SPECTROPHOTOMETRIC DETERMINATION OF THE EQUILIBRIUM

CONSTANT OF A REACTION / EXPERIMENT 5

S. M. R. BAUTISTA
DEPARTMENT OF MINING, METALLURGICAL AND MATERIAL ENGINEERING , COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN , QUEZON CITY, 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-Lambert’s 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-Lambert’s 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 [𝐶]𝑐𝑒𝑞 [𝐷]𝑑𝑒𝑞

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 the concentration and order of the
products and dividing it by the concentration
and order of the reactants. Given the reaction:
𝐾𝑒𝑞 =
[𝐴]𝑎𝑒𝑞 [𝐵]𝑏𝑒𝑞
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:
3+
𝐹𝑒(𝑎𝑞) −
+ 𝑆𝐶𝑁(𝑎𝑞) <==> [𝐹𝑒𝑆𝐶𝑁]2+
(𝑎𝑞)
The product produced is a blood- red
complex that absorbs light in the visible
region that enables us to use Spectroscopy.

𝑎𝐴 + 𝑏𝐵 <==> 𝑐𝐶 + 𝑑𝐷
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 Beer-Lambert’s Law,
𝐴 = 𝜖𝑏𝐶
where in, “ε” 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.
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 FeCl3 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 50-mL 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.

The objectives of this experiment are Table 1: Components of Standard Solutions

to prepare solutions quantitatively, to employ Solution 0.002 M 0.20 M 0.10 M
Beer-Lambert’s Law, to identify the FeCl3 KSCN HCl
components of a spectrophotometer, to relate Blank 0.00 1.00 9.00
the color of the solution to the analytical Standard 1 0.10 1.00 8.90
wavelength of the chromophore, to employ Standard 2 0.25 1.00 8.75
spectrophotometry in determining the Standard 3 0.50 1.00 8.50
equilibrium concentration of a chromophore, Standard 4 1.00 1.00 8.00
to calculate Keq for the formation of [FeSCN]2+, Standard 5 2.00 1.00 7.00
and to write a formal report.
Afterwards, they prepared the
Unknown Solutions by preparing the
following solutions in 6-inch test tubes. The RESULTS AND DISCUSSION
units are all in mL.
Water is normally used in diluting a
Table 2: Components of Unknown Solutions solute since it is considered as the universal
Solution 0.002 M 0.002 M 0.10 M solvent. However, in this experiment 0.10 M
FeCL3 KSCN HCl HCl was used because the reaction of Iron
Blank 0.0 5.0 5.0 (II)) ion with water forms iron hydroxide,
Unknown 1 3.0 5.0 2.0 which is insoluble in water:
Unknown 2 4.0 5.0 1.0
Unknown 3 5.0 5.0 0.0
𝑭𝒆𝟑+ +
(𝒂𝒒) + 𝟑𝑯𝟐 𝑶(𝒍) <==> Fe(OH)3(s) + 3H(aq)

Part 2 is the calibration of the UV-Vis Or

Spectrophotometer. The group rinsed the [𝐹𝑒(𝐻20)6 ]3+ <==> [𝐹𝑒(𝐻20)5 (𝑂𝐻)]2+ + 𝐻 +
cuvette three times with distilled water
To avoid the precipitation of iron (III)
followed by the blank solution. Then they
hydroxide, a reddish orange crystalline
properly placed the cuvette in the sample
precipitate which is a highly insoluble
holder inside the spectrophotometer. Since
compound, it is necessary to add the excess
the spectrophotometer used is single-beam,
HCl because the formation of iron (III)
they performed Autozero. They used
hydroxide will be a hindrance to the
Standard 5 to measure the wavelength of
formation of [FeSCN]2+. Moreover if this
maximum absorption. They used this value
hydrolysis takes place the reading for the
for the rest of the readings.
absorbance of the solution will not only be
given by [FeSCN]2+ but also with Fe(OH)3.
Then they removed the cuvette,
For the determination of the
discarded the solution and rinsed it again
analytical wavelength, the solution with
three times with distilled water. Afterwards,
highest concentration must be used because
they rinsed it with Standard 1, discarded the
it is where the strongest or maximum
rinse and filled the cuvette with Standard 1.
absorption occurs. In the experiment the
They placed the cuvette inside the
analytical wavelength garnered was 465 nm
spectrophotometer and recorded the
at 1.006 absorption. The color of the solution
absorbance. Then the cuvette was removed
was observed to be near the red region so the
and the solution was disposed. They repeated
analytical wavelength is found in the blue
the above steps for Standards 2 to 5.
region which was the complementary of the
color red because what passes through a
For Part 3, they used the unknown
colored solution is the spectrum of light
solutions to aide in the determination of the
complementary to the spectrum of the
Equilibrium Constant for the Formation of
absorbed light.
[FeSCN]2+. They performed the same steps as
above for all the unknown solutions using the
same wavelength but different blank
solutions.
 x-coordinate ad the absorbance for the y-
coordinate.

1.5

Absorbance
1 y = 2507.5x - 0.026
R² = 0.999
0.5

0
0 0.0001 0.0002 0.0003 0.0004 0.0005

Figure 1: Light Spectrum Concentration (M)

Figure 2: Concentration vs. Absorbance

The analytical wavelength must be
used to measure the absorbance because it is
The equation of the best fit line is y =
where the molecule is most sensitive which
2507.5x – 0.026. This type of equation is also
gives accurate measurements.
shown by the Beer-Lambert’s Law which
means that the slope, 2507.5 L/mol∙cm is the
In the calibration, the blank solutions
molar absorptivity or ε of [FeSCN]2+ the
served as the basis of the absorbance of the
difference of 0.026 can be neglected since the
standards and the unknowns. It was leveled
R2 (0.999) value of the curve is really close to
to zero to make up for the absorbance of the
1 the R2 of a line. Using the Beer’s Law and
cuvette and the SCN- that was left in the
the maximum absorbance which is 1.006 at
solution. The limiting reactant of the solution
465 nm, the calculated theoretical molar
is Fe3+. To ensure that all of it will react to
absorptivity is 2515L/mol∙cm. The actual
form [FeSCN]2+, excess SCN- was added to the
molar absorptivity is close to the theoretical
solution, giving possibility to find for the best
molar absorptivity with a 0.29% error.
fit line when performing linear regression of
the Concentration vs. Absorbance.
After the determination of the
absorbance for the standard solutions, the
After calibrating the spectrophoto-
spectrophotometer was again calibrated for
meter, Standards 1 to 5 were put to test and
the testing of the unknown. Another blank
each of its absorbance were recorded.
solution was used because there is a
difference between the standard solutions
Table 3: Calibration Curve
and the unknown solutions. In the standard
Std [Fe3+]int [SCN-]int [Fe(SCN)]2+eq Abs
solutions, 0.20 M KSCN was used while in the
1 0.00002 0.02 0.00002 0.043
2 0.00005 0.02 0.00005 0.092 unknown solutions 0.002 M KSCN was used.
3 0.00010 0.02 0.00010 0.214 The reason for this is to isolate the
4 0.00020 0.02 0.00020 0.469 absorbance reading to that of [FeSCN]2+ alone
5 0.00040 0.02 0.00040 0.983 because in diluted form , SCN- and Fe3+ have
small absorbance. This will give results that
The concentration of [FeSCN]2+ and will follow the calibration curve.
the absorbance recorded were plotted in a
graph in which the concentration will be the
 By solving mathematically using the The theoretical value of Keq for
Beer-Lambert’s Law and the equation of the [FeSCN]2+ is 890. Given the data in Table 6, it
best fit curve, the concentration of [FeSCN]2+ shows that there is a large discrepancy
for each solution was acquired. This will also between the actual and theoretical
be the equilibrium concentration for equilibrium constant values. It exhibits
[FeSCN]2+. 56.89% of error. The error could have arisen
from:
Table 4: Unknown Solutions
Unk [Fe3+]int [SCN-]int [[FeSCN]2+]eq Abs Table 8: Sources of Error
1 0.0006 0.001 0.000148 0.346 Error Type of Error
2 0.0008 0.001 0.000189 0.449 Impurity of the Determinate Error -
3 0.0010 0.001 0.000229 0.548 reagents. Systematic Error
The outside of the Determinate Error -
Given the data on Table 4, the cuvette was not Gross Error
equilibrium concentration for Fe3+ and SCN- wiped thoroughly.
were calculated respectively using the ICE The unfrosted part of Determinate Error -
the cuvette was Gross Error
table.
touched.
Inconsistent Ambient Indeterminate Error
3+ −
𝐹𝑒(𝑎𝑞) + 𝑆𝐶𝑁(𝑎𝑞) <==> [𝐹𝑒𝑆𝐶𝑁]2+
(𝑎𝑞) Temperature
Improper rinsing of Determinate Error -
I [Fe3+]int [SCN-]int 0 the cuvette Gross Error
C -x -x +x Dilution of the test Determinate Error -
E [Fe int -x [SCN-]int -x
3+] x samples present Systematic Error
Figure 2: ICE Table inaccuracy.
Poor Pipetting Determinate Error –
Table 5: Equilibrium Concentration Techniques Gross Error
Unk [Fe3+]eq [SCN-]eq [[FeSCN]2+]eq Presence of Stray Indeterminate Error
1 0.000452 0.000852 0.000148 Light
2 0.000611 0.000811 0.000189 Inconsistency with Determinate Error –
3 0.000771 0.000771 0.000229 the amount of Systematic Error
solution placed in the
cuvette.
The data on Table 5 were substituted CONCLUSION AND RECOMMENDATION
to the expression:
This experiment was performed using
[𝐹𝑒(𝑆𝐶𝑁)2+ ] a single beam spectrophotometer to
𝐾𝑒𝑞 =
[𝐹𝑒 3+ ][𝑆𝐶𝑁 − ] determine the absorbance of [FeSCN]2+ in
different concentrations. By plotting the
Table 6: Equilibrium Constant values of the standard solutions’
Unknown Keq concentration vs. its respective absorbance
1 384.3118 and applying linear regression, the equation
2 381.4167
of the calibration curve was found to be y =
3 385.2359
2507.5x – 0.026 with a linearity coefficient of
Average 383.6548
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-Lambert’s work/determining-an-equilibrium-constant-
Law, the concentration of the unknown using-spectrophotometry/
solution was determined. The use of the ICE
table enabled the calculation of the [7] Ibale J., Spectrophotometric
equilibrium concentrations of the products Determination of the Equilibrium Constant of
and the reactants thus gave way to the a Reaction. Retrieved on January 20, 2014
computation of the equilibrium constant of from http://www.scribd.com/doc/12236-
the unknown solutions. However the Keq 4270/Formal-Report-Experiment-5-RDR
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/chemeq.html

[4] Reiser T., Advance Placement Chemistry.

Retrieved on January 19, 2014 from
http://www.scienceteacherprogram.org/che
mistry/Tehilla98.html

[6] Capriola A., Determining the

Equilibrium Constant of a Reaction using
Spectrophotometry. Retrieved on January
19, 2014 from http://adamcap.com/school-
APPENDIX

Calculations:

A. Calibration Curve:

Finding the initial moles of the reactants and products:

𝑀1 𝑉1 = 𝑀2 𝑉2
𝑀2 𝑉2
𝑀1 =
𝑉1

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

0.002 𝑀 (0.1 𝑚𝑙)

Standard 1:[[𝐹𝑒𝑆𝐶𝑁]2+ ] = 10 𝑚𝑙
= 0.00002 𝑀
0.002 𝑀 (0.25 𝑚𝑙)
Standard 2:[[𝐹𝑒𝑆𝐶𝑁]2+ ] = 10 𝑚𝑙
= 0.00005 𝑀
0.002 𝑀 (0.5 𝑚𝑙)
Standard 3:[[𝐹𝑒𝑆𝐶𝑁]2+ ] = 10 𝑚𝑙
= 0.00010 𝑀
0.002 𝑀 (1.0 𝑚𝑙)
Standard 4:[[𝐹𝑒𝑆𝐶𝑁]2+ ] = 10 𝑚𝑙
= 0.00020 𝑀
0.002 𝑀 (2.0 𝑚𝑙)
Standard 5:[[𝐹𝑒𝑆𝐶𝑁]2+ ] = 10 𝑚𝑙
= 0.00040 𝑀

[SCN-]

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

0.002 𝑀 (1.0 𝑚𝑙)

Standard 1-5:[𝑆𝐶𝑁 − ] = = 0.02 𝑀
10 𝑚𝑙

B. Absorbance of Unknown Solutions

𝑀1 𝑉1 = 𝑀2 𝑉2
𝑀2 𝑉2
𝑀1 =
𝑉1

[𝐹𝑒 3+ ]int

0.002 𝑀 (3.0 𝑚𝑙)

Unknown 1:[𝐹𝑒 3+ ] = = 0.0006 𝑀
10 𝑚𝑙
0.002 𝑀 (4.0 𝑚𝑙)
Unknown 2:[𝐹𝑒 3+ ] = = 0.0008 𝑀
10 𝑚𝑙
0.002 𝑀 (5.0 𝑚𝑙)
Unknown 3:[𝐹𝑒 3+ ] = 10 𝑚𝑙
= 0.0010 𝑀
[𝑆𝐶𝑁 − ]int

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

0.002 𝑀 (5.0 𝑚𝑙)

Unknowns 1-3:[𝑆𝐶𝑁 − ] = 10 𝑚𝑙
= 0.0010 𝑀

C. Molar Absorptivity

Actual:
A=εbC
y=2507.5x – 0.026
ε= 2507.5 cm-1M-1

Theoretical:
𝐴(𝜆max)
𝜀=
𝑏𝐶
𝜆max = 1.006
C = 0.0004 M, Most concentrated solution

1.006
𝜀= = 2515 𝑐𝑚−1 𝑀−1
(1𝑐𝑚)(0.0004𝑀)

Percent Error:
|𝑎𝑐𝑡𝑢𝑎𝑙 − 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙|
%𝑒𝑟𝑟𝑜𝑟 = 𝑥 100%
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙
|2507.5 − 2515|
%𝑒𝑟𝑟𝑜𝑟 = 𝑥 100% = 0.29%
2515

D. Equilibrium Constant Determination

Calibration Curve:
A=εbC
y=2507.5x – 0.026
where
y= A (Absorbance)
b= 1 cm
ε= 2507.5
C= [[FeSCN]2+]eq
𝑦+0.026
𝐶=
2507.5
[[FeSCN]2+]:

0.346+0.026
Unknown 1: 𝐶 = = 0.000148 𝑀
2507.5
0.449+0.026
Unknown 2: 𝐶 = 2507.5
= 0.000189 𝑀
0.548+0.026
Unknown 3: 𝐶 = = 0.000229 𝑀
2507.5

3+ −
𝐹𝑒(𝑎𝑞) + 𝑆𝐶𝑁(𝑎𝑞) <==> [𝐹𝑒𝑆𝐶𝑁]2+
(𝑎𝑞)

I [Fe3+]int [SCN-]int 0
C -x -x +x
E [Fe3+]int -x [SCN-]int -x x

X = [[FeSCN]2+]eq

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

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

Unknown 1: [Fe3+ ]int = 0.0006 M − 0.000148 M = 0.000452 M

Unknown 2: [Fe3+ ]int = 0.0008 M − 0.000189 M = 0.000611 M
Unknown 3: [Fe3+ ]int = 0.0010 M − 0.000229 M = 0.000771 M

Unknown 1: [SCN− ]int = 0.0010 M − 0.000148 M = 0.000852 M

Unknown 2: [SCN− ]int = 0.0010 M − 0.000189 M = 0.000811 M
Unknown 3: [SCN− ]int = 0.0010 M − 0.000229 M = 0.000771 M

Equilibrium Constant:

[𝐹𝑒(𝑆𝐶𝑁)2+ ]
𝐾𝑒𝑞 =
[𝐹𝑒 3+ ][𝑆𝐶𝑁 − ]

0.000148 𝑀
Unknown 1: 𝐾𝑒𝑞 = (0.000452 = 384.3118
𝑀)(0.000852 𝑀)
0.000189 𝑀
Unknown 2: 𝐾𝑒𝑞 = (0.000611 𝑀)(0.000811 𝑀)
= 381.4167
0.000229𝑀
Unknown 3: 𝐾𝑒𝑞 = (0.000771 𝑀)(0.000771 𝑀)
= 385.2395
Actual:
Keq average = 383.6548

Theoretical:
Keq = 890

Percent Error:
|𝑎𝑐𝑡𝑢𝑎𝑙 − 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙|
%𝑒𝑟𝑟𝑜𝑟 = 𝑥 100%
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙
|383.6548 − 890|
%𝑒𝑟𝑟𝑜𝑟 = 𝑥 100% = 56.89%
890