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1.
K. Chrissafis K. M. Paraskevopoulos C. Manolikas 《Journal of Thermal Analysis and Calorimetry》2006,84(1):195-199
The
thermal effect accompanying the transition of Cu2–xSe
into a superionic conduction state was studied by non-isothermal measurements,
at different heating and cooling rates (β=1, 2.5, 5, 10 and 20°C
min–1). During heating the peak temperature
(Tp) remains almost
stable for all values of β, (136.8±0.4°C for Cu2Se
and 133.0±0.3°C for Cu1.99Se). A gradual
shift of the initiation of the transformation towards lower temperatures is
observed, as the heating rate increases. During cooling there is a significant
shift in the position of the peak maximum (Tp)
towards lower temperatures with the increase of the cooling rate. A small
hysteresis is observed, which increases with the increase of the cooling rate, β.
The mean value of transformation enthalpy was found to be 30.3±0.8
J g–1 for Cu2Se and
28.9±0.9 J g–1 for Cu1.99Se.
The transformation can be described kinetically by the model f(ǯ)=(1–ǯ)n(1+kcatX), with activation energy E=175 kJ mol–1,
exponent value n equal to 0.2, logA=20 and log(kcat)=
0.5. 相似文献
2.
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
3.
The phase transition at T
p (~109 °C) of RbH2PO4 and its composite with SiO2 has been investigated by thermal analysis here. In the case of neat RbH2PO4, there is a linear relationship between endothermic peak temperature (T
m) and square root of heating rate (Φ
1/2), from which the onset temperature of phase transition can be determined. Besides, Kissinger method and another calculation
method were employed to obtain the activation energy of phase transition. The detailed deduction process was presented in
this paper, and the estimated activation energies are E
1 ≈ 126.3 kJ/mol and E
2 ≈ 129.2 kJ/mol, respectively. On the other hand, the heterogeneous doping of RbH2PO4 with SiO2 as dopant facilitates its proton conduction and leads to the disappearance of jump in conductivity at T
p. The heats of transition in the composites decrease gradually with increasing the molar fraction of SiO2 additives. In the cooling process, a new and broad exothermic peak appeared between ~95 and ~110 °C, and its intensity also
changes with the SiO2 amount. These phenomena might be related to the formation of amorphous phase of RbH2PO4 on the surface of SiO2 particles due to the strong interface interaction. 相似文献
4.
S. F. Santos M. C. de Andrade J. A. Sampaio A. B. da Luz T. Ogasawara 《Journal of Thermal Analysis and Calorimetry》2007,87(3):743-746
TiO2–CeO2 oxides
for application as ceramic pigments were synthesized by the Pechini method.
In the present work the polymeric network of the pigment precursor was studied
using thermal analysis. Results obtained using TG and DTA showed the occurrence
of three main mass loss stages and profiles associated to the decomposition
of the organic matter and crystallization. The kinetics of the degradation
was evaluated by means of TG applying different heating rates. The activation
energies (E
a) and
reaction order (n) for each stage were
determined using Horowitz–Metzger, Coats–Redfern, Kissinger and
Broido methods. Values of E
a
varying between 257–267 kJ mol–1 and n=0–1 were found. According to the kinetic
analysis the decomposition reactions were diffusion controlled. 相似文献
5.
A. Migdał-Mikuli N. Górska E. Szostak 《Journal of Thermal Analysis and Calorimetry》2007,90(1):223-228
Phase transition and thermal decomposition of hexadimethylsulfoxidealuminium chloride were studied by differential scanning
calorimetry (DSC), thermogravimetry (TG) and simultaneous differential thermal analysis (SDTA). The gaseous products of the
decomposition were on-line identified by a quadrupole mass spectrometer (QMS). In the temperature range of 95–300 K, [Al(DMSO)6]Cl3 indicates one phase transition at T
ch=244.96 K (on heating) and at T
cc=220.87 K (on cooling). Large thermal hysteresis of the phase transition (∼24 K) indicates its first order character. Large
value of transition entropy (ΔS≈40 J mol−1 K−1) suggests its configurational character. Thermal decomposition of the title compound proceeds in four main stages. In the
first stage, which starts just above ca. 300 K, the compound loses two DMSO molecules per one formula unit and undergoes into
[Al(DMSO)4]Cl3. In the second stage, the next three DMSO ligands are released and simultaneously decomposed. The third stage, which continues
up to ca. 552 K, is connected with a loss of the last DMSO ligand and the formation of AlCl3. In the fourth stage AlCl3 reacts with carbon monoxide that originates from the decomposition of DMSO, and first aluminium oxychloride and next solid
Al2O3 plus carbon are created. 相似文献
6.
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
7.
M. Hampl J. Leitner K. Růžička M. Straka P. Svoboda 《Journal of Thermal Analysis and Calorimetry》2007,87(2):553-556
The heat capacity and the heat content of
bismuth niobate BiNb5O14 were
measured by the relaxation time method, DSC and drop method, respectively.
The temperature dependence of heat capacity in the form C
pm=455.84+0.06016T–7.7342·106/T
2 (J K–1
mol–1) was derived by the least squares method
from the experimental data. Furthermore, the standard molar entropy at 298.15
K S
m=397.17 J K–1
mol–1 was derived from the low temperature
heat capacity measurement. 相似文献
8.
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
9.
Digo Hermínio P. Pinto Susana S. Moura Ramos Joaquim J. 《Journal of Thermal Analysis and Calorimetry》2004,77(3):893-904
The thermal behaviour of salicylsalicylic acid (CAS number 552-94-3) was studied by differential scanning calorimetry (DSC).
The endothermic melting peak and the fingerprint of the glass transition were characterised at a heating rate of 10°C min-1. The melting peak showed an onset at T
on = 144°C (417 K) and a maximum intensity at T
max = 152°C (425 K), while the onset of the glass transition signal was at T
on = 6°C. The melting enthalpy was found to be ΔmH = 28.9±0.3 kJ mol-1, and the heat capacity jump at the glass transition was ΔC
P = 108.1±0.1 J K-1mol-1. The study of the influence of the heating rate on the temperature location of the glass transition signal by DSC, allowed
the determination of the activation energy at the glass transition temperature (245 kJ mol-1), and the calculation of the fragility index of salicyl salicylate (m = 45). Finally, the standard molar enthalpy of formation of crystalline monoclinic salicylsalicylic acid at T = 298.15 K, was determined as ΔfHm
o(C14H10O5, cr) = - (837.6±3.3) kJ mol-1, by combustion calorimetry.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
10.
Electrical conductivity in the monoclinic Li2TiO3, cubic Li1.33Ti1.67O4, and in their mixture has been studied by impedance spectroscopy in the temperature range 20–730 °C. Li2TiO3 shows low lithium ion conductivity, σ300≈10–6 S/cm at 300 °C, whereas Li1.33Ti1.67O4 has 3×10–8 at 20 °C and 3×10–4 S/cm at 300 °C. Structural properties are used to discuss the observed conductivity features. The conductivity dependences
on temperature in the coordinates of 1000/T versus loge(σT) are not linear, as the conductivity mechanism changes. Extrinsic and intrinsic conductivity regions are observed. The change
in the conductivity mechanism in Li2TiO3 at around 500–600 °C is observed and considered as an effect of the first-order phase transition, not reported before. Formation
of solid solutions of Li2–
x
Ti1+
x
O3 above 900 °C significantly increases the conductivity. Irradiation by high-energy (5 MeV) electrons causes defects and the
conductivity in Li2TiO3 increases exponentially. A dose of 144 MGy yields an increase in conductivity of about 100 times at room temperature.
Electronic Publication 相似文献
11.
S. K. Tripathi Balbir Singh Patial Nagesh Thakur 《Journal of Thermal Analysis and Calorimetry》2012,107(1):31-38
Differential scanning calorimetry data at different heating rates (5, 10, 15 and 20 °C min−1) of Se70Te15In15 chalcogenide glass is reported and discussed. The crystallization mechanism is explained in terms of recent analyses developed
for use under non-isothermal conditions. The value of Avrami exponent (n) indicates that the glassy Se70Te15In15 alloy has three-dimensional growth. The average values of the activation energy for glass transition, E
g, and crystallization process, E
c, are (154.16 ± 4.1) kJ mol−1 and (98.81 ± 18.1) kJ mol−1, respectively. The ease of glass formation has also been studied. The reduced glass transition temperature (T
rg), Hruby’ parameter (K
gl) and fragility index (F
i) indicate that the prepared glass is obtained from a strong glass forming liquid. 相似文献
12.
Latifa A. Al-Hajji Muhammad A. Hasan Mohamed I. Zaki 《Journal of Thermal Analysis and Calorimetry》2010,100(1):43-49
The formation of Barium monotungstate (BaWO4) particles in equimolar powder mixtures of BaCO3 and WO3 was examined under isothermal and non-isothermal conditions upon heating in air at 25–1200 °C, using thermogravimetry. Concurrence
of the observed mass loss (due to the release of CO2) to the occurrence of the formation reaction was evidenced. Accordingly, the extent of reaction (x) was determined as a function of time (t) or temperature (T). The x–t and x–T data thus obtained were processed using well established mathematical apparatus and methods, in order to characterize nature
of reaction rate-determining step, and derive isothermal and non-isothermal kinetic parameters. Moreover, the reaction mixture
quenched at various temperatures (600–1,000 °C) in the reaction course was analyzed by various spectroscopic and microscopic
techniques, for material characterization. The results obtained indicated that the reaction rate may be controlled by unidirectional
diffusion of WO3 species across the product layer (BaWO4), which was implied to form on the barium carbonate particles. The isothermally determined activation energy (118–125 kJ/mol)
was found to be more credible than that (245 kJ/mol) determined non-isothermally. 相似文献
13.
S. Vecchio 《Journal of Thermal Analysis and Calorimetry》2007,87(1):79-83
The vaporization enthalpies of two acetanilide pesticides, alachlor
(2’,6’-diethyl-N-(methoxymethyl)-2-chloroacetanilide) and metolachlor
(2-chloro-N-(2-ethyl-6-methylphenyl)-N-[(1S)-2-methoxy-1-methylethyl] acetamide),
were determined by processing non-isothermal thermogravimetry data according
to the Clausius-Clapeyron equation. The reliability of the procedure proposed
was tested carrying out some experiments at different heating rates using
acetanilide as a reference compound. A good agreement is found among the vaporization
enthalpies derived from all the multi-heating rate experiments as well as
with the one predicted from the vapor pressure data taken from literature.
The vaporization temperatures (T
vap=470±2
K and T
vap=479±2
K) and enthalpies (Δvap
H°(436
K)=85±1 kJ mol–1 and Δvap
H°(436 K)=70±1 kJ mol–1)
for alachlor and metolachlor, were selected, respectively. 相似文献
14.
Ju-Lan Zeng Sai-Bo Yu Bo Tong Li-Xian Sun Zhi-Cheng Tan Zhong Cao Dao-Wu Yang Jing-Nan Zhang 《Journal of Thermal Analysis and Calorimetry》2011,103(3):1087-1093
An N-tert-butyloxycarbonylated organic synthesis intermediate, (S)-tert-butyl 1-phenylethylcarbamate, was prepared and investigated by means of differential scanning calorimetry (DSC) and thermogravimetry
(TG). The molar heat capacities of (S)-tert-butyl 1-phenylethylcarbamate were precisely determined by means of adiabatic calorimetry over the temperature range of 80-380 K.
There was a solid–liquid phase transition exhibited during the heating process with the melting point of 359.53 K. The molar
enthalpy and entropy of this transition were determined to be 29.73 kJ mol−1 and 82.68 J K−1 mol−1 based on the experimental C
p–T curve, respectively. The thermodynamic functions, [HT0 - H298.150 H_{T}^{0} - H_{298.15}^{0} ] and [ST0 - S298.150 S_{T}^{0} - S_{298.15}^{0} ], were calculated from the heat capacity data in the temperature range of 80–380 K with an interval of 5 K. TG experiment
showed that the pyrolysis of the compound was started at the temperature of 385 K and terminated at 510 K within one step. 相似文献
15.
We studied thermal transitions and physical stability
of oil-in-water emulsions containing different milk fat compositions, arising
from anhydrous milk fat alone (AMF) or in mixture (2:1 mass ratio) with a
high melting temperature (AMF–HMT) or a low melting temperature (AMF–LMT)
fraction. Changes in thermal transitions in bulk fat and emulsion samples
were monitored by differential scanning calorimetry (DSC) under controlled
cooling and reheating cycles performed between 50 and –45°C (5°C
min–1). Comparison between bulk fat samples
and emulsions indicated similar values of melting completion temperature,
whereas initial temperature of fat crystallization (Tonset)
seemed to be differently affected by storage temperature depending on triacylglycerols
(TAG) composition. After storage at 4°C, Tonset
values were very similar for emulsified and non-emulsified AMF–HMT blend,
whereas they were lower (by approx. 6°C) for emulsions containing AMF
or mixture of AMF–LMT fraction. After storage at –30°C, Tonset values of re-crystallization
were higher in emulsion samples than in bulk fat blends, whatever the TAG
fat composition. Light scattering measurements and fluorescence microscopic
observations indicated differences in fat droplet aggregation-coalescence
under freeze-thaw procedure, depending on emulsion fat composition. It appeared
that under quiescent freezing, emulsion containing AMF–LMT fraction
was much less resistant to fat droplet aggregation-coalescence than emulsions
containing AMF or AMF–HMT fraction. Our results indicated the role of
fat droplet liquid-solid content on emulsion stability. 相似文献
16.
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
17.
J. Leitner M. Hampl K. Růžička M. Straka D. Sedmidubský P. Svoboda 《Journal of Thermal Analysis and Calorimetry》2008,91(3):985-990
The heat capacity and the enthalpy increments of strontium metaniobate SrNb2O6 were measured by the relaxation method (2-276 K), micro DSC calorimetry (260-320 K) and drop calorimetry (723-1472 K). Temperature
dependence of the molar heat capacity in the form C
pm=(200.47±5.51)+(0.02937±0.0760)T-(3.4728±0.3115)·106/T
2 J K−1 mol−1 (298-1500 K) was derived by the least-squares method from the experimental data. Furthermore, the standard molar entropy
at 298.15 K S
m0 (298.15 K)=173.88±0.39 J K−1 mol−1 was evaluated from the low temperature heat capacity measurements. The standard enthalpy of formation Δf
H
0 (298.15 K)=-2826.78 kJ mol−1 was derived from total energies obtained by full potential LAPW electronic structure calculations within density functional
theory. 相似文献
18.
Cellulose powder and cellulose pellets obtained by pressing the microcrystalline powder were studied using differential scanning
calorimetry (DSC), differential thermal analysis (DTA), and thermal gravimetry (TG). The TG method enabled the assessment
of water content in the investigated samples. The glass phase transition in cellulose was studied using the DSC method, both
in heating and cooling runs, in a wide temperature range from −100 to 180 °C. It is shown that the DSC cooling runs are more
suitable for the glass phase transition visualisation than the heating runs. The discrepancy between glass phase transition
temperature T
g found using DSC and predictions by Kaelbe’s approach are observed for “dry” (7 and 5.3% water content) cellulose. This could
be explained by strong interactions between cellulose chains appearing when the water concentration decreases. The T
g measurements vs. moisture content may be used for cellulose crystallinity index determination. 相似文献
19.
V. N. Smirnov 《Kinetics and Catalysis》2011,52(2):166-169
The results of our experimental studies and an analysis of the published data on the rate constant for the reaction Fe + O2 = FeO + O in the forward (I) and reverse (−I) direction are reported. The data obtained in this work are described by the
expressions k
1 = 6.2 × 1014exp(−11100 K/T) cm3 mol−1 s−1 and k
−1 = 6.0 × 1013exp(−588 K/T) cm3 mol−1 s−1 (T = 1500–2500 K). The generalized expressions for the temperature dependences of these rate constants derived by combining
our results with the literature data can be presented as k
1 = 9.4 × 1014(T/1000)0.022exp(−11224 K/T) cm3 mol−1 s−1 (T = 1500–2500 K) and k
−1 = 1.8 × 1014(1000/T)0.37exp(−367 K/T) cm3 mol−1 s−1 (T = 200–2500 K). 相似文献
20.
J. G. P. Binner G. Dimitrakis D. M. Price M. Reading B. Vaidhyanathan 《Journal of Thermal Analysis and Calorimetry》2006,84(2):409-412
The nature
of the β to α phase transition in silver iodide was investigated
by conventional and modulated temperature DSC and dielectric property measurements.
On cooling, the high temperature phase remained stable 2.5°C below its
normal transition temperature even at a very slow cooling rate 0.2°C h–1.
Dielectric property measurements under conventional and microwave heating
suggested an anomalous effect of the latter on the β to α phase
transition in this material. 相似文献