Beruflich Dokumente
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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
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)
aA + bB xX + yY
(2)
(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
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
Table 1.
Standard Solutions to Establish Calibration Curve
[Fe(NO3)3]
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
1.0 X 10
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+
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
0.00015
0.0002
0.00025
[FeSCN2+], M
After
finding
the
equilibrium
concentration for our reactants, the values simply
need to be entered into the equation
Kc =
[FeSCN 2+ ]
[Fe3+ ][SCN ]
Table 2.
B. Absorbance for Test
Solutions
[NaSCN] = 0.002 M
[Fe(NO3)3] = 0.002 M
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
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
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
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
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
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
1.65 X 10
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
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%