Differential pulse polarographic determination of trace levels of iron(III) by using the catalytic current

Trace of iron(III) are determined by differential pulse polarography in a medium of sodium hydroxide and sodium bromate using the catalytic current. Various cations do not interfere. The relative standard deviation is 2%.

Enhanced sensitivity for the differential pulse polarographic determination of molybdenum(VI) based on adsorption catalytic current

A differential pulse polarographic (DPP) method based on the adsorption catalytic current in a medium containing chlorate and 8-hydroxyquinoline (oxine) is suggested for the determination of molybdenum(VI). Experimental conditions such as pH and the composition of supporting electrolyte have been optimized to get a linear calibration graph at trace levels of Mo(VI). The sensitivity for molybdenum can be considerably enhanced by this method. The influence of possible interferences on the catalytic current has been investigated. The sensitivity of the method is compared with those obtained for other DPP methods for molybdenum. A detection limit of 1.0 x 10(-8) mol/L has been found.

Effect of packing density and adsorption parameters on the throughput of a thermal compressor

Vapour adsorption refrigeration systems (VAdS) have the advantage of scalability over a wide range of capacities ranging from a few watts to several kilowatts. In the first instance, the design of a system requires the characteristics of the adsorbate-adsorbent pair. Invariably, the void volume in the adsorbent reduces the throughput of the thermal compressor in a manner similar to the clearance volume in a reciprocating compressor. This paper presents a study of the activated carbon +HFC-134a (1,1,1,2-tetrafluoroethane) system as a possible pair for a typical refrigeration application. The aim of this study is to unfold the nexus between the adsorption parameters, achievable packing densities of charcoal and throughput of a thermal compressor. It is shown that for a thermal compressor, the adsorbent should not only have a high surface area, but should also be able to provide a high packing density. Given the adsorption characteristics of an adsorbent-adsorbate pair and the operating conditions, this paper discloses a method for the calculation of the minimum packing density necessary for an effective throughput of a thermal compressor. (C) 2002 Elsevier Science Ltd. All rights reserved.

Unimolecular HCl elimination from 1,2-dichloroethane: A single pulse shock tube and ab initio study

Thermal decomposition of 1,2-dichloroethane (1,2-DCE) has been studied in the temperature range of 10501175 K behind reflected shock waves in a single pulse shock tube. The unimolecular elimination of HCl is found to be the major channel through which 1,2-DCE decomposes under these conditions. The rate constant for the unimolecular elimination of HCl from 1,2-dichloroethane is found to be 10(13.98+/-0.80) exp(-57.8+/-2.0/RT) s(-1), where the activation energy is given in kcal mol(-1) and is very close to that value for CH3CH2Cl (EC). Ab initio (HF and MP2) and DFT calculations have been carried out to find the activation barrier and the structure of the transition state for this reaction channel from both EC and 1,2-DCE. The preexponential factors calculated at various levels of theory (BF/6-311++G**, MP2/6-311++G**, and B3LYP/6-311++G**) are (approximate to10(15) s(-1)) significantly larger than the experimental results. If the torsional mode in the ground state is treated as free internal rotation the preexponential factors reduce significantly, giving excellent agreement with experimental values. The DFT results are in excellent (fortuitous?) agreement with the experimental value for activation energy for 1,2-DCE while the MP2 and HF results seem to overestimate the barrier. However, DFT results for EC is 4.5 kcal mol(-1) less than the previously reported experimental values. At all levels, theory predicts an increase in HCI elimination barrier on beta-Cl substitution on EC.