The Riddle of the Rhine:
V >>
Victor LeFebure >> The Riddle of the Rhine:
Pages:
1 |
2 |
3 |
4 |
5 |
6 |
7 |
8 |
9 |
10 | 11 |
12 |
13 |
14 |
15 |
16 |
17 |
18 |
19
Chlorine was important, nor only as a raw material for most of the known
chemical warfare products, but also, in the liquid form, for cloud attack.
Owing to the development of protection, the use of liquid chlorine
for the latter purpose became obsolete.
_Phosgene_.--This was produced in considerable quantity
before the war at Leverkusen and Ludwigshafen, leading to many
exceedingly important dyes, amongst the most commonly used at
present being the brilliant acid fast cotton scarlets so largely
used in England. More expansion of plant was necessitated.
At Leverkusen the existing plant can produce at least thirty tons
a month, and we learn "the plant remains intact ready for use."
At Ludwigshafen the capacity was considerably higher, amounting to
600 tons per month. As production was commenced before the war,
there were no difficulties in developing the process,
expansion alone being necessary.
_Xylyl Bromide_.--This was one of the early lachrymators, and was produced
at Leverkusen in a plant with a maximum monthly output of sixty tons.
Production began, according to a statement on the works, in March, 1915.
Its case can be judged from the fact that this compound was used almost
as soon as the first chlorine cloud attack at Ypres.
The Germans undoubtedly attached considerable importance to their
brominated lachrymators. In this connection their persistent
efforts to retain the bromine monopoly with their Stassfurt product
and to crush the American industry before the war are significant.
The success of these efforts certainly placed us in a difficult
situation during the war, both with regard to production of
drugs and lachrymators.
German bromine was associated with potash in the Stassfurt mineral deposits,
whereas the American product was produced from numerous salt springs
and rock salt mines. Although Germany had not succeeded in crushing
the American industry, yet the outbreak of war found her in a
predominant position, for her two chief opponents, France and England,
were cut off from their supplies, which were German; and American production
was of little use, owing to the great excess of demand over supply,
and the manipulation of output by German agents in America. A possible
source of bromine existed in the French Tunisian salt lagoons,
whose pre-war exploitation had been considered by an Austrian combination.
The French wisely developed a Tunisian bromine industry sufficient for their
own needs, and, on different occasions, supplied us with small quantities.
But the development of such an enterprise in time of war was
a severe handicap.
_Diphosgene or Trichlormethyl Chloroformate_.--This substance was toxic,
a lachrymator, and slightly persistent. It attained a maximum
monthly Output Of 300 tons at Leverkusen, and about 250 tons
at Hochst. This was not a simple compound to make, and had no direct
relationship with the stable product of the peace-time industry.
At the same time, it provides an example of the way in which general technique
developed by the industry was rapidly used to master the new process.
In particular their method of lining reaction vessels was of value here.
The reaction occurs in two stages by the production of methyl formate
and its subsequent chlorination. The methyl-formate plant was part
of an existing installation, but the chlorination and distillation
plant were specially installed.
_Chlorpicrin_.--This was mixed with diphosgene and used
in the familiar Green Cross shell. The production was very
readily mastered and attained the rate of 200 tons per month.
Picric acid, chlorine, and lime were required, all three
being normal raw materials or products of the industry.
At Hochst no new plant was installed, the manufacture being
carried out in the synthetic indigo plant.
_Phenylcarbylamine Chloride_.--This was used in German chemical shell,
and was not particularly effective against us, although produced in large
quantities by the Germans, in vessels used in peace time for a very
common intermediate, monochlorbenzene. The ease of production of this
substance may account for its use in large quantities by the Germans,
in order to increase their gas shell programme.
_Mustard Gas or Dichlordiethyl Sulphide_.--This was prepared
in four stages:
(1) Preparation of Ethylene--by heating alcohol with an aluminium
oxide catalyst at 400'0 C.
(2) Preparation of Ethylene-chlor-hydrin, by passing ethylene
and carbon dioxide into a 10 per cent. solution of bleaching
powder at a temperature below zero centigrade, and subsequent
concentration of the product to a 20 per cent. solution.
(3) Conversion of the chlor-hydrin into thiodiglycol by treatment
with sodium sulphide.
(4) Conversion of the thiodiglycol into mustard gas
(dichlordiethyl-sulphide), using gaseous hydrochloric acid.
The thiodiglycol was produced at Ludwigshafen and provides one
of the best examples of the adaptation of the German dye works
for the purpose of producing war chemical. Technically, ethylene is
a fairly difficult gas to produce in large quantities, but, for the
Ludwigshafen works, these difficulties were a thing of the past.
There were twelve big units before the war, and, by the time
of the Armistice, these had been increased to seventy-two
in connection with mustard gas manufacture. In a similar way,
the number of the units for chlorhydrin, the next step, was increased
from three to eighteen. These two processes had all been worked
out very thoroughly in connection with the production of indigo.
These new plants were identical with the peace-time units.
The expansion was a mere question of repetition requiring no
new designs or experiments and risking no failure or delay.
Success was assured. The last step, the production of thiodiglycol,
occurred in the causticising house, to which no substantial
alterations or additions appear to have been made for the purpose.
As sodium sulphide is used in large quantities as a raw material
in the dye industry, and was already produced within the I.G.,
no difficulty was presented in connection with its supply.
The thiodiglycol was forwarded to two other factories, one of which
was Leverkusen, where 300 tons of mustard gas were produced monthly.
The reaction between thiodiglycol and hydrochloric acid was one which
required very considerable care. At one stage of the war the Allies viewed
with much misgiving the possibility of having to adopt this method.
But the technique of the German dye industry solved this as satisfactorily
and as steadily as other chemical warfare problems, bringing its technical
experience to bear on the different difficulties involved.
_Diphenychlorarsine_.--This was the earliest and main constituent
of the familiar Blue Cross shell. It was prepared in four stages:
(1) The preparation of phenyl arsinic acid.
(2) The conversion of the above to phenyl arsenious oxide.
(3) The conversion of the latter into diphenyl arsinic acid.
(4) The conversion of the latter into diphenyl-chlor-arsine.
This is another example of a highly complicated product
which might have presented great difficulties of production,
but the problem of whose manufacture was solved, almost automatically,
by the German organisation.
The first step, that of the manufacture of phenyl arsinic acid,
was carried out at Ludwigshafen in one of the existing azo dye
sheds without any alteration of plant, just as a new azo dye
might have been produced in the same shed. It is believed
that another dye factory also produced this substance.
At Ludwigshafen the conversion to diphenyl arsinic acid occurred.
This was again carried out in the azo colour shed, with no
more modification than that involved in passing, from one azo
dye to another.
This chemical mobilisation of a huge dye unit was, and could still be,
practically invisible in operation. Not only was the process practically
the same as azo dye production, but, as the compounds were not particularly
poisonous in the intermediate stages, there was no risk to the workers,
and no need to violate secrecy by indicating special precautions.
The final stage, the preparation of diphenylchlorarsine,
the actual Blue Cross shell constituent, occurred at Hochst,
which also carried out the first three stages, already outlined
as occurring at Ludwigshafen and Leverkusen. The last stage
was a simple one and was carried out in plant and buildings
previously used for peace purposes.
The other substances employed provide further examples of this ease
of production. Ethyl-dichlor-arsine was produced in homogeneously
lead-lined vessels, identical with those used for diphosgene.
Dichlor-methyl-ether presented difficulties which were solved
by applying the German method of using tiled vessels.
The part played by the I.G. in the German chemical warfare organisation
has already been outlined, and we have seen how the German Government was
content simply to place its demands before the directors of the dye combine.
The latter were left to choose the process and exploit it by making the best
use of their organisation, which was done after reviewing the plant at their
disposal in the different branches. An interesting feature of the production
of war chemicals by the I.G. is thus revealed by examining the actual locality
of the separate operations leading to any one of the individual poison gases.
The attached table shows us how the production of any particular war chemical
involved a number of stages, each of which occurred in a different factory.
The directors of the I.G. simply chose a particular plant in a particular
factory which was most suited for the operation concerned. They
{The table (spread over pages 162-163) are "raw OCR" feed! NEEDS FIXED!!!}
FIRST STAGE
RAW
WAR CHEMICAL MATERIALS FROM THE I.G. PROCESS FACTORY
Phenyl Carbylamine 1. Aniline Condensation of aniline Kalle Chloride 2.
Chlorine with carbon bisul 3. Caustic phide to phenyldithio soda carbamic
acid Mustard Gas 1. Carbon Preparation of Ethyl-Ludwigs dioxide lene
from Alcohol hafen 2. Bleaching
powder 3. Sodium
sulphide 4. Hydro chloric
acid Diphenylchlorarsine I. Aniline Conversion of Diazo- Ludwigs 2.
Sodium benzene to Phenylar- hafen
nitrite sinic acid Kalle 3. Sodium Hochst
bisulphite 4. Sodium
hydrate 5. Sulphur
dioxide 6. Hydro chloric acid Ethyl -dichl or a rsine 1.
Ethyl Production of Ethylar-Ludwigs chloride sinic acid from
Ethyl hafen 2. Caustic chloride
soda 3. Sulphur
dioxide 4. Hydro chloric
acid gas 5. Iodine Sym-dichlor-methyl- I. Chlorsul- Production
of Formal- Mainz
ether phonic dehyde from Methyl116chst
acid alcohol
Z. Sulphuric
acid 162
Review of Production
SECOND STAGE THIRD STAGE FOURTH STAGE
PROCESS FACTORI PROCESS FACTORi PROCESS FACTORY
Conversion of Kalle Chlorination of Hochst
Phenyidithio- Phenyl Mus carbamic acid tard Oil giving
to Phenyl Mus- Phenyl Carby tard Oil by lamine Chlo zinc chloride ride
Conversion of Lud- Conversion of Lud- Conversion of Lever Ethylene
into wigs- Chlorhydrin wigs- Thiodiglycol kusen
Ethylene hafen to Thio-di- hafen to Mustard
Chlorhydrin glycol Gas
Reduction of Lever- Conversion to Lever- Reduction of A.G.F.A. Phenyl arjinic
kusen Diphenylar- kusen Diphenylar- Hochst acid to Phenyl and sinic acid
by and sinic acid to arsenious oxide Hochst treatment Hijchst Diphenyl:
with Diazo chlor-arsine
benzene by Sulphur
dioxide in
HCl solution
Reduction of Lud- Conversion of W)chst
Ethyl arsinic wigs- Ethyl arseni acid to Ethyl hafen ous Oxide to
arsenious oxide Ethyl dichlor by sulphur arsine by
dioxide HCl and iodine Conversion of H8chst
paraformalde hyde to sym
dichlor methyl
ether by means
of chlorsul phonic acid {END OF TABLE NEEDING FIXED!} aimed at
the minimum conversion, and in a number of cases none was required.
The above analysis can leave us with no doubt in our minds that
the organic chemical industry is the logical place for efficient
chemical warfare production. It cannot leave us unconvinced as to
the vital importance of the dye industry in national defence.
Allied Difficulties.--Our own production was nothing but a
series of slow and relatively inefficient improvisations.
We have already referred to the fluctuations in chemical
warfare organisation for research and supply during the war.
These added to the difficulties of the supply department,
just as they did to its complement, the research department.
Only great patriotic endeavour could have made possible
the relative success achieved, not only by the departments,
but in particular by the firms with whom they were called
upon to co-ordinate.
We wanted mustard gas, and realised its need in July, 1917.
Research work began almost from that date, yet successful large scale
production did not materialise in England until more than a year later.
We must admit, however, that the French were in a position to use
their product on the front in July, 1918. Let us examine some
of our difficulties.
The first efforts were directed towards the process by which,
as we eventually ascertained, the Germans produced the whole
of their mustard gas. The actual chemical laboratory details
of the process presented no serious obstacle, but difficulties
multiplied as soon as we attempted large scale work.
We wanted ethylene-monochlor-hydrin. Some work had been done on this
during the war for the National Health Insurance Commissioners
in connection with the production of novocain. Half scale
work had occurred at the works of a Midland chemical firm,
and experience so gained was freely offered and used
in a scheme for the large scale production of mustard gas
by the co-operation of a number of big chemical manufacturers.
Pressing requests for the material were continually coming from
G.H.Q., the programmes outlined being more and more ambitious.
We had to reproduce the result of years of German effort spent
in developing their monochlor-hydrin process for indigo.
As a consequence, large sums of money were expended on the process,
although it never eventually operated. Its difficulties,
and other reasons, led us to research on other and more
direct methods which the French were also investigating.
The successful outcome of this early research was due, in particular,
to Sir William Pope and those associated with him in the work.
The process was so promising that the long and cumbersome chlor-hydrin
method was abandoned. As a result our five or six months'
work on the German method meant so much time lost.
The new direct, sulphur monochloride method was taken up
actively and several private firms attempted to develop
the small scale manufacture. The work was dangerous.
Lack of that highly developed organic chemical technique,
which was practically a German monopoly, rendered the task much
more dangerous than it would have been if undertaken by one
of the I.G. factories.
The French, realising the importance of the new methods,
spared nothing in their attempts to develop them.
Their casualties multiplied at the works, but the only reply was
to put the factories concerned under the same regime as the front,
and the staffs were strengthened by well-chosen military personnel.
The French realised the nature of their task, and organised
for it. When the difficulties of production were pointed
out in August, 1917, in the British Ministry of Munitions,
reports were instanced that the Germans had used forced labour.
The French in their production at Rousillon, on the Rhone,
employed volunteer German prisoners. It was a curious
contrast to see mingling together amongst the producing plants
representatives of the American, Italian, and British Missions,
with French officers, French technical men, and German prisoners.
The latter appeared to be perfectly satisfied in their work.
They were used for certain limited purposes, such as handling
raw materials, and were not, as a rule, exposed to the dangerous
operations against which the French struggled so heroically
and successfully. It was as though a small section of the front
had been transferred to the heart of France. We saw the minister
visiting a factory and pinning the Legion of Honour on to
the breast of a worker blinded by yperite. We saw messages
of congratulation from the front to the factories themselves.
The morale was wonderful. As a result, the French mastered
the technical difficulties of mustard gas production and shell
filling by June, 1918. They shared information with us, but the race
had started neck and neck, and it was impossible to discard
completely the large plants to which we were already committed.
Without disparaging our own efforts, we must pay a tribute to the
achievement of the French yperite producing and filling factories.
It is impossible to give personal credit in this matter without
going beyond our scope, and we can only draw general comparisons.
But we must draw attention to the following. The German factories
passed with ease to mustard gas production by a process which,
compared with the final Allied method, was clumsy and complicated,
but which suited their pre-war plant. Their policy was,
therefore, sound from the point of view of the campaign.
The Allies experienced great difficulty and danger in attaining
large scale manufacture with a simpler process.
The same self-sacrificing zeal and patriotic endeavour was
shown in this country, but we were handicapped in mustard gas
production by the energetic way in which we had pressed forward
the industrial realisation of the monochlor-hydrin method.
The French, less committed in terms of plant and finance, could more
readily adjust their energy, materials, and money to the new method.
It must not be forgotten, also, that, at this period,
chemical warfare supply organisation was experiencing certain
critical changes which could not but reflect upon our efficiency.
Here again the earlier centralisation of research and production
by France was a great factor in her favour.
Our difficulties with phosgene, and in particular with the arsenic compounds
described above, were of the same nature, involving us in casualties,
great expenditure, and little success, when compared with German production.
The great need for these arsenic compounds was realised as early as February,
1918, and investigations began even at that date, but they had not appeared
in the field by the time of the Armistice. Whatever mistakes we may have made
locally during the war, they are small compared with the big mistake which
was responsible for our comparative failure in chemical warfare production.
We were almost completely lacking in organic chemical industrial experience.
It is interesting to note that the activities of those elements
of organic chemical industry which did exist in France and England
fully justified the conclusions we have drawn. Thus, although
entering late into the field of chemical warfare production,
Doctor Herbert Levinstein, Professor A. G. Green, and their
collaborators of the firm of Levinstein Limited were able to develop
rapidly a successful industrial mustard gas process which was
of considerable assistance to England and America. This work,
both in research and production, deserves the greatest credit.
Again, the dye factories were called upon much earlier to assist
in French production and were of considerable assistance.
It would be well at this juncture to review very briefly the other
war activities of our own dye industries. The outbreak of war found
them by no means inactive. In this country, for example, our own dye
factories were able to keep pace with the increasing demand for dyes
created by the rapid mobilisation of military and naval equipment.
In particular the rapid large-scale production of indigo by the
Levinstein firm, at Ellesmere Port, was a considerable achievement.
In addition, the new State-aided enterprise at Huddersfield was largely
diverted to explosives production, and rendered very valuable services
in the supply of Tetryl, T.N.T., synthetic phenol, picric acid, and oleum.
For such reasons, the need for essential dyes, and the use of dye capacity
for explosives, the important part which the rapidly expanding industry
could have played in chemical warfare production was not recognised
quickly enough by the relevant authorities. This is not surprising,
for the war significance of the German dye industry was not fully
realised until the Armistice. It required the Hartley Mission
to drive this fact home. When, however, the brilliant researches,
referred to above, on the mustard gas method had decided our policy,
the dye factory of Levinstein Limited vigorously converted the process
into a technical success, and what was still a laboratory reaction
in the spring of 1917 became a successful manufacturing process in July
of that year.
Released from its war responsibilities at the time of the Armistice,
the British industry developed so rapidly that Lord Moulton, in a speech
to the Colour Users Association on November 28th, 1919, stated:
"A few months before the war broke out England produced only one-tenth
of the dyes she needed, but the amount which I am informed we shall
be able to turn out at the end of this year would, in weight,
be within one-fifth of the amount which England used before the war."
But the Allies were not only in difficulties with regard to the lack
of suitable peace-time plant, and industrial organic chemical experience--
they were hindered at almost every turn by difficulties with regard to raw
materials and intermediates, the products of other chemical manufacture.
They had to create a liquid chlorine industry. In April, 1915, the only
liquid chlorine plant in England was in the hands of the firm of
Castner Kellner, whose maximum output was not more than a few tons per day.
Increase in capacity was rendered necessary by chemical warfare developments.
Chlorine was a raw material for mustard gas and--practically every important
substance employed in chemical warfare including bleaching powder.
Tremendous tonnages of bleach were involved in the manufacture of
chlorpicrin and for use as an antidote against mustard gas on the front.
We refer elsewhere to the developing use of bleach in order to create
lanes for troops and transport through areas infected by mustard gas.
A very simple calculation will show what quantities would be required
for such an operation. It is true that, as regards chlorine, we were
more favourably situated than France, and forwarded her considerable
supplies in exchange for phosgene. This chlorine was essential for
phosgene production. New plants were brought into being at different places,
largely through the energy and experience of the above-mentioned firm,
but so great was the demand that it finally became necessary, in order
to protect the trade users and war interests at the same time, to institute
a control of chlorine. More than 20,000 tons of liquid chlorine were
produced under the administration of the supply department concerned.
When we consider the effort which such an increase in production must
have involved, and the fact that expansions occurring did not do so under
the steady and well-regulated influence of a simple demand, but were
continually being modified to meet expansions or diminutions of programme,
we can realise what a great advantage was possessed by the Germans owing
to their large initial experience and production.
We have no hesitation in stating that great credit is due to the old
Trench Warfare Supply Department and the firms with which it was in contact,
notably the one referred to above, in connection with the Loos attack.
But for them, we would not have been in a position to retaliate,
even at that date.
The Allied lachrymator campaign was terribly handicapped by lack of bromine.
The French performed the phenomenal task of creating a bromine
industry in Tunis, the development of which reads like a romance.
Apparently this industry is dying out, and German predominance in bromine
is again asserted.
French mustard gas production, for which they made such huge sacrifices,
was threatened by the lack of carbon-tetra-chloride, and examples
can be multiplied. The Germans were in a very different position.
The development of their dye industry had followed the policy
of absolute independence of external chemical industry.
This independence was acquired either by the absorption of other
enterprises or by the definite development of processes and plant
for raw materials and intermediates. In every case the war has
strengthened these factories for the manufacture of these products.
In 1918 they produced nearly thirty times as much ammonia
as in 1914, three times as much nitric acid, fifty per cent.
as much again of sulphuric acid, and twice as much
liquid chlorine. This was not purely a commercial question.
Our lack of such products was due to the fact that the Allies,
in pre-war times, possessed few or feeble industries whose
consumption would stimulate the production of these raw materials.
They lacked these industries because of a blameworthy disregard
for the fundamental importance of science, and particularly
chemical science, in industry.
Pages:
1 |
2 |
3 |
4 |
5 |
6 |
7 |
8 |
9 |
10 | 11 |
12 |
13 |
14 |
15 |
16 |
17 |
18 |
19