White Phosphorus (P4)

The epiphany for the friction match occurred with the addition of a phosphorus component to the match, Charles Sauria, a French chemistry student, did this in 1830. Phosphorus is itself not the fuel, but acts as the initiator for the flame. Phosphorus-oxygen bonds are very strong (P-O 407 kJ mol-1, P=O 560 kJ mol-1) and hence their formation releases plenty of energy to initiate the lucifer match reaction:

Sb2S3 + 3KClO3 Sb2O3 + 3KCl + 3SO2

Combusting white phosphorus, image from http://www.ux1.eiu.edu/~cfrlk/Combust.html

Phosphorus readily oxidizes in air, but the glue in the lucifer match-head proved to be sufficient protection against premature oxidation. The new match was comprised of white phosphorus (20%), sulphur (15%), KClO3 (30%), chalk (10%) and glue (25%). Initially phosphorus was considered as a fuel element for the match, but when its role as the initiator was realised the phosphorus content of the match was reduced, only one milligram of phosphorus per match is necessary. The new match was named   congreve after William Congreve, who had pioneered rockets as a weapon in the early 1800's. However the name lucifer persisted.
Matchsticks were warmed and dipped into paraffin wax, enabling the wax to soak into the stick, as an improved way to increase the flammability of the matchstick. Matchsticks were also impregnated with ammonium phosphate, a fire retardant, to prevent afterglow; matches had acted as a fire hazard even after use as they continued to glow after being blown out.

The new lucifer had other dangers associated with it aside from afterglow. It was easy to ignite and the white phosphorus content caused them to be toxic if sucked, inhaled or touched thus the matches proved to be a hazard, particularly for young children. Accidents would occur daily as boxes of matches ignited due to shaking or being left in direct sun light. In 1867 the Archduchess Matilda stepped on an unused match and ignited her dress, she died from her injuries.

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