Electric flame

Operating Principles — There are many similarities between ICP-AES and the combustion flame spectroscopy techniques of flame atomic emission (FAE) and flame atomic absorption (FAA). In fact, the source of the ICP-AES has been referred to by Fassel as an electric flame. The final prepared analytical sample is presented in liquid form for analysis except for unique situations. The liquid sample is drawn (or... 

Fassel, V. A. Electrical Flame Spectroscopy in Proceedings XVI Colloquium Spectroscopicion Internationale, Adam Hilger, London, 1971, pp. 63-93. 

From the perspective of the atomic spectroscopist, desirable properties of plasmas include high thermal temperature and sufficient energy to excite and ionize atoms which are purposefully introduced for the purposes of analysis. In terms of atomic spectrometry, this means that we would generally wish to measure the absorption or emission of radiation in the near-ultraviolet (180-350 nm) and visible (350-770 nm) parts of the spectrum. In this sense, plasmas have been variously described as electrical flames or partially ionized gases. A working definition for atomic spectrometry could be as follows ... 

In 1897, Lord Rayleigh isolated argon from atm. air by confining a mixture of 9 vols. of air and 11 vols. of oxygen in a glass globe in which the electric flame... 

In K. Birkeland and S. Eyde s furnace, the arc between the electrodes is maintained by an alternating current of about 5000 volts and 50 periods per second, and is spread by a strong magnetic field into two semicircular discs of flame at right angles to the axis of the electrodes. The sheets of flame alternately rise and break with great rapidity in the upper and lower half of the reaction chamber. The impression on the eye is that of a steady circular sheet of flame about 1-8 metres in diameter. The electric flame is produced in a flat box of refractory... 

Pyrogenic reactions of organic compounds with the electric-flame, (flaming discharge) as produced at a lower tension and higher intensity than required for the production of the spark (at about 2000-4000 volts and 0.05-0.15 amp.) have not yet been carried out. 

F2. Fassel, V. A. Electrical flame spectroscopy. Int. Colloq. Spectrosc., 16th, Plenary Led., Heidelberg, 1971 in press (1972). 

Properties and Good electrical, Flame-resistant, Fligh temperature Good mechanical, Tough, easy... 

Outstanding mechanical, electrical, flame, and chemical resistance... 

Electrical flames or electrically generated flame-like plasmas possess physical and spectroscopic properties that make them potentially very useful as free atom generators and excitation sources for the determination of the rare earths. The ultimate potential of these plasmas for the analysis of rare earth mixtures has not been evaluated, but the preliminary result so far obtained in our laboratories are indeed encouraging. For example, the detection limits that have been measured in an electrodeless induction coupled plasma (ICP) (see table 37D.3 in section 2.2.5) are at least two to three orders of magnitude lower than the lowest values so far reported by flame emission. 

The luminometer index (ASTM D 1740) is a characteristic that is becoming less frequently used. It is determined using the standard lamp mentioned above, except that the lamp is equipped with thermocouples allowing measurement of temperatures corresponding to different flame heights, and a photo-electric cell to evaluate the luminosity. The jet fuel under test is compared to two pure hydrocarbons tetraline and iso-octane to which are attributed the indices 0 and 100, respectively. The values often observed in commercial products usually vary between 40 and 70 the official specification is around 45 for TRO. 

Concentrate each of the two solutions (or eluates) to about 20 ml, by distilling off the greater part of the benzene, the distilling-flask being immersed in the boiling water-bath. Then pour the concentrated solution into an evaporating-basin, and evaporate the remaining benzene (preferably in a fume-cupboard) in the absence of free flames, i.e., on an electrically heated water-bath, or on a steam-bath directly connected to a steam-pipe. Wash the dry residue from the first eluate with petrol and then dry it in a desiccator pure o-nitroaniline, m.p. 72°, is obtained. Wash the second residue similarly with a small quantity of benzene and dry pure />--nitroaniline, m.p. 148" , is obtained. Record the yield and m.p. of each component. 

For temperatures up to 100°, a water bath or steam bath is generally employed. The simplest form is a beaker or an enamelled iron vessel mounted on a suitable stand water is placed in the vessel, which is heated by means of a flame. This arrangement may be used for non-inflammable liquids or for refluxing liquids of low boiling point. Since numerous liquids of low boiling point are highly inflammable, the presence of a naked flame will introduce considerable risk of fire. For such liquids a steam bath or an electrically-heated water bath, provided with a constant-level device, must be used. If the laboratory is equipped with a... 

Ether. The most satisfactory method for the removal of (diethyl) ether is either on a steam bath fed from an external steam supply or by means of an electrically-heated, constant-level water bath (Fig. 77, 5, 1). If neither of these is available, a water bath containing hot water may be used. The hot water should be brought from another part of the laboratory under no circumstances should there be a free flame under the water bath. It caimot be too strongly emphasised that no flame whatsoever may be present in the vicinity of the distillation apparatus a flame 10 feet away may ignite diethyl ether if a continuous bench top lies between the flame and the still and a gentle draught happens to be blowing in the direction of the flame. 

If crystallisation commences as soon as the solvent cools or if large quantities of hot solution are to be filtered, the funnel (and fluted filter paper) should be warmed externally during the filtration (hot water funnel). Three types of hot water funnel are illustrated in Fig. 11,1, 6 no flames should be present whilst inflammable solvents are being filtered through the funnel of Fig. 11, 1, 6, a. Alternatively, the funnel may be surrounded by an electric heating mantle (see Section 11,57) the heat input may be controlled by a variable transformer. When dealing with considerable volumes of aqueous or other solutions which do not deposit crystals rapidly on cooling, a Buchner funnel may be used for filtration (see detailed account in Section 11,1 and Fig. 11 1, 7, c). The filter paper... 

For solids which melt above 100° and are stable at this temperature, drying may be carried out in a steam oven. The crystals from the Buchner funnel should then be placed on a clock glass or in an open dish. The substance may sometimes be dried in the Buchner funnel itself by utilising the device illustrated in Fig. 77, <33, 1. An ordinary Pyrex funnel is inverted over the Buchner funnel and the neck of the funnel heated by means of a broad flame (alternatively, the funnel may be heated by a closely-fltting electric heating mantle) if gentle suction is applied to the Alter flask, hot (or warm) air will pass over the crystalline solid. 

Attention is directed to the fact that ether is highly inflammable and also extremely volatile (b.p. 35°), and great care should be taken that there is no naked flame in the vicinity of the liquid (see Section 11,14). Under no circumstances should ether be distilled over a bare flame, but always from a steam bath or an electrically-heated water bath (Fig.//, 5,1), and with a highly efficient double surface condenser. In the author s laboratory a special lead-covered bench is set aside for distillations with ether and other inflammable solvents. The author s ether still consists of an electrically-heated water bath (Fig. 11, 5, 1), fitted with the usual concentric copper rings two 10-inch double surface condensers (Davies type) are suitably supported on stands with heavy iron bases, and a bent adaptor is fitted to the second condenser furthermost from the water bath. The flask containing the ethereal solution is supported on the water bath, a short fractionating column or a simple bent still head is fitted into the neck of the flask, and the stUl head is connected to the condensers by a cork the recovered ether is collected in a vessel of appropriate size. 

In a 1 litre round-bottomed flask provided with an efficient double surface condenser, place 40 g. (39 ml.) of aniline, 50 g. (40 ml.) of carbon sulphide CAUTION inflammable) (1), and 50 g. (63-5 ml.) of absolute ethyl alcohol (2). Set up the apparatus in the fume cupboard or attach an absorption device to the top of the condenser (see Fig. 11, 8, 1) to absorb the hydrogen sulphide which is evolved. Heat upon an electrically-heated water bath or upon a steam bath for 8 hours or until the contents of the flask sohdify. When the reaction is complete, arrange the condenser for downward distillation (Fig. 11, 13, 3), and remove the excess of carbon disulphide and alcohol (CA UTION inflammable there must be no flame near the receiver). Shake the residue in the flask with excess of dilute hydrochloric acid (1 10) to remove any aniline present, filter at the pump, wash with water, and drain well. Dry in the steam oven. The yield of crude product, which is quite satisfactory for the preparation of phenyl iao-thiocyanute (Section IV.95), is 40-45 g. Recrystalhse the crude thiocarbanihde by dissolving it, under reflux, in boiling rectified spirit (filter through a hot water funnel if the solution is not clear), and add hot water until the solution just becomes cloudy and allow to cool. Pure sj/m.-diphenylthiourea separates in colourless needles, m.p, 154°,... 

The focus of this section is the emission of ultraviolet and visible radiation following thermal or electrical excitation of atoms. Atomic emission spectroscopy has a long history. Qualitative applications based on the color of flames were used in the smelting of ores as early as 1550 and were more fully developed around 1830 with the observation of atomic spectra generated by flame emission and spark emission.Quantitative applications based on the atomic emission from electrical sparks were developed by Norman Lockyer (1836-1920) in the early 1870s, and quantitative applications based on flame emission were pioneered by IT. G. Lunde-gardh in 1930. Atomic emission based on emission from a plasma was introduced in 1964. 

Fundamentally, introduction of a gaseous sample is the easiest option for ICP/MS because all of the sample can be passed efficiently along the inlet tube and into the center of the flame. Unfortunately, gases are mainly confined to low-molecular-mass compounds, and many of the samples that need to be examined cannot be vaporized easily. Nevertheless, there are some key analyses that are carried out in this fashion the major one i.s the generation of volatile hydrides. Other methods for volatiles are discussed below. An important method of analysis uses lasers to vaporize nonvolatile samples such as bone or ceramics. With a laser, ablated (vaporized) sample material is swept into the plasma flame before it can condense out again. Similarly, electrically heated filaments or ovens are also used to volatilize solids, the vapor of which is then swept by argon makeup gas into the plasma torch. However, for convenience, the methods of introducing solid samples are discussed fully in Part C (Chapter 17). 

In practice, direct insertion of samples requires a somewhat more elaborate arrangement than might be supposed. The sample must be placed on an electrode before insertion into the plasma flame. However, this sample support material is not an electrode in the usual meaning of the term since no electrical current flows through it. Heating of the electrode is done by the plasma flame. The electrode or probe should have small thermal mass so it heats rapidly, and it must be stable at the high temperatures reached in the plasma flame. For these reasons, the sort of materials used... 

Schematic diagram of a flame ionization detector. Ions and electrons formed in the flame provide an electrically conducting path between the flame at earth potential and an insulated cylindrical metal electrode at high potential. surrounding the flame the flow of current is monitored, amplified, and passed to the recording system.

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