Concentration-dependent sensing mechanism

Considering the H+ dependent redox reaction between two oxidation states of the iridium oxide as the basis of the pH sensing mechanism, the electrode potential changes to the hydrogen ion concentration are expressed by Nemstian equation ... 

Although the most usual sensing mechanism is the direct luminescence quenching of the indicator dye by the analyte species (or by a relay molecule whose concentration depends on the analyte levels) or the reversible reaction of the indicator dye with the analyte, in some cases a more complex sensing scheme has been designed. For instance, the analyte itself may compete with the indicator molecules in a reversible manner for a third reactive group or molecule present in the sensor polymer matrix. This is the case of the (homogeneous)... 

Now we get to the meaning of 2 in Sn2. Remember from the last chapter that nucleophilicity is a measure of kinetics (how fast something happens). Since this is a nucleophilic substitution reaction, then we care about how fast the reaction is happening. In other words, what is the rate of the reaction This mechanism has only one step, and in that step, two things need to find each other the nucleophile and the electrophile. So it makes sense that the rate of the reaction will be dependent on how much electrophile is around and how much nucleophile is around. In other words, the rate of the reaction is dependent on the concentrations of two entities. The reaction is said to be second order, and we signify this by placing a 2 in the name of the reaction. 

The mechanism predicts that the rate of this reaction depends on the concentrations of enzyme (E) and the reactant that binds to it (S) but does not depend on additional reactants (R). This makes sense from a mechanistic point of view provided there is enough of R present that the third step proceeds rapidly once distortion is complete. Experimentally, many enzyme-catalyzed reactions obey this form of rate law. 

The strategy depends on the situation and how we measure the concentration. If we can rely on pH or absorbance (UV, visible, or Infrared spectrometer), the sensor response time can be reasonably fast, and we can make our decision based on the actual process dynamics. Most likely we would be thinking along the lines of PI or PID controllers. If we can only use gas chromatography (GC) or other slow analytical methods to measure concentration, we must consider discrete data sampling control. Indeed, prevalent time delay makes chemical process control unique and, in a sense, more difficult than many mechanical or electrical systems. 

In many studies of asymmetric reductions no attempts were made to rationalize either the extent or the sense of the observed asymmetric induction, that is, the absolute configuration of the predominant enantiomer. It is believed that it is premature in certain cases to attempt to construct a model of the transition state of the key reaction step, given the present state of knowledge about the mechanism of these reduction processes. The complexity of many of the reducing systems developed is shown by the fact that the enantiomeric excess or even the sense of asymmetric induction may depend not only on the nature of the reducing agent and substrate, but also on temperature, solvent, concentration, stoichiometry of the reaction, and in some cases the age of the reagent. 

To examine the effect of turbulence on flames, and hence the mass consumption rate of the fuel mixture, it is best to first recall the tacit assumption that in laminar flames the flow conditions alter neither the chemical mechanism nor the associated chemical energy release rate. Now one must acknowledge that, in many flow configurations, there can be an interaction between the character of the flow and the reaction chemistry. When a flow becomes turbulent, there are fluctuating components of velocity, temperature, density, pressure, and concentration. The degree to which such components affect the chemical reactions, heat release rate, and flame structure in a combustion system depends upon the relative characteristic times associated with each of these individual parameters. In a general sense, if the characteristic time (r0) of the chemical reaction is much shorter than a characteristic time (rm) associated with the fluid-mechanical fluctuations, the chemistry is essentially unaffected by the flow field. But if the contra condition (rc > rm) is true, the fluid mechanics could influence the chemical reaction rate, energy release rates, and flame structure. 

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