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Section 15. Chemistry
Список литературы:
1. Геворгян А. М., Яхшиева З. З. Оптимизация условий амперометрического определения некоторых благородных металлов раствором тиоацетамида.//Журн. Хим. пром. Санк-Петербург. 2010. Т. 87. № 2. С. 85-88.
2. Москвин Л. Н., Царицына Л. Г. Методы разделения и концентрирования в аналитической химии. М. Химия. 1991. 234.с.
3. Байзер М. М. Электрохимия органических соединений./М.; Мир. 1976. 728 с.
4. Геворгян А.М., Талипов Ш.Т., Хадеев В.А., Мухамеджанова Д.В. Вольтамперометрическое поведение ди-этилдитиокарбамината натрия на платиновом аноде в среде диметилформамида//Журн. аналит. химии. 1980. Т.35. №10. С.2026 - 2028.
Khentov Victor Yakovlevich, South-Russian State Potechnical University, Professor, Doctor of Chemical Sciences E-mail: [email protected] Hussain Hanaa Hassan, South-Russian State Potechnical University,
Graduate student Semchenko Vladimir Vladimirovich, South-Russian State Potechnical University, Associate Professor, Candidate of Science.
Interrelations of Valence fluctuation frequencies and Force constants with the Debye temperature of a Chemical compound metal
Abstract: The relationship ofvalence fluctuation frequencies and force constants ofthe IR spectra of inorganic compounds with the metal element Debye temperature has been established. The Debye temperature plays the role of a genetic factor. Keywords: IR spectra, inorganic compounds, valence fluctuation requencies, force constant, Debye temperature.
Infrared spectroscopy (IR) as a physical method for investigating the structure of molecules has been of widely spread in chemistry. Valence fluctuation frequency is determined by the equation:
=— K
2лсу ц ’
where c - velocity of light; K - connection (relation) force constant which can be regarded as the coefficient of elasticity for certain structural molecular fragments; ^ - reduced mass of a particle. Value K increases with the increase of connection multiplicity. For diatomic molecules HF, HCl, HBr and HI it was found that their dissociation energy in the force constant function is described by the first degree polynomial [1, 23-24].
According to the theory of fluctuation spectra of polyatomic molecules the atom displacement is assumed to be inversely proportional to the atom masses. In this regard, it is interesting to consider the impact of the metal nature on the valence fluctuation frequencies and force constants in the series of similar chemical compounds.
The characteristic Debye temperature was chosen as the main parameter defining the nature metal 0 [2, 229], which appears to be a data carrier being a complex wave function. Physical properties of solids are connected with this parameter [3, 143-145].
Let’s show that the frequencies of valence fluctuations of the Group I s-element v-chlorides of the periodic system [4, 78] are closely related to the metal Debye temperature. For the entire set of halides (LiCl, NaCl, KCl, RbCl, CsCl) the following equation (correlation factor 0.986) was derived:
v = 81.3517 + 2.30460.
For NaCl, KCl, RbCl and CsCl this association (correlation factor 0.999) is shown in Fig. 1.
Let’s consider relationship of characteristic valence symmetric fluctuations of Group I s-elements azides (N3) with the metal Debye temperature. For compounds LiN3, NaN3, KN3, RbN3 and CsN3 Spectrums of combinational dispersion [5, 26] were taken. For the entire set of azides the correlation dependence (correlation factor 0.94) was obtained: (N3) = 1331.4469+0.1190.
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Interrelations of Valence fluctuation frequencies and Force constants with the Debye temperature of a Chemical compound metal
Fig. 1. The dependence of valence fluctuation frequencies of the Group 1 s-elements chlorides on the metal Debye temperature
For the same set of azides the correlation depen- polynomial with a higher correlation factor of 0.98 dence without lithium is described by the first degree (Fig. 2).
Fig. 2. Dependence of the characteristic valence symmetrical fluctuations vc (N3) of the metal Debye temperature: 1 - CsN3, 2 - RbN3, 3 - KN3, 4 - NaN3
Table. 1 shows the relation of fluctuation frequencies 149] to the metal Debye temperature. It is notable that of tetrahalides GeCl4, TiCl4, ZrCl4, SnCl4 and PbCl4 [1, these dependencies are given by d- andp-elements.
Table 1. - The correlation equation, the correlation factor R
Frequency correlation dependency of osculation колебаний v1, v2, v3, v4 R
v, = 318.5741 + 0.19790 0.90
v, = 307.3816 + 0.25820 без TiCl4 0.96
v2 = 79.8722 + 0.10770 0.85
v3 = 309,3384+0,40740 0.98
v = 78.4716 + 0.18030 4 0.76
Ideal dependence of v3 tetrahalides frequency with a high correlation coefficient of 0.98 (Fig. 3). [1,149] on the metal Debye temperature was obtained
Fig. 3. The frequency of the metal Debye temperature v3 1 - PbCl4, 2 - SnCl4, 3 - ZrCl4, 4 - GeCl4, 5 - TiCl4
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Section 15. Chemistry
The frequencies of valence fluctuations of the chloride emission spectra of d-elements ZnCl2, CoCl2, NiCl2, FeCl2 [4, 79] in the function of the metal Debye temperature are satisfactorily described by the first degree polynomial with a high correlation factor of 0.976 (Fig. 4).
For force constants of the NO F (NO) group in the ion nitrosyl complexes [IrCl5NO]-, [Fe (CN)5NO] 2-, [IrBrsNO]-, [RuCl5NO]2-, [Os (NH3)4NO]3+ and [Os (NH3)4 (OH)NO] the connection with the Debye temperature of the metal-complexing agent was defined (correlation factor 0.89) [6, 171]:
F (NO) = 2909.537 - 3.20680.
Frequencies of combinational dispersion spectra of cyano-complexes (K3 [Cr (CN)6], K3 [Co (CN)6], K3 [Rh (CN)6], K3 [Ir (CN)6]) [1, 235] in the Debye temperature function is satisfactorily described by the first degree polynomial (correlation factor 0.95): v = -339.9638 + 1.74980.
There are a lot of similar examples available. Importantly, that valence fluctuation frequencies and force constants are associated with Debye temperature of the metal forming an inorganic compound. It is possible to speak of genetic impact of a metal element on the physical and chemical properties of inorganic compounds.
Fig. 4. Dependence of the valence fluctuation frequency of transition metal halides v on the metal Debye temperature: 1 - ZnCl2, 2 - CoCl2, 3 - NiCl2, 4 - FeCl2
Table. 2 shows the relations of frequencies of ion the metal Debye temperature. fluctuations of octahedral molecules MeCl6 [1, 166] with
Table 2. - Octahedral molecule ions MeCl6, correlation equation the correlation coefficient R
MeCL Correlation equations R
[TiClJ 2, [SeClJ2, [SnClJ 2, [PtClJ 2, [PdClJ 2- v, = 265.8831 + 0.36890 0.72
[TiClJ 2, [SnClJ 2, [PtClJ 2, [PdClJ2- v, = 160.8693 + 0.6980 0.94
[TiClJ 2, [SeClJ2, [PtClJ 2, [PdClJ 2- v2 = 257.0428 + 0.19220 0.88
[TiClJ 2, [SnClJ 2, [PtClJ 2, [PdClJ2- v5 = 54.5151 + 0.45670 0.96
References:
1. Nakamoto K. Infrared Spectra of Inorganic and Coordination Compounds./Per. from English. Ed. YA Pentin. - M.: Mir, 1966.
2. Kittel Ch. Introduction to Solid State Physics. Trans. the fourth American edition. Edited by AA Gusev. - M.: Nauka, 1978.
3. Khentov. VYa./Связь физических свойств твердого тела с температурой Дебая./ZApphed Sciences and technologies in the United States and Europe: common challenges and scientific findings: 5th International Scientific Conference. February 12, 2014. - New York, 2014.
4. Vibrational spectra in inorganic chemistry./Ed. Editor YY Kharitonov. - M.: Nauka, 1971.
5. Chemicals pseudo halides./Ed. AM Blue, H. Kohler, VV Skopenko. Kiev: Publishing Association «Vishcha School», 1981.
6. Kukushkin YN Reactivity of coordination compounds. - L.: Chemistry, 1987.
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