Chapter 2

In the following experiments the standard temperature of the water was taken as 60° F., and as the coal gave 13.4° of rise of temperature, 67° F. was selected as the standard room temperature. The reason for this room temperature is obvious, for, whatever heating effect the higher temperature of the room may have upon the water in the cylinder during the time occupied by the first half of the experiment, would be compensated for by the loss sustained during the second half of the experiment, when the temperature of the water exceeded that of the room. The mean of numerous trials gave 13.4° F. rise of temperature, equal to 14.74 lb. of water per lb. of coal. When the water was at 50° and the room at 57°, the mean of several experiments gave 13.5° rise of temperature. When the water was 40° at starting and the room at 47°, 13.65° was the average rise of temperature. Trials were made at intermediate temperatures, and the results always showed that higher figures were recorded when the water was coldest. With a view of getting uniformity in the results it was thought well to make experiments, in order to find out what temperature the room should be at, so that this coal might give the same result with the water at 50°, 40°, or at intermediate temperatures. Without going much into detail, it was found that when the temperature of the room was at 40° and that of the water 40°, and the experiment was rapidly and carefully performed, 13.4° rise of temperature was given; but this result could be obtained without special effort when the room was 42° and the water 40° at starting. It is evident that the cooling effect of the air in the room upon the water cylinder is very appreciable when the water has reached 13° above that of the room. When the water was at 50° and the room at 55°, the coal gave 13.4° rise with ease and certainty, and it would not be out of place to remark here that with those coals which burn well in Thompson's calorimeter, the results of several trials are remarkably uniform when properly performed. With the water at 70° and the room at 80°, a like result was worked out. Experiments at intermediate temperatures were also carried out (see table in sequel). It is true that the whole difference of temperature we are dealing with in making these corrections is only 0.25, but 0.2 in the result, when multiplied by 537 to bring it into calories, as is done by the authorities in Italy, makes more than 100 heat units--a serious difference when 5d. per ton fine is attached to every 100 calories lower than the number guaranteed.

Taking the latent heat of steam as 537° C., and multiplying this number by 14.74, the evaporative power of the coal used in these experiments, its equivalent in calories is 7,915. From the analysis of this coal, disregarding the nitrogen and deducting an equivalent of hydrogen for the oxygen present, the _total heat units_ given by Favre and Silbermann's figures for carbon (8,080) and hydrogen (34,462) will be 8,746. It will be seen, therefore, that the calorific power, as determined by Thompson's apparatus, gives a much lower result when multiplied by 537 than the heat units calculated from the chemical composition of the coal. When I used Thompson's apparatus in the chemical laboratory at Turin to determine the evaporative power of various cargoes of South Wales coal, it was agreed by mutual consent that the temperature of the water at starting should be 39° F. (the temperature at which the _heat unit_ was determined). The temperature of the room was about 60°, but this varied, as the weather was somewhat severe and changeable. Under these conditions, with the water at 39° and room 60°, the coal which gives 14.74 lb. of water per lb. of coal, will give as high as 15.88 lb. of water per lb. of coal. This result multiplied by 537=8,496 calories, approaching much more nearly to the theoretic value. This method of working is still practiced abroad, but experience has shown that very widely differing results follow when working in this manner, especially if the temperature of the room is changeable, as it naturally is where ash determinations and other chemical work is proceeding simultaneously. The time the experiment lasts, taking the reading on a quickly rising thermometer and other considerations, render the experiments anything but trustworthy when 0.2 of a degree makes a difference of more than 100 calories. In the instructions supplied with Thompson's calorimeter nothing is said as to the temperature of the room in which the experiment is performed, but simply that the water shall be at 60° F. If, with the water at 60°, a room were at 50°, as it often is in winter, a good coal would give 14 lb. of water per lb. of coal as the evaporative power; but if in summer, the room were at 75° and the water at 60°, the same coal would give 15 lb. of water per lb. of coal. If further evidence were needed of the effect of temperature consideration of the experiments already referred to will show how necessary it is that some general rule shall be adopted. Considerable stress is laid (in the instructions) upon the quantity of oxygen mixture used being determined by rough experiments. This I have found leads to erroneous conclusions unless a number of experiments are tried in the calorimeter, as it often happens that the quantity which appears to be best adapted is not that which yields a trustworthy result. There are many samples of South Wales coal, 30 grains of which will require 10 parts of oxygen mixture in order to burn completely, but since a little oxygen is lost in drying and grinding, and few samples of chlorate are free from chloride, it is not safe to use less than 11 parts of oxygen mixture, but this amount is sufficient in _all_ cases, and never need be exceeded. I have made numerous experiments with various coals (anthracite, steam, semi-bituminous, and bituminous, including a specimen of the ten yard coal of Derbyshire), and find that with 11 parts of chlorate and nitrate of potash, they are all perfectly manageable and yield the best results. It is quite clear that the excess of chlorate is decomposed in all instances, and the latent heat of the oxygen evolved, but those coals which are best to experiment with did not yield results that differed when the quantity of oxygen mixture was reduced to nearly the limit required for combustion of the coal. Under these circumstances, therefore, the constant use of 11 parts of oxygen mixture--a suitable quantity for all coals exported--would enable operators to obtain similar figures, and make the test uniform in different hands.

The following is a brief outline of the method of procedure recommended: Sample the coal until an average portion passes through a sieve having 64 meshes to the square inch. Take about 300 grains (20 grammes) of this and run through a brass wire gauze having 4,600 meshes to the square inch, taking care that the whole sample selected is thus treated. One part of nitrate of potash and 3 parts of chlorate of potash (dry) are separately ground in a mortar, and repeatedly sifted through another wire gauze sieve, having 1,000 meshes to the square inch, in order that the oxygen mixture shall _not_ be ground to an impalpable powder, as this is very undesirable. It absorbs moisture rapidly, and interferes with the regularity of the combustion when very fine. 330 grains of the powder are weighed out (after drying), and intimately incorporated with 30 grains of coal--better with a spatula than by rubbing in a mortar--and then introduced into a copper cylinder (3½ inches long by ¾ inch wide, made from a copper tube), and pressed down in small portions by a test-tube with such firmness as is required by the nature of the coal, not tapped on the bottom, since the rougher portions of the oxygen mixture rise to the surface. As the temperature of a room is almost invariably much higher than the water supply, a little hot water is added to that placed in the glass cylinder, until the difference of temperature between the water and the room is about the mark indicated in the following table:

Room at The water should be

80° F. 70° F. 72 64 67 60 60 54 55 50 50 46 42 40

Say, for example, the room was at 57° and the water placed in the cylinder was at 46°: add a little hot water and stir with the thermometer until it assumes 52°. By the time the excess of water has been removed with a pipette until it is exactly level with the mark, and all is ready, the temperature will rise nearly 0.5°. Let the thermometer be immersed in the water at least three minutes before reading. The fuse should be placed in the mixture, and everything at hand before reading and removing the thermometer. After igniting the fuse and immersing the copper cylinder in the water, the apparatus should be kept in the best position for the gases to be evolved all around the cylinder, and the rate of combustion noted. Some coals are very unmanageable without practice, and samples of "patent fuel" are sometimes met with, containing unreasonable proportions of pitch, which require some caution in working and very close packing, inasmuch as small explosions occur during which a little of the fuel escapes combustion.

In order that the experiment shall succeed well, experience has shown that the nature of the fuse employed has much to do with it. Plaited or woven wick is not adapted, and will fail absolutely with dry coals, unless it is made very free burning. In this case not less than three-quarters of an inch in length is necessary, and the weight of such is very appreciable. I always use Oxford cotton, and thoroughly soak it in a moderately strong solution of nitrate of potash. When dry it should burn a little too fast. The cotton is rubbed between two pieces of cloth until it burns just freely enough; then four cotton strands are taken, twisted together, and cut into lengths of ¾ inch and thoroughly dried. Open out the fuse at the lower end when placing it in the mixture so as to expose as much surface as possible in order to get a quick start, but carefully avoid pressing the material, and use a wire to fill up close to the fuse. A slow start often spoils the experiment, through the upper end of the cylinder becoming nearly filled up with potassic chloride, etc.

By paying attention to such details, and following the method recommended, the apparatus yields very satisfactory results with bituminous and semi-bituminous coals.--_Chemical News_.

* * * * *

EXPLOSION AS AN UNKNOWN FIRE HAZARD.

Words pass along with meanings which are simple conventionalities, marking current opinions, knowledge, fancies, and misjudgments. They attain to new accretions of import as knowledge advances or opinions change, and they are applied now to one set of ideas, now to another. Hence there is nothing truer than the saying, "definitions are never complete." The term explosion in its original introduction denoted the making of a _noise_; it grew to comprehend the idea of _force_ accompanied with violent outburst; it is advancing to a stage in which it implies _combustion_ as associated with destruction, yet somewhat distinct from the abstract idea of the resolution of any form of matter into its elementary constituents. The term, however, as yet takes in the idea of combustion as a decomposition in but a very limited degree, and it may be said to be wavering at the line between expansion and dissociation.

Strictly, in insurance, fire and explosion are different phenomena. A policy insuring against fire-loss does not insure against loss by explosion. It thereby enforces a distinction which exists, or did exist, in the popular mind; and fire, in an insurance sense, as distinct from explosion, was accurately defined by Justice McIlvaine, of the Supreme Court of Ohio (1872), in the case of the Union Insurance Company vs. Forte, i.e., an explosion was a remote cause of loss and not the proximate cause, when the _fire_ was a burning of a gas jet which did not destroy, though the explosion caused by the burning gas-jet did destroy. Earlier than this decision, however (in 1852), Justice Cushing, of the Supreme Court of Massachusetts, in Scripture _vs_. Lowell Mutual Fire Insurance Company, somewhat anticipated later definition, and pronounced for the liability of the underwriter where all damage by the explosion involves the ignition and burning of the agent of explosion. That is, for example, the insurer is liable for damage caused by an explosion from gunpowder, but not for an explosion from steam. The Massachusetts Judge did not conceive any distinction as to fire-loss between the instantaneous burning of a barrel of gunpowder and the slower burning of a barrel of sulphur, and insurance fire-loss is not to be interpreted legally by thermo-dynamics nor thermo chemistry. While the legal principles are as yet unsettled, the tenor of current decisions may be summed up as follows: If explosion cause fire, and fire cause loss, it is a loss by fire as _proximate_ cause; and if fire cause explosion, and explosion cause loss, it is a loss by fire as _efficient_ cause. Smoke, an imperfect combustion, damages, in an insurance sense, as well as flame, which is perfect combustion; and where there is concurrence of expanding air with expanding combustion, the law settles on the basis of a common account. It's all "heat as a mode of motion."

Explosions are the resultants of elemental gases, vaporization, comminution, contact of different substances, as well as of the specifically named explosives. With new processes in manufacture, involving chemical and mechanical transformations, and other uses of new substances and new uses of old substances, explosions increase. The flour-dust of the miller, the starch-dust of the confectioner, increase in fineness and quantity, and they explode; so does the hop-dust of the brewer. In 1844, for the first time, Professors Faraday and Lyell, employed by the British government, discovered that explosion in bituminous coal mines was the quickening of the comparatively slow burning of the "fire-damp" by the almost instantaneous combustion of the fine coal-dust present in the mines. The flyings of the cotton mill do not explode, but flame passes through them with a rapidity almost instantaneous, yet not sufficient to exert the pressure which explodes; the dust of the wood planer and sawer only as yet makes sudden puffs without detonating force. Naphtha vapor and benzine vapor are getting into all places. One of the latest introductions is naphtha extracting oil from linseed, and then volatilized by steam superheated to 400° F. This combination reminds us, as to effectiveness, of the combination at the recent Kansas City fire, when cans of gunpowder and barrels of coal oil both went up together.

But it is the unsuspected causes of explosion which make the great trouble, and prominent among these is conflagration as itself the cause of explosion, and such explosion may develop gases which are non-supporters of combustion as well as those which are inflammable. You throw table salt down a blazing chimney to set free the flame-suppressing hydrochloric acid, you discharge a loaded gun up a blazing chimney to put out the fire by another agency; still the salt, with certain combinations, may be explosive, a resinous vapor may be combustive in a hydrochloric atmosphere, and gunpowder isn't harmless when thrown upon a blaze--in fact, our common fire-extinguisher, water, has its explosive incidences as liquid as well as vapor.

Gases explosive in association may be set free by the temperature of a burning building and get together. In respect to the old conundrum, "Will saltpetre explode?" Mr. A. A. Hayes, Prof. Silliman, and Dr. Hare's views were, as to the explosions in the New York fire of 1845, that in a closed building having niter in one part and shellac or other resinous material in another, the gaseous oxygen generated from the niter and the carbureted hydrogen from the resins mingling by degrees would at length constitute an explosive mixture. A brief consideration of specific explosives uniting may serve to illustrate this phase of the subject.

Though the explosion of gunpowder is the result of a chemical change whereby carbonic acid gas at high tension is evolved (due to the saltpeter and the charcoal), the effect and rapidity of action are greatly promoted by the addition of sulphur. On the contrary, dynamite, now so important, and various similar explosives, are but mixtures of nitro-glycerine with earthy substances, in order to diminish and make more manageable the development of the rending force of the base. The explosive power of any substance is the pressure it exerts on all parts of the space containing it at the instant of explosion, and is measured by comparing the heat disengaged with the volume of gas emitted, and with the rapidity of chemical action. In the case of gunpowder, the proper manipulation and division of the grains is important, because favoring _rapid_ deflagration; but in a purely chemical explosion, each separate molecule is an explosive, and the reaction passes from the interior of one to the interior of another, suddenly driving the atoms much further apart than their naturally infinitesimal vibrations.

Purely chemical explosives like nitro-glycerine, gun-cotton, the picrites, and the fulminates, present a terrible danger from the unknown mode of the new union of atoms, and reaction of the particles within themselves, in spontaneous explosions happening in irregular manner. Some curious circumstances attend the manufacture and use of gun-cotton,[1] nitro-glycerine, and dynamite. Baron von Link, in his system of the artillery use of gun-cotton, diminishes the danger of sudden explosion by twisting the prepared cotton into cords or weaving it into cloth, thereby securing a more uniform density. Mr. Abel's mode of making gun-cotton, which explosive is now used more than any other by the British government, includes drying the damp prepared cotton upon hot plates, _freely open to the air_. If ignited by a flame, however, in an unconfined place, gun-cotton only burns with a strong blaze, but if _confined_ where the temperature reaches 340° F., it explodes with terrific violence. Somewhat similar is the action of nitro-glycerine and dynamite, which simply _burn_ if ignited in the open air, while the same substance will _explode_ through a very slight concussion or by the application of the electric spark; a red-hot iron, also, if applied, will explode them when a flame will not. With care, nitro-glycerine can be kept many years without deterioration; and it has been heated in a sand-bath to 80° C. for a whole day without explosion or alteration. One curious experiment is deserving of mention: If a broad-headed nail be partly driven into pine wood, and then some pieces of dynamite placed on the head of the nail, the latter may be struck hard blows with a wooden mallet without exploding the dynamite _so long as the nail will continue to enter the wood_.

[Footnote 1: The purest gun-cotton may be regarded as a _cellulose_, in which three atoms of hydrogen are replaced by three molecules of peroxide of nitrogen.]

Taking gunpowder as the unit, picrate of potash (picric acid and potassium) has five times more force, gun-cotton seven and a half times, and nitro-glycerine ten times more force. There are others still more powerful, but less known and used, and some explosives are quite uncontrollable and useless.

But the particular object of these remarks is to refer to articles of merchandise non-explosive under general conditions, but so in particular circumstances, as the two fire-extinguishers, water and salt, are explosive under given conditions. The memorable fire which, in July, 1850, destroyed three hundred buildings in Philadelphia, upon Delaware avenue, Water, Front, and Vine streets, was largely extended by explosions of possibly concealed or unknown materials, the presence of the generally recognized explosives being denied by the owners of the properties.

"The germ of the first knowledge of an explosive was probably the accidental discovery, ages ago, of the deflagrating property of the natural saltpeter _when in contact with incandescent charcoal_."[1] Although much manipulation is deemed necessary to form the close mechanical mixture of the materials of gunpowder, it has never been proved that such intimate previous union is necessary to precede the chemical reaction causing explosion; indeed, some explosions in powder works, before the mixture of the materials, or just at its commencement, seem to point to the contrary. It is also certain that in the manufacture of gunpowder the usual nitrate of potassium (saltpeter) can be replaced by the nitrates of soda, baryta, and ammonia, also by the chloride of potassium; charcoal by sawdust, tan, resin, and starch; and though a substitute for sulphur is not easily found, the latter, or a similar substance, is not an absolute necessity in the composition of gunpowder.[2]

[Footnote 1: Encyclopædia Britannica, new edition, viii, p. 806.]

[Footnote 2: _Vide_ Abel's Experiments in Gunpowder, as detailed in Phil. Trans. Eoy. Soc, 1874.--_Vide_ also _Bull. Soc. d'Encouragement_, Nov., 1880, p. 633, _Sur les Explosives_.]

The generally received theory of the chemical action which makes gunpowder explosive is that it is due to the superior affinity of the oxygen of the niter (KNO_3) for the carbon of the charcoal, and the production of carbonic acid gas (CO_2) and carbonic oxide (CO) suddenly and in great volume. The latter extinguishes flame as well as the former, unless its own flammability is supported by the oxygen of the atmosphere until the degree of oxygenation CO_2 is reached. Considering that water (H_2O) is composed of two volumes of hydrogen and one of oxygen, and that under an enormously high temperature and the excessive affinity of oxygen gas for potassium or sodium (freed from nitrate union), dissociation of the water may be possible, aided by its being in the form of spray and steam, we would hesitate to deny that an explosive union of suitable crude salts could occur during the burning of a building containing them when water for extinguishment was put on. Any one who has seen the brilliance with which potassium and sodium burn upon water can easily imagine how such strong affinity of oxygen for these substances might aid in severing its union in water in their presence and under extraordinary heat. It might be safe so say that the presence of water under very high temperature may be as aidful to form an explosive among such salts as have been named, as sulphur is for the rapid combustion of gunpowder.

In the review for August, 1862 (Saltpeter Deflagrations in Burning Buildings and Vessels--Water as an Explosive Agency), it was shown that Mr. Boyden's experiments in 1861-62 proved that explosions would occur when water was put upon niter heated alone, and stronger explosion from niter, drywood, and sulphur; also explosion when melted niter was poured on water. The following points we reproduce for comparison: If common salt be heated separately to a bright heat, and water _at_ 150° F. poured on it, an explosion will occur. Niter mixed with common salt, placed upon burning charcoal, and water added, produce a stronger explosion than salt alone. Heating caustic potash to a white heat, and adding _warm or hot water_, produces explosion. At a Boston fire small explosions were observed upon water touching culinary salt highly heated. Anthracite coal and niter heated in a crucible exploded when _sea water_ was poured on them.