Name___________________________________________________________Lab

Day__________Lab Time_________

Experiment 6 Equilibrium

Pre-lab questions
Answer these questions and hand them to the TF before beginning work.

(1) What is the purpose of this experiment?

_________________________________________________________________________________________________________

_________________________________________________________________________________________________________

(2) You will measure the absorbance of a solution at 447 nm. What is the formula of the
compound that is absorbing light at 447 nm?

_________________________________________________________________________________________________________

_________________________________________________________________________________________________________

(3) The BeerLambert Law states that the absorbance of a solution is proportional to what
property of that solution?

_________________________________________________________________________________________________________

_________________________________________________________________________________________________________

(4) Define the term equilibrium.

_________________________________________________________________________________________________________

_________________________________________________________________________________________________________

(5) You will measure the value of an equilibrium constant Keq: what does a large value of
Keq imply about the relative amount of reactant versus product at equilibrium?

_________________________________________________________________________________________________________

_________________________________________________________________________________________________________

Experiment 6 Equilibrium

6-1

Experiment 6

Equilibrium

Mathematical development

Measurement of the equilibrium constant Keq
When a system reaches equilibrium, the macroscopic observe-
ables (e.g., temperature, pressure, concentration, color, mass,
etc.) that characterize the system stop changing. The equilib-
rium state of the generic balanced reaction

a A + b B + + y Y + z Z

in which a mol of A react with b mol of B and so on to produce
y mol of Y, z mol of Z and so on, can be quantified by an equilib-
rium constant Keq such that

K eq =

y
z
[Y]eq
[Z]eq

[A]aeq[B]beq

where the quantities in brackets refer to the concentration in
moles per liter of each substance at equilibrium. Note that the
concentration of each species is exponentiated to a power
equal to the stoichiometric coefficient pertaining to that spe-
cies in the balanced reaction. The definition of the equilibrium
constant suggests that, when Keq >> 1, a lot of product forms
and little reactant remains when equilibrium is attained.
A system that both comes to equilibrium very quickly and
has a respectably large Keq is the reaction of ferric ion (Fe3+)
Experiment 6 Equilibrium

6-2

with thiocyanate ion (SCN) to produce ferric thiocyanate

(FeSCN2+):

Fe3+ + SCN FeSCN2+

The equilibrium constant of the reaction is given by

K eq =

[FeSCN2+ ]eq
[Fe3+ ]eq[SCN ]eq

(Eqn. 6-1)

In this experiment we will measure the value of this Keq.
Your lecture textbook presents a method of evaluating
equilibrium constants that involves constructing tables such as
Table 6-1. The table shows the concentrations of all species
that occur in the equilibrium-constant expression before and
after equilibrium is established. In terms of the quantities
listed in Table 6-1, the equilibrium constant in Eqn. 6-1 can be
expressed as

K eq =

[FeSCN2+ ]eq
[Fe

3+

]eq[SCN ]eq

[FeSCN2+ ]eq

(Eqn. 6-2)
[Fe3+ ] [FeSCN2+ ] [SCN ] [FeSCN2+ ]
i
eq
i
eq

The quantities [Fe3+]i and [SCN]i in Eqn. 6-2 are easy to
measure. Ascertaining the value of [FeSCN2+]eq is more in-
volved.
We will determine [FeSCN2+]eq by measuring the amount
of light that FeSCN2+ absorbs (i.e., its absorbance) at a wave-
length of 447 nm. According to the BeerLambert Law the con-
centration of a substance in solution is directly proportional to

Table 6-1 Equilibrium table pertaining to the reaction Fe3+ + SCN FeSCN2+
Species
Initial
Change
Concentration at equilibrium

concentration
2+
FeSCN
0
+x
x = [FeSCN2+]eq
Fe3+
[Fe3+]i
x
[Fe3+]i x = [Fe3+]i [FeSCN2+]eq = [Fe3+]eq
SCN
[SCN]i
x
[SCN]i x = [SCN]i [FeSCN2+]eq = [SCN]eq

Experiment 6 Equilibrium

6-3

its absorbance at an arbitrarily chosen wavelength. Applied to

the reaction we are to study,

A447 = 447[FeSCN2+]d

where A447 represents the absorbance of FeSCN2+ at 447 nm,
447 (the extinction coefficient of FeSCN2+ at 447 nm) is a
measure of how efficiently a substance absorbs light, and d is
the diameter of the cell (called a cuvet) in which the absor-
bance is measured.

Measurement of H and S
One of the most important relationships in chemical thermo-
dynamics is expressed by the equation


G = RT ln Keq
(Eqn. 6-3)

where G is the standard change in free energy, R is the gas
constant (8.31 J/(molK)), and T is the temperature in units of
degrees Kelvin. The value of G in Eqn. 6-3 indicates whether
a reaction is spontaneous (i.e., takes place without any inter-
vention on the part of the surroundings) at standard condi-
tions and at the temperature T. If G < 0, the reaction is spon-
taneous at standard conditions; if G > 0, the reaction is not
spontaneous at standard conditions. Combining Eqn. 6-3 with
the definition

G = H TS

where H represents the standard enthalpy change and S
the standard entropy change, gives after some manipulation

S H


(Eqn. 6-4)
ln K eq =

R
RT


Eqn. 6-4 indicates that ln Keq varies linearly with 1/T: a plot of
ln Keq as a function of 1/T results in a straight line whose slope
is equal to H/R and whose y-intercept is equal to S/R. We
will measure Keq at two temperatures and use Eqn. 6-4 to de-
termine H, S and G of the reaction.
Experiment 6 Equilibrium

6-4

Procedure
Do not contaminate the stock
solutions! Pour the approxi-
mate volumes of Fe(NO3)3(aq)
and KSCN(aq) stock solutions
that you need into appropri-
ately sized beakers, take the
beakers back to your lab
bench and continue working
with the solutions there. If you
take too much solution, do not
pour the excess back into the
reagent bottle: dispose of the
excess in a hazardous-waste
receptacle.

Preliminaries
Using tape or a glass-marking pen, label eight dry 150-mm test
tubes Solution 1, Solution 2, etc. In separate, dry beakers
obtain 80 mL of 0.200 M Fe(NO3)3(aq) stock solution and
80 mL of 0.0005 M KSCN(aq) stock solution.
Obtain three burettes and clamp them to a ring stand using
two burette holders. Prepare one burette to measure out
KSCN(aq) stock solution and fill it with that stock solution.
Prepare the second burette to measure out Fe(NO3)3(aq) stock
solution and fill it with that stock solution. Prepare the third
burette to measure out deionized water and fill it with water.
Discard all rinses in a hazardous-waste receptacle.
Make up in the labeled test tubes the eight solutions de-
scribed in Table 6-2. Measure all volumes using the appropri-
ate prepared burette. Do not use graduated cylinders!
theyre not accurate enough.
The solutions in the eight test tubes must be well mixed be-
fore continuing. Place a disposable dropper in each of the eight
test tubes. Draw solution into the dropper by suction and gen-
tly squirt the solution back out into the test tube. Repeat this
operation several times. Be careful not to lose any solution
over the side of the test tube. Inspect each solution after the
mixing process: if the color is not uniform, continue mixing.

Table 6-2 Initial make-up of the solutions required for the measurement of Keq
Solution
Volume of
Volume of
Volume of

0.0005 M KSCN(aq)
0.200 M Fe(NO3)3 (aq) H2O

[mL]
[mL]
[mL]
1
5.00
0.50
14.50
2
5.00
1.00
14.00
3
5.00
1.50
13.50
4
5.00
2.00
13.00
5
5.00
2.50
12.50
6
5.00
10.00
5.00
7
5.00
13.00
2.00
8
5.00
15.00
0.00
Experiment 6 Equilibrium

6-5


For each of the eight solutions you prepare, calculate
[Fe3+]i using the formula

3+

[Fe

(molarity of Fe3+ stock sol'n)(milliliters of Fe3+ stock sol'n)

]i =
20 mL

[Fe3+]i will vary from

(0.200)(0.50 mL)
[Fe3+ ]i =
= 0.005 M
20 mL


in Solution 1 to

(0.200)(15.00 mL)
[Fe3+ ]i =
= 0.15 M
20 mL


in Solution 8.
[SCN]i for each of the eight solutions is calculated using
the formula

(molarity of SCN stock sol'n)(milliliters of SCN stock sol'n)

[SCN ]i =
20 mL


but, because the volume of KSCN(aq) stock solution (5.00 mL)
added to each test tube is the same, [SCN]i in all eight solu-
tions is

(0.0005)(5.00 mL)
[SCN ]i =
= 1.25 104 M
20 mL


Obtain eight short (80 mm) test tubes. Using a glass-
marking pen, label each short test tube Solution 1, Solution
2, etc.; be sure to place the mark quite near the top of the
short test tube because marks down low on the short test
tubes body interfere with measurement. Using the droppers
for mixing in each big test tube and being careful to avoid
cross-contamination, fill each short test tube with the appro-
priate solution to within a centimeter of the top.

Experiment 6 Equilibrium

6-6

Using the Spectronic-200 spectrophotometer

You will use the Thermo Scientific Spectronic-200 spectropho-
tometer (see Figure 6-1) to measure the amount of light ab-
sorbed by FeSCN2+. Before taking measurements on actual
samples, the response of the Spectronic-200 must be calibrated
in a process called zeroing against the blank. The blank is a
solution identical to the actual sample whose absorbance you
will measure except that the blank does not contain any sub-
stances that absorb light at the wavelength of interest.
To zero the Spectronic-200 against the blank, follow these
steps:

Open the sample compartment. Make sure there are no sam-
ples in the sample holders. Close the sample compartment
tightly.
Turn the Spectronic-200 on; the power button is on the back.
Press ENTER; the instrument executes its initialization proto-
col.
When HOME MENU appears on screen, press DOWN ARROW to
select SPEC 20D+ EMULATION then press ENTER.
Twirl button until 445 nm appears on screen, then hold
down button and twirl to 447 nm.
Press RIGHT ARROW to select TRANSMITTANCE.
Open the sample compartment. Place a short (80 mm) test
tube filled with distilled water in the sample holder that is
not square. The test tube should fit tightly. Close the sample
compartment tightly.
Press 0.00 button. The instrument should read about 100%.
Remove the short test tube and press RIGHT ARROW to select
ABSORBANCE.

You record data in ABSORBANCE mode. Make sure that your
samples are in the sample holder that is not square and that
the sample compartment is closed tightly. At the end of the ex-
periment, remove your last sample and power the instrument
down.

Measurement of Keq at room temperature
Measure the absorbance of Solutions 18 at 447 nm. Remem-
ber to measure the diameter d of the short test tube in units of
Experiment 6 Equilibrium

6-7

centimeter and remember to record the air temperature T1. Do

not discard the short test tubes filled with Solutions 18: you
will need them later.

Measurement of Keq at low temperature
Prepare a 50:50 mixture of ice and water in a beaker large
enough to accommodate all eight short test tubes holding Solu-
tions 18. Place the eight short test tubes in the ice bath for at
least 20 min. During the 20-min interval, occasionally monitor
the temperature of the ice bath; refresh it by adding more ice
and pouring out water if the temperature rises above 6 C. At
the end of the 20-min interval, record in your notebook the
temperature T2 of the ice bath. You want the temperature to be
as low as possible, preferably below 6 C.
Measure the absorbance of Solutions 18 at 447 nm. The
short test tube will be wet when you withdraw it from the ice
bath: quickly wipe it dry with a clean paper towel before in-
serting the short test tube into the Spec-200: water will dam-
age the instrument.

Figure 6.1 The Spectronic-200

Experiment 6 Equilibrium

6-8

Data analysis

Evaluation of the Keqs
The BeerLambert Law says that the absorbance of FeSCN2+ is
proportional to the amount of FeSCN2+ present in solution. We
will assume that the solution that exhibits the maximum value
of A447 contains the maximum equilibrium concentration of
FeSCN2+. Given the one-to-one stoichiometry of the reaction

Fe3+ + SCN FeSCN2+

and given that Fe3+ is present in excess in all eight solutions,
we conclude that SCN is the limiting reagent. The maximum
possible equilibrium concentration of FeSCN2+ is thus

[FeSCN2+]eq,max = [SCN]i = 1.25 104 M

In other words, we assume that all of the SCN present initially
reacts in the solution that exhibits A447,max. Because the Beer
Lambert Law says that the absorbance of FeSCN2+ is directly
proportional to its concentration, for those solutions in which
A447 < A447,max

[FeSCN2+ ]eq

and

[FeSCN2+ ]eq,max

A447
A447,max

A447
[FeSCN2+ ]eq = [FeSCN2+ ]eq,max

A447,max

A447
= (1.25 104 M )

A447,max

(Eqn. 6-5)

When we apply Eqn. 6-5 to the equilibrium-constant
expres-

sion in Eqn. 6-2, we obtain a formula that allows us to deter-
mine the equilibrium constant of all eight solutions except
that solution in which A447,max is attained:
Experiment 6 Equilibrium

6-9


2+

K eq =

[FeSCN

]eq

[Fe3+ ]eq[SCN ]eq

[FeSCN2+ ]eq
[Fe3+ ] [FeSCN2+ ] [SCN ] [FeSCN2+ ]
i
eq
i
eq

A447
(1.25 104)

A447,max
=
3+

4 A447

4 A447
[Fe
]

(1.25

10
)
[SCN
]

(1.25

10
)
i
i

A

A

447,max
447,max

Because [SCN]i = 1.25 104 M in all eight solutions, the ex-
pression for Keq simplifies to

A447
A

447,max
K eq =

(Eqn. 6-6)

A
3+
4
447
447
[Fe ]i (1.25 10 )
1 A

A
447,max 447,max

Evaluation of H and S
As was pointed out in the Mathematical development section,
H and S of the reaction can be determined by graphical
methods. To expedite the procedure, we choose instead to
evaluate these thermodynamic quantities using the following
formulas derived from the pointslope equation of a straight
line:

RT T K eq,T1
H = 1 2 ln

T1 T2 K eq,T2


R
S =
T1 ln K eq,T1 T2 ln K eq,T2
T

T
1
2


In these formulas, T1 corresponds to your measurement of
room temperature in degrees Kelvin; T2 corresponds to the
temperature in degrees Kelvin of the solutions after cooling in
the ice bath for at least 20 min; Keq,T1 represents the value of
Keq at T1; Keq,T2 represents the value of Keq at T2; R is the uni-

Experiment 6 Equilibrium

6-10

versal gas constant (8.31 J/(molK)). Recall that degrees Kel-

vin = degrees Celsius + 273.15.

Experiment 6 Equilibrium

6-11

Name___________________________________________________________Lab Day__________Lab Time_________

Experiment 6 Equilibrium

Lab report form
Page 1

(I) Report the data items and calculated quantities required to determine the equilibrium
constant Keq,T1 at T1 (room temperature) from Eqn. 6-6. Calculate [FeSCN2+]eq from Eqn. 6-
5; calculate 447 from the BeerLambert Law

A447 = 447[FeSCN2+]eq d

Draw a prominent arrow () in the right-hand margin to indicate the solution that exhib-
ited A447,max; Keq,T1 cannot be calculated for that solution. Calculate the mean, standard
deviation of the mean, and the 95% confidence interval about the mean of 447 and Keq,T1.

T1 = ________________________________________________________________________________________________ C

d = _________________________________________________________________________________________________ cm

Soln [Fe3+]i
A447
[FeSCN2+]eq
447
Keq,T1
[mol/L]
[mol/L]
[units?]
[units?]
1





2

mean

standard deviation

95% confidence interval

Experiment 6 Equilibrium

6-12

Name___________________________________________________________Lab Day__________Lab Time_________

Experiment 6 Equilibrium

Lab report form
Page 2

(II) Report the data items and calculated quantities required to determine the equilibrium
constant Keq,T2 at T2 (the temperature of the cold bath) from Eqn. 6-6. Calculate
[FeSCN2+]eq from Eqn. 6-5; calculate 447 from the BeerLambert Law

A447 = 447[FeSCN2+]eq d

Draw a prominent arrow () in the right-hand margin to indicate the solution that exhib-
ited A447,max; Keq,T2 cannot be calculated for that solution. Calculate the mean, standard
deviation of the mean, and the 95% confidence interval about the mean of 447 and Keq,T2.

T2 = ________________________________________________________________________________________________ C

d = _________________________________________________________________________________________________ cm

Soln [Fe3+]i
A447
[FeSCN2+]eq
447
Keq,T2
[mol/L]
[mol/L]
[units?]
[units?]
1





2

mean

standard deviation

95% confidence interval

Experiment 6 Equilibrium

6-13

Name___________________________________________________________Lab Day__________Lab Time_________

Experiment 6 Equilibrium

Lab report form
Page 3

(III) On separate sheets present plots of the absorbance data as a function of [Fe3+]i col-
lected during the runs at T1 and T2. Include the origin {0,0} as a data point. Prepare a sepa-
rate plot for each run. Give each plot a truly informative title (i.e., dont just call it Plot 1),
label the axes, and include appropriate units and divisions of those axes. Do not submit
small plots: use a whole sheet of paper. Scale the horizontal and vertical axes so that the
data points occupy most of the area of the plot.

(IV.A) Using the formulas

RT T K eq,T1
R
H = 1 2 ln
S =
T1 ln K eq,T1 T2 ln K eq,T2
and

T1 T2
T1 T2 K eq,T2






evaluate H and S of the reaction. Use the mean values of Keq,T1 and Keq,T2 from the ta-
bles in (I) and (II), the Kelvin temperatures T1 and T2 (degrees Kelvin = degrees Celsius +
273.15), R = 0.00831 kJ/(molK) in the calculation of H and R = 8.31 J/(molK) in the cal-
culation of S.

T1
T1
T2
T2
Keq,T1
Keq,T2
H
S
[ C] [K]
[ C] [K]
[units?]
[units?]
[kJ/mol]
[J/(molK)]

(IV.B) Using the definition G = H TS, where G is the standard free energy change
and T is in units of degree Kelvin, evaluate G in units of kilojoule per mole at T1 and T2.
Pay attention to units!

GT1 = _______________________________________________________________________________________ kJ/mol


GT2 = _______________________________________________________________________________________ kJ/mol

Experiment 6 Equilibrium

6-14

Name___________________________________________________________Lab Day__________Lab Time_________

Experiment 6 Equilibrium

Lab report form
Page 4

Post-lab questions
(1.a) What is the percent yield of FeSCN2+ at equilibrium in the solution that exhibited
A447,max at room temperature?




(1.b) What is the percent yield of FeSCN2+ at equilibrium at room temperature in Solu-
tion 2? Show the calculation.







(2.a) Absorbance A has no units; however, the extinction coefficient does have units. What
are the units of ? Show how you arrived at your answer.







(2.b) Although equilibrium constants are usually reported without units, in fact they do
have units. What are the units of the Keq measured in this experiment? Show how you ar-
rived at your answer.

Experiment 6 Equilibrium

6-15

Name___________________________________________________________Lab Day__________Lab Time_________

Experiment 6 Equilibrium

Lab report form
Page 5

(3) Do your data indicate that the reaction studied in this experiment releases heat or ab-
sorbs heat under the experimental conditions you employed? Explain your answer.









(4) You should obtain a value of S in units of joule per moledegree Kelvin that is close to
zero. Interpret the algebraic sign (positive or negative) of the S value you reported in
(IV.A).








(5) Is the reaction studied in this experiment more spontaneous or less spontaneous at low
temperature? Explain your answer.

Experiment 6 Equilibrium

6-16

Name___________________________________________________________Lab Day__________Lab Time_________

Experiment 6 Equilibrium

Lab report form
Page 6

(5) The plot of your room-temperature data submitted in (III) probably resembles the
curve marked by circles (Actual data) in the figure below. But suppose the plot of your
room-temperature data looked like the curve marked by squares (Hypothetical data).
What would the hypothetical data imply about the magnitude of Keq? What would the hy-
pothetical data imply about the percent yield of the reaction?

Experiment 6 Equilibrium

6-17