The design, the abilities and a characteristic application of an in-house made interface for combining thermogravimetry (TG)
with mass spectrometry (MS) are presented. The TG-MS interface consists mainly of three co-axial tubes. The position of the
intermediate tube was determined after calculation of the temperature profile at the TG furnace exit tube. The inner tube
position was determined taking into consideration its protection against condensation of heavy molecules and the time delay
for the transfer of the evolved gases. This interface allows either continuous sampling and transferring of the evolved gases
from the TG to the MS or repetitive introduction of short sampling pulses of TG evolved gases to MS. The interface is capable
of coupling various commercial instruments. In the present work two configurations of this interface are demonstrated. Finally
an example of application of this interface on forest fuel pyrolysis is presented.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
The ESR of the spin glassAgMn (2.7 and 9.6 at %) has been investigated below and aboveTg(0.1Tg<T<5Tg) at various microwave frequencies. The analysis yields:1) No explicit frequency dependence but strong magnetic field effects, inherent with ESR-experiments.2) Part of the excess line width is identified as critical spin fluctuations, following a power law. However, because of the presence of the applied field, the reduced temperaturet is not a good scaling variable. We choose the non-linear susceptibility Xs divided byH2, which scales as the order parameter susceptibility. The experiment yieldsWex(Xs/H2)p,p=0.42. From this we deduce z3. 相似文献
Thermogravimetry-mass
spectrometry (TG-MS) was used to study the effect of the inorganic salts (NH4)2SO4 and (NH4)2HPO4,
active substances of many commercial forest fire retardants, on the pyrolysis
of Pinus halepensis needles and their main
components (cellulose, lignin and extractives). These salts seemed to affect
the pyrolysis of cellulose by increasing significantly the char residue, decreasing
the pyrolysis temperature and changing the composition of the evolved gases,
that is, increasing levoglucosenone and decreasing oxygen containing volatile
products. (NH4)2SO4
seemed to have negligible effect on the pyrolysis of lignin, while (NH4)2HPO4 increased the char residue and decrease the relative contribution of guaiacols
in the evolved gases. No effects of the inorganic salts on the extractives
were observed. Finally, the inorganic salts seemed to affect the pyrolysis
of pine-needles, mainly the cellulose component, but the effects were not
as intense as in the pyrolysis of cellulose. 相似文献
Two types of Equations of State (EoS), which are characterized here as “simple” and “complex” EoS, are evaluated in this study. The “simple” type involves two versions of the Peng–Robinson (PR) EoS: the traditional one that utilizes the experimental critical properties and the acentric factor and the other, referred to as PR-fitted (PR-f), where these parameters are determined by fitting pure compound vapor pressure and saturated liquid volume data. As “complex” EoS in this study are characterized the EoS derived from statistical mechanics considerations and involve the Sanchez–Lacombe (SL) EoS and two versions of the Statistical Associating Fluid Theory (SAFT) EoS, the original and the Perturbed-Chain SAFT (PC-SAFT).
The evaluation of these two types of EoS is carried out with respect to their performance in the prediction and correlation of vapor liquid equilibria in binary and multicomponent mixtures of methane or ethane with alkanes of various degree of asymmetry. It is concluded that for this kind of systems complexity offers no significant advantages over simplicity. Furthermore, the results obtained with the PR-f EoS, especially those for multicomponent systems that are encountered in practice, even with the use of zero binary interaction parameters, indicate that this EoS may become a powerful tool for reservoir fluid phase equilibria modeling. 相似文献
The combined use of a dual‐UV detector, a fluorimetric one and of a multiple electrochemical (EC) detector equipped with a dual electrode, consisting of a conventional size 3 mm diameter glassy carbon electrode (GCE) and of a pair of 30 μm thick carbon microfibers, is proposed for the determination of 15 amino acids, two dipeptides and creatinine. This online coupling of the above detection modes could partially replace amino acid analysis by derivatization methods, since it solves problems concerning the direct detection of selected underivatized amino acids. Additionally, it was proved that the use of multiple‐detection allows positive peak identification in a single chromatographic run, yields more information for free amino acids and solves in some cases the problem of chromatographic resolution. In order to optimize the detection conditions of the underivatized amino acids and related compounds by different detectors, their detection characteristics were determined by adequate preliminary experiments. The electro‐oxidation characteristics of the underivatized compounds of interest were determined by hydrodynamic voltammetry using a flow cell with a macrodisc GCE and by ex‐situ voltammetry using both a GCE of conventional size and a carbon fiber disk microelectrode. Important practical advantages of microfiber and microdisk electrodes with respect to macroelectrodes were demonstrated. 相似文献
The UNIFAC model is extended to mixtures of ionic liquids consisting of the imidazolium cation and the hexafluorophosphate anion with alkanes, cycloalkanes, alcohols and water. Two new main groups, the imidazolium and the hexafluorophosphate groups, are introduced in UNIFAC. The required group interaction parameters between these groups and the existing UNIFAC main groups, CH2, OH and H2O, are determined by fitting binary liquid–liquid equilibrium and infinite dilution activity coefficient experimental data. The predictive capability of the extended UNIFAC model is examined against experimental data for vapour–liquid equilibrium, liquid–liquid equilibrium and activity coefficients at infinite dilution of binary and ternary systems containing 1-alkyl-3-alkyl′-imidazolium hexafluorophosphate ionic liquids, alkanes, cycloalkanes, alcohols and water. The results indicate that UNIFAC is a reliable model for phase equilibrium predictions in mixtures containing this type of ionic liquids. 相似文献
In order to evaluate the feasibility of CO2 sequestration in geological formations detailed knowledge of the mutual solubilities of the CO2/H2O system is required. In this work we employ three models, which all involve the well-known Peng–Robinson equation of state, to study the CO2/H2O phase equilibrium, with emphasis on the solubility of CO2 in the aqueous phase and the solubility of H2O in the CO2-rich phase. The considered models include the Peng–Robinson equation of state coupled with the conventional van der Waals one fluid mixing rules or the universal mixing rules, and the cubic-plus-association equation of state that uses the Peng–Robinson equation of state in order to account for the usual attractive and repulsive forces and an extra association term to account for the strong hydrogen bonding interactions. The required model parameters are calibrated using experimental data up to 1500 bar for pressure, and up to 673 K for temperature. To improve the accuracy of the proposed models we consider two temperature ranges. Temperatures lower than 373 K are of interest to the geological CO2 sequestration, while higher temperatures are of interest to fluid-inclusion studies. Good agreement is obtained between the experimental and the correlated solubilities. 相似文献