The Determination of an Equilibrium Constant

Purpose: The purpose of this lab is to determine the value of the equilibrium constant, Keq, for
the reaction between iron (III) ions and thiocyanate ions, SCN-:
Fe3+(aq) + SCN- ---> FeSCN2+(aq)
This will be done by measuring absorbencies of different solutions with varying concentrations
of thiocyanate ions and discovering the relationship between absorption and concentration of
thiocyanate ions. This relationship can then be used to find equilibrium concentrations of each
component and thus the equilibrium constant. This lab will also ascertain the concentration of an
unknown thiocyanate ion solution by using the relationship we discovered before.
Hypothesis: I hypothesize that the equilibrium constant, Keq, for the reaction between iron (III)
ions and thiocyanate ions, SCN- will be a large positive number greater than one because the
product of this reaction (FeSCN2+) is more stable than the separated ions. This means that
products are favored over reactants and it leads to an equilibrium constant greater than one.
Introduction: In order to calculate the equilibrium constant for a reaction, one must first be
familiar with the notion of dynamic equilibrium. A dynamic equilibrium occurs in a reaction
when product and reactant concentrations cease to change and both are being
produced/consumed at an equal rate. In other words, the forward reaction and the reverse
reaction proceed at the same rate. In the equilibrium reaction between iron (III) ions and
thiocyanate ions, iron (III) and thiocyanate combine to form thiocyanatoiron, and at the same
time thiocyanatoiron disassociates into iron and thiocyanate ions. There are two types of
dynamic equilibrium: homogeneous equilibrium and heterogeneous equilibrium. In a
homogeneous equilibrium, all the components of the reaction are in the same phase, whether that
be a gas or a solution. On the other hand, components in a heterogeneous equilibrium are in
different phases. The reaction between iron (III) ion solution and thiocyanate ion solution results
in a homogeneous equilibrium, because both reactants and products are aqueous solutions. At
any given point during a reaction, the equilibrium can be characterized by the equilibrium
constant, K. An equilibrium constant is obtained by letting a reaction proceed to equilibrium and
then measuring the concentrations of each component involved in that reaction and creating a
ratio of products to reactants. The equilibrium constant will remain the same for each reaction
irregardless of initial concentrations. For the generic reaction aA+bB--->cC+dD, the equilibrium
constant is written as:
Kc = [C]^c[D]^d/[A]^a[B]^b
The rate constant of a reaction is important, because it can tell whether the reaction is product
favored or reactant favored. If K>1, the reaction is product favored. However, if K<1, the
reaction is reactant favored. The value of K only changes with a change in temperature. It is
important to note that only concentrations of aqueous solutions and gases are taken into account
in the equilibrium constant expression, solids and liquids are not.
A great deal of this lab involves using a colorimeter to find absorbencies of different
solutions at equilibrium. A colorimeter measures the absorbance of particular wavelengths of
light for different solutions. The absorption of these solutions is directly variable to the
concentration of solutes in the solution. The red FeSCN2+ solution created in this lab absorbs
blue light, which is why the colorimeter must be set to 470nm in order to emit blue light and
measure the absorbency of each solution.

Procedure: In the first part of this lab, five solutions will be prepared with varying amounts of
SCN-. They will be mixed with a constant volume of Fe(NO3)3 solution in all five test tubes in
order to have the concentration of Fe(NO3)3 be a control. There will be a colorimeter connected
to a Logger Pro module that is connected to a computer. The solutions of iron(III) nitrate and
water will be held in separate test tubes from SCN- until they are ready to be mixed and
recorded. As soon as the two are mixed, a cap will be placed on the test tube and there will be a
wait period of one minute before the cap is opened. The colorimeter will be calibrated with
distilled water before any tests are performed in order to prevent error. The cuvette used to hold
liquids in the colorimeter will be rinsed with small amounts of the solution before testing in order
to eliminate other liquids that may be leftover. Once a solution is ready to be tested, it will be
filled in the cuvette and placed in the colorimeter. Once the absorbency value stabilizes, the data
will be recorded. This is repeated for each test tube with varying concentrations of SCN-. The
graph on the computer will be used to find the concentration of SCN- in the unknown solution
used in Part II. In part III of the lab, solutions with varying volumes of SCN- and Fe(NO3)3 will
be tested in the colorimeter to find the equilibrium concentration of FeSCN2+ using the graph
made in part I. These concentrations will then be used to calculate equilibrium concentrations of
Fe3+ and SCN- for the mixtures in part III. With all equilibrium concentrations known, the value
of the equilibrium constant, K, can then be calculated.
Data:
Beaker

Absorbance

1
2
3
4
5
Unknown, Part II

.028
.241
.360
.467
.575
.316

Best-fit line equation for the Part I standard solutions: y=2744x+0.02674

Room Temperature: 23 degrees Celsius
Test Tube Number
1
2
3
4
5

Absorbance
0.00
0.143
0.193
0.256
0.289

Net absorbance
-----------------------------------0.143
0.193
0.256
0.289

Observations:
The mixture turned red as soon as the two solutions combined
It was difficult to get the cap on the test tube right away
The test tube was open for about a minute at times while the cuvette was being rinsed and
filled

Paper towels used to wipe cuvette for fingerprints are unreliable in cleaning up the
simplest of messes.

Data Analysis:

Discussion of Theory: A dynamic chemical equilibrium in a reaction occurs when both reactants
and products cease to change concentrations and both the forward and reverse rates of reaction
are equal. The equilibrium point of a reaction can be characterized by equilibrium constant, K.
For the general reaction aA+bB-cC+dD, this constant can be expressed as:
Kc = [C]^c[D]^d/[A]^a[B]^b
The goal of this lab was to ultimately calculate the equilibrium constant of the reaction between
iron(III) ions and thiocyanate ions:
Fe3+(aq) + SCN- ---> FeSCN2+(aq)
The equilibrium constant only changes with a change in temperature, which is why the
temperature of the room was initially recorded before mixing any chemicals. The temperature of
the room was 23 degrees Celsius. In order to calculate the constant, the concentrations of the
reactants and products at equilibrium needed to be ascertained first. This was done by measuring
absorbency values of mixtures at a state of equilibrium that varied in their initial concentration of
SCN- ions. The pre-lab exercise showed the concentration of FeSCN2+ ions that would be in
each test tube if the reaction ran to completion. This could be directly correlated to the
concentration of SCN- because one mol of SCN-= one mole of FeSCN2+. The first five solutions
were prepared by adding exactly 5.00mL of 0.200 M Fe(NO3)3 solution into each test tube.
Enough water was also added to these test tubes so that the total volume of Fe(NO3)3, SCN-,
and water would yield 50.0mL. The first test tube contained no amount of SCN- solution and its
absorbency would function as a base for the rest. Before beginning any tests, the calorimeter
was calibrated with diluted water placed in the cuvette. Then, for the first test, the solution
containing no SCN- was used to rinse the cuvette thoroughly two times. The third time, the
cuvette was filled about with the solution. During this process of rinsing the cuvette and filling
it with solution, the test tube of solution would often be left exposed to air for the entire period of
time. This error would have resulted in the forward reaction proceeding at a rate faster than the
reverse reaction, because conditions around the reaction vessel werent held constant throughout.
This would cause the concentration of FeSCN2+ to be greater than its equilibrium concentration,
and the equation for the best-fit line to be at a greater slope than it should be because the more
than predicted FeSCN2+ will absorb more light than it should at a predicted concentration. When
the unknown solution is tested at the end and it is capped immediately, the resulting absorption
value would correspond to a concentration less than its actual value. After filling the cuvette with
solution, it was then wiped for fingerprints in order to ensure that the maximum amount of light
would enter the solution. Several times, the paper towels used to wipe the cuvette clean were
unreliable and didnt appear to completely remove traces of fingerprints. This would result in
less light entering the cuvette and an absorption value that is less than expected. This lower
absorption value would correspond to a lower than predicted concentration. After wiping down
the cuvette, the colorimeter was set to blue light, 470nm, because FeSCN2+ absorbs this
wavelength of light. Once the absorbency reading for the solution remained stable at 0.00, the
value was recorded on the Logger Pro graph. This process was repeated for solutions with
increasing volumes of SCN-, which meant increasing concentrations of SCN- in the solution.
After mixing SCN- into the Fe(NO3)3 solution, the tube was capped for about a minute to allow
the reaction to run to equilibrium before testing. Due to human error in the experiment, there was
often difficulty placing the cap on tightly enough immediately after mixing the solutions; as a
result, the test tube became exposed to the air for longer periods of time than expected. Just as
leaving the test tube open while withdrawing solution resulted in a greater concentration of
FeSCN2+ ions at the end, this error would also cause a similar result. This same result would

eventually predict a lower concentration value for the unknown SCN- solution than it should be.
Once the chemicals were mixed and as the reaction proceeded, Fe(NO3)3 disassociated into
nitrate ions and Fe3+ ions that react with SCN- ions. The concentration values of SCN- in each
test tube/beaker obtained in the pre-lab were used to correlate the absorbency values with
concentration of SCN- in a linear relationship. This line of best fit could be described as:
y=2744x+0.02674
In this equation, y represents absorbency and x represents the concentration of FeSCN2+
initially. One purpose of this lab was to determine the concentration of an unknown SCNsolution. This was done by reacting it with the same amount of Fe(NO3)3 solution used in part
one and measuring the absorbency. This absorbency value measured with the calorimeter could
be traced on the line of best fit to find the corresponding concentration of thiocyanate. The
experimental concentration of SCN- was ascertained to be 1.05x10^-4 M. The actual molarity of
the SCN- solution was 2.0*10^-3 M. The percent error in this lab was calculated to be -94.8%

Part III of the lab involved finding absorption values for solutions similar to those in part
I and II, except this time the total volume of the solution would only be 10.0 mL instead of
50.0mL. Once the absorption values were acquired they could be plugged into the equation
determined in part I to calculate for the concentration of FeSCN2+ at equilibrium. The initial
concentrations of the reactants could be determined by using dimensional analysis to multiply
the molarity before mixing by the volume-to-volume ratio of the solute to the total solution
respectively. With the initial concentrations of reactants determined, along with the equilibrium
concentration of the product, the concentrations of the reactants at equilibrium could be
determined by using a simple I.C.E table (Initial Change Equilibrium). Since the product,
FeSCN2+ started out at an initial concentration of zero and only increased by one multiple of
concentration change (x), the equilibrium molarity of FeSCN2+ would represent the change in
molarity of all components in the reaction equation. Also, since all the coefficients in the reaction
are simply one, the absolute values of change in concentrations are equal for all components. For
example, the reaction occurring in test two had an initial Fe3+ concentration of 6.0*10^-4 molar,
initial SCN- concentration of 4.0*10^-4 molar, and an equilibrium FeSCN2+ concentration of
4.24*10^-5 molar. The I.C.E table for this reaction would look like:

Since, the equilibrium concentration of FeSCN2+ has been determined using the absorption
value and equation for line of best fit, the value of x has been ascertained to be that as well. The
equilibrium concentrations of Fe3+ and SCN- can be determined by subtracting the value of x
from the initial concentrations of these reactants. The equilibrium concentrations for Fe3+ and
SCN- are calculated to be:

This process was used to calculate the equilibrium concentrations of all reactants and products in
all five test tubes of Part III.
The final piece to solving the equilibrium constant at 23 degrees Celcius was plugging in
all equilibrium concentrations into the equation for Kc:
Kc=[C]^c[D]^d/[A]^a[B]^b
The equilibrium constants for test tubes 2-5 were calculated to be 210, 210, 220, and 210
respectively. The overall constant for the reaction was calculated by averaging these values out;
it was calculated to be 210.
Conclusion: The purpose of this lab was to determine the value of the equilibrium constant,
Keq, for the reaction between iron (III) ions and thiocyanate ions, SCN- by measuring
absorbencies of different solutions with varying concentrations of thiocyanate ions and
discovering the relationship between absorption and concentration of thiocyanate ions. This
relationship can then be used to find equilibrium concentrations of each component and thus the
equilibrium constant. The equilibrium constant for this reaction at 23 degrees Celcius was
ascertained to be 210. This labs goal was also to calculate the concentration of an unknown
thiocyanate ion solution by using the relationship we discovered before. The experimental
concentration was discovered to be 1.0*10^-4M, which has a -94.8% error from the actual
concentration of 2.0*10^-3 M.