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81.
V. D. Kiselev G. G. Iskhakova E. A. Kashaeva L. N. Potapova A. I. Konovalov 《Russian Chemical Bulletin》2004,53(11):2490-2495
The densities of anthracene, tetracyanoethylene, maleic anhydride, N-phenylmaleineimide, trans, trans-1,4-diphenylbuta-1,3-diene, and their Diels-Alder adducts were measured in the solid state and in solution at 25 °C. The reaction volumes in the solid state were calculated from the difference in molar volumes. They turned out to be low, close to each other (–4 to –11 cm3 mol–1), and slightly different from the reaction volumes (–8±1 cm3 mol–1) calculated from the van der Waals radii. The reaction volumes in solutions (–15 to –32 cm3 mol–1) were found from the difference in partial molar volumes of the reactants in dioxane, acetonitrile, and 1,2-dichloroethane, The experimental Diels-Alder reaction volumes in solution are determined not only by the formation of new bonds in an adduct: a considerably higher contribution (to 75%) is made by a change in the volume of intermolecular empty spaces in solution on going from reactants to adducts.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2386–2390, November, 2004. 相似文献
82.
83.
Densities and apparent molar volumes of aqueous 2-chloroethanol were determined at temperatures from 15.0 to 34.4°C using digital densimetry. The results of the volumetric measurements have been used to calculate the following thermodynamic quantites at 25°C: V
2
o = 55.05 ± 0.02 cm3-mol–1, (V
2
o/T)p = 0.01486 ± 0.00318 cm3-K–1-mol–1, and (2
V
2
o/T
2)p = 0.02972 ± 0.00318 cm3-K–2-mol–1. Partial molar volumes of transfer from water to 1 mol-dm–3 2-chloroethanol have also been determined for L-glycine, L-alanine, L-serine, L-glutamic acid, and L-aspartic acid at 35.0°C. The transfer results have been explained in terms of the nature of the interactions of the groups in the solute and solvent. Hydration numbers of L-glycine and L-alanine have also been calculated in aqueous 2-chloroethanol. 相似文献
84.
A new theoretical approach of the isothermal crystallization of a thin polymer film is proposed. This model, derived from Evans' theory, is in very good agreement with a previous one, but is much more interesting because it makes it possible to calculate the transformed volume fraction anywhere in the film. The main effects of decreasing thickness are a slower average crystallization of the film and a decrease in the Avrami exponent caused by a slower crystallization of the polymer close to the surfaces.A slight modification of the model allows us to calculate the isothermal crystallization kinetics at any point of the film when it contains two identical transcrystalline regions on its surfaces.All the models are well verified by computer simulations. 相似文献
85.
The volume and compressibility changes on mixing aqueous solutions of the amino acid and poly(ethylene glycol) were measured with a vibration densimeter and a sing-around velocimeter at 298.15 K. For the system of alanine-PEG-H2O, the additivity rule for the mean apparent molal volume and compressibility at infinite dilution held, and the excess volume and compressibility changes on mixing were obtained. For the system of glycine-PEG-H2O, the additivity rule for the mean apparent molal compressibility at infinite dilution did not hold. While the mean apparent molal volume and compressibility changes were negative and positive for the systems of another amino acid-PEG-H2O, respectively, where amino acids were valine, isoleucine, leucine, phenylalanine, and tryptophan. These results suggest that glycine and alanine are excluded from the hydration layer around PEG chain and the amino acids with a larger side chain than alanine are bound to the PEG chain due to the hydrophobic interaction. The hydration number per monomer around PEG chain was estimated to be 3.9. 相似文献
86.
The apparent molar volumes V of KCl, BaCl2, K2SO4, LaCl3, Co(en)3Cl3 [Tris(ethylenediamine)cobalt(III) chloride], K3Co(CN)6, K3Fe(CN)6, K4Fe(CN)6, and Ba3[Co(CN)6]2 have been determined at 25°C in both light and heavy water. The V values in D2O are systematically lower and increase more rapidly with salt concentration than the V in H2O. The volume of transfer from H2O to D2O as well as the partial molar volume at infinite dilution in both solvents have also been calculated. These results together with literature values for other electrolytes were used to estimate both of these quantities for D2O solutions of individual ions. The predictions of ion hydration models and ion-ion interactions are compared with experimental observations. 相似文献
87.
E. V. Ivanov E. Yu. Lebedeva V. K. Abrosimov N. G. Ivanova 《Russian Chemical Bulletin》2004,53(4):751-757
Densities of Bun
4NBr solutions in MeOH, MeOD, and CD3OH were measured at salt concentrations of up to 1.5 solvomolality units (nearly 2.63·10–2 mole fraction) at 278.15, 288.15, 298.15, 308.15, and 318.15 K. The limiting partial molar volumes of Bun
4NBr dissolved in these alcohols were calculated. The isotope effects in the volume characteristics of the stoichiometric mixture of ions, [Bun
4N+ + Br–], are mainly due to the vibrational changes in the solvent structure upon deuteration of different molecular fragments. Structural transformations in infinitely dilute solution of Bun
4NBr in methanol are governed by non-specific solvation of the symmetrical Bun
4N+ cation. 相似文献
88.
溶液的过剩热容是热力学的重要函数,对其测定与研究具有理论与实际意义.过剩热容不仅可检验溶液中分子间的相互作用,并可利用其计算混合物的热容.本文报告了用微量热仪对环乙烷一本等七个二元物系全浓度范围内在29815K、常压下过剩热容CEp进行的测定工作,上述体系是由具有 相似文献
89.
G. V. Kotelnikov Sophia P. Moiseyeva E. V. Mezhburd E. I. Maevsky Elena V. Grishina 《Journal of Thermal Analysis and Calorimetry》2005,81(2):255-259
Summary Measurements of energy transformation in mitochondria are done on a capillary differential titration calorimeter CTD2156. It is important to mention that a sediment is quickly formed by the mitochondria suspension without mixing by means of a vibrating needle. During the measurements, the vibrating needle is located inside the working volume of the chamber. The design of the calorimeter is substantiated theoretically. It provides a new mode of a reagent input in the measuring volume of the calorimetric chambers. It expands the spectrum of tasks that can be solved using this instrument. In the capillary calorimeter the calorimetric chambers unit is simple and small in size. These advantages of capillary chambers provide an opportunity to unite 20 capillary calorimetric chambers in one calorimetric block. It allows designing a multi-channel titration calorimeter. There are obvious advantages of such a calorimeter over other instruments in screening researches and in researches of objects maintaining stability only for a short time. 相似文献
90.