Fast kinetics

How does one monitor a chemical reaction tliat occurs on a time scale faster tlian milliseconds The two approaches introduced above, relaxation spectroscopy and flash photolysis, are typically used for fast kinetic studies. Relaxation metliods may be applied to reactions in which finite amounts of botli reactants and products are present at final equilibrium. The time course of relaxation is monitored after application of a rapid perturbation to tire equilibrium mixture. An important feature of relaxation approaches to kinetic studies is that tire changes are always observed as first order kinetics (as long as tire perturbation is relatively small). This linearization of tire observed kinetics means... 

A kinetic method of analysis designed to rapidly mix samples and reagents when using reactions with very fast kinetics. 

Chemical kinetic methods are particularly useful for reactions that are too slow for a convenient analysis by other analytical methods. In addition, chemical kinetic methods are often easily adapted to an automated analysis. For reactions with fast kinetics, automation allows hundreds (or more) of samples to be analyzed per hour. Another important application of chemical kinetic... 

Very Fast Kinetics. One nanosecond is by no means the limit for kinetic measurements. The state-of-the-art for direct, time-domain measurements Hes close to s (10 fs). At times shorter than a few nanoseconds, however, there is usually not a weU-stinred solution. Even usiag a... 

Kinetics. Details of the kinetics of polymerization of THF have been reviewed (6,148). There are five main conclusions. (/) Macroions are the principal propagating species in all systems. (2) With stable complex anions, such as PF , SbF , and AsF , the polymerization is living under normal polymerization conditions. When initia tion is fast, kinetics of polymerizations in bulk can be closely approximated by equation 2, where/ is the specific rate constant of propagation /is time [I q is the initiator concentration at t = 0 and [M q, [M and [M are the monomer concentrations at t = 0, at equiHbrium, and at time /, respectively. 

In this section we discuss the basic mechanisms of pattern formation in growth processes under the influence of a diffusion field. For simphcity we consider the sohdification of a pure material from the undercooled melt, where the latent heat L is emitted from the solidification front. Since heat diffusion is a slow and rate-limiting process, we may assume that the interface kinetics is fast enough to achieve local equihbrium at the phase boundary. Strictly speaking, we assume an infinitely fast kinetic coefficient. 

Temperature-jump experiments showed an evident increase of the rate of transition by using methanol as solvent instead of water. According to Fig. 31, this is mainly caused by the increase of the fast kinetic phase at the expense of the following slow phase. 

Unfortunately there have been no more recent investigations using fast kinetic methods such as stopped flow, by adding methanol or even methanol with some water to the ether solution obtained by the procedure of Muller and Haiss, so as to check whether an equilibrium mixture of nitrosoamine and diazohydroxide is formed. 

This type of cell operates at the highest temperature (1000 °C) of all current fuel cell types. This high operating temperature has many advantages including producing steam suitable for co-generation, the ability to reform many fuels efficiently and the overall fast kinetics of the... 

One of the advanced concepts for capturing CO2 is an absorption process that utilizes dry regenerable sorbents. Pure sodium bicarbonate from Dongyang Chemical Company and spray-dried sorbents were used to examine the characteristics of CO2 reaction in a flue gas environment. The chemical characteristics were investigated in a fast fluidized reactor of 0.025 m i.d., and the effects of several variables on sorbent activity, including gas velocity (1.5 to 3.5 m/s), temperature (40 to 70 °C), and solid concentration (15 to 25 kg/m /s)], were examined in a fast fluidized-bed. Spray-dried Sorb NX30 showed fast kinetics in the fluidized reactor. 

The reactivities of pure NaHCOa solid. Sorb NHR, NHR5, and NX30 sorbents were examined in a fast fluidized bed reactor. The CO2 removal of the pure NaHCOa solid increased from 3 % to 25 % when the variables were altered. Removal increased as gas velocity was decreased, as the carbonation temperature was decreased, or as the solid circulation rate was increased. The CO2 removal of Sorb NHR and NHR5 was initially maintained at 100 % for a short period of time but quickly dropped to a 10 to 20 % removal. However, the Sorb NX30 sorbent showed fast kinetics in the fast fluidized reactor, capturing all of the 10 % of the CO2 in the flue gas within 3 seconds in the fast fluidized reactor. 

Micro reactors show, under certain conditions, low axial flow dispersion reactions with unstable intermediates can be carried out in a fast, stepwise manner on millisecond time-scales. Today s micro mixers mix on a millisecond scale and below [40]. Hence in micro reactors reactions can be carried out in the manner of a quench-flow analysis, used for determination of fast kinetics [93]. 

Transient measnrements (relaxation measurements) are made before transitory processes have ended, hence the current in the system consists of faradaic and non-faradaic components. Such measurements are made to determine the kinetic parameters of fast electrochemical reactions (by measuring the kinetic currents under conditions when the contribution of concentration polarization still is small) and also to determine the properties of electrode surfaces, in particular the EDL capacitance (by measuring the nonfaradaic current). In 1940, A. N. Frumkin, B. V. Ershler, and P. I. Dolin were the first to use a relaxation method for the study of fast kinetics when they used impedance measurements to study the kinetics of the hydrogen discharge on a platinum electrode. 

In the earliest SFG experiments [Tadjeddine, 2000 Guyot-Sionnest et al., 1987 Hunt et al., 1987 Zhu et al., 1987], a first-generation data acquisition method was used, and, because of the limited signal-to-noise ratios, IR attenuation by the electrolyte solution was a substantial handicap. So, in earlier SFG studies, as in IRAS studies, measurements were performed with the electrode pressed directly against the optical window [Baldelli et al., 1999 Dederichs et al., 2000]. With the in-contact geometry, the electrolyte was a thin film of uncertain and variable depth, probably of the order of 1 p.m. However, the thin nonuniform electrolyte layers can strongly distort the potential/coverage relationship and hinder the ability to study fast kinetics. 

Gregor, W. Grabner, G. Adelwohrer, C. Rosenau, T. Gille, L. Antioxidant properties of natural and synthetic chromanol derivatives study by fast kinetics and electron spin resonance spectroscopy. J. Org. Chem. 2005, 70(9), 3472-3483. 

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