Sal Ammoniac-A Case History in Industrialization-Robert P. Multhauf

Sal Ammoniac: A Case History in Industrialization
Author(s): Robert P. Multhauf

Source: Technology and Culture, Vol. 6, No. 4 (Autumn, 1965), pp. 569-586
Published by: The Johns Hopkins University Press and the Society for the History of Technology
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SAL AMMONIAC:A CASE HISTORY IN

INDUSTRIALIZATION
ROBERT
P. MULTHAUF
1. The Substance,Its Uses and Sources

Sal ammoniac (ammonium chloride) seems to have first become
known as a product of the wastelandsof CentralAsia-the Tarim Basin
-from which it was exportedboth to the Arabiccountriesand to Tang
China. Two circumstancesmade it something of a sensation among
Arabic alchemists:its property of coloring (and in some cases utterly
dissolving)metals,and their discoverythat sal ammoniacis producedin
the distillationof some animalsubstances.Obtainedas a sublimatein the
distillationof hair, it convinced the Jabirianalchemists-or perhapsfitted their preconception-that alchemical elixirs should be sought
through the distillationof organicmaterials.'
Sal ammoniacwas no less coveted by Europeanthan by Arabic alchemists,and as alchemy gave way to medical chemistryits role easily
shifted from that of a key to the preparationof the Philosopher'sStone
to that of a crucial ingredientin the production of medical elixirs. It
was a common ingredient, for example, in various processes for the
preparationof mercurialremedies. From these misty lucubrationsit
emerges in the European Renaissanceas one of the more important
exotic substancestradedby the Italianmercantilecities, particularlyby
the Venetians,who not only imported it but maintainedfactories for
its purification,thus effectively compoundingthe secret of its origin.
Used in a variety of industrialapplications,in dyeing, in cleaningmetal
surfaces (as in tinning processes),in drug manufacture,and as a source
of ammonia,it appearsto have been producedthroughthe first part of
the nineteenth century on a scale justifying its inclusion among the
"heavy chemicals."The nineteenthcentury, however, saw the diminuDR. MULTHAUF,Chairmanof the Department of Science and Technology of the
Smithsonian Institution, is editor of Isis, the journal of the History of Science Society, and the author of many works on the history of science and technology.
1 On the early history of sal ammoniac, see H. E. Stapleton, "Sal Ammoniac,
a Study in Primitive Chemistry,"Memoirs of the Asiatic Society of Bengal, I (1905),
25-41; Julius Ruska, "Sal ammoniacus,Nusadir und Salmiak,"Sitzber. d. Heidelbergische Akad. d. Wissensch., Phil. Hist. KI. (1923), and "Die Salmiak in die
Geschichte der Alchemie," Zeits. f. Ang. Chemie, XLI (1928), 1321-24.
569

570
Robert P. Multhauf
tion of its use in every one of these industrialapplicationsuntil by 1850

it had revertedto the statusof a minorraw materialscarcelynoticed in
books on chemicaltechnology.
As a substanceof importancein alchemy and medical chemistry sal
ammoniacwas regularlydiscussedby early Europeanchemicalauthors,
as a rule with little consequence,but in 1620 we find in the Synopsis
aphorismorumchymiatricorumof Angelo Sala an account of the synthesisof sal ammoniacfrom "volatilesalt" (of urine,i.e., ammonia)and
the spirit of common salt (hydrochloricacid), two substancesthat had
been known, at least vaguely, for over a century. A generationlater
JohannGlauberdemonstratedthe analysisof sal ammoniacthrough the
"mortification"of its acid (with quicklime) and the liberation of its
"volatilesalt."2Thanks to Sala and Glauber, science probably had at
this time-the 1650's-a securer foothold on the understandingof sal
ammoniacthan any other substanceof commercialimportance.
Sal ammoniacwas frequentlymentionedas a materialimportedfrom
Egypt, where, according to the general opinion, it was a product of
solardistillationof camelurinein desertsands.But by the latter half of
the seventeenthcentury there is impressivetestimony that most, if not
all, of the sal ammoniacused in Europewas artificiallymadeby a somewhat analogousprocess through the boiling down, followed by sublimation, of a mixture of five parts urine, one part common salt, and
one-half part soot. The recipe was an old one, having appearedin the
late thirteenth-centuryInventionof Verity of the celebratedalchemist,
the "Latin Geber."3That it was in use in Europe is implied, where
not actually claimed,by Lefevre, Glaser,and Boyle, perhapsthe three
most well-informed chemists of the 1660's.Lefevre says that he has
never seen naturalsal ammoniac.All say that it is made in Venice. Lefevre says that it is also made in Holland and at Antwerp, and Nicolas
Lemery, the leading chemist of the next generation,declaredthat the
processis carriedon at Venice "andmany other places."4
When chemistrybeganto flourishat the ParisAcademiedes Sciences
just before 1700-in consequenceof a reorganizationwhich increased
severalfoldthe numberof chemistmembers-sal ammoniacemerged as
2
Angelo Sala, Opera medico-chymica (Frankfurt, 1747), p. 246;Johann R. Glauber, Opera chymica (2 vols.; Frankfurt, 1658-59), II, 136-38.
3 Geber, Works, trans. Richard Russell (1676), reissued with an Introduction
by E. J. Holmyard (London, 1928), pp. 205-6.
4 Nicolas Lefevre, A CompleatBody of Chymistry,trans.P. D. C. (London, 1664),
Part II, pp. 302-3; Robert Boyle, Works (6 vols.; London, 1772), II, 225; Nicolas
Lemery, Cours de chymie (2d ed.; Paris, 1677), p. 344. Many eighteenth-century
writers also give the recipe (e.g., John Harris, Lexicon technicum [1710]).

HistoricalRelationsof Scienceand Technology
571
a topic of particularinterest.The academiciansstudied it in all its aspects, and it is a measureof their thoroughnessthat in 1720 they publisheda firsthandaccount of its productionin Egypt. It seemsthat it was
producedneitherfrom urinenor from desertsandsbut was sublimedfrom
chimney soot collected from furnacesthat burnedcamel dung. By 1735
we find Duhameldu Monceauarguingthat the salt is a uselessingredient
in the Europeanprocess,and by mid-centuryit had been decided that
the urine is also superfluous.5This raisedquestionsabout the supposed
European process, and a suspicion was confirmed that had been expressedby Lemery himselfbefore his deathin 17156that the Venetians
had been creditedwith producingsomethingthat they really imported.
Had anyone ever produced sal ammoniacfrom urine, salt, and soot?
The literaturethat has been cited becomes conspicuously unspecific
when skeptically reconsidered.Of all the chemists I have mentioned,
only Sala and Glauber were personallyfamiliarwith the chemical industriesof Venice and Amsterdam,and they do not appearto mention
this process. Most important,according to modern theories of affinity,
the reactionwill not take place.
Egyptian sal ammoniacwas pre-existentin the soot of camel dung
and could be similarlyobtained,as was subsequentlyshown in France,
from the dung of any herbivorousanimalthat feeds on saline vegetation. In his celebratedchemicaltextbook of 1732, HermannBoerhaave
further reported sal ammoniacto be obtainableby sublimationfrom
ordinary coal soot. This hardly seems to save the reputationsof the
seventeenth-centurychemists,since soot comprisedonly one-thirteenth
of their formula, and the quantity of sal ammoniacin coal soot is so
slight that modernaccountsof coal chemistrymentionit only as a trace
ingredient.But there is substantial,although not quite conclusive, evidence that coal soot was the source of the first sal ammoniacproduced
commerciallyin Europe. The factory in question was establishedin
Edinburghin 1756 by JamesDavie and JamesHutton, the latter being
the famous geologist, who is supposed to have supported his science
through the profits of the sal ammoniacfactory. Secrecy was maintainedin this chemicalworks, as it was in virtuallyall othersat the time.
5
H. L. Duhamel du Monceau, "Surla sel ammoniac,"Mem. Par. (1735), pp. 10616, 414-34, 483-504. Antoine Baume (Chymie experimentale et raisonee [3 vols.,
Paris, 1773], II, 94-99), reviewing the work of the Academie on sal ammoniac,
says it was no help in devising his own process-but then he does not tell what
his process was!
6Nicolas Lemery, Dictionnaire universel des drogues simples (Paris, 1759), p. 765
(the first edition appearedin 1698).

572
Robert P. Multhauf
Clow and Clow, however, have published the following circumstantial

account:
Globular glass vessels, about a foot in diameter, are filled to within a few inches of their mouth with it [soot], and are then arranged
in an oblong furnace, where they are exposed to a heat gradually
increased. The upper part of the glass balloon stands out of the
furnace, and is kept relatively cool by the air. On cooling, the upper parts of the globes are found to be lined with sal ammoniac in
hemispherical lumps, about 2.5 inches thick. 26 lbs. of soot yield 6
of sal ammoniac.7
It is curious, to say the least, that two knowledgeable chemists who
lived and wrote in Edinburgh during this period do not seem to have
thought that Davie and Hutton obtained sal ammoniac in this way.
There was no disputing the utilization of soot-for a time they reportedly took the entire collection of the Edinburgh Society of Chimneysweepers-but Joseph Black thought that the soot provided only volatile
alkali (ammonia), which was converted to sal ammoniac through sulfuric acid and common salt in a manner to be described below (see
"Sulfate Process"). The author, probably James Tytler, of the article
on chemistry in the second edition (1778) of the Encyclopaedia Britannica also thought that the soot provided volatile alkali but that its conversion into sal ammoniac, although it also used sulfuric acid and salt,
was by a different process (see "Direct Process," below).8 In view of
the history of the urine-salt-soot process it is reasonable to ask if the
supposed soot-sublimation process may not also have been a myth.
Unlike the former process, that of soot sublimation is at least theoretically tenable, for coal does contain sal ammoniac, and indeed a number
of processes for its recovery have been patented in the twentieth century.9 In a typical chloride-containing coal, about 25 per cent of the
ammonia present will appear on distillation as sal ammoniac, and it seems
likely that the soot collected by the Edinburgh chimney-sweepers
would have been a more promising source of sal ammoniac than of the
volatile ammonia. It is worth noting, moreover, that whereas sal ammoniac was at this time a well-identified substance, ammonia was not,
and its presence in coal had been little noticed before Black and Tytler.
7 Archibald Clow and Nan Clow, The Chemical Revolution (London, 1952),
p. 420. The source of this appears to be the Session papers in the Library of the
Writers to H. A. Signet, Edinburgh.
8 Joseph Black, Lectures on the Elements of Chemistry,ed. John Robison (Edinburgh, 1803), I, 469-70. "Chemistry,"Encyclopaedia Britannica (2d ed.; Edinburgh,
1778), III, 1850-51.
9 See H. H. Lowry, Chemistry of Coal Utilization (New York, 1945),
p. 1075.

573
Its characteristicodor made ammoniaeasily recognizablelong before it

was differentiatedas a discrete substance,which is credited to Priestley (1775). Previously,volatile alkaliand sal ammoniacwere mutually
confused. In occupying himself (in 1700) with the study of "the famous English drops" (which we know as smelling salts), Tournefort,
who had been informed that the "drops"were "the volatile spirit of
crude soot," recognized their identity with the volatile salt in sal ammoniac and with "spiritsof hartshorn."He obtainedthese volatile salts
and spirits,as was usual,with quicklime.10It would appearthat Tournefort had a reasonablyclear conception of the relationshipbetween sal
ammoniacand ammonia.When in 1767,however, we encounter"volatile alkali"as a product of coal distillationin the voluminoustreatiseof
JeanF. L. Morandon coal, we find it describedas "a mucous deposit of
a yellow color,"'1and thus probablysal ammoniac.One reasonfor the
establishmentof a sal ammoniacindustrywas, of course,that sal ammoniac was a source of ammonia,and this remainedtrue even after the sal
ammoniacitself was madefrom ammoniafrom naturalsources,for that
ammoniawas so impurethat its conversioninto sal ammoniacwas continued as a mode of purification.
The most troublesomeaspect of the testimony of Black and Tytler
is their claimthat the Edinburghsal ammoniacworks importedsulfuric
acid and exported Glauber'ssalt, for this can hardly be accounted for
unlessDavie and Hutton were using one of the synthetic processesto
be describedin the next section of this paper.PerhapsDavie and Hutton had changedprocessesby the time Tytler wrote (Black'sopinionis
not datable), for severalsynthetic processeshad been introducedelsewhere by the 1770's.In any case, both Black and Tytler admitnot having seen the Edinburghworks, and their reports are contradictedby
others,such as Hutton's biographer,Playfair,who says they used soot
alone.The balanceof evidence seemsto indicatethat the Edinburghsal
ammoniacworks of 1756producedthe substanceby simplesublimation
from coal soot.
II. Synthetic Sal Ammoniac
A numberof truly synthetic processesfor sal ammoniacproduction
were undertakencommerciallyin the last forty years of the eighteenth
century, and among them were the processespostulatedby Black and
Tytler. The secrecy that preventedthem from obtainingdefinitivein10J. P. Tournefort, "Comparaisondes analyses du sel ammoniac, de la soie et
de la come de cerf," Mem. Par. (1700), pp. 71-74.
11J. F. L. Morand, L'Art d'exploiter les mines de charbon de terre (Paris, 176879), p. 31. Many other writers also speak of a solid form of volatile alkali.

574
RobertP. Multhauf
formationseemsto have been successfullymaintainedby all sal ammoniac manufacturersinto the 1790's,priorto which I find no eye-witness
descriptionof a factory.
It is clear enough that severaldifferentsynthetic processeswere used
and that they can be distinguishedin modern chemical terms. In order
of increasingsophisticationthey can be describedas follows.
1. Direct interactionof ammoniaand hydrochloricacid:
NH3+ HCl-NH4Cl.
The possibilityof thus combining "volatilealkali"and "spiritof salt"
was frequently mentionedfrom the time that Sala observedit, usually
with the remarkthat it could be commerciallyuseful if spirit of salt
could be made more economically than by the traditionalmethod of
decomposingsalt with sulfuricacid.12The developmentof the chamber
processfor sulfuric acid after about 1750 was to so reduce the cost of
sulfuricacid as to remove this obstacle,a condition that seems to have
come about in Englandand Scotlandin the 1770'sbut not for another
two decadeson the Continent.
With very few exceptions,writers on volatile alkalispeak of animal
matter,usually slaughterhousewaste or urine, as the sole source. Accounts of its productionare spectacular.As Davie and Hutton are supposed to have collected all the chimney sweepings in Edinburgh,so a
London sal ammoniacmanufactureris said to have had an army of
women and childrencollecting animalbones throughoutthe metropolis, and a Parismanufactureris reported (until his neighborsdemurred)
to have collected urinefrom all the sewersin Paris.13In any case, almost
all of the factoriesrelied on animalwaste. The first exceptionwas probably that of Lord Dundonald,whose establishment(1781) for the distillationof coal yielded by-product ammoniawhich was almost immediately appliedto the manufactureof sal ammoniac.
By the mid-nineteenthcentury the direct process had supersededall
others for the manufactureof sal ammoniac,and it was accomplished
with utter simplicity through the additionof hydrochloricacid to the
12See J. H. Zedler, Universal Lexicon (Leipzig, 1742), XXXIII, col. 1015. The
seventeen-thousand-word article on "Salmiak" in Zedler is the longest early treatment of the subject known to me. By contrast the Diderot encyclopedia covers sal
ammoniac in about twenty-five hundred words.
13 The
London manufacturer, not identified, is reported in J. H. Kriinitz,
(Berlin, 1822) CXXXI, 181-82. The
Oeconomisch-technologische
Encyklopidie
article on sal ammoniac in Kriinitz runs to more than twenty thousand words. The
report on the French manufacturer refers to the works at Grenelle and comes from
Dictionnaire technologique (Paris, 1831), XIX, 239-40.

575
"ammonialiquor" from coal distillation.14While it is possible that

Dundonald used this process, it is far from certain, and the only
eighteenth-centurysal ammoniacworks that beyond doubt used the
direct process attemptedit rather through the interactionof the two
gases,ammoniaand hydrogen choloride.This was the factory of Nicolas Leblanc, establishedbetween 1791 and 1794, supposedly as an adjunct to his soda works, but by all indicationsa more successfulundertakingeven though it only lastedabout a decade.
2. Double decompositionof ammoniumsulfate and sodium chloride:
(NH4) 2C03 + CuSO4- CuCO031+ (NH4) 2S04
(NH4)2S04+ 2NaCl--Na2SO4+ 2NH4C1.

Ammonium carbonateis the form taken by ammoniawhen distilled
from carbonaceousmaterialwithout drying. Although its conversion
into ammoniumsulfate is accomplishedhere through copper sulfate
(blue vitriol), othersulfates,such as calciumsulfate (gypsum) could be,
and were, used. The requirementis that an insoluble carbonate be
formed, permittingthe separationof the ammoniumsulfate. The separationof the sal ammoniacin the second reaction was accomplished
either by its sublimationor by differentialcrystallization.
This appearsto have been the earliestcommercialprocess for artificial sal ammoniacif, as is probable,it was used in the works established
by Johann H. Gravenhorstat Brunswick in 1759.15It is also probable that the majorityof all sal ammoniacworks used variationsof this
method, but for an adequatedescriptionof the commercialproduction
of sal ammoniacin such a processwe must go to one that used gypsum,
the factory of Payen, Bourlier,and Pluvient,which had its beginnings
in 1797.
3. Double decomposition of ammoniumcarbonate and magnesium
chloride (bittern):
(NH4)2C03+ MgCl2-MgCO3+ 2NH4C1.
This involved one step less than the preceding process and moreover
utilized as a source of magnesiumchloride the waste mother liquor,
"bittern,"of the ordinaryprocess for the production of common salt.
This processwas introducedcommerciallyby the well-known hydrom14 See
Fig. 5.
15 There are
many conflicting accounts, all speculative, of the Gravenhorst process. The most plausible is in Kriinitz, op. cit., pp. 182-83. In general, for processes
associated with particularpersons (or places) I have placed supporting data in the
Appendix, pp. 583ff.

576
Robert P. Multhauf
eter inventor, Antoine Baume, only a year after the establishmentof

the Gravenhorstfactory, and we have a circumstantialaccount of his
works written in 1776,16while it was still in operation.
In the discussionthat follows I shallrefer to these, respectively,as the
direct,sulfate,and bitternprocesses.
III. The Sal AmmoniacIndustry
While synthetic production of some other materials,notably soda,
may have been more urgently sought in the eighteenthcentury, it does
not appear that commercialproduction was so widely achieved, and
certainly not by such a variety of methods, as was the case with sal
ammoniac.Its history as a substanceproduced on a large scale lasted
less than a century, and it had reverted before 1850 to a by-product
which, however useful, was no longer of much interesteither to chemists or engineers.In Muspratt'saccount of the direct process as practiced in Liverpoolin 186017we encounter a descriptionof its production after a manner of astonishingcrudity by comparisonwith the
ingeniousand almosteleganttrainsof apparatuslaid out by the nascent
chemical engineers of the eighteenth century. Their history affords
what is perhapsan unequaledopportunityto observethe beginningsof
modernindustrialchemistry.
From the time of Baume'sundertakingat Gravellenear Charentonin
1760 there was a successionof sal ammoniacfactories in the Paris region. Baume'sfactory ceasedoperationin 1787,after which, according
to AnselmPayen,18there was no productionof the substancein France
for a decade. Two works using the sulfate process were establishedin
the latteryear, that of BernardPluvinetnear Rouen and that of Payen
(whom I conjectureto be Anselm'sfather) at Grenelle on the Seine
below Paris. Subsequentlyamalgamatedinto the firm of Payen, Pluvinet, and a third party, Bourlier,at Clichy, they were still, according
to French patent literature,primarily concerned with sal ammoniac
manufactureas late as 1817.
In the meantime,Leblanchad establishedhis chemicalworks at Maison de Seine near St. Denis, which began its sporadic operation between 1791 and 1794.Contemporaryevidence indicatesthat sal ammo16J. F. Demachy, L'Art du destillateur d'eau forte et du liquorist (Paris, 1776),
pp. 120-23 (copied in part in Encyclopedie methodique [1789], VI, 747-50).
17 Sheridan Muspratt, Chemistry . . . as Applied and Relating to the Arts and
Manufactures (2 vols.; Glasgow, 1860), I, 184-92.
18
In Dictionnaire technologique, p. 220.

577
niac was merely a by-product in Leblanc'ssoda factory,19but writers

of the generationafter Leblancappearto have regardedit as primarily
a sal ammoniacfactory.20In any case, it never achieved much importance for soda manufacture,but it did get into the literatureas one of
the more importantsal ammoniacworks.
Although writers of the late eighteenth and early nineteenthcenturies imply that sal ammoniacwas continuously produced in England,
the record is largely one of obscure inventorswho have left no traces
in the history of industry. Both SamuelParkesand Thomas Thomson
wrote of a Mr. Goodwin who had attemptedthe bittern processin the
early eighteenthcentury.This may refer to JamesGoodwin, a London
"chymist"who was censoredby the Society of Apothecariesfor drug
adulterationin 1724,and the processmay be that mentionedby Robert
Dossie as having been in operation in 1740.21Other obscure Englishmen
are occasionally mentioned as undertakersin sal ammoniac,William

Sedgwick (1749), SamuelFalconbridge(1769), and, at the end of the
century, Hector Campbelland William Menish. The only one who
seems commerciallysignificantwas Menish,who practiced the sulfate
processfor about a decadeafter obtaininga patent in 1792.According
to Parkes22he retireda wealthy man but was discouragedby the application of the excise tax to his by-product, Glauber'ssalt.
The Society of Arts apparentlygave a numberof premiumsfor improvementsin sal ammoniacmanufacture,amountingin value to 15 per
cent of the prize money awardedbetween 1754 and 1782.The society
claimedsome credit for what they called the flourishingstate of the industry by the latter date, but the proprietorsand factories responsible
for a flourishingindustryby that date remaina mystery. Scatteredreferences suggest that sal ammoniacwas produced in London through
19See Annales de chimie, XIX (1797), 60-76 (part of "Extrait d'un rapport sur
les diverses moyens d'extraire avec avantage la soude du sel marin," by Citizens
Lelievre, Pelletier, D'Arcet, and Alexandre Giroud). This account, and a description of the Liege process by "Citizen Baillet" (Journal des Mines, II, No. 10
[1795], 3-11), are the earliest eye-witness accounts of sal ammoniac factories
known to me.
20 See the articles on sal ammoniac
by Samuel Parkes in ChemicalEssays (5 vols.;
London, 1815), IV, 339-98; S. F. Gray, The Operative Chemist (London, 1828),
pp. 532-34. It is interesting to note that Leblanc's own book (which I have not
seen) was entitled, Memoires sur la fabrication du sel ammoniac et de la soude
(Paris, 1798).
21 Parkes (op. cit.,
p. 380), who quotes a work written by Dossie in 1759,thinks
two different persons are involved.
22 Op. cit.,
pp. 364-65.

578
RobertP. Multhauf
much of the eighteenthcentury, using sulfuricacid, ammonia,and salt,

either in the direct or the sulfate process,23but this remainssupposititious for it has left no definitiverecord in the literature.
Scottish enterprisesin sal ammoniacare more fully reported, and it
appearsto have been Scotland that was, from beginning to end, the
most importantcenter of the sal ammoniacindustry.Dundonaldis principally distinguishedin the history of industry as the first to attempt
to commercializecoal tar, with a factory establishedin 1781at Culross
on the Forth (between Glasgow and Edinburgh),but he seemsto have
attemptedalmostimmediatelythe recovery of by-product ammoniaby
convertingit to sal ammoniac.His product pleasedDavie and Hutton,
to whom he sent a sample.They contracted for his sal ammoniac,as
their own was inadequateto supply the market,and ultimatelygave up
their own soot-distillationprocessaltogether.
Very little behindDundonaldwas CharlesMacintosh,a twenty-yearold clerk who enteredthe chemicalbusinessin 1786 with a sal ammoniac factory in Glasgow. Macintoshwas to prosperas a chemicalmanufacturer and to gain immortality in 1823 with the invention of the
rubberizedwaterproof garmentcalled the "Macintosh."He had abandoned the sal ammoniacbusinessin 1792,but Dundonald'sinvolvement
continued,and there is evidence of his continualinterest in improving
the processthroughinquiryinto the processesof othersand through his
own effort, in testimony of which we have a patent of 1794. In 1814,
however, we hear that there was only one important sal ammoniac
works in Scotland,24and that not Dundonald's,but the undertakingof
yet anotherinventor,JosephAstley, who had obtaineda patentin 1807,
which he was successfully exploiting at Bo'ness, directly across the
Clyde from the Dundonaldfactory at Culross.
Despite the fact that Germany alone seems to have produced an extensive literatureon sal ammoniacmanufacturein the eighteenth century,25the Germanindustryremainsthe least known. Gren, writing in
1782, spoke of factories in five German towns but confessed to no
"authenticproof" of the processesused in any of them. He attempted
to reconstructthe Gravenhorstprocessfrom scrapsof evidence and is
consoled in his failureby the fact that he has himself discoveredalong
the way a new process, apparentlythe sulfate process using alum. In
23 Cf. the quotation of Dossie by Parkes, op. cit., pp. 385-86.
24 Clow and Clow, op. cit., p. 421.
25The bibliography in Kriinitz (see n. 13 above) lists a number of monographs,
including a book by W. C. Alberti, Anleitung zur Salmiakfabrikation(Berlin, 1780),
which is summarizedin Kriinitz.

P,i os. Trans. Vo.LZ. TAB.XI. . 55.
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FIG. 1.-Sal ammoniac production: the Egyptian process. From a report by Hasselquist, as published in Philosophical Transactions,LI (1760), 504-6.

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FIG. 2.-Sal ammoniac: Baume's process. Figs. 1 and 2, gallery furnaces for producing ammonia from wool waste. They are 5 ft. long. Ammonia, collected in the globes
outside the furnace, is added to bittern in apparatus not shown. Fig. 3, a sublimation
flask. From Demachy, L'art du distillateur (Paris, 1780), pl. 9.

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FIG. 4.-Sal ammoniac: Leblanc's works; a and a are salt furnaces, one lead lined to
start the process of hydrochloric-acid production from salt and sulfuric acid and one
brick lined to finish it; h is the furnace for production of ammonia from organic waste;
c is the lead-lined reaction chamber; k is an"aeolopile" for blowing steam into the reaction
chamber. From Gray, The Operative Chemist (London, 1828), Fig. 227.

Fil. 113.
?, :
-t
-I
~~~~~~~..
--
w~~~~~~~~~~~
X
.?
_,:,#
. @
...
r-C-?
FIG. 5.-Sal ammoniac: The direct process as practiced by Kurz, Cropper and Co.,
Liverpool. Ammoniacal liquor is being pumped into the "tuns" of fourteen-eighteen
thousand gals. On the right gutta-percha carboys of hydrochloric acid are being raised to
be poured into the tuns. From S. Muspratt, Chemistry (Glasgow, 1860), I, 89.

579
1786 he was reported to be applying it in a factory that also produced

soda, Glauber's salt, and other products.
IV. Science, Technology, and Sal Ammoniac
More than a century elapsed between the time when Sala and Glauber unraveled the constitution of sal ammoniac and the corresponding
scientific elucidation of its constituents, hydrochloric acid and ammonia, which occupied the years 1774-1807 and commanded the attention
of Scheele, Priestley, Berthollet, Davy, and other well-known scientists. In 1809 Gay Lussac determined the quantitative composition of
sal ammoniac as part of the proof of his "law of combining volumes"
of gases.26It would be difficult to contradict the view that technological
developments during this period made no contribution to the scientific
understanding of sal ammoniac-to which it should be added, however,
that we are considering an era when there was no clear differentiation
between science and technology. Later generations tend to rate as scientists the more eminent practical chemists, such as Glauber, and hence
to exaggerate the importance of science vis-a-vis technology.
Our principal concern, however, is with the significance of scientific
investigation for industrial development. It can be shown that the
chemistry involved in the complex of processes used for sal ammoniac
production is to be found in the early scientific literature. The combination of volatile alkali and spirit of salt in the direct process from the
time of Sala was mentioned often enough as a possibility, and there is
little doubt that its implementation was inhibited by the cost of sulfuric
acid used to prepare the spirit of salt. The role of the scientist in the
successful effort to circumvent this difficulty is highly questionable,
however. It was circumvented in the Liege process, practiced in Flanders from about 1780, which involved the combusion of briquettes of
coal, soot, salt, and clay, and in the process patented by Astley in 1807
in which sal ammoniac was sublimed directly from a mixture of animal
waste and bittern. Sedgwick's proposal of 174927was of this type, and
indeed the urine-soot-salt process itself may be regarded as an abortive
prototype of this kind of process. Coming to an evaluation of the role
of science and technology in the development of these processes, we
observe that the scientific literature is full of the urine-soot-salt process,
which did not work, while largely ignoring the other processes which
were actually capable of producing sal ammoniac. The exposure of the
26 On the determination of the constitution of ammonia and
hydrochloric acid
see Hermann Kopp, Geschichte der Chemie (4 vols.; Braunschweig, 1843-47), III,
246-48, 349-51.
27
British patent No. 641 of February23, 1749.

580
RobertP. Multhauf
fallacy of the urine-soot-saltprocess,moreover,came as a result of attempts to reconcile it with the Egyptian process and does not seem
directly connected with the ultimatescientific explanationof that fallacy through the doctrine of affinities.Indeed, its exposurewas painfully achievedby the academiciansof Paris,for ClaudeGeoffroy, who
first called their attentionto the Egyptian process,was intent on proving its identity with the supposedurine-soot-saltprocess.The voluminous literatureproducedin Paris between 1700 and about 1740 sometimesverges on the ludicrousin the characterof the argumentsresorted
to over the animal,vegetable,or mineralorigins of sal ammoniac.
And yet the efforts of the Paris academiciansclearly representthe
beginningsof a comprehensiveand continuousexplorationof the chemistry of familiarsubstanceswhich was finally to revolutionizenot merely the science of such materialsas sal ammoniacbut chemistryitself. In
the mid-eighteenthcentury the scientific study of sal ammoniacbecame more fruitful, althoughthe evidence comes less from Paris than
from what was then somethingof a satelliteenterprise,the new Academy of Sciences in Berlin.Although the doctrine of affinitieshad been
particularlyassociatedwith the Paris chemists, its applicationto the
explanationof the fallacy of the urine-soot-saltprocess seems to have
been more evident to the less imaginativebut more systematicchemists
of Berlin.28In studying a substancethey systematicallyobservedits interactionwith other commonplacematerials,and as ammoniumsulfate
(then known as "Glauber'ssecret sal ammoniac")and bitternfell under
their scrutiny they did not fail to observe those interactionsin which
sal ammoniacwas produced.Thus in 1754 we find the sulfate process
mentioned-incidentally-in connectionwith a study by JohannPott of
and under similarcircumstancesthe
"Glauber'ssecret sal ammoniac,"29
reactionsinvolvedin the bitternprocessappearin 1759as part of Marggraf's studiesin the analysisof the mother liquor of common salt.30
Despite this notable advancein the scientist'scommandover sal ammoniac, the dependence of the technologist on that advance remains
unclear. Pott and Marggrafwere interested only in analysis, and although the latter makes reference to the possibility of producing sal
ammoniacin the bittern process,he adds that he had just learnedthat
28The affinityrelationships
areclearlyexpoundedin Zedler,op. cit., col. 1015.
29 J.
H. Pott, "Recherches sur le melange d'un acide du vitriol avec le salmiac
Mem.Berlin(1752),pp. 67,81.
&surles produitsqui en resultent,"
30A. S. Marggraf,"Experiencechymiquesconcernantce qu'on nomme la
du sel de cuisine,relativementa I'aspectde
dernierelessivemere incristallisable
ternequi y est contenu,"Mem.Berlin(1759),pp. 19-27.

581
this was already being done. It is not clear what this refers to, as
Baume'sworks began operationonly in the following year, but as we
have seen, the history of sal ammoniacproduction presents entrepreneurs of all degrees of obscurity. The factory in which Gravenhorst
used the reactionsrevealedin Pott's articlefollowed that publicationby
five years, but here again we have such precursorsas the ill-famed
Goodwin. It becomes more doubtful that these processes depended
upon any scientific formulationwhen we considerthe incidentalcharacter of the observationsof Pott and Marggraf.Ammoniumsulfateand
magnesiumchloride remainedwrapped in mystery so far as most scientistswere concerned.Baumehimself was still vague on the natureof
bittern in his textbook of 1773, although his own process depended
upon its properties.
Still, the fact that virtually all of the chemical data applying to the
variousprocessesfor producingsal ammoniaccan be found in the scientific literatureprior to the effective foundation of the Europeansal
ammoniacindustry can hardlybe irrelevantto the explosivegrowth of
that industry after 1756. It seems very probablethat the obscure men
who were primarilyresponsiblefor the success of that industry were
beneficiariesof the literatureof popularscience which flourishedin the
mid-eighteenthcentury. But if the technology of sal ammoniacwas
ultimately dependentupon science, the scientist played a very minor
role in the industrializationof sal ammoniacproduction,which was accomplished primarily by men whose principal qualificationsseem to
have been ingenuity and a spirit of enterprise.SamuelSmiles was not
yet aroundto immortalizemen of ingenuity and enterprise,and Davie,
Gravenhorst,Pluvinet, and their fellows are barely identifiablein the
literature.
They would appearto be the ancestorsof the chemicalengineer,for
the surviving evidences of their factories indicate a remarkabledevelopmentof the techniquesof chemicalmanipulationon a large scale,
involving problems the existence of which was scarcely known to
scientists.There are indicationsof the developmentof corrosion-resistant apparatusand of large-scalefluid transfer.Gravenhorstand Pluvinet
accomplishedthe separationof salts on a large scale by differential
crystallization,and Leblancsucceededin reacting gases in an industrial
process.The sulfateprocesswas worked as a continuoussystem.31
The sal ammoniacmanufacturersalso encountered,and to some degree mastered,economic problems of which science showed a bare
awareness.The earliestof the synthetic processes,that of Gravenhorst,
31
Most of these innovations are shown in the accompanying illustrations.

582
RobertP. Multhauf
was part of an industrialcomplex which producedalum,Glauber'ssalt,

and "Brunswickgreen" (basic copperchloride) as well as sal ammoniac.
The almostinvariablecombinationof severalprocesses,and production
of severalproducts,may go far to accountfor the difficultyencountered
by scientific writers in describingthese factories-a difficulty that is
pointed up in the fact that JosephBlack, who was a friend of Hutton,
Dundonald,and Macintosh (and who had probably instructed one or
two of them in chemistry) did not know how they produced sal ammoniac.32It is clear enoughthat sal ammoniacwas the primaryproduct
of all of the works I have mentioned,with the apparentexception of
that of Leblanc;but Glauber'ssalt was the most importantby-product,
and this led the sal ammoniacmanufacturersto play a prominentpart
in the researchesthat led to the synthesisof soda from Glauber'ssalt,
which was accomplishedat the end of the eighteenthcentury.33
Sal ammoniacwas largely produced from waste materials,which
provided the substanceitself in the soot-sublimationprocess and the
ammoniain all processes.With the developmentof the bittern process,
sal ammoniacwas againproducedentirely from waste materials.Yet it
was economics that finally defeated the sal ammoniacmanufacturers.
Their enterpriseswere repeatedlyblunted by the strangetariff laws of
the eighteenthcentury, above all by the salt taxes. Menish gave up in
the face of the refusal of the governmentto exempt his Glauber'ssalt
from duty. The bittern process assumedits greatestimportancein that
it liberatedthe sal ammoniacmakersfrom dependenceupon salt,34but
it was too late. Parkesrecommendedfurther economies to obviate the
cost of shippingbittern by moving to its source, but the difficulty in
his time seemsratherto havebeen that the demandfor sal ammoniacwas
in an irreversibledecline. Methodshad been devisedfor obtainingpure
ammoniadirectly from coal without the intermediacyof sal ammoniac,
and for cleansingmetal surfacesit was being replacedby hydrochloric
speculation on the process used at Edinburgh would appear of necessity to refer to the Davie-Hutton works. He tells us nothing of the factories of
his friends Dundonald and Macintosh.
33 There is even some
question about Leblanc. Gillispie has surmised (Isis,
XLVIII [19571, 167-70) that Leblanc may have been influenced by an account
of Dundonald's work publishedby J. C. de la Methrie in 1789 (Journalde physique,
XXXIV [1789], 42-44). La Methrie says as much about Dundonald's sal ammoniac
enterprise as he does about soda, but it is clear enough that Dundonald was trying
to decompose the by-product Glauber'ssalt with carbon (see also Archibald Clow
and Nan Clow, "Archibald Cochrane, 9th Earl of Dundonald," Chemistry and
Industry [June 10, 1944], pp. 217-19).
34
Although this factor is frequently mentioned, it is dwelt upon most by Parkes,
who includes among his observations the discovery that there was a duty on bittern in England but not in Scotland (op. cit., pp. 373-78).
32 Black's

583
acid. It proved after all not to be sal ammoniacthat was wanted in

commercebut its ingredients!
Epilogue
It would seem that an industrialchemist of the time of Parkescould
with justificationregardconsiderationsof economicsand engineeringas
of primary importancein the establishmentof an industrialprocess.
Within the half-century after him science diminishedin the views of
British industrialchemists almost to the vanishing point. Those who
reviewedthe history of the sal ammoniacindustrymadea whippingboy
of Baume,the most conspicuousscientific figure in the business-and a
Frenchmanto boot. The Britishsoda manufacturer,SheridanMuspratt,
remarkedin 1860that Baume'sfactory "failedafter 27 years,leavingthe
shareholderssufferersto the amountof four hundredthousandfrancsanotheramongmany instanceson record of a purely theoreticalchemist
not being always the fittest person to conduct a manufacturingoperation."35 Although only two or three other factories seem to have lasted
as long as Baume's,Andrew Ure called it "a foolish manipulationof 27

years, one out of a thousandinstanceswhere theoreticalchemistshave
shown their total incapacityfor conducting operationson the scale of
manufacturingeconomy."36
But it seemsto have been economics,ratherthan engineering,that led
to the extraordinarypolarization between science and technology
which is implied by these words. Ure and Musprattwere hardly engineers.The former held a degree in medicine from Glasgow and occupiedthe post of professorof chemistryat the AndersonianUniversity
there. Muspratt,who inheriteda chemicalworks, was trainedin chemistry at several universitiesand worked for some time under Liebig.
Baume, their favorite example of a pure theoretical scientist, had by
contrast been a self-educatedpharmacistand manufacturingchemist
who seemsto have had some difficultyconvincing his colleaguesat the
academy of his pedigree as a scientist.While the scientist was clearly
in eclipse in the nineteenthcentury, it seems to have been the shareholder ratherthan the engineerwho was in ascendancy.
APPENDIX
NOTES ON EARLY SAL AMMONIAC MANUFACTURERS
JosephAstley received a Britishpatent on July 28, 1807,for the bittern
process.According to the article "SalAmmoniac"in Rhees EncycloMuspratt, op. cit., p. 184.
36Andrew Ure, Dictionary of Arts, Manufactures,and Alines (New York, 1851),
p. 1087.
35

584
Robert P. Multhauf
pedia (1819), his processinvolved the mixing,drying, and heatingof

animalmatterand bittern.
Antoine Baume'(1728-1804), a well-known French chemist and member of the Academie des Sciences, establishedin 1760 a factory at
GravellenearCharentonand operatedit until 1787.See n. 16; J. A. C.
Chaptal, La cbimie appliquee aux arts (Paris, 1806), IV, 181; and
Dictionnairetechnologique (cited in n. 13), pp. 219-20. But see also

Charlard,below.
Bourlier,an associateof Pluvinet, otherwiseunknown.
Hector Campbellattemptedunsuccessfulyto exploit the sulfateprocess
usingmagnesiumsulfate,accordingto SamuelParkes(n. 20), pp. 36667. That he lived shortly before Parkeswrote is suggestedby the fact
that a person of this name received a British patent for chlorine
bleachingin 1792.
Charlardhad operateda sal ammoniacfactory nearParisfor some time,
according to Demachy (n. 16), writing in 1780. The Encyclopedie
methodique (n. 16) quotes Demachy but attributes this work to
Baumeand placesit at Charenton.
JamesDavie was a contemporaryand associateof JamesHutton in the
sal ammoniacworks establishedin Edinburghin 1756. One receives
the impressionfrom John Playfair'sbiography of Hutton (Transactions of the Royal Society of Edinburgh,V [1803], 39-99) that
Davie may have been the principaldeveloperof this process.
MichaelJ. J. Dize (1764-1852) was a Parisapothecaryassociatedwith
Leblanc.See Gillispie (n. 33), pp. 152-70.
Dundonald,9th Earlof (ArchibaldCochrane,1749-1831),was a notable
Scottish chemical inventor and industrialist.See the Dictionary of
National Biographyand Clow and Clow (n. 7 and 33). His patent of
1781, for coal distillation,included reference to the production of
"essentialoils, volatile alkali,mineralacids,saltsand cinders."In 1794
he received a patent for preparing "alum . . . and other salts, saline
matters,and substances,"which includedsal ammoniacby the sulfate

process (see Repertory of Arts, IV [1796], 1-8).
Samuel Falconbridgereceived an award from the Society of Arts in
1796for sal ammoniacproduction.
JamesG. Goodwin was a London chemist censoredby the Society of
Apothecariesin 1724. Parkes (n. 20) and Thomas Thomson ("Sal
Ammoniac,"EncyclopaediaBritannica[suppl. to 4th, 5th, and 6th
eds.; 1824]) said that a chemist named Goodwin produced sal ammoniacby the bitternprocessabout a century earlier.
Johann H. Gravenhorst (1719-81) was a Brunswick tradesmanand
beer brewer who establisheda chemicalworks for sal ammoniacand

585
other chemicals in 1759. It was continued after his death by his

brother Christoph (1731-94). See Allgemeine Deutsche Biographie.
On his processsee Crelle'sNeusten Entdeckungenin der Chemie,VII
(1782), 19-38; Encyclopedie methodique (n. 16); Klaproth and
Wolff, Dictionnairede chimie (Paris,1810-11), IV, 167-68;and J. H.
Kriinitz (n. 13), pp. 182-83.
FriedrichA. C. Gren (1760-98) was professorof chemistryand medicine at Halle. He wrote on the production of sal ammoniac in
Crelle'sNeusten Entdeckungenin der Chemie (loc. cit. [cited under
Gravenhorst]) and is described later in that same journal (XIII
[1786], 275) as a manufacturerof soda, sal ammoniac,Glauber'ssalt,
etc.
James Hutton (1726-97), the celebrated "father" of geology, with
James Davie establishedwhat is generally regarded as the first sal
ammoniacfactory in Europe (1756). On his biographysee Playfair,
op. cit. (cited under Davie). On his sal ammoniacworks see Clow
and Clow (n. 7) and J. H. Beckmann, "Salmiak,"Beytrdge zur
Geschichteder Erfindungen,Vol. V (1805).
Nicolas Leblanc (1753-1806) was surgeonto the Duke of Orleans;after
the Revolution,administratorof the Seine Department;and inventor
of the Leblancsoda process.On his sal ammoniacprocesssee Annales
de chimie, XIX (1797), 60-76. Leblanc wrote a Memoires sur la
fabricationde sel ammoniacet de la soude (n. 20), which I have not
seen.
Liege process,involving the fabricationof briquettesof coal, soot, salt,

and clay, and their ignition interlayeredwith bones, is sometimes
called the Dutch process.It is describedby "CitizenBaillet"(n. 19).
Chaptal(op. cit. [cited under Baume], pp. 178-80) calls it the most
importantprocess.
Charles Macintosh (1766-1843) was a Glasgow chemical manufacturer
and inventor of the rubberized coat (1823) (the "Macintosh"). See
Dictionary of National Biographyand George Macintosh,Biographical Memoir of Charles Macintosh (Glasgow, 1847). On sal am-
moniac, which was his first enterprise (1786), see Clow and Clow
(n. 7), pp. 254-55, 446, etc.
WilliamMenishreceivedBritishpatentNo. 1898,datedJuly 5, 1792,for

making "sal ammoniac and Glauber and other salts for all commercial
purposes" (Repertory of Arts, I [1794], 303-5). Accounts of a sulfate
process using the mother liquor of vitriol by Nicholson (A Diction-
ary of Chemistry [London, 1795]) and by Aiken (Dictionary of
Chemistry and Mineralogy [London, 1807]) probably refer to Menish's works. See also Parkes (n. 20), pp. 364-65.

586
Robert P. Multhauf
Samuel Parkes (1761-1825) reviews numerous processes for sal ammoniac in his ChemicalEssays (n. 20) and concludes by developing
one of his own, which he seemsnever to have applied.
Payen was proprietorof a sal ammoniacworks at GrenellenearParisin
1797. His works was later amalgamatedwith that of Pluvinet. I
conjecturethat he was the father of AnselmPayen, who discusseshis
works in Dictionnairetechnologique(n. 13).
Bernard Pluvinet (1775-1800) was a Paris manufacturing chemist
and one-timesupplierto Lavoisier.See D. McKie, Antoine Lavoisier
(New York, 1952), pp. 392, 412. Anselm Payen says (Dictionnaire
technologique[n. 13], pp. 218-42) that he hada sal ammoniacfactory
at Rouen in 1797. Cadet (Dictionnaire de chimie, III [1803], 352)
and Chaptal(op. cit. [cited underBaume],p. 182) call Pluvinet'sthe
best process. French patent records mention "Payen, Bourlier, et
Pluvinetfreres fabricansde sel ammoniac"in 1812and 1817.
WilliamSedgwick received BritishpatentNo. 641, dated February23,
1749, for "the art, mystery or method of making a drug called sal
ammoniac."


Sal Ammoniac-A Case History in Industrialization-Robert P. Multhauf

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