The Chemistry and Manufacture of Hydrogen - P. Litherland Teed (Edward Arnold, 1919)

THE
IHEMISTRY
A N D
M A N U F A C T U R E
OF
H
BY
P. L l T H E R L A N D T E E D
\R is MjMlNINC* AND METALLURGY), A I M M
MAJOR, KAI-,
LONDQ.
E D W A R D
1
1919
DEDICATECBTO
M ^ I T L A N D . J L M . G , D.S.O., R.A.F
ANI>
. A-F.C, R . A F .
DEFACE.
aiH&nal requirements a r e p e r h a p s
the
greatest, it i3 t&sJUfrortl^ that our contribution to the

technology o$%vMfe"en & probably the least of any
of the Qreat* F f l w W ;
work
in
so, should it h a p p e n t h a t this
a n y way stimulates
interest,
resulting
in
further i m p r o v e m e n t in the technology of t h e subject,

the author will feel himself more than amply rewarded
T h e author would like to express his t h a n k s
to
the Director of Airship Production for permission to

publish this book, and to Major L. R u t t y ,
for m a n y helpful
R.A.F.,
suggestions in the compilation of
t h e text and assistance in correcting the proofs.

P. L.
EYNSKORD, KENT
CONTENTS.
CHAP.
PAGE
I. HYDROGENITS USESDISCOVERY, AND OCCURRENCE

IN NATURE
II
THE CHEMICAL PROPERTIES OF HYDROGEN
III
THE
MANUFACTURE
OF
IV
THE MANUFACTURE OF HYDROGEN.
METHODS
METHODS
V
HYDROGEN
CHEMICAL
.
.
39
CHEMICO-PHYSICAL

APPENDIX,
PHYSICAL CONSTANTS
113
PHYSICAL METHODS
.
126
145
CHAPTER
HYDROGENITS
I.
USESDISCOVERY,
RENCE IN NATURE.
AND
OCCUR-
T h e U s e s of H y d r o g e n . T h e commercial production of h y d r o g e n has received a great stimulus during the last few years owing to its being required for
industrial a n d war purposes in quantities never previously
anticipated.
T h e discoveries of M. Sabatier with regard to t h e
conversion of olein and other unsaturated fats and their
corresponding acids into stearin or stearic acid have
created a n enormous demand for hydrogen in every industrial c o u n t r y ; 1 the synthetic production of ammonia
by t h e H a b e r process has produced another industry
with great hydrogen requirements, while the Great W a r
has, t h r o u g h the development of the kite balloon and
airship, m a d e requirements for hydrogen in excess of
t h e two previously mentioned industries combined.
T h e increase in hydrogen production has modified
t h e older processes by which it was made, and has also
led to t h e invention of new processes, with the result
t h a t t h e cost of production has decreased and will probably continue to decrease, thus allowing of its employment in yet new industries.
1
The weight of oil hardened by mean&xSBk*.fliQKenin Europe

in 1914 probably exceeded 250,000 tons.
I
HYDROGEN
T h e Discovery of H y d r o g e n . T h e discovery of
hydrogen should b e attributed to T u r q u e t d e Mayerne, 1
who in 1650 obtained, b y the action of dilute sulphuric
acid on iron, a gas, or " inflammable air,", which we now
know to have been hydrogen.
T u r q u e t de M a y e r n e recognised thergpf he obtained
as a distinct substance. Robert B o y l e 9 made some
experiments with it, b u t many of its m o r e important
properties were not discovered until Cavendish's investigations, 8 beginning in 1 7 6 6 ; while the actual name
" H y d r o g e n , " m e a n i n g " w a t e r former," was given to
t h e g a s by Lavoisier, w h o may be r e g a r d e d as the first
philosopher to recognise its elemental n a t u r e .
Occurrence in N a t u r e ,
H y d r o g e n occurs in small quantities in Nature in
the uncombined state. It is found in a state of condensation in many rocks and in s o m e specimens of
meteoric iron. It is present in t h e gaseous discharges
from oil and g a s wells a n d volcanoes, a n d is also a constituent to a very m i n u t e extent of t h e atmosphere.
Hydrogen in the uncombined s t a t e exists in enormous masses upon t h e sun, a n d is p r e s e n t in the
" p r o m i n e n c e s " observed in solar eclipses, while by
optical means it may also be detected in m a n y stars and
nebulae.
1
Paracelsus, in a similar experiment in the sixteenth century,

obtained the same gas, but failed to recognise it as a distinct substance.
2
" New Experiments touching the Relation between Flame and
Air," by the Hon. Robert Boyle, 1672.
8
James Wat^^discoverer of the steam engine, did many similar
experirffl^^^^^^^game time, but his interpretation of his results
Was r ^ j j f f i ^ ^ y ^ ^ ^ f e l
OCCURRENCE IN N A T U R E
In. the combined state hydrogen is extremely a b u n dant. It is present t o the extent of one part in nine (by
weight) in water, and is a constituent of all acids a n d
most organic compounds.
In R o c k s . I n a state of "occlusion," or molecular
condensation, hydrogen is to be found in most igneous
rocks in association with other gases, the total volume
of occluded gases being on the average about 4*5 times
the volume of the rock.
T h e following analyses of Sir William T i l d e n 1 give
the composition of the occluded gases in several rocks
from different parts of the world :
Granite.
Gabbro
Pyroxene
gneiss.
Gneiss .
Basalt .
Skye .
Lizard
Ceylon
.
.
.
23-6
55
7 72
6-45
2-16
8*o6
303
2-03
56
5-13
1-90
ri6
6r68
88*42
12*49
Senngpatam
Antrim
.
31*62
32*08
5-36
2008
51
10*00
-56
I*6I
6193
36*15
In Meteoric Iron # An examination of certain

meteoric irons, made by Sir William Ramsay and D r .
Travers, 3 showed that these contained occluded gas, a n d
that this gas was hydrogen :
D
MetSrite.f
Toluca
.
.
Charca
.
.
Rancho de la Pila
1(
Weight Taken. Hydrogen Evolved.

1 grm.
,,
'Proc. Roy. Soc," 1897.
2*8 c.c
"28
*57
HYDROGEN
Observing that meteoric iron contains occluded

hydrogen, it is interesting to note that the examination
of steel shows that it also possesses this property of condensing gases. Steel of the following composition
Per Cent
Combined carbon
.
.
.
.
*8io
Silicon
. . .
. . .
"o8o
Manganese
.
050
Sulphur
'028
Phosphorus
.
.
.
.
-019
Iron (by difference)
.
9 9 "013
IOO'OOO
in pieces 6 x i x i cm. was heated (ultimate temperature
979 0 C.) for ten days in vacuo and the gases evolved
analysed, with the result that they were found to have
the following composition :
Per Cent
by Volume.
Hydrogen
. . .
.
52*00
Carbon monoxide .
45'52
dioxide
.
.
1 68
Methane .
.
.
72
Nitrogen
.
08
IOO'OO
T h e total weight of steel was 69*31 grammes, while
the total volume of gas evolved was 19*86 c c . 1
A n examination of a defective Admiralty b r o n z e
casting showed that there was an appreciable quantity
of occluded gas in it, containing J'6 per cent, of hydrogen by v o l u m e 2
1
" GasesOccluded in Steel," by T. Baker, Iron and Steel Institute,

"Carnegie Scholarship Memoirs," vol. 1., 1909.
2
" Ast4gyf||ff1aon on Unsound Castings of Admiralty Bronze,
by H^&LiimfflHIfcej: and C. F. Elam, Inst. of Metals, 1918.
In Discharge from Oil and Gas W e l l s , T h e

gas discharged from g a s and oil wells contains small
quantities of hydrogen, as will be seen from the following analyses of natural g a s discharges in Pennsylvania,
W e s t Virginia, Ohio, Indiana, and Kansas.
AVERAGE COMPOSITION By VOLUME 1
Pa. & W. Va. Ohio & Ind.

Hydrogen
Carbon dioxide
Sulphuretted hydrogen
Oxygen
Carbon monoxide
Methane
Other hydrocarbons
Nitrogen
'10
<0
5
oo
trace
40
80-85
14 00
4 60
1-50
20
15
15
"5
93 60
.30
3'60
Kansas
00
3
00
00
1'00
93'65
25
480
In Gases from V o l c a n o e s . 2 T h e nature of the

gases discharged from volcanoes has been most carefully studied from about the middle of the last century,
with the result that the chemical composition of the gas
discharged has been determined at many different volcanoes, and a t different times at the same volcano.
F r o m these investigations it would appear that in the
more violent discharges there are very considerable
amounts of hydrogen, while in the more placid eruptions
there is little gas of a n y description, except steam,
generally accompanied b y water containing mineral
salts.
^ S A . Geological Survey, "Mineral Resources of U S.A.,"
1909, 2, 297.
2
For further information on this subject-^see F. W. Clarke's
" The Data of Geochemistry," U.S G.S.. Bull, tufi
HYDROGEN
Below are given analyses of volcanic gas from different parts of the world by different authorities :
From a group of fumaroles
at Reykjalidh,
Ice1
land :
Hydrogen .
25*14
Oxygen
Nitrogen
o"72
Carbon dioxide
. . .
5'
Sulphur dioxide
. . . .
.
.
.24*12
From afumarole
on Mont Pelee,
Hydrogen
Oxygen
Nitrogen . . .
.
Carbon dioxide .
.
Sulphur dioxide.
.
Carbon monoxide
. . . .
Methane .
.
.
Argon
.
.
Martinique*:
8fi2
13 67
. 54"94
.
15 "38
. .
i"6o
.
.
5'46
-71
99-88
From
Kilattea :
Hydrogen
Oxygen
10*2
Nitrogen
II*8
Carbon dioxide
monoxide
Sulphur dioxide.
73 9
4-0
99'9
1
R. W Bunsen, " Annales Chim. Phys.," 3rd ser., vol. 38, 1853
H . Moissan^^Comptes Rend.," vol. 135, 1902.
8
A. L. Day*andE. S Shepherd, "Bull. Geol. Soc. America,"
vol. 24,
2
From
Santonn1:
Hydrogen .
Oxygen
.
Nitrogen
Carbon dioxide
.
Carbon monoxide
.
Methane .
.
.
.
.
.
29 43
-32
32*97
. 36 43
-86
100 00
In C l a y s . N o t only is hydrogen present in most

igneous rocks, but it is to be found to a small extent
in some clays. Sir William Crooks, O.M., F . R . S . ,
was kind enough to investigate for the author the
gases occluded in the celebrated " Blue G r o u n d "
a clay in which the Kimberley diamonds are found.
T h i s clay was found to contain gas composed of 82
per cent, of carbon dioxide, the bulk of the residue
being oxygen and nitrogen, with detectable traces of
hydrogen.
I n Air*As is not surprising, hydrogen is present
in the atmosphere to a very small extent, as will be
seen from the following analysis of air under average
conditions. It is doubtless derived from the sources
already mentioned, and also from the decay of organic
matter containing hydrogen
T h e following represents the average composition of
normal a i r :
Volumes per 1000.
Nitrogen .
. . . .
769 500
Oxygen
.
.
.
.
206*594
Aqueous vapour . . .
.
i4"ooo
1
F Fouque, " Santonn et ses eruptions," Pans, 1879.
HYDROGEN
Argon
Carbon dioxide
Hydrogen
Ammonia .
Ozone
Nitric acid .
Neon
Helium
Krypton
Xenon
.
.
.
.
Volumes per iooo.

9"358
"336
'19
*oo8
"0015
.
-0005
"oi
"ooi
*ooi
00005
THE CHEMICAL PROPERTIES OF HYDROGEN.

HYDROGEN in the free state h a s a capability of entering into combination with a large variety of substances,
forming chemical compounds, while h y d r o g e n in t h e
combined state reacts with m a n y other chemical compounds, forming new c o m p o u n d s .
Reaction of H y d r o g e n w i t h O x y g e n i n the Free
State*
By far the most important chemical reaction of hydrogen is undoubtedly t h a t which it e n t e r s into with
oxygen. W h e n h y d r o g e n is mixed with oxygen a n d
the temperature of t h e mixed g a s e s raised, they combine with explosive violence, p r o d u c i n g steam. T h i s
reaction may be expressed by t h e following equation :
2H2 + O2 = 2H 2 O.
If a stream of h y d r o g e n issues into air and a light is
applied to it, it burns (in a c c o r d a n c e with the above
equation) with an almost non-luminous flame. (This
reaction is, of course, reversible, i.e. a stream of air
would burn in the s a m e w a y in an a t m o s p h e r e of hydrogen.) It was discovered b y F r a n k l a n d 1 that while
at atmospheric pressure t h e flame of h y d r o g e n burning
in oxygen is almost non-luminous if t h e pressure is
1
" Proc. Royal Soc ," vol. xvi, p. 419.

(9)
io
HYDROGEN
increased to two atmospheres the flame is strongly

luminous.
T h e combination of oxygen and h y d r o g e n is most
violent if the t w o gases are present in t h e relative
quantities given in t h e equation, viz. two volumes of
hydrogen a n d one of oxygen. If one or other of the
gases is in excess of these quantities the violence of the
reaction is reduced a n d the quantity of the gas in excess
of that required by the equation remains as a residue.
W h e n one gas is enormously in excess of the other
a condition may arise in which the dilution is so great
that on sparking the mixture n o reaction takes place. 1
Mixtures of air a n d hydrogen in which the air is under
20 per cent. (i.e. u n d e r 4 per cent, of oxygen) of the
total volume b e h a v e in this way.
T h i s point is of importance in airships, as, providing
the purity of t h e h y d r o g e n in the envelope is above
80 per c e n t by volume, a n internal spark in the envelope
will not cause a n explosion, b u t if t h e quantity of
hydrogen by volume falls below this a m o u n t there is a
risk of explosion ; h e n c e the procedure of deflating
airships when t h e purity has dropped to 80 p e r cent,
hydrogen by volume.
T h e Temperature of Ignition of H y d r o g e n and
O x y g e n , W h e n the two gases are mixed in the proportion of two volumes of hydrogen a n d one volume
of oxygen it has been found t h a t t h e temperature of
the mixed gases m u s t b e raised to about 580 0 C. 2
1
Schoop states that when either gas contains 6 to 8 per cent,

of the other it is explosive.
a
Victor Meyer, "Berichte," No. 16, 1893, gives the temperature
of violent reaction as 612-15 C. Gautier and Helier, "Comptes
Rend.," 125, 271, 1897, gwe about 5500 C
CHEMICAL PROPERTIES
before explosion t a k e s place.

H o w e v e r , Professor
a
B a k e r has shown that, if t h e t w o g a s e s a r e n o t only
perfectly pure b u t also perfectly d r y (dried b y b e i n g
kept in contact for as long as t h r e e w e e k s with a n h y d r o u s
phosphoric acid) a t t h e t e m p e r a t u r e of i o o o 0 C , t h e y
do not combine, but even in this d r y condition t h e y
will explode with an electric spark. 2 T h i s p h e n o m e n o n
is of great interest, a n d opens a wide field of philosophic
speculation, but t h e conditions of purity a n d d r y n e s s a r e
such that this h i g h t e m p e r a t u r e of ignition can n e v e r
be attained under commercial conditions.
Professor B a k e r has also s h o w n that, w h e n a mixture
of ordinary h y d r o g e n a n d o x y g e n is exposed t o t h e influence of strong sunlight, t h e t w o g a s e s v e r y slowly
react, with the production of w a t e r in m i n u t e q u a n tities.
In the experiment b y which Professor B a k e r m a d e
this discovery h e placed a m i x t u r e of these two gases in
a state of great purity b u t not of absolute d r y n e s s (in
the ratio of two volumes of h y d r o g e n a n d one of
oxygen) in a h a r d glass t u b e closed a t o n e end a n d
sealed at the other b y mercury. T h i s t u b e w a s exposed
outside a south window for four m o n t h s , from S e p t e m b e r
to December, at t h e e n d of which time it w a s found,
after due correction for t e m p e r a t u r e a n d pressure, t h a t
the mixture of t h e two gases h a d contracted b y ^ of its
original v o l u m e 3 b y t h e formation of water. A similar
experiment with the g a s e s in a n exceptionally d r y state,
lf
'Jour. Chem Soc.," April, 1902.

Dixon, "Jour. Chem. Soc," vols. 97 and 98.
3
The volume of the resulting water is almost negligible, as
one volume of hydrogen and oxygen in the ratio stated produces
only "006 volume (approximately) of water.
2
12
HYDROGEN
but otherwise under exactly similar conditions, showed

n o such contraction.
W h e t h e r the union of h y d r o g e n with the infiltrating
oxygen of the atmosphere takes place in airship envelopes, which are comparatively transparent, h a s not b e e n
determined, b u t since in airship practice there is n e v e r
more t h a n 4 per cent, of o x y g e n in the envelope, it is
1
!>530
I
:525
520
" r s i
60
100
160
200
Z5O
300
350
400
Volumes jofOjg to 100 Volumes offy

FIG. I.
t o b e a n t i c i p a t e d t h a t s u c h a c t i o n , if it t o o k p l a c e , w o u l d
of necessity be relatively slower.
T h e temperature of ignition
hydrogen and oxygen has been
by Professor H .
B. D i x o n ,
of v a r y i n g m i x t u r e s o f
most
carefully
studied
who, besides much very
in-
g e n i o u s a p p a r a t u s , e m p l o y e d t h e c i n e m a t o g r a p h for
ob-
taining c o n c l u s i v e e v i d e n c e of t h e conditions p r e v a i l i n g
during explosion.
1(
'Jour. Chem S o c , " vols. 97 and 98, and vols 99 and 100
CHEMICAL PROPERTIES
13
B y means of adiabatic compression, the temperature

of ignition of different mixtures of hydrogen a n d oxygen
was determined, with results which may b e seen in
Fig. 1. F r o m a s t u d y of this curve it will b e noticed
that t h e most easily ignited mixture is not o n e in which
the proportion of h y d r o g e n to oxygen is as t w o to one,
as might perhaps b e expected, b u t when t h e ratio is
one volume of h y d r o g e n t o four of oxygen.
IGNITION TEMPERATURES OF HYDROGEN AND OXYGEN MIXTURES.
(As determined by Prof. H B Dixon, M.A., F R.S.)

[Ignition by Adiabatic Compression)
Composition of Mixture.
By Volume.
Ignition
Temperature
Oxygen.
Hydrogen.
Centigrade.
33"33
100
557
40
5o
542
536
100
53
150
525
200
520
250
300
5i6
350
509
507
400
512
T h e temperature of ignition of a mixture fired by

adiabatic compression is lower than when the same
mixture is fired by b e i n g h e a t e d in a glass or silica tube
at atmospheric pressure. Professor H B. Dixon in a
private communication to t h e author states that h e found
the ignition t e m p e r a t u r e of electrolytic gas under the
latter conditions t o be 580" C.
i4
HYDROGEN
Besides studying the temperature of ignition of

various gaseous mixtures Professor H . B. Dixon investigated t h e nature of explosions 1 and found that
Berthelot's conception of an explosion as being an advancing locus of high pressure and of rapid chemical
change, which he described as " l ' o n d e explosive," was
fundamentally correct.
Without going into detail with regard to this very
interesting subject, it may b e stated that " the velocity of
the explosion wave in a gaseous mixture is nearly equal
to the velocity of sound in the burning gases ".
While this statement does not satisfy all cases of
gaseous explosion, it may be regarded as fundamentally
correct, exceptions to the rule being capable of explanation on the basis of undoubted secondary reactions.
O n the basis of this relationship between the velocity
of sound in t h e burning gases and the velocity of explosion, Professor H . B. Dixon calculated the velocity
of the explosion wave in certain gaseous mixtures and
also determined it experimentally, with the results given
below:
Velocity of Explosion Wave in
Metres per sec
Gas Mixture.
Calculated
Found
8H2 + Oa
3554
3535
H 2 + 3O2
1740
1712
While it has been said that the temperature of igni1
"The Rate of Explosion in Gases," by H. B. Dixon, Bakenan

Lecture, Phil. Trans. Royal Society, 1893
CHEMICAL PROPERTIES
15
tion of hydrogen a n d o x y g e n in their m o s t readily

ignited proportions m u s t b e at s o m e point a t least 500
C. in t h e mixture of t h e gases, this s t a t e m e n t requires
modification in that, t h o u g h it is perfectly t r u e in the case
of a mixture of t h e g a s e s contained in glass or nonporous vessels, in t h e presence of certain substances of
a porous nature this t e m p e r a t u r e of ignition is greatly
reduced. T h i s is particularly so in t h e case of platinum
in a spongy condition. If a piece of spongy platinum
is introduced at o r d i n a r y atmospheric t e m p e r a t u r e into
an explosive mixture of h y d r o g e n a n d oxygen, t h e
platinum is observed to glow and, a n explosion almost
immediately takes place. T h i s p r o p e r t y is m o r e m a r k e d
if the platinum is in t h e s p o n g y condition, b u t it is
equally true if it is in t h e form of wire or foil.
T h e r e is no complete explanation of this phenomenon,
but it h a s been observed that certain substances possess
the property of a b s o r b i n g m a n y t i m e s their own volume
of different gases, a n d t h a t these a b s o r b e d gases possess
a greatly increased chemical activity over their normal
activity a t the same temperature. N e u m a n a n d Strientz 1
found that one volume of various metals in a fine state
of division is capable of a b s o r b i n g t h e following amounts
of hydrogen :
Palladium black
Platinum sponge
Gold
Iron .
.
Nickel
Copper
.
Aluminium
Lead.
.
1
.
.
.
.
.
.
.
.
.
502*35 volumes.
49*3
.
46-3
19*17
i7'57
4-5
.
2*72
-15
"Zeitschrift fur analytiscbe cheraie," vol. 32.
16
HYDROGEN
T h i s p r o p e r t y of certain s u b s t a n c e s , without themselves u n d e r g o i n g chemical c h a n g e , 1 of b e i n g able to

i m p a r t increased chemical activity to t h e gases they
a b s o r b is not confined to t h e metals, b u t is possessed by
charcoal (particularly a n i m a l charcoal), m a g n e s i t e brick,
a n d p r o b a b l y to s o m e e x t e n t b y all p o r o u s substances.
I t is a subject of v e r y g r e a t interest, a n d in m a n y cases
of practical i m p o r t a n c e 2 which is n o w b e c o m i n g a subdivision of Physical Chemistry, u n d e r t h e n a m e of " Surface E n e r g y ".
T h e T e m p e r a t u r e Produced b y the Ignition of
H y d r o g e n and O x y g e n . I n the p r e v i o u s p a r a g r a p h
t h e t e m p e r a t u r e a t w h i c h the ignition of h y d r o g e n and
o x y g e n begins h a s b e e n given, a n d n o w t h e t e m p e r a t u r e
which t h e flame r e a c h e s will be considered.
B u n s e n d e t e r m i n e d t h e t e m p e r a t u r e of the flame
p r o d u c e d t o b e :
Flame of hydrogen burning in air
oxygen
.
.
20240 C.
28440 C.
A later d e t e r m i n a t i o n by Fe"ry ( " C o m p t e s R e n d , "

1902, 134, 1201) g i v e s t h e values 1900 C. a n d 2420 C.
respectively, while B a u e r (ibid., 1909, 148, 1756) obt a i n e d figures for h y d r o g e n b u r n i n g in o x y g e n varying
from 2200 0 C. to 2300 0 C , according to t h e proportion of
o x y g e n present.
T h e reason that t h e flame of h y d r o g e n burning in
o x y g e n is h o t t e r t h a n t h e flame p r o d u c e d in air is due
1
It is contended by Troost and Hautefeuille that in the case of

palladium the absorption of the hydrogen is chemical and not
physical, palladium hydride (Pd2H) being formed.
2
The Bonecourt flameless boiler depends on the surface energy
of magnesite brick.
CHEMICAL PROPERTIES
17
to the fact t h a t the speed of burning in oxygen is g r e a t e r

t h a n in air, because of the absence of a n y dilution, a n d
also because the nitrogen a n d other inert constituents
in the air a r e themselves heated at the expense of the
flame t e m p e r a t u r e . 1
T h e calculated value for the flame t e m p e r a t u r e of
h y d r o g e n b u r n i n g in air, assuming that the heat of
reaction is distributed a m o n g t h e inert constituents of
the air, is 1970 0 C. ( L e Chatelier), a n d this agrees a p proximately with t h e a b o v e figures of 202 4 0 C. and
1900 0 C.
A comparison between the flame temperature of
h y d r o g e n a n d other gases burning in air is given in the
following table :
Hydrogen 2
.
Acetylene3
Alcohol2
Carbon Monoxide 4
.
.
.
.
.
.
.
.
.
.
i9ooC.
2548C
1705 C
2iooC
T h e Q u a n t i t y of Heat Produced by B u r n i n g
H y d r o g e n . T h e t e m p e r a t u r e of ignition a n d the flame
temperature of h y d r o g e n h a v e already been considered.
It now o n l y remains for the quantity of h e a t produced
by a g i v e n weight of hydrogen to be considered in
comparison with s o m e other gases combustible in air.
1
In the case of Zeppelin airships brought down in flames, it is

not surprising that considerable amounts of molten metal have been
found in the locality, observing that the melting point of aluminium
is 6570 C, copper 10870 C.
2
Fery, le
3
Fery, / c. The temperature of acetylene burning in oxygen is
about 40000 C , but this arises from circumstances not present in the
case of hydrogen flames
4
Le Chatelier.
2
18
HYDROGEN
i lb of hydrogen on combustion gives
marsh gas
,,
benzene
,,
,,
carbon monoxide
62,100 B.T U x
24,020
18,090 ,,
4,380
Reactions of H y d r o g e n w i t h O x y g e n in the Com*

bined State*
S o far the reaction of h y d r o g e n and oxygen has
only been considered when b o t h are in the gaseous
form. However, such is the attraction of hydrogen
for oxygen that w h e n the latter is in combination
with some other element the h y d r o g e n will generally combine with the oxygen, forming water and
leaving the substance formerly in combination with the
oxygen in a partially or wholly reduced state. Thus,
oxides of such metals as iron, nickel, cobalt, tin, and lead
are reduced to the metallic state by heating in an atmosphere of hydrogen.
Thus:
(1) FeaOa + 3H2 - 2Fe + 3H2O
(2) NiO + H2 - Ni + H a O
(3) CoO + H2 = Co + H3O
(4) SnOa + 2H2 - Sn + 2HaO
(5) PbO + Ha - Pb + H 2 O
T h e temperature at which the reduction by the
hydrogen takes place varies with t h e different oxides
and also with the same oxide, depending on its physical
condition. " Crystalline haematite," as t h e natural ferric
oxide is called, requires to be at a r e d heat (about 500
C.) before reduction begins to t a k e place, while if iron
is precipitated from one of its salts (as ferric hydrate by
1
The latent heat of the steam produced is included in the heat

units of fuels containing hydrogen.
CHEMICAL PROPERTIES
19
a m m o n i a ) t h e resulting ferric h y d r a t e can b e reduced

to the metallic state at t h e t e m p e r a t u r e of boiling water.
W i t h nickel t h e s a m e variation oi t h e t e m p e r a t u r e
of reduction is noted, d e p e n d i n g on t h e physical condition. T h u s Moisson states that t h e sub-oxide of nickel
( N i O ) which h a s not been calcined, is r e d u c e d by hydrogen a t 23O-24O C. ; Muller, on t h e o t h e r hand, states
that t h e reduction of t h e oxide at this t e m p e r a t u r e is not
complete b u t only partial, but that if t h e t e m p e r a t u r e is
raised to 270 C. a complete reduction t a k e s place. If
the oxide of nickel h a s b e e n strongly h e a t e d its temperature of reduction to t h e metallic state is a t least 420 C ,
in which case it is q u i t e unsuitable for use as t h e catalytic a g e n t in t h e hydrogenation of organic oils.
S u c h is t h e affinity of h y d r o g e n for o x y g e n that
hydrogen will u n d e r certain circumstances r e d u c e hydrogen peroxide. If a n acid solution of h y d r o g e n peroxide
is electrolysed, o x y g e n will be liberated a t t h e positive
pole (or anode), but n o g a s will be liberated at the
negative (or cathode), for the h y d r o g e n which is set
free there immediately reduces t h e h y d r o g e n p e r o x i d e
in the solution to water, as s h o w n in the following
equation:
H2Od + H 2 - 2 H 2 O.
It h a s been m e n t i o n e d that t h e t e m p e r a t u r e of reduction of t h e metallic oxides by h y d r o g e n varies with
the different oxides a n d with the physical condition of
the s a m e oxide. It m i g h t further b e a d d e d t h a t t h e
physical condition of t h e h y d r o g e n also modifies t h e
temperature of reduction. T h i s can b e well s h o w n by
taking s o m e artificial binoxide of tin ( S n O 3 ) a n d placing
it in a m e t a l tray in a solution of slightly acidulated
water. T h e metal tray is then c o n n e c t e d to t h e
20
HYDROGEN
negative pole of a n electric supply, and another conductor placed in the liquid c o n n e c t e d to the positive of
the supply. O n the current b e i n g switched on electrolysis
takes place, that is to say, t h e w a t e r is decomposed into
hydrogen and oxygen, t h e hydrfigen being liberated on
the surface of t h e metal t r a y containing the binoxide of
tin, and the oxygen a t t h e other pole. T h e nascent
hydrogen liberated in the neighbourhood of the white
tin oxide reduces it on t h e surface of the particle to
metallic tin, in accordance w i t h t h e following equation :
SnOa + 2H2 = Sn + 2H2O,
a fact which can easily b e p r o v e d by chemical means,
but which is also detectable b y the c h a n g e of the oxide
from white to the-dark g r e y of metallic tin.
Chemical Combination o f H y d r o g e n w i t h Carbon.
It has been shown t h a t if hydrogen is passed over
pure carbon heated to 1150 C , direct chemical union
takes place, 1 m e t h a n e or m a r s h g a s being formed :
C + 2H S - CH 4 .
This reaction is of s o m e i m p o r t a n c e , as formerly in the
production of blue water g a s t h e presence of m e t h a n e
was entirely accounted for b y t h e presence of hydrocarbons in the fuel. H o w e v e r , t h e experiments of B o n e
and Jerdan show t h a t e v e n if no hydrogen whatever
were present in t h e fuel, m e t h a n e would b e formed if
the temperature of t h e fuel b e sufficient.
If the temperature of t h e carbon is somewhat hotter
than 1150 C , direct u n i o n continues to take place, but
the product of the reaction is n o t methane b u t acetylene.
1
Bone and Jerdan, "Chem Soc Trans.," 71, 41, 1897
CHEMICAL PROPERTIES
21
T h u s if a small p u r e carbon electric a r c is m a d e in a n

a t m o s p h e r e of hydrogen, small quantities of acetylene
are produced, b u t no m e t h a n e .
Chemical C o m b i n a t i o n of H y d r o g e n w i t h Chlorine,
B r o m i n e , and Iodine.
W i t h C h l o r i n e . H y d r o g e n will c o m b i n e with
chlorine, in accordance with t h e following chemical
equation, to m a k e hydrochloric acid :
H a + Cl2 = 2HCI.
If the two g a s e s are mixed in equal proportions in a
diffused light a n d are subjected to a n electric spark, the
above reaction takes p l a c e with explosive violence. If
a glass t u b e containing a m i x t u r e of t h e g a s e s is heated,
the s a m e reaction takes place with violence.
If a mixture of h y d r o g e n a n d chlorine at atmospheric
t e m p e r a t u r e is exposed t o s t r o n g sunlight, hydrochloric
acid is immediately formed, with t h e characteristic explosion. Investigation of this increase in t h e chemical
activity of h y d r o g e n a n d chlorine in t h e presence of
sunlight h a s shown t h a t it is t h e actinic rays which produce the p h e n o m e n o n ; t h u s if t h e r a y s which are p r e s e n t
at the blue a n d violet e n d of t h e s p e c t r u m a r e p r e v e n t e d
from r e a c h i n g t h e m i x t u r e of t h e gases b y protecting
this b y a red glass screen, n o reaction b e t w e e n t h e m
takes place. W h e n sunlight is n o t available, t h e explosive combination of these t w o g a s e s can be s h o w n
by exposing a mixture of t h e m in a glass vessel to the
light of b u r n i n g m a g n e s i u m , such a s is frequently used
by photographers.
T h e r e m a r k s which h a v e a l r e a d y b e e n m a d e with
regard t o t h e reduction in chemical activity of h y d r o g e n
22
HYDROGEN
and-oxygen w h e n perfectly dry apply also in the case

of h y d r o g e n and chlorine.
W h i l e referring to t h e production of chemical union
between h y d r o g e n a n d chlorine b r o u g h t a b o u t by the
influence of light, attention may be drawn to what is
known a s t h e " D r a p e r Effect," which is best demonstrated in the following apparatus :
FIG
2.
Insolation Vessel
T h e mixed gases, in the ratio of o n e volume of
hydrogen to one of chlorine, are contained in a flat glass
bulb A, called t h e insolation vessel. T h e lower part of
the insolation vessel usually contains some water saturated with the t w o gases. T h e capillary t u b e B C contains a thread of liquid ac, to serve as an index.
Under
the influence of a flash of light the t h r e a d of liquid ac is
pushed outwards, to r e t u r n immediately to its original
position. T h u s , a travels to b, a n d immediately returns
to a. W i t h every flash of light t h e same p h e n o m e n o n
takes place. A t the time of its discovery (1843, " Ph^Mag.," 1843, "*> 23 43 4*5) t n e reason for this
sudden rise in pressure was not understood, b u t careful
investigation by J. W . Mellor a n d W . R. A n d e r s o n 1
has shown that a t each flash m i n u t e quantities of hydrochloric acid are formed, with the production of a little
heat, thus causing a rise in pressure until it is dispersed
1
"Jour. Chera. Soc," April, 1902.
CHEMICAL PROPERTIES
23
in fact, t h e D r a p e r effect m a y b e likened to a very

small explosion without sufficient e n e r g y to propagate
itself t h r o u g h o u t t h e gas.
Such is t h e attraction of chlorine for hydrogen that
even w h e n t h e latter is in combination with some other
element the chlorine often will combine with the hydrogen, liberating t h a t element. T h u s , if chlorine is passed
through turpentine, t h e carbon is liberated, in accordance
with t h e following equation :
C10H10 + 8Cla = 10C + 16HCI.
Again, at ordinary temperatures a n d in ordinary diffused
light, but m o r e rapidly in sunlight or other light of
ictinic value, chlorine will decompose water, liberating
Dxygen, in accordance with the following equation :
2H2O + 2CI2 = 4HCI + Oa.
T h e combination of hydrogen with chlorine is attended with the evolution of heat. A c c o r d i n g to Thornsen, the combination of 1 g r a m m e of h y d r o g e n with
35'5 g r a m m e s of chlorine is a t t e n d e d with the evolution
3f 22,000 gramme-calories of heat.
W i t h B r o m i n e . T h e element bromine will combine
with h y d r o g e n to form hydrobromic acid, in accordance
H a + Br2 - aHBr.
This reaction between h y d r o g e n a n d bromine is in many
'espects comparable with the combination of hydrogen
with chlorine, b u t unlike the latter, t h e reaction cannot
be brought a b o u t b y sunlight. H o w e v e r , if the two
^ases are heated, they will combine, b u t their combination is a t t e n d e d with t h e evolution of less heat t h a n
24
HYDROGEN
in the case of chlorine. T h o m s e n states that the combination of i g r a m m e of hydrogen with 80 grammes
of bromine (liquid) is a t t e n d e d with the evolution of
8440 gramme-calories of heat.
W i t h I o d i n e , H y d r o g e n will combine with iodine,
in accordance with the following equation, providing
the iodine is in the form of vapour a n d t h e mixture of
the two gases is strongly heated in the presence of
spongy platinum :
H 2 + I2 - 2HI.
T h o m s e n h a s s h o w n that this combination, unlike
t h e two previous ones, is n o t attended with evolution of
heat, but by the absorption of it. T h u s when 1 gramme
of hydrogen combines with 127 g r a m m e s of iodine (solid),
6040 gramme-calories of heat are absorbed.
Chemical Combination of H y d r o g e n w i t h
Sulphur,
S e l e n i u m , and T e l l u r i u m .
W i t h Sulphur.If a mixture of sulphur vapour and
hydrogen is passed t h r o u g h a tube h e a t e d to at least
250 C , a chemical union of t h e two elements takes
place, in accordance with the equation
H2 + S = H<jS.
T h e resulting gas, which is known as " sulphuretted
hydrogen," h a s a characteristic and extremely unpleasant
odour, a n d is poisonous when inhaled. According to
The"nard, respiration in an atmosphere containing shs
part of its volume of sulphuretted h y d r o g e n is fatal to
a dog, and smaller animals die when half that quantity
is present.
CHEMICAL PROPERTIES
25
S u l p h u r e t t e d h y d r o g e n is an inflammable gas, and

b u r n in air, in a c c o r d a n c e with t h e following equaion:
aH a S + 3O2 - 2SO2 + 2H2O,
>roducing sulphur dioxide a n d water.
If the g a s is mixed with oxygen in t h e proportions
equired b y t h e equation, a n d subjected to a n electric
park, it explodes with violence, g i v i n g t h e s a m e prolucts as w h e n b u r n t in air.
S u l p h u r e t t e d h y d r o g e n is soluble in water at o C.
0 the e x t e n t of 4*3706 p a r t s b y volume p e r unit v o l u m e
>f water.
T h e density of sulphuretted h y d r o g e n is 17 times
hat of h y d r o g e n .
W i t h S e l e n i u m . W h e n selenium is h e a t e d to 250
I. with h y d r o g e n , chemical union results, with t h e prouction of selenuretted h y d r o g e n .
H 2 + Se - H2Se
T h e resulting g a s is colourless, r e s e m b l i n g sulhuretted h y d r o g e n in smell a n d in its chemical properes. It is, however, m u c h m o r e poisonous t h a n the
)rmer g a s .
S e l e n u r e t t e d h y d r o g e n is inflammable a n d b u r n s in
le same w a y a s s u l p h u r e t t e d h y d r o g e n . If the g a s is
:rongly h e a t e d it b r e a k s u p into its t w o constituents,
le selenium b e i n g deposited in the crystalline form.
Selenuretted h y d r o g e n is soluble in water at 13*2 C.
) the extent of 3 31 p a r t s b y volume p e r unit volume of
ater.
T h e density of s e l e n u r e t t e d h y d r o g e n is 40*5 times
lat of h y d r o g e n .
26
HYDROGEN
W i t h T e l l u r i u m * W h e n tellurium is heated to 400

C. in hydrogen, the elements combine, forming hydrogen
telluride :
H 2 + Te - H2Te.
T h i s gas, like sulphuretted a n d selenuretted hydrogen,
is both offensive smelling and poisonous. Like selenuretted hydrogen, on strongly heating it is decomposed
into its components, t h e tellurium b e i n g deposited in
the crystalline form.
T e l l u r e t t e d h y d r o g e n is soluble in water to some
extent, b u t in course of time t h e telluretted hydrogen is
decomposed a n d tellurium deposited.
T h e density of telluretted h y d r o g e n is 63*5 times
that of h y d r o g e n .
Chemical Combination of H y d r o g e n w i t h Nitrogen,
P h o s p h o r u s , and A r s e n i c .
W i t h N i t r o g e n * D o n k i n has shown that when a
mixture of h y d r o g e n a n d nitrogen is subjected to the
silent electric discharge, a partial union of the two gases
takes place, with the formation of a m m o n i a :
N2 + 3 H 2 - 2 NH 3 .
H o w e v e r , this reaction could in no w a y b e regarded as
commercial, as the quantity of ammonia produced after
the gases have long been subjected to the silent electric
discharge is only j u s t sufficient to b e identified by the
most delicate means.
R e c e n t investigations have, however, shown that if
t h e two gases are mixed and subjected to very great
pressure (1800 lb. per sq. inch) in the presence of a
catalytic agent, union to an appreciable extent takes
place. T h i s process, which is now being used on a
CHEMICAL PROPERTIES
27
commercial scale in G e r m a n y , is k n o w n as t h e H a b e r
process, b u t few details as to t h e m e t h o d of operation
are available. I n t h e earlier s t a g e s of t h e working of
this process the catalytic a g e n t w a s probably osmium,
but it is considered doubtful if this is still being employed.
THE
U S E S OF AMMONIA.
S u c h is the importance of a m m o n i a in the existence

of a modern country t h a t it is desirable t h a t some account of its use should b e given, o b s e r v i n g that it is not
improbable that t h e H a b e r process m a y be p u t into
operation in this country in the near future, consequently
enormously increasing t h e d e m a n d for t h e commercial
production of hydrogen.
A m m o n i a or its salts are employed in a variety of
ways in m a n y trades. F r o m it nitric acid, the vital
necessity for t h e manufacture of all h i g h explosives, can
b e m a d e ; it is a n essential for t h e B r u n n e r M o n d or
Solvay a m m o n i a soda process for t h e production of
alkali; in t h e liquid form it is employed all over the
world in refrigerating machinery, b u t its e n o r m o u s and
increasing use is in agriculture, where, in the form of sulphate of ammonia, it constitutes o n e of, if not t h e most
important chemical m a n u r e s known to m a n .
During
the year 1916 350,000 tons of a m m o n i u m sulphate
were produced in this country, the larger proportion of
which was consumed in agriculturea proportion likely
to increase a n d not diminish if t h e d e m a n d for home
production of food continues.
PROPERTIES
OF A M M O N I A .
A m m o n i a is a strongly smelling gas, possessing a

most characteristic odour. It is lighter t h a n a i r ; taking
28
HYDROGEN
the density of hydrogen as i, air is 14 39, and ammonia

8'5. A m m o n i a is not in the ordinary sense combustible
in air, but if the air is heated or oxygen is supplied it
will burn with a feeble, almost non-luminous flame, in
accordance with the following equation :
4 NH 3
+ 3O2 - 2N2 + 6H2O.
A m m o n i a is strongly basic, i.e. it possesses the

property of combining with acids to make neutral salts.
T h u s with the common acidssulphuric acid, hydrochloric acid and nitric acidit forms salts, in accordance
with the following equations :
2 NH 3
+ H2SO4 = (NH4)2SO4,
NH 8 + HC1 - (NHJCl,
NH 3 + HNOa = (NH4)NO3
A m o n g the physical properties of ammonia the outstanding features are its solubility in water, its absorption by charcoal, and its liquefaction.
Solubility of Ammonia
in Water. A m m o n i a is
very soluble in water. Its solubility decreases with
increase of temperature, and, as is of course natural,
increases with increase of pressure.
T h e following
table for the solubility of ammonia in water is
interesting :
Temperature.
oC.
8
16
3o
5
Grammes of NH3
Dissolved in 1 c.c
of Water.
875
713
582
4O3
229
C c of Nl
\J and 7c
1148
923
764
S29
306
CHEMICAL PROPERTIES
29
A feature of t h e absorption of a m m o n i a by water, is

the reduction of t h e specific gravity of the solution.
T h u s at 15 C. a s a t u r a t e d solution containing 34*95 per
cent, of t h e g a s b y w e i g h t h a s a density of 882, while
pure water at t h e s a m e t e m p e r a t u r e has a density of
99909.
Absorption of Ammonia
by CharcoalReference
to
the surface e n e r g y of charcoal h a s already been made.
Its absorption of a m m o n i a is very considerable, b u t varies
with the physical condition of t h e charcoal, as well as
with the m a t e r i a l from which it h a s b e e n made. Saussure
found t h a t freshly ignited boxwood absorbs about 90
times its own v o l u m e of ammonia, while H u n t e r has
shown t h a t freshly p r e p a r e d charcoal m a d e from cocoanut shell absorbs about 171 times its own volume of
ammonia.
Liquefaction
of Ammonia.Ammonia
is an easily
liquefiable g a s , a n d consequently it is o w i n g to this
property t h a t it is employed in refrigerating plants on
land and in ships, for b y t h e rapid evaporation of the
liquid g a s a h i g h d e g r e e of cold m a y be obtained.
The
critical t e m p e r a t u r e of ammonia, i.e. that temperature
i b o v e which b y m e r e pressure it cannot b e liquefied, is
131 C. A t this t e m p e r a t u r e a p r e s s u r e of approximately
1700 lb. p e r sq. inch must b e applied to produce liquefaction ; if, h o w e v e r , t h e t e m p e r a t u r e is below the
zxitical o n e for t h e gas, t h e pressure required for liqueaction is greatly reduced. T h u s , if the ammonia is
:ooled to 15*5 C , a pressure of 101 lb. per sq. inch is
-equired, while if t h e g a s is cooled to o C , a pressure
}f only 61 "8 lb. p e r sq. inch will effect liquefaction.
Liquid a m m o n i a is a colourless, mobile liquid. It boils
lt
~ 3 3 7 C-i a n d a * o C. h a s a specific gravity of 0*6234.
30
HYDROGEN
A t - 75 0 C. liquid a m m o n i a solidifies into a white crystal*

line solid.
W i t h P h o s p h o r u s . I f red phosphorus is gently
heated in a stream of hydrogen, direct chemical union
takes place to a small extent, with t h e production of a gas
termed " Phosphoretted H y d r o g e n " or " Phosphine " :
2P
+ 3 H 2 - 2PH8,
Phosphine is a n offensive smelling, poisonous gas

which in the p u r e state is not spontaneously inflammable.
However, its t e m p e r a t u r e of ignition is v e r y low ; thus,
if a stream of phosphine is allowed to impinge in air on
a glass vessel containing boiling water, it will immediately
burst into flame, b u r n i n g with considerable luminosity,
in accordance with t h e equation :
PH 3 + 2O2 = HPO3 + H 2 O.
Phosphine possesses a n exceedingly interesting reaction with oxygen. T h u s , if a mixture of phosphine
and oxygen is subjected to a sudden reduction in pressure
at ordinary atmospheric temperature, chemical combination immediately t a k e s place with explosive violence, in
accordance with t h e equation already given.
Phosphine, which is produced in small quantities in
the Silicol process for m a k i n g hydrogen, 1 h a s under
certain conditions a deteriorating effect on cotton fabrics,
not as a n immediate action but as a secondary reaction.
T h e examination of a balloon envelope which burst at
M i l a n 2 in 1906 showed that a t some spots t h e material
could b e easily torn, while over the g r e a t e r portion it
1
The total volume of phosphine and arsme does not exceed

025 per cent, and is usually about "oi per cent
2
Namias, "L'Ind. Chim," 1907, 7, 257-258; "Chem. Cent.,"
1907, 2, 1460-1461.
CHEMICAL PROPERTIES
31
showed a g r e a t resistance t o t e a r i n g . T h e d a m a g e d
spots w e r e found to b e i m p r e g n a t e d with phosphoric
acid and a r s e n i c acid, p r o d u c e d b y t h e oxidation of the
phosphine a n d arsine contained in t h e h y d r o g e n with
which the balloon h a d b e e n inflated.
Phosphine in small quantities in h y d r o g e n containing over 1 p e r cent, of o x y g e n a t t a c k s copper, producing
an acid liquid which h a s a m o s t corrosive action on
fabric. H o w e v e r , it does not a p p e a r u n d e r these circumstances t o h a v e a n y action o n aluminium or zinc ;
consequently a n y m e t a l p a r t s inside t h e envelope of
a n airship should b e of aluminium. P h o s p h i n e under
the above conditions a t t a c k s h e m p a n d o t h e r textiles
which h a v e b e e n t r e a t e d with copper compounds,
b u t it does not a p p e a r to h a v e a n y action on fabrics
free from copper c o m p o u n d s or copper or brass
fastenings.
T h o u g h it has b e e n stated t h a t phosphine, is not
spontaneously inflammable, with quite small admixtures
of liquid h y d r o g e n p h o s p h i d e it immediately bursts into
flame on c o m i n g into contact with air.
Phosphine p r o d u c e d b y t h e reaction of water on
calcium phosphide always contains a q u a n t i t y of the
liquid h y d r o g e n p h o s p h i d e sufficient t o m a k e the g a s
spontaneously inflammable.
U s e of this property is
m a d e in t h e H o l m e s ' L i g h t used a t s e a a s a distress
signal, a n d also as a m a r k e r a t t o r p e d o practice.
Phosphine is soluble in water to a slight extent.
T h e solution of phosphine in w a t e r is not very stable,
particularly in s t r o n g light, w h e n it b r e a k s up, depositi n g red p h o s p h o r u s .
T h e d e n s i t y of p h o s p h i n e is 17*5 times that of
hydrogen.
32
HYDROGEN
W i t h A r s e n i c , H y d r o g e n does not directly combine with arsenic, but if an arsenic compound is in solution in a liquid in which hydrogen is being generated,
i.e. hydrogen in the nascent state, chemical union takes
place. T h u s , if arsenious oxide is dissolved in dilute
hydrochloric acid and a piece of metallic zinc is added,
t h e hydrogen produced by the action of the acid on the
zinc will combine with the arsenic, in accordance with
t h e following equation :
AS4O6 + I2H a = 4ASH3 + 6H2O.
T h e g a s produced, which is called " A r s i n e " or
" Arsenuretted H y d r o g e n , " is unpleasant smelling and
poisonous. It burns in air with a lilac-coloured but not
very luminous flame, thus :
4ASH3 + 6O2 - As4Ofl + 6H2O.
If the g a s is strongly heated it is decomposed and
elemental arsenic deposited.
Arsine is produced to a small extent in the Silicol
process of making hydrogen, and has a deteriorating
effect on fabric (see phosphine), while with many metals
it is decomposed, arsenic being deposited and hydrogen
liberated. It can be liquefied easily (the liquid g a s
boiling at - 54*8 C), and it solidifies at - H 3 ' 5 C.
Arsine is soluble in water, one volume of water at o C.
dissolving 5 volumes of arsine. T h e density of arsine
is 39 times that of hydrogen.
Chemical Combination of Hydrogen w i t h Lithium,
Sodium, P o t a s s i u m , M a g n e s i u m , Calcium, and
Cerium,
T h e chemical combination of hydrogen has so far
only been considered with regard to a few non-metallic
CHEMICAL PROPERTIES
33
elements, b u t n o w a n e w series of reactions will be considered in which h y d r o g e n combines chemically with a

metal. T h e s e metals a r e those of the alkaline and
alkaline earth g r o u p .
W i t h Lithium.If h y d r o g e n is passed over metallic
lithium a t about 200 C , the h y d r o g e n is absorbed, not
as h y d r o g e n is absorbed by platinum, etc., but chemically absorbed, in accordance with t h e following equation :
4L1 + H 2 - LI^HJJ
If the resulting lithium hydride is allowed to cool a n d

is placed in water it becomes a source of h y d r o g e n , not
only giving up w h a t it h a s already received, b u t also a
volume twice as much as this, which it has derived from
the water, as may be seen in the following equation :
Li4H2 + 4H a O = 4L1OH + 3H3
W i t h S o d i u m . U n d e r similar circumstances the
n e t a l sodium absorbs h y d r o g e n with the production of
1 hydride :
4Na + H 2 = Na4H3.
This hydride, like t h a t of lithium, behaves in a similar
nanner with water. It, however, has a n o t h e r interesting
)roperty in t h a t if sodium hydride is h e a t e d in vacuo to
-bout 300 C , the whole of t h e h y d r o g e n is given off
,nd metallic sodium again remains.
W i t h P o t a s s i u m . I f the metal potassium is heated
a the presence of hydrogen, a hydride is formed .
4K. + H 2 = K4H2.
"his hydride has the s a m e characteristic reaction with
3
34
HYDROGEN
water, b u t it has a distinctive reaction, in that on exposure to air it catches fire:

2K4Ha + 9O3 - 4 K A +
2H
a0.
W i t h M a g n e s i u m . I f hydrogen is passed over hot

metallic magnesium t h e hydrogen is absorbed :
Mg + H 2 = MgHjj.
T h i s hydride is decomposed with water, with the production of magnesium hydrate a n d hydrogen :
MgH2 + 2H2O = Mg(OH)2 + zH 2 .
W i t h Calcium.If h y d r o g e n is passed over hot
metallic calcium the hydrogen is absorbed :
Ca + H 2 = CaH2
T h e hydride is decomposed by water, according to the
equation
CaH2 + 2H2O = Ca(OH)a + 2 H 2 .
Calcium hydride, unlike the metallic hydrides already
mentioned, is a commercial possibility, and under t h e
n a m e of " H y d r o l i t h " has been used by the F r e n c h
A r m y in the field for the inflation of observation
balloons. Its use for this purpose is g o v e r n e d by F r e n c h
p a t e n t No. 327878, 1902, in the name of Jaubert.
W i t h Cerium.If hydrogen is passed over hot
metallic cerium the hydrogen is absorbed :
Ce + H2 = CeH2.
T h i s hydride is decomposed with water in the same
m a n n e r as calcium hydride, but as a source of hydrogen
it is far too rare to be employed.
However, if an alloy of cerium with magnesium and
CHEMICAL PROPERTIES
35
iluminium is h e a t e d below its m e l t i n g p o i n t in a stream

)f h y d r o g e n , t h e latter is a b s o r b e d , with t h e formation
)f cerium h y d r i d e within t h e alloy, which, after cooling,
Dossesses to a r e m a r k a b l e d e g r e e t h e p r o p e r t y of emiting sparks w h e n r u b b e d with a n y r o u g h surface.
These s p a r k s a r e sufficiently h o t to ignite coal g a s and
)etrol vapour, h e n c e t h e e m p l o y m e n t of this h y d r o g e n ited alloy in t h e p a t e n t lighters which h a v e of recent
r
ears b e c o m e so c o m m o n in this country.
Zhemical C o m b i n a t i o n of H y d r o g e n w i t h
a n d V e g e t a b l e Oil.
Animal
O w i n g to the discoveries of M . S a b a t i e r a new

se h a s b e e n found for h y d r o g e n , a n d a v a s t a n d everrowing industry created, k n o w n as " fat h a r d e n i n g ".
T h e chief uses for animal a n d v e g e t a b l e fats are for
be m a k i n g of candles, soap, a n d edible fats s u c h as are
icorporated in b u t t e r substitutes, sold generically under
i e n a m e of " M a r g a r i n e ".
A n i m a l a n d v e g e t a b l e fats are g e n e r a l l y m i x t u r e s of
certain n u m b e r of complicated o r g a n i c chemical comounds, a m o n g s t t h e chief of which m a y b e mentioned
nolein, olein, stearin, a n d palmitin.
T h e physical
roperties of these c o m p o u n d s a r e s o m e w h a t different.
'hus, those containing considerable p r o p o r t i o n s of
earin a n d palmitin are usually solid at atmospheric
imperature, while t h o s e in which t h e chief constituent
either linolein or olein a r e liquids at such t e m p e r a t u r e .
T h e s e chemical c o m p o u n d s l i n o l e i n , olein, stearin,
i d palmitinare w h a t a r e k n o w n a s " glycerides,"
1. they a r e c o m p o u n d s of glycerine with a n organic
36
HYDROGEN
N o w since glycerine is of great value in a variety of

ways, chiefly for the production of nitro-glycerine, it is
customary to split these glycerides up into glycerine and
their organic acid before indulging in a n y other process
T h i s may be accomplished by t h e use of superheated
steam. T h u s , when such steam is blown through palmitin t h e following reaction takes place :
( W C U H J A ) . + 3H2O Falmitin
Steam
3H(C16H31O2)
Palmitic acid
+ C8H6(HO)8
Glycerine
Or through olein :
C3HB(C1BH33Oa)3 + 3HaO = aHCQsHsA) + C8H6(HO)3.
Olein
Steam
Oleic acid
Glycerine
T h e physical properties of these organic acids are
very interesting and important. T h e i r melting points
are:
Palmitic acid
Stearic acid .
Oleic acid
.
.
Melting point, 62 6 C
,,
69 30 C.
14*0 C.
N o w this oleic acid, owing to its low melting point,

is not of great value, as it cannot b e used for candles
However, the discoveries of M. Sabatier have shown
that u n d e r certain conditions of temperature and in
the presence of nickel or cobalt (which themselves
undergo n o p e r m a n e n t change), the low melting linoleic
a n d oleic acids m a y be converted into stearic acid by
the introduction of hydrogen into t h e liquid organic
acid. T h u s :
C17H38COOH + H 2 = CnH
Oleic acid
Stearic acid
T h e nickel in this process m a y be introduced into
the liquid organic acid by merely a d d i n g spongy nickel
to the molten oleic acid ; or as a volatile compound
CHEMICAL PROPERTIES
3;
k n o w n a s " Nickel C a r b o n y l " it may b e blown in tog e t h e r with t h e h y d r o g e n .

I n either case, for t h e conversion of t h e linoleic and
oleic acids into stearic acid, the t e m p e r a t u r e of t h e acids
should b e b e t w e e n 200 and 220 C. W h e n t h e nickel
is introduced, in the form of carbonyl, at t h e s a m e time
as t h e h y d r o g e n , t h e carbonyl is decomposed into metallic nickel a n d carbon m o n o x i d e t h e latter t a k i n g no
p a r t whatever in t h e reaction a n d being available for
t h e production of further nickel carbonyl.
T h e nickel which is used in this process performs
merely a catalytic function a n d does not of itself underg o p e r m a n e n t change. H o w e v e r , its catalytic property
m a y be d e s t r o y e d either by the m e t h o d b y which it is
prepared or b y certain impurities in the h y d r o g e n with
which the h y d r o g e n a t i o n is carried out. W h i l e it is not
important t h a t t h e h y d r o g e n should be v e r y purein
fact, it may contain carbon monoxide, nitrogen, carbon
dioxide, a n d m e t h a n e i t is absolutely essential that it
should be entirely free from sulphur dioxide, sulphuretted
hydrogen, a n d o t h e r sulphur compounds, bromine,
chlorine, iodine, hydrochloric acid, a r s e n u r e t t e d h y d r o gen, selenuretted h y d r o g e n , a n d teluretted h y d r o g e n .
If the nickel is introduced into t h e fatty acid in the
solid form it is important t h a t it should b e absolutely
free from sulphur, selenium, tellurium, arsenic, chlorine,
iodine, bromine. F u r t h e r , it is important t h a t t h e nickel
should h a v e b e e n p r e p a r e d by the reduction of t h e oxide
at a t e m p e r a t u r e not e x c e e d i n g 300 C , a n d should not
h a v e been long exposed to the air prior to its use.
T h e w e i g h t of nickel used is about o ' l part to 100
parts of oil or fatty acid ; however, larger quantities do
no harm. After t h e hydrogenation of t h e fatty acid or
38
HYDROGEN
oil, practically the whole of the nickel is recovered by

merely filtering the hot oil or fatty acid.
In this note the use of hydrogen in the fat hardening industry has been described with particular reference to t h e conversion of the unsaturated oleic and
linoleic fatty acids into stearic acid. However, what
has been said in regard to this matter is equally applicable to the conversion of olein and linolein into stearin,
cotton-seed and most fish oils being quite easily converted into solid fats.
CHAPTER
III.
T H E MANUFACTURE OF HYDROGEN.
CHEMICAL METHODS.
THE
PRODUCTION OF
HYDROGEN.
W H I L E all t h e processes d e s c r i b e d yield h y d r o g e n ,

some are of merely laboratory use, o t h e r s of commercial
use, and yet others of u s e for t h e g e n e r a t i o n of h y d r o g e n for w a r purposes, u n d e r conditions w h e r e rapidity
of production a n d low weight of r e a g e n t s a r e m o r e important t h a n t h e cost of t h e final product.
W h e r e h y d r o g e n is w a n t e d for commercial purposes,
two types of process will generally b e found m o s t useful . the electrolytic, w h e r e not m o r e t h a n i o o o cubic
feet of h y d r o g e n a r e required p e r h o u r a n d conditions
are such t h a t t h e o x y g e n p r o d u c e d c a n b e e i t h e r advantageously used or sold locally ; t h e I r o n C o n t a c t
process, t h e L i n d e - F r a n k - C a r o process, or t h e B a d i s c h e
Anihn Catalytic process, w h e r e yields of 3000 a n d m o r e
cubic feet a r e required per hour. H o w e v e r , local conditions a n d t h e r e q u i r e m e n t s of a particular t r a d e m a y
m a k e s o m e of t h e other processes t h e m o r e desirable.
F o r w a r h y d r o g e n m a y b e economically p r o d u c e d a t
a base, a n d used t h e r e for the inflation of airships, or
the filling of high-pressure bottles for transport t o t h e
K i t e Balloon Sections in t h e field. W h e r e transport conditions a r e difficult it m a y b e a d v a n t a g e o u s to g e n e r a t e
(39)
40
M A N U F A C T U R E OF H Y D R O G E N
t h e hydrogen on the field at t h e place where it will

b e u s e d ; then, probably, the Silicol, H y d r o g e n i t e or
Hydrolith processes will have t h e a d v a n t a g e , b u t here
again it is not possible to speak with a n y great precision,
as local conditions, even in war, must h a v e g r e a t influence on the selection of the most suitable process.
T h e production of h y d r o g e n can b e accomplished
by a large variety of methods, which m a y b e divided
into two main classes, viz. chemical a n d physical, while
there is a n intermediate class in which the production
of hydrogen is accomplished in two stages, one being
chemical a n d t h e other physical.
CHEMICAL M E T H O D S O F PRODUCING
HYDROGEN.
T h e chemical m e t h o d s of producing h y d r o g e n may

be divided into four classes :
1. Methods using a n acid.
2. Methods using an alkali.
3. Methods in which the hydrogen is derived from
water.
4. Methods in which the hydrogen is produced b y
methods other than the a b o v e
(1) M e t h o d s U s i n g an Acid,
W i t h Iron.If dilute sulphuric acid is b r o u g h t into
contact with iron, chemical action takes place, with t h e
production of h y d r o g e n a n d ferrous sulphate, in accordance with the following equation :
Fe + H2SO4 H2 + FeSO4.
Theoretically, to produce 1000 cubic feet of hydrogen
at 30 inches barometric pressure a n d 40 F . b y this process, 155 Ib. of iron a n d 272 lb. of pure sulphuric acid a r e
CHEMICAL METHODS
41
equired, or a total weight of p u r e r e a g e n t s equal to

27 1b. per 1000 cubic feet of h y d r o g e n p r o d u c e d . F r o m
be figures g i v e n a b o v e , t h e a p p r o x i m a t e cost of material
>er 1000 cubic feet of h y d r o g e n can b e calculated if the
revaihng prices of iron a n d sulphuric acid a r e known.
)f course, p u r e sulphuric acid is n o t a n essential for t h e
rocess, b u t allowance for t h e impurity of t h e sulphuric
cid and iron m u s t be m a d e in a n y calculation for cost
r weight.
T h e h y d r o g e n p r o d u c e d by this m e t h o d varies conderably in purity. It is liable to contain m e t h a n e to
n extent which d e p e n d s on the carbon c o n t e n t of t h e
on ; it m a y also contain phosphine, d e p e n d i n g o n t h e
hosphorus c o n t e n t of t h e iron, sulphuretted h y d r o g e n ,
epending on t h e sulphur c o n t e n t of the iron, a n d traces
f silicon hydride, d e p e n d i n g on t h e silicon c o n t e n t of
le iron. It is also liable to contain arsine or a r s e n u itted h y d r o g e n , d e p e n d i n g on t h e arsenic content of
le sulphuric acid, t h e commercial acid frequently conLining considerable a m o u n t s of this impurity.
Unless
Decially treated, t h e h y d r o g e n p r o d u c e d is a l w a y s acid,
id therefore unsuitable for balloon a n d airship purDses.
T h e i m p u r e g a s p r o d u c e d by this m e t h o d m a y b e
jrined b y b e i n g passed t h r o u g h or s c r u b b e d b y w a t e r ;
lis will r e m o v e m u c h of t h e acid carried by t h e gas,
jst, and some of t h e m e t h a n e , p h o s p h i n e , arsine, a n d
ilphuretted h y d r o g e n .
If after this t r e a t m e n t t h e g a s
passed t h r o u g h a solution of a lead salt, t h e r e m a i n g acidity a n d sulphuretted h y d r o g e n can b e r e m o v e d ,
his m e t h o d of t h e t r e a t m e n t of the impure g a s is
vered b y E n g l i s h p a t e n t 16277, 1896, in t h e n a m e s of
ratis a n d M a r e n g o . F u r t h e r p a t e n t s in connection
42
MANUFACTURE OF HYDROGEN
with this method of producing h y d r o g e n have been

taken out by Williams (English p a t e n t 8895, I 8 8 6 )
H a w k i n s (English p a t e n t 15379, 1891), Pratis and
Marengo (English p a t e n t 15509, 1897), H a w k i n s
(English patent 25084, 1897), a n d Fielding (English
patent 17516, 1898).
W i t h Zinc*If dilute sulphuric acid is brought into
contact with zinc, chemical action t a k e s place, with t h e
production of zinc sulphate~and h y d r o g e n , in accordance
Zn + H2SO4 - H a + ZnSO*.
Theoretically, to produce 1000 cubic feet of hydrogen
at 30 inches barometric pressure and 40 F . by this process, 180 lb. of zinc a n d 27? lb. of p u r e sulphuric acid
are required, or a total weight of p u r e reagents equal to
452 lb. per 1000 cubic feet of h y d r o g e n produced.
T h e h y d r o g e n produced by this process is liable to
fewer impurities t h a n -frhen iron is used, but it is always
acid a n d liable to contain arsine if commercial sulphuric
acid is used.
T h e zinc sulphate produced in this process can be
turned more easily t o commercial account than iron
sulphate. If to t h e solution of the zinc sulphate resulti n g from the process sodium carbonate or sodium
h y d r o g e n carbonate is added, a precipitate of hydrated
zinc basic carbonate or zinc carbonate is obtained, which
on ignition in a furnace yields zinc oxide (commercially
known a s " z i n c w h i t e " ) , water, a n d carbon dioxide.
Zinc white has a commercial value as a basis or body
*n paints ; it h a s one g r e a t a d v a n t a g e over white lead,
which is used for t h e same purpose, in t h a t it is far less
poisonous. T h i s m e t h o d of t r e a t m e n t of the residual
CHEMICAL METHODS
43
zinc sulphate is t h e subject of a p a t e n t by B a r t o n

( E n g l i s h p a t e n t 28534, 1910).
T h e previous list of p a t e n t s for t h e reaction of iron
and sulphuric acid also c o v e r t h e use of zinc a n d
sulphuric acid for the production of hydrogen.
T h e r e a r e other metals which will yield h y d r o g e n
with sulphuric acid, such as cadmium a n d nickel, while
m a n y metals will yield h y d r o g e n with hydrochloric acid,
such as tin, nickel, a n d aluminium. However, these
reactions c a n n o t b e r e g a r d e d as commercial m e a n s of
producing h y d r o g e n .
(2) M e t h o d s U s i n g an Alkali,
W i t h Zinc*If a solution of caustic soda in water
is b r o u g h t into contact with metallic zinc, chemical
reaction t a k e s place, with t h e production of sodium
zincate a n d h y d r o g e n .
T h e reaction is expressed in
the following equation :
Zn + 2NaOH => H 2 + Na2ZnC>2.
Theoretically, to produce 1000 cubic feet of h y d r o gen at 30 inches barometric pressure a n d 40 F . , 180 lb.
of zinc a n d 224 lb. of p u r e caustic s o d a a r e required, or a
total weight of p u r e r e a g e n t s equal t o 404 lb. p e r 1000
cubic feet of h y d r o g e n produced.
T h e h y d r o g e n p r o d u c e d b y this process is generally
very pure, but, d e p e n d i n g on the purity of the zinc, it is
liable to contain arsine. A s t h e g a s is alkaline, owing
to the caustic s o d a carried in suspension, it requires to
b e scrubbed to m a k e it suitable for balloons a n d airships.
A modification of this process h a s been the subject
of a patent. Zinc as a fine powder is mixed with dry
44
slaked l i m e ; then when hydrogen is required, t h e mixture is h e a t e d in a retort a n d hydrogen is evolved, the
reaction being expressed :
Zn + Ca(OH)3 = H 2 + CaZnO3.
In this modification of t h e process to produce i o o o
cubic feet of hydrogen at 30 inches barometric pressure
and 40 F . , 180 lb. of zinc and 207 lb of slaked lime
are required, or a total weight of pure r e a g e n t s equal to
387 lb. per 1000 cubic feet of hydrogen produced.
By t h e substitution of magnesium hydroxide instead
of slaked lime a similar reaction takes place, b u t t h e
total weight per 1000 cubic feet of h y d r o g e n produced
is reduced t o 341 lb.
T h i s process, with its modification, is covered by
a patent by Majert a n d Richter ( E n g l i s h patent
4881, 1887), and is primarily intended as a process for
the generation of h y d r o g e n in t h e field for t h e inflation
of observation balloons.
THE
HYDRIK
OR A L U M I N A L
PROCESS.
W i t h A l u m i n i u m . I f a solution of caustic soda is

brought into contact with metallic aluminium, chemical
reaction takes place,' with t h e production of sodium
aluminate a n d hydrogen, in accordance with t h e following equation :
2AI + 6NaOH = 3 H 2 + 2Al(ONa)3.
Theoretically, to p r o d u c e 1000 cubic feet of hydrogen
at 30 inches barometric pressure a n d 40 F . , 50 lb. of
aluminium and 225 lb. of p u r e caustic soda are required,
or a total weight of pure reagents equal to 275 lb. per
1000 cubic feet of h y d r o g e n .
T h e h y d r o g e n produced by this process is generally
CHEMICAL METHODS
45
sry pure, b u t t h e g a s is frequently alkaline from m i n u t e

a c e s of caustic s o d a carried in suspension, which m u s t
s r e m o v e d b y s c r u b b i n g with w a t e r before t h e h y d r o g e n
suitable for balloons a n d airships.
THE
SILICOL
PROCESS.
W i t h S i l i c o n , I f a solution of caustic soda is b r o u g h t

to contact with elemental silicon, chemical reaction
ikes place, with t h e production of sodium silicate a n d
y d r o g e n . T h e following equation was supposed to
ipresent t h e reaction
Si + 2NaOH + H 2 O - NajjSiOa + 2H 2 .
Theoretically, to p r o d u c e 1000 cubic feet of h y d r o g e n
: 3 0 inches barometric pressure a n d 40 0 F . , 38*8 lb. of
licon a n d 111 lb. of p u r e caustic soda a r e required, or
t o t a l weight of p u r e r e a g e n t s equal to 149*8 lb. p e r
DOO cubic feet of h y d r o g e n .
T h e g a s p r o d u c e d b y this process is singularly pure,
enerally containing 99'9 p e r cent, h y d r o g e n b y v o l u m e
f t h e w a t e r vapour is r e m o v e d before analysis), "oi per
snt. of arsine a n d phosphine, "005 p e r cent, a c e t y l e n e ,
l e r e m a i n i n g impurity b e i n g air, which is introduced
1 t h e p o w d e r e d silicon a n d also in solution in t h e
r
ater.
I n w o r k i n g this process practically, p u r e silicon is
ot used, h i g h - g r a d e ferro-silicon, c o n t a i n i n g 82-92 p e r
snt. silicon, b e i n g employed. A s will b e seen from t h e
b o v e equation, theoretically 2 '86 parts of a n h y d r o u s
austic s o d a by weight should b e used for o n e p a r t of
licon: H o w e v e r , in w o r k i n g in practice, o n e p a r t of
u r e silicon a n d 1 7 p a r t s of p u r e caustic s o d a a r e emloyed.
T h i s discrepancy b e t w e e n t h e theoretical
46
quantity of soda a n d that actually used has b e e n investigated by the author, who originally considered t h a t the
following reaction might b e taking place :
Si + 2HaO = SiO2 + 2H2.
T h a t is to say, the silicon was being oxidised by the
oxygen of the water, and hydrogen liberated.
T h e first experiment performed was t h e h e a t i n g of
the ferro-silicon* (92 per cent Si) in a flask with boiling
w a t e r ; the resulting steam was condensed, b u t t h e r e
was no residual gas. Therefore it was concluded that
at the temperature of boiling water no reaction b e t w e e n
ferro-silicon a n d water took place.
R e m e m b e r i n g t h a t t h e temperature of t h e caustic
soda solution used in the silicol process is a b o v e iocf C ,
frequently rising to 120 0 C , it was thought t h a t a higher
temperature might perhaps produce t h e suspected rea c t i o n ; ferro-silicon was accordingly heated in an atmosphere of steam in a n electric resistance furnace to
a temperature of 300 C , but still n o h y d r o g e n was
produced. Consequently it was concluded t h a t t h e explanation of the smaller consumption of caustic soda t h a n
would b e anticipated from theoretical considerations must
b e explained on some basis other t h a n t h e reaction of
silicon with water.
T h e next experiment attempted was the h e a t i n g of
ferro-silicon with sodium silicate, i.e. with a p u r e form of
t h e product of the usual equation. W h e n ferro-silicon
was h e a t e d with a n aqueous solution of p u r e sodium
mono-silicate, considerable quantities of h y d r o g e n w e r e
1
The ferro-silicon employed was of French manufacture. I have

since found that some high-grade Canadian ferro-sihcons give traces
of hydrogen with water under the conditions cited in the experiments
CHEMICAL METHODS
47
evolved, thus w a r r a n t i n g t h e conclusion t h a t the o r d i n a r y

equation
Si + 2NaOH + H2O - Na 2 Si0 3 + 2H 2
s not entirely correct, a n d t h a t a silicate richer in silica
Jian that indicated in the equation was formed, a n d t h a t
Drobably t h e following reaction p r o c e e d s to s o m e exent:
Si + Na 2 Si0 3 + 2H,0 Na2Si20B + 2H,.
A s s u m i n g this second reaction t o t a k e place a t t h e
same time as the first, the reaction can b e e x p r e s s e d :
2S1 + 2NaOH + 3H2O = NaSijO + 4H2,
which is e q u i v a l e n t to 1000 cubic feet of h y d r o g e n a t
30 inches b a r o m e t r i c p r e s s u r e a n d 40 F . b e i n g p r o d u c e d
Dy 38*8 lb. of silicon a n d 55*5 lb. of caustic soda, t h e
atio of p u r e caustic soda to pure silicon b e i n g a s 1 "43
s to 1.
U s i n g a plant p r o d u c i n g about 30,000 cubic feet of
l y d r o g e n p e r hour, it was found that 1 "9 p a r t s of caustic
soda (j6 per cent. N a O H ) to 1 part of C a n a d i a n ferrojilicon (84 p e r cent. Si) g a v e very satisfactory results,
;he ratio of t h e p u r e r e a g e n t s being as 1 7 2 p a r t s of
;austic soda b y weight to 1 p a r t of silicon.
Theoretically, 22*5 cubic feet of h y d r o g e n should h a v e
seen produced p e r lb. of the commercial ferro-silicon
ised, but in practice it was found that 2 0 7 cubic feet w e r e
obtained, t h e discrepancy of 1 *8 cubic feet b e i n g t o s o m e
extent accounted for b y t h e protective action of impurities,
oss through leaks a n d also b y hydrogen b e i n g m e c h a n i ;ally carried a w a y b y t h e w a t e r used for cooling t h e
ssuing h y d r o g e n .
Description of Silicol P l a n t . T h e essentials of a
iilicol plant a r e shown in the diagram (Fig. 3).
The
48
MANUFACTURE OF
HYDROGEN
r e q u i s i t e q u a n t i t y of c a u s t i c s o d a is p l a c e d in t h e t a n k
o n t h e r i g h t a n d t h e n e c e s s a r y w a t e r a d d e d t o it t o m a k e
a 25 p e r cent, s o l u t i o n .
T o a s s i s t s o l u t i o n t h e r e is a
s t i r r e r i n this t a n k , w h i c h , in s m a l l p l a n t s , is h a n d - o p e r a t e d a n d in l a r g e o n e s p o w e r - o p e r a t e d .
W h e n the whole
of t h e c a u s t i c s o d a h a s g o n e i n t o s o l u t i o n , w h i c h it r e a d i l y
CHEMICAL METHODS
49
does a s a result of the heat of solution a n d the stirring,

the valve D is opened, allowing t h e whole of t h e soda
solution to r u n via the pipe E into the generator. W h e n
t h e solution has run from t h e caustic soda t a n k into t h e
g e n e r a t o r t h e valve D is closed, t h e n the necessary
quantity of ferro-silicon is placed in the h o p p e r on t h e
top of t h e g e n e r a t o r a n d t h e lid of the h o p p e r closed,
m a k i n g a gas-tight joint. In small plants a little mineral
grease is a d d e d to the generator, via the g r e a s e box.
T h e p l a n t is then ready for operation, a n d silicol is
cautiously fed into the g e n e r a t o r b y means of t h e h a n d operated feed worked from F .
D u r i n g the generation the fluid charge in t h e g e n e rator is k e p t stirred b y m e a n s of t h e stirring mechanism
worked from G. T h e h y d r o g e n produced passes t h r o u g h
the t u b e condenser (where it is cooled a n d t h u s freed
from s t e a m ) a n d then on to t h e g a s holder.
A n excessive pressure, d u e to rapid g e n e r a t i o n of
hydrogen, is g u a r d e d against b y means of a water seal
as shown.
W h e n generation is complete, t h e resulting sodium
silicate solution is rapidly run out via the t r a p p e d discharge pipe a n d the interior of the g e n e r a t o r washed
with cold water supplied from the tap B.
Thermometers
at T i , T 2 , T 3 , a n d T 4 enable the t e m p e r a t u r e at different parts of the a p p a r a t u s to be observed and, if
necessary, controlled.
T h e description of the apparatus has, of necessity, to
be s o m e w h a t general, as these plants a r e m a d e in sizes
v a r y i n g from 1500 to 60,000 cubic feet per h o u r production a n d consequently differ in d e t a i l ; thus, in large
plants, t h e t u b e condenser is not employed a n d t h e hot
h y d r o g e n passes u p a tower packed with coke, down
4
50
which water is falling. F u r t h e r , in large plants, the

generator itself is water-jacketed, as t h e heat of chemical
reaction would otherwise be excessive.
T h e silicol process has t h e a d v a n t a g e of giving a
very g r e a t h y d r o g e n production per hour from a plant
of small costits d i s a d v a n t a g e is that at the prevailing cost of t h e r e a g e n t s employed the hydrogen is
expensive.
T o sum up, this process is exceedingly useful where
large quantities of h y d r o g e n a r e from time to time
required, but it is not t h e best process to use where
there is a constant hour-to-hour d e m a n d for hydrogen.
T h e Silicon Content of the FerrO'Silicon.The
g r a d e of ferro-silicon used in this process is very important, as low-grade material does not yield anything like
t h e theoretical quantity of h y d r o g e n which should be
obtained from t h e silicol present. T h i s arises to a slight
extent from t h e protective action of t h e impurities, which
enclose particles of silicon and therefore prevent the
caustic soda from attacking it.
T h e curve ( F i g . 4), obtained experimentally, shows
that to g e t even m o d e r a t e efficiency ferro-silicon of over
8 0 per cent, silicon c o n t e n t should b e used.
T h e Degree of F i n e n e s s of the Ferro'Silicon.
T h e degree of subdivision of t h e ferro-silicon is also
important, not so m u c h because of its effect on the total
yield of hydrogen, b u t because of its influence on the
rapidity of generation.
F i g . 5 indicates t h e speed of evolution of hydrogen
from t w o samples of t h e same material, under identical
conditions, except t h a t o n e sample was much coarser
than t h e other
CHEMICAL
METHODS
"$18
Relation of Sihco! Content
to Hydrogen Yield.
ID
20
30
40
50
60
70
80
90
100%
Silicon in Ferrosilicon
FIG. 4
JU-!
^ >
1/
f
/
Evolution of Hydrogen from
88% Fenrosf I icon, 20-30 Mesh
and same Material ground to
pass 100 Mesh.
6& D
I
12 14- 16 18
Time in Minutes
FIG.
5.
20
22
Z4- 26
28
30
52
T h e Strength of the Caustic S o d a . T h e strength

of the caustic soda is v e r y important in this process. If
t h e solution is too dilute, a very poor yield of hydrogen
is obtained, a n d also another difficulty is introduced.'
W h e n t h e caustic s o d a solution is very weak, on the
introduction of t h e ferro-silicon or " silicol" reaction takes
place, but the whole solution froths violently, the froth
being carried along t h e pipes from t h e generator, causing
trouble to be experienced in t h e valves, a n d tending to
ultimately block t h e pipes themselves. O n t h e other
hand, the caustic soda solution m a y b e too strong. In
this case, before t h e whole of t h e caustic soda has reacted with t h e requisite a m o u n t of silicol, t h e solution
b e c o m e s either v e r y viscous or actually solid, so a poor
yield is obtained a n d t h e sludge cannot b e got out of
t h e generator without allowing it to cool down and then
digging it out b y manual labour.
T h e following laboratory e x p e r i m e n t s with ferrosilicon containing 92 per cent silicon a n d caustic soda
containing 98 per cent, of sodium hydroxide illustrate the
effect of soda solutions of v a r y i n g strength, a n d also the
effect of varying ratios of p u r e silicon t o pure sodium
hydroxide. F r o m these it will b e seen t h a t the most
economical results a r e obtained w h e n a 40 per cent,
solution of caustic soda is employed a n d the ratio of
silicon to sodium h y d r o x i d e is approximately 1 to 1 "6.
In practice such s t r o n g solutions a r e not used, as,
owing to t h e e v a p o r a t i o n of a g o o d deal of the water
during t h e process, t o w a r d s the e n d a d e g r e e of concentration would be reached which would prevent the
sludge from being r u n out of the plant. A solution containing about 25 p e r cent, of caustic s o d a is found to
give in practice v e r y satisfactory results. Such a solu-
CHEMICAL
METHODS
53
tion of commercial caustic soda, c o n t a i n i n g a b o u t 25 p e r

cent, of p u r e sodium hydrate, h a s at i o o F . a specific
gravity of a p p r o x i m a t e l y 1-32a figure which is very
useful to r e m e m b e r , a s by m e a n s of a h y d r o m e t e r a
rapid check can b e m a d e of t h e caustic soda solution
being p r e p a r e d for use in the process.
T h e ratio of silicol to caustic soda should be such
that t h e ratio of p u r e silicon to p u r e sodium h y d r a t e is
as 1 t o 1 7 2 , b u t this figure is capable of modification
to a slight extent, d e p e n d i n g on t h e t e m p e r a t u r e of t h e
mixture, which is naturally higher in large p l a n t s than
in small ones.
of Silicon Yield in Cubic Feet per lb
of Soda Ratio
of Silicol.
to pure Caustic 1
Experiment. Strength
Solution.
(At 30" Bar. and 6o F.).
Soda.
10 per cent.
10
10
10
30
30
The
23-90
23 5 3
2 4 10
2450
U s e of S l a k e d L i m e instead of C a u s t i c
experiments
obtain h y d r o g e n
to react
i5 3 6
16-80
3 9
158
3 19
40
40
The
13 62
r to o 745
1 1 065
1*480
3 200
o 852
2 13
with
it.
already
described
indicate
that
from ferro-silicon a b a s e m u s t b e
It therefore
occurred
to t h e
t h a t t h e c o s t of t h e o p e r a t i o n of t h e p r o c e s s
reduced
Soda,
by the substitution
of
slaked
lime
author
might
for
to
used
be
caustic
soda.
1
Theoretically t h e m a x i m u m possible yield u n d e r t h e s e condi-
tions of t e m p e r a t u r e a n d p r e s s u r e would b e 2 5 4 c u b i c feet p e r lb of

sihcol of this purity
54
Laboratory experiments, using ferro-silicon containing 92 per cent, silicon a n d p u r e slaked lime, w e r e m a d e
to see if the following reaction took place :
Si + Ca(OH)2 + H3O = CaSiO3 + 2H2.
T h e results of these experiments indicated t h a t w h e n
1 part of ferro-silicon, 2*5 parts of slaked lime, a n d
10 parts of water w e r e used, a yield of 1*53 cubic feet
of hydrogen was obtained per lb. of ferro-silicon used.
Theoretically, u n d e r t h e conditions of t h e experiment,
25*4 cubic feet should h a v e been produced p e r lb. of
ferro-silicon; consequently it can b e safely concluded
t h a t without a n external supply of heat t h e suspected
reaction only takes place to a v e r y limited extent.
R e m e m b e r i n g t h a t slaked lime will decompose
sodium silicate, p r o d u c i n g caustic soda a n d calcium
silicate, in accordance with the following equation :
Ca(OH)2 = 2NaOH + CaSiO3,
it was thought that t h e following reactions might t a k e
place if both caustic soda a n d slaked lime w e r e employed
at the same time :
(1) 2S1 + 2NaOH + 3H2O = NagSiaOa + 4H 2 .
(2) Na2Sia06 + Ca(OH)2 = 2Na0H + CaSi3OB.
Since the caustic soda in t h e solution would be r e g e n e r a t e d after it h a d reacted with t h e silicol, it would
b e available for reacting with yet more silicol, a n d would
consequently reduce t h e quantity of caustic soda used in
t h e process.
T h e following experiments, using a mixture of slaked
lime a n d caustic soda, appear to indicate that the surmise was partly or wholly correct, for with approximately
only half as much caustic soda as ferro-silicon a yield
of almost 16 cubic feet of hydrogen per lb. of ferro-
C H E M I C A L METHODS
55
silicon was obtained. By contrasting these experiments

with those already given, using caustic soda alone, it will
b e seen t h a t the yield obtained from the caustic soda is
much g r e a t e r t h a n t h a t which would have been obtained
were no lime present. W h e t h e r in operating on a large
scale equally g o o d results would b e obtained has not y e t
b e e n determined. 1
Expenment. ^ o , o f Silicon to fetao of Sihcon
pure Caustic Soda.
to Lime.
1
2
3
i to 0426
1 0426
1 0-426
1 to 1*52
1 272
1 3 04
^ ^ S S S ^ t
* Bar and 5 F.
I
4'9S
15-95
15-23
T h e Chemical Composition of the S l u d g e . T h e

equations which h a v e already been given indicate that the
p r o d u c t s of this process are h y d r o g e n a n d sodium disilicate in solution in water. Since, however, neither t h e
ferro-silicon nor caustic soda employed are pure, in the
practical production of h y d r o g e n b y this method, products o t h e r than those shown in the equations are found.
T h e commercial caustic soda employed always contains a certain a m o u n t of carbonate of soda, which takes
no p a r t in the reaction and is found unaltered in the
sludge. T h e s a m e r e m a r k applies to the iron contained
in the ferro-silicon.
T h e following analysis gives t h e chemical composition of t h e sludge produced w h e n 1414 1b. of ferrosilicon, containing 84 per cent, of silicon, and 2688 1b.
1
Since the above experiments the author has found that there is
a patent for the use of lime in conjunction with caustic soda and
silicon, which, under the name of " Hydrogenite," has been employed
by the French Army for inflating observation balloons in the field
56
MANUFACTURE O F
HYDROGEN
of caustic soda, containing 76 per cent, of sodium hydrate,

was employed. Besides the sludge 29,300 cubic feet of
hydrogen was produced, measured at a temperature of
6o F . a n d a barometer of 30 inches.
CHEMICAL COMPOSITION OF SLUDGE.
Moisture .
Silica
.
. . .
Sodium carbonate
. . .
Soda (NaaO, other than carbonate)
Insoluble and undetermined
.
.
Per Cent
by Weight
27 74
3 6 79
6 04
20 08
9"35
IOO'OO
CHEMICAL COMPOSITION OF SODA SOLUTION USED.
Caustic soda
.
Sodium carbonate
Specific gravity at ioo F
.
.
. 24 5
3"o
1 324
CHEMICAL COMPOSITION OF FERRO-SILICON USED.
Silicon
Iron .
Aluminium .
Carbon
Undetermined
.
.
.
.
.
.
.
84 o
6*9
c7
f
2
3-6
100 o
.
.
SCREEN l ANALYSIS OF FERRO-SILICON.
Through 20, on 30
ii
3 4O
31
40 1 50
II
So , , 60
II
60 , 7O
>>
70 , , 80
80 , , 9O
>)
)>
90 ,, TOO
)}
TOO , , I2O
91
120 , 150
>>
150 , 200
3
200
assing
1
Standard I M.M. screens,
Grms Per Cent.

141-5 = 10 28
85 "o = 617
CHEMICAL METHODS
57
T h e U s e of Mineral Grease*To reduce t h e frothing a n d p r i m i n g in this process it is customary to introduce a little mineral g r e a s e , which floats on t h e surface
of the caustic soda solution and p r e v e n t s the formation
of the froth to a considerable e x t e n t
A b o u t 32 lb. of mineral g r e a s e a r e advocated per
1000 l b . of silicol used. H o w e v e r , if t h e caustic soda
solution is strong, i.e. a b o u t 25 p e r c e n t , sodium hydrate,
and t h e g e n e r a t o r is wide, giving a large surface and a
shallow d e p t h t o t h e caustic s o d a solution, n o grease
need b e used at all.
Precautions to be O b s e r v e d . I n this process very
great care m u s t b e t a k e n in the introduction of t h e ferrosilicon.
W h e n t h e ferro-silicon is a t t a c k e d by the
caustic s o d a l a r g e quantities of h e a t a r e g i v e n out,
raising t h e t e m p e r a t u r e of t h e caustic soda solution. If
the caustic soda solution is cold, ferro-silicon can be
introduced into the solution far m o r e rapidly t h a n it is
attacked b y t h e s o d a ; consequently t h e r e is likely to
exist an accumulation of ferro-silicon in t h e solution, the
temperature of which is gradually rising.
A certain
critical t e m p e r a t u r e is ultimately reached w h e n t h e whole
of the accumulated ferro-silicon is a l m o s t instantly attacked, with large yield of h y d r o g e n a n d consequently
the production of high pressure in t h e generator.
Several explosions h a v e been caused in this country
from this reason. W h i l e it is impossible to g i v e any
definite figures, in t h e ordinary commercial plant for the
Droduction of h y d r o g e n b y this process the ferro-silicon
ihould b e a d d e d in small quantities, with a period of
vaiting b e t w e e n each addition, until t h e caustic soda
olution r e a c h e s a t e m p e r a t u r e of a b o u t 180 F
At
58
MANUFACTURE OF
HYDROGEN
this temperature, with a 25 per cent, solution of caustic

soda, high-grade ferro-silicon is almost instantly attacked,
so it can then be a d d e d continuously at a rate which
does n o t produce a p r e s s u r e above the w o r k i n g pressure
of the plant.
In plants for t h e operation of this process no red or
white lead w h a t e v e r should b e used for making joints,
as both these substances at a comparatively low temperature are reduced to metallic lead by ferro-silicon, with
the evolution of large quantities of h e a t a n d the production of incandescence, t h e reaction t a k i n g place with such
rapidity as to constitute almost a n explosion. T h i s can
b e easily illustrated by m a k i n g a mixture of finely
divided ferro-silicon a n d dry red lead, in which the ratio
of the two is 1 part of pure silicon t o 12*2 parts of red
lead. If a match or t h e end of a cigarette is put to this
mixture it goes off violently, with t h e production of great
heat, in accordance with the following equation :
Pb8O4 + 2S1 = 3Pb + 2SiO3.
T h a t the t e m p e r a t u r e produced is exceedingly high can
b e well illustrated b y p u t t i n g , say, half a n ounce of an
intimate dry m i x t u r e of ferro-silicon a n d red lead, in
which t h e proportions of the active principals are as
indicated in the a b o v e equation, on a sheet of thin aluminium, say -ik of a n inch thick. O n putting a match
to this mixture it will be found a hole is melted in the
aluminium sheet. 1
All air must, if possible, be excluded from t h e plant
prior to the introduction of t h e caustic soda, as otherwise in the early stages of generation of hydrogen an
explosive mixture m i g h t arise which on ignition would
1
The melting point of aluminium is 658 C
CHEMICAL METHODS
59
produce a d a n g e r o u s explosion. Such ignition m i g h t

arise from a spark produced from t h e mechanism inside
the generator, b y ferro-silicon coming in contact with
red lead which m i g h t h a v e been used in m a k i n g the
joints in t h e plant, by incandescence produced b y t h e
reaction of ferro-silicon with caustic soda itself. If a n
intimate mixture of p o w d e r e d caustic soda is m a d e with
ferro-silicon in t h e ratio indicated in the equations on
the silicol process, and this mixture is just m o i s t e n e d
with water, h y d r o g e n is rapidly evolved a n d the r e a c t i n g
mass frequently becomes incandescent. Such conditions
might arise in a plant for operation of this process, by
the caustic soda b e i n g splashed o n to s o m e r e c e s s in
the generator, t h e r e b e c o m i n g concentrated, a n d ferrosilicon coming into contact with this concentrated
solution. I t is for this reason t h a t caustic soda a n d
ferro-silicon should never b e stored in close proximity
to each other, as this dangerous reaction m a y arise from
the b r e a k i n g of d r u m s containing t h e two reagents.
Since this process is generally operated in conjunction with a gas-holder, the m o s t e a s y way to exclude air
is to allow h y d r o g e n from t h e gas-holder t o blow b a c k
through t h e p l a n t prior to p u t t i n g this in operation.
H y d r o g e n equal to about four times the v o l u m e of the
plant is required to thoroughly exclude t h e air.
T h e following patents with r e g a r d to this process are
in existence :
Consort. Elektrochem. I n d . E n g l i s h patent 21032,
September 14th, 1909
F r e n c h p a t e n t 418946, July 18th, 1910.
English p a t e n t 11640, M a y 13th, 1911.
J a u b e r t F r e n c h patent 430302, A u g u s t 6th, 1910
60
THE
HYDROGENITE
PROCESS.
T h e r e is a modification of this m e t h o d k n o w n as the

hydrogenite process whereby t h e use of an aqueous
solution of caustic soda is avoided.
A n intimate m i x t u r e of ferro-silicon a n d powdered
caustic soda or lime is packed in s t r o n g cylinders communicating with a high pressure storage. B y means of
a fuse t h e t e m p e r a t u r e is locally raised so t h a t chemical
reaction takes place, with the production of h y d r o g e n
and sodium and calcium silicates.
T h i s modification is covered by Jaubert, English
patent 422296, 1910; English p a t e n t 153, 1911.
W i t h Carbon,If caustic soda is h e a t e d to dull
redness with .charcoal or anthracite or some o t h e r form
of pure carbon, h y d r o g e n is evolved a n d sodium carbonate a n d sodium oxide produced, in accordance with the
following equation :
4NaOH + C = Na2CO8 + Na2O + 2H2.
Theoretically, t o produce 1000 cubic feet of hydrog e n at 30 inches barometric pressure a n d 40 F . by this
process, 222 lb. of caustic soda and I 6 ' 6 I lb of carbon
are required, or a total weight of pure r e a g e n t s equal to
238*61 per 1000 cubic feet of hydrogen produced.
T h e hydrogen produced by this process would be
liable t o contain traces of methane, arsine, a n d sulphuretted hydrogen, t h e a m o u n t d e p e n d i n g on t h e purity of
the coal used.
A modification of this process, w h e r e b y t h e caustic
soda is replaced by slaked lime, is covered b y a patent
taken out in U . S . A . b y Bailey in 1887.
W i t h a Formate or Oxalate.If sodium formate is
CHEMICAL METHODS
61
heated with caustic soda in t h e form of soda lime, t h e

following reaction takes place :
H COONa + NaOH = NasCOg + H a
T h i s m e t h o d h a s b e e n used for t h e p r o d u c t i o n of
hydrogen in t h e laboratory ; however, it c a n n o t b e regarded a s singularly convenient.
If t h e sodium formate is replaced b y sodium or
potassium oxalate a similar reaction takes place :
Na2C2O4 + 2NaOH = 2Na2CO8 + H 2 .
This last method, it is interesting to note, w a s e m ployed b y A m a g a t for t h e p r e p a r a t i o n of t h e h y d r o g e n
for his classic experiments on t h e relationship of pressure
to volume.
(3) M e t h o d s in w h i c h H y d r o g e n i s Derived
Water.
from
H y d r o g e n can b e derived from w a t e r b y m e a n s of

the alkali a n d alkali e a r t h s groups of metals, b u t since
all these a r e expensive, t h e production of h y d r o g e n from
these sources is limited to t h e r e q u i r e m e n t s of t h e
chemical laboratory.
W i t h L i t h i u m . I f metallic lithium is placed in
water it is a t t a c k e d b y it, in a c c o r d a n c e with t h e
following equation, with the production of h y d r o g e n
and lithium h y d r a t e :
2L1 + 2HaO - 2L1OH + H 2 .
It is i n t e r e s t i n g to n o t e that since metallic lithium
has a density of "59 (the smallest density of a n y solid),
it floats on t h e surface of t h e w a t e r while it is b e i n g
attacked.
62
M A N U F A C T U R E OF HYDROGEN
W i t h S o d i u m . I f metallic sodium is placed in

w a t e r it is attacked b y it, in accordance with t h e followi n g equation, with t h e production of hydrogen and
sodium h y d r a t e :
2Na + 2 H 2 O = 2NaOH + H 3
Since considerable quantities of heat a r e given out
when the sodium is attacked by the water, much of
which h e a t is communicated to t h e metal, it frequently
melts while being attacked, the melting point of the
metal being 95 6 C.
W h i l e t h e a b o v e equation expresses t h e principal
reaction which takes place, a second reaction also
occurs, leading to the production of sodium hydride,
which is s o m e w h a t unstable under these conditions and
occasionally explodes with violence, to avoid which a
piece of apparatus has been designed by J. Rosenfeld. 1
W i t h P o t a s s i u m , I f metallic potassium is placed in
water it is attacked, in accordance with the following
equation, with t h e production of h y d r o g e n a n d potassium
hydrate:
2K + 2H2O = 2KOH + H 2 .
Such is the heat which is liberated during the reaction that if a piece of potassium is placed in a bucket
of water, the metal is carried to t h e surface b y the
vigorous stream of h y d r o g e n produced, a n d t h e r e b e comes so hot as to ignite the hydrogen evolved.
T h e s a m e r e m a r k s which h a v e been m a d e as to a
secondary reaction with regard to sodium, apply with
like force to potassium.
1
"Prakt Chem.," 48, 599-601.
CHEMICAL METHODS
63
With the A l k a l i n e Earths,

W i t h M a g n e s i u m . I f metallic m a g n e s i u m is placed
n water which is h e a t e d to its boiling point, h y d r o g e n is
slowly evolved, in accordance with t h e following equa:ion, producing h y d r o g e n a n d m a g n e s i u m h y d r a t e :
Mg + 2 H 2 O = Mg(OH)3 + H 2
T o accelerate t h e reaction, the m a g n e s i u m
heated in a t u b e a n d steam passed over it
is gently
W i t h Calcium.If metallic calcium is placed in

water at ordinary atmospheric t e m p e r a t u r e it decomposes
it in accordance with the following equation, p r o d u c i n g
a. vigorous s t r e a m of h y d r o g e n a n d calcium hydrate :
Ca + 2 H a O = Ca(OH)2 + H 2
W i t h S t r o n t i u m . A similar reaction t o that already
given for calcium takes place, but s o m e w h a t more vigorously
W i t h B a r i u m . A similar reaction t o that a l r e a d y
given for calcium takes place, b u t much m o r e vigorously.
THE
BERGIUS
PROCESS.
W i t h Iron.If metallic iron is heated in t h e presence of water u n d e r v e r y high pressure, h y d r o g e n is

evolved a n d magnetic oxide formed, in accordance with
the following equation :
3Fe + 4H2O = Fe8O4 + 4H2.
T h i s method, which is k n o w n as t h e Bergius process,
was put into commercial operation in 1913 at H a n o v e r .
It has t w o great a d v a n t a g e s a v e r y p u r e h y d r o g e n is
produced, a n d since it is u n d e r g r e a t pressure, it can b e
64
MANUFACTURE OF H Y D R O G E N
used to fill bottles without the use of a compressor. T h e

chemical composition of the hydrogen p r o d u c e d is given
as follows :
Hydrogen .
.
Carbon monoxide .
Saturated hydrocarbons.
Unsaturated hydrocarbons
. 99-95 per cent

'ooi
'042
.
"008
b u t a m o u n t of the carbon compounds must be greatly

influenced by purity of the iron e m p l o y e d ; however,
it appears to be a 'fact that little or no sulphuretted
hydrogen is produced even if the iron contains appreciable quantities of sulphur.
W h i l e it has been stated that the hydrogen is produced by the action of water at high t e m p e r a t u r e and
pressure upon metallic iron, this does not entirely describe the chemistry of the process, for the inventor has
found t h a t the presence of certain metallic salts in the
solution, and also other metals, greatly increase the
speed of production of hydrogen. T h e following comparative table of productions of hydrogen from equal
weights of iron clearly illustrates this p o i n t :
Temperature
Volume of Hydrogen
rf
C.
per Hour.
Iron and pure water .
Iron, water, and ferrous chloride
Iron, water, ferrous chloride, and
metallic copper
.
.
.
Iron, water, ferrous chloride, and
metallic copper .
.
300
300
230 c.c.
1390
300
1930
340
345 ,,
In t h e commercial employment of this process it is

believed that the working pressure is about 3000 lb.
per sq. inch and the temperature 350 C.
CHEMICAL
METHODS
65
I n t h e d i s c h a r g e from t h e vessel in which t h e h y d r o g e n is p r o d u c e d t h e r e is a reflux c o n d e n s e r which effectively p r e v e n t s a n y s t e a m from escaping from t h e p l a n t

w h e n t h e h y d r o g e n is d r a w n off.
O n e of t h e r e m a r k a b l e features of this process is t h e
fact t h a t since the water pressure is so high, it p e n e t r a t e s
right into the iron p a r t i c l e s ; consequently they a r e entirely e m p l o y e d , a n d a yield closely a p p r o a c h i n g t h e
theoretical is obtained.
Theoretically, 1000 cubic feet of h y d r o g e n (at 30
inches b a r o m e t e r a n d 40 F . ) would b e p r o d u c e d with
a n e x p e n d i t u r e of 116*5 ^D- of metallic iron.
T h e size of t h e p l a n t is v e r y small for t h e yields
obtained, it b e i n g stated t h a t a g e n e r a t o r of 10 g a l l o n s '
capacity gives 1000 cubic feet of h y d r o g e n a t a t m o s p h e r i c t e m p e r a t u r e a n d p r e s s u r e per h o u r
After t h e completion of the reaction the pressure can
b e let off from t h e g e n e r a t o r a n d t h e magnetic oxide of
iron p r o d u c e d r e m o v e d a n d reduced by w a t e r g a s to
t h e metallic state, when it can again be employed in t h e
process
I t is claimed that t h e cost of h y d r o g e n b y this
p r o c e s s is exceedingly low ; consequently, if this is corr e c t a n d the mechanical difficulties of manufacturing
g e n e r a t o r s t o w i t h s t a n d t h e v e r y high pressures a n d
c h e m i c a l action a r e satisfactorily overcome, this process
would a p p e a r to be o n e of t h e highest value for t h e commercial production of h y d r o g e n .
A certain a m o u n t of information with r e g a r d t o this
process can b e found in t h e following p a p e r : " P r o d u c tion of H y d r o g e n from W a t e r a n d Coal from Cellulose
a t H i g h T e m p e r a t u r e s a n d Pressures," b y F . Bergius,
5
66
MANUFACTURE O F HYDROGEN
t h e " Journal of the Society of Chemical Industry," vol

xxxii., 1913.
T h e process is protected by t h e following patents :
G e r m a n Patent, 254593, 1911.
F r e n c h Patent, 447080, 1912.
English Patents, 19002 and 19003, 1912.
U n i t e d States P a t e n t s , 1059817, 1059818, 1913,
all in t h e n a m e of F . Bergius.
W h i l e the previous method is of commercial importance, t h e following method is of i n t e r e s t :
W h e n the ordinary process of rusting of iron takes
place, hydrogen is evolved.
It is generally considered t h a t iron does not rust
w h e n it is in contact with perfectly p u r e water, free
from carbon dioxide or any other mild acid. In the
following method iron filings are placed in a steel bottle
partly filled with water saturated with carbon dioxide,
t h e bottle is then closed a n d sealed. It is then agitated,
t h e following reaction taking p l a c e :
Fe + H2O + COa = FeCO3 + H 2 .
T h i s method is o n e of interest a n d is described by
B r u n o in the " B u l l . Soc. Chim.," 1907, [iv.], 1661. It
cannot, however, be regarded as h a v i n g a commercial
use.
W i t h Hydrides.As has already been stated, the
hydrides of the metals of t h e alkali and alkaline earth
groups produce hydrogen on being placed in water.
H o w e v e r , in only two cases are these reactions worth
consideration.
W i t h Lithium Hydride.If lithium hydride is
brought into contact with water, hydrogen is evolved
CHEMICAL METHODS
67
i lithium h y d r a t e formed, in accordance with t h e folding equation :

Li4H2 + 4 H 2 O = 4L1OH + 3H2.
Such is t h e rarity of lithium at t h e present time t h a t
above is neither a commercial nor a laboratory m e t h o d
Droducing hydrogen. It is, however, of t h e g r e a t e s t
srest, owing to the large yield of h y d r o g e n obtained
m a small weight of lithium h y d r i d e
Theoretically,
30 cubic feet of h y d r o g e n at 30 inches b a r o m e t e r
1 40 F . a r e produced from 2 7 7 6 lb. of p u r e lithium
Iride a n d 66 6 lb. of water. M a n y ingenious ideas
re been p u t forward for t h e e m p l o y m e n t of lithium
iride in airships so that in the e v e n t of a n airship
sing g a s from some cause, this m a y b e replaced by
Irogen manufactured in t h e airship. A s has b e e n seen,
oretically, 94*36 lb. of reagents a r e required t o pro:e 1000 cubic feet of h y d r o g e n at 30 inches b a r o m e t e r
I 40 F . N o w this a m o u n t of h y d r o g e n would h a v e
ft of 74*06 lb., so if t h e products of the manufacture
hydrogen were d r o p p e d the b u o y a n c y of t h e ship
aid be increased by 94*36 + 74*06 lb., or 168*42 lb.
every 94*36 lb. of material d r o p p e d from t h e ship,
wever, interesting as these suggestions are, such
ihe rarity a n d cost of lithium t h a t at t h e p r e s e n t
e they a r e not capable of realisation, t h o u g h future
-overies of lithium minerals and cheaper m e t h o d s for
production of lithium hydride m a y possibly r e n d e r
se ideas of practical value.
THE
HYDROLITH
PROCESS.
W i t h C a l c i u m H y d r i d e , I f calcium h y d n d e is
j g h t into contact with water, h y d r o g e n is evolved
68
a n d calcium h y d r a t e formed, in accordance with the

following equation :
CaH2 + 2H2O =* Ca(OH)2 + 2 H 2 .
Theoretically, to p r o d u c e i o o o cubic feet of hydrogen
at 30 inches barometric pressure and 40 F . , 58*4 lb. of
p u r e calcium hydride a n d 49 Mg5 lb. of water are required,
or a total weight of 108*4 lb. of pure reagents per 1000
cubic feet of hydrogen. Since, however, water does not
h a v e to b e carried in most parts of Europe, the theoretical weight to b e carried per 1000 cubic feet of
hydrogen required is 58*4 lb. T h i s method, k n o w n as
the Hydrolith process, has been satisfactorily employed
by the F r e n c h A r m y in t h e field for t h e inflation of
observation balloons, the calcium hydride being packed
in air- and water-tight boxes for transportation. In the
commercial production of calcium hydride small quantities of calcium nitride a r e produced, which, when the
hydride is attacked with water gives rise to ammonia,
in accordance with t h e following equation :
Ca3Na + 6H2O = 3Ca(OH)2 + 2 NH 3 .
H o w e v e r , as a m m o n i a is very readily soluble in
water, if t h e h y d r o g e n produced in t h e process is
scrubbed with w a t e r the a m m o n i a is almost entirely removed a n d an exceedingly p u r e h y d r o g e n results.
T h i s process is protected by a F r e n c h patent, No.
327878, 1902, in t h e n a m e of Jaubert.
W i t h Metallic S o d i u m and A l u m i n i u m Silicide.
If a mixture of metallic sodium a n d aluminium silicide
is placed in water, h y d r o g e n is evolved, with the production of sodium silicate and aluminium hydrate, in
accordance with the following equation .
Al2Si4 + 8Na + i8H 2 O = Al2(OH)fl + 4Na2Si0J + 15H2
CHEMICAL M E T H O D S
69
Theoretically, 1000 cubic feet of h y d r o g e n a t 30

hes barometer a n d 40 F . are produced from 64*8 lb.
this m i x t u r e
It is, however, believed t h a t t h e
ictical yield is a b o u t 80 per cent of this figure.
T h i s process is essentially one for the p r o d u c t i o n of
drogen for w a r purposes, t h o u g h the a u t h o r does not
ow of any actual use of it. T h e m i x t u r e can b e m a d e
0 briquettes, which must b e packed into air- a n d w a t e r ht boxes. T h e method, which is sometimes k n o w n
the " S i c a l process," is protected by a U n i t e d S t a t e s
:ent977442, 1910in the n a m e of F o e r s t e r l i n g a n d
ilipps.
W i t h A l u m i n i u m . I f ordinary metallic aluminium
placed in even boiling water, little or n o chemical
ion takes place. H o w e v e r , if the aluminium is first
algamated with mercury it is rapidly a t t a c k e d b y h o t
ter, with t h e formation of aluminium h y d r a t e a n d
irogen, in accordance with the following equation :
2AI + 61-LjO = A12(OH)0 + 3H0.
Theoretically, to produce 1000 cubic feet of h y d r o 1 at 30 inches barometric pressure a n d 40 F . , 5 0 lb.
aluminium a r e required.
In the commercial application of this m e t h o d it is
necessary to a m a l g a m a t e the metallic aluminium
h mercury by h a n d , as a d v a n t a g e is taken of t h e
t that aluminium will reduce aqueous solutions of
s of mercury to t h e metallic state, in a c c o r d a n c e with
following equation
2AI + 3HgCl2 = 2AICI3 + 3Hg
nsequently, if there is an excess of aluminium over
t required by the equation, this excess will be
70
automatically a m a l g a m a t e d by the metallic mercury as

it is produced.
In a practical application of this method by
Mauricheau Baupre, 1 fine aluminium filings a r e mixed
with a small proportion of mercuric chloride (HgCla)
a n d potassium cyanide ( K C N ) , which causes a slight
rise in t e m p e r a t u r e and produces a coarse powder, which
is quite stable if kept free from moisture. T h i s mixture
can be kept in air- a n d water-tight boxes until it is required, w h e n it can be gradually added to water kept at
about 70 C. A brisk evolution of h y d r o g e n then takes
place which closely approximates to the theoretical yield
A n o t h e r very interesting application of this increased
chemical activity of aluminium when amalgamated with
mercury is incorporated in a toy which is sometimes
seen on sale under t h e n a m e of " D a d d y T i n W h i s k e r s ".
T h i s toy consists of an aluminium stamping of a face
a n d a pencil, the core of which is filled with a preparation
chiefly composed of a mercury salt. It is operated by
rubbing t h e eyebrows and chin with this special pencil.
Shortly afterwards white hairs of aluminium oxide
(A1 2 O 3 ) gather w h e r e v e r t h e pencil h a s touched the
aluminium.
T o operate the a b o v e process for the manufacture
of h y d r o g e n it is necessary that the aluminium should
be as p u r e as possible a n d should not contain copper.
T h e commercial light alloy k n o w n as " d u r a l u m i n , "
which contains about 9 4 per cent, of aluminium and 4
p e r cent, of copper, is entirely unsuitable for generating
hydrogen in the method above described, as it is almost
unattacked by even boiling water containing a small
quantity of a mercury salt.
1
"Comptes Rend.," 1908, 147, 310-1.
T h e following p a t e n t s deal with this process
F r e n c h p a t e n t 392725, 1908, in t h e n a m e of
cheau Baupre.
E n g l i s h p a t e n t 3188, 1909, in t h e n a m e of
heim
G e r m a n p a t e n t 229162, 1909, in t h e n a m e of
heim.
y\
:
MauriGriesGries-
W i t h A l u m i n i u m A l l o y * T h e following a l l o y
Aluminium
Zinc
Tin
.
.
.
78-98 parts
15-15
.7-05
is m a d e a n d cast into a p l a t e ; after cooling it is a m a l g a mated with mercury. After a m a l g a m a t i o n t h e p l a t e is

heated a s strongly as possible without volatilising t h e
mercury. W h e n it has become thoroughly a m a l g a m a t e d
it is allowed to cool a n d is then ready for use.
If this alloy is put into hot water it readily yields
hydrogen ; the h y d r o g e n yield is proportionate t o t h e
aluminium a n d zinc content.
T h e g a s produced is very pure.
T h i s process is protected by the following p a t e n t
U y e n o , ' B r i t i s h patent, 11838, 1912.
W i t h Steam.
In considering the production of h y d r o g e n from
steam, a considerable n u m b e r of processes must b e considered in which t h e first s t a g e (which is c o m m o n to
all the processes) consists in the manufacture of blue
water g a s ; consequently, prior to t h e description of
these processes, a m o n g s t the most important of which
are:
72
T h e Iron Contact process,

T h e Badische process,
T h e L i n d e - F r a n k - C a r o process,
t h e manufacture of water gas will b e described.
T H E MANUFACTURE
OF W A T E R
GAS.
W h e n steam is passed over red-hot carbon, t h e two

following chemical reactions take place .
(1) C + H2O = CO + Ho.
(2) C + 2H2O = CO2 + 2 H2
T h e question a s to which equation represents the
predominant reaction t a k i n g place, d e p e n d s on the
temperature of t h e c a r b o n ; roughly speaking, the higher
t h e temperature the more closely does the reaction
coincide with the first chemical equation.
T h e following experimental results ( H . Bunte, " J . fur
Gasbeleuchtung," vol. $y, 81) clearly illustrate the effect
of temperature on t h e chemical composition of the p r o ducts of the reaction
Temperature
*C.
674
758
838
954
IOIO
1125
Per Cent, of Steam

Decomposed
Q.Q
0
25 30
41-0
70*2
94 'o
99 4
Composition, by Volume of Gas

rroaucea.
Ha.
CO.
COa
65-2
65 2
61 9
53 3
488
509
49
7*8
15 1
39 3
49 7
48-5
298
27 0
22 9
6-8
15
06
In the first of t h e chemical equations given, it will

b e seen that the products are composed of 50 per cent.
CHEMICAL METHODS
73
ydrogen a n d 50 per cent, c a r b o n monoxide, while in

ie second, t h e composition is 66"66 per cent, h y d r o g e n
n
d 33'33 per cent carbon dioxide ; in D r . B u n t e ' s
tperiments, figures closely approximating to t h e first
luation were obtained w h e n t h e t e m p e r a t u r e of t h e
irbon was IOOO-IIOO C C , while figures similar t o t h e
-oducts indicated in the second equation w e r e found
hen the t e m p e r a t u r e was 674 0 C.
Now, w h a t e v e r purpose w a t e r g a s may b e required
r, its use for this purpose d e p e n d s on the fact t h a t t h e
is will combine with oxygen with t h e evolution of
iat, consequently t h e plant should be worked to m a k e
e product with the highest calorific power for t h e
west fuel consumption. T h i s requirement is r e a c h e d
ore closely if t h e plant is operated so t h a t the first
uation represents the chemical reaction which t a k e s
ice; consequently, in the practical manufacture of w a t e r
s the coke or other fuel in the g a s p r o d u c e r should
at a t e m p e r a t u r e of a b o u t iooo C.
T h e chemical reaction producing the d e c o m p o s i 11 of the steam is endothermic, t h a t is to say, a s t h e
iction proceeds, t h e t e m p e r a t u r e of t h e coke falls, so
it in order t o obtain a g a s approximating t o the p r o cts in the first equation, heat must b e supplied t o t h e
ce, to counteract t h e fall in temperature, d u e t o its
LCtion with the steam.
In the oldest type of plant, the c o k e which was used
the manufacture of the water gas was in a cylinder,
ich was externally h e a t e d by a coke or coal fire ;
vever, this p r o c e d u r e was not very efficient, a n d t h e
ctice is not in use at all a t t h e p r e s e n t time.
In practice to-day there a r e two m e t h o d s of m a k i n g
:er gas, one the E n g l i s h or H u m p h r e y a n d G l a s g o w
74
M A N U F A C T U R E OF
method, a n d t h e
Fleischer method.
other
HYDROGEN
t h e Swedish
or
Dellwick-
E n g l i s h M e t h o d . I t has already been pointed out

t h a t from t h e r m a l chemical reasons, t h e c o k e t h r o u g h
which t h e steam is passing in the manufacture of w a t e r
g a s should b e a t a b o u t iooo C. in order to obtain g o o d
results, a n d that as a result of t h e reaction b e t w e e n t h e
c o k e a n d steam, t h e t e m p e r a t u r e of t h e former falls,
necessitating t h e addition of heat to t h e coke mass, in
order to k e e p up the efficiency of the process.
It is in the m e t h o d of maintaining the coke t e m p e r a t u r e t h a t t h e E n g l i s h a n d Swedish systems differ.
In
b o t h systems t h e coke is kept at t h e proper t e m p e r a t u r e
by shutting off the steam supply from time to time, a n d
blowing air through the coke, t h e products of t h e air
blast passing out of t h e generator t h r o u g h a different
passage to those of t h e steam blast.
T h e effect of blowing air t h r o u g h t h e coke is of
course to produce heat, for the following reactions t o
a lesser or greater e x t e n t take place .
(i) C + O2 - CO2j
(a) CO2 + C = 2CO,
a n d the heat, which is produced by the combustion of
some of the coke, h e a t s the remainder, thus raising its
temperature, so that the air blast can b e shut off, a n d
t h e steam blast again turned on.
In t h e English s y s t e m the depth of t h e coke in t h e
g e n e r a t o r is considerable, consequently t h e carbon d i oxide formed at the base of the fire tends to be r e d u c e d
in the u p p e r p a r t of t h e fire by t h e h o t coke, in accordance with equation (2), therefore in t h e English s y s t e m
during t h e air blast a combustible g a s is produced.
CHEMICAL METHODS
75
owever, while at first sight this m i g h t appear to b e a n

Ivantage, there a r e several d i s a d v a n t a g e s -associated
ith this m e t h o d of working. In t h e first place, t h e
is which is produced d u r i n g the air blast, t h o u g h c o m lstible, is not a gas of high calorific power, a s it contains
ich a l a r g e a m o u n t of atmospheric n i t r o g e n ; in fact,
ider the m o s t favourable circumstances, t h e g a s p r o iced d u r i n g the air blast will not contain over 30 per
nt. of carbon monoxide, while t h e rest of it will b e in>mbustible, b e i n g chiefly nitrogen t o g e t h e r with s o m e
rbon dioxide
A n o t h e r d i s a d v a n t a g e of this s y s t e m
that since t h e c o k e is p e r m a n e n t l y b u r n t only t o
-rbon monoxide, t h e a m o u n t of h e a t actually g e n e r a t e d
the coke mass is comparatively small, consequently
e rate of temperature rise in the coke m a s s is slow.
In t h e Swedish or Dellwick-Fleiscker
method, the
>ke t e m p e r a t u r e is from time to t i m e raised by m e a n s
an air blast, b u t in this case t h e d e p t h of fuel is
latively shallow, so t h a t t h e carbon b u r n t remains
irmanently in the form of carbon dioxide ; and since in
irning equal weights of carbon to carbon m o n o x i d e
id carbon dioxide over t h r e e times as much h e a t is
merated in situ w h e n the carbon is b u r n t to c a r b o n
oxide t h a n w h e n b u r n t to carbon monoxide, t h e rate
rise of t e m p e r a t u r e of t h e coke m a s s in t h e g e n e r a t o r
much m o r e rapid t h a n is the case in the E n g l i s h
-stem, a n d consequently t h e period occupied b y t h e
r blast is very much reduced.
Fig. 6 shows a diagram from Dellwick's E n g l i s h
itent 29863, 1896, illustrating his plant for the p r o d u c Dn of blue w a t e r g a s .
A is the g e n e r a t o r provided with a c o k e receptacle
, which passes t h r o u g h a stuffing-box D placed o n
76
MANUFACTURE O F H Y D R O G E N
t h e cover or top of the generator. T h e object o f this

receptacle is to keep the fuel height constant i n t h e
generator , if B is kept filled with fuel, as t h a t which
is on the grate burns away, fresh fuel will run in f r o m B
and will keep the depth of fuel on the g r a t e c o n s t a n t
L is the main air inlet, while a secondary s u p p l y

of air takes place t h r o u g h the vertical pipe G , the
purpose of this latter air inlet being to ensure a t h o r o u g h
supply of air to all parts of the fuel bed.
S and S ' are steam inlets, I a n d I ' are g a s o u t l e t s ,
a n d E is an outlet for t h e products m a d e during t h e air
blast.
CHEMICAL METHODS
77
T h e m e t h o d of w o r k i n g this g e n e r a t o r would b e as
follows :
W h e n a c o k e o r o t h e r fire of suitable d e p t h h a s b e e n
obtained o n t h e g r a t e , t h e receptacle B is c h a r g e d
with fuel, a n d t h e lid C firmly closed ; v a l v e s I a n d
I ' a r e closed a n d v a l v e F opened, t h e n air u n d e r
suitable p r e s s u r e is a d m i t t e d t h r o u g h L a n d G ; this
causes t h e fuel to b u r n with rise in t e m p e r a t u r e of
t h e u n b u r n t portion, while the p r o d u c t s of combustion, containing a b o u t 20 p e r cent, of carbon dioxide
a n d 70 per cent, of nitrogen, escape by t h e p a s s a g e E .
W h e n t h e t e m p e r a t u r e of the coke on the hearth has
b e e n raised to a b o u t i o o o 0 C. the air blast is stopped,
v a l v e F closed, v a l v e I ' opened, a n d s t e a m a d m i t t e d
t h r o u g h S ' with t h e c o n s e q u e n t production of blue g a s ,
which passes out t o a scrubber a n d holder, via the
valve I'.
W h e n a s a result of t h e decomposition of t h e steam
by the fuel mass, the t e m p e r a t u r e of the latter h a s fallen
below the economic limit, t h e steam supply is s h u t off,
a n d the air blast started again to raise t h e fuel t e m p e r a ture. W h e n t h e t e m p e r a t u r e is a g a i n suitable, t h e air
is shut off a n d steam a g a i n passed t h r o u g h t h e fuel, b u t
o n this occasion d o w n w a r d s from t h e s t e a m supply S,
t h e w a t e r g a s p a s s i n g o u t by t h e outlet I.
T h e object of this alternation of t h e direction of the
s t e a m blast is to k e e p t h e t e m p e r a t u r e as uniform as
possible t h r o u g h o u t t h e fuel mass.
F i g . 7 shows a m o d e r n water g a s producer, which
is self-explanatory, t h e fuel c h a r g i n g is d o n e after
every third s t e a m blast, a n d t h e d e p t h of t h e fuel k e p t
correct by m e a n s of a g a u g e rod, d r o p p e d t h r o u g h t h e
lid at t h e t o p of t h e g e n e r a t o r . T h e s a m e alternation
78
in the direction of t h e steam blast is maintained, while

during the air blast the products of combustion escape
through the lid at t h e top of the generator, which is
open d u r i n g this stage.
Steam
Inlet
\ Gas Outlet
\~Ash Outlet
FIG
T h e sequence of operation with a s t a n d a r d g e n e r ator, having a circular hearth about 5 feet 6 inches in
diameter, would be :
1. Air blast
2 Steam up
3. Air blast
.
.
,
2 minutes
6
j minute
CHEMICAL METHODS
4. Steam down
5. Air blast
6. Steam up
79
. 6 minutes
1 minute
. 6 minutes.
Lt the end of the last operation, additional fuel would

e added a n d the sequence again started. T h e air
jpply main would b e a t a pressure of a b o u t 15 inches
f water a b o v e the atmospheric, while t h e s t e a m main
p
ould be at about 120 lb. per sq. inch, t h e rate of flow
F the steam being about 45 lb per m i n u t e , d u r i n g the
earning periods.
W o r k i n g under t h e conditions described, using coke
f the following composition as a fuel:
Moisture
.
Ash .
Volatile sulphur
.
Nitrogen .
Carbon, etc. (by difference)
Per Cent.
6'o by
9o
1-35
.0*6
. 83x5
weight.
,,
100 00
water g a s of a b o u t t h e following composition would
e obtained :
Per Cent.
Hydrogen
. 52*0 by volume
Carbon monoxide
39*6
Methane . . . .
0 4 , ,
Carbon dioxide
.
.
.
-3*5
0*5
Nitrogen
.
.
. 4 0
,,
100 o
>r a consumption in t h e g e n e r a t o r of a b o u t 35-40 lb. of
Dke per 1000 cubic feet of blue water gas m e a s u r e d at
tmospheric temperature a n d pressure.
A consideration of this coke consumption is instruc-
80
t i v e ; from the analysis of the water gas, it will be seen in

i o o o cubic feet of the gas there a r e
396 cubic feet of carbon monoxide.
35
11 .. .. dioxide.
If the barometer is 30 inches and the temperature 6o F ,
1000 cubic feet of carbon monoxide weighs 74*6 lb.
74-6 x 396
' 39 >
.
.1
IOOO
= 29*6 lb
But carbon monoxide contains i | of its total weight of carbon.
28
20 6 X 12
.. 396 cubic feet of carbon monoxide contains
lb.
carbon = 1 2 7 lb.
Similarly,
1000 cubic feet of carbon dioxide weighs 117 3 lb
35 x " 7 3
35 !
Iooo
= 4 1 lb.
But carbon dioxide contains of its total weight of carbon.
44
.. 35 cubic feet of carbon monoxide contains
lb. of
44
carbon = 1 1 lb
A d d i n g these two results together, it is seen that while
35-40 lb. of coke, equivalent to 29-33 lb. of carbon, a r e
consumed in the generator per 1000 cubic feet of water
gas, only 13 8 lb. of this carbon, or 42-46 per cent., are
present in the g a s produced, the bulk of t h e remainder
of the carbon consumed in the generator b e i n g burnt
during the air blast period, and the remainder lost in the
ash pit, and during clinkering; however, while these
figures are instructive, as indicating the m a g n i t u d e of
air blast consumption of fuel, to gain comparative figures
it is necessary to obtain the calorific power of the coke
CHEMICAL METHODS
81
consumed, a n d of t h a t of t h e w a t e r g a s p r o d u c e d from
a given w e i g h t of coke.
If 35 lb. of t h e coke, t h e analysis of which h a s been
already given, a r e c o n s u m e d in t h e production of 1000
cubic feet of water g a s at 30 inches b a r o m e t e r a n d 6o
F. f of t h e composition which h a s also been given, it will
b e found t h a t t h e calorific power of t h e coke consumed,
c o m p a r e d w i t h t h a t of the g a s produced, is as
516:342,
t h a t is to say, j u d g e d o n a t h e r m a l efficiency basis, t h e
efficiency of t h e p r o d u c e r w o r k i n g u n d e r these conditions is
342 x 100 _
516
which is a figure such as is obtained in ordinary commercial w a t e r g a s manufacture.
T h e analysis of t h e water g a s so far g i v e n e n u m e r ates t h e chief constituents, but in reality t h e r e are traces
of other products, such as carbon bisulphide, carbonyl
sulphide, a n d thiophene, derived from t h e sulphur in t h e
"uel, which, m i n u t e in quantity, m a y nevertheless in the
:ertain chemical processes p r o d u c e appreciable a n d uniesirable r e s u l t s : from t h e iron contained in t h e fuel,
n i n u t e a m o u n t s of iron carbonyl a r e formed, which in
n o s t processes in which water g a s is used is a m a t t e r
>f n o importance, b u t if the g a s is to b e used for
i g h t i n g with incandescent mantles, its removal is deirable.
T h e producer, which has been described, is not in
>ractice absolutely continuous in operation, as from
ime t o t i m e t h e process has to b e interrupted in order
o r e m o v e t h e clinker from t h e fire.
6
82
MANUFACTURE OF
HYDROGEN
T h e process of " clinkering," besides requiring labour,

is wasteful, as h o t fuel as well as clinker is d r a w n from
the fire, consequently various devices h a v e b e e n d e s i g n e d
to m a k e self-clinkering producers.
T h e majority of these designs consist essentially
of a rotating conical hearth.
F i g . 8 s h o w s a device
described in E n g l i s h patent 2461 n , 1909, which is almost self-explanatory. T h e clinker p a n h a n d t h e blast
nozzle i are connected a n d free to rotate o n t h e ball r a c e
shown in the vertical section. T h e end of t h e blast
nozzle i is fitted with helical excrescences w i t h holes k
for steam and air in their trailing edge.
During the
working of the producer, the nozzle and clinker p a n a r e
rotated, a n y clinker forming being b r o k e n u p b e t w e e n
the helical vanes on the fixed water j a c k e t e d b o d y of
the producer a n d those on the rotating b l a s t nozzle.
T h e clinker on b e i n g broken up falls into t h e clinker
hearth, which is filled with water to such a d e p t h a s t o
make a water seal b e t w e e n t h e producer b o d y a n d t h e
moving hearth.
T h e bottom of the clinker h e a r t h h a s fixed ribs,
which t e n d to hold t h e crushed clinker, w h i c h d u r i n g
the rotation of t h e hearth is carried r o u n d until it is
brought against the fixed v a n e 0 , this lifts it out of t h e
water.
Producer h e a r t h s of t h e type described d o n o t a p pear to effect a n y appreciable saving in fuel, b u t since
they eliminate clinkering, they h a v e a decided a d v a n t a g e ,
as the g a s yield is g r e a t e r in a given t i m e t h a n w o u l d
otherwise be t h e case.
Purification of W a t e r G a s , F o r m o s t industrial
purposes, it is necessary t h a t the crude w a t e r g a s should
CHEMICAL
METHODS
TV
71/
S e c t i o n CD.
FIG 8.
84
b e purified before its ultimate use. F o r practically

every process in which water g a s is used it is necessary
t h a t it should b e freed from t h e impurities which it
mechanically contains, a n d which are composed of ash
a n d dust, carried b y the g a s from t h e producer.
T h e mechanically retained impurities in water g a s
a r e r e m o v e d b y s c r u b b i n g the g a s with water, t h a t is
to say, b y passing it up a tower, down which water is
falling. N o t only does this water scrubbing r e m o v e t h e
mechanically retained impurities, b u t it also, by reducing
t h e t e m p e r a t u r e of t h e gas, causes the condensation and
r e m o v a l of the m i n u t e quantity of iron carbonyl contained in the gas.
R e m o v a l of Sulphuretted H y d r o g e n . F o r most
purposes for which water gas is required it is desirable
t h a t it should b e free from sulphuretted h y d r o g e n , this
is usually accomplished b y passing t h e g a s a t about
55-65 F . over h y d r a t e d oxide of iron, when the following reaction takes place :
Fe3(OH)6 + 3H2S = 2FeS + 6HaO + S.
After lapse of time, t h e hydrated ferric oxide ceases to
h a v e a n y sulphuretted hydrogen-absorbing power, so
t h e g a s is diverted t h r o u g h other h y d r a t e d oxide, and
t h e spent oxide r e m o v e d and placed in the open air,
when, after moistening with water a n d exposure, the
following reaction takes place .
4FeS + 6HSO + 3O2 - 2Fea(OH)<j + 4S
T h u s it is seen the original oxide can b e reproduced,
a n d on reproduction can b e used for t h e absorption of
fresh sulphuretted hydrogen. In practice each revivification increases t h e free sulphur content of t h e oxide
CHEMICAL METHODS
85
>out 7 per cent., a n d as time goes o n t h e free s u l p h u r

t h e iron oxide increases to 50-60 per cent, sulphur,
hen it c o m m a n d s a ready sale to manufacturers of sulmric acid ; r o u g h l y speaking, 1 ton of oxide will purify
000,000 cubic feet of g a s before it is finally spent.
I n this country, it is n o t generally necessary t o h e a t
e hydrated oxide of iron t h r o u g h which the crude
ater gas is passed, as t h e h e a t evolved by t h e chemical
action is sufficient to k e e p t h e oxide at a suitable t e m Tature. H o w e v e r , in m a n y parts of t h e world, w h e r e
e winter t e m p e r a t u r e is exceedingly low, it is n e c e s ry to pass steam coils through t h e oxide, a s otherwise
) absorption of sulphuretted h y d r o g e n t a k e s place.
T h e reason for this failure to absorb the s u l p h u r e t t e d
'drogen is d u e to t h e fact, already given in t h e e q u a m, that with t h e absorption of t h e s u l p h u r e t t e d
r
drogen, water is produced, which freezes on t h e sur:e of the h y d r a t e d iron oxide, and thus p r e v e n t s further
lphuretted h y d r o g e n coming in contact with i t
In the practical removal of sulphuretted h y d r o g e n ,
is desirable to h a v e quite a considerable a m o u n t of
iter in t h e h y d r a t e d oxide (about 15 per cent, b y
sight), as this tends to k e e p it open a n d t h u s k e e p t h e
essure necessary to g e t the water g a s t h r o u g h t h e
.ide quite l o w ; it is also desirable to k e e p t h e oxide
kaline, consequently a b o u t 1 per c e n t of lime is m i x e d
th it to accomplish this.
W h e n new h y d r a t e d oxide is p u t in w a t e r g a s
irifiers, e v e n t h o u g h it m a y contain a sufficiency of
iter, it tends to cake t o g e t h e r a n d create b a c k
essure.
T h i s can b e p r e v e n t e d , either b y mixing s a w d u s t
th the n e w oxide before p u t t i n g it in t h e purifiers
86
HYDROGEN
(about i part to 5 of oxide by volume) or by mixing s o m e

already used oxide containing a considerable a m o u n t of
free sulphur with the n e w oxide ; this also tends to p r e v e n t caking.
In ordinary commercial purification of water g a s ,
100 tons of h y d r a t e d ferric oxide will effectively purify
200,000 cubic feet of crude water g a s per 24 h o u r s ;
this allows of k e e p i n g 20-30 tons of " r e v i v i f i e d " oxide
in reserve, available to replace t h e working oxide a s it
becomes " s p e n t " .
T h i s d e g r e e of purification of crude water gas to b e
used in t h e manufacture of h y d r o g e n is common t o all
t h e processes using i t ; in some of t h e processes special
m e t h o d s of purification a r e employed, a n d these will b e
g i v e n in the description of t h e process which r e n d e r s
such m e t h o d s necessary.
T h e Iron Contact P r o c e s s .
Of all the processes for the production of h y d r o g e n
in which water g a s represents one of the active r e a g e n t s ,
t h e Iron Contact process is the most important, as it is
b y this process t h a t t h e greater a m o u n t of t h e w o r l d
production of h y d r o g e n for use in industry a n d w a r is
at present m a d e ; b u t important as this process is, it is
doubtful if it will maintain its p r e s e n t pre-eminent position d u r i n g the next few years, as other processes, m o r e
economical, but at p r e s e n t n o t so reliable, are a l r e a d y in
existence, and with lapse of time g r e a t e r reliability will
p r o b a b l y b e obtained in these later processes, which will
result in the I r o n Contact process occupying a less imp o r t a n t position in h y d r o g e n production than it d o e s
to-day.
When
steam is passed over h e a t e d metallic
iron,
CHEMICAL METHODS
87
drogen is produced in accordance with t h e following

uation;
3Fe + 4 H / ) - Fe3O4 + 4H2
Theoretically, to produce 1000 cubic feet of h y d r o g e n
30 inches barometric p r e s s u r e a n d 40 F . , 116*5 lb.
iron and 49*95 lb of s t e a m are required : h o w e v e r , in
actice these figures a r e not closely a p p r o a c h e d b e c a u s e
e magnetic oxide of iron formed t e n d s to shield t h e
stallic iron from the action of t h e s t e a m ; indeed, t h e
action m a y b e r e g a r d e d as merely a surface one.
W h e n the protective action of t h e m a g n e t i c o x i d e
s reached such a d e g r e e that t h e yield of h y d r o g e n
s become negligible, t h e supply of steam is stopped,
Ld the water g a s is passed over the m a g n e t i c oxide,
ducing it to metallic iron, in accordance with t h e folwing equations .
Fe3O4 + 4H2 = 3Fe + 4H2O
F e A + 4CO - 3Fe + 4CO*.
hen further steam can b e passed over t h e iron, with
e production of further h y d r o g e n .
T h u s , it is seen t h a t t h e same iron is u s e d continuisly, and steam a n d blue water g a s are t h e t w o rerents consumed. S u c h is t h e chemical outline of t h e
on Contact process ; however, in practice, t h e process
somewhat more complex and v e r y much less efficient
tan either t h e Electrolytic process or t h e B a d i s c h e
-ocess, b o t h of which a r e described at a later stage, nor
in the hydrogen produced b e r e g a r d e d as so satisfactory
>r some industrial purposes, such as fat h a r d e n i n g , as
lat m a d e by t h e other two processes.
In the practical w o r k i n g of the Iron Contact process,
le process is not b e g u n b y passing s t e a m over h o t
88
MANUFACTURE O F H Y D R O G E N
metallic iron, b u t by manufacturing t h e iron in situ, by

reducing iron ore, such as hematite, with the water gas,
which can be expressed by the following equations :
2Fe2O8 + 3H2 = 2Fe + 3H2O
Fe2O8 + 3CO - 2Fe + 3CO2.
T h e a d v a n t a g e of this procedure is t h a t a s p o n g y
coating of metallic iron is obtained on the refractory
iron oxide, with the result that the iron and the resulting
magnetic oxide tend to be held together, a n d so keep
t h e material open, and therefore free from back pressure
t o the passage of t h e steam and water gas.
In practice, to obtain a yield of 3500 cubic feet of
hydrogen per hour, a b o u t 6 tons of iron ore are required.
T h i s ore, both in its original form and its subsequently
surface altered state, is kept at a temperature of 650 0 900 C . ; if lower than 650 0 C. the reactions b e c o m e very
slow, a n d if higher t h a n 900 C. t h e material tends to
frit, and become less open, thus creating resistance to
t h e flow of gas a n d steam.
In t h e practical working of t h e Iron Contact process,
t h e process consists of three s t a g e s :
1. Reducing.
2. Purging.
3. Oxidising.
Reducing*The reducing stage consists in passing
water g a s over t h e heated oxide, thus producing a coati n g of metallic iron on the oxide. D u r i n g t h e first
moment of reducing the reaction is comparatively
effective, but with fewer opportunities for the gas to
come into contact with unacted-upon oxide, the water
g a s is less and less effectively used, a n d consequently
the gas on leaving the retorts contains m o r e and more
CHEMICAL METHODS
89
jrdrogen a n d carbon monoxide as the reaction connues.

T h i s variation in t h e efficiency of reduction, with
pse of time, is clearly illustrated in the g r a p h , F i g . 9,
hich shows the carbon monoxide a n d carbon dioxide
Dntent of t h e water g a s after passing at the r a t e of
DOO cubic feet p e r hour over 4*2 tons of iron oxide,
sated to 750 0 C.
In practice, it is found t h a t the speed of reduction is
60
56
'60
i>40
i
1
Weight of Oxide =4-2 tons

_
Volume of Water Gae -9000 cu ft per hour
"
| i i i I l I l I
1S
0 1 2 3 4 5 6 7 8 9 3D 11 1Z 13 14 15 16 17 38
Minutes
FIG 9
Luch slower than the speed of oxidation, consequently,
L practice, t h e duration of the various stages is :
Reducing
.
.
.
. 2 0 minutes.
Purging .
.
35 seconds.
Oxidising
. . .
9 minutes, 25 seconds.
20
...*-
.--"""
P u r g i n g , W h e n the reducing s t a g e is stopped, t h e

itort or retorts, containing the surface reduced oxide,
, or are, rilled with an atmosphere of partly altered
p
ater g a s ; consequently w h e n steam is t u r n e d on
ydrogen is produced contaminated with the residual
ater g a s ; thus impure h y d r o g e n is allowed to flow
9o
MANUFACTURE O F HYDROGEN
into some receptacle, where it is subsequently used for

heating, or some other process, which will be described
later.
A t the end of 35 seconds the outflow of the g a s is
altered, and the now comparatively pure h y d r o g e n is
directed into a g a s holder, or wherever it may be r e quired.
O x i d i s i n g . T h e oxidising stage is exactly the s a m e
as the purging stage, except as to the direction of o u t flow of the resulting hydrogen.
In normal working the gas produced has approximately the following composition :
Per Cent,
by Volume
Hydrogen
97 5
Carbon dioxide
15
monoxide
5
'03
Nitrogen (by difference)
47
100 00
Purification of Crude H y d r o g e n . T h e crude h y drogen is first scrubbed with water, which besides r e moving mechanically contained impurities also reduces
t h e amount of carbon dioxide, as this gas is soluble in
water.
T h e hydrogen is then passed through boxes containing slaked lime, where both the carbon dioxide a n d
sulphuretted hydrogen are absorbed in accordance w i t h
the following equations :
Ca(0H)2 + C0 2 = CaCO8 + H 2 0,
Ca(OH), + H2S = CaS + 2 H 2 O.
However, since there is no simple process of revivi-
CHEMICAL METHODS
91
ring the lime after use, it is probably better practice to

ass the crude hydrogen first t h r o u g h an iron oxide box,
lentical with that used in purifying water g a s ; h e r e the
jlphuretted hydrogen would be absorbed, a n d t h e n t h e
as would pass on to a lime box, where t h e carbon dixide would b e absorbed, as already s t a t e d ; h o w e v e r ,
r
hichever procedure is adopted as to the purification,
gas of t h e following a p p r o x i m a t e composition is
btained:
Hydrogen
Carbon dioxide
monoxide
Nitrogen (by difference)
.
.
.
.
.
.
.
.99-0
ml
.
-5
trace
"5
IOO'O
Secondary Chemical R e a c t i o n s . T h e fundamental

lemical reactions, whereby h y d r o g e n is p r o d u c e d b y
le use of water g a s a n d steam alternately, in t h e
resence of iron oxide, h a v e now been g i v e n in conderable detail, and so far there does not a p p e a r a n y
iason w h y t h e same iron ore should not b e used inefinitely ; however, there are two reasons which necestate the replacement of the ore from time to time,
'he first reason for the deterioration of the ore is purely
hysical, while the second is partly chemical and partly
hysical. T h e physical reason for the g r a d u a l failure
f the material is d u e to t h e fact that with constant use
le ore tends to b r e a k up into smaller a n d smaller pieces,
IUS creating back pressure to the flow of water g a s a n d
earn , consequently a condition arises from this disitegration of the ore which necessitates its replacelent.
92
W h e n carbon monoxide is in contact with hot metal-
lic iron, t h e following reaction slowly takes place :

Fe + 6CO - FeC8 + 3COa
Such a condition arises in the I r o n Contact process
towards the end of t h e reducing stage, while during the
oxidising stage the following reaction slowly takes
place:
3FeC3 + 13H2O = 9CO + F e A + i3H 2
T h u s , by the continued operation of the process, there
tends to b e an increasing amount of carbon monoxide
in the resulting hydrogen. T h e r e are t w o methods
whereby this difficulty can be dealt with : one is anticipatory, a n d consists in adding a volume of s t e a m x to
t h e water gas, prior to its passage over the iron oxide,
equal to a b o u t one-half t h e carbon monoxide content of
the gas. This, while slightly retarding t h e speed of
reduction of the oxide, prevents the absorption of carbon
b y the metallic iron, formed during the reduction, a n d
consequently allows of hydrogen of high purity being
produced. T h e o t h e r method is intermittently employed
a n d consists in occasionally passing air over the carboncontaminated iron oxide, when the following reaction
takes p l a c e :
4FeQ, + i5O a = zFeaOs + 12CO2,
thus allowing after reduction a purer hydrogen to be
made. H o w e v e r , this process, k n o w n as " b u r n i n g off,"
while undoubtedly improving the purity of t h e hydrogen
subsequently produced, appears to hasten the disintegration of t h e oxide, contributing to t h e necessity for its
ultimate replacement, owing to the high back pressure
this physical condition produces.
French patent 395132, i9o8,Dellwick-Fleischer Wassergas Ges
93
T h e minute quantities of sulphuretted h y d r o g e n

present in t h e crude h y d r o g e n arise from two causes,
t h e first of which is sulphur in the original ore, which,
during t h e oxidising stage, produces sulphuretted h y d r o gen, while the other is due to t h e small quantities of
sulphuretted h y d r o g e n present in the purified w a t e r gas,
which during t h e reducing stage are absorbed b y t h e
iron in t h e retorts as ferrous sulphide, which is subsequently decomposed d u r i n g the oxidising stage, t h u s :
FeS + H2O = FeO + H2S,
3FeO + HaO - Fe3O4 + H 2
W i t h r e g a r d to t h e sulphuretted h y d r o g e n , which is
produced merely from t h e sulphur originally contained
in the ore, this decreases with t i m e ; ore which w h e n
put in the retorts contained 7 5 per c e n t of sulphur, after
a year in continuous use contained only 0*03 per cent.
I r o n C o n t a c t P l a n t * T h e fundamental a n d secondary chemical reactions involved in this process h a v i n g
been considered, t h e r e remains only t h e plant, a n d t h e
actual fuel consumption per 1000 cubic feet of h y d r o g e n
to b e described.
T h e Iron Contact plant is commercially manufactured
in two distinct types :
1. T h e Multi-Retort t y p e .
2. T h e Single R e t o r t type.
Fig. 10 shows a purely diagrammatic a r r a n g e ment of a multi-retort generator. T h e retorts a r e externally h e a t e d b y means of a g a s producer incorporated
in the retort bench. T h e even h e a t i n g of the retorts is
secured by t h e use of refractory baffles (not s h o w n ) a n d
by the admission of air for the proper combustion of t h e
producer g a s a t different points.
94
T h e retorts are a r r a n g e d so that either blue w a t e r

g a s or steam can b e passed through them by t h e operation of t h e valves A a n d B.
D u r i n g the reducing stage t h e valves A a n d D are
open, and B and C s h u t ; thus t h e reducing g a s passes
through the oxide, a n d since in practice t h e whole of the
carbon monoxide and hydrogen in t h e water g a s is not
used up in its passage through t h e retorts, it is passed
^Blue Water
Gas Inlet
Steamlnlet
FIG
IO.
back outside of them, giving up its remaining heat, and

consequently contributing to the external heating.
On t h e reducing stage being complete, the valves
A and D are closed, and B and C opened ; steam passes
through t h e retorts, a n d hydrogen issues past t h e valve
C to the water seal, a n d thence to scrubbers and purifiers,
a n d finally to t h e gasholder.
W h e n high purity hydrogen is required, on the reducing stage being complete, the valve A is first closed,
a n d then t h e valve B t u r n e d on, allowing the hydrogen
CHEMICAL
METHODS
95
st m a d e to pass, t o g e t h e r with t h e residual g a s , in

e retorts via the valve D . W h e n this p u r g i n g h a s
mtinued for a b o u t half a minute, C is o p e n e d a n d D
Dsed, t h e h y d r o g e n p r o d u c e d p a s s i n g via t h e w a t e r
al ultimately to the gasholder.
Fig. I I s h o w s a d i a g r a m of a single r e t o r t plant
FIG
II.
ten from Messerschmitt's specification, c o n t a i n e d in

lghsh p a t e n t N o . 18942, 1913.
T h i s p l a n t is circular in plan, a n d consists essentially
two cast-iron cylinders (19) a n d (20), t h e first of
lich is supported on its b a s e a n d free t o e x p a n d uptrds, while the other is h u n g from a flange at its top,
d is free to e x p a n d d o w n w a r d s
T h e a n n u l a r space
96
(3) between the two cylinders is filled with suitable

iron ore, while t h e circular space inside t h e smaller
cylinder (19) is filled with a checker w o r k of refractory
brick (8). T h e plant is operated b y first h e a t i n g t h e
refractory bricks (8) b y means of water g a s a n d air,
admitted through pipes (15) a n d (16), t h e products of
combustion g o i n g out to a chimney by the pipe (18).
T h e heating of the checker work is communicated by
conduction to t h e ore mass (3) ; w h e n this is at a suitable temperature (about 750 C.) the gas supply (15) is
shut a n d water g a s enters by the pipe (10), passing
up through the ore and reducing it in accordance with
t h e equations already given. W h e n t h e reducing g a s
reaches the top of the annular space (3) it mixes with
air entering by the pipe (16) and t h e unoxidised portion
(the amount of which varies, as has been shown in t h e
graph, Fig. 9) burns, heating u p t h e brick work,
and finally passing away to t h e chimney by the pipe
(18).
W h e n reduction is complete (after about twenty
minutes) pipes (16) and (10) are closed, and steam is
admitted through t h e pipe (17), which passes upwards
through the checker work (8) becoming superheated,
a n d then down through t h e contact mass (3), where it is
decomposed in accordance with t h e equations already
given, producing hydrogen, which passes out b y t h e
pipe (12), through a water seal, a n d t h e n c e to a g a s holder. W h e r e very pure hydrogen is required, a
p u r g i n g period can be introduced b y a d o p t i n g the
following procedure :
W h e n reduction is complete, pipes (18) a n d (16) are
closed, but pipe (10) is left open, a n d (12) still remains
closed.
CHEMICAL METHODS
97
O n the admission of steam by t h e p i p e (17) hydrogen

generated in the reaction space (3), which, together
h the residual water gas, is forced back into t h e
ter gas m a i n ( i o ) , thus t e n d i n g to increase t h e
irogen content of t h e w a t e r g a s in t h e gasholder.
After t h e lapse of sufficient t i m e (about half a
nute) pipe (12) is opened a n d (10) shut, t h e hydrogen
>sequently produced p a s s i n g via t h e water seal to
hydrogen holder. After t h e ore h a s originally been
ited by m e a n s of water g a s a n d air, admitted b y
ies (15) a n d (16), the h e a t can b e maintained entirely
the combustion of t h e unoxidised water gas, d u r i n g
reducing stage, by the admission of air by the pipe
" Burning off" can b e accomplished by the admisn. of air by the pipe (11), the products passing out b y
pipe (18). T h e top of the plant is fitted with four
ighted valves, o n e of which is s h o w n at (14).
The
:sserschmitt plant is not in commercial employment
this country, b u t it is considerably used b o t h in
rmany a n d in the U n i t e d States, w h e r e the standard
t contains about 5 t o n s of iron ore, with a production
Dver 3000 cubic feet per hour.
Fuel C o n s u m p t i o n * I n the multi-retort type of
nt, the consumption of w a t e r g a s is about 2*5 cubic
t per cubic foot of h y d r o g e n produced, while in t h e
gle retort type, where t h e water g a s is employed
h for reduction and heating, t h e consumption is
>ut 3'5 per cubic foot of h y d r o g e n produced
In
h type of plant, if t h e s a m e kind of coke is used,
h for t h e production of water g a s a n d for all heating,
luding steam raising, b o t h for t h e process and for its
7
98
auxiliary machinery, such as blowers, feed pumps, e t c ,

t h e hydrogen yield from each is a b o u t :
6500-7000 cubic feet of h y d r o g e n per ton of
average soft coke.
Relative A d v a n t a g e s of the Multi* and Single Retort Plants*While in fuel consumption there is little
to choose between the two plants, there is undoubtedly
less complication in t h e single retort p l a n t than in the
multi, owing to the fewer joints, etc., which are at high
temperature.
A n o t h e r a d v a n t a g e in the single retort type lies in
the fact that fuel is consumed at two points only :
1. F o r the production of steam, for t h e process and
auxiliary machinery.
2. F o r the production of the necessary water gas.
In the multi-retort type, there is also fuel required
for the supply of t h e producer, which heats the retort
b e n c h ; however, this additional complication can be
eliminated by h e a t i n g the retorts externally by means
of water gas, a procedure which is a d o p t e d in at least
one commercial h y d r o g e n plant.
W i t h the gradual failure of the retorts themselves
from their oxidation by t h e steam, the advantage again
lies with the single r e t o r t type, as it is a simpler job to
draw the cast-iron liners, and replace them, than it is to
replace the individual retorts a n d m a k e the various pipe
joints.
T o sum up, while in chemical efficiency there is
little to choose b e t w e e n the two types, the advantage on
t h e whole appears to lie with t h e single retort type, on
account of its greater simplicity of repair.
T h e following patents with regard to this process are
in existence :
Oettli.
Betou.
Lewes.
Hills & L a n e .
Elworthy.
Vignon.
L a n e & Monteux.
Dellwick & Fleischer.
Lane.
Caro.
Strache.
Messerschmitt.
a
Lane.
English
jj
U.S.
French
16759.
75i8.
20752.
10356.
778182.
373*7*'
386991
M
English
395132
I759I11878.
German
249269
2537O5971206.
12117.
263390
263391.
268062.
1028366.
1040218.
US.
English
German
US
II
Badische Anilin
und S o d a
Fabrik.
French
Messerschmitt.
Badische Anilin
und S o d a
Fabrik.
Badische Anilin
und S o d a
Fabrik.
99
1885.
1887.
1890.
1903.
1904.
1907.
1908.
1908.
1909.
1910.
1910.
1910.
191c.
1912.
1912
1912.
1912.
1912.
1912.
1912.
English
440780.
461480.
461623.
461624.
18942.
19131913
19131913.
French
453077-
1913
459918.
1913.
ioo
Lane.
U.S.
patent
Berlin A n h a l t i s c h e
Maschinenbau. E n g l i s h
,,
Pintoch.
French
Berlin Anhaltische
Maschinenbau English
1078686.
1913.
28390
466739.
1913.
1913.
6155
1914
W i t h B a r i u m S u l p h i d e . I n t h e previous process
which was considered, steam was decomposed by means
of spongy i r o n ; in t h e present process, instead of iron,
barium sulphide is used.
If s t e a m is passed over barium sulphide h e a t e d to a bright red heat, the following
reaction takes place :
BaS + 4H 2 O - BaSO4 + 4H 2 .
T h e barium sulphate p r o d u c e d m a y b e reduced by
heating with coke t o barium sulphide in accordance
with the following equation :
BaSO4 + C = BaS + 4CO.
T h e barium sulphide can b e e m p l o y e d for the
g e n e r a t i o n of fresh h y d r o g e n a n d t h e carbon monoxide
can be used for s u p p l y i n g a portion of t h e heat which is
required for the process.
T h e process is protected b y F r e n c h p a t e n t 361866,
1905, in t h e n a m e of Lahousse.
A s o m e w h a t similar process to t h e L a h o u s s e has
been protected by F r e n c h p a t e n t 447688, 1912, in the
names of Teissier a n d Chaillaux. In this process barium sulphate is h e a t e d with m a n g a n o u s oxide, when the
following reaction t a k e s place .
BaSO4 + 4M11O = BaS + 4MnO2.
T h e resulting m i x t u r e of b a r i u m sulphide a n d m a n -
CHEMICAL METHODS
101
ganese dioxide is t h e n raised to a w h i t e heat, w h e n the

following reaction takes place -
BaS + 4MnO2 = BaS + 4MnO + 2O2
W h e n the
is passed over
ganous oxide,
cordance with
reaction is complete, s t e a m u n d e r p r e s s u r e
t h e mixture of b a r i u m sulphide a n d m a n with t h e production of h y d r o g e n , in acthe following equation :
BaS + MnO + 4H 2 O = BaSO4 + MnO + 4H 2 .

T h e process is t h e n ready to b e s t a r t e d again.
W h e t h e r it will h a v e a considerable commercial application remains y e t to b e proved.
THE
BADISCHE CATALYTIC
PROCESS
U s i n g a Catalytic A g e n t . I n t h e processes so far

described for t h e production of h y d r o g e n from s t e a m ,
the steam has b e e n decomposed b y t h e action of s o m e
solid which itself u n d e r g o e s a distinct chemical c h a n g e
requiring t r e a t m e n t to b r i n g it back into a form in which
it can be a g a i n used for t h e production of h y d r o g e n .
In the process a b o u t to b e described t h e s t e a m is d e composed by virtue of a catalytic a g e n t which itself
undergoes n o p e r m a n e n t c h a n g e .
T h i s process, which is protected b y p a t e n t s ( e n u m e r ated at t h e e n d of this n o t e ) by t h e Badische Anilin
und Soda F a b r i k Gesellschaft, consists of t h e following
stages:
First, Blue W a t e r G a s is p r e p a r e d in a n ordinary
producer a n d purified from suspended m a t t e r b y m e a n s
Df a scrubber ; t h e n into this clean w a t e r g a s steam is
introduced a n d t h e mixture p a s s e d o v e r a catalytic
naterial, w h e r e t h e following reaction t a k e s place :
Water gas
H a + CO + H 2 O - 2H2 + CO2.
102
Thus it is seen that the carbon monoxide contained

in the blue gas is oxidised by the steam, which itself is
decomposed with the production of hydrogen.
Now carbon dioxide is readily soluble in water,
consequently the product of the reaction is passed under
pressure through water, where it is absorbed, leaving a
comparatively pure hydrogen.
Starting with blue water gas, which may be roughly
taken as being composed of 50 per cent, hydrogen and
50 per cent, carbon monoxide, the composition of the
gas, after the introduction of the steam and passage over
the catalyst, is approximately as follows :
Per Cent,
by Volume.
Hydrogen
.
65
Carbon dioxide
.
30
monoxide .
.
1*2-1 "8
Nitrogen . . .
.
.
2*5-4
The bulk of the carbon dioxide is absorbed by
means of water, but if the hydrogen is required for
aeronautical purposes, the gas is finally passed through
either a caustic soda solution or over lime. Traces of
carbon monoxide are removed by passing the gas under
pressure through ammoniacal cuprous chloride solution.
As a result of these final purifications a gas is obtained
of approximately the following composition :
Per Cent,
by Volume
Hydrogen
97
Nitrogen .
.
.2*7
Carbon dioxide .
.
,, monoxide .
.
'3
In practice it was stated that in commercial ironcontact plants the consumption of blue gas was from
103
'3 t 0 3"5 cubic feet per cubic foot of h y d r o g e n ultimately produced.

In t h e method which has just been described t h e
Dnsumption of blue g a s is about i"i to 1*3 cubic feet
er cubic foot of h y d r o g e n , or assuming a consumption
35 lb. of coke per 1000 cubic feet of water g a s proiiced, t h e h y d r o g e n yield is 49,000 to 58,000 cubic feetj
er ton of soft coke.
In the operation of this process, the blue water gas,
)gether with a requisite a m o u n t of steam, is passed over
le catalytic material at a temperature of 400 to 500 C.
ince t h e oxidation of t h e carbon m o n o x i d e is exotherlic, after the reaction chamber is heated to t h e temerature of 400 to 500 C , no more heat n e e d be
applied from external sources.
T h e chemical composition of the catalyst a p p e a r s to
e somewhat variable, but, as in the case of the catalyst
sed in the fat-hardening industry, its physical condition
Efects t h e efficiency of the process. I n the p a t e n t s pro:cting this process a variety of methods a r e described
>r the preparation of t h e catalyst, but t h e following
lay be given as r e p r e s e n t a t i v e .
" Dissolve a mixture of 40 parts by weight of ferric
itrate, 5 parts of nickel nitrate, a n d 5 parts of chromium
itrate, all free from chlorine
Precipitate with potasum carbonate, filter, wash, form into masses a n d dry."
T h e quantity of nickel can be varied, for example,
etween t h e limits of 10 parts and three parts of nickel
itrate
T h i s contact mass is used at a t e m p e r a t u r e of 400
5 5OO C.
A s is t r u e of all catalysers, the above a p p e a r s to
e subject to " poisoning," the chief poisoners being
104
chlorine, bromine, iodine, phosphorus, arsenic, boron,

and silicon in some forms ; hence in the preparation of
the catalyser, as well as in the manufacture of the water
gas, precautions must be taken to prevent the presence
of these " poisons ".
The mixture of blue water gas and steam is passed
over the catalyst at approximately atmospheric pressure.
On leaving the reaction chamber after passage through
suitable regenerators, the gas is compressed to a pressure
of 30 atmospheres (441 lb. per sq. inch) and then passes
to the bottom of a high tower packed with flints, in
which it meets a downward flow of water which absorbs
the carbon dioxide, and also the sulphuretted hydrogen
which is present in the gas to a very slight extent. The
energy in the water leaving the tower is recovered in
the form of power by letting it impinge on a Pelton
wheel.
The removal of the 2 per cent, of carbon monoxide
is accomplished in a similar tower , only in this case
a solution of ammoniacal solution of cuprous chloride is
used instead of water. Given an adequate size of tower
and volume of the cuprous chloride solution, the pressure
at which the gas is introduced into the tower may be as
low as 30 atmospheres (441 lb. per sq inch); however,
where the gas is to be used for making synthetic ammonia it is usual to compress it to 200 atmospheres
(2940 lb. per sq. inch) before passing it through the carbon
monoxide absorbing tower. The use of this high pressure is ultimately necessary in the ammonia process and
it reduces the size of the tower which has to be employed.
The cuprous chloride solution, after leaving the absorption tower, is passed through a small vessel, in which
it gives up its carbon monoxide. The gas evolved from
CHEMICAL METHODS
105
e solution is passed t h r o u g h water in o r d e r to p r e v e n t

y ammonia loss.
T h e a d v a n t a g e s of this process o v e r t h e I r o n C o n t a c t
ocess are :
1. It is continuous in operation.
2. It is more economical.
3. T h e whole of t h e sulphur c o m p o u n d s in the b l u e
s are converted into sulphuretted h y d r o g e n a n d a r e
mpletely absorbed b y t h e high p r e s s u r e w a t e r scrubT h e disadvantages as c o m p a r e d with t h e I r o n Con:t process a r e :
1. G r e a t e r complexity of operation
2. F o r aeronautical purposes t h e p e r c e n t a g e of nitron is high.
Description of Plant, T h e d i a g r a m ( F i g . 12)
ows the m e t h o d of operation of this process.
Steam
ters by the pipe A a n d mixes with blue w a t e r g a s
tering b y t h e pipe B, t h e speed of flow of each b e i n g
dicated o n separate g a u g e s a s shown. T h e m i x t u r e of
iam and g a s p a s s e s ' t h r o u g h the r e g e n e r a t o r or supera t e r C a n d flows, as indicated b y t h e arrows, over
fractory tubes, through which t h e h o t products of the
action a r e flowing in t h e reverse direction. T h e h e a t e d
xed gases flow via the p i p e F into t h e g e n e r a t o r and,
:reasing in t e m p e r a t u r e , pass t h r o u g h t h e catalytic
iterial, w h e r e reaction takes place with t h e evolution
heat
T h e y then flow a s indicated by t h e arrows
ck t h r o u g h t h e regenerator, parting with their heat to
e incoming m i x t u r e of blue water g a s and steam.
Thermo-couples a r e placed in t h e contact mass so
at its t e m p e r a t u r e may b e controlled by increasing or
io6
r e d u c i n g t h e q u a n t i t y of s t e a m in t h e i n c o m i n g g a s e o u s
mixture.
The
whole apparatus
is v e r y
effectively
lagged
to
reduce the heat losses to a minimum.

To Milli -voltmeter
Thermo-couples
for Temperatures
between 450 & 500'C
Superheater or
Regenerator
Contact
Material
WaterGas
Inlet
Orifice Gauge
Diatomite Brick Cover

throughout, bound with
Painted Cloth
Hydrogen
and C02
Outlet
To Mi Hivoltmeter
FIG
i2.
T h e following p a t e n t s o n this process b y the B a d i s c h e

A n a l i n a n d S o d a F a b r i k a r e in e x i s t e n c e :
English patent
French
27117.
1912.
27963.
1913.
459918.
1913.
CHEMICAL METHODS
iojr
T h e following p a t e n t s relating to the g e n e r a l chemi1 reaction in this process h a v e been taken o u t :

sssie du Motay.
,,
,,
,,
patent 229338.
229339.
M
IJ
229340.
>>
M
English
22340.
French
,,
355324
U.S.
854I57-
1880.
1880.
1880.
1891.
1905.
1907.
,,
1909.
1910.
U . S.
i)
>> J>
illman & E l worthy.
[worthy.
His & Eldred.
lem. F a b r i k Greisheim
British
Elektron
German
aber & Muller.
2523.
237283.
- U s i n g Lime.If carbon monoxide together with

:am is p a s s e d over lime a t a t e m p e r a t u r e of a b o u t
o C , t h e m o n o x i d e is a b s o r b e d with the formation of
lcium carbonate, a n d h y d r o g e n is evolved in accordce with t h e following e q u a t i o n :
CaO + H 2 0 + CO = CaCO3 + H 2 .
Investigation of the a b o v e reaction by Levi & P i v a x
iicates t h a t t h e chemical c h a n g e takes place in two
iges, in t h e first of which calcium formate is produced,
lile in t h e second it is d e c o m p o s e d with t h e evolution
hydrogen and carbon m o n o x i d e as is shown in the
[lowing e q u a t i o n s .
(1) CaO + H 2 0 + 2CO = Ca(COOH)2j
(2) Ca(COOH)2
- CaCO3 + CO + H a .
It can, however, b e s e e n from these equations t h a t
latever volume of carbon monoxide is p e r m a n e n t l y
isorbed, an equal volume of hydrogen is evolved.
Now, since blue water g a s is, roughly speaking, half
r
drogen a n d half carbon monoxide, by passing it over
lc
'Journ Soc. Chem Ind," 1914, 310
108
lime under the conditions stated above, a gas equal in

volume to the water gas, but wholly composed of hydrogen, is produced.
In the commercial operation of this process, the lime
is contained in a tower, which is initially heated to a
temperature of about 5000 C , but since the absorption
of the carbon monoxide is exothermic, after the process
has started, no further heating is required.
When the lime has become sluggish in its action, by
the formation of a crust of calcium carbonate, the blue
gas is diverted through a similar tower, while the contents of the original tower are heated m situ to a temperature sufficiently great to decompose the calcium
carbonate, and thus the tower is again ready for use.
This process is protected by the following patents :
Chem. Fabrik Greisheim
Elektron.
British patent 2523. 1909.
Dieffenbach & Moldenhauer.
8734. 1910
Ellenberger.
U.S.
989955 1912.
Chem. Fabrik Greisheim
Elektron.
British
13049. 1912.
(4) Miscellaneous Methods of Making Hydrogen*
THE CARBONIUM GESELLSCHAFT PROCESS.
From Acetylene.If acetylene is compressed and

then subjected to an electric spark it undergoes dissociation into its elements.
Acetylene can be most easily generated from the
action of water on calcium carbide, thus :
CaC2 + 2H2O - C2H2 + Ca(OH)2.
109
T h e acetylene produced is then compressed in very

trong cylinders and subjected to an electric spark, when
tie following reaction takes place :
C2H2 = Q + H 3
If the acetylene is produced from calcium carbide,
pproximately 178 lb. of calcium carbide a n d 100 lb. of
/ater are theoretically required to produce 1000 cubic
set of h y d r o g e n at 40 F . and 30 inches barometer,
/hile, at t h e s a m e time, 39 lb. of carbon in t h e form of
imp-black is produced.
This process is employed by t h e Carbonium Gesellchaft of F r e d e r i c k s h a v e n for the inflation of airships,
irhile the carbon produced is sold a n d is used in m a k i n g
irinters 1 ink. A s u s e d by this company, the g a s is
ompressed to a b o u t 2 atmospheres (29*4 lb. p e r sq.
nch) prior to sparking.
T h e following patent, relative to this process, is in
xistence:
Bosch. G e r m a n patent 268291.
1911.
T h e decomposition of acetylene m a y b e obtained b y

leating ; thus, if acetylene derived from calcium carbide
r some other source is passed through a t u b e h e a t e d to
bout 500 C. it decomposes, in accordance with t h e
ollowing equation, with the evolution of h e a t :
CgHg = Ca + Hg.
Such is t h e quantity of heat liberated t h a t after t h e
emperature of t h e t u b e has been raised until decom)osition of the acetylene begins no further external heat
s required.
T h e carbon p r o d u c e d may be chiefly r e m o v e d b y
iltering t h e gas, while t h e residue which still remains
nay be removed b y scrubbing with water.
HO
This process is protected by t h e following p a t e n t s :
Picet. French p a t e n t
English
German
421838.
421839.
24256.
255733.
1910.
1910.
1912.
F r o m Hydrocarbon Oils*While the decomposition

of acetylene is attended with the evolution of heat, most
other hydrocarbon gases absorb heat when they decompose into their constituents; consequently, to produce
hydrogen from other hydrocarbon g a s or volatilised
hydrocarbon oils, it is necessary to supply h e a t during
t h e process.
T h e necessary heat may be supplied by passing t h e
hydrocarbon g a s or vaporised oil t h r o u g h a t u b e of r e fractory material which is externally heated, or t h e ingenious Rincker-Wolter method may b e used. I n this
process t h e rough principle is to use a g e n e r a t o r similar
to a " blue-gas " generator filled with coke. B y m e a n s
of a n air blast t h e t e m p e r a t u r e of the coke is raised to
about 1200 C , then, when this t e m p e r a t u r e h a s b e e n
reached, the air supply is stopped and crude oil is blown
in a t the bottom of the h o t coke.
T h e oil is immediately volatilised, a n d passes by expansion u p through t h e h o t coke, during which process
it is decomposed into hydrogen and carbon, t h e latter
to a large extent attaching itself to the coke a n d becoming a source of fuel. W h e n the t e m p e r a t u r e h a s fallen
too low t o effect a complete decomposition of t h e crude
oil the injection is stopped and t h e t e m p e r a t u r e of t h e
coke again raised by m e a n s of t h e air b l a s t T h e g a s
produced b y this process is stated to h a v e t h e following
composition :
CHEMICAL
METHODS
in
Per Cent,
by Volume
96*0
1*3
Hydrogen .
Nitrogen
Carbon monoxide
T h e cost of h y d r o g e n m a d e by this process must

lepend almost entirely on t h e price of crude o i l ; it is
tated that, with crude oil at twopence a gallon, hydrogen can b e produced for about seven shillings a t h o u s a n d
ubic feet. 1
T h e following patents deal with this o r s o m e w h a t
imilar p r o c e s s e s :
xeisenberger.
lincker & W o l t e r .
Jerlin Anhaltische
/[aschinenbau A. G
). Ellis.
F r e n c h patent
,,
,,
German
French
English
U.S.
361462.
391867.
391868.
1905.
r9o8.
1908.
267944.
466040.
2054.
1092903.
1913.
1913.
1914
1914.
F r o m S t a r c h . W h e n yeast, which is a living

rganism, is introduced into a solution containing
jgar, fermentation results with t h e production of
[cohol a n d carbon dioxide, which m a y b e e x p r e s s e d in
n equation as follows :
A n analogous process to the above is employed
)mmercially for t h e production of acetone a n d butyl
cohol.
W h e n what is k n o w n as t h e F e r n b a c h bacillus is inoduced into starch jelly, (C 6 H I O O 5 ), acetone, ( C H 3 ) 2 C O ,
* Ellis, "The Hydrogenation of Oils" (Constable).
112
and butyl alcohol, CH3CH3CHaCH3OH, are produced ;

at the same time there is an evolution of gas which is
chiefly hydrogen and carbon dioxide, but it also contains a little nitrogen.
As there is a great demand for acetone in certain
localities, large quantities of hydrogen in this impure
form are being produced as a by-product. If the
carbon dioxide is absorbed by passing the gas under
pressure through water (Bedford method), a gas is produced of about the following composition
Hydrogen .
.
. 94fo
Nitrogen
.
. . .
6'o
The above is not a process for the production of
hydrqgen, but the hydrogen produced may be frequently
usefully employed if there is a local demand for it.
CHAPTER
IV.

CHEMICO-PHYSICAL
METHODS.
Lindc*Frank'Caro P r o c e s s * T h e m o s t i m p o r t a n t
ethod of producing hydrogen, in which chemical a n d
lysical m e t h o d s are employed, is one in which t h e
emical process results in t h e production of blue w a t e r
s, and t h e physical in t h e separation of t h e chemical
mpounds (chiefly carbon monoxide) from t h e h y d r o g e n
liquefaction.
'HE SEPARATION OF H Y D R O G E N FROM B L U E
WATER
GAS.
T h e separation of mixed gases by liquefaction is

subject of very great complexity a n d o n e into the
ricacies of which it is not intended to g o in this work,
t for further information the attention of t h e reader
directed to t h e t w o following books :
" T h e Mechanical Production of Cold," by J. A.
ving. ( C a m b r i d g e University Press.)
" Liquid Air, O x y g e n , Nitrogen," by G. Claude.
& A. Churchill.)
All gases a r e capable of being liquefied, but in t h e
e of h y d r o g e n and h e l i u m l t h e difficulties a r e so g r e a t
1
This gas, which was the last to resist liquefaction, was first
efied on ioth July, 1908, by Professor Kamerhngh-Onnes.
(113)
8
H4
t h a t it is only b y m e a n s of t h e highest technical skill a n d

very costly a p p a r a t u s t h a t this can b e accomplished.
Originally it was considered that to obtain a g a s in
t h e liquid state t h e sole necessity was p r e s s u r e ; however, all g a s e s possess a physical property k n o w n as
critical temperature}
T h e critical t e m p e r a t u r e of a
g a s is t h a t t e m p e r a t u r e a b o v e which the g a s cannot b e
liquefied, h o w e v e r g r e a t the pressure to which it is subjected.
Prior to the realisation of the existence of t h e critical
temperature, chemists a n d physicists subjected various
gases to enormous pressures in t h e hope of causing t h e m
to liquefy, and, t h o u g h they failed, it is interesting to
observe from t h e accounts of their experiments that t h e
compressed gas attained a density g r e a t e r than t h e
s a m e g a s in t h e liquid state at atmospheric pressure.
Besides critical t e m p e r a t u r e , a n o t h e r term requires
definition, that is, criticalpressure\
which is the pressure
which must b e exerted on a g a s cooled to its critical
t e m p e r a t u r e to p r o d u c e liquefaction.
T h e following t a b l e of critical t e m p e r a t u r e s a n d
pressures of the constituents of blue water g a s is interesti n g :
Gas
"
Hydrogen .
.
Carbon monoxide
dioxide.
Nitrogen
Methane
Oxygen
1
Template
Cnfcal Pressure.
- 2 34*0 C.
136 o
+ 3 9 2
- 146 o
- 82*0
+ 100 o
- 118-0
294 lb. per sq in

492
"3*
485
,,
820 ,,
1304
735
Discovered by Andrews, 1863
CHEMICO-PHYSICAL METHODS
115
F r o m this t a b l e it is seen that t h e critical temperaure of h y d r o g e n is 88 C. below t h a t of its nearest

.ssociate, n i t r o g e n ; consequently, if t h e blue water g a s
vere cooled to 146 0 C. while subjected to a pressure of
o m e w h e r e a b o u t 500 lb. per s q u a r e inch, the whole of
he gas, with t h e exception of t h e hydrogen, would
iquefy; t h e r e f o r e , separation of a liquid from a g a s
>eing a simple m a t t e r , t h e problem of the production of
lydrogen from b l u e water g a s would be solved.
If a g a s is c o o l e d below its critical t e m p e r a t u r e t h e
>ressure which h a s to b e applied to p r o d u c e liquefaction
3 much r e d u c e d .
N o w , since t h e boiling point of a
[quid a n d the c o n d e n s i n g point of a vapour u n d e r the
a m e pressure a r e t h e s a m e temperature, t h e boiling
ioints of t h e v a r i o u s g a s e s contained in blue water g a s
an b e studied w i t h a d v a n t a g e .
BOILING P O I N T S
OF SOME
PHERIC
Gas
Hydrogen
. . .
Carbon monoxide .
,,
dioxide
.
Nitrogen .
Methane .
.
.
.
Oxygen
L I Q U I D G A S E S AT A T M O S PRESSURE.
.
.
.
.
.
Boiling Point.
- 253*0 C.
- 190 o
- 8o#o
- 195*5
. - 164 7
. - 61 "6
- 182-5
.
Therefore, it can b e seen that, if blue water g a s

rere cooled a t a t m o s p h e r i c pressure to a temperature
elow - 195 '5 C , the whole of t h e constituents of t h e
as, other t h a n h y d r o g e n , would b e liquefied, a n d consquently a n e a s y separation could b e made.
T o s u m m a r i s e , t h e liquefaction of the constituents of
n6
blue water gas, other t h a n h y d r o g e n , can b e accomplished either b y a m o d e r a t e d e g r e e of cooling a n d t h e

application of pressure, or by intense cooling a n d no
application of pressure.
PRODUCTION OF HYDROGEN FROM WATER GAS BY THE
LINDE PROCESS
H2S
COa
Sulphuretted Carbon
Hydrogen. Dioxide.
5%
3-5%
CH 4
Meth
-47O
CO
N2
Carbon
^
6
Monoxide.
39 67.
4/.
H2
Hydrogen.
J
57.
Oxide Boxes. H2S partly absorbed.

Compressor.
Pressure Water Scrubber
20 Atmospheres (294 lb / Q " ) .

COa & HaS almost entirely absorbed.
Caustic Soda Scrubber (NaOH 307J, last traces CO2 & H2S absorbed
Ammonia Cooler. Water Vapour condensed,
Temperature reduced to - 25 C.
Linde Still. Final Temperature - 2050 C.
Methane, Carbon Monoxide & Nitrogen liquified.
Gaseous Hydrogen
Ha
977O by Volume
CO
2
N2
1
Methane, Carbon Monoxide

& Nitrogen. On evaporation to gas engine operating the whole plant.
In t h e L i n d e - F r a n k - C a r o process t h e b l u e w a t e r
g a s is compressed to 20 atmospheres, a n d under
pressure it is passed t h r o u g h water, which r e m o v e s
CHEMICO-PHYSICAL M E T H O D S
117
practically t h e whole of the carbon dioxide a n d sulphuretted h y d r o g e n . It is t h e n passed t h r o u g h t u b e s

:ontaining caustic soda, which r e m o v e s t h e r e m a i n i n g
traces of c a r b o n dioxide, sulphuretted h y d r o g e n , a n d
water.
T h e g a s thus purified from these constituents n o w
passes to t h e separator proper ; the r e a s o n for this p r e liminary removal of s o m e of the constituents of t h e blue
water g a s is d u e to t h e fact that, in t h e separation of t h e
zarbon monoxide a n d nitrogen, such low t e m p e r a t u r e s
have to b e reached t h a t t h e water, sulphuretted h y d r o g e n ,
i n d carbon dioxide would b e in t h e solid state, a n d
would, therefore, tend to block up t h e pipes of t h e a p paratus.
T h e a p p a r a t u s operates in t h e following manner,
which will b e more readily understood by consulting t h e
diagram ( F i g . 1 3 ) :
T h e purified w a t e r g a s passes d o w n t h e t u b e A,
through coils in the vessel B, which is filled with
liquid carbon monoxide boiling at a t m o s p h e r i c p r e s s u r e
( 190 C ) . N o w , since the water gas is u n d e r pressure and is p a s s i n g t h r o u g h coils cooled t o its t e m p e r a ture of liquefaction a t atmospheric pressure, t h e b u l k of
it liquefies (theoretically m o r e g a s should b e liquefied in
the tubes t h a n is e v a p o r a t e d outside t h e m ) .
T h e gas, containing a considerable a m o u n t of liquid
saturated with hydrogen, passes into t h e vessel C,
which is surrounded by liquid nitrogen boiling u n d e r
reduced pressure g i v i n g a t e m p e r a t u r e of 205 C.
H e r e t h e remainder of the carbon m o n o x i d e a n d t h e
nitrogen originally contained in t h e g a s liquefies a n d
hydrogen of approximately the following composition
passes u p t h e t u b e E :
US
MANUFACTURE OF
HYDROGEN
ki
s
!
_AJVaterGasIn/et A **i
""*
Carbon Monoxide Outlet
=njU
D Nitrogen Outlet D.
u
Liquid Nitrogen Inlet
F I G
13 D i a g r a m
s h o w i n g
L i n d e - F r a n k - C a r o
Process.
Per
by
1
H y d r o g e n
Nitrogen
C a r b o n
m o n o x i d e
h y d r o g e n
sulphur
W h e n
t h e
Messrs
97*0
-
O r g a n i c
supplied
Sulphuretted
Cent,
Volume
A r d o l
t h e author
c o m p o u n d s
g a s
i s
r e q u i r e d
of Selby,
with
this
.
.
.
.
t o
o f
Yorks, w h o e m p l o y
information
nil.
b e
h i g h
2 0
p u r i t y
this process,
it
is
kindly
119
lbsequently passed over calcium carbide or s o d a lime,

le reactions of which processes will b e dealt with later.
D u r i n g t h e operation of the process liquid c a r b o n
lonoxide a n d s o m e liquid n i t r o g e n collects in C.
Tow this liquid g a s is u n d e r pressure a n d can therefore
2 run b a c k t h r o u g h t h e tube F via t h e cock G
Lto t h e vessel B ; b u t B is at a t m o s p h e r i c pressure,
Dnsequently some of t h e liquid g a s passing t h r o u g h G
ill be volatilised, with consequent fall in t e m p e r a ire of t h e remainder.
T h e liquid nitrogen used in t h e vessel D is prouced in a special L i n d e machine from the a t m o s p h e r e .
T h e vapour of carbon monoxide, with a little
itrogen a n d h y d r o g e n , from t h e vessel B is used to
ool the incoming purified water gas, as is shown in t h e
iagram. T h i s m e t h o d of using t h e cold s e p a r a t e d
ases for cooling t h e g a s g o i n g into the a p p a r a t u s is
;rmed " Cooling by counter-current heat exchangers,"
nd it m a y b e r e g a r d e d as the essence of efficiency in
11 low t e m p e r a t u r e g a s separation.
T h e consumption of power in this process is theoetically v e r y small, as much carbon monoxide should
>e liquefied in t h e coil in the vessel B as is volatilised
>utside it (this is theoretically t r u e w h e n t h e pressure
>f the g a s passing t h r o u g h the coil is atmospheric)
-lowever, in practice, the necessity for p o w e r c o n s u m p 1011 arises from t h e fact t h a t liquid n i t r o g e n must
)e continuously supplied to the vessel D in order to
jrevent t h e t e m p e r a t u r e of the plant rising from exernal infiltration of heat, which t a k e s place in spite of
he most effective lagging.
In practice, t h e p o w e r obtained from using t h e sepa*ated carbon monoxide as a fuel is sufficient to run all
120
the machines necessary for the operation of a plant producing 3500 cubic feet of hydrogen or more per hour.
Thus, to very roughly indicate the cost of operation
of this process, neglecting all depreciation, etc., it may
be said that, on a plant of the size mentioned above,
unit volume of blue water gas yields "4 volume of
hydrogen of about 97 per cent, purity, or, on the basis
of a coke consumption of 35 lb. per 1000 cubic feet of
water gas, the hydrogen yield is 25,500 cubic feet per
ton of coke.
Purification of Hydrogen.Where very pure
hydrogen is required it is necessary to employ chemical
methods to remove the 3 per cent, of impurity, which
may be done by passing the gas through heated soda
lime, where the carbon monoxide is absorbed in accordance with the following equation :
2Na0H + CO = Na2CO3 + H2,
or, on the other hand, it may be passed through heated
calcium carbide (over 300 C), which possesses the
advantage of not only removing the carbon monoxide
but also the nitrogen. The reactions taking place are
indicated in the following equations :
CaCa + CO = CaO + 3C,
CaC2 + N2 - CaCN2 + C.
The following is given as an analysis of the gas
purified by means of soda lime .
Per Cent,
by Volume,
Hydrogen . . .
. 9 9 2-99-4
Carbon monoxide
.
.
nil
Nitrogen . . .
.
o*8-o 6
The following patents are in existence for the pro-
121
ztion of h y d r o g e n by liquefaction m e t h o d s from blue

ter g a s :
worthy.
ank.
aude.
:s-fur Linde's E i s tnaschinen A . G .
von Linde.
French patent
English
French
>]
U.S.
lemical purification
ank.
French
ti
37599L
1905.
1906.
1906
4179831020102.
1020103.
1027862
1027863
1911.
1912.
1912.
1912
1912.
371814.
1906.
35532426928.
D i f f u s i o n . T h e separation of h y d r o g e n from t h e
ler constituents of blue w a t e r g a s h a s b e e n proposed,
lploying diffusion for t h e purpose. G r a h a m expressed
2 law of diffusion of gases as .
" T h e relative velocities of diffusion of a n y t w o
ses are inversely as the s q u a r e roots of their densities."
T h a t is to say, if a m i x t u r e of t w o gases of different
nsities is passed t h r o u g h a p o r o u s t u b e , e.g. unglazed
rcelain, in a given time, m o r e of t h e lighter g a s would
ve passed t h r o u g h t h e walls of t h e t u b e t h a n of t h e
avier, or, t o t a k e a concrete example, s u p p o s e t h e
ixture of g a s e s was o n e composed of equal p a r t s b y
lume of h y d r o g e n a n d o x y g e n , then, since their
nsities a r e as 1 t o 16, a n d since, therefore, t h e roots
their densities a r e as 1 to 4, in a g i v e n t i m e four
nes as much h y d r o g e n would diffuse t h r o u g h t h e
sdium a s o x y g e n .
T h e densities a n d t h e s q u a r e r o o t s of the densities
the constituents of blue water g a s a r e g i v e n below ;
122
Hydrogen .
Carbon monoxide
,, dioxide
Nitrogen
Methane .
Oxygen
Density.
jW
i
14
22
14
8
17
16
1
3*7
47
37
28
41
4'
From which it will be seen that, if blue gas were

passed continuously through a porous tube, the gas diffusing through the tube would contain more hydrogen
than the blue gas originally contained. Of course, in
the successful operation of a diffusion separation it is
necessary to remove the gas which diffuses through the
porous medium as well as the residue which is left undiffused. The former may be done by maintaining a
constant pressure by means of a suction pump, while
the latter can be done by regulating the speed of flow
through the diffusion tube. It is, of course, essential
that the undiffused gsCs must be removed from contact
with the porous medium after a certain time, as it is only
a matter of time before the whole of the gas will diffuse
through the medium, and thus destroy the work of
separation.
THE DIFFUSION MEDIUM.
The selection of the diffusion material is a subject

of considerable difficulty , if the porosity of the material
is too great no diffusion takes place, but the gas passes
through the material without any appreciable separation
taking place. Thus, if a mixture of hydrogen and
oxygen is passed through a fine capillary tube, the gas
123
i n g will b e found to b e of the same composition as

original g a s .
It is interesting to note in this connection that, if
2 h y d r o g e n were first passed t h r o u g h t h e t u b e a n d
1 p u r e oxygen, in a g i v e n time m o r e h y d r o g e n by
ime would pass through the t u b e t h a n oxygen.
s differential rate of flow t h r o u g h tubes is called
ranspiration ".
If the porosity of t h e material is insufficient, t h e time
lired to effect separation is unduly long. It m a y , in
connection, b e mentioned that it has from t i m e to
i been s u g g e s t e d that by means of diffusion it would
)ossible t o separate a mixture of gases of different
sities without t h e consumption of power. 1
How-, in practice this has not been found to b e the case,
n order to obtain a reasonable speed of separation,
fference of pressure between the two sides of t h e
ision material has to b e maintained.
J o u v e a n d Gautier h a v e employed a diffusion
hod in o r d e r to separate h y d r o g e n from blue w a t e r
and it is stated that, by a single p a s s a g e t h r o u g h a
JUS partition, the p e r c e n t a g e of carbon m o n o x i d e in
g a s passing through the medium was reduced from
jer cent, in the original g a s to 8 per c e n t
Whether
process h a s been employed on a commercial scale
ot known to the author, nor h a s h e a n y k n o w l e d g e
0 the a m o u n t of power required to obtain a definite
ime of h y d r o g e n practically free from carbon monle.
T h e following patents, in which diffusion h a s b e e n
1
It is theoretically impossible to separate a mixture of two gases

DUt the consumption of power, but the theoretical requirements
ilmost negligible.
i24
employed for separating mixed gases, have been taken

out:
Jouve & Gautier. French patent 372045. 1908
Hoofnagle.
U.S.
1056026. 1913
Separation by Centrifugal Force,When a mass is
compelled to move in a circular course a force acts on it
which is a function of its mass, linear velocity, and the
radius of curvature of its path, which may be expressed
as
Centrifugal force = 5
is.
where m = mass of the body5
v = its linear velocity,
R = the radius of curvature of its path.
Therefore, since a greater force is acting on the heavier
of two particles moving on the same course with the
same velocity, the heavier particle will tend to move
outward from its centre of rotation to a greater extent
than the lighter. This principle of centrifugal force is
employed industrially for many purposes, such as the
separation of cream from milk, water from solid bodies,
honey from the comb, etc., and it has been suggested
that it might be used to separate hydrogen from blue
water gas. However, though a certain amount of work
has been done on this problem by Elworthy1 and
Mazza,2 as far as the author knows no satisfactory results
have been obtained.
The special physical questions involved in the separation of gases of different densities by means of a
centrifugal machine have been considered theoretically
1
2
Elworthy, English patent, 1058 rgo6.

Mazza, English patent, 7421 1906
125
a n u m b e r of physicists, whose conclusions a r e t h a t

y high velocities must b e given t o the g a s t o obtain
7 appreciable separation ; it has b e e n s h o w n that, if a
im 3 feet in diameter a n d one foot l o n g filled with a
cture at 15 0 C , containing 80 per cent, of h y d r o g e n
1 20 per cent, of air, is rotated a t 20,000 revolutions
minute, a condition of dynamical equilibrium will
se w h e n t h e peripheral g a s a n d t h e axial g a s will
re the following composition :
Hydrogen
Air
.
.
.
Axial Gas.
97 8
. 2 - 2
Peripheral Gas
66i
33-9
Since t h e density of air a n d that of carbon m o n o x i d e

almost t h e s a m e (14*4 a n d 14*0) almost identical
oretical results could b e obtained b y g i v i n g a similar
ary motion to a mixture of 80 per cent, h y d r o g e n a n d
per cent, carbon monoxide. H o w e v e r , t h e enormous
ed of rotation a n d a practical m e t h o d of r e m o v i n g t h e
al and peripheral gases makes this question one of the
atest technical difficulty, a n d it m a y well b e t h a t t h e
ver consumption to p r o d u c e a g i v e n v o l u m e of h y d r o 1 from blue w a t e r gas may b e g r e a t e r t h a n t h a t
uired t o produce a n equal v o l u m e of h y d r o g e n b y
ctrolysis.
CHAPTER
V.

PHYSICAL
METHODS.
E l e c t r o l y s i s . W h e n an electric current passes

through a solid conductor a magnetic field is created
round t h e conductor and the conductor is h e a t e d b y the
passage of t h e current, both of which effects bear a
definite relationship to the m a g n i t u d e of the current
passing. S o m e liquids are also conductors of electricity,
e.g. m e r c u r y ; the passage of a current through such a
conductor produces results identical with those produced
in solid conductors. O t h e r liquids a r e also conductors,
but, besides the passage of the current creating a m a g netic field a n d a heating effect, a portion of the liquid is
split u p into two parts which m a y each b e a chemical
element, or one or either may be a chemical group.
T h u s , if two platinum plates a r e placed as shown in
the diagram, one plate being connected to the positive
pole of the battery and the other to the negative, then,
if a s t r o n g aqueous solution of hydrochloric acid is put in
the vessel containing the plates, decomposition of the
liquid will take place ; hydrogen will b e given off at the
negative plate or cathode, and chlorine at t h e positive
or anode.
If t h e solution of hydrochloric acid is replaced by o n e
of caustic soda t h e caustic soda is split up b y the current
(126)
PHYSICAL METHODS
127
ito oxygen, which is liberated at t h e anode, a n d metallic

idium which is deposited on the c a t h o d e ; b u t since
letallic sodium cannot exist in contact with water, t h e
llowing reaction t a k e s place a t t h e c a t h o d e
2Na + 2H2O 2NaOH + H 2 .
T h u s , b y a secondary reaction, h y d r o g e n is libered at t h e cathode, or, in other words, water is split into
3 constituents, while t h e caustic soda is reformed.
N o w , let t h e caustic soda solution b e replaced by a n
jueous solution of sulphuric acid. I n this case h y d r o m will b e liberated a t t h e cathode a n d t h e g r o u p SO*
the anode, but t h e g r o u p S O 4 c a n n o t exist in contact
ith water, as t h e following reaction takes p l a c e :
2SO4 + 2H2O - 2H2SO4 +0^.
T h u s , by a secondary reaction, oxygen is liberated
the anode, or, in other words, w a t e r is split into its
nstituents while t h e sulphuric acid is reformed.
I
^
1
Electrolyte
FIG
Battery
14.Electrolytic Cell.
Liquids which, under
t h e i n f l u e n c e of t h e e l e c t r i c
r r e n t , b e h a v e in t h e m a n n e r of t h e a b o v e a r e t e r m e d
i l e c t r o l y t e s , " a n d t h e process w h e r e b y t h e y a r e split
is c a l l e d " E l e c t r o l y s i s ".
128
HYDROGEN
T h e laws relating to this decomposition of liquids

by the electric current were enunciated by F a r a d a y as
follows:
1. T h e quantity of a n electrolyte d e c o m p o s e d is proportional to t h e quantity of electricity which p a s s e s .
2. T h e mass of a n y substance liberated b y a given
quantity of electricity is proportional to t h e c h e m i c a l
equivalent weight of t h e substance.
By t h e chemical equivalent weight of a s u b s t a n c e is
meant in the case of elements, t h e figure w h i c h is obtained by dividing its atomic weight b y its v a l e n c y ,
while in the case of compounds, it is t h e m o l e c u l a r
weight divided b y t h e valency of the c o m p o u n d .
However, m a n y elements h a v e more t h a n one v a l e n c y , therefore they h a v e m o r e than o n e chemical e q u i v a l e n t
weight, as can be seen from the following t a b l e :
Eleme t
Hydrogen
Oxygen .
Gold
.
Tm
.
Phosphorus
Tungsten .
.
.
.
.
..,.
Weigh?
ValenC
i
16
197
118
31
184
i
2
3 or
4
5
6 ,,
y-
Chemical Equivalent
Weight, ^ T ' .
1
2
3
4
i
8
65 6 or
29-5
6*02
306
197
59
10-03
46 o
F r o m F a r a d a y ' s laws it can b e seen that, if the

weight of any substance liberated by a definite c u r r e n t
in a definite time is known, the theoretical w e i g h t of a n y
substance which should be liberated by a definite c u r r e n t
in a definite time can b e calculated, if t h e chemical e q u i v a lent weight of this substance is known. V e r y careful
experiments h a v e been m a d e with regard to t h e a m o u n t
PHYSICAL M E T H O D S
129
silver deposited b y a current of o n e a m p e r e flowing

one second (one c o u l o m b ) ; this current deposits
'ooi 118 g r a m of silver
m a n aqueous solution of a silver salt.
N o w t h e atomic weight of silver is
107-94
d its valency is unity, therefore its chemical equivalt weight is
107-94,
t t h e atomic weight of hydrogen is
I'O
d its valency is unity, therefore its chemical equivalent
ight is
I'O,
:refore it follows from
F a r a d a y ' s second law
that
= -000010357 g r a m of h y d r o g e n will be liberd by one "ampere flowing for o n e second, or the mass
hydrogen liberated by a n y current in any time m a y be
Dressed as
1-0357 x i o " 5 A /
ere A is the current in amperes a n d t the t i m e it flows
seconds ; which is equivalent to saying that, at o C.
i 760 mm. barometric pressure (29^92 inches), one
pere-hour will liberate
0147 cubic foot of hydrogen.
So far t h e relationship between current a n d v o l u m e
l y d r o g e n which would b e produced theoretically h a s
:n considered; it now remains to d e t e r m i n e t h e
itionship between power a n d the volume of hydrogen
9
130
which should be theoretically liberated. To refer to

the diagram, it will be at once appreciated that, to get
the current to flow through the electrolyte requires an
electrical pressure, or, in other words, there will be
found to be a voltage drop between the anode and
cathode.
This voltage drop is due to two types of resistance,
one of which is identical to the resistance of any conductor and is dependent on the cross-sectional area of
the path of flow of the current and on the length of the
path, i.e. the distance between the plates. The other
resistance is one that is due to a condition analogous to
the back E M. F. of an electric motor. Assume that
electrolysis has been taking place in the diagrammatic
cell and that the battery has been removed ; if a voltameter is then placed between the anode and cathode it
will be found that there is a difference of potential
between the two plates and that the direction of this
electromotive force is the reverse of that of the current
which was supplied in the first instance by the battery.
This resistance is called the back E M.F. of the cell,
or the polarisation resistance. While the first type of
resistance can be practically eliminated by placing
the plates close together, the second is not a function
of the cell design^ but a constant of the electrolyte in
the cell; therefore, to obtain electrolysis in a cell it
is- necessary that the current must have a certain
theoretical potential to overcome the polorisation resistance of the electrolyte.
The minimum voltage to produce continuous electrolysis in a cell whose resistance other than that due
to polarisation is negligible is given below for various
aqueous solutions of bases, acids and salts containing
PHYSICAL METHODS
131
aeir chemical equivalent weight in g r a m s p e r litre ; with

Dnsiderable variation in the degree of concentration of
le solution it has been found that those solutions given
elow whose minimum voltage is about 1 7 require n o
ppreciable variation in pressure to p r o d u c e continuous
'ectrolysis .
Solution of
11
Zinc sulphate
Cadmium sulphate
nitrate
Zinc bromide
Cadmium chloride
Orthophosphonc acid
Nitric acid
Caustic soda
potash .
Lead nitrate
Hydrochloric acid
Silver nitrate
Minimum Voltage for

Continuous Electrolysis
. 2*35 volts 1
2 03
1
1 98
1
i'8o
1
1-78
170
1
1*69
1
1 69 11
. 1*67 11
I-S2
1
1-31 11 1
70
1
Now it h a s been previously deduced from F a r a d a y ' s

ws that a current of one a m p e r e for one hour should
oduce "0147 cubic foot of hydrogen (at o C. a n d 760
m. pressure), but if a solution of caustic s o d a was used
e current would h a v e h a d to be supplied a t 1 '69 volts,
erefore 1 x 1 "69 watt-hour produces '0147 cubic foot
hydrogen, or
1000 watt-hours produce
,
= 8*7 cubic feet.
r 69
it, at t h e same time a s the h y d r o g e n is liberated a t
2 cathode, o x y g e n is being liberated at t h e anode, a n d
ice from F a r a d a y ' s laws the volume of oxygen is o n e
If of that of the hydrogen, on t h e electrolysis of a
1
Determined by Le Blanc.
132
solution of caustic soda i kilowatt-hour (B.T. U) theoretically produces

87 cubic feet of hydrogen at o C. 760 mm. (29*92").
and 4-4
oxygen -
The theory of electrolysis having been considered, it
remains to describe some of the more important applications of this phenomenon for the production of hydrogen
and oxygen.
To refer again to the diagrammatic cell, if the
distance between the anode and cathode is great the
resistance of the cell is high, and consequently the production of hydrogen is much below the theoretical, but
if, on the other hand, the distance between the two
plates is small, the gases liberated are each contaminated
with the other, hence the design of a cell for the commercial production of oxygen and hydrogen has of
necessity to be a compromise between these extremes.
A large number of commercial cells put the anode
and cathode comparatively close together, but, in order
to obtain reasonably high purity in the gaseous products,
a porous partition is placed between the electrodes: this,
like increasing the distance between the plates, creates
a certain amount of resistance, but it has one advantage
of the latter procedure in that it makes for compactness,
which is very desirable in any plant and particularly so
in the case of electrolytic ones, as one of the greatest
objections to their use is the floor space which they
occupy.
A glance at the list of patents at the end of the
chapter will show what an amount of ingenuity has
been expended in the design of electrolytic plant for the
production of oxygen and hydrogen. On account of
this multiplicity of different cells it is intended merely
PHYSICAL METHODS
) describe
rpes:
J.
2.
3.
4.
t h e following,
133
which are
representative
Filter press type.

T a n k type.
Non-porous non-conducting partition type.
Metal partition type.
Section on Line A B
E
Porous Partition
sz
f
'bber
Electrode
H
Section
on CD.
Section
onE.E
Hydrogen Liberated
! SS S23 3 2 SEE ^
"T
Hydrogen Outlet
Oxygen Liberated
FIG.
Filter P r e s s T y p e , I f ,
:
ig.
15.
in t h e d i a g r a m m a t i c
15), a p l a t e of c o n d u c t i n g m a t e r i a l w a s
cell
placed
tween t h e a n o d e a n d c a t h o d e a n d t h e c u r r e n t s w i t c h e d
L, h y d r o g e n w o u l d b e l i b e r a t e d a t t h e o r i g i n a l c a t h o d e
d o x y g e n a t t h e o r i g i n a l a n o d e , b u t , b e s i d e s t h i s , it
134
would be found that on the side of the plate facing the

original cathode oxygen would be liberated, while on its
other side hydrogen would be given off ; thus it is seen

that the intermediate plate becomes on one face an anode
PHYSICAL METHODS
135
i d on the other a cathode. Further, it will b e found that

le polarisation or back E . M F . resistance of t h e cell
om the original a n o d e to t h e original cathode is doubled ;
IUS the placing of a conductor, to which n o electrical
mnections h a v e been made, turns t h e original cell into
vo cells. T h e filter press cell is constructed on lines
lalogous to t h e above.
T h e filter press cell is composed of a series of iron
ates, which are recessed on either side as s h o w n in t h e
agram, from which it will be seen that, if two of these
ates are p u t together, a space will b e enclosed b y them
f virtue of the recess
In each plate there are three holes, o n e at X and
vo along the line A B , so that, when t h e plates are
aced together, the enclosed recess could b e filled with
ater by means of the hole X. A small hole comlunicates with recess and the holes on A B , but in t h e
ise of o n e this communication is on the right-hand side
hile on t h e other it is on t h e left. N o w , b e t w e e n a n y
vo plates is placed a partition, the shape a n d holes in
hich exactly coincide with those in the plates.
The
i g e of this partition is composed of rubber, while t h e
sntre portion, which is of the same size as t h e recess in
le plate, is m a d e of asbestos cloth.
If four of these plates are pressed together with the
artitions between, they will m a k e t h r e e symmetrical
dls which can b e filled with electrolyte by blocking u p
le hole X in one outside plate and r u n n i n g it in t h r o u g h
lis hole in the other outside plate. Since the asbestos
ortion of t h e partition is porous, the electrolyte will
oon reach the same level in each cell
Now, if a positive electric connection is m a d e to one
utside plate and a negative to the other, w h a t current
136
passes must flow through the electrolyte and consequently

electrolysis will take place. Since each plate is insulated
from the other by the rubber edge of the partition each
plate becomes on one face an anode and on the other a
cathode, as was described in the diagrammatic cell, but
the two plates which go to make the recess are divided
by the asbestos partition, so the gases liberated have
little opportunity of mixing. Since, as has been already
mentioned, one of the holes in the top of the plate is in
communication with one side of the recess and the other
hole with the opposite side, the hydrogen and oxygen
formed pass via separate passages to different gasholders.
The description is applicable to all filter press type
cells. The actual voltage of the electrical supply determines the number of plates which are in the complete
unit, for the individual resistances are in series. In
practice, using a 10 per cent solution of caustic potash
as the electrolyte, the voltage drop j>er plate is 2 '3-2 "5.
The current density is generally about 18-25 amperes
per square fodlt, while the production is 5*9 cubic feet
of hydrogen ajid 3 cubic feet of oxygen, at mean temperature and pressure, per kilowatt-hour, the purity of
the hydrogen being about 99*0 per cent, and that of the
oxygen 97*5 per cent.1
The filter press type of"cell has a considerable advantage by being compact, but, on the other hand, since
1
The reason for the difference in purity is due to the fact that a
small amount of diffusion takes place through the porous partitions,
and since on account of its density the volume of hydrogen diffusing
into the oxygen will be greater than the amount of oxygen diffusing
into the hydrogen, the purity of the oxygen must of necessity be less
than that of the hydrogen.
PHYSICAL METHODS
137
ie water and g a s tightness of the individual cells d e 5nds on the rubber in the partition and on the m e t h o d
pressing t h e plates together, both t h e s e require a
rtain a m o u n t of attention ; probably a cell of this type
ould require overhauling in these particulars about once
every t w o a n d a half months, if it w e r e kept r u n n i n g
mtinuously.
!-__
//_
*_ -
_-"
B
\ m ''
0 0 0 0 0
p o o
_^H
--^.,
Similar Holes frilled

&I1 Wtr CylmderC
FIG 17.Tank Cell.

T h e following are probably the best-known com;rcial cells of this type . Oerlikon a n d S h r i v e n
T h e T a n k Cell.This type of cell will b e readily
derstood by looking at the diagram ( F i g . 17). It
nsists of a circular tank H m a d e of dead mild steel,
138
standing o n insulators M, with an annular ring a t t h e

top. In this tank a n iron cylinder C, perforated with
holes, is h u n g from t h e cast-iron lid of the cell K b y
means of an electrode E . Between the side of t h e t a n k
--
-^i ii ail
FIG. I 8 International Oxygen Company's Cell.

H a n d t h e cylinder C an asbestos curtain A
f r o m a p l a t e of n o n - c o n d u c t i n g m a t e r i a l B .
is h u n g
T h e lid of
t h e t a n k , w h i c h is i n s u l a t e d from b o t h H a n d C, h a s t w o
f l a n g e s O a n d N w h i c h form a n a n n u l a r r i n g .
t w o outlet pipes G a n d F .
It also has
P H Y S I C A L METHODS
139
T h e annular space in the tank H is filled with water,

hile the interior of the tank is filled with a 10 p e r cent,
'lution of caustic soda in distilled water.
T h e m e t h o d of operation of the cell is a s follows: If
e negative lead of t h e circuit is connected t o D , which
metallically fastened to t h e t a n k body H , a n d the
>sitive lead is connected t o E , electrolysis will t a k e place
id h y d r o g e n will b e liberated on t h e side of t h e tank
, rising t h r o u g h the electrolyte into t h e a n n u l a r space
lclosed by t h e flanges N and O on t h e lid K, from
hence it is free to circulate to the outlet pipe G. W h i l e
^drogen is b e i n g liberated on the sides of the t a n k H ,
cygen will b e liberated on both sides of t h e cylinder C,
om whence it will rise up, ultimately finding its way
rough holes in the plate B into the annular space
lclosed by the flange N , a n d thus on t o the outlet
pe F .
T h e r e is a trapped inlet pipe (not shown) in t h e cover
. for introducing further distilled w a t e r from time to
Tie, to replace that decomposed by the operation of the
'ocess
T h e voltage drop between a n o d e a n d cathode is
Dout 2'5 volts.
T h e outlet pipes G and F are usually trapped in a
lass-sided vessel, which enables the w o r k i n g of t h e cell
) be examined.
F i g . 18 shows a t a n k cell of t h e International
>xygen C o m p a n y , which is not unlike the diagrammatic
2II which has j u s t been explained. T e s t s on four of
lese cells by t h e Electrical T e s t i n g Laboratories of
lew Y o r k give t h e following
figures1:
1
Ellis, "The Hydrogenation of Oils" (Constable)
I4O
Temp. 20 C. and Bar. 29*92 In8.
.
Max. o u TJ. TJ Cubic Ft. per
Average Average Average ^le"IT
Cubic Ft. per Hr
K W Hr
Amps. Volts Watts. P
39 2 '7
2609
1022
30 l
Oxygen.
Hydro- Oxygen
gen.
3 114
6075
3OSI
gen.
95
Hydrogen
Outlet
6lass
Plan View
FIG
19.
T h e purity of the oxygen was 98*34 per cent, a n d

that of t h e hydrogen (from another test) 9 9 7 0 per cent.
T h e best-known plant of this type is that of the
International O x y g e n Company.
The
Non-Conducting, Non^Porous
Partition
T y p e . T h i s cell, which is illustrated by the d i a g r a m
( F i g . 19), consists of a metal tube A, which forms the
PHYSICAL METHODS
141
Iectrode a n d g a s outlet, a n d which is m a d e of lead w h e r e

n acid electrolyte is used, a n d of iron w h e r e an alkaline
ne is employed. T h i s metal electrode is s u r r o u n d e d
y a glass or porcelain t u b e perforated at t h e b o t t o m .
T h e r e are four of these electrodes per cell, which
re a r r a n g e d as indicated in the diagram. W h e n the
urrent is switched on t h e gases are liberated o n t h e
lectrodes within t h e glass tube ; consequently no mixing
f the liberated gases can take place.
T h e best-known commercial cell of this t y p e is t h e
Jchoop.
T h e Metal Partition T y p e . I n t h e preliminary
escription of t h e filter press t y p e of cell it was s t a t e d
hat a conducting partition between t h e a n o d e a n d
a t h o d e itself b e c a m e on o n e face a n a n o d e and o n t h e
ther face a cathode ; this, however, requires modificaion, as it is only t r u e w h e n the voltage d r o p b e t w e e n
he original a n o d e or cathode a n d t h e metal partition is
sss t h a n t h e m i n i m u m voltage required for continuous
'lectrolysis.
I n t h e metal partition t y p e of cell a m e t a l partition
s placed between t h e a n o d e a n d cathode. T h i s partiion is insulated from the poles, is not so d e e p a s t h e
ilectrodes, a n d is perforated on the lower e d g e with
mall holes which, t h o u g h reducing t h e electrical resistince, do not allow of the gases mixing.
T h e best-known cell of this t y p e is the G a r u t i ,
Arhich, since the t r u e electrodes a r e only a b o u t half a n
nch apart, gives a m o r e compact cell t h a n if a non:onducting partition w e r e employed.
Since t h e voltage d r o p b e t w e e n electrodes is slightly
less for t h e s a m e electrolyte t h a n if a non-conducting
142
partition were employed the yield is good, b ^ i ^ g a b o u t

6*i cubic feet of h y d r o g e n at mean t e m p e r ^ - t l a r e a n < ^
pressure per kilowatt-hour. T h e current d e n s i t y is a s
high as 25 to 28 amperes per square foot, u s i n g f a 10 p e r
cent, solution of caustic soda.
T h e a d v a n t a g e of this type of cell is its c o r " * P a c t n e s s ,
due to t h e small distance between t h e electr*<=> c les, a n d
its lightness, due to the fact that it is m a d e t * r u g h o u t
(with the exception of t h e insulating strips) o f : r r i i l d steel
sheet. H o w e v e r , t h e small distance b e t w e e n t h e electrodes necessitates care being taken to p r e v e n t a n internal short circuit in the individual cells.
C a s t n e i v K e l l n e r Cell.Besides those c e l l s
already
described, the object of which is to p r o d u c e
oxygen
and hydrogen, t h e r e a r e some which, t h o u g h
not
designed for t h e production of hydrogen, y i e l d it as
a by-product.
Probably the m o s t important of t h e s e e l e c t r o l y t i c
processes yielding h y d r o g e n as a b y - p r o d u c t
is t h e
Castner-Kellner.
T h e primary purpose of t h i s p r o c e s s
is to m a k e caustic soda from a solution o f b r i n e ; b u t
both hydrogen a n d chlorine are produced a t
t h e same
time.
T h e working of this process can be u n d e r s t o o d from
the diagram ( F i g . 20).
T h e plant consists of a box A, d i v i d e d i n t o t h r e e
compartments by t h e partitions B, which, h o w e v e r , d o
not touch the b o t t o m of t h e box A. O n t h e floor of
this box t h e r e is a l a y e r of mercury, which is o f
sufficient
depth to m a k e a fluid seal between the c o m p a r t m e n t s .
In t h e two end c o m p a r t m e n t s there a r e c a r b o n electrodes, connected t o a positive electric s u p p l y , w h i l e in
PHYSICAL METHODS
143
le middle t h e r e is a n iron electrode, connected t o t h e

egative supply. O n e side of t h e box A is carried on a
inge H , while the other is slowly lifted u p a n d down
y an eccentric G, which gives a rocking motion t o t h e
ontents of-the box.
In t h e two e n d c o m p a r t m e n t s is placed a s t r o n g
olution of brine, while t h e middle is filled with water.
) n t h e current b e i n g switched on electrolysis takes
ilace, t h e current passing from t h e positive c a r b o n elecrodes t h r o u g h t h e brine to the mercury, a n d from t h e
Hydrogen Outlet
r ^ X ~ & J
~i
"Mercury
FIG. 20'-Castner-Kellner Cell

m e r c u r y t o t h e n e g a t i v e electrode in t h e c e n t r e c o m p a r t ment.
N o w , c o n s i d e r i n g o n e of t h e e n d c o m p a r t m e n t s , b y
t h e s p l i t t i n g u p of t h e s o d i u m c h l o r i d e , c h l o r i n e will b e
l i b e r a t e d a t t h e p o s i t i v e e l e c t r o d e , a n d will u l t i m a t e l y
p a s s o u t a t E , t o b e u s e d for m a k i n g b l e a c h i n g p o w d e r ,
o r for s o m e o t h e r p u r p o s e , w h i l e s o d i u m will b e d e p o s i t e d o n t h e m e r c u r y , w i t h w h i c h it will a m a l g a m a t e .
O w i n g t o t h e r o c k i n g of t h e b o x , t h e s o d i u m m e r c u r y
a m a l g a m will p a s s i n t o t h e c e n t r e c o m p a r t m e n t , w h e r e
144
it is decomposed at the negative electrode, in accordance

with the following equation :
2Na + 2H2O - 2NaOH + H3.
T h u s , b y the operation of t h e process, chlorine is
produced in the end compartments, and caustic soda
a n d hydrogen in the centre one.
T h e following patents h a v e been t a k e n out for t h e
production of h y d r o g e n electrolytically :
Delmard.
Garuti.
Baldo.
Garuti.
Garuti & Pompili.
G e r m a n patent
English
58282.
16588
18406.
534259.
23663
629070.
111131.
646281.
12950.
2820
27249.
1890.
1892.
1905.
1906.
1906.
1907.
11
U.S.
English
U.S.
11
n
Schmidt.
German
H azard-Flamand. U . S .
G a r u t i & Pompili. English
11
.1
i.
11
ii
Vareille.
,,
Aigner.
Cowper- Coles.
E y c k e n Leroy &
Moritz.
Schuckert.
Fischer, L u e n i n g
& Collins.
Moritz.
Hazard-Flamand
L'Oxhydrique
Francaise.
11
11
French
U.S.
German
English
>.
355652.
823650.
198626.
14285
French
German
,,
397319.
231545.
1908.
1910
11
11
1004249.
981102.
1003456.
1911.
1911.
1911.
,,
II
U.S.
11
11
French
1895.
1895.
1896.
1899.
1899.
1900.
1900.
1902.
1903.
1012
P H Y S I C A L METHODS
Benker.
F r e n c h patent
Knowles O x y g e n
Co. & G r a n t .
English
,,
Maschinenfabrik
Surth.
French
,,
Burdett.
U.S.
Ellis.
Levin.
145
461981.
1913.
1812.
1913.
462394.
1086804.
1087937.
1092903.
1094728.
1913.
1914.
1914.
1914.
1914.
APPENDIX.
PHYSICAL CONSTANTS.
PHYSICAL PROPERTIES OF HYDROGEN.
Critical temperature .
.
. 2340 C.
pressure
. 20 atmospheres
[elting point at atmospheric pressure - 259 C. \ -T>avers
oiling point
- 252-7 C.J
D E N S I T Y OF L I Q U I D
HYDROGEN.
At boiling point .
At melting point
07
086
VAPOUR PRBSSURB OF LIQUID HYDROOEN (Travers & Jacquerod, 1902).
'emperatureC - 258 2 - 256 7 - 2557 - 255-0 - 254 3 - 253 7 - 253 2 - 252 9

'ressure mm
100
200
LATENT
300
400
500
600
700
760
H E A T OF HYDROGEN.
123 cal. per grm,

IO
146
DENSITY OF GASEOUS HYDROGEN.
At o C. and 760 mm.

08987 grm. per litre.
5*607 1b. per 1000 cubic feet
SPECIFIC HEAT OF GASEOUS HYDROGEN.
At constant pressure.
At atmospheric pressure
30 atmospheres
.
At constant volume
At 500 C
.
. 3'42)
. 3-788/ Lussana '
.
2 402 (Joly, 1891).
VELOCITY OF SOUND IN HYDROGEN.
At o C. => 12 86 x io4 cm. per sec. (Zoch, 1866)

SOLUBILITY OK HYDROGEN IN WATER.
The coefficient of absorption is that volume of gas

(reduced to o and 760 mm.) which unit volume of a
liquid will take up when the pressure of the gas at the
surface of the liquid, independent of the vapour pressure
of the liquid, is 760 mm.
Temperature.
Coefficient of Temperature
Coefficient of
" C.
AbHorption.
" C.
Abnorptinn.
o .
. . . 0214H11
do
. . . . oi44aa
10 .
. . 01955l
70 .
.
'oi46
20
.
*oi8iy1
80 .
. oi491Ju
30 .
'oifiyy
yo .
. oi55 a
40
'0152"
100 .
. .
*oi66
50 .
. .
014ft'
TUANM'IKATION O|- G\SEf)llS I IVDHOCKN.
Oxygt-tJ
.
.1*0
Hydrogen
.
.
*4.1
1
Wmrklcr (Her., 1 Sy 1, yy).
-Bohr and Berk (Wicd. Ann., i8yi, 44, 316)
PHYSICAL CONSTANTS
REFRACTIVITY OF
. '
Hydrogen .
RELATIONSHIP BETWEEN
'
.
147
HYDROGEN
l ooo
\ Ramsay & Travers.

-473!
P R E S S U R E AND V O L U M E
W e r e Boyle's L a w correct then the product of t h e

ressure multiplied by the volume would be a c o n s t a n t ;
owever, Boyle's Law is only an approximation, all
ases near to their critical temperature being much m o r e
ompressible than the law indicates. A t atmospheric
smperature the common gases, such as oxygen and
ltrogen, are very slightly more compressible t h a n would
e expected from theory. H y d r o g e n a n d helium under
he same conditions are less compressible, hence R e g Lault's description of hydrogen as " g a s plus que
>arfait".
T h e behaviour of hydrogen at low pressures (from
>5O to 25 mm. of mercury) was investigated b y Sir
Afilliam R a m s a y and Mr. E . C. C. Baly, who found
hat, at atmospheric temperature, Boyle's L a w held
hroughout this r a n g e of pressure.
T h e relationship between volume a n d pressure when
he latter is great has been investigated by A m a g a t a n d
Witkowski, whose results are incorporated in the g r a p h
Fig. 21), which shows the relationship between t h e
heoretical volume of h y d r o g e n which should be obtained
Dn expansion to atmospheric pressure a n d t h a t which
s obtained from a standard h y d r o g e n cylinder.
From
this it is seen that, on expansion from 2000 lb. per
square inch t o atmospheric pressure, 9 2 per c e n t less
volume of h y d r o g e n is obtained t h a n is indicated b y
theory.
148
aSgggss-gggsgssgs
s__s s_
THE JOULE-THOMSON EFFECT.
Down to at least - So C. hydrogen on expansion by

simple''outflow rises in temperature, which, is unlike all
other gases with the possible exception of helium. The
variation in temperature for drop in pressure of unit
atmosphere for air and hydrogen is given below :
PHYSICAL CONSTANTS
149
1
Variation per
Atmospheric Pressure.
Air
1 \
91 6
'8
90-3
Lift
of
ydrogen -
Hydrogen
Lift
Hydrogen*
" ' 3 4 *
460 +
J_*
T
+
+
of
0*203
o o 8
9
0-046
1000
cubic
of
feet
h e r e P = P u r i t y o f h y d r o g e n b y v o l u m e e x p r e s s e d
in
percentage.
B = B a r o m e t r i c pressure in inches.
T T e m p e r a t u r e
of air
in
degrees Fahrenheit
on the
dry
thermometer
This formula
i s c o r r e c t if t h e a i r i s d r y .
small correction must

sllowing
b e applied, which
in t h e a s s u m p t i o n
of
wet
in
the
curve.
T h e purity of t h e h y d r o g e n
as
If it is
is g i v e n
is
expressed
that the impurity
t h e s a m e specific g r a v i t y as
by
volume
is a i r o r s o m e
air
under
other
the
same
o n d i t i o n s ; if t h e i m p u r i t y i s n o t a i r d u e a l l o w a n c e
must
>e m a d e .
Humidity
of
urve gives the correction
Correction
which
h e lift f o r m u l a
for
for
humidity
of
A i r T h e
must
the
be
attached
employed
atmosphere.
in
T h e
hfference b e t w e e n t h e t e m p e r a t u r e of t h e air o n t h e
Liid
dry
thermometers
he graph ; the
Iry
t e m p e r a t u r e of t h e a i r a s s h o w n
thermometer
)erpendiculars
is f o u n d o n t h e l e f t - h a n d
is
from
found
these
on
the
two
bottom;
points
Joule and Lord Kelvin.
side
on
find
intersect
wet
of
the
where
and
I5O
estimate the value of the correction from the position of

the point of intersection relative to the curved lines.
EXAMPLE.Let the air temperature be
Dry.
6o F.
Wet
5oF
t h e n difference is io F . , a n d the intersection of t h e

perpendiculars is between the curved lines '35 a n d '4 at
05 i -15 Z Z5-3-354-+5-55
30 ,, ,
75
' !
,' ' / / ; 'tf

i
'
3
20
Z$
10
7
t
'
T
J
' J
35 4p 4S
i
i
I
l
,
/
r
/
I
it
i
w
i
*
/
$b 95 60
I
ii
i
I
\
i
I
6ft TO "75 80
Temperature of Dry Thermometer/n F?

F I G . 22.Correction for Humidity m lb per i o o o Cubic Feet.
a p o s i t i o n w h i c h m a y b e e s t i m a t e d a t '2,6 l b . ; t h e r e f o r e
36
feet
lb. m u s t b e s u b t r a c t e d f r o m
of h y d r o g e n as determined
t h e lift p e r
1 0 0 0 cubic
b y t h e formula
when
t h e t e m p e r a t u r e of t h e air b y t h e d r y t h e r m o m e t e r w a s
6o F. a n d the difference b e t w e e n w e t a n d dry i o F .
INDEX.
ABSORPTION of hydrogen by metals, 15
Air, composition of, 7.
hydrogen in, 7
Aluminal process, 44.
Ammonia, 26.
absorption by charcoal, 29
liquefaction, 29.
properties, 27.
solubility, 28.
uses, 27.
Arsme, 32.
production in Silicol process, 32.
Electrolysis, 126.
Explosions of mixtures of hydrogen and
oxygen, 14
FAT hardening, 35
Ferro-sihcon, 50
HEAT produced by ignition of hydrogen

and oxygen, 17.
Hydrik process, 44
Hydriodic acid, 24.
Hydrobromic acid, 23.
Hydrochloric acid, 21.
Hydrogen and arsenic, 32.
BADISCHE Catalytic process, 101.
bromine, 23.
patents, 106.
carbon, 20
plant, 105.
chlorine, ai
preparation of catalyst, 103.
iodine, 24.
Bergius process, 63.
nitrogen,
36
patents, 66.
oxygen,
9.
Boiling point of gases, 115
phosphorus, 30
hydrogen, 145
selenium, 25
Bronze, hydrogen in, 4.
sulphur, 24
tellurium, 26.
CALCIUM hydride, 34.
Carbomum-Gesellschaft process, 108 physical constants, 145.
Centrifugal separation of hydrogen, 124 production. See Production of
hydrogen.
Cerium hydride, 34
Hydrogenite process, 60
Clays, hydrogen in, 7.
Hydrohth process, 67.
Critical pressure, 114.
of hydrogen, 145
IGNITION temperature of hydrogen and
temperature, 114.
oxygen, 10.
of hydrogen, 145
Iron Contact process, 86
Fuel
consumption, 97.
DENSITY of gaseous hydrogen, 145
Oxidising, go.
liquid hydrogen, 145.
Diffusion, separation of hydrogen by, Patents, gg.
Plant
121
Multi-retort type, 93.
Discovery of hydrogen, 2.
Single retort type, gs
Draper effect, 22.
Purging, 8g
Purification of hydrogen, go.
ELECTROLYTIC cells
Reducing, 88
Castner-Kellner cell, 142.
Secondary reactions, 91
filter press type, 133
metal partition type, 141
Sulphuretted hydrogen in, g3
non-conducting, non-porous partition
JouLE-Thomson effect, 148.
type, 140
patents, 144
LATENT heat of hydrogen, 145
tank cell, 137.
(I 5 0
1-52
Lift of hydrogen) 149.

Lmde-Frank-Caro process, 113.
patents, iai.
purification of gas, 120
Lithium hydride, 33.
MAGNESIUM hydride, 34
Manufacturing processes
Badische Catalytic, 101.
Bergiue, 63
Carbomum-Gesellschaft, 108.
Electrolytic, 132.
Hydnk, 44.
Hydrogenite, 60
HydroHth, 67.
Iron Contact, 86.
Linde-Frank-Caro, 113.
Sical, 69.
Silicol, 45.
Meteoric iron, hydrogen in, 3.
Production from water and aluminium

amalgam, 69.
silicide, 68.
metallic hydrides, 66.
metals, 61.
hydrocarbon oils, no
starch, n r
steam and barium sulphide, 100
iron, 86
water gas, 101.
REFRACTIVITY of hydrogen, 147.
Rocks, hydrogen in, 3.
SELENURETTKD hydrogen, 25.
Sical process, 69
Silicol process, 45.
composition of sludge, 55.
lime, use of, 53.
mineral grease, use of, 57.
patents, 59
OCCURRENCE of hydrogen, 2.
Oil and gas wells, hydrogen in discharge plant, 47.
precautions to be taken, 57
from, 5
Oxygen, explosion of hydrogen and, 14. purity of hydrogen produced, 45
heat produced by ignition of hydro- strength ot caustic, 52
Sodium hydride, 33.
gen and, 17.
ignition temperature of hydrogen Solubility of hydrogen in water, 146.
Sound, velocity in hydrogen, 146
and, io, 15.
Specific heat of hydrogen, 146
reaction of hydrogen with, 9
Sulphuretted hydrogen, 24
removal from water gas, 84
PHOSPHINB, 30
action on metals, 31.
Phosphoretted hydrogen, 30
TBLLURHTTED hydrogen, 26
Physical constants of hydrogen, 145 Transpiration of hydrogen, 146.
Polarisation resistance, 130.
Potassium hydride, 33.
USES of hydrogen, 1
Production of hydrogen, 39.
from acetyline, 108
VOLCANOES, hydrogen in gases from, 5
acid and iron, 40.
acid and zinc, 42.
WATER gas manufacture, 72.
alkali and aluminium, 44
carbon, 60.
Dellwick method, 75
formate, 60.
English method, 74.
oxalate, 61.
Swedish method, 75
silicon, 45
purification of, 82
zinc, 43.
removal of sulphuretted hydrogen
water and aluminium alloy, 71.
from, 84.

The Chemistry and Manufacture of Hydrogen - P. Litherland Teed (Edward Arnold, 1919)

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The Chemistry and Manufacture of Hydrogen - P. Litherland Teed (Edward Arnold, 1919)

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THE

greatest, it i3 t&sJUfrortl^ that our contribution to the

so, should it h a p p e n t h a t this

further i m p r o v e m e n t in the technology of t h e subject,

the Director of Airship Production for permission to

suggestions in the compilation of

t h e text and assistance in correcting the proofs.

I. HYDROGENITS USESDISCOVERY, AND OCCURRENCE

THE CHEMICAL PROPERTIES OF HYDROGEN

THE MANUFACTURE OF HYDROGEN.

THE MANUFACTURE OF HYDROGEN.

The weight of oil hardened by mean&xSBk*.fliQKenin Europe

Paracelsus, in a similar experiment in the sixteenth century,

In Meteoric Iron # An examination of certain

Weight Taken. Hydrogen Evolved.

'Proc. Roy. Soc," 1897.

Observing that meteoric iron contains occluded

" GasesOccluded in Steel," by T. Baker, Iron and Steel Institute,

In Discharge from Oil and Gas W e l l s , T h e

Pa. & W. Va. Ohio & Ind.

In Gases from V o l c a n o e s . 2 T h e nature of the

In C l a y s . N o t only is hydrogen present in most

F Fouque, " Santonn et ses eruptions," Pans, 1879.

Volumes per iooo.

THE CHEMICAL PROPERTIES OF HYDROGEN.

" Proc. Royal Soc ," vol. xvi, p. 419.

increased to two atmospheres the flame is strongly

Schoop states that when either gas contains 6 to 8 per cent,

before explosion t a k e s place.

'Jour. Chem Soc.," April, 1902.

but otherwise under exactly similar conditions, showed

Volumes jofOjg to 100 Volumes offy

who, besides much very

B y means of adiabatic compression, the temperature

(As determined by Prof. H B Dixon, M.A., F R.S.)

T h e temperature of ignition of a mixture fired by

Besides studying the temperature of ignition of

While it has been said that the temperature of igni1

"The Rate of Explosion in Gases," by H. B. Dixon, Bakenan

tion of hydrogen a n d o x y g e n in their m o s t readily

"Zeitschrift fur analytiscbe cheraie," vol. 32.

T h i s p r o p e r t y of certain s u b s t a n c e s , without themselves u n d e r g o i n g chemical c h a n g e , 1 of b e i n g able to

A later d e t e r m i n a t i o n by Fe"ry ( " C o m p t e s R e n d , "

It is contended by Troost and Hautefeuille that in the case of

to the fact t h a t the speed of burning in oxygen is g r e a t e r

In the case of Zeppelin airships brought down in flames, it is

Reactions of H y d r o g e n w i t h O x y g e n in the Com*

The latent heat of the steam produced is included in the heat

a m m o n i a ) t h e resulting ferric h y d r a t e can b e reduced

Bone and Jerdan, "Chem Soc Trans.," 71, 41, 1897

T h u s if a small p u r e carbon electric a r c is m a d e in a n

and-oxygen w h e n perfectly dry apply also in the case

"Jour. Chera. Soc," April, 1902.

in fact, t h e D r a p e r effect m a y b e likened to a very

S u l p h u r e t t e d h y d r o g e n is an inflammable gas, and

W i t h T e l l u r i u m * W h e n tellurium is heated to 400

S u c h is the importance of a m m o n i a in the existence

A m m o n i a is a strongly smelling gas, possessing a

the density of hydrogen as i, air is 14 39, and ammonia

+ 3O2 - 2N2 + 6H2O.

A m m o n i a is strongly basic, i.e. it possesses the

A feature of t h e absorption of a m m o n i a by water, is

A t - 75 0 C. liquid a m m o n i a solidifies into a white crystal*

Phosphine is a n offensive smelling, poisonous gas