Reaction of Copper(I) Nitrotetrazolate (DBX-1) with Sodium m-Periodate

The reaction of the lead-free primary explosive copper(I) 5-nitrotetrazolate (DBX-1) with sodium m-periodate yields a green precipitate of copper(II) iodate. The energetic properties of the copper(I) nitrotetrazolate starting material are lost since the nitrotetrazolate is removed into the aqueous phase during rinsing, leaving only non-explosive copper(II) iodate and copper(II) periodate. Based on the results of this investigation, the use of oxidizing components in DBX-1 formulations may be limited due to the readiness of copper(I) to be oxidized to copper(II).

Plutonium(IV) peroxide formation in nitric medium and kinetics Pu(VI) reduction by hydrogen peroxide

Reduction of plutonium (VI) to Pu(IV) with hydrogen peroxide is a step in industrial processes used to purify plutonium nitrate solutions. This operation must be carefully controlled, in order to avoid any formation of the Pu(IV) peroxide green precipitate and to obtain exclusively Pu(IV). This led us to study the acidity and Pu and HWith the exception of 0.5 M nitric acid medium, the kinetic curves show two distinct regims: the first one corresponds to an induction period where the Pu(VI) concentration doesn´t change, the second corresponds to a linear decrease of Pu(VI). An increase of the temperature greatly accelerates the Pu(VI) reduction rate while [H

Molten lithium nitrate-potassium nitrate eutectic: the reaction of chromium(II) chloride

The strong reducing agent chromium(II) chloride reacted rapidly in molten lithium nitrate-potassium nitrate, at or above the melting point of the eutectic, initially forming a dark-brown-black solution [probably containing chromium(III) and chromium(VI)] and gaseous nitrogen dioxide, but at 200�C giving a green precipitate (Cr2O3) and an orange solution of dichromate. Above 450�C, a further slow reaction converted both compounds into a yellow solution of chromate(VI) containing nitrite partly formed by thermal decomposition of the nitrate.

V. Note on the constitution of chlorophyll

An examination of some products derived from chlorophyll, which has occupied me for some time, has led to the question of the true nature and constitution of chlorophyll, a question on which widely different opinions prevail. Without entering into matters which concern the physiologist only, it may be said that to the chemist chlorophyll is simply an organic colouring-matter, the substance to which the green colour of leaves and other parts of plants is due. Now colouring-matters are of three kinds. To the first class belong such as occur ready formed and in a free state in vegetable and animal organisms, such as the colouring-matters of turmeric and safflower. The second class comprises those that are formed from colourless chromogens by the combined action of alkalis and oxygen, the colouring-matters of log-wood and archil being well-known examples of this class. These colouring-matters change rapidly when exposed to the further action of oxygen in the presence of alkali, but are quite stable when in contact with acids. The third class consists glucosides, bodies which do not undergo any considerable change under the influence of alkalis, but are rapidly decomposed when acted on by acids or ferments, yielding, on the one hand, some kind of glucose, and, on the other, substances in which the tinctorial properties of the parent substance are much more pronounced. To this division belong the colouring-matters of madder, quercitron, cochineal. &c. Now chlorophyll in its general properties so much resembles the members of the last class that one cannot help suspecting that to this class it may belong—that it is in fact a glucoside. It shows considerable stability in the presence of alkalis, but acids decompose it rapidly, giving rise to substances which are intensely coloured and show a power of absorbing particular parts of the spectrum much more strongly than chlorophyll itself. Whether, along with the latter bodies, it yields by decomposition with acids some kind of glucose, seemed to me a question worthy of attention. If it was possible to obtain chlorophyll in a state of purity, it would be very easy to settle this question; unfortunately all attempts hitherto made to separate and purify chlorophyll have ended in its decomposition. I consider it as certain that the so-called crystallised chlorophyll which has been described by several authors is in fact a derivative of chlorophyll formed during the process employed for preparing it. It is, however, very easy to obtain a solution of chlorophyll which shall be quite free from everything soluble in water extracted at the same time from the plant, and therefore free from ready-formed glucose. In order to effect this, I proceed as follows:— Having extracted leaves of any kind with boiling alcohol, I allow the extract to stand for some time, filter off the deposit which usually forms, and then mix it with its own volume of ether and with about two volumes of water, shaking up well. The liquid now separates into two layers, an upper green one, containing all the chlorophyll of the extract, and a lower bright yellow one, which contains tannin, a yellow colouring-matter, a substance giving the glucose reaction with Fehling’s solution, and probably other substances besides. The two liquids are separated in the usual way, and the upper one is shaken up with fresh water, which now usually only shows a trace of colour. This process of washing may be repeated, adding each time a little fresh ether, until the lower layer ceases to give the glucose reaction. The upper liquid leaves on spontaneous evaporation a bright green residue, which, though far from being pure chlorophyll, is free from everything soluble in water, and may therefore be employed to determine whether anything soluble in water, such as glucose, is formed by the action of acids on it. If some of the residue be treated with concentrated sulphuric acid in the cold it dissolves, forming a green solution, which, after standing for some time, gives. on the addition of water, a dark green precipitate. This precipitate consists essentially of two substances, the phyllocyanin and phyllo-xanthin of Frémy, which are undoubtedly products derived from chlorophyll, showing the absorption bands of what is usually called “acid chlorophyll.” The liquid filtered from this precipitate, when mixed with copper sulphate and an excess of caustic alkali, becomes blue, and the mixture, on boiling, deposits cuprous oxide. The experiment may be made in a slightly different manner. The residue left by the green ethereal solution of chlorophyll having been dissolved in alcohol, sulphuric or hydrochloric acid is added to the solution, which is then boiled for some time, evaporated so far as to drive off most of the alcohol, filtered from the products insoluble in water, made alkaline, then mixed with Fehling’s solution and boiled, when the usual glucose reaction takes place. In order to make sure that the reaction was not due to ready-formed glucose, I took in every case the precaution of testing a portion of the green chlorophyllic residue with Fehling’s solution before acting on the rest with acid. This was easily done by treating with weak alcohol, to which a little alcoholic potash and some Fehling’s solution were added, and heating, when the whole dissolved easily, giving a green solution, which, on boiling, in no case deposited the least trace of cuprous oxide, whereas, after adding an excess of hydrochloric acid to the liquid, boiling, filtering off the insoluble products, again making alkaline and boiling, the glucose reaction took place in a marked manner.

On the nitroprussides, a new class of salts

When nitric acid is made to act on yellow prusside of potassium, in the proportion of one equivalent of acid for every equivalent of potassium present in the salt, the following reactions are observed. The salt dissolves in the acid with a dark red, almost black colour, a very little nitric oxide is evolved, which soon ceases, and is fol­lowed by a copious evolution of cyanogen mixed with nitrogen. The continued action of the acid causes the liquid to cease the usual reactions of red prusside of potassium; the addition of sulphate of iron now produces a slate-coloured instead of blue precipitate. On allowing the solution to cool, abundance of nitrate of potash cry­stallizes out, mixed with a little prussian blue, and about 5 percent, of the original weight of the salt, of a white granular substance, which is scarcely soluble in cold, and only very slightly so in boil­ing water. This white substance, on examination, proves to be the remarkable body oxamide , the production of which in an oxidising medium is highly singular. The dark red supernatant liquor, being neutralized with an alka­line carbonate, and boiled, deposits a green precipitate and yields a clear ruby-red solution. This solution furnishes the new class of salts, which is the subject of this paper. It may be evaporated to crystallization, and yields the nitroprusside of the base used in the neutralization.