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1.
在束-气装置上的单次碰撞条件下,利用低压直流放电选择性地激发碱土金属到亚稳态,观察了Ca(~1S)、Ca(~1S’~3P)、Ba(~1S)、Ba(~1S,~3D)+ClO_2。反应的化学发光.通过测量化学发光总包光强的空间分布,得到这些反应的总碰撞截面为:Ca(~1S)+ClO_2,97(A~2);Ca(~3P)+ClO_2,138(A~2);Ba(~1S)+ClO_2,136(A);Ba(~3D)+ClO_2,239(A~2),计算机模拟化学发光光谱,发现新生产物MO(M=Ca,Ba)的电子激发态A~1П态的相对振动布居分布是非玻尔兹曼分布的,求出反应Ba(~3D)+ClO_2和Ca(~3P)+ClO_2产生的MClC~П→X~2 ∑~+跃迁的化学发光截面分别为51(A~2)和31(A~2),计算光谱中不同成份的光强,得到了反应产生MO、MCl的产物分支比.最后,讨论了这类反应的机理。 相似文献
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在束-气装置上的单次碰撞条件下, 利用低压直流放电选择性地激发碱土金属到亚稳态, 观察了Ca(~1S)、Ca(~1S’~3P)、Ba(~1S)、Ba(~1S, ~3D)+ClO_2。反应的化学发光. 通过测量化学发光总包光强的空间分布, 得到这些反应的总碰撞截面为: Ca(~1S)+ClO_2, 0.97 nm; Ca(~3P)+ClO_2, 1.38 nm; Ba(~1S)+ClO_2, 13.6 nm; Ba(~3D)+ClO_2, 2.39 nm, 计算机模拟化学发光光谱, 发现新生产物MO(M=Ca, Ba)的电子激发态A~1П态的相对振动布居分布是非玻尔兹曼分布的, 求出反应Ba(~3D)+ClO_2和Ca(~3P)+ClO_2产生的MClC~П→X~2 ∑~+跃迁的化学发光截面分别为0.51 nm和0.31 nm, 计算光谱中不同成份的光强, 得到了反应产生MO、MCl的产物分支比. 最后, 讨论了这类反应的机理。 相似文献
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含呋喃环系西佛碱型大环化合物的合成 总被引:3,自引:0,他引:3
利用 Mn~(++)和 Ba~(++)作为模板离子,合成了一类新型的含呋喃环系西佛碱型大环化合物L~1 和配合物 L~2 Ba(ClO_4)_2、L~3 Ba(ClO_4)_2 和 L~4 Ba(ClO_4)_2.L~2~L~4 的 Ba~(++)配合物经与 Na_2 SO_4 水溶液反应解络,得到自由配体 L~2、L~3 和 L~4。配体 L~2 和 L~3 分别与 Sr~(++)作用,得到配合物 L~2 Sr(ClO_4)_2 和 L~3 Sr(ClO_4)_2。上述大环配体和各种配合物均经元素分析、IR、~1HNMR、MS 等证实了它们的结构和组成。 相似文献
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测定了三个三元体系LaX_3-PIAP-H_2O(X~- = ClO_4~-,NO_3~-,Cl~-, PIAP为4-(邻苯二甲酰基)亚基安替比林)在30℃时的溶解度。研究发现La (NO_3)_3-PIAP-H_2O和LaCl_3-PIAP-H_2O体系均为简单共饱型;La(ClO_4)_3- PIAP-H_2O体系有一个新固相形成,其组成为La(PIAP)_3(ClO_4)_3·4H_2O和体 系均为简单共饱型;La(ClO_4)_3-PIAP-H_2O体系的相平衡研究结果,合成了相应 的镧系配合物Ln(PIAP)_3(ClO_4)_3·4H_2O(Ln = La, Pr, Nd, Sm, Gd, Yb),通 过化学分析、元素分析TG-DTG'IR谱和密度对化合物进行了表征。 相似文献
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合成了四(三苯基氧膦)高氯酸稀土络合物。有关鉴定和元素分析表明,络合物的分子式为Ln(ClO_4)_3·4PhPO,其中Ln=La、Pr、Nd、Sm、Eu。用X射线单晶衍射法测定了CNd(ClO_4)_2·4Ph_3PO]ClO_4·2CH_3COCH_3的晶体和分子结构,该晶体属单斜晶系、P2_(1/c)空间群:a=13.469(5)、b=19.540(8)、c=28.437(9)、β=90.79(3)°、V=7483(5)(?)~3,Z=4。钕与八个氧配位,其中四个氧来自四个三苯基氧膦的膦酰基,四个氧由两个双齿配位的高氯酸根提供,组成了[Nd(ClO_4)_24Ph_3PO]~+络阳离子,它与外界的另一个ClO_4~-以静电相互作用形成分子。溶剂分子CH_3COCH_3不与钕成键。钕的配位多面体具有D_(2d)P_(2m)对称性,是一个不规则的三角十二面体。 相似文献
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我们测定了三元体系 Ln(ClO_4)_3—4-ClCH_2COA_p—H_2O(Ln=La,Sm,Er)存30℃时的溶度及饱和溶液的折光指数,绘制了相应的溶度图和饱和溶液的折光指数曲线图.体系的溶度曲线和折光指数曲线均由四支组成,分别与4-ClCH_2COA_p、Ln(4-ClCH_2COAp)_3(ClO_4)_3·nH_2O(Ln=La,n=7;Sm,8;Er,4)、Ln(4-ClCH_2COAp)_2(ClO_4)_3·nH_2O(Ln=La,n=7;Sm,6;Er,4)和 Ln(ClO_4)_3·nH_2O(Ln=La,n=8;Sm,9;Er,6)相对应,两类配合物均为固液异组成化合物. 相似文献
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三苯基氧膦钕盐配合物的振动光谱 总被引:2,自引:0,他引:2
本文测定了Ph_3PO、Nd(NCS)_3·4Ph_3PO、[Nd(ClO_4)_2·4Ph_3PO]~+ClO_4~-·2CH_3COCH_3以及Nd(NO_3)_3·2Ph_3PO·C_2H_5OH在4000~100 cm~(-1)区域内的FT-IR和激光Raman光谱,分析和讨论了各主要谱带的性质和配位结构. 相似文献
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高氯酸镧甘氨酸水体系及其新相中配合物La(Gly)_3(ClO_4)_3·2H_2O结构的研究 总被引:1,自引:0,他引:1
测定了La(ClO_4)_3-Gly-H_2O在25℃时体系的溶度,并绘制了相应的溶度图.体系中形成了2个新配合物La(Gly)_3(ClO_4)_(3)·2H_2O(Ⅰ)和La(Gly)_4(ClO_4)_3(Ⅱ).(Ⅰ)为固液异成分溶解、(Ⅱ)为固液同成分溶解的化合物,同时以相图为依据合成并培养了配合物(Ⅰ)的单晶,测定了晶体结构,其化学式为(La_2(Gly)_6(H_2O)_4]·6ClO_4,晶体属三斜晶系,P1空间群,每个晶胞中有2个化学式量.晶胞参数:a=1.0693(3)nm,b=1.2956(3)nm,c=0.8762(3)nm,α=82.83(3)°,β=67.25(3)°,γ=71.50(2)°,配位单元中镧为9配位,其配位多面体为畸变的三冠三角棱柱体. 相似文献
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采用溶解度等温法研究了La(ClO_4)3-C_(11)H_(12)2ON_2(安替吡啉)-H_2O三元体系在0℃时的相平衡,并由此合成了La(C_(11)H_(12)ON_2)_6(ClO_4)_3配合物。还确定了该配合物的制备条件,测定了它的一些性质,并对其结构作了初步分析。 相似文献
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本文研究了低浓度的碘酸盐在硫酸介质中, 在铂电报上的电化学还原。用旋转盘环电极检测到了碘酸盐阴极还原的中间产物I_2及最终产物I~-。测定了电化学反应的动力学参数。最后提出了磺酸盐阴极反应的机理。 相似文献
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Agnieszka Nosal-Wiercińska 《Central European Journal of Chemistry》2014,12(2):213-219
The results of the kinetic measurements of Bi(III) electroreduction on a mercury electrode in 1–8 mol dm?3 chlorate (VII) solutions and in the presence of cystine demonstrate a dependence of the process on the temperature. The applied electrochemical techniques (DC polarography, cyclic and SWV voltammetry) allowed for the determination of the kinetic and thermodynamic parameters and their correlation with water activity. The catalytic activity of cystine was confirmed by the decrease in overall enthalpies of activation. The changes in the values of ΔH ≠ and ΔS 0 for Bi(III) electroreduction in the presence of cystine with the increase of chlorate (VII) concentration showed that the mechanism is different in solutions with low water activity as compared to those with high water activity. Probably it is connected with a different structure of the activated complexes (Bi-Hg(SR)2), mediating electron transfer. 相似文献
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An electrode has been prepared, consisting of a PVC membrane containing Corning 477316 nitrate liquid ion-exchanger in the chlorate form, which responds to chlorate ions. It has a faster response (1-2 sec) and lower limit of detection (3 x 10(-5)M) than the nitrate electrode for chlorate determination. Selectivity coefficients for the electrode towards several other ions have been measured. 相似文献
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M. Yu. Chaika E. V. Bulavina A. S. Solyanikova T. A. Kravchenko P. V. Seredin 《Russian Journal of Electrochemistry》2012,48(2):212-217
Based on a MK-40 sulfocation-exchange membrane, a hybride electrode material containing nanodispersed copper is prepared.
The methods of scanning electron microscopy and X-ray diffraction (XRD) analysis reveal the formation of copper agglomerates
measuring 250–470 nm and consisting of individual particles of 20–30 nm. The procedure of multistage chemical deposition of
copper into the ion-exchange carrier makes it possible to obtain a continuous cluster of metal particles which determines
the electron conducting properties of the resulting hybrid material. The electrochemical activity of the nanocomposite electrode
is studied in the reaction of nitrate ion electroreduction. Nanodispersed copper deposited into the membrane is shown to intensify
the electroreduction of nitrate ions by a factor of 1.5–2 as compared with a compact copper electrode. The electroreduction
of nitrate ions on compact copper is shown to involve 6 electrons, whereas the electroreduction on the nanocomposite involves
8 electrons. The electroreduction products of nitrate ions are identified by the IR spectroscopy method. 相似文献
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Jolanta Nieszporek 《Electroanalysis》2012,24(7):1584-1590
The results of kinetic measurements of Zn2+ electroreduction on mercury electrode in the presence of tetramethylthiourea showed the two‐step character of the electrode process. The acquisition of nonlinear wide potential range Tafel plots was found to offer a good opportunity to examine the Zn2+ electroreduction mechanism. Three mechanisms including the ion transfer step followed by the electron exchange step (IE mechanism), the adsorption step (IA mechanism) and the chemical step followed by electron transfer (CE) were applied. The accelerating influence of tetramethylthiourea on Zn2+ electroreduction was found to result from possible complexes formation in the diffuse layer. The ion transport step is probably combined with the loss or exchange of a ligand. The second step probably consists in the electron transfer or adsorption process connected with partial charge transfer. 相似文献
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Tang W Peterson AA Varela AS Jovanov ZP Bech L Durand WJ Dahl S Nørskov JK Chorkendorff I 《Physical chemistry chemical physics : PCCP》2012,14(1):76-81
This communication examines the effect of the surface morphology of polycrystalline copper on electroreduction of CO(2). We find that a copper nanoparticle covered electrode shows better selectivity towards hydrocarbons compared with the two other studied surfaces, an electropolished copper electrode and an argon sputtered copper electrode. Density functional theory calculations provide insight into the surface morphology effect. 相似文献
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The fast detection of 5-hydroxymethyl-2-furfural (HMF) in food industry is vital because of its toxicity and mutagenicity. A glassy carbon electrode (GCE) modified with black phosphorene (BP) nanosheets was prepared and coated with Nafion to improve stability. The electrode has excellent electrochemical stability and current response for HMF electroreduction. The good linear relationship is in the concentration range of 0.1–10 μg/mL with the detection limit of 0.012 μg/mL. HMF electroreduction is a diffusion-controlled process involving two electrons and two protons. The sensor was successfully applied to the measurement of HMF in milk with the recovery values of 92.92 %–96.33 %. 相似文献