伟大的门捷列夫的预见

今年2月8日是俄罗斯天才的化学家门捷列夫(1834—1907)诞生125周年纪念。特选此译文刊出以为纪念。     

氨的制造的教学法

苏联共产党第十九次代表大会的决议指示出化学教师应该提高关于综合技术教育的教学质量,更密切地联系学习与生活,使学生认识重要化学生产的科学原理。氨的制造是属于重要化学生产之列的。研究氨的制造是具有重要的教育教养意义。这课题的材料,可以提供作复习和更深入地去认识以前所熟悉的物质的性质和扩大瞭解关于反应进行的条件,以及在工业上的管理方法.在八年级末学期已经学过硫酸的制造,从而熟悉了一些化学工业制造原理,如阶段的划分和流水作业的装置,扩大反应物质的表面,逆流原理,温度和压力的影响,热的交换等等,在研究氨的制造中巩固了这些原理,并且增加了关于适当的压力和循环作业的利用等概念。     

一氧化氮的合成的演示及其方法的讨论

一、反应原理在放电条件下,N2和O2能直接化合生成无色的一氧化氮。放电N2+O2（?）2NO一氧化氮在常温下很容易和O2化合,生成棕色并有刺激性气味的NO2。二、仪器及药品打气球、贮气瓶2个（一个标出刻度）、两口玻璃球（容积140ml）、铁架台、铁丝电。     

有机试剂的结构与性质的关系的研究

前言有机试剂是用于化学元素和化合物的测定、分离与浓集、掩蔽的有机化合物。这类化合物数量很多,在分析化学中得到极其广泛的应用。有机试剂结构及其与反应性能之间关系的研究是有机试剂理论研究的基本问题。早在本世纪二十年代Feigl就提出了分析功能团的概念。这个概念广泛地应用于有机试剂的研究中,并不断得到丰富和发展。这一概念的出现,为人们研究有机试剂结构与反应性能的关系奠定了基础。随着现代科学技术的不断发展,X射线衍射、红外光谱、拉曼光谱等现代技术也相继用于有机试剂的研究,使人们对有机试剂的认识进一步加深。此外近代迅速发展起来的络合物结构理论、量子化学方法以及计算技术也被用于有机试剂的研究中,从而使得从理论上     

对公认的Clapeyron方程的推导的不同意见

对公认的Ｃｌａｐｅｙｒｏｎ方程的推导的不同意见郭余年，赵凤云（吉林工学院轻化工程系长春１３００１２）Ｃｌａｐｅｙｒｏｎ方程问世干热力学第二定律成立之前。第二定律建立以后，赋予了它以新的内容，使其成为描述单元系任意温度（压力）、任意两相平衡的普遍公式。...     

基于Matlab的二元共聚合反应的竞聚率的求解

以直线交叉法为依据,根据最小二乘原理,采用Matlab GUI工具设计了一款用于计算二元共聚合反应竞聚率的图形用户程序。与传统的求解竞聚率方法相比,该图形用户程序具有设计原理简单、计算快捷的特点;同时程序提供界面简洁、交互友好的数据输入平台,实用性强。实际应用表明:采用该款图形用户程序所测得的数据与微机动态搜索法、Tidwell-Mortimer法相近,而比采用斜率截距法计算竞聚率的最小差方和更小,并且也避免了采用斜率截距法由于所用方程的非对称性造成的计算结果的不一致性。     

紫精的负离子对耐水的紫精—聚合物膜的光致变色性能的影响

将含不同负离子的苄基紫精分散在混合有ＰＶＰ的ＭＭＡ－ＨＥＭＡ共聚物基质中可制成耐水的光致变色膜。它们的光致变色速度的大小随紫精负离子的不同而有如下序列：Ｖ６（ＰＦ６＾－）〉Ｖ５（ＢＦ４＾－）￣Ｖ４（ＣｌＯ４＾－）〉Ｖ３（ＣＨ３－苯环－ＳＯ３＾－）〉Ｖ２（Ｂｒ＾－）￣Ｖ１（Ｃｌ＾－）。这与这些紫精在ＤＭＦ中的溶解度以及在共聚物基质中的溶解性大小的序列相一致。负离子对这些光致变色膜在空气中的氧化退色速     

具有好的溶解性和高的热稳定性的富勒烯-苝化合物的合成

在氩气保护下,利用N-(正丁基)-N’(4-甲酰基苯氧戊基)-1．6,7,12-四-(4-叔丁基苯氧基)-3,4,9,10-苝酰亚胺和N-甲基甘氨酸产生的亚胺叶立德与富勒烯反应,合成了含富勒烯的苝化合物,用NMR、FT—IR、UV-Vis及TGA等方法对其结构和性能进行了表征和测试。研究结果表明此类化合物具有好的溶解性和高的热稳定性。     

金的快速测定方法的改进

自从本刊1975年第二期“金的快速测定”一文发表以后,读者来信提出了宝贵的意见,认为此法测定金时铊有干扰,且试样分解方法可能使金的结果偏低。过去,我们分析的样品中不含有铊,故对铊的干扰未作考虑。现经试验,在溴氢酸存在下,三价金在低温蒸干时,随时间、温度、溴氢酸用量的不同,均有部份金被还原造成结果偏低。铊的存在对金的测定有干扰。因此对金的快速测定作如下的补充。     

砷的光度分析法的进展

文中着重介绍了近年来砷的光度测定方法的新进展，包括砷斑法、Ag（DDC）光度法、分单质银分散体系光度法、砷钼蓝光度法等。引用文献85篇。     

纳秒强激光场中苯电离产生高价离子的研究

用25 ns脉冲Nd-YAG 532 nm的激光，在1010～1011 W•cm－2的光场强度下，利用飞行时间质谱对He、 N2、Ar载气条件下苯的激光电离过程进行了研究.发现当利用氩作为载气时，除观察到C2＋、C2H2+、C3H3+、C6H6+离子外，还观察到很强的Cq＋(q=1～3)高价离子.这些离子都有很高的平动能， C2＋的最可几平动能为12.9 eV， C3＋为37.5 eV.通过改变载气种类和压力及在不同光场强度条件下的实验，可以认为这些高价离子来源于含苯团簇的库仑爆炸过程.     

Multiphoton ionization of metal cluster complexes Os3(CO)12 and Ir4(CO)12: Determination of the ionization energy and coordination energy of the complex ions

Multiphoton ionization and the subsequent dissociation process of metal cluster complexes Os₃(CO)₁₂ and Ir₄(CO)₁₂, prepared in a supersonic jet, were studied by means of multiphoton ionization with time-of-flight (TOF) mass detection. The ionization energies of Os₃(CO)₁₂ and Ir₄(CO)₁₂ were determined to be 7.95 and 8.3 eV, respectively, from the laser wavelength at the ionization threshold. The coordination energies of Os₃(CO)₁₂⁺ and Ir₄(CO)₁₂⁺ ions were also determined to be 1.6 and 1.2 eV, respectively, from the excitation energy needed to cause the appearance of fragment ions. The observed values agreed reasonably well with the ones calculated by using the density functional theory method.     

Single photon ionization of van der Waals clusters with a soft x-ray laser: (SO2)n and (SO2)n(H2O)m

van der Waals cluster (SO2)n is investigated by using single photon ionization of a 26.5 eV soft x-ray laser. During the ionization process, neutral clusters suffer a small fragmentation because almost all energy is taken away by the photoelectron and a small part of the photon energy is deposited into the (SO2)n cluster. The distribution of (SO2)n clusters decreases roughly exponentially with increasing cluster size. The photoionization dissociation fraction of I[(SO2)(n-1)SO+] / I[(SO2)n+] decreases with increasing cluster size due to the formation of cluster. The metastable dissociation rate constants of (SO2)n+ are measured in the range of (0.6-1.5) x 10(4) s(-1) for cluster sizes 5< or =n< or =16. Mixed SO2-H2O clusters are studied at different experimental conditions. At the condition of high SO2 concentration (20% SO2 partial pressure), (SO2)n+ cluster ions dominate the mass spectrum, and the unprotonated mixed cluster ions (SO2)nH2O+ (1< or =n< or =5) are observed. At the condition of low SO2 concentration (5% SO2 partial pressure) (H2O)nH+ cluster ions are the dominant signals, and protonated cluster ions (SO2)(H2O)nH+ are observed. The mixed clusters, containing only one SO2 or H2O molecule, SO2(H2O)nH+ and (SO2)nH2O+ are observed, respectively.     

Evidence of CH2O (a3A2) and C2H4 (a3B1u) produced from photodissociation of 1,3-trimethylene oxide at 193 nm

We investigated the dissociative ionization of formaldehyde (CH(2)O) and ethene (C(2)H(4)) produced from photolysis of 1,3-trimethylene oxide at 193 nm using a molecular-beam apparatus and vacuum-ultraviolet radiation from an undulator for direct ionization. The CH(2)O (C(2)H(4)) product suffers from severe dissociative ionization to HCO(+) (C(2)H(3) (+) and C(2)H(2) (+)) even though photoionization energy is as small as 9.8 eV. Branching ratios of fragmentation of CH(2)O and C(2)H(4) following ionization are revealed as a function of kinetic energy of products using ionizing photons from 9.8 to 14.8 eV. Except several exceptions, branching ratios of daughter ions increase with increasing photon energy but decrease with increasing kinetic energy. The title reaction produces CH(2)O and C(2)H(4) mostly on electronic ground states but a few likely on triplet states; C(2)H(4) (a(3)B(1u)) seems to have a yield greater than CH(2)O (a(3)A(2)). The distinct features observed at small kinetic energies of daughter ions are attributed to dissociative ionization of photoproducts CH(2)O (a(3)A(2)) and C(2)H(4) (a(3)B(1u)). The observation of triplet products indicates that intersystem crossing occurs prior to fragmentation of 1,3-trimethylene oxide.     

Experimental and quantum-chemical studies on photoionization and dissociative photoionization of CH2Br2

The dissociative photoionization of CH2Br2 in a region approximately 10-24 eV was investigated with photoionization mass spectroscopy using a synchrotron radiation source. An adiabatic ionization energy of 10.25 eV determined for CH2Br2 agrees satisfactorily with predictions of 10.26 and 10.25 eV with G2 and G3 methods, respectively. Observed major fragment ions CH2Br+, CHBr+, and CBr+ show appearance energies at 11.22, 12.59, and 15.42 eV, respectively; minor fragment ions CHBr2+, Br+, and CH2+ appear at 12.64, 15.31, and 16.80 eV, respectively. Energies for formation of observed fragment ions and their neutral counterparts upon ionization of CH2Br2 are computed with G2 and G3 methods. Dissociative photoionization channels associated with six observed fragment ions are proposed based on comparison of determined appearance energies and predicted energies. An upper limit of DeltaH0f,298(CHBr+) < or = 300.7 +/- 1.5 kcal mol(-1) is derived experimentally; the adiabatic ionization energy of CHBr is thus derived to be < or = 9.17 +/- 0.23 eV. Literature values for DeltaH0f,298(CBr+) = 362.5 kcal mol(-1) and ionization energy of 10.43 eV for CBr are revised to be less than 332 kcal mol(-1) and 9.11 eV, respectively. Also based on a new experimental ionization energy, DeltaH0f,298(CH2Br2+) is revised to be 236.4 +/- 1.5 kcal mol(-1).     

Ionization energies of multiply protonated polypeptides obtained by tandem ionization in Fourier transform mass spectrometers

Ionization energies (IE) of [M + zH](z+) (z+) electrospray-produced polypeptides were determined by electron ionization in a Penning cell of 4.7 and 9.4 T Fourier transform mass spectrometers. For z = 1+ and substance P, the found IE value of 11.0 +/- 0.4 eV is in agreement with that obtained earlier for ions generated with matrix-assisted laser desorption/ionization. For higher z, the following values were found: 11.7 +/- 0.3 eV for 2+ of [Arg-8]-vasopressin, 11.1 +/- 0.6 eV for 2+ of substance P, 12.2 +/- 0.7 eV for 2+ of renin substrate, 13.3 +/- 0.4 eV for 3+ of B-chain of insulin and 14.6 +/- 0.6 eV for 4+ and 15.1 +/- 0.4 eV for 5+ of melittin. It was found that 90% of existing IE data on polypeptides in the 1.0-3.5 kDa mass range are described with 相似文献   

Cross sections and ion kinetic energy analysis for the electron impact ionization of acetylene

Using a Nier-type electron impact ion source in combination with a double focusing two sector field mass spectrometer, partial cross sections for electron impact ionization of acetylene are measured for electron energies up to 1000 eV. Discrimination factors for ions are determined using the deflection field method in combination with a three-dimensional ion trajectory simulation of ions produced in the ion source. Analysis of the ion yield curves obtained by scanning the deflectors allows the assignment of ions with the same mass-to-charge ratio to specific production channels on the basis of their different kinetic energy distributions. This analysis also allows to determine, besides kinetic energy distributions of fragment ions, partial cross sections differential in kinetic energy. Moreover a charge separation reaction, the Coulomb explosion of the doubly charged parent ions C2H2++ into the fragment ions C2H+ and H+, is investigated and its mean kinetic energy release (KER=3.88 eV) is deduced.     

激光解吸电离飞行时间质谱下的银簇行为

近年来,对金属簇的研究已成为化学与物理学中最活跃的研究领域之一［１］．金属簇被认为是介于单个原子与固体之间的中间相［２］．深入地研究其结构、形成机理及物理与化学行为,对于寻找新的催化剂［３］,重新认识气相化学与凝聚相化学的关系［４］,都有非常重要的意...     

Design and calibration of an electrostatic energy analyzer-time-of-flight mass spectrometer for measurement of laser-desorbed ion kinetic energies

The design of a hybrid electrostatic energy analyzer-time-of-flight mass spectrometer for measurement of ion kinetic energies produced by laser desorption ionization is presented. The need for experimental evaluation of the calibration and performance of the instrument is discussed and a novel laser multiphoton ionization technique, which allows experimental calibration of the energy bandpass of the electrostatic energy analyzer, is described. Laser multiphoton ionization at varying electric field strengths also allows the effects of electric field distortions on energy resolution of the instrument to be probed. Measurement of the translational energies of ions produced by 266-nm laser desorption ionization at 48 mJ/cm² of material adsorbed to a stainless steel probe by using this instrument also is presented. Ion translational energies of +19±5, +10±5, and +10±5 eV are found for adsorbed Na⁺, K⁺, and m-xylene M⁺, respectively.     

Double ionization and Coulomb explosion of the formic acid dimer by intense near-infrared femtosecond laser pulses

Ionization and fragmentation of formic acid dimers (HCOOH)(2) and (DCOOD)(2) by irradiation of femtosecond laser pulses (100 fs, 800 nm, ~1 × 10(14) W/cm(2)) were investigated by time-of-flight (TOF) mass spectrometry. In the TOF spectra, we observed fragment ions (HCOOH)H(+), (HCOOH)HCOO(+), and H(3)O(+), which were produced via the dissociative ionization of (HCOOH)(2). In addition, we found that the TOF signals of COO(+), HCOO(+), and HCOOH(+) have small but clear side peaks, indicating fragmentation with large kinetic energy release caused by Coulomb explosion. On the basis of the momentum matching among pairs of the side peaks, a Coulomb explosion pathway of the dimer dication, (HCOOH)(2)(2+) → HCOOH(+) + HCOOH(+), was identified with the total kinetic energy release of 3.6 eV. Quantum chemical calculations for energies of (HCOOH)(2)(2+) were also performed, and the kinetic energy release of the metastable dication was estimated to be 3.40 eV, showing good agreement with the observation. COO(+) and HCOO(+) signals with kinetic energies of 1.4 eV were tentatively assigned to be fragment ions through Coulomb explosion occurring after the elimination of a hydrogen atom or molecule from (HCOOH)(2)(2+). The present observation demonstrated that the formic acid dimer could be doubly ionized prior to hydrogen bond breaking by intense femtosecond laser fields.