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
Vorwort/Suchen Zeichen/Abkürzungen Impressum