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1.
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
2.
A. Miyake M. Wakakura T. Uchida A. Ushikubo 《Journal of Thermal Analysis and Calorimetry》2006,85(3):643-649
Cellulose, chitosan and piroxicam were investigated
by TG and DSC at heating up to 215°C, and by X-ray powder diffraction
before and after the heating.
Dehydration of cellulose and chitosan
comes to the end near 160°C. Thermal decomposition of chitosan starts
at the final stage of its dehydration, and the mass losses after these two
reactions overlap with one another. Enthalpy of dehydration is 47.1±2.4
kJ mol–1 of water for cellulose and 46.2±2.0
kJ mol–1 for chitosan. Thermal decomposition
of chitosan is an exothermic process. Crystal structure of cellulose after
heating remains unchanged, but that of chitosan contracts.
Piroxicam
melts at 200.7°C with the enthalpy of melting 35 kJ mol–1.
Heat capacity of the liquid phase is greater than that of the solid phase
by approximately 100 J mol–1K–1.
Cooled back to ambient temperature, piroxicam remains glassy for a long time,
crystallizing slowly back into the starting polymorph. 相似文献
3.
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
4.
The effect of the water vapor pressure on the thermal dehydration of manganese(II) formate dihydrate was studied by means
of isothermal gravimetry under various water vapor pressure, ranging from 4.6 to 24.4 torr.
The kinetics of dehydration was described by a two-dimensional phase-boundary model,R
2. The rate of dehydration decreased with increasing atmospheric water vapor pressure, but the Smith-Topley phenomenon was
not observed for the present dehydration. The activation energy and the frequency factor for the dehydration were 110–170
kJ·mol−1 and 1010–1016 cm·s−1, respectively. These values increased with increasing water vapor pressure, and were much larger than those reported for
the dehydration in vacuum. 相似文献
5.
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
6.
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
7.
Luciana S. Guinesi C. A. Ribeiro Marisa S. Crespi A. F. Santos Marisa V. Capela 《Journal of Thermal Analysis and Calorimetry》2006,85(2):301-307
This work aims the evaluation of the kinetic triplets
corresponding to the two successive steps of thermal decomposition of Ti(IV)–ethylenediaminetetraacetate
complex. Applying the isoconversional Wall–Flynn–Ozawa method
on the DSC curves, average activation energy: E=172.4±9.7
and 205.3±12.8 kJ mol–1, and pre-exponential
factor: logA=16.38±0.84 and 18.96±1.21
min–1 at 95% confidence interval could be
obtained, regarding the partial formation of anhydride and subsequent thermal
decomposition of uncoordinated carboxylate groups, respectively.
From E and logA values,
Dollimore and Málek methods could be applied suggesting PT (Prout–Tompkins)
and R3 (contracting volume) as the kinetic model to the partial formation
of anhydride and thermal decomposition of the carboxylate groups, respectively. 相似文献
8.
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
9.
H. Polli L. A. M. Pontes M. J. B. Souza V. J. Fernandes Jr A. S. Araujo 《Journal of Thermal Analysis and Calorimetry》2006,86(2):469-473
The degradation kinetics
of polycarbonate with flame retardant additive was investigated by means of
thermogravimetric analysis. The samples were heated from 30 to 900°C in
nitrogen atmosphere, with three different heating rates: 5, 10 and 20°C
min–1. The Vyazovkin model-free kinetics
method was applied to calculate the activation energy (E
a)
of the degradation process as a function of conversion and temperature. The
results indicated that the polycarbonate without flame retardant additive
starts to loose mass slightly over 380°C and the polycarbonate with flame
retardant additive, slightly over 390°C (with heating rate of 5°C
min–1). The activation energy for flame retardant
polycarbonate and normal polycarbonate were 190 and 165 kJ mol–1,
respectively. 相似文献
10.
Manmeet Singh Manhas Parveen Kumar Athar A. Hashmi Zaheer Khan 《Kinetics and Catalysis》2009,50(1):82-87
The kinetics and mechanism of the oxidation of D-galactose by chromium(VI) in the absence and presence of cerium(IV) and manganese(II) were studied spectrophotometrically
in aqueous perchloric acid media. The reaction is first order in both [D-galactose] and [H+]. The cerium(IV) inhibits the oxidation path, whereas manganese(II) catalyzes the reactions. The observed inhibitory role
of cerium(IV) suggests the formation of chromium(IV) as an intermediate. In the manganese(II) catalyzed path, the D-galactose-manganese(II) complex was considered to be an active oxidant. In this path, the complex forms a ternary chromate
ester with chromium(IV) which subsequently undergoes acid catalyzed redox decomposition (one-step three-electron transfer:
Indian J. Chem., 2004, vol. 42A, p. 1060; Colloids and Surfaces, 2001, vol. 193, p. 1) in the rate determining step. On the basis of kinetic data, the mechanism of D-galactose oxidation is proposed for parent, the manganese(II) catalyzed and cerium(IV) — inhibited reactions. The activation
parameters E
a = 59 kJ ΔH
# = 57 kJ mol−1, and ΔS
# = −119 J K−1 mol−1 are calculated and discussed. Reaction products are also examined.
Published in Russian in Kinetika i Kataliz, 2009, Vol. 50, No. 1, pp. 90–95.
This article was submitted by the authors in English. 相似文献
11.
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
12.
C. Sanchez-Pedreño M. S. García J. A. Ortuño M. I. Albero E. Ballester 《Analytical and bioanalytical chemistry》2001,369(7-8):680-683
A flow-through bulk optode based on the use of 1-(2-pyridylazo)-2-naphthol (PAN) immobilized in a plasticized poly(vinyl
chloride) membrane entrapped in a cellulose support, in conjuntion with the flow injection analysis technique, is proposed
for the determination of manganese(II). The calibration graph obtained at 570 nm was linear in the range 0.27–27.5 mg L–1 (5 × 10–6– 5 × 10–4 M) Mn(II) with a detection limit of 0.18 mg L–1. The coefficients of variation of the sensor response for 5.5 mg L–1 of Mn(II) were ±0.22% for consecutive measurements (n = 10), ±0.48% between days (n = 5) and ±0.38% between different membranes
(n = 6). The sensor was readily regenerated with the carrier acetic acid/acetate buffer of pH 4.5. The method was applied
to the determination of manganese in steels, waters and lemon tree leaves.
Received: 13 December 2000 / Revised: 25 January 2001 / Accepted: 26 January 2001 相似文献
13.
P. J. Masset 《Journal of Thermal Analysis and Calorimetry》2009,96(2):439-441
The dehydration of LiCl·H2O was studied under inert helium atmosphere by DTA/TG for different heating rates. The dehydration of LiCl·H2O proceeds through a two step reaction between 99–110 and 160–186°C, respectively. It leads to the formation of LiCl·0.5H2O as intermediate compound. The proposed mechanism is:
and
Based on the temperature peak of the DTA signals the activation energies of the two reactions were determined to be 240 kJ
mol−1 (step 1) and 137 kJ mol−1 (step 2), respectively. 相似文献
14.
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
15.
F. Langmaier P. Mokrejs K. Kolomazník M. Mládek R. Karnas 《Journal of Thermal Analysis and Calorimetry》2007,88(3):857-862
Differential scanning calorimetry was employed to investigate the reaction of diglycidyl ethers of bisphenol A (DGEBA) of
mean molecular mass 348–480 Da, with collagen hydrolysate of chrome-tanned leather waste in a solvent-free environment. The
reaction leads to biodegradable polymers that might facilitate recycling of plastic parts in products of the automotive and/or
aeronautics industry provided with protective films on this basis. The reaction proceeds in a temperature interval of 205–220°C,
at temperatures approx. 30–40°C below temperature of thermal degradation of collagen hydrolysate. The found value of reaction
enthalpy, 519.19 J g−1 (= 101.24 kJ mol−1 of epoxide groups) corresponds with currently found enthalpy values of the reaction of oxirane ring with amino groups. Reaction
heat depends on the composition of reaction mixture (or on mass fraction of diglycidyl ethers in the reaction mixture); proving
the dependence of kinetic parameters of the reaction (Arrhenius pre-exponential factor A (min−1) and activation energy E
a (kJ mol−1)) did not succeed. Obtained values of kinetic parameters are on a level corresponding to the assumption that reaction kinetics
is determined by diffusion. 相似文献
16.
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
17.
Thermodynamic stability of CdMoO4 was determined
by measuring the vapor pressures of Cd and MoO3 bearing
gaseous species. Th vaporization reaction could be described as CdMoO4(s)+MoO2(s)
=Cd(g)+2/n(MoO3)n
(n=3, 4 and 5). The vapor pressures of
the cadmium (p
Cd)
and trimer (p
(MoO3)3)
measured in the temperature range 987≤T/K≤1111
could be expressed, respectively, as ln (p
Cd/Pa)
= –32643.9/T+29.46±0.08 and
ln(p
(MoO3)3/Pa) = –32289.6/T+29.28±0.08. The standard molar Gibbs free
energy of formation of CdMoO4(s),
derived from the vaporization results could be expressed by the equations:
°f
G
CdMoO4
(s)
0= –1002.0+0.267T±14.5 kJ mol–1
(987≤T/K≤1033) and °f
G
CdMoO4 (s)
0
= –1101.9+0.363T±14.4 kJ mol–1
(1044≤T/K≤1111). The standard enthalpy
of formation of CdMoO4(s)
was found to be –1015.4±14.5 kJ mol–1
. 相似文献
18.
Francisco Ros Pilar Jiménez María Victoria Roux 《Monatshefte für Chemie / Chemical Monthly》2007,138(10):941-949
Summary. The cohesion potential energy of the crystal of one enantiomer of ethyl 3-cyano-3-(3,4-dimethyloxyphenyl)-2,2,4-trimethylpentanoate,
−47.7 ± 0.1 kJ mol−1 (0–90°C), was found out from the heat of sublimation (123.2 ± 5.1 kJ mol−1, 78.6°C) and the kinetic energies for the gas phase and the crystal. It was found that the entropy function of Debye’s theory of solids mathematically agreed with the vibrational entropy of the gas (variationally obtained), allowing to disclose
the vibrational energy using the Debye energy function (E
vib 835.0 kJ mol−1 (78.6°C), E
0 included). E
kin for the crystal (771.1 kJ mol−1 (78.6°C)) was obtained by Debye’s theory with the experimental heat capacity. The cohesion energy represented a moderate part of the sublimation energy.
The cohesion energy of the racemic crystal, −44.2 kJ mol−1, was obtained by the heat of formation of the crystal in the solid state (3.0 kJ mol−1, 83.3°C) and E
kin for the crystal (by Debye’s theory). The decrease in cohesion on formation of the crystal accounted for the energy of formation. The change in potential
energy on liquefaction of the racemate from the gas state was disclosed obtaining added-up E
vib + rot for the liquid in the way as to E
vib for the gas, the Debye entropy function being increasedly suited for the liquid (E
vib + rot 763.4 kJ mol−1 (115.4°C)). Positive ΔE
pot, 13.0 kJ mol−1, arised from the increase in electronic energy (Δ
l
νmean − 154.3 cm−1, by the dielectric nature of the liquid), added to the cohesion energy. 相似文献
19.
Francisco Ros Pilar Jiménez María Victoria Roux 《Monatshefte für Chemie / Chemical Monthly》2007,28(4):941-949
The cohesion potential energy of the crystal of one enantiomer of ethyl 3-cyano-3-(3,4-dimethyloxyphenyl)-2,2,4-trimethylpentanoate,
−47.7 ± 0.1 kJ mol−1 (0–90°C), was found out from the heat of sublimation (123.2 ± 5.1 kJ mol−1, 78.6°C) and the kinetic energies for the gas phase and the crystal. It was found that the entropy function of Debye’s theory of solids mathematically agreed with the vibrational entropy of the gas (variationally obtained), allowing to disclose
the vibrational energy using the Debye energy function (E
vib 835.0 kJ mol−1 (78.6°C), E
0 included). E
kin for the crystal (771.1 kJ mol−1 (78.6°C)) was obtained by Debye’s theory with the experimental heat capacity. The cohesion energy represented a moderate part of the sublimation energy.
The cohesion energy of the racemic crystal, −44.2 kJ mol−1, was obtained by the heat of formation of the crystal in the solid state (3.0 kJ mol−1, 83.3°C) and E
kin for the crystal (by Debye’s theory). The decrease in cohesion on formation of the crystal accounted for the energy of formation. The change in potential
energy on liquefaction of the racemate from the gas state was disclosed obtaining added-up E
vib + rot for the liquid in the way as to E
vib for the gas, the Debye entropy function being increasedly suited for the liquid (E
vib + rot 763.4 kJ mol−1 (115.4°C)). Positive ΔE
pot, 13.0 kJ mol−1, arised from the increase in electronic energy (Δ
l
νmean − 154.3 cm−1, by the dielectric nature of the liquid), added to the cohesion energy. 相似文献
20.
Z. Fengqi G. Hongxu L. Yang H. Rongzu C. Pei G. Sheng-li Y. Xu-wu S. Qizhen 《Journal of Thermal Analysis and Calorimetry》2006,85(3):791-794
The constant-volume combustion energies of
the lead salts of 2-hydroxy-3,5-dinitropyridine (2HDNPPb) and 4-hydroxy-3,5-dinitropyridine
(4HDNPPb), ΔU
c
(2HDNPPb(s) and 4HDNPP(s)),
were determined as –4441.92±2.43 and –4515.74±1.92
kJ mol–1 , respectively, at 298.15 K. Their
standard enthalpies of combustion, Δc
m
H θ(2HDNPPb(s) and 4HDNPPb(s), 298.15 K), and standard enthalpies of formation,
Δr
m H θ(2HDNPPb(s) and 4HDNPPb(s),
298.15 K) were as –4425.81±2.43, –4499.63±1.92 kJ
mol–1 and –870.43±2.76, –796.65±2.32
kJ mol–1 , respectively. As two combustion
catalysts, 2HDNPPb and 4HDNPPb can enhance the burning rate and reduce the
pressure exponent of RDX–CMDB propellant. 相似文献