Causticum Anhang

 

Siehe: Causticum Anhang 2

 

[A. Grimm]

Causticum.: Ätzstoff oder Phantasieprodukt?

Causticum Hahnemanni ist zweifellos das umstrittenste Präparat der Materia medica. Es wurde schon zu Lebzeiten Hahnemanns zum Zankapfel innerhalb der homöopathischen Ärzteschaft, jedoch nicht wegen fehlender oder ungenügender Arzneiwirkung sondern wegen seiner chemischen Zusammensetzung. Die „wahre Natur"

des Causticum hat damals wie heute viele Spekulationen ausgelöst. Die Frage nach den Inhaltsstoffen stellt sich keineswegs nur aus theoretischen Erwägungen, sondern

hat für die tägliche Praxis Bedeutung. Eine sichere Arzneitherapie ist nur möglich, wenn die zur Therapie verwendete Arznei und die geprüfte Arznei identisch sind.

(Zur Überprüfung dieser Übereinstimmung muss die chemische Zusammensetzung aufgeklärt oder die Originaltreue des Herstellungsverfahrens gewährleistet sein).

Übrigens fand Causticum, obwohl zu den Polychresten gehörend keine Aufnahme ins homöopathische Arzneibuch (HAB1)

Nach 150 Jahren scheint es an der Zeit, einen Versuch zur endgültigen Klärung seiner chemischen Beschaffenheit zu unternehmen.

Zur Geschichte der Causticum-chemie

 

Originaltext von Samuel Hahnemann

Man nimmt ein Stück frisch gebrannten Kalk von etwa zwei Pfund, taucht dieses Stück in ein Gefäss voll destillirten Wassers, eine Minute lang, legt es dann in einen trocknen Napf, wo es bald, unter Entwicklung vieler Hitze und dem eignen Geruche, Kalk-Dunst genannt, in Pulver zerfällt. von diesem feinen Pulver nimmt man zwei Unzen, mischt damit in der (erwärmten) porcellänenen Reibeschale eine Auflösung von zwei Unzen bis zum Glühen erhitztem und geschmolzenem, dann, wieder erkühlt, gepülvertem, doppelsaurem schwefelsaurem Kali (bisulphas kalicus) in zwei Unzen siedend heissem Wasser, trägt diess dickliche Magma in einen kleinen gläsernen Kolben, klebt mit nasser Blase den Helm auf, und an die Röhre des letztern die halb in Wasser liegende Vorlage, und destillirt unter allmähliger Annäherung eines Kohlenfeuers von unten, das ist, bei gehörig starker Hitze, alle Flüssigkeit bis zur Trockenheit ab. Dieses etwas über anderthalb Unzen betragende Destillat, von Wasser-Helle, enthält in konzentrirter Gestalt jene erwähnte Substanz, das Causticum, riecht wie Aetz-Kali-Lauge und schmeckt hinten auf der Zunge schrumpfend und ungemein berennend im Halse, gefriert nur bei tiefern Kälte-Graden als das Wasser und befördert sehr die Fäulniss hinein gelegter thierischer Substanzen; auf Zusatz von salzsaurem Baryt lässt er keine Spur Schwefelsäure, und auf Zusatz von Oxal-Ammonium, keine Spur von Kalkerde wahrnehmen.

 

„Causticum. Ätzstoff" wurde von Hahnemann in seinen „Chronischen Krankheiten", 4. Band, 1830 beschrieben und in die Materia medica eingeführt, die endgültige

Fassung erschien dann 1837 in der 2. Auflage.

Hahnemann glaubte, im Causticum ein vollkommeneres und reineres Produkt der Aetzstofftinktur (Tinctura acris)", erstmals in der „Fragmenta", dann in der Reinen Arzneimittellehre erwähnt, gefunden zu haben und lobt die antipsorischen Tugenden seines neuen Präparates.

Griesselich unternahm 1835 „mit einem geschickten Chemiker" den Versuch, genau nach Hahnemanns Vorschrift Causticum zu präparieren.

Da er nach wiederholten Versuchen kein mit Hahnemanns Beschreibungen übereinstimmendes Präparat herstellen konnte, forderte er die Ärzte auf, über ihre Erfahrungen

zu berichten und entweder Hahnemanns Angaben zu bestätigen oder zu widerlegen. Die Resonanz blieb aus, und er kam zu dem Schluß: „Ein Causticum gibt es nicht und kann es nicht geben". Da es für Griesselich offenbar von Wichtigkeit war, die Diskussion um Causticum aufrechtzuerhalten, weil er damit hoffte, Hahnemanns Autorität

in Frage stellen zu können, und er außerdem der Meinung war, „... in naturwissenschaftlichen Dingen müsse Klarheit herrschen, und Wein könne nicht Wasser genannt werden, wie Causticum nicht Causticum, wenn es keines gibt", setzte er 1837 einen Preis von 12 Ducaten für die endgültige Klärung der chemischen Natur des Causticums aus.

Aber „...kein Mensch bewarb sich und wollte gratis oder für 12 lumpige Ducaten Hahnemanns Causticum-Ehre im Destillirkolben die Feuerprobe bestehen lassen...

Die Wortführer des Causticum, die Ritter ohne Schärfe, mögen mit besseren als mit Wortbeweisen kommen, die Eher des chemischen Nichts zu retten".

Einerseits vielleicht angespront durch diese kernigen Worte, andererseits initiiert von Anhängern Hahnemanns, die ihrem Meister Hilfestellung geben wollten, setzte eine langanhaltende Diskussion ein und zahlreiche chemische Versuche wurden unternommen. Die Experimentatoren kamen zu ganz unterschiedlichen Ergebnissen, was wiederum zu den abenteuerlichsten Spekulationen Anlass gab.

1835: Griesselich beschreibt sein Präparat als fade schmeckend, mit Geruch nach schwachem Kalkwasser, weder saure noch alkalische Reaktion zeigend.

1836 glaubt derselbe Autor, Calcium causticum sei der Inhaltsstoff.

1837 erhält Buchner ein wasserhelles, farbloses Präparat von laugenhaftem Geruch und Geschmack, das kein Brennen, höchstens ein Kratzen im Schlund verursacht, mit deutlich alkalischer Reaktion und weist Ammoniak nach.

Im gleichen Jahr hält Veith Causticum für nichts anderes als Kali causticum, ohne jedoch experimentelle Ergebnisse für diese Behauptung anzugeben.

1840 beschreibt Piper ein Präparat mit schwachem, unbestimmten Geschmack und deutlichem Geruch nach Kalk und siedendem Leim. Er weist darin Spuren von Schwefelsäure, aber keinen Ammoniak nach.

1840 beschließt die Vereinsversammlung in Mainz, das Präparat sein Ammoniak, worauf Griesselich vorschlägt, statt des Causticum reines Ammonium causticum anzuwenden.

1841 beschreibt Lappe, den Hahnemann 1829 in einem Brief um eine Analyse bat, sein Präparat so: Wasserhelle, farblose Flüssigkeit, alkalisch wie Kalk beim Löschen riechend. In zahlreichen Versuchen konnte er Ammoniak, eine „Spur von Kalkerde" und eine kohlenstoffhaltige Substanz unbekannter Herkunft finden.

1841: Griesselich bezeichnet Causticum als „... chemisches Unding"[xx], schließt aber später aus Buchners und Lappes Ergebnissen, dass Causticum „aller Wahrscheinlichkeit" geringe Mengen an kohlensaurem Ammoniak (nicht reinen Ammoniak) enthalte.

1843 stimmt die 10. Versammlung des rheinischen Vereins darin überein, dass Causticum „ein unsicheres Präparat sei, dessen Ursprung auf einer irrigen chemischen Idee beruhe". Im gleichen Jahre schließt sich dem Rummel an: „Causticum ist auch so ein Mittel von zweideutigem Ruf."

1843 werden beim Vergleich zweier Präparate wider unterschiedliche Qualitäten gefunden, Henkings Causticum ist wasserhell, schmeckt mild, riecht etwas nach Kalkwasser und wird milchig-trübe, wenn es der Luft ausgesetzt wird. Walches Causticum hingegen riecht wie ein in Zersetzung begriffener Stoff.

1844: Gruners Präparat riecht stark nach Ammoniak und verfärbt Korkstopfen schwarz. Pettes Präparat dagegen ist wasserhell und gänzlich geschmack- und geruchlos.

1845: Das Causticum von Starke besitzt einen eigentümlichen, der Seifensiederlauge ähnlichen Geruch. Ammoniak lässt sich nachweisen und beim Versetzen mit Schwefelsäure nach dem Eindampfen entsteht ein gelbbrauner Faserstoff.

1858: Goullons Causticum ist wasserhell und hat die von Hahnemann beschriebenen Geschmacksqualitäten. Es riecht nach Kalkdunst, verursacht Brennen im Hals, zeigt aber keine alkalische Reaktion und enthält keinen Ammoniak. Daraus schließt Goullon, dass es sich um „dynamisierten Kalk" handeln müsse.

1861 beschreibt Streintz ein Präparat von schwachem, eigentümlich fadem Geruch, das alkalische Reaktion zeigt und Spuren von Ammoniak enthält.

1877 stellt Lorbacher in einer mehrteiligen Publikation zahlreiche Arbeiten zu Causticum zusammen, kommt aber bezüglich seiner chemischen Zusammensetzung zu keinem Ergebnis.

1926: Nach einer längeren Pause in der Diskussion um Causticum glaubt Wagner, die endgültige Lösung gefunden zu haben. er weist Ammoniak und Ammoniumsulfit als Inhaltsstoffe nach. Experimentell konnte er zeigen, dass der gefundene Ammoniak aus dem gebrannten Kalk stammt. Wagners Ergebnisse nimmt Möckel im gleichen Jahr zum Anlass, in einem Übersichtsreferat mit immerhin 62 zitierten Literaturstellen die Problematik um Causticum als abgeschlossen zu betrachten. P. Schmidt lobt 1928 Wagners Untersuchungen in den höchsten Tönen als die einzig ernst zu nehmenden. Er zieht aus dessen Ergebnissen den spektakulären Schluß, die antipsorische und antisycotische Wirkung des Causticums sei auf den Gehalt an Schwefel zurückzuführen.

T.F. Allen hält Causticum für identisch mit Tinctura acris sine Kali und Kali causticum für den Inhaltsstoff.

Hughes vermutet ebenfalls Kali causticum als Inhaltsstoff.

Farrington ein Kaliumpräparat ihm unbekannter Zusammensetzung. Alle drei zuletzt genannten Autoren geben aber keine Quellen oder experimentellen Befunde an.

Was in neuerer Zeit zum Thema Causticum geboten wurde, wirk eher mystifizierend als erhellend und beruht mehr auf Spekulationen als auf solider chemischer Analytik.

1969 hält Hochstetter Causticum „für ein alchemistisches Problem" und vermutet, dass eventuell Kalilauge bei der Destillation, ähnlich wie bei der Wasserdampfdestillation ätherischer Öle,

„mit hinübergerissen wird". (Kalilauge gehört aber nicht zu den wasserdampfflüchtigen Substanzen, s. unten).

Mezger behauptet, Causticum sei durch Ammonium carbonicum ersetzbar. Vithoulkas bringt Hahnemanns Causticumzubereitung in Zusammenhang mit der Alchemie und stellt sie als Beispiel hin für die einzelnen Bearbeitungsschritte eines mineralischen Stoffs und die „unglaubliche Genauigkeit", mit der Hahnemann Stoffe auf ihre chemische Eigenschaften untersuchte. Hagers Handbuch der Pharmazie stellt fest, dass die arzneiliche Wirkung des Causticum nur auf der des Alkohols oder auf Suggestion beruhe,

da das Destillat nur Wasser enthalte.

 

Eigene Untersuchungen

Um die Frage nach den Inhaltsstoffen von Causticum Hahnemanni wider aufzunehmen, bedarf es einmal des historisch getreuen Nachvollzugs der Herstellungsschritte Hahnemanns, andererseits der modernen analytischen Methoden, mit denen die einzelnen Stufen kontrolliert werden.

Daher muss zunächst einmal Hahnemanns Verfahren rekonstruiert werden.

Hahnemanns Präparation von Causticum

Wir finden sie in Band III (S.84-85) der „Chronischen Krankheiten", und sie soll hier wörtlich und vollständig wiedergegeben werden.

„Mann nimmt ein Stück frisch gebrannten Kalk von etwa zwei Pfunden, taucht dieses Stück in ein Gefäss vol destillirten Wassers, eine Minute lang, legt es dann in einen trockenen Napf, wo es bald, unter Entwicklung vieler Hitze und dem eignen Geruche, Kalk-Dunst genannt, in Pulver zerfällt. Von diesem feinen Pulver nimmt man zwei Unzen, mischt damit in der (erwärmten) porcellänenen Reibschale eine Auflösung von zwei Unzen bis zum Glühen erhitzten und geschmolzenen, dann wieder erkühlt, gepulvertem, doppelsaurem schwefelsaurem Kali (bisulphas kalicus) in zwei Unzen siedend heißem Wasser, trägt diess dickliche Magma in eine kleinen gläsernen Kolben,

klebt mit nasser Blase den Helm auf, und an die Röhre des letzteren die halb in wasser liegende Vorlage, und destillirt unter allmäliger Annäherung eines Kohlefeuers von unten, das ist, bei gehörig starker Hitze, alle Flüssigkeit bis zur Trockenheit ab. Dieses etwa über anderthalb Unzen betragende Destillat, von Wasser-Helle, enthält in konzentrierter Gestalt jene erwähnte Substanz, das Causticum, riecht wie Aeth-Kali-Lauge und schmeckt hinten auf der Zunge schrumpfend und ungemein brennend im Halse, gefriert nur bei tiefern Kälte-Graden als das Wasser und befördert sehr die Fäulnis hineingelegter thierischer Substanzen: Auf Zusatz von salzsaurem Baryt lässt es keine Spur Schwefelsäure, und auf Zusatz von Oxal-Ammonium, keine Spur von Kalkerde wahrnehmen."

 

Die Wiederholung der Hahnemannschen Präparation

Um Hahnemanns Arbeitsweise tatsächliche genau nachvollziehen zu können, war die Kenntnis der ihm zur Verfügung stehenden Gerätschaften, Laborbedingungen und chemischen Ausgangssubstanzen Voraussetzung. Aufschluss darüber kann wohl Hahnemann selbst am besten geben, und zwar im Apothekerlexikon, das sich für diese Arbeit als hervorragende Quelle anbietet. Hier werden verschiedene Destillationsapparaturen beschrieben, auch was eine Destillierblase, was ein zugehöriger Helm ist, auch was man unter „... klebt mit nasser Blase den Helm auf..." zu verstehen hat. Da für unseren Zweck Hahnemanns Versuchsbedingungen genau nachzuahmen sind, heutige Destillationsapparaturen aber völlig anders aussehen, wurde ein Helm aus Ton nachgebildet, bei ca. 1200°C gebrannt und anschließend innen glasiert. Der Übergang vom Destillierkolben zum Helm wurde mit nasser Schweinsblase abgedichtet, ebenso die Verbindung von Helm und Vorlage (Abb. 2). Als Wärmequelle diente ein Holzkohlengrill, der direkt, ohne Sandbad unter dem Kolben platziert wurde. Als Ausgangssubstanzen wurden frisch gebrannter Kalk und zuvor geglühtes und geschmolzenes Kaliumhydrogensulfat verwendet.

Was haben wir gefunden? Als endgültiges Produkt Causticum erhielten wir ein Destillat des wässrigen, dicklichen Magmas der Reaktionsprodukte. Allgemein findet man in einem Destillat übergegangene Lösungsmittel, in diesem Fall Wasser. Außer dem Lösungsmittel können flüchtige Stoffe, z.B. wasserdampfflüchtige ätherische Öle, aber auch andere flüchtige Stoffe wie Ammoniak, Schwefelwasserstoff usw. mit dem Lösungsmittel ins Destillat übergehen. Die dazu notwendigen Voraussetzungen erfüllen aber weder die Ausgangssubstanzen noch eines der Endprodukte, da keine wasserdampfflüchtigen Substanzen entstehen. Falls dies zutrifft, müsste das Destillat und damit Causticum Wasser sein. Woher stammen dann aber die von Hahnemann so ausführlich beschriebenen Eigenschaften wie Geruch nach Aetz-Kali-Lauge, schrumpfender und brennender Geschmack, Gefrierpunktserniedrigung und Förderung der Fäulnis hineingelegten Fleisches?

2 KHSO4 -> K2S2O7 + H2O

K2S2O7 -> K2SO4 + SO3

CaO + H2O -> Ca(OH)2

Ca(OH)2 + K2SO4 -> CaSO4 + 2 KOH

Folgende Details der Arbeitsvorschrift verdienen besondere Aufmerksamkeit: Gläserner Kolben, Helm. Kohlefeuer, gehörig starke Hitze. - Diese Beschreibung ist hinreichend genau, dass man mit Kenntnis der damaligen Laborgeräte Hahnemanns Vorgehensweise und Resultate gut verstehen kann.

Im wässrigen Überstand des Reaktionsgemisches befindet sich Kalilauge in konzentrierter Lösung. Diese Lösung wird durch Annäherung eines Kohlefeuers weiter eingedampft. Dabei setzt der in der Chemie sehr gut bekannte und gefürchtete Effekt des Siedeverzuges (plötzliches, stoßartiges Sieden von Flüssigkeiten, die über ihren Siedepunkt erhitzt wurden) ein. Besonders bei Alkalien ist dieser stark ausgeprägt.

Bei zunehmender Eindickung der Lösung und Eintreten eines Siedeverzuges spritzt Kalilauge bis an den Helm und gelangt von dort in die Vorlage, also ins Destillat.

Beim Vergleich mit modernen Destillationsapparaturen erscheinen Hahnemanns gläserner Kolben und der mit nasser Blase aufgesetzte Helm recht primitiv. Es ist deutlich einsehbar, dass ein Emporspritzen vom Kolben zum Helm stattgefunden haben muss, ohne dass dies von Hahnemann bemerkt worden wäre, da ein aus Steinzeug oder Zinn bestehender Helm undurchsichtig war und weiße Spritzer von Kaliumhydroxid nicht zu sehen waren.

Bei weiterer Betrachtung der chemischen Eigenschaften der Reaktionspartner fällt außer dem Siedeverzug noch eine weitere Eigenschaft des Kaliumhydroxids auf: KOH sublimiert unzersetzt ab Temperaturen von 350 - 400° C. Diese Temperatur könnte Hahnemann mit dem von ihm verwendeten Kohlefeuer („gehörig starke Hitze") überschritten haben. Sollte Hahnemann seine Destillation fortwährend überwacht und durch gelegentliches Wegnehmen des Kohlenfeuers einen Siedeverzug verhindert haben, könnte er durch die direkte Einwirkung des Feuers die Temperatur erreicht haben, bei der KOH sublimiert. Auch Hahnemanns Beschreibungen der Eigenschaften seines Destillates lassen nur Kalilauge als mögliches Produkt in Frage kommen. Alle bisher angeführten Argumente sprechen somit dafür, dass Causticum Hahnemanni aus Kalilauge besteht.

 

Die Analysen unseres Causticum

Um festzustellen, ob aus der von uns verwendeten Destillationsapparatur Substanzen ins Destillat gelangen können, wurden vor Versuchsbeginn ca. 250ml Wasser überdestilliert. Darin waren mit analytischen Methoden des DAB9 keine Natrium-, Kalium-, Ammonium- oder Sulfationen nachzuweisen. In unserem Causticum-Präparat, dem Destillat der Reaktionsprodukte, konnten jedoch eindeutig Kaliumionen nachgewiesen werden. Dagegen waren keine Ammoniumionen, mit Ammoniumoxalat keine Calciumionen und mit Bariumchlorid auf Sulfationen feststellbar. Die Nachweisreaktion mit Bariumchlorid auf Sulfat ist, im Gegensatz zu der von Oxalat auf Calcium, hinreichend empfindlich, um Hahnemanns Angabe, dass „keine Spur Schwefelsäure" wahrnehmbar sei, glauben zu können. Dagegen verfügte Hahnemann über keinen empfindlichen Kaliumnachweis, der es ihm ermöglichte, die Anwesenheit von Kalilauge, außer durch seinen Geruchssinn, zu erkennen. Der PH Wert lag etwa bei

7,4 - 7,6. Diese Ergebnisse stehen also in guter Übereinstimmung mit den Eigenschaften, die Hahnemann seinem Präparat zuschreibt, so dass eine schwache Kalilauge als

der geheimnisvolle Inhaltsstoff des Causticum anzusehen ist.

 

Weitere Experimente und: wie konnten andere Autoren zu ihren unterschiedlichen Ergebnissen kommen?

Aus den wenigen detaillierten Angaben einiger Autoren erklären sich diese auch von Hahnemann abweichende Arbeitsweisen. So setzte Buchner andere stöchiometrische Verhältnisse ein und hat seine Apparatur weder verkittet noch mit einer Blase verbunden. Lappe verwendete eine beschlagene Tubularetorte und einen Kitt aus Mehl und Lutum. Goullon hat 48 Stunden lang destilliert.

Piper destillierte mit Spirituslampe, Sandbad und Retorte.

Starke meinte, das „... Fortsetzen der Destillation bis zur völligen Trockenheit... ist... nicht zweckmäßig", weshalb er sicher niedrigere Temperaturen als Hahnemann benutzte.

Wagners Untersuchungen verdienen besondere Beachtung, da sie in die Neuzeit der Chemie fallen und offenbar die gegenwärtige industrielle Causticumproduktion beeinflußt haben.

Wagner wich in einigen Vorschriften deutlich von Hahnemanns Vorschriften ab: 1. Er setzte Kaliumhydrogensulfat direkt mit Calciumhydroxid um, ohne dieses vorher geglüht zu haben. Beim Glühen entsteht daraus das Kaliumsulfat (siehe Reaktionsgleichungen). 2. Er destillierte ca. 5 l statt ca. 0,045 l aus einem Zinnblechkesses statt aus einem Glaskolben. Außerdem unterlag er zwei Irrtümern: 1. Er glaubte, durch das Ausbleiben der alkalischen Reaktion nach dem Glühen des Trockenrückstandes (aus dem Destillat) die Anwesenheit von Alkali ausschließen zu können.

Daraus interpretierte er, dass eine flüchtige Ammoniumverbindung für die alkalische Reaktion verantwortlich sei, übersah aber dabei, dass Kaliumhydroxid beim Glühen sublimiert. 2. Seine Vermutung, der nachgewiesene Ammoniak entstehe aus zuvor gebildetem Calciumnitrid, ist wenig stichhaltig, da Calciumnitrid durch Oxidation von elementarem Calcium entsteht (3 Ca + N2 -> Ca3N2), nicht aus Calciumoxid und Luftstickstoff.

Da auch zahlreiche andere Autoren Ammoniak gefunden haben, wurden noch weitere Experimente durchgeführt. Nach deren Angaben stammt der Ammoniak aus dem gebrannten Kalk, der diesen mit Wasser gelöscht und unmittelbar danach destilliert. Frisch gebrannter Kalk wurde nach dem Abkühlen ebenso behandelt, desgleichen ein Stück Kalkstein der Schwäbischen Alb. In keinem der drei Destillate konnte mit DAB 9-Methoden Ammoniak nachgewiesen werden. Eventuell im Kalk enthaltene organische Substanzen werden beim Glühen offensichtlich zerstört. Als nächstes wurde Schweinsblase mit Kalilauge gekocht und destilliert. Hier konnte im Destillat tatsächlich Ammoniak nachgewiesen werden. Dies legt den Verdacht nahe, dass der gefundene Ammoniak durch Hydrolyse organischer Verbindungen mit Kalilauge entstanden sein könnte, was davon abhängt, ob die entstehende Kalilauge in direktem Kontakt mit der Blase gekommen war.

 

Analyse einiger Causticum-Präparate der pharmazeutischen Industrie

Causticum Urtinkturen der Firmen DHU, JSO und Staufen-Pharma wurden auf Natrium, Kalium, Ammonium und Sulfat untersucht: In allen drei Präparaten war der Ammonium-Nachweis des DAB9 positiv, der auf Kalium dagegen negativ!

Das JSO-Präparat fiel durch eine besonders hohe Ammoniumionenkonzentration auf. Für eine so hohe Ammoniumionenkonzentration hatte zuvor Starke[xlvii] eine Erklärung parat, als er den Ammoniakgeruch eines Präparates anprangerte:

„Der wirkliche Ammoniumgeruch des Grunerschen Causticum wird dadurch veranlasst worden sein, dass ein Gehülfe desselben, im dieß Präparat zu verstärken, einige Tropfen Liquor ammonii caustici hinzugethan haben zu dürfte; in dem diese Leute sich gar nicht von der Idee trennen können, dass nur Viel und recht starke Arzneimittel viel helfen können, ... unter welchen Verhältnissen aber die Zuverlässigkeit in den homöopathischen Apotheken sehr getrübt werden muss."

Dies dürfte für das JSO-Präparat nicht in dieser Form zutreffen. Jedoch kann selbst Wagners Theorie zur Entstehung des Ammoniaks bei der Präparation des Causticum diese Konzentration, bei Berücksichtigung der stöchiometrischen Verhältnisse, nicht befriedigend erklären.

 

Diskussion der Ergebnisse

Hahnemann unterlag bei Darstellung seines Causticum tatsächlich dem Irrtum, „die kaustische Kraft" der Alkalimetalle isolieren zu können. Dieser ist aber aus den historischen Gegebenheiten, d.h. dem damaligen Wissensstand der Chemie zu verstehen. Ganz und gar unverständlich ist dagegen, dass die Irrtümer seiner Zeitgenossen und Nachfolger bis zur heutigen Zeit tradiert und von pharmazeutischen Herstellern offensichtlich kritiklos übernommen wurden. Niemand hielt es bisher für notwendig, Hahnemanns Versuchsbedingungen genau nachzuvollziehen.

Entscheidend für die Qualität eines homöopathischen Arzneimittels ist die Übereinstimmung mit dem tatsächlich geprüften Arzneimittel, von dem die Symptome der Materia medica stammen, und nicht seine „Verbesserung" durch Anwendung moderner Verfahren bei der Herstellung, die es gegenüber dem Prüfstoff verändern! Man fragt sich auch, wie die bisherigen Therapieerfolge mit Causticum, das Ammonium causticum statt Kali causticum enthält, zustande kommen konnten.

Es ist hier vielleicht der Ort auf zweierlei hinzuweisen: Das Verhältnis der homöopathischen Pharmazeuten zu den homöopathischen Ärzten ist ein völlig anderes als bei der naturwissenschaftlichen Medizin. Hier sind die Ärzte als Empfänger und Verteiler der gelieferten Produkte untergeordnet. In der Homöopathie dagegen hat die ärztliche Arbeit wesensmäßig den Vorrang vor dem Apotheker, an den sie die Herstellung nun delegiert hat (d.h. heute delegieren muss), um das zu erhalten, was aufgrund des homöopathischen Heilgesetzes notwendig ist: ein mit dem Prüfstoff völlig identisches Produkt. Anders kann die gesetzmäßig-wissenschaftliche Heilung nicht gewährleistet werden, was das Eigentliche der Homöopathie ausmacht.

Dringend notwendig und zur Erweiterung der Materia medica unerlässlich ist die Überprüfung der durch Ammonium causticum statt Kali causticum tatsächlich geheilten

Fälle in Bezug auf das Vorliegen von Ammonium-Symptomen.

 

[Gothe/Drinnenberg]

MITfühlend/will aktiv anderen helfen

Setzt sich für Schutz anderen/Familie/Tieren/Natur ein.

Bedrohung von Lebewesen aller Art lässt sie aktiv gegen Widerstand werden lassen.

Ihr GerechtigkeitsSINN macht sie mutig bis fanatisch (unbequem) gegenüber Chef/Autorität.

Aufmüpfig/rebellisch wegen hohe Vorstellung von Recht/Moral.

Schulsprecher/Gewerkschaftsführer/Umweltschützer. Mutter stellt sich vor ihr Kind.

Hilft Unterdrückte/Schwache ohne Rücksicht auf persönliche Konsequenzen.

Voller Sorgen wegen anderen/Umwelt.

Am Ende überlastet, danach ERschöpft/SCHWACH (Lähmung: r./Stimmbänder/Blase)/depresSIV

Nervensystem „abgekämpft“ (M.S.)

Ursache: Tod geliebter Personen

 

[John Morgan]

This article is based on a talk given at the Irish Homoeopathic Conference, Galway in 1997.

Introduction

The development of remedies has been very prolific since Hahnemann developed his first 70 remedies, and, on the whole, the preparation of most remedies is quite straightforward and well documented. Homoeopathic pharmacy is a science of mimicry and the various pharmacopoeias and ancient texts provide the guidelines needed

to create a remedy which mirrors the original proving. Apart from the difficulty of obtaining the raw materials for some rare remedies, such as nosodes, tincture making

from medicinal herbs and trituration of elements and inorganic materials is a long but basically uncomplicated process. Even the imponderabilia, such as the Magnetic Poles, Sol, Luna and X-Ray are quite easy to make. However there is a special group of unique remedies which Hahnemann developed himself which present there own challenges. They are Calc Carb, Hepar Sulph, Merc Sol, Silica and Causticum - the so-called Hahnemannii remedies. The first two are related by the use of the shell from the european edible oyster, Ostrea Edulis, as a source of calcium carbonate. It seems, from Hahnemann's experiments, that there was a shortage of pure chemicals and the preparation of

lime water (calcium hydroxide Ca(OH)2 solution) so often used in chemistry, was procured from impure calcium carbonate sources. In an early formula of Merc., given in lesser writings, he uses burnt egg shells to make lime water. Hepar Sulph is an impure calcium sulphide and is made by putting an equal parts mixture of powdered oyster shell and pure flowers of sulphur in a sealed porcelain crucible and heating to white heat for 10 minutes. The off white powder has an odour of hydrogen sulphide (rotten eggs) and is insoluble so is triturated to potency.

Merc. was created by Hahnemann in the days before he used potencies. The aim was to produce a palatable form of mercury which could be absorbed into the body easily

as existing mercurial medicines were so poisonous and particularly corrosive. The 'solubilis' part of its name refers to its easy solubility in gastric acids and absorption by the stomach when ingested and not to its physical properties. The complicated Merc Sol formula of 1788, given in the preface to lesser writings, dissolves mercury metal in nitric acid and precipitates out the insoluble black di-mercurous ammonium nitrate. 2(NH Hg2) NO3H2O by the addition of ammonia. The resultant insoluble black powder is washed and triturated to potency.

Silica is made by melting one part of clean white sand, or rock quartz, with four parts sodium carbonate. The resulting glassy mass is pulverised and dissolved in water to release the silica as a precipitate which is then washed many times to free it from sodium salts. Presumably this formula was developed because pure silica was not available

in the early 1800's so Hahnemann had to make it himself.

And finally to Causticum which is without doubt the most challenging of them all. I have made this remedy five times in the last eleven years with three successes and two complete failures.

It demands skill, great care and patience and compels the pharmacist to heed the great master's words 'follow me, but follow me well'. It is by far the most complicated and involved process of all Hahnemann's special remedies, involving hazardous chemical reactions and distillation apparatus which needs constant care and attention.

Making Causticum is an experience which is different every time and has been a deep learning experience for me personally. It is also the only one of these remedies for

which the final chemical composition has been the subject of debate and it is still not known what Causticum actually is. Even before Hahnemann's death it was controversial.

In 1835 a chemist called Griesselich followed Hahnemann's instructions to the letter but failed to reproduce the remedy concluding that there was no such thing as Causticum. He offered a prize of 12 ducats to anyone who could clarify its chemical nature - an offer which was not taken up by anyone.

The recorded attempts of other chemists, during Hahnemann's lifetime, and the analysis of different preparations from different manufacturers, more recently, has revealed variable and inconclusive results. Also, as I shall explain later, chemically there are good reasons why it should be nothing other than distilled water which was what Griesselich's experiments mostly produced.

To try and unravel this mystery we must look at the preparation in detail, in the Causticum monograph in Chronic Diseases. I will go through it step by step to explain the chemical changes.

Lime, in the state of marble, owes its insolubility in water and its mildness to an acid of the lowest order which is combined with it; when heated to red heat the marble allows this acid to escape as a gas.

Hahnemann is describing the liberation of carbon dioxide (CO2) from marble when it is heated and its transformation from a hard insoluble form into a soft and water soluble substance which is calcium oxide (CaO). His use of the word 'lime' to describe marble relates to limestone, from which marble is derived and not to the modern chemical definition of 'lime' or 'quicklime' which is calcium oxide. Carbon dioxide is an acidic gas and will make carbonic acid (H2CO3) when dissolved in water.

During this process the marble, as burned lime, has received (besides the latent heat) another substance into its composition, which substance, unknown to chemistry, gives

to it its caustic property as well as its solubility in the water, whereby we obtain lime-water.

From this statement is seems that Hahnemann did not know the chemical composition of calcium oxide which is formed after heating marble or any other calcium carbonate such as egg or oyster shells. Calcium oxide is caustic, can create burns on the skin and reacts quite violently with water giving off much heat creating lime water, a solution

of calcium hydroxide Ca(OH)2, which has alkaline properties.

This substance, though not itself an acid, gives to it its caustic virtue, and by adding a fluid acid (which will endure fire) which then combines with the lime by its closer affinity, the watery caustic (Hydras caustici) is separated by distillation.

This passage describes the reaction of the alkaline quicklime with a heated acid to create the watery Causticum which is recovered by distillation.

 

The  Preparation

Take a piece of freshly burned lime of about two pounds,

Two pounds of white marble has to be heated to red heat to effect the necessary chemical change by driving off the carbon dioxide as follows:

CaCO3 + fire (heat)  = CaO + CO2

dip this piece into a vessel of distilled water for about one minute, then lay it in a dry dish, in which it will soon turn into powder with the development of much heat and its peculiar odour called lime vapour.

When the burnt marble, now quicklime CaO, is put into water it fizzes quite dramatically giving off heat and hydrating to form calcium hydroxide some of which, in solution, steams to create the vapour Hahnemann mentions. The formula is as follows:

CaO + H2O = Ca(OH) 2 + heat

Of this fine powder take two ounces and mix with it in a warmed porcelain triturating bowl a solution of two ounces of bisulphate of potash, (potassium bisulphate KHSO4) which has been heated to red heat, melted, cooled again and then pulverised and dissolved in two ounces of boiling hot water.

Potassium bisulphate is an acid salt with some water in its crystals. Just why Hahnemann melts it to red heat and cools it again is unclear. Perhaps in his day it was only available in hard lump form instead of the modern fine crystals and needed this treatment to make it a quickly dissolving powder. It melts easily at red heat, is dried by this heating and easily dissolves in hot water. Another possible reason for heating is to bake the crystals so ensuring that no more than two ounces of water and two ounces of the two solids are present in the final mixture so that all of it can react completely as per the following formula:

Ca(OH)2+ KHSO4 + H2O = KOH + CaSO4 + 2H2O

The thick, white paste formed by this mixture of components is just fluid enough to be pourable though needs a spatula to put it all in the retort. The hydrated calcium sulphate so formed is commonly known as Plaster of Paris hence its insoluble pasty quality and the potassium hydroxide formed is in the solution which binds the mass.

This thickish mixture is put into a small glass retort, to which the helm is attached with a wet bladder; into the tube of the helm is inserted a receiver half submerged in water; the retort is warmed by the gradual approach of a charcoal fire below and all the fluid is then distilled over by applying the suitable heat.

The glass apparatus Hahnemann used was the well known distillation retort known as the alembic. They are difficult to find these days but are commonly seen in old chemistry or alchemical books. A glass bulb elongates into the conical helm which ends in a small spout. The absence of modern water cooled glass condensers in the early 1800's gave rise to the use of a pigs bladder full of water to cool and condense the distillate vapour as it rose from the heated glass bulb. The receiving bottle is attatched to the helm, with a moistened pig's bladder, to create a porous seal and is also cooled to complete the liquefaction of any uncondensed vapour. Using gradual heat, as the charcoal fire infers, it takes many hours (4-6) to completely distil all the liquid and it is important that it is heated to dryness. My experience up to now has been with the use of modern distillation equipment, rather than the alembic, which I feel physically mimics the properties of the original adequately although cannot replace the authentic ritual of the real thing with all its beautiful subtleties. I'm sure that I will have more experiences of this remedy preparation each time getting even closer to the impossible goal of perfectly repeating Hahnemann's own remedy.

The distilled fluid will be about an ounce and a half of watery clearness, containing in concentrated form the substance mentioned above, i.e. Causticum;

It smells like the lye of caustic potash. On the back part of the tongue the caustic tastes very astringent, and in the throat burning; it freezes only in a lower degree of cold than water, and it hastens the putrefaction of animal substances immersed in it.

When muriate of Baryta is added, the Causticum shows no sign of sulphuric acid, and on adding oxalate of ammonia it shows no trace of lime.

A dictionary definition of 'lye' is ' the technical term for the alkaline liquor obtained by leaching wood ashes with water commonly used for washing and in soap making; more generally the common name for any strong alkaline solution or solid such as sodium or potassium hydroxides.'

The chemical tests mentioned at the end, using barium chloride, shows there is no presence of sulphate ions and ammonium oxalate shows there are no calcium ions present in Causticum. The physical properties mentioned, of freezing point and putrefaction, are common characteristics of caustic alkalis.

 

Modern Documentation

One of the drawbacks to the industrialisation of remedy preparations by large homoeopathic manufacturers, over the years, is the imposition of allopathic methods of quality control and analysis on raw materials in order to licence remedies as medicines for retail sale. This can impose strict testing of  original remedy materials to prove identity, quality and the validation of potentisation methods which, of course, is a good thing. When pure sources of elements and compounds are used there is no problem achieving this, but when the starting point is already an impure source this can cause difficulties. For example it is impossible to know the exact analysis of the marble Hahnemann used for the original remedy and it is not documented from where the sample was obtained. Also uncertainty as to the exact composition of the finished Causticum, and the many trace elements it may contain, would mean very involved analytical discussions about criteria and tests . Pharmacopoeias over the years have avoided this issue by substituting two pounds of marble with two pounds of burnt lime, without indicating a source, to avoid having to introduce such a variable. This means pure industrially prepared 99.9% calcium oxide is put forward as the starting point. Causticum is not found in either the French or German homoeopathic pharmacopoeia (GHP) which are both widely used in the UK and Europe. The recent British homoeopathic pharmacopoeia, brought in to preserve some of the remedies not found in the GHP, has an entry with testing for the absence of sulphates, calcium and heavy metals. Neatby & Stonham's book describes Causticum as being 'of somewhat uncertain nature' and that 'the modern liquor potassium hydrate (i.e. KOH) is often dispensed as a substitute'.  Understandably the variables possible with different marble qualities would make standardisation, via the pharmacopoeia, very difficult to reproduce by manufacturers. However this sacrifice to analysis looses certain important subtleties just as making Calc Carb from pure chalk would be slightly different from that prepared from the oyster shell. My first experiences making Causticum used pure calcium oxide, instead of marble, I have to say the end product passed all the organoleptic (taste and smell) and chemical tests given by Hahnemann and has undoubtedly worked well as a remedy. The quality of remedy potencies reflects perfectly the original so if an oyster shell is 99.5% calcium carbonate and 0.5% impurities then using pure 99.99% pure chalk would still be 99.5% of the Calc Carb picture, perhaps in most cases enough similarity to cure and not significant, we do not know - but Hahnemann's voice rings out again "....... but follow me well"! That 0.5% missing may have provided the essential part of the resonant stimulus needed to cover the similimum fully and thus cure the patient in front of us.

 

Causticum Raasay

My interest in Causticum was rekindled when on a visit to the Burren school in Galway, Eire. Nuala Eising had just finished the Fire proving and asked me if I thought a Marble woman and a Fire man would produce a Causticum child. The answer is, of course, only if she had a fling with a potassium bisulphate lover! Despite not offering this as a serious reply, not wishing to interrupt the speculation inspired by the question, it did get me thinking about making the great anti-psoric again using marble and to see if  any characteristics of the newly proved remedies are literally carried over into Causticum.

Back in the lab, some months later, the initial problem of how to heat an entire two pounds of marble to red heat soon arose. Large flame bunsens, and gas fires take ages to do it and by the time you have got to one end, of the marble block, the other end has taken up moisture again reducing the calcium oxide content. Just how did Hahnemann do it?  Visions of blacksmiths forges appeared so I tried burning it on glowing hot coals for a few hours. It works very well but contaminates the marble with sulphur fumes from the coal. So the first marble sourced remedy was a long day of burning and scraping marble until two ounce of the transformed marble was available. Still a long way from the two pound burned lump ready to dunk into water. Possibly the best method is to bake it in a pottery kiln, although I am told this can be very dangerous due to risk of explosions from possible water pockets embedded in the stone, but perhaps this will be one for the future.

However as the years go by I am more and more convinced that remedies themselves choose when to be made and the timing must be right to create the perfect conditions. This is especially true for new proving remedies, a good example being the coincidental major astrological movements of Pluto at the start of the Plutonium proving previously unknown by the proving team. The conditions for a superb Causticum firing came together one night last June at Jeremy Sherr's summer school on Raasay island off the Isle

of Skye. The Dynamis school has been holding summer gatherings there for many years and presence of twenty or so homoeopaths together supported the event beautifully. The idea came to have a wood fire on the beach so the marble was placed on a large stone while group participation gathering wood, and passing the Jamesons, soon had everything prepared. Duncan, one of the local seafarers who regularly visited Raasay, was also with us, He was very keen to join the event because he had been cured of a

very serious condition, by Jeremy, with Causticum. It, apparently, was his remedy and he set himself the task of feeding the fire with great enthusiasm as the blaze grew and the marble got redder. The weather conditions were also special with the first cloudless starry night of the week giving a clear view of the north star, Polaris, the telescopically focused light of which we were all proving at the time - just to add another dimension to it all. As the time moved on we all wandered back to bed in the early hours, leaving Duncan Causticum tending the fire, which he did until 3am. Early next morning it was sunny and I walked down to the beach to collect the burnt offering. To my amazement it was lying clean, white and exposed on the stone with not a speck of wood ash around it. I assumed Duncan had cleaned up before he retired for the night but no he had not - the highland wind had blown any remnants of the fire away and the marble was completely burned and ready. That evening it was distilled following  Hahnemanns directions as closely as possible, in an atmosphere of collective support and wonder resulting in a superb liquor which is without doubt the best quality Causticum I have made to date.

 

Questions Unanswered

I have not found as yet a satisfactory answer to why Hahnemann went to so much trouble to make this remedy. What were his intentions? If the goal was to make potassium hydroxide (KOH) this method is not very efficient and apparently unnecessary. Chronic diseases describes the smell of Causticum like the 'lye' of caustic potash (KOH) so it was obviously already available and known to him so why bother? Andreas Grimm, who reproduced the original method exactly in 1989, speculates that Hahnemann was trying to isolate and distil the 'caustic principle' i.e. the OH- ion which is, unknown to him, and a fruitless task using this crude method. Perhaps we will never know the truth but the combination of so many alchemical elements seriously leans towards an experiment with another dimension. The use of the great transforming fire, the meeting of the two principles masculine (acid) and feminine (base) in equal measure, the hermetically sealed unit and the final distillation in the alembic are all well known alchemical processes. Whatever the true reason the result is undeniably one of the most important remedies in the materia medica and it is important to be clear as to its composition and reproducibility.

 

Chemical Possibilities

According to the formulas  the thickish mixture in the flask contains only three components KOH + CaSO4 + 2H2O. i.e. Potassium hydroxide, calcium sulphate and water. There are actually no volatile gases or products which would pass over during distillation except water. Potassium hydroxide dissolves in water but remains behind as the water boils off. Calcium sulphate is insoluble and remains behind as a white hard mass. So how is the final product alkaline at all. For many years it was thought that the alkalinity was due to ammonia which is created when elemental calcium metal reacts with nitrogen 3Ca + N2 = Ca3N2 and the resulting calcium nitride reacts with water to form ammonia gas. Ca3N2 + 6H2O = 2NH3 + 3Ca(OH)2  This gas then forms ammonium hydroxide, sometimes called ammonium causticum, when it contacts water. NH3 + H2O  = NH4OH. 

Scholten states in his recent book that Causticum contains ammonia but is different from ammonium causticum.

However reactive elemental calcium metal is not present in our process and calcium oxide, which is, does not form this liaison with nitrogen and thus ammonia is not formed. It is possible for ammonia to be formed if potassium hydroxide comes into contact with the protein of the pigs bladder but this is very remote. So how is the potassium hydroxide present in Causticum? Grimm gives, what I believe, is the most likely explanation. At 350 - 400o C, temperatures, created by the charcoal fire, potassium hydroxide sublimates without decomposing. Sublimation means that the solid vaporises into the condenser and is carried over into the receiving vessel by water vapour thus resulting in a weak solution. Grimm also suggests that bumping may also occur, which is common with alkalis, creating a spitting effect up the tube. Thus Causticum is a weak solution of potassium hydroxide by these effects. If there are traces of unfired calcium carbonate in the calcium oxide then the addition of the acid may liberate carbon dioxide gas which may be present as a trace as in CaCO3 + KHSO4 = CaSO4  + KOH +CO2.  However there is also another subtle dimension which must also be remembered. The starting point was an impure marble which could have had trace elements of many different elements. Ornamental marble gains it colours from the presence of impurities such as iron creating red, chlorites the greens and graphites the blues. Quartz (silica) is also often found as an impurity in marble, so there are still many possible trace elements which are unknown

and may be present.

 

The Kali Element

With the recent use of the periodic table to expand materia medica by Sankaran, Sherr and especially Scholten, verification of the composition of Causticum can be supported by analysis of the characteristics of the element. The well known Causticum theme of the sympathetic, serious, intense, sensitive type who can become a social activist, working on behalf of others, to overcome injustice can be seen as being made up of  the three elements KOH, potassium, oxygen and hydrogen.

Scholten describes the potassium element themes as :

Doing  their work and duty without thinking. Steady plodding conscientiousness to get the job done. Have and need fixed rules and like to stick to them. Have strong principles and can be depended upon to fulfil their responsibility. Often work alone and decide for themselves how to do it. Don’t like interference. Can even turn away from the family. Fixed attention to principles and duty leads to an inability to identify with their action. Loose their sense of self. Brainwashed. Are naive. Over control suppresses free thinking. Are not open to debate and become closed, dogmatic, moralistic.

Using MacRepertory to compare Kali salts the following characteristic Causticum mind symptoms appear:

ANARCHIST; revolutionary

DICTATORIAL, domineering, dogmatic, despotic

FEAR; happen; something will

INDUSTRIOUS, mania for work

INJUSTICE, cannot support

OBSTINATE, headstrong

PASSIONATE

SELF-CONTROL; wants to control himself

SELF-CONTROL; loss of

Kali brings in many symptoms concerning the will. The well know Kali theme of control and lack of it is also seen in Causticum characteristic symptoms such as: paralysis of throat, larynx and respiratory system preventing mucus being expelled, involuntary urination on coughing or laughing, contracted tendons or paralysis in the extremities.

 

The Oxygen Element

Scholten's description give themes of avarice, selfishness, greed, egotism, envy and self centredness. Issues of self worth. They feel they haven’t been given their due and are determined to get it.

They complain and whine about things even becoming aggressive. Attention seeking like children who want things now. Leads to the element of blame, feelings of being used

and abused by others, its always the other persons fault. Victim mentality. they can’t come to terms with the unfairness of life and that they should make the best of it. Even small things get blown out of proportion and are reasons to complain. Action is hampered by a laziness, as they feel its a lost cause. Feel others should put it right. Have a passive attitude. Nonchalance and indifference to resolving the problems. Image of the tramp muttering to himself about the injustice of it all, resort to being beggars.

Here we see, in the oxygen, the more emotive side, hurt feelings, low self esteem, sensitivity to injustice and possibly a feeling of being a victim without the will to do anything about it. However combined with the strong willed and dutiful Kali element the principled, controlled and steadfast action is brought in as demonstrated by the Causticum stereotype.

Causticum and Ozone (O3) share mind symptoms such as:

ABUSIVE, insulting

COMPLAINING

CONFIDENCE; want of self

HORRIBLE things, sad stories affect her profoundly

LAMENTING, bemoaning, wailing

MOOD; changeable, variable

MOROSE, sulky, cross, fretful, ill-humour, peevish

QUARRELSOMENESS, scolding

SELFISHNESS, egoism

WORK; aversion to mental

 

The Hydrogen Element

Hydrogen brings the desire for and the experience of unity which brings the element of working for a cause for themselves and others. This search for unity can be expressed and religious feelings or as a great love for everyone. There is a sympathy out of a love for others and their emotional sensitivity allows them to feel what others feel because they are one with them.  The fight for injustice is extended beyond the personal to the collective by hydrogen's influence. It can be seen to bring in the intellectual element to the trio and extend the aspiration of Causticum to the higher purpose; they can work on behalf of others for their greater good whether it be society as a whole or their own family.

 

Causticum and Hydrogen (H2) share mind symptoms such as:

ABSORBED, buried in thought

ABSTRACTION of mind

CONTENTED

COMPANY; desire for

ELATED

POSITIVENESS

RELIGIOUS affections

THOUGHTS; rush, flow of

TRANQUILLITY, serenity, calmness

 

Putting these three elements together also shows the true polychrest nature of Causticum. Kali bringing the will which is linked to the syphilitic miasm and the search for truth; Oxygen brings the emotional element linked to the sycotic miasm and the search for love; Hydrogen represents the mental element linked to the psoric miasm the search for wisdom. Of course the whole is always greater than the sum of the parts but these generalised themes seem to fit.

The task of trying to show a remedies chemical composition by materia medica is a huge task as there are so many overlaps which go on and on. There are some interesting keynotes of Causticum which may point to other directions. For example the black type symptom 'Fear of dogs' is well known for Causticum. Kali Carb is the only kali salt which has 'fear of animals' but not of dogs although Silica is there. Kali Carb is in italics with Causticum black type in the rubric ' aversion to sweets'. Causticum also has a few symptoms about ghosts and seeing images on closing the eyes.

The Carbon series, such as Carbo Veg and Graphites, are well known for symptoms of this sort suggesting perhaps there is some carbon present. Silica also is well represented with these symptoms. Perhaps the marble impurity is present as a trace element or compound. Dogs, ghosts and desires for smoked meat also links very strongly with the Calcium element from which Causticum originates but the barium chloride discounts the presence of this element although it is interesting how close the calcium salts are. Calc Phos for example also sharing the tubercular smoked meat desire.

 

Conclusions

At present Causticum still holds some secrets and speculation and attempts to use materia medica to decipher constituents is very inexact because of the differences in numbers of rubrics between the remedies in the repertories. Perhaps continued chemical analysis of preparations in the future, ideally by many companies, will give rise to some definitive answers as to what Causticum is. Up to now the documented variations have been inconsistent and more samples, willingness and time is needed to standardise this remedy correctly. I am sure it is a Kali salt, and should be thought of as one, but alchemy is a mysterious thing and I'm sure this wonderful substance will still keep some of its secrets hidden for some time to come.

If any of you have any comments or information which can shed more light on the subject I would be very  grateful to receive it.

 

Acknowledgements

I would like to thank Bob Lawrence, at Helios, for his technical support of several preparations of Causticum, Andreas Grimm for his formidable work, insight and wonderful dedication to Causticum, Alan Crook for his translating skills and finally Jeremy Sherr, Diane Goodwin and the Raasay north stars for supporting, so beautifully, the making

of Causticum on that memorable night last June.

 

[Karl Heinz Jansen]

Karl-Heinz Jansen and Dirk Thomas Quak

First published in AHZ 4 2018; 263: 1–15, translated by Chris Kurz, with permission of the Georg Thieme Verlag KG Stuttgart. New York

Summary

The homeopathic materia medica of Causticumdescribed by Hahnemann is, due to the mixing of the symptoms of “Tinctura acris sine kali” with those of the Causticumdistillate later described in chronic diseases, still uncertain today. However, the substances produced by Hahnemann’s Causticumsyntheses are also not clearly defined chemically. We therefore repeated Hahnemann’s production procedure of Causticumseveral times in a modern research laboratory under various conditions and analyzed the distillations with elaborate chemical investigations, the results of which bring essential and new aspects into discussion.

Keywords Causticum, hydras caustici, silicates, ammonium silicates, trace analysis.

Method of Preparation of “Causticum” by Samuel Hahnemann (bold emphasis by authors):

“Take a piece of freshly burned lime of about two pounds, dip this piece into a vessel of distilled water for one minute, then lay it in a dry dish, in which it will soon turn

into powder with the development of much heat and its peculiar odor, called lime – vapor. Of this fine powder take two ounces and mix with it in a (warmed) porcelain triturating bowl a solution of two ounces of bisulphate of potash, which has been heated to red heat and melted, cooled again and then pulverized and dissolved in two ounces of boiling hot water. This thickish mixture is put into a small glass retort, to which the helm is attached with wet bladder; into the tube of the helm is inserted the receiver,

half submerged in water; the retort is warmed by the gradual approach of a charcoal fire below and all the fluid is then distilled over by applying the suitable heat.

The distilled fluid will be about an ounce and a half of watery clearness, containing in concentrated from the substance mentioned above, i.e., Causticum; it smells like the

lye of caustic potash. On the back part of the tongue the caustic tastes very astringent and in the throat burning; it freezes only in a lower degree of cold than water, and it hastens the putrefaction of animal substances immersed in it. When Muriate of Baryta is added, the Causticum shows no sign of sulphuric acid, and on adding oxalate of ammonia it shows no traces of lime.”

 

Background

Pierre Schmidt and Jost Künzli von Fimmelsberg recommended purportedly a local application of Causticumin liquid form in simple cases of burns. Our idea to develop a lotion, gel or spray with Causticum for external application required us to manufacture our own Causticumto satisfy the requirements of a sterile manufacturing chain.

After an exhaustive study of the literature we were puzzled by the question: what actually is Causticum. A question previous experimental researchers have been puzzled

by as well.

Excursion into the Chemistry of Hahnemann’s period

The “caustic principle” as Hahnemann understood it.

In manufacturing Causticum, Hahnemann, like many other chemists and alchemists of his time, was motivated by the search for the “caustic principle” of alkaline and basic substances.

“… the caustic lye salts …, which now forms their composition, gives them also the corrosive property and deserves the name aceture or causticum.” (Hahnemann S: Aetzstoff and Hydras Caustici, Journal for chemistry and physics, in connection with several scholars, LVI volume, hall at Eduard Anton 1829).

There existed the idea that the effect of alkaline substances on living organisms (corrosive, burning, irritating, biting, tanning, dissolving, etc.) is caused by a specific caustic substance, waiting to be discovered.

“What is the caustic principle found in living lime and corrosive alkalis is not yet clear; but that it does exist, and that it does not depend on an alkaline base, becomes clear on account of the strong medicinal effects of the (tincture-saturated) tincture of caustics “(from: Hahnemann:” Fragmenta “, note to Acris Tinctura, 1824).

Composed Matter

Hahnemann held the opinion that one never encountered absolutely pure substances in chemistry. He considered all matter “composed” and therefore of complex composition. Understandably, he thought that a yet unknown substance had to be responsible for the “caustic action”:

“All material perceptible by our senses, as simple as it appears, is always composed, just as every decomposition is conditioned by a new, different composition. Thus the caustic lye salts are not uncomposed substances, just as the freshly calcined (and extinguished) lime is simply lime earth. “(From Hahnemann: Journal for Chemistry and Physics 1829: Aetzstoff and Hydras Caustici).

Accordingly, composed matter was considered in Hahnemann’s times to consist of individual particles. “Binding agents and active principle” were also held to be material particles. There was, of course, no notion of charged atomic nuclei and electrons to explain the principle of chemical bonds. The molecular structure of water was also still unknown.

Principles of Modern Acid-Base Chemistry

According to Brønsted and Lowry, we today define a base as a substance capable of accepting H+- ions, i.e., a proton acceptor. In aqueous solutions, the proton acceptor

is the hydroxyl ion, OH-. The corresponding cation is called the H+-ion.

At the time of Hahnemann, the principles of acid-base chemistry were still unknown. The hydroxyl ion OH- as proton acceptor (base) and the hydronium ion H3O+ as

proton donor (acid) were only postulated in 1887 (44 years after Hahnemann’s death) by Svanthe Arrhenius and incorporated into a complete model in 1923 by Johannes Nikolaus Brønsted.

Modern chemistry explains atomic bonds and electrons involved therein through their difference electronegativity, i.e., the varying capability of atoms to attract electrons

in a chemical bond. The dipole moment of water, with its negative charge distribution around the oxygen atom and the resulting positive net-charge around both hydrogen atoms the mediator of the “caustic property” when a base is added. A OH–ion is formed by protolysis (the “caustic principle” of alkaline substances).

Acids and basis in the “old school” chemistry

At Hahnemann’s time, the term “alkaline basis”, denoted the alkaline reaction of substances, which formed bases by dissolving in water. Alchemy, the predecessor of chemistry, knew several forms of lye as bases:

    Limestone: calcium carbonate(CaCO3),

    burnt lime, quicklime: calcium oxide (CaO)and

    slaked lime: calcium hydroxide(Ca(OH)2),

but also natron (NaHCO3), sodium carbonate (Na2CO3), potash (K2CO3) and ammoniac (NH3).

The chemical composition of these compounds lay still in the dark and chemical formulas like the ones quoted above were also unknown. The periodic table of elements

would only be discovered in 1869.

“… burnt lime (has) … added another substance to its composition, which, unknown to chemistry, gives it its corrosive nature, and its solubility in water to lime water.

This substance, although not acid itself, gives it the caustic power … “(from Hahnemann:” The chronic diseases: Causticum “, 1828).

The term “basic” (in the meaning of alkaline) was hardly used at the beginning of the 19thcentury. Rather, one talked of substances with caustic properties. In English, potassium hydroxide is still today called “caustic potash”. This property as ascribed to the “fire element” (derived from ancient Greek καυστόςmeaning”burnt”), because

this corresponded to the haptic and sensory experience associated with these substances. Chemistry back then was largely experienced, felt, smelled and tasted than understood by abstract formulas like today.

The considerable amount of heat released (exothermic reaction) when calcium oxide is slaked with water, forming calcium hydroxide, was interpreted as part of the caustic principle, similar to the corrosive and burning properties on the skin and mucus membranes. These were imagined to be some kind of “fiery agent”, because fire has the quintessential property of “burning”.

Manufacturing of Bases in the 18th century

Through a reaction of burnt lime (calcium oxide) with dissolved soda (sodium bicarbonate) or potash (potassium carbonate) one knew already how to produce the “caustics”, caustic of sodium (NaOH) and caustic of potassium (KOH). This “caustification” (to render caustic, corrosive) of soda and potash was essential to the manufacture of soap. These procedures were common knowledge and already used semi-industrially. From his writings, e.g., Apotherlexikon of 1793 [3], one can infer that Hahnemann was an experienced chemist, experimenter and physician, who was up-to-date on the knowledge of his time.

 

Transference of the “caustic principle” onto water

“Causticum sine Kali” meant to Hahnemann “caustic principle separated from potassium”, which heimagined as a separable, material substance he called Causticum:

“I would like to know how such a strange substance, promising as it is for the Arztey art, which gives it the corrosive property as constituent element of the etching bases,

and in this composition has such a great affinity for the oxygen, that it quickly becomes with it transformed into chalkegas, which makes the bases (to a certain extent neutralized and) mild, while separating the atmospheric air from the etching bases by adding a completely moist acid to the bases and then by distillation, in combination

with water, as hydras caustici I am interested in, I say, how one can still refuse this essential substance of citizenship in the realm of chemistry “(from Hahnemann: Journal

of Chemistry and Physics 1829: Aetzstoff and Hydras Caustici).

We therefore interpret Hahnemann’s manufacturing procedure of Causticumas the attempt to chemically separate the postulated (and as he writes himself) “hitherto unknown by chemistry” caustic (basic) principle (by today’s standards the properties of the hydroxyl ion OH-) from burnt and slaked lime (i.e., calcium hydroxide, Ca(OH)2) and transfer it onto water by distillation.

 

Saturation of Bases to liberate Causticum

The article published in Journal fürChemie und Physik, 1829, and cited above shows clearly Hahnemann’s intention to transfer the caustic principle to water by distillation.

He defends is hypothesis about Causticum:

“When the caustic bases are saturated by a liquid acid, the caustic substance is transferred onto the water in the mixture and yields a Hydras caustici. Distilling this compound of caustic base with the acid – provided the acid is not in excess - over a sand bed until all water has evaporated, drives this new composite (Hydras caustici), by all appearances as pure water, over to the other side. Was the amount of water initially small, and hence the aggregate of the caustic principle with water concentrated, its taste on the tongue will at first be cool, then astringent and finally burning on the palate, similar to Mezereum…”

It was Hahnemann’s intention to isolate the caustic principle as material substance from a “liquid acid” (a solution of potassium sulfate) saturated by a “base” (slaked lime) by distillation. This is the reason which led him to the circuitous process of synthesizing a solution of caustic potash (KOH) as a step to his distillation of Causticum, even though he was familiar with the usual preparation of caustic potash from burnt lime (CaO) and potash (K2CO3).

 

The Idea of “Hydras Causticum”

Hahnemann’s idea of a “Hydras Causticum” (caustically reacting water), in which water is the carrier medium of the caustic property, is not far removed from the mechanism of protolysis in water.

Particularly considering how clearly Hahnemann already spoke to the reaction of carbon dioxide with water (published in Journal fürChemie und Physik, 1829). He was able to explain the reaction of carbonic acid with calcium hydroxide (slaked lime) only via “Hydras Causticum”, because gaseous carbon dioxide (i.e., CO2, which, however, in water forms H3O+ + HCO3 ) does not react with calcium hydroxide, as he was able to demonstrate in meticulous experiments[6]:

“Perhaps only, or at least most frequently, the caustic principle is contained in three compounds,

    with bases (alkaline salts, Fuller’s earth etc.);

    with carbon (in glowing coals, extinguished under mercury) (Note by the authors: Hahnemann perhaps refers to the writing of Joseph Priestly (1733- 1804), the first to discover oxygen (“air freed of phlogiston”) and

    with water.

Only in the first two cases can Causticumby contact with atmospheric air (the oxygen contained therein) be converted to acids, (Note of the authors: It is not oxygen but CO2which reacts in connection with water. Maybe Hahnemann thought that carbon, in connection with Causticum and oxygen, yields carbonic acid, in the sense of: carbon (C) + oxygen (O2) will not react to H2CO3 but 2OH- + CO2 = H2CO3)) which we will, by tradition, call chalk-acid, while recently they have been termed carbon-acid.

Thus the bases become bland and the coal turns to chalk-acidic gas (carbon dioxide).”

At this point Hahnemann goes on to describe the chemical properties of CO2 and not, as he assumes, of Causticumand oxygen. If one mixes “air” (which contains CO2)

with water, CO2 is dissolved under dissociation (HCO3 ). Is the solution saturated with calcium hydroxide (slaked lime), chalk precipitates (chalk milk; it is converted to calcium carbonate and hence “bland”).

He calls carbonic acid “chalk-acidic gas”, because of its emergence during burning of lime and because pure carbonic acid can only be produced under very specific circumstances outside of an aqueous solution. It does, under normal conditions, not exist in liquid form.

In his explanations Hahnemann follows the thoughts of the Frenchman Antonine de Lavoisier (1743- 1794) who discovered that solutions of certain oxides (e.g., sulfur dioxide) react acidic. This proved to Lavoisier that all acids had to contain oxygen. A belief that was only disproved by Justus von Liebig (1803-1874) who showed in

his Elementar analyse(1831) that there, indeed, exist acids which do not contain oxygen. But Liebig, just as Hahnemann, failed to develop a general model forbases.

The “caustic principle” (Causticum) is Hahnemann’s model for the transformation of slaked lime to chalk-water by introduction of air into the aqueous solution.

For him, the decisive factor is oxygen, who reacts with the “chalk-acid gas” (carbonic acid). He considers Causticum to be the catalyst of this reaction.

Isolation of the caustic principle by distillation

Furthermore, he is convinced that the caustic principle can be isolated by distillation, if he saturates the “bases” (slaked lime) with a “wet acid” (solution of potassium sulfate), so that the caustic principle is released.

This is the point at which Hahnemann went wrong, we realize today. Steam distillation does not transfer either acid components (cations) nor alkaline components (anions)

to the other phase, since they remain as salts in the distillation flask. Using chemically pure substances, the distillate contains only water (H2O) with its own temperature dependent auto-protolysis. Such a distillate is, ideally,pH-neutral and contains nocontaminations. Hahnemann writes:

“Every (acid), even chalk-acid (carbonic acid), separates Causticumfrom the corrosive bases, in the presence of water with which Causticumcombines to Hydras caustici.”

In his understanding, the principle of base-acid chemistry lies in the transference of the alkaline properties of a substance by way a “substance”, which exists only in connection with water. This is, in principle, correct, except one cannot separate the OH–ion from KOH as the alkaline properties (i.e., the pH) is determined by the modified behavior of valence electrons of molecules in solution. In other words, the alkaline properties are determined by the extent of protolysis (relative abundance of H3O+-ions to OH–ions) in an aqueous solution.

According to Hahnemann, the “material” property being transferred is corrosiveness. The more of the caustic principle is contained in a substance, the more corrosive it is.

This is analogous to the idea of a “heat principle”, which he mentions sometimes. The “heat principle” is, in his interpretation, a substance added to a compound by heating, and which is released again by burning. At his times this theory (Phlogiston theory) was wide spread and capable of explaining oxidation and reduction processes. It yielded, for the first time, a framework to classify certain groups of substances which form acids and bases. It was also the starting point for the investigation of the physics of gases.

Until the beginning of the 20thcentury, it was a commonly held belief that qualitative properties of matter are conveyed by specific carrier substances. The concept of “ether” as a carrier of electromagnetic waves was only finally disproved by quantum physics and Einstein’s theory of relativity. Modern physics has expanded this idea and now speaks of “gauge particles” as mediators of forces, e.g. photons, gravitons and gluons as the quanta for the electromagnetic, gravitational and strong nuclear force, respectively.

Hahnemann’s Causticum hence describes the „relationship“ between acids and bases. It is the substance of common inter-est (inter-est: from Latin inter-esse, that which is in between): they both are “corrosive”

“Entirely and absolutely simple substance are not detected by our senses: no man has ever seen such…This caustic principle in isolation and by itself is likewise undetectable, just as undetectable as are the simple substrates of gases (oxygen, nitrogen, and so forth) to our senses…That, which is part of their composition, also lends them their corrosive property and deserves to be called caustic principle or Causticum.”

The substance carrying the corrosive property is, to Hahnemann,Causticum.

Experimental Setup and Procedure

Prior to the determination of the experimental setup it was expected that, according to current know-how, the procedure described by Hahnemann can only result in pure

water in the condensed distillate. Therefore, considerable attention was put on historic conditions (impurities, apparatus, handling), which determined the experimental setup

at Hahnemann’s time.

According to Hahnemann’s original instructions, 50 g (2 oz.) each of slaked lime Ca(OH)2 and potassium sulfate, K2SO4, were homogenized with 50 ml of boiling water in a porcelain mortar. This suspension (“magma”) was heated in a distilling flask to dryness. The escaping vapor was condensed in a cooler and collected in fractions. The entire experiment lasted about 90 minutes, resulting in individual distilled fractions of ca. 10 ml.

Three different apparatus were used for the experiment:

    500 ml Duran flask with ground glass seal (Schott); Claisen distillation bridge with 40 cm Liebig cooler (Lenz Laborglas); 20 ml Duran culture vials (Schott) with screw top for collection of individual fractions.

    500 ml Duran flask with ground glass seal (Schott); 1000 ml alchemic still (alembic) of Duran glass with bent run-off (Neubert glass); 20 ml Duran culture vials (Schott) with screw top for collection of individual fractions.

    1000 ml historic flask of green lime-natron-glass with matching historic alembic; historic glass vials (ca. 30 ml) for collection of individual fractions.

Controlled heating, in order to test the effect of temperature, was accomplished on one hand by an oil bath and a laboratory-grade heating stirrer (Bibby Sterlin) up to 200° C.

And on the other hand (comparable to a classic sand bed over an open flame) over an electronically controlled heating mantle (Witeg Heating Mantle) up to 420° C.

(e) experimental setup with flask and alembic from Hahnemann’s period.

Temperature was recorded over the entire duration of the distillation by Pt100 temperature sensors and, additionally, by contactless infrared thermometer.According to setup and research goal, different temperature profiles and different final temperatures between 200 and 400° C were employed.

The following parameters were measured in the individual distilled fractions:

    Cation-chromatography (detection threshold [DT] ca. 10 μg/l) for Li, Na, K, NH4, Mg, Ca and

    Anion-chromatography (DT ca. 10 μg/l) for F-, Cl-, NO2-, Br-, NO3-, PO43-, SO42- and organic

    Amino-acid analysis (DT ca. 10 pM) for the 40 most commonamino-acids.

    pH-value via apH-sonde.

    Photometry (DT ca. 20 μg/l) forsilicates.

    Determination of silicates was only carried out once in some trials (due to the volume required for the test) using 1 ml of each of the final three fractions. In later trials,

with already higher concentrations of silicates detected in the mixed fractions, 1 ml was taken from each individual fraction, diluted 1:5 with water, and tested individually

for silicates, without mixing.

For the individual trials, chemicals were used from different sources and preparations: For calcium hydroxide we used the following preparations:

    Calcium hydroxide, chemically pure (GPR RECTAPUR®VWR)

    Calcium oxide (VWR), chemically pure, slaked with demineralized water (Sartorius, IP Arium Comfort)

    Certified marble, chemically pure calcium carbonate (Merck), burnt 4 h at 1100° C in tantalum oxide crucibles, slaked with demineralized water.

    Isar-chalk, calcium carbonate, burnt 4 h at 800° C in corundum crucibles, slaked with demineralized water

    Isar-chalk, calcium carbonate, burnt 4 h at 1100° C in corundum crucible, slaked with demineralized water

For potassium sulfate we used the following preparations:

    Potassium sulfate, chemically pure, (GPR RECTAPUR®VWR)

    Potassium hydrogen-sulfate (Alpha Aesar), melted and roasted over open flame (ca. 1100° C) in a porcelain crucible.

For water we used the following sources.

    Tap water from Fürstenfeldbruck

    Demineralized water from a mixed-bed preparation with activated charcoal filter and UV irradiation. Conductance less than 0,1 μS (Sartorius, IP AriumComfort)

During particular trials, 0.5 g of crushed chalk-natron glass was added to simulate the quality of glass used at the time of Hahnemann.

In reproductions of historic setups used in Hahnemann’s period, original (ca. 1830) glass apparatus was used, which was sealed with dried pig bladders, cut in stripes and

re-moistened (as described in the literature of the period). This kind of sealant was also used for several trials in conjunction with modern equipment for simulation purposes.

Each setup was tested by distilling 50 ml of pure water in order to determine the base values for the particular materials used.

Since the particular usage history of the historic apparatus was unknown they were carefully cleaned mechanically and rinsed for several days with demineralized water. The affluent water was examined and found to be unremarkable in all analyzedparameters.

 

The Chemistry of the Reaction

In his manufacturing instructions for Causticum, Hahnemann uses slaked lime (calcium hydroxide) in conjunction with molten potassium hydrogen-sulfate (potassium sulfate) with the addition of water in a classical exothermic reaction to yield potassium hydroxide (in solution solution) and calcium sulfate (gypsum). This aqueous suspension (termed “Magma” by Hahnemann) was then distilled.

By melting of potassium hydrogen sulfate Hahnemann synthesizes potassium sulfate under evaporation of SO3:

2KHSO4   T              K2S2O7+H2O   T             K2SO4     +         SO3

He then goes on to mix pulverized potassium sulfate with slaked lime and hot water:

K2SO4  + Ca(OH)2+Aqua          2 KOH (potassium hydroxide) + CaSO4(gypsum)+ Aqua

Afterwards, he distils the reaction mixture to dryness.

Ratio of Molar Masses

Two ounces (ca 50 g) of each of the reactants are mixed:

50 g potassium sulfate (K2SO4: M =174,3g/mol)       =>287mmol 50 g calcium hydroxide (Ca(OH)2: M =74,1g/mol) =>676mmol 50 g Aqua (H2O: M =18g/mol)                          => 2780mmol

Assuming complete stoichiometric reaction of potassium sulfate in KOH, we arrive at the following stoichiometric yields:

287 mmol K2SO4  + 670 mmol Ca(OH)2 + 2780 mmol H2O

574 mmol KOH + 287 mmol CaSO4 * 2 H2O + 383 mmol Ca(OH)2 + 2206 mmol H2O

Checking the input quantities against the yield of the reaction products:

574 mmol KOH:            (KOH: M = 56,1 g/mol)            =>32,3 g

287 mmol CaSO4 *2 H2O            (CaSO4 *2 H2O: M = 172,1 g/mol)            =>49,4 g

383 mmol Ca(OH)2            (Ca(OH)2 : M = 74,1 g/mol)            =>28,4 g

2206 mmol H2O            (H2O: M = 18 g/mol)            =>39,8 g

 

As expected, this yields a mol-mass of 3450 mM (1244 mM without water) and a total weight of149.9 g (discrepancy due to rounding errors). Stoichiometric

ratios of ions in the reaction product:

KOH                    (574 / 1244) = 46%

Ca(OH)2              (383 / 1244) = 31%

CaSO4*2H2O      (287 / 1244) = 23%

If bumping during boiling (boiling delay) should happen, then the “splashes” ought to contain the individual ions in the calculated stoichiometric ratio.

 

Calcium hydroxide as “Causticum”: the bumping hypothesis of Grimm

In the article “Causticum: Caustic Principle or Phantasy?”, published 1989, Grimm presumes delayed boiling with ensuing bumping during the distillation process.

This has become a widely accepted hypothesis today, even though it is known that Hahnemann was familiar with the problem of bumping during distillation.

He describes in detail how to avoid it in his Apothekerlexikon. He recommends using a thermometer and knows about controlled heating using a sand bed.

Furthermore, Hahnemann checks his distillate using specific precipitating reactions to exclude impurities due to bumping or other causes. He wants to ensure that his Causticumis not contaminated by sulfuric acid or calcium hydroxide. He manages to do this, employing state-of-the- art methods of his time.

Exclusion of KOH-Concentrations above 1% by Hahnemann’s Oral Test

Hahnemann starts by describing a test based on taste:

“…tastes astringent at the back of the tongue and extremely burning in the throat…”

Should, as Grimm describes, a bumping during delayed boiling have led to concentrations above 1% of KOH, this would have resulted in cauterized and necrotized

tissue in the oral cavity. The oral test, as described by Hahnemann, excludes the possibility of this having happened.

If Transference by Bumping then Transference of All Minerals

Then Hahnemann checks his distillate for impurities using two precipitating reactions:

“…upon addition of salt-acidic barite (barium chloride), no trace of sulfuric acid; and upon addition of oxalic-ammonium(ammonium oxalate), no trace of chalk detectable.”

Grimm’s hypothesis of bumping during boiling (transference of KOH to the distillate) explains the important “corrosive” properties of Causticum, but not the absence of sulfate and calcium.

If one supposes bumping, like Grimm does, as an inadvertent mechanism of transferring minerals or salts, one should be able to detect all other minerals, e.g., calcium sulfate, in their respective abundances, next to KOH.

This, however, Hahnemann disproves using the precipitating reaction with ammonium oxalate:

Ca2+ (aq) + (NH4)2C2O4 → CaC2O4 (white precipitation) + 2 NH4+ (aq)

Hahnemann’s demonstration of absence of sulfur also excludes transference of gaseous SO2 or SO3 dissolved in the vapor to the distillate.

Hahnemann uses the precipitation of insoluble barium sulfate with barium chloride to demonstrate the absence of sulfate ions.

SO42- (aq) + Ba2+ → BaSO4

Possibility of Transference by Bumping Only within the Solubility Product of Barium Sulfate and Calcium Oxalate. Since both Hahnemann’s tests, for sulfate as well as for calcium, were negative, one can safely assume that no bumping during delayed onset of boiling happened.

From our point of view, only transference in minute amounts within the solubility product of barium sulfate and calcium oxalate are conceivable, because those would not have been detectable by Hahnemann. What does this mean for possible concentrations of KOH in the distillate?

SolubilityBaSO4: 2,2 mg·l−1  (18°C)

SolubilityCaC2O4:      6,1 mg·l−1  (20°C)

Of BaSO4 (M=233.4 g/mol) there are, hence, only 9.4 µmol/l soluble. Rounding up to 10 µmol/l this results in a maximum possible ion concentration in the distillate:

10 µmol/l CaSO4*2H2O:              400 µg/l Ca + 960 µg/lSO4

13,5µmol/lCa(OH)2                      539 µg/l Ca + 459 µg/lOH

20µmol/lKOH                               780 µg/l K + 340 µg/lOH

If there had been bumping during the distillation process (in the form of minute splashes), then Hahnemann’s detection method excludes concentrations in excess of 1mg/

l for all involved ions (anions as well as cations).

This means that Hahnemann’s detection reaction by precipitation of barium sulfate (solubility product 2.2 mg/l) with ammonium oxalate is capable to exclude involuntary transference of the order of the 150-th part of a single droplet.

Concentration of at most 799 µg/l of free OH–ions can arise. This modifies the calculated pH of water to that of a very weak base (pH 9.67). In vivo this theoretical value

is never reached, because the small number of OH–ions are buffered immediately by the reaction equilibrium between liquid and external air. Furthermore, not all OH–ions

are completely dissociated.

 

Causticum Anhang

 

 

 

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