Iodine Chloride Research Articles

The Photo-Reaction of Hydrogen and Iodine Monochloride

WE are able to confirm the observations of D. P. Mellor and T. Iredale 1 on the photo-reaction between iodine monochloride and hydrogen, as against the photo inactivity of the mixture reported by Rollefson and Lindquist.2 A rapid photo-reaction between these substances when not specially purified had been observed by us before the appearance of Rollefson and Lindquist's paper ; the reaction, however, is much influenced by traces of impurities, for when special pains are taken to avoid contamination by organic materials, stopcock grease and the like, the rate of reaction under the influence of light is much decreased. There remains, however, an easily measurable reaction under the influence of the light of a mercury arc. The main products are hydrogen chloride (HC1) and iodine (I2); no appreciable amount of hydrogen iodide has been found. The photo-reaction between iodine chloride and methane has also been established in this laboratory ; the rate here is great compared with that of the hydrogen reaction. Both reactions are being investigated in detail.

Determination of the Iodine Number of Raw Rubber

Abstract In the course of an investigation dealing with the nature of the state of unsaturation of raw rubber, it became necessary to have available a precise and convenient method for determining the iodine number of raw rubber. Though iodine reacts only slowly with unsaturated compounds, chlorine and bromine form both addition and substitution products. In the substitution reactions, the hydrogen halide is evolved, and by addition of potassium iodate, e.g., in the method of MacIlhiney, it is possible to determine the hydroden halide formed and thus the quantity of halogen substituted. In all methods, however, where extensive substitution as well as addition take place, the results are variable and uncertain. Accordingly in the chemistry of fats where the iodine number is of the greatest importance, iodine halides have been used for determining the iodine number, for under certain conditions there is very little substitution. Thus Hübl, Waller and Wijs solutions contain iodine chloride and Hanus solution contains iodine bromine. The Hanus method has in fact to a great extent replaced all other methods For determining the iodine number of rubber, the Wijs method in the form in which it was modified by Kemp is probably used more than any other. In the Kemp method about 0.1 gram of rubber is swollen in 75 cc. of carbon disulfide, and is then allowed to react for 2 hours at 0° C. with 25 cc. of Wijs solution, i.e., 0.5 N iodine chloride in acetic acid.

The influence on basal metabolism of some derivatives of di-iodotyrosine.

The structure of thyroxin as recently determined by Harrington1 represents the substance as a derivative of di-iodotyrosine and as containing two benzene rings. It is, therefore, of some interest to know what effect, if any, other derivatives of di-iodotyrosine containing two aromatic nuclei, would exert on basal metabolism.Two such substances have been examined, namely, di-iodotyrosyl-di-iodotyrosine and the cyclic anhydride (diketopiperazine) of di-iodotyrosine. The former substance may be prepared by the action of iodine in feebly alkaline solution upon tyrosyl-tyrosine, or by the regulated action of alkali on the cyclic anhydride of di-iodotyrosine. The latter substances cannot be obtained by the direct action of iodine upon tyrosine anhydride, but may be readily attained by the action of iodine chloride in acetic acid upon the anhydride. Both substances are cream colored microcrystallin compounds, which in their solubilities and general chemical deportment, colour reactions, etc., show considerable r...

The Treatment of Diphtheria by Anti-Toxic Serum

FOUR years ago Prof. Behring published his remarkable paper “On the mechanism of immunity agains experimental diphtheria in animals.” In this memoir the author stated that it was possible to immunise animal; against the diphtheria bacillus by the injection of culture attenuated by heat or the addition of 1 in 500 tri chloride of iodine to the cultivating medium. The same result could be obtained by the inoculation of the pleura exudation of animals dead of experimental diphtheria or by the injection of chemical compounds, such a trichloride of iodine, after inoculation of virulent diphtheria-bacilli.

VI. On the formation of chlor-iodide and brom-iodide of ethylidene

Chlor-iodide of ethylidene CH 3 | CHClI. This body I have succeeded in preparing by two processes. First Process.—A quantity of iodide of ethylidene, which had been prepared by Gustavson’s method, and heated to 160°C. but not distilled, was vigorously agitated for some time with a weak solution of chloride of iodine without the application of heat. The excess of chloride was then poured off, and the product well washed with dilute potash and distilled. Almost the entire quantity passed over between 110 and 150°C. This yielded, on fractioning, a large quantity of fluid boiling between 116 and 120°C., most between 117 and 119.° This was the body in question. The chloride of iodine used in this process was prepared by passing washed chlorine into 4 oz. of water, holding 400 grains of iodine in suspension, till almost all the iodine was dissolved. The vessel containing the iodine must be surrounded with cold water, ind repeatedly shaken during the passage of the gas.

II. Chemistry notes

The first step towards the direct formation of this and other chloro-bromides is, of course, the preparation of the solution of chloride of bromine. This I endeavoured to prepare by a process analogous to that by which I had formed the chloride of iodine. I found, however, that in passing the chlorine into the bromine and water, a larger quantity of the former is carried off in the form of vapour. I continued the passage of the gas, nevertheless, till all the bromine was dissolved and the solution assumed a faint yellow tint. On conducting olefiant gas into this, I obtained a very small quantity of an oily liquid, part of which boiled between 106° and 110° Cent. Altogether, it is by no means a productive progress. I made an ineffectual effort to improve it by surrounding the vessel containing the bromine with ice.This, however, only made matters worse, as it caused the formation of solid hydrate of chlorine and of bromine, which prevented the completion of the process. After several unsuccessful experiments I at last hit upon the following process, which answers remarkably well:—500 grains of bromine are dissolved in 4 fluid ounces of a mixture of equal volumes of strong hypochloric acid and water. This solution is introduced into a flask with a long neck, and surrounded with ice. Washed chlorine is then passed into it with repeated agitation, till it ceases to be absorbed. In this way not a trace of bromine is lost, nor are any solid hydrates formed during the passage of the gas. On conducting olefiant gas into this solution, which should be surrounded with cold water and repeatedly agitated, I obtained a large quantity of an oily liquid, which I separated from the acid solution, washed with dilute potash, and distilled. Almost the entire quantity passed over between 106° and 110°, most between 108° and 110°. The following analysis proves that this was the body in question in a state of purity:— C 2 H 4 ClBr. Theory. Experiment. Carbon. . . . . . 16.72 16.57 Hydrogen . . . . 2.78 3.01 This process yields nearly 80 per cent. of the theoretical quantity. Chloro-bromide of propylene (C 3 H 5 ClBr).

I. On the brom-iodides

Some years ago I ascertained that chloride of iodine combines directly with the olefines and the non-saturated haloid ethers in the same manner as free chlorine or bromine. I have since ascertained that bromide of iodine also enters into direct combination with these bodies. In the following experiments I have invariably used a solution of bromide of iodine in water, which was prepared by adding rather more than a molecule of iodine in fine powder to a molecule of bromine previously mixed with about six times its weight of water. The bromine was repeatedly agitated during the addition of the iodine, and kept cold by being surrounded by water. An almost black liquid was thus obtained, which was separated from the excess of iodine.

On the absorption-spectra of chlorine and chloride of iodine

On the absorption-spectra of chlorine and chloride of iodine

XXXIX.—Action of chloride of iodine on picric acid

The first page of this article is displayed as the abstract.

II. On the action of chloride of iodine upon organic bodies

In a former communication I stated to the Society that chloride of iodine combines directly with ethylene and propylene gases. I have since ascertained that it also directly combines with those radicals which are at the same time both mono- and tri-atomic. Iodide of allyle and bromide of aldehydene, having the desired atomicity, were the bodies I selected for my experiments. Action of Chloride of Iodine on Iodide of Allyle .—In order to determine the union of these bodies, it was simply necessary to mix and agitate them. The chloride of iodine used was in the form of a watery solution. During the agitation the mixture became warm, and assumed a dark colour from the liberation of iodine. To complete the reaction, it was gently heated over the lamp for a short time. By these means a dark oily liquid was obtained, which was separated from the excess of chloride of iodine, washed with dilute potash, then with pure water, and distilled. Almost the entire liquid passed over between 190° and 215° Cent, The fraction distilling between 205 and 210 being very considerable in quantity, was collected separately and analyzed, having been previously decolorized by agitation with mercury. The numbers obtained correspond sufficiently well with the formula C 6 H 5 Cl 2 I, as will be seen from 'the following Table.

XXXVI.—Action of chloride of iodine on certain organic substances

The first page of this article is displayed as the abstract.

XL.—Note on the action of chloride of iodine on certain organic substances

XL.—Note on the action of chloride of iodine on certain organic substances

IV. On the action of chloride of iodine on iodide of ethylene and propylene gas.—Second notice

In my last communication to the Society I announced that a body having the composition expressed by the formula C 4 H 4 I Cl was formed when iodide of ethylene was subjected to the action of chloride of iodine. I have since ascertained that the same body may be obtained by the direct action of ethylene gas on the latter reagent. By this process it can be prepared in large quantity with great facility.

II. On the action of chloride of iodine on iodide of ethylene and propylene gas

I have already shown that the cyanides of the diatomic radicals can be prepared by submitting their bromides to the action of cyanide of potassium. In the hope of forming the cyanides of the triatomic radicals in a similar manner, I subjected the bromides of several of these latter radicals to the action of the same reagent. Finding, how ever, the reaction not quite satisfactory, it occurred to me that the iodides of these radicals might possibly yield better results.

Precipitate of chloride of iodine by sulphuric acid

Precipitate of chloride of iodine by sulphuric acid