Nonideal effects behind reflected shock waves in a high-pressure shock tube

Abstract. Shock tubes often experience temperature and pressure nonuniformities behind the reflected shock wave that cannot be neglected in chemical kinetics experiments. Because of increased viscous effects, smaller tube diameters, and nonideal shock formation, the reflected-shock nonidealities tend to be greater in higher-pressure shock tubes. Since the increase in test temperature () is the most significant parameter for chemical kinetics, experiments were performed to characterize in the Stanford High Pressure Shock Tube using infrared emission from a known amount of CO in argon. From the measured change in vibrationally equilibrated CO emission with time, the corresponding ddt (or for a known time interval) of the mixture was inferred assuming an isentropic relationship between post-shock temperature and pressure changes. For a range of representative conditions in argon (24–530 atm, 1275–1900 K), the test temperature 2 cm from the endwall increased 3–8 K after 100 s and 15–40 K after 500 s, depending on the initial conditions. Separate pressure measurements using a shielded piezoelectric transducer confirmed the isentropic assumption. An analytical model of the reflected-shock gas dynamics was also developed, and the calculated 's agree well with those obtained from experiment. The analytical model was used to estimate the effects of temperature and pressure nonuniformities on typical chemical kinetics measurements. When the kinetics are fast (s), the temperature increase is typically negligible, although some correction is suggested for kinetics experiments lasting longer than 500 s. The temperature increase, however, has a negligible impact on the measured laser absorption profiles of OH (306 nm) and CH (216 nm), validating the use of a constant absorption coefficient. Infrared emission experiments are more sensitive to temperature and density changes, so nonuniformities should be taken into account when interpreting ir-emission data. Received 25 April 2000 / Accepted 8 September 2000     

灭鼠药介绍

本文介绍了灭鼠药的发展,常见灭鼠药的分类和化学结构,以及其毒理和中毒症状,以期更安全地使用灭鼠药。     

Synthesis of Nicotinic Acid by Potassium Dichromate Oxidation

IntroductionNicotinic acid,whose IUPAC name is 3-pyridine formic acid,also known as Vitamine B5,ismainly used as an additive in food,drink andforage industry[1— 3 ] .In medical practice,it is usedto cure pellagra and other relative vitaminedeficiency illness. It is also an intermediate for thesynthesis of important medicines and chemicalmaterials[1,4] . In China,the demand of nicotinicacid is very big. However,there are manyproblems in the current preparation methods ofnicotinic acid,such…     

Halodemetallation of (Z)-1-[2-(Triarylstannyl)vinyl]-cyclooctanol and Correlation of Proton Chemical Shift with Electronegativity

IntroductionOrganotin compounds have attracted attentionas an optimal model for antitumour agents due tothe function of the interesting intramolecularO→Sn coordination[1,2 ] . Our recent concern hasbeen focused on the preparation of ( Z) - 1 - [2 -( triarylstannyl) vinyl]- cyclooctanol[3 ] .In order tofind more appropriate compounds used asanticancer agents and explore the effect of thecoordinate O→ Sn interaction to the antitumoractivity,the new compounds werehalodemetallated and characte…     

Purification of Single-walled Carbon Nanotubes Grown by a Chemical Vapour Deposition (CVD) Method

ＩｎｔｒｏｄｕｃｔｉｏｎＳｉｎｇｌｅ ｗａｌｌｅｄｃａｒｂｏｎｎａｎｏｔｕｂｅｓ(ＳＷＮＴｓ)ｈａｖｅｂｅｅｎｓｙｎｔｈｅｓｉｓｅｄｂｙｕｓｉｎｇｖａｒｉｏｕｓｍｅｔｈｏｄｓ[1— 3] ａｎｄｔｈｅｃｈｅｍｉｃａｌｖａｐｏｕｒｄｅｐｏｓｉｔｉｏｎ (ＣＶＤ )ｍｅｔｈｏｄｈａｓｂｅｅｎｃｏｎｓｉｄｅｒｅｄａｓａ ｐｒｏｍｉｓｉｎｇｍｅｔｈｏｄｔｏ ｐｒｏｄｕｃｅＳＷＮＴｓｏｎａｎｉｎｄｕｓｔｒｉａｌｓｃａｌｅ[3— 5] .Ｈｏｗｅｖｅｒ ,ａｌｌｔｈｅＳＷＮＴ ｐｒｏｄｕｃｔｓｓｙｎｔｈｅｓｉｓｅｄｔｏｄａｔｅｃｏ…     

Proficiency evaluation as a traceability link in chemical metrology

Traceability implies comparison of the results of measurements, or comparison to national or international measurement standards. One of several approaches that have been used in chemistry to provide for such comparisons is distribution of proficiency evaluation materials which have been measured by a reference laboratory. A newer approach is based on receipt and measurement at a reference laboratory of materials that have been produced and analyzed by other laboratories. Traceability concepts and approaches to realization will be described together with discussion of the relative merits of various approaches. Extension into metrological fields other than chemistry will also be explored. Received: 14 November 2000 Accepted: 11 December 2000     

Chemical analyses of martian soil and rocks obtained by the Pathfinder Alpha Proton X-ray spectrometer

The US Mars Pathfinder spacecraft, which landed on the red planet on the 4th of July 1997, carried an Alpha Proton X-ray Spectrometer (APXS) that obtained the chemical composition of martian soil and rocks. The principles of the APXS operation are based on three interactions of alpha particles with matter: Rutherford alpha backscattering; (, p) nuclear reactions; and X-ray generation by charged particles and X-ray excitation. The APXS, as was implemented on the Pathfinder mission, uses for all three modes of operation a monoenergetic beam of alpha particles from about 40 mCi of ²⁴⁴Cm radioisotope. It employs Si charged particle detectors for alpha and proton modes and a specially designed silicon PIN detector for its X-ray mode that does not require cooling for its operation. The APXS can detect all of the elements (except H and He) present above a few tenths of a percent for all major elements and several hundred ppm for many minor and trace elements.

The APXS on Pathfinder was transported to various locations on the martian surface by the Sojourner rover which enabled it to analyze multiple soil and rock samples selected by the science team from the lander camera images. The APXS performed excellently under the adverse martian environment conditions and provided important information about the chemical composition of the martian soil and rocks. All of the analyzed rocks at the Pathfinder site were found to have high concentrations of silica, sulfur and iron, and low in magnesium, similar to those of the terrestrial basaltic andesites and definitely different from the SNC meteorites that are believed to have originated from Mars. All of the soil samples analyzed by the APXS have similar composition and are very close to the soil analyses obtained by the two Viking missions. The information derived from the Pathfinder APXS has significant implications about the origin and evolution of planet Mars.     

用加速量热仪研究KClO3/CuO/S/Mg-Al/C6Cl6的热分解

The thermal decompositions of two systems(NO.1,KClO₃(52.2%)/CuO(26.0%)/S(9.6%)/Mg-Al(3.5%)/C₆Cl₆(4.35%)) and NO.2,(KClO₃(52.2%)/CuO(26.0%)/S(9.6%)/Mg-Al(3.5%)/C₆Cl₆(4.35%)) are studied using Accelerating Rate Caorimeter (ARC).Temperature vs time curve and pressure vs time curve of reactions are shown in Fig.1 and Fig.2 respectively.The basic data including reaction time(1.3 and 7.3 min respectively),initial temperature (159 and 150℃ respectively),temperature at the maximum rate(272 and 272℃ respectively),the maximum pressure (420 and 190kPa respectively) and the activation energies(175.6 and 135.2 kJ mol-1 respectively) of the thermal decomposition are given to evaluate the safety of the two systems.Results indicate that system NO.2 is safer than NO.1.Compared with the traditional methods,ARC technique can be used to measure temperature and pressure of exothermic reaction concurrently,to find the tiny exothermicity and to determine the initial temperature of exothermic reaction.     

Probing Chemical Dynamics at Surfaces

An account is given of recent progress concerning chemical reaction dynamics at surfaces. The goal is to elucidate the reaction dynamics at the molecular level, both as time and distance is concerned. The methods of study include molecular beam scattering, scanning tunnelling microscopy, and (femtosecond) laser spectroscopy. Systems studied include elementary interactions of NO, CO, and O₂ at single crystal metal surfaces.     

A one-bead, one-stock solution approach to chemical genetics: part 1

BACKGROUND: In chemical genetics, small molecules instead of genetic mutations are used to modulate the functions of proteins rapidly and conditionally, thereby allowing many biological processes to be explored. This approach requires the identification of compounds that regulate pathways and bind to proteins with high specificity. Structurally complex and diverse small molecules can be prepared using diversity-oriented synthesis, and the split-pool strategy allows their spatial segregation on individual polymer beads, but typically in quantities that limit their usefulness. RESULTS: We report full details of the first phase of our platform development, including the synthesis of a high-capacity solid-phase bead/linker system, the development of a reliable library encoding strategy, and the design of compound decoding methods both from macrobeads and stock solutions. This phase was validated by the analysis of an enantioselective, diversity-oriented synthesis resulting in an encoded 4320-member library of structurally complex dihydropyrancarboxamides. CONCLUSIONS: An efficient and accessible approach to split-pool, diversity-oriented synthesis using high-capacity macrobeads as individual microreactors has been developed. Each macrobead contains sufficient compound to generate a stock solution amenable to many biological assays, and reliable library encoding allows for rapid compound structure elucidation post-synthesis. This 'one-bead, one-stock solution' strategy is a central element of a technology platform aimed at advancing chemical genetics.