Boron measurement

Two colorimetric methods are recommended for boron analysis. One is the curcumin method, where the sample is acidified and evaporated after addition of curcumin reagent. A red product called rosocyanine remains it is dissolved in 95 wt % ethanol and measured photometrically. Nitrate concentrations >20 mg/L interfere with this method. Another colorimetric method is based upon the reaction between boron and carminic acid in concentrated sulfuric acid to form a bluish-red or blue product. Boron concentrations can also be deterrnined by atomic absorption spectroscopy with a nitrous oxide—acetjiene flame or graphite furnace. Atomic emission with an argon plasma source can also be used for boron measurement. 

Marquis and Lebel [534] precipitated potassium from seawater or marine sediment pore water using sodium tetraphenylborate, after first removing halogen ions with silver nitrate. Excess tetraphenylborate was then determined by silver nitrate titration using a silver electrode for endpoint detection. The content of potassium in the sample was obtained from the difference between the amount of tetraphenyl boron measured and the amount initially added. 

The procedure of Mortier et al. (32) for the determination of boron in aluminium and aluminium-magnesium alloy is as follows The sample is irradiated for 20 min with a 2 uA beam of 7 MeV deuterons, which are degraded to 5.3-5.7 MeV, and a surface layer is removed by chemical etching (2.3.1). To separate the sample is dissolved in an oxidizing mixture of phosphoric acid, sulphuric acid and potassium dichromate. The C02 released is absorbed in 0.5 M sodium hydroxide and the activity measured with a t-t coincidence set-up. A pure decay is obtained. The chemical yield was checked by comparing, in a separate experiment, the activity of an aluminium sample, doped with 5000 tig/g of boron, measured instrumentally and after chemical separation. The yield was 100 %. 

The relative basicities of aromatic hydrocarbons, as represented by the equilibrium constants for their protonation in mixtures of hydrogen fluoride and boron trifluoride, have been measured. The effects of substituents upon these basicities resemble their effects upon the rates of electrophilic substitutions a linear relationship exists between the logarithms of the relative basicities and the logarithms of the relative rate constants for various substitutions, such as chlorination and... 

The methods of choice for beryUium oxide in beryUium metal are inert gas fusion and fast neutron activation. In the inert gas fusion technique, the sample is fused with nickel metal in a graphite cmcible under a stream of helium or argon. BeryUium oxide is reduced, and the evolved carbon monoxide is measured by infrared absorption spectrometry. BeryUium nitride decomposes under the same fusion conditions and may be determined by measurement of the evolved nitrogen. Oxygen may also be determined by activation with 14 MeV neutrons (20). The only significant interferents in the neutron activation technique are fluorine and boron, which are seldom encountered in beryUium metal samples. 

For the most part boric acid esters are quantitated by hydrolysis in hot water followed by determination of the amount of boron by the mannitol titration (see Boron compounds, boric oxide, boric acid and borates). Separation of and measuring mixtures of borate esters can be difficult. Any water present causes hydrolysis and in mixtures, as a result of transesterification, it is possible to have a number of borate esters present. For some borate esters, such as triethanolamine borate, hydrolysis is sufftciendy slow that quantitation by hydrolysis and titration cannot be done. In these cases, a sodium carbonate fusion is necessary. 

The electron probe X-ray microanalyzer provides extraordinary power for measuring the elemental composition of solid matter with pm lateral spatial resolution. The spatial resolution, limited by the spread of the beam within the specimen, permits pg samples to be measured selectively, with elemental coverage from boron to the actinides. By incorporating the imaging capability of the SEM, the electron probe X-ray microanalyzer combines morphological and compositional information. 

NAA cannot be used for some important elements, such as aluminum (in a Si or Si02 matrix) and boron. The radioactivity produced from silicon directly interferes with that ftom aluminum, while boron does not produce any radioisotope following neutron irradiation. (However, an in-beam neutron method known as neutron depth profiling C3J be used to obtain boron depth profiles in thin films. ) Another limitation of NAA is the long turn-around time necessary to complete the experiment. A typical survey measurement of all impurities in a sample may take 2-4 weeks. 

Fig. 3.24. Di rect-imaging mode SIMS image of a passivation layer on a niobium alloy [3.54], Boron enrichment at the interface is not visible with EPMA. Measurement time 10 s image diameter 150 pm primary ions OJ primary energy 5.5 keV.

As a second example, results from a TOP ERDA measurement for a multi-element sample are shown in Fig. 3.65 [3.171]. The sample consists of different metal-metal oxide layers on a boron silicate glass. The projectiles are 120-MeV Kr ions. It can be seen that many different recoil ions can be separated from the most intense line, produced by the scattered projectiles. Figure 3.66 shows the energy spectra for O and Al recoils calculated from the measured TOF spectra, together with simulated spectra using the SIMNRA code. The concentration and thickness of the O and Al layers are obtained from the simulations. 

The preceding restrictions on engineering constants for orthotropic materials are used to examine experimental data to see if they are physically consistent within the framework of the mathematical elasticity model. For boron-epoxy composite materials, Dickerson and DiMartino [2-3] measured Poisson s ratios as high as 1.97 for the negative of the strain in the 2-direction over the strain in the 1-direction due to loading in the 1-direction (v 2)- The reported values of the Young s moduli for the two directions are E = 11.86 x 10 psi (81.77 GPa) and E2 = 1.33x10 psi (9.17 GPa). Thus,... 

As an illustration of the results of the measurements just described, the mechanical properties for four unidirectionally reinforced composite materials, glass-epoxy, boron-epoxy, graphite-epoxy, and Kevlar 49 -... 

Pipes and Cole [2-25] measured the interaction term F,2 in various off-axis tests for boron-epoxy. They reported significant variation of F,2 for off-axis tension tests and acceptable variation for off-axis compression tests. However, compression tests are much more difficult to perform than simple off-axis tension tests on a flat specimen with a high length-to-width ratio. A compression specimen with a high length-to-... 

Rate constants have been measured for the reactions of boron compounds with a series of bromomethanes and bromofluoromethanes. Previously it was shown that the reactivity of the chlorine in chlorofluoromethane is substantially reduced by increasing fluorine substitution. The corresponding decrease in the reactivity of bromolluoromethane u as not observed [ifS]. 

Abundances of lUPAC (the International Union of Pure and Applied Chemistry). Their most recent recommendations are tabulated on the inside front fly sheet. From this it is clear that there is still a wide variation in the reliability of the data. The most accurately quoted value is that for fluorine which is known to better than I part in 38 million the least accurate is for boron (1 part in 1500, i.e. 7 parts in [O ). Apart from boron all values are reliable to better than 5 parts in [O and the majority arc reliable to better than I part in 10. For some elements (such as boron) the rather large uncertainty arises not because of experimental error, since the use of mass-spcctrometric measurements has yielded results of very high precision, but because the natural variation in the relative abundance of the 2 isotopes °B and "B results in a range of values of at least 0.003 about the quoted value of 10.811. By contrast, there is no known variation in isotopic abundances for elements such as selenium and osmium, but calibrated mass-spcctrometric data are not available, and the existence of 6 and 7 stable isotopes respectively for these elements makes high precision difficult to obtain they are thus prime candidates for improvement. 

On ihe Mohs scale diamond is 10 and quartz 7. An abemative measure is the Knoop hardness (kgmm ) as measured with a 100-g load typical values on this scale are diamond 7000, boron carbide 2750, corundum 2100. topaz 1340, quartz 820. hardened tool steel 740. 

For the particle size measurements of boron and barium dichromate, components of pyrotechnic delay compns, Freeman (Ref 46) evaluated the MSA. Particle Size Analyzer versus microscopy, gravitational liq sedimentation,... 

Olivier and Berger335, who measured the first-order rate coefficients for the aluminium chloride-catalysed reaction of 4-nitroben2yl chloride with excess aromatic (solvent) at 30 °C and obtained the rate coefficients (lO5/ ) PhCI, 1.40 PhH, 7.50 PhMe, 17.5. These results demonstrated the electrophilic nature of the reaction and also the unselective nature of the electrophile which has been confirmed many times since. That the electrophile in these reactions is not the simple and intuitively expected free carbonium ion was indicated by the observation by Calloway that the reactivity of alkyl halides was in the order RF > RC1 > RBr > RI, which is the reverse of that for acylation by acyl halides336. The low selectivity (and high steric hindrance) of the reaction was further demonstrated by Condon337 who measured the relative rates at 40 °C, by the competition method, of isopropylation of toluene and isopropylbenzene with propene catalyzed by boron trifluoride etherate (or aluminium chloride) these were as follows PhMe, 2.09 (1.10) PhEt, 1.73 (1.81) Ph-iPr, (1.69) Ph-tBu, 1.23 (1.40). The isomer distribution in the reactions337,338 yielded partial rate factors of 2.37 /mMe, 1.80 /pMe, 4.72 /, 0.35 / , 2.2 / Pr, 2.55337 339. 

Benkeser et a/.431 measured the relative rates of acetylation of alkylferrocenes using acetic anhydride catalysed by boron trifluoride etherate, in dichloromethane at 0 and 25 °C. The relative reactivities are given in Table 115, and are interesting... 

Shatenshtein et a/.S19 have also measured the effect of boron trifluoride as a catalyst for hydrogen exchange in acetic acid and have compared it with stannic chloride (Table 157). The logarithm of the rate coefficient was linearly related to... 

Rate coefficients for protodeboronation of a number of substituted benzene-boronic acids were measured by Kuivila et al.621 at pH 6.70 and 6.42 at 90 °C, p = 0.14. The relative rates at the two pH values were reasonably constant, indicating that the same reaction was being studied for each compound (Table 200). The results indicate that all substituents increase the rate of reaction but... 

Rate coefficients have been determined for protodeboronation of benzene- and thiophene-boronic acids in a range of aqueous perchloric acid mixtures at temperatures between 25 and 90 °C630. First-order rate coefficients are given in Table 204, but not all of the rates were measured at the acidities indicated (see Table footnote), but were corrected to these making use of the linear relationship which was found, in preliminary experiments, to exist between log rate and H0. Similarly, the relative reactivities to thiophene-2-, thiophene-3-, and benzene-boronic acid (8.5 x 10s, 7.1 x 103, and 1.0, respectively) were obtained at an H0... 

In 159 and 163-166 the tertiary amine function is coordinated to the boron atom and transmits the electronic change due to the ester formation to the chromophore. In 160-162 the boron atom is directly connected to the chromophore. After the complexation of the saccharide, the change of the charge transfer, e.g., for 159 [249-251], or the fluorescence bands, e.g., for 160-166 [252-255], can be measured and interpreted. The most selective binding of n-glucose has been achieved with host 164 that forms a 1 1 complex with a macrocyclic structure (Scheme 1). 

Compounds 167-171 outlined in Fig. 43 form another series of diboronic acids that form complexes with mono- and disaccharides. In these cases the asymmetrical immobilization of chromophoric functional groups, e.g., aromatic rings in 167-170 or Fe -complexation with the related boronate 171, can be analyzed by circular dichroism measurements [256-262]. 

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