Phase transitions in chlorobenzene-cis-decalin mixtures

The dielectric constant ?' and loss tangent tan δ of chlorobenzene-cis-decalin mixtures have been measured in the temperature range 77 K to 330 K and frequency range 0.1 to 100 kHz. On cooling, ?' increases with decreasing temperature upto about 135 K, after which it drops rapidly with decreasing T followed by a slow decrease. This indicates that the liquid mixture goes to an amorphous phase which transforms to a glass phase of restricted dipole rotation below T_g; however, the peak in ?' is due to relaxation in the amorphous phase (α relaxation) and does not give an exact T_g. On heating, the behaviour of the cooling curve is retraced upto 160 K, after which ?' drops suddenly to a value lower than that at 77 K in the glass phase. This indicates the transition to a crystalline phase in which dipole rotational freedom is completely lost. The crystalline phase changes to a eutectic liquid phase of high ?' at a temperature (200 K) lower than the melting point of chlorobenzene and cis-decalin. Dielectric dispersion is observed only in the glass and amorphous phases. The dielectric relaxation time is independent of the concentration of chlorobenzene.     

The use of fluorescence in determining formation constants of complexes : Part II. Complexes which fluoresce

Four different methods for the calculation of the formation constants of fluorescing complexes are discussed. The methods were used to determine constants for the complexes of aluminum(III), gallium(III) and indium(III) with 8-quinolinol-5-sulfonate anion.     

Determination of the valence distribution of vanadium in polyolefin catalysts prepared from vanadium trichloride

An electrochemical method has been developed for determining the relative amounts of V(II) and V(III) in polyolefin catalysts prepared using aluminum alkyls and vanadium trichloride. The catalyst, usually obtained as a slurry in n-heptane, is titrated potentiometrically with ceric sulfate using a platinum indicator electrode. Under proper experimental conditions, 2 breaks are obtained, corresponding to the reactions V(II) →V(III) + e and V(III) →V(IV) + e. Interferences from other components of the catalyst are negligible. The method is useful for the analysis of both laboratory catalysts and grab samples taken from pilot plant reactors.     

Oxine complex of molybdenum

Molybdenum was reported to be precipitated quantitatively by 8-hydroxyquinoline in the pH range 3.3–7.6, the precipitated compound having the composition MoO₂(ox)₂. The pH range reported and the composition of the complex do not seem to be compatible with present knowledge of the pH stability of anionic and cationic molybdenum. It is now shown that under defined conditions, the precipitate is not formed at pH values higher than 2.24. In several estimations of other metals, molybdenum was masked by using a complexone at high pH values. It is now pointed out, that maintaining the solution at high pH value is itself sufficient and no other external complexing agent is necessary for masking molybdenum.     

Isocyanide addition to MN2(CO)5(Ph2PCH2PPh2)2 and the formation of a four-electron doubly-bridging isocyanide

The reactions of Fe(CO)₅, Fe(CO)₄P(C₆H₅)₃, M(CO)₆ (M  W, Mo, Cr), and (CH₃C₅H₄Mn(CO)₃ with KH and several boron and aluminium hydrides were investigated. Iron pentacarbonyl was converted quantitatively to K⁺Fe(CO)₄-(CHO) by hydride transfer from KBH(OCH₃)₃ allowing isolation of [P(C₆H₅)₃]₂-Nⁿ⁺Fe(CO)₄(CHO)^? in 50% yield. Lower yields were obtained with LiBH(C₂H₅)₃, and other hydride sources gave little or no formyl product. The stability of Fe(CO)₄(CHO)^? in THP was found to depend on the cation, decreasing in the order [P(C₆H₅)₃]₂N⁺ > K⁺ > Na⁺ > Li⁺. No formyl complexes were isolated and no spectroscopic evidence for formyl formation was observed in the reactions of the other transition metal carbonyls with several hydride sources. Fe(CO)₄-P(C₆H₅)₃ gave K₂Fe(CO)₄ when treated with KHB(OCH₃)₃. When treated with LiBH(C₂H₅)₃, W(CO)₆ gave a mixture of HW₂(CO)₁₀^?and (OC)₅W(COC₂H₅)^?; the latter was methylated to give the carbene complex (OC)₅WC(OCH₃)C₂H₅.     

Stability constants of iron(III)-8-hydroxyquinoline complexes

Spectrophotometric determination of the formation constants of iron(III)-8-hydroxyquinoline complexes in 0.1 M sodium perchlorate solution at 25° gave the values K₁=[FeOx²⁺]/([Fe³⁺][Ox^-])=4.9·10¹³, K₂=[FeOx₂⁺]/([FeOx²⁺][Ox^-])=4.2·10¹² and K₃=[FeOx₃]/([FeOx₂⁺][Ox^-])=3.9·10¹⁰. FeOx₂OH and FeOx(OH)₂ are obtainable as solid phases. FeOx₃ (K_sp=3·10^-44, intrinsic solubility 1.6·10^-7 M) dissolves in basic solutions to form FeOx₂(OH)₂ -In a solution saturated with FeOx³, ([FeOx₂(OH)₂^-][Ox^-])/[OH^-]²=7.7·10^-5.     

Total synthesis of (±) zoapatanol: a stereospecific synthesis of a key intermediate

The development of a stereospecific synthesis of a key intermediate in the synthesis of (±)-zoapatanol from the Weiland-Miescher ketone is described.     

Evaluating impacts of fish stock enhancement and biodiversity conservation actions on the livelihoods of small‐scale fishers on the Beijiang River,China

Inappropriate development and overexploitation have seriously degraded aquatic resources in China. Stakeholders identified three fish stock enhancement and biodiversity conservation scenarios for the Beijiang River: S1, increased fish restocking; S2, no fishing season and habitat conservation; and S3, strict pollution control. Potential impacts of these actions on the livelihoods of fishers were evaluated using applied economic modeling. Baseline costs and benefits came from logbooks from 30 fishers and a survey of 90 households in three villages. The financial net benefit for a household was US$1583 (￥11,160) annually, representing a 142% and 387% return on capital and operating costs, respectively. Larger catches associated with S1 and S2 generated a net benefit of US$1651 and US$1822, respectively. Strict pollution control resulting in higher catches (+20%) and lower operating costs (?20%) would increase the net benefit by 15.9% to US$1835 annually. Pollution control would benefit other resource users and is a prerequisite for ecological restoration. Recommendations for Resource Managers

• Stringent pollution control measures are essential to conserve aquatic biodiversity and enhance the livelihoods of fishers but will require considerable public and private sector investment.
• Enhanced fish stocks in the Beijiang River could benefit poor livelihoods but may not be sufficient to lift households out of poverty, aged fishers require government assistance to diversify their livelihoods, access alternative urban employment, and survive with dignity.
• Adopting the economic modeling approach presented here could enable responsible authorities to simultaneously evaluate fish stock enhancement and biodiversity conservation options.
• Broader application of the approach presented here could help ensure small‐scale inland fisheries are managed sustainably and aquatic ecosystems are restored and protected by 2020, in line with Target 6 of the United Nations’ Convention on Biological Diversity Strategic Plan for Biodiversity.

     

中职本科贯通应用型人才培养的无机化学教学探索

中职本科贯通生的中职阶段学习与普通高中学习存在着较大的区别,由于对基础知识未进行过系统强化训练,中职学生的理论知识较为薄弱;但由于较早进相关工厂见习或顶岗操作,其形象思维能力较强。在无机化学教学中,根据中职本科贯通生的特点,多采取探究式教学,让学生根据工厂生产中遇到的情况用自己的语言来描述一些概念和定义,"发现"一些原理,有利于培养应用型人才。     

济南地区表层土壤及沉积物中饱和烃分布特征及源解析

研究了济南地区不同功能区的表层土壤及沉积物中饱和烃的组成和分布特征,在此基础上初步分析了其来源.结果表明,饱和烃主要有正构烷烃、类异戊二烯、环烷烃等组成,正构烷烃碳数分布范围为n-C10-n-C34,类异戊二烯类主要是姥姣烷、植烷及甲基C13-C17烷等,同时还检出烷基环己烷,甾烷、三萜烷及藿烷等环烷烃.饱和烃总体含量分布为北高南低,北部化工区、高速入口处等饱和烃主要来源于原油或成品油等化石燃料及其燃烧产物;南部山区、水库沉积物及农田土壤等饱和烃主要来源于化石燃料的燃烧及高等植物.