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1.
Wincel H 《Journal of the American Society for Mass Spectrometry》2011,22(9):1570-1576
The thermochemical properties ΔH
o
n
, ΔS
o
n
, and ΔG
o
n
for the hydration of sodiated and potassiated monosaccharides (Ara = arabinose, Xyl = xylose, Rib = ribose, Glc = glucose,
and Gal = galactose) have been experimentally studied in the gas phase at 10 mbar by equilibria measurements using an electrospray
high-pressure mass spectrometer equipped with a pulsed ion beam reaction chamber. The hydration enthalpies for sodiated complexes
were found to be between −46.4 and −57.7 kJ/mol for the first, and −42.7 and −52.3 kJ/mol for the second water molecule. For
potassiated complexes, the water binding enthalpies were similar for all studied systems and varied between −48.5 and −52.7
kJ/mol. The thermochemical values for each system correspond to a mixture of the α and β anomeric forms of monosaccharide
structures involved in their cationized complexes. 相似文献
2.
B. A. Knyazev V. F. Vakher 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2011,85(5):804-810
The heats of the reaction of sodium with ethyl and methyl alcohol were determined by calorimetry. The difference in the standard
heats of the formation of triethylarsenite and arsenic trichloride was obtained by calorimetration of the reaction of arsenic
trichloride with sodium ethylate, the value of which was −382.42 ± 3.60 kJ/mol. The standard enthalpies of formation were
determined from a critical analysis of all data on thermochemistry of trialkylarsenites for the following compounds: triethylarsenite
Δf
H
298ℴ [(C2H5O)3As(liquid)] = (−704.38 ± 3.85) kJ/mol; trimethylarsenite Δf
H
298ℴ [(CH3O)3As(liquid)] = (−599.36 ± 1.88) kJ/mol. The values of standard enthalpies of formation were not adjusted for the following
substances in liquid state: arsenic trichloride (−321.96 ± 3.85 kJ/mol), tris-(diethylamido)arsenic(III) As(NEt2)3(liquid) (−129.81 ± 4.41 kJ/mol), tri-n-propylarsenite (−720.61 ± 4.49 kJ/mol), triisopropylarsenite (−756.11 ± 4.65 kJ/mol), tri-n-butylarsenite (−775.11 ± 4.53 kJ/mol), and triisobutylarsenite (−809.71 ± 4.59 kJ/mol). The use of sodium alcoxide solutions
for the calorimetration of halogen anhydrides of various acids was demonstrated. 相似文献
3.
Egle Girdauskaite Helmut Ullmann Mahmoud Al Daroukh Vladimir Vashook Martin Bülow Ulrich Guth 《Journal of Solid State Electrochemistry》2007,11(4):469-477
Perovskite-type oxides with A, A′=La, Ba, Sr; B, B′=Mn, Fe, Co were investigated by means of thermal analysis, solid electrolyte cells, and X-ray
diffraction. Partial molar thermodynamic quantities are determined and their relations with O/M stoichiometry, unit cell volume,
and phase stability were studied. The absolute values of partial molar enthalpies of perovskite-type oxides increase with
increasing O/M stoichiometries and with decreasing unit cell volumes of the cubic perovskite-type structure, corresponding
to higher chemical stabilities. The substitution of Ba for La, Ba for Sr, Co for Fe, and Fe for Mn lead to increase in unit
cell volumes and decrease in absolute values of ΔH
0. The ΔH
0 values of the cobaltites/ferrites range from −33.5 kJ/mol for SrCo0.8Fe0.2O3−x
to −72.5 kJ/mol for La0.2Sr0.8Co0.6Fe0.4O3−x, and of the manganates up to −132 kJ/mol for Ca0.5Sr0.5Mn0.8Fe0.2O3−x
. 相似文献
4.
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
5.
Taihong Yan Chen Zuo Weifang Zheng Guoan Ye Xiaorong Wang 《Journal of Radioanalytical and Nuclear Chemistry》2009,280(3):585-588
The kinetics of the reductive stripping of plutonium(IV) by dihydroxyurea (DHU) in 30% TBP/kerosene-HNO3 system was studied with a constant interfacial area cell. The stripping rate of plutonium(IV) increases with the increase
of the stirring speed of two phases and the interfacial area. The activation energy of this process is 28.4 kJ/mol. Under
the given experimental conditions, the mass transfer of Pu is not controlled by redox reaction, but controlled by molecular
diffusion from the organic phase to organic film layer and from the aqueous film layer to aqueous phase. The rate equation
of reductive stripping (process is controlled by diffusion) was obtained as: r
0 = k′[Pu(IV)]0[DHU]a
0.16[HNO3]a
−0.34. The rate constant k′ is (5.0±0.4)·10−2 (mol/L)0.18·min−1 at 18.0°C. 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.
Nonempirical methods are used to calculate the geometric parameters, the frequencies of normal vibrations, and thermochemical
characteristics of ions existing in saturated vapors over sodium bromide and iodide: Na2X+, NaX2−, Na3X2+, and Na2X3− (X = Br, I). According to the calculations, Na2X+ and NaX2− triatomic ions have a linear equilibrium configuration of D
∞h
symmetry. Pentaatomic ions can exist in the form of three isomers: linear with D
∞h
symmetry, planar cyclic with C
2v
symmetry, and bipyramidal with D
3h
symmetry. At a temperature of ∼1000 K, Na3X2+ and NaX3− pentaatomic ions are shown to be present in vapor mainly in the form of linear isomers. The energies and enthalpies of ion
molecular reactions with the participation of the above ions are calculated, and the formation enthalpies of the ions are
determined, Δ
f
H
o(0 K): 293±2 kJ/mol (Na2Br+), 354±2 kJ/mol (Na2I+), −536±2 kJ/mol (NaBr2−, −458±2 kJ/mol (NaI2−, 24±5 kJ/mol (Na3Br2+, 143±5 kJ/mol (Na3I2+, −810±5 kJ/mol (Na2Br3−, and −675±5 kJ/mol (Na2I3−. 相似文献
8.
V. P. Kheidorov Yu. A. Ershov G. Yu. Chalyi O. V. Titorovich 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2011,85(8):1358-1362
The kinetics of the oxidative conversion of 1,3,7-trimethylxanthine upon treatment with hypochlorite ions (OCl−) in aqueous medium at 283–298 K and pH 8.2 was studied. The reaction order with respect to each component was determined
and proved to be 1. It was established that the temperature dependence of the reaction rate follows the Arrhenius equation.
The activation parameters of the reaction were measured: E
a
= 33.58 kJ/mol, ΔH
≠ = 31.12 kJ/mol, ΔS
≠ = −170.02 J/(K mol), ΔG
≠ = 81.45 kJ/mol. The stoichiometry of the reaction was studied, and the chemistry of the oxidative conversion of caffeine
treated with OCl− is discussed. 相似文献
9.
The relative enthalpies, ΔHo (0) and ΔHo (298.15), of stationary points (four minimum and three transition structures) on the •O3H potential energy surface were calculated with the aid of the G3MP2B3 as well as the CCSD(T)–CBS (W1U) procedures from which
we earlier found mean absolute deviations (MAD) of 3.9 kJ mol−1 and 2.3 kJ mol−1, respectively, between experimental and calculated standard enthalpies of the formation of a set of 32 free radicals. For
CCSD(T)-CBS (W1U) the well depth from O3 + H• to trans-•O3H, ΔHowell(298.15) = −339.1 kJ mol−1, as well as the reaction enthalpy of the overall reaction O3 + H•→O2 + •OH, ΔrHo(298.15) = −333.7 kJ mol−1, and the barrier of bond dissociation of trans-•O3H → O2 + •OH, ΔHo(298.15) = 22.3 kJ mol−1, affirm the stable short-lived intermediate •O3H. In addition, for radicals cis-•O3H and trans-•O3H, the thermodynamic functions heat capacity Cop(T), entropy So (T), and thermal energy content Ho(T) − Ho(0) are tabulated in the range of 100 − 3000 K. The much debated calculated standard enthalpy of the formation of the trans-•O3H resulted to be ΔfHo(298.15) = 31.1 kJ mol −1 and 32.9 kJ mol −1, at the G3MP2B3 and CCSD(T)-CBS (W1U) levels of theory, respectively. In addition, MR-ACPF-CBS calculations were applied
to consider possible multiconfiguration effects and yield ΔfHo(298.15) = 21.2 kJ mol −1. The discrepancy between calculated values and the experimental value of −4.2 ± 21 kJ mol−1 is still unresolved.
Note added in proof: Yu-Ran Luo and J. Alistair Kerr, based on the discussion in reference 12, recently presented an experimental
value of ΔfHo(298.15) = 29.7 ± 8.4 kJ mol−1 in the 85th edition of the CRC Handbook of Chemistry and Physics (in progress). 相似文献
10.
V. S. Sudavtsova M. I. Ivanov V. V. Berezutskii V. G. Kudin M. A. Shevchenko 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2011,85(12):2237-2240
Partial and integral mixing enthalpies of melts of the Eu-Sn system were determined by calorimetry at 1300 (1250) K in the
concentration intervals 0 < x
Sn < 0.16 and 0.7 < x
Sn < 1. It was found that the first partial mixing enthalpies of Sn and Eu were −215.6 ± 10.6 and −161.2 ± 7.6 kJ/mol, respectively.
The thermodynamic properties of the Eu-Sn alloys were modeled using the theory of ideal associated solutions over a wide interval
of concentrations and temperatures. In was found that the activities of components exhibit strong negative deviations from
Raoult’s law. At minimum, the calculated integral Gibbs energies of mixing reach −43.4 kJ/mol at x
Sn = 0.48; ΔG
ex = −36 kJ/mol, ΔS
ex = −22 J/(mol K). 相似文献
11.
Stefan Perişanu Iulia Contineanu Mircea D. Banciu Hui Zhao Nigam Rath James Chickos 《Structural chemistry》2006,17(6):639-648
Condensed and gas phase enthalpies of formation of 3:4,5:6-dibenzo-2-hydroxymethylene-cyclohepta-3,5-dienenone (1, (−199.1 ± 16.4), (−70.5 ± 20.5) kJ mol−1, respectively) and 3,4,6,7-dibenzobicyclo[3.2.1]nona-3,6-dien-2-one (2, (−79.7 ± 22.9), (20.1 ± 23.1) kJ mol−1) are reported. Sublimation enthalpies at T=298.15 K for these compounds were evaluated by combining the fusion enthalpies at T = 298.15 K (1, (12.5 ± 1.8); 2, (5.3 ± 1.7) kJ mol−1) adjusted from DSC measurements at the melting temperature (1, (T
fus, 357.7 K, 16.9 ± 1.3 kJ mol−1)); 2, (T
fus, 383.3 K, 10.9 ± 0.1) kJ mol−1) with the vaporization enthalpies at T = 298.15 K (1, (116.1 ± 12.1); 2, (94.5 ± 2.2) kJ mol−1) measured by correlation-gas chromatography. The vaporization enthalpies of benzoin ((98.5 ± 12.5) kJ mol−1) and 7-heptadecanone ((94.5 ± 1.8) kJ mol−1) at T = 298.15 K and the fusion enthalpy of phenyl salicylate (T
fus, 312.7 K, 18.4 ± 0.5) kJ mol−1) were also determined for the correlations. The crystal structure of 1 was determined by X-ray crystallography. Compound
1 exists entirely in the enol form and resembles the crystal structure found for benzoylacetone. 相似文献
12.
The geometrical parameters, normal vibration frequencies, and thermochemical characteristics of the Na2Cl+, NaCl
2
−
, Na3Cl
2
+
, and Na2Cl
3
−
ions in saturated vapors over sodium chloride were calculated by the ab initio methods including electron correlation. According to calculations, the Na2Cl+ and NaCl
2
−
triatomic ions have a linear equilibrium D
∞h
configuration. The pentaatomic ions can exist in the form of the D
∞h
linear isomer, C
2v
planar cyclic isomer, or D
3h
bipyramidal isomer. At ∼1000 K the Na3Cl
2
+
and Na2Cl
3
−
ions exist predominantly in the form of the linear isomers. The energies and enthalpies of the ion-molecule reactions involving
the above ions were calculated. The formation enthalpy of the ions Δf
H
0(0 K) was determined: 230 ± 2 kJ/mol (Na2Cl+), −96 ± 4 kJ/mol (Na2Cl
3
−
), −616 ± 2 kJ/mol (NaCl
2
−
), and −935 ± 4 kJ/mol (Na2Cl
3
−
).
Original Russian Text Copyright ? 2007 by T. P. Pogrebnaya, A. M. Pogrebnoi, and L. S. Kudin
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 6, pp. 1053–1061, November–December, 2007. 相似文献
13.
M. R. Bisengalieva L. P. Ogorodova M. F. Vigasina L. V. Mel’chakova 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2010,84(11):1838-1840
A calorimetric study of natural pyromorphite Pb5[PO4]3Cl was performed. Its enthalpy of formation was determined by melt solution calorimetry from elements Δf
H
el∘(298.15 K) = −4124 ± 20 kJ/mol. Value Δf
G
elo(298.15 K) = −3765 ± 20 kJ/mol was calculated. 相似文献
14.
Lei Zhang Hongmei Li Xueyan Liu Pingli Kang 《Russian Journal of Inorganic Chemistry》2012,57(4):622-628
Titanium dioxide nanoparticles were employed for the sorption of Ge(IV) ions from aqueous solution. The process was studied
in detail by varying the sorption time, pH, and temperature. The sorption process was found to be fast, equilibrium was reached
within 3 min. A maximum sorption could be achieved from solution when the pH ranges between 4.0 and 11.0. Sorbed Ge(IV) ions
can be completely desorbed with 2 mL of 0.3 mol L−1 K3PO4-1.0 mol L−1 H2SO4 mixture solution. The kinetic experimental data properly correlate with the second-order kinetic model (k
2 = 0.88 g mg−1 min−1 (25°C)), Reichenberg equation and Morris-Weber model. The estimated E
a
for Ge(IV) adsorption on nano-TiO2 was 19.66 kJ mol−1. The overall rate process appears to be influenced by intra-particle diffusion. The sorption data could be well interpreted
with the Langmuir and Dubinin-Radushkevich (D-R) type sorption isotherms. The D-R parameters were calculated to be K = −0.00321 mol2 kJ−2, q
m
= 0.59 mmol g−1 and E = 12.48 kJ mol−1 at room temperature. Furthermore, the thermodynamic parameters were also determined, and the ΔH
0 and ΔG
0 values indicated a spontaneous exothermic behavior. 相似文献
15.
Quinolin-8-ol-bonded polyurethane foam (Ox-PUF) was synthesized by coupling the polyurethane foam matrix with oxine through
an azo (-N=N-) group. The chromatographic retention behavior of Ag+, Pb2+, and Al3+ onto the Ox-PUF was studied. The extraction of Ag+, Pb2+, and Al3+ was accomplished within 15–20 min at pH ranges of 1–4, 4–6, and 6–12, respectively. The kinetics and thermodynamics of the
sorption of tested metal ions onto Ox-PUF have been studied. The average values of ΔH, ΔS, ΔG; k
1, k
−1, k′, and t
1/2 at 298 K were −28.7 kJ/mol, 210.1 J/(mol K), −6.74 kJ/mol, 0.095, 0.01, 0.113, and 7.184 min, respectively. The sorption
capacities of the Ox-PUF were 0.16, 0.07, and 0.59 mmol/g for Ag+, Pb2+, and Al3+, correspondingly. The proposed method has been successfully applied to the preconcentration and removal of tested metal ions
from wastewater. Recoveries between 80 and 99% were obtained (RSD ∼ 7).
The text was submitted by the authors in English. 相似文献
16.
M. F. Butman L. S. Kudin V. B. Motalov D. A. Ivanov V. V. Sliznev K. W. Krämer 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2008,82(5):767-772
The thermodynamic stability of the LaBr 4 ? anion was for the first time studied by high-temperature mass spectrometry and nonempirical quantum-chemical methods. The experimental and theoretical enthalpies of the reaction $ LaBr_4^ - = Br^ - + LaBr_3 The thermodynamic stability of the LaBr4− anion was for the first time studied by high-temperature mass spectrometry and nonempirical quantum-chemical methods. The
experimental and theoretical enthalpies of the reaction were Δr
H°(298.15 K) = 302 ± 14 and 303 kJ/mol, respectively. The value Δf
H° (LaBr4−, g, 298.15 K) = −1105 ± 14 kJ/mol was recommended as the enthalpy of formation of the LaBr4− anion.
Original Russian Text ? M.F. Butman, L.S. Kudin, V.B. Motalov, D.A. Ivanov, V.V. Sliznev, K.W. Kr?mer, 2008, published in
Zhurnal Fizicheskoi Khimii, 2008, Vol. 82, No. 5, pp. 885–890. 相似文献
17.
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
18.
The non-isothermal decomposition process of the powder sample of palladium acetylacetonate [Pd(acac)2] was investigated by thermogravimetric (TG) and the X-ray diffraction (XRD) techniques. Model-free isoconversional method
of Tang, applied to the investigated decomposition process, yield practically constant apparent activation energy in the range
of 0.05≤α≤0.95. It was established, that the Coats-Redfern (CR) method gives several statistically equivalent reaction models,
but only for the phase-boundary reaction models (R2 and R3), the calculated value of the apparent activation energy (E) is nearest to the values of E obtained by the Tang’s and Kissinger’s methods.
The apparent activation energy value obtained by the IKP method (132.4 kJ mol−1) displays a good agreement with the value of E obtained using the model-free analysis (130.3 kJ mol−1). The artificial isokinetic relationship (aIKR) was used for the numerical reconstruction of the experimental integral model
function, g(α). It was established that the numerically reconstructed experimental function follows R3 reaction model in the range of
α, taken from model-free analysis. Generally, decomposition process of Pd(acac)2 starts with initial nucleation which was characterized by rapid onset of an acceleratory reaction without presence of induction
period. 相似文献
19.
Relative enthalpies for low-and high-temperature modifications of Na3FeF6 and for the Na3FeF6 melt have been measured by drop calorimetry in the temperature range 723–1318 K. Enthalpy of modification transition at 920
K, δtrans
H(Na3FeF6, 920 K) = (19 ± 3) kJ mol−1 and enthalpy of fusion at the temperature of fusion 1255 K, δfusH(Na3FeF6, 1255 K) = (89 ± 3) kJ mol−1 have been determined from the experimental data. Following heat capacities were obtained for the crystalline phases and for
the melt, respectively: C
p(Na3FeF6, cr, α) = (294 ± 14) J (mol K)−1, for 723 = T/K ≤ 920, C
p(Na3FeF6, cr, β) = (300 ± 11) J (mol K)−1 for 920 ≤ T/K = 1233 and C
p(Na3FeF6, melt) = (275 ± 22) J (mol K)−1 for 1258 ≤ T/K ≤ 1318. The obtained enthalpies indicate that melting of Na3FeF6 proceeds through a continuous series of temperature dependent equilibrium states, likely associated with the production of
a solid solution.
相似文献
20.
M. R. Bisengalieva L. V. Mel’chakova L. P. Ogorodova M. F. Vigasina 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2010,84(9):1481-1484
A thermal and thermochemical study of natural aqueous hydroxyl-containing diorthosilicate, hemimorphite Zn4[Si2O7](OH)2 · H2O, was performed. The step character of its thermal decomposition was studied using FTIR spectroscopy. Melt solution calorimetry
was used to determine the enthalpies of formation from oxides Δf
H
OOX (298.15 K) = −69.3 ± 9.9 kJ/mol and elements {ie1481-2} (298.15 K) = −3864.3 ± 10.2 kJ/mol. 相似文献