Activation analysis neutron reactions

Neutron Activation Analysis Few samples of interest are naturally radioactive. For many elements, however, radioactivity may be induced by irradiating the sample with neutrons in a process called neutron activation analysis (NAA). The radioactive element formed by neutron activation decays to a stable isotope by emitting gamma rays and, if necessary, other nuclear particles. The rate of gamma-ray emission is proportional to the analyte s initial concentration in the sample. For example, when a sample containing nonradioactive 13AI is placed in a nuclear reactor and irradiated with neutrons, the following nuclear reaction results. 

All the techniques discussed here involve the atomic nucleus. Three use neutrons, generated either in nuclear reactors or very high energy proton ajccelerators (spallation sources), as the probe beam. They are Neutron Diffraction, Neutron Reflectivity, NR, and Neutron Activation Analysis, NAA. The fourth. Nuclear Reaction Analysis, NRA, uses charged particles from an ion accelerator to produce nuclear reactions. The nature and energy of the resulting products identify the atoms present. Since NRA is performed in RBS apparatus, it could have been included in Chapter 9. We include it here instead because nuclear reactions are involved. 

Neutron activation analysis of a polymer suggests that when Py is used as the electron doner (D), the initiation proceeds through the Cl atom, but when D = DMSO, both Cr and DMSO residues are the primary radicals produced from the photoexcited ion-pair complex. The following reaction scheme is proposed ... 

Radioactive nuclei are used extensively in chemical analysis. One technique of particular importance is neutron activation analysis. This procedure depends on the phenomenon of induced radioactivity. A sample is bombarded by neutrons, bringing about such reactions as... 

A modem technique for nitrogen detn is known as fast neutron activation analysis. Materials such as RDX are exposed to a high density fast neutron flux which converts the 14N content of the sample into unstable 13N. The N is detd by measuring the 13 N produced by the 14N (n, 2n) 13N reaction. This technique is extremely sensitive, but requires specialized instrumentation (Refs 44, 51 61)... 

This can result in a radioactive product from the A(n, t)A reaction where A is the stable element, n is a thermal neutron, A is the radioactive product of one atomic mass unit greater than A, and y is the prompt gamma ray resulting from the reaction. A is usually a beta and/or gamma emitter of reasonably long half-life. Where access to a nuclear reactor has been convenient, thermal neutron activation analysis has proven to be an extremely valuable nondestructive analytical tool and in many cases, the only method for performing specific analyses at high sensitivities... 

Neutron Activation Analysis X-Ray Fluorescence Particle-Induced X-Ray Emission Particle-Induced Nuclear Reaction Analysis Rutherford Backscattering Spectrometry Spark Source Mass Spectrometry Glow Discharge Mass Spectrometry Electron Microprobe Analysis Laser Microprobe Analysis Secondary Ion Mass Analysis Micro-PIXE... 

Principles and Characteristics In neutron activation analysis (NAA) the sample is irradiated by neutrons. The principal reaction in NAA is ... 

May et al. [73] used neutron activation analysis to determine 237neptunium in waste waters. The determination used the 237Np(rc,y)238Np reaction. The detection limit was 5 x 10 6 xg of 237neptunium, which corresponds to 2.5 x 10 6 xg/kg for 200 ml seawater samples. 

The radioactive tin-125 isotope in the bis(tributyltin-125) oxide enabled Klotzer and Gomer40 to use a neutron activation analysis to determine the percent tin in the organotin compounds formed in the photochemical reaction between bis(tributyltin-125) oxide and glucose (equation 39). 

The y particle is emitted virtually instantaneously on the capture of the neutron, and is known as a prompt y - it can be used analytically, in a technique known as prompt gamma neutron activation analysis (PGNAA), but only if such y s can be measured in the reactor during irradiation. Under the conditions normally used it would be lost within the nuclear reactor. In this reaction, no other prompt particle is emitted. The isotope of sodium formed (24Na) is radioactively unstable, decaying by beta emission to the element magnesium (the product nucleus in Figure 2.13), as follows ... 

Until it was known that the half-life of Tc is much shorter than 10 years Herr looked for technetiimi-98 in a munber of minerals from Norway and South Africa by neutron activation analysis. This most sensitive method was also used by Alperovitch et al. and Anders et al. to detect this isotope in nature. According to the nuclear reaction... 

Selenium is converted to its volatile hydride by reaction with sodium boro-hydride, and the cold hydride vapor is introduced to flame AA for analysis. Alternatively, selenium is digested with nitric acid and 30% H2O2, diluted and analyzed by furnace-AA spectrophotometer. The metal also may be analyzed by ICP-AES or ICP/MS. The wavelengths most suitable for its measurements are 196.0 nm for flame- or furnace-AA and 196.03 nm for ICP-AES. Selenium also may be measured by neutron activation analysis and x-ray fluorescence. 

Radioactive lateling of this cluster and neutron activation analysis of the g)ld enabled us to determine the extent of Nnding of the cluster to the particles. The results of both analytical methods show that a spacer of minimum length of about 10 A between the -SH group of a ribosomal protein and the N-atom on the cluster is n ed for significant binding. Preliminary experiments indicate that the producte of the derivatization reaction with SOS particles can be crystallized. 

The concentration of silver nanoparticles and ions in solntions was determined by neutron activation analysis [15]. Samples were irradiated in the nuclear reactor at the Institute of Nuclear Physics, Tashkent, Uzbekistan. The product of nuclear reaction ° Ag(n,y)" Ag has the half-life Tj j=253 days. The silver concentration was determined by measnring the intensity of gamma radiation with the energy of 0.657 MeV and 0.884 MeV emitted by "" Ag. A Ge(Li) detector with a resolution of about 1.9 keV at 1.33 MeV and a 6,144-channel analyzer were used for recording gamma-ray quanta. 

During the late 1960s and early 1970s, neutron activation analysis provided a new way to measure bulk chemical composition. Neutron activation analysis utilizes (n,y) reactions to identify elements. A sample is placed in a nuclear reactor where thermal neutrons are captured by atoms in the sample and become radioactive. When they decay, the radioactive isotopes emit characteristic y-rays that are measured to determine abundances. Approximately 35 elements are routinely measured by neutron activation analysis. A number of others produce radioactive isotopes that emit y-rays, but their half-lives are too short to be useful. Unfortunately, silicon is one of these elements. Other elements do not produce y-ray-emitting isotopes when irradiated with neutrons. There are two methods of using neutron activation to determine bulk compositions, instrumental neutron activation analysis (INAA) and radiochemical neutron activation analysis (RNAA). 

The most common sources are based on the 3H(d, n) reaction. Deuterons are accelerated to 150 keV with currents 2.5 mA and strike a tritium target. They produce 2 x 1011 of 14-MeV neutrons/s under these conditions. The neutrons produced are widely used in fast neutron activation analysis for the determination of light elements. The tritium targets are typically metals such as Ti, which have been loaded with titanium tritide. The accelerators are usually small Cockcroft-Walton machines or small sealed-tube devices where the ion source and accelerator structure are combined to produce a less expensive device with neutron yields 108/s. 

Bromine-82 has a half-life of about 36 hours this is not sufficient for the isotope to be used conveniently in tracer work especially if labelled reagents have first to be prepared and purified. Low concentrations of bromine in small specimens of organic materials, such as polymers, can be determined by the method of neutron activation analysis (2). The various substances are prepared using ordinary bromine and then samples are bombarded with thermal neutrons so that the nuclear reaction 81Br(n, y)82Br occurs. Activity is therefore induced in the samples comparison with standards treated similarly permits determination of the bromine contents of the unknowns. For this technique to be applicable, it is necessary to have access to a powerful source of thermal neutrons. Neutron activation analysis can be used for the determination of very low concentrations of many elements and its general features have been fully discussed (3). 

Troth (32) has studied the polymerization of vinyl acetate in the presence of triphenylmethane and observed the effects discussed above. In practice, there are complications resulting from reactions involving the initiator radicals and the transfer agent. These complications were found also when carbon tetrabromide was used as a transfer agent in the polymerization of styrene in this case, the bromine contents of the polymers were determined by neutron activation analysis (17). 

The authors are grateful to W. Reifschneider and R. A. Hickner for their suggestions on the thioglycolic acid addition reaction, to D. L. Schechter for his permission to use his data on fatty acid adsorption, and O. U. Anders for determining the degrees of carboxylation by neutron activation analysis. 

In 14 MeV neutron activation analysis the four principal nuclear reactions leading to the formation of indicator radionuclides are as follows ... 

It is obvious, therefore, that 14 MeV neutron activation analysis can not compete with thermal neutron activation analysis as a technique for trace element analysis. In simple matrices, however, the rapid and non-destructive nature of the technique recommends its use for routine analysis of large numbers of samples for elemental abundances at the one milligram level, or above. It is unfortunate that the element carbon can not be determined by this technique. The nuclear reaction 12C(n, 2n)1 C which would be of great analytical importance is endoergic to the extent of nearly 19 MeV. This reaction is obviously not energetically possible using the 14.7 MeV neutrons produced by the 2H(3H,w)4He reaction commonly employed in most neutron generators. 

Neutron activation analysis is based upon the production of radioisotopes by nuclear reactions resulting from neutron bombardment, followed by identification and measurement of the different radioisotopes formed. Element activation can also be carried out by bombardment with high-energy charged particles, X-rays or gamma rays (5). 

In PIGE the y-emission is usually prompt. If very low amounts of trace elements have to be detected it can be advantageous to use a delayed decay. In this case, the technique is called charged particle activation (CPA) and is an analogue to neutron activation analysis (NAA). It has the advantage that the prompt background from interfering reactions is completely removed as irradiation and analysis are completely separated in time. This also allows to remove external contaminants in the short time between irradiation and measurement which further improves detection limits. A comprehensive description of the technique can be found in the ion beam analysis handbook [2], For 19F CPA is conceivable in special cases via the 19F(d,dn)18F reaction. However, we have found only one application in the literature [64],... 

Selenium forms a volatile derivative, piazselenol, which can be subjected to GC analysis (Scheme 5.39). Young and Christian [612] treated selenium with 2,3-diaminonaph-thalene at pH 2.0 and extracted the resulting piazselenol into -hexane. With the use of an ECD, down to 5 10-I° g of selenium could be detected. The procedure, applied to the analysis of selenium in human blood, urine and river water, led to results equivalent to those obtained by neutron activation analysis. Similarly, Nakashima and Toei [613] performed the reaction of selenium (as selenious acid) with 4-chloro-o-phenylenediamine at pH 1 and extracted the derivative into toluene. They reported a detection limit of 0.04 jug. Shimoishi [614] analysed the content of selenium in metallic tellurium by this method. The sample was dissolved in aqua regia, followed by reaction with 4-nitro-o-phenylenediamine and extraction into toluene. Down to 10 ng of selenium could be determined using only a few milligrams of sample. Common ions did not interfere even when present in a large excess. Selenium in marine water was determined after the same derivatization step [615],... 

Examples of thenoyltrifluoroacetone (TTA) (in benzene) extraction can be found in the separation of. 3.8-minute V 2 in. neutron activation analysis (90), of zirconium activities in niobium bombarded by protons (128), and of 1.8-minute Pa22 from the reaction products of thorium bombarded.by a cyclotron (172,173,175)- 16-second Y89"1 (109) and 25-minute Am246 (74), the daughter products of Zr and Pu2 respectively, were separated by back extraction into acidic aqueous solution from the parent in TTA-benzene solution. 

---