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31.
In order to examine the reason why the magnitude of the synergistic effect observed in the extraction of lanthanoids(III) with a β-diketone and a monodentate Lewis base generally decreases along with increasing atomic number, the hydration number of the extracted species when lanthanoids(III) are extracted with TTA (2-thenoyltrifluoroacetone, HA) and benzoic acid (HB) into chloroform by Karl Fischer titration and the enthalpy change in complexation between LnA3 and HB by calorimetric titration were determined across the lanthanoid series at 25 °C.It has been concluded that since the decrement of entropy change caused by the change in the number of released water molecules and in the coordination number of lanthanoids(III) upon complexation is larger than the increment of the enthalpy change, the values of the second formation constants of the complexes decrease with increasing the atomic number across lanthanoid series so that the magnitude of the synergistic extraction decreases with increasing the atomic number. 相似文献
32.
Summary. Several compounds may exist in LnCl3–MCl mixtures. Those corresponding to the M
2
LnCl5 and MLn
2Cl7 stoichiometries are formed in a few systems only, with diverse stability strongly dependent on both the corresponding lanthanide
and alkali metal. On the other hand, M
3
LnCl6 that occur in most systems have a far larger stability range and melt congruently. These latter compounds were investigated
in the present work by differential scanning calorimetry and electrical conductivity measurements. The thermodynamic and transport
properties were correlated to structural features and related to the mechanism of compound formation.
Corresponding author. E-mail: Marcelle.Gaune-Escard@polytech.univ-mrs.fr
Received October 2, 2002; accepted November 6, 2002
Published online April 24, 2003
RID="a"
ID="a" This paper is dedicated to Professor H. Gamsj?ger on the occasion of his birthday 相似文献
33.
Akio?OhtaEmail author Satoru?Nakashima Hiroki?Matsuyanagi Tsuyoshi?Asakawa Shigeyoshi?Miyagishi 《Colloid and polymer science》2003,282(2):162-169
The Krafft temperatures and enthalpies of solution of N-hexadecanoyl alaninate and valinate, and N-tetradecanoyl phenylalaninate were obtained from differential scanning calorimetry. The Krafft temperature of N-acyl amino acid surfactant increased with decreasing size of the counter ion, with some exceptions. The enthalpy of solution was endothermic and increased with decreasing size of the counter ion except for the cases of lithium salt. The results showed that the L-L interaction in the solid state of N-hexadecanoyl amino acid surfactant salt was superior to the D-L interaction for both the alanine and valine systems when the counter ion size increased. However, the D-L interaction was still advantageous for the phenylalanine system with Cs+ as a counter ion. Both Fourier transform infrared spectroscopy studies and theoretical calculations suggested that the difference in magnitudes of the interactions between peptide and counter ion was a dominant factor for the chiral effect. 相似文献
34.
Enthalpy‐entropy compensation remains a mystery in chemistry and biophysics. Recent study suggested that the solvent reorganization might constitute the physical origin of the compensation, which was unfortunately not widely applicable because compensation was also observed in solid phase reactions. In this study, a general theoretical model based upon strict mathematical deduction was presented, which indicated that the redistribution of the distinguishable subspecies might be the physical origin of the enthalpy‐entropy compensation in complex systems. As examples, the enthalpy‐entropy compensations in solvation and surface adsorption were discussed. 相似文献
35.
The enthalpies of dilution of
-alanine and
-serine in various aqueous urea solutions have been determined by flow microcalorimetry at 298.15 K. The homogeneous enthalpic interaction coefficients over the whole range of aqueous urea solutions have been calculated according to the excess enthalpy concept. The results were interpreted from the point of view of solute–solute interactions moderated by solvent effects. 相似文献
36.
The variations of thermal conductivity with temperature for Pb–Sn alloys were measured using a radial heat flow apparatus. The variations of electrical conductivity with the temperature for same alloys were determined from the Wiedemann–Franz law by using the measured values of thermal conductivity. According to present experimental results, the thermal and electrical conductivity of Pb–Sn alloys linearly decrease with increasing temperature but exponentially increase with increasing the composition of Sn. The enthalpy of fusion and the change of specific heat for Pb–Sn alloys were also determined by means of differential scanning calorimeter (DSC) from heating trace during the transformation from eutectic liquid to eutectic solid. 相似文献
37.
Thomas J. Bruno Lisa S. OttTara M. Lovestead Marcia L. Huber 《Journal of chromatography. A》2010,1217(16):2703-2715
The analysis of complex fluids such as crude oils, fuels, vegetable oils and mixed waste streams poses significant challenges arising primarily from the multiplicity of components, the different properties of the components (polarity, polarizability, etc.) and matrix properties. We have recently introduced an analytical strategy that simplifies many of these analyses, and provides the added potential of linking compositional information with physical property information. This aspect can be used to facilitate equation of state development for the complex fluids. In addition to chemical characterization, the approach provides the ability to calculate thermodynamic properties for such complex heterogeneous streams. The technique is based on the advanced distillation curve (ADC) metrology, which separates a complex fluid by distillation into fractions that are sampled, and for which thermodynamically consistent temperatures are measured at atmospheric pressure. The collected sample fractions can be analyzed by any method that is appropriate. The analytical methods we have applied include gas chromatography (with flame ionization, mass spectrometric and sulfur chemiluminescence detection), thin layer chromatography, FTIR, corrosivity analysis, neutron activation analysis and cold neutron prompt gamma activation analysis. By far, the most widely used analytical technique we have used with the ADC is gas chromatography. This has enabled us to study finished fuels (gasoline, diesel fuels, aviation fuels, rocket propellants), crude oils (including a crude oil made from swine manure) and waste oils streams (used automotive and transformer oils). In this special issue of the Journal of Chromatography, specifically dedicated to extraction technologies, we describe the essential features of the advanced distillation curve metrology as an analytical strategy for complex fluids. 相似文献
38.
The stability of the disordered structure in liquid or glass states could be characterized by the glass-forming ability (GFA) and thermal stability (TS), respectively. The two quantities are often, but not always, positively correlated. Here we show that the discrepancy between GFA and TS originates from the competition between entropy and enthalpy which fairly much relies on local structural characteristics. This inherent interaction and competition determines hierarchy of phase stability against temperature. As a result, the time susceptibility of GFA and temperature susceptibility of TS were derived from the time-temperature-transformation diagram, which are coincided with the above mentioned entropy-enthalpy competition perspective. Thus, the interrelationship among entropy, enthalpy and local cluster feature provides a potential resolution to design and optimize glass formers, and have implications for better understanding the nature of glass transition. 相似文献
39.
Differential scanning calorimetry and dc conductivity measurements were used to study structural relaxation of Se70Te30 glass. A single set of Tool-Narayanaswamy-Moynihan (TNM) parameters was obtained from the curve-fitting procedure. The value of apparent activation energy Δh∗ was further confirmed by two non-fitting techniques. Results of the Δh∗ evaluation from the Tg dependence on cooling rate are discussed in terms of how the Tf determination might be influenced by the material’s structure type and by the interference of the crystallization process. 相似文献
40.
The vapour pressuresof liquid cyclohexane + N, N, N′, N′-tetramethylalkanediamine, (CH3)2 N(CH2)uN(CH3)2 (u = 1,2) + cyclohexane mixtures were measured by a static method between 303.15 and 343.15 K at 10 K intervals. The excess molar enthalpies at 303.15 K were also measured.
The molar excess Gibbs energies, calculated from the vapour-liquid equilibrium data, and the molar excess enthalpies compare satisfactorily with group contribution (DISQUAC) predictions.
The proximity effect of N atoms produces a regular decrease of the interactional parameters. 相似文献