Cyanides thiocyanate

In the former, it gives precipitates with halides (except the fluoride), cyanides, thiocyanates, chromates(VI), phosphate(V), and most ions of organic acids. The silver salts of organic acids are obtained as white precipitates on adding silver nitrate to a neutral solution of the acid. These silver salts on ignition leave silver. When this reaction is carried out quantitatively, it provides a means of determining the basicity of the acid... 

Pseudohalides of Se in which the role of halogen is played by cyanide, thiocyanate or selenocyanate are known and, in the case of Se are much more stable with respect to disproportionation than are the halides themselves. Examples are Se(CN)2, Se2(CN)2, Se(SeCN)2, Se(SCN)2, Se2(SCN)2. The selenocyanate ion SeCN is ambidentate like the thiocyanate ion, etc., p. 325), being capable of ligating to metal centres via either N or Se, as in the osmium(IV) complexes [OsCl5(NCSe)], [OsCl5(SeCN)], and trans-[OsCU(NCSe)(SeCN)]2-.920) Tellurium and polonium pseudohalogen analogues include Te(CN)2 and Po(CN)4 but have been much... 

Determination. To an aliquot of the silver(I) solution containing between 10 and 50 pg of silver, add sufficient EDTA to complex all those cations present which form an EDTA complex. If gold is present (>250 xg) it is masked by adding sufficient bromide ion to form the AuBr4 complex. Cyanide, thiocyanate or iodide ions are masked by adding sufficient mercury(II) ions to complex these anions followed by sufficient EDTA to complex any excess mercury(II). Add 1 mL of 20 per cent ammonium acetate solution, etc., and proceed as described under Calibration. 

Finally, anions that are incompatible with oxidants will give rise to violent reactions with iodates. This goes for cyanides, thiocyanates and sulphides. In the last case, arsenic, antimony, copper and tin sulphides were the main ones cited. 

Cyanide and thiocyanate anions in aqueous solution can be determined as cyanogen bromide after reaction with bromine [686]. The thiocyanate anion can be quantitatively determined in the presence of cyanide by adding an excess of formaldehyde solution to the sample, which converts the cyanide ion to the unreactive cyanohydrin. The detection limits for the cyanide and thiocyanate anions were less than 0.01 ppm with an electron-capture detector. Iodine in acid solution reacts with acetone to form monoiodoacetone, which can be detected at high sensitivity with an electron-capture detector [687]. The reaction is specific for iodine, iodide being determined after oxidation with iodate. The nitrate anion can be determined in aqueous solution after conversion to nitrobenzene by reaction with benzene in the presence of sulfuric acid [688,689]. The detection limit for the nitrate anion was less than 0.1 ppm. The nitrite anion can be determined after oxidation to nitrate with potassium permanganate. Nitrite can be determined directly by alkylation with an alkaline solution of pentafluorobenzyl bromide [690]. The yield of derivative was about 80t.with a detection limit of 0.46 ng in 0.1 ml of aqueous sample. Pentafluorobenzyl p-toluenesulfonate has been used to derivatize carboxylate and phenolate anions and to simultaneously derivatize bromide, iodide, cyanide, thiocyanate, nitrite, nitrate and sulfide in a two-phase system using tetrapentylammonium cWoride as a phase transfer catalyst [691]. Detection limits wer Hi the ppm range. 

About 100 gal of process wastewater is typically generated from 1 t of coke produced.15 These wastewaters from byproduct coke making contain high levels of oil and grease, ammonia nitrogen, sulfides, cyanides, thiocyanates, phenols, benzenes, toluene, xylene, other aromatic volatile components, and polynuclear aromatic compounds. They may also contain toxic metals such as antimony, arsenic, selenium, and zinc. Water-to-air transfer of pollutants may take place due to the escape of volatile pollutants from open equalization and storage tanks and other wastewater treatment systems in the plant. 

Another premise cannot be excluded and will be investigated eventually. As in the case of cyanide ion, isothiocyanate ion may be a precursor in the biosynthesis of some marine isothiocyanates. Like cyanide, thiocyanate ion is an ambident nucleophile. Specific incorporation of this ion by a carbocationic site... 

For a given carbonium ion the order of degree of ionization appears to be hydroxide, alkoxides, and carboxylates < cyanide < thiocyanate < ferrocyanide < azide < chloride < bromide < sulfate and perchlorate. 

Intimate mixtures of chlorates, bromates or iodates of barium, cadmium, calcium, magnesium, potassium, sodium or zinc, with finely divided aluminium, arsenic, copper carbon, phosphorus, sulfur hydrides of alkali- and alkaline earth-metals sulfides of antimony, arsenic, copper or tin metal cyanides, thiocyanates or impure manganese dioxide may react violently or explosively, either spontaneously (especially in presence of moisture) or on initiation by heat, friction, impact, sparks or addition of sulfuric acid [1], Mixtures of sodium or potassium chlorate with sulfur or phosphorus are rated as being exceptionally dangerous on frictional initiation. 

Cadmium hydroxide is more basic than zinc hydroxide. It forms anionic complex Cd(OH)42 when treated with concentrated caustic soda solution. It forms complexes with cyanide, thiocyanate and ammonium ions when added to the solutions of these ions. 

When heated with alkali cyanide, thiocyanate salt is obtained ... 

The group VIB cyanides, thiocyanates and selenocyanates and their complexes with species such as thiourea have been described.1,45 For example, the tellurium dithiocyanate complex has been prepared45 by treatment of tellurium dichloride or tellurium dibromide with ammonium thiocyanate. It seems that little information exists on the preparation of tellurocyanates and there is a sparsity of data on polonium derivatives. Indeed, the only known cyanide of polonium is probably a salt of the quadrivalent element.1... 

Mercuric Selenocyanate, Hg(CNSe)a, forms a crystalline mass when mercuric acetate is treated with potassium selenocyanate. The crystalline mass consists of white needles which are slightly soluble in cold water but readily soluble in alkali cyanide, thiocyanate and selenocyanate solutions. Mercuric selenocyanate turns brown in air and is decomposed by heat.4... 

Arsenic carbonate has not been prepared, but arsenic salts of several organic acids, including arsenic cyanide, thiocyanate, acetate and tartrate, are known. Arsenic chromithiocyanate, As[Cr(SCN)g], has also been described.5... 

Transition-metal ions are employed as nodes and bifunctional ligands as spacers. Commonly used spacer ligands are pseudohalides such as cyanide, thiocyanate, and azide, and N-donor ligands such as pyrazine, 4,4 -bipyridine, and 2,2/-bipyrimidine. Besides discrete supermolecules, some one-, two-, and three-dimensional architectural motifs generated from this strategy are shown in Fig. 20.3.9. 

Bromides and iodides interfere because of the liberated halogen the test is not trustworthy in the presence of chromates, sulphites, thiosulphates, iodates, cyanides, thiocyanates, hexacyanoferrate(II) and (III) ions. All of these anions may be removed by adding excess of nitrate-free Ag2S04 to an aqueous solution (or sodium carbonate extract), shaking vigorously for 3-4 minutes, and filtering the insoluble silver salts, etc. 

Cyanides, thiocyanates, hexacyanoferrate(II)s, and hexacyanoferrate(III)s also yield ammonia under these experimental conditions. The reaction is somewhat slower for these anions up to 5 minutes may elapse before ammonia can be detected from hexacyanoferrate(II)s and hexacyanoferrate(III)s. If these are present, or are suspected as a result of the preliminary tests, particularly that with concentrated sulphuric acid, they must first be removed as follows. Treat the soda extract with excess of nitrate-free silver sulphate, warm the mixture to about 60°, shake vigorously for 3-4 minutes, and filter from the silver salts of the interfering anions and excess of precipitant. Remove the excess silver ions from the filtrate by adding excess sodium hydroxide solution and filter off the precipitated silver oxide. Evaporate the filtrate to about half bulk and test with zinc, aluminium or Devarda s alloy. If cyanides alone are present, they may be rendered innocuous by the addition of a little mercury(II) chloride solution. 

The relative insolubility of some of the salts of silver is in the order chloride, cyanide, thiocyanate, bromide, iodide, and sulphide. The metal is usually estimated gravimetrically as chloride, or by electrolytic deposition. It can also be weighed as chromate.1 Other gravimetric methods are reduction to metal by hypophosphorous acid,2 and by alkaline glycerol and other reagents.3... 

Crystallography revealed a bound chloride ion at the amino terminus of the helix containing the proximal His336 which can be replaced with bromide. Crystal structures of the human MPO-cyanide, MPO-cyanide-bromide, and MPO-cyanide-thiocyanate have also been determined by Fenna and coworkers to 1.9 A. These results support a model for a single common binding site for halides and thiocyanate as substrates or as inhibitors near the S-meso carbon of the porphyrin ring in myeloperoxidase. 

Write balanced equations to describe the oxidation of the following substances with strongly alkaline permanganate in the presence of barium ion (Stamm reaction) iodide, phosphite (HP03 ), hypophosphite (H2PO2 ), cyanide, thiocyanate, formate. 

Besides explaining the ammonia complexes in this manner, Werner extended the same kind of reasoning to hydrates, cyanides, thiocyanates, amine complexes, cyanates, carbonyls, and similar compounds. He also reasoned that there must be isomerism owing to the arrangement of ions in the inner, or coordination, sphere and the outer sphere where ordinary, or primary, valence relations hold—e.g., [Co(NH3)5CL]Br2 and [Co(NH3)5Br]ClBr. 

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