P. J. Schestakov (J. Russ. Phys. Chem. Soc., 1905, 37, p. 1) obtained hydrazine by oxidizing urea with sodium hypochlorite in the presence of benzaldehyde, which, by combining with the hydrazine, protected it from oxidation. F. Raschig (German Patent 198307, 1908) obtained good yields by oxidizing ammonia with sodium hypochlorite in solutions made viscous with glue. Free hydrazine is a colourless liquid which boils at 113.5° C., and solidifies about 0° C. to colourless crystals; it is heavier than water, in which it dissolves with rise of temperature. It is rapidly oxidized on exposure, is a strong reducing agent, and reacts vigorously with the halogens. Under certain conditions it may be oxidized to azoimide (A. W. Browne and F. F. Shetterly, J. Amer. C.S., 1908, p. 53). By fractional distillation of its aqueous solution hydrazine hydrate N2H4·H2O (or perhaps H2N·NH3OH), a strong base, is obtained, which precipitates the metals from solutions of copper and silver salts at ordinary temperatures. It dissociates completely in a vacuum at 143°, and when heated under atmospheric pressure to 183° it decomposes into ammonia and nitrogen (A. Scott, J. Chem. Soc., 1904, 85, p. 913). The sulphate N2H4·H2SO4, crystallizes in tables which are slightly soluble in cold water and readily soluble in hot water; it is decomposed by heating above 250° C. with explosive evolution of gas and liberation of sulphur. By the addition of barium chloride to the sulphate, a solution of the hydrochloride is obtained, from which the crystallized salt may be obtained on evaporation.
Many organic derivatives of hydrazine are known, the most important being phenylhydrazine, which was discovered by Emil Fischer in 1877. It can be best prepared by V. Meyer and Lecco’s method (Ber., 1883, 16, p. 2976), which consists in reducing phenyldiazonium chloride in concentrated hydrochloric acid solution with stannous chloride also dissolved in concentrated hydrochloric acid. Phenylhydrazine is liberated from the hydrochloride so obtained by adding sodium hydroxide, the solution being then extracted with ether, the ether distilled off, and the residual oil purified by distillation under reduced pressure. Another method is due to E. Bamberger. The diazonium chloride, by the addition of an alkaline sulphite, is converted into a diazosulphonate, which is then reduced by zinc dust and acetic acid to phenylhydrazine potassium sulphite. This salt is then hydrolysed by heating it with hydrochloric acid—
C6H5N2Cl + K2SO3 = KCl + C6H5N2·SO3K, |
Phenylhydrazine is a colourless oily liquid which turns brown on exposure. It boils at 241° C., and melts at 17.5° C. It is slightly soluble in water, and is strongly basic, forming well-defined salts with acids. For the detection of substances containing the carbonyl group (such for example as aldehydes and ketones) phenylhydrazine is a very important reagent, since it combines with them with elimination of water and the formation of well-defined hydrazones (see Aldehydes, Ketones and Sugars). It is a strong reducing agent; it precipitates cuprous oxide when heated with Fehling’s solution, nitrogen and benzene being formed at the same time—C6H5·NH·NH2 + 2CuO = Cu2O + N2 + H2O + C6H5. By energetic reduction of phenylhydrazine (e.g. by use of zinc dust and hydrochloric acid), ammonia and aniline are produced—C6H5NH·NH2 + 2H = C6H5NH2 + NH3. It is also a most important synthetic reagent. It combines with aceto-acetic ester to form phenylmethylpyrazolone, from which antipyrine (q.v.) may be obtained. Indoles (q.v.) are formed by heating certain hydrazones with anhydrous zinc chloride; while semicarbazides, pyrrols (q.v.) and many other types of organic compounds may be synthesized by the use of suitable phenylhydrazine derivatives.
HYDRAZONE, in chemistry, a compound formed by the condensation
of a hydrazine with a carbonyl group (see Aldehydes; Ketones).
HYDROCARBON, in chemistry, a compound of carbon and
hydrogen. Many occur in nature in the free state: for example,
natural gas, petroleum and paraffin are entirely composed of
such bodies; other natural sources are india-rubber, turpentine
and certain essential oils. They are also revealed by the spectroscope
in stars, comets and the sun. Of artificial productions the
most fruitful and important is provided by the destructive or
dry distillation of many organic substances; familiar examples
are the distillation of coal, which yields ordinary lighting gas,
composed of gaseous hydrocarbons, and also coal tar, which,
on subsequent fractional distillations, yields many liquid and
solid hydrocarbons, all of high industrial value. For details
reference should be made to the articles wherein the above
subjects are treated. From the chemical point of view the
hydrocarbons are of fundamental importance, and, on account
of their great number, and still greater number of derivatives,
they are studied as a separate branch of the science, namely,
organic chemistry.
See Chemistry for an account of their classification, &c.
HYDROCELE (Gr. ὕδωρ, water, and κήλη, tumour), the
medical term for any collection of fluid other than pus or blood
in the neighbourhood of the testis or cord. The fluid is usually
serous. Hydrocele may be congenital or arise in the middle-aged
without apparent cause, but it is usually associated with chronic
orchitis or with tertiary syphilitic enlargements. The hydrocele
appears as a rounded, fluctuating translucent swelling in the
scrotum, and when greatly distended causes a dragging pain.
Palliative treatment consists in tapping aseptically and removing
the fluid, the patient afterwards wearing a suspender.
The condition frequently recurs and necessitates radical
treatment. Various substances may be injected; or the
hydrocele is incised, the tunica partly removed and the cavity
drained.
HYDROCEPHALUS (Gr. ὕδωρ, water, and κεφαλὴ, head),
a term applied to disease of the brain which is attended
with excessive effusion of fluid into its cavities. It exists
in two forms—acute and chronic hydrocephalus. Acute hydrocephalus
is another name for tuberculous meningitis (see
Meningitis).
Chronic hydrocephalus, or “water on the brain,” consists in an effusion of fluid into the lateral ventricles of the brain. It is not preceded by tuberculous deposit or acute inflammation, but depends upon congenital malformation or upon chronic inflammatory changes affecting the membranes. When the disease is congenital, its presence in the foetus is apt to be a source of difficulty in parturition. It is however more commonly developed in the first six months of life; but it occasionally arises in older children, or even in adults. The chief symptom is the gradual increase in size of the upper part of the head out of all proportion to the face or the rest of the body. Occurring at an age when as yet the bones of the skull have not become welded together, the enlargement may go on to an enormous extent, the spaces between the bones becoming more and more expanded. In a well-marked case the deformity is very striking; the upper part of the forehead projects abnormally, and the orbital plates of the frontal bone being inclined forwards give a downward tilt to the eyes, which have also peculiar rolling movements. The face is small, and this, with the enlarged head, gives a remarkable aged expression to the child. The body is ill-nourished, the bones are thin, the hair is scanty and fine and the teeth carious or absent.
The average circumference of the adult head is 22 in., and in the normal child it is of course much less. In chronic hydrocephalus the head of an infant three months old has measured 29 in.; and in the case of the man Cardinal, who died in Guy’s Hospital, the head measured 33 in. In such cases the head cannot be supported by the neck, and the patient has to keep mostly in the recumbent posture. The expansibility of the skull prevents destructive pressure on the brain, yet this organ is materially affected by the presence of the fluid. The cerebral ventricles are distended, and the convolutions are flattened. Occasionally the fluid escapes into the cavity of the cranium, which it fills, pressing down the brain to the base of the skull. As a consequence, the functions of the brain are interfered with, and the mental condition is impaired. The child is dull, listless and irritable, and sometimes imbecile. The special senses become affected as the disease advances; sight is often lost, as is also hearing. Hydrocephalic children generally sink in a few years; nevertheless there have been instances of persons with this disease living to old age. There are, of course, grades of the affection, and children may present many of the symptoms of it in a slight degree, and yet recover, the head ceasing to expand, and becoming in due course firmly ossified.
