ISSN 1087-6596, Glass Physics and Chemistry, 2019, Vol. 45, No. 5, pp. 360–364. © Pleiades Publishing, Ltd.

, 2019.
Russian Text © The Author(s), 2019, published in Fizika i Khimiya Stekla.

Optimization of the Sample Preparation Technique

for the Gas-Chromatography Determining of Micro-Concentrated
2-Chlorovinyl Dichloroarsine Vapor in Air
E. A. Spetsova, * and L. A. Nefedovab
aSPS
Eurochim Ltd., St. Petersburg, 195267 Russia
b
JSC SZRC Concern VKO Almaz-Antey, St. Petersburg, 192012 Russia
*e-mail: evgenii.spetsov@gmail.com
Received February 14, 2019; revised May 27, 2019; accepted June 6, 2019

Abstract—In this work, a new method for preparing samples with 2-chlorovinyl dichlorosine is optimized: its
main difference from the prototype consists in the application of the combined adsorption–extraction pro-
cess instead of the method of absorption by bubbling. The optimization includes the selection of an adsorbent
and the sampling conditions (concentration of the analyzed substance vapors, composition of the eluent, and
rate of the vapor-air flow). The positive effect of the low specific surface of the adsorbent on the degree of the
extraction of the adsorbate is established. The optimal volume ratio of ethanol and hydrochloric acid is pro-
posed, which allows us to almost completely extract the reagent.

Keywords: 2-chlorovinyl dichloroarsine, sorption, gas chromatography, extraction

DOI: 10.1134/S1087659619050134

INTRODUCTION in the air, it is necessary to increase the sampling time

In accordance with the Convention on the Prohibi-
tion of Chemical Weapons, in particular, 2-chlorovi-
nyl dichloroarsine (CVDCA) [1], the methods of ana-
lytical chemistry aimed at accurately determining the
microconcentrations of this substance in the air of the
working zones of destruction facilities for toxic sub-
stances are being actively developed.
Mobile gas detectors, for example, those of the
GSA-01F, GSA-KR, GSA/AIG, and SIP-1 grades are
used on the territory of such facilities and in field con-
ditions: strict demands are placed on their reliability in
the course of continuous operation in an environment
with low concentrations of vapors of potent poisons.
Such devices are subject to periodic calibration using
the validated methods of quantitative analysis. The reli-
ability of the analysis for most of the substances nor-
mally decreases near the lower concentration limit of
detection, so that the measurement error increases. For
CVDCA vapors in air, this limit is 2 × 10–4 mg/m3 [2].
The same concentration value corresponds to the max-
imum permissible concentration for the working zone,
which is considered as the norm only when remaining
in the contaminated atmosphere for a short period.
However, the procedures used to neutralize this poison
must be carried out around the clock. The objective of
the present study was dictated by the insufficient sensi-
tivity of the applied gas chromatography analysis, for
which this concentration of CVDCA represented the
lower detection limit. With a lower content of CVDCA
(absorption of the substance from the analyzed gas–
vapor mixture (GVM) into the absorption solution) or
the volumetric rate of GVM upon bubbling, which
increases the loss of the absorbent due to the drop car-
ryover and, as a result, the total measurement error.
The adsorption of CVDCA with its subsequent liq-
uid extraction (elution) from the adsorbent layer rep-
resents a promising alternative method of sample
preparation prior to the gas chromatography analysis.
Mathematical calculation demonstrated that this
technique was promising due to the significant reduc-
tion of the sampling time to 0.10–0.15 h with the GVM
volume flow rate of 360 to 600 dm3/h compared to the
absorption method (at least 0.5 h at the maximum
possible flow rate of 60 dm3/h), while providing the
almost complete capture of CVDCA in an ergonomic
absorption tube. The tasks of the study are to compare
the adsorption and desorption capacity of the main
types of industrial adsorbents; to select a high-perfor-
mance eluent for 2-chlorovinyl dichloroarsine; and to
determine the gas-dynamic conditions to ensure the
optimal criteria for the maximum sampling rate and
compactness of the applied adsorption tube.
METHODS OF STUDY
The absorption capacity of the industrial adsor-
bents was investigated at temperature (28 ± 1)°С in a
gas-dynamic installation (GDI) made of glass (Pyrex)

360
 OPTIMIZATION OF THE SAMPLE PREPARATION TECHNIQUE
and mounted in a thermostated box. The CVDCA was
dosed from a removable capillary cell by blowing it
with nitrogen at a volume flow rate of 18 dm3/h. There-
after, the stream of nitrogen contaminated by 2-chlor-
ovinyl dichloroarsine was mixed with dry (dew point –
60°C) and moist airflows with volume flow rates of 162
and 180 dm3/h, respectively. The relative humidity of
the GVM was maintained at a level of (50 ± 5)% under
constant recording by a VIT-2 automatic psychromet-
ric hygrometer (Russia).
When developing the conditions for the adsorption
of 2-chlorovinyl dichloroarsine on the experimental
sorbent samples, their weights were selected empiri-
cally so that the CVDCA breakthrough concentrations
behind the adsorbent layer were absent, which, in
turn, was determined by the gas chromatography anal-
ysis of the absorbing solution from the bubbler
installed after the mixture.
Sampling at the GDI outlet was carried out simulta-
neously through the absorbent using a Richter absorber
(by bubbling through 10 cm3 of 0.1 N aqueous HCl
solution); through the adsorbent poured into the glass
tube with an internal diameter of 8 mm and using an
aspirator (Technical Conditions (TU) no. 64-1-862-
82) with rotameters of the inhalation anesthesia appa-
ratus (Technical Conditions (TUs) no. 64-1-0801-256-
80) with the GVM volume flow in each line of 60 dm3/h
for 0.5 h.
The GVM for the content of CVDCA, both
selected in the absorption solution and extracted from
the adsorbents, was analyzed using an Agilent 7890B
gas chromatograph (United States) with a flame ion-
ization detector. The column filler (grade HP-5:
length 30 m, diameter 0.32 mm), Tenax sorbent
(USA); thermostat heating rate ranged from 40 to
170°С, 25°С/min; carrier gas rate (nitrogen),
7.1 cm3/min; temperature of the detector, 160°С, that
of the evaporator, 100°С (in Splitless mode at a flow
rate of 40 cm3/min for 2 min); gas flow rates: air,
300 cm3/min; H2, 30 cm3/min; N2 (blowing),
25 cm3/min. The retention time of acetylene (the
product of the chemical reaction of CVDCA with
sodium hydroxide) was (2.90 ± 0.05) min. Acetylene
vapor was sampled (in a volume of 1 cm3) by a syringe
at a distance of 1 cm from the gas–liquid interface in the
closed tube immediately after elution of the sorbent.
A photocolorimetric method of analysis was
applied to calibrate the gas chromatograph. It con-
sisted in the registration of changes in the color of the
indicator solution upon its contact with the CVDCA
decomposition product—acetylene [3]. To find the
value of the change in the intensity of the monochro-
matic light (wavelength 400 nm) passing through the
indicator solution with the 2-chlorovinyl dichloroarsin
sample relative to the reference solution not containing
the latter, a KFK-2 photoelectric photometer (Russia)
was used (optical density measurement error ± 1%
GLASS PHYSICS AND CHEMISTRY Vol. 45 No. 5
361
(Russian state standard no. 12083-78), cuvettes with a
working length of 30 mm). The concentration of
CVDCA corresponding to the measured intensity in
the sample and in air was determined according to the
preset calibration characteristic.
The adsorbent loading weight was measured via the
gravimetric method using a Shinko AF-R220CE lab-
oratory electronic balance (Japan) (accuracy class I
(spec.) with a measurement error of 10–4 g).
EXPERIMENTAL
RESULTS AND DISCUSSION
In order to compare the sorption properties, the
following commercial adsorbents were selected: BAU-
A and OU-A active carbons (Russia), ASK silica gel
(Russia), AOK-63-21 aluminum oxide for chroma-
tography (Russia), alkoxylated glass fiber (United
States), and a fine-fraction Tenax sorbent, linear poly-
n-2.6-diphenylphenylene oxide (United States) [4, 5].
Their main physical and textural characteristics are
provided in Table. 1.
At the first stage, the GVM was passed through the
adsorbents and bubblers with the absorbent (0.1 N
aqueous solution of HCl) indicated in Table 1, and the
resulting samples of the absorption solutions and
extracts were analyzed for the content of CVDCA.
Technical rectified ethanol (Russian state standard
no. 18300-87) and a 0.1 N aqueous solution of hydro-
chloric acid of 5.5 cm3 each were used as eluents for
sequential extraction. The experimental results are
provided in Table 2.
Based on the data of Table 2, the highest degree of
extraction of the sorbate was attained upon the elution
of CVDCA from sorbents such as Tenax, fiberglass,
and BAU-A. In the course of the experiments, it
appeared that the mentioned active carbon (due to its
low resistance to abrasion) and aluminum oxide (due
to the high degree of grinding during elution) were
partially transferred to the extract as a suspension. The
actual concentration of 2-chlorovinyl dichloroarsine
in the extract could be underestimated, since the fine
particles of the adsorbent, which were also inside it,
were able to concentrate the analyzed component.
As a result of the experiments, it was established
that only the fiberglass and the Tenax sorbent could be
considered as suitable materials for further research.
The extraction capacity of the previously used eluents
(11 cm3) was estimated for these materials; see Table 3.
As seen from Table 3, a higher degree of CVDCA
extraction was attained on the Tenax sorbent. How-
ever, the additional experiments revealed some diffi-
culties associated with an increase of the hydraulic
resistance of the layer of the fine-fraction batch mix-
ture of the sorbent to the GVM flow upon the increase
of the volume flow rate of the latter. Because of the
higher cost of this sorbent, the preference was given to
2019
362 SPETSOV, NEFEDOVA

Table 1. Properties of the commercial adsorbents

Dimensions Shape Specific surface area Volume of pores
Grade
of granules, mm of granules/material of pores by BET, m2 g–1 by H2O, cm3 g–1
Tenax 0.18–0.25 Round-shaped, oval-shaped 18.6 ± 0.5 0.67
ASK 0.25–0.50 Sand 260 ± 10 1. 0
Fiberglass – Thread-like fiber 40 ± 2 –
AOK-63-21 0.10–0.16 Powder 60 ± 3 0.3
BAU-A 1.0–4.0 Irregular-shaped 750 ± 50 1.6
OU-A 1.0–2.0 '' >1200 2.0

Table 2. Comparison of desorption capacity of the commercial adsorbents in the extraction of 2-chlorovinyl dichloroarsine
from them sequentially by ethanol and HCl solution
Initial concentration of CDVCA Concentration of CDVCA Degree of extraction of CVDCA
Grade
10 4 mg m–3 after extraction 10 4 mg m–3 from the sorbent, %
Tenax 2.86 2.76 96.8
Fiberglass 2.30 1.65 71.8
ASK 3.01 1.87 62.1
BAU-A 2.71 2.11 78.1
OU-A 3.01 1.43 47.6
AOK-63-21 3.34 1.55 46.4

Table 3. Comparison of desorption capacity of ethanol and hydrochloric acid solution upon single-stage extraction of
2-chlorovinyl dichloroarsine from the commercial adsorbents
Initial concentration Concentration of CDVCA Degree of extraction of CVDCA
Grade Eluent
of CDVCA 104 mg m–3 in the extract 104 mg m–3 from the sorbent, %
Tenax Ethanol 2.99 2.83 94.6
0.1 N of HCl (aq.) 4.31 1.60 37.2
Fiberglass Ethanol 5.41 1.76 32.5
0.1 N of HCl (aq.) 2.88 2.03 70.5

the glass fiber, which was used to further optimize the
sampling conditions. It was suggested that the maxi-
mum degree of the CVDCA extraction from this sor-
bent (70.5% on extraction by diluted hydrochloric
acid) could be increased by selecting the optimal elu-
ent and its composition.
Upon elution from the glass fiber, sequential
extraction was applied by dimethyl sulfoxide (DMSO);
and thereafter, with the solution of 0.1 N HCl, as well as
one-stage extraction by a mixture of aqueous solutions
of ethanol (5.5 cm3) and 0.1 N of HCl (5.5 cm3) at var-
ious concentrations of alcohol. The results are provided
in Table 4.
DMSO was characterized with a pronounced
extracting ability relative to the combined alcohol–
acid eluent. Note that it was possible to achieve its
almost complete extraction due to the application of
the latter with the ethanol concentration of 2.0 N at
the initial content of CVDCA in the GVM of 4.37 ×
10–4 mg/m3. Apparently, with the CVDCA concentra-
tion increase in the GVM, its extraction from the glass
fiber required increasing the volume of the eluent.
This enabled us to suggest that, upon sampling air with
target concentrations of CVDCA below 2 × 10–4 mg/m3,
it will be possible to achieve the almost complete
desorption of this sorbent.
The desorption capacity of CVDCA from the fiber-
glass was investigated at variable linear rates of the
GVM and in two extraction modes: single-stage, by a
2.0 N ethanol solution in a 0.1 N HCl solution of the
total volume of 11 cm3, and two-stage, sequentially
with the same solutions of ethanol and HCl, of 5.5 cm3
each. Each sample was prepared according to the
scheme shown in Fig. 1 for 0.5 hours. The results are
shown in Table 5.
The data from Table 5 indicate that application of
the single-stage extraction of CVDCA from the glass
fiber by an aqueous acid–alcohol solution was slightly
more efficient than the two-stage extraction, i.e., at
the sequential application of the components—solu-
tions of ethanol and HCl. It was possible to almost
completely extract the adsorbed CVDCA even at the
linear flow rate of the GVM of about 13 cm/s (the vol-
ume flow rate of 368 dm3/h). This allowed reducing

GLASS PHYSICS AND CHEMISTRY Vol. 45 No. 5 2019

 OPTIMIZATION OF THE SAMPLE PREPARATION TECHNIQUE 363

Air 3

GVM 2

Nitrogen
1

4
4

Fig. 1. Scheme of the samples preparation from the GVM flow. (1) GDI; (2) sampling tube with the sorbent; (3) aspirator;
(4) Richter absorbers (bubblers).

the sampling time with the minimum amount of
CVDCA necessary for the GC-analysis from 30 (with
the absorption sampling method) to 5 minutes.
Apparently, CVDCA vapors can be completely
absorbed not only by porous adsorbents (for example,
Tenax) but also by materials with high values of the
external surface area (glass fiber). The high sorption
capacity of silicon oxide, which was a component of
the glass fiber, was of particular interest, because the
other materials based on it could be of greater interest
than the glass fiber itself. The absence of pores, espe-
cially fine ones, in a sorbent can contribute to its abil-

Table 4. Efficiency of the combined eluents in extraction of 2-chlorovinyldichlorosin from fiberglass

Initial concentration Eluent Concentration of CVDCA Degree of extraction of CVDCA
of CVDCA 10 4, mg m–3 (volume 11 cm3) in the extract 10 4 mg m–3 from the sorbent, %
3.01 DMSO, then 0.1 N of HCl (aq.) 2.17 72.1
5.71 3.0 N ethanol + 0.1 N of HCl (aq.) 4.74 83.0
4.37 2.0 N ethanol + 0.1 N of HCl (aq.) 4.37 100.0
5.41 5.08 93.9
5.64 4.64 82.3
6.56 4.84 73.7
6.61 4.11 62.1

Table 5. Change in the desorption capacity of the fiberglass with varying linear flow rate of the GVM and depending on the
extraction mode
Adsorbent layer parameters Volumetric flow rate, Concentration of Degree of extraction
Initial concentration 3 h–1/Linear rate,
dm CVDCA in the extract of CVDCA from the
of CVDCA 104,
weight, g diameter, mm cm s–1 of GVM through after one-/two-stage sorbent, % after one-/
mg m–3
the layer of adsorbent extraction 104 mg m–3 two-stage extraction
0.797 8.0 4.37 56.2/3.11 4.37/– 100.0/–
0.724 4.67 137.4/7.60 4.67/– 100.0/–
0.758 2.30 56.2/3.11 –/1.65 –/71.8
0.736 2.54 137.4/7.60 –/1.80 –/70.9
1.048 10.0 4.68 368.6/13.04 4.65/– 99.4/–
0.842 1.47 365.8/12.94 1.47/– 100.0/–
0.951 1.63 365.8/12.94 –/1.59 –/97.6
0.941 1.51 365.8/12.94 –/1.48 –/98.0

GLASS PHYSICS AND CHEMISTRY Vol. 45 No. 5 2019

364 SPETSOV, NEFEDOVA
Table 6. Desorption ability of quartz sand on 2-chlorovinyl
dichloroarsine. Weight of the sorbent, 3.0 g; diameter, 10.0 mm;
linear rate of GVM, 13.0 cm/s; sampling time, 0.083 h
Initial The degree
Concentration
concentration of extraction of
of CVDCA in the
of CVDCA 104 CVDCA from the
extract 104 mg m–3
mg m–3 sorbent, %
Single-stage extraction
2.11 2.11 100.0
1.47 1.47 100.0
Two-stage extraction
1.63 1.47 90.2
1.51 1.36 90.1
ity to regenerate, i.e., to improve the efficiency of the
adsorbate extraction process. Quartz is a low-cost
sorption material that is potentially effective with rela-
tion to polar molecules forming the vapor phase [6, 7]
and allows broad variations of its particles shapes and
sizes for actual hydrodynamic conditions.
The experiments were carried out on the
extraction of CVDCA from quartz sand (particle size
0.25–0.50 mm, specific surface area ((1.0 ± 0.5) m2)
using the above-described two-stage extraction
method (2.0 N aqueous solutions of technical ethanol,
followed by 0.1 N of HCl) and the single-stage
extraction (their mixture in equal volumes) under
constant hydrodynamic parameters. The results are
provided in Table 6.
In the single-stage extraction (Table 6), the effi-
ciency of the application of quartz sand for the
extraction of CVDCA from it was almost 100%, which
was in accordance with the efficiency of the glass fiber.
In the two-stage elution method, this value was sig-
nificantly lower—by approximately 90%, which was
probably due to the lower extraction capacity of the
hydrochloric acid solution compared to ethanol.
The suggested method of sample preparation, the
process of CVDCA elution, and the introduction of
the extrudate into the chromatograph evaporator
implied application of the volumetric measuring
devices—pipette (10 mL) and syringe dispenser (1 mL),
whose relative measurement errors were 0.5 and 1.0%,
respectively. The relative error of the chromatography
method of measurement did not exceed 10%.
CONCLUSIONS
The investigated method of the sample prepara-
tion, including the process of adsorption of 2-chlor-
ovinyl dichloroarsine and its extraction into the bulk of
the eluent, can be applied as part of the existing gas
chromatography method for the quantitative analysis
of air in the working areas of facilities for the destruc-
GLASS PHYSICS AND CHEMISTRY
tion of chemical weapons and test sites, as well as for
the calibration of measuring and alarming devices. An
important advantage of the new method lies in the
possibility of carrying out remote work on sampling in
an absorption tube with a solid sorbent while remain-
ing in the contaminated atmosphere for a short period.
It has been methodologically and economically advised
to use fiberglass or silica sand characterized with an
undeveloped texture for the sorption of 2-chlorovinyl
dichloroarsine vapor from (1.5–2.1) × 10–4 with up to
100% efficiency to ensure sample preparation for its
quantitative analysis. These sorbents have allowed
sampling 2-chlorovinyl dichloroarsine vapor at a rate
of the analyzed airflow that is 6 times faster than the
existing method, which has reduced the operation
time from 30 to 5 minutes. The effective eluent that
allowed the complete extraction of the sorbed 2-chlor-
ovinyl dichloroarsine from the surface of the investi-
gated sorbents was made up of a mixture of aqueous
solutions of ethanol and hydrochloric acid in concen-
trations of 2.0 and 0.1 N, respectively, with their vol-
ume ratio of 1 : 1.
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Translated by D. Marinin
Vol. 45 No. 5 2019