--%>
Assignment Help - homework help

What is Flash Photolysis Reactions. Explain with examples.

An example illustrates the type of mechanism that can be written to explain the development of flash photolysis reactions.

Often, as the reactions in the ozone layer of the earth's atmosphere, we are interested in the kinetic behavior of species that are not available as on the shelf chemicals. The rate constants of reactions involving such species as H atoms, O atoms, and OH and HO2 radicals must be known if the dynamics of complex reaction mixtures are to be understood. Rate constant data can sometimes be obtained by generating such species by a high intensity short duration flash of light and then following their subsequent reaction. This approach is known as flash photolysis.

A typical flash used in such studies can generate about 1 mol of produces in the several microsecond duration of the flash. The amount of one or more of the products formed directly or indirectly, is usually determined by measuring the absorption of light at a suitable wavelength. As an illustration of this technique, studies of the formation and reaction of the perhydroxyl radical,H2O are described.

The two reactions are: 

H2O = hv  72_First order reactions1.png OH + H

OH + H2  72_First order reactions1.png H2O + H 

The formation of HO2 radicals by this flash photolysis route and studies of the kinetics of subsequent reactions has been reported†. The reaction system contained small amounts of H2Oand O2 and enough H2 to produce a total pressure of 1 atm. The formation of H atoms from the photolysis at water and their attachment to O2 to form HO2 occurred rapidly. Within about 10μs the intermediates, H and OH, were largely consumed. The kinetics of the subsequent reactions ofH2O radicals could then be studied.

The optional transmission at 210 nm, where HO2 absorbs, can be used to follow the decrease of this species. If the reaction that removes HO2 is second order in HO2, the H2O concentration will vary with the time according to:

1/c = 1/ c0 + kt

That the reaction is indeed order is confirmed by the linear relation for 1/ {log (I0 /i)}, which is proportional to 1/c, versus t, as shown in this order and the net product of the reaction, H2O2, suggest that the decay of H2O occurs by the reaction:

HO2 + HO2  72_First order reactions1.png H2O2 + O2

The reaction following the initial photolysis process can be changed by changing the reagents in the reaction system.

The principle reaction sequent system then is:

OH + HO2  72_First order reactions1.png H2O + O2

Principal reactions used for the simulation curves:

Reaction Rate constant
OH + H2 72_First order reactions1.png H2O + H 4 × 104 L mol-1 s-1
H + O2 H2 72_First order reactions1.png HO2 + H2 2 × 1010 L2 mol-2 s-1
H + O2 + Ar 72_First order reactions1.png HO2 + Ar 6 × 109 L2 mol-2 s-1
H + O2 + H2O 72_First order reactions1.png HO2 + H2O 1.4 × 1011 L2 mol-2 s-1
HO2 + HO2 72_First order reactions1.png H2O2 6 × 109 L mol-1 s-1
OH + HO2 72_First order reactions1.png H2O + O3 1.2 × 1011 L mol-1 s-1

   Related Questions in Chemistry

  • Q : State substituted hydrocarbon Elaborate

    Elaborate a substituted hydrocarbon?

    		•
  • Q : What are isotonic and hypotonic

    The two solutions which are having equivalent osmotic pressure are called isotonic solutions. The isotonic solutions at the same temperature also have same molar concentration. If we have solutions having different osmotic pressures then the solution having different

    		•
  • Q : Molarity of sodium hydroxide Can

    Can someone please help me in getting through this problem. Determine the molarity of a solution having 5g of sodium hydroxide in 250ml  solution is: (i) 0.5  (ii) 1.0  (iii) 2.0   (d) 0.1Answer: The right answer i

    		•
  • Q : Microwave Adsorption The absorption of

    The absorption of microwave radiation increases the rotational energy of molecules and gives information about the moment of inertia of the molecules.Now we can begin the study of the spectroscopy that explores the different ways in which the energy of the

    		•
  • Q : Determining maximum Osmotic pressure

    Which of the following would have the maximum osmotic pressure (assume that all salts are 90% dissociated): (a) Decimolar aluminium sulphate (b) Decimolar barium chloride (c) Decimolar sodium sulphate (d) A solution obtained by mix

    		•
  • Q : What are homogenous catalyst? Give few

    When a catalyst mixes homogeneously with the reactants and forms a single phase, the catalyst is said to be homogeneous and this type of catalysis is called homogeneous catalysis. Some more examples of homogeneous catalysis are:    SO2

    		•
  • Q : Problem on partial pressure i) Show

    i) Show that the equilibrium constant Kp for the reaction CaCo3(s) ↔ CaO(s) +CO2(g)is about unity (i.e. = 1.0) at 895 °C.ii) If two grams of calcium carbonate are pl

    		•
  • Q : Molar solution of sulphuric acid Choose

    Choose the right answer from following. The molar solution of sulphuric acid is equal to: (a) N solution (b) 2Nsolution (c) N/2solution (d) 3Nsolution

    		•
  • Q : Problem on Adiabatic expansion

    Calculate the change in entropy for the system for each of the following cases. Explain the sign that you obtain by a physical argument a) A gas undergoes a reversible, adiabatic expansion from an initial state at 500 K, 1 MPa, and

    		•
  • Q : Reactivity of allyl and benzyl halides

    why allyl halide and haloarenes are more reactive than alkyl halide towards nucleophilic substitution

    		•