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Lab 06 Equilibrium Constant
Lab 06 Equilibrium Constant
The spectrophotometer that we will be using is a Spectronic 20-D. So what is it that the Spectronic 20-D
is measuring? It is measuring the amount of light that is transmitted through your sample and hits the
detector as a percentage of the light transmitted with a “blank” sample,
I
%T= 100% (1)
Io
where %T is the percent transmittance, I is the intensity or amount of light that is transmitted through the
sample and Io is the intensity or amount of light transmitted through the blank, a sample that doesn’t
absorb at all. Since %T is not linear with concentration, what we would like to know is slightly different:
how much light is being absorbed by our sample?
1
http://www.chem.vt.edu/chem-ed/spec/uv-vis/singlebeam.html accessed 8/12/05
Beer’s Law:
A=lc (3)
Where:
is called the molar extinction coefficient (aka molar absorptivity). It is an attribute that is
specific to the absorbing species. It is a measurement of how strongly a chemical species absorbs
light at a given wavelength (at a given wavelength, is a constant) (We will use nm
l is the path length (width of the cuvette) (another constant) which contains the solution that is
being analyzed and
c is the concentration of the absorbing species expressed as molarity, M. (The absorbing species
in this experiment is FeSCN2+. Hence, the concentration, c, of FeSCN2+ is directly proportional
to the absorbance of that solution with a y-intercept equal to zero.)
A = (constant) c (4)
A graph of absorbance vs. concentration is known as a Beer’s Law Plot. The constant is the slope of the
calibration curve made from the data in Procedure 1A. Once the constant is determined, you can measure
the absorbance of any solution and then know its concentration of FeSCN2+. Let me restate this with
direct reference to the procedure for this lab: once the calibration curve has been constructed using
Procedure 1B, then any absorbance you measure in Procedure 2 can be used to calculate the concentration
of FeSCN2+. It is the concentration of FeSCN2+ that is needed to then determine Kc for reaction (5).
In this experiment, each group will use different cuvettes. It is imperative that the path length l is constant
for all of these cuvettes. Therefore, each of these cuvettes is made with a width that is precisely 1.00 cm.
Each cuvette is marked with a white line near the lip. This white line must be aligned precisely with the
black groove in the sample holder to ensure that the path length is 1.00 cm.
Operating instructions for the Spectronic 20-D are available at the end of this experiment.
B. Determining the Equilibrium Constant
The main purpose of this lab is to determine the equilibrium constant for the complex ion formed by the
reaction of Fe3+ with SCN–,
As noted in lecture and the text, when Kc is >> 1, a reaction is product-favored, goes essentially to
completion and the concentrations of products at equilibrium are much larger than the concentration of
reactants (essentially, there are no reactants left). When Kc is <<1, a reaction is reactant-favored, does not
go at all and the concentrations of reactants at equilibrium are much larger than the concentration of
products (essentially, no products form).
In Procedure 1B, the concentration of Fe3+ initially, after accounting for dilution, will be the
equilibrium or final concentration of FeSCN2+ because the above reaction will go essentially to
completion. We will use LeChatelier’s Principle (the subject of experiment 5-we’re just using it here) to
drive the reaction to the right. We will add a known concentration of Fe3+. We will then add more than
100 times higher concentration of SCN– than Fe3+ to the reaction mixture. Using LeChatelier’s Principle,
the excess SCN– will push the position of equilibrium far to the right and essentially to completion. The
Fe3+ is the limiting reactant and all of the Fe3+ will be reacted to produce FeSCN2+.
FeSCN2+ absorbs light at = 447 nm. We will construct a “calibration” or “standard” curve (a.k.a.
Beer’s law Plot) that plots the known [FeSCN2+] on the x-axis and the absorbance A of FeSCN2+ on the
y-axis to establish a linear relationship between these two variables. The power of the calibration curve is
that for any solution containing FeSCN2+ as the only absorbing species, we can measure the absorbance
and use the linear relationship to calculate the [FeSCN2+]. This is exactly why we are preparing the
calibration curve.
For Procedure 2, we add approximately equal concentrations of Fe3+ and SCN–. Under these conditions,
the reaction will not go to completion. In fact, we will not know how far the reaction went to completion
because we don’t know the equilibrium constant Kc. However, if we measure the absorbance of the
unknown solutions in Procedure 3, then we can use the calibration curve prepared from Procedure 1
to calculate what the equilibrium [FeSCN2+] is in that solution. Once we have the equilibrium
[FeSCN2+], we can fill in the rest of an ICE table to determine Kc.
2. Measure the absorbance of a series of solutions for which [FeSCN2+] is unknown. For these
solutions, reaction (1) will not be complete, but there is still the same relationship between
absorbance and concentration. Use this relationship (equation of the line) and the absorbance to
calculate [FeSCN2+].
II. Experimental
A. Equipment Needed:
From stock room: 1 spectrophotometer cuvette, 10mL volumetric flask(s)
Equipment in lab: Spectronic 20-D spectrophotometer, digital micropipettes, aluminum foil
Chemicals in lab: 0.200 M KSCN in 0.500 M HNO3,
2.0010–3 M Fe(NO3)3 in 0.500 M HNO3,
0.500 M HNO3
B. Disposal:
Combine and collect all used chemicals from this experiment in a large beaker. At the end of the lab
period, transfer waste chemicals to the provided waste container.
I 8.0010–4 8.0010–5 0
C
E 3.0010–5
From the three columns in Table 3, there is enough information to determine the value of Kc.
Because we know the initial concentration (we start with none) and the equilibrium concentration
of FeSCN2+ (we do assume that the reaction is at equilibrium by the time we get it into the
spectrophotometer, but this is a very good assumption born out by the fact that we don’t see the
color of the solutions changing with time), we can figure out the change in concentration of
FeSCN2+. Since the change must be the same for all of them (taking into account coefficients), we
can fill in our table using arithmetic to make it look like this:
Fe3+(aq) + SCN– (aq) 2+
FeSCN (aq)
I 8.0010–4 8.0010–5 0
C –3.0010–5 –3.0010–5 +3.0010–5
E 7.7010–4 5.0010–5 3.0010–5
From here, we need to use the Kc expression for reaction (5) to get the value of Kc for this
reaction. Because reaction (5) forms complex ion FeSCN2+, it is also called Kf (even though it
follows all the same rules as any Kc). Show the ICE table calculations for all 5 solutions.
e.) Calculating the Average and Standard Deviation of Kc.
Calculate the average and standard deviation for the 5 individual values calculated for Kc.
B. In-Class Work (Before going home)
1. All dilution concentrations, Q-tests, and averages for absorbance values collected in
Procedure 1A must be calculated.
2. Prepare a hand-drawn Beer’s Law plot (calibration curve) from your individual group’s data that
takes up at least half a page in your notebook. If your notebook does not have quadrille squares,
obtain a half sheet of graph paper from your instructor. (Put concentration FeSCN2+ on the x-axis and
absorbance on the y-axis.) This graph is intended to identify if your group needs to re-prepare and/or
re-measure the absorbance of any of the 5 solutions before sharing that data with the class. Be sure to
use a ruler for your graph and that it includes all the standard requirements of a good graph. From the
line of the hand-drawn graph, calculate the slope of the graph using a 2 point-slope formula: [slope =
(y2-y1)/x2-x1)]. Have your graph checked by your instructor before going on to Procedure 2. Once
your instructor has approved your graph, record your group’s data on the board to share with the rest
of the class. If your notebook does not have graph paper in it, then obtain a piece of graph paper from
the instructor, draw the graph on the paper and tape or staple the graph into your lab notebook. Your
excel graph that you prepare at home (using class averages) should have a similar slope!
C. Results: at home
1. Prepare a Beer’s Law plot (calibration curve) via Excel using the average absorbances for the
class data set from Procedure 1. Include the equation of the best-fit line and R2 value on graph. R2
is a statistical function known as the coefficient of determination. The value of R2 for data in a
2
Cobb, C. L.: Love, G. A., J. Chem Ed. 75, 1 (1998)
G.S. lawrene, Trans. Faraday Soc., 52, 236 (1956)
M.W. Lister and D.E. Rivington, Can. J. Chem, 33, 1572 (1955),
2 0.200
3 0.400
4 0.600
5 0.800
Note: All solutions contain 2.0 mL _______ M SCN- & final volumes were made up to _______ ml with
________ M HNO3.
A 3.00 1.00
B 3.00 2.00
C 3.00 3.00
D 3.00 4.00
E 3.00 5.00
Note: All final volumes were _________ml made up with _________M HNO3.
7. Print Button
If a printer is attached, this will print the value shown
on the digital display.
8. Wavelength Control
The wavelength control selects the desired analytical
wavelength of the instrument. The selected wavelength
appears on the left side of the LED display. The Filter