Action of Ethylic Chloromaleate on Ethylic Acetoacetate.

The chloromaleic acid was prepared by distilling chlorofumaric acid, and by dissolving the resulting anhydride in water (Perkin, Trans., 1888, 53, 695). In the distillation, part of the chlorofumaric acid passes over unchanged, together with chloromaleïc anhydride, as already observed by Kauder (J. pr. Chem., 1885, 31, 1); the purification is brought about by distillation under diminished pressure, when the chlorofumaric acid remains behind (Zincke, Ber., 1893, 26, 508). The ethereal salt of chloromaleic acid, obtained, according to Perkin's direction, by the action of ethylic iodide on the dry silver salt, boils at 122° under a pressure of 15 mm.

Ethylic chloromaleate acts on the sodium derivative of ethylic acetoacetate as readily as the derivative of fumaric acid does, giving rise to the formation of the same compound as that obtained from chlorofumaric acid. It boiled at 187-188° under a pressure of about 15 mm., and gave on analysis the following numbers.

0-2196 gave 0.4507 CO2 and 0·1306 H2O.

CH20O, requires C 560; H =

=

C = 55·97; H = 6·60 6.67 per cent.

The determination of the density of the ethereal salt gave the following result. d 12°/12° 1·1588; the refractive index was found by Mr. Wilberforce to be na = 1.470.

The identity of the product formed from ethylic chloromaleate with that from the corresponding derivative of fumaric acid, which is proved by its physical properties, follows also from the chemical behaviour. Ammonia acts on the substance obtained from the ethereal salt of chloromaleïc acid with formation of a compound of the formula CH1N2O5, the identity of which, with the product resulting from ethylic chlorofumarate, is proved by the melting point (1950) and by a nitrogen determination.

0.200

gave 21 c.c. moist nitrogen at 18° aud 732 mm. N = 11.66. C10H1N2Os requires N = 11·56 per cent.

We are at present engaged in the further study of the compounds described in this paper, and hope shortly to communicate the result to the Society.

Gonville and Caius College

Cambridge.

XXXIX.-Analysis of the Water from the Dropping Well at Knaresborough, in Yorkshire.

By BENJAMIN ARTHUR BURRELL.

THE history of Knaresborough dates from before the Norman Conquest, and the remarkable petrifying qualities of this spring must have attracted attention at a very early period. Its character was well known in 1534, for Leland thus describes it (Leland's Itinerary) :

"A little above March Bridge, but on the farther ripe of Nidde as I cam, is a Welle of a wonderful nature, caullid Dropping Welle, for out of the great Rokkes by it, distilleth water continually ynto it. This water is so could, and of such a nature, that what thing soever faullith oute of the Rokkes ynto this pitte, or ys caste in or growith about the Rokke and is touched of this water, growith ynto stone; or else some sand, or other fine ground that is about the Rokkes, cummith doune with the continualle droping of the Springs in the Rokkes, and clevith on such things as it taketh, and so clevith aboute it and giveth it by continuance the shape of a stone. There was ons, as I hard say, a conduct of stone made to convey water from this welle over Nidde to the priory of Knaresborough; but this was decayed afore the dissolution of the house."

It would, therefore, appear that some time prior to 1534, the water was used for drinking purposes.

From 1626 up to as late as 1838, it had a considerable reputation as a spa water, and numerous references as to its medicinal qualities are to be found in the works of Short, Elliott, Walker, and Hunter.

Dr. Short, in 1734, found it "to be twenty-four grains in a pint heavier than common water, on exhaling eighteen pints it left seventeen scruples of sediment."*

In 1783, Dr. Walker states, "the petrefying spring at Kuaresborough contains a considerable quantity of selenitical, and a smaller quantity of calcareous earth."+

This water was analysed in 1830, by Mr. W. West, of Leeds. His numbers were‡

* The Natural, Experimental, and Medicinal History of the Mineral Waters of Derbyshire, Lincolnshire, and Yorkshire. By Thomas Short, M.D., of Sheffield. London, 1734.

An Essay on the Waters of Harrogate and Thorp Arch in Yorkshire. By Joshua Walker, M.D. London, 1784.

The Waters of Harrogate and its Vicinity. By Adam Hunter, M.D. London, 1830; also, On Mineral Springs and other Waters of Yorkshire. By W. West. British Association Report, 1844,

So far as I am aware, no analysis has been made since 1830, and it seemed very desirable that a more complete examination should be made of this cnrious water. The investigation was commenced in 1894, and extended over the following year, various samples of the water having been taken from time to time.

The strata on which Knaresborough is built is mostly magnesium limestone. The Dropping Well is situated in the Long Walk, on the south-west bank of the river Nidd, where the water rises in the steep declivity of a hill, at the foot of a limestone rock, and flows in a small stream for about 24 yds. It is then caused to spread over the surface of a large rock, some 30 ft. high and 32 ft. long, over which it trickles. The upper part of this rock projects considerably over the base, and it is to this projection that the articles to be petrified are hung.

The water for analysis was collected immediately as it issues from the ground; at this point it is very clear and free from suspended particles. The flow is about 20 gallons a minute, and the temperature very constant, two readings giving

August

December....

Temp. of air, 15.5° C.; temp. of water, 9.7° C.

The specific gravity = 1·0024 at 15.5°; it was taken by means of a Sprengel tube, the capacity of which had been very carefully determined. In each case the determination was made the same day as that on which the water was collected.

Analysis. The general course adopted was that recommended by Fresenius; the numbers given are the means of at least two, and in some cases three or more concordant results. For the estimation of substances present in minute quantity, 25 litres were evaporated, but no traces of bromine, iodine, fluorine, or lithium could be detected.

Strontium was separated by the Rose-Stromeyer process, which has been carefully examined by Fresenius (Abstracts, 1893, ii, 301), who finds it to give very perfect results. The method was checked by making up mixtures of calcium and strontium sulphates in proportions similar to those found in the well water, the results

obtained show that the process is trustworthy. In each estimation, the separated strontium sulphate was subjected to spectroscopic examination, but contained only the merest trace of admixed calcium sulphate.*

In estimating the gases dissolved in the water, the apparatus devised by Sidney Harvey was employed (Analyst, 1894, 19, pp. 121, 122, 123); by means of this apparatus, the water may be collected at the source in the bulb in which it is afterwards boiled, thus reducing contact with the atmosphere to a minimum.

The atomic weights used are those given in Clowes and Coleman's Quantitative Analysis, 1894.

In the first table, the quantities of the different constituents are given in grams per litre under I, and in grains per gallon under II. In III the acids and bases are combined together, and the results stated in grains per gallon; and Table IV gives the gases dissolved in the water.

In combining the various acids and bases, a deviation from the usual course has been adopted, the sulphuric acid being first combined with the magnesium in preference to the calcium, as practically the whole of the magnesium was found in the boiled water, and none in the sediment thrown down on boiling.

*For the occurrence of strontium sulphate at Knaresborough the following may be consulted: Trans. Geological Society, 1817, 4, 445; Edinburgh Phil. Journal Jan. 1825, 12, 178, 179.

It should be stated that all the reagents used in the analysis were not only of the highest degree of purity obtainable, but were carefully tested, the impurities estimated, and (as measured quantities were used throughout) allowed for in the final results.

It is intended to make the analysis of the deposit or sinter the subject of a future paper.

XL.-Charas.

The Resin of Indian Hemp.

By T. BARLOW WOOD, M.A., W. T. NEWTON SPIVEY, M.A., and THOMAS HILL EASTERFIELD, M.A., Ph.D.

SEVERAL preparations of Cannabis indica (syn. sativa), differing in physiological activity and in the manner of application to the human subject, are familiar to the Eastern nations. Of these, "charas" is an Indian drug, and is regarded by the natives as the most potent substance obtainable from the plant. It is chiefly used in the Punjab, and consists essentially of the resinous exudation from the stems, leaves, and flower heads of the unfertilised female plant. By the kindness of Mr. Charles A. Silberrad, B.A., I.C.S., at present resident at Etawah, N.W.P., the authors have been provided with several pounds of the resin, the examination of which has furnished the materials for the present communication.

Cannabis indica has been employed medicinally, both in this country