Part 30

579. The effect of a solution of caustic potassa in preserving the platina plates was tried in a similar manner. After being retained in such a solution for forty hours, they acted exceedingly well on oxygen and hydrogen, and one caused such rapid condensation of the gases, that the plate became much heated, and I expected the temperature would have risen to ignition.

580. When similarly prepared plates (569.) had been put into distilled water for forty hours, and then introduced into mixed oxygen and hydrogen, they were found to act but very slowly and feebly as compared with those which had been preserved in acid or alkali. When, however, the quantity of water was but small, the power was very little impaired after three or four days. As the water had been retained in a wooden vessel, portions of it were redistilled in glass, and this was found to preserve prepared plates for a great length of time. Prepared plates were put into tubes with this water and closed up; some of them, taken out at the end of twenty-four days, were found very active on mixed oxygen and hydrogen; others, which were left in the water for fifty-three days, were still found to cause the combination of the gases. The tubes had been closed only by corks.

581. The act of combination always seemed to diminish, or apparently exhaust, the power of the platina plate. It is true, that in most, if not all instances, the combination of the gases, at first insensible, gradually increased in rapidity, and sometimes reached to explosion; but when the latter did not happen, the rapidity of combination diminished; and although fresh portions of gas were introduced into the tubes, the combination went on more and more slowly, and at last ceased altogether. The first effect of an increase in the rapidity of combination depended in part upon the water flowing off from the platina plate, and allowing a better contact with the gas, and in part upon the heat evolved during the progress of the combination (630.). But notwithstanding the effect of these causes, diminution, and at last cessation of the power, always occurred. It must not, however, be unnoticed, that the purer the gases subjected to the action of the plate, the longer was its combining power retained. With the mixture evolved at the poles of the voltaic pile, in pure dilute sulphuric acid, it continued longest; and with oxygen and hydrogen, of perfect purity, it probably would not be diminished at all.

582. Different modes of treatment applied to the platina plate, after it had ceased to be the positive pole of the pile, affected its power very curiously. A plate which had been a positive pole in diluted sulphuric acid of specific gravity 1.336 for four or five minutes, if rinsed in water and put into mixed oxygen and hydrogen, would act very well, and condense perhaps one cubic inch and a half of gas in six or seven minutes; but if that same plate, instead of being merely rinsed, had been left in distilled water for twelve or fifteen minutes, or more, it would rarely fail, when put into the oxygen and hydrogen, of becoming, in the course of a minute or two, ignited, and would generally explode the gases. Occasionally the time occupied in bringing on the action extended to eight or nine minutes, and sometimes even to forty minutes, and yet ignition and explosion would result. This effect is due to the removal of a portion of acid which otherwise adheres firmly to the plate .

In proof that this is the case, refer to 1038.--Dec. 1838.

583. Occasionally the platina plates (569.), after being made the positive pole of the battery, were washed, wiped with filtering-paper or a cloth, and washed and wiped again. Being then introduced into mixed oxygen and hydrogen, they acted apparently as if they had been unaffected by the treatment. Sometimes the tubes containing the gas were opened in the air for an instant, and the plates put in dry; but no sensible difference in action was perceived, except that it commenced sooner.

584. The power of heat in altering the action of the prepared platina plates was also tried (595.). Plates which had been rendered positive in dilute sulphuric acid for four minutes were well-washed in water, and heated to redness in the flame of a spirit-lamp: after this they acted very well on mixed oxygen and hydrogen. Others, which had been heated more powerfully by the blowpipe, acted afterwards on the gases, though not so powerfully as the former. Hence it appears that heat does not take away the power acquired by the platina at the positive pole of the pile: the occasional diminution of force seemed always referable to other causes than the mere heat. If, for instance, the plate had not been well-washed from the acid, or if the flame used was carbonaceous, or was that of an alcohol lamp trimmed with spirit containing a little acid, or having a wick on which salt, or other extraneous matter, had been placed, then the power of the plate was quickly and greatly diminished (634. 636.).

585. This remarkable property was conferred upon platina when it was made the positive pole in sulphuric acid of specific gravity 1.336, or when it was considerably weaker, or when stronger, even up to the strength of oil of vitriol. Strong and dilute nitric acid, dilute acetic acid, solutions of tartaric, citric, and oxalic acids, were used with equal success. When muriatic acid was used, the plates acquired the power of condensing the oxygen and hydrogen, but in a much inferior degree.

586. Plates which were made positive in solution of caustic potassa did not show any sensible action upon the mixed oxygen and hydrogen. Other plates made positive in solutions of carbonates of potassa and soda exhibited the action, but only in a feeble degree.

587. When a neutral solution of sulphate of soda, or of nitre, or of chlorate of potassa, or of phosphate of potassa, or acetate of potassa, or sulphate of copper, was used, the plates, rendered positive in them for four minutes, and then washed in water, acted very readily and powerfully on the mixed oxygen and hydrogen.

588. It became a very important point, in reference to the cause of this action of the platina, to determine whether the positive pole only could confer it (567.), or whether, notwithstanding the numerous contrary cases, the negative pole might not have the power when such circumstances as could interfere with or prevent the action were avoided. Three plates were therefore rendered negative, for four minutes in diluted sulphuric acid of specific gravity 1.336, washed in distilled water, and put into mixed oxygen and hydrogen. All of them acted, though not so strongly as they would have done if they had been rendered positive. Each combined about a cubical inch and a quarter of the gases in twenty-five minutes. On every repetition of the experiment the same result was obtained; and when the plates were retained in distilled water for ten or twelve minutes, before being introduced into the gas (582.), the action was very much quickened.

589. But when there was any metallic or other substance present in the acid, which could be precipitated on the negative plate, then that plate ceased to act upon the mixed oxygen and hydrogen.

590. These experiments led to the expectation that the power of causing oxygen and hydrogen to combine, which could be conferred upon any piece of platina by making it the positive pole of a voltaic pile, was not essentially dependent upon the action of the pile, or upon any structure or arrangement of parts it might receive whilst in association with it, but belonged to the platina at all times, and was always effective when the surface was perfectly clean. And though, when made the positive pole of the pile in acids, the circumstances might well be considered as those which would cleanse the surface of the platina in the most effectual manner, it did not seem impossible that ordinary operations should produce the same result, although in a less eminent degree.

591. Accordingly, a platina plate (569.) was cleaned by being rubbed with a cork, a little water, and some coal-fire ashes upon a glass plate: being washed, it was put into mixed oxygen and hydrogen, and was found to act at first slowly, and then more rapidly. In an hour, a cubical inch and a half had disappeared.

592. Other plates were cleaned with ordinary sand-paper and water; others with chalk and water; others with emery and water; others, again, with black oxide of manganese and water; and others with a piece of charcoal and water. All of these acted in tubes of oxygen and hydrogen, causing combination of the gases. The action was by no means so powerful as that produced by plates having been in communication with the battery; but from one to two cubical inches of the gases disappeared, in periods extending from twenty-five to eighty or ninety minutes.

593. Upon cleaning the plates with a cork, ground emery, and dilute sulphuric acid, they were found to act still better. In order to simplify the conditions, the cork was dismissed, and a piece of platina foil used instead; still the effect took place. Then the acid was dismissed, and a solution of potassa used, but the effect occurred as before.

594. These results are abundantly sufficient to show that the mere mechanical cleansing of the surface of the platina is sufficient to enable it to exert its combining power over oxygen and hydrogen at common temperatures.

595. I now tried the effect of heat in conferring this property upon platina (584.). Plates which had no action on the mixture of oxygen and hydrogen were heated by the flame of a freshly trimmed spirit-lamp, urged by a mouth blowpipe, and when cold were put into tubes of the mixed gases: they acted slowly at first, but after two or three hours condensed nearly all the gases.

596. A plate of platina, which was about one inch wide and two and three-quarters in length, and which had not been used in any of the preceding experiments, was curved a little so as to enter a tube, and left in a mixture of oxygen and hydrogen for thirteen hours: not the slightest action or combination of the gases occurred. It was withdrawn at the pneumatic trough from the gas through the water, heated red-hot by the spirit-lamp and blowpipe, and then returned when cold into the same portion of gas. In the course of a few minutes diminution of the gases could be observed, and in forty-five minutes about one cubical inch and a quarter had disappeared. In many other experiments platina plates when heated were found to acquire the power of combining oxygen and hydrogen.

597. But it happened not infrequently that plates, after being heated, showed no power of combining oxygen and hydrogen gases, though left undisturbed in them for two hours. Sometimes also it would happen that a plate which, having been heated to dull redness, acted feebly, upon being heated to whiteness ceased to act; and at other times a plate which, having been slightly heated, did not act, was rendered active by a more powerful ignition.

598. Though thus uncertain in its action, and though often diminishing the power given to the plates at the positive pole of the pile (584.), still it is evident that heat can render platina active, which before was inert (595.). The cause of its occasional failure appears to be due to the surface of the metal becoming soiled, either from something previously adhering to it, which is made to adhere more closely by the action of the heat, or from matter communicated from the flame of the lamp, or from the air itself. It often happens that a polished plate of platina, when heated by the spirit-lamp and a blowpipe, becomes dulled and clouded on its surface by something either formed or deposited there; and this, and much less than this, is sufficient to prevent it from exhibiting the curious power now under consideration (634. 636.). Platina also has been said to combine with carbon; and it is not at all unlikely that in processes of heating, where carbon or its compounds are present, a film of such a compound may be thus formed, and thus prevent the exhibition of the properties belonging to pure platina.

When heat does confer the property it is only by the destruction or dissipation of organic or other matter which had previously soiled the plate (632. 633. 634.).--Dec. 1838.

599. The action of alkalies and acids in giving platina this property was now experimentally examined. Platina plates (569.) having no action on mixed oxygen and hydrogen, being boiled in a solution of caustic potassa, washed, and then put into the gases, were found occasionally to act pretty well, but at other times to fail. In the latter case I concluded that the impurity upon the surface of the platina was of a nature not to be removed by the mere solvent action of the alkali, for when the plates were rubbed with a little emery, and the same solution of alkali (592.), they became active.

600. The action of acids was far more constant and satisfactory. A platina plate was boiled in dilute nitric acid: being washed and put into mixed oxygen and hydrogen gases, it acted well. Other plates were boiled in strong nitric acid for periods extending from half a minute to four minutes, and then being washed in distilled water, were found to act very well, condensing one cubic inch and a half of gas in the space of eight or nine minutes, and rendering the tube warm (570.).

601. Strong sulphuric acid was very effectual in rendering the platina active. A plate (569.) was heated in it for a minute, then washed and put into the mixed oxygen and hydrogen, upon which it acted as well as if it had been made the positive pole of a voltaic pile (570.).

602. Plates which, after being heated or electrized in alkali, or after other treatment, were found inert, immediately received power by being dipped for a minute or two, or even only for an instant, into hot oil of vitriol, and then into water.

603. When the plate was dipped into the oil of vitriol, taken out, and then heated so as to drive off the acid, it did not act, in consequence of the impurity left by the acid upon its surface.

604. Vegetable acids, as acetic and tartaric, sometimes rendered inert platina active, at other times not. This, I believe, depended upon the character of the matter previously soiling the plates, and which may easily be supposed to be sometimes of such a nature as to be removed by these acids, and at other times not. Weak sulphuric acid showed the same difference, but strong sulphuric acid (601.) never failed in its action.