Now all roads lead to France and heavy is the tread
Of the living; but the dead returning lightly dance.
Edward Thomas, Roads

Sunday, March 25, 2018

The Haber Process in War and Peace


By James Patton

Many have heard of the brilliant German chemist Fritz Haber (1868–1934), infamously remembered as the Father of Chemical Warfare due to his work developing and deploying weaponized chlorine, phosgene and diphosgene, and considered by some to be a quintessential "mad scientist." However, gas was actually his second-most important contribution to WWI. For what was vicariously his most important contribution, Haber received the Nobel Prize for Chemistry in 1918.

Fritz Haber
In 1909 Haber first demonstrated the Haber Process (also called the Haber-Bosch Process) by which he successfully synthesized ammonia, which is a precursor to the synthesis of nitrates and nitrates, which form the basis for both fertilizers and explosives. With the major natural sources of these substances denied to the Central Powers by the Royal Navy’s blockade, without the synthetic ammonia they would have quickly run out of ammunition, making the Haber Process probably the single most important factor that prolonged and intensified the war, so that it could be a horrific disaster.  

Born to a Jewish family in Breslau, Prussia, Haber’s father ran his family’s chemical works, making dyes, paints, and drugs. Haber received his doctorate from the Frederick Wilhelm University in Berlin in 1891. After a brief stint in the family business, he agreed to convert to Lutheranism to get a position in the laboratory of Hans Bunte (1848–1925) at the Technical Institute of Karlsruhe (Baden), and in 1898 he received a royal appointment to the faculty there. During this time he married the brilliant Clara Immerwahr (1870–1915), one of the first women to hold a doctorate in chemistry.

While at Karlsruhe Haber became interested in the work of his French colleague Henri Louis Le Chatelier (1850–1936), who in 1894 postulated the principle that bears his name, which he stated as:

When any system at equilibrium is subjected to change in concentration, temperature, volume, or pressure, the system readjusts itself to counteract the effect of the applied change and a new equilibrium is established.

To physical chemists this meant that chemical reactions could be reversible. Haber was particularly interested in producing ammonia (NH₃) from gaseous nitrogen and hydrogen. Ammonia is found in nature, a waste byproduct of living organisms and previous research had successfully decomposed natural ammonia into elemental nitrogen and hydrogen. Pursuant to Le Chatelier’s Principle, Haber reasoned that the process could be reversed, and on an industrial scale. If he was right the result would be a significant find because natural ammonia was scarce. 

Haber’s desired chemical reaction is expressed thus: N₂ + 3H₂  → 2NH₃

Sounds simple, but the process proved to be complicated, involving a pressure vessel and a metal catalyst, originally osmium (Os), which is the densest element and not abundant. Later research by Carl Bosch (1874–1940) of BASF led to the satisfactory substitution of iron compounds, particularly magnetite (Fe3O4), which dramatically reduced the production cost. Years later, Bosch shared a Nobel for Chemistry in 1931. 

Haber on Right in the Laboratory

There are six steps to the process, which occur as the pressure and temperature are increased (adsorbed means accumulated on the surface of the catalyst, akin to freezing rain adhering to a car window):

1. N2 (g) → N2 (adsorbed)
2.  N2 (adsorbed) → 2 N (adsorbed)
3.  H2 (g) → H2 (adsorbed)
4.  H2 (adsorbed) → 2 H (adsorbed)
5.  N (adsorbed) + 3 H(adsorbed)→ NH3 (adsorbed)
6. NH3 (adsorbed) → NH3 (g)

The process requires pressure at 2,200 to 3,600 psi and a temperature of 750 to 930°F. In this environment, the mixture of 3 parts hydrogen gas to 1 part nitrogen gas is repeatedly passed over the catalyst. On each cycle about 15% conversion occurs until 97% conversion is attained. 

The Haber Process is not just a footnote in history. It remains vitally important to humanity, as ammonia-based fertilizers are used everywhere to increase and improve crop yields and start "Green Revolutions." Without these chemicals half of us would starve.

3 comments:

  1. Should read nitrates and nitrites

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  2. While the Allies were getting their nitrates via bird guano from Chile to fuel their explosives works, Germany was using Haber's process. It would be interesting to discuss management's failure in its allocation between explosive mfg and agricultural fertilizer mfg. If better allocated could the effects of the British Blockade have been appreciably lessened?

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  3. But for the Haber-Bosch process, the war might well have been over by Christmas, or spring 1915, a "fact" which many popular histories (and the National WW-1 Museum) do not mention. After Haber had used poison gas at Ypres, his wife, Clara, declared that she could not stay married to a war criminal and shot herself. When Hitler came to power, Haber, who was "racially Jewish", left Germany. He applied for a visa to the US, but we wouldn't give him one. Later, when he was dying, he tried to re-enter Germany so as to be buried next to Clara. He couldn't get in and was buried near the Swiss border. His friends then went to Germany and recovered Clara's remains so they could be buried together in Switzerland.

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