Unique Aspects of Radiochemistry

Radiochemistry involves the application of the basic ideas of inorganic, organic, physical, and analytical chemistry to the manipulation of radioactive material. However, the need to manipulate radioactive materials imposes some special constraints (and features) upon these endeavors. The first of these features is the number of atoms involved and the solution concentrations. The range of activity levels in radiochemical procedures ranges from pCi to MCi. For the sake of discussion, let us assume an activity level, D, typical of radiotracer experiments of 1 p,Ci (= 3.7 x 104 dis/s = 3.7 x 104 Bq), of a nucleus with mass number A 100. If we assume a half-life for this radionuclide of 3 d, the number of nuclei present can be calculated from the equation 

This tiny quantity of material, if prepared as an aqueous solution of volume 1 L, would have a concentration of 10 14 mol/L. This simple calculation demonstrates a number of the important features of radiochemistry, that is, (a) the manipulation of samples involving infinitesimal quantities of material, (b) the power of nuclear analytical techniques (since 1 j.Ci is a significant, easily detectable quantity of radioactivity), and (c) in an extension of the calculation, since the decay of a single atom might occur by a-particle emission (with 100% detection efficiency), the ability to do chemistry one atom at a time. 

The small number of atoms involved in some radiochemical procedures can alter the expected behavior. Although time-dependent processes obeying first-order kinetics are not changed by changes in concentration, the same is not true of second-order kinetics. For example, at 10-2 M, isotopic exchange between U(IV) and U(VI) has a lifetime of 2h, whereas at 10-10M, the same lifetime is 400 d. Another example is Np(V), which is unstable with respect to disproportionation and yet jjrCi / L solutions of NpOj are stable. The extreme dilution in some solutions can mean that equilibrium is not reached due to kinetic limitations. Fallout plutonium, present in the aqueous environment at concentrations of 10 18-10 17 M, has not reached equilibrium in over 40 y. 

Conventional analytical techniques generally operate at the part per million or higher levels. Some techniques such as laser photo acoustic spectroscopy are capable of measuring phenomena at the 10-8-10-6 mol/L level. The most sensitive conventional analytical techniques, time-resolved laser-induced fluorescence, and ICP-MS are capable of measuring concentrations at the part per trillion level, that is, 1 part in 1012, but rarely does one see detection sensitivities at the single atom level as routinely found in some radioanalytical techniques. While techniques such as ICP-MS are replacing the use of neutron activation analysis in the routine measurement of part per billion concentrations, there can be no doubt about the unique sensitivity associated with radioanalytical methods. 

Along with the unique sensitivity and small quantities of material associated with radiochemistry, there is the need to comply with the regulations governing the safe use and handling of radioactive material. This task is a primary focus in the design and execution of radiochemical experiments and is often a significant factor in the cost of the experiment. Because so many of these rules are site specific, they are not treated in this chapter. 

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