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 диэтилдитиокарбамината 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 of valence fluctuation frequencies and force constants of the 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:
ν=
1
2π c
K
,
µ
where c – velocity of light; K – connection (relation)
force constant which can be regarded as the coefficient
of elasticity for certain structural molecular fragments;
μ ‒ 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.
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The characteristic Debye temperature was chosen as
the main parameter defining the nature metal Θ [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:
ν = 81.3517 + 2.3046Θ.
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 νс
(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: νс (N3) = 1331.4469+0.119Θ.
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 dependence without lithium is described by the first degree
polynomial with a higher correlation factor of 0.98
(Fig. 2).
Fig. 2. Dependence of the characteristic valence symmetrical fluctuations νс (N3) of
the metal Debye temperature: 1 ‒ CsN3, 2 ‒ RbN3, 3 ‒ KN3, 4 ‒ NaN3
Table. 1 shows the relation of fluctuation frequencies
of tetrahalides GeCl4, TiCl4, ZrCl4, SnCl4 and PbCl4 [1,
149] to the metal Debye temperature. It is notable that
these dependencies are given by d‑ and p‑elements.
Table 1. – The correlation equation, the correlation factor R
Frequency correlation dependency of osculation колебаний ν1, ν2, ν3, ν4
ν1 = 318.5741 + 0.1979Θ
ν1 = 307.3816 + 0.2582Θ без TiCl4
ν2 = 79.8722 + 0.1077Θ
ν3 = 309,3384+0,4074Θ
ν4 = 78.4716 + 0.1803Θ
Ideal dependence of ν3 tetrahalides frequency
[1,149] on the metal Debye temperature was obtained
R
0.90
0.96
0.85
0.98
0.76
with a high correlation coefficient of 0.98 (Fig. 3).
Fig. 3. The frequency of the metal Debye temperature ν3
1 ‒ PbCl4, 2 ‒ SnCl4, 3 ‒ ZrCl4, 4 ‒ GeCl4, 5 ‒ TiCl4
155
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).
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):
ν = –339.9638 + 1.7498Θ.
Fig. 4. Dependence of the valence fluctuation frequency of transition metal halides ν
on the metal Debye temperature: 1 ‒ ZnCl2, 2 ‒ CoCl2, 3 ‒ NiCl2, 4 ‒ FeCl2
Table. 2 shows the relations of frequencies of ion
fluctuations of octahedral molecules MeCl6 [1, 166] with
the metal Debye temperature.
Table 2. – Octahedral molecule ions MeCl6, correlation equation the correlation coefficient R
MeCl6
[TiCl6] 2‒, [SeCl6] 2‒, [SnCl6] 2‒, [PtCl6] 2‒, [PdCl6] 2‒
[TiCl6] 2‒, [SnCl6] 2‒, [PtCl6] 2‒, [PdCl6] 2‒
[TiCl6] 2‒, [SeCl6] 2‒, [PtCl6] 2‒, [PdCl6] 2‒
[TiCl6] 2‒, [SnCl6] 2‒, [PtCl6] 2‒, [PdCl6] 2‒
Correlation equations
ν1 = 265.8831 + 0.3689Θ
ν1 = 160.8693 + 0.698Θ
ν2 = 257.0428 + 0.1922Θ
ν5 = 54.5151 + 0.4567Θ
For force constants of the NO F (NO) group in
the ion nitrosyl complexes [IrCl5NO]‒, [Fe (CN)5NO] 2‒,
[IrBr5NO]‒, [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 ‒ 3.2068Θ.
R
0.72
0.94
0.88
0.96
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.
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. V.Ya./Связь физических свойств твердого тела с температурой Дебая.//Applied 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.
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