scholarly journals VII. The conditions of chemical change between nitric acid and certain metals

The science of chemistry presents few problems at once of such technical importance and such almost infinite complexity as the transformations of nitric acid; few problems, therefore, have been studied with so much diligence by a number of investigators. The preparation of certain metallic nitrates, the chemical changes and correlated electromotive forces of certain forms of batteries, require but to be mentioned, while the preparation of nitric oxide gas from metallic copper and moderately concentrated nitric acid forms both an exercise set before the veriest tyro in chemistry and the subject of several extensive memoirs. Within the last ten years no investigations have attracted so much attention as those which have proved beyond doubt that chemical changes hither6to regarded as almost fundamental, and as occurring between two substances, whether elementary or compound, do not in reality take place except in presence of some third substance. Thus, Dixon has shown that carbonic oxide will not combine with oxygen; H. B. Baker, that sulphur, phosphorus, and carbon do not burn in oxygen; Wanklyn, as also Cowper, that certain metals will not burn in chlorine; and other results might also be enumerated. In all these cases the necessary tertium quid is water.

It has long been known that in a mixture of solid salts chemical reaction may take place. Experiments on the subject have been made by Spring ( vide infra ), Thorpe,* and others. My attention was first called to the question by observing that a mixture of arsenious oxide and cadmium nitrate underwent a slow but complete change of composition, the final result being that the nitric acid was eliminated, arsenic acid taking its place. Preliminary Experiments .—Some experiments were made in order to discover what salts would be suitable for a careful investigation. The following were selected for trial, since a chemical change could be traced by an accompanying change of colour. The salts were finely powdered, but not specially dried.


The evolution of a gas, as a product of a chemical change, from a homogeneous liquid is among the earliest and most common experiences presented to a student of chemistry. Thus, oxygen and nitrogen, among the elementary gases, and nitrous oxide, nitric oxide, carbonic oxide, and hydrogen sulphide, among the compound gases, can be readily prepared either from certain salts in a state of fusion, or from aqueous or acid solutions of certain compounds. The effects produced on the rate and magnitude of these changes by varying the conditions of mass, temperature, pressure, and material of the containing vessel have not, hitherto, attracted the attention of investigators. In preference, similar dynamical problems have been studied of chemical changes occurring either between two or more gases, forming a gaseous product, or between homogeneous liquids, or between solutions of solids.


1891 ◽  
Vol 48 (292-295) ◽  
pp. 458-459 ◽  

This paper is in continuation of a preliminary communication on the same subject; the main points contained in it are as follows: I. The metals copper, mercury, and bismuth do not dissolve in nitric acid of about 30 per cent, concentration (the acid commonly employed for the preparation of nitric oxide gas) and heated to a temperature of 30ºC., provided that nitrous acid is neither present initially nor formed subsequently. To prevent this, it is nocessary in the cases of copper and bismuth to add a small quantity of some oxidising substance, such as hydrogen peroxide or potassium chlorate, or, as less efficacious, potassium permanganate, or to pass a current of air or, lastly, such a substance as urea, which destroys the nitrous acid by its interaction.


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.


1849 ◽  
Vol 139 ◽  
pp. 477-518 ◽  

1. In an inquiry into the constitution of the prussides, I found it necessary to examine into the somewhat anomalous action of nitric acid on the yellow prusside of potassium. This examination has led to the discovery of a singular class of compounds, which form the subject of the present memoir. The previous knowledge on the action of nitric acid on the prussides may be summed up very briefly. Thomson examined the gases produced during the action, and recognized them to be nitrogen, cyanogen, nitric oxide, and carbonic acid, while the residue was believed to consist of pernitrate of iron and nitrate of potash. Dobereiner remarked that previous to the complete decomposition of the prussides, a strong coffee-coloured liquid was produced, which, after neutralization, precipitated protosalts of iron of a dark blue colour. Gmelin, to whom chemistry was already indebted for important discoveries in the prussides, observed that the coffee-coloured liquid noticed by Dobereiner was rendered of a magnificent purple or blue colour on the addition of an alkaline sulphide. The same fact was noted by Mr. Mercer of Oakenshaw, without his being aware that it had already been remarked by Gmelin. Campbell, in repeating Gmelin’s experiment, threw out the intelligent suggestion that the purple colour might be due to the production of a sulphuret of nitrogen, which Gregory had already remarked produced an amethystine colour when mixed with an alcoholic solution of potash. Smee, in an examination of the action of nitric acid on the prussides, observes that ferridcyanide is produced, nitric oxide being evolved.


Of the commoner mineral acids the chemical changes of Nitric Acid, from their evident complexity, have formed the subject of numerous memoirs, while those of sulphuric acid, from their assumed simplicity, have been to some degree neglected; on the other hand, the physical properties of the latter have been studied with considerable elaboration, while those of the former have been passed over, doubtless on account of the corrosive nature of the acid and the difficulty of preparing and preserving it in a reasonable degree of purity. Further, with certain exceptions, the alterations in physical properties induced by the products of reduction, be they nitrogen peroxide or nitrous acid, either singly or conjointly, have attracted but little attention, though it is a common matter of observation that the current intensity of a Grove’s or other cell containing nitric acid remains constant, even though the fuming acid, originally colourless or red, has become of a deep green tint. It is more than probable that of the factors of Ohm’s law, both the E. M. F. and internal resistance are continually varying. At the earliest stages of the enquiry it was found that the passage of a few bubbles of nitric oxide gas into a considerable volume of nitric acid produced an alteration of one percent, in the resistance, and the same result could be effected to a less degree by exposure to sunlight, and to a still less degree by exposure to artificial illumination. Therefore, we determined to investigate the alterations of conductivity produced by changes of concentration and temperature in samples of acid purified with necessary precautions, more especially as former workers upon the subject have either used samples of acid confessedly impure, or have been silent as to any method of purification, or have adopted no special care in dealing with a substance so susceptible of polarisation.


1851 ◽  
Vol 141 ◽  
pp. 433-459 ◽  

Among the many discussions to which the subject of madder has given rise among chemists, there is none which is calculated to excite so much interest as that concern­ing the state in which the colouring matter originally exists in this root, and there is no part of this extensive subject which is at the same time involved in such obscurity. It is a well-known fact that the madder root is not well adapted for the purposes of dyeing until it has attained a growth of from eighteen months to three years, and that after being gathered and dried it gradually improves for several years, after which it again deteriorates. During the time when left to itself, especially if in a state of powder, it increases in weight and bulk, in consequence probably of absorp­tion of moisture from the air, and some chemical change is effected, which, though not attended by any striking phenomena, is sufficiently well indicated by its results. There are few chemical investigations that have thrown any light on the nature of the process which takes place during this lapse of time, and in fact most of the at­tempts to do so have merely consisted of arguments based on analogy. It has been surmised that the process is one of oxidation, and that the access of atmospheric air is consequently necessary. We are indeed acquainted with cases, in which substances of well-defined character and perfectly colourless, as for instance orcine and hematoxyline, are converted by the action of oxygen, or oxygen and alkalies combined, into true colouring matters. A more general supposition is, that the process is one of fermentation, attended perhaps by oxidation, and in confirmation of this view the formation of indigo-blue from a colourless plant, by a process which has all the cha­racters of one of fermentation, may be adduced. What the substance is however on which this process of oxidation or fermentation takes effect, what the products are which are formed by it, whether indeed the change is completed as soon as the madder has reached the point when it is best adapted for dyeing, or whether further changes take place when it is mixed with water and the temperature raised during the process of dyeing, are questions which have never been satisfactorily answered, if answered at all. It has indeed been suspected by several chemists, that there exists originally some substance in madder, which by the action of fermentation or oxida­tion is decomposed and gives rise by its decomposition to the various substances endowed either with a red or yellow colour, which have been discovered during the chemical investigations of this root. That several of these substances are merely mixtures, and some of them in the main identical, has been satisfactorily proved by late investigators. But there still remain a number, which, though extremely similar, have properties sufficiently marked to entitle them to be considered as distinct. In my papers on the colouring matters of madder, I have described four substances derived from madder, only one of which is a true colouring matter, but all of them capable, under certain circumstances, as for instance in combination with alkalies, of developing red or purple colours of various intensity. To seek for a common origin for these various bodies so similar to one another and yet distinct, is very natural, and the discovery of it no improbable achievement.


2020 ◽  
Vol 21 (8) ◽  
pp. 2703 ◽  
Author(s):  
Tommaso Gori

Amyl nitrite was introduced in 1867 as the first molecule of a new class of agents for the treatment of angina pectoris. In the following 150 years, the nitric oxide pathway has been the subject of a number of pharmacological approaches, particularly since when this elusive mediator was identified as one of the most important modulators of vascular homeostasis beyond vasomotion, including platelet function, inflammation, and atherogenesis. While having potent antianginal and antiischemic properties, however, nitric oxide donors are also not devoid of side effects, including the induction of tolerance, and, as shown in the last decade, of oxidative stress and endothelial dysfunction. In turn, endothelial dysfunction is itself felt to be involved in all stages of atherogenesis, from the development of fatty streaks to plaque rupture and thrombosis. In the present review, we summarize the agents that act on the nitric oxide pathway, with a particular focus on their potentially beneficial antiatherosclerotic and unwanted pro-atherosclerotic effects.


1867 ◽  
Vol 157 ◽  
pp. 117-137 ◽  

The reaction of hydric permanganate upon hydric oxalate, which formed the subject of the first part of this inquiry, having proved to be of a complex character, consisting in fact of several distinct reactions, it became necessary to seek for investigation a simpler case of chemical change. The reaction selected must at the same time combine all the other qualifications before enumerated, that it might be possible successively to vary its conditions and to measure its conditions and its amount. After making trial of several reactions which appeared suitable, and being as often foiled by some practical difficulty in the proposed methods of investigation, we at last succeeded in devising for a very simple case of chemical change a method of investigation at once easy and exact. The reaction is that of hydric peroxide and hydric iodide, H 2 O 2 +2HI = 2H 2 O+I 2 .


1973 ◽  
Vol 12 (6) ◽  
pp. 1369-1373 ◽  
Author(s):  
Siegfried Jordan ◽  
Francis T. Bonner

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