1212-Exp 4

Valdosta State University
Experiment 4
Determination of an
Equilibrium Constant
Purpose
Determine the equilibrium constant for a reaction.

Background
Consider the reaction:
NO
2
+ CO D NO + CO
2

Forward reaction:
NO
2
+ CO NO + CO
2
rate
1
=k
1
[NO
2
][CO]

Reverse reaction
NO + CO
2
NO
2
+ CO rate
-1
=k
-1
[NO][CO
2
]

Background
NO
2
+ CO D NO + CO
2

Since the concentrations are constant, the rates are
equal.
rate
1
= rate
-1

k
1
[NO
2
][CO] = k
-1
[NO][CO
2
]

Background
NO
2
+ CO D NO + CO
2
| || |
| || |
2
2
1
1
CO NO
CO NO
k
k
=

Background
NO
2
+ CO D NO + CO
2
| || |
| || |
2
2
CO NO
CO NO
K
c
=
K
c
= equilibrium constant
Background
Law of Mass Action
When a reversible reaction has attained equilibrium at a
given temperature, the reaction quotient is a constant
mA + nB D xC + yD
Background
Law of Mass Action
When a reversible reaction has attained equilibrium at a
given temperature, the reaction quotient is a constant
mA + nB D xC + yD
| | | |
| | | |
n m
y x
c
B A
D C
K =
Background
In this experiment:
Fe
3+
+ SCN
-
D FeSCN
2+

The experimental problem is determining the
equilibrium concentrations.
Because the product is a deep red, Beers law can be
used to relate absorbance to concentration.
This will require the construction of a calibration curve.

Background
Calibration Curve
A graph that relates one quantity to another. In this
case, absorbance and [FeSCN
2+
].
Background
Calibration Curve
For a calibration curve to work the absorbance for a
given concentration of [FeSCN
2+
] must be known.
In an equilibrium reaction this means the equilibrium
must be forced completely to the right.
In this experiment this is accomplished by using a huge
excess of [Fe
3+
].
[SCN
-
] = [FeSCN
2+
]
Background
Solution # Volume of NaSCN
pipeted in 0.25 M
HNO
3

Volume of 0.200 M
Fe(NO
3
)
3
in 0.25 M
HNO
3

Volume of 0.25
M HNO
3

1 (blank) 0.00 mL 15 mL dilute to 50.0 mL
2 1.00 mL 15 mL dilute to 50.0 mL
Background
Determining Concentration [SCN
-
] for calibration curve
(Part A)
( )( )
M 10 68 . 7 M
) mL 00 . 50 ( M mL 00 . 1 M 00384 . 0
V M V M
5
d
d
d d c c
=
=
=
Background
Assumption
[SCN
-
] is much smaller than [Fe
3+
]; therefore,
[FeSCN
2+
] = [SCN
-
]
Background Sample Table for Part A
Conc.
Fe(NO
3
)
3
0.2
Conc.
NaSCN 0.00384
Solution 1 2 3 4 5 6
ml NaSCN 0 1 2 3 4 5
[NaSCN] 0 0.0000768 0.000154 0.000230 0.000307 0.000384
[FeSCN
2+
] 0 0.0000768 0.000154 0.000230 0.000307 0.000384
%T 100.0 55.5 28.4 14.6 7.8 4.0
A 0.000 0.256 0.547 0.836 1.108 1.398
Background
Frank N. Stei n - Exp. 4 - Cal i brati on Curve
y = 3660.7x - 0.0119
R
2
= 0.9997
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0 0.00005 0.0001 0.00015 0.0002 0.00025 0.0003 0.00035 0.0004 0.00045
Concentrati on (mol / L)
A
b
s
o
r
b
a
n
c
e
Background
The calibration table can now be used to determine the
[FeSCN
2+
] concentration.
If the following reagents are use:
1.00 mL 0.00200M NaSCN
5.00 mL 0.00200M Fe(NO
3
)
3

4.00 mL 0.25M HNO
3
The resulting solutions %T is 61.6%
Background
Converting %T to A
|
.
|
\
|
=
T %
100
log A
Background
Converting %T to A
210 . 0
6 . 61
100
log A
T %
100
log A
=
|
.
|
\
|
=
|
.
|
\
|
=
Background
Now use the graph to determine the [FeSCN
2+
].
Frank N. Stei n - Exp. 4 - Cal i brati on Curve
y = 3660.7x - 0.0119
R
2
= 0.9997
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0 0.00005 0.0001 0.00015 0.0002 0.00025 0.0003 0.00035 0.0004 0.00045
Concentrati on (mol / L)
A
b
s
o
r
b
a
n
c
e
Background
2+
].
Alternatively, use the equation of the line to determine
the concentration.
Background
2+
].
Alternatively, use the equation of the line to determine
the concentration.
M 10 06 . 6
7 . 3660
0119 . 0 210 . 0
] FeSCN [
0119 . 0 ]) FeSCN ([ 7 . 3660 210 . 0
0119 . 0 ]) FeSCN ([ 7 . 3660 A
b mx y
5
2
2
2
+
+
+
=
+
=
=
=
+ =
Background Sample Table for Part B
Fe(NO
3
) 0.002
NaSCN 0.00384
Solution # 7 8 9 10 11
mL Fe(NO
3
)
3
5 5 5 5 5
mL NaSCN 1 2 3 4 5
%T 61.6 40 25.2 17 11.5
A 0.210 0.398 0.599 0.770 0.939
[FeSCN
2+
] 6.06 x 10
-5
1.12 x 10
-4
1.67 x 10
-4
2.14 x 10
-4
2.60 x 10
-4
Background
From the equilibrium concentration of FeSCN
2+
, initial
concentrations of Fe
3+
and SCN
-
, and stoichiometry, the
equilibrium concentrations of Fe
3+
and SCN
-
can be
determined.
One way of presenting these data is to use an ICE
(Initial, Change, Equilibrium) table. Remember that ICE
tables are cool, and if you are having trouble with an ICE
table, just chill.
Background
Fe
3+
SCN
-
FeSCN
2+
Initial
Change
Equilibrium 0.0000606
The equilibrium concentration of FeSCN
2+
is determined
using the slope intercept equation.

Background
Fe
3+
SCN
-
FeSCN
2+
Initial 0
Change
Since no FeSCN
2+
was added to the solution, the initial
concentration of FeSCN
2+
is assumed to be zero.
Background
Fe
3+
SCN
-
FeSCN
2+
Initial 0
Change -0.0000606 -0.0000606 +0.0000606
Using the equilibrium equation, it can be determined that
for every molecule of FeSCN
2+
made, one Fe
3+
and one
SCN
-
are consumed.
Fe
3+
+ SCN
-
D FeSCN
2+
Background
Fe
3+
SCN
-
FeSCN
2+
Initial 0.00100 0.000384 0
Change -0.0000606 -0.0000606 +0.0000606
Equilibrium 0.0009394 0.0003234 0.0000606
The initial concentrations of Fe
3+
and SCN
-
can be
determined, using the dilution equation and noting the
total volume of the final solution.
Background
The equilibrium concentrations can now be used to
determine K
c
.
| |
| || |
1
3
2
c
M 199
0003234 . 0 0009394 . 0
0000606 . 0
SCN Fe
FeSCN
K
+
+
=
=
=
Background
[Fe(NO
3
)
3
]

.00200
[NaSCN] 0.00384
Solution # 7 8 9 10 11
mL Fe(NO
3
)
3
5 5 5 5 5
mL NaSCN 1 2 3 4 5
%T 61.6 40 25.2 17 11.5
A 0.210 0.398 0.599 0.770 0.939
[FeSCN
2+
] 0.0000606 0.000112 0.000167 0.000214 0.000260
[Fe
3+
] 0.0009394 0.000888 0.000833 0.000786 0.000740
[SCN
-
] 0.000303 0.000656 0.000985 0.001332 0.001660
K
eq
199 192 204 206 212
Average K
eq
203
Std. Dev. 7
Procedure Experiment 4
- For this experiment, work in pairs. If you do not like
working in pairs, then you may work in groups of two.
Technique - Colorimeter
Experimental Setup
1. Plug the DIN plug of the colorimeter into The GLX adapter. The function
of the GLX unit is to power the colorimeter. No laptop computer is
required.
2. Fill a cuvet almost full with the standard Solution #1 (your blank
solution). Wipe the cuvet windows with a Kimwipe.
3. Place the cuvet into the colorimeter with the ribbed side facing you.
Close the lid.
4. Simultaneously press the Select and the Start/Stop buttons on the
colorimeter.
5. Because your reference solution is already in the colorimeter, press
Select on the colorimeter.
6. Wait until the colorimeter displays that calibration is complete. Remove
the blank solution.
7. Press Select on the colorimeter. Keep pressing Select until the
display shows Blue 460 nm.
Experimental Setup Calibration Curve Data
1. To take a reading, first rinse the cuvet with a small portion of Solution
#2. Then fill the cuvet with Solution # 2. Place the cuvet in the
colorimeter with the ribbed side facing you. Close the lid on the
colorimeter.
2. Press Start on the colorimeter. Record the % T reading on your report
sheet.
3. To measure the % T for your other solutions, remove the previous cuvet
from the colorimeter and dispose of the contents. Rinse the cuvet with
about 1 mL of the next solution then fill the cuvet. Close the colorimeter
lid. Record the % T reading on your report sheet. Since you have
pressed Start in the previous step, it is not necessary to press Start
again.

Experimental Setup Equilibrium Constant
1. Now measure % T for Solutions 7 11. Rinse a cuvet with
approximately 1 mL of solution # 7. Then fill the cuvet and place it in the
colorimeter. Record the % T reading on your report sheet. Repeat this
procedure for the remaining solutions.
Technique Volumetric Flask
A container which is calibrated to contain an accurate amount of
liquid.
These flasks have a scribed mark on the neck, when filled to this
mark, the volume of the substance is known to 0.01mL.
liquid.
liquid.
To make an accurate solution, the bottom of the meniscus of the
solution must line-up with the scribe mark.
liquid.
To make an accurate solution, the bottom of the meniscus of the
solution must line-up with the scribe mark.
To make a calibration standard, add the following to a volumetric flask:
1. NaSCN solution (as per table 4.1)
2. Fe(NO
3
)
3
solution (as per table 4.1)
3. HNO
3
solution of make 50mL
Add the last 1 2 mL of acid with a clean dropper until the
bottom of the meniscus lines-up with the scribe mark on the
flask.
4. Mix the solution by capping and slowly inverting the flask
several times.
5. The use of the volumetric flask permits the final volume to be
measured more precisely.
Technique Calibration Solutions
Technique Equilibrium Solutions
To make an equilibrium solution, add the following to a flask:
1. NaSCN solution (as per table 4.2)
2. Fe(NO
3
)
3
3. HNO
3
4. Mix the solution by swirling the flask.
Technique Equilibrium Solutions
Technique Volumetric Pipet
A container which is calibrated to deliver an accurate amount of
liquid.
These pipets have a scribed mark on the neck, when filled to this
A container which is calibrated to deliver an accurate amount of
liquid.
These pipets have a scribed mark on the neck, when filled to this
Hold the pipete about 8 cm below the
top with one hand. Then with your
other hand squeeze the bulb and
touch the opening to the top of the
pipete.
Insert no more than one-half cm of
the pipete into the bulb.
The rubber bulb should easily fall off
if released.
Place the tip into the colored liquid
and slowly release the pressure on
the bulb.
The liquid will be drawn up into the
pipete and will form a curved
surface against the glass.
This surface is called the meniscus.
Pull the bottom of the meniscus up
about 1 cm past the desired level.
Then quickly, but carefully, remove the
bulb as you slip your free index finger
over the hole at the top.
Never use your thumb -- your index
finger will allow better control and will also
enable you to hold other items with your
free fingers when necessary.
Then with your finger still on the end of
the pipete, gently lift the pipete out of the
solution.
Then raise your finger just enough to allow the
bottom of the meniscus to line up with the
desired graduation mark. You should observe
the meniscus at eye-level while doing this.
When the meniscus is at the desired level, touch
the tip of the pipete to the inside of the container
holding the colored water, to remove any drops
of liquid on the end of the pipete. Now, there is
precisely (0.354 + 0.001) ml of colored water in
your pipete.
Keeping your finger on the end of the
pipete, gently move it to the flask.
Touch the tip to the inside of the
container, lift your finger off the end
and allow the liquid to drain out of the
pipete.
Hold the pipete in this position for a
few seconds after it stops draining.
Safety
If any 0.25 M HNO
3
contacts your skin, wash the
affected area with water for two minutes. If any acid
contacts your eyes, wash them out with water for ten
minutes. Seek medical attention.
Note that all solutions in this experiment contain 0.25 M
HNO
3
.
Waste Disposal
All wastes from this experiment can be flushed down the
drain with plenty of running water.

1212-Exp 4

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