Journal of Analytical Chemistry, Vol. 57, No. 9, 2002, pp. 758772. Translated from Zhurnal Analiticheskoi Khimii, Vol.

57, No. 9, 2002, pp. 902917. Original Russian Text Copyright 2002 by Ivanov, Kochelaeva, Prokhorova.

REVIEWS

Methods for Determining Molybdenum

V. M. Ivanov, G. A. Kochelaeva, and G. V. Prokhorova
Moscow State University, Vorobevy gory, Moscow, 119899 Russia
Received September 20, 2001; in nal form, November 19, 2001

AbstractThe data on determination methods for molybdenum published from 1985 to 2001 are surveyed.

The position of molybdenum in the periodic table of the elements explains a wide variety of reactions and methods for its determination. It exhibits positive oxidation states of II, III, IV, V, and VI in compounds, and some reagents can stabilize these states. High coordination numbers of molybdenum (up to 9) and its trend to coordinate oxygen explain its complex ionic states. Thus, molybdenum(V) and molybdenum(VI) oxo 2+ anions can occur as either cationic [Mo O 2 , MoO2(OH)+, MoO2Cl+, MoO3+] or anionic [Mo O 4 , HMoO 4 , MoO2(OH) 3 ] species, depending on the acidity of solution and on the anion of an acid or a base added. Oxygen-free compounds of Mo(VI) 4 2 [Mo(CN) 8 ] or Mo(V) and Mo(VI) [Mo2Cl10, Mo F 8 , and MoF6] and isopoly and heteropoly Mo(V) and Mo(VI) compounds [Mo7 O 24 , SiMo12 O 40 ] are known; many of these compounds are stable in solutions. Molybdenum compounds with oxygen are most numerous. Thus, the following homopolynuclear molybdenum(VI) complexes can be formed as the acidity is 4 4 2 5 increased: Mo3 O 11 , Mo4 O 14 , Mo4 O 13 , HMo6 O 21 , Mo7O 24 , HMo7O 24 , H7Mo12O 41 , HMo24 O 78 , and Mo36O 112. The ionic state of molybdenum is strongly affected not only by the acidity of solution and temperature but also the concentration of molybdenum. Therefore, the ionic state of molybdenum should be known in the development of determination methods. In the determination of molybdenum, the analyte is most frequently stabilized as molybdenum(VI) in a weakly alkaline medium. All types of reactions such as acidbase, redox, and complexation reactions were proposed for the determination of molybdenum. They formed the basis of gravimetric, titrimetric, and physicochemical determination techniques. Very high sensitivity procedures based on the catalytic reactions of molybdenum and radiochemical techniques in various versions are well known. Molybdenum forms sparingly soluble compounds with inorganic and organic reagents; these compounds lie at the basis of not only
8 6 5 3 3 6 4 2

determination methods for molybdenum but also preconcentration and separation methods, including various versions of extraction and chromatography. Some of the reactions are used in the processing of molybdenum-containing raw materials. Molybdenum is primarily used for the production of special alloys and steels. They are heat-resistant, corrosion-resistant in solutions and alkali metal vapors, and refractory; they exhibit high coefcients of elasticity and shear moduli. Molybdenum is of considerable biological and physiological importance. This is one of the ten biologically active elements. It participates in nitrogen, protein, carbohydrate, and fat metabolism as well as in other biochemical processes. Molybdenum stimulates the biosynthesis of nucleic acids and proteins; it increases the chlorophyll and vitamin contents of plant organisms, and it is necessary for plants throughout their life. Molybdenum is a constituent of many enzymes (xanthine oxidase, aldehyde oxidase, and sulte oxidase). The concentration of molybdenum in human blood is 5 g/L. Molybdenum-decient soils cause leaf blotch and rolling. A deciency of molybdenum in the human diet inhibits cellular growth and increases susceptibility to caries, whereas an increased concentration of molybdenum in blood is associated with the risk of gout and disseminated sclerosis. At the same time, along with Cu, Cd, Hg, Pb, Cr, and V, molybdenum is grouped with widespread elements that are potentially hazardous to humans. The abundance of molybdenum in the Earths crust is about 3 104%; however, it can be classied with rare elements, because minerals (molybdenite MoS2 and molybdates like wulfenite PbMoO4 and MgMoO4 are known) and ores are almost absent. The molybdenum content of soil, such as chernozem, is 2.5 104 or 1.9 104% at a depth of 028 or 140150 cm, respectively (for comparison, the upper horizon of chernozem contains 0.61% Ti, 7.7 102% Mn, and 3.4 102% Zn). Among plants, buckwheat, all legumes (from 0.2 to 4.7 g/kg), vegetables, and cereals (from 0.12 to 1.14 g/kg) concentrate molybdenum. The human daily requirement for molybdenum is 0.0750.250 mg for adults and 0.06 mg for children. For comparison, the daily requirements (in mg) for

1061-9348/02/5709-0758$27.00 2002 AIK Nauka /Interperiodica

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other elements are the following: Al, 0.00140.008; Cd, 0.070.3; Cr, 0.011.2; Cu, 0.56.0; Fe, 640; and Mg, 250380. The molybdenum content of food must be currently monitored. Molybdenum plays very important roles in engineering and biology. New ore deposits should be explored and mined; the molybdenum contents of alloys and environmental samples should be monitored; the natural migration of molybdenum, in particular, in plant and animal organisms, should be studied. Thus, we can state that a topical problem is to develop selective and rapid methods for the determination of molybdenum over a wide concentration range with good metrological characteristics. At concentrations of 150, 0.55, or <0.1%, molybdenum is determined by gravimetry, titrimetry, or physicochemical techniques, often combined with preconcentration, respectively. Of spectroscopic and electrochemical techniques, spectrophotometry and voltammetry, respectively, are used most frequently, although the use of atomic emission and atomic absorption spectrometry, amperometry, and potentiometry for the determination of molybdenum is known. High-sensitivity techniques (inductively coupled plasma mass spectrometry, kinetic methods, and neutron activation analysis) are used more rarely. These techniques are most frequently used after molybdenum preconcentration and separation from a matrix. Moreover, these techniques are time consuming (neutron activation analysis) or expensive because of the instrumentation used, or they require highly skilled personnel. Therefore, spectroscopic and electrochemical techniques used for determining molybdenum, spectrophotometry and voltammetry, respectively, are primarily surveyed in this review. The analytical chemistry of molybdenum was considered in a monograph [1]. The electrochemical behavior of molybdenum was considered in monographs [2, 3] and reviews [4, 5]. The determination of molybdenum in mineral raw materials, steels, alloys, and soils attracted the greatest interest until 19851987. More recently, major attention has been focused on methods for the determination of molybdenum in plants, human and animal tissues, drinking water, and food products. This review covers data published from January 1985 to 2001; earlier publications are cited only in a historical aspect. The use of inorganic reagents is beyond the scope of this review because of the low sensitivity of these determinations. Such reagents were used before for the determination of large amounts of molybdenum and for the standardization of solutions. SPECTROSCOPIC TECHNIQUES Spectrophotometry. Molybdenum(VI) reacts with organic reagents that primarily contain oxygen as donor atoms. Molybdenum(V) reacts with sulfur-containing reagents, which initially reduce molybdenum(VI) to
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molybdenum(V) and then form chelate complexes with the latter. The interaction with nitrogen-containing reagents is less typical; if the reagents contain =NH, NH2, or quaternary ammonium groups, ion-associate complexes are formed. In this case, the ligand in the inner coordination sphere is responsible for the color and intensity of absorption. Of oxygen-containing reagents, the following are most sensitive to molybdenum(VI) (the absorption maximum wavelengths and molar absorption coefcients are given in parentheses after reagent names): 6,7-dihydroxy-2,4-diphenylbenzopyrilium chloride (535; 5.0 104), 9-(2-nitrophenyl)fluorone (570; 5.60 104), and Pyrogallol Red in the presence of dodecanoltrimethylammonium bromide (587; 8.15 104). The following sulfur-containing reagents are most sensitive to molybdenum(V): thioglycolic acid, toluene-3,4dithiol, 8-mercaptoquinoline, xanthogenates, dithiocarbamates, dialkyl dithiophosphates, and diaryl dithiophosphates [6, 7]. Reactions with molybdenum(V) are less sensitive but more selective, because they occur in a more highly acidic medium. The molar absorption coefcients of complexes, which are unstable, are no higher than 1 104 (the exception is toluene-3,4dithiol; the molar absorption coefcient of its complex is equal to 2 104). To improve the sensitivity of the determination, complexes are often extracted. Binary complexes are formed with reagents from the following classes (Table 1): hydroxamic acids, uorones, pyrocatechols, and aldehyde hydrazones. The reagents were used for the determination of molybdenum in soils [9, 10], pharmaceuticals [9, 10], and steels [16]. The complexation of molybdenum(VI) with 2-(2-furyl)-3-hydroxy-4H-chromen-4-one [20]; 3hydroxy-2-(4-methoxyphenyl)-6-methyl-4H-chromen4-one [21]; and 3-hydroxyavone [22] was studied. In the majority of cases, homogeneous aqueous organic mixtures were used for dissolving the complexes. The following o,o'-dihydroxyazo compounds were found to be the most promising reagents: 2,2'-dihydroxyazobenzene, Solochrome Violet R, Solochrome Dark Blue B, Solochrome Dark RN, Solochrome Black AS, Solochrome Green, Acid Chrome Blue 2K [1], Beryllon II IREA [23], Gallion IREA [24], Lumomagneson IREA, Lumogallion IREA [25, 26], and Magneson IREA [26]. These reagents contain an o,o'-dihydroxyazo functional analytical group, at which complexation takes place; the nitrogen atoms of the azo group are electron-donor atoms. Therefore, these reagents can be classied with tridentate ligands. This is responsible for the valuable analytical properties of the reagents and complexes: a large bathochromic shift upon complexation, a wide range of optimum acidities, and the absence of stepwise complexation because of the interaction in a ratio of 1 : 1. At the same time, not all of these reagents are used in actual practice because of low selectivity; they are mainly of theoretical interest
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Table 1. Chemical and analytical characteristics of the binary complexes of molybdenum(VI) Reagent 2-Benzylidenaminobenzohydroxamic acid 2-Salicylidenaminobenzohydroxamic acid Hydroxamic acid Phenylbenzohydroxamic acid Mandelohydroxamic acid max, nm Hydroxamic acids 358 380 375 350 0.55 0.65 1.62 7.2 12.0 11.0 1.66 0.16 0.54 3.30 0.88 0.9 0.94 [8] [8] [9,10] [11] [12] [13] [14] [15] [15] [15] [16] [17] [18] [19] 104 References

Fluorones p-Dimethylaminophenylfluorone 535 2,3,7-Trihydroxy-9-dibromohydroxyphenylfluorone 530 Azo derivatives of pyrocatechol Dihydroxyazobenzene 475 505 Thiazolylazopyrocatechol 530 p-Nitrobenzeneazopyrocatechol 540 Aldehyde hydrazones 3,4-Dihydroxybenzaldehyde guanylhydrazone 550 Resacetophenone isonicotinoylhydrazone 440 Salicylaldehyde isonicotinoylhydrazone 2,4-Dihydroxyacetophenone benzoylhydrazone 402

for the determination of relationships between the structure of reagents and the properties of the resulting complexes. In the past decades, Lumomagneson IREA and Magneson IREA [25, 26] attracted attention because of their ability to form mixed-ligand complexes, whose optical, electrochemical, sorption, and colorimetric properties are interesting from the standpoint of analytical chemistry. The structure of the reagents and the pH range of their interaction with molybdenum(VI) suggest that the cationic species 2+ Mo O 2 participates in the complexation. In contrast to Lumomagneson IREA and Magneson IREA, which react with molybdenum(VI) in the cold, bisazo compounds with analogous analytical functional groups do not form binary complexes with molybdenum(VI). Ternary complexes. The following two types of complexes can be recognized: ion associates and mixed-ligand complexes. Ion associates. Colored organic reagents, most of them are summarized in Table 1, occupy the inner coordination sphere of these complexes, whereas surfactants occur in the outer sphere. Most frequently, these are cationic surfactants, which compensate for the charge of the inner coordination sphere or the charge of dissociated sulfo groups of the reagents. A monograph [27] and a review [28] were devoted to the complexation of various metal ions in the presence of surfac-

tants. Table 2 gives some examples of ion associates [2942]. It is likely that, of this group, the ion associates of uoronates are most promising. Among these complexes, the previously proposed complex of molybdenum with o-nitrophenyluorone in the presence of diantipyrilmethane is most sensitive [43, 44]; the molar absorption coefcient of an associate with this complex is 1.31 105 (at 530 nm). Of inorganic reagents, thiocyanate ions are most frequently introduced into the inner coordination sphere of complexes. N1-Hydroxy-N1, N2-diphenylbenzamidine [45], its chlorine derivative [46], metoclopramide, oxybuprocaine [47], ethyl violet [48, 49], and xanthene dyes [50] can occupy the outer sphere. Many examples of the complexation and determination of molybdenum as ion associates and micellar or solubilized complexes with surfactants are given in a monograph [51]. It is most interesting that, upon the introduction of a surfactant, a very large bathochromic shift was observed in the complexation of molybdenum(VI) with pyrocatechol violet (PV) in the presence of cetylpyridinium (CP). The binary complex Mo(PV) exhibits an absorption maximum at 560 nm, whereas the ternary complex Mo(PV)(CP)2 exhibits an absorption maximum at 710 nm [52]; in this case, the molar absorption coefcient of the complex increased from 3.7 104 to 15.0 104. Mixed-ligand complexes. Hydroxylamine is commonly used as the second component of these comVol. 57 No. 9 2002

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METHODS FOR DETERMINING MOLYBDENUM Table 2. Chemical and analytical characteristics of the ion associates of molybdenum(VI) Reagent and surfactant Fluorones 3,4-Dimethylhydroxyphenylfluorone + Tween 80 p-Diethylaminophenylfluorone + cetylpyridinium Dibromohydroxyphenylfluorone + cetylpyridinium Phenylfluorone + dodecylmethylbenzylammonium Phenylfluorone + cetylmethylammonium o-Nitrophenylfluorone + cetylpyridinium Azo derivatives of pyrocatechol 4-(6-Bromo-2-benzothiazolylazo)pyrogallol + cethyltrimethylammonium Azo derivatives of pyrocatechol + cetylpyridinium Other reagents Quinalizarin + cetylpyridinium 7,8-Dihydroxy-4-methylcoumarin + cetylpyridinium 2,7-Dihydroxyfluorescein + cetylpyridinium Rutin + cethyltrimethylammonium Bromopyrogallol red + cetylpyridinium 526 532 532 550 524 530 531 585 580 425 630 11.6 11.0 11.9 11.8 11.0 15.5 16.3 5.76 12.7 13.2 13.3 3.54 6.0 [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40] [41] [42] max, nm 104

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References

pounds, whereas monoazo and bisazo derivatives are responsible for optical characteristics. In 1971, Savvin et al. [53] reported on the interaction of molybdenum with o,o'-dihydroxyazo compounds in the presence of hydroxylamine. The formation of mixed-ligand compounds with molybdenum, hydroxylamine, and the following bisazo derivatives based on chromotropic acid was reported: Sulfonitrophenol K, Sulfochlorophenol K, Picramine M, Sulfochlorophenol M, Sulfonitrophenol M, Sulfonitrophenol B, Sulfochlorophenol B, Sulfonitrophenol S, Picramine S, and Sulfochlorophenol S [53]. The reagents exhibit a single absorption maximum of 540560 nm, and the complexes exhibit two maximums of 600630 and 650680 nm. The bathochromic shift on the complexation is 90135 nm; the complexes are formed in an acidic medium (pH 1.5). The molar absorption coefcients of symmetrical reagents [(2.122.94) 104] are lower than those of unsymmetrical reagents (a maximum value of 5.0 104 for Sulfonitrophenol K). Note that the bisazo derivatives of ,'-hydroxyazo compounds are the least sensitive to the interaction with molybdenum and compounds containing a phenol hydroxyl group in the lefthand side and a carboxyl group in the right-hand side are the most sensitive. The 1 : 1 ratio between components, which was found with an excess of reagent, suggests that molybdenum reacts with only reagents from the phenol series, even in the case of symmetrical bisazo reagents. The mixed-ligand complexes of molybdenum with hydroxylamine and Lumogallion IREA or Magneson IREA were studied in more detail from the standpoint
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of complexation kinetics and thermodynamics [26, 54]. The complexes are formed over a wide range of pH 1.04.5 on heating. Their absorption spectra exhibit a somewhat larger bathochromic shift of absorption maximums, and the molar absorption coefcients in the presence of hydroxylamine are higher than those of binary complexes by a factor of 2 to 3. Only this fact made it possible to detect the formation of a mixedligand complex, because binary complexes are formed in the cold. The activation energies of molybdenum complexes with Lumogallion IREA and Magneson IREA are equal to 26.0 and 19.2 kJ/mol, respectively, and the ratio between components is 1 : 1 : 1 in all cases [54]. That is, a coordinatively saturated complex is formed, in which the coordination number of molybdenum is equal to 8, hydroxylamine is a monodentate ligand, and the central atom is molybdenum(VI) as 2+ Mo O 2 . The linearity range of a calibration graph is 550 g molybdenum in 20 mL of solution. As well as ,'-dihydroxyazo compounds, heterocyclic azo compounds are tridentate. However, they react with many ions that occur in only a cationic form; therefore, they do not form binary complexes with molybdenum(VI) in a weakly acidic medium [55]. In 1969, Lassner et al. [56] reported on the reaction of molybdenum(VI) with 4-(2-pyridylazo)resorcinol (PAR) at pH 67 in the presence of hydroxylamine. The resulting mixed-ligand compound with the 1 : 1 : 1 stoichiometry exhibited an absorption maximum at 530 nm and = 2.75 104. More recently [54], the kinetics and thermodynamics of complexation in this system were studied, and another pyridine azo com2002

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Table 3. Properties of molybdenum(VI) complexes with o,o'-dihydroxyazo and heterocyclic azo compounds in the absence and in the presence of hydroxylamine [54] Reagent Lumogallion IREA Lumogallion IREA + hydroxylamine Magneson IREA Magneson IREA + hydroxylamine PAR PAR + hydroxylamine 5-Br-PADAP 5-Br-PADAP + hydroxylamine max, nm HR 510 530 570 580 530 570 complex 430 430 490 490 420 420 440 440 pHopt 1.05.0 1.04.7 1.04.7 1.05.0 4.65.3 4.65.3 104 Ea , kJ/mol 1.1 2.1 0.9 2.9 Vant Hoffs tempelog rature coefficient 17.20 18.00 17.09 17.66 11.82 11.92

26.0

1.2

19.2 1.2 No complex formation 2.9 33.6 1.5 No complex formation 3.9 39.8 1.6

pound, 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP), which is the most sensitive reagent for all metal ions among the group of heterocyclic azo compounds [57], was added to PAR. The activation energies are equal to 33.6 and 39.8 kJ/mol for the Mo(VI)PARhydroxylamine and Mo(VI)5-BrPADAPhydroxylamine systems, respectively. Table 3 compares some properties of binary and ternary complexes. The activation energies and vant Hoffs temperature coefcients of complexes increase in the following order of reagents: Magneson IREA Lumogallion IREA PAR 5-Br-PADAP. The molar absorption coefcients increase in the same order; however, they are always lower in binary complexes than in mixedligand complexes. This fact also indicates that hydroxylamine enters the inner coordination sphere of the complex. The optimum range of pH 4.55.3 in the complexation with PAR, which was recommended as a reagent for the determination of molybdenum, was supported by the following almost identical calibration functions (n = 5; P = 0.95; c is the concentration of molybdenum, M): A = (2.9 0.1) 104c + (0.12 0.02) 104c (pH 4.9), + (0.2 0.1) (pH 5.3). A = (3.0 0.6) The calibration graphs were linear at molybdenum concentrations of 5.0 1062.5 105 M; the detection limit of molybdenum was 4.7 107 (3s value). The best reproducibility in the determination of molybdenum was achieved at pH 4.9. Although the determination of molybdenum in the presence of surfactants is more sensitive than the determination as mixed-ligand compounds, the selectivity is higher in the latter case. The complexes of all ions can be prepared in both the presence and the absence of hydroxylamine at equal pH and temperature conditions (on heating). The difference between the absorbances in the presence and the absence of hydroxylamine cor-

responds to the light absorption of the molybdenum complex. In another version, the effect of temperature on the complexation in the presence of hydroxylamine can be used: the absorbance should be measured on heating and in the cold; the difference between the absorbances corresponds to the light absorption of the molybdenum complex. However, such versions remain to be implemented. There are new possibilities to determine molybdenum with a higher sensitivity, which will be considered below. In the determination of molybdenum in real samples, extractionphotometric techniques were often used for improving both sensitivity and selectivity [59 69]. Flow-injection analysis was used for improving rapidity [7073]. Diffuse-reectance spectroscopy. The linear relationship between the diffuse reection coefcient (R1) or the KubelkaMunk function (F) and the concentration of an analyte, which was converted into a colored species and sorbed on a solid support, is used in this technique. Usually, complex formation and sorption occur at the same pH values; therefore, the conditions of photometric determination in solutions can be used for sorption. The concentration factors are no lower than 60, because the weight of a sorbent cannot be lower than 0.3 g (in the case of Silochromes and ion exchangers) and the volume of a solution with a colored compound varies over a range 1550 mL with good metrological characteristics. Ion exchangers (for charged complexes) or Silochromes (for neutral complexes or complexes with a charge compensated by the introduction of surfactants as counterions) can be used as sorbents. Thus, in the case of Lumogallion IREA and Magneson IREA, the complexes are sorbed by an AV-17 anion exchanger because of the negative charge of a sulfo group [74]. The concentration factors were no lower than 66 at an aqueous phase volume of 20 mL. This made it possible to lower the analytical range of molybdenum to 0.191.9 g in 20 mL and to use diffuseVol. 57 No. 9 2002

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reectance spectroscopy. Table 4 compares calibration functions for the determination of molybdenum as binary and ternary complexes in solutions and in an AV-17 sorbent phase. In the case of heterocyclic azo compounds, an AV-17 anion exchanger was used for the sorption of a complex with PAR (a negative charge at the dissociated p-hydroxyl group of resorcinol) and Silochrome C-120 was used for the sorption of a complex with 5-BrPADAP [75]. The calibration graphs were linear at molybdenum contents of 1.97.7 g in 20 mL of solution (PAR, AV-17) or 1.04.5 g in 20 mL (PAR or 5-Br-PADAP on C-120). In the determination of molybdenum as complexes with Lumogallion IREA and Magneson IREA in both the absence and the presence of hydroxylamine, the calibration graphs were linear at 0.54.5 g of molybdenum(VI) in 20 mL of solution. The sensitivity of the determination of molybdenum as complex sorbates with analytical signal measurements by diffuse-reectance spectroscopy is at least 20 times higher than that of the determination in solution. Diffuse-reectance spectroscopy was applied to determine molybdenum as a complex with pyrocatechol violet after its sorption on the AV-17 anion exchanger [76]. The following two interesting facts were found: the absorption maximum of the complex sorbate (660 nm) was bathochromically shifted as compared to the maximum of the same complex in solution (550 nm), and the maximum in the spectrum of the sorbate was shifted by 220 nm as compared to the absorption maximum of the reagent in solution (440 nm). This effect of a strong bathochromic shift was observed previously in solutions of this complex in the presence of cationic surfactants [52, 77] and, more recently, in the sorption of the same complex on silica with chemically bound propylamine groups [78]. The second anomaly consists in a shift of complexation pH on sorption to a more acidic medium and in a wider range of complexation pH 1.04.0 in place of 3.04.0 in solutions with no sorption. This shift to lower pH values in solutions was explained [79] by an increase in the acid properties of the reagent upon its interactions with cationic surfactants. The advantages of (I) sorption combined with determination by diffuse-reectance spectroscopy over (II) determination in solutions are obvious. The linearity range of a calibration graph in method I is 03 g in 20 mL, whereas it is 1.957 g in 20 mL of solution in method II; the detection limits are 0.015 and 0.32 g/mL, respectively. The narrowed linearity range in method I can be explained by a decrease in the concentration of pyrocatechol violet in a sorbent phase as compared to its concentration in solution: the total exchange capacity of AV-17 for the reagent is 6.27 106 mol/g [76].
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Table 4. Calibration functions for the determination of molybdenum by photometry [26] and diffuse-reflectance spectroscopy [74] (n = 5; P = 0.95) Reagent Lumogallion IREA Lumogallion IREA + hydroxylamine Lumogallion IREA Lumogallion IREA + hydroxylamine Magneson IREA Magneson IREA + hydroxylamine Magneson IREA cR , M 1 105 1 105 1 106 1 106 1 105 1 105 1 106 Calibration function A = (0.111 0.002)c (0.006 0.001) A = (0.142 0.006)c (0.014 0.002) F = (0.295 0.011)c (0.073 0.007) F = (0.469 0.027)c (0.032 0.003) A = (0.099 0.003)c (0.007 0.001) A = (0.193 0.005)c (0.001 0.001) F = (0.247 0.009)c (0.060 0.001) F = (0.781 0.021)c (0.045 0.004)

Magneson IREA + hy- 1 106 droxylamine

Note: A is the absorbance of the solution; F is the KubelkaMunk function for the sorbate; and c is the concentration of molybdenum(VI) (g per 20 mL of solution for A or g/mL for F).

Solid-phase spectrophotometry. Solid-phase spectrophotometry is a combination of the sorption of colored complexes on sorbents with the measurement of light absorption in a thin layer (usually, 0.1 cm) [80, 81]. Almost all analytical forms of complexes can be used in solid-phase spectrophotometry. It is difcult to choose a solid support: it should not only sorb the complex but also be transparent in an optimum range of wavelengths, desirably, in the visible region of the spectrum. In this respect, silica gels and polyurethane foams are hardly promising, although they were found to be good sorbents [82, 83]. Studies on the determination of molybdenum by solid-phase spectrophotometry are scarce; this can be explained by difculties in the lling of a very narrow cell using a wet technique and by the nonuniformity of the distribution of a complex over a support. Because of this, the reproducibility of determination results is worse than that in diffusereectance spectroscopy. Note that the above technical problems of solid-phase spectrophotometry are absent from diffuse-reectance spectroscopy with the use of the same sorbates. These techniques are comparable in terms of sensitivity. The advantage of solid-phase spectrophotometry over diffuse-reectance spectroscopy consists in the possibility of better monochromatization (1 to 2 nm depending on the type of the spectrophotometer), whereas it is equal to 10 nm and restricted by the visible region of the spectrum in diffuse-reectance spectroscopy.
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Table 5. Detection limits of molybdenum determined as a complex with 5-Br-PADAP and hydroxylamine using optical techniques [84] Technique Spectrophotometry Chromaticity characteristics of solutions for spectrophotometry Chromaticity characteristics of solutions for sorption Sorption on C-120 Chromaticity characteristics of the sorbate Analytical cmin , signal g/L A L L F L 200 130 40 30 7.5

bance A in spectrophotometry. For example, for the Lumogallion IREA complex with molybdenum in a concentration range of 0.401.90 g per 20 mL, the slopes of calibration graphs (sensitivity factors) of the chromaticity characteristics X, B, S, L, and T increased in magnitude by a factor of 1025 as compared to the slope of the KubelkaMunk plot (F) as a function of molybdenum concentration. Table 5 compares the detection limits of molybdenum in the determination by various optical techniques. Note that the maximum permissible concentration of molybdenum in natural water is 250 g/L, and even spectrophotometry is suitable for determining it in terms of sensitivity. However, the volume of a test sample can be decreased by a factor of 25 with the use of sorbates and chromaticity characteristics. The Lumogallion IREA, Magneson IREA, PAR, and 5-BrPADAP reagents were applied to the determination of molybdenum in steels, soils, and seawater by various versions of optical techniques [85, 86]. Test methods. Although the number of color reactions for molybdenum is great, the number of test methods for determining it is limited [82]. The reaction with gallic acid in the presence of hydroxylamine, which is performed on polymer plates [87], and the reaction with phenyluorone in the presence of cetylpyridinium [88], which is performed on paper impregnated with the reagents, were mentioned. Molybdenum concentrations are determined visually (0.011 mg/L) or from the length of a colored zone (0.0510 mg/L). The procedure was used for the determination of molybdenum in wastewater. Test scales were developed for the determination of molybdenum as complexes with heterocyclic azo compounds in the presence of hydroxylamine [75, 89], with pyrocatechol violet [76], and with thiocyanate ions (on polyurethane foam) [90]. Other methods of molecular spectroscopy. Thermal lens spectrometry was proposed for the determination of molybdenum by the thiocyanate reaction with the use of ascorbic acid as a reducing agent. The detection limit of molybdenum was 19 pg/mL; 1000-fold amounts of iron were masked with tartrate. This method was applied to the determination of molybdenum in drinking water and natural water [91]. Molybdenum (0.0140.149%) in alloys was determined by uorimetry using the quenching of 2-hydroxynaphthoquinone luminescence by molybdenum ions in the presence of cetylpyridinium [92]. Derivative spectrouorimetry was used in the determination of molybdenum in plant tissues, multivitamin preparations, and food products; hexadecyl red S [93] and alizarin red [94] were used as the reagents. The detection limit of molybdenum was 1.7 ng. Carminic acid [95], thiocyanate, Rhodamine S, and lauryl sulfate [96] were also used as the reagents. Molybdenum in seawater was determined by X-ray uorescence analysis with preconcentration as dithioVol. 57 No. 9 2002

Solid-phase spectrophotometry in combination with diffuse-reectance spectroscopy was used for choosing optimum conditions for molybdenum complexation with Lumogallion IREA, Magneson IREA, PAR, and 5-Br-PADAP [74, 75, 84]. Calibration functions were obtained for all of the systems. Solid-phase spectrophotometry was applied to examine complexation in the molybdenum(VI)pyrocatechol violetAV-17 anion exchanger system and to study ionic equilibria of the reagent on the above anion exchanger [76]. At the total exchange capacity of the sorbent for pyrocatechol violet equal to 6.27 106 mol/g, the exchange capacity for the molybdenum complex was 7.8 107 mol/g. Chromaticity measurements. The chromaticity measurement as a science on color measurements and quantication is based on the calculation of color characteristics from the available spectral parameters. It provides an opportunity to distinguish between substances with spectrally similar characteristics and to obtain additional data on these substances [83]. This method provides information on the color saturation (S, lightness (L), yellowness (G), whiteness (W), and tint (T), as well as on color differences with respect to these characteristics (S, L, T, E). Functional relationships between the above characteristics and analyte concentrations can be found with the use of A, B or X, Y, Z chromaticity coordinates. Both complex solutions and sorbates can be used; the sensitivity of determination is additionally improved in the latter case. Only a single publication [84] was devoted to the study of the chromaticity characteristics of molybdenum complexes. Lumogallion IREA, Magneson IREA, PAR, and 5-Br-PADAP were studied as the reagents, and binary (with Lumogallion IREA and Magneson IREA) and ternary (with all of the above reagents) complexes with the participation of hydroxylamine were examined both in solutions and as sorbates on AV-17 or C-120. It was found that the value of any chromaticity characteristic of a complex in solution or a complex sorbate is higher than the diffuse reection coefcient F in diffuse-reflectance spectroscopy or the absor-

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carbamates [9799]; the detection limit was 1 g/L [98]. ATOMIC SPECTROSCOPY Atomic absorption spectrometry (AAS). AAS is the second most important technique for the determination of molybdenum. AAS was used as an investigation technique for revealing parameters that affect the determination of molybdenum by ame AAS [100102] and electrothermal AAS (with the use of pyrolytic graphite and tungsten-coated Lvov platforms) [103, 104]. The molybdenum concentrations varied from 0.1 to 4.0 g/g; the absolute amount of molybdenum introduced into a graphite furnace was 813 g. The majority of researchers used electrothermal atomization in the determination of molybdenum in alloys [100], biological samples [101, 102, 105107], plant tissues [108], food products [109112], drinking water [113], and soils [114]. Table 6 summarizes data on the detection limits of molybdenum in various samples by AAS. It was proposed to determine low molybdenum concentrations after coprecipitation with metal chelates [115118] on various collectors: microcrystalline naphthalene [119, 120], active carbon [121], chelating sorbents [122], and anion exchangers [122124]. Extraction was also widely used [125127]. A method for the ultratrace determination of molybdenum in seawater with preconcentration in a system for ow-injection analysis was proposed [128, 129]. Several procedures for the AAS determination of trace molybdenum without sample decomposition were developed with the use of hydrazine sulfate [130], hydroxylamine hydrochloride [131], barium hydrouoride [132], and other uorides [133] as matrix modiers. Atomic emission spectrometry (AES). Molybdenum was determined by AES in surface water, seawater, mineral water, drinking water [134136], molybdenum glasses [137, 138], human body uids (0.001 0.08 g/mL) [139141], and soils (0.034.09 g/g) [142144]. Sample preparation in AES includes wet and dry mineralization followed by the preconcentration of a group of elements by sorption or liquid extraction. Most often, carbamates, 8-hydroxyquinoline, acetylacetone, N-benzoyl-N-phenylhydroxylamine, and 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone were used as extractants and chloroform, carbon tetrachloride, and benzene were used as solvents [145]. To intensify sample preparation, it was proposed to use autoclaves and microwave [146148] or ultrasonic [149] digestion. Inductively coupled plasma mass spectrometry (ICP MS). The hybrid ICP MS technique and other techniques were applied to routine analyses in water quality laboratories [150153]. Problems that appear when a method is transferred from research laboratoJOURNAL OF ANALYTICAL CHEMISTRY Vol. 57

Table 6. Detection limits of molybdenum determined by AAS in various materials Test material Sheep blood plasma Human urine Human body fluids Food products (bread, meat, eggs, potatoes, and apples) Baby foods and dried milk Milk Tap (drinking) water cmin 3 g/L 0.2 g/L 0.03 0.053.86 0.063 0.28 ng/g References [102] [106] [107] [109] [111] [112]

0.092.31 mg/L [113]

ries to industrial laboratories were discussed; an automated system for the purication of water and samples and for preconcentration to remove the effects of matrix elements was developed. This technique determines ultratrace amounts of molybdenum in blood serum at a level of n pg/g; in this case, the samples should be diluted by a factor of 510 without sensitivity losses [154157]. The ICP MS technique was used for the determination of molybdenum in silicate rocks [158] and wheat and rice our [159]. NUCLEAR PHYSICAL AND RADIOCHEMICAL METHODS Neutron activation analysis (NAA). NAA was used for checking the accuracy of the determination of molybdenum in biological materials by AAS [160] or spectrophotometry [161]. This technique is most often combined with the radiochemical separation of radioactive molybdenum isotopes from the matrix after irradiation. The extraction of molybdenum dithiocarbamate was used for the separation. NAA was used for the determination of molybdenum in scheelite [162], food products [163], seawater [164], human body uids [165167], biomaterials [168170], biological matrices [171, 172], and bovine blood serum [173]. The high sensitivity of this technique (108%) is attractive; however, it is achieved upon the irradiation with a highpower beam of thermal neutrons. At the same time, NAA is a time-consuming technique because of the necessity of cooling the sample after irradiation for the decay of short-lived isotopes (up to a month [173]). The use of NAA is restricted by cumbersome irradiation facilities, special requirements on safe practice, and a small number of extraction systems for separating the radioisotope from the matrix. In contrast to other elements, the sample is usually dissolved for the determination of molybdenum [174176]. Radiochemical methods. Radiochemical methods are used for the determination of molybdenum in medicinal plants [177] and food products [178].
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VOLTAMMETRIC DETERMINATION OF MOLYBDENUM Of the electrochemical methods for determining molybdenum in minor amounts, voltammetry is most widely used [179181]. Molybdenum(VI) is electroactive on a dropping mercury electrode only in an acidic medium [182185]. The solutions of H2SO4, HCl, HNO3, HClO4, and H3PO4 were studied as supporting electrolytes. The majority of authors believed that the reduction of molybdenum(VI) occurs in the two steps Mo(VI) Mo(V) and Mo(V) Mo(III), and both of these steps are irreversible. However, additional waves appeared in some cases; the number of these waves depended on the concentration of a depolarizer and on the nature and acidity of supporting solution. As a rule, in the presence of HCl and H2SO4, diffusion is the rate-limiting step of Mo(VI) reduction. In a number of cases, diffusion is complicated by adsorption and other phenomena, for example, the occurrence of coupled chemical reactions [186]. Ionic molybdenum(VI) species in the bulk of solution and in a near-electrode layer can be different. Because of this, it becomes more difcult to determine the molybdenum(VI) species that participates in the electrode process. However, classical polarography, which is based on the measurement of diffusion currents, was used for the determination of molybdenum in various naturally occurring (ores and rocks) and industrial (alloys and steels) materials [5, 187]. A comparative study of the above supporting electrolytes demonstrated that the height of the Mo(VI) Mo(V) reduction wave in an HClO4 solution was much greater than the heights of waves in other acid solutions because of the appearance of catalytic currents. In this case, the rate-determining step is not diffusion but a chemical reaction of the reduction product, that is, Mo(III), with the substrate (Cl O 4 ) with the regeneration of the electroactive substance, that is, Mo(VI). These homogeneous catalytic reactions also occurred in H2SO4 solutions in the presence of oxidizing agents such as NO 3 , Cl O 4 , Cl O 3 , and Br O 3 . The mechanisms of the appearance of catalytic currents were studied in most detail in the following systems: Mo(VI)KClO3mandelic acid [188], Mo(VI) H2O2 at pH 15 [189], Mo(VI)pyrocatecholBrO 3 [190], and MoPARNaBrO3 [191]. The applicability of the catalytic polarographic currents of hydroxylamine in the presence of tungsten and molybdenum complexes with pyrocatechol was demonstrated. A procedure for the simultaneous determination of n 106 n 105% tungsten and molybdenum in sedimentary rocks was developed [192]. Catalytic currents in the presence of oxidizing agents made it possible to considerably lower the detection limit of molybdenum(VI), particularly, with the

use of such versions as linear sweep voltammetry and differential pulse voltammetry. The complex compounds of molybdenum(VI) with many organic reagents are surface active; that is, they can be adsorbed or chemisorbed on the surface of a mercury electrode. This makes it possible to concentrate trace amounts of molybdenum(VI). Such a preconcentration is impossible in the classical version of anodic stripping voltammetry with electrolytic concentration, which is suitable only for elements that are reduced to metals and are readily soluble in mercury. It is well known that molybdenum(VI) does not fall into this category. The following feasible procedures were proposed for the adsorption accumulation of metal ions as complexes: (1) the complex of a metal ion with a surfaceactive ligand (L) is formed in the solution and then is adsorbed on an electrode; (2) a ligand undergoes adsorption on an electrode and then reacts with a metal ion to form a complex; (3) the metal ion reduced at an electrode reacts with a ligand in solution, and the resulting complex is adsorbed on the electrode; and (4) the metal ion reduced at an electrode forms a complex with a ligand adsorbed on the electrode. As a rule, the adsorption of a ligand, the complexation in solution and at the electrode surface, and the adsorption of the complex occur simultaneously, and it is difcult to determine which of the mechanisms takes place in a particular case. In a cathodic sweep of the potential, a cathodic peak is detected in the voltammogram. This peak can result from the following: (1) the reduction of the central atom of an adsorbed complex, (2) the reduction of a ligand of an adsorbed complex, and (3) catalytic hydrogen evolution. The adsorption reduction currents of the central atom or a ligand from an adsorbed complex can be used for further decreasing the detection limit, because adsorption preconcentration is one of the most efcient techniques for improving the analytical signal-to-noise ratio in voltammetry. The high sensitivity of determination with adsorption preconcentration mainly depends on the facts that the concentrated element occurs on the electrode surface and peaks in the voltammogram are higher that in the case of concentrating the element as an amalgam because of the absence of diffusion into an electrode phase. As a rule, monomolecular layers are formed, and the peak values are independent of the mass-transfer rate of the depolarizer to the electrode surface. Thus, more highly sensitive techniques with higher sweep rates of the polarization voltage (linear sweep voltammetry and high-speed ac voltammetry) can be used in the measurements of voltammograms. Adsorption accumulation can be successfully combined with the catalytic currents of oxidants (Table 7); this is also favorable for an increase in the sensitivity of determination.
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METHODS FOR DETERMINING MOLYBDENUM Table 7. Voltammetric determination of molybdenum in biological materials and environmental samples Reagent Electrode; Eads ; supporting electrolyte; detection technique (Epeak) cmin (tads) Test sample

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References [193] [194] [195] [196]

HClO4 After sorption on Chelex-100; KClO3 KNO3 Ascorbic acid + NH4NO3 Mandelic acid + Cl O 3 Benzilic acid + diphe Cl O 3

By the catalytic currents of Mo(VI) in the presence of oxidizing agents Hg electrode (hanging drop); DPV (0.25 V) 0.1 mg/L Glasses Hg electrode (DME); classical polarography 870 pM Seawater Hg electrode (DME); 1 M H2SO4 ; classical polarography; (E1/20.2 V) Hg electrode (DME); 0.14 M HCl and 1.2 102 M (NH4)2Fe(SO4)2 ; DPV (0.56 V) Hg electrode (DME); H2SO4 ; classical polarography; (E1/20.17 V) Hg electrode (DME); H2SO4 classical polarography; (E1/20.17 V) 1 107 M 0.06 mg/kg 0.01 mg/kg 0.002 mg/L Alloys Leaves, fruits, and soil

nylguanidine + By the catalytic currents of Mo(VI) in the presence of oxidizing agents after adsorption accumulation 8-Hydroxyquinoline + KNO3 Hg electrode (hanging drop); DPV; (0.7 V) Pb, PbBa glasses, [193, 2 104% and biological mate- 199] rials 8-Hydroxyquinoline Hg electrode (hanging drop); 0.2 V; DPV; [184] 4 109 M Seawater (0.59 V) (120 s) 8-Hydroxyquinoline, Br O 3 8-Hydroxyquinoline, Mandelic acid
N O3

H2SO4 ; quality con- [197] trol Tap water and spring [198] water

Hg electrode (static); open-circuit line Hg electrode (hanging drop); 0.0050.5 M HNO3 ; DPV

7 1010 M

Formation water Biological samples and plant materials Drinking water and rainwater Natural water and soil Soils and plants Biological samples

[185] [179, 199] [200] [201] [186, 202] [203]

Hg electrode (hanging drop); H2SO4; Cl O 3 9.4 1011 M third-order derivative voltammetry After adsorption preconcentration Tolidine blue Hg electrode (static); 0.1 V (Ag/AgCl elec1 1010 M trode); 0.048 M H2C2O4 ; LSV (0.3 V) (240 s) Cupferon DME (3 s); 0.2 M acetate buffer solution 1 1010 M (pH 2.73.0); DPV (0.33 V) 3 Hg electrode (hanging drop); 0.1 V (SCE); 4 109 M P O4 3 M NaH PO + 2 102 M H PO (120 s) 5 10 2 4 3 4 (pH 2.4); LSV (0.39 V) Eriochrome Blue Black R Hg electrode (hanging drop); pH 1.6; 5 109 M LSV (0.17 V) Lumogallion IREA DME (5 s); pH 2.0 (0.20 V)* 3.7 107 M* (0.30 V) 3.9 107 M** Magneson IREA DME (5 s); pH 2.0; LSV (0.27 V)* 7.9 108 M* Lumogallion IREA + hydrox- DME (5 s); pH 2.0; LSV (0.20 V)* 4.5 107 M* ylamine (0.40 V)** 5.2 107 M** 1.5 107 M* Magneson IREA + hydroxyDME (5 s); pH 2.0; LSV (0.27 V)* lamine (0.49 V)** 1.7 107 M** PAR + hydroxylamine DME (5 s); pH 2.0; LSV (0.38 V)* 1.7 107 M* (0.49 V)** 2.6 107 M** 5-Br-PADAP + hydroxyDME (5 s); pH 2.0; LSV lamine (0.42 V)* 2.4 107 M* (0.58 V)** 2.6 107 M**

Seawater Seawater

[204] [205]

Seawater Seawater Seawater Seawater Seawater

[205] [205] [205] [205] [205]

Note: DPV is differential pulse voltammetry, DME is a dropping mercury electrode, LSV is linear sweep voltammetry, and SCE is a saturated calomel electrode. * Determined using the peak of the free reagent. ** Determined using the peak of the reagent from the complex. JOURNAL OF ANALYTICAL CHEMISTRY Vol. 57 No. 9 2002

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IVANOV et al. 4. Speranskaya, E.F., Mertsalova, V.E., and Kulev, I.I., Usp. Khim., 1966, vol. 35, no. 12, p. 2192. 5. Agasyan, P.K., Nikolaeva, E.R., and Khasykov, V.M., Zh. Anal. Khim., 1985, vol. 40, no. 2, p. 181. 6. Umland, F., Janssen, A., Thierig, D., and Wunsch, G., Theorie und praktische Anwendung von Komplexbildnern, Frankfurt am Main: Akademische Verlagsgesellschaft, 1971. Translated under the title Kompleksnye soedineniya v analiticheskoi khimii, Moscow: Mir, 1975. 7. Holzbecher, Z., Divis, L., Kral, M., Sucha, L., and Vlacil, F., Organica Cinidla v Anorganicke Analyze (Organic Reagents in Inorganic Analysis). Praga: SNTL-Nakladatelstvi Technicke Literatury, 1975. Translated under the title Organicheskie reagenty v neorganicheskom analize, Moscow: Mir, 1979, p. 530. 8. Salinas, F., Mahedero, M.C., Garcia-Martin, J.P., and Fernandes, M.F., Anal. Lett., 1986, vol. 19, nos. 1314, p. 1359. 9. Nichai, K.G., Aslanov, Kh.A., Muftakhov, R.A., and Leiman, O.A., Issledovaniya v oblasti kompleksnykh soedinenii (Studies of Chelates), Tashkent: Fan, 1987, p. 5. 10. Salinas, F., Jimenez, A.M., and Duran, M.I., Anal. Chim, 1987, vol. 77, nos. 78, p. 705. 11. Yunawawardhana, H.D. and Fernando, S.A., Can. J. Chem., 1987, vol. 65, no. 5, p. 1124. 12. Martinez-Vidal, J.L., Fenandez-Alba, A.R., and Salinas, F., Analyst (London), 1990, vol. 115, no. 3, p. 329. 13. Inoue, S., Rakahashi, T., and Matsubara, M., Nippon Kaisui Gakkaishi, 1990, vol. 44, no. 4, p. 257. 14. Jiaomai, P., Wen, T., Hengtai, Y., and Weimin, M., Lihua Jianyan, Huaxue Fence, 1991, vol. 27, no. 2, p. 70. 15. Zagruzina, A.N., Ivanov, V.M., and Busev, A.I., Zh. Anal. Khim., 1978, vol. 33, no. 12, p. 2395. 16. Kalventis, E., Mikrochim. Acta, 1986, vol. 1, nos. 12, p. 27. 17. Mallikarjuna, R.K., Sreenivasulu, R.T., and Brahmaji, R.S., J. Indian Inst. Sci., 1986, vol. 66, no. 1, p. 39. 18. Kuznetsov, V.V. and Biryukova, O.V., Zh. Anal. Khim., 1993, vol. 47, no. 9, p. 1619. 19. Dass, R. and Mehta, J.R., Indian J. Chem., 1994, vol. 33, no. 5, p. 438. 20. Dass, R. and Mehta, J.R., Bull. Chem. Soc. Sap., 1993, vol. 66, no. 8, p. 2251. 21. Dass, R. and Mehta, J.R., Bull. Chem. Soc. Sap., 1994, vol. 67, no. 4, p. 999. 22. Rubio-Barroso, S. and Polo-Diez, L.M., An. Quim., 1987, vol. 83, no. 1, p. 67. 23. Tr. IREA, Moscow: Coskhimizdat, 1961, no. 3, pp. 19, 47. 24. Lukin, A.M. and Bozhevolnov, E.A., Zh. Anal. Khim., 1960, vol. 15, no. 1, p. 43. 25. Busev, A.I. and Chzhan Fan, Zh. Neorg. Khim., 1961, vol. 6, no. 6, p. 1308. 26. Ivanov, V.M., Rybakov, A.V., Figurovskaya, V.N., et al., Vestn. Mosk. Univ., Ser. 2: Khim., 1997, vol. 38, no. 5, p. 345.
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Because a substance is accumulated at the electrode surface, particular attention is focused on its reproducibility and purity. The renewable surface of a certain size can be easily produced in mercury electrodes. Therefore, hanging mercury drop electrodes or other stationary dropping electrodes are most widely used. The deposition potential, the duration of deposition, the rate of stirring, the nature and composition of the solution (pH and ionic strength), the temperature, and the concentration of an organic reagent affect the value of an analytical signal. Molybdenum belongs to the elements that are unsuitable for electrolytic preconcentration. Because of this, its traces are preconcentrated at an electrode only as complex compounds with organic (rarely, with inorganic) reagents. Differential pulse stripping voltammetry and linear sweep voltammetry on a dropping mercury electrode or a stationary (hanging drop) electrode are most frequently used for measuring voltammograms. Usually, this technique is used for the determination of molybdenum in biological materials and environmental samples (Table 7). CONCLUSIONS This review demonstrates the predominant development of optical techniques for the determination of molybdenum. This results from not only the advantages of optical techniques over other techniques but also from the extreme complexationability of molybdenum. The preconcentration of molybdenum is used in increasing frequency, and extraction methods give way to more perfect sorption methods with preconcentration as colored compounds. Concentrates can be immediately used for the determination of molybdenum by new optical techniques: diffuse-reectance spectroscopy and the chromaticity measurements of sorbates. The preconcentration of molybdenum complexes on electrodes combined with the subsequent determination by stripping voltammetry (measuring the reagent current in the complex) considerably increases the sensitivity of the determination of molybdenum. In the last decade, environmental samples, food products, and biological materials were added to the materials that are usually analyzed for molybdenum (steels, alloys, and minerals); therefore, new procedures should be developed. REFERENCES
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METHODS FOR DETERMINING MOLYBDENUM 27. Pilipenko, A.T. and Tananaiko, M.M., Raznoligandnye i raznometallnye kompleksy i ikh primenenie v analiticheskoi khimii (Heteroligand and Heterometal Complexes and Their Application in Analytical Chemistry), Moscow: Khimiya, 1983. 28. Andreeva, I.Yu. and Lebedeva, L.I., Problemy Sovremennoi Analiticheskoi Khimii (Leningrad), 1986, no. 5, p. 57. 29. Fukong, W., Yankuang Ceshi, 1994, vol. 13, no. 4, p. 277. Cited by Chem. Abstr., 1995, 229557x. 30. Zeng, S., Zhang, H., and Xie, Wuhan Daxue Xuebao, Ziran Kexueban, 1990, no. 1, p. 92. 31. Vishnikin, A.B., Sundukova, L.V., Vishnikina, E.V., and Chmilenko, F.A., Abstracts of Papers, VII Vseross. konf. Organicheskie reagenty v analiticheskoi khimii (VII All-Russian Conf. Organic Reagents in Analytical Chemistry), Saratov: SGU, 1999, p. 131. 32. Feng, Y., Lihua Jianyan, Huaxue Fence, 1994, vol. 30, no. 3, p. 168, Cited by Chem. Abstr., 1995, 80869. 33. Fang, G., Zhang, H., Yiang, Y., and Dai, R., Fenxi Huaxue, 1987, vol. 15, no. 11, p. 1012. 34. Hsu, Z. and Liao, X., Talanta, 1988, vol. 35, no. 12, p. 1007. 35. Tongsen, C., Zhanguang, C.H., and Zhanrong, Y., Yejin Fenxi, 1994, vol. 14, no. 4, p. 31. Cited by Chem. Abstr., 1995, 150403k. 36. Zhou, H. and Zhang, M., Lihua Jianyan, Huaxue Fence, 1992, vol. 28, no. 5, p. 267. 37. Amelin, V.G., Ivanov, V.M., and Svistunova, G.P., Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 1990, vol. 33, no. 1, p. 41. 38. Zaki, M.T.M., El-Zawawy, F.M., Abdel-Kader, A.K., and Abdalla, M.M., Anal. Sci., 1990, vol. 6, no. 1, p. 61. 39. Zaki, M., Tarer, M., Abdel-Kader, A.K., and Abdalla, M.M., Talanta, 1990, vol. 37, no. 11, p. 1091. 40. Amelin, V.G., Steklo Keram., 1986, no. 9, p. 28. 41. Xu, M. and He, Y., Fenxi Huaxue, 1988, vol. 16, no. 3, p. 207. 42. Andreeva, I.Yu., Problemy Sovremennoi Analiticheskoi Khimii (Leningrad), 1986, no. 5, p. 73. 43. Ganago, L.I. and Bukhteeva, L.N., Zh. Anal. Khim., 1979, vol. 34, no. 11, p. 2186. 44. Ganago, L.I. and Bukhteeva, L.N., Zh. Anal. Khim., 1980, vol. 35, no. 6, p. 1138. 45. Berhanu, B. and Chanddravanshi, B.S., Anal. Lett., 1995, vol. 28, no. 9, p. 1681. 46. Chandrakar, L.P., Singh, R., and Mishra, R., Analyst (London), 1987, vol. 112, no. 11, p. 1511. 47. Bermejo, B.P., Vazquez, G.J.F., and Bermejo, M.F., Microchem. J., 1987, vol. 35, no. 1, p. 1. 48. Li, Z. and Xu, Q., Fenxi Huaxue, 1987, vol. 15, no. 10, p. 870. 49. Shen, H. and Liu, Y., Gaodeng Xuexiao Huaxue Xuebao, 1988, vol. 9, no. 9, p. 897. 50. Ganago, L.I. and Ivanova, I.F., Zh. Anal. Khim., 1987, vol. 42, no. 9, p. 1641. 51. Savvin, S.B., Chernova, R.K., and Shtykov, S.N., Poverkhnostno-aktivnye veshchestva (Surfactants), Moscow: Nauka, 1991.
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