大量锆存在下铪镧钼杂多酸-耐尔蓝体系测定铪

本文研究了耐尔蓝(NB)-铪镧钼杂多酸(HfLaMo-聚乙烯醇(PVA)体系测定铪的超高灵敏光度法。在PVA存在下,铪、镧和钼酸铵形成杂多酸,继而与耐尔蓝形成离子缔合物。其适宜条件为[HClO_4]=1.2mol/L,[La~(3+)]=2.9×10~(-7)mol/L,[MoO_4~(2-)]=1.1×10~(-3)mol/L,[NB]=2.7×10~(-6)mol/L,PVA0.08％。离子缔合物的最大吸收波长在590nm,表观摩尔吸光系数ε值为1.5×10~7L·mol~(-1)·cm~(-1),至少稳定96h,服从比耳定律范围为0～250ng/25ml。考察了35种共存离子的影响,容许200倍量Zr(Ⅳ)、As(Ⅲ),300倍量TiO_2、Sb~(3+)、SiO_3~2,100倍量Ge(Ⅳ)及10倍量P(Ⅴ),大多数元素不干扰,几种干扰可用溶剂萃取分离。本法已用于岩矿中铪的测定,结果满意。用摩尔比法和平衡移动法测定缔合物的摩尔比为Hf:La=1:3,探讨了反应机理。     

丁基罗丹明B-碲钼杂多酸缔合显色反应的研究

本文研究了在聚乙烯醇(PVA)存在下,丁基罗丹明B(BRB)与碲钼杂多酸的离子缔合显色反应,碲钼杂多酸在0.025～0.075 mol/L硫酸溶液中形成丁基罗丹明B-碲钼杂多酸离子缔合物。形成酸度为1.26～2.16 mol/L硫酸,钼酸铵、丁基罗丹明B及PVA的适宜条件分别4.6×10~(-3)mol/,5.3×10~(-5) mol/L和0.16％。缔合物最大吸收波长为570 nm,表观摩尔吸光系数ε值为3.2×10~5 L·mol~(-1)·cm~(-1),符合比耳定律范围0～16μg Te/25ml。探讨了反应机理,用平衡移动法确定缔合物的摩尔比为Te:Mo:BRB=1:7:2,缔合物的可能化学式为(BRB)_2[TeMo_7O_(24)]。方法已用于烟尘中碲的测定,结果满意。     

铑(Ⅲ)-钼酸盐-丁基罗丹明B缔合显色反应的研究

在聚乙烯醇(PVA)存在下,铑与钼酸盐和丁基罗丹明B(BRB)形成寓于缔合物,缔合物的最大吸收峰位于570nm,摩尔吸光系数ε值为3.22×10~5L·mol~(-1)·cm~(-1),服从比耳定律范围0～8μgRh/25ml,摩尔比Rh:BRB1:4:,缔合物至少稳定240h。测定铑的适宜条件为C_(HCIO_4)=1.5mol/L,C_(MoO_4~(8-)),3.3×10~(-8)mol/L,C_(BRA)=3.8×10~(-5)mol/L,PVA0.08％。考察了41种共存离子的影响,常见元素不干扰。本法已用于催化剂和回收液中铑的测定,结果满意。本文还探讨了反应机理。     

磷钼钛酸-耐尔蓝-聚乙烯醇体系光度法测定痕量钛

在0.9～1.3mol/L高氯酸介质中,Ti(Ⅳ)、P(Ⅴ)与钼酸铵反应形成磷钼钛杂多酸,在聚乙烯醇(PVA)存在下,杂多酸与耐尔蓝(NB)形成离子缔合物。离子缔合物的最大吸收位于590nm,表观摩尔吸光系数为1.94×10~5L·mol~(-1)·Cm~(-1),服从比耳定律范围0～4.8μgTi/25ml。主要组成摩尔比为Ti:P:NB:1:3:3。至少稳定5h。此法用于某些钢样和铝合金中钛的测定,结果满意。     

金-钼酸铵-罗丹明B体系显色反应的研究

研究了在高氯酸和聚乙烯醇(PVA)存在下金与钼酸盐和罗丹明B(RB)的显色反应,其适宜条件为C_(HClO)=0.81mol/L,C_(MoO)~(2-)=1.4×10~(-3)mol/L,C_(RB)=3.3×10~(-5)mol/L及0.08％PVA。λ_(max)=570nm,表观摩尔吸光系数C为2.65×10~5L·mol~(-1)·cm~(-1),服从比耳定律范围0～10μg Au/25ml。缔合物至少稳定2周,摩尔比Au:RB=1:2。考察了39种共存离子的影响,大多数贱金属不干扰。泡沫塑料分离富集金后,用于岩矿及冶金产品中金的测定,结果满意。     

夜蓝与阴离子表面活性剂在水溶液中显色反应——吸光光度法测定环境水样中阴离子表面活性剂

在聚乙烯醇存在的1.8mol/L磷酸溶液中,夜蓝与阴离子表面活性剂形成离子缔合物。溶液由绿色变为蓝色,可用于水相直接光度测定阴离子表面活性剂。最大吸收波长555nm,摩尔吸光系数分别为5.72×10~4L·mol~(-1)·cm~(-1)(十二烷基苯磺酸钠),5.77×10~4 L·mol~(-1)·cm~(-1)(十二烷基硫酸钠),4.36×10~4 L·mol~(-1)·cm~(-1)(十二烷基磺酸钠)。方法简便、快速,具有良好的选择性。可用于河水和生活废水中10~(-6)—10~(-7)mol/L阴离子表面活性剂的测定。     

铂（Ⅳ）—钼酸盐—丁基罗丹明B缔合显色反应的研究

本文研究在聚乙烯醇(PVA)存在下,铂与钼酸铵和丁基罗丹明B(BRB)形成离子缔合物,该缔合物的最大吸收位于570nm,摩尔吸光系数ε值为9.26×10~5L·mol~(-1)·cm~(-1),服从比耳定律范围0～3.0μg Pt/25ml,缔合物至少稳定3周。测定铂的条件为C_(HClO_4)=1.4mol/L,C_(MoO_4~(2-)=1.1×10~(-3)mol/L,C_(BRB)=3.8×10~(-5)mol/L,0.08％PVA。考察了40多种共存离子的影响,除形成杂多酸的元素外,大多数不干扰。本法已用于催化剂和某些铂矿中铂的测定,结果较满意。     

耐尔蓝-12-钼锗酸-聚乙烯醇体系测定锗

本文报告了在聚乙烯醇(PVA)存在下,在高氯酸水溶液中以耐尔蓝(NB)-12-钼锗酸体系灵敏光度法测定锗。讨论了定量形成12-钼锗酸(GeMo)及耐尔蓝-12-钼锗酸离子缔合物(NB-GeMo)的适宜条件。NB-GeMo的最大吸收位于605nm,表观摩尔吸光度ε值为9.08×10~5L·mol~(-1)·cm~(-1),服从比耳定律范围为0～4.0μgGe/25ml,至少稳定16h。用平衡移动法和摩尔比法测定了主要组分的摩尔比为NB:GeMo=9:1。红外光谱图表明,高氯酸根参与了缔合物组成。本法已用于实物中锗的测定,结果满意。     

分光光度法测定高纯氧化铝中的二氧化硅

在含有明胶聚乙烯醇 (PVA)和草酸的 0 .0 1 2～ 0 .0 60 mol/L 盐酸介质中 ,罗丹明 B(RB)与硅钼杂多酸能形成离子缔合物 ,发生高灵敏显色反应 ,缔合物在 585nm处的表观摩尔吸光系数ε=1 .8× 1 0 5L· mol-1· cm-1,缔合物可稳定 2 4 h以上 ,此法已用于测定高纯氧化铝中的二氧化硅     

耐尔蓝-铌钼杂多酸-聚乙烯醇-124体系测定铌

在聚乙烯醇-124存在下,耐尔蓝与铌钼杂多酸形成离子缔合物的适宜条件为:在0.025～0.10mol/L硫酸溶液中形成铌钼杂多酸;在1.1～1.8mol/L硫酸溶液中耐尔蓝与铌钼杂多酸形成离子缔合物。缔合物的组成比为NB:NbMo=3:1,λ_(maX)在615nm处,摩尔吸光系数ε为2.46×10~6L.mol~(-1).cm~(-1),符合比耳定律范围0～1.2μg Nb/25ml,至少稳定5h。考察了43种共存离子的影响,绝大多数元素不干扰测定。方法选择性好,灵敏度高,已用于合金钢和岩矿中铌的测定,结果满意。     

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.     

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。     

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.

     

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.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

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.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。