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Cold Vapour Technique.

Another frequently used alternative sample introduction technique in


atomic spectrometry is the determination of mercury by the cold vapour technique that is based on
the unique properties of this element. Mercury has an appreciable vapour pressure at ambient
temperatures (0.16 Pa at 293 K) and the vapour is stable and monoatomic. The mercury vapour
may be entrained in a stream of an inert gas or in air and measured by the atomic absorption of the
cold vapour without the need of either flame or flame atomizers. However, with atomic
fluorescence spectrometry even lower detection limits are obtained. The equipments used in cold
vapour method are in principle quite the same described earlier for the hydride generation method.
Hence batch systems, continuous flow systems and FI-systems are employed. Previously batch-
type systems were used, but during the 90's they were gradually replaced with commercial
mercury-vapour generators based either on continuous-flow or flow injection principle. Reduction
Methods. Mercury can easily be reduced to metal from its compounds. Mercury is usually reduced
to metallic mercury by tin(I1) chloride or by sodium tetrahydroborate:

Sodium tetrahydroborate is a stronger reducing agent and the reaction rate is faster than with tin(I1)
chloride. The concentration of 64 Chapter 2 used NaBH, solution is usually between 0.1-O.5%
(wh) compared to 1-10% (wh) when tin(I1) chloride is used. Typically, SnCl, only reduces
inorganic mercury compound whereas NaBH, also reduces most of the organically bound mercury.
Tin(I1) chloride is more sensitive to the acid matrix of the samples (acid type and concentration)
than NaBH,. A drawback of NaBH, is its ability to reduce transition metals to elemental states as
mentioned earlier. Reduced mercury may be adsorbed by the precipitated metal resulting in
systematic errors. Hypophosphoric acid, hydrazine, or Cr(I1) also be used as reductants for
mercury. By selective reductions of inorganic mercury(I1) compounds and organomercury
compounds, it is possible to determine successively the inorganic and organic mercury fraction in
the same sample. Inorganic forms of mercury are reduced with Sn(I1) chloride and then the organic
forms are reduced with Sn(I1) chloride - Cd(I1) chloride solution.

Enrichment of Mercury. Due often to very low mercury contents of the samples to be analysed,
enrichment procedures are required. Mercury can be extracted with PDDC into MIBK or with
dithiazone into chloroform. It can also be electrolysed on the copper or silver cathode. The mercury
vapour can be collected in several traps such as various solution traps, gold trap, and active carbon.
Adsorption solutions may be nitric acid, bromine water-nitric acid, or potassium permanganate
solutions.