Vol. VIII. No. 89. 
IMPERIAL INSTITUTE JOURNAL. 
[May, 1902.] 
125 
at the same time cheaper and keeping better than potassium sulphide. In all, 55 separate 
tests were made in the counties of Galway, Mayo and Donegal, and in each case two plots 
were sown with smutted grain of the previous year, one after treatment with the fungicide, 
the other without such treatment, so that a direct comparison was possible. The results 
again proved most satisfactory ; in every district but one the crop from the treated grain, 
was either entirely free from smut or was very much less affected than that from the untreated 
grain, which in many cases was so bad as to be useless. It was noticed, too, that the treat- 
ment with “sax - ” appeared to strengthen the plants and certainly hastened germination, so that 
the oats may be advantageously sown the same day they are soaked, after a few hours’ drying. 
In one case it was found that grain soaked in a solution which had been previously used did not 
give such a good result as the first lot, but was better than that which had not been steeped 
at all. Only in the Westport district of Co. Mayo was “ smut ” plentiful on both the treated 
and untreated plots, and here the rotation of crops is simply oats and potatoes, so that land 
which carried oats in 1S99 was again employed in 1901 for the same crop. If the grain used 
was effectively soaked the infection would appear to have come from the soil, and the 
necessity of allowing an interval of at three least years between the crops is emphasised. 
These experiments conclusively prove that “smut ” in oats, hitherto so prevalent in the 
west of Ireland, can be almost, if not entirely, prevented by a cheap and simple treatment of 
the seed oats with some fungicide, such as “sar” or potassium sulphide solution. The 
former appears to be the more convenient for general use, and in one day two men can treat 
enough oats to sow 20 acres, the cost of the solution required being only from 1/- to i/6per acre, 
whereas the yield may be increased to 40-80 bushels per acre instead of half these 
quantities. The farmers were greatly impressed by the success of the experiments, and there 
is every probability that the treatment will be widely adopted in the future. 
THE EMPLOYMENT OF CATALYTIC METHODS IN 
CHEMICAL MANUFACTURES. 
The term “ catalysis ” was first employed by the Swedish chemist Berzelius to describe 
a group of reactions in which some substance appeared to bring about a chemical change 
without itself undergoing any alteration, A familiar example of such a catalytic action is to 
be found in the operation of a certain form of automatic gas-lighting apparatus, consisting of 
a small plate or sponge of platinum, or asbestos coated with a thin layer of platinum black, 
and suspended just above the gas jet. When the latter is turned on the gas impinges on the 
platinum black or sponge, the latter becomes incandescent and so inflames the issuing gas. 
The platinum black in this instance of catalytic action enables the oxygen of the surrounding 
atmosphere to combine with the carbon and hydrogen of the coal-gas, A e . , to burn the latter, 
but is itself quite unaltered and retains this property for unlimited periods, provided the 
platinum be raised to incandescence from time to time. At first it was supposed that reactions 
of this kind were comparatively rare, but recent investigations have shown that catalysis 
plays a very important part in bringing about chemical changes, and attention has thereby 
been directed to this subject both from the technical and scientific sides. Professor Ostw r ald, 
of Leipzig University, has recently, in an address delivered to an assembly of medical men and 
naturalists at Hamburg, discussed the various explanations which have been offered as 
accounting for obscure reactions of this nature, and has shown that, in general, catalysis is 
merely produced by a great increase in the velocity of a reaction already proceeding ; i.e., in 
the example already given, the gas would be slowly oxidised by the oxygen of the 
atmosphere alone, but the presence of the platinum black induces a great increase in the rate 
of this oxidisation and so causes the lighting-up of the plate and the inflammation of the gas. 
OStwald, therefore, defines catalytic actions as those changes brought about by agents capable 
of affecting the velocity of chemical reactions without themselves appearing in the final 
products. These agents are conveniently termed catalysts. Accepting this definition it will 
be seen that a very large number of chemical reactions are included under this heading ; thus, 
the changes brought about by enzymes or unorganized ferments, such as the conversion 
of starch into sugar, which occurs in the malting of barley, the conversion of food stuffs 
into soluble peptones and amides by the agency of pepsin and trypsin in animal metabolism, 
and the fermentation of sugar solutions by the enzymes of yeast with the formation of alcohol, 
are all examples of catalysis. Similarly a large number of reactions are known in which 
minute quantities of water and mineral acids are necessary agcnLs : thus, the conversion of 
starch into glucose is carried on, on an enormous scale, in the United States and is 
generally brought about by boiling the starch with an infinitely small amount of mineral acid, 
the latter undergoing no change in condition or quantity during the process. During the last 
few years it has been shown that many chemicals which readily react with each other in a 
moist condition, are inactive when perfectly dry ; thus, mixtures of oxygen and hydrogen are 
not explosive when thoroughly dried, but the introduction of a mere trace of moisture into the 
mixture restores this property. In these cases the small quantities of water, mineral acids and 
enzymes are to be regarded as true catalysts. 
Turning to the industrial applications of this property an excellent resume of technical 
catalytic actions is contained in a lecture recently given by Dr. Conroy to the Liverpool 
section of the Society of Chemical Industry and printed in the current number ol the Society’s 
Journal (March 15, 1902), and from this source the following abstract has been compiled : — 
Sulphuric Acid. 
The material employed as a source of sulphur for the manufacture of this acid is iron 
pyrites which, when burned in an unlimited supply of air, furnishes sulphur dioxide, and the 
latter by further oxidation yields sulphur trioxide, which when dissolved in water constitutes 
sulphuric acid. The most difficult step in this series of operations is the oxidation of the 
sulphur dioxide, and this is brought about at the present time in most vitriol works by the 
combined action of nitric-oxide and atmospheric air in large specially constructed leaden 
chambers. In this process the first material obtained is a weak, impure sulphuric acid, which 
requires to be concentrated before it can be sent into commerce. During the last few years 
processes have been elaborated in Germany for the oxidation of sulphur-dioxide, produced 
from burning pyrites, with the aid of platinum black and similar catalysts. It has long 
been known that by passing mixtures of sulphur dioxide and atmospheric air over asbestos 
coated with platinum black, sulphuric acid could be obtained, and this is the principle 
underlying the new process, but much investigation has been necessary in order to secure 
satisfactory working on the industrial scale. It was found that the efficacy of the platinum 
was rapidly reduced by impurities in the mixed gases passing from the pyrite burners, 
and so it was necessary to purify these from arsenic and other substances by passing them 
through a system of cooled pipes and eventually through concentrated sulphuric acid, before 
bringing them into contact with the heated platinum. The latter is generally employed in the 
form of platinised asbestos, but other forms have also been used, such as pumice stone 
impregnated with platinum-black, etc. The temperature at which the platinum must be 
maintained is also an important matter, since this greatly affects the yield of acid obtained ; 
the limits appear to lie at 200° C. and i,ooo° C., the best temperature being from 400° to 
500° C. 
In spite of the many difficulties experienced in working this process it appears to be 
efficient and cheap, since one of the most important chemical firms in Germany has abandoned 
the lead chamber process in favour of this method, and now converts about So, 000 tons of 
iron pyrites into sulphuric acid per annum by its aid. 
- 3 &/ ^ 
Chlorine and Chlorine Products. 
The most important catalytic method of obtaining chlorine is the long-established Deacon 
process, which depends upon the decomposition of hydrochloric acid into chlorine in presence 
of cuprous chloride and atmospheric air at a temperature of 450°-5oo°C. This process, how- 
ever, depends upon the Leblanc process of soda manufacture, in which hydrochloric acid is 
obtained as a bye-product, and since this method of alkali manufacture is now gradually being 
replaced by electrolytic methods in which chlorine itself is a product, the importance of the 
Deacon process is likely to decline in the future. As an adjunct to the electrolytic process 
for the decomposition of sodium chloride into caustic soda and chlorine, there will probably 
arise in the future a necessity for a method of converting chlorine into hydrochloric acid ; 
several patents for this purpose have already been taken out, but so far none of these have 
been successfully worked. Pataky (Eng. Patent 1900, 1S31) has proposed to reverse the 
Deacon process by passing chlorine and hydrogen over charcoal heated by means of a water 
bath, and Lorenz (Eng. Patent 1894, 25,073) has found that the interaction of chlorine, 
carbon and super-heated steam gives, under certain prescribed conditions, a satisfactory yield 
of hydrochloric acid, whilst at a French electrolytic soda works, part of the chlorine is 
stated to be converted into the acid by burning a jet of hydrogen in it. 
An account of the development of methods for Lhe electrolytic production of chlorates has 
already been given in this Journal, Vol. vii., p. 96, but it may be pointed out here that it 
has recently been observed by Imhoff that the yield of chlorate obtained by direct electrolysis 
of chlorides is greatly increased by adding to the bath a small quantity of a soluble 
chromate, thus the yield of potassium chlorate for the same current employed in a 30 per cent, 
solution of potassium chloride can be increased from 32 to 69 per cent, by the addition of 
‘18 per cent, of potassium chromate. 
So far no salt but the chromate has been found to produce this effect, the corresponding 
manganese salts having no influence, whilst, curiously enough, cobalt salts prevent the forma- 
tion of chlorate entirely. 
Formaldehyde. 
This substance has during recent years come into extensive use as a disinfectant, and is 
commonly produced by means of the so-called formaldehyde lamps. The latter depend for 
their efficacy on the production of methyl alcohol vapour, which issues from a fine jet and 
impinges upon a small sponge of platinum black, which is at first slightly heated in order to 
start the action. Once started, the oxidation of the spirit to formaldehyde proceeds 
automatically, the heat of the reaction maintaining the platinum at a sufficiently high tempera- 
ture to effect the change. 
This method has also been applied to the production of other organic substances, but 
not on a large scale ; thus, Trillat has obtained vanillin, the odorous principle of vanilla beans, 
from isoengenol by this means, whilst Ipatiew, by a somewhat similar method, has prepared 
benzaldehyde, acetone and other substances from the corresponding alcohols. 
Carbon Tetrachloride. 
This material is of considerable importance in the aids as a solvent of rubber, gutta- 
percha and similar substances and, unlike most solvents of these bodies, is not highly inflam- 
mable. 
It is usually prepared by the action of chlorine on carbon bisulphide, but at ordinary 
temperatures practically no action occurs betiveen these substances, except in the presence of 
certain catalytic agents of which iodine, antimony and aluminium chlorides, bromine, and even 
finely divided iron, have been successfully employed on the large scale. 
In addition to the organic compounds already mentioned as produced by catalytic 
methods, attention may be drawn to the oxidation of naphthalene to phthalic acid by 
means of hot sulphuric acid, which forms the first step in the complicated process by which 
synthetic indigo is made. This reaction only proceeds easily in presence of metallic mercury 
or one of its salts. A similar influence of mercury in a reaction of this kind has been recorded 
by Rosenthal (German patent 127) in his investigation of the oxidation products of aromatic 
amines. 
Many of these reactions are at present inexplicable, but it is very probable that they are 
to be accounted for by the alternate formation and decomposition of compounds between the 
catalyst and the substance undergoing change. The utility of platinum and palladium in such 
actions is no doubt associated with the property possessed by these metals of occluding 
oxygen, hydrogen, and other gases, the latter appearing to be more active in the “ occluded *’ 
condition than in the free state. 
NATURAL GAS IN ONTARIO. 
The first search for natural gas in Ontario w r as made in 1S8S by the Ontario Natural Gas 
Company, and a w ell was put down near Ruthven, which struck gas at a depth of 1,020 feet in 
the upper bed of the Guelph formation, and the yield at the commencement was a little more 
than 10 million cubic feet of gas per day. After the well was tubed and the gas shut in, it 
registered a rock pressure of 460 lb. to the square inch. This well opened up the Essex 
County gas field, now supplying gas to the cities of Windsor, Detroit and Toledo. The 
second well, drilled in Lhe following year, opened up an entirely new field in the County 
of Welland, seven miles from east of Port Colbome. This was opened with a view to 
supplying the city of Buffalo, and the gas w’as struck in a while sandstone of the Medina 
formation at S36 feet from the surface. The flow from the well at its mouth measured 
1,700,000 cubic feet per day, with a rock pressure of 525 lb. per square inch. 142 w ells have 
since been drilled in this field at a total expense of §703,000, and the gas has supplied Fort 
Erie, Bridgeburg and Buffalo. 
The following table shows the strata passed through in the first gas well of the Essex 
field, which w : as called the Coste Well ; — 
Formation. 
Strata. 
Thickness, 
Depth. 
— 
Soil .... 
5 feet to 
5 feet to 
Drift, grey sand 
115 feet 
120 feet 
Onondaga 
Brown and grey dolomitic 
limestones with gypsum 
and flints 
3S0 feet to 
500 feet 
Do. 
Grey blue, shaly and drab 
dolomites wdth gypsum . 
360 feet 
860 feet 
Do. 
Dark brown dolomites and 
gypsum 
1 60 feet 
1,020 feet 
Guelph 
Grey blue crystalline 
vesicular dolomite. 
1 1 feet 
1,031 feet 
The principal features revealed by this and other sections are that in thesouLh and south- 
east part of the county of Essex, along Lake Erie, the first formation met with under the sand 
drift is the Onondaga and that a fault runs in a direction N.N.W. to E.S.E., passing a little 
north of the Coste Well, where the dip of the strata is 8o° to the horizon. An extensive bed 
of gypsum 10 to 20 feet thick is found in the lower part ol the formation ; oil has not 
been found in payable quantity. 
