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

net/publication/225154887

Use of the standard addition method in quantitative chromatographic analysis

Article in Journal of Analytical Chemistry · October 2006

DOI: 10.1134/S1061934806100042

CITATIONS READS
16 2,976

2 authors, including:

I. G. Zenkevich
Saint Petersburg State University
308 PUBLICATIONS 3,222 CITATIONS

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Analysis of the chemical composition of the products of La-catalyzed mathanolysis of Russian VX View project

Chromatography, theory View project

All content following this page was uploaded by I. G. Zenkevich on 19 June 2020.

The user has requested enhancement of the downloaded file.

ISSN 1061-9348, Journal of Analytical Chemistry, 2006, Vol. 61, No. 10, pp. 967–972. © Pleiades Publishing, Inc., 2006.
Original Russian Text © I.G. Zenkevich, I.O. Klimova, 2006, published in Zhurnal Analiticheskoi Khimii, 2006, Vol. 61, No. 10, pp. 1048–1054.

ARTICLES

Use of the Standard Addition Method

in Quantitative Chromatographic Analysis
I. G. Zenkevich and I. O. Klimova
Research Institute of Chemistry, St. Petersburg State University, Universitetskii pr. 26, St. Petersburg, 198504 Russia
Received March 16, 2005; in final form, August 18, 2005

Abstract—Using the standard addition method as an example, several versions of it recommended for the
determination of volatile components in complex hydrophobic matrices additionally containing compounds
with sorption properties were considered. It was demonstrated that, along with the extrapolation of results to
the zero standard addition, the most efficient techniques are the artificial transformation of similar samples into
heterophase systems, when the analytes are distributed between both phases and the interfering components are
predominantly localized in only one of the phases.
DOI: 10.1134/S1061934806100042

Methods of quantitative analysis that are used in matographic analysis is substantially behind the
chromatography are conventionally subdivided into requirements of analytical practice. In some of the
several types, depending on the character of sample existing manuals, the differences between the methods
preparation operations and algorithms of data process- are either discussed at the level of brief enumeration [2]
ing. These are the absolute calibration method (I), the or not mentioned at all [8]. Up to now, one can run
external standard method (II), the internal standard across instructions that calibration coefficients (fi) must
method (III), the standard addition method (IV), and be measured for all mixture components using the
the internal normalization method (V) [1–4]. Several internal normalization method (V) [4]. However, in the
techniques for quantitative determination that are not case of multicomponent samples, this is practically
used in chromatography are also known, e.g., the isoto- impossible. For a long time, this technique of data pro-
pic dilution method (version of the standard addition cessing was used only in the approximation fi ≡ 1, e.g.,
method, which can be implemented only in chromatog- in the analysis of petroleum products or in the represen-
raphy–mass spectrometry [5]) or detailed recommen- tation of the results of analyses by chromatography–
dations for performing these analyses in spectropho- mass spectrometry. Even more out-of-date is such a
tometry [6]. known limitation on the use of this method as the neces-
However, there are many examples when this strict sity of the detection of the signals of all components in
classification of methods (I–V) cannot adequately rep- chromatograms. Actually, it can be used for any of the
resent the variety of their versions, which are used in groups of components irrespective of the presence of
real analytical practice. For example, the controlled other compounds in the samples (an arbitrary name is
internal normalization method was considered in “local” internal normalization). For example, to esti-
monograph [1] as an independent method, and “refer- mate the ratio of isomeric octanes in petroleum frac-
ence standard” method was considered in manual [3] tions by this technique, there is no need to take other
along with the external (II) and internal (III) standard hydrocarbons into account.
methods and recommended for routine industrial con- All methods of quantitative chromatographic analy-
trol. There are versions of the standard addition method sis were historically recommended for the analysis of
(IV) involving the additional comparison of the results homogeneous samples. Only in 1998 was it demon-
with auxiliary compounds either existing in the sample strated that one of these methods, the standard addition
or introduced into it artificially [1]. Nearly all methods method (IV), is applicable to the determination of the
(except for internal normalization, V) are adapted to total concentration of components of heterophase sys-
head-space analysis [4, 7], the technique for the gas- tems [9]. For the additional accuracy control of the
chromatographic determination of the composition of results, the double (successive) standard addition of a
condensed phases from the data for vapor–gas media reference sample into the same sample was proposed in
that occur in contact with condensed phases, which [9]. An alternative technique of the implementation of
requires different experimental operations and special an analogous recommendation is known: the introduc-
techniques for processing the results. tion of nonidentical additions into a series of identical
The current characterization of the possibilities and samples with the subsequent actual extrapolation of
limitations of different methods for quantitative chro- results to the “zero” standard addition [10], which was

967
968 ZENKEVICH, KLIMOVA

also mentioned in the manual [4, p. 361]. This tech- (as the gel-forming agent), and about 1.7% (when pre-
nique was also used in [11] in the determination of pared) peppermint essential oil. Some samples addi-
residual amounts of pesticides in vegetable materials. tionally contained phosphatidyl choline (lecithin) and
The frequent use of a brief list of different versions α-tocopherol acetate. The analytical problem was the
of the standard addiction method without their detailed quantitative determination of the concentration of mul-
characterization is unsatisfactory if for no other reason ticomponent peppermint oil in this system.
than it commonly remains unclear when it is necessary Sample preparation included the dissolution of
to use a particular version. In particular, this is true for weighed portions of gel samples (mx about 2 g) in 4 mL
the determination of volatile components in complex of hexane with the subsequent determination of the
matrices that are nonvolatile, viscous, hydrophobic, total mass of the solution (m). The resulting viscous
and sometimes thermally unstable compounds in a homogeneous solutions were divided into two approxi-
mixture with ingredients possessing pronounced sorp- mately equal parts (weighed portions m1 and m2) and
tion properties. The most important methodological placed in tightly sealed bottles with a volume of 7–
technique in the analysis of these samples is their arti- 10 mL (of the penicillin type). The amount of the sam-
ficial transformation into heterophase systems. In this ple in each of the replicate samples was mx1 = mx m1/m
case, the suitable selection of solvents partially misci- and mx2 = mx m2/m, respectively. A weighed portion
ble with each other can provide a situation when all (about 50 mg) of peppermint oil (reference sample) was
interfering components are predominantly localized in introduced into the second of these samples; next, equal
one of the phases, whereas the analytes are distributed amounts (1–2 mL) of acetonitrile were added to both
between both phases. The aim of this work was to con- samples, the mixtures were vigorously shaken and left
sider this version of the standard addition method. for segregation for 5–10 min, samples of the upper
(hexane) layers of the heterophase systems were
EXPERIMENTAL injected into the chromatograph, and the total areas of
all peaks eluted after the solvent were measured. The
Gas-chromatographic analysis was performed on a main components of peppermint oil are menthol (reten-
Tsvet-500M chromatograph with a flame-ionization tion index on the Carbowax 20M stationary phase is
detector and a glass packed column 3 m × 2 mm with 1652 ± 20), menthone (1481 ± 22), pulegone (1658 ±
15% Carbowax 20M polyethylene glycol on Chroma- 22), and menthyl acetate (1641 ± 15). In these determi-
ton N AW DMCS (0.16–0.20 mm) under isothermal nations, it is reasonable to introduce an additional layer
conditions at a temperature of 120°C. The temperature of glass wool (3–5 cm) into the initial portion of the
of the detector thermostat was 150°C; the temperature chromatographic column and replace it within 20–
of the injection port was 200–250°C. Nitrogen was 25 sample injections (working day), because the accu-
used as the carrier gas; the flow rate was 30 mL/min. mulation of nonvolatile components of samples in the
The volume of injected samples was 0.3–1.2 µL (MSh-1 layer can substantially decrease the efficiency of chro-
and MSh-10 microsyringes). Chromatograms were matographic separation.
processed using MutiChrom software (version 1.52).
As a model sample of a mixture of a volatile analyte,
a hydrophobic matrix, and a sorbent, we selected a mix- RESULTS AND DISCUSSION
20
ture of 4-tert-butyltoluene (Tb = 192.8°ë, d 4 = 0.861, General features of the standard addition
method. Speaking about the standard addition method,
20
n D = 1.492; 4.75%), lubricating oil (TU 6-15-691-77; it is necessary first to comment on some historically
91%), and graphitized carbon black (Sspecific about prevalent stereotypes in its use, which deal with the
main computational relationships. Indeed, both in
100 m2/g, a pilot sample from the All-Russia Research monograph [1] and in the most recent tutorials [4], the
Institute of Luminophors, Stavropol’, Russia, 1978; following formula is presented for the calculation of the
4.3%). One milliliter of hexane (or less volatile hep- concentrations of analytes in samples (cx) by this
tane) was added to two weighed portions of the sample
(about 1 g each), a weighed portion of the analyte method:
(24.5 mg) was added to one of the solutions, and both m add /M samp
samples were transformed into heterophase systems by c x = -----------------------------------------------------------------
-, (1)
( P i ( 1 ) /P i ( 2 ) ) ( P x ( 2 ) /P x ( 1 ) ) – 1
the addition of 1 mL of acetonitrile with the subsequent
separation of the acetonitrile layer. where Msamp is the mass of the sample, madd is the mass
Experimental samples of an anticongestive gel, a of the addition, Px(1) and Px(2) are the parameters of the
medicine that is at the stage of development, were pro- chromatographic peaks (areas or heights) of the analyte
vided by the Interregional center “Adaptogen” before and after addition, respectively, and Pi(1) and Pi(2)
(St. Petersburg, Russia). The medicine contains about are the parameters of the chromatographic peaks (areas
90% oil extract of several types of vegetable medicine or heights) of any other component of the mixture
raw materials, 5–10% finely dispersed silica gel (Aero- (occurring in it or introduced artificially) before and
sil A-380) with a specific surface area of 380 ± 40 m2/g after addition, respectively.

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 10 2006

 USE OF THE STANDARD ADDITION METHOD 969

The derivation of this rather simple relationship was is approximately two times larger than in the external
presented in Novak’s monograph [1]. In subsequent standard method.
manuals (see, e.g., [4]), it is commonly given without As for Eq. (1), its differentiation leads to a cumber-
justification and, as a result, is perceived inadequately some expression inconvenient for practical use and
(the standard addition method is used much less fre- containing four rather than two contributions from dif-
quently than the absolute calibration or external stan- ferent components δPi. Hence, the random component
dard method). Indeed, the Pi(1) and Pi(2) parameters of the error in determinations cx (or mx) can be at least
must be taken into account only in the particular (rare) two times larger than with the use of the simplest ver-
cases when the volumes of addition solutions are com- sion based on relationship (2) and substantially exceeds
parable with the volumes of initial sample solutions and random errors in quantitative determinations by other
their mixing leads to a substantial dilution of the ana- methods (I–III, V). Naturally, this version has not
lyzed samples. In practice, it is much more convenient received practical acceptance. Moreover, uncritical rep-
to use the standard addition method for the determina- resentation of formula (1) produces a distorted notion
tion of the total amount of the analyte in the sample of the possibilities of the standard addition method as a
when the reference compound (madd) practically does whole.
not change the volume of the sample, which can even
remain unknown. The main computational relationship Of particular interest is the comparison of the possi-
follows from the simplest proportion bilities of different methods for quantitative analysis in
the case when some part of the analyte contained in ini-
Px/Px + add = mx /(mx + madd). tial samples (mx) is lost at the step of sample prepara-
tion, i.e., their recovery from the matrix (the ratio of the
Then actually available (extracted) amount of the analyte
(mextr) to its true amount) is generally unknown
m add P x
m x = --------------------------
-, (2) (α = mextr/mx < 1). Under these conditions, the majority
P x + add – P x of methods for quantitative analysis fail to provide
accurate results. For example, in the case of the external
where Px and Px + add are the parameters of the chro- standard method, from the proportion
matographic peaks (areas or heights) of the analyte
before and after addition, respectively. αPx /Pst = mx /mst,
Basic differences in formulas (1) and (2) manifest it follows that
themselves not only in a significant simplification of
calculations and the elimination of the necessity for αm st P x
m x = ----------------
-.
measuring the chromatographic peak parameters of P st
other compounds, but also in a decrease in the random
component of the error in determination. For the func- Thus, the result is underestimated by a factor of
tion of several variables y = f(x1, x2, …, xn), these errors (1/α). However, in the standard addition method on the
(δy) are estimated on the basis of known differential introduction of additional amounts of the analyte into
relationships the sample and approximately equal losses at the step of
sample preparation, the errors in determinations are
2 largely cancelled:
δy ≈ Σ ( df /dx ) .
αPx /αPx + add = mx /(mx + madd).
Then, for Eq. (2) on the condition that δm
δPi, we
obtain Then
αm add P x
P x + add 2 2 m x = -----------------------------------
-, (4)
δm ≈ --------------------------
- δP x + δP x + add , (3) α ( P x + add – P x )
P x + add – P x
which, after the cancellation of α, yields relationship (2).
where δPx and δPx + add are the errors in the determina- If we assume that the recovery of the analyte depends
tion of peak areas (heights) of the analytes in the initial on its concentration in the sample (i.e., α = f(mx)) and,
sample and in the sample with the addition, respec- consequently, the addition of a reference sample
tively. changes its value (α2 > α1), relationship (4) must be
The presence of the factor [Px + add /(Px + add – Px)] in rewritten in the following form:
this formula means that the highest accuracy is attained α1Px /(α2Px + add) = mx /(mx + madd).
on the condition that Px + add  Px, whereas at small
additions Px + add – Px
Px the degree of uncertainty of Then
the results can be too high. For example, if the addition α 1 m add P x
is about one-third of the analyte contained in the ana- m x = --------------------------------------
-
lyzed sample, the random component in this technique α 2 P x + add – α 1 P x

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 10 2006

970 ZENKEVICH, KLIMOVA

or where r = V2/V1 is the ratio between the volumes of the

phases.
m add P x The amount of the compound in phase 1 is related to
m x = ---------------------------------
-, (5)
α*P x + add – P x the total amount of the analyte in the system as c1V1 =
βmx, where β = (1 + Kpr)–1. Consequently, to use the
where α* = α2 /α1. standard addition method in this case, we can proceed
These are the cases when it is reasonable to use such from the following proportion:
a modification of the method as the extrapolation of the βPx /(βPx + add) = mx /(mx + madd),
results (mx) to the zero value of the standard addition,
when α2 α1 and α* 1. In this case, the form of which, after the cancellation of the coefficient β, leads
to computational relationship (2). If, to increase the
the extrapolating function mx = f(madd) in the general amount of the analyte in the system, the values of Kp or
case is unknown; however, at a first approximation, this r are significantly changed (β ≠ const), the extrapola-
dependence can be assumed to be linear. This technique tion of results to the zero value of the standard addition
was used in [11] in the determination of residual can be recommended similarly to the previous case.
amounts of pesticides in vegetable materials, when the
distribution of analytes in vegetable tissues is unknown. An alternative technique for the quantitative analy-
Artificially introduced standard additions predomi- sis of the samples of this type is a much more time-con-
nantly arrive at the surface of matrix particles; conse- suming and laborious procedure of the successive liq-
quently, the conditions of their subsequent extraction uid extraction, which was mentioned in manual [1] and
are substantially different (α2 > α1). The technique with considered in detail in [12].
the introduction of several standard additions into sev- The transformation of samples into heterophase sys-
eral replicate aliquot portions of analyzed samples [4, tems at the step of sample preparation allowed, e.g., the
p. 361; 10] and the previously recommended verifica- determination of menthol in the antimigraine medicine
tion of the results of determinations using the second “Menthol pencil” (solid solution of racemic menthol in
(successive) standard addition to heterophase systems paraffin) and m-toluic acid diethylamide in an aqueous
[9], which are combinations of two organic solvents emulsion stabilized with detergents (domestic deter-
partially soluble in each other, have the same purpose. gent DETA) by a common scheme (varying only sol-
vent combinations) [9]. However, in spite of the obvi-
Use of the standard addition method in the deter- ous advantages of quantitative analysis by the standard
mination of components of complex matrices (con- addition method, the selection of particular versions of
taining sorbents) and heterophase systems. The this method is governed by the character of analyzed
quantitative determination of components of het- samples rather than by some theoretical principles.
erophase systems is of particular importance for the There are more complex samples for which the use of
analytical practice. The number of real samples of this the above techniques is insufficient. In particular, these
type is rather small; however, there are many complex are viscous matrices additionally containing com-
samples for which the artificial transformation into het- pounds with the pronounced sorption properties men-
erophase systems is the optimum operation of sample tioned above; i.e., the samples contain two phases, and
preparation. their artificial segregation leads to three-phase systems.
Among these samples are, e.g., mixtures of com- It is expected that, unlike heterophase systems, sam-
pounds with viscous, hydrophobic, and, frequently, ples containing components with sorption properties
thermally unstable matrices; the direct injection of are rather common in the analytical practice. For exam-
these samples (or their solutions) into chromatographic ple, these properties are characteristic of vegetable
columns is undesirable. Such a seemingly natural tech- materials [11], many inorganic materials, and, evi-
nique as exhaustive extraction of analytes in each par- dently, complex systems such as soils. Therefore, it is
ticular case requires such long-term preliminary opti- interesting to note that, according to manual [13],
mization of conditions that, in practice, it is used very which presents about 500 official EPA procedures
rarely. If these samples are transformed into het- (Environment Protection Agency, United States), none
erophase systems at the step of sample preparation, so of them takes into account potential sorption properties
that interfering matrix components are predominantly of the matrices, which is obviously invalid.
concentrated in one of the layers and the analytes are To reveale the main features of the analysis of sam-
distributed between both layers according to their par- ples of this type, we prepared (see the Experimental
tition coefficients (Kp = c2/c1), the phase containing a section) a model mixture of hydrocarbon lubricating oil
smaller amount of interfering compounds can be (hydrophobic matrix) with graphitized carbon black
selected for analysis. The total amount of the analyte (hydrophobic sorbent). As the analyte component, we
(mx) is distributed between the two phases with the vol- selected 4-tert-butyltoluene (4.7%). The direct gas-
umes V1 and V2, and then chromatographic analysis of this sample is impossible
not only because of the ingress of matrix components
mx = c1V1 + c2V2 = c1V1 + Kpc1V2 = c1V1(1 + Kpr), into the chromatographic column, but mostly because

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 10 2006

 USE OF THE STANDARD ADDITION METHOD 971

Table 1. Results of the determination of the concentration of 4-tert-butyltoluene in a model sample (from the data of the anal-
ysis of the acetonitrile layer of the heterophase system)

Portion Portion Mass of the addition, Total peak areas, mV ms

c = mx/M, %
of the sample mx1, g of the sample mx2, g mg Px Px + add
1.106 1.065 24.5 1591.9 2254.5 4.52
1616.3 2361.9
1582.1 2342.5
1596.8 2319.6
Specified, % 4.75
δc, % –4.8

of an ambiguous degree of sorption of the target analyte As an additional example, we can consider experi-
on the sorbent. The use of the previously proposed tech- mental preparations of a gel containing an oil extract of
nique of the transformation of the sample into a het- different medicinal herbs, several artificial additives
erophase system [9], e.g., using a combination of hex- (including peppermint essential oil, which should be
ane and acetonitrile, which are partially soluble in each determined), and additionally 5–10% finely dispersed
other, does not give satisfactory results either, because polar (hydrophilic) inorganic sorbent (Aerosil A-380).
the conditions of the sorption of the target compound The version of the standard addition method recom-
and the reference sample in this case are not identical. mended previously [9] for heterophase systems (addi-
Therefore, to solve this analytical problem, it is nec- tion is introduced into the previously obtained het-
essary to provide identical conditions of analyte distri- erophase system) was found unsuitable in the presence
bution between the sorbent and the matrix before and of compounds possessing sorption properties, because
after the addition of the reference sample. Unsatisfac- it gave nonreproducible results (spread of values was
tory results cause the necessity of the further optimiza- 6–7 times):
tion of analytical procedures and the method as a
whole, preferably, without its complication. For exam- Determined
ple, the above technique of data extrapolation to the Sample Portion, g Addition, mg concentration of
zero standard addition could be used; however, in this peppermint oil, %
case we found a more efficient technique, which
involved an insignificant modification of the procedure 1 1.36 22 1.77
of sample preparation. When sorbents occur in the 2.96 56 0.64
composition of complex samples, it is more reasonable
to introduce the standard addition before rather than 2 1.64 26 1.71
after their transformation into heterophase systems 2.55 49 2.75
when the sorbent is localized in one of the phases. The
implementation of this simple condition means that the 49 + 57 = 106 1.58
initial sample (mx) must be divided into two approxi- 0.83 40 1.99
mately equal parts, one of which (mx1) is analyzed 2.34 63 2.56
directly and to the other (mx2) the reference sample
(madd) is added, and only after that are both samples 3 1.04 27 2.22
segregated by additions of the second solvent. Then, 3.69 78 4.25
taking into account that in the general case mx2 ≠ mx1, a
somewhat modified general relationship (2) should be
used for the correction of the results: In this case, unlike the previous example, the aceto-
nitrile layer is unsuitable for the chromatographic anal-
m add P x ysis, because nearly all finely dispersed hydrophilic
m x = -----------------------------------
-. (6) sorbent is concentrated in this layer. Only the hexane
m x2
P x + add – -------- P x phase is suitable for injection in spite of the fact that
m x1
nonpolar matrix components are transferred into this
This division of analyzed samples into several repli- phase and, consequently, the initial portion of the chro-
cate samples does not substantially complicate the ana- matographic column must be regenerated after every
lytical procedure and was known previously [4, p. 361]. 20–25 determinations. If the order of the introduction
This simple modification of the procedure provides of the reference sample addition and the formation of
reliable results of the analysis of a model sample com- the heterophase system is reversed, it is possible to
plying with the added–found criterion (see Table 1). attain the repeatability of replicate determinations at a

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 10 2006

972 ZENKEVICH, KLIMOVA

Table 2. Results of the determination of the concentration of peppermint oil in experimental samples gel with the use of the
discussed version of the standard addition method

Portion of the Portion Mass of the Total peak areas, mV ms Concentration

Sample
sample mx1, g of the sample mx2, g addition, mg Px Px + add of peppermint oil, %

1 1.099 1.083 52 145.0 602.7 1.60

158.5 591.4
1.358 1.322 58 99.9 352.4 1.62
91.6 338.3
2 1.135 1.118 64 95.8 420.4 1.54
88.2 434.8
1.133 1.149 63 87.4 393.5 1.60
88.4 396.9
3 1.128 1.147 62 90.8 422.2 1.52
90.7 418.8
1.089 1.139 57 108.4 473.1 1.49
101.6 487.6

level of 1.9–3.2 rel %, which is illustrated by the data 3. Guiochon, G. and Guillemin, C., Quantitative Gas Chro-
presented in Table 2. matography for Laboratory Analyses and On-Line Pro-
cess Control, Amsterdam: Elsevier, 1988.
The accuracy of the obtained results in this case can- 4. Stolyarov, B.V., Savinov, I.M., Vitenberg, A.G., et al.,
not be verified, because the specified concentration of Prakticheskaya gazovaya i zhidkostnaya khromatografiya
peppermint oil in the samples was 1.7% when prepared (Practical Gas and Liquid Chromatography), St. Peters-
and the concentration of volatile compounds can some- burg, 2002.
what decrease on storage. The determination of the 5. Khmel’nitskii, R.A. and Brodskii, E.S., Khromato-mass-
degree of their loss was the final aim of the determina- spektrometriya (Chromatography–Mass Spectrometry),
tions. The obtained results and the proposed procedure Moscow: Khimiya, 1984.
are recommended for use in the development of the 6. Bernshtein, I.Ya. and Kaminskii, Yu.L., Spektromet-
pharmacopoeia article of the enterprise for the corre- richeskii analiz v organicheskoi khimii (Spectrometric
sponding medicine. Analysis in Organic Chemistry), Leningrad: Khimiya,
1986.
Thus, the standard addition method can be used in 7. Vitenberg, A.G. and Ioffe, B.V., Gazovaya ekstraktsiya v
the quantitative determination of the concentration of khromatograficheskom analize (Gas Extraction in Chro-
volatile components in complex matrices additionally matographic Analysis), Leningrad: Khimiya, 1982.
containing compounds with sorption properties. The 8. Kogan, L.A., Kolichestvennaya gazovaya khromato-
main point of the proposed recommendations is that grafiya (Quantitative Gas Chromatography), Moscow:
two replicate samples must be prepared from the ana- Khimiya, 1975.
lyzed sample, the reference sample addition is intro- 9. Zenkevich, I.G. and Ragozina, T.N., Zh. Prikl. Khim.,
duced into one of these two samples, and only then are 1998, vol. 71, no. 5, p. 763.
both samples transformed into heterophase systems 10. Vigdergauz, M.S. and Krauze, I.M., Zh. Anal. Khim.,
with the subsequent chromatographic analysis of the 1986, vol. 41, no. 11, p. 2064.
layer containing the smallest amount of interfering 11. Ostroukhova, O.K. and Zenkevich, I.G., Zh. Anal.
components. Khim., 2006, vol. 61, no. 5 [J. Anal. Chem. (Engl.
Transl.), vol. 61, no. 5].
12. Zenkevich, I.G., Pimenov, A.I., and Makarov, V.G.,
REFERENCES Labor. Zh., 2002, no. 1, p. 10.
1. Novak, I., Quantitative Analysis by Gas Chromatogra- 13. Drugov, Yu.S. and Rodin, A.A., Monitoring orga-
phy, New York: Marcel Dekker, 1975. nicheskikh zagryaznenii prirodnoi sredy: Prakticheskoe
rukovodstvo (Monitoring of Organic Contamination in
2. Quantitative Analysis Using Chromatographic Tech- Natural Environments: A Practical Manual), St. Peters-
niques, Katz, E., Ed., New York: Wiley, 1987. burg: Nauka, 2004.

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 61 No. 10 2006

View publication stats