Propyl Acetate Research Articles

Solubility modeling, mixing properties and solvent effect of 5-norbornene-2,3-dicarboximide in eleven pure solvents at various temperatures

Mole-fraction solubility of 5-norbornene-2,3-dicarboximide (NODI) in eleven solvents including methanol (MtOH), ethanol (EtOH), 2-ethoxyethanol, methyl acetate (MAC), ethyl acetate (EAC), n-propyl acetate (NPAC), isopropyl acetate (IPAC), n-butyl acetate (NBAC), acetone (DMK), N,N-dimethylformamide (DMF) at (278.15–323.15) K and 1,4-dioxane at (288.15–323.15) K was experimentally measured by laser monitoring technique under 0.1 MPa. Solubility of NODI increased with the increasing temperature. Hansen Solubility Parameter was employed to explain the solubility behavior. The Kamlet-Taft parameters were calculated to investigate the solvent effect based on linear solvation energy relationships concept. Thermodynamic modeling including the Two-Suffix Margules model, Wilson model, NRTL model, NRTL-SAC model and UNIQUAC model were employed to correlate the experimental solubility. Wilson model and NRTL-SAC model were more suitable in correlation with solubility data. Furthermore, thermodynamic properties of mixing process (ΔmixG, ΔmixH, ΔmixS, lnγ1∞, H1E,∞, ζTS and ζH) were discussed based on Wilson equation.

Solid-liquid equilibrium solubility and thermodynamic properties of cis-5-norbornene-endo-2,3-dicarboxylic anhydride in fourteen pure solvents and three binary solvents at various temperatures

Solubility of cis-5-norbornene-endo-2,3-dicarboxylic anhydride (carbic anhydride) in fourteen pure solvents including methyl acetate (MAC), ethyl acetate (EAC), n-propyl acetate (NPAC), isopropyl acetate (IPAC), n-butyl acetate (NBAC), n-amyl acetate (NAAC), isoamyl acetate (IAAC), hexyl acetate (HAC), octyl acetate (OAC), ethanol (EtOH), 1,4-dioxane, 1-methyl-2-pyrrolidinone (NMP), acetone, N,N-dimethylformamide (DMF) and three binary solvents of (DMF + EtOH), (1,4-dioxane + EtOH) and (EtAC + EtOH) with various mass fractions was experimentally studied at various temperatures under 0.1 MPa. The results showed that solubility of carbic anhydride increased with the increasing temperature in all pure/binary solvents and decreased with the increasing mass fractions of ethanol in binary solvents. The Hansen solubility parameter was used for explaining the solubility order of carbic anhydride in selected solvents. Solubility of carbic anhydride in pure solvents was correlated by van't Hoff equation, modified Apelblat equation, and λh equation. Experimental solubility of carbic anhydride in binary solvents was correlated by Jouyban-Acree model, Jouyban-Acree-modified Apelblat model, Jouyban-Acree-van't Hoff model, Sun model and Ma model. Moreover, thermodynamic properties of solutions were calculated by the van't Hoff analysis. The dissolution process was always endothermal and entropy-driven.

A Series of Polyhydric Esters As Novel Candidates for Battery Solvents in Lithium Metal Cells: Electrochemical Investigations and Influences of Moisture and Alcohol Residues in Contact with Lithium Metal

In recent years, the lithium metal anode has aroused great interest, not at least through the development of the lithium//sulfur and the lithium//air battery technologies, in all-solid-state batteries. However, the application of lithium metal anodes is limited by safety issues and several failure mechanisms, including, dendrite growth and direct chemical reactions with electrolyte components like battery solvents, which leads to fast capacity losses. In this context, a new series of polyhydric propyl-based esters were investigated, namely n-propyl acetate, isopropyl acetate (monohydric esters), trimethylene diacetate, 1,2-propylene glycol diacetate (dihydric esters) and triacetin (trihydric ester) as attractive and environmental friendly candidates for electrolyte solvents in lithium metal battery applications.The above mentioned organic esters were examined in respect to their reactivity in contact with lithium metal, influenced by water or alcohol impurities. The resulting reaction products were analyzed and determined via 1H-NMR spectroscopy. Additional experiments were performed and the resulting products compared to anticipated reaction products which were prepared separately, to evidence possible reaction mechanisms like the occurrence of a CLAISEN-condensation. Furthermore, the here mentioned propyl-based esters and the reaction products were analyzed by cyclic voltammetry against copper, platinum and aluminum as working electrode to evaluate the anodic and cathodic stability, as well as possible anodic dissolution reactions in the presence of LiTFSI as conducting salt. In both cases, the reactivity in contact with lithium metal and the anodic dissolution of aluminum, a reactivity could be observed whereupon the trihydric esters were least reactive followed by the dihydric and monohydric esters. In absence of water and alcohols all investigated esters show no detectable reaction with lithium metal. ACKNOWLEDGMENT The authors want to acknowledge the German Federal Ministry for Economic Affairs and Energy (BMWi) for funding within the project FesKaBat (03ET6092E). The authors also acknowledge the analytical group of Sascha Nowak (MEET Battery Research Center, University of Münster) for all performed TXRF measurements.

Catalytic hydrogenolysis of glycerol into propyl acetate with ruthenium complexes

Ru complexes have been utilized as catalyst precursors for glycerol hydrogenolysis under mild conditions, which gave propyl acetate (PA) as a major product. Notably, the esterification reaction of acetic acid with glycerol can prevent glycerol from polymerization. In(OTf)3 played a critical role in facilitating esterification of glycerol and sequential dehydration, while the Ru complexes' function was hydrogenation. The promoter (FeCl3) can suppress the reduction of Ru complex to Ru particles, improving the catalytic performance. The present catalytic system can give full glycerol conversion and 57% yield of PA. Finally, the reaction pathway was proposed accordingly.

Isobaric Vapor–Liquid Equilibria of Binary Mixtures of Diethyl Carbonate with Methyl Acetate, n-Propyl Acetate, or Amyl Acetate at 100.17 kPa

Carbonate esters and esters are widely used in the pharmaceutical industry. It is important to enrich the vapor–liquid equilibrium (VLE) database of these components. In this article, the isobaric ...

Study of Vapor–Liquid Equilibria for Acetic Acid + n-Propyl Acetate + Isopropyl Acetate Systems

A mixture of acetic acid, n-propyl acetate, and isopropyl acetate, which needs to be separated, is obtained when isopropyl acetate is produced from acetic acid and propene. The vapor–liquid equilibria (VLE) for the acetic acid + n-propyl acetate + isopropyl acetate ternary system and three subsystems were studied with ebulliometry at (20, 40, 60, 80, and 101.3) kPa. The vapor-phase nonideality was described by the Hayden–O’Connell (HOC) equation, and the liquid-phase nonideality was represented by the NRTL model and the UNIQUAC model, respectively. The model parameters for acetic acid–n-propyl acetate, acetic acid–isopropyl acetate, and n-propyl acetate–isopropyl acetate were acquired from the experimental data with the aid of Aspen Plus. The maximum overall average deviation of temperature between the experiment and model predictions is 0.46 K for the NRTL-HOC model and 0.47 K for the UNIQUAC-HOC model. The VLE data and the model parameters acquired may provide basic information for the separation of iso...

Synthesis and Characterization of Schiff Bases Derivatives of Heterotrimetallic [Al(III); Sn(II); Ti(IV)]-µ-oxo-isopropoxide-µ-oxon-propoxide [SnO2TiAl(OPri)2(OPrn)3

Tin diacetate and aluminium isopropoxide in equimolar proportion in xylene affords the complex [(OAc)SnOAl(OPr i ) 2 ] which on reaction with Ti(OPr n ) 4 in 1:1 molar ratio yielded a new organoheterotrimetallic-μ-oxoisopropoxide-μ-oxon-propoxide [SnO 2 TiAl(OPr i ) 2 (OPr n ) 3 ] with continuous liberation of isopropyl acetate and propyl acetate formed during the course of reaction. The preparation of Schiff base complexes of the compound [SnO 2 TiAl(OPr i ) 2 (OPr n ) 3 ] was carried out in refluxing benzene by the reaction of µ-oxomixedpropoxide compound in different molar ratios (1:1 and 1:2) with Schiff bases (1-(2-Pyridyl) ethanonehydrazine carboxamide (HSB 1 ) and 1-Furanyl) ethanonehydrazin carboxamide (HSB 2 ). The complexes were characterized by spectral analysis (IR, 1 H, 13 C, 119 Sn, 27 Al NMR and mass spectra). The spectral studies confirmed that the proposed framework of the new organoheterotrimetallic complexes and indicated a tetrahedral geometry around the central metal atom.

Atmospheric oxidation chemistry of 1–methoxy 2–propyl acetate initiated by OH radicals: kinetics and mechanisms

Kinetics and mechanism of the gas-phase reaction of CH3C(O)OCH(CH3)CH2OCH3 (MPA) with OH radicals in the presence of O2 and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311 + G(d,p)//BH&HLYP/6-311++G(d,p) + 0.9335×ZPE. The calculations predict that the H-abstraction from the −CH2−O− position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH3C(O)OCH(CH3)C(O •)HOCH3 under atmospheric conditions. This activated radicals CH3C(O)OCH(CH3)C(O •)HOCH3 will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH3 and acetic anhydride CH3C(O)OC(O)CH3). In the presence of water, acetic anhydride can convert into acetic acid CH3C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372 K are used to derive a negative activation energy (E a= −5.88 kJ/mol) and an pre-exponential factor (A = 1.78×10−12 cm3 molecule−1 s−1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263−1000 K can be described by k = 5.60 × 10−14×(T/298 K)3.4×exp(1725.7 K/T) cm3 molecule−1 s−1.

Solution thermodynamics of tris-(2,4-ditert-butylphenyl)-phosphite in a series of pure solvents

In this work, to help the development and design of separation and purification processes for tris-(2,4-ditert-butylphenyl)-phosphite which is an antioxidant of plastic processing, its solution thermodynamics was investigated. Using a static gravimetric method, solubilities of tris-(2,4-ditert-butylphenyl)-phosphite in twelve pure solvents (including acetone, ethyl acetate, methyl acetate, ethyl formate, isopropyl acetate, butyl acetate, n-hexane, n-heptane, n-octane, isooctane, propyl acetate and ethyl butyrate) were measured at temperatures varying from 278.15 K to 323.15 K. It was found that, in all investigated solvents, the solubility data of tris-(2,4-ditert-butylphenyl)-phosphite increased with the increasing of temperature over the entire investigated temperature range. The modified Apelblat equation, the λh equation and the NRTL model were employed to correlate the solubility data. The computed data showed that the modified Apelblat equation correlated the solubility data better. Moreover, the mixing and dissolution thermodynamic properties of tris-(2,4-ditert-butylphenyl)-phosphite in various pure solvents were also calculated according to the NRTL model and the experimental solubility data.

Isobaric vapor-liquid equilibrium of a ternary system of ethyl acetate + propyl acetate + dimethyl sulfoxide and binary systems of ethyl acetate + dimethyl sulfoxide and propyl acetate + dimethyl sulfoxide at 101.3 kPa

Isobaric vapor-liquid equilibrium data were measured for three systems, namely, ethyl acetate + dimethyl sulfoxide, propyl acetate + dimethyl sulfoxide and ethyl acetate + propyl acetate + dimethyl sulfoxide at 101.3 kPa in this work. The experimental data were checked by the Van Ness (point-to-point test) and Herington (integral test) methods. The binary systems’ vapor-liquid equilibrium data tested by experiments were fitted well with the NRTL, UNIQUAC and Wilson models. The binary interaction parameters regressed by the three models and experimental data were accepted to predict vapor liquid equilibrium data of a ternary system. The maximum absolute deviations and mean absolute deviations between the experimental and thermodynamic model data were within a reasonable range, indicating that corrected binary interaction parameters can be used to accurately predict vapor-liquid equilibrium data of the ternary system.

Energy-saving hybrid processes combining pressure-swing reactive distillation and pervaporation membrane for n-propyl acetate production

The production of n-propyl acetate by transesterification is an environmentally and economically beneficial option for handling a huge amount of methyl acetate from the polyvinyl alcohol industry. This article proposes several energy-saving transesterification processes by combining pressure-swing reactive distillation with pervaporation for the production of n-propyl acetate. Among these, the combined PV unit with a polyoctylmethylsiloxane-based commercial membrane aims to separate the high purity methanol at the retentate side, and the solution diffusion-based PV model is developed by using Aspen Custom Modeler (ACM). The proposed processes with and without heat integration are optimized based on the minimum total annual cost, along with conventional and divided-wall reactive distillation processes. The results show that the partial heat-integrated pressure-swing reactive distillation assisted with pervaporation process provides a clear competitive advantage over the conventional reactive e distillation process, reducing the total annual cost by 58.15% and CO2 emission by 67.32%.

Both Penicillium expansum and Trichothecim roseum Infections Promote the Ripening of Apples and Release Specific Volatile Compounds.

Blue mold and core rot caused by Penicillium expansum and Trichothecium roseum are major diseases of apple fruit in China; however, their differential aggressiveness in apples and effect on fruit postharvest physiology are unclear. The effects of colonization of apples cv. Red Delicious by both pathogens were compared to physiological parameters of ripening and release of volatile compounds (VOCs). P. expansum colonization showed increased aggressiveness compared to T. roesum colonization of apple fruits. P. expansum enhanced colonization occurred with differential higher ethylene production and respiratory rate evolution, lower membrane integrity and fruit firmness in correspondence with the colonization pattern of inoculated apples. Moreover, P. expansum caused lower contents of total soluble solid and titratable acid, and higher malondialdehyde compared with T. roesum colonization. While both pathogen infections enhanced VOCs release, compared with T. roseum inoculated apples, P. expansum inoculated apple showed a higher total VOCs production including alcohols, aldehydes and esters, being the C6 alcohols, aldehydes and esters amount. PLS-DA analysis indicated that hexanoic acid was the most important factor to distinguish the inoculated fruits from the controls. Interestingly, propyl acetate and hexyl benzoate, and undecylenic acid and hexadecane were only identified in the P. expansum and T. roseum inoculated fruits, respectively. Taken together, our findings indicate that both fungi inoculations promote apple fruit ripening and release specific VOCs; moreover, apple fruits are more susceptible to P. expansum colonization than T. roesum.

Ester-Based Battery Solvents in Contact with Metallic Lithium: Effect of Water and Alcohol Impurities

Organic ester-based battery solvents were examined with respect to their reactivity with water and alcohols in contact with metallic lithium. The investigation was focused on monohydric esters (n-propyl acetate, isopropyl acetate), dihydric esters (trimethylene diacetate, 1,2-propylene glycol diacetate), and trihydric esters (triacetin). Experiments with lithium metal, the respective ester and water, and the matching alcohol were done. The resulting reaction solutions were analyzed with 1H NMR spectroscopy and compared to spectra recorded with the anticipated reaction products that were synthesized separately. The study reveals a tandem reaction from ester saponification to a catalytic Claisen condensation. Thus, the products formed during the reaction showed early degradation in cyclic voltammetry measurements in both the anodic and cathodic regions. A reactivity trend could be examined whereupon the trihydric esters were the least reactive followed by the dihydric and monohydric esters. In the absence o...

Use of Dairy and Plant-Derived Lactobacilli as Starters for Cherry Juice Fermentation

Background: Lactic acid bacteria (LAB) exhibit a great biodiversity that can be exploited for different purposes, such as to enhance flavours or metabolize phenolic compounds. In the present study, the use of dairy and plant-derived LAB strains to perform cherry juice fermentation is reported. Methods: The growth ability of Lactobacillus plantarum, Lactobacillus casei, Lactobacillus paracasei and Lactobacillus rhamnosus was studied in cherry juice. Profiling of sugars, organic acids and volatile compounds was performed by GC-MS (Gas Chromatography-Mass Spectrometry), while the phenolic fraction was characterized using UHPLC (Ultra High Performance Liquid Chromatography) equipped with a linear ion trap-mass spectrometer. Results: Sucrose significantly decreased in all fermented samples as well as malic acid, converted to lactic acid by malolactic fermentation. The total amount of volatile compounds increased. Specifically, propyl acetate, an ester with fruit notes, reached the highest concentration in L. rhamnosus and L. paracasei (dairy strains) fermented juices. Phenolics were extensively metabolized: caffeic acid was converted into dihydrocaffeic acid, p-coumaric acid into 4-ethylphenol and phenyllactic acid was produced. Conclusion: Lactic acid fermentation confer fruit notes to the juice and enhance phenyllactic acids, especially employing dairy strains (L. rhamnosus and L. paracasei). The level of dihydrocaffeic acid, a compound with putative biological activity was also increased (in particular with L. plantarum).

Determination of Abraham model solute descriptors for xanthone based on experimental solubility measurements at 298.2 K

ABSTRACTExperimental solubilities have been determined for xanthone dissolved in 15 different alcohol solvents (ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-methyl-1-propanol, 3-methyl-1-butanol, 2-ethyl-1-hexanol, 2-propanol, 2-butanol, 4-methyl-2-pentanol, 2-methyl-2-propanol and 2-methyl-2-butanol), in five alkyl acetate solvents (methyl acetate, ethyl acetate, propyl acetate, butyl acetate and pentyl acetate), in diisopropyl ether and in 2-ethoxyethanol at 298.2 K. In total, solubility measurements were performed in 22 organic solvents of varying polarity and hydrogen-bonding character. Results of the experimental measurements were used to calculate the Abraham model solute descriptors for xanthone. The calculated solute descriptors describe the experimental solubility data to within 0.096 log units.

Competitive and synergistic adsorption of binary volatile organic compound mixtures on activated carbon**Project supported by the National Natural Science Foundation of China (Grant No. 11574401), the Science Foundation of China University of Petroleum, Beijing (Grant Nos. 2462017YJRC029 and yjs2017019), and the Beijing Natural Science Foundation, China (Grant No. 1184016).

The adsorption of four substances and their binary mixture is investigated via the terahertz time domain spectroscopy (THz-TDS). The selected unary compound (ethanol, acetone, ethyl acetate, and n-propyl acetate) and binary mixture (solution 1 is composed of ethanol and acetone, and solution 2 is composed of ethyl acetate and n-propyl acetate) exhibit different adsorption behaviors with varied polarities. In comparison with single component, solution 1 shows shorter adsorption equilibrium time, faster adsorption rate, and stronger adsorption capacity, which conform to a synergistic adsorption mechanism, while the competitive behavior is attributed to the slower adsorption in solution 2. In addition, the pseudo-second-order equation with terahertz parameter is used to assess the rate of binary component organics. The present results indicate a further understanding of multicomponent adsorption mechanisms.

Convenient preparation of 2″-O-rhamnosyl icariside II, a rare secondary flavonol glycoside, by recyclable and integrated biphase enzymatic hydrolysis

Background: 2″-O-rhamnosyl icariside II, a rare secondary flavonol glycoside in Epimedii Folium (EF), has much better in vivo bioactivities than its original glycoside epimedin C. Its preparation methods, such as acidic hydrolysis, are of low efficiency, with by-products generated. Objective: The objective of this study was to establish a novel catalysis system for convenient preparation of this compound based on the recyclable and integrated biphase enzymatic hydrolysis. Materials and Methods: β-dextranase was selected from five commercial enzymes due to the best catalysis performance. After optimization of conditions, the biphase system was constructed with propyl acetate and HAc-NaAc buffer (pH 4.5) (3:2, v/v) containing β-dextranase/epimedin C (1:2, w/w), and the hydrolysis was performed at 60°C for 40 min. Results: Epimedin C was completely hydrolyzed to 2″-O-rhamnosyl icariside II, and 93.38% of the product has been transferred into organic phase; moreover, a high conversion rate had been achieved at 91.69% even after the enzyme solution was used for four cycles. In addition, the procedure was much simplified compared with conventional enzymatic hydrolysis. Conclusion: The newly proposed strategy is an efficient and promising approach for the preparation of 2″-O-rhamnosyl icariside II in industrial application. Abbreviations used: EF: Epimedii Folium; ACN: Acetonitrile; MeOH: Methanol; PTFE: Polytetrafluoroethylene; SD: Standard deviation; ILO-ICSC: International Labor Organization-The International Chemical Safety Cards; HMDB: Human Metabolome Database; HSDB: Hazardous Substances Data Bank.

Odor-Active Volatile Compounds from the Gonads of the Sea Urchin <i>Mesocentrotus nudus</i> in the Wild in Miyagi Prefecture, Tohoku, Japan

Background and Aims: Mesocentrotus nudus is commercially harvested from shallow rocky bottoms in northern Japan. The gonads are targeted as an edible product. The objective of this study was to identify odor-active volatile organic compounds (VOCs) from the gonads of adult M. nudus collected at a fishing ground in Miyagi Prefecture, Tohoku, Japan. Methods and Results: Gas chromatography-mass spectrometry analysis and gas chromatography-sniffing techniques identified 42 compounds categorized as alcohols, aldehydes, aromatic hydrocarbons, esters, halomethanes, hydrocarbons, ketones, sulfur-containing compounds, and nitrogen-containing compounds. GC-sniffing analysis characterized four compounds with preferable odors of sea urchin gonads; limonene, propyl acetate, acetone, dibromochloromethane. On the other hand, the analysis characterized three compounds with unpreferable odors; methyl mercaptane, dimethyl sulfide, and s-methyl thioacetate. Several VOCs from the gonads were derived from seaweeds, terrestrial plants, and fish flesh as food because M. nudus is omnivorous. Conclusion: This is the first study to identify VOCs from edible sea urchin gonads in the wild in Japan. These VOC data comprise a typical standard in order to evaluate a higher quality of sea urchin gonads.

Process Development, Assessment, and Control of Reactive Dividing-Wall Column with Vapor Recompression for Producing n-Propyl Acetate

As a combination of the conventional reactive distillation (RD) and diving-wall column, reactive diving-wall column (RDWC) is the highly thermally integrated process that has the advantages of high...

Convenient preparation of sagittatoside B, a rare bioactive secondary flavonol glycoside, by recyclable and integrated biphase enzymatic hydrolysis

Sagittatoside B, a rare secondary flavonol glycoside in Epimedii Folium, has much better in vivo bioactivities than its original glycoside epimedin B. Its preparation methods, such as acidic hydrolysis, are of low efficiency, and byproducts are generated. The objective of this study was to establish a novel catalysis system for convenient preparation of this compound based on recyclable and integrated biphase enzymatic hydrolysis. β-glucanase was selected from five commercial enzymes based on the best catalysis performance. After optimization of the conditions, the biphase system was constructed with propyl acetate and HAc-NaAc buffer (pH 4.5) (1:1, v/v) containing β-glucanase/epimedin B (1:2, w/w), and the hydrolysis was performed at 60 °C for 1 h. Consequently, epimedin B was completely hydrolyzed to sagittatoside B, and 95.7% of the product was transferred into the organic phase. Moreover, a high conversion ratio of 94.0% was achieved, even after the enzyme solution was used for six cycles. Additionally, the procedure was much simplified compared with conventional enzymatic hydrolysis. The newly proposed strategy is an efficient and promising approach for the preparation of sagittatoside B in industrial applications.