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Thermochemical Properties (thermochemical + property)
Selected AbstractsA Theoretical Study of the Structure and Thermochemical Properties of Alkali Metal Fluoroplumbates MPbF3CHEMINFORM, Issue 38 2007A. I. Boltalin Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] On the Spectroscopic and Thermochemical Properties of ClO, BrO, IO, and Their AnionsCHEMINFORM, Issue 15 2007Kirk A. Peterson Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Synthesis, Thermochemical Properties and Crystal Structure of Bi7Cl10.CHEMINFORM, Issue 16 2005Silke Hampel Abstract For Abstract see ChemInform Abstract in Full Text. [source] The ×NO3 Radical and Related Nitrogen Oxides, Characterized by ab initio Calculations of Thermochemical Properties.CHEMINFORM, Issue 1 2003Rudolf Janoschek No abstract is available for this article. [source] Effects of Isomerization on the Measured Thermochemical Properties of Deprotonated Glycine/Protic-Solvent ClustersCHEMPHYSCHEM, Issue 18 2008Robert J. Nieckarz Dr. Abstract The thermochemical properties associated with the formation of an isomeric distribution of ROH,,,NH2CH2COO, clusters (R=H, CH3, C2H5) are measured by using high-pressure mass spectrometry. A comparison of the measured properties with calculated values provides new insights into the thermochemical effects arising from the isomeric nature of this clustering system. When the distribution of isomers is correctly accounted for, the measured values of ,H°, ,S°, and ,G°298 consistently agree, to a very high degree of accuracy, with those predicted by MP2(full)/6-311++G(d,p)//B3LYP/6-311++G(d,p) calculations. [source] Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate MonohydrateCHINESE JOURNAL OF CHEMISTRY, Issue 1 2007Jian Wu Abstract Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is (28.795±0.182) kJ/mol (298.15 K), and the standard molar enthalpy of formation of the title complex is (,2185.43±13.80) kJ/mol (298.15 K). Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction:an nth-order reaction (Fn) with n=4.28, E1=147.35 kJ/mol, A1=3.63×1013 s,1 is followed by a second-order reaction (F2) with E2=212.71 kJ/mol, A2=1.82×1018 s,1. [source] Reaction of H + ketene to formyl methyl and acetyl radicals and reverse dissociationsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 1 2003Jongwoo Lee Thermochemical properties for reactants, intermediates, products, and transition states important in the ketene (CH2CO) + H reaction system and unimolecular reactions of the stabilized formyl methyl (C·H2CHO) and the acetyl radicals (CH3C·O) were analyzed with density functional and ab initio calculations. Enthalpies of formation (,Hf°298) were determined using isodesmic reaction analysis at the CBS-QCI/APNO and the CBSQ levels. Entropies (S°298) and heat capacities (Cp°(T)) were determined using geometric parameters and vibrational frequencies obtained at the HF/6-311G(d,p) level of theory. Internal rotor contributions were included in the S and Cp(T) values. A hydrogen atom can add to the CH2 -group of the ketene to form the acetyl radical, CH3C·O (Ea = 2.49 in CBS-QCI/APNO, units: kcal/mol). The acetyl radical can undergo ,-scission back to reactants, CH2CO + H (Ea = 45.97), isomerize via hydrogen shift (Ea = 46.35) to form the slight higher energy, formyl methyl radical, C·H2CHO, or decompose to CH3 + CO (Ea = 17.33). The hydrogen atom also can add to the carbonyl group to form C·H2CHO (Ea = 6.72). This formyl methyl radical can undergo , scission back to reactants, CH2CO + H (Ea = 43.85), or isomerize via hydrogen shift (Ea = 40.00) to form the acetyl radical isomer, CH3C·O, which can decompose to CH3 + CO. Rate constants are estimated as function of pressure and temperature, using quantum Rice,Ramsperger,Kassel analysis for k(E) and the master equation for falloff. Important reaction products are CH3 + CO via decomposition at both high and low temperatures. A transition state for direct abstraction of hydrogen atom on CH2CO by H to form, ketenyl radical plus H2 is identified with a barrier of 12.27, at the CBS-QCI/APNO level. ,Hf°298 values are estimated for the following compounds at the CBS-QCI/APNO level: CH3C·O (,3.27), C·H2CHO (3.08), CH2CO (,11.89), HC·CO (41.98) (kcal/mol). © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 20,44, 2003 [source] Thermochemistry for enthalpies and reaction paths of nitrous acid isomersINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2007Rubik Asatryan Recent studies show that nitrous acid, HONO, a significant precursor of the hydroxyl radical in the atmosphere, is formed during the photolysis of nitrogen dioxide in soils. The term nitrous acid is largely used interchangeably in the atmospheric literature, and the analytical methods employed do not often distinguish between the HONO structure (nitrous acid) and HNO2 (nitryl hydride or isonitrous acid). The objective of this study is to determine the thermochemistry of the HNO2 isomer, which has not been determined experimentally, and to evaluate its thermal and atmospheric stability relative to HONO. The thermochemistry of these isomers is also needed for reference and internal consistency in the calculation of larger nitrite and nitryl systems. We review, evaluate, and compare the thermochemical properties of several small nitric oxide and hydrogen nitrogen oxide molecules. The enthalpies of HONO and HNO2 are calculated using computational chemistry with the following methods of analysis for the atomization, isomerization, and work reactions using closed- and open-shell reference molecules. Three high-level composite methods G3, CBS-QB3, and CBS-APNO are used for the computation of enthalpy. The enthalpy of formation, ,Hof(298 K), for HONO is determined as ,18.90 ± 0.05 kcal mol,1 (,79.08 ± 0.2 kJ mol,1) and as ,10.90 ± 0.05 kcal mol,1 (,45.61 ± 0.2 kJ mol,1) for nitryl hydride (HNO2), which is significantly higher than values used in recent NOx combustion mechanisms. H-NO2 is the weakest bond in isonitrous acid; but HNO2 will isomerize to HONO with a similar barrier to the HONO bond energy; thus, it also serves as a source of OH in atmospheric chemistry. Kinetics of the isomerization is determined; a potential energy diagram of H/N/O2 system is presented, and an analysis of the triplet surface is initiated. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 378,398, 2007 [source] Theoretical investigation of an energetic fullerene derivativeJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2010Bisheng Tan Abstract A self-consistent estimation method for the thermochemical properties of N -methyl-3-(2,,4,,6,-trinitrobenzene)-fulleropyrrolidine (MTNBFP) is presented. This method is based on enthalpy of formation (,fH) and enthalpy of combustion obtained from BLYP/DNP calculations of the total energies and frequencies for MTNBFP. The enthalpy of formation was calculated by an optimized set of isodesmic reactions given the available experimental ,fH of relative compounds. MTNBFP has a high enthalpy of formation, 2782.2 kJ/mol. Detonation velocity and detonation pressure were also presented in terms of Kamlet and Jacobs equations. Drop hammer impact sensitivity tests and blasting point per 5 s tests indicate MTNBFP may be a potential candidate primary explosive. To understand the test results well, we proposed a series of chemical reaction mechanisms and interpreted the relationship between impact sensitivity and electronic structures from the viewpoint of nitro group charge, electrostatic potential, and vibrational modes. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] linear free energy relationships;JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 11 2007UB3LYP/6-31G(d The substituent effect on the reactivity of the CN bond of molecular ions of 4-substituted N -(2-furylmethyl)anilines toward two dissociation pathways was studied. With this aim, six of these compounds were analyzed by mass spectrometry using electron ionization with energies between 7.8 and 69.9 eV. Also, the UB3LYP/6-31G (d,p) and UHF/6-31G (d, p) levels of theory were used to calculate the critical energies (reaction enthalpies at 0 K) of the processes that lead to the complementary ions [C5H5O]+ and [M , C5H5O]+, assuming structures that result from the heterolytic and homolytic CN bond cleavages of the molecular ions, respectively. A kinetic approach proposed in the 1960s was applied to the mass spectral data to obtain the relative rate coefficients for both dissociation channels from ratios of the peak intensities of these ions. Linear relationships were obtained between the logarithms of the relative rate coefficients and the calculated critical energies and other thermochemical properties, whose slopes showed to be conditioned by the energy provided to the compounds within the ion source. Moreover, it was found that the dissociation that leads to [C5H5O]+ is a process strongly dependent upon the electron withdrawing or donating properties of the substituent, favored by those factors that destabilize the molecular ion. On the contrary, the dissociation that leads to [M , C5H5O]+ is indifferent to the polar electronic effects of the substituent. The abundance of both products was governed by the rule of Stevenson,Audier, according to which the major ion is the one of less negative electronic affinity. Copyright © 2007 John Wiley & Sons, Ltd. [source] Synthesis of the Ammonium Salt of 6-Amino-2-hydroxy- 3,5-dinitropyrazine and a Comparison of its Properties with those of Ammonium 3,5-Diaminopicrate (ADAP)PROPELLANTS, EXPLOSIVES, PYROTECHNICS, Issue 5 2009Anthony Abstract The ammonium salt of 6-amino-2-hydroxy-3,5-dinitropyrazine has been synthesised from 2,6-dimethoxy-3,5-dinitropyrazine and its properties (DSC, crystal structure, impact sensitiveness and thermochemical properties) are compared with the analogous benzene derivative, ammonium 3,5-diaminopicrate. [source] | ||||||||||