Fresenius Zeitschrift liir
Fresenius Z Anal Chem (1983) 316:765- 769
9 Springer-Verlag 1983
Analytical Chemistry in the USSR Yu. A. Zolotov V.I. Vernadsky Institute of Geochemistry and Analytical Chemistry, Academy of Sciences, 47A VorobievskoeRoad, 117975, GSP-I, Moscow V-334, USSR
Analytische Chemie in der UdSSR
Table1. Some organic analytical reagents synthesized in the USSR
Zusammenfassung. Es wird ein allgemeiner Uberblick fiber die Analytische Chemie in der UdSSR gegeben. Behandelt werden folgende Themen: Geschichte; haupts/ichliche Errungenschaften; entwickelte Analysenmethoden, Ger~ite und neue Reagentien; untersuchte Materialien; analytische Kontrolle in der Industrie und anderen Gebieten; Unterricht und Ausbildung; Ver6ffentlichungen und internationale Kontakte.
Reagent
Authors
Year
Dipicrylamine Thorin Stilbazo Berillon II Diantipyrylmethane Lumogallion Arsenazo III Sulphochlorophenol S Carboxyarsenazo
N.S. Poluektov V.I. Kuznetsov V.I. Kuznetsov A.M. Lukin S.I. Gusev A.M. Lukin S.B. Savvin S.B. Savvin V.I. Kuznetsov, S. B. Savvin, N. N. Basargin Yu. M. Dedkov
1933 1942 1950 1950 1950 1960 1959 1964 1960
Summary. A general review is given of analytical chemistry in the USSR. The following points are discussed: history; main achievements; developed analytical methods, instruments and new reagents; materials analysed; analytical control in industry and other fields; education; publications and international contacts.
The main aims of analytical work in the USSR are not different from those generally pursued in this field of science. They include the improvement of sensitivity, accuracy, precision, selectivity and analysis time. Sometimes, it is necessary to deal with more particular problems concerning localization, non-destructive, long-distance or continuous flow analysis. Analysts working in various research institutes, universities, industrial and other laboratories are engaged in these activities. Colleagues in many countries believe that analytical chemistry in the USSR plays the leading role in several branches, i.e. in U.V. and visible spectrophotometry, organic analytical reagents, electrochemical techniques (particularly stripping voltammetry), solvent extraction, analysis of highpurity and mineral raw materials, of noble and other rare metals. Interesting results have been obtained in the fields of gas chromatography, atomic absorption and emission spectrometry, spark source mass spectrometry, and chemometrics.
1. History The development of analytical chemistry in the USSR began in the late 19th century. At that time M. A. II'insky described the reaction of nitrosonaphthols with cobalt. N. A. Menshutkin published his textbook on analytical chemistry, which appeared in 15 editions and was translated into many languages. M. S. Tsvet introduced chromatography in 1903 and M. A. Chugaev found in 1905 the selective reaction of
Picramine e
1970
nickel with dimethylglyoxime. The latter also developed the theory of chelate formation; he showed in particular that fiveand six-membered rings form the most stable chelates. N. A. Tananaev (simultaneously with F. Feigl) proposed the spot-test technique. Thin-layer chromatography was first described by N. A. Ismailov and M. S. Shreiber in 1938. Plasma sources were suggested for atomic emission analysis in the fourties. The ICP technique was initiated by a paper of Babat published in the USSR in 1942. Extensive experiences were gathered with regard to the analysis of minerals and metals. After the Second World War, the analysis of nuclear and electronic materials became an important task of applied analytical chemistry. A. K. Babko and his coworkers dealt with the examination and wide analytical application of various mixed ligand complexes. The theory of the reaction of organic reagents was developed, in particular, by V. I. Kuznetsov, L. M. Kulberg and S. B. Savvin. Many sensitive and selective organic reagents were synthesized, e.g. Thorin, Arsenazo III and Berillon II (see Table 1). B. V. L'vov was the first to use electrothermal atomization in AAS and he was awarded the Talanta Gold Medal for his work. Analytical chemistry has promoted scientific and technical progress, has constantly solved complex problems concerning analytical control in industry, and has assisted in the development of new materials and substances. Several analytical methods, particularly separation and concentration procedures have been applied on a commercial scale.
2. Development and Application of Analytical Techniques Among the analytical methods used in the USSR spectrometry is of main importance. Atomic emission spectrometry is
766
Fig. 1
From left to,right: Dr. M. Williams (Talanta), Prof. I. P. Alimarin, Prof. B. V. L'vov with Talanta Gold Medal and Prof. Yu. A. Zolotov
chiefly employed for geological and metallurgical materials and, after pre-concentration of trace elements, for high-purity materials, e.g. semi-conductors. It plays an important role in the analysis of platinum containing natural and industrial samples, usually in combination with pre-concentration by fire-assay or other techniques. Atomic emission spectrometry with photoelectric recording and multi-channel instruments is applied for the determination of minor and trace impurities in metals and alloys. Various types of domestic instruments are available for that purpose. Many examinations have been carried out in that field concerning the influence of carriers and other additives, of inert atmosphere, of the excitation sources and of the enrichment procedures. A great number of combinations with such procedures has been developed and many are used in industrial laboratories for routine analyses. As little as 10 -6 to 1 0 - 8 % of a trace element can be determined. ICP has intensively been studied as a promising excitation source for the analysis of solutions, for instance of geological samples. The flame technique of AES is at present not practically used in the USSR. Atomic absorption spectrometry has become one of the most important methods for trace analysis of environmental, metallurgical and other materials. In the sixties, B. V. L'vov introduced his graphite furnace and in the seventies his wellknown platform for AAS (Fig. I). He also carried out many fundamental investigations on AAS with electrothermal atomization. A few types of domestic AAS spectrometers are available, but their number is not sufficient and many instruments have to be purchased from Perkin-Elmer and other companies. A multi-channel instrument for AAS and AES has been designed, which allows the determination of 12 elements simultaneously by means of a continuous source (Xe-lamp). Atomic fluorescence is not of practical importance yet, but quite a number of interesting research results has been obtained. Laser AFS allows theoretically the determination
Table 2. Detection limits (in ppb) for the determination of several elements by LAFS and FLAAS
Element
LAFS
FLAAS
Lead Iron Copper Silver Cobalt
2.5 x I0 -s 0.001 0.002 0.003 0.002
0.05 0.05 0.05 0.005 0.4
Table3.
Comparison of methods for trace analysis
Method
Detection limit ( p p b )
Selectivity
AAS NAA SSMS LAFS LSPI
1- 10,000 0.01 - 100 1 - 100 0.1 - 100 0.001 - 0.1
medium medium high high very high
of some hundred or even ten atoms, reaching in this case the natural absolute detection limit. Very low detection limits have already been achieved and work is going on at the Institute of Spectroscopy of the Academy of Sciences and in Moscow University. Table 2 shows the detection limits of several elements for laser atomic fluorescence spectroscopy (LAFS) and flameless AAS (FLAAS). Another variant of laser spectroscopy is the step-by-step photoionization of atoms. This technique offers the following advantages: extremely high sensitivity, analysis of the sample without pre-treatment, no addition of impurities during analysis, possible distinction between bulk and surface impurities. A comparison of the detection limits and selectivities for several techniques is given in Table 3.
767 Table4.
Detection limits for noble metals determined by NAA
Element
Detection limit (g/g)
Iridium Gold Osminum Palladium Platinum Silver Rhodium
1 x 10- it 1 • 10-11 1 x 10 -9 5 • 10- a 1 • 10-a 1 x 10-8 1 x 10-8
X-ray fluorescence spectrometry is considered to be one of the most precise and powerful techniques. It has become a conventional method in the USSR for the iron, non-iron and mining industries. For trace analysis, however, it is not very efficient because the detection limits are not sufficiently low (usually 10 -3 to 10-4%). Powerful XRF multi-channel quantometers are manufactured and marketed in Leningrad; they are often used in combination with optical quantometers for the determination of various minor components. Fundamental research work is being made in mass spectrometry of solids, particularly with regard to SSMS. Main aim is the improvement of the precision of this technique by studying the physical and chemical processes occurring during spark discharge in vacuum. G. I. Ramendik's plenary lecture at the Euroanalysis IV conference in Helsinki (1981), which dealt with the results of these studies, met with considerable interest. It has been possible to develop a general probe method for analysing both solids, including non-conducting materials, and solutions. At present, SSMS can be employed for the determination of 70 elements in concentrations as low as 10 -5 to 1 0 - s % with a relative Standard deviation of 0.05 to 0.1 and a material consumption of 3 to 8 mg. SSMS techniques have been worked out for local and layer-by-layer analysis of metals, alloys, semiconductor materials, and epitaxial films of silicon and germanium with a depth resolution of 0.1 ~tm. Radioactivation analysis, one of the most sensitive methods, in particular if slow neutrons are employed, has found wide application both in its instrumental variant and in the variant with separation of radioisotopes of the test elements and their radiochemical purification. Various methods of activation are used, including activation with slow and fast neutrons, gamma quanta and charged particles, the latter being especially suitable for the determination of gaseous impurities. Neutron activation analysis has proved to be a convenient routine method for the determination of gold in rocks and ores. Besides nuclear reactors, neutron generators and neutron sources of the zszcf and also Sb-Be type can be used for this purpose. Detection limits for noble metals are compiled in Table 4. Many electrochemical methods have been developed in the USSR. Essential progress has been made in the theory of voltammetric methods and their application. The number of elements, which can be determined, has been extended essentially by the use of various solid electrodes, of effective organic reagents and masking agents, and of non-aqueous media. The theory of stripping voltammetry has been successfully worked out for various electrode processes, and the kinetics of the formation and dissociation of intermetallic and complex compounds has been examined. High sensitivity and short analysis time are the advantages of stripping voltam-
Table5. Detection limits for platinum metals determined by kinetic methods Element
Detection limit ~g/ml)
Rhodium Iridium Osmium Ruthenium Palladium Platinum
1 • 10-s 1 • 10-5 1 x 10-5 1 • 10- 5 1 x 10-3 1 • 10-z
metry and application has been found especially for highpurity materials, metals, pure water and thin films. A wider use in practical analysis would certainly be suitable. New ion-selective electrodes have been designed, particularly liquid membrane electrodes. Selective solvent extraction systems are used for this purpose. Recently, mixed ligand complexes of copper(I) with halides (or thiocyanate) and N-substituted thioureas have been suggested as membraneactive components, and a thiocyanate-selective electrode has been constructed. This is a membrane of a new type in which coordinatively solvated complexes are used. Controlled potential coulometry is now considered as a method for the most precise determination of the major components of a variety of materials. Advances have been made in the development of spectrophotometric methods. New organic reagents permitted a significant increase in sensitivity. At present, virtually any element can be determined and there are extensive application possibilities in analytical practice. Kinetic methods for trace analysis have been developed in the USSR at several well-known analytical centres: Moscow University, Moscow Institute of Fine Chemical Technology, Kiev Institute of Physical Chemistry, and Ivanovo Institute of Chemical Technology. Various highly sensitive catalymetric methods have been described and some of these are employed in routine analysis, e.g. for the determination of iodine, silver, rhenium and platinum metals. Traces of ruthenium and osmium are determined by means of these methods in the Norilsk Plant for Mining and Metallurgy. Detection limits for platinum metals are compiled in Table 5. Several books on kinetic methods of analysis have been published, one concerning environmental analysis. Finally, it should be mentioned that such physical methods of analysis have in general become more important in recent years and have been widely used which do not require a preceding decomposition of the sample. However, in many cases a chemical pre-treatment is necessary and methods for decomposition, separation and pre-concentration are being examined in many laboratories of the USSR.
3. Inorganic Materials Analysed The analysis of mineral raw materials and various geological and space samples is of importance for the geological survey, mining and metallurgical industries and for many research activities in the USSR. Methods employed in the geological survey of 1974 for the determination of trace elements have 1teen compiled in Table 6 (only those are included used for routine analysis in at least two laboratories). At present, the importance of the methods has changed; the significance of AAS and NAA has increased whereas that of photometry,
768 Table 6. Met hods used for the determination of 34 trace elements in 1974
Table 8. Determination of oxo-anions by ion-chromatography
Method
Anion
Detection limit (ng/ml)
Standard deviation (~)
SeO2AsO3WO2MoO]CrO2-
0.01 0.10 0.35 0.25 0.50
4.2 5.2 4.8 3.6 6.8
Number of elements determinable
Photometry Atomic emission Fluorescence Atomic absorption Neutron activation Polarography Atomic emission, flame Kinetic methods
28 22 15 8 8 7 4 3
frequently determined 19 9 5 4 2 4 2
Table 7. Routine microtrace analysis in the USSR Geological Survey Method
Element
Amount (mg)
Detection limit (ppm)
Atomic emission
B Hf Mn Bi, Co, Cr, Ga and others F Eu
7 - 10 10 1 - 10
4 2 200
10 10- 200 3 - 10
20 100 5
Atomic absorption Neutron activation
fluorescence spectrometry and flame emission methods has decreased. Microtraee analysis of natural minerals is also of importance, not only for inclusions in minerals but also for the distribution of trace elements in one or several phases. Absolute detection limits of 10- 7 to 10-10 or even 10-12 to 10-1Sg have been achieved. The methods employed are: NAA, SSMS .(and other MS techniques), AES (especially with laser excitation), FLAAS, LAFS and others. Table 7 shows a few examples of routine methods employed in the USSR geological survey. A very sensitive method is the track technique used in N A for the determination of uranium. This method is based on the recording of the tracks of fission products in a specially designed solid dielectric detector. It can be employed for the analysis of very small samples of natural materials, in particular meteorites. Its advantages are: exact measurement of the distribution of uranium in very small samples, sensitivity of 10 -3 ppb, no destruction of the sample, maximum relative error only 25 ~. High-purity substances are the second important group of analysed materials. Great experience has been gathered in that field and many complex analytical problems have been solved. Atomic emission methods (including chemical preconcentration) and partly atomic absorption and spectrophotometric procedures are mainly employed in industrial laboratories. N A A and SSMS are used for this purpose chiefly in research institutes. Extensive investigations have been carried out on the trace analysis of semiconductors, pure chemical reagents and other high-purity substances. For certain problems methods with higher sensitivity are required. Blank experiments and the calibration of instruments are often necessary as standard reference materials are not always available.
It is necessary to develop methods which allow the determination of 15 to 20 impurities at a concentration of 10 -8 to 1 0 - 9 m a s s - ~ , i.e. 0.01ppb or less. A promising method in that regard is laser spectroscopy as mentioned above. Another possibility is the increase of the neutron flux in the nuclear reactor up to 1015 n/cm 2 s, permitting detection limits of 10 -8 to 10 -11 ~ for 25 to 30 elements. This is very important for the analysis of weakly activated matrices, e.g. silicon and graphite. Trace analysis of environmental materials is being investigated in many laboratories. As an example, ionchromatography should be mentioned which was recently applied at Moscow University for the determination of selenium, arsenic, chromium, molybdenum and tungsten in natural and waste waters. This determination is based on the use of oxo-anions, e.g. selenate. The sensitivity is very high; as little as 0.1 ng/1 of arsenic can be determined. Detection limits and standard deviations for several oxo-anions are given in Table 8. 4. Pubfications and Education There are three scientific journals in the USSR publishing papers on analytical chemistry: Zhurnal Analiticheskoi Khimii (Journal of Analytical Chemistry), Zavodskaya Laboratoriya (Industrial Laboratory) and Zhurnal Prikladnoi Spektroskopii (Journal of Applied Spectroscopy). Many papers are also published in other Russian journals, including all-union and local ones. Soviet scientists also publish papers in international journals. According t ~ available data the USSR is first among other countries with regard to the number of publications on analytical chemistry. Several series of monographs on analytical chemistry are published regularly, e.g. "Analytical Chemistry of the Elements", "Analytical Reagents", "Problems of Analytical Chemistry" (Nauka Publishers) and ,,Methods of Analytical Chemistry" (Khimia Publishers). Other books appear apart from these series, too. There are more than 70 universities and approximately 50 chemotechnological institutes in the USSR, from which students can graduate in analytical chemistry. In addition, many agricultural, medical and technical institutes have departments of analytical chemistry. The total number of such departments is not exactly known, but there are about 200 to 300 of them. The M. V. Lomonosov Moscow University has a large analytical department, Prof. I. P. Alimarin being the head. During the third and fourth term all students of the Chemical Department have to study analytical chemistry. If a student selects analytical chemistry as the main subject, he has to attend an advanced course of analytical chemistry during the eighth and ninth terms. During the tenth term students deal
769 with their diploma (research) works. The whole training covers a period of 5 years. In addition, there is the graduate school of 3 years for preparing the Ph.D. thesis.
5. International Contacts There are various international contacts of Soviet scientists with those of other countries. Since 1983 ten Soviet specialists are members of the IUPAC Commissions. Analysts of the USSR are members of the editorial or advisory boards of 24 international or foreign national journals on analytical chemistry or closely related fields. Several analysts have been invited as plenary lecturers for the most important international conferences on analytical chemistry (Euroanalysis, Microchemical Symposium and others). Prof. Alimarin is a honorary member of many societies and doctor honoris causa of many universities. There is a joint symposium on analytical chemistry between the USSR and Japan.
6. Institutes and Coordinating Boards Several leading institutions of analytical chemistry should be mentioned: V. I. Vernadsky Institute of Geochemistry and Analytical Chemistry, Institute of the Rare Metal Industry, Institute of Chemical Reagents and High-Purity Substances, M. V. Lomonosov State University, Institute of Mineral Raw Materials, D. I. Mendeleev Institute of Chemical Technology. All these institutions are situated in Moscow. Interesting research work is also carried out at the Physico-Chemical Institutes of Odessa, Kiev and Leningrad Universities and the Novosibirsk and Riga Institute of Inorganic Chemistry and many others. There is a body for the coordination of research work in analytical chemistry in the USSR, i.e. the Science Council on Analytical Chemistry, which belongs to the Academy of Sciences of the USSR. This council is responsible for the development of analytical chemistry all over the country. In particular, the council organises conferences and symposia, promotes the design and manufacturing of analytical instruments, reagents and standard reference materials. The D. I. Mendeleev All-Union Chemical Society is the second coordinating body; it has a division of analytical chemistry.
7. Analytical Control It is well known that the control of the chemical composition of materials plays a significant, sometimes decisive role in many branches of the national economy. Iron and non-iron metallurgy, chemical and petroleum industries, mining industry, electronics, food and pharmaceutical industries should be mentioned in that regard. Consequently, analytical methods have attracted considerable attention and the requirements still increase.
W. Ostwald wrote in 1912: ,,The aim of any science is finally to find application, because science without application, or more precisely without the aim of prediction, does not deserve the name of science: it is of no interest to society and therefore cannot demand support from society." These words are particularly true for analytical chemistry, whose aim is to organise analytical control in industry, agriculture, environment, medicine etc. This problem is solved by the laboratories of factories, geological institutes, clinics, hydrogeological service and others. The total number of laboratories in the USSR is very large, being tens and hundreds in many branches. In the geological service alone there are about 250 chemical laboratories. A large number of people is employed in these laboratories, e.g. 10,000 to 13,000 in noniron metallurgy. Many analysts are also working in iron metallurgy and in the chemical industry. Not only the analytical problems are dealt with in these laboratories, but the properties and other characteristics of the starting materials and finished products are also determined. In addition, the laboratories are also engaged in many instances in improving production technology. However, analytical aspects are invariably most important. The main task of production laboratories is the daily monitoring of the production processes. In order to work efficiently these laboratories should constantly be provided with new methods, reagents and instruments. The practising analyst is not always satisfied with the information obtainable from literature, in particular from journals. That, however, is not surprising:journals reflect the progress of science, but not every scientific solution can find direct use in practice. Certain generalisations, theories and new approaches serve as a basis for numerous procedures and experimental techniques; however, these procedures still have to be modified so that they can be applied to a particular group of analysed materials. The most urgent problem in production control is automation and excellent automatic analytical systems are available in the USSR for the iron and non-iron metallurgy. They are based on optical spectral and XRF multi-channel instruments, computers and devices for sampling and sample pretreatment.
8. Analytical Chemistry and Society It can be said that analytical chemistry is not the most popular science in the USSR. In contrast, there are some people who consider it to be a relatively unimportant and fading discipline. However, most scientific and administrative specialists are aware of the significance of analytical chemistry as an interesting branch of science and as an important tool of quality control. Nevertheless, analysts should pay more attention to the propagation of the achievements of our discipline making use of various media, e.g. newspapers, cinema, television etc. Received April 23, 1983