Chemical Education Today
From Past Issues
Fire Making, Part 2 by Kathryn R. Williams
Part 1 of Fire Making (1) summarized primitive means of fire production described in 1939 by Warren Watson (2). Although many of those methods remained in usage into the 20th century in limited regions of the world, chemical fire making (the match) had gained preeminence by the late 1800s. In 1941, M. F. Crass, Jr. published a series of five articles on the development of this important industry (3). Prior to the introduction of the friction match, homes of the wealthy displayed a variety of contrivances for chemical fire making. An example is the “instantaneous light box”, which contained a small bottle of sulfuric acid and wooden splints tipped with a mixture of KClO3, sugar, and a gum binder. To start a fire, a splint was dipped into the acid, liberating HClO3, which exothermically oxidized the sugar. Potassium chlorate (with antimony sulfide, gum, and starch) also served as an essential ingredient in early “Friction Lights”, first marketed in the 1820s. However the poor lighting properties of these devices soon led to the use of elemental phosphorus as the friction-sensitive component. Although several entrepreneurs patented their own phosphorus-containing concoctions for ignition tips, “it was found that the simple splint of soft wood, first dipped in melted sulphur and then in paste made of phosphorus and glue, with a little fine sand and red ochre, supplied the most convenient, cheap, and safe match that could possibly be devised” (4). Not all consumers agreed with this opinion, however, due in part to the obnoxious fumes from sulfur oxides. To avoid the problem of odor, manufacturers devised “parlor matches” that utilized nonsulfur splint dips, most importantly paraffin wax, prior to coating with the phosphorus formulation. Crass devoted one article in his series to the historical aspects of mass production of matches. Figure 1 portrays the stages in the coil dipping process, the industry’s first practical large-scale production method, patented in 1863 by Anson and Ebenezer Beecher. The Beecher process was widely adopted by large match manufacturers until 1888, when the same Ebenezer Beecher invented the first continuous automatic match machine, shown in Figure 2. Several decades ago I learned that “safety” matches owed their descriptive name to preventing ignition unless the head was rubbed on a special surface on the cover or the box. But when I read the Crass series, I realized that the required second surface originated as a result of efforts to remove white phosphorus from the match formulation. In addition to being an incendiary hazard, the high toxicity of the white allotrope led to phosphorus necrosis in match factory employees. Crass quoted descriptive accounts of this horrible affliction from Bureau of Labor circulars. Briefly, workers absorbed phosphorus fumes via damaged teeth and gums. The resulting inflammation caused tooth loss and jawbone decomposition (“phossy jaw”), eventually spreading to the cerebrum and other organs.
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Figure 1. The Beecher coil dipping process. Workers in the upper left and upper right corners mix and grind the phosphorus-containing composition. The center drawing shows the novel feature of the method, the coiling machine which wrapped several thousand splints into a roll for mass dipping. Workers in the lower panel dip the coils first in melted sulfur followed by the phosphorus paste. (JCE, 1941, 18, 382.)
Phosphorus necrosis became evident in the first half of the 19th century, about a decade after introduction of white phosphorus into the match industry. By the early 1900s, many European countries banned manufacture or sale of matches containing white phosphorus. Unfortunately, use in the United States increased during the same period due to consumer preference and reduced world prices for white phosphorus. In 1910, the Bureau of Labor made public the findings of a two-year investigation into workplace hazards in the match industry. Since federal law could not prohibit manufacture within a state, Congress addressed the issue in 1913 by imposing a preclusive tax on U.S.-made phosphorus matches and by banning their importation. Crass states, “the elimination of this industrial disease with its ghastly and disgusting effects stands out as a tribute to the research workers who made possible the development of the modern nonpoisonous friction match” (3). European scientists discovered red and amorphous phosphorus in the mid-1800s, and later found that a striking surface containing one of these nontoxic allotropes ignited matches composed of oxidizing agents such as KClO3. In 1855, J. E. Lundstrom produced the first safety (or “hygienic”) matches in Jonkøping, Sweden. Various
Journal of Chemical Education • Vol. 79 No. 5 May 2002 • JChemEd.chem.wisc.edu
Chemical Education Today
From Past Issues modifications soon became popular in Europe, but American consumers preferred matches with tips capable of ignition on any rough surface. Research on a nontoxic “strike-anywhere” friction match resulted in a number of possibilities in the second half of the 19th century, but all either cost too much or failed to ignite smoothly. The breakthrough discovery occurred in 1898, when two Frenchmen, Henri Sévène and Emile Cahen introduced, according to Crass, “the most outstanding contribution in the history of the industry to chemical firemaking” (3). In their U.S. Patent application, the inventors wrote, “We have tried to substitute for white phosphorus in the mixed pastes a body which, while being harmless to the health of workpeople, might enjoy its essential properties of possessing a definite chemical composition and being easily inflammable. The sesquisulfid [sic] of phosphorus (P4S3) fulfils [sic] these prime conditions. Moreover, it offers a sufficient resistance to moisture and to atmospheric agents” (5). The Diamond Match Company purchased the U.S. patent rights in 1900, but replacement of white phosphorus with the sesquisulfide was not immediate. As described above, it was not until later in that decade that the U.S. Bureau of Labor undertook an extensive investigation of the industrial problem. Obviously seeing the light, Diamond Match deeded the sesquisulfide patent to the public soon after Congressional hearings began. Thus in 1913 when Congress instituted the federal tax on white phosphorus matches, the Sévène–Cahen
formulation was already available to all match manufacturers in the country. The saga of the match industry presents opportunities for relevant anecdotes and stories on a variety of topics—the chemistry of several ignition processes, a ghastly workplace disease, research efforts to find safe alternatives, societal and industrial resistance to change, government action in behalf of labor. I encourage teachers at all levels to read the Crass series. More recent information may be found in the account by M. C. Bean (6). References Cited 1. Williams, K. R. J. Chem. Educ. 2002, 79, 408. 2. Watson, W. N. J. Chem. Educ. 1939, 16, 36–45. 3. Crass, M. F., Jr. J. Chem. Educ. 1941, 18, 116–120, 277–282, 316–319, 380–384, 428–431. 4. Oil, Paint, and Drug Reporter 1874 (August 19) in Crass, M. F., Jr. J. Chem. Educ. 1941, 18, 278. 5. Sévène, H.; Cahen, E. U.S. Patent #614350; 1898 in Crass, M. F., Jr. J. Chem. Educ. 1941, 18, 429. 6. Bean, M. C. “Matches” in Kroschwitz, J. I.; Howe-Grant, M., Eds. Kirk Othmer Encyclopedia of Chemical Technology, 4th ed., Wiley Interscience: New York, 1995, vol 16, pp 1–8.
Kathryn R. Williams is in the Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 326117200;
[email protected].
Figure 2. The first continuous, automatic match machine, patented in 1888 by Ebenezer Beecher. (JCE, 1941, 18, 384.)
JChemEd.chem.wisc.edu • Vol. 79 No. 5 May 2002 • Journal of Chemical Education
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