钇(Ⅲ)的二特戊酰基甲烷螯合物的合成、表征及热稳定性和升华性能研究

合成了钇(Ⅲ)的二特戊酰基甲烷螯合物(简称Y(DPM)₃)，并以红外光谱、核磁共振谱及X-射线物相分析进行了表征和鉴定。研究了这种β-二酮类螯合物的升华性能。结果表明，其升华速率与温度呈指数关系，与载气流量呈线性关系；通过测定蒸气压与温度之间的关系，求得130℃～164℃温度范围内的升华焓和升华熵，分别为135 kJ·mol^-1和265 J·mol^-1·K^-1。实验研究表明，该螯合物具有良好的挥发性和热稳     

标准差标准化方法修正的PBBs多效应3D-QSAR模型及其在环境友好性分子修饰中的应用

构建了标准差标准化方法修正的兼具多溴联苯(PBBs)分子红外振动强度、 生物富集性和毒性3种效应的CoMFA模型, 分析了PBBs分子力场对其综合值的影响, 确定取代位点, 并进行兼具易红外光谱检出、 低生物富集性和毒性特征的PBB分子修饰(以PBB-153为例). 研究结果表明, 构建的CoMFA模型对PBBs分子的红外振动强度、 生物富集性和毒性3种效应综合值具有较好的预测和拟合能力, 且具有较好的稳定性, 静电场和立体场的贡献率分别为59.9%和40.1%. 根据模型三维等势图选择正电性高于Br原子的5种取代基团对目标分子PBB-153进行单、 双取代, 筛选出6个3种效应综合值上升的PBB-153衍生物. PBBs衍生物分子单效应计算或预测结果验证表明所构建的兼具PBBs分子红外振动强度、 生物富集性和毒性3种效应综合值的CoMFA模型可以有效应用于PBBs分子的修饰. 设计的PBB-153衍生物分子具有较好的稳定性, 同时阻燃性与目标分子相当, 环境持久性及迁移性方面优于目标分子. 2D-QSAR模型表明, PBBs分子的偶极矩、 最负电荷及邻位Br原子数对其红外振动强度、 生物富集性和毒性单效应和综合值影响趋势一致.     

页岩油馏分的沸点与蒸气压

我们研究了抚顺页岩油馏分的温度与蒸气压的关系,谈现其变化规律基本上与天然石油或纯烃类近似.並且,丛实验结果,求得了计算页岩油馏分蒸气压经验式log P=A-B(T-43)中的常数A、B;制出页岩油的沸点压力对线图,换算误差最大为±2℃.     

外压与凝聚态物质饱和蒸气压关系的讨论

应用外压与饱和蒸气压的关系公式,推导了范霍夫公式和开尔文公式。温度一定时,平液面的饱和蒸气压只会大于或等于真空密闭系统中纯物质气液平衡时的饱和蒸气压。毛细管的凹液面还会出现比平液面的饱和蒸气压小的情况。该关系公式称为"凝聚相表面的压力与饱和蒸气压的关系公式"更为合理。     

稀溶液的渗透压、化学势、外压与蒸气压关系

以外压对化学势的影响为主线,从外压对化学势的改变和外压对稀溶液蒸气压的改变两个方面,讨论了稀溶液的渗透压、化学势、外压与蒸气压关系。以帮助学生更好地理解和掌握这些基本概念。     

共沸点存在的充分条件

以纯液体蒸气压和亨利系数为出发点,讨论了二组分气液相图存在共沸点的充分条件。结合纯液体蒸气压和亨利系数的物理意义,对共沸点存在的条件进行了说明。     

宽广温度范围的水离子积计算公式

宽广温度范围的水离子积是在理论上和实际应用上涉及面很广的重要物理化学性质之一.傅培鑫,Quist及Marshall等在总结实验数据的基础上提出了相应的计算水离子积的经验公式;Taylor还用热力学方法进行了计算.在饱和蒸气压及0～800℃范围内,以Marshall-Franck的经验公式准确度为最高,并由国际蒸气性质协会(IAPA)于1980年公布为计算宽广温度范围的水离子积公式.但是在温度较高(200～300℃)时,此公式的计算值与实验值之间的误差随温度升高而逐渐增大,平均误差为0.033pK_w单位.     

纯液体饱和蒸气压测定实验的改进

对纯液体饱和蒸气压测定实验进行了装置创新设计,该装置解决了该实验的一些关键问题:保证相平衡时的气相为纯液体蒸气;准确测定相平衡时的温度;方便有效地调节外压与液体蒸气压相等。改进后的装置设计合理,操作简单、快捷,消除了安全隐患,大大缩短了实验时间,可一人单独操作。     

钇(Ⅲ)的二特戊酰基甲烷螯合物的合成、表征及热稳定性和升华性能研究

合成了钇（Ⅲ）的二特戊酰基甲烷螯合物（简称Ｙ（ＤＰＭ）３），并以红外光谱、核磁共振谱及Ｘ射线物相分析进行了表征和鉴定。研究了这种β二酮类螯合物的升华性能。结果表明，其升华速率与温度呈指数关系，与载气流量呈线性关系；通过测定蒸气压与温度之间的关系，求得１３０℃１６４℃温度范围内的升华焓和升华熵，分别为１３５ｋＪ·ｍｏｌ－１和２６５Ｊ·ｍｏｌ－１·Ｋ－１。实验研究表明，该螯合物具有良好的挥发性和热稳定性，适用于气相色谱研究和制备薄膜的金属有机化合物源。     

气相色谱-质谱联用检测塑料产品中溴化阻燃剂

建立了气相色谱-质谱联用测定塑料产品中多溴联苯和多溴联苯醚的方法.以甲苯为提取溶剂,超声提取电子电气产品中多溴联苯(PBBs)和多溴联苯醚 (PBDEs),采用气相色谱-质谱法(GC-MS)检测.SCAN和SIM同时扫描,采用质谱特征离子定量分析.结果表明: 9种多溴联苯(PBBs)和10种多溴联苯醚(PBDEs)的线性关系、检出限、回收率和精密度都较好,RSD均<5.0%,PBBs回收率在97%～111%之间;PBDEs回收率在82%～115%之间.本方法前处理简便,灵敏度高,定性、定量分析准确可靠,且分析时间短,适用于塑料产品中PBBs和PBDEs的测定.     

Photolytic transformation of polybrominated biphenyls leading to the structures of unknown hexa- to nonabromo-congeners

Polybrominated biphenyls (PBBs) have been used as flame-retardants mainly in the 1970s. Nowadays, they are found as ubiquitous contaminants in environmental samples. 2,2',4,4',5,5'-hexabromobiphenyl (PBB 153) is one of the persistent organic pollutants whose global ban is currently under discussion. Like the polychlorinated biphenyls (PCBs), 209 PBB congeners are existing in theory. However, only approximately 40 PBBs have been identified to date. In this work, we therefore used UV light, a sun simulator and natural sunlight for the photochemical debromination of PBB 209. All techniques led to the reductive debromination of PBB 209 albeit at different speed. Shifts of bromine substituents were not observed. Normal phase and reversed phase high performance liquid chromatography (HPLC) was used for the isolation of 12 reaction products some of which could be identified by (1)H NMR (PBB 202, 201, 197, 208, and 207). The other isolates (PBB 179, 178, 176, 199, 197, 196, and 194) were identified by realization of photolytic transformation studies with all isolates followed by comparison and evaluation of the obtained product spectra. In this way, we were able to establish (relative) retention times of the three nonabromobiphenyls, 9 of the 12 octabromobiphenyls, 14 of the 24 heptabromobiphenyl, and 16 of the 42 hexabromobiphenyls. Data on 24 PBBs are presented for the first time. Evaluation of the samples showed that Br was alternately removed from both phenyl rings and that positions with two vicinal Br substituents were most affected. Likewise, ortho-substituted PBBs were enriched.     

Chromatographic enrichment and enantiomer separation of axially chiral polybrominated biphenyls in a technical mixture

The separation properties of different chromatographic methods regarding the enantioselective separation of axially chiral (atropisomeric) polybrominated biphenyls (PBB) were studied. For this purpose, the technical hexabromobiphenyl product Firemaster BP-6 was characterised by gas-chromatography coupled to electron capture detection (GC/ECD) and electron-capture negative ion mass spectrometry (GC/ECNI-MS) as well as by liquid chromatographic fractionating on active carbon and celite. Twelve individual PBBs including potential atropisomeric PBBs were isolated from Firemaster BP-6 by reversed-phase high-performance liquid chromatography (HPLC) on three serially coupled octadecylsilane columns. Six of the 12 isolated PBBs (three tri-ortho and di-ortho substituted PBBs, respectively) were separated into atropisomers on a HPLC column containing permethylated beta-cyclodextrin on silica. Moreover, the temperature dependency of the enantiomer separations is discussed. Gas chromatographic enantiomer separation of PBBs is a very demanding task due to high elution temperatures. However, the atropisomers of one tri-ortho substituted PBB congener (PBB 149) could be resolved on a column coated with randomly modified heptakis(6-O-tert.-butyldimethylsilyl-2,3-di-O-methyl)-beta-cyclodextrin in OV 1701.     

Analytical strategies for successful enantioselective separation of atropisomeric polybrominated biphenyls 132 and 149 in environmental samples

Some of the polybrominated biphenyls (PBBs) found in the environment are axially chiral, due to hindered rotation about the interannular phenyl-phenyl bond. This applies for PBB congeners having two or more bromine substituents in ortho-position to this bond. In this study analytical methods were developed that allow determining the enantiomer fraction (EF) of axially chiral (atropisomeric) PBBs in environmental samples. A white-tailed sea eagle egg was used as test sample. The egg extract was purified and further fractionated by normal phase (NP) high performance liquid chromatography (HPLC), yielding enriched fractions of axially chiral PBB 132 and PBB 149. Gas chromatographic (GC) enantioseparation of the atropisomers of PBB 149 was achieved on one of nine tested modified cyclodextrin phases. Due to coelution with an unknown brominated compound, conventional GC/ECNI-MS, which is based on the detection of the bromide ion, did not allow for the establishment of the EF. However, by means of GC/EI-MS-MS it was possible to verify an EF of 0.42-0.43, i.e. a significant enantiomeric enrichment of the second eluting atropisomer of PBB 149 in the white-tailed sea eagle egg. This is the first proof of non-racemic proportions of a chiral PBB in environmental samples. Despite the testing of nine different chiral stationary phases, GC enantioseparation of PBB 132 or other atropisomeric PBB congeners failed. For this reason, an enantioselective reversed-phase HPLC method was developed. This method proved to be a powerful tool for the separation of PBB atropisomers. It was found that even a standard of the di-ortho substituted PBB 153 could be partially separated into atropisomers at 0 degrees C but already enantiomerized at 5 degrees C. For establishing the EF of PBB 132 in the bird egg sample a combination of enantioselective HPLC followed by non-chiral gas chromatography was employed. Using enantioselective HPLC, the atropisomers of PBB 132 were quantitatively targeted into two separate fractions at room temperature (20 degrees C). After addition of internal standards for volume adjustment the relative amounts of the atropisomers in the isolated fractions were quantified by using non-chiral GC/EI-MS analysis. A deviation from the racemic mixture of the atropisomers of PBB 132 in the egg extract could not be statistically proven.     

Determination of vapor pressures using gas chromatography

The determination of vapor pressures, p0, of compounds with low vapor pressures (10(-8) Pa < p0 < 10(3) Pa) is becoming increasingly important as a result of the need to measure p0 for environmentally sensitive compounds such as organophosphorus pesticides, biphenyls, dioxins and alkylbenzenes. Under strict conditions, the components of gas-liquid chromatography (GLC) (a volatile solute, an involatile solvent and a mobile carrier gas) are in equilibrium and as a result it is possible to use the technique to measure equilibrium properties such as vapor pressure. The technique is rapid, reliable and reproducible. These advantages have tempted many workers to measure physiochemical properties, including vapor pressures, under conditions for which the basic theories do not hold. In this review, the GLC techniques used to measure vapor pressures from GLC data together with the basic theory, limitations of the techniques and some recent measurements are discussed.     

气相色谱质谱法分析土壤中多溴联苯和多溴联苯醚类化合物

建立了气相色谱-质谱法(GC-MS)分析土壤中的18种多溴联苯(PBBs)和多溴联苯醚类(PBDEs)化合物的方法.利用快速溶剂萃取(ASE)技术和凝胶净化系统(GPC)进行土壤样品的前处理,(13)C标记物作为进样内标和替代标,采用电子轰击源气相色谱质谱法(GC-EI/MS )分析-溴至七溴代PBBs和PBDEs,负...     

气相色谱-质谱法测定人血清中多溴联苯

建立了血清中8种多溴联苯(PBBs,包括BB-15、18、52、101、153、180、194和206)的气相色谱-质谱检测方法。采用Oasis HLB固相萃取柱对血清样品中的多溴联苯进行萃取和初步净化,再使用自制的硅胶/酸化硅胶固相萃取柱(Sep-Pak silica/acidified silica)进行进一步的净化,并以正己烷为洗脱溶剂洗脱,氮吹洗脱液浓缩至100 μL后上样分析。以DB-5ms色谱柱(15 m×0.25 mm×0.1 μm)分离样品,在选择离子监测(SIM)模式下进行质谱检测,使用同位素内标法对8种目标物进行准确定量。结果显示,8种多溴联苯单体的方法检出限(LOD,以3.14倍标准偏差计)为0.002～0.029 ng/mL,方法定量限(LOQ,以10倍标准偏差计)为0.008～0.092 ng/mL;低、中、高3个加标水平的平均回收率为74.24%～119.49%,相对标准偏差(RSD)为1.23%～12.02%。采用本方法测定标准参考物质SRM1957和SRM1958中的BB-153含量,结果在参考值范围内。本方法准确、灵敏、操作简便,适用于血清中多溴联苯的测定。     

Vapor pressure and density of thermotropic liquid crystals: MBBA, 5CB, and novel fluorinated mesogens

The vapor pressures and densities of six thermotropic liquid crystal-forming molecules (mesogens) have been determined experimentally as functions of temperature. The ubiquitous mesogenic compounds n-(4-methoxybenzylidene)-4-butylaniline (MBBA) and 4'-cyano-4-n-pentylbiphenyl (5CB), which both exhibit room-temperature nematic phases, are examined in this study, as are a number of trifluorinated bicyclohexyl and cyclohexylbiphenyl derivatives which find modern use in display applications. Although thermotropic mesogens are of prime importance in modern optoelectronic technologies, there is a scarcity of reliable saturation pressure data for such systems. An apparatus suitable for measurements of vapor pressures between 0.1 and 1333 Pa in the temperature range 298-523 K has been constructed. The adequacy of the apparatus has been verified by measurements on n-hexadecane at temperatures between 304 and 372 K, corresponding to vapor pressures between 0.4 and approximately 100 Pa. To our knowledge, our measurements represent the first reliable data for the saturation pressure of the fluid phase of these types of thermotropic compounds; we show that existing data for MBBA is thermodynamically inconsistent. The densities of the fluid phases of these compounds are also measured by means of a glass pycnometer at temperatures between 293 and 368 K.     

Determination of polybrominated biphenyls in Tasmanian devils (Sarcophilus harrisii) by gas chromatography coupled to electron capture negative ion tandem mass spectrometry or electron ionization high‐resolution mass spectrometry

Two gas chromatography/mass spectrometry (GC/MS) methods for the determination of polybrominated biphenyls (PBBs) by isotope dilution analysis (IDA) using ¹³C₁₂‐PBB 153 in the presence of polybrominated diphenyl ethers (PBDEs) were compared. Recovery of ¹³C₁₂‐PBB 153 which was added to the extracted lipids before sample purification was commenced ranged from 88–117% (mean value 98.2 ± 8.9%). Nevertheless, IDA analysis of PBBs using ¹³C₁₂‐labelled congeners is limited by the potential co‐elution of PBBs with polybrominated diphenyl ethers (PBDEs). The pair PBB 153 and BDE 154 was inspected since M⁺ and [M–2Br]⁺ ions of ¹³C₁₂‐PBB 153 and BDE 154 were only separated by 4 u. Gas chromatography/electron ionization high‐resolution mass spectrometry with selected ion monitoring (GC/EI‐HRMS‐SIM) was suitable when m/z 475.7449 and m/z 477.7429 were used for ¹³C₁₂‐PBB 153 because they are below the monoisotopic peak of the [M–2Br]⁺ fragment ion of hexaBDEs at m/z 479.7. Gas chromatography/electron capture negative ion tandem mass spectrometry selected reaction monitoring (GC/ECNI‐MS/MS‐SRM) measurements could be applied because ¹³C₁₂‐PBB 153 and BDE 154 were separated by GC on a 25‐m Factor Four CP‐Sil 8MS column. Comparative measurements with GC/EI‐HRMS‐SIM and GC/ECNI‐MSMS‐SRM were carried out with samples of Tasmanian devils from Tasmania (Australia), an endangered species due to a virus epidemy which has already proved fatal for half of the population. Both techniques verified concentrations of PBB 153 in the range 0.3–11 ng/g lipids with excellent agreement of the levels in all but two samples. The PBB residue pattern demonstrated that PBB pollution originated from the previous discharge with technical hexabromobiphenyl which is dominated by PBB 153. Other congeners such as PBB 132 and PBB 138 were detected in the Tasmanian devils but the proportions relative to PBB 153 were lower than in the technical product. Samples of healthy and affected Tasmanian devils showed no significant difference in the PBB pollution level. The PBB concentrations in the Tasmanian devils were significantly below those causing toxic effects. On the other hand, PBB concentrations were one level or even higher than PBDEs. Copyright © 2008 John Wiley & Sons, Ltd.     

Predicting gas chromatographic retention times of 209 polybrominated diphenyls (PBBs) for different temperature programs

A method has been developed to predict the retention times of 209 individual polybrominated diphenyl congeners for different temperature programs. The retention equations lnk=A+B/T of five PBBs in gas chromatography (GC) were used to evaluate the properties of the regression coefficients A and B, which are widely accepted as being highly reliable chromatographic retentions. The quantitative relationships between the A and B values of PCBs and those of PBBs were found. The regression equations derived have coefficients of determination greater than 0.999. The A, B values of any PBB can be predicted by using the A, B values of the PCB according to these relationships. Using these predicted A and B values, the retention times of all PBBs can be predicted. This is an important advance in the identification of PBBs because at present there are only a few PBB standards available.