Antimony and Bismuth

Antimony and Bismuth - Tri-n-butylstibine (Bu Sb) mediates the olefination of carbonyl groups with a-bromoacetates (a Sb-Wittig reaction). No base is required for this reaction to take place.2 3 

Bismuth chemistry has seen another quite active period over the last twelve months. For example, aldehydes undergo allylation with 

4 Antimony and Bismuth. - IR bands were assigned to VasSbC (458-472 cm- for (Ph3GeCHRiCHR C02)nSbAr5 n, where Ri = H,Ph R = H,Me n = 1, The Raman spectrum of PhSb(dmit), where dmiP = 4,5-dithiolato-l,3- 

IR and Raman data gave skeletal mode assignments for SbCl(N3)2 - Table 1 462 Raman spectrum of ClsSb-NCCN-SbCb included vSbN 195 cm  

A new series of T1 — Sb — O phases was reported, in which vSb — O modes gave an IR band near 570 cm vSbO bands were assigned from the Raman spectra of the species Cs2Sb40n and A3Sb50i4, where A = Rb or Cs. These were related to different types of oxide connectivities.  

Dissolving Sb2S3 in aqeous Na2S solution (25-130 °C) produced SbS, 

IR spectroscopy was used to follow the low-temperature phase transitions of the ionic compound (CH3ND3+)3[Sb2Br9] .  

Complexes Involving Chromium, Molybdenum, and Tungsten 1. Monoelement Complexes 

Huttner has described the reaction between [SbCI Cr(CO)5 2] and [Na]2[M2(CO)10] (M = Cr, Mo, W) that affords the anionic complexes [Sb Cr(CO)s 2 M(CO)s ]- (91, M = Cr 92, M = Mo 93, M = W) (see Fig. 26) (46) containing a trigonal-planar antimony atom. These complexes are isoelectronic with the trimanganese-indium compound 6 (together with 

Transition Metal Bond Lengths to Antimony and Bismuth 

Trigonal-planar coordination is rare for antimony and the possibility of multiple bonding between antimony and chromium must be considered. However, as has already been pointed out, the presence of multiple bonding 

One other class of compound is known, namely, the trimetallastibine species [Sb M(CO)3(CsHs) 3] (96, M = Mo 97, M = W). Compound 96 was originally reported by Malisch (98) and subsequently by Norman (99) along with the related tungsten complex. The bismuth analogues [Bi M-(CO)3(CsH5) 3] (98, M = Mo 99, M = W) have also been described (100) 

The work in this group has focussed mainly in antimony and bismuth because of the thermoelectric properties of the chalcogenides186 and as low temperature single-source precursors to related semiconductor materials.187 The use of bismuth compounds in the treatment of gastrointestinal disorders has lead to the study of several thiolate compounds as models to understand the bioactivity. 

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France M R, Buchanan J W, Robinson J C, Pullins S FI, Tucker J T, King R B and Duncan M A 1997 Antimony and bismuth oxide clusters growth and decomposition of new magic number clusters J. Phys. Chem. A 101 6214... 

Arsenic and antimony resemble phosphorus in having several allotropic modifications. Both have an unstable yellow allotrope. These allotropes can be obtained by rapid condensation of the vapours which presumably, like phosphorus vapour, contain AS4 and Sb4 molecules respectively. No such yellow allotrope is known for bismuth. The ordinary form of arsenic, stable at room temperature, is a grey metallic-looking brittle solid which has some power to conduct. Under ordinary conditions antimony and bismuth are silvery white and reddish white metallic elements respectively. 

Antimony and bismuth do not react with sodium hydroxide. 

A complete set of trihalides for arsenic, antimony and bismuth can be prepared by the direct combination of the elements although other methods of preparation can sometimes be used. The vigour of the direct combination reaction for a given metal decreases from fluorine to iodine (except in the case of bismuth which does not react readily with fluorine) and for a given halogen, from arsenic to bismuth. 

Solutions of many antimony and bismuth salts hydrolyse when diluted the cationic species then present will usually form a precipitate with any anion present. Addition of the appropriate acid suppresses the hydrolysis, reverses the reaction and the precipitate dissolves. This reaction indicates the presence of a bismuth or an antimony salt. 

Give an account of the oxides and the chlorides of arsenic, antimony and bismuth, including an explanation of any major... 

Many nonferrous metals can be extracted by reduction smelting, eg, copper, tin, nickel, cobalt, silver, antimony, and bismuth. Blast furnaces are sometimes used for the smelting of copper or tin, but flash and reverberatory furnaces are more common for metals other than lead. 

Metals less noble than copper, such as iron, nickel, and lead, dissolve from the anode. The lead precipitates as lead sulfate in the slimes. Other impurities such as arsenic, antimony, and bismuth remain partiy as insoluble compounds in the slimes and partiy as soluble complexes in the electrolyte. Precious metals, such as gold and silver, remain as metals in the anode slimes. The bulk of the slimes consist of particles of copper falling from the anode, and insoluble sulfides, selenides, or teUurides. These slimes are processed further for the recovery of the various constituents. Metals less noble than copper do not deposit but accumulate in solution. This requires periodic purification of the electrolyte to remove nickel sulfate, arsenic, and other impurities. 

Purification. Tellurium can be purified by distillation at ambient pressure in a hydrogen atmosphere. However, because of its high boiling point, tellurium is also distilled at low pressures. Heavy metal (iron, tin, lead, antimony, and bismuth) impurities remain in the still residue, although selenium is effectively removed if hydrogen distillation is used (21). 

F. G. Mann, The Heterocyclic Derivatives of Phosphorus, Arsenic, Antimony and Bismuth, 2nd ed., Wiley-Interscience, New York, 1970. 

G. O. Doak and L. D. Freedman, Organometallic Compounds of Arsenic, Antimony, and Bismuth,]ohn Wiley Sons, Inc., New York, 1970. 

The precipitated copper from this reaction is an important constituent of the slime that collects at the bottom of the electrolytic cells. The accumulation of copper as well as of impurities such as nickel, arsenic, antimony, and bismuth is controlled by periodic bleed-off and treatment in the electrolyte purification section. 

Although some changes occur in the melting furnace, cathode impurities are usually reflected directly in the final quaUty of electrorefined copper. It is commonly accepted that armealabiUty of copper is unfavorably affected by teUurium, selenium, bismuth, antimony, and arsenic, in decreasing order of adverse effect. Silver in cathodes represents a nonrecoverable loss of silver to the refiner. If the copper content of electrolyte is maintained at the normal level of 40—50 g/L, and the appropriate ratio of arsenic to antimony and bismuth (29) is present, these elements do not codeposit on the cathode. 

The final ceU product contains 250—300 g/L H2SO in the last stages of electrolyte purification, and antimony and bismuth precipitate, resulting in heavily contaminated cathodes that are recycled through the smelter. Arsenic and hydrogen evolved at the cathodes at these later stages react to form arsine, and hoods must be provided to collect the toxic gas. 

By-Product Recovery. The anode slime contains gold, silver, platinum, palladium, selenium, and teUurium. The sulfur, selenium, and teUurium in the slimes combine with copper and sUver to give precipitates (30). Some arsenic, antimony, and bismuth can also enter the slime, depending on the concentrations in the electrolyte. Other elements that may precipitate in the electrolytic ceUs are lead and tin, which form lead sulfate and Sn(0H)2S04. 

Arsenic, Antimony and Bismuth Table 13.4 Some physical properties of Group 15 elements... 

C. A. McAulifee and A. G. Mackie Chemistry of Arsenic, Antimony and Bismuth, Ellis Horwood, Chichester, 1990, 350 pp. 

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