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81.
The concentration dependence of the apparent molar volumes of lithium halides (and electrolytes in general) in alcohols (and
solvents permitting association in general) is, in the first instance, due to changes in the degree of association and to
the inherent difference between the apparent molar volumes of the ions and of the ion pairs. Previous publications on the
molar volumes of electrolytes in organic solvents, disregarding altogether ion pairing, appear to be incorrect. Data from
the literature for lithium chloride and lithium bromide in normal primary alcohols and several branched alcohols from C1 to C8 and data from our laboratory for lithium halides in 1-hexanol and 2-ethyl-1-hexanol served for the determination of φ
V
and φ
E
. Electrical and structural contributions to the values of these functions for the ions and for the ion pairs are discussed. 相似文献
82.
R.?R.?NazmutdinovEmail author T.?T.?Zinkicheva 《Russian Journal of Electrochemistry》2005,41(2):206-212
The fluoride ion adsorption from a gas phase on various faces of a single crystal of silver is studied by a density functional method within a cluster model for metal. The adsorption bond energy is found to increase in the series Ag(100) < Ag(111) < Ag(311) < Ag(110). A substantial structural and energetic heterogeneity of various adsorption sites is revealed. The results are utilized to simulate the electrochemical interface between individual faces of a single crystal of silver and aqueous solutions containing the fluoride ion. It is assumed that the adsorption potential may be represented as the sum of two contributions, one of which describes the metal–ion interaction and the other, the ion solvation energy. The plotted adsorption terms take into account partial degradation of the fluoride ion when adsorbed from an aqueous solution. Estimates of discreteness of the electrical double layer are presented. A conclusion on the maximum manifestation of specific adsorption of the fluoride ion for the Ag(100) face is made.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 232–238.Original Russian Text Copyright © 2005 by Nazmutdinov, Zinkicheva.This revised version was published online in April 2005 with corrections to the article note and article title and cover date. 相似文献
83.
Attempts to theoretically address the problems involved in transferring linear gradient elution methods have been somewhat ad hoc due to the simplifying assumptions usually made in conventional gradient elution theory. Until now, all equations based on the k* parameter of linear gradient elution theory used as the basis for predicting the separation selectivity have not explicitly included the effect of the dwell volume (VD). Using an exact equation for predicting k*, that is, one which fully accounts in an a priori fashion for VD, we find a set of simple yet exact equations which unequivocally must be satisfied to transfer an optimized linear gradient elution method from one system (column or instrument or both) to another. These relationships absolutely mandate that a change in the instrument dwell volume requires a proportional change in the column volume; in turn, a change in the column volume requires a proportional change in the flow rate and/or gradient time to maintain a constant gradient steepness. Although we are not the first to suggest these guidelines, this work provides a complete theoretical foundation for these exact guidelines for the maintenance of gradient selectivity for the case of transferring a linear gradient elution method between different columns packed with the same particles and/or between different instruments. 相似文献
84.
Using a precise technique of scanning microcalorimetry the heat capacity differences between water and dilute aqueous solutions of ethanol, n-propanol, n-butanol and n-pentanol were measured from 5 to 125°C and the partial molar heat capacities of these substances in water were determined. It was found that the heat capacity increment for alcohol disolved in water is proportional to the number of the-CH
2
–
groups and decrease with a temperature increase. The heat capacity increment of hydration of non-polar groups is shown to be positive and large at room temperature and decreases in magnitude as the temperature increases. In contrast, the heat capacity increment of hydration of polar groups is negative at room tempreature and increases as the temperature increases. From the temperature dependence of the heat capacity increment one can assume that the water molecules solvated by the non-polar groups of the alcohols behave in a non-cooperative manner. 相似文献
85.
The apparent molal volumes and compressibilities of NaCl, KCl, and CsCl in mixtures of 18-Crown-6 and water have been calculated from density and speed-of-sound measurements at 25°C. The partial molal volumes and compressibilities of the salts when all cations have formed complexes with 18-Crown-6 molecules have been evaluated. The sign and magnitude of the volume and compressibility changes of complex formation strongly suggest that the charge of the cation becomes very effectively screened by the crown ether. 相似文献
86.
酞侧基聚芳醚酮的热学性能谢红卫,李滨耀(中国科学院长春应用化学研究所长春130022)关键词酞侧基聚芳醚酮,pvT行为,导热系数,定压比热容酞侧基聚芳醚酮(PEK-C)具有较高的玻璃化转变温度,其流变加工性能和力学性能已被广泛研究[1~3],被证明是... 相似文献
87.
A new method for predicting conduction anesthesia has been suggested. The method is based on calculation of theP matrix probabilities of interatomic contacts for each molecule of the compounds considered. TheP matrix enables one to evaluate the main tendencies of atoms and atomic groups to interact in biochemical sorption on the
nerve fiber surface. The minimum effective concentrations calculated for 25 compounds are in good agreement with the experimental
data. The correlation coefficient between the experimental and calculated values is 0.98 when the standard deviation is 0.1
mmol L−1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1781–1784, October, 1997. 相似文献
88.
J. M. Igartua G. Aguirre-Zamalloa I. Ruiz-Larrea M. Couzi A. López-Echarri T. Breczewski 《Journal of Thermal Analysis and Calorimetry》1994,41(6):1211-1215
The specific heat of N(CH3)4CdBr3 from 50 to 300 K has been measured by adiabatic calorimetry, using both static and dynamic methods. The obtained results have permitted a careful study of the ferro-paraelectric phase transition the crystal shows at 160 K. The available spectroscopic data have been used to generate a reliable baseline which accounts for the normal lattice contribution to the specific heat. These results allow for an accurate estimation of the phase transition thermodynamic functions: ΔH=2620 J·mol?1 and ΔS=18.04 J·(mol°C)?1. These high values are in agreement with the predictions of the 6 well potential Frenkel model. 相似文献
89.
The viscosities of seven n-alkylamines from n-butylamine to n-decylamine were determined from 15 to 80°C at 5°C intervals. The intrinsic volumes were determined by extrapolation of the plot of fluidity against molar volume to zero fluidity and found to be a linear function of the number of carbon atoms. Plots of the logarithm of viscosity vs. reciprocal absolute temperature were almost linear. The energies of activation for viscous flow for the n-alkylamines were calculated and found to increase with increase in the carbon number. The B values, based on Hildebrand's equation and representing a measure of a molecules resistance to transport of momentum, were calculated for each of the n-alkylamines. A modified form of the equation describing the change fluidity with temperature was then formulated. It is suggested that the activation energy for viscous flow consists of the sum of the energy required for the expansion of the void volume and the energy required to overcome intermolecular interactions. These energies were calculated and discussed. 相似文献
90.
Summary A flow-through two electrode wall-jet cell with a platinum measuring electrode and a cell volume of 20 nl has been designed and evaluated. It has been used to detect phenols by reversed phase liquid chromatography using short micro bore columns. The linear dynamic range between the measured current and the concentration is greater than 103 (1.5×10–7–5×10–4 mol/l) and the minimum analyzable amount was found to be 10 pg for pyrocatechol. A negligible broadening in the detector permits the use of micro columns down to 0.5 mm internal diameter, packed with 5 m particles, without any substantial distortion of eluted zones.Presented at the 14th International Symposium on Chromatography London, September, 1982 相似文献