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2 Polish Journal of Chemistry

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Synthesis of New Thia-Derivative Salens, Their Complexes with Copper(II) and Analytical Application for Potentiometric Sensors

Saghatforoush L. A., Ershad S., Karim-nezhad G., Aminkhani A., Kabiri R.

Polish Journal of Chemistry

2007

Vol. 81, nr 12

2069-2069

Three new salen derivative ligands (L1, L2 and L3), containing mixed-ligand donor sets of NSNO, have been synthesized. The thermodynamics of complexation reaction between new synthesized salens and copper(II) ion in acetonitrile solution was studied by conductometric method. Formation constants of the resulting 1:1 complex was determined from the conductance-moleratio data. The results have shown that the new salens, as a neutral chelating agent formed selective and stable complex with Cu(II) ion. Thus, the L1 new salen compound was used as neutral ion carrier in the construction of a Cu2+-PVC membrane electrode. The influence of some exper i mental parameters such as membrane composition, nature and amount of plasticizer, additive and concentration of internal solution on the potential response of the Cu2+-sensor were investigated. The electrode exhibits a Nernstian response for Cu2+-over wide concentration range (5.0×10-6-1.0×10-1 M) with a slope 29.7š0.5 mV/decade and detection limit 1.0×10-6 M. It could be used in a pH range of 4.0-8.0. The electroe shows excellent discriminating ability to wards Cu2+ ion with regard to several alkaliand alkaline earth metal ions. It has a fast response time of about 20 s. The proposed sensor as an indicator electrode was used success fully in the potentiometric titra tion of Cu2+-ions with EDTA.

Synthesis of a new naphthol-derivate salen and spectrophotometric study of the thermodynamics and kinetics of its complexation with copper(II) ion in binary dimethylsulfoxide-acetonitrile mixtures

Alizadeh N., Ershad S., Naeimi H., Sharghi H., Shamsipur M.

Polish Journal of Chemistry

1999

vol. 73 nr 6

915-925

A synthetic procedure has been developed for the preparation of new salen (2,2'-[1,2-ethanediyl bis(nitriloethylidyne)]bis(1-naphthalenol). The thermodynamics and kinetics of complexation reaction between the new salen and Cu2+ ion were investigated spectrophotometrically in different dimethylsulfoxide-acetonitrile mixtures. Formation constant of the resulting 1:1 complex was determined from the absorbance-mole ratio data and found to increase with increasing acetonitrile content of the solvent mixtures. Enthalpy and entropy data for complexation were determined from the temperature dependence of the formation constant. In all solvent mixtures, the salen-copper complex is entropy stabilized but enthalpy destabilized. Order of reaction, rate constants and activation parameters for the complexation reaction in different solvent mixtures were also investigated. The Arrhenius plots showed a distinct isokinetic temperature at about 88 oC, at which the reaction rate is approximately independent of the solvent composition. Activation parameters are strongly solvent dependent.