On the Nature of “Palladium Hydrogen”

1899 ◽  
Vol 22 ◽  
pp. 169-186 ◽  
Author(s):  
John Shields

Ever since the remarkable discovery by Graham in 1866 that palladium possesses the power of occluding hydrogen gas in large quantity, various views have from time to time been put forward to explain the true nature of the phenomenon. Whilst some observers regard hydrogenised palladium as an alloy or solid solution, others again consider it to be, or at least to contain, a definite chemical compound or hydride. Those who hold the latter opinion, however, are not agreed as to which compound or hydride is formed, as is proved by the fact that different formulae have been ascribed to it. Graham himself recognised the possibility that a definite chemical compound might be formed, for he says (Researches, 287) that in fully-charged palladium there exists one equivalent of palladium to 0·772 equivalent of hydrogen, or an approximation to single equivalents which would be represented by the formula PdH. His opinion was, nevertheless, opposed to the idea of such a definite chemical combination, one of his chief objections being that no visible change is occasioned to metallic palladium by its association with hydrogen. He regarded the product simply as an alloy of the volatile metal hydrogenium, in which the volatility of the one element is restrained by its union with the other, and which owes its metallic aspect equally to both constituents.Considerations of a purely chemical character have up to the present time proved insufficient to decide which of these views is correct.

The law of Neumann assumes that when an atom enters into chemical combination it retains the same capacity for heat as when in the uncombined or elemental state. This generalisation is, however, based on the values observed for the mean specific heats of elements and their compounds between 0° and 100° C. Attention was directed in Part II. of this investigation to the great differences found in the influence of temperature on the specific heats of various metals, such as aluminium on the one hand, and silver or platinum on the other. The experiments now about to be described were undertaken with the object of ascertaining to what extent these differences persist in the compounds of such elements.


1871 ◽  
Vol 161 ◽  
pp. 477-510 ◽  

A few preliminary words may he necessary to prevent misunderstanding respecting the claims and objects of the following memoir. When I entered upon the investigation of which it records the results, I found, in the writings of various British and foreign authors, a copious Calamitean literature; hut the widest discrepancies prevailed amongst them both as to facts and to inductions. I therefore determined to pursue the study of this group of fossils as if de novo, to record the facts which I observed, and to draw from those facts alone such inferences as seemed legitimate, both facts and inferences being in a certain sense, and so far as was possible under the circumstances, new and original. But it necessarily follows that some of these facts and inferences are not absolutely new, though many of them, I think, will he found to he additions to our knowledge of the subject; whilst others, though not new, have presented themselves to me in a light different to that in which they have been regarded by my able predecessors in the study. Such being the object of the memoir, I have not deemed it desirable to include in it a record of all the observations made by preceding writers. As a rule I have only referred to them when the discussion of some moot point rendered such a reference necessary. The fundamental aim of the memoir is to demonstrate the unity of type existing amongst the British Calamites. Brongniart, Dawson, and other writers believe that there exist amongst these plants two types of structure, the one Cryptogamic and Equisetaceous, the other Exogenous and Gymnospermous; on the other hand, Schimper and Carruthers regard the whole as Equiseceous, affording an example of the diversity of opinion on fundamental points to which I have already referred. Of course, before arriving at their conclusions, Brongniart, and those who adopt his views, had fully apprehended the exogenous structure of the woody zone of the Calamite, which is further illustrated in this memoir. The separation of each internode into vertical radiating plates of vascular and cellular tissues, arranged alternately, was familiar to Brongniart, Unger, and other early observers. Cotta regarded the cellular tracts (my primary medullary rays) as medullary rays ; but this interpretation was rejected by Unger, and the same divergence of view on this point has recurred amongst subsequent writers. Unger also noticed what I have designated secondary medullary rays, but at a much more recent date Mr. Carruthers disputed their existence. In their 'Fossil Flora of Great Britain,' Lindley and Hutton gave very correct illustrations of the position of the roots of Calamites relatively to the stem ; and yet for years afterwards some of their figures reappeared in geological text-books in an inverted position, the roots doing duty as leaves ; so far was even this elementary point from being settled. The true nature of the common sandstone form of Calamites, viz. that they are inorganic casts of the interior of the woody cylinder from which the pith has been removed, has been alike recognized by Germar, Corda, and Dawes; but they referred the disappearance of the cellular tissues of the pith to inorganic decay which took place subsequently to the death of the plant. It appears to me that the condition in which we find these cellular tissues affords no countenance to this conclusion. They are as perfectly preserved, when present, as any of the other tissues of the plant. Their inner surface, nearest the fistular cavity, presents no appearance of death and decay, but of rupture and absorption, which I conclude has occurred during life,—a different hypothesis from that adopted by my predecessors, and for which my reasons will be assigned in the memoir. The labours of Mr. Binney are referred to in the text. He figured the longitudinal internodal canals, but was disposed to believe that they had merely formed passages for vessels. He gave, however, excellent figures of the woody wedges, the primary medullary rays, and the cellular medulla, with its nodal septa or diaphragms .


1899 ◽  
Vol s2-42 (168) ◽  
pp. 477-495
Author(s):  
EDWIN S. GOODRICH

According to the foregoing account, the evidence of carefully executed injections strongly favours the view that a continuity exists between the contractile vascular system and the noncontractile sinus system in Hirudo. This continuity is proved to exist in various regions of the body by means of serial sections. The communication takes place through the capillary systems. The hæmolymph system of Hirudo consists of four main longitudinal trunks, sending out transverse branches to the body-wall. The dorsal branches of the lateral vessels pass into small annular vessels communicating with the plexus of minute capillaries in the epidermis. From these, again, arise capillaries going to small sinuses which run into the lateral transverse sinuses, and so into the dorsal sinus. Similarly (he ventral sinus sends annular sinuses along the ventral region of the body-wall opening into the epidermal plexus, whence arise capillaries joining the latero-abdominal vessels. Continuity between the two systems has also been shown to take place by means of capillaries on the wall of the alimentary canal, and probably exists on the other internal organs of the body. Two questions still remain to be solved: firstly, as to the circulation of the hæmolymph; secondly, as to the exact homology of the channels in which it flows. With respect to the first of these problems, I have no direct observations to record; but it may be pointed out that the presence of the valves described above show, at least, that the hæmolymph must flow in a constant direction--that there is a real circulation, not a mere motion backwards and forwards. It seems to me extremely probable that the annular vessels collect the oxygenated blood from the epidermal plexus, and carry it into the latero-dorsal and latero-lateral vessels, whence it would be pumped into the lateral vessels. From these some of the hæmolymph must be carried by the latero-abdominal vessels to the various organs of the body, and to the ventral cutaneous plexus. The annular sinuses would collect it from this plexus and carry it into the ventral sinus. The abdominodorsals and the dorsal sinus would appear to supply the dorsal and lateral cutaneous plexus. We are left in considerable uncertainty as to the true nature of some of the spaces. That the lateral vessels belong to the real vascular system, and that the ventral sinus and perinephrostomial sinuses belong to the true cœlomic system, seems to be clearly established both by comparative anatomy and by the embryological researches of Bürger (2). This observer, however, could not trace the dorsal sinus to a cœlomic origin, and since its branches bear the same relation to the cutaneous plexus as those of the latero-abdominal vessels, I am inclined to think that the dorsal sinus may represent the dorsal vessel of other annelids. In that case the cœlomic cavities do not persist dorsally, or have never reached the median dorsal region in the Gnathobdellidæ. The annular channels may possibly represent the annular cœlomic lacunæ so well described and figured by Oka in Clepsine (10), and it may perhaps be through them that the chief communication between the cœlom and the vascular system has been established. The observation of the some-what variable relations of these annular channels tends to support this view. With the very imperfect knowledge of the development of the cœlom and blood-vessels in Hirudo at our disposal, we cannot say for certain at present where the one ends and the other begins, nor whether a given capillary really belongs to the one or the other. Nor can we safely conjecture how the continuity has actually taken place. But one thing seems fairly certain, namely, that it is not only by means of the botryoidal channels that the communication has been brought about. It is very tempting to compare the leech with the Vertebrate, in which a third system of spaces--the lymphatic system--has been interpolated, allowing a communication to take place between the originally distinct cœlom and blood-vascular system.1 But the botryoidal tissue is not so inter-polated in the case of Hirudo; if it were obliterated, the two systems would still be in free continuity by means of capillaries. The botryoidal channels would seem to be rather of the nature of a by-path, through which the hæmolymph does not necessarily circulate. In this connection it should be mentioned that in sections they are rarely seen to be as much distended with the fluid as the neighbouring capillaries of similar size. Whatever may be the process whereby the continuity between the cœlom and vascular system has been established in the Gnathobdellidæ, there can be little doubt that it is a secondary condition, and that the structure of such a form as Acanthobdella, in which a closed blood-system lies in a normally developed cœlom, is really the more primitive.


PMLA ◽  
1927 ◽  
Vol 42 (2) ◽  
pp. 443-464 ◽  
Author(s):  
James R. Foster

The true nature of the so-called Gothic novel has been misunderstood, and the problem of its origin rendered unnecessarily difficult in consequence of a classification which takes only one of the many features into account. The critics who have hit upon supernaturalism as the most distinctive and significant element, have done this in spite of the fact that a part of the body of the fiction they pretend to describe is plainly controlled by a rationalism that forbids anything more than a mere toying with the appearances of the marvellous. No procedure of the authors of such novels is more usual than the lifting of the mask when the mysterious scene has gone far enough to produce its emotional effect. To insist upon the usual classification is to render oneself incapable of differentiating between the Radcliffian novel on the one hand, and Otranto, the Monk and the German Schauerroman on the other.


Valency implies the existence of something equivalent to the possession by an atom of points of attachment, and is inseparable from the idea of chemical combination; but it must not be confused, as has often been done, with the force acting at those points. The properties of a mass of matter are the sum of those of its constituents, and, since molecules combine together, the affinities and valencies effecting their union must be those of the constituent atoms. The satisfaction of such additional valencies will represent a comparatively small expenditure of energy, for, even when principal valencies are concerned, as when an element forms pairs of oxides or halides, the heat evolution on combining with the additional oxygen atom is, on the average, only 38 per cent. of what it is on combining with the first atom or atoms (17 cases), and 52 per cent. in the case of the halides (10 cases). At this rate residual affinity must soon become reduced to a quantity insufficient for the attachment of another free atom, but might still be sufficient to unite with it if it were already in combination, and had only its own residual affinity available. Platinum is hexavalent in Cl 4 Pt ClK ClK , though Cl 6 Pt cannot exist. It is, therefore, only in so-called molecular compounds that the highest valencies of an atom can be expected, though no fundamental differences can be imagined between the higher and the principal valencies; this is admitted even by those who have coined a distinctive name for the higher valencies ( e. g. , Werner’s “co-ordination values”). The general rule that additional valencies come into existence in pairs is not invalidated by certain apparent exceptions. Thus, the most stable arrangement of five atoms round a central one is two in one plane, and three in the plane at right angles; according as the positions occupied are those in the one, the other, or both planes, the atom will show valencies of 2, 3 or 5, and by the suppression or development of pairs of valencies, other values of 1, 4, 7, 9, etc., might be shown.


1869 ◽  
Vol 17 ◽  
pp. 212-220 ◽  

It has often been maintained on chemical grounds that hydrogen gas is the vapour of a highly volatile metal. The idea forces itself upon the mind that palladium with its occluded hydrogen is simply an alloy of this volatile metal, in which the volatility of the one element is restrained by its union with the other, and which owes its metallic aspect equally to both constituents. How far such a view is borne out by the properties of the compound substance in question will appear by the following examination of the properties of what, assuming its metallic character, would have to be named Hydrogenium . 1. Density .—The density of palladium when charged with eight or nine hundred times its volume of hydrogen gas is perceptibly lowered; but the change cannot be measured accurately by the ordinary method of immersion in water, owing to a continuous evolution of minute hydrogen bubbles which appears to be determined by contact with the liquid. However, the linear dimensions of the charged palladium are altered so considerably that the difference admits of easy measurement, and furnishes the required density by calculation. Palladium in the form of wire is readily charged with hydrogen by evolving that gas upon the surface of the metal in a galvanometer containing dilute sulphuric acid as usual. The length of the wire before and after a charge is found by stretching it on both occasions by the same moderate weight, such as will not produce permanent distention, over the surface of a flat graduated measure. The measure was graduated to hundredths of an inch, and by means of a vernier, the divisions could be read to thousandths. The distance between two fine cross lines marked upon the surface of the wire near each of its extremities was observed.


1935 ◽  
Vol 8 (3) ◽  
pp. 437-440
Author(s):  
B. V. Buizov ◽  
M. K. Popova

Abstract The results of our previous study of the thermal vulcanization of rubber made it sufficiently clear that during the heating of rubber mixed with sulfur two complex phenomena take place. On the one hand, sulfur interacts with rubber, and on the other, rubber itself undergoes a depolymerization, as well as a polymerization. In reality, however, vulcanization does not proceed under ideal conditions. The rubber and sulfur in the mixture cannot be conceived in an isolated state. On the one hand, the mixture contains the accompanying substances of rubber, such as resins, albumin, etc., whose role in the vulcanization is far from being explained, and on the other hand, the system: rubber + sulfur always exists in some medium. The latter may be either a gaseous or a liquid medium. Hot vulcanization in the industry is most frequently performed in an atmosphere of hot air or in water vapor. We know how great is the difference in the effects of these two conditions. To be sure, the pressure under which the vulcanization takes place is also of importance here; however, the nature of the gaseous medium has evidently a considerable influence on the vulcanization process, which has never been investigated. It seemed to us therefore of interest to investigate this problem, considering the above mentioned two factors, i. e., chemical binding of sulfur and physical changes in the rubber. The previous investigation had shown that the chemical binding of sulfur alone does not explain the nature of vulcanization. Thus, in some cases rubber on heating combines with sulfur, but at the same time disintegrates into a sticky mass and shows no signs of vulcanization with respect to its physico-mechanical properties. Conversely, cases are known where the chemical combination of sulfur proceeds only feebly (and which with chloroprene rubber is entirely unnecessary), whereas the physico-mechanical effects of vulcanization are well pronounced. We therefore undertook an investigation of the processes of chemical combination of sulfur and changes in the solubility of rubber on heating its mixtures with sulfur in atmospheres of various gases. For these vulcanization tests, a mixture of rubber with 7% sulfur and 0.4% magnesium carbonate in the form of sheets of 0.5 mm. thickness containing 6.5% sulfur was used. A piece of such a sheet was wound in one layer around the glass tube A and was then inserted into the test tube B. Gas was slowly conducted at the top of the tube A escaping through the side tube of the test tube B. In the vulcanization tests in alcohol, water and formaldehyde solution, the liquid was poured into the teat tube B, and on evaporation filled the entire space of the tube. All gases were previously dried.


2016 ◽  
Vol 31 (1) ◽  
pp. 1-31 ◽  
Author(s):  
Paul von Mühlendahl

A maritime delimitation is, in its very nature, a delicate process, whose complexity can be further compounded by the presence of tiny land features, as they can considerably distort the final delimitation line. In several recent maritime delimitation cases, the question of the legal status of such a feature has arisen on the one hand, and of the potential effect that its presence in the delimitation area should have on the boundary on the other hand. Among the multiple options that international judges or arbitrators may use, they have chosen, and rightly so, a conservative approach, consisting in attributing a largely secondary role, if any, to these chunks of emerged land. This raises the larger issue about the true nature of a maritime delimitation decided by a judge or an arbitrator and, by extension, the relationship between law and nature.


2019 ◽  
Vol 13 (1) ◽  
pp. 51-56
Author(s):  
Kamil Wojteczko ◽  
Krzysztof Haberko ◽  
Mirosław Bucko ◽  
Paweł Rutkowski ◽  
Marian Rączka

Yttria stabilized tetragonal zirconia polycrystals were prepared using mixtures of two different powders. One is composed of nanometric particles of 3.5mol% Y2O3 solid solution in ZrO2 and the other one of pure zirconia particles. The latter shows elongated particles of about 200 nm length and monoclinic symmetry and the former consists of isometric tetragonal particles of about 7 nm size. Both powders were synthesized under hydrothermal conditions at 240?C in water (the 3.5mol% Y2O3-ZrO2 solid solution) or in 4M NaOH solution (the pure ZrO2 powder). Two homogenous mixtures of these powders were prepared; the one with 5wt.% and the other one with 10 wt.% of the elongated zirconia particles. Compacts of 10mm diameter were isostatically pressed (250MPa) and sintered in a dilatometer furnace at 1400?C with no soaking time. A set of samples heated up to the selected temperatures allowed us to follow phase changes of the materials vs. temperature by X-ray diffraction. It was confirmed that all materials show tetragonal symmetry at the final temperature (1400?C). Density and mean grain size decrease with the elongated zirconia particle additives. The dense samples were polished and their hardness and fracture toughness were determined by Vickers indentation. No hardness changes, due to the elongated zirconia particles additives, were observed, but essential increase of fracture toughness occurred. The observations of the crack runs suggest crack deflection as a potential mechanism of the fracture toughness increase.


1859 ◽  
Vol 9 ◽  
pp. 341-345 ◽  

The very remarkable composition and properties of that class of substances comprehending kakodyl and zinc-ethyl, have justly attached no ordinary degree of interest to the so-called organo-metallic compounds. Influenced by that interest, I was led to inquire whether the series might not include members into whose composition the alkali-metals entered. It was a question whether combination between so powerfully electro-positive a body as potassium or sodium on the one hand, and a hydrocarbon radical on the other, did not involve impossible conditions. It seemed that the answer to this query would not be valueless as a contribution to the store of facts out of which we may hope some day to evoke the conditions of chemical combination.


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