反气相色谱法对八异辛基倍半硅氧烷热力学性质的表征

采用反气相色谱技术,以23种溶剂为探针分子,表征了八异辛基倍半硅氧烷(octaisooctyl-POSS)的热力学性质,包括摩尔溶解焓、分子间相互作用参数、质量活度系数、Hansen溶度参数,并有效判断了溶剂探针分子与共聚物分子间的相互作用以及共聚物在这些溶剂中的溶解性.结果表明,在实验温度范围内(343 ～393 K),烷烃、芳香烃、卤代烃类、乙醚以及乙酸甲酯是octaisooctyl-POSS的良溶剂,乙酸乙酯、乙酸正丙酯、乙酸正丁酯与乙酸正戊酯是中等溶剂,醇类、丙酮以及四氢呋喃是不良溶剂;Hansen溶度参数表明,octaisooctyl-POSS与烷烃分子强烈的色散作用使其在烷烃溶剂中具有优良的溶解性能.     

Activity Coefficients at Infinite Dilution of Organic Compounds in Acetonitrile and Methanol by Liquid Chromatography

Abstract

Activity coefficients at infinite dilution of series of n-alkanes, n-alcohols, n-alkylbenzenes, cresols, α- and β-toluidine and γ -picoline in acetonitrile and methanol were determined at 25 °C by liquid-liquid chromatography. Apiezon L and Porapak Q were used as the stationary phases. For those components for which activity coefficients were available in the literature, there is reasonably good agreement with the data reported in this work, though in some cases the literature data were obtained by other techniques.     

反气相色谱法研究结晶聚合物的结晶行为

 :采用反气相色谱法(IGC)测定了结晶聚合物聚乙二醇(PEG)的熔点和结晶度,探讨了探针分子的性质、固定相中聚合物的涂布量对测定结果的影响,同时与热分析(DSC)方法测得的结果作了比较。结果表明,IGC法测定结晶性聚合物熔点和结晶度是一种非常实用可靠的技术,其优点在于并不依赖100%纯结晶聚合物的性质,PEG的熔点测得值为67℃,结晶度为89.7%,测定结果与DSC法的测得值(Tm=67.9℃,Xc=90.6%)相近,所测定的结果与探针分子的性质无关,但受PEG在担体上的涂布量的影响显著。     

Investigation of the Surface Properties of Graphene Oxide and Graphene by Inverse Gas Chromatography

The surface properties of graphene oxide (GO) and graphene (rGO) have been investigated for the first time using inverse gas chromatography at infinite dilution. The GO and rGO were prepared by classical Hummers method and chemical reduction method, respectively, and their structures were characterized using FT-IR, XDR, XPS, SEM, and TEM. It is found that their dispersive ( $ \gamma_{\text{s}}^{\text{D}} $ ), polar ( $ \gamma_{\text{s}}^{\text{P}} $ ), and total ( $ \gamma_{\text{s}}^{\text{T}} $ ) surface energies were 28.5, 18.0, 46.5 mJ m^?2 and 98.3, 6.60, 104.9 mJ m^?2 at 313.15 K, respectively. The results indicate that these samples differ in their surface properties, due to their structure (existence of oxygen-containing functional groups, of defects). By referencing the empirical relationship to establishing the donor (K _D) and acceptor (K _A) interaction parameters of the various samples, the Lewis acid–base character of the surface can be reliably identified. As a result, it is revealed that GO is a Lewis-base material, whereas rGO tends to be amphoteric but is also a Lewis-base material. Evaluation of surface properties of graphene could be used to guide the processing and application in graphene-based nanocomposites in the future.     

反相气相色谱法研究聚合物共混物的相溶性

 用反相气相色谱法测定了聚氯乙烯(PVC)／ 乙烯-醋酸乙烯共聚物(EVA)共混体系中分子间表观热力学相互作用参数χ′23,并以χ′23 为判定依据,研究了共混物的相溶性。 初步探讨了共混物的组成、聚合物分子 链结 构、温度与χ′23的关系以及探针分子性质 对χ′23参数的影响。结果表明：χ[ HT6〗′23值能够准确有效地判定PVC与EVA共混物的 相溶性,醋酸乙烯质量分数低的EVA与PVC的共混物是热力学不相溶的;而醋酸乙烯质量 分数中等的EVA与PVC的共混物则具有部分相溶性。结果与其它方法得到的结论是一致的 。     

反气相色谱法表征聚合物表面性质的方法比较

以聚甲基丙烯酸甲酯-丙烯酸丁酯-苯乙烯基七环戊基多面齐聚倍半硅氧烷三元共聚物为模型聚合物,全面介绍了反气相色谱技术表征聚合物表面性质的方法,探讨了不同的计算方法对测定结果的影响。结果表明:Schultz方法和Dorris/Gray方法均可用于计算聚合物的表面能的色散分量γsD,但两者测得的γsD值存在一定的差异,且随温度的升高,差异逐渐增大,Dorris/Gray方法更适合于计算聚合物的γsD;而Sawyer、Schultz和Papirer 3种方法都能表征聚合物表面与极性探针的特殊相互作用以及聚合物表面的酸碱特征,其中以溶剂探针的沸点作参照点的Sawyer计算方法更具有简单、快捷的优点,更具有实用性。     

气相色谱法测定汽油含氧化合物与苯

本着降低生产成本,开发仪器功能,提高工作效率,建立了双柱切换-反吹技术-气相色谱法(内标法)同时测定汽油中含氧化合物与苯。考察色谱阀的切换时间,柱温等因素对结果的影响,确定了最佳操作条件,同时对方法的精密度和重复性进行验证。结果表明,含氧化合物和苯的相对标准偏差为0.05%～0.2%,加标回收率分别为98.8%和96.7%,同时测定汽油中含氧化合物和苯方法的建立,其分析结果与石化标准方法分析结果一致。     

反相气相色谱法研究1,3,5-三氨基-2,4,6-三硝基苯的表面特性

采用反相气相色谱技术(IGC)研究了4种不同粒度的1,3,5-三氨基-2,4,6-三硝基苯(TATB)的表面性质。4种不同粒度的TATB表面自由能的色散分量（γds）随着温度的升高而增加;粒度越大的粒子,其色散自由能上升越快;在较高温度下,粗颗粒TATB显示了更强的色散作用(γds=193.2 mJ/m2,353 K),粒度最小的亚微米TATB显示了最弱的色散作用(γds=64.0 mJ/m2,353 K)。由于制备方法不同和粒子大小的差异,4种TATB的表面酸碱性质显示了明显的差别,细颗粒TATB表面有较强的亲电子特性;而其他3种TATB在极性探针分子的作用下的吸附均表现为吸热吸附,表现出在分子内和分子间具有强烈的相互作用,其Ka和Kb值均为负。     

Structures and Unexpected Dynamic Properties of Phosphine Oxides Adsorbed on Silica Surfaces

Solid‐state NMR spectroscopy of selected phosphine oxides adsorbed on silica surfaces establishes the surface mobilities, even of phosphine oxides with high melting points. Crystal structures of the adducts Ph₃PO ? HOSiPh₃ and Cy₃PO ? H₂O indicate that the interactions with silica involve hydrogen bonding of the P?O group to adsorbed water and surface silanol groups.     

丙酮—环烷烃体系的无限稀释活度系数的气提法测定研究

如果溶剂是高挥发性物质,当用气提法测定无限稀释活度系数时需要加预饱和釜以消除气提时因溶剂量损失过大而带来的问题.本文就丙酮-甲基环戊烷、丙酮-环己烧和丙酮-甲基环己烷3个体系在298.2～318.2K温度范围内的γ~∞作了测定,用所得数据作全浓度范围的汽液平衡推算,与文献中实验值对比,发现Wilson方程结果最佳.     

Polarity of Thymine and 6-Methyluracil-Modified Porous Polymers,According to Data from Inverse Gas Chromatography

Russian Journal of Physical Chemistry A - The affinity of surfaces of porous polymer Polysorb-1 samples modified with thymine (5-methyluracil) and 6-methyluracil toward sorbates capable of various...     

Study of CO Dissociative Adsorption over Pt and Rh Catalysts by Inverse Gas Chromatography

Carbon monoxide dissociative adsorption was studied over silica-supported platinum, rhodium and Pt-Rh alloy catalysts, by Reversed Flow-Gas Chromatography. Using appropriate mathematical analysis physicochemical quantities such as fractional catalytic conversions of CO to CO₂, as well as rate constants for the adsorption, desorption and surface reaction, describing the dissociative adsorption of CO, were determined. From the variation of the above parameters against the nature of the studied catalysts (Rh content) useful conclusions concerning the mechanism of CO dissociative adsorption were extracted.     

Thermodynamics of Adsorption ofn-Alkanes on Maleated Wood Fibers by Inverse Gas Chromatography

The adsorption ofn-heptane,n-octane,n-nonane, andn-decane on untreated wood fiber and wood fiber treated with maleated polypropylene was studied by inverse gas chromatography (IGC) at infinite dilution or zero surface coverage. The specific retention volume increased with increasing probe chain length, decreased with increasing column temperature, and increased with increasing maleated polypropylene concentration. The enthalpy of adsorption increased with increasing chain length of the probe vapors. The enthalpy of adsorption remained constant after the treatment of wood fiber. The London dispersive component of the surface free energy decreased with the column temperature and showed no dependency with either the type of wood fiber or the maleated polypropylene concentration.     

气相色谱法研究有机物在河流沉积物上的吸附

本文提出用有机物在沉积物上的色谱比保留体积值估算沉积物有机碳吸附系数，为此，以河流沉积物作气相色谱固定相，用测定气相色谱固定液相对极性和有机物比保留体积的方法，测定了沉积物相对极性和有机物在其上比保留体积，研究了Ｖｇ与Ｋｏｃ的相关性，结果表明，萘的线性关系式为ｌｏｇＫ＝０．１８＋３．１１（ｒ＝０．９８３１，ｎ＝５）。硝基苯的关系为ｌｏｇＫ＝０．２４ｌｏｇＶｇ＋２．５９（ｒ＝０．９５４４，ｎ＝５）．     

气相色谱法直接测定植物生长素

 建立了一种采用 5 3 0 μm大口径毛细管色谱柱、不经衍生化处理而直接测定吲哚乙酸 (IAA)、吲哚丁酸(IBA)和萘乙酸 (NAA)等植物生长素的气相色谱分析方法。以邻苯二甲酸二丁酯为内标物 ,用 FID检测 ,IAA,IBA和 NAA的相对标准偏差分别为 1 .1 4% ,0 .61 %和 0 .78%。方法简便、快速、准确、重现性好 ,可用于生长素类单组分和混合制剂的质量检测。     

气相色谱法研究聚辛烯-1与不同溶剂的热力学相互作用

用气相色谱法测定了聚辛烯－１与８种溶剂的Ｆｌｏｒｙ－Ｈｕｇｇｉｎｓ相互作用参数χ１和聚辛烯－１的溶解度参数,确定了χ１与温度的数学关系式。测定结果表明聚辛烯－１溶于正辛烷是一个放热过程。     

分子筛吸附性质的气相色谱研究

应用气相色谱分析法,研究了空气、氮气、氧气、甲烷在两种新合成的4A、5A分子筛上的吸附和分离性质,根据相关的吸附动力学模型导出了色谱峰与吸附热和吸附活化能关系的公式,并应用他们对检测数据进行了处理,得出了这两种分子筛对上述气体的吸附特征、选择性及吸附热和吸附活化能,以及气体保留时间、吸收峰面积与温度的关系。并且从分子筛的结构特征分析了吸附热和吸附活化能变化的原因。     

用气相色谱考察雌二醇的衍生化方法

用SP 370 0型气相色谱仪配以SE 5 2玻璃毛细管柱 (37m× 0 .33mmi.d .) ,以三氟乙酸酐等为衍化剂 ,对雌二醇的衍生化方法进行了研究 .着重讨论了衍生化条件、衍生化试剂、色谱条件对结果的影响 .确定了最佳衍生化和测定条件     

Evaluation of the Thermodynamic Parameters for the Adsorption of Some Hydrocarbons on Chemically Treated-Bentonites by Inverse Gas Chromatography

Inverse gas chromatography has been used to evaluate the adsorption parameters (ΔH_a, ΔH_st, ΔS_a and ΔG_a) of some probe molecules, each representing a class of organic (n-hexane, cyclohexane, benzene, n-octane, 1-octene and isooctane) on bentonite and chemically treated-bentonites. The adsorption parameters of the probes on the bentonite samples were determined in infinite dilution region. Adsorption of the organic species was investigated in the temperature range of 200–275^∘C, using a flame ionization detector, and nitrogen as a carrier gas. The net retention volumes (V_n) of the probes were determined by the help of the retention times (t_R) observed on gas chromatograms for each probe. Injection was made at least three times for each probe, obtaining reproducible results of ± 0.5%. It was found that benzene exhibits more negative ΔH than for n-hexane and cyclohexane on all of the adsorbents. In addition, it was found that 1-octene exhibits more negative ΔH than for n-octane and isooctane on the chemically treated-bentonites, whereas n-octane exhibits more negative ΔH than for 1-octene and isooctane on the natural bentonite. Also, interactions of benzene with the natural- and chemically treated-bentonites were found to be stronger than those of n-hexane and cyclohexane with the same carbon number. Again, interactions of the 1-octene with the chemically treated-bentonites were found to be stronger those of n-octane and isooctane with the same carbon number. On the contrary, interactions of n-octane with the untreated-bentonite were found to be stronger than those of 1-octene and isooctane.