Mercury, atomic isotope

Even when conditions can he found which result in a distribution of isotopes in upper states, different from that in AIIg a reaction is still required which fixes this upper state distribution as stable compounds of mercury. Therefore, a developer reaction is required, which usually involves substrate molecules which contain Cl, O, OH, etc. Such reactive fragments, however, react not only with excited, but also with ground-state mercury atoms. Isotopic fractionation will therefore occur only in an isotopieally-specific primary process of the type ... 

Seven naturally occurring isotopes of mercury are known. They are mercury-196, mercury-198, mercury-199, mercury-200, mercury-201, mercury-202, and mercury-204. Isotopes are two or more forms of an element. Isotopes differ from each other according to their mass number. The number written to the right of the element s name is the mass number. The mass number represents the number of protons plus neutrons in the nucleus of an atom of the element. The number of protons determines the element, but the number of neutrons in the atom of any one element can vary. Each variation is an isotope. 

The gas chromatograph may be interfaced with atomic spectroscopic instruments for specific element detection. This powerful combination is useful for speci-ation of different forms of toxic elements in the environment. For example, a helium microwave induced plasma atomic emission detector (AED) has been used to detect volatile methyl and ethyl derivatives of mercury in fish, separated by GC. Also, gas chromatographs are interfaced to inductively coupled plasma-mass spectrometers (ICP-MS) in which atomic isotopic species from the plasma are introduced into a mass spectrometer (see Section 20.10 for a description of mass spectrometry), for very sensitive simultaneous detection of species of several elements. 

When freshly exposed to air, thallium exhibits a metallic luster, but soon develops a bluish-gray tinge, resembling lead in appearance. A heavy oxide builds up on thallium if left in air, and in the presence of water the hydride is formed. The metal is very soft and malleable. It can be cut with a knife. Twenty five isotopic forms of thallium, with atomic masses ranging from 184 to 210 are recognized. Natural thallium is a mixture of two isotopes. A mercury-thallium alloy, which forms a eutectic at 8.5% thallium, is reported to freeze at -60C, some 20 degrees below the freezing point of mercury. 

For organometailic compounds, the situation becomes even more complicated because the presence of elements such as platinum, iron, and copper introduces more complex isotopic patterns. In a very general sense, for inorganic chemistry, as atomic number increases, the number of isotopes occurring naturally for any one element can increase considerably. An element of small atomic number, lithium, has only two natural isotopes, but tin has ten, xenon has nine, and mercury has seven isotopes. This general phenomenon should be approached with caution because, for example, yttrium of atomic mass 89 is monoisotopic, and iridium has just two natural isotopes at masses 191 and 193. Nevertheless, the occurrence and variation in patterns of multi-isotopic elements often make their mass spectrometric identification easy, as depicted for the cases of dimethylmercury and dimethylplatinum in Figure 47.4. 

The isotope patterns for two simple organometallic compounds in the molecular ion region (a) dimethylmercury and (b) dimethylplatinum. The seven isotopes of mercury show clearly and appear quite different from the six isotopes of platinum. Since there are only two carbon atoms, the contribution from C is negligible. 

Mercury was determined after suitable digestion by the cold vapour atomic absorption method [40]. Lead was determined after digestion by a stable isotope dilution technique [41-43]. Copper, lead, cadmium, nickel, and cobalt were determined by differential pulse polarography following concentration by Chelex 100 ion-exchange resin [44,45], and also by the Freon TF extraction technique [46]. Manganese was determined by flameless atomic absorption spectrometry (FAA). 

The following analytical techniques seem to be adequate for the concentrations under consideration copper and nickel by Freon extraction and FAA cold vapour atomic absorption spectrometry, cobalt by Chelex extraction and differential pulse polarography, mercury by cold vapour atomic absorption absorptiometry, lead by isotope dilution plus clean room manipulation and mass spectrometry. These techniques may be used to detect changes in the above elements for storage tests Cu at 8 nmol/kg, Ni at 5 nmol/kg, Co at 0.5 nmol/kg, Hg at 0.1 nmol/kg, and Pb at 0.7 nmol/kg. 

Mass balance measurements for 41 elements have been made around the Thomas A. Allen Steam Plant in Memphis, Tenn. For one of the three independent cyclone boilers at the plant, the concentration and flow rates of each element were determined for coal, slag tank effluent, fly ash in the precipitator inlet and outlet (collected isokinetically), and fly ash in the stack gases (collected isokinetically). Measurements by neutron activation analysis, spark source mass spectroscopy (with isotope dilution for some elements), and atomic adsorption spectroscopy yielded an approximate balance (closure to within 30% or less) for many elements. Exceptions were those elements such as mercury, which form volatile compounds. For most elements in the fly ash, the newly installed electrostatic precipitator was extremely efficient. 

Further information on this system is available from studies directed at photochemical isotope enrichment (16). In this work a mercury resonance lamp containing only Hg19S was used as a source. A flowing mixture of natural mercury and water vapor exposed to the Hg198 fine structure component of the mercury resonance radiation (2537 A.) was found to result in HgO considerably enriched in Hg198. It was concluded that this could only occur if Hg(3Pj) atoms reacted in a primary step to form either a compound which is removed from further contact with the reaction or which itself may react further but must not regenerate free Hg. Either reaction (55) or (56) would satisfy these conditions. If reaction (55) is the primary reaction, the further reaction... 

Reaction (56) can occur between chlorine atoms and any isotope of mercury in the system while (50) will occur only with those isotopes of mercury which have been excited by the absorption of radiation. 

In some of the experimental work on this system a mercury resonance lamp made with isotope 202 has been used. Mercury with the usual isotopic distribution was mixed with the methyl chloride. Let X1 be the atomic fraction of isotope 202 in the HgCl formed and X1 be the atomic fraction of isotope 202 in ordinary mercury. Then... 

These various studies on reactions caused by monochromatic light from specific isotopes have been of great value in elucidating the entire question of mercury sensitization. By the use of scavengers which will remove atoms and radicals it has been possible to eliminate certain secondary reactions and further to determine the true nature of the primary processes. 

Isotopic enrichment has also been found by monoisotopic photosensitization for mixtures of natural mercury and alkyl chlorides and vinyl chloride by similar processes. Isotopic enrichment is dependent on such factors as lamp temperatures, flow rates, and substrate pressures. Enrichment increases with decreasing lamp temperature and increasing flow rate, since process (VIII-1) is more ellicient at low temperatures and Cl atoms react with natural mercury containing higher fractions of 202Hg in (VIII-3) at higher flow rates of HC1 or under intermittent illumination. The intermittent illumination results in higher enrichment than the steady illumination. 

The diffusion method depends on the fact that the velocity of a molecule is inversely proportional to the square root of its molecular weight. Slight separations were made years ago in the case of hydrochloric acid and of mercury but the results were disappointing on account of the very small yields. The isotopes of neon with atomic weights of 20 and 22 have been separated rather successfully by diffusion. Hydrogen and deuterium also have been separated by diffusion. 

This very simple case is rare because of the small wavelength shifts involved but has been observed for mercury-202 [235]. A cooled low-pressure mercury-202 microwave source and a low-pressure mercury vapour atom cell were used, to ensure minimal line broadening (0.0002 nm at the 253.7 nm line). Only mercury-202 and mercury-200 could be determined in this way, as the other isotopic lines showed overlap, and even this was only possible as, for mercury, low-temperature, low-pressure atom cells can be used. 

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