Kinetics of esterification of acetic acid with propyl alcohol by heterogeneous catalysis

Kinetic data on the esterification of acetic acid with propyl alcohol catalyzed by the ion exchange resin DOWEX MONOSPHERE 650 C have been obtained using a stirred batch reactor. It was checked if there is an influence of pore diffusion and film resistance on the reaction rate when varying reaction temperature, initial molar ratios, and amount of resin. The possible mechanisms of reaction were mathematically treated using the theories of Langmuir-Hinshelwood and Rideal-Eley. Taking the nonideal behavior of the system acetic acid, propyl alcohol, propyl acetate, and water into account, all calculations were realized with activities using the UNIQUAC-equation. By using the experimental results in a process of model discrimination the best kinetic parameter set was found out by the aid of the commercial software package SIMUSOLV. The resulting data of rate constants and the experimental determined equilibrium constants served as a basis for the calculation of the thermodynamic parameters of esterification, as reaction enthalpy, reaction entropy, and activation enthalpies. © 1996 John Wiley & Sons, Inc.     

Kinetics of esterification of acetic acid with n-butanol over different homogeneous acid catalysts

The esterification reaction of n-butanol and acetic acid has been performed in batch reactor in the presence of different homogeneous acid catalyst, namely sulfuric acid, nitric acid, and para toluene sulfonic acid (p-TSA). The objective of present research work is to investigate kinetic behavior of esterification reaction over the temperature range of 60°C–80°C. The effect of reaction parameter such as catalyst loading varied from 1% to 5% v/v and acid to alcohol molar ratio of 1:1, 1:3, and 1:5 has been observed. A pseudo homogeneous kinetic model has been applied. Kinetic parameters such as equilibrium constant, reaction rate constant, enthalpy, activation energy, and entropy were calculated by the experimental data for different acid catalyst system. It was observed that sulfuric acid gives higher conversion 73% than p-TSA 68.5% and nitric acid 66.25% at temperature of 80°C, 1:1 molar ratio and 3% catalyst concentration. The activation energy was estimated 36448.49, 23324.31 and 19060.156 J/mol K for three different catalyst sulfuric acid, nitric acid and p-TSA respectively. The enthalpy and entropy of the esterification reaction of acetic acid with n-butanol over three different catalysts has been calculated (Enthalpy: 25.788 KJ/mol, 12.256 KJ/mol, 28.320 KJ/mol, Entropy: 88.1 J/mol K, 45.298 J/mol K, 91.44 J/mol K) and found enthalpy is having positive value that shows reaction is endothermic.     

Modification of sturgeon protamines with succinic anhydride

The modification of the - and -NH₂ groups of sturins A and B — protamines fromAcipenser güldenstadti — with succinic anhydride has been studied. Succinylation was carried out at 20°C, pH from 7.5 to 10.5, using a 50 to 180-fold excess of succinic anhydride. The modification products were separated by reversed-phase HPLC on a Zorbax ODS column. A linear relationship has been established between the retention times of the succinyl derivatives and the number of succinyl groups introduced. The influence of the pH and of the excess of succinic anhydride on the modification of the sturins has been studied by the method of experimental planning and mathematical modeling. The optimum conditions have been found for the succinylation of the proteins: a 150- to 180-fold excess of succinic anhydride and pH values of 9.8–10.2 for sturin A and of 8.4–9.4 for sturin B.Moscow Technological Institute of the Meat and Dairy Industry. All-Union Scientific-Research Institute for the Search for New Antibiotics, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 238–243, March–April, 1989.     

Cascade catalysis for the homogeneous hydrogenation of CO2 to methanol

This communication demonstrates the homogeneous hydrogenation of CO(2) to CH(3)OH via cascade catalysis. Three different homogeneous catalysts, (PMe(3))(4)Ru(Cl)(OAc), Sc(OTf)(3), and (PNN)Ru(CO)(H), operate in sequence to promote this transformation.     

Homolytic alkylation of succinic anhydride with 1-alkenes

Conclusions The reaction of succinic anhydride with C₈−C₁₈-alkenes, initiated by tert-butyl peroxide, leads to the formation of n-alkylsuccinic anhydrides, the yield of which under the optimum conditions is 50–75%. N.D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2389–2392, October, 1976.     

Kinetics of the esterification of maleic anhydride with octyl, decyl or dodecyl alcohol over dowex catalyst

Summary Esterification of maleic anhydride over acid ion exchange resin catalyst has been investigated in an isothermal semi batch reactor. Although this is a bimolecular reaction, first order kinetics with respect to acid has been observed.     

Kinetics and mechanism of myristic acid and isopropyl alcohol esterification reaction with homogeneous and heterogeneous catalysts

The reaction of myristic acid (MA) and isopropyl alcohol (IPA) was carried out by using both homogeneous and heterogeneous catalysts. For a homogeneously catalyzed system, the experimental data have been interpreted with a second order, using the power‐law kinetic model, and a good agreement between the experimental data and the model has been obtained. In this approach, it was assumed that a protonated carboxylic acid is a possible reaction intermediate. After a mathematical model was proposed, reaction rate constants were computed by the Polymath* program. For a heterogeneously catalyzed system, interestingly, no pore diffusion limitation was detected. The influences of initial molar ratios, catalyst loading and type, temperature, and water amount in the feed have been examined, as well as the effects of catalyst size for heterogeneous catalyst systems. Among used catalysts, p‐toluene sulfonic acid (p‐TSA) gave highest reaction rates. Kinetic parameters such as activation energy and frequency factor were determined from model fitting. Experimental K values were found to be 0.54 and 1.49 at 60°C and 80°C, respectively. Furthermore, activation energy and frequency factor at forward were calculated as 54.2 kJ mol^?1 and 1828 L mol^?1 s^?1, respectively. © 2008 Wiley Periodicals, Inc. 40: 136–144, 2008     

Enhancement of mechanical and thermal properties of oil palm empty fruit bunch fiber poly(butylene adipate-co-terephtalate) biocomposites by matrix esterification using succinic anhydride

In this work, the oil palm empty fruit bunch (EFB) fiber was used as a source of lignocellulosic filler to fabricate a novel type of cost effective biodegradable composite, based on the aliphatic aromatic co-polyester poly(butylene adipate-co-terephtalate) PBAT (Ecoflex?), as a fully biodegradable thermoplastic polymer matrix. The aim of this research was to improve the new biocomposites' performance by chemical modification using succinic anhydride (SAH) as a coupling agent in the presence and absence of dicumyl peroxide (DCP) and benzoyl peroxide (BPO) as initiators. For the composite preparation, several blends were prepared with varying ratios of filler and matrix using the melt blending technique. The composites were prepared at various fiber contents of 10, 20, 30, 40 and 50 (wt %) and characterized. The effects of fiber loading and coupling agent loading on the thermal properties of biodegradable polymer composites were evaluated using thermal gravimetric analysis (TGA). Scanning Electron Microscopy (SEM) was used for morphological studies. The chemical structure of the new biocomposites was also analyzed using the Fourier Transform Infrared (FTIR) spectroscopy technique. The PBAT biocomposite reinforced with 40 (wt %) of EFB fiber showed the best mechanical properties compared to the other PBAT/EFB fiber biocomposites. Biocomposite treatment with 4 (wt %) succinic anhydride (SAH) and 1 (wt %) dicumyl peroxide (DCP) improved both tensile and flexural strength as well as tensile and flexural modulus. The FTIR analyses proved the mechanical test results by presenting the evidence of successful esterification using SAH/DCP in the biocomposites' spectra. The SEM micrograph of the tensile fractured surfaces showed the improvement of fiber-matrix adhesion after using SAH. The TGA results showed that chemical modification using SAH/DCP improved the thermal stability of the PBAT/EFB biocomposite.     

Recycling of homogeneous hydrogenation catalysts by dialysis coupled catalysis

Although transition-metal complexes are very attractive as homogeneous catalysts in fine chemistry, their high prices often limit their applications. A means to recycle those catalysts would solve this problem and would simultaneously facilitate the downstream purification of the product. This is now realized in a new concept in which homogeneous catalysis is coupled to dialysis. The advantages of homogeneous catalysis (off-the-shelf catalysts, high activities and selectivities) are thus combined with those of heterogeneous catalysis (easy catalyst separation from product solution, reuse of catalyst, and possibility for continuous operation). Since the heart of the process is the membrane, self-prepared membranes were preferred as they allow a better control and understanding of the separation characteristics. Rhodamine B was used as a probe molecule to define the working conditions of the membrane. The concept is proven to work for two relevant chiral reactions: a hydrogenation with Ru-BINAP and a hydrogen transfer reaction with Ru-TsDPEN [BINAP=(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine); TsDPEN= tosyl-N,N'-diphenyl-1,2-ethanediamine].     

Reactions of Bi-, Tri-, and tetracyclic amines with succinic anhydride

Succinic anhydride reacted with cage-like amines {bicyclo[2.2.1]hept-5-en-exo-and-endo-2-yl-methanamines, 2-(bicyclo[2.2.1]hept-5-en-endo-2-yl)ethanamine, exo-5,6-epoxybicyclo[2.2.1]heptan-exo-2-yl-methanamine, tetracyclo[6.2.1.1^3,6.0^2,7]dodec-9-en-endo-4-ylmethanamine, 1-(bicyclo[2.2.1]heptan-2-yl)ethanamine, and 4-azatricyclo[5.2.1.0^2,6]dec-8-ene} to give the corresponding amido acids having a cage-like fragment. The latter were converted into carboximides by the action of hexamethyldisilazane in boiling benzene in the presence of zinc(II) chloride and then into epoxy derivatives. The structure of the newly synthesized compounds was confirmed by IR and NMR spectroscopy.     

Transesterification and esterification with subcritical methanol. Synthesis of biodiesel

Benzoic acid esterification and ethyl benzoate transesterification with subcritical methanol were carried out at 220 °C without any catalyst. A procedure for biodiesel production from vegetable oil under indicated conditions was proposed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 102–104, January, 2008.     

Comparison of alkenyl succinic anhydride emulsions stabilized by laponite modified with ethylamine,diethylamine and triethylamine

The modifications of laponite particles with three short amines, that is, ethylamine, diethylamine and triethylamine, were compared and the amine-modified laponites were used to stabilize alkenyl succinic anhydride emulsions. The results show that the emulsion stability can be improved while the emulsion droplet size can be reduced by using the amines to modify laponite particles. Among the three amines, the diethylamine exerts the largest while the triethylamine exerts the smallest effects on the zeta potential of laponite, the turbidity of laponite aqueous dispersion and the emulsion stability and morphology. The emulsion with the smallest droplet size shows the highest sizing performance.     

Study of the products of the reaction of succinic anhydride derivatives with urea

Conclusions The product of the reaction of isododecenylsuccinic anhydride with urea at 120–160°C is isododecenylsuccinimide.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1900–1902, August, 1988.     

Kinetics of esterification for octylphenylphosphoric acids

Extraction power of octylphenylphosphoric acids for uranium is sensitive to the di/mono ratio of the ester concentration in a diluent. This work describes the esterification kinetics of p-octylphenol and phosphorus oxychloride in kerosine, understanding of which is essential in controlling the di/mono ratio during the preparation of the esters. A differential equation, solved independently of the reaction history, agrees very well with the experimental data.     

Kinetics of oxidation of methanol by chlorine dioxide

The kinetics of oxidation of methanol by chlorine dioxide has been investigated at 35 °C. The reaction is first order with respect to both substrate and chlorine dioxide. Molecular chlorine dioxide is the principal oxidant. The influence of various factors, e.g. ionic strength, inorganic salts, D₂O and temperature on the initial rate has been studied. The activation parameters have been calculated and a mechanism involving hydride abstraction has been suggested.

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New coupling reagents for homogeneous esterification of cellulose

A group of known, but in cellulose chemistry new coupling reagents for homogeneous esterification has been investigated: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methyl-morpholinium chloride, N-methyl-2-bromopyridinium iodide, N-methyl-2-chloropyridinium iodide, and N-methyl-2-bromopyridinium tosylate. In order to study their ability to activate carboxylic acids in esterifications of cellulose they have been employed in synthesis of cellulose adamantate esters. Their effectiveness has been estimated in terms of degree of substitution of resulting esters and compared to that obtained with the commonly used N,N′-carbonyldiimidazole.     

Determination of cyanide ion by homogeneous catalysis and gas chromatography

A simple procedure for the determination of trace levels of cyanide ions is described and evaluated. The procedure is based on the cyanide-catalyzed cleavage of benzil in the presence of methanol to produce benzaldehyde and methyl benzoate. The concentrations of these products are determined by gas chromatography. Linearity between gas chromatographic response and cyanide concentration is observed from 0.05 to 3 ppm cyanide; a detection limit of 1 ppb is calculated. A series of anions is shown not to interfere.     

Functionalization of syndiotactic polystyrene with succinic anhydride in the presence of aluminum chloride

Syndiotactic polystyrene has been chemically modified with succinic anhydride by use of Friedel-Crafts acylation reaction in the presence of anhydrous aluminum chloride in carbon disulfide. The modified syndiotactic polystyrene containing -COCH₂CH₂COOH fragments in side phenyl rings, named succinoylated syndiotactic polystyrene (s-sPS), was characterized by FTIR and ¹H NMR spectroscopy. The effects of reaction conditions on the degree of succinoylation of s-sPS were investigated. In addition, the effects of incorporation of carboxyl groups into syndiotactic polystyrene on the thermal behavior were studied by differential scanning calorimetry in comparison with pure syndiotactic polystyrene. It was found that the crystallization temperature, melting temperature, and degree of crystallinity of the modified polymer decreased with increasing the degree of succinoylation, while the glass transition temperature increased.     

Iridium-catalyzed oxidative methyl esterification of primary alcohols and diols with methanol

Oxidative methyl esterification of primary alcohols and diols with methanol was successfully achieved, using acetone as a hydrogen acceptor, under the influence of an iridium complex combined with 2-(methylamino)ethanol (MAE) as catalyst.     

Advances in homogeneous and heterogeneous catalysis with metal-containing silsesquioxanes

Metal-containing silsesquioxane derivatives provide new catalysts with both homogeneous and heterogeneous applicability. The steric and electronic properties of silsesquioxane silanolate ligands render metal centers more Lewis acidic than conventional alkoxide or siloxide ligands do. This concept has been exploited in newly developed catalysts for alkene metathesis, polymerization, epoxidation, and Diels-Alder reactions of enones. Other applications are envisioned in the near future.