ISSN 10619348, Journal of Analytical Chemistry, 2015, Vol. 70, No. 1, pp. 87–91. © Pleiades Publishing, Ltd., 2015.

Original Russian Text © O.V. Rodinkov, E.A. Smirnova, L.N. Moskvin, 2015, published in Zhurnal Analiticheskoi Khimii, 2015, Vol. 70, No. 1, pp. 78–82.

ARTICLES

Effect of Temperature on the Performance Characteristics

of Continuous Chromatomembrane Gas Extraction
O. V. Rodinkov*, E. A. Smirnova, and L. N. Moskvin
Department of Chemistry, St. Petersburg State University, Universitetskii pr. 26, Peterhof, St. Petersburg, 198504 Russia
*email: rodinkov@rambler.ru
Received May 8, 2013; in final form, March 31, 2014

Abstract—The effect of temperature on the analytical characteristics of the continuous chromatomembrane

gas extraction of volatile organic compounds from aqueous solutions for their subsequent gaschromato
graphic determination is studied theoretically and experimentally. It is found that an increase in temperature
to 80°C lowers the detection limits of analytes by several times and significantly improves the performance of
the gasextraction system. The repeatability of the results does not depend on temperature when a water vapor
condenser is used in the line of extraction gas.

Keywords: gas extraction, headspace analysis, chromatomembrane mass transfer process, gas chromatog
raphy
DOI: 10.1134/S106193481501013X

The method of collecting information on the com EXPERIMENTAL

position of a condensed phase by analyzing the extrac
tion gas in contact with the phase (headspace analysis)
firmly entrenched in analytical practice for the gas
chromatographic determination of volatile organic
compounds in aqueous solutions [1–5]. The results of
previous studies [7–10] have shown that chro
matomembrane gas extraction is one of the most
effective options for gas extraction. The conditions
necessary for the implementation of chromatomem
brane mass transfer processes were described in detail
previously [7, 10]. However, the effect of temperature
on the analytical capabilities of chromatomembrane
gas extraction (CMGE) has not been studied. In
accordance with the trend towards the automation of
chemical analysis, the improvement of performance in
a continuous version of headspace analysis based on
the principles of CMGE, enabling the recording of
instant spontaneous changes in the composition of the
test object, is a no less important problem [11]. The
performance characteristic of chromatomembrane
cells (CMCs) is the time for which the concentration
of extractable substance in the extraction gas flow is
changed after the change of its concentration in an
aqueous sample stream.
The goal of this work was to evaluate the effect of
temperature on the detection limits of analytes, the
repeatability (convergence) of the results of headspace
analysis, and the performance of CMC under the con
ditions of continuous CMGE.
The gas chromatographic determination of com
ponents was carried out using a Tsvet 500M laboratory
chromatograph with a flame ionization detector. A
stainless steel analytical column (150 × 0.3 cm) was
packed with Chromosorb101, particle size 0.16–
0.22 mm. The conditions of gaschromatographic
determination were as follows: the temperature of the
injector and detector was 210°С, and the column tem
perature was varied in the range from 160 to 200°С
depending on the analytical task. The extraction gas,
coming out from the CMC, was metered using a man
ual unheated valve with a sampling loop 1.9 mL in vol
ume.
The chromatomembrane mass transfer process was
carried out in a selfengineered CMC with a polytet
rafluoroethylene biporous matrix of a cylindrical
shape (16 mm in diameter and 20 mm in height). The
method for manufacturing biporous matrices was
described previously in [12]. The size of macropores in
the matrix was 1 to 2 mm, and the size of micropores
was from 10 to 30 µm. The injection of the extraction
gas into the biporous matrix and the output from it
were carried through microporous polytetrafluoroeth
ylene membranes (Ecoflon, Russia) with an average
pore diameter of 0.5 µm. The CMGE process was
investigated using a cocurrent version of the circuit of
relative movement of phases, in which the flows of liq
uid and gas phases are moved in the same direction. It
was shown previously that this version is only slightly
inferior to other versions in terms of the detection lim
its of analytes, but surpasses them in performance
[13]. The flow rates of the extraction gas and aqueous

87
88
h/h0
18
16
14
12
10
8 of сst.
6
4
2
0 stant; and Ai = µ i0,II – µi0,I is the difference of the stan
290 310 330 350
T, К
Fig. 1. Relative peak heights as functions of temperature;
h0, the height of the peaks at 25°С; WG = 4.5 mL/min;
WL = 4 mL/min; analyte (сL, mg/L): (1) ethyl acetate
(50), (2) acetone (150), and (3) benzene (2).
sample through the CMC were set with additional flow
regulators. The extraction gas flow rate was measured
by a soapfilm flow meter, and the flow rate of liquid
phase was determined using a graduated cylinder and
a stopwatch. The test CMC was placed in a LOIP LT
200 liquid circulation thermostat. For the experi
ments, we used model aqueous solutions of test com
pounds such as acetone, ethyl acetate, and benzene at
a known concentration (сL). These analytes differ from
each other in partition coefficients (K) by several
orders of magnitude in the system of aqueous phase–
gas phase. At 25°С, the values of K for acetone, ethyl
acetate, and benzene are 551, 150, and 4.0, respec
tively [2], which allows the generalization of the
results.
To investigate the performance of the CMC, the
flows of distilled water and the model aqueous solution
with a known concentration of analytes were sequen
JOURNAL OF ANALYTICAL CHEMISTRY
RODINKOV et al.
tially passed through the cell with predetermined flow
rates. In both cases, the flow of extraction gas was
simultaneously passed through the CMC, and then it
was directed into the chromatograph for recording
1 changes in the concentration of analytes in the extrac
tion gas over time. Experiments were carried out at
four different temperatures of the thermostat.
To assess the effect of temperature on the detection
limits, the concentrations of analytes in the extraction
gas flow were recorded at each temperature and at dif
ferent ratios of flow rates of the gas and aqueous phases
2 through the CMC. The detection limits (сmin) of the
analytes were calculated by the equation [14]
сmin = 2σ(сst/hst),
where σ was the detector noise and hst was the height
of the chromatographic peak in the analysis of an
aqueous solution with a concentration of the analyte
The accuracy of the results was evaluated by the
standard addition method.
RESULTS AND DISCUSSION
3 It is known [2] that a change in temperature results
in a significant change in the partition coefficient in a
liquid–gas system of K = cL/cG. The temperature
dependence of the partition coefficients is
lnKi = (Ai/RT) – B, (1)
where T is temperature, K; R is the universal gas con
dard chemical potentials of the component in vapor
and liquid. Value В includes the logarithms of the
activity coefficients of the ith component in the equi
librium phases and the transition modules from mole
fractions to molar concentrations.
According to Eq. (1), with increasing temperature,
K should decrease and the concentrations of analytes
in the extraction gas should correspondingly increase,
resulting in a decrease in their detection limits. Within
the linear range of the detector signal dependent on
the analyte concentration, the ratio of the peak heights
of an analyte in the chromatogram of h/h0 at this tem
perature and 25°C is the ratio of the corresponding
concentrations of the analyte in the flow of extraction
gas. The dependences in Fig. 1 illustrate the positive
effect of increasing temperature, which is manifested
in an increase in the concentrations of analytes in the
gas phase. On the basis of these data, we could con
clude that heating from room temperature to 80°C
lowers the detection limit for acetone by 12 times; for
ethyl acetate, by 16 times; and for benzene, by approx
imately 4 times (Table 1).
In a narrow temperature range, values Ai and В in
Eq. (1) are practically independent of temperature;
therefore, a linear increase in lnKi should be observed
with increasing reciprocal temperature (1/Т) and, as a
Vol. 70 No. 1 2015