Talanta, Vol. 35, No. 8, pp.

655-657, 1988
Printed in Great Britain. All rights reserved

0039-9140/88 $3.00 + 0.00

Copyright 1988 Pergamon Press pie

SPECTROPHOTOMETRIC DETERMINATION OF
FORMALDEHYDE
GHAZI AL-JABARI and BRUNO JASELSKIS
Department of Chemistry, Loyola University of Chicago, 6525 N. Sheridan Road, Chicago,
IL 60626, U.S.A.

(Received 17 March 1988. Accepted 12 April 1988)

Summary--A new spectrophotometric method for the determination of micro amounts of formaldehyde
in aqueous and methanol solutions is based on the oxidation of formaldehyde by hydrous silver oxide
at pH 11-12.5 and oxidation of the metallic silver produced, with iron(IlI) in the presence of Ferrozine.
The absorbance of the resulting iron(II)-Ferrozine complex at 562 nm is proportional to the amount of
formaldehyde and corresponds to an apparent molar absorptivity of 5.58 x 104 l.mole-t.em -'.

Large volume production and usage of formaldehyde

and its possible exposure-related health effects have
caused much concern over the sensitivity and accuracy of analytical methodology for this compound.
In general, large amounts of formaldehyde or other
aliphatic aldehydes have been determined titrimetrically by reaction with alkaline silver(l) and backtitration of the excess o f silver(I) ~ or by the Ripper
method with sulphite and back-titration of the excess
of sulphite with standard iodine solution. 5
Small amounts of formaldehyde are determined
by gas chromatography, 6"7 high-performance liquid
chromatography, s.9 electrochemicaP 'H and spectrophotometric ~2-~s methods. Spectrophotometric methods are c o m m o n l y used and one of these, the chromotropic acid method, is recommended by N I O S H in its
P & C A M 125 and P & C A M 235 reference methods. ~9
This study describes a colorimetric procedure for
the determination of formaldehyde and aliphatic
aldehydes in aqueous and methanolic solutions, by
use o f a modified P o n n d o r f method (hydrous silver
oxide) coupled with the iron(III)-Ferrozine system.
EXPERIMENTAL

Instrumentation
A Cary 14 spectrophotometer and a Coming model XII
pH-meter were used. A PAR 170 A polarographic analyser
with a dropping mercury electrode in a three-electrode
system was operated in the differential mode at a scan-rate
of 5 mV/sec, a modulation amplitude of 25 mV, a drop-rate
of 1 drop per sec, recorder sensitivity of 1 #A/25 era, and
scan-range from - 1.5 to - 2 . 0 V.

in 1 litre of 0.1M sulphuric acid and 2.12 g of silver nitrate

in 250 ml of demineralized water. Acetate buffer of pH 3.5
was prepared by adding concentrated sodium hydroxide
dropwise to 0.SM acetic acid. Polarographic determinations
were performed with a 0.1M lithium hydroxide, 0.01M
lithium chloride supporting electrolyte.

Procedures
Standardization and determination of formaldehyde in
aqueous solutions. Suitable aliquots (0.050-0.500 ml) of
2.58 10-3M standard formaldehyde solution, 0.25 ml of
0.05M silver nitrate and 0.1 ml of 0.1M sodium hydroxide
were added to 25-ml test-tubes, in that order. The solutions
were stirred for 10 min, then 2 ml of 0.004M iron(III)
solution, 2 ml of Ferrozine solution, and 5 ml of acetate
buffer were added, and the mixtures were transferred to
50-ml standard flasks and diluted to volume. The absorbances at 562 nm were measured after 10 rain against a blank.
The same standard formaldehyde solution was used for a
comparative study of the chromotropic acid and polarographic methods.
Determination of formaldehyde in dilute(3-10 IO-SM)
aqueous and methanolic solutions. Dilute formaldehyde solutions were analysed in a similar manner to the more
concentrated samples. The conditions were changed to 5 or
10 ml of sample, 0.5 ml of silver nitrate solution, 2-3 mi of
sodium hydroxide solution, and 25 min reaction time before
the addition of iron(liD, Ferrozine, and acetate buffer. Very
dilute samples were analysed by the standard-addition
method, as described below for methanol.
The amount of formaldehyde (or other aliphatic aldehyde) in technical and reagent grade methanol was determined by the standard-addition method. Three 0.500-ml
samples of the methanol were placed in 50-ml standard
flasks, and diluted with 6 ml of demineralized water, then
two of the samples were spiked with known amounts of
standard formaldehyde solution. The other reagents were
added in the same order as for dilute solutions.
The absorbance was measured against a blank containing
all the reagents used in the analysis of the sample, except the
silver nitrate.

Reagents
All chemicals were analytical or primary grade.
Formaldehyde standard stock solution (2.58 x lO-3M)
was prepared from 37% formalin and standardized argentometrically? Approximately 1.24 g of Ferrozine [3-(2RESULTS
pyridyl)- 5,6-diphenyl- 1,2,4-triazine-p,p - disulphonic acid
monosodium salt monohydrate (Aldrich)] was dissolved in
The amount of formaldehyde in the sample can be
250 ml of demineralized water. Stock solutions of 0.004M
iron(Ill) and 0.05M silver nitrate were prepared by dis- determined by several methods: (i) calibration curve,
solving 1.932 g of ammonium ferric sulphate dodecahydrate (ii) calculation by using the apparent molar absorp655

656

SHORT COMMUNICATIONS

Table 1. Determination of formaldehyde in aqueous and methanolic solutions by the

proposed method and the ehromotropic acid and differential pulse polarography (DPP)
methods
Ag20-Fe(III)
Final CH20
concentration,
#M

Chromotropic acid
E,

DIP
peak
height,

A*

104 l.mol-l.cm -t

mm

0.097
0.194
0.292
0.390

1.55
1.54
1.55
1.55

13
25
37
49

~,
A*

104 I.mole-l.cm -I
Water

6.3
12.6
18.9
25.2

0.350
0.705
1.055
! .403

5.56
5.59
5.59
5.57

6.3
12.6
18.9
25.2

0.349
0.701
1.050
1.400

5.56
5.56
5.55
5.56

10% Methanol-water

13
25
38
50

-----

*Average of four determinations, corrected for the blank.

tivity of 5.58 x 104 1.mole-~.cm -~, and (iii) the

standard-addition method (used with very dilute
solutions). In the calculation method, the amount
of formaldehyde in the 50 ml of final solution is
26.9A #g, where A is the absorbance measured in a
l-cm cell.
Results for determination of formaldehyde in
standard aqueous and methanolic solutions and in
methanol samples and the comparison experiments
are summarized in Tables 1 and 2.

DISCUSSION

Ponndorf i reported that hydrous silver oxide

oxidizes formaldehyde to formate:
Ag20.xH20 + HCHO 4- O H -* 2Ag + H C O O - + xH20
In the Ponndorf procedure the excess of silver ion
is determined by titration with standard thiocyanate
solution, whereas in the proposed method the

amount of metallic silver is obtained colorimetrically

from the amount of iron(II)-Ferrozine complex2
produced:
Fe(III) + Ag ~ Ag + + Fe(II)
Fe(II) + 3Ferz:- ~ Fe(II)Ferz4Siggia and Segal 2 used an ammoniacal silver ion
solution instead of hydrous silver oxide. However,
ammoniacal silver solution (Tollen's reagent)
presents a potential danger of explosion, particularly
when the solution becomes concentrated or dries out.
Because of this, Mayes et a l ) modified the method
by replacing the ammonia with tert-butylamine. The
use of ammoniacal silver solution does not prevent
aldehydes from undergoing the Cannizzaro reaction,
whereas in the Ponndorf method the side-reactions of
aldehydes such as the Cannizzaro reaction or aldol
condensation do not occur, since the solutions are
strongly basic and dilute. However, the pH must be
kept in the range 11-12.4. Below pH 11 the reaction
is too slow, while with pH above 12.5 the results are
low.

Table 2. Determination of formaldehyde in methanol and simulated

samples
CH20 found
Aliquot,
CH20
Net
in the original
Sample
ml
added,gg absorbance
sample,#g
Bulk methanol
0.500
0.500
0.500
Aqueous dilute sampler
0.030t
0.030?
0.030"["

0.00
8.80
17.60

0.055
0.390
0.720

1.7 _+0.2*

0.00
8.80
17.60

0.1 l0
0.440
0.755

3.5 + 0.2*

9.4
18.9
28.3

0.350
0.710
1.060

9.4 _ 0.2
19.1 ___0.3
28.5 _ 0.3

Aqueous
0.050
0.100
0.150

*Value obtained by the standard-addition graphical method.

tFormaldehyde concentration 5.93 x 10-3M.

SHORT COMMUNICATIONS

Hydrous silver oxide does not oxidize alcohols,

ketones, carboxylic acids, phenols and acetals. Aliphatic aldehydes react readily with it, the reactivity
decreasing with increasing molecular weight. Aromatic aldehydes are considerably less reactive than
aliphatic aldehydes and their interference is not
serious as long as their concentration is not much
greater than that of the formaldehyde and the reaction time is kept to 25 min or less. Monosaccharides
and citric, tartaric and ascorbic acids interfere, and
formaldehyde must be separated from them by distillation or other methods. Sulphite and sulphide
reduce iron(III) to iron(II) and must be eliminated
when present in amounts greater than that of the
formaldehyde. The sulphite-formaldehyde addition
compounds do not react readily with hydrous silver
oxide.
Trioxan does not react with hydrous silver oxide,
whereas paraformaldehyde is quantitatively oxidized.
The absorbance of the iron(II)-Ferrozine complex
produced in the method is directly proportional
to the formaldehyde concentration in the sample.
The apparent molar absorptivity of 5.58 x 104
I. m o l e - l , cm-m corresponds to the oxidation of formaldehyde to formate, with transfer of two electrons.
The modified Ponndorf method coupled with the
iron(III)-Ferrozine reaction is approximately 3.5
times more sensitive than the chromotropic acid
method and can be used with aqueous methanol
solutions provided that the methanol concentration is
less than approximately 10% v/v. Otherwise, the
reaction of formaldehyde with silver oxide is slow and
incomplete. However, the procedure cannot be used
with formaldehyde absorbed in sulphite solutions,
unless the sulphite is eliminated. On the other hand,
chromotropic acid can be used with sulphite solutions
but not with methanolic solutions.
The reproducibility has been checked for various
levels of formaldehyde by quadruplicate analysis. The
relative standard deviations of individual sets varied
from 1.5 to 3.5% depending on the concentration of
formaldehyde.
The procedure does not differentiate between individual aliphatic aldehydes and in a mixture they are
all determined as though they are formaldehyde.

TAL 35/~-E

657

Also, alcoholic beverages containing sucrose, citric,

tartaric acids and hemiacetals cannot be analysed by
this procedure, since these as well as formaldehyde
reduce hydrous silver oxide to metallic silver.
The proposed method allows the determination of
formaldehyde in amounts from 9 to 40 /zg when
50-ml standard flasks are used. Also, the concentration of formaldehyde in the original sample must
be greater than 3 x 10-SM, or the reaction time
will be long and the results low. However samples
more dilute than 3 x 10-SM can be analysed by the
standard addition method.
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