Pressure-jump relaxation conductivity detection

Conductivity and Optical Detection Using p-Jump Relaxation 75 Evaluation of p-Jump Measurements 76 Commercially Available p-Jump Units 78 Application of Pressure-Jump Relaxation Techniques to Soil Constituents 81 Stopped-Flow Techniques 91 Introduction 91... 

A pressure perturbation results in the shifting of the equilibrium the return of the system to the original equilibrium state (i.e., the relaxation) is related to the rates of all elementary reaction steps. The relaxation time constant associated with the relaxation can be used to evaluate the mechanism of the reaction. During the shift in equilibrium (due to pressure-jump and relaxation) the composition of the solution changes and this change can be monitored, for example by conductivity. A description of the pressure-jump apparatus with conductivity detection and the method of data evaluation is given by Hayes and Leckie (1986). 

Figure 4.12. Typical relaxation curves in aqueous y-ATOj-PbfNO, suspension observed by the pressure-jump method with (a) electric conductivity and (b) turbidity detection. Concentration of A1203, Cp, is 15 g dm 3 at 293 K sweep, 2 ms/division wavelength in (b), 525 nm, [From Hachiya et al., 1979), with permission.]...

The kinetic measurements were carried out in the aqueous suspension of y-Al203 containing PbCNOg) at 20°C. A typical relaxation curve obtained by means of the pressure-jump technique with conductivity detection is shown in Figure 1(a) in which the electric conductivity increases with the pressure. As seen from Figure 1(a), at the beginning of the relaxation a very fast change in conductivity was also found. To resolve this, measurements were performed by the electric field pulse technique. 

The kinetics of micellization of perfluorinated surfactants has been investigated by Hoffmann and co-workers [74-80] by pressure jump and a shock wave method with conductivity detection [74-80]. Hoffmann and Ulbricht [75] also used a temperature jump relaxation technique [81] with optical detection, utilizing a pH indicator (thymol blue) to observe relaxation processes of a 1 1 mixture of perfluorooctanoic acid and its sodium salt. For micellar systems in which fast relaxation times could be measured, the parameters k /n, k lcr, a ln, and k /n were calculated. 

However, p-jump techniques are not without fault (Takahashi and Alberty, 1969). Most chemical reactions are less sensitive to pressure than to temperature alterations. Thus, a highly sensitive detection method such as conductivity must be employed to measure relaxation times if p-jump is used. Conductometric methods are sensitive on an absolute basis, but it is also fundamental that the solutions under study have adequate buffering and proper ionic strengths. In relaxation techniques, small molar volume changes result, and consequently, even if a low level of an inert electrolyte is present, conductivity changes may be undetectable if pressure perturbations of 5-10 MPa are utilized (Takahashi and Alberty, 1969). 

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