COULOMETRIC TITRATION OF ASCORBIC ACID

WITH ELECTROGENERATED IODINE

Aguilar, J., Antazo, F., Lumayag, L., Naguit, P., Ragos, E.
Department of Chemistry, College of Science
University of Santo Tomas

ABSTRACT
Coulometry is an electroanalytical method used to measure the quantity of electricity
used in either to transform the substance in a redox reaction or to produce a reactant in an
analytical reaction and is based by on the Faraday’s Law. The experiment aims to calculate the
amount of ascorbic acid using coulometric titration with electrogenerated iodine. A mixture of
NaNO3, KI, starch indicator, and the aliquot of the ascorbic sample with a red carbon electrode
in the solution attached and a crucible also containing the NaNO3 and KI solution but with the
black carbon electrode inside the solution was titrated together until it the solution reached a
purple color. The time on which the reaction is completed is recorded and is marked as the end
point of the titration. Based on the time recorded, the amount of ascorbic acid was calculated.
Results show that an average mol of Vitamin C or ascorbic acid was computed to be 1.918x10 -5
mol with a percentage error of 35.17%. Possible sources of error are personal errors and
instrumental error.

INTRODUCTION F is the Faraday number (96.500 coulombs

Coulometry is the universal term
referring to an electroanalytical method
which consists in the measurement of the
quantity of electricity used either to
transform the substance to be determined in
a redox reaction or to produce a reactant of
an analytical reaction. Thus the species to
be determined reacts either at one of the
electrodes or with a reagent produced by
electrolysis. The second method is also
referred to as coulometric titration [1].
This method is based on Faraday’s
second law:
where m is the amount of substance
transformed in the electrolysis, M is the
molecular weight of substance, n is the
number of electrons involved in the
electrode reaction, Q is the amount of
electricity used in the reaction in coulombs,
= 26.8 A hours) [1].
Iodine is very useful in titration methods,
such as Iodometric and Iodimetric titration.
These methods are used to determine the
concentration of vitamin-C, sodium
thiosulphate, amount of copper in super
conductor etc [3]. Vitamin C is also called
ascorbic acid and antioxidant. It is titrated in
a solution with electrogenerated iodine
(Equation 1) [1]. The endpoint of the titration
is indicated by purple or blue coloration due
to the reaction of excess iodine with a
starch indicator. Ascorbic easily oxidize to
dehydroascorbic acid. Thus in the
iodometric titration of ascorbic acid, the
ascorbic acid is quantitatively oxidized by
iodine (Figure 1) [1] [2] [3].
2 I-→ I2 + 2e- (Equation 1)

Figure 1. The reaction mechanism for the
oxidation of iodine
A basic requirement in coulometric
analysis consists in selecting an electrode
reaction which takes place 100% current
efficiency as the amount of electricity is
employed to calculate the quantity of the
substance to be determined. Current
efficiency can be affected by interfering
reactions, e.g., the solvent or the supporting
electrolyte can react at the electrode, the
electrode material can react with some
components of the solution, or a secondary
reaction can take place involving the
product of electrolysis [1].
By a filtering crucible covered with
glass frit, the cathode is isolated from the
test solution to maintain 100% generating
efficiency. Using Faraday’s law, the amount
of ascorbic acid was calculated [1].
METHODOLOGY
A. Materials and reagents
In performing the experiment, 0.5g Vitamin
C was crushed and diluted to 100 mL then
filtered before titrating. Apart from this, a
mixture of 0.1 M NaNO3/ 0.1 M KI and 0.5
% starch indicator was freshly prepared.
B. Coulometric titration of the sample
A mixture of 75 mL of 0.1 M NaNO3/ 0.1 M
KI, 5mL starch indicator, and 0.5 mL aliquot
of the ascorbic acid sample was placed in a
beaker. Inside the beaker, a magnetic stirrer
was used and above it is a filtering crucible
that also contains 10 mL of 0.1 M NaNO3/
0.1 M KI mixture. The Black carbon
electrode was inserted into the filtering
crucible while the red carbon electrode was
in the solution of the beaker. It is important
that the stirring is begun before switching on
the apparatus. After observing a color
change, the time at which the solution turns
completely purple was noted marking as the
endpoint of the titration. The duration of the
titration was determined. Multiple trials are
highly recommended for more accurate and
precise results.
RESULTS AND DISCUSSION
Coulometric titration is a method in
which the titrating agent is generated in a
solution electrochemically in the titration
cell. Constant current is applied and
monitored as a function of time. This kind of
titration uses a current system to accurately
quantify the concentration of the species of
interest.
Table 1. Time elapsed when the violet color
shows each trials
TRIAL TIME (min)
1 6:55
2 9:44
3 6:29
4 7:33
Table 2. Mean value of the time elapsed
MEAN 7:40 min or 460 s
The iodine is generated at the
anode. A titration cell is consisted of two
parts: an anodic and cathodic compartment.
As the iodine is added during
titration, the ascorbic acid is oxidized to
dehydroascorbic acid, while the iodine is
reduced to iodide ions.
𝑎𝑠𝑐𝑜𝑟𝑏𝑖𝑐 𝑎𝑐𝑖𝑑 + 𝐼2 → 2 𝐼 − + 𝑑𝑒ℎ𝑦𝑑𝑟𝑜𝑎𝑠𝑐𝑜𝑟𝑏𝑖𝑐 𝑎𝑐𝑖𝑑
Due to this reaction, the iodine
formed is immediately reduced to iodide as
long as there is any ascorbic acid present.
Once all the ascorbic acid has been
oxidised, the excess iodine is free to react
with the starch indicator, forming the blue-
black starch-iodine complex. This is marks
the endpoint of the titration. The time is
measured until the blue-violet color spreads
throughout the solution.
Electrodes have large surface areas
so the current density is low.
The values were tested using the Q-
test due to the outlier, 9:44, as seen on
Table 1. This is to test if 9:44 is to be
accepted or rejected. The formula:
𝑋𝑎 − 𝑋𝑏
𝑄=
𝑅
where;
Xa = is the suspected outlier
Xb = value closest to Xa
R = Range of the values (highest to lowest)
After the computation, the Q was
accepted which provides the leeway to
consider it with the other values.
The number of moles of the vitamin
c used was calculated. This was used as
the true value. The experimental values
were calculated using the time lapsed in
seconds. Using these values, the
percentage error was determined. The
formula for finding the percentage error is,
𝐸𝑉 − 𝑇𝑉
% 𝑒𝑟𝑟𝑜𝑟 = 𝑥100
𝑇𝑉
The resulting percentage error was
35.17%. There are several factors that
could have led to such a high percentage
error.
There are different factors to
consider in coulometric titration. It could be
(1) variation in the current during
electrolysis, (2) departure of the process
from 100% current efficiency, (3) error in the
current measurement, (4) error in the
measurement of time, and (5) titration error
due to the difference between the
equivalence point and the end point.
Situations wherein the indicator error is the
limiting factor would prove difficult to
correct. However, proper observation is
advised.
CONCLUSION
Coulometric titration is a method in
which the titrating agent is produced in a
solution through electrolysis. It was
successfully used to determine the mole
concentration of vitamin c in the solution.
The data, due to producing an outlier,
underwent the Q-test. After calculations, the
outlier, 9:44 min, was accepted which
means that she will not be removed from
the equation all throughout the experiment.
The true value and the experimental value
of the mole concentration of vitamin c was
computed to be able to get the percentage
error. Based on the time recorded, the
amount of ascorbic acid was calculated.
Results show that an average mol of
Vitamin C or ascorbic acid was computed to
be 1.918x10-5 mol with a percentage error of
35.17%. After resulting to 35.17% error,
several factors could be behind such a large
percentage error. All of the objectives for
this experiment were met, however, strict
surveillance is suggested for the the repeat
of this experiment to avoid errors.
REFERENCES
[1] Pungor, E. (1995). A practical guide to
instrumental analysis. Boca Raton: CRC
Press.
[2] Iodometric Titration. (n.d.). Retrieved
March 15, 2018, from
https://chemistry.tutorvista.com/analytical-
chemistry/iodometric-titration.html

[3] Skoog, D. A., West, D. M., Holler, F. J.,

& Crouch, S. R. (2014). Fundamentals of
analytical chemistry. Belmont, CA:
Brooks/Cole, Cengage Learning.
APPENDIX Conclusion: 0.6719 < 0.829, outlier is
accepted
TIME (CONVERTED TO SECONDS)

60 𝑠𝑒𝑐 TRUE VALUE OF MOL VIT C

1. 6: 55 𝑚𝑖𝑛 ( 1 𝑚𝑖𝑛 ) = 360 + 5
= 415 𝑠𝑒𝑐𝑜𝑛𝑑𝑠 1 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶 0.5
1. (0.5 𝑔)( 176.12 𝑔 )(100)
𝑚𝑜𝑙

60 𝑠𝑒𝑐
= 1.419𝑥10−5 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶
2. 9: 44 𝑚𝑖𝑛 (
1 𝑚𝑖𝑛
) = 540 + 44 =
548 𝑠𝑒𝑐𝑜𝑛𝑑𝑠 EXPERIMENTAL VALUE OF MOL VIT C

2. a.
1 𝑚𝑜𝑙 𝐼 1 𝑚𝑜𝑙 𝐼 1 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶
60 𝑠𝑒𝑐
3. 6: 29 𝑚𝑖𝑛 ( 1 𝑚𝑖𝑛 ) = 360 + 29 = (389 𝑠)(0.00804)(96,487 2𝑐)(2 𝑚𝑜𝑙 𝑒2− )( 1 𝑚𝑜𝑙 𝐼 )
2

389 𝑠𝑒𝑐𝑜𝑛𝑑𝑠 = 1.621𝑥10−5 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶

2. b.
1 𝑚𝑜𝑙 𝐼 1 𝑚𝑜𝑙 𝐼 1 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶
60 𝑠𝑒𝑐
4. 7: 33 𝑚𝑖𝑛 ( 1 𝑚𝑖𝑛 ) = 420 + 33 = (215 𝑠)(0.00804)(96,487 2𝑐)(2 𝑚𝑜𝑙 𝑒2− )( 1 𝑚𝑜𝑙 𝐼 )
2

453 𝑠𝑒𝑐𝑜𝑛𝑑𝑠 = 1.729𝑥10−5 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶

2. c.
1 𝑚𝑜𝑙 𝐼 1 𝑚𝑜𝑙 𝐼 1 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶
MEAN TIME (453 𝑠)(0.00804)(96,487 2𝑐)(2 𝑚𝑜𝑙 𝑒2− )( 1 𝑚𝑜𝑙 𝐼 )
2
= 1.887𝑥10−5 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶
6: 55 + 9: 44 + 6: 29 + 7: 33
= 7: 40 𝑚𝑖𝑛𝑠
4 2. d.
1 𝑚𝑜𝑙 𝐼2 1 𝑚𝑜𝑙 𝐼2 1 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶
(584 𝑠)(0.00804)( )( − )( )
96,487 𝑐 2 𝑚𝑜𝑙 𝑒 1 𝑚𝑜𝑙 𝐼2
415 + 548 + 389 + 453 = 2.433𝑥10−5 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶
= 460 𝑠𝑒𝑐𝑜𝑛𝑑𝑠
4
AVERAGE MOL VIT C (EXPERIMENT)
Q-TEST AT 95% CONFIDENCE
INTERVAL 1.621𝑥10−5 + 1.729𝑥10−5 + 1.887𝑥10−5 + 2.433
4
TIME, in increasing order
389 seconds
415 seconds = 1.918x10-5 mol Vit C
453 seconds
PERCENTAGE ERROR
584 seconds
1.918𝑥10−5 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶 − 1.419𝑥10−5 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶
584 − 453 𝑥 100
𝑄= = 0.6718 1.419𝑥10−5 𝑚𝑜𝑙 𝑉𝑖𝑡 𝐶
584 − 389
% 𝑒𝑟𝑟𝑜𝑟 = 35.17%
Number of
Computed
Observatio Q95
Q
ns
4 0.829 0.6719