共查询到20条相似文献,搜索用时 15 毫秒
1.
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
2.
N. Wiegand L. Vámhidy B. Patczai E. Dömse P. Than L. Kereskai D. Lőrinczy 《Journal of Thermal Analysis and Calorimetry》2009,95(3):797-800
The Dupuytren contracture - degenerative shortening of the palmar aponeurosis - is a common disease of the hand in Europe.
The aetiology of the degenerative changes in the collagen structures is still not clear. To describe the clinical manifestation
of the disease we use an international classification according to Iselin. Our hypothesis was that in Dupuytren disease there
is a clear pathological abnormality in the tissue elements building up the palmar aponeurosis, which is responsible for the
disease, and could be monitored besides the classical histological methods by differential scanning calorimetry.
The thermal denaturation of different parts of human samples was monitored by a SETARAM Micro DSC-II calorimeter. All the
experiments were performed between 0 and 100°C. The heating rate was 0.3 K min−1. DSC scans clearly demonstrated significant differences between the different types and conditions of samples (control: T
m=63°C and ΔH
cal=4.1 J g−1, stage I.: T
m= 63°C and ΔH
cal=5.1 J g−1, stage II.: T
m=64°C and ΔH
cal=5.2 J g−1, stage III.: T
m=60°C and ΔH
cal=5.2 J g−1, stage IV.: T
m=60.2°C and ΔH
cal=5.3 J g−1). The heat capacity change between native and denatured states of aponeurosis samples increased with the degree of structural
alterations indicating significant water loosing. These observations could be explained with the structural alterations caused
by the biochemical processes.
With our investigations we could demonstrate that DSC is a useful and well applicable method for the investigation of collagen
tissue of the human aponeurosis. Our results may be of clinical relevance in the future i.e. in the choice of the optimal
time of surgical therapy of different clinical level Dupuytren contractures. 相似文献
3.
B. Tong Z. C. Tan J. N. Zhang S. X. Wang 《Journal of Thermal Analysis and Calorimetry》2009,95(2):469-475
The low-temperature heat capacity C
p,m of erythritol (C4H10O4, CAS 149-32-6) was precisely measured in the temperature range from 80 to 410 K by means of a small sample automated adiabatic
calorimeter. A solid-liquid phase transition was found at T=390.254 K from the experimental C
p-T curve. The molar enthalpy and entropy of this transition were determined to be 37.92±0.19 kJ mol−1 and 97.17±0.49 J K−1 mol−1, respectively. The thermodynamic functions [H
T-H
298.15] and [S
T-S
298.15], were derived from the heat capacity data in the temperature range of 80 to 410 K with an interval of 5 K. The standard
molar enthalpy of combustion and the standard molar enthalpy of formation of the compound have been determined: Δc
H
m0(C4H10O4, cr)= −2102.90±1.56 kJ mol−1 and Δf
H
m0(C4H10O4, cr)= − 900.29±0.84 kJ mol−1, by means of a precision oxygen-bomb combustion calorimeter at T=298.15 K. DSC and TG measurements were performed to study the thermostability of the compound. The results were in agreement
with those obtained from heat capacity measurements. 相似文献
4.
J. N. Zhang Z. C. Tan Q. F. Meng Q. Shi B. Tong S. X. Wang 《Journal of Thermal Analysis and Calorimetry》2009,95(2):461-467
The heat capacities (C
p,m) of 2-amino-5-methylpyridine (AMP) were measured by a precision automated adiabatic calorimeter over the temperature range
from 80 to 398 K. A solid-liquid phase transition was found in the range from 336 to 351 K with the peak heat capacity at
350.426 K. The melting temperature (T
m), the molar enthalpy (Δfus
H
m0), and the molar entropy (Δfus
S
m0) of fusion were determined to be 350.431±0.018 K, 18.108 kJ mol−1 and 51.676 J K−1 mol−1, respectively. The mole fraction purity of the sample used was determined to be 0.99734 through the Van’t Hoff equation.
The thermodynamic functions (H
T-H
298.15 and S
T-S
298.15) were calculated. The molar energy of combustion and the standard molar enthalpy of combustion were determined, ΔU
c(C6H8N2,cr)= −3500.15±1.51 kJ mol−1 and Δc
H
m0 (C6H8N2,cr)= −3502.64±1.51 kJ mol−1, by means of a precision oxygen-bomb combustion calorimeter at T=298.15 K. The standard molar enthalpy of formation of the crystalline compound was derived, Δr
H
m0 (C6H8N2,cr)= −1.74±0.57 kJ mol−1. 相似文献
5.
Griesser U. J. Weigand D. Rollinger J. M. Haddow M. Gstrein E. 《Journal of Thermal Analysis and Calorimetry》2004,77(2):511-522
Five crystal polymorphs of the herbicide metazachlor (MTZC) were characterized by means of hot stage microscopy, differential
scanning calorimetry, IR- and Raman spectroscopy as well as X-ray powder diffractometry. Modification (mod.) I, II and III°
can be crystallized from solvents and the melt, respectively, whereas the unstable mod. IV and V crystallize exclusively from
the super-cooled melt. Based on the results of thermal analysis and solvent mediated transformation studies, the thermodynamic
relationships among the polymorphic phases of metazachlor were evaluated and displayed in a semi-schematic energy/temperature-diagram.
At room temperature, mod. III° (T
fus =76°C, Δfus
H
III =26.6 kJ mol-1) is the thermodynamically stable form, followed by mod. II (T
fus =80°C, Δfus
H
II =23.0 kJ mol-1) and mod. I (T
fus =83°C, Δfus
H
II=19.7 kJ mol-1). These forms are enantiotropically related showing thermodynamic transition points at ~55°C (T
trs, III/II), ~60°C (T
trs, III/I) and ~63°C (T
trs, II/I). Thus mod. I is the thermodynamically stable form above 63°C, mod. III° below 55°C and mod. II in a small window between
these temperatures. Mod. IV (T
fus =72-74°C, Δfus
H
II =18.7 kJ mol-1) and mod. V (T
fus =65°C) are monotropically related to each other as well as to all other forms. The metastable mod. I and II show a high kinetic
stability. They crystallize from solvents, and thus these forms can be present in commercial samples. Since metazachlor is
used as an aqueous suspension, the use of the metastable forms is not advisable because of a potential transformation to mod.
III°. This may result in problematic formulations, due to caking and aggregation.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
6.
V. N. Emel’yanenko S. P. Verevkin C. Schick E. N. Stepurko G. N. Roganov M. K. Georgieva 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2010,84(9):1491-1497
The enthalpies of combustion and formation of S-lactic acid at 298.15 K, Δc
H
mo(cr.) = −1337.9 ± 0.8 and Δf
H
mo(cr.) = −700.1 ± 0.9 kJ/mol, were determined by calorimetry. The temperature dependence of acid vapor pressure was studied
by the transpiration method, and the enthalpy of its vaporization was obtained, Δvap
H
o(298.15 K) = 69.1 ± 1.0 kJ/mol. The temperature and enthalpy of fusion, T
m (330.4 K) and Δm
H
o(298.15 K) = 14.7 ± 0.2 kJ/mol, were determined by differential scanning calorimetry. The enthalpy of formation of the acid
in the gas phase was obtained. Ab initio methods were used to perform a conformational analysis of the acid, calculate fundamental
vibration frequencies, moments of inertia, and total and relative energies of the stablest conformers. Thermodynamic properties
were calculated in the ideal gas state over the temperature range 0–1500 K. A thermodynamic analysis of mutual transformation
processes (the formation of SS- and RS(meso)-lactides from S-lactic acid and the racemization of these lactides) and the formation
of poly-(RS)-lactide from S-lactic acid and SS- and RS(meso)-lactides was performed. 相似文献
7.
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
8.
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
9.
T. Sillinger P. Than B. Kocsis D. Lőrinczy 《Journal of Thermal Analysis and Calorimetry》2005,82(1):221-223
Summary Treatment of a bacterial arthritis is a challenging task for a clinician as inadequate therapy can cause cartilage destruction
and can result in severe osteoarthritis of the affected joint. The development of cartilage destruction in septic arthritis
is not known in details. The aim of this study was to follow this process by calorimetric method. We induced experimental
septic arthritis in knee joints of seven New Zealand rabbits by single inocculation of Staphylococcus aureusOKI 112001 culture (1.5 mL 8·108±5% c.f.u.). The first rabbit died on the 11thday. At that time all the other subjects were made overslept and samples were isolated from the cartilage of the femurs for
calorimetric measurement. The DSC scans clearly demonstrated the development of infective structural destruction in cartilage
from the first to the tenth day of incubation. In case of healthy control the melting temperatures (Tm) were: 49.7, 55 and 63.4°C and the total calorimetric enthalpy change (ΔH) was 0.55 J g-1. After the first day the enthalpy decreased (0.375 J g-1), the first two transition temperature shifted towards higher temperature: 57 and 63.15°C. Up to the fourth day the effect
of infection culminated with Tmof 49.3, 55.9, 59.4, 62.8°C and further decrease of the ΔH. At the fifth day the effect of infection is culminated in two separable thermal denaturation events (with 55 and 63.3°C
Tms) with high jump in ΔHindicating the dramatic change of the structure of rabbit cartilage, so this time elapsed seems to be critical from the point
of view of practical clinical relevance too. Between the 7thand 11thdays practically we had same melting temperatures (50 and 63°C) with low (~0.24 J g-1) enthalpy. 相似文献
10.
Summary The third-law method has been applied to determine the enthalpies, ΔrHT0, for dehydration reactions of kaolinite, muscovite and talc. The ΔrHT0values measured in the equimolar (in high vacuum) and isobaric (in the presence of water vapour) modes (980±15, 3710±39 and
2793±34 kJ mol-1, for kaolinite, muscovite and talc, respectively) practically coincide if to take into account the strong self-cooling effect
in vacuum. This fact strongly supports the mechanism of dissociative evaporation of these compounds in accordance with the
reactions (primary stages): Al2O3·2SiO2·2H2O(s)→Al2O3(g)↓+2SiO2(g)↓+2H2O(g); K2O·3Al2O3·6SiO2·2H2O(s) →K2O(g)↓+3Al2O3(g)↓+6SiO2(g)↓+2H2O(g) and 3MgO·4SiO2·H2O(s) →3MgO(g)↓+4SiO2(g)↓+H2O(g). The values of the Eparameter deduced from these data for equimolar and isobaric modes of dehydration are as follows: 196 and 327 kJ mol-1for kaolinite, 309 and 371 kJ mol-1for muscovite and 349 and 399 kJ mol-1for talc. These values are in agreement with quite a few early results reported in the literature in 1960s. 相似文献
11.
I. Zięborak-Tomaszkiewicz 《Journal of Thermal Analysis and Calorimetry》2006,83(3):611-615
The energies of combustion
in fluorine of gallium nitride and indium nitride in wurzite crystalline structure
have been measured in a two-compartment calorimetric bomb, and new standard
molar enthalpies of formation have been calculated: ΔfHm0(GaN(cr)
298.15 K)= –(163.7±4.2) kJ mol–1
and ΔfHm0(InN(cr) 298.15 K)= –(146.5±4.6) kJ mol–1
. Comparison with the recommended values of the ΔfHm0 nitrides
from the literature is also presented. 相似文献
12.
This
study discussed the phenomena on thermal polymerization of α-methylstyrene
(AMS). A curve scanned by temperature-programmed technique was performed by
differential scanning calorimetry (DSC). Heat of polymerization (ΔH) and onset temperature of exothermic (T0) behavior were determined
to be 280±10 J g-1 and about 138±1°C,
respectively. A dimer formation mechanism was proposed for initiation of the
propagating chain. Spectroscopic identification of dimer structure was conducted
by infrared (IR) spectroscopy in the wavenumber from 650 to 1100 cm-1associated
with molecular fingerprint characteristics. The mechanism of thermal polymerization
on α-methylstyrene proposed in this study was similar to that of styrene
suggested by Mayo. 相似文献
13.
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
14.
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
15.
M.-H. Wang Z.-C. Tan Q. Shi L.-X. Sun T. Zhang 《Journal of Thermal Analysis and Calorimetry》2006,84(2):413-418
The
heat capacities of 2-benzoylpyridine were measured with an automated adiabatic
calorimeter over the temperature range from 80 to 340 K. The melting point,
molar enthalpy, ΔfusHm,
and entropy, ΔfusSm,
of fusion of this compound were determined to be 316.49±0.04 K, 20.91±0.03
kJ mol–1 and 66.07±0.05 J mol–1
K–1, respectively. The purity of the compound
was calculated to be 99.60 mol% by using the fractional melting technique.
The thermodynamic functions (HT–H298.15) and (ST–S298.15) were calculated based
on the heat capacity measurements in the temperature range of 80–340
K with an interval of 5 K. The thermal properties of the compound were further
investigated by differential scanning calorimetry (DSC). From the DSC curve,
the temperature corresponding to the maximum evaporation rate, the molar enthalpy
and entropy of evaporation were determined to be 556.3±0.1 K, 51.3±0.2
kJ mol–1 and 92.2±0.4 J K–1
mol–1, respectively, under the experimental
conditions. 相似文献
16.
J. Leitner K. Růžička D. Sedmidubský P. Svoboda 《Journal of Thermal Analysis and Calorimetry》2009,95(2):397-402
Heat capacity and enthalpy increments of calcium niobates CaNb2O6 and Ca2Nb2O7 were measured by the relaxation time method (2–300 K), DSC (260–360 K) and drop calorimetry (669–1421 K). Temperature dependencies
of the molar heat capacity in the form C
pm=200.4+0.03432T−3.450·106/T
2 J K−1 mol−1 for CaNb2O6 and C
pm=257.2+0.03621T−4.435·106/T
2 J K−1 mol−1 for Ca2Nb2O7 were derived by the least-squares method from the experimental data. The molar entropies at 298.15 K, S
m0(CaNb2O6, 298.15 K)=167.3±0.9 J K−1 mol−1 and S
m0(Ca2Nb2O7, 298.15 K)=212.4±1.2 J K−1 mol−1, were evaluated from the low temperature heat capacity measurements. Standard enthalpies of formation at 298.15 K were derived
using published values of Gibbs energy of formation and presented heat capacity and entropy data: Δf
H
0(CaNb2O6, 298.15 K)= −2664.52 kJ molt-1 and Δf
H
0(Ca2Nb2O7, 298.15 K)= −3346.91 kJ mol−1. 相似文献
17.
Yu H. G. Yu Dong J. X. Qin C. Q. Liu Y. Qu S. S. 《Journal of Thermal Analysis and Calorimetry》2004,75(3):807-813
The energy of combustion of crystalline 3,4,5-trimethoxybenzoic acid in oxygen at T=298.15 K was determined to be -4795.9±1.3 kJ mol-1 using combustion calorimetry. The derived standard molar enthalpies of formation of 3,4,5-trimethoxybenzoic acid in crystalline
and gaseous states at T=298.15 K, ΔfHm
Θ (cr) and ΔfHm
Θ (g), were -852.9±1.9 and -721.7±2.0 kJ mol-1, respectively. The reliability of the results obtained was commented upon and compared with literature values.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
18.
G. Bognár Cs. Pintér B. Horváth T. Sydo E. Ligeti J. Pulai D. Lőrinczy 《Journal of Thermal Analysis and Calorimetry》2009,95(3):769-774
Osteonecrosis (ON) of the femoral frequently occurs after steroid medication. One of the final pathways leading to steroid
induced ON is thought to be pathologic fat metabolism. The pathobiological mechanism underlying the induction of fat metabolism
outslides by steroids leading to ON has not been fully elucidated. The purpose of this study was to examine the intraoperative
obtained gluteal fat tissue from ON patients with histology, gas chromatography (GC) and differential scanning calorimetry
(DSC) and to compare them with otherwise healthy patient’s samples. The histological sections showed no significant differences
compared with the control group. GC revealed that fraction of saturated fatty acids decreased in ON samples from mean values
of controls of 24% to 21, the polyunsaturated fraction from 20 to 14%. The monounsaturated acids showed an increase from mean
rate of 52% of the controls to 65% of steroid treated samples. DSC curves correlate with chromatographic analysis of the tissue
fatty acids (Steroid treated, heating between 0–100°C: T
m=5.7°C, ΔH= −15.8J/g−1; heating between −20–100°C: Tm= −9.96 and 5.85°C, ΔH= −59.17 and −16.2 J g−1. Non-necrotic, heating between 0–100°C: two separable transition with Tm=5.7 and 9.9°C, total ΔH= −20.8 J g−1; heating between −20–100°C: Tm= −10.9 and 4.95°C, total ΔH= −75.8 J g−1.)
Our preliminary findings are rather tendentious. Further investigations are needed with higher sample rate and under other
anamnestic circumstances too. 相似文献
19.
Ronaldo S. Nunes Felipe S. Semaan Alan T. Riga Éder T. G. Cavalheiro 《Journal of Thermal Analysis and Calorimetry》2009,97(1):349-353
The thermal properties of verapamil hydrochloride (VRP) and its physical association as binary mixtures with some common excipients
were evaluated. Thermogravimetry (TG) was used to determine the thermal mass loss, as well as to study the kinetics of VRP
thermal decomposition, using the Flynn-Wall-Ozawa model. Based on their frequent use in pharmacy, five different excipients
(microcrystalline cellulose, magnesium stearate, hydroxypropyl methylcellulose, polyvinylpyrrolidone and talc) were blended
with VRP. Samples were prepared by mixing the analyte and excipients in a proportion of 1:1 (m/m). DSC curves for pure VRP
presented an endothermic event at 143 ± 2 °C (ΔHmelt = 132 ± 4 J g−1), which corresponds to the melting (literature Tm = 143.7 °C, ΔHmelt = 130.6 J g−1). Comparisons among the observed results for each compound and their binary physical mixtures presented no relevant changes.
This suggests no interaction between the drug and excipient. 相似文献
20.
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