By inspecting the flame of a candle burning under usual circumstances, we perceive at the bottom of the flame a portion which is of a light blue color (a b), Fig. 2, which gradually diminishes in size as it recedes from the wick, and disappears when it reaches the perpendicular side of the flame. In the midst of the flame there is a dark nucleus with a conical form (c). This is enveloped by the illuminating portion of the flame (d). At the exterior edge of the part d we perceive a thin, scarcely visible veil, a, e, e, which is broader near the apex of the flame. The action of the burning candle may be thus explained. The radiant heat from the flame melts the tallow or wax, which then passes up into the texture of the wick by capillary attraction until it reaches the glowing wick, where the heat decomposes the combustible matter into carbonated hydrogen (C4H4), and into carbonic oxide (CO).
While these gases are rising in hot condition, the air comes in contact with them and effects their combustion. The dark portion, c, of the flame is where the carbon and gases have not a sufficiency of air for their thorough combustion; but gradually they become mixed with air, although not then sufficient for complete combustion. The hydrogen is first oxidized or burnt, and then the carbon is attacked by the air, although particles of carbon are separated, and it is these, in a state of intense ignition, which produce the illumination. By bringing any oxidizable substance into this portion of the flame, it oxidizes very quickly in consequence of the high temperature and the free access of air. For that reason this part of the flame is termed the oxidizing flame, while the illuminating portion, by its tendency to abstract oxygen for the purpose of complete combustion, easily reduces oxidated substances brought into it, and it is, therefore, called the flame of reduction. In the oxidizing flame, on the contrary, all the carbon which exists in the interior of the flame is oxidized into carbonic acid (CO2) and carbonic oxide (CO), while the blue color of the cone of the flame is caused by the complete combustion of the carbonic oxide. These two portions of the flame—the oxidizing and the reducing—are the principal agents of blowpipe analysis.
If we introduce a fine current of air into a flame, we notice the following: The air strikes first the dark nucleus, and forcing the gases beyond it, mixes with them, by which oxygen is mingled freely with them. This effects the complete combustion of the gases at a certain distance from the point of the blowpipe. At this place the flame has the highest temperature, forming there the point of a blue cone. The illuminated or reducing portion of the flame is enveloped outside and inside by a very hot flame, whereby its own temperature is so much increased that in this reduction-flame many substances will undergo fusion which would prove perfectly refractory in a common flame. The exterior scarcely visible part loses its form, is diminished, and pressed more to a point, by which its heating power is greatly increased.
The Blast of Air.—By using the blowpipe for chemical purposes, the effect intended to be produced is an uninterrupted steady stream of air for many minutes together, if necessary, without an instant's cessation. Therefore, the blowing can only be effected with the muscles of the cheeks, and not by the exertion of the lungs. It is only by this means that a steady constant stream of air can be kept up, while the lungs will not be injured by the deprival of air. The details of the proper manner of using the blowpipe are really more difficult to describe than to acquire by practice; therefore the pupil is requested to apply himself at once to its practice, by which he will soon learn to produce a steady current of air, and to distinguish the different flames from each other. We would simply say that the tongue must be applied to the roof of the mouth, so as to interrupt the communication between the passage of the nostrils and the mouth. The operator now fills his mouth with air, which is to be passed through the pipe by compressing the muscles of the cheeks, while he breathes through the nostrils, and uses the palate as a valve. When the mouth becomes nearly empty, it is replenished by the lungs in an instant, while the tongue is momentarily withdrawn from the roof of the mouth. The stream of air can be continued for a long time, without the least fatigue or injury to the lungs. The easiest way for the student to accustom himself to the use of the blowpipe, is first to learn to fill the mouth with air, and while the lips are kept firmly closed to breathe freely through the nostrils. Having effected this much, he may introduce the mouthpiece of the blowpipe between his lips. By inflating the cheeks, and breathing through the nostrils, he will soon learn to use the instrument without the least fatigue. The air is forced through the tube against the flame by the action of the muscles of the cheeks, while he continues to breathe without interruption through the nostrils. Having become acquainted with this process, it only requires some practice to produce a steady jet of flame. A defect in the nature of the combustible used, as bad oil, such as fish oil, or oil thickened by long standing or by dirt, dirty cotton wick, or an untrimmed one, or a dirty wickholder, or a want of steadiness of the hand that holds the blowpipe, will prevent a steady jet of flame. But frequently the fault lies in the orifice of the jet, or too small a hole, or its partial stoppage by dirt, which will prevent a steady jet of air, and lead to difficulty. With a good blowpipe the air projects the entire flame, forming a horizontal, blue cone of flame, which converges to a point at about an inch from the wick, with a larger, longer, and more luminous flame enveloping it, and terminating to a point beyond that of the blue flame.
To produce an efficient flame of oxidation, put the point of the blowpipe into the flame about one third the diameter of the wick, and about one twelfth of an inch above it. This, however, depends upon the size of the flame used. Blow strong enough to keep the flame straight and horizontal, using the largest orifice for the purpose. Upon examining the flame thus produced, we will observe a long, blue flame, a b, Fig. 3, which letters correspond with the same letters in Fig. 2. But this flame has changed its form, and contains all the combustible gases. It forms now a thin, blue cone, which converges to a point about an inch from the wick. This point of the flame possesses the highest intensity of temperature, for there the combustion of the gases is the most complete. In the original flame, the hottest part forms the external envelope, but here it is compressed more into a point, forming the cone of the blue flame, and likewise an envelope of flame surrounding the blue one, extending beyond it from a to c, and presenting a light bluish or brownish color. The external flame has the highest temperature at d, but this decreases from d to c.
If there is a very high temperature, the oxidation is not effected so readily in many cases, unless the substance is removed a little from the flame; but if the heat be not too high, it is readily oxidized in the flame, or near its cone. If the current of air is blown too freely or violently into the flame, more air is forced there than is sufficient to consume the gases. This superfluous air only acts detrimentally, by cooling the flame.
In general the operation proceeds best when the substance is kept at a dull red heat. The blue cone must be kept free from straggling rays of the yellow or reduction flame. If the analysis be effected on charcoal, the blast should not be too strong, as a part of the coal would be converted into carbonic oxide, which would act antagonistically to the oxidation. The oxidation flame requires a steady current of air, for the purpose of keeping the blue cone constantly of the same length. For the purpose of acquiring practice, the following may be done: Melt a little molybdenic acid with some borax, upon a platinum wire, about the sixteenth of an inch from the point of the blue cone. In the pure oxidation flame, a clear yellowish glass is formed; but as soon as the reduction flame reaches it, or the point of the blue cone touches it, the color of the bead changes to a brown, which, finally, after a little longer blowing, becomes quite dark, and loses its transparency. The cause of this is, that the molybdenic acid is very easily reduced to a lower degree of oxidation, or to the oxide of molybdenum. The flame of oxidation will again convert this oxide into the acid, and this conversion is a good test of the progress of the student in the use of the blowpipe. In cases where we have to separate a more oxidizable substance from a less one, we use with success the blue cone, particularly if we wish to determine whether a substance has the quality, when submitted to heat in the blue cone, of coloring the external flame.
A good reduction flame can be obtained by the use of a small orifice at the point of the blowpipe. In order to produce such a flame, hold the point of the blowpipe higher above the wick, while the nozzle must not enter the flame so far as in the production of the oxidation flame. The point of the blowpipe should only touch the flame, while the current of air blown into it must be stronger than into the oxidation flame. If we project a stream, in the manner mentioned, into the flame, from the smaller side of the wick to the middle, we shall perceive the flame changed to a long, narrow, luminous cone, a b, Fig. 4, the end a of which is enveloped by the same dimly visible blueish colored portion of the flame a, c, which we perceive in the original flame, with its point at c. The portion close above the wick, presenting the dull appearance, is occasioned by the rising gases which have not supplied to them enough oxygen to consume them entirely. The hydrogen is consumed, while the carbon is separated in a state of bright ignition, and forms the internal flame.
