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101.
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
102.
E. T. Denisov 《Russian Chemical Bulletin》2005,54(4):914-923
Interatomic distances in the reaction centers of the addition reactions of (i) H· to the C=C, C=O, N≡C, and C≡C bonds, (ii) ·CH3 radical to the C=C, C=O, and C≡C bonds, and (iii) alkyl, aminyl, and alkoxyl radicals to olefin C=C bonds were determined
using a new semiempirical method for calculating transition-state geometries of radical reactions. For all reactions of the
type X· + Y=Z → X— Y—Z· the r
#
X...Y distance in the transition state is a linear function of the enthalpy of reaction. Parameters of this dependence were determined
for seventeen classes of radical addition reactions. The bond elongation, Δr
#
X...Y, in the transition state decreases as the triplet repulsion, electronegativity difference between the atoms X and Y in the
reaction center, and the force constant of the attacked multiple bond increase.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 894–902, April, 2005. 相似文献
103.
Z. H. Zhang Z. J. Ku H. R. Li Y. Liu S. S. Qu 《Journal of Thermal Analysis and Calorimetry》2005,79(1):169-173
The solid-state ternary complex of terbium chloride with L-tyrosine and glycine, [Tb(Tyr)(Gly)3Cl3·3H2O], was synthesized and characterized. Using a solution-reaction isoperibol calorimeter, the enthalpy of reaction for the following reaction, TbCl3·6H2O(s)+Tyr(s)+3Gly(s)=Tb(Tyr)(Gly)3Cl3·3H2O(s)+3H2O(l), was determined to be (5.1±0.6) kJ mol-1. The standard enthalpy of formation of Tb(Tyr)(Gly)3Cl3-3H2O at T=298.15 K has been derived as -(4267.3±2.3) kJ mol-1. The thermal decomposition kinetics of the complex was studied by non-isothermal thermogravimetry in the temperature range of 325-675 K. Two main mass loss stages existed in the process of the decomposition of the complex, the kinetic parameters for the second stage were analyzed by means of differential and integral methods, respectively. Comparing the results of differential and integral methods, mechanism functions of the thermal decomposition reaction for its second stage were proposed. The kinetic equation can be expressed as: d/dt=Aexp(-E/RT)(1-)2. The average values of the apparent activation energy E and pre-exponential factor A were 213.18 kJ mol-1 and 2.51·1020 s-1, respectively. 相似文献
104.
I. Zięborak-Tomaszkiewicz 《Journal of Thermal Analysis and Calorimetry》2006,83(3):611-615
The energies of combustion
in fluorine of gallium nitride and indium nitride in wurzite crystalline structure
have been measured in a two-compartment calorimetric bomb, and new standard
molar enthalpies of formation have been calculated: ΔfHm0(GaN(cr)
298.15 K)= –(163.7±4.2) kJ mol–1
and ΔfHm0(InN(cr) 298.15 K)= –(146.5±4.6) kJ mol–1
. Comparison with the recommended values of the ΔfHm0 nitrides
from the literature is also presented. 相似文献
105.
Enthalpies of solution of sodium benzoate, potassium benzoate, and potassium halo-substituted benzoates are reported at 298.15°K
in water and in nine water-tert-butyl alchol mixtures. Transfer enthalpies from water to the mixed solvent go through a maximum for about 0.055 mole fraction
of alcohol. Additivity of ionic contributions in the enthalpies of transfer is verified. Substituent effects on the transfer
enthalpies of benzoates are discussed in terms of size of the solutes and cohesion of the solvent mixtures.
For Part V, see ref. 1. 相似文献
106.
Thermal oxidative treatment enhances the activity of a schungite rock in the sorption of petrochemicals from aqueous solutions.
The effect of the thermal oxidative activation on the content and distribution of carbon in the rock and the dependence of
the sorption activity on the texture of sorbents were studied.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2233–2238, October, 2005. 相似文献
107.
J. L. Oscarson R. M. Izatt P. R. Brown Z. Pawlak S. E. Gillespie J. J. Christensen 《Journal of solution chemistry》1988,17(9):841-863
The aqueous reactions,
相似文献
108.
Stefan Motiu Daniela Dogaru Valentin Gogonea 《International journal of quantum chemistry》2007,107(5):1248-1252
This work puts forth a reaction pathway for the reactivation of exogenous ligand inhibited H‐cluster, the active site of Fe‐only hydrogenases. The H‐cluster is a dimetal complex, Fe–Fe, with the metal centers bridged by di(thiomethyl)amine. Exogenous ligands, H2O, and OH?, are bound to the distal iron (Fed). Density functional theory (DFT) calculations on the native and ruthenium‐modified H‐cluster have been performed using the B3LYP functional with 6‐31+G** and 6‐311+G** basis sets. We have ascertained that there is a thermodynamically favorable pathway for the reactivation of the OH? inhibited H‐cluster, which proceeds by an initial protonation of the Fed–OH? complex. The proposed reaction pathway has all its intermediate reactions ensue exothermically. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
109.
Temperature-modulated calorimetry (TMC) allows the experimental evaluation of the kinetic parameters of the glass transition from quasi-isothermal experiments. In this paper, model calculations based on experimental data are presented for the total and reversing apparent heat capacities on heating and cooling through the glass transition region as a function of heating rate and modulation frequency for the modulated differential scanning calorimeter (MDSC). Amorphous poly(ethylene terephthalate) (PET) is used as the example polymer and a simple first-order kinetics is fitted to the data. The total heat flow carries the hysteresis information (enthalpy relaxation, thermal history) and indications of changes in modulation frequency due to the glass transition. The reversing heat flow permits the assessment of the first and higher harmonics of the apparent heat capacities. The computations are carried out by numerical integrations with up to 5000 steps. Comparisons of the calculations with experiments are possible. As one moves further from equilibrium, i.e. the liquid state, cooperative kinetics must be used to match model and experiment.On leave from Toray Industries, Inc., Otsu, Shiga 520, Japan.This work was supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, U. S. Department of Energy at Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the U. S. Department of Energy, under contract number DE-AC05-96OR22464. Support for instrumentation came from TA Instruments, Inc. Research support was also given by ICI Paints, and Toray Industries, Inc. 相似文献
110.
Manuel Temprado 《Thermochimica Acta》2005,435(1):49-56
The vaporization enthalpies and vapor pressures of acetoin, ethyl 3-hydroxybutyrate and ethyl 3-hydroxyhexanoate, found in a variety of foods and flavors, are evaluated at T = 298.15 K using correlation-gas chromatography; values of (48.7 ± 0.4), (55.9 ± 0.6) and (61.9 ± 0.6) kJ mol−1, respectively, were obtained. These values are in good agreement with estimated values. Vapor pressures of the standards as a function of temperature were also used to calculate vapor pressures of the target compounds and all resulting data were fit to second order polynomials. These polynomials were then used to predict boiling temperatures of both standards and target substances. Agreement with experimental boiling temperatures was generally within 10 K suggesting that vapor pressures are accurate to within a factor of two. Acetoin exists as an equilibrium mixture of monomer and dimer. This report provides an example of the utility of using correlation-gas chromatography to obtain thermochemical data on an impure material. 相似文献
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