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1.
The enthalpies of combustion (ΔH
comb) of five primary, secondary, and tertiary alkyl(aryl)arsines in the condensed state were calculated using the equation ΔH
comb = −385.8–110.3N, where N is the number of bond-forming electrons. The dependence presented is used for the calculation of the enthalpies of combustion
of full esters and amidoesters of arsinous acid of noncyclic and cyclic structures.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1042–1043, May, 2007. 相似文献
2.
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
3.
B. V. Lebedev K. B. Zhogova Ya. V. Denisova G. P. Belov O. N. Golodkov 《Russian Chemical Bulletin》1998,47(2):277-281
The temperature dependence of the heat capacity of the alternating copolymer (ACP) of carbon monoxide with ethylene was studied,
and temperatures and enthalpies of its phase transformations were measured by adiabatic vacuum, dynamic, and isothermal calorimetry
in the temperature range from 8 to 600 K. The energy of burning of ACP was measured at 298.15 K in a calorimeter with the
static bomb and isothermal shell. The thermodynamic parameters of transformation of the α-form of ACP crystals into the β-form
and fusion of the β-form were determined. The thermodynamic functions for the 0–507 K range and thermodynamic characteristics
atT=298.15 K andp=101.325 kPa were calculated. The thermodynamic parameters of the alternating copolymerization of ethylene and CO at 0–507
K and standard pressure were calculated for the bulk reaction.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 284–288, February, 1998. 相似文献
4.
The standard molar enthalpies of formation
f
H
m
°
(cr) at the temperature T = 298.15 K were determined using combustion calorimetry for di-tert-butyl-methanol (A), di-tert-butyl-iso-propyl-methanol (B), and di-phenyl-methyl-methanol (C). The standard molar enthalpies of sublimation
cr
8
H
m
°
of these compounds and of di-phenyl-methanol (D) were obtained from the temperature variation of the vapor pressure measured in a flow system. Molar enthalpies of fusion
cr
1
H
m
°
of the compounds A–D and of tri-phenyl-methanol (E) were measured by differential scanning calorimeter (DSC). From these data and data available from the literature, the following standard molar enthalpies of formation in gaseous phase
f
H
m
°
(g) for A, (–397.0 ± 1.2); B, (–418.1 ± 2.3); C, (–34.2 ± 1.3); and D, (0.9 ± 2.1) kJ · mol–1 were derived, which correspond to strain enthalpies (H
S) of 46.1, 114.7, 8.1, and 5.0 kJ · mol–1, respectively. 相似文献
5.
The standard molar enthalpies of vaporization
l
g
H
m
º
of 2,5-dimethylfuran, 2-tert-butylfuran, 2,5-di-tert-butylfuran, cyclopentenyl methyl ether, cyclohexenyl methyl ether, and tert-amyl methyl ether were obtained from the temperature variation of the vapor pressure measured in a flow system. The standard (p° = 0.1 MPa) molar enthalpies of formation f H
m
º
(1) at the temperature T = 298.15 K were measured using combustion calorimetry for 2,5-dimethylfuran, 2-tert-butylfuran, and 2,5-di-tert-butylfuran. From the derived standard molar enthalpies of formation for gaseous compounds, ring correction terms and non-nearest neighbor interactions useful in the application of the Benson group additivity scheme were calculated. 相似文献
6.
Maria D. M. C. Ribeiro da Silva Joana I. T. A. Cabral Chelsea Givens Stephanie Keown W. E. Acree Jr. 《Journal of Thermal Analysis and Calorimetry》2008,92(1):73-78
The standard (p
0=0.1 MPa) molar enthalpies of formation, in the gaseous phase, at T-298.15 K, for 2,5-dimethylpyrazine (2,5-DMePz) and for the two dimethylpyrazine-N,N′-dioxide derivatives, 2,3-dimethylpyrazine-1,4-dioxide (2,3-DMePzDO) and 2,5-dimethylpyrazine-1,4-dioxide (2,5-DMePzDO), were
derived from the measurements of standard massic energies of combustion, using a static bomb calorimeter, and from the standard
molar enthalpies of vaporization or sublimation, measured by Calvet microcalorimetry.
The mean values for the molar dissociation enthalpy of the nitrogen-oxygen bonds, 〈DH
m0〉(N-O), were derived for both N,N′-dioxide compounds. These values are discussed in terms of the molecular structure of the two N,N′-dioxide derivatives and compared with 〈DH
m0〉(N-O) values previously obtained for other N-oxide derivatives. 相似文献
7.
Verevkin Sergey P. Beckhaus Hans-Dieter Schüle Ursula Rüchardt Christoph 《Structural chemistry》1998,9(1):1-7
The standard molar enthalpies of formation H
f
00B0;
(liq) at the temperature t = 298.15 K were determined using combustion calorimetry for N-methyl-3-methyl-3-phenyl-2-butaneamine 1a, N,N-dimethyl-3-methyl-3-phenyl-2-butaneamine 1b N-methyl-2,3-dimethyl-3-phenyl-2-butaneamine 2a, and N,N-dimethyl-2,3-dimethyl-3-phenyl-2-butaneamine 2b. The standard molar enthalpies of vaporization H
vap
00B0;
of these compounds were obtained from the temperature variation of the vapor pressure measured in a flow system. The following standard molar enthalpies of formation in gaseous phase H
f
00B0;
(g) are obtained from these data: for 1a – 10.9 ± 1.9; 1b – 3.6 ± 1.8; 1c – 26.6 ± 1.4, and 1d – 23.0 ± 1.8 kJ mol–1. From the standard molar enthalpies of formation for gaseous compounds which are available in the literature, improved values for the increments of the Benson group addivitiy scheme of amines were calculated. They are used to determine the strain enthalpies of the amines 1 and 2 from this investigation. 相似文献
8.
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
9.
The standard molar enthalpies of formation
f
H
m
°
(l) at the temperature T = 298.15 K were determined using combustion calorimetry for N-methylpiperidine (A), N-ethylpiperidine (B), N-propylpiperidine (C), N-butylpiperidine (D), N-cyclopentylpiperidine (E), N-cyclohexylpiperidine (F), and N-phenylpiperidine (G). The standard molar enthalpies of vaporization
l
g
H
m
° of these compounds were obtained from the temperature variation of the vapor pressure measured in a flow system. From these data the following standard molar enthalpies of formation in gaseous phase
f
H
m
°
(g) were derived for: A –(61.39 ± 0.88); B –(88.1 ± 1.3); C –(105.81 ± 0.66); D –(126.2 ± 1.3); E ( –88.21 ± 0.75); F –(135.21 ± 0.94); G (70.3 ± 1.4) kJ · mol–1. They are used to determine the strain enthalpies of the cyclic amines A–G. The N-alkylated piperidine rings have been found to be about strainless. 相似文献
10.
T. A. Bykova N. N. Smirnova T. G. Kulagina L. V. Nikishchenkova G. P. Belov E. V. Novikova 《Russian Chemical Bulletin》2005,54(6):1527-1531
The temperature dependence of the heat capacity of an alternating copolymer of bicyclo[2.2.1]hepta-2,5-diene and carbon monoxide
in the temperature range 6–550 K (with an error of 0.2–0.5% at 6–350 K and 0.5–1.5% at 330–550 K) was studied by the adiabatic
vacuum and dynamic calorimetry. Physical transformations of the copolymer in the studied temperature region were identified,
and their thermodynamic characteristics were determined. The combustion energy of the copolymer at 298.15 K was measured in
a calorimeter with a static bomb and isothermal jacket. The thermodynamic functions for a region of 0–550 K, enthalpy of combustion,
and thermodynamic parameters of copolymer formation from simple substances at T = 298.15 K and p = 101.325 kPa were calculated from the obtained experimental data. The new results and earlier published data were used for
the calculation of the thermodynamic characteristics of the alternate copolymerization of bicyclo[2.2.1]hepta-2,5-diene and
CO under standard pressure for a region of 0–350 K for the bulk reaction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1483–1487, June, 2005. 相似文献
11.
Liquid and solid cyclic peroxides derived from aliphatic ketones are explosive materials so their enthalpies of vaporization
and other thermodynamic or condensed-phase properties cannot be measured directly. In this work the enthalpies of vaporization
of peroxides at 298.15 K were estimated simply from gas chromatographic retention times measured at different temperatures.
The technique correlates changes in the retention times of compounds whose enthalpies of vaporization are known (called the
reference series), with those of the compounds of interest. If t
R′ is the adjusted retention time (retention time of each compound minus the retention time of unretained diethyl ether, used
as solvent) a plot of ln t
R′ against 1/T for each compound (reference compounds and cyclic peroxides) results in a straight line (r
2 > 0.99 for all compounds). The enthalpy of transfer from solution to the vapor state (Δsolg
H
m) can be obtained by multiplying the slope by the gas constant (R). A second plot correlates the enthalpies of transfer from
solution to the vapor state (Δsolg
H
m), as measured by gas–liquid chromatography (GLC), with enthalpies of vaporization of reference materials (Δvap
H
m at 298.15 K) available in the literature. C9–C15 fatty acid methyl esters and hydrocarbons were used as reference compounds. The enthalpies of vaporization of the cyclic
organic peroxides were calculated from the equation of the line obtained in this second correlation, the slope of which was
Δvap
H
m (at 298.15 K)/Δg
sol
H
m. The experiments were performed under isothermal conditions with a DB-5 capillary column, flame-ionization detection (FID),
and nitrogen as carrier gas. The column temperature was varied over a range of at least 30–70 K between 403 and 473 K, with
chromatograms being acquired at 10 K intervals. Enthalpies of vaporization of cyclic organic peroxides are not available in
the literature, and the values given in this paper, obtained by gas chromatography, are the first to be reported. 相似文献
12.
V. V. Ovchinnikov L. I. Lapteva E. Yu. Sitnikova A. I. Konovalov 《Russian Chemical Bulletin》2000,49(9):1522-1525
The enthalpies of solvation of four geometric isomers of 2,5-dimethyl-1-phenyl-1-thioxophosphorinan-4-one in chloroform, nitrobenzene,
and methanol were calculated using the enthalpies of vaporization of the isomers determined by the modified Solomonov—Konovalov
method from the enthalpies of solution of the compounds in CCl4 andp-xylene and molar refractions. The enthalpies of formation (ΔH
f
o) of the isomers in the condensed and gas phase were assessed in the framework of Benson's group additivity scheme by summing
the ΔH
f
o values for phosphacycloketone fragments obtained from molecular mechanics calculations with the contributions of the phenyl
group and S atom attached to the P atom.
Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1533–1536, September, 2000. 相似文献
13.
The first measurements of the enthalpies of combustion, sublimation, and fusion of an organo-phosphorus sulfide, triphenylphosphine sulfide, are reported: c
H
m
o
(C18H15PS, cr)=–(10752.58 ±2.90), sub
H
m
o
(C18H15PS, 403 K)=(136.80±6.09), and fus
H
m
o
(C18H15PS, Tm=435.92 K) =(30.53±0.21) kJ·mol–1. Correction of the phase change enthalpies toT=298.15K and po =0.1 MPa results in the standard phase change enthalpy values of sub
H
m
o
(298.15 K)=(142.8 ±6.8) and fus
H
m
o
(298.15 K)=(19.28±0.21) kj·mol–1. Accordingly, the enthalpies of formation of solid, liquid, and gaseous triphenylphosphine sulfide are derived: f
H
m
o
(C18H15PS, cr) =(63.20±2.56), fH
m
o
(C18H15PS, l)=(82.48±2.57), and fH
m
o
(C18H15PS, g)=(206.0±7.3) kJ·mol–1. From these ancillary data, the P=S double-bond enthalpy is 394 kJ-mol–1 and in good agreement with earlier reaction calorimetry results. These phosphorus sulfide values are compared with those for the arsenic sulfides. Plausibility arguments are given for our results. 相似文献
14.
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
15.
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
16.
V. V. Ovchinnikov L. R. Khazieva L. I. Lapteva A. I. Konovalov 《Russian Chemical Bulletin》2000,49(1):33-38
The vaporization enthalpies (ΔH
vap) of 97 primary, secondary, and tertiary alkylphosphines and alkyl(aryl)phosphines with different spatial structures were
calculated using the Trouton and Wadso equations and the first-order topological solvation index1χs. The contributions of the H2P and HP groups and the phosphorus atom to the vaporization enthalpies of primary, secondary, and tertiary phosphines, respectively,
were calculated. The results obtained can be used in calculations of ΔH
vap for related phosphorus compounds.
For Part 16, see Ref. 1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 32–37, January, 2000. 相似文献
17.
The vaporization enthalpies (ΔH
vap) of 97 primary, secondary, and tertiary alkylphosphines and alkyl(aryl)phosphines with different spatial structures were
calculated using the Trouton and Wadso equations and the first-order topological solvation index1χs. The contributions of the H2P and HP groups and the phosphorus atom to the vaporization enthalpies of primary, secondary, and tertiary phosphines, respectively,
were calculated. The results obtained can be used in calculations of ΔH
vap for related phosphorus compounds.
For Part 16, see Ref. 1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 32–37, January, 2000. 相似文献
18.
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
19.
The formal GaCl3-assisted [3+2] cycloaddition of two (Me3Si)2N–N(SiMe3)–PCl2 molecules resulting in the formation of a triazadiphosphole has been studied by means of B3LYP/6-31G(d,p) computations. These calculations revealed a stepwise reaction mechanism starting from the disguised 1,3-dipole and dipolarophile
(Me3Si)2N–N(SiMe3)–PCl2. Comparison of the potential energy surface for the formation of a triazadiphosphole in the presence and without a Lewis
acid indicate, that addition of a Lewis acid such as GaCl3 decreases the activation barriers to Me3Si–Cl elimination, in accord with experiment.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
20.
James S. Chickos Raphaël Sabbah Sarah Hosseini Joel F. Liebman 《Structural chemistry》1996,7(5-6):391-395
The sublimation enthalpy of dimethyl oxalate has been measured by calorimetric and head space analysis. These results along with vaporization enthalpy measured by correlation gas chromatography and fusion enthalpy measurements are compared to results predicted by two estimation techniques. A previous experimental measurement was found to be in error. A mean value of (75.2±0.5) kJ/mol was obtained which results in a corrected molar value of (–681.5±0.8) kJ/mol for the enthalpy of formation of gaseous dimethyl oxalate, f
H
m
o
(g, 298.15 K). This new value of f
H
m
o
(g, 298.15 K) for dimethyl oxalate, in combination with other enthalpies of formation, suggests that the ground state of oxalates are destabilized relative to -diketones by approximately 25 kJ/mol. 相似文献