JOURNAL of the Tunisian Chemical Society

serving the Research, the Education and the Industry

Synthesis and reactivity of 2-azabutadiene functionalizes. Complexation and luminescence properties

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During this work, we are interested in the synthesis of π-conjugated azadienic ligand, and their coordination study to two transition metals Rhenium and Ruthenium; we report also in this paper, the luminescence properties of some mono and binuclear complexes of Re(I) with 2-azabutadiene [1], furthermore, the study of their reactivity toward some nucleophiles. Ligand and complexes structures have been confirmed by IR, 1H and 13C NMR spectroscopic data.

A. Ben Esseghaier, M. Askri

2-azabutadienes, cycloaddition; rhenium, ruthenium, luminescence

Pages 1-7

Direct conversion of β, β’-dihydroxythioethers into thiols: Synthesis of new tridentate ligands

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Various β, β’-dihydroxythioethers, derived from oxirane were readily converted to their corresponding new mono-substituted thioethers dithiols in good yields, by treatment with thiourea and hydrochloric acid in aqueous solution. The method is applicable to aliphatic and functional diols as well as primary and secondary alcohols.

I. Gara Dallali, H.M. Sbihi, M.M. Chaabouni, M. Romdhani-Younes

hydroxythioethers, thiols, thiourea

Pages 8-12

Dicarbamates: Synthesis and substituent effects on the barrier to rotation around the N-CO bond

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A series of dicarbamates have been synthesized by addition of diols to isocyanates. These products were characterized by NMR, IR, and HRMS analyses. Substituent effects on the barrier to rotation around N-CO bond were investigated using variable temperature 1H NMR spectroscopy.

H. Maouati, I. Chniti, M.A.K. Sanhoury, D. Merlet, I. Chehidi

Dicarbamates, diols, isocyanates, barrier to rotation, variable temperature 1H NMR

Pages 13-19

Use of the Brönsted βnuc parameters in Mechanistic interpretation

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Kinetic studies for the reactions of N1-methyl-4-nitrobenzofurazanium tetrafluoroborate 1a with a series of 4-X-substituted anilines 2a-d (X = OH, OMe, Me and H) have been carried out in MeCN at 20 °C. The derived second-order rate constants (k1) have been combined with the pKa values of the conjugate acids of the anilines 2a-d to calculate the Brönsted parameters βnuc according to the linear free-energy relationship log k1 vs. pKa. The large Brönsted βnuc of 1.40 obtained suggest that the reactions proceed trough a single electron transfer (SET) mechanism. On the other hand, the finding of satisfactory correlation between the log k1 of the reactions and the oxidation potentials (Eo ) of anilines 2a-d supports this mechanism.

S. Ben Salah, R. Goumont, T. Boubaker

Kinetics, Linear Free Energy Relationships, Substituent Effects, SET Mechanism

Pages 20-25

Effect of cobalt substitution on the structural and magnetic properties of nanopowders Ni0.4Cu0.2Zn0.4Fe2O4 by hydrothermal method

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In this work, the effect of Co substitution in the structural and magnetic properties has been investigated in Ni-Cu-Zn ferrites Ni0.4-xCu0.2Zn0.4CoxFe2O4, Ni0.4Cu0.2Zn0.4-xCoxFe2O4 (x=0, 0.2, 0.4) and Ni0.4Cu0.2-xZn0.4CoxFe2O4 (x=0, 0.1, 0.2). Nanoparticles of ferrites were obtained by hydrothermal method with stirring. A single phase from Ni-Cu-Zn ferrites with cubic spinel structure was formed for all the powders. The lattice parameter has been found to decrease with increasing Co content for all the samples, and this variation in the spinel unit cell is attributed to the difference in the ionic radius of Ni2+, Cu2+, Zn2+ and Co2+ ions. The results show an improvement in magnetic properties by substitution with cobalt, especially for the samples Ni0.4Cu0.2-xZn0.4CoxFe2O4 and Ni0.4-xCu0.2Zn0.4CoxFe2O4 with x=0.2. The saturation magnetization (Ms) of samples increases with the increase of crystallite size after sintering to reach the value of 81.68 Am2 kg-1 . However, the Curie temperature decreased with increasing Co content for the spinel ferrite Ni0.4-xCu0.2Zn0.4CoxFe2O4 and does not change for Ni0.4Cu0.2-xZn0.4CoxFe2O4.

F. Saida, H. Harzali, A. Marzouki, A. Mgaidi, A. Megriche

Spinel Ni-Cu-Zn ferrites, hydrothermal method, cobalt substitution, magnetic properties.

Pages 26-31

Treatment of a Tunisian textile effluent containing Bromothymol Blue dye using anodic oxidation on Boron Doped Diamond electrode

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In the present study, Anodic oxidation (AO) as an Advanced Oxidation Process (AOP), was applied to degrade and mineralize a synthetic solution of a textile dye, Bromothymol Blue (BTB) on a Boron Doped Diamond (BDD) anode. An industrial discharge, sampled from a Tunisian textile industry containing BTB, was then treated, at the same operating conditions by AO. The effect of key parameters such as current density, reaction medium pH, treatment time, bubbling and cathode nature was investigated for the synthetic BTB solution. Discoloration yield was optimal and it reached 99% after 60 min of BTB treatment at pH 3, using a carbon felt as a cathode, operating at 60 mA cm-2 as current density and maintaining bubbling during the electrolysis. BTB mineralization was investigated under these optimal conditions by monitoring the discoloration, the Chemical Oxygen Demand (COD) and the Total Organic Carbon TOC) during 360 min of treatment, recording 100% of discoloration, 67% of COD abatement and 59% of TOC abatement. Thereupon the optimization of BTB synthetic dye solution, AO method was applied to oxidize an industrial textile effluent. Results found after 360 min of treatment at the same optimal conditions showed almost 94% of discoloration, 59% and 52% of COD and TOC removal respectively. The energy consumption per unit COD mass (ECCOD) of the AO was also calculated for the treatment of both BTB synthetic solution and the Tunisian textile effluent. 0.7 kWh (g COD)-1 and 0.91 kWh (g COD)-1 were found respectively after 360 min of treatment.

M. Maamar, N. Bellakhal

Bromothymol Blue, Advanced Oxidation Process, Anodic Oxidation, Boren Doped Diamond anode, Textile Effluent

Pages 32-42

S235JR steel corrosion behavior in neutral chloride media

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We investigated the electrochemical behavior of S235JR steel in chloride media. The results of studying the effect of chloride concentration were reported and compared to those obtained for ordinary carbon steel (OS). Potentiodynamic polarization and cyclic voltammetry techniques were employed. For S235JR steel, it was revealed that the corrosion rate increased at higher chloride concentration and a first order kinetics was obtained. The pitting potential varied linearly with the logarithm of chloride concentration and the slope value was 110.9 mV/decade. In comparison with the ordinary carbon steel corrosion behavior, S235JR steel showed generally a better general corrosion resistance in chloride media. This was reflected by a lower value of corrosion current density equal to 8.6 mA cm-2 compared to OS (28.3 mA cm-2). The pitting potential determined for S235JR steel (-336 mV/SCE) was more positive than the one of OS (-365 mV/SCE) highlighting that S235JR steel is less subjected to pitting corrosion.

K. Nasr, M. Fedel, F. Deflorian, N. Bellakhal, N. Souissi

S235JR steel, chloride, pitting, polarization, voltammetry

Pages 43-51

Characterization of two clay minerals of the Niger River Valley: Téra and Boubon

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This work presents some results of a characterization by X-ray diffraction (XRD), infrared spectroscopy (IR), Scanning Electronic Microscopy (SEM), Thermo gravimetric analysis (TGA) and differential thermic analysis (DTA) of two samples of clay minerals collected from Téra and Boubon in the valley of the Niger River. The results reveal that these samples contain a significant amount of kaolinite ranging from 60.99 to 61.61 %. We note also, the presence of Illite at low quantities.

M.A. Maman, A. Rabani, F. Habbachi, F. Menai, A. Abdoulaye, A. M’nif

clay minerals, kaolinite, XRD, IR, SEM

Pages 52-58

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