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Showing papers in "Applied Spectroscopy in 1968"


Journal ArticleDOI
TL;DR: The Fourier transform technique has been successfully applied to a number of spectral measurements from the visible through to the far infrared as discussed by the authors, and some of the more recent applications are discussed.
Abstract: This paper provides an introduction to Fourier transform spectroscopy. The basic concepts of the Fourier transform technique are reviewed. These include the characteristics and generation of interferograms and the generation of spectra by the Fourier transformation of interferograms. The multiplex and throughput advantages and the data handling disadvantages are also discussed. The optical, electronic, and data-handling instrumentation and techniques necessary for a Fourier transform spectrometer system are, in general, quite different from those of a conventional prism or grating spectrometer. The requirements of these areas are outlined and recent developments are reviewed. The Fourier transform technique has been successfully applied to a number of spectral measurements from the visible through to the far infrared. Some of the more recent applications are discussed.

65 citations


Journal ArticleDOI
TL;DR: In this paper, the spectral properties of ortho-and meta-substituted styrenes including F, Br, Cl, methyl, and meta-nitro derivatives were investigated in the liquid state while selected regions and isomers have been studied in the solid and gas phase.
Abstract: Infrared and Raman spectra have been obtained over the region 4000 cm−1 to 33 cm−1 on ortho- and meta-substituted styrenes including F, Br, Cl, methyl, and meta-nitro derivatives. The entire spectral region has been investigated in the liquid state while selected regions and isomers have been studied in the solid and gas phase. Gas phase and interferometric spectra in the far ir of ortho- and meta-fluorostyrene did not reveal the torsional modes. Assignment of most fundamental modes of vibrations are reported and discussed.

43 citations


Journal ArticleDOI
TL;DR: In this paper, it was found that water solutions of arsenic oxide contain the compounds As4O6 · XH2O and As(OH)3 and the acid OAsOH was not present in these solutions.
Abstract: It was found that water solutions of arsenic oxide contain the compounds As4O6 · XH2O and As(OH)3. The acid OAsOH is not present in these solutions. The presence of alkali halide in arsenic oxide solutions results in the formation of an ortho arsenite. Oxyarsenic halides and AsCl4− are not present in solutions of AsCl3. The stability of these ions is questioned.

38 citations


Journal ArticleDOI
TL;DR: In this article, the operation of the furnace is described and results are given for the analysis of samples containing diverse matrix elements, where the gas stream in the furnace has an inert, nonturbulent, slow moving atmosphere with a controllable uniform temperature.
Abstract: Some years ago, flame methods of spectrochemical analysis were very popular. In recent years atomic absorption in flames has been extensively applied to the analysis of both industrial and geologic materials. Now the application of electrically heated tubes for evaporation and atomization of samples promises to provide the basis for even greater sensitivity and accuracy. In the furnace, we have an inert, nonturbulent, slow moving atmosphere with a controllable uniform temperature. The gas stream in the furnace is at a lower temperature than the walls. This tends to force suspended particles to the center where they evaporate and pass on into the light beam. It also tends to minimize or eliminate memory effects and matrix effects. The operation of the furnace is described and results are given for the analysis of samples containing diverse matrix elements.

37 citations


Journal ArticleDOI
TL;DR: The laser microprobe has been applied to the excitation of trace elements homogeneously distributed in powdered materials as mentioned in this paper, and the precision of intensity ratios is about ±11% (coefficient of variation), and detection levels are comparable to those of the dc arc.
Abstract: The laser microprobe has been applied to the excitation of trace elements homogeneously distributed in powdered materials. Precision of intensity ratios is about ±11% (coefficient of variation), and detection levels are comparable to those of the dc arc. Matrix effects were studied for four different materials and found to be significantly less than in the dc arc. Use of the probe as the source in a

33 citations


Journal ArticleDOI
TL;DR: Transmission and attenuated total reflection (ATR) spectra of collagen and normal, adult human bone have been compared with literature data and band assignments for bone spectra are given.
Abstract: Transmission and attenuated total reflection (ATR) spectra of collagen and normal, adult human bone have been compared with literature data and band assignments for bone spectra are given. Except for slight shifts in some absorption bands (the amide I band at 1650 cm−1 and some of the phosphate absorption bands), most frequencies of both spectra are in fair agreement with previously reported values for the individual components. An improvement in resolution of some protein bands was achieved with the ATR technique.

30 citations


Journal ArticleDOI
TL;DR: In this article, the authors describe a variable temperature cell which is also used in conjunction with the laser source for Raman spectra of liquids, solids, and condensed gases.
Abstract: A number of cryostats1–5 have been designed previously for use with the Cary 81 Raman spectrophotometer equipped with the Toronto arc source The advent of laser Raman spectroscopy has necessitated the development of new sampling techniques and new cryogenic devices Two cryostats which permit 90° viewing of the Raman scattering were developed for laser excitation by Gee and O’Shea6 and by Perry7 Carlson8 has described a fixed-temperature Raman cell which is suitable for studying solids and condensed vapors with the laser source We wish to describe a variable temperature cell which is also used in conjunction with the laser source The versatility of this new Raman cell is exemplified by the fact that Raman spectra of liquids, solids, and condensed gases may be investigated over a wide temperature range

29 citations


Journal ArticleDOI
TL;DR: The infrared spectra of 141 highly purified acyclic, monocyclic and bicyclic terpene alcohols, their reduced derivatives, and related compounds are presented in this article.
Abstract: The infrared spectra of 141 highly purified acyclic, monocyclic and bicyclic terpene alcohols, their reduced derivatives, and related compounds are presented. The majority of these spectra are new to the literature. These spectra provide a broad basis for the correlation of structure and infrared absorption.

28 citations


Journal ArticleDOI
TL;DR: In this paper, the diffracting power of graphite monochromator with ethylenediamine-d-tantrate and LiF was compared with LiF.
Abstract: The use of highly oriented graphite as a monochromator was recently discussed by Sparks, and has been found to be highly suitable for light-element (Z≥15) x-ray, spectroscopy. This paper compares the diffracting power of the graphite monochromator with ethylenediamine-d-tantrate and LiF.

23 citations


Journal ArticleDOI
TL;DR: In this article, the infrared spectra for chloromethylphosphorous dichloride, chlorophosphoric dibromide, and bromomethythiophosphonic diβromide were obtained at different temperatures and showed that the pentavalent compounds exist as rotational isomers at room temperature.
Abstract: Infrared data were obtained for chloromethylphosphorous dichloride, chloromethylphosphonic dichloride (also Raman data), and chloromethylthiophosphonic dichloride over the region 45–3800 cm−1. Infrared data were also obtained for bromomethylphosphonic dibromide in the region 300–3800 cm−1. Infrared spectra for these compounds were recorded at different temperatures, and show that the pentavalent compounds exist as rotational isomers at room temperature. A previous study of chloromethylphosphonic dichloride and chloromethylthiophosphonic dichloride has established that these two compounds exist as rotational isomers, but the present study gives additional significant information. The infrared spectrum for methylphosphonic dichloride in the region 45–600 cm−1 has been recorded for purpose of comparison with the ClCH2–P series. No spectral evidence was observed for the P–CH3 torsion vibration in methylphosphonic dichloride.

21 citations


Journal ArticleDOI
TL;DR: In this article, the results of a series of experiments were reported in which buffers, consisting of a range of concentrations of various lithium compounds in graphite, were mixed with synthetic samples containing suitable concentrations of selected elements and the mixtures were then burned in the anode of a dc arc.
Abstract: The results of a series of experiments are reported in which buffers, consisting of a range of concentrations of various lithium compounds in graphite, were mixed with synthetic samples containing suitable concentrations of selected elements and the mixtures were then burned in the anode of a dc arc. Anode temperatures during the lifetime of the arc have been observed with the help of a thermistor bolometer and chart recorder. Arc-column temperatures were calculated from the relative intensities of the Mg lines 2783.6 and 3336.7 A. From these observations, and the measured intensities of spectrum lines, conclusions are drawn regarding the effect of each buffer compound on arc and electrode temperature, vaporization rates, are wandering, and general efficiency of the arc source.

Journal ArticleDOI
TL;DR: In this paper, the far-ir spectra of ices 1h and 1c were compared with those of ordered and disordered ices II, V, VI, and IX.
Abstract: Over the past few years the ir spectra of six of the nine known phases of ice have been studied between 4000 and about 50 cm−1. These spectra show the influence of six different intermolecular environments upon the spectra of the same molecule. In this paper the far-ir spectra of ices 1h and 1c will be reviewed and compared with those of ices II, V, VI, and IX, which are discussed in detail for the first time. The far-ir absorptions arise from the translational lattice vibrations of the solid. The spectra of the orientationally disordered phases, 1h, 1c, V, and VI differ strikingly from those of the ordered phases, II and IX. The ordered phases have spectra that are qualitatively similar to the spectra of nonhydrogen-bonded ordered molecular crystals, and agree approximately with the predictions of the Factor Group analyses. The disordered phases all shown extremely broad absorptions owing to the relaxation of the zero-wavevector selection rule.

Journal ArticleDOI
TL;DR: In the past five years, the number of papers concerned with far-ir studies of hydrogen bonding has increased by an order of magnitude as discussed by the authors, and the results of some of these papers are presented in this review.
Abstract: In the past five years the number of papers concerned with far-ir studies of hydrogen bonding has increased by an order of magnitude. The results of some of these papers are presented in this review. Most of this work is concerned with the assignment of low frequency hydrogen bond vibrations. Since the major problem is reliable assignments, we discuss techniques used in making the assignments and emphasize the past work in which attempts have been made to substantiate those assignments. These assignments are discussed in terms of the different hydrogen bond vibrations associated with various types of hydrogen bonds. The main needs for future far ir hydrogen bond studies are listed.

Journal ArticleDOI
TL;DR: In this paper, the results of a series of experiments were reported in which a number of selected buffer compounds were mixed with a synthetic sample containing elements of a wide range of volatilities.
Abstract: The results of a series of experiments are reported in which a number of selected buffer compounds were mixed with a synthetic sample containing elements of a wide range of volatilities. The mixtures were burned in a dc arc and measurements were taken of the anode temperature, arc temperature, and spectrum line intensities throughout the life time of the burn. From these results conclusions are drawn regarding the effect of the buffer cation and buffer anion on the arc and anode temperature, vaporization rates, and arc wandering. Some general rules for the selection of buffer compounds are suggested.

Journal ArticleDOI
Z. van Gelder1
TL;DR: In this paper, a spectral source is desired that has a resonance spectral line of high intensity without self-absorption, and this spectral line must have a profile as narrow as possible without self absorption.
Abstract: In absorption measurement techniques a spectral source is desired that has a resonance spectral line of high intensity. This spectral line must have a profile as narrow as possible without self-absorption. Different solutions of the problem in which a hollow cathode is used are given in the literature.1–7

Journal ArticleDOI
TL;DR: In this article, a combined chemical x-ray fluorescence method is described for determining rare-earth elements in small amounts of complex rare earth minerals, including lanthanides, yttrium, and scandium.
Abstract: A combined chemical x-ray fluorescence method is described for determining rare-earth elements in small amounts of complex rare-earth minerals. These elements yield a complex x-ray spectrum in which many of the analytical emission Lα lines of a given element coincide with the Lβ and/or Lγ lines of a lighter rare-earth element several atomic numbers removed. The proposed analytical scheme corrects for these interferences. Sixteen elements consisting of the lanthanides, yttrium, and scandium can be determined on as little as a 1-mg portion of the separated oxides. The oxides are dissolved in 1 ml of dilute acid, absorbed onto cellulose powder and pressed into a pellet for x-ray excitation. Chemically analyzed geologic standards are not required for calibration.

Journal ArticleDOI
TL;DR: In this paper, a small water-cooled are chamber was constructed so that an arc could be struck through the aerosol vapor, and the spectrum of the arc was examined, but no trace of light from the element in the nebulized spray was found.
Abstract: One way to improve spectrographic methods is to improve light sources. Flame sources are convenient to use but they often suffer from lack of intensity. In order to get stronger excitation than is ordinarily obtained with a flame, a small water-cooled are chamber was constructed so that an arc could be struck through the aerosol vapor. When the spectrum of the arc was examined, no trace of light from the element in the nebulized spray was found. The method was a failure, as, I suspect, many similar efforts have been in the past. Spark excitation gave a spectrum of the element being nebulized. But even here the intensity was not what would be expected compared to the flame, at least for the alkali and alkaline earth elements.

Journal ArticleDOI
TL;DR: In this paper, an improved technique for quantitative determination of trace amounts of silicon in organic matrices is described, which can be used to determine silicon in levels as low as 0.1 μg/ml in organic solution.
Abstract: Trace silicon analysis in organic matrix materials is complicated by time-consuming concentration schemes and/or a lack of suitable organic standards. This paper describes an improved technique for quantitative determination of trace amounts of silicon in organic matrices. The method utilizes recent improvements in atomic absorption spectrometry and can be used to determine silicon in levels as low as 0.1 μg/ml in organic solution. Matrix interferences have been overcome by controlling solids of polymers and preparing standards using Si-free matrix materials. Suitable instrumentation and experimental conditions are described. Model organic silicon compounds and polydimethyl siloxane oils have been examined for use as standards. Experimental data, including a comparison of this method with wet-chemical and x-ray results, is presented. This method can be used for accurate determination of trace silicone contamination in the 1–10 ppm range in (1) paper products, (2) resinous and elastomeric polymers, and (3) oils.

Journal ArticleDOI
TL;DR: In this paper, a four-constant generalized transcendental equation was used to relate emission spectroscopy data to concentration of trace elements in biological fluids for each element the constants in the empirical equation are evaluated by a three-step successive approximation, based on the data from standards.
Abstract: It has been found that a four-constant generalized transcendental equation can be used to relate emission spectroscopy data to concentration of trace elements in biological fluids For each element the constants in the empirical equation are evaluated by a three-step successive approximation, based on the data from standards The functional relationship, which gives values well within the range of experimental error, is then used in the quantitative determination of the concentration of each of 17 trace elements in unknown samples In these studies a Jarrell–Ash direct reading spectrometer was used The entire procedure of data reduction and concentration printout was done on a digital computer

Journal ArticleDOI
TL;DR: In this article, the spectral properties of organic phosphorus compounds have been analyzed using the infrared spectra of these compounds and they have been used to give important information concerning their composition. But, the P=O stretching vibration in many compounds appears in the region of 1170-1310 cm−1.
Abstract: Recently, the organic phosphorus compounds have gained attention because of their use in solvent-extraction separations. The infrared spectra of these compounds may be used to give important information concerning their composition. The infrared spectral assignments of these compounds have been conducted by several workers. According to them, the P=O stretching vibration in many compounds appears in the region of 1170–1310 cm−1. The C–O and P–O stretching vibrations in the P–O–C bond are also assigned at 1020–1050 cm−1 and 1020 cm−1, respectively. As these vibrations are coupled to each other, it is difficult to distinguish between the P–O and C–O bands.

Journal ArticleDOI
Seymour Meyerson1
TL;DR: The value of isotope labeling in probing the chemistry underlying mass spectra is well established as mentioned in this paper, and the usefulness of this approach and the reliability of conclusions reached thereby can be greatly increased by checking dependence of label retentions in fragment ions on operating conditions.
Abstract: The value of isotope labeling in probing the chemistry underlying mass spectra is well established. The usefulness of this approach and the reliability of conclusions reached thereby can be greatly increased by checking dependence of label retentions in fragment ions on operating conditions. For example, varying the ionizing voltage, source temperature, or repeller potential alters the relative contributions of the two competing processes by which methylcyclopentane loses a methyl radical to form isomeric C5H9+ ions. The ions resulting from the two processes are derived from different parts of the original molecule and so can be distinguished by appropriate labeling.

Journal ArticleDOI
D. L. Nash1
TL;DR: In this article, a dc arc burning in a controlled atmosphere of argon and oxygen is used together with a spectrograph of very high dispersion in order to provide optimum signal-to-noise ratio.
Abstract: This paper discusses investigations conducted to achieve optimum sensitivity for the determination of rare earths in yttrium oxide and describes a specific technique evolved for the above analysis. A dc arc burning in a controlled atmosphere of argon and oxygen is used together with a spectrograph of very high dispersion in order to provide optimum signal-to-noise ratio. Because the excitation efficiency is not uniform along the entire height of the arc column, only the most efficient portion is transmitted to the slit. Without any treatment or concentration of the sample other than dilution with graphite powder, the above method achieves sensitivities for the rare earths in yttrium oxide ranging from about 50 ppm for the least sensitive rare earths (Pr, Ce) to about 0.5 ppm for the most sensitive rare earths (Lu, Sc, Yb).

Journal ArticleDOI
TL;DR: In this article, a comprehensive study has been made of the efficiency of copper fluoride as a carrier for quantitative determination of more than thirty impurities in high purity metallic copper, and the results obtained for 15 different elements gave a coefficient of variation of 6.5% on 15 replicate samples.
Abstract: A comprehensive study has been made of the efficiency of copper fluoride as a carrier for the quantitative determination of more than thirty impurities in high purity metallic copper. Although other halides of copper and silver have been shown to improve the sensitivity of their detection, copper fluoride was found to be by far the most versatile and effective. The carrier is added directly to the metallic sample, making the method both simple and unusual. The line intensities of the impurities are apparently independent of the size of the copper sample and dependent only on the quantity of impurities present, a fact which greatly simplifies both calibration and analysis. The limits of detection range down to 10 ppb and are lower than those reported by other spectrographic methods in a number of cases. The results obtained for 15 different elements gave a coefficient of variation of 6.5% on 15 replicate samples. Since extremely pure copper fluoride is vital, a simple method for its preparation is described.

Book ChapterDOI
TL;DR: The most popular techniques for collection of microsamples on KBr powder prior to infrared spectroscopic examination are evaporation from a solution of the sample in the presence of kBr powder and lyophilization as mentioned in this paper.
Abstract: The most popular techniques for collection of microsamples on KBr powder prior to infrared spectroscopic examination are evaporation from a solution of the sample in the presence of KBr powder and lyophilization.1

Journal ArticleDOI
TL;DR: A review of the development of electron microprobe analysis in the last ten years is given in this article, where progress and instrumentation, progress in the theory of quantitative analysis, and the future development of micro probe analysis are discussed.
Abstract: This review covers the development of electron microprobe analysis in the last ten years. After a brief decription of the instrument, the following subjects are discussed: progress and instrumentation; progress in the theory of quantitative analysis; and the future development of microprobe analysis.

Journal ArticleDOI
TL;DR: The nuclear magnetic resonance spectra of the aromatic protons of DDT and 31 of its analogs and derivatives have been analyzed in this article, showing that the chemical shifts of these molecules are functions of the electronegativities of the substituents on the ring, as well as those in the aliphatic portion.
Abstract: The nuclear magnetic resonance spectra of the aromatic protons of DDT and 31 of its analogs and derivatives have been analyzed. Chemical shifts of these molecules are functions of the electronegativities of the substituents on the ring, as well as those in the aliphatic portion, although substitution of the ring chlorine in DDT by either a nitro or a t-butyl group leads to anomalous values. Molecular orbital calculations show that the chemical shift of the proton ortho to the ring substituent depends upon the π electron density at the corresponding carbon, but the chemical shift of the proton meta to this substituent is independent of the π electron density at the corresponding carbon. The data also indicate that the two aromatic rings in DDT are independent of each other.

Journal ArticleDOI
H. C. W. Skinner1
TL;DR: In this article, the lattice constants of apatites have been determined using computer analyses of x-ray powder diffraction data and compositional fluctuations of a phase within a mixture containing several phases can be monitored.
Abstract: Hydrothermal synthesis studies in portions of the system CaO-P2O5-H2O-CO2-F have produced apatites with composition variations. The lattice constants of the apatites have been determined using computer analyses of x-ray powder diffraction data. By this method compositional fluctuations of a phase within a mixture containing several phases can be monitored. Lattice characteristics of hydroxyapatite (molar CaO/P2O5=3.3) synthesized at pressures of 2000 bars and temperatures from 300° to 800°C from bulk compositions over the range 2.0 to 5.0 CaO/P2O5 are discussed.

Journal ArticleDOI
TL;DR: In this paper, the ir and Raman spectroscopic studies of metal complexes with nitrogen-containing ligands have been reviewed and a special emphasis has been placed on the stretching and bending fundamentals of the metal-ligand bond.
Abstract: The ir and Raman spectroscopic studies of metal complexes with nitrogen-containing ligands have been reviewed. A special emphasis has been placed on the stretching and bending fundamentals of the metal–ligand bond. The following ligands are included in the discussion: nitrosyl, nitro, nitrite, nitride, azido, molecular nitrogen, hydrazine, isocyanate, isothiocyanate, isoselenocyanate, pyridine, and ethylenediamine.

Journal ArticleDOI
TL;DR: One of the variables in internal reflection spectroscopy is the angle of incidence on the reflecting surface, which may improve spectral quality, change the beam penetration within the sample, and change the number of reflections, thus changing total absorbance as mentioned in this paper.
Abstract: One of the variables in internal reflection spectroscopy is the angle of incidence on the reflecting surface. Varying the angle may (1) improve spectral quality, (2) change the beam penetration within the sample, and (3) change the number of reflections, thus changing total absorbance.

Journal ArticleDOI
TL;DR: In this article, a laser microprobe was used to perform spectroscopic determinations of Fe, Mg, Mn, and Ca in garnets by use of a laser macroprobe in matrix.
Abstract: Spectrochemical determinations of Fe, Mg, Mn, and Ca in garnets by use of a laser microprobe were performed in matrix. Standards were prepared by fusion of chemically analyzed mineral powders and these standard glasses were excited in the same manner as the mineral unknowns. Comparison of results with the rock standard W-1 showed good accuracy and reproducibility. The precision and accuracy of the method as a whole deems it suitable for most mineralogic investigations where analysis in matrix is desirable.