全文获取类型
收费全文 | 696篇 |
免费 | 24篇 |
国内免费 | 74篇 |
专业分类
化学 | 389篇 |
力学 | 17篇 |
综合类 | 3篇 |
数学 | 158篇 |
物理学 | 227篇 |
出版年
2024年 | 3篇 |
2023年 | 4篇 |
2022年 | 11篇 |
2021年 | 5篇 |
2020年 | 10篇 |
2019年 | 11篇 |
2018年 | 4篇 |
2017年 | 14篇 |
2016年 | 19篇 |
2015年 | 25篇 |
2014年 | 26篇 |
2013年 | 54篇 |
2012年 | 28篇 |
2011年 | 43篇 |
2010年 | 31篇 |
2009年 | 43篇 |
2008年 | 40篇 |
2007年 | 49篇 |
2006年 | 56篇 |
2005年 | 42篇 |
2004年 | 44篇 |
2003年 | 40篇 |
2002年 | 25篇 |
2001年 | 24篇 |
2000年 | 19篇 |
1999年 | 17篇 |
1998年 | 9篇 |
1997年 | 16篇 |
1996年 | 13篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 9篇 |
1991年 | 8篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有794条查询结果,搜索用时 31 毫秒
21.
A pure calcium borate Ca2[B2O4(OH)2]·0.5H2O has been synthesized under hydrothermal condition and characterized by XRD, FT-IR and TG as well as by chemical analysis. The molar enthalpy of solution of Ca2[B2O4(OH)2]·0.5H2O in HC1·54.582H2O was determined. From a combination of this result with measured enthalpies of solution of H3BO3 in HC1·54.561H2O and of CaO in (HCl + H3BO3) solution, together with the standard molar enthalpies of formation of CaO(s), H3BO3(s) and H2O(l), the standard molar enthalpy of formation of −(3172.5 ± 2.5) kJ mol−1 of Ca2[B2O4(OH)2]·0.5H2O was obtained. 相似文献
22.
在(298.15 ±0.01) K下用转动弹热量计测定了离子液体硫酸乙酯-1-甲基-3-乙基咪唑(EMIES)及合成它的原料1-甲基咪唑的恒容燃烧热,通过计算得到它们的标准燃烧焓 分别为(-2671±2) 和(-286.3±0.5) kJ·mol-1;标准生成焓 分别为(-3060±3) kJ·mol-1和(-2145±4) kJ·mol-1.结合文献上硫酸二乙酯的标准生成焓数据,得到了合成离子液体EMIES的反应热(-102.3±1.0) kJ·mol-1,与合成实验中观察到的强烈放热现象是一致的.根据离子液体EMIES的热容数据,计算了不同温度下EMIES的标准生成焓. 相似文献
23.
M. Slavík J. Šedlbauer K. Ballerat-Busserolles V. Majer 《Journal of solution chemistry》2007,36(1):107-134
The heat capacities of aqueous solutions of acetone, 2,5-hexanedione, diethyl ether, 1,2-dimethoxyethane, benzyl alcohol and
cyclohexanol at concentrations of 0.1 to 1.0 mol⋅kg−1 were determined at temperatures of 298.15, 423.15, 473.15 and 523.15 K and pressures up to 28 MPa. The measurements were
performed at ambient conditions using the commercial Picker differential flow calorimeter and at high temperatures and pressures
with a customized Picker type calorimeter constructed at the Blaise Pascal University, Clermont-Ferrand. Standard molar heat
capacities were obtained by weighted extrapolation to the infinite dilution limit. The contributions of –CO–, –O– and –OH
groups to the standard molar volume and standard molar heat capacity were determined from the newly determined and literature
data. The variation of the three oxygen-containing group contributions with temperature and molecular structure is examined
qualitatively. 相似文献
24.
Two new marine sediment standard reference materials (SRMs) for the determination of organic contaminants 总被引:3,自引:0,他引:3
Wise SA Poster DL Schantz MM Kucklick JR Sander LC Lopez de Alda M Schubert P Parris RM Porter BJ 《Analytical and bioanalytical chemistry》2004,378(5):1251-1264
Two new marine sediment standard reference materials (SRMs), SRM 1941b Organics in Marine Sediment and SRM 1944 New York/New Jersey Waterway Sediment, have been recently issued by the National Institute of Standards and Technology (NIST) for the determination of organic contaminants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCB) congeners, and chlorinated pesticides. Both sediment SRMs were analyzed using multiple analytical methods including gas chromatography/mass spectrometry (GC/MS) on columns with different selectivity, reversed-phase liquid chromatography with fluorescence detection (for PAHs only), and GC with electron capture detection (for PCBs and pesticides only). SRM 1941b has certified concentrations for 24 PAHs, 29 PCB congeners, and 7 pesticides, and SRM 1944 has certified concentrations for 24 PAHs, 29 PCB congeners, and 4 pesticides. Reference concentrations are also provided for an additional 58 (SRM 1941b) and 39 (SRM 1944) PAHs, PCB congeners, and pesticides. SRM 1944, which was collected from multiple sites within New York/New Jersey coastal waterways, has contaminant concentrations that are generally a factor of 10–20 greater than SRM 1941b, which was collected in the Baltimore (Maryland) harbor. These two SRMs represent the most extensively characterized marine sediment certified reference materials available for the determination of organic contaminants.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material. 相似文献
25.
The apparent molar volumes, V
φ
, of glycine, L-alanine and L-serine were obtained in aqueous 0 to ∼4 mol⋅kg−1 N,N-dimethylacetamide (DMA) solutions from density measurements at 298.15 and 308.15 K. The standard partial molar volume,
V
φ
o, and standard partial molar volumes of transfer, Δtr
V
φ
o, were determined for these amino acids. It has been shown that hydrophilic-hydrophilic interactions between charged groups
of the amino acids and the —CON= group of DMA are predominant in the case of glycine and L-serine, but for L-alanine the interactions
between its side group (—CH3) and DMA are predominant. An increase in temperature increases the standard partial molar volumes but decreases the transfer
volumes of the amino acids. The results have been interpreted in terms of cosphere overlap model. 相似文献
26.
Two new standard reference materials (SRM) for drugs of abuse in human hair have been developed. SRM 2379 consists of hair spiked with cocaine, benzoylecgonine, cocaethylene, phencyclidine, amphetamine, and methamphetamine. SRM 2380 consists of hair spiked with codeine, morphine, monoacetylmorphine, and tetrahydrocannabinol (THC). The SRMs were prepared by soaking the hair in a solution of the target analytes in water-dimethylsulfoxide. The concentration of each analyte was determined using two methods, one based upon gas chromatography/mass spectrometry (GC/MS) and one based upon liquid chromatography/mass spectrometry (LC/MS). Both methods used 0.1 M HCl for extraction of all the analytes from the hair, except for THC, which was extracted with 1 M NaOH. For isolation of the analytes from the extracts, the GC/MS-based methods used different clean-up procedures from those used for the LC/MS-based methods. The results from the two methods were in good agreement with mean differences for the analytes ranging from 4% to 16%. These materials will enable laboratories performing analyses of hair for drugs of abuse to test the accuracy of their methods. 相似文献
27.
T.D. Klots P. Devlin W.B. Collier 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1997,53(14):2445-2456
Infrared and Raman measurements for benzimidazole are presented and discussed, including its argon-matrix infrared spectrum. To assist in the assignment, benzimidazole's harmonic force fields for the 321G* and 631G* levels were scaled by scaled factors derived by fitting the respective computed force fields of other indene derivatives to previously reported experimental vibrational frequencies. Comparison to the best set of experimental wavenumbers, usually taken from the matrix, shows mean 321G* and 631G* deviations of 7.0 and 5.8 cm−1 for the planar modes, and 14.0 and 6.8 cm−1 for the nonplanar modes, respectively, with much of the error residing in imino-hydrogen group modes. Standard entropies are derived with the matrix wavenumbers and the methods of statistical mechanics. An attempt to determine standard entropies by calorimetric methods was unsuccessful. The triple-point temperature Ttp and enthalpy of fusion Δ1crHm only are reported. 相似文献
28.
A coordination polymer [Cu(nip)(phen)]n was hydrothermally synthesized by the reaction of Cu(NO3)2 with 5-nitroisophthalic acid and phen. Single-crystal structure analysis showed that the complex crystallized in the monoclinic space group P21/c; a = 10.6566(13); b = 12.5931(15); c = 13.0514(16) Å; β = 95.474(2)°, V = 1743.5(4) Å3; Z = 4. The standard molar enthalpy of formation of the complex was determined to be −554 ± 11 kJ mol−1. 相似文献
29.
Jeffrey S. Boyer 《The Journal of chemical thermodynamics》2003,35(12):1917-1928
The standard molar heat capacity C°p,m of adenine(cr) has been measured using adiabatic calorimetry over the range 6<(T/K)<310 and the results used to derive thermodynamic functions for adenine(cr) at smoothed temperatures. At T=298.15 K, C°p,m=(142.67±0.29) J · K−1 · mol−1 and the third law entropy S°m=(145.62±0.29) J · K−1 · mol−1. The standard molar Gibbs free energy of formation ΔfG°m at T=298.15 K for crystalline adenine was calculated, using the standard molar enthalpy of formation for the compound and entropies of the elements from the literature, and found to be ΔfG°m=(301.4±1.0) kJ · mol−1. The results were combined with solution calorimetry and solubility measurements from the literature to yield revised values for the standard molar thermodynamic properties of aqueous adenine at T=298.15 K: ΔfG°m=(313.4±1.0) kJ · mol−1, ΔfH°m=(129.5±1.4) kJ · mol−1, and Sm°=(217.68±0.44) J · K−1 · mol−1. 相似文献
30.