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Methods and Devices for the Preparation of Standard Gas Mixtures

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DOI: 10.1134/S1061934818020090

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ISSN 1061-9348, Journal of Analytical Chemistry, 2018, Vol. 73, No. 2, pp. 109–127. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © I.A. Platonov, O.V. Rodinkov, A.R. Gorbacheva, L.N. Moskvin, I.N. Kolesnichenko, 2018, published in Zhurnal Analiticheskoi Khimii, 2018, Vol. 73,
No. 2, pp. 83–105.

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Methods and Devices for the Preparation of Standard Gas Mixtures

I. A. Platonova, *, O. V. Rodinkovb, A. R. Gorbachevab, L. N. Moskvinb, and I. N. Kolesnichenkoa
aSamara
National Research University, Samara, 443086 Russia
b
Institute of Chemistry, St. Petersburg State University, Petrodvorets, St. Petersburg, 198504 Russia
*e-mail: pia@ssau.ru
Received May 26, 2017; in final form, August 24, 2017

Abstract⎯A review of methods for the preparation of standard gas mixtures (SGMs) with the known concen-
trations of organic and inorganic gases and vapors is presented. The classification of methods is proposed and
their advantages and disadvantages are compared. Along with the widely known thermal diffusion and gas-
extraction methods and devices for the preparation of SGMs functioning on their basis, i.e., sources of gas
and vapor microflows and vapor-phase sources of gas mixtures, the review considers and discusses metrolog-
ical possibilities proposed by Russian researchers of chromatomembrane and chromato-desorption methods
of SGM preparation and corresponding instrumentation.

Keywords: gas mixtures, standard, methods and devices for preparation, chromatomembrane, chromato-
desorption
DOI: 10.1134/S1061934818020090

The development and improvement of methods
and devices for the preparation of standard samples of
the composition of substances and materials is an
urgent problem of present-day analytical chemistry.
Such samples are widely used for the calibration of
analytical instruments and the control of the accuracy
of the results of chemical analysis [1]. Because of spe-
cific features of the gaseous state, the most difficulties
arise in the preparation of standard samples of the
composition of gas mixtures [2]. In view of the lack of
available methods for the preparation of standard gas
mixtures with the known concentrations of volatile
organic compounds (VOCs), in most cases, the devel-
opment and control of the accuracy of procedures for
the analysis of gas media, in particular, air, is done
using standard solutions of target components. The
application of SGMs is not limited only by the sphere
of chemical analysis, but is also associated with the
need in the creation of model atmospheres for testing
and studying reactions and processes, assessing the
efficiency of catalysts, creating artificial atmospheres
in the cultivation of cells and tissues, and for solving
many other problems.
The methods proposed so far and devices for the
preparation of SGMs are quite numerous and diverse.
However, this variety points more to the restrictions
and drawbacks of the corresponding methods
rather than to the simplicity of solving the above
problem. Recent reviews are indicative of the impor-
tance of problems dealing with the preparation of
SGMs [3–5]. These reviews virtually did not reflect
the progress of Russian researchers and instrument
makers in the specified area, and the problems of the
preparation of SGM directly at the working place, like
the preparation standard liquid solutions in the chem-
ical analysis in these reviews are considered in insuffi-
cient detail.
The aim of the present review was a comprehensive
consideration of methods and devices for the prepara-
tion of SGMs, including chromatomembrane and
chromato-desorption ones, which are aimed at pre-
paring gaseous VOC mixtures with the specified con-
centrations of target components directly in an analyt-
ical laboratory in performing an analysis.
METROLOGICAL ASPECTS
OF THE PREPARATION
OF STANDARD GAS MIXTURES
Standard gas mixtures are used as means for the
storage, reproduction, and transfer of units of compo-
nent concentration in the gas phase. In accordance
with the CIS interstate standard GOST 8.578-2014
[6], depending on their performance characteristics,
SGMs are divided into 3 types: categories 0, 1, and 2.
Standard gas mixtures are standard samples of the
composition of gas mixtures stored in cylinders under
pressure [7] and gas mixtures generated by gas-mixing
installations and generators. In the first case, the target
components contained in SGMs under standard con-
ditions are, usually, gaseous substances and their con-
centrations can be expressed in mole or volume frac-
tions or percent and, in the second case, SGMs con-
tain vapors of liquid or solid substances, and their

109
110 PLATONOV et al.
Table 1. Requirements for performance characteristics of standard gas mixtures of different categories [6]
Concentration range
SGM source
of the target component
Cylinders under pressure 5 × 10–5–99.5%
99.5–99.9%
Gas-mixing installations 1 × 10–6–100%
Generators of gas mixtures 1 × 10–6–1.5 × 103 mg/m3
concentration is quite often expressed in mg/m3. The
requirements to performance characteristics of SGMs
of various types are summarized in Table 1.
CLASSIFICATION OF METHODS
FOR THE PREPARATION
OF STANDARD GAS MIXTURES
Despite a wide variety of the known methods for
the preparation of SGMs, they can be divided into two
big groups: static and dynamic [3–5]. Sometimes
chemical and electrochemical methods, in which tar-
get components are formed as a result of chemical and
electrochemical reactions, respectively, are assigned to
a separate group (Table 2).
Static methods actually copy the scheme of the
preparation of standard liquid solutions and are based
on the dilution of a known amount of target compo-
nents by a dilution gas, which, in contrast to liquids,
has no certain occupied volume, which creates addi-
tional experimental difficulties. Static methods can be
implemented both at elevated and atmospheric pres-
sures of the dilution gas in rigid or flexible vessels.
Dynamic methods are based on the introduction of
target components into a flow of a dilution gas. They
can be divided into nonequilibrium and equilibrium
ones. In the most widespread nonequilibrium meth-
ods, target components from a liquid or a gas phase at
a constant rate diffuse into a dilution gas flow through
a capillary or a membrane. Equilibrium methods are
based on the saturation of a dilution (extractant) has
flow with target components on its contact with a gen-
erating solution with certain concentrations of these
components.
STATIC METHODS FOR THE PREPARATION
OF STANDARD GAS MIXTURES
Static methods are most often used to obtain stan-
dard mixtures of small volumes. A vapor−gas mixture
with a specified concentration is prepared by the
introduction of a certain weighed portion or a volume
of a volatile compound into a container of a known
volume [8–15]. The preparation of SGMs by the static
method includes the following stages: control of the
internal surface of tanks and valve equipment; pump-
JOURNAL OF ANALYTICAL CHEMISTRY
Relative error, %
category 0 category 1 category 2
6–0.03 10–0.05 12–0.1
0.03–0.008 0.05–0.1 0.1–0.05
6–0.0015 10–0.003 12–0.05
7–3 13–6 25–10
ing out the tank and its purging with an inert gas; ther-
mostatic control; input of individual components;
homogenization of the system; and analysis of the sys-
tem (measurements of the concentrations of individ-
ual components, their pressure, volume or weight).
On the availability of precise equipment for weighing
and dispensing, static methods are irreplaceable in the
preparation of SGMs, including those of categories
0 and 1; however they have a great number of possible
sources of errors. The application of these methods is
limited to concentrations not lower than 10−4−10−5%,
because, at lower concentrations of individual compo-
nents, the stability of SGMs is deteriorated because of
sorption effects, and, in certain cases, losses can reach
50%. The containers can be big glass bottles, metal
cylinders, or capacities made of polymeric materials;
the main condition is the inertness of the vessel mate-
rial to the components of gas mixtures. For example,
one cannot use glass vessels for the preparation of mix-
tures of fluorinated substances and metal cylinders in
the presence of acid-forming gases (hydrogen chlo-
ride, sulfur and nitrogen oxides) in the mixture. In
using polymeric materials, one should take into
account a possibility of the diffusion of the studied
component through the vessel walls.
Depending on the pressure in the system, we can
distinguish several groups of static methods.
The manometric method is based on the exact dos-
ing of gas mixture components at a certain pressure
into the cylinder [12–15]. Gas pressure in the vessel is
determined with a precise manometer. The composi-
tion of the mixture is calculated by the equations of the
state of pure gases and gas mixtures. Based on the
assumption that the mixed components satisfy the
ideal gas law, their concentrations are proportional to
partial pressures of individual components. However,
because of the influence of various factors (molecular
and electrostatic interactions, hydrogen bond forma-
tion, quantum effects, etc.), real systems differ from
ideal gases and, in the description of real systems of
mixed gases, one should take into account the com-
pressibility factor [15]. Up-to-date complexes imple-
menting the manometric method include not only
precision dispensing devices, but also computer sys-
tems and software for the control of the process,
Vol. 73 No. 2 2018
 METHODS AND DEVICES FOR THE PREPARATION 111

Table 2. Classification of methods for the preparation of standard gas mixtures [3–5]
Conditions Name Principle of the method
Static methods
At elevated pressure Manometric Precise dosing of mixture components to the cylinder
at a certain pressure
Volumetric Consecutive introduction of specified volumes of mix-
ture components into the cylinder
Gravimetric Consecutive introduction of weighed mixture compo-
nents into the cylinder
At atmospheric pressure Use of rigid chambers Introduction of specified amounts of mixture compo-
nents in a preevacuated vessel of constant volume
Use of flexible chambers Similarly to the previous case, but in the vessel of var-
ied volume
Static gas extraction Equilibrium distribution of components between
the solution and gas phase in the vessel
Dynamic methods
Nonequilibrium Exponential dilution Substance introduction into a vessel with a stirrer,
through which dilution gas is passed continuously
Mixing gas flows Mixing of several regulated gas flows with specified
flow rates
Injection Dosing of liquid in a flow of dilution gas
Diffusion Diffusion of liquid vapors to a flow of dilution gas
through a capillary
Membrane Diffusion of liquid vapors to a flow of dilution gas
through a membrane
Chemical and electrochemical Dilution of substances forming in chemical or electro-
chemical reactions with a flow of dilution gas
Equilibrium Continuous gas extraction Distribution of target components between the solution
and a flow of gas passing through the solution or over it
Chromatomembrane Distribution of target components between the liquid
and gas phases in a biporous medium nonwettable
with a liquid
Chromato-desorption Distribution of target components between a gas flow
and a liquid applied on a solid support

which ensures the reduction of possible random errors
[12, 13].
The volumetric method [16] consists in the consec-
utive introduction of gas mixture components mea-
sured in temperature-controlled vessels of a constant
volume into a cylinder. The composition of the pre-
pared mixture is calculated by equations of the state of
pure gases. It is necessary to determine the compress-
ibility factor, because it considerably differs from
unity. The concentration of a component to be diluted
in the SGMs is calculated as the ratio of the amount of
the analyte (mol) to the amount of the dilution gas.
The gravimetric method opens a possibility of
avoiding errors due to sampling and precise dispensing
of components and arising in the measurements of
pressure and volume. This method is based on the
consecutive introduction of gas mixture components
weighed with a high precision into a cylinder [17–20].
A distinguishing feature of the method is the calcula-
tion of the composition of SGMs by the mass ratio of
the dosed components. In the absence of sorption and
desorption effects, the calculations take into account
only the correction for the purity of the initial gases.
The accuracy of the method is limited by the accuracy
class of balances, which are intended for work at high
loads, and by the skills of the operator. In combining
the gravimetric method with the dynamic dilution of
the flow, there appears a possibility of the consider-
able expansion of the range of working concentrations
[21–31].
The group of static methods for the preparation of
SGM under atmospheric pressure is based on the
introduction of a known amount of a substance into a
previously evacuated vessel using a soldered ampoule,
a syringe, or a calibrated pipette. After that, pressure in
the vessel is brought to atmospheric by slightly open-
ing the valve. In the introduction of a liquid into a ves-
sel, for the creation of the necessary concentration of

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 73 No. 2 2018

112 PLATONOV et al.
vapors, one should take into account the volatility of
substances at the specified temperature conditions
(mass of dosed substance should not exceed the prod-
uct of volatility by the vessel volume). The instrumen-
tal implementation of methods for the preparation of
SGMs under atmospheric pressure is quite diverse; the
main systems will be considered below.
Single rigid chamber of varied volume equipped with
a heater for liquid evaporation and a stirrer for system
homogenization. A mixture is displaced from the
chamber usually using air, which leads to the continu-
ous reduction of analyte concentration, because of
which only 10% of the chamber volume can be
removed without the reduction of the concentration of
the diluted component [32–35].
A series of consecutively connected identical rigid
chambers. In the removal of a mixture from the last
chamber, its place is occupied by a mixture from the
previous chamber (instead of air, as in the system with
single rigid chamber). This method is suitable for pre-
paring SGMs in amounts proportional to the number
of used chambers [32, 36].
Flexible chambers from inert polymeric materials.
The volume of such chambers can be very great, and
their application is sometimes combined with prelim-
inary dilution [37]. Flexible chambers offer certain
advantages over rigid containers. They are cheaper,
light, and offer a possibility of varying the volume of
the gas mixture by changing of their volume. The most
widespread materials for the production of flexible
chambers are polyethylene, fluoroplastic, tedlar, poly-
vinyl chloride, etc.
The long storage of mixtures prepared by the static
method is not recommended because of a possibility
of losses of the diluted component through diffusion
and adsorption on the vessel walls. Almost all authors
working in the preparation of SGMs point to the effect
of “memory.” To reduce these effects, preliminary
treatment of container walls with conc. HNO3, wash-
ing with distilled water, purging with oxygen, condi-
tioning by the dosed gas, and pumping out was recom-
mended. All these stages considerably complicate the
procedure of SGM preparation and increase the cost
of the technology. The main drawbacks of static meth-
ods, limiting their application, are the impossibility of
the preparation of SGMs of reactive and unstable
compounds because of chemical transformations pro-
ceeding in the vessel; deterioration of the stability of
SGMs with a decrease in the analyte concentration;
adsorption losses of active and polar components and
their interaction with the container walls; possibility of
the condensation of high-boiling compounds; limited
volumes of the obtained SGMs; possibility of the
preparation of SGMs of only one concentration,
whereas the creation of multipoint calibrations
requires additional dilutions, which increases the level
of complexity of the preparation of SGMs and, corre-
spondingly, their error.
JOURNAL OF ANALYTICAL CHEMISTRY
A new wave of interest in methods for preparing
calibration gas mixtures arose in the 2000s and was
connected with the toughening of requirements for the
control of the concentration of pollutants. Papers
[19–22, 38–46] were devoted mainly to the improve-
ment of the known methods and the accuracy of the
composition of SGMs prepared by the known meth-
ods. Special attention was paid to the validation of
methods for the preparation of gas mixtures and stud-
ies of the stability of the composition of gas mixtures
on their storage and use as reference samples, and also
to the identification of error sources of a method [19–
21, 26, 39]. A complex of normative documents regu-
lating methods for the preparation of calibration solu-
tions in the normalized concentration range has been
developed and remains in force in EU countries [18].
Static gas extraction. Static gas extraction is the
distribution of target components between liquid and
gas phases in a closed system. After the establishment
of an interphase equilibrium, the concentration of a
component in the gas phase over the solution cG is as
follows [47]:
сG = c L0 /(K + r),
where c L0 is the initial concentration of a component in
the liquid phase (solution); K is partition coefficient of
a component, equal to the ratio of its molar concentra-
tion in the liquid and gas phases at an equilibrium; r is
the ratio of geometrical volumes of the gas and liquid
phases F in the system. At a rather high number of tar-
get components in the liquid phase (high values of K),
the specified concentration of these components in
the gas phase will be maintained constant because of a
dynamic equilibrium between the phases even at a
noticeable adsorption of the components from the gas
phase on the vessel walls. A similar process, which
was named “buffer effect in a heterogeneous system”
[48, 49] is the basis of all equilibrium methods used of
obtain SGMs. By this property, static gas extraction
favorably differs from the other static methods for pre-
paring SGMs in homogeneous systems.
To obtain SGMs by the method of static gas
extraction, analysts use the same devices as in the
static headspace analysis: glass syringes (system of var-
ied volume) or penicillin bottles (system of constant
volume) [50]. This method was used to obtain SGMs
of aliphatic oxygen-containing compounds and aro-
matic hydrocarbons with air or nitrogen [51]. One of
the reasons for the low popularity of this method can
be the lack of information on partition coefficients of
a wide range of volatile organic compounds in the sys-
tems liquid–gas. However, these coefficients can be
easily measured experimentally [52] or can be a priori
calculated [53, 54].
Vol. 73 No. 2 2018
 METHODS AND DEVICES FOR THE PREPARATION
DYNAMIC METHODS
FOR THE PREPARATION
OF STANDARD GAS MIXTURES
In contrast to static methods, in which SGMs are
prepared in a closed system, dynamic methods are
based on the introduction of target components into a
flow of a dilution gas, which can be pure laboratory air
or an inert gas (carrier gas). These methods have virtu-
ally no limitations by the nature and concentration of
target components and can be used for the preparation
of SGMs of both gaseous components, and vapors of
organic and inorganic compounds.
In nonequilibrium dynamic methods, the concentra-
tions of target components in the generated SGMs
depend on the volume flow rate of dilution gas WG.
The error of SGM preparation is in many respects
determined by the errors of measurement and mainte-
nance of the volume rate of the dilution gas. The sim-
plest dynamic methods are methods of exponential
dilution and flow mixing. In contrast to the majority
of nonequilibrium methods, in these methods, the
long attainment of the working generation mode and
the thermostatic control of the process are not
required. Some authors [5] assign them to a separate
intermediate group.
In the method of exponential dilution, a certain
amount of a target component as a pure gas, a gas mix-
ture, or a liquid is introduced into a vessel supplied
with a device for stirring, previously evacuated when
necessary. Then, after the uniform distribution of the
component over the whole volume of the vessel, a flow
of a dilution gas is passed through the vessel under
continuous stirring [55, 56]. Among the important
advantages of the method are a possibility of preparing
SGMs with the lowest concentrations of target com-
ponents at the insignificance of their adsorption on
the vessel walls and a possibility calibrating gas analyz-
ers in the continuous mode in the widest range of ana-
lyte concentrations. The change in the mass concen-
tration of the target components in a flow of dilution
gas cG in the implementation of this method is given by
the following expression:
(V V 0 )
cG = (m/V0)/e , the diluted component from 0.01 to 1%, and two-step
where m is mass of component added to the vessel, V0
is vessel volume, V is volume of dilution gas passed
through the vessel (V = WGt, where t is time of passing
dilution gas through the vessel). At the initial stages of
passing the dilution gas, when V ! V0, the concentra-
tions of target components can be considered quasi-
constant. This buffer effect can be enhanced using sev-
eral consecutively connected mixing vessels with equal
concentrations of target components. In this case, we
obtain for n vessels
n −1
1 ⎛V ⎞
∑
(V V 0 )
cG = (m/V0)/e
n =1
(n − 1)! ⎜⎝V 0 ⎟⎠
JOURNAL OF ANALYTICAL CHEMISTRY
113
Among the drawbacks of the method we can note
the duration of preparing SGMs with low concentra-
tions of target components, and also an increase in
error with increasing the dilution of the mixture.
The method of flow mixing is based on mixing sev-
eral gas flows, the rate of which is known and regulated
by corresponding flow meters. Method of dynamic
mixing can be used to prepare SGMs with almost any
component ratio; however, in practice, the degree of
dilution is limited by the technical characteristics of
measuring devices and the design features of the gas-
mixing installation. Usually cascade dilution in two or
three steps is used [57–59].
The composition of the gas mixture after the first
dilution step is determined from the ratio:
c 0 f1
c1 = , (1)
F1 + f1
where c1 is the concentration of a target component in
the prepared mixture, c0 is the concentration of a tar-
get component in the initial gas, f1 is the flow rate of
the target component, F1 is the flow rate of the dilu-
tion gas.
The concentration of the target component in the
gas mixture after the second dilution step c2 is deter-
mined by the equation
c1F1
c2 = , (2)
F1 + F2
where F1 is the flow rate of the prepared mixture at the
first step, F2 is the flow rate of dilution gas at the sec-
ond step.
The total dilution coefficient is
c0
k= . (3)
c2
Equations (1)–(3) ensure the determination of the
necessary degree of dilution for obtaining the desirable
concentration. Using single-step dilution, analysts
usually obtain gas mixtures with the concentration of
dilution can give mixtures with concentrations lower
than 1 ppm.
A schematic diagram of an installation for multi-
step dilution is shown in Fig. 1. It consists of a number
of units of identical design; their number is equal to
the number of dilution steps. At multistep dilution, the
mixture obtained in the first unit of the installation is
precisely divided into two flows, and the flow contain-
ing 10% of the volume of the initial flow is introduced
into the next unit, while the second flow is removed
from the installation limits. The flow of dilution gas
n −1 corresponding to 90% of the volume of the removed
. mixture is delivered to the second unit. Therefore, the
concentration of the component to be determined in
Vol. 73 No. 2 2018
114 PLATONOV et al.
Flow meter
F1
Exit of gas
Dilution gas
1 mixture
f1
Component 1
2 measuring flow rates of the mixed flows, and particu-
f2
Component 2
3 ibrated on real gases, which are analytes. However,
Fig. 1. Scheme of installation for multistep dilution [20].
the second unit is 10 times lower than that in the first
unit.
The applicability of the method and the efficiency
of the systems is determined by the technical capabili-
ties of the production of superfine flow rate regulators,
ensuring the division of the gas mixture into two flows.
The degree of dilution can be considerably increased
using two different regulators of gas flow rate, one for
low and another for high flow rate of the gas. If reac-
tive gases are used for dilution, special attention
should be paid to the material of the flow meter; an
important requirement for which is inertness and
resistance to aggressive working media [57–59]. The
instrumental design of the used dynamic installations
is quite diverse and determined by specific character-
istics of the prepared mixture. To prevent effects of the
separation of mixed components, one should carefully
select the design of the mixing chamber.
The method of gas flow mixing has received com-
mercial implementation in some commercially
released generators of gas mixtures. JSC Monitoring
(St. Petersburg) releases a dynamic GGS-03-03 gen-
erator, the operation principle of which consists in
mixing flows of target component with a dilution gas.
The generator is a working calibration standard of the
1st category according to GOST (State Standard) [6] is
included in the State Register of Measuring Instru-
ments under the number 19351-00. The maximum
dilution coefficient is 3000. The limits of the relative
error of measurement of the dilution coefficient are
±(0.8−2.5)%. The time of attainment of a preset value
of the volume fraction of the normalized component
in the gas mixture at the exit from the generator is
~30 min. The limitation of this generator is the impos-
sibility of preparing mixtures containing explosive or
aggressive components.
The verification gas mixtures obtained on dynamic
installations based on gas flow mixing are certified by
the preparation procedure, by measuring flow rates,
pressure, and temperature of gas flows [60]. The
JOURNAL OF ANALYTICAL CHEMISTRY
advantages of the method of mixing gas flows appear
in multipoint calibration: to prepare a mixture with a
new concentration, it is sufficient to change flow rates
of the dilution gas and the substance to be determined.
Another important advantage of the method is that it
can be used in very a wide concentration range (from
99% to 1 ppm).
The accuracy of the preparation of mixtures by the
method of flow dilution is limited by the accuracy of
larly of the flow containing the target component.
Usually gas flow rates are measured using electronic
thermal mass flow meters. These devices must be cal-
because of the limited range of the available standards
of flows, the flow meters are calibrated on an artificial
gas, for which a primary standard is available. In this
regard, to obtain calibration by a real gas, one should
use a correction coefficient for primary calibration.
Because of this, the real relative error of measuring gas
flow rates for the majority of flow meters is closer to
+5% than to theoretical ±1% [58, 59]. In addition, the
preparation of SGMs containing exact trace concen-
trations of substances requires a number of dilution
steps, which is associated with certain applied prob-
lems. The preparation of the mixtures containing
vapors of liquid substances is also difficult because of
the problem of the creation of a stable flow of vapors
from a liquid source. The method of direct mechanical
mixing requires highly qualified maintenance, which
determines the level of random errors of the dilution
procedure.
Injection methods are based on the slow introduc-
tion of a dosed impurity into a dilution gas flow, which
gives SGMs in the wide concentration range with an
error of ±1%. These methods are used to prepare
SGMs of substances of different volatilities in a dilu-
tion gas, which implies the introduction of a sample
preventing the condensation of liquids. The compo-
nent can be dosed manually, using a syringe, a
microsyringe, a controlled automatic syringe, an
autosampler, and pumps [2, 60, 61]. The concentra-
tion of the analyte, and the accuracy and reproducibil-
ity of SGM preparation are determined by the accu-
racy of dosing units. An advantage of injection meth-
ods is in their relative versatility, wide working
concentration range, and various ranges of analytes.
Its main disadvantage in interrupted operation.
The next two nonequilibrium dynamic methods of
SGM generation have many common features and can
be united under one common name, thermal diffusion
methods.
The diffusion method is based on the diffusion of
vapors of a target substance, which is in a liquid state,
through a capillary with certain geometrical parame-
ters to a flow of a dilution gas [4, 36, 59, 62–65]. The
method is quite simple in instrumentation and is used
to obtain SGMs of sufficiently volatile organic com-
Vol. 73 No. 2 2018
 METHODS AND DEVICES FOR THE PREPARATION 115

pounds. Another advantage of the method is a possi-

bility of preparing gas mixtures with very high (up to
several g/dm2) concentrations of target components.
Among its drawbacks is the impossibility of preparing
SGMs of low-volatile compounds. 3 4
A typical diffusion device consists of a tank with a
pure liquid and a capillary, by which vapors of this liq-
uid diffuse from the tank to the flow of a dilution gas
(Fig. 2).
The flow of a substance can be calculated by the
equation
2
⎛ p ⎞
r = DMPA ln ⎜ ⎟, (4)
RTL ⎝P − p⎠
where r is substance flow rate through the diffusion
tube, g/s; D is its coefficient of molecular diffusion in
the gas phase, cm2/s; M is molar mass of the sub-
stance, g/mol; P is total pressure in the diffusion tube,
MPa; p is partial vapor pressure of this substance,
MPa; A is cross section area of the diffusion tube, cm2;
T is temperature, K; L is tube length, cm; and R is uni-
versal gas constant. Therefore, the concentration of a
component in the gas mixture cG (g/cm3) is
сG = r/WG, (5)
1
where WG is volume flow rate of dilution gas, cm3/s. It
was found that r is virtually independent of WG if the Fig. 2. Scheme of implementation of diffusion method of
last value is in the range 0.1–7 L/min [66]. SGM generation: (1) vessel with a target substance in the
Of applied interest are diffusion installations pro- liquid state; (2) capillary; (3) input of dilution gas; (4) an
exit of generated SGM [65].
ducing substance flow rates of 1–1000 ng/s. For the
typical sizes of the capillary, such as length of
10−15 cm and diameter of 0.01–1 mm, the specified masses of the target components [72]. A satisfactory
flows are reached for substances with boiling tempera- coincidence of the predicted and found concentra-
tures from 40 to 200°C. As the diffusion coefficient tions of the target components from different classes of
and pressure of a saturated flow strongly depend on organic substances (halogenated hydrocarbons,
temperature, the installation must be thermostatically alkanes, alkenes, aromatic hydrocarbons) was shown.
controlled with an error of temperature maintenance It was found that the difference between the calculated
not less than ±0.1°C. and experimental values of concentrations also
Despite the existence of calculation equations (4) depends on the chosen diameter of diffusion capillary.
and (5), the exact determination of component con-
centrations in the generated SGMs is possible only The urgent problem of the preparation of SGMs of
after the calibration of diffusion cells by decreasing reactive formaldehyde, tending to associate in the gas
substance mass [67–69]. In this regard, the diffusion phase, was solved in [73] by the diffusion of trioxane
method does not differ from the membrane method vapors present in a vessel through a capillary at 35°C,
described below. Multicomponent gas mixtures, as a followed by its conversion to formaldehyde at 230°C.
rule, are generated using several diffusion cells, sup- The diffusion method was successfully used to obtain
plied with capillaries of different geometrical sizes [59, SGMs of biogenous monoterpenes and sesquiterpene
66]. Thus, reusable diffusion tubes graduated within [74], and also of 2-dichlorodioxin [75]. In the latter
several weeks are presented in [70]. In [71], to mini- case, substance vapors formed as a result of sublima-
mize the adsorption of toluene on the walls, the diffu- tion were diffused through a capillary. The work [76],
sion capillary was made of a fluoroplastic, and the in which acetone was a target component, can provide
impurity of water vapor was adsorbed with an ion- an example of a combination of the diffusion method
exchange resin with a fluoropolymer matrix, Nafion. with the one-step dilution of the formed SGMs. The
diffusion method was also successfully used to gener-
As the last achievements in the development of the ate SGMs of inorganic substances, for example Br2,
diffusion method, let us note the development of a ICl, IBr, and I2 [77].
mathematical model for the a priori prediction of the
concentration of target components in the generated The membrane method is based on the penetration
gas mixtures based on boiling temperatures and molar (diffusion) of molecules of target components into a

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 73 No. 2 2018

116 PLATONOV et al.
dilution gas flow through a membrane, for which one
can use walls of an ampoule permeable for volatiles or
a sealed tube made of polymeric materials. The
ampoule is previously filled with a target substance in
a liquefied, liquid, or solid state.
Now membrane method is the most widely used
dynamic method for the preparation of SGMs, and
the “microflow sources of gases and vapors” working
on its basis are included in the state primary standard
of the mole fractions and mass concentrations of com-
ponents in the gas media [6]. The undoubted advan-
tages of the membrane method are as follows:
—possibility of generating SGMs of almost all
organic and inorganic substances, including aggres-
sive and reactive ones, except for the most low-boiling
gases;
—possibility of generating SGMs in a wide concen-
tration range;
—high degree of study of the process and its metro-
logical justification;
—a wide choice of generators for gas mixtures,
working on the basis of this method;
—ease of automation and the simplicity of mainte-
nance of these generators.
Among the drawbacks of this method in compari-
son with the other ones we can note the rather high
cost of equipment, long duration of the attainment of
the working mode of SGM generation, and a need in
the careful thermostatic control of the process with an
error of temperature maintenance not less than
±0.1°C. We should also note a need in the continuous
and precise weighing of ampoules or tubes with the
working liquid in the process of SGM generation for
calculating the precise concentration of the target
components.
According to the standard sorption and diffusion
model of the penetration of substances through a nonpo-
rous membrane, the flow of a substance through it r (g/s)
can be calculated by the equation [78]
DMAS ( p1 − p2 )
r = , hydrogen fluoride and chloride, and also for several
d dozens of the most widespread volatile organic com-
where S is the solubility of a substance passing through a
membrane in the membrane material, mol/(cm3 MPa);
p1 and p2 are partial pressures of the substance in the
ampoule (tube) and outside it; d is the thickness of the
ampoule wall (membrane), cm; designations of other val-
ues see above in Eq. (4). The concentration of a compo-
nent in the SGM in using the membrane method is
inversely proportional the volume flow rate of the dilution
gas through the cell in which it is present and can be calcu-
lated by Eq. (5).
As in diffusion methods, the membrane methods
require the stringent thermostatic control of the pro-
cess with an error of temperature maintenance not less
than ±0.1°C, because the change of temperature by
1 degree leads to a change of r by 8–10% [4]. The prac-
JOURNAL OF ANALYTICAL CHEMISTRY
tically important flow rates of target substances in the
range 1−1000 ng/s are reached in the temperature
range 30−150°C. The mass concentration target com-
ponents in the generated SGMs (cG) calculated by the
weight decrease of a substance in an ampoule Δm,
weighed before and after experiment, is
cG = Δm/(tWG),
where t is time of dilution gas passing through the cell
with an ampoule and WG is volume rate of its flow.
Today the most widespread material used for mem-
brane production is polytetrafluoroethylene [71, 78].
The effect of the flow rate of dilution gas in the
range 20−1200 mL/min and temperature in the range
30−100°C on the generation of SGMs of benzene, tol-
uene, and m-xylene was investigated in detail in [79–
82]. A possibility of the a priori prediction of the con-
centration of aromatic hydrocarbons in SGMs in the
range 0.1−200 mg/m3, also for multicomponent mix-
tures of the specified substances, was shown. A com-
parison of the results of gravimetric and membrane
methods of SGM preparation made in the above
works showed their satisfactory coincidence at a level
of several ppm, both for inert propane and for highly
reactive methanethiol [82–84]. To generate of SGMs
of highly reactive formaldehyde, easily associating in
the gas phase, at a level of ppm by the membrane
method, Nobuyuki et al. conducted the thermal depo-
lymerization of the initial paraformaldehyde [85].
The membrane method was used to generate SGMs
of ten terpenes at a level of ppb with a relative error of
less than 10% at a flow rate of dilution gas of
100 mL/min [86].
The membrane method is widely used for the gen-
eration not only organic but also inorganic substances,
in particular, reactive NO2 [77] and highly inert
SF6 [87].
By now, microflow sources (MSs) of gases and
vapors we developed in Russia for ammonia, nitrogen
dioxide, sulfur dioxide, hydrogen sulfide, chlorine,
pounds with boiling temperatures in the range
35−250°C; these sources entered the State Register of
Measuring Instruments [88]. The productivity of the
released MSs (value r), as a rule, lies in the range
0.1−30 μg/min. The permissible limits of relative
error of the productivity of MSs, except for the sub-
stances listed below, are ±7% at the productivity
<1.0 μmol/min and ±5% at the productivity
≥1.0 μmol/min and for MS of formaldehyde, tributyl
phosphate, and phosphoric acid esters, these limits are
±10% at the productivity <1.0 μmol/min and ±7% at
the productivity ≥1.0 μmol/min. The geometrical sizes
of MSs are as following: length 15–135 mm, diameter
4–10 mm, and weight no more than 20 g. The perme-
able material is usually polytetrafluoroethylene.
Vol. 73 No. 2 2018
 METHODS AND DEVICES FOR THE PREPARATION
1 6
2 3
Fig. 3. Scheme of single-channel thermal diffusion SGM generator: (1) input of dilution gas; (2) activator of the flow rate of dilu-
tion gas; (3) electronic measuring device and regulator of the flow rate of dilution gas; (4) thermostat; (5) ampoule with a target
substance; (6) exit of generated SGM [60].
Sources of microflows form the basis for the work
of the most widespread thermal diffusion generators of
gas mixtures produced in Russia and abroad. An oper-
ation scheme of the simplest single-channel generator
is shown in Fig. 3.
In Russia, generators of this type, used to obtain
gas mixtures of the zero, first, and second categories,
were introduced into the State Register of Measuring
Instruments. The thermal diffusion and combined
(thermal diffusion and mixing) generators differ in the
number of thermostats containing MSs of various sub-
stances, and their working temperature ranges, the
number of channels of dilution gas flow formation,
and the ranges of volume flow rates in these channels.
Thus, various modifications of one of widespread
domestic generator of gas mixtures, Mikrogaz-F, have
up to four thermostats, maintaining temperature in
range 30−120°C, and up to 6 gas channels, forming
gas fl ows in the range 2−6000 cm3/min [89].
Chemical and electrochemical methods. These old-
est dynamic methods are based on the dilution of sub-
stances formed as a result of chemical or electrochem-
ical reactions by a flow of a dilution gas. These meth-
ods are usually used to obtain SGMs of aggressive
reactive substances, for which preparation by other
methods is impossible or associated with difficulties.
Chemical methods are quite often used to obtain
SGMs on the basis of thiols [90], hydrogen cyanide,
and dicyanogen [91], hydrogen sulfide [92], and dif-
ferent fluorine compounds [93]. Chemical reactions
of thermal decomposition are used most often [90,
94], along with reactions of hydrolysis [95], dehydra-
tion [96], oxidation [97], and reactions of photochem-
ical [98] or electrolytic [99] decomposition of the cor-
responding reagents. Among the main advantages of
the chemical method are a possibility of generating
SGMs of highly reactive organic and inorganic com-
pounds and the simplicity of instrumentation. To its
drawbacks we can assign the limited field of applica-
tion and rather low accuracy.
Electrolysis can be successfully used for the follow-
ing purposes (direct method): anode generation of
CO2 from a saturated aqueous solution of oxalic acid,
anode generation of oxygen and cathode generation of
hydrogen from acid or alkaline aqueous solutions,
cathode generation of NO in the electrolysis of a nitro-
sulfonic acid solution, and generation of H2S in the
cathode reduction of bis(β-ethylcarboxy)trisulfan [36,
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 73
117
4
5
59]. New possibilities are opened for the indirect
method: electrolysis in combination with chemical
transformations of its products. This combination
allows the researcher to obtain carbon oxide after the
catalytic reduction of electrolytically generated carbon
dioxide, nitrogen dioxide after the oxidation of elec-
trolytically obtained NO by electrolytic oxygen, water
by the catalytic oxidation of electrolytically generated
hydrogen in the presence of an excess of oxygen or a
stoichiometric amount of electrolytic oxygen, and
methane by the catalytic reduction of carbon dioxide
formed in the course of electrolysis [36, 59].
To the main advantages of the electrochemical
method we should refer its specificity, possibility of
the creation of portable devices, ease of automation,
possibility of interrupting a generation process at any
time instant, and short response time. The drawbacks
are limited applicability, need in using special technol-
ogies, and possible deviation from the Faraday law
because of the evaporation of water or the exhaustion
of an electrolyte.
Equilibrium dynamic methods are based on an equi-
librium distribution of target components between the
gas and condensed (liquid or solid) phases. The gas
phase is mobile, and the condensed phase can be
either stationary or mobile. In contrast to nonequilib-
rium methods, the concentrations of target compo-
nents in these methods are independent of the volume
flow rate of the gas phase if an interphase equilibrium
is attained. For this reason, in the description of equi-
librium methods, the flow of the gas phase can be
named a carrier or extractant (in extraction methods),
rather than dilution gas.
Evaporation method. This simplest equilibrium
dynamic method is based on passing a carrier gas flow
through a liquid layer or over it. Under the condition
of an equilibrium, the concentration of a component
in the gas mixture cG (g/dm3) is independent of the
rate of this flow and can be calculated by the equation
[36, 59]
pM P
сG =  ,
RT P − p
where p is partial vapor pressure (MPa) of a target
component with a molar mass of M (g/mol) at the
temperature T (K), and P total pressure (MPa).
To create a concentration of a target component
corresponding to the saturated vapor pressure, the
No. 2 2018
118 PLATONOV et al.
flow rate of the carrier gas must be low and the device
must have special design. For this purpose, bubbling
devices of different types (sometimes arranges in a
series) or U-shaped absorbers are used. The saturation
temperature in this case can be both lower and higher
than the ambient temperature.
The evaporation of a liquid can be carried out
under the influence of microwave radiation; in this
case, the evaporation method from the category of
equilibrium methods changes to the category of non-
equilibrium ones. The generation of SGMs of a few
volatile organic compounds under the influence of
microwave radiation was described in [100]. For better
evaporation, water was added to the samples. The effi-
ciency of moisture evaporation was estimated by com-
parison with the classical method. The prepared mix-
tures were analyzed by gas chromatography with solid-
phase extraction.
An installation was developed for the dynamic gen-
eration of SGMs, which consisted of a vaporization
chamber and a mixing chamber. The analyte was
introduced into the vaporization chamber, which con-
tained an absorbing substrate; then a flow of air was
passed through the chamber; and the obtained mix-
ture arrived at the mixing chamber, where it was
diluted by an additional flow of air [101]. It should be
noted that the methods considered in this section have
found wide application for the preparation of standard
gas mixtures with precisely known concentrations of
water vapor in the range of relative humidities 7–98%
[101, 102].
Continuous gas extraction is based on passing a rel-
atively small extractant gas flow, ensuring the estab-
lishment of an interphase equilibrium, through the
bulk or over the surface of a condensed phase, a liquid
or a solid containing certain amounts of target compo-
nents. The method is simple and well-studied, and is
characterized by the presence of certified devices for
its implementation, so-called “vapor-phase sources of
gas mixtures” (VSGMs), whose application is permit-
ted by the state validation scheme for devices for the
determination of concentrations of components in gas
media [6]. Among the drawbacks of the methods are
rather small volumes of generated SGMs with con-
stant concentrations of target components and low
volume rates of the generated mixtures. In this
method, as well as in the majority of other equilibrium
methods, one should take into account the change
(reduction) of the concentration of target components
in the course of SGM generation (in contrast to ther-
mal diffusion and evaporation methods).
Regularities of continuous gas extraction were
studied in detail, first of all, because of its wide appli-
cation to the headspace gas-chromatographic analysis
of water media [47]. For components with K > 100
(this method is used just for these components), the
concentration of a component in the generated SGM
cG can be calculated by the equation
JOURNAL OF ANALYTICAL CHEMISTRY
c0 ⎛ −v ⎞
cG =  L exp ⎜ G ⎟ , (6)
K ⎝ KV L ⎠
where cL0 is the initial concentration of a target compo-
nent in the condensed phase; VL is its volume; and vG
is the volume of extractant gas passed through the sys-
tem.
The maximum volume of the generated SGM with
a quasiconstant concentration of the target compo-
nents v Gmax can be calculated from Eq. (6) using
Eg. [7]:
v Gmax = –KVL ln(1 – δ), (7)
where δ is the reduction of component concentration
admissible in the course of generation in percents of its
initial concentration in the gas phase. If one liter of
condensed phase is used for generation, for a compo-
nent with K = 10000 and error of concentration mea-
surement δ ≤ 3%, one can obtain SGM volume equal
to 304 L. At the admissible error δ = 10%, this volume
increases to 1050 L.
The maximum permissible flow rates of extractant
gas in SGM generation depend on the volume of con-
densed phase and on the design of the dispenser of the
gas flow, which must provide rather small gas bubbles
for increasing the area of interface between the gas and
the condensed phase. At a corresponding design, an
equilibrium is attained at gas flow rates to 0.5 L/min.
The VSGMs introduced into the RF State Register
of Measuring Devices are metal vessels of the volume
1 L with two fittings for the entrance and exit of a flow
of extractant gas (Fig. 4) and have four different
designs [103, 104]: “M” – a solution of a target sub-
stance in vacuum or dielectric oil, “E” – a solution of
a target substance in ethylene glycol, “G” – a solution
of a target substance in triethylene glycol, and “U” –
activated charcoal SKT-6 with the adsorbed target
substance. The weight of a VSGM does not exceed
1 kg. The ranges of extractant gas flow rates in the
work of VSGMs are 10–300 mL/min for liquid fillers
and 10–150 mL/min for the charcoal adsorbent. In
this characteristic they are much inferior to thermal
diffusion generators (to 6 L/min).
The limits of the permissible relative error of the
mass concentration of target components at the ther-
mostatic control (±0.1°C) of VSGMs are ±7% in the
concentration range from 1 to 1000 mg/m3 and ±10%
in the concentration range from 0.01 to 1 mg/m3. In
contrast to thermal diffusion generators, VSGMs can
be used at room temperature (18–25°C) without ther-
mostatic control. The relative error in this case is
±20% in the whole concentration range. VSGMs
belong to unrepairable and unrestorable devices. The
characteristics of VSGMs released by VNIIM are
summarized in Table 3.
The VSGMs working under atmospheric pressure
gives only one SGM with a certain concentration of a
Vol. 73 No. 2 2018
 METHODS AND DEVICES FOR THE PREPARATION 119

target component. However, if SGMs are prepared at

elevated pressures, one and the same VSGM can be 5 1
used to obtain SGMs with different concentrations of
target components. In this case, in accordance with
ideal gas laws, the concentration of target components
will decrease in inverse proportion to the working
pressure of the extractant gas in the VSGM [105].
The main drawback of the traditional scheme of
continuous gas extraction from the viewpoint of SGM
generation are rather small volumes of the generated
SGMs with quasiconstant concentrations of target
components, see Eq. (7). Several methodological
solutions proposed by the present time substantially
overcome this drawback. The simplest solution is pro-
vided by so-called “polybubbler systems,” in which the
flow of an extractant gas passes through several con-
secutively connected bubbler vessels filled with a solu-
tion with a certain concentration of target compo-
nents. 4
Polybubbler method. The use of multistep flow sys-
tems was the further sophistication of heterogeneous 2
flow systems. Figure 5 presents a scheme of a polybub-
bler system, implementing the principle of multistep 3
gas extraction of a volatile compound from a low-vol-
atile liquid, which consists of consecutively connected
vessels containing solutions of a volatile compound in
a nonvolatile liquid with different initial concentra-
tions [106–110]. At the entrance to such system, a pure Fig. 4. Scheme of a vapor-phase source of gas mixtures:
gas phase is fed to the system at a constant volume rate (1) input extractant gas; (2) metallic vessel; (3) gas flow
dispenser (bubbler); (4) condensed phase with a target
and, at the exit from it, a gas mixture of a certain con- component; (5) exit of generated SGM [103].
centration is generated.
The use of systems with equal initial concentrations
of the volatile compound in the nonvolatile liquid and passes through a sharply expressed maximum. For the
equal volumes of solutions in all bubblers allows the system with different volumes of liquid phase in con-
researcher to obtain a gas flow with a constant concen- secutively connected bubblers, the behavior of the
tration, but only at the initial step of system operation; concentration of the volatile compound in the flow of
in the course its further operation, the concentration an inert gas was similar. The system with three vessels
of an analyte in the SGM also exponentially decreases. in a multistep system was optimum. The smaller num-
From the viewpoint of the duration of operation and ber of steps did not ensure the stability of SGM com-
the stability of analyte concentration in the SGM, the position and their bigger number did not lead to a pro-
most efficient are systems of consecutively connected portional increase in efficiency. Therefore, a certain
vessels with a 25% concentration gradient at a constant (optimum) distribution of a volatile compound
volume and other equal conditions being equal or with between the bubblers at equal volumes of the liquid
a 25% volume gradient in the first vessel, which phase ensures an increase in the period of the con-
ensures a two- to fourfold increase in the duration of stancy of the concentration of a volatile compound in
stable operation of the system. Such increase in the the flow of an inert gas at the exit from the system.
duration of maintenance of a constant analyte con- The physicochemical model of the process of the
centration in the SGM is explained by the buffer redistribution of a volatile compound in a multistep
effect, because of which volatile compounds are redis- bubbler system allows the calculation of the composi-
tributed from the first bubbler, in which the initial tion of the gas phase at the exit from the system as a
concentrations of these substances are higher, to the function of time [107]. The theoretical description of
second and then to the third vessel, which ensures the the polybubbler process was based on the following
stable supply of the analyte to the solution with a lower assumptions: the temperature and volume rate of the
concentration. A considerable (by more than 25%) gas phase in the flow system were constant during the
increase in the initial concentration of a volatile whole process; the distribution of a volatile compound
organic substance in the solution in the first vessel between the gas and liquid phases was characterized by
prevents generation of SGMs of a constant composi- a partition constant independent of the concentration
tion. The concentration of a substance in this case of substance in the liquid phase; and the adsorption

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 73 No. 2 2018

120 PLATONOV et al.

Table 3. Characteristics of vapor-phase sources of gas mixtures (VPSGM) [104]

Target component Filling agent Concentration range, mg/m3 Volume resource, L
Acetaldehyde Triethylene glycol 0.5–200 200
Acetone The same 0.5–1000 1000
Benzene '' 0.5–1000 1000
Butanol '' 0.5–1000 1000
Hexane '' 0.5–1000 1000
Decane '' 0.5–1000 1000
1,2-Dichloroethane '' 0.5–1000 1000
Isobutanol '' 0.5–1000 1000
Isopentane '' 0.5–1000 1000
o-Xylene '' 0.5–1000 1000
Oil 1.0–1000 200
m-Xylene Adsorbent 0.5–1000 1000
Oil 1.0–1000 200
p-Xylene Adsorbent 0.5–1000 1000
Oil 1.0–1000 200
Methanol Adsorbent 0.5–1000 1000
α-Methylstyrene Oil 1.0–1000 200
Propanol Adsorbent 0.5–1000 1000
Styrene Oil 1.0–1000 220
Toluene Adsorbent 0.5–1000 1000
Oil 1.0–1000 70
Phenol Ethylene glycol 1.0–1000 10000
Cyclohexane Adsorbent 0.5–1000 1000
Ethylbenzene The same 0.5–1000 1000
Oil 1.0–1000 200

effects at the interfaces and in connecting communi- polybubbler method, a substantial number of devices
cations were absent or negligible. The process of inter- was developed to obtain SGMs [64–68] differing in
phase distribution in the system was considered as an instrumental design, which were intended for the gen-
isobaric–isothermal process proceeding under steady- eration of a big number of SGMs of organic and inor-
state conditions in the region of linear adsorption iso- ganic gases, including aggressive and highly reactive
therm of the redistributed component. The mathe- substances, such as hydrogen sulfide, sulfur dioxide,
matical description of the process was given by the oxygen, etc.
equation
n
The theoretical description of the process of con-
tinuous gas extraction of hydrogen sulfide and sulfur
cG i ( X ) = ∑ i1! c exp ( − X ) ,
i
n−i X dioxide from aqueous solutions of sodium sulfide and
i =0 sulfite is based on the analysis of the material balance
Fτ equation for the system on the assumption that both
where X = is extraction coefficient; the hydrolysis equilibrium and that of the redistribu-
K CV L + VG
∅ tion of volatile compounds in the liquid−gas system
cL iV L are attained instantaneously [110].
ci =   is equilibrium concentration of a vol-
K CV L + VG
atile compound in the gas phase of the i-th vessel at the A comparison of the experimental data with the
theoretical description of the process of equilibrium
initial time point; and cL∅i   is the initial (nonequilib- continuous gas extraction in a three-step flow system
rium) concentration of a substance in the liquid phase. of a solution of a volatile organic compound in a low-
Flow systems have found wide application in phys- volatile liquid–inert gas showed their good agreement:
ical chemistry and chromatography. Based on the the difference did not exceed 10% (Fig. 6).

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 73 No. 2 2018

 METHODS AND DEVICES FOR THE PREPARATION 121

Dilution
gas

6
2

6 Fτ cG0 i , cGi (τ) cG n (τ) 2

Dilution … …
gas
VGi
3 3
6
i VLi n
D SGM
0 1 4 5
cL∅i , cL0i , c Li (τ)
1

Fig. 5. The scheme of device for preparing a vapor-gas mixture and gas-chromatographic control of its composition: (1) system
of consecutively connected bubblers; (2) six-way dosing valves; (3) loops of calibrated volume; (4) column of the gas chromato-
graph; (5) detector; (6) fine adjustment valves; F, volume rate of inert gas passing through the system; τ , time; cL∅i  , cL0 i , cL i  ( τ )  are
analyte concentrations in the liquid phase of the i-th bubbler (initial nonequilibrium, initial equilibrium, and at timepoint τ ,
, cG i  ( τ ) are analyte concentration in the gas phase being in equilibrium contact with the liquid phase in the i-th
0
respectively); cG i
bubbler (initial and at timepoint τ , respectively); V L i , VG i  are volumes of liquid and gas phases in the i-th bubbler; cG n  ( τ ) is con-
centration of volatile organic compound in the flow of inert gas at the exit from the system [64].

A comparison of the polybubbler method for
obtaining SGMs (Table 4) with the method of diffu-
sion through a permeable polymeric membrane on an
example of the Mikrogaz thermal diffusion generator
of gas mixtures (TU (Technical Specifications) 4215-
004-07518800-02) with fluoroplastic ampoules filled
with volatile compounds (TU (Technical Specifica-
tions) IBYaL. 418319.013-95, State Register of Mea-
suring Instruments no. 15075-95) showed that the rel-
ative random errors of the preparation of vapor–gas
mixtures of saturated and aromatic hydrocarbons δ in
the polybubbler device and the Mikrogaz generator
were almost equal and did not exceed 7%. The advan-
tages of polybubbler devices are the simplicity of oper-
ation, the rapidly attained equilibrium mode, and a
possibility of the preparation of multicomponent gas
mixtures.
Method of thermal decomposition of immobilized
compounds. The method of preparing gas mixtures
based on the controlled thermal decomposition of a
solid substrate with immobilized target compounds,
developed by the group of researchers leaded by
Namiesnik (Gdansk, Polytechnical University) [59,
90, 112, 113] offers considerable promise. In this
method, the substrate is a previously chemically mod-
ified matrix, and the decisive parameters of the pro-
cess are temperature and time of action, and also sub-
strate nature. The authors classify the method as a ver-
sion of the dynamic method of chemical reactions. In
[90], SGMs were generated by the thermal decompo-
sition of a modified silica and a possibility of multi-

Table 4. Comparison of methods for the preparation of gas mixtures of hydrocarbons [64]*
Volatile Polybubbler system Mikrogas installation
component theory experiment δ, % theory experiment δ, %
Benzene 112 110 ± 2 3 129 127 ± 2 3
n-Heptane 155 150 ± 2 5 199 196 ± 3 3
Toluene 87.5 84 ± 3 6 77.1 75 ± 2 5
n-Octane 76.2 74 ± 3 5 65.7 65 ± 1 3
о-Xylene 51.3 59 ± 2 4 45.7 44 ± 2 7
Ethylbenzene 52.8 50.8 ± 0.8 5 58.6 56 ± 2 7
* Concentration of components in the gas mixture cG are given in mg/m3.

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 73 No. 2 2018

122 PLATONOV et al.

cG(τ), ppm through a chromato-desorption system (CDS). The

3×103
2
6.0
4.5
3.0 3 VOC source in [111] was a system of Richter absorbers
4
1.5
5 consists in the desorption of VOCs on passing an inert
0 5 10 15 20 25
Fig. 6. Comparison of time dependences of the concentra-
tion of volatile compounds in the flow of inert gas (nitro-
gen) for a polybubbler system with a 25% concentration
gradient in the first vessel, experimentally obtained (solid
lines) and theoretically calculated (dashed lines):
(1) hydrogen sulfide; (2) toluene; (3) n-heptane; (4) ethyl
benzene; (5) ethanol [64].
point calibration by varying desorption temperature
was considered. Using the specified method, the
authors obtained gas mixtures of СО, CO2, NH3,
CH3SH, C3H7SH, CH3NH2, (C2H5)2NH, CH3Cl,
C2H4, and (C2H5)3N. Aluminum, iron(III), chro-
mium, and titanium oxides were recommended as
solid substrates. The advantages of the method are a
possibility of obtaining multipoint calibrations,
including reactive and foul compounds, directly in the
course of the analysis. The main drawback of the
method is a change in the reproducibility of SGM
composition from one batch to another and its depen-
dence on the degree and efficiency of substrate modi-
fication and the conditions of preparation of immobi-
lized compounds.
The chromato-desorption method of SGM genera-
tion is based on the equilibrium saturation of an inert
gas flow with volatile compounds on its passing
scheme of a CDS is shown in Fig. 7: tubular flow con-
tainer 2 is connected with gas flow rate regulator 1 and
placed in thermostat 3. The tubular flow container is
filled with a substrate with a known amount of volatile
1
compounds. The substrates are polymeric, modified
inert, inorganic, or a nanostructured adsorbent.
Gas mixtures are obtained by the chromato-
desorption method in two steps: (1) the chromato-
graphic sorption step consists in an equilibrium satu-
ration of an sorbent with VOCs at the temperature Tsat
exceeding working temperatures of the system Tdes; the
(AKG.5.886.027) with a VOC solution (trichloro-
methane and tetrachlormethane) in low-volatile liq-
uid (tetradecane); (2) the chromato-desorption step
gas through the system at the temperature Tdes lower
t, h than saturation temperature Tsat. Therefore, the value
of the partition constant of substances in the system
adsorbent–gas is regulated, which provides flows with
the specified concentrations of VOCs; in this case, no
additional dilution and no change in other parameters
of the system are required. The regularities of the
chromato-desorption method are well described
within the theory of the method of the adsorption
equilibrium concentration [47]. The practical imple-
mentation of a chromato-desorption process for
obtaining mono- and multicomponent gas mixtures
containing trace concentrations of aliphatic hydrocar-
bons and polar, aromatic, and halogenated organic
compounds was described in [114–116]. A compara-
tive assessment of polybubbler and chromato-desorp-
tion methods for generating single- and multicompo-
nent SGMs of volatile organic compounds is pre-
sented in Table 5. It can be seen that, at equal
productivity (period of maintenance of the constancy
of analyte concentration in the SGM with the accu-
racy 3−7%), in the chromato-desorption method, the
amount of reagents required is 10 times lower and
there is no need in the utilization of exhausted solu-
tions, which satisfies the principles of “green” chem-
istry. Among the advantages of the method are a pos-
sibility of obtaining multicomponent gas mixtures in
one cycle and the simplicity of instrumentation and
operation, which opens possibilities for the use of the

1 3
Inert gas Gas mixture
2

Fig. 7. Schematic diagram of a chromato-desorption system: (1) regulator of gas flow rate; (2) tubular flow container with an sor-
bent; (3) thermostat [111].

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 73 No. 2 2018

 METHODS AND DEVICES FOR THE PREPARATION 123

Table 5. Comparison of methods for the preparation of standard gas mixtures of volatile hydrocarbons [114]
Error of maintaining Time of maintaining Weight of nonvolatile
Analyte cG, mg/m 3 the composition, δ, % constant composition τ, h liquid, g
PB CDS PB CDS PB CDS
Single-component mixtures
Benzene 0.3 3 4 10 12 168 18
Toluene 0.08 5 6 50 48
n-Heptane 0.04 5 7 >30 >30
Multi-component mixtures
Benzene 0.3 5 5 10 11 56 6
Toluene 0.07 6 7 50 48
n-Octane 0.03 7 7 >60 >60

chromato-desorption method outside the laboratory.
In addition, chromato-desorption devices can be min-
iaturized, for example, using a medical needle 40 mm
long, inner diameter 0.5 mm (discrete chromato-
desorption microsystems) or microfluid systems as
tubular flow containers. The important factors deter-
mining the capacity of the system will be not only the
properties of the sorbent, but also dead volume, deter-
mined by the ratio of geometrical sizes of the container
and adsorbent particles. In general, the trend to min-
iaturization is inherent in all directions of the develop-
ment of analytical chemistry, because this creates
methodological and instrumental basis for the imple-
mentation of in situ analysis.
Chromatomembrane gas extraction. An increase in
the number of bubbler vessels with the aim to increase
the volume of the generated SGMs with a quasicon-
stant concentration of target components is the sim-
plest but by no means the most efficient solution of the
specified problem. New prospects in the field of SGM
generation were opened by the chromatomembrane
mass-exchange process, proposed in the end of the
20th century [117, 118]. In the chromatomembrane
generation of SGMs, the flow of an extractant gas is
passed through micropores of a biporous hydrophobic
matrix contacting with macropores, along which a
generating aqueous solution of target substances
moves [119]. The area of the liquid–gas interface and
rate of establishment of interphase equilibrium in
comparison with the traditional bubbler sharply
increases in the porous medium. This allows the use of
one order of magnitude higher flow rates of extractant
gas for generation of SGMs at other conditions being
equal [120].
In the implementation of continuous chro-
matomembrane gas extraction (CMGE) with a simul-
taneously passing a generating solution of target com-
ponents and an extractant gas through a biporous
matrix, the volume of SGMs is almost unlimited.
CMGE gives SGMs with trace concentrations of polar
organic and inorganic substances at a level of
several mg/m3 and lower stable within several hours.
The methodological possibilities of chromatomem-
brane SGM generation were investigated in [121] on
an example of sulfur dioxide and vapors of ammonia
and acetic acid. In contrast to nonequilibrium genera-
tion methods, the chromatomembrane system reaches
steady-state concentrations of target components in
the extractant gas flow within less than 1 min from the
moment of the beginning of passing extractant gas
flow. As one would expect, based on the equilibrium
condition, the change in the flow rate of the extractant
gas virtually does not affect the concentration of target
components in the flow of generated SGMs (Fig. 8).
Another important advantage of chromatomembrane
generation is a possibility of the creation of an SGM
flow with preset concentrations of target components
based on their partition coefficients.
Mass-exchange biporous matrixes made of polytet-
rafluoroethylene (PTFE) modified by materials, for
example, active charcoal [122], sorption-active to tar-
get components open additional possibilities for chro-
matomembrane SGM generation. In this case, there is
no need in the constant passing of the generating solu-
tion through the used chromatomembrane cell
(CMC). After the saturation of the matrix with the
generating solution with a specified concentration of
target components, an extractant gas flow is passed
through it. In this case, the regularities of variation of
the concentration of target components in the gener-
ated SGMs (cG) on passing a flow of an extractant gas
are described by the equation obtained within the plate
theory of chromatography [123]:
N −1
cG = cG0 ex p ( −v G N F ) ∑ (−v GN F ) S S ! , (8)
S =0
F = (V L K LG +V
  P K PG + VC K CG + VG ) ,
where cG0 is the initial concentration of a component in
the generated SGM; vG is the volume of extractant gas
passed through the CMC; N is the number of equiva-

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 73 No. 2 2018

124 PLATONOV et al.

cG, μg/L increase in the volume of the generated gas mixture, in

which the concentration of target components
60 remains almost constant. This value of N corresponds
to height of a composite matrix in CMC equal to about
3 5 cm. At a further increase in N, this volume increases
40 insignificantly. At the increase in N from 10 to infinity,
the value of V0.95 (volume of gas at which cG/cG0 = 0.95)
2 increased only twofold.
20 1 Along with obvious experimental convenience (use
of one CMC instead of 5–10 consecutively connected
bubblers filled with a generating solution), the chro-
matomembrane method ensures the variation of the
extractant gas flow rate in wider range (to 200 mL/min
0 20 40 60 at the diameter of the matrix 16 mm) without a change
WG, mL/min of the concentration of target components in the gen-
erated gas mixture. In this case, the drop carryover of
Fig. 8. Influence of the flow rate of extractant gas (WG) on the generating solution with the extractant gas flow,
the concentration of components in chromatomembrane characteristic for bubbler and being a reason for the
SGM generation. (1) Ammonia (concentration in solution low reproducibility of SGM generation in the bubbler
0.004 M); (2) sulfur dioxide (concentration of sodium version, is completely excluded. The experimentally
hydrosulfite in solution 0.004 M, pH 3.35); (3) acetic acid
(concentration in solution of 0.05 M) [121]. found values of partition and adsorption coefficients
of some organic substances and the volumes of gener-
ated SGMs with concentrations of these substances
lent theoretical plates; VL, VP, VC and VG are volumes 50 mg/m3 are summarized in Table 6 [124].
of liquid phase (generating solution), PTFE, active The volumes of generated SGMs in the chro-
charcoal, and gas phase, respectively; KLG is partition matomembrane method can be increased using com-
coefficient between the liquid and gas phases; KPG and posite matrixes of larger volumes, sorption and active
KCG are adsorption coefficients on corresponding materials with higher adsorption coefficients to the
interfaces. target components, and increased concentrations of
these materials in the matrix [125]. It has been found
The value of cG0 is determined by the concentration recently [126] that chromatomembrane generation is
of target components in the generating solution cL0 : also possible on granulated composite coal–fluoro-
plastic matrixes with the concentration of active char-
cG0 = cL0 /KLG. coal up to 30%.
As follows from Eq. (8), the volume of the gener- The same principle of equilibrium saturation of a
ated SGMs with a quasiconstant concentration of a flow of extractant gas with target components in the
generation of SGMs causes approximately equal errors
target component, equal to cG0 , increases with an of measurements of concentration of these compo-
increase in F, i.e., partition coefficients and adsorp- nents using VSGMs and CMCs. However, in contrast
tion of the target components, and also with an to VSGMs, chromatomembrane cells are intended for
increase in the number N. Thus, the increase in N repeated application, and they can be filled in any
from 1 to 10 leads approximately to a twentyfold chemical analytical laboratory, though CMCs have
not passed tests for the type and are not included in the
State Register of Measuring Instruments.
Table 6. Values of partition and adsorption coefficients
(20°C) and volumes of generated SGM (V0.95) [124] (the
volume of chromatomembrane matrix in the CMC – 5 wt % ACKNOWLEDGMENTS
of the BAU active charcoal on PTFE − 4 cm3, volume rate
of SGM 200 cm3/min) This work was supported by the Ministry of Educa-
tion and Science of the Russian Federation within the
Component KLG KPG KCG V0.95, L State Contract, project no. 4.6875.2017/8.9.
Chloroform 8.1 12 55000 2.2 ± 0.2
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Translated by E. Rykova
2018