Smoke-screening properties - white phosphorus

USS Alabama hit by a white phosphorus bomb in bombing tests by General Billy Mitchell,
September 1921.

Weight-for-weight, phosphorus is the most effective smoke-screening agent known, for two reasons: first, it absorbs most of the screening mass from the surrounding atmosphere and secondly, the smoke particles are an aerosol, a mist of liquid droplets which are close to the ideal range of sizes for Mie scattering of visible light. This effect has been likened to three dimensional textured privacy glass—the smoke cloud does not simply obstruct an image, but thoroughly scrambles both visual and infrared radiation.

When phosphorus burns in air, it first forms phosphorus pentoxide (which exists as tetraphosphorus decoxide except at very high temperatures):

P₄ + 5 O₂ → P₄O₁₀

However phosphorus pentoxide is extremely hygroscopic and quickly absorbs even minute traces of moisture to form liquid droplets of phosphoric acid:

P₄O₁₀ + 6 H₂O → 4 H₃PO₄ (also forms polyphosphoric acids such as pyrophosphoric acid, H₄P₂O₇)

Since an atom of phosphorus has an atomic mass of 31 but a molecule of phosphoric acid has a molecular mass of 98, the cloud is already 68% by mass derived from the atmosphere (i.e. 3.2 kilograms of smoke for every kilogram of WP you started with); however, it may absorb more because phosphoric acid and its variants are hygroscopic. Given time, the droplets will continue to absorb more water, growing larger and more dilute until they reach equilibrium with the local water vapour pressure. In practice, the droplets quickly reach a range of sizes suitable for scattering visible light and then start to dissipate from wind or convection.

Because of the great weight efficiency of WP smoke, it is particularly suited for applications where weight is highly restricted, such as hand grenades and mortar bombs. An additional advantage for hand smoke grenades—which are more likely to be used in an emergency—is that the WP smoke clouds form in a fraction of a second. Because WP is also pyrophoric, most munitions of this type have a simple burster charge to split open the casing and spray fragments of WP through the air, where they ignite spontaneously and leave a trail of rapidly thickening smoke behind each particle. The appearance of this cloud forming is easily recognised; one sees a shower of burning particles spraying outward, followed closely by distinctive streamers of white smoke, which rapidly coalesce into a fluffy, very pure white cloud (unless illuminated by a coloured light source).

Various disadvantages of WP are discussed below, but one which is particular to smoke-screening is "pillaring". Because the WP smoke is formed from fairly hot combustion, the gasses in the cloud are hot, and tend to rise. Consequently the smoke screen tends to rise off the ground relatively quickly and form aerial "pillars" of smoke which are of little use for screening. Tactically this may be counteracted by using WP to get a screen quickly, but then following up with emission type screening agents for a more persistent screen. Some countries have begun using red phosphorus instead. Red phosphorus ("RP") burns cooler than WP and eliminates a few other disadvantages as well, but offers exactly the same weight efficiency. Other approaches include WP soaked felt pads (which also burn more slowly, and pose a reduced risk of incendiarism) and PWP, or plasticised white phosphorus.