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151.
B A Finnin M A A O'Neill S Gaisford A E Beezer J Hadgraft P Sears 《Journal of Thermal Analysis and Calorimetry》2006,83(2):331-334
Isothermal
calorimetry is becoming indispensable as a tool for the study of a wide variety
of systems. As with all scientific instruments it is essential that robust
calibration routines be developed in order to validate the data obtained.
Chemical test reactions offer many advantages over (the traditionally used)
joule effect heating methods, not least because they have the potential to
validate instrument performance (i.e. they can be used to assess all aspects
of calorimeter operation). In this work the results of a validation exercise,
conducted by Thermal Hazard Technology as part of an installation routine,
using the base catalysed hydrolysis of methyl paraben are discussed. In the
case described, a systematic misreporting of the reported temperature of a
calorimeter was identified, caused by an upgrade to the calorimeter's
firmware, a discrepancy which may not have been noted using traditional electrical
calibration methods and one which highlights the importance of both manufacturers
and end-users adopting chemical test reactions into their test and validation
routines. 相似文献
152.
The absorption spectrum of neodymium (III) (Nd3+ doped in poly(methyl methacrylate) was measured. The Nephlauxetic effect was found in the spectrum compared to other spectra of Nd3+ doped in various matrices. The experimental data used, Slater-Condon parameters (F2,F4,F6) and Lander parameter (ζ4f) were calculated by the Taylor series expansion based on the assumption that the energy separation between J-levels of the 4fn-configuration is a function of F2,F4,F6 and ζ4f. The Judd-Ofled intensity parameters (Ω2,Ω4,Ω6) were also calculated. Analysis of the Nephlauxetic effect and the parameters variation on the host matrices was carried out. 相似文献
153.
A method is proposed for the simultaneous determination of albumin and immunoglobulin G (IgG1) with fluorescence spectroscopy and multivariate calibration with partial least squares regression (PLS). The influence of some instrumental parameters were investigated with two experimental designs comprising 19 and 11 experiments, respectively. The investigated parameters were excitation and emission slit, detection voltage and scan rate. When a suitable instrumental setting had been found, a minor calibration and test set were analysed and evaluated. Thereafter, a larger calibration of albumin and IgG1 was made out of 26 samples (0-42 μg ml−1 albumin and 0-12.7 μg ml−1 IgG1). This calibration was validated with a test set consisting of 14 samples in the same concentration range. The precision of the method was estimated by analysing two test set samples for six times each. The scan modes tested were emission scan and synchronous scan Δ60 nm. The results showed that the method could be used for determination of albumin and IgG1 (albumin, root mean square error of prediction (RMSEP) <2, relative standard error of prediction (RSEP) <6% and IgG1, RMSEP <1, RSEP <8%) in spite of the overlapping fluorescence of the two compounds. The estimated precision was relative standard deviation (R.S.D.) <1.7%. The method was finally applied for the analysis of some sample fractions from an albumin standard used in affinity chromatography. 相似文献
154.
155.
反应条件对煤加氢热解产物分布的影响 总被引:2,自引:3,他引:2
本文以内蒙古红庙煤为研究对象,在温度450-650℃和氢氯压力2-5MPA的范围内,在加压固定床反应器上考察了各种因素包括传质作用对煤加氢热解产物分布的影响。研究表明,转化率和焦油收率随最终反应温度,氢气压力和流速的升高而升高,随加速速率的增大而降低。 相似文献
156.
The polarography of lead ion in dimethyl sulfoxide (DMSO) was investigated in the DMSO concentration range 0–80 vol.%. The complex species identified were Pb2(DMSO)4+3, Pb(DMSO)2+3 and Pb(DMSO)2+6 in [DMSO]<10 vol.%, 10< [DMSO]<43 vol.% and [DMSO]>43 vol.%, respectively. In the presence of pamoic acid, the reduction of lead ion in DMSO was two-electron reversible diffusion-controlled at pH≤6.0, but it became irreversible at pH>6.0. The complex species identified was Pb(Dm)2(Pm)3(OH)6? at pH>6.0. The rate constants of electro-reduction and electro-oxidation, activation energies were determined. The hydrolysis constants of lead ion in dimethyl sulfoxide concentration 40–70 vol.% at pH 4.5–6.0 were found to be of the order of 10?6. The stability constants of the Pb(DMSO)2+3 and Pb(DMSO)2+0 were also determined to be of the orders of 101 and 105, respectively. 相似文献
157.
A new approach is developed for estimating the limit of detection in second-order bilinear calibration with the generalized rank annihilation method (GRAM). The proposed estimator is based on recently derived expressions for prediction variance and bias. It follows the latest IUPAC recommendations in the sense that it concisely accounts for the probabilities of committing both types I and II errors, i.e. false positive and false negative declarations, respectively. The estimator has been extensively validated with simulated data, yielding promising results. 相似文献
158.
B. V. Lebedev L. Ya Tsvetkova N. N. Smirnova 《Journal of Thermal Analysis and Calorimetry》1994,41(6):1371-1377
The heat capacitiesC 0 p of polybutene-1, polypentene-1, poly-4-methylpentene-1 and 4-methylphentene-1 were studied calorimetrically from 6 to (500–700) K. Temperatures, enthalpies of melting of various crystalline forms and the parameters of the glass transition were determined. The thermodynamic functionsH 0(T)?H0(0), S0(T) andG 0(T)?H0 (0) were calculated between 0 K and (500–700) K. From the calorimetric values obtained and literature data, the thermodynamic characteristics of the following processes were estimated for the corresponding alkenes-1, andcis-andtrans-alkenes-2: the polymerization of alkenes-1, the monomer-isomerization polymerization ofcis- andtrans-alkenes-2 to polyaklenes-1 and the isomerization ofcis- andtrans-aklenes-2 to alkenes-1 in the same temperature interval at standard pressure. 相似文献
159.
The viscosity deviation (Δη), the excess molar volume (V
E) and the ultrasonic speed (u) have been investigated from viscosity (η) and density (ρ ) measurements of binary liquid mixtures of 1,2-dimethyoxyethane with methanol, ethanol, propan-1-ol, butan-1-ol,
pentan-1-ol, hexan-1-ol or octan-1-ol over the entire range of composition at 298.15 K. The excess volumes are negative over
the entire range of composition for all of the mixtures with the exception of hexan-1-ol and octan-1-ol. The excess isentropic
compressibilities (K
S
E) and viscosity deviations are negative for all of the mixtures. The magnitudes of the negative values of V
E decrease with the number of carbon atoms of the alkan-1-ol. The trend of increasing K
S
E values with the chain length of the alkanol is similar to that observed in the case of V
E. Graphs of V
E, Δ η, K
S
E, Δ u, L
f
E and Z
E against composition are presented as a basis for a qualitative discussion of the results. 相似文献
160.
Zois Syrgiannis 《Tetrahedron letters》2006,47(17):2961-2964
The thermodynamic parameters, ΔΔH# and ΔΔS#, were determined for the interception of an intermediate, with the structural characteristics of an aziridinium imide, by nucleophilic solvents during the reaction of 2-methyl-2-butene with N-phenyltriazolinedione. The experimentally measured parameters were found to be in favor of an SN2-‘like’ transition state and showed strong dependence on the bulkiness of the incoming molecule of the nucleophile-solvent. 相似文献