Esterification activity and stability of Candida rugosa lipase immobilized into chitosan

Microbial lipase from Candida rugosa immobilized into porous chitosan beads was tested for esterification selectivity with butanol and different organic acids (C2–C12), and butyric acid and different aliphatic alcohols (C2–C10). After 24 h, the acids tested achieved conversions of about 40–45%. Acetic acid was the only exception, and in this case butanol was not consumed. Different alcohols led to butyric acid conversions >40%, except for ethanol, in which case butyric acid was converted only 26%. The system’s butanol and butyric acid were selected for a detailed study by employing an experimental design. The influence of temperature, initial catalyst concentration, and acid:alcohol molar ratio on the formation of butyl butyrate was simultaneously investigated, employing a 2³ full factorial design. The range studied was 37–50°C for temperature (X₁), 1.25–2.5% (w/v) for the catalyst concentration (X₂), and 1 and 2 for the acid:alcohol molar ratio (X₃). Catalyst concentration (X₂) was found to be the most significant factor and its influence was positive. Maximum ester yield (83%) could be obtained when working at the lowest level for temperature (37°C), highest level for lipase concentration (2.5% [w/v]), and center level of acid:alcohol molar ratio (1.5). The immobilized lipase was also used repeatedly in batch esterification reactions of butanol with butyric acid, revealing a half-life of 86 h.     

Microwave saturation of EPR spectra of oxidised coal

Microwave saturation of multi-component EPR spectra of oxidized lignite Mequinenza (Spain) with a carbon content of 65.1 wt % and with a high sulphur content of 10.3 wt % was studied. The coal was oxidized with nitric acid (NHO₃), peroxyacetic acid (PAA), and in O₂/Na₂CO₃ system. Three different groups of paramagnetic centres exist in the coal samples analyzed. The EPR spectrum of the demineralised coal was a superposition of broad Gauss (ΔB _pp = 0.75 mT), broad Lorentz 1 (ΔB _pp = 0.42 mT) and narrow Lorentz 3 lines (ΔB _pp = 0.08 mT). The three EPR components with linewidths: 0.58–0.77 mT (Gauss line), 0.30–0.39 mT (Lorentz 1 line) and 0.05–0.06 mT (Lorentz 3 line) were recorded for the oxidized coal. The g-values were obtained for the samples studied in the ranges 2.0043–2.0046 (Gauss lines), 2.0035–2.0038 (Lorentz 1 lines) and 2.0032–2.0034 (Lorentz 3 lines). The broad Gauss and Lorentz 1 lines saturate at low microwave powers. The narrow Lorentz 3 lines of demineralised coal were not saturated at microwave power from the range considered. After the coal oxidation with HNO₃, PAA and in O₂/Na₂CO₃ system, the microwave saturation of the narrow Lorentz 3 lines was also observed, which indicated a degradation of the multi-ring aromatic structures upon oxidation.      

Adding value to the Brazilian sisal: acid hydrolysis of its pulp seeking production of sugars and materials

The present work is inserted into the broad context of the upgrading of lignocellulosic fibers. Sisal was chosen in the present study because more than 50% of the world’s sisal is cultivated in Brazil, it has a short life cycle and its fiber has a high cellulose content. Specifically, in the present study, the subject addressed was the hydrolysis of the sisal pulp, using sulfuric acid as the catalyst. To assess the influence of parameters such as the concentration of the sulfuric acid and the temperature during this process, the pulp was hydrolyzed with various concentrations of sulfuric acid (30–50%) at 70 °C and with 30% acid (v/v) at various temperatures (60–100 °C). During hydrolysis, aliquots were withdrawn from the reaction media, and the solid (non-hydrolyzed pulp) was separated from the liquid (liquor) by filtering each aliquot. The sugar composition of the liquor was analyzed by HPLC, and the non-hydrolyzed pulps were characterized by viscometry (average molar mass), and X-ray diffraction (crystallinity). The results support the following conclusions: acid hydrolysis using 30% H₂SO₄ at 100 °C can produce sisal microcrystalline cellulose and the conditions that led to the largest glucose yield and lowest decomposition rate were 50% H₂SO₄ at 70 °C. In summary, the study of sisal pulp hydrolysis using concentrated acid showed that certain conditions are suitable for high recovery of xylose and good yield of glucose. Moreover, the unreacted cellulose can be targeted for different applications in bio-based materials. A kinetic study based on the glucose yield was performed for all reaction conditions using the kinetic model proposed by Saeman. The results showed that the model adjusted to all 30–35% H₂SO₄ reactions but not to greater concentrations of sulfuric acid. The present study is part of an ongoing research program, and the results reported here will be used as a comparison against the results obtained when using treated sisal pulp as the starting material.     

Gas chromatographic analysis of C2−C16 dicarboxylic acids esterified in aqueous solutions as n-propyl esters

Summary C₂−C₁₆ dicarboxylic acids were esterified in aqueous solution in the presence of sulfuric acid. Esterification in water/n-propanol mixtures with mole ratios between 0.03 and 2.21 can be utilized for the quantitative determination of dicarboxylic acids by gas chromatography. The presence of water does not interfere at water/n-propanol mole ratios below 0.45. For mole ratios above 0.45 anhydrous sodium sulfate has been used for binding the water. The mole ratio range tested was 0.12–0.99 for anhydrous sodium sulfate/water, and 0.16–2.55 for sulfuric acid/anhydrous sodium sulfate.     

Physico-chemical properties of ambiently dried sodium silicate based aerogels catalyzed with various acids

Experimental results on the physico-chemical properties of ambiently dried sodium silicate based aerogels catalyzed with various acids are reported. The aerogels were prepared by hydrolysis and polycondensation of sodium silicate followed by subsequent washings, surface chemical modification and ambient pressure drying using 10 various acid catalysts consisting of strong and weak acids. The strength and concentration of acids have the major effect on the gelation of sol and hence the physico-chemical properties of the silica aerogels. Strong acids such as HCl, HNO₃ and H₂SO₄ resulted in shrunk (70–95%) aerogels whereas weak acids such as citric and tartaric acids resulted in less shrunk (34–50%) aerogels. The physical properties of silica aerogels were studied by measuring bulk density, volume shrinkage (%), porosity (%), pore volume, thermal conductivity, contact angle with water, Transmission Electron Microscopy (TEM), Atomic Absorption Spectroscopy (AAS), Fourier Transform Infrared Spectroscopy (FTIR), Thermo Gravimetric-Differential Thermal (TG-DT) analyses and N₂ adsorption–desorption BET surface analyzer. The best quality silica aerogels in terms of low density (0.086 g/cm³), low volume shrinkage (34%), high porosity (95%), low thermal conductivity (0.09 W/m K) and hydrophobic (148°) were obtained for molar ratio of Na₂SiO₃:H₂O:citric acid:TMCS at 1:146.67:0.72:9.46 with 20 min gelation time. The resulting aerogels exhibited the thermal stability up to around 420 °C.     

Surface treatment of LLDPE and LDPE blends by nitric acid,sulfuric acid,and chromic acid etching

Surface treatment of linear low density polyethylene and low density polyethylene blends is investigated herein using nitric acid, sulfuric acid, and chromic acid. These chemical treatments not only make the surface rough but also introduce polar groups. A new method, “sulfonic groups index” (SI) is employed to quantify the newly generated polar groups in the wavenumber of 1,250–840 cm⁻¹ in the Fourier transform infrared spectra. The SI values effectively indicate that the most polar groups are incorporated into the chromic acid-etched samples among the three inorganic acids, which is also confirmed by scanning electron microscopy and roughness tests. Besides, annealing treatment can enhance the crystallinity X _c of all etched samples which plays a predominant role in the increase of roughness within 2 h. As etching time increases, chain scission and destruction of amorphous parts happen and roughness increases a lot for chromic acid-treated samples, but for sulfuric acid- and nitric acid-treated samples, the destruction of amorphous parts may not happen so that the roughness has not many changes.     

Simultaneous GC-MS quantitation of acids and sugars in the hydrolyzates of immunostimulant, water-soluble polysaccharides of basidiomycetes

Summary The simultaneous quantitation of acids and sugars as their trimethyl silyl (TMS) derivatives has been extended in order to identify and quantitate the simple acid and sugar constituents in the hydrolyzates of various immunostimulant, water-soluble polysaccharides obtained from various Basidiomycetes, such as Armillariella mellea, Auricularia auricula-judae, Coriolus versicolor, Flammulina velutipes, Fomes fomentarius, Ganoderma applanatum, Ganoderma lucidum, Pleurotus ostreatus, Schizophyllum commune, Trametes hirsuta. Optimum hydrolysis conditions, performed with 2 M trifluoroacetic acid (TFAA) for five hrs, proved the presence of several sugars and acids with maximum recovery. (i) the total sugar/sugar alcohol content of polysaccharides varied between 20- and 65% and consisted of arabitol (0.01–10.2%), arabinose (0.09–1.3%), ribose (0.2–1.8%), fucose (0.3–1.2%), mannitol (0.01–5.3%), sorbitol (0.01–0.05%), galactiol (0.04%), fructose (0.08–0.8%), galactose (0.9–29%), glucose (10–53%), uronic acids (0.14–3.7%), sucrose (0.03–2%), trehalose (0.2–1%), cellobiose (0.01–0.6%), maltose (0.2–1.9%), other disaccharides (0.2–8%). (ii) The total of acids varied from 1.5 to 30% including o-phosphoric (1.3–19%), malic (0.08–4.7%), citric (0.08–4.7%), isocitric; (3%) and C₁₆−C₁₈ fatty acids (1–6%).     

Comparison of SO2 and H2SO4 impregnation of softwood prior to steam pretreatment on ethanol production

The pretreatment of softwood with sulfuric acid impregnation in the production of ethanol, based on enzymatic hydrolysis, has been investigated. The parameters investigated were: H₂SO₄ concentration (0.5 – 4.4% w/w liquid), temperature (180 – 240°C), and residence time (1-20 minutes). The combined severity (log Ro-pH) was used to combine the parameters into a single reaction ordinate. The highest yields of fermentable sugars, i.e., glucose and mannose, were obtained at a combined severity of 3. At this severity, however, the fermentability declined and the ethanol yield decreased. In a comparison with previous results, SO₂ impregnation was found to be preferable, since it resulted in approximately the same sugar yields, but better fermentability.     

Liquid-liquid extraction separation of uranium(VI) from associated elements using dibenzo-24-crown-8 from hydrobromic acid medium

Liquid-liquid extraction of uranium (VI) from hydrobromic acid solutions with dibenzo-24-crown-8 in nitrobenzene have been investigated. Uranium(VI) was quantitatively extracted from 6.0–8.0M hydrobromic acid with 0.001–0.01M dibenzo-24-crown-8 and was quantitatively stripped from the organic phase with 0.1–1.0M hydrochloric acid, 0.5–10M nitric acid, 2–10M perchloric acid, 3.0–10M sulfuric acid or 3.0–10M acetic acid. It was possible to separate uranium(VI) from a number of elements in binary mixtures. Most of the elements showed very high tolerance limit Uranium(VI) was also separated from a number of associated elements in multicomponent mixtures. The method is very simple, selective, rapid and highly reproducible (approximately±2%) and was applied to the analysis of uranium in geological samples.     

On the emitters of sulfuric acid sonoluminescence

A comparative study of the sonoluminescence spectra of water and argon-saturated aqueous H₂SO₄ solutions was carried out. At an H₂SO₄ concentration of 18 mol L⁻¹, the sulfuric acid sonoluminescence is fifty times more intense than water sonoluminescence. The sulfuric acid luminescence spectrum differs from the water sonoluminescence spectrum caused by the emission of excited water molecules and OH radicals from the gas phase of cavitation bubbles. The sulfuric acid sonoluminescence spectrum exhibits maxima at 330, 420, 500, and 630 nm. Emitters of sonoluminescence of sulfuric acid are the singlet (330–340 nm) and triplet (∼420 nm) excited SO₂ molecules formed by sonolysis of H₂SO₄ molecules. Another product of sonolysis of H₂SO₄, atomic oxygen, is assumed to be responsible for the luminescence at λ = 630 nm. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1742–1745, August, 2005.     

Reactivities of heterocyclic compounds in niration. 4. Kinetics and mechanism of nitration of 2-picrylaminopyridine in sulfuric acid

The kinetics of nitration of 2-picrylaminopyridine with nitric acid in 85– 96% sulfuric acid were studied by a spectrophotometric method. It is shown that 2-picrylaminopyridine undergoes the reaction in the protonated form. The kinetic parameters of the nitration and the relative reactivity as compared with benzene were calculated. See [1] for communication 3. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 363–365, March, 1980.     

Nitration of photochromic spirophenanthroxazine

Nitration of photochromic spirophenanthrooxazine with three different reagents (cupric nitrate, NaNO₂ in acetic acid, and HNO₃-H₂SO₄) was studied. The major reaction products were specified and characterized by ¹H and ¹³C NMR and mass spectra. The mechanisms of their formation were proposed. Only the nitration with a mixture of nitric and sulfuric acids yielded a photochromic product containing the nitro group in the phenanthrene fragment. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1670–1677, July, 2005.     

Effects of the composition of acid solutions and the presence of organic acids on oxygen electroreduction to hydrogen peroxide in a carbon black gas-diffusion electrode

This paper reports on the effects of the K₂SO₄, H₂SO₄, NaCl, HCl, and tetrabutylammonium bromide concentrations (0.01–0.0002 M) and the presence of formic, acetic, and butyric acids in the electrolyte on the kinetic characteristics of oxygen reduction to H₂O₂ in a carbon black gas-diffusion electrode (GDE) and on the H₂O₂ accumulation kinetics in electrolyte at current densities of 30–100 mA/cm². The introduction of K₂SO₄ and tetrabutylammonium bromide in the electrolyte led to an increase in the transfer coefficient α and a decrease in the coefficients in the Tafel equation. The concentration and the current efficiency of H₂O₂ decreased with the salt to acid concentration ratio. The organic acids reduced the current efficiency of H₂O₂ and increased the electrode polarization. Peracids with a current efficiency of up to 0.27% and concentration of up to 7.5 mM were obtained. Solutions of H₂O₂ with concentrations of 0.6–3.3 M and current efficiencies of 17–75% were obtained at current densities of 30–100 mA/cm² in electrolytes with salt and inorganic acid concentrations of 0.9–40 g/l and in the presence of organic acids.     

Solvent extraction of chromium(VI) from base metal ions with diphenyl-2-pyridylmethane as a liquid anion exchanger

The extraction of chromium(VI) from aqueous hydrochloric, nitric and sulfuric acid solutions by diphenyl-2-pyridylmethane(DPPM) dissolved in chloroform has been studied. Chromium(VI) is quantitatively extracted from hydrochloric acid solutions in the range 0.1–1M. With increasing acid concentration, the extraction of chromium diminishes and in concentrated acid solutions practically all the chromium remains in the aqueous phase. The quantitative back-extraction of chromium from the organic phase is possible with HCl or HNO₃ at concentrations higher than 5M through the use of reducing agents. The composition of the extracted chromium(VI) species was studied in solution. The complexes (DPPMH)⁺HCrO ₄ ⁻ and (DPPMH)₂Cr₂O ₇ ⁻ are extracted for tracer and macro amounts of chromium(VI) respectively. The data have been utilized for the separation of chromium(VI) from base metal ions.     

Synthesis and characterization of trichlorogermyl dioic acids: crystal structures and complementary hydrogen bonding motifs in 3-(trichlorogermyl) pentanedioic acid and 2-[(trichlorogermyl)methyl]butanedioic acid

A series of trichlorogermyl-substituted dicarboxylic acids of general formula HOOC–R′–COOH where R′=–CH₂CH(GeCl₃)CH₂– 1, –CH(CH₂GeCl₃)CH₂– 2, –CH(GeCl₃)CH₂– 3 and –CH(CH₃)CH(GeCl₃)– 4 were synthesized by the hydrogermylation reaction of unsaturated acids, such as trans-glutaconic (2-pentenedioic acid), itaconic (methylenebutanedioic acid), fumaric (2-butenedioic acid), and citraconic (2-methyl-2-butenedioic acid) acids with HGeCl₃, which was produced in situ by the reaction of GeO₂ with 37% HCl in presence of NaH₂PO₂ · H₂O. All these compounds were characterized by melting point, CHN analysis, FTIR, and multinuclear NMR (¹H; ¹³C; H,H-COSY). X-Ray crystal structures of 1 and 2 were analyzed to show supramolecular structures in which central Ge atom in each of these structures is four-coordinated with a slightly distorted tetrahedral geometry. Structurally, both compounds adopt supramolecular forms via strong intermolecular O–H–O interactions through 8-membered and 22-membered hydrogen bonded rings. Supplementary material to this paper is available in electronic form at Correspondence: Muhammad Mazhar, Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan.     

Kinetics of sodium ethylenediaminetetraacetate mineralization by cerium(IV) in nitric acid medium

The process of sodium ethylenediaminetetraacetate (EDTA) mineralization by cerium(IV) in nitric acid medium was studied in batch and continuous feeding modes. In the batch mode EDTA solution was fed into the reactor in one stroke and in the continuous mode it was fed with a constant flow rate during a definite time interval. Cerium(IV) concentration was kept at high and constant level by selecting correct relation between cerium(IV) production in the electrochemical cell and the EDTA added. During the organic mineralization process cerium(IV) is reduced to cerium(III). The process was carried out at different temperatures, concentrations of nitric acid and cerium(IV). To obtain the limiting factors in the batch mode reaction, the dependence of CO₂ evolution with time and carrier gas blowing rate was studied. Application of the model previously developed by us to the continuous process gave us the possibility to calculate pseudo first order kinetic constant on the basis of CO₂ evolution data of both EDTA destruction regimes during feeding mode and after stopping organic addition. The efficiency of organic destruction estimated on the basis of CO₂ evolved was in the range 75–95% and on the basis of liquid phase residual organic carbon analysis 95–99%.     

Experimental study of a closed system in the chlorine dioxide–iodine–ethyl acetoacetate–sulfuric acid oscillation reaction by UV–vis and online FTIR spectrophotometric methods

The appearance of oscillations depends critically on the pH for a closed system of ClO₂–I₂–ethyl acetoacetate in the absence of sulfuric acid, and was investigated by determining the absorbance of I₃⁻ with reaction time at 280 nm. The pH should be 2.2–3.8. The initial concentration of ethyl acetoacetate, chlorine dioxide, iodine, and sulfuric acid has great influence on the oscillation at 581 nm for I₃⁻–starch complex (SI₃⁻). The oscillation occurs as long as the reactants are mixed at 280 nm. There is no pre-oscillatory period. However, at 581 nm, there is an induction period. The curve’s shape at 581 nm is very different from that at 280 nm. The oscillation becomes more obvious by adding starch at 581 nm for I₃⁻–starch complex (SI₃⁻) than that observed without adding starch at 280 nm. The oscillation curve is more regular and smooth by adding starch at 581 nm than that without adding starch at 280 nm. The amplitude and the number of oscillations are associated with the initial concentration of reactants. The higher the initial concentration of ethyl acetoacetate, the bigger the amplitude. Also, the number of oscillations becomes small. An opposite influence exists for chlorine dioxide and iodine. The higher the initial concentration of sulfuric acid, the bigger the amplitude. Also, the number of oscillations becomes large. The equations for the triiodide ion reaction rate changing with reaction time and the initial concentrations on the oscillation stage were obtained. The intermediates were detected by the online FTIR analysis. Based upon the experimental data in this work and in the literature, a plausible reaction mechanism was proposed for the oscillation reaction.     

4-(5-Nonyl)pyridine as an extractant for cobalt thiocyanate complexes from mineral acid solutions

The partition behaviour of cobalt into 4-(5-nonyl)pyridine (NPy) in benzene from aqueous hydrochloric, nitric and sulfuric acid media containing variable amounts of potassium thiocyanate is described. Cobalt is quantitatively extracted by NPy from 0.1–1M KSCN solutions at 0.01 M concentration of the mineral acids. The extraction mechanism and the possible compositions of the extracted species are discussed. The effects of foreign salts on the extraction of cobalt from three mineral acid solutions are reported. Several elements including those which are of some interest in connection with the separation of cobalt were tested for extraction from 0.01 M solutions of mineral acids 0.3 M with respect to KSCN and their factors for separation from cobalt were estimated.     

Kinetics of β-picoline oxidation to nicotinic acid over vanadia-titania catalyst. 3. The oxidation of nicotinic acid

The oxidation of nicotinic acid (NA) over binary vanadia-titania catalysts with different contents of residual sulfate ions (0.2 and 2.8 wt. %) was studied at 250–300°C in the feed reaction mixture of the composition NA: O₂: H₂O = 0.01–0.17: 5–20: 0–20 (vol. %), with nitrogen as a balance. The kinetic parameters of the process were determined. It was shown that even a ten-fold increase in the content of residual sulfate ions in the samples has no significant effect on the kinetics of the NA oxidation.     

Determination of Hydrofluoric Acid in Mixed Acids with an Acid Concentration Meter

Abstract

A commercial acid concentration meter containing an N-type silicon anode and stainless cathode has been used to selectively measure hydrofluoric acid in mixtures containing nitric, phosphoric and sulfuric acids. At very high weight ratios of acid to HF (> 10:1) a suppression in HF response was noted for all acids examined. At lower ratios or higher HF values only nitric acid influences HF response with a sensitizing or catalytic effect not appreciably dependent on HNO, concentration.