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Adam Lorenz

Lab Partner: Robin Sunsong


Chem 1412.001
7/2/12

An Equilibrium Constant

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_______________________________________________________________________________________
This experiment aims to shows that a spectroscopic analysis can be done for unknown concentrations of
reactants in a solution, which with further data analysis can be used to obtain an equilibrium constant. In
order to determine the equilibrium constant (Kc) of a chemical system, the concentrations of the reactants
and the products at equilibrium must be determined quantitatively. While the initial concentrations of
reagents can be easily measured and determined before they are combined in a solution, once combined and
reacting some technique must be used to determine what concentration the reagents are at without disturbing
the solutions integrity. In this experiment the equilibrium constant was determined for a chemical system
where known quantities of iron(III) ion, Fe3+, and thiocyanate ion, SCN-, are combined to react and produce
an unknown quantity of thiocyanatoiron(III) ion, FeSCN2+. To ascertain the concentration of FeSCN2+ a
spectroscopic analysis was used to get an absorptivity coefficient for a known concentration of solution,
which was used with further spectroscopic data of unknown concentrations to arrive at an equilibrium
constant. This experiment resulted in an average Kc value for this chemical system of 263.2, a 3.04% error
in comparison to the accepted value of 271.49.
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_______________________________________________________________________________________

Purpose:
To find the equilibrium constant for a chemical
system involving iron(III) ion Fe3+, thiocyanate

ion SCN-, and thiocyanatoiron(III) ion FeSCN2+,


using spectrophotometer and data analysis to
determine the molarity of FeSCN2+ produced in

the reaction where the initial concentration of the


reactants is known.

Introduction:
Understanding the electromagnetic (EM)
radiation spectrum has proven to be an invaluable
tool for understanding and analyzing the world
around us. The study of the interaction between
EM radiation and matter, spectroscopy, has
enabled scientists to study stars and planets across
vast distances of the universe, and to study the
microscopic matter that makes up the world
around us. This is because matter and EM
radiation interact in predictable ways that can be
measured and used for analyses. While the EM
spectrum also consists of the ultraviolet and
infrared wavelengths, this experiment needs only
to look at and use the visible spectrum, form
approximately 400 to 700nm.
As EM radiation in the visible spectrum
passes through a solution some of the energy can
be absorbed by the molecules and atoms that it
consists of, while the light that is not absorbed
passes through the solution, or is transmitted. Like
with all matter, the colors we see in the solution
are not from the wavelengths that are absorbed,
but from the wavelengths that are transmitted. In
order to quantify the light that is transmitted or
absorbed, a Spectrophotometer is used which can
measure the percent of light transmitted or amount
of light absorbed in a solution.
According to Beers Law, the amount of
light that is absorbed by a solution is affected by
three factors in a relationship that can be
expressed as

A=abc

(1)

The absorption of a solution, A, is a function of


the wavelength dependent absorptivity coefficient,
a, the length the light travels through the solution
or cuvet width, b, and the analyte concentration, c.
This experiment will use the fact that due to
Beers law the absorption is proportional to
concentration to figure out the concentration of a
reactant so that the equilibrium constant can be
discovered for a chemical system of unknown
concentrations at equilibrium..
For a chemical reaction such as

aA + bB xX + yY

(2)

the reaction will not just occur where A and B


form X and Y, but X and Y will also form A and
B. These reactions will continue to happen until
the reactants and products reach equilibrium,
where the amount of new formation of the
molecules on the right side of the equation equals
the formation of molecules on the left. The
equilibrium constant can be deduced from the
equation

(3)
where the reactants are measured in their molar
concentration at equilibrium.
This is fine if the equilibrium
concentrations are known, and it can also be
worked out if the initial concentration of reactants
and the Kc value are known. But what if the Kc
value is unknown, as well as the molarity of
reactants at equilibrium? A measurement of the
reactants in solution must be made without
disturbing the solution, or in any way changing
the concentrations once the solution is made. This
is the problem this experiment tries to handle,
with a reaction system that includes iron(III) ion
Fe3+,
thiocyanate
ion
SCN-,
and
2+
thiocyanatoiron(III) ion FeSCN in an HNO3
solution, represented by the equation,
Fe3+ (aq) + SCN- (aq) FeSCN2+ (aq) (4)
where only the concentration of the initial
reactants is known.
To find Kc in this experiment, a
spectrophotometer will be used since, according
to Beers law, absorbance is directly proportional
to concentration. What will be needed then is to
create a calibration curve based on known
concentrations in a solution to find the
absorptivity coefficient so further analysis can
occur. So In this experiment, a set of samples with
different concentrations of FeSCN2+ were created
by reacting an excess amount of Fe3+ with a much
smaller quantity of SCN-. These solutions should
have pushed the equilibrium of the reaction far to
the product side, making the equilibrium
concentration of FeSCN2+ very near the initial
concentration of SCN-. To ensure that the data
from the spectrophotometer only represents
absorption of FeSCN2+, a blank sample of
excess FeSCN2+ was created and run first to set

absorbance to zero to calibrate the machine to the


presence of the other ions in solution. By using
the spectrophotometer to ascertain the absorbance
of the other standard set solutions at a set
wavelength, in this case 447nm, the assumed
concentration of FeSCN2+ based on the initial
concentration of SCN- were then graphed against
the absorbance creating the calibration curve.
Plotted, this data can be used to find the
concentration of FeSCN2+ when the concentration
and Kc are unknown. The slope of the line
graphed will be the absorptivity coefficient in
Beers Law.
Next, several samples with similar initial
concentrations of Fe3+ and SCN- are created and
allowed to react before ascertaining the absorption
of the solution by use of the spectrophotometer.
Since we have the absorptivity coefficient, a, and
the same size cuvets were used as in the standard
set, the concentration of FeSCN2+ can be derived
by the altered equation of Beers law:
(5)
Where A is the absorption of the test samples, and
a, the absorptivity coefficient derived from the
calibration curve. Using this data we can find the
equilibrium concentration of all the reactants and
use the equilibrium equation (3) to find Kc for this
reaction system.

Procedure:
Reagents and Materials: 0.2 M Fe(NO3)3 in 0.1
M HNO3 ; 0.001 M NaSCN in 0.1 M HNO3 ; 0.1
M HNO3 ; 0.002 M Fe(NO3)3 in 0.1 M HNO3 ;
0.002 M NaSCN in 0.1 M HNO3 ; 6 25-mL
volumetric flasks; 6 10-mL volumetric flasks; 6
cuvets;
2
10-mL
graduated
cylinders;
spectrophotometer
Preparing standard solutions set: All glassware
was thoroughly cleaned and dried before the
beginning of the experiment.
In a 10-mL graduated cylinder, measured
10-mL of 0.2 M Fe(NO3)3 precisely and added to
each of the 6 25-mL volumetric flasks. In a
separate 10-mL graduated cylinder measured out
0, 1, 2, 3, 4 and 5-mL of 0.001 M NaSCN and
added each measured amount to a separate

volumetric flask. Labeled the volumetric flasks


from 0 to 5 for the amount of 0.001 M NaSCN, in
mL, that were added to the flask. Filled each of
the 25-mL volumetric flasks the rest of the way up
to their 25-mL measured mark with 0.1 M HNO3.
Mixed each solution thoroughly by inverting the
flasks several times for approximately 30 seconds.
Absorbance of Standard Set: Each of the 6
standard set solutions was poured into a separate
cuvet which was marked for the solution it
contained. Each cuvet was thoroughly cleaned,
inside and out.
After setting up the spectrophotometer and
allowing it to warm up for about 10 minutes, the
spectrophotometer was set to read absorbance at
447nm. Using solution 0 as our blank, the cuvet
was wiped clean with a lint free wipe and placed
into the spectrophotometer, and the absorbance
was zeroed. Subsequently, each of the standard
solution cuvets was wiped down with a lint free
wipe, and placed into the spectrophotometer and
the absorbance was recorded at 447nm.
Calibration Curve: Assuming that the
equilibrium concentration of FeSCN2+ is equal to
the initial concentration of NaSCN, the
concentration of FeSCN2+ was graphed on the X
axis against the Absorbance on the Y axis. From
this, a best fit line was applied across the points,
and the slope is determined. The R2 value was
used to check the precision of the data.
Preparing Test Set: In a 10-mL graduated
cylinder, measured 1, 2, 3, 4, and 5-mL of 0.002
M NaSCN in 0.1 M HNO3 and added each
volume to a separate 10-mL volumetric flask that
were labeled 6 through 10, with the smallest
volume of NaSCN starting at 6 and the largest
volume 10. Measured out 6 times, in a separate
10-mL graduated cylinder, 5-mL of 0.002 M
Fe(NO3)3 in 0.1 M HNO3 to be added to each
labeled 10-mL flask. Another blank was created,
labeled 0, that contains just 5-mL of 0.002 M
Fe(NO3)3 in 0.1 M HNO3. Each volumetric flask
then filled to the measured 10-mL mark with 0.1
M HNO3 .

The precision of this data was found by


doing a standard deviation for the Kc values, as
well as a relative standard deviation and a percent
error against the accepted value.

Each flask was then capped and mixed


thoroughly by inverting the flask repeatedly for 30
seconds.
Absorbance of Test Set: In 6 clean cuvets, each
test set was poured into a cuvet which was labeled
from 0-5 for the test solution that was added.
The spectrophotometer was set to 447nm,
and the 0 test sample cuvet was wiped down
and placed into the spectrophotometer to zero the
absorbance. Subsequently, each of the other 5 test
samples was placed into the spectrophotometer
after being wiped clean, and the absorbance was
recorded.

Results and Disscussion:


Analyzing the Standard Set: The results of the
standard set, where an excess amount of Fe(NO3)3
is used to get a calibration curve for FeSCN, can
be seen in Table 1. Since Fe is in excess, its
molarity is not very important at this stage of the
experiment, as we only need the molarity of
NaSCN to do our calculations, as shown in Figure
1, since we are assuming all the SCN reacted. In
figure 1, the molarity of NaSCN was used with
the volume added to the solution to get the mols
of SCN that would react to form FeSCN.
After the calculations were carried out, the
samples were tested using the spectrophotometer,
and their absorbance recorded, Table 1, the data
was graphed to find the calibration curve, Chart 1.
From the linear regression, we can see that our
data has an R2 value of 0.9958, which indicates
strong precision with our data. Meaning the data
gathered so far should yield a reasonably accurate
molarity for FeSCN, and eventually the Kc value.

Finding Kc Value Through Data Analysis:


After finding the absorbance of the test set, the
values are set into Beers equation (5) with the
absorbtivity coefficient which will give the molar
concentration of FeSCN2+. Since one mol of Fe
and SCN react to form one mol of FeSCN, the
equilibrium concentrations of the reactants can be
found by subtracting the concentration of FeSCN
from the initial concentration of Fe and SCN.
From here the concentration values were entered
into the equilibrium constant equation (3) and Kc
values for the Test were found. From the 5 test
samples, an average was averaged.

Table 1.
Standard Solutions to Establish Calibration Curve
[Fe(NO3)3]

Vol. NaSCN (mL)


-

0.200 M

Blank

1.0mL

[NaSCN]

2.0mL
-6

3.0mL
-6

3.0 X 10

4.0mL
-6

4.0 X 10

5.0mL
-6

5.0 X 10-6

Mol. SCN (mol)

1.0 X 10

[SCN-] (25.0 mL)

4.0 X 10-5

8.0 X 10-5

1.2 X 10-4

1.6 X 10-4

2.0 X 10-4

[FeSCN2+]

4.0 X 10-5

8.0 X 10-5

1.2 X 10-4

1.6 X 10-4

2.0 X 10-4

Absorbance (AU)

0.089

0.195

0.316

0.432

0.568

mx =

2850

b=

-0.018

y=

2.0 X 10

0.001 M

Chart 1
Plotted Absorbance FeSCN against Absorbance
2+

Absorbance vs. [FeSCN ]


0.6

0.5

y = 2850x - 0.0183
R2 = 0.9958

Absorbance, AU

0.4

0.3

0.2

0.1

0
0

0.00005

0.0001

-0.1

Also from the Chart 1 we find the equation of


y= 2850x 0.0183.
that is actually the absorptivity coefficient for
Beers Law. The b value of -0.0183 must be
subtracted from the absorbance before dividing by
the m value 2850 to find the concentration of
FeSCN.
Analyzing the Test Set: The concentrations and
absorption results of the test set of solutions can
be seen in Table 2. Precise measurements of mols
in the initial concentrations of the Fe and SCN
solutions needed to be added and accounted for,
Figure 2, or otherwise the Kc value will be way
off.
After ascertaining the mols in the solution
and gathering their absorbance, much of what is
left is calculation.
Using Beers Law, Figure 3, the molarity
of FeSCN can be derived by using the absorbance
of the test sample, divided by the absorptivity
coefficient. From their, by multiplying by the
volume of the solution, the mols are found, as in
sample 6 where 3.48 X 10-7 mol FeSCN were
recorded.

0.00015

0.0002

0.00025

[FeSCN2+], M

After finding the mols of FeSCN in the test


solutions, then the equilibrium concentration of Fe is
found by subtracting the mols of FeSCN from the initial
concentration of Fe, Figure 4. The same is done to
with SCN, Figure 5.

After
finding
the
equilibrium
concentration for our reactants, the values simply
need to be entered into the equation
Kc =

[FeSCN 2+ ]
[Fe3+ ][SCN ]

and the value for Kc can be found. For sample 6,


Figure 6, a value of 219 is found. This process
was repeated for the rest of the samples and their
data was logged in Table 3. An average Kc value
was found for this experiment as 263.
Finally, the data can all be collected and
analyzed to check for precision. As seen in Figure
7, a standard deviation and relative standard
deviation were used. Unfortunately, despite the
earlier high precision with the sample set, the test
set ended with a much higher error margin. A
standard deviation of Kc was found to be 29.6, and
the relative standard deviation was found to be
11.4%, Figure 7. However, the difference from
the accepted value is not far off, at a 3.04% error
disagreement.

Since the first sample set had a high


precision, the likeliest culprit for the error was too
little reactants added to the solutions. While
precision was the intended goal while mixing
reagents, it is possible that while transferring
measured amounts, some got left out of the flask,
yet was still recorded in the data tables. This can
be explained partially due to equipment used,
since precise pipets or titration were not used to
directly transfer solutions, but were measure in
plastic graduated cylinders, then transferred. The
error, while not massive, can still lead to less than
accurate results for Kc values, which would defeat
the whole experimental purpose. Such small
concentrations of reactants were used that even a
missed or added drop can greatly alter the
experiment.
The lab area has been prone to large
fluctuations in temperature, from very warm to
excessively cold. Temperature plays a part in the
rate of reaction, and could have altered the

formation of products, changing absorption


readings.
A better lab environment would certainly
help with the accuracy and precision of the result
of the experiment.
Conclusion: This experiment sought out to find
the equilibrium constant for the chemical system
Fe3+ (aq) + SCN- (aq) FeSCN2+ (aq)
with unknown equilibrium concentrations by way
of spectroscopic analysis. While there was some
error, the experiment succeeded in proof of
concept. First, by discovering the absorptivity
coefficient by use of sample sets and a
spectrophotometer, the value of which was 2850.
From this, the absorption of a solution of known
initial concentrations can yield the concentration
of the product FeSCN, which will help yield the
equilibrium concentrations of Fe and SCN. From
this, a equilibrium constant of 263 was
discovered, with a standard deviation of 29.6.

Table 2.
B. Absorbance for Test
Solutions
[NaSCN] = 0.002 M

[Fe(NO3)3] = 0.002 M

1. Vol. Fe(NO3)3 (mL)


2. Mol Fe3+, initial (mol)
3. Vol. NaSCN (mL)
4. Mol SCN-, initial (mol)
5. Absorbance (AU)

10

1.00 X 10-5

1.00 X 10-5

1.00 X 10-5

1.00 X 10-5

1.00 X 10-5

1.0

2.0

3.0

4.0

5.0

2.00 X 10

-6

4.00 X 10

0.081

Figure 2
Calculations for Initial Concentrations of Test
Set 6
1. 0.002 M Fe(NO3)3 X 0.005 L = 1.00 X 10-5 mol
Fe
2. 0.002 M NaSCN X 0.001 L = 2.00 X10-6 mol
SCN

0.195

-6

6.00 X 10
0.319

-6

8.00 X 10
0.416

-6

1.00 X 10-5
0.527

Table 3.
C. Calculation of Kc
6
2+

7
-5

1.91 X 10-4

Mol. FeSCN2+eq (mol)

3.48 X 10-7

7.48 X 10-7

1.18 X 10-6

1.52 X 10-6

1.91 X 10-6

Mol. Fe3+, reacted (mol)

3.48 X 10-7

7.48 X 10-7

1.18 X 10-6

1.52 X 10-6

1.91 X 10-6

Mol. Fe3+eq (mol)

9.65 X 10-6

9.25 X 10-6

8.82 X 10-6

8.48 X 10-6

8.09 X 10-6

[Fe3+]eq (10 mL)

9.65 X 10-4

9.25 X 10-4

8.82 X 10-4

8.48 X 10-4

8.09 X 10-4

Mol. SCN-, reacted (mol)

3.48 X 10-7

7.48 X 10-7

1.18 X 10-6

1.52 X 10-6

1.91 X 10-6

-6

-6

-6

-6

8.09 X 10-6

Mol. SCN eq (mol)

1.65 X 10

[SCN-]eq (10 mL)

1.65 X 10-4

3.25 X 10-4

4.82 X 10-4

6.48 X 10-4

8.09 X 10-4

218

249

279

278

293

Kc =

[FeSCN 2+ ]
[Fe 3+ ][SCN ]

Average Kc
Std. Dev. Kc
Relative Std. Dev. Kc

4.82 X 10

1.52 X 10

10
-4

3.48 X 10

3.25 X 10

1.18 X 10

9
-4

[FeSCN ]eq (mol/L)

7.48 X 10

8
-5

263
29.6
11.4%

Figure 3
Calculations of [FeSCN-] for test sample 6
1. (0.081 + 0.018) 2850 = 3.48 X 10-5 M FeSCN
2. 3.48 X 10-5 M FeSCN X .010 L = 3.48 X 10-7 mol FeSCN

Figure 4
Calculations of [Fe3+] for test sample 6
1. 0.002 M Fe X 0.005 L = 1.00 X 10-5 mol Fe
2. 1.00 X 10-5 mol 3.48 X10-7 mol = 9.65 X 10-6 mol Fe
3. 9.65 X 10-6 mol Fe 0.010 L = 9.65 X 10-4 M Fe

Figure 5
Calculations of [SCN-] for test sample 6
1. 0.002 M SCN X 0.001 L = 2.00 X 10-6 mol SCN
2. 2.00 X 10-6 mol 3.48 X10-7 mol = 1.65 X 10-6 mol SCN
3. 1.65 X 10-6 mol SCN 0.010 L = 1.65 X 10-4 M SCN

Figure 6
Calculations of Kc from test sample 6
Kc = 3.48 X 10-5 M FeSCN (1.65 X 10-4 M SCN X 9.65 X 10-4 Fe) = 218

6.48 X 10

Figure 7
Calculations of Standard Deviation and Relative Standard
Deviation

sum =

Kc
218
249
279
278
293
1317

(x-bar )=

263.4

di = (x-bar) - x
45.4
14.4
-15.6
-14.6
-29.6

d i2
2061.16
207.36
243.36
213.16
876.16
3601.2
s=(di 4) =
%RSD= [ di (x-bar) ] X
100% =

29.6
11.39%