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Conductometric Studies of the Thermodynamics for Complexation of 1,1-Diethyl-3-(4-methoxybenzoyl)thiourea and Cobalt(II) Cation in Aqueous Binary Mixtures of Polar Organic Solvents

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Abstract

The complexation reaction of Co2+ (M) and the 1,1-diethyl-3-(4-methoxybenzoyl)thiourea (L) ligand in the binary mixtures: acetonitrile–dimethylsulfoxide (MeCN–DMSO), acetonitrile–dichloromethane (MeCN–DCM), water–dimethylsulfoxide (H2O–DMSO) and acetonitrile–water (MeCN–H2O), was investigated using a conductometric method at temperatures of (288.15, 298.15, 308.15 and 318.15) K. In all cases, the conductance data showed that the stoichiometry of the neutral complex formed between M and L is 1:3 [M:3L], which indicates that the Co2+ ion was oxidized to Co3+ during the reaction. The best estimate of the stability constant, log10 K f, = 3.31 for the [CoL3] complex, was observed with the MeCN–DCM (20:80 %) binary mixture at 298.15 K. The values of the thermodynamic parameters (i.e., \( \Delta G_{\text{c}}^{^\circ } \) and \( \Delta S_{\text{c}}^{^\circ } \)) for the formation of the [CoL3] complex were obtained from the temperature dependence of the stability constant via van’t Hoff plots. The results show that, in most cases, the [CoL3] complexes are enthalpy destabilized but entropy stabilized. The values and signs of the thermodynamic parameters are affected by the nature and composition of the mixed solvents but are independent of the temperature.

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Acknowledgments

We thank the Universiti Kebangsaan Malaysia (UKM) for financial support via research Grants FRGS/1/2014/ST01/UKM/02/2, DIP-2012-11, DLP-2013-001, DPP-2013-043 and DPP-2014-048.

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Authors and Affiliations

  1. Department of Chemistry, Mathematic and Natural Science Faculty, Universitas Syiah Kuala, Banda Aceh, 23111, Indonesia

    Khairi Suhud

  2. School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor Darul Ehsan, Malaysia

    Khairi Suhud, Lee Yook Heng, Madjid Rezayi, Aisha A. Al-abbasi, Siti Aishah Hasbullah & Mohammad B. Kassim

  3. Chemical Technology Program, Faculty of Science Technology, Universiti Sains Islam Malaysia, Bandar Baru Nilai, 71800, Nilai, Negeri Sembilan, Malaysia

    Musa Ahmad

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  1. Khairi Suhud
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Suhud, K., Heng, L.Y., Rezayi, M. et al. Conductometric Studies of the Thermodynamics for Complexation of 1,1-Diethyl-3-(4-methoxybenzoyl)thiourea and Cobalt(II) Cation in Aqueous Binary Mixtures of Polar Organic Solvents. J Solution Chem 44, 181–192 (2015). https://doi.org/10.1007/s10953-015-0308-2

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