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1.
Polymorphism of paracetamol 总被引:1,自引:0,他引:1
G. L. Perlovich Tatyana V. Volkova Annette Bauer-Brandl 《Journal of Thermal Analysis and Calorimetry》2007,89(3):767-774
The thermodynamic relationship between crystal modifications of paracetamol was studied by alternative methods. Temperature
dependence of saturated vapor pressure for polymorphic modifications of the drug paracetamol (acetaminophen) was mea sured
and thermodynamic functions of the sublimation process calculated. Solution calorimetry was carried out for the two modifications
in the same solvent. Thermodynamic parameters for sublimation for form I (monoclinic) were found: ΔG
sub298=60.0 kJ mol−1; ΔH
sub298=117.9±0.7 kJ mol−1; ΔS
sub298=190±2 J mol−1 K−1. For the orthorhombic modification (form II), the saturated vapor pressure could only be studied at 391 K. Phase transition
enthalpy at 298 K, ΔH
tr298(I→II)=2.0±0.4 kJ mol−1, was derived as the difference between the solution enthalpies of the noted polymorphs in the same solution (methanol). Based
on ΔH
tr298 (I→II), differences between temperature dependencies of heat capacities of both modifications and the vapor pressure value
of form II at 391 K, the temperature dependence of saturated vapor pressure and thermodynamic sublimation parameters for modification
II were also estimated (ΔG
sub298=56.1 kJ mol−1; ΔH
sub298=115.9±0.9 kJ mol−1; ΔS
sub298=200±3 J mol−1 K−1). The results indicate that the modifications are monotropically related, which is in contrast to findings recently reported
found by classical thermochemical methods. 相似文献
2.
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
3.
M. A. V. Ribeiro da Silva C. P. F. Santos M. J. S. Monte C. A. D. Sousa 《Journal of Thermal Analysis and Calorimetry》2006,83(3):533-539
The
standard (p0=0.1
MPa) molar enthalpies of formation, ΔfHm0, for
crystalline phthalimides: phthalimide, N-ethylphthalimide
and N-propylphthalimide were derived from
the standard molar enthalpies of combustion, in oxygen, at the temperature
298.15 K, measured by static bomb-combustion calorimetry, as, respectively,
– (318.0±1.7), – (350.1±2.7) and – (377.3±2.2)
kJ mol–1. The standard molar enthalpies of
sublimation, ΔcrgHm0, at T=298.15
K were derived by the Clausius-Clapeyron equation, from the temperature dependence
of the vapour pressures for phthalimide, as (106.9±1.2) kJ mol–1
and from high temperature Calvet microcalorimetry for phthalimide, N-ethylphthalimide and N-propylphthalimide
as, respectively, (106.3±1.3), (91.0±1.2) and (98.2±1.4)
kJ mol–1.
The derived standard molar enthalpies of formation,
in the gaseous state, are analysed in terms of enthalpic increments and interpreted
in terms of molecular structure. 相似文献
4.
Thermochemical
studies on the thioproline 总被引:3,自引:0,他引:3
The combustion energy of thioproline was determined
by the precision rotating-bomb calorimeter at 298.15 K to be Δc
U= –2469.30±1.44 kJ mol–1.
From the results and other auxiliary quantities, the standard molar enthalpy
of combustion and the standard molar enthalpy of formation of thioproline
were calculated to be Δc
H
m
θC4H7NO2S,
(s), 298.15 K= –2469.92±1.44 kJ mol–1
and Δf
H
m
θC4H7NO2S, (s), 298.15K= –401.33±1.54
kJ mol–1. 相似文献
5.
M. A. V. Ribeiro da Silva Cláudia P. F. Santos 《Journal of Thermal Analysis and Calorimetry》2007,87(1):21-25
The standard (p
0=0.1
MPa) molar enthalpy of formation, Δf
H
0
m, for crystalline N-phenylphthalimide
was derived from its standard molar enthalpy of combustion, in oxygen, at
the temperature 298.15 K, measured by static bomb-combustion calorimetry,
as –206.0±3.4 kJ mol–1. The
standard molar enthalpy of sublimation, Δg
cr
H
0
m
, at T=298.15 K, was derived, from high
temperature Calvet microcalorimetry, as 121.3±1.0 kJ mol–1.
The derived standard molar enthalpy of formation, in the gaseous state,
is analysed in terms of enthalpic increments and interpreted in terms of molecular
structure. 相似文献
6.
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
7.
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
8.
N. B. Morozova P. P. Semyannikov S. V. Sysoev V. M. Grankin I. K. Igumenov 《Journal of Thermal Analysis and Calorimetry》2000,60(2):489-495
The temperature dependency of the saturated vapor pressure of Ir(acac)3 has been measured by the method of calibrated volume (MCV), the Knudsen method, the flow transpiration method, and the membrane
method. The thermodynamic parameters of phase transition of a crystal to gas were calculated using each of these methods,
and the following values of ΔH
T
0 (kJ mol−1) and ΔS
T
0 (J mol−1K−1), respectively, were obtained: MCV: 101.59, 156.70; Knudsen: 130.54, 224.40; Flow transpiration: 129.34, 212.23; Membrane:
95.45, 149.44
Coprocessing of obtaining data (MCV, flow transportation method and Knudsen method) at temperature ranges 110−200°C as also
conducted:ΔH
T
0 =127.9±2.1 (kJ mol−1 ); ΔS
T
0 =215.2±5.0 (J mol−1 K−1 ).
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
9.
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
10.
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
11.
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
12.
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
13.
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
14.
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
15.
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
16.
F. J. Martínez Casado M. Ramos Riesco J. A. R. Cheda 《Journal of Thermal Analysis and Calorimetry》2007,87(1):73-77
The temperature and enthalpy vs. composition diagrams of the binary
system [xC3H7CO2Li+(1–x)C3H7CO2Rb],
where x=mole fraction, were determined
by differential scanning calorimetry (DSC). This binary systems displays the
formation of two mixed salts with a composition 1:1 and 1:2, which melt incongruently
at T
fus=590.5 K,
with Δfus
H
m=11.6
kJ mol–1, and congruently at T
fus=614.5
K, with Δfus
H
m=20.2
kJ mol–1, respectively. The phase diagram
also presents an ionic liquid-crystalline phase in a wide temperature range:
95 K. 相似文献
17.
S. Vecchio 《Journal of Thermal Analysis and Calorimetry》2006,84(1):271-278
The standard sublimation enthalpies of (2,4,5-trichlorophenoxy)acetonitrile
and (2,4,5-trichlorophenoxy)aniline were determined by isothermal thermogravimetry
using the Langmuir equation and by non-isothermal differential scanning calorimetry
for comparison. The used procedure was previously tested using three reference
compounds: benzoic acid, succinic acid and salicylic acid. The results compared
to those reported in literature show an excellent agreement for two of the
three compounds while the third agrees quite well. For (2,4,5-trichlorophenoxy)acetonitrile
and (2,4,5-trichlorophenoxy)aniline, the extrapolation of data at 298.15 K
were obtained, respectively: ΔsubH°(298
K)={(106±4) and (101±4)} kJ mol–1.
From Clausius Clapeyron equation obtained after the determination of the vaporization
constant α′, the following standard sublimation entropies for
(2,4,5-trichlorophenoxy)acetonitrile and (2,4,5-trichlorophenoxy)aniline equal
to ΔsubS°(298
K)=(251 and 237) J K–1 mol–1,
respectively, were derived, with an error of ±4 J K–1
mol–1 equal for the studied herbicides. 相似文献
18.
Y. Y. Di Z. C. Tan L. W. Li S. L. Gao L. X. Sun 《Journal of Thermal Analysis and Calorimetry》2007,87(2):545-551
Low-temperature heat capacities of a solid
complex Zn(Val)SO4·H2O(s) were measured by a precision automated adiabatic
calorimeter over the temperature range between 78 and 373 K. The initial dehydration
temperature of the coordination compound was determined to be, T
D=327.05
K, by analysis of the heat-capacity curve. The experimental values of molar
heat capacities were fitted to a polynomial equation of heat capacities (C
p,m) with the reduced temperatures
(x), [x=f (T)], by least
square method. The polynomial fitted values of the molar heat capacities and
fundamental thermodynamic functions of the complex relative to the standard
reference temperature 298.15 K were given with the interval of 5 K.
Enthalpies of dissolution of the [ZnSO4·7H2O(s)+Val(s)] (Δsol
H
m,l
0)
and the Zn(Val)SO4·H2O(s) (Δsol
H
m,2
0) in 100.00 mL of 2 mol dm–3 HCl(aq) at T=298.15
K were determined to be, Δsol
H
m,l
0=(94.588±0.025) kJ mol–1 and Δsol
H
m,2
0=–(46.118±0.055)
kJ mol–1, by means of a homemade isoperibol
solution–reaction calorimeter. The standard molar enthalpy of formation
of the compound was determined as: Δf
H
m
0
(Zn(Val)SO4·H2O(s), 298.15 K)=–(1850.97±1.92) kJ mol–1,
from the enthalpies of dissolution and other auxiliary thermodynamic data
through a Hess thermochemical cycle. Furthermore, the reliability of the Hess
thermochemical cycle was verified by comparing UV/Vis spectra and the refractive
indexes of solution A (from dissolution of the [ZnSO4·7H2O(s)+Val(s)] mixture
in 2 mol dm–3 hydrochloric acid) and solution
A’ (from dissolution of the complex Zn(Val)SO4·H2O(s) in 2 mol dm–3
hydrochloric acid). 相似文献
19.
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
20.
The thermodynamics of the conversion of aqueous glucose to fructose has been investigated using both heat conduction microcalorimetry
and high pressure liquid chromatography (HPLC). The reaction was carried out in both aqueous Tris/HCl buffer and in aqueous
phosphate buffer in the pH range 7–8 using the enzyme glucose isomerase and the cofactors CoCl2 and MgSO4. The temperature range over which this reaction was investigated was 298.15–358.15 K. We have found that the enthalpy of
reaction is independent of pH over the range investigated. A combined analysis of both the HPLC and microcalorimetric data
leads to the following results at 298 15 K:ΔG° = 349 ± 53 J mol-1, ΔH° = 2.78 ± 0.20 kJ mol-1, and ΔC
p
°
= 76 ± 30 J mol-1 K-1. The stated uncertainties are based upon an analysis of both the random and systematic errors inherent in the measurements.
Comparisons are made with literature data. The percent conversion of glucose to fructose has been calculated for the temperature
range 300–373.15 K. 相似文献