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High field pulse measurements of the electric anisotropy of polarizability and the electric dipole moment of poly-γ-benzyl-L-glutamate 聚γ-苄基-谷氨酸的电各向异性极化率和电偶极矩的高场脉冲测量
Pub Date : 1971-01-01 DOI: 10.1039/TF9716701630
M. Gregson, G. Jones, M. Davies
High electric field pulse measurements have been made on dilute solutions of poly-γ-benzyl-L-glutamate (PBLG) in trans-1,2-dichlorethylene(I) and dioxan(II). One millisecond pulses of field amplitude up to 60 kV/cm have been used and the resulting changes in permittivity measured at 6 MHz. The measurements, which are analogous to Kerr effect birefringence work, yield values of the dipole moment and anisotropy of polarizability for PBLG. The values of the apparent dipole moment are 1930 D for (I) and 1410 D for (II), while the effective molecular anisotropy (α∥–α⊥) is 8.3 × 10–21cm3 for (I) and 10.5 × 10–21 cm3 for (II). Dispersion measurements on solution (I) led to a dipole moment of 1780 D.
对聚γ-苄基- l-谷氨酸(PBLG)在反式-1,2-二氯乙烯(I)和二氧六(II)中的稀溶液进行了高电场脉冲测量。使用了场振幅高达60 kV/cm的一毫秒脉冲,并在6 MHz下测量了由此产生的介电常数变化。测量结果与克尔效应双折射工作类似,包括偶极矩的屈服值和极化率的各向异性。(I)的视偶极矩值为1930 D, (II)的视偶极矩值为1410 D,而(I)的有效分子各向异性(α∥-α⊥)为8.3 × 10-21cm3, (II)的有效分子各向异性(α∥-α⊥)为10.5 × 10-21 cm3。溶液(I)的色散测量导致偶极矩为1780 D。
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引用次数: 19
Shear viscoelastic relaxation of a nitrate melt 硝酸熔体的剪切粘弹性松弛
Pub Date : 1971-01-01 DOI: 10.1039/TF9716701960
G. Glover, A. J. Matheson
The viscoelastic behaviour of a melt containing 62 mol % KNO3 and 38 mol % Ca(NO3)2 has been studied between 330 and 450 K using shear waves of frequencies 75 and 160 kHz and 5 and 30 MHz. The relaxation mechanism does not change over this range of temperature and frequency. Results may be described by a viscoelastic analogue of the Cole-Davidson expression for dielectric relaxation. This relationship also fits other common forms of viscoelastic behaviour such as that described by Barlow, Erginsav and Lamb.
用频率为75和160 kHz、5和30 MHz的剪切波,研究了含有62 mol % KNO3和38 mol % Ca(NO3)2的熔体在330和450 K之间的粘弹性行为。松弛机制在这个温度和频率范围内不会改变。结果可以用介电弛豫的Cole-Davidson表达式的粘弹性模拟来描述。这种关系也适用于其他常见形式的粘弹性行为,如Barlow, Erginsav和Lamb所描述的。
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引用次数: 15
Reactions of atomic carbon C(23PJ) by kinetic absorption spectroscopy in the vacuum ultra-violet 原子碳C(23PJ)在真空紫外线下的动力学吸收光谱研究
Pub Date : 1971-01-01 DOI: 10.1039/TF9716702025
D. Husain, L. Kirsch
Time-resolved attenuation of the atomic emission transition C(33P°J→23PJ) at 166 nm has been used to study the reactions of C(23PJ). The decay of this atom, following its generation by the vacuum ultra-violet flash photolysis of carbon suboxide, has been monitored directly in the presence of a number of gases. The following rate data for 300 K have been obtained: C(23PJ)+ NO →CN + O, k= 7.3±2.2 × 10–11 cm3 molecule–1 s–1, C(23PJ)+ O2→CO + O, k= 3,3±1.5 × 10–11 cm3 molecule–1 s–1, C(23PJ)+ N2O →CO + N2, k= 2.5±1.6 × 10–11 cm3 molecule–1 s–1, or CN + NO, C(23PJ)+ H2O →CO + H2k⩽3.6 × 10–13 cm3 molecule–1 s–1, or CH2O, C(23PJ)+ CO2→2CO, k≤ 10–14 cm3 molecule–1 s–1, C(23PJ)+ CH4→C2H4, k < 2 × 10–15 cm3 molecule–1 s–1, C(23PJ)+ N2+ M →CN2+ M, k= 3.1±1.5 × 10–33 cm6 molecule–2 s–1(M = Ar), C(23PJ)+ H2+ M →CH2+ M, k= 7.1±2.5 × 10–32 cm6 molecule–2 s–1(M = He), C(23PJ)+ CO + M →C2O + M, k= 6.3±2.7 × 10–32 cm6 molecule–2 s–1(M = He).
利用原子发射跃迁C(33P°J→23PJ)在166 nm处的时间分辨衰减,研究了C(23PJ)的反应。这个原子的衰变是在真空紫外线闪光光解一氧化碳后产生的,在许多气体的存在下直接监测到。300k的速率数据如下:C (23 pj) +没有→CN + O k = 7.3±2.2×10 - 11立方厘米molecule-1 s - 1, C (23 pj) + O2→CO + O k = 3, 3±1.5×10 - 11立方厘米molecule-1 s - 1, C (23 pj) +一氧化二氮→CO + N2, k = 2.5±1.6×10 - 11立方厘米molecule-1 s - 1,或CN +不,C (23 pj) + H2O→CO + H2k⩽3.6×10 - 13立方厘米molecule-1 s - 1,或CH2O, C (23 pj) +二氧化碳→2有限公司k≤10 - 14立方厘米molecule-1 s - 1, C (23 pj) + CH4→C2H4 k < 2×10 - 15立方厘米molecule-1 s - 1, C (23 pj) + N2 + M→CN2 + M k = 3.1±1.5×10-33 cm6 molecule-2 s - 1 (M = Ar), C (23 pj) + H2 + M→CH2 + M k = 7.1±2.5×10-32 cm6 molecule-2 s - 1 (M =他),C(23PJ)+ CO + M→C2O + M, k= 6.3±2.7 × 10-32 cm6分子- 2 s-1 (M = He)。
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引用次数: 96
Anodic oxidation of oxalic acid on gold 草酸在金上的阳极氧化
Pub Date : 1971-01-01 DOI: 10.1039/TF9716702167
J. W. Johnson, S. Mueller, W. James
The anodic oxidation of oxalic acid on Au has been studied at 80°C in aqueous media. The reaction rate was measured as a function of potential, oxalic acid concentration, pH, and temperature in H2SO4+ K2SO4+ KOH solutions of unit ionic strength. The oxalic acid was oxidized in acidic media to CO2. A first-order dependence of the rate on both pH and undissociated oxalic acid was found. The first decarboxylation step appears to be rate determining.
研究了80℃水溶液中草酸对金的阳极氧化反应。在单位离子强度的H2SO4+ K2SO4+ KOH溶液中,测定了反应速率与电位、草酸浓度、pH和温度的关系。草酸在酸性介质中氧化为CO2。发现了pH和未解离草酸对反应速率的一级依赖性。第一个脱羧步骤似乎是速率决定的。
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引用次数: 20
Thermal isomerization of cyclobutenes. Part 18.—1-Chlorocyclobutene and 1-bromocyclobutene 环丁烯的热异构化。部分18。- 1-氯环丁烯和1-溴环丁烯
Pub Date : 1971-01-01 DOI: 10.1039/TF9716702328
D. Dickens, H. Frey, J. Metcalfe
The thermal isomerization of 1-chlorocyclobutene yielded 2-chlorobuta-1,3-diene quantitatively by a homogeneous first-order reaction. In the temperature range 423–473 K and at pressures of 1 kN m–2 and above, rate constants were determined and yielded the Arrhenius equation, log (k1/s–1)= 13.26±0.03–140 750±270 J mol–1/2.303 RT. At pressures below 150 N m–2 the rate constant decreased with decreasing pressure. The thermal isomerization of 1-bromocyclobutene yielded 2-bromobuta-1,3-diene. This reaction was homogeneous and first order at pressures above 1 kN m–2. In this pressure region, rate constants were determined at 10 temperatures in the range 424–458 K. The rate constants fitted the Arrhenius equation, log (k2/s–1)= 13.53±0.06–141 270±510 J mol–1/2.303 RT. At 446.6 K the rate constant was determined at various pressures in the range 1.26 kN m–2–1.18 N m–2. The “fall-off” curve so obtained was compared with those obtained by the application of the RRKM theory.
1-氯环丁烯经一级均相热异构化反应定量生成2-氯-1,3-二烯。在423 ~ 473 K的温度范围内,在1 kN m-2及以上的压力下,测定了反应速率常数,得到了Arrhenius方程:log (k1/ s-1)= 13.26±0.03-140 750±270 jmol - 1/2.303 rt。在低于150 N m-2的压力下,反应速率常数随压力的减小而减小。1-溴环丁烯的热异构化反应生成2-溴环丁烯-1,3-二烯。当压力大于1kn - m-2时,反应是均匀的一级反应。在该压力区,在424-458 K范围内的10个温度下测定了速率常数。反应速率常数符合Arrhenius方程,log (k2/ s-1)= 13.53±0.06-141 270±510 jmol - 1/2.303 rt。在446.6 K下,在1.26 kN - m-2 - 1.18 N - m-2范围内测定了反应速率常数。并与应用RRKM理论得到的“衰减”曲线进行了比较。
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引用次数: 6
Heats of ionization of HO2 and OH in aqueous solution 水溶液中HO2和OH的电离热
Pub Date : 1971-01-01 DOI: 10.1039/TF9716702532
J. Baxendale, M. Ward, P. Wardman
Acid dissociation constants of OH and HO2 were measured over a range of temperature and give heats of ionization of 10 and 0 kcal mol–1 respectively. These values lead to ΔH°f of (O–2)aq and (O–)aq=–8(±2) and 9(±2) kcal mol–1 respectively. Solvation energies of O–2 and O– are estimated to be 94 and 113 kcal mol–1 and the E° of the couples O2/O–2, O/O–, –0.19 and 1.64 V respectively.
测定了OH和HO2在一定温度范围内的酸解离常数,得到的电离热分别为10和0 kcal mol-1。这些值导致(O - 2)aq和(O -)aq分别= - 8(±2)和9(±2)kcal mol-1的ΔH°f。O - 2和O -的溶解能分别为94和113 kcal mol-1, O2/O - 2、O/O -、-的E°分别为0.19和1.64 V。
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引用次数: 19
Spectroscopic and thermodynamic study of hexafluorobenzene + aromatic amine complexes 六氟苯+芳香胺配合物的光谱和热力学研究
Pub Date : 1971-01-01 DOI: 10.1039/TF9716702548
D. Armitage, T. G. Beaumont, K. C. Davis, D. Hall, K. W. Morcom
U.-v. spectrophotometric measurements of the association constants and enthalpies of formation for the complexes formed by hexafluorobenzene with N,N-dimethyl aniline (DMA) and N,N-dimethyl toluidine (DMT) are reported. Enthalpies of mixing of hexafluorobenzene with isopropylcyclohexane at 323.15 and 343.15 K are also reported. The spectrophotometric results correlate with the present enthalpy of mixing data taken in conjunction with the enthalpies of mixing for the hexafluorobenzene and amine systems reported previously.1
U.-v。用分光光度法测定了六氟苯与N,N-二甲基苯胺(DMA)和N,N-二甲基甲苯胺(DMT)的缔合常数和生成焓。还报道了六氟苯与异丙基环己烷在323.15 K和343.15 K下的混合焓。分光光度结果与当前混合焓数据相关联,并与先前报道的六氟苯和胺体系的混合焓相关联
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引用次数: 8
Equilibrium properties of polar gases. Part 2.—The second dielectric virial coefficients of some polar gases 极性气体的平衡性质。第2部分。-某些极性气体的二次介电维利系数
Pub Date : 1971-01-01 DOI: 10.1039/TF9716702915
A. N. Barnes, L. E. Sutton
The second dielectric virial coefficients ℬ for five polar gases CHF3, CHF2Cl, CH3Cl, CH2:CF2 and (CH3)2O were measured at 30, 50 and 70°C. for the gases CF3Cl and CF2Cl2, ℬ was measured at 50°C only. The experimental results were compared with those predicted by the forms of intermolecular potential that have been suggested for polar gases. None of these proves to be entirely satisfactory.
测定了5种极性气体CHF3、CHF2Cl、CH3Cl、CH2:CF2和(CH3)2O在30、50和70℃时的二次介电系数。对于CF3Cl和CF2Cl2气体,仅在50°C下测量。实验结果与极性气体分子间势的预测结果进行了比较。事实证明,这些方法都不完全令人满意。
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引用次数: 6
Heats of adsorption of organic bases on aerosilogels containing small quantities of aluminium 有机碱在含有少量铝的气凝胶上的吸附热
Pub Date : 1971-01-01 DOI: 10.1039/TF9716703118
S. G. Ash, A. V. Kiselev, B. Kuznetsov
Calorimetric heats of adsorption of the organic bases triethylamine and benzene on aerosilogels have been measured. The aerosilogels were prepared from industrial aerosils and dehydroxylated in vacuo at temperatures up to 1150°C. One sample of aerosilogel, which contained 0.4 % by weight of aluminium impurity, produced very active surface sites, which were characterized by a high initial heat of adsorption—about 50 kcal mol–1(209 kJ mol–1) for triethylamine and 20 kcal mol–1(84 kJ mol–1) for benzene. Other samples containing less than 0.02 % aluminium did not show this activity. Aluminium was artificially introduced into a pure sample of aerosilogel using aluminium nitrate solution. The adsorption properties of this sample were similar to those of the aerosilogel prepared from the impure aerosil containing 0.4 % aluminium.
测定了有机碱三乙胺和苯在气凝胶上的吸附热。气凝胶由工业气凝胶制备,并在真空中在高达1150℃的温度下脱氢。一种含有0.4%重量铝杂质的气凝胶样品产生了非常活跃的表面位点,其特征是高初始吸附热-三乙胺约为50千卡摩尔- 1(209千焦摩尔- 1),苯约为20千卡摩尔- 1(84千焦摩尔- 1)。其他含铝量低于0.02%的样品没有表现出这种活性。用硝酸铝溶液将铝人工引入到纯气凝胶样品中。该样品的吸附性能与由含0.4%铝的不纯气硅制备的气硅凝胶相似。
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引用次数: 10
Molecular acoustics. Part 7.—Ring inversion and internal rotation in some 2-halomethyl-1,3-dioxans 分子的音响。第7部分。-某些2-卤代甲基-1,3-二恶烷的环反转和内旋
Pub Date : 1971-01-01 DOI: 10.1039/TF9716703223
G. Eccleston, B. Walsh, E. Wyn-Jones, H. Morris
A double ultrasonic relaxation has been observed in some 2-halomethyl-1,3-dioxans. Using n.m.r., infra-red and previous knowledge of the ultrasonic relaxation behaviour of simple 1,3-dioxans the two relaxations have been assigned, in turn, to the perturbation of conformational equilibria involving ring inversion and internal rotation. From the temperature dependence of the relaxation times the barriers opposing these conformational changes have been derived.
在一些2-卤甲基-1,3-二恶烷中观察到双超声弛豫。利用新核磁共振,红外和先前对简单1,3-二恶烷的超声弛豫行为的了解,这两种弛豫依次被分配到涉及环反转和内旋转的构象平衡的扰动。根据弛豫时间的温度依赖性,推导出了阻止这些构象变化的势垒。
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引用次数: 6
期刊
Transactions of The Faraday Society
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