CHAPTER V.

ELECTROLYSIS.

Having seen how electricity can be generated and stored in

considerable quantity, let us now turn to its practical uses. Of

these by far the most important are based on its property of

developing light and heat as in the electric spark, chemical

action as m the voltameter, and magnetism as in the electromagnet.

The words "current," "pressure," and so on point to a certain

analogy between electricity and water, which helps the imagination

to figure what can neither be seen nor handled, though it must not

be traced too far. 'Water, for example, runs by the force of

gravity from a place of higher to a place of lower level. The

pressure of the stream is greater the more the difference of level

or "head of water" The strength of the current or quantity of

water flowing per second is greater the higher the pressure, and

the less the resistance of its channel. The power of the water or

its rate of doing mechanical work is greater the higher the

pressure and the stronger the current. So, too, electricity flows

by the electromotive force from a place of higher to a place of

lower electric level or potential. The electric pressure is

greater the more the difference of potential or electromotive

force. The strength of the electric current or quantity of

electricity flowing per second is greater the higher the pressure

or electromotive force and the less the resistance of the circuit

The power of the electricity or its rate of doing work is greater

the higher the electromotive force and the stronger the current.

It follows that a small quantity of water or electricity at a high

pressure will give us the same amount of energy as a large

quantity at a low pressure, and our choice of one or the other

will depend on the purpose we have in view. As a rule, however, a

large current at a comparatively low or moderate pressure is found

the more convenient in practice.

The electricity of friction belongs to the former category, and

the electricity of chemistry, heat, and magnetism to the latter.

The spark of a factional or influence machine can be compared to a

highland cataract of lofty height but small volume, which is more

picturesque than useful, and the current from a voltaic battery, a

thermopile, or a dynamo to a lowland river which can be dammed to

turn a mill. It is the difference between a skittish gelding and a

tame carthorse.

Not the spark from an induction coil or Leyden jar, but a strong

and steady current at a low pressure, is adapted for electrolysis

or electrodeposition, and hence the voltaic battery or a special

form of dynamo is usually employed in this work. A flash of

lightning is the very symbol of terrific power, and yet, according

to the illustrious Faraday, it contains a smaller amount of

electricity than the feeble current required to decompose a single

drop of rain.

In our simile of the mill dam and the battery or dynamo, the dam

corresponds to the positive pole and the river or sea below the

mill to the negative pole. The mill-race will stand for the wire

joining the poles, that is to say, the external circuit, and the

mill-wheel for the work to be done in the circuit, whether it be a

chemical for decomposition, a telegraph instrument, an electric

lamp, or any other appliance. As the current in the race depends

on the "head of water," or difference of level between the dam and

the sea as well as on the resistance of the channel, so the

current in the circuit depends on the "electromotive force," or

difference of potential between the positive and negative poles,

as well as on the resistance of the circuit. The relation between

these is expressed by the well-known law of Ohm, which runs: A

current of electricity is directly proportional to the

electromotive force and inversely proportional to the resistance

of the circuit.

In practice electricity is measured by various units or standards

named after celebrated electricians. Thus the unit of quantity is

the coulomb, the unit of current or quantity flowing per second is

the ampere, the unit of electromotive force is the volt, and the

unit of resistance is the ohm.

The quantity of water or any other "electrolyte" decomposed by

electricity is proportional to the strength of the current. One

ampere decomposes .00009324 gramme of water per second, liberating

.000010384 gramme of hydrogen and .00008286 gramme of oxygen.

The quantity in grammes of any other chemical element or ion which

is liberated from an electrolyte or body capable of

electrochemical decomposition in a second by a current of one

ampere is given by what is called the electrochemical equivalent

of the ion. This is found by multiplying its ordinary chemical

equivalent or combining weight by .000010384, which is the

electrochemical equivalent of hydrogen. Thus the weight of metal

deposited from a solution of any of its salts by a current of so

many amperes in so many seconds is equal to the number of amperes

multiplied by the number of seconds, and by the electrochemical

equivalent of the metal.

The deposition of a metal from a solution of its salt is very

easily shown in the case of copper. In fact, we have already seen

that in the Daniell cell the current decomposes a solution of

sulphate of copper and deposits the pure metal on the copper

plate. If we simply make a solution of blue vitriol in a glass

beaker and dip the wires from a voltaic cell into it, we shall

find the wire from the negative pole become freshly coated with

particles of new copper. The sulphate has been broken up, and the

liberated metal, being positive, gathers on the negative

electrode. Moreover, if we examine the positive electrode we shall

find it slightly eaten away, because the sulphuric acid set free

from the sulphate has combined with the particles of that wire to

make new sulphate. Thus the copper is deposited on one electrode,

namely, the cathode, by which the current leaves the bath, and at

the expense of the other electrode, that is to say, the anode, by

which the current enters the bath.

The fact that the weight of metal deposited in this way from its

salts is proportional to the current, has been utilised for

measuring the strength of currents with a fine degree of accuracy.

If, for example, the tubes of the voltameter described on page 38

were graduated, the volume of gas evolved would be a measure of

the current. Usually, however, it is the weight of silver or

copper deposited from their salts in a certain time which gives

the current in amperes.

Electro-plating is the principal application of this chemical

process. In 1805 Brugnatelli took a silver medal and coated it

with gold by making it the cathode in a solution of a salt of

gold, and using a plate of gold for the anode. The shops of our

jewellers are now bright with teapots, salt cellars, spoons, and

other articles of the table made of inferior metals, but

beautified and preserved from rust in this way.

Figure 44 illustrates an electro-plating bath in which a number of

spoons are being plated. A portion of the vat V is cut away to

show the interior, which contains a solution S of the double

cyanide of gold and potassium when gold is to be laid, and the

double cyanide of silver and potassium when silver is to be

deposited. The electrodes are hung from metal rods, the anode A

being a plate of gold or silver G, as the case may be, and the

cathode C the spoons in question. When the current of the battery

or dynamo passes through the bath from the anode to the cathode,

gold or silver is deposited on the spoons, and the bath

recuperates its strength by consuming the gold or silver plate.

Enormous quantities of copper are now deposited in a similar way,

sulphate of copper being the solution and a copper plate the

anode. Large articles of iron, such as the parts of ordnance, are

sometimes copper-plated to preserve them from the action of the

atmosphere. Seamless copper pipes for conveying steam, and wires

of pure copper for conducting electricity, are also deposited, and

it is not unlikely that the kettle of the future will be made by

electrolysis.

Nickel-plating is another extensive branch of the industry, the

white nickel forming a cloak for metals more subject to corrosion.

Nickel is found to deposit best from a solution of the double

sulphate of nickel and ammonia. Aluminium, however, has not yet

been successfully deposited by electricity.

In 1836 De la Rue observed that copper laid in this manner on

another surface took on its under side an accurate impression of

that surface, even to the scratches on it, and three years later

Jacobi, of St. Petersburg, and Jordan, of London, applied the

method to making copies or replicas of medals and woodcuts. Even

non-metallic surfaces could be reproduced in copper by taking a

cast of them in wax and lining the mould with fine plumbago,

which, being a conductor, served as a cathode to receive the layer

of metal. It is by the process of electrotyping or galvano-

plastics that the copper faces for printing woodcuts are prepared,

and copies made of seals or medals.

Natural objects, such as flowers, ferns, leaves, feathers,

insects, and lizards, can be prettily coated with bronze or

copper, not to speak of gold and silver, by a similar process.

They are too delicate to be coated with black lead in order to

receive the skin of metal, but they can be dipped in solutions,

leaving a film which can be reduced to gold or silver. For

instance, they may be soaked in an alcoholic solution of nitrate

of silver, made by shaking 2 parts of the crystals in 100 parts of

alcohol in a stoppered bottle. When dry, the object should be

suspended under a glass shade and exposed to a stream of

sulphuretted hydrogen gas; or it may be immersed in a solution of

1 part of phosphorus in 15 parts of bisulphide of carbon, 1 part

of bees-wax, 1 part of spirits of turpentine, 1 part of asphaltum,

and 1/8 part of caoutchouc dissolved in bisulphide of carbon. This

leaves a superficial film which is metallised by dipping in a

solution of 20 grains of nitrate of silver to a pint of water. On

this metallic film a thicker layer of gold and silver in different

shades can be deposited by the current, and the silver surface may

also be "oxidised" by washing it in a weak solution of platinum

chloride.

Electrolysis is also used to some extent in reducing metals from

their ores, in bleaching fibre, in manufacturing hydrogen and

oxygen from water, and in the chemical treatment of sewage.

The Story of Electricity · 第 5 / 11 章