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Stanislao Cannizzaro, F.R.S.

(1826-1910) and the First International Chemical Conference at


Karlsruhe in 1860
Author(s): Harold Hartley
Source: Notes and Records of the Royal Society of London, Vol. 21, No. 1 (Jun., 1966), pp. 56-
63
Published by: The Royal Society
Stable URL: http://www.jstor.org/stable/530818 .
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56

STANISLAO CANNIZZARO, F.R.S. (I826-I9I0)


AND THE FIRST INTERNATIONAL CHEMICAL CONFERENCE
AT KARLSRUHE IN i860

By SIRHAROLDHARTLEY,
F.R.S.

[Plate6]

M /Y interest in the KarlsruheConference dates from the day in I899


when I bought for one markthe copy of Cannizzaro'sclassicpamphlet,
Suntodi un corsodifilosophiachimica,which Pavesi gave to Hermann Kopp
after the last session of the Conference, containing some notes in Kopp's
handwriting (I). I have always been puzzled as to why the Conference, in
spite of Cannizzaro'spresenceand his eloquent speeches,failed to achieve its
object, and yet when they read his pamphlet on the way home, as Lothar
Meyer says, 'the scalesfell from my eyes' (2). At long last I think I see how it
happenedand on whose shouldersthe responsibilityrests.
During the years 1825-I860the effortsof most of the outstandingchemists
-Liebig, W6hler, Dumas, Laurent,Gerhardt,Wurtz, Williamson, Kekule,
Kolbe and Franklandwere directed to the organic field, the compounds of
carbon, where they found a rich harvest. Each of them had his own theory
which was of specialvalue to him in stimulatinghis line of attack.As a result,
rapid progress was made in a number of different directions,which were
bound to lead eventually to a common understandingof the structureof
carbon compounds. Probably at no time in the history of chemistry was
there such bitter personalanimosity between these holders of rival theories,
culminatingin the unfortunatepersecutionof Laurentand Gerhardtand the
death of Laurentfrom sheerwant. So great was the lack of a common point
of view that in 1859Kekule filled a whole page of his textbook with different
formulaeof such a simple compound as acetic acid and the formula of water
was written in four differentways, H,O, HO, -tO, H202.
It was this confusion of ideas that stimulatedthe young Cannizzaroin
I858 to give a courseof lecturesto his studentsin which he tried to rationalize
the conceptionsof atom and molecule and of atomic and molecularweight.
A year later Kekule had the idea of initiating an internationalchemical
conferenceto try to reachsome agreementin orderto end the chaos that was
bedevilling progress.
Cannizzarowas born in Palermoin 1826and he inheritedfrom his parents
much of the fiery temperamentof the Sicilians.He first studied medicine

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Plate 6

SIJNTO DI UN CORSO
DI

VIU00OVIA a*IMIua
F A T r 0

5)(94o( of. uvwr"tetsomIN Ceiova

S.CANNIZZARO
DAtPROF.

NO TA
SULLE CONDENSAZIONI DI VAPORE

DILL' AUToiE STESSO

Wa^
TIPOGRAFIA PIERACCINI

1858

Title-page of Cannizzaro'sSuntodi un corsodifilosophiachitnica.

[Facingpage 56

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57
at the Universityof Pisaandlaterchangedto chemistry,in i850 becoming
In hisresearches
Piria'sassistant. on benzylalcoholhe discoveredthereaction
which bearshis name. From 1853 to i858 he held a professorship at the
TechnicalInstituteof Alessandra andin I858 was appointedto the Chairof
Chemistry in the Universityof Genoa. It was therethathe gave the classic
courseof lectureson atomicandmoleculartheorythatis a landmarkin the
historyof chemistry.Cannizzarosaw so clearlythat this confusedstateof
chemicaltheory was due to the reluctanceof chemiststo acceptwhole-
heartedlythelogicalconclusions fromtheworkof GayLussacandAvogadro
owing to theirpreconceived ideason one aspector another.He was anxious
thathis studentsshouldbe savedfrom the confusedthinkingof the period.
Fortunatelywe know the run of Cannizzaro's mind from the precisof the
lecturessent to de Lucawhich was printedin the NuovoCimentoin May
I858 (3). The lectureswere basedon a historicalexpositionof the courseof
events,startingwith theworkof GayLussac,AvogadroandAmpere,making
logical deductionsfrom the known experimentalfacts. Cannizzaronext
showed how Berzelius,misled by his own electrochemicaltheory and
dualisticapproach,disregarded the distinctionmadeby Avogadrobetween
the atomsandmoleculesof elementarygasesandcontinuedto regardtheir
elementaryparticlesas monatomic.Basinghis approachsolelyon molecular
weights determinedby vapour densitiesand on the proportionsof the
elementspresentin the molecularweights of elementsand compounds,
Cannizzaro showedthe conclusivenatureof the criteriaregardingtheatomic
weights of the elementswhich agreedwith the valuesassignedto them by
Berzeliusin 1826 with the exception of the alkali metals and silver.
Cannizzaronext showed that his values for atomic weights were con-
firmed by the values of the specific heats of elements and compounds
following Dulong and Petit and Regnault's later work.
Turning then to organic chemistry and following Gerhardtand Laurent
he showed how the vapour densities of organic compounds were all con-
sistent with his atomic weights and with Gerhardt'sformulae. He pointed
out that Gerhardt'sassumption, that metallic monoxides all had the same
formulaeas water, had led him to assignwrong values to the atomic weights
of many metals. The formulae and the equations with which Cannizzaro
illustratedhis later lecturesare those in use today. Finallyhe explainedquite
correctly the apparent anomalies presented by the vapour densities of
ammonium chloride, hydrogen sulphate and mercuric chloride as due to
dissociationin the vapour state.
These lectures must have been a beautifully clear piece of exposition

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58
aidedby Canni77aro's naturaleloquence.However,the publishedaccountof
them seems to have attractedlittle notice and he had to wait for the
Karlsruhe Conferencefor his opportunity.
Early I860 Kekulewrote to Weltzien,the professorof chemistryin
in
Karlsruhe,about the possibilityof calling an internationalchemicalcon-
ference,andfoundhim an enthusiastic supporter.Wurtzhadalsopromised
his supportandso in Marchall threemet in Paristo discussthe projectwith
the Frenchchemists,who agreedto supportit. AprilandMaywere spentin
correspondencewith other colleaguesand in June a letter, printedin
English,FrenchandGerman,signedby forty-fiveof the leadingchemistsin
each country,was widely circulatedinviting the recipientsto attendan
internationalconferenceat Karlsruheon 3 to 5 September.The objectof
thisconferencewas to try to get agreementon the followingpoints:precise
definitionsof the ideasconveyedby the words,atom,molecule,equivalent,
atomicity,basicity;examinationof the true equivalentsof substancesand
theirformulae;initiationof a uniformnotationanda rationalnomenclature.
Mostof the replieswerefavourableandWeltzienwent aheadwith arrange-
mentsfor the conference.
Inthepreliminary discussionsaboutprocedure with WeltzienandWurtz,
Kekuleopposedthe appointment of a permanentchairmanas the choice
would arousejealousyandthe individualviews of the chairmanmightcarry
too muchweight.So it was agreedthata new chairmanshouldbe electedat
each session.Kekulemistrustedthe older men and was anxiousthat the
directionof the discussions shouldbe in the handsof a strongsecretariatof
the younger generation. He was not in favour of inviting any prepared
contributions, but hopedthat generaldiscussionwould bringout the main
issuesthat were in disputeand lead to some measureof agreement.He
anticipateddifficultiesandwas clearlyafraidthatthe resultmightbe incon-
clusive.Most of the prominentEuropeanchemistscameto Karlsruheand
I40 were presentat the openingmeetingon 3 September.
Fortunately we have eye-witnessaccountsof the proceedingsby Lothar
Meyer(2), Mendeleev (3) andVasich(4) andalsothe long reportwrittenby
Wurtz,one of the secretaries, includingthe text of Cannizzaro's speechon
the lastday (5). All the documentsat Karlsruhe relating to the Conference
were collectedandindexedby CarlEnglerwhen he wrotehis accountof it
in I892 (6). They were usedlater by Alfred Stock in a more detailedaccount
including extracts from eleven of the interesting letters from Berthelot,
Bunsen, Liebig, Pasteur,Roscoe and W6hler (7). All these documentswere
destroyed by bombing during the last war but luckily Kekule had kept a

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59
copy of Wurtz's precis which was reproducedin his biographyby
Anschutz(5). This also containsKekule'snotesfor his openingspeechand
importantdetailsof the planningof the Conference.So we know fairly
accuratelythe courseof events.
At the openingsessionWeltzienwelcomedthe membersand took the
Chairwith Wurtz,Roscoe, Kekule,Streckerand Schishkoffas Secretaries.
The notesof Kekule'sopeningspeechshow thathe failedentirelyto give a
cleardirectiveto the Conference.He rambledon suggestinga varietyof
subjectsthatthey might discussgoing far beyondthe limitedobjectivesset
out in the letterof invitation.He proposedthatthey shouldappointa com-
mittee to formulatequestionsfor discussionby the Conferenceon the
followingday. This was agreedand a committeewas appointedconsisting
of the Secretariesand a numberof membersincludingCannizzaroand
Mendeleevwith Kopp as Chairman.It was agreedthat the committee
meetingsshouldbe privatebut LotharMeyersaysthatadditionalmembers
were co-opteduntilthe committeeincludednearlyhalfthe Conference.
The firstmeetingof the committeerevealeda fundamental differenceof
approachby Kekule and Cannizzaro as Kekulewould acceptonly chemical
evidencefor the determination of atomicandmolecularweightsandwould
not acceptCannizzaro's view of the identityof the physicaland chemical
molecule,pointingout the anomaliesof the vapourdensitiesof sulphur,
ammoniumchlorideand sulphuricacid. Eventuallythey decidedon three
questionsfor discussion:
(I) Is it convenientto distinguishbetweenatomsandmolecules?
(2) Canthe termcompoundatombe replaced by the expressionsradical
or residue?
(3) The idea of equivalentsis empiricalandindependentof the ideaof
atomsandmolecules.
At the secondsessionof the Conference,Boussingeult,one of the older
generation,was in the Chair, more familiar,as he said, with applied
chemistrythan with theory.He protestedagainstthe view that the Con-
ferencewas to seek to reconcilethe old chemistryand the new, since,he
said,chemistrydoes not grow old, but chemistsdo. Kekulespoke to the
firstquestionandinsistedthatthe magnitudeof the chemicalmoleculecould
only be determinedby chemicalevidenceand thatphysicalmethodswere
not acceptable,quotingsulphurasanexample.Cannizzaro opposedthisview
saying that the distinction
between the and
chemical physicalmoleculewas
unnecessary and unsupported by evidence.The meetingadjournedwithout

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6o

reachingany decisionon this point. At the second meeting of the committee


Kekule and Cannizzarohad an argument about notation and Kopp, the
Chairman,saidtheirbusinesswas to pose questionsand not to discussthem in
detail. He then spoke of the need to adopt symbols representingan agreed
value. As it had been found necessaryto double the atomic weights of certain
elements he suggested the use of a barred atomic symbol to representthe
doubled atomic weights and proposedthe following questionfor discussion:
'Is it desirableto double certainatomic weights in order that the notation is
in accordwith recent progress?'
At the third meeting of the committee in the evening of 4 September
Dumas took the Chair as Kopp had to leave early. Kekule proposed an
alterationin Kopp's questionand the Chairmanthen interposedand spoke of
the ill effects due to the present confusion, and the need to remedy it. He
reminded them that twenty years ago the atomic weights of Berzeliuswere
accepted by everyone and that nothing had happened to replace their
authority. Wurtz supportedthis view taking advantageof the opportunity
to point out Gerhardt'smistake in assigning to all metallic monoxides the
same constitution as water. After a discussion it was agreed to put the
following questionsto the final sessionof the Conference:
(i) Is it desirableto make chemicalnotation conform to the progressof
the science?
(ii) Is it acceptableto adopt anew the principlesof Berzeliuswith certain
modifications?
(iii) it desirable to distinguish by certain signs the new chemical
Is
symbols from those in use fifteen years ago?
No doubt Dumas' authority as the doyen of chemistry carriedthe day,
but could the Conference have met for its fial discussionwith a less
auspiciousprogramme?Dumas by his substitutiontheory had done more to
discredit Berzelius than anybody, and now with the aid of Wurtz he is
reinstatingBerzelius with the object of discreditingGerhardt.Vasich, who
like Cannizzaro was a supporter of Gerhardt, stigmatizes Dumas in his
spiritedaccount of the Conferencefor his attitude to Gerhardtand Laurent
at this stage, saying that he took advantageof his position as Chairmanto
continue his attack on the dead men, which had had such tragic con-
sequencesin their lives.
At the final sessionDumaswas againin the Chairand Odling had replaced
Roscoe as one of the Secretaries.Accordingto LotharMeyer and Mendeleev,
Dumas opened the proceedingswith a long speech, which Wurtz does not

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6I

record.Developingthe theme that there are two chemicalsciences,the


inorganicand the organic,he proposedthat the older equivalentweights
would be used in the former and the new in the latter. This roused
Cannizzaroto the most vigorousopposition,deploringthe habitof using
differentatomicweightsin the two branchesof the scienceandemphasizing
its essentialunity.In thishe waslatersupportedby Odling.He opposedthe
secondquestionwhichsoughtto resuscitate the atomicweightsandformulae
of Berzeliuswhich he saidwas illogicalas much had happenedto change
them. He spokeat length of the value of Gerhardt's system,basedon the
work of Avogadro,Ampere,Dumasandhis pupilGaudin.He pointedout
the one inconsistency of Gerhardt's theorywhenhe departedfromthe logic
of Avogadro.Cannizzaro traversedmostof the groundcoveredin his course
of lecturesandhis hearersmay well have had difficultyin followingall his
detailsthoughthereis evidencethathis speechdrew generalapplause.His
final words show that he did not expect to win completesupportfor
Gerhardt's system,although,as he said,it was gainingnew adherentsevery
day amongthe youngerchemists.He thereforeadvocatedthe use of barred
symbolsto expressthe doubleatomicweightsin orderto avoidthe present
confusion,althoughhe musthaveseenthatthiswas a retrogadestep.
After Streckerand Kekulehad expressedagreementwith Cannizzaro's
view, Erdmannproposedthatthey shoulddropthe firsttwo questionsas it
was difficultto arriveat agreementon questionsof principleor to imposea
notationby a vote. HereWurtzinterposedto saytherewasno ideaof voting
on fundamentalquestionsbut simplyon mattersof formalnotation.There
followeda long discussion of takinga vote on question(iii).
on theadvisability
Cannizzaro opposedit, Kekule was in favour,Koppandotherssaidthatyou
cannotsolve scientificquestionsby voting and that eachinvestigatormust
retainhis full freedom.Ultimatelyit was left to the Chairman.Dumasthen
expressedthe view that barredatomsrepresenting atomicweightsdouble
thosein previoususe shouldbe introduced.He thenthankedthe organizers
andhostsof the Conferenceand the meetingended,as LotharMeyersaid,
withoutreachinganyconclusions,usefulasit hadbeenas an opportunityfor
the exchangeof views. Stockcommentsthattheymusthavepartedin anicy
mood.
No officialrecordof the Conferencewas issuedalthoughWurtz'sreport
hadobviouslybeenwrittenfor thatpurpose.Weltziensenta copy to Kekule
who haveredover it. He wrote in Novembersayingthathe had been too
busy to attendto it. It was only a firstdraftand he wantedto adjustthe
differencesit revealedbetweenCannizzaro's andhisown 'unfortunate speech',
5

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62

buthe didnot seehow it waspossibleto makesimilaradjustments in Dumas'


speech(5).He hadobviouslylostinterestandwasabsorbed in hisexperiments
on organicacids,so nothingwas done.
However,thatwasnot the end.The decisivemomenthadcomeafterthe
closeof theConference whenPavesidistributed somereprintsof Canni77aro's
Sunto.LotharMeyerwas givena copywhichhe putin hispocketto readon
his way home(2). 'I readit againandagain',he wrote,'andI was amazedat
the clearlight which that little papershed on the main subjectsof our
debates.The scalesfell from my eyes, doubtsdisappeared and a feelingof
certaintytook theirplace.If I was ablelaterto helpin clearingup the points
at issueandcoolingthe hot tempers,I owe muchto Cannizzaro's pamphlet.
Many other members of the Conference felt the same.The tides of battle
to
began ebb; the old atomic weightsof Berzelius once more came into their
own. After the apparentdiscrepancies betweenthe laws of Avogadroand
Dulong andPetithadbeen explainedby Cannizzaro, both couldbe usedto
the full and therebythe doctrineunderlyingthe chemicalvalues of the
elementswasput on a soundfoundationwithoutwhichthe theoryof atomic
linkagecouldnot haveprogressed.'
It is thus certainthat it was only afterreadingCannizzaro's Suntothat
LotharMeyerrealizedthe logic and clarityof his exposition.Withoutthe
convincingtablesof valuesin the paperit must have been difficultto do
justiceto it verbally.How differentthe resultmighthavebeenif Cannizzaro
had had lanternslidesor a hand-out.Mendeleev'senthusiasticpraiseof
Cannizzaroin his letterof 7 Septemberto his teacherVoskresensky must
alsohavebeenwrittenafterhe hadreadthe paperas he quotesthe tablesin
it (3).
Two yearslaterLotharMeyerwrote his Modernen TheorienderChemie,
in
published I864 which did much to clarifychemists'thinkingabout atoms
andmolecules, so thatby 1870 Cannizzaro's views were generallyaccepted,
except in France. Academician Figurovsky'sbiography of Mendeleev contains
the followingstatementaboutthe genesisof the PeriodicTable,takenfrom
some unpublishedreminiscencesby his son, D. I. Mendeleev(8): 'The
decisivemomentin the developmentof my theoryof the periodiclaw was
in i860, at the conferenceof chemistsin Karlsruhe,in whichI took part,and
at whichI heardthe ideasof the ItalianchemistS. Cannizzaro. I regardhim
as my immediatepredecessor, becauseit was the atomicweightswhichhe
found,whichgaveme thenecessaryreferencematerialfor my work.1noted
immediatelythat the modificationshe proposedto the atomic weights
introduceda new patterninto Dumas'groupings,andit was thenthatI was

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63
struckwith the essentialidea of a possibleperiodicityin the propertiesof the
elements on increase in the atomic weight. I was still hindered by the
incongruitiesin the atomic weights accepted at this time; but I was firmly
convinced that this was the directionin which to pursuemy work.'
So in spite of its inauspicious ending the Conference, thanks to
Canni7.7aro's presence, was destined to have a decisive influence on the
progressof chemical theory and to be a great landmarkin its history.
I am grateful to AcademicianFigurovskyfor his help and advice.

REFERENCES

(I) Cannizzaro. Sunto di un corsodifilosofia chimicafatto nella R. Universita di Genova dal


Prof. S. Cannizzaro.Pisa, Tipografia Pieraccini, I858.
(2) Ostwald's KlassikerNr go. AbrisseinesLehrganges der TheoretischenChemievorgetragen an
derK. UniversititGenuavon Prof. S. CannizzaroHerausgegebenvon Lothar Meyer.
Leipzig, Verlag Engelmann, 1891.
(3) Mendeleev. Letter to Prof. Voskresensky.
Dmitrii IvanovichMendeleev,his Life and Works by M. I. Mladentsev and V. E.
Tischenko. U.S.S.R. Academy of Sciences, 1938. Vol. I, pp. 250-258.
(4) Vasich. Anonymous account of the KarlsruheConference in the Journal, Recordsof the
Fatherland, 134, 77-82 (I86I).
(5) R. Anschiitz.AugustKekule Verlag Chemie, G.M.B.H., Berlin, 1929. Vol. i, pp. 183-209
and 671-69I.
(6) Carl Engler. Festgabezum Jubildumder vierzigjihrgenRegierungSeinerKoniglichenHoheit
derGrossherzogs FriederichvonBaden.Karlsruhe,1892, pp. 346-355.
(7) Alfred Stock. Der internationaleChemiker-KongressKarlsruhe3-5 September1860 vor und
hinterden Kulissen.Zusammengestelltvon Alfred Stock. Verlag Chemie, G.M.B.H.,
Berlin, I933.
(8) N. A. Figurovsky. DmitriiIvanovichMendeleev.Izd. Akad. Nauk. SSSR, Moscow: 1961,
PP. 44-5 .
Among the many articleswritten about the KarlsruheConference the following are of
specialinterest:
E. von Meyer. Die KarlsruheChemiker-VersammlungimJahre i86o.J. prakt.Chem.,n.s. 83,
I82 (1911).
Clara de Milt. Carl Weltzien and the Congress at Karlsruhe.Chymia,I, 153 (I948).
Clara de Milt. The Congress at Karlsruhe.J. chem.Educ.,28, 421 (I95I).

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