Chemistry and the First World War

Submitted by AWL on 7 April, 2015 - 6:08 Author: Les Hearn

In April 1915, American newspapers reported that the USA faced a “dye famine”, with only two months’ supply left. This was not a minor inconvenience but threatened the livelihoods of two million workers as dyes were essential in the textile, paint, paper, and printing industries, among others. What had happened?

You may recall the Bunsen burner, the Liebig1 condenser, and the Haber2 process from your school days, named after just three of the many world-leading chemists underpinning the German chemical industry, the largest in the world by the outbreak of the Great War. Developing in the 19th century, this industry made steel, dyestuffs, explosives and medicines. In 1913, Germany produced getting on for 90% of the world’s artificial dyestuffs or raw materials for these, mostly produced from coal tar. They also dominated in other areas, such as production of potash fertiliser.

After the war started, Germany could no longer export dyes due to a naval blockade: hence the “dye famine.” In any case, the Central Powers needed these chemicals themselves for the war effort but so did the Allied Powers. The latter had to rapidly scale up their chemical industries. By the end of the war, chemicals production had expanded greatly in many countries, setting the scene for the development of an extraordinarily effective and lucrative industry that has dominated the world economy ever since.

Why were chemicals needed? In short, to make explosives, fertilisers, medicines and antiseptics, dyes, and poison gases.

The warring nations needed raw materials for dyestuffs, explosives and fertilisers. Much came from coal tar with which all were well supplied but they needed sources of “fixed” nitrogen for explosives and fertilisers. A major source of suitable nitrogen compounds was Chile saltpetre (sodium nitrate) but this was soon denied to Germany by naval blockades. Britain and its allies were also partly cut off by German naval activity and were faced with a similar though less acute shortages.

The First World War was a war of shells, projectiles packed with high explosive and fired by guns. Just one type of gun, the standard 18-pounder British field gun fired 86 million shells, two for every three seconds of the war. Shells, including shrapnel, are said to have caused 70% of battlefield casualties.

The Central Powers expected the war to be won quickly and only had sufficient supplies to last until 1916. In particular, sources of “fixed” nitrogen, needed for both explosives and fertilisers, and of glycerine, needed mainly for explosives, were inadequate.

Fritz Haber described the choice as whether “to starve or to shoot.” Haber had developed a solution to the nitrogen problem with the Haber process (remember your chemistry lessons!) which combines nitrogen from the air with hydrogen to make ammonia. There was no shortage of air or hydrogen! The ammonia was used to make fertilisers or converted to nitric acid (for explosives) by the Ostwald process.

Thus Haber and Ostwald allowed Germany to carry on making enough munitions for another two years but, the choice between “guns or butter” having been made in favour of guns, severe food shortages caused malnutrition and loss of morale.3 Britain could make nitric acid from Chile saltpetre and did not suffer so much from these problems.

The Allies expected a swift conclusion, too, and stockpiles of munitions were rapidly depleted, resulting in the “shell crisis of 1915.” This caused the failure of a major British offensive. The response was to set up over 200 munitions factories, staffed largely by women filling cartridges, shells and bombs. The “munitionettes” ran many health risks from hazardous chemicals, in addition to the risk of fire and explosion.

There were five particularly serious explosions. In 1916, at the Explosives Loading Company, near Faversham, Kent, 15 tons of TNT and 150 tons of ammonium nitrate exploded.

“The Great Explosion” killed 116, left a 40-yard crater, shattered windows in Southend 20 miles away across the Thames estuary, and was heard in France. In 1917, in densely-populated Silvertown, London, a fire set off 50 tons of TNT, causing an explosion heard 100 miles away, killing 73 and injuring 400. The greatest loss of life was at the National Shell Filling Factory in Chilwell, Nottingham. In 1918, 8 tons of TNT exploded, killing 134 and injuring 250. Thirty-five “Barnbow lasses” were killed in Leeds in 1916; 38 were killed at Low Moor, near Bradford, also in 1916; and many others died in smaller explosions.

Acetone, an organic solvent, was essential for making cordite (without which shells and bullets could not go anywhere). British acetone was either imported from the USA or made by distilling wood, neither of which was sufficient. The chemist Chaim Weizmann5 successfully developed a fermentation process to make acetone from maize. Schoolchildren were enlisted to collect conkers (horse chestnuts) as it was found that these could be used as well. Over half the UK’s cordite was produced at the munitions plant at Gretna.4 Here, the munitionettes would knead nitroglycerine and guncotton with acetone into what Conan Doyle termed “devil’s porridge.”

Potash was an important chemical fertiliser whose use was encouraged by Liebig. At the start of the war, world supplies mostly came from potash mines in Germany, while nitrogenous fertilisers came largely from Chile as saltpetre. British chemical fertilisers were not in short supply but the US was greatly affected by the loss of potash from Germany. The “potash crisis” increased prices ten-fold and led to ingenious schemes to obtain potassium compounds (from rocks, wastes from iron blast furnaces, seaweed, banana stalks, salt lakes, cement kilns). This new potash industry collapsed after the war, leaving several ghost towns.

Glycerine, an oily substance, was needed to make nitroglycerine (for cordite). Obtained from plant and animal oils and fats, it rapidly ran short. This led to a massive increase in whaling as blubber was a rich source of glycerine. Whale oil was also used to rub into troops’ feet to combat “trench foot” which could lead to temporary or permanent inability to fight.

Whaling was then dominated by Britain and Norway. Neutral Norway sold its whale oil to both sides but was eventually persuaded by strong-arm tactics to sell most of its oil to Britain at a bargain price. The Central powers used sugar fermentation to restore self-sufficiency in glycerine (the other product, alcohol, did not go unused!).

At least 50,000 whales “gave their lives that men might die”!

These are chemicals that combust (burn) or decompose extremely rapidly to produce large amounts of hot gases and therefore a huge shock (pressure) wave.

Low explosives (LE) are typically used to propel projectiles (bullets, cannonballs, rockets), though they can cause explosions if in a sealed container. They include gunpowder (the first explosive invented) and cordite.

High explosives (HE) produce such a powerful shock wave that they would destroy a gun barrel. They are used to shatter things (shell casings, rocks, buildings). They are used as sticks or moulded in mining or sabotage, in artillery shells, or in bombs.

They include nitroglycerine, TNT and ammonium nitrate. Dynamite, invented by Alfred Nobel (see box) in 1867, is a mixture of nitroglycerine and kieselguhr, a soft sedimentary rock largely composed of silica. This is much safer than pure nitroglycerine in that it does not spontaneously explode when dropped or heated but only when detonated.

Artillery shells comprised a steel casing containing lyddite (picric acid) or amatol (TNT and ammonium nitrate), with a mercury fulminate fuse as detonator. A bag of cordite propellant was placed behind the shell in a cartridge case.

Most explosives rely on the rapid oxidation of a compound containing carbon, hydrogen and, usually, nitrogen. Such compounds are less stable than their oxidation products, water and carbon monoxide; also, nitrogen compounds are less stable than the element nitrogen. This means that, firstly, the reaction is very exothermic — it releases a lot of heat energy. And, secondly, the products, carbon monoxide, steam and nitrogen, are gases. Since these take up thousands of times more space than the explosive chemicals, there is an enormous increase of pressure: in short, a hot blast.

Just burning the chemicals would release the same energy but slowly, as the oxygen would have to diffuse through the air to the fire. Explosive chemicals therefore either have to contain a lot of oxygen or be mixed with an oxidant, a chemical which releases oxygen when required. In gunpowder, sulfur and carbon burn rapidly in the presence of the oxidant potassium nitrate (nitre), exploding if in a confined space. More modern HE, such as picric acid, nitroglycerine or trinitrotoluene (TNT: C7H5N3O6), contain substantial amounts of oxygen and are their own oxidants.

The propellant (LE) pushes the shell at great speed out of the gun barrel. The fuse detonates the HE which blows the casing apart. A supersonic blast or pressure wave causes great damage to the surroundings.

Shells can also contain smoke-producing chemicals, incendiary substances such as phosphorus, metal objects (shrapnel), bright-burning chemicals (flares), or poison gases.

The chemicals needed came from a variety of sources: coal tar for phenol and toluene; saltpetre for nitric acid; cotton for guncotton; glycerine from animal and plant fats and oils; acetone for cordite from distillation of wood. All were in shortage to some extent for both sides.

Born in 1833, a son of an armaments manufacturer who provided weaponry to the Russian army in the Crimean War, Alfred Nobel studied chemistry and then worked on improving the stability of explosives so that they could be handled safely.

Nobel was sympathetic to anti-war views and supported the peace movement, expressing the belief that his inventions with their unprecedented power of destruction would make war morally impossible (In 1891, he said: “On the day that two army corps can mutually annihilate each other in a second, all civilised nations will surely recoil in horror and disband their troops”). This idealism had in fact been disproved some 20 years earlier when the newly-invented dynamite had been used in the Franco-Prussian war. Nevertheless, he continued in his work, perhaps justifying it to himself in terms of a theory of deterrence.

In 1888, his brother died in France: obituaries of Alfred were erroneously published, one entitled “Le marchand de la mort est mort” (“The merchant of death is dead”).

Alfred was said to have been saddened by this and concerned with how he was to be remembered. On his death in 1896, it was found that he had left almost all his considerable fortune to a trust which was to award yearly what became known as the Nobel prizes, one of which was for activities promoting peace.

1 Justus von Liebig invented the meat extract later named Oxo. He was also known as “father of the fertiliser industry.”

2 Fritz Haber, “father of industrial nitrogen fixation.” The tragedy of Haber will be covered in a future article.

3 Food shortages were also important in the outbreak of the February revolution in Russia 1917.

4 HM Factory Gretna stretched for 12 miles along the Scottish-English border in four sites, with a dedicated coal-fired power station and 125 miles of narrow-gauge railway. Two townships housed the mainly female workforce, with kitchens, bakeries and laundries. Their “moral” welfare and factory discipline was looked after by a women’s police force. Local pubs and breweries were nationalised to control alcohol consumption.

5 Russian-born Chaim Weizmann, “father of industrial fermentation,” emigrated to Britain to help advance the Zionist cause. He discussed Zionist aspirations with Arthur Balfour, gaining his support for a Jewish homeland. He became the first president of Israel.

Note: much credit goes to Michael Freemantle’s books Gas! Gas! Quick, boys! (2012) and the more extensive The Chemists’ War: 1914-1918 (2015, Royal Society of Chemistry; ISBN 978-1-84973-989-4).

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