Antimony-carbon

Exchange of antimony-carbon bonds with antimony-halogen bonds in triphenylantimony and antimony trichloride upon heating at 250° C for 75 hours has been utilized for the preparation of phenylantimony chlorides (108,109). Also exchange of vinyl groups with chlorine atoms on antimony has been observed (155). Recently, however, a quantitative study of the kinetics of the reaction between trimethylantimony and antimony trichloride has been reported (298), details of which have been discussed in Section IV, A,1. 

Exchange of antimony-carbon bonds with antimony-oxygen bonds is reported in a thorough study of the disproportionation of arylantimony oxides, RSbO (126, 127). At moderately elevated temperatures ( 100° C) in the solid state, the reaction of Eq. (157)... 

They concluded that three types of behaviour were in fact competing 1) a ligand coupling, which gives biaryl without intervention of any free aromatic species, such as free radical or anion 2) a homolytic fission of the antimony-carbon bond, and the two radical species evolve by complicated radical chain reactions 3) an ionic fission of the antimony-carbon bond forming an aryl anion, the... 

The elements antimony, carbon, copper, gold, iron, lead, mercury,... 

It is recommended that the eompound be fused with a mixture of sodium carbonate (2 parts) and sodium peroxide (1 part) as in the test for Plvoaphoms. Extract the fused mass with water, filter, and acidify with dilute hydrochloric acid. Pass hydrogen sulphide through the hot solution arsenic is precipitated as yellow arsenic sulphide. If antimony is present, it will be precipitated as orange antimony trisulphide. 

Sellaite, see Magnesium fluoride Senarmontite, see Antimony(III) oxide Siderite, see Iron(II) carbonate Siderotil, see Iron(II) sulfate 5-water Silica, see Silicon dioxide Silicotungstic acid, see Silicon oxide—tungsten oxide—water (1/12/26)... 

Valentinite, see Antimony(III) oxide Verdigris, see Copper acetate hydrate Vermillion, see Mercury(II) sulflde Villiaumite, see Sodium fluoride Vitamin B3, see Calcium (+)pantothenate Washing soda, see Sodium carbonate 10-water Whitlockite, see Calcium phosphate Willemite, see Zinc silicate(4—)... 

Perchloric acid Acetic acid, acetic anhydride, alcohols, antimony compounds, azo pigments, bismuth and its alloys, methanol, carbonaceous materials, carbon tetrachloride, cellulose, dehydrating agents, diethyl ether, glycols and glycolethers, HCl, HI, hypophosphites, ketones, nitric acid, pyridine, steel, sulfoxides, sulfuric acid... 

Inert Gas Dilution. Inert gas dilution involves the use of additives that produce large volumes of noncombustible gases when the polymer is decomposed. These gases dilute the oxygen supply to the flame or dilute the fuel concentration below the flammability limit. Metal hydroxides, metal carbonates, and some nitrogen-producing compounds function in this way as flame retardants (see Flame retardants, antimony and other inorganic compounds). 

Cblorina.ted Pa.ra.ffins, The term chlotinated paraffins covers a variety of compositions. The prime variables are molecular weight of the starting paraffin and the chlorine content of the final product. Typical products contain from 12—24 carbons and from 40—70 wt % chlorine. Liquid chlotinated paraffins are used as plasticizers (qv) and flame retardants ia paint (qv) and PVC formulations. The soHd materials are used as additive flame retardants ia a variety of thermoplastics. In this use, they are combiaed with antimony oxide which acts as a synergist. Thermal stabilizers, such as those used ia PVC (see vinyl polymers), must be used to overcome the inherent thermal iastabiUty. 

The tetramethylol derivative of DABT, prepared by reaction of DABT with alkaline aqueous formaldehyde, polymerized readily on cotton. It imparted excellent flame retardancy, very durable to laundering with carbonate- or phosphate-based detergents as well as to hypochlorite bleach. This was accomphshed at low add-on without use of phosphoms compounds or antimony(III) oxide (75—77). 

Organic fluorine compounds were first prepared in the latter part of the nineteenth century. Pioneer work by the Belgian chemist, F. Swarts, led to observations that antimony(Ill) fluoride reacts with organic compounds having activated carbon—chlorine bonds to form the corresponding carbon—fluorine bonds. Preparation of fluorinated compounds was faciUtated by fluorinations with antimony(Ill) fluoride containing antimony(V) haUdes as a reaction catalyst. 

Replacement of Labile Chlorines. When PVC is manufactured, competing reactions to the normal head-to-tail free-radical polymerization can sometimes take place. These side reactions are few ia number yet their presence ia the finished resin can be devastating. These abnormal stmctures have weakened carbon—chlorine bonds and are more susceptible to certain displacement reactions than are the normal PVC carbon—chlorine bonds. Carboxylate and mercaptide salts of certain metals, particularly organotin, zinc, cadmium, and antimony, attack these labile chlorine sites and replace them with a more thermally stable C—O or C—S bound ligand. These electrophilic metal centers can readily coordinate with the electronegative polarized chlorine atoms found at sites similar to stmctures (3—6). 

Rubidium metal alloys with the other alkaU metals, the alkaline-earth metals, antimony, bismuth, gold, and mercury. Rubidium forms double haUde salts with antimony, bismuth, cadmium, cobalt, copper, iron, lead, manganese, mercury, nickel, thorium, and 2iac. These complexes are generally water iasoluble and not hygroscopic. The soluble mbidium compounds are acetate, bromide, carbonate, chloride, chromate, fluoride, formate, hydroxide, iodide. 

Other important uses of stannic oxide are as a putty powder for polishing marble, granite, glass, and plastic lenses and as a catalyst. The most widely used heterogeneous tin catalysts are those based on binary oxide systems with stannic oxide for use in organic oxidation reactions. The tin—antimony oxide system is particularly selective in the oxidation and ammoxidation of propylene to acrolein, acryHc acid, and acrylonitrile. Research has been conducted for many years on the catalytic properties of stannic oxide and its effectiveness in catalyzing the oxidation of carbon monoxide at below 150°C has been described (25). 

OtherTitanates. Nickel titanate [12035-39-1/, NiTiO, is a canary-yeUow soHd having a density of 73(00). When a mixture of antimony oxide, nickel carbonate, and titanium dioxide is heated at 980°C, nickel antimony titanate [8007-18-9] forms, which is used as a yellow pigment (95). 

Some of the chemicals mentioned above and others, such as chlorinated mbber or paraffin, antimony trioxide, calcium carbonate, calcium borate, pentaerythrithol, alumina trihydrate, titanium dioxide, and urea—melamine—formaldehyde resin, may be used to formulate fire retardant coatings. Many of these coatings are formulated in such a way that the films intumesce (expand) when exposed to fire, thus insulating the wood surface from further thermal exposure. Fire retardant coatings are mostly used for existing constmction. 

Iron Precipitation. Rich sulfide ore or Hquated antimony sulfide (cmde antimony) is reduced to metal by iron precipitation. This process, consisting essentially of heating molten antimony sulfide ia cmcibles with slightly more than the theoretical amount of fine iron scrap, depends on the abihty of iron to displace antimony from molten antimony sulfide. Sodium sulfate and carbon are added to produce sodium sulfide, or salt is added to form a light fusible matte with iron sulfide and to faciHtate separation of the metal. Because the metal so formed contains considerable iron and some sulfur, a second fusion with some Hquated antimony sulfide and salt foHows for purification. 

Carbon (qv) impregnated with antimony gives a dense nonporous material with a low tendency to seizure or galling which may be useflil in bearings and seals under high loads and velocities at temperatures up to 500 °C (27). 

Antimony Trioxide. Antimony(III) oxide (antimony sesquioxide) [1309-64-4] Sb203, is dimorphic, existing in an orthorhombic modification valentinite [1317-98-2] is colorless (sp gr 5.67) and exists in a cubic form and senarmontite [12412-52-17, Sb O, is also colorless (sp gr 5.2). The cubic modification is stable at temperatures below 570°C and consists of discrete Sb O molecules. The molecule is similar to that of P40 and As O and consists of a bowed tetrahedron having antimony atoms at each corner united by oxygen atoms lying in front of the edges. This solid crystallizes in a diamond lattice with an Sb O molecule at each carbon position. 

Antimony trioxide is insoluble in organic solvents and only very slightly soluble in water. The compound does form a number of hydrates of indefinite composition which are related to the hypothetical antimonic(III) acid (antimonous acid). In acidic solution antimony trioxide dissolves to form a complex series of polyantimonic(III) acids freshly precipitated antimony trioxide dissolves in strongly basic solutions with the formation of the antimonate ion [29872-00-2] Sb(OH) , as well as more complex species. Addition of suitable metal ions to these solutions permits formation of salts. Other derivatives are made by heating antimony trioxide with appropriate metal oxides or carbonates. 

Na[Sb(OH)g], respectively. The latter compound is one of the least soluble sodium salts known and is useful in sodium analysis. Numerous polyantimonate(V) derivatives are prepared by heat treatment of mixtures of antimony trioxide and other metal oxides or carbonates. Of these, K Sb O [12056-59-6] and K Sb O [52015-49-3] have been characterized by x-ray. These consist of three-dimensional networks of SbO in which corners and edges are shared with K" ions located in tunnels through the network (23). Simple species such as SbO and Sb20 2, analogous to orthophosphate and pyrophosphate, apparendy do not exist. 

Both antimony tribromide and antimony ttiiodide are prepared by reaction of the elements. Their chemistry is similar to that of SbCl in that they readily hydroly2e, form complex haUde ions, and form a wide variety of adducts with ethers, aldehydes, mercaptans, etc. They are soluble in carbon disulfide, acetone, and chloroform. There has been considerable interest in the compounds antimony bromide sulfide [14794-85-5] antimony iodide sulfide [13868-38-1] ISSb, and antimony iodide selenide [15513-79-8] with respect to their soHd-state properties, ferroelectricity, pyroelectricity, photoconduction, and dielectric polarization. 

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