Oxidative dimerization of primary alcohols to esters catalyzed by iridium complexes

Primary alcohols undergo efficiently oxidative dimerization by iridium complexes under air without any solvent to form esters in fair to good yields. For instance, the reaction of 1-dodecanol in the presence of [IrCl(coe)₂]₂ (3 mol %) at 95 °C for 15 h produced dodecyl dodecanoate in 91% isolated yield. This is the first successful Ir-catalyzed oxidative dimerization of primary alcohols to esters using air as an oxidant. Various primary alcohols are converted to the corresponding esters in fair to good yields.     

Liquid-phase alkylation of phenol with long-chain olefins over WOx/ZrO2 solid acid catalysts

The liquid-phase alkylation of phenol with 1-dodecene was carried out over WO_x/ZrO₂ solid acid catalysts. The catalysts were prepared by wet impregnation method using zirconium oxyhydroxide and ammonium metatungstate. Catalysts with different WO₃ loading (5–30 wt.%) were prepared and calcined at 800 °C and catalyst with 15% WO₃ was calcined from 700–850 °C. All the catalysts were characterized by surface area, XRD, and FTIR. The catalyst with 15% WO₃ calcined at 800 °C (15 WZ-800) was found to be the most active in the reaction. The effect of temperature, molar ratio and catalyst weight on dodecene conversion and products selectivity was studied in detail. Under the optimized reaction conditions of 120 °C, phenol/1-dodecene molar ratio 2 and time 2 h, the catalyst 15 WZ-800 gave >99% dodecene conversion with 90% dodecylphenol selectivity. Comparison of the catalytic activity of 15 WZ-800 with sulfated zirconia calcined at 500 °C (SZ-500) and Hβ zeolite showed that activity of SZ-500 was lower than that of 15 WZ-800, while Hβ zeolite showed negligible activity. It is observed that the presence of water in the reaction mixture was detrimental to the catalytic activity of WO_x/ZrO₂. The catalyst 15 WZ-800 also found to be an efficient catalyst for alkylation of phenol with long-chain olefins like 1-octene and 1-decene.     

Liquid phase mononitration of chlorobenzene over WOx/ZrO2: A study of catalyst and reaction parameters

To study the effect of W concentration and activation temperature of the catalysts a series of WO_x/ZrO₂ samples with varying concentration of W (10–25 wt.%) were prepared and activated at 650/750 °C. XRD of sample shows 15 wt.% W stabilizes the tetragonal phase of zirconia up to 750 °C. Above and less than 15 wt.% shows peaks corresponding to monoclinic WO₃ and monoclinic ZrO₂, respectively. Further, the tungsten modification stabilizes the specific surface area of ZrO₂. There is an increase in the surface area observed up to 15 wt.% W, which declines on further increase in the concentration. The NH₃ TPD confirms the presence of acid sites with varying strength from the broad desorption profile. The 15 wt.% W and activated at 750 °C shows maximum acidity. The results of the nitration reaction of chlorobezene imply the 15 wt.% W and activation at 750 °C shows maximum activity. Not only yield, a better para-selectivity is also achieved with WO_x/ZrO₂ samples. Effect of activation temperature, W concentration and reaction parameters such as reaction temperature, reaction time, the presence of solvent and solvent free medium on activity and selectivity are studied in details.     

Synthesis and properties of polyether ketones

Polyether ketones were prepared by the nucleophilic reaction of dihaloaromatic ketones with aromatic bisphenols (hydroquinone, resorcinol and 4,4-dihydroxybenzophenone) using various solvents in the presence of anhydrous K₂CO₃. Dihaloaromatic ketones (4,4-difluorobenzophenone/4,4-dichlorobenzophenone) were prepared from the reaction of fluorobenzene/chlorobenzene with carbon tetrachloride in the form of AlCl₃. The polymers were characterized by different physico-chemical techniques. Thermogravimetric studies showed that all the polymers were stable upto 500°C with a char yield above 50% at 900°C in N₂ atmosphere. Isothermal degradation at 400°C under air and N₂ atmosphere reveals about 5% weight loss and about 1% weight loss at 75 min respectively. The effect of solvents, reaction temperature and reaction time on molecular weights are discussed. The effect of the annealing time on crystallinity of the polymers is also discussed.     

Thermal solid–solid interactions and physicochemical properties of NiO/Fe2O3 system doped with K2O

The effects of calcination temperature and doping with K₂O on solid–solid interactions and physicochemical properties of NiO/Fe₂O₃ system were investigated using TG, DTA and XRD techniques. The amounts of potassium, expressed as mol% K₂O were 0.62, 1.23, 2.44 and 4.26. The pure and variously doped mixed solids were thermally treated at 300, 500, 750, 900 and 1000 °C. The catalytic activity was determined for each solid in H₂O₂ decomposition reaction at 30–50 °C. The results obtained showed that the doping process much affected the degree of crystallinity of both NiO and Fe₂O₃ phases detected for all solids calcined at 300 and 500 °C. Fe₂O₃ interacted readily with NiO at temperature starting from 700 °C producing crystalline NiFe₂O₄ phase. The degree of reaction propagation increased with increasing calcination temperature. The completion of this reaction required a prolonged heating at temperature >900 °C. K₂O-doping stimulates the ferrite formation to an extent proportional to its amount added. The stimulation effect of potassium was evidenced by following up the change in the peak height of certain diffraction lines characteristic NiO, Fe₂O₃, NiFe₂O₄ phases located at “d” spacing 2.08, 2.69 and 2.95 Å, respectively. The change of peak height of the diffraction lines at 2.95 Å as a function of firing temperature of pure and doped mixed solids enabled the calculation of the activation energy (ΔE) of the ferrite formation. The computed ΔE values were 120, 80, 49, 36 and 25 kJ mol⁻¹ for pure and variously doped solids, respectively. The decrease in ΔE value of NiFe₂O₄ formation as a function of dopant added was not only attributed to an effective increase in the mobility of reacting cations but also to the formation of potassium ferrite. The calcination temperature and doping with K₂O much affected the catalytic activity of the system under investigation.     

Equilibrium of the reaction between dissolved sodium sulfide and biologically produced sulfur

The equilibrium of the heterogeneous reaction between dissolved sodium sulfide and biologically produced sulfur particles has been studied. Biologically produced sulfur was obtained from a bioreactor of a hydrogen sulfide removal process in which the dominating organism is Thiobacillus sp. W5. Detailed knowledge of this reaction is essential to understand its effect on the process. The results were compared with the equilibrium of the reaction of sulfide with ‘inorganic’ elemental sulfur. The equilibrium between dissolved sodium sulfide and biologically produced sulfur particles can be described by an equilibrium constant, K_x, which consists of a weighted sum of constants for polysulfide ions of different chain length, rather than a true single equilibrium constant. For biologically produced sulfur pK_x = 9.10 ± 0.08 (21 °C) and 9.17 ± 0.09 (35 °C) with an average polysulfide chain length x = 4.91 ± 0.32 (21 °C) and 4.59 ± 0.31 (35 °C). The pK_x value for biologically produced sulfur is significantly higher than for reaction of dissolved sodium sulfide with inorganic sulfur (pK_x = 8.82; 21 °C). This difference is probably caused by the negatively charged polymeric organic layer, which is present on biologically produced sulfur but absent with “inorganic” sulfur. Specific binding of polysulfide ions to the organic layer results in a higher polysulfide concentration at the reaction site compared to the bulk concentration. This results in an apparent decrease of the measured equilibrium constant, K_x.     

Benefits of donor solvents as additive on ROMP of norbornene catalyzed by amine Ru complexes

With the aim of understanding the influence of donor solvents on the reactivity of the amine complexes [RuCl₂(PPh₃)₂(piperidine)] (1) and [RuCl₂(PPh₃)₂(imidazole)₂] (2) in the presence of ethyldiazoacetate, and on the properties of the resulting polymer, a ring opening metathesis polymerization of norbornene was carried out in the presence of small amounts of common solvents such as additives (isopropanol, THF, N,N-dimethylformamide, 2,6-lutidine, isopropanethiol, acetonitrile, dimethyl sulfoxide, NEt₃, NH₂Me and pyridine). From observations, typical coordinating solvents like DMSO, NEt₃, NH₂Me and pyridine, hardly affected the yields when either complex was employed. With other additives, the major advantage was the decrease in the polydispersity indices. On using complex 1 with 2,6-lutidine, observed values of M_w/M_n were as low as 1.3, while the yield decreased from 99% to about 20–30% at RT for 1 min in pure solution. In the case of complex 2, which is almost inactive to ROMP (19% at 50 °C for 5 min with M_w/M_n = 6.30), the yield was three-fold (60% at 50 °C for 5 min with M_w/M_n = 1.95) compared to that of without THF. Further, the M_w/M_n was observed to decrease to 1.34 with 200 eq. of THF.     

Solid state synthesis and characterization of iron（Ⅱ） pyrophosphate Fe2P2O7

Offwhite pure Fe_2P_2O_7 was synthesized through solid phase reaction using Fe_2O_3 and NH_4H_2PO_4 in argon atmosphere.The reaction products of Fe_2O_3 and NH4_H_2PO_4 at a series of temperatures from 400 to 900℃were characterized by XRD.Comparison and analysis of XRD patterns of resultant products indicated well-crystallized Fe_2P_2O_7 could be obtained over 630℃and Fe_2P_2O_7 prepared at 700℃was triclinic in cell type.Comparison of the cell parameters proved that the as-prepared Fe_2P_2O_7 belonged toβ- Fe_2P_2O_7 in crystal phase and SEM showed its size distribution was 0.5-2μm.     

Decomposition of toluene using an atmospheric pressure plasma/TiO2 catalytic system

Application of atmospheric pressure plasma as an alternative technology for the destruction of toluene is demonstrated in this study. Used TiO₂ colloidal solution was obtained by an improved sol–gel method, and coated on glass beads to prepare decomposition of toluene. The physical property of synthesized TiO₂ catalyst film was analyzed by XRD and SEM spectroscopy. From these results, it was identified that the catalyst film exhibited anatase structure with particle size of about 50–100 nm after calcination at 500 °C for 1 h. The decomposition of toluene in TiO₂/O₂ plasma system was investigated. Amounts of the catalyst and toluene concentration were fixed as 3 wt.% and 1000 ppm, respectively. The analyses for performance of toluene decomposition and intermediates in reaction were done by the in situ method using the mass spectroscopy and gas chromatography. The toluene of 40% was decomposed at pulse voltage of 13 kV in the only O₂ plasma condition without TiO₂ catalyst. Furthermore, the conversion enhanced remarkably in the TiO₂/O₂ plasma system, and it reached 70% at pulse voltage of 13 kV after 120 min. This result was very notable compared with that in photocatalytic system, with below 40% after 120 min reaction.     

Zwitterionic titanoxanes {Cp[η-C5H4B(C6F5)3]Ti}2O and {(η-PrC5H4)[η-1,3-PrC5H3B(C6F5)3]Ti}2O as catalysts for cationic ring-opening polymerization

Zwitterionic titanoxanes {Cp[η⁵-C₅H₄B(C₆F₅)₃]Ti}₂O (I) and {(η⁵-ⁱPrC₅H₄)[η⁵-1,3-ⁱPrC₅H₃B(C₆F₅)₃]Ti}₂O (II), which contain two positively charged Ti(IV) centres in the molecule, are able to catalyse the ring-opening polymerization of -caprolactone (-CL) in toluene solution and in bulk. The process proceeds with a noticeable rate even at room temperature and accelerates strongly on raising the temperature to 60 °C. The best results have been obtained on carrying out the reaction in bulk. Under these conditions, the use of I as a catalyst (-CL:I = 1000:1) gives at 60 °C close to quantitative yield of poly--CL with the molecular mass of 197 000. An increase in the -CL:I ratio to 6000:1 increases the molecular mass of poly--CL to 530 000. Tetrahydrofuran (THF) is also polymerized under the action of I albeit with a lesser rate. However, the molecular mass of the resulting poly-THF can reach rather big values under optimal conditions (up to 217 000 at 20 °C and the THF:I ratio of 770:1). A rise in the reaction temperature from 20 to 60 °C results here to a decrease in the efficiency of the process. Titanoxane II is close to I in its catalytic activity in the -CL polymerization but it is much less active in the polymerization of THF. Propylene oxide (PO), in contrast to -CL and THF, gives with I only liquid oligomers in wide temperature and PO:I molar ratio ranges (−30 to +20 °C, PO:I = 500–2000:1). γ-Butyrolactone and 1-methyl-2-pyrrolidone are not polymerized under the action of I at room temperature. The reactions found are the first examples of catalysis of the cationic ring-opening polymerization by zwitterionic metallocenes of the group IVB metals.     

Preparation and characterization of sulfated zirconia (SO4/ZrO2)/Nafion composite membranes for PEMFC operation at high temperature/low humidity

Fine particle superacidic sulfated zirconia (SO₄²⁻/ZrO₂, S-ZrO₂) was synthesized by ameliorated method, and composite membranes with different S-ZrO₂ contents were prepared by a recasting procedure from a suspension of S-ZrO₂ powder and Nafion solution. The physico-chemical properties of the membranes were studied by ion exchange capacity (IEC) and liquid water uptake measurements, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis, thermogravimetry–mass spectrometry (TG–MS) and Fourier transform infrared (FT-IR) spectroscopy. The results showed that the IEC of composite membrane increased with the content of S-ZrO₂, S-ZrO₂ was compatible with the Nafion matrix, the incorporation of the S-ZrO₂ could increase the crystallinity and also improve the initial degradation temperature of the composite membrane. The performance of single cell was the best when the S-ZrO₂ content was 15 wt.%, and achieved 1.35 W/cm² at 80 °C and 0.99 W/cm² at 120 °C based on H₂/O₂ and at a pressure of 2 atm, the performance of the single cell with optimized S-ZrO₂ was far more than that of the Nafion at the same condition (e.g. 1.28 W/cm² at 80 °C, 0.75 W/cm² at 120 °C). The 15 wt.% S-ZrO₂/Nafion composite membrane showed lower fuel cell internal resistance than Nafion membranes at high temperature and low relative humidity (RH).     

Effects of heat on physicochemical properties of whey protein-stabilised emulsions

The effect of heating has been studied for whey protein-stabilised oil-in-water emulsions (25.0% (w/w) soybean oil, 3.0% (w/w) whey protein isolate, pH 7.0). These emulsions were heated between 55 and 95 °C as a function of time and the effect on particle size distribution, adsorbed protein amount, protein conformation and rheological properties was determined. Heating the emulsions as a function of temperature for 25 min resulted in an increase of the mean diameter (d₃₂) and shear viscosity with a maximum at 75 °C. Heating of the emulsions at different temperatures as a function of time in all cases resulted in a curve with a maximum for d₃₂. A maximum increase of d₃₂ was observed after about 45 min at 75 °C and after 6–8 min at 90 °C. Similar trends were observed with viscosity measurements. Confocal scanning laser micrographs showed that after 8 min of heating at 90 °C large, loose aggregates of oil droplets were formed, while after 20 min of heating compact aggregates of two or three emulsion droplets remained. An increase of the adsorbed amount of protein was found with increasing heating temperature. Plateau values were reached after 10 min of heating at 75 °C and after 5 min of heating at 90 °C. Based on these results we concluded that in the whole process of aggregation of whey protein-stabilised emulsions an essential role is played by the non-adsorbed protein fraction, that the kinetics of the aggregation of whey protein-stabilised emulsions follow similar trends as those for heated whey protein solutions and that upon prolonged heating rearrangements take place leading to deaggregation of initially formed large, loose aggregates of emulsion droplets into smaller, more compact ones.     

Oxidative dehydrogenation of ethane to ethylene over NiO loaded on high surface area MgO

The oxidative dehydrogenation of ethane over NiO-loaded MgO with high surface area was carried out using a fixed-bed flow reactor at 600 °C under atmospheric pressure.

At 600 °C, the oxidative dehydrogenation of ethane (C₂H₆/O₂ = 1) without dilution with an inert gas resulted in C₂H₆ conversion of 68.8% and a high C₂H₄ selectivity of 52.8%, which corresponds to a C₂H₄ yield of 36.3%. In addition, the catalytic activity did not decrease for at least 10 h. X-ray photoelectron spectra of the catalysts after the reaction exhibited that the initial valence state of Ni²⁺ (NiO) was maintained during the oxidative dehydrogenation of ethane. However, when NiO-loaded MgO was reduced with H₂ prior to the reaction, C₂H₄ selectivity decreased to nearly zero and high CO and H₂ selectivities were observed with the C₂H₆ conversion of 50 %, indicating that partial oxidation of C₂H₆ proceeded. Therefore, it seems important to keep Ni species as an oxide phase on the support, and for this purpose, use of the high surface area of MgO is essential.     

1-Butyl-2,3-trimethyleneimidazolium bis(trifluoromethylsulfonyl)imide ([b-3C-im][NTf2]): a new, stable ionic liquid

Using imidazole as the starting material, the synthesis of a new bicyclic ionic liquid [b-3C-im][NTf₂] is described. Except for the alkylation reaction in the second step (40% yield) of this four-step synthesis of [b-3C-im][NTf₂], others were all high yielding reactions (85-94% isolated yields). We investigated intrinsic reactivity of this and other imidazolium-based ionic liquids and found that, under strongly basic conditions (KOD in CD₃OD/D₂O (1:1) solution), the new ionic liquid was stable to solvent deuterium isotope exchange while the previously reported [bdmim][NTf₂] and [bdmim][PF₆] ionic liquids were 50% deuterium exchanged at its C-2 methyl in 30 min at ambient temperature. At the same experimental condition, the most commonly employed [bmim][PF₆] ionic liquid was deuterium exchanged instantaneously at its C-2 hydrogen. In the absence of bases (CD₃OD/D₂O = 1:1), only [bmim][PF₆] was deuterium exchanged (50% within 1 h) and other ionic liquids gave no detectable exchanges even after one week at ambient temperature. It is therefore concluded that the new [b-3C-im][NTf₂] ionic liquid is far more chemically stable than previously reported [bmim][PF₆], [bdmim][NTf₂], and [bdmim][PF₆].     

Stabilisation of emulsions using hydrophobically modified inulin (polyfructose)

Oil-in-water (O/W) emulsions were prepared using a hydrophobically modified inulin surfactant, INUTEC^®SP1. The quality of the emulsions was evaluated using optical microscopy. Emulsions, prepared using INUTEC^®SP1 alone had large droplets, but this could be significantly reduced by addition of a cosurfactant to the oil phase, namely Span 20. The stability of the emulsions was investigated in water, in 0.5, 1.0 and 2 mol dm⁻³ NaCl as well as 0.5, 1.0, 1.5 and 2 mol dm⁻³ MgSO₄. All emulsions containing NaCl did not show any strong flocculation or coalescence up to 50 °C for almost 1 year storage. With MgSO₄ they were stable up to 50 °C and 1 mol dm⁻³. The stability of the emulsions against strong flocculation and coalescence could be attributed to the conformation of the polymeric surfactant at the O/W interface (multipoint attachment with several loops) and the strong hydration of the polyfructose chain in such high electrolyte concentrations. This was confirmed using cloud point measurements, which showed absence of any cloudiness up to 100 °C and at NaCl concentrations reaching 4 mol dm⁻³ and MgSO₄ reaching 1 mol dm⁻³. These high cloud points in electrolyte solutions could not be reached with polyethylene glycol. This clearly demonstrated the superiority of INUTEC^®SP1 surfactant as an emulsion stabiliser when compared with surfactants based on polyethylene glycol. Viscoelastic measurements showed a gradual increase in the storage modulus G′ with storage time both at room temperature and 50 °C. This was indicative of weak flocculation and absence of coalescence. The weak flocculation of the emulsions could be attributed to the presence of an energy minimum, G_min, in the energy–distance curve.     

An investigation on the solid state pyrolytic decomposition of bimetallic oxalate precursors of Ca, Sr and Ba with cobalt: A mechanistic approach

The mixed metal oxalate precursors, calcium(II)bis(oxalato)cobaltate(II)hydrate (COC), strontium(II)bis(oxalato)cobaltate(II)pentahydrate (SOC) and barium(II)bis(oxalato)cobaltate(II)octahydrate (BOC) have been synthesized and their thermal stability was investigated. The complexes were characterized by elemental analysis, IR spectral and X-ray powder diffraction studies. Thermal decomposition studies (TG, DTG and DTA) in air showed that the compound COC decomposed mainly to CaC₂O₄ and Co₃O₄ at 340 °C, and a mixture of CaCO₃ and Co₃O₄ identified at 510 °C. A mixture of CaCO₃ and Ca₃Co₂O₆ along with the oxides and carbides of both the cobalt and calcium were attributed at 1000 °C as end products. DSC study in nitrogen ascertained the formation of a mixture of CaO and CoO along with a trace of carbon at 550 °C. The mixture species, SrC₂O₄, CoC₂O₄ and Co₃O₄ were generated at 255 °C in case of SOC in air, which ultimately changed to CoSrO₃, SrCO₃ and oxides of strontium and cobalt at 1000 °C. The several mixture species also generated as intermediate at 332 and 532 °C. The DSC study in nitrogen indicated the formation of CoSrO_x (0.5 < x < 1) as end product. In case of BOC in air, a mixture of BaCoO₂, BaO, CoO and carbides are identified as end product at 1000 °C through the generation of several intermediate species at 350 and 530 °C. A mixture of BaO and CoO is identified as end product in DSC study in nitrogen. The kinetic parameters have been evaluated for all the dehydration and decomposition steps of all the three compounds using four non-mechanistic equations. Using seven mechanistic equations, the kind of dominance of kinetic control mechanism of the dehydration and decomposition steps are also inferred. The kinetic parameters, ΔH and ΔS of all the steps are explored from the DSC studies. Some of the decomposition products are identified by IR and X-ray powder diffraction studies.     

Gaseous nitryl azide N4O2: A joint theoretical and experimental study

Gaseous nitryl azide N₄O₂ is generated by the heterogeneous reaction of gaseous ClNO₂ with freshly prepared AgN₃ at −50 °C. The geometric and electronic structure of the molecule in the gas phase has been characterized by in situ photoelectron spectroscopy (PES) and quantum chemical calculations. The experimental first vertical ionization energy of N₄O₂ is 11.39 eV, corresponding to the ionization of an electron on the highest occupied molecular orbital (HOMO) {4a″(π_{nb(N4–N5–N6)})}⁻¹. An apparent vibrational spacing of 1600 ± 60 cm⁻¹ (ν_asO1N2O3) on the second band at 12.52 eV (π_{nb(O1–N2–O3)}) further confirms the preference of energetically stable chain structure in the gas phase. To complement the experimental results, the potential-energy surface of this structurally novel transient molecule is discussed. Both calculations and spectroscopic results suggest that the molecule adopts a trans-planar chain structure, and a five-membered ring decomposition pathway is more favorable.     

Supported carbon molecular sieve membranes based on a phenolic resin

The preparation of a composite carbon membrane for separation of gas mixtures is described. The membrane is formed by a thin microporous carbon layer (thickness, 2 μm) obtained by pyrolysis of a phenolic resin film supported over a macroporous carbon substrate (pore size, 1 μm; porosity, 30%). The microporous carbon layer exhibits molecular sieving properties and it allows the separation of gases depending on their molecular size. The micropore size was estimated to be around 4.2 Å. Single and mixed gas permeation experiments were performed at different temperatures between 25°C and 150°C, and pressures between 1 and 3.5 bar. The carbon membrane shows high selectivities for the separation of permanent gases like O₂/N₂ system (selectivity≈10 at 25°C). Gas mixtures like CO₂/N₂ and CO₂/CH₄ are successfully separated by means of prepared membranes. For example, the membrane prepared by carbonization at 700°C shows at 25°C the following separation factors: CO₂/N₂≈45 and CO₂/CH₄≈160.     

A simultaneous TG–DTA study of the thermal decomposition of 2-hydroxybenzoic acid, 2-carboxyphenyl ester (salsalate)

Simultaneous thermogravimetry–differential thermal analysis (TG–DTA) and gas and liquid chromatography with mass spectrometry detection have been used to study the kinetics and decomposition of 2-hydroxybenzoic acid, 2-carboxyphenyl ester, commercially known as salsalate. Samples of salsalate were heated in the TG–DTA apparatus in an inert atmosphere (100 ml min⁻¹ nitrogen) in the temperature range 30–500 °C. The data indicated that the decomposition of salsalate is a two-stage process. The first decomposition stage (150–250 °C) had a best fit with second-order kinetics with E_a=191–198 kJ/mol. The second decomposition stage (300–400 °C) is described as a zero-order process with E_a=72–80 kJ/mol. The products of the decomposition were investigated in two ways:

(a)Salsalate was heated in a gas chromatograph at various isothermal temperatures in the range 150–280 °C, and the exit gas stream analyzed by mass spectrometry (GC–MS). This approach suggested that salsalate decomposes with the formation of salicylic acid, phenol, phenyl salicylate, and cyclic oligomers of salicylic acid di- and tri-salicylides.

(b)One gram samples of salsalate were heated in a vessel under nitrogen to 150 °C, and the residues were analyzed by liquid chromatography–mass spectrometry (LC–MS). The major compound detected was a linear tetrameric salicylate ester.

     

High temperature reaction of SiCl4 and O2 in quartz tubes

The reaction between SiCl₄ and O₂ at 1 atm between 25 and 1200°C has been followed by mass spectrometry. Below 600°C no reaction with O₂ is noted. Above 600°C the reaction proceeds in two steps. Between 800 and 1000°C the ²⁸Si/³²O₂ peak height ratio is constant with no evolution of Cl₂. It is suggested that silicon oxychlorides are being formed in this temperature regime. Above 1000°C the reaction between SiCl₄ and O₂ intensifies with concomitant production of Cl₂. It is suggested that above 1000°C the reaction SiCl₄ + O₂ → SiO₂ + Cl₂ becomes important.

At low temperatures (<800°C) adsorbed H₂O and OH groups from the surface of the fused silica tube react with SiCl₄ to form HCl. The importance of this reaction decreases with increasing temperature. The increased production of HCl above 1000°C is ascribed to H₂O and H₂ diffusing from the tube.