Sulfur vapor

The sulfur vapor is condensed and recovered in the liquid or solid form. 

Total Sulfur and Sulfide Sulfur. Total sulfur is predominately in the form of metal sulfate, and because sulfates act as inerts, these materials have htde impact on the process. Sulfide sulfur compounds, on the other hand, react and leave the furnace as a sulfur vapor, which may deposit in the gas handling system. A possible mechanism for this is the partial reaction of SO2 to H2S, followed by... 

Thiothionyl Fluoride and Difluorodisulfane. Thiothionyl fluoride [1686-09-9] S=SF2, and difluorodisulfane [13709-35-8] FSSF, are isomeric compounds which may be prepared as a mixture by the action of various metal fluorides on sulfur vapor or S2CI2 vapor. Chemically, the two isomers are very similar and extremely reactive. However, in the absence of catalytic agents and other reactive species, FSSF is stable for days at ordinary temperatures and S=SF2 may be heated to 250°C without significant decomposition (127). Physical properties of the two isomers are given in Table 6. The microwave spectmm of S=SF2 has been reported (130). 

Other Fluorosulfanes. Difluorotrisulfane [31517-17-6] FSSSF, and difluorotetrasulfane [31517-18-7] FSSSSF, have been identified as the constituents of the yellow oil obtained when sulfur vapor reacts with AgF. Their existence was demonstrated by nmr and mass spectroscopy (134,135). 

Sulfur vapor and ammonia react to give ammonium sulfide and nitrogen sulfur and hquid anhydrous ammonia react to produce nitrogen sulfide... 

The molecular composition of sulfur vapor is a complex function of temperature and pressure. Vapor pressure measurements have been interpreted in terms of an equiHbtium between several molecular species (9,10). Mass spectrometric data for sulfur vapor indicate the presence of all possible molecules from S2 to Sg and negligible concentrations of and S q (H)- In general, octatomic sulfur is the predominant molecular constituent of sulfur vapor at low temperatures, but the equihbrium shifts toward smaller molecular species with increasing temperature and decreasing pressure. 

Hydrogen sulfide has been produced in commercial quantities by the direct combination of the elements. The reaction of hydrogen and sulfur vapor proceeds at ca 500°C in the presence of a catalyst, eg, bauxite, an aluminosihcate, or cobalt molybdate. This process yields hydrogen sulfide that is of good purity and is suitable for preparation of sodium sulfide and sodium hydrosulfide (see Sodium compounds). Most hydrogen sulfide used commercially is either a by-product or is obtained from sour natural gas. 

A basic research study on combustion of sulfur led to the postulation that sulfur trioxide may actually be the primary combustion product and that sulfur dioxide may then be produced by the further reaction of sulfur trioxide with sulfur vapor ki the oxygen-deficient region of the flame (261). 

Titanium disulfide can also be made by pyrolysis of titanium trisulfide at 550°C. A continuous process based on the reaction between titanium tetrachloride vapor and dry, oxygen-free hydrogen sulfide has been developed at pilot scale (173). The preheated reactants ate fed iato a tubular reactor at approximately 500°C. The product particles comprise orthogonally intersecting hexagonal plates or plate segments and have a relatively high surface area (>4 /g), quite different from the flat platelets produced from the reaction between titanium metal and sulfur vapor. The powder, reported to be stable to... 

Thermodynamic calculations for reactions forming carbon disulfide from the elements are compHcated by the existence of several known molecular species of sulfur vapor (23,24). Thermochemical data have been reported (12). Although carbon disulfide is thermodynamically unstable at room temperature, the equiHbtium constant of formation increases with temperature and reaches a maximum corresponding to 91% conversion to carbon disulfide at about 700°C. Carbon disulfide decomposes extremely slowly at room temperature in the absence of oxidizing agents. 

Charcoal—Sulfur Process. Sulfur vapor reacts with charcoal at temperatures of 750—900°C to form carbon disulfide ... 

Sulfur vapor is an equiUbrium mixture of several molecular species, including Sg, S, and S2. The equiUbrium shifts toward S2 at higher temperatures and lower pressures. The overall reaction is endothermic and theoretically consumes 1950 kj/kg (466 kcal/kg) of carbon disulfide when the reactants are at 25°C and the products are at 750°C. Most of the heat input goes into dissociation of sulfur vapor to the reactive species, S2. Equation 25 is slightly exothermic when the reactants are at a constant temperature of 750°C. 

For equation 26, starting with methane and soHd sulfur at 25°C, and ending with gaseous products at 600°C, the reaction is endothermic and requires 2.95 MJ /kg (705 kcal/kg) of CS2. The reaction of methane and sulfur vapor in the diatomic form is actually exothermic (23,78). Superheating of the sulfur is claimed to be preferable (79), and series operation of reactors offers a means of reducing process temperatures at which the sulfur dissociates (80). 

Potential Processes. Sulfur vapor reacts with other hydrocarbon gases, such as acetjiene [74-86-2] (94) or ethylene [74-85-1] (95), to form carbon disulfide. Higher hydrocarbons can produce mercaptan, sulfide, and thiophene intermediates along with carbon disulfide, and the quantity of intermediates increases if insufficient sulfur is added (96). Light gas oil was reported to be successflil on a semiworks scale (97). In the reaction with hydrocarbons or carbon, pyrites can be the sulfur source. With methane and iron pyrite the reaction products are carbon disulfide, hydrogen sulfide, and iron or iron sulfide. Pyrite can be reduced with carbon monoxide to produce carbon disulfide. 

Copper does not form protective oxide fdms. Therefore, its corrosion resistance is poor against most acids and salts. Many gases-haloids, sulfurous anhydride, sulfur vapors, hydrogen sulfide, carbon dioxide, ammonium-destroy copper. However, copper is highly corrosion resistant to alkali solutions. 

Schwefel-cyanwasserstoffsaure, /. thiocyanic acid, -dampf, m. sulfur vapor, -dioxyd, n, sulfur dioxide, -dunst, m. sulfurous vapor, schwefelecht, a. (Dyeing) fast to stoving, fast to sulfurous acid. 

Elemental sulfur is a yellow, tasteless, almost odorless, insoluble, nonmetallic molecular solid of crownlike S8 rings (9). The two common crystal forms of sulfur are monoclinic sulfur and rhombic sulfur. The more stable form under normal conditions is rhombic sulfur, which forms beautiful yellow crystals (Fig. 15.12). At low temperatures, sulfur vapor consists mainly of S8 molecules. At temperatures above 720°C, the vapor has a blue tint from the S, molecules that form. The latter are paramagnetic, like O,. 

F. Reactions of Trifluoromethyl Radicals with Sulfur Vapor. 188... 

Although belonging to a slightly different class of reactions, the reaction of trifluoromethyl radicals with sulfur vapor has been shown to provide a route to trifluoromethyl polysulfide compounds (20). Instead of using sulfur halides, which undoubtedly would also give positive results, elemental sulfur (Ss) was vaporized and dissociated into atomic and polyatomic sulfur species. 

With the exception of the reactions of trifluoromethyl radicals with sulfur vapor, which is really a separate class of reactions, if the power supplied to the load coil surrounding the reactor (see Fig. 2) was maintained at, or near, the minimum amount needed to support the discharge, in only two cases were compounds found that clearly resulted from reactions other than replacement of halogen by trifluoromethyl. The reaction of tellurium tetrabromide (or the chloride) gave, in addition to the products just reported, very small proportions of such species as BrCF2TeCF2Br and (C2F5)2Te, which were isolated in yields of... 

Despite the fact that natural elemental sulfur contains 0.75% of the isotope [4] with a nuclear spin of 7 = /2 no NMR spectra of elemental sulfur have ever been reported. Such spectra are however well-known for compounds containing just one or two sulfur atoms [5]. Electron spin resonance spectra of irradiated elemental sulfur samples and of quenched sulfur vapor have been reviewed elsewhere [6-8]. 

Sulfur vapor contains all molecules with between 2 and 8 atoms which are related by temperature- and pressure-dependent equilibrium reactions ... 

Below 250 °C the spectrum of saturated sulfur vapor consists of unresolved absorption bands at 210, 265, and 285 nm caused by the electronic transitions of cyclo-Ss [11]. These bands have also been observed for Sg solutions in organic solvents and for thin films of sohd Sg (see below). 

The large energy differences between the global minimum structure of C2v symmetry and the other isomers indicate that equilibrium sulfur vapor will contain only minute amounts of the latter, even at very high temperatures. However, under non-equilibrium conditions as in electrical discharges or by illumination with a laser as in Raman spectroscopy unstable isomers may be formed and detected. 

The other Raman lines calculated for this species at 471 and 225 cm may have been obscured by the strong lines of Sg, Sy, and Se near 475 cm (stretching) and 213/232/ 263 cm (totally symmetrical bending) in the Raman spectra of sulfur vapor... 

Billmers and Smith recorded the UV-Vis absorption spectra of sulfur vapor at various pressures (9-320 Torr or 1.2-42.7 kPa) and temperatures (670-900 K) but failed in obtaining the correct reaction enthalpy for the interconversion of S3 and S4 from the absorption intensities [19]. The molar extinction coefficient of S3 at 400 nm exceeds that of S4 at 520 nm by more than one order of magnitude. While the S3 absorption band at 360-440 nm exhibits a vibrational fine structme, the two broad S4 absorption bands at... 

High-temperature sulfur vapor at low pressure is said to be pale-violet due to the presence of S2 [22]. The S2 molecule in its triplet ground state has also been produced by photolysis of H2S2 [23], S2CI2 [20, 24], and Me2S2 [25], for example. The S2 vapor spectrum is characterized by the Schumann-Runge bands transition Voo=316 nm [26]) which at high temper-... 

In addition to the chain-like and cyclic species discussed so far the presence of branched rings and chains in sulfur vapor and in liquid sulfur has been discussed [46] but no conclusive experimental evidence for such iso-... 

In addition to the branched rings and chains, cyclic Ss conformations of lower symmetry than Did are also likely components of liquid sulfur. For example, the following exo-endo isomer of Ss (Cs symmetry) is by just 28 kJ mor (AG°29s) less stable than the ground state conformation and therefore its relative concentration in liquid sulfur and sulfur vapor at the boiling point will also be 1% of all Ss species [35]. 

If hot sulfur melts or hot sulfur vapors at low pressure are frozen at low temperatures highly colored samples are obtained which may be black, green or red depending on the temperature and pressure conditions and on the rate of quenching [69]. These colors originate from the small molecules and radicals, present at high temperatures, which become trapped in the solid sample. At room temperature these samples turn yellow, provided the sulfur has been very pure. 

Raman spectra of S2 in its triplet ground state have been recorded both in sulfur vapor and after matrix isolation using various noble gases. The stretching mode was observed at 715 cm in the gas phase [46], and at 716 cm in an argon matrix [71]. From UV absorption and fluorescence spectra of sulfur vapor the harmonic fundamental mode of the S2 ground state was derived as t e = 726 cm . The value corrected for anharmonicity is 720 cm [26, 27]. Earlier reports on the infrared absorption spectrum of 2 in matrix isolated sulfur vapor [72] are in error the observed bands at 660, 668 and 680 cm are due to S4 [17] and other species [73]. 

Since 1960 mass spectrometry has always been an important tool to investigate the molecular composition of sulfur vapor, sulfur melts, and the solid dlotropes [201]. Mostly spectra obtained by electron impact (El) ionization have been reported, except for one study in which the main species present in sulfur vapor (S2-Ss) were studied by photoionization mass spectrometry [202]. The following ionization potentials were reported (in eV) [202] ... 

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