CHEMISTRY OF KUPPAKWA RASAYANA

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    Vol : No. XXVII (4) April, May, June 2008

    Chemistry of Kupipakwa Rasayanas A Review

    Prasanta Kumar Sarkar, Neky J. Mehta, P. K. Prajapati.

    Department of Rasashastra and Bhaishajya Kalpana Drug Research, I. P. G. T. & R. A., GujaratAyurved University, Jamnagar- 361008.

    Received : 03.10.2007 Accepted : 12.02.2008

    Abstract :

    Kupipakwa Rasayanas are very popular and commonly prescribed preparations among theAyurvedic physicians, and are looked upon as panacea. These are prepared in a speciallydesigned glass bottle by gradual heating immersion in sand bath (Valuka Yantra). Particularchemical processes are involved in these preparations which also bear testimony to the greatchemical knowledge prevailing in ancient India. In the present review, the probable chemistry

    of Kupipakwa Rasayanas has been discussed.

    Key words : Rasasindura, Makaradhwaja, Malla-sindura, Shilasindura, Talas-indura,Rasakarpura, Rasapushpa, Swarna Vanga.

    Introduction :

    Chemistry in ancient India had its origin inthe development of practical arts to meetthe demand for the necessities of life, as alsoin the speculation about the nature and

    composition of matter. Since the beginningof this civilization, the evaluation ofchemistry may be said to have proceeded ina more or less uninterrupted course in spiteof numerous political and social changes inthe country. Use of various metals andminerals and transformation of these intoeffective drugs in Ayurvedic system ofmedicine serve as evidence for this fact1.Metallic and mineral preparations areunique in Ayurveda and are known by the

    name of Bhasma, KupipakwaRasayana, etc.

    The terminology Kupipakwa itself denotesthe pharmaceutical processing that isinvolved in these preparations by heating inglass bottle. The products thus obtained arevery favourite and frequently used remedyby the Ayurvedic physicians. These are

    reputed to be panacea for a variety of ills

    that human flesh is heir to2. The generalbelief is that by association with mercuryand sulphur, these products acquire the

    most potent efficacy.

    The process of Kupipakwa Rasayanapreparation employs many of thealchemical principles and observations. Inthese processes mercury (Hg) has been usedextensively to bring about the desiredchemical changes in the final product. Theother element used freely is sulphur (S).High chemical reactivity of both these

    elements is well known today3, and it

    seems that the Ayurvedic scholars wereconscious of their properties. Many studieshave so far been carried out on variousKupipakwa Rasayana preparations, and theproperties and chemical composition of

    these preparations have been reported4,5,6.

    Preparation of Kupipakwa Rasayana :

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    The authentic raw metals or minerals(Parada (Mercury), Gandhaka (Sulphur) andother metals and minerals) are procuredfirst, and are subjected for Shodhana

    (purification) procedure according toclassical Ayurvedic references. Thenspecified quantity of Shuddha materials(mostly Parada and Gandhaka) are mixed andtriturated together for several hours untilthe mixture is converted into a black,lusterless, fine, impalpable powder ofuniform consistence. This is known asKajjali. In some preparations(Makaradhwaja, etc.), Shuddha Parada isrubbed with ShuddhaDhatu (metal like gold,etc.) to make an amalgam. ShuddhaGandhaka is added to the amalgam and thewhole are triturated for several hours untilthe mixture is converted into Kajjali. Otherpurified materials (Haritala(orpiment),Manahshila (realgar), etc.) are mixed withthe prepared Kajjali for different KupipakwaRasayana preparations (Talasindura, etc.).The Kajjali is then levigated by specificliquid media. The prepared Kajjali is thenplaced in a specially designed glass bottle(with seven layers of mud smeared clothes),

    and the heating process is carried out byimmersing the filled bottle in ValukaYantraand gradually increasing temperature forspecific duration. On cooling the preparedKupipakwaRasayana is found to be depositedin the inner surface of either the neck orbottom of the bottle and is collected bybreaking the bottle.

    Various Kupipakwa Rasayana and theirChemistry:

    Rasasindura :

    Equal quantity of ShuddhaParada (purifiedmercury) and Shuddha Gandhaka (purifiedsulphur) are triturated together for severalhours until the mixture is converted into ablack, lusterless, fine, impalpable powder of

    uniform consistency. This is known asKajjali. The Kajjali is then levigated byliquids like aloe gel (leaf pulp juice of Aloebarbadensis Mill.) or juice of leaf buds ofFicus bengalensis Linn. (Vatankura Swarasa).

    It is allowed to complete dryness. The driedKajjali is then placed in a long neck,narrow mouthed bottle (beer bottle) and isgradually heated on a sand bath (ValukaYantra). On cooling Rasasindura is found tobe deposited in the inner surface of the neckof the bottle and is collected by breaking ofthe bottle7.

    Chemistry : Rasasindura is identical withred sulphide of mercury and has the samecomposition as that of the mineral cinnabar,HgS. During trituration and when heated toabout 50OC, the black mass of mercuricsulphide (metacinnabar) is formed. Andwhen heated, it slowly becomes red andcrystalline and sublimed in the long neckedglass bottle.

    Hg + S = HgS

    The black sulphide becomes red onsublimation; the unstable black form isbeing converted into stable red form on

    heating8.

    Makaradhwaja :

    Eight parts of Shuddha Parada (purifiedmercury) and one part of Shuddha Swarna(purified gold) leaf are rubbed together in astone mortar to make an amalgam. Sixteenparts of Shuddha Gandhaka (purifiedsulphur) are added to the amalgam and thewhole are triturated for several hours until

    the mixture is converted into Kajjali.Further procedures are same as Rasasindurapreparation. The only difference is, herelevigation is done with juice of Gossypiumarboreum Linn. (RaktaKarpasa) flower9.

    Chemistry: Makaradhwaja is also identicalwith red sulphide of mercury and has the

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    same composition as that of the naturallyoccurring cinnabar, HgS. It also containsvery minute quantity of gold incombination with mercuric sulphide10.

    Malla / Tala / Shila Sindura :

    Equal quantity of ShuddhaParada (purifiedmercury) and Shuddha Gandhaka (purifiedsulphur) are triturated together to makeKajjali, then varying proportion (equal orhalf or quarter) of purified arsenicals(Shuddha Malla, arsenite, As

    2O

    3and/or

    Shuddha Haratala, orpiment, As2S

    3and/or

    Shuddha Manahshila, realgar, As2S

    2) are

    mixed and triturated. Further procedures

    are same as Rasasindura11

    .

    Chemistry : Malla/Tala/Shila Sindura arealso identical with red sulphide of mercuryand have the same composition as that ofthe mineral cinnabar, HgS. These alsocontain varying quantity of arsenic incombination with mercuric sulphide12,13.

    Rasakarpura :

    Specified quantity of Shuddha Parada(purified mercury), Shuddha Sphatika(purified alum), Shuddha Kasisa (purifiedferrous sulphate), Saidhava Lavana (rocksalt), and other substances like brickpowder, Gairika (red ochre), etc. aretriturated together for several hours untilthe mixture is converted into lusterless,fine, impalpable powder of uniformconsistence. The mixture is subjected in along neck glass bottle (bear bottle) and isgradually heated on a sand bath (ValukaYantra). After self-cooling the preparedRasakarpura is collected from the neck of thebottle after breaking14.

    Chemistry : Alum or ferrous sulphate,when heated, yields some sulphuric acid.This reacts with rock salt to liberatehydrochloric acid. The latter undergoes

    aerial oxidation in contact with ferric oxidefrom the brick dust, Gairika (red ochre), clay,etc., acting as catalyst, and sets free chlorine,which attacks the mercury, giving rise tocalomel (Hg

    2Cl

    2). Alumina from alum or

    from clay may also catalyze the reaction to acertain extent like the ferric oxide15.

    K2SO

    4,Al

    2(SO

    4)

    3,24H

    2O = K

    2O + 4H

    2SO

    4+

    Al2O

    3+ 20H

    2O

    Hg + 2H2SO

    4= HgSO

    4+ 2H

    2O + SO

    2

    Hg2SO

    4+ 2NaCl + Hg = Na

    2SO

    4+ Hg

    2Cl

    2

    Rasakarpura of Rasatarangini:

    ShuddhaParada (Purified mercury) is mixed

    with one and half times its weight ofGandhakamla (sulphuric acid) and heated.Thus the white moistureless powderformed, is mixed with equal quantity ofpowdered Saindhava Lavana (rock salt) andtriturated. The fine, lusterless, uniformmixture is placed in a long necked bottle(beer bottle) and is subjected on mild heatgradually on a sand bath (Valuka Yantra).After self-cooling the sublimed material iscollected from the neck of the bottle by

    breaking it11.

    Chemistry : Mercury when boiled with oneand a half times its weight of concentratedsulphuric acid, mercuric sulphate(HgSO

    4) is

    formed.

    Hg + 2H2SO

    4= HgSO

    4+ 2H

    2O + SO

    2

    On heating the dry mixture of equalweights of mercuric sulphate and rock salt,

    mercuric chloride is prepared. It separatesby sublimation on the cooler upper part ofthe bottle. It forms colourless needle shapedcrystals having melting point 277OC andboiling point 320OC16.

    HgSO4

    + 2NaCl = Na2SO

    4+ HgCl

    2

    Rasapushpa :

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    Equal quantity of ShuddhaParada (purifiedmercury) and Shuddha Kasisa (purifiedferrous sulphate) are mixed and trituratedtogether, until a lusterless, fine, impalpable

    powder is formed, then equal part ofSaindhava Lavana (rock salt) is added withthe mixture and triturated again. Themixture is then placed in a long neckedglass bottle (beer bottle) and heatedgradually on a sand bath (Valuka Yantra).On cooling, Rasapushpa is found to bedeposited in the inner surface of neck of thebottle and is collected by breaking of thebottle11.

    Chemistry: During trituration of mercuryand ferrous sulphate, mercuric sulphate isformed and some part of mercury remainsfree. The intimate mixture of convertedmercuric sulphate, mercury and rock saltare, when heated mercurous chloride isformed. It sublimes to the cooler upper partof the bottle and the crust of the sublimateis collected. It sublimes at 380OC17.

    Hg2SO

    4+ 2NaCl + Hg = Na

    2SO

    4+ Hg

    2Cl

    2

    Swarna Vanga :

    ShuddhaVanga (Purified tin) is melted andmixed with equal quantity of ShuddhaParada (purified mercury) and rubbedtogether in a stone mortar to form anamalgam. Equal parts of ShuddhaGandhaka(purified sulphur) and Shuddha Navasadara(purified ammonium chloride) are added tothe amalgam and the whole are trituratedfor several hours until the mixture is

    converted to lusterless, fine, homogeneouspowder. The mixture is then placed in aglass bottle and is gradually heated on asand bath (Valuka Yantra), until the fumesdisappear completely. On cooling, thegolden-yellow coloured crystalline SwarnaVanga is collected from lower part of thebottle by breaking it18.

    Chemistry: Swarna Vanga is obtained asgolden yellow scales of crystalline SnS

    2,

    better known as mosaic gold. By heating amixture of tin, sulphur and ammonium

    chloride in glass bottle, a stannate and thio-stannate is formed19.

    Sn + 4NH4Cl = (NH

    4)

    2SnCl

    4+ H

    2+ 2NH

    3

    2(NH4)

    2SnCl

    4+ 2S = SnS

    2+ (NH

    4)

    2SnCl

    6+

    2NH4Cl

    Discussion :

    The Kupipakwa Rasanayas are prepared inespecially prepared glass bottle, designedinstrument, known as Valuka Yantra. The

    glass bottle with a long neck (beer bottle) iswrapped with several folds of clothsmeared with clay, and then dried in thesun. That makes the bottle more heat stable.The bottle is buried up to its neck in sandplaced in an iron pot; heat is applied fromunder the pot. This arrangement helps ingradual and homogeneous heating.

    Mercury and sulphur are the elementsmostly used in preparation of various

    Kupipakwa Rasayanas. In many processesmercury has been used to amalgamate withthe metals and form an intermediateproduct, which could increase the surfacereactivity of the metal with other chemical.Sulphur facilitates the formation ofrespective sulphide. In these cases mercuryand sulphur have acted as promoters for thefinal chemical reaction. Mercury itself isbeing in liquid state, readily reacts withsulphur to form HgS (black sulphide)3.

    When mercury is amalgamated with metals,it gets converted into semisolid mass andeasily reacts with sulphur to form blacksulphide, HgS, and thus it promotes thehigh temperature reaction with othermetals.

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    Most of the chemical reactions involve inKupipakwa Rasayana preparations areheterogeneous kinetics i.e. reaction betweensolid-gas or solid-liquid and it is knownthat the rate of such reactions is

    proportional to the interfacial area. Duringsuch reactions, at first a surface layer of thechemical is readily formed (chemical ratecontrolled) and afterwards the rate ofreaction becomes diffusion, rate controlledand slow. The ancient Ayurvedic scholarswere conscious of these facts and overcamethis problem firstly by increasing theprimary surface area and secondly byremoving the chemical layer formed on themetal particles and thus exposing newmetallic surface. These conditions wereachieved by intermittent trituration. Insolid-solid reaction, trituration increasedthe chemical rate kinetics1.

    Sublimation is the chemical process,involved in most of the KupipakwaRasayanapreparation. It is the unique processconverting a solid directly into vapour andcondensing the vapor into solid state havingthe same composition3. The ancient scholarsof Rasashastra (12th cen. AD) may be

    acknowledged as the pioneers of thesublimation process. The gradual heatingpattern, use of sand bath (ValukaYantra) forindirect and homogeneous heating and longnecked glass bottle for providing adequatespace for re-solidification, should beconsidered as examples of great knowledgeof chemical processes.

    Now a days electric muffle furnace isbrought into practice instead of Valuka

    Yantra for preparation of KupipakwaRasayanas with added advantage of easyregulation of temperature, lack of need offuel (coal), elimination of smoke and dust,etc. But there are some disadvantages alsolike high product cost due to electricitycharges, and difficulty in large scaleproduction. The temperature pattern in

    muffle furnace for preparation of KupipakwaRasayanas is also being standardized, likefor mild temperature (Mriduagni) thetemperature range will be 150OC 200OC,for moderate temperature (Madhyamagni)

    the temperature range will be 200O

    C - 400O

    Cand for higher temperature (Tivragni) thetemperature range will be 400OC 600OC20.

    The temperature pattern and duration forpreparation of all the Kupipakwa Rasayanasare different, but gradual heating system isfollowed for all. Preparation of Rasasindura,Makaradhwaja, Malla/Tala/Shila Sinduraneed almost same grade of heating butduration depends on amount of freesulphur in the Kajjali, here requiredhighest temperature is around 600OC. Forpreparation of Rasakarpura the highesttemperature should not exceed 300OC andrequired duration is 9 h. The highesttemperature and duration for preparation ofRasapuspha are 400OC and 9 h respectively.For preparation of SwarnaVanga the highesttemperature given is 450OC and is neededfor longer duration, not less than 12 h.

    It must be remembered that all the

    KupipakwaRasayanas are not pure chemicalcompound, rather cocktail of many traceelements also. Those make the producttherapeutically more potent and less toxic16.The drugs for levigation (BhavanaDravyas)may contribute these trace elements to thefinal product.

    Conclusion :

    In conclusion it may be said that all the

    KupipakwaRasayanas are product of complexchemical processes. The modern analysis ofthese processes confirms the high level ofunderstanding of the physico-chemicalprinciples and the skill achieved at an earlydate in ancient India.

    Acknowledgement :

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    Authors are thankful to Dr. B. J. Patgiri andDr. Galib, lecturer, Department ofRasashastra and Bhaishajya Kalpana,

    I.P.G.T.&R.A., Gujarat Ayurved University,Jamnagar, for their valuable suggestion andco-operation in writing the manuscript.

    References :

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    2. Upadhyay Madhav, Ayurved Prakash, Mishra GS: Hindi commentary, ChaukhambaBharati Academy, New Delhi, 1994.

    3. Dutta P. K., General and Inorganic Chemistry, Vol. II, Sarat Book House, Kolkata, 11thed., 1996.

    4. Choudhary AK, Standardization of Kupipakwa Rasa- A Pharmaceutical Approach,Seminar proceedings, National Seminar, Gujarat Ayurved University, 2004.

    5. Jha CB, Mohapatra S, Hiremath RR, Impact of Indigenous Processes on Certain Mineralsand Metals, Seminar proceedings, Ayurvedic Medicines and Practices- Focus on Bhasma,Amhedabad, 2006.

    6. Vohora SB, Kim HS, Shah SA, Khanna T, Dandiya, Trace and Toxic elements in Nutritionand Health, Wiley Eastern Ltd., New Delhi, 1993.

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    12. Joshi CJ, Sharma HS, A Study on Silasindura w. s. r. to Its Toxicity and Its ClinicalEfficacy on Eosinophilia, Ph. D. Thesis, Gujarat Ayurved University, Jamnagar, 1993.

    13. Inamdar MP, De S, Ravishankar B, Pandey D, Standardization of Manikyarasa(Talasindura) and Its Pharmaceutical Study w. s. r. to its Toxicity, M. D. Thesis, GujaratAyurved University, Jamnagar, 2000.

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