43

Experiment 4
DETERMINATION OF THE EQUILIBRIUM CONSTANT
FOR A CHEMICAL REACTION
When chemical substances react, the reaction typically does not go to completion. Rather, the system
goes to some intermediate state in which both the reactants and products have concentrations that do not change
with time. Such a system is said to be in chemical equilibrium. When in equilibrium at a particular temperature,
a reaction mixture obeys the Law o f Mass Action (or the Law o f Chemical Equilibrium), which imposes a
specific condition on the concentrations of reactants and products that is expressed by the equilibrium constant
for the reaction.
In this experiment, the reaction between iron(III) ion (Fe3+), and thiocyanate ion (SCN-), will be studied.
When solutions containing Fe3+ and SCN- are mixed, a reaction occurs forming the FeSCN2+ complex ion that has a
deep red color. The reaction may be written:

Fe3+ (aq) + SCN- (aq)

FeSCN2+ (aq) .

(1)

The reaction between iron(III) ion and thiocyanate ion does not go to completion. Instead, equilibrium is
established at some intermediate state where both the reactants and products have concentrations that do not
change with time. As a result of the reaction, the amounts of Fe3+ and SCN- at equilibrium will be less than the
amount of each present before the reaction occurred. From the balanced chemical equation, we can see for every
mole of FeSCN2+ that is formed, one mole of Fe3+ and one mole of SCN- will be consumed.
According to the Law of Mass Action, the equilibrium constant (Kc), for Equation (1) may be
formulated as shown in the following expression:

Kc =

FeSCN2+
Fe3+ SCN-

,
(2)

where the molar concentrations of FeSCN2+, Fe3+, and SCN- are measured at equilibrium. The value of Kc in
Equation (2) is constant at a given temperature. As a result, mixtures containing Fe3+ and SCN- will react
until Equation (2) is satisfied. Additionally, the same value of Kc will be obtained no matter what initial amounts of
Fe3+ and SCN- were used.
The purpose of this experiment is to measure Kc for several mixtures of Fe3+ and SCN- made up in different
ways. The mixtures will be prepared by mixing solutions containing known concentrations of iron(III) nitrate
[Fe(NO3)3], and potassium thiocyanate (KSCN). The reaction between iron(III) ion and thiocyanate ion is a
particularly good one to study because the value of Kc is of a convenient magnitude and the intense color of the
FeSCN2+ complex ion makes the determination of its equilibrium concentration quite simple. Knowing the initial
composition of a mixture and the equilibrium concentration of FeSCN2+, the equilibrium concentrations of the rest
of the pertinent species may be calculated and then used to determine Kc.

44

Example:

Given the equilibrium concentrations of [Fe3+] = 8.50 x 10-4 M, [SCN-] = 7.60 x 10-4 M, and
[FeSCN2+] = 1.50 x 10-4 M at 40C, calculate the equilibrium constant from Equation (2).

Answer:

Substituting the equilibrium concentrations into Equation (2) yields:

Kc =

1.50 x 10-4
= 232 .
8.50 x 10-4 7.60 x 10-4

The equilibrium concentration of FeSCN2+ in the various mixtures will be determined using a
spectrophotometer by measuring the amount of light absorbed by the red complex ion at 447 nm, the wavelength
at which the complex ion most strongly absorbs. The absorbance (A), of the complex ion is proportional to its
molar concentration, M, and can be measured directly on the spectrophotometer:

A=kM ,

(3)

where k is simply a proportionality constant.

In order to determine the concentration of an unknown solution, a calibration plot must be prepared.
Essentially, each spectrophotometer is slightly different and a calibration plot that gives the absorbance values for
a series of known concentrations must be constructed. From the calibration plot it is then possible to determine
the concentration of an unknown solution from its absorbance.

45

Example:

Given the calibration data in the table below, calculate the equilibrium concentration of FeSCN2+,
if the absorbance is 0.405.
[FeSCN2+]
0.250 x 10-4
0.500 x 10-4
1.00 x 10-4
1.60 x 10-4

In order to determine the concentration of FeSCN2+, a calibration plot must first be constructed
as shown in the graph below.
Calibration Plot for FeSCN2+

0.800

y = 4906.034x - 0.005 r2 = 0.999

0.700

0.600

Absorbance

Answer:

Absorbance
0.121
0.243
0.475
0.786

0.500

0.400

0.300

0.200

0.100
0.00E+00 2.50E-05 5.00E-05 7.50E-05 1.00E-04 1.25E-04 1.50E-04 1.75E-04 2.00E-04

[FeSCN2+]

From the calibration data, a least squares analysis was performed and the best straight line fitting
the data was drawn. The equation for the line is given at the top of the plot:
y = 4906.034x - 0.005

r2 = 0.999 .

The concentration of FeSCN2+ can be determined by substituting the value of the absorbance
into the equation for the least squares line and solving for the concentration.

0.405 + 0.005
x=

4906.034

= 8.36 x 105M

46

In preparing a calibration plot, in addition to the equation for the least squares line, the correlation
coefficient (r2) is also determined. The correlation coefficient indicates how well the data fits the equation for a
straight line. A value of 1.000 indicates a perfect fit. The farther the correlation coefficient is from 1.000 indicates
that the data is less well represented by a straight line. From the example above, the correlation coefficient of
0.999 indicates that the data is linear.
In the preceding example, the assumption was made that the reaction that occurred was given by
Equation (1). There is no inherent reason why the reaction might not have been

Fe3+ (aq) + 2SCN- (aq)

Fe(SCN)2+ (aq) ,

(4)

for which the equilibrium constant would be given by the expression:

Kc =

Fe(SCN)2 +
Fe3+ SCN-

.
(5)

The obvious question to be answered is how is it possible to determine whether we are actually observing the
reaction given in Equation (1) or the reaction given in Equation (4)? The line of reasoning by which we can
accomplish this task is that if the reaction in Equation (1) is the one that is occurring, the Kc value for that reaction,
as we calculate it, should remain constant for different reagent mixtures. If however, the reaction given in
Equation (4) is the one that is occurring, the Kc value, as calculated for that reaction, should remain constant.
Thus a determination can be made as to which reaction is occurring by comparing the constancy in the values of
the equilibrium constants for the two reactions.

47

EXPERIMENTAL PROCEDURE
Obtain from the cart in the front of the laboratory two 5 mL graduated pipets, a 5 mL pipet and a pi pump
pipet aid (green). Clean and rinse the pipets as directed by your instructor.
Label five clean, dry 10 mm x 150 mm test tubes 1 to 5, with a pencil or by noting their positions in your
test tube rack.
Using a repipet, deliver 30 mL of 2.00 x 10-3 M Fe(NO3)3 into a clean, dry 50 mL beaker. Using the 5 mL
pipet, carefully pipet 5.00 mL of the Fe(NO3)3 solution into each test tube. Discard any remaining Fe(NO3)3 into the
sink.
Using a repipet, deliver 20 mL of 2.00 x 10-3 M KSCN into another clean, dry 50 mL beaker. Using the
graduated pipet, carefully pipet 1, 2, 3, 4, and 5 mL of the KSCN solution into each of the corresponding test
tubes labeled 1 to 5, respectively. Discard any remaining KSCN solution into the sink.
Rinse one of the 50 mL beakers twice with tap water and once with approximately 10 mL of distilled water
and then fill the beaker with approximately 20 mL of distilled water.
Using the second clean graduated pipet, carefully pipet the proper amount of distilled water into each test
tube to bring the total volume in each test tube to 10.00 mL. Mix e a c h solution thoroughly with a glass
stirring rod. Improper mixing is a large source of error in this experiment. Be sure to dry the stirring rod with a paper
towel after mixing each solution. The volumes of reagents to be added to each test tube are summarized in
Table 1.
Table 1. Composition of test tube mixtures
Test Tube Number
1
2
3
4
5
______ ______ ______ ______ ______
Volume Fe(NO3)3 solution (mL)

5.00

5.00

5.00

5.00

5.00

Volume KSCN solution (mL)

1.00

2.00

3.00

4.00

5.00

Volume H2O (mL)

4.00

3.00

2.00

1.00

0.00

Check out a cuvette from the stockroom. A cuvette looks like a 10 mm x 100 mm test tube. However, it is
made from special optical glass and tested to be optically pure. Cuvettes are much more expensive than ordinary
test tubes. Handle them with care!
Using a Turner Spectrophotometer Model SP-830, measure the absorbance at 447 nm of each of the five
solutions. Rinse the cuvette with a small portion of the solution to be measured. Be sure to fill the cuvette over
half full with solution.

48

Using one of the sets of calibration standards, determine the absorbance at 447 nm of each of the four
standard solutions on the same spectrophotometer that you used to measure the absorbance of your unknown
solutions. The standard solutions of [FeSCN2+] are 1.00 x 10-4 M, 0.750 x 10-4 M, 0.500 x 10-4 M, and
0.250 x 10-4 M. Record the calibration data on the laboratory report. Also, be sure to record the number of the
instrument you used on the laboratory report.
Return the equipment to the cart upon completion of the experiment. Return the cuvette to the
stockroom.

Lamp

Field lens
Entrance slit

Objective lens

Occluder

Grating

Measuring phototube Sample

Light control
Filter

Exit slit
Wavelength cam

Figure 1. Optical system of a typical spectrophotometer.

The operation of the optical system of a typical spectrophotometer is shown schematically in the Figure 1.
White light emitted by the tungsten lamp is focused by the field lens on the entrance slit. The objective lens
focuses the image of the entrance slit at the exit slit after it has been dispersed and reflected by the diffraction
grating (the diffraction grating acts like a prism).
When setting the wavelength, a cam positions the grating so that only the desired wavelength passes
through the exit slit. The monochromatic light that passes through the exit slit continues on through the sample
contained in a cuvette placed in the light path. Finally, the monochromatic light beam terminates at the measuring
phototube, where the light energy is converted to an electrical signal. When the sample is removed from the
instrument, an occluder automatically falls into the light path so that the zero light level (total absence of light) may
be set automatically. A light control is provided to set the 100% transmittance/0 absorbance with a reference
solution in the sample holder.

49

Turner Spectrophotometer Model SP-830

Stray Light
Filter

Display Panel

Sample
Compartment
Wavelength
Dial

TRANS/ABS
100%T/0 A

Wavelength Display
FUNCTION
The Turner SP-830 is a simple to use yet highly reliable spectrophotometer. This instrument uses a digital
microprocessor to provide a photometric readout of transmittance and absorbance of light over the range 330 to
999 nm.
NOTE: Always wipe the outside of the cuvette with a tissue or soft cloth to remove dirt or fingerprints that may
affect the reading before inserting the cuvette into the sample compartment.
Operating Instructions
1.

Turn the power on and allow the spectrophotometer to warm-up for at least 20 minutes.

2.

Rinse and then fill a cuvette with the solvent that will be used to zero the spectrophotometer. This is the
blank (or background solvent) that your sample is dissolved in. In this experiment, the blank is distilled
water.

3.

Place and align the cuvette in the cuvette holder in the sample compartment. (When a cuvette is properly
aligned in the sample compartment, the alignment mark on the cuvette should face to the front of the
instrument.

4.

Turn the wavelength dial to the desired wavelength (447 nm for this experiment).

5.

Set the stray light filter to the appropriate setting, as noted on the underside of the sample compartment
lid (2 for this experiment). Carefully close the door on the sample compartment.

6.

Select the Absorbance mode by pressing the TRANS/ABS button (the appropriate light will be
illuminated under the display, indicating Transmittance or Absorbance mode).

7.

Zero the instrument by pressing the 100%T/0 A button. The display should show "0.000".

8.

Carefully open the sample compartment and remove the cuvette.

9.

Rinse the cuvette with a small portion of the next sample to be measured and then fill the cuvette with
sample. Place and align the cuvette in the cuvette holder in the sample compartment.

10.

Close the sample compartment door. The absorbance of the sample solution is shown on the display.
Record the value on the data sheet.
Repeat steps 8-10 for each sample.

50

Graphing Instructions
In the computer lab in BH-128, find an open Apple Macintosh computer.
Find and open the program: CA - Cricket Graph III
The program will open to a blank spreadsheet.
Click on the title for column 1 and type Absorbance.
Click on the title for column 2 and type Concentration.
Enter the appropriate calibration data into the cells in the first two columns (click on the first cell in a column and
enter the data--hitting the return or enter key moves down a column).
Under GRAPH, select NEW GRAPH, SCATTER.
Assign the appropriate variables to the x-axis and the y-axis. The plot should be Absorbance (y-axis) versus
Concentration (x-axis).
Hit OK.
The least squares line is plotted and the plot becomes a calibration plot.
Under OPTIONS, select CURVE FIT;
Method - select LINEAR
Coefficient Display - select R SQUARED
Hit OK
Under FILE, select PRINT.
The graph should look very much like the calibration plot given in the example in the instructions for the experiment.

51

Ex. 4

Name ________________________________________ Section _______

Drawer _______

PRELABORATORY ASSIGNMENT: EQUILIBRIUM CONSTANT DETERMINATION

1. A student mixes 5.00 mL of 2.00 x 10-3 M Fe(NO3)3, 4.00 mL of 2.00 x 10-3 M KSCN, and 1.00 mL of distilled
water and finds that in the equilibrium mixture the concentration of FeSCN2+ is 1.31 x 10-4 M.
Fe3+ (aq) + SCN- (aq)

FeSCN2+ (aq) .

a. Find the number of moles of Fe3+ and SCN- initially present.

___________ moles Fe3+

___________ moles SCNb. How many moles of FeSCN2+ are in the mixture at equilibrium?

___________ moles FeSCN2+

c. How many moles of Fe3+ and SCN- are used up in making the FeSCN2+?

___________ moles Fe3+

___________ moles SCNd. How many moles of Fe3+ and SCN- remain in the solution at equilibrium?

___________ moles Fe3+

___________ moles SCNe. What are the concentrations of Fe3+, SCN-, and FeSCN2+ at equilibrium?

[Fe3+] = ___________ M

[SCN-] = ___________ M

[FeSCN2+] = ___________ M
f.

What is the value of Kc for the reaction?

K c = ___________

Absorbance

2. Given the calibration data in the table below, calculate the equilibrium concentration of [FeSCN2+] if the absorbance is 0.460.
[FeSCN2+]
-4

0.500 x 10-4

0.250 x 10

[FeSCN2+]

Absorbance

Absorbance

0.120

1.00 x 10

-4

0.481

0.240

1.60 x 10-4

0.770

1.00

0.90

0.80

0.70

0.60

0.50

0.40

0.30

0.20

0.10

0.00
0.00

0.20 x 10 -4

0.40 x 10 -4

0.60 x 10 -4

0.80 x 10 -4

1.00 x 10 -4

1.20 x 10 -4

1.40 x 10 -4

Concentration [FeSCN 2+ ]

[FeSCN2+] = ___________ M

1.60 x 10 -4

53

Ex. 4

Name ________________________________________ Section _______

Drawer _______

LABORATORY REPORT: EQUILIBRIUM CONSTANT DETERMINATION

DATA
Mixture

Absorbance

___________

Calibration Data: Instrument # _______

[FeSCN2+]

Absorbance
-4

___________

0.250 x 10

___________

___________

0.500 x 10-4

___________

___________

-4

0.750 x 10

___________

___________

1.00 x 10-4

___________

CALCULATIONS
1.

Using Cricket Graph, construct a calibration plot for your instrument. Have the computer draw the least
squares line and give the equation and correlation coefficient (r2) for the line.

Cut out the graph and tape it here.

2.

Using the least squares line, determine the concentration of FeSCN2+ for each mixture.
Mixture

[FeSCN2+]

___________

___________

___________

___________

___________

CALCULATIONS
A. Calculation of Kc assuming the reaction: Fe3+ (aq) + SCN- (aq)
Mixture

Initial No. Moles

Fe

3+

FeSCN2+ (aq) .

Equilibrium No. Moles

SCN-

Fe

3+

SCN

Equilibrium Concentration
FeSCN

2+

3+

[Fe ]

[SCN-]

[FeSCN2+]

Kc

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

B. Calculation of Kc assuming the reaction: Fe3+ (aq) + 2SCN- (aq)

Fe(SCN)2+ (aq) .

N O T E : Because of the procedure used for calibrating the spectrophotometer, [Fe(SCN)2+] will equal one-half the [FeSCN2+] obtained for each solution
in Part A. Also note that two moles of SCN- are needed to form one mole of Fe(SCN)2+.
Mixture

Initial No. Moles

Fe

3+

Equilibrium No. Moles

-

SCN

Fe

3+

Equilibrium Concentration

SCN

Fe(SCN)2

3+

[Fe ]

[SCN-]

[Fe(SCN)2+]

Kc

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

_________

QUESTIONS
1. On the basis of the results in Parts A and B, what would you conclude about the formula of the iron (III) thiocyanate complex ion?

2. What value would you report for Kc? Explain how you obtained this value.