Stopped-flow

Developed for solutions, this has the advantage that only small samples are required. Two solutions are rapidly forced through a mixing chamber from which there is an exit into a tube. The flow is rapidly halted and a detector at the position of halting of 

The time of analysis must be very rapid. Stopped flow methods always require an inbuilt timing device, and time intervals at which analysis is made are dictated by the speed at which successive analyses can be carried out. Spectroscopic methods using pulsed radiation are very useful here because they can be both analytical and timing devices. 

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During the course of these studies the necessity arose to study ever-faster reactions in order to ascertain their elementary nature. It became clear that the mixing of reactants was a major limitation in the study of fast elementary reactions. Fast mixing had reached its high point with the development of the accelerated and stopped-flow teclmiques [4, 5], reaching effective time resolutions in the millisecond range. Faster reactions were then frequently called inuneasurably fast reactions [ ]. 

Chance B 1951 Rapid and sensitive spectrophotometry. I. The accelerated and stopped-flow methods for the measurement of the reaction kinetics and spectra of unstable compounds in the visible region of the spectrum Rev. Sci. Instrum 22 619-27... 

Figure C3.1.2. Stopped-flow apparatus with motor-driven syringes. Syringe plungers force tire reactants A and B tlirough a mixing chamber into a spectral cell. Kinetic data collection begins when tire effluent syringe plunger is pushed out to contact an activation switch, about a millisecond after tire initiation of mixing. (Adapted from Pilling M J and Seakins P W 1995 Reaction Kinetics (Oxford Oxford University Press)...

The example above of tire stopped-flow apparatus demonstrates some of tire requirements important for all fonns of transient spectroscopy. These are tire ability to provide a perturbation (pump) to tire physicochemical system under study on a time scale tliat is as fast or faster tlian tire time evolution of tire process to be studied, the ability to synclironize application of tire pump and tire probe on tliis time scale and tire ability of tire detection system to time resolve tire changes of interest. 

Stone conservations Stonegroundwood Stone treatment Stoneware Stone-washing Stony coal Stop-flow ftir techniques Stopped-flow mixing Stop Scald Storage... 

Physical Methods. Vitamins D2 and D exhibit uv absorption curves that have a maximum at 264 nm and an (absorbance) of 450—490 at 1% concentration (Table 8). The various isomers of vitamin D exhibit characteristically different uv absorption curves. Mixtures of the isomers are difficult to distinguish. However, when chromatographicaHy separated by hplc, the peaks can be identified by stop-flow techniques based on uv absorption scanning or by photodiodearray spectroscopy. The combination of elution time and characteristic uv absorption curves can be used to identify the isomers present in a sample of vitamin D. 

Fire Hazards - Flash Point Not pertinent Flammable Limits in Air (%) 1.6- 10 Fire Extinguishing Agents Stop flow of gas Fire Extinguishing Agents Not To Be Used Not pertinent Special Hazards of Combustion Products Not pertinent Behavior in Eire Containers may explode in fires. Vapor is heavier than air and may travel considerable distance to ignition source and flash back Ignition Temperature (deg. F) 725 Electrical Hazard Not pertinent Burning Rate No data. 

The procedure which had originally been used by Lehn et al. involved slow addition (over a period of ca. 8 h) of ca. 0.1 M solutions of diamine and diacyl halide in benzene. Dye et al. found that the reactions could be conducted more rapidly as long as stirring was kept efficient. This observation suggested the use of a mixing chamber of the type normally used for stopped-flow kinetic studies. Utilizing this type of set-up, the latter authors were able to obtain a 70% yield for 1, slightly inferior to the yield reported by Lehn, but a similar yield of 3 which is better than that previously ob-tained. Note that the chemical features of this synthetic method are essentially identical to the approach shown in Eq. (8.1) and differ primarily in the mechanics. 

These special throttling valves use an elastomer diaphragm to restrict or stop flow (Figure 15-7). They are suitable for slurry service and make an excellent valve for sand drains. Unfortunately, they do not provide a reliable, positive shut-off and should be installed in series with a ball or other on/off valve if positive shut-off is required. 

Figure 4-11. Schematic diagram of stopped flow kinetic system.

The dead time is typically 3-5 ms. so stopped flow is not quite as fast as continuous flow, but it requires less than a milliliter of each solution per run. Methods have been described for measuring the dead time " " these are based upon standard reactions whose kinetic behavior is well known. The error introduced by collecting data before mixing is complete can be corrected." ... 

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