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Phase-shift studies of Hg(3 P 0) reactions. Part 3.?Complexes of Hg(3 P 0) with some primary amines 汞(3p0)反应的相移研究。第3部分。Hg(3p0)与某些伯胺的配合物
Pub Date : 1971-01-01 DOI: 10.1039/tf9716703247
C. G. Freeman, M. McEwan, R. Claridge, L. F. Phillips
Rate constants for bimolecular and termolecular reactions with Hg(3P0), lifetimes of complexes with Hg(3P0), and lower limits for dissociation energies of complexes with Hg(3P0), have been determined for ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine and tert-butylamine. These results, when supplemented by previous values for the quantum efficiencies of mercury-sensitized luminescence, allow us to assess the relative importance of Hg(3P0) in the sensitized decompositions of amines.
测定了乙胺、正丙胺、异丙胺、正丁胺、仲丁胺、异丁胺和叔丁胺与Hg(3P0)的双分子和三分子反应速率常数、与Hg(3P0)配合物的寿命以及与Hg(3P0)配合物的解离能下限。这些结果,当与先前汞敏化发光的量子效率值相补充时,使我们能够评估汞(3P0)在胺敏化分解中的相对重要性。
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引用次数: 6
Kinetics of oxidation of α-hydroxyisobutyric acid by aquomanganese (III) ions in aqueous perchlorate media 高氯酸水溶液中水锰离子氧化α-羟基异丁酸的动力学研究
Pub Date : 1971-01-01 DOI: 10.1039/TF9716703297
C. F. Wells, C. Barnes
The kinetics of the oxidation of α-hydroxyisobutyric acid by aquomanganese(III) ions have been investigated in aqueous perchlorate media using conventional and stopped-flow spectrophotometry. The acidity range is more restricted than that used for the oxidation of other organic substrates by MnIIIaq as the MnII added to maintain the ionic strength at µ= 4.00 and to suppress the formation of MnIV has a small effect on the rate at [HClO4]⩽ 1.0 M. The rate-determining step involves the decomposition of an intermediate complex, Mn3+(CH3)2COHCOOHaq, and the overall energy E and entropy ΔS* of activation are compared with E and ΔS* for other organic substrates oxidized by MnIIIaq: the high reactivity of α-hydroxyisobutyric acid arises from the high positive ΔS* derived from chelation. A value is estimated for the protonation constant of α-hydroxyisobutyric acid.
采用常规和停流分光光度法研究了高氯酸水溶液中α-羟基异丁酸被水锰离子氧化的动力学。酸度范围更受到的限制比用于其他有机底物的氧化MnIIIaq MnII添加到维护的离子强度µ= 4.00和抑制MnIV的形成有一个小对速率的影响(高氯酸)⩽1.0 m的分解速率决定步骤涉及到一个中间复杂,Mn3 + (CH3) 2 cohcoohaq,和整体能量E和熵Δ*的激活与E和ΔMnIIIaq S *其他有机底物氧化:α-羟基异丁酸的高反应活性来源于螯合产生的高正电荷ΔS*。对α-羟基异丁酸的质子化常数进行了估计。
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引用次数: 2
Specular reflectance and ellipsometric spectroscopy of oriented molecular layers 定向分子层的镜面反射率和椭偏光谱
Pub Date : 1971-01-01 DOI: 10.1039/TF9716703306
M. Dignam, M. Moskovits, R. W. Stobie
Assuming an oriented molecular layer to behave optically as a homogeneous, uniaxial medium with its optic axis normal to the interface, such a system is treated theoretically to yield equations relevant to both specular reflectance and ellipsometric spectroscopy. Explicit expressions are derived for the empirical quantities (relating them to the optical constants of the media and other system parameters) which are both reasonably simple and correct to second-order terms in the film thickness. From ellipsometric measurements alone, it is not possible to distinguish between very thin uniaxial and isotropic films. However, data for a very thin non-absorbing uniaxial film on an absorbing substrate (e.g., a metal), if analyzed on the assumption of film isotropy, lead to an apparent absorption index for the film of the magnitude of the absorption index found for semi-conductors. A similar result is predicted for specular reflectance measurements, except that in that case the apparent optical constants of the film depend on the angle of incidence.
假设定向分子层在光学上表现为均匀的单轴介质,其光轴垂直于界面,这样的系统在理论上可以得到与镜面反射和椭偏光谱学相关的方程。导出了经验量的显式表达式(将它们与介质的光学常数和其他系统参数联系起来),这些显式表达式对膜厚度的二阶项既合理简单又正确。仅从椭偏测量,是不可能区分非常薄的单轴和各向同性薄膜。然而,在吸收基板(例如,金属)上的非常薄的非吸收单轴薄膜的数据,如果根据薄膜各向同性的假设进行分析,则会导致薄膜的表观吸收指数与半导体的吸收指数相当。对于镜面反射的测量,除了薄膜的视光学常数取决于入射角外,还预测了类似的结果。
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引用次数: 99
Partial molal enthalpies, excess partial molal heat capacities and structural effects of Bu4NBr and NaBPh4 in aqueous binary solvent mixtures 双溶剂水溶液中丁腈丁烷和NaBPh4的偏摩尔焓、偏摩尔热容及结构效应
Pub Date : 1971-01-01 DOI: 10.1039/TF9716700305
R. K. Mohanty, T. S. Sarma, S. Subramanian, J. C. Ahluwalia
Integral heats of solution of Bu4NBr in aqueous binary solvent mixtures (containing 0.0 to 0.30 mol fraction of consolvent) of t-butanol, acetone, dioxan and ethylene glycol were determined at 15, 25, and 35°C. Integral heats of solution of NaBPh4 in the same aqueous binary solvents containing 20 % by volume (about 0.05 mol fraction) of cosolvent were also determined at 15, 25 and 35°C. Corresponding excess partial molal heat capacities Δtext-decoration:overlineC°p were derived at 20 and 30°C. The partial molal enthalpies Δtext-decoration:overlineH°s of Bu4 NBr increased (sharply in aqueous t-butanol up to 0.06 mol fraction) with the addition of increasing amount of cosolvent to water till the maximum value was attained at 0.1–0.3 mol fraction of cosolvent. The endothermicity maxima Δtext-decoration:overlineH°smax were in the decreasing order of t-butanol > acetone > ethylene glycol > dioxan. text-decoration:overlineH°smax decreased with increasing temperatures in all aqueous binary solvents. text-decoration:overlineC°p results indicate that addition of small amounts of t-butanol and acetone stabilize the water structure, the maximum stabilization occurring around 0.04 mol fraction of acetone and t-butanol. Further addition of t-butanol to 0.06 mol fraction results in complete collapse of the water structure, whereas further addition of acetone results in gradual breakdown of the water structure which continues up to 0.3 mol fraction of acetone. Dioxan and ethylene glycol seem to have net structure breaking influence on the water structure.
测定了丁醇、丙酮、二氧杂环己烷和乙二醇在15、25和35℃的二元溶剂混合物(含0.0 ~ 0.30 mol分数的溶剂)中的溶液积分热。同时测定了NaBPh4在含有20%(约0.05 mol分数)共溶剂的相同二元水溶剂中,在15、25和35℃时的积分热。相应的超额部分摩尔热容Δtext-decoration:overlineC°p在20和30℃下得到。随着共溶剂加入量的增加,硝酸丁醇的偏摩尔焓Δtext-decoration: overline_°s增大(在0.06 mol分数的t-丁醇水溶液中急剧增加),在0.1 ~ 0.3 mol分数的共溶剂中达到最大值。吸热性最大值Δtext-decoration:上面的eh°smax依次为丁醇→丙酮→乙二醇→二氧二辛。在所有二元水溶剂中,随着温度的升高,h°smax减小。结果表明,少量的丁醇和丙酮的加入稳定了水的结构,在0.04 mol分数的丙酮和丁醇时达到最大的稳定性。当t-丁醇进一步加入到0.06 mol分数时,水结构完全破坏,而当丙酮进一步加入时,水结构逐渐破坏,直至0.3 mol分数的丙酮。二氧嘧啶和乙二醇似乎对水的结构有破坏网状结构的作用。
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引用次数: 24
Orthonormal chemical reactions and chemical relaxation. Part 3.—Reactions in solution under various thermodynamic conditions 标准正态化学反应和化学松弛。第3部分。-不同热力学条件下溶液中的反应
Pub Date : 1971-01-01 DOI: 10.1039/TF9716703240
H. Hayman
The method described previously 2 for obtaining the relaxation times, normal coordinates and normal modes of relaxation of a non-ideal chemical system at constant temperature and pressure is extended to relaxation under adiabatic conditions and/or at constant volume; in each case the normal modes of relaxation are obtained as an orthonormal set satisfying orthonormality conditions similar to those pertaining to constant temperature and pressure. First-order perturbation theory is used for evaluating the various corrections required when the simple dilute-solution theory 1 is used at concentrations which are too high for the theory to be strictly applicable.
先前描述的获得非理想化学系统在恒温常压下的弛豫时间、法向坐标和法向模态的方法推广到绝热条件下和/或在恒体积下的弛豫;在每种情况下,松弛的正常模式都是作为满足标准正交条件的标准正交集得到的,这些标准正交条件与恒温恒压条件类似。一阶摄动理论用于评估在浓度过高而不能严格适用的情况下使用简单稀溶液理论1时所需的各种修正。
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引用次数: 4
Degrees of association of n-pentyl lithium and n-octyl lithium in benzene 苯中正戊基锂和正辛基锂的缔合度
Pub Date : 1971-01-01 DOI: 10.1039/TF9716700353
D. Margerison, J. D. Pont
The degrees of association of n-pentyl lithium and n-octyl lithium in benzene at 30°C have been measured using the method of vapour pressure lowering. The value from n-pentyl lithium is 6.00 ± 0.09 [degrees of freedom (D.F.)]= 13]; the value for n-octyl lithium is 5.953 ± 0.016 (D.F. = 9). It is argued that the two compounds exist predominantly as hexamers in solution.
用蒸汽降压法测定了30℃时正戊基锂和正辛基锂在苯中的缔合度。正戊基锂的值为6.00±0.09[自由度(D.F.)]= 13];正辛烷锂的值为5.953±0.016 (D.F. = 9),认为这两种化合物在溶液中以六聚体形式存在。
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引用次数: 13
Predissociation by the continuum of a bound state without curve crossing. Application to the spectrum of OH 通过无曲线交叉的束缚态连续体预解离。OH光谱的应用
Pub Date : 1971-01-01 DOI: 10.1039/TF9716703395
S. Durmaz, J. Murrell
Calculations of the Franck-Condon overlaps between the bound vibrational levels of the A2∑+ state of OH and the continuum levels of the ground state X2Π suggest that the weak predissociation of the levels ν= 2-5 could be due to a direct predissociation to the ground state and not to the crossing by another excited state. Accurate measurements of the intensity of the emission lines could test this hypothesis.
对氢氧根A2∑+态的束缚振动能级和基态的连续能级X2Π之间的frank - condon重叠的计算表明,ν= 2-5能级的弱预解可能是由于基态的直接预解,而不是由于另一个激发态的交叉。对发射线强度的精确测量可以验证这一假设。
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引用次数: 8
Chemical reactions with accelerated ions. Chemical effects of 32P+-ions implanted in NaCl single crystals 与加速离子的化学反应。32P+离子注入NaCl单晶的化学效应
Pub Date : 1971-01-01 DOI: 10.1039/TF9716703540
T. Andersen, A. Ebbesen
An electromagnetic isotope separator has been used for implantation of 40 keV 32P+ ions in single crystals of sodium chloride. The penetration of the implanted ions and their diffusion during storage at various temperatures have been measured by a new chemical sectioning technique. The chemical distribution of the 32P-ions has been determined after dissolution of the crystals. It reflects the variation in range distribution observed by varying the angle between the incident beam and the (100) plane. Deeply penetrating tails have a high content of the 32P(V)-precursor. A close correlation is established between the 32P(V)-precursor and changes in the range distribution due to diffusion. The chemical distribution depends to some extent on reactions occurring during dissolution. Thermal- and photo-annealing show the existence of two 32P(I)-precursors.
用电磁同位素分离器将40kev - 32P+离子注入氯化钠单晶中。用一种新的化学切片技术测量了注入离子在不同温度下的渗透和扩散。在晶体溶解后,测定了32p离子的化学分布。它反映了通过改变入射光束与(100)面之间的角度所观察到的距离分布的变化。深穿透尾翼中32P(V)前驱体含量高。32P(V)前驱体与扩散引起的范围分布变化密切相关。化学分布在一定程度上取决于溶解过程中发生的反应。热退火和光退火表明存在两种32P(I)-前驱体。
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引用次数: 6
Ion-exchange equilibria of synthetic 4A zeolite with Ni2+, Co2+, Cd2+ and Zn2+ ions 合成4A沸石与Ni2+、Co2+、Cd2+和Zn2+离子的离子交换平衡
Pub Date : 1971-01-01 DOI: 10.1039/TF9716700999
I. Gal, O. Janković, S. Malčić, P. Radovanov, M. Todorović
Linde 4A zeolite was converted to Ni, Co, Zn and Cd forms by replacing sodium ions with divalent cations. The replacement was from 82%(Ni) up to 100%(Cd). Chemical, T.G.A., D.T.A. and X-ray analysis of the divalent metal zeolites have been made and data on the composition of the unit cells and the thermal stability of the lattices were obtained. Ni-zeolite is unstable, its crystal lattice being completely destroyed above 70°C, whereas Co-, Zn- and Cd-zeolites are stable up to 750–850°C. The adsorption of water on the latter zeolites is reversible. Ion-exchange isotherms for Co2+, Zn2+ and Cd2+ at three temperatures were obtained and the thermodynamic functions, ΔG°, ΔH° and ΔS°, of the ion-exchange equilibria calculated. The thermodynamic data are discussed with respect to hydration and size of the cations. A possible explanation of the instability of Ni-zeolite is suggested.
用二价阳离子取代钠离子,将林德4A沸石转化为Ni、Co、Zn和Cd。替换量从82%(Ni)到100%(Cd)。对二价金属沸石进行了化学分析、热能谱分析、差热能谱分析和x射线分析,得到了单元胞的组成和晶格的热稳定性数据。ni -沸石不稳定,其晶格在70°C以上完全破坏,而Co-, Zn-和cd -沸石在750-850°C时稳定。后一种沸石对水的吸附是可逆的。得到了三种温度下Co2+、Zn2+和Cd2+的离子交换等温线,并计算了离子交换平衡的热力学函数ΔG°、ΔH°和ΔS°。热力学数据讨论了有关水化和大小的阳离子。对镍沸石的不稳定性提出了一种可能的解释。
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引用次数: 48
Ultra-violet spectrum of SiBr SiBr的紫外光谱
Pub Date : 1971-01-01 DOI: 10.1039/TF9716701870
G. Oldershaw, K. Robinson
The absorption spectrum of SiBr, observed in the flash photolysis of SiBr4, consists of the B2Σ—X2Π system and a number of new band systems at shorter wavelengths. One of these is shown to be analogous to the C2Π—X2Π systems of SiF and SiCl, and state C has the following parameters : Te= 41 051 cm–1, A= 12 cm–1, ωe= 531 cm–1, ωexe= 2 cm–1. Analyses of the remaining band systems are also discussed.
在SiBr4的闪光光解过程中观察到的SiBr的吸收光谱由B2Σ-X2Π体系和一些波长较短的新波段体系组成。其中一个被证明类似于SiF和SiCl的C2Π-X2Π系统,状态C具有以下参数:Te= 41 051 cm-1, A= 12 cm-1, ωe= 531 cm-1, ωexe= 2 cm-1。对剩余波段系统的分析也进行了讨论。
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引用次数: 6
期刊
Transactions of The Faraday Society
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