Propellants and Explosives 4, 27-29 (1979)
Indirect Determination of Water in Nitroglycerin-Nitrocellulose
Pastes by Gas-Liquid Chromatography
J. A. Blanco, A. 0. Rutci, S. C. Revuelto, A. A. Dubini and R. A. Gonzalez
Laboratorio d e Quimica Analitica, CITEFA, Villa Martelli, 1603 Pcia. Buenos Aires (Argentina)
Indirekte Wasserbestimmungin Nitroglycerin-Nitrocellulose-
Mischungen mittels Gas-Fliissigchromatographie
Fur die Wasserbestimmung in Nitroglycerin-Nitrocellulose-
Pasten wurde eine gas-fliissigchromatographische Arbeitsvorschrift
ausgearbeitet. Die Methode beruht auf der Reaktion von 2,2-
Dimethoxypropan mit Wasser unter Umsetzung zu Aceton, das dann
anschlieaend bestimmt wird. Die Arbeitsweise ist einfach, schnell und
zeichnet sich durch gute Reproduzierbarkeit und MeRgenauigkeit
aus. Eine einfachere, nicht chromatographische, weniger genaue
Methode wird zusiitzlich vorgeschlagen.
Summary
A gas-liquid chromatographic procedure was developed in connec-
tion with the determination of water in nitroglycerin-nitrocellulose
pastes. The method is based on the reaction of water with 2,2-
dimethoxypropane and its conversion to acetone which is subse-
quently determined. The technique is simple, rapid, and shows good
accuracy and precision.
A simplified method, which is less accurate but does not involve
chromatography, is also proposed.
1. Introduction
The water content of nitroglycerin(NG)-nitrocellulose(NC)
pastes must be determined in a short time during the manu-
facture of solventless powders in factories. Such water content
may range from 35-30% (after the centrifugation of the
slurry) to 1@8% (after the drying, mixing and ripening of the
dough). The drying of the mixture can be followed and the
time of process may be adjusted to a wanted final moisture
content if a quick and reliable method of water determination
is available.
In previous studies, rapid results were obtained using a high
frequency equipment(’) and also by means of a procedure
involving desiccation by a forced flow of dry air(’).
Methods for determining water in NG-NC pastes, whose
results are based on a loss of weight by evaporation are ob-
jectionable from the point of view of the partial volatilization
of NG. Furthermore, classical desiccation techniques are time-
consuming.
The reaction of 2,2-dimethoxypropane (DMP) with water:
OCHJ 0 Hydrogen flow: 30 ml/min
H’ I/
CH3 - C - CH3 + H 2 0 -CH, - C-CH, + 2 CH30H
I
OCH,
has been studied by a number of investigator^(^-^).
T h e DMP reaction has been employed in indirect gas-liquid
chromatographic (GLC) procedures for the determination of
water in some organic systems(’-’) and in natural products(*)
with good results. Nevertheless, its applicability in NG-NC
systems has not yet been described.
0 Verlag Chemie, GmbH, D-6940 Weinheim, 1979
27
Determination indirecte de la teneur en eau des melanges de nitro-
glycerine et de nitrocellulose par chromatographie gaz-liquide.
On a mis au point un mode operatoire de chromatographie gaz-
liquide pour dtterminer la teneur en eau des pstes de nitroglycerine/
nitrocellulose. La mtthode est fondee sur la reaction du 2,2-
dimethoxypropane avec l’eau avec formation d’acttone qui est ensuite
dosee. Le mode operatoire est simple, rapide, bien reproductible et
precis. On indique en outre une methode simplifiee mais moins
precise, ne faisant pas appel aux techniques chromatographiques.
The present work was undertaken in an effort to find a
simple and rapid procedure as an aid for the analysts con-
cerned with the water content determination in NG-NC
pastes.
2. Experimental
2.1. Apparatus, materials and reagents
All results were obtained with a Varian Aerograph 2740
gas chromatograph, equipped with a flame ionization detector
(FID) and a servo-potentiometric recorder (Model 252 A,
Linear Instruments Corp.) provided with a n integration chan-
nel.
The gas chromatographic conditions were as follows:
Column: 4.5 m X 2 mm I.D. stainless steel (s.s.) packed with
30% tetrahydroxyethyl ethylenediamine (THEED) on
8&100 mesh Varaport 30. For operation, the instrument was
equipped with a device for adding extra carrier gas at the
outlet of the column. This was attained, for the sake of
convenience in our chromatograph, simply installing a length
of li8-inch S.S. tubing packed with glass beads between the
remainder injector in our apparatus and a 1/8-inch Swagelok
brass “T”, which in turn was connected between the outlet of
the column and the inlet of the detector system.
Oven temperature: 105“ Cin isothermal operation
Injection port temperature: 140°C
Detector temperature: 1 5 0 ° C
Air flow: 350 mllmin
Nitrogen carrier flow: 10 ml/min
Extra nitrogen flow: 20 mllmin
Sensitivity: 1 x a. f. s.
Attenuation: X 128
Injected sample: 0 3 p1 to 0.8 p.1
Reagents used: 2,2-dimethoxypropane, 99 + 70,and methane-
sulphonic acid, 98%, were obtained from Aldrich. Dioxane
and 4-methylpentan-2-one (iso-butyl methyl ketone) (MIBK)
were analytical grade from E. Merck, Darmstadt.
0340-7462179 /0402-0027$02.50/0
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28 J. A. Blanco, A. 0. Rucci et al. Propellants and Explosives 4,27-29 (1979)

Methanesulphonic acid was used to catalyze the reaction
according to literature(','). Dioxane as solvent and MIBK
as internal standard were selected in this study.
Molecular sieve 4 A beads from E. Merck, Darmstadt were
used for the removal of water from dioxane and 0.1 N metha-
nesulphonic acid in dioxane (solution employed for adding
the catalyst).
2.2. General procedure
Table 1. Recovery Data
Sample No. Water Recovered [%]
1 98.6
2 100.0
3 100.0
4 101.2
5 100.1
6 99.9

A step-by-step procedure is presented:

- Estimate the approximate water content of the NG-NC
paste.
- Weigh into a 25 ml volumetric flask, a sample of such weight
as to contain approximately 100 mg of water (the flask
must be well-stoppered all along the determination).
(Note: 100 mg is the recommended amount in order to get
an useful acetone peak size at the proposed chromatogra-
phic parameters. Nevertheless, samples containing 50 mg to
150 mg of water may be assayed without affecting seriously
the accuracy).
- Add approx. 10 ml of dried dioxane.
- Allow the mixture to stand at room temperature for 1&15
minutes, shaking it occasionally in order to ensure complete
wetting of the paste.
- Add 2 ml of DMP and 5 ml of 0.1 N methanesulphonic acid
dried solution.
- Allow it to stand for about 3-5 minutes, shaking it occasion-
ally.
- Add an accurately known amount of MIBK. (For example,
0.40 ml is a suitable amount according to the acetone to be
formed. Such size of MIBK may be conveniently and accu-
rately added by means of an appropriate pipette).
- Dilute to volume (accuracy is not needed) with dried
dioxane. Inject (0.5 pl-0.8 pl) into the gas chromatograph
at the forementioned operating conditions.
- Run the blank and the standard determinations on the same
amounts of reagents, at the same time as the sample deter-
mination, including all steps. Standard solution includes an
accurately known amount of water (i.e. 0.10 ml) added.
Each sample should be bracketed with the standard solution
before proceeding to the next unknown. A blank must be
run with each set of analytical determinations.
Results are obtained by means of the internal standard
technique, based on the acetone and MIBK peaks.
3. Results and Discussion
3.1. Accuracy
3.2. Precision
A study of the precision (6 replicates) showed the relative
standard deviation to be 1.3% when measuring the peak areas
and 0.8% when considering the peak heights, which is highly
satisfactory.
3.3. Selection of operating materials and parameters
Dioxane was the solvent chosen because of its unusual pro-
perty of dissolving both water and organic compounds (NG,
DMP, MIBK, methanesulphonic acid, and the acetone and
methanol formed in the reaction). Furthermore, it may be
dried to a negligible amount of water.
The stationary phase and solid support were selected after
investigation of several types of both chemicals. Gas solid
chromatography by means of Porapak Q gave satisfactory
separation between acetone and methanol, but the DMP in
excess decomposed, probably undergoing similar elimination
reaction as dimethylacetals of long-chained fatty aldehydes on
adsorptive GLC@).Extra peaks due to DMP decomposition
caused distortion of acetone and methanol peak shapes as they
were unresolved.
We were not able to obtain satisfactory separation of the
DMP reaction mixture at the chromatographic operating
conditions employed by Mary(g),so we modified some para-
meters (see section 2.1.) in order to achieve a desirabIe resolu-
tion between DMP and acetone peaks. A typical sample
chromatogram is shown in Fig. 1.
A:Extra peak
owing to DMP
decomposition
B=W(unchanged
excess)
CrAcet one
EMIRK
E=Oioxane(sdvent)

Specially prepared NG-NC pastes were analyzed to estab- E

lish the validity of the technique. These standard samples
and the respective standard solutions were added with known 1 D
weights of water. The results are shown in Table 1.
This study was carried out on samples containing amounts
of water ranging from 4% to 25%. Another sample of low
water content was assayed for water using the Karl Fischer
(KF) method and the gas chromatographic method according
to the general procedure described previously. KF titrations
were made on aliquots of an appropriate dilution of the sample
in dry dioxane. Good agreement was obtained between both
techniques. GI Figure 1. Typical sample chromatogram.

Propellants and Explosives 4, 27-29 (1979) Indirect Determination of Water in Nitroglycerin-Nitrocellulose Pastes
Another recommendation should be made on the experi-
mental factors that affect the resolution between DMP and
acetone peaks and, consequently, the precision and accuracy
of the determination. It was noticed that when the column
was installed in injector for flash vaporization, an extra peak
was visible in the chromatogram. This extra peak showed a
shorter retention time than the DMP and its size increased
when the injector temperature was raised (see Fig. 1) to about
140 "C.
As it was verified, the phenomenon is undoubtedly due to
the partial decomposition of the DMP excess (each increase
in the extra peak area is approximately in accordance with
the expected decrease in the DMP peak area as it was estab-
lished in the course of separate experiments). No production
of acetone and methanol is associated with this kind of
thermal decomposition with catalytic wall effects of S.S.
On the other hand, on-column injection produced nil or
negligible DMP decomposition when performing current
normal injection techniques. Decomposition could be induced
at some extent in on-column injection, when the needle was
intentionally forced to touch the inner wall of the column,
discharching the sample there.
The decrease in the DMP area improves resolution between
DMP and acetone peaks. Therefore, that is the reason by
which we have recommended flash vaporized injection, setting
injector tube temperature to 140 "C. At higher temperatures
than 140 "C, the decomposition phenomenon remained
essentially unchanged.
During the course of the work we took notice of an extra
phenomenon('*). When working at low flow rates of carrier
gas, the response of the FID to acetone was lower than the
normal according to FID relative sensitivities(''). The phe-
nomenon was not so evident for the other compounds peaks.
The trouble was avoided by adding an extra nitrogen flow as
it was previously described (section 2.1.).
MIBK was selected after investigation of several other
ketones, and complies with good advantage all requirements
for its use as internal standard.
Some NG-NC pastes used in this study included 2-nitrodi-
phenylamine which did not interfere with the determination.
4. Conclusions
The GLC method described here is an attractive alternative
to the methods at present being used to determine the water
content of NG-NC pastes. The procedure is simple and rapid,
and has been demonstrated to be very accurate and precise.
The total time for the determination on duplicate NG-NC
paste samples is within 2 6 2 5 minutes.
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29
5. Simplified method
A simplified procedure is suggested, which does not require
a gas chromatograph but gives less accurate results. It may be
useful for its application where GLC equipment is not avail-
able or when requiring only an approximate value of water
present in the pastes (for instance, intermediate determina-
tions, controlling the progress of the drying process of the
dough). The method is also based upon the water conversion
to acetone and methanol with DMP, which acts as a water
scavenger. The excess DMP (b.p. 83°C) and the methanol
and acetone formed are all highly volatile and will evaporate
at lower temperature and shorter time than water.
As it was previously discussed (section l.), results based on a
loss of weight by water evaporation are mainly objectionable
from the point of view of the partial volatilization of NG.
Nevertheless, the mild conditions required for the excess Dh4P
removal minimize NG volatilization, giving at the same time a
considerable practical advantage to the proposed simplified
procedure over currently desiccation techniques.
NG-NC paste samples were assayed at this laboratory for
water content by the DMP-reaction method on the basis of
loss of weight on heating at 85 "C at atmospheric pressure.
The results obtained were compared with those from the GLC
method (more accurate and less time-consuming) and the
comparative evaluation confirmed the noteworthy value of
the DMP-reaction-drying method for giving approximate
values of water content when the arrangement of GLC
equipment is not possible or necessary.
6. References
(1) P. Miaud, Mem. Poudres 37,465 (1955).
(2) M. Parpaillon, Mem. Poudres 40,217 (1958).
(3) F. E. Critchfield and E. T. Bishop, Anal. Chem. 33, 1034 (1961).
(4) D. S . Erley, Anal. Chem. 29, 1564 (1957).
(5) M. Hager and G. Baker, Proc. Montana Acad. Sci. 2 2 , 3 (1963).
(6) A. Badinand, C. Quincy and R. Guilluy, Trav. Soc. Phamz.
Morztpellier23, 207 (1963).
(7) J. H. Martin and A. M. Knevel, J. Pharm. Sci. 54,1464 (1965).
(8) M. B. Evans and B. Williamson, Chem. Ind. (London) 1171
(1970).
(9) N. Y. Mary, J. Chromatogr. 42,411 (1969).
(10) A. T. Blades, J . Chromatogr. Sci. 14,45 (1976).
(11) W. A. Dietz, J. Gas Chromatogr. 68, 5 (1967).
(Received October 23, 1978)