全文获取类型
收费全文 | 3084篇 |
免费 | 394篇 |
国内免费 | 415篇 |
专业分类
化学 | 1331篇 |
晶体学 | 11篇 |
力学 | 181篇 |
综合类 | 73篇 |
数学 | 1052篇 |
物理学 | 1245篇 |
出版年
2024年 | 18篇 |
2023年 | 45篇 |
2022年 | 99篇 |
2021年 | 85篇 |
2020年 | 75篇 |
2019年 | 82篇 |
2018年 | 94篇 |
2017年 | 129篇 |
2016年 | 152篇 |
2015年 | 113篇 |
2014年 | 170篇 |
2013年 | 237篇 |
2012年 | 197篇 |
2011年 | 222篇 |
2010年 | 169篇 |
2009年 | 190篇 |
2008年 | 175篇 |
2007年 | 199篇 |
2006年 | 171篇 |
2005年 | 126篇 |
2004年 | 147篇 |
2003年 | 113篇 |
2002年 | 112篇 |
2001年 | 107篇 |
2000年 | 92篇 |
1999年 | 84篇 |
1998年 | 79篇 |
1997年 | 67篇 |
1996年 | 65篇 |
1995年 | 46篇 |
1994年 | 38篇 |
1993年 | 21篇 |
1992年 | 17篇 |
1991年 | 18篇 |
1990年 | 16篇 |
1989年 | 17篇 |
1988年 | 9篇 |
1987年 | 7篇 |
1986年 | 8篇 |
1985年 | 7篇 |
1984年 | 13篇 |
1983年 | 5篇 |
1982年 | 9篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 17篇 |
1978年 | 9篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1973年 | 2篇 |
排序方式: 共有3893条查询结果,搜索用时 31 毫秒
101.
Tumbiolo S Gal JF Maria PC Zerbinati O 《Analytical and bioanalytical chemistry》2004,380(5-6):824-830
The aim of the study was to analyse BTEX compounds (benzene, toluene, ethylbenzene, xylenes) in air by solid phase micro-extraction/gas chromatography/mass spectrometry (SPME/GC/MS), and this article presents the features of the calibration method proposed. Examples of real-world air analysis are given. Standard gaseous mixtures of BTEX in air were generated by dynamic dilution. SPME sampling was carried out under non-equilibrium conditions using a Carboxen/PDMS fibre exposed for 30 min to standard gas mixtures or to ambient air. The behaviour of the analytical response was studied from 0 to 65 g/m3 by adding increasing amounts of BTEX to the air matrix. Detection limits range from 0.05 to 0.1 g/m3 for benzene, depending on the fibre. Inter-fibre relative standard deviations (reproducibility) are larger than 18%, although the repeatability for an individual fibre is better than 10%. Therefore, each fibre should be considered to be a particular sampling device, and characterised individually depending on the required accuracy. Sampling indoor and outdoor air by SPME appears to be a suitable short-delay diagnostic method for volatile organic compounds, taking advantage of short sampling time and simplicity. 相似文献
102.
建立了加速溶剂萃取同步净化-同位素内标-气相色谱-高分辨质谱同时测定水产品中32种多氯联苯含量的方法。通过在加速溶剂萃取仪中加入2 g无水硫酸钠、1 g弗罗里硅土、50 g中性氧化铝作为吸附剂实现同步净化的效果,萃取溶剂为二氯甲烷-正己烷(1:1,v/v),萃取温度为100℃,循环2次。萃取结束后分别用0.5 mL浓硫酸净化两次,净化液浓缩定容后,采用气相色谱-高分辨质谱测定,同位素内标法定量。32种多氯联苯在0.1~20 μg/L范围内平均相对响应因子(RRF)的相对标准偏差(RSD)值(n=7)均小于15%,定量限(S/N=10)为0.3~1.9 ng/kg。在草鱼和海鲈鱼空白基质中做加标回收试验,添加水平为5、20和50 ng/kg,得到的平均回收率为71.9%~119.0%(n=6),RSD为3.5%~19.6%。该方法背景干扰低,灵敏度高,重现性好,回收率稳定,适用于水产品中多氯联苯的检测。 相似文献
103.
Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate Monohydrate 总被引:1,自引:0,他引:1
Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is (28.795 ± 0.182) kJ/mol (298.15 K), and the standard molar enthalpy of formation of the title complex is (-2185.43 ± 13.80) kJ/mol (298.15 K). Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction: an nth-order reaction (Fn) with n=4.28, E1=147.35 kJ/mol, A1=3.63×10^13 s^-1 is followed by a second-order reaction (F2) with E2=212.71 kJ/mol, A2= 1.82 × 10^18 s^-1. 相似文献
104.
Y. M. Dan Y. R. Zhao Y. Liu S. S. Qu 《Journal of Thermal Analysis and Calorimetry》2006,84(3):531-534
The two complexes, [Ln(Ala)2(Im)(H2O)](ClO4)3 (Ln=Pr,
Gd), were synthesized and characterized. Using a solution-reaction isoperibol
calorimeter, standard enthalpies of reaction of two reactions: LnCl3⋅6H2O(s)+2Ala(s)+Im(s)+3NaClO4(s)=[Ln(Ala)2(Im)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(l) (Ln=Pr, Gd),
at T=298.15 K, were determined to be (39.26±0.10)
and (5.33±0.12) kJ mol–1 , respectively.
Standard enthalpies of formation of the two complexes at T=298.15
K, ΔfHΘm
{[Ln(Ala)2(Im)(H2O)](ClO4)3(s)} (Ln=Pr, Gd),
were calculated as –(2424.2±3.3) and –(2443.4±3.3)
kJ mol–1 , respectively. 相似文献
105.
106.
Thermochemistry of the solid complex Gd(Et<Subscript>2</Subscript>dtc)<Subscript>3</Subscript>(phen)
Summary A ternary solid complex Gd(Et2dtc)3(phen) has been obtained from reactions of sodium diethyldithiocarbamate (NaEt2dtc), 1,10-phenanthroline (phen) and hydrated gadolinium chloride in absolute ethanol. The title complex was described by chemical and elemental analyses, TG-DTG and IR spectrum. The enthalpy change of liquid-phase reaction of formation of the complex, ΔrHΘm(l), was determined as (-11.628±0.0204) kJ mol-1 at 298.15 K by a RD-496 III heat conduction microcalorimeter. The enthalpy change of the solid-phase reaction of formation of the complex, ΔrHΘm(s), was calculated as (145.306±0.519) kJ mol-1 on the basis of a designed thermochemical cycle. The thermodynamics of reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A), the reaction order (n), the activation enthalpy (ΔrHΘ≠), the activation entropy (ΔrSΘ≠), the activation free energy (ΔrGΘ≠) and the enthalpy (ΔrHΘ≠), were obtained by combination of the thermodynamic and kinetic equations for the reaction with the data of thermokinetic experiments. The constant-volume combustion energy of the complex, ΔcU, was determined as (-18673.71±8.15) kJ mol-1 by a RBC-II rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, ΔcHΘm, and standard enthalpy of formation, ΔfHΘm, were calculated to be (-18692.92±8.15) kJ mol-1 and (-51.28±9.17) kJ mol-1, respectively. 相似文献
107.
P. De Bièvre 《Accreditation and quality assurance》2000,5(6):224-230
Traceability is a property of the result of a measurement. Since values carried by (reference) materials must also have been
obtained, of necessity, by measurement, the definition of traceability also applies to reference materials. It is extremely
helpful to give the traceability (of the origin) of a reference material a separate name, i.e. 'trackability'. An analysis
of the function of values carried by reference materials, shows that they can fulfill different functions, depending on the
intended use. One of the functions located outside the traceability chain – and hence not very relevant for establishing traceability
– is evaluating the approximate size of the uncertainty of the measurement of an unknown sample by performing a similar measurement
on a reference material, used as a 'simulated sample'. Another function is located inside the traceability chain, where the
reference material is used as an added 'internal standard'. Then, the value carried by the reference material is essential
for establishing the traceability of the measured value of an unknown sample. In the latter application, the reference material
acts as an 'amount standard' (the certified value for amount is used).
Received: 11 November 1999 / Accepted: 24 February 2000 相似文献
108.
诱导效应指数与含硫含氮的低碳直链有机化合物的标准汽化热 总被引:2,自引:0,他引:2
本文利用诱导效应指数建立了含硫含氮的低碳直链有机物的标准汽化热的简单估算方法,我们利用此法计算了一些含硫含氮的直链有机物的标准汽化热,41个可比较值的相对误差均在5%以内。 相似文献
109.
介绍可燃气体报警器的检测现状,分析可燃气体报警器检测元件中毒的原因,强调了检测可燃气体报警器时使用标准气体的重要性,以及标准气体的正确使用。 相似文献
110.