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91.
Thorwirth S McCarthy MC Gottlieb CA Thaddeus P Gupta H Stanton JF 《The Journal of chemical physics》2005,123(5):054326
The sulfur molecules thiozone S3 and tetrasulfur S4 have been observed in a supersonic molecular beam in the centimeter-wave band by Fourier transform microwave spectroscopy, and in the millimeter- and submillimeter-wave bands in a low-pressure glow discharge. For S3 over 150 rotational transitions between 10 and 458 GHz were measured, and for S4 a comparable number between 6 and 271 GHz. The spectrum of S3 is reproduced to within the measurement uncertainties by an asymmetric top Hamiltonian with three rotational and 12 centrifugal distortion constants; ten distortion constants, but an additional term to account for very small level shifts caused by interchange tunneling, are required to reproduce to comparable accuracy the spectrum of S4. Empirical equilibrium (r(e)(emp)) structures of S3 and S4 were derived from experimental rotational constants of the normal and sulfur-34 species and vibrational corrections from coupled-cluster theory calculations. Quantum chemical calculations show that interchange tunneling occurs because S4 automerizes through a transition state with D2h symmetry which lies about 500 cm(-1) above the two equivalent C2upsilon minima on the potential energy surface. 相似文献
92.
Indoles undergo smooth coupling with phenylacetylene in the presence of 10 mol % of gallium(III) chloride or gallium(III) bromide under mild conditions to afford the corresponding 1,1-bis(1H-3-indolyl)-1-phenylethanes in high yields and with high selectivity. 相似文献
93.
94.
Summary Rate constants for the oxidation of thiosulphate by hexachloroplatinate(IV) have been measured. The kinetics of the oxidation of thiosulphate follow a second-order rate law, first order with respect to thiosulphate and first order with respect to platinum(IV). The influence of pH is small. The rates are found to depend on the nature and concentration of the cations and follow the order: Cs+>Rb+>K+>Na+>Li+. The activation parameters calculated from the temperature studies are: H=42.9 k J mol–1 and S=–102 JK–1 mol–1. A mechanism of the reaction in terms of intermediate formation of free radicals followed by the formation of tetrathionate is postulated to explain the kinetic behaviour. 相似文献
95.
Dinesh Kumar Ashu Rani D. S. N. Prasad K. S. Gupta 《Reaction Kinetics and Catalysis Letters》1991,43(1):133-141
The kinetics of the oxidation of 2-furancarboxaldehyde by thallic perchlorate at 50°C obeys the rate law
相似文献
96.
Kalyan Kali Sen Gupta Ambikesh Mahapatra Balaram Ghosh 《Transition Metal Chemistry》1991,16(5):500-502
Summary The reactivities of - and -glycerophosphates towards MnO
4
–
in HClO4 medium have been examined. The reactions between glycerophosphates and MnO
4
–
are first order with respect to [glycerophosphate], [MnO
4
–
] and [H+]. There is no evidence for cleavage of the C–O–P bond rather than the terminal –CH2OH group being oxidized to the respective phosphoglyceraldehyde. 相似文献
97.
98.
99.
100.
The progress of high temperature processes is generally described in terms of variation of the degree of conversion () with time (t). The present paper outlines a procedure for making use of-t plots for comparative assessment of productivity and energy requirements for a test system with respect to a reference, on the basis of some simplifying assumptions. It is assumed that the throughput is inversely proportional to reaction time as in the case of batch reactors and plug flow reactors. It is also assumed that the energy requirement is a simple function of process temperature. The principles outlined is illustrated with reference to some laboratory data for reduction of iron oxide by coal.The authors wish to thank Prof. P. R. Rao, Director National Metallurgical Laboratory, Jamshedpur, India, for providing facilities for experimental work and for according permission to publish this work. 相似文献
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