Additivity rules for the estimation of thermochemical properties

Benson, Sidney W.; Cruickshank, F. R.; Golden, David M.; Haugen, G. R.; O’Neal, H. E.; Rodgers, A. S.; Shaw, Robert; Walsh, Robin

doi:10.1021/cr60259a002

Cited by 1,387 publications

(758 citation statements)

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“…The most common monomers used in ROMP are cyclic olefins having considerable ring strain (45 kcal mol -1 ), such as cyclobutene, cyclopentene, cis-cyclooctene and norbornene. 7 ROMP is commonly accompanied by intermolecular and intramolecular chain-transfer reactions as illustrated in Scheme 4. In the intermolecular chain transfer, a polymer chain having an active metal alkylidene on its terminus reacts with a double bond in another polymer chain.…”

Section: Introductionmentioning

confidence: 99%

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Sutthasupa

Shiotsuki

Sanda

2010

Polym J

328

273

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This article reviews the development of catalysts for ring-opening metathesis polymerization (ROMP), synthesis of polymers bearing amino acids and peptides by ROMP of functionalized norbornenes, formation of aggregates and micelles, and applications of the polymers to medical materials. It also describes the control of monomer unit sequences, that is, living polymerization to synthesize block copolymers, and alternating copolymerization that is achieved on the basis of acid-base interactions. Polymer Journal (2010) 42, 905-915; doi:10.1038/pj.2010.94; published online 13 October 2010Keywords: alternating copolymerization; amino acid; block copolymerization; living polymerization; metathesis catalyst; peptide; ROMP INTRODUCTIONOlefin metathesis reactions are metal-mediated carbon-carbon (C-C) double bond exchange processes, 1,2 which were discovered in the mid 1950s. Chauvin proposed the commonly accepted mechanism for metathesis involving a metallacyclobutane, as illustrated in Scheme 1. 3 Initially, olefin metathesis was regarded as an odd reaction, but now it has undoubtedly established the position as one of the most important C-C bond formation reactions applicable to synthesis of a wide variety of useful products. In the early stages, transition metal chlorides were used as catalysts for the reaction, but the transition metal carbene complex catalysts designed by Schrock and Grubbs have remarkably advanced mechanistic analysis and control of catalytic activity by the choice of ligands. In 2005, Chauvin, Grubbs and Schrock were awarded the Nobel Prize in chemistry for development of the metathesis method in organic synthesis.Olefin metathesis polymerization is an application of metathesis reactions to polymer synthesis and includes ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polycondensation (Scheme 2). ADMET has been extensively developed by Wagener since 1987 4 for the synthesis of polyolefins having regularly spaced functional group branches and high thermal stability and crystallinity. 5,6 ADMET is also useful for synthesizing polymeric materials containing in-chain functionality. Although the general structures of the polymers obtained by ROMP and ADMET are illustratable in the same fashion as shown in Scheme 2, a completely different treatment is necessary from the viewpoint of polymerization kinetics. The former involves chain polymerization, whereas the latter is a step-growth polymerization process.

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Section: Introductionmentioning

confidence: 99%

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Sutthasupa

Shiotsuki

Sanda

2010

Polym J

328

273

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“…However, not all the physical properties of the chemicals could be obtained from handbook, the group contribution methods were investigated to estimate the physicochemical properties of organic compounds, such as Joback method [11], Constantinou-Gani method [12], Benson method [13] and so on [14,15]. In this paper, the liquid heat capacities of cyclopentanol and cyclopentyl acetate, the standard enthalpy of formation and standard entropy of gaseous cyclopentyl acetate at the temperature of 298.15 K, and the standard vaporization enthalpy of cyclopentyl acetate were estimated by Ruzicka-Domalski method [16], Yoneda method (ABWY) [17] and Ducros method [18,19], respectively [20].…”

Section: Thermodynamic Calculation Reaction Equationsmentioning

confidence: 99%

Thermodynamic analysis of synthesis of cyclopentanol from cyclopentene and comparison with experimental data

et al. 2015

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Cyclopentanol is a very important chemical intermediate, which has been widely used in the chemical industry, and could be prepared from cyclopentene by two steps: an initial addition-esterification reaction of cyclopentene with acetic acid and the subsequent transesterification reaction with methanol. However, so far, no direct theoretical or experimental work has been reported on this process. In this work, we have carried out the thermodynamic calculation of the indirect process and also validated the thermodynamic prediction through experimental work. The liquid heat capacities of cyclopentanol and cyclopentyl acetate were estimated using the Ruzicka-Domalski group contribution method, the standard enthalpy of formation and standard entropy of gaseous cyclopentyl acetate by the Yoneda group contribution method, the standard vaporization enthalpy of cyclopentyl acetate by the Ducros group contribution method. The enthalpy changes, free energy changes, equilibrium constant and equilibrium conversion of the addition-esterification and transesterification reactions were calculated according to the principles of chemical thermodynamics in the temperature range from 273.15 to 373.15 K. The results showed that both the addition-esterification reaction and transesterification reaction were exothermic, the free energy changes increased with a rise on temperature, which indicated that low temperature was favorable for the reactions in the temperature range from 273.15 to 373.15 K. The optimal addition-esterification reaction conditions were a temperature range from 333.15 to 353.15 K, molar ratios of acetic acid to cyclopentene in the range from 2:1 to 3:1. For the transesterification reaction, the ideal temperature ranges from 323.15 to 343.15 K, with a molar ratio of methanol to cyclopentyl acetate in the range from 3:1 to 4:1. These thermodynamic calculation results for the addition-esterification reaction of cyclopentene and acetic acid experiments results are in good agreement with the experimental results.

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“…Dorofeeva & Moiseeva (2006) calculated the Δ f H°(298) of organic compounds containing phosphorus. Their purpose was: a) to assess generally accepted experimental data on organophosphorus(III) compounds using the G3X method; b) to recommend a set of consistent Δ f H°(298) values based on best quality experimental values and G3X results; c) to calculate accurate Δ f H°(298) values for organophosphorus(III) compounds with missing experimental thermochemical data; d) to derive a consistent and accurate set of group activitiy values (GAVs) needed to estimate the Δ f H°(298) of larger organophosphorus(III) molecules, account taken that the empirical group additivity method of Benson (Benson et al, 1969) (Cohen & Benson, 1993) can predict the thermochemical properties of organic compounds with chemical accuracy, i.e. within 4 kJ/mol.…”

Section: Organophosphorous Compoundsmentioning

confidence: 99%