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OFFERING AT HIS LOTUS FEET,[object Object]
Aum Sri Sai Ram,[object Object],              Department of Chemistry,[object Object],ELECTROCHEMICAL MONITORING,[object Object],                                  OF,[object Object],      PHOTOLYTIC INTERMEDIATES,[object Object],Hari Kumar Y,[object Object]
Introduction:,[object Object],Photochemical reactions often involves species that are electrochemically interesting, for example excited states , radicals , and    metals with light influenced oxidation states are very common intermediates or products. ,[object Object],“So we can  study  ,[object Object],           photochemical processes  ,[object Object],                        with  ,[object Object],              electrochemical tools”,[object Object]
Experimental techniques are divided into different types based on the way in which the solution containing compounds to be studied is irradiated.  ,[object Object],     Different approaches are:,[object Object],1.Irradiating  the solution continuously by an    ,[object Object],        intense source.,[object Object],     2.Irradiating  the solution with a short burst of ,[object Object],        light of high intensity.,[object Object]
                            Method 1,[object Object],[object Object]
This is done so that  the overall photochemical reaction hapens at steady state approximately.
 Any electrometric method can be used to monitor the intermediates or products.     Some techniques used are:,[object Object],     (1) Potentiometric measurements,[object Object],     (2) Photopotential studies + Faradic pproaches,[object Object],         (thesehave more sensitivity and selectivity),[object Object],    These Faradic approaches include polarography,[object Object],      and amperometry at the DME.  ,[object Object]
Drawbacks of the Method 1:,[object Object],(1)High light fluxes cannot be introduced without serious heating,so the concentration of  intermediates are low and hence monitoring becomes difficult.,[object Object],(2)Since the reaction proceeds steadily , all the intermediates are present simultaneously.This makes it difficult to find the order in which the intermediates appear in the course of the reaction(since they create interference problems regarding electro chemical responses.,[object Object],[object Object],[object Object]
Absorption by the photo active solute creates a high initial concentration of the primary intermediate, its decay with time often leads to the rise and fall of other transient species that appear later in the reaction scheme.
Because these time dependencies tell much about the photolysis mechanism flash methods are immensely valuable to photochemistry and have become very common.
The intermediates are monitored by various methods .       (1) Spectroscopic methods like UV or visible absorption,[object Object],            spectroscopy.,[object Object],       (2) Electrochemical monitoring (like observing the current,[object Object],           transient arising from the electrolysis of flash generated      ,[object Object],           species at an eletrode held at constant potential ),[object Object],       (3) Cascaded approaches like using both spectroscopic  ,[object Object],            approaches + electrochemical  approaches    ,[object Object],             simultaneously ,[object Object]

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Electrochemical Monitoring of Photolytic Intermediates

  • 1.
  • 2.
  • 3.
  • 4.
  • 5.
  • 6. This is done so that the overall photochemical reaction hapens at steady state approximately.
  • 7.
  • 8.
  • 9. Absorption by the photo active solute creates a high initial concentration of the primary intermediate, its decay with time often leads to the rise and fall of other transient species that appear later in the reaction scheme.
  • 10. Because these time dependencies tell much about the photolysis mechanism flash methods are immensely valuable to photochemistry and have become very common.
  • 11.
  • 12.
  • 13. The current decay is not linked simply to a time dependent bulk concentration of the electroactive substance. Superimposed on that time function is the normal cottrell decay from the diffusion process.
  • 14.
  • 15.
  • 16. At time τ the switch closes, electrolysis begins and for a period thereafter one see a current decay that is governed by a corttell relation unperturbed by reactant disappeareance caused by decay.
  • 17. An observation proportional to the bulk concentration of the transient species can be obtained by sampling the current at a fixed interval following τ.
  • 18. Repeating the experiment with different potentials or different τ values enables one to derive current – potential curves for a sequence of delay times, hence we can obtain both qualitative and quantitative information about the transients.
  • 19.
  • 20.
  • 21. Many groups have contributed to this.
  • 22.
  • 23.