CHEMISTRY

INDUSTRIAL

BEING

SERIES

OF

VOLUMES

GIVING

COMPREHENSIVE

SURVEY

CHEMICAL

THE

Edited

D.Sc.

RIDEAL,

FELLOW

UNIVERSITY

OP

A.

BACON,

W.

F.

S.

H.

H.

B.Sc.,

BARROWCLIFF,

M.

H.

B.Sc.

AUDLEY,

GARNER

H.

CARR,

H.

C.

GREENWOOD,

R*

PARTINGTON,

R.

F.I.C.

M.Sc.,

B.Sc.

"C.

W.

SIMMONS,

M.

WHITTAKER,

D.Sc.

F.C.S.

SUTHERLAND,

HUGH

S.

B.Sc.

M.A.,

F.C.S.

SMILES,

A.

Ph.D.,

B.Sc.

SINDALL,

SAMUEL

D.

D.Sc.

H.

TAYLOR,

(Vict.)

B.Sc.

PRATT,

RIDEAL,

K.

W.

F.I.C.

D.Sc.

E.

ERIC

M.Sc

COLLINS,

GRAY,

LONDON

ARTHUR

F.I.C.

F.I.C.

BY

J.

F.I.C.

BENNETT,

HOARE

Lond.,

COLLEGE,

ASSISTED

JAMES

OF

INDUSTRIES

SAMUEL

by

D.Sc.

F.I.C.

INDUSTRIAL
ELECTROMETALLURGY
INCLUDING

ELECTROLYTIC

AND

ELECTROTHERMAL

PROCESSES

BY

K^RIDEAL,

ERIC

JOINT

AUTHOR

MA.

WITH

S.

NEW

D.

VAN

(Cantab.), Ph.D.,
R1DEAL

OP

WATER

SUPPLIES

YORK

COMPANY

NOSTRAND
25

"

PARK

PLACE
1919

F.LC,

PRINTED

IN

GREAT

BRITAIN

GENERAL

The

PREFACE

of

rapid development

has

brought about

This

has

growth

British

has

now

during the

materials

The

subject in this series of handbooks

available

industrial
the

rather

will

give

of

of

industrial

Historical
different

of

branches

within

moderate

future

developments

will be

devoted

to

chief

each
in

far

as

it

book

Each

chapters, and
of the

will
the

information

attempt

manner

will

but

of

will, in fact, be

on

the

also

the

with

the

be

kept

will

they

and

and

industrial

possible

some

space

methods

There

and

will be

bibliography to follow
only be introduced

line of argument.

into
deal

affected

as

dealing

will

the

divided

sections

subject in the
An

be

in

select

how

stimulating invention.

countries.

illustrate

to

serves

also

shown,

attention,
of

of

that

have

tendencies

producing

Statistical

be

feature

have

than

inventions

in

comparison

general bibliography,and
section.

will

Present

will

and

new

subject,

the

limits.

in the

progress

of

requirements
a

The

complete in itself,and

applied

been

be

from

industry, showing

the

industry

will

notes

world.

treated

prominent

will be

influence

the

the

to

parts of the
will be

more

of

survey

The

development

increasing its

engineering standpoint.

be

principles have

manufacture.

so

the

volume

Each

general

chemical

effect

than

aspect will also

laboratory.

different

in the

the

and

by the application of this knowledge

output

chemical

years

technology.

war,

of

opportunity

an

raw

the

of

in all branches

accelerated

been

Empire

industrial

revolution

in recent

Applied Chemistry

sections

with

separate

special article
made

to

of

instead
branches
or

get away

graph.
mono-

from

vi

GENERAL

the

orthodox

textbook

by

of affairs

men

who

in

matters

if

time

for fuller details

works

useful

knowledge,

but

technical

to

with

compass,

there

found

refer

to

ment
treat-

of which

also be

time

to

the

large class of

very

special technical

no

of moderate

book

the

to

should

books

having

large standard

the

The

require from

may

appeal

make

to

possessing good textbooks,

already

quite sufficient.

are

only

not

manner,

also to

original,but
readers

PREFACE

references

to

special points

on

required.
To

His

valuable.
details

and

student

advanced

the

mind

is often

his

of

such

remedy

basic

essential

industrial

career,

knowledge

academic

industrial

current

to the

and

this

which

so

the

thus

for
save

chief

the

the

than

larger

they

more
a

in
not

are

serve

can

elaborate

go

hensive
compre-

material

ordinary

textbooks

of

the

at

books,
text-

present
have

who

when
of

the

concerned.
to

the

value

to

to

once

information

they

branches

to

standard
the

comprehensive

on

probably find these

guide

prove

obtained

he

his

immediately
a

industry

regard

as

his

by

very

objects of

will

our

information

of

to

in the

limits

narrow

industry,

authorities
and

of

that, having

whole

of

commencing

on

giving

be

can

adjunct

an

as

of

book

reality

drawback

of his lack

subject, and

of the

literature

the

positively handicapped

industry

one

recapitulating the

been

of

intended

are

presenting

at

facts

power

is

will also

volume

The

is

the

collegegraduate,

their memories

to refresh

subject with

While

hard

the

student

readable

more

affairs.

"because

the

rather

specializedin
books

books

actually engaged

Those

series.

These

conditions.

of

survey

assistance

whole.

long

especially

the

out

It has

that

with

crammed

facts, they will aim

education

technical

wish

of

state

be

crowd

living industry.

of the

his

as

should

books

subject which

realizingthe industry
to

the

view

the

sultant,
con-

of

proper

special points,

on

couple of days spent in hunting through the

libraries of scientific societies.

As
the

and

far

as

this

general scheme
it

is

country
of

is

concerned,

this series

confidently hoped

that

of

it is believed

handbooks
it will

is

supply

that

unique,
mental

munitions
fortunate

are

for
in

securing

Industrial

Chemistry,

contribute

to

throughout

writers

connected

specially

the

the

industrial

coming

the

further

vii

PREFACE

GENERAL

for
with

and

the

trust

development

different
several

the
that

war.

have

volumes

who

departments

the

whole

of

applied

series

chemistry

Empire.
SAMUEL

been

RIDEAI,.

of
will

AUTHOR'S

Amongst

the

shown

following

the

of

the

both

indicate

and

electrolytic
is

It

matter

Electrochemistry

in

"subject"
a

limits

and

of

past

and

has

not

yet,

raised

to

lack

this

sufficient
the

of

that

text-books

to

eliminate

in

ceptional
ex-

of

standing

As

system.
but

scant

lectures

in

excellent

an

electrochemistry,

the

English

the

two

or

exists

there

element

that

chemistry.

theoretical

on

personal

of

physical

fact

one

few

domain.

concern

receive

to

to

application

this

dignified

confined

the

of

in

and

made

the

present

considerations

whole

the

of

educational

higher

being

been

in

except
the

metallurgy
electro-

teaching

research

has

been

student

from

field.
As

result

either

ill

there

with

awaiting

capable

of

Industry

in

in

raw

at

knowledge.

in

the

the

great

hands

time
gators
investi-

by

out

materials

having

both

waste

English-speaking

and

power

part

carried

requisite
the

suffered
to

or

work

development
taking

has

processes

the

that

of

sources

are

variety,

foreign

equipped

forgotten

be

English

experimental

in

money

not

the

purchase

to

and

are

regret

English

Notwithstanding
bibliography

possibilities
methods

our

covering

has

electrothermal

usually

attention,
course

an

chemistry
development,

endeavour

pages

electrochemical

result

applied

technical

great

been

cases,

of

branches

many

has
in

PREFACE

It

must

countries
in
of

post-war

very

great

those

who

period

of

reconstruction.
In

both

many

economic,

specific

cases

aesthetic,

electrochemical
industrial

and
IX

processes

advantages

offer
over

AUTHOR'S

older

chemical

old

it is the

ones,

that
In

electrode
of

standard

of

pressure

elements

which
noble

In

of

form

although

upon

of

application

assist

in

for

electrolytic

June,

19

S.

the

account

on

compounds
the

at

of

and
the

high

reactions

where
include

emphasis
in

have

the

gives

has

electrolytic
tion
dissocia-

the

and

temperatures,

coefficient

metals,

in

purposes

Special
colloids

their

usually

processes

partition'

slags

shown

as

of

of

necessarily

must

electrothermal

in

derivation

practical

of

formation

of

substances

been

used

involved.

E.
London,

i.e. those
whilst

of

correct,

effects.

influence

elucidation

the

tional
conven-

electrolytic

value

method,

observation

immiscible

between

the

active,

the

strictly

not

the

of

arbitrary

hydrogen,

heats

for

This

accurate

stable

many

the

basis

the

electrode

whilst

deposition,

the

calculations

the

experimental

laid

normal

an

negative

the

the

possess
of

end.

pressures.

sufficiently

been

given

are

irreversible

whilst

before

that

chemistry
electro-

this

the

as

chemically

potentials.

introduction,

small

than

most

solution

decomposition

direct

which

greater

compounds

results

metals

elements

many

certain

placed

are

small

their

taken

is

sign

to

processes,

difference,

potential

those

solution

been

has

zero

positive
potentials

Electrolytic

on

new

consideration,

contribute

may

of

for

case

deliberated

and

due

the

that

velopment
de-

the

exploitation

the

author

volume

present

sections

hydrogen

of

the

both

have

the

the

more

of

in

in

and

treatment,

or

processes

hope

may

and

metallurgical

or

of

PREFACE

K.

Iv.

to

CONTENTS

PAGE

GENERAL

PREFACE

AUTHOR'S

PREFACE

ix

INTRODUCTION.

The

Ionic

Electrolytic

theory.

Reaction

velocity.

and

Diaphragms

metalliferous

The

Power.

Over-potential

potentials.

Fused

cataphoresis.
of

resources

British

the

and

passivity.
electrolytes.

Commonwealth

"
.

SECTION

ELECTROLYSIS

I."

IN

AQUEOUS

SOLUTIONS.

Copper

refining,

Winning,

"

addition

of

and

gold

for

Complex
Zinc.

brass.

and

Detinning.

Tin.

Bismuth.
nickel

Bronze

agents.

Parting

Gold.

Conditions

plating.
electrodes.

Rotating

metals.

of

silver.

uniform

Galvanizing.
Silver.

Plating.

deposition
Colloid

electrolytes.

Lead.

Nickel.

Cadmium.

Antimony.

Cobalt.

Cobalt-

alloys

28

SECTION

ELECTROLYSIS

II."

IN

FUSED

ELECTROLYTES.

Sodium.

Zinc.

Lead.

Calcium.

Magnesium.

Potassium.

Aluminium,

aluminium

Strontium.

Barium.

alloys

109

.....

III.-

SECTION

THE
OF

Gallium.

Indium.

Lanthanum.

Thallium.
Boron.

ELECTROLYTIC
THE

TION
PREPARA-

RARER

Cerium.

METALS.

Neodymium.

Vanadium.

Titanium.
XI

Praseodymium.

Manganese.

Uranium

135

CONTENTS

xii

SECTION

PROCESSES.

ELECTROTHERMAL

IV"

PAGB

Zinc.

Nickel.

Copper.
Vanadium.

Uranium.

Tellurium.

Phosphorus.

SECTION

disulphide

Silundum.

OXYSILI-

AND
OF

CIDES

Carborundum.

139

CARBORUNDUM

V."

Graphite.

Silicon.

Zirconium.

Carbon

Arsenic.

Tungsten.

Molybdenum.

Chromium.

Manganese.

Silfrax.

CARBON.

Siloxicon.

Monax.

.164

Fibrox
.

VI."

SECTION

Properties

furnaces.

ingot

or

carbides.

the

of

THE

Calcium

Tapping

CARBIDES.

carbide.

furnaces.

Heat

of

Continuous

formation.

Block

furnaces

.172

SECTION

ELECTROTHERMAL

VII."

METALS

BY

FIXATION

NITROGEN
AND

METALLIC

COMPOUNDS.
The

nitrogen

Arc

problem.

Biochemical

Hausser's

processes,

the

method,

nitrides, cyanides

The

methods

and

Haber

cess.
pro-

cyanamides
"

VIII."

SECTION
Electrolytic
of
and

The

functions

desulphurization.
The

furnaces.
furnace.

"pinch

Ferro-alloys.

molybdenum,

AND

Electrothermal

iron.

steel.

IRON

vanadium,

pig
the

of
Arc

slag.

furnaces.

effect

"

The

production

tungsten,

uranium,

Composite

high frequency

The

and

refining

deoxidation

furnaces.

Induction

Ferro-silicon,

and

Dephosphorization,

furnace.

titanium,

FERRO-ALLOYS.

THE

iron.

183

induction

chromium,

manganese,
boron
.

APPENDIX

205

237

INDEX
.

239

INDUSTRIAL
ELECTROMETALLURGY

INTRODUCTION
The

foundations

lurgy
general principlesof electro-metallaid by Michael
Faraday in 1833, wh" introduced

were

the

of the

nomenclature,

present

e.g. such

electrode, cathode,

anion, and

quantitativelaws

which

on

electrolyticprocesses
it is to

that
that

Faraday
each

suggestionof
in

solute

solution

the

the

solution

is

velocities

FromHittorf

to calculate

the

actual

forgotten

electronic

first

ciated
asso-

tangible

theory of electricity.
concentration

the

during

of

the

electrolysis. The

sulphate, for example, in

aqueous

anode

cathode

decreases

and

subjected
he

at the

electrolysis.

to

able

was

ions, whilst

of the

calculate

to

Kohhrausch

investigation on

solutions,

able to

was

ions under

few

the
years

molecular

the

determine

definite

the

potential

'sandKohlrausch'sfiguresitis possible
ionic velocities

potentialgradient of one
The following figureswere
a

industry of

important generalization

element, the

an

that

elaborate

of dilute

conductivities

gradient.

an

and

quantity of electricityis

experiments
of the

fundamental

It is frequently

altered

at

series of

of the

noticed

of copper

transport number
later (1869),by
values

or

solvent

increases

such

By

atomistic

the

concentration

when

valency of

1853 Hittorf

In

owe

we

science

the

the

unalterable

definite and
with

both

electrolyte

as

the

us

gave

founded.

are

terms

volt

per

obtained

in
cm.

cms.

per

in dilute

for solutions

hour

under

solutions.
at

180

C.

ELECTROMETALLURGY

INDUSTRIAL

The

calculated

figures

of the

migration velocity of
Steele, and

Ix"dge, Whetham,
Up

solvent

the

dissociation

development in the principlesof

hypothesis as to the state of the solute

was

1887

In

necessary.

theory of Arrhenius

to this

theory

scheme

and

Grotthusian

the

the

replaced by

was

ing
Accord-

't Hoflf.

Van

dissolved

salt when

partiallydissociated

in

ionizing solvent

an

ing
follow-

into free ions, according to the

"

is established

Equilibrium

action, and

mass

by

others.

hypothesis of electrolytic conduction

is

in solution

ions

the

ment
measure-

this stage in the

to

electro-chemistryno
in

by actual

confirmed

were

the

with

in accordance

solution

as

whole

is

of

laws

the

electrically

neutral.
A

further

Hoff,

molecules

ated

equivalent

is

There
service
a

doubt

no

in

undissoci-

regarded

were

partialpressures

or

that

this

rigorous application of the

been

have

solvent

the

electro-chemist,

the

to

in solution.

substances

to

't

Van

as

of gases

mixture.

gaseous

subject by

reacting constituents,

concentrations

the

to

ions

or

laws

gas

of the

in the

made

was

applied the

who

concentration

The

in

advance

and

been

has

results

the
laws

gas

only extremely

not

conception
to

great

obtained

dilute

varied, but

of

of

by

solutions

far-reaching

importance.
It

the

is somewhat

ionic

't Hoff

theory

exclude
case

and

treated

could
between
when

the

be

the

originallysuggested by

somewhat

other

this

that

development

Arrhenius

chiefly accomplished in Germany,

was
a

"

unfortunate

pedantic train

important
function

rather

as

factors

of the
the

distributed.

from

solvent

convenient

Many

of
due
was

thought

and

Van

quently
fre-

where
tends

consideration.

of

to

In

entirely neglected

vacuum

in which

discrepancies

were

gases
noticed

experimental and calculated results, especially

genious
dealing with stroog electrolytes,and as a result inthe

theories

and

formulae

were

proposed

to

square

the

INTRODUCTION
facts

either

scientific
The

frankly empirical

generalization from

the

of

originally stated
the

by Arrhenius

advantages
consider

now

the

solvent

the

problem

itself

been

in

which

as

At

the

of

at

rate

any

must

we

in which

one

if not

performs important,

of the

one

was

light,as

new

form

proposed capable

but

one,

simple

't Hoff.

Van

treatment

old

of the

indicated

solvents

in the

and

theory has

new

no

the

(1904, et scq.)on

be retained

not

simple thermodynamic

great

Waal's

der

Walden

of

pseudoequation.

some

on

electrolytes in various

theory could

present time

based

or

Van

experimental work

conductivities
that

the

portant,
im-

most

functions.
Ionization
solution

to

the

be

must

regarded

taking place subsequent

as

(usually hydration) of the solute

following scheme

according

to

"

MX-"MX(H20)m^M(H20)rc+X,(H20)
both

undissociated

the

salt and

ions

the

being surrounded

The
of the forces
nature
envelopes of the solvent.
holding the envelope round the solute, as well as the number
in each
molecules
of solvent
of
envelope, is as yet a matter

by

uncertainty, but it
ionic

the

mobilities, that

small, rising to 6
ions of small

or

atomic

ionic

the

9 molecules

such

ones,

Electrolytic
addition

In

"

electrode

1889

science.
pressure

solution
been

has

or

metallic

the

electrons

the

this

On

the

metallic

to

of

the

ions

ions

potential

or
are

ionic

F', and

Cs* and

may

are

case

of the

be

entirely

I'.

hypothesis, all
drive

leaving the

ions

negative charges
between

are
are

forced
the

by

in

metals

metal

consequently

hypothesis

advanced

assistance

great

difference

in the

theory, the

pressure

to

of

Potentials.

"

tendency

ion

or

as

consideration

hydration numbers

per

weight, e.g. Uv

in the heavier

absent

probable, from

seems

into

in

Nernst

developing

possess

of

the

solution

solution.

Since

positivelycharged,
kept
into
metal

in the

metal

solution
and

until

layer of

in contact

solution

further

the

ions.

This

ions from

where

solution
C

solvent

and

its

enough

gm.

ions

to

the

solution.

of

to

by

8n

gm.

bringing hn

gm.

of osmotic

solution

concentration

of the

to

degree of ionization, and

log

metal

electrical

The

the

pressure

8"RT

prevent

valent

charge carried

equivalent

is the

to

ions.

8n

is also

aC, where

pressure

is great

is the

ve8n

transfer
the

of

electrode

the

is evVSn

work

metal

the

transfer

the

from

pass

with

discharge of metallic

Imagine
to

ELECTROMETALLURGY

INDUSTRIAL

equal

salt in the
to

-^

aC

virtual

principleof

the

By

work,
PT

log X

V^8w=8"RT

V=

or

aC
We

following
If

also

can

risen to

of

valency
and

electric

charge

relationship in

placed in

the

the

metal

ions
metal

the

when

the

solution
of the

in the

solution

has

metal

further, if fa and

aC, and
the

and

concentration

ionic

the

in
on

ve

electrolyte containing

an

equilibrium is established

risen to

has

molecules

uncharged

be

potentialsof

chemical

the

and

value

solution

in the

similar

potential between

of
a

at

"

its ions,
difference

aC

ve

manner

metal

arrive

log f-

"

[l be

and

respectively,with

the
an

ion, equilibrium is established

each

when

fa" fx"Vve

fa^+RT

But

log aC

Vas_ft-ri+RT

hence

logaG

ve

putting

/*"

log

/x0=RT

VRT

aC

ve

where
metal

is to

in the

The
calculated

be

form

regarded

as

of metallic

electrolytic solution
from

the measurements

the

solubility constant

of the

ions.
pressures

of

the

of the electrode

metals

as

potentials

ELECTROMETALLURGY

INDUSTRIAL

6
zinc

sulphate/zinc,the

wire, and

imagine it

dissolved

and

of

amount

again

to

If

charge

E.M.F.

per

done

by

work
a

is

given

energy

""eirv). The
in

dissolve

cell

so

the

same

cool

cell to

the

as

at

t+8t, tt-Stt,

equal

to

ve8nn, where

case

2,

and

monovalent

equal

heat

the

"

element

of solution

is the
whilst

q is the

where

8nq"

to

of

heat
of

gm.

vSneSn

not

the
and

is

temperature

the

at

consequently

8n(q

higher temperature

will

change sensibly with

cycle, the
the

cell is

by the

equal to8n{q"ve(ir+8ir)) if the heat

manner

does

During

out

absorbed

heat

similar

of reaction

external

quantity of

work

the temperature.

given

heat

is

performed

at the

out

equal
lower

8n(q" etro).
v8ne8iT

the

perature
tem-

volts,

metal, in this

of zinc

atom

gm.

cell is

the

equivalent of

gm.

of

The

to

and

the

are

of copper.

atom

be

of zinc

cell at t is

of the

valency of the

solution

through

subsequently allowing

work

chemical

the

raise

then

we

of zinc

gms.

the

is the

until 8n

current

ions

gm.

copper,

electrical

the

at

pass

being joined by

copper

deposited,

copper

redeposit the 8n

to

and

work

at

t+8t and

to

zinc

ow

__8n(q"e7Tv)

"

or

7T

.877

-L

"

8t

ve

8it

In

the

cases

many

temperature

coefficient

is

so

small

8t

that

the

term

lations of

t"
ot

may

be

neglected for approximate calcu-

n.

OVERPOTENTIAI,
With
the

passage

AND

potential difference
of

the

smaller

is

current

PASSIVITY.
than

only associated

changes in the electrolyte,provided

*

/ is measured

in degrees

on

that

the

absolute

calculated,

with
of

tration
concen-

course

temperature

scale.

that

INTRODUCTION
ions

other
are

not

capable

example, in the
between
platinum

electrolyte. For

the

sulphuric acid
following ionic discharges take

electrolysis of

dilute

electrodes, the

potential

lower

at the

being discharged

of

in

present

with

place

increasing applied potentialdifference.

P.D.

Ionic

in volts.

discharge.

{nrvn-i

ro8

o"-"o. "2

aOH'-"HfO+0,

167 '

Ih-"h2
S04"-"H2S04+02

"95

H-"HS

IH-"H2
130"-"03

2-83

practice

In

than

has

electro-depositionat

thus

the

Frequently
be

the

traced

general
of the

theory

is used

with

the

at

the

of

causes

of the

amount

to

expense

found

sary
neces-

mena
phenoApart

loss due

the

to

sistance
re-

discrepancy between

accounted

for

by

of the

one

"

In

"

identical

and

the

at

electrodes.

of the

Joule heat

be

order

of irreversible

surface

polarizin
de-

subsequent sections.

in

occurrence

of the

of

uses

electrolysis,and

consumption

those

been

nature

has
for

of the

always
each

to

the

increased

particular metal.

the

P.D.

electrolyte

same

take

cathode.
be

that

noted

reactions

anodic

cathode

where

processes

hydrogen liberation, when

applied E.M.F.
definite

for

necessary

is liberated, it has

independent

The

Overpotential.
for

rate.

electrolytes in

the

dealt

circuit, those

following factors

necessary

to

one

to

potential difference

practice may

and

hydrogen

be

excess

taking place
the

to

bring about

applied

economic

electrical energy

the

depolarizer,will

can

be

to

applied voltages

lower

of the

from

an

added

agents
reduce

considerably higher

potential difference

calculated

that

H2S20,

and

HSO/-"HS04

2*60

place,
The

by

is not

theoretical
a

certain

According

to

ELECTROMETALLURGY

INDUSTRIAL

Caspari,

following

the

forthcoming,

correlate

although

t\ values

the

of absorbed

gas

and

ions

the

gas

and

the

with

diffusivities

the

metal.

in the

electrolyticreduction
of zinc

and

Passivity.
anodic

evolution

in

the

case

anodic

is the

electrolytes metals
solution

; the

to

metal

this

cause

probably all metals

following exhibit

iron, aluminium,

molybdenum.
summarized
for

1916
I

of

cathodic

The

in certain

tion
deposi-

hydrogen,

exhibit

may

be

tendency

to

anodic

is

actually

"

noble

than

amongst
formation

others, and

the characteristics

of

the
of

more
a

suitable

gas

to

marked

been

more

although
treatment,

degree

Faraday

of the

important
on

may

the

have

to

been

Society

be mentioned

surface.

and

proposed

passivity,which

film

are

platinum, tungsten,
have

"Transactions

of

disturbance

no

than

theories

quite

certain

passifiedby

phenomenon

of

In

more

phenomenon
may

ible
irrevers-

passivity.

"

appears

with

the

of

cobalt, chromium,

in the
;

of the

technical

serious

more

occurrence

Various

for the

account

in the

Electrolytes containing oxidizing acids

case.

prone

is taken

usually, however,

magnitude

processes

molecules

metals

and

thetical
hypo-

of gas

is also associated

of oxygen

overpotential phenomena,
inconsiderable

of

to

cadmium.
As

"

processes

as

formation

Advantage
by certain

is

the

tensions, with

high overpotentialsexhibited

the

over-

made

of formation

heat

surface

been

have

attempts

with

hydrides, with

the

the

satisfactory explanation for this phenomenon

No

yet

of

values

the

are

"

INTRODUCTION
of

formation

The

2.

retarded

speed.

Velocity.

Reaction

place is

by

set

link.

intermediary

This

use

we

of

imagine

copper

one

ion will be
of the
the

factors

in

by

followingexamples

the

electrode

becomes

; at the

instant

next

the

cupric ion will be discharged

be

can

represented

electrodes,
the anode

The

can

we

S04"

the

solution

is reversed, and

current

of the

total

sum

follows

as

lysis
perform the electro-

to

current

electrical

of

cause

discharged, forming cupric sulphate with

metal

reactions

the

copper

one

slowest

is nevertheless

but

process,

sulphate with

when

that

tfo

made

looked
over-

alternating

an

be

generalization is frequently

be indicated

may

which

at

velocity of the

maximum

the

important

inefficiency,as

speed

cycle of operations may

in electro-chemical
most

maximum

The

"

change involving

If

allotropic

an

the

its normal

below

the

into

metal

electrolyticsolution pressure is low.

velocity of ionization or hydration of the ion is

4. The

of

film.
,

modification, of which

take

oxide

an

of the surface

conversion

3. The

any

two

Cu^Cu"'
It

is evident

should

that

place if the

take

the

electrode

in

the

solution

instantaneously,
found

by experiment that

periodicity of
for

frequent

less

place.

If

solution
From

occurred

metallic
anode

to

various

the

cathode

in

instantaneous,

and

to

to

that

uniergo

velocity of electrolysis.

an

do

Leblanc
of

current

to

in solution, but

were

did

periods, but

modifications

has

of

occurs

actually take

present in the electrolyte,

were

500

copper

hydration

solution

figures it is clear

the

ions

the

alternations

up

whilst

removed

sufficiently quick

were

potassium cyanide

these
of

unless

fro from

and

to

are

alternations

the

loss, whilst

such

they

electrode

the

weight will result.

above

and

50

prevent

means

loss in

net

if

hydration,

by

of

weight

simply oscillate

ions

solution, but

the

to

in

change

no

the

ceased

rates

into
before

other, which

each

it passes

set

10,000.

of transformation

electrolytic cell,
actually

at

from
are

limit

by
to

the
no

the

INDUSTRIAL

io

ELECTROMETALLURGY

Electrolysis

Fused

in

Electrolytes

Electro-

and

thermics.

The
fused

isolation of the

hydroxides, and

adopted
H.

the

at

day,

first

pupils,who

laws

at

these

to

fused

showed

the

current

the

more
1.

loss

occur

may

This

Chemical

intermediary
solutions

the
causes

formation

of

reduction

mist.

form

To

obviate

of the

in

It is

entirely of the
colloidal

quantity of the
or

alkali
minimize

of

as

the

siderable
con-

very

posited
de-

since

the

liquid

exerts

an

fused

In

"

of

electrolytes

unstable

in

the

aqueous

notable

occurrence.

chloride,

subchloride,

coloured

yield of metal.

will

certain

of

electrolysis

electrolytes containing

fused

the

coalesce,

frequently not

electrolyte in

yet uncertain

the

form

of

the

cloud

whether

cathodically deposited in the

metal

solution

electrolyteshould

4. Solution

"

always larger for metals

During

precipitated metal

consists
of

"

metal,

the

of the

in the
"

or

the

sub-salts

formation

are

during the electrolysisof calcium

dissipated through

fine cloud

of

frequent

metals, especially lead,

is

following

increasingly important

which

is

pressure

formation.

alkalis, the

The

vaporization of the

to

through

reactions.

cathode

3. Cloud

but

disturbing influences,

becomes

side

is found

solutions, but

aqueous

efficiencies

point

is of somewhat

example
where

due

melting

appreciable vapour
low melting point.

and

by Lorenz

deposited metal.

factor

interval

temperature

CaCl,

of low

causes

of the

higher the

2.

to

various

to

Evaporation
metal.

the

made

efficiencyis usually lower.

important

Sir

general the conductivity of

In

superior

time, owing

same

the

is much

accomplished by

of Faraday's
general applicability

the

electrolytes.

solutions

of manufacture

systematic investigation of the

properties of the fused salts has been

his

the

by electrolysisof
method

was

1810).

to

metals

technical

the

present

(1800

Davy

alkali

or

metal, alloyed
cloud

it contains

whether

formation,

Metal

in

as

the

the

low

small

with

combined

or

be maintained

it.

temperature
as

possible.

Electrolyte.As
"

in

INTRODUCTION
the

of

case

been

owing

with

construction

the

values

to

of

of

of known

in aqueous

composition

The
indicated

by its

produced

by

The

furnace
of carbon

of

heat

liberated

becomes
to

number

of

has

been

appreciable and

has

of

with

the

colloids

few

received

have
in

which

last

the

During

and

fail to

be

industry of the future.

but

lies somewhat
be

it may

time

there

which

are

have

industry

remarked
three

already

the

estimated

been
the

distinct

proved

preparation
curable
unprothe

hand

increased

has

operation.

electrical

the

the

and

properties of
gators
by investi-

electro-chemistry,

in the

discussion

in

at

Cataphoresis.

physical

outside

electric

electro-chemical

of the

results

already

province of this volume,*

passing that

at

lines of research

extremely

the

present

in this

helpful

in

field
the

"

The

1.

smelting

reflected
A

an

second

of sublimation

ever-increasing attention

subject of

the

cannot

obtained

years

or

in

rate

means

of the

whilst
great difficulty,

no

of
simplification

Diaphragms

first

the

is

as

effects

passage

products hitherto

high-temperature

efficiencyof high-temperature
in hand

this

By

matter

the

limit obtainable
the

36000 C.

of

chemical

the

by

which

at

has,

processes
to

either

temperature

temperature

30000 C.

confined

resistances

upper

is that

been

Joule

the

through

class.

from

name,

amalgams

from

electrolytes.

electro-thermal

of

development

current

usually approximated

figures obtained

the

and

electrolytes. The

fused

the

by interpolation from

connection

in

auxiliary cathode,

electrolyticpotentialsare

of the

was

accuracy

difficulties

suitable

diffusion

of

rapidity

high degree of

no

experimental

obtained

the

but

attempted,

solutions

fused

in

metals

the

of the

determination

electrolytes,the

aqueous

electrolytic potentials of
has

preparation of

colloidal

metals

sols in various

as

these
For
information
further
to :
on
subjects, the reader is referred
Die Methoden
V. Weizur
Svedberg,
Hersteliung Kolloider
Losungen."
der Dispersoid Chemie."
Freundlich
Grundzuge
marn,
Kapillarchemie."
Membrane
Donnan,
equilibria,Zeit.f. Elektrochemie, 17, 572, 191 1.
"

"

"

ELECTROMETALLURGY

INDUSTRIAL

12

dispersion media

by the

(b)dispersion by

and

The

2.

electric

an

protective colloids

of

use

of

means

dispersion,

(a)cathodic

methods,

two

arc.

in the

position
electrolyticde-

of metals.
3. The

calculation
also the

and
the

of the

pores

of the

of ionic

velocities

materials

it is desirable

where

drop of potential

to

in

used

migration through

electrolytic operations,
cathode

and

anode

the

separate

phragms,
dia-

across

compartments.
Power.

deciding factors

The
for the

preparation of

values

of

market

from

materials,

raw

costs

place

localitycannot
method,

such

marking

off the

raw

material

and

calculating the position of

has

shown

that

the

factor

energy

big industrial

that

by

and, indeed,

at

enterprisesspring

all

at

centre

D,

experience

important,
the

round

up

point A,

Practical

is

given

strictlyscientific

source

site.

relative

factory in

power

the

scale

transportation

country,

map

method

the

C, the distribution

and

at B

sources

and

and

ideal site for

on

suitable

manufacturing

to

country

be indicated
as

on

labour

energy,

The

place.

to

of

complicated,

from

vary

choice

product

any

generally exceedingly

are

to

in the

and

power

sources.

Industrial

form,
dominant
The

two

solar

electro-chemistry requires its

and

the

for

factors

chief

organic fermentation
extensive
that

owing

the

to

electricitycompared
in

scale.

power.

kilowatt

year

to

obtaining
produced

Many
are

both
and

It has

relative

coal,
can

been

coal, although

compete

various

turf, and
on

from

and
a

to

the

an

creasing
in-

frequently claimed
of

water

with

produced
industries

electro-chemical

no

the

industries.

these
and

are

countries

figuresgiven for the actual

supply

delivered

form

being utilized

cheapness

fallacious,owing
in

and

are

processes,

of

water

are

gasified peat

coal-producing country

in water

formation

the

energy,

in this

energy

of power

sources

radiant

of

values

in electrical

power

cost

rich
of

different conditions

consumption

of

the

generating station.

energy

14

INDUSTRIAL

ELECTROMETALLURGY

flatten

their

curve,

in their

production
desire

turn

discontinuous

furnace

work.

At

various

up

consumers

power

afford

cannot

is liable to

which

but

the

be

stations

using electrical

areas

its

difficulty. Economy

supplying
rate, and

the

heating load
small

must

for the

labour

production

transmission

of the

first

1891.
in

were

In

at

lines

The

increased

quantities of power

distances

at

however,

limits

distance

minimum
both

which

over

the

raisingthe voltage,not
loss)loss by heating on

power

volts) increases

100,000

the

and

pressure
the

radius

conductor,

loss

corona

earlier

substituting steel
lines,and

the

line

the

Again,

commence.

of dust

or

does

with

we

the

the
The

or

voltage
longer

There
and

are,

the

to

On

Joule (Watt
loss

corona

critical

fog

electric

in the
The
brush

towers

for

(above

voltage

the

on

high voltage lines, the

ferro-concrete

to

110,000

for

same

conductors.
this

were

transmitted.

be

to

depends

commences

presence

of

the

rapidly.

volts

10,000

conductor.

line, but

the

aluminium

or

transmitted

be

has

only have

power

tendency

present

voltage employed

the

to

of

raising the

By

for the

cost

conditions

present time

the

can

60,000 volts transmission

constructed.

are

be but

problem

the

to

at

steady

must

these

transmit'at

50,000

1901

sidered,
con-

producers

consumers

Under

important.

operation, and

volt

150,000

which

load.

to

being

by

industries

consumption

attempts

ing
of link-

great that the lightingand

so

in the

total

becomes

The
in

lines

and

effected
to

any

considerable

of

one

high voltage transmission, using copper

lines.*
made

be

amount

proportion

leans to

of power

large amount

be

only

can

at

for electric

is

power

is

practicaloperation

buy

clashing of peak

avoid

to

to

off

cut

problem

the

moment

present

power

in the

currents

as

but

cheap power

current,

the

by the producers, except in special cases

moment

of

whilst

at

ture
tempera-

air, as

well

smaller

the

discharge
expense
wood

of

pole

fittingof high voltage insulators, raises the

cost

of line construction.
*
is only one
Although the specificconductivity of aluminium
of copper,
conductor.
is a better
yet per unit of weight, aluminium
sodium
has
also been
protected by glass tubes
suggested as
conductor.

half

that

Metallic
a

possible

INTRODUCTION

factors, which

These
areas

where

when

the

station

is

distance

generating

plant.

economical

the

where

is further
own

is

population

the
lines

of

distance

miles,

instal one's

to

transmission

of

cost

of 250

considerably

transmission

would

still shorter.
The

Interim

Great

600

some

Report

points

about

generating
thirtieth

machine

of the
"

"

one-fourth
of

economical

size of what

power-station

stations

present

divided

into the

have

the

stations

capacity of

be

single

one

about

considered

Thirteen

of

average

power

size, and

may

unit."

as

one-

an

nomical
eco-

"

of such

power
super-

contemplated.

are

The

the

in

necessity for the

centres

Britain

undertakings in Great

Supply

Power

the

out

large power

of very

h.p., or

5000

Electric

the

on

Britain, April 1917,

development
of

economical

limiting

station

If the

or

generating
the

neighbourhood

England,

plant

power

America

miles.

more

In

the

enhanced,
be

becomes

and

denser

150

be considered

distant

some

western

in the

about

east

it then

away

In

be

to

appears

from

power

considered.

in the

and

be taken, must

to

question of installing a separate

of

in industrial

speciallyimportant

are

precautions have

transmission

the

15

of

methods

following groups

1.

Hydro-electric.

2.

Coal.

production

power

be

can

"

3. Gas.
4. Oil.

Power.

Hydro-electric
in Great

scarce

Kinlochleven,

production
both

in

there

are

of

Wales

Britain, the
about

where

aluminium

notably in Ireland

very
on

South

Egypt,

India,

Guiana.

The

cost

considerably

from

is

kw.

20,000

Within

the

large undeveloped
the

Erne

and
New

installation

country

exceedingly

being at
developed for the

potential sites

Africa,

of

is

power

only large installation

Scotland.

and

several

Water

"

to

sources,

power

Zealand

running

country.

found

Commonwealth

Shannon,

and

be

may

The

in

Canada,

and

British

vary

very

following

16

INDUSTRIAL

figures may
costs

ELECTROMETALLURGY

be

taken

the

as

approximate

running

pre-war

"

Place.

Total

cost

3^.
yd.
68s. $i.
81s.

California, U.S.A.
Saulte-Ste.
Marie, U.S.A.

54s. 6d.
67s. id. to

Niagara, U.S.A. side

I^egnano, Italy
Turin, Italy
Brian9on, France
Scandinavian

the

last few

low

figures are

in Norway
per

kw.

full

running

are

included,

year.

remarkably
cost

selling costs

actual

during

power

large

Odda

at

The

Very

one.

Svaelgfos

and

e.g. from

to

ns.

of this power,

be

of the

lie between

sellingcosts

that

opinion

when

Swedish
natural

the

and

25s.

12s.

royalties

depreciation,and Government
higher. The
Norwegian and
to

seem

economic

been

in Sweden,

are

Governments

of water

Trolhatten

costs,

4d.
2\d.

545.
18s.

quoted for the

and

8d.

112s.

20s.

development
has

years

consumer.

41s.

Zealand

New

N.

The

to

year

45s. 8d.

Ontario, Canada
Hora-Hora,

kw.

per

Kinlochleven

40s.

per

kw.

year.*
figures cited

the

Although

above

subject

are

variations, the approximate figure of 40s. per kw.

be taken
for

as

fair average

hydro-electric power,

sellingprice, on
where

the

may

year

basis,

pre-war

installation

wide

to

costs

are

not

high.
As
costs

the

installation
expected, the pre-war
for hydro-electric power
widely, depending on
vary
is

naturally

size of
with

as

to

the

"20

is said
costs

kw.

"26

cost, whilst

in
at

large choice

Norwegian

U.S.A.

In the

installed

plants were
that

per

engineering difficulties

the

standard

installation

over

fact

and

in Scotland

the

rising to

be

the erection.

installation

earlier

plant

the

conservative

Norway

to

to

have

the
a

later
much

kw.

"15

per

installations.

In

kw.,
The

cheaper rate, owing

of available

Royal Commission,

per

"27

about

be taken

Kinlochleven

the

cost

average

to

seem

ciated
asso-

Sept.

sites

191 5.

was

missible.
per-

INTRODUCTION
The

17

feasibilityof using tidal energy

from

time

from

the

This

time.

to

disadvantage

large reservoirs

would

periods of slack

water.

Coal

Power.

from
taken

as

"

potentialsource

that

to

ensure

have

to

be

of

pound

11,500

to

13,000

B.T.U.s

been

has

of energy

erected

the

is

efficient steam-driven

most

turbo

the

undoubtedly

of

advantages

since

and

be

can

For

costs.
to

sizes

minimum

about

capacity,
compatible

Smaller

plants
B.T.U.s

20,000

some

efficiencyof
be

large units

installed, figureswhich

kw.

cited

those

with

In

for

tons, and

such

on

the

lower
the

valuable

price for

average

in 1915,

12s.

"

Quarries."
I,.

10s.

Mineral

for the

"11 and

"13

per

1916, 256,348,381 tons

material

that

about

slight export

would

considerably

It is stated

consumer.

one-

that

sellingprice of coal in 1914 was

9s. irygd., and
It would,,therefore,
5'6orf.per ton.
appear

possibleto deliver
contemplated by
7s. 6d. to

sume
con-

therefore

costs

Britain, of which

raw

home

the

in

It is evident

quarter left the country.

tax

kw.

per

extremely favourably
tions.
installahydro-electric power

in Great

mined

were

ency,
effici-

dynamic
thermo-

set would

lie between

the

compare

the

1915, 253,179,000

of coal

The

capital installation
to

be

to

operation

hour.

generating

estimated

are

kw.

20,000

working

in

stallatio
in-

cheap

required

present

ditional
ad-

changes,

very

economic

per

such

The

cent.

per

227

at

offers the

at

be

able

present existent

considered

would

is

lb. of coal.

per

generators, units of

with

B.T.U.s

be

maintenance

are

be

hour

should

at

units

large

large turbo

15,000

produced.

low

having

which

kw.

50,000

generator

in

the

may

kw.

generator, which

constructed

with

average

equivalent to 3415 B.T.U.s, an ideal engine

of electrical energy
to produce 4 kw. hours
The

deal

to

good quality coal will produce

pound

per

suffers

continuity of supply

B.T.U., and

14,000

discussed

coal

in bulk

the

reconstruction

Production

the

Taking ys. 6d.

per ton.

Pt. iii.,
c.

at

of

the

United

large

stations

power

committee
as

Kingdom

the
in

at

minimum

1915

from
we

Mines

8444.
2

and

18

INDUSTRIAL

obtain

the

ELECTROMETALLURGY

following minimum

of

cost

production

year

"

Coal
..

..

Running
cent,

..

and

costs
on

..

..

depreciation=10

Installation

33s. zod.

..

per

cost
.

21s.

Total
.

To

produce

kw.

for 40s.,

year

the

54s. xod.

price for hydro-electric power

than

the

raising steam

freight rates

delivered
the

It is

expected.

at

post-war

considerably higher

still greater increase

of

in the

cost

extremely probable,

altogether disproportionate rise in the

the
will be

sufficient

of those

side

the

be

must

that

however,

to

rate, yet

pre-war

be

may

value

pre-war

coal would
to
have
be
hydro-electric power,
the power
plant for 4s. 3d. per ton.
Although

of

kw.

per

swing the pendulum

to

installations

power

which

over

situate

are

close to their markets.

Gas

Power,

"

boiler

gas

firingis

steam

is raised

where

coal is employed,
fuel

the

fixed
coal

of

air

for

air
with

the

value

as

in

scarcely

can

their

for

sounder

to

fuel value

other

obtain

hand

countries

The

with

large quantities

for their various

relative

to^the

power

increased

an

is

these

recover

production

pow^r

coal

raising steam,

lost

were

naturally necessitate
electrical

of

of

was

be

value

market

distillation

the

fuel suitable

economically

whilst

than

one

case

definite

in the

supply ; thus, liberation of unburnt

the depositionof partly carbonized
tar

heating system,

obtained

in the

requiring

combustion,

this consideration, the

from

fact that

to the

better

and
of

case

proceeds in stages, necessitatinga

firing,combustion

smoke,

as

owing

plant where

cent,

5 per

some

perfectlyhomogeneous,

quantity

variable

of

is

by

efficiency of

The

coal

fuel

of the

parts

on

avoided.

Apart

by-products

greatly above
and

it would

This

consumption

concerned,

but

supplies of coal available

products useful

as

their
appear

by-products
plant.

as

if

even

would
as
on

far
the

would

materials

raw

industries.

advantages

gasificationof the coal

at low

and
or

disadvantages

of

high temperatures,

partial
under

INTRODUCTION

slight pressure
book.

It is

or

of

market

coke,

power

to

of

70

produce

B.T.U.s.,
cubic

for

have

better

required

boiler to

that

give

kw.

coal

B.T.U.s

kw.

Against this
in

than

tons

ton,

cost

of coal
kw.

Present

Rectified

tar
.

Ammonium

sulphate

Benzol

coke

and

2S.

breeze

Net

value

represents

educting working costs

of any
specialmachinery

may
*

3s.

with

44s. 8d.
32s.

od.

21s.

od.

97s. 8d.

by-products

set.

obtained

be mentioned

"

value.

yd.
41s.
8s. zod.
is.

Total

net

5s.

Sulphocyanide
Sulphuric acid
Pan

which

be

would

year

turbo-generator

coal-fired

gasificationof coal, amongst

would

"

depreciation

cent,

5 per

be set the value of

must

million

required

B.T.U.s

5*96

year,

Total
dearer

assume

30

are

; with

hour

7s. 6d. per

at

gasification
Running costs and

42s. xod.

will

B.T.U.s.

For

or

fied
gasi-

operation

one

we

coal
.

the

generating plant.

15,000

gas-fired turbo-generator would

For

which

firing, 14,250

gas

for

in

coal, containing

million

21

noted

With

metallurgical

gasification will give nearly 60,000

containing

Hence

conditions

only consider

clinker

main

the

of

ton

efficiency for

required.
be

One

further

coal-fired

suit the

producer is in the neighbourhood

gas

complete

on

and

of steam,

from

waste

cent.

feet of gas

We

introduction
as

amounts

the conditions

on

will

We

gas.

by-products

gas,

efficiencyof
per

to

as

so

and

nature

the coal is practicallycompletely

where

case

be obtained
The

be controlled

illuminating

by the suitable
can

the

for fertilizers,
benzol, chemicals,
or

hypothetical

that

province of this

the

by-products being dependent

gasification,can

of the

lie outside

vacuum,

evident, however,

of the various

19

(Ifsold
20s.

as

crude

tar

g$d.)

nji.
3jd.
4%d.

10S.

63s. io\d.

rates, after
possible profit on sale at current
for depreciation
and making allowance

for recovery
utilized.

Under
of
or

kw.

65. 2d.

below

fall and

with

conditions

97s. 8d. by

the

tend

which

If

costs.

large,

the

price of by-products on
costs of the
disparitybetween

to

as

iod.,

gasificationof coal in
turbo-generator stations contemplated,
for

the
the

price

the

63s. lod. =335.

water-power

average

erected

production would

doubt

would

system

alternate

disappear,but

to

be

would

market

the

there

methods
be

can

advantageous

most

no

to

nation.

the

Gas

Engines.

B.T.U.s
B.T.U.s

in

produce
from

The

plant.

steam

words, the

other

use

of

be

to

duce
pro-

B.T.U.s

spite of the
prime

to

to

heat

subsidiary

of gas

exploded
B.T.U.s.

3,500
kw.

per

is

hour

advantages

apparent

limitations

the

mover,

large

of the
a

to

14,250

necessary

use

consumption

efficient

to

modern

run

equivalent

steam

In

more

would

of 13,500

energy

B.T.U.s.

10,000

good

be raised

can

net

In

addition, by the

heat

exhaust

be reduced

figure may

In

engine will raise

in the gas

in the

hour.

that

turbo-generator, 15,000

B.T.U.s

13,500

exhaust,

the

only

kw.

firing is adopted.

if gas

engine only

gas

coal-fired

required, which

are

already noticed

have

We

"

hour

kw.

In

the

were

connection
doubtless

fall from

would

year

idealistic

somewhat

these

installations

of

ELECTROMETALLURGY

INDUSTRIAL

20

size, 3000

kw.

units

being the

largest constructed,

together with

the

heavy

installation

expenses,

working

and

in

costs

counterbalance
The

any

Power-gas

fuel economy

which

for power

sources

in the

hydrolysis of

in various

in

efficient

prime movers
consumption per kw.

relatively small
present several

Diesel
in
hour

oil

technical

be obtained.
of gas

means

gas

turbine.

industries, such

retting of flax, and

low

advantages.

engines

grade oil

the

are

operation, the

being only

electro-chemical

engine operating on

than

more

in peat, turf, natural

fermentation
the

the

the

septictanks.

The

"

is to

generation by

be found

of acetone,

sewage

Engines.

to

are

production

machinery

long-sought machine, the

of that

oil, gas wells, and

Oil

on

natural solution

is the realization

as

depreciation

make

some

most

B.T.U.

8,500.

For

installations, a

Diesel

gas-works

would

or

tax

22

INDUSTRIAL

British

Commonwealth

ELECTROMETALLURGY

given below

Report of the Advisory Council

Industrial

and

Society of Engineers.!

the
at

present available

future

date

and

capable

ore

deposits could

means

the

world's

the

greater portion of the

Iron.

The

"

tons

in the

24

was

Great

Britain.

at

some

if stock

within

of

tons, of

this

area.

United

8 million

which

iron

few

some

in the

smelted

ore

million

with

ores,

located

to be

ores

found

are

"

Hematite,

"

supplies

the

being developed

Large depositsof

followingcountries

that

to

taken, it is probable that

be

quantity of iron

imported.

were

of

tific
of Scien-

by C. Cullis

paper

metalliferous

be found

in 1913

Kingdom

inconsiderable, and

by

no

and

last

the

Department

It will be noted

are

exceptions,would

to the

Research,*

from

drawn

are

ironstone

and

magnetite

in

counties.

many

Scotland.

in

Ironstone

"

Linlithgow, Midlothian,
Ireland.
in

County

and

and
in

bauxite

County

Down,

Stirling.

County Antrim.

Wicklow,

tite
Hema-

Cork, Clare, Longford

Leitrim.

Newfoundland.
Canada.
Yukon.

Renfrew

Ferriferous

"

Fife, Lanark,

Ayr, Dumbarton,

"

Hematite

Hematite

"

in

Magnetite in

on

Nova

Bell Island.

Scotia, Ontario

Brunswick,

New

Quebec

and

and

the

British

Columbia.
India.

Hematite

"

and

and

Central

the

ironstones

Provinces.

in

dency
Bengal Presi-

the

in the

Magnetite

Madras

Presidency.
South
and

Africa.

Bechuanaland.

round

Pretoria.

Siliceous

hematite

in

Griqualand
Siliceous magnetite in the
regions
Low-grade ore is stated to be plentifulin
"

W.

Rhodesia.
Australia.

Hematite

"

Wales, Victoria, and

Iron

in

Australia,

New

Australia

and

parts of Western

in Western

ore

South

Australia,

few

miles

25

million

South

land.
Queensnorth

of

Perth.
Tasmania.
stated
*

to

be

Published

"

Magnetite, estimated

at

tons, is

available.
May

191

7.

Trans.

Sec.

Eng.,

Dec.

1916, p. 25.

INTRODUCTION
New
the

Zealand.

The

"

23

magnetite deposits at

Plymouth

New

and

deposits of limestone

Parapara

reported

are

be

to

extensive.

Chromium.
British
were

chief exporters of chromite

The

"

Commonwealth,

according

Date.

Canada
.

India
Australia
also

Deposits

and

Cobalt.

the

have
cobalt.

to

The

In

output.

silver

cobalt

Commonwealth

of

sources

Balmoral

Manganese.

supply

1914

1915

that

year

1914

1910

to

of manganese

ores

Office

was

in

Egypt, New

statistics,

Zealand,

Coast.

Gold

world's

the

"

tons.

35

Queensland

Canada
.

Jaipur

"

S. Wales

at

Metric

"

tons,

in India

Country.

401

Home

also found

in 1915

of

10

the

"

molybdenite

these

Transvaal.

of the

According

depositsare

began, and

Metric

Cape Colony and the

The
Molybdenum.
following was

N.

foundland
New-

supplied 90 per
the development

mines

Newfoundland,

of

Transvaal,

the

be found

may

district

"

production

Extensive

Date.

in the

1915

63,384
11,486
5,888
638

in the
production
monopoly
producers of cobalt ore are

the

S. Wales

Other

nickel

Country.
Canada
N.

Caledonia

New

1904,

obtained

now

1913

tons.

Zealand.

world's

Ontario

Metric

Scotland,

in

occur

New

Up

"

of the

cent,

the

returns,

"

Rhodesia

and

recent

the

Country.

of

to the most

within

99
128

tion
produc-

INDUSTRIAL

24

ELECTROMETALLURGY
is also

Molybdenum

in

found

Scotland

England,

and

India.

Nickel.
confined

The

"

Ontario.

In

area

over

are

was

said

extensive

the

to

of

production
the

1915

nickel

Cobalt

ta exist,notably in Northern

also been

reported to

in this

mined

ore

in

deposits

Other

tons.

1,300,000

deposits of

Sudbury

and

of nickel

amount

practically

is

ore

Nickel

Alberta.

present in deposits in East

be

Canada
has

Griqua-

land, S. Africa.
Titanium.
are

found

S.

Adelaide,
to

the

Quebec,

near

Australia,

present time

Tungsten.

have

Deposits which
Before

war

the

consumption

is

now

for the

mined

was

was

but

as

Widnes,

Luton

near

but

within

ores

follows

worked

Subti

up

"

found

are

river

world's

in

at

Rhodesia.

tungsten

ore

yet

no

quantity of metallic

England.
and

the

Commonwealth,

small
in

at

was

the

very

Zealand,

of tungsten

of the

within

and

ore

developed.

the

manufactured

produced

Ferro-tungsten

Sheffield,in England,

English Steel Industry.

Vanadate)
Wiltshire

Hill,

on

one-half

over

in New

yet been

not

India, and

Vanadium.

worked

been

not

have

ferro-tungsten and
tungsten

as

production
during 1914-1915

Commonwealth

in

well

as

Wales

South

; New

The

"

Rajputana

Canada

iron

titaniferous

of rutile and

Deposits

"

"

have
and

on

Small
been

deposits of
observed

Shropshire, but
commercial

Rhodesia,

may

in

to

(Pb and

England

appear

scale.
prove

mottramite

It

be

to

be

Cheshire,

small

too

is stated
a

in

that

useful

Cu

to

be

Broken

source

of

INTRODUCTION

vanadinite, whilst

smaller

25

quantities

found

are

in Western

Australia.

Zirconium.
available

are

As

in the

sylenite,it

Australia

the

form

heavy

sea

In

"

and

but

Canada,

of S. India

sands

localities in

in several

occurs

zircon, large quantities

of

of these

none

Ceylon.

and

Scotland, Ireland,
have

sources

been

developed.

Copper.
just

over

In

"

Dominions

provided

is obtained

production
Wales,
metal
in

in

where

reached.

Extensive

Columbia

and

was

British

of

nearly
depositshave

output

an

and

the

British
South

New

of

tons

50,000

worked

been

in South

whilst

Ontario,

was

and

of the

cent,

per

Queensland

from

1913

Britain

Great

80

one-tenth.

consumption

copper

tons, of which

million

one

world's

the

1912,

Africa,

and
Rhodesia
offer fields
Cape Province, the Transvaal
for further
development. Chalcopyrite deposits are found
in Cornwall, Devon
and N. Wales, and cupriferouspyrites in
the

Co.

Ireland.

Wicklow,

British

and

Lead
before

Guinea

New

the

to be

are

Zinc.

"

ore

British

Isles,chieflyin Wales

and

exported for reduction.

before

ores

Wales, where

the

was

war

the

zinc

and

W.

chief

The

tons

500,000

of

tons

11,700

Broken

of ore,

tons, and

order.

same

of lead

on

the

lead

world's

1,000,000

of the

much

was

deposits in
largescale.
production just

that

developed

The

exceeded

war

is stated

It

In
ore

the

zinc

mined

England, and
Hill

in the
this

of lead

source

was

zinc

and

in New

area

tons

25,500

1912,

were

sumption
con-

South

consistingof galena blende

mixtures

of garnet quartz
containing pyrites with a gangue
and
rhodanite, were
annually exported. Other Australian
deposits are found in W. Australia, Queensland, Tasmania

and

New

The
the

Zealand.
chief lead

and

zinc

ore

producing

Koolenay district,British Columbia,

of lead

tons

ore

and

11,000

tons

of zinc

in Canada

area

where
ore

86,000

over

were

is

raised

in

I9I3It is claimed,

Broken
in

Hill

according to prospectors, that

Rhodesia
West
deposits in North

Australia, and

are

capable

of

extensive

the Rhodesian
exceed

those

development.

26

ELECTROMETALLURGY

INDUSTRIAL

Deposits

also

are

worked

were

at

The

Tin.

in

formed
a

world's

tin

which

the

of

tons,

Cornwall,

In

number

of

Tin
in

ores

in

found

Tasmania,

Australia.

There

is

within

deposits

of

is

deposit

from
be

must

alternative

deposits

capable
potassium
India,

laterite,

of

economic

on

possible
as

in

Co.

for,

neighbourhood

the

that

Ireland,

Antrim,

the

annual

the

it is unfortunate

only

to

which

Guinea

and

low

grade

metal

production

and

the

metal.

economically

be

can

our

where
of

tons

1,500

bauxite

from

these

Island

utilization
future

source

in

of

the

of

this

extensive

States,
rich

whilst
is found

sulphate,
Vancouver

Malay

the

development,

aluminium
and

rising,

sought

British

of

rapidly
the

in

is

bauxite

encouraged.

ores

India,

deposits

considered

Western

of

Since

aluminium

equivalent

sources

obtained

The

found
is

output

Other

is

and

tons,

100,000

annual

in

tons,

and

scarcity

Commonwealth.

the

consumption

world

In

5,000

Nigerian

the

marked

"

sole

great

expected.

Aluminium.

of

of

very

abundantly

less

Wales

development

still

and

South

50,000.

improvement.

and

Burma,

New

Africa

In

be

development

also

are

Australia,

is to

further

of

about

over

for
is

be

to

provide

production

silver.

for

stated

mined

mines

the

Chinese

the

is

been

has

where

States

Malay

annual

the

years,

capable

and

tin

where

by

consumption

"

130,000

date

early

very

Burma,

Upper

in

iron,

alunite,
in

New

South

appear

hydrated
Wales,

Canada.

felspars
metal.

must

also

be

27

INTRODUCTION

LITERATURE.

REFERENCE

"

"

"

of

Principles

"

"

*'

"

"

Macmillan.

Electrometallurgy."
of

Electrodeposition

G.

Metals."

B.

Electrochemistry."

'Practical

of

Textbook

S.
Le

Elektrochemie."
der

S.

Van

W.

of

the

American

The

Transactions

of

the

Faraday

Elektrochemie.

Partington.

Laar.

H.

Transactions

fiir

R.

Blanc.

The

Zeitschrift

Blount.

J.

Elektrochemie."
Chemie."

Theoretische

Langbein.

Thermodynamics."

Elektrochemie."

Grundniss

Albnand.

Electrochemistry."

applied

Jahn.

Nernst.

Electrochemical

Society.

Society.

Section

I."

AQUEOUS

IN

ELECTROLYSIS
SOLUTIONS

Copper.

The

electrolytic

largest

of

per

Of

recent

development
of

cent,

of copper

recovery
a

suitable

solvent

in

from

directly

and

and

where

of

electrodeposition

subsequent

with

leaching

by

ore

with.
lytic
electro-

the

on

over

is dealt

made

the

had

has

America,

been

has

and

oldest

the

production

copper

advance

some

years

far

by

processes,

especially

world's

the

is

copper

electrometallurgical

remarkable

85

of

refining

the

metal.

The

Early

Electrolytic
experiments

jew,

made

metal

indicated

in

anodes

electrolytic
free

this
in

the

acid
to

electrolyte
of

electrolyte,

as

and

the

sulphur

adhered

above

economical

could

be

used,

Borchers

Mansfield,
in
the

0*3

in which

metalloids

amp.

1908
the

converter,
into

of

for

impurities
anodes.

the

"

+Cii-"Cu+S"

anode

caused
whilst

pressures,

in

Bessemer

the

to

of

solution

uneven

Cu2S-"CuS'
which

unsuitable

were

use

ing
contain-

sulphate

accumulation

rapid

the

cast

for

conductivity

ferric

and

copper

easily

although

electrical

white

and

metallurgical

ordinary

the

sulphides,

sufficient

owing

liberation

these

cells, using

sulphuric

purpose

The

of

and

in

"

Nicola-

and

Marchese

(Cu2S,Fe2S3)

matte

obtained

that

of

its Ores,

from

Copper

those

as

metal

(Cu2S)

matte

process,

into

such

coarse

on

of

Recovery

per

100

only

then
anodes.

low

some

further

was

fusing
An

rise

to

densities

current

cms.

sq.

conducted
matte

voltage

the

the
acid

experiments
refined

Cu^S

now

copper

by

at

blowing
free

from

sulphate

INDUSTRIAL

30

This

ELECTROMETALLURGY
been

has

process

Mines, Arizona,

in

and

Cananea,

at

with

experimented

modified

the

at

form

Ray
Rio

at

Tinto, Spain.
With
80

over

extraction

cent,

per

is conducted
The

containing 3 per

ores

in

divided

of

problem

baths

has

not

ruled

out

on

sulphate
lead

from

of

of

low

their

oxide

Manganese
on

whole

the

the

horizontal

cells

the

deposition of

copper

enters

the

top.

each
The

reverse

situ

operations.

asbestos

is

usually

are

expensive.

compartments

generally used.

employed,

although

suggested.
flows

the

through

on

the

copper

the

sulphate-

cathode

chambers.

cathodes

chamber
flow

during the flow

at the

takes

(Fig.1).
ferrous
The
sulphate produced
Cu2S and Cu20 on ferric sulphate

partments
com-

Owing

specifically lighter, and

cathode

in

account

on

more

anode

through the anode

returns

electrolyte becomes

the

by

solution

sulphate

(formed

lead, but

arranged in series,and

are

in

occurring

magnetite (Fe304) electrodes

are

been

have

ones

graphatized

technical

dividing the

electrodes

and
to

for

is

electrolytes,are

sheets

most

satisfactorythan

more

Vertical

ferrous

fused

and

cathode, millboard

the

The

for

sulphate

Platinum

successfullyused, and

used

cathodes.
in

use

evolution

peroxide

copper,

Electrolysis

and

chloride

oxygen

been

are

diaphragm

As
from

cost

for

Carbon

cost.

Lead

sheet) have

obtained.

material

satisfactory in

solutions.

cent,

per

satisfactorilysolved.

account

rapidly destroyed by

19

using thin sheet copper

anode

yet been

carbon, although

to

be

can

cell

suitable

cent,

base

and

place in the

quently
conse-

leaves
anode

compartment

anode

according

the

to

Cathode

Anode

instead of the evolution

equations

from

the

serves

to

of

depolarize the

"

CuS04-"Cii +S04"

SO"4+2FeS(V"Fe2(S04)8
of oxygen

according

2SO"4 +2H20-"2H8S04
The

interaction

saving in the electrical energy

to the

equation

"

+02
required

to

bring about

ELECTROLYSIS

the

follows

with

of

is very

data

of

the

at

of the

great and

requiring 56,300

"

of copper

sulphate

at

electrode

and

from

be

can

The

ferrous

in

B.

the

sulphate

of copper.

deposition
electrolytes.

voltage

copper

is therefore

VOltS.

I"22

of

compartment

4-2
_

96,540
ferrous

with

from

for

Anode

decomposition
x

cells

sulphate

compartment.

56,300

With

calculated

atom

gramme

per

circulation,

cnpric

theoretical

and

pressure

the

t
-r-HjjSOj-r-Os

+2H20-"2Cu

of

Cathode

one

atmospheric

other,

calories

Arrangement

A.

calculated

voltage

1.

be

can

reaction

2CuS04

Fig.

solution

sulphate

copper

copper

under

oxygen

overvoltage

thermal

decomposition

deposition

liberation

from

31

"

minimum
the

SOLUTIONS

AQUEOUS

copper

depolarizer

anode

an

The

no

of

deposition

with
as

IN

anodic

as

depolarizer

we

have

the

equation
CuS04+2FeS04-*.Cu-f-Fej.(S04)3

requiring only 16,800

voltage

calories

hence

the

requisite

position
decom-

is

16,800
96,540
The

introduction

of

4'2
X

.0-36

volt.

diaphragm

into

the

cell,however,

INDUSTRIAL

32

necessitates

the

of

use

force.

electromotive
i'8 volts

and

ELECTROMETALLURGY

the

In

experimental

with

used

were

greater externally impressed

much

density of

current

between

runs,

02

o*8
amp.

per sq. dcm.

The

(b)
The

Process.

sulphuric acid as a leaching agent for copper

advanced
more
rapidly than the ferric sulphate
of

use

has

ores

Sulphuric Acid

and

process,

be said to have

may

experimental

the

outgrown

stage.
As
leached
be

ferric

in the
without

sulphate

oxidized

but

sulphide

treatment,

any

ores

be

can

first must

ores

roasted.
At

of

of copper

per

erection

day

about
pass

cent,

mastic

per

cent,

with

from

large plant

pounds

of

tons

10,000

is in

ore

taining
con-

(an oxy-sulphate of copper) averaging

It

copper.

is

to

leach

sulphuric acid
asphalt. It

in

concrete

was

found

efficientlyfiltered through

proposed

it with

0-25" mesh,

capacity of 335,000

extracted

brochantite

in Chile,

mine

Chuquecamata

the

course

the

to

method

cocoanut

crush

the

approximately

leaching
that

to

the

lined

vats

solution

matting

12

set

ore

per
with

would
between

be

ELECTROLYSIS

IN

will be

It

absent, both

noted

being

SOLUTIONS

AQUEOUS
arsenic

both

that

deleterious

very

and

for

33

antimony

are

deposition

copper

(seep. 40).
The

main

is the

objectionableimpurity

chloride, since

only is part of the chlorine evolved at the anode during

but part is included
in the deposited copper
electrolysis,
as
chloride ; it was
therefore
the
proposed to remove
cuprous
not

chlorides

previous

electrolysis. This

to

agitatingthe solution with shot copper

Cuprous chloride is formed according to

effected

was

in

by

revolving drums.

the

equation

2CuCl2 +2Cu-"2Cu2Cl2
which

reduced

and
is

be filtered off,dried, fused

can

proposed

wide

and

sheet
The

metallic

to
to

inches

thick, with

leaching

vats.

close

91

on

and

copper,

The

density of 0*5

Montana

Butte

by leaching with
to

to

steam

with

6o" C.

4 feet

and

deep.

contained

this stage to the

was

found

to

"

be

per

to

cent,

amp.

per

of copper,

per cent,

91 per cent,
sq. dcm., with an
over

obtained

carbonate

sulphuric acid

cent,

electrolysisthe

to

At

efficiencyof

ore

by this

is treated

after

crushing

electrolyteis heated

by

neighbouring plant electrolysis

proceeds

agitated electrolyteusing 1*4 amps,

per sq. dcm.
of effective leaching with sulphuric
Ricketts 4 cites a case
an

acid

on

an

oxidized

being crushed
coke-lead
kw.

10

Previous

J".

at

extraction

an

electrolytecontaining3 per
leaching process.
At

It

cent.

per

current

returned

average

coke.

long, 5 inches
vat, and the ordinary

experimental plant

was

I^aszczynski3 obtained
with

chloride,

4 feet

five to

spent electrolytein the

cent,

anodes

anodes, 3 feet wide

electrolyticcopper

i*5 per

calcium

by smelting with

copper

magnetite

use

with

hour

carbonate

\"

to

anodes

(63#5 gms.

at

ore

subsequent
gave

per o#o8 kw.

Ajo, Arizona,

electrolysisusing

yield of

posite
com-

lb. of copper

Sulphate Process, using Sulphur

Depolarizer.
I*.

ore

per

hr.).

(c) The

Occasionally sulphur dioxide

the

is

Dioxide

as

injected into the anode

3

INDUSTRIAL

34
chamber

of

dioxide

may

ELECTROMETALLURGY

divided

cell to act

be made

tubes

effective

most

are

the

agitate the liquid round

to

in

suggested by Carmichael,

as

or
depolarizer,

as

for

simple cell.

conducting

the

powerful

oxygen

sulphur
anode,

the

rubber

Hard

into

S02

the

electrolyte.

Sulphur

dioxide

ferrous

than

for copper
with

more

sulphate ;

critical

the

sulphate solution
is

S02

is

given from

in

cejl anodically depolarized

evolution

the

of

data

calories,

7,300

"

+2H2S04

CuS04 +S02 +2H20-"Cu

with

voltage

decomposition

thermochemical

the

depolarizer

theoretical

the

or

voltage is
x

"7300

96,540

sulphate

copper

This

energy.
Neill

words, S02 should

other

In

4*2
~"

"

and

Van

for

others

be able to
without

is actually the

case,

from

precipitatecopper

the
and

electrical

aid of any
forms

basis

the

of the

developed by Weidlein
solutions.
depositing from

and

processes

leaching and

cycle of operations claimed

the

0-15

"

solution

Arsdale

14.
volt.

"

followingequation

for these

is

processes

The

given in

"

CuO+S02=CuS03
Cupric sulphiteis

soluble
of

driving

off the

is not

deposited, but
The

formed.

with

pressure
to

the

excess

in

of

excess

sulphurous

heating

on

sulphuric acid precipitates copper

equation

on

sulphurous acid the cupric sulphite

red precipitate,Cu2S03.CuS03,
is
cupric sulphite

cuprous

acid ;

under

according

"

Cu2S03.CuS08+2H2S04=Cu+2CuS04+2S02+2H20
The

copper

In

by the

addition

of

precipitationof
practice anodic

usually only about

o*2

similarly be converted

cupric sulphate can

to

i*5 volts have

At

the

60

International

the

double

dioxide

cent.6

and

and

the

mediary
inter-

sulphite.

depolarization

per

been

sulphur

into metallic

is

not

complete,

applied voltages

from

used.

Copper Company's

plant in Canada,

ELECTROLYSIS
lead

witlra

used

sulphuric acid

cent,

is

"5 to

in the

07

pass

Chloride

The

originalchloride
in Silesia.
chloride

chloride

heated

chloride

would

iron

ions

the

2*5 per

applied voltage
with

The

finelycrushed

current

be

removed

by lime.
small

C.

700

Owing

of

amount

becomes

complex

I"ead

metalloids

the

chlorine

excess

solution

going into

copper

calcium

drums.

of

presence

ner

with

or

in wooden

the

to

sodium

cooling, and

on

by Hoepf

is leached

ore

containing

about

to

detailed

is that

process

solution

chloride

cuprous

The

Processes.

cupric

and

and

cent,

dcm.

sq.

cathodes

copper

of 2*5 per

per

35

cent.

(d)
at work

sheet

electrolyte.

ampere

efficiencyof 90 per

from

content

copper

SOLUTIONS

AQUEOUS
inches

separated i|

anodes

are

IN

as

Cu+2Cl'^CuCl'2
permitting of

thus

solutions
consists
or

tized

the

of copper
of

in the

series

mica

be

can

solutions, although
refractory, and

used

cuprous

chloride

depolarizerfor

of

In

the

followingreactions

Anode

the

Cu2Cl2

asbestos

Carbon

these

use

employed.

Cathode

the

found

the

electrolyzer

ment
parchgraphi-

or

material

anode

as

Hoepfner

are

the

compartments

cells with

diaphragms.

suggested

cathodes

copper

The

state.

cuprous

divided

of

perforated

carbon

preparation of relativelyconcentrated

in

chloride

sufficiently

not

ferrosilicon.

Sheet

cathode

anode

take

and

place

"

t
Cu+CuCl2

-"

Cu2Cl2+2Cl/-"2CuCl?

in the

electrolyte acting

liberated

chlorine.

The

as

an

catholyte and

anolyte consisting chiefly of cupric chloride, after

through the cells,are mixed
The
the

theoretical

thermochemical

and

as

follows

to the

data

"

+35,ooo

calories,

"

35,000

4*2
=

"**,,.

96"54o

",

'53 volts,
M

passing

leachingpiant.

decomposition voltage obtained

2Cu+Cl2=Cu2Cl2
is

returned

anodic

from

INDUSTRIAL

36
the

in this

copper

required

energy

ELECTROMETALLURGY

being monovalent.

case

deposit

to

metal), viz. 96,540 x 1*53

If

cupric chloride
voltage would
Cu

,6^500X4-a
96"54"

in this

the copper

gramme

being 96,540x2x1*35

watt

to

There

is,therefore,

chloride

than

molecule
sees.

distinct

electrical energy

be

expected by

=0*075

of the

in

using cuprous
electrolyte,although
salt is
not

divalent

the

ion, viz. double

metallic

metal)

hour.

kw.

advantage

change from

of

(63-5 gms.

of

instead

state

kw.

The

cupric chloride as
the decomposition voltage of the cuprous
of the cupric,the energy
that
gain is

since

to

yolts

being divalent.

case

deposit a

required

calories

volts,

1-35

position
decom-

"

CuCl2 + 62,500

hour.

electrolyte the

as

of

(63*5 gms.

kw.

=0*043

sees.

used

were

Cl2

watt

be

molecule

gramme

electrical

The

quite
the

to

the

higher
that

valent
mono-

output per

hour.
The

further

calculated

of anodic

advantage

from

heat

the

of reaction

"

calories

Cu+CuCl2==Cu2Cl2+i9,400
The

theoretical

be

depolarizationcan

voltage is therefore
19,400

4'2
=

Q.8ol

96,540
or

the

minimum

molecule
or

to

(635
kw.

0*022

required

energy
gms.

of the

The

hour.

be o*6 to o*8 volt

metal) is

gramme

voltage required

actual

per cell.

deposit
96,540 xo*84
to

watt
was

sees.

said

Early experiments in Saxony

(1892) proved unsuccessful, chiefly owing to difficultyof

according to the following
leaching with cupric chloride
equation

"

2CuCl2 +CU2S
Further
chloride

investigation

solution

is

good

=2Cu2Cl2

has

shown

leach

for

+S
that
certain

cupric

sodium

oxidized

ores

INDUSTRIAL

38
With

dcm.,

sufficient

make

to

current

consumption

surface

and

X2

ft.)a

sq.

required.
surface

amps,

of

current

tanks

of

over

5000

(3x1*5
is

tank

per

electrode

the

to

up

15,000

consumption

average

deposited is 0-166

of copper

pound

make

of cathode

amps,

currents

The

With

sq. dcm.

100

is to

proposed.

in series

dcm.

sq.

each

larger;

approximately

circuit.

volt

per

amperes

connected

per

tendency

the

been

per

2*2

2*2

is

are

200

or

cathodes

modern

have

current

the

total

The

of

30

large and

amperes
of

with

ioo

up

bath

of tanks

number

to

i'i

voltage loss per

the

o*4 volt.

to

0*2

density of from

current

square

ELECTROMETALLURGY

kw.

hour,

The
electrolyte
efficiencybeing 90 per cent.
consists
acid
essentiallyof an
sulphate solution
copper
containing 5 to 10 per cent, free sulphuric acid and 10 to
ampere

+..

re

4-..
Fig.

2.

General

"

cent,

15 per
from
are

arrangement

tank

to

removed

theoretically no
must

from

but,

bus

electrolyte.
refining gets
of

E.M.F.

0*3

In

volt

above-mentioned
balances
has

the

coefficient

falls

5000
case.

heat

risen to about
of the

to

energy

35 C,

deposited on

cent,

the

amperes

fall in

the
P.D.

of

by

supplied
owing

electrolyte it has

radiation

when

to the

been

per

the

the

copper

absorbed,

watts

=900

to

potential

resistance

energy

Cooling
but

other,

small

electrolyte in

the
to

of the

ohmic

the

on

the

transfer

to

necessary

is

copper

electrodes, amounting

the

Sixty per

owing
x

and

parallel.

electrodes

Since

weeks.

be

consequence

warm

The

already pointed out,

applied
bars

four

should

been

has

be

or

plates

in

continually circulated

is

stratification.

electrode

one

0*4 volt.

to

the

across

cent,

as

always
o*2

three

at

which

avoid

to

every

being dissolved

copper,

sulphate

copper

tank

electrolyticcells with

of

cell

60

per

in the

normally
temperature

high temperature
found

economical

ELECTROLYSIS

IN

still further

to

heat

SOLUTIONS

AQUEOUS

it

about

to

550 "

39

with

exhaust

been

adopted

steam.

alternative

An
in

each

and

vat,

anode

opposing

face

removed

has

and

are

cathode

off

electrodes

side

one

electrodes

end

bipolar,

are

deposited

and

the

on

bipolar electrodes
When
electrolyticdepositstrippedoff

of the

and

arrangement

intermediate

the

being dissolved

copper

are

The

plants.

some

in

electrode

electrode.

next

the

The

the
the

electrolyte becomes

The

Impurities

Blister

copper

may

the

nature

of

91

cent,

per

amounts

iron.

of scrap

copper
over

usual

the

the

materials

content

may

and

ore

Its

indicate

analyses

use

"

rise to

or

further

present in Electrolytic Copper.

widely in composition according
vary

the

smelting process.

for

and
by crystallization

sulphate is partly removed

copper

completely by the addition

to

contaminated

too

used
fall

as

in

the

low

as

following

The
98 per cent.
impurities present

their

and

:
"

Copper

Arsenic

Antimony
Bismuth
Carbon
Iron

Iyead
Nickel
Silver
Gold
Zinc

Sulphur
Oxygen

o*i2

pay

per

of

cent.

It

is evident

special attention

blister
low

demanded
The

should

impurities in electrolyticcopper

The

copper

grade
and

than

to
to

be

impuritiesin

more

preparation

attempt
when

anodes
can

the

it is

that

the

such

of

not

exceed

economical

high grade

to
raw

electrolyticpurification
high grade of purity is

obtained.

refined

copper

may

be due

to

variety

INDUSTRIAL

40

of causes,7 such
the

ELECTROMETALLURGY
inclusion

(i)the

as

growing crystals on

deposition ; (3) mechanical

These
impuritiesadversely
or

valuable

and

palladium
During

bottom

deposited in
occlusion
become

the

silver

is found

density

this

cathode;

agitation of
densities

Arsenic

the

silver loss in the

the

to

of

use

in

of

deposited

varies

electrolyte,since

the

only with
is not

electrolyte and

the

float

and

in

affected

mechanical
of

increased

by

"

the

arsenic

of arsenic

concentration

the

or

quantity

the

current
"

slimes

the

greater

high

quantity of suspended
both

slimes,

anode

electrolyte; it is probably deposited only by

occlusion

slimes

the

increasing current

that

attributed

is

is present

become

may

as

gold and

electrolyte with

increasing the

slimes.

in the

phenomenon

the

fall to the

or

means.

It is found

increase

an

the

by direct mechanical

entirely eliminated

are

in solution.

causes

anode

copper

solution

either

copper

by mechanical

occluded
and

raw

electrolytic deposition whilst

by

or

Gold
none

cathode

the

cathode.

impurities in

The

conductivity,

go into solution

either

copper

slimes.

as

the

disintegrationof

deposited

rarely platinum

more

or

in the

be removed

may

the

impuritiesin

gold

slimes.

the

the

electrical

of low

as

from

quality of

affect the

such

by-products

(2)electrolytic

contamination

it brittle and

by making

copper

surface

cathode

the

electrolytebetween

of the

in

current

density.
Nickel
with

which

the difference

of

continued

of

potential between

be sufficient to
and

copper

copper
be

can

in

nickel

containing

and

copper

made

to

but

copper,

nickel

the

relative

electrodes, viz. 0*4 volt,

very

sulphate

E.M.F.

is much

generated

It

as

electrodeposition, inclusion

occluded

is still

importance
of

is

Oxygen

of

higher
between

little nickel

generally present

gas

matter

these

The

little nickel.

alloy containing but

either

in solicjsolution.
the

nickel

infinitelysmall.

deposited copper

oxide
as

of

that

the

electrolyticallydeposit a solid solution

decomposition potential of
than

of solid solutions

mixture

(Fig. 3) is probably electricallydeposited, since

copper

would

forms

or

of

three

electrolyte and

as

cuprous

speculation
factors,
inclusion

viz.
of

ELECTROLYSIS

slime, on

the

IN

and

amount

deposited copper.

voltage points to slime inclusion

whilst increasingcontamination
contamination

be stated

increasing current

with

points only

41

impurities in

of the

nature

Generally it may

of contamination

SOLUTIONS

AQUEOUS

that

the

increase

an

applied
electrolyticdeposition,

or

with

density and

increasing electrolytic

electrolyticinclusion.

to

Nh"**o'

*"

Fig.

80

jo

nickel-copper alloys.
Freezing'melting-pointfcurves'of

"

Copper.

electrolytic copper

pure

for

necessary

is

electroplatingwith
usually employed as
trouble

no

is

impurities in the metal or the

has to be paid to the conditions
obtaining uniform, even, and compact deposits
of

electrolyticcopper.
The

practice of
of the

movement
a

violent

Various

current

agitation of the

electrolyte or

cathode, e.g. for electrotype rolls,rotation

high speed is used

refining.
the

In

"

consequently, although

by the presence
attention
electrolyte,more

at

3.

occasioned

of

AVom70Co

material

anode

A*bm

1 00

100

Electroplating with
copper,

100

60

7t"

"""

"*o

to

greater

extent

electrolyticcompositions

density is usually less than

than
aie

that

in copper
and

in use,

employed

in

refining processes.
are

The

two

the

acid

most

important electrolytesused

sulphate and

the

cyanide bath.

for this

work

INDUSTRIAL

42

ELECTROMETALLURGY
"

Copper

Sulphate

electrolytesmay
with

"

vary

sulphate pentahydrate

copper

the

addition

sulphate

Electrolytes.
Copper
in composition from
a
5

of from

to

to

content
10

per

solution

saturated

sulphuric

of free

cent,

cent,

per

acid.
The
to

2*5

amperes

rotational

speeds for the cathode

Coles up to 40 amperes
The

addition

of

been

advocated.

used

by Elmore,

by Consiglio

iron

salts to

decimetre

burnishers

Mechanical

are

be

can

electrolyte has

the

1*5

high

suggested by S. Cowper

as

per square

with

although

decimetre,

square

per

from

varies

density usually employed

current

employed.
frequently

such

sheepskin by Dumoulin,
frequently employed in

agate

as

glass beads

and

addition

either

to

agitatingthe electrolyteor rotating the cathode.

Cyanide Solutions."
Copper plating is frequently used
for coating iron or steel as an
intermediary film for nickel
plating. A
iron

by

film

thin

simple

for the

deposition

obtained

by

the.

of

the

Efc and

iron

and

solution, as

deposited
long as

necessary

directly
of

metals.

and

in

the

of iron

expense

of

pressures

CFe, CCii,be

cuprion

the

Epe

copper
copper,

are

solution
electrolytic'

at

the

on

hypothesis

Nernst's

of

to

iron

will be

acid

an

another

by

respectively,and

ferrous

in

conditions

the

metal

ECu be the

of
copper

described
one

deposited

than
electropositive

more

pressures

copper

iron

the

application

electrolyticsolution
If

is

already been

has

as

Iron

of

be

can

copper

immersion

sulphate solution.
and

of

the

centration
con-

solution,

going into

Ecu
^

Cf6
and

the

driving force

or

E.M.F.

Cco
of the

system

will be

^log^-^log^1
2F

The

iron is,however,

ceases.
a

porous

In

and

Cfc

Cca

quickly entirely coated

practice,however,
spongy

2F

deposit,and

flashing
other

"

and

deposition

is liable to

electrolyteshave

give
to

ELECTROLYSIS
be

The

chosen.

in which

exhibit

to

This
In

is

or

tendency

no

iron.

zero

depressed,making

iron

the

deposited
by the

following

use

are

"

less

an

alkaline

lyte.
electro-

cuprion

of

is

equation

of the above
its

apparent

The

is lowered.

E^

must

of the

passive, i.e.

is rendered

or

of

one

expense

the

at

concentration

the

pressure

noble

more

The

be

right-hand term

the

to

i.e. copper
practicallynegligible,

to

electrolytic solution
becomes

hypothetical equation

solutions

these

43

limited

electrolyteis

an

be obtained

can

greater, and

of

of the

E.M.F.

the

is reduced

choice

SOLUTIONS

AQUEOUS

IN

metal

easily attacked.
of such

typical examples

some

tions
solu-

"

(i)Copper

salts and

Copper

carbonate

Cyanide.
.

Potassium

cyanide

U.S. patent

cyanide

Potassium

carbonate

with

the

mixture

"

following solution

Copper sulphate
(*88o)
.

150

gms.

150

gms.

Cyanides.

and

"

most

as

The

effective

36
.

"

gms.

26 gms.
182 c.c.

cyanide
.

solutions

are

Electrolysis is conducted
0*5 ampere

Cowper Coles

"

Potassium
Water

gms.

Water

with

gms.

200

Ammonia

mixed

100
.

litre of water.

(ii)Copper salts,ammonia,
describes

200

gms./litre.
gms./litre.

100

Potassium

up

describes

129,124

Copper sulphate
Copper acetate

made

per sq. dcm.

mixed
with

and
a

made
current

38
148
up

gms.
c.c.

to

one

litre.

density of 0*4

to

ELECTROMETALLURGY

INDUSTRIAL

44

recommends

Watt

followingsolution

the

"

Copper sulphate

230

Water
to

which

just

ammonia

monium

added

until

solution

(*88o) is

redissolved.

potassium

To

this

cyanide is added

until

cyanide is just changed

been

bisulphite have
As

Alkaline

thiosulphates

have

alkaline

which

use

of

Oxalate
with

The
of

also
do

been

solubility of copper
baths
containing copper
oxalic

and

acid

be mentioned

may

tartrate

tartrates

"

and
Other

success.

in

caustic

soda.

ammonium

oxalate

suggested by

Classen,

and

been

have

taining
con-

cyanide usually make

contain

not

C.

Pfanhauser

by

with

used

cupro-

Baths

"

containing both

the

free

Gauduin

baths

cupram-

at 6o"

Cyanides.

this class two

typicalof

cyanide

baths

of the

recommended

of

solution

lilac of the

the

to

(iii)
Copper salts, Bisulphite,and
others.

strong
blue

the

precipitateis

the

Electrolysis is best conducted

cyanide complex.

and

gms.

litre.

others.

Conditions

Copper.

"

necessary
We

have

types of electrolytesused

for

Uniform

already tabulated

in the

tion
Distributhe

of
electrodeposition

various
copper,

INDUSTRIAL

46

Consequently
would

ELECTROMETALLURGY.
back

the

rise to the value

supply

of

surface

was

of further

at

diffusion

of

and

the

cell

if the further
cathode

the

at

by the electrical

electrode

ve

of

from

the

electrolyteat

the

electrolysis. After

distant

point x

of

"

concentration

the

commencement

cuprion

electrolyte

electrode

vc

I"et Co be

the

to

force

impressed voltage

supplied by

not

"

of the

ions

copper

migration

electromotive

time

electrode

/ the

the

tion
concentra-

becomes

C", and

dc
"

concentration

is the

gradient from

the electrode.

dx

quantity of salt diffusing per unit time

The

across

unit

dc
with

area

gradient

"

is

given by

equation

the

"

dx

where

diffusion

is the

between

x=*o

at which

the

and

#=

oo

according
alters is

concentration

fk
on

Fick's

to

law

the

rate

given by the equation

"

dx*

integration
"

VttD
the
At the electrode itself,
t becomes

4D/

Vt

concentration

after

time

interval

"

(!) C

The

C=C0

2=o,

D"

"

dt
or,

When

constant.

quantity

C"

aQ^/jLCo

of copper

*/I

n284Q

sulphate which

has

to

be

supplied

ELECTROLYSIS

deposited and

equal

"

96,540

96,540

i is the

in

current

and

of

i.e. at the

C=o,

when

moment

when

no

to

the

is

It

deposition can

large value

diffusion

factors

two

for

and

constant

be

can

the

C0,

adopt

applied

Nernst,10

in

solid

regarded
whence

of

the

as

the

the

rate

salt

from

to

be

electrode

the
to

decompose

initial concentration,

the

solution

the

surrounded
salt diffuses
of solution

the

prolonged by starting

sensibly increased

course

the

at

necessary

high

of

of

and
a

effect of

Whitney

solute

solution, in their

by

into
is

saturated

thin
the

in

less concentrated

the

the

view,

film of saturated

governed by
to

elevating

by

beneficial

hypothesis of Noyes

the

electrolysiscan

high migration constant, which

temperature.
For
the investigation on
can

"

present in the electrolyte.

under
equilibrium conditions

is

evijlent that

period of uniform

are

discharge of hydrion

which

sulphuric acid

electrode

passed, further

has

higher potential difference

the

with

'V

cupric ions

/96'54Q"
(i-wc)2tAri284/

the

only proceed by

and

we

Co2D

time

this

When

96,540

f=r

or-

equation,

V"

*-*-"-

we

or

migration

the

nc

above

in the

present in the layer of elctrolytenear

at

migration,

"

"

or,

that

between

equivalents,

gm.
s

amperes

cupric ion.
Substituting the value

47

of the

constant

obtain

ionic

the

__j

"

difference

the

to

supplied by

that

q
*

where

is

(Q)

diffusion

by

SOLUTIONS

AQUEOUS

IN

rate

unsaturated

last
the

stirring
9

and

of

solvent.
is to

be

solution

solution,
of passage
solution.

ELECTROMETALLURGY

INDUSTRIAL

48

film,then A

If 8 be the thickness of the saturated

per unit

constant

the solution

is given by

area

A-D
According
i
solution
..

is

to

the

Whitney, when

and

Noyes

rate

of

dc
"

dt

A(CMt.-C)

where

G^. is

the

saturation

(Csat.-C)
concentration

and

C the

centration
con-

of the

surrounding solvent.
Applying this equation to the case
consideration

where

Cq

of

depositionunder

"

is the

initial concentration

of the

solvent

and

rate

of

dc
the

concentration

at

electrode.

the

But

-",

the

dt

is equal to Q,
deposition,

where

"

i(i

"

nc)

96,54""

Q=^(Co-C)

or

Co""C==f

or

We

have seen,
of the

however, that

when

rotation

or

ment
move"

4=Vi"
82?T
t

"

~w

4D

//

no

is'considered, from equation (1)

electrolyte

o"-c-*y"

or

(3)

ELECTROLYSIS
From
to

up

this

equation

time

AQUEOUS

the

conclusion

electrolysis

SOLUTIONS

IN

be

drawn

that

continued

with

can

be

can

49

4D
the

same

efficiencyeither

the

electrolyte.

current

rotation

rapid

By

electrolyte,the

of the

electrode

thickness

film

with

period of efficient deposition increased.

calculated

8, the

from

film

this

thickness

sulphate with

the

in the

mechanical

the

of the

burnishing

by

use

higher

the

of

Nature

have

we

between

the

noted
and

copper

equation E.M.F.

the

that

the
=

vary

due

to

in

marked

on

of copper

be

derived

from

lating
by the circuof

deposition

is effected.

From

the

Electrolytes
preceding

electromotive

the

siderations
con-

force

surrounding electrolytegiven
C

log

"

2F
may

to

Complex

RT

by

solution

in time

or
"

has

"

densities

Simple
Deposit.

of rotation

deposited metal

of

the

and

Fischer

A.

the

economy

current

Influence

The
on

of

advantage

electrolytea distinct
the

of

case

followingresults

apart from

Thus,

decreased

influence

the

equation

stirring

agitationof

or

be

can

without

or

manner

Cu

is not

constant, but

Ceo

quite close

electrode

the

to

impoverishment of the electrolyte in cupric

ions by electrodeposition.The
advantage of supplements
ing the supply of cupric ions normally migrating to the
cathode
densities have to be
high current
by agitationwhen
the

is thus

employed

concentration
of the

at

of the

deposit is by

densities

and

once

apparent, but the influence

cupric ion
means

no

economical

so

E.M.F.

the

concentration

1*.

between
of

solution

clear.

seem

electrode

and

cupric

ions.

on

vSince

consumption

energy

desirable,at first sight it might

the

in the

the nature

high

current

always

are

advantageous

to

solution
In

of the

lower

by increasing
practice, however,
4

INDUSTRIAL

50
for

ELECTROMETALLURGY

electroplatingand

coherent
to

round

the

electrode

impoverishment
rapidly that,

is not

unless

must

required

place ;

that

work

fine

hard

has

been

concentration

spite of the fact that

if it

even

adopted,

occurs

low

too

so
a

centration
con-

at.

metal

to

in

agitation be

assume

worked

advisable

take

may

is arrived

to

deposit is desired, quite the converse

hold ; namely, that a high cuprion

found

We

electro-analysis,where

obtain

to

have

we

burnish

or

deposit similar

the

supply

to

metal

the

hard

it

extra

energy

electrically.In
RT

words,

other

limitingvalue

below

which,

occurs

in

although

to the

metal

the

is

form.

non-compact

is set

It

==

must

log

-="

be

not

due

to

ions, since

the

P.D.

exceed

critical

the

cation.

The

attributed
ion

is

to

it, according

of the

which

to

metal,

the

on

deposited

the

ion

the
and

the

on

or,

other
may

deposit the

to

necessary

of

metal

and

metal

high potential gradient under

the

loses its charge

and

P.D.

great

disturbances

deposition

solution

between

compactness

deposited

rapidity with

simultaneous

the

too

Ceo

by the depressionof the cuprion concentration,

occur

forgotten,

be made

"

2F

may

log -^"

"

deposited, the deposit

RT
that if the term

however,

term

other

which

other

of

form

hydration associated

following scheme

the
to the

hand,

changes into the metallic

water

be

may

with

"

Cu(H20),-"Cu(H20),r"Cu

is strong

There

solution, but

hydration

we

water

evidence

that

yet certain

not

are

proceeds

as

ions

the

are

whether

rapidly

the

the

as

hydrated

in

loss of the

loss of electric

charge.
Since

in

complex
ions

is

ion

electrolytes the

low, the view

the

metallic

the

electrolytic deposition of the

so

direct

discharge of the

but

secondary

effect

metallic
due

to

ion
the

is

of

frequently held that

metal
as

concentration

has

is not
been

discharge of

simple

suggested,
other

ions.

ELECTROLYSIS
For

IN

SOLUTIONS

AQUEOUS

51

example, in potassium cuprocyanide, an anion

followingequilibria are undoubtedly present :

the

complex,

"

KaCu^CNJ^K'+zCuCCNJ'j

Cu(CN)'2^Ctt+2(CN)'
KCN^K'+(CN)'
The

value

of

="

g"?

log

obtain

We

io"~3%.

value

of

the

cation

as

solution
a

of

salt

cuprous

concentration
assumed

of
be

to

and

the

cuproions

present, the

"

|"log I*

represents

In

normal

which

*~Cu

potential difference
If cupric ions are

observed
of

for

volt.

0658

of the

case

of io_48w.

concentration

ammonia

copper

volt,

0-329

cupric ions.

cupramine

or

complex

"

Cu(NH3)-4^Cii+4(NH3)
solution

normal

formation
"

of the

-0*329 to
With

cupric ions is reduced

cupramine complex, the
of

"0*0694
these

volt between
small

very

metal

and

ion

metal

to

potassium ions, where

the

E=

solution.

concentrations

rise to

must

may

possibly

potassium

the

solution

volts

+3*20

then

according

to

take

for

log
*

the

and

discharge

P.D.

necessary

"

by the

rising from

P.D.

high electrolyte-electrodepotentialdifferences
of

9w.

io~~

E-"
Ck-

normal

place under

potassium

working

ion solution,

conditions

secondarily deposits copper

the equation

from

the

"

2K+K2Cu2(CN)4=2Cu+4KCN
Since
metal
or

equally good results

electrolyteswhether

cation, Daniel's

view

12

the
that

are

obtained

metallic
the

with

complex

is

complex
an

anion

migration of the complex

ELECTROMETALLURGY

INDUSTRIAL

52

from

away

in

results

Deposit.

in all

that

probabilitythe

of

by

cupric

the

being

scheme

the

tribution
dis-

current

Agents on the
been
pointed out

Addition

section

previous

greatly influenced

density

current

correct.

of Various

the

In

"

of

readjustment

scarcely be

Influence

points of highest

at

automatic

an
can

The

cathode

the

it has
of the

nature

the

conditions

ion

is

which

under

charge
dis-

the

matic
diagram-

the

about,

brought

is

deposited copper

"

Cu(R20)tt-"Cu(H20)tt-"Cu+2$
When

the

electrode

speed

potential

is great

at

complex

difference

the

cupric

the

electrode

surface

has

but

this
variation

of

in the

stability of

cathodic

unstable

which

the

metal

be

can

copper

the

made

which

tolerable

unif

ormity of surface

it is

The

and

such

so

vary

thetical
hypo-

of the

nature

suit

to

as

density will suffice

hardness
and

desirable

are

hardness

wire

as

is

the

electro-refining a

In

and

smoothness

work

special

to

intended.

electroplatingsmoothness
electroanalysis
great

hydrate

deposition.

for

for

only by

not

by influencing the

purpose

and

discharge

fluence
in-

likewise

can

potential difference, but

intermediary in

deposited

We

great

intermediate

labile

the

and

and

discharged with

is

existence.

short

process

ion

solution

between

in
in

necessary

are

construction

tube

or

is necessary.
ductility*
The

crystal size.

the

substances
have

to

must

be

with

the

tannic

be

warmed

are

copper

In

effect
to

is

acid

solutions

i.e. it must

colloids of this type.

25"-35"

ing
Vary-

the

marked
C.

usual
if

the

tend
;
One

to

Such

added
be

codeposited

part of glue in

act

iooo

fine-grained

of

electrolysis.

electrolyte be

colloids

colloid

gelatine,glue and

conditions

the

colloidal

add

to

sulphate electrolytewill give

more

"

following conditions

the

by electric endosmosis

deposit under

tenacious
The

electrolyte,when

positivelycharged,

acid

acid

general practice is

observed.

copper

Deposition.

Copper

intermediary phase directly influences

the

The

the

to

in

Colloids

stabilityof

the

of

of

Use

as

slightly

protective

ELECTROMETALLURGY

INDUSTRIAL

54
of the

of the

course

colloidal

material

is

sufficient

above, but

mentioned

reaction

usually present

act

to

as

protective

colloid.
The
cent,

in the
and

concentration

will

cathode
form

to

the

The

Use

The

use

of

oxidizing agents,

^"u may

hydride

copper

rapid

acts
to

as

cathodic

to

evolution

assume

depolarizerfor

such

of low

high

electrode

hydrogen

formation

the

point

spongy

that

the

causes

appearance,
of

unstable

an

solution.

hydrogen

copper

Nitric

acid

hydrogen, being reduced

ammonia.14

Electrodeposition
Electrolytic depositionsof

"

true

brass

or

for tin

and

Bronze
"

bronze

been

have

Brasses.

made,

"

both

alloys of copper and tin, and also of

copper-zincalloys. Nickel has also been substituted

or

been

appearance
The

of

bronzes, namely
zinc, and

bronze-coloured
has

of

the

to

The

as

We

required for evolution

brown

attributed
or

is

acid,

conditions

rise to

hydrogen.
been

nitric

potentialbetween

of

of

has

Copper Depositions.

sulphate electrolysisand

in

approaches the potentialdifference

which

this

salt.

usually

it

deposited copper

present

log

"

The

ions

place from

take

certain

under

that

RT

beneficial

electroanalysis of copper.

the

to

density, the difference

solution

be

cuprous

in

Oxidizing Agents

cupric ion concentration

and

chlorides

to

simple ionized

the

of

already noticed

current

the

partiallyreact with the

Deposition
+ 2G'^CuCr.

therefore

will

of from

practically confined
have

Cti

complex

ions

instead

complex

it

undoubtedly

the

cuprous

the

per

bismuth

and

solubilityof
it appears

'004

only does

not

to

up

silver, antimony

deposit ;

of the

smoothness

chloride

"

of the

oxyehlorides formed), but

the

of

advocated

electrolyte (by the limited

the

at

quantities of chlorides

frequently been

have

limit the

to

of small

use

even

arsenic

deposit.

The

has

been

demand

by their actual

potential difference

the

their

metal

equation

"

and

deposits

colour

and

composition.

between

containing its ions is given by

by

obtain

to

bronze

for

chiefly regulated rather

than

used

solution

ELECTROLYSIS

IN
RT

Ew=the

and

Cm

the

solution.

metals
the

electrolyticsolution
concentration

the

from

For

Ctnx

Jiog"

or

in normal

of

deposition
metals

in

two

ions

as

"

"g

w2F

Cw2

-l=log=-^

following are

Ew2
equilibrium potential differences

the

solutions

and

ions

Cm2

n2

metals

hold

must

"g

n{$

between

metallic

valent

simultaneous

the

following relation

The

of the

metal,

of the

pressure

electrolyte containing both

an

55

JSitn

"

where

SOLUTIONS

AQUEOUS

containing

__RT

hydrogen

P.
1

ions

value

the

concentration, taking

metallic

the

at

atmosphere

~"

normal

ion solution

M"

M.

as

zero

:
"

"0*329

Zinc

+0770

Tin

+0*192
+0*228

Nickel

Advantage
tin

"

complex cyanides,

"

and

The
varies

with

the

mixed

is

possible

dissociation

to

of

to

copper
be
the

point

that

deposited.
various
complexes

by electrodepositionfrom

and

electrolyte

deposit either

to

variation

examples

cases

begins

of zinc, nickel

that

various

at

metallic

one

it

temperatures
constituent

or

alloys.

potential

of the

also

temperature,

complex

series of

It

of

degree

The

metal

other

the

of the

possible to raise the

it is thus
for

complexity

the

greater than

deposition potential difference

where

(divalentions only)

"

of the fact that

cyanide ion is much

cuprous
or

is taken

(divalentions only)

volt

Copper

of the
various

the

at

shown

are

will be noted
cathode
since

the

complexity

and

followingcurves

there

potential on
ionic

given by

temperatures,

in the
that

is

is
the

concentration

very

current

of

the

cathode

few

typical

"

marked

dependence

density.
the

metals

In

in

these
the

INDUSTRIAL

56

solutions

is low

must

we

ions

with

be

noted

rapidly, whilst
The

the

potentials

of

measured

deposition
noble
take

their

against

ion

on

to

by

the

place,

between

nature

two

the
the

In

The

(i)

metal

(a)'
The

complex

breaks

down

noble

to

course

cr"r

in

in

constituent

again

most

of

are

","

ion.

stable.

most

metals

respective

tending

the

lower

of the

less

alloy

the
the

of

case

will

divergence

discharge potentials.
of

complexity

metal

(2)

more

deposit by

the

ions

the

depends

speed

alloy partial depolarization

an

practice

of the

(i)

thus

of

appears

_"""

metallic

instantaneous,

The

complex

"

v^Agiefa

is not

speed.

complex

of

ion, e.g. Cu(CN)'g-"

complexity
silver

the

copper

discharge

reformation

complex

reaction

the

on

that

of

rate

the

slow

rapidly by electrodeposition,

equilibrium again

at

probability

Tt will

the
of

arrive

to

proceeds
all

that

dissociation

2CN'-|-Cu

in

is removed

and

assume

by

but

ELECTROMETALLURGY

temperature

alloy deposition
the

we

can

followingindependent

of the

control
variables

electrolyte affecting

affecting (1) and

(3).

the

the
:

"

ratio

ELECTROLYSIS

(3) The
,

IN

densities

current

complex-"ion

reactions

-.

".

"

complex-"ion

SOLUTIONS

AQUEOUS

57

velocities

affecting the

of

(1)
;-'
(2)

(4) The

composition of the deposit.

following examples indicate some

The
where

the

same

depositionpotentialof

solutions

of the

ions is the

metallic

the two

"

Copper-zinc.
(1) Copper sulphate
Zinc

sulphate
cyanide

Potassium

25 gms.
29 gms.
to dissolve

precipitate.

the

Water

(2) Copper acetate

Zinc sulphate
Potassium

4'5 8ms9-0 gms.

67*0 gms.

hydroxide
cyanide
(*88o sp. gr.)

Potassium

Ammonia

litre.

"

"

7'5 gras-

Water

30*0 gms.
1 litre.

Copper-tin.
(1) Cuprous
Stannous

chloride
.

"

"

1-5 gms.

chloride

Potassium

cyanide

Potassium

carbonate

1 #2
.

"

"

"

"

"

10*0
ioo'O

Water
.

"

(2) Copper phosphate

'

Sodium

pyrophosphate
pyrophosphate

Sodium
Stannous
added

chloride

j saturated
.,

gms,
gms,

litre.

gms.

"

,.

solution.

"

to"

Sodium

pyrophosphate

Water

(3) Copper sulphate

Stannic

70 gms.
8 gms.

chloride

Potassium

hydroxide

Water

oxalate
acid
"

Water

small

"

amount.

litre.

15-0 gms.

oxalate

Ammonium
Oxalic

(4) Copper sulphate

Stannous

50 gms.
1 litre.

4*2 gms.
550

gms.

5-0 gms.
1 litre.

58

INDUSTRIAL

ELECTROMETALLURGY

Zinc.

The

conditions
and

recovery
from

that

economical,

is very

of zinc, however,

only

Not

takes

lytic
electrodifferent

somewhat

are

its

the

are

place according to

only of

recent

of the metal

roasted

ore,

retorts

in

years

feasible.

appeared

the recovery
the

by purely thermal

ores

it is

and

have

generally from

more

economical

the

zinc

from

copper

electrolyticmethods

case
or

refining of
of

recovery

processes

for

for copper.

those

The

obtaining

is

from

In

the

the

ore,

of great difficulty.

one

which

reduction

the

equation

the

C+ZnO=Zn+CO

fragile, owing

very

condensation

the
be

bring about

to

necessary

zinc

without

accomplished

into

vapour

the

loss

of

temperature

(over 12000

distillation

the

of the

high

extremely

the

to

blue

C),

regulus

but

cannot

(see

powder

p.

142).
Successful
electric
these

heating for the reduction

will be

With

methods

the

problem

pure

of

that

to

internal

use

distillation of the zinc ;

and

later section.

against reduction
made

were

by

utilize

to

means

electrolytic

uniformity

obtained

cost

of copper

zinc
in the

early

the

of copper.

in

for shell

brass

for

certain

in

but

is

for
where

also

of

vacuo

Belgian fuel furnaces

the

the

crude

easily accomplished

reasons

which

low

will be

electrolytic purificationof

always be

manufacture,

is necessary,

by redistillation
of the

is not

only is the demand

Not

except

case

boiling-pointof the metal.

electrolyticrefining of zinc is higher than that

account
of

electro-refiningof zinc the

limited

zinc

on

up

to

eventually entirely replace

may

purificationof

for

made

processes.

absolute

The

in

early attempts

comparable

zinc

with

disadvantages

which

thermal

very

dealt

these

of carbon,

In

been

have

attempts

limited

technical

one,

but

stated.

zinc

metal

undoubtedly

by-products,

such

as

Thus

the

will

probably

useful

for

field

working
galvanizer'sdross

ELECTROLYSIS

IN

(averaging 90 per cent, zinc

from
lead) and zinc scum
(averaging 50 per
lead, silver and any gold
process

richer in zinc

scum

probable

that

zinc

and

"

the

blue

regulus from

cent,

zinc

and

that

may

be

returning it in

electric

furnace
"

powder

available

for

It is also

extremely

portion of the

uncondensed
be

With

zinc

the

such

some

carbon
of the

growth

"

quantity of

the

wet

zinc

economically

more

by briquetting with

of

production

yields

process

consisting chiefly of zinc

"

furnace.

the

Parkes

minium
alu-

The

present).

than
disposed of electrolytically

and

desilverizing

containing copper,

cent.)

furnace, could

zinc

the

of the

powder

the

oxide, being

lead

Parkes

the

80 per

(70 to

59

containing iron, tin and

and

modification

amalgam

SOLUTIONS

AQUEOUS

blue

will

process

be

extremely large.
The

Electrolytic Recovery

of

Zinc.

early attempts

were

made

of copper,
and
in

many

roasted

briquetted with

ores

cells,but
electrolytic

Sulphuric

Acid

of war,

Germany

supply

of

controlled

Australia.

Their

rights

the

over

the

concentrate

is

ore

of

The

basis

into
with

sulphates and
dilute

The

and
Small

anodes

shipping

operation

most

of the

This

being

gangue,

galena complex.
at

is the

sulphate electrolyteprocesses
low

red

oxides.

heat

to

oxidized

The
and

the

convert

sulphides

is thenleached

ore

submitted

to

preliminary

electrolysis.

acid
silver

was
are

quantities of other
soluble

to

consists

and

English market,

electrolytic sulphate process was

Halske
and
Laszczynski in Poland.

sulphuric

in

area

Europe.

to

and

ore

acquiring the
in

processes

zinc

earliest

by Siemens
cent,

ores

Hill

by

little silver

sulphuric acid

purificationbefore

zinc

of the

Broken

the

enforced

for the

of all the

primary roasting

in

was

sulphides of zinc, lead,

case

outbreak

the

to

greater part

before

available

now

use

the

soluble

as

Previous

flotation

ore

essentiallya blende

and

mined

various

coke

"

the

control

to

in

all unsuccessful.

were

Processes.

world

the

As

"

silica,are

used

as

removed

as

by

Ten

leaching agent.

metals, such

removed

devised
per
Lead

sulphate by filtration.
as

iron

fractional

and

copper

neutralization

60

INDUSTRIAL

with

lime, followed
ferric state

the

zinc

is used

of zinc

anodes

P.D.

of

per

thin

showing

Modifications

difficulties

found

Material.

Carbon

anodes,

deteriorate
anode.

under

zinc,

of

ing
follow-

The

of zinc.

original

in the

lead

trials with

of the

as

of

ferric

to

thus

zinc

the

anodic

reduction

ferric

the

ferrous

the

by the lower

sought

divided

to

at

the

eliminate

cell,using ferrous
ferrous

sulphate
of the

reduction

accomplished

was

deposited. In this case

as
leaching agent. Since

is used

required, and

not

cathodic

sulphate proceeds practicallyquantitatively,

number

extra

evolved

oxygen

produced

depolarizationis

of the

been

had

sulphate solution

complete

of

use

substances.

indicated, rapidly

depolarizer,the
sulphate ; cathodic

solution

sulphate
most

by the

material

anode

as

other

already been

action

the

evolution

being oxidized

oxidize

ampere

increasingly

becoming

adoption of

has

as

sulphate solution

ferric

cent.

Early experiments by Ashcroft

oxygen

after

The

"

after extensive

only made

ferric

kgm.

inherent

be

to

With

cathodes.

deposit
are

sheet

containing

density of

electrolyticrecovery

were

is circulated

"

Anode

the

method

oxide

zinc

process

was

will

hours

in

nearly neutral

vats

current

iron

little bleaching

obtained, which

is thus

of

agitation with

filtration.

cell and

of this

for the

important

of

efficiencyof 80 per

current

addition

electrolyticzinc

3*4 kw.

dcm.,

presence

electrolyzing

3*8 volts per

sq.

The

final

sulphate

and

the

before

wooden

through
lead

by

Frequently

dust

solution

by filtration.

is ensured

powder.
or

ELECTROMETALLURGY

of ampere

sulphate was

required

hours

to

practicallycompensated

operating potential difference

due

re-

for

anodic

to the

depolarization.
Soluble
in

iron

anodes

practice that
and

sufficient
are

now

the

the
make

to

also

were

trouble

cost
the

due

used,

associated
to

process

the

but

it

with

the

loss of

iron

phragms
of dia-

use

alone

impracticable. Lead

practically general, and

found

was

usually prepared

were

anodes
in

situ
.

from

sheet

lead, but

protected by

thick

as

in the

case

depositioncarbon
peroxide,1* magnetite

of copper

deposit of lead

ELECTROMETALLURGY

INDUSTRIAL

62

top, unless

the

to

prevented from

corrosion

The

is

the

of

course

few

plates
The

hours.

the

by

be eaten

may

usual

lation.
circu-

by active

so

greatly assisted

and

atmospheric oxygen,16

doing

of

through

in

prevention

of

method

presence

Zinc

\jU

vo

Fig.

is

5.

by the

Surface

"

of

use

corrosion

just below

the

aluminium

plates as

unqualified

been

obtained

for

electrode

easier

deposit
than

of zinc

can

cell in

in

of
that

also

zinc could

be

normal
It

The

hydrogen.
zinc

ion

follows

if

to

liberate

experimentally
of

the

arrived

zinc

and

gas.
the

at
a

low

at

is

the

on

the

zinc
of

anode

ion and

be

liberated
anodic

and

conclusion

acidity

normal
before

potential

applied

was

Mylius

same

and

zinc

excess

solution

sulphate

hydrogen

would
an

the

electrolyticpotential

deposited

deposited,until

to

consequently

copper

solution

that

or

is

it

acid

an

deposition

Ecu referred

volt ;

from

against the

volt

necessary

concentration

with

necessary

of copper

electrolytecontaining normal

+0770

of

sulphate electrolyte

metal

the

hydrion concentrations, hydrogen

any

to

use

attended

conditions

case

"0*329

copper

volt.

The

"

the

In

reversibly liberated
an

paint

investigations,but the results

many

was

liberate

to

+0770
be

has been

deposits from

conflicting.

hydrogen

scale

by bitumastic

material

Deposition.

subject of

are

solution

readily

not

are

success.

the

to

which

deposition.

electrolyte. Recently, the

electrolyticpotentialof

the

in zinc

cathodes

cathode

obtaining uniform

have

cathode

if necessary

line of the

Conditions
for

zinc

pure

by acid, and

attacked

of zinc

above

Fromm
that
were

17

high
most

ELECTROLYSIS
desirable
to

in

work

to

high

of

keep

salts is to

be
in

deposit,and

spongy

unstable

an

Pring

The

and
and

high

carried
of

current

with

out

small

Their

find

that

densities

the

to the presence

tion
forma-

to the

not

as

of spongy

formerly

was

sidered.18
con-

reinvestigated the problem,

with

strongly acid
deposition of zinc

solutions
could

be

high efficiency,
especiallyafter the addition

colloidal

of

trace

is

process

19

Tainton

surprised to

were

and

the

to

is necessary

cause

be due

hydride of zinc,

and

necessary

owing

practiceit

definitelyto
depositionhas been shown
of oxidizing impuritiesnear
the anode,
of

found

was

avoided

electrolytedistinctlyacid.

the

63

density.

current

of basic

presence

formation

SOLUTIONS

AQUEOUS

electrolyte. Further, it

an

with

The

IN

basis

the

now

material

the

to

several

of

electrolyte.

semi-technical

deposition installations.
The
100

electrolyte contains
of zinc

gms.

anodes

sulphate

zinc

and

density from

current

An

to

20

sulphuric acid
perforated sheet

litre ;

per

cathodes,

each

over

of

gms.

aluminium

or

potential difference

150

50 amperes

lead
The

used.

are

is about

vat

and

5 volts, and

decimetre.

square

per

the

be obtained
at a temperaefficiencyof 95 per cent, can
ture
The
zinc deposited by this method
of 180 to 250 C.

from

solutions

from

remarkably
The

small

and

impurities
obtained

containing

pure,
in

curve

of

traces

Broken

roasted

using 0*05

in

electrolytecontaining 13
10

to

19

per

cent,

zinc

per

to

results

the

14 per

usually
is

cent.

obtained

arabic

gum

sulphuric acid

grosser

concentrates,

99*80 per

cent,

authors,

and

Hill

as

substances

other

averaging well over

Fig. 6 represents

these
an

lead, iron

manganese,

with

colloid

as

zinc

cent,

by

sulphate
cent,

o*i

per

the

ratio

of

iron.
The
zinc

explanation

deposited

rising hydrion

to

of these

the

results

in the

of the

increases

liberated

hydrogen

concentration

where

with

electrolyte is far from

satisfactory.
As
the

has

already been

overpotential

metallic

surface

necessary

varies

with

pointed
for
the

out

in

the

hydrogen

nature

of the

introduction,

liberation
metal.

at

In

the

INDUSTRIAL

64

of zinc

case

applied E.M.F.

an

reversible

the

applied
excess

ELECTROMETALLURGY

difference

required

of zinc, which

in

the

scale.

hydrogen

under

that

to

normal
In

of

the

the

of the

be

must

This

potential
deposition

is +0770

neighbourhood
ions

acid

hydrogen.

for

necessary

both

higher than

critical

the

zinc ion solution

conditions

these

raises

volt

of the

evolution

the

theoretical

the

over

to o*8o

decomposition potential

bring about

to

of 070

volt

on

electrode

equally susceptible

are

100

93

98

80

I75
70

(3
65

60

65

30
So

10

3o

So

Oo

Amperes
Fig.

6.

"

Influence

of current

deposition,since
practicallythe same.
to

preferment
assumption
some

such

for

the

scheme

as

be

that

of the

however,

be

~*

to

hydrogen

Zn

deposition,which

depicted as

2H(H80), J

the

"

UC
|Zn(H20)J

12H(H20), J jH2(H20),
"*

~*

H2

is

natural

IZii(H20)B

zinc

explained on
deposition according

may

velocity of

(
is greater than

zinc ions have,

follows

of

deposition potential

deposition which

that

9o

efficiencyin deposition

on

necessary

The

bo

per ""j.dcm

density

the

70

60

may

IN

ELECTROLYSIS
Not

only

have

hydration numbers
but
an

the

series

second

the

not

are

that

changes is bimolecular

of

ions,

for both

same

the

and

not

change like the first ; both these factors

the
velocity of conversion.
greatly influence

intermolecular

probably
Bennet

(H

and

evidence

independent

other

we

65

SOLUTIONS

AQUEOUS

sulphate solution.
reaction

If

between

2H(H20)*
equation

and

the

H2

zinc

the

active

that

hydrogen

H") can deposit zinc from zinc

this assumption be correct a secondary
hypothetical intermediary compound

distinguishedfrom

as

believe

Thompson20

and

or

ions

according

occur

may

the

to

"

Zn+2H-^Zn+2H
"

investigators have

Many

accepted

"

of this

modifications

and decomposition
theory representingthe change by the formation
of unstable
hydrides. The
advantage of a high

emphasized by the consideration

that the resolution of the depositedzinc proceeds at a constant
rate
for smooth
deposits depending on the acidity of the
electrolyte,thus by increasing the rate of deposition the
efficiency is also increased.
apparent
Spongy surfaces
density is further

current

will

naturally dissolve

the

greater
The

Tainton

exposed

area

Use

quicker than

of

to the

Colloidal

recommend

the

zinc and

smooth

to

solution.

Addition

Agents.

of colloids to

use

owing

ones,

Pring and

"

tion
deposi-

the

ensure

impuritieswhich are likely

to
be deposited at
high working potential difference
a
between
electrodes.
This
the
point has already been
discussed in dealing with the depositionof copper.
The usual
colloids employed are
dextrin, gum
tragacanth and gum
of the

arabic

of about

Watts

and

to eliminate

concentration.

0*05 per cent,

Sharpe

21

suggest

the

of

use

per

cent,

of

eikonogen, pyrogallol or j3-naphthol.

The
process

Brunner,

berg and

Chloride
was

Mond

developed
and

Fiirfurt

preference to
**

Processes.
and

Co., and

in

calamine

"

Hoepfner's original chloride

is

is said to

Germany,22
as

raw

still worked

but

be

the

material

at work
use

has

Messrs.

by

at

Duis-

of blende
stimulated
5

in
the

66

ELECTROMETALLURGY

INDUSTRIAL

employment

of

chloride

the

than

sulphate electrolytes,more

method.
A

solution
zinc

roasted

the

with

calcium

calcium

when

tower,

chloride

ore

equation

ore

and

Iron

be

present.

used

chloride,

10

such

density

Foerster

to

sulphate solutions,
with

Operating

provided

cell

or

be

may

analyzing 99 '97 per

cent,

may

be

efficient circulation

in the

that

The

said

to

asbestos
be

be

of

that

nitrated
been

the

be well
cent,

per

The

chlorine

carbon

anodes

over

94

stated

per

to

of

cathodic

diaphragms
silica

give,good results.

efficiency is obtained

on

addition

are
on

It may

agents

is

efficiency is stated

current

cent., whilst

used

are

hydrated

colloidal

evolved

for chlorination,

liquefied. The

cellulose, but

addition

general practice. The

to

and

cathode

revolving cathodes

preparing bleaching powder,

fibre has

noted

of

use

where

compartment

compressed

current

cell,

anode

for

on

per

from

be used

Fromm

high

at 3-5 to

advantages for this process.

can

carried

who

7 volts

sq. dcm.

per

possesses
the

cent.),and

be basic.

not

and

is

of sodium

(o*i per

Giinther,

may

chloride

as

cent,

electrolytemust

is maintained.

compartment

which

Mylius and

of

diaphragm

deposits of zinc

zinc
per

and

those

to

the

3 to 4 amperes

obtained

20

final filtration

copper

of

hydrochloric acid

similar

experiments

as

solution

cent,

per

According

good

little alkali whilst

addition

by the

removed

are

with

chloridizing roast

deposit metals

little free

gypsum.

the

given

electrolyte,containing about

as

out

be

can

and

zinc will

scrap

to

+CaCOs

+C02-"ZnCl2

manganese

bleaching powder

over

deposited according

is

"

Alternativelythe
of

chloride

carbonate

CaCl2 +ZnO

salt.

by treating the
in a carbonating

is obtained

of zinc

at

the

the

only 85

anode

chlorine

actually

As

already

collected.
The
been

of

Electrolytic Refining

mentioned,

except

by-products the method

in

of

certain
has

but

Zinc.
cases

"

for

the

has

utilization

little commercial

value.

ELECTROLYSIS
Richards

when

cent,

acetate.

used

With

cathodes

zinc

of

300

deposits could

volts, good

1*25
air

agitation

and

efficiencyvaried

current

the

average

The

iron

analysis showed
from

the

electrolyte by the
the

hydrated

the

acetate

The
the

Gold

to

10

Silver

and

50

per

frequently up
o*2

to

and
be

from

the

filtration

by

of

precipitatedfrom

was

Hamburg

at

obtained

scum

containing from
zinc, and

cent,

to

70

cent,

of silver and

cent,

attempted

in the

50

5 per

zinc

sulphate

granulated pieces lying

or

With

anode.

Anstalt

zinc

7 per

They employed
anodes

which

impurity.

cent,

removed

was

The

cent., and

per

per

that

cent,

per

and

copper,

little

Parkes'

gold, and

aluminium.

cent,

per

at

solution.

desilvering process,

lead,

material

hydroxide

purification of the

lead

100

agitation,followed

air

ferric

and

only 0*05

anode

provided
employed.

were

80

between

the

dcm.

sq.

per

obtained

be

from

cm.

voltage fall per cell of

circulation

good

17

sodium

cent,

per

ampere

320 C. and

to

08

separated
1

As

sulphate hydrate,

acid, and

density of

current

zinc

anode

as

aluminium.

cent,

per

cent,

per
acetic

temperature

15

o-i

commercial

and

anodes

with

cast

electrolyte he
per

galvanizer's dross

successfully used

material

67

SOLUTIONS

AQUEOUS

IN

per cell

at 1*3 volts

obtained,

of o*8 to

current

but

the

good

solution
on

horizontal

ampere

did

carbon
dcm.

square

per

cast

deposits of zinc could

coherent

process

either

and

not

commercially

prove

successful.
A
as

chloride

electrolyteis said

silver

chlorides

obtain

using zinc

process

be successful, in which

to

deposited

accomplished

by

cleaning the
dipping it in

iron

outside
The

sludge

the

be

can

lead

and

cupelled to

silver.

the

Electrogalvanizing.

4500 C.

in the

chlorides

magnesium

and

bath

"

hot

the

galvanizing

steel

or

of molten

superficialalloy
of

commonly

most

process,

namely,

by

plate, pickling it in acid, and

zinc at
is made

containing the compounds

formation

is

Galvanizing

temperature

with

FeZny

film of iron-zinc

pure
and

alloy

of about

zinc

on

the

FeZn3.
on

the

surface

68

INDUSTRIAL

ELECTROMETALLURGY

considerably lower

may

articles,such

as

temperatures

employed

the

tensile

acid

The
with

(4500 C.) may

Under

this

to

zinc

conditions

necessary

sulphate solutions,and

lowering in

electrodeposition
lead

peroxide anodes

for

deposition are
electrodepositionof

obtaining in the

those

subsequent thermal

circumstances

these

have

thin

the

relativelyhigh

the
cause

sulphate electrolytewith
feasibly employed.

be

can

cables, whilst

or

strength of steels due

treatment.28
from

hooks

of

strain

breaking

the

already been

referred

identical
from

zinc
to.

Cadmium.
electrochemical

The
similar

does

its

is

Thus

ions

hydrogen
yet,

with

for the

demand

refiningof
24

Brand

887

Cu

metal

1*35

cent,

cast

cent., Zn

per
per

cent.

zinc

cadmium

sulphuric

acid.

successful

be

has

the

is very
necessary

former

the

as

hydrogen

scale

of +0770

volt.

cadmium

first to

be

and

deposited,

high, being
for

deposition

the

is very

Technically there
not

+0*400

density practicallyidentical

current

metal, and

accomplished

practice of

and

pure

purifying

on

Cd

the

high

metal.

former

the

value

the

little

electrolyticrecovery

and

accomplished on any scale ;

large-scaleexperimental work
of the
following composition,

been

some

anodes

8*55 per cent., Pb 1*35 per cent., and

usual
As
the
electrolyte he followed

refining,using a solution containing 10

cadmium
as
sulphate and 5 per cent,
His

electrodes

deposition was

in the

spaced 5

were

accomplished

density of 1*4 amps, per sq. dcm.

at first practicallyzero
owing to
electropositivezinc

very

zinc, the overpotentialof hydrogen

conditions
a

the

is

ever,
solution, how-

containing both

cathode

with

metal

of the

has

would

with

case

against a cadmium
volt, making the

zinc

solution

hydrogen

the

was

as

electrolyticpotential on

from

though

cadmium

great difficulties

volt, whilst

only +0*420

of

deposition from

Its

present such

not

metal, since

zinc.

of

that

to

behaviour

anode

The

cms.

with

E.M.F.

per
free

apart,
current

applied was
the presence
of the highly
causing direct deposition

ELECTROMETALLURGY

INDUSTRIAL

70

earliest made
with

There

is

"

sickens

hindering
of

power

becomes

and

its coalescence

amalgamation

it the

be

may

Two

mercury.

the

recovery

and

potassium cyanide.
the

crushed

of

process

and

This

of

method

disadvantage
the

other

that

very

the

and

is

ore

solution

associated

is

of
for

viz. free chlorine

ores,

bleaching powder

some

employed

also

aqueous

an

The

effect

amalgamating

extraction

chlorine

extraction

and

gold,

sulphide of

are

by

addition

the

or

oxide

the

wash

oxide

tendency.

its poorer

with

extracted

prepared from

water

to

gold from

in the

mercury

or

its

lessen

to

away

the

solvents

other

both

rectifies the
the

resist

may

the

of

with

with

of oxide,

film

electrolyticcell

an

coated

which

metal

In

of

quantity of sodium

gold-itself
other

in

with

carried

be

to

making

small

the

ally
occasion-

mercury

tending

and
and

cathode

The

coated

Electrolytic reduction

and

removed

difficulties associated

process.

water.

of

mates
gold amalga-

; the

subsequently

technical

ordinary amalgamation
"

solvent

by distillation,leaving the gold.

several

are

as

which

mercury,

recovered

mercury

the

of mercury,

use

finely

of chlorine

sulphuric acid.
with

dissolved

the

in

metals

are

impure

electrolyte results.

great

addition
More

of potassium
by means
practice is the extraction
cyanide or potassium-sodium cyanide solution, in wooden

common

tanks

with

continuous

cyanide

solutions

solution

the

other

of

requires

agent according

is

gold

that

air.

The
dilute

in

comparatively rapid whilst

relativelyslowly attacked.

are

dissolution

solutions

of

compressed

advantage

the

possess

solution

substances

The

agitation by

the

to the

gold by potassium
presence

equation

of

or

sodium
or

oxygen

an

cyanide
oxidizing

88
"

4Au+8KCN+2H20+02=4KA.u(CN)2+4KOH
Furthermore,

by

the

of

sodium

use

the
of

slightly alkaline

peroxide

quantities is said
five times

velocity of solution

the

to

normal

or

rate

the

in the

greatly accelerated

medium.

potassium

increase

is

rate

The

addition

ferricyanide in
of solution

presence

of air.

to

small
four

or

ELECTROLYSIS

The

IN

solution
zinc-lined

be

course

boxes

sulphate
for

is
the

solutions

of

recovery

of

solution

be

can

least

instal.

0*9

the

Prussian

wide,

metre

cyanide

electrolyte

in

of zinc

handle,

to

The
and

iron

and

linen

anodes

long,

metres

2'i

bags

to

the

pensive
inex-

comparatively

from

iron

the

0*05

as

means

prevent
of the

action

anodically by the

on

low

as

thick,

mm.

weaker

is necessary.

cathodes

enclosed

are

formed

blue

is

lead

anodes,

to

advantages
much

Very

form

necessary

Sheet

The

employed.

and

several

strong

as

convenient

electrolyticinstallation

are

cess
pro-

deposition by

times

ten

gold is in
to

Siemens-Halske

used, down

for

been

have

ferrous

precipitationmethod.

cyanide

at

recovered

The

The

solutions

chloride

gold possesses

cyanide, whilst

cent,

per

for the

generally employed.

the chemical

over

whilst

cyanide

or

cyanide

the

ing
Leach-

chemically.

accomplished

shipping

71

from

chloride

for

used

for this purpose,

used

of

can

from

Deposition

"

Gold

of

Electrolytic Deposition

Solutions.

SOLUTIONS

AQUEOUS

contaminating

the

electrolyte.
The
o-oi

ampere

an

E.M.F.

100

per

4 volts,

3 to

sq.

above

5 volts.

divided

are

electrolyteat

an

30

feet

long by 6 feet by 6 feet,

compartments

top and

so

exit at the

cyanide rapidly dissolves

Auric
form

the

to

0*005

electrolyte is slowly circulated

The

vats

into

of the

usually from

applied voltage of
cyanide taking place with

with

cm.

decomposition

through large wooden

which

is

density employed

current

practicallycolourless

bottom
in

admit

to

as

of the
of

excess

complex cyanide

the

cell.

cyanide

to

"

Au(CN)3 +KCN$KAu(CN)4
The

complex
potassion and
dissociated

cyanide is dissociated

auric
the

complex

according

to the

anion

which

Au(CN)/4,

equation

into

in solution
is

again

"

Au(CN)'^tAu"+4CN'
As

in the

smooth

The

and

case

of

complex

copper

cyanides,

bright depositof gold is obtained

gold, averaging from

lead,is subsequently

to

recovered

12

per

cent,

very

uniform,

by this method.
in

weight of

by cupellation.

the

INDUSTRIAL

72
The

ELECTROMETALLURGY
of

disadvantages

inherent

in

the

of iron, and

by Prussian
lead

blue.

of this

process

According

unaffected
also

by

been

lead

removed

by immersion

Keith

cupellation.
In

the

used,

Haycroft

between

leaching chamber
finely crushed

and

the

leaching

the

ore

partly by

ore

The

experiments
mixture

of

substituting the
Efficient
of ICN
of

of

can

using
the

the

of the

anode.

not
29

anodes

iron

to

be

be

the

by

Coles

from

continuously removed

promising
cyanamide,

refractory magnetite

due

in the

the

the

use

for the

deposition
gold deposit is

electrode

form

formation

suggested

has

the

cathode.

as

to

electrolyte. The

easily detachable

the

electrolyte a

as

more

cathode

liberated

some

leaching chamber

Cowper

from

passed

calcium

and

gold is claimed

cyanide

have

to

by using

KCNS

and

of the

conducted

lines

the

by electrolysis

and

seem

has

of

gold is removed

action

the

slowly rotating aluminium

gold from

said

KI

carbon

solution
at

Clancy

Haycroft's

on

KCN,

and

does

process

electrolysis

mechanically stirred

The

by

formed

experimental stage.

is

brine

warm.

is

leach

base

the

at

amalgamation

direct

of

suspended in the roof

anodes

in the

kept

vat

auri-chloride

chlorine.

carbon

and

the

of the

electrolyzed brine

situated

cathode

mercury

sequent
sub-

and

co-deposition

being generated in situ by

chlorine

the

is

precipitation.
an

process

have

iron

the

on

be

to

carbon

lead

the

suggests

to facilitate

gold

and

mercury

foil and

of molten

bath

said

are

gold deposited

in

employs

modification

peroxide anodes

The

suggested.

in

sumption
con-

electrolyte

the

Andrioli

cathodes

electrolyte. Tin

the

of

Blount,

to

iron

and

the

material, the

contamination

the

peroxide anodes

anode

as

difficulties

the

are

process

iron

of

use

the

of

surface, and
ribbon

of thin

gold sheet.

Electrodeposition and Refining

of
electroplatingwith gold, as in the case
The

discussed, copper
the
the

uniformity
use

of

less than

and
and

complex electrolyte.
o*i

per cent,

gold

the

of
For

the

Gold.80"
other

is

In

metals

again taken
deposits obtained

zinc, advantage
smoothness

of

of

by

ing
electrolytescontain-

temperature

of

deposition

ELECTROLYSIS
should

6o"

lie between

than

more

electrolytes used

various

with

The

less

electrolytes for
The

"

of

excess

to

the

phosphate,

of

to

gether
to-

coloured

producing

cyanide

potassium cyanide

followingequations

the

formation

of auric

addition

the

on

contain

more

important

deposits.31
Electrolytes.
Cyanide
cyanide

deposits

matte

important complex
sulphocyanides, cyanide, ferro-

the

are

Reddish

C.

73

electrolytes should

gold.

chloride;

cyanide, and

"

70

Cold

cent.

0*4 per

SOLUTIONS

AQUEOUS

and

obtained.

usually

are

IN

complex

solution

taining
con-

place according

takes

:
"

Au(CN)3 +KCN^KAu(CN)4
KAu(CN)4^K+Au(CN)'4

Au~+4(CN)'
When

gold chloride

is used

electrolyte, primary
to

the

equation

as

the

decomposition

gold in

of the

source

the

place according

takes

"

AuCl3+3KCN=Au(CN)3+3KCl
1

Fulminating gold, Au(NH8)2(OH)3, is frequently

an
intermediary by precipitationwith ammonia
the

of chlorides

presence

proceeds

smoothly

according

to

solutions

the

formation

in the

to

as

avoid

solution

electrolyte. Anodic

potassium cyanide electrolytes,but

in

Jacobsen and

Cohen,32 in dilute sodium

is liable to

metal

formed

of insoluble

sodium

cyanide

passive owing

become

to

the

cyanide, NaAu(CN)2.

aurous

The

followingbath suggested by Roseleur

typical of the cyanide electrolytes:

may

be

taken

as

"

Ten

and

water

per
that

of

gms.

cent,

gold

mixed

with

pure)

in 750

boiled

this be

to 0*41

012

of from

27

to

gms.

c.c.

500 and

depositionis brought

about

100

before

sq. cm.,

optimum
6o"

by

c.c.

of

Langbein recommends

gold sheet,

per

in 250

potassium cyanide (98-99

of

hour

an

The

dissolved

are

of water.

of pure

ampere

4 volts.

lies between

20

half

densities,with anodes
from

chloride

as

use.

Small

current

usually employed
with a bath voltage

are

tion
temperature of deposi-

C.

Dipping

baths

the

insertion

of sheet

in which
copper

INDUSTRIAL

74
zinc

or

ELECTROMETALLURGY.
less

usually contain
the

concentration

Ferrocyanide
according

gold ions in

of

"

potassium' auric

place in

take

potassium ferrocyanide

crease
in-

to

as

following reactions,
of

the

gold salt

and

formation

the

from

complex

cyanide

so

solution.

the

The

Electrolytes.

Beutel,33

to

potassium cyanide,

"

HCl.AuCl3+K4Fe(CN)fl+02-"KAu(CN)4+KCl+KCN
+Fe7(CN)18+H20
His
to

numerical
doubt

cast

the

this

upon

The

place.
over

relationshipsare, however,
interpretationof

ferrocyanide baths

of

are

other

hand

not

addition

do

time

34

chloride, 90

equal
The

of

gms.

of

and

and

Chloride

**

improvements

used
are
are
10

as

anode

avoided.
amperes

volt.

of

gms.

addition

the

the

are

by

The

auric
of an#

solution

same

as

the

introduced

the

and

Bottger

and

is the
the

refininggold by

those

mann,36
Neu-

electrolyte

N.

Deutsche
certain

with

system

where

Philadelphia Mint,

gold containing both

material, and

employed,

for the

15*9

is necessary.

large

installed.

now

Crude

Tuttle

into

the

electrolyte, originally

This
studied

and

for

Hamburg
Dr.

readily and

per litre.

developed by Wohlwill,87

Raflinerie.38

plant is

of

densities

"

at

the

electrolytes.

suggested by Eisner

employed

use

on

hydroxide precipitateis filtered off.

Electrolytes.

was

longer exist.

no

chloride

auric

carbonate

current

for cyanide

methods

modern

so

ferrocyanide, with

ferric

temperatures

employed

of

the

potassium

the

gold anode

the

parative
com-

cyanide baths, but

the

time

to

the

advantages

as

recommends

amount

is boiled

dissolve

not

from

Pfanhauser

poisonous

so

With

advantage
their

of

account

on

purity.

cyanide preparation these

They

the

as

taking

reactions

the

formerly had

cyanide electrolytes
cheapness and

complicated

so

anode
The

The
per

leads

the

current
sq.

; the

platinum

large thin
of

being

sheet

gold wire

density employed

dcm.,

and

fall of

potentialover

up

electrolytecontains

to

30

about

is

palladium

and

gold cathodes

; soldered

is,for

amperes
the bath

the

per

joints
cathode

sq. dcm.

is less than

25 to 30 grammes

of

ELECTROLYSIS

gold per litre

IN

about

chloride, and

as

acid, the temperature

The

bath.

the

The

solution

aurichloride, which
to the

It is

equation

chloric
hydro-

500

at

jo".

to

anodes
some

small

uniform

the

ensure

+4CI'

chlorine.

at the

gold

of the

solution

The

excess

primary formation
anode probably takes

subsequent decomposition into auric chloride

its

is either

the

anode

very

small

redeposited on

crystals to the bottom

3 AuCl

is oxidized

according

hydrochloric acid in

free

chloride, AuCl,

aurous

+Au"

AuCl'^H-

pure

liberated

gold, which

and

to have

the

place, with

partial ionization

undergoes

electrolyteto
by

hydrogen

gold complex

the

"

important

in the

or

of free

3 per cent,

being maintained

contains

HAuCl^H-

as

75

deposit of gold is uniformly pure and both adherent

to
little gelatin is added
crystalline,especiallywhen
a

and

of

SOLUTIONS

AQUEOUS

of the

falls

or

cell

"

=AuCl3 +2Au

by the dissolved

chlorine

"

AuCl+Cl2=AuCls
thus

serving

diffuses
will be

anodic

an

into the

bulk

depositedin

of trivalent
the

as

of

solution.

of that

to the

demanded

would

from

recovered
the

by

be

slimes.

iridium

this process
The
solution
of the

goes

raising the anode

and

chlorine

York

into

are

of

not

are

electrolysis.
in the

recovered
are

refined

by

chloride

volts, indicating that

the bulk

potential of

solution

liberated

taining
con-

palladium

They

gold per week

in the

gold

when

in

trivalent

potential the gold is apt

will be

solution

Philadelphia alone.

and

E*=+i'i5

per

concentrated
sufficiently

conditions

chloride
of

ounces

solution

is about

the

silver

and

in New

anodic

gold

consequently

and

precipitation methods.

76,000

Over

Platinum

electrolytewhen

the

usual

from

obtained

cathodically deposited under

Osmium,

deposition

the

ions present ;

aurous

only the trivalent gold ions.

are

by

gold

cathode

the

At

amount

gold deposited is usually slightlymore

than

ampere-hour

of the

excess

gold due

weight

depolarizer. A

the

to become

state.

On

passive,

voltage has

risen

76

INDUSTRIAL

to

ELECTROMETALLURGY

volts.

+173

of the
When

Addition

anodes

said

to

the

be

of

use

chloride

from

internal

resistance

adhering

baths

of silver

amounts

in

present

are

is
alternating currents
good results, preventing the silver

been

The

bath.

subject

the

and

anode

the

to

of the

has

dency
ten-

asymmetric

with

attended

the

passive.

relatively large

the

iodide

become

gold to

ions lessens

chlorine

of

raising the

thus

of bromide

use

of

matter

few

and

early

patents.
Perkin
and
Electrolytes. Withrow,39
41
and Smith's
good depositswith Wallace

Miscellaneous
Preeble

40

"

obtained

modification

complex

of

electrolyte formed

sulphide

to

in

of sodium

excess

gold salt, or

utilizes

patent, which

Ruolz's

Von

the

on

of

addition

of auric

by the solution

the

sodium

sulphide

sulphide
"

AU2S3 +3Na2S^"2Na3AuS3
The

deposition of gold

that

of

antimony

only due
the

the

to

from

from

its

simple

followingscheme

this

electrolyte,if similar

complex sulphide (seep. 90),is

ionization

of the

salt

according

to
not
to

"

+AuS'"3
AuS'"8^Atr+3S"

NaaAuSa^Na
but

according

plays

Ost

to

important

an

Klapproth,42 the

and

r61e

sodium

sulphide

"

NagS^Na+S"
At

the

cathode

the

discharged

sodion

reacts

both

with

the

aurisulphide
"

Na3AuS3
and

assists

according

in the

to

the

at

into the

the

=Au

+3Na"S

intermediary formation

of

aurosulphide,

equation
"

Na3AuS3
whilst

+3Na

anode

+2Na

the

=NaAuS

sulphur
yellow polysulphide

converts

"

Na2S+S=Na2S2

+2Na2S
the

monosulphide

The

electrolysis is

tanks,
a

ft. 6

anodes,

filter cloth

Silver

foil

anode.

by

bags,
cathodes

The

usually

from

avoid

which

electrodes

which
are

of

the

prongs

plate,
off the

of

the
about

its

The

provided
current

the

from

at

each

density,

current

cm.

volts,

14-17

The

loose

feathery

detached

mechanically

the

bags placed

caused
in

and

agitate

of

silver
that

to

density

trays, allowed

the
the

roller

its passage.
of

fork
to

from
the

at

on

the

bottom

and

wooden

of the

placed

fork,
cathode

above

each

forwards, scraping

simplificationintroduced
distance

some

backwards

above

forwards

and

(Fig. 6b).
should

of the

drain,

employed,

of wood

are

form

rail

crystals.

usually

and

oscillate

employed

silver

surfaces

two

which

acidity

to

early

suspended

suspension

of

electrolyte,

backwards

run

crystals,
the

the
In

deposits

scrapers

scraped

caused

point

Dvftl of

forms.

two

consists

cathode

sq.

silver.

mechanical
to

crystals

in America

100

canvas

another.

one

distant

high

of
metal

in

6 in. from

4 per

dore

size, enclosed

in.

to

amount

The

used.

are

at

canvas

suspended by
and

varying

the

on

into

of which

was

cathode

per

be

for

The
serve

one

cent,

per

about

deposited

to

scrapers

vats.

also

and

6a.

Mechanical

the

lyte
electro-

inserted

charges

swept

are

as

in. in

12

amperes

have

Fig.

of

is

2-3-5

interest

crystals

by

are

silver

long, containing

slimes

separated

are

wooden

with

usually

in.

or

to

o-i

copper

ft.

acid

45

when

in.

and

deep

nitrate

in earthenware

conducted

of nitric

nitrate

copper

to

in.

mixture
silver

cent,

or

ELECTROMETALLURGY

INDUSTRIAL

78

not

bath
too

washed

contain
is

kept high

great,
and

no

are

melted

copper
and

removed
into

the
on

ingots.

IN

ELECTROLYSIS
The

black

pulverent anode

slime, if washed

practicallypure

gold, but

of

consists

of lead

traces

have

into

cast

of

employment

placed

anodes

separated

above.

The

from
is in

process

crystals deposited

on

elevated

scraping and

it

thus

slimes

for

moving

out

of the

is

of horizontal

placed

in Mexico.

cathode
bath

as

It

diaphragms

Monterey

the

cathode.

as

number

with

such

scrapers,

canvas

at

use

can

suggested

been

wooden

with

by

may

These

The

silver band

of the vat

the bottom

at

which

anode

electrolyticallyrefined

of the

moving

contain

to

copper.

plant have

of the

melted,

dissolution

acid.

and

anodes

elimination

the

to

and

with

the

of

process

79

and

is liable

pieces of

silver

treatment

Modifications

view

the

by

are

gold.
a

gold with

the

removed

small

or

during the

off

contaminate

treated

bismuth,

or

dropped

be

SOLUTIONS

AQUEOUS

The

removed

are

by another

by

travelling

band.

the

block

travellingsilver band

cathodes

amperes
to

100

per

with, but

the

without

are

densities

as

possible.

E.M.F.

of

1*2

been

used,

the

and

position
inter-

the

agitation is dispensed
from

down

time

time

to

simple,viz.
the

valuable

more

2
cases

separation

the

metals
than

to 3 amperes

volts
up

per
to

cell

locked

unsound
be

low

in the
current

than

in

maintained

100

per
are

up

low

copper,

practice must

current

silver

high acidity and

economically
in

of

electrolyticparting of gold and

in the

From

although in certain
have

for

more

to

electrodes

pressed

As, however,

even

r8-2

viz.

vat.

deposition,and

copper

high

are

is

Mechanical

practicevery

great deal

works,

higher voltage, 3*5 volts, owing

necessary

density.

current
vats

in

are

Mexican

replaced by graphite
silver crystals are
deposited.

the

crystals are

copper

any

between

conditions

The

at

cms.

of the

separated

density is employed,

slimes.

the

the bottom

silver

sq.

as

Moebius

anodes

in the

cathode

the

current

distance

greater
of

an

which

on

slightly lower

employed

are

of the

Horizontal

success.

diaphragms

by cloth

to

with

is worked

plant
but

modification

Balbach, U.S.A., Thum's

At

sq.

as

with

cms.

usually employed,

6 amperes

density'being

per

100

decreased

sq.
as

cms.

the

ELECTROMETALLURGY

INDUSTRIAL

80

concentration

of the

normal

volt

discharge potentials

of

potential voltage

of

is about

070

used

considerably

are

this

minimum

higher

In

the

contain
the

over

vats

30

are

deposition,

be

formed

place

while

white, but

addition

the

salts

as

of

of

nitric

(0*4 per

the

small

in
made

acid

and

of

partly
silver

addition

in
of

of

with

iron

the
is

tities
quan-

deposit.
are

not

oxide

size

this

by

the

addition

the

the
rich

deposited
in

copper

electrolyte

spent

copper

taking

partly destroyed

in

become
the

ion

corrects

in

it is

removed

may

unstable

an

up

which

spongy

alcohol

as

anode

an

small

gelatine, but

removal

deposition

reduced

day,

adherent

deposited

are

electrolyte has

the

of

of

ampere

an

even

of

be

can

every

Subsequent

chemical

formation

quantity

o*8

nitrate

of

formation

10,000

cent.), the
by

of

is necessary,

of the

presence

anodes

used, but

are

ammonia

any

volts.

the

as

acid

crystals which

to

be

the

recovered

in

crystals

part

When

or

silver

Large

chloride.

The

due

gelatine must

silver.

be

the

dulled

tendency.

by

acid, to

salts results

Occasionally

of

nitric

free

neutralize

cathode.

the

at

addition

of

The

1*35

where

behind

remains

gold

and

obtaining

by the possible reduction

of basic

the

the

paid

to

volt

0*5

deposited.

density

current

is

addition

cent,

per

low

slightly

nearly

diaphragms

no

silver,

the

to

therefore

mints

the

gold,

attention

The

skeleton.
to

at

in

out

cent,

per

run

dcm.,

sq.

per

carried

processes

being approximately

1*28

between

solution

electrolytes

the

be

to

position
decom-

nitrate

raised

be

can

lies

operating voltage

is

the

The

respect

voltage

commencing

copper

any

usual

volt, and

070

in

normal

"0771

between

normal,

than

decomposition

than

without

and

o*i

and

silver

practice

in

taining
con-

discharge

the

volt.

0*5

normal

weaker

ion

difference

nearly
a

solution

"0*324

are

since

volt, and

between

silver

being

there

In

silver

normal

and
and

copper

respectively,

two

ion

cupric

potentials of the

salts increases.

copper

or

copper

can

precipitation
by

lysis
electro-

usually employed.

ELECTROLYSIS

IN

SOLUTIONS

AQUEOUS

81

Shaver.
The

application of
from

the

of

the

processes

of

one

wet

of silver from

electrolyticrecovery

received

of

methods

of scrap iron
day economic

usual

leaching agents

silver

extraction

does

deposition
employed in the

not

conditions

have

precipitationby
that

shown

have

to

seem

means

being usually employed.

copper

or

by the

ores

electrochemical

attention, chemical

any

its

the

Present

electrolytic

in certain localities,
be remunerative
winning of copper may
of silver would
and
the electrolyticrecovery
probably be
favourable.

even

more

leach

would

probably

in

As

offer several

together

containing

anodes
whilst
cent,

the

York

New

gold, 60 'per

many

Co.

cyanide

silver

is

"

practised
containing gold, copper
minor
impurities. The
crude
silver
Pittsburg use
now

at

lead, bismuth

per

cent,

and

Philadelphia refineries

cent,

material.

anode

with

Lead

Pennsylvanian

gold

silver

extensively, utilizing crude

lead

of

case

advantages.

electrolytic refining of

The

and

the

silver,and

10

per

cent,

and

copper,
30

use

base

per

metal

Electrolytic refining could

possibly
for cupellationof the zinc-lead-coppercombe substituted
plexes
obtained in the various processes for removing silver
The
from
lead.
parting of gold and silver as well as the
in the refiningof silver
practical conditions to be observed
as

from

nitrate

electrolyteshave

already been

discussed.

The
nitrate electrolyte
Silver.
Electroplating with
is unsuitable
for electroplating
; the depositis macrocrystalline
and spongy,
of a suboxide
probably owing to the formation
46
due to the absorption of oxygen.47 The
or
deposit
be improved by rapidagitationor rotation of the cathode
can
"

as

by Sand48

shown

silver

purposes

the

addition

of

as

or

plating.
Cyanide
Iy.

by

suggested by Kiister,60 or by the addition of

quantitiesof colloids such as gelatine. These improved
good for silver refining
deposits,although sufficiently

alcohol
small

Snowden,49

and

even

for

electroanalysis,are

Electrolytes.
"

The

cyanide

not

suitable

complex
6

for

silver

ELECTROMETALLURGY

INDUSTRIAL

82

electrolyteis probably, in
gold, the

suitable

most

Dissociation

in

with

common

electrolyte for silver

and

deposition.

according

electrolyte proceeds

the

of copper

those

the

to

followingequations :

"

AgN03+KCN=AgCN+KNOs
precipitate of

The

cyanide

form

to

is dissociated

cyanide

silver
soluble

the

is soluble
silver

potassium

in

of

excess

cyanide which

"

Ag(CN) +KCN"_KAg(CN)2

KAg(CN)2";K+Ag(CN)'2
Ag(CN)'2$Ag+2(CN)'
of the

The

presence

the

silver salt

influence

1840, and

of the

nature

originallyby

oxide, used

due

A.

of silver have

carbonate

investigatorsinsist on
silver cyanide from
insoluble

all been

is

to

apt

10

uses

give the deposit a

of

gms.

silver

primary separation of

the

soluble

cyanide per litre. With

density of 0*3 ampere
heavier

For
with

40

current
"

coats

good

electrodes
100

per

he

gms.

cathode

the

1*25,

chloride,

of chlorides

of

20

gms.

potassium

apart and

cms.

current

the

potential drop
good deposit is obtained.
cms.

gms.

cyanide

of

silver

chloride,

as

litre and

per

the

same

density.
work

"

baths

such

as

for

giving

steel

are

electrolyte contains

hydrogen. Foerster
without

about

and

Namias

62

of any

coat

in

of

silver

A
brisk

thin

weak

gms.

litre.

ensure

of silver

very

1*5

per

the presence

suggests 25 gms.

preliminary

generally

of

cyanide baths
former

of

use

the

and

sq.

potassium cyanide
density should be employed to
70

making up

Pfaunhauser

10

suggests 25

potassium

gms.

Striking

certain

salt

the

structure.61

coarse

being about

the bath

across

the

chloride

as

whilst

advocated,

beyond certain limits the presence

that

of

considerable

the

electrolyte. Langbein advocates

states

decomposition

deposit,the nitrate,chloride,
H.
Elkington in Sheffield in

"

other

but

the

to

by the potassium cyanide has

the

on

salt formed

high

silver.

advocated

cyanide and

with

current

evolution

neutral

for

of

double
salt.

25 gms.

The
pure

ELECTROLYSIS

potassium
ampere

100

of

use

sq. cms.,

with

addition

agents

obtaining bright

SOLUTIONS

AQUEOUS

litre,using

cyanide per

per

The

IN

of

instead

of

P.D.

density of 0*3

current

83

volt.

cyanide electrolytes for

to

deposits

matte

is very

usual,

nished.
cannot
easily be burespeciallyfor plating articles which
Carbon
disulphide has been used as an addition
should
exceed
not
quantity added
agent since 1847. The
2*5 parts per 10,000
and

but

chloroform,
of

The
a

time

to

or

suspension of

addition

of these

use

of the

particularcase

agents

glue, linseed oil,mucilage

Miscellaneous

of

the

used,

These

they do

as

Some

silver in

potassium ferrocyanide, 56

litre of water.

been

suggested.

dissolve

of

to be

such

as

have

of

8*4

ammonia,
been

not

gms.

and

extensively

silver anodes

the

earlier

the

solution

of '88o

gms.

solutions

not

The

collodion.

ferrocyanide electrolytes.

of

use

of

7 gms.

gested
sug-

gelatine.

or

"

dissolved

63

Eisner

and

protectivecolloids

Electrolytes.

advocate

experimenters

been

brighteners appears

as

of

action

normal.

more

sulphur and
sulphidehas also

silver

'

important
guttapercha in

the

of

mixture

be avoided,

have

agents

iodine

or

should

little higher than

amongst

iodine

mentioned

be

may

time

be

addition

effective

less

from

use

density should

the current

Other

agitation of the bath

in

regular

manner.

Krutwig
a

silver

64

the

reducing agent
phate is

deposited from
electrolyte provided that rapid

such

not

so

as

efficient

acid

sulphurous

be

The
or

presence

sodium

organic acids such

Various

citrates

could

ensured.

electrolytewas

necessary.

acetates,
are

silver

that

hydroxide ammonia

agitationof

but

claimed

have

of

thiosul-

as

the

tates,
lac-

subject of patents,
the cyanide electrolytes already

as

been

the

discussed.
IvBAD.

The
The

common

lead

ores

consist

containing varying
the

and

Electrolytic Recovery

usual

thermal

of

amounts

treatment

the

Refining of Lead."
lead zinc sulphide complexes
of

gold and

sulphide

ores

silver.
are

In
first

ELECTROMETALLURGY

84

INDUSTRIAL

roasted.

actions
During the process of roasting two series of reproceed simultaneously according to the equations
"

2PbS+302=2PbO+2S02l
PbS+PbS04
PbS +2PbO
"

If the

general procedure

side reaction

Roastin_

takes

of

also

to

The

obtain

small

-" CaS04+PbO

is

the

oxide

an

reduction, and

of easy
ensures

an

treatment
would

be

metal

and

hydrogen

quantity of gold.
which

process

lead

of

formation

easy

ore

and

that

the

could

the

It

since

one,
are

is then

described

roasting and

sulphide
low

from

in which

of

will be

economical

the

removal

of the

the

compete

direct

later.
to

heats

of

low, permitting

melting-point of
furnace.

mitted
sub-

reduction

Any
with

the

metal

electrolytic
this process

production of
the other by-product sulphur, either as
ensured
sulphide or sulphur dioxide, was
one

further

"

thermal

crude

oroCesses
Processes.

place

refining processes

purely

Reductl0n

adding lime be followed

PbS04+CaO

Frequently

orocesses
processes.

} Koasung
1 Redllction

=PbS04
=2Pb+2S02
=3Pb +S02

PbS+202

the
such
with

pure
or

as

the

86

ELECTROMETALLURGY

INDUSTRIAL
lead

sulphate,both metallic lead and

possibilityof casting it directly into anodes
to the

Burleigh

67

concentrated

can

E.M.F.

impressed

an

Refining

Lead.

of

in the

be recorded

lead several schemes

lead

deposition of

soda, where

with

The

have

economical

of recent

to

nickel
and

is removed

antimony

by

surface

and

of

recovery

much

now

more

refining

Parkes

or

the

bulk

ments
improve-

various

is subjected

lead

crude

of the zinc, iron, and

by introducing air,forming
of lead, which

removed.

are

progress

injection,whilst the tin, arsenic,

steam

antimonate

arsenate, and

nate,

The

removed

are

for the

it is

that

process

oxidizing melt.

an

tained
ob-

be

much

not

PattinSon

the

Pattinson

the

In

processes.

in hot

ore

could

lead

years

the process

either

than

roasted

suggested for refiningthecrude

been

modified

so

Although

"

presents itself.

volts.

of 17

electrolyticprocess

and
electrolytically,
have

of the

suggested the solution

oxide, the

lead

to

come

the

crystallization

fractional

On

stan-

tains
copper-lead alloy which conarsenic ;
the rest of the nickel, cobalt, sulphur, and
removal
of the bismuth
is never
complete. In the Parkes
to the partiallypurified
desilverizingprocess zinc is added

the

first fraction

molten

consists

lead, when

solidifies

surface

alloy is removed

During

the

(over

12

litharge by
on

the

air blast,

an

cupel, the

oxide

For

cent.

ton) the whole

per

oz.

per

distillation.

by

quantity

small

leads

of the lead

of silver

rich in silver

very

be removed

can

again reduced

being then

as

gold behind

leaving the silver and

lead

solidified

The

lead.

removed

of distillation

i\

to

zinc

the

which

silver is formed

molten

of the

and

process

is also lost up

alloy of gold and

an

the

on

of

to

metal.
The
that
the
lead

earliest

of Keith.
slimes

Crude

in

used

were

deposited on

the

thin

which

the

bottom

fused

fell to

together.

sulphate and

150

The

in

sheet

in muslin

sodium

cathodes

lead

of the

cell and

of

sodium

20

per

gms.

or
was

crystals,

removed

were

acetate

acetate

small

as

was

retain

to

Lead

acetate.

electrolyte contained

gms.

bags

electrolyte of lead

an

dissolved

sulphate

anodes

lead

refining lead

for

electrolytic process

and
of lead

litre.

The

ELECTROLYSIS

100

per

at

cms.

sq.

rotating cathode
rotations
100

per
on

each

on

to

side of the

at

the

most

Crude

by

performing

density of 72
By

amperes

of scrapers

means

crystals could

drained, washed

successful

removed

be

fused with

and

is melted

is cast

with

separated from
cathodes

when

feet 6 inches
with

each.
amperes
to 0*42

the

and

The
per

next

anodes

$nd

volt, the E.M.F.

anode

by

sheet

lead

hold

not

when

are

cms.

thick

feet

long,

of wood

deep, made
and

anodes

the

they still retain

cathodes

21

0*9 to

essentiallyof

solution

nearly

are

original form.

their

fluoride in free fluosilicic acid, first

2*2

of lead

pletely
com-

The

silico-

suggested by I^eucks.60

hydrofluoric acid is repeatedly filtered

lead

fluosilicic acid, until

100

12

over

cms.

the

and

dissolved

per

of 11*3

distance

anodes

22

Even

through quartz, and

75

top in size. Each

weighs about 170 kilos,being

anodes.

cent,

by

75

applied E.M.F. from 0*15

gradually risingas the slime adheres

sq. cms.,

electrolyte consists

of lead

about

density employed varies from

current

Thirty-five per

said to be

the

at

cms.

3 feet 6 inches

wide, and

bitumen,

Chicago,

be

may

electrolytic tanks

The

100

into

cast

3*8

to

refined

are

finished.

lined

England, and

lugs and

the

Trail, B.C., near

at

use

electrolytic lead- refiningprocesses.

of

extending

cms.

The

is in

process

Newcastle-on-Tyne,
lead

anode

68

Betts

and

to

lead

axis

disc of

bronze

horizontal

ampere

employed

aluminium

an

employed.

to be

0*35

Tommasi

current

disc the

to

0*2

87

little charcoal.
The

be

sieve conve}'or

on

could

cms.

of

mounted

from

volt.

05

form

minute.

per

sq.

to

0*4

in the

diameter

3 metres
2

varied

density employed

current

SOLUTIONS

AQUEOUS

IN

is added

carbonate
solution

the

ing
result-

contains

of free fluosilicic acid.

gms.

the

to

60-90 gms.
The
optimum

300 C. and 350 C.

temperature lies between
Pring 60 gives the following suitable electrolyte:
"

H2SiF6
Pb

as

PbSiF6

Sp.gr.
has

been

colloid

such

It

glue

necessary
or

9*5-10*5

4'5-5'2

per

cent.

per cent.

113-1-16

..

..

found
as

to

add

gelatine not

small

exceeding

quantity
0'i

per

of

cent.

88

ELECTROMETALLURGY

INDUSTRIAL

1/5000. Owing

generally about

and

it

anode, where

the

0*007

of

cent,

Per

followinganalyses
slimes

prevents the formation

additions

small

frequent

its destruction

to

typical of

and

deposited lead

the

The

day.

other

every

peroxide,

Trail, B.C.,

At

necessary.

are

glue is added

are

of lead

at

the

"

Impurities

in the

Cu

0*0010

Bi

0*0022

Slime.

lead.

Pb

per cent.
"

As

0*0025

Sb

has

Betts

addition

glue and

resorcin, and

47
25*32

As

44*58

Bi

0*52

Cu

9*3

"

suggested the

to

Ag
Sb

"

0*0017

gelatine,such

as

anodic

saligenin,including

agents in

addition

of other

use

cent.

10*3 per

pyrogallol,phenol,
depolarizerslike

sulphurous acid, hydroquinone, and

o.amidophenol. The
61
Senn
current
yield is said to be from 85 to 90 per cent.
and

62

Kern

confirmed

Fischer, Thiele
with

and

the

Maxted

utility of
63

also obtained

electrolytes,in addition

other

salts,have

been

suggested and
Siemens

patents.

numerous

the

use

and

an

of lead

fluostannates.

as

accumulator

Hagener

an

works

fluosilicic acid

subject

Halske

and

perchlorate containing

organic colloid

to

the

are

patented
perchloric acid

It is said that

using this

large scale.

and

other

been

vegetable mucilages have

the

electrolyte on

Peptone appears to be the best addition

for perchlorate baths, although mucilage, albumen,

of

matter

have

free

electrolyte.
are

deposits

good

fluosilicates,
fluoborates, fluozincates, and
Various

electrolyte.

Betts'

patented

agent

salep,
by the

firm.

same

suitable bath
Pb

found

was

as

in

electrolytecontaining

an

perchlorate, 5 per

cent.

HCIO4, 2-5 per cent.

Peptone, 0*05 per cent.
A
of

current
0*21

density of 2-3 amperes

with

deposits with

electrodes
a

current

2*5

cms.

per

sq. dcm.

apart,

efficiencyof

over

gave

at

solid

99 per cent.

voltage
smooth

ELECTROLYSIS
Mathers

IN
Overman

of merit

to be

and

agents in order
Clove

oil

100

Peptone

c.c.

found

89

SOLUTIONS

AQUEOUS

suitable addition

the most

"

of lead

ton

per

350gms.

deposited.

"

Phloridizin.

Snowden
cathode

high speed and

at

investigated, but

solutions

not

are

already

have

of

been

slimes

the

refining plants. The

antimony, with smaller

adopted

per cent.

the

slimes

contain

traces

solution

the

by

with

anodes
been

and

tellurium.

One

this
with

water

slimes

the

thus

copper
Other

and

chlorination

most

is the

The

slimes

are

and

weak

are

boiled

recovered

details

then

are

From

and
such

methods,

fractional
or

and
the

the

gold
as

traction
ex-

antimony

residues

casting the

of technical

suggestions.

are

electrolyticprecipitation,
slime

electrolytic treatment,

subsequent

about

of air.

removed

one

hydrofluoric acid, to which

processes

of these

and

removed

potassium fluoride
electrodeposition,whilst

majority

of the

complex

in the presence

with

antimony

suggested, but

for the

iron, silver, and

90).

p.

residue.

amalgamation

arsenic, and

of copper,

sodium

added

to

silver
the

of the

subjected

is

sulphuricacid

from

recovered

not

satisfactory

the

sulphide solution, containing

Antimony

Na^

with hot

recovered

protection

as

lead,

of acid

last traces

electrodeposition (see

is then

the

electrolyticlead-

in the

recovered

sodium

cent,

in

encountered

dealing with
After
washing

the

remove

6 per

leached

from

electrolytes has

above

of

Trail.

at

alkali to

by

oxalates,

electrolytes

the

lead

with

the

rarely bismuth, gold, and

satisfactorymethods

and

as

expectation.

Difficulties
treatment

with

corrosion

to

up

from

those

as

metals

electroplatingof

against acid

in

gelatine

solutions

lactates

enumerated.

The

more

of nitrate

as

of

cent,

per

depositsobtained

the

good

as

o*i

using

by

process

use

complex electrolytes,such

been

come

Tommasi

the

electrolyte. The

acetate

as

have

modified

rotating

in the
well

66

working

have
are

into
all

lacking

ELECTROMETALLURGY

INDUSTRIAL

go

Antimony.
The

electrolytic deposition of

developed
As

on

technical

sulphide
with

is used, the

the

divided

cell

used, the

was

the

circulating catholyte

the

anode

slimes

lead

cell is
to

be

and

are

used

With

with

dcm.,

is

deposited as
deposited metal

The

of soda
the

anodes

6o"

C,

dull warty

A 6 per cent,

solution

as

follows

sulphite

about

an

practically
3

mm.

melting under

by

per

amp.
and

thick.
flux

effectuallyremoves
ingots showing

into

crystallinestructure.
of sodium

electrolyte; antimony

solution

divided

volt

antimony

sheet

is removed

stellate

sodium

of about

placed,

is allowed

density of 07

current

of

to

in

Trail, where

sulphide

potassium sulphide,which
of sulphur, and
traces
cast

the characteristic

sulphideis used as
pentasulphide dissolves

solvent
in this

"

SbgSg +3Na2S
which

sodium

lead

At

are

antimony, the

and

last

and

of

applied E.M.F.

an

electrolyte temperature
pure

salt solution.

the

at

anodes

carbon

from

iron cathodes, whilst

source

and

original process

the

sheet

a
a

dispensed with,
partiallyoxidized

sulphate.

sq.

as

leached

being deposited

where

from

sodium

antimony
on

compartment
is liberated

chlorine

antimony

of

electrolyte. In

spent

Halske.

and

sulphide in
antimony sulphide ore being

solution

electrolyte a

b}r Siemens

scale

been

has

antimony

partiallydissociates into

=2Na3SbS4
the

following:

"

NaaSbS^Na+SbS*'"
Since the

complex SbS'"*

is not

readily dissociated

again

"

SbS///4$Sb-+2S'+2S,/
the

equilibrium

antimony

of

Sb""

ions

in

per

cent,

solution

of

sodium

sulphide being only io~60w (EaSb/N.Sb"*

==-0-463, whilst EASb/"Sb- in
Na2S=+0709
volt).
Ost and Klapproth 87 assumed
that the depositionof antimony
was

caused

of sodions

by the secondary reaction

at the

cathode

as

follows

5Na +Na2SbS4

=Sb

caused
:

"

+4Na2S

by the discharge

ELECTROLYSIS
Whether

the

antimony

or

is

always

by

electrodepositionof

direct

91

secondary decomposition, there

sulphur. Free sulphur

the polysulphide"

liberation of free

anodic

an

with

reacts

is

mechanism
is caused

SOLUTIONS

AQUEOUS

IN

sodium

sulphideto

form

NajS+S^NaaSg
which

diffusion

on

to form

thioantimonate

2Sb

Consequently only
in

the

to

antimony

will dissolve

cathode

"

+3Na2S2=2Na2SbS3
low

single cell process

sulphur depolarizeris

such
added

efficiencylying between

efficiencycan

current

45

is used

as

claimed

be

Trail, unless

at

electrolyte,the average
the
Among
50 per cent.

the

to

and

important sulphur depolarizerswhich have

technical
mentioned
be
application may
sulphiteand potassium cyanide

not

more

yet

ceived
re-

sodium

"

Na2S2 +Na2S03
NagSa +KCN

Experiments

in addition

on-Tyne

in

potassium

is

sodium

use

of acid

the

ferric salts

more

antimony

trifluoride

in
w

=KCNS

with

conducted

sulphides. At Newcastlesolution
of the
a
deposited from
68

Betts

has

containing

suggested the

salts in

containing iron

divided

generated #nodically being used

from
the

ith the

lytes
electro-

other

alkaline

fluoride.

solutions

found

+Na2S
+Na2S

electrolyte of hydrofluoric acid

an

and

been

the

to

antimony

fluoride

were

also

have

=Na2S208

the

mixtures
addition

slimes.
of

electrolytes

trichloride

antimony

of ferrous

dissolve

to

Successful

cell,

and

chloride.

sulphate or

Bismuth.
The

technical

of
electrodeposition
successfully developed on
a
large
in
electrolyticpotential of bismuth
lies

its ions

evolution
to

the

considerably below

should

tendency

solution
conditions

commence

for this element

hydrogen, evolution
bismuth

Ea=

is

scale.

form

been

Although

the

in

where

containing
hydrogen

complex

is unavoidable.

deposited,either

not

volts, yet, owing

0*393

to

has

solution

point

the
"

bismuth

Under
spongy

salts in
these

condition

ELECTROMETALLURGY

INDUSTRIAL

92
or

closely adherent

as

efficiency.Foerster
good
nitrate

is

from

be eliminated

if

divided

cell

anodic

depolarisationunder
carefullyregulated terminal

potential

deposition.

the

possibfy

potential could

cathode

the

tartarate

cathode

the

carefullyadjusted continuously during

regulation of

sodium

from

depositsmay be obtained
solutions provided that

oxalate

The

Sand70

solutions.

Excellent
and

obtained

have

to

electroanalytical work

for

deposits suitable

current

solution, whilst

fluosilicate

low

very

claim

6g

Schwabe

and

deposits from

obtained

crystals, with

used, in which

were

density and

current

constant

voltage could

constant

maintained.

be

Tin.
There

has

winning

the

methods

been

and

tin.

refiningof

The

sufficientlysimple and

are

=233" C), and the impurities in

antimony, and iron, with but small
not

to

warrant

have

Fusion
soda

have

become

not

be mentioned

may

economical

tin, chiefly lead,

crude

solution

Leaching
(B)

soda

become
led

to

for

the

an

i'5 per cent.,

which

to Goldschmidt's

the

ore

with

electro-

and

water

caustic

process.

subsequent
sulphur and
and
electrodepositionfrom the thioaccording to Claus's process.
soda

caustic

and

(A)

"

soda

leaching

Alkaline

containing sodium

with

sulphide.

sulphuric,hydrochloric

of

acid

solutions.

recovery
an

the

leaching with

ferric chloride
The

to

Various
traction
exprocess.
subject of patent literature,

(A) Fusion of
leaching with

"

Processes.
or

Acid

technically successful, amongst

subsequent

stannate

gold,

of silver and

traces

"

deposition,according
with
(B) Fusion
leaching with water

caustic

been

Processes.

and

Sn

(m.p,

electrolyticrefining

an

processes
but

metallurgical

usual

sufficientlyvaluable, totallingonly

are

for

devised

electrolytic process

no

of tin from

important
of

iron

electrochemical

investigation into
deposition

scrap

tin.

the

most

Although

plate has, however,

industry, and
suitable
the

has

conditions

Goldschmidt

INDUSTRIAL

94
the

divalent

the

oxygen

ELECTROMETALLURGY

alkaline

liberated.

alkaline

solution

stannic

hydroxide;

is

raised

being anodically

Tin

owing

becomes

this

when

of Sn",#

reduction

anodic

evolution
before

Sn"

place.
favours
agitation of

Gelstharpe 74
the
reduces
applied E.M.F.
by about

volt.

0*5

than

Sodium

dissolved.

advocated

potential
of

oxygen.

deposition does

addition

(2) Borchers'

Process.

containing 15 per

cent,

sodium

as

and

Keith

chloride

Borchers

deposition

advocated

the

electrolyte. If

is added

iron is also

cyanide have

unsatisfactory results.

proposed

chloride

sodium

76

sodium

as

agents with

"

and

alkaline

well

as

which
electrolyte,

the

stripping

the

to

of sodium

nitrate

as

76

chloride

cent,

3 per

for

Borchers

of sodium

addition

been

film of colloidal

the

the
to

by

to take

appear

more

of

occurs

cause

oxidized

readily passive in

formation

to the

sufficientlyto

Cathodic
not

stannite

and

electrolyte. With

electrolyte

an

of

cent,

3 per

temperature of
500 C. and a P.D. of 2-3 volts per cell,tin could be effectually
density of 0*5 to 1*5
stripped and deposited with a current
stannate

per

amps,
for the

100

same

sq.

thiostannate
per

Process.

electrolyte,a solution

As

of free caustic

current

warm

bath

density of 3-4

impurities except
Steiner

78

amperes

arsenic
advocated

the

tin

cent,

per

and

place

iron cathodes

sheet

100

per

antimony

and

of sodium

Electrolysis takes

soda.

electrolyteat 8o" C. with

slimes.

"

used,77 containing 4-5

was

cent,

in

fluoride

purpose.

(3) Claus's

10

advocated

Luckow

cms.

sq.

of

All

cms.

removed

are

addition

and

as

of

cent,

per

flowers of
B.

sulphur to the electrolyte.

Acid
Electrolytes.

(1) The

Neil

Brown

and

Process.19

stripped in boiling ferric chloride

equation
2FeCl3 +Sn-"2FeCl2

"

The

solution

is

scrap

tin

according

plate
to the

"

The

disadvantage
of iron
is

through

during

circulated
the

of this
the

process

period

through

cathode,

then

+SnCl2
is the

of immersion.

divided
back

tion
solu-

simultaneous

cells

The
of

through the

lyte
electro-

concrete

anode

first
com-

ELECTROLYSIS
The

partments.

graphite

the

IN

tin is

cathodes

cathodes

anodes

SOLUTIONS

AQUEOUS

separated from
diaphragms. At the

sheet

are

tin, and

earthenware

by

95

deposited
"

Sn"-"Sn+2"
whilst

anodes

at the

ferric chloride

the

is

regenerated

"

2FeCl2 4-2C1'=2FeCl3 +20

Provided

that

economical

sulphate

as

sulphate is reoxidized

ferrous

as

follows

"

cells

be

more
80

uses

used, but the

not

are

nitrate.
tetrachloride

tin

tin

without

Hemingmay

Cold

Bergsoe Process.
stripping solution, the

would

process

by sodium

(2) The
used

stripped

be

one.

Divided

leach.

this

iron

Goldschmidt

the

than

could

plate

of

solution

simultaneous

ferric

tin

the

going into

is

solution

as

"

SnCl4+Sn-"2SnCl2

is open

the

to

solutions

electrolytewith

as

of the

Solution

chloride.

the

tin

Brown,
the

proceeds

both

stripping cell,
subsequently removed

electrochemically in the
in

tin

is

solution

utilizing graphite anodes.

amperes

per

100

sq.

with

acid

containing

with

current

is

carried

Gelstharpe82
Manchester

cms.

a
a

1*25

per

trace

of

cent,

suggested the

of

sulphate. A good depositwas

of

02

to

03

ampere

per

the

in

of

excess

separate

cells,

to

experiments

solution

of

acid

as

amperes

per

100

efficiencyof

addition

chemically and

sulphuric

density of 17

current

stannic

of ammonium

and

successful

out

suggested by Smith

claiming a

and

employed.

practicallypure tin sponge

stripping and
Sulphuric Acid
been

the

Rienders81

density of

current

i'5 volts

have

tin.

addition

the

process

namely

chloride

stannous

on

The

used.

are

with

iron

of

experiments

conducted

anodes

objection as

same

solution

simultaneous

acid

graphite

and

cathodes

Tin

could

be

at

hydrochloric
electrolyte;
sq.

cms.

at

obtained.

depositing electrolytes

and

Englehardt,83 the latter

over

60 per

small

Nauhardt

quantity of ammonium

obtained

sq. dcm.

cent.

with

current

density

Quintaine84 deposited tin

ELECTROMETALLURGY

INDUSTRIAL

96

used

85

Nodin
sulphate solution on lead cathodes.
by
sulphuric acid as a stripping agent, followed
depositionin separate cells on the basis of the Neil and
from

electroBrown

process.

Miscellaneous

C.

86

Matuschek
in

dissolved
as

agent
of

ioo

NaH2P04

suggested the
Mennicke

obtained

tin

and

10

with
per

conducted

was
ioo

sq.

that

the

two

metals

with

density

current

of

iron

the

Hollis87

electrolyte.

deposition

for
10

of

cent,

per

Electrolysis
i

per

ampere

The

of the

referred
than

of
is

tin

solution

simultaneous

the

unsuitable

more

junction

the

whole

already been

even

dioxide, and

carbon
at

their

from

practice

alloy formed

dissolved.

has

in

atmospheric

tin

is not

strippingagents

these

suitable

hydrochloric acid.

electrolytes suffer

which

iron

the

conditions

by acid electrolytes,but

removed
of

as

as

quantity

small

suitable.

most

the best

free

instabilityin presence
fact

be

to

cent,

alkaline

the

and

gum,

high

as

colloidal addition

some

electrolyte containing

an

Good

20" C.

at

cms.

The

Tannin,

that

observed

88

provided

of tin fluosilicate

use

chloride

densities

current

at

stated

were

oxalate

depositing electrolyte.

sq. cms.,

employed.

of ammonium

use

of tin ammonium

solution

obtained

be

per

were

were

suggested the

stripping and

deposits could
3 amperes

has

saturated

suitable

Electrolytes.

renders

to

the alkaline

ones.

Tin
with

are
Plating. There
electrodepositionof

the

deposit.
of

excess

the

deposited

before
the

and
the

must

complex

of
be

the

on

to

irregularly in

the

deposithave
a

adherence

ensure

employed,
are

and

found

as

thin

loosely

cleanliness

of

to be taken.

copper

of the

Very

suitable.

deposit

tin, due
low

electrolytesthose

most

the

but

cathode,

regards

as

alloys, CugSn, Cu^n.

ions

adherent

dense

dissolve

generally given

are

tin coat

white

associated

generally dull, powdery, and

is to receive

steel

formation

densities
form

which

as

anodes

Special precautions

surface
Iron

is

the

tin

deposited

amount

metal

adherent.
the

only do

Not

difficulties

many

"

For

to

current

which

good

ELECTROLYSIS

IN

electrolyteare

be

obtained

deposit with

fine wire

60
a

dissolved

of caustic

100

sq.

soda

20

gms.

of caustic

good depositsmay

cm.

and

potassium cyanide
World90
the following
brass

iron

and

are

"

Brass

"

Gms.

per

KOH
"

"

"

"

75

"

"

KCN
Brass

(2) On

350
or

Steel

"

KOH

SnCi2

"

"

"

"

"

"

"

"

"

"

"

"

"

15

"

"

"

15

KCN

35

It is recommended

bath

litre.

7-5

SnCl2

ampere

Steel

(1) On

with

O'l

of

electrolytesfor giving good deposits on

stated

potash forms

obtained.

be

Brass

the

containing

density of

addition

the

electrolyte. In

the

to

litre of water

current

of

grammes

in

or

recommended

Eisner89

time

brush.

suitable electrolyte. With

per

at

to

of

depositscan only
high speed or by
and scraping the

"

chloride

gms.

time

97

circulation

Electrolytes. Twenty-five

Alkaline
stannous

cathode

from

electrode
a

Thick, dense

rotating the

by

the

removing

essential.

efficient

and

deposition high temperatures

the

SOLUTIONS

AQUEOUS

to

use

voltage of

2'

the solutions
5 to 3 volts.

and

warm

electrolyze
surface

large anode

is desirable.

Acid

Electrolytes.
"

The

in acid solution

of acid oxalates

use

form

the basis of

and

great

phosphates
pyro-

number

electrolyte
electrolytes for tin deposition. Roseleur's
is the most
generally used, and gives satisfactorydeposits.
of

employed, and the electrolyte

containing 125 gms. of sodium pyrophosphate and 1*5 gms.
chloride
Field 9l
be kept hot.
of stannous
per litre must
oxalate bath of the following composition :
mentions
an
Pure

tin

anodes

must

be

"

Grammes

Stannous
Acid
Acetic

chloride
.

ammonium

25-30

55-65

oxalate

acid
.

*""

per

litre.

3-4

ELECTROMETALLURGY

INDUSTRIAL

98
The

is

bath

density of

conveniently worked

ampere

tartaric

Kern92
of

gives a

tin and

of

further

effect

chloride

in stannous

deposition
addition

of

in the

found

was

taining
con-

suggested.

the

deposit. Tannin

to 1*5 litres of solution

gramme

been

published on

investigated the

of the

nature

beneficial

most

of the work

r"ume

also

have

current

solutions

Other

cm.

sq.

acids

lactic

and

has

agents in the

100

per

650 C. with

at

tion
proporthe

to be

fluoride solutions.

and

Nickei,.

arsenide, is associated

and

sulphide
as

the

nickel

of

copper

quantities

in

anodes

matte

have

in

electrodes
free

for

process

electrolytesin

solution.

Orford

the

As

in the

matte,

extraction

or

fouling

of copper

case

both

either
are

The

by chlorine

obtained

concrete

volt, copper

0*35

cathodes.

sheet

and

the

nickel

was

bulk

the
80

the

chloride
of

: 1

unduly

the

by

the

have
matte

into

same

solution

used,

was

desulphurized matte

ratio
rest

salt removed

finallyremoved

to avoid

conducted

sulphide,the

of the

desulphurization of

scale.

iron, casting

deposited

When

by sodium

the

first series, with

was

electrolyte exceeded

that

Copper Co.
desulphurized nickel

treatment

; in the

vats

such

is liberated

It is said

necessary

Electrolysis was

solution.

brine

of

Canadian

and

copper

electrolyte, a

As

anodes.

lyte
electro-

developed a
using nickel sulphide

small

experimented successfully on
containing

sulphur

solution.

processes

electrolyte.

the

nickel

Trumm9*

Co.

Copper

proved satisfactoryon

process

solution

The
W.

chloride

nickel

relativelylarge

uniform

and

anode.

the

at

state

much
inasdifficulties,

technically successful, although

good

sulphate

chiefly

Attempts to use
sulphate or chloride

nickel

obtained

with

its ores,

iron.

and

from

always* contains

ore

proved

not

Giinther93

in

of nickel

electrolyticrecovery

The

an

in

series

applied E.M.F.

of
of

electrolyticcopper

on

nickel

to

of the

in

copper

copper

iron removed

by

in

as

was

cipitated
pre-

hydroxide,

concentration.

deposition on

the

nickel

The
sheet

ELECTROLYSIS

diaphragms
of

to

3*6 volts, nickel

to

3*5

could

purity

enclosed

chlorine.

the

remove

with

deposited

be

SOLUTIONS

AQUEOUS

using graphite anodes

cathodes,

E.M.F.

IN

With

applied

an

99*85

over

in

cent,

per

efficiency of 93

current

earthenware

cent.

per

Extraction
his

equation

the

all the

construction

as

cathode

graphite

having
nickel

been

passed
removing the
was

was

substituted

was

depolarized by

of

the

iron

by agitation with
about

100

cathodes

density of
cell,a

gms.

and

be

can

The

one.

cuprous

made

air, and

the

of nickel

per

amps,

anodes
per

in that

96

after

"

quantity

is heated
as

the

being ground

further

the solution
is removed

volt

chlorine

when

is

potential

their solutions

and

nearly

potential,as

cathode

solution,

in solution

carbon

1-1*2

current

little

nickel

returning

by Wannschaft

with

chloride

being added

The

C.

but

copper

nickel

the

modified

treated

was

calcium
ore

to

cells of similar

to

the metals

between

was

process
ore

ground

according

copper,

EA= +0228
Ni/ttNisalt
0308
Cu/w Cii salt E*="
Fe/w Fe salt E* =+0*340

of

chemically and

on

for

and

copper

adjustment

equilibrium values

with

solution

by the following figures for the cathodic

indicated

roasted

nickel

and

chloride solutions.

complete by

This

render

to

ore

copper

removed

for

separation of

The

already

+NiCl2 +S

used

anode

nickelous

and

has

the electrolyte containing but

electrically,

and

sheet

the

+2CuCl2-"Cu2Cl2
iron

and

copper

copper

which

ores

roasting the
of

fied
35) modi-

p.

"

NiS
silver

(see

of
accomplished by means
chloride
containing calcium

was

chloride

cupric

After

insoluble, extraction

sulphides

The

for copper

nickel.

to

Hoepfner

"

electrolyticprocess

iron

the

the

Processes.

discussed,

been

700

in

99

ferric

to 6o"

of
to

hydroxide

liquid after filtration contains

litre
are

100

efficiencyof 93 per

as

NiCl2.

employed

sq. cm.,
cent,

and

Nickel

with

4-4*5

is?seated

to

sheet
current

volts
have

per
been

INDUSTRIAL

ioo

obtained.

The

by
showed

chlorine

of

traces

Cu, and

per cent.

liberated

impurities, o*o6

per cent.

0*02

in

be

can

nickel

is removed

with

applied E.M.F.

already

has

It

separation of

of
for

from

those

from

the

which

acid

solution.

fact

that

The

be

can

higher

of

these

obtained

by careful

The

electrolytes

potential.

potentialof

nickel

volt, it follows
than

nickel

in

of

difficultyis further

even

to

velocity of reaction

not

nickelic

hydrogen

that

out

normal

would

moderately

emphasized by
nickel

overpotential of hydrogen on
volt,
Caspari, less than 0*20

the

according

copper

however,
deposition of copper
are,
nickel can
be deposited successfully.

easily liberated

more

copper

the

salt solution is +0*228

be

the

Plating of Nickel.
practicallycomplete

that

copper

cathode

the cathodic

Since

of

the

Details

anodes.

indicated

been

nickel

adjustment
favourable

After

C.

lacking.
Electrolytic Refining and

The
"

insoluble

crude

acid

an

0*02

however,

are,

processes

that

by electrolysisat

be recovered

can

Fe,

cent.

per

desulphurization

by

successfully refined
at 300
sulphate electrolytemaintained
sulphides

lected
col-

was

It is stated

Si02.

alloys obtained

copper

anodes

the

at

Analyses of the deposited nickel

of hoods.

means

only

nickel

ELECTROMETALLURGY

and

the

is low

that

the

"

Ni""*Ni+2"
is very

density of

potential difference
It

follows

is most

that

In

passive,such

as

amperes
of

common

gold in

metallic

accelerated

conditions

nickel

marked

tendency

chloride
nickel
the

cm.

found

metals

solution
anode

ionic

tating
necessi-

working

cathode

electrolyte

of basic

that

and

condition

to

necessary.

for the

formation

the

other

With

sq.

was

solution

with

of the
from

100

per

0*64 volt

"

nearly neutral

velocity of solution

polarization.

desirable, provided that

is avoided.

of

ro

have

cathodically passive, thus

cathodic

increased

an

iron

and

anodically and

become

current

Nickel

slow.96

salts

easilybecome
and

iron, the

of

deposition

are

greatly

by rise in temperature.97 Accordingly the best

for

depositionare

found

at

relatively high

ELECTROMETALLURGY

INDUSTRIAL

loz

Chloride

"

litre)gives
equal

nickel

salt

obtained.

chloride

as

from

Dechert

has

substitute

of calcium

use

of ammonium

addition

the

into

deposits

when

suggested the

for

per

sulphate electrolyte

double

the

(15 gms.
converted

chloride

ammonium

obtained

to those

be

may

chloride

unsatisfactory deposit unless

an

double

the

Nickel

Electrolytes.

chloride.
acid

Other
time.

to

from

used

complex electrolyteshave been

Pott's
electrolyte containing

nickel

time

acetate

calcium
acetate
(20 gms. per litre),
(16 gms. per litre)and
is stated to be an
cellent
exglacial acetic acid (3 gms. per litre),
electrolytefor the depositionof the metal.
Pfanhauser
of

boric

whilst

citric acid

or

10"

Powell

Nickel

ammonium
in

patents

for the

acid.

suggested benzoic

fluosilicate
108

fluoride

various

deposition of

found

dilutions

dense

fluothe

among

more

electrolytes

suitable

as

smooth

and

aluminium

with

are

sodium

with

phosphate

ethyl sulphate,101nickel

silicate,and

addition

the

sulphate electrolyte,

double

the

to

pyrophosphate,102 nickel
recent

recommend

I^angbein both

and

zinc

deposits on

or

brass.
is claimed

It

from

either of the

(1) 8

will be

as

addition

from

very

contain

1.

that

nickel

Desmur's

Sodium
Bischof's

nickel

as

; nickel

cent.

only

"

fluoborate.

borate

best

per cent.

acids

weak

very

the

that

nearly neutral

Nickel

2.

per

noted

suitable

are

deposits are

obtained

electrolytes.

Electrolytes.
the complex
as
"

be mentioned

may

nickel

deposited

be

may

following electrolytes

agents and

Alkaline

nickel

104

per cent,

(2) NiCl2 5
It

malleable

that

few

A
ion

electrolytes

suggested

Ni(NH3)"4, amongst

"

solution

"

ammonium

sulphate

7 gms.
8

bicarbonate
solution

litre.

per

"

Nickel

sulphate
Ammonium
sulphate
Ammonia
(o'88o)
.

86
n

ft

tt

t"

17
120

which

ELECTROLYSIS
The

IN

complex
for
have

agents

been

have

Certain

deposition.

for

recommended

deposits. Tannin,
glycerine have

solutions

cyanide

nickel

SOLUTIONS

AQUEOUS

the

factory
unsatis-

proved

addition

organic

ensuring

gelatine, glue, certain

all been

103

smooth

even

glucosides and

subject of patent literature,

Cobai/t.
The
its

electrolyticpreparation
has

ores

Doubtless,
could

be

the

been

not

methods

refiningof

or

subject of technical
the

applicable to

adapted

suit this metal

to

investigations.
deposition of nickel
of their close

account

on

similarity; the electrolyticpotential of cobalt

being only +0*004

to the

than

lack
that

vo^

of demand
for

from

cobalt

higher than

that

of nickel.

Owing

price rules higher

available supplies are

for this element

nickel, although

E*=* +0*232

the

the

large.
have

indicated

advantages
the merits
as

of the

for the

as

nickel

speed of
both

in

has

respect

cobalt

that

"

sulphate

sulphate, thus
with the same
electroplating
cobalt

film

was

is 2*5 times

as

In

dm.

one
was

the

up

to

permitting of a greater
applied E.M.I?.

strongly adherent

4 amperes

current

electrolytea
used

for

soluble

and

hard

iron.

and

current

times

to

Harper and Savell,106

per

sq. dm.

be

can

plating baths which

density permissible with

is

continuously in cobalt
three

marized
sum-

to
experiments, came
superior to nickel
plating was

ammonium

brass

(3) A

Kalmus,

ammonium

(2) The
on

metals.

two

followingreasons

(1) Cobalt

O. P. Watts

some

long series of technical

conclusion

the

deposits.

105

conflicting evidence

somewhat

result of

nickel

cobalt

on

this

that

over

the

electroplating with
metal
apparently ofiers

experiments

Recently,

ployed
em-

over

nickel.

density of 26*4 amperes

per sq.
short period,and produced a satisfactory
current

deposit.
(4) The deposited cobalt is harder
white
a high polishshowing a beautiful

than

nickel, it takes

lustre with

slightly

104

INDUSTRIAL

bluish

tint.

computed
the

to

ELECTROMETALLURGY
actual

The

give the

of hard

weight

4 times

protectionas

same

metallic

is

cobalt

its

weight of

softer nickel.

(5) Both

rolled

and

cast

cobalt

anodes

used

be

may

passivityphenomena do not appear to be so much in evidence

in the electrolytesemployed by these investigators.
(6) Plates

per

with

thickness

100

densities up

current

to

and

could

cent,

per

posited.
de-

be

may

be

5 amperes

over

dm.

sq.

The

followingcompositions

(1) Cobalt

ammonium

in

found

satisfactory electrolytes were

most

two

of the

baths

desirable

any

efficiencies of nearly

(7) Current
obtained

to

up

:
"

sulphate (cryst),200

per

gms.

litre.

(2) Cobalt

per litre.

sulphate,312 gms.
chloride, 19*6

Sodium

"

Boric
Cobalt

acid, nearly

is also

noted

that

can

generally be attributed

to the

metal,
films

metal

of this gas

solution

the

to

former

peelingpropertiesof

the

we

owing

in the

less soluble

and

have

nickel

probably superior to

hydrogen is much

fact that

,,

saturation.

to

in the

metal.
The

electrolytescontaining the complex

Co(NH)3)'#4, suggested by Boettger, Beardslee, and

ion

others, have
The

without
In
would

proved satisfactoryin practice.

not

double

modified

on

ammonia

cobalt

by
a

addition

the

small

be indicated

removing the
depositingbath

Boric

of

quantity

practice the

Cobalt

mentioned

sulphate bath

use

baths

to the

plating
suitable

ammonium

magnesium

or

articles.

for

Deposition of Cobalt
gives the composition of a

(2)

loss of solution

unavoidable

Langbein

suggests

as

electrolysis
"

sulphate
.

with

(1) and

than

weaker

40 gms.

acid
.

sulphate

been

of citric acid.

of

owing

has

above

litre.

per

20

,,

,,

Nickel
bath

Alloys.

from

which

"

O.

P.

Watts

it is claimed

IN

ELECTROLYSIS
the

alloy of nickel

hardest

(75 per

Ni

cent.

cobalt

and

sulphate
Cobalt
ammonium
sulphate
Ammonium
sulphate
.

the addition

I^angbein suggests
Deposition of
of 3

ratio

the

anodic

the

Ni

to

of the

solution

corresponding

ratio.

by which

could

this

of two

passing

electrode,
nickel

cobalt

anode

uniformity, since

for

would

litre.

""

)9

"l

99

solutions

such

be

and

dissolution

of

schemes

cobalt, and

through

alloyed anode.

an

dissolve

are

miscible

TO

SECTION

with

in all

Metall., 5. 27

Trans.

Metall., 8,

Trans.

Metallurgie, 1908, p.

"

Blount,

Addicks,

Electrochem.

820

Practical

"

Chetn.

Trans

Soc, 25, p. 193

Soc,

190,

Electrochemistry,"
Electrochem.

Atner.

J.C.S.I., 347,

"

Zeit. Phys.

Chem.,

28, 1897, 689.

Chem.,

47, 1904,

91,

10

Zeit. Phys.

11

"

18

Zeit. Elektrochem.,

18

Amer.

Trans.

15

Firchland,
"

17

Zeit. Phys.

18

Siemens

18
80

Eng.

and

9, 1903,

Pat,

Chem.,
vol.

1916,

Zeit. Elektrochem., 10, 688;

88

Bunger,

84

Chem.

86

Chem.

Rideal.

E.

1913.

1895.
288

1893.

1914.

Trans.

"

1906.

Steel."

20, 296.

81

Electrochem.

Electrochem.

1912.

; 1880.

11

Dingl. Pol., 258,

105

45-79.

Stuttgart, 1908.

Methoden."

of

and

88

86

(6), 1901,

Soc, 21, 236;

p. 158;

Halske,

26, 1914.

762.

24806

of Iron

J.S.C., p. 710,
/. Phys. Chem.,
Amer.

Mag.

Anorg. Chem., 19,

Corrosion

The

p. 44.

Soc,

52.

Schnell

Electrochem.

Zeit.

16

; Phil.

1907

Elektroanalytische

Luckow,

xxxvii.

202.

14

; 1914.

1906.

Electrochem.

Atner.

II.

1908.

Amer.

Soc, 27, pp.

291

191

4.

1904.

Ind., 8, 17;

1905.

Tech., 2, 23.
Treatise

on

Zeit., 28,

Electrometallurgy/'p. 258.
1209;

1904,

Macmillan.

each
The

perfect

proportions

in solid solution.
REFERENCES

tion
inser-

by the

other

the

in the

be

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either

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obtained,

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probably

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from

two

nickel

casting

the

by

or

per

undoubtedly

are

current

correct

gms.

acid.107

accomplished,
one

deposited

56

metals

There
be

be

40

of boric

can

two

electrodes,

the

Co

147

metals

two

can

"

ammonium

Nickel

105

Co)

cent.

25 per

SOLUTIONS

AQUEOUS

io6

INDUSTRIAL

ELECTROMETALLURGY

87

Met.

88

Michailenko,

88

Trans.

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Frary,
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81
88
88

84

88

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87

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88

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Ber., 1892, 25, 779.

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Electrochem.

Trans.

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Met.

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11, 575;

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Chem.
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200;

and

C. R.

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48

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88
88

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88

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Lead

68

D.R.P.,

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Trans.

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1903.

1843.

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24,

7, 143.

1905,

1878.

1907.

1908.

1000;

Ind., 2, 355 ; 1904.

Refining by Electrolysis,"A. W.

38,

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43.

193

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Electrochemical

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668

67,

of

302

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Zeit.

88

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16, 279;
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10, 500

Anorg. Chem.,

Soc.

70

J.C.S.,
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78

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74

Trans.

78

Zeit.

Farad.

Soc,

1,

11

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1912.

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1905.

1910.

Engineering, 10,
16, 599

21, 313;

1900.

827.

71

Chem.

Electrochem.

78

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1910.

1900,

373,

13, 441

Soc,

/. Phys.

1907,

1905.

1908.

87

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1908.

Soc,

66

Chem.,

Betts.

of 1886.

202

; 1910.
1 ;

1905.

1912.

; 1912.

1908.

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Electrochem.

77

Electrical

Eng.

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78

U.S.

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Eng.

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628

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82

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6*

SOLUTIONS

AQUEOUS

IN

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191 1, p. 345.
p. 440.

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Die

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and

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Foerster,

98

Engermann,

99

Electroplating.

100

U.S.

101

D.R.P.,

188

Langbein,

"

U.S.

Kern,

Trans.

105

Trans.

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188

Bureau

of

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of Mines,

1909.

1915.

p. 208.

TO

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SECTION

Elektrolytischen Metallniederschlage,"

1903.
Leipzig. 5th edit.
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W.
Elektrochemie,"
Monographien fiber angew.
W.
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"

Practical

'"

Electrometallurgy," Kershaw.
Electroplating," P. Hasluck.
Electroplating," Barclay and
Electroplating and Refining
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1896.

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2.

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191

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The

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108

107

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et d'Electrometal.

d' Electrochem.

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602

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Pa.

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of

Metals," Watt

and

Phillipp. Crosby

ELECTROMETALLURGY

INDUSTRIAL

108

"

Electroanalysis,"

"

Analyse

des

E.

Smith.

Metaux

Pa.

Blakeston,

Bertiaux.

L.

and

Holland

A.

Electrolyse/'

par

Paris.

Dumond,
"

Elektroanalytische

It

Quantitative

Methoden,"

Schnell

Analyse

Fischer.

A.

Elektrolyse,"

durch

Enke,

Stuttgart.

Springer,

Classen.

A.

Berlin.

Electrolytic
it

Practical

"

Some

Methods

of

Analysis/'

Kershaw,

Neumann-

Bedell.

Electroplating/'
Electrochemical

Centres,"

G.

N.

Univ.

Pring.

Press,

chester.
Man-

Journals,
Transactions
Transactions

of

the

of

the

Electrochemist

Electrochemical

Society.

Society.

Faraday

Metallurgist.

and

Electrotnetallurgie.
L'

Industrie

Electrochemique.

L'Electriden.
Metal

Industry.

Metallurgical

and

Engineering

Chemical

and

fur

Zeitschrift

Mining

Zeitschrift.
Review.

Electrochemical
Mineral

Journal.

Elektrochemie.

Elektrochemische
Electrical

Engineering.

Industry.

Industry.

Literature.

Special
"

Modern

"

Metallurgy
""ie

"

Electrolytic

Lead

'

'

"

191

Zinks

des

Ulke.

Refining,"

Louis.

auf

Wiley

"

Sons.

tische

Metallurgie

Elektrometallurgie

by

Electrolysis/'

Verzinkung,
des

Zinns/'
des

'

Elektrolytischem

A.
'

H.

Nickels,"

S.

1903.

1.

Gunther.

Wege,"

Halle.

Refining

Elektroly

"Die

Copper

Tin,"

Darstellung

Knapp.
"

of

W.

Betts.

Cowper

Coles.

Mennicke.
W.

Borchers.

Wiley
1

905.

"

Sons.

INDUSTRIAL

no

of free circulation

permit

to

is

cathode
the

ELECTROMETALLURGY

ring of nickel

surface

floats to

screen.

The

or

largest cells

holding

about

60

about

are

of

kgm.

100

deep

cm.

molten

200
density is about
anode
density 170 amps,

current

the

total current

cell

per

efficiency of about
tained

fused

being

45

by the

1200

The

the cell to ensure

placed round
protecting crust of caustic soda
cathode

cell

the

be

can

Electrolysis is

burner.

and

sq. dcm.,
at

giving

volts, the
current

electrolyte is main*
formation

the
and

started

by

at

C.

of

low

as

Above

5250

for
of

means

thin

seal

good

up

conducted

possible,3i5"-320"

as

cathode

just sufficient lagging is

and

current,

The

per

amps.,

hood.1

diameter,

cm.

soda.

forated
per-

the

to

45

sq. dcm.

cent.

per

and

amperes
per

of

means

is fitted

discharge pipe

at the

by the wire-gauze
by

out

under

liberated

sodium

ladled

be

can

the

dipping

B,

gauze,

is retained

top and

the

metal

spoon,

wire

electrolyte. Above

electrolyte. The

of the

cathode

The

of the

the
gas

rature
tempe-

C. the

yield

is

3000 C), due

practically zero
(m.p. crude NaOH
the increased
diffusivityof the metal in the electrolyte.
The

exceed

50

electrolysis and

simultaneous

according

at the cathode

hydrogen

the

to

and

efficiency could

current

owing

cent,

per

of

mechanism

Blanc

Le

"

electrical

the

that

showed

Electrolysis.

the

investigated

Brode2

of

of

Mechanism

to

to the

never

liberation

equations
"

2NaOH="2Na+20H1

4OHI at the anode-"2H20+02+4"

electrolysis
on
2H20-"2H2+02
Net

See

reaction

also V.

formed

Hevesy,

at

and

sodium

the

anode

there

the anode
Further

sodium
difEuse

hydrogen
reactions

the

cathode

and

through the bulk

rapidly

more

compartment,

at

and

than

oxygen

the

of the

liberating hydrogen;

react,

diffuses
both

Zeit. Elcktrochem., 15, 539 ; 1909.

liberated

the

Both

(cathodic)+02.

2NaOH=Na2+H2

since

water

at

may

be

water

lyte
electrometallic

high temperatures,
liberated

in

causing explosions.
between

the

liberated

sodium

and

IN

ELECTROLYSIS

resulting from

oxygen

for

in

also

electrolysismay

the

efficiencyloss, according

small

ELECTROLYTES

FUSED

the

to

account

equation
"

2Na+02=Na202
again reduced

then

peroxide being

the

sodium

at

produced

by

the

by

the cathode.

electrolysisis

the

efficiencycan
have

the

out

returning

water

the

with

is conducted

this

removal,
caustic

patents

using

by

eg.

soda

such,

current

Various

cent.

cathode

to

prevent

by passing dry air

or

but

have

they

potential of

Blanc,8 is

Le

to

the

oxygen,

per

compartment,

decomposition

according

electrolyteas

not

ceived
re-

application.

technical
The

the

by molten

to

anode

the

through

50

effect

*to

water

and

hydrogen

unattacked

diaphragm

from

exceed

never

the

as

removed

into

taken

been

long

as

not

decomposed

but

that

is evident

It

2*2

volts.

Technical
of 5 volts

applied E.M.F.

an

efficiencyof 45 per

cent.,

giving

hours

are

fused

dry

electrolysis
and

current

efficiencyof

energy

an

NaOH,

20

cent.

per

Hence

k.w.

1000

produce 79 kgm.

to

necessary

of sodium.

Griesheim

The

"

electrode

"

the

contact

production of calcium and

for preparing magnesium,

employed.
caustic

soda

vertical

iron

fused
of

gearing
of the

make

to

bath.

is raised and
as

per
cent,

process
the

process.

sq.

ring in
serves

fast

the

end

current

lowered

by

is liberated

of the

sodium

rod

density

current

is claimed

for the

efficiency. The

this

of

the metal
the

must

thus
as

chief

so

electrolyte as
be

set

the

very

centre

cathode

formed

high

much
in

serves

1000

as

giving

advantage

is not

of

means

the

process,

the

consists

electrolyte in the

sodium

action

Against

cathode

the

as

lies in the fact that

solvent

the

containing

The

be

can

with

cathode
dcm.

bath

anode.

which

rod

As

shallow

as

contact

cathode.

amps,
per

iron

circular

to

for

occasionally used

and

this process

In

"

principlegeneral

strontium,
is

Process.

the

35

of the

exposed
Castner

high voltage

ELECTROMETALLURGY

INDUSTRIAL

H2

to

necessary

cathode

operate

of the

Modifications
the

was

provided

with

The

addition

of

raises

to

evolved

of

collector

above

of

conditions

at

the

anode.

P.

cent,

sodium

ever,
how-

soda,

4800

of

C.

caustic

soda
free

The

to

reform

sodium

is

suggested the addition

caustic

fused

the

soda.

decomposition potential of 2*2 volts for

being reduced to i*8 volts.
anodically react9 with
sulphur liberated

caustic

fused

is

sodium

theoretical

The

50

dioxide

carbon

no

Scholl

sulphide to

cathode.

yield of

the

small, and

B.

the

temperature

expected, very

cell, which

electrolyte; with

the

be

carbonate

caustic

the

to

working

these

sodium
Castner

carbonate

Under

of 50 per

high

Becker*

"

modified

melting-point

the

necessary.

is, as

the

Electrolyte.

mixture

sodium

carbonate

cent,

Castner

electrolyte in

soda

per

of

use

and

as

with

process

density.

current

suggested

electrode

contact

sulphide, which

is

the

the

again

electrolyzed.

Na2S=2Na+S"
+2S =2NaaS

4NaOH
will

It
the

noted

be

salts

other

two

are

which

sodium

of metallic

are

Darling process

The

central

cathode, stated

by

perforated coaxial

is the cast-iron
With

at the cathode

of

are

condensation.
is difficult to

for

on

accomplished
the

production

technical

scale.

Philadelphia, U.S.A.)

at

nitrate

electrolyte. The

as

of carbon, is surrounded

made

metal

cylinders,whilst

the

anode

containing vessel.
of 15

and

is there

space

From
find

and
the

out

whilst
the

between

removed

volts

recovered

perforated ladle

annular

cylinders

to be

applied E.M.F.

an

worked

sodium

fused

to

employ

utilized

(worked

is said

the

in

fundamental

the

water, is not

of the

reduction

means.

There

means

is

potential required

viz. the removal

difficulty,

two

+02

although there

that

decomposition

by this

+2H20

in the
the

the

nitric

manner

the

into

nitric

acid

by

products from

and

details available

how

usual

anode

anode

converted

is liberated

sodium

of this
is

perforated
acid
process

produced

by
it

by

direct

condensation,

ELECTROLYTES

FUSED

IN

ELECTROLYSIS

anode

the

as

entirely of nitrogen dioxide

and

products

113

consist

would

oxygen

2NO'8-"2N02+02+2e
The

production

absorption
the

in water

Castner

nitre

the

8.

"

when

lo

4t

Melting-point
(G. v. Hevesy,

would

vapour
of

i*.

sodium

so

loo

of Soda

Chem.t

be

be
and

would

the

Potash.

Alkali

by
anode

the

dustry
Inthis
and

regulated

compartment,

conceivably take place :"

=4HN03
made

phuric
sul-

73, 676.)

obtained
to

over

mjcw
and

with
expensive even
preparation of sodium

steam

by

Liquefaction

too

direct

followingreactions

preparation of

flO

usual

the

(see Partington, "The

might

could

acid.

Zeit. Phys.

superheated

this reaction

strong

70

mixture

advantages
and

of mixtures

4N03' +2H20
If

this gas

sodium

to

probably be
gas.

acid

the

ib

curve

concentrated

admission

for

process

from

offer any

not

making

nitrogen dioxide

")
nitric

for

lo

""

of

would

process

acid

Fig.

of nitric acid

+02
to

+40

proceed smoothly

concentrated

nitric acid
8

in

the
one

INDUSTRIAL

H4

operation

would

of the
The

Castner

which

processes

has

nation
combi-

the

for the

chloride

process.

of metallic

production
frequently attempted.

been

arrived

have

than

sulphuricacid distillation

and

chlorine

and

economical

more

prove

of sodium

use

sodium

ELECTROMETALLURGY

at

technical

some

The
in

stage

be grouped into three classes.

development may
using direct electrolysis between
(A) Processes

their

solid

electrodes.

(B)

using

Processes

molten

lead

diaphragm

serving as

intermediary electrode.
(C)

using a molten lead cathode.

The
Electrolytic Process.

Processes

(A) Direct
of

sodium

on

the

fused

from

lines of the

loss of metal

C. has

Early
indicated
sodium
into

experiments
this

to

the

vessel.
in

placed

in

metal

could

be

the

of

other.

resultant

The

the

780

"

lyte
electro-

C, whilst

iron

the

that

an

anode

metal

the

cathode

electrolyte,sodium

tubular

was

orifice.

Further
of the

suitable

more

about

potassium.
The
Virginia Electrolytic Company's

as

per

cent,

process,

based

V.
and
Kiigelgen plant installed
designs of Seward
Basel, is practicallythe only one in successful operation.

which

circular
is

furnace

protected by

CC

is

the

employed,
salt

crust

lined

EE,

with
and

an

chloride.

the

of

temperature

higher melting-point sodium

contained

taining
con-

disposed

was

horizontal

the

the

as

equimolecular mixture

sodium

and

of

divided

bath

used

was

of

scale

partition extending

maintaining
that

at

production

the

shallow

bath

technical

for

carbon

through

sodium

to

pressure.

on

hollow

below

investigationsshowed
of potassium
chlorides
electrolyte than

the

By

off

above

vertical

horizontal

electrode
drawn

by

and

of the

m.p.

vapour

necessary

temperature.
bottom

owing

process,

the

Fischer

by

conditions

compartment

one

the

considerable

scarcely feasible

boiling point of 8770 C, and

compartments

two

nearly

already

has

is

Greisheim

or

chloride) lies well

sodium

the
at

chloride

by volatilization, since

liberated

8oo"

sodium

Castner

(crude sodium
the

preparation

"

of

on

at

firebrick,
contains

ELECTROLYSIS

circular
The

IN

graphiticanode

cathode

cooled

DD.

under

circular

higher
used

into

space

than

200

without

amps,

per

destruction

cell constructed

sq.

dcm.

lines

F.

cannot

sodium

current

conveniently

be

about

through
A

The

graphite anode.
takes

water-

down

collecting vessel

of the

these

on

arid flows

hood

the

by

deposited

the

10,000

largest

amps.
outltl

(KLonns

(B) Process

using

Molten

Lead

A.

cathode

is surrounded

electrolysis

water-cooled

115

iron

hollow

extremity

On

the

ELECTROLYTES
with

BB,

its upper

at

hood

floats up
the

FUSED

Intermediary

Electrode.
The
which

has

absorbing

and

were

of

an

the

with

inner
vessel

into

molten

is

technical

3000

of

is maintained
cathode

vessel

magnesia
8oo"

in the

this

Several

have

in
the

whilst

the

base

The
and

manner;

adjoining

which

C.

built,

operation.

J,

is

The

sketch.

provided

temperature

cell is
a

type
unit

been

satisfactory

from

seen

at

scale.

longer

no

cast-iron

lining
lead

in

of

one

each

amps,

is

cell will be
the

only

the

function

process

of the

is fed

to
to

the

mechanism

on

2000

stated

nevertheless

with

tried

been

cells

Salt

Process6

Ashoroft

vertical

provided
carbon

n6

INDUSTRIAL

anode

F.

wire

The
is

cathode

helix

vessel.

ELECTROMETALLURGY
molten

given

rotational

between

placed

.The

electrolyteas

whole

well

by

movement

current

magnesia

the

proceeding to the
electromagnetic force field

vertical

since

vessel, and

electrolyte can

the

direction

resolved

be

the

component

of the

means

liningand the
operating the cell is passed

the

through the helix before

way

molten

the

as

into

of

anode
is

the

both

generated
in

current

in

the
zontal
hori-

and

the horizontal

field will cut

magnetic

first

in this

vertical

iron

Fig.

io.

Cell for

"

Fused

Electrolysis of

at

component

current

of the

movement

By

of

means

suitably situated

is caused

flow

electrolysiscell K, and

to

the

surrounding

first tube

orifice H.

second

cell

containing fused

maintained
is liberated
formed

in

at

3300
the

at

the

returned

and

deposited

On

anode

on

tube

lead

caustic

iron

the

soda
of the

F,

the

and

cathode

sodium
C.

has

vessel

acts

as

lytic
electro-

chlorine

current

sodium

the

The

the

electrolyte is

lead

into

the

annular

second

as

passage

into

an

thus

rotating

into

back

The

first after the

the

the

through

first cell is circulated

to the

and

C.

diaphragm

return

interchanger for the molten

heat

rotational

through the orifice

second

the

mediary
Inter-

electrolyte.

lead

through

with

Process.

right angles, causing

molten

space

Chloride

Sodium

Ashcroft

Electrode.

alloy

second

been
molten

cell,

removed
sodium

n8

INDUSTRIAL

is

easily

operation
700"

fused

the

far below

electrolyte

710" C,

at

is maintained

tlie double

but

this temperature.

it floats to

camallite,

from

accomplished

in the

technical

In

between

6500

C. and

liberated

of

means

sectional

chlorine

liberated

The

from

the

molten

the

This

indicated

as

steel

or

be

to

chlorine.

iron

from

than

there

porcelain hood,

protected

and

has

surface, and

diagram.

container

the

as

the

specifically lighter

anodically

the

by

following

serves

is

magnesium

molten

kept separate
is

melts

C.

Since
fused

chloride

magnesium

Pure
salt

ELECTROMETALLURGY

pot

action

of

the

electrolyte by

rw

solidified

porcelain cylinder
slits in the

cylinder
A

part

open

carbon
the

at

immersed

immersed

continuous

dioxide)

The

I".

crust

in

in the

is maintained

sweep

have

cathode

In

practice
energy

the

to the

penetrated

the

is all that

can

occur

be

the

out

due

to

having

(nitrogen
part

upper

chlorine

any

the

as

in

vertical
iron

an

cathode.
carbon

or

of

the

which

cell
may

compartment.

6330

permitted

serves

gas

is maintained

dissipated in heating
is

and

is inserted

electrolyte, whilst

inert

temperature

of magnesium

m.p.

the

through

during electrolysis,to

bottom

electrolyte
of

stream

anode

in

C.

the

solidification

of the

the

electrolyte.

somewhat

working,

by

and
metal.

narrow

trical
elecSince
range

difficulties

quently
fre-

ELECTROLYSIS

Although
chloride

is

the

If too
and

is

01

of

cent,

per

iron

efficiencyover

20

into
to the

of

little calcium

fairly high cathode

10

to

up

15

high

high

per

working with

and

efficiency is

produce
The

with

use

as

of

(27-30 amps,
The

current

have

been

its action
in

the

A.

although
a

sq.

to

will

Works

Magnesium

and

of sodium
The

the

to be

by

is worked

the

position of
The

iron

rod

frequent
the

Both

density

usually employed.

70 per

process

are

chloride and

process

higher than

are

make

vessel.

energy

hours

kw.

electrolyteis renewed

dcm.)

very

cent.,

90 per

over

1000

proportions.

by reversing the

containing

efficiency70 kgm. of metal.

efficiencyis stated
made

density

working

chloride.
magnesium
cathode
current
(750"-8oo") and

per

Oettel8

current

careful

By

cent.

per

Aluminium

the

the

will coalesce.

anhydrous

temperatures

By

voltage of 5*5 volts per cell the

carnallite in molecular

addition

cell.

by

suggested hy Deville,

cell with

electrolytea mixture

continuously, and

film, is caused

be maintained,

50 per cent,

Hemelingen

said to

sq. dcm.

nearly 52

fog

phenomenon,

in the

dcm.,

small

efficiencycan

current

metal

moved
re-

density is usually employed

per
a

as

magnesium

the

again

are

This

oxygen

and

current

magnesium

but

thin oxide

fluoride,as

amps,

40 amps,

as

I^ess than
the

carried

are

current

successfullyoperated

has

of

and

means.

reoxidized.

are

containing

gas

reduction

reduce

coalesce

not

electrolyte and

film is dissolved

oxide

from

as

do

they

impurity,

globules of molten

to the formation

inert

an

addition
the

the

anode, where

chieflydue

using

surface

the

to

in the

of iron

anode.

and
can

by this

small

Occasionally the
floating

chloride

cent,

per

Traces

alternate

the

to

salt at cathode

ferric

fire and

nearly unavoidable

working due

of the

cell.

the

alloy of potassium

an

readily catches

which

and

common

lead to inefficient

oxidation

formed

6 volts

5 to

of the melt.

the temperature

explosions in

carnallite, a

magnesium

of

voltage

high voltage be employed

small

119

volts, yet in practicefrom

to maintain

magnesium

causes

decomposition

only 325

employed

are

ELECTROLYTES

FUSED

IN

Attempts

cent.

more

anode
which

continuous
and
now

in

cathode
serves

ELECTROMETALLURGY

INDUSTRIAL

120

adhering

magnesium
by

from

current

density is, however,

and

high

rod-like

control

of the

difficult under
in

form

serves

cathodic

conditions,

these
metal

is

usually

below
attempted the electrolysis

the

melting

potassium

content

the

tected
pro-

of which

carnallite,the base

electrolyte. The

in the

the molten

the solution, and

it solidifies in

to

of fused

coat

cathode

as

slowly raised

is

cathode

as

obtained.
10

Tucker
of

point

has

magnesium

form

in the

of

together under
have

which

sponge,

unsuccessful

proved

electrolyticsolution pressure
The

of

use

chloride

metal

for

subject of patent literature,but

utility.

is obtained,

the

electrolyte.

the

lytes
electro-

aqueous
of

the

high

Eh =+i'55
salts

has

volts.

been

the

proved of practical

have

none

melted

and

account

on

of the

solvents

organic

and

from

deposit magnesium

to

metal

the

be removed

can

flux of calcium

Attempts

500" C, when

at

Calcium.
The

preparation

chloride

is

the

form

calcium

Pure

although
of

use

containing
Since

of

is

the

Ruff

lower
12

and

same

of calcium

cent,

per

obtained.
from

calcium

magnesium,

is

essentially

the

Stockem,13

and

and

by

this

immersed

of calcium

The

is fused

chloride.

(m.p.

66o"

calcium

is 8oo"

C.

first

petroleum

containing 50

metal

chloride

7800

C).
it is

C. and

electrode

operated

(1).

produced

calcium

continuously, removed

method
it in

advocated

fluoride

above

who

residue

adherent

Wohler12

contact

described

as

lyte,
electro-

as

directlyby electrolysis.This

of

means

used

electrolytebetween

the

solid calcium

manner

large scale

porous

and

melting point mixture

accomplished by

calcium

Plato11

melting point of metallic

Borchers
a

of

production

(m.p. 7800 C.) is

chloride

C. to prepare

in the

the

fused

from

electrolyzer employed

possibleby maintaining
8oo"

calcium

in construction.

same

the

difficult than

more

the

although

of metallic

in

to
a

60

sealed

to

per

on

the

quench it,whence
cent,

vessel and

metal

was

separated

ELECTROLYSIS
The
about
must
an

decomposition

employed,
applied E.M.F.
be

of

of calcium,
the

high

only

necessitating

yield9

small

in the

obtained

are

case

production

continuous

of

process

in the

observed

factor

important

very

electrode

contact

is

densities

current

per dcm.,

amps,

fog formation

an

chloride

volts.

of 20-30

becomes

and

10,000

to metal

tendency

magnesium

about

121

calcium

of

potential

volts,but in practicevery

3*25

The

ELECTROLYTES

FUSED

IN

unless

removal

be

employed.
Laboratory
however,

that

chloride

can

units
small
have
shown,
experiments on
from
the fused
the preparation of calcium
smaller
much
cathode
be accomplished with

densities

current

than

practice,provided

accurate

an

Frary, Bicknell
sq. dcm.
K.

Wohler,15

50 to 250

used

Tronson

Goodwin,16

technical
tained.
is main-

control

temperature

and

in

used

be

to

9*3

amps,

to

32

per

; and

20

Arndt,*7 60.
For

economical

of the

metal, but

possiblebelow

fusion
the

of the

and

without

through

to

exceeds

cent.

hours

will

from

the
occur

may

which

With

these

coalesce

15

energy

per

and

calcium

cent,

m.p.

point

of

conditions
round

the

in the

form

of

fused

calcium

fog distributed

metal

as

the

much

as

the

layer of

produce 34*6 kgm.

magnesium

Both

loss

electrolyte. The

the

to

be

above

continuously removed
serious

but

made

protected by

15 per

kw.

1000

be

the

just exceed

maintaining

be

can

in

temperature

electrolyteshould

this temperature,

may

chloride

the

should

of

mass

calcium

irregular rod

an

the

cathode

electrolyte. By

deposited

cathode,

production

of the

neighbourhood

as

stated

are

efficiency rarely
energy

efficiency

calcium.

chloride electrolytessuffer

disadvantage that in the preparation hydrolysis

of a hydroxychloride,
resultingin the formation

forms

an

insoluble

metal.

This

chloride

by the addition
moist

can

be

calcium

to

the

of

an

be

impracticable.18

oxychloride with

avoided

in

of

the

liberated

initial fusion

15 per cent, ammonium

carnallite.
chloride
or

electrolytecontaining much

the

of

the

chloride

Regeneration

oxychloride is stated

to

ELECTROMETALLURGY

INDUSTRIAL

122

Strontium

small

on

scale

chemical

of

requirements

is,

manufacture
for
their
apparatus
slightmodifications, similar to those detailed

some

the

manufacture

and

barium

magnesium

of

do

show

not

calcium, but

as

the

meet

The

laboratories.
with

to

only conducted

is

elements

of these

manufacture

The

Barium.

and

tendency

the

at

appear

coalesce

which

drops of metal

such

produce

to

cathode

with

Strontium

calcium.

and

for

molten

small

as

fog

difficulty.

Lead.

Electrolytic lead
solution

aqueous

an

refined

lead

density

current

furnace

The

another

and

electrical

the

surrounded
The

in

which

retain

hopper

cell collects

collects

removed

by

off

second

potassium and
at about
5500
a

current

lead

could
19

C.

be

obtained

of

obtained
a

mixture

good

The

amps,
per

kw.

per

an

electrical

angle,

platforms
lead

hearth

fed

The

of lead

in

of the

it is

where

tinuously
con-

resultant
it is

oxychloride,

is maintained

bath

of 0*5

sq. dcm.

hour.

is

itself is

side, whence

applied E.M.F.

an

loo

from

cathode

chlorides.

With

density

in the

syphon.

the

on

syphon.
employed

sodium

is at

molten

crude

lead

of

means

solidified salt.

deep horizontal

reservoir

of the

hearth

electrolyteis

As

of the

top.

by

in the
a

some

is

which

electrolyticcell which

series of

residues

the

run

lead

the

at

insulating joint,

the

ment*
encourage-

no

auxiliary furnace

an

having

to

serve

from

flue of

the

surface

its inner

of the

side

high

parts, separated from

coating of

sponge

any

received

is in two

protected by

fully
success-

of its salts at

without

has

water-cooled

and
anode

placed

method

iron

has

efficiency. Although

lead

dense

Borchers

solution

of cast

by

fused

from

distinct advantage

one

(seep. 83), but

production of

direct

in

refining is usually accomplished

Betts

volt

and

kg. of pure
and

tine
Valen-

efficiency,using molten

ELECTROLYSIS
chloride

lead

of

to

time

12.

the

caused

Borchers'

"

heat, when

time.

Cell

the process

applied

an

lead could

galena

soon

COOUNG

refiningLead

for

melting point

With

in the

impurities present

the

ATER
Fig.

electrolyte,adding

as

to

123

good yields of molten

volts

1*25

obtained, but

be

chloride

from

galena

finely crushed
E.M.F.

sodium

and

ELECTROLYTES

FUSED

IN

of the

bath

becomes

in Fused

Electrolytes.

rise above

to

low

red

impracticable.

^Dsrc.

accomplished

The

preparation of metallic zinc has been

only by electrolyticprocesses in aqueous

not
p.

and

58),

electrolysisof fused

also by
The

by Borchers,
with

zinc

employed,
chlorine

chloride.
and

gas.

furnace, which

As

for

Extraneous
was

after

action

of

treatment

anode
a

vertical

piece

bent

heat

subsequently

with

lead

on

to

in

vessel

position by

carbon

rod

strip zinc.

required

maintained

at

6oo"

the

to

start

by the

zinc chloride

blende
remove

leaden

was

vision
Pro-

drawing off the liberated

was

process

dry chlorine

of

conducted

were

electrolyticcell

recharging and

the Ashcroft-Swinburne

the

experiments

as

cathode

as

made

was

In

(see p. 139), but

close-fittinglid hermetically sealed

fused

used

who

(see

zinc chloride.

semi-technical

first

methods

electrothermal

by

solutions

the

current.

produced by
C. to 7000 C,

silver

and

scrap

ELECTROMETALLURGY.

INDUSTRIAL

124
zinc

to

the

remove

of the water,

the

of the

rest

primary-electrolysisbetween
carbon

anodes,

The

deposition of
vessel

cathode.

Carbon

tight roof

was

*"

pans

to

remove

being removed

water

zinc

molten

zinc

the

on

took

by

cathode

and

similar

to

maintained

was

firebrick-lined

zinc

molten

used

were

employed

in

place

of which

base

anodes

slight vacuum

and

to

cast-iron

that

acted

gas-

by Borchers.

used

of

removal

the

ensure

as

chlorine.

the

sodium

When
molecular

chloride

quantities

of 4*5

drop

volts

of

current

cathode

3000

over

surface.

chloride

is 1*49

gives 1*57

or

43

Thus

the

formation

the

volatilization

noted

of metal

above,

chloride,24 which
the

of zinc.

by

the

also

those

of Ashcroft

and

electrolyte without
found

He

it

than

16

amps,

volts

at

4500

This

to

25

Swinburne,
the

sq. dcm.

of
a

with

an

traces

by

zinc chloride
both

due

much

to

also to

reduced,

as

sodium

or

conductibility of

experiments

to

zinc chloride

as

chloride.

sodium

higher

density

current

applied E.M.F.

of 45

C.

adopted
as

be

high temperature

zinc

the

disadvantage of these processes is

preparation of the fused zinc chloride
whilst,

pure

any

The

Vogel

similar

use

would

hours

using fused

addition

28

Suchy

efficiency is

energy

potassium

increase

conducted

impracticable to
per

of

of
zinc

of

potential

be

and

sq. dcm.

electrolyteand

can

addition

serves

electrolyte. Vogel

in the

cloud

high

voltage

Lorenz,22 whilst

to

4500 C,

per

kw.
cent. ; 1000
approximately 35 per
When
to deposit 260
kgm. zinc.
necessary
is used (6oo" C. and over, the m.p. of
is 3650 C), there is a considerable
loss of
the

of

amps,

decomposition

volts.

with

temperature

according

volts

present,

obtained

was

amps,

The

i'6o

to

cent,

electrolyte in

the

to

chloride

zinc

the

to

cell at

per

added

was

efficiencyof 98 per

current

iron

filtration and

suggested by Lorenz.21

as

sheet-iron

by solution

in enamelled

concentration, is fused
most

followed

lead

the

expedient

of

free

found

in the

from

water.

in

evaporation

already indicated, Swinburne

electrolysisusing carbon

to be

the

removed

anodes

as

vacuo,

an

last

oxygen

126

INDUSTRIAL
electric

carbon-lined
low

alumina

not

owing

aluminium

has

powder

impuritiesinstead
Heroult

the

In

roasted

to
to

as

pass

digested with
of

pressure

caustic

lined

Silica is also

by

thrown

dissolved

The

alumina

The

into

through
is

bauxite

of

gently

is

then

powdered
is

material

powdered

solution

in

the

to

sodium

hydroxide

made

in

aluminium

dried

and

recausticized.

objections
solution
some
tated
precipia
previous operation,

hydroxide

is washed,

the

these

agitation,about

under

since

and

to be

overcome

aluminate

dioxide.

carbon

process,

it has

lead-

filters into

pulp

wood

alumi-

sodium

$s

reprecipitatedby

process

36 hours

the

of metallic

addition

The

organic matter,

down

this
the

to

after

form

electrolyte employed

the

into carbonate

aluminium

when,

in

prepared

crushed

screen.

alumina

modified

adding

and

passes

alkali is converted

Bayer

is

soda

filtration

the

vats,

bauxite

the

solution, sp. gr. 1*45, under

atmospheres for three hours, during which

After

nate.

the

process

aluminium

period the

alloy.

of carbon.

30-mesh

metallic

suggested for the reduction

been

water

remove

as

prepared by the wet

high temperature
employed

C.) the alumina

does not
easily dissolve in
production of aluminium.

for the

impurities

alumina

as

the

to

is too

content

purificationof

20000

(m.p. A1203
which

iron

easily reducible

the

suitable

so

since

processes,

so

the

and

resultingfrom

is,however,

the

If the

by settlingto the bottom

removed

The

furnace.

is added,

more

are

ELECTROMETALLURGY

70

of

recovered.

be

can

cent,

per

finally roasted

to

about

non-hygroscopic, whilst the soda

in a triple-effect
vacuum
solution, after concentration
rator,
evapobauxite.
of
of a fresh quantity
is utilized for extraction
Over
40 per cent, of the cost of manufacturing aluminium
11000

C.

is stated
The

to

purificationof

in the

be found

electrolyte consists

alumina

in fused

addition

of

variable

Hall

essentially of

amount

of sodium

fluoride, and

of the chlorides
the

the bauxite.

cryolite (AlF3.3NaF), with

fluoride, aluminium

In

it

render

to

of sodium

process

the

or

or

solution
without

of
the

fluoride, calcium

occasionally small

tities
quan-

calcium.

electrolyte is prepared by

IN

ELECTROLYSIS

treating

in

acid

hydrofluoric

is

127

cryolite, and

alumina,
lead-lined

fluorides

mixed

of

of

mixture

ELECTROLYTES

FUSED

melted

in

the

drying,

After

vat.

with

fluorspar

mass

electrolytic smelting

the

furnaces.
is stated

It

Heroult

that
have

processes

Per

590

NaF

CaFa..

dissolve

Hall

at

furnaces

N.Y.,

Lockport,

of

are

13.

wide,

and

whilst

Hall

"

number
in

The
250

the

and

With

the

at

Aluminium

total

rods

44

per

cent.

A1203

iron

lined

with

at

the

in

of

from

180

cms.

3 to

of
is

cathode,

as

in cross-section,
the

to

series,

density

cell

Aluminium.

holder

and

anodes.

being

temperature

of

serves

cms.

40

each

of

100

10,000

per

the

cent,

of

amps,

amps,

per

sq.

(below 9800 C.)

approximately
on

taking

anode

nearly

working

regularly deposited

addition

liner
sq.

as

current

per

carbon,

long by

metre

some

serve

current

E.M.F.
is

an

cent.

per

156
564

""

carbon

worked

cathode

The

bath,

are

The

applied

each

to

amps.

dcm.,

Electrolytic Production

the

special holder,

furnaces

represents

280
.

anodes

of carbon

holders

for

deep.

metre

mounted
four

Furnace

cast

some

are

carbon

Fig.

"

employed.

temperatures
and

Heroult.

20

some

and

Hall

the

cent

AlF^NaF
CaF2*..
AIF3

cent.

200

electrolytes

The

Per

21-0

...

These

per

in

used

following components

the

Halt

cent

A1F3

electrolytes

the

5-5

volts.

carbon

base

calcium

chloride.

and

128

INDUSTRIAL

serves

as

the

ELECTROMETALLURGY

anodic

in contact

being

cathode,

with

the

liberated by the reaction

oxygen

whilst

carbon,

"

2Al203-"4Al+302
the carbon

consumes

anodes

according to

equation

the

"

A1203+3C=2A1+3C0
which

have

aluminium.

molten
I

The

by

The

rise in

by
the

bath

terminals.

to maintain

low

as

According

to

keep the bath

which

of the

monoxide.

carbon

suggested

as

method

Not

only is

The
and

are

cathodes

anodes,
35*5
the

of

however,

Heroult

in

are

diameter.

design

to

solidified electrolyte.

in

which

is

alumina,
to

serves

formation

or

lyte,
electro-

of

carbon

or

the

lated
granu-

burning

the

anodes

has

also been

externally heated, but

has

heating

the

on

dispensed

been

now

surfaces.

cooler

designs

to

the

rectangular in section.
vessel

are

of the

are

Hall,

Carbon
;

the

up

to

taken

in

employed

Special precautions
use

tion
forma-

by the

attack

similar

with.

economical,

more

usually stouter, occasionally

make

thick

point where they enter

reducing atmosphere of

were

electric

are

of the

for this trouble.

containing

iron

an

across

energy

the

obviate

to

the

at

electrolyteon

either round

made

the

surface

protected from

furnaces

Heroult

cms.

is

vessel

crust

in

internal

shunted

of

heat

to the

serves

furnaces

procedure

the

iron

the
of

good remedy

the

Whitewashing

of

this

but

also

originalHall

The

into

maintaining

electrolyte by

the

panied
accom-

continuously fed

la}rerof powdered

is

temperature.

electrodes

anode

is

decomposing

temperature

This

charcoal.
away

of

work

proper

with

day.

electrodes, indicated

one-half

usually solid owing

crust, is covered

the

is convenient.

is converted

the

is

alumina

from

once

electrolyte

the

across

voltage as
Pring*7 about

at the

maintain

the

remainder

the

tapped

low-voltage lamp

Fresh

in the chemical

expended

To

of

inches

two

are

from

voltage

luminescence

the

less than

furnaces

alumina

of

removal

and

maintained

be

to

protecting crust

of

ELECTROLYSIS

Working
7*0 with
A

Temperature.

cathode

The
8oo"
as

C,

operating temperature

of the

temperatures
been

10000

raised

C.28

low

substances

addition

of alumina,

to

iq

it

\h

le

low

is necessary,

as

it is remembered

temperature

falls off
due
ii.

b.p. 18000

the

If too

high

owing
to

for alumina

electrolytes the
has

is said

of the

the

to

of

m.p.

to

tioned.
men-

have

somewhat

7100

under

aluminium

C.,29 the importance of working

C.
is
at

will be obvious.
cathode

to the

the

that

addition

already been

of 8200 C, whilst the addition

m.p.
chloride
lowers the m.p.
volatile sodium

is

20

temperature

an

6570 and

as

composition diagram.

electrolyte2(AlF33NaF)3CaF2

The

When

low

as

melting point is first

Melting-point composition diagram

dissolved
in cryolite.

14."

obtain

of other

C. and

10000

of

(too

To

lytes.
cryoliteelectro-

neighbourhood

the

as

The

by the

indicated by the temperature

Fig.

high

as

per sq. dcm.

the published

employed.

at

then

and

is in

temperature

Cryolite melts
lowered

working voltage is about

amongst

7500 C. have

129

density of 190 amps,

current

usual

but

The

"

divergence is found

considerable

figuresfor the

ELECTROLYTES

FUSED

IN

density be employed the efficiency

resolution

formation

of aluminium

of metal

fog

in the

lyte
electro-

furthermore, the
9

INDUSTRIAL

130

ELECTROMETALLURGY

deposited metal
formed

The

closely the molten

V*l

metal

solid

actually greater than

Aluminium,
V

Vyli

LC

calcium

following figures by

electrolyte; when
is

of calcium

traces

by electrolysisof the

present.
how

contain

may

sodium

and

Richards

W.

in

approximates

the
that

sodium

and

fluoride
indicate

30

density

to the

specificgravity of electrolyte
metal

of the

"

commercial
.

""

""

""

""

""

""

Cryolite saturated with A1203

aluminium
Cryolite and
fluoride, AlF33NaF
Cryolite and

aluminium

fluoride

with

saturated

alumina

practice it

In

sodium

advisable

is found

not

fluoride, since although this lowers

yet it increases
formation

solubilityof

the

Aluminium

occur.

may

melting point, but

addition

should

appears

to

eutectic

at

the

be

various

salts

known.

the

The

melt;

of

S1

A1F3.

G.

by

figures of Richards

the

its

it forms

as

ages
volt-

electrolyte are

made

Experiments

the

fluoride

decomposition
the

arc

Gin
and

not
and

Minet

by calculation.

at

Decomposition
Voltages calculated.
Salt.

Gin.

A1203

actual

comprising

generally confirm

the

Calcium

cent,

and
lowers

substance,
per

melting point

also

of

sp. gr.

much

too

aluminium,

controlled.

37 mols.

the

fluoride

addition

best

"

accurately
arrived

therefore

Efficiency.

of the

32

raises

it

8150 C. with

Current

Minet

be

the

add

to

Calculated
Observed

Richards.

value

assuming

value.

complete
depolarization.

anodic

279

2*8

2*3

22

393

40

249

250

C+4F'

AlFg

NaF

47

...

"

j =Cf4+4@

"

E*(Al)/wAl2(S04)3=+i-28 volts.
The

current

of

efficiency of

9000 C.

is about

furnace

65 per

cent.

operating
An

at

increased

rature
tempe-

efficiency

ELECTROLYSIS
results in

of

95

of metal
has

cent,

per

noticed

that

assuming

the

the

ELECTROLYTES

At

fog.

7500 C.

frequently been

working

will

It

be

is low

furnace

with

maintained

are

in

efficiency

current

obtained.

conditions

efficiencyand

current

131

the reduction

to

efficiency of the

energy

best

95 per cent,

5*5 volts per furnace, the

efficiencyis only

energy

95
With

100

produce

output

is

Anode

monoxide

with

monoxide

high

densities

according

obtained

by

mixture

the

to

that

noted

forming carbon

anodes,

current

dioxide

and

hours.

kw.

already been

the

the

works

depolarization is

consuming

hours

kw.

most

1000

per

has

It

in

metal;

25 kgm.

anodic

oxygen

and

efficiency 1000

of

"

cent.

per

energy

approximately
Consumption.

liberated

=38

"

kgm.

153*2

practically complete

carbon

cent,

per

would

the

FUSED

lowering the temperature owing

formation

the

IN

equations

of
"

Al203+3C=2Al+3CO
2A1203+3.C=4A1+3C02
voltage of the

the

When

of dissolved

lack

the liberation
chloride

complete

formation

of

produced

the

06

from

maintained
to

this

can

this

this temperature,

cause

two

of

the

The

of the

tion
depolariza-

resulting in the
of metal

electrode

carbon

alone.

is

electrodes

molten

voltage loss

arcing is caused,

electrode

loss.

If the

anodes

and

ammeter

internal

roughly
must

the

are

not

are

they

enter

the

crust

drop

into

furnace

by

by the air

bath.

at

the

electrolyte,and
These

by

Frequently
an

thickly protected by

of molten
the

voltmeter.

be

in order

metal

over

accompanied

occasionally oxidized

they

carbon

of

to

if sodium

kilogramme

every

to

due

only be accomplished by regulating the distance

observation

of

For

inches

resistance

the

chlorine

or

owing

occur

electrolyte. Halogen

CF4 or CC14.
consumption

within

reduce

at

rise

to

effects may

halogens, either fluorine

of

is also

kgm.

anode

alumina,

present in the

be

is allowed

bath

increased

whitewash

point

where

long pieces

additional

losses

INDUSTRIAL

132

bring
with

electrode

the

former

the
obtained.

anode

working
33

Blount

aluminium,
obtained

carbon

anode

with

of

be

of the

metal

aluminium

Heroult

ing
workbe

can

high grade

densities

current

weight

careful

kgm.

per

must

in the

sq. dcm.

100

per

kgm.

contamination

undue

Technical

deposited,although
0*6

for

nearly weight

to

up

figure of

The

prevent

Hall.

loss

aluminium

the

amps,

ELECTROMETALLURGY

with

over

iron.

from

vary

to

to

80

in the

400

gives the followinganalysis of commercial

high degree of purity actually

indicating the

"

Al
..

..

Si

il

99-59

99-00

025
016

Fe
...

...

34

Wright
per

gives

UL

I.

98-45

0*87

1-29

0*13

o-io

of costs

followingestimates

the

kgm. aluminium

of production

"

1.

Power
Carbon

electrodes

Alumina

repairs,interest
capital, superin-

Labour,
on

tendance

22'4

electrolytes have

Other
but

have

received

not

important

more

been

suggested from

technical
be

may

23'3

time

to

application; amongst

mentioned

AI2S3 in molten

time,
the
lite.35
cryo-

gained owing to the low decomposition

than
more
voltage of the sulphide (0*90 volt) are
negatived in practice by the difficultyin preparing the
The

advantages

sulphide from
in sodium
The

produced
two

bauxite.

Minet

36

used

solution

of

cryolite

chloride.
annual

world's

in eleven

in France

and

Switzerland, Austria

output

exceeds

factories,of which
Great
and

three

Britain, and
Germany.

10,000

some

one

are

tons

in the U.S.A.,

each

in Canada,

INDUSTRIAL

134

ELECTROMETALLURGY

REFERENCES
1

Electrochem.

Zeit

Ind., 1, 14;
Elektrochem, 8, 817

Zeit.

Elektrochem.,

Elektrometailurgie

der

Trans.

"

Met.

Partington,

Zeit.

Elektrochem., 7,

Zeit.

Elektrochem.,

Ind., 4, 218;

Met.

Chem.

and

1902.

1902.

Alkali

Metalle.

Electrochem.

Atner.

"

10

Trans.

11

Zeit.

Elektrochem.,

12

Zeit.

13

Zeit.

14

Trans.

Alkali
252;

1901.

Soc,

17, p. 244

11, 612;

1905.

Elektrochem.,

8, 757;

Soc., 18, 117;

15

Zeit.

18

Journ.

17

Zeit.

18

Allmand,

19

Zeit.

80

Electrochem.

Ind., 8, 63

81

Zeit.

Anorg.

Chem.,

89, 389;

1904.

88

Zeit.

Anorg.

Chem.,

12,

272;

1896.

88

Zeit.

Anorg.

Chem.,

27,

152

Elektrochem.,

Griinauer,

25

Trans.

Farad.

88

Electrochem.

27

"

Pyne,

29

Greenwood,

30

Zeit.

18,

1905.

219;

1912.

1905.

1905.

Chem.,

2, 56;

89, 389;

1905.

Centres."

1908.

Electrochem.
and

1, 307;

1904.

1906.

"Electrochem.

367

1905.

1907.

Ind., 4, p. 152,

Elektrochem.,

Int.

27, 1403;
1902.

Anorg.

Amer.

1910.

1910.

Electrochemistry."

Soc,

Trans.

J. S.C.I.
V.

Nov.

Electrochemical

Some

28

32

Zeit.

612

Soc,

"Applied

84

81

81,

Chem.

1902.

Electrochem.

Elektrochem.,

and

1901.

7, 408;

Elektrochem.,

Amer.

Electrochem.

1910.

1908.

Elektrochem.,

Industry."

14, 216;

Amer.

1906

1906.

Electrochem.

Amer.

9, p. 123,

Soc,

Eng.t 8, p. 253
The

II.

; 1902.

8, 697;

SECTION

TO

Soc,

10, 63

Metal.

Ind.,"

1906.
p. 408, 1909.

1895.

; 1913.

Congress Applied Chemistry.

33

"

84

"Electric

36

G.

86

Borchers,

Practical

Electrochemistry."
Furnaces."

Gin, D.R.P.
"

1901.

1904.

148627

of

1908.

Elektrometailurgie,"

p. 108.

1905.

BIBLIOGRAPHY.
"

ElektrolyseGeschmolzenerSalze."

"

Principles

4*

"

"

The

Die

Alkali

R.

of

Lorenz.

Applied Electrochemistry."
Industry."
J. R. Partington.

Gewinnung

des

Elektrometailurgie

Aluminiums."
der

Alkalimetalle."

A.

Knapp.

Halle.

1905

Allmand.

Bailliere, Tindall

Minet.
H.

Knapp.
Becker.

"

Halle.
1903.

Cox.
1902.

Section

ELECTROLYTIC

THE

III."

PREPARATION

OF

METALS

RARER

THE

Gaiaxum.
Gaujum
from

is
the

salt in
the

conveniently deposited

gallate formed

complex

caustic

excess

cathode

under
o"

supercooled to

deposit

of

gallium

melted

be

can

(m.p. 30*15",

water

warm

cathode

platinum

solution

on

The

soda.

on

but

off
be

can

C).
Indium.

According
suitable

electrolyte

nitrate

the

such

agent

to

neutral

the

formic

Thiel

acid.

and

The

electrolytic potential of

indium

resembles

most

suggest

reducing

acid

weakly

ammonium

containing sulphuric acid

volt, and

of

suggests

bath

Ea=+o*45

Geer2

and

addition

the

is the

sulphate

Dennis

use.

chloride, with

or
as

Schucht

to

sulphate.

is

approximately

cadmium.

Thaujxtm,
in

I,epi"me
ammonium
made

of

use

platinum
at

amps,
Partial

35

The

E*=

neutral

a
on

of

anode
volts.

the

electrolyte. Forster

of

cathode

8 sq.

and

cm.

metal

The

presence

suitable

the

anode

of

can
as

100

be

resembling

volt
cobalt

iron.

1*5

KCN.

under

reducing agents such

The

1*3 to

is liable to occur,

is

(for Tl/Tl' solutions),the

or

of

fused

T1203

using

dcm.,

sq.

current

electrolyticpotential of thallium

+0322

of

oxalate

sulphate electrolyte, deposition

copper

precipitation on

especially in

as

double

the

suggested

thallium

and

taking place
a

1893

reducing

as

acetone.

approximately
metal
power

thus
of

the

INDUSTRIAL

136
thallium

ELECTROMETALLURGY

salts in terms

electrolyticpotentialdifference

of the

is"

Tryrr

tt*

log,

EA=I-I99+0024
Fused

Electrolytes.

mium,

conveniently

most

They

being the
each

temperature

metal,

in air, lanthanum

fairly stable

easily oxidized.

most

The

fused
with

metals

all white

are

slightlyyellowish tinge and

are

electrolysis of the

prepared by

chlorides.

anhydrous

neody-

samarium

and

lanthanum

praseodymium,

cerium,

elements

The

"

volts.

-j^r

from

seen

as

electrolysis varies

for

necessary

following table

the

for

"

Ce
.

La
Nd
,

Pr
.

Sm
Hildebrand

and

the

being placed in

cathode

fused

the

chloride.

the

In

anode
mixture

advocated

the

electrolytic

containing

electrodes.

As

electrolyte he

without

potassium

and

barium.

of

use

He

water-cooled

of

fused

the

used

chlorides

the

the

recommends

copper
carbon

chlorides,
of

sodium,

following

:
"

CeCl2
Na.Cl.KCl

parts.
parts.
15-20

BaCl2

200

Electrolysis with
yielded 750

the

potassium

and

vertically situated

two

addition

the

electrolytefor cerium

With

ing
contain-

surrounding

sodium

fused

layer of ammonium

compartment
of

electrodes

porcelain cell

porous

cell

or

of iron

use

used.

was

Muthmann

with

the

chloride, protected by

porcelain cell
chloride

advised

Norton

gms.

samarium

current

of metallic
a

very

of
cerium

120

trace.

amps,

at

12-15

volts

in 6 hours.

high cathode

current

density is

PREPARATION

required
of

to

OF

fusion

the

ensure

J part by weight

RARER

THE

137

The

addition

metal.

of the

chloride

of barium

METALS

the

to

is

chloride

advised.
Boron.

Experiments
indicated

borax
at

the

electrolyte and

carbon

by reduction

The

alloy

boron
fused

borate
of

preparation

the

B203.

B2C2, B6C,

reduction

sodium

claim

anode,

of the

carbides

of

Broadrill,6 using

and

Lyons

electrolysisof molten

the

on

formation

the

cathode.

boron

by Hampe

the

are

products

thermal
electro-

of

(seep. 172).
Vanadium.

Gin

M.

fluoride

between

iron cathode

an

of carbon

and

vanadium

cell lined

with

alumina.

of
per

be

600

amps,

dcm.

and

at

the

With
and

E.M.F.

an

of

compressed

cathode

anodic

an

of

one

in

density

current
200

amps,

vanadium

volts, pure

11-12

mixture

material

anode

as
a

could

of vanadium

the reformation

with

the cathode
anode

and

trioxide

dcm.

per

deposited on

fluoride

vanadium

suggested the electrolysisof molten

"

2VF3=2V+3F2
3^2+ V203 +3C=2VF3
+3CO
An

alternative

method

is the

electrolyteof V203 dissolved

Wood's
oxide

as

entails

process

in
the

of

use

double

carbon

electrolyte,requiring a much

in

an

fluoride,2VF3.3CaF2.

of the

use

anode

oxide

calcium

and

higher temperature.

Titanium.
Borchers7

electrolytewith
for the

patented
the

continuous

preparation of

Pederson8

alloy suitable
electrolysis of

the pure

suggests
for

many

titanium

electrolyte,using

the

copper

of

use

calcium

addition

chloride

of titanium

as

dioxide

metal.

copper

titanium

purposes;
dioxide
cathode.

it is
in

as

an

industrial

prepared

calcium

by

fluoride

the
as

138

INDUSTRIAL

ELECTROMETALLURGY

Manganese.

Experiments
of

solutions

concentrated

that

the

oxide
obtained
in

alkali

an

fluoride

the

electrolyte, adding

as

the

to

the

electrolyte

in

indicated

all

chloride

Simon11

similar

to

are

fluoride

or

calcium

suggests
oxide

of

traces

results

Better

manganese

manner

from

fused

electrolyte.

chloride

free

difficulty.

great

electrolysis

the

on

chloride

metal

electrolysis of

by

10

Bunsen

manganous

the

of

matter

and
of

of

preparation

was

Guntz

by

continuously

that

in

adopted

of aluminium.

production

Uranium.

This
methods

conveniently

most

can

(see

153),

p.

electrolysis of

by

but

be

very

fused

the

prepared
metal

pure

chloride

UC14

by electrothermal
can

be

deposited

between

carbon

electrodes.12

REFERENCES

Berg.

Hutten.

U.

Ber.,

Zeit.

Anorg.

Chem.

Zeit.

U.S.

Int.

37, 961

D.R.P.

Elektrochem.

Bull.

1880.

39;

40, 280;

1904.

1905.

Chem.,

1903.

150557.

Zeit., April,

Soc.

Pogg.

IIL

12, 841.

Appl.

Cong.,

SECTION

; 1904.

785962,

'

10

Zt.,

Chem.
,

Pat.

TO

Chem.,

Ann.,

11

Eng.

18

Rideal,

Pat.

Bonn,

91, 619;
17190,

"

3, 275

1892.

1854.

1900.

Elektrochemische

Das
191

1914.
;

Verhalten

des

Urans."

Diss.

3.

BIBLIOGRAPHY.
"

Die

Darstellung
Blanc.

Halle.

des

Chromes
1902.

und

Seiner

Verbindungen."

W.

Le

PROCESSES

ELECTROTHERMAL

IV."

Section

Zinc.

already referred

have

We

in both

rival to the

practice the

into

carbonate

slack

Owing

(over iioo"

of

whilst

coal

is short,

retort

coal

inside, but

high lime

The

half

consumption,

ore

be

may

low-grade

and

one

is

from

30

gases

outside

to

required
The

ore.

life

days, being

40

by the slags,especiallyby those

with

J
the

W.

of the

and

Richards

has

calculated

furnace

average

infusible

to

under

be

complicated by

is further

process

difficultyof removal

of

zinc

the

zinc

efficiency of

cent.*

per

ore

some

the

hot

iron content.

or

thermal

the

with

the

also

of

minimum

ton

per

zinc

the

expel

to

high-grade

averaging

only by

not

vapour

of

fireclay retorts.

distillation

the

or

weight

small, holding only

is the

ore

small

in

be

badly operated furnace

attacked

of

ton

4 tons

With

hours.

20

per

even

charge

of

sulphide

half its

about

necessary

must

retorts

of the

in

completed

of

C.) the

kgms.

30-40

in

high temperature

the

to

found

general

In

the

convert

heated

and

coke,

to be

ordinary method

with

oxide, is mixed

the
or

to

serious

most

disadvantages.

roasting

after

ore,

serious

the

practice is

The

processes.

suffers from

smelting zinc

of coal

solutions, but

ordinary Belgian thermal

electrothermal

in the

tons

in fused

and

aqueous

electrolyticdepositionof zinc

the

to

the

in the

slags remaining

retorts.
Not

only

labour
*

liners,

shapes
others
"

Der

as

and
in

the

information
well

furnace

material, but

and

For

are

as

sizes,
Trans.

Elektrische

the
see

on

heat

the
loss

Northrup,

Atner.

Of en."

operation

great difficulties
thermal
from

McLeod,

Electrochem.

conductivities
furnaces

and

Kanolt,

Soc,

1912

high in both

costs
are

of

with

met
various

electrodes

of

furnace

different

Fitzgerald, Langmuir,
to

191

7 ;

also

in

and

Bronn,

ELECTROMETALLURGY

INDUSTRIAL

140

the condensation
loss due

diffusion

to

and

retort

of the

especially if the
zinc

of the

of
has

sulphur

only

remainder

electrothermal
means

There

influence

the

on

blue

in the

formation

"

of

"

in the

factor

of

is

"

slag,

spelter,"the

more

in

common

is

Belgian, but

by

no

latter.
considered

are

blue

have

to

"

powder

electrostatic

an

in the

powder."

powder

which

formation

I. The

charge

zinc

the

on

globules daring the process of condensation.

The rapid chillingof the zinc globules in the condenser

vapour
II.

of the

(the

m.p.

say,

4000
are

considerably undercool
than

5000 C. and

concentration

of the

oxide

This

skin.

where

very

low

of the

zinc

oxide

is

vapour

concentrated

more

liable

more

The

ones.

issuingvapour.

Superficialcoating

III.

zinc

Rapid cooling to,

the globules before

found
lie
to
temperature has been
the
8500 C, depending entirely upon

condensing

between

Dilute

together.

undercooled

optimum

being 4190 C).

metal

C. may
run

be

to

"

as

of the

walls

of condensation

regulus

substantial

entirely eliminated

process

to

factors

three

the

actual

than

processes

are

through
been

not

blue

unimportant

an

they

"

of

formation

is

part of the zinc

part coalesces

being recovered

The

an

vapour

roasting. Again, in the

by

an

of the

retention

the

to

There

zinc vapour.

condensing globules

of the

factor

is

probably

spelter recoveries

followingequations

important

most

Reduction

made.

are

place according

take

may

the

with

of the

either

to

"

(i) ZnO+C$Zn+CO
(ii)ZnO+CO$Zn+C02
The

main

reaction

equation. Owing
sufficient

with
not

in the

case

with

gaseous

most

phase.

sphere
The

reaction
of
space

the

in
does

the
not

or

is

proceed

by condensation,
copper,

but

the

zinc

is
as

remains

consequently

reduced

between

second

metal

C, the reduced

of action

metals, e.g. iron

partial reoxidation
place,especiallyif the free
and

noo"

rapidity under
the

indicated

reduction

to the fact that

from

removed

is the

following that

may

ible
revers-

take

packed charge

time

same

has been

therefore,

can,

always formed,
of

production

dioxide.

to the

gas rich in zinc vapour

rapid fall in temperature from 11000

and 7000 C. in a very
short space.
is taken

advantage

re-established

will be
low

of redistillation

"

of the

electrolysisin fused

suggested

on

p.

(briquetted

of

of

refiningprocess.

blende

would

in test

calamine

calamine,

and

recovered

mixture

and

from

this

charge

was

20

per

relatively

solution

the

blue

the

of, the

use

operation

to the

following

Hill ore,

blue

powder

lead) and

cent,

further

distilled

as

anodic

If
"

gives the

with

mixed

lime, and

and

librium
equi-

with

Trollhatten, working

dust)

zinc

dust

C.

alternative

made

(30 parts Broken

7*5 parts coke

coke

be

very

(iii).
"

in

be reduced

at

runs

cent,

blende

which

this

zinc

could

Harbord

"

per

54

with

aqueous

free

the

conditions

these

to

"

6oo"

practicable.

the

anodes)

to

Consumption.

figures obtained

of

of

electrolyterecovery

Power

by

powder

or

prove

means

cost

might

59

depolarization by

reduced

between

Under

blue

by

powder

C. to

cooling

treatment

"

powder

providing a

and

slowness

by

bine

and
according to equations (ii)

temperature
Instead

relative

of the

"

complete ;
quantity can be

the

but

effective condensation

The

be

never

monoxide

original carbon

of the

75 per cent,

over

converted

of zinc
is

ELECTROMETALLURGY

INDUSTRIAL

142

part

taining
(conoxide

quantity

in

second

furnace.
Electrode

Energy consumption per

1000
kgm. of ore smelted.

2078
The

the

blue

in these

works

of

cent,

31*5 kgm.

figures include

above

recovery

of the

lead, and

the

necessary

powder.

Mounden

to

80

Artege, in France, using

hours,
were

zinc

kgm.

1000

or

with

required.
for

zinc

at

Gin

smelting
1500

kw.

1000

cent,

per

smelted

ore

calculates

kgm.

hours, while

of

the

for

energy
4

tillation
redis-

estimates

per

Salgues

silver.

zinc ore,
of

2016
current

the

zinc, 80

of the

consumption

current

of

cent,

of the

cent,

40-45

kgm.

G.

be 75 per

per

1000

per

required
cent,

consumption.

hours.

kw.

at

obtained

4800 kw.
kw.
of

hours
energy

containing 50 per
according to Stansfield 6
ore

ELECTROTHERMAL

Snyder

smelted

has

of 1050
Harbord's

kw.

at

600

take

the

kw.

kw.

coal

consumption

in the
Under

estimated

hours,

kgm. of oxide.

the

electrical

4^.

costly than

6d. per

to

of 4 and

the

of

ton

the

ij

tons

powder,

powder.

of

8d.

ton

per

maximum

and
of

ton

per

used, and

ore

sumption
con-

electrode

the

consumption

retort

of blue

to

Belgian process.
normal
working conditions
at

blue

consumption

opposed

sumption
con-

energy

of the

ton

per

power

as

energy

an

1000

hours

average

143

with

redistillation

1500

minimum
used

per

for the
to

500

may

ore

hours

oxide

figure includes

being about
of

zinc

pure

necessary

We

PROCESSES

per

ore

is

loss

is thus

less

in

ton

the

Belgian process.
7

Johnson
1

to

kgm. per

15

obtained
rates

estimates

essential

are

zinc

Furnaces

gained

be

to

Belgian retorts, and

Furnaces

taking

that

difficulties

in

employed.

possibilityof

the

three

to

operating

low-grade zinc

does
10-ton

cheap

is used

ore

(especiallyin
addition

to

possiblein

addition
carbon.9

and
small

the

The

"

chief advantages

smelting

processes

with

continuous

with

the

operation.

per

charge have

proved

not

contemplate

serious

capacity

units.

Other

as

silver

and

metal

slag

while

copper,
may

relatively high lead

the

of providing
possibilities
be tapped off and
worked

molten

separate from

be

o"E

run

content)

conditions

in

scarcely

retorts.

slag fusion

just above
to

ores

may

such

conditions

certain

The

metals

the

are

easily fusible slag which

under

power

increasingly important when

become

valuable

tons

Johnson8

which

advantages

for

those

thermal
operation of electro-

electrothermal

by

two

satisfactory,while

zinc

evident

feasibilityof working with charges larger than

is the

up

is

successful

the

from

at

figures considerably under

It

to

consumption

smelting process.

Types of Zinc

an

of ore,

ton

Harbord.

by

electrode

the

temperature

temperature

avoid

inclusion

of

silica is the

should

necessary

of the

metal.

be

adjusted

for distillation
In

silicious

to

lie

of the

slags the

controlling factor, in basic

slags

ELECTROMETALLURGY

INDUSTRIAL

144

Resistance
electrical

heating

who

1880,

Furnaces.

adopted

in

are

and

Pyrenees

{3000 kw.)

United

The

Cowles

and

operated

with

horizontal

arched

an

such

Fig.

and

coke

15.

used

was

intermittent

furnace,
and

in

as

The

roasted

flux, is

fed in

J, in which

together
is

passed

in

D,

the

hopper

carbon

is

separate

off to

mixture
the

Salgues,

of

ends

refractory,

forms

of

ore

type.
furnaces

the

have

were

the

Johnson

the

vertical

silver
a

were

Johnson
electrodes

(E)

into

when

the

carbon

through

The

covered

with

containing

slag
The

dioxide
the

chamber
D.

B, C, and

holes.

other

or

smelting

ores

of molten

tapping

condenser

lime

and

plate, is usually

layer

of

carbon

electrodes

three

containing

with

in

use

containing

charge

later

with

mixed

this

10

operation.

situated

; above

have

of

in

with

lined

Furnace.

The

those

through

are

lead

used

layers

as

ore,

electrode

molten
are

well

continuous

are

lower

action.

at

furnaces

inserted

resistance, and

as

In

kw.). Sarpsborg

20,000

The

Zinc

Resistance

"

Salgues

Johnson

firebrick

bauxite.

or

by

electrodes

of

furnace.

Norway.

earlier

the

chamber

fireclay

as

in

in
'

designed by Johnson

(Sweden,

Hallstahammer

Cowles

by

of resistance

furnaces

of

application

made

was

States, and

Trollhatten

and

form

resistance

in the

use

original

smelting

simple

form

modern

more

zinc

to

The

"

F.

These
zinc

and
column

lead
two

vapour

monoxide

I, which

PROCESSES

ELECTROTHERMAL
is filled with
this

means

and

with

zinc

pure

carbon

maintained

vapour

with

is

produced

receiver.

Johnson

only diluent
cooled

broken

60 per
this

monoxide

claimed

has

80

an

from

as

per

the
airzinc

cent,

per

30

By

in the

rapidly condensed

and

C.

cent,

ore

furnace.

of

type

11000

at

carbon

spelterrecovery

cent,

145

By introducing the fresh charge under the surface of the

is said to be minimized, ing
resultslag the production of smoke
in

gives

Johnson

For

of blue

decrease

low-grade zinc

of

lead, copper,

2#8

2600

amps,

ton

every

resistance

each

about

Two

be avoided

can

remove

i/.

the

to

volts
a

treatment

complete
before

the

by the additions

sulphur in

the

of

is used

duction
introeffects

employed

charge, and
A

to

powder

modifications

sulphide
removal

of the

of

flux which

slag,such

as

iron

or

lime.

been

sulphur by

This

suitable

with

overcome

reduction.
a

amps,

have
to

ores

of
each

operate

re-smelted

are

can

current

density of 128

current

of

furnaces

hours.

24

Various

liberated

gas

tons

per

of blue

ore.

roasting

three

ore

100

difficultyof the

prolonged

about

tons

of fresh

The

of

tons

suggested for the

the

charge before

metric

sq. dcm.

the

by the

furnace, corresponding
per

of

offers distinct

process

electric furnace

hold

at

silver the

preheating

economy.

at Trolhatten

smelt

containingrelativelylarge quantities

gold and

into the
considerable

following compositions of the slag

the

ores

The

advantages.

13

12

formation.

powder

difficulty
will

Snyder
10

16

INDUSTRIAL

146

fluxes

calcium

disulphideand
The

and

carbon

the

disulphide.
this

upon

of

production
17

process

sulphide according

ferrous

with

and

patent

zinc, carbon

carbide.

Pierron

C6te

iron

furnace, with

improved

simultaneous

claiming the

by

zinc

further

16

Oesterle

with

resistance

of

production

and

unroasted

ore

in

carbon

and

simultaneous
Brown

of the

treatment

suggests
lime

ELECTROMETALLURGY

uses

the

to

iron

scrap

reversible

produce

to

equation

"

Fe+ZnS^FeS+Zn

The

with
be

the

set

iron

of

kgm.

900

zinc and

of the

cost

300

following

The

Cost

Savoy.18

depreciation 9s. 6d.,

of

for

necessary

production

of zinc

diluted
must

reduction,

kgm.

1000

every

entailed

are

produced

of

4s. 2d. ;

total

Ugine,

at

Power

4$. 6d., iron

10s.

6d.,

4^., labour

3s.

38s. 6d.

used

are

of

mixture

of blende

Eleven

used

as

added

flux
on

at

in

the

would

usual
must

Dorsemagen

be

per

in

suggested

the

of zinc

and

of siliceous zinc ores,

simultaneous

while

use

Borchers

the

sulphur

as

carbon

copper,

is used.

resistance

The

furnace

for

by the reduction
patented

of ferro-silicon

modified

The

reducing atmosphere.

carborundum

production

majority of these

of

or

copper

resulting sulphide

practice iron

naturally be worked

six parts

of molten

the

parts of iron

which

to

carbon

furnace.

condensed.

from

in

three

C,

off and

but

manner,

production

from

11000

recovered

for the

and

addition

the

the zinc is volatilized

course,

The

wedge-shaped

resister

permanent

part of ferric oxide

are

of

furnace

as

one

sulphide are
pig iron

19

Imbert-Fitzgerald furnace

the

In

the

is not

lead

of zinc is lost in the process.

cent,

rods

the

kg. of lead.

1000

electrodes

6s. 6d., miscellaneous

liquid phase.
since

ores,

required for

every

ton

per

iron

scrap

costs

of the

right

Against these advantages

being

kgm. for

the

to

the zinc vapour

and

monoxide.

carbon

zinc out

for lead-zinc

directly recovered,

any

entirely

over

of the

is suitable

process

be

can

volatilization

the

through

the

shifted

equilibrium being

the

processes

and

for

process
zinc.

in which

disulphide or

products
by-

silica

as

ELECTROTHERMAL

carborundum
on

of their

technical

utility to
Furnaces.

employed

which

has

for

been

enable

to

been

not

assessment

an

important

most

smelting

in

have

made.
The

zinc

used

scale

be
"

147

obtained

are

sufficientlylarge

Radiation
furnace

ferrostticon

or

worked

PROCESSES

the

is that

United

radiation

of C. de

States

Laval,80
also

and

at

Trolhatten.
The
the

shaft

where

D,

between

arc

the

electrodes
zinc

A.

be

The

CO
at

be

noted

hole

to

slag

It will

is

arc

ably
consider-

electrode

the

although

electrodes

of

the

reducing

consumption,

kgm.

C.

which

lessens

the

in

atmosphere

from

radiation

through

that

operated

through

enters

high

the

removed

tapping

the

to

and

through

the

exposed

flux

and

horizontal

condenser, while

can

coke

ore,

it is

leave

vapours

temperature
the

of roasted

charge

40
metric

per

figure considerably

higher

of

ton

for

given

than

ore

required,

are

resistance

furnace

operations.
Reduction
obtained

in

retained
the

ore

cent,

these

in the

slag.

simple

the
to

very

low

resistance

the

of

type

be

can

metal

is

of the

diathermacy

consuming

poor,

zinc

pure

little of

very
the

to

efficiency is

power
is very

Owing

than

and

while

furnaces,

electrical

more

furnace

quietly,

proceeds

about

70

furnace.

per
The

operate.

Copper.

Very

few

large-scaleexperiments

electrical

smelting

of

promising

results.

The

may

be

(A)

roughly
Ores

divided

containing

ore,

copper
treatment

into

three

metallic

have
but
for

some

complex

classes
copper

been

made

in the

have

shown

copper

ores

(e.g.native

copper)

INDUSTRIAL

148
be

can

ELECTROMETALLURGY

directly separating the

smelted,

metal

from

the

gangne.

(B)

Ores

addition

containing
iron

to

smelted

be

can

part of the sulphur in the

assisting in the
should

contain

iron, while

the

(C) Oxidized
careful

By

ores

be
of

iron

bulk

carbon

of

of the

most

as

the

as

copper

of iron.
with

carbon.

in the

content

in the

of oxidation

resulting slag

selectivelyreduced

the

in

in which

heat

well

as

quantity

retained

be

can

the

small

can

adjustment

of the

most

with

furnace

The

ore.

silica

and

contains

matte

blast

of the

fusion

arsenide

sulphide or

in

arsenide

or

is oxidized, the

ore

oxides

the

sulphide

copper

slag in

charge

oxidized

an

condition.

Experiments
to

1903

1907

sulphide
on

The
Keller
zones

Vattier

used

of the

chamber,

furnace

be maintained

The

Vattier

power

of

and

cubic

kgm. electrode

gives the
matte

of

one

the

in separate
fused

in

one

the

second

to

ore

could

be

matte.

metres
was

ore

point in

fusion

of

capacity.

500

kw.

hours

1000

per

material.

following percentage

analysis of

ore,

consumption

volts with

the

that

twenty-four hours

consumption

charge, slag and

119

so

at the

per

furnace

power

ore

tons

favourably reported

were

pairs of electrodes

two

from

matte

copper

simple resistance

separation of slag from

in

treated

at

with

Twenty-four

The

was

of

from

Government.

Chilian

type furnished

effect the

kgm.

furnaces,

for the

furnace

could

zone

production

the

on

Iyivet in France

and

Praz

at La

in resistance

ore

M.

by

made

power

"

for the furnaces

factor

of 0*9.

averaged 4750

amps.

ELECTROMETALLURGY

INDUSTRIAL

150
carbon

hearth

and

entering through
with

one

roof.

the

broken

coke,

silicon metal

of the

or

of

ore

after

The

JC

""

Ol

..

""

Other

""

"

""

""

aO

""

""

ft

metals

2
.

ft

slag consistingchiefly of aluminium

silicate containing about
0*5 per cent, of
kw.
hours
1200
consumption is about
F.

smelted.

his process
also p.

furnace

for the

The

nickel.

of

use

power

revolving

of ferro-nickel ;

production

(see

operation at Essen, Germany

is said to be in

of

kgm.

1000

per

Clergue has suggested the

electric radiation

magnesium

and

ore

ferro-

nickel

14 per cent.

""

and

crushing is mixed

reduction
yielding on
followingcomposition

Ni

electrodes

vertical

series

228).
Manganese.
is

Manganese

ferro-manganese, the

and

limited.

it

Although

electrolytic methods

quicker and

are

Moissan
a

small

27

effected

several

minutes.

He

present

in the

cpuld

not

method.

sodium
under
at

metal
the

carbon

by

processes

is

of the

mixture
small

below

the

its

metal

which

has

of

means

melting point

produced
vaporization (m.p.
can

manganese

sodium

this

By

be

12470 c.).
Tin.
Harden
for

the

3"

has

reduction

given
of

details

tin

ores.

of the

by this

with

Mn02

few

Borchers

carbon

excess

carbon

excess

furnace.

point

in

Mn02.

of

arc

produced

which

well

with

volts,

at 60

amps,

the

in

by carbon

Mn02

the

remove

refusion

in

C, from

temperature

to

removal

used

of

gms.

by

of

of 150

current

hundred

manganate
20000

being

form

pure

electrothermal

reduction

attempted

Gin29

sulphate and

the

with

confirm

in

prepared

metal

pure

convenient.

more

preparing

be

can

(p. 138), the

furnace

arc

for the

demand

spiegeleisen

of

usually produced in the forms

conditions

Although

necessary

electrothermal

PROCESSES

ELECTROTHERMAL
of tin

smelting

scale, with

ordinary

of

exception

the

oxide

by

are

have

methods

losses

where

plate

of

the

volatilization

by

prospect of future

some

in tin

inconsiderable, the

means

no

technical

unsatisfactory working

the

to

furnace

blast

accomplished on
tin dross smelting

been

not

yet, owing

works,31

stannic

has

151

of

thermal
electro-

development.

Chromium.
Metallic
small

is

chromium

industrial

simple

metal
is
the

It

being

usually accomplished by

comparatively

with

charging, the

broken
of

means

production

obtained

be

can

using intermittent

by reduction

produced

on

electric furnace

(see p. 234).

furnace

arc

chief

scale, the

being ferro-chromium
a

only prepared

Reduction

out.

carbon

fused

according

to

equation

"

Cr208+3C=2Cr+3CO
The

reaction

metal

usually contains

which

is difficult to

Refusion

with

11850

at

commences

the

calculated

the

removal

effectual

More

of lime

to the

3Cr3C2 +2CaO

under

small

these

developed

reduction

with

crucible

process

charge

antimony

the

in

accomplished

"

calcium

Aschermann
for

be

can

oxide

carbon

and

oxygen

=9Cr +2CaC2

quantities of

conditions.

of chromic

amount

the

although

resultinggrey
carbide, Cr3C2,

remove.

of both

by the addition

hard

extremely

usually entails the presence

metal.

The

C.32

+2CO
chromite

at

Cassel

are

formed

successfully

by
preparation of chromium
sulphide in a small graphite

"

2Cr203+Sb2S3=4Cr
The

antimony

uses

silicon

as

is
a

+2Sb

entirely removed

reducing agent

+3S02

by reheating.

"

2Cr2Os +3Si =4Cr +3Si02

Becket

33

INDUSTRIAL

152

ELECTROMETALLURGY

Molybdenum.
Metallic
demand

in the

with

chromium

carbon.

increasing

an

of

deficit

easily

more

of

reduction

the

by

small

is

there

special steels, is

of

production

than

prepared

for which

molybdenum,

oxide

the

according

carbon

the

to

equation

"

the

ensures

of

presence

=Mo

+2C

Mo02

+2CO
in the metal.

oxide

excess

is sufficiently
volatile to be

easilyremoved

from

common

melt.

the

is the

sulphide, and

molybdenite
and

The

!Lehner

direct

the

suggested the

by the sublimation
of

form

molybdenum

preparation of

subject of

is the
*"

most

with

reduction

ore

metal

the

from

Guichard34

patents.

many

oxide

The

in

carbon

the

of lim"

presence

MoS2+2CaO+2C=Mo+2CaS+2CO
Becket

36

has claimed

of carbon

amount

indicated

than

2MoS2+2CaO
Calcium

carbonate

for reduction

the process

by the above
+2CaS

=2Mo

+3C

of course,

may,

with

smaller

equation

"

+CS2+2CO

be used

of lime

instead

"

2MoS2+2CaC08+5C=2Mo+2CaS+CS2-f6CO
The
to

addition

proceed

of calcium

smoothly.37

more

in the

molybdenite

fusion

of the

by

are

metal.

as

Small

flux

the reaction

causes

of iron

traces

by volatilization

removed
38

Neumann

of silicon ;

means

fluoride

according

to

has

present

on

further

suggested the reduction

39

Keeney

"

MoS2+Si=Mo+SiS2
unsatisfactory results
a

growing

effective

market

for the

as

were
a

reducing agent, and

preparation of

5MoS2 +2CaC2

Calcium

obtained.

metals

=5Mo

like

+2CaS

carbide
is

especially

molybdenum

+4CS2

has

"

ELECTROTHERMAL

PROCESSES

153

Tungsten.
This
the

metal

is also

preparation of

industries.

For

isolated,but

reduced

Owing, however,
ferro

alloy pure

manufacture
filaments
in

steel

most

tungsten is used

oxide

is

of carbon

amount

in the

furnace

arc

preparation of

carbon

The

resultingmetals
The

and

the

containing

melted

to

variable

prepared

be

can

for the

used

those

lamp

Uranium.

and

be

can

prepared by

reduction

respectiveoxides, V2Os, Ti02 and U308.

always contain small quantitiesof the

of their

nitrides.

industrial

they

In

hydrogen

subsequently

similar

Titanium

elements

with

and

of

means

free carbon

and

the

chromium.

three

carbides

not

of

electric

and

by

Metal

by methods

contents

work

and

metal.40

Vanadium,
These

furnace

carbide

as

usually

high-grade steel.

for

usually reduced

ductile

the

to prepare

carbon

steel

for

electric-resistance

an

is

metal

the

variable

the

of tungsten
the

work

lighting

electric

in the

and

produce ferro-tungsten (see p. 232).

to

to

increasing quantitiesfor

in

being used
specialsteels

is in the

demand

always produced

are

ferro-alloys,

of the

form

such.

as

Zirconium.

According
reduction

by
at
that

with

volts

40
no

The

Moissan

to

in

reduction
element

41

with

carbon

simple
took
is not

this

arc

element
a

be

can

current

of

1000

Greenwood

furnace.

produced
amperes
42

found

place below 14000 C.

produced industrially.
SnjcoN.

is

There
as

Its

distinct

limited

from

the

growing demand

but

ferrosilicon

for this element

alloy for reduction

purposes.

cule,
moleoxidation, being 215,692 calories per gram
is only exceeded
and the alkali metals.
thermite
by

heat

of

"

Crude

silicon

is

prepared

"

from

silica

by reduction

with

carbon,

in this

and

impurities.
the

treat

with
A

ELECTROMETALLURGY

INDUSTRIAL

154

effective

An

material

crude

stir in

coke, then

be

poured off
at
14600 C,

14300 C.
lined

The

current

passing

The

furnace

is

28000

had

at

furnace

kgm. of silicon

350

from

can

as

be

of

tapped

the

few

off every

According to Stansfield 46 a high-grade

the followingcomposition :

the

(b.p.

arc

from

kw., and

1000

hearth.

the

furnace, since

temperature

uses

being
carbon-

use

to

resistance

the

44

depending electrodes,

electrodes

mences
com-

metal

the

works

two

the

silicon

Reduction

moulds.

with

powder.

the

separated,and

to

covered

crucible

magnesium

Carborundum

operated

Each

C).

is

melting point of

the

is volatilized

43
purification

of

cent,

sand

furnaces

the

other

in

hours

per

into

Acheson

firebrick

element

for two

"-3

Si02, N2, and

of

method

silicate is

slag of magnesium

can

it contains

state

250

to

hours.
silicon

unrefined

"

Si

9571

Fe

24

Al

96

001

008

per

cent.
a

it

Potter48
a

has

reducing agent

suggested the

of

use

silicon

carbide

as

"

Si02+2SiC=3Si+2CO
Attempts

have

been

made

to

cally,notably by Deyille, Minet

either sodium

adding
A

silica from

interaction

some

of which
These

of
have

silica and
become

or

have

results

been

in the

carbon

as

lyte
electro-

potassium silicate,

; indifferent

to time

great variety of compounds

the

work.

time

electrolyti-

Grosz, using

and
silicate

potassium

silicon

prepare

were

tained.
ob-

prepared by

electric furnace,

extremely important in technical

will be referred

to in

later section

(p.164).

well-known

tions,
modifica-

Graphite.
Carbon
two

can

exist in at least three

crystalline47

and

one

amorphous

diamond,

ELECTROTHERMAL

graphite

The
coke

low

at

form

graphite was

that

the

was

very

tedious

aluminium

direct

formation

of

graphite

is the

of

coal

anthracite,

of pure

or

He

the

graphite

into

carbon

of small

presence
such

such

non-metals

Townsend

to

the

function

of

conversion

boron, catalyticallyhastened

According

stable

developed by E. Acheson.

first

certain

and

for

whilst

operation,but that the

impurities,especiallymetals

quantities of

is the

diamond

temperatures,
transformation

found
a

155

5000 C.

above

technical

into

The

ordinary carbon.

and

modification
stable

PROCESSES

iron

as

and

silicon

as

or

conversion.

preliminary ionization
graphite from carbon,

is

sary
neces-

the

and

catalytic material

the

to
apparently serves
decomposition of a carbide formed

produce graphite by the

by the catalyst with the carbon.

is assumed

It

place

in the
is

behind

hottest

but

there

form

of

the

as

decomposed

takes

temperature
leaving

volatilized

the

to

of carbon

conversion

the

recommence

of

graphite
be

of

catalyst is not absolutely

11000

say,

at

C. will not

higher
11000

C. carbon

redeposited in

Fitzgerald and
the

relative

low

temperatures

vapour

vapour

form

the

Forssell

between

at

6400

the

be

solid

will
of

others,

thus

and
carbon

the
the

In

vapour

carbon

same,

pressure.

presence

gradually sublime

graphite.

of

attempted

7000

of carbon

C. 5*4 times

as

great.

at

by

studying

when

carbon

found

They
was

measure

graphite

C.

C+C02^t2CO,
is present.

to

and

carbon

5000 and

equilibrium composition
graphite in the solid state
5000 C. the vapour
pressure
graphite,and

the

have

pressures

the

consequently

above

vapour

and

Borchers
be

that

5000 C,

above

carbon

the

noted

necessary

dispensed with.
graphite is the stable

it cannot

production

carbon

possessing

of

is

catalyst is

the

already been

has

graphite at,

at

furnace, and

by the experiments of Acheson,

pressures

or

to

the presence

for technical
It

the

of the

zone

carbide

of the

graphite.

is shown

and

formation

gradually raised the carbide

zones,

That

of

the

graphite, whilst

colder
to

that

times

37
.

that
that

At

Niagara,
into

oxide

which

of iron, and

heating

the

30

feet

of

fireclay bricks

long and

terminal

plates

they have

with

to

carry

core

is about

deep, constructed

and

15,000

over

rice

of

size

furnace

The

liner.

slab

furnace

of the

end

cent,

per

electrode

Each

wide

the

carborundum

at each

with
to

version
con-

long trough

carbon

current.

feet 6 inches

of

mixed

surrounds

for

carbon

consists

furnace

finely crushed

is

anthracite

carries

since

The

the

as

of anthracite

6 tons

grains. The

is used

anthracite

graphite.

holding about
of

ELECTROMETALLURGY

INDUSTRIAL

156

water-cooled,

are

amperes.

HH

for graph

carbon
St..

Fig.

17.

8000

end

The

furnace

kw.

at

day

The

20,000

to heat

pure,

usually containing only from

has

o*i

been

not

to

resistance

from
is

o*8 per

volt.

four to five

remarkably

cent,

completely

at

current
at 0'8o

amperes

up, and

ing
commenc-

the

resulting graphite

to

Graphite.

the

as

temperature

days

ash, chieflyiron which

of

furnace,

volts, and

200

of the

about

down.

production

per

operation is about

takes

cool

for the

consumed

are

elevation

of the

the

Furnace

amperes

with

decreases

couples

Resistance

"

1600

About
at

thermo

ih*ing

mineral

removed

by

volatilization.
The

adequate

embedded

in

difficulty. The
well

20000

over

ensure

between

the
the

of

protection

the

limits

of

C, have

to

presence

is

anthracite

of

graphite and

the
be

the
a

pyrometer

matter

considerable

graphitizing zone,

continuously observed

non-graphiticcolder
the

of

couples
which
so

anthracite

fusible firebrick.

as

is
to

liner

INDUSTRIAL

158

of electrical

Processes

various

ELECTROMETALLURGY

graphitizationhave

grades of coals, and

dried

to

even

been

applied
have

peat, but

to

not

proved technically successful.

Phosphorus.
is

Phosphorus
by electrothermal
of

smelting

wavelite, and
obtain

methods.

mixture

phosphorus vapour
to the equations

The

of bone

rock

liquid

in

being produced
ash

the

or

with

with

essentially

minerals

carbon

aluminium

or

diluted

consists

process

phosphates

calcium

increasing quantities
apatite,
silica to

and

silicate

carbon

slag

monoxide,

and

according

"

Ca8(P04)2+3Si02+5C=3CaSi03+5CO+2P
2MP04+3Si02+3C=M2(Si03)3+5CO+2P
chief

The

production

of

will

vapour

phosphorus
and

condensation

in

fed

commence

The

14600

C.

under

water.
ores

per cent,
In

with

the

with

its

phosphorus

materials,

porous

the

on

domed

the

through
exclude

resistance

even

every
at

roof

three

11500

containing but
is obtained

or

hours.
to

is condensed

be

in

tinuously
con-

screw

off

by

Reduction

completed

copper

at

vessels

quantities of iron, 80-90

in this kind

designs of furnace,

of
is drawn

slag

four

the
in

base

charge is

means

C.60 and

small

the

The

by
the

Readman

system,

near

roof.

air, and

phosphorus

recovery

later

electrical

walls.

tapping

intermittent
to

to

as

so

conveyer

With

which

through

operated

were

cylinder

firebrick

with

the

associated

being disposed horizontally

electrodes

is said

those

are

ease

with

satisfactory furnaces, designed by

first

Parker,

and
\

the

penetrate

through the furnace

The

associated

difficulties

such

as

of furnace.
those

of

Irvine,

I^andis
(Anglo-American Chemical
Co.) and
(American Phosphorus Co.),certain improvements have been
slag resisting furnace
incorporated, eg. phosphorus and
Machalske

liners

made

of

vitrified brick

set

in

an

asbestos

sodium

PROCESSES

ELECTROTHERMAL
silicate

Horizontal

mortar.

either

eliminated, and
tuted.

The

system,

more

either

furnaces

electrodes
annular

an

the

on

former,

the

have

been

pendent electrodes

more

operate either

the

and

electrodes

carbon

or

frequently

between

electrodes

one

159

the

arc

being formed
the

between

or

ring

carbon

resistance

or

arc

themselves

substi-

in the

set

furnace

walls.
The
80

earlier pattern

kgm.

furnaces

of

phosphorus
capable of producing

be

According
smaller

the

furnaces

phosphorus.
reduced

In

61

hours

the

about

modern

later

said

are

to

hour.

one

for

consumption

energy
kw.

11*5

ones

in

amount

same

was

more

5 kw.

to

the

output capacity of

an

; the

day

per

S. Richards

to

had

hours

kgm.

per

larger units this has been

and

kgm.

per

Arsenic.

Arsenical

by the
Westman
The

thioarsenide
a

or

chiefly of

of iron.

On

is condensed
In

process

between

cast-iron

dealing with
is

matte

furnace
with

gas

by combustion

period

the

external

of

kw.

some

condensers

hours

to

in

set

at

the

and

for treatment.

furnace

capable of
ferrous sulphide

current

of

the

of the

the

and

arsenic

nitrogen

oxygen

in the furnace.

is

gas.

closed

of

commencement

run

removed

During

arsenic, condensation

place.

metric

the

forms

of condensers

system

takes

whilst

time

of the arsenic

Hering,

the

gold

is volatilized

The

hour.
to

by

of volatilization

According
1000

time

blower

round

air is circulated

the

and

space

per

ore

furnace

the

containing any

arsenic

electrodes

tapped off from

from

removed

system

kgm. of

90

Co., applying

parts of the furnace.

is heated
the
by alternating
ore

colder

the

on

veloped
de-

reducing atmosphere

obtained
The

ore.

Westman's

current

The

in the

silver present

being

mispickel, FeS2.FeAs2,

heating in

sulphide is

of ferrous

matte

is

deposits in Ontario.

ore

consists

ore

arsenic

Reduction

Ore

the

to

process

of

production

electrothermal

The

ton

of

ore

requires some

in

ELECTROMETALLURGY

INDUSTRIAL

160

Carbon
All the carbon
in the

United
in E.

Taylor's resistance

electrical

over

the

ordinary thermal
and

(p.161} consists of

furnace

at the

packed carbon
is not

carbon

in at

the

of the

column.

chamber

at the

disulphide is formed,
cool

the

liberated

current

of

and

through

four

section

and

as

situate

and

stated

are

in the
be

to

long,

metres

the

sulphur can

be

double

the

between

the

at

at which

action
re-

the carbon

interchanger

heat

each

are

of iron, and

to

feet

41

they require

to

60

volts, transmitted

each

25

sq.

right angles

at

Fresh

top of the column,

furnaces

40

D,

of the

base

built
at

amperes

Dense

through

it arrives

means

The

electrodes, D,
1 '2

at the

space

serves

vapours.

4000

Raw

temperature

same

high, 16 feet in diameter, and

a

four.

are

this

By

resistor.

to time

time

annular

the

down

runs

as

by sulphur vapour.

through four similar hoppers

B, B, and
walls

there

The

cylinder containing

serves

from

base

of production,

cost

to the workmen.

double-walled
which

base

hoppers A, A, of which
in

danger

appreciably attacked

is fed

carbon

of

absence

great advance

regards

as

N.Y.

Yann.,

at Penn.

both

method,

is produced

year,

per

sulphide is

the

industries

various

tons

2000

furnaces

preparation of

purity

in the

disulphide used

States, exceeding

The

fed

Disulphide.

furnace.

in

dcm.
to

Still

cross-

another,

one

larger furnaces

contemplated.

the

sulphur (m.p. 1150 C.) flows to the base of

furnace, where it slowly vaporizes (b.p.444*5" C), passing

up

through

The

molten

800-10000

the
C.

formation

heated

to

of carbon

layer of

is maintained

which

carbon

charcoal

in

the

disulphideaccording to

the

from

at

The

tower.

equation

C-f-S2==:CS2
-

is

complete

at

Charcoal
fed in

containing less than

furnace

CS2 before

ash.

bright red heat.

3 per cent,

through the hopper F situated

Each
of

The

"

will

yield approximately

it is necessary

output

at the

from

each

to

dismantle
furnace

ash

is used,

being

top of the furnace.

1000

and
is about

metric
clean
7500

out

tons

the

kgm.

ELECTROTHERMAL
per

day, representing

kw.

hour.
2000

at

If

C,

we

we

that

calculate

from

of

output

an

assume

can

necessary

PROCESSES

leave

gases

data.

kgm.

12

theoretical

following

the

about

the

the

161

the

energy
The

CSj per
furnace

tion
consumpof formation

heat

"

C+2S=CS2

LJ

"G5"

-Carbon

is 19,000

calories.

per

kgm.,

200

The

is
kw.

0-45

furnace

vaporize

the

the

calories

necessary
to

furnace.

heat

to

0-24=48

energy

equal

and

To

disulphide

thus

shows

an

"Met.

"

Ind.

"

"

Calculations,"

Chetn.,

Iron

Mining

"

"The
1907.

at

Mag.,

Oct.,

C.

we

amount

total

2'2

kgm.

need
of

calories,
per

kw.

efficiency of 55 per

hour.
cent.

IV.

SECTION

8t":

Trollhatten,"

117.

Eng.

and

Min.

Journal

Feb.,

1914.

1910.

Electrometallurgy
p.

required

7, 873.

1917,

Smelting

18,

or

energy

TO

p.

2000

are

250+72+48=370

kgm.

REFERENCES

to

The

kgm.

therefore
per

up

N.Y.

Yann.,

CS2 72 calories

vapour

per

hour

Perm.

of

Zinc,"

Trans.

Amer.

Electrochem.

Soc,

ELECTROMETALLURGY

INDUSTRIAL

i6s
"

"

"

Furnace,"

Electric

The

Trans.

Atner.

Electrochem.

Trans.

Amer.

Electrochem.

Trans.

18

U.S.

814050,

11

Proc

Pat.

18

Chem.

18

Met.

14

Trans.

11

U.S.

10

Trans.

17

"

Eng.,

18

Chem.

li

Met.

6*

10

U.S.

Pat.

81

Mining

11

Chem.

Kremakoff,
Zeit.

84,

88

Met.

87

C.R., 116, 3549

18

Elektrometallurgie, 3rd

88

Bull.

and

Trans.

Hutton,

88

Electrochem.

84

C.R., 122, 1270.

88

Metallurgie,

40

E.

x, p.

1910.

p.

519

277

191

315.

1903.

19".

453;

18, 1910,

Soc,

p. 205.

1908, p. 1483.

Soc,

116,

"

CJl.,

I.S.C., 98, 1483

48

Chem.

44

Electrochem.

48

"

122

Zeit., p.
and

and

Electrochem.
H.

Electrochem.

"

Bragg,

48

Allmand,

Hempel

81

Electrochem.

1905.

and

24,

Soc,

191

3, p.

186.

Industry/'

Lighting

1897.
1908.

215

; 1914.

Met.

Ind., 7, p. 142.

Met.

X-Rays
Applied
Muller,

p. 281.

Ind., 7,
and

Ind., 4, pp.
"

60

Furnace,"

Electric

48

1907.

The

41

47

1906.

Electrochem.

Rideal,

The

Soc,

28, 356

41

44

20,

1901.

1904.

of

1016;

p.

Eisen,
Amer.

K.

1900.

3549;

835052
,

u.

84, 333

Ind., 5, 239.

Pat.

Trans.

1910.

1909.

Auf.

Chem.

88

89

1910.

3.

Electrochem.

Amer.

Stahl

Ottawa,

1893.

Eng., 9,

Chem.

88

Eng., 8,

Chem.

Technologique,

J. S.C.I.

furnaces

electric

of

zinc."

and

209

Electrochem.

Trans.

U.S.

1905.

Chem.,

Anorg.

Chem.,

Amer.

84

1912.

1192;

Zeit.

Anorg.

87

8, 171

191

18

Trans.

Soc,

steel

p.

p. 909,

Zeit., 86,

Metal.

1914.

380.

3, p.

Eng., 8,

Journ.,

14

81

768054.

"s

80

191

construction

pig iron,

191

Chem.

1903.

p.

the

in

of

production

1913.

1905.

advances

Recent

France,

Soc,

Electrochem.

Amer.

24,

Soc,

5.

p. 281.

1912,

Electrochem.

814810,

Pat.

24, 1913.

191

1913.

Eng.,

Amer.

Soc,

de

Civils

Zeit., p. 416;
""" Chem.

25, p. 176;

1904.

Ing.

des

Soc.

Soc,

Electrochem.

Amer.

Petersen,

p. 324.

Crystal
343,

p.

1909,

502

86.

Structure."
;

1906.

Electrochemistry,"
Zeit.

Ind., 1, 17;

Angew.
1902.

Chem.,

p. 444.

18, 632

1905,

for

the

PROCESSES

ELECTROTHERMAL

TO

BIBLIOGRAPHY

"The

Electric

"Der

Elektrische

"

Kunstlicher

"Die

Metallurgie

Furnace,"
Ofen,"

Graphit,"
des

163

IV.

SECTION

Stansfield.
Bronn.
F.

Zinns,"

A.

Fitzgerald.
H.

1904.

Henniche"

V.-CARBORUNDUM

Section

AND

OXYSILICIDES

reactions

The

occurring between
of the

high temperatures
and

OF

led to the commercial

have

carbide, named
of
under

the

is used

Carborundum

material

the

in

drills and

bits for rock

the

applicationas

its

mentioned
steel and

as

infusible

an

is

Carborundum

production

of

coverer
dis-

time

was

crystalline

metres

of

brickwork

an

in

high and

metres

and

intimate

containing the
of

mixture

that

the
a

fired furnaces.
furnace

ing
follow-

furnace

for the
is about

broad, built up

carbon
coke.

core,

about

charge

sisting
con-

followingcomposition

52*2

to

54*4 per

"

cent.

35-4 to 35-1
6 to
10
7*0
r8 to
3*5

Salt

loosely packed round

usual

of the

Sawdust
.

metres

be

may

preparation of

coke

Each

to.

put

by E. Acheson

f-inch crushed

Coke

noted

be

substance

in the

that

uses

can

resistance

adopted

Sand

It will be

of the

liner for coal and

prepared

in diameter,
of

diamond

as

abrasive,

an

of other

multitude

graphite (see p. 156).

long, 5

10

the

the

the

at

contained

deoxidant

general construction

the

is

is silicon

these

large quantities as

hard
as
crystallinesubstance
the other
important uses
Among

metre

ally
industri-

Acheson,

who

1891,

by E.

varied,

very

of many

of

the

(corundum).

alumina

as

in

the

are

chief
"

carborundum

compound
impression that

furnace

The

silica at

and

production

important compounds.
"

CARBON

carbon

electric

THE

core.

slight excess

of coke

the

equation

proportions corresponding

to

Si02+3C=SiC+2CO

is used
"

above

166

ELECTROMETALLURGY

INDUSTRIAL

(Si2C20)

in

not

are

from

silica and

agreement

carborundum.

It

may

siloxicon by carbon

or

the

to

as

complete, investigators

is

carbon

of

formation

of

method

produced by the reduction

silicon at a higher temperature
be

of

"

(i) Si2C20+C^2SiC+CO

Si02+C^SiO+CO
SiO+C^Si+CO
Si+Si2C20^2SiC+SiO

(2)

or

the

interaction

produced by
silicon being

equations
.

formed

and

either

to

(b) From

carbide

In

Richards

calculated

has

various

at

the

probable

temperatures,

the

sure
pres-

following

"

presence

of the

Hg.

0001

19200

C.

0005

i9600

C.

001

2000"

C.

0*02

20600

c.

0-03

2100"

C.

005

21550

c.

O'lO

22150 c.
22550 C.

0'20

that

interaction

pressure

mm.

18200

for

account

thus

vapour

with

considers

the

following

silica,Si02+2SiC^3Si+2CO

and

Vapour

the

of the

SiO+C^Si+CO

Temperature.

to

vapour,

"

of carbon

He

carbon

siloxicon,

results

silicon

according

{a) From

of

030

this small

the

of

of

growth

of silicon
an

and

pressure

in the

carbon

formed

would

of

is

quite enough

crystals from

carborundum

of silicon vapour

excess

silicon carbide

vapour

course

vapour

form.

the dissociation
be

depressed,

permitting of slightlyhigher working temperatures.

Tone

brought

believes

about

silicon vapour

that

by the

the

formation

interaction

according

to the

of

of carbon

equation

3Si+2CO^Si02+2SiC

"

the

carbide

monoxide

is
and

CARBORUNDUM
the

By
write

the

interaction

direct

equations

siloxicon

as

167

for the

follows

of

and

carbon

silica

we

can

of silicon carbide

production

and

"

(1) Si02+3C=SiC+2CO
(2) 2Si02+5C=Si2C20+3CO
view

In

such

of the

the

of these

outlined

does

compounds
series of

Allmand

production

The

we

calculate

of carborundum

the

follows

as

part

of

11*3 and
heat

o" and

to

the

the

specificheats

between

99

29,200

99

kilomol

is heated

passing through

molecular

To

of

:
"

and

(40*3 kgm.)

requires

calories.

19,000

carborundum

effective

necessary

carbon

calories.

2,000

temperature

room

(2 X 29,200)="i

on

energy

"

production

at

The

those

as

respectively

are

the

Hence

are

direct

the

such

of silica,silicon carbide

Si+C=SiC+
C+0=CO+

the

of

place,but they

reactions

Si+02=Si02+i8o,ooo

CO

take

not

simpler

may

of formation

heats

monoxide

the

that

probable

extremely

reactions

above.

With
for the

of

result

of molecular

rareness

it is

high order

formation
are

extreme

We
21000
cold

charge

whilst

C,

C. and

that

assume

the

liberated

surrounding charge leaves

C.

14000

at

of carborundum

21000

180,000+2000"

further

can

of carborundum

and

o" and

The

mean

carbon

14000

C.

ide
monox-

respectively

7*1.

required can

be

To

forming carborundum
heating up SiC, 113

To

heating

up

CO,

X71

summarized

as

follows

=119,600
X 2100

Xi4""0=
Total

"

calories.

23,700
19,900

=163,200

99

_i63,20QX4'i9
~~

40-3x3600
=47

hours

kw.

kgm.
hours
ton.

or

per

4700
per

kw.

metric

168

INDUSTRIAL

ELECTROMETALLURGY

technical

In

working

ton

of carborundum

the

charge is converted.
The

at

8360 kw.

about

product is manufactured

Niagara (10,000kw.), and

Germany,

is controlled

smaller

by the

same

Owing
substance

moulded
found

SlI^FRAX.

moulded

semi-metallic

its

It is

carborundum.

Carbon

for

required

of the

furnace

into
to

and

in

are

of

vapour

propertiesof
be

can

12000

used

C.

charge of the composition

in

carborundum

resistance

usual

to

up

It

silundum,

all the

possesses

The

type.

silundum,

beginning
depth depending on

silicon

to

exposure

for temperatures

packed
production

the

form.

be converted

articles could

by

high

to prepare

compact

electrically
conducting and

material

articles

in

made

been

resulting product, termed

originalshape

for resistance

have

the

to very

up

even

material

carbon

state

The

(" silidizing
").
retains

by oxygen

articles of the
that

Dusseldorf,

at

company.

by acids, attempts

or

Co.

Carborundum

plant

of

cent,

properties of carborundum,

unattacked

being

temperatures

into

resistant

the

to

metric

per

only 50 per

the

by

Sn,UNDUM,

was

and

consumed,

are

hours

the

is

carbon

outside

the

at

heating

period

and
of

verted
continuing
con-

heating.

Fitzgerald has attempted to prepare articles of carborundum

into
desired
the
crystallized carborundum
by moulding
form

and

subsequently recrystallizingthe
Tone

.furnace.
to

carbon

the

also
at

15500 and

sand"

or

using

water

of
most

action

investigated the

18200

variety.

was

purpose,

same

various

silicon carbide

solutions

"fire

an

electric

rundum
amorphous carboglass or glue as a

binder.

temporary
He7

adopted

in

mass

18200

between
He

and

temperatures,

C. the carbon

found

silicon

in

and

silicon

preparation

showed

22200
of

vapour

that
into

C. into

the

carbide

effective,i.e. if silica in

required for the

silicon

converted

was

evidence

of

excess

of carborundum

between

amorphous
the

existence
when

on

line
crystalof

solid

the

tion
penetra-

of the

quantity

be

added

to

169

CARBORUNDUM
the

charge in which
of siltindum

"

silfrax."

into pure
Siemens
with

"

is 0*5 inch.

carbon
in

conditions

these

penetration

maximum

Germany,

terms

vapour

prepared by the

have

to

he

silicon

of

Silit," as

appears

tion
modifica-

The

packed.

are

under

produced

The

Co.

articles

the

identical

been

silundum.
Monax.

Potter,8 who
the

reddish-brown

monax."

agent,

It has

suggested
of

(ithas

polisher of

to

as

oxycarbide in

to

the

of the

one

The

furnace.

in 1881,9 who
by Cohen
compounds on heating silicon in
In 1903,

tion
prepara-

of siloxicon

outer

of

zones

first

different
dioxide.

of carbon

stream

borundum
car-

were

various

obtained

the

"

"

in

of carborundum.
"

Siloxicon

apparently

general formula

averaging

acids ; forms

series of

large samples
highly

includes

Si,C*0, where

when

powder

amorphous

preparation

developed the preparation of siloxicon

and
not
merely as a by-product
purposes,

manufacture

most

in the

and

also

.It has

10

Acheson

for technical

and

density of only

oxycarbides of silicon

isolated

of the

reducing

FlBROX.

AND

already referred

have

silicon

"

name

printers'inks.

We

the

as

power.

pigment

the

gave

apparent

an

SlLOXICON

or

he

fair abrasive

it

use

which

to

in

monoxide

silicon

crude

field of usefulness

limited

insulator

heat

0*04), and
been

powder,

products formed

various

furnace, isolated

carborundum

as
"

investigatedthe

lies between

It

is

indifferent

furnace

liningto

and

taken.

are

refractory and

suitable

compounds

walls, but

7,
an

to

is

silica
superficial
a
easily oxidized than carborundum,
glaze being produced according to the equation
more

"

2Si2C20 +702
It

can

shapes.

be
At

decomposes

moulded

and

=2Si02 +4C02

baked

high temperatures
into carbide

and

to

form

in

an

inert

as

follows

silicon

Si2C20=SiC+Si+CO

vessels

of

various

atmosphere
:

"

it

INDUSTRIAL

170
Tone

has

with

treatment

on

silica and
remains

silicon, and

Graphite

it is freed

from

carbide

silicon

amorphous

introduction
The

thirds

of

silica with
salt.

As

siloxicons

Co.'s

multiple

of

at

been

lower

one-third

admixture

already

has

modified

instead

cores

by

single

and

two-

little sawdust

of

formation

the

noted,

that

than

temperature

of

coke

of

the

rundum
carbo-

Niagara.

at

carbon

usual

the

occurs

works

at

out

although occasionally

consists

charge

is carried

preparation

is used,

furnace

and

of

carbide,

silicon

hydrofluoric acid

of

method

International

one.

in

consist

may

behind.

Acheson's

the

silica

of

residue

siloxicon

that

solution

solid

view

the

expressed

essentially of
since

ELECTROMETALLURGY

necessary

for carborundum.
F.

Both

preparing

Tone

and

"

termed

threads

of

siloxicon

several

inches

long.

time, in

owing

conductor.

Its

and

00025

(2J

0*0030

silicon

to

vapour

of the

density
3 gms.

per

required for the formation

fibres ;
it is

diffuse

of carborundum.

REFERENCES

TO

V.

SECTION

/. Amer.

Chem.

Soc,

/. Phys.

Chem.,

15,

Trans.

Amer.

Electrochem.

Soc,

21, 438;

Trans.

Amer.

Electrochem.

Soc,

Trans.

Amer.

Electrochem.

Soc,

26, p. 194;
1914.
26, 1914, p. 181.

"

Trans.

Amer,

Electrochem.

Soc,

Trans.

Amer.

Electrochem.

Soc,

"

CM.,

10

U.S.

Applied

213;

Electrochem.,"

92, p. 1508;
Pat.

28, 850;

722793.

1881.

1906.

1911.
1912.

p. 491.

24, p. 181 ; 1904.

12, 223;
1907.

same

can

between
formed

be

into

just below

temperature

lie

to

litre). It
to

the

at

good electrical

said

is

slowly

at

fine

efficient heat

remarkably

carborundum,

monoxide

by allowing carbon

containing

as

fineness

apparent

of

consists

0'6/i diameter), frequently

to

It serves

with

The

siloxicon.

of

Weintraub

by

(0*3

the

to

common

"

Fibrox

in

succeeded

have

modification

interesting

an

material

insulator

Weintraub

E.

vessel
that

171

CARBORUNDUM

TO

BIBLIOGRAPHY

"

Carborundum/'

"The

Electric

"'Applied

F.

A.

Furnace,"

Electrochemistry,"

J.

Fitzgerald.
Stansfield.
A.

Allmand.

SECTION

1904.

V.

Section
Our

of

knowledge

is due

chiefly

carbide,

e-g-

off

in

with

furnace

who

electrical

furnace

isolated

the

state, in December,

pure

all

are

the

Moissan,

carbides

The

carbon.

of them

with

reformation

react

of

first

1892,

prepared

as

metallic-looking

dark

Most

hydrocarbons

with
the

solids
water

oxide,

CaC2+2HaO=Ca(OH)2+C2H2.

The
list

of

work

calcium

of

products

crystalline fracture.

give

to

these

BORIDES

AND

CARBIDES

the

of lime

electric

the

with

to

of

that

by reduction
in

THE

VI."

products

of

decomposition

are

shown

following

in the

"

Carbide.

Product.

Fe8C
Cr4C and

Cr3C2

Mo2C

action

No

with

water.

W2C
SiC
TiC

Cs2C2

Na2C2
K2C2
Rb2C2

C2H.

142C2

CaC2
SrC2

"42"C2
BC2
CH4

A1A

Mn3C

"

""

CH4

and

H2

CeC2
LaC2
PrC2

NiC2

CH4,

H2,

other

C2H2

volatile

SnC2

and

traces

of

hydrocarbons.

YC2
ThC2

U2C2

Volatile

and

liquid hydrocarbons.

174

INDUSTRIAL

nearly

two

ELECTROMETALLURGY

the carbide
raised

be

dissociation

would

be

and

carbon.

into lime

back

of the carbide

If the

graphite and

into

to

necessary

"

is said to be

carbide

the

high

too

CO

of

atmospheres

convert
re-

rature
tempeburnt,"

calcium

vapour

taking place according to reaction (3),the resultingcalcium

acting with the carbon monoxide
present to reform lime and
dust, which

carbon
There

have

(Gin).
the

which

at

supposed

are

uncertainty in the

some

carbon

at

formation

various

the

adopt

the

on

from

lime

hours

details

there

specificheats
well

the

as

to

as

and

(CO

products

as

and

kw.

3837
no

retical
theo-

production

the

furnace, and

of the

values

to

given

high temperatures,

of calcium

will

We

hours

the

leave

to

for
carbide

investigators have

temperature

CaC2)
and

Several

kw.

1523

stream.

gas
made

necessary

calcium

pure

from

varying

carbon,

of

ton

off in the

calculations

expenditure

metric

one

several

been

energy
of

carried

are

is still
of lime
of

heat

carbide.

the

followingvalues

as

tions
the basis of calcula-

"

Atomic

specificheat of
Molecular
specificheat
of formation

Heat

carbon
of

lime=n,4+o,ooiT

of CaO

the

furnace

incoming
follows

at

3,900

the carbide

20000

charge,

C,

we

and

and
not

are

calculate

may

carbon
used

the

monoxide
heat

to

leave
up

the

required

energy

as

"

J m"l
(ra*se

Heat

supplied
p^
Heat

that

assume

per gram
molecule

29,200

CaC2
we

calories

=145,000

CO

If

4,26+ooo72T

to

from

1decomposer

mol.

(raise3

of C from

liberated!of

by formation

CaO

mols

mol

CO

(of 1

mol

CaC2

CaO

o" to 200c0

o" to 20000

C.=

24,800
into Ca and O2=i45,ooo
=

30,000

199,800

29,200
3,900
33**00

Net

energy

required=i66,700
=

3,040

calories
kw.

ton,

or

hours

per

metric

CARBIDES

THE

figure closely approximating

(3100 kw.

hours) by

value

the

that

he assumed

which

that

to

different

somewhat

BORIDES

AND

175

in which

method,

Q in the reaction

of

obtained

Haber

"

CaO+3C+Q=CaC2+CO
3*3T, a value determined
by Thompson
equal to 121,000
calcium
carbide
85 per
{loc.
cit.). Commercial
averages
cent,
purity,and the energy consumption per ton of 85 per
and
varies between
carbide
cent,
5960 kw. hours,
3500
was

"

depending
of

and

the system

operation.
carbide

The

by

of

means

furnace

led

heating has

the
to

types of furnace
carbide

owing
in the

vapour

the

that

best

small

which

arcs

have

been

obtained

with

the

is

there

Both

chaige.

currents

used

the

former,

frequently a

smothered

as

furnaces, in

arc

broken

in

uniform

direct
is

product

badly designed furnaces

loss of energy

considerable

by the

alternating and
most

but

striking
probable

more

and

any

carbon

for

It appears

the

principle,

and

necessary

continually made

are

the

act

whether

calcium

both

8 volts.

to

furnaces

of

movements

of

of

increased

resistance

the

on

"

resistance

an

doubtful

charge, the E.M.F.

hot

"

incidentally to

and

presence

be reduced

can

arc

the

of

thermal
electro-

modifications

is, however,

It

other

use

considerable

operates purely

to

in most

as

to make

tendency

employed

furnace

since

but,

arc,

very

efficiency.

thermal

originally designed for heating

was

electric

an

processes,

an

of the furnace

the construction

on

due

self-

to

induction.

charge consists

The

limestone

in the

maintained

kgm.
of
two

of

yield and

the
of

It has

been
The

of

kgm.

carbide

important

mixture

theoretical

1440

charge have

of

in

been

proportions.
the

found

energy

in

the

evolution

(2)

are

carbon

loss

no

were

produce
to

3000

1000

kgm.

influence

(1) Size

Presence

finely comminuted
of

crushed

for this output.

charge which

consumption

that

1700

necessary

composition, and
found

from

and

If

charge should

practice

factors

of carbon

monoxide

of

and

The
the
formity
uni-

impurities.

visable.
charge is inad-

during

the

INDUSTRIAL

176

channels

glazed
a

their

considerable

hot

gas

When

the

charge

may

load

from

the

become

with

carries

it

by using lime

crushed

with

ease

of

overlying

large fluctuation in the furnace

liberating a sudden

the

heating it.

mass

loss of

which

without

charge

of

inch

results

and

of gas

burst

finely powdered

the

uniform

most

to

frequently

in the

results

to the

portion

practice the

In

of the mass,

numerous

time

same

due

honeycomb

causes

; this

the

subside, causing
at

charge.

of heat

escape

channels

and

which

interior

interior surfaces
amount

can

carbide

the

in the

formed

to be
on

of

formation

of

process

ELECTROMETALLURGY

coal

the

obtained

are

J-inch

to

or

inch.

lime

The

manufacture

for carbide

free from

burnt

and

coke,

anthracite,

The

moisture.
charcoal

or

should

have

than

as

ash

and
only be used with great difficulty,
is desirable.

ash

cent,

ash,

less,

or

carbonized

wood

and

the

sawdust,

their

into

way

per cent,
5 per
cent,

per

quantities of
of

by-product

the

ash

an

less than

Small

of

form

10

containing 3

usually employed.

are

distillation, find

Anthracites

thoroughly
low

as

content
can

be

in the

carbon

containing more

Coke

possible.

should

carbide

wood

industry and

give the best results.

The

usual

assist in the

viscous

formation

molten

the

cause

impurities

and

not

lime

as

phosphate

phosphine,
account

on

phosphine

arsine

and

of their
is

to

quantities

in the

sulphate

beeome

are

coal

or

reduced

of
in
to

the furnace.

impure carbide will liberate

hydrogen sulphide, all objectionable
water

toxic

properties. In addition, impure

The
other
coal
spontaneously inflammable.

constituents, silica,oxide

ash

or

sulphidesin

and

with

small

and

furnaces

larger furnaces

sulphur present

and

calcium

treated

in the

which

alumina,

and

in small

crusts

easily tapped

so

phosphides, arsenides
When

magnesia

of thick

carbide

arsenic, phosphorus
the

are

of iron and

the

alkalis, do

not

sensibly affect the operation of the furnace.

Various
ensure
so

as

the
not

alternative

schemes

preparation of
to limit

the

pure

have

from

carbide

manufacturer

to

proposed to
impure materials

been

the

purchase

of pure

CARBIDES

THE
anthracite

iron to the

melt

carbide.

dioxide

The
of
a

the

addition

of crude
mixture

The
to

serves

carbide

Calcium
at the

carbide

furnaces

lime

and

is said

of three

"

"

of lime

and

carbide

is formed

contents

distinct

The

earlier Willson

pendent electrode
carbide

which

by

introduced

of

as

taking

of
a

such

200

to

250

Willson,

charge

with

the

material

basal and

Owing

the

loss of

through

current

Willson

improved

one

the block

as

to

charge.

next

one

of the

carbide

fused

the

of

to cool.

allowed

non-converted

in size.

(Fig.19, B)

pendent electrodes.
only part of the charge

observed,

and

unconverted

charge of about
of

1,.

two

furnaces

and

and

up

furnace

the

mass,

protecting

in

are

sufficient amount

transmission

having
the

give

carbide

the

as

continually raised

was

already been

is converted,

when

(Fig.19, A) had

increased

partly solidified

to

types

furnaces

these

and

the

furnace

occasioned

Several

broken

to

type, such

is removed

the half-formed

latter is returned

"

In

in, and

then

the

has

ingot

furnace

the

are

separated from

of molten

"

is fed

coke

"

furnaces.

Horry

instead

"

all of the

were

and

acting

formed

oil to the lime

hydrocarbon

furnaces

present time

Bullier

As

to

carbide, permitting

"

was

purities
im-

carry

block
ingot type.
or
(1) The
(2) Tapping furnaces.
furnaces.
(3) Continuous
The
earlier forms
(1) Ingot Furnaces.

the

carbon

phosphides

manganese

of carbon

"

energy

about

non-hygroscopic carbide.

loose non-coherent,

The

the

and

charge.

sulphides and

the

of

easilytapped.

heating up

use

to

below

of limestone

melting point of the calcium

the

it to be

tlie calcium

addition

the

ferrosilicon,which

as

carbonate

crust, whilst

surface

lowers

dioxide
the

177

of the furnace

quantity

from

as

silica

the bottom

adds

liberated

suggested

the

remove

of manganese

such
the

to

Hewes

cent,

per

Rathenau

off from

be drawn

may

lime.

and

BORIDES

AND

liner
are

1400
kw.

for

the

semi-fused
iron

generally
kgm.
at

50

to

furnace

70

walls.

together, each

run

and

materials

an

energy

sumption
con-

About

volts.
12

178

13-hour

of

ton

kw.

4500

The

run.

metric

per

carbide

of

kgm.

800

but

ELECTROMETALLURGY

INDUSTRIAL

labour

formed

85 per

carbide

cent,

later

of

cost

this

from

of

consumption

energy

in the

hours

the

is

designs of

breaking

kw.

6000
been

the

Willson

hours

reduced

has

to

furnace,

sorting the ingot is

and

up

charge after

always high.
the

In

Horry

(Fig. 19, C),

the

to

spindle

diameter

and

of the

successful

ingot system

horizontal

furnace

been

has

attempt

carries

made

rings about

two

By

apart.

Co., Niagara

apply

to

wide

operation.

semi-continuous

metre

Carbide

Union

of movable

means

in

metres

25

plates

acKd
car

"

A
Fig.

the

hopper
outside

from

in which

Two

the

After
the

revolution

base
a
a

rotated

of the

fresh

so

as

complete rotation

the

ring of solidified carbide

is made

produced.

in 24 hours
With

load

and

molten

of

375

The
carbide

it is formed,
the

old

plates are
up.
two

kw,

tons

per

ring, the

the

broken
about

in the

purpose.

above

cover

in

the

rapidly as

to accumulate

of the

mounted

point

to remove

as

chamber

reduction

are

for

type.

into

the

electrodes

hopper

charge

"Ingot"

be converted

supplying the charge at one

plates being then removed

allowing

are

furnaces.

platescan

place.

takes

spindle is slowly

and

carbide

rectangular cross-section

carbide

'

-0

Calcium

"

between

the space
of

19.

bide

thus

one.

removed

complete
of carbide

furnace

CARBIDES

THE
of

production
obtained.
be

can

metric

According
metric

of

working and

increase in the furnace

an

loss and

heat

the labour

increase

corresponding

in

of control of temperature

ease

is thus

hours

hours.

With

"

the radiation
a

179

kw.

4500

per

3800 kw.

Furnaces.

of material,

ton

BORIDES

Stansfield,8 the energy consumption

kw.
to 310
per furnace, thus
ducing
pro-

to

for

ton

(2) Tapping
size to reduce

ton

down

brought
1

AND

cost

per

the

efficiency

was

obtained.

The

of tapping a large mass

of molten
carbide
practicability
of
impossible in the smaller furnaces owing to the formation
crusts
and the high viscosity of the impure melt was
gated
investiin many
The

Alby Carbide

similar

very

holes

kw.

50

at

end

carbide

of

ton

The

1400

kgm.

4200

to 4500

energy

kw.

hours

with

will take

1000

in current

both

against

as

in

arc

open

furnaces

are

by the
from

fumes.

phase

The

current

is minimized

limit

loss from
the

and

power

the

the upper
of

sumption
con-

nuisance

large multiple-

totally enclosed.

opportunity
used

has
three

satisfactory results.

consumption in

use

large

surface

By

of the

collectingthe

this

charge
carbon

presents itself.

evolved

with

When

and

is to

in

Memmo

the

to

have

continuity

works.

working

are

from

to vary

improvements

is set

present tendency

furnaces, which

Helfenstein
furnished

used

difficulties of

the radiation

monoxide

charge of

of carbide.

carbide

Norwegian

the

in

produce

to

is stated

Several

"

and

theoretical

consumption
for 1000
kgm.

minutes.

45

every

in

made

Italy, and

an

9000-kw.

electrodes,
The

enclosed

of the electrodes, which

500

provided

tapping furnaces so as to ensure

production, especially by Helfenstein,9 by

been

means

once

furnace

charge being used

Furnaces.

(3) Continuous
of

of

use

unit

Each

tapped

kgm.

works

pattern

is effected

economy

material, 1500
metric

Odda

walls.

is

and

volts

their

at

early Willson

in the

considerable

raw
1

Co.

the

to

tapping
A

works.

carbide

amperes per sq. dcm.

each

to

one

practical limit
furnace

should

not

is set
carry

furnace,

3-phase

to

phase, with
the

current

only by the size

current

exceeding

180

INDUSTRIAL
Borchers

suggested

of steam

purpose
does

ELECTROMETALLURGY

not

carbon

generation

to

seem

have

monoxide

utilized for

burning

with

received

the

waste

heat

C.
the

preheating

and

; this

2000"

at

the

for

idea
The

application.

furnace

limestone

the

furnace

technical

the

leaving

the

cooling

water

be

can

entering

charge.
The

liberated

energy

molecule

of

carbon

calories, whilst
of

carbon

and

equation

in

combustion

monoxide

the

is

of

of

one

gram-

approximately

required

energy
molecule

one

the

heat

to

molecules

up

in accordance

CaO

67,700
with

the

"

CaO+3C=CaCt+CO
from

o" to

20000

30.

Calcium

Fig.

"

It should,

reaction
monoxide
amount
the
1

The

parting
in

the

carbide

therefore,

liberated

of carbide

carbon
with

By
of

accompanying

the

be
can,

reduced
of

diagram.

The

the

to

carbon

equivalent
to

20000

kw.

2100

be

charge,
energy

to the

production

the

course,

incoming

the

charge

for

type.

charge

of
of

the

required

the

up

formation

preheating

would

to

heat

continuous

combustion

the

energy

monoxide
its heat

Three-phase

the

during

only 54,800 calories.

seen,

possible to
by

of carbide.

ton

have

we

furnace.

be

temperature

consumption

metric

C. is, as

burnt
as

thus

C.
of

hours.
after

indicated
derived

ELECTROMETALLURGY

INDUSTRIAL

i82

TO

BIBLIOGRAPHY

of

"Principles

Electric

"Der

Electrische

Carbide

their

of

Bronn.

Ofen,"
Calcium,"

Industrial

Stansfield.

Furnace,"

"The

"'

and

Furnaces

"Electric

Electrochemistry,"

Applied

C.

Bingham.

VI.

SECTION

A.

Allmand.

Applications/'

Wright.

VII. ^ELECTROTHERMAL

Section
NITROGEN

FIXATION

Sir William

1898

world
of

economic

of

four-fifths
are

find

we

used

world's

the

industries, chiefly
as

nitric acid
for

forms

cyanides

for

production

of

as

for the

diverse

the

is

essential

an

materials

nitrogenous

in the chemical

extraction

the

land

the

Approximately

one-fifth

of

gold,

in various

explosives,and

of

branches

around

land.

of

supply

the remaining
fertilizers,

as

international

and

nitrogen
the

scientific

of the

all centre

from

to

satisfactory solution

National

fixed

that

of food

production

the

for

politicalexistence

and

question, and
for

attention

the

problem.1

nitrogen

the

drew

growing importance

the

to

presidentialaddress

in his

Crookes,

Association,

British

the

AND

COMPOUNDS

METALLIC

In

METALS

BY

organic chemistry

the

industry, especiallythe dyes.

With

increase

corresponding

necessary,

and

populated

areas

per

acre

find that

we

of the
than

in the

increase

natural

the

Belgium,
uses

other

any

intensive

in

world,

density of the

horticulture

of the most

one

and

is

densely

nitrogenous

more

country,

tion,
popula-

izers
fertil-

corresponding

increased

of foodstuffs
is obtained, whilst in
yield per acre
almost
in America,
virgin soils of the wheat
areas

the

Canada

and

fertilizer
these
of

has

natural

artificial

factors, such
a

Siberia
not

been

yet

tendencies

as

the

system

greater interest
of the

the

of the

found

towards

fertilizers, the

education
needs

application

the

an

of

increased

peasant
land, the

people leading to
the

more

increased

nitrogenous

any

necessary.

development

in the

soil ; and

of

of

Apart

from

consumption
certain

social

suring
proprietorship en-

scientific

increased
rational
power

view

of

as

to

purchase

by

of

means

for artificialfertilizers is certain to increase

present

follows

as

Nitre.

of

sources

in the
be

supply may

past.
brieflyenumerated

"

in

found

are

of

deposits

Large

"

"caliche,"
on

it has done

greater rate than

The

indicate

co-operativesocieties,all

guilds and

that the demand

at

ELECTROMETALLURGY

INDUSTRIAL

184

Chile.

natural
These

nitrate,

sodium
have

worked

been

ever-extending scale since 1830, the present output

an

amounting to over two and a half million tons per annum.

Although these depositsappeared inexhaustible when first
worked, the increasing consumption has led to various
of the area
to determine
carefully investigatedsurveys
the probable available
supplies. The reports submitted
Chilean

the

diversityof
opinion,and although the somewhat
alarming figure of
the maximum
21 years
as
period of life can be rejected,it

to

Government

that before

appears

exhibited

have

the end

of the

nomic
present century the econitre will no longer be possible.

exportationof Chilean
and
important deposits of nitrates of sodium
found
British
the
within
Commonwealth,
potassium are
in
the
and will
and
Persia,
India,
Sahara, Egypt
namely
probably be developedlocally.
The other chief source
of supplyof combined
Ammonia.
Less

"

nitrogenis ammonia, which is used in the form of ammonium

sulphate. Recently experimentsby Rossi and others have
indicated

that

fertilizer. It

be

may

nitrate
remarked

into nitric acid

converted

be

ammonium

the

surface

on
oxygen
oxidation in aqueous
is not
from ammonia

can

that

also
since

combustion

by

of suitable

used

be

as

ammonia
with

catalyticmaterial

solution, the productionof

can

air

or

or

by

fertilizer

necessarilydependent on the sulphuric

acid industry. Practicallyall the natural ammonia
able
availis recovered
or

coke

in the
but

is obtained

somewhat

Producers
recovered

coal distillation either from

better

(60 per
from

gasworks
fixed nitrogen

per cent, of the

in the usual distillation process,

Only about

ovens.

coal

from

20

recovery

cent.),whilst

is obtained
still smaller

shale distillation and

in Mond

Gas

amounts

are

blast furnaces.

ELECTROTHERMAL
The

NITROGEN

world's

million tons, of which

Since

coal

with
in

of

form

the

Great

contains

the

on

20-per-cent.

that

alone

could

source

would

of

the

all

introduced.

is

reserve

of economical
Other
of

larger than

the

working is by

no

distillation

destructive

the

residues

in

fermentation

nitre

if the

Although the world's

caliche,their period
indefinite.

means

found

are

this

supplies from

Chilean

of ammonia

sources

least

compulsory.

entirely replace the Chilean

requisite legislationwere
coal

if at

made

were

available

present

nitrogen,
fixed nitrogen
of

available

be

coal

thousand
15 per cent.

of

tons

185

one

cent,

per

million

two

ammonia

is evident

average

recovery

partial carbonization
It

production is over
Britain suppliesover

coal

annual

FIXATION

of

in the

bones

industries.

by-products
the

and

Probable

organic
of

sources

fixed

nitrogen will possiblybe found in the extended

of the low-grade fuels such as
development of the gasification
natural

turf, of which

and

peat
the

British

and

in the

sludges

potential

more

of

sources

has
for

As
a

The

A.
the

The

B.

difficulties

sludge, peat and

turf

satisfactorily

yet been
ten

there

years

"

preparation

of gaseous

of fuel

atmospheric nitrogen

combustion

coal

suitable
development in methods
of atmospheric nitrogen. These

follows

as

not

technical

nomically
eco-

the

methods

during the last

fixation

direct

the

for fuel have

considerable

be classified

nitrogen in

extravagant

whilst

consequence,

technical

the

the

to

these

being

not

of
in

nitric
the

acid

by

electric

oxidation
and

arc,

by

fuel.

preparation

of

synthetic ammonia

from

its

elements.
C.

The

fixation

of

atmospheric nitrogen by

biochemical

methods.
D.

The

works

sewage

are

of the

bulk

drying of sewage

the

it suitable

been

may

of

with

render

solved.

the

employed,

associated
to

Ireland

and

present time

the

ammonia

natural

entirely lost owing

combustion

At

purposes.3

within

found

are

especially in Canada
extensive
application of

developed
is

areas

Empire,
manurial

to

extensive

preparation

of

combined

nitrogen from

which

t86

INDUSTRIAL

ammonia

ELECTROMETALLURGY

be

can

obtained,

cyanides

cyanamides,

e.g.

and

nitrides.

(i) The

A.
with

this

Arc

method

investigations of
1897,

pioneer work connected

was
accomplished in England by the
Cavendish
1800, Rayleigh
1781, Davy

McDougall

and

technical

plant

in

arc

The

"

Howies,

and

1899

industrial

present

Process.

who

Manchester.

at

the

processes,

discussed

is very

process

smaller

The

efficiency of

Birkeland,
follows

as

65

of

The

according
evolution

recoverable

to

00256
nitric

of

hour,

is not

Since
this

Haber's

of

last

the

in water

energy.

kw.

stages of

of

25000

C.

It

must,

however,

equilibrium is obtained
temperatures
may

of

be
gas

attained

electrical

gases

At

low

are

sufficientlyquickly
temperatures

mean

in the

arc

remembered

the

to
to

the

gms.

of nitric
absolute
to

give

neighbourhood

great rapidity

due

63

or

Jellinek and

the

higher mean
practice,and that the

actually obtained

coolingthe

with

be
be

energy

concentrations

considerable
in

equivalent

are

Nernst,

passing through
must

heat

cooling the

of nitric oxide
of

cals.

technically available
of

amount

concentration

NO

cent.

per

air

is

this

oxide in ordinary air at high temperatures, the

of the

hour.

dioxide

nitrogen

cals.

22,000

supplied
30 gms.
acid.
Taking the mean
figuresfor the equilibrium

temperature

kw.

13,500

2NO+02=2N02,

to form

be

must

reaction

absorption

as

processes

per

although

formation

the

occurring during

and

in technical

equation N2+02=2NO

the

to

calories, and

during
the

may,

of the
operating furnace
be calculated
or
Pauling type can
required to form a gramme-molecule

22,000

to

It

efficiencyof the

of nitric acid

gms.

according

liberated

series.

normally

energy

approximately

gases

75

Schonherr

nitric oxide

are

yields obtained

to

this

plants

Germany,

and

electrical

the

that

out

poor, the

being only from

of

volume

another

pointed

be

however,

in

is

which

of

operation

to
Norway,
although
practically confined
in operation in Switzerland, Italy, France
are
are

of the

outline

An

first

the

erected

at

that

since

these

high

gas

temperature

low

percentages

impossibilityof

relativelylow temperatures.

apparent

stability of

ELECTROTHERMAL
gas

rich in NO

the

reverse

is assured

reaction

of the

2NO

equilibrium
heat

to

necessary

=N2+02

14

of
is

temperature

(6-8+0 0006X2500)
"

represents the

*u.

of

gms.
X2X

2500
"

4.4.1

The

energy

16

approximately

20,600 calories.

or

the

nitrogen and

that
value

true

25000 C,

at

which

Assuming

proceeds.

gms.

with

slowness

the

of NO

187

FIXATION

to

concentration

up

this

to

oxygen

owing

concentration

cent,

per

NITROGEN

total

lrrecover-

able

kw.

0*050

for

hours

acid, representing

acid

for

cent,

5 per

per kw.

remaining 95 per
with
the unchanged

is effected
Willcox

be

of
the

of the

cent,

nitric

nitric

of

63 gms.

or

"

"

air.

Partial
arc

the

process

through

chief

merits

are

action.

The
of gas

has

are
can

wasteful

in

simplicityand

costs

are

formity
uni-

high owing

heated, cooled

be

to

data

no

extremely

extreme

that

and

recovered, there

so

erection

loss

Babcock

Although
is

passes

of this

recovery

gas

of energy

amount

large volume

electrical energy

raising steam.

that

Its

power.

for

the

as

doubt

no

of

production

of the

by passage

boilers

available

of

gms.

or

hour.

The
out

63

efficiencyof only

electrical

technical

of

production

the

an

42,600 calories,

is therefore

consumption

energy

to

and

passed through absorption towers.

on

The

work

the

use

and

of Haber
of

Koening

and

furnaces

arc

chilled arcs,

on

worked

under

and

Strutt

recently of Lowry

reduced

of Rossi
pressure,

production
an
allotropicactive modification of atmospheric nitrogen,
indicate
that arc
methods
be capable of modification
may
and
the original
improvement, possibly departing from
more

on

the

of

electrothermal
it suitable
power

(2) By

owing

for those

is the

to

of oxides

explosion and

factor

Combustion
work

of
of

electronic

an

countries

governing

the
the

to

process

where

the

so

and

Gaseous
his

number

of

ment.
developChiefly

Fuel."

pupils

render

of electrical

cost

nitrogen during the process

combustion,

to

as

in electrochemical

of

Haber

one

on

the

duction
pro-

of gaseous

patents have

been

188
taken
of

ELECTROMETALLURGY

INDUSTRIAL
for

out

oxides

of
on

which

only

semi-technical

mixture

The

nitrogen.

of
air

and

gas

oven

has

is that

scale

of coke

which

one

formation

direct

fuel for the

utilizinggaseous

been

veloped
dein

Hausser,

is

oxygen

or

is made
of large capacity. Provision
exploded in a bomb
for a rapid cooling of the gases by water
injection and rapid
release into the cooling system.
The
of charging,
process

release, ignitionand
modified

Otto

The

rich coke

with

claims

The

B.

u.

few

hydrogen

experiments
made

was

Fabrik

at

previous

years

determined

the

3H2+N2$2NH3,

various

temperatures.

equilibrium

constant

from

It

of

equation

and

in

Ramsay

nitrogen
Anilin

Germany

equilibrium

the

pressures

gas

and

that

from

equilibrium

amount

noticed

first

Haber

war.

in

high
be

of

technical

Badische

the

ammonia

will

the

to

explosion.

elements

the

outbreak

under

put

formation

Regnault

Leverkusen

of

due

successful

and

the

or

substantiated.

and

amount

mixture

of

centration
con-

has

period of

by Haber

Oppau
to

of NO,

when

cent,

per

cent,

The

"

synthesis of ammonia

Soda

on

NO

an

inventor

the

to be

Process.

of the

development
the

remain

Haber

only 05

favouring the

during

compounds

claims, however,

These

5 per

yield

C.

The

hour.

to

endothermic

and

kw.

per

of

gases

21000

of

should

gas

obtaining over
photochemical action

induced

on

oven

resulting

the

5-56 gms.

forth

cyclic

made

explosion temperature
in

about

be

can

cycle.

mean

operating

scavenging,

at

the

"

C"h,lCNi

increase
ammonia
over

the

beneficial
From

of

increases

pressure

present, and
stoichometric

the

furthermore
ratio

H2

for

high concentrations

the

general equation

"gK2

an

excess

N2

: :

of ammonia.

"

RYf2

TV

of
:

of

hydrogen

is

likewise

INDUSTRIAL

190

calculated

temperature,

K=n-C^-^1
present

is about

is

to

Small

pressure.

air and

preparer
The

the

absence
The
but

electrical
the

"

catalyst

interchange

coils.

exothermic,

local

when

the

electrical

is small

temperature
mixture
current

gas,

with

washing

by

off

"

the

for the
low
of

only

very

low

catalyst

is

may

occur,

to

the

of
in

catalyst

the

supply

and

to

the

inert

the

such

present

in

the

the
low

as

the

is important

gases
At

very

yield per litre

velocity of the

high speeds equilibrium is

percentage of ammonia

unused

gases

of ammonia.
but

counter

Periodic

bomb.

of

gaseous

the compressor,

argon

production
is obtained,

from

the

eliminate

owing

and

pressure,

change
inter-

heat

by liquefactionor

under

The

present.

formed

through

is small

catalyst space

of heat

N2+3H3-"3NH3

good system

hydrogen,

speed equilibrium

gas-flow. At
and

additional

economic

through

system

maintaining

velocity of circulation

The

nitrogen.

externally,

circulates

already

ammonia

water

is necessary

from

methane

an

the

ensure

by the combined

gas

reaction

for

when

recirculated

and

blowing

The

subsequently removed

augmented

dried
"

is

over

generated automatically falls owing

The

is installed.

passed
to

catalyst and

the

necessary

energy

operation.

high temperature, internal

the

ammonia

of

decomposition

to

metal

over-heating of the
of heat

amount

and

to

water-vapour.

applied.

Since

adjusting

producer

originallyheated

the

nitrogen

so

one

chloride

of the

and

contains

which

bomb,

and

weakening

heating is now

in

compressed

were

hydrogen

The

water-gas

mixture

"

bombs

the

of the

now

removed

are

scrubber.

calcium

and

monoxide

in the

now

of oxygen

of traces

to

is

steam

sulphur

any

alternatively by

or

blasts

are

asbestos

owing

action

carbonate

steam

purified gases

palladium

constant

excess

and

of the

traces

nitrogen-hydrogen

The

C02

the

liquid air

prepared from

the

equilibrium

cent.

per

ammonium

cuprous

the

by pressure washing with water, and the CO

formate
by scrubbing with hot caustic soda

H2S

as

is converted

by

from

by condensation,

removed

under

ELECTROMETALLURGY

not

is formed,

obtained,
but

the

ELECTROTHERMAL

yield
the

is

hour

per

higher owing

gas-flow. The

191

velocity of

increased

the

to

time

space

ammonia

of

FIXATION

NITROGEN

yield, i.e. the

grammes
yield in kilo-

litre of

the

catalyst per hour, is

determining factor as far as output of a unit is concerned.
technical
In
operation the space time yield may

rise

as

high

per

gas-flow,the difficulties of heat

are

the

by

and

gases

the

skilled

(C) Biochemical
soil
to

the

varieties

preparation
of the

ordinary

In

"

present, frequently rising

are

These

per gramme.
of

saprophytic
anaerobic, pathogenic organisms

include

bacteria

amongst

moulds,

and

aerobic

both

number

organisms capable of fixingatmospheric nitrogen, entirely

distinct

from

the

nitrifyingbacteria

the

more

are

capable of oxidizing

nitrites

recently discovered

The

first

fixingnitrogen

Pastorianutn.
have

or

already in the soil

substances.
of

chiefly

is

compression

supervisionnecessary.
Fixation.
Nitrogen

million

10

several

and
of

than

more

tion
gas circula-

in the

the

hydrogen,

of bacteria

number

vast

velocity of

of the process

cost

entailed

expense

purification of the

and

increased

regeneration and

The

greatly enhanced.

determined

with

Naturally

15.

as

been

was

Since

shown

such

as

isolated

and

agilis,and

and

successful

this property,

of calcium,

of sodium
2.

Bacillus

and

Large

glaucum,

this

of

in soil

property

are

fixed

organisms
the

as

fungus

beta

Phoma

and

chroococcum
conditions

The

brieflyas follows

phosphorus and

potassium.
quantities of

such

Azotobacter

radiciola.

nitrogen fixation

Presence

nitrogenous organic

possessing

bacteria

the

among

as

by Benjerink, viz. Aostridium

Aspergillusniger, Penecillium
others,

or

period a large number

to possess

and

Winogradsky

denitrifyingorganisms which
nitrates and
reducing ammonia,

organism

this

of

smaller

nitrogen

for
:

"

quantities

hinder

further

absorption.
3.

The

4. The
less than
Most

temperature
earth

range

should

well

aerated

io" and
and

not

500 C.
contain

of moisture.

15 per

cent,

of the

organisms

growing in symbiosis

be

lies between

with

function
other

most

successfully when

organisms.

The

azobacter

ELECTROMETALLURGY

INDUSTRIAL

192

showed

the B. radicicola

that

with

leguminous plants

and

bacillus exhibit

several

strains

cultivated

certain algse whilst

with

abundantly

most

grow

parasitism. Of
nitrogen-fixing organisms

artificial

media

for

recent

years

have

been

agricultural purposes,

it has been
during the period of the war
large quantities of nitrogen-fixingyeasts have
in Germany
for supplying pigs and other animals
and

requisite organic nitrogen.

choice

of the

nature

the

organism

when

employed
contemplated

of the

the

controlled
for

grown

before

pabulum
to the

Up

present time

commercially
and

Fixation

Compounds.
by purely thermal

industrial

scale.

mentioned

the

All

by

these

pressure

of

in

processes
the

compounds

+3H20

be

can

steam

Nitrides.

important

under

nitrogen

the

problem

(under 6 atmospheres
pressure)
in water

+NH3
(at 5000 C.)

technical

prevented

fixation
would

atmospheres
"

fixation

in the
the

is

so

process

great that

probably prove

of

Savoy,

successful,yet the advantages

of

few

+3XOH

The

be

may

ammonia

into

=NH3

an

on

cyanamides.

the

followingequations :

"

difficulties

forms

to the

=XCOOH

+2H20

by Metals

nitrogen has been

or

accomplished by Serpek

several

peptone.
scarcely proved

converted

XCN+2H20=XOH+NH3+CO

been

and

several

more

2X2NNC+2H20=(H2NNC)2+2H20

The

media.

little bacterial

water

X2NNC+3H20=X2C08+2NH3

XCN

deteriorates

Nitrogen

nitrides,the cyanides and

according

X3N

have

Elementary

"

Amongst

with

treatment

methods

of

by

activity of

artificial

sugar

grape

of soils the

this

in

their

successful.

Metallic

fixed

as

these

Electrothermal

D.

since

use,

grown

with

the

and

crop,

by the addition

soil, such

the

to

been

determined

be

generations

several

good growth is ensured

should

bacillus

that

stated

inoculation

the

In

plant

the

case

alternate

of

on

in this

peas

as

associated

practicallyonly

was

such

Hellriegal

nitrogen has
and

from
of such

although
being
a

nomically
eco-

process

reinvestigation of

remunerative.

ELECTROTHERMAL

NITROGEN

FIXATION

193

devoted
to
Serpek's early experiments (1906-1 907) were
nitride by passing nitrogen
preparation of aluminium
carbide
aluminium
at a red heat, when
according to

the
over

Caro

following reactions

the

take

place

"

A14C3$4A1+3C
4A1+2N2^4A1N
dissociation

The

carbide, and

that of the

From

Serpek

1907-1910

technical

scale

higher than

is 21200

quickly

construction

followingreaction

out

the

A1N

+3CO

"

this

=2

the nitride

and

C,

place below

take

the

at which

temperature

in

engaged

was

A1203 +3C +N2

The

is

consequently the nitride is actually

apparatus suitable for carrying

on

nitride

through the intermediary preparation of aluminium.

formed

of

of the

temperature

decomposes relatively
the

consequently

reaction

Serpek

temperature.

states

C. ;
at 11000
absorption of nitrogen commences
the absorption is fairlyrapid,whilst from
17000
reaction
is a
the
comparatively violent one.

aluminium.

preparation of
by Serpek in
is

Bauxite

connection

resistors
The

was

heating

second

type

shaft

containing

space

is

1..

18500
We

to

nitride

much

lower

C.

have

electrothermal

the

for the
made

was

formation

of
than

nitride.

alumina,

temperature.

results

these

which

and

came

to

bauxite.

in the

charged with

axial
a

sociated,
again dis-

carbon

In

the

coke
of

of bauxite

by radiation.

hollow

resistor.

first

carbon

transverse

and

consisted

mixture

Savoy.

having

charge of bauxite

an

is

Serpek successfully operated

employed
of furnace

nitride

the

by suitable catalysts usually

types of furnace

kiln

rotary

to

observation

the

brought about

be

different

at

with

ease

present in French
two

15000 C.

low-temperature fixation,desirable owing

that

relative
can

with

confirmed

Read6

the conclusion
the

similar

readily converted

more

and

Tucker

to

absorption commences

and

purified by

the

at

readily soluble in the electrolyteused

is not

method

alumina

that

already noted

must

The
and

vertical
annular

coke, and
13

INDUSTRIAL

194
a

of

current

nitrogen passed through the charge

of 16000
is burnt

17000

to

heat

to

superheated

from

steam

The

C.

alkali

at

rature
tempe-

monoxide

carbon

charge.

nitride

the

weak

or

liberated

incoming

the

up

recovered

be

can

ELECTROMETALLURGY

alumina

Pure

by decomposition with

"

MN+3H20=A1(0H)3+NH3
Attempts

to

in

used
future

of

development
lines is

these

could

process

devised

of the

need

From

both

charge.

of

supply
Serpek and
a

that

possible

appears

render

to

if

the

of fresh

bauxite

synthetic catalyst could

permit

Another
the

be

would

which

is treated

imagined

as

of the

At

into
nearly completely dissociated
according to the reversible equation

hydrogen

iron
cessful
suc-

which

reactions
of

temperature

is

methane

the

in

process

catalyst for gaseous

follows

as

of

as

be

alumina.

the

possible development

alumina

may

of

for each

observations,

Tucker's

titanium

utilization

pendent
inde-

process

oxides, such

chromium,

process

continuous

prepared presumably containing other

or

nomically
eco-

yet the

aluminium,

successful

be

as

so

be

course

nitrogen fixation

technical

likely to

more

be

of

of

not

of suitable

absence

could

preparation

the

did

dehydration

the

to

alumina

the

catalysts. Although

it

after

successful, probably owing

prove

on

alumina

the

use

15000

carbon

C.

and

"

CH4^C+2H2
whilst

carbon

monoxide

hydrogenation
mixture

over

contain

may

nickel

less than

10

be

converted

into

methane

catalyst (provided the

per

CO)

cent.

by

CO,H2

"

CO+3H2=H20+CH4
when

comparatively

under

3800 C.

according

low

temperatures

higher temperatures
equation

At

to the

employed, i.e.
is deposited
carbon
are

"

CO+H2^C+H20
Either

of these

of carbon

reactions
in

obviously

finelydivided

permit

form.

It

of the
would

tion
preparatherefore

ELECTROTHERMAL

possible

seem

carbon

blow

NITROGEN
alternate

to

or

the

fixation

the

at the

conditions

nitrogen

would
The

process.

through

with

low

at

theoretical

reaction

the

A1203 +3C

+N2

lysts
cata-

It has

been

facilitates

gases

these

temperatures,

and

in

imaginary

the

above

for the

consumption

power

shaft

suitable

in the

hydrogen

maintained

be

is small, since

process

of

nitrogen

requisite temperatures.

presence

of

195

and

blow

especially sensitized

maintained
that

blow

steam

nitrogen, hydrocarbon

containing alumina
stated

FIXATION

Serpek

"

A1N

=2

calories per
requires only 213,000
of
fixed
ton
nitrogen calculated

+3CO
mol

kgm.

or

ammonia

as

metric

per

kw.

7300

hours.
It will be

formed

carbide

of the
If

is

the

energy

of

"5 kilomols

amount

of

calories, or

from

magnesium,
that

those

The

used

other

ton

of

Cyanides.

of

mol

per

by

energy

bustion
com-

of

15000 C.

of

alumina,

the

to

reacting

By the combustion
calories

102,000

of

from

cals.

of

able.
obtain-

are

able
avail-

are

to

nitrides

them
the

5170

taken

been

kw.

the

as

for the

There

passed the
principlesinvolved

Since

151,000

hours.

titanium.

have

which

to

preparation
aluminium, especially

out

besides
and

213,000

nitrogen calculated

fixed

Serpek

"

nitrogen

calories.

hours

silicon, boron

by

CO

kilomol

one

up

supplied

be

kw.

7300

laboratory scale, and

as

of

case

nitrogen absorption, reducing the

of

to

any

mol

one

theoretically 62,000

metric

from

the

are

speciallyprepared alumina,

monoxide

patents have

of ammonia

evidence

40,000

process

per

Various

and

that

energy

in

utilizable

of

heat

to

of carbon

the

ammonia

choice

carbon

follows

It

monoxide

reacting temperature

the

is about

temperature

carbon

consequently far greater.

necessary

kilomols

for

by

only

gaseous

that

utilized

be

CO

assume

we

can

The

of

nitride, whilst

the

manufacture

is obtained.

CaC2

mols

1*5

of

molecule

per

calcium

that

noted

have

market

is

no

experimental
are

the

already been
value

of

same

cussed.
dis-

fixed

ELECTROMETALLURGY

INDUSTRIAL

196

nitrogen in the form

actual

value

successful
utilizes

as

cyanide is greatly in

of

and
fertilizer,6

synthetic

expensive

cyanide

at

viz.

process,

of

production
to

the

to

Up

with

combined

with

as

cyanide

sufficient

cyanide

produced

so

in

having

ammoniacal

redirected

sodium

that

cyanide

cyanamide
considered

technical

heating has

this

included

which

those

would

electric

the

form

of

when

the

has

been
there

and

modifications,

newer

and

or

feasible

for

may

the calcium

only those

used

viz.

Bucher,

in

methods
will

suggested

be

large number,

representativeand

most

compete

years

processes,

naturally exclude

be

to

but

developed by

been

will be

and

union

of

acid

proceeds

formation

of
a

hydrocyanic

mixture

acetylene and
more

Acid.

Hydrocyanic

sparks through

The

is used.

will

developed

to

be

application on

appear

scale.

Cyanogen
indicated

these

this section

In

be

last few

synthetic ammonia

the

before

research, attention

process,

processes.

electric

yet those

of

one

finallysupplant both
which

stimulated

is evident

transportable

synthetic cyanide

these

to

prospects

the

has

at

the

of

providing
to permit of the
so
as
fertilizer prices after

some

During

nitrogen.

nitrogen shortage

are

into

converted

been

form

overcome

operation

costs

sold

able

been

some

could

the

nitrogen.

not

already extant,

be

to

be

to

process

working

in

have

in which

have

for

proposed

starting-point. It

would

processes

margin

been

ones

nitrogen fixation

the

and

+H2

processes

only sufficientlyeconomical

not

difficulties

cyanide

these

existing

the

ammonia

utilizing atmospheric

nitrogen is used

many

have

processes

time

Castner,

"

cyanides

present

compete

that

of

number

great

the

most

equations

to the

=2NaNH2
2NH3 +2Na
NaNH2+C=NaCN+H2
a

the

present

materials, sodium,

raw

charcoal, according

that

its

of

excess

of

Berthelot
acid

by

acetylene and

nitrogen

smoothly when

"

to

diluent

form
such

first

passing
nitrogen.

hydrocyanic
as

hydrogen

ELECTROMETALLURGY

INDUSTRIAL

198

data

No

of these

any

available

are

yield obtained

Gruszkrewicz

by

if a 03

that

into

converted

be

can

per cent,
a

by Lepinski by simple transition

yield as claimed

19 per cent,
from

it is evident

but

processes,

efficiencies of

conversion

the

to

as

spark discharge to

high temperature arc discharge

when
utilizingcrude
riched
producer gas or producer gas enwith
some
hydrocarbon, a cyclic process of heating,
heat interchanging and
scrubbing the gases with an alkali
would
certainlyprove worthy of investigation.
The
Alkaline
first
Earth
Readmann7
Cyanides.
a

"

the

suggested

nitrogen by
carbonate

of

use

of

means

and

electrical
a

carbon.

mixture
As

of alkaline

suitable

mixture

or

suggested

he

"

BaC03

50

Charcoal
intimate

The

10

mixture

coke-lined

of

air

Deoxygenated
When
as

electric

an

water

or

latter is used

the
fuel.

The

according

to

absorption
the equation

sides

is passed

denitrified
said

was

into

high temperature

introduced

in the

gas

the

to

current

inserted

kgm.
kgm.

is introduced

substances

is heated

and

electrodes

carbon

of these

crucible

by the passage
of

oxide

earth

of

following :

the

fixation

for the

heating

of

by

means

crucible.

the

through the mixture.

residue

be

may

used

proceed smoothly

to

"

BaO+3C+N2=Ba(CN)2+CO
Part

of the

opening

situate

volatilized

by
was

with

14000

C.
and

chromium
charcoal

the

gases,

The

above

with

commence

high temperatures

mixture
these
at

which

necessary

it

was

can

previously

recovered

absorption

molybdenum,
added

to

formation

heat, thus

red

when

part

the

absorption of nitrogen.

catalysts the
dull

and

be
of

lateral

slightly modified

titanium,

before

crucible

temperature

which
was

through

out

the

process

in

manganese

that

of

from

optimum

earth

flows

bottom

The

alkaline

cyanide will
the

the

Kendall,

or

is stated

formed

so

in

absorption.

by Swan

It

cyanide

no

of

avoiding

catalyst is present.

ELECTROTHERMAL

NITROGEN

FIXATION

199

suggested the following ingenious process : Fused

cyanide is electrolyzed between
granulated carbon

Mehner
barium

electrodes

in

is liberated
caustic
at

the

anode

the

at

alkali;

preferably charcoal,

confirmed
who
at

erected

Margueritte
alkaline
form

to

to

cyanides

easily,and

most

cyanide
blast

furnaces

the

catalytic effects

and

chromium,

recently investigated
of
as

of
the

the

Barium

reacted
made

been
it

render

mercially
com-

potassium reacted
formation
of potassium
Clarke

in

1835 and

1837.

Thompson

Clyde

the

in

catalytic effect of iron, and

metals,

by

such

as

Margueritte

Kendall

process,

is

steam

nitrogen

and

and

9000 C, by briquettes of sodium

a
catalyst. Decomposition of
superheated

and

alkalis

in

and

claims

complete

at

C,

has

rapid

temperature

coke

iron

and

cyanide by

6oo"

to obtain

carbonate,
sodium

Sourdeval

Bucher

at

gas

manganese

and

1895.

nitrogen in producer

the

alkalis

the

to

as

world

Swindel, and

attempts have

the

other

and

in the

carbon

so

the

to

noted

were

absorption of

with

the

as

of

by Swan

i860, and

both

Mond

Boissiere,

and

factories

that

Dawes

attention

1839 fast drew

in

in

and

by

early

as

barium

of

1843, of Newton,

Amongst

noticed

was

reacts

reform

to

of Possoz

process

sodium,

easily than

or

granulated carbon,

observations

unsuccessful

many

feasible.

cathode

high temperatures.

at

Readmann's

modify

more

in

readily reacted

earths

the

The

"

Sourdeval,

and

the

at

nitrogen fixation

Newcastle

and

in water

absorbed

nitrogen

experiments

first

the

Grenall

the

Cyanides.
earlier

the

with

Cyanogen

gas.

continuously reformed.

is thus

Alkali

be
free

set

and

nitrogen

can

melt

of the

temperature

The

and

barium

the

cyanide, which

of

atmosphere

an

means

according

to

following equations :

"

+4C +N2
NaCN
+2H20

Na2C03

=2NaCN
=HCOONa

+3CO
+NH3

2NaCN+4H20=Na2C03+2NH3+CO+H2
To

heat

carbon
the

up

and

reaction

one

kilomol
of

of

nitrogen

itself is

sodium
to

carbonate,

4 kilomols

900"C. requires 43,000

slightlyendothermic,

140

of

Calories;

Calories

being

absorbed,

and

3 kilomols

of

evident
a

ELECTROMETALLURGY

INDUSTRIAL

200

the

is

CO

that

reaction

the

as

in

and

one,

is therefore

It

be

can

considered

practice should

without

production

continuous

whole

of

the combustion

from

calories.

200,000

over

strongly exothermic

of

available

energy

be
of

supply

the

as

capable
traneous
ex-

any

energy.
The

carbon

produced would
that
much

lower

nitrides

be

working

the

metric

equal

to

1300

kgms.

of the

temperatures
those

than

preparation

formation

conditions

the

cyanamides.

favourable

According

expressed by the equation

CaO

+3C

place in

really takes

the

to

of

for the

gated
Caro, in 1895, investi-

intermediary

the

carbides, and

earth

are

formation

the

cyanides through

alkaline

of the

study

to

of

noted

will be

intermediaries

and

"

the

for

necessary

preparation of cyanamides.
Frank
The
Cyanamides.

It

ammonia

of

ton

cyanide processes

necessary

carbides,

of the

or

per

consumption

to

authors

first
of

formation

the
the

the

were

reaction

usually

"

=Ca

+N2

several

(CN) 2 +CO

stages

"

CaO+C^lCa+CO
Ca+2C^CaC2

1.
2.

3(a). CaC2+N2==CaCN2+C

(6).CaC2+N2^Ca(CN)2
following conditions

The

of calcium

formation

found

were

cyanamide

(1) The nitrogen

amount
required.

should

With

place

at

cyanamide

the

overproduction

the

beginning

utilizing these
fixation

of

large

one,

of

observations

atmospheric

themselves, and
is

11000

excess

at

the

of

century
Frank

to be

be

employed ;
the optimum.

carbide
the

and

theoretical

which

the

took

possibilityof
Caro

nitrogen immediately

the present time

annual

of the

should

C. appears
of calcium
the

the

"

(2) A porous carbide is desirable.

(3) Relatively high temperatures
for calcium

to

in

be

favourable

cyanamide

for

the

presented
industry

production being nearly

half

ELECTROTHERMAL
million

exclusive

tons

Central

NITROGEN

of

and

cyanamide

conclusion

to the

came

degree of dissociation

the
"

and

amount

dependent

were

carbide

of the

of calcium

the relative

that

formed

cyanide

of

Leblanc

war.

cyanamides

of

201

production

period of the

formation

investigated the

increased

the
the

during

Empires

barium, and

of

FIXATION

the

on

"

CaC2^CaC+C

1.

CaC+N2=CaCN2

CaC2+N2^Ca(CN)2

2.

Absorption
of

case

the

carried

found

The

Cyanamide

of

is

process

In

the

carbide

packed

is crushed

in small

capacity and
The

drums, which

amperes

contain

at

volts.

70
than

more

0*4

or

the

by

passage

the

exothermic.
hours'

passage

of the

that

gas,
at

to

and

by

ton

of

to

heated

are

is

some

should

prepared

Claude

10000

by

processes

absorption

finally turned

the

not

passed in when

when

C, and

kgms.

taking

oxygen
or

and

capacity.

reaction, which
about

is

800

mittent
inter-

500

tons

drum

copper,

"

tinuous
con-

powder

complete after
during which
period

from

metric

fine

metric

Linde

8oo"

absorption

is maintained
it is found

of

being maintained

The

is reduced

current

the temperature

to

of 300

each

hot

two

in Norway

nitrogen, which

the

over

risen

has

temperature

commences

of air

Odda

refractory bricks,

cent,

per

fractionatingliquid air by
the

to

Pure

cium
cal-

by

earlier

at

to

each

resistors,

carbon

the

higher grade product.

work

drums,

lined with

are

of

The

the

than

at

recently of

more

internally by
20

sheet-iron

fluoride

continuous.

ground

and

experiments
facilitate

to

and

somewhat

process

cyanide.

manufactured

now

and

barium

the

results.

economical

more

intermittent

the

is

produces

and

ones

calcium

of

agents

best

intermittent

the

processes,

series

chloride

give the

to

out

addition

absorption of nitrogen.
were

carbide, but

in the

C.

large quantities of

suitable

of

use

7000

at

commence

calcium

and

Carlson

and

to

contained

always

Polzenius
on

barium

both

product

found

was

C.

cyanamide

the
In

is

off,
is
30

rature
tempe-

practice
produced

INDUSTRIAL

202

from

078

drums

the

energy

expenditure required for heating

is about
metric

by the

alternative

guide

the

to

conservation

of

of nitre
of that

nitre

of the

most

economical

in

the

to

practice, since manual

problem
the

it.

The

the

by

process

in terms

of

become

the

alluded

to

of the

of the

relative

in

of the

two

and

energy

of

sources

energy

in the

carbon
at

In

the

alternativelybetween

two

of

the

as

whole,

taking nitrogen
with

areas

efficiencyof
fix

to

costs

different
and

given

the

to

forms

running

of

costs

the

various

are

usually required,

of coke

factory in these

or

following table

form

modern

only, viz.

by the

nation, erection

for that

great

entirely replaced

transportation

costs

too

In the

required

energy

the

thedeciding factors between

the

be

cost

different, the choice

solely determined

be

In

large supplies

taken

involved

deciding factors.

viz. electrical
costs

the

available

energy

if

solution

process

is somewhat

nitrogen and
but

consumer,

of the
natural

of the

consideration

one

costs

problem

is not

amount

really offer

the soil in the chosen

fertilizing

method

fixingnitrogen

would

international

material

national

The

problem

that

be almost

can

energetic efficiency of the

i.e. the power

and
from
the air and

of

development.

the

decided

be

exceed

not

Processes."

utilization

consumer

labour

work,

will

ton

nearly inaccessible region, the

some

delivered

mechanical

should

fundamental

It is evident

permit of their economical

by

liquid air

to

metric

one

already described

processes

world.

existed

of

kw.

500

or

According

production of

solution

of the

fixed.

Nitrogen Fixation
comparing the costs

for

and

kilogram

per

nitrogen

cost

of

estimates

of

of

ton

hour

nitrogen by fractionation

various

to

kw.

o*i

estimates, the

resources

some

electrical

Comparison

no

Nitrolim," containing

as

nitrogen.

per

recent

of

market

packing

crushing and

of fixed

carbide

hours

after

"

the

of

contents

per cent,

20

The

The

carbide.

cool, and

to

the

on

of

ton

allowed

are

15 to

o-8o

to

placed

are

ELECTROMETALLURGY

two

processes

the

relative

forms

would

equally efficient processes

different proposed factory sites.
two

the

approximate

consumption

NITROGEN

ELECTROTHERMAL
and

of energy

coke

fix

given

required to

by the different processes

are

FIXATION
metric

203
of

ton

nitrogen

"

16,900
It

is
a

of

the

interestingto
relativelylarge

hydrogen,

and

that

note
amount

that

any

the

Haber

of coke
technical

process

for the

sumes
con-

production

development

of

ELECTROMETALLURGY

INDUSTRIAL

204

either

the

would

be

Bucher

rivals

serious

Serpek

modified

or

the

to

Haber

"

also

S.

Zeit.

Trans.
Over
French

in

Reviewed

10

9,

Chem.,

17,

Elektrochem.,

Zeit.

"

the

1912.

1917.

233

20,

194.

Alkali

R.

R.

J.

Industry,"

TO

Industry,"

Cyanide

1914.

BIBLIOGRAPHY

"The

64

p.

1895.

of

Eng.

Ind.

24,

Soc,
in

value

the

Patent

series.

2412.

Electrochem.
times

nine

28,

Chem.,

Amor.

1917.
this

Purification."

Sewage

Angew.

/.

"

edit.,

Partington,

Industry/'

Alkali

The

Rideal,

"

processes

VII.

3rd

London.

Problem."

Wheat

The

See

1Q2)

p.

cyanamide.10

or

SECTION

TO

REFERENCES

(see

"

series.

VII.

SECTION

Robine

this

Partington,

Wiley

Lenglen.

M.

"

Sons.

1906.
of

Fixation

"The

Escard.

Nitres,"
Die

"

u.

Ausnutzung

Coal

"

der

Atmospharischen

of

Tar

and

Atmospheric

T.

Nitrogen,"

Ammonia,"

Lunge.

Cyan

verbindungen,

'
'

'

14.
des

composes

Sticks

toff,"

Donath

1907*

Utilization

"

19
et

1901.

Technische

Frenzel.

Knox.

Nitrique

l'Acide

de

Electrochemique

"Fabrication

J.

Nitrogen,"

Atmospheric

Technologic

der

'

Norton.

Bertelomann.

Washington,

906.

191

2,

206

ELECTROMETALLURGY

INDUSTRIAL

warmed

650 C.

to

with
that

density of

current

than

01

of

cent,

per

metal.

E.M.F.

Pfanhauser

and

Langbein

CaCl2, 600

FeCl2

gms.

(900 C),
Sulphate
have

Electrolytes.
of 99*97

the

addition

as

low

as

to

an

overcome
6

Storey

300 C.

With

15

Hambuechen4

purity with

volt

both

at

iron

at

found

was

anode
an

per

rature
tempe-

to

very

ferrous

gms.

density of 06
of

of Swedish

anodes

following analysis of

conditions

from

chloride,

iron

current

applied E.M.F.
the
passivity

gives the

these

under

and

cent,

per

of ammonium

ingot and

per sq. dcm.

(700 gms.

density from

current

Burgess

"

litre with

American

chloride

higher temperature

efficiency(over 90 per cent.)

sulphate solution containing 40

current

ammonium

or

water), at

higher

use

I^ess

deposited

in addition

chloride

litre of

volt.

in the

likewise

anodes

dcm.

sq.

deposited iron

high

with

and

amperes per

20

to

o*6o

is occluded

provided

iron

Wrought

is about

hydrogen

electrolytecontaining calcium

to

per sq. dcm.,

3 to 5 amps,

the

and

employed,

obtained

depositsare

electrolyte is circulated.

the

are

electrolyte. Good

as

bar

ampere

necessary

and

cathode.

iron

produced

"

Fe, 99963 per

cent.

H2, 0083

per cent.

C, 0013

per cent.

P,

cent.

S,

per

cent.

Si, 0*003

Per cent.

0020

O.

per

P.

chloride

and

Watts

and

0001

H.

find

I4

that

electrolyte containing

mixed

150

sulphate
crystallized

gms.

ferrous
per

sulphate (7H2O), and 75 gms. ferrous chloride (4H2O),

litre is better than either sulphate or chloride electrolyte

alone.

As

ammonium

oxalate

ammonia)
Other
and

or

per

been

of ammonium
can

suggested

oxalate, is the
be

deposited

procedure be followed

dehyde
(formal-

tartrates, citrates

complex

as

only

and

in detail.

this

time

from

ferrous

equal weight of oxalic acid, and

an

gms.

electrolyte.

electrolyte,containing

Classen's7

hexaminetetramine

0*5 gm.
litre of

advised

they

agents

electrolytes,such

oxalates, have

free iron

addition

suitable

one

to

ammonium
7 times

from

only when

time.
phate,
sul-

its

weight

which

carbon-

the

author's

IRON
Coles

Cowper
aromatic

acids

The

or

has

FERRO-ALLOYS

patented the

for the

charcoal

Production

Pig iron

"

is

The

limestone.

and

of iron salts of several

use

Iron.

of

generally produced
of iron

smelting oxide

by

207

deposition of electrolyticiron.

Smelting.

furnace

blast

THE

I"bctrothermai,

Ore

A.

AND

fuel

with

ores

is burnt

coke

the

at

in

base

furnace.

of the

ordinary blast furnace

The

into five

zones

(1) The

"

top

in which

zone,

the

entering charge is heated

this

In

in the lower

produced

dioxide

conveniently divided

by the ascending hot gases.

monoxide

be

can

part of the carbon

zone

is oxidized

zones

carbon

to

"

2CO+02^2C02
the
to

drive

off the

in the

water

this

(2) In

and

ore,

ferric

the

zone

monoxide

by the carbon

third

the

(3) In

incoming charge
calcium

the

convert

+C02

to

ferrous

+CO
reduction

actual

temperature

the reduction

bring about

is reduced

"

where

zone,

place, the

takes

oxide

=2FeO

Fe203 +2CO

metal

the

warm

into oxide.

carbonate

oxide

assisting to

liberated

heat

the

to

is

sufficientlyhigh

zone,

together with

the

containing the

ash

to

"

FeO+C=Fe+CO
The

of the

gangue

the

immiscible
Both

slag and

The

gases

8oo"

C),

carbon

the

the

third

third

pig

are

at the

lime

zone,

layers, the slag

being admitted
to

with

of the

base

in

chiefly silicious,and

ore,

fuel fluxed

of the
to

melted

metal

on

tapped

where
the

dioxide

is not

are

of the

complete,

fusible

the

slag,flow

they separate into

molten

intervals, fresh

top of the furnace

combustion

top of the

off at

leaving the furnace

and

form

to

two

metal.

charge

shaft.

still hot

monoxide

carbon
ratio

(from 3000

CO

to

C.

into

C02 being

208

INDUSTRIAL

about

2:1.

ELECTROMETALLURGY

The

waste

gas

furnace

the

is

generally

used

for

is

controlled

steam

raising.
that

ideal

the

In

oxide

only the

impurities,such
actual

In
a

small

temperature

of iron

is reduced

half the

practice the phosphorus,

of silicon

sulphur

and

the

not

the

and

silica, manganese

as

quantity

and

so

other

phosphates.
and

manganese,
retained

are

in the

iron.
The

Consumption.

quantity
the

of coke
of

amount

pig

and

sulphur

for

not

for

blast

has

energy

that

the

that

the

same

hours

or

fuel is about

charcoal

of

of the

two

in
ton

fuel

good

as

electric

oxide,

consumption
fuel

is

required

charge electrical
modern
If

pig.

systems

course

of the

the

the

of

of

the

In

of

heat

equal

impurities such

coke.

the

iron

practice
we

the

are

assume
same

and

quality of pig is produced, electric smelting

of electrical

grade coke
The

costs

cheaper than

will become

To

pig

as

one-third

about

supplied, and
will produce one

working

the

charge;

be

hours

kw.

2000

to

used

of

only for reduction

operation.

furnace

production

absence
in

present

to

the

produced

to the

heating the

reduced

therefore

iron

is used

carbon

the

furnace

silica

In

"

charcoal

or

being preferable,owing

and

used

"

Power

to

represent those

ores

practice :

in actual

the

of iron

following analyses

energy

blast

furnace

cost

less than

data

necessary

pig

when

0*66

ton

2000

kw.

of

high-

charcoal.

thermochemical

for

calculating

IRON

FERRO-ALLOYS

THE

AND

efficiencyof the ore-smelting

accurately the theoretical

more

process

If

be

can

broadly summarized

take

we

of water,

cent,

8 per

and

by experiment that
addition

the

in the

of

12

charge, we

ores

calculate

used,

are

increase

Fe2Os, 2
impurities,and

of limestone

cent,

per

for this reduction.

grade

"

easilytappable slag is obtained

an

can

cent.

per

of other

cent,

follows

as

containing 90

ore

an

209

in

the necessary

of

ton

by
ore

ture
expendi-

energy

necessarilyfollows that if lower-

It

flux will be

more

each

to

per
find

wasted

energy

sponding
required and a correfor slag production

will result.
The

of

heat

to the

production of
equations
Fe203 +CO
2FeO

is found

equal

to

metric

one

=2FeO

+2CO

"

(Fe2,Q8)-(C,08)-(C,0)
Since

+C02

=2Fe

+2C

of iron according

ton

calorfes per
calories

(Fe2,03)=201,000
(C,02)= 97,200
(C,0)
29,200

"

k.lomol

the

required

energy

metric

per

ton

of

metal

is

565,250

calories.
To

heat

melt

to

further

the

it and
350,000

For

each

ore) 200
For

ton

iron

so

produced

bring it

to

calories

are

of molten

kgms. of limestone
calcining

85,000 calories will

be

will be
of

limestone

required, and

calories

and
i*.

will

requiredfor slag formation

If

we

assume

contain

that
carbon

melting-point,

the gases
monoxide

of

required.

produced (112 kgms. CaO+128

in the
ore). For reducing the
melting the slag to bring it up
heat

the

the

approximately

kgms. of slag will

240

kgms.

be

600x240=144,000

to

tapping temperature,
required.
pig produced (from 16 tons
to

kgms.

200

up

other

impurities,heating and
to tapping temperature,
be
total
required. The

is therefore
leave
and

impurities

calories.

239,000

the furnace

dioxide

in the

\ ::"l
"
.

5000 C.

at

ratio of
14

INDUSTRIAL

210

the

2:1,
as

and
to

off

of metal

kilomol
of

0-5 kilomol

in the gas

of CO

in the

C02,

in the

CO

or

per

of

calories

X69

is 500

and

metric

C02

of

combustion

of

metric

of the

available

the

carbon

monoxide

of water

i.e.

"

"

637

+-

1000

"'

calories, making
for the

Hence,

composition

energy

required is

of

one

slag

the

lost in the

energy

is

steam

0*48

to

1000

kilomol

production
.

of

production

for the

gases

of metal

theoretically required, or

of the

"

the

ore

239,000

1,167,500

produced
per

metric

cals.

of
.

915,250

kilomol

y*

2,321,750

..

every

the
X

400
^

Total
For

evaporation

distribution

the

above,

follows

required

energy

Total

as

Total

in

1,046,000 calories

or

metal

the

sequent
sub-

1,167,500 calories.
iron
ton of pig from

total of

indicated

required for

energy

production

of the

Total

the

100

100

=30,000

"

"

calories.

present

superheating

and

in

lost in the

heat

the

pig, and

cent,

per

5000 C,

of

ton

calories

53,000

energy

the gas, viz. 68,000 calories per kilomol,

per

calories

total of 91,500

lost

heat

and

the

added

be

must

CO

the

100,

as

pig produced

38,500 in the C02,

and

produced according
Taking the molecular

in the

ton

monoxide

of carbon

are

above.

6*9

as

kilomol

dioxide

carbon

equations given

this

calculated

be

can

"

every

the

by the gases

specificheat

To

carried

energy

follows
For

ELECTROMETALLURGY

of

ton

pig

of carbon
214

kilos

of carbon.
For
of

calculating the total

metric

ton

of

required for the production

the followingfigures :

energy

have

pig, we

"

Energy required for metal production

Energy required for slag production
Energy

lost

as

heat

in the

gases

915,250
239,000
121,000

Total
.

equivalent to

150Q

kw.

hours

for

very

1,275,250

high grade

ore.

cals.

IRON
If

fuel

AND

be

for

used

FERRO-ALLOYS

THE

heating the

injected for supplying the

therefore
to

contain

its greater

combustion

of

ratio, viz.

the

large quantities of
"

viz.

temperature,

1:2,

C.

900

the

If

carbon

complete

we

the

be

gas

will

resulting

owing

furnace

higher

at

fractional

that

assume

electric

must

nitrogen, and

the

proceeds

in the

as

sufficient air to

furnace, air

oxygen;

velocity will leave

211

the

to

furnace,

C02

same

require

shall

we

following reaction

CO

"

3C+8N2+202=8N2+2CO+C02
The
to

heat
CO

C02 in the above

and

heat

absorbed

molecular

giving

by the combustion

liberated

by the

83,000 calories.
therefore

iron

To

as

this

total of

the

case

increased

total

would

we

for reduction

kilos

214

of

of

of carbon

the

are

quired,
re-

764 kilos.
lost in the

energy
of

production

greater, viz. 4,390,000

calories,

of carbon

calories

1,275,250

that

seen

7, is 72,000

for 3 kilomols

produce

have

we

making
the

nitrogen

the

9000 C, taking the

at

require 550 kilos of carbon

oxide

In

of

of carbon

155,600 calories,and

leaving

of combustion

heat

net

ratio is

gases

specificheat

of 3 kilomols

is

monoxide

carbon

calories, than

owing

gases

electrical

when

to

much

heating

is used.
As

to

gases

how
be

can

wide
noted

that

total

energy

In

the

variations

in the

CO

pure

is diluted

gas

in

two

process,

actual

found

down

first

the

and

case

one-third

elevenths

the

fuel

as

times

four

of the

cent,

50 per

is thus
the

consist

with

large

the

combustible

CO

The

successful

with

in

cally
practifurnace

combustible

the

nine

The

nitrogen, the

consisting of two-thirds
diluent, while

of

blast

of

amount

lost.

quantity

smelting operation is lost.

C02 mixture, whilst

of

effluent

preheating or power
duction
proin practice. It will be

process

over

in

heat

the electric furnace

products from

with

are

for

electrothermal

thermal

gas

CO,

available

supplied electricallyand

usual

gaseous

the

feasibly utilized

requisite for the

of

much

second
elevenths

only
of

diluent.

Furnaces.

"

earliest

furnaces

employed

for

production

the

and

Heroult,

The
in

and

shafts

is fed in

the

other

with

through

Haanel's
details

si.

quality

good

able

of

low
kw.

2200

coke

carbon
In

the

fed

and
in

round

Haanel
at

Sault

thu

Livet

and

bound
In

Dr.
he

(1904),
(France),

where

white

with

0"i7

kgm.

of carbon

furnace

carbon

but

base

level
metal
the

of

the

are

reported

favourably

of

which
on

of

91

ceedingly
ex-

of

cent,

per

as
as

by

the

smelting
is
this

(U.S.A.), producing

the

liner

other

tapping
fresh

gradually
furnace

is

electrode

pendent

serves

removed

period

will,

electrode.

continued

slag

at

was

expenditure

kgms.

one

plate

electrode,

Marie

360

Using

iron),he

iron

energy

an

visit.

cent,

cast

grey

using

ton,

and

or

ferro-alloys.

his

during

(48-1 per

ore

and

smelted

were

the

Ste

lining

Government
at

gases.

B,

lining.

productj

per

During

B.

metal,

the

convenient

furnace

sulphur,

the

Slag

electrodes,

escaping

dolomite

Canadian

hematite

Heroult

little above

ore

in

and

employed.
a

for

either

hours

for

one

the

the

The

CC.

of

produce

to

off

basic

most

the

to

Furnaces

"

tons

30

the

H^""ir

(A)

over

A.

slag,

round

placed

alloys.
ferro-

electrodes

passage,

Keller

of

pendent

two

drawing

of

production

by

provided,

experimental

an

Fig,

for

found

report

the

of

hoppers

are

the

was

for

consists

is made

for

tar

used

those

were

communicating

holes

tapping

iron

pig

furnace

provision

Two

of

originally

Keller

vertical

charge

ELECTROMETALLURGY

INDUSTRIAL

212

in

pig iron

trode.
elecholes

charge

raised.

to

is
Dr.

operation
from

such

ELECTROMETALLURGY

INDUSTRIAL

214
Tjndblad
of

and

series

of

in

operated
this

design

and

at

from

Stalhane

The

shaft

large

subsequently

were

kw.

to

furnace

kw.

7500

has

in

is
to

the
and

with

electrodes

60

the

the

transformed
to

10,000

and

the

to

90

50

to

each

of

stated
and

Shaft

furnace

be

to

pig

The

pig produced

of

consumption
(50-60
dust

consist

of

nitrogen.
the

4-5

carbon
with
The

hearth

to

03

kgms.

iron).

scrubbing part

together

to

cent.

per

and

is from

monoxide

or

and

gas

ton

the

whilst

thermal

80

for

the

means

electrode
ore

the

removing
gases,

the

of

ton

magnetite

smaller

by

per
an

in

ton

one

obtained.

be

with

is

cent.,

per

nearly

evolved

dioxide
and

amperes

furnaces

can

of

is made

is returned

through tuyeres,

of

from

pressure

The

consumption

reduction

all of

little hydrogen
clean

of

Provision

volts

nearly

hour

per

fuel

07

for

to

is used,

20,000

output

an

for

of

current

these

ElictToiUs
"

diameter

furnace

phase.

efficiency

22.

spaced

current

at

12,000

on

ia.

of

hearth.

Three-phase

"

in

cms.

brick,
fire-

tar.

equally

conduct

to

serve

shaft,

lining

with

six

or

it

with

inner

bound

Four

of

constructed

lined

an

high,

Both
are

shell

of

where

cms.

hearth

magnesite

hearth

diameter

shaft.

steel

the

metres

25

enters

roof

whilst

diameter

and

metre

*of

sizes,

varying

maximum

constricted

Ttppint

of

in Sweden

Hagfors

at

high,

metres

of

furnaces

furnace.

metres

erection
These

and

manner,

in Norway

per

is 15

shaft

the

to

TrolMtten.

at

erected

Arendal

and

led

furnaces

highly satisfactory

Hardanger

3000

Domnarfvet

at

ratio

which
2

quantity
of

unscrubbed

blower
excess

1,

of

IRON
is

gas

AND

piped
owing

FERRO-ALLOYS
for

used
has

content

raising.

deleterious

215

steam

partial combustion

to

reaction

to the

and

away

dioxide

carbon

THE

effect

on

of the carbon,

high

the

trodes
elec-

according

"

C+C02-"2CO
The
hours

is

material

but

It

is

with
of

extremely

gas

that

probable

furnaces

circulation

will

of the

be

circulated

degree

same

is not

of heat

in the

as

disadvantage.

is

It

together with

of

some

of combustion

of the
inside

employed

is

air

gas

monoxide
furnace

the

ing
smelt-

shaft

the

by

the

to

the

more,
further-

injected

through

tuyeres

itself,the

could

be

outside

than

obvious

an

were

smelting chamber

carbon

ore

type,

the

furnace, and

if

that

liberated

the

the

just above

from

smelting chamber

evident

shaft

preheat the charge

ordinary blast
the

of

present conditions

the

charge in
to

the
cent.

0*5 per

of the

abstracted

the

to

per

of

development

lines

Under

o*oi

nature

less than

at

the

on

sufficient

chilling of

the

situated

carried

and

the

future

gases.

operation,the quantity
chamber

with

than

grade

carbon,

cent,

per

usually less

varies

content

high

very

3*5

kw.

2200

averages

some

usually maintained

be

reduction

iron.

pig

phosphorus

silicon

can

furnaces

analyzing

produced

The

of

ton

sulphur and

cent.
ore,

metric

per

with

of these

consumption

power

heat
fully
use-

more

for

steam

raising.

The

B.

Production

Although
production

the

of

is very
is

supplant

has

where

areas

the

open

furnaces

of

electric

slow

in

Steei,.

furnace

for the

development

and

the

price of electric power

production and refining of steel

electrical

hearth

the

been

large industry, and

Electrical
purposes

iron

to

low, the

already

application of

pig

is still confined

Refining

and

and

in time
Martin

probably entirely

processes.

employed

are

will

for

several

distinct

"

(a) Refining
steel with

open

the

hearth
aid of

and
flux.

Bessemer

or

acid

verter
con-

216

INDUSTRIAL

ELECTROMETALLURGY

(b) Fusion

of pure

(c) Fusion

of

without

Power

charge is inserted
raise

any

oxide

iron

to

cold, the

the

tapping temperature,

y6

cent,

the

and

0*28

produced

is

0*02

The

that

and

the

phosphorus,
of these
for

necessary

used.

ton

Cold

kgms.
45 kgms.
285 kgms.
Same
charge
675 kgms.
210

350
Same

kgms.

500

both

slag above
of

phase, whilst

contact

functions

take
both

underlying metal.

460

230

two

pig

with

up
in the

sets

may

reactions

of

and

as

reactions

330
210

of

reactions

slag. The

slag and

53

process

the

reactions

protector

Both

The

phases, and

separate

heterogeneous

280

"

place between
as

Slag.11

the

steel and

it form

cold

scrap,

purificationhomogeneous

each
of

in the

pig

refining is intimately bound

occur

scrap
molten

of

Function

lime

charge molten
365 kgms. pig
650 kgms. scrap, cold
Same
charge with molten
The

190

cold

ore,

the

hrs. per
of steel.

metric

pig iron and flux

Iyiquid pig and flux
670 kgms. pig

carbon

cent,

Kw.
Materials

pig

silicon,

of oxidation

energy

melt

reduce

to

cent,

per

0*96 per

heat

from

subtracted

includes

cent,

per

contain

to

silicon.

cent,

per

impurities
refining-

and

one

the

assumes

i*68

carbon,

cent,

per

further

He

present.

manganese,

steel

to

the

When

melting-point,to

the

it to

contain

and

supplied

energy

charge

iron

per

materials.

raw

of

production

the

the

of

or

calculated

has

heat

to

necessary

i#i

for

consumption
steel,using various

of

10

Neumann

"

fluxes, with

of iron.

energy

ton

it and

steel with

scrap

of oxide

Consumption.

necessary
metric

pig iron,

addition

the

materials.

and

in the
take

metal.
a

which

metal

at

steel

the

course

place

the

surface

The

refiner

require

in

to
a

slag
the

high

IRON
to

temperature
The

with

ease

of the
The

AND

ensure

of the

metal, when

taking

which

by

the

series of chemical

varied

following

impurities, phosphorus,
in

selective
be

the

order

oxidation

Oxidation

is

the

case

the

slag and

the

of

the

period

sulphur,
the

at

the

metal

in

in

the

slag if basic

sulphur

as

the

ferrous
oxides

and

the

phase.

the

oxide

absorbed

by

the

of

Part

of the

itself.

To

oxide

reducing agents
formed
slagged
calcium

the

slag are

carbide

can

off.
have

then

be

of

in

the
the

to

is

there

reduced

added

Aluminium,
all been

and

by

the

return

to

is

reduced

metal
as

metal

continuously
of

disturbance

silicon
used

the

carbon

high temperatures.

very

in the

the

nickel

reduced

of oxide

to

and

chromium,

metal

and

ferric

of

in

iron

is

phosphorus

oxides

at

last traces

the

remove

enters

part of the

removal,

only reduced

also be

can

between

is retained

manganese

any

slag owing

partition equilibrium,

in

As

phosphorus

more

is elevated, the

respective metals, which

Any

is

ratio, consequently

removal

with

is

which

sulphur dioxide.

as

in the

oxide

oxide

can

carbon.

or

is distributed

phosphorus

high temperatures

Silicon

by

phosphate.

temperature

vanadium

silicon

phosphorus

the

together

at

tungsten and

of

When

"

oxide
and

calcium

volatilized

Deoxidation.

complete

oxidized

process

be

may

slag,

removed

13500 C. it

; at

definite

chief

three

of its formation.

phosphorus

The

is

ferric

the

slag

silicon,

sulphur, usually takes

either

by

and

of the

temperatures
than

occurs,

"

Phosphorus

about

metal.

During

to

low

it is oxidized
the

and

oxygen

named.
at

removal

brought

present in the

from

The

"

easily oxidized

more

when

metal

reactions, amongst

important

most

are

one

by the boiling-point

mingling of the slag and

Dephosphorization.
place

is set

is

processes.

long time to separate.

chief impurities,phosphorus, sulphur,

removed

are

viscosity.

electrothermal

limit of the temperature

upper

The

of the

advantages

low

is obtained

high temperature

217

high diffusivityand

which

distinct

FERRO-ALLOYS

THE

to

metallic

the

metal.

phase

rapidly,various
and

the

ferrosilicon

for this purpose.

oxide
and
It

is

evident
a

ELECTROMETALLURGY

INDUSTRIAL

218

during this period of reduction

that

danger of phosphorus

the

reduction

slag by

obviated

reduction

phosphide, Ca3P2,
Both
effect

sulphur

their

effected

of

in

which

acid

but

slag using
The

"

iron

divides

itself between

in

definite

ratio

of the

with

solubilityof FeS

increases

with

in the

original

molten

metal

general principles

ratio

in

solubility of FeS

to

be

can

oxygen

the

the

since the

slags

lining.

slag and

in accordance
;

basic

sulphur present
the

partition coefficient

of

silica brick

calcium

by the steel.

require

removal

before

during

endothermic

reabsorbed

the

be

can

temperature

the

phosphorus

Desulphurization.
a

form

is not

and

This

dephosphorizing slag
the

from

metal

the

to

phosphate.

the

period to

removal,
an

the

rapidly raising

by

or

the actual

of

removal

by

reduction,

being returned

exists

there

slag

in metal

rising temperature,

for

high temperature

of the
is essential.
Removal
sulphur is
sulphur removal
to sulphur dioxide, during the
partly effected by oxidation
period of phosphorus removal, but chiefly due to reactions

taking place in the

metal

re-establish

to

in the

brought about
carbide

and

Silicon

formed

and

only

is used

active

as

sulphur diffusing from

more

equilibrium.
slag by

according

is most

formation

slag ;

to

at

lower

at

temperatures,

desulphurizing agent

present, since

the

reaction

carbide

the

carbide

of

means

large

melt.

whilst

lime

When

high temperatures.

very

lime

the

of

temperature

desulphurization by

occurs

is

Desulphurization
of silicon, carbon,

means

the

the

be

must

excess

"

CaO+FeS^FeO+CaS
is

reversible

complete
owing

removal

2CaO
Prior

elimination

high temperatures,

at

to the

The

one.

+2FeS

to this the

usual

of the ferrous

+CaC2-"2CO
reaction

"

CaO+FeS+C=CO+Fe+CaS

of

sulphur is practically

when
oxide

is

carbide
from

+2CaS

the

+2Fe

formed

slag
"

IRON
takes
the

At

place.
such

silicon.

This

entails

intermediate

by

be

to

extra

an

in

formation

an

in

oxide

added

reducing

form

of ferro-

in the
and

too

cause

may

resulting steel.

the

of silicon

ferrous

of

means

expense,

present

219

the

temperatures

silicon,usually added

as

silicon

much

low

FERRO-ALLOYS

only be removed

slag can

agent,

THE

AND

The

sulphide
"

2FeS+Si=SiS2+2Fe
probably
added

also

plays

part in the

furnace

the

16000

C.

of

the

attained

these

At

lies

slag

The

work

lining.

In

various

the

materials

for

used

not

much

so

of the
of the

has

work

composition

shortens

liners

tion
operaC. and

melting-points
largely been

has

Washington,

at

accomplished

been

on

the

fluence
in-

melting-pointand viscosity

the

on

perfectly

12000

and

accomplished by the Geophysical Laboratory

but

sulphur

furnace

normal

composition

the

on

of
be

must

softening point of slags lies between

C.

between

probably

period

the

furnace

of the temperature

elevation

furnace

the

leaves

in the

and

last

the

temperatures

fluid,since unnecessary

14000

C,

17000 C. during the

and

life of

16000

to

steel

Liquid

"

temperature

removal.

the

Slag.

15500 C.

about

at

itself

of

sulphur by

ferrosilicon.

Composition

the

of

removal

slags themselves.
and

Vogt
silica in

the

of calcium
furnace

Doelter

slag raised

fluoride
75

l2

per

the

Bureau

this

problem,

Feild.18

He

points of

various

the

made

cent,

of Mines,
and

showed

more

fluid.

have

been

preliminary report has

technical

the

In

following data
slags :

"

of

lime

or

addition

the

slag is still tappable.

Washington,

gives the

of

excess

viscosity,whilst

slags

lime

that

electric

Recently

investigating
been
the

given by
softening-

determined

He

and

found

figures refer

found
20"

to

blast

The

to be

furnace

times

301

silicates have

pure

of

Types
furnaces

the

following melting-points:

"

been

the

and

arc

but

at

former

than

temperatures

are

in

induction

furnaces

the

time

same

principleof heating

employed.

In

the

the

than

induction

and

14000

C.

in the

have

each

faults

have
to the

furnace

arc

Resistance

operation

slag, although it

obtained

C.

"

Arc, Induction,

two

12000

Three
employed.
types
employed for steel production

Furnaces

have

only

hotter

of water

that

greater than

10500 C.
11500 C.

refining, viz. the

the

have

we

ably
is consider-

furnace

FeSi03
MnSi03
CaSi03
Mg2Si04

The

as

C.

The

but

mined
deter-

thermocouple.

by

slags, and,

electric

slags

viscosity of the slags at 15000 C.

average

about

also

and

in the

temperature

higher.
at

lie

tapping temperature of various

between
and
15720 C. as
1470

optical pyrometer

noted, the

was

the

it to

by
The

ELECTROMETALLURGY

INDUSTRIAL

220

never

furnace.

large scale.

distinct

type

metal

and

furnaces,

tages
advan-

peculiar more

actual
the

on

of

to

of furnace
is relatively

actually attains

the

INDUSTRIAL

222

The
35

ELECTROMETALLURGY

of

carbons,
in

cms.

diameter,

at

operates

which

to

70

there

volts

12 ton

Fig.

kgms.
I^ess

Conducting

"

The

carbon.

per
6

23.

furnace

for

is

or

Heroult

which
one

metal

current

The

has

six
been

furnace

for
in

electrodes

Heroult

types.

arc

and

Keller

series

to

naces
fur-

type,

arc

current

and

passes
the

other

phase-current,

are

for

in

three

used

whilst

simple alternating
hearth

arcs

electrodes

Frequently

electrodes

to

than

metal, striking

passage.

one

appear

in the

electrode

between

three

of

the

the

its

electrodes

the

through

pendent
four

of

arc

has

treatment

series

from

use

about

of

type
lining

Stassano

in

The

is

would

furnace

obtains

are

used

it

which

The

H^nulr

this

severer

that

EU-".

in
but

the

stand

has

amperes

production.

steel

obtained

that

""",

4000

consumption

carbon

furnace,

ip

furnace

J.

furnace

hearth

of

current

are

ones,

the

parallel,and

Girgd

average

fluctuation

load

with

pendent

of steel.

ton

per

in

connected

75

four

are

for

Keller
current.

three-phase

suggested.
follows

the

normal

construction, consisting

IRON
of

AND

steel shell with

roof
hearth

The

voltage lies between

consumption
charge is from
from

to

200

thus

have

kgms.

At

Chicago,15
and

is then

poured

half
fresh

flux

the

of

and

suitable

amounts

added,

are

from

When

is

furnace

the

coke

metal
iron

.lime and
At

phosphorus.

the

is added
is

ferrosilicon

to

of

end
and

slag removed,

removal

the

of carbon,

until the
The

removed.

is tilted, the

furnace

uses.

remove

the

complete,

ferromanganese

and

the

again tilted, and

metal

run

the ladle into the moulds.

At
an

the

remove

sulphur.

variety of

electric furnace, and

lime, fluorspar and

oxygen

loss

electrode

steel is blown

practicallyall

are

diameter

type, being about

to

put

converter

into the
to

hour

an

been

Bessemer

added

are

Girod

the

slag

produced.

have

silicon

carbon

ore

of steel

furnaces

in

than

very

of the

cms.

The

used.

one

usually

are

60

to

up

cold

hot

surface

the

to

on

liner ;

roof

with

electrodes

actually been

per ton

These

The

the power

with

produced

hours, and

down

arc

naturally heavier

12

kw.

tected
pro-

pitch.

volts,and

100

of steel

ton

hours.

protect the

electrodes
is

kw.

300

90 and

800

to

700

reflect the

large, to
and

metric

per

with

bound

no

be further

liner may

employed, the
magnesite slag mixture

The

is

electrode

by

223

magnesite or dolomite lining.

of silica brick.
Since
frequently made

is

liner

FERRO-ALLOYS

THE

Syracuse, phosphorus
hearth

open

transferred
At

to

furnace

and

H6roult

furnace

I"a Praz, three

final addition

the

carbon

made

to the

slag

removal

are

Each
additional

50 to 60 kw.

Stassano's
one

iron

of the

runs

installed
steel in

at
one

formed

at

Darfo

removed

and
of

before

ferro-alloyand

steel.
necessitates

the

per ton of steel

Captain Stassano

hours
"

investigatorsinto

in the

ores

subsequently

desulphurization.

requisiteamounts

Furnace.

first

for

electric

supply of
produced.
in

Italy

furnace.

Turin.

an

was

possibilityof smelting
series of experiAfter
mental
a

the

Cerchi, large electric smelting plants

and

in

removed

are

metal

molten

the

slags are

of the

carbon

and

He

operation directlyfrom

endeavoured
the

ore.

to

were

produce

It is evident

INDUSTRIAL

224

for the

that

pig

iron

ELECTROMETALLURGY
refinement

further

usually produced, provision must

supply of only the requisiteamount

addition

In

in such

that the

maimer

by which

actual

the

time

have

jnolten pig

the

be

and

retained

be

of

more.

no

furnace

in the

slag reactions,

heterogeneous metal

process

for the

made

of carbon

must

of the

decarburization

and

purificationis accomplished,

complete themselves.
Stassano
accomplished the first by careful analysis of
the high-grade ore
employed and briquetting it with the
of carbon
and
flux, using pitch or water
requisiteamount
glass
a

as

to

binding material.

magnesia-lined cylinder with

slow

revolution

around

electrodes, three

in number,

diametrically,introduced

slightlyinclined

and

at the

is introduced

briquetted charge
furnace, and two tapping
operation

short

within

the furnace

owing

to the

Since

obtained.
the

With
iron

of

consumption

of

may

of

but

the

as

becomes

40

some

not

of the

commencement

temperature

conducting

more

the electrodes

impurities,and

does

arc

to

make

be taken

as

could

to

5900

to

15

kgms.

10

and
the

the

50

long is

cms.

with

contact

any

to

50

and

hours,

have

limits of the carbon

Per

cent,

an

of

energy

electrode

an

been

investigators. The

alone.
cent,

per

produced with

resulting metal

by other
extreme

be
kw.

4800

analyses of

by Stassano

containing 48

ore

of metal

ton

expenditure

both

the

gap

of
arc

an

magnetite

metric

Various

arc

top of the

the

at

metal, heating is accomplished by radiation

or

ore

rises the

until

cavity

drawal
provided for the with-

are

employed,

volatilization

withdrawn

are

is

arc

holes

slag. At the

and

furnace

horizontal.

to the

The

of the metal

being

employed,

of the

centre

Horizontal

axis.

are

of

capable of

roof

domed

nearly vertical

four

or

itself consists

furnace

The

16

given

following
content

composition.

"

The
of

IRON

AND

process

has

FERRO-ALLOYS

THE

extended

not

confines

the

beyond

Italy.
Induction

furnace
which

Furnaces.

The

"

essentiallyof

consists

This

A.

of force

is excited

the thin sheet-iron

The
in

Sweden.
at

steel,

molten

volts,

the

system

installed

was

estimated

the

lines

the

at

by

Gyringe
of

primary alternating current

3000

annular

an

C, C.

core

of this type

With

replaced by

possiblein

as

laminated

first furnace

amp"res

is

containing the

far

as

in

step-down transformer

by the primary B, B, and

retained

are

This

Furnace.

Kjellin

secondary winding

the

trough of refractory material

A,

225

induced

90

current

WV,

Fig.

25.

was

30,000

amperes

was

found

to

with

cold

hot.

the power

uses

factor

kw.

the

s=the
C=a

1,.

per

hours

when

ton

per

ton

following formula

when

for

charged
charged

determining

"

p*

Is

VW'^WV

/"=the power factor.

ft=the
frequency.
/

and

hours

consumption

power

^--(theratio

W5

furnace.

The

volts.

650 kw.

metal, and

V
where

at

800

be

Lindblad

Kjellin induction

"

W*=the

of

area

to

length of the steel in the

channel.
sp. resistance

of the

steel.

constant.

magnetic

resistances

of the two

circuits.

15

The

have

The

very

high secondary

low

resistance

furnace

referred

therefore

would

It

frequency
operated

to

long thin trough.

quency
of fre-

current

on

appear

employing

current

of

in the form

the

when

consequently greatest

small.

is

term

to

necessary

is

factor

power

right-hand
a

ELECTROMETALLURGY

INDUSTRIAL

226

factor as
having a power
low
as
0*635. A further disadvantage is to be found in
the fact that the secondary cannot
be completely emptied
of metal, if it be desired
to keep the furnace
warm
prior
to the insertion of a fresh charge.
If a hot charge be placed
in the furnace
its capacity is considerably augmented.

cycles per

13*5

In

Colby and

the

second,

Gronwall

difficulties

furnaces, these

coiled
Colby utilizes a water-cooled
partly overcome.
pipe as primary circuit, permitting of it being placed in
closer proximity to the secondary.
factor of 0*90
A power
to o*93 is claimed, and
the calculated
comsumption
power
are

per

ton

of

steel is 590

490

kw.

hours

for

serpentinetrough
in the

hot

spite of

furnaces

such

normal

the
as

hours

in order
;

for

high

to

disadvantages
the

low

frequency, together

of

with

long

high resistance

factor

is claimed.

simple induction

the

with

factor

power

furnace,
a

ensure

power

charge and

cold

In Gronwall's

one.

is used

secondary circuit

In

kw.

of

currents

difficulty of

the

tecting
pro-

excessive
heat
from
metal
long trough of molten
radiation, several of the Kjellin type have been employed,
usually for the preparation of special steels and ferro-alloys
a

in which

fusion

simple
overheating is to

be avoided, and

The

slag is

usually sufficientlyheated, and

from

the annular

Frick

not

trough is a

furnaces, which

Kjellin,are

in

no

matter
are

is desired.

slag formation

its removal

difficulty.

of considerable

simple

operation at Krupp's

local

required,where

operations are

of

modifications

works

at

Essen

the

for the

production of ferromanganese and melting scrap.

The
following figures have been published relating
these

furnaces

"

Kw.

Ferromanganese production
Melting scrap
Steel refining

hrs. per

600
.

587
90

ton.

to

AND

IRON

Composite
furnace

Furnaces.
in the

employed

Rodenhauser

with

furnaces

common

two

provided.

heating

of the

metal

induced

extra

an

in

meet

large reservoir

supply of energy

//////

IZZZZZZZ

the

trough is provided by

in the

current, but

by

troughs

and

A, A,

cores

protected by

are

The

cores,

is thus

of the

which

CE.

metal

of molten

means

the

Rochling

surrounded

are

troughs

between

space

The

soft iron

laminated

magnesia-lined fireclaywalls

composite

of steel is the

furnace.

primary windings B, B,

the

227

successful

most

preparation

the

secondary molten-metal
the

The

"

induction

resistance

these

In

FERRO-ALLOYS

THE

/t

(/,////

7JZ-L

UV/////V

Fig.

has

to

26.

Rochling

"

This

temperature.
turns

maintain

of

is

cable

heavy

induction

resistance

Rodenhauser

supplied to

be

/Y//"

reservoir

the

accomplished by
wound

the

at

desired

of

means

the

round

furnace.

few

pole pieces and

in the magnesia
plates F, F, embedded
liner E, E, at the opposite ends of the trough. The magnesia
becomes
sufficientlyconducting at high temperatures to
induced
in the cable
of the current
permit of the passage

connected

through

to

iron

molten

the

current

goes

remaining 35 per
Furnaces

capacity,
and
the

of
and

steel.

About

through

the

cent,

this
have

annular

design have
been

been

The

rotation

built

up
for

to

both

difficulties associated
of

the

duced
inthe

reservoir.

suitable

found

of the

cent,

troughs, and

through the central

refiningsteel.

electromagnetic

65 per

molten

metal

tons

paring
prewith
when

ELECTROMETALLURGY

INDUSTRIAL

228

three-phase
referred

overcome

viz.

furnace,
electrodes

the

in

as

low

temperature
suggested

advantages

dissolved

somewhat

of

Gin

to

obtained

the

over

and

the

furnaces,

by

additional

an

induction

furnaces

type, inasmuch

arc

as

renewal, perfectlygas-free

impurities from

no

The

the

Furnaces.
have

wear

spin

in

ash

carbon

lining due

the

on

Two

is

metal

the

in view,

purpose

and

refining,

necessitated

scale

which

have

by

not

yet
since

be mentioned,

may

principlesemployed are
laboratory experiments

the

as

metal.

of furnaces

technical

such

for steel

employed

molten

interestingtypes

furnaces

suitable

currents

of the

applied on a
applicationof

Resistance

"

proved

not

high

very

resistance

the low

the

slag

heavy.

Miscellaneous

been

arc

supplementary

as

electromagneticallyproduced

the

slag, small

the

to erect, the

metal.

the

by

this

against

Nathusius

for carbon

obtained,

be

can

owing

been

cores.

expensive

is entailed

expense

those

the

raised

of

and

Paragon

on

more

offer considerable

to

already

have

objection

being naturally

secondary winding

are

chief

the

requisitepower
Although

the

been

have

heaters,

metal

employed

to.

To

no

is

current

novel

for the

have

yielded

highly satisfactory results.

The

Hering "Pinch"
Effect Furnace.1*
Hering, when
investigatingthe operation of the Kjellin furnace, noticed
that

"

of the

ring
that

high

when

metal

became

divided

was

the

towards
coaxial

the

caused

has

to the

of the

that

axis of the

current

Consequently
metallic

shown

and
any

conductor

pressure.

ceased.

current

caused

was

by the

cylinders of metal

Northup

axial

and

axis

employed

were

occasionally depressed

depression
the

densities

current

by

the

this pressure

ultimately the

pointed

He

induced

the

slight difference
will

produce
these

in
a

diameter

of

the
the

the

square
radius.

of the

great alteration

conditions

the

larly
perpendicu-

exerted

square

of

currents.

cylinder is proportional to
to

out

directed

pressure
attraction

mutual

carrying

inversely

Under

the

surface

the

fluid

fluid

in
will

the
be

INDUSTRIAL

230
with

to

of

capable
The

coil.

electrodes

the

The

of

Tesla

in the

20-kw.

to

the

furnace

discharge.

cent.,

serves

has

The

connected

are

and

condensers

the

natural

thermal

and

constructed

terminal

condenser

found

to

oscillation

of

period

small

the

voltage of

efficiencyis stated
the

of

secondary

the

as

been

high figure when

coil fitted with

crucible

volts, and

7200

primary

of

primary

the

as

high voltage oscillatingdischarges.

operate successfully with

5400

serve

of this

ends

providing very

metal

coil.

of wire, which

fiftyturns

about

induction

the

ELECTROMETALLURGY

size

of

60 per

to be

furnace

of the

is

considered.
C. The
The
of

one

to

the

Ferro-au,oys.

production of ferro-alloysin the electric furnace

earliest

the

preparation

of iron

silicon, ferro-tungsten,
smaller

and

Ferro
for the

resistance

In

the

90

has

and

cases

of

the

manufacture

and
been

is

combined
series

the

or

trode
elec-

basal

and

arc

type

arc

in

as

originally iron

employed.

now

It

ore

in

is made

carbon

to

over

grades. The
in the form

the

be

poisoning, formerly

containing

lower

since

handling

of

70 per cent,
raw

materials

but

scrap
of

presence
of

source

frequent

used
or

of

coke.

is liable to choke

of

calcium

in

occurrence

more

are

iron

explosions

substance.

the

silicon is

of anthracite

experimented with,

from

the
of

preparation

described.

prepared

shown

and

The

already been

be

content,
been

silicon.

cent,

per

should

phosphorus

phosphide

the

which

ferro-silicon

silicon grade has

Ferro-silicon

silicon

iron

scrap

over

purer

low

generally employed

are

grades, containing 25 per cent., 50 per cent., 75 per

and

cent.,

of

preparation

the

several

in

employed,

are

titanium.

and

ferro-alloys,either with

Hfroult,

ferro-

(p. 212).

used, but

was

of

most

molybdenum

chrome,

furnaces

the

mentioned

be

ferro-uranium

Arc

"

the

as

heating

Keller

the

silicon.

methods

Amongst

may

manganese,

quantitiesof

production
such

steel.

and

alloys manufactured

important

electrothermal

applications of

was

Ferro-

stable than

crushed
Sand

quartz
has

also

the furnace.

IRON
The

furnace

charge crushed

sufficient carbon

iron

from

is added

metric

in

for

80

utilizable

30

the

grade of

the

on

single-arc furnace

is

kw.

roughly 5000
ferro-silicon

varies
for

consumption

power

cent,

per

of

cent,

per

ferro-silicon;

off the

impurities

absorbs

very

hours

75
per
kw.

only 3500

in

the

remainder

the

the

is converted

charge

is used

and

quartz

for

into

slagging

Ferro-silicon

coke.

little carbon

during the process of formation,

liners of carbon
are
frequently employed.

furnace

partly successful,

Attempts,
blast

furnace

source

of the

slags,20 and

have

been

made

to

sandstone21

ordinary

utilize

rock

as

silica.

application of

An

the

to

necessary.

About

and

with

ferro-silicon

grade

are

according

quartz,

depending

amount

volts, and

75

ton,

hours

contain

size should

small

required.

to

cent,

per

the

voltage employed

70

231

Si02+3C=2CO+Si

ferro-silicon
The

to

reduce

to

equationand

FERRO-ALLOYS

THE

AND

electric furnace

the

recently been

has

preparation of specialferro-silicon and silicized

iron having resistant properties,
probably associated with the
of superficial
formation
layers of iron silicides,
FeSi* and FeSi2made

the

to

Owing
of

acids,

strong

been

castings have
Tantiron,

as

stimulus

to the

The

earlier

be

machined,

machined

introduced

have

production

non-corroding

these

variety of

Illenit, Neutraleisen

Metaldtir.

and

could

recently large castings capable of

introduced, and

been

the

such

names,

exceedingly brittle, and

were

but

under

to the

war

of

number

great

Narki,

forms

given by the

presence

of

not

being
flaws

eliminated.
practically

Ferro

the

on
a

charge

electrode.

When

Attempts
avoid

intermittent
lined

is

allowed
have

the time

Ferro

"

furnace

simple

basal

tungsten.

to

also
wasted

system.

with

in

made

to

pendent and
is completed,

reduction

solidify, and

been

generally pared
preis
fused
in
charge

The

clay having

the

is

tungsten

is
use

cooling the melt.

then

broken

tilting furnaces

one

the
out.
to

ELECTROMETALLURGY

INDUSTRIAL

232
As

used, the

are

is

most

of iron has

used

proposed

has

instead

agent

economical

of

the

+CaS+4CO

and

important tungsten

ores,

volatilized

the

at

and

does

process

reducing

not

appear

formation

of

oxide

avoided

owing

higher grades,
of calcium

kw.

to

and
hours

are

and

the

metric

ton.

two

iron

is

The

usually

oxide

is to

with

Percentage

flux

in the

of lime.

consumption
reduced

Hutton24

typicalindustrial

be

For

tungstate.

silica present

be

most

can

strictlylimited

ferro-silicon

power

can

following analyses of

of

any

decarburization
per

of

by the addition

Keeney28

C.

alloys

of feirous

employed,

fluxed

28000

carbide, W2C.

Excess

carbide

being

reduction

addition

formation

calcium

being

According

iron.

the

fluoride

concentrates

reduction

to

of

of

low-grade tungsten
the

with

alloy is usually essential

o" tungsten

for

other

are

manganese

of reduction,

of the

easily be accomplished by
amount

of the

operation

decarburization

to the

(Fe,W)

directly reduced

be

can

temperature

Decarburization

7500

the

as

wolframite, FeMnW04,

in the

tungsten

small, but

owing

but

electric furnace, most

in the

of

ferro-silicon

of

+4Fe2Si =3CaSi03 +FeSi03

Ferberite, Fe2W04,

loss

Sulphide

"

3CaW04

carbon

the

22

use

carbon,

hematite.

of

CaW04+FeS+4C=(Fe,W)
Gin

duction
Re-

of coke, and

means

addition

the

also been

concentrates

ore

being scheelite, CaW04.

common

supplied by

and

ores

usually accomplished by

is

iron

various

of tungsten,

source

to

under

gives

alloys :

"

composition.

for

the

IRON
Metallic
for

used
lower
for

AND

higher

the

steels

-hearth

open

of crucible

production

grades with

233

high-grade tungsten

and

tungsten

the

FERRO-ALLOYS

THE

content

containing

low

are

steels,whilst

tool

carbon

alloys

the

employed

are

of

percentage

the

metal.

Ferro-manganese.

usually pared
predifferent grades of the alloy

in the blast furnace,25 but

are

prepared by the fusion

the

electric

furnace.

furnaces

although Heroult
for the

of scrap

As

(p. 225)

metal

and

Girod

in

manganese

tion
indicated, induc-

already been

has

most

suitable

furnaces

have

appear

and

is

Ferro-manganese

"

this work,

for
been

employed

purpose.

by the calcined
prevent absorption of manganese
dolomite
liner, the walls are frequently protected with a tar
To

or

of retort

mixture

Ferro-chrome.
field for

in

also

and

in

use

with

is

the

with

three

mineral

usually accomplished by
aluminium

and

The

processes

latter

The
anthracite
reduction

of

charge
or

of carbon

have

proved

ferro-chrome
can

be

run

chromite
of

at

liner

chromium

reduction

is

although silicon,
been

suggested.

economically

chromite

and

requisite quantities to
at

commences

tapping
cent,

the

is fed into the furnace

Reduction

per

in

of

and

of carbon,

finely powdered

coke

usually lined

are

source

FeO.Cr203,

not

being

employed, being

be

walls

carbide

have

of

"

acids.

chief

means

calcium

rustless

frequently a
operation,the life

The

chromite,

"

but

careful

years.

military purposes,

capable

can

furnace

increasing

an

so-called

and

furnace

magnesite,

or

employed

exceed

The

base.

and

and

water

sea-

operating

dolomite

liner is
may

the

at

to

found

has

malleable

although

continuous

tapped

Ferro-chrome

"

resistant

are

coal tar.

and

specialsteels for naval

the
production of the

steels, which,
welded,

coke

cessful.
suc-

coarse
ensure

regular intervals.

11850 C.26
containing only

about

By
from

off,although the carbon

mittent
inter2

to

content

considerably higher. For the purpose of preparing a

low carbon
ferrochrome, a decarburizing process is necessary,
may

run

INDUSTRIAL

234
since

ELECTROMETALLURGY

direct

the

according

production

in the

of

iron, lime

alloy is,

carbon

by

loss

excessive

an

Refining is usually accomplished

slag.

by fusion of the alloy with

oxide

low

Keeney,27 always attended

to

of chromium

or

of

suitable

slag containing chromite

fluorspar. Decarburization
the followingequation :

is

and

accomplished according

to

"

2Fe3C+6CraC3+5FeO.Cr2O3=iiFeCr2+20CO
The

carbon

and

may

of the

resultingalloy is usually below

0*5 per cent,

be lower.

gives

Hutton

ferro-chromium

commercial

of

analysis

following

the

"

Percentage composition.

The
kw.

7200
25

consumption

power
hours

metric

per

with

ton,

6000

between

ranges

tool

metal

alloys for

have

the

recently been

production

of

molybdenite

MoS2.
coal

or

The
coke

heated
basal

to the

correct

and

the

in

an

electrode

equation

prepared

averaging 90 per cent.

proportions of iron turnings, anthracite,
or

concentrates

or

raw

roasted

intermittent

type.

ore,

electric

Reduction

+3C

+Fe

=FeMo2

resulting alloy usually contains

of carbon.

being

together with

lime,

furnace, usually of

place according

takes

"

2M0S2 +2CaO
The

ore

are

is

"

from

high speed

and

introduced

prepared in increasing quantities.

Ferro-molybdenum.
Ferro-molybdenum

the

of

kgms. of carbon.
Chromium-nickel

are

loss

electrode

an

and

typicalanalysis is

as

+2CO

+2CaS
from
follows

3 to
:

"

+CS2
4 per

cent,

IRON

AND

Decarburization

by

of

235

desulphurization

and

means

FERRO-ALLOYS

THE

slag containing lime

be

can

plished
accom-

oxide

and

of

of carbides, aluminium
and
by means
slag. Reduction
silicon,including ferro-silicon,have all proved too expensive
iron

loss
by volatilization
practice. The
amount
oxide is frequently very
high and may

commercial

for

molybdenum
to

much

as

Ferro

preparing
been

have

which

The

"

ferro-vanadium
thermite

electric

furnace

for

method

only recently supplanted the

has

great variety of processes

process.

suggested for the production of the alloy,amongst

be mentioned

may

Fusion

1.
1

vanadium.

usual

more

30 per cent.

as
-

of

of

"

mixture

part of silica and

of

parts vanadium

10

parts of carbon, with

pentoxide,
the requisite

of iron.

amount

trioxide

vanadium

Briquetting

2.

ferro-silicon

and

by

of tar.

means

3.

Electrolysis with

fluoride
4.

iron

an

from

cathode

double

electrolyte.
silicide,SiFeV

ferro-vanadium

From

and

vanadium

fluoride.
5. From

by
in

small

furnace

arc

4 to 6 per cent,
of oxide
The

reduction

oxides,

of carbon.

means
a

the

largestsource

provide

content

of

can

is the

of
to

that

limited amount

to under

that

in

the
manner

employed for ferro-molybdenum.

Boron."
and
Ferro-titanium, Uranium

ium, used

as

deoxidizer

for cast

50 volts

per

cent.

sulphide ore, patronite,

experiments by Keeney have shown

the ferro-alloycan
be accomplished

and

at

alloy containing from

an

be reduced

supply

about

brought

amp"res

By reheating with

carbon.

the carbon

of 900

current

will

being

iron, is made

preparation
similar

Ferro-titan-

by smelting

INDUSTRIAL

236

titaniferous
uranium

iron

with

ore

alloy has

sodium

been

with

calcium

carbide

boric

with

acid

the

oxide, U308,
with

or

The

of scrap

of iron

oxide

alloy is

boron
iron

by

and

borax

carbon.

"

Zeit. Elehtrochem.,

D.R., patent

Trans.

16,

859 of

VIII.

SECTION

TO

of Iron

Rusting

lime

and

mixture

REFERENCES
The

uranium

or

whilst

quantitiesfrom

in small

ferrosilicon.

or

of

aluminium,

or

prepared

Na2Ur207,
iron sulphide

prepared by reduction
or

carbon

uranate,

smelting
and

ELECTROMETALLURGY

and

Steel," by E. K.

20;

1910.

Rideal.

1900.

Amer.

Electrochem.

Trans.

Amer.

Electrochem.

Trans.

Amer.

Electrochem.

Soc., 19,

181

1.

191

*
0
7

Elektrolyse," 5th Auf, p. 172 ; 1908.

Quantitative Analyse durch
Electrochem.
Wright, "Electric
Ind.,
7, 16; 1907.
J. Richards,
Furnaces."
Allmand,
Applied Electrochemistry."
and
Chem.
Met.
Eng., 11, 1913. P- 383"
Crawford,
J.

Soc., 25, p. 489 ; 1914.

25, 1914. P#*"i^

Soc,

"

"

"

Einfiihrung in die technische

Congress of Applied Chemistry." 7
Zeit., 86, p. 564 ; 1912.
Faraday Soc, Dec., 191 6.

10

Askenasy,

11

See

"

13

Chem.

13

Trans.

Elektrochemie."

"

15, 127

Soc,

Electrochem.

191

14

Trans.

14

Stansfield,

13

Electrochem:

17

Trans.

Amer.

Ind., vol. 6, 1908, p. 315 ; vol. 9, 1911,

Electrochem.
Soc, 15, p. 205 ; 1907.

18

Trans.

Amer.

Electrochem.

Soc,

19

Trans.

Farad.

Soc, Nov.

7, 19x7.

30

G.

31

Met.

Amer.

Met.

and

Chem.

Eng., 8, p. 134
Jour., 18, 173;

Min.

33

Eng. and

33

Trans.

34

"

38

F. W.

36

J.C.S., 93, 1484

37

Trans.

Soc,

Electrochem.

Amer.

Industry,"

Electrochem.

"

Harbord,

; 1909.

; 1910.
1912.

24, p. 182

vol. 5, p.

Metallurgyof

The

; 1914.

10.

Steel."

1908.

Electrochem.

Amer.

15, 255

p. 642.

Electro., April, 1901.

Gin, Industrial
and

; 1909.

Furnace."

Electric

The

"

o.

1912.

Soc,

24, p. 177;

19".

BIBLIOGRAPHY.
"

Elektrische

' '

Electric

"

The

"

Furnaces

Electric

"Applied
"The

Ofen

and

Furnace,"

Metallurgy

their
A.

Industrial

Applications,

Stansfield.
A.

of Steel," F. W.

in die technische

Eisen."

Rodenhauser.

Eisenindustrie,"

Electrochemistry,"

Einfiihrung

"Stahlu.

in der

' '

S.

Wright.

1914-

J. Allmand.

1912.

Harbord.

ElektTochemie,"

Askenasy.

1910.

904.

NAME

ACHESON,

165, 169

155,

Acker, 117
Allmand,
166,

Anderson,

INDEX

Carmichael,

173

85

Caspari, 8,

Andrioli, 72
Arndt, 121
3

Clancy,

151

Clarke, 199
Classen, 44,
Claude, 201
Claus, 92

115,

123

53

72

Bassett, 69

Clergue,

Bayer, 126
Beardslee,

Cohen,

Bennet,

74,

155.

120,

179

104

Brand, 68
Broadrill, 137
Brochet, 101
Brode, no
Brown,
146
94,
Brunner, Mond,
65
Bucher, 196, 199
Bullier, 177
Bunsen,
138

Burgess, 206
Burleigh, 86

Coles, 42, 43,

Davy

122,

123,

137,

144

183

22

Daniel,
Darling,

37

Boissiere, 199
Borchers, 28, 94,

Bottger,

133,

Cowper
Cullis,

65

150,

169

Cowles.
Crookes,

191

28
Bessemer,
Betts, 85, 87, 91
Beutel, 74
Bicknell, 121
Bischof, 102
Blount, 72, 123, 132

146,

150

73,

Consiglio, 42

Bergsoe, 95
Berkeland, 186
Berthelot, 196

Body,

207

Colby, 227

104

Beatson, 93
Becker, 112
Becket, 152

Benjerink,

100

Castner, 109, 196

186
Cavendish,

Arrhenius, 2,
Aschermann,
Ashcroft, 60,
Bancroft,

34

Caro, 200
Carrier, 117

10,

51
112

186

Dawes,
199
Dechert, 102
De
Laval, 147
Dennis, 135
Desmur,
102
Deville, 119, 154
Diesel, 20
Doelter, 220
Dolch, 93

Dorsemagen,
Dumoulin,

146
42

Elkington,
Elmer,

82

97

Elmore, 42
Eisner, 74, 83
Englehardt,
95
Faraday,
Feild,

219

Field, 97

r,

10

72,

206,

208

NAME

240

Imbert,

Fischer, 49, 69, 88, 117

Fitzgerald, 146,
Foerster,

155,

66, 82, 92,

146
Irvine, 158

168

93.

INDEX

*35

Forsell, 155
Frank, 200
Frary, 121

Jacobsen, 73
Jellinek, 186
Johnson, 141,

Frick,
Fromm,

Kalmus,

103

Keeney,

152,

145

226

62, 66

233,

235,

236

Keith, 86, 94
Gaudin,
Geer,

Keller,

44

Gelsthorpe,

94,

Gillet, 165
Gin,
130,

137,

Kern,

95

213,

220,

150

229,

Greenwood,
Griesheim,
Gronwall,

Kuster,

37

81

153

Ladd,

in

214,

Grosz, 154
Grotthus,
2
Gruszkrewicz,

Langbein, 73, 82, 102,

Laszczynski, 33, 59

197

LebJanc,

Hausser,

135
197

Leucks, 87
Li, 207
Lindblad, 214,
Linde, 201

Lodge,

10,

Lowry,

187

150

Luckow,

94

214

Lyon,

103
188

Lyons,

Haycroft,

179,

214

124

'

214
137

Machalske,
Marchese,

72

Helfenstein,

158
28

Hellriegel,192

Margueritte,

Helmholtz,

Mathers,

Hemingmay,

95

Henderson,

35,

65,

177

233,

235

231,

234

99

96
186

Meliner, 199
Memmo,
179
Mennicke,
96
Merke,
Minet,

136

1, 45

186
Howies,
Hnlin, 117

Hutton,

222,

149

Hoepfner,
Holfis, 96
Horry,

213,

125,

McDougall,

230

177

Hildebrand,
Hittorf,

229,

159,

Heroult,

199

89
Matuscheck,
88
Maxted,

226

Lorenz,

Harmet,

Harper,

152

Lepieme,
Lepinske,

142

104,

201

no,

9,

Leaner,

137

Harbord,
Harden,

165
158

Landis,

Haanel,
213
Haber,
175, 187, 188
Hall, 125
206
Hambuechen,

Hampe,

149

Lampen,

227

Guichard,
152
Gunther,
66, 98
Guntz,
138

Heyn.

90

Krupp, 227
Krutwig, 83

93

Greenawalt,

Hewes,

231

226

Klapproth, 76,
Koenig, 187
Kohlrausch,

234

Goldschmidt,
121
Goodwin,

Hering,

222,

198
88, 98

Kjellin,
142,

233

Girod,

148,

Kendall,

135

206

130,

154

Moebius, 77, 79
Moissan, 150, 153,
Morrison, 149
Mounden,
142
Muthmann,
136

Mylius, 62,

66

172

206

NAME
Namias,

241

Scholl, 113
186
Schonherr,
Schucht,
135

82

Nathusius,
Nauhardt,

INDEX

222

95

Neil, 94

Schwabe,

Neill, 34
Nernst, 15, 42, 47,
Neumann,
157, 217
Newton,
199

Senn,

Nicola

jew,

Nodin,

Serpek,

186

192

Seward,

114

Sharpe, 65
Siemens

28

Halske,
138

Simon,

96

Northrup, 229,
136
Noyes, 47, 48

92

88

Snowden,

81, 89

Snyder,

Stockem,

Suchy,

Swindel,

101,

102,

201

Regnault,

Thomson,

Townsend,
155
Tronson, 121
Trumm,
98
Tucker, 120, 165, 193
Tuttle, 74

95

186

158, 198

Valentine,

188

173

65, 175
5

Thum,
79
Tommasi,
89
Tone, 166, 168, 170

128

Richards, 67, 130, 139,

Ricketts, 33
Rienders, 95
Rochling Rodenhauser,
Roseleur, 73, 97
Rossi, 184, 187

Rudolphi,

63
168

Thompson,

188

Read, 193
Readmann,

Tainton,

Taylor,

123

199

Tesla, 231
Thiel, 135
Thiele, 88

199

Ramsay,

124

Swan,
198
Swinburne,

186

Rayleigh,

120

Strutt, 187

Pederson, 137
Perkin, 76
Pfanhauser, 74, 82,
Planck, 5
Plato, 120

Quintains,

199

214

Stansneld, 142, 154* 214

Stassano, 222, 224, 225
Steele, 2
Steiner, 94

Palmabk,
5
Parker, 158
Parkes, 59, 67, 86
Paschen, 5
Pattison, 86

Pott, 102
Potter, 154, 169
Powell, 102
Preeble, 76
Priag. 63, 77. 87"

125

Sourdeval,
Stalhane,

Obstbrlb,
146
Oettel, 119
Ost, 76, 90
Overman, 89

Possoz,

159,

228

166

85

Van

Arsdale,

Van

der

Van

Laar,

Van

*t Hoff, 2, 3

Vautin,

Vogel,
Vogt,
Von

34

Waal,

117
124

220

Ruff, 120
Russell, 69

Von
Von

Ruolz, 76

Salgues,
142, 144
Sand, 45, 81, 92
Saunders,
165

Waldbn,
Wallace,

I,.

Hevesy, no
Kugelgen,

Savell, 103

59, 71, 90

Smit, 5
Smith, 32, 76, 95

230

Norton,

Pauling,

29,

114

76
Wannschaft,
Watt, 44

99

16

NAME

242

Watts,

65,

103,

Weidlein,

Wilson,

Wood,

47,
177

191

76
120

Wohlwill,

159

Whetham,

Winogradsky,

W6hler,

170

Westman,

207

Withrow,

34

Weintraub,

Whitney,

104,

INDEX

48

79

136

Woolrich,

Wright,

69
132

INDEX

SUBJECT
Abrasives,

164, 169, 173

Benzoic

Absorption,

Acetate

electrolytes,

Active

Alcohol

Algae,

102

hydrogen, 65

Addition

acid,

agents, 52
reducers, 53

furnaces,

Blast

Bleaching

192

Allotropy,
Alloys, 54

Blende,

187

9,

177

208

Blowing off waste

gas,
Blue
powder, 59, 140
Boiler
efficiency,18

alloys, 133
carbide, 193
cathodes, 62

Bombs,

190

acid, 102, 105, 237

Borides, 181
Boron, 137, 195
nitride, 195

preparation, 125
reduction, 218, 234, 237
Alumite, 26
Alunduxn,
157
Ammonia,
157, 184, 186

Brighteners, 83
Briquetting, 59,

Analysis,

52

Broken

Anodes, 30, 60, 131

Anthracite, 155, 157
Antimony, 39, 84, 89,
Apatite, 158

Bromide

Arc

Brass,

Argentium,
Argon, 190

186,

198,

221,

133

Aromatic
acids, 208
Arsenic, 39, 40, 84, 88, 89, 159,
Arsine, 176

Asymmetric

59

electrolytes, 76
54, 133

phosphide,

radicMa,
122

cyanamide, 201
cyanide, 198, 199
Basic

salts, 63
Bauxite, 22, 125,

193

204

200,

233

220,

2x9,

231

Caliche, 184
Carbon, 39
Carborundum,

Carnallite,

Cast

191

72,

fluoride, 120,

disulphide, 83, 146,

Auric

salts, 71
salts, 72
Auxiliary electrodes,

Cadmium,
8, 68, 84, 135
Calamine, 65
Calcium, 120
carbide, 152, 234

cyanamide,
176

alternating current, 76
theory of electricity,x

Aureus

Bacteria,
Barium,

225

ore,

Burnishing, 50
By-products, 13

151

222

BACILLUS

Hill

Bronze.
92,

54

157

furnaces, 153,

Atomistic

190

Boric

deposits, 26
nitride, 193

Aquadag,

60

powder,

59

furnaces,

Block

Aluminium,

102

naphthol, 65
Biochemical
nitrogen, 191
Bipolar electrodes, 31
Bismuth.
39, 79, 81, 84, 88, 89,

191,

192

147,
1

17,

160

164, 170

121

iron, 213

Catalysis, 155, 190, 193. 198,

Cataphoresis, 11
Cathode
depolarisation, 54
material,

61

potential, 99
rotation, 45
Cerium, 136

199

91

SUBJECT

244
Channel

formation,

Charcoal,

209,

Chemical

potential, 4
side

Chilled

arcs,

Chloride

reactions,
187

nickel

Chrome

Chromite,

23,

Electronic

124

theory,

Electrostatic

charges,

Electrotype,

41

Emulsification,

234

Engines, 20
Equilibrium constant,

formation,

10,

229

1,

alloys,235

Chromium,
8, 23, 151,
Citric acid, 102,
107

222,

187
Electroplating, 41, 52, 81, 89

10

removal,
33
evolution,
66,

Chlorine

Cloud

Electrolytic agitation, 45
potentials, 3
Electromagnetic fields,116,

146

214

Chemical

INDEX

198, 218, 235

140

222

1S8,

zoo

Evaporation,
10

Explosives, 183

127

Coal, 17
tar, 19,

Cobalt,

Felspars,

234

84,
matting,

4, 23,

Coconut

charges, 175
electrolytes,44,

Complex
Contact

electrc

Copper,

25,

hydride,

55

81, 147

79,

steel, 239

Cryolite, 125, 132

Cuppelation, 77
Cupramines, 51
Cupriferous pyrites, 25
Cyanamide, 192, 200, 204
Cyanides, 183, 192
electrolytes,42, 82
gold process,

Ferro

alloys, 153,

Fire

234,

235,

218

165, 218

Flashing,

42

Float

40
of ores,

154

arc,

153,

186,

induction,
radiation,

79
no

films, 47

resistance,

theory,

Fused

Dolomite

liners, 213, 224,

Dropping electrode, 5
Duralium,

electrolytes, 85, 92,

Electrode

Galena,

25, 59

135
tannic
acid, 157
Galvanizer's
dross, 57
Gallo

45

65
arrangements,
157

59,

Garnet,
25
Gas
films, 8

21

preparation,

228

electrolytes,10,

Galvanizing,
Eikonogen,

147

Gallium,

Dyes, 183
equilibrium,
Dynamic
Education,

222

226

234

133

39

131

supply, 183
86
Fractional
crystallization,

Furnaces,

Dissociation

224,

102

235

Fluxes, 152, 208

Fog formation,
120,

Dextrin,
Diamond,

65

59

electrolytes,

Fluoborate

Food

45,

74
91

slimes,

distillation, 176, 185

Desulphurization, 219, 236

32,

231

168

sand,

Fluosiucate

Destructive

Diaphragms,
5, n,
Diffusion currents,

220,

tungstate,233

Fluorspar,

Dephosphorization,
Depolarizers, 7

235

Fertilizers, 183

70

233,

226, 227, 234

silicon, 35, 146, 153,

titanium, 236
tungsten, 232
uranium, 236
vanadium,
236

Flotation

Deoxidation,

234

Ferrocyanides, 73,
Ferrous
sulphate,
depolarizer, 60

196

Decarburization,
236

208

150,

molybdenum,

41,

61

Cyanogen,

chloride

manganese,

54

Corrosion,
Crucible

39,

18, 185
leach, 37

Ferric

boron,
237
chrome,
151,

: js, in

28,

233

Fermentation,

32

Collodion,
83
Colloids, 12, 52, 63, 65, 81, 87
188
Combustion,
Comminuted

21

Ferberite,

189

103,

power,

18,

20

producers, 189

67

109

102

246

SUBJECT

Passivity, 6, 8,

INDEX

Patronite, 236

Silver, 39, 79, Si, 84, 159

Slags, 143. 147, 150, 208, 217,

Peasant

Slimes,

43

proprietors, 183

77,
loss, 18

Peat, 185

Smoke

Peeling
104
Peptone, 89, 193
Perchlorate
electrolytes,88

Smothered

arc

Sodamide,

189

of metal,

Phenol,

Sodium,
Sodium,

88

Phosphate electrotytes,73,
Phosphine, 176
Phosphorus, 158, 191, 209
Pig iron, 208

furnace, 175
113,

109,

of

Pigments,
109
Pinch
effect, 229
Platinum,
8, 75

Solid

40

Polishing, 169
Porous
deposits, 42

Spark discharge, 198

Spelter, 140
Spiegeleisen, 150
Spongy deposits, 42, 65,

Potassium,
Power,

Solution

Soot,

117

cyanide,

197

12,

15,

Praseodymium,

solutions,

17, 18, 209,

217,

226

slags,220

Stannates,

94

Steel,

Protective

Striking baths, 82,

Pyrrhotite,
Quartz,
Radiation

87, 231,

furnaces, 147

Reaction

Resistance
Resources

of ores,
carbide

Revolving
Rhodamite,

processes,

Rotation

of

Rustless

175,

furnace, 178

160

218

Symbiosis, 192
Synthetic ammonia,
96, 98,

Tannin,

Tantiron,

Tapping

59

cathodes, 45, 97

24

steel, 234

188, 196

of mercury,
Silfrax, 168
Silica bricks, 219,
224

Sickening

220,

Silidizing,168
Silit, 169
Siloxicon, 165, 176
168
Silundum,

103

232

furnaces,

179

electrolytes,
Tellurium,
89

Tartrate

Thallum,
135
Thermite,
153
Thioantimonates,

Samarium,
136
Self-induction, 175
Sewage sludge, 185
Shaft
furnaces, 214

soluble, 59
Silicon, 153, 195,
carbide, 165
monoxide,
165
nitride, 195

221

166

21

25

Roasting
Rubite,

145,

tension,

Surface

219

furnaces,

n,

pressure,

53

Sulphide of carbon,
gold, 76
Sulphocyanides, 73
Sulphur, 39, 82
Sulphur dioxide, 35,
Sulphuric acid, 32

232

velocity, 9
Reducing agents, 53,
Refining, 37, 66

xoi

122

Sublimation

214

25,

216

Strontium,

Sugar,

81

deposits, 117

Printer's

ink, 169
colloids, 12, 52, 53
Prussian
blue, 71
Pyrogallol, 53, 65, 88
Pyrometers, 156

10

3,

pressure,
197

Stassfurt

131

196

191,

114,

cyanide, 199
peroxide, 70
sulphide, 113
Softening Doint

97

220

86

40,

92

14

energy,

Tilting furnaces,
Tin, 26,

234

Titanium,
24,
236
nitride, 195

92,
93

scrap,

Transmission

Transport

137,

153,

Turf, 185

Tuyeres,

215

15

187, 218, 234

233

Turbo-generators,

!95"

153.

of power,
1
numbers,

Tungsten, 8,
carbide,

232

96, 150

70

Tin

98, 207

91

Thiostannates,
Tidal

92,

13

198

INDEX

SUBJECT
electrodes, 45

Unattackablb
Uniform

deposits, 44

Water

cooling,

Water

gas,

Uranium,

138, 153. 236,

carbide, 153, 189

Vanadium,
carbon,

24,

137,

153,

247

12

power,

Wolframite,

233

Zinc, 8,

25,

218, 236

166

21,

139
Zinc scrap.

Waste

Zones

THE

"

of

39,

58, 62, 84,

66, 71

Zircon, 25
Zirconium,

209

BaiUiire, Tindall

electrodes, 128

Whitewashing

Vapour pressure of zinc, 141

Velocity of reaction, 9, 70
Viscosity of slags,179, 221
gas,

179

197

25,

153

reduction,

208

KND

Cox, 8, Henrietta

Street, Covert

Garden, W.C.

123,