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1.
IR and Raman spectra of (NH4)3ZnCl5 have been recorded. The observed spectra have been analysed on the basis of the vibrations of ZnCl
4
2−
and NH
4
+
ions. The appearance of multiple Raman bands indicates the presence of two different types of ammonium ions. The effect of
anisotropic crystalline field over the ZnCl4 and NH4 tetrahedra is also discussed. The assignment of internal modes has been verified by the potential energy distribution calculations. 相似文献
2.
We introducegeneral starvation and consider cyclic networks withgeneral blocking and starvation (GBS). The mechanism of general blocking allows the server to process a limited number of jobs when the buffer downstream is full, and that of general starvation allows the server to perform a limited number of services in anticipation of jobs that are yet to arrive. The two main goals of this paper are to investigate how the throughput of cyclic GBS networks is affected by varying (1) the total number of jobsJ, and (2) the buffer allocationk=(k1..., km) subject to a fixed total buffer capacityK=k
1 +... + km. In particular, we obtain sufficient conditions for the throughput to be symmetric inJ and to be maximized whenJ=K/2. We also show that the equal buffer allocation is optimal under the two regimes of light or heavy usage. In order to establish these results, we obtain several intermediate structural properties of the throughput, using duality, reversibility, and concavity, which are of independent interest.Research supported in part by NSF Grant No. ECS-8919818. 相似文献
3.
D. W. Kang G. P. Rajendran M. Zeldin 《Journal of polymer science. Part A, Polymer chemistry》1986,24(6):1085-1095
The thermal degradation of Me3SiO end-blocked polydimethylsiloxane (eb-PDMS) and polydimethylsiloxane-N-phenylsilazane (eb-PDMS–NPhSz) copolymer was studied. For both polymers relative degree of polymerization (DP /DP 0) as a function of conversion (1 – W/W0) data were obtained. For eb-PDMS the results were consistent with a mechanism involving a rate determining random siloxane bond cleavage initiation step followed by a rapid and complete depropagation of the active fragments evolving volatile cyclic oligomers. Rate constants (k) for initiation were obtained at four temperatures from plots of DP ?1 vs. time. An Arrhenius activation energy of approximately 80 kcal/mol was determined and is consistent with a SiOSi scission transition state. The degradation of eb-PDMS–NPhSz appears to follow the same depolymerization process evolving cyclic oligomers. Although DP /DP 0 vs. C data suggest a random cleavage–complete depolymerization mechanism, an Arrhenius plot suggests a more complex degradation mechanism. The role of impurities as degradation catalysts is discussed. 相似文献
4.
Fragmentation patterns resulting from electron impact ionization of 3-(2′-hydroxyethyl)quinolin-2(1H)-one, three of its monosubstituted derivatives and four of its disubstituted derivatives were studied. The molecular ion of quinolinone-2-etbanol undergoes initial fragmentation with the loss of OH·, H2O, CO, ·CHO, CH2O, CH2OH·, CH2?CHOH and HCNO species. The [M – CHO]+ ion is tentatively suggested to have been formed by the expulsion of H· from the [M – CO]+· ion and the [M - CHO]+ peak may be considered as diagnostic of a 2-quinolone-3-ethanol. 相似文献
5.
K. Nagarajan M. Bhupathy Rajendra Prasad Ziley Singh V. Venugopal D.D. Sood 《Thermochimica Acta》1980,36(1):85-89
The thermal decomposition kinetics of Pr2(SO4)3 to Pr2O2SO4 have been studied by isothermal weight change determination. The reaction was found to obey a linear law up to α = 0.5; beyond α = 0.5 it could be described as a phase-boundary controlled process. A dependence of the activation energy upon the sample weight was observed. The changes in surface area and density which occur during the decomposition are also given. 相似文献
6.
A.?H.?Naik N.?V.?Thakkar S.?R.?DharwadkarEmail author K.?D.?Singh Mudher V.?Venugopal 《Journal of Thermal Analysis and Calorimetry》2004,78(3):707-713
Sodium zirconium phosphate [NaZr2P3O12], a potential ceramic matrix for fixation of high level nuclear waste, was synthesized by heating the mixture of sodium carbonate [Na2CO3], zirconyl nitrate hydrate [ZrO(NO3)2·5H2O] and ammonium dihydrogen phosphate [NH4H2PO4] in air, in a resistance heated furnace and a microwave heating system respectively in the temperature range 450 to 650°C. The mixture heated for 1 h in a resistance furnace at 450°C yielded a poorly crystalline NaZr2P3O12 [NZP]. Increasing the temperature to 650°C produced a highly crystalline product. The same mixture heated in a microwave oven at 450°C for 1 h however, yielded the most crystalline NZP.In an alternate method, the mixture of sodium dihydrogen phosphate (NaH2PO4), zirconium dioxide (ZrO2) and diammonium hydrogen phosphate [(NH4)2HPO4] heated in resistance furnace at 650°C for the same period did not react in air. It also did not yield the pure product at 450°C when heated in microwave assembly for 1 h.The authors thank the Board of Research in Nuclear Sciences (BRNS) of the Department of Atomic Energy (DAE) for the financial support for this work under the project No. 2000/37/19/BRNS/1959 dtd09-02-02. 相似文献
7.
[reaction: see text] Chelation between gamma-hydroxybutynenitrile and Grignard reagents triggers a particularly facile anionic conjugate addition reaction. Structurally diverse Grignard reagents add with equal efficiency, providing an intermediate anion that stereoselectively alkylates benzaldehyde in an overall addition-alkylation reaction. 相似文献
8.
M. M. Charyulu K. Venugopal Chetty D. G. Phal Veena Sagar SagarD. M. Sagar S. M. Pawar R. Swarup V. V. Ramakrishna V. Venugopal 《Journal of Radioanalytical and Nuclear Chemistry》2002,251(1):153-154
Recovery of americium from nitric acid solutions was studied by co-precipitation as hydroxide with various ions like calcium, ferric, nickel using sodium hydroxide and ammonium hydroxide. Studies were also carried out to recover americium using lanthanum fluoride and bismuth phosphate co-precipitation. All the methods are able to co-precipitate Am quantitatively. However, co-precipitation of Am with optimum concentration iron using ammonia is found to be better from nitric acid solutions containing large concentrations of calcium ions. Approximately 2 g of Am was recovered from 150 litres of solution batch wise using iron. 相似文献
9.
Chelation-controlled conjugate addition of Grignard reagents to γ-hydroxyalkynenitriles stereoselectively generates tri- and tetra-substituted alkenenitriles. t-BuMgCl-initiated deprotonation of hydroxyalkynenitriles followed by addition of a second Grignard reagents triggers a facile conjugate addition leading to a cyclic magnesium chelate. Protonation of the chelate stereoselectively generates trisubstituted nitriles whereas the addition of t-BuLi causes conversion to an ‘ate’ complex that allows alkylation with aldehyde electrophiles. The chelation-controlled conjugate addition-alkylation generates tri- and tetra-substituted alkenenitriles that are otherwise difficult to synthesize. 相似文献
10.
M. M. Charyulu D. G. Phal D. M. Noronha V. V. Ramakrishna V. Venugopal 《Journal of Radioanalytical and Nuclear Chemistry》2001,247(3):553-555
The extraction of Am(III) from nitric, hydrochloric, oxalic, phosphoric and hydrofluoric acids was studied using 0.4F di-2-ethyl hexyl phosphoric acid (HDEHP) containing 0.1M phosphorous pentoxide (P2O5) in dodecane/xylene. The extraction with pure 0.4F HDEHP was found to be negligible from all the media studied. However, the presence of a small amount of P2O5 in it increased the extraction substantially. The distribution ratios of Am(III) obtained for HDEHP - P2O5 mixture 3M nitric acid containing different concentrations of oxalic acid/phosphoric acid/hydrofluoric acid are in the order of 200-250. The same for 3M hydrochloric acid is very high (800). These distribution ratios are sufficiently high for the quantitative extraction of Am(III) from all the acid media studied. Different reagents such as ammonium oxalate, sodium oxalate, oxalic acid, hydrofluoric acid, sodium carbonate and potassium sulphate were explored for the back extraction of Am(III) from 0.4F HDEHP + 0.1M P2O5 in dodecane/xylene. Of these, 0.35M ammonium oxalate and 1M sodium carbonate were found to be most suitable. The back extraction of Am(III) was also attempted with water and 1M H2SO4, HNO3, HClO4 and HCl solutions after allowing the extracted organics to degrade on its own. It was found that more than 90% of Am could be back extracted with these acids. Using this method more than 90% of Am(III) was recovered from nitric acid solutions containing calcium and fluoride ions. 相似文献