Design of a large,rigid, modular optical bed for versatile optical and spectroscopic experimentation

Described is a mechanically-rigid and referenceable, vibrationally-isolated, modular optical support bed which has demonstrated significant utility in recent research on the physical—chemical nature of the atmospheric pressure spark discharge. By interconnecting an assembly of pre-aligned, truss-like sub-structures, a complete instrumental complex has been fabricated which exhibits high mechanical stability. This stability is sufficient to allow alignment of, for example, a 5 m focal length, high-dispersion optical spectrometer, to be maintained for months without detectable degradation. The approach is versatile and can be easily extended to include a wide variety of optical and other research applications. Supporting mechanical, vibration, and optical data are included as well as documentation of fabrication details.     

Observations on the formation of spark discharge and its influence by an external magnetic field

Described are a series of experiments executed to characterize the physical and chemical nature of spark discharge in argon at atmospheric pressure. Results are reported concerning the expansion properties of the spark and the distribution and longevity of cathode material in and around the spark channel following cessation of the discharge current. The nature of a previously reported symmetrical post-discharge torus is studied at high spark repetition rates. The interaction of residual vapor on following sparks is investigated. Basic features of the spark process are generalized with a set of Schlieren photographs that show bulk motion of the spark plasma. Time-resolved and space-resolved emission and absorption experiments on magnesium electrodes suggest a charged nature to the post-discharge environment. The bulk plasma character is probed further with external magnetic fields to determine the existence of charged species within the post-discharge torus, and the effects of magnetic forces on its formation.     

Electrode processes in the oxidation of tetrahydroisoquinoline derivatives

The electrochemical oxidation of the alkaloid laudanosine (Ia) to O-methylflavinantine (II) has been studied in acetonitrile solvent. Using cyclic voltammetry, rotating disc voltammetry and preparative electrolyses on several alkaloids, simple aliphatic amines and aromatic compounds, some aspects of the mechanism of this coupling reaction are elucidated. The first anodic wave for laudanosine at platinum has E_p=0.55 V vs. Ag/Ag⁺. The electrode rapidly becomes partially passivated at potentials above 0.5 V. This is due to a film which “dissolves” below 0.5 V, at a rate independent of the potential. It is shown that the reaction (Ia)→(II) proceeds at 0.5 V by initial oxidation of the amine moiety. If acids such as sodium bicarbonate are added to the anolyte the amine is protonated causing the first wave to disappear. Oxidation at 1.1 V under these acidic conditions produces the same product, but more rapidly and in significantly higher yield because electrode filming and side reactions resulting from the amine oxidation are abrogated.     

The electrochemical stripping determination of tin in aqueous and nonaqueous media after its extraction

The anodic stripping voltammetric and chronopotentiometric determination of tin(IV) in aqueous and nonaqueous medium after its extraction using the rotating disc electrode made of glassy carbon with the mercury film was studied. The optimum composition of nonaqueous medium for the determination of tin is 0.2 M NaBr+5×10^?5M Hg²⁺ in 20 ml of the extract +30 ml of methanol. Tin(IV) was determined by anodic stripping voltammetry or chronopotentiometry down to the concentration 10^?7M. The selective determination of tin was studied. 10^?6M of tin(IV) was determined with an error ±4–5% even in the presence of metals: Co²⁺, Ni²⁺, Cd²⁺, Zn²⁺ (5×10^?3M), Ag⁺ and Pb²⁺ (5×10^?4M), Cu²⁺ (1.5×10^?4M), Sb³⁺ and Bi³⁺ (5×10^?5M).     

The effects of isotopic substitution and competitive adsorption on the oxidation of aldehydes and alcohols at gold electrodes

The nature of the mechanism of the anodic oxidation of aldehydes in aqueous base on gold electrodes has been probed using isotopic substitution and competitive adsorption studies. A primary kinetic isotope effect of k_H/k_D=3?4 was observed upon substitution of deuterium for protium on the formyl group of benzaldehyde and cyclohexanecarboxaldehyde on gold in aqueous base using the techniques of cyclic voltammetry, rotating disc electrode voltammetry and chronoamperometry. Similar results are reported for the same aldehydes on a silver electrode, and also for the anodic oxidation of 2-propanol and 2-propanol-2-d on gold under similar conditions. Inhibition of the anodic cyclic voltammetric peak for benzaldehyde on gold by a variety of adsorbed species including CN^?, I^?, Br^?, (C₂H₅)₄N⁺ and diethylenetriamine is also described. These observations are used to propose a mechanism for the low potential oxidations of aldehydes and alcohols on gold involving a rate limiting dissociative adsorption step with cleavage of the α-carbon-hydrogen bond.     

Calculations of van der Waals forces in thin liquid films using Lifshitz' theory

For the study of thin, free liquid films (soap films) van der Waals dispersion forces were calculated from Lifshitz' theory for some three-layer models with film thicknesses between 5 and 150 nm. The complete expression as given by [2.] was used to calculate the force, the energy, and the second derivative of the energy after the thickness, as a function of film thickness. The second derivative of the energy after the thickness is needed in light scattering of soap films. The calculations are based on the dielectric data of [14.]. Some effects of the hydrocarbon layers on and electrolyte in the aqueous layer are considered. In order to make the results readily usable, the calculations are presented in the form of accurate empirical equations.     

Synthesis of phenethylamines from phenylacetonitriles obtained by alkylation of cyanide ion with mannich bases from phenols and other benzylamines

Benzylamines, obtained by the Mannich reaction on phenols or by reductive alkylation of aldehydes, have been used in place of benzyl chlorides to alkylate cyanide ion to obtain nitriles which may be reduced to phenethylamines. Yields of 4-hydroxy-3-methoxyphenylacetonitrile were about the same from the primary, secondary, and tertiary amines. Benzylamines not having either an ortho or para OH group did not function as alkylating agents. With such compounds it was necessary to prepare the quaternary salts before alkylation could be achieved. 6-Hydroxydopamine was prepared from 2,4,5-trimethoxybenzaldehyde utilizing the latter approach. 3,5-Dimethoxy-4-hydroxyphenethylamine was cyclized to the corresponding dihydroisoquinoline. The isoquinoline and tetrahydroisoquinoline analogs were also prepared. 4-Hydroxy-3-methoxyphenylacetonitrile was hydrolysed to homovanillic acid, the naturally occurring metabolite of dopamine.     

Electrochemical oxidation of tetramethylhydrazine, 1,1-dimethyl-2,2-dibenzylhydrazine and tetrabenzyl-hydrazine

Cyclic voltammetric studies of the title hydrazines have shown that the first step of oxidation yields stable radical cations. Though the electron transfer reaction is somewhat slow and very dependent on surface condition when solid electrodes are used, the process is quite reversible at mercury electrodes. Chemical analyses of electrolysis solutions were used to supplement rotating ring-disk voltammetric studies of the second stage of oxidation. The initially formed dication undergoes rapid deprotonation and the protons so formed can react with incoming starting material reducing the currents observed below the two-electron level. Deprotonation of the dication at an α-carbon gives a postulated cationic intermediate which can undergo two reactions whose products were observed: dealkylation to form a hydrazone and deprotonation with N-N cleavage giving an imine.     

Comportement polarographique et solvatation de quelques cations dans le mélange binaire diméthylsulfoxyde-carbonate de propylène

The electrochemical oxidation of 2,4,6-tri-tert-butylphenol as well as the phenoxide and phenoxy radical derived from it has been investigated in acetonitrile and ethanol+water. The ease of oxidation decreases in the order phenoxide, phenoxy radical, phenol with the separation between potentials for phenoxide oxidation and phenoxy radical oxidation being 1.2 V in acetonitrile. The phenoxide is oxidized to the stable phenoxy radical in a highly reversible reaction in acetonitrile and alkaline ethanol+water. Oxidation of the radical produces a phenoxonium ion which is attacked by water giving 2,4,6-tri-tert-butyl-4-hydroxy-2,5-cyclohexadienone. This two electron product is also formed upon oxidation of the phenol in either solvent. However, in acidic media the hydroxydienone dealkylates give 2,6-di-tert-butylhydroquinone which is oxidized to the final product 2,6-di-tert-butyl-1,4-benzoquinone. The dealkylation is quite rapid in anhydrous acetonitrile but the rate is depressed by the addition of water.A novel double potential step experiment was used to characterize the oxidation of the phenoxy radical. A step to a potential where the phenoxide is oxidized to the phenoxy radical is followed by a step to a potential where the phenoxy radical is oxidized. The current during the second step is unusually small because protons produced by the oxidation of the radical deactivate the phenoxide. The current-time curve was found to agree with that predicted by digital simulation.     

Brillouin scattering in liquid mixtures: CCl4/CHCl3

The Brillouin light scattering spectra of mixtures of liquid CCl₄ and CHCl₃ have been obtained. The resulting relaxation rates and the relaxing energy reservoir were studied as a function of the mole fraction over the entire concentration range. The energy exchange between the pertinent degrees of freedom are discussed in terms of the relaxation rates of homomolecular and heteromolecular collisions. We came to the conclusion that the resonance energy transfer between vibrational levels play a significant role in determining the vibration—translation energy migration observed by Brillouin scattering'     

Electron density spatial profiles of the DCP source

Electron densities are measured in the high current, analytical and intervening zones of a DCP whose operating parameters are systematically varied. Detailed N_e distribution profiles are obtained for various sleeve flow, nebulizer flow, arc current and matrix concentration regimes. Flowing argon is found to establish a thermal pinch in the high current zone and to steepen gradients in plasmas employed for spectrochemical analysis. The distinctive electron density distributions in the DCP are more sensitive to modulation of gas flow variables than to changes in arc current. Magnetic pressure has no discernible role in pinch formation. Electron densities in spectroscopic regions are minimally affected by easily ionized or other matrix constituents at usual analytical concentrations.     

A phosphorimetric investigation of the external heavy-atom effect in aqueous solution and its correlation with phosphorescence intensity and quantum yield

Excitation and emission phosphorescence spectra, lifetimes, and relative quantum yields of benzene and ten monosubstituted benzenes were determined at 77 K in methanol/water 10/90 v/v and in sodium iodide/methanol/water solutions. Substituents CHO, COCH(3), COC(2)H(5), OH, OCH(3), H(3), C(2)H(5), CH(2)OH and N(CH(3))(2) were investigated. Aqueous sodium iodide solutions were found to be a suitable heavy-atom solvent for phosophorimetry. Heavy-atom enhancement factors ranged from 1.2 to 8.3 according to the molecular structure and a marked decrease of the lifetime was observed for nine compounds in aqueous sodium iodide solution. A linear log-log correlation was obtained between the relative corrected phosphorescence signal and the heavy-atom enhancement factor of the monosubstituted benzenes. A similar correlation was found between the quantum yields and the heavy-atom enhancement factors. The analytical usefulness of these correlations is evident for the prediction of the magnitude of the heavy-atom effect.     

The synthesis of cypridina etioluciferamine and the proof of structure of cypridina luciferin

An unambiguous synthesis of Cypridina etioluciferamine was accomplished in order to prove the structure of this important bioluminescent natural product. Several 2-aminopyrazine 1-oxides were synthesized in order to establish a spectroscopic method for determining the placement of substituents on the pyrazine nucleus of Cypridina etioluciferamine. Titanium tetrachloride was used to improve the yields of these compounds; for example, the yield of 2-amino-3-methyl-5-phenylpyrazine 1-oxide (19) from reaction of phenylglyoxal 1-oxime and α-aminopropionitrile was raised from 3% to 51% by the use of titanium tetrachloride. The pyrazine ring proton is found at τ 1·37 (DMSO-d₆). The isomeric 2-amino-3-methyl-6-phenylpyrazine 1-oxide (22) was similarly prepared and its pyrazine ring proton is found at τ 2·18. This large difference (0·81 ppm) in chemical shift was used to determine whether a 2-aminopyrazine 1-oxide was 5- or 6- substituted. Prepared in an analogous fashion were 2-amino-5-(indol-3-yl)-3-methylpyrazine 1-oxide (23) and 2-amino-5-(indol-3-yl)-3-(3-phthalimidopropyl)pyrazine 1-oxide (16). The structures of these compounds were verified by NMR spectroscopy. By treatment with Raney nickel and hydrogen gas, then 100% hydrazine hydrate, 16 was converted to 2-amino-3-(3-aminopropyl)-5-indol-3-ylpyrazine (5), isolated as the dihydrochloride. This compound, with the indole moiety definitely placed at C-5, is identical with Cypridina etioluciferamine dihydrochloride (IR, UV, TLC). These results show that the structures of Cypridina etioluciferamine and luciferin are correct as published.     

Evaluation of the analytical capabilities of frequency modulated sources in multielement non-dispersive flame atomic fluorescence spectrometry

Frequency modulated sources of Cd and Zn are used to produce modulated atomic fluorescence signals (at two different frequencies) in a non-dispersive flame atomic fluorescence spectrometer. To reduce the flame background level, a chlorine filter, a separated air—acetylene flame, and a solar blind photomultiplier are used. Even so, there is shown experimentally and theoretically to be a multiplex disadvantage, as compared to the conventional single slit scanning dispersive spectrometer, as a result of the flame background photon noise and an additional multiplex disadvantage at high concentrations of an interference, e.g. in the measurement of Zn (213.9 nm), Cd (228.8nm) results in a reduced S/N for Zn when the Cd signal level becomes comparable with the flame background signal level. Little future for multiplexed techniques in atomic flame spectrometry in the u.v.- Visible is predicted.     

Determination of cobalt by pyrogallol chemiluminescence

The chemiluminescence reaction involving pyrogallol in alkaline hydrogen peroxide solution is described. With reaction conditions selected for the determination of Co(II), the detection limit for Co(II) was at least two orders of magnitude below the detection limit of all other species tested. The results suggest that Ca, Mg, Mn, and Fe are the most likely interferents for environmental and biological samples. The log-log calibration graph for Co(II) is linear from a detection limit of 0.5 ng/ml up to 10 microg/ml.     

On the shape of atomic fluorescence analytical curves with a laser excitation source

The effect of high irradiance levels (approaching saturation) upon the shape of atomic fluorescence analytical curves is considered theoretically for both line and continuum sources. The linear range of the analytical curve may be greatly extended over that obtained with normal (low irradiance) sources, as is experimentally verified using a pulsed dye laser as an excitation source.     

A comparison of signal-to-noise ratios for single channel methods (sequential and multiplex) vs multichannel methods in optical spectroscopy

Four major types of spectroscopic systems for quantitative analysis of one or more spectral components we compared, with regard to signal-to-noise ratio for constant analysis time. These four methods are based on sequential-linear scan, sequential-slew scan, multichannel, and multiplex approaches. The multiplex methods can generally be classified into two types, namely Fourier transform spectroscopy and Hadamard transform spectroscopy. It is shown that for the same spectral source, for the same resolving power luminosity product of the optical system, and the same detector, the multichannel approach is the best and the sequential slew scan system is nearly as good for relatively simple spectra in the u.v.- Visible region. Multiplex methods have little to offer in the u.v.- Visible region, where the detector noise limitation seldom applies and where background shot and/or fluctuation noise are dominant but could find considerable use in the u.v.- Visible region for atomic fluorescence or emission spectroscopy especially if the density of spectral lines in the measurement region is not too great and the background intensity is low.     

Noise power spectra of the inductively coupled plasma

Noise power spectra for the ICP were determined under various conditions, by Fast Fourier Transform (FFT) digital techniques. The major noise types observed were white noise, low frequency noise, and high frequency proportional noise. The high frequency proportional noise increased with concentration of analyte and radio frequency input power. The high frequency proportional noise decreased with increasing nebulizer flow rate and coolant gas flow rate.. The low frequency noise components extended to higher frequencies as the resonance wavelengths of the measured transitions increased. Changing the observation height in the plasma determined which noise types were present in the noise power spectrum. At observation heights near the power coils, all three noise types were present, whereas, low frequency noise predominated at significantly greater heights. Changing the torch design changed the relative amplitudes of the different high frequency proportional noise components, but did not greatly change their respective peak frequencies.     

Optimization of thermostated electrodeless discharge lamps for analytical atomic spectrometry

Thermostated and unthermostated electrodeless discharge lamps (EDL's) operated at 2450 MHz with either an A-antenna or a $\text{3}\text{4}$-wavelength Broida cavity have been critically studied with respect to the effect of type and pressure of fill gas, lamp temperature, microwave power and the form of element and/or compound within the lamp, upon the source radiant output, atomic absorption and atomic fluorescence signals of Zn-213·8 nm, Pb-283·3 nm, Mn-279·5 nm, Hg-253·7 nm and Tl-377·6 nm. Temperature control of electrodeless discharge lamps eliminates most of the problems which have previously plagued their operation. Also as a result of these studies, certain misconcepts in the operation and characteristics of electrodeless discharge lamps have been clarified; e.g., the ‘skin effect’ is present in many electrodeless discharge lamps, but all lamps also exhibit a homogeneous glow discharge; at high microwave powers and/or at high lamp temperatures, spectral lines apparently exhibit little self-absorption and self-reversal; and most important, control of lamp temperature is the most critical parameter controlling spectral output because atomization within the lamps is predominantly thermal in origin. Also, contrary to the conclusions reached by some workers evaluating the analytical usefulness of atomic fluorescence flame spectrometry, it is shown that detection limits one-to-three orders of magnitude lower result when thermostated EDL's are used in atomic fluorescence spectrometry with C₂H₂-air flames.