The effect of capillary column diameter on the performance of thermal conductivity detectors

The concentration sensitivity of a thermal conductivity detector (TCD) depends, among other factors, on the amount of sample mixture in the detector's sensing cell. Since the cell volume has to be appropriately matched with column diameter, it makes the concentration sensitivity of a TCD dependent on column diameter and, therefore, on the speed of gas chromatography. Through reduction of column diameter, higher speed tends to lead to a reduction in the concentration sensitivity of the cell. The factor which the most directly affects the concentration sensitivity of a TCD cell is the heat power conducted through the cell. The higher the power, the greater the sensitivity. The limit of detection of a TCD depends on the concentration-sensitivity of its cell and on the level of statistical errors in the measurement. The errors increase with increasing analysis speed. As the column diameter is reduced, the errors cause additional worsening (on top of the decrease in concentration sensitivity) of the detection limit, dynamic range, and other performance characteristics of the TCD.     

氯化聚乙烯弹性体的固相法合成

讨论了以固相法合成氯化聚乙烯（ＣＰＥ）弹性体的过程．实验结果表明，以固相氯化反应所得的ＣＰＥ，其大分子链上Ｃｌ取代基的分布比水相悬浮法更均匀．氯化过程的温度直接影响氯化速度及分子结构，如残留结晶、氯分布等．而聚乙烯颗粒表面与内部的氯化程度取决于氯化速度．大分子链上Ｃｌ取代基对邻近基团的氯化起阻碍作用     

Effect of take-up speed on physical properties and permeation performance of cellulose acetate hollow fibers

Cellulose acetate (CA) ultrafiltration hollow fibers were spun via the dry-jet wet spinning technique. The effect of the take-up speed on the mechanical properties, morphology, thermal properties, pure water permeation, retention, and surface characterization of hollow fiber membranes were investigated. Both the inner and outer diameters of the hollow fiber decreased with the increase of take-up speed. Macrovoids were observed on the inner surface of the drawn hollow fibers. The d-space decreased with the increase of the take-up speed. The ultimate tensile stress (UTS) increased and the breaking elongation decreased with the increase of take-up speed. The permeation performance was measured. The hydraulic permeability increased and the retention decreased slightly with the increase of the take-up speed. The surface roughness increased with the increase of the take-up speed. The thermal analysis results showed that the endothermic peak shifts to the higher temperature region and coefficient of thermal expansion (CTE) decrease for a higher take-up speed.     

Analysis of dissolution test sample solutions by high speed capillary electrophoresis

Summary The quantitative use of high speed capillary electrophoresis (HSCE) is examined by applying high voltages across short capillaries. Acceptable performance in terms of injection precision and migration times were achieved within 1–2 minute analysis times. HSCE was used for the novel CE application of dissolution test sample solution analysis. The results generated by HSCE compared well with those generated using validated on-line UV absorbance measurements. It is concluded that HSCE is a viable alternative and supplement to standard analytical methods employed in dissolution test analysis.     

Sample decomposition in an electrically heated cold-trap inlet system for high speed gas chromatography

Thermal decomposition of some hydrocarbon and chlorinated hydrocarbon compounds in metal capillary tubes used in an inlet system for high speed gas chromatography has been investigated. The metal tube is cooled to about ?75°C by a flow of cold nitrogen gas in order to focus a vapor sample cryogenically. A capacitive discharge power supply is then used to heat the metal tube resistively in order to revaporize the sample and introduce it to the separation column as a plug 5-10 ms wide. The effects of tube temperature, tube material, sample vapor residence time, and type of carrier gas on thermal cracking are described. Use of a copper-nickel alloy tube resulted in less cracking than either pure platinum or pure nickel. Cracking is more significant with hydrogen as carrier gas than with helium. Cracking also increases with increasing sample residence time in the hot tube. Quantitative sample injection with minimum decomposition can be obtained for a variety of aliphatic and aromatic hydrocarbons and chlorinated hydrocarbon compounds.     

Thermodynamic properties of peptide solutions: 7. Partial molar isentropic pressure coefficients of some dipeptides in aqueous solution

The partial molar isentropic pressure coefficients at infinite dilution, K _S,2 ^o , have been determined for a number of dipeptides in aqueous solution at 25°C. For a series of dipeptides of sequence gly-X, where X is an amino acid with a neutral side chain, the K _S,2 ^o values are all more negative than that for diglycine. The results are discussed in terms of the hydration of the side chains. There are significant differences in the K _S,2 ^o values for sequence isomeric dipeptides. These differences can be rationalized in terms of the mutual interactions between the side chain and the ionic end groups in the dipeptides. Possible relationships between K _S,2 ^o and V ₂ ^o , the partial molar volume at infinite dilution, were investigated. For the dipeptides of sequence gly-X there is an interesting linear relationship between K _S,2 ^o /V ₂ ^o and V ₂ ^o .     

Effect of solvent composition on free release static coating of capillary columns

Summary Three aspects with respect to the selection of solvents for static coating of capillary columns, i.e. coating speed, occurrence of bumping and solubility of stationary phases are discussed. Hypotheses are proposed in an attempt to explain the observed facts that mixed solvents result in much higher coating speeds than those obtained from pure solvents, that a proper choice of solvents together with a good and uniform deactivitation of the column inner wall is needed to prevent bumping. Stationary phase solubility vs. solvent composition is also briefly discussed.     

The asymptotic equivalence of Bayes and maximum likelihood estimation

Let (X, $\text{A}$) be a measurable space, Θ ? $\text{R}$ an open interval and P_Ω ∥ $\text{A}$, Ω ? Θ, a family of probability measures fulfilling certain regularity conditions. Let $\text{Ω}{}_{\mathrm{n}}$ be the maximum likelihood estimate for the sample size n. Let λ be a prior distribution on Θ and let $\text{R}{}_{\mathrm{<mtext>n,</mtext><mtext>x</mtext>}}$ be the posterior distribution for the sample size n given $\text{x}\text{? X}{}^{\mathrm{n}}$. $\text{L:}\text{Θ}\text{× Θ →}\text{R}$ denotes a loss function fulfilling certain regularity conditions and T_n denotes the Bayes estimate relative to λ and L for the sample size n. It is proved that for every compact K ? Θ there exists c_K ≥ 0 such that

This theorem improves results of Bickel and Yahav [3], and Ibragimov and Has'minskii [4], as far as the speed of convergence is concerned.     

Influences of aerodynamic loads on hunting stability of high-speed railway vehicles and parameter studies

The influences of steady aerodynamic loads on hunting stability of high-speed railway vehicles were investigated in this study.A mechanism is suggested to explain the change of hunting behavior due to actions of aerodynamic loads：the aerodynamic loads can change the position of vehicle system（consequently the contact relations）,the wheel/rail normal contact forces,the gravitational restoring forces/moments and the creep forces/moments.A mathematical model for hunting stability incorporating such influences was developed.A computer program capable of incorporating the effects of aerodynamic loads based on the model was written,and the critical speeds were calculated using this program.The dependences of linear and nonlinear critical speeds on suspension parameters considering aerodynamic loads were analyzed by using the orthogonal test method,the results were also compared with the situations without aerodynamic loads.It is shown that the most dominant factors a ff ecting linear and nonlinear critical speeds are different whether the aerodynamic loads considered or not.The damping of yaw damper is the most dominant influencing factor for linear critical speeds,while the damping of lateral damper is most dominant for nonlinear ones.When the influences of aerodynamic loads are considered,the linear critical speeds decrease with the rise of cross wind velocity,whereas it is not the case for the nonlinear critical speeds.The variation trends of critical speeds with suspension parameters can be significantly changed by aerodynamic loads.Combined actions of aerodynamic loads and suspension parameters also a ff ect the critical speeds.The effects of such joint action are more obvious for nonlinear critical speeds.     

Physical Dimensions/Units and Universal Constants: Their Invariance in Special and General Relativity

The theory of physical dimensions and units in physics is outlined. This includes a discussion of the universal applicability and superiority of quantity equations. The International System of Units (SI) is one example thereof. By analyzing mechanics and electrodynamics, it naturally leads one, besides the dimensions of length and time, to the fundamental units of action $\mathfrak{h}$, electric charge q, and magnetic flux ?. Also, $q\times ?=\text{action}$ and $q/?=1/\text{resistance}$ are known. These results of classical physics suggests to look into the corresponding quantum aspects of q and ? (and also of $\mathfrak{h}$): The electric charge occurs exclusively in elementary charges e, whereas the magnetic flux can have any value; in specific situations, however, in superconductors of type II at very low temperatures, ? appears quantized in the form of fluxons (Abrikosov vortices). And $\mathfrak{h}$ leads, of course, to the Planck quantum h. Thus, one is directed to superconductivity and, because of the resistance, to the quantum Hall effect. In this way, the Josephson and the quantum Hall effects come into focus quite naturally. One goal is to determine the behavior of the fundamental constants in special and in general relativity.