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111.
Liquid and solid cyclic peroxides derived from aliphatic ketones are explosive materials so their enthalpies of vaporization
and other thermodynamic or condensed-phase properties cannot be measured directly. In this work the enthalpies of vaporization
of peroxides at 298.15 K were estimated simply from gas chromatographic retention times measured at different temperatures.
The technique correlates changes in the retention times of compounds whose enthalpies of vaporization are known (called the
reference series), with those of the compounds of interest. If t
R′ is the adjusted retention time (retention time of each compound minus the retention time of unretained diethyl ether, used
as solvent) a plot of ln t
R′ against 1/T for each compound (reference compounds and cyclic peroxides) results in a straight line (r
2 > 0.99 for all compounds). The enthalpy of transfer from solution to the vapor state (Δsolg
H
m) can be obtained by multiplying the slope by the gas constant (R). A second plot correlates the enthalpies of transfer from
solution to the vapor state (Δsolg
H
m), as measured by gas–liquid chromatography (GLC), with enthalpies of vaporization of reference materials (Δvap
H
m at 298.15 K) available in the literature. C9–C15 fatty acid methyl esters and hydrocarbons were used as reference compounds. The enthalpies of vaporization of the cyclic
organic peroxides were calculated from the equation of the line obtained in this second correlation, the slope of which was
Δvap
H
m (at 298.15 K)/Δg
sol
H
m. The experiments were performed under isothermal conditions with a DB-5 capillary column, flame-ionization detection (FID),
and nitrogen as carrier gas. The column temperature was varied over a range of at least 30–70 K between 403 and 473 K, with
chromatograms being acquired at 10 K intervals. Enthalpies of vaporization of cyclic organic peroxides are not available in
the literature, and the values given in this paper, obtained by gas chromatography, are the first to be reported. 相似文献
112.
F. Munari A. Trisciani G. Mapelli S. Trestianu K. Grob J. M. Colin 《Journal of separation science》1985,8(9):601-606
Two-dimensional chromatography of gasoline by on-line coupled HPLC-HRGC, as described in this paper, allows separate GC analysis of paraffins and aromatics. The GC system contains a retention gap of only 10 m length for introducing HPLC fractions of 100 μl volume. This becomes possible through evaporation of part of the solvent during introduction of the HPLC eluent. This “partially concurrent solvent evaporation” technique allows transfer of large volumes of HPLC eluent into relatively short retention gaps, maintaining the full efficiency of the solvent effects in reconcentrating the bands of the early eluted solutes. 相似文献
113.
The molecular intrinsic characteristic contour (MICC) is defined as the set of all the classical turning points of electron movement in a molecule. Studies on the MICCs of some medium organic molecules, such as dimethylether, acetone, and some homologues of alkanes, alkenes, and alkynes, as well as the electron density distributions on the MICCs, are shown for the first time. Results show that the MICC is an intrinsic approach to shape and size of a molecule. Unlike the van der Waals hard-sphere model, the MICC is a smooth contour, and it has a clear physical meaning. Detailed investigations on the cross-sections of MICCs have provided a kind of important information about atomic size changing in the process of forming molecules. Studies on electron density distribution on the MICC not only provide a new insight into molecular shape, but also show that the electron density distribution on the boundary surface relates closely with molecular properties and reactivities. For the homologues of alkanes, Rout(H), Dmin, and Dmax (the minimum and maximum of electron density on the MICC), all have very good linear relationships with minus of the molecular ionization potential. This work may serve as a basis for exploring a new reactivity indicator of chemical reactions and for studying molecular shape properties of large organic and biological molecules. 相似文献
114.
Summary We have investigated to which extent retention data, acquired on single capillary columns, can be used for predicting retention factors in a coupled column system. For this purpose we utilized a model mixture of 18 lipid components with widely different vapor pressures and polarities. The sample was chromatographed on two columns, SB-biphenyl-30 (70% methyl-30% biphenylpolysiloxane) and SB-cyanopropyl-50 (50% methyl-50% cyanopropylsiloxane). Experimental retention factors, acquired in coupled column systems with two columns connected in different order, were thus compared with values calculated from runs on each single column. The agreement between calculated and experimental values generally was better than 5% without any pressure drop correction.To study the possibility of predicting retention behavior in a wide pressure range from a limited number of experiments, we also investigated the relation between solute retention and mobile phase density. We found that all data could be fitted to second order equations, which gives the possibility to optimize the resolution with respect to pressure from a limited number of runs at different pressures. 相似文献
115.
The molecular intrinsic characteristic contour (MICC) is defined based on the classical turning point of electron movement in a molecule. Three typical organic molecules, I.e. Methane, methanol and formic acid, were employed as examples for detailed introduction of our method. Investigations on the cross-sections of MICC provide important information about atomic size changing in the process of forming molecules. The electron density distributions on the MICCs of these molecules were calculated and shown for the first time. Results showed that the electron density distribution on the MICC correlates closely with molecular chemical properties, and it provides a new insight into molecular boundary. 相似文献
116.
Summary The influence of the isothermal temperature, program rate, initial temperature and flow rate on retention indices was studied. The methods of Kováts, Van Den Dool and Local Lagrange Interpolation are compared. Ten experimental measurements were carried out on a capillary column coated with OV-101 stationary phase. 相似文献
117.
Janina Lulek Maurycy Opielewicz Katarzyna Szyrwińska Bart?omiej Milanowski 《Analytica chimica acta》2005,540(1):25-31
The database of the relative retention times (RRTs) of polychlorinated biphenyls (PCBs) reported in literature was used to calculate the retention indices (RIs) of all 209 PCB congeners on temperature programmed capillary column Rtx-5. Calculation of retention indices was based on reference series of seven congeners (PCB IUPAC Nos. 18, 52, 101, 143, 185, 203 and 206) that exhibit linear relative retention time behaviour as a function of chlorine number. The calculated indices were compared to those determined in our laboratory as well as to those obtained by other authors. The proposed indices system was applied for identification individual congeners in mixture of Aroclors 1242:1254:1260, using only reference series of PCBs. 相似文献
118.
以去离子水与乙二醇的混合液(体积分数分别为36.5%,48.7%,59.0%及71.2%,以下简称混合液)作为同轴传输线的绝缘介质,进行了μs级高电压负充电条件下的正电极击穿实验,研究了混合液的击穿电压、击穿时间、相对介电常数及电阻率与体积分数的关系。实验结果表明:在充电电压为20kV时,71.2%的混合液比36.5%的混合液的平均击穿电压提高25.1%,平均击穿时间延长10.49%,而相对介电常数减小868%。同时,随着充电时间的缩短,混合液的击穿电压提高。 相似文献
119.
《高分子化学》课程是大部分工科化工、材料类专业的必修课程,如何在工科专业高分子化学课程教学中体现工科特色,成为大家关注的热点.针对什么是工科特色,提出了本人的见解.并就如何在教学过程中体现工科特色介绍了本人的探索与尝试. 相似文献
120.
In the dynamics analysis and synthesis of a con-trolled system, it is important to know for what feedback gains can the controlled system decay to the demanded steady state as fast as possible. This article presents a sys-tematic method for finding the optimal feedback gains by taking the stability of an inverted pendulum system with a delayed proportional-derivative controller as an example. First, the condition for the existence and uniqueness of the stable region in the gain plane is obtained by using the D-subdivision method and the method of stability switch. Then the same procedure is used repeatedly to shrink the stable region by decreasing the real part of the rightmost charac-teristic root. Finally, the optimal feedback gains within the stable region that minimizes the real part of the rightmost root are expressed by an explicit formula. With the optimal feedback gains, the controlled inverted pendulum decays to its trivial equilibrium at the fastest speed when the initial val-ues around the origin are fixed. The main results are checked by numerical simulation. 相似文献