Doloso, Mon Averille T. Date Performed: Feb.

22, 2011

Date Submitted: March 3, 2011

Kinetics of the Oxidation of Ascorbic Acid by Hexacyanoferrate (III) Ion

Abstract

Introduction

Dehydroascorbic acid is an oxidized form of ascorbic acid. Counting on the type of the
oxidizing agent, and the acidity of the medium, preferentially the ascorbic acid (H2Asc), the
ascorbate anion (HAsc-), or the ascorbate dianion (Asc2-) is the kinetically significant species.
Among the oxidizing agents which have been studied are metal-ion complexes, excited states of
metal complexes, and phenothiazene radicals. This particular experiment covers the oxidation
of ascorbic acid (C6H8O6) by hexacyanoferrate (III) ion to dehydroascorbic acid (C6H6O6).

Mathematical variables controlling the oxidation of ascorbic acid by hexacyanoferrate

(III) ion can be obtained experimentally by checking the disappearance of yellow, [Fe(CN) 6]3- in
the reaction mixture. Two moles of [Fe (CN) 6]3- must react to oxidize one unit of ascorbic acid to
dehydroascorbic acid. According to chemical literature, Fe(III) complex absorbs in the 420 nm
bounds, and neither the reduced Fe(II) complex nor any derivatives and by-products of ascorbic
acid absorb at 420 nm. Thus, the absorbance at 420, acquired by UV-Vis spectrophotometer
corresponds to the concentration of [Fe (CN) 6]3- alone.

The simplified rate law and the equivalent reaction mechanism indicate a second order,
with the electron transfer of ascorbate to hexacyanoferrate (III) being the rate determining step.
Since both species are charged the ionic strength I, can be affected and will eventually change
the reaction rate. This event is called the primary salt kinetic effect. To effectively present the
effect of varying the ionic strength on the observed rate constant, inputting the charges of
reactants- the Debye-Huckel equation was incorporated in data analysis.

Besides that change in reaction rate because of variation in ionic strength, the rate is
also affected by fluctuations in temperature. Its effects can be clearly evaluated by carrying out
an Arrhenius plot of ln k0 vs. 1/T. In addition to this, Arrhenius plot also allows calculation of
activation enery, Ea for the chemical reaction. There also many constituents in the mixture for
the oxidation of ascorbic acid to dehydroascorbate by hexacyanoferrate (III) ion. For instance,
NaNO3 in the solution is the sole source of ions. The ions present act to break the electrostatic
repulsion felt by the ascorbate and [Fe (CN) 6]3-. The nitric acid acts as a buffer keeping the
reaction conditions at same pH. As of convention, EDTA was used to bind any metal impurities
present in the reaction mixture that could affect the observed absorbances and the reaction
rate, of course. EDTA, technically speaking will not chelate the iron in [Fe (CN) 6]3 because it is
strongly complexed with CN- but will chelate the likes of Ca2+.

Methodology

Solution Preparation

As prerequisite to absorbance readings, five solutions were prepared. Solution A was

made by securing a 1.0 x10-3 M K3[Fe(CN)6] solution in a 250-ml volumetric flask. This solution
was particularly used as a stock solution both for dilutions to confirm Beer’s Law and evaluate
molar absorptivity at lambda max. While solution B was prepared by adding solid NaNO3 to a 50
ml volumetric flask in the appropriate weight to obtain a concentration of 0.02 M in NaNO 3;
followed by dilution to mark with solution A. Also Solutions C, D, and E were prepared by adding
the necessary amount of solid NaNO3 to a 25-ml volumetric flask so as to obtain a concentration
of 0.05M, 0.1 M, and 0.20 M respectively.

Beer-Lambert Analysis

First and foremost, ½, 1/3, ¼, and 1/5 dilutions of solution A were secured to obtain 5
solutions of K3Fe (CN) 6. Next, initialize and warm-up the UV-visible spectrophotometer. The
spectrum was scanned for each five solutions of K3Fe (CN) 6 from 360-550 nm. Exact value of
lambda max (~420nm) was then determined. Later, the absorbance of each of the five solutions
at lambda max was recorded.

Kinetics Run

At this stage, the UV-visible spectrophotometer was set to “Kinetics” mode and a
background reading was made by using a cell filled with distilled water. 3ml of one of the K3Fe
(CN) 6-NaNO3 solutions was then pipette out into an E-flask and 3 ml of the ascorbic acid-HNO3-
EDTA solution. The solution was then swirled for a few seconds and poured into a UV-vis cell.
Later, walls of cuvette were clean and dried and placed in the spectrophotometer. Next,
absorbance was recorded at 1 minute intervals for 20 minutes. Temperature of the thermostated
cell was recorded. Following, that the kinetic experiment was performed for all other solutions at
same temperature as that of the previous step. Solution B was then selected and was run-
through at same procedure at different temperatures (30°C, 40°c, and 50°C).

Results and Discussion

Table 1. Data for Beer-Lambert Equation

= 419.52
max

[K3Fe(CN)6], M Absorbance
0.001 1.045
0.0005 0.549
0.0003333 0.373
0.00025 0.259
0.0002 0.204

ε = 1044.654171
Table 2. Ionic strengths of solutions B-E

Solution Molarity Ionic Strength

B 0.02 0.029
C 0.05 0.059
D 0.1 0.109
E 0.2 0.209
 B(45
B(27.7) B(30) B(40) ) B(50) C D E
0.000524576 0.000506 0.000481 0 0.000529362 0.000508 0.000483 0.000386
0.000518832 0.000501 0.000474 #DIV/0! 0.000518832 0.000512 0.000466 0.000388
0.000518832 0.000508 0.000463 #DIV/0! 0.000503516 0.000507 0.000461 0.000374
0.000509259 0.000503 0.000456 #DIV/0! 0.000491072 0.000496 0.000458 0.000367
0.000504473 0.000495 0.000446 #DIV/0! 0.000480542 0.000492 0.000453 0.00036
0.000497772 0.000489 0.000438 #DIV/0! 0.000470012 0.000491 0.000447 0.000354
0.000492029 0.000483 0.000432 #DIV/0! 0.000461397 0.000484 0.000441 0.000349
0.0004882 0.000478 0.000424 #DIV/0! 0.000453739 0.000479 0.000436 0.000345
0.000486285 0.000473 0.000418 #DIV/0! 0.000445123 0.000473 0.00043 0.000338
0.000483414 0.000467 0.000413 #DIV/0! 0.000437465 0.000466 0.000425 0.000334
0.000479585 0.000463 0.000407 #DIV/0! 0.000429807 0.000462 0.00042 0.000328
0.000476713 0.000458 0.000415 0.000325
0.000472884 0.000454 0.000412 0.000322
0.000469055 0.00045 0.000407 0.000317
0.000465226 0.000446 0.000403 0.000314
0.000463311 0.000443 0.000399 0.00031
0.000459482 0.000438 0.000395 0.000306
0.00045661 0.000435 0.000392 0.000303
0.000453739 0.000431 0.000388 0.0003
0.00044991 0.000428 0.000386 0.000296
0.000446081 0.000425 0.000382 0.000293

Hexacyanoferrate (III) ion concentration for each solution at each time t