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Daniel G.

Marsh,
Deborah 1. Jacobs,
and Hans Veening
Bucknell University
Lewisburg, Pennsylvania 17837

Analysis of Commercial Vitamin C Tablets


by lodometric and Coulometric Titrimetry

Since the publication of Professor Pauling's well-known


book "Vitamin C and the Common C o l d (I), there has
been a marked increase in the use of vitamin C as a preventive medicine. In view of the controversy concerning
the relative merits of kitamin C as a common cold and flu
~reventive,i t seemed that the determination of ascorbic
acid as a lahoratory exercise in the elementary analytical
chemistry course would be an interesting undergraduate
experiment. This experiment achieves three objectives:
(1)the student carries out a classical titrimetric oxidationreduction procedure; (2) the determination provides experience for the student with an instrumental electro-analytical technique; (3) the student learns how to apply routine analytical procedures to a problem which is both
timelv and relevant.
~ i G i m e t r i ctechniques are generally the most frequently
cited analytical methods for the determination of ascorbic
acid. The 1J. S. Pharmacooeia recommends the titration
of ascorbic acid with staidard iodine solution ( 2 ) . The
methods used bv the Food and Drue Administration include a direct titration with 2,6-d~chlor~indo~henol
as
well as a fluorimetric ~rocedure(3).A continuous determination of ascorbic acidby pbotobleaching of methylene blue
has also been r e ~ o r t e drecently (4). Other techniques which
have been used for the determination of ascorbic acid in
multivitamin samples include gas chromatography i.5) and
polamgraphy (6).
The experiment described here was included as part of
the laboratory work in the elementary analytical course
(96 students) a t Bucknell during the spring of 1972.
Ascorbic acid was determined in commercial vitamin C
tablets by utilizing its quantitative oxidation with bromine, a reaction first reported by Schulek, Kovkcs, and
Rozsa (7),and later suggested as a possible coulometric
determination by Skoog and West (8). It was the latter
citation which prompted us to formulate this undergraduate experiment.
The experiment consists of two parts. First, the student
determines the ascorbic acid content of vitamin C tablets
iodometricallv utilizine a back titration witb standard
thiosulfate. Yhiswell l&wn method has been outlined by
Kolthoff. Sandell. Meehan, and Bruckenstein (9). The en-.
tire class performed this part of the experiment. The second part utilizes an instrumental technique. Ascorbic acid
is titrated coulometrically by direct oxidation to dehydroascorbic acid using electrolytically generated bromine.
The end ooint is detected amnerometricallv. Because of
equipmeni limitations, this portion of the experiment was
limited to about 35 specially selected students.
lodometric Titration of Ascorbic Acid (Koppeschaar
Method)
The procedure .given by Skoog and West (10) was followed for the iodometric titration. The eauioment
and
. .
skills necessary to carry out this portion of the experiment
are tvoical of classical oxidation-reduction titrimetry. The
oxidiiion-reduction reaction of bromate with exceis bromide in acid solution is used to generate an excess of bromine which oxidizes the ascorbic acid in the unknown
sample. This reaction is fast and stoichiometric (7, 8).
626 /Journal of Chemical Education

rk!!,
1.5V

Batt.

Switch
SPST

E
25K ohm

DPDT

Switch

Pt Indicator
Electrodes

Figure 1. Detector circuit for amperometric end point detection. DPDT


= double pole double throw. SPST = single pale single throw.

The excess bromine is then converted to iodine by reaction witb potassium iodide. Finally, the iodine (triiodide)
produced by this reaction is titrated with standard thiosulate using starch indicator.
The unknown samples issued to the students consisted
of commercially available vitamin C tablets with ascorbic
acid levels ranging from 100-500 mg per tablet. The unknown tablet is weighed to the nearest *0.1 mg and
transferred to a 250.0-ml volumetric flask, dissolved in approximately 100 ml of distilled water (dissolution takes
about one-half hour), diluted to volume and mixed. The
resulting solution will be somewhat cloudy due to the
presence of inert substances in the tablet. The solution
must he kept out of the light as much as possible and
must be titrated within 2 hr or significant deterioration
will result.
Coulometric Titration of Ascorbic Acid at Constant
Current
The determination of ascorbic acid is carried out in this
part of the experiment by using a slightly modified version of the coulometric procedure reported by Evans (11).
The apparatus includes a constant current amperostat of
the type described by Vincent and Ward (12). A milliammeter was used to monitor the curr?nt through the generator electrodes. The titration flask and the generating and
indicator electrodes were identical to those previously described (11). The amperometric end point detection sysPresented at the 165th National Meeting of the American Chemical Society, Dallas, Texas, April, 1973.

tem consisted of two platinum electrodes, a 1.5-Vdry cell,


a 25-Kohm single turn potentiometer and a sensitive microammeter. These comDonents were assembled in a
small case. In addition, a standardized millivoltmeter
(Beckman Zeromatic) was used to monitor a n a p d i e d DOtential of 0.25 V across the indicator electr&ies. The
amperometric detector circuit is shown in Figure 1 and
the coulometric assembly is shown photographically in
Figure 2.
The electrolysis is carried owt a t 20 mA using platinum
electrodes in an aqueous, acidic medium containing dissolved potassium bromide and the dissolved unknown sample. The mixture is stirred magnetically and the bromine
generated a t the anode instantly reacts with the dissolved
ascorbic acid from the unknown sample.
~

~~

OH
HO-CH,-CH-C.

H
I/\/O

.C

Br;

Figure 2. Caulometric apparatus used for ascorbic acid titratians.

ascorbic acid

dehydraascorbic acid
Reagents and Procedure

1) Electrolytic Soluent. The solvent consists of 1:I glacial acetic


aeid-water and dissolved KBr (0.15 F ) .
2) Unknown Solution. The same unknown solution used in the
first part of the experiment can he used here.
3) Coulometric Titmtion. A blank titration is initially carried
out in order to remove oxidizable impurities, and known quantities of ascorbic acid (from 2-20 mg) are then successively
added and titrated using the procedure of Evans (11). Each
electrolysis is terminated at a steady indicator current of 20
@amp.Finally, the titration is repeated for each of three identical 10.0 ml unknown samples.
The students prepare a calihration curve of mg ascorbic acid
versus titration time. A linear plot which passes through the origin is obtained and is utilized to calculate the number of mg of
ascorbic acid (or percentage by weight) in the titrated sample
and in the unknown. A typical calihration plot is shown in Figure
3. The average value of three titrations is reported. As part of the
laboratory report, the answers to several questions on eoulometry
and ampemmetry were assigned.

Titration rime (min)

Figure 3. Coulometric calibration


electrodes current: 20.0 mA.

for ascorbic acid. Generating

Table 1. lodometric Analysis of Commercial Vitamin C Tablets


and Pure Ascorbic Acid Samples

me Ascorbic
A G in~sample (Manu- mg Ascorbic Number
of
facturer's
Acid
Found
Trials
Label)

Results and Discussion

Results for the iodometric and coulometric methods are


given in Tables 1 and 2. It is seen that this experiment
gives very satisfactory results when performed by students. A careful analysis of the deviations of the measurement yields an uncertainty of f2% depending on the accuracy of the student's standardization of the thiosulfate
solution. It was thought that the presence of particulate
matter &om the tablets in the unknown solutions could
indicate incomplete extraction of ascorbic acid from the
tablets. Several control experiments in which the students
pulverized and ground the tablets prior to the analysis indicated that this was not the case. The presence of the
undissolved material did require extra care, however,
when pipetting the solutions.
The advantage of coupling the rather involved iodometric procedure with the faster and simpler cou~ometric
analysis illustrates the obvious advantage of the latter:
The coulometric method also illustrates the very useful
amperometric end point detection technique, as well a s
the use of a reagent, such as electrolytically generated
bromine which is difficult to use a s a standard buret titrant. It is essential t h a t the instructor explain the theory

curve

Sam&
Rexall Chewable
Vitamin C Tablets
(Lot No. K12003)
Squibb Ascorbic Acid
Tablets (U.S.P.)
(Control No. 037223
Purepac Vitamin C
Tablets
(Lot No. 0170K3)
Squibb Ascorbic Acid
Tablets (U.S.P.)
(Control No. 0L561)
Purepae Vitamin C
Tablets
(Lot No. 0167K3)
C. P. Reagent Grade
Ascorbic Acid
(Eastman)

100

101f5

100

108 f 2

250

255 + 6

250

259 f 6

500

499 f 2

562

563 f 1

504
469

504 + 1
468 1

3
3

Volume 50, Number 9. September 1973 / 627

Table 2. Coulometric Analysis of Vitamin C Tablets

Sample
Squibb Ascorbic Acid
Tablets (U.S.P.)
(Control No. 0B695)
Squibb Ascorbic Acid
Tablets (U.S.P.)
(Control No. 0E722)
Squibb Ascorbic Acid
Tablets (U.S.P.)
(Control No. 0L567)
Purepae Vitamin C
Tablets
(Lot No. 0167K3)

mg Ascorbic
Acid in samole (Manu- ma Ascorbic Number
'faiturer's
- Acid
of
Label)
Found
Trials

50

50.4 + 1

100

101 + 1

250

255 -L. 4

500

498 + 2

of constant current electrolysis, and particularly amperometric end point detection.


There was some concern that the accuracy of the coulometric method might suffer by omitting the separate glass
frit cathode compartment often employed in this technique. The linearity of the calibration plot and the analytical results, however, indicated that this added mea-

628 1 Journal of Chemical Education

sure was unnecessary. We constructed and utilized two


complete coulometric titration units and assigned a pair
of students to each instrument. By staggering the laboratory schedule over several weeks, it was possible for 35
students to perform this part of the experiment.
Acknowledgment
Partial support for this work by a departmental grant
from E. I. duPont de Nemours and Company, Inc. is
gratefully acknowledged. The authors also wish to thank
Mr. Hamy D. Wilson and Mr. Peter J. Bergonia, Jr. for
their assistance in the construction of the coulometric
equipment.
Literature Cited
(1) Psuling, I.C.. -vitamin C and The common Cold," W. H. Freeman and co., s a n
Francisco. 1970.
(2) The P h m a e o p e i a of The United Stat-, (18th Ed.), Beth-da, Md., 1970, pp. 5153.
(3) H~nuit.. W- iEdit0,i. "Otfieisl Methods of Ans?vsi. of tho Amociatio" of Offici.4
Weshindrm.D.C..
Analvtieal Chemiaul."lllthEd.l.A.O.A.C..
. .
. .
. 1970.o. 777.
(41 Whifa.V.R..andFitzgeraid. J.M.,Anai. Chsm., 44.1267(19721.
151 Sennella.. LT..
.and4moudeIis. C. J..Anvl. Chem.. 41. 171 119691
Krize, I.. Formotaiyo, i8.59 (1959).
Schulek,E.,Kov&cs. J., andRasa,P.,Z.Anal. Chem.. 121.17 119411.
Skwg. D. A,, and West. D. M., "Principle of Instrumental Analysis: Holt, Wnehart, and Winston. Ino.. NeuYork, 1971 p. 552.
Kolthoff. I. M.. Sendell, E. B., Meehan. E. J., and Bruckenstoin. 8.. "Qusntitative Chemical Anslysia: Macrnillan Co.. London. 1969, pp. 820snd862.
Skwg, D. A,. and West, D. M., "Fundamentala of Analytical Chemistry," Holt,
Wnehert, and Winston, Inc., NeuYork, 1969, pp. 449-58.
Evans, 0. H.. J. CHEM.EDUC., 45.88 (19681.
Vineenf, C.A., and Ward,J. G..J. CHEM.EDUC., 46,613(19691.