钠的两个性质实验的创新设计

钠是典型的金属元素,在中学阶段,研究钠的化学性质主要包括2个方面:一是钠与非金属(主要是氧气)的反应,即钠在空气中燃烧;二是钠与水的反应.钠在空气中燃烧的实验多数教材采用的方法是在石棉网上加热,这种方法不仅实验成功率低,而且会损坏石棉网,造成不必要的浪费;人教版普通高中课程标准实验教科书<化学1(必修)>采用的方法是钠在坩埚中燃烧[1],用这种方法实验,学生不容易观察到实验现象,演示效果较差.钠和水的反应,不容易收集到反应时生成的气体,气体产物的检验成为实验的难点,3套新课程标准高中化学教材中都略去了该项实验操作.为了克服以上困难,我们对上述2个实验进行了改进.     

SO_2和H_2O(g)对新疆高钠煤中钠挥发和形态迁移的研究

在水平管式炉上进行了400-1 100℃新疆高钠煤恒温燃烧实验,并利用逐级提取的方法分析煤及煤灰中钠的赋存形态,研究煤中钠的释放和形态迁移特性。重点考察700和1100℃下H_2O(g)和SO_2(g)单因素及双因素对煤中无机钠挥发和形态迁移的影响。结果表明,随着温度的升高,煤中钠的释放比例逐渐增大,其中,有机态钠最先析出,其次是水溶态无机钠,硅铝酸盐形式的无机钠则由于高热稳定性不易分解或挥发。低温下(700℃)H_2O(g)的存在降低了钠的挥发,而较高温度下(1 100℃)焦炭与水蒸气反应生成的局部还原性气氛促进煤中钠的挥发,但当入口气氛中H_2O(g)浓度高于20%时,促进作用减小。SO_2的存在抑制了煤中钠的挥发,随着燃烧温度升高,SO_2对钠的抑制作用减弱。H_2O和SO_2双因素作用下,低温下(700℃)抑制了煤中钠的挥发,而较高温度下(1 100℃)钠的挥发特性取决于两者在入口气氛中的浓度。对于选取的高钠煤,20%H2O和2.0×10-3SO_2入口气氛下,1 100℃煤燃烧钠的挥发比例由86%提高到了87.1%。     

"乙醇与钠的反应"实验改进

1问题的提出笔者在课堂演示人教版教材《化学2(必修)》第三章第三节实验3-2乙醇与钠的反应时,学生提出2个问题:(1)乙醇为易挥发液体,且钠与乙醇反应放热,故放出的氢气中含有一定浓度的乙醇蒸气。教材中通过气体燃烧产物的检验,判断钠与乙醇反应放出     

煤中钠在燃料初期行为的研究

煤中钠是影响增压流化床（PFBC）和整体煤气化（IGCC）发展的一个重要因素。本文对煤中钠分别在800℃和900℃以及富氧和贫氧两种气氛下燃烧初期的释放规律进行了研究。结果表明,煤中钠在燃烧初期变化不大,钠的释放将主要发生在煤燃烧的后期。不同形态钠在燃烧初期的变化规律不同。随燃烧时间的增加水溶钠线性减小,盐酸溶钠线性增加。醋酸铵溶钠在燃烧初期总体表现为增加,不可溶钠则总体减少。研究显示,不同形态钠在燃烧初期存在转化,并主要表现咪水溶钠向盐酸溶钠的转化。温度和气氛对钠释放的影响主要取决于煤种。     

不同反应气氛下准东高钠煤中钠的迁移转化与积灰特性

为了获得循环流化床工艺下不同反应气氛对准东高钠煤中钠的迁移转化与积灰特性的影响,在0.4t/d循环流化床实验装置上开展了相同床温(950℃)下的新疆沙尔湖高钠煤的气化(还原性气氛)与燃烧(氧化性气氛)实验研究。结果表明,气化和燃烧气氛下飞灰与积灰中Na主要以NaCl的形式存在;气化比燃烧更容易将Na、Cl固留在底渣和飞灰中,相应的进入气相中的Na、Cl更少;燃烧气氛下,部分NaCl会被烟气中的SO_2硫化,生成稳定性更高的Na_2SO_4并冷凝在飞灰和积灰棒表面,燃烧过程中产生的飞灰粒径更细,积灰更严重;沙尔湖煤燃烧与气化过程中存在HCl对金属壁面的腐蚀。     

新课标中钠在空气中燃烧实验的探究与改进

为解决新课标《化学1(必修)》和普通中学化学教科书中钠燃烧实验存在的玻璃管易破裂、现象不易观察以及空气污染等问题,对该实验的装置、材料和演示方法进行了探讨,设计了在封闭的装置里进行钠燃烧实验的新方案,取得了良好的实验效果.     

燃烧放热对准东煤成灰过程中钠盐释放的影响

选取典型的准东煤五彩湾煤为研究对象,在马弗炉内制备400-1200℃的燃烧灰和再热灰,采用K型热电偶测量燃烧过程中样品表面温度,通过XRF、XRD分析获得灰的成分和结晶形式,取部分灰样逐级萃取,通过微波消解及电感耦合等离子体质谱仪(ICP-MS),获得灰中钠的赋存特性。结果表明,燃烧和再热灰在成分和晶体形式上差异显著,再热灰钠含量明显高于燃烧灰且灰熔点偏低;随着温度升高灰中钠盐总量明显减少,其中,水溶钠、醋酸铵溶钠迅速减少,而盐酸溶钠含量先增加后减少,不可溶钠增加,释放的钠以可溶钠为主;加热温度和时间影响钠的释放,燃烧反应放热导致煤粉表面温度超过环境温度200℃以上,是钠盐过多释放的主要原因。     

钠在空气中燃烧生成过氧化钠的热力学讨论

从热力学基本原理出发,探讨钠在空气中燃烧生成过氧化钠的原因,得出过氧化钠是钠在空气中燃烧反应的最稳定产物的结论。     

离子选择电极在聚合研究中的应用—聚丙烯酰胺衍生物中钠的测定

本文介绍了一种测定聚丙烯酰胺衍生物中钠的新方法:样品在氧气中燃烧,稀酸溶液吸收,电位法测定。方法简便,其误差在0.2—0.7％之间。此方法适用于有机聚合反应过程中钠的测定。     

高温燃烧法测定钠中微量碳

由于金属钠的应用日益广泛,人们对钠中碳含量测定的研究工作给以很大地注意,建立了各种分析方法。报导过的有:湿法氧化法、高温燃烧法、低温燃烧法、含氧酸助熔剂氧化法、蒸馏分离残渣燃烧法、同位素稀释法和光子活化法。有些方法已经作为一些实验室中钠分析工作的规范,但国内还未见     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。