两相滴定法测定对-叔丁基杯芳烃乙酸的基本常数

在25℃,利用两相滴定法测定了对-叔丁基杯芳烃乙酸tBu[4]CH2 COOH和tBu[6]CH2 COOH在纯水中的溶解度S和离解常数K,氯仿中二聚常数K2和氯仿.水两相之间的分配系数KD.实验测得tBu[4]CH2 COOH:S4=(2.03±0.04)×10-4 mol/L,Ka,4=(1.50±0.02)×10-5,KD,4=1.55×102和K2,4=3.73×102;tBu[6]CH2 COOH:S6=(1.25±0.05)×10-4 mol/L,Ka,6=(8.71±0.05)×10-6,KD,6=1.28×102和K2,6=3.88×102.     

第33届国际化学奥林匹克竞赛理论试题

一些有用的信息 　阿伏加德罗常数　ＮＡ=6 .0 2 2× 10 2 3 ｍｏｌ-1;电子电荷　ｅ=1.6 0 2× 10 -19Ｃ ;摩尔气体常数　Ｒ =8.315Ｊｋ-1ｍｏｌ-1;普朗克常数　ｈ =6 .6 2 6× 10 -3 4 Ｊｓ ;光速 (真空 )　ｃ =2 .998× 10 8ｍｓ-1;1原子质量单位　 1ｕ =931.5ＭｅＶ/ｃ2 ;1道尔顿　 1Ｄａ =1.6 6 1× 10 -2 7Ｋｇ ;1电子伏特　 1ｅＶ =1.6 0 2× 10 -19Ｊ ;1ｂａｒ=10 5Ｐａ　 10 5Ｐａ =10 5Ｎｍ-2 ;1 =10 -10 ｍ对于一个连续进行的一级反应 :Ａ Ｋ1 Ｂ Ｋ2 Ｃ[Ｂ]ｔ=Ｋ1[Ａ]0 [ｅ-Ｋ1 ｔ-ｅ-Ｋ2 ｔ]/ (Ｋ2 -Ｋ1)第 1题瑞士的一个教师巴…     

伪极谱法测定铅的氟化物存在下的形态及络合物稳定常数

采用阳极溶出伏安技术（ASV）──伪极谱法研究了铅在氟化物体系中的存在状态。结果表明：当Pb~(2+)浓度为2×10~(-7)mol/L,pH=8时,铅在NaF体系中以PbF~+、PbF_2、PbF_3~-、PbF_4~(2-)形式存在,并测定了形成这些络合物的积累稳定常数分别为:β_1=5．0,β_2=1．8×10~2,β_3=2．6×10~3,β_4=1．2×10~3。     

极谱催化波法测定马蔺子素

报道了在Na2 B4 O7 KH2 PO4 K2 S2 O8体系中马蔺子素的极谱催化波。拟定了测定马蔺子素的新方法。在 8.0× 10 - 3mol/LNa2 B4 O7 1.6× 10 - 2 mol/LKH2 PO4 (pH =7.7) 5 .0× 10 - 3mol/LK2 S2 O8底液中 ,极谱催化波峰电位Ep=-1.2 3V(vs .SCE) ;二阶导数峰峰电流i″p 与马蔺子素浓度在 2 .0× 10 - 9～ 2 .0× 10 - 6 mol/L范围内呈良好线性关系 ,检出限为 1.0× 10 - 9mol/L。催化波灵敏度比相应马蔺子素还原波高 75倍。采用该法测定了胶囊中马蔺子素的含量     

电泳中介微分析法测定铁(Ⅱ)和铜(Ⅱ)

利用电泳中介微分析通过与邻菲罗啉的络合反应完成了对Fe2+与Cu2+的同时测定。在压差作用下,淌度较小的邻菲罗啉在金属离子区带之前首先进样,加高电压后,两区带电泳在磷酸缓冲液中 (pH=4. 5)混合、反应形成络合物并实现电泳分离。研究了缓冲液pH、试剂和样品区带长度对分离效果的影响。对于Fe2+与Cu2+两离子,方法的检出限(S/N=3)分别为 1. 6和 11μmol/L;线性范围分别为 5. 0×10-6 ~3. 0×10-4 mol/L(r=0. 9979)和 8. 0×10-5 ~3. 0×10-4 mol/L(r=0. 9996)。采用标准矿样验证了测定Fe2+的可行性。     

第33届国际化学奥林匹克竞赛理论试题答案

1 - 1　ｎ =3时波长λＬ 最长 ,对于Ｈｅ+ ,1¨ｅ =ＲＨ(112 - 1ｎ2 )¨ｅＬ=16 4 1.1 1- 2　 1¨ｅ =ＲＨ(112 - 1ｎ2 ) ;ｎ =2 ,3,4 ,…Ｅ =-ｈｃＲＨ=- 13 6ｅＶ1- 3　最低能量 =- 2 0 7× 133.6 =- 2 .82ｋｅＶ第一玻尔轨道半径 =0 .5 3/ 2 0 7=2 .6× 10 -3 1- 4　几率 =|ψ(ａｏ) |2 4πａｏ2 × 0 .0 0 1ａｏ=0 .0 0 4ｅ-2 =5 .4 1× 10 -41- 51- 6　 (ｉ) 4 .7ｅＶ　　 (ｉｉ) 17.6ｅＶ1- 7　电子亲和能 =- 13.6 - (- 14 .3) =0 .7ｅＶ1- 8　 (13.6 +2 7.2Ｚ2 ｅｆｆ=0 .7Ｚｅｆｆ=0 .72 - 1　磷酸二氢根 (Ｈ2 ＰＯ-4)的共轭碱是磷…     

以酸性铬蓝K作为氢供体的酶催化光度法测定过氧化氢

研究了以酸性铬蓝 K作为氢供体底物的过氧化氢酶 -过氧化氢催化反应体系 ,拟定了测定痕量过氧化氢的新的酶催化光度法。测得该体系的最大反应速率 Vmax值为 6.2 5× 1 0 -3 mol· L-1·S-1,米氏常数 Km值为 2 .78× 1 0 -5mol/L。测定过氧化氢的线性范围为 0 .0 3～ 0 .6mg/L。检出限为 4.6× 1 0 -4 mol/L。方法可应用于雨水中过氧化氢的测定     

铁-荧光镓极谱络合吸附波的研究

在 p H6.1 0的 0 .1 mol/L ( CH2 ) 6 N4-HCl底液中 ,用单扫示波极谱法可获得铁( ) -荧光镓体系灵敏的络合吸附波。在 1 .0× 1 0 - 7～ 7.0× 1 0 - 6 mol/L范围内 ,铁浓度与波高呈线性关系 ,检测限达 7.0× 1 0 - 8mol/L,已成功地应用于金属镁粉中的铁和铝的测定 ,并测得电活性络合物的组成为铁∶荧光镓 =1∶ 1 ,条件形成常数β=3 .2× 1 0 4,表面电极反应速率常数 ks为 2 .9s- 1 。     

海水中二甲基硫亨利常数的测定

 推导了多次相平衡顶空气相色谱法测定海水中二甲基硫 (DMS)亨利常数 (K)的理论关系式 ,根据两次或多次气、液相平衡的关系式 ,只测定DMS在气相中的浓度就可测定亨利常数。实测 2 2℃时DMS在胶州湾海水中的亨利常数是 0 0 89,相对标准偏差为 5 5 0 %。亨利常数的对数与环境水体中NaCl的质量分数 [w(NaCl) ]之间的关系为 :logK =0 0 688·w(NaCl) - 1 3 5 68,相关系数为 0 997。亨利常数的对数与环境水体的绝对温度 (T)的倒数之间的相关方程为 :logK =- 15 4 4 8/T + 4 2 112 ,相关系数为 0 996。     

铍试剂Ⅲ/钙色素双偶氮染料-示波计时电位法快速测定天然水中不同形态铝

采用铍试剂Ⅲ (简称BER)和钙色素 (简称CAL)双偶氮染料 示波计时电位法快速测定天然水中不同形态铝。实验条件和结果如下 :在pH 5 .0NH4Ac HAc缓冲溶液中 ,BER在dE dt E示波图上出现一个切口 ,Ep1 =-0 .3 5V。加入铝后出现一新切口 ,Ep2 =-0 .70V ,该切口深度与加入铝量在 1 .0× 1 0 - 6 ～ 2 .0× 1 0 - 5mol L浓度范围内呈线性关系 ;检出限为 5 .0× 1 0 - 7mol L ;在 5 .0× 1 0 - 6 mol LAl时相对标准偏差为 5 5 % (n=1 0 )。在pH 8.0NH4Ac NH3·H2 O缓冲溶液中 ,CAL在示波图上出现一个切口 ,EP′1 =-0 .60V。加入铝后出现一新切口 ,EP′2 =-0 .75V ,该切口深度与加入铝量在 1 .0×1 0 - 6 ～ 1 .0× 1 0 - 5mol L浓度范围内呈线性关系 ,检出限为 5 .0× 1 0 - 7mol L ;在 2 .0× 1 0 - 6 mol LAl时 ,相对标准偏差为 5 .5 % (n =1 0 )。分别采用两种试剂在弱酸性和弱碱性条件下测定了天然水样中的铝浓度 ,发现在弱酸性下测定的是无机单核铝 ,而在弱碱性下则是总单核铝 ,据此可以实现对 5种铝形态的区分。测定了实际天然水样 ,与Driscoll方法进行了对照 ,结果基本一致     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate

The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m²g^-1 instead of aerosil with one of 175 m²g^-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended. This revised version was published online in July 2006 with corrections to the Cover Date.     

小环化合物中饱和碳质子化学位移的计算

小环化合物由于其张力、构型、构象和各向异性效应等原因,环碳上质子化学位移缺乏规律性,难以预测,对此作者曾提出一种近似算法。本文根据303种小环化合物中饱和碳质子的化学位移实验数据,将适于计算这类质子化学位移的公式表述为:     

解决能源问题的新途径--光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。