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Chemical reactions laser studies

Same laser for Raman and one optical tweezers 514.5 nm Microdroplets CH-stretching region 2,800-3,000 cm and C = C at 1,628 cm Mie and Raman scattering of microdroplet polymerization. Size, refractive index, and morphology are determined. Droplet evaporation and chemical reactions are studied... [Pg.512]

Chemical reactions were studied by exposing small molecules to BH, generated by excimer laser photolysis of B2H6 at 193 nm [31], and monitored by laser-induced fluorescence of BH. With NO or C2H4 in the temperature range 250 to 340 K, graphs of first-order decay rates versus reactant pressure were used to determine second-order rate constants. A theoretical treatment of the BH + NO reaction indicates intermediate formation of HBON [32]. [Pg.12]

Finally in the last two sections we present preliminary calculations on two other interesting phenomena. The possibility of laser inhibition of a chemical reaction is studied using a collinear model with parameters similar to H + H2. This inhibition is a very large effect which can be seen at quite small laser field strengths, and which can sometimes destroy the effect of increased reaction probability on the lower state. The last section deals with the isotopic effects on reaction probability induced by the substitution of deuterium for hydrogen in the collinear reaction LiF 4 H. [Pg.640]

Recently, in situ studies of catalytic surface chemical reactions at high pressures have been undertaken [46, 47]. These studies employed sum frequency generation (SFG) and STM in order to probe the surfaces as the reactions are occurring under conditions similar to those employed for industrial catalysis (SFG is a laser-based teclmique that is described in section A 1.7.5.5 and section BT22). These studies have shown that the highly stable adsorbate sites that are probed under vacuum conditions are not necessarily tlie same sites that are active in high-pressure catalysis. Instead, less stable sites that are only occupied at high pressures are often responsible for catalysis. Because the active... [Pg.302]

The first half of this section discusses the use of the crossed beams method for the study of reactive scattering, while the second half describes the application of laser-based spectroscopic metliods, including laser-mduced fluorescence and several other laser-based optical detection teclmiques. Furtlier discussion of both non-optical and optical methods for the study of chemical reaction dynamics can be found in articles by Lee [8] and Dagdigian [9]. [Pg.2061]

Optical metiiods, in both bulb and beam expermrents, have been employed to detemiine tlie relative populations of individual internal quantum states of products of chemical reactions. Most connnonly, such methods employ a transition to an excited electronic, rather than vibrational, level of tlie molecule. Molecular electronic transitions occur in the visible and ultraviolet, and detection of emission in these spectral regions can be accomplished much more sensitively than in the infrared, where vibrational transitions occur. In addition to their use in the study of collisional reaction dynamics, laser spectroscopic methods have been widely applied for the measurement of temperature and species concentrations in many different kinds of reaction media, including combustion media [31] and atmospheric chemistry [32]. [Pg.2071]

The most widely employed optical method for the study of chemical reaction dynamics has been laser-induced fluorescence. This detection scheme is schematically illustrated in the left-hand side of figure B2.3.8. A tunable laser is scanned tlnough an electronic band system of the molecule, while the fluorescence emission is detected. This maps out an action spectrum that can be used to detemiine the relative concentrations of the various vibration-rotation levels of the molecule. [Pg.2071]

Another variation is the mode-locked dye laser, often referred to as an ultrafast laser. Such lasers offer pulses having durations as short as a few hundred femtoseconds (10 s). These have been used to study the dynamics of chemical reactions with very high temporal resolution (see Kinetic LffiASURELffiNTS). [Pg.9]

Because of the tunabiUty, dye lasers have been widely used in both chemical and biological appHcations. The wavelength of the dye laser can be tuned to the resonant wavelength of an atomic or molecular system and can be used to study molecular stmcture as well as the kinetics of a chemical reaction. If tunabiHty is not required, a dye laser is not the preferred instmment, however, because a dye laser requires pumping with another laser and a loss of overall system efficiency results. [Pg.9]

The possible mechanism of ionization, fragmentation of studied compound as well as their desoi ption by laser radiation is discussed. It is shown that the formation of analyte ions is a result of a multi stage complex process included surface activation by laser irradiation, the adsoi ption of neutral analyte and proton donor molecules, the chemical reaction on the surface with proton or electron transfer, production of charged complexes bonded with the surface and finally laser desoi ption of such preformed molecules. [Pg.103]

Photolytic methods are used to generate atoms, radicals, or other highly reactive molecules and ions for the purpose of studying their chemical reactivity. Along with pulse radiolysis, described in the next section, laser flash photolysis is capable of generating electronically excited molecules in an instant, although there are of course a few chemical reactions that do so at ordinary rates. To illustrate but a fraction of the capabilities, consider the following photochemical processes ... [Pg.264]

The events that happen to an atom in a chemical reaction are on a time scale of approximately 1 femtosecond (1 fs = 10 ",5 s), the time that it takes for a bond to stretch or bend and, perhaps, break. If we could follow atoms on that time scale, we could make a movie of the changes in molecules as they take part in a chemical reaction. The new field of femto-cbemistry, the study of very fast chemical processes, is bringing us closer to realizing that dream. Lasers can emit very intense but short pulses of electromagnetic radiation, and so they can be used to study processes on very short time scales. [Pg.652]

It is particularly important to study process phenomena under dynamic (rather than static) conditions. Most current analytical techniques are designed to determine the initial and final states of a material or process. Instmments must be designed for the analysis of materials processing in real time, so that the cmcial chemical reactions in materials synthesis and processing can be monitored as they occur. Recent advances in nuclear magnetic resonance and laser probes indicate valuable lines of development for new techniques and comparable instmmentation for the study of interfaces, complex hquids, microstmctures, and hierarchical assemblies of materials. Instmmentation needs for the study of microstmctured materials are discussed in Chapter 9. [Pg.88]

Generally, the more intense the available beam source, the shorter the time scales, the weaker the heterogeneities, and the longer the distances that can be probed by a scattering method. Hence, there is a strong drive to utilize high-powered lasers, synchrotrons, and intense neutron somces in research on surfaces, interfaces, and microstmctures. This is particularly tme in the study of liquid materials and of systems that undergo rapid physical transformations or chemical reactions. [Pg.184]

Chemical advances frequently are driven by technology. The discovery that atoms have inner structure was an outgrowth of the technology for working with radioactive materials. In Chapter 2 we describe a famous experiment in which the structure of atoms was studied by bombarding a thin gold foil with subatomic particles. A contemporary example is the use of lasers to study the details of chemical reactions. We introduce these ideas in Chapters 7 and 8. [Pg.7]

Kinetics on the level of individual molecules is often referred to as reaction dynamics. Subtle details are taken into account, such as the effect of the orientation of molecules in a collision that may result in a reaction, and the distribution of energy over a molecule s various degrees of freedom. This is the fundamental level of study needed if we want to link reactivity to quantum mechanics, which is really what rules the game at this fundamental level. This is the domain of molecular beam experiments, laser spectroscopy, ah initio theoretical chemistry and transition state theory. It is at this level that we can learn what determines whether a chemical reaction is feasible. [Pg.24]

Since there are a large number of different experimental laser and detection systems that can be used for time-resolved resonance Raman experiments, we shall only focus our attention here on two common types of methods that are typically used to investigate chemical reactions. We shall first describe typical nanosecond TR spectroscopy instrumentation that can obtain spectra of intermediates from several nanoseconds to millisecond time scales by employing electronic control of the pnmp and probe laser systems to vary the time-delay between the pnmp and probe pnlses. We then describe typical ultrafast TR spectroscopy instrumentation that can be used to examine intermediates from the picosecond to several nanosecond time scales by controlling the optical path length difference between the pump and probe laser pulses. In some reaction systems, it is useful to utilize both types of laser systems to study the chemical reaction and intermediates of interest from the picosecond to the microsecond or millisecond time-scales. [Pg.129]

The F + H2 — HF + FI reaction is one of the most studied chemical reactions in science, and interest in this reaction dates back to the discovery of the chemical laser.79 In the early 1970s, a collinear quantum scattering treatment of the reaction predicted the existence of isolated resonances.80 Subsequent theoretical investigations, using various dynamical approximations on several different potential energy surfaces (PESs), essentially all confirmed this prediction. The term resonance in this context refers to a transient metastable species produced as the reaction occurs. Transient intermediates are well known in many kinds of atomic and molecular processes, as well as in nuclear and particle physics.81 What makes reactive resonances unique is that they are not necessarily associated with trapping... [Pg.30]

Photoionization ti me-of-fli ght mass spectrometry is almost exclusively the method used in chemical reaction studies. The mass spectrometers, detectors and electronics are almost identical. A major distinction is the choice of ionizing frequency and intensity. For many stable molecules multi photon ionization allowed for almost unit detection efficiency with controllable fragmentation(20). For cluster systems this has been more difficult because high laser intensities generally cause extensive dissociation of neutrals and ions(21). This has forced the use of single photon ionization. This works very well for low i oni zati on potential metals ( < 7.87 eV) if the intensity is kept fairly low. In fact for most systems the ionizing laser must be attenuated. A few very small... [Pg.52]

It is now possible to design the experiments using molecular beams and laser techniques such that the initial vibrational, rotational, translational or electronic states of the reagent are selected or final states of products are specified. In contrast to the measurement of overall rate constants in a bulk kinetics experiment, state-to-state differential and integral cross sections can be measured for different initial states of reactants and final states of products in these sophisticated experiments. Molecular beam studies have become more common, lasers have been used to excite the reagent molecules and it has become possible to detect the product molecules by laser-induced fluorescence . These experimental studies have put forward a dramatic change in experimental study of chemical reactions at the molecular level and has culminated in what is now called state-to-state chemistry. [Pg.204]

The explosive phenomena produced by contact of liquefied gases with water were studied. Chlorodifluoromethane produced explosions when the liquid-water temperature differential exceeded 92°C, and propene did so at differentials of 96-109°C. Liquid propane did, but ethylene did not, produce explosions under the conditions studied [1], The previous literature on superheated vapour explosions has been critically reviewed, and new experimental work shows the phenomenon to be more widespread than had been thought previously. The explosions may be quite violent, and mixtures of liquefied gases may produce overpressures above 7 bar [2], Alternative explanations involve detonation driven by phase changes [3,4] and do not involve chemical reactions. Explosive phase transitions from superheated liquid to vapour have also been induced in chlorodifluoromethane by 1.0 J pulsed ruby laser irradiation. Metastable superheated states (of 25°C) achieved lasted some 50 ms, the expected detonation pressure being 4-5 bar [5], See LIQUEFIED NATURAL GAS, SUPERHEATED LIQUIDS, VAPOUR EXPLOSIONS... [Pg.216]

Rousseau and Leroi studied the two-photon-induced chemical reaction in AgCl by 30 kW ruby-laser pulses which results in a decomposition of AgCl into collodial silver and chlorine. The resultant blue-green emission was proportional to the square of the laser intensity and the measured quantum yield was 10". ... [Pg.40]

The observation of the induced emission, its time behavior and threshold conditions allow to study with new techniques details of chemical reactions which lead to specific states of the molecular or atomic reaction product A quantitative study of such laser systems will also yield information about collisional deactivation rates of the excited states (see also Section 111.4). [Pg.78]

The importance of chemical laser studies for basic research aimed at more detailed understanding of chemical reactions results from the possible selective population of definite energy levels of the reacting molecules. [Pg.82]


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See also in sourсe #XX -- [ Pg.7 , Pg.8 , Pg.9 , Pg.10 , Pg.11 , Pg.12 , Pg.13 , Pg.14 , Pg.15 ]




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