THERMODYNAMICS

EXPERIMENT 11
Spectroscopic Determination of an
Equilibrium Constant (2 Weeks)
GOAL AND OVERVIEW
The equilibrium for the reaction of iron (III) with thiocyanate to yield the colored
product, iron (III) thiocyanate,
Fe3+ + SCN- ' FeSCN2+

will be studied and its equilibrium constant determined spectroscopically using the Spec 20 UV-
visible spectrometer. The spectral profile of iron (III) thiocyanate will be obtained to determine
the wavelength of light absorbed most strongly by the product. A Beer's law plot will be made
for iron (III) thiocyanate. Using a set of different starting concentrations and measuring the
concentration of iron (III) thiocyanate spectroscopically, the equilibrium constant for the reaction
will be determined.

OBJECTIVES (SKILLS GAINED THROUGH THIS EXPERIMENT)

Overall
• familiarity with equilibrium principles and manipulating equilibrium constant expressions
• usage of Beer’s Law to characterize amounts of molecules

Prelab
• familiarity with equilibrium concepts and calculations
• gaining a clear vision of the procedure with outlines, flowcharts and data tables.

Doing the Experiments (collecting data)

• To a variety of equilibrium states using quantitative lab technique.
• practice using a lab notebook to thoroughly document an experiment
• To employ the Spec 20 and Beer's law in quantitative analysis in the way countless chemists
and biologists employ it every day.
• practice doing dilutions
• observation of equilibrium

Data Analysis (determining desired quantities from experimental measurements)

• To gain further expertise at calculating solution concentrations resulting from volumetric
dilutions.
• to become skilled with determining equilibrium concentrations and equilibrium constants
• to consider the effects of error when assumptions are needed

Reporting Results
• practice realizing the entire experiment or "putting it all together" as you write the abstract
• communicating creatively, clearly and consciously an overview and details of the experiment

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SUGGESTED REVIEW AND EXTERNAL READING
• in Section 2C Introduction to spectroscopic studies and Experiment 9 Usage of Beer’s Law
• in Section 3B on the use of Spec-20 UV-visible spectrometer
• in Section 3.5 of Silberberg on preparing and diluting aqueous solutions
• in Section 2D Introduction on the fundamentals of equilibrium constants
• in Chapter 17 of Silberberg on equilibrium constants
o Section 17.5 on using equilibrium quantities to determine equilibrium constants

EXPERIMENT PREPARATION (PRELAB HOMEWORK)

Week 1
(to be filled out in your bound lab notebook before you perform the experiment)
Write a Title and Purpose for the experiment (what are you trying to determine?)

Write Definitions of Vocabulary Words: (1) equilibrium constant, (2) transmittance,

(3) absorption, (4) lambda max, (5) molar extinction coefficient

Answer These Questions:

1. If a substance in solution is orange, in what range of colors and wavelengths is it
likely to have its λmax?
2. In order to make 100 mL of 0.1 M Fe(NO3)3⋅ 9H2O solution, what mass of this
hydrated salt should you weigh out? (The molar mass of the salt includes the nine
waters.)
3. State LeChatelier's principle.
4. What is a blank used for in spectroscopy?
5. Suppose you make up a solution by adding 2 mL of 2 x 10-3 M NaSCN and 5 mL of 2
x 10-3 M Fe(NO3)3 and 3 mL of 2 x 10-3 M NaNO3. Before these reactants begin to
react, what is the concentration of the SCN- ion and of the Fe3+ ion?
6. How is Beer’s law used to determine an unknown concentration?

Write the procedure in bound lab notebook (Plan to Do the Experiment)

(detailed guidelines and examples are given in Section 3 of the manual)
You will have two weeks to do this experiment. It is possible to complete most of it in
the first week, and the second week can be dedicated to working up the data, confirming
your results and analysis of the assumption with your TA and other students.

Week 2
(to be completed before you perform the last part of the experiment)
Conclusions based on Temperature Dependent Observations:
Is the reaction exothermic or endothermic? Explain.

Spectral Profile: Graph of Absorbance versus Wavelength noting λmax.

Beer’s Law Plot: Graph of Absorbance versus [FeSCN+2] noting ελmax.

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BACKGROUND
This experiment explores the equilibrium established by the reaction of the iron (III),
Fe , and the thiocyanate, SCN-, ions:
3+

Fe3+ + SCN- ' FeSCN2+ (1)

The reactants are colorless, but the FeSCN2+ ion is orangish colored. At equilibrium, the
concentrations of these three ions must be related to each other according to the equilibrium
constant expression:
[Fe SCN 2+ ]
K = (2)
[ Fe3+ ][ SCN - ]
One of our goals in this experiment will be to measure the value of K, using the spectrometer for
the quantitative analysis of the concentration of FeSCN2+ ion. Near the end of the introduction
to section 2C, absorption studies and Beer’s Law are discussed in detail and were used in
experiment 9 to determine an unknown concentration of allura red. This same method will be
utilized to determine [FeSCN+2], the colored product. Then, using an understanding of
equilibria, we will deduce the equilibrium concentrations of the reactants. Knowing all three
concentrations listed above in equation 2 will allow the calculation of the equilibrium constant
for this reaction.

PROCEDURE (work in pairs)

Part 1. Qualitative Observations of Equilibrium: determining if the reaction is exothermic

or endothermic.
Using a 10 mL graduated cylinder, measure out approximately 2 mL of 2 x 10-3 M
NaNO3 and put it in a test tube. Then add approximately 8 mL of 2 x 10-3 M NaSCN. Then add
approximately 10 mL of 2 x 10-3 M Fe(NO3)3. Note the color of the solution. Fill a Spec 20
cuvette no more than 2/3 full and split the remaining solution among three test tubes. Place one
of these tubes in an ice bath and one in the hot water bath on the hot plate. After about 10
minutes, compare them with the solution at room temperature. Discuss the implications of your
observations, basing your discussion on your knowledge of LeChatelier's principle. Do
your observations imply an exothermic or endothermic reaction?

Part 2. Determining the Spectral Profile and λmax (most sensitive wavelength) of FeSCN2+
Measure the transmittance of the mixtures in your cuvette in the range from 370 to 560
nm. Take readings at 20 nm intervals. In the region of minimum transmittance, shrink your
intervals to 10 or even to 5 nm. Use a cuvette containing the NaNO3 as a blank to set 100%
transmission. Plot absorbance against wavelength and indicate your experimental value of λmax.
How does your spectral profile and λmax fit with your answer to Question 1 of the pre-lab
assignment?

Part 3. Making a Beer's Law Curve for FeSCN2+: determining how strongly (ε) the
product absorbs light at λmax.
To make solutions of known concentrations of FeSCN2+, you cannot simply dissolve a

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salt containing FeSCN2+ in water, because the ion will dissociate in order to satisfy the
equilibrium constant expression. If we knew the value of K, we could make up solutions with
known initial concentrations of FeSCN2+ and solve the algebra to find how much dissociated,
thus how much was left undissociated at equilibrium. However, we do not know the value of K,
so we must be cleverer than that.
We will take our spectral curve data using a set of solutions with a very high
concentration of Fe3+ and quite small concentrations of SCN-. We will assume that the SCN- is
then the limiting reactant, i.e., that almost all of it is used up to make FeSCN2+. If so, we can
equate the desired equilibrium concentration of iron thiocyanate ion, [FeSCN2+], to the initial
concentration of thiocyanate ion, [SCN-]o. Once we have actually measured K for the reaction,
we will have to return to this assumption and verify that it is valid.

Make 100 mL of 0.1M Fe(NO3)3 (which we will call solution B) using the following
process: (See Question 2 of the pre-lab assignment.) Weigh out the appropriate amount of this
hydrated salt to the nearest 0.0l g. (The nine waters of hydration that are present in the crystals
of this salt and must be figured into the mass you weigh out.) Put this salt into a 100 mL
volumetric flask, and add about 50 mL of distilled water. What is the color of the solution? Add
concentrated nitric acid drop by drop until the solution is faint straw-colored (This may require
as many as 50 drops.). What do you think is happening here? The nitric acid does not contribute
to the concentration of the Fe3+ ion. It just makes sure that the iron present in the solution is
present as Fe3+. Dilute with water to the 100ml mark.
Make your strongest colored solution of sodium thiocyanate and iron (III) nitrate (which
we will call solution A) as follows: Using a volumetric pipet, put 5 mL of 2 x 10-3 M NaSCN
(from the lab shelf, concentration known to 1%) into a 50 mL volumetric flask and fill to the
mark with solution B above.
Using only volumetric glassware (Do not use graduated pipets or cylinders. You have
the following volumetric pipets available: 1, 2, 5, 10 mL. You have the following volumetric
flasks available: 10, 50, 100 mL.), accurately create 10 mL volumes of the following dilutions of
solution A with solution B:
Pure B for use as a blank, faint straw-colored, no colored complex
1 mL A into 10 mL flask, filled to mark with B
3 mL A into 10 mL flask, filled to mark with B
5 mL A into 10 mL flask, filled to mark with B
7 mL A into 10 mL flask, filled to mark with B
9 mL A into 10 mL flask, filled to mark with B
Pure A, the pure most colored solution
As each of these solutions is created, measure its absorbance. You now have 7 points to
enter onto a Beer's law plot of absorption against concentration of FeSCN2+. Fit a straight line to
your points. Express this line mathematically in the form of Beer’s Law (Eq. 6 of Experiment 9
found in the Section 2C Introduction). Using the measured path length of your cuvette, what is
the value of the extinction coefficient for FeSCN2+ at its λmax?
You should get to this point by the end of the first week's lab work. Be sure to note
which spec 20 you are using, because you just determined the λmax and εFeSCN+2 for that specific
spec 20.

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Part 4. Determining the Equilibrium Constant for the Formation of FeSCN2+
In this part of the experiment, you prepare five solutions with the same initial
concentration of iron (III) ion but different initial concentrations of thiocyanate ion. As you
make each solution, you measure its percent transmittance at the λmax of Part 2 and use your
Beer's law plot to establish the equilibrium concentration of FeSCN2+. From the initial
concentrations of the reactants and the equilibrium concentration of the product, you can
calculate for each of the five solutions its experimental value of K, using Eq. 2.
Use a 10 mL volumetric flask to prepare each of the following five solutions, using the
solutions provided, each of which is 2 x 10-3 M: NaSCN, Fe(NO3)3, and NaNO3. The
concentration of the first, when you figure in its dilution in the 10 mL flask, will be the initial
concentration of SCN-. The concentration of the second, again figuring in the dilution in the 10
mL flask, will be the initial concentration of Fe3+. The third is added to fill the flask to 10 mL.

2 x 10-3 M NaSCN 2 x 10-3 M Fe(NO3)3 2 x 10-3 M NaNO3

0 mL 5 mL 5 mL (blank)
1 mL 5 mL 4 mL
2 mL 5 mL 3 mL
3 mL 5 mL 2 mL
4 mL 5 mL 1 mL
5 mL 5 mL 0

Waste Disposal
The solutions from all parts of this experiment must be neutralized with
sodium bicarbonate before they are put into the labeled waste bottles. Check that
they are neutral with pH paper before you pour them into a waste bottle (in the
hood). If you are ever in doubt, ask your TA.

DATA ANALYSIS
Most of the analysis of data is described above in the descriptions of the four parts of the
experiment. Here we review how to calculate the equilibrium constant, K, for the reaction in Eq.
1. The standard approach to these problems is first to write the balanced chemical equation, with
a grid below it with rows for initial amounts, changes in amounts, and final equilibrium amounts
and concentrations:

Fe3+ + SCN- ' FeSCN2+

I_nitial amount (mole/L)
C_hange in amount (mole/L)
E_quilibrium amount (mole/L)

“ICE” table

• the initial amounts of reactants (the amounts before the reaction has begun) are determined

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using the dilution equation.
• The initial amount of product (the amount before the reaction has begun) is zero.
• The equilibrium concentration of product was determined spectroscopically. The
product’s absorption and εb from part 2 are used with Beer’s Law to determine the
equilibrium concentration.
Given this information, the ICE table can be filled in, box-by-box, until the equilibrium
concentrations of reactants are determined allowing the calculation of the equilibrium constant.
Begin by filling out the product column from the bottom up. Then relate the change in amount
of product to the change in amount of reactant. Because of the simple stoichiometry of this
reaction (1:1:1), the moles of reactant consumed will be equal to the moles of product created.
Here is a filled-in table using variables for initial amounts and the amount of product created:

Fe3+ + SCN- ' FeSCN2+

initial concentration [Fe+3]ini [SCN-]ini 0
change in concentration -x -x x
equilibrium concentration [Fe+3]ini - x [SCN-]ini – x x

• x is the amount of product created, and is determined using the experimentally determined
extinction coefficient and absorption with Beer’s Law.
You now are able to calculate the experimental equilibrium constant, using Eq. 2 and the
equilibrium concentrations from the bottom row of the ICE table.
Calculate K for each of the five solutions in Part 4. Find the average value of K and the
relative error (standard deviation divided by the average). Are the values similar? Should they
be?
Check of Assumption Used in Making Beer's Law Plot
Given your value of K, go back and check the validity of the assumption you made in
Part 3. Solve equation 2 for [FeSCN+2] eq /[SCN-]eq. You now know Keq and the iron
concentration was approximately 0.1M in part 3. Therefore you can check for the approximate
ratio of [FeSCN+2] eq /[SCN-]eq. The assumption that all or most of the SCN- reacted, thus
creating FeSCN+2 would mean that this ratio would need to be large. Is it? If the ratio is small
the assumption was clearly a bad one and the experiment is useless in determining the
equilibrium concentration of FeSCN+2 and thus the equilibrium constant. You should discuss
how good the assumption was and how the assumption effected the final Keq that you calculated.
Based on your understanding of the assumption you should be able to explain if the Keq you
determined is too large or too small. Also, based on the size of error in your Keq, which you
determined in this checking of the assumption, you should be able to predict about how far your
experimentally determined result is off from the true value. Please be aware that checking the
assumption is only part of doing a thorough analysis of the experiment and should not be
considered the main point of the experiment. You did the experiment to determine a Keq for a
certain reaction, and used a “trick” (the assumption) to determine that Keq.

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Once you have worked up all your data and understand the entire experiment, you are
ready to communicate your results.

REPORTING RESULTS
(to be turned in one week after experiment is performed.)

Do a COMPLETE report for this experiment.

COMPLETE report guidelines are outlined in Sections 1 and 3 of this manual.
Include items listed below as well as those asked for in the procedure and data sections of
the experiment.

Abstract including:
• Method of determining results (experiment and analysis)
• Results summary

Introduction:
• Equilibrium, equilibrium constants and LeChatelier’s principle
• Using absorption spectroscopy and Beer’s law to determine an equilibrium
concentration

Results
• Observations for part 1
• Spectral profile for part 2 including λmax
• Beer’s law plot for part 3 including slope(εb)
• Ice tables, individual and average Keq values

Sample Calculations for determinations of:

• absorbance from transmittance
• concentration calculations
• Keq calculation
• assumption testing

Discussion of:
• what you found out and how
• relating your results to predictions of theory
• how was part 3 dependent on part 2?
• validity of the assumption
• what can you conclude from this experiment

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REVIEW QUESTIONS

1. Suppose you make up a solution by adding 4 mL of 2 x 10-3 M NaSCN and 5 mL of 2 x 10-3

M Fe(NO3)3 and 1 mL of 2 x 10-3 M NaNO3. Before these reactants begin to react, what is
the concentration of the SCN- ion and of the Fe3+ ion?
2. What assumption did you make in determining you Beer's law curve? How did you verify
that your assumption was correct?

3. What equation describes how the absorption of a molecule is dependent on the molecule’s
concentration?
How can this dependence be determined?

4. What is Le Chatelier’s Principle? give an example.

5. Know how to write an equilibrium constant expression given a certain reaction.

6. How might you experimentally determine if a reaction is exothermic or endothermic if the

reaction had a colored reactant or product?

part 1 (Le Chatelier’s principle)

7. If in the reaction of Fe+3 and SCN- to form FeSCN+2, were to be light colored in hot bath and
dark colored in the cold bath, is this an endothermic or exothermic reaction?

part 2 (spectral prolfile)

8. Why is a spectral profile always done before a beer’s law plot? hint: what is the goal of the
spectral profile?

9. Does λmax refer to the wavelength of maximum absorbance or maximum transmittance?

part 3 (Beer’s Law Plot)

10. What is the primary use of beer’s law?
How is the law used?

11. In part 3, the equilibrium concentration of the product was assumed to be approximately that
of the limiting reactant.
Is this true if the equilibrium constant for the reaction is large or small? explain your answer.

12. How was part 3 dependent on part 2?

part 4 (Keq determination)

13. Know how to determine a concentration given an experimental transmittance and the slope
of a beer’s law plot for the absorbing species.

14. Know how to fill in an ICE table and use it to find a equilibrium constant.

15. How was part 4 dependent on part 3?

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