Temperature jump measurements

Markwalder B, Gozel P and van den Berg H 1992 Temperature-jump measurements on the kinetics of association and dissociation in weakly bound systems N2O4 + M = NO2 + NO2 + M J. Chem. Phys. 

This report has been written in order to demonstrate the nature of spin-state transitions and to review the studies of dynamical properties of spin transition compounds, both in solution and in the solid state. Spin-state transitions are usually rapid and thus relaxation methods for the microsecond and nanosecond range have been applied. The first application of relaxation techniques to the spin equilibrium of an iron(II) complex involved Raman laser temperature-jump measurements in 1973 [28]. The more accurate ultrasonic relaxation method was first applied in 1978 [29]. These studies dealt exclusively with the spin-state dynamics in solution and were recently reviewed by Beattie [30]. A recent addition to the study of spin-state transitions both in solution and the... 

The most significant results obtained for complexes of iron(II) are collected in Table 3. The data derive from laser Raman temperature-jump measurements, ultrasonic relaxation, and the application of the photoperturbation technique. Where the results of two or three methods are available, a gratifying agreement is found. The rate constants span the narrow range between 4 x 10 and 2 X 10 s which shows that the spin-state interconversion process for iron(II) complexes is less rapid than for complexes of iron(III) and cobalt(II). 

The value of indicates, as had been assumed, that formation of the chelate is mainly controlled by the k step. Information on cannot be easily obtained from temperature-jump measure-... 

An indication has been obtained that the opening of the salicylate hydrogen bond may become partially rate limiting in proton transfer (33) from substituted salicylate ions to hydroxide ions and buffer species in 50% (v/v) MejSO-HjO (Hibbert and Spiers, 1989a). Temperature-jump measurements of the equilibration between the salicylate ion and its dissociated species lead to curved plots of against buffer concentration and against hydroxide-ion concentration. Analysis of the results in terms of the mechanism in (33) gave the approximate values ki = 5x 10 s" and A, = 3 X 10 s ... 

Laser flash photolysis studies using the deazariboflavin system [80, 81] have shown that pyruvate binding also exerts a strong influence on intramolecular ET. In the one-electron reduced enzyme, ET from the FMN semiquinone to the oxidized heme can be observed only in the presence of pyruvate for this reaction, k j = 500 s. When the enzyme is completely reduced by stoichiometric addition of lactate prior to laser photolysis with dRf alone, pyruvate binding inhibits ET from fully reduced flavin to oxidized heme. This reaction has an observed /cet = 2000 s in the absence of pyruvate [81]. Similar values for these two rate constants have been obtained by temperature-jump measurements [82]. 

Figure 3. QMS response in a temperature-jump measurement during the catalytic reaction of methanol on Mo( 112)-p( 1 x2)-0 at Pch30H=2. 1 x 10-5 Pa and Pq2=6.5x 10-6 pa.

The amplitudes of chemical relaxation processes are determined by the equilibrium concentrations (and strictly speaking, associated activity coefficients) and by thermodynamic variables appropriate for the particular perturbation method used. Thus, for example, an analysis of the amplitudes of relaxation processes associated with temperature jump measurements can lead to determination of the equilibrium constants and enthalpies associated with the mechanism under study. As might be anticipated from our previous discussion, the relaxation amplitudes are determined by normal mode thermodynamic variables which are linear combinations of the thermodynamic variables associated with the individual steps in the mechanism. The formal analysis of relaxation amplitudes has been developed in considerable detail [2, 5,7],... 

HIGH-RESOLUTION TEMPERATURE-JUMP MEASUREMENTS USING COOLING-CORRECTION... 

Other properties of association colloids that have been studied include calorimetric measurements of the heat of micelle formation (about 6 kcal/mol for a nonionic species, see Ref. 188) and the effect of high pressure (which decreases the aggregation number [189], but may raise the CMC [190]). Fast relaxation methods (rapid flow mixing, pressure-jump, temperature-jump) tend to reveal two relaxation times t and f2, the interpretation of which has been subject to much disagreement—see Ref. 191. A fast process of fi - 1 msec may represent the rate of addition to or dissociation from a micelle of individual monomer units, and a slow process of ti < 100 msec may represent the rate of total dissociation of a micelle (192 see also Refs. 193-195). 

Fig. 2. Schematic of apparatus for temperature-jump (T-jump) measurements.

Following the general trend of looldng for a molecular description of the properties of matter, self-diffusion in liquids has become a key quantity for interpretation and modeling of transport in liquids [5]. Self-diffusion coefficients can be combined with other data, such as viscosities, electrical conductivities, densities, etc., in order to evaluate and improve solvodynamic models such as the Stokes-Einstein type [6-9]. From temperature-dependent measurements, activation energies can be calculated by the Arrhenius or the Vogel-Tamman-Fulcher equation (VTF), in order to evaluate models that treat the diffusion process similarly to diffusion in the solid state with jump or hole models [1, 2, 7]. 

In the study of reactions of the types ether than exchange mentioned previously, the usual technique involves the spectrophotometric examination of reaction mixtures. The absorbance changes that occur, at a suitable wavelength where only one species (either reactant or product) absorbs, as the reaction proceeds are measured (manually or recorded). Treatment of the data via the Beer-Lambert law enables rate coefficients and laws to be found in the usual manner. Stopped flow and temperature jump techniques have been used for very rapid reactions. 

Benderskii VA, Velichko GI. 1982. Temperature jump in electric double-layer study. Part I. Method of measurements. J Electroanal Chem 140 1-22. 

The first experimental data for a reaction involving proton transfer from a hydrogen-bonded acid to a series of bases which were chosen to give ApK-values each side of ApK=0 are given in Fig. 15 (Hibbert and Awwal, 1976, 1978 Hibbert, 1981). The results were obtained for proton transfer from 4-(3-nitrophenylazo)salicylate ion to a series of tertiary aliphatic amines in aqueous solution, as in (64) with R = 3-nitrophenylazo. Kinetic measurements were made using the temperature-jump technique with spectrophoto-metric detection to follow reactions with half-lives down to 5 x 10"6s. The reciprocal relaxation time (t ), which is the time constant of the exponential... 

Results which have an important bearing on the mechanism of proton removal from intramolecular hydrogen bonds have been obtained quite recently for the second ionisation of phenylazoresorcinols (73). Kinetic measurements were made using the temperature-jump technique (Perlmutter-Hayman and Shinar, 1975 Perlmutter-Hayman et al., 1976). 

The most common methodology for measuring fast kinetics in real time is to perturb a system at equilibrium for a time duration that is much shorter than the relaxation kinetics that follow perturbation. This perturbation can be achieved by changing the concentration of chemicals through fast mixing (stopped-flow), changing the temperature of the solution (temperature jump), simultaneously changing the... 

Studies on the dynamics of complexation for guests with cyclodextrins have been carried out using ultrasonic relaxation,40 151 168 temperature jump experiments,57 169 183 stopped-flow,170,178,184 197 flash photolysis,57 198 202 NMR,203 205 fluorescence correlation spectroscopy,65 phosphorescence measurements,56,206 and fluorescence methods.45,207 In contrast to the studies with DNA described above, there are only a few examples in which different techniques were employed to study the binding dynamics of the same guest with CDs. This probably reflects that the choice of technique was based on the properties of the guests. The examples below are grouped either by a type of guest or under the description of a technique. 

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