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Determination of an Equilibrium Constant
PURPOSE
To determine the equilibrium constant for the reaction:
Fe
3+
+ SCN
−
⇌
FeSCN
2+
GOALS
1
To gain more practice using a pipet properly.
2
To gain more practice diluting stock solutions.
3
To gain more practice using a spectrophotometer.
4
To gain practice plotting a calibration curve and use it to determine the concentration of an
unknown solution.
INTRODUCTION
A typical chemical equation has the following form:
aA + bB
→
cC + dD
(1)
This form of the equation assumes that the reaction proceeds completely to products. In prac-
tice, many reactions do not proceed to completion. If we measure the concentration of a reactant, it
eventually reaches a value that does not change further over time. If we measure the concentration
of a product, it reaches a constant value short of that predicted by the theoretical yield calculation.
In these cases, we say that the reaction has reached equilibrium
1
. We write the chemical reaction
using equilibrium arrows instead of a single arrow:
aA + bB
⇌
cC + dD
(2)
At equilibrium, the rates of the forward and reverse reactions are equal and, unless equilibrium
is disturbed (stressed), no changes in reactant or product concentrations will be measured. The
equilibrium arrows, one of which points in each direction, reinforce this idea.
At equilibrium, the molar concentrations of products and reactants will be fixed in a given
ratio.
This ratio is the equilibrium constant, K
eq
, which is determined by substituting molar
concentrations (indicated by the square brackets) into the equilibrium constant equation.
The
general form of this equation is:
K
eq
=
[C]
c
[D]
d
[A]
a
[B]
b
(3)
1
http://en.wikipedia.org/wiki/Equilibrium
2010-2013
Advanced Instructional Systems, Inc. and North Carolina State University
1
Reactants mixed in arbitrary concentrations will react until the ratio of the concentrations
reaches the value of the equilibrium constant according to equation 3. The value of K
eq
varies with
temperature; therefore, the temperature at which the equilibrium constant was determined must
be referenced.
In this laboratory experiment, a combination of solution chemistry, stoichiometry, and spec-
trophotometric analysis will be used to determine the equilibrium constant for a reaction between
the iron (III) ion (Fe
3+
) and the thiocyanate ion (SCN
-
).
In acidic solution, these ions form a
blood-red complex ion as shown in equation 4:
Fe
3+
(
aq
) + SCN
−
(
aq
)
⇌
FeSCN
2+
(
aq
)
(4)
The equilibrium constant for equation 4 can be expressed using the concentrations of the three
components:
K =
[FeSCN
2+
]
[Fe
3+
][SCN
−
]
(5)
In order to calculate the equilibrium constant, one must simultaneously determine the concen-
trations of all three of the components. In this experiment, you will measure the concentration of
FeSCN
2+
at equilibrium by measuring its absorbance at 470 nm. Since Fe
3+
and SCN
-
do not ab-
sorb light at this wavelength, they do not interfere with the measurements. If you know the initial
(before equilibrium) concentrations of Fe
3+
and SCN
-
, you can use a reaction table to calculate the
equilibrium concentrations of these two ions at equilibrium.
For example, you might initially mix equal volumes of 2.0 M Fe
3+
and 2.0 M SCN
−
.
The
term “initial concentration” can be confusing.
Even though the reaction appears to take place
instantaneously upon mixing the reactants, the “initial concentrations” in the reaction table are
those after dilution has been taken into consideration but before any reaction occurs. Thus, the
initial line in the reaction table for mixing equal volumes of 2.0 M Fe
3+
and 2.0 M SCN
−
should
have entries of 1.0 M under Fe
3+
and SCN
−
due to dilution. The initial concentration of FeSCN
2+
is
0.0 M. In our example, you might measure an equilibrium (final) concentration of 0.6 M FeSCN
2+
.
With the final concentration of the product, you can determine the change in product concentration
and, therefore, the changes in the reactant concentrations. The reaction table is shown below:
In this experiment, 0.2 M HNO
3
serves as the solvent.
The acid adds a large (compared to
the reactants) amount of H
+
.
This prevents side reactions such as the formation of FeOH
2+
, a
brownish species that can affect the results. The acid concentration is high enough that it is not
affected by the reaction and remains constant at 0.2 M.
You will prepare six standard solutions of FeSCN
2+
to calibrate a spectrophotometer. A fair
2010-2013
Advanced Instructional Systems, Inc. and North Carolina State University
2
question is ”How do I know the concentration of FeSCN
2+
in my standard solutions if it is in
equilibrium with Fe
3+
and SCN
-
?” In the standard solutions, the concentration of Fe
3+
is much
higher than that of SCN
-
.
This forces the equilibrium as far to the right (toward FeSCN
2+
) as
possible. Therefore, the concentration of FeSCN
2+
in a standard solution will be very nearly equal
to the initial concentration of SCN
-
used in preparing it.
The absorbance measurement at 470
nm will correlate to the concentration of complex ion, and an accurate calibration curve (Beer’s
Law plot) can be obtained. Recall that the calibration curve gives you a relationship between the
concentration of a species in solution and its absorbance at a given wavelength: (A =
ϵ
l
c). Using
the linear regression of the calibration curve in Part A, you will determine the concentration of
FeSCN
2+
ion in each of five equilibrium mixtures in Part B. An equilibrium constant can then be
calculated for each mixture; the average of all of these values should be reported as the equilibrium
constant value for the formation of the FeSCN
2+
ion.
In Part A of this experiment, you will prepare FeSCN
2+
solutions of known concentrations, mea-
sure their absorbance at 470 nm, and produce a calibration curve. In Part B, you will make equi-
librium mixtures of Fe
3+
, SCN
-
, and FeSCN
2+
. You will determine the concentration of FeSCN
2+
from its absorbance at 470 nm and your calibration curve from Part A. Then, using reaction tables,
you will calculate the equilibrium concentrations of Fe
3+
and SCN
-
and use those values to deter-
mine the equilibrium constant for the formation of FeSCN
2+
. You will calculate the equilibrium
constant for each mixture you prepare and then use each value to find the average equilibrium
constant for the formation of FeSCN
2+
.
EQUIPMENT
1
MicroLab Spectrophotometer
1
MicroLab Spectrophotometer Instruction
6
vials
3
Serological pipets
1
pipet bulb
3
30 mL beakers for reagents
6
13
×
100 mm test tubes for mixtures
6
stoppers
1
test tube rack
1
250 mL beaker for waste
1
deionized water squirt bottle
REAGENTS
∼
10 mL 0.100 M Fe(NO
3
)
3
in 0.2 M HNO
3
∼
10 mL 6.00
×
10
-4
M NaSCN in 0.2 M HNO
3
∼
15 mL 0.002 M Fe(NO
3
)
3
in 0.2 M HNO
3
2010-2013
Advanced Instructional Systems, Inc. and North Carolina State University
3
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Related Questions
What is the value in the concentration of the SCN
Suppose the Keq for this experiment is 523.
The initial concentration of the Fe+ is 4.00 x 10-2 M
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The concentration of the SCN at equilibrium is : Y x 104M
Your answer should have 2 sf
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If OH- (from a strong base such as sodium hydroxide) is added to a solution of carbon dioxide, what happens to the OH- and what effect will this
have on the equilibria above?
Select one:
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O
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1
U
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(
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6
6
(s)
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N
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3 1₂(s) + 2 Cr³+ (aq) + 7 H₂O(1)→ Cr₂O² (aq) +61¯ (aq) + 14 H* (aq)
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X
Ś
00
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Question 10 options:
right
left then right
left
at equilibrium then right
at equilibrium then left
not enough information
at equilibrium
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1
U
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determine the equilibrium constant for this reaction shown:
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Flask #
0.2 M Fe(NO3)3 in 0.50M HNO3
0.50M HNO3
2.00 x 10–3 M KSCN in 0.50M HNO3
Initial
[Fe3+]
Initial [SCN-]
Initial [FeSCN2+]
Blank
5 mL
5 mL
0 mL
1
5 mL
4 mL
1 mL
2
5 mL
3 mL
2 mL
3
5 mL
2 mL
3 mL
4
5 mL
1 mL
4 mL
5
5 mL
0 mL
5 mL
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Name Marlysa Rackmyre #13
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5.
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