See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/225622856

Gas-chromatographic determination of carboxylic acid anhydrides in oxidation

products of alcohols and other organic compounds

Article  in  Journal of Analytical Chemistry · January 2006

DOI: 10.1134/S1061934806120124

CITATIONS READS

3 65

3 authors, including:

S. G. Voronina A. L. Perkel’
Kuzbass State Technical University Kuzbass State Technical University
46 PUBLICATIONS   109 CITATIONS    93 PUBLICATIONS   237 CITATIONS   

SEE PROFILE SEE PROFILE

All content following this page was uploaded by A. L. Perkel’ on 12 April 2014.

The user has requested enhancement of the downloaded file.

ISSN 1061-9348, Journal of Analytical Chemistry, 2006, Vol. 61, No. 12, pp. 1194–1197. © Pleiades Publishing, Inc., 2006.
Original Russian Text © T.S. Kotel’nikova, S.G. Voronina, A.L. Perkel’, 2006, published in Zhurnal Analiticheskoi Khimii, 2006, Vol. 61, No. 12, pp. 1297–1300.

ARTICLES

Gas-Chromatographic Determination of Carboxylic Acid

Anhydrides in Oxidation Products of Alcohols
and Other Organic Compounds
T. S. Kotel’nikova, S. G. Voronina, and A. L. Perkel’
Kuzbass State Technical University, ul. Vesennyaya 28, Kemerovo, 650026 Russia
Received July 7, 2005

Abstract—A procedure was developed for the gas-chromatographic determination of carboxylic acid anhy-
drides in the composition of oxidation products of organic compounds after their conversion into alkyl formate
by formic acid and benzyl alcohol or other primary alcohol introduced into the reaction medium. The reaction
proceeds through the mixed anhydride, which is formed in situ from formic acid and the determined anhydride
and is predominantly transformed into the corresponding alkyl formate in alcoholysis with alcohol. The poten-
tialities of the procedure were illustrated by the determination of anhydrides in oxidation products of cyclohex-
ane, cyclohexanone, and cyclohexanol.
DOI: 10.1134/S1061934806120124

Carboxylic acid anhydrides can appear in the oxida-
tion of saturated hydrocarbons and their oxygen-con-
taining derivatives under the action of molecular oxy-
gen and peroxide compounds [1, 2]. Because of the
interaction with water or hydroxyl-containing oxida-
tion products (alcohols and hydroperoxides), the con-
centration of anhydrides in the reaction medium is
commonly low. This fact, as well as the presence of car-
boxylic acids, esters, lactones, and ketoenols in the
composition of oxidation products, hinders the deter-
mination of anhydrides by known methods of func-
tional analysis [2]. Previously [3] a gas-chromato-
graphic method was proposed for the determination of
anhydrides as esters obtained by the treatment of the
analyzed sample with excess alcohol, which is absent in
the composition of oxidation products, under condi-
tions precluding the esterification of carboxylic acids
and the transesterification of esters. The method was
successfully used for the determination of carboxylic
acid anhydrides in oxidized 2-hydroxycyclohexanone,
benzyl benzoate, and products of the interaction of
8,9-hexadecandione and benzyl with peroxylauric
acid. However, it was found that the use of the method
for the determination of the anhydride function in oxi-
dized cyclohexane, cyclohexanone, and, especially,
oxidation products of cyclohexanol leads to underes-
timated results because of the reactions of the transa-
cylation of adipic anhydride by mono- and dicarboxy-
lic acids that occur in the reaction medium [4] and
because of the competing interaction of oxidized alco-
hol and alcohol introduced for alcoholysis with anhy-
dride. The development of a method for the esterifica-
tion of formic acid with benzyl alcohol in the presence
of acetic anhydride [4] for its subsequent gas-chro-
matographic determination allowed the assumption
that this reaction can be used for the quantitative
determination of anhydrides.
The aim of this work was to develop a gas-chro-
matographic method for the determination of the total
concentration of carboxylic acid anhydrides in oxida-
tion products of organic compounds as esters of formic
acid.
EXPERIMENTAL
Formic acid (85%, analytical grade) was kept over
anhydrous MgSO4 for dehydration and distilled in vac-
uum using a water-jet pump. The concentration of for-
mic acid in the compound according to the data of gas–
liquid chromatography (after the conversion into ben-
zyl ester by the procedure reported in [4]) was 98.2 ±
0.4% (n = 10, P = 0.95). Methods for the purification of
benzyl alcohol, pyridine, and acetic anhydride were
described previously [4]. 1-Dodecanol of the reagent
grade was dried over anhydrous MgSO4 and distilled in
vacuum. Butyric acid of reagent grade was used with-
out additional purification.
Determination of anhydrides. The determination
of the amount of formic acid required for the quantita-
tive conversion of carboxylic acid anhydrides into ben-
zyl formate was performed as follows. Different
amounts of formic acid taken in excess (1–12 M) and
1 mL of a mixture (2 : 1) of benzyl alcohol and pyridine
were added to aliquot portions of a sample containing
1.5 × 10–5–4.0 × 10–5 mol of anhydride. The reaction
mixtures were kept at 20°C for 24 h. Next an internal
standard (tetradecane) was added, and the concentra-

1194
 GAS-CHROMATOGRAPHIC DETERMINATION OF CARBOXYLIC ACID ANHYDRIDES
tion of benzyl formate was determined. From the
dependence of the concentration of carboxylic acid
anhydride on the amount of added formic acid, the
value of the addition of the latter necessary for the
quantitative determination of anhydride was found. In
the determination of anhydrides in samples whose
components interfere with the gas-chromatographic
determination of benzyl formate, aliphatic primary
alcohol ë5–ë12 can be used for the alcoholysis of mixed
anhydrides with the subsequent determination of alkyl
formate. In the determination of anhydrides in oxidized
alcohols, a correction must be introduced for the
amount of anhydride converted into the formate of the
oxidized alcohol.
The determination of benzyl formate and (or) alkyl
formate was performed on an LKhM-8MD chromato-
graph with a flame-ionization detector. We used a col-
umn with sizes 3 × 1000 mm with a sorbent containing
5% XE-60 polysiloxane on Chromaton N-AW (0.20–
0.25 mm). On this column, formates have shorter reten-
tion times than corresponding alcohols. The time of a
single determination is 15 min.
Samples of oxidized cyclohexane were obtained by
its oxidation with air in a stainless-steel bubble reactor
at 150°ë under a pressure of 1.5 MPa. Cyclohexanone
and cyclohexanol were oxidized with air at 120°ë in a
glass reactor as a 4 M solution in chlorobenzene.
O C(CH2)4C O + R1COOH
O O
+R2COOH
–HOOC(CH2)4COOH
The alcoholysis of these anhydrides by alcohols
yields a mixture of esters, and their quantitative deter-
mination in complex mixtures such as oxidation prod-
ucts of organic compounds is not necessarily possible.
On the introduction of formic acid into the reaction
mixture, mixed formic anhydrides are formed along
with others. It can be assumed that these anhydrides
will exhibit the highest reactivity among other anhy-
drides and will undergo alcoholysis, first of all trans-
forming mostly into esters of formic acid [4, 5]:
+ROH
HC O CR1 HCOR or R1COR . (2)
–R1COOH
O O or HCOOH O
O formic acid on the results of the determination of acetic
The use of the ester of formic acid as the analyte
imposes additional requirements upon the selection of
alcohol for alcoholysis. The low sensitivity of the
flame-ionization detector to free formic acid [6, 7], as
well as the high volatility of low-molecular formates,
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61
1195
cBF × 102, å
3
2
1
0 3 6 9 12 15 18 21
ëHCOOH × 102, M
Fig. 1. Effect of the value of the addition of formic acid on
results of the determination of acetic anhydride in chlo-
robenzene.
RESULTS AND DISCUSSION
The difficulties mentioned above in the determina-
tion of carboxylic acid anhydrides in oxidation prod-
ucts of cyclohexane, cyclohexanone, cyclohexanol, and
the majority of other organic compounds are mostly
due to the occurrence of the rapid reaction of the transa-
cylation of the initially formed anhydride, e.g., adipic
anhydride, by mono- and dicarboxylic acids that occur
in the reaction medium yielding an equilibrium mixture
of mixed anhydrides [2, 3]:
HOOC (CH2)4C O CR1
O
(1)
R2C O CR1 .
O O
require the use of rather high-boiling alcohols, e.g.,
benzyl alcohol [4, 8]. In the case of difficulties in the
gas-chromatographic separation of benzyl formate and
oxidation products of the organic compound, another
high-boiling primary alcohol can be used instead of
benzyl alcohol.
According to the problem at hand, at the first step
we carried out studies on the development of a method
for the quantitative conversion of anhydrides into ben-
zyl formate. Acetic anhydride was used as a model
compound.
The study of the effect of the value of the addition of
anhydride in its 3.6 × 10–2 M solution in chlorobenzene
(Fig. 1, curve 1) demonstrated that, at a ratio of the con-
centrations of formic acid and acetic anhydride of 4.0
and above, the results of the determination of acetic
anhydride are independent of the concentration of for-
mic acid. Because carboxylic acids participate in reac-
No. 12 2006
1196 KOTEL’NIKOVA et al.

0 1 2 3 4 5 cHCOOH × 10, M the method is accurate. The lower determination limit

of acetic anhydride is close to 3 × 10–5 M (RSD = 32%)
1 (Table 1), although, it can probably increase with the
4 concentration of carboxylic acids in analyzed samples.
2
The total concentration of mixed anhydrides in oxi-
cBF × 102, M

3 dized cyclohexanone and cyclohexane was determined

2 work (Table 2). In Table 2, it is seen that, in the latter
1 the known procedure.
0 4 8 12 16 cHCOOH × 102, M
Fig. 2. Effect of the value of the addition of formic acid and
the concentration of butyric acid (cRCOO) on the results of
the determination of acetic anhydride in chlorobenzene:
(1) cRCOOH = 0.43 M; (2) cRCOOH = 3.8 M.
tions of type (1), they can also affect the determination
of anhydride. We studied the effect of the value of the
addition of formic acid on the results of the determina-
tion of acetic anhydride in its solutions in chloroben-
zene (4.3 × 10–2 and 3.8 × 10–2 M) containing 0.43 and
3.8 M butyric acid (Fig. 2). The completeness of the
determination of acetic anhydride in these cases
depends both on the concentration of formic acid and
on the concentration of butyric acid and is attained at a
ratio of the concentrations of the acid and the anhydride
of 5–10 and above (Fig. 2).
The above data indicate that the amount of formic
acid required for the complete conversion of acetic
anhydride into benzyl formate depends on the compo-
sition of analyzed samples. Although quantitative
results in most cases can be probably attained with the
use of a 12-fold molar excess of formic acid, it is rea-
sonable to previously obtain dependences like those
presented in Figs. 1 and 2 for the selection of the nec-
essary amount of formic acid. The results of the deter-
mination of acetic anhydride in chlorobenzene solu-
tions of known concentration in Table 1 indicate that
by the known method and the method developed in this
case, the results of the determination are 1.8–2.1 times
higher than in the determination of adipic anhydride by
Additional difficulties appear in the determination
of carboxylic acid anhydrides in oxidation products of
alcohols. In these cases, underestimated results are
caused by the competing interaction of mixed anhy-
drides with oxidized alcohol (R1OH) and alcohol intro-
duced for alcoholysis (R2OH):
+R1OH, k1 +R2OH, k2
HCOR1 HC O CR HCOR2 . (3)
O O O O
Commonly, the amount of the formate of the deter-
mined alcohol that is formed in the alcoholysis of
mixed anhydrides cannot be determined analytically,
because it is usually formed in the course of oxidation
in concentrations substantially higher than the concen-
tration of anhydride. However, the correction for the
formation of the formate of oxidized alcohol can be cal-
culated on the basis that the ratio of the concentrations
of formates mentioned above is equal to the ratio of the
rate of the bimolecular reactions of corresponding alco-
hols with mixed anhydrides:
dc f 2 k 2 c R 2 OH c an cf 2
---------- = ------------------------ = -----
-, (4)
dc f 1 k 1 c R 1 OH c an c f1
where c R 2 OH , c R 1 OH , cf2, and cf1 are the concentrations
of the determined alcohol and the alcohol that is used
for alcoholysis and their formates, respectively; can is
the concentration of anhydrides; and k1 and k2 are the
rate constants of the reactions in scheme (3).

Table 1. Results of the determination of acetic anhydride in solutions of known concentrations in chlorobenzene (n = 8, P = 0.95)

c fa ⎞ * Taken Found
Sample no. ⎛ -----
- Concentration
⎝ c aa⎠ of added butyric acid, M ( c ± δ) × 102, M ( c ± δ) × 102, M RSD, %
1 5 – 0.0034 ± 0.001 0.0031 ± 0.001 32
2 5 – 0.0332 ± 0.003 0.033 ± 0.001 3
3 5 – 3.61 ± 0.03 3.63 ± 0.06 2
4 8 0.43 4.32 ± 0.02 4.3 ± 0.1 3
5 12 3.80 3.78 ± 0.03 3.8 ± 0.1 4
* Ratio of the concentrations of formic acid and acetic anhydride.

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 12 2006

 GAS-CHROMATOGRAPHIC DETERMINATION OF CARBOXYLIC ACID ANHYDRIDES 1197

Table 2. Results of the determination of anhydrides in oxidation products of cyclohexane and cyclohexanone by the devel-
oped and known methods (n = 8, P = 0.95)
By the developed method By the known method [3]
Time
Analyzed material
of oxidation, min ( c ± δ) × 103, M RSD, % ( c ± δ) × 103, M RSD, %
Oxidized cyclohexane 80 0.31 ± 0.02 8 0.17 ± 0.02 11
140 0.85 ± 0.04 6 0.45 ± 0.03 9
Oxidized cyclohexanone 300 4.6 ± 0.2 5 2.2 ± 0.1 8
420 17.2 ± 0.7 5 9.1 ± 0.5 7

Table 3. Results of the determination of anhydrides in oxidized cyclohexanol (n = 8, P = 0.95)

Time
Sample no.
of oxidation, min
Alcohol used for alcoholysis ( c ± δ) × 102, M RSD, %

1 180 Benzyl alcohol 1.8 ± 0.1 8

Dodecanol 1.9 ± 0.1 7
2 300 Benzyl alcohol 2.3 ± 0.1 6
Dodecanol 2.2 ± 0.1 6

Using relationship (4), we can obtain the equation ACKNOWLEDGMENTS

for the calculation of the concentration of anhydride in
oxidation products of alcohol:
⎛ k 2 c R 2 OH⎞
c an = c f 1 + c f 2 = c f 1 ⎜ 1 + -----------------
-⎟ .
⎝ k 1 c R 1 OH⎠
The ratio k2/k1 required for calculations by Eq. (5)
was determined in special experiments in the treatment
of acetic anhydride (0.04 M) and formic acid (0.5 M)
with a mixture of alcohols of known composition in a
pyridine solution. For cyclohexanol and benzyl alcohol,
k2/k1 = 0.47 ± 0.01; for cyclohexanol and 1-dodecanol,
k2/k1 = 0.56 ± 0.01.
Results of the determination of anhydride in sam-
ples of oxidized cyclohexanol (Table 3) indicate that
the developed method can be used for the determination
of carboxylic acid anhydrides in oxidized alcohols and,
according to the data in Table 2, practically all oxidized
products.
We are grateful to P.I. Sviridenko (department
Okislenie-3, KOAO Azot) for his help in obtaining
samples of oxidized cyclohexane.
(5) REFERENCES
1. Perkel’, A.L., Voronina, S.G., and Freidin, B.G., Usp.
Khim., 1994, vol. 63, no. 9, p. 793.
2. Perkel’, A.L. and Voronina, S.G., Zh. Anal. Khim., 1998,
vol. 53, no. 4, p. 343 [J. Anal. Chem. (Engl. Transl.),
vol. 53, no. 4, p. 299].
3. Perkel’, A.L. and Freidin, B.G., Zh. Anal. Khim., 1993,
vol. 48, no. 2, p. 353.
4. Kotel’nikova, T.S., Vdovenko, O.V., Voronina, S.G, and
Perkel’, A.L., Zh. Anal. Khim., 2006, vol. 61, no. 4,
p. 370 [J. Anal. Chem. (Engl. Transl.), vol. 61, no. 4,
p. 338].
5. Fieser, L. and Fieser, M., Reagents for Organic Synthe-
sis, New York: Wiley, 1973, vol. 5.
6. Schaefer, B.A., J. Chromatogr. Sci., 1975, vol. 13a,
no. 2, p. 86.
7. Eek, L. and Galceran, M.T., Quim. Ind., 1973, vol. 19,
nos. 7–8, p. 466.
8. Doms, E.K., J. Chromatogr., 1975, vol. 105, no. 1, p. 79.

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 12 2006

View publication stats