barrel punt guns of 112-in. bore, weighing 100 ℔. While no conspicuous advance in improved gun-mechanism and invention has been made during the last few years, the materials and methods of manufacture, and the quality and exactitude of the gun-maker’s work, have continued gradually and steadily to improve. English, and particularly London-made, guns stand pre-eminent all over the world. (H. S.-K.)
GUNA, a town and military station in Central India, in the
state of Gwalior. Pop. (1901) 11,452. After the Mutiny, it
became the headquarters of the Central India Horse, whose
commanding officer acts as ex-officio assistant to the resident of
Gwalior; and its trade has developed rapidly since the opening
of a station on a branch of the Great Indian Peninsula railway
in 1899.
GUNCOTTON, an explosive substance produced by the action
of strong nitric acid on cellulose at the ordinary temperature;
chemically it is a nitrate of cellulose, or a mixture of nitrates,
according to some authorities. The first step in the history of
guncotton was made by T. J. Pelouze in 1838, who observed that
when paper or cotton was immersed in cold concentrated nitric
acid the materials, though not altered in physical appearance,
became heavier, and after washing and drying were possessed
of self-explosive properties. At the time these products were
thought to be related to the nitrated starch obtained a little
previously by Henri Braconnot and called xyloidin; they are
only related in so far as they are nitrates. C. F. Schönbein of
Basel published his discovery of guncotton in 1846 (Phil. Mag.
[3], 31, p. 7), and this was shortly after followed by investigations
by R. R. Böttger of Frankfort and Otto and Knop, all of whom
added to our knowledge of the subject, the last-named introducing
the use of sulphuric along with nitric acid in the nitration process.
The chemical composition and constitution of guncotton has
been studied by a considerable number of chemists and many
divergent views have been put forward on the subject. W. Crum
was probably the first to recognize that some hydrogen atoms
of the cellulose had been replaced by an oxide of nitrogen, and
this view was supported more or less by other workers, especially
Hadow, who appears to have distinctly recognized that at least
three compounds were present, the most violently explosive of
which constituted the main bulk of the product commonly
obtained and known as guncotton. This particular product was
insoluble in a mixture of ether and alcohol, and its composition
could be expressed by the term tri-nitrocellulose. Other products
were soluble in the ether-alcohol mixture: they were less
highly nitrated, and constituted the so-called collodion guncotton.
The smallest empirical formula for cellulose (q.v.) may certainly be written C6H10O5. How much of the hydrogen and oxygen are in the hydroxylic (OH) form cannot be absolutely stated, but from the study of the acetates at least three hydroxyl groups may be assumed. The oldest and perhaps most reasonable idea represents guncotton as cellulose trinitrate, but this has been much disputed, and various formulae, some based on cellulose as C12H20O10, others on a still more complex molecule, have been proposed. The constitution of guncotton is a difficult matter to investigate, primarily on account of the very insoluble nature of cellulose itself, and also from the fact that comparatively slight variations in the concentration and temperature of the acids used produce considerable differences in the products. The nitrates are also very insoluble substances, all the so-called solvents merely converting them into jelly. No method has yet been devised by which the molecular weight can be ascertained.[1] The products of the action of nitric acid on cellulose are not nitro compounds in the sense that picric acid is, but are nitrates or nitric esters.
Guncotton is made by immersing cleaned and dried cotton waste in a mixture of strong nitric and sulphuric acids. The relative amounts of the acids in the mixture and the time of duration of treatment of the cotton varies somewhat in different works, but the underlying idea is the same, viz. employing such an excess of sulphuric over nitric that the latter will be rendered anhydrous or concentrated and maintained as such in solution in the sulphuric acid, and that the sulphuric acid shall still be sufficiently strong to absorb and combine with the water produced during the actual formation of the guncotton. In the recent methods the cotton remains in contact with the acids for two to four hours at the ordinary air temperature (15° C.), in which time it is almost fully nitrated, the main portion, say 90%, having a composition represented by the formula[2]2</a> C6H7O2(NO3)3, the remainder consisting of lower nitrated products, some oxidation products and traces of unchanged cellulose and cellulose sulphates. The acid is then slowly run out by an opening in the bottom of the pan in which the operation is conducted, and water distributed carefully over its surface displaces it in the interstices of the cotton, which is finally subjected to a course of boiling and washing with water. This washing is a most important part of the process. On its thoroughness depends the removal of small quantities of products other than the nitrates, for instance, some sulphates and products from impurities contained in the original cellulose. Cellulose sulphates are one, and possibly the main, cause of instability in guncotton, and it is highly desirable that they should be completely hydrolysed and removed in the washing process. The nitrated product retains the outward form of the original cellulose. In the course of the washing, according to a method introduced by Sir F. Abel, the cotton is ground into a pulp, a process which greatly facilitates the complete removal of acids, &c. This pulp is finally drained, and is then either compressed, while still moist, into slabs or blocks when required for blasting purposes, or it is dried when required for the manufacture of propellants. Sometimes a small quantity of an alkali (e.g. sodium carbonate) is added to the final washing water, so that quantities of this alkaline substance ranging from 0.5% to a little over 1% are retained by the guncotton. The idea is that any traces of acid not washed away by the washing process or produced later by a slow decomposition of the substance will be thereby neutralized and rendered harmless. Guncotton in an air-dry state, whether in the original form or after grinding to pulp and compressing, burns with very great rapidity but does not detonate unless confined.
Immediately after the discovery of guncotton Schönbein proposed its employment as a substitute for gunpowder, and General von Lenk carried out a lengthy and laborious series of experiments intending to adapt it especially for artillery use. All these and many subsequent attempts to utilize it, either loose or mechanically compressed in any way, signally failed. However much compressed by mechanical means it is still a porous mass, and when it is confined as in a gun the flame and hot gases from the portion first ignited permeate the remainder, generally causing it actually to detonate, or to burn so rapidly that its action approaches detonation. The more closely it is confined the greater is the pressure set up by a small part of the charge burning, and the more completely will the explosion of the remainder assume the detonating form. The employment of guncotton as a propellant was possible only after the discovery that it could be gelatinized or made into a colloid by the action of so-called solvents, e.g. ethylacetate and other esters, acetone and a number of like substances (see Cordite).
When quite dry guncotton is easily detonated by a blow on an anvil or hard surface. If dry and warm it is much more sensitive to percussion or friction, and also becomes electrified by friction under those conditions. The amount of contained moisture exerts a considerable effect on its sensitiveness. With about 2% of moisture it can still be detonated on an anvil, but the action is generally confined to the piece struck. As the quantity of contained water increases it becomes difficult or even impossible to detonate by an ordinary blow. Compressed dry guncotton is easily detonated by an initiative detonator such as mercuric fulminate. Guncotton containing more than 15% of water is uninflammable, may be compressed or worked without danger and is much more difficult to detonate by a fulminate
- ↑ The composition of the cellulose nitrates was reviewed by G. Lunge (Jour. Amer. Chem. Soc., 1901, 23, p. 527), who, assuming the formula C24H40O20 for cellulose, showed how the nitrocelluloses described by different chemists may be expressed by the formula C24H{46-x}O20(NO2)x, where x has the values 4, 5, 6, . . . 12.
- ↑ This formula is retained mainly on account of its simplicity. It also expresses all that is necessary in this connexion.
