Pulsed photothermal laser deflection for low-level smoke and NO2 measurements in engine exhausts

Pulsed Photothermal Laser Deflection (PLD) is developed to make temporally and spatially resolved measurements of NO₂ and smoke. The rapid response PLD signal is produced when a HeNe probe beam is deflected by a thermal lens produced by a pulsed XeCl-excimer laser pumped dye laser. The fast time response (30 ns) and good spatial resolution make the PLD method a candidate for future in situ measurements in turbulent engine exhausts. The PLD signals, measured in a sample cell, exhibit a linear response for NO₂ concentrations from 3 ppm to 208 ppm and for smoke concentrations from 0.3 mg/m³ to 10 mg/m³. With a low pulse energy of 4 mJ, single-shot PLD measurements in a sample cell have accuracies of ± 14 ppm for NO₂ indicating accuracies of ±0.7 mg/m³ for smoke. With increased pulse energy and multi-shot averaging, sensitivities of ± 0.4 ppm of NO₂ or ± 20 µg/m³ of smoke are expected.     

The nilpotence height of

A 20-year-old conjecture about the mod 2 Steenrod algebra The method of Walker and Wood is used to completely determine the nilpotence height of the elements in the Steenrod algebra at the prime 2. In particular, it is shown that for all , . In addition, several interesting relations in are developed in order to carry out the proof.

     

Salting-in of alcohols in aqueous solutions by tetraalkylammonium bromides at the freezing temperature

The freezing-point depression of the ternary systems tetraalkylammonium bromides-t-butanol-water for the first five homologs of R₄NBr was measured. In the case of Bu₄NBr, the effect of size of the alcohol (methahol ton-butanol) was also investigated. From the corresponding freezing-point data for the binary systems the apparent salting constants were calculated. The true salting constantsk _s were obtained by extrapolation to infinite dilution. These are all very close to zero at the freezing temperature. From the corresponding thermochemical data the temperature dependence ofk _s was calculated, and above 5°C all the R₄NBr salts int-butanol; the salting-in increases with temperature and with the size of the hydrophobic cations. The scaled-particle theory is at present the only one which can account semiquantitatively for the temperature dependence of the salting-in effect. On leave of absence from Chemistry Department, The University, Sheffield S3 7HF, England To whom correspondence should be addressed.     

Effects of concentrated matrices on the determination of trace levels of platinum and gold in aqueous samples using solvent extraction—Zeeman effect graphite furnace atomic absorption spectrometry and inductively coupled plasma—mass spectrometry

Two methods of determining trace levels of platinum and gold in aqueous solutions with high concents of total dissolved solids were investigated. The first involves preconcentration and separation of the precious metals from the interfering matrix by solvent extraction, followed by graphite furnace atomic absorption spectrometry (GFAAS) with Zeeman effect background correction. The direct determination of Pt and Au in solutions of high ionic strength by GFAAS is not desirable because of interference between elements in the matrix and the analyte, increased imprecision of analysis, greatly increased background absorbance leading to increased detection limits and rapid deterioration of the graphite tube. All the extraction methods for gold examined in this study resulted in decreased imprecision, increased sensitivity and lower background absorbance compared with direct measurements on the aqueous solution. All techniques also exhibited good recoveries (> 8%) and reproducibilities (relative standard deviation < 10%). The highest sensitivities for gold extraction from distilled water were obtained for dibutyl sulfide (DBS)—toluene and the lowest for cyanide—dibutyl ketone. The degree of extraction of Au was, however, dependent on the composition of the solution, indicating that standard and sample matrices should be closely matched even when employing solvent extraction. Solvent extraction was generally less successful for Pt. In order to obtain an acceptable imprecision in the Pt extractions, it was found that the use of SnCl₂ as a labilizing agent is essential for most of the techniques investigated.The second method was direct measurement by inductively coupled plasma mass spectrometry (ICP—MS). ICP—MS offers the advantages of a very low detection limit (100 ng l^?1 or better) without preconcentration and a large dynamic range. However, severe matrix effects can occur in concentrated solutions. Whereas high concentrations in solution of both sodium perchlorate and sodium chloride decrease the sensitivity, the presence of sulfide and natural organic (fulvic) acid increase the sensitivity for Pt and Au by a factor of up to 4. Sulfate, on the other hand, decreases the sensitivity of ICP-MS for Pt. The method of standard additions or isotope dilution is recommended for routine use to circumvent this problem, especially when the nature of the matrix is unknown or cannot be easily matched in the standards.