Chapter 6

The secondary battery was the only available means of propelling vessels by electrical power, and considering that these batteries might be made to serve the purpose of keel ballast, their weight, which was still considerable, would not be objectionable. The secondary battery was not an entirely new conception. The hydrogen gas battery suggested by Sir Wm. Grove in 1841, and which was shown in operation, realized in the most perfect manner the conception of storage, only that the power obtained from it was exceedingly slight. The lecturer, in working upon Sir Wm. Grove's conception, had twenty-five years ago constructed a battery of considerable power in substituting porous carbon for platinum, impregnating the same with a precipitate of lead peroxidized by a charging current. At that time little practical importance attached however to the object, and even when Plante, in 1860, produced his secondary battery, composed of lead plates peroxidized by a charging current, little more than scientific curiosity was excited. It was only since the dynamo machine had become an accomplished fact that the importance of this mode of storing energy had become of practical importance, and great credit was due to Faure, to Sellon, and to Volckmar for putting this valuable addition to practical science into available forms. A question of great interest in connection with the secondary battery had reference to its permanence. A fear had been expressed by many that local action would soon destroy the fabric of which it was composed, and that the active surfaces would become coated with sulphate of lead, preventing further action. It had, however, lately been proved in a paper read by Dr. Frankland before the Royal Society, corroborated by simultaneous investigations by Dr. Gladstone and Mr. Tribe, that the action of the secondary battery depended essentially upon the alternative composition and decomposition of sulphate of lead, which was therefore not an enemy, but the best friend to its continued action.

In conclusion, the lecturer referred to electric nomenclature, and to the means for measuring and recording the passage of electric energy. When he addressed the British Association at Southampton, he had ventured to suggest two electrical units additional to those established at the Electrical Congress in 1881, viz.: the watt and the joule, in order to complete the chain of units connecting electrical with mechanical energy and with the unit quantity of heat. He was glad to find that this suggestion had met with a favorable reception, especially that of the watt, which was convenient for expressing in an intelligible manner the effective power of a dynamo machine, and for giving a precise idea of the number of lights or effective power to be realized by its current, as well as of the engine power necessary to drive it; 746 watts represented 1 horse-power.

Finally, the watt meter, an instrument recently developed by his firm, was shown in operation. This consisted simply of a coil of thick conductor suspended by a torsion wire, and opposed laterally to a fixed coil of wire of high resistance. The current to be measured flowed through both coils in parallel circuit, the one representing its quantity expressible in amperes, and the other its potential expressible in volts. Their joint attractive action expressed therefore volt-amperes or watts, which were read off upon a scale of equal divisions.

The lecture was illustrated by experiments, and by numerous diagrams and tables of results. Measuring instruments by Professors Ayrton and Perry, by Mr. Edison and by Mr. Boys, were also exhibited.

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ON THE PREPARATION OF GELATINE PLATES.

[Footnote: Being an abstract of the introductory lecture to a course on photography at the Polytechnic Institute, November 11.]

By E. HOWARD FARMER, F.C.S.

Since the first announcement of these lectures, our Secretary has asked me to give a free introductory lecture, so that all who are interested in the subject may come and gather a better idea as to them than they can possibly do by simply leading a prospectus. This evening, therefore, I propose to give first a typical lecture of the course, and secondly, at its conclusion, to say a few words as to our principal object. As the subject for this evening's lecture I have chosen, "The Preparation of Gelatine Plates," as it is probably one of very general interest to photographers.

Before preparing our emulsion, we must first decide upon the particular materials we are going to use, and of these the first requisite is nitrate of silver. Nitrate of silver is supplied by chemists in three principal conditions:

1. The ordinary crystallized salt, prepared by dissolving silver in nitric acid, and evaporating the solution until the salt crystallizes out. This sample usually presents the appearance of imperfect crystals, having a faint yellowish tinge, and a strong odor of nitrous fumes, and contains, as might be expected, a considerable amount of free acid.

2. Fused nitrate, or "lunar caustic," prepared by fusing the crystallized salt and casting it into sticks. Lunar caustic is usually alkaline to test paper.

3. Recrystallized silver nitrate, prepared by redissolving the ordinary salt in distilled water, and again evaporating to the crystallizing point. By this means the impurities and free acid are removed.

I have a specimen of this on the table, and it consists, as you observe, of fine crystals which are perfectly colorless and transparent; it is also perfectly neutral to test paper. No doubt either of these samples can be used with success in preparing emulsions, but to those who are inexperienced, I recommend that the recrystallized salt be employed. We make, then, a solution of recrystallized silver nitrate in distilled water, containing in every 12 ounces of solution 1¼ ounces of the salt.

The next material we require is a soluble bromide. I have here specimens of various bromides which can be employed, such as ammonium, potassium, barium, and zinc bromides; as a rule, however, either the ammonium or potassium salt is used, and I should like to say a few words respecting the relative efficiency of these two salts.

1. As to ammonium bromide. This substance is a highly unstable salt. A sample of ammonium bromide which is perfectly neutral when first prepared will, on keeping, be found to become decidedly acid in character. Moreover, during this decomposition, the percentage of bromine does not remain constant; as a rule, it will be found to contain more than the theoretical amount of bromine. Finally, all ammonium salts have a most destructive action on gelatine; if gelatine, which has been boiled for a short time with either ammonium bromide or ammonium nitrate, be added to an emulsion, it will be found to produce pink fog--and probably frilling--on plates prepared with the emulsion. For these reasons, I venture to say that ammonium bromide, which figures so largely in formulæ for gelatine emulsions, is one of the worst bromides that can be employed for that purpose, and is, indeed, a frequent source of pink fog and frilling.

2. As to potassium bromide. This is a perfectly stable substance, can be readily obtained pure, and is constant in composition; neither has it (nor the nitrate) any appreciable destructive action on gelatine. We prepare, then, a solution of potassium bromide in water containing in every 12 ounces of solution 1 ounce of the salt. On testing it with litmus paper, the solution may be either slightly alkaline or neutral; in either case, it should be faintly acidified with hydrochloric acid.

The last material we require is the gelatine, one of the most important, and at the same time the most difficult substance to obtain of good quality. I have various samples here--notably Nelson's No. 1 and "X opaque;" Coignet's gold medal; Heinrich's; the Autotype Company's; and Russian isinglass.

The only method I know of securing a uniform quality of gelatine is to purchase several small samples, make a trial emulsion with each, and buy a stock of the sample which gives the best results. To those who do not care to go to this trouble, equal quantities of Nelson's No. 1 and X opaque, as recommended by Captain Abney, can be employed. Having selected the gelatine, 1¼ ounces should be allowed to soak in water, and then melted, when it will be found to have a bulk of about 6 ounces.

In order to prepare our emulsion, I take equal bulks of the silver nitrate and potassium bromide solutions in beakers, and place them in the water bath to get hot. I also take an equal bulk of hot water in a large beaker, and add to it one-half an ounce of the gelatine solution to every 12 ounces of water. Having raised all these to about 180° F., I add (as you observe) to the large beaker containing the dilute gelatine a little of the bromide, then, through a funnel having a fine orifice, a little of the silver, swirling the liquid round during the operation; then again some bromide and silver, and so on until all is added.

When this is completed, a little of the emulsion is poured on a glass plate, and examined by transmitted light; if the mixing be efficient, the light will appear--as it does here--of an orange or orange red color.

It will be observed that we keep the bromide in excess while mixing. I must not forget to mention that to those experienced in mixing, by far the best method is that described by Captain Abney in his Cantor lectures, of keeping the silver in excess.

The emulsion, being properly mixed, has now to be placed in the water bath, and kept at the boiling point for forty-five minutes. As, obviously, I cannot keep you waiting while this is done, I propose to divide our emulsion into two portions, allowing one portion to stew, and to proceed with the next operation with the remainder.

Supposing, then, this emulsion has been boiled, it is placed in cold water to cool. While it is cooling, let us consider for a moment what takes place during the boiling. It is found that during this time the emulsion undergoes two remarkable changes:

1. The molecules of silver bromide gradually aggregate together, forming larger and larger particles.

2. The emulsion increases rapidly in sensitiveness. Now what is the cause, in the first place, of this aggregation of molecules: and, in the second place, of the increase of sensitiveness? We know that the two invariably go together, so that we are right in concluding that the same cause produces both.

It might be thought that heat is the cause, but the same changes take place more slowly in the cold, so we can only say that heat accelerates the action, and hence must conclude that the prime cause is one of the materials in the emulsion itself.

Now, besides the silver bromide, we have in the emulsion water, gelatine, potassium nitrate, and a small excess of potassium bromide; and in order to find which of these is the cause, we must make different emulsions, omitting in succession each of these materials. Suppose we take an emulsion which has just been mixed, and, instead of boiling it, we precipitate the gelatine and silver bromide with alcohol; on redissolving the pellicle in the same quantity of water, we have an emulsion the same as previously, with the exception that the niter and excess of potassium bromide are absent. If such an emulsion be boiled, we shall find the remarkable fact that, however long it be boiled, the silver bromide undergoes no change, neither does the emulsion become any more sensitive. We therefore conclude, that either the niter or the small excess of potassium bromide, or both together, produce the change.

Now take portions of a similarly washed emulsion, and add to one portion some niter, and to another some potassium bromide; on boiling these we find that the one containing niter does not change, while that containing the potassium bromide rapidly undergoes the changes mentioned.

Here, then, by a direct appeal to experiment, we prove that to all appearance comparatively useless excess of potassium bromide is really one of the most important constituents of the emulsion.

The following table gives some interesting results respecting this action of potassium bromide:

__________________________________________________________ Excess of potash bromide. | Time to acquire maximum | | sensitiveness. | --------------------------+------------------------------+ 0.2 grain per ounce | no increase after six hours. | 2.0 " " | about one-half an hour. | 20.0 " " | seven minutes. | --------------------------+------------------------------+

I must here leave the _rationale_ of the process for the present, and proceed with the next operation.

Our emulsion being cold, I add to it, for every 6 ounces of mixed emulsion, 1 ounce of a saturated cold solution of potassium bichromate; then, gently swirling the mixture round, a few drops of a dilute (1 to 8) solution of hydrochloric acid, and place it on one side for a minute or two.

When hydrochloric acid is added to bichromate of potash, chromic acid is liberated. Now, chromic acid has the property of precipitating gelatine, so that what I hope to have done is to have precipitated the gelatine in this emulsion, and which will carry down the silver bromide as well. You see here I can pour off the supernatant liquid clear, leaving our silver and gelatine as a clot at the bottom of the vessel.

Another action of chromic acid is, that it destroys the action of light on silver bromide, so that up to this point operations can be carried on in broad daylight.

The precipitated emulsion is now taken into the dark room and washed until the wash water shows no trace of color; if there be a large quantity, this is best done on a fine muslin filter; if a small quantity, by decantation.

Having been thoroughly washed, I dissolve the pellicle in water by immersing the beaker containing it in the water bath. I then add the remaining gelatine, and make up the whole with 3 ounces of alcohol and water to 30 ounces for the quantities given. I pass the emulsion through a funnel containing a pellet of cotton wool in order to filter it, and it is ready for coating the plates.

To coat a plate, I place it on this small block of leveled wood, and pour on down a glass rod a small quantity of the emulsion, and by means of the rod held horizontally, spread it over the plate. I then transfer the plate to this leveled slab of plate glass, in order that the emulsion on it may set. As soon as set, it is placed in the drying box.

This process, as here described, does not give plates of the highest degree of sensitiveness, to attain which a further operation is necessary; they are, however, of exceedingly good quality, and very suitable for landscape work.--_Photo. News_.

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PICTURES ON GLASS.

The invention of M. E. Godard, of Paris, has for its object the reproduction of images and drawings, by means of vitrifiable colors on glass, wood, stone, on canvas or paper prepared for oil-painting and on other substances having polished surfaces, e. g., earthenware, copper, etc. The original drawings or images should be well executed, and drawn on white, or preferably bluish paper, similar to paper used for ordinary drawings. In the patterns for glass painting, by this process, the place to be occupied is marked by the lead, before cutting the glass to suit the various shades which compose the color of a panel, as is usually done in this kind of work; the operation changes only when the glass cutter hands these sheets over to the man who undertakes the painting. The sheets of glass are cut according to the lines of the drawing, and after being well cleaned, they are placed on the paper on the places for which they have been cut out. If the window to be stained is of large size and consists of several panels, only one panel is proceeded with at a time. The glass is laid on the reverse side of the paper (the side opposite to the drawing), the latter having been made transparent by saturating it with petroleum. This operation also serves to fix the outlines of the drawing more distinctly, and to give more vigor to the dark tone of the paper. When the paper is thus prepared, and the sheets of glass each in its place, they are coated by means of a brush with a sensitizing solution on the side which comes into contact with the paper. This coating should be as thin and as uniform as possible on the surface of the glass. For more perfectly equalizing the coating, a second brush is used.

The sensitizing solution which serves to produce the verifiable image is prepared as follows: Bichromate of ammonia is dissolved in water till the latter is saturated; five grammes of powdered dextrin or glucose are then dissolved in 100 grammes of water; to either of these solutions is added 10 per cent. of the solution of bichromate, and the mixture filtered.

The coating of the glass takes place immediately afterward in a dark room; the coated sheets are then subjected to a heat of 50° or 60° C. (120° to 140° Fahr.) in a small hot chamber, where they are laid one after the other on a wire grating situated 35 centimeters above the bottom. Care should be taken not to introduce the glass under treatment into the hot chamber before the required degree of heat has been obtained. A few seconds are sufficient to dry each sheet, and the wire grating should be large enough to allow of the dried glass being laid in rows, on one side where the heat is less intense. For the reproduction of the pictures or images a photographic copying frame of the size of the original is used. A stained glass window being for greater security generally divided into different panels, the size of one panel is seldom more than one square meter. If the picture to be reproduced should be larger in size than any available copying frame, the prepared glass sheets are laid between two large sheets of plate-glass, and part after part is proceeded with, by sliding the original between the two sheets. A photographic copying frame, however, is always preferable, as it presses the glass sheets better against the original. The original drawing is laid fiat on the glass of the frame. The lines where the lead is to connect the respective sheets of glass are marked on the drawing with blue or red pencil. The prepared sheets of glass are then placed one after the other on the original in their respective places, so that the coated side comes in contact with the original. The frame is then closed. It should be borne in mind that the latter operations must be performed in the dark room. The closed frame is now exposed to light. If the operations are performed outdoors, the frame is laid flat, so that the light falls directly on it; if indoors, the frame is placed inclined behind a window, so that it may receive the light in front. The time necessary for exposing the frame depends upon the light and the temperature; for instance, if the weather is fine and cloudless and the temperature from 16° to 18° C. (60° to 64° Fahr.), it will require from 12 to 15 minutes.

It will be observed that the time of exposure also depends on the thickness of the paper used for the original. If, however, the weather is dark, it requires from 30 to 50 minutes for the exposure. It will be observed that if the temperature is above 25° C. (about 80° Fahr.), the sheets of glass should be kept very cool and be less dried; otherwise, when exposed the sheets are instantly metallized, and the reproduction cannot take place. The same inconvenience takes place if the temperature is beneath 5° C. (41° Fahr.). In this case the sheets should be kept warm, and care should be taken not to expose the frame to the open air, but always behind a glass window at a temperature of from 14° to 18° C. (about 60° Fahr.). The time necessary for the exposure can be ascertained by taking out one of the many pieces of glass, applying to the sensitive surface a vitrifiable color, and observing whether the color adheres well. If the color adheres but slightly to the dark, shady portions of the image, the exposure has been too long, and the process must be recommenced; if, on the contrary, the color adheres too well, the exposure has not been sufficient, the frames must be closed again, and the exposure continued. When the frame has been sufficiently exposed, it is taken into the dark room, the sensitized pieces of glass laid on a plate of glass or marble with the sensitive surface turned upward, and the previously prepared vitrifiable color strewed over it by means of a few light strokes of a brush. This powder does not adhere to the parts of the picture fully exposed to light, but adheres only to the more or less shady portions of the picture. This operation develops on the glass the image as it is on the paper. Thirty to 40 grammes of nitric acid are added to 1,000 grammes of wood-spirit, such as is generally used in photography, and the prepared pieces of glass are dipped into the bath, leaving them afterward to dry. If the bath becomes of a yellowish color, it must be renewed. This bath has for its object to remove the coating of bichromate, so as to allow the color to adhere to the glass, from which it has been separated by the layer of glucose and bichromate, which would prevent the vitrification. The bath has also for its object to render the light parts of the picture perfectly pure and capable of being easily retouched or painted by hand. The application of variously colored enamels and the heating are then effected as in ordinary glass painting. The same process may be applied to marble, wood, stone, lava, canvas prepared for oil painting, earthenware, pure or enameled iron. The result is the same in all cases, and the process is the same as with glass, with the difference only that the above named materials are not dipped into the bath, but the liquid is poured over the objects after the latter have been placed in an inclined position.

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PREPARATION OF HYDROGEN SULPHIDE FROM COAL-GAS.

By I. TAYLOR, B.A., Science Master at Christ College, Brecon.

Hydrogen sulphide may be prepared very easily, and sufficiently pure for ordinary analytical purposes, by passing coal-gas through boiling sulphur. Coal-gas contains 40 to 50 per cent, of hydrogen, nearly the whole of which may, by means of a suitable arrangement, be converted into sulphureted hydrogen. The other constituents of coal-gas--methane, carbon monoxide, olefines, etc.--are not affected by passing through boiling sulphur, and for ordinary laboratory work their removal is quite unnecessary, as they do not in any way interfere with the precipitation of metallic sulphides.

A convenient apparatus for the preparation of hydrogen sulphide from coal-gas, such as we have at present in use in the Christ College laboratory, consists of a retort, R, in which sulphur is placed. Through the tubulure of the retort there passes a bent glass-tube, T E, perforated near the closed end, F, with a number of small holes. (The perforations are easily made by piercing the partially softened glass with a white-hot steel needle; an ordinary crotchet needle, the hook having been removed and the end sharpened, answers the purpose very well.) The end, T, of the glass tube is connected by caoutchouc tubing with the coal-gas supply, the perforated end dipping into the sulphur. The neck of the retort, inclined slightly upward to allow the condensed sulpur, as it remelts, to flow back, is connected with awash bottle, B, to which is attached the flask, F, containing the solution through which it is required to pass the hydrogen sulphide; F is connected with an aspirator, A.