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61.
The key factors influencing the Diels—Alder reaction rate at ambient and elevated pressures were elucidated using data on the reactivity of various diene—dienophile systems in usual and Lewis acid-catalyzed Diels—Alder reactions, the reaction enthalpy, complex formation, dissolution, and solvation, and the donor-acceptor properties of the reactants. It was found that taking account of both the orbital interaction energy and the balance of bond rupture and formation energies allows correct prediction of the reaction rate in the absence or in the presence of Lewis acids. 相似文献
62.
E. Robens 《Journal of Thermal Analysis and Calorimetry》1996,47(2):619-622
A survey is given on important standardized definitions by which the capability of balances may be characterized. Some modifications are proposed with regard to the use of mass sensors for the continuous determination of mass variations. An important supplement is the relative resolution introduced by Jenemann. Optimum values are presented.I am indepted to H. R. Jenemann for his critical remarks. 相似文献
63.
J.?MajumdarEmail author F.?Cser M.?C.?Jollands R.?A.?Shanks 《Journal of Thermal Analysis and Calorimetry》2004,78(3):849-863
Differential scanning calorimetry has been used to study the heat flow during melting and crystallisation of a range of polypropylene post-consumer waste (PP PCW) grades and blends. The heat flow curves and the heat capacity curves indicated that the PP PCW grades and blends contained contaminants even after manual sorting and a cleaning process. The enthalpies of the PP PCW grades were lower than that for the virgin grades, as a result of degradation. Small amounts of polymeric contaminants (up to 10%) did not affect the enthalpies of PP PCW although other contaminants may have had some effect. The enthalpies of the PCW blends could in general be predicted by a linear additive rule, which is of importance for recycling a variety of PP PCW products.The authors would like to thank Dr. M. Killen (Basell Australia Pty. Ltd.), Mr. P. Slaven (Citiwide MRF), Dasma Valley Waste Prop. Ltd. and Mr. I. Janetzki (Huhtamaki Australia Ltd.) for supplying materials for this project. Financial support for the project was provided by Basell Australia and Ecorecycle Victoria, Australia. 相似文献
64.
M. Domínguez-Pérez J. Jiménez de Llano L. Segade C. Franjo O. Cabeza 《Journal of Thermal Analysis and Calorimetry》2005,79(2):289-293
Summary This paper reports excess molar enthalpies of the binary systems hexane+ethyl benzene, hexane+o-xylene, hexane+m-xylene and hexane+p-xylene at 298.15 K and atmospheric pressure, over the whole composition range. The data was measured directly using a Calvet microcalorimeter. The excess magnitude was correlated to a Redlich-Kister type equation for each mixture. Also, we will discuss the results for the four mixtures studied here and by comparison with the same binary systems but containing propyl propanoate as first component. Finally, we will correlate our results with the Nitta-Chao and the three UNIFAC theoretical approximations. 相似文献
65.
The connection between the dielectric and calorimetric relaxation behaviours of synthetic polyisoprene Cariflex IR 305 is studied. A similar comparison of dielectric and dilatometric results was described in [1]. The heat capacity was measured during heating of samples prepared with different thermal history. Experimental results were compared with the heat capacity curves calculated for a model based on the multiparameter theory of Kovacs et al. [4]. The model considers the relaxation system as being composed of a set of subsystems characterized by different relaxation times. The distribution of relaxation times and their temperature dependence were taken from the diclectric measurement. The relaxation time of a subsystem from posed to depend, not only on the actual, temperature of the sample, but also on the deviation of this subsystem from equilibrium, or alternatively, on the deviation of the system as a whole. The comparison between the measured and modeled curves shows that both influences must be taken into account in order to explain the experimental results.Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday. 相似文献
66.
By using a micro-bomb calorimeter, the standard enthalpies of combustion of C60 and C70 have been determined to be - (25 947.1±8.5) and - (29 956.1 ± 8.9) kJ/mol respectively. A g. 1. c. analysis indicated that
the amounts of residual organic solvents in the samples were very small, and their effects on the final results were negligible.
The energy of combustion ofC60 determined in this work is in agreement in the uncertainty interval with that determined by means of traditional calorimeter
using macro amount of sample. The enthalpies of formation of these two substances have been derived. The strain energies in
the molecules of C60 and C70 were estimated by a bond energy scheme and by using corannulene as the model compound, the results estimated from different
methods are very close.
Project supported by the National Natural Science Foundation of China (Grant No. 29473143) 相似文献
67.
Sergey P. Verevkin Wei-Hong Peng Hans-Dieter Beckhaus Christoph Rüchardt 《Structural chemistry》1996,7(5-6):397-404
The standard enthalpies of combustion c
H
o of aliphatic diacetates1 and aromatic diacetates2 were measured calorimetrically. The enthalpies of vaporization vap
H
o or sublimation sub
H
o of1 and2 were obtained from the temperature function of the vapor pressure measured in a flow system. From f
H
o(g) of1 and2 new values of group increments for the estimation of standard enthalpies of formation of these classes of compounds were derived. The geminal interaction energy between the geminal acyloxy groups shows no anomeric stabilization.Geminal Substituent Effects, Part 12, for part 11 see Ref. 7. 相似文献
68.
The thermodynamics of the conversion of aqueous glucose to fructose has been investigated using both heat conduction microcalorimetry
and high pressure liquid chromatography (HPLC). The reaction was carried out in both aqueous Tris/HCl buffer and in aqueous
phosphate buffer in the pH range 7–8 using the enzyme glucose isomerase and the cofactors CoCl2 and MgSO4. The temperature range over which this reaction was investigated was 298.15–358.15 K. We have found that the enthalpy of
reaction is independent of pH over the range investigated. A combined analysis of both the HPLC and microcalorimetric data
leads to the following results at 298 15 K:ΔG° = 349 ± 53 J mol-1, ΔH° = 2.78 ± 0.20 kJ mol-1, and ΔC
p
°
= 76 ± 30 J mol-1 K-1. The stated uncertainties are based upon an analysis of both the random and systematic errors inherent in the measurements.
Comparisons are made with literature data. The percent conversion of glucose to fructose has been calculated for the temperature
range 300–373.15 K. 相似文献
69.
R. L. Arenosa R. G. Rubio C. Menduiña M. Díaz Peña 《Journal of solution chemistry》1985,14(5):345-354
The molar excess enthalpies for the ethylbenzene + n-decane and ethylbenzene + n-tetradecane systems have been measured at 25°C over the complete concentration range. These results and others from the literature for alkanes + ethylbenzene, and alkanes + toluene have been discussed in terms of the Prigogine-Flory-Patterson theory. 相似文献
70.
O. V. Prokuda V. R. Belosludov I. K. Igumenov P. A. Stabnikov 《Journal of Structural Chemistry》2006,47(6):1032-1041
Experimental data have been analyzed and interpreted for four volatile acetylacetonates of trivalent metals Al, Cr, Fe, and Ir. The crystal lattice energies were calculated by the atom-atom potential method. The lattice energies obtained by using the Buckingham potential are in better agreement with the sublimation heats of these metal complexes than those calculated from the Lennard-Jones potential. The experimental dependences of vapor pressure for the complexes are in satisfactory agreement with the values obtained from the calculated lattice energies and entropies of crystal-gas transitions. 相似文献