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45Section 6. Physical chemistry
Khentov Victor Yakovlevich, South-Russian State Potechnical University, Professor, Doctor of Chemical Sciences E-mail: vkhentov@mail.ru
Semchenko Vladimir Vladimirovich, South-Russian State Potechnical University, Associate Professor, Candidate of Science
Hussain Hanaa Hassan, South-Russian State Potechnical University,
Graduate student
Connection of valency vibrations of inorganic and complex compounds with metal Debye temperature
Abstract: For a number of inorganic and complex compounds shown to exist due to the stretching vibrations of the Debye temperature of the metal element. Noting the high value of the correlation coefficient.
Keywords: The frequency of stretching vibrations, inorganic compounds, complex compounds, correlation, Debye temperature, the correlation coefficient.
Vibrational spectroscopy is widely used in the investigation of complex compounds both in the solid phase and in solutions. The basic information can be obtained by studying characteristic frequencies of valence vibrations of certain groups such as carboxyl and phosphonic ones, C-H, N-H [1, 409].
Fig. 1. The dependence of harmonic frequencies Qe of Group I s-elements chlorides on the metal Debye temperature (correlation coefficient of 1) : 1 — CsCl, 2 — RbCl, 3 — KCl, 4 — NaCl, 5 — LiCl
With the formation of a metal-ligand relation a displacement of vibration frequencies of individual functional groups is observed. The interpretation of IR spectra of complex compounds is empiric in its
basis. However, there is an example of successful correlation of bonding energy values for N (1s) electrons with charges on the nitrogen atom for complexes of ethylene diamine-N, N, N’, N’-tetra acetic acid [1, 414]. Correlation dependences with the first degree polynomial in particular, are distinguished by visualization and are of great interest. In this regard, it is attractive for the valence vibrations to establish correlation dependences based on fundamental parameters of solids. To those we should refer the Debye temperature of the metal-complexing agent. For a number of simple and complex materials close links between the physical properties of the solid body and the metal Debye temperature have been established [2, 145-147].
Fig. 1 shows the dependence of harmonic frequencies of diatomic molecules - group I s-elements chlorides in [3, 115] on the metal Debye temperature [4, 229].
Table 1 shows the dependence of harmonic frequencies w of two- and three-atom molecules [3, 115] on the Debye temperature of the metal. All the correlation equations are given for the same type of metal, with an exception of d-elements (AgCl is a diatomic molecule).
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Connection of valency vibrations of inorganic and complex compounds with metal Debye temperature
Table 1. - Correlation dependences of harmonic frequencies Qe on the Debye temperature of the metal, (the correlation coefficient R)
The metal-non-metal relations Correlation equations R
Li-F, Na-F, K-F, Rb-F, Cs-F w = 258.6144 + 1.86420 е 0.998
Li-Cl, Na-Cl, K-Cl, Rb-Cl, Cs-Cl w = 150.1139 + 1.41850 е 1.000
Li-Br, Na-Br, K-Br, Cs-Br w = 126.9792 + 1.16840 е 0.993
Li-I, Na-I, K-I, Cs-I w = 95.5733 + 1.15360 е 0.996
Be-F, Mg-F, Ca-F, Sr-F, Ba-F w = 451.1329 + 0.5710 е 0.995
Be-Cl, Mg-Cl, Ca-Cl, Sr-Cl, Ba-Cl w = 272.613 + 0.40310 е 0.993
Be-O, Mg-O, Ca-O, Sr-O, Ba-O w = 504.6998 + 0.74610 е 0.994
Li-Li, Na-Na, K-K, Rb-Rb, Cs-Cs w = 17.2692 + 0.95750 е 0.995
Al-Cl, Ga-Cl, In-Cl, Tl-Cl w = 251.3034 + 0.47720 е 0.940
Si-Cl, Ge-Cl, Sn-Cl, Pb-Cl w = 260.8842 + 0.41980 е 0.997
Si-O, Ge-O, Sn-O, Pb-O w = 626.0447 + 0.95750 е 1.000
Si-S, Ge-S, Sn-S, Pb-S w = 365.1013 + 0.58960 е 0.999
Zn-Cl, Cd-Cl, Hg-Cl, Cu-Cl, Ag-Cl w = 253.5698 + 0.43770 е 0.972
Table 2 shows correlation dependences ofvibra- metal. All of them are described by the first degree tion frequencies v1, v2 and v3 chlorides of the Group II polynomial with with high enough value of a correla-
s-elements [3, 122] on the Debye temperature of the tion factor (coefficient).
Table 2. - The vibrational frequencies of molecules MeCl2 v1 v2 and v3, the correlation coefficient R
Molecules Correlation equations R
BeCl2, MgCl2, BaCl2, CaCl2, SrCl2 V1= 261.3582 + 0.09350 0.950
v2 = 25.9597 + 0.15630 0.999
v3 = 245.1703 + 0.63380 0.984
MgCl2, BaCl2, CaCl2, SrCl2 v, = 231.1751 + 0.24040 0.998
v3 = 126.9526 + 1.19280 1.000
Molecules BeCl2, MgCl2, CaCl2 are characterized by a linear structure, whereas molecules BaCl2 and SrCl2 are characterized by a curved structure. Nevertheless, the obtained correlation equations are characterized by high values of correlation coefficients.
The vibrational frequencies of d-metal chlorides MeCl2 v2 and v3 [3, 123], the molecules of which are characterized by expression of a linear structure, are also associated with the Debye temperature of the metal (Table 3). This connection is less reliable because d-elements from different periods are considered.
Table 3. - The vibrational frequency of d-metal chlorides, the correlation coefficient R
Molecules MeCl2 Correlation equation R
CdCl2, HgCl2, MnCl2, FeCl2, CoCl2, NiCl2 v2 = 104.0621 - 0.03840 0.71
HgCl2, MnCl2, FeCl2, CoCl2, NiCl2 v2 = 109.9073 - 0.04980 0.86
ZnCl2, CdCl2, HgCl2, CrCl2, MnCl2, FeCl2, CoCl2, NiCl2 v3 = 402.2862 + 0.19450 0.81
ZnCl2, CdCl2, HgCl2, MnCl2, FeCl2, CoCl2, NiCl2 v3 = 383.7411 + 0.26210 0.89
CdCl2, HgCl2, MnCl2, FeCl2, CoCl2, NiCl2 v3 = 376.8071 + 0.2660 0.95
It is interesting that frequencies v2 decrease with Vibration frequencies of v1 ions of pyramidal
Debye temperature magnification, whereas frequen- molecules MeCl3 - [InCl3]-, [GeCl3]-, [SnCl3]-, cies v3 increase. [PbCl3]- [3, 133] are also associated with the 47
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Section 6. Physical chemistry
Debye temperature of the metal (correlation coefficient 0.87):
v1 = 236.2434 + 0.19830.
For complex compound ions [Fe (CN)6] 3-, [Cr (CN)6] 3-, [Mn (CN)6] 3-, [Co (CN)6] 3- - at low frequency field [5, 232] the dependence ofvalence vibrations of the Me-C v on the Debye temperature of the metal-complexing agent was obtained (correlation coefficient 0.77):
v = 672.2892 - 0.32950.
For cyano-complex ions [Zn (CN)4] 2-, [Cd (CN)J 2-, [Hg (CN)J 2-, [Pt (CN)4] 2-, [Ni (CN)J2-, [Cr (CN),] 2- in the low-frequency field the vibration frequencies Me-C v [5, 234] as a function of the Debye temperature of the metal-complexing agent are described by the following equation (correlation coefficient is 0.80):
v = 277.297 + 0.60230.
For spectrums of Raman effect of complex compounds K3 [Fe (CN)6 ], K3 [Co (CN)6 ], K3 [Cu (CN)6 ], K3 [Rh (CN)6 ], K3 [Ir (CN)6 ] and frequencies 2136, 2137, 2147, 2143, 2074 см-1 respectively [5, 235] the following equation was obtained (correlation coefficient 0.90): v = 1912.7816+0.49730.
For basic valence vibrations v (CN) of complex compounds CdPy4 (NCSe)2 , CoPy4 (NCSe)2 , FePy4 (NCSe)2, MnPy4 (NCSe)2, where Py - C5H5N (pyridine) [6 271], the dependence of v (CN) on the Debye temperature of the metal-complexing agent was established (correlation coefficient 0.94): v (CN) = 2011.4218 + 0.1360.
The above mentioned specific examples allow to argue that that the Debye temperature has a significant impact on the valence vibration frequencies of inorganic and complex compounds.
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3. Nakamoto K. Infrared and Raman Spectra of Inorganic and Coordination Compounds. Trans. from English. - M.: Mir, 1991. - 536 p.
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