that is the concentration of Fe(SCN) 2+(aq), and range composed of values of absorbance with respect
to the system’s concentration. Then, unknown solutions are prepared for the absorbance test. Using the Beer’s Law, A = εbc, and plugging the
slope of the best-fit line in ε, the molar absorptivity coefficient, and the absorbance in A, c or the equilibrium concentration of Fe(SCN) 2+ is
obtained. Then will follow the calculation of the reactant’s equilibrium concentration. And finally, using the equilibrium constant expression,
Keq of 186 for this reaction is determined.

INTRODUCTION of the absorbed light. The relative intensity of color is

Chemical Equilibria requires the determination
of equilibrium constants. In order to find the condition
on where a reaction has equal and reversible sides,
constant of equilibrium is calculated based from the
concentrations of the reagents involved.
As said, one way of determining equilibrium
constant (Keq) is through calculation. In this
experiment, another way of determining Keq is studied. This
is thru the process Spectrophotometry using an apparatus
called Spectrophotometer. This machine measures the
intensity as a function of a color, or specifically, a
wavelength of light. The amount of light absorbed by
the system is called the absorbance.
Absorbance, on the other hand, is described by
the time when continuous electromagnetic radiation
(light) passes through a material, a portion of the light
may be absorbed. The remaining light exits the sample
and, when passed through a prism, will yield a
spectrum with gaps in it. The color that our eyes see is
due to the wavelengths of light that the sample did not
absorb, that is, we see the transmitted color. The
transmitted color is opposite the complementary color
proportional to the concentration of the dissolved compound. The
greater the compound's concentration, the darker (more intense)
the solution color appears.
A quantitative relationship exists between the
amount of light absorbed at each individual wavelength
and the concentration of the substance dissolved in a
given solvent. This relationship is known as the Beer-
Lambert Law (or Beer's Law),
A=εbc
where A is the measured absorbance of a solution, ε
is the molar absorptivity constant (M-1cm-1), b is the cell path
length through the solution (usually 1 cm), and c is the
concentration of the solution (M). The molar absorptivity
constant has a unique value at each wavelength of the
spectrum of a solution. If a solution of compound
obeys the Beer-Lambert Law, a plot of absorbance at a
given wavelength vs. concentration give a straight line. In this
case, y is the absorbance and x is the concentration.
Now, the purpose of this experiment is to
determine a value for the equilibrium constant for the reaction
between Iron (III) Chlorate (FeCl3) and Potassium Thiocyanate
(KSCN). Also, the concentrations of the thiocyanate
iron(III) complex ion, Fe(SCN)2+ will be measured, with concentration with respect to solving to K eq of a
which forms when you mix solutions containing ferric reaction.
ion, Fe3+ and thiocyanate ion, SCN-, as indicated by the
following equation: Given the reaction,

Fe3+(aq) + SCN1-(aq) <-----> Fe(SCN)2+(aq) Fe3+(aq) + SCN1-(aq) <-----> Fe(SCN)2+(aq)

Wherein the equilibrium constant expression for , using spectrophotometry with the Absorbance
this system is: equation , A = ε b c, its equilibrium constant has
been determined.
Kc = [FeSCN2+] / [Fe3+][SCN-]
For the K determination be possible, a
The equilibrium system is prepared from calibration test has been done using standard solutions.
known concentrations of Fe3+ and SCN-, carefully Next is solving for the initial concentration of Fe3+ and
measured with pipets and mixed in volumetric flasks. SCN1- with its absorbance of an unknown mixture. And
Since the Fe(SCN)2+ formed is a complex ion with an then, finally, the determination of Keq using concepts in
absorption maximum at about 447 nm, its concentration concentrations and absorbance relation.
can be determined with a spectrophotometer. By
knowing the initial concentrations of Fe3+ and SCN-, and by A. CALIBRATION CURVE
measuring the Fe(SCN)2+ equilibrium concentration, the
equilibrium concentrations of Fe3+ and SCN- can be calculated. Given the molar concentration of FeCl3 and
Using these quilibrium concentrations, the K for several solutions
in which the ratios of reactant and product species are varied can also of KSCN, with their respective volumes in each
be determined. test tube, here is the table showing the calculated initial
concentration of Fe3+ and the equilibrium
In the first part of the experiment, a graph concentration of SCN-.
was plotted using the values of Fe(SCN)2+ as the x
variable and the absorbance readings as the y variable. Using the formula M1V1=M2V2, where in to
The graph was called the calibration curve. Next, linear find M2, let M1 be the given molarity of the reagent, V1
regression was used to find an equation of the best fit be its volume on that particular test tube, and V2 be the
line. total volume of the solution in liter, the desired
concentration of the reactants would be obtained.
Then next part is the absorbance readings
from five unknown solutions were taken. The initial On the other hand, for the product’s
concentrations of Fe3+ and SCN- were calculated using concentration, let M1 be SCN- ‘s initial concentration,
the dilution equation, M1V1 = M2V2.
V1 be the respective volume of SCN-, and V2 be the
total volume of the system again.
The last and most important part of the
experiment was the determination of the equilibrium
constant using all the data gathered from the previous Solution Absorbance [Fe3+]initial [SCN-]eq [FeSCN2+] eq
parts. The equation of the best fit line was then related
to Beer’s Law, A = εbc to find the equilibrium Standard 1 0.745 5.00 x 10-2 4.00 x 10-5 4.00 x 10-5
concentration of Fe(SCN)2+. Subtraction of this value Standard 2 0.906 5.00 x 10-2 8.00 x 10-5 8.00 x 10-5
from the initial concentrations of the two reactants Standard 3 1.052 5.00 x 10-2 1.20 x 10-4 1.20 x 10-4
yielded the equilibrium concentrations. And to finally Standard 4 1.171 5.00 x 10-2 1.60 x 10-4 1.60 x 10-4
determine the equilibrium constant, the equilibrium Standard 5 1.262 5.00 x 10-2 2.00 x 10-4 2.00 x 10-4
expression, Keq = [C]c[D]d / [A]a[B]b was used.

Now, as per the purpose of this part, the

RESULTS AND DISCUSSION
Spectrophotometry has been an effective
method of determining the equilibrium constant of a
reaction. This process shows the relation of absorbance
calibration must be set first.
Dealing with the Beer - Lambert’s Law, A = εbc,
we let A (absorbance) be the y-coordinate of the line, ε
(molar absorptivity coefficient) be the slope over b, and
c (molar concentration) be the x-coordinate.
 Through linear regression, presented in the Solution [Fe3+]initial
Absorbance [SCN-]initial
graph below is the best-fit line of the data mentioned
above. Unknown 1 0.121 1.00 x 10-3 2.00 x 10-4
Unknown 2 0.2 1.00 x 10-3 4.00 x 10-4
GRAPH OF THE CALIBRATION CURVE 0.328 1.00 x 10-3 7.27 x 10-4
Unknown 3

Absorbance vs. Concentration Unknown 4 0.416 1.00 x 10-3 1.00 x 10-3

Unknown 5 0.459 1.00 x 10-3 1.23 x 10-3
1.5 As the concentration of SCN increases with respect to the
ABSORBANCE

constant concentration of Fe3+, the concentration of the product also

1 increases same with the absorbance.
y = 3247.5x + 0.6375
0.5 R² = 0.9882 From the data above, it can inferred that the
concentration of reactants has the same trend with the
0
concentration of the products. Meaning, given a
0 0.00005 0.0001 0.00015 0.0002 0.00025
constant concentration of one of the reagents of a
[Fe(SCN)2+] system, the larger the concentration of the other
reagent the larger the concentration of the product.

By letting [Fe(SCN)2+] be the x-values and the
absorbance be the y-values, there is the obtained
equation of the best-line to be used as the reference for
calibration for this spectrophotometry process.
As seen, 3247.5 is the slope of the line
representing the molar absorptivity coefficient since ‘b’
or the path length is always assumed to be 1cm.
Therefore this absorbance coefficient will be used on
calculation for determining the equilibrium constant on
the later part of this study.
Moreover, same goes with the system’s
concentration and the light absorbance of the solution.
The more concentrated a solution, the higher is its
absorptivity.. In other words, the darker the color of a
solution meaning it has greater absorptivity, the more
concentrated it is.
The calculation of the initial concentration of
the products is the same as on that on part A using the
dilution equation.

Furthemore, the R2 value found which was C. EQUILIBRIUM CONSTANT DETERMINATION,

near to 1, affirmed the equation of the best fit line. This
equation was essential in that it was related to Beer’s
Law. The slope being εb, the y value being the
absorbance and the x value being the concentration of
Fe(SCN)2+..
Keq
Now that we have the initial concentrations of
the reactants, the equilibrium concentration of the
product, and the molar absorptivity coefficient from
the calibration, we can now proceed to the actual
determination of equilibrium constant.

B. ABSORBANCE OF UNKNOWN Below is a table presenting the equilibrium

SOLUTIONS concentrations of the reactants and that of the product.

Solution [Fe3+]eq [SCN-]eq [FeSCN2+] eq Keq

After the calibration, as we obtained the best-
Unknown 1 9.63 x 10-4 1.63 x 10-4 3.73 x 10-5 238
fit line that is going to be used for the purpose of this
study, is to test the absorbance of other system. Unknown 2 9.38 x 10-4 3.38 x 10-4 6.16 x 10-5 194
Another concern is for us to know how Unknown 3 8.99 x 10-4 6.26 x 10-4 1.01 x 10-4 179
absorbance and concentration relate to each other with Unknown 4 8.72 x 10-4 8.72 x 10-4 1.28 x 10-4 168
respect to the determination of equilibrium constant. 1.41 x 10-4 151
Unknown 5 8.59 x 10-4 1.09 x 10-3
Also, there is the obtained equilibrium constants from 2. Calibration, same goes with the solution
its respective solution. preparation and spectrophometric
reading, must be amount-wise for a larger
a. Equilibrium Concentration of the possibility of obtaining a precise
Product equilibrium constant.
3. The darker the solution meaning the
more concentrated it is, the greater its
This is calculated by using the Beer’s law absorptivity.
and the best-fit equation in the data 4. The following points on calculation must
where the concentration of the product is be remembered:
equal to absorbance over molar a. Calibration curve
absorptivity coefficient. In order to convert your
measured absorbance values to
concentration (M), a calibration
b. Equilibrium Concentrations of the
"curve" must be constructed to find
Reactants the molar absorptivity value. Use
the product’s equilibrium
This is the difference when the concentration and absorbance to
equilibrium concentration of the product plot Absorbance vs. Concentration
is subtracted from the initial to obtain a best fit line that will give
concentration of that particular reactant. the absorptivity value.

b. Conversion of measured
c. EQUILIBRIUM CONSTANT
absorbance values and the
Kc = [FeSCN2+] / [Fe3+][SCN-] product equilibrium
concentration values.
In determining the equilibrium constant, the
equation above is used, where in K is the List your measured
quotient of the product’s concentration raised absorbance values for each sample.
to its stoichiometric coefficient over the Convert absorbance to
reactant’s concentration also raised to it’s concentration using your value of ε
stoichiometric coefficient. (from the calibration curve) and
Beer's Law.
From the values of Keq on the table, the c. Calculation of initial
obtained average equilibrium constant is 186. concentration values
Compared to the literature value ___ of the
formation of FeSCN2+ from ferric chlorate and Using the formula
potassium thiocyanate, the experimental equilibrium
M1V1=M2V2, where in to find M2, let
constant differs by __ %.
M1 be the given molarity of the
reagent, V1 be its volume on that
CONCLUSION and RECOMMENDATION particular test tube, and V2 be the
total volume of the solution in liter,
After the analysis and systematic deliberation the desired concentration of the
of the method spectrophotometry in determining the reactants would be obtained.
equilibrium constant of a system, the results presented
hereunder are concluded to be significant points in this
experiment. d. Calculation of reactant
equilibrium concentration
1. The trend of the degree of concentration values
of the reactants has been the same as the This is the difference when
trend of degree of that of the products. the equilibrium concentration of the
Thus, the more concentrated the
product is subtracted from the initial
reactants, the more concentrated the
obtained solution would be. concentration of that particular
reactant.

e. Equilibrium constant, K, values
In determining the
equilibrium constant, the equation
above is used, where in K is the
quotient of the product’s
concentration raised to its
stoichiometric coefficient over the
reactant’s concentration also raised
to it’s stoichiometric coefficient.
5. Spectophotometry’s primary advantage
over other methods is its ability to
investigate different species in solution
through a variety of wavelengths without
disturbing the system being studied.
Another thing is it may be employed to a
wide range of solute concentrations and
to solutions having solvents other than
water.
ANSWERS TO QUESTIONS
1. Discuss the significance of the HCl in the solution
preparation.
Fe3+ will show complication because
of its reaction with water, given by Fe3+ +
3H2O ↔ Fe(OH)3 + 3H+ if HCl is absent in
system. With this, a solid precipitate Fe(OH)3
will form.
In order to avoid this reaction, HCl
was added to the solution to shift the
equilibrium of this system far to the left so
that no Fe3+ will precepitate to its hydroxide.
The formation of more Fe3+ from the
addition of HCl will not affect the iron(III) –
thiocyanate equilibrium system because Fe3+
is the supposed excess reagent in the system.
2. Explain why is there a need to do a blank reading.
Why not use distilled water as the balnk which has
zero absorbance?
In equilibrium, iron(III)
thiocyanate system consists excess yellow Fe3+
ion, the blood red [Fe(SCN)]2+ complex ion,
and the colorless HCl. Since we obtain the
absorbance of the system to determine the
concentration of [Fe(SCN)]2+, we need to
assure that the absorbance read by the
spectrophotometer is caused solely by
[Fe(SCN)]2+.
By setting these species’ absorbances
to auto zero, the future spectrophotometric
reading will plainly be caused by [Fe(SCN)]2+.
Using distilled water for blank
reading is inappropriate because if we do so,
the future readings remain to be affected by
the absorbance of HCl and FeCl3. Thus
rendering wrong absorbance and
concentration of product.
3. Account for the difference between the literature value
and the experimentally determined value of the
equilibrium constant.
Here are the possible grounds on the
difference between the experimental and
theoretical value of equilibrium constant for
the tested system: inaccurate preparation of
reagents, mistake in calibration, contamination
that result to be a great foreign disturbance in
absorption in spectrophotometer, or possibly
misexecution of procedures.
APPLICATIONS
(1) Determination of Cholesterol in Clinical Samples
(2) Ionization of an amino acid in an aqueous
environment
(3) Determination of drug’s effects
(4) Evaluation of the concentrations of the various
metal coplexes in a solution
REFERENCES
[1] Petrucci, Ralph H., William S. Harwood and
F. Geoffrey Herring. General
Chemistry: Principles and Modern
Applications. 8th ed. Singapore: Pearson
Education South Asia Pte Ltd., 2004.
[2] Cobb, C. L., and G. A. Love. “Iron(III)
Thiocyanate Revisited: A Physical Chemistry
Equilibrium Lab Incorporating Ionic Strength
– Effects.” Journal of Chemical Education. 75.1
(1998): 90-92.
[3] Measuring an Equilibrium Constant I: Using
Color to Analyze an Equilibrium Mixture.
University of Southern Maine. 10 Jan. 2011
<http://www.usm.maine.edu/chy/manuals/1
16/text/KeqSpec.html>
[4] Whitten, K.W., Davis, R.E., Peck, M.L., Stanley, B. CALCULATIONS
G.G. Chemistry 8th Edition. Thomson
Brooks/Cole, Belmont. 2007 1. Determine the equilibrium constant of
FeSCN2+ in the standard solutions.

[5] Brown, T.L., Le May Jr., H.E., Bursten, B.E.

Chemistry The Central Science Eighth
edition. Prentice – Hall Inc., New Jersey, 2000

[6]

APPENDIX

A. WORKING EQUATIONS

1. Beer-Lambert’s Law:

A = εbC,

where: A = measured absorbance; ε = wavelength

– dependent molar absorptivity coefficient; b =
path length (cm); and C = molar concentration

2. Dilution Equation:

M1V1 = M2V2,

3. Equilibrium Expression: 2. For the standard solutions, plot the absorbance

(ordinate) against the FeSCN2+ (abscissa). Use
Keq = [C]c[D]d / [A]a[B]b the least square method to determine the
equationof the best fit line. This will serves as the
where: calibration curve.
C, D = products
A, B = reactants
a,b,c,d = coefficients in the stoichiometric
equation
1.5
ABSORBANCE

1
4. Percent Difference: y = 3247.5x + 0.6375
0.5
R² = 0.9882
0
|actual – theoretical / theoretical| X 100 = __%
0 0.0001 0.0002 0.0003
[Fe(SCN)2+]
3. Use the calibration curve determined from 2 to
calculate for the concentration of the FeSCN2+ in
the unknown solutions.

5. Calculate Keq using the results from nos. 3 and

4. Solve for the average value of Keq.

4. Determine the equilibrium concentration of

[SCN-] and [Fe3+].