Speed of sound and isentropic compressibility of organic solvents + sunflower oil mixtures at 298.15 K

The speed of sound in binary liquid mixtures of organic solvents with sunflower oil was measured over the entire range of concentrations at 298.15 K. The solvents considered were: n-hexane, n-heptane, n-octane, n-nonane, ethanol, 1-propanol, 2-propanol, 1-butanol, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and vinyl acetate. The speed of sound data were used to calculate isentropic compressibilities and excess isentropic compressibilities. The excess isentropic compressibilities vs. concentrations were correlated using Redlich-Kister polynomials. Speed of sound determinations in the mixtures were predicted using two mixing rules proposed in the literature, and values were compared with experimental data. In all cases, SD between predicted and experimental data were less than 3.5%.     

Oviposition stimulants of the mothEctomyelois ceratoniae: The effect of short-chain alcohols

Females of the mothEctomyelois ceratoniae prefer to oviposit on carobs,Ceratonia siliqua L., infested with the fungusPhomopsis sp. (Gothilf, 1964). An extract of the steam distillate of fungus-infested carobs was more effective in stimulating female moths to oviposit than was an extract of uninfested carobs. The extract of the fungus-infested carobs was found to be composed mainly of simple alcohols: ethanol (60%),n-propanol3 (15%), 2-propanol (2.5%), isobutanol (15%),n-butanol (2.5%), and isopentanol (5%). In addition, the extract contained a small proportion (1–2%) of unidentified compounds. All of the alcohols, with the exception of isopentanol, stimulated oviposition by female moths. However, the alcohols, when tested separately or as a mixture, were not as stimulating as the total extract. The unidentified compounds were less stimulating than the alcohols.     

In-situ alcoholysis of soybean oil

In-situ alcoholysis of soybean oil with methanol, ethanol,n-propanol, andn-butanol was investigated, as well as the extraction of the oil with these solvents, to explain the progress ofin-situ alcoholysis and to determine the parameters that affect this reaction. Because methanol is a poor solvent for soybean oil, the amount of oil dissolved in methanol and converted to methyl esters was low afterin-situ alcoholysis. Ethyl, propyl, and butyl esters of soybean fatty acids could be obtained in high yields fromin-situ alcoholysis of soybean oil with these alcohols.In-situ alcoholysis proceeded through dissolution and alcoholysis of triglycerides successively, and the overall reaction rate was determined by the extraction and alcoholysis rates. The parameters, affecting yield and purity of the product esters, were mainly those that favor extraction rate.     

Chemical and ultrastructural analysis of corn cuticular lipids and their effect on feeding by fall armyworm larvae

The cuticular lipid composition of lower and upper leaves of five genotypes of field-grown corn,Zea mays L., was determined by combined gas chromatography-mass spectrometry. Surface lipids of the upper leaves had a higher proportion ofn-alkanes (45–52%) than the lower leaves, while the lower leaves had higher percentages of fatty alcohols (12–18%) than the upper leaves. Scanning electron microscopy showed that the upper leaves of two corn genotypes, MpSWCB-4 and Cacahuacintle X's, had a smooth amorphous appearance, while the lower leaves had a dense array of wax crystals.Spodoptera frugiperda (J.E. Smith) larvae weighed more and developed more rapidly when they were reared on diet containing corn foliage from which the cuticular lipids had been removed than when they were fed untreated foliage. However, growth was not inhibited when larvae were fed diet containing the cuticular lipid extracts or individual cuticular lipid components.     

Partition coefficient calculation of selected terpenes and low molecular weight solvents between tall oil fatty acid and air and polydimethyl siloxane oil and air

Headspace gas chromatography-mass spectrometry (GC-MS) has been applied to the analysis of the temperature-dependent tall oil fatty acid (TOFA)/air partition coefficient (k ₁) and the polydimethyl siloxane oil/air partition coefficient (k ₂) of selected terpenes and low molecular weight solvents. As expected, both the TOFA and the silicone oil are effective trapping media for the nonpolar terpenes, but they are also efficient traps for acetone, methanol, n-propanol, and n-butanol. However, several species of low and moderate molecular weight (less than 150 amu) aldehydes, ketones, and organic acids that might adversely affect its trapping capacity were detected in the TOFA. This article will report the empirically gathered data and the subsequent calculation of the partition coefficients for the terpenes: α- and β-pinene, limonene, and α-terpineol and the solvents: acetone, methanol, n-propanol, and n-butanol between 50 and 130°C.     

Experimental and predicted enthalpies of mixing of mixtures formed from alcohols and sunflower oil at 298.15 K

The enthalpies of mixing of systems formed from alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol) and sunflower oil at 298.15 K are presented. Enthalpies were measured in the composition range in which the compounds were miscible. From the experimental measurements, we calculated the heat capacities of the mixtures. Several group contribution models were applied to estimate the enthalpies of mixing of these mixtures. The average deviations varied from 10 to 60%, depending on the model and compound. The best prediction in all cases was the Nitta model, with average deviations from 10 to 30%. The novelty of the work is that models of this type have not been applied previously to predict enthalpies of such large molecules, and the results of the estimates are of the same order as other types of compounds (pure compounds of small size).     

Improvement in the gas chromatographic resolution of petroselinate from oleate

In the extraction of oils from seeds of the genus Coriandrum, GC separations of petroselinate from oleate often gave poor resolution of these two isomers. Oleic and petroselinic acids were esterified with a series of alcohols (methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 3-methyl-1-butanol, and 2-ethyl-1-hexanol). GC resolution of the Δ6 from the Δ9 and Δ11 octadecenoates was examined for all ester derivatives on a polar phase column. The Δ6 and Δ9 isomers were unresolved as methyl esters; however, the 2-ethyl-1-hexyl esters gave baseline separation of all three isomers under temperature programming conditions. When isothermal conditions were optimized for each ester, separation of these isomers was possible with good resolution values (>89%) for all the alcohols except methanol, which had a partial resolution of 51%. The rates of esterification of all the alcohols were determined for reactions with both oleic acid and triolein using potassium hydroxide as the esterification catalyst. Methanol gave the largest rate constant in both acid and oil esterification reactions with a rate constant 10-fold better than all of the other alcohols. Based on rates of reaction, resolution of petroselinate from oleate, and removal of residual alcohol, the ethyl ester derivative appears to be the best choice for seed oils containing petroselinic acid.     

Critical temperatures and pressures and high temperature vapour pressures of seven alcohols

Critical temperatures and pressures have been determined experimentally for the four lowest n-alcohols, 2-propanol, 2-butanol, and 2-methyl-1-propanol, and are given in the penultimate line of Table 3. The last line of Table 3 lists the weighted mean critical pressures, with the corresponding critical temperatures obtained from he vapour pressure equation. Comparison with the corresponding data from standard reference books reveals deviations from the experimental data in some [2, 4] and incorrect critical pressure for ethanol in all five reference books quoted in Table 3. In addition, vapour pressure data were obtained for the same alcohols in the temperature range approaching the critical point. The measurements are reproduced by the simplified Clausius-Clapeyron equation with the constants and standard deviation given in Table 2.     

A generalized corresponding states method for predicting the limits of superheat of mixtures: Application to the normal alcohols

The limits of superheat of the normal alcohols from methanol to octanol and of ethanol/n-propanol, n-propanol/n-butanol, and n-butanol/n-pentanol mixture were measured at atmospheric pressure. The results were predicted using a new method based on the generalized corresponding states principle (GCSP) in which properties of two reference substances were used to predict the superheat limits of the fluids studied. Ethanol and n-butanol, and the two components of each mixture studied, were used as reference fluids for predicting the superheat limits of the pure alcohols and mixtures respectively.Results showed that it is possible to predict superheat limits to well within the accuracy of measured values ( < 1%). The method requires only accurate vapor pressure correlations and acentric factors of the reference fluids, and an accurate method for predicting the variation of the true critical mixture temperature with composition. It is shown that the GCSP reduces to an expression for the superheat limit of a mixture which is a mole fraction weighted average of the limits of superheat of the individual components in solution when the mixture and its components satisfies certain conditions. In the general case, both linear and nonlinear variations of mixture superheat limit with mole fraction can be predicted with the proposed method.Considerable simpiflication using the GCSP over the approach based on classical homogeneous nucleation theory is derived from the fact that no mixture surface tension or bubble point pressure data are required.     

Synthesis of fatty acid esters from acid oils using lipase B from Candida antarctica

Esterification of corn and sunflower acid oils with straight‐ and branched‐chain alcohols were conducted using lipase B from Candida antarctica (Novozym 435) in n‐hexane. Sunflower acid oil consisted of 55.6% free fatty acids and 24.7% triacylglycerols, while the free fatty acids and triacylglycerols contents of corn acid oil were 75.3% and 8.6%, respectively. After 1.5 h of methanolysis of sunflower acid oil, the highest fatty acid methyl ester content (63.6%) was obtained at 40 °C and the total fatty acid/methanol molar ratio was 1/1, using 15% enzyme based on acid oil weight. The conversion of both acid oils with straight‐ and branched‐chain alcohols was not significantly affected by the chain length of the alcohols. However, the lowest fatty acid methyl ester content (50%) was obtained in the reaction of corn acid oil with methanol. Sunflower acid oil was converted to fatty acid esters using primer alcohols such as n‐propanol, i‐ and n‐butanol, n‐amylalcohols, n‐octanol, and a mixture of amylalcohol isomers, resulting in a fatty acid ester content of about 70% at 40 °C.     

Base-catalyzed derivatization methodology for FA analysis. Application to milk fat and celery seed lipid TAG

In this paper, an alternative base-catalyzed methodology for the facile derivatization in mild conditions of lipid TAG prior to FA analysis is proposed. Reagents were prepared by proton exchange between potassium tert-butoxide and either ethanol, n-propanol, n-butanol, or 2-methoxyethanol and used for the synthesis, at 40°C for 15 min, of the corresponding derivatives, which were directly analyzed by GC. This methodology can be used on a routine basis and has been applied to standard and complex natural lipid samples. Tripalmitin was used to determine optimal reaction conditions; and bovine milk fat, containing C₄ to C₂₂ acids, and celery (Apium graveolens) seed oil, characterized by a high level of petroselinic acid, were comparatively analyzed as their ethyl, n-propyl, n-butyl, and 2-methoxyethyl esters.     

Epicuticular Wax Chemicals in Zea mays Influence Oviposition in Ostrinia nubilalis

The chemical basis of oviposition elicitation in a generalist herbivore was determined by examination of oviposition responses in Ostrinia nubilalis to corn (Zea mays) chemicals in two-choice laboratory bioassays. A pentane extract of corn leaves stimulated oviposition and the activity persisted for three days, indicating that oviposition in O. nubilalis is elicited by low-volatility chemicals. Chemicals in the extract were fractionated by column chromatography on Florisil, using a sequence of solvents of increasing polarity. Bioassays of Florisil fractions indicated that the stimulants were eluted with nonpolar solvents. Positive bioassay results with an extract prepared by dipping corn leaves in pentane for 20 sec for extraction of leaf surface chemicals suggested that some of the active material was present in the leaf epicuticle. Gas chromatographic analyses and comparisons with retention times of standards suggested the presence of several n-alkanes in the dip extract. Five n-alkanes—hexacosane, heptacosane, octacosane, nonacosane, and tritriacontane—known to be present in the epicuticle of corn leaves were bioassayed, and all five elicited oviposition responses. These results suggest that oviposition elicitation in O. nubilalis is influenced by the presence of n-alkanes in the host plant epicuticle.     

Supercritical alcohols as solvents and reducing agents for the synthesis of reduced graphene oxide

We report on a facile, simple, and green graphene oxide (GO) reduction method based on a supercritical alcohol approach. The influence over the chemical, thermal, morphological, and textural properties of reduced graphene oxides (RGOs) of five different alcohols in their supercritical conditions – methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol – was investigated in detail. Although the thermal stabilities and Fourier-transform infrared spectra of RGOs produced using the different alcohols are very similar, a substantial difference in the carbon-to-oxygen ratios measured by X-ray photoelectron spectroscopy and Brunauer–Emmett–Teller surface areas are observed. The RGO produced using supercritical ethanol exhibited a much higher carbon-to-oxygen ratio of 14.4 and a much larger surface area of 203 m²/g compared with that produced using the other supercritical alcohols. Raman spectra showed that the RGOs produced using supercritical ethanol and supercritical 2-propanol retained more of the graphitic structure. X-ray diffraction analysis revealed that RGOs produced using supercritical 1-propanol and supercritical 1-butanol retained at least two different interlayer spacings. The deoxygenation mechanism of GO in supercritical ethanol is proposed based on gas and liquid product analysis.     

Excess molar enthalpies of ternary and constituent binary systems {1,2-dichloropropane+2-propanol+2-butanol} at T=298.15 K

Ternary excess molar enthalpies at T=298.15 K and P=101.3 kPa for the system of {1,2-dichloropropane+2-propanol+2-butanol} and their constituent binary systems {1,2-DCP+2-propanol}, {1,2-DCP+2-butanol}, and {2-propanol+2-butanol} have been measured over the whole composition range using an isothermal micro-calorimeter with flow-mixing cell. All of the binary and ternary systems, including three pseudobinary systems, show endothermic behavior except for the binary mixture {2-propanol+2-butanol}, which shows small exothermicity. The Redlich-Kister equation was used to correlate the binary H _{m, ij} ^E data, and the Morris equation to correlate the ternary H _{m, 123} ^E data. Comparisons between the Morris and Radojkovi equations for the prediction of H _m,123 ^E have been also made. The experimental results have been qualitatively discussed in terms of self-association, isomeric effect and chain length among molecules.     

Ionic solvation—I. Free energies of transfer of copper(II) ion from water to alcohols and to their mixtures with water

The emf of the cell: Cu|Cu²⁺ in water||Cu²⁺ in water + alcohol|Cu for different alcohols (methanol, ethanol, 1-propanol, 2-propanol, t-butanol, ethylene glycol, propylene glycol and glycerol) and their mixtures with water have been measured at 25°C. These data were used for calculation of Gibbs free energies of transfer of copper(II) ion from water to nonaqueous alcohols and to their mixtures with water, with the help of negligible liquid junction potential assumption. Determined free energies of transfer are positive for all solvents studied, which may be simply interpreted assuming that copper(II)ion interacts more strongly with water molecules than with alcohol molecules, without reference to any special structural properties of these solvents.     

Esterification of styrene–maleic anhydride copolymer by mixed alcohols

A copolymer (MW = 1800) of styrene (St) and maleic anhydride (MAn) was esterified with an excess amount of an alcohol mixture, and then the relation between the esterification rates of the individual alcohols and the contents of the esters in the esterific copolymer was examined. At first, the rate constant of an individual esterification was obtained for four different alcohols (n-butanol, i-amylalcohol, and benzylalcohol) in a noncatalyst system. Then, the mixed esterification of n-butanol and i-amylalcohol was carried out; from the analysis of the ester contents, the following equation was obtained: From this result, it was concluded that, in esterification with alcohols involving n species, the content of the individual ester can be expressed by the following equation: where [P] = concentration of esters in the copolymer, [B]₀ = initial concentration of alcohols, and k = rate constant of esterification (i,j = 1,2…,n).     

TLC and <Superscript>31</Superscript>P-NMR Analysis of Low Polarity Phospholipids

High-performance TLC and ³¹P-NMR were assessed as methods of observing the presence of numerous low polarity phospholipids: bis-phosphatidic acid (BPA), semi-lyso bis-phosphatidic acid (SLBPA), N-acyl phosphatidylethanolamine (NAPE), N-(1,1-dimethyl-3-oxo-butyl)-phosphatidylethanolamine (diacetone adduct of PE, DOBPE), N-acetyl PE, phosphatidylmethanol (PM), phosphatidylethanol (PEt), phosphatidyl-n-propanol (PP), phosphatidyl-n-butanol (PB). Both techniques are non-discriminative and do not require the prior isolation of individual lipids. It appears that 2D TLC is superior to ³¹P NMR in the analysis of low polarity phospholipids. All phosphatidylalcohols were well separated by 2D TLC. However, some compounds which can present difficulty in separation by 2D-TLC (e.g., SLBPA and NAPE; or DOBPE and N-acetyl PE) were easily distinguished using ³¹P NMR so the methods are complimentary. A disadvantage of 2D TLC is that Rf values can vary with different brands and batches of TLC plates. The chemical shifts of ³¹P NMR were less variable, and so a library of standards may not be necessary for peak identification. Another advantage of ³¹P NMR is the ease of quantification of phospholipids. The applicability of the methods was tested on natural extracts of fish brain and cabbage stem.     

Study of phase behavior and Congo red dye partitioning in aqueous two-phase systems composed of hydrophilic alcohols (1-propanol/ 1-butanol) and sodium salts

ABSTRACT

The partitioning of the Congo red dye in ATPSs formed by alcohols (1-butanol, 1-propanol)/sodium salts was considered. Binodal and the LLE data were experimentally determined at 298.15 K. The salting-out abilities of the salts follow the order Na₃C₆H₅O₇ > NaH₂PO₄ > C₂H₃ O₂Na. The phase-forming abilities of the alcohols follow the order: 1-butanol > 1-propanol. The four-parameter equation was applied to correlate the binodal curves data. Therefore, The Bancroft and Othmer-Tobias equations were used to prove the reliability of the corresponding LLE data. ATPS composed of 6.5% of 1-butanol and 20% of Na₃C₆H₅O₇ had the highest values of extraction by the yield of 98.54%.     

FTIR study of gas-phase alcohols photocatalytic degradation with TiO2 and AC-TiO2

In this paper the degradation of gaseous alcohols (methanol, ethanol, 1-propanol and 1-butanol) has been studied in a continuous reaction system. Methanol and ethanol, but not 1-propanol and 1-butanol, have caused the catalyst bare-TiO₂ to become deactivated. The catalyst containing activated carbon, AC-TiO₂, has not shown almost deactivation in any experiment.

To explain this behaviour variation, a thorough FTIR study concerning the interaction of gaseous alcohols with the catalyst surface and the effect of light on the process was performed. Thus, the interaction of the different catalysts with the selected alcohols, the formed species and the hydroxyl group evolution under irradiation was studied.     

Composition of waxes from crude rice bran oil

Hard and soft waxes were separated from the tank settling of crude rice bran oil by solvent extraction and analyzed for their composition by gas liquid chromatography (GLC). The results showed that the melting points of the hard wax and the soft wax were 79.5 C and 74 C, respectively, and that the hard wax was mainly composed of saturated fatty alcohols of C24, C26 and C30, saturated fatty acids of C22, C24 and C26, andn-alkanes of C29 and C31. The soft wax was mainly composed of saturated fatty alcohols of C24 and C30, saturated fatty acids of C16 and C26, andn-alkanes of C21 and C29. In the soft wax, lauric acid was also detected.