The Second-Order Reaction of Hexacyanoferrate (III) Ion, Fe(CN) 6 with Ascorbic Acid,

C6H8O6
Blaine Marceau
Lab Partner: Angela Tipton

Abstract
While investigating the absorbance of different mixtures of
hexacyanoferrate (III) and ascorbic acid, and the reduction of
hexacyanoferrate (III) to hexacyanoferrate (II) by ascorbic acid, it was
discovered that higher concentrations lead to higher absorbances and lower
reaction rates.

Introduction
The purpose of this lab was to introduce the concept of first-order
dependency of a second order reaction.3 This lab does so by looking at the
intermediates formed by both hexacyanoferrate and ascorbic acid.3 We also
look at the effect of concentration on both the rate of the reaction and the
absorbance of the reaction.

Experimental
To start this lab, prepare four 1 X 10-3 M solutions of Potassium
Hexacyanoferrate (K3Fe(CN)6), and have varying concentrations of Sodium
Nitrate (NaNO3). The concentrations should be as follows, 0.025 M, 0.05M,
0.1M, and 0.2M.
When this part is done, you then need to make 500 mL of Ascorbic acid
using 0.001 M Nitric Acid containing 0.001% EDTA dehydrate as the solvent.
Note that Ascorbic acid solutions must be made daily as it is highly
hydroscopic.
Once all of the solutions are made, the spectrophotometer must be
turned on and allowed to heat up. The solutions can be measured at room
temperature. Once the spectrophotometer is warmed up and ready to go,
pipette 25 mL of the ascorbic acid into four 250 mL Erlenmeyer flasks each,
then one 25 mL aliquot of each one of the hexacyanoferrate and sodium
nitrate into a 100mL beaker. You will then mix the two in the 100 mL beaker,
swirl shortly and put some in a cuvette, then run in the spectrophotometer,
after running a blank. Complete this for all four concentrations, then save
your data, export into an excel file and make a graph. These procedures
were taken from the book Physical Chemistry: Methods, Techniques,
Experiments by Rodney J. Sime with some slight changes.

Results
Run 2
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0.00E+00
-0.05

5.00E+02

1.00E+03

1.50E+03

2.00E+03

This one overarching graph contains four separate graphs within itself. Each
exponential decay looking graph is the graph of one of the mixtures. It starts
with the highest concentration and moves down to the lowest, and has a
decreasing starting absorbance. For the first one, its initial absorbance is
0.365. The initial absorbance for the second graph is down to 0.239. The
initial absorbance for the third graph is 0.200. For the final graph, the initial
absorbance is 0.122.
For the rate of reaction, the final time is subtracted from the initial time. For
the highest concentration the reaction time was

Error Analysis
25 mL Pipette = 0.02mL per transfer= 0.08% per transfer * 8 total
transfers= 0.64% total percent from transfers
Another big error came from the temperature of the reaction. Because the
spectrophotometer was not thermostatted, and we did not have the ability to
let the solutions and the spectrophotometer sit together overnight, we
simply had to let the reactions run at the temperature of the room, which
was five degrees Celsius lower than the recommended settings.

Discussion

During the reaction, hexacyanoferrate is reduced by ascorbic acid by

the formation of an ascorbate anion.3 The intermediate is then attacked by
the hexacyanoferrate.3 The Debye-Huckel theory states that this happens at
a rate according to its concentration. It happens faster at a low concentration
because there is less intermediate that can be formed, and therefore the
reaction is finished faster. Because the reaction is finished faster, and the
hexacyanoferrate is the only product that holds any color, once the reaction
is complete, the absorbance will quit reading.1

Conclusion
This lab has showed that the rate of the reaction for the reduction of
hexacyanoferrate (III) by ascorbic acid is largely dependent on the
concentration. Low concentrations will produce a reaction rate that is almost
immeasurable, while higher concentrations slow the reaction down to a point
where you can measure it much easier.

References
1) Sime, Rodney J. "Computerized Data Acquisition of a Second-Order Reaction." Physical
Chemistry: Methods, Techniques, and Experiments. Philadelphia: Saunders College Pub.,
1990. 628-40. Print.
2) The oxidation of ascorbic acid by hexacyanoferrate(III) ion in acidic aqueous
media: Application of the Marcus cross relation. (n.d.). Retrieved March 07, 2016,
from http://pubs.acs.org/doi/pdf/10.1021/ed065p176
3) Kinetics of the reduction of hexacyanoferrate(III) by ascorbic acid. (n.d.). Retrieved
March 07, 2016, from http://pubs.acs.org/doi/pdf/10.1021/j100726a058
4) Ionic Strength Effect on the Rate of Reduction of Hexacyanoferrate(III) by Ascorbic
Acid: A Flow Injection Kinetic Experiment. (n.d.). Retrieved March 07, 2016, from
http://pubs.acs.org/doi/pdf/10.1021/ed074p560