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1.
Małecki A. Prochowska-Klisch B. Gajerski R. 《Journal of Thermal Analysis and Calorimetry》1998,54(1):25-34
It has been found that the modified Zhuravlev equation, [(1−α)−1/3−1]2=ktn, which describes the kinetics of oxidation of V2O4 and V6O13 in the temperature range 820–900 K and in the oxygen pressure range 1.0–20 kPa, can be derived via the assumption that the
changes in the observed activation energy result from the changing contributions of the two diffusion processes controlling
the reaction rate. The values of the observed activation energy are in the range 160–175 kJ mol−1 for V2O4 and 188–201 kJ mol−1 for V6O13 in the scope of the experimental oxygen pressures and temperatures and conversion degrees of 0.1–0.9.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
2.
The temperature dependences of the equilibrium constants of two chain reversible reactions in quinonediimine (quinonemonoimine)—2,5-dichlorohydroquinone
systems in chlorobenzene were studied. The enthalpy of equilibrium of the reversible reaction of quinonediimine with 4-hydroxydiphenylamine
was estimated from these data (ΔH = − 14.4±1.6 kJ mol−1) and a more accurate value of the N-H bond dissociation energy in the 4-anilinodiphenylaminyl radical was determined (D
NH = 278.6±3.0 kJ mol−1). A chain mechanism was proposed for the reaction between quinonediimine and 2,5-dichlorohydroquinone, and the chain length
was estimated (ν = 300 units) at room temperature. Processing of published data on the rate constant of the reaction of styrylperoxy
radicals with 2,5-dichlorohydroquinone in the framework of the intersecting parabolas method gave the O-H bond dissociation
energy in 2,5-dichlorohydroquinone: D
OH = 362.4±0.9 kJ mol−1. Taking into account these data, the O-H bond dissociation energy in the 2,5-dichlorosemiquinone radical was found: D
OH = 253.6±1.9 kJ mol−1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1661–1666, October, 2006. 相似文献
3.
Einar Uggerud 《Theoretical chemistry accounts》1997,97(1-4):313-316
The potential energy hypersurface of protonated glycine, GH+, has been investigated. The calculated G2(MP2) value for the proton affinity (PA) of glycine, PA
calc=895kJ mol−1, is in good agreement with the experimental value which has been estimated to lie in the range 864kJ mol−1 < PA
exp
<891kJ mol−1. Ab initio quantum chemical calculations of relevant parts of the potential energy surface of GH+ give a reaction model which is consistent with the observed mass spectrometric fragmentation pattern. The lowest energy unimolecular
reactions of GH+ are two distinct processes: (1) loss of CO, which has a substantial barrier for the reverse reaction, and (2) loss of CO
plus H2O, which has no barrier for the reverse reaction.
Received: 15 November 1996 / Accepted: 6 May 1997 相似文献
4.
The non-isothermal decomposition process of the powder sample of palladium acetylacetonate [Pd(acac)2] was investigated by thermogravimetric (TG) and the X-ray diffraction (XRD) techniques. Model-free isoconversional method
of Tang, applied to the investigated decomposition process, yield practically constant apparent activation energy in the range
of 0.05≤α≤0.95. It was established, that the Coats-Redfern (CR) method gives several statistically equivalent reaction models,
but only for the phase-boundary reaction models (R2 and R3), the calculated value of the apparent activation energy (E) is nearest to the values of E obtained by the Tang’s and Kissinger’s methods.
The apparent activation energy value obtained by the IKP method (132.4 kJ mol−1) displays a good agreement with the value of E obtained using the model-free analysis (130.3 kJ mol−1). The artificial isokinetic relationship (aIKR) was used for the numerical reconstruction of the experimental integral model
function, g(α). It was established that the numerically reconstructed experimental function follows R3 reaction model in the range of
α, taken from model-free analysis. Generally, decomposition process of Pd(acac)2 starts with initial nucleation which was characterized by rapid onset of an acceleratory reaction without presence of induction
period. 相似文献
5.
W. Xinmin Q. Chuansong Q. Songsheng T. Zhicheng 《Journal of Thermal Analysis and Calorimetry》2007,90(2):569-573
Rare-earth perchlorate complex coordinated with glycine [Nd2(Gly)6(H2O)4](ClO4)6·5H2O was synthesized and its structure was characterized by using thermogravimetric analysis (TG), differential thermal analysis
(DTA), chemical analysis and elementary analysis. Its purity was 99.90%. Heat capacity measurement was carried out with a
high-precision fully-automatic adiabatic calorimeter over the temperature range from 78 to 369 K. A solid-solid phase transformation
peak was observed at 256.97 K, with the enthalpy and entropy of the phase transformation process are 4.438 kJ mol−1 and 17.270 J K−1 mol−1, respectively. There is a big dehydrated peak appears at 330 K, its decomposition temperature, decomposition enthalpy and
entropy are 320.606 K, 41.364 kJ mol−1 and 129.018 J K−1 mol−1, respectively. The polynomial equations of heat capacity of this compound in different temperature ranges have been fitted.
The standard enthalpy of formation was determined to be −8023.002 kJ mol−1 with isoperibol reaction calorimeter at 298.15 K. 相似文献
6.
The relative acid strength and acid amount of solid acids has been determined from the adsorption and desorption of small molecules, such as argon. The order of activation energy for desorption of Ar from a solid acid, determined using temperature-programmed desorption (TPD), is sulfated zirconia > Cs2.5H0.5PW12O40 > proton-type zeolites > silica–alumina. The adsorption isotherms were analyzed using Langmuir and Henry equations. The Henry-type adsorption isotherms were also analyzed using the theory of Cremer and Flügge. The heat of Ar adsorption was 22 kJ mol−1 for sulfated zirconia and ca. 17 kJ mol−1 for mordenite, ZSM-5, and beta-zeolite. Molybdenum oxides reduced at 623 and 773 K exhibited a large heat of adsorption (19.3 and 19.7 kJ mol−1, respectively), and these materials are classified as superacids. W-Nb mixed-oxides and tungstated tin oxide (calcined at 1373 K), which are newly developed solid acids, had a heat of adsorption of 18.1 and 16.9 kJ mol−1, respectively. The type of acid site could be distinguished by comparing the heat of adsorption of Ar and N2. Our data indicate that Ar is useful for the characterization of solid acids. 相似文献
7.
V. A. Drebushchak Tatiana N. Drebushchak N. V. Chukanov Elena V. Boldyreva 《Journal of Thermal Analysis and Calorimetry》2008,93(2):343-351
Five polymorphs of chlorpropamide (α, β, δ, γ, and ε) were investigated near the melting point by using DSC. Structure of
samples was tested by X-ray powder diffraction. Four first polymorphs were found to transform into ε-polymorph, which melts
at T
m=128°C, Δm
H=24 kJ mol−1. Enthalpy of the polymorph transitions ranges from +3 kJ mol−1 for α→ε to −0.8 kJ mol−1 for β→ε.
Structure of three first polymorphs was published elsewhere, and the structure of δ-polymorph is published for the first time.
XRPD patterns for all polymorphs are reported, together with the atomic coordinates for the δ-polymorph. 相似文献
8.
Javed MR Rashid MH Nadeem H Riaz M Perveen R 《Applied biochemistry and biotechnology》2009,157(3):483-497
Monomeric extracellular endoglucanase (25 kDa) of transgenic koji (Aspergillus oryzae cmc-1) produced under submerged growth condition (7.5 U mg−1 protein) was purified to homogeneity level by ammonium sulfate precipitation and various column chromatography on fast protein
liquid chromatography system. Activation energy for carboxymethylcellulose (CMC) hydrolysis was 3.32 kJ mol−1 at optimum temperature (55 °C), and its temperature quotient (Q
10) was 1.0. The enzyme was stable over a pH range of 4.1–5.3 and gave maximum activity at pH 4.4. V
max for CMC hydrolysis was 854 U mg−1 protein and K
m was 20 mg CMC ml−1. The turnover (k
cat) was 356 s−1. The pK
a1 and pK
a2 of ionisable groups of active site controlling V
max were 3.9 and 6.25, respectively. Thermodynamic parameters for CMC hydrolysis were as follows: ΔH* = 0.59 kJ mol−1, ΔG* = 64.57 kJ mol−1 and ΔS* = −195.05 J mol−1 K−1, respectively. Activation energy for irreversible inactivation ‘E
a(d)’ of the endoglucanase was 378 kJ mol−1, whereas enthalpy (ΔH*), Gibbs free energy (ΔG*) and entropy (ΔS*) of activation at 44 °C were 375.36 kJ mol−1, 111.36 kJ mol−1 and 833.06 J mol−1 K−1, respectively. 相似文献
9.
H. X. Ma B. Yan Z. N. Li J. R. Song R. Z. Hu 《Journal of Thermal Analysis and Calorimetry》2009,95(2):437-444
The title compound 3,3-dinitroazetidinium (DNAZ) 3,5-dinitrosalicylate (3,5-DNSA) was prepared and the crystal structure has
been determined by a four-circle X-ray diffractometer. The thermal behavior of the title compound was studied under a non-isothermal
condition by DSC and TG/DTG techniques. The kinetic parameters were obtained from analysis of the TG curves by Kissinger method,
Ozawa method, the differential method and the integral method. The kinetic model function in differential form and the value
of E
a and A of the decomposition reaction of the title compound are f(α)=4α3/4, 130.83 kJ mol−1 and 1013.80s−1, respectively. The critical temperature of thermal explosion of the title compound is 147.55 °C. The values of ΔS
≠, ΔH
≠ and ΔG
≠ of this reaction are −1.35 J mol−1 K−1, 122.42 and 122.97 kJ mol−1, respectively. The specific heat capacity of the title compound was determined with a continuous C
p mode of mircocalorimeter. Using the relationship between C
p and T and the thermal decomposition parameters, the time of the thermal decomposition from initiation to thermal explosion (adiabatic
time-to-explosion) was obtained. 相似文献
10.
L. Peng X. Jiangjun M. Fangquan L. Xi Z. Chaocan 《Journal of Thermal Analysis and Calorimetry》2008,93(2):485-488
The standard molar enthalpy of combustion of cholesterol was measured at constant volume. According to value of Δr
U
mθ(−14358.4±20.65 kJ mol−1), Δr
H
mθ(−14385.7 kJ mol−1) of combustion reaction and Δf
H
mθ(2812.9 kJ mol−1) of cholesterol were obtained from the reaction equation. The enthalpy of combustion reaction of cholesterol was also estimated
by the average bond enthalpies. By design of a thermo-chemical recycle, the enthalpy of combustion of cholesterol were calculated
between 283.15∼373.15 K. Besides, molar enthalpy and entropy of fusion of cholesterol was obtained by DSC technique. 相似文献
11.
Non-isothermal Studies on Mechanism And Kinetics of Thermal Decomposition of Cobalt(II) Oxalate Dihydrate 总被引:1,自引:0,他引:1
B. Małecka E. Drożdż-Cieśla A. Małecki 《Journal of Thermal Analysis and Calorimetry》2002,68(3):819-831
Thermal decomposition of CoC2O4⋅2H2O was studied using DTA, TG, QMS and XRD techniques. It was shown that decomposition generally occurs in two steps: dehydration
to anhydrous oxalate and next decomposition to Co and to CoO in two parallel reactions. Two parallel reactions were distinguished
using mass spectra data of gaseous products of decomposition. Both reactions run according toAvrami–Erofeev equation. For
reaction going to metallic cobalt parameter n=2 and activation energy is 97±14 kJ mol–1. It was found that decomposition to CoO proceeds in two stages. First stage (0.12<αII<0.41) proceeds according to n=2, with activation energy 251±15 kJ mol–1 and second stage (0.45<αII<0.85) proceeds according to parameter n=1 and activation energy 203±21 kJ mol–1.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
12.
Summary The kinetics of the acid-catalysed hydrolysis of the [(imidazole)4Co(CO3)]+ ion was found to follow the rate law -dln[complex]/dt = k
1
K[H+](1 + K[H
+]) in the 25–45 °C range, [H+] 0.05–1.0 m range and I = 1.0m. The reaction sequence consists of a rapid protonation equilibrium followed by the one-end dissociation of the coordinated
carbonato ligand (rate-determining step) and subsequent fast release of the monodentate carbonato ligand. The rate parameter
values, k
1 and ITK, at 25 °C are 6.48 × 10−3s−1 and 0.31m
−1, respectively, and activation parameters for k
1 are ΔH
1
≠ = 86.1 ± 1.2kJ mol−1 and ΔS
1
≠ = 2.1 ± 6.3 J mol−1K−1. The hydrolysis rate increases with increase in ionic strength. The different ways of dealing with the data fit are presented
and discussed. The kinetic results are compared with those for the similar cobalt(III) complexes. 相似文献
13.
S. -X. Wang Z. -C. Tan Y. -S. Li L. -X. Sun Y. Li 《Journal of Thermal Analysis and Calorimetry》2008,92(2):483-487
Synthesis, characterization and thermal analysis of polyaniline (PANI)/ZrO2 composite and PANI was reported in our early work. In this present, the kinetic analysis of decomposition process for these
two materials was performed under non-isothermal conditions. The activation energies were calculated through Friedman and
Ozawa-Flynn-Wall methods, and the possible kinetic model functions have been estimated through the multiple linear regression
method. The results show that the kinetic models for the decomposition process of PANI/ZrO2 composite and PANI are all D3, and the corresponding function is ƒ(α)=1.5(1−α)2/3[1−(1-α)1/3]−1. The correlated kinetic parameters are E
a=112.7±9.2 kJ mol−1, lnA=13.9 and E
a=81.8±5.6 kJ mol−1, lnA=8.8 for PANI/ZrO2 composite and PANI, respectively. 相似文献
14.
15.
Stefan Perişanu Iulia Contineanu Mircea D. Banciu Hui Zhao Nigam Rath James Chickos 《Structural chemistry》2006,17(6):639-648
Condensed and gas phase enthalpies of formation of 3:4,5:6-dibenzo-2-hydroxymethylene-cyclohepta-3,5-dienenone (1, (−199.1 ± 16.4), (−70.5 ± 20.5) kJ mol−1, respectively) and 3,4,6,7-dibenzobicyclo[3.2.1]nona-3,6-dien-2-one (2, (−79.7 ± 22.9), (20.1 ± 23.1) kJ mol−1) are reported. Sublimation enthalpies at T=298.15 K for these compounds were evaluated by combining the fusion enthalpies at T = 298.15 K (1, (12.5 ± 1.8); 2, (5.3 ± 1.7) kJ mol−1) adjusted from DSC measurements at the melting temperature (1, (T
fus, 357.7 K, 16.9 ± 1.3 kJ mol−1)); 2, (T
fus, 383.3 K, 10.9 ± 0.1) kJ mol−1) with the vaporization enthalpies at T = 298.15 K (1, (116.1 ± 12.1); 2, (94.5 ± 2.2) kJ mol−1) measured by correlation-gas chromatography. The vaporization enthalpies of benzoin ((98.5 ± 12.5) kJ mol−1) and 7-heptadecanone ((94.5 ± 1.8) kJ mol−1) at T = 298.15 K and the fusion enthalpy of phenyl salicylate (T
fus, 312.7 K, 18.4 ± 0.5) kJ mol−1) were also determined for the correlations. The crystal structure of 1 was determined by X-ray crystallography. Compound
1 exists entirely in the enol form and resembles the crystal structure found for benzoylacetone. 相似文献
16.
Zuojun Wei Yong Huang Shuguang Deng Dipendu Saha Yingxin Liu Qilong Ren 《Reaction Kinetics and Catalysis Letters》2008,95(2):257-264
Alcoholysis of soybean isoflavone glucosides by butanol catalyzed by acidic ionic liquids was studied. The effects of the
ionic liquid catalyst type, catalyst concentration, reaction time and reaction temperature on glycoside conversions, and aglycons
yields were investigated. The optimum reaction conditions are found to be as follows: 0.036 g mL−1 of ionic liquid [BIM]HSO4 as catalyst, reaction temperature at 104±1°C, reaction time of 100 min. Under these optimum reaction conditions near complete
conversions of the three kinds of glycosides (daidzin, glycitin and genistin) are obtained. Furthermore, the kinetics parameters
for the alcoholysis were estimated. The activation energies of alcoholysis for the three kinds of isoflavone glucosides are
124 kJ mol−1, 67 kJ mol−1 and 115 kJ mol−1, respectively. 相似文献
17.
The basic kinetic parameters of thermal polymerization of hexafluoropropylene, namely, general rate constants, degree of polymerization,
and their temperature and pressure dependences in the range of 230–290 °C and 2–12 kbar (200–1200 MPa) were determined. The
activation energy (E
act = 132±4 kJ mol−1) and activation volume (ΔV
0
≠ = −27±1 cm3 mol−1) were calculated. The activation energy of thermal initiation of polymerization was estimated. The reaction scheme based
on the assumption about a biradical mechanism of polymerization initiation was proposed. 相似文献
18.
Lebedev B. V. Bykova T. A. Lobach A. S. 《Journal of Thermal Analysis and Calorimetry》2000,62(1):257-265
The temperature dependence of the molar heat capacity (C0
p) of hydrofullerene C60H36 between 5 and 340 K was determined by adiabatic vacuum calorimetry with an error of about 0.2%. The experimental data were
used for the calculation of the thermodynamic functions of the compound in the range 0 to340 K. It was found that at T=298.15 K and p=101.325 kPa C0
p (298.15)=690.0 J K−1 mol−1,Ho(298.15)−Ho(0)= 84.94 kJ mol−1,So(298.15)=506.8 J K−1 mol−1, Go(298.15)−Ho(0)= −66.17 kJ mol−1. The standard entropy of formation of hydrofullerene C60H36 and the entropy of reaction of its formation by hydrogenation of fullerene C60 with hydrogen were estimated and at T=298.15 K they were ΔfSo= −2188.4 J K−1 mol−1 and ΔrSo= −2270.5 J K−1mol−1, respectively.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
19.
Maria Luisa A. Gonçalves Deusa Angélica da Mota Pinto Ana Maria R. F. Teixeira M. A. G. Teixeira 《Journal of Thermal Analysis and Calorimetry》2008,91(2):341-346
Dynamic kinetic analyses were performed on different Brazilian petroleum fractions by thermogravimetry. The data were treated
by a multiple heating rate methodology. The apparent activation energies for the light and middle fractions within the range
of 62–74 kJ mol−1 and for heavy distillation residues were within the range of 80–100 kJ mol−1 at lower conversions and 100–240 kJ mol−1 at higher conversions. The kinetic study can be a criterion for tells apart the main phenomena involved in the thermal behavior
of the refinery feedstock. 相似文献
20.
Jonathan F. Ojo Jide Ige Grace O. Ogunlusi Olanrewaju Owoyomi Esan S. Olaseni 《Transition Metal Chemistry》2006,31(6):782-785
The kinetics of the reactions between Fe(phen)
3
2+
[phen = tris–(1,10) phenanthroline] and
Co(CN)5X3− (X = Cl, Br or I) have been investigated in aqueous acidic solutions at I = 0.1 mol dm−3 (NaCl/HCl). The reactions were carried out at a fixed acid concentration ([H+] = 0.01 mol dm−3) and the second-order rate constants for the reactions at 25 °C were within the range of (0.151–1.117) dm3 mol−1 s−1. Ion-pair constants K
ip for these reactions, taking into consideration the protonation of the cobalt complexes, were 5.19 × 104, 3.00 × 102 and 4.02 × 104 mol−1 dm−3 for X = Cl, Br and I, respectively. Activation parameters measured for these systems were as follows: ΔH* (kJ K−1 mol−1) = 94.3 ± 0.6, 97.3 ± 1.0 and 109.1 ± 0.4; ΔS* (J K−1) = 69.1 ± 1.9, 74.9 ± 3.2 and 112.3 ± 1.3; ΔG* (kJ) = 73.7 ± 0.6, 75.0 ± 1.0 and 75.7 ± 0.4; E
a
(kJ) = 96.9 ± 0.3, 99.8 ± 0.4, and 122.9 ± 0.3; A (dm3 mol−1 s−1) = (7.079 ± 0.035) × 1016, (1.413 ± 0.011) × 1017, and (9.772 ± 0.027) × 1020 for X = Cl, Br, and I respectively. An outer – sphere mechanism is proposed for all the reactions. 相似文献