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Medieval Gunpowder ChemistryA Commentary on the Firework Book
Geoff Smith
Summary
:  Arguably the most important Western source on the early history of gunpowder technology is the late thirteenth century manuscript, Das Fuerwerkbuch. When it was translated into English in 2, it contained a commentary on the chemistry of many of theformulations gi!en. "hese were largely dismissed as useless alchemical nonsense which could not work. Although some mysteries remain, much of the formulation can be understood either as contemporary #best practice# or by comparison with modern pyrotechnic and e$plosi!e knowledge."his paper re%e$amines the underlying chemistry and demonstrates some surprising inno!ations anticipating much later claims.
Keywords
& 'unpowder, Firework book, Fuerwerkbuch, Alchemy
The Firework Book
 "he Firework (ook )FW(* is one of the earliest, and certainly the most widely disseminated work of its time describing gunpowder in Western literature. +t was, in the fashion of the day, copied many times by or for aspiring artillerists and about  copies areknown dating from about -."he original was written in /iddle 0igh 'erman as Das Fuerwerkbuch and a full translation was published in 2 which made this work readily accessible in English for the first time
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. +n translation, the editors ha!e made a!ailable a significant contribution to the literature of early gunpowder. 0owe!er the accompanying comments on the medie!al chemistry described lea!es much to be desired. +n particular, the assertion that the saltpetre of the time was the calcium salt rather than the uni!ersally accepted potassium nitrate is readily dispro!ed but still appears to ha!e some acceptance among historians. "wo published papers ha!e dealt e$tensi!ely with this error 
-, 2
 but critical re%e$amination of the translation re!eals a significant number of additional instances where the te$t has been either glossed o!er or dismissed as medie!al hyperbole or Alchemical nonsense. +n addition, it also clearly identifies sources of potassium which were missed in the translation+t is the intention of this paper to point out at least some of these omissions and in doing so indicate some remarkable inno!ations which anticipate much later practice. +n re!iewing the translation, the following important facts should be noted: Firstly no complete manuscript e$ists. "he translation refers to Freiburg /1 32 and indi!idual sections ha!e been dated between about -4 and-. "his is a time span in the order of fifty years 5 a long working life span 5 and it is unlikely that the same author was responsible throughout. +t is possible that other sections might come to light. "here is alsothe problem of accurately translating some words where the language of the time was -"he Firework (ook, 'unpowder in /edie!al 'ermany, Arms 6 Armour 1ociety 2
 
imprecise. "his is particularly important in the naming of chemical compounds which at that time were far from fi$ed
2
. +n the te$t saltpetre, for instance, is gi!en different names depending on the degree of purification&
salniter, salpertica, salbratica
etc. Although the manuscript refers to 'erman practice, it is interesting to consider English e!idence for the period. Although no contemporary e7ui!alent document is known,the materiel stored at the "ower of 8ondon at that period are well documented and from these some insight can be gained into the gunnery practice of the time."he FW( manuscript is contained in sections referred to as Folio 9 to 43. As mightbe e$pected of a manuscript compiled from sections of different dates and different copying scribes, not all sections flow in logical order and there is strong e!idence of inattention where for instance a rubric is repeated !erbatim immediately beneath. Althoughthe scribes may well ha!e been students of the master, some sections may ha!e been made by professional copyists and there may be errors and omissions. "his paper follows the order of the /1 as far as reasonably practicable. Folio references refer to the 2 translation and 7uotations from that document are italicised.utting aside the difficulties of translating from -; middle high 'erman, the language of the time simply did not ha!e precise words to describe some chemicals or chemical operations but this is not to infer that these were unknown. "he principles of crystallisationand distillation were well established long before."he te$t is presented as a dialogue between the /aster 'unner and his pupil. +t is e!ident that at the time of writing, gunpowder technology was well de!eloped and the ad!ice and formulations gi!en represented the state of the art current at that time. +t follows, and is born out by the te$t that the /aster 'unner was well !ersed in the acceptedtechnology of his day, Alchemy. 1ome elementary knowledge of this ancient art helps to e$plain some of the more esoteric additi!es recommended. /odern chemistry, for instance, offers nothing to e$plain the significance of #
Living Sulphur 
.# Appendi$ A offers a !ery brief appreciation of medie!al alchemy. Although written by the #/aster 'unner#, the /1 makes clear that this is not an artillery training manual. Although it contains some pertinent comments on gun management, its primary purpose is an aide memoir to record a large number of formulations which would now be considered the remit of an Ammunition "echnician. 1incegunpowder was e!idently known in the west, at least from (acon#s
Opus Majus
 and
Opus Tertium
 )c.-23%-24*, the /1 must be considered as a record of the technology as de!eloped o!er the pre!ious century. Following a preamble on the need to ha!e good knowledge in the field of artillery, in F 9, the master poses and answers twel!e 7uestions. "he first #
...Does the fire drive stone out of the gun or is it the vapours caused by the fire?,
reflects the state of knowledgeat the time. "he /aster replies #
...enerally, it is said that the fire has the po!er... but " say that the po!er comes from the vapours.# 
 "his shows ad!anced thinking for the time and a di!ergence from the Aristotalean tradition. +t should be noted that there was no distinction between smoke, !apour and gas, all of which were referred to as #airs# until the early -9th ;. "hus an increase in smoke could well be e7uated with increased power and we shall see e!idence of this later.
2"he author has e$perienced sulphate being purchased in error for sulphite and precipitated chalk mistaken for #French chalk# by a well%meaning buyer<
 
The gun
 F9"he manuscript throughout refers almost entirely to one type of gun, the
Steinb$chse
 which simply translates as #1tone 'un#. +t is clear from the te$t that this is what is commonly referred to in English as a (ombard. =nly one other type, the
%lotenb$chse
 is mentioned once !ery late in the te$t and will be dealt with later. =ther types of gun were in e$istence in -. "he earliest )Western* illustration of a cannon is in the well known /ilemete manuscript reliably dated at -23. hysical e!idenceis seen in the 8oshult gun
, the />rk> gun )c.-* and the "annenburg )c.-??*, all well before the earliest stratum of the FW(."he bombard is characterised by the small diameter powder chamber and the large calibre barrel. "hese are dictated by the stone pro@ectile
, which must be necessarily large to ha!e sufficient mass, and the limitations of the contemporary metallurgy. A parallel bore would ha!e been difficult to charge with the rather small !olume of powder re7uired while still achie!ing reliable ignition. "he /aster 'unner recommends a powder charge filling one 7uarter to a third of the chamber which is then closed with a wooden plug before the ball is inserted so that thecharge will burn more rapidly. owder filling the chamber and possibly compressed by the plug would burn progressi!ely from the ignition point )iobert#s 8aw* and would push out the plug and much of the unburned powder into the larger calibre bore where the pressure,and hence burning rate, would significantly fall
. (y only partly filling the chamber, the flame front has access to a much larger surface area. Although not reported until the -4th ; there is a possibility of a partly filled chamber producing a #pressure wa!e# with disastrous results. +t is significant that the te$t states 5
 This !ay you can shoot further and can also burst a gun more easily than if you fill the chamber !ith meal po!der right up to the plug.
)author#s emphasis*"here follows e$cellent ad!ice for using up sub%standard powder: i.e. part load with good powder and complete the load with the poor on top 5 ensuring ignition of the less perfect materiel. "his is followed by ad!ice that powder
 pressed into ca&es
 )
%nollenpulver 
* is more powerful than meal powder )serpentine* in the ratio :2. "he section concludes with a persuasi!e account of how gunpowder was in!ented by (ertoldus iger. "he contribution, and e!en the e$istence, of this ;istercian monk
3
 has been e$tensi!ely debated for many years. 0owe!er since the date attributed to his disco!ery is gi!en as -44 which is  years after the first record of cannon in the West it will not be further discussed here.
Gunpowder Chemistry
F 93"he section begins with the most important ingredient, saltpetre. At that time saltpetre was har!ested from cellar walls where it was obser!ed to #grow# and could be simply scraped off and purified. An impro!ed method is propounded where the wall is replaced with a porous )unglaBed * pot which is coated with a mi$ture of tartar, limestone and salt made into a paste with the urine of a man who drank wine. "o e$plain these ingredients, it is necessary to understand the chemistry of saltpetre production.
o precise date but mid -;1tone was the common pro@ectile for large calibre bombard of this period. "hese guns had limited mobilityand were primarily used for attack or defence of fortifications. A hea!y pro@ectile was necessary to be effecti!e. +ron could not be readily cast at that time )in Europe* and would ha!e placed an intolerable strain on the gun. "he gunstone was a direct descendent of the rocks thrown by the old ballista, and is often misidentified as such.An e$ample of the high%low pressure system such as currently employed in the mm grenade launcher.3"he ;istercian habit is white. #(lack friars# usually refers to the Dominican order although (enedictines also wear black. resumably the soubri7uet refers to his alleged dealings in the #black arts#.
 
1altpetre does not occur naturally but is always the result of decay of some organic matter. Crine, a commonly used natural resource in medie!al times, is used by mammals
9
 to e$crete e$cess nitrogen from the body largely in the form of urea
4
 ;=)0
2*2.
 "his is broken down biologically by bacteria. First soil commonly contains the enByme urease, which catalyses the con!ersion of the urea molecule to ammonia. itrosomas bacteria o$idises ammonia salts to nitrite and then spirobacter con!ert this to nitrates. "he reaction is only efficient within a restricted range of acidity )p0 3.4%9.4*
?
 1ince the first of these stages releases some acid, which must be neutralised and this is achie!ed by the limestone
 )calcium carbonate*. "he bacteria are not acti!e below c.-; and so we are ad!ised to stand the pot in the sun for three days before remo!ing it to a cellar 5 where saltpetre #flowers# will form on the pot
."artar was another well known resource at the time. When wine ferments a crystalline crust deposits on the side of the !at mostly composed of potassium hydrogen tartarate. "he porous pot pro!ides a large surface area gi!ing the bacteria access to o$ygen in the air. "hus all the re7uirements are met for a highly sophisticated bio%digester to both produce nitrate ions and pro!ide them with potassium. +t is not suggested that in - the underlying reactions were understood, but the credibility of the proposed processis undeniable."he presence of salt is not easily e$plained but since salt readily separates during the following recrystallisation stage, it is unlikely to ad!ersely affect the critical reactions . 0a!ing produced saltpetre, it re7uires purification by recrystallisation, a process long established and well known to any Alchemist
. "he solubility of saltpetre increases !ery rapidly with temperature and thus, when its solution is cooled it will crystallise out longbefore any other salts present. +f competently done, the result should be fairly pure potassium nitrate. 0owe!er, the /aster 'unner has, probably unwittingly, pro!ided meansof dealing with any small residual impurities
2
. ;harcoal contains potash and when ground intimately with nitre any calcium salt containing water of crystallisation undergoes a solid state reaction to produce potassium nitrate and release the water thus becoming #
' a littlemoist. Do not let this trouble you.
# which then e!aporates .F4-. "he recrystallisation is normally carried out with water but the FW( says that wine or brandy )alcohol* is better and strong !inegar )acetic acid* better still. +n modern chemistry this process would be known as salting out )also known as anti%sol!ent crystalliBation, precipitation crystalliBation, or drowning out* and could well impro!e the yield but probably not economically./odern chemists will recognise the occasional reluctance of some preparations to crystallise, and here we ha!e a recommendation to introduce small pieces of wood to aid what we would now call nucleation. uality control is not ignored. For lack of a thermometer, the time and temperature are compared with the conditions for boiling fish, greasy pans must be a!oided, the end product must be tasted and when dropped on burning charcoal must burn with a blue flame. +n spite of the additions of calcium in the form of 7uicklime, the obser!ation that when sprinkled on glowing charcoal #.
..the fire colours blue# 
 is proof positi!e that the product is potassium nitrate. )FW( pp-62*. ot only is the blue )usually now described as lilac* characteristic of potassium but it is !ery easily masked by e!en small amounts of
9"he a!ian e$cretory system is slightly different and an e!en more !aluable source of nitrogen. 0ence the popularity of pigeon droppings in later times and e!en more prolific seabird sources as ;hile 1altpetre4An adult e$cretes about 2g of urea per day.?"he reactions ha!e been e$hausti!ely researched in recent times in the conte$t of waste water treatment and are here simplified as appropriate to this paper..-ust as lime is added to soil in standard agricultural practice.--"he formation of chemical salts on brickwork, efflorescence, is a commonly obser!ed phenomenon.-2"he earliest known complete purification process for potassium nitrate was outlined in -29 by the chemist and engineer 0asan al%ammah of 1yria in his book
al()urusiyya !a al(Manasib al(*arbiyya
 )#"he (ook of /ilitary 0orsemanship and +ngenious War De!ices#*.

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