Raman spectra from very concentrated aqueous NaOH and from wet and dry, solid, and anhydrous molten, LiOH, NaOH, and KOH

High-temperature, high-pressure Raman spectra were obtained from aqueous NaOH solutions up to 2NaOHH2O, with X(NaOH)=0.667 at 480 K. The spectra corresponding to the highest compositions, X(NaOH)> or =0.5, are dominated by H3O2-. An IR xi-function dispersion curve for aqueous NaOH, at 473 K and 1 kbar, calculated from the data of Franck and Charuel indicates that the OH- ion forms H3O2- by preferential H bonding with nonhydrogen-bonded OH groups. Raman spectra from wet to anhydrous, solid LiOH, NaOH, and KOH yield sharp, symmetric OH- stretching peaks at 3664, 3633, and 3596 cm(-1), respectively, plus water-related, i.e., H3O2-, peaks near LiOH, 3562 cm(-1), NaOH, 3596 cm(-1), and, KOH, 3500 cm(-1). Absence of H3O2- peaks from the solid assures that the corresponding melt is anhydrous. Raman spectra from the anhydrous melts yield OH- stretching peak frequencies: LiOH, 3614+/-4 cm(-1), 873 K; NaOH, 3610+/-2 cm(-1), 975 K; and, KOH, 3607+/-2 cm(-1), 773 K, but low-frequency asymmetry due to ion-pair interactions is present which is centered near 3550 cm(-1). The ion-pair-related asymmetry corresponds to the sole IR maximum near 3550 cm(-1) from anhydrous molten NaOH, at 623 K. Bose-Einstein correction of published low-frequency Raman data from molten LiOH revealed an acoustic phonon, near 205 cm(-1), related to restricted translation of OH- versus Li+, and an optical phonon, at 625 cm(-1) and tau approximately 0.05 ps, due to protonic precession and/or pendular motion. Strong H bonding between water and the O atom of OH- forms H3O2-, but the proton of OH- does not bond with H significantly. Large Raman bandwidths (aqueous solutions) are explained in terms of inhomogeneous broadening due to proton transfer in a double well. Vibrational assignments are presented for H3O2-.     

Analysis of preparation and combustion characteristics of NaOH/KOH catalyzed straw pyrolytic carbon

Journal of Thermal Analysis and Calorimetry - In this paper, wheat straw, corn straw and sorghum straw were used as raw materials. KOH and NaOH were used as catalysts to prepare straw pyrolytic...     

Characterization of hydroxyaromatic compounds in vegetable oils by capillary electrophoresis with direct injection in an oil-miscible KOH/propanol/methanol medium

The separation of hydroxyaromatic compounds in vegetable oils, including synthetic antioxidants (3-tert-butyl-4-hydroxyanisol and 2,6-di-tert-butyl-4-hydroxytoluene), E-vitamers and other natural oil components, by nonaqueous capillary electrophoresis in an oil-miscible background electrolyte (BGE) was investigated. The BGE contained 40 mM KOH in a methanol/1-propanol (PrOH) mixture (15:85 v/v). The oil samples were 1:1 diluted with PrOH and directly injected in the capillary. Under negative polarity (cathode at the injection end), the anionic solutes moved faster than the electroosmotic flow, being well-resolved among them and from the triacylglycerols. Using virgin palm, extra virgin olive, wheat germ, virgin soybean and other oils, the capability of the procedure to quickly yield a characteristic profile of the biophenols present in the sample was demonstrated. The alpha-, (beta + gamma)- (as unresolved pair) and delta-tocopherols of a soybean oil sample were quantified.     

Measurement and modelling of solubility for calcium sulfate dihydrate and calcium hydroxide in NaOH/KOH solutions

The solubility of calcium sulfate dihydrate (CaSO₄·2H₂O) and calcium hydroxide (Ca(OH)₂) in alkali solutions is essential to understand their desilication behavior from Bayer liquor. In this work, solubilities of calcium sulfate dihydrate and calcium hydroxide for the ternary systems of CaSO₄·2H₂O–NaOH–H₂O, CaSO₄·2H₂O–KOH–H₂O, and Ca(OH)₂–NaOH–H₂O were measured by using the classic isothermal dissolution method over the temperature range of 25–75 °C. The Pitzer model embedded in Aspen Plus platform was used to model the experimental solubility data for these systems. The experimental solubility data was employed to obtain the new binary interaction parameters for Ca(OH)⁺–OH⁻, Ca(OH)⁺–Ca²⁺ and Ca(OH)⁺–K⁺, suggesting that the species Ca(OH)⁺ is a dominant species in simulated solubility for alkali systems. Validation of the parameters was performed by predicting the solubility for the ternary systems of Ca(OH)₂–NaOH–H₂O, CaSO₄·2H₂O–NaOH–H₂O and CaSO₄·2H₂O–KOH–H₂O with the overall average relatively deviation (ARD) of 2.12%, 0.75% and 1.63%, respectively.     

Hydrogen/chlorine exchange reactions of gaseous carbanions

Gas-phase reactions of three typical carbanions CH(2)NO(2)(-), CH(2)CN(-), and CH(2)S(O)CH(3)(-) with the chloromethanes CH(2)Cl(2), CHCl(3), and CCl(4), examined by tandem mass spectrometry, show a novel hydrogen/chlorine exchange reaction. For example, reaction between the nitromethyl anion CH(2)NO(2)(-) and carbon tetrachloride CCl(4) forms the ion CHClNO(2)(-). The suggested reaction mechanism involves nucleophilic attack by CH(2)NO(2)(-) at the chlorine of CCl(4) followed by proton transfer within the resulting complex [CH(2)ClNO(2) + CCl(3)(-)] to form CHClNO(2)(-) and CHCl(3). Two other carbanions CH(2)CN(-) and CH(2)S(O)CH(3)(-) also undergo the novel hydrogen/chlorine exchange reactions with CCl(4) but to a much smaller extent, their higher nucleophilicities favoring competitive nucleophilic attack reactions. Proton abstraction is the exclusive pathway in the reactions of these carbanions with CHCl(3). While CH(2)CN(-) and CH(2)S(O)CH(3)(-) promote mainly proton abstraction and nucleophilic displacement in reactions with CH(2)Cl(2), CH(2)NO(2)(-) does not react.     

Rate coefficients for the reactions of OH with n‐propanol and iso‐propanol between 237 and 376 K

The rate coefficients for the reaction OH + CH₃CH₂CH₂OH → products (k₁) and OH + CH₃CH(OH)CH₃ → products (k₂) were measured by the pulsed‐laser photolysis–laser‐induced fluorescence technique between 237 and 376 K. Arrhenius expressions for k₁ and k₂ are as follows: k₁ = (6.2 ± 0.8) × 10^?12 exp[?(10 ± 30)/T] cm³ molecule^?1 s^?1, with k₁(298 K) = (5.90 ± 0.56) × 10^?12 cm³ molecule^?1 s^?1, and k₂ = (3.2 ± 0.3) × 10^?12 exp[(150 ± 20)/T] cm³ molecule^?1 s^?1, with k₂(298) = (5.22 ± 0.46) × 10^?12 cm³ molecule^?1 s^?1. The quoted uncertainties are at the 95% confidence level and include estimated systematic errors. The results are compared with those from previous measurements and rate coefficient expressions for atmospheric modeling are recommended. The absorption cross sections for n‐propanol and iso‐propanol at 184.9 nm were measured to be (8.89 ± 0.44) × 10^?19 and (1.90 ± 0.10) × 10^?18 cm² molecule^?1, respectively. The atmospheric implications of the degradation of n‐propanol and iso‐propanol are discussed. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 42: 10–24, 2010     

Interfacial reactions of duplex stainless steels with molten aluminum

The morphology and constitution of the intermetallic layers formed on the surface of duplex stainless steels (DSSs) immersed in molten aluminum at 750 °C for 30 min have been studied in detail by scanning electron microscopy and electron probe micro‐analyzer. Compared with H13 steel, the DSSs exhibited a better corrosion resistance. The weight loss rates, as expressed in terms of weight loss per square centimeter of the specimen per minute, of DSSs are smaller than that of H13. The thickness of the intermetallic layers of DSSs is comparatively thinner. And the interface between the intermetallic layers and DSSs substrate is much flatter. The intermetallic layers of duplex stainless steels are consisted of inner continuous (Fe,Cr)₂Al₅ phase and outer porous (Fe,Cr)Al₃ phases. Microstructure observations suggest that the retarded interfacial reaction between DSSs and molten aluminum is associated with a continuous Al‐Fe‐Cr intermetallic phases layer formed on the solid/liquid interface, which acts as an effective diffusion barrier. The precipitation phase particles distributed along the austenite/ferrite and ferrite/ferrite interfaces also had a good effect on the corrosion resistance properties of DSSs to molten aluminum. Copyright © 2015 John Wiley & Sons, Ltd.     

The investigation of sodium titanates by the hydrothermal reactions of TiO2 with NaOH

The hydrothermal reactions of TiO₂ with NaOH were performed in the molar range of Na₂O from 0 to 30% between 250 and 530°C. The compounds obtained were TiO₂ (rutile, brookite, and anatase), Na₂O·nTiO₂ (n = 3, 4, 6, and 9) and Na_xTiO₂, the formation ranges for which are shown in a reaction diagram. The roles of water in this hydrothermal system are investigated, to discuss the differences among the known and the present reaction diagrams and to raise a reliability of diagrams. From the present reaction diagram, phase relations in the system TiO₂Na₂O are estimated taking account of direct or indirect actions of hydrothermal water on solid phases.     

Gas phase infrared multiple-photon dissociation spectra of methanol, ethanol and propanol proton-bound dimers, protonated propanol and the propanol/water proton-bound dimer

The infrared multiphoton dissociation (IRMPD) spectra of three homogenous proton-bound dimers are presented and the major features are assigned based on comparisons with the neutral alcohol and with density functional theory calculations. As well, the IRMPD spectra of protonated propanol and the propanol/water proton-bound dimer (or singly hydrated protonated propanol) are presented and analysed. Two primary IRMPD photoproducts were observed for each of the alcohol proton bound dimers and were found to vary with the frequency of the radiation impinging upon the ions. For example, when the proton-bound dimer absorbs weakly a larger amount of S(N)2 product, protonated ether and water, are observed. When the proton-bound dimer absorbs more strongly, an increase in the simple dissociation product, protonated alcohol and neutral alcohol, is observed. With the aid of RRKM calculations this frequency dependence of the branching ratio is explained by assuming that photon absorption is faster than dissociation for these species and that only a few photons extra are necessary to make the higher-energy dissociation channel (simple cleavage) competitive with the lower energy (S(N)2) reaction channel.     

Low temperature synthesis of layered NaxCoO2 and KxCoO2 from NaOH/KOH fluxes and their ion exchange properties

We report a low temperature synthesis of layered Na_0.20Co0₂ and K_0.44CoO₂ phases from NaOH and KOH fluxes at 400°C. These layered oxides are employed to prepare hexagonal HCoO₂, Li_xCoO₂and Delafossite AgCoO₂ phases by ion exchange method. The resulting oxides were characterised by powder X-ray diffraction, X-ray photoelectron spectroscopy, SEM and EDX analysis. Final compositions of all these oxides are obtained from chemical analysis of elements present. Na_0.20Co0₂ oxide exhibits insulating to metal like behaviour, whereas AgCoO₂ is semiconducting. Dedicated to Professor C N R Rao on his 70th birthday     

Heterogeneous reactions of gaseous methanesulfonic acid with calcium carbonate and kaolinite particles

Heterogeneous reactions of gaseous methanesulfonic acid (MSA) with calcium carbonate (CaCO₃) and kaolinite particles at room temperature were investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatography (IC). Methanesulfonate (MS^?) was identified as the product in the condensed phase, in accordance with the product of the reaction of gaseous MSA with NaCl and sea salt particles. When the concentration of gaseous MSA was 1.34 × 10¹³ molecules cm^?3, the uptake coefficient was (1.21 ± 0.06) × 10^?8 (1σ) for the reaction of gaseous MSA with CaCO₃ and (4.10 ± 0.65) × 10^?10 (1σ) for the reaction with kaolinite. Both uptake coefficients were significantly smaller than those of the reactions of gaseous MSA with NaCl and sea salt particles.     

Heterogeneous reactions of gaseous methanesulfonic acid with NaCl and sea salt particles

Methanesulfonic acid (MSA) has been identified as one of the most important intermediate products of DMS reactions in the atmosphere. Although considerable amounts of MSA have been found in the marine boundary layer, little is known about the interaction of gaseous MSA with sea salt particles. To understand the fate of MSA in the atmosphere and its potential importance in atmospheric chemistry, the heterogeneous reactions of gaseous MSA with micron-scale NaCl and sea salt particles were studied using diffuse reflectance infrared Fourier transform spectrometry, X-ray photoelectron spectroscopy, and scanning electron microscopy. The CH₃SO₃Na and CH₃SO₃ ⁻ were the major products of the condensed phase of the reaction of gaseous MSA with NaCl and with sea salt particles. The steady-state uptake coefficient was determined to be (5.94±2.32)×10⁻⁷ (1 σ) for the reaction of gaseous MSA with NaCl particles and (2.23±1.25)×10⁻⁷ (1 σ) for the reaction of gaseous MSA with sea salt particles. The heterogeneous reaction of MSA with NaCl particles was found to be first-order for MSA. The reaction mechanisms were discussed. Supported by the National Natural Science Foundation of China (Grant No. 40490265) and the National Basic Research Priorities Program (Grant No. 2002CB410802)     

The formation of metal—carbon bonds via insertion reactions in gaseous negative ion/molecule reactions

The negative ion mass spectra under chemical ionization conditions for a series of copper(II), nickel(II), and cobalt(II) Schiff base complexes have been measured. Reagent gases employed include methane, isobutane, and methane-d₄. For all complexes, molecular negative ions were produced with all three reagent gases via secondary electron capture processes. Ion/molecule reactions between the molecular negative ion and the neutral reactant gas appear to be the dominant processes for the formation of secondary ions. The secondary reactions lead to the incorporation of the CH₂ moiety into the nickel(II) complexes and the CH₃ group into the cobalt(II) compounds.     

Anodic reactions of sulphate in molten salts

Electrochemical behaviour of sulphate under anodic polarization in molten sodium chloride, cryolite and sodium fluoride was investigated by cyclic voltammetry and chronopotentiometry at the temperatures of 820°C, 1010°C, and 1000°C, respectively. Using a platinum working electrode, two waves were observed on the chronopotentiograms in the systems: NaCl-Na₂SO₄ and Na₃AlF₆-Na₂SO₄. The first wave was attributed to the formation of oxygen. The second wave probably originated from the reaction of oxygen with platinum, or from oxidation of SO₃ decomposition products. Three waves were observed for the anodic process of sulphate ions dissolved in molten sodium fluoride. The first wave was attributed to the formation of oxygen. The second and the third wave were attributed to the formation of PtO and PtO₂. This conclusion was supported by cyclic voltammetry experiments of the in-situ formed sulphide in molten NaCl at 820°C and by chronopotentiometry on a gold working electrode in the system NaCl-Na₂SO₄, where no anodic wave was observed.     

Electroactive-paper actuator made with cellulose/NaOH/urea and sodium alginate

In an earlier work we reported the discovery of cellulose as a smart material that can be used in sensors and actuators. While the cellulose-based Electro-Active Paper (EAPap) actuator has many merits – lightweight, dry condition, biodegradability, sustainability, large displacement output and low actuation voltage – its performance is sensitive to humidity. We report here on an EAPap made with a cellulose and sodium alginate that produces its maximum displacement at a lower humidity level than the earlier one. To fabricate this EAPap, we dissolved cellulose fibers into a aqueous solution of NaOH/urea. Sodium alginate (0, 5 or 10% by weight) was then added to this cellulose solution. The solution was cast into a sheet and hydrolyzed to form a wet cellulose-sodium alginate blend film. After drying, a bending EAPap actuator was made by depositing thin gold electrodes on both sides of it. The performance of the EAPap actuator was then evaluated in terms of free displacement and blocked force with respect to the actuation frequency, activation voltage and content of sodium alginate. The actuation principle is also discussed.     

Thermodynamics for ionization of water at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa: apparent molar volumes of aqueous KCl,KOH, and NaOH and apparent molar heat capacities of aqueous HCl,KCl, KOH,and NaOH

Apparent molar volumes V_φof aqueous KCl, KOH, and NaOH and apparent molar heat capacities C_{p, φ}of aqueous HCl, KCl, KOH, and NaOH have been determined at the pressure p =  0.35 MPa, and at molalities 0.015 ⩽m / mol · kg ^− 1⩽ 0.5. Densities were measured using a vibrating-tube densimeter (DMA 512, Anton Paar, Austria) at temperatures 278.15 ⩽T / K⩽ 368.15. These values were used to calculate the apparent molar volumes. A fixed-cell, differential-output, power-compensating, temperature-scanning calorimeter (NanoDSC model 6100, Calorimetry Sciences Corporation, Spanish Fork, UT, U.S.A.) was used to measure the heat capacities of the same solutions at temperatures 278.15 ⩽T / K⩽ 393.15. Results were fitted by using equations that describe the surfaces (m, T, V_φ) and (m, T, C_{p, φ}). Using these equations, we have calculated the surfaces (m, T, Δ_rV_m), (m, T, Δ_rC_{p, m}), (m, T, Δ_rH_m), (m,T , p Q_a), and (m, T,Δ_rS_m ) for the ionization of water in the presence of combinations of the above electrolytes. The last three surfaces were calculated by integration using our (m,T , Δ_rC_{p, m}) surface and literature values for the molality dependence of Δ_rH_mand pQ_a at T =  298.15 K.     

Products of the gas‐phase photooxidation reactions of 1‐propanol with OH radicals

An experimental investigation of the hydroxyl radical initiated gas‐phase photooxidation of 1‐propanol in the presence of NO was carried out in a reaction chamber using gas chromatography mass spectrometry. The products identified in the OH radical reactions of 1‐propanol were propionaldehyde and acetaldehyde, with corresponding formation yields of 0.719 ± 0.058 and 0.184 ± 0.030, respectively. Errors represent ±2σ. The experimental product yields were compared to predictions made using chemical mechanisms. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 810–818, 1999