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。     

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。     

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。     

二烷基锡聚合物的研究——Ⅲ.顺丁烯二酸二丁基锡酯与丙烯酸甲酯、丙烯酸丁酯的共聚合

近年来,新的有机锡聚合物的合成及其在许多领域内的应用研究取得很大的进展,然而,侧链上带有有机锡基团的二烷(芳)基锡聚合物的研究报道较少。众所周知,二烷基锡化合物是一类重要的聚氯乙烯热稳定剂。制备对聚氯乙烯具有改性作用的有机锡共聚合型热稳定剂,以实现聚氯乙烯热稳定剂的高分子化和多功能化,是未来热稳定剂的发展方向之一。我们已研究了顺丁烯二酸二丁基锡酯分别与苯乙烯、甲基丙烯酸甲酯的共聚反应及其共聚物对聚氯乙烯热稳定性的影响。本文报道顺丁烯二酸二丁基锡酯分别与丙烯酸甲酯、丙烯酸丁酯的共聚反应。     

EFFECT OF TEMPERATURE ON COPOLYMERIZATION PARAMETERS OF HYDROXYETHYL ACRYLATE AND METHYL METHACRYLATE

The copolymerization of 2-hydroxyethyl acrylate (HEA, M_1) and methylmethacrylate (MMA, M_2) in cyclohexanone was studied. The multiple experiments ofsolution copolymerization with low conversion were carried out at two sensitive compositionfeed points at 60, 80, 100, 120 and 140℃, respectively. The composition of the copolymerswas analyzed by ~1H-NMR. The reactivity ratios which were estimated by the Error-in-Variable Method (EVM) of Mayo-Lewis equation were found to be r_1 = 0.328, r_2 = 1.781for 60℃; 0.375, 1.709 for 80℃; 0.406, 1.654 for 100℃; 0.439, 1.540 for 120℃ and 0.455,1.400 for 140℃, and the 95% joint confidence intervals of the reactivity ratios were alsodetermined. According to r_1 and r_2, Arrhenius relations and the activity energy differencebetween the homo- and cross-propagation were calculated.     

Copolymerization of glycidyl methacrylate with alkyl acrylate monomers

A newer approach to obtaining acrylic thermoset polymers with adequate hydrophilicity required for various specific end uses is reported. Glycidyl methacrylate (GMA) was copolymerized with n-butyl acrylate (n-BA), isobutyl acrylate (i-BA), and 2-ethylhexyl acrylate (2-EHA) in bulk at 60°C. with benzoyl peroxide as free radical initiator. The copolymer composition was determined from the estimation of epoxy group. Reactivity ratios were calculated by the Yezrielev, Brokhina, and Roskin method. For copolymerization of GMA (M₁) with n-BA (M₂) the reactivity ratios were r₁ = 2.15 ± 0.14, r₂ = 0.12 ± 0.03; with i-BA (M₂) they were r₁ = 1.27 ± 0.06, r₂ = 0.33 ± 0.031; and with 2-EHA (M₂) they were r₁ = 2.32 ± 0.14, r₂ = 0.13 ± 0.009. The reactivity ratios were the measure of distribution of monomer units in a copolymer chain; the values obtained are compared and discussed.     

THE MECHANISM OF THE COPOLYMERIZATION OF BF_3-COMPLEXED ETHYL ACRYLATE WITH PROPYLENE

The copolymerization of BF_2-omplexed ethyl acrylate with propylene in the presence ofAIBN at 25℃was investigated. It was found that the rate of the copolymerization was propor-tional to the square root of the initiator concentration. The chain transfer agent CCl_4 greatly af-fects the inherent viscosity of the resulting copolymer. The smaller the dielectric constant of thesolvent, the greater the rate of copolymerization is. The equal concentration of the two monomersgive the maximum copolymerization rate. The ~1H-NMR and ~(13)C-NMR analysis indicated, when[EA.BF_2]/[EA.BF_2]+[P]>0.5, the resulting copolymer was the acrylate-rich random copoly-mer. Through the kinetic experiments we suggest that copolymerization follows the mechanismof the random copolymerization of the ternary complex with binary complex. When [EA.BF_3]/[EA.BF_2]+[P]<0.5, the resulting copolymer is always strictly alternating, and the alternatingcopolymerization follows the mechanism of the ternary complex homopolymerization. Usingthe homolog of the propylene, 1-pentene, we found that BF_3-complexed ethyl acrylate can forma ternary complex with 1-pentene identified by UV spectroscopy. This is a strong evidence forthe mechanism of ternary complex homopolymerizetion.     

Anionic synthesis of in-chain 3° amine-functionalized polybutadienes

Anionic copolymerizations of butadiene (M₁) with excess 1-(4-dimethylaminophenyl)-1-phenylethylene (M₂) were conducted in benzene at room temperature for 24–48h using sec-butyllithium as initiator. Anisole, triethylamine and t-butyl methyl ether were added in ratios of [B]/[RLi] = 60, 20, 30, respectively, to promote copolymerization. Narrow molecular weight distribution copolymers with M̄n = 14 × 10³ to 32 × 10³ g/mol (M̄_w/M̄n =1.02–1.03) and 8,12 and 30 amine groups per chain for anisole, triethylamine and t-butyl methyl ether, respectively, were obtained. The butadiene monomer reactivity ratios (r1) were 42, 33 and 14 for anisole, triethylamine and t-butyl methyl ether, respectively.     

Copolymerization of 4-cyclopentene-1,3-dione with p-chlorostyrene and vinylidene chloride

The copolymerization of 4-cyclopentene-1,3-dione (M₂) with p-chlorostyrene and vinylidene chloride is reported. The copolymers were prepared in sealed tubes under nitrogen with azobisisobutyronitrile initiator. Infrared absorption bands at 1580 cm.^?1 revealed the presence of a highly enolic β-diketone and indicated that copolymerization had occurred. The copolymer compositions were determined from the chlorine analyses and the reactivity ratios were evaluated. The copolymerization with p-chlorostyrene (M₁) was highly alternating and provided the reactivity ratios r₁ = 0.32 ± 0.06, r₂ = 0.02 ± 0.01. Copolymerization with vinylidene chloride (M₁) afforded the reactivity ratios r₁ = 2.4 ± 0.6, r₂ = 0.15 ± 0.05. The Q and e values for the dione (Q = 0.13, e = 1.37), as evaluated from the results of the vinylidene chloride case, agree closely with the previously reported results of copolymerization with methyl methacrylate and acrylonitrile and confirm the general low reactivity of 4-cyclopentene-1,3-dione in nonalternating systems.     

Radical polymerization of butadiene-1-carboxylic acid

The homopolymerization and copolymerization of butadiene-1-carboxylic acid (Bu-1-Acid) (M₁) were studied in tetrahydrofuran at 50°C with azobisisobutyronitrile as an initiator. The initial rate of polymerization was proportional to [AIBN]^1/2 and [Bu-1-Acid]¹. The overall activation energy for the polymerization was 22.87 kcal/mole. For copolymerization with styrene (M₂) and acrylonitrile (M₂), the monomer reactivity ratios r₁, r₂ were determined by the Fineman-Ross method, as follows; r₁ = 5.55, r₂ = 0.08 (M₂ = styrene); r₁ = 11.0, r₂ = 0.03 (M₂ = acrylonitrile). Alfrey-Price Q-e values calculated from these values were 6.0 and +0.11, respectively. The Bu-1-Acid unit in the copolymer as well as the homopolymer was found from infrared and NMR spectral analyses to be composed of a trans-1,4 bond. The hydrogen-transfer polymerization of Bu-1-Acid leading to polyester was attempted with triphenylphosphine as initiator, but did not occur.     

Copolymerization of sodium 2-crylamido-2-methylpropanesulfonate with sodium acrylate in concentrated aqueous solutions

The kinetic features of potassium persulfate-initiated homogeneous radical copolymerization of sodium 2-acrylamido-2-methylpropanesulfonate (M₁) with sodium acrylate (M₂) in concentrated aqueous solutions and NaCl aqueous solutions at pH 9 and T = 60°C have been studied. The initial rate of copolymerization increases with the concentration of each monomer, the total concentration of comonomers (M₁ + M₂), the concentration of initiator, and the concentration of NaCl and shows an extreme change with an increase in the content of M₂ in the initial monomer mixture. The molecular mass of the copolymer shows an extreme dependence on the content of M₂ in the initial monomer mixture; it drops with an increase in the concentration of NaCl and remains unchanged with conversion. For copolymerization in water and 2 M NaCl, r ₂ > r ₁. The number of M₂ units in the copolymer does not change with conversion and increases on addition of NaCl owing to a gain in r ₂.     

Copolymerization of Tri-n-butyltin Acrylate and Tri-n-butyltin Methacrylate Monomers with Vinyl Monomers Containing Functional Groups

A new approach to obtaining thermoset organotin polymers, which permits control of crosslinking site distribution and, through it, a better control of properties of organotin antifouling polymers, is reported. Tri-n-butyltin acrylate and tri-n-butyltin methacrylate monomers were prepared and copolymerized, by the solution polymerization method with the use of free-radical initiators, with several vinyl monomers containing either an epoxy or a hydroxyl functional group. The reactivity ratios were determined for six pairs of monomers by using the analytical YBR method to solve the differential form of the copolymer equation. For copolymerization of tri-n-butyltin acrylate (M₁) with glycidyl acrylate (M₂), these reactivity ratios were n = 0.295 ± 0.053, r₂ = 1.409 ± 0.103; with glycidyl methacrylate (M₂) they were r₁ = 0.344 ± 0.201, r₂ = 4.290 ± 0.273; and with N-methylolacrylamide (M₂) they were r₁ = 0.977 ± 0.087, r₂ = 1.258 ± 0.038. Similarly, for the copolymerization of tri-n-butyltin methacrylate (Mi) with glycidyl aery late (M₂) these reactivity ratios were r₁ = 1.356 ± 0.157, r₂ = 0.367 ± 0.086; with glycidyl methacrylate (M₂) they were r₁ = 0.754 ± 0.128, r₂ = 0.794 ± 0.135; and with N-methylolacrylamide (M₂) they were r₁ ?4.230 ± 0.658, r₂ = 0.381 ± 0.074. Even though the magnitude of error in determination of reactivity ratios was small, it was not found possible to assign consistent Q,e values to either of the organotin monomers for all of its copolymerizations. Therefore, Q,e values were obtained by averaging all Q,e values found for the particular monomer, and these were Q = 0.852, e = 0.197 for the tri-n-butyltin methacrylate monomer; and Q = 0.235, e = 0.401 for the tri-n-butyltin acrylate monomer. Since the reactivity ratios indicate the distribution of the units of a particular monomer in the polymer chain, the measured values are discussed in relation to the selection of a suitable copolymer which, when cross-linked with appropriate crosslinking agents through functional groups, would give thermoset organotin coatings with an optimal balance of mechanical and antifouling properties.     

Free Radical Copolymerization of N‐Cyclohexylmaleimide with Cyclohexene

The radical copolymerization of cyclohexene (M₁) and N‐cyclohexylmaleimide (M₂) was carried out with 2,2′‐azobis(isobutyronitrile) as an initiator in various solvents at 55°C. The copolymerization of cyclohexene with N‐cyclohexylmaleimide in chloroform, dioxane and benzene proceeded in a homogeneous system to give an alternating copolymer when the monomer of cyclohexene was over 40 mol% in the feed. It was found that the initial rate of the copolymerization (R_p), as well as the number‐average molecular weight of copolymers, were dependent on the monomer composition and was at maximum at about 30 mol% of cyclohexene in the feed. The effects of solvents on the R_p and reactivity ratios were also investigated in this copolymerization system. The copolymerization in dioxane produced a higher R_p than that in chloroform and benzene, and the monomer reactivity ratios were found to be r₁=0, r₂=0.032 in chloroform; r₁=0, r₂=0.065 in benzene and r₁=0, r₂=0.14 in dioxane, respectively.