Kinetics curves

Anions of another group were derivatized with formation of gaseous chemiluminescing species. Chemical reaction - gas extraction has been used with chemiluminescence detection in the stream of canier gas in on-line mode. Rate of a number of reactions has been studied as well as kinetic curves of extraction of gaseous products. Highly sensitive and rapid hybrid procedures have been developed for the determination of lO, BrO, CIO, CIO, NO,, N03, CrO, CIO, Br, T, S, 803 with detection limits at the level of pg/L, duration of analysis 3 min. 

In case of a pure Fe-9-2 Cq alloy in 0 05 M tljS04, ip vybjch thie corrosion rate is high, the rate was found to increase yhen the oxygenated acW was deoxygenatedi Ihese exaniples show that the role of pxygen. ip corrosion reactionis is far more complex than would appear from the kinetic curves illustrated above., ... 

If the flow is accompanied with CBA decomposition, the G value in Eq. (5) should be substituted with its time function, G(t). In the general case, thermal decomposition of a solid substance with gas emission is a heterogeneous topochemical reaction [22]. Kinetic curves of such reactions are S -shaped the curves representing reaction rate changes in time pass a maximum. At unchanging temperature, the G(t) function for any CBA is easily described with the Kolrauch exponential function [20, 23, 24] ... 

Fig. 6. Kinetic curves of the shift of Amax in the luminescence spectra of PAN samples thermally treated in solid phase. ( ) at 200 °C (o) at 180 °C (A) 150 °C. Dotted lines refer to PAN-r, solid lines refer to PAN-c...

It should be noted that the properties of a CTC depend to a considerable degree on the conditions of their preparation. Temperature increase, in particular, favors the accumulation of complete charge transfer states in a CTC. In the case of a CTC obtained in solution, the increase of dielectric constant of the solvent has the same effect. The method of preparation of a CTC also affects the kinetic curves of the accumulation and depletion of complete transfer states arising at protoirradiation. 

Fig. 21. Kinetic curves of photosensitized oxygen absorption by thermally treated PAN samples during irradiation with white light. ( ) PAN (450 °C,...

Fig. 22. Kinetic curves of oxygen absorption by ascorbic acid in the presence of polytpro-pionitrile). (1) in the dark (2) in red light (3), (4) in white light...

The shape of the kinetic curves depends on the catalyst type and polymerization conditions (ethylene pressure, temperature, concentration of inhibitors in reaction medium) (89, 97, 98). The types of the kinetic curves obtained. at ethylene polymerization under various conditions are presented in Fig. 1. 

Fig. 1. Examples of the kinetic curves during ethylene polymerization by chromium oxide catalysts. Support—SiOs temperature—80°C polymerization at constant ethylene pressure in perfect mixing reactor. Curve 1—catalyst reduced by CO at 300°C. Curve 2— catalyst activated in vacuum (400°C) polymerization in the case of (1) and (2) in solvent (heptane) ethylene pressure 10 kg/cm2 02 content in ethylene 1 ppm, HsO 3 ppm. Curves 3, 4, 5, 6—catalyst activated in vacuum (400°C) polymerization without solvent ethylene pressure 19 (curve 3), 13 (curve 4), 4 (curve 5), and 2 (curve 6) kg/cm2 02 content in ethylene 1 ppm, HsO = 12 ppm.

However, when using supports with weak linkage between the primary particles of the catalyst, its splitting occurs quickly and it is unlikely to influence the shape of the kinetic curve. For example, in the case of chromium oxide catalyst reduced by CO supported on aerosil-type silica, steady-state polymerization with a very short period of increasing rate is possible (see curve 1, Fig. 1). 

The change of shape of the kinetic curves with monomer and inhibitor concentration at ethylene polymerization by chromium oxide catalysts may be satisfactory described 115) by the kinetic model based on reactions (8)-(14). 

Another interesting case is the much higher solvent resistance of the P crystalline form of s-PS, with respect to the other ones. In fact, it has been found that the sorption of solvents (which are suitable to produce transformations from the a or the y form toward clathrate structures) occurs only in the amorphous phase, for the case of P form samples [122-124]. Sorption kinetic curves of liquid methylene chloride in s-PS samples in the a and p form are, for instance, compared in Fig. 21 [124]. 

A simulation was performed for an experiment with [O3] = 3.16 X 10-5 M and [OH-] = 7.17 X 10-3 M. The kinetic curve calculated by the kinsim program form this model is depicted in Fig. 5-4. Also shown is an experimental curve calculated from an empirical equation, based on the equation that applies at this OH- concentration ... 

Kinetic measurements were performed on a Hitachi 150-20 UV/VIS spectrophotometer. Dehydrobrominations were studied in DMF solution using cyclohexyl amine (CHA) as the base. Applied CHA concentrations were 2, 2.5, 3, 3.5, 4 and 5 10 3 mole.dm-3, initial concentration of 1 was 5 10 5 mole.dm-3 in every case (pseudo-first-order conditions). Ionic strength was adjusted to lO l mole.dm 3 with potassium nitrate. Kinetic curves / D(t) / were recorded at fix wavelength, X = 290 ran and the temperature was maintained at 30, 35.5, 40°C. Stock solutions were made daily for la and freshly for every measurement of Ih. The reaction was started by injection of solution of 1 to the thermostated solution of CHA. 

Kinetic curves were analyzed and the further correlations were determined with a nonlinear least-square-method PC program, working with the Gauss-Newton method. 

The shape of kinetic curves shown by Figure 1 clearly indicates the complexity of the reaction which requires at least five-parameter correlation (Eqn. 1). 

Based on these integrated equations, the kinetic curve, i.e. the change of absorbance in time, can be written as follows ... 

The kinetic curve of the reaction starting from ds-3-bromoflavanone (Ih) may be derived similarly to give Equation 7. 

It means, an exact evaluation of both kinetic curves may be given using the five-parameter equation represented by Equation (1). 

Recorded kinetic curves were fitted to the five-parameter Equation (1). The parameters pj with their errors and the standard deviation of regressions are summarized in Tables 1-6. Comparison of the data confirm the previously reported (refs. 8,12) similarity in the behavior of the two isomers in the presence of strong bases in spite of the different shape of the kinetic curves. The relatively good agreement of exponents p2, P4 computed for the diastereomers at the same temperature and amine concentration demonstrates the validity of the model used. From comparison of Equations (4) and (7) it follows that both reaction must give the same exponent. 

Table 1. Exponents of five-parameter approximation of kinetic curves for trans-i, (t=30°C) ...

Figure 8.3 Typical kinetic curves of AG hydrolysis to arabi-nose and galactose at 90 °C and pH 1 [20].

Figure 3 shows some examples of kinetic curves dp(t) for the disintegration of floes in stirred tanks. 

As can be seen even from the kinetic curves in Fig. 3, the type of impeller has a decisive influence on particle disintegration in stirred tanks. This is particularly clear from a comparison of other impeller systems on the basis of the reference particle diameter dp in Fig. 4. 

Two kinetic experiments with different CD concentrations were used for kinetic modeling. In this simulation all of the rate constants not involved in the hydrogenation step were not altered. The calculated and simulated kinetic curves and optical yield-conversion dependencies are shown in Figure 9a and 9b. The results of kinetic modeling indicates that the whole kinetic curve and the optical yield - conversion dependencies can be well described by a kinetic model derived from the shielding effect model. 

The catalyst reuse is carried out without treating Pd/ ACF between the runs. Negligible leaching (<10% within the experimental error) was observed after catalyst reuse. Figure 8 shows the initial reaction rate and the selectivity for several runs. After activity drops in the first run, it stabilizes at 0.085 0.008 kmolHj/kgp /s, while selectivity to 1-hexene is 94+1%. Kinetic curves are identical from the second to the sixth runs. 

For the amino-borane dehydrocoupling using [Rh(l,5-cod)(p-Cl)]2 as starting catalyst, an induction period and a sigmoid-shaped kinetic curve (plot of substrate conversion versus time) were also observed, consistent with metal-particle formation. But, for Ph2PH BH3... 

In our previous work [63], we studied the hydrolysis kinetics of lipase from Mucor javanicus in a modified Lewis cell (Fig. 4). Initial hydrolysis reaction rates (uri) were measured in the presence of lipase in the aqueous phase (borate buffer). Initial substrate (trilinolein) concentration (TLj) in the organic phase (octane) was between 0.05 and 8 mM. The presence of the interface with octane enhances hydrolysis [37]. Lineweaver-Burk plots of the kinetics curve (1/Uj.] = f( /TL)) gave straight lines, demonstrating that the hydrolysis reaction shows the expected kinetic behavior (Michaelis-Menten). Excess substrate results in reaction inhibition. Apparent parameters of the Michaelis equation were determined from the curve l/urj = f /TL) and substrate inhibition was determined from the curve 1/Uj.] =f(TL) ... 

The kinetics of soybean lipoxygenase-1 in a biphasic medium is different from the kinetics in an aqueous system [Fig. 5(a),(b)]. The kinetic curve in the two-phase system has a sigmoid shape, which is due to surface active properties of LA and HP [25]. When initial LA concentration is small in the organic phase (0-5 mM) its transfer is poor and bioconversion in the aqueous phase is slow. 

Furthermore, in the system with coupled lipase and lipoxygenase, the production rate of HP is governed by the first enzymatic reaction and mass transfer. When TL,- is small (0 to 1 mM equiv. 3 mM LA), the kinetic curve has a sigmoid shape due to surface active properties of LA and HP [25]. Hydrolysis of TL and the increase of LA favor the transfer of LA. Such a transfer allows the lipoxygenase reaction to progress. Since lipox-ygenation consumes LA and produces HP, catalysis and transfer demonstrates a reciprocal influence. 

Consequently, for high concentration of adsorption particles (which is directly linked either with their high partial pressure in gaseous phase or with high value of their adsorption heat) all kinetic curves ait) whose shape (as it will be showed below) is notably dependent on concentration of adsorption particles Nt tend (at long times) to a specific value of (Tp dependent on the nature and history of adsorbent and independent on the value of Nt-... 

Fig. 1.10. Kinetic curves of surface charging of semiconductor of n-type during adsorption. Acceptors 1 - rj> 2 - ij <. Eionors 3-Nt Ng, 4-Nt> Ng-...

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