uslizahm 6leetie E E ofpen3ha Tayl, Univesise

ELECTROLYTIC PROCESSES 259

aTect is that copper is dissolved from the anode and

deposited
ea the cathode.
CHAPTER I V
Applications.-The commercial applications' of the above prin-
aple are as follows:
ELECTROLYTIC PROCESSES
Extraction of Metals from their Ores.-The ore is either melted
or treated with strong acid and current passed
THE fact that metals can be deposited in a
through the
resulting solution; the solution is dissociated and pure metall
very pure form from deposited on the cathode.
solutions of their salts by passing a current
has
through
them (elec
trolysis) been known since about 1800, and processes
based Refining of Metals.-Anodes of impure metal are placed in a
on this are widely
used for the extraction of metals from
ores, for the
theirsuitable electrolyte and, on passing a current through the bath,
refining of metals, and for the electro-deposition of pure metal is deposited on the cathode.
metals, including electroplating, electrotyping, and the building
up of worn parts. Simila electrolytic processes are also used Electroplating and Electrotyping.-The article to be plated is
the manufacture of various ehemicals. 1 ade the cathode in a suitable electrolyte together with an anode
sf the metaB to be deposited.
. FUNDAMENTAL PRINGIPLES
Manufactere of Chemicals.-Current is passed through a solu-
Although the processes mentioned above differ widely in detal on of some compound, causing it to dissociate into its con-
the underlying principles are the same in each and consist simply situent parts, which are liberated at the anode and cathode, and
of the
passing of a direct current through a solution of a chemic hich can be collected or allowed to take part in a secondary
compound in order to dissociate the solution into its constituerd action with the original solution to obtain the desired
parts. Froduct.
Ionic Dissociation araday s Laws
Solutions with which the above process can be carried out are The laws which govern the above electrolytic processes were
known as electrolytes, and in such solutions each molecul of the mulated by Faraday and may be stated as follows:
substance dissolved dissociates into two ions, one of which i ) The weight of a substance deposited from an electrolyte is
negatively charged and the other positively charged. Thus whez roportional to the quantity of electricity (coulombs) which has
copper sulphate is dissolved in water it dissociates into positively assed through it.
charged copper ions and negatively charged sulphions (SO). ii) If the same current is passed through different electroly tes
now two electrodes are placed in the solution and a potentia e weights of the
substances deposited from each will be pro-.
difference maintained between them, the negative ions (aulphions tional to the chemical equivalents of those substances.
will be attracted to the positive electrode (anode) and thepositive
copper ions to the negative electrode (cathode). As soon as t OundergtaelectrolysIs, the reader must have a clear
1on reach the electrodes they give up their charges and becore ncept of the following terms and
definitions
ordinary molecules. Thus in the above case the. copper ions 1. The electrochemical equivalent of a substance is the mass of
become ordinary molecules of copper, which are deposited on tE iberated in a process of electrolysis by thiS passage of unit
cathode, while the sulphions, on reaching the anode, becoE atantity electricity, i.e. by unit current (ampere) for unit
of
orainary SO, molecules. With the latter a secondary reactics me (second). The SI Unit of
takes place as they react with the water to produce oxyge fie kilogram per coulomb. (kg/C).electrochemical equivalent Z, is
is iberaterl as a
wlch gas, and sulphuric acid, which dissolves
in
the water or, if the anode is of copper, attacks the anode an 2. The atomit weighi of an element is a number, which is
produces more copper suiphate. In this case, therefore, t te average of the masses of its various isotopes,
weighed
258
 ELECTROLYTIC PROCESSES 261
UTILISATION OF ELECTRIC ENERGY
260
TABLE XIII
on a scale in which 12,C
relative abundance,
according to their scale the CHEMICAL AND ELBCTRo-CHEMICAL EgUIvALENTS
e.g. on this
nuclide of carbon is designated exactly,
because this is the average Electro-chemical1
chlorine is 35.543
atomic weight of regard to their Element (atomn or At, wt. or equivalent kg/
of the various isotopes having valency equivalent
v a l e n c y C h e m i c a l

of the masses radicle) form. W coulomb

relative percentage occurrence.

of chemical entity (atom, radicle, 26.9815 9.1 9-321 x 1078

3. The formulae weight
a
of its Aluminium 56.2 58. 20
is the s u m of the atomic weights Cadmium 112.4
20 75
molecule, ion, etc.) an oxygen molecule Calcium 40.008 20.04
Under ordinary conditions, Chlorine 35.4453 35 37 36 740
constituents. the
wt. of oxygen=15.999 4), 63.54 3] 8 32937
consists of two oxygen atoms (at. 4=31.998 8. Copper (cupric).. 65.4 6768
is 2X 15.999 Gold 197-2
formula weight of moletular oxygen has a formula weight= Hydrogen 1.008 1.045
28-90
H,SO), 85 27.9
Sulphuric acid (formula:
follows:
Iron (terrous)
207.21 103.2 107 16
Leead
98.063 59 calculated as Magnesium 24 32 97 2.43
349
weight formula wt. ofsulphate Nickel 58 69 29.3
formula92 atomic
formula X radicle Nitrogen 14.008 4.67 4 85
of hydro5 .062 98-00
98.063 594 Oxygen2 15.9994
100
7.98
39.04
8-29
40.54
=
2 X 1.000 797+ 96.062 Potassium
107.880 107.6 l1.80
Silver
to its formula 22 991 22.99 23.8
chenmical entity numerically equal 31.988 8
Sodium 118.70 59 3 40
61
A m a s s of a weight in SI Units. Thus,
Tin (stannous)
Zinc 65.38 32.45 33 88
weight is termed a kilogram
formula weight' of oxygen.
kg is the "kilogram
of an atom or radicle (i.e. group
a of Calculation of Current reguired:-From the electro-chemical
4. Valency: The valency with which it will
number of hydrogen
atoms equivalent it is possible to calculate the theoretical value of
atoms) is the
react chemically; valency is vays
an integer (1, 2, 3, etc.) but urrent required to deposit any given quantity of metal or
radicle, it can have different values in diffe- alternatively the amount of metal which should theoretically
for a given atomn or
rent chemical reactions. be desposited by a given current.
The equivalent weight of a
substance is Example 21-A sheet of iron having a total surface area o
5. Eguivalent Weight: divided by its valency, i.e. p.36 ma is to be electroplated with copper to a thickness of 0.0254
the quotient of its
formula weight
. What quantity of electricity will be required? The iron will
equivalent weight =
formula weight e made the calhode and immersed, together with an anode of pure
valency copper, in a solution of copper sulphate.
the e l e c t r o c h e m i c a l equivalent
In the case of hydrogen, displaced from a
coulomb, so that for coPpper
Mass density of copper as 8.96 x 103 kg. m3; A
1-045 X 10-8 kg. per second law, 1.045 X
to Faraday's
cupric salt it is, according the atomicor formula e. C. e. of copper as 32.9 10-3 kg. C-1
(63.54/2)=32.927 x10-8 kg./C. Values of of the various
e l e c t r o c h e m i c a l equivalents
and Solution :
weight, valency in commercial
e l e c t r o c h e m i c a l processcs

substances concerned Mass of copper to be deposited = 0-36 X 0-0254 X 10- X

are in Table XIII.
given 8-96 X108 kg = 0-082 kg.
The e. C. e. of copper 32:9 kg-pes-eoulomb X1
32.9X1O-8 x 3600 x1000-kg per 1000 Ah.
1-184-kg per t000-Ah.
Cha 2
 2Sx lo e
UTILISATION OF ELECTRIC ENERGG¥ ELECTROLYTIC PROCESSES 263
262
0-082 the tendency of the metal to go intosolution. This is known as
Ampere hours required 1.184 the electrode potential, and its value depends on the exact condi-
= 69-24 or say 69.5ar-hours tions (e.g. temperature and concentration), and also upon the
nature of the metal and the electrolyte. For most substances
The current density normally used in opper-plating bath is the value as measured under ideal conditions lies between 0'5
of |l5 A
about 330 Am, so that in the above case, a current and 1:0 V. The total voltage required to pass current through
would be required. The time taken to perform the plating an electrolytic cell is thus not more than about 1 or 2 V,
process would, therefore, be: Energy Eficiency.-The theoretical value of the metal depo-
69.5 = 0-604 hour. sited by a given current can be calculated from Faraday's laws,
115 he voltage from the electrode potentials of the metal and
above theoretica solution concerned, and the specific resistance of the solution, so
In practice certain losses occur, so that the
and the current requireda
quantities would not be obtained increased
that the theoretical amount of energy required can be found. Due
by about 10 pea o various secondary effects and reactions, the metal deposited
the time taken would have to be than the theoretical value and the
cent.
ya given current is less
substance or su
Toltage will be higher, so that the energy consumption
Current Efficiency.-The quantity of a ill also be higher.than the theoretical value. The ratio
stances liberated is usually slightly less than the quantiti
rtheoretical energy requireais known as the energy efficiency (n)
calculated from Faraday's laws as above on account of impuri5 actual energy required
This is taken is
which cause secondary reactions to
occur.

factor, known as the current eficien EXTRACTION AND REFINING OF METALS

account by employing a
of substance
which is defined as the ratio of the actualInquantity
practice it is usua Electrolytic methods of extraction and refining result in a
liberated to the theoretical quantity.
have an apparept rer product than most of the metallurgical processes and, as
between 90 and 98 per cent. Certain processes
low current efficiency on account of. the fact
that there is result of the tendency of electric power costs to be reduced,
substances other than that whici becoming widely used. In some cases, e.g. aluminium and
unavoidable production of me of the rarer metals, electrolytic extraction is the
chromium plating, in which the electrolyte
2ilable method. Large quantities of energy are required, only
required: thus, in
about 12 to 15 per cent. of
acid, only andd
a solution of chromic
current passed is actually used
in depositing chromium from the process is usually continuous the load factor approaches
solution, the remainder being used in producing hydrogen per cent., so that it forms a desirable load for. any power-
oxygen which, for the purpose
in hand, are useless. 9ply company, and can generally, be supplied at a fairly
eap rate.
Voltage.-The voltage necessary to pass current through
due to the resistancz
casse
electrolytic cell is made up of the drop traction ofMetals
the electrolyte and the drops at the
anode and the cathode
can easily be calculated from Proces[es for the extraction of metals may be divided into two
resistance of the electrolyte area and lengtt sses according to whether the electrolyte is a solution of a salt
specific resistance and the, cross-sectional resistance shee he metal obtained by treatment of the ore with strong acid or
the current path. To economise power this
be kept as low as possible, and in many cases sp ether it consists of the ore in a molten state. Summaries of
obviously solution to reduce its achief processes in commercial use are shown in Table XIV.
conducting agents are added to theo r refining, sulphuric
in copper plating
ance. Thus,
dded to the capper-sulphate bath.
At the anode and cathode there is
a potential difiea
between the electrode and the electrolyte, which is a measze
 ELECTROLYTIC PROCESSEs 265
264 UTILISATION OF ELECTRIC ENERGGY
cathode and settles at the bottom of the bath, from whence it is
TABLE XIV
tapped off as required. A furnace having an area of 13.6 m
ExTRACTION Or MsTALS will require a pressure of 5 or 6 V. and a current of about
40,000A. It may be noted that the whole of the rapidly
Metal Treatment of ore Solution Consumption, kWh increasing world consumption of aluminium is produced electro-
per tonne (approx.)
lytically.
Aluminium. Fused cryolite 20,000 25,000
Copper Roasted and lea- Copper sulphate 2,000 2,500 Reflning of Metals
ched with sul-
phuric acid The metal obtained by electrolytic extraction is 98 to 99, per
Magnesium . Fused magnesium 17,000 20,000 cent. pure, and this forms one of the chief advantages of that
chloride or car
nallite method of production. Sometimes, however, extraction cannot
be economically carried out, and in such cases only the refining
Sodium Fused sodium hy- 10,000 20,000
drate or sodium process is done electrolytically. Anodes of the impure metal
nitrate and so- obtained from metallurgical reduction furnaces are placed in an
dium chloride
electrolytic cell containing a suitable electrolyte and the pure
Zinc Leached with sul- Zinc chloride and 3,000 5,000
phuric acid zinc sulphate metal is deposited at the cathode. A summary of the more
important refining processes is given in Table XV, Although
both metallurgical and electrolytic processes are used for the
Extraction of Zinc.-As an example of the processes emplo extraction of copper, the whole of the very pure metal required
ing an aqueous solution as electrolyte; the extraction of zi by the electrical industry is refined electrolytically.
from zinc ore may be cited. The ore, consisting largely of zin
oxide, is treated with strong sulphuric acid, roasted, and pass
TABLE XV
through various chemical processes to precipitate cadmiuz REFINING OF METALS
zinc sulpha
copper, and any other impurities; the resulting
solution is passed to the electrolytic cells. These consist
a number
Consumption kWh.
Metal Solution
large lead-lined wooden boxes, each containing per tonne (approx.)
aluminium cathodes and Head anodes and carrying a current
the
sisE
several hundred or thousand amperes, according to Copper Copper sulphate 150 300
The current density on the cathodes is about 1100A/m*. T Gold Chloride of gold 300. 350
so that with 100 Lron Iron ammonium sulphate 1,000- 1,500
potential drop in each cel is about 3'5V., is require Lead Lead fluosilicate 100 120
I 50 of them in series a pressure of aboue 500V., Nickel Nickel chloride and sulphate 2,5004,000
the cathodes, which are removed ont Silver Nitric acid and silver nitrate 400 420
The zinc is deposited on
-

or twice a day for stripping8.

Extraction of Aluminium.-An example of the fused-electrólv2 3. ELECTRO-DEPOSITION
extraction of aluminium from its ores
process occurs in the
bauxite and cryolite. The bauxite is first treated chemically The term electro-deposition is usually regarded as covering
reduce it to aluminium oxide and this is then dissolved
in fusw the various processes whereby a coating of metal is electrically
in which the fusion a deposited on some other metal or non-metal. It includes electro-
cryolite and electrolysed.The furance bath lined
electrolysis take place consists of a shallow rectangular plating, where a layer of metal is added for decorativeor protec
anodes project downwards into the bath am
tivepurposes, electrotyping for the production of printing-blocks,
with carbon ; carbon
te bottorn of the bath torms the cathode. 1he high temperatone electro-forming for the production of thin sheet or foil, the mak
tused state is mais ing of gramophone records, and for the building up of worn
1,000C.) necessary to keep the ores in a
tained by the ohmic losses of the current passing through tiz parts to their original thickness.
electrodes and the electrolyte. Aluminium
is deposited at he
266
UTILISATION OF ELECTRIC ENERGY ELECTROLYTIC PROCESSES 267

Factors governing Deposition Processes

techni-
Although electro-deposition processes, where such are
with any alter-
cally possible, can usually compete economically
difficulties which limit
native process, there are various pactical
be used to give a satis-
the number of metals which can actually
the processes which have been
factory deposit. A summary of is slhown in Table XVI.
found practicable
commercially
Throwing Power.-One of the most important properties of
or deposition bath is
its throwing power, that is, its
a plating
on an article of irregular shape.
ability to produce an even deposit The potential difference
Consider a bath as shown in Fig. 117.

i!
FiG. 117-ELECTROPLATINc BATH.

be plated
between the anode and any point on the article to
the the surface AB is howeve
(cathode) is; of course, same;
surface CD, so that the
twice as far from the anode as the
resistance of the current path through the
electrolyte" to the
twice as great; the current density
former will be approximately
will thus be smaller
and therefore the thickness of the deposit,
The dificulty can be overcome to
on this part of the surface.
the anode and cathode farther apart, so
some exent by placing
that the relative variation in resistance between the anode and
different parts of the cathode is
less. The voltage drop at the ::
effect. In some cases.decrease o
cathode surfacè also has an
decrease in cathode drop, leaving
current density causes a
for overcoming the resistance of the
more voltage available change in curre
counteract
electrolyte, thus tending tosolutions ofany
the cyanides of meta
For this reason
density. of th
greater throwingpower than solutions
usually give a

sulphates.
 268 UTILISATION OF ELECTRIC ENERGY

ELECTROLYTIC PROCESSES 269

Addilion Agents.-The addition of acids or other substances to
the electrolytefor reducing its resistance has previously been anode and be deposited on it. Current densities of about 100 A
mentioned. There is another class of addition agent which takes per square metre are enployed, and deposits up to about 10mm
little or direct part in the chemical reactions, but which, in
no thick can be obtained.
some way, influences the nature of the deposit,
sometimes even
Anodic Oxidation of Aluminium.-When aluminium is made the
making an otherwise unworkable process into one of practical anode in a suitable electrolyte (usually chromic or sulphuric
in the deposition of zinc
importance. A typical example occurs
from zinc sulphate solution, when the addition of glucose or c e r acid), a very hard and adherent oxide film is deposited on it
tain types of sugar is essential to the production of a satisfactory which is resistant to nearly all corroding media. The coating
can be made to absorb dyes, so that coloured finishes can be
deposit. obtained and are becoming widely used for decorative purposes
that many
Healing of the Bath.-Reference to Table XVI shows on shipboard and in other situations where a corroding atmosp-
of the processes require the bath to be heated to fairly high here exists.
be employed
temperature. Steam, gas, or electric heating may
this the heating pipes or cables being placed in the 4. MANUFACTURE OF CHHEMICALs
fo purpose,
ensure that
bottom of the bath; care must, of course, be taken to .The most important processes for the production of chemicals
the chemicals in
they are of materials which are not attacked by in the works. involve the electrolysis of brine, although other processes arealso
the bath. Steam is of ten required for other processes in commercial operation ánd are summarised in Table XVII.
the most economical method of
and in such cases provides
be preferable. In the electrolysis of brine, chlorine is given off at one pole and
heating, otherwise gas or electricity may the vat. In the
hydrogen at the other, leaving caustic soda in
Deposition of Alloys first of the two processes listed in the table, the chlorine and the
potentials of the constituent metals
Provided the electrode are TABLE xVII
approximately.similar, possible to deposit alloys, Anodes
it is PRODUCTION OF CIIEMICALs
of a mixture of
of the alloy are used in an electrolyte consisting
which would be used for the separate deposition
the electrolytes
and bronze are widely plated in Product Solution Consumption (approx.)
of the metals concerned. Brass
indicate that the deposition of
this way, and recent researches
will soon be commercially Caustic soda Brine 3,000-4,000 kWb./tonne
various copper and nickel alloys
Chlorine compounds of
practicable. sodium (chlorates, per-
chlorates, hypochlorates) Brine 3,000-7.000 1&Wh./tonne
Miscellaneous Depositlon Processes Oxygen and hydrogen Water 125-150 kWh. (for
28.32 mH+14.16 m0)
the principles of electro-deposition Potassium permanganate. Potussium manganate | 70-80 kWh-/tonne
Other processes involving
the most important of which are the deposi- Ammonium persulphatc. .Ammonium sulphate 2,000-2,500 kWh./tonne
have been developed,
oxidation of aluminiumn. Both
tion of rubber and the anodic
these processes involve reactions occurring at the anode instead hydrogen are pumped off as quickly as they are produced and
from metallicsalts
of the cathode, as with the ordinary deposition form valuable by-products; in the second process no attempt is
Rubber.-Rubber latex as obtained from
made to separate the hydrogen from the chlorine, and they there-
Electro-deposition of fore combine to form hypochlorates, chlorates, or perchlorates,
the tree consists ofveryfine colloidal particles of rubber suspened according to the exact method of carrying out the process.
in
water. In common with othercase
collodical solutions, the particles
in this negatively; if electrodes are Certain industrial effluents, notably those from the soap in
areelectriçallycharged, and a potential diference applied dustry, contain appreciable quantities of common salt, and these,
put in the solution, therefore, towards the as well as others, can sometimes be treated electrolytically to
between them, the rubber particles will migrate
yield valuable by-products.
270 UTILISATION OF ELECTRIC ENERGY ELECTROLYTIC PROCESSES 271

5. POWER SUPPLY FOR ELEGTROLYTIC PROGESSES CHAPTER IV

The salient features of the power supply for QUESTIONS
electrolytic pro-
cesses are that it must be direct current and a. relatively low
1. The worn out part of a circular shaft 0.15 m in diameter
voltage. For electro-deposition the amount of power usually and 0.3 m. long is to be repaired by depositing on it 1.6 mm of
required is small (up to 100 or 200 amps. at 10 or 12V.) and can nickel by an electro-deposition process. Estimate the quantity
be obtained without difficulty from the ordinary supply system
of electricity required and the time taken if the current is to be
through a suitable convertor. The majority of installations
215.0 A/m The current efficiency of.the process may be taken
employ a motor-generator set consisting of a standard induction
as 95%
motor driving a heavy-current generator. The mercury-arc 2. A group of 400 cells in a copper refning plant carries a
rectifier is ruled out on account of its low efficiency at the low current of 5,000 A. The voltage per cellis 0.25 V. If the plant
voltages which are required, but the copper-oxide rectifier has works for 100 hours per week, estimate the annual output of
been developed for this purpose and, being a static piece of
apparatus, has a lower maintenance cost than a motor-generator refined copper from the cells and the energy consumption in
set, and also a higher efficiency, especially at low loads. kWh per tonne.
Where only a single bath is supplied from a generator, the con- 3 How much aluminium would be produced from aluminium
trol of the current to the bath is carried out by variation of the Oxide in a working week of 100 hours in a cell carrying an aver
generator excitation, but in other cases a variable resistance is age current of 5,000 A? The current efficiency is 70% If the
connected in series with each bath, so that the supply to each can; voltage of the cell is 6 Vand energy costs 3 paise per unit, what
be controlled independently. would be the energy cost per tonne of aluminium produced ?
Extraction and refining of metals and large-scale manufacture
. 4. Calculate the amount. of energy required to produce
of chemicals require very large amounts of powerthe British
2700 m of hydrogen by the elecirolysis of water in cells operat
Aluminium Co., Ltd., use 90,000 kW. at their Lochaber works.
ing at 2 V per cell. The current efficiency is 97%.
With most processes the cost of this power is a major expense, and
special attention must be paid to the obtaining i it at the mini-
mum possible cost. Fortunately this is assisted by the fact that
most prOcesses are continuous and therefore have a load factor
which approaches 100 per cent. The usual procedure is to locate
the works near to a source of hydro-electric power, even if this
necessitates extra trans-shipment of the raw materials, sincé the
advantage of a high load factor is greater with such stations than
with steam stations, and also transmission costs are eliminated
Electro-chemical works are thus built or are being built around
the power stations at Niagara, Dnieprostroi, Boulder Dam, and
elsewhere.
number of
Although the voltage per cell is only about 10, a
such cells can be connected in series, so that the voltage required
thousand amperes
is 500 to 800 with currents of up to several
can be made to
With privately owned plants the water turbines
mentioned above
drive d.c. generators, as at the Lochaber works
but where the generating station is also connected withgeneral
to a
network, a.c. generation must be employed, special
supply convertors, or even mer
heavy-current motor-generators, rotary
cury-arc rectifiers to convert to d.c. at the requird voltage.