Thermochemical Parameters of 3-Chloroaniline Complexes of Certain Bivalent Transition Metal Bromides

Pedro Oliver Dunstan, Abdul Majeed Khan

Instituto de Química, Universidade Estadual de Campinas, Campinas, Brazil.

DOI: 10.4236/ojpc.2013.34020                

Abstract

Complexes of general formula [MBr₂(3-clan)_n] (where M is Fe, Ni, Cu or Zn; 3-clan = m-chloroaniline; n is 1.5 or 2) were prepared and their characteristic properties, such as capillary MP; C, H, N, Br and metal contents; TG/DTG and DSC curves; and IR and electronic spectra were determined. By calorimetric measurements in solution, the values of some thermodynamic parameters of the complexes were determined. From these values, the standard enthalpies of the metal-nitrogen coordinated bonds were calculated, and the standard enthalpies of the formation of the gaseous phase complexes were estimated.

Keywords

Enthalpies of Formation; Thermodynamic; Coordinated Bond Enthalpies; Calorimetric Measurements

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	A. V. Ablov and L. V. Nazarova, “Effect of Functional Groups in the Ligand Molecule on the Stability of Complex Salts of Nickl,” Zhurnal Neorganicheskoi Khimii, Vol. 5, 1960, pp. 1735-1737.
[2]	A. V. Ablov and Z. P. Burnashava, “Addition Compounds of Aniline and Its Derivatives with Zinc Halide,” Zhurnal Neorganicheskoi Khimii, Vol. 5, 1960, pp. 604-609.
[3]	A. V. Ablov and V. Ya. Ivanova, “Addition Compounds of Aromatic Amines with Cadmium Halides” Zhurnal Neorganicheskoi Khimii, Vol. 6, 1961, pp. 883-889.
[4]	S. R. Jain and S. Soundararajan, “Dipole Moments and Structure of Molecular Compounds of Zinc and Cadmium Halides,” Current Science (India), Vol. 31, 1962, pp. 458-459.
[5]	P. Spacu, V. Voicu and I. Pascaru, “Paramagnetic Resonance of Some Copper(II) Complexes,” Journal of Chemical Physics, Vol. 60, 1963, pp. 368-873.
[6]	S. R. Jain and S. Soundararajan, “Electric Polarization and Structure of Molecular Complexes of the Metallic Halides of Group II of the Periodic Table,” Journal of Inorganic and Nuclear Chemistry, Vol. 26, 1964, pp. 1255-1261.
[7]	D. P. N. Satchell and R. S. Satchell, “Spectroscopic Study of the Equilibrium in Acetone Solution between Zinc Halides and Aromatic Amines,” Transactions of the Faraday Society, Vol. 61, 1965, pp. 1118-1126. http://dx.doi.org/10.1039/tf9656101118
[8]	I. S. Ahuja, D. H. Brown, R. H. Nuttall and D. W. A. Sharp, “The Preparation and Spectroscopic Properties of Some Complexes Formed between Transition Metal Halides and Substituted Anilines,” Journal of Inorganic and Nuclear Chemistry, Vol. 27, No. 7, 1965, pp. 1625-1634. http://dx.doi.org/ 10.1016/0022-1902(65)80026-4
[9]	K. R. Monolov, “Thiocynate Complexes,” Zhurnal Neorganicheskoi Khimii, Vol. 11, 1966, pp. 684-686.
[10]	I. S. Ahuja, “Preparation and Spectroscopic Studies of Aniline, Substituted Anilines and Morpholine Complexes with Cobalt(II) Thiocynate,” Indian Journal of Chemistry, Vol. 7, 1969, pp. 509-511.
[11]	P. O. Dunstan, “Thermochemistry of Adducts of Some Bivalent Transition Metal Bromides with 4-Chloroaniline,” Thermochimica Acta, Vol. 450, No. 1-2, 2006, pp. 5-11. http://dx.doi.org/10.1016/j. tca.2006.05.022
[12]	U. G. da Silva, O. A. Oliveira and R. F. de Farias, “Synthesis, Characterization and Calorimetric Study of Zinc Group Halide Adducts with Aniline,” Thermochimica Acta, Vol. 450, No. 1-2, 2006, pp. 2-4. http://dx.doi.org/10.1016/j.tca.2006.04.010
[13]	T. S. Sikha and P. Indrasenan, “Thermal Decomposition Kinetics of Some Aniline Complexes of Zinc Group Metals,” Indian Journal of Chemistry Section A, Vol. 43A, 2004, pp. 1393-1402.
[14]	E. Akalin and S. Akyuz, “Force Field and IR Intensity Calculation of Aniline and Transition Metas(II) Aniline Complexes,” Journal of Molecular Structure, Vol. 482-483, pp. 175-181. http://dx.doi.org/ 10.1016/S0022-2860(98)00780-7
[15]	K. R. Zurowski and M. Labanowska, “Coordination of Ammonia and Aniline by Copper(II) Chloride,” Polish Journal of Chemistry, Vol. 69, 1995, pp. 998-1002.
[16]	G. Beech, G. Marr and B. W. Rockett, “Thermochemical and Spectroscopic Properties of Transition-Metal Complexes,” Journal of the Chemical Society A, Vol. 4, 1969, pp. 629-631.
[17]	Sh. Dinkov and M. Arnaudov, “IR-Spectral Study of 2-Aminopyridine and Aniline Complexes with Palladium (II),” Spectroscopy Letters, Vol. 32, No. 1, 1999, pp. 165-180. http://dx.doi.org/10.1080/ 00387019909349975
[18]	I. S. Malesnnikova and T. G. Balicheva, “IR-Spectroscopy Studies of the State of Water in Kaolin Ando f the Processes of Kaolin Dehydration,” Journal of Molecular Structure, Vol. 114, 1984, pp. 313-316. http://dx.doi.org/10.1016/0022-2860(84)87152-5
[19]	S. Akyuz and J. E. D. Davies, “Solid-State Vibrational Spectroscopy. Part II. An Infrared and Raman Vibrational Spectroscopic Study of Metal(II) Halide Aniline Complexes,” Journal of Molecular Structure, Vol. 95, 1982, pp. 157-168.
[20]	P. C. Kong and F. D. Rochon, “Cisand Trans-Platinium Complexes of Anilines,” Inorganica Chimica Acta, Vol 61, 1982, pp. 269-271. http://dx.doi.org/10.1016/S0020-1693(00)89152-5
[21]	M. Goldstein and R. J. Huges, “Vibrational Spectra of Some Bis(aniline)Complexes of Metal Dihalides Having Planar or Octahedral Halogen Bridged Chain Structures,” Inorganica Chimica Acta, Vol. 40, 1980, pp. 229-237. http://dx.doi.org/10.1016/S0020-1693(00)92010-3
[22]	J. Lee-Thorp, J.. E. Rueede and D. A. Thornton, “The Infrared Spectra (3500 - 150 cm-1) of Aniline Complexes of Cobalt(II), Nickel(II), Copper(II) and Zinc(II) Halides,” Journal of Molecular Structure, Vol. 50, No. 1, 1978, pp. 65-71. http://dx.doi.org/10.1016/0022-2860(78)87097-5
[23]	I. S. Ahuja, “Aniline Complexes of Cadmium(II) Acetate,” Australian Journal of Chemistry, Vol. 21, No. 11, 1968, pp. 2805-2807. http://dx.doi.org/10.1071/CH9682805
[24]	J. M. Haigh, M. A. Van Dam and D. A. Thorthon, “Complexes and Ligands II. Complexes of Mercury(II) and Zinc(II) with Primary Aromatic Amines: Infrared Spectra and Bonding,” Journal of the South African Institute, Vol. 20, 1967, pp. 113-122.
[25]	I. S. Ahuja, D. H. Brown, R. H. Nuttall and D. W. A. Sharp, “The Preparation and Properties of Some Aniline Complexes of Metal(II) Sulfates and Nitrates,” Journal of the Chemical Society A, Vol. 7, 1966, pp. 938-941.
[26]	M. A. J. Jungbauer and C. Curran, “Infrared Spectra of Complexes of Aniline with Metal(II) Halides,” Spectrochimica Acta, Vol. 21, 1965, pp. 141-148.
[27]	J. A. Riddick and W. B. Bunger, “Organic Solvents,” 3rd Edition, Wiley, New York, 1970.
[28]	J. B. Niederl and J. A. Sozzi, “Microanáslisis Elemental Orgánico,” Methopress, Buenos Aires, 1958.
[29]	I. M. Kolthoff and E. B. Sandall, “Tratado de Química Analítica Cuantitativa,” 3rd Edición, Nigar, Buenos Aires, 1956.
[30]	H. A. Flaschka, “EDTA Titrations: And Introduction to Theory and Practice,” 2nd Edition, Pergamon Press, London, 1964.
[31]	P. O. Dunstan, “Thermochemistry of Adducts of Bis(2,4-pentanedionato)Zinc with Heterocyclic Amines,” Journal of Chemical & Engineering Data, Vol. 44, No. 2, 1999, pp. 243-247. http://dx.doi.org/10.1021/je980113m
[32]	E. F. Herington, “Recommended Reference Materials for the Realization of Physicochemical Properties (Recommendation Approved 1974),” Pure and Applied Chemistry, Vol. 40, 1974, pp. 391-450.
[33]	D. A. Thornton, “Metal Complexes of Aniline: Infrared and Raman Spectra,” Journal of Coordination Chemistry, Vol. 24, No. 3, 1991, pp. 261-289. http://dx.doi.org/10.1080/00958979109407887
[34]	S. Akyuz and J. E. D. Davies, “Solid-State Vibrational Spectroscopy. Part 11. An Infrared and Raman Vibrational Spectroscopic Study of Metal(II) Halide Aniline Complexes,” Journal of Molecular Structure, Vol. 95, 1982, pp. 157-168.
[35]	J. Reedijk, P. W. N. M. Leeuwem and W. L. Groenveld, “A Semiempirical Energy-Level Diagram for Octahedral Nickel Complexes,” Recueil des Travaux Chimiques des Pays-Bas, Vol. 87, 1968, pp. 129-141.
[36]	A. B. P. Lever, “Electronic Spectra of Some Transition Metal Complexes,” Journal of Chemical Education, Vol. 45, 1968, pp. 711-712.
[37]	M. W. G. Bolster, “The Coordination Chemistry of Amino-Phosphinoxide and Related Compounds,” Thesis, Leiden, 1972, pp. 88-89, 95, 98, 100.
[38]	P. O. Dunstan, “Thermochemistry of Morpholine Adducts of Some Bivalent Transition Metal Bromides,” Journal of Chemical & Engineering Data, Vol. 54, 2009, pp. 842-846.
[39]	T. N. Sevast’yanova and A. V. Suvorov, “The Structure and Thermal Stability of Group III Halide Complexes with Pyridine,” Russian Journal of Coordination Chemistry, Vol. 25, 1999, pp. 679-688.
[40]	P. O. Dunstan, “Thermochemistry of Adducts of Some Bivalent Transition Metal Bromides with Quinoline,” Thermochimica Acta, Vol. 468, 2008, pp. 21-6.
[41]	P. O. Dunstan, “Thermochemistry of Aniline Derivatives Complexes of Arsenic Trihalides,” Thermochimica Acta, Vol. 268, 1995, pp. 83-93.
[42]	D. D. Wagman, W. H. Evans, V. B. Parker, R. H. Schumm, I. Hallow, S. M. Churney and R. L. Nuttall, “The NBS Table of Chemical Thermodynamic Properties. Selected Values for Inorganic and C1 and C2 Organic Substances in SI Units,” Journal of Physical and Chemical Reference Data, Vol. 2, 1982, pp. 50-191.
[43]	P. O. Dunstan, “Thermochemistry of Adducts of Some Bivalent Transition Metal Bromides with Aniline,” Thermochimica Acta, Vol. 441, 2006, pp. 1-7.