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Under the conditions of stir speeds 400 r·min~(-1) and distance between anode and cathode 1 mm, by using the orthogonal design, the optimum technological conditions were found that the current density was 0.3 A·cm~(-2), initial NaOH concentration in catholyte was 50 g·L~(-1), reaction times of two steps were all theoretical electrochemical reaction times. In the first electrosynthesis, initial Na_2CrO_4 concentration in anolyte was 650 g·L~(-1), and reaction temperature was 80℃. In the second electrosynthesis, initial Na_2Cr_2O_7 concentration in anolyte was 700 g·L~(-1), and reaction temperature was 85℃.

324全氟磺酸增强复合阳离子交换膜、阴阳极液中搅拌速度均为400r·min~(-1)条件下,通过正交实验得到优化工艺条件为:电流密度0.3A·cm~(-2),阴极液氢氧化钠初始浓度50g·L~(-1),两步反应时间均为理论电催化反应时间,第一步阳极液铬酸钠初始浓度650g·L~(-1),反应温度80℃,第二步阳极液重铬酸钠初始浓度700g·L~(-1),反应温度85℃。

1 At a reaction temperature of 100 ℃ and a reaction time of 30 min to give 2,which was then subjected to condensation reaction with p-propoxy mandelic acid in the presence of phosphoric acid at a molar ratio of m(2)∶m( p-propoxy mandelic acid )∶m=1∶1∶1 at a reaction temperature of 60 ℃ for 3 h to yield 3,which was further oxidized by chloranil to give t.

对现有分散红356合成工艺进行了优化,以n∶n=1.2∶1投料,100℃反应30 min得缩合物2,再在等质量磷酸催化下与分批加入的等质量对丙氧基扁桃酸60℃缩合3 h得缩合物3,经温和氧化剂四氯苯醌氧化得标题化合物,总收率55%。

First, a chlorinator was self-designed in this paper, and dichloride of 2-methyl-1-propene was synthesized by 2-methyl-1-propene reacted with chlorine fast in this reactor. By means of the Orthogonal Experiments design and single factor experiments, the influence of several reaction variables on the yield were examined and the optimum reaction conditions under the intervallic operation were obtained, the yield and selectivity of dichloride of 2-methyl-1-prop-ene were more than 65% and 80% respectively. Second, the preparation of 2-methylene-1, 3-propanediol, which dichloride of 2-methyl-1-propene reacted with alkali was investigated. By means of the Orthogonal Experiments design and single factor experiments, the influence of several reaction variables on the yield were examined and the optimum reaction conditions under the intervallic operation were obtained, the conversion of dichloride of 2-methyl-1-propene was 100%. Moreover the preparation of MPO, which 2-methylene-1, 3-propanediol reacted with hydrogen, in presence of Al_2O_3-Pd catalyst, was gotten, and the product was appraised.

本文在氯化反应过程中,自行设计制作出了氯化管式反应器,在该反应器中异丁烯和氯气迅速混合反应生成二氯异丁烯,根据该氯化反应特征利用正交试验和单因素试验考察了有关因素的影响并优化得到了最佳工艺条件,二氯异丁烯的总收率达65%以上,选择性达80%;接着,对二氯异丁烯进行水解反应制得了2-甲烯-1,3-丙二醇,讨论了相关因素对水解反应的影响,并通过正交试验和单因素试验得到了较佳工艺条件,二氯异丁烯的转化率达100%;同时还对制备的2-甲烯-1,3-丙二醇在常压下采用三氧化二铝负载钯催化剂催化加氢得目的产物MPO,并对产品进行了鉴定,从而打通了整个工艺路线。

Transmission Electron Microscope and other properties testing results show that the complex emulsifier system is the crucial influence factor of the polymerization process and the properties of products. It may influence the coagulum content and reaction rate of the polymerization process, the performance, particle diameter,viscosity, electrolyte stability and storage stability of the emulsion products and the contact angle of the film.The initiator mainly influences the coagulum content and reaction rate.The acrylic monomers mainly influence the solid content, Minimum Film Formation Temperature of the emulsion and the Glass Transition Temperature of the film.The organic silicone monomer mainly influences the water absorption of the film.The reaction temperature mainly influences the reaction rate and conversion.The stirring intensity mainly influences the coagulum content of the polymerization process.

透射电镜等性能测试结果显示:复合乳化剂体系是硅丙共聚乳液的聚合过程及产品性能的主要影响因素,它可以对聚合过程的凝胶率、反应速率以及乳液的外观、粒径、粘度、耐电解质稳定性及贮存稳定性,还有乳液涂膜的接触角等造成不同程度的影响;引发剂主要影响反应速率和凝胶率;丙烯酸酯单体主要影响到乳液的固含量、最低成膜温度以及涂膜的玻璃化转变温度,有机硅单体主要影响涂膜的吸水率等;聚合反应温度主要影响乳液的反应速率和转化率等;搅拌强度主要是影响到聚合过程的凝胶率。

The effects of various factors on the reaction were studied.It has been found that the optimum reaction conditions are that the amount of catalyst is 13.3% of the amount of cyclohexanol, the reaction time is 80 minutes and the reaction temperature is 200~210℃.

考察了催化剂用量、反应温度、反应时间等因素对脱水反应的影响,得出了其最佳的反应条件:催化剂用量为环己醇质量的13.3%,反应时间80 m in,油浴温度200~210℃。

The catalytic oxidation of cyclohexane to cyclohexanone and cyclohexanol in air as probe reaction was performed without any organic solvent or cocatalyst, and the influences of the amount of metal porphyrin, reaction pressure, reaction temperature and reaction time on the catalytic activity were investigated.

以空气氧化环己烷制备环己酮和环己醇为探针反应,在不加入任何有机溶剂或助催化剂的条件下考察了金属卟啉用量、反应压力、温度、时间等对其催化活性的影响。

Effects on the reaction of factors such as reactant ratio, reaction time, and reaction temperature were investigated, and optimum reaction conditions were determined as follows: mole ratio of cyanuric chloride to ethylamine to sodium hydroxide to sodium methyl mercaptide was 1:2.1:2.0:1.7, and the temperature and time of the first, second, and third substitution reactions were -2, 0, and 82℃ and 30, 60, and 180 min, respectively.

讨论了原料配比、反应时间和反应温度等因素对反应的影响,获得了较佳的反应条件。较佳反应条件为三聚氯氰:乙胺:氢氧化钠:甲硫醇钠=l:2.1:2.0:1.7,第一、第二、第三取代反应的反应温度和反应时间分别为-2℃、0℃、82℃和30、60、180min。

The results were as follows:(1) Reaction-time is a distinguishable item;(2)Reaction-time of seamen is longer than seafaring students;(3)Reaction-time are different of age group;(4)Reaction-time got one or two difference of seaman s work age,sailing age,headship,education,source and marriage.

结果表明:①反应时是一项鉴别力很高的项目;②海员的反应比航海专业学员的反应时长;③不同年龄海员组的反应时存在差异;④海员的其它个人特征如工龄、海龄、职务、学历、来源和婚否的不同对反应时的影响只表现在其中的个别方面或没有影响。

Cyclic voltammetry indicated that there were Cr→Cr, Cr →Cr oxidation reaction on anode, while there were Cr→Cr, Cr→Cr, Cr →Cr deoxidization reaction on cathode. The graphite electrodes treated by acid and heating could enhance the reversibility and kinetic of the electrode reaction. The nature graphite electrodes had been eroded during charge/discharge process, while the graphite electrodes by activation could avoide corroding by hexad chromium ion. The reversibility and kinetic of the electrode reaction of chromium ion on activation electrode had been increased, so which indicated that graphite surface augment oxygenous function corps which could increase electrode hydrophile capability.

循环伏安实验表明:铬液流电池的电极反应非常复杂,在阳极存在Cr→Cr,Cr→Cr的氧化反应,在阴极存在Cr→Cr,Cr→Cr,Cr→Cr的还原反应;热处理的石墨电极和重铬酸钾处理的石墨电极能提高电极反应的活性和可逆性;在充放电实验中未处理的石墨电极发生严重腐蚀;分别用这两种方法处理过的石墨电极具有防止六价铬侵蚀的功能;铬离子在活化处理过的石墨电极上的反应活性和可逆性增加,可以认为:重铬酸钾溶液活化处理和加热处理后的石墨表面的含氧官能团增加,电极亲水性增强。

The effects of different factors on the laser-induced graft polymerization on the PET surface were analyzed, and the mechanisms were discussed. The factors were: 1 Monomers with smaller molecules resulted in better modification than polymeric monomers. Acrylamide monomer was chosen as hydrophilic modifier finally; 2 Higher concentration of the monomer solution favored the graft reaction; 3 With the increasing laser fluence, the surface hydrophilicity of PET films increased at first, then decreased. More laser pulses led to a more hydrophilic surface; 4 Benzophenone as a photosensitizer hindered the graft polymerization; 5 The homopolymer retardant of ammonium iron sulfate hexahydrate in a proper concentration retarded the formation of homopolymers and promotes the graft copolymerization; 6 The solvent of monomer solution also affected the graft reaction. Different solvents functioned in different ways. Ethanol can promote the graft reaction because of the activity of hydrogen in its structure; 7 pH value of the monomer solution affects the polymerization rate, and a lower pH value was favorable to the graft reaction.

这些影响因素的作用分别为:1小分子单体的表面改性效果好,确定以丙烯酰胺为亲水性改性单体;2较高的单体溶液浓度有利于接枝反应;3激光能量密度增大,薄膜表面亲水性先显著增强,后又减弱;激光脉冲次数越多,改性后表面亲水性越强;4光敏剂BP对PET表面接枝聚合反应有阻碍作用;5适当浓度的均聚物抑制剂六水合硫酸铁铵能减少单体均聚物的生成,促进接枝聚合;6单体溶液的溶剂也影响接枝聚合的反应进程,不同溶剂的影响作用原理不同,含较活泼氢的乙醇能促进接枝反应;7溶液pH值影响单体聚合速率,pH值较低有利于接枝反应。

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