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Hydrazine

Module by: Andrew R. Barron. E-mail the author

Hydrazine (N2H4) is a colorless liquid with an odor similar to ammonia. Hydrazine has physical properties very close to water, with a melting point of 2 °C and a boiling point of 114 °C. The similarity in its chemistry to water is as a result of strong intermolecular hydrogen bonding.

Warning:

Hydrazine is highly toxic and dangerously unstable, and is usually handled as aqueous solution for safety reasons. Even so, hydrazine hydrate causes severe burns on the skin and eyes. Contact with transition metals, their oxides (e.g., rust), or salts cause catalytic decomposition and possible ignition of evolved hydrogen. Reactions with oxidants are violent.

Synthesis

Hydrazine is manufactured on the industrial scale by the Olin Raschig process using the reaction of a sodium hypochlorite solution with ammonia at 5 °C to form chloramine (NH2Cl) and sodium hydroxide, Equation 1. The chloramines solution is the reacted with ammonia under pressure at 130 °C, Equation 2. Ammonia is used in a 33 fold excess.

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(1)
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(2)

If transition metals are present then decomposition occurs, Equation 3, and therefore, ethylenediaminetetraacetic acid (EDTA, Figure 1) is added to complex the transition metal ions. The as produced hydrazine solution can be concentrated by distillation to give a 65% solution. Anhydrous hydrazine is formed by the distillation from NaOH.

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(3)
Figure 1: The structure of ethylenediaminetetraacetic acid (EDTA).
Figure 1 (graphics4.jpg)

Alternative routes to hydrazine include the oxidation of urea with sodium hypochlorite, Equation 4, and the reaction of ammonia and hydrogen peroxide, Equation 5.

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(4)
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(5)

Structure

The nitrogen atoms in hydrazine adopt sp3 hybridization (Figure 2a), and molecule adopts a gauche conformation in the vapor, liquid and solid states (Figure 2b).

Figure 2: The structure of hydrazine.
Figure 2 (graphics7.jpg)

In a similar manner to ammonia, Equation 6, hydrazine is a self-ionizing, Equation 7. While there is a wide range of salts of the N2H5+ cation, only the sodium and potassium salts of N2H3- are stable.

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(6)
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(7)

Reaction chemistry and uses

Hydrazine is polar, highly ionizing, and forms stable hydrogen bonds, and its resemblance to water is reflected in the formation of aqueous solutions and hydrates. In the solid state the monohydrate is formed, i.e., N2H4.H2O. In solution hydrazine acts as a base to form the hydrazinium ion, Equation 8 where Kb = 8.5 x 10-7. The presence of a second Lewis base site means that hydrazine can be protonated twice to form the hydrazonium ion, Equation 9 where Kb = 8.9 x 10-16. Salts of the cation N2H5+ are stable in water; however, the salts of the dication are less stable.

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(8)
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(9)

The reaction of hydrazine with oxygen is highly favored, Equation 10, and the explosive limit is 1.8 – 100 vol%.

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(10)

Hydrazine is useful in a number of organic reactions for the synthesis of a wide range of compounds used in pharmaceuticals, textile dyes, and in photography, including:

  • Hydrazone formation, Equation 11 and Equation 12.
  • Alkyl-substituted hydrazine synthesis via direct alkylation with alkyl halides.
  • Reaction with 2-cyanopyridines to form amide hydrazides, which can be converted using 1,2-diketones into triazines.
  • Use in the Wolff-Kishner reduction that transforms the carbonyl group of a ketone or aldehyde into a methylene (or methyl) group via a hydrazone intermediate, Equation 13.
  • As a building block for the preparation of many heterocyclic compounds via condensation with a range of difunctional electrophiles.
  • Cleavage N-alkylated phthalimide derivatives.
  • As a convenient reductant because the by-products are typically nitrogen gas and water.
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(11)
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(12)
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(13)

Messerschmitt Me 163 Komet

Designed by Alexander Lippisch (Figure 3), the Messerschmitt Me 163B Komet (Figure 4) was the first rocket-powered fighter plane. With a top speed of around 596 mph (Mach 0.83) and a service ceiling of 40,000 ft, the Komet’s performance of the Me 163B far exceeded that of contemporary piston engine fighters. However, despite its impressive performance, it was only produced in limited numbers (ca. 370 as compared to the 1,430 built of its jet powered compatriot the Me 262) and was not an effective combat airplane.

Figure 3: German pioneer of aerodynamics Alexander Martin Lippisch (1894 – 1976).
Figure 3 (graphics16.jpg)
Figure 4: The Messerschmitt Me 163B-1.
Figure 4 (graphics17.jpg)

The Komet was powered by the HWK 109-509 hot engine (Figure 5) that used a mixture of a fuel and an oxidizer. The fuel was a mixture of hydrazine hydrate (30%), methanol (57%), and water (13%) that was designated by the code name, C-Stoff, that burned with the oxygen-rich exhaust from hydrogen peroxide (T-Stoff) used as the oxidizer. The C-Stoff was stored in a glass tank on the plane, while the T-Stoff was stored in an aluminum container. An oxidizing agent cocktail of CaMnO4 and/or K2CrO4 was added to the T-Stoff generating steam and high temperatures, this in tern reacted violently with the C-Stoff. The flow of reagents was controlled by two pumps, to regulate the rate of combustion and thereby the amount of thrust. The violent combustion process resulted in the formation of water, carbon dioxide and nitrogen, and a huge amount of heat sending out a superheated stream of steam, nitrogen and air that was drawn in through the hole in the mantle of the engine, thus providing a forward thrust of approximately 3,800 lbf. Because of the potential hazards of mixing the fuels, they were stored at least 1/2 mile apart, and the plane was washed with water between fueling steps and after missions.

Figure 5: A photograph taken by Professor A. D. Baxter of the HWK 109-509 hot engine.
Figure 5 (graphics18.jpg)

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