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Electrochemical cell

Primary Cells

Galvani, an Italian physician, discovered, in 1786, that a current of electricity could be produced by chemical action. In 1800, Volta, a physicist, also an Italian, threw further light on Galvani's discovery and produced what we know as the voltaic, or galvanic, cell. In honor of these two discoverers we have the words volt, galvanic, and the various words and terms derived therefrom.

Simple Voltaic Cell. A very simple voltaic cell may be made by placing two plates, one of copper and one of zinc, in a glass vessel partly filled with dilute sulphuric acid, as shown in Fig. 60. When the two plates are not connected by a wire or other conductor, experiment shows that the copper plate bears a positive charge with respect to the zinc plate, and the zinc plate bears a negative charge with respect to the copper. When the two plates are connected by a wire, a current flows from the copper to the zinc plate through the metallic path of the wire, just as is to be expected when any conductor of relatively high electrical potential is joined to one of relatively low electrical potential. Ordinarily, when one charged body is connected to another of different potential, the resulting current is of but momentary duration, due to the redistribution of the charges and consequent equalization of potential. In the case of the simple cell, however, the current is continuous, showing that some action is maintaining the charges on the two plates and therefore maintaining the difference of potential between them. The energy of this current is derived from the chemical action of the acid on the zinc. The cell is in reality a sort of a zinc-burning furnace.

In the action of the cell, when the two plates are joined by a wire, it may be noticed that the zinc plate is consumed and that bubbles of hydrogen gas are formed on the surface of the copper plate.

Theory. Just why or how chemical action in a voltaic cell results in the production of a negative charge on the consumed plate is not known. Modern theory has it that when an acid is diluted in water the molecules of the acid are split up or dissociated  into two oppositely charged atoms, or groups of atoms, one bearing a positive charge and the other a negative charge of electricity. Such charged atoms or groups of atoms are called ions. This separation of the molecules of a chemical compound into positively and negatively charged ions is called dissociation.

Thus, in the simple cell under consideration the sulphuric acid, by dissociation, splits up into hydrogen ions bearing positive charges, and SO 4 ions bearing negative charges. The solution as a whole is neutral in potential, having an equal number of equal and opposite charges.

Illustration: Fig. 60. Simple Voltaic Cell 
Fig. 60. Simple Voltaic Cell
View full size illustration.

It is known that when a metal is being dissolved by an acid, each atom of the metal which is torn off by the solution leaves the metal as a positively charged ion. The carrying away of positive charges from a hitherto neutral body leaves that body with a negative charge. Hence the zinc, or consumed  plate, becomes negatively charged.

In the chemical attack of the sulphuric acid on the zinc, the positive hydrogen ions are liberated, due to the affinity of the negative SO 4  ions for the positive zinc ions, this resulting in the formation of zinc sulphate in the solution. Now the solution itself becomes positively charged, due to the positive charges leaving the zinc plate with the zinc ions, and the free positively charged hydrogen ions liberated in the solution as just described are repelled to the copper plate, carrying their positive charges thereto. Hence the copper plate, or the unconsumed  plate, becomes positively charged and also coated with hydrogen bubbles.

The plates or electrodes of a voltaic cell need not consist of zinc and copper, nor need the fluid, called the electrolyte, be of sulphuric acid; any two dissimilar elements immersed in an electrolyte that attacks one of them more readily than the other will form a voltaic cell. In every such cell it will be found that one of the plates is consumed, and that on the other plate some element is deposited, this element being sometimes a gas and sometimes a solid. The plate which is consumed is always the negative plate, and the one on which the element is deposited is always the positive, the current through the connecting wire always being, therefore, from the unconsumed to the consumed plate. Thus, in the simple copper-zinc cell just considered, the zinc is consumed, the element hydrogen is deposited on the copper, and the current flow through the external circuit is from the copper to the zinc.

The positive charges, leaving the zinc, or consumed, plate, and passing through the electrolyte to the copper, or unconsumed, plate, constitute in effect a current of electricity flowing within the electrolyte. The current within the cell passes, therefore, from the zinc plate to the copper plate. The zinc is, therefore, said to be positive with respect to the copper.

Difference of Potential. The amount of electromotive force, that is generated between two dissimilar elements immersed in an electrolyte is different for different pairs of elements and for different electrolytes. For a given electrolyte each element bears a certain relation to another; i.e., they are either electro-positive or electro-negative relative to each other. In the following list a group of elements are arranged with respect to the potentials which they assume with respect to each other with dilute sulphuric acid as the electrolyte. The most electro-positive elements are at the top and the most electro-negative at the bottom.

+Sodium Lead  Copper
 Magnesium  Iron  Silver
 Zinc Nickel  Gold
 Cadmium Bismuth  Platinum
 Tin Antimony  -Graphite (Carbon)
 

Any two elements selected from this list and immersed in dilute sulphuric acid will form a voltaic cell, the amount of difference of potential, or electromotive force, depending on the distance apart in this series of the two elements chosen. The current within the cell will always flow from the one nearest the top of the list to the one nearest the bottom, i.e., from the most electro-positive to the most electro-negative; and, therefore, the current in the wire joining the two plates will flow from the one lowest down in the list to the one highest up.

From this series it is easy to see why zinc and copper, and also zinc and carbon, are often chosen as elements of voltaic cells. They are widely separated in the series and comparatively cheap.

This series may not be taken as correct for all electrolytes, for different electrolytes alter somewhat the order of the elements in the series. Thus, if two plates, one of iron and the other of copper, are immersed in dilute sulphuric acid, a current is set up which proceeds through the liquid from the iron to the copper; but, if the plates after being carefully washed are placed in a solution of potassium sulphide, a current is produced in the opposite direction. The copper is now the positive element.

Table II shows the electrical deportment of the principal metals in three different liquids. It is arranged like the preceding one, each metal being electro-positive to any one lower in the list.

TABLE II

Behavior of Metals in Different Electrolytes

Caustic Potash Hydrochloric Acid Potassium Sulphide
+ Zinc + Zinc + Zinc
  Tin   Cadmium   Copper
  Cadmium   Tin   Cadmium
  Antimony   Lead   Tin
  Lead   Iron   Silver
  Bismuth   Copper   Antimony
  Iron   Bismuth   Lead
  Copper   Nickel   Bismuth
  Nickel   Silver   Nickel
- Silver - Antimony - Iron
 

It is important to remember that in all cells, no matter what elements or what electrolyte are used, the electrode which is consumed  is the one that becomes negatively charged  and its terminal, therefore, becomes the negative terminal  or pole, while the electrode which is not consumed  is the one that becomes positively charged, and its terminal is, therefore, the positive terminal  or pole of the cell. However, because the current in the electrolyte flows from the consumed  plate to the unconsumed  plate, the consumed plate is called the positive  plate and the unconsumed, the negative. This is likely to become confusing, but if one remembers that the active  plate is the positive  plate, because it sends forth positive  ions in the electrolyte, and, therefore, itself becomes negatively  charged, one will have the proper basis always to determine the direction of the current flow, which is the important thing.

Polarization. If the simple cell already described have its terminals connected by a wire for some time, it will be found that the current rapidly weakens until it ceases to be manifest. This weakening results from two causes: first, the hydrogen gas which is liberated in the action of the cell is deposited in a layer on the copper plate, thereby covering the plate and reducing the area of contact with the liquid. This increases the internal resistance of the cell, since hydrogen is a non-conductor. Second, the plate so covered becomes in effect a hydrogen electrode, and hydrogen stands high as an electro-positive element. There is, therefore, actual reduction in the electromotive force of the cell, as well as an increase in internal resistance. This phenomenon is known as polarization, and in commercial cells means must be taken to prevent such action as far as possible.

The means by which polarization of cells is prevented or reduced in practice may be divided into three general classes:

First—mechanical means. If the hydrogen bubbles be simply brushed away from the surface of the electrode the resistance and the counter polarity which they cause will be diminished. The same result may be secured if air be blown into the solution through a tube, or if the liquid be kept agitated. If the surface of the electrode be roughened or covered with points, the bubbles collect more freely at the points and are more quickly carried away to the surface of the liquid. These means are, however, hardly practical except in cells for laboratory use.

Second—chemical means. If a highly oxidizing substance be added to the electrolyte, it will destroy the hydrogen bubbles by combining with them while they are in a nascent state, and this will prevent the increase in internal resistance and the opposing electromotive force. Such substances are bichromate of potash, nitric acid, and chlorine, and are largely used.

Third—electro-chemical means. Double cells, arranged to separate the elements and liquids by means of porous partitions or by gravity, may be so arranged that solid copper is liberated instead of hydrogen at a point where the current leaves the liquid, thereby entirely obviating polarization. This method also is largely used.

Local Action. When a simple cell stands idle, i.e., with its circuit open, small hydrogen bubbles may be noticed rising from the zinc electrode instead of from copper, as is the case where the circuit is closed. This is due to impurities in the zinc plate, such as particles of iron, tin, arsenic, carbon, etc. Each of these particles acts with the surrounding zinc just as might be expected of any pair of dissimilar elements opposed to each other in an electrolyte; in other words, they constitute small voltaic cells. Local currents, therefore, are generated, circulating between the two adjacent metals, and, as a result, the zinc plate and the electrolyte are needlessly wasted and the general condition of the cell is impaired. This is called local action.

Amalgamated Zincs. Local action might be prevented by the use of chemically pure zinc, but this, on account of its expense, cannot be employed commercially. Local action, however, may be overcome to a great extent by amalgamating the zinc, i.e., coating it with mercury. The iron particles or other impurities do not dissolve in the mercury, as does the zinc, but they float to the surface, whence the hydrogen bubbles which may form speedily carry them off, and, in other cases, the impurities fall to the bottom of the cell. As the zinc in the pasty amalgam dissolves in the acid, the film of mercury unites with fresh zinc, and so always presents a clear, bright, homogeneous surface to the action of the electrolyte.

The process of amalgamating the zinc may be performed by dipping it in a solution composed of

Nitric Acid 1 lb.
Muriatic Acid 2 lbs.
Mercury 8 oz.

The acids should be first mixed and then the mercury slowly added until dissolved. Clean the zinc with lye and then dip it in the solution for a second or two. Rinse in clean water and rub with a brush.

Another method of amalgamating zincs is to clean them by dipping them in dilute sulphuric acid and then in mercury, allowing the surplus to drain off.

Commercial zincs, for use in voltaic cells as now manufactured, usually have about 4 per cent of mercury added to the molten zinc before casting into the form of plates or rods.

Series and Multiple Connections . When a number of voltaic cells are joined in series, the positive pole of one being connected to the negative pole of the next one, and so on throughout the series, the electromotive forces  of all the cells are added, and the electromotive force of the group, therefore, becomes the sum of the electromotive forces of the component cells. The currents through all the cells in this case will be equal to that of one cell.

If the cells be joined in multiple, the positive poles all being connected by one wire and the negative poles by another, then the currents  of all the cells will be added while the electromotive force of the combination remains the same as that of a single cell, assuming all the cells to be alike in electromotive force.

Obviously combinations of these two arrangements may be made, as by forming strings of cells connected in series, and connecting the strings in multiple or parallel.

The term battery is frequently applied to a single voltaic cell, but this term is more properly used to designate a plurality of cells joined together in series, or in multiple, or in series multiple so as to combine their actions in causing current to flow through an external circuit. We may therefore refer to a battery of so many cells. It has, however, become common, though technically improper, to refer to a single cell as a battery, so that the term battery, as indicating necessarily more than one cell, has largely lost its significance.

Cells may be of two types, primary and secondary.

Primary cells are those consisting of electrodes of dissimilar elements which, when placed in an electrolyte, become immediately ready for action.

Secondary cells, commonly called storage cells  and accumulators, consist always of two inert plates of metal, or metallic oxide, immersed in an electrolyte which is incapable of acting on either of them until a current has first been passed through the electrolyte from one plate to the other. On the passage of a current in this way, the decomposition of the electrolyte is effected and the composition of the plates is so changed that one of them becomes electro-positive and the other electro-negative. The cell is then, when the charging  current ceases, capable of acting as a voltaic cell.

This chapter is devoted to the primary cell or battery alone.

Types of Primary Cells . Primary cells may be divided into two general classes: first, those adapted to furnish constant current; and second, those adapted to furnish only intermittent currents. The difference between cells in this respect rests largely in the means employed for preventing or lessening polarization. Obviously in a cell in which polarization is entirely prevented the current may be allowed to flow constantly until the cell is completely exhausted; that is, until the zinc is all eaten up or until the hydrogen is exhausted from the electrolyte or both. On the other hand some cells are so constituted that polarization takes place faster than the means intended to prevent it can act. In other words, the polarization gradually gains on the preventive means and so gradually reduces the current by increasing the resistance of the cell and lowering its electromotive force. In cells of this kind, however, the arrangement is such that if the cell is allowed to rest, that is, if the external circuit is opened, the depolarizing agency will gradually act to remove the hydrogen from the unattacked electrode and thus place the cell in good condition for use again.

Of these two types of primary cells the intermittent-current cell is of far greater use in telephony than the constant-current cell. This is because the use of primary batteries in telephony is, in the great majority of cases, intermittent, and for that reason a cell which will give a strong current for a few minutes and which after such use will regain practically all of its initial strength and be ready for use again, is more desirable than one which will give a weaker current continuously throughout a long period of time.

Since the cells which are adapted to give constant current are commonly used in connection with circuits that are continuously closed, they are called closed-circuit cells. The other cells, which are better adapted for intermittent current, are commonly used on circuits which stand open most of the time and are closed only occasionally when their current is desired. For this reason these are termed open-circuit cells.

Open-Circuit Cells. LeClanché Cell:—By far the most important primary cell for telephone work is the so-called LeClanché cell. This assumes a large variety of forms, but always employs zinc as the negatively charged element, carbon as the positively charged element, and a solution of sal ammoniac as the electrolyte. This cell employs a chemical method of taking care of polarization, the depolarizing agent being peroxide of manganese, which is closely associated with the carbon element.

The original form of the LeClanché cell, a form in which it was very largely used up to within a short time ago, is shown in Fig. 61. In this the carbon element is placed within a cylindrical jar of porous clay, the walls of this jar being of such consistency as to allow moisture slowly to permeate through it. Within this porous cup, as it is called, a plate or disk of carbon is placed, and around this the depolarizing agent, consisting of black oxide of manganese. This is usually mixed with, broken carbon, so as to increase the effective area of the carbon element in contact with the depolarizing agent, and also to reduce the total internal resistance of the cell. The zinc electrode usually consisted merely in a rod of zinc, as shown, with a suitable terminal at its upper end.

Illustration: Fig. 61. LeClanché Cell 
Fig. 61. LeClanché Cell
View full size illustration.

The chemical action taking place within the LeClanché cell is, briefly, as follows: Sal ammoniac is chemically known as chloride of ammonium and is a combination of chlorine and ammonia. In the action which is assumed to accompany the passage of current in this cell, the sal ammoniac is decomposed, the chlorine leaving the ammonia to unite with an atom of the zinc plate, forming chloride of zinc and setting free ammonia and hydrogen. The ammonia is immediately dissolved in the water of the cell, and the hydrogen enters the porous cup and would speedily polarize the cell by adhering to the carbon plate but for the fact that it encounters the peroxide of manganese. This material is exceedingly rich in oxygen and it therefore readily gives up a part of its oxygen, which forms water by combination with the already liberated hydrogen and leaves what is termed a sesquioxide  of manganese. This absorption or combination of the hydrogen prevents immediate polarization, but hydrogen is evolved during the operation of the cell more rapidly than it can combine with the oxygen of the manganese, thereby leading to polarization more rapidly than the depolarizer can prevent it when the cell is heavily worked. When, however, the cell is left with its external circuit open for a time, depolarization ensues by the gradual combination of the hydrogen with the oxygen of the peroxide of manganese, and as a result the cell recuperates and in a short time attains its normal electromotive force.

The electromotive force of this cell when new is about 1.47 volts. The internal resistance of the cell of the type shown in Fig. 61 is approximately 1 ohm, ordinarily less rather than more.

A more recent form of LeClanché cell is shown in cross-section in Fig. 62. This uses practically the same materials and has the same chemical action as the old disk LeClanché cell shown in Fig. 61. It dispenses, however, with the porous cup and instead employs a carbon electrode, which in itself forms a cup for the depolarizing agent.

Illustration: Fig. 62. Carbon Cylinder LeClanché Cell 
Fig. 62. Carbon Cylinder LeClanché Cell
View full size illustration.

The carbon electrode is in the form of a corrugated hollow cylinder which engages by means of an internal screw thread a corresponding screw thread on the outer side of the carbon cover. Within this cylinder is contained a mixture of broken carbon and peroxide of manganese. The zinc electrode is in the form of a hollow cylinder almost surrounding the carbon electrode and separated therefrom by means of heavy rubber bands stretched around the carbon. The rod, forming the terminal of the zinc, passes through a porcelain bushing on the cover plate to obviate short circuits. This type of cell has an electromotive force of about 1.55 volts and recuperates very quickly after severe use. It also has considerably lower internal resistance than the type of LeClanché cell employing a porous cup, and, therefore, is capable of generating a considerably larger current.

Cells of this general type have assumed a variety of forms. In some the carbon electrode, together with the broken carbon and peroxide of manganese, were packed into a canvas bag which was suspended in the electrolyte and usually surrounded by the zinc electrode. In other forms the carbon electrode has moulded with it the manganese depolarizer.

In order to prevent the salts within the cell from creeping over the edge of the containing glass jar and also over the upper portion of the carbon electrode, it is common practice to immerse the upper end of the carbon element and also the upper edge of the glass jar in hot paraffin.

In setting up the LeClanché cell, place not more than four ounces of white sal ammoniac in the jar, fill the jar one-third full of water, and stir until the sal ammoniac is all dissolved. Then put the carbon and zinc elements in place. A little water poured in the vent hole of the porous jar or carbon cylinder will tend to hasten the action.

An excess of sal ammoniac should not be used, as a saturated solution tends to deposit crystals on the zinc; on the other hand, the solution should not be allowed to become too weak, as in that case the chloride of zinc will form on the zinc. Both of these causes materially increase the resistance of the cell.

A great advantage of the LeClanché cell is that when not in use there is but little material waste. It contains no highly corrosive chemicals. Such cells require little attention, and the addition of water now and then to replace the loss due to evaporation is about all that is required until the elements become exhausted. They give a relatively high electromotive force and have a moderately low internal resistance, so that they are capable of giving rather large currents for short intervals of time. If properly made, they recuperate quickly after polarization due to heavy use.

Dry Cell. All the forms of cells so far considered may be quite properly termed wet cells  because of the fact that a free liquid electrolyte is used. This term is employed in contradistinction to the later developed cell, commonly termed the dry cell. This term "dry cell" is in some respects a misnomer, since it is not dry and if it were dry it would not work. It is essential to the operation of these cells that they shall be moist within, and when such moisture is dissipated the cell is no longer usable, as there is no further useful chemical action.

The dry cells are all of the LeClanché type, the liquid electrolyte of that type being replaced by a semi-solid substance that is capable of retaining moisture for a considerable period.

As in the ordinary wet LeClanché cell, the electrodes are of carbon and zinc, the zinc element being in the form of a cylindrical cup and forming the retaining vessel of the cell, while the carbon element is in the form of a rod or plate and occupies a central position with regard to the zinc, being held out of contact with the zinc, however, at all points.

A cross-section of an excellent form of dry cell is shown in Fig. 63. The outer casing is of zinc, formed in the shape of a cylindrical cup, and serves not only as the retaining vessel, but as the negatively charged electrode. The outer surface of the zinc is completely covered on its sides and bottom with heavy pasteboard so as to insulate it from bodies with which it may come in contact, and particularly from the zinc cups of other cells used in the same battery. The positively charged electrode is a carbon rod corrugated longitudinally, as shown, in order to obtain greater surface. This rod is held in the center of the zinc cup out of contact therewith, and the intervening space is filled with a mixture of peroxide of manganese, powdered carbon, and sal ammoniac. Several thicknesses of blotting paper constitute a lining for the inner portion of the zinc electrode and serve to prevent the manganese mixture from coming directly into contact therewith. The cell is sealed with pitch, which is placed on a layer of sand and sawdust mixed in about equal parts.

Illustration: Fig. 63. Dry Cell 
Fig. 63. Dry Cell
View full size illustration.

The electrolyte in such cells varies largely as to quantities and proportions of the materials employed in various types of cells, and also varies in the method in which the elements are introduced into the container.

The following list and approximate proportions of material will serve as a fair example of the filling mixture in well-known types of cells.

Manganese dioxide 45 per cent
Carbon or graphite, or both  45 per cent
Sal ammoniac 7 per cent
Zinc chloride 3 per cent
 

Water is added to the above and a sufficient amount of mixture is taken for each cell to fill the zinc cup about seven-eighths full when the carbon is in place. The most suitable quantity of water depends upon the original dryness and fineness of material and upon the quality of the paper lining.

In some forms of dry batteries, starch or other paste is added to improve the contact of the electrolyte with the zinc and promote a more even distribution of action throughout the electrolyte. Mercury, too, is often added to effect amalgamation of the zinc.

As in the ordinary wet type of LeClanché cell, the purpose of the manganese is to act as a depolarizer; the carbon or graphite being added to give conductivity to the manganese and to form a large electrode surface. It is important that the sal ammoniac, which is the active agent of the cell, should be free from lumps in order to mix properly with the manganese and carbon.

A small local action takes place in the dry cell, caused by the dissimilar metals necessarily employed in soldering up the zinc cup and in soldering the terminal rod of zinc to the zinc cup proper. This action, however, is slight in the better grades of cells. As a result of this, and also of the gradual drying out of the moisture within the cell, these cells gradually deteriorate even when not in use—this is commonly called shelf-wear. Shelf-wear is much more serious in the very small sizes of dry cells than in the larger ones.

Dry cells are made in a large number of shapes and sizes. The most useful form, however, is the ordinary cylindrical type. These are made in sizes varying from one and one-half inches high and three-quarters inch in diameter to eight inches high and three and three-quarters inches in diameter. The most used and standard size of dry cell is of cylindrical form six inches high and two and three-quarters inches in diameter. The dry cell when new and in good condition has an open-circuit voltage of from 1.5 to 1.6 volts. Perhaps 1.55 represents the usual average.

A cell of the two and three-quarters by six-inch size will give throughout its useful life probably thirty ampere hours as a maximum, but this varies greatly with the condition of use and the make of cell. Its effective voltage during its useful life averages about one volt, and if during this life it gives a total discharge of thirty ampere hours, the fair energy rating of the cell will be thirty watt-hours. This may not be taken as an accurate figure, however, as the watt-hour capacity of a cell depends very largely, not only on the make of the cell, but on the rate of its discharge.

An examination of Fig. 63 shows that the dry cell has all of the essential elements of the LeClanché cell. The materials of which the electrodes are made are the same and the porous cup of the disk LeClanché cell is represented in the dry cell by the blotting-paper cylinder, which separates the zinc from the carbon electrode. The positively charged electrode must not be considered as merely the carbon plate or rod alone, but rather the carbon rod with its surrounding mixture of peroxide of manganese and broken carbon. Such being the case, it is obvious that the separation between the electrodes is very small, while the surface presented by both electrodes is very large. As a result, the internal resistance of the cell is small and the current which it will give on a short circuit is correspondingly large. A good cell of the two and three-quarters by six-inch size will give eighteen or twenty amperes on short-circuit, when new.

As the action of the cell proceeds, zinc chloride and ammonia are formed, and there being insufficient water to dissolve the ammonia, there results the formation of double chlorides of zinc and ammonium. These double chlorides are less soluble than the chlorides and finally occupy the pores of the paper lining between the electrolyte and the zinc and greatly increase the internal resistance of the cell. This increase of resistance is further contributed to by the gradual drying out of the cell as its age increases.

Within the last few years dry batteries have been so perfected mechanically, chemically, and electrically that they have far greater outputs and better recuperative power than any of the other types of LeClanché batteries, while in point of convenience and economy, resulting from their small size and non-breakable, non-spillable features and low cost, they leave no room for comparison.

Closed-Circuit Cells. Gravity-Cell:—Coming now to the consideration of closed-circuit or constant-current cells, the most important is the well-known gravity, or blue-stone, cell, devised by Daniell. It is largely used in telegraphy, and often in telephony in such cases as require a constantly flowing current of small quantity. Such a cell is shown in Fig. 64.

The elements of the gravity cell are electrodes of copper and zinc. The solution in which the copper plate is immersed is primarily a solution of copper sulphate, commonly known as blue-stone, in water. The zinc plate after the cell is in action is immersed in a solution of sulphate of zinc which is formed around it.

The glass jar is usually cylindrical, the standard sizes being 5 inches diameter and 7 inches deep; and also 6 inches diameter and 8 inches deep. The copper electrode is of sheet copper of the form shown, and it is partly covered with crystals of blue-stone or copper sulphate. Frequently, in later forms of cells, the copper electrode consists merely of a straight, thick, rectangular bar of copper laid horizontally, directly on top of the blue-stone crystals. In all cases a rubber-insulated wire is attached by riveting to the copper electrode, and passes up through the electrolyte to form the positive terminal.

Illustration: Fig. 64. Gravity Cell 
Fig. 64. Gravity Cell
View full size illustration.

The zinc is, as a rule, of crowfoot form, as shown, whence this cell derives the commonly applied name of crowfoot cell. This is essentially a two-fluid cell, for in its action zinc sulphate is formed, and this being lighter than copper sulphate rises to the top of the jar and surrounds the zinc. Gravity, therefore, serves to keep the two fluids separate.

In the action of the cell, when the external circuit is closed, sulphuric acid is formed which attacks the zinc to form sulphate of zinc and to liberate hydrogen, which follows its tendency to attach itself to the copper plate. But in so doing the hydrogen necessarily passes through the solution of sulphate of copper surrounding the copper plate. The hydrogen immediately combines with the SO 4  radical, forming therewith sulphuric acid, and liberating metallic copper. This sulphuric acid, being lighter than the copper sulphate, rises to the surface of the zinc and attacks the zinc, thus forming more sulphate of zinc. The metallic copper so formed is deposited on the copper plate, thereby keeping the surface bright and clean. Since hydrogen is thus diverted from the copper plate, polarization does not ensue.

The zinc sulphate being colorless, while the copper sulphate is of a dark blue color, the separating line of the two liquids is easily distinguishable. This line is called the blue line  and care should be taken that it does not reach the zinc and cause a deposit of copper to be placed thereon.

As has been stated, these two liquids do not mix readily, but they will eventually mingle unless the action of the cell is sufficient to use up the copper sulphate as speedily as it is dissolved. Thus it will be seen that while the cell is free from polarization and local action, there is, nevertheless, a deteriorating effect if the cell is allowed to remain long on open circuit. Therefore, it should be used when a constant current is required.

Prevention of Creeping:—Much trouble has been experienced in gravity cells due to the creeping of the salts over the edge of the jar. Frequently the upper edges of the jars are coated by dipping in hot paraffin wax in the hope of preventing this. Sometimes oil is poured on top of the fluid in the jar to prevent the creeping of the salts and the evaporation of the electrolyte. The following account of experiments performed by Mr. William Reid, of Chicago, throws light on the relative advantages of these and other methods of preventing creeping.

The experiment was made with gravity cells having 5-inch by 7-inch glass jars. Four cells were made up and operated in a rather dry, warm place, although perhaps under no more severe local conditions than would be found in most telephone exchanges. Cell No. 1 was a plain cell as ordinarily used. Cell No. 2 had the top of the rim of the jar treated with paraffin wax by dipping the rim to about one inch in depth in melted paraffin wax. Cell No. 3 had melted paraffin wax poured over the surface of the liquid forming a seal about 3/16 inch in thickness. After cooling, a few small holes were bored through the seal to let gases escape. Cell No. 4 had a layer of heavy paraffin oil nearly 1/2 inch in thickness (about 6 oz. being used) on top of the solutions.

These cells were all run on a load of .22 to .29 amperes for 15-1/2 hours per day for thirty days, after which the following results were noted:

(a ) The plain cell, or cell No. 1, had to have 26 ounces of water added to it to replace that which had evaporated. The creeping of zinc sulphate salts was very bad.

(b ) The waxed rim cell, or cell No. 2, evaporated 26 ounces of water and the creeping of zinc sulphate salts was not prevented by the waxed rim. The wax proved of no value.

(c ) The wax sealed cell, or cell No. 3, showed practically no evaporation and only very slight creeping of zinc sulphate salts. The creeping of salts that took place was only around spots where the edges of the seal were loose from the jar.

(d ) The paraffin oil sealed cell, or cell No. 4, showed no evaporation and no creeping of salts.

It was concluded by Mr. Reid from the above experiments that the wax applied to the rim of the jar is totally ineffective and has no merits. The wax seal loosens around the edges and does not totally prevent creeping of the zinc sulphate salts, although nearly so. The wax-sealed jar must have holes drilled in it to allow the gases to escape. The method is hardly commercial, as it is difficult to make a neat appearing cell, besides making it almost impossible to manipulate its contents. A coat of paraffin oil approximately 1/2 inch in thickness (about 6 ounces) gives perfect protection against evaporation and creeping of the zinc sulphate salts. The cell, having the paraffin-oil seal, had a very neat, clean appearance as compared with cells No. 1 and No. 2. It was found that the zinc could be drawn out through the oil, cleaned, and replaced with no appreciable effect on voltage or current.

Setting Up:—In setting up the battery the copper electrode is first unfolded to form a cross and placed in the bottom of the jar. Enough copper sulphate, or blue-stone crystals, is then dropped into the jar to almost cover the copper. The zinc crowfoot is then hung in place, occupying a position about 4 inches above the top of the copper. Clear water is then poured in sufficient to fill the jar within about an inch of the top.

If it is not required to use the cell at once, it may be placed on short circuit for a time and allowed to form its own zinc sulphate. The cell may, however, be made immediately available for use by drawing about one-half pint of a solution of zinc sulphate from a cell already in use and pouring it into the jar, or, when this is not convenient, by putting into the liquid four or five ounces of pulverized sulphate of zinc, or by adding about ten drops of sulphuric acid. When the cell is in proper working condition, one-half inch in thickness of heavy paraffin oil of good quality may be added.

If the blue line gets too low, and if there is in the bottom of the cell a sufficient quantity of sulphate of copper, it may be raised by drawing off a portion of the zinc sulphate with a battery syringe and replacing this with water. If the blue line gets too high, it may be lowered by short-circuiting the cell for a time, or by the addition of more sulphate of zinc solution from another battery. If the copper sulphate becomes exhausted, it should be replenished by dropping in more crystals.

Care should be taken in cold weather to maintain the temperature of the battery above 65° or 70° Fahrenheit. If below this temperature, the internal resistance of a cell increases very rapidly, so much so that even at 50° Fahrenheit the action becomes very much impaired. This follows from the facts that the resistance of a liquid decreases as its temperature rises, and that chemical action is much slower at lower temperatures.

The gravity cell has a practically constant voltage of 1.08 volts. Its internal resistance is comparatively high, seldom falling below 1 ohm and often rising to 6 ohms. At best, therefore, it is only capable of producing about 1 ampere. The gravity cell is perhaps the most common type of cell wherein depolarization is affected by electro-chemical means.

Fuller Cell:—A form of cell that is adapted to very heavy open-circuit work and also closed-circuit work where heavier currents are required than can be supplied by the gravity battery is the Fuller. In this the electrodes are of zinc and carbon, respectively, the zinc usually being in the form of a heavy cone and placed within a porous cup. The electrolyte of the Fuller cell is known as electropoion fluid, and consists of a mixture of sodium or potassium bichromate, sulphuric acid, and water.

The various parts of the standard Fuller cell, as once largely employed by the various Bell operating companies, are shown in Fig. 65. In this the jar was made of flint glass, cylindrical in form, six inches in diameter and eight inches deep. It is important that a good grade of glass be used for the jar in this cell, because, on account of the nature of the electrolyte, breakage is disastrous in the effects it may produce on adjacent property. The carbon plate is rectangular in form, about four inches wide, eight and three-quarters inches long, and one-quarter inch thick. The metal terminal at the top of the carbon block is of bronze, both it and the lock nuts and bolts being nickel-plated to minimize corrosion. The upper end of the carbon block is soaked in paraffin so hot as to drive all of the moisture out of the paraffin and out of the pores of the block itself.

The zinc, as is noted from the cut, is in the form of a truncated cone. It is about two and one-eighth inches in diameter at the base and two and one-half inches high. Cast into the zinc is a soft copper wire about No. 12 B. & S. gauge. This wire extends above the top of the jar so as to form a convenient terminal for the cell.

The porous cup is cylindrical in form, about three inches in diameter and seven inches deep. The wooden cover is of kiln-dried white wood thoroughly coated with two coats of asphalt paint. It is provided with a slot for the carbon and a hole for the copper wire extending to the zinc.

The electrolyte for this cell is made as follows:

Sodium bichromate 6 oz.
Sulphuric acid 17 oz.
Soft water 56 oz.

This solution is mixed by dissolving the bichromate of sodium in the water and then adding slowly the sulphuric acid. Potassium bichromate may be substituted for the sodium bichromate.

In setting up this cell, the amalgamated zinc is placed within the porous cup, in the bottom of which are about two teaspoonfuls of mercury, the latter serving to keep the zinc well amalgamated. The porous cup is then placed in the glass jar and a sufficient quantity of the electrolyte is placed in the outer jar to come within about one and one-half inches of the top of the porous cup. About two teaspoonfuls of salt are then placed in the porous cup and sufficient soft water added to bring the level of the liquid within the porous cup even with the level of the electrolyte in the jar surrounding the cup. The carbon is then placed through the slot in the cover, and the wire from the zinc is passed through the hole in the cover provided for it, and the cover is allowed to fall in place. The cell is now ready for immediate use.

The action of this cell is as follows: The sulphuric acid attacks the zinc and forms zinc sulphate, liberating hydrogen. The hydrogen attempts to pass to the carbon plate as usual, but in so doing it meets with the oxygen of the chromic acid and forms water therewith. The remainder of the chromic acid combines with the sulphuric acid to form chromium sulphate.

Illustration: Fig. 65. Fuller Cell 
Fig. 65. Fuller Cell
View full size illustration.

The mercury placed in the bottom of the porous cup with the zinc keeps the zinc in a state of perpetual amalgamation. This it does by capillary action, as the mercury spreads over the entire surface of the zinc. The initial amalgamation, while not absolutely essential, helps in a measure this capillary action.

In another well-known type of the Fuller battery the carbon is a hollow cylinder, surrounding the porous cup. In this type the zinc usually took the form of a long bar having a cross-shaped section, the length of this bar being sufficient to extend the entire depth of the porous cup. This type of cell has the advantage of a somewhat lower internal resistance than the standard form just described.

Should the electrolyte become supersaturated by virtue of the battery being neglected or too heavily overworked, a set of secondary reactions will occur in the cell, resulting in the formation of the yellow crystals upon the carbon. This seriously affects the e.m.f. of the cell and also its internal resistance. Should this occur, some of the solution should be withdrawn and dilute sulphuric acid inserted in its place and the crystals which have formed on the carbon should be carefully washed off. Should the solution lose its orange tint and turn blue, it indicates that more bichromate of potash or bichromate of sodium is needed. This cell gives an electromotive force of 2.1 volts and a very large current when it is in good condition, since its internal resistance is low.

The Fuller cell was once largely used for supplying current to telephone transmitters at subscribers' stations, where very heavy service was demanded, but the advent of the so-called common-battery systems, in some cases, and of the high-resistance transmitter, in other cases, has caused a great lessening in its use. This is fortunate as the cell is a "dirty" one to handle and is expensive to maintain.

The Fuller cell still warrants attention, however, as an available source of current, which may be found useful in certain cases of emergency work, and in supplying special but temporary needs for heavier current than the LeClanché or gravity cell can furnish.

Lalande Cell:—A type of cell, specially adapted to constant-current work, and sometimes used as a central source of current in very small common-battery exchanges is the so-called copper oxide, or Lalande cell, of which the Edison and the Gordon are types. In all of these the negatively charged element is of zinc, the positively charged element a mass of copper oxide, and the electrolyte a solution of caustic potash in water. In the Edison cell the copper oxide is in the form of a compressed slab which with its connecting copper support forms the electrode. In the Gordon and other cells of this type the copper oxide is contained loosely in a perforated cylinder of sheet copper. The copper oxide serves not only as an electrode, but also as a depolarizing agent, the liberated hydrogen in the electrolyte uniting with the oxygen of the copper oxide to form water, and leaving free metallic copper.

On open circuit the elements are not attacked, therefore there is no waste of material while the cell is not in use. This important feature, and the fact that the internal resistance is low, make this cell well adapted for all forms of heavy open-circuit work. The fact that there is no polarizing action within the cell makes it further adaptable to heavy closed-circuit service.

These cells are intended to be so proportioned that all of their parts become exhausted at once so that when the cell fails, complete renewals are necessary. Therefore, there is never a question as to which of the elements should be renewed.

After the elements and solution are in place about one-fourth of an inch of heavy paraffin oil is poured upon the surface of the solution in order to prevent evaporation. This cell requires little attention and will maintain a constant e.m.f. of about two-thirds of a volt until completely exhausted. It is non-freezable at all ordinary temperatures. Its low voltage is its principal disadvantage.

Standard Cell. Chloride of Silver Cell:—The chloride of silver cell is largely used as a standard for testing purposes. Its compactness and portability and its freedom from local action make it particularly adaptable to use in portable testing outfits where constant electromotive force and very small currents are required.

Illustration: Fig. 66. Chloride of Silver Cell 
Fig. 66. Chloride of Silver Cell
View full size illustration.

A cross-section of one form of the cell is shown in Fig. 66. Its elements are a rod of chemically-pure zinc and a rod of chloride of silver immersed in a water solution of sal ammoniac. As ordinarily constructed, the glass jar or tube is usually about 2-1/2 inches long by 1 inch in diameter. After the solution is poured in and the elements are in place the glass tube is hermetically sealed with a plug of paraffin wax.

The e.m.f. of a cell of this type is 1.03 volts and the external resistance varies with the age of the cell, being about 4 ohms at first. Care should be taken not to short-circuit these cells, or use them in any but high-resistance circuits, as they have but little energy and become quickly exhausted if compelled to work in low-resistance circuits.

Conventional Symbol. The conventional symbol for a cell, either of the primary or the secondary type, consists of a long thin line and a short heavy line side by side and parallel. A battery is represented by a number of pairs of such lines, as in Fig. 67. The two lines of each pair are supposed to represent the two electrodes of a cell. Where any significance is to be placed on the polarity of the cell or battery the long thin line is supposed to represent the positively charged plate and the short thick line the negatively charged plate. The number of pairs may indicate the number of cells in the battery. Frequently, however, a few pairs of such lines are employed merely for the purpose of indicating a battery without regard to its polarity or its number of cells.

Illustration: Fig. 67. Battery Symbols 
Fig. 67. Battery Symbols
View full size illustration.

In Fig. 67 the representation at A  is that of a battery of a number of cells connected in parallel; that at B  of a battery with the cells connected in series; and that at C  of a battery with one of its poles grounded.