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61.
62.
The apparent and limiting apparent molar volumes of dilute aqueous solutions of KBF4, and the complexes [Fe(DMSO)6](BF4)3, [Fe(Py)4(H2O)2](BF4)3, [Fe(4-Mepy)2(H2O)2](BF4)3, and [Fe(4-Etpy)2(H2O)2](BF4)3 were determined from density data measured at 5, 15, and 25°C. The apparent and limiting apparent molar adiabatic compressibilities of these complexes were determined from ultrasonic sound velocities measured at the same temperatures in dilute aqueous solutions. The volume change associated with complex formation is discussed in terms of the nature of the coordinate bond and also the role of the central metal atom and ligands in the solvation behavior of these complexes. 相似文献
63.
64.
J. Canosa 《The Journal of chemical thermodynamics》2003,35(12):2021-2031
Density, refractive index and speed of sound at T=298.15 K and atmospheric pressure have been measured over the entire composition range for (dimethyl carbonate (DMC) + methanol + ethanol) and (DMC + methanol + 1-propanol). Excess molar volumes, changes of refractive index on mixing and deviations in isentropic compressibility for the above systems have been calculated. The calculated quantities are further fitted to the Cibulka equation to estimate the ternary fitting parameters. Standard deviations from the regression lines are shown. 相似文献
65.
Marcos Mandaji Tiago Buckup Rafael Rech Ricardo Rego Bordalo Correia Tarso Ledur Kist 《Talanta》2007,71(5):1998-2002
The performance of fluorescence detectors in capillary electrophoresis is maximized when the excitation light intensity is modulated in time with optimal frequencies. This is especially true when photomultiplier tubes are used to detect the fluorescent light. The photomultiplier tube amplified raw output signal can in principle be captured directly by a personal computer sound card (PCSC) and processed by a lock-in emulated by software. This possibility is demonstrated in the present work and the performance of this new setup is compared with a traditional data acquisition system. The results obtained with this “PCSC and lock-in emulated by software” were of the same quality or even better compared to that obtained by conventional time integrators (Boxcars) and data acquisition boards. With PCSC the limits of detection (LOD) found for both naphthalene-2,3-dicarboxaldehyde-derivatized tyrosine and alanine were 3.3 and 3.5 fmol (injection of 5 nL of samples at 0.66 and 0.70 μmol/L), respectively. This is at least three times better compared to conventional systems when light emitting diodes (LEDs) are used as the excitation source in fluorescence detectors. The PCSC linear response range was also larger compared to conventional data acquisition boards. This scheme showed to be a practical and convenient alternative of data acquisition and signal processing for detection systems used in capillary electrophoresis. 相似文献
66.
The spatial relaxation of electrons to homogeneous states under the action of space-independent electric fields is investigated
in helium, krypton, and N2 plasmas for various electric field strengths. These investigations are based on a new method recently developed for solving
the one-dimensional inhomogeneous electron Boltzmann equation in weakly ionized, collision-dominated plasmas. Elastic as well
as conservative inelastic collisions of electrons with gas atoms have been included in the kinetic treatment. The spatial
relaxation is caused by an imposed direct disturbance in the velocity distribution of the electrons on a spatial boundary.
A pronounced dependence of the relaxation structure and the resultant relaxation length on the atomic data of the electron
collision processes in different gases has been found. Furthermore the relaxation process sensitively depends on the electric
field strength in the region of medium field values. 相似文献
67.
Densities (ρ), viscosities (η) and speeds of sound (u) of the ternary mixture (1-heptanol + tetrachloroethylene + methylcyclohexane) and the corresponding binary mixtures (1-heptanol + tetrachloroethylene),
(1-heptanol + methylcyclohexane) and (tetrachloroethylene + methylcyclohexane) at 298.15 K were measured over the whole composition
range. The data obtained are used to calculate the excess molar volumes (V
E), excess isobaric thermal expansivities (α
E), viscosity deviations (Δη), excess Gibbs energies of activation of viscous flow (ΔG
*E) and excess isentropic compressibilities (κ
S
E) of the binary and ternary mixtures. The data from the binary systems were fitted by the Redlich–Kister equation whereas
the best correlation method for the ternary system was found using the Nagata equation. Viscosities, speeds of sound and isentropic
compressibilities of the binary and ternary mixtures have been correlated by means of several empirical and semi-empirical
equations. The best correlation method for viscosities of binary systems is found using the Iulan et al. equation and for
the ternary system using the Heric and McAllister equations. The best correlation method for the speeds of sound and isentropic
compressibilities of the binary system (1-heptanol + methylcyclohexane) is found using IMR (Van Deal ideal mixing relation)
and for the binary system (tetrachloroethylene + methylcyclohexane) it is found using the NR (Nomoto relation) and for the
binary system (1-heptanol + tetrachloroethylene) and the ternary system (1-heptanol + trichloroethylene + methylcyclohexane)
it is obtained from the FLT (Jacobson free length theory). 相似文献
68.
In this paper, excess thermodynamic functions have been computed from the measured values of density, viscosity, and refractive index at T = (298.15, 303.15, and 308.15) K, ultrasonic velocity at T = 298.15 K over the entire mixture composition range of (anisole with ethanol, propan-1-ol, propan-2-ol, butan-1-ol, pentan-1-ol, or 3-methyl butan-1-ol). Excess molar volume, VE has been calculated from densities, whereas deviations in viscosity, Δη, were computed from the measured viscosities. From ultrasonic velocities, isentropic compressibilities were calculated, from which deviations in isentropic compressibility, Δks have been computed. Lorenz-Lorentz mixture rule was used to compute molar refractivity, R from refractivity index data and from these data, deviations in molar refractivity, ΔR have been computed. Computed thermodynamic quantities have been fitted to Redlich and Kister polynomial equation to derive the coefficients and standard errors between experimental and predicted quantities. Intermolecular interactions between anisole and alkanols have been studied based on the computed excess thermodynamic quantities. 相似文献
69.
Excess volumes (VE) ultrasonic sound velocities (u), isentropic compressibilities (Ks) and viscosities (η) have been measured for the binary mixtures of dimethylsulphoxide (DMSO) with 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,4-trichlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-nitrotoluene and m-nitrotoluene at T = 303.15 K. The measured VE values were positive over the entire composition range in all the binary mixtures. Isentropic compressibilities (Ks) have been computed for the same systems from precise sound velocity and density data. Further, deviation in isentropic compressibility (ΔKs) from ideal behaviour was also calculated. The viscosity data are analysed on the basis of corresponding states approach. Deviation in viscosities are positive over the entire composition range. The measured data is explained on the basis of intermolecular interactions between unlike molecules. 相似文献
70.
The partial molar isentropic pressure coefficients at infinite dilution, K
S,2
o
, have been determined for a number of dipeptides in aqueous solution at 25°C. For a series of dipeptides of sequence gly-X, where X is an amino acid with a neutral side chain, the K
S,2
o
values are all more negative than that for diglycine. The results are discussed in terms of the hydration of the side chains. There are significant differences in the K
S,2
o
values for sequence isomeric dipeptides. These differences can be rationalized in terms of the mutual interactions between the side chain and the ionic end groups in the dipeptides. Possible relationships between K
S,2
o
and V
2
o
, the partial molar volume at infinite dilution, were investigated. For the dipeptides of sequence gly-X there is an interesting linear relationship between K
S,2
o
/V
2
o
and V
2
o
. 相似文献