No abstract

Galvanostatic steady state current potential measurements were carried out for oxidation of a series of aliphatic alcohols having varying number of hydroxyl groups. The anodically deposited layer of MnO 2 on platinum was used as the electrode material. The deposit was characterised by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrode potential measurements. The catalytic role of MnO 2 in the electrooxidation of alcohols was indicated by the chronopotentiograms and the cyclic voltammograms. An analysis of the electrochemical data indicated a catalytic EC mechanism in which Mn (V) is generated electrochemically and consumed chemically in succession. Based on this and the hydrogen bonding interaction between alcoholic hydroxyl groups and MnO 2 layer, a mechanism was proposed which accounts for the variation in the observed electrochemical reaction orders. Tafel behaviour was found to be followed only approximately. Current efficiency of the electrochemical oxidation of polyols was studied. Replacement of platinum by carbon as current collector was found to leave the electrocatalytic activity of the MnO 2 deposit practically unaltered.

The reducing behaviour of methanol and ethanol towards permanganate in perchloric acid medium have been investigated in the absence and presence of the surfactant Tween-20. In the absence of surfactant the reaction is of first order with respect to both oxidant and H + but of complex order in substrate. The alcohol molecule reacts with HMnO 4 to form an intermediate complex which decomposes in the rate-determining step to give the product and Mn v . Effects of urea and acetonitrile on the reaction rate have also been studied. In the presence of Tween-20, the reaction appears to follow Berezin's model where both the oxidant and the substrate are partitioned between the aqueous and the micellar phase and then react. Different thermodynamic and kinetic parameters have been evaluated. The reaction in the presence of the surfactant is entropy-controlled rather than enthalpy-controlled.

The kinetics of the oxidation of propan-1-ol and propan-2-ol by KMnO 4 in HClO 4 medium has been studied in absence and presence of Tween-20. In the absence of Tween-20 the reaction is of first order with respect to each of permanganate and H + , but of complex order with respect to substrate. The active oxidant species HMnO 4 reacts with the alkanol molecule to form an intermediate complex, which decomposes in the rate-determining step to form the respective product and Mn v . In the presence of Tween-20, both the oxidant and the substrate are distributed between the aqueous phase and the micellar pseudo-phase and then react. Different kinetic and thermodynamic parameters have been evaluated. Compensation between water structure destruction and substrate-micelle interaction plays an important role in the presence of the surfactant.

Jute stick is the woody portion of jute plant. It remains as the leftover after extracting the fibre. The ratio of the stick to fibre is about 2.5:1. For producing dissolving pulp, prehydrolysis is carried out prior to pulping to remove hemicelluloses from the lignocelluloses. In this investigation ethylenediamine (EDA) was used with the cooking liquor to remove hemicelluloses from the jute stick. Increasing EDA charge in soda and kraft liquor decreased pentosans content in the pulp. EDA in kraft liquor showed lower kappa number and pentosans content than in the soda-liquor. Prehydrolysis further improved cellulose content and kappa number of jute stick pulp with the sacrifice of pulp yield. The bleachability of soda-EDA pulp was inferoior to the kraft-EDA and prehydrolysed soda-EDA in ECF bleaching sequences. The final brightness of soda-EDA pulp was 85.1% and kraft-EDA pulp 89.7%. Degraded cellulose (R 18 -R 10 ) in soda-EDA and kraft-EDA pulps was lower than prehydrolysed pulps. Dissolving pulp can be produced to 93% purity without prehydrolysis by reinforcing EDA in kraft liquor.