Temperature-jump method

Temperature-jump kinetics. The kinetics of complexation of lutetium(III) with anthrani-late ion was studied by the use of a temperature-jump method.25 The principal reaction is... 

Taft equation, 229-230 Temperature, effect on rate, 156-160 Temperature-jump method, 256 Termination reaction, 182 Thermodynamic products, 59 Three-halves-order kinetics, 29... 

Temperature jump method. " Stopped flow method. Direct spectrophotometry. 

The kinetics of a series of guests that form 2 1 (guest CD) complexes were studied using temperature jump methods.179 183,210 The formation of the 1 1 complex was determined to be fast and to occur within the time resolution of the equipment, while... 

Temperature gradients in microfluidics, 26 968 Temperature-induced gelation, 9 75 Temperature-jump method, 73 425-427 Temperature level (TL)... 

The dimerization reaction is fast and has been studied by the temperature-jump method (70). At 25°C and ionic medium 3.0 M LiC104 the... 

Catalytic reactions of methanol on an Mo(112)-(lX2)-0 surface under a constant flow of CH3OH and 02 (10 6—10 5 Pa) were monitored as a function of reaction time by the temperature-jump method. Total amounts of the products are summarized in Table 8.3. When only CH3OH was fed, the reaction rate exponentially decayed with reaction time. After the reaction ceased in both conditions, the surfaces were covered with nearly 1 ML of C(a) (Table 8.3) and the sharp (1X2) LEED subspots of the surface before the reaction almost disappeared due to an increase in background intensity. As shown in Table 8.3, the selectivity of the reaction at 560 K is similar to that obtained by TPR (Table 8.2). The C(a) species formed with 26% selectivity cover the surface, resulting in the exponential decay of the reaction rate. O(a) species are also formed on the surface but they are desorbed as H20 by reaction with hydrogen atoms. It should be noted that neither C(a) nor a small amount of O(a) change the selectivity in this case. 

Fig. 13. Typical tracing of a kinetic process observed through the use of the temperature-jump method.

SUBSTRATE SYNERGISM SLOW TEMPERATURE-JUMP METHODS DEPOLYMERIZATION, END-WISE SLOW, TIGHT-BINDING INHIBITOR... 

Temperature dependence of rate constants, ARRHENIUS EQUATION RLOT Temperature-jump method,... 

During the past year, in association with Manfred Eigen in Gottingen, Germany, I examined a number of substitution reactions of nickel to see if there was indeed a direct relationship between the charge of a complex and its rate of water substitution. The temperature jump method was used to measure the rate of substitution of NH3 for water with various complexes. 

To answer the above question new results have been obtained by the study of very fast protolytic reactions in aqueous solution. These were carried out during the last few years by means of relaxation methods (sound absorption, dispersion of the dissociation field effect, temperature jump method) (for a survey cf. [3]). The neutralization reaction HgO+ -j- OH- - (Ha0)8 is the most characteristic example. It was possible to determine the rate constant of this reaction by measuring the time dependence of the dissociation field effect of very pure water of specific conductivity of 6 7 10-8 (at 25°C). 

Observing relaxation. Kinetic measurements over periods of tens of microseconds or less can be made by rapidly inducing a small displacement from the equilibrium position of a reaction (or series of reactions) and observing the rate of return (relaxation) of the system to equilibrium. Best known is the temperature jump method devised by Eigen and associates. Over a period of about 10-6 s a potential difference of -100 kV is applied across the experimental solution. A rapid electrical discharge from a bank of condensers passes... 

The dynamic tautomerism of formycin A (54a) was investigated by a temperature jump method and the mechanism of tautomerism discussed (78JA3957). 

FIG. 13.37 Schematic diagram of volume—temperature path in the temperature jump method.The solid line is the equilibrium line. 

Refs. [i] Bard AJ, FaulknerLR (2001) Electrochemical methods, 2nd edn. Wiley, New York, pp 487-516 [ii] Amatore C, Maisonhaute E (2005) Anal Chem 77-.303A [iii] FeldbergSW, Newton MD, Smalley JF (2003) The indirect laser-induced temperature jump method for characterizing fast interfacial electron transfer concept, application, and results. In Bard AJ, Rubinstein I (eds) Electroanalytical chemistry, vol. 22. Marcel Dekker, New York, pp 101-180... 

Relaxation experiments with the temperature jump method (18) give valuable information about the kinetics of nucleotidepolyphosphate and metal ion interaction in solution (20). Differences of kinetic dissociation or association constants of such metal complexes are helping to reveal some biochemical specificities of certain metal ions in metal-nucleotide complexes. 

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