共查询到19条相似文献,搜索用时 156 毫秒
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本文报道了用流动放电-化学发光技术测定O(~3P)和硅烷化学反应速率常数.在293—413K范围内, 结果为k=(1.05±0.36)×10~(-10)exp[(-3.06±0.10) kcal·mol~(-1) /RT] cm~3·molecule~(-1)·s~(-1)并用过渡态理论将上述实验结果外推到200—2000 K范围内. 计算结果以三参数公式表示为: k=7.67×10~(-19) T~(2.59) exp(-720 cal·mol~(-1)/RT) cm~3·molecule~(-1)·s~(-1). 相似文献
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碳氢化合物被NO_x光氧化过程中会产生中间物质酮类化合物,与烷烃、烯烃不同的是,这类化合物与大气化学中感兴趣的自由基,如O、OH等的基元反应研究得不多。除有少量关于O(~3p)与丙酮反应速率常数测定的报道外,前文还报道了O(~3p)与丁酮反应速率常数的测定,并得出该反应速率常数与温度关系的Arrhenius表达式。 相似文献
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酮类分子反应是大气化学反应中的一个中间反应.在300--500K范围内,我们对酮类分子和O(~3P)原子反应速率常数作了系列测定.为了估算大气化学和燃烧化学反应条件下的反应速率常数,本文用过渡态理论将实验结果外推到200—2000K范围内.同时对 相似文献
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ZHANG Jun SUN Xiao-min CAI Zheng-ting FENG Da-cheng 《高等学校化学研究》2006,22(5):663-664
In the stratosphere,CF3Cl(CFC13)can either photodecompose or react directly with atomic oxygen to generate ozone-depleting agents such as Cl and ClO in the gas phase[1—3].Since the1970s,attention has been focused on the effects of these compounds on the … 相似文献
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(NH3CH2CH2NH2)3[Mo(Ⅴ)O2(O2C6H4)2] (1), (NH3CH2CH2NH2)2.5[Mo(Ⅴ)o.sW(Ⅵ)o.502(O2C6H4)2] (2) and(NH3CH2CH2NH2)2[VC(Ⅵ)O2(O2C6H4)2] (3) were synthesized, structurally characterized by X-ray diffraction analysis, and studied on their interactions with ATP, their DNA cleavage activities and antitumor properties. The redox state of molybdenum was not changed on going from crystal to aqueous solutions in complexes 1 and 2, while tungsten underwent reduction from W(VI) to W(V) in complexes 2 and 3. ATP promoted the oxidation of both molybdenum and tungsten from M(Ⅴ) to M(Ⅵ) and the hydrolysis of catecholate ligands in solution consisting of ATP and the complexes. Complex 1 possesses fairly good activity to DNA cleavage and against tumor S180 in mice, and is more effective than the control drug cyclophosphamide under the identical conditions. However, complexes 2 and 3 exhibited marginal effectiveness. The effectiveness of anti-tumor of the complexes was related positively to their DNA cleavage activities and their hydrolysis of catecholate ligands. 相似文献
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JianGONG ChangLuSHAO LunYuQU 《中国化学快报》2004,15(3):333-334
A new organophosphazene polyoxotungstate, [(N3P3)(SiW11O39H2)3]^12-, has been prepared by reaction of hexachlorocyclotriphosphazene with undecatungstosilicate, and characterized by elemental analysis, infrared spectroscopy, and multinuclear ^31p NMR. 相似文献
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1 INTRODUCTIONTransition metal clusters have been attracting intensive attention largely because they are suggested as active catalysts in a variety of homogeneous catalyzed reactions. However, no unequivocal proof exists that metal clusters themselves serve as the true catalysts among the catalytic process. In many cases it is known that fragments of the original clusters are the actual catalytic species. The unambiguous proof would be the use of a rigid chiral cluster to catalyze an asy… 相似文献
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Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme. 相似文献
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In the stratosphere, CF3Cl (CFC 13) can either photodecompose or react directly with atomic oxygen to generate ozone-depleting agents such as Cl and ClO in the gas phase[1-3]. Since the 1970s, attention has been focused on the effects of these compounds on the destruction of ozone in the stratosphere and on global warming[4,5]. 相似文献
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On the Knowledge of the New Ionic Ozonides P(CH3)4O3 and As(CH3)4O3 P(CH3)4O3 and As(CH3)4O3 were prepared via ion exchange in liquid ammonia and characterized by X-ray-powder, IR, MS and DTA techniques. P(CH3)4O3 and As(CH3)4O3 are isotypic and have a wurtzite-like arrangement of ions with rotationally disordered O3?. (Powder data: P63mc; P(CH3)4O3: a = 687.8(2), c = 964.6(3) pm; As(CH3)4O3: a = 708.6(1), c = 991.0(3) pm). As(CH3)4O3 shows a displacive phase transition at ?135°C. The low temperature phase is orthorhombic (a = 715.8(7), b = 1 209(1), c = 943.3(1) pm). 相似文献
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O(3P)+O2H→OH+O2反应机理的密度泛函理论研究 总被引:1,自引:3,他引:1
用密度泛函理论方法研究了O(3P)与O2H反应生成羟基和氧分子的反应机理. 在PW91/6-31+G水平上用梯度解析技术全自由度优化上述反应物、产物和反应路径上的中间体及过渡态几何构型, 并通过频率振动分析加以确认, 计算IRC反应路径及中间体异构化过程, 确定了此反应的可能反应通道. 结果表明: 该反应是多通道多步骤的强放热反应. 首先形成顺式或反式O3H富能中间体, 此过程无能垒; 然后跨过一个能垒分解成产物OH和O2. 通道IM1→TS1比IM2→TS2克服的能垒要大, 反应放热372.822 kJ*mol-1. IM1TS3IM2 可相互转化. 相似文献
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CH_3自由基和O(~3P)反应机理的量子化学研究 总被引:4,自引:0,他引:4
用分子轨道从头计算MP2(full)方法和密度泛函理论(DFT)中的B3LYP方法 研究了CH_3自由基和三线态O原子反应的微观机理,优化得到了反应途径上的反应 物、过渡态、中间体和产物的几何构型,通过振动分析对过渡态和中间体构型进行 了确认,在G3不平上计算了能量,同时用经典过渡态理论对该反应的绝对速率常数 进行了理论计算。研究结果表明:CH_3自由基与O(~3P)反应有四条不同的放热反 应通道,主反应通道为IM1→TS1→CH_2O + H,同时反应可彻底裂解生成CO, H_2 及H。 相似文献
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新显色剂1—(对偶氮苯)—3—(2—吡啶)—三氮烯与镍显色反应的研究 总被引:24,自引:7,他引:17
提出了用新试剂1-(对偶氮苯)-3-(2-吡啶)-三氮烯分光光度法测定镍的方法,研究结果表明,显色反应有很好的选择性,常见离子除镉外,基本上不干扰。 相似文献
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非负载Ni(Co)-Mo-Al_2O_3纳米催化剂的制备及其生物油模型化合物加氢脱氧性能研究 总被引:1,自引:1,他引:1
采用热沉淀法制备了纳米级(粒径在15~30nm)非负载Ni(Co)-Mo-Al2O3催化剂,并用BET、XRD、SEM、TEM等技术对催化剂进行了表征;并以乙酸为探针分子,在连续流动固定床反应器上评价了催化剂的加氢脱氧活性,考察了Ni、Co活性组分、焙烧温度对催化剂的晶态结构及催化性能的影响.结果表明:在考察的反应条件下,Ni、Co活性组分加入后,使Mo-Al2O3催化剂的活性明显提高;而且Ni-Mo-Al2O3催化剂的加氢脱氧活性明显高于Co-Mo-Al2O3催化剂的活性;焙烧温度由500℃升高到550℃时,催化剂的比表面积增大,晶化度提高,催化剂的活性提高. 相似文献