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time during the transient regime which allows for the measurement of the associated induction period. The results obtained for the ignition of lean to stoichiometric n -pentane/air mixtures using this technique are reported and discussed. Although n

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Fluid radiation effects in the transient hot-wire technique

Measurement of thermal conductivity of propane

Journal of Thermal Analysis and Calorimetry
Authors: Y. Shi, L. Sun, F. Tian, J. Venart, and R. Prasad

Abstract  

The transient hot-wire technique is widely used for absolute measurements of the thermal conductivity of fluids. Refinement of this method has resulted in a capability for accurate and simultaneous measurement of both thermal conductivity and thermal diffusivity together with a determination of the specific heat. However, these measurements, especially those for the thermal diffusivity, may be significantly influenced by fluid radiation. The present work investigates the effect of fluid radiation on the measurements of the thermal conductivity of propane. Recently developed corrections have been used to examine this assumption and rectify the influence of even weak fluid radiation. Measurements at 372 K with a hot-wire instrument demonstrate the presence of radiation effects in both the liquid and vapor phase. The influence is much more pronounced in liquid propane at 15.5 MPa than in the vapor phase at 881.5 kPa. The technique employed to obtain radiation-free thermal conductivity measurements is described.

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Abstract  

The pulse-height distributions for131mXe in PPO solutions of aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, 2,4-dimethylpentane, 2,3,4-trimethylpentane, 1-pentene, 1-hexene and 1-heptene are investigated as a function of temperature. The pulse-height distributions are found to be shifted toward higher pulse-heights with decreasing temperature. The count rates of131mXe remain unchanged with decreasing temperature. The mechanism of the effect is also discussed.

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Abstract  

Adsorption of n-pentane, triethylamine, diethyl ether, acetonitrile and chloroform has been investigated on pyrogenic alumina (S=140 m2 g−1). The results of our studies have shown the presence of active sites on the surface of pyrogenic alumina with irreversible adsorption of electron-donating molecules and CHCl3 and the dependence of energetic surface properties on electronic structure of adsorbate, quantity of adsorbed substance and hydration degree of the surface. On the hydrated oxide surface the water molecules screen the active sites of the surface, which resulted in changing of interaction energy of adsorbent-adsorbate and decreasing the region of irreversible adsorption of organic bases and CH-acid.

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Abstract  

Heat capacity measurements have been made to investigate the formation of two solid monolayers each of n-pentane, n-heptane and n-dodecane adsorbed on graphite, one at submonolayer coverages and the other coexisting with the liquid. At submonolayer coverages the monolayers are found to melt respectively at 99.8, 151.6, and 217.3 K, well below the bulk melting points. The monolayers coexisting with the liquid melted at 205.6 for heptane and at 287.8 K for dodecane, whereas no evidence was obtained for pentane on the formation of such solid monolayer above the bulk melting point. The order persisting in the liquid near the interface depends upon the length of the molecules. The dodecane monolayers showed another transitions below the melting points both at submonolayer and multilayer coverages.

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Radiation effects in the transient hot-wire technique

Measurement of the thermal conductivity of n -pentane

Journal of Thermal Analysis and Calorimetry
Authors: Y. Shi, L. Sun, J. Venart, and R. Prasad

Abstract  

The transient hot-wire technique is widely used for absolute measurements of the thermal conductivity and thermal diffusivity of fluids. It is well established that fluid radiation effects significantly influence these measurements, especially those for the thermal diffusivity. Corrections for radiation effects are based on the models developed and deviations of the measured data from the ideal line source model. In this paper, the effect of fluid radiation on the measurements of the thermal conductivity of n-pentane is presented. For comparison, the influence of thermal radiation effect on measurement of transparent fluids, such as argon is also shown. The difference between the influence of natural convection and thermal radiation is also demonstrated.

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A 2D-separation of 16 polyaromatic hydrocarbons (PAHs) according to the Environmental Protecting Agency (EPA) standard was introduced. Separation took place on a TLC RP-18 plate (Merck, 1.05559). In the first direction, the plate was developed twice using n-pentane at −20°C as the mobile phase. The mixture acetonitrile-methanol-acetone-water (12:8:3:3, v/v) was used for developing the plate in the second direction. Both developments were carried out over a distance of 43 mm. Further on in this publication, a specific and very sensitive indication method for benzo[a]pyrene and perylene was presented. The method can detect these hazardous compounds even in complicated PAH mixtures. These compounds can be quantified by a simple chemiluminescent reaction with a limit of detection (LOD) of 48 pg per band for perylene and 95 pg per band for benzo[a]pyrene. Although these compounds were separated from all other PAHs in the standard, a separation of both compounds was not possible from one another. The method is suitable for tracing benzo[a]pyrene and/or perylene. The proposed chemiluminescence screening test on PAHs is extremely sensitive but may indicate a false positive result for benzo[a]pyrene.

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Abstract  

Fourteen organic compounds, 1-pentene, 2-methylbutane, 2-methyl-1,3-butadiene (isoprene),n-pentane, 2-chloropropane, ethyl alcohol, 2,2,4-trimethylpentane,n-hexane,n-hepatane, 1,3-difluorobenzene, 1,2-dichloroethane, hexafluorobenzene, cyclohexane and diphenyl ether, as new reference materials for energy and temperature calibrations of differential thermal analysers (DTA) and differential scanning calorimeters (DSC) in the temperature range 100–300 K, were investigated. The purities, triple point and transition temperatures, fusion and transition enthalpies of these compounds were measured using a low-temperature DTA apparatus developed by the CTM of the CNRS in Marseille. The results obtained were compared with those produced by adiabatic precision calorimetry. Our data are in good agreement with literature values. Enthalpies of fusion and transition, triple point and transition temperatures are reproduced within ±1% and ±0.1K, respectively.

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The present paper proposes a method that includes optimization of extraction process and high-performance thin-layer chromatographic (HPTLC) method for the rapid and simple quantification of two isomeric anticancer compounds (isogarcinol and garcinol) in Garcinia indica fruit and its validation according to the International Conference on Harmonization (ICH) guidelines. HPTLC of isogarcinol and garcinol was performed on precoated silica 60 F254S HPTLC plates. For achieving good separation, the mobile phase of n-pentane-ethyl acetate-formic acid (7:3:0.5, v/v/v) was used. Densitometric determinations of the investigated compounds were carried out at 327 nm in reflection-absorption mode. The calibration curves were linear in the range of 990 to 6900 ng for isogarcinol and 200 to 1400 ng for garcinol. The method was found to be reproducible and convenient for quantitative analysis of garcinol and isogarcinol in different solvent extracts of G. indica fruit. Our work demonstrated the optimization of the extraction procedure — rapid and sensitive quantification of two isomeric anticancer compounds — and its validation in the fruit extract of G. indica.

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Abstract

Compound-specific isotope analysis (CSIA) is fast becoming an important tool to provide chemical evidence in a forensic investigation. Attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large dataset is analyzed and the isotopic differences between samples are subtle. Thus, this study intends to demonstrate any linkages between diesel fuels in a large number of datasets where subtlety in the isotopic values is accentuated by the near single-point source of origin. Diesel fuels were obtained from various locations in the South Island of New Zealand. Aliquots of these samples were diluted with n-pentane and subsequently analyzed with gas chromatography-isotope ratio mass spectrometry (GC-IRMS) for carbon and hydrogen isotope values. The data obtained were subjected to principal component analysis (PCA) and hierarchical clustering. A wide range of δ13C and δ2H values were determined for the ubiquitous alkane compounds (the greatest values being −4.5‰ and −40‰, respectively). Based on the isotopic character of the alkanes it is suggested that diesel fuels from different locations were distinguishable and that the key components in the differentiation are the δ2H values of the shorter chain-length alkanes. However, while the stable isotope measurements may provide information to classify a sample at a broad scale, much more detailed information is required on the temporal and spatial variability of diesel compositions. The subtle differences of the stable isotope values within the alkanes of different diesel fuels highlighted the power of CSIA as a means of differentiating petroleum products of different origins, even more so when two or more stable isotopes data are combined. This paper shows that CSIA when used in tandem with multivariate statistical methods can provide suitable tools for source apportionment of hydrocarbons by demonstrating a straightforward approach, thus eliminating lengthy analytical processes.

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