共查询到20条相似文献,搜索用时 31 毫秒
1.
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
2.
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
3.
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
4.
V. A. Lukyanova T. S. Papina K. V. Didenko A. S. Alikhanyan 《Journal of Thermal Analysis and Calorimetry》2008,92(3):743-746
The standard enthalpy of combustion of crystalline silver pivalate, (CH3)3CC(O)OAg (AgPiv), was determined in an isoperibolic calorimeter with a self-sealing steel bomb, Δc
H
0 (AgPiv, cr)= −2786.9±5.6 kJ mol−1. The value of standard enthalpy of formation was derived for crystalline state: Δf
H
0(AgPiv,cr)= −466.9±5.6 kJ mol−1. Using the enthalpy of sublimation, measured earlier, the enthalpy of formation of gaseous dimer was obtained: Δf
H
0(Ag2Piv2,g)= −787±14 kJ mol−1. The enthalpy of reaction (CH3)3CC(O)OAg(cr)=Ag(cr)+(CH3)3CC(O)O.(g) was estimated, Δr
H
0=202 kJ mol−1. 相似文献
5.
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
6.
In this work, a kinetic study on the thermal degradation of carbon fibre reinforced epoxy is presented. The degradation is
investigated by means of dynamic thermogravimetric analysis (TG) in air and inert atmosphere at heating rates from 0.5 to
20°C min−1 . Curves obtained by TG in air are quite different from those obtained in nitrogen. A three-step loss is observed during
dynamic TG in air while mass loss proceeded as a two step process in nitrogen at fast heating rate. To elucidate this difference,
a kinetic analysis is carried on. A kinetic model described by the Kissinger method or by the Ozawa method gives the kinetic
parameters of the composite decomposition. Apparent activation energy calculated by Kissinger method in oxidative atmosphere
for each step is between 40–50 kJ mol−1 upper than E
a calculated in inert atmosphere.
The thermo-oxidative degradation illustrated by Ozawa method shows a stable apparent activation energy (E
a ≈130 kJ mol−1 ) even though the thermal degradation in nitrogen flow presents a maximum E
a for 15% mass loss (E
a ≈60 kJ mol−1 ).
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
7.
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
8.
The relative thermodynamic stabilities of 2,5-dihydrofuran (1) and 2,3-dihydrofuran (2), and of 3,4-dihydro-6H-pyran (3) and 3,4-dihydro-2H-pyran (4), were determined at several temperatures by base-catalyzed equilibration in DMSO solution. For 1 → 2, = –15.4±0.1 kJ mol−1, =–12.6±0.5 kJ mol−1, and =9.5±1.3 J K−1 mol−1 at 298.15 K. The second-law reaction enthalpy agrees with literature data based on calorimetric enthalpies of hydrogenation of the isomeric forms in hexane. For 3 → 4, =–19.3±0.2 kJ mol−1, = –18.9±1.1 kJ mol−1 and =1.1±3.0 J K−1 mol−1 at 298.15 K: the experimental reaction enthalpy is in marked disagreement with literature data based on estimation. On the other hand, both of the experimental reaction enthalpies of the present study are in good agreement with DFT calculations using the B3LYP functional and 6-311+G(2d,p) basis set. 相似文献
9.
G. Xie S. P. Chen S. L. Gao X. X. Meng Q. Z. Shi 《Journal of Thermal Analysis and Calorimetry》2006,83(3):693-700
A novel solid complex, formulated as Ho(PDC)3
(o-phen), has been obtained from the reaction
of hydrate holmium chloride, ammonium pyrrolidinedithiocarbamate (APDC) and
1,10-phenanthroline (o-phen·H2O)
in absolute ethanol, which was characterized by elemental analysis, TG-DTG
and IR spectrum. The enthalpy change of the reaction of complex formation
from a solution of the reagents, ΔrHmθ (sol), and the molar heat capacity of the complex, cm,
were determined as being –19.161±0.051 kJ mol–1
and 79.264±1.218 J mol–1 K–1
at 298.15 K by using an RD-496 III heat conduction microcalorimeter. The enthalpy
change of complex formation from the reaction of the reagents in the solid
phase, ΔrHmθ(s), was calculated as
being (23.981±0.339) kJ mol–1 on the
basis of an appropriate thermochemical cycle and other auxiliary thermodynamic
data. The thermodynamics of reaction of formation of the complex was investigated
by the reaction in solution at the temperature range of 292.15–301.15
K. The constant-volume combustion energy of the complex, ΔcU, was determined as being –16788.46±7.74
kJ mol–1 by an RBC-II type rotating-bomb
calorimeter at 298.15 K. Its standard enthalpy of combustion, ΔcHmθ, and standard enthalpy of formation,
ΔfHmθ, were calculated to be –16803.95±7.74 and –1115.42±8.94
kJ mol–1, respectively. 相似文献
10.
V. V. Nedel'ko A. V. Shastin B. L. Korsunskii N. V. Chukanov T. S. Larikova A. I. Kazakov 《Russian Chemical Bulletin》2005,54(7):1710-1714
Ditetrazol-5-ylamine (DTA) was synthesized from cyanuric chloride in four steps. The thermal decomposition of DTA in the solid
state was studied by thermogravimetry, volumetry, mass spectrometry, IR spectroscopy, and calorimetry. Under isothermal conditions
at 200–242 °C, thermal decomposition obeys the first order autocatalytic kinetics. The kinetic and activation parameters of
DTA decomposition were determined. The composition of gaseous reaction products and the structure of condensed residue were
studied. The thermal effect of thermal DTA decomposition is 281.4 kJ mol−1. The nitrogen content in a mixture of gaseous products formed by the reaction in a temperature interval of 200–242 °C exceeds
97 vol.%.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1660–1664, July, 2005. 相似文献
11.
It has been shown that the exothermic decomposition of KMnO4 in vacuum is accompanied by a significant self-heating effect. It manifests itself in the reduction of the molar enthalpy
of the reaction, determined by the third-law method. In comparison with the value 138.3±0.6 kJ mol−1 that is valid for the decomposition of KMnO4 under atmospheric pressure at 493–553 K, the molar enthalpy in vacuum (10−4-10−7 bar) at 484–511 K varies in the range of 136 to 126 kJ mol−1. This is related to the reduction of the thermal conductivity of residual air in the furnace and, as a result, to the self-heating
of the reactant, that accelerates the exothermic reaction. A simple method of evaluation of the self-heating effect has been
developed. By analogy with the known method for evaluation of the self-cooling effect, it is based on the determination of
the molar enthalpy by the third-law method at two different temperatures. The increase of sample temperature above the furnace
temperature Tf in the case of the exothermic decomposition of KMnO4 in a high vacuum and T
f≥490 K reaches a few tens of degrees. 相似文献
12.
H. Polli L. A. M. Pontes A. S. Araujo Joana M. F. Barros V. J. FernandesJr. 《Journal of Thermal Analysis and Calorimetry》2009,95(1):131-134
The degradation kinetics of the ABS terpolymer (acrylonitrile-butadiene-styrene) was investigated by means of thermogravimetric
analysis. The samples were heated from 30 to 900°C in nitrogen atmosphere applying three different heating rates: 5, 10 and
20°C min−1. The Vyazovkin model-free kinetic method was used to calculate the activation energy (E) of the degradation process as a function of conversion and temperature. Between 20 and 80% of conversion, E was calculated
and the figures were: for ABS GP, E is 204.5±11.5 kJ mol−1 (medium value); for ABS HI, E is 239.0±9.8 kJ mol−1; for ABS HH, E is 242.4±5.4 kJ mol−1. 相似文献
13.
Tanmay Chattopadhyay Manami Ghosh Arpita Banerjee Kazi Sabnam Banu Debasis Das Munirathinam Nethaji 《Transition Metal Chemistry》2007,32(4):531-535
Linkage isomers trans-bis(N-propyl-1,2-diaminoethane)dinitronickel(II) (brown, 1), trans-bis(N-isopropyl-1,2-diaminoethane)dinitritonickel(II) (blue-violet, 2a) and trans-bis(N-isopropyl-1,2-diaminoethane)dinitronickel(II) (brown, 2b) have been synthesized from solution and X-ray single crystal structure analysis of complex (1) has been performed. Simultaneous TG-DTA analyses reveal that complex (1) exhibits two successive phase transitions before to undergo decomposition (initial temperature of decomposition, Ti = 215
°C). The first one is reversible (82–98 °C; ΔH = 1.75 kJ mol−1 for heating and 93–77 °C; ΔH = −1.65 kJ mol−1 for cooling) and the second one is irreversible endothermic (135–150 °C kJ mol−1; ΔH = 1.80 kJ mol−1) phase transition. No visual color changes are observed in any of the two transitions. The causes related to the first phase
transition remain unexplored. However, on the basis of IR spectral studies the second phase transition is supposed to be due
to conformational changes of the diamine chelate rings. On the other hand, complexes (2a) and (2b) undergo decomposition without showing any phase transition [Ti = 185 and 195 °C for (2a) and (2b), respectively]. 相似文献
14.
A. A. Saboury H. Ghourchaei M. H. Sanati M. S. Atri M. Rezaei-Tawirani G. H. Hakimelahi 《Journal of Thermal Analysis and Calorimetry》2007,89(3):921-927
Binding properties and structural changes of human growth hormone (hGH) due to the interaction by cobalt ion (Co2+) were done at 27°C in NaCl solution, 50 mM, using different techniques of UV-Vis spectroscopy, circular dichroism (CD), isothermal
titration calorimetry (ITC) and differential scanning calorimetry (DSC) techniques. There is a set of three identical and
non-interacting binding sites for cobalt ions. The intrinsic association equilibrium constant and the molar enthalpy of binding
obtained by ITC are 0.80 mM−1 and −16.70 kJ mol−1, respectively. The intrinsic association equilibrium constant obtained by a standard isothermal titration UV-Vis spectrophotometry
method is also 0.79 mM−1, which is in good agreement with the value obtained from ITC. The Gibbs free energy and entropy changes due to the binding
of cobalt ion on hGH are −16.67 kJ mol−1 and −0.1 J K−1 mol−1, respectively. Energetic domains analysis by DSC shows that phase transition of hGH in the presence of cobalt occurs at one
main transition. Deconvolution of the main transition provides two sub-transitions with different values of the melting point
and enthalpy of unfolding (33°C and 164 kJ mol−1 for the first and 49°C and 177 kJ mol−1 for the second, respectively). Interaction of cobalt ions with hGH prevents aggregation by an affect on the hydrophobicity
of the protein macromolecule and provide useful information about its structure due to becoming reversible of protein thermal
denaturation. 相似文献
15.
16.
Ladislav Kosa Iveta Macková Ivo Proks Ondrej Pritula Ľubomír Smrčok Miroslav Boča Håkan Rundlőf 《Central European Journal of Chemistry》2008,6(1):27-32
Three thermal effects on heating/cooling of K2TaF7 in the temperature interval of 680–800°C were investigated by the DSC method. The values determined for the enthalpy change
of the individual processes are: ΔtransIIHm(K2TaF7; 703°C) = 1.7(2) kJ mol−1, ΔtransIHm(K2TaF7; 746°C) = 19(1) kJ mol−1 and ΔtransIIIHm(K2TaF7; 771°C) = 13(1) kJ mol−1. The first thermal effect was attributed to a solid-solid phase transition; the second to the incongruent melting of K2TaF7 and the third to mixing of two liquids. These findings are supported by in situ neutron powder diffraction experiments performed in the temperature interval of 654–794°C.
相似文献
17.
The dissociation pressure for the process PtCl2(s) → Pt(s) + Cl2(g) was measured by the static method with diaphragm zero-pressure gauges. The approximating equation for the temperature
dependence on the dissociation pressure for the above reaction was found. The enthalpy (137.7±0.3 kJ mol−1) and entropy (163.6±0.4 J mol−1 K−1) of PtCl2(s) dissociation and enthalpies of formation and absolute entropies of platinum di- and trichlorides at 298.15 K were calculated.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1345–1348, June, 2005. 相似文献
18.
1. Results of thermodynamic and kinetic investigations for the different crystalline calcium carbonate phases and their phase
transition data are reported and summarized (vaterite: V; aragonite: A; calcite: C). A→C: T
tr=455±10°C, Δtr
H=403±8 J mol–1 at T
tr, V→C: T
tr=320–460°C, depending on the way of preparation,Δtr
H=–3.2±0.1 kJ mol–1 at T
tr,Δtr
H=–3.4±0.9 kJ mol–1 at 40°C, S
V
Θ= 93.6±0.5 J (K mol)–1, A→C: E
A=370±10 kJ mol–1; XRD only, V→C: E
A=250±10 kJ mol–1; thermally activated, iso- and non-isothermal, XRD
2. Preliminary results on the preparation and investigation of inhibitor-free non-crystalline calcium carbonate (NCC) are
presented. NCC→C: T
tr=276±10°C,Δtr
H=–15.0±3 kJ mol–1 at T
tr, T
tr – transition temperature, Δtr
H – transition enthalpy, S
Θ – standard entropy, E
A – activation energy.
3. Biologically formed internal shell of Sepia officinalis seems to be composed of ca 96% aragonite and 4% non-crystalline calcium carbonate.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
19.
E. G. Klimchuk G. M. Avetisyan A. A. Khodak V. T. Minasyan K. G. Gazaryan A. S. Mukas'yan A. G. Merzhanov 《Russian Chemical Bulletin》1999,48(12):2245-2258
The regularities of chemical reactions in solid 8-hydroxyquinoline—chloramine B mixtures were studied under conditions of
organic self-propagating high-temperature synthesis (SHS), isothermal reaction, and thermal explosion in the 20–220 °C temperature
range. Comprehensive physicochemical analysis and microstructural study of the reaction products were carried out. The temperature
of SHS initiation (58 °C), the heat of the reaction (129±9 kJ mol−1), the stoichiometric coefficient (1), the maximum temperature (T
max=98–140 °C), and the velocity of SHS wave propagation (u=0.15–0.55 mm s−1) were determined. Depending on the ratio of the reactants (n), a low-temperature non-degeerate stable gasless mode (n≤1,T
max=115 °C,E
a=42 kcal mol−1) and a high-temperature mode (n>1,T
max=140 °C,E
a=0.4 kcal mol−1) are possible for SHS. The SHS affords monohydroxy and monochloro derivatives of 8-hydroxyquinoline, benzenesulfonamide,
NaCl, NaOH, and H2O. The mechanism of the solid-phase reaction at temperatures below 58 °C includes surface, solid-phase, and gas-phase diffusion;
that for SHS is capillary spreading of the hydroxyquinoline melt.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2271–2284, December, 1999. 相似文献
20.
N. I. Matskevich 《Journal of Thermal Analysis and Calorimetry》2007,90(3):955-958
Enthalpy of formation of the perovskite-related oxide BaCe0.9In0.1O2.95 has been determined at 298.15 K by solution calorimetry. Solution enthalpies of barium cerate doped with indium and mixture
of BaCl2, CeCl3, InCl3 in ratio 1:0.9:0.1 have been measured in 1 M HCl with 0.1 M KI. The standard formation enthalpy of BaCe0.9In0.1O2.95 has been calculated as −1611.7±2.6 kJ mol−1. Room-temperature stability of this compound has been assessed in terms of parent binary oxides. The formation enthalpy of
barium cerate doped by indium from the mixture of binary oxides is Δox
H
0 (298.15 K)=−36.2±3.4 kJ mol−1. 相似文献