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Translations Whatever Happened to Homberg's 9 h plt prr nldn lt f ttnd vn dtr nrl f lbrr rrh t nrvl th tr n Wrdr "rdn f th Cnr n Chtr ld n h rlt hh t ntrtn ppr th Ch Illn At 1 t 193" . A. Ch. S., 193 Whatever Happened To ... ? ln , 35 (n nbr d Otbr 1h ppr r ttrd thrht . A. Ch. S. fr WHATEVER HAPPENED TO HOMBERG'S 193 nd 19 bt r prl dntfd hvn rntd t th PYROPHORUS? Cnr 11 W Clr t l "Intrntnl Chl Cnr" . William B. Jensen, University of Cincinnati A. Ch. S., 19 6, 880. 1h nl ntn f th rl tn b th St "br rphr" dntll dvrd b rrd n th prlnr nnnnt fr th nd Intrntnl Wlhl br (15-1715 t rnd 1 hl Cnr f Appld Chtr hld n r n 19; Ann . ttptn t extract n "drl ht l" fr hn A. Ch. S., 19 , 37 xrnt fr th prp f trntn rr nt lvr (1 In th r f th xprnt br dtlld th xrnt th d vrt f thr trl n f James J. Bohning is Professor of Chemistry at Wilkes College, hh hppnd t b n pth r pt l Wilkes-Barre, PA 18766 and is particularly interested in the [K2(SO4Al2(SO4321 nd ntd tht ftr ln th history of the ACS. He is a Past-Chair of the Division and is pprt nd brn pn th ltn th dr rd n th currently serving as its historian. rtrt pntnl brt nt fl h rlt t ntrll ht br ttntn n f h bdn fntn l tht f n f h ntprr th th prprtn nd td f tr- TRANSLATIONS l hh r thr pntnl nflbl r phph- rnt r bth Indd drn h tdnt trvl n Itl h The following experiment is taken from Tiberius Cavallo' s "A hd nvttd th prprtn nd prprt f th -lld Treatise on the Nature and Properties of Air," London, 1781. ln Stn fr f phphrnt br lfd nd Readers wishing to submit their interpretations of the chemis- h ltr prftd rp fr phphrnt vrt f try involved, complete with balanced equations, should send l dhlrd (nn "br hphr" d their answers to the editor by the copy due date listed inside the b htn xtr f ld l [C(O2] nd l - front cover. Answers will appear in the next issue along with n [(Cl] br l rdtd th hvn btnd a fresh puzzle. th rnl rp fr th prprtn f lntl phphr fr hnn Knl ppdl n xhn fr t Dr. Higgins' Experiment of Detonating Cupreous Nitre by brtr nvntd b Ott Gr n hh th hdt f Contact with Tin. h lt ( pr ntr] tn t th r ndtd b " lttl n h t f h h bt nt vr t nd btn t th fnn f bt -lt nd td t th dr n dr thr bt rtrd ndr vr n n rtr t b trd t th thn f hlln n t thr"( Apprntl n th 17th ntr trnt p f tn tlv nh n lnth nd thr n brdth ld b r thn jt pr Yr rl tt hn th fl t b ntntl rlld p t nld th Inrdbl vn h prtnt ntrt n bth prphr lt t l btn th l h nd r t b ht b nd phphrnt btn br fld t fll p pnhn th tthr nd th hl t b prd flt nd n h l-xrnt brvtn ntl 1711 r nrl 3 l r ftr th rnl xprnt hn h n rtrnd t All th bn dn pbl th frt prt f th th bjt nd fnll pblhd ppr drbn th prp- phnn prt f th lt dl h prt rtn nd ffrn rtnl fr t prprt (3 An prntd th tn hnd n lr nd f thr th prdt t b xtr f tr-fr lt (btnd fr ntn bn t frth frth fr th nd f th l 3 th l nd n l nflbl l (btnd fr th A trn frthn pnd th drt rth xrnt h ptltd tht t pntn ntn d h n f p ntr f 5 t ntlrbl t t th rtn f th lt th th tr n th r th th fnr Expln nd fr hh brt nd f th tn- rtn f l [CO] nd tr th rtn pp- fl n vrl pl f t b vr thn dl nrtd ffnt ht t nt th nflbl l br ntll drbd h xtr t nthr nd h Anr t t I zzl f "phphr" bt ltr dptd th r pprprt tr f "prphr" - rd hh vntll t nf ll rdr rpn r rvd nd ndd t t th pntnl nflbl ld h r prprt f 22 ll t Ch 3 (199 pyrophorus by heating together a mixture of charcoal and potassium sulfate. He further showed that both moisture and fire air were essential for ignition. His explanation of the ignition process was based on his personal version of the phlogiston theory in which the charcoal saturated the liver of sulfur with phlogiston. In the presence of moist air, the attraction for water of the alkali in the liver of sulfur forced out this excess phlogiston, which was then seized by the oxygen of the air to produce heat in accord with Scheele's hypothesis that: phlogiston + fire air --> heat and the resulting increase in temperature kindled the remaining charcoal. The same year Lavoisier (1743-1794) did a quantitative study of both the formation and ignition of the pyrophorus (8). Shl ntd th nt f tr nd xn In the first of these processes he showed that, in addition to fr th ntn pr elemental sulfur and liver of sulfur in the pyrophorus itself, a mixture of fixed air [CO 2] and heavy inflammable air [CO] was also produced, and he further showed that the pyrophorus the material intrigued Homberg's contemporaries and the could be synthesized by directly heating a mixture of charcoal, attempts to unravel its chemistry would eventually command sulfur and fixed alkali (potassium or sodium carbonate). Dur- the talents of some of the 18th century's most celebrated ing ignition, Lavoisier found that the pyrophorus gained weight chemists (4). while simultaneously absorbing oxygen from the air - a process The first advance was made by Homberg's associate, Louis corresponding to the reoxidation of the sulfur and liver of Lemery (1677-1743), who demonstrated in 1714 that the sulfur to sulfuric acid and its eventual combination with the excrement could be replaced by a variety of other combustible fixed alkali to produce an alkali sulfate. animal and plant substances, including wood, blood, flesh and Though Lavoisier's rationale is essentially the one Spanish fly (5). He further postulated that the function of the accepted today, his contemporaries continued to debate both combustible was to reduce the vitriolic acid in the alum to sulfur and that the resulting intimate mixture of sulfur and the unused organic combustible accounted for the mixture's inflammability. An even more significant observation was made by Le Jay de Suvigny in 1760, when he discovered that alum was also not an essential ingredient, but rather an indirect source of alkali sulfate, and that, consequently, suitable pyrophors could be made by directly using pure potassium or sodium sulfate (6). He further postulated that the product contained a mixture of sulfur and sulfuric acid and that the heat generated by the latter on reacting with the moisture of the air was sufficient to inflame the sulfur and so account for the ignition. In 1777 the Swedish apothecary and chemist, Carl Wil- helm Scheele (1742-1786), devoted a section in his famous book on Ar nd r, in which he first described his discovery of fire air or oxygen, to the now infamous pyrophorus (7). After first observing that "the kindling of this strange chemical product has already caused vain efforts to many in the endeavor to explain it clearly", Scheele suggested that the net result of heating the alum and combustible was to produce an intimate mixture of charcoal and liver of sulfur [K2S]. He then pro- vr frt rnzd th xtn f nd xd f ceeded to test this hypothesis by successfully synthesizing a rbn rlt f h ntttv td f th prphr ll t Ch 3 (199 3 th ntr f th prphr nd th hn f t ntn bl h hrdn f th Intn tn ll nt th frt dd f th 19th ntr h rt (175-1 hllnd Svn ntn hpth tn A/l AS/l K -1 AG/l t 93 K n 177 nd Shl nd th Grn ht hnn Göttln (1755-19 rrd t pl n 17 n th nt f 4 - -1 - fxd ll n t prprtn In 17 ltr d zr (175- 5 -95 2.06 -9 175 ntd tht h lntl phphr hd t b 6 -1917 777 - prnt n rdr t nt fr th pntn nfl- bllt hr n 17 th Enlhn n ptltd bntn th ntr-l d n th r nd ftr v ltn f th ll tl rtd tn nvlvn C + C 2( ( (5) th prn f tll pt nd d bn t ppr (9- nd th ntr pr nttd b th tr ttrtd b h fnl nn rhd b th 13 lttl r th nhdr lfd h th pplr ld tt rtn thn nr lbrtn f vr rnl r (1 In btn zn tl nd ld dn r n ntrt drn tr t nvlv th rdtn f th ll lft nl d ltr dntrtn r nttd b th rbn v t lt thr ptn rt th th fnl ddn drp f tr t tht rtn r thn t dprd ll lfd fr rtn 1 nd nd th n- xthr th btn f rbn n rtn 5 nd rtd rbn prfrrbl prprd b ltn prl- l r xthr thn th btn f thn f n rn pnd bn th t prtnt tv prdt h vrbl nt f fr lfr prdd hh C( + 2w -- CO( + 1-120( ( l ntd b vr prbbl nrtd b th thrd rtn Intrtnl rtn rltd t tn 1-3 hv l bn tdd pbl t n th ntn f bl pdr (11 nd n th f d lt pbl t n th 2 4 ( ) 2 4) K (SO )( + C , — K S + C( bln pr fr th nftr f d rbnt (1 hh br prphr ntnd t b ntnd KZ(SO4)3 + C (,) KS(g) + CO( n f th r prhnv txtb n th frt hlf f th 19th ntr t n tt hllnd b th K2(S04( + 2C (,) — K2(CO3)( S (,) + CO( dvr f vrt f thr prphr n th 13 nd 1 In 131 th Arn ht brt r (171- 15 rprtd th dvr f prphr d v th A ndtd b th thrdn dt n bl 1 ll f th thrl dptn f rn bl (13 nd n th prd pr b thrdnll fbl t hh t- btn 137 nd 1 th Grn ht dlph Mr prtr nd ndd prbbl prd ll bl th t- (1-11 hd h t lr nbr f pr- prtr d t th p f th prdt nt th phr v prl f ld rbxlt lt (1 h r rrndn tphr h plr t prpr thn br prphr nd r Intn d t th hhl xthr (bl xdtn tll d ltr dntrtn f th fnl dprd ll lfd h hl b f th n prphr lrl dffrnt fr tht f br prprtn nd lntd KS(,) + 24) — K2(SO4 ( th hp f n hl rtnl An ndrtndn f th thrdn vr th nt pt f th hh n trn nt th rbn trl ntrll n fr th ltrtr f th prd thh th rl f rf r nd ntt xn pprtd nd xpltl dd b Mrr rl bl 1 h hrdn f th rprtn tn 17 (1 A/l AS/l K-1 TIC at AG = 0 tn frn nd t 1 137 13 51 1 r brphl dt n br rtntn A 2 1 84.00 1 tr f Chtr, l 3 Mlln ndn 19 pp - 3 31 44.00 9 2.
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