E X P L O S V E S

A RT H U R M A RSH AL L

C h e mic a l I n sp e c to r , I n dia n Or dna n c e D e p a r tm n t

e

SE C OND EDI TI ON

Vol . I

H I S T O RY AND M AN U FA C T U R E

WI TH 77 I LLUS TRATIONS

P H I L AD E L P H I A

P B L A K I ST O N S SO N
’
. C O .

10 1z W AL NU T ST RE ET
 D E D 6 A T E D .

352 T e r mi s s i o n
G the fl i g ht Tl fo n o u m b le
" '
o

D A V lD L LOQD G E O RG E , MP . .

P R I ME MIN lS T ER

iEu mp e a n W
e

w ho b a r i ng the g r e a t ar l
a so s er v e b

his W i ng a nb (fl o u n tr g as

G ha n c e llo r o f the T x c he q u er
mi n is te r o f m u ni ti o ns

a nb

S e c r e ta r y o f S ta te fo r W ar

“
Ar ma Vi r u mq u e C a n o

V ir g i l .
 PRE FAC E TO SE C O ND E D I TI O N
TH E fact that a s econd edition of thi s work has been c alled fo 1 only a year
after the publication of the first indicates that it was really wanted The .

Great War has meantime c ompleted the second year of its c ourse but has ,

not caused the introduction o f any ve 1 y novel explosives despite sensational ,

statements of s o me j ournalists Certai n aspects of the manufactu re of e x

.

plosives have h owever become of greater importance and have therefore

, , ,

been treated in greater detail i n thi s edition P icric acid trinitrotoluene .

,

and other nitro aromatic comp ounds were formerly m erely b y products of
- -

th e dye industry and c onsequently their manufacture seemed only to call

,

for brief notice in a work on explosives Now however they are bei n g made
.
,

on a very large scale m factories specially erected and thei l supply has become ,

a matter of national importa nce i n every c ount 1 y in E urope B e fo 1 e the W a i .

nitric aci d made from the air could hardly anywhere c ompete with that manu
fa c tu r e d from sodium nitrate but the blockade of Germany has altered this
, .

Thu s does history repeat herself for in th e Napoleonic wars E ngland c ut

,

o ff the supply of potassium nitrate from India to France and caused a great

development of the French saltpetre industry The blocka d e has also cause d .

Germany to pay m ore attention to chlorate and perchlorate explosives and

th ose made with liqui d oxygen .

The publication of L es P ou dr es a i E x p lo s ifs by L Ve n n in and G Ches , . .

neau has enabled me to improve the description of French explosives and

,

methods As in the first e dition but little space has been given to explosiv e
.
,

sub stances that have not any commercial military or theoretical impor ,

tance A systematic account of all classes of explosives orga ni c and inorganic

.
, ,

will b e found in the work of Ve n nin and Chesneau j ust mentioned .

'

I h ave spared no trouble to make the work as reliable and useful as pos
sible to those engaged i n making and dealing with the explosives used in thi s
tit a n tic struggle and I h e pe that in thi s way I have assiste d slightly in spite
of the fact that I am detained far from the principal theatres o f war There
, ,

are of c ourse some matters in c onne x ion with explosive s which cann o t be
published .

My best thanks are given to my former fellow student G C Jones fo r very ,

. .
,

kin dl y un dertaking the revi s ion of the proofs a n d the preparation of th e

index thus not only relieving me of much work but also greatly expediti n g
, ,

the publication of this edition My former colleague William Barb o u r h a s

.
, ,

made a number of u seful s u ggesti o ns a n d s u pplied me w ith c o pie s o f s ome

papers which I c ould not o therwise have o btained i n time .

A MA R SHALL . .

NAI N I TAL I N D I A , .

Feb r u a r y , 1 9 1 7 .
 PRE FA C E TO FI RST E D I TI O N
S IN C E t he late Mr . Oscar Guttmann published his work on the Ma n u fa c tu r e
o f E x p lo s iv es in 1 8 9 5 no c o mprehens ive book on thi s subj ect has appeared

in E nglish . In t he interval t he e x plosives industry has un dergone many

c hanges every branch of it has developed enorm o usly e ven that of black —

po w der ; and scientific investigations have t hrown light on many of the

pr o blems that arise in the manufa c tur e a nd use of explosives E specially .

d ur ing the last few years many obscure points have been cleared up It i s .

h oped therefore t hat t he presen t work wil l be f o un d to supply a real want .

I n a si ngle book of modera te size it is not possible to treat in detail every

p o int t hat arises in con nexi o n with e x plosives Consequen t ly it has bee n .

ne c essary t o restric t i t s scope in some d irec tions The methods of using .

explosives belong rather to the subj ect s of ball i stics blasting etc a n d the ir , , .
,

ful l di sc ussion w oul d alone requ ir e a larger work than t hi s Therefore they .

have only been referre d to briefly Detail s of manuf acture al t hough often
. ,

of mu c h practical importance can o nly be learnt properly in the factory :

,

c onsequen t ly they have been omit te d in many cases Pr e p o sa ls made in .

patent specifications have not bee n dealt wi th unless they possess practical
or theoretical importance for more deta iled information concerni ng pate nts
relating to explosives the reader sho ul d refer t o w o rks such as those of
R E s c ales
. . Subj ects which are treate d ful ly in the ordi nary scientific or
te ch nical te xtbooks have o nl y been d ealt wi th in so far as they t hrow new
light on problems c onnecte d w ith explosives .

On the other hand an endeavour has been made to increase the useful ness
,

o f the book by colle c ting allied facts from scatte red source s and placi ng them ,

in j uxtapositi o n w ith o n e another Some subj e c ts which are o nl y mentioned

.
,

briefly or not at a ll in other book s have been trea te d more full y t han their
. .

intrin s i c imp o rtance w ould other w i s e have c all ed fo r Numer o u s references .

to original paper s e tc have been given to assis t t hose w h o require more

, .
,

d etail ed inf ormation concerning the subj e c ts d ealt with Co nsi d erable s pace .

ha s been g iven to matters connecte d w ith the di ffic ult and intricate que s tion
of the s tability of ni tro ce llul ose and allied compound s
-

I am indebted to my “ i fe for her valued help in revi s ing the bo o k My

.

thanks are also due to Mr W Rin t o ul Mr J Th o rburn and Mr \V R Mo o re

. .
, . .
,
. . .

for assis tance in re v is ing the proofs .

It is my earnest hope that t he b ook may be of help to my c o untry in the

pre s ent time o f emergency .

A MA RSHALL . .

NAI N I TAL I N D IA
, .
 C O N TE N TS
P AG E

L I ST OF P R INCIPAL ABB RE V I AT ION S

IN T R OD U C T ION
Ex pl o si o n Ex plo s i ve G a s e v o lu t i o n Hea t li b era t i o n Sens i t i vene s s :
Co ns t i t uen t s o f e x plo s i ve s Ox ygen c arriers Co m b u s t i b le c o ns t i t uen t s
Ni t ro ar o ma t i c c o mp o und s Ni t ri c e s t ers S mo kele s s p o w der s En do
—

t hermi c c o mpo un d s Vel o ci t y o f e x pl o s i o n I n c o mple t e d e t o na t i o n :

S t ab ili t y Summary

PA RT I : H I S T O R I C AL
C HA PT ER I
E ARLY H I ST O R Y
Gunpo w der Co nfu s i o n o f t erms Inc endiary mi x t ure s Greek fire
fi r e Sal t pe t re The Chinese The In dians Ro ger Ba c o n The
In v en t i o n o f fi r e arm s Summary Gi b b o n
-

C HA PT ER II
D E V E L OPM E N T OF G U NP OV
VD ER

Early manuf ac t ure E arly p o w der makin g machinery Inc o rpo ra t ing mil l :
-

S t amp mill s Ad di t i o ns to gunpo w der Co rne d p o w der P re s s e d po w der

Breaki ng do w n Co mpo s i t i o n o f gunp o w der Te s t ing gunp o w der Fire
arm s Do u b le b arrelle d gun s Rifle s Cann o n : Pr o j e c t ile s Incen di ary
-

mi s s iles Shell Fuse s Hand grenades Infernal ma c hine s

-
Fire
w o rk s Mili t ary mine s Blas t ing

C HA P T ER III

P R O G RE SS OF E XP L O S I V E S IN TH E E I G HT EE NTH
AND NIN E T EE NT H C E NTU R I E S
Ber t h o lle t Chl o ra t e Igni t ers Fo rsy t h s de t o na t o r l o c k Ful mina t es Cap s
,
’

Fu s e s Gun c o tt o n Ni t ro gly c erin e Amm o nium ni t ra t e e x pl o s i ve s :

- -

Sprengel e x pl o si v es Co al mi ne dangers
-
Cheddi t e I n s pe c t i o n o f
e x plo s ive s Smo kele ss po w ders Pi cri c a c id Tro t y l
 C O NT E NT S
PAG E

PA R T II : B L A C K P O ‘V D E R

C HAP T ER IV
MAN UFA C TURE OF SALT P E T RE
Ni t re depo s i t s Frenc h s al t pe t re in du s t ry Art ifi c ial ni t re b e ds En li s h g

sal t pe t r e indu s t ry Fo rma t io n o f ni t ra t es Bert hel o t s researc he s Ba c ’

te r ia l ac t i o n Indi an s al t pe t re in du s t ry In dian refinery Ch ili ni t ra te

”
de p o s i t s Co n versio n sal t pe t re Refining sal t p e t re Sal t p e t r e fro m
t he a t mo s phere

C HA PT ER V
MANUFA C TU RE OF C HA R CO AL AN D SUL P HU R
Ch arc o al Wo o d u s e d Di s t il la t i o n Compo s i t io n Bro w n c harco al :

Sul phur Si c ilian s ulphur B y pro du c t s ulphur Lo ui s iana sul phur

-

Re fining sulphur P ro pert ie s Fu nc t i o n s o f s u lphur

C HA PT ER VI
MA N UFA C TU RE OF G U NPO W D ER

Adv an t ages a nd di sad van ta ges Co mpo s i t io n Grin ding t he ingre dien t s :
Weighing a nd mix in g Inc o rp o ra t in g o r milling Au to ma t i c drenc hers
Rem o vin g t he mill c a ke Breaking d o w n P re s s ing G r anula t ing o r co rn
-

i ng Dus t ing a n d glazing S to vin g o r drying Fini s hing a nd b len ding :

Cu t po w der s Mo ul ded po w ders Blas t ing po w ders Sprengs alpe ter :
C a h u ec it P e tr o kla s t it B o b b ini te “ a te r s o lu b le po w der P ro du c t s
l -

o f e x pl o s i o n

PA R T III : AC I D S

C HA PT ER VII
SUL P HU R IC A CID
Manufac t ure P urifi c a t i o n Co nc ent ra t i o n Mel t ing po ints -
S pec ific gra vi
t ies Cal c u la t i o ns Supplie s in w a r t ime -
.

C HA PT ER V III
NI T R IC A CI D
Manufac t u re Re c o v ery of ni t ro u s fumes Sto rage The di s t ill a t i o n Ni t r e
cake Ni t ri c a c i d fro m t he a t mo s phere D irec t o x i dat io n Cyana mi de
pro c e s s Se r p e k s pro c e s s Ha b er s pro c e s s Os t w ald s pro c e s s Pro
' '
’

pe r t ie s S p ec ifi c g ra vi t ie s Free zing p o in t s Bo iling po in t s Va po ur

- -
 C O NT E NT S x 1

P AG E

C HA PT ER IX
MI X E D AND WAST E A CID S . MANIP ULAT I ON
Mi x e d a ci d Mi x ing t he a c i ds
Pr o per t ie s o f mi x e d a c i d s Spe c ifi c gra v i t ies
Vapo ur pre s s ures Wa s t e a c i d Gun c o tt o n w as t e ac i d Ni t r o glyc erine
- -

w as t e a c i d Ni t r e c o mp o und w a s t e a c i d Deni t ra t i o n plan t Ma ni pula t i o n

-

o f ac i ds Ma t erial s Rai s ing a c i d Oleum

PA R T IV : N I TR I C E STE R S OF C A R BO H Y D R A T E S
C HA P T ER X

TH E O R Y OF NI T R AT ION OF C E LLUL O S E
S t age s o f ni t ra t i o n o f c ellul o s e Highe s t a tt aina b le ni t ra t i o n S o lu b ili t y :
S o l u b le ni t r o c ellul o s e : Quan t i t y o f a c i d Co ns ump t i o n o f a ci d Eff e c t o f
—

ni t r o us a c i d Tempera t ure a nd t ime o f ni t ra t i o n Na t ure o f t he c o tt o n

Ni t ro c o t t o ns o f lo w ni t ra t i o n Pyr o x ylin Co llo di o n
-

C HA PT ER XI
C E LLUL O S E
Na t ure o f c ellul o s e Lign o c ellul o s e Co mp o und c ellul o s e s Rea c t i o ns o f
-

c ell ul o s e Wi t h s ulphuri c ac i d Wi t h ni t ri c a c i d Mer cerize d c o tt o n :

Vi s c o s e Cellul o s e b en z o a t e s A ce t a t es S c h w ei t z er s reagen t Hydra t e ’

c e llul o s e Ox y c ellul o s e
-
Ni t ro o x yc ellul o se e tc
-
Vi s c o si t y
, Over
.

b lea c he d c o tt o n Ni t ra t e d mer ceri z e d c o tt o n Eff e c t o f dilu t e al kali

Co tt o n u s e d in manufa c t ure ; Wo o d c ell ul o se Ac t i o n o f b a c t eria S t rue
t ure o f c o tt o n fi b re Dea d c o tt o n

CHAPTER x ii

MA N U FA C TU RE or NI T R O C E LLUL O S E
- L/
Pi c kin g t he co tt o n Tea s ing Dry ing Ni t ra t ing Ab el s pro ce s s Cen t rifugal ’

pro c ess Dir e c t di pping Di s pla c emen t pr o c e s s Hya t t ni t ra t o r High

ni t r o gen gun c o tt o n P ar t ially s o lub le ni t ro c o tt o ns
—
S o lu b le ni t ro
-

c o tt o n s P yr o c o ll o di o n Co ll o di o n fo r b las t ing gela t ine Co ll o di o n fo r

o t her purp o s es

C HA P T ER X III
TH E STAB I L I ZAT ION OF NI T R O C E LLUL O S E
-

Earl y me t h o ds B o iling P ulping Rem o val o f fo reign b o dies Po a ching :

Blending Add i t i o n o f c al ciu m c ar b o na t e Mo ulding e tc The b ea t er : , .

Al kaline me t h o d o f s t a b ili z a t i o n Sulphuri c e s t er s Vel o c i t y o f h y dr o ly s i s

o f ni t r o c ellul o s e
-
U S Ord nan c e me t h o d
. Cellul o s e ni t ri t e s P ro duc t s
o f de c o mp o s i t i o n \Va s h ing c o ll o d i o n c o tt o n
x ii C O NT ENT S
P AG E

NI T R IC ES T ER S OF O TH ER C AR B O HY D R AT E S
Ni t ro s ta rc h Ni t re sugars
- -

PA R T V : NI T R I C E STERS OF G L Y C E R I NE
C H APT ER XV
G LY C ER IN E
So urc e of g ly oe r ineS o ap b o ilin g P ur ifi c a t i o n o f spen t ly e Co nc en t ra t i o n
Au t o c la v e pr o c ess Co m b ine d pro c ess Tw i t c hell pro c e ss Fermen t p r o
c es s Di s t illat i o n

C HA PT ER XVI
MA N UF A CTUR E or NI T R O -
G LY C ER I N E
Early me t h ods Mo d ern plan t Ni t ra to r Inj ec to r Separator Prew a s h
ta nk Wa s hing Fil te ring IVa sh w a te rs Af t er separa t io n Re c en t
- -

impro vemen ts Ab o li t io n o f coc ks Fume ho o ds P lugs fo r air h o les : -

So fte ning t he w as hin g w a te rs Was hing o perat io ns Lab yrin t hs Ni t ra to r

arran emen t s Ac i ds a n d y iel ds Time o f separa t i o n Co n veyan c e o f
g

ni t ro glyce rine Gu t te r s Lo c a t i o n o f fac t o ry Ai r supply Limi t b o ard s :

- -

Thund er s t o rm s -
General prec au t io ns Se n si t i venes s

X VI I
C H AP T ER
L O W F REE ZI N G NI T R O G LY C ER IN E
- —

Freezin g o f ni t ro gly c erine e x pl o s i ve

-
E ff ec t o f a ddi t i o n s
s Super c o o ling :
-

Din i t ro gly cerin e Dini t ro c hl o r hy dr in Dini t ro a c e t in

- — -
Dini t ro fo r mm :
-

Te t rani t ro dig lv ce r in e Di ni t ro glyc o l Ni t ro i so b u t yl

- - - -
glyc erine ni t ra te 2 2
23

PA R T V I : N I T R O A R O MA T I C
-
C O MP O U ND S
C HA P T ER X VI I I
B Y — P R OD U C TS OF CO AL D I ST I LLAT I ON
Aro ma t i c c o mpo un d s Di s t illa t i o n o f c o al Co al ta r : No menc la t ure Be n zo l
—

fro m ga s Di s til la t i o n o f c o al ta r To luene fro m pe t ro leum C a r b o h c a c rd

P hen o l fro m b enz ene : Naph t halene : Yiel d s
 C O N T E NT S xiii
P AG E

C HA P T ER XIX
NI T R O D ER I VAT I V E S OF A R O MAT IC HY D R OCA R B ON S
Nitro benzene C H NO Ac c i den t s Dini t r o b en z ene C H (N0 ) Trini t r o
-
, B 5 2
-
, G 4 2 2

b en z ene , Ni t r o t o luene C H NO Dini t ro t o luene C H

~

, 7 7 2
-
, 7 e

N 0 2 4 Trin i t ro t o luene C H N O -
Was t e aci ds
,
P urific a t i o n o f
7 5 3 s

t rini t ro t o luene The t rini t ro t o luene s Ac c i dents Pro perties Dens ity
- -

Mon o ni t ro naph t halene C mH NO

- -
Dinitr o naph t halene C H N 0
, 7 2
-
, JO 6 2 4

Trini t r o naph t halene C mH N 0 Te t ranitro naph t halene C H 4N 0

-
, ,, 3 G
-
, IO 4 8

C HA P T ER XX
O TH ER NI T R O A R O MAT IC CO M PO UND S -

Anil ine C GH 5NH 2 Diphenylamine (C 6H 5) 2NH H e x a n itr o diphenylamine , ,

-

(C GH 2N 3 O G) 2NH Ni t ro aniline s Ni t r o me thy la niline s

—
Manufac ture -

o f t e t ryl P r o per t ie s o f t e t ryl Higher ni t r o deri v a t i v e s o f me t hyl aniline - -

Pi c ri c a c i d , C GH 3N 3 0 7 Pr o per t ie s Higher ni t r o pheno l s S t yphni c a c i d , -

C GH 3N 3 0 3 Tri ni t r o c re s o l -
,
Pi c ra t e s a n d t rini t ro
c r e s y la te s Trini t r o anis o le C GH gOCH , (NO z) 3 Kine t ic s o f nitra t i o n
-
,

PA RT VI I : S M O KE L E S S P O W D ERS
C HA P T ER XXI
SL OW BU R NIN G SM O K E L E SS PO W D ER S
-

Drying t he n itro c ellul o se Al c o h o li z ing Inc o rpo ra t i o n Shaping the

-

p o w der P o u dr e B Ru s s ian po w der Rumanian p o w der Belgian

p o w der : Am eri c an p o w der Spani s h p o w der Balli s t i t e Fili t e : S o leni t e
German po w ders Co r di t e Weighing t he gun c o tt o n Measuring the -

ni t r o glyc erin e
-
Mi x ing In co rp o ra t ing P ressing Drying Japanese
p o wder Spo r t ing rifle p o w ders Ax i t e Mo ddite

XX II
C HA P T ER
RE QU I RE M E NTS OF A SL O W BU R NIN G SM O K E L E S S PO W D ER
-

Rate o f b ur ni ng Fo rm o f p o w der Pr o gre s s i v e p o w der Ero si o n Nitro gly -

c erin e v ni tro c ellul o se po w ders Er o s i o n B a ckfl a sh Muz z le flame

.
-

Pr o du c t s o f e x pl o s i o n Test ing pro pellan t s Effi c ien cy

C HA P T ER XX III
FAST BU R NIN G SM O K E L E SS PO W D ER S
-

Sh o t gun p o w ders Co ndens ed po w ders Bulk p o w ders Ingre dien t s Manu

-

fac t ure o f b ul k po w ders Ameri c an me t ho d 33 grain p o w ders 30 grain - -

p o w ders Frenc h p o w ders German p o w der s Americ an po w der s

Aus t rian p o w ders Requiremen t s Tes t ing s h o t gun p o w ders P o w ders -

fo r tren ch ho witz ers Blank po w ders

 CO NT E NT S
P AG E

So l ven t s a va ila b le E t her alco h o l Na t ur e o f co ll o id s Ma nuf ac t ure o f

ac e t o ne P ermangana t e t es t Impur i t ie s Ac e t o ne fro m s t arc h Ac e t o ne
fro m ace t y lene Rec o very o f so l ve n t s Ace to ne rec o very Vo la t ili t y of
ni t ro glyce rine Va po ur e x plo s ions To xi c i t y o f v apo urs
-

PA RT VI I I : BL A S I I NG
' ‘
E X PL O S I VE S

NI T R O -
G LY CERIN E HI G H E X P L O S IV E S
V
ufac tu re of d yna mi t e P ro pert ies of d ynami t e Frenc h
dyn ami t es Ameri ca n
po w der Dyna mi t e No s 2 a nd 3 Gela ti nized explo si ves Bo x es fo r j e lly
.

Diminu ti o n o f se n s i t i venes s a nd s t a b ili t y Ge ligni t e Ge la t ine d yna mi t e

W ra pp er s 40 per ce n t d ynami t e Am erican gela t in dynami t e s Fo rci te
.

Fr enc h gela t inized e x pl o si v es Lo w fre e z ing explosi v es Safet y explosi ve s

-

Chlo ra t e dangers Sprengel e x plo si ves Pr o méth ée o r 0 3 Ra c k a ro c k - -

Cheddi t e Stee li te Sil es ia Po t a s ium pe rc hl o rat e ex plo s i ves Pe r mo ni te

s

Alk a l ite P o la r ite M B po w der Amm o nium perc hl o r a t e explo si v es

s . .

Favier e x plo si v es G ris o uni tes Ammonals Sa b uli t e Griso u t in e

Ix max or N AMES
Ix mzx or S UB J EC TS
 L I ST O F P RI NC I P A L A B B RE V I A TI O NS

J O U R N ALS , ETC .

A a nd
. E . A r ms a nd E x p lo s iv es .

A ng . Z ei t ch
s ri ft fur a n g e u a nd te
'
C h em ie .

AR . . A n n u a l Rep o r ts f H al l I ns p ec to r s o f E x p lo s i ves
o .

B er . B er ich te f th e
o G er ma n C h e mi ca l S oc i e ty .

B u ll . B u lle ti n o f U S B u r ea u . . o f Ill i n es .

C h em I . nd . D ie ch emis che I nd us tr i e .

C he m Tr a de J C h emi ca l Tr a de Jo u r na l
‘

. . . .

C ornp t. R en d . C o mp tes Rend u s .

C Z . C h emiker -
Zeitu ng .

J . S o c C h em . . Jo u r na l o f th e S oc iety o f C h emica l I n d u s try .

I nd .

P
. et S . Ill émo r i a l des P o u d r es S a lp é tr es et .

P h il . Tra ns . P h ilo s o p h i ca l Tr a n s a c tio n s 0 / th e Ro y a l S o ciety .

P r oc . RS . . P r o ceedi n g s o f th e Ro y a l S oc i ety .

S R.. S p eci a l Rep o r ts of H al l I n s p ecto r s o f Ex p l os i ves . .

S S . Z e its chr ift fur da s ges a mte S ch ies u nd S p ren gs tofi w es en

Tr a ns . C h em . Tra ns a ctio ns o f the C h emi ca l So ci e ty .

S oc .

B O OKS
C halo n . L es Ex p lo s ifs 111 oder n es .

C u n dill a n d D ic ti o na r y o f E x
p lo s i ves .

h
T o ms o n .

Gu n p o w de r a nd A mmu n i tio n , b y L ie ut H im
.
-
C o lo n el e.

The RI a n u fa c tu r e of E x p lo s iv es , b y O G u tt mann
. .

I o nu men ta P u lver i s P y r ii , b y O
IV . G u tt mann .

Tw en ty Yea r s
’
P r o gr es s i n E x p lo s i v s b y O G u tt man n
e , . .

Th e R is e a nd P r og res s o f th e B r i tis h Ex p lo s i ve s I n dus tr y .

Th e N i tr o -
cellu los e b y I Vo r d e n
I ndu s tr y , .

Ill ili ta ri s ch e S p e ng teckn i k, b y B Zs c h o kk e . .

L es P o u dr es et E x/ p los ifs , 1 9 1 4 .

O TH ER ABB RE V I AT I ON S
b o iling p o in t-
G 0 . .
g un c o o tt n .

c ub ic c e n t ime t r es . tn
m e l i g p o in t -
.

c o ll o di o n c o tt o n N c . . n tr u
i o c e ll l o s e
-
.

d in itr o g ly c e in e N g r . . n itro g ly c e rine

-
.

di nit r t o lu e n e
o Sp g . . r. s p c ifi c g ra v i t y
e .

g ram m e s . T/ n / t . t rin itr t lu n o o e e.

Te m p e ra t ur e s a r e lw a y s in d e g re e C n t igra de u nle s s
a . s e o t h e r w is e s t a t e d .
 I N TRO DU C TI O N

E p l i n E p l s ive G a E vo lut io n H e a t L ib ra t io n
x os o x o s e Se n s i t iv e n ees Con
st it ue n t o f E p l ive O y g e n C arrier C o mb u t ib le
s x os s x s s Co ns t i t u e n t s N t r i o
aro mat i C mp und N it ric E t ers Sm ke le s P w d r
c o o s s o s o e s E nd o t he rmie C o m
p o un d s Ve l c it y f E p lo io n I n c o mp le t e D e t o na t io n
o o x s St a b ili t y Su mmary

WH E N gas or vap our is released so suddenly as to cause a loud noise a n E plo ion x s ,

explosion i s said to occur as for instance the e x plosion of a ste am b oiler or

, , ,

a cylinder of compressed gas Great and increasing use is made of explosive .

processes in gas petrol and oil engines for driving ma c hinery of all kinds
, , .

In these engines the material that e x plodes is a mixture of air w ith com
bustible gas vap our or fi n e lv com minute d li quid and in the explosi o n these
, ,
-
,

are suddenly c onverted into water vap our and the o x ides of carbon which ,

latter are gases Although all these things are liable to e x plode none of
.
,

them are called explosives ; this term is confined to liquid and solid sub
sta nces which produce much more violent eff ects than e x ploding gaseous
,

mixtures because th e y o c cupy much smaller volumes originally

,
.

An e x plosive i s a so lid or liquid sub sta nce or mixture of substances which E plo i e x s v .

i s liable on the application of heat or a blow to a small portion of the mass

, ,

to be c onverted in a very short interval of time into other more stable

substan c es largely or entirely gaseous A considerable amount of heat i s .

also invariably evolved and consequently there is a flame ,

.

That evolution of gas (or vapour ) is essential in an e x plosion is rendered G a E lu s vo

evident by considering thermit This consists of a mixture of a metallic “ n .

0

o x ide generally o x ide of iron with alumi ni um p o w der When suitably

, ,
.

igni ted the aluminium i s converted into o x ide and the iron or o ther metal
i s s e t free in a short interval of time with the evolution of an enormous quantity
of heat but th ere is no exp losion It i s indeed because n o gas is evolved
, .

that thermit can b e used as it is for local heating and welding , ,

.

It i s also an essential condi tion that heat should be ev o lved in an explosive H a t L ib e er a

reaction otherwi se the absorption o f energ y d u e to the work done by the

,

e xplosion would cool the explosive and consequently slow do w n the reaction
until it ceased unless heat were supplied from w ith o ut Ammonium car
,
.

bonate for instance readily decomposes into carbon dioxide ammonia and
, , , ,

V OL . I . l 1

W W !
 I NTROD UC TI ON
w a t er b u t in s o d o ing it ab s orb s heat c onse quently t he re a ction is mu c h t oo
,

sl o w t o be explosive Ammoni um ni t rate on the o t her hand is decompose d

.
, ,

in t o o xygen ni t ro gen and w a t er w i t h t he e v o lu t i o n of heat and i s con

, , , ,

sequen tly li able t o expl o de A vi o lent impul s e is requi red t o s t a r t the

.

explo s ion b u t o nce i t is s tar t e d t he energy (or heat ) liberated suffi c es to

,

propagate t he explo s ion unle s s t he c on di t ions be su c h that the energy is

,

di s s ipated m o re rapi dly t han it is liberate d .

l ans iti v enes s . An o ther e s sen t ial fo r an e x pl o s ive i s t ha t t he reac t ion s ha ll not se t in
until an impulse is app lied If t he rea c t ion set in sp o ntane o usly it is ob v iou s
.
,

tha t its energy c ann o t be u t ilized in the form of an explosion A mi xture .

of s odium and w ate r e v olve s hy drogen wi t h t he li bera t ion of heat but reaction ,

s e t s in im mediately t he tw o sub s tance s c o me in con t ac t wi th one another .

Different explo s i v es require imp ul s e s of very di fferent strengths to cau se

them to explode S ome s uch a s di azobenzene ni trate are exploded b y
.
, ,

a s li ght touch ; t he s e e x plosi v es are of n o practical u t ility as th ey are too

unsafe Others such as fulminate of mer c ury are expl o ded by a m oderate
.
, ,

bl o w or a small flame ; the s e are u s ed p rinc ip a ll v for c harging caps and

det o na t o r s a s mall quantity serving to expl o de a large a moun t of s ome o t her
,

le s s sen s i t i v e e x plo s i v e Mos t o f t he explosive s n o w used can be e x ploded

.

by a blo w o nly if it be extremel y vi o lent and man y of t hem cannot be ,

exploded b y a flame in t he o pen in ordi nary c ircumstance s The te nde nc y is .

to use le s s sen s i t ive e x p lo s ives be c au s e they are s afer to handle but it sho u ld ,
”
ne v er be forg o t t en t hat t he term safe w hen app li e d to an e x plosive i s
“

, ,

only a c o mpara t i v e one The duty of an explosive is to expl o de and if i t

.
,

is not t rea t ed w i t h proper respect i t w ill sooner or later explode at the wrong
, ,

time w i t h extremely u npleasant re s ults .

Before the subj ec t of explosi v es w a s understo od s o w ell a s it is now ,

inventors w ere v ery liable to t hink an e x pl o sive was very po w erful and t here ,

fo re valuable merely because i t w a s very sensi t ive w herea s too great a degree ,

o f s en s i t iveness is really a most obj ectionable featur e In the mi d dl e of .

t he nine t een t h c en t ury many su c h mi x tures a s p otassium chlorate and pi c ric

a c id w ere proposed t hrough t hi s w ant of comprehension of a fundamenta l
c on di t ion .

tt
C ons i uen s t The e xp losive gaseous mixtures used i n gas and o il engines to w hi ch refer
o f Ex p l os iv es .
ence has b e en made are composed o f a c ombustible material c onsistin g largely ,

of carbon a nd hydr o gen and a ir the useful constituent of whi ch is ox y gen

, , .

Similarly nearl y a ll commercial explosives are c omposed partly of combustible

,

elemen t s of w hich c arbon a nd hy drogen are t he mo s t important and pa r t ly

, ,

of o x ygen c o mbined but not dire c t ly w i t h t he hydro gen and carbon On

. .

explosion t he o xygen combines with t he hydrogen to form w ater and with ,

the c arbon t o form c arb o n mon o xide or di oxi de o r a mixture of the two , .

It is the heat set free in this combus t ion t hat is the main o r ent ir e ca use of
 INT ROD UCTI ON
the rise of te mperatu r e The formation of th ese two oxides of carbon liberates
.

very di fferent quantitie s of heat ; 1 2 gram mes of carbon unite with 1 6

grammes of oxygen to form 28 grammes of carbon m ono x ide with the libera
tion of 29 large Calories and the same quantity of carbon unites wi th 32
,

gram mes of oxygen with the liberation of 9 7 large Calories .

Conse quently an explo s ive is considerably more e ffi cient if it contains

s u fficient o x ygen to oxidi ze the carbon entirely to di oxide but the e ffect is '

reduced to some extent by the relatively high specific heat of carbon dio x ide .

In some classes of explosives however a very high temperature is o b je c

, ,

tio na b le this is the case with smokeless powders and explosives for use in
c oal mines Smokeless p owders therefore are generally made of such a
.
, ,

comp osition that the greater part of the carbon is oxidized only to monoxide .

B ut there i s always some carbon dioxi de formed for it takes up some of the ,

oxygen from the water vapour and liberate s hydrogen or if the total quantity
of oxygen be V ery small there may even be free carbon produced In the
,

case of safety explosives for c oal mines the temperature of explosion is also
,

s ometimes kept low by restricting the prop ortion of oxygen but this means ,
'

i s not free from objection because carbon mono x i de i s poisonous Other .

met h ods are therefore adopted in some safety explosives to reduce the
te mperatur e .

The oxygen may either be contained in a separate compound such as O y g en , x

saltpetre which is mixed mechanically with the combustible material or ca ie s

, ,
rr r

the two may be combined together in a s ingle compound as i s the case with ,

ni tro glycerine trotyl and many othe r modern explosives

—
, ,
The substances .

rich in oxygen are often referred to as o x ygen carriers those most used
are ni trates chlorates and pe rchlorates in which the oxygen is uni ted to
, , ,
”
ni trogen and chlorine respectively Ordin ary g unpowder or
. black powder , ,

belongs to the class of explosives that have separate oxygen carriers in this ,

case saltpetre The table on page 4 shows the prop erties of th e principal
.

oxygen carrier s .

I t w ill be seen from this table t hat the prop orti on of available oxygen is
“

about the same in the chlorates as in the corresponding ni trates but whereas ,

the chlorates decompose with the evolution of a small amount of heat the ,

nitrates re quire a c onsiderable amount of heat to spli t them up excep t in the ,

case of the ammoni um compound E xplosives contain ing chlorates are con
.

sequently much more powerful than those containi ng nitrates but they are also ,

very sensitive unl ess special measures are adopted to render them more inert .

The perchlorates re quire considerably less heat to decompose them than

th e nitrate s and have more available oxygen
,
As they are now produced
.

at quite low cost by electrolytic methods it is not surprising to find that

,

they are being used more and more for the manufacture of explosives Ammo .

nium nitrate and perchlorate decompose with the evolution o f heat thi s ,
4 I XTROD UCT I OX
be ing due to t he fo rma t ion of w a t er bu t t he a v aila ble oxygen is di min i s h e d ,

b v t he s ame ca u se Ammoni um ni t r a t e ca n b e de t ona t ed b y i t se lf al t hough

. .

onl y w i t h diffi c ul t y and t hen gives a large v o l u me of g a s a t a compa ra t i v ely

,

lo w t e mpe r a t ure I n c o nse q uence o f t hi s lo w t empera t ure i t ha s been foun d

.

v ery u seful as a con s t i t uen t of sa fe t y e x plo s i v es for use in c oa l mine s bu t ,

i t al s o fo rm s par t o f many o t her hi gh explo s i v es A mmoni u m perc hlo ra t e .

s u ff e rs un d er t he di sa d v an t age t ha t amongs t i t s p ro duc t s of e x p losion is

t he poisonou s g a s hydrogen chl ori d e or h y dr ochlo r ic a cid
, ,
.

H ea t e v lv d
o e
O x y ge n a v
ai l

Mo lec u la r De n s it v Re a c t io n
c a rr i e r

1 0 1 -
1 —
75 -6 4 4s
8 0
5 -
4 30 -5 4 13
-
70 -6 13 0
- - ‘
9
2G l 5 °
—
94 4
- —
3 6- 1
3 3 1 -1 —
1 6-5
Amm o ni u m 1 -71 N H 4N O 3 = 2H SO + N 3 + O

20 0 x e io , z x el 30
10 6 5 -
Xa C 10 3 = X a C l 30
30 4 3 3 -1 8 so

P e i chl o ra tes
-
.

Po ta s s iu m . l 38 6 °

KC lO 4 = K C l + 4O 51 5
1 226 Na C lO 4 = X a C l 4 0 10 -2
3 36 3 -
B a
(C l O , ) 2 SO
1 76 1 -8 9 3H , O 29 -5 25 - 1
50 + 3 }

P o ta ssium permangana t e and bi ch roma t e ha v e also been u s ed bu t t he v .

,

p osse s s no special a d v an t ages P ermangana t e exp lo s i v es a re of t en inc o n

. .

v e ni e n tl
y sensi t i v e A t t emp t s ha v e al.s o bee n mad e t o u se li qui d ox y gen .
,

w hi ch has t he ad v an t age of being c heap a n d con t aini ng 10 0 per cen t o f avail .

able ox y gen bu t t he di fi i c u ltie s o f empl o yin g a li q ui d w hi ch boils a t 20 0

,
°

C belo w t he ordinary t e mpera t u re are so g rea t t ha t t hese a t t emp t s w e r e

. .

given up The Germans a re ho w e v er ma kin g grea t eff ort s t o develop t h e se

. . ,

e xplosives for w ork in min es s o as to se t fre e a co rr espondin g quan t i t y of

,

ni t r a t es for mili ta r v u s e For t he sa me r eason t he G erman au t ho r i t ies a re

.

encoura gin g the u s e of chlorat e s and pe r chlo r a t es .

 I NT ROD UCTI ON
I n black p owder the combustibles are charcoal and sulphur in blasting Co mb tib le ; us
0 ° Stituent8
explosives many sorts o f organic matter have been used or proposed and ,
“ ‘

some inorganic substances su c h as potassium ferro c yanide ammonium , ,

o x ala te and antimony sulphide but those in common use are not very numer
, ,

ous For explosives containing nitroglycerin an absorbent material must be

.

used and of these wood meal is the most usual but flour a n d starch are con
, ,

s titu e n ts of some nitro glycerine exp losives and in a few cases such substances
-
,

as tan meal and prepared horse dung are present Cork charcoal has great -
.

absorptive p ower but its high cost prevents its use Or di nary charcoal
, .

i s a constituent of some e x plosives as also is coal dust American dyn amites ,

-
.

often c o ntain resin and sulphur and these constituents are sometimes met ,

with in other e x plosives Oily materials such as castor oil vaselin and
.
, , ,

paraffin wax reduce t h e sensitiveness of an explosive and one or other of

, ,

them may usually be found in a chlorate blasting explosive The addi tion .

of aluminium greatly i ncreases the heat of explosion ; it is present in the

explosives of the ammonal typ e .

Modern high e x plosives very frequently contain nitro derivatives of the Nitr e a ro - -

”
aromatic compounds obtained from coal tar especially the mono di and gig? ,

tri nitro derivati ves of benzene toluene and naphthalene The nitro group s
- -
, ,
.
-

in these compounds contribute o x ygen for the e x p losive reaction The .

trinitro comp ounds of substances containing only one benzene ring are
-

explosives in themselves ; trinitrotoluene for instance Trinitrotoluene is ,

.

not only a constituent of composite exp losives but is also very largely used ,

by itself as a charge for shell and submarine mines and for other m ili tary ,

and naval purp oses for which its insensitiveness c ombined with its great
,

violence render it suitable P icric acid (trinitrophenol ) i s also much used

.

for these purposes and trinitrocresol to a less extent Although they de to n

,
.

ate with great violence these trini tro comp ounds do not contain su ffi cient
,
-

oxygen to oxi di ze the whole of the carbon they contain even to the stage
of carbon monoxide Their p ower as explosi ves is t h erefore increased
. , ,

by mixing them with o x ygen car r iers Commercial expl o sives c o n taining .

trinitrotoluene always have also some other c o nstituent which can supply
the deficient oxygen .

Nitr o glycerine and the nitro celluloses are the principal members of Nit ic E te s
— - r s r .

another very important group of substances that can b e use d as expl o sives
without admi x ture Strictly speaking they are not nitro derivatives but
.
,
-
,

nitric esters The more highly nitrate d cell u lo s es su c h as gun cotton c o ntain
.
, ,

enough oxygen to c onvert all the hydr o gen int o water and the c arbon i nto
monoxide and even some of it i nto di o x i de Nitro glycerine C H s O not
,
.
-
, a g,

o nly has enough to o x idi ze entirely all its hydrogen and carbon but also ,

has a little oxygen left o ver Nitro glycerine is the most powerful explosive
.
-

c ompound known but its power i s increased by d issolving in i t a small pro

,
 6 I NTRODUCT I ON
p ortion of ni tro c ell ulose whi ch u t iliz es the excess of oxygen and at the sa me
-
,

t ime c onvert s it in t o a gela t in ous soli d known a s bl a stin g gelatin .

All smokeless po w de r s c onsist largely of ni troce llulose which has been ,

mo r e or less gela t iniz ed and c onverte d into a compac t colloid by means of

a sui table solvent ; many of them c onta in prac ticall y nothi ng else but in ,

o th ers the r e is a c onsiderable prop ort ion of ni tro glycerine Small percent —
.
:

ages of mi neral j e lly inorganic ni t rates and other substa nces are also added
, , ,

i n many c ases to immo v e t he balli s t ic s or the s ta bili ty P owders for rifl e d .

arm s a re always c o ll o ide d as completely a s p ossible whether they be for ,

small arms or ordnance to make t hem bur n slowly and regularly but
-
, ,

in sho t g un powders th e origin al stru ctur e of the nitro ce llul ose i s not
- -

a l w ays destroyed entirely as th ey are required to burn c omparatively

,

rapi dl y .

The r e are some exp losive c ompo u nds which do not depend for t heir action
on oxi da t ion or reduction These are endo t her mic substa nces whi ch de c o m
.
,

po se wi th t he evolution of gas and heat ; they are usually rather sensitive .

The onl y c ompo u nds of t hi s class that are of commercial i mportance are
ful mina te of merc ury E g (C NO) and lead azide Pb N b oth of whi ch are
, 2, , e,

used only for explodi ng other e xplosives .

There a re o t her endo t hermi c explosive c ompoun ds in whi c h th e heat

li berated on decomp osi ng i nto their elements i s only of minor impor t a nce
c ompa r ed with the larger amount set free by the re di stribution of t he oxygen .

Su c h are te tryl and mono and di ni tro naphthalene -

.

The heat and gas evolved are the t wo principal factors which govern the
p ower of an e x plosive i e th e amount of work i t can do in t he way of
,
. .

di spl a c ing obj ects B u t t he t ime ta ken by the e xplosion is also a matter of
.

g reat import a nce .The rate of explosion i s measured by m aki n g a c olumn

of the explosive confi ni ng i t i f nece ssary i n a metal tube and measuring
, , , ,

t he t ime t ha t t he e xplosive wave takes to t ravel a kno w n di sta nce In black .

powder and similar ni t ra t e mixtures the velocity of exp losion i s onl y a few
hun dr ed metre s a s ec ond but w ith m oder n high explosives the veloci t y of
,

de t ona t ion is fro m t wo to seven t housand metres a second Thi s n a tu r a ll v .

makes them much more vi olent and d e s tructive E xplosives of the gunpowder .

type are used when earth o r sof t r o ck i s to be blasted or w hen the material ,

mu s t not be broken up to o much P ropellan t s for u se i n firearms are requi red

.

t o bu r n slowly ; for rifled arm s t hey mu s t be slower even th an gunpowder .

They are not e xplo ded by means of another hi gh explosive bu t me rely li t ,

by a powerful flame and shoul d t hen burn by c oncen t ric layers

,
The rate of .

burning increase s w ith the pressure i n the gun bu t for c ompletely gelat inized ,

po w ders i t is less t han a metre a second .

I nc o mp le te The mo re insensi t ive e xplosives such as trini t roto luene if fi red wi t h

, ,

a weak de t o na t or are only partially decompo s ed Not onl y is some of the .

 INT R O D UCTI ON
“

exp losive merely scattered but the velocity of the explosive wave is low
, .

Consequently the eff ect produced is comparatively small .

Another important property of an e xplosive is its stability I t should Sta b ility

. .

retain its properties and composition unchanged when stored even for a
long period . Above all it should not be li able to e xplode or ignite spon
ta n e o u s ly
. Nitr e ce llulose u nf ortunately i s liable to this defect and c o n s e
-
,

quently special precautions have to be taken in the case of smokeless powders

and other explosives c onta ini ng it .

The m ost important properties of explosives are : p ower sensitiveness S mma y

, ,
u r .

velocity of explosion stability and te mperature of exp losion The power

, .

depends up on the temperature of e xplosion and the quantity of gas a n d

.

vap our evolved The prices of the constituents and the ease and safety of
.

manufactur e a r e also of importance All these factors are dependent on the

.

c omposition of the explosive and some of them on its physical state .

H I ST O RIC A L
 C H AP TE R I

EARLY HI STORY

G un p o w d er C o nfu s io n o f t e rms I n ce ndiary mi x t u es G re e k fi r e \ Vi ld fi r e

r -

Sal t p e t r e Th e C hin e e Th e I n d ians Friar B a c o n Th e Arab s I n ve n t io n

s o f
fi r earms Su mmary G ib b o n
S IN C E the very earli est times man has been search ing for more and more G unp o wde r

effective means of killin g his fellow s and the beasts and bir ds that threatened
his safety or provided his food or clot h in g but there i s reason to beli eve that
,

the first exp losive gun p owder was not kn o wn before the thirteenth cent u ry
, , .

This i s a mixture of three sub s tances saltpetre sulphur and charcoal two
, , ,

of which have been kn own from time immemorial for sulphur occurs native ,

i n a state o f considerable pur ity in some volcanic di stricts and charcoal is ,

made by simply heatin g wood The early history of gunpowder and

.

exp losives generally is therefore closely c onnecte d with the di scovery of

methods of preparin g and purifying Saltpetre .

The in vestigation of t h is and other s imilar matters is rendered difficult C nf ion o us of

ter ms
not only by the scarcity of early records but also by the great uncertainty
,
.

a s to their true in terp retation W hen saltpetre g u npowder and guns were
.
,

discovered or invente d new words were not made but old terms were adopted
, ,

w hi ch had previously been used for somewhat similar obj ec ts Ou r word .

p owder for instance means any dust lik e material but the term smokeless
, ,
-
,

p owder i s now used to denote a class of substances which have nothing in

”
common with dust Gun is from the old E ng lish gonne which was
.
,

used to denote an instrument for thro w ing proj ectiles before the introduction
of gunpowder Sim ilarly the Ar abic bundu q (O W ) now used fo r any
.

rifle or sp orting gun formerly meant a pellet shot from a small catapult used
,

for sporting purposes Saltpetre (sal p e tr ae ) merely means salt of the ro c k

. ,

and the other Latin term for the same material nitrum (nitron nitre ) , , ,

formerly meant soda or any other white e ffl o re s ce nc e B oth nitron a nd .

natron in late Latin were derived from the Arabic ev j ku some of

the vowels being usuall y omit ted in writing that language as in shorthand .

Similar di fficulties occur with the term s i n other languages Nevertheless .

,

c onsiderable progress has lately b een made in ascertaining t he early history

of gunp owder a n d fi r e arms a n d vari o us wil d sta t emen t s as to the grea t
-
,

11
 EX PL OSI VE S
an t iquity o f t he kn o w ledge of gunp o w der in s o me c oun t rie s are now quit e
d isc r edit e d a s it is fou nd t ha t t he evi d en c e up o n w hi c h t h e se s t a t emen t s
,

were made w ill no t b ea r s c ru t in y .

t r l y I ucen
u
L o ng befo re t he di s covery o f sal t pet r e incen di ary ma t erial s had b ee n ,

used in warfare su c h as pitc h sulphur pe t roleum and o t her o ils B urni ng

, , , .

brand s were frequen t ly a t ta c hed to arro w s o r w e r e t h ro w n by means o f engines

( c at a pul t s )
, and t he d e s c rip t ions o f t he eff e c t s pro d uce d b
y t he s e e a rly fi re .

arms i s of t en s o fan c iful a n d exaggera t e d t hat t hey have bee n t hough t

t o imply t he u s e o f gunp o w der wi t h whi c h t hey reall y have no c onnexi on
, .

A ball o f burni ng pi tc h mix e d w i t h sulphur and naph t h a t h r o w n a g a in s t

a wooden bu ilding or s hip w ould cau s e a fire whi c h if n o t qui ckly e x tin ,

i s hed might r ve di s a s t rou s Su ch incen d i ary mix t ures were kn own

g u p o .

"
in E ngland as w ild fi r e The prompt appli ca tion of a bu c ket of w a t er
-
. .

or some sand w oul d h o w ever remove the danger Hen c e although is o la t ed

, , .
,

insta nces occur i n an c ien t hi s to ry where g r eat suc ce ss was a c hi ev ed wi t h

t hese incendiary mi xt u res they mus t generally have proved ineff ec t ive
, .

The one nota ble exception to t hi s is t he Gree k fi r e or -

t he s ecret of whi c h prevented t he conques t o f Cons ta n t in ople a n d E ur ope

by the Mo slem s for s everal cen t urie s About the yea r A D 668 some for t y . . .
,

six years after the flight of Mohame d from Mec c a to Medina the Arab s s t ill , ,

at the height of t heir conquering enthu siasm c ommenced to belea guer Con ,

s ta n tin o p le by land and sea w hen an ar c hi t ec t nam e d K a llinik o s fl ed fro m

,

Heli o p o lis in Syria to the Imperial ci t y and impar t c d t he sec r et of t he sea -

fi re .
”
This repeate dly spread such terror a nd destru c t ion among t he Moslem
fleet t ha t it was t he prin c ipal cause of th e siege being eventuall y raised after
,

seven years In A D 71 6 to 71 8 the Arabs again appeared before Cons tanti

. . .
,

n e ple wi t h eighteen h u ndred ship s bu t again w ere d efea t ed by the fi re ,

so e ffec t ually t hat afte r a stormy pa s sage only fi v e galleys re ente red t he
,
-

port of Alexandria to relate t he t a le of t heir various a n d alm os t in c r edi ble

di saste rs .

Ru ssian naval forces w ere similarly d efeated in 9 4 1 and 1 0 1 3 a n d t he -

,

P isans at the end of t he eleventh c entury .

What then w a s t he na t ure of t hi s sea fi r e

, ,
From the c ontemporary -

accoun t s w e kno w t hat i t was di s c harged from tube s or siphons in t he b o w s

of th e ships but its mode of preparati o n w a s kep t a c l o s e s e c r e t and it w a s
,
.

never u sed succe s sfully by any bu t t he Greek ruler s o f By zantium There .

appear s to be n o d o ubt t hat naph t ha w a s t he prin c ipal ingredi en t and i t ,

may also have c o ntaine d s ulphur and pitc h Col o nel H W L Hime ca me . . . .

to t he c onclusi o n tha t i t mu s t have bee n mixed w ith qui c kli me t he s lakin g .

of which by t he s e a w ate r rai s e d t he t e mpera t u r e to t he i gni t ion poin t of

-

t he s ul phur ‘
. I have m ade a number of a t t emp t s to produce igni t ion in t his
G np 1
dc nd A mm n it i n
u ou rL o n d n 1 90 4
a u o , o , .
 E A RLY HIST ORY
way but al t hough a fairly high temperature w a s reache d the sulphur never
,

caught fire The heat set free by the slaki ng of t he lime w oul d be ample
.

to raise the temperature to the igni tion point if there w ere n o loss of heat ,

but the reaction i s a slo w one c o mpare d with an e x plosion for instance and , ,

consequently much of the heat i s di ssipate d It seem s more probable that .

the naphtha w a s simply discharge d from a squirt or fi r e engine (sipho ) and -

,

t hat it w a s ignite d by means of a flame i n front of t he orifice a n d that the ,

se c ret consisted in t he method of c onstructing t he squirt or pump and of ,

using it so a s n o t to inj ure the u sers If this be so t he Greek fire di d not

.
,

di ff er greatly from the flame proj ectors n o w employe d by the Germans

-
.

”
Later the name Greek fi re w a s given also t o combus t ible mate rials W ild fi re - .

w hich w ere ignite d and then thrown by balli st ae or other mac h ines and w ere ,

used on land These compositions w ere semi solid masses o f sul phur pitch
.
-

, ,

naphth a a n d other substances that burn readily and w hen saltpetre had ,

been dis c overed this also w a s ad de d Su c h mi x tures may more corre c tly .

be called w il d fi r e ”
They w ere mu c h used by the Moslems in the Crusade s
-
. .

Thus J o invill e the faithful and devote d c o mpanion of St Louis in the di s

, .

astrou s si x th Crusade (A D 1 250 ) says t hat it c a me flying through the A D 1 250

. .
“
. .

air like a w inged long taile d dragon about the thi c kne s s of a hogshead with
—
, ,

the report of thunder and the velo c ity of li ghtning ; a n d the darkn ess of
”
the night w a s di spe lled by this dea dl y i llumination Nevertheless t he .
,

Greek fire on this oc c asion did very li ttle d amage That men li ke St Louis . .

and J oinville u sually ab solutely fearless shoul d have been terrifi ed by such
, ,

a cause and described it in such exaggerated la ng u a ge se e ms to have been

'

due to the fa c t that they looked upon it as a product of th e Devil B y 1250 . .

,

however the Arab s were acquainte d w ith saltpe t re and it is quite li kely
,
.
,

that they mi xed some with the incendi ary causing it to burn far more fiercely , .

Similar la n guage i s used in describing the incen di a ry missiles di scharged by

the Moors in Spain in battles and sieges of about the same date .

Saltpetre (potassi u m nitrate ) is formed in t he decomposi tion of ani mal a n d Saltpetr e .

vegeta ble matters U nder favo u rable condi tions it form s an e ffl o r c scc n c c
.

on the ground I t must have been by the investigation of such e ffl o r c sc c n ce s

.

that saltpetre wa s first discovered These e ffl o r e s c e n c e s are ne v er pure

.

and seldom c ontain more than a small percentage of p o tassium nitrate The .

ancients did not clearly di stin guish such deposits of sal t petre from t he simil a r
ones of soda which are found in some l o c ali t ies The first preparation of .

saltpetre of even m oderate purity from su c h a deposit w ould require con

s ide r a b le chemical k nowledge and i t coul d only have b e e n done in a country
,

where the deposits are plentiful that is in a c ountry suffi ciently w arm to
, ,

accelerate the decomposition o f t he organi c ma t ter and ha v ing a regular and

prolonged dr y season du ring w hich the depo s i t w ould c o lle c t and not be
washed a w ay Th e clim a te o f \Ye stern E ur o pe is consequently not favou r
.
 E XP L OSIV E S

able and moreover scien t ifi c kno w ledge and in ves t igation w ere very b a ckward
,

in E u rope in the ea rly Mid dl e Ages The p e ople w h o were most proficient .

in t his bran c h of knowledge a t that t ime were the Arab s or rather the Arabic
s pe a king people of Spa in Nor t he r n Af r i ca and S yr ia and many part s of
, ,

these coun t ri es have c limate s sui ta ble fo r the forma tion of sa ltpetre deposits .

Consequently i t is no t su r p r is ing that i t i s in Arabic that the first clear refer

,

en c e t o sa l t pe t r e i s to be fo un d T hi s is in t he w ritin gs of Abd Allah ibn

.

a l B a y t h a r a Spanis h Arab w h o di ed at Damascu s in 1 24 8

-
,
I t seems probable .

t hat t he Arab s and E gyptians kn ew s al t pe tr e in a fa irly pur e sta te about

1 225 .

The C hin ese appa r en t ly became ac qua inte d w i th saltpetre at about the
same peri od and i t i s possible that they were the origi nal di scoverers of salt
,
” 1
pe t re The E gyptians ca lled it Chinese sno w
. and it is si g nifica nt that ,

Chingis t he Mongol c onqueror brought Chi nese engineers wi th him in 1 21 8

, ,

to r edu c e the fortifi cations of t he cities of e ia P rs

2
The sta te ments made .

b y t he ea rly Jesuit fa t hers as to the great antiquity of t he manufacture of

gunpo w der in Chi na ha v e b een sho w n to be in a cc urate and foun ded on
,

erroneous translations 3
Marco P olo who was in the Far E ast from about
.
,

1 274 to 1 29 1 says con c erning the city of Chan Glu in P a r t II

,
Chapter L —
.
,

of his book In t hi s city and the di strict surroun ding it they make great
quan t i t ies of sal t by the followin g process ; in the country i s foun d a sal
,

s u gin o u s eart h ; upon thi s w hen laid in heap s they p o u r water w hich in , ,

it s pas sa ge through the mass imbibes the particles of salt and is t hen coll ected ,

in chann e ls from w hen c e i t is c onveyed to ver y w ide pans not m ore than
four inches d ee p In these i t is w ell boiled and t hen left to crysta lli ze The
. .

”
sa l t t hus made is whi t e and g o od and i s e xported to variou s part s The
, .

ma t e ri al prepared in thi s way could not fail to conta in a considerable pro

po r t ion of sal t petre m oreover the soil in the provi nce of Che Ii in w hi ch
,
-
,

t he ci t y mentioned seem s to have b e en situate d i s kn o w n to be rich in ,

sal t pe t r e Bu t from Marco P olo s statement it is probable that the pro d uc t

.
’

was u sed a s common salt In fact the Chi nese appear to have used saltp et r e
.
,

as ordin ary salt e v en at much later periods .

In t he c hroni cles called Tu ng Klo n Ka ng ma there is an accoun t of the - - -

siege of P ien Kin g (n o w Kai fun g fu ) in 1 232 and thi s was translated into
- - -
,

French by Re ina u d and Fa v é in the J o u r na l As ia tiq u e for October 1 8 49 :

At t ha t t ime u se was m ad e of the h o pao or fi r e pao ca lled T obi n -
,

tien lo ni or t h under that shake s the sky

-
For thi s pur pose an ir on p o t .
’

w a s u sed w hi ch w a s fil l e d with yo As soon a s a li ght wa s appli ed the ’

.
,

p a o rose and fi r e s pread in every di r ection Its noi s e resembled that of thun der .

1 Hi m e, G u n p o wd e r a nd A mmu n it io n,
p . 17 .
2 G ib b o n , c ha p . lx iv .

H im e, c ha p . v ii .
 EA RLY HIST ORY
and could be heard m o re than 1 0 0 lis (thirt y three English miles ) it could -

spread fire over more than a thir d of an acre Thi s fire even penetrated .

”
the breast plates on which it fell .

The Mongols constructed with o x hides a passage which enabled them -

to reach righ t to the foot of th e rampart They commenced to sap the walls .
,

and made holes i n them in which they could remain sheltered from the men
above One of th e besieged proposed that they should hang fi r e paos from
.
-

iron chains and let them down the face of the wall When they reached .

the places that were mined the paos burst and shattered the enemies and
,
”
the o x hides so as not to leave a ve stige of them
-
,
.

In addi tion the besieged had at their di sposition some arrows of flying
,

fire (fei h o tiang ) : to an arrow was attached a substance susceptible of

- -

taki ng fire ; the arrow flew suddenly in a straight line and spread flames
over a width of te n paces No one dared approach The fi r e paos and . .
-

arrows of flying fire were much feare d by the Mongols .

This arrow may have been a squi b or a rocket or merely an arrow to ,

which a sa ltpetre mi x ture w as attached The effects described could hardl y .

have been produced without the use of saltpetre nor the great noise without ,

an explosive but we need not take literally the statement that it coul d be
,

heard thirty three miles away -

.

By A D 1 259 the C hi nese had made a further advan c e The same annals
. .

state : In the first y ear of the period Khai K ing was made an appli ance -

called tho h o tsiang that i s to say lan c e with violent fire

- -
,
’
A nest o f ,
‘
.
’

grains was introduced into a long bamboo tube w hi ch was set light to
’

, .

A violent flame came out and then the nest of grains was shot forth with
a noise like that of a p ao whi ch c ould be heard at a di stance of about 500
,
”
paces . This w a s e v ide n tlv the device now kn o w n as a Roman candl e .

Statements have been made with regard to the anti qui ty of gunpowder Th e I ndia n s.

in India upon similarly incorrect evidence It i s improbable that the refi ning .

of saltpetre can have been di scovered in India as the habits of mind of the ,

educated classes would prevent their interesting themselves in such matte rs ,

and the institution of caste would render it impossible for them to handle
m any of the materials involved But the same institution has enabled the .

saltpetre industry to be developed very widely when once the process had ,

been di scovered elsewhere and introduced as a special caste of saltpetre ,

workers was formed and In di a still supplies a large proportion of the saltpetr e
,

used The saltpetre at first must have been very impure as the methods
.
,

of refining it were crude .

About 1 249 Roger Bacon wrote an account of the composition and manu Friar B a c o n
1 29 4
facture of saltpetre and gunpo w der in his D c Secr etis a n d Op u s Ter tiu m
‘

Those in the former work are fairly full but were concealed by me a ns of ,
 Pic . 1 . Po rt r a it of Ro ge r Ba co n .

pe r mi s s io n o f Lo r d Sa c kx i lle ,
fr o m a p ho t o gr a p h b y H E
. .
 E A RLY HIST ORY
ciphers w hich however have been de c iphered by Col o nel Hime with great
, , ,

ingenuity l
Bacon s statements when not cryp ti c are generally vague
.
’

, ,
.

In his Op u s Tcr tiu m w ritten about 1 250 a clearer passage has recently
, ,

been found by P rof P D u h e m in a fragment discovere d in the Biblioth eque

. .

Na tio n a ls P aris The following free translation has been publi she d by
,
.

Colonel Hime inthe j ourna l of the Royal Arti llery fo r July 1 9 1 1

Fr o m the flashing and flaming of certain igneous mixtures and the
terror inspired b y their noise w onderful consequences ensue As a simple
'

example may be mentioned the noise and flame generated by the powder ,

known in divers places comp osed of saltpetre charcoal and sulphur W hen
, , .

a quantity of this p owder no bigger than a man s finger i s wrapped up in ’

a piece of p a r c h me n t a n d ignited it explodes w ith a blindi ng flash and a ,

stunning noise I f a larger quantity were used or if the case were made
.
,

of some solid mate ri al the explosion w ould of c ourse be much more violent
, ,

and the fl a s h a n d din altogether unbearable

b
.

If Greek fire or any fire of th e same spe c ies be employed nothing can
, , ,

resist the inten sity of its combustion .

Thes e compositions may be used at any di stan c e we please so that the ,

operators escape all hurt from them while those against whom they are ,

employed are suddenly filled with confusion

'

There can be little doubt that soon afte r the di scovery of saltpetre the .
Ar a b s

Ar abs introduced it int o their Greek fire and other incendiaries In ?

;
. .

E urope saltpetre must have been more scar c e than in Africa and Asia
, More .

over the chivalry o f Western E urop e looked upon such means of war with
,

horror and perhaps w ere h a lf aware that the u se of them mu st eventuall y

destroy the Order .

In the M oor I gm u m of Marcus Gr aecus w hi ch was probably translated ,

‘

into Latin from an Arabic source about there are several references
to such mixtures but the translator d oes not appear to have understood
,
'

the subj ect he was writing on and consequently it i s not n o w possible to

’

be sure whether he is endeavouring to describe fi r e b r a n ds rockets or other ,

”
fi re works flying fire (ignis v o la tilis ) i s composed of
“
-
On e .

Resin 1
Sulphur 1
Saltpetre 2

di ssolved in linseed oil and put into a (hollow ) reed or pie c e of wood . This
was apparently an incen di ary (wil d fi r e ) -
.

1
Gu n p o w de r a nd A mmu n i tio n , c h a
p . viii . S ee a ls o fi rt
s ed i ti n
o o h
f t is w o k r .

2
S ee H ime , p . 10 3 .

VOL . I .
 E X P L OSIV E S

Another is made of
Sulphur
Vine or will o w charc o al
Saltpetre
The s e w ere rubbed do w n t o gether on a marble s lab and put into a case
( tuni c a ) in d iff erent manner s a c c o rding to t h e eff ect to be produced To .

make a l o ud n o i s e the c ase w a s to be sh o rt and wi de and filled only half full , ,

and w a s to be bound with strong ir o n wire E vidently this w a s a c racker .

n o t unl ike one described b v Bacon On the other hand the

. flying tunica ,

w a s to be thi n and long a n d filled w ith the above p owder well rammed in
, .

This w a s apparently an imperfec t rocket or squib The same w ork c ontains .

a second description of th ese fi r e works (recipes 1 2 1 3 3 2

-
but this does , , ,

not help to c lear up the uncertainties .

That the Arabs were probably using saltpetre in their fi r e b r a nds in 1 250 ,

i s shown by the passage in J o inville quoted above (page , At the siege

of Niebla in Spain in 1 257 we are told that the Moors launched stones
, , ,
“

”
and d ar ts from machines and missiles of thunder and fire
, .

t
I nven io n of The Chinese do not appear to have developed explosives beyond this
fi r ea r ms
.
point or to have made the ne x t step namely of causing the p owder to throw
, , ,

a heavy proj ectile instead of a ball of fi re P erhap s they made the attempt .
,

but with di sastrous results to themselves .

This step could only be taken by a nation which was at once progressive
and well ac quainted with the working of metals For some time the develop .

ment of gunpowder must have been impeded by the scarcity a n d poor quali ty
o f saltpetre . B efore any great advance could be made i t was necessary ,

for a considerable organization to grow up for c ollecting the saltpetre and

refining it In the meantime all the available supply was no doubt absorbed
.

by the makers of warlike combusti bles .

I n the thirteenth centur y therefore saltpetre was known and used from
, ,

China to Spain and E ngland but before the invention of fi r e arm s its
,
-

utility can have been but small No reliable fuse havi ng yet been discovered
.
,

hand grenades or bomb s can have been o f little use and must have been more
dangerou s to those using them than to the enemy The fi r e works which .
-

have been alluded to must have been very uncertain in thei r action and not
w ithout risk to the fi re worker
-
It does not seem t o have occurred to anyone
.

to use explosives to blow up the walls of a besieged town by mining u nder

neath and firing o ff a large quantity ; the primitive p owder was no doubt
too un c ertain in its action and its properties were not well enough known .

There is evidence to s how that for getting mineral s gunp o wder was not
, ,

u sed until the seventeenth century

l
.

1
S ee ch ap . 1 1.
 E A RLY HIST ORY 19

The real development of g u npowder and its extensive use had to wait ,

therefore for the i nvention of the gun I t i s genera lly c onsidered that t hi s
,
.

was accomp lished by the German monk Berthol d Sch w artz as he i s name d ,

as the invento r in many old manuscripts There is however a c urious .

, ,

inconsistency about the dates mentioned The year 1 3 8 0 i s given by Flavi us .

Blo n du s E nea s Sylvi us Baptista Saccu s and man y others livin g i n th e

, ,

fifte enth centur y Other w r iters have state d that the in vention w a s made .

in 1 3 54 1 3 9 0 and B ut on the other hand there is no doub t that

, , ,

g u ns were used much earlier There i s a manuscrip t in the Asiatic museum .

at P etrograd probably c ompiled by S hem s ed Di n Mohammed about 1 320

which shows tubes for fir ing off both arrows and balls by means of p owder 2
.

In an ill uminate d manuscrip t entitled D e Ofi c iis B egu m written by IVa lte r ,

de Mille me te in 1 3 25 and preserved in Chr ist Chur c h Library Oxf ord t h ere , ,

i s a drawin g reproduced in Fig 2 of a rudimentary gun shaped like a bottle

, .
, ,

and dischargi ng a dart A man i s applyi ng a light to the touch hole On .

-
.

February 1 1 1 326 the Rep ubli c of Veni ce or dered the provision of iron bul lets
, ,

and metal cannon for th e defence of its castles and vi llages and i n 1 33 8 3
,

cann on and p owder were provi ded for the protection of the p orts of H a rfi e ur
and l H e u r e again st E dw ard III
’
4
.

In two frescoes in the church of the former monastery of St Leonardo in .

L e c c e tto near Siena p ain ted by P aolo del Maestro Neri in 1 3 40 are shown a
, ,

large cylin drical cannon di scharging a spherical cannon ball and many h and
"

g u ns 5
.

In 1 33 1 cann on w ere apparently used by the Moors at the siege of Alicante 6

,

and in 1 3 42 in the defence of Algec iras aga inst Al phonso X I of Castill e .

The Coun ts of Derby and Salisbur y w ere present wi th the Spani ards and ,

it i s supposed that they introduced gun s into E ngland In the follo w in g years .

there are several references in the accounts of the Wardr obe of E dward III of
payments on a ccoun t of saltpetre Thus Thomas de Ro lde s to n Clerk of the .
,

King s P rivate War drobe in the Tower of London gives an accoun t for forty
’

s hi llings for ma kin g p o w der and repa iring various arm s in the period 1 344 to
1 3 47 E idem Thom ae super factur am p ul v e r i s per in g e nii s e t e me n da tio n e
”
div e r s a r u m a r ma tur a m XL sol And an acco u nt w a s discovered by Gutt .
7

mann delivered by J ohn Cok Clerk of the King s Great l Va r dr o b e for the date ,
’

1
G utt mann Bl a n ufac tu e o / E p l i v es 1 8 9 5
, r x os , ,
v o l. i .
, pp . 10 1 1 —
.

2
O G utt m nn J I o n u me ni a P u l e i P y i i
. a , i
‘
r s r .

3
L ib r is H is to i e de s S c ie nces m the ma tiq u
, en r a es I ta lic , v o l. iv , p . 48 7 ; P . et S .
, v o l.

v ii .
, p 33 . .

4
P et S . .
, v o l. v ii .
p . 34 .

5
S ee G u t t mann , Al onu me nta P u lr er is P y r ii , 1906 .

6 U t e s ch e r S . S . 1 9 14, p . 10 1 .
, ,

7
Gutt ma nn , Al a n u fa ctu r e o f E x p lo s i v e s , v ol. i .
, p . 13 ; H un t r e , A r chw o lo g ia , 1 8 47

Vo l . x x x ii
FI G 2 ro m W alt r d Mi ll m t
F Ma n u s c r pt
1 i

2
e e e e e s
i
. .

:C
(B y kind p e rmi s i n o f t h
s o eD n of
ea C hr i s t ( I n ” a
) e d )

20
 EA RLY HIST ORY 21

Ma y 1 0 1 346 fo r
, , 9 12 lbs of saltpetre and 8 8 6 lbs of quick sulphur for the
.
, .

King s guns :
’
1
Et ei d em Th o mas de Ro ld e s to n per manus W illie lmi de
C XX

Stanes ad opu s ip s iu s Rei s pro gunnis suis I X XII lib sal p e tr ae e t DCCC I I I I VI .

lib sulphur vivi per breve Regis datum X die Ma n dicto anno X X
. When .

all possible allowance has been made for alterations in the meanings of words ,

there can b e no doubt that in 1 3 46 King E dward had g u ns a n d powder On

-
.

November 25 1 3 46 and again on September 21 1 347 an o ffi cial order was

, , , ,

given to buy all available saltpetre in the c ountry On the first occasion .

750 lbs of saltpetre and 3 1 0 lbs of sulphur were obtained ; on the second
. .
,

20 21 lbs of saltpetre and 466 lbs of sulphur

. The price of the saltpetre was . .

l 8 d per lh
. cf the sulphur 8 d
.
, .

At the battle of Crecy (August 26 1 346) guns were used by the English , .

The French are also believed to h ave p ossessed them but apparently left ,

them be h ind i n order not to be encumbered with them in their pursui t of the
E ngli sh .

We see then that saltpetre became known about 1 225 and that by 1 3 50 Summa ry .

fi r e arms were in use to a c onsiderable extent in Western E urope

-
.

Saltpetre was apparently discovered by one of the Oriental nations and ,

was used for making fi r e works and incendiary mi x tures both in the E ast
-

and West but especially the E ast The explosive properties of saltpetre
, .

mixtures must have been kn own to many people besides Roger Bacon but ,

they were of little use until the discovery of fi r e arms which apparently was '
-
,

made in Italy or Germany early in th e fo u r te e n th century .

Th e period of the first development of fi r e arm s was in many respects an -

important one The division of the p ower in Italy France and Germany
.
,

among a great number of p etty rulers had given the opp ortunity for the
growth of the free cities on the one hand and the P apacy on the other The .

latter had used its p ower to crush the Albigeois in S outhern France the most ,

civilized and cultured people of the time and by 1 250 had extinguished them ,

with fire and sword The free cities were frequently richer than important
.

countries and it was in them that the skill and knowle dge were developed
,

which made it p ossible to construct ordnance and make gunp owder Only .

in E ngland did the king retain much p ower In the E ast the prestige of .

”
Christianity and the Franks was then at its lowest ebb but a steady
“
,

advance was to come The Christian religi o n had been e x tirpated from
.

Africa and a great part of Spain and in Syria the Crusaders had finally faile d ,

to retrieve the H o ly Sepulchre The Arabs h a d long since been obliged to .

resign most of their c onquests to the Turks who h a d reduced the E astern ,

Roman E mpire to little more than the city o f Constantinople and that had ,

become the spoil alternately of Fren c h Norman s Venetian s and G en o ese , ,

.

1 P u li
b c R rd Offi c L nd n L T R E n r ll d
e co Ae nt N
,
4 o o , . . . o e c co u o . .
 22 E XP L O SIVE S
The final fall of th e ci t y w a s however postponed by the app earance of anothe r
, ,

race w h o came like the Turk from Cen tral Asia The s e were the Tarta rs or
,
s
,
.

Mogul s t he g r ea t es t conquerors k no w n in human hi sto ry U nder Ching is

, .

they c onquered Chi na in 1 210 to 1 21 4 C a ri zme Tr a n s o x i a na and P ersia in , , ,

1 21 8 to 1 224 The ci t ies of t he Middl e E ast were r e duced w i t h the aid of a

.

s t a ff of ski lful Chinese engin eers who perhap s brough t wi t h t hem the secret
,

of sa l t pe t re U nder t he succes s ors of Chi ngis fi re and destruction w ere carried

.

in t o Russia P oland and H u ngary At t he beginni ng of t he fourteenth century

,
.

the Mogul E mp ire declin ed under t he civil wars whi ch alm ost inevitably
resul t on t he dea t h of a monarch in the E ast The Tur ks regain e d th eir .

ascendancy for a t im e in Wes t e rn Asia In 1 3 61 to 1 40 5 Timour or Tamerlane .

usur p ed t he w hole of Chi n g is E mp ire except C hina and added to it Northern

’

India par t of Syria and Asia Min or

,
.

But already t he forces were being born w h ich were to revolu tioni ze th e
world In the ci t ies of I t aly Ge rman y E ngland and France a spiri t of
.
, ,

freedom in i nquiry adventure and c ul t ure was ari sing which now dominate s
,

the w hole ea rth .

G ib b on N O TE —
The accoun t of the Greek fi r e i s largely derived from Gibbon s ’

D ec li ne a nd Fa ll Al t hough t hi s remarkable w ork was w ri tten in the

.

eigh t eenth century yet such is it s accur acy that even upon such a di fficul t
,

and techni cal mat t er as thi s subsequent research has been able to fi n d no
,

e r rors in t he statements In a footnote relatin g t o the di scovery of gun powder

.
,

Gibbon s ays
The vani t y or envy of shakin g the esta bli shed property of fame has
, ,

temp t ed some mode m s to carry g u np owder above the fourteenth and Greek
fi re above t he seventh century Bu t their evi dence which precedes the .
,

vulgar aera of t he invention i s seldom clear or satisfactory and subsequent

, ,

writers may be suspected of fraud or credu li t y In the earliest sieges some .

combustibles of o il and sulphur h ave b een used and the Greek fire has s o me ,

a ffini ties w i t h gun powder bo t h in nat u re and effec ts .

I t is impossible to sum the m a tter up bet t er .

 C H AP TE R I I

D E V E OPMENT OF GUNPOW DER L

E arly manu fa c t u e Early p w d e r ma kin g ma chine ry I n c o rp o ra t in g mill
r o -

St amp mill s Add it io n s t o g un p o w d e r C o rn e d p o w d e r P re s e d p o w d e r s

B r e a ki n g d o w n C o mp o s it io n f g un p o w d er Te s t in g g u np o w d e r Fir e arm
o -
s

D o ub l e b arr elle d g un
-
Ri fl e s C anno n s P r o j e c t ile
z I n ce nd iary m i s iles s s :

Sh e ll Fu s e s H and g r e nad e I nfe rnal ma c h ine s Fire w o r ks Milita ry mine s

-
s -

B la s t in g

IN the four teenth century gunpowder was only used on a small scale and Ea ly r
ma nufa c’um
was made in or di nary houses with pestle and mortar We hear for in stance
'

.
, ,
’

that the Rathau s at L ii b eck w a s des tr o y ed by fire in 1 3 60 through the care

lessness of powder makers 1
Berthelot has stated that there were powder .

mills at Augsburg in 1 340 at Spandau in 1 344 and Liegnitz in ,but

Feldhaus could find no confirmation of these statements in the archives of
th ese towns There i s no mention of gunp owder or fi r e arm s in Augsb u rg
.
-

before 1 3 72 to 1 3 73 and the firs t p owder mill was erected at Spandau in

,

1 578 The scale of operations grad uall y increased and in 1 461 we fi nd th e

.
,

first mention of a p owder house i n the Tower of London ; p owder was -

made there for many years as also in orchester Castle

P 3
In the sixteenth ,
.

century mill s of considerable size were i n existence : the Liebfrauenkirche

in Liegnitz suffered at this time from the effects of explosions in a mill near
by In 1 554 to 1 555 a gunpowder mil l i s said to have been erected at Rother
.

hithe and about 1 561 George E velyn the grandfather of John E velyn the
, , ,

diari st had mills at Long Ditton and Godstone having learned the methods
, ,

of manufacture in Flanders A few years later he obtained from Queen .

E li zabeth a monopoly of the manufacture of gunpow d er which he a n d his ,

sons were able to maintain more or less until 1 63 6 when Samuel C o r de w e ll ,

o btained the monop oly whi c h was abolished by P arliamen t in 1 64 1 the

, ,

year before the o utbreak of the Civil War George E velyn made a fo rtune .

out of gunpowder and some of his sons did well but i t is doubtful whether
, ,

1
F . M . Fe ld ha us, S S . 1 90 9 p 275
., , . .

2
Revu e des d eu ce Al o u d es , Au g 1 5 1 8 9 1 .
, , p 8 17
. .

3
B r it E x p I n d
. . .
, pp . 183 et s e q . S ee a ls o H is to r y o f th e E ve ly n Fa m ily , by H e le n
E v e ly n , 1 9 1 5, p p .
19 a nd 26 .
 E X P L OSI VE S

any one else made much money out of it in E ngland After the Resto ratio n .

the m o nopoly of gunpow der as of many other mate ri al s w a s r e establi shed

, ,
-

for a time but d o es not a ppear to have been maintained long

, .

In the reign of Charles I the c ontra c tors suppli ed to t he Crown every

year 240 lasts of gunpowder at 7d or 8d per lb and the Crown sold it again . . .
,

at about a shill ing the retail price being about 1 6d A last consisted of 24
,
.

barrels containing 1 00 lbs each 1

. .

Ea rly p o w der
At first gunpowder wa s made by simply poundi ng u p the c onstituents
and mixing t hem together i n a mortar Of t en the pestle was suspended from .

mac hinery .

a flexible w ooden rod which acted a s a sp ri ng to assist the li f t ing The very
, .

earliest known example of such an appli ance i s shown in an illustrate d manu

script the Co dex Germani cu s preserved in Muni ch (No : 600 of the Hof und
,
”
,

Sta a ts b ib li o th e k )
- Guttmann assigns to thi s the very early date of
.

Similar pictures appear in late r manuscripts such a s the Rust und fe u e rw e r ck ,

b uy ch of the fifte enth cent u ry in th e Sta dtbibliothek at Frankfur t a / M , .

The latte r also sh ows th e next step in the adoption of mac hi nery the stamp ,

mill Guttmann in hi s M on u men ta P u li er is P yr ii gives reproductions of

.
, ,

many old dr awings of such plant In the fif teenth and sixteenth centur ies .

t here were generall y two stamp s workin g in each m ortar They were raised .

alternately by a cam proj ecting from an a xle which was t u r ned by hand At .

a later date water wheels and treadmills were used as the motive power and ,

only one stamp worked in each mortar H orses do not seem to have been used . .

I nc o r p o r a tin g There is a picture of an inco r p orating mill with a n edge runner in a book -

enti t led C o r on a e P a lma M i lita r e di Ar teg licr ia by A Capo Bianco and .

,

pub lished at Venice i n 1 59 8 It ha s only one edge runner and the machine .
-
,

i s apparen t ly turned by a horse working i n the same building .

t
S a mp mins .
S tamp mills w ere still u sed exte nsively on the Continent at the end of
the nineteen t h century but in E ngland they were forbidden Tilt hammers
, .

were also used sometimes especially in Switzerland and i n more m o dern , ,

times rotating drums containing hard wood balls have been employed .

A t fir s t the p owder was used in the fine state In this condi tion i t burned .

slowly as the interstices were very small : i t was li able to foul the fi r e arm
,
-

very badly af t er a few rounds and it was di fficult to regulate th e effect which , ,

depended very much upon the ramming B ourne i n his Ar t 0 / Sho o ting .
,

i n G r e at Or dna n ce 1 5 8 7 said The p owder rammed too hard and the wad “
, ,

al s o it will be long befo re the pie c e goes off

, The po w der too loose .

will make t he shotte to com e short of the mark P u t up the powder .

’

with the rammer head s o mewhat close bu t bea t i t not too hard O t her , .

di sadvantages o f the fine powd e r were t hat i t ab s orbed moisture very rapi dly ,

and t he c on s t i t uents were liable to s eparate one from t he o t her if t he powder

were subj ected to much vibration Fo r al t hough amorphou s carbon has .

1
B it
r . Ex p . I nd .
, p . 278 .
2 il l o n u me n la ,
p . 1 9 , Fig . 48 .
 D E V E L OPMENT OF G UN P OW DE R
much the s ame absolute density as s a ltpetre and sulphur p owdere d c harcoal ,

contains many cavities which make it lighter than the other c o nstituents .

Additions to
It was partly to prevent this separation of the con stituents that the early un o er -

g p wd .

p ow der makers added camphor sal ammoniac and gum dissolved in spirit
-
,

to their p owder Thu s in the Codex Germanicus of the fourteenth century

.

the follo w ing recipe i s given W iltu ein gut starck pulver ma c hen So n y m
IIII lb Sa lnite r und I lb s w e b e l und I lb kol / 1 u n c z s a lp e tr i und I nuez salar
ma n ia k I tem und a in e n XII tail campfer u n d s to z daz alls wol u n de in a n d/
und tu ge p r a n te n wein da r c z u und stoss damit ab und derre daz wol an .

der sunn / so b astu ein u b e r s ta r c k b e liw ig pulver / dez p h un t mer tut denn
”
sust III p h u n t getun mdc h te n / und ist auch b e h a ltig und wirt lenger p e s s e r .

Translation If you want to make a good strong p ow der take 4 lb , .

of saltpetre 1 lb of sulphur and 1 lb of charcoal 1 oz of sa lp r a tic a and 1 oz

, . .
, . .

of sal ammoniac and one twelfth part of camphor P ound it all well up
-
.

together and add spirit of wine and mix it in and dry in the sun Then
, , .

you have a very strong powder of which 1 lb w ill do more than 3 lb other
, . .

”
wise It also keeps well and becomes better w ith time
. .

In another part of the same manuscript i t is stated : Wenn w a nicht

g a m p fe r pey ist daz pulver e r w ir t und verdirbt gern Aber daz g a mfe r h alt .

allez pulver auf/ und ist auch kr e ftig und p r u n s tig in allem pulver wenn
”
man in darin tut Translation
. When there is no camphor it crumbles
“

and easily spoils B ut the camphor holds all powder together and is also
.
,

strong and quick in all powder if one puts it in , .

“
Sa lp r a tica was a mi x ture of saltpetre camphor and sal a mmoniac , ,

made by di ssolving them all in spirit placing the mi x ture in an unglazed ,

earthenware vessel and scraping o ff the e ffi o r e s c e n ce that was formed The

, .

composition must have been very variable These volatile materials were .

also supposed to improve the power of the exp losive by increasing the amount
”
of air .

The separation of the ingredients was restrained at a later date by c o m Oorned ‘

ing the powder that i s breaking the cakes into small grains only instead
, , ,

of to a fine powder In order to get a hard mill cake which would give good
.
-
,

grains the contents of the mortar were moistened before the end of the stamp
,

ing operation with water wine or urine After it had been broken down
, .

the grains of the required size were separated by sifting .

The earliest known reference to corned powder i s in the Fire b o o k

of Conrad von Schongau dated It left less fouling i n the fi r e arm -

and burned faster and m ore regularly than the very fine p owder but it deve ,

loped greater pressure and c onsequ ently i t could not be used in the ordnan c e
of the time but only i n hand guns The fine powder c ame to be calle d ser
,
-
.

”
pentine apparently from the name of the small c annon
, .

1
M J ah ns G es ch ich te des K i egs w es en s L e ip ig 1 8 8 0
. , r , z , .
 EXP L OSIV E S

W h ite h o rn e
in hi s C er ta i n W a ies fo r the Or der in g o / So u ld ier s in Ba ttelra y
'

1 5 60 s ays :
,
If serp entine p o w der s hould be occupied (used ) i n han d guns ,

i t w oul d scant be able to d rive their pellets a q uoit s cast from their m ou t h s ’

and if handgun (i e corned ) p owder shoul d be used in pieces of ordn ance

. .
,
”
thout grea t di s c retion it woul d qui ckl y break or mar them , .

Accordi ng to Guttmann the French p owder mills began in 1 525 to grain ,

-

and classify th eir powder by pass ing i t th rough sieves 1

Apparently corn ed .

powder came gradually in t o use for small arm s and hand grenades during t he - -

fif t eenth centu ry and for big gun s i n the si x teenth th e c ons t ruc t ion of t hese
, ,

being suffi c ientl y improved by that time In an engraving by P hil lip Gall e .
,

after a dra w ing by John Str a da n u s to whi ch the date 1 570 has been a ss i g ned 2 , ,

the operations of cast ing and fini shing gun s are sho w n and the manufac t ur e ,

had evi dently reached a fairly hi gh state of development by th a t t ime .

A really hard compact grain c ould not be made by thi s method c o n se ,

owder .
quently af ter a t ime presses were introduced to compress the mi ll cake before -

c o mi ng According to Guttmann presses were first used for thi s purp ose in
.
3

1 78 4 .At Faversham i n 1 78 9 the powder w a s c ompressed by means of a

screw press sh own in drawi ngs in a c on t emp orary note b ook
,
4
In the -
.

nineteenth c entury hydr aulic presses were introduced .

The cake was broken down by hand wi th wooden mallets and then pressed ,

through sieves to granulate and sort it At one time wooden rollers were .

used to press it through the sieves but later di scs of lignum vi t ae were placed ,

in the sieves whi ch were suspended by means of cords and s w ung backwards
,

and forwards Colonel Congreve in 1 8 1 9 introduced hi s granula t ing machi ne

.
,

whi ch i s desc ri bed in Chapte r VI .

Colonel H ime has given tables to show t he development t hat took place
n the composition of gunpowder in t he c ourse of time some al t era t ions
i l Vi t h .

these are reprodu c ed here :

E N G LI S H G UN P O W D ER

Au th o r i y t t
Sa l pe t r e C ha rco a l Su lp h u r

Ro g e r B a c o n
Ar d e r n e (L a b o r a t o ry re ce i
p ) t
\ Vh it e h o r n e
G o v rnm n t
e e co n t ra t c

Si J Tur n
r . er

R b in
o s

B i ho p
s

1
JV
I a n u / a c tu r e , v o l. i .
, p . 17 .
2
J l on u me n ta , F ig . 8 .

3
Al a n u/ a ctu r e , v o l. ii .
, p . 20 4 .
4
B r it
. Ex p . I nd .
,
F ig . 13 a nd
p . 36 .
 DEV EL OPMEN T OF G UN POWD E R
F ORE I G N GU NP OWD E R

Co u n t r
y t t
Sa l p e re Ch a r c o a l Su lp h u r

1 4t h C e nt ur y G ermany
1 560 Sw e d e n
1 59 5 G ermany
1 59 8 Fran ce
1 60 8 D e n mar k
1 69 7 Sw e d e n
1882 Ge rmany

The proportions 6 : 1 1 known as as as s ix , were first adopted in , , ,

France at the end o f the sixteenth century and have been adhered to there
more or les s ever since 1
.

The fo u rteenth century German p owder has been substituted for a French
-

p owder of about the same date mentioned by Hime as it is a more satisfactory ,

example The last item in the li st i s German cocoa powder ballistically the
.
,

best black p owder ever made .

But in reali ty the composition was extremely variable E very p owde r

‘

maker had his own formula in early days and in the absence of testing appa ,

r atus there was no means of j udging which was best W ith the invention .

of corned p owder another variable was introduced the size of the grains , ,

and the confusion became still worse .

In the Middle Ages the only tests applied to powder were to feel it to T ting es

ascertain whether it was m oist and to b u r n a little to see W hether much

,
”w e
~ “

residue was left The first instrument for testing powder of which we have
.
, ,

any knowledge i s that described by B ourne in his I n ven tio n s a n d D evices

, ,

published in 1 578 It was a small metal cylinder wi th a heavy lid o n e 1 573

. .

hinge . The lid was prevented from fa lling by a ratchet and the an gle ,

to which it rose when powder was fired i nside the b ox measured its
strength .

A much better instrument was that devised by C u r te n b a c h and described 1 627 .

by him in his H a lin itr o P y r o b o lia in 1 627 This consisted of a heavy conical
, .

shot which rested on the mouth o f a small mortar and could travel vertically
upwards along a stretched wire It was prevented from falli ng again by .

a series of catches There i s a copy of this in the Imperial Museum in Vienna

.
,

and Guttmann gi v es a reproduction of a photograph o f i t as Fig 67 of .

Mon u men ta P u lvi s P y r ii

. .

Maste r Gunner Nye i n his Ar t o f G u nn er y 1 647 described the same 1 647

-
, , ,
.

in strument and also proposed that the strength of powder be measured by

,

1
C halo n E , x p lo s ifs lV
I o de r ne s , p . 228 .
 28 E X P L OSIV E S
,

fi ri ng bull e t s from a p istol into clay or b y fi ring a heavy b a ll from a morta r ,

and fin ding out h o w far it t ravelle d Thi s last t he mo r ta r é p r o u te tte w a s .

, ,

adop t ed by t he French and o t her Gover nmen t s and le d to c onsiderable ,

improvement s in t he po w ders By t h e beginning of the eighteenth centur y .

the propor t i o ns of t he c o ns t i t uent s w ere fa irly well fi x e d and t he po w ders ,

for di fferen t gun s di ff ere d only i n the size o f grain In 1 742 Rob ins place d .

the ma t te r o n a m o re s c ien t ifi c ba si s by the i nven t i o n o f t he ba lli s t ic pen d ulum ,

by means of w hich t he actual velo c i t y o f a proj e c tile coul d be mea sured By . .

the e n d of the centur y practi c ally every country h a d come t o use t he ,

propor t i on s 75 of saltpe t re 1 5 of c har c oal a nd 1 0 of s ulphur

, , , .

r e-a r ms . To trace in detail t he development of fi r e arm s i s beyon d t he scope o f -

thi s w ork Mo reover it ha s depen de d far m ore upon t he engineer t han the
. .

po w der maker w h o has nearly al w ays been able t o supply p o w der more
-
,

po w erful than t he gun maker has been able to use th rough insu ffi cien t engineer
—
,

i ng skill A t first t he chi v a lry of “ estern E ur ope w a s entirely opposed to

. .
T

the use of fi r e arms but it soon had to ac quiesce in the employmen t of gun
-
,
~

p o w der in w arfare but made a longer struggle a s regar d s the hunting of

,

animals H a w king a n d the c hase w ere the only respec t able form s of sp ort
.
,

but poachers w ere no t governed by the same scrup les and laws were c o n se ,

q uen t ly passed t o pre v ent the use of fi r e arm s by them For inst a nce in -
.
,

1 5 55 the E le c tor Augustus of Saxony prohibited the p ossession of fi r e arm s, ,

-

by peasants a n d shepher d s and in 1 562 small shot w a s ab solute ly prohibite d

,

throughout t he Duchy of Mecklenburg

.
1
Never t heless i t w a s not po s sible .
,

to prevent the u se of mili ta ry muskets for sporting purposes I ta lv in thi s .

,

respec t as i n so many o t her s w a s ahea d of Northern E urope Benvenuto

, , .

Cellini (b 1 50 0 (I 1 571 ) w hen a young man w a s very fon d of s hooting for

. .

sport a n d ma d e his o w n gunpo w der He shot w i th a single bull et and boasted

,
. .

of his s kill a s a marksman H e m ake s no mention of there bein g any prej udice
.

or la w again s t the u se of fi r e arm s -

.

It was n o t until t he double barrelled gun was introduced that t here w a s -

any real di ff erence between the milita ry and s porting w eap o n s Double .

guns w ere first ma de su ffi c ien t ly ligh t to be pra c t icable in t he middle o f the

seventeenth c entury ; in t he eigh t eenth c entur y t he rib s w ere a dde d and ,

the fl in t lock and hammer w ere introdu c ed .

Rifles w ere a lrea dy kno w n in t he fir s t half o f t he sixteenth cen t ur y and ,

are s aid to have been invente d b y Augus t us K o t t er o f Nuremberg 1 11 1 520 , , ,

b ut fo r a l o ng t ime t he rifle w a s u s e d prin c ipall y fo r sp o rting pu rp o s e s be c au se .

the ne c e s s i t y o f ram ming t he b ullet d o w n t he b arrel w i t h i t s spi ral gr o o ving

ma de t he l o adi ng very slo w Mo re o ver t he p o w der lef t mu c h fouling in the.
,

grooves a nd con s equen t ly it w a s necessary to c lean t he arm af ter a few roun d s

, .

1
G n e r J l d n S h t Gu n 2n d ed p l
r ee o cr o s, .
, . .

2
l it d i B n n t C ll in i p ar t i
'

a e re u o e . .
 D E V E L OP MENT OF G U NP OWD E R

With the old musket on the other hand the b ullet w a s smaller than the bore
, , ,

and this trouble did not ari s e to anything like the same extent In the seven .

te e n th century the rifle w a s trie d i n several continental armies but in every ,

case it was given up again 1

For sporting purposes ac c ura c y was of more
.

importance than rapidity of fire a n d the rifle was able to h o ld its own espe , ,

c ia lly in mountainous c o untries such as the Tyrol and S w itzerland In the .

Ameri c an War of Indepen den c e the sporting rifle was necessarily used for
military p mp o s e s and the E nglish G overnment found it advisable to enlist
'

o n the Continent a corp s of J tigers to put against the c olonial marksmen .

Afterwards the Rifle Brigade was raised and this proved a success from the ,

first Robins the inventor of the ballisti c pendulum had already prophesied
.
, ,

that w onderful eff ects would be produced by the State which could first make
the military rifle a practical success .

Since then every part of the rifle has been further improved the action ,

the r ifl ing the sights ; a n d magazines have been ad de d to increase the rate
,

of fire In 1 8 8 6 smokeless powder for rifles was introduced and this has
.
,

added greatly to the e fficien c y of the weapon The final development i s .

th e introduction of automatic rifles and machine guns su c h as that of Maxim , ,

but thi s part of the evolution of small arm s is still in progress The develop -
.

ment of the pistol has pro c eeded on similar lines .

The first guns were tubes or pots which could withstand only very slight Ca u , a cu .

pressures Then they were made of strips of wrought iron welded together
. .

By the sixteenth c entury they were being cast in bronze and by the eighteenth ,

in iron U ntil the second half of the nin e teenth century a gun consisted
.

simply of a block of c ast metal with a smooth bore machined out and a vent
drilled near the breech It is true that breech loa ding guns were made at
.
-

a much earlier date for e x amples o f t h e m may be seen in the museums but
, ,

the cr u dity o f the w o rkmanshi p i s sufficient to e x plain why they were given
up again In the Crimean war (1 8 54) many of the guns used had seen service
.

in the Napoleonic campaigns In 1 8 58 a committee recommended the intro .

duction of rifled ordnan c e into the British naval service and from that time ,

there has been rapid and continuous improvement in all sorts of guns The .

introduction of the buffer has made the guns much steadier breech loading -

guns were r e introdu c ed and the mechanism of the breech has since then
—

been impr o ved enormously .

To meet the requ i rements of the longer a n d more accurate guns the grains
of the p owder wer e gradually increased in size so as to make them burn more
slowly In 1 8 71 P ebble or P p o w der w a s ma d e by cutting cubes from pressed
.

slabs and in 1 8 8 1 P ri s m p o w der w a s made by m o ul ding hexag o nal pri s ms

,

and pressing them i n a special pres s Th e German s i n 1 8 8 2 ma de a bro w n .

rism powder a n d in spite of att empts to keep t he meth o d of manufa c tu re

p ,

1 Tex tb o o k o f S ma ll A r ms
-
, 1 90 9 , p
p . (5, 7,
 E X PL OSIV E S

se cre t it w a s bein g made a t \Va lth a m Abbey also tw o years later Thi s
, .

ver y large and dense p o w d er was requi red o n accoun t of the great increase in
t he size of naval guns In 1 8 8 2 at the bombardment of Alexan dria w e had
.

8 0 t on gun s of 1 6 inch bore a nd in 1 8 8 6 1 1 0 ton guns of 1 6i inch ca libre

- -
,
- -
.

This po w der di d not reta in i t s importance long however for in the nineties , ,

smokeless p o w der ent irely di splaced black powder as a propulsive explosive

in cann on W ith smokeless po w der it is now possible to throw a shell weighi n g
.

a ton a distance o f t w enty mi les .

r oi ec til es . The firs t proj ec t iles u se d w ere made m ore or less like arrows with metal
”
fea t hers and arro w hea d s j ust as the first railway carriages were bui lt
1 -
,

li ke stage coa c hes These w ere so o n foun d to be unsuita ble and w ere replaced
-
.

by round shot made of iron bronze lead or stone All these materials r e , , .

ma ine d in use for several centuries but stone w a s the most comm on for large ,

guns par t l y because i t s cost w a s o nly a fracti on of that of a metal shot of

,

t he same size a nd part ly because the guns w ould not stand the strain of
,

di scharg ing t he heavier materials Lead and iron bull ets w ere usually used .

for sma ll a rm s bu t in an emergency a n y small handy article was made

-
,

use of .

A t tempts w ere made very early t o throw from gun s incendi ary missiles
i is s il es .
su c h as had been di scharged pre v iously from machin es but some diffi cul ty ,

must have been exp erienced from the flames be ing extin gui shed by the rapid
mo t ion th rough the a ir A t th e siege of W eissenbur g in 1 469 stone balls.
’

w ere use d considerably smaller than th e bore of the g i m and these were ,

smeared over w i t h incendi ary matter and wr apped in a cloth soaked in the
same mi x tur e 2
.

Actual shell could not be used at that time because it wa s not known ,

h o w to cast them in metal But a sort of w eak shell was made of earthen
.

w are o r by j oini ng t w o hemispheres of metal

, These w ere filled with a slow .

burning po w der w ell rammed in or other incen diar y matter and were provided , ,

wi t h an i g niter w hi ch w a s set li ght to by th e flame from the gunpowder of

,

the pr o pellin g charge but there must have been considerable 1mce r ta in ty
,

about the i gni t i o n and of course it w a s m uch too dangerou s to introduc e

,

a li ghted shell in to the bore of a g un whi ch had been c harged with serpent ine
p o w der by means of a shovel The difficulty w a s sometimes overcome by .

enclosin g the p o w der in a paper c art r idge but thi s method did not find general ,

a c cep t ance Re d hot sh o t coul d not be used for the same reason until Stephen
.
-
.
,

Bathory King of P oland in 1 5 79 used a thi c k w e t wad to prevent the fire

, ,

spreadin g t o t he c harge H ot shot w ere used with great e ffect in th e defence

.

of Gibral t ar by t he E nglish in 1 78 2 .

S o li d s ho t are no t u s e d now except fo r pra c t i c e and exp eri mental purposes .

1 S l l n me nta P la t
ee i o u 69 70 7 1 H im p 19 9 ; Ris e a nd P r g s Fig 3
, es , , e, . o res , . .

3 Hi m e p 220 . .
,
 D E VE L OPME NT OF G UN P OWD ER 3]

The shell for the early muzzle loa di ng rifled guns w ere pro v ided with
-

studs to fit into the r ifl ing and with c opper plates (gas checks ) over the base -

to prevent th e escape of the gases past the she ll For som e of the early r ifled .

breech loading guns th e shell w ere coated w ith lead but now they are provided
-
,

with copper bands near the base to take the r ifli ng and prevent the escape
of the gases Originally of course shell were filled with black p o w der but
.
,

n o w high e x p losives are used a lmost exclusively for common she ll Shrapnel .

shell were devised ab ou t 1 78 4 by Lieutenant Shrapnel for use against tr 0 0 p s

in the open They were adopted offi ciall y in 1 8 03 and c onsisted of a round
.

she ll containi ng only a sma ll charge of po w der j ust sufficient to break the ,

envelope into fragments which conti nued to travel more or less in the same
,

di rection and with the same velocity as the shell did before After the intro .

duction of rifled cannon the Shrapnel shell developed into a cylindrical missile
fill ed with bullets embedded in rosin with a small charge o f black powder ,

which when ignited by a time fuse expels the bu llets Against troop s in
, , .

the open its kill ing p ower i s great but it i s in eff ective against them w hen
,

entrenched and it has not the nerve shattering effec t of c ommon shell c harged
,

with high exp losive .

Formerly case shot was used against troop s at short range It consisted .

of a case c ontaini ng a large number of bull ets w hi ch spread out from the ,

muzzle of th e gun the case being broken up in the bore The principal sorts
, .

of case shot were grape cani ster and spherical case They are not used
, .

much now as their place has been taken by shrapnel shell and machine guns
, .

Chain shot was fired against the rigging of ship s i t consisted of tw o balls
o r half balls uni ted by a chain and are said to have been invented by De
,

Witt P ensi oner of Holl and ab out 1 666

, ,
.

For exp losive shell the difficul ty was to make a satisfactory i gniter o r Fus es .

fuse The earliest record of really successful explosive shell is in the accoun t s
.

on the sieges of W a c h te ndo n ck and Bergen o p Zoom in 1 58 8 the master — -

,

gunner bei ng an Italian refugee from P arma in th e employment of the Dutch .

The fuses used were apparently tubes or pipes filled with slow bur ni ng powder -
,

which were driven into the fuse hole of the shell and th is typ e was adhered
-
,

to unt il the middl e of the nin eteenth century and later when concussion and ,

percussion fuses were invented .

The fuses were made to burn 1 4 to 20 seconds corresp ondi ng to ranges of ,

1 00 0 to 20 00 yards in the mortars w hich were always used instead of ordinary

,

g un s fo r thro w ing she ll The shell were used for the destruction of stone
.

fortifications and ship s ; again st men they w ere not eff ective as there w a s ,

usua lly plenty of time to get away from them before they e x p lode d U ntil .

after the introdu c tion of w atch es which were invented by Huygens in 1 674
, ,

no conven ient means e x isted o f testing the time of burning of a fuse In .

the middle of the eighteenth century fuses were made o f bee c h w ood with
 E X PL OSIV E S

a hole d o w n t he mid d le filled w ith fuse powder Th e fuse c ould be cut to .

a ny re qu ir e d leng t h Grea t a c curacy w a s n o t d e man d e d of t hem until

.
.
,

Cap t ain Mer cier during t he siege o f Gibral tar in 1 779 p ro p o s e d to fire s hell
fro m gun s ins t ead o f ho w itzers or m ortars Short c alculated fuses were .
“

t hen u s ed s o as t o m ake t he shell burst over the Spanish working parties .

The eff e c t pro du c e d w a s consi derable .

Accura t e fuses w ere al s o re quired for the Shrapnel shell w hich wa s devised ,
-

by Lieutenant Shrapnel R A about 1 78 4 and offi c ially adopt e d iii 1 8 0 3

, . .
, , ,

bu t t hey w ere made up o n the sam e pri n c iple u ntil the s e cond half of the
n ineteen t h cen t ury .

H and grenades seem to ha v e been used t o a con s iderable extent in the

-

firs t half of t h e sixteenth century at w hich time they were pr o bably m ade ,

of ear t hen w are They are said to ha v e been use d at the siege of Arles
.

”
in W h ite h o r ne w riting in 1 560 says that earthen bottles or p osses
“

, ,

had been formerly use d but he rec o mmen d s hollo w ball e s of meta l as big
, ,

as s mal b o ules and ! in thick cast in mo u lde s and m ade of 3 partes of brasse
,

”
and 1 of tinne They w ere charged w i th 3 partes serpenti ne 3 partes
.
“

,
”
fine corne po w der and 1 part rosen A little fine c orned p owder was used .

”
as p riming and he directs that the grenades be qui c kly thrown as t h ey
,
“

”
will a lmost immedi ately b r e a ke and fl y e into a thousand pieces .

I n the seventeenth century the p roblem of the fuse for hand grenades -

w a s fairly well solved and regiments were formed of

, Grenadiers powerful ,

men spe c ially trained to throw grenades Maj or Ady e writing in 1 8 0 2 .

, ,

sai d grenades c ould be thrown t w enty si x yards -

.

Inf ernal The doubtful honour of having invented infern al machin e s is ascribed
to a Nuremberg citizen i n 1 5 1 7 but there i s a drawing of one by Le o nardo da ,

Vinci who lived from 1 452 t o 1 5 1 9

,
In 1 645 attempt s were made to blow .

up S w e di sh shi p s in Wismar harbour b v means of clock w ork bombs The -

.

clock work a c tuat e d a flint lock wi th a revolving steel wheel

-
Clock work .
-

infernal ma c hin e s c o ntaini ng a nitro glycerine e x plosive were used also by -

t he I ri s h Ameri c an Fenians i n 1 8 8 3 and 1 8 8 4 but now clock work i s not

-
,
-

generally applied in these criminal attempts .

f ir e- w o rk s .
Fi re works seem to have been made soon after the di scovery of gunpo w der
-

referen c es to them are foun d i n the writings of Ha s san e r Rammah Ro ger - -

,

Ba c on Mar c u s Gr aec u s and Albertu s Magnus in the thirteenth and fourteenth

, ,

c enturies They w ere pr o bably made fir s t i n China and introduced into

.

E urope i n the thirteenth century They were u sed to celebrate pea c e at .

Vi c enza i n The e ssential features were developed ea r ly and later ,

centu ries ha v e a dded nothing really novel Impr o vements have been made .

in the ar ti s t i c eff e c ts preci s ion o f exe c uti o n a n d s afety bu t t he general p rin

, ,

1 l I l él
i z W h n b lt S p t 1 1 1 9 1 5
'

a r oc e
’
.a ,
2
H im c h p
e .
, . e, a . x .

3
A G n a d e w it z
. , 19 1 5, p . 273
 D E V EL OPMENT OF G U N P OWD E R
c ip le sare the same Th e introduction of chlorates at the end of the eighteenth
.

century ha s been of some assistance but their use has been restricted on ,

account of the dangerou s character of many chlorate mi x tures In the .

seventeenth and eighteenth centuries large sum s were spent i n Europe on

fi r e w o rk displays to celebrate special events b u t they were not much used
-
,

in war Carcasses c ontaining incen di ary comp osition smoke balls and light
. ,
—

balls were used h owever i n the P eninsula

,
1
The I n di ans fire d rockets in
,
.

the defence of Seringapatam in 1 792 but th e y do not appear to have done ,

much damage At the siege of the same town in 1 79 9 explosive rockets

.

seem to have been used wi t h some effect 2

Soon afte r this the Ordnance .

Office applied to the Royal Lab oratory Woolwich for the services of som e , ,

one who understood the manufacture of rockets The Laboratory referred .

the Or dnance Office to the E ast Indi a Company who repli ed that they kn ew ,

of no one who possessed such knowledge .

Colonel Congreve of the H anoverian Army (afterwards Sir W Congreve ) .

was thus le d to make e x periments and he devised the Congreve rocket the , ,

most p owerful thing of the kin d that had been used in warfare It proved .

very effective at Copenhagen and Walcheren in 1 8 0 7 and at the passage of ,

the Adour in 1 8 1 3 but it was at the battle of L eip sic that it achiev e d the
,

greatest renown for a French infantry brigade in the village of P aunsdorf

, ,

unable to withstand their well directed fire surrendered there to the Rocket —

Brigade At Waterloo also good service was rendered

. .

Since the Nap oleonic wars the improvements in ordnance have been so
great that the war rocket i s no longer used For military purp oses rockets are .

o nl y fired now as signals and to illuminate the enemy s p osition at ni ght and ’

for th e latter purp ose they have been displaced to a great extent by star shell .

The use of gunp owder for blowing up the enemy s walls and fortifications ’

commenced in the fifteenth century Mines charged with gunp owder were .

used in 1 4 1 5 by the E ngli sh at the siege of H o n fl e u r .

For blasting minerals gunp owder does not appear to have been used until Bla sting .

th e seventeenth c entur y Th e first recor de d blasts were made by Gaspar

.

W e indl at Schemnitz in Hungary and from there the method was introduced
, ,

into Germany in 1 627 P rince Rupert son of the Queen o f Bohemia and.
,

nep h ew of Charles I is said to have brought the practice of blasting to England

,

i n 1 629 but t h is i s doubtful 1 670 is a more probable date

,
3
In 1 68 9 Thomas .

Ep s ly Senior started th e use of gunp owder in the Cornish mines 4

The late .

Mr Oscar Guttmann in his book on B la s ting published in 1 9 0 6 gave the

.
, , ,

foll owing concise account of the further progress

When bore h o les first came into
-
use they were made with iron mouthed -

1
R is e a nd P r o g r es s ,
p . 1 74. 2 H im p e, . 1 29 .

3
B r it E x p
. , I nd .,
p 255.
.
4 Fe ld haus , S .S .
, 1 90 8 , p . 21 8 .

V OL . I .
3
34 E X P L OSIV E S

b o rer s fa irly large nearly 3 in che s i n diameter and then closed w ith a w o o d en
,
—
,

plug t e rmed the s hooting plug

,
‘
.
’

“
Hen ning H u t man in 1 68 3 employed a kin d of dri lling machin e In
-
.

1 68 5 clay t a mpings and in 1 68 6 fi r in g tubes began to be u s ed

,
-
,
I n 1 68 9
.

paper c artridge cases were used to replace the ol d er form of lea t her and in ,

1 71 7 bore h o les of sma ller di ameter came into vogue

-
The use of th e chisel
.

borer date s from 1 749 bla sting the un touched breast from 1 767 (fi rst at
,

I t is onl y by blast ing operations tha t m any o f the engineering fea t s of

m odern time s have been ma d e possible In c onstru c ting means of com
.

mu ni c a tio n such a s road s canals and railways immense quantities of

, , ,

expl o sives have been use d .

 C H AP TE R I I I

PROGRESS OF EXPL OSI V ES I N TH E EI GH TEENTH AND

NI NETEENTH CENTURIES

Be r t ho lle t C hl o ra t e I gnit er s Fo r s y t h s d e t o n a t o r lo c k Ful mi n at es C ap s

,
’ '

Fus e s G un c o tt o n f N i t r o g ly ce rine
- -
Ammo ni um ni tra t e e p lo s ive s Sp r e n ge l
x

ex
p lo s ive C o a l min e d an g e r s
s C h e dd i t e I n s p e c t io n o f e x p lo s iv s Smo k e e
-

le s s p o w d e r s Pi cric a c id Tr o t y l

IN the nineteenth century commenced the active appli cation of s c ience to

exp losives with the result that this industry li ke so many others developed
,

enormously In this chapter no attemp t will be made to give in detail the

.

history of each invention ; only the principal discoveries will be mentioned ,

and an attemp t will be made to show how one has led up to a nd assisted
another .

When chemistry was put on a fir m basis at the end of the eighteenth

century there was a great increase in the number of chemical comp ounds
,

which could be made in the laboratory No man had more influence upon .

chemical science than Count Claude L Berthollet (1 748 . Amongst

the substances which he di scovered was potassium chlorate or at least he in ,

1 78 6 first showed clearly h ow it c o ul d be prepared in the pure s tate and he ,

investigated and described its prop ertie s for it seem s to have been kn own to
Glauber (1 60 3 Berthollet found that potassium chlorate if substituted ,

for saltpetre produced a more p owerful (or vi olent ) explosive and proposed
, ,

in 1 78 8 to manufacture gunp owder with it B ut the results were most .

disastrous A party had been made up to see the first of the new p owder
.

made in the mills M and Mme Lavoisier M Bertho llet the Commissary
. .
, .
, ,

M de Ch ev r a u d and hi s daughter the engin eer M Lefort and others W hilst

.
, ,
.
,
.

th e mixture was being inco r porated in a stamp mi ll the party went to break -

fast Lefort and Mll e de C h e v r a u d were the first to return and as they di d
. . ,

so the charge exploded with great vi olence throwing them to a great di stance
,

and caus ing them such in j uries that they both died in a few minutes .

In spite of repeated attempts it has not been found possible to make a

satisfactory propulsive exp losive with c h lorate the explosion is always liable
to b e too Vi ol ent and uncontroll able .

35
 E X P L OSIV E S

U n t il
the inventi o n of Che ddite all the chl o rate mixtures proposed w ere
t o o sensitive t o be used with safety even as blasting explosives C u n di ll .

and Thom s on s D ictio na r y o f E x p lo s ives issued in 1 8 9 5 in c ludes the de s criptions

’

of 1 50 mi x t ures c ontain ing potassium chlorate but w ith the exception o f a ,

fe w cap and fuse compositions none of these have pr o ved to be of practical use .

I gniters The first fi r e arm s were set off by means of a lighted match which was
- .
,

appli e d to a p ri ming of fine po w der Rain or wi nd seriously interfered w ith .

t he o peration I n the eighteenth century the flint lock was devised and a
.

lighted match was no longer necessary In its best form the priming powder .

was conta ined in a small chamber which wa s uncovered only at the instant
w hen the des c ending flint struck a spark from the steel Although thi s was .

a great improvement i t left much to be desired as regards ease of loading ,

rapidity of ignition and fouling of the touch hole H ence the persevering
,
-
.

attempts to devise an easier and simpler method .

Fo y th
rs
’
s In 1 8 0 5 the Re v A J Forsyth a Scotch minister made a sporting gun
. . .
, ,

deto na to lock with a detonator lock and in the ne x t year submitted his invention to the
r .
,

Master General of Ordnance who asked him to adapt it to the requirements

-
,

of the Ser v ice Forsyth s devi ce consisted of a receptacle or m agazine shaped

.
’

like a scent bottle which was attached to the lo ok of the gun It contained
—
, .

a detonating mixture of potassium chlorate charcoal and sulphur By , .

rotating the magazine a small quantity of thi s was cau sed to fall into a small
hole in a plug communicating w ith the touch hole of the gun and on again -
,

rotating the magazine it was brought i nto such a position that the portion
of detonating priming could be set o ff by the fall of the hammer .

Forsyth spent some £ 600 in trying to produce a satisfactory device for

military purposes and he claimed to have succeeded but the Government
, ,

authorities were not convinced and did not adop t it At the time they only .

paid Forsyth s expenses but they granted £ 1 000 to hi s relatives shortly after
’

hi s death .

For sporting purposes Forsyth s invention had some success but the ’

p rofits must have been largely swallowed up by th e numerou s lawsuits that

he instituted to protect it from 1 8 1 1 to 1 8 1 9 Before very many years had .

elapsed Forsyth s device was displaced by the copper tube or cap containing
’
,

fulminate of mercury .

Ful mina tes . Fulminates of gold and silver have long been known and their discovery ,

was as c ribed to Basil Valentine a fictitiou s person of the fifteenth century , .

They were perhap s invented by Cornelius Drebbel a Dutchman about , ,

P epys in his diary for November 1 1 1 663 recount s a conversation wi th a

, , ,

Dr Allen who told him abou t Au r u m fu lmina n s

.
, of whi ch a grain put ,

i n a silver spoon and fi red will give a blow like a mu s q u e tt and s trike a hole
,

”
throu gh the silver spoon do w nward without the least force u pward , .

1 F M F l hau 1 9 0 9 p 258
d S S , . e s
, , , , , . ,
 PROG RE SS OF E X P L OSIV E S
Mercury
The fulm inate s of gold and s ilver are however too sensitive and dangerou s , ,
f ul mina te .

for any p ractical use but th ey have played the ir part as t oys and scientifi c
,

curiosities Liebig w h o wa s b o rn in 1 8 03 when a boy s a w a quack in th e

.
, ,

market place of Darmstadt make fu lminating silver

-
The alcohol he recog .

n iz e d from th e smell of a garment whi c h the qua c k had cleaned with li quid

from the same bottle He w ent home and succeeded in making the substance
. .

In 1 8 23 when he was in P aris with Gay Lussac he investigated the fulm inates
, ,

at the suggestion of the latter and i solated fulminic aci d By that time the , .

comparati v ely stable fulminate of mercury was well known having been ,

described by E d w ard H oward in a paper before th e Royal Society ,

in 1 8 0 0 It i s stated that it was manuf actured in France in 1 8 1 9

. .

The re i s some uncert a inty as to who first invented the ful minate of mercury
cap but it seems that several people were working at the idea at t he same
,

time and contribut e d to w ards the final su c cess Accor din g to H Wil kinson 1
. .
,

J Shaw of P hiladelphi a in vented a steel cap in 1 8 1 4 in 1 8 1 5 a pewter c a p

.
, , ,

and i n 1 8 1 6 a c opp er cap The London gun m aker Joseph Egg seem s to .
-
, ,

have a dopted the idea from Shaw The P a ri s gun makers P rélat and .
-
,

D e b o u b e r t in 1 8 20 patented cap s fill ed with f ul min ates of sil ver and mercury
,

respectively E Goode Wright of Hereford in 1 8 23 published a paper

. .
2
, ,

on the ful m inate of mercur y cap and subse quent workers seem to have derived ,

mu c h information from it Frederick Joyce was the first t o make a real .

success of the p ercussion cap about 1 8 24 The firm of Joyce and Co claim . .

an ear lier date but although experi ments may have been made in previou s
,

years there appears to be no evidence of manufacture on a onsiderable scale

c
3
.

The next important step was to combin e shot p o w der and cap in one Th e ca pp ed
.
,

c artridge w hi ch could be inserted in the breech of the arm

,
Many attempts c a tfi dg e
.
r ‘

had been made from very early times to make breech loa ding fi r e arms but - -
,

wor kmanship and kn owledge of engineeri ng were not suffi c iently advanced
to make a success of it In 1 8 3 6 L e fa u c h e u x introduced his pin fi r e breech
.
-

loa ding shot gun the barrels of which w ere made to drop as in the modern
—

shot gun to allow the cartridges to be introduced This gun al t hough it had
-
.
,

ma ny imperfections combined all the principal features of t hose made at the

,

present day About 1 8 53 the E nglish and French gun makers introduced
.
-

the central fire hammer g un which fired cartridges having a cap in the middle ,

of the base of the cartridges but the first really successful central fire gun ,

w a s that made by Daw in 1 8 61 4

In 1 8 4 1 the P russians adopted a breech loa ding rifle the Ziin dna g el ggfi g ifi e '
-
, r e

1
E ng in es o f Wa r p , . 1 8 7. g , v o l l x i i , p 20 3 .
P h il . ll l a . . . .

3
Th e a c co r mt of t h e d is c o ve r y o f t h e p e c s s ioru ca p is l g e lyn ke f o m t h e p a p ear ta n r r
by E . H ul me , B A
. ., in t h e R is e a nd P r o g r es s o f th e B r i ti s h x p lo s iv e s I nd us try , E
L ondo n 1 90 9
, . S ee a ls o U t e s c h e r , S S . 1 9 14 ,
p . 10 1 .

4
G r en e r
e , fi l o de r n S h o t G u n s , 2n d cd ., 1 8 9 1, p . 4.
 E X P L OSI VE S

ge w ehr in v ented in 1 8 3 8 by D r e y se In this i gni t ion was effec t ed b y a

,
.

nee dle being d ri v en right t h rough th e base of the cartridge into a di sc of

fulmina t ing mate ri al Af t er a fe w roun ds th e rifle c o u l d not be fired from
.

t he shoul d er in c o nsequence of the escape of flame The needles also rus te d .

and broke But in spite of its defec ts the gain in rapidity of fire caused i t
. .

t o be mainta in e d as the general arm in the wars o f 1 8 4 8 1 8 66 and , ,

The French adopte d the Chassep ot in 1 8 66 Thi s wa s a c onsiderable .

i mprovement upon the P russian rifle ; escape of gas at the breech was pre
vented by means o f a rubber w asher About the same time a commi ttee sat .

in E ngland to decide up on a rifle and fin all y selec ted that of Mr Jacob Sni der , .
,

an Ameri can But a t the suggestion of Colonel B oxer the cart r idge case
.

was made of brass ins t ead of t hi n paper a s in previ ou s rifles This not onl y .

grea t ly i mproved the accuracy o f shooting but effectuall y prevente d the ,

escape of gas at the b reech 2

.

t
Sa fe y fuse . The old method of firing a blasting charge was to lay a train of powder
up to i t or u se a quil l or rush fill ed w ith p owder The t ime ta ken by these
, .

t o burn w a s very uncertain ho w ever and t hi s cau sed numerous accidents

, ,

in th e min es Thi s led Mr Willi am Bic kford of Tuckin gmill Cornwall in

. .
, , ,
”
1 8 3 1 to d evise his min er s safety fuse wherein a continuou s thin core of
’
-
,

powder was c ontain ed in cable of j ute and strin g 3

This gradua ll y cam e .

more and more into u se and the fuse was improved in quality as experience
,

was ga ined in its manuf acture For u se in wet places a special quality wa s .

made covered wi th ta p e and var nished Soon after 1 8 40 the Bickford fuse .

w a s a d opted by the E ngli sh mili tary authorities In 1 8 3 6 a factory was .

started i n America ; in 1 8 3 9 in France and in 1 8 44 in Germany B efore , .

1 8 40 guttapercha covered fu se had been adop ted for blasting un der water
-
.

Various modifi c ations ha v e since been in ven ted in cludin g fuse cased i n meta l , ,
”
Colliery Fu se w hi c h emi t s no sparks and variou s sort s of instanta neou s
,
4
,

fuse ,which burn very rapidly and enable many shot s to be fi red
simul taneou sly .

Sh ell fuses . As stated in the last chap ter th e fuses of shell were originall y ar r anged
to be ignited by the flash of the po w der charge in the g un The invention .

of the percussion cap however made it possible to sta rt the action of the
, ,

fu se in another and more certa in manner In 1 8 46 Quartermaster F r e e b u rn .

,

R A invented the fi rst E ngli sh time fu se sta rted by the concussion of t he

. .
,

di scharge ; a nd in 1 8 50 Commander Mo o r s o n R N brought forward th e , . .

,

first per c ussion fuse w hi c h was actuated by the shock of impact of t he she ll 5
.

The s e tw o t y pes of fuse are s t ill i n u se and are m a d e to s c rew into either th e
1
Te x tb o o k o f S ma ll A r ms , 1 9 0 9 ,
-
c hap . ii .

2
Te x tb o o k of S n w ll A r ms ,
-
1 90 9 .
3 Eng . Pa t . No . 61 5 9 of 1 8 31.
4 Pa te nt ed b y Sir G . S mi t h in 1 8 8 6 .
5
H im e,
p . 24 5 .
 PROG RES S OF EXP OS I VES L
n ose or base of the shell Very often both methods are c o mbine d in a time
.

”
and percussion fuse Shell were used with great effect by the Russian
.

fleet against the Turkish at Sinop e in

Gun cotton wa s discovered in 1 8 45 1 8 46 by C F S chonbein P rofessor G n cotton
- -
. .
, u -
.

1 8 46
of Chemistry at Basle in the course of some exp eriments w hi ch he was making
,
.

up on highly o x idized bo di es followin g up a train of thought suggested by ,

his di scovery of ozone in 1 8 44 P e lo u z e had made an e x plosive in 1 8 3 8 by

’

the action of nitric acid on cotton but he did not take the imp ortant step of ,

mix ing sulphuric with the nitric a c id and he did not make any practicable ,

app lication of his explosive Sc h fi nb ein at once recogn ized its imp ortance a s .

an exp losive and kept the method of preparation secret w hil st he endeavour ed ,

to sell the process to variou s Governments H e showed th at when fired in .

a musket gun cotton produced the same velocity as a much greater weight of
-

gunp owder P rofessor B ottger of Frankfort o n Main discovered gun cotton

.
,
- -
,
-

i n 1 8 46 independently of Sch onbein but he entered into an arrangement with

, ,

h im t o share the profits of the invention Several others attracted by the .

,

great stir that was caused by the in vention endeavoured to make gun cotton -

and some of them succeeded but Sch onbein was able to main tain the start
, ,

he had obta ined In the autumn of 1 8 46 he came over to E ngland and gave
.

some very successful demonstrations at W oolwich and P ortsmouth and before

the B ritish Asso ciation In the name of John Taylor he took out a British
.

P atent ,
2
and he entered into an agreement for t h ree years with J ohn Hall
and S ons that they should have the sole right to manufactur e g un cotton at -

their p owder works at Faversham and in ret u rn should p ay one thir d of the ,
—

net profit with a min imum of £ 1 00 0 down and the same each year B ut .

before a year had elap sed on J uly 1 4 1 8 4 7 there was an exp losion of the , , ,

g u n
-
cotton wh i ch destroyed the factory and kil led twenty one men After -
.

thi s Hall and S ons refused to proceed with the manufacture About the .

same time th ere were disastrou s gun c otton exp losions at Vincennes and -

B ouchet and these produced such an e ff ect that no more gun cotton was
,
-

manufactur ed in E ngland or France for some sixteen years .

Meant ime Sc h ii nb e in had offered his process to the German U nion

(Deutscher Bund ) for thalers and a committee had been forme d ,

to consider the matter on which Liebig represented the state of Hesse and
, ,

Baron von Lenk who was secretary represented Austria T hi s c ommittee

, , .

sat un til 1 8 52 but finall y refused to buy the process partly on political grounds
, , .

The i ndivi dual members of the U nion were then able to make separate
negotiations and at the suggestion of von Lenk who had done most of the
, ,

actual work of the c ommittee Austria ac quir ed the process for gulden ,
.

In 1 8 52 the E mperor of Austri a appointed a committee to inquire int o v on L nk e .

the use of gun cotton for military purposes and with some interrup t ions this
-
,

1
Ru s c h S S 1 90 8 p 1 8 9
, .
2
. N ,
1 1 40 7 O c t b r 8 1 8 4 6
, . . o .
, o e , .
 EXPL OSI VE S

con t inu e d to si t un t il 1 8 65 In 1 8 53 a fa c t o ry w a s erecte d a t Hir t enberg to

.

ca r ry ou t v on Le nk s me t hod of makin g gun co t t on In t hi s th e pur ifi c ation

'

-
.

w a s some w ha t more t ho r ough t han in Sc h ii n b e in s original p rocess for in s te ad

’

of me r el y w ashi ng wi t h w a t er u n t il neu t r al von Le n k w ashed for th ree weeks , ,

t hen b oil ed wi t h dil u t e po ta s h solution fo r fif t een minute s washe d again ,

for seve r al da ys imp r eg na t ed t he y arn w i t h water glas s and finall y d ri ed

,
-
, .

Von Lenk al s o cons t ru c t e d some ba t t e r ie s of 1 2 p oun der guns to b e fire d -

wi t h gun co t t o n c art ridg e s

-
Th e se guns w ere s o much da maged by fi ri ng
. .

ho w ever t ha t no o t her na t ions adop t e d t hem

, About 1 8 60 v on Lenk .

in t r oduc ed bronz e gun s which w e r e less liable t o burs t than iron ones and
, ,

t he s e no t onl y had a p ropul sive c h arge of g un cotton but also had shells -
,

con t a ining a burs t ing c harge of t he same explosive I t wa s found however . .

,

t ha t t he se of t en burst in t he bo r e and t his was evi den t ly due t o t he very ,

sudden s h o ck of t he di scharge exp lodin g t he shell charge for when gunpowder ,

w a s u sed to fire t he g un co t ton shells no bursts t ook place

-
On July 20 ,
.
,

1 8 63 t he magazin e a t H ir t e nberg explod e d and thi s seem s to have finall y ,

d e cided t he Au s t rian au t hori t ies t o gi ve up g rm cot t o n as a propulsive -

exp losive and von Lenk w a s t hen all o w ed t o commu nica t e t he me t hod of
,

manuf ac t u re t o o t her P owers In 1 8 65 ano t her magazine e xp loded on

.

S t e inf elder Hea t h nea r Vienna and on Oc to ber 1 1 1 8 65 th e m anufacture , ,

w a s o fficially sto pped in Austria .

The f u rt her developmen t then to ok p lace i n other c ountries Von Lenk .

m ad e commun ica t ions to t he E mp eror Napoleon I I I and exp e ri men t s were ,

sta rte d in France In 1 8 64 he t o ok ou t an Ame ri can pa t ent

. .

In 1 8 62 and 1 8 63 von Lenk t o ok ou t pa t ents in E ngland in th e name

of Rév y t o pro t ec t his methods of p u rifi ca tio n a n tl in t he la t t er year he
1
.

came over w i t h t he perm is s i o n of the E mperor to de scribe hi s proce ss to a

commi t t ee of t he B ri t i s h Association The same year Messrs P r entice and . .

Co s t ar t ed t o make gun co t t on a t S t o w m arket b v von L e n k s process but

.
-
’

an exp lo s ion occurred t here soon af te r .

U n d er t he di re c t ion of Fre deri c k Abel t he Chemis t of the E ngli sh War ,

Depar t men t manufac t ure w a s also starte d abou t t he same t im e on a small

,

s ca le in t he Ro yal G unp owder Factory a t V Va lt h a m Abbey This made i t .

po s sible for Abel to carr y ou t t h ose e xp erimen t s a n d researches w hich led

t o a r e v olu t ion in t he e xplosive s indu stry and have rendered gun co t to n ,
-

one of t he safes t e x plosive s in m anufa ct u re a n d u s e In 1 8 65 he to ok out .

a pa t e n t for pul ping gu n co t t on and pre s sing it in t o blo c ks and in 1 8 66 and

-
2
,

1 8 67 he publi s hed his Re ea r che o n G u n co tto n s 3

He s ho w ed that b y pulping
s -
.
.

E ng P a t s 10 90 o f 1 8 62 a n d 2720 o f 1 8 63
. . .

3 En
g P a t No 1 1 0 2 o f 1 8 65
. . .Th e p lp i g o f gu n c o t to
. ha d oweu n -
n , h v r e , b ee n ca rried
o u t a t L e Bo u c e h t
in Fr a n c e (se e s ca le s
, S eb z E
es s b a u m u o lle 1 90 5 p
'

, , .

3
P h il Tra ns o f Ro ya l S oc ie ty 1 8 66 p 269 ; a n d 1 8 67 p 18 1
. . . , . , . .
 PROG RESS OF EXP L OSIVES

g u n cotton in the same way as i s done w ith rags etc in the manufac t ure
-
, .
,

of paper he not only g o t it in a m ore convenient sta t e for pressing into blo c ks
, ,

but the violent mechanical treatment rem oved m uch of the imp u rity and ,

the gu n cotton was r e duced to a condition i n whi ch it was much easier to

-

wash it thoroughly The obj ect of compressin g the pulped g un cotton w a s to.
-

restrain the violence with w hich i t explo ded in the gun but alth o ugh i t was
1
,

better t han von L e nk s yarn it w a s still uncontroll able ; it d amag e d t he ’

guns and the accuracy of t h e shoo t ing was un satisfactory I t w a s not un t il

,
.

some seventeen years later that a su c cessful smokeless military p o w der w a s

made Gun cotton w a s therefore only used for blasting purp oses P renti c e
.
-
.

and C o of Sto w market adopted Abel s process of pur ification a n d have

.
, ,
’

continued to use it ever since In 1 8 68 its utili ty was much increased by the .

discovery by Abel s assistant E A Brown that dr y c ompressed gun cott o n

2 ’

, . .
,
-

could be caused to exp lode very violently by a detonator contain ing fulminate ’

of m ercury this app liance ha v ing been already use d by Nobel fo r de t ona t ing
,
3

nitro glycerine B ro wn afterwards made the further discovery t hat a slab o f

-
.

wet g u n cotton could be e x p loded by means of a sma ll primer of dry gun cotton
- -
.

Thi s rendered it p ossible to store t he greater part of the gun cotton in the -

wet state a great advantage for mi litary p urp oses and in t hi s fi eld gu n c otton
, ,
-

as ori g inall y prepared under the superin tendence of Abel st ill holds its ground
to some extent .

In 1 8 47 Maynard di scovered that ni tro cell ul ose was soluble in a mixture Oth s e -
er u s

nit o
of ether and alcohol although it di d no t di ssolve in either li qui d alone and c ell l o
, ,
r
u s e.

thi s led t o the in vention o f the c ollodi on photography by S cott Archer in

1 8 51 and to other u ses of c ollo di on
,
Cellul oi d made by di ssol vi n g nitro .
,

cell u lose in camphor with the aid of hea t and pressur e wa s patented by ,

J W and I S Hyatt in
. . The art ificial silk industry may be said to
. .

have started in 1 8 8 4 w hen Count H ila ire de Chardonnet took out hi s firs t
patent 5
.

In 1 8 46 nitro glycer ine was di scovered by So b r e r o P rofessor of Chemistr y Nit o

-
,
r

g ly c rin e e.
at Turin who had been assistant to F elouze in 1 8 3 8 w hen he made his first
,

exp eriments on nitratin g various bodies B ut no practi cal app lication w a s .

made of it e x cep t that very small quantities were used in medi cine as a cure
for angina pectoris P eople were no doubt deterre d by t he d angerous na t ure
.

of the material and the inconvenience of dealin g with a li qui d explosi v e as ,

also by the di fficulty in causing it to e x plode In 1 8 59 t o 1 8 61 however .

,

Alf red Nobel and his father made e x p eriments with it and foun d t ha t i t ,

could be exploded by means of a detonator containi ng fulminate and in 1 8 6"

,

1
S ee C h e m N e w s 1 8 66 (4 ) p 250 .
, , . , a nd 1 8 71 , (24 ) p . 14 1 .

2
E n g P a t NO 3 1 1 5 o f 1 8 68
. . . .
3 Eng . Pa t . No . 1 3 45 o f 1 8 67 .

4
Ame r
Pa t J ly 1 2 1 8 70
. . u , . S ee J . Soc . C he m I . nd 1 9 1 4, p . 225 .

5 F e c rn h
Pa t .
 EXP L OSI VES

commenced t o manufactur e it a t H e le n e b o r g near Stockh o lm Many serious , .

a c ciden t s occurred in the transpor t and use of the explosive and in 1 8 64 an ,

exp losion took place at the H e le n e b o r g works which destroye d them kille d , ,

t he head chemist and Nobel s brother and caused hi s father a paraly t ic ’

s t roke from whi ch he never recovered Nobel however wa s no t dete rred .

, ,

by thi s and proceeded to r e erect hi s factory at Vin te rv i kke n and build a

,
-

new one at K r iimme l in Germ any H e was c onvinced t hat ni tr o glyce r ine .
-

w a s t he most p owerful explosive known or lik ely to be di scovere d and he ,

a llowed not h in g to prevent him tur ni ng its properties to p r o fi table a c c ount - .

The c ontinual catastrophes however caused the variou s states to pass , ,

laws restrictin g or prohibiting the transp or t and use of nitro glyceri ne In -

.

consequence Nobel searched for means to make the material safer a n d m ore
c onvenient to han dl e and di scovered that kieselguhr had the power to absorb
,

three t imes its w eight of nitro glycerine 1

Thi s comb ined with the f u lmina t e
-
.
,

detonator mentioned in the same specification pro d uced a very convenient ,

and fair ly safe exp losive Nobel t hen proceeded to exploit his inventions
.
,

and h e did thi s with such success that by 1 8 73 fifteen factories had been
buil t or founded in the variou s c ountries of E urope and America In 1 8 75 .

he made anoth er i mp ortant in vention that of blasting gelatine

2
The , .

nitro glycerine in thi s explosive was soli di fi ed by havin g about 8 p er cent

-
.

of co llodi on cotton dissolved in it As c ompared with kieselguhr dy namite .

t his has two advantages : the ni tro glycerine is not liable t o be displaced -

from it by w ater a defect whi c h in the case of dynam ite has led to
,

m any accidents ; and secondl y the substance added i s itself an exp losive
, , ,

and consequently blastin g gelat ine is 25 per cent more p owerful than dynamite . .

Gelatini zed ni tro glycerine c ontaini n g a small proportion of collodion has

-

been made a c onstituent of many blasting exp losives the nature of the o t her ,

constituents and the method of preparation being m o dified to produce

explosives sui table for blasting d ifferent sorts of rock and other materials 3 .

In 1 8 67 the Swe di sh chemists C J Ohlsson and J H No r r b in took out , . . . .

,

a patent for exp losives consisting of a mm oni um nitra te ei t her by itself or ,

in admi x ture with other substances such as charcoal sawdust nap h thalene , , ,

picric acid ni tro glycerin e or nitro benzene They were led to their invention
,
- -
.

by theoreti c al calcul ations which showed that a very large am ount of heat
,

and gas was g iven o ff in the exp losion of these mixtures They selecte d .

t he p ro portions so that a ll the carbon should be converted t o carbon

d ioxi d e and the hy drogen to water Considerable difficul t y was however .
, ,

exp erienced in igni tin g the charges and consequently they usually added ,

s o me nitro glycerine to assist the explosion After w ards they used th e

-
.

1
Eng . Pa t . No . 1 3 45 of 1 8 67 .
2 E ng . Pa t . No . 4 1 79 o f 1 8 75 .

3
A ve ry n t e r t in g a cco un t
i es of Al fr e d No b el a nd h is i nve n t i n s o wa s co n t rib u t ed
b y de Mo s e n t ha l to t h e fo r 1 8 9 9 , p . 44 3 .
 PROG RE SS OF E X P L OSIV E S
f ul min ate detonator The explosive was used to some extent in Sweden
. .

E arly in the seventies Alfred Nobel bought up the invention and took out
further patents in connexion with it but great di fficulties were experienced ,

in c onse quence of the very hygroscopic nature of ammoni um n i trate Soon .

after this Nobel invented blastin g gelatin e and he di d not take much active ,

interest in ammonium nitrate explosives for some time .

In 1 8 71 Dr H ermann Sprengel . the celebrated inventor o f the ,

Sp r eng el
ex p l os m s'
mercury vacuum pump took out patents for a whole series of mi ning ,

explosives to be made by mixing an oxi di zing substance with a combustible

one 1
in such proportions that their mutual oxidation and de o x idation
“
-

should be theoretica lly complete The essential feature was that the two .

constituents were to be mixed together on the sp ot j ust before the explosive

was required and the mixture was to be exploded by means of a fulminate
‘

detonator As oxidizing agents he mentions amongst others nitric acid and

.

chlorate of potash ; as combustibles a very large number of substances ,

including nitro benzene nitro naphthalene carbon bisulphide petroleum

-
,
-
, , ,

picric acid Liquid nitric acid is a most obj ectionable material to handle
.
,

nevertheless several inventors have t aken out patents for Sprengel explosives
c ontai ni ng nitric acid either enclosed in glass tubes or ab sorbed in fossil flour
or other similar material 2
Nee dl ess to say they have never found favour .
, .

In addi tion to its other disa dvantage there is the serious danger that th e
nitric acid may c ome in contact with th e detonator and cause a premature
explosion This actually happened in 1 8 8 4 to the inventor P u n sh o n
. .

Sprengel explos i ves c onsistin g of c hl orate of potash and a li quid c o mb u s

tible material have h owever been used to a c onsiderable extent The Ameri
, ,
.

can S R Divine took out a patent in 1 8 8 0 for mi xtures of this sort and
, . .
,

several E ngli sh patents in the follo w ing years On e of these mi xtures under 3

m
.
,

the na e of Ra c ka r o c k was used on October 1 0 1 8 8 5 for the great blasting

, , ,

Operation of Hell Gate i n New York Harbour On thi s occasion lb . .

of Ra cka r o ck were used together with lb of dynamite . .

There are c onsiderable advantages in transportin g separately two such

inert substances as nitro benzene and chlorate of potash but against this -
,

must be put the di ffic ul ty and inconveni ence of mi x ing the c o n s titu te n ts in
the right proportions on the spot If made up beforehan d the cartridges .

are dangerously sensitive and become more so on keeping U nder the E nglish .

E xplosives Act this mixi ng i s considered to c onstitute the manufacture of

an explosive and consequently may only be carried out in a duly li censed
,

1
rt
B i . P ats . No s 9 21 . a nd 2642 of 1 8 71 . Jou r . C h em S o c . ., 1 8 73 , p . 79 6 ; S S . .
, 1 90 7,
p . 184 .

H e llh o ff, B it P t s 1 3 1 5 o f 1 8 79 , 1 28 5 8 7
2
r . a .
—
a nd 2775 of 1 880 . Punsho n B i ,
rt . Pa ts .

2242 o f 1 8 8 0 , 2428 o f 1 8 8 3 B ic e l , F e n c P a t . h r h . of 18 85 .

3
E n g P a t No s
. . . 55 8 4 a nd 559 6 o f 1 8 8 1 , 1 4 61 of 1 8 8 2, 5624 25 —
o f 188 3 .
 44 E X P L OSIV E S

factory Therefore Sprengel expl o sives ha v e n ever been u s ed in the Bri t i s h

.

Isle s but they w ere i ntro duced by t h e American s into China a n d Siberia
,

w hen t he fir s t rail w ays were built there a n d one o f them is n o w licen s ed in ,

Italy .
1

Ox y liq uit . A s o me w hat s imilar expl o s ive O x y liq u it invente d by Lin de c o n s i s te d , ,

o f liqui d o x ygen ab s orbe d in w adding c harc o al o r other organic material

, , .

I t was f o un d t hat the s e mi x t ures w o uld not d e t o nate rea dily s o kie s elguh r ,

w a s sub s t itu t e d a s abs o rbent w ith an ad dition o f liquid pe t roleum Thi s .

det o nate d all righ t but w a s m o re s en s itive t o a bl o w or s park than dynami t e

, .

I t w a s very in c o nvenient to use as the cartri dge h a d to be fire d w ithi n five

,

o r fifteen mi nutes o f its preparati on ac c o r ding to the diameter The e x plo

, .

s ive was tried i n 1 8 9 9 by a c ommission i n Austria a n d o n a fairly large scale ,

i n t he buildi ng of the Simplon tunnel but i n spite o f t h e lo w c o s t o f liq u i d

,

o xygen it was foun d that the prac ti c al diffi culties were very grea t .

During the War h o wever the use of e x plosive s o f thi s class is being
, ,

enc ouraged in Germany in o rder that th e available suppl y o f ni t rates may be

use d as far as possible fo r mili tary purpose s The in dus t rial u se o f chlorate .

explosives is being extended fo r the same reas o n .

Picr ic a c id. Sprengel also drew attention to the fact that picric acid by itself c o ul d
be detonated by a powerful detonator a n d was a very violent explosive bu t ,

no u se was made of it i n this way until many years later .

The revi val of amm o niu m nitrate explosives w a s due to the demand for
such as w ould not ignite the fi r e d amp i n coal mines Numerous disaster s
- -
.

d u e to the explosion of fi r e damp led to the appointment of commi s s ions in

— .

many of the countries of E urope t o inquire into the matter and pr o po s e

reme die s The nature of the d anger w a s investigated in 1 8 1 5 by Sir Humphry
.

Davy and one source of disaster was remove d by the sub s tituti o n of the
,

Davy lamp for the nake d li ght As time went on gunpowder was u s e d m o re
.

and more fo r breaking the coal a n d after 1 8 70 dynamite w a s al s o used Ab o u t

,
.

1 8 73 Macnab proposed to insert a cyli nder fill e d with w ater in front o f the
charge Others h ave suggeste d w e t m oss j ell y c o ntaining 9 0 per cent water
.
, .

a n d sawdust saturated w ith a s o lution of alum and sal ammonia c But .

the s e devices w ere found to be cumbersome a n d e x pensive and not very

e ffective .

In 1 8 70 d uring the Siege of P aris Pr o fe s s or M Ber t helot w h o h a d hithert o

, , .
,

d ev o ted himself to pure s c ience was calle d up o n t o give h is city a n d c o untry

,

the benefit of his s c ientific kno w ledge a n d he w a s t hu s le d t o s tudy the s u b

,

j e c t of e x plo s ive s and e s pecially to c o nsider the amount of heat o r energy

liberate d in the reactions w hi c h take place fo r he h a d been w o rking at therm o ,
.

chemistry for s ome years a n d w a s practically t h e f o un der of thi s bran c h o f

s c ien c e Af ter the war w a s over Ber t hel o t s s ervi c e s w ere s till re t ained by
'

G u t t ma n n Tw nty Y
1 ?
, P g e
p 10 ea rs ro r es s , . .
 P ROG RE SS OF E X P L OSIV E S 45 ;

the State in c onne x ion with all matters conn ected with explosives On the .

recommendation of the French Academy of Sciences he was in 1 8 76 appointed

a member of the Com mittee on P oudres e t Sa lp étr e s ”
In order to deal .

adequately w ith the many new inventions he recommended the formation of

a special commission This was done in 1 8 78 and Berthelot was appointed
.
,

”
president of the new Commission des Substances explosives a position ,

which he occupied for many years .

In 1 8 77 a commission was appointed in France to inquire into the question

of ignitions of coal damp In the report which it made in 1 8 8 0 it was obliged
-
.

to admit that there was then no explosive known that would not ignite coal
damp An E ngli sh Commission which reported in 1 8 8 6 was forced to come
.

to an equall y unsatisfactory c onclusion .

In 1 8 8 5 the P russian Government built at Neun kirchen the fir st testing Pr u ssia .

station for investigating mining explosives and adopted a method of testing ,

which wi th sli ght modifications has been copied by the Governments of E ngland
and several other nations A long ir on cylinder w a s fi lled with mi x tures
.

of coal damp c oal dust a n d air and the e x plosives were fired At first the
-
, , .

explosive was simply suspende d in the gas mi x ture and it was found that the ,

gas was ignited every time Af terwards it w a s fired from a small m ortar
.

without tamping and it was f o und that under these condi tions kieselguhr
,

dynamite was safe up to 1 0 0 grammes and gelati ne dynamite up to ab out 8 0 , .

It was now that amm o nium nitrate e x plosives came to the fore again ,

as experience sh o w ed that considerably larger c harges could be used without

igniting the gaseous mixture Two of the fi rst of the s e were roburite and
.

s e c ur ite mixtures of amm o n ium nitrate with dinitro benzene But it was
,
-
.

also found possible by suitable admixtures so to alter the character of nitro

glycerine explosives that they can be used in coal mines with comparative —

safety In 1 8 8 5 Schmidt and Bichel introduced carboni te a mixture

.
,

of nitro glycerine saltpetre and flour

-
, Thi s has been able to h old its .

o w n to the present day and is still considered one of the best safety ex
plosives .

In 1 8 8 7 another commission was appointed in France to inquire into the Fr a nce.

matter Influenced by Berthelot s work and theories it directed its attention

.
’

mainly to the question of the heat developed by an e x plosive and the resulting
temperature of the products E xplosives h aving a high temperature of e x p lo
.

sion such as nitro glycerine

,
-
gun cotton or c ollodi on cotton —

should be mixed with a substance having a low temperature of e x p lo

sion such as ammonium ni trate Three sorts of safety explosives
were therefore intro duce d into France Grisoutine a mi x tu r e of ammoni um ,

nitrate and nitro glycerine ; Blasting P o w der P amm o nium nitrate and
-
,

co llo di on cotton ; a n d Grisounite ammoniu m nitrate and nitro aromatic

,
-

c ompounds such a s n itro na phthalene -

.
 E XP L OSI VE S
The great dra w b ac k to the u s e of amm oni u m ni trate i s it s hygrosc opic
n a t ur e but t he te ndency to ab sorb water from the a tmosphere has bee n
,

o ve r co me to a grea t ext en t by coa tin g the grains with p a r a ffi n wax or -

o ther w a te r pro ofin g mate ria l and b y enclosin g the ca rtridges in suita ble
,

envelo p es .

I n Ge rm a ny a n d E ngla nd it ha s long been recogni zed th at the te mpera

tur e o f explosi o n is only one of the f a cto rs in making an exp losive safe or
da ngerou to u se in fiery min es a n d c onsequently reliance h as been placed
s ,

m o r e u pon tr ial s in testing galleries w hich are inte nde d to imitate as nearly
,

as po s s ible the co n di t ions in a min e The Nort h of E ngland In stitute of

.

Minin g a n d Mech a ni c al E ngineers appoin t ed a Co mmittee in 1 8 8 8 to inquire

in t o t hi s m a t ter Their tr i a l galle r y at Hebburn Co lli er y w a s c omplete d in
.

1 8 9 2 a n d aft er experiment ing wi th various e xplosives un til 1 8 9 5 they r ec o m

mended t he u se o f several t h e maj ority of whi ch wer e a mm oni um ni t r ate
,

explosives .

It w a s u pon the resul t s ob ta ined by thi s Co mmi ttee that the Co al Mines
Regula t ion Act of 1 90 6 w a s foun ded This Act which is sti ll in force author
.
, ,
'
i zes t he Home Secreta ry t o prohi bit the u e of any e xplosive in coa1 mi nes s -
,

a n d to a ppo int Inspecto rs of E xplosives to admi niste r the Act A testin g .

ga ll e r y w a s erected in Woo l w ich Arsenal and there a ll exp losives h ad to be

,

t es t ed b efore t hey w ere permi tted to be u sed in coal mi nes in the Uni ted Kin g -

dom Mo r e r ece n tlv a larger testing gallery h as bee n erected at Ro therham

.
,

w he r e t es t s ca n be carr i e d out on lin es more n e arly approachin g th ose that

h a v e been a d opte d in Ge r many and Bel gium .

M di te. I n 1 8 9 7 F A G Str eet to ok out patent s fo r explosives consistin g of p o ta s

. . .

sium chl ora t e mi x e d wi t h c a sto r oil in w hi ch aromatic ni tro c ompounds are

- -

dissolved . The grea t sensitiveness of chlorate mixture s is thu s overcome .

Th e exp losive thu s produce d is called Cheddi te and is u sed largely in E ngland , ,

F ra n ce a nd Germany
,
.

I n 1 8 75 w a s p a ssed the E ngli sh E xp losives Ac t whi ch h as h a d such ,

a grea t influen ce upon the development of the e xplosives in du try Its form s .

w a s largely due to t he late Co lonel Sir V D Ma j e ndi e wh o was appo inte d . .

,

t he fir st permanent Inspecto r of E xplosives to a dmin i ster its provisions The .

nece ssi t y for legislati on w a s re vea led by an e xplosion at Messrs Lu dl ow s .

’

a t B ir min gham which ca used the death of fif ty three persons Co lonel

,
-
.

Ma j e ndie w a s instr ucted to r ep ort upon it P re vious to thi s there h ad bee n.

m a ny o t her ac cidents la rge a n d small in clu di ng that of tw o powder magazin es

,

on t he banks of the Thames at Er i t h w hi ch kill e d thir t ee n people and did

,

grea t da m a ge to property .

The Ins pe c to rs o f E xp losives w ere given power t o ins pec t a ll magaz ines
a nd f a cto ries a n d see that operati ons a re ca rr i e d out in a reasonably sa fe

m a nn er As a re sul t the n u m be r of deaths in explosives fac to r ies h as bee n

.
 P ROG RE SS OF E X P L OSI VE S

very greatly reduced in spite of the fact tha t the number of people employed
i s several times as great
Av g n mb e k ill d pe nn m e ra e u r e r a u
in p l iv f t i ex os es a c o r es

43
32

69
9 -0

By the wi se and tactful manner in which they carried out their duties Colonel
Ma j e n die and h is colleagues conferred this great benefit upon the employees
i n the explosive factories w ithout in any way seriously interferi ng with the
development of the in dustry In fact the precautions which th e inspectors .
, ,

insisted on have been advantageous to the shareholders as well as to the

,

workpeople and the general publi c In 1 8 9 8 Sir Vivi an Ma je n die di ed in .

harness but the work has been carried on in the same spir it by hi s successors
, ,

Colonel Ford Captain J H Thom son and Maj or A Cooper Key a n d the
, . .
, .
-
,

other Inspectors of E x plosives working under them The pro v isions o f the .

E ngli sh E xp losives Act of 1 8 75 have been largely adopted in the legislation

of foreign countries British Coloni es and Indi a , , .

It has already been pointed out that the early attempts of von Lenk Smok eless
and others to m ake a satisfactory smokeless po w der from gun cotton were p ow d -
er s .

unsuccessful because it was much too vi olent in i ts e ffects The gun cotton .
-

being in a state of fi ne fibre interspersed with air spaces the explosion trav
e ll e d thr ough it almost instantaneously Black powder on the other hand .
, ,

being a m echa ni cal mi xture the explosion can onl y start at the points where
,

the particles o f saltpetre are in actual contact with the particles of sulphur
and charc oal consequently the time of explosion i s comparatively long
, .

The first successful smokeless powder was that of Maj or Schultze of the Sch lt ,
u ze

p owd er .
Prussian Ar till ery Fir st he appears simply to have impregnated little
.
,

grains of wood with saltpetre but afterwards he purified the wood t o some
1
,

extent by washing b oilin g and bleaching it and then ni trated it and purified
, , ,

the nitrated lignose by much the same process as that used by von Lenk for
g un c otton The grain s thu s obtained were then impregnated with salt
-
.

petre alone or mixed with barium ni trate 2 This was intro d uced about 1 8 65 1 865
, . . .

Accor di ng to an analysis publi shed by Cu n di ll in the D ictiona r y of E x p los ir es

the nitro ligni n c ontained more than 20 per cent of u nni tr a te d li gnin Thi s
-
. .

and the diff erent physical structure of wood as compared w ith cotton made
the ma terial burn more slowly in the gun and the rate was still f urther ,

reduced by the ad di tion of the nitrates of potas s ium and barium The e x p lo .

1 S anfo rd , N i tr e - E x
p lo s i ves , 1 8 9 6, p . 1 73 .
2 Eng . P a t . 90 0 o f 1 8 64 .
 E X P L OSIVE S

s i v e w a s s t ill t oo v iolen t for ri fles h o w ever but was foun d t o be quite suit a ble
, ,

for sho t guns The Aus t ri an righ t s t o Schul tze s inven t ion w ere ac quired
-
.
’

b y a fi r m ca lled Vo lkmann s K K pri v C o llo di nf a b r iks Ge sellschaf t H P e r

'

. . . .
,

n rc e a n d Co Volkmann t o o k ou t Au s t ri an pa t en t s in 1 8 70 and 1 8 71 w hi c h
.
,

w ere kep t s e c re t a t t he t ime bu t Gu t t mann obtaine d copies of them and pub

lis h e d t ran s la t ions in hi s 7 ev e nly l t a r s P ro g res s i n E x p lo s ir es

'
’
-
.

From t he s e i t i s seen t ha t Vo lkmann h a d made the fur t her s t ep of

par t ly gela t ini zing t he gra ins b y t rea t in g t hem w i t h a mixtur e of ether and
alc ohol w hereby t he e x plo s ion w oul d be restrained s t ill more Thi s powder
, .

w a s ma d e un d er t he name of C o ll o di n from 1 8 72 t o 1 8 75 but then the Au strian ,

Governmen t s t opped t he manufac t ure on t he ground t hat it wa s an inf ri nge

ment of t he ir g rmp o w de r monopoly The ni t ro li gni n made as descri b ed by .
-

Vol kmann mus t have be en decidedl y impure a n d t herefore un s t able and , .

di ffic u l t ies w ere no doubt exp eri enced in ob t aini ng uni form results .

A c ompany w a s formed in E nglan d in 1 8 68 t o w ork Schul tze s invention

'

and a fac t ory w a s e s t ab li s hed a t Ey e w or t h in t he Ne w Forest in 1 8 69 and .

, ,

t his af t er a t ime achi e v ed grea t su c c ess af t er t he metho d s h a d be en altered by

Griffi t h s B y 1 8 8 1 Sch u l t ze p o w der had be c o me so popul ar wi t h sport smen
.

o n a c c o u n t of t he li ght rec o il and absence of smoke as c o mpared w ith black

po w der t ha t t he London gun makers found irk s ome the rest ri c t ions upon the
,
-

quan t iti es t he y w ere all o w ed t o s t ore The manufac t urers of t h is powder .

ha v e modi fied t heir me t hods fr o m t ime t o t ime t o meet the demands of sport s
men and t o keep abrea s t of t he general ad v ance in the technology of e x p lo
s iv e s s o t ha t t he S c h u l t ze po w ders are s t il l amongs t t he
. bes t In 1 8 8 3 .

Schul t ze s t art ed a fac t ory in part nership w i t h Vol t z and Lich t enberger a t
He t zba c h in He sse Darms t adt and po w der i s s t ill made there under Sch u ltze s
'

-
,

paten t s .
l

E 0
. . po w der
The nex t successfu l s mokeless po w der w a s i nven t ed at t he w ork s of
1 88 2.
th e E xplosives C o mpany a t S t owmarket w hich formerly belonged to Th os , .

P ren t ice a n d Co I t w a s pro t ec t e d by pa t en t No 61 9 t aken out in 1 8 8 2 by

. .
,

F Reid and D Johnson Thi s w a s c a lle d E C Po w der (Ex p lo s iv e s

. . . . .

Company ) and c ons is t e d o f ni t r o co t t on mi xed wi t h t he ni t ra t es of potassium

,
-

and bari um w i t h t he addi t i o n o f colouring ma t t er and small quan t ities of other -

organi c compo u n d s I t w a s ma d e in t o grains w hi ch w ere hardened by bein g

.

par t iall y gela t ini ze d b y me a ns o f a s o l v en t e t her alcoh o l A separa t e c om ,

-
.

pan y w a s formed to w ork t he inven t ion a n d a fac t o ry w a s s t art ed at Gre en

S t ree t Green near Dart ford in Ken t T his i s st ill in exi stence and E C
, , .
, . .

P o w der con t inues to be much u sed .

For u s e in ri fled fire arm s t hese po w ders are too quic k For this purpose
-
.

p o w ders .
i t ha s b een f o und nece s sary t o de s t r o y en t irely t he struc t ure of th e origi nal
cell ul ose b y t h o roughl y gela t ini z ing it The fir st to produce a good smokeles s .

1
A Vo ig t H t ll u ng dU S p reng l o fi c i
. , e rs e
p 1 16
’
s , .
, . .
 P ROG RE SS OF E X P L OSIV E S 49

rifle po w der w a s the Fren c h engineer Vi eille w o rking on behalf of the French ,

Government in 1 8 8 4 He incorporated the nitro cotton w ith ether alcohol

.
- -

in a machi ne such as is used for kneading bread The resulting paste w a s .

rolled out into thin sheets and cut into small squares and dried The powder .

was called P oudre B after General Boulanger In 1 8 8 9 a gelatini zed ni tro

, .

cellul ose flake powder wa s i ntrodu c e d in Germany 1 In 1 8 8 8 Nobel invented .

a powder called Balli stite consisting of a nitro cotton of low nitration gela ,
-

tiniz e d with ni tro glycerine and in the same year an E ngli sh committee
-
,

adopted Cordi te a mi x ture of highly nitrate d gun cotton nitro glycerine and
,
-
,
-

vaseli ne (mineral j elly ) gelatinized by means of acetone A nitro glycerine

, .
-

powder of the cor di te type was adopted in Austria Hungary in -

E very nation now uses propellants consisting principally of gelatinized

nitro cotton either by itself or mi x ed with nitro glycerine These gelatini zed
- —
.

powders when suitably ignited in the gun burn from the surface inwards ,

consequently the time of explosion can be increased by maki ng the individual

pieces of explosive bigger Without altering the composition powders can be .

produced suitable for every sort of ri fled fi r e arm from a pistol to a 1 4 inch - -

gun .

P icric acid has been used for a long time as a dye and was in fact the fir st ,
Picric

artificial dye to be di scovered for its formation was ob served in 1 771 by ,

Woulf e by the action of nitric acid on silk Laurent was the first to make .

it in 1 8 43 by the ni tration of phenol and di nitrophenol and to rec ogni ze th at

it i s tri ni trophenol The fact that picric acid combines with metals and bases
.

to f orm explosive picrates has also been known fo r a long time and when its ,

manufacture fr om phen ol had reduced its price m any mixtures contain in g

them were proposed P icric acid also was added to explosives as a c ombust
.

ible constituent None o f these mixtures were u sed to any great extent
.
,

however In 1 8 71 Sprengel demonstrated that picric acid by itsel f could be

.

detonated by means of fulminate 3 but thi s also led to no practical result ,

until E Tur pin i n 1 8 8 5 pointed out the great advantages of us ing picri c acid
.

for fil ling shell } in c onsequence of its stability in sensitiveness and vi olence ,

.

Thi s was adopted by the French Government under the name of Meli ni te .

Other high explosives are mostly too sensitive to u se in shell they are li able to
explode i n the bore of the gun from the shock of di scharge For this reason .

gunpo w der only was previously used and it sti ll form s the bursting charge ,

of shrapnel shell and other sorts which only require a moderate disruptive

1
Vo n N e y man J , a h r b u ch der A r me e u nd fl/I a r in e , D e c
'
. 1 9 14, S S . 1 9 1 5, p . 1 45 .

G r o to u s ki , 111 m
. Ar t .
-
u nd G e n i e w e s en th r oug hSS
1 9 1 4, p . .
, . 38 6 .

3
Eng . Pa t . 2642 o f 1 8 71 ; J . C h e m S o c , 1 8 73, p 79 6
. . . .

4
F re n ch Pa t . of Fe b . 7, 1 8 8 5, w i h t a
d d i io s O c t t n . 1 7, 1 8 8 5, a nd Se p t . 1,
1 8 92 . En g . P a t . o f 1885 . G erm . Pa t . o f Jan . 1 2, 1 8 8 6 .

V OL . I .
 E X P L OSI V E S

power P i c ri c a c id however is nearly as in s ensi t ive as blac k powder and

.
, ,

c a n t herefore be u sed wi th s afe t y for she ll In fact i t requ ires a very power
.

ful de t o na t ing primer to ensure complete de t ona t ion Wi t h vari ou s mo difi c a .

ti on s pi c r ic aci d w a s a d op t e d in a h ost every c ountry for t his purpose I t .

h a s t he di s ad v antage h o w ever tha t it re ad il y form s picrates if it comes in

, ,

c on t ac t w i t h me t als or ea r t hy ma t erials a n d t hese picrate s are much more

,

sensi t ive t han picri c acid I ts mel t ing point also i s inconveni ently high
. .

In hi s pa t en t s Turpin p o inted o u t t hat t he sensi t iveness c oul d be reduce d

s t i ll f u r t her b y c o mpres sion o r by mi x ing the pic ric aci d w ith hea v y oi ls or
,

wi t h c oll odi o n
. At first coll o di o n w a s used in t hi s way but later the acid h a s ,

genera lly been use d by itse lf either in compressed block s or melte d a nd cast
,

d irec t ly in t o t he shell . In 1 9 1 1 t he Civil Court in P aris granted T u rp in

fran c s in c ompensa t i o n because he had not been permi tted to u t ili ze hi s inv e n
t i o n t o h is o n p r o fi t
w 1
In 1 8 8 8 pic ri c acid w a s adopted by the Ge rman
.

Army bo t h for fi lling shell and fo r mili tary blastin g and about t he same date ,

shell w ere fil led in England w ith molten pic ri c acid under t he nam e of Lyd di t e ,

derived fr o m Ly dd the place where the exper iments w ere carried out
, .

t
Tro y l. I n 1 90 4 t he Germans commenced to use trinitrotoluene other w ise trotyl , ,
'
u

ins t ead as i t is free from the di sadvantages of picric acid r e fer r e d t o a b o v e

. .

T hi s is n o w used v ery largely fo r high explosive shell and is also ofte n mix ed .

w i t h o t her substances to form complex e x p l osives .

1
S ee S S
. .
, 1 9 1 2, p . 57
.
 P A RT I I

BL A C K P OW D E R
 C H AP TE R I V

MANUFACTURE OF SAL TPETRE

N it re d e p o it Fren c h alt p e t r i ndu t ry A ti fi cial n it re b e d E ng li h alt

s s s e s r s s s

p t re i n d u s t ry Fo r mat io n o f ni t ra t e s B e r t he lo t r e se ar c he B a c t e ria l a t i n
’
e s s c o

I nd ian s l t p t r e in d u t ry I nd ian re fi n e ry C hi li ni t ra t e d e p si t s
“
a e s Con o

ve r io n s al t p e t re Re fi n in g s al t p e t re Sal t p t re fro m t h e a t m ph r e
s e os e

SO far as is possible in the almost entire ab sence of all records an ac c ount h a s ,

been given in Chapter I of the fir st di scovery of saltpetre .

_
U ntil the middl e of the nineteenth century a ll saltpetre w a s obtained by Nitre dep o
dissolvi ng it from earth a n d deposits in cellars and caves a n d similar places ,

where it had formed naturall y In E urope there are very few localities where .

ni trate can accumulate in the soil to such an extent that a profit could be

m ade b v e x tracting it There is no prolonged dr y season during which

.

deposits can form withou t being washed away again Consequently salt .

petre could only accum u late in sheltered places such as cellars and stables , ,

especially those in which there was much nitrogenous matter undergoing

decomposition As it was of the utmost importance in every country to have
.

a suffi cient supply of saltpetre especially in time of war its production forme d
, ,

the subj ect of royal decrees and orders at an early date In France o fficers F ench 8 .
,
r

p et e ind
(s a lp étr ier s c o mmissio n és ) were appointed in 1 540 to search fo r and extract
r

saltpetre and no doubt the industry was in e xistence some time before
,
1
This .

e dict was c onfir med and renewed in 1 572 and again whenever France was ,

waging a serious war The saltpetre workers operated on the earth of stables
.
,

sheep pens cattle sheds cellars and pigeon houses and on the plaster and
-
,
-
,
-
,

rubbish removed when h ouses were pulled down They had the right to .

gather material every w here w ith scrapers and brushes in the houses with
, ,

picks and shovels in places not inhabite d No buil di ng or w a ll could be p u lled .

do w n unt il notice had been given to the saltpetre workers who stated which ,

parts they wanted reserve d .

I n the eighteenth century the saltpetre workers in France received m any

ad di tional privi leges For in stance they could set up their vats a n d o ther
.
,

plant in pub lic halls private courtyards or wherever they th ought fit The
,
.

1
rh
Be t e lo t , Su r l a F o r ce de s Al a tze re s ex p lo s iv es , 1 8 8 3, v o l. i .
, p . 3 45 cl s eq .

53
 E XP L OSIV E S

l o cal au t hori t ies h a d to supply t he w o o d requi red for heating and provi de ,

c arts for t ranspor t in g t he plan t and t he sal t petre to t he refin ery As a rule .

e a c h lo c a lit v was visited once ever y three years .

t
ni r e b e ds .
Sal t pe t re w a s als o ob t ained from artificial nitre be d s c onsist ing of earth -
,

mi xed wi t h ani mal and vegetable matters ashes refuse of b uildings li me and , , ,

marl This w a s all pla c e d in a large barn and c ollecte d in heaps mi xed with
.
,

t wigs a n d in t erse c ted w i t h h oles t o a ll ow access of t he air I t was tur ned .

over also from t ime to t ime and w atered wi t h uri ne Nitrate graduall y formed .

in t he mass and w a s ex t rac t e d wi t h water There w ere many m o di fica tions .

of this process ad o p t e d in d iff erent places .

In t he reign o f Loui s XIII (1 61 0 t o 1 643 ) t he ann ual crop of sal t pe t re

amoun t ed to lb b u t i t gradua lly di min i shed in the eighteenth
.
,
.

c en t ury largely on ac c ount of t he s t rong obj ection the people nat u rall y had

to t he presence of sal t petre workers in their h ouses and doma ins In 1 775 .

t he quan t i ty had fallen to lb and half the a n nual requi rement was
.
,

importe d from India If it had not been for the many privileges the nitrate
.

w orkers enj oye d t he home produc t c ould no t have competed at all wi t h t ha t

,

impor t ed from In di a I n 1 78 9 t he year of th e fall of the Bas t ille a g rea t e ff ort

.
, ,

w a s ma d e ho w ever t o revi v e the in d us t ry and

. 1b were obtained ,
. .

In 1 79 1 h o w ever t he Na t ional Assembl y propose d t o aboli sh t he pri vileges

, ,

of t he sal tp e t re w orkers but w a r broke out the harbours of France w ere

.
,

blocka ded a n d i t became necessary t o produce i n t he coun t ry all the saltpetre

,

fo r t he po w der required The recen t increase of chemical knowledge and t he

.

hear ty c o opera t ion of t he grea t er part of t he population made it possible to

-

pro d uce 1 6 lb in a single year a nd . in t he nex t ,

The w hole .

organi za t ion w a s place d under t he c on t rol of the departmen t of P ou dr es

e t s a l é tr e s
p w hi c h still c on t inues t o reg u la t e mat t ers c oncerning e x pl o sives
, .

When p ea c e w a s fi nally r e es t abli she d the rene w ed c o mpe t i t i o n o f In di an

-
,

salt pe t re deal t a severe blo w t o t he indus t ry in France and in 1 8 40 t he boun t ie s ,

w ere ab o lished bu t i t s t ruggled on u n t il the exploita t ion of t he so di um ni t rate

,

d eposi t s in Chi le and t he po t ash d eposi t s in Ge rmany in t he sec ond half of

t he ni nete en t h cen t ury led to th e produc t ion of ar t ificial sal t pe t re The .

conse quen t reduc t ion of price almos t en t irely kil led the French sal t pe tre
ind ustry a n d in 1 8 70 when a scien t ifi c c ommi t t ee w a s engaged in providing
, ,

P aris w i t h all stores nece s sary fo r i t s d efence Ber t helo t c oul d find onl y on e .

or t wo sma ll producers in Champagne .

t
E ng lis h s al U n t il t he si xt een t h cen t ury sal t pe t re s eems mos t ly t o have been imported
t t
p e r e indus ry into E ngland ru u c h of it c o ming fr o m Spain bu t in 1 5 1 5 Hans \Vo lf a for
, , ,

eigner was appoin t ed to be one of t he King s gunpo w der makers in the T o wer
'

o f Lon d o n and else w here He was t o go from sh ire t o s hire t o find a place
.

where t here i s s tu ff t o make saltpe tre o f and w here he and his laborers
'

”
sha ll labor di g o r b reak in any gr o un d
, He i s t o make c o mpensa t i on t o
.
 MANU FACT URE OF SAL T P E T RE 55

its o w ners A nd in 1 53 1 Thomas a Le e o ne of the King s gunners w a s

’

.
, ,

appointe d pr incipal searcher a n d maker of g u npo w der .

1

As already stated gunpo w der w a s onl y manufacture d in E nglan d on a

small scale until the sec on d half of th e sixteenth century when George E velyn ,

started mills on a c omparatively large scale Consequentl y there w a s li ttle .

di fficulty before that time in obtaini ng suffi cient saltpetre but then it became ,

necessary to grant the saltpetre men special pri vi leges for digging up the floors
of stables dovec ot s and e v en private d w e llings a n d t he ki n gd o m was di vided
, ,

into a number of areas i n which the c ollection a n d working of the saltpetre

—

was assigned to various people In 1 561 Queen Eli zabeth grante d Gerar d .

H o m ic k a Dutchman £ 50 0 (or £ 30 0 ) for teaching t w o of her subj ects h ow

'

, ,

t o make saltpetre 2
In 1 58 8 she granted a monopoly for gathe ri ng and w o rk
.

ing saltpetre to George E velyn Richard H ills and John E velyn The monopoly , .

exte nded over the w hole of t he South of E ngland and the Midl an d s except ,

the City of Lon d on and tw o miles outside it In 1 5 9 6Rober t E vel yn ac qui r e d .

the rights in London and “ e s tmi ns te r from the licensees there As a rul e
I

.
,

however the E velyns did not work sal t petre themselves but b ought it from
, ,

the saltpetre men .

In the reign of Charles I there w a s c onsi derable friction between the salt
petre men and the publi c but i t was probably due more t o the weakness of
,

th e Cr own than to any real diffic ul t y in obtaini ng in E ngland t he quantity of

saltpetre require d v iz 240 lasts per annum ,
There w a s also compe t i t ion
. .

between the saltpetre men and t he soap boil ers for w oo d ashes whi ch w ere -
,

th en practically the only source of potash and w ere requir ed for the conver
sion of sodi um ni trate int o the p o tassium c o mpou nd In 1 8 34 the Lords of .

the Admi ralty gave orders t o t he Governor and Compan y of soap boilers t ha t -

t he saltpetre men w ere t o have the pre emp t ion of wood ashes on the g roun d -
,

that saltpetre w a s a c ommodi t y of such necessary use for t he King and publi c
that it ought to be preferred before t he ma king o f soap 3
The monopoly of .

saltpetre was aboli she d in 1 64 1 at t he same time as the monopoly of gunp o w der .

It w a s revived for a t ime af t er t he Res t ora t i o n but ma n uf a c tm e t hen w as ,

'

on a c onsi derably larger scale .

The E ast In di a Company then in i t s infanc y imp o r t ed In di an sal t pe t re

, ,

into E ngland as ear ly as 1 625 a n d set up a po w der m ill i n I l in ds o r F o res t

'

w hi ch ho w ever was stoppe d on the ground t ha t i t in t erfere d wi th the Ki ng s

’

, ,

deer Ne x t year the C o mpany received a li c ense to erect mill s in Surre y

. ,

Kent a n d Sussex At thi s t ime its imp o r t a t i o ns w ere on a sma ll scale bu t

. ,

w hen its charter was rene w ed in 1 69 3 i t w a s stipul a t e d t hat 50 0 t o ns o f sal t pe t re

shoul d b e suppli e d every year t o t he Or dnance E ver s ince t hen In di an sal t . .

petre has been u sed very largely in E nglan d fo r the manufacture o f gunp o w der .

1 Ex p I nd 21 0
B r it . Ex p . I nd . ,
p . 18 5 . B r it . . .
pp . .

3
B r it . Ex p . 1 nd .
, 269 .
 EXP L OS I VE S

Whence c ome t hese large quan t i t ies of ni t ra t es ? The ni t r ogen o f the

a t m o sphere does no t form che mical c om p o un d at all rea d ily U n d er t he s .

influence of ligh t ning and hi gh t ensio n elec t rici t y gene r ally small quantities
, ,

of ni t ric ac id are formed and these are ca r r ied down by ra in into the soil and
r endered available for plan t life Bu t La wes a nd Gil be rt in t he ir researches
.

a t Ro t h a ms te d fo u nd t ha t t he amount of ni t rogen removed wi t h t he crops

wa s more t han the t otal sum of t ha t added as manur e and brough t do w n by
t he rain toge t her wi t h t he loss of ni trogen from t he soil No plan t s can grow .

w i t hou t absorbing ni t rogen c ompoun d from t he soil a n d when ani mal s

a n d vege t a ble ma t t ers dec ompose a po r tio n of t he c omb ined ni t rogen is lib er
,

a t ed a s ni t rogen gas bu t in spi t e of t h i s t ead y loss t here is no in di ca t ion t hat

,
s

the s urfac e of t he ear t h a s a w h ole is bec omi ng poorer in combined nitrogen .

Ber t helo t inve s t iga t ed t hi s ma t t er abou t 1 8 76 and di scovered t ha t ni t rogen

and oxygen a lso c omb ine d un d er t he influence of elec tricity of qui t e lo w
t ension su c h as t ha t v ie lde d b y tw o or t hree elec t r ic cells alth ough only very ,

slo w l y and moreover t ha t in t he presence of carbohydrates such a s dex t r ine

,

t he c ombina t ion w a s c o n s ide r a b lv more rapid 1

Al t hough t he quan t i t ies .

t hus ob t ained in small labora t ory experiments only amoun ted to a fe w milli
grammes in several mon t hs y e t as t here are al w ays di fferences of poten t ial of
,

t hi s o r d er over t he w h ole surface of t he globe bet w een t he earth and t he air

abo v e i t he c onsidered t hat t hi s phenomenon w a s sufficient t o acc oun t for
a ll t he ni t ra t es and o t her c ompoun d s of nitrogen tha t are formed .

B ac teria l Since t hen ho w ever i t ha s bee n foun d t ha t t hi s is by no means the only

,
.

cause of t he fo r ma t ion of ni t rogen compound from t he nitrogen of t he a t m o s

s phe r e
. There a re bac t e ri a in t he soil w hi ch c an t a ke up ni t rogen from t he
air and cause i t t o c ombine w i t h o t her elemen t s to form ni t ra t e s a n d more
c omplex bodi es s u c h a s albu minoids Some of t hese such a s Az o b a c te r iu m
.
,

C hr o o c oc c u m Be ij e r i nc k can li ve and ac t free ly in t he soil

,
o t hers seem only
t o e xi s t in t he n odules t ha t are found on t he roo t s of cert ain sor t s of plan t s .

The Bac t e r ium Ra dicic ola i s perhaps t he m o s t import an t of t hese i t is found

on t he roo t s of t he legu mi nos ae (b eans p eas ) and renders i t possible for t hese
, ,

crops t o gro w on o t her wi s e s t erile soil w hi ch aft erwards i s able to suppor t,

o t her crops Some o t her plan t s such as t he alder t ree have similar n od ul es
.

on t heir roo t s There are some soil bac t eria also w hich c onvert ni t rate s
. .

in t o ni t ri t es o t hers carry ou t t he reverse change o t hers again li bera t e ni t ro

, ,

gen from ni t ra t es or ni t ri t e s and se v eral of t hese ac t ions may b e going on

,

simul t aneou ly in t he soil

s .

B a cterial a c t ion proc ee d s m os t rapi dl y in a w a rm mois t cli mate like t hat

of Bengal The accumula t ion o f ni t ra t e t o s uch a n ex t en t t ha t i t can readi l y
.

b e c o llec t ed in large quan t i t ies als o requir es t ha t t he r e sh a ll b e regul ar se a sons

,

of t he vear when li t t le or no rain falls In t hi s re s pect Bengal and m o s t o t her

.
,

S u la F ce d s J I a t é re Ex p l i l i c ha p vi
'

r or e 18 83
r s os ve s , ,
vo . .
, . .
 MAN U FACTU RE OF SALT PE T RE
parts of Indi a satisfy the conditi ons It w a s found by Leather that at P usa .

i n Behar the nitrification takes place m ostly in t he t op 6 or 1 2 inches of soil

and principally at the c ommencement of the rainy season There is more .
.

ni trate in fallow soil than i n that that i s c overed with crops The mean .

quantity that w a s w ashed out of the soil into the drain gauges w a s 70 lb of .

nitric ni trogen per acre from fallo w soil a n d 1 3 lb from croppe d soil 1
Hea d . .

de n has foun d that in Colorado s o il s are often rendered s t erile by t he presence

of too much saltpetre w hich at times amounts t o 6 per cent of the soil It ,
. .

is forme d by azobacte r 2
.

Bihar is the prin cipal seat of the saltpetre in dus t ry in In di a but c onsider ,
t
I ndi a n s a l
pe trej ndustr :
able quanti t ies also c ome from the U nite d P rovinces and t he P unj ab and ,

sma ller am oun t s from o t her parts of In di a a n d from Burma E x cep t what .

is c onsumed in the c ountry the greater part i s exporte d from Calcutta Fif t y , .

or sixty years ago the average quantity e x p o rted was o v er , tons per
annum now it i s ,
to In th e places w here th e nitrou s ear t h
i s c ollected t he natur al vegetation i s scan t as the soil in many cases is too salt ,

for crops t o grow even dur ing the rains It i s obtained in a n d aroun d exi sting .

village sites and on the mu d w alls of h ouses and c o w she d s In the rain y -
.

season last ing from June to October the pr o cess of ni tri fication goes on in t he
, ,

w arm moi st soil assisted by the a ddi t ion of ni t rogenou s refuse

,
The foll ow .

ing account by R W Bingham 3 gi v es a clear picture of the in dustry i n the

. .

last cen t ury

It i s a ll made by a peculiar caste ca lled nun i a b and so far a s my e x p e r i ,
’
,

ence sho w s i s principal l y in the hands of ma h a j u n s w h o make yearly

’

, ,

advances charging 1 2 per cent for the same The nuni a h s are a tolerably
,
. .

safe class compare d w i t h the ordi nary riot (peasant ) t o deal with and pay
, , ,

the zemi ndars (lan d owners ) a comparatively large price (if measured by
‘ ’

the bigah for the old w a lls and old sites in whi ch they revel The supply .

of saltpetre from these old sites appears to be practically in exh au stible for
.

w e fi n d the nuni a b very busy makin g up his piles j ust after the setting in
‘

of t he rains Thi s earth he e x poses to the sun and rain and takes care by
.
, ,

erecting w a lls et c that the preci ou s stuff i s not wasted away A casual
, .
,
.

vi sitor woul d not be able t o understand what he is af t er but w hen the hot ,
.

suns of Ap ril Ma y and June c ome on then himself a n d hi s fa mily boil mer r ilv
, ,

away and eli minate saltpetre and salt from this apparen t ly useless soil Then
,
.

the mahaj an i s on the look out and secures the saltpetre a s it i s ma de a n d -

,

carries it to his o w n re fi nery for fin al manipulation w hile t he sal t w hich i s

1 J . “ Z Le t ahr e , J l em . D ep . A g r i n I nd ia
. ,
v o l. ii .
,
no . 2. J a n . 1 9 12 .

2 P . H ea dd e n , C o lo ra d o Ag r C o l E x p l
. . . S ta ti n o , B u lle ti n s 1 55, 1 60 . t hr u gh o

N a tu r e 1 9 1 1 p 3 64
, J I nd E n g C h e m 1 9 14 p 5 8 6
, . . . . . .
, , . .

3 J
ou r A g ri cu ltu r a l a nd H o r ti c u ltu r a l S o c x ii p
. .
, .
,
. 1 0 7, o ld se ri es ; D ie t . E co n o mic
P r o d u c ts o f I ndia , S . 68 6, v o l. V 1. pa rt ii .
p . 4 37 .
58 EX P L OSIVE S

al w ay s bi t t er and I shoul d sa y un wh olesome un der t he name of khari nimuk

, ,

is sold to t he lowes t cla sses of the communi ty at a cheap ra t e The bu iness .

s

mus t be a profi t able one as t he la rge bank ers of G h a zip o r e P atna and Benares ,

a re al w a y s re a d v to go in t o the t r a de and to ad va nce money to respon ible s

mi ddlemen . So me t imes t hese men e xperience c on s iderable trouble in

r ec o v e r i ng t he ir a d vances bu t in that case t hey quietly walk o ff wi th t he
,

FIG . 3 . Pe rco l to
a rs fo r E x t ra c t in g I nd ia n C ru d e Sa l pe t t re .

b ulloc ks of t he nuniab w h o never dreams of maki n g a c ompla int bu t

be gs or b o r ro w s from hi s c omrad es and f riends t ill he has go t money enough t o
release t hem b y pa yi ng bac k principal a n d in t e r es t w ell kn o wi ng t hat he
wi ll ge t no m ore a d vances a n d wi ll besides b e pu t out of cas t e by hi s cas te
.
, ,

ma t es if he does no t a t all even t s p a y t he o ri ginal ad vance If on the c on

.
,
. .

t r a r y h e makes more sa lt pe t r e than wi ll c over his a dvan c e a n d he ha s no

, ,

p ar t ic ul a r c e remony going on he wi ll c l andes

,
t inely sell hi s partially refin ed
sa l t pe t re t o o t her p e t t y purchase rs a n d ge t dru nk while the m one y las ts and
, ,
 MANUFACT U RE OF SALT P ET RE 59

a sk contemptuously What am I a poor man that I sho ul d work ?

, , The
trade is too hazardous a one and the petty advances spread over too wide
,

an extent of country to make it worth the wh ile of E ur opeans w ith capital

,

to attend to in consequence it is almost wholly in the hands of the large

houses ab ove named (who a r e connected w ith Calcutta native firms and who
in turn have their small br anches in every petty town in the di strict ) .

The industry i s conducted on the same lines now as then except that it ,

( FI G . 4 . E vap o ra t in g L iq uo r fr o m Pe r c o la t o r .

is not as remunerative as it used to be Hooper made analyses of a large .

'
l
1

number of samples of the earth c ollected b y th e n u n ia h s the amount of

nitrates in them varied from 1 to 27 per cen t but as a general rule they con .
,

tain 3 to 5 per cent also several per cent of sodi um chlori de and sul phate A
.
,
.
.

des cription of the process of extraction has been given by Leather and Mukerj i 2
.

1
A gr ic u ltu r a l L ed ger 1 9 0 5 N o 3
, , . .

2
B u lle ti n N o 24 o f t h e Agric ul t ur a l Re s e ar c h I n s t it u t e P u s a
. , , 19 1 1 S S
. . 1 9 12, 1 1 6

a nd 1 36.
60 E XPL OSI VE S

The n u n ia h buil d s an ear t hen changi er call e d the kuri a or kothi

w i t h w e t mu d which is all o w e d to dry
, Thi s chamber (s ee Fi g 3) has either . .

c ircular w alls s o me 5 or 6 fee t i n diam eter or oblong wall s and a floor w hich , ,

s l o pe s s lightly from ba c k to fron t In the front wall i s a h ole at the level of

.

the b e d w hich allows the ni t rate liqu o r to drain away into a pot Above the
, .

b o t t o m o f t hi s ear t hen chamber a fal s e bott o m i s laid consisting of bamboos ,

a n d mat t ing pla c ed o n a fe w l o o se b ri c ks The nitrate earth is filled in on .

t hi s wi t h great care St o nes e t c a r e removed fr o m it as far as possible and

.
,
.
, ,

i t is pu t in s ligh t ly moi s t a n d tro dden d own so as to leave no channels thr o ugh ,

w hi c h t he w ater w o ul d run t o o rapi d ly Wood ashes are generally mixed .

w i t h t he ear t h s o that t he p o t a s h in them may convert int o saltpetre the

.

ni t ra te s o f lime a n d magne s i a A small pie c e of m atting is place d over th e

.

to p o f t he ear t h a n d w a t er i s p o ure d on c autiou s ly The li quor that percolate s .

t hr o ugh fir s t i s fairly s t r o ng it i s transferred to shall o w earthenware or iron

ba s in s a nd evapora t e d d o w n (Fig 4) by means of a fire o f wood leaves or .
,

t w igs or in the P unj ab to sh a llow masonry trays in w hich the concentrati o n

,

t ake s pla c e t hrough the ac t ion o f the very dry air a n d the heat of th e sun .

The w eak liqu o r th at perc o lates t hr o ugh afterwards is thrown on to a heap ,

o f alrea d y extra c te d ear t h where it evaporates : thi s earth is afterwar d s

,

e x tra c t e d again The s trong liqu o r is boile d do wn u ntil crystals begin to

.

appear a n d then is all o w ed to c o o l ; t he c rystals are then fished out fresh

, ,

liqu o r is a dde d to the m other li qu o r and the c oncentrati o n is c arried out as

bef o re The c o mp o sition of t he c ru de saltpetre thu s pr o duce d varies c on
.

s i d erably Ho o per gives t he analysi s of fi fty fi v e samples and of these the

.
-
,

f o ll o w ing ha v e been s ele c te d by Leather as being typi c al

Fa r u kh a b ad O ka r a
Mo z a f Bu rb an

fe r p o r c pu ra
I

Po ta iu m
ss ni t rat e

lc i u m
‘
( a n it r a t e

Ma g n e s iu mn it ra t e

S d iu m h l r id
o c o e

S di u m s u lp ha t
o e

I n lu b l ma t t
so e er

No at t empt is ma de to s eparate th e sod ium chl o ri de at thi s s tage b e cau se

 MAN U FACT U RE OF SAL T P E T RE
there is an ex cise du t y o n it a nd the salt depart ment only allows the recovery
,

to take place in the refinerie s w here a proper c ontrol can be kept Some of
, .

the cru de saltpetre is used as manure but the greater part g o es to the refin ery
, .

In the refinery the processes are very similar to those carried out by the
n u ni a h. There i s al w ay s a large heap of saltpetre ear t h whi c h is worked ,

over and over again the w eak li quors being always thro w n on to it This i s
, .

e x tracted in ko thia s but t he strong liquors are not evaporated down by

,

themselves ; c rude saltpetre i s dissolved in them at the b o iling point The -

.

quantity added i s such that the potassium nitrate i s all dissolved to form a
boiling saturated solution whereas the greater part of the s o dium chloride
,

remains un dissolved (s ee Table of Solubil ities on p 63 ) together with the .

insoluble matter The hot li quid i s a llowed to settle for a little while and
.
,

then r u n into wooden vats where it i s allowed to cool slowly and deposit
crystals of potassium nitrate The residue in the di ssolving tank is w ashed
.

with w ater to recover the saltpetre in it and the common salt may be purified
,

by di ssolving it in weak nitre li quor de c anting o ff and evaporating down

, .

The insoluble matter and all weak liquors are added to the heap of earth ,

whi ch stea dil y gro w s from year to year The mother liquor from the cr y s ta lli za
.

tion of the saltpetre i s als o added to it after it has been used three or four
tim es as it i s then too impure
,
.

The refined saltpetre i s in large crystals of a browni sh colour To purify .

it further and improve the c olour it is sometimes subj ected to a was hi ng

process it is put in sacks over w ooden tubs and cold water i s poured through
it Thi s of co urse di ssolves some of the p otassium nitrate as well as the
.

impurities and is consequently retur ned to the refinery process Leather

,
.

and Mukerj i give the following analyses of refined saltpetre before and after
washi ng

van B a kr a ma n

W a she d W a shed
w a she d w a s he d

°
93 '
15 °
15

Leather has designed a simple plant on m o re up to date lines to ca r ry - -

out the refining pr o c ess and i s endeavouring to get the In di an refiners to take
,

it up This consists o f a diss o lving vessel provided w ith a stirrer a filter in

.
,
 E X P L OSIVE S

which t he li quor i s ra pidl y fil te r e d at a high te mperat ure and a series of ,

coolers in w hi ch t he s a ltpet r e is ca used to crysta llize rapi dl y The c rysta ls .

are then fr ee d a s far as possible from the mother li quor in a centrifugal

ma c hin e Th e s altpetre produced h as a p urity of 90 to 9 3 per cent
. .

The pla in of Ta ma r u g a l in C hili is even more favourably situate d than

Bihar or Bengal It li es bet w ee n the An des and the c omparatively low Coast
.

H ills at a height of abou t 30 00 feet above the sea wi thin the tropics As a .

rul e the r e is very li t t le ra in there but about once in s ix or seven years the
,

pla in w hi ch i s about 45 mil es wide i s flooded

,
The plain slopes gently
,
.

t o w ards t he Coas t Hi ll s and as there i s no outlet for the wate r it coll ects there ,

and evapo r ate s and a ll the ni trate it has di ssolved from the entir e p lain
,

is deposi te d in a comparatively narrow area The entire produc t of the .

bacterial action upon many hun dreds of s quare miles for many centuries is
foun d in the Chi li ni trate beds As the soil conta ins so di um compo u nds
.

and c omparatively little potassium it is prin cipall y so di um ni trate that has

,

been de s p o s ited 1
.

The follo wi n g gives the resul ts of analysis of commercial Chili ni trate °

So d iu m t rat e
ni

P o t a s ium ni t rat e
s

So di um c hl o rid e
So di u m io dat e
P o ta s s ium c hl o ra t e
Ma gn e s iu m s ul p ha te
Ma gn e su m c hl o rid e
C alc ium s ul p ha te
I n s o lub le
\ Va t e r

During the Crimean War (1 8 54 the demand for saltpetre was so

great t ha t the e x isting sources of supply in E urope and In di a di d not suffice ,

and c onsiderable quantities were made from Chi li nitrate whi c h had been ,

supplied to E u rope in consta ntly inc r easing quantities since 1 8 30 The .

sa l t beds at S ta ssf ur t ho w ever did not commence to yi eld potassi um chloride

, ,

(Carnall ite ) until about 1 8 63 therefore other sour ces of p ota sh had to be
,

used to c onvert the so di um ni tra te from C hili in to the correspon di ng p o ta s

si u m salt The o n ly sources of p ota sh then ava ilable were kelp and the
.
,

ash of w ood e tc When the war was over saltpetre prepared in thi s way
, .
,

coul d no longer c ompete with the natur al product from India But shortly .

”
af terwards fresh so u rces of p ota sh w ere fo u nd i n suin t the dr ied sweat ,

of sheep whi ch is washed from the wool and in the cinder o f v inass e
, ,

1
See N t n J
ew o , . S oc . C h em. I nd .
, 190 0 ,
p . 40 8 .
 MANU FACTU RE OF SALT PE T RE
(Schl emp e ko hle ) hi ch i s obtain ed a s a b y product in th e re fi nin g of beet
,
w -

sugar l Vith the develop ment of the Stassfurt p ota sh industry these lost
.

their importa nce ho w ever .

Large quantities of potassium nitrate are no w made b y the interaction Conv ers io n”
of Chili nitrate and c ommercial chloride of p otash w hi ch is made by lixi viat ing ,
s al tp tr e
e .

”
“
carnalli te a double c hloride of p otassium and magnesium o cc urring in
, ,

im mense dep osit s near Stassf u rt in Germany In the heated and conc e ntrated .

mother li quor from a previ ous operation co mmercial so di um nitrate (about

95 per cent p u rity ) and p otassium chloride (not less than 8 0 per cent p u rity )
.
.

are dissolved the nitrate being in sli ght e x cess Of the four salts that mi ght
, .

be present in the solution thu s formed so di u m c hl oride has the least solu ,

b ili ty at a high temperatur e and p otassium ni trate the greatest (s ee Table

below ) At a low temperatur e p otassium ni trate has the lowest solubil ity
.
.

The figur es are of co u rse for p u re salts dissolved in di still ed wate r and the ,

presence of other substances in solution wo ul d alte r the solubili ties some

’

what but the figures given in the last two columns the solubili ties of so di um
, ,

chl oride and pota ssium nitrate in water whi ch is s imul ta neously saturate d
wi th both salts show that in thi s case the salts have li ttle effect upon one
,

another s solubility Consequently in the h o t c oncentrated solution of sodium

’
.

ni trate and potassium chloride most of the so di um c hl o r ide is precipita ted out
Na NO3 K CI Z K O3 N
N3 0 ] .

TAB LE or SO LU B I LI TI E S

G r a mm e m o ls .
p e r 10 00 g w a . t er

Te m pe r a t ur e On e sa l t o nl y p re s e n t

Na C l Na N 0 3

a
C l cu l a te d fr o m fi gur e in Seid ell s S o lu b il it ie s o f I n o g n ic a nd O g n ic S b t nce s
s
’
r a r a u s a ,

1 90 7. A gr a mm e m o l is t h e m
-
o l e
. cu”
l ar w e i g h t o f a s u b t an c e in gra m me To fin d s s.

t h e a c t ua l w e igh t o f t h e sa lt s dis s o l ve d b y 1 0 00 p a rt o f w a t er mul t ip ly t h e a b v fi gur s

s ,
o e e

b y t h e c o rre p ond in g m le cul a r w igh t f Na C l 58 5 K C l 74 6 N N O 3 8 5 1 K N O 3 - -

s o e s or , ,
a ,

1 0 1 -
1.
 E X P L OSIV E S

Th e u t so f th di ff r n t
l b ili ie s lt in t h p r
o n
e se f n an t h r h a v r
e e n t ly sa s e ese ce o o e o e e e ce

b n in v t iga t ed b y J
ee es Le a t h r n d J N Mu k r j i w h
. re ult d n t d iff r v ry
e a . . e , o se s s o o e e

r r o ve er tu h w v r t h un d th t
°

g t
ea ly f m t h ob A t te m p a b l w 30 C
. e y f a r es e o o e e . e o a a

s m ll p re po r t io n o f K C l i f m ed in a
a lut i n t urat ed w it h K NO n d N C l nd
s or so o sa 3 a a . a a

co rr po nd in g a mo ru t f lid N N O i d e p it e d At t mp r t u e a b o v 30 C n
es i o so a s
s os . e e a r s e
°
. o

th t h r h nd K C l i d e po it ed a n d N N 0 fo rmed in s lut i n nd t h t m pe rat ur

e o e a s s a 3
o o , a as e e e

ri t h q u nt it i o f t he e t
s es e a s s l i
esn c r rap y
id l l
a s ea se .

The li qui d is boiled for half an h o ur to complete t he rea c tion a s far as

p o s s ible t hen i t is run t hrough a fil t er in t o shallo w coo ling ta nks some more
,

w a t er may n o w be adde d w i t h ad v antage t o preven t s odium c hlo ride s eparating

ou t w i t h t he p otassium ni tra t e .

The s o lu t ion is kept st irred w hilst it c ools s o t hat the potassium nitrate ,

FI G . 5. Pl ant fo r Re fi n in g Sa l pe t t re a t Ab b e y .

may s epara t e i n s mall c r y s t al s w hi ch do no t contain so much m other li quor ,

as large one s The cr y s t als are drained and then w a s hed with the li quors
.

from the ne x t cry s t a lli zation Thi s is b es t done in a centrifugal machi ne a s .

,

t he quan t i t y o f w a s hing li quor is t hereby reduce d to a m inim um .

The c rude sal t pe t re t hu s ob t ained s till c o nta ins several per c en t of sodium .

chl o r i d e and abou t a half per c ent o f magne ium c hlo r ide I t is purified by . s .

di s s o lving i n t he w ashings of the purifie d salt allowing it to cry s t a lli ze and ,

w a s hi ng wi th w ater w hereby t he percentage of chloride i s reduced to 0 0 5

,

per c ent o r le s s and t he ma t erial is rendered practica lly free from a ll other
.
,

imp u rities F inall y it i s dr ied

. .

The s odi um chlori d e formed in the conver s ion is w a s hed on the filter wi th
li quors conta in ing graduall y di min ishing a mo i mts of nitrate until the solid ,

conta ins onl y 0 8 per cent or le s s This s altpetre salt t hen con ta in s about
-
. . .

1
dI e m f D p t f Ag ic u lt u e in I nd ia C h mi l S r i
. o e . o ol iii
r No 7 1 9 1 4 r .
, e ca e es ,
v . .
, .
, .
 MAN U FACT U RE OF SALT P E T RE
98 per cent of sodium chloride in the dry state It i s unsuitable for the
. .

manufacture of hydrochl o ric a c id beca u se thi s would be c ontaminated with ,

ni trous compounds and moreover the plant would be strongly attacked

, .

It i s therefore either sold to farmers to put on the land or use d in c opper

extractio n or o t her metallurgical processes .

Artificial or conversion saltpetre made as above is usually supplied ,

by the chemical works to the e xpl os ives fa c tory in su c h a state of purity that
no further purification i s necessary Natural saltpetre from In di a on the .

o ther hand always conta ins a considerable amount of impurity and requires

to be refi ned before use .

Although the quantity of black po w der made is still very considerable ,

it is not nearly so large as it w a s twenty years ago The black p o w der factories .

now being worked were a ll in exi stence at that ti me and they mostly have ,

large saltpetre refineries attached w h ich more than su ffice to refine all the ,

material that they requi re It has not been foun d w orth while to recon .

struct the refineries as they are still capable of turning out saltpetre of good
,

quali ty I t wo ul d nowadays be p ossible ho w ever to erect up to date plant

.
, ,
- -

that would save much space and some fuel and labo u r .

At Waltham Abbey as at some other English p owder factories In di an R fi ning e

m
, ,

a m a“
saltpetre is used exclusively The total quantity imported into E ngland .

every year i s howe v er only ,tons and the total consumption for maki ng
,

p o w der etc several times that amount The balance is made u p with
, .
, .

conversion saltpetre .

The method of refinin g st ill followed at W altham Abbey is as foll ows : W a lth a m
b ey m
The c rude or gro ugh saltpetre is di ssolved up in a large iron copper A ,

( Fig. which has a capacity of 50 0 gallons and is fitted with a perforated ,

false bottom whi c h prevents the saltpetre adhering to the vessel For each .

charge ab out 25 cwts of grough saltpetre are taken and 5 c w ts of crystals

, .
, .

recovered from li quors and 5 c w ts of crystals left in the crystalli zing cisterns
, . .

This is all di ssolved in about 28 0 gallons of the w ashi ngs of the purified salt
petre whi ch a lso c ontains a considerable amount of the salt The fire is li t
, .

under the copper a n d in about two hours the saltpetre is dissolved and the
,

liquid boili ng J ust before it boils a thi ck scum rises to the surface consisting
i
.

mostly o f impurities This i s skimmed o fi and the fa lse b ottom i s removed

c
.
,

and col d water i s added from time to time to induce fresh scum to form if it ,

will The fire is then wi thdrawn and the li qui d is allowed to settle for two
.

hours Then a hand pump is lowered into the copper and the li quid is pumped
.

into filters B where it p a sses through li nen cloth From here it runs to
,
.

shallow copper crystalli zing trough s 0 As it cools down the liquid is kep t .
,

stirred by a workm an in order to make the saltpetre separate in small crystals ,

and the saltpetre fl o ur as it form s is drawn up on to an inclined draini n g

platform D and from there is passed to a w ashing vat E After the tempera
,
.

V OL . I .
5
 E X P L OSIV E S

t ure has fall en to abou t 3 2 C (90 F ) t he s olution i s no longer s t irred and any
°
.
°
.

c r v s ta ls t ha t f o rm af t er t ha t are t reated as grough nitre .

W a s hing . The w a s hi ng va t E i s abou t 6 fee t long by 4 fee t wide by 3 feet 6 inches , ,

d eep a nd is fi t te d wi t h a false bo tto m made of wood w i t h small holes bored

,

in i t Belo w the false bottom is a plug which can be removed to all ow the
.

w ashing s t o flow a w ay .First the charge is w ashed with 70 gallons of wate r

s prin kle d o v er it by means o f a rose t he plug be ing left o u t so that the w ashi ngs
,

can d rain a w ay t o a li quor ta nk F Af t er drai ning half an hour the plug

.

is in s er t e d a n d t he s al t pe t re c overed w i th fresh water which afte r s tan di ng ,

ha lf an hour i s also allowe d t o dra in into F Finall y t he salt i s washed by .

s p r inkling w i t h 1 00 gall ons of w ate r the plug r e ma l mng out The saltpetre
, .

is no w a llo w ed t o drain a ll ni ght and is then rem oved to the s t ore house w here -

i t i s a llo w ed to dry sponta neou s ly In about t hree days the m oist u re has
.

fa llen t o 3 or 5 per cent .

Moth er li q uor .
The m o t her li quors and o ther impur e solutions are boiled down to about
a qua r te r o f t he ir origin al volume Any sc u m or deposit that forms during
.

the boilin g should be removed and w ate r then be added The solution i s .

n o w fil t e red and all owed to crysta lli ze The crysta ls are treated as grough
.

sa ltpe t re a n d the mother liquor return ed t o the evaporat ing pots .

The me t hods of re fi n ing adop ted in France Germany and o th er c ountries ,

a re sub s tantially t he same as that at Wal t ham Abbey A small proportion .

o f size is , ho w ever ofte n added in the refining c opper to assist the formation
,

of s c um .

P o t a s s ium ni t rate could also be made from the calcium nitrate produced
fro m a t mo s pheri c oxygen and nitrogen by processes such as t hat of Birkeland
a nd Ey d e as c ar r ied ou t a t Notodden but the calcium c hl oride ob t a ined as a
,

b y pr o du c t w ould be o f no value
-
Or the di lute ni t r i c acid obta ined in the
.
.

B irkeland Eyde pro c ess c o ul d be treate d wi t h li me s t o ne or c halk and p ota ss ium

-

c hlori d e
2R ( I 2H NO, 2KNO3 ( Cl 2 CC +H 0
‘ ‘
a 2 2 .

In this c a s e t he c arb o ni c a c id c ould be c oll e c te d and c ompres s ed into c ylinders

and s o ld U p t o t he pre s ent t hese m etho d s d o not appear to have been
.
,

ad o p t e d bu t ni t ri c acid and ammoni um ni t rate are being made on a very

,

large s cale e s pecially in Germany

,
1
.

1
S e c h p v iii
e a . .
 C H AP TE R V

MANUFACTURE OF CH ARCOAL AND SULPH UR

Char co al W o o d us e d D is t illa t io n C o mp o s it io n B ro w n char co al Sulp hur :

Sicilian s u lp hu B y p ro d u c t s ulp hu r L o ui iana s ul p hur

r : -
R e fi n in g s ul p hur
s

P ro p e r t ie s Fun c t io n o f s u lp hur s

AT one time the charcoal for black p owder was made almost exclusively from W ood
alder wood b ut later other soft woods w ere used and straw charcoal was also
-
, ,

introduced for the brown p owders for heavy ordnance Charcoal from soft .

woods is generally used especially for the better qualities of gunpowder

, ,

because it i s more easy to ignite In E ngland dog wood i s much used espec
.
-
,

ia lly for rapid burning p owders of small grain for larger p owders alder and ,

will ow In Germany alder and wi llow are the principal woods used ; in
.

Austria alder and hazel in Switzerland hazel in France black alder is used
, ,

for hi gh class powders for mining powders common white woods such a s
,

w hi te alder p oplar aspen birch and hazel ; in Spain the O leander yew
, , , , , ,

willow hemp stems and vine in Italy alm ost exclusively hemp stems
, , , .

Charcoal burnt in heap s or ki lns has not been used very largely for gun
powder since even the very earliest days for it was soon found that to produce ,

good powder it was necessary to select the wood careful ly and burn it very
uniformly It has therefore been heated in ovens or iron vessels and the
.
,

procedure of the present day does not di ffer materially from that of the
fourteenth century .

The wood should be cut in the spring as the sap in it at that time of the ,

year contains much less inorganic matter so that although the proportion ,

of sap i s larger yet the percentage of ash in the wood is much smaller More
,
.

over wood cut in the spring i s much more easily freed from its bark which
, ,

also contains a large proportion of ash The wood i s kept at least eighteen .

months and generally not less than three years to all ow the sap to dry out
, ,

of it and other changes to take place The practice varies considerably as .

regards protectin g the wood from rain at Dresden it is kep t in sheds at

Spandau in the open at Waltham Abbey also the wood is kept in the open ,

but the dog wood i s c overed with thatch whereas the alder and willow are
-
,
 E X P L OSIV E S

The w oo d is spli t if necessa r y in t o piec e s ab o u t 1 in c h t hi ck and t hese ,

a re plac ed in an i ron c y lin der abou t 2 fee t in di ame t er and 3 fee t 6 in c he s

long This c y li nder is t hen r aised by mea ns of suita ble t ackl e a nd place d
.

i n a furnace w hi ch is hea ted as uni formly a s possible

, The higher t he t em .

e ra t u re and t he longer t he hea t ing t he lower i s the percentage o f hydrogen

p ,

and o x ygen in t he c ha r coal a n d t he grea t er is its hardness and t he di ffi c ul t y

wi t h w hi c h i t i s igni t ed A t IVa l
.t h a m Abbey dog wo o d for R P G or N G l -
. . . . .

po w ders is he a t ed 4 ho u rs for ,
8 hours Alder and willo w for R L G 2 . . . .

a re hea t ed hours for R L G P and ris m Blac k 4 hours for P 6

.
4
P
.
1
. . .
3
,

hen t he t em p e ra t ure of th e wood atta ins abou t 28 0 C volatile pro duc t s °

'

U .

of d e c omposi t ion of t he wood come o ff plentif u lly These coul d be conden s ed .

b y mea ns of a suitable condenser and w orked up i nto aceta t e of li me a n d

,

wood spir i t The charcoal plan t of a powder mill is ho w ever on su c h a

.
, ,

sma ll scale a s c ompare d wi t h the fac to ries in whi ch charcoal i s produced for
me t a ll urgica l processes w i t h reco v ery of the b y product s tha t it i s not u s ually -
,

considered w or t h whil e to do thi s The vola t ile products are therefore simply
.

led in t o t he fur nac e by w hi ch t he wood is being heated and so some e x p e n di ,

tur e of fu el is sa v ed To enable t he gases and volatile products to escape

.

t he c y lin der h a s some holes bored in it a t one e n d and the furn ace i s provided ,

wi t h a pipe t o lead a w a y t hes e product s I Vh e n the carboni za tion has .

‘

p roce ed e d far enough the flame of the burnin g gas becomes blue The furnace
, .

is t hen o p en e d t he cylin der ta ken ou t by mea ns of the tackle and a fre sh

, ,

cylinder of w oo d pu t in before the furnace h as had time to cool The cylin d er .

t ha t has been taken ou t is placed insi d e a larger cylin der which has a cl o sely ,

fit t ing lid and is t here allo w ed t o cool I t is necessary tha t the cooling should
,
.

t a ke pla ce out of con t act of the a ir as o t herwi se the charcoal will c atc h fi re
.
, .

E v en w hen cold i t a t first absorbs large quantities of oxygen from the air ,

and in so doing may be c ome sufficien t ly ho t to catc h fi r e Therefore oxygen .

m ust onl y b e allo w ed g r adual access to the charcoal it shoul d not be ground
u n t il a w eek af t er i t h a s been b u rn t Before use it i s carefull y picked over
.

by hand to rem ove a n y that has not been properly bur nt as also any forei gn ,

ma t t e rs t hat have got in t o i t Charc o al intended for powders for ord nance
.

s h oul d be jet bl a ck in c olour ; its f r ac tur e sh oul d show a clear velve t like -

sur fa ce ; i t shoul d be light and sonorous w hen dropped on a hard surface ,

a n d so sof t that i t will not sc r atc h poli she d c opper The yi eld of such char
.
1
.

coal i s 28 to 30 per cent of t he dri ed w ood For small arm s a more sla c kl y
. .
-

bur n t charc oal ca n b e u sed and the yi eld may be as much a s 40 per cent
,
.

Such charcoal h a s a red di s h bro w n c olo u r w hich is percep t ible in the powder
-
,

un t il i t h a s been gla ze d wi t h graphi t e .

1
Trea tis e on S e r v ice E x
p lo s i ve s , 1 90 7, p . 10 .
 MAN UFACT URE OF C H A RC OAL AND SULP H UR

The composition of s o me typical charcoals i s sh o wn in the Table below 1

. C o mp os itil

Spani sh hemp charcoal i s u s u all y burnt in pits h o l di ng l tO 1 ton When z

‘

the carboni zation has procee ded far enough the pit i s covere d with a woollen
cloth on w hich earth i s placed This probably account s for the high p er .

centage of ash in the analysis below .

D e s c r ip io n t Ca r b o n H y d r o ge n O x y ge n

F r o m P P w d er \ Va lth a m Ab b e y
. o ,

Fr o m “ a lt h m Ab b e y
Y
a

Fr o m Ab b y e

Fr o m F G W lt ha m Ab b y
. .
, a e

Cu rti s n d H ar ve y Sp o r t in g
‘

s a ,

C u rt i a n d H ar v e y Min in g
’
s s ,

Sp a ni h H m p C h r c a l
s , e a o .

G erman Sp o r t ing P w d e r (B S ) o . . .

Au s t r ian C ann o n P o w d r (K ) e . .

A t r ian Sm ll Ar m P w d r
us a o e .

Rus i n P o w d e r
s a (F ) .

The char c oal fo r brown or co c oa p ow d er was made from rye straw -

B r o wn
\

\
m"
,

“ ato
whi c h was only carbonize d very sli ghtly 2
It w a s heate d only about half .

a n hour then taken out of the furnace The carb oni zati o n proceeded sp on
, .

ta n e o u s ly a little further and t hen the charcoal coole d The resul t was a sof t .

g
c harcoal c onta inin g a lar e per c entage of oxygen a n d hydrogen In the .

operation of pressing the p ow der this became a c oherent c olloi d w hi ch bound

the other constituents together to a dense imp ervious mass w hich burnt ,

comparatively slowly The c ocoa p owder gave the best balli stics in heavy .

or dnan c e of any bla c k p o w d er ever produced but it has now been entirely ,

displace d by smokeless p owders .

For cheap blast ing powder and p owder for s c a r ing bir d s a n d s upplying
natives of Afri c a etc charcoal of an inferior qua lity can be u s e d
, .
,
.

SULPH UR

S ulphur oc c urs native in many volcanic districts c sp e cia llv i n Sicily , ,

a n d un t il recent t imes practically the whole of t he w orl d s supply came from

’

there The sulphur in Sicily i s mi x ed w ith limest o ne t he ores containi ng

.
,

1
N ob le a nd Ab e l T r a n s Ro y S o c
, . . .
, 1 8 75 a nd 1 8 79 N o b le , A r ti lle r y a nd E x p lo s i ve s
,

1 90 6, p p . 1 27 129 . B . 8: S .
”
me a n s an a ly s is b y B l ms e n a nd Sc h is c h ko ff ,
K by
K ra o ly i , F
‘

b y Fe d e o w .

2
G ut t m nn a , i
’
ll a n u a cl u r e , v o l .
/ i .
, p . 90 ; C u n d ill a nd T h o m p s o n p 21 , . T r ea tis e on

S e r vi c e E pl i x os ve s , 1900 ,
p . 1 10
 '

Ex p L o s rv Es

usua lly from 20 to 40 per ce n t of sulp hur Formerly the sulphur wa s rec c y
. .

ered b v t he was te ful cal c aroni pr o cess The ore was pil ed in a la rge hea p .

and c o v er ed over wi t h mois tened ash ex c ept for a sma ll opening C ombus t ion .

w a s s tar te d wi t h bur ni ng wood but th e comb ustion of part of the sul ph ur

,

provi ded most of t he necessary heat The sul phur melte d out and flo w ed .

do w n on to a p repared fi o o r Onl y about 60 p er cent of the sulphur in t he

. .

ore was recovered by thi s process and t he large quantiti es of s ul phur dioxi d e
,

set fre e w ere very inj ur ious to the sur roun di ng vegetation This method .

has been largely superseded by the introduction of r e cupera t ive furnaces

i nvente d by Gill a n d m odi fied by Sa nfi llip o About six large chambe rs are .

arrange d in a se ri es so t hat the hot gases from one ca n be m a de to hea t t he

next By t hi s process the recovery is about 8 0 per cent At t emp t s have
. .

been ma d e to introduce m ore efficient methods whereby practi ca lly t he whole

of t he sul phur co ul d be recovered by melting it out with hot brine or s te a m ,

or di s t ill ing it wi th superheate d stea m These methods have no t atta ined .

any great success however t he ob stacles being the ab sence of any local supply
, ,

of fu el and t he backwa r d state of the country The s ul phur is refin e d by .

di still ation the principal di stilleries being situate d in Marseilles S ome powder
, .

mills have small sulph ur refine r ies of their own as at Wal t ham Abbey for ,

instance .

Two sort s of sulp hur can be obtain e d by di still at ion : flowers and
stick sul phur The form er consists of mi nu te crystals w hi ch have bee n
.
,

d eposi t e d on the i nterior surface of a large chamber or dome i nto which

th e vapour s have been passed The flowers conta in a small per centa ge
.

of sulph u ric acid formed by the action of the air on the sulphur a nd ,

conse quently are not sui table for the man uf acture of exp losives S t ick .

sulphur on the oth er hand i s very p ure and o nly requi res to be ground
, ,
.

For the manufacture of s ul p hur ic acid elemen ta ry sulphur is but li t t le

used now a s i t pays be t te r to roast various ores in w hi ch i t is combined wi t h
,

metals such as copper p yrit e s and zinc blende b u t i t does not pay to ex t r ac t
,
- -
,

sul phur as such from these ores A certa in proport ion of i t comes on t he
.

market however as i t i s obta in e d a s a b y pro duct in the Leblanc sod a pro

, ,
-

cess The sul ph u ric aci d u se d in t hat process is ul t im a t e ly c onver t ed in t o

.

calcium sul phi de C a S and for many yea rs thi s accum ul ate d in grea t hea p s
, , ,

whi ch were a public nui sance no method bein g kno wn by which i t c oul d
,

be worked up excep t at a prohi bi tive c os t E ventually t h e Clau s Chance .

-

process was d evi sed and perfec ted whi c h enabled t hi s to b e done Kil n g a s
,
.

”
i s passed over the so d a waste converting it in to calcium ca rbona t e a n d
-
,

s ul ph urette d hydr ogen C a S H O CO Ca C O H S gAs t he s ul , , g .

h u r e t te d hydr ogen i s ra t her dil ute and variable in c oncen t ra t ion t he gas is
p ,

led t hr ough a fresh quantity of the waste by whi ch i t i s absor b ed fo rmin g , ,

t he bisulphi de : C a S + H S C a H S W hen kiln gas i s led t hrough t hi s

'

2 Z Z.
 MANUFACTURE OF C HA RC OAL AND S UL P H UR
the sulphuretted hy d rogen is again given o ff but is of double the previou s ,

concentration Ca H S H 0 CO C a C 0 + 2H S This gas is col

g 2 2 Z 3 g .

le cte d in a gas holder and can be fed from there into the chambers where it
-
,

i s converted into sul phuric acid or it can be mixed with gas from the pyrites ,

burners whereby sulphur i s caused to deposit in accordance with the equation

,

2H S + 8 0
z 2H 0 + 3S
2
: The sulphur th us obtained is of c onsiderable
2 .

purity .

S ul phur is also obtain ed in the purification of c oal gas from sulphuretted -

hydrogen and other sulphur compounds .

U ntil recently the market was entirely controlled by an E nglish asso c ia

tion the Anglo Sici lian Sulphur Company formed in 1 8 9 5 Sulphur had
,
-
, .

been found in Louisiana in 1 8 65 during some boring op erations for petroleum , ,

but it was s itu a te d un der n e a th 500 feet of qu icksand and all attempts to
'

work it commercially failed until the matter was taken up by Hermann Frasch
in 1 8 9 1 and eve n then years of work were re quired and a large amount of
,

capital before success was achieved The sulp hur i s mixed with a much .

small er proportion of limestone than in Sicily the ore contain in g about 70 ,

per cent sulphur The method that has been adop ted i s to put down a pipe
. .

of 1 0 inches diameter until the sulp hur dep osit i s reached then the hole i s ,

continued with a 9 inch drill through the sulphur dep osit w hi ch i s about
—
,

20 0 f eet thick A 6 in ch pip e i s passed to the bottom and a 3 inch pip e

.
-
,
-

through t hi s both being p erforate d near their lower ends Superheated

,
.

water is passed down the 6 inch pipe but the sulp hur p asses up the 3 inch -
,
-
.

At first it was raised by means of pump s but now air is forced down this ,

mixes w ith the sulphur and reduces its density and it is raised to the surface ,

of the ground by the pressure of the water used for melting .

The U nion Sulphur Company has been so successful that it has ac quired
the whole of the trade of the U nited States and also exp orts considerable
quantities The production amounts to several hundred thousand tons p er
.

annum .

The sulp hur as it comes up from the well is said to have a purity of 9 9 9 3 -

to 9 9 9 8 per cent It is simply run into great bin s whi ch hold as much as
-
.
,

tons each W hen it has cooled the sides of the bins are removed the
.
,

sul phur is broken up and i s then ready for shi pment ,

.

The Anglo Sicil ian S ul phur Company findi ng itself unable to contend
-

with Frasch s Company fina lly retired from the bus iness but it h a d made
’

enormous profits for many years The Italian Government has forme d a .

c ompulsory trust to control the marketing of Sicili an sulphur and ensure a

li ving wage to the Sicilian workmen Thi s has proved very successful and .

the workers in Sicily are now better o ff than they have been for many years
past.

On the oc c asion of the presentation to him of the P erki n Medal Frasch ,

 EXPL OSI VE S
gave a very in te res t ing accoun t of the vari ou s diffi c ul t ies he h ad to con t en d
wi t h in w orkin g ou t his in v en t ion and t hi s i s publi s hed in t he J Soc C he m
, . . .

I nd . 1 9 1 2 pp 1 68
, ,
.

Sicili an sul ph u r requi res to b e refined before i t can b e u sed and t h i s i s ,

d o ne by di s t il lin g it The crude or grough sulph ur i s p lac e d in an ir on po t

. .

w hi c h i s hea t e d from be low by a furn a c e un t il the sulphur boils The vapour .

pa s s e s over in t o a chamber w here t he sul phur is d ep o s i t ed on the wa lls in

t he form of small c rystals w hich c ons t i t ute flowers of sulphur
, If t he wa ll s .
“

of t he chamber are allowed to get ho t enough to mel t t he c ry s t a ls t he s u lphur

r u ns d own and is ta pped off and cas t into sticks or rolls The s t ill i s of t en - .

so arrange d that t he w aste h e at from the furnace melt s ano t her charge of crude
sulphur ready to run into t he s t ill as soon as t he firs t charge has b een di s t i lled
off
. The refin ery at Waltham Abbey i s p ro vid ed not o nly wi t h a large
c hamber or d ome but also wi t h a c ondenser lea di ng to a receiver Onl y .

t he fir s t por t ion of vapour is a d mi t te d to t he dome t hen t he vap o urs are tu r ned ,

in to t he c ondenser Flo w ers of sulphur are no t fit for makin g explosive s

.

because t hey con ta in a small propor t ion of sulphuric and sulphurou s ac ids .

The flo w ers from the dome are therefore redi still ed .

t
Pr o p er ies .
Roll sul phur consists of pale yello w brit t le crys ta ls belonging to the rhombic
sys te m havi ng a d ensity of 2 0 7 at
. It melts a t abou t to an am be r
c o lo u re d li qui d but when t he heat ing is c ontin ued a bove 1 20 i t gra dually
,
°

b ecomes d arker and more viscous Bet w een 1 60 and 220 i t is so v i scous ° °
.

t ha t t he vessel c onta in ing i t can be inverte d wi t hou t l o s ing a n y If t hi s .

vi s c ou s amorphou s mass be c ooled rapidl y par t of i t reta in s t he amorphou s

c on di t ion a n d is insoluble i n carbon bi s ul phide w hich di ssolve s ordi nar y ,

rhombi c sulphur wi t h ea se : Fl o w ers of sulphur al w ays c o n t a in a propor t ion

of t hi s in s o luble m odi fi ca t ion Sulphur boils at .

t
Func i o ns of One reason w h y sulphur i s a d ded to black p o w der is t ha t i t s t empera t u r e
s ul p h ur .

of igni t ion 2GI C is low a n d c onsequen t ly i t makes t he p o w d er bur n more

,
°
, ,

rea di ly Bu t ano t her rea son is t ha t un der t he influence of pres s ure no t only
. .

in t he pre s s bu t al s o in t he i ncorporating mi ll i t flo w s a n d be c o mes colloidal ,

cemen t i ng t oge t he r t he par t icles of charcoal and the minu t e c rys t a ls of sa l t

pe t re From t he examination of microph o to graphs Cronqui s t found t ha t
.
2

brown c harc oal has a similar power of becomin g c oll oidal un d er p re s sure .

Thi s i s w h y brown gunpowders burn more slowl y a nd r egularl y t han blac k ,

and why t he perc en ta ge of sulphur i n them c a n b e reduced or aboli s hed

alto ge t her 3 .

Sulphur oxi di zes s l o w ly in t he air forming sulphur dioxide and a li t tle ,

sulphuri c a c id If a chlorate be present c hlo ri c a c id i s li bera t e d and t hi s

.
,

accelerate s t he o xi da t ion and there i s grave danger of s pontaneou s igni t ion

.

occ urri ng .

1 2 3
S ee a ls o 19 1 1 ,
p . 23 6
. S S
. ., 1 90 6, p . 53 . S ee p . 86
.
 C H AP TE R V I

MANUFACTURE OF G UNP OW D ER

Ad va nt a g e s a nd va nt a g
d is a d C m p it i o n es G rin d in g t h in gred i nt :
o os e e s

n d mi in g
a I n c rp ra t in g o mi llin g Au t o m t ic d r e n h e r
x o o r Re m a c s ov

i ng t h e mill ca k e -
B re a kin g d w n P r e s in g G r nul a t in g c m in g D u t in g
o s a or o s

a n d g la zin g St o vin g o d r y in g Fin is hin g a n d b l e n di n g C u t p w d r

r M uld ed o e s o

p o w d e r Bs la s t in g p o w d e r Sp r n g s a lp e t e r C a h u e c it P t o kl t it B o b b in it
s e e r as e

lub l e p o w d e r
-
so P r d u ct f e pl i n o s o x os o

TH E invention of so many oth er blasting e x plosives a n d smokeless powders

has g r e a tlv restricte d t he c onsumption of bla c k p owder but it has been able ,

to hold its o w n in certain fields i n consequence of its a dvantages : its lo w

price the ease with whi c h it c a n be igni te d its in sensiti v eness to sh o c k its
, , ,

stab ili ty at m oderately hi gh temperatur es its regular rate of burnin g and , ,

the non corrosive nature of the resi d ue that it leaves i n the g u 1 But aga inst
—
.

these must be place d its great di sadvantages : its w ant of p o w er and t he

great quantity of sm oke that it evolves For shot gun s it s rate of e x p losi o n .
-

i s sui table only the recoil and smoke are di sagreeable but for ri fl e s t he rate
, ,

of bur nin g cannot b e c ontroll ed s u fficiently ; for d riving the bulle t s o u t of

shrapnel shell there is no bette r e x p losive and it is still use d for armour piercing ,
-

shell because the hi gh e x plosives use d for other sorts of shell wi ll not wi t hstan d
,

the great shock of impa c t w it out explodin g prematur ely for fi lli ng t he rings
h

of t ime fuses for shell no satisfactory sub stitute has yet been foun d .

Guttmann in hi s book on the Ma n u fa ctu r e o f E r p los ir es p ubli shed in

, , Comp o sition .

1 8 9 5 gave the foll owing as the c ompositions of the prin cipal p owders ma de
,

at that time :

1
Ven m n et C h es nea u p 322 g ive t h e p o p o t io s 75 l 2 5 1 2-5 r r n
'
°

. . , .

2
Th e p o p o t io s a ft e w a d s s e d in G e r ma n v fo r ifl e p o w d e w e
r r n r r u r r r e 75 9 15 .

73
74 EX P L OSIVES

(b ) C a n no n P o wde r s

Fr an ce 1

(c ) S p o r t ing P o w de r s

(d ) B la s ting P o w de r s

Bla s t ing po w ders h o w ever ; vary in composi t ion far m o re t han t hi s Table
,

indica t e s powders wi t h di fferen t ra t es of burn in g being u sed for rocks o f

,

di ff eren t degr e es of hardne s s Thus t he Fren c h Govern men t fac to ri e s make

.

t hree sort s of mi ning po w d er :

Or d in ary Po w de r
Slo w P o w d e r

1
Ve rm i n e! C he s n
ea u ,
p . 322 gi v e t h e p r o p o r t io ns 75
,
 MAN UFACT URE OF GU N P OWD ER
The p owders manufactured in Belgium ha ve the following compositions

Ri fl e P o w d e r
Can n o n P o w d e r
Sp o r t in g P o w d e r

B la s t in g P w d e ro

Slo w P o w d r o r P ul vé rin
e

Slo w P o w d e r in c ar t rid g e s
E x p o rt P o w der

In France pul vérin is also prep ared for the manuf acture of fireworks ,

etc Accor di ng to Chalon it has the comp osition 75

. but
Ve nn in gives the proportions as 62 20 P4 03 ,

B efore they are mixed together the three ingredi ents are p ow d ered As G inding th e . r

ing edients r
they are not e x plosive when separate they can b e ground up in any s ui table ,
.

m ill In this respect however some reserve must be made as regards the
.
, ,

sulphur : thi s has a great tendency to become electrified and as it is also ,

very inflammable an electric spark may easily set it a light or cause the e x p lo
sion of a mixture o f sulp hur dust and air Rapid m oving mach inery is
-
.
-

”
therefore to be avoided the p arts should all be made of metal and earthed .

Accordi ng to Voigt the drum for p ul veri zing s ul phur should not make more
than ten revolutions per minute 3
In some works the s ul phur is mi x ed with a
.

small proportion of the saltpetre before grin di ng to prevent this electrifi cation ,

which has the further di sadvantage that it causes the sulphur to cake together
and so escape proper grinding At W altham Abbe y the sulp hur is ground
.

under steel edge runners s imilar to those used for incor p oratin g the p owder
-
.

The charcoal is generally groun d in a machine resembling a large coffee

mill (s ee Fig but in some factories ball mill s are used the charcoal being
.
-
,

placed i n a drum with bronze balls The drum i s then rotated unt il the .

c onstant falli ng of the balls on to the charcoal has reduced it to a sufficiently

fine state of di vision .

S ulphur and saltpetre may also be ground in the E xcelsior mill but if ,

the saltpetre is already in fine crystals it need not be ground but only sifted ,
.

In France the saltpetre is mixe d with 6 per cent of charcoal and p u lverized .

in an iron drum with bronze balls The charcoal makes the saltpetre easier .

to grind and this small proportion does not make it e x plosive The r emainder
,
.

of the charcoal is mi x e d with the sulphur and pulverized in a similar drum .

After grinding these binary mixtures are passed through a sieve with holes
1
E x p lo s if
s rl f o dé r n es ,
pp . 228 , 263 .
2
Ven m n
'

el C h es n ea u , p . 322 .

3
H er s tellu n g der S p r en gs tofi e , vol i , p
. . . 52 .
 76 Ex p L Os I v Es

0 65 mm in di amete r to separa t e fo reign ma t te rs The t w o bin ar y mix t ur es

. .

a re t hen mixe d t oge t her b y han d before being mill ed 1 .

W eig hing a nd
The t hree ingre di en t s are c arefull y w eighe d ou t preferably ea ch in separa t e ,

scales An ex t ra amo u n t of sal t pe t re i s o f t en t a ken to a llo w for t he mois t ure i n

.

i t t he actual pr o por t ions w eighe d ou t being some t imes

, 15 0 10 0 -

instea d of 75 0 1 5 0 1 0 0 -
Bu t t he c harc o al u s u a llv c onta in s qui t e a s hi gh a
-
.

percen t age o f mois t ure a s the

s al t pe t re I t i s no t surpris ing
.

t herefore t ha t analysis some t ime s

s ho w s a percen t age of c harc oal
w hi c h is belo w t he t heore t i c al .

The in gre di en t s a re t hen gi v en

a preliminary mi xing In Ger .

ma n v t his is d one in a ro t a t ing

d rum w i t h li gnum vi t ae balls .

The dr um i s ma d e of wo o d a n d
may be lined wi t h lea t her ; iron
mus t be a v oi d e d in t s c ons t rue
t ion : t he axle mus t be c o v ere d
w i t h lea t her A t “ a ltham Abbe y
.
-

t he mixing is d o ne ii a c y lin d ri c al .

drum o f c o pper or gun me t a l -

ab o u t 1 8 in c he s long a n d 2 fee t
9 in c he s in diame t e r Thr o ugh .

t he c en t re pa s se s an axle c arrying
eigh t ro w s of f o rk shape d a rm s -
,

c alle d fly er s The d rum ‘

r o ta te s in o n e direc t i on maki n g
4 0 revolu t ions per minu t e The .

a X le m o v es in t he O t he r d ire c t ion FI G 6 E c l i r Mi ll m d b M hi n n b a u . . x e s o . a e v a sc e

and makes 1 20 revolu t ion s per A ( l l ze n G i n n n a . o r -

r .

m inu te The ingre dien t s are

.

mixe d for fi v e minu te s a nd t hen sif t e d t hrough a fi n e mesh sie v e of copper or

.
-

brass wire The sif t ing a t thi s s ta ge is v ery impor t a nt a s a n y hard par t icle s
.
,

left in the c harge are likel y t o c ause an e x 1) lo s io n in t h e in c orp o ra t ing mill .

Fo r thi s reason t h e s if t in g i s some t ime s d one b y han d The green charge

'

i s no w placed in a w a te rp roof bag rea dy to b e t a ken to t he in c o rpora t ing mi ll .

t
I nco r p o r a i ng On the Con t inent stamp mills are s t ill u s e d t o a small ex t e n t fo r in c o r p o ra t
-

o r milli ng .
ing a s w ell as mi x ing gunp o w d er In German y t he s t a mp head s ma y be mad e .
-

of c o pper zinc bronze o r o t her s ui ta ble all o y

, ,
The c harge is pla ce d in a .
2

spheri c al hole in a b lo c k o f w o o d w ith a pie c e o f s pe c iall y hard w o o d in s er te d

.

' 0
l e n n in cl C IM S N C G N. p . 3 27 . 1 9 12 .
p . 1 82.
 MAN UFACT U RE OF G U NP OWD ER 77

at the bottom for the stamp to play upon The stamping is carried on for .
“

about fourteen hours I f contin ued l o nger the density of t he p ow der diminishes
.

and t he ba lli stic s deteriorate .

In France the u se of stamp mills w a s defi nitely abandoned in 1 8 8 4 the

-
l
,

powders there being in c o rporated in drums and mills The cheaper sorts of .

po w der are in c o r p orate d

ent irely in drum s c ontain
ing wooden balls In .

E ngland also stamp mill s -

are not u se d a n d the,

stan dard metho d is to

grind the in gredi ent s to
gether in incorp o rating
mi lls
. Formerly t hese
consisted of tw o heavy
stone edge runners work
—

ing on a stone be dplate .

Now it i s m ore usual to

have iron runners work
ing on an iron b e d plate -

of course iro n must not

work upon stone or vice ,

versa on ac c o u nt of the
,

d a n g e r o f generating
sparks In the most usual
.

typ e of mill the run ners

are 6 or 7 feet in di ameter
.

and about 1 5 inches wide ,

and weigh ab ou t 4 tons

each They rotate on the
.

oppo site ends of a hori

z o n ta l shaft whi ch i s
,

carrie d by a cross hea d -

FI G 7
, G ru n G m p w d r Mill . . so r o e .

w hi ch again i s attached
to a vertical shaft making abou t eigh t revolu t ions a minu t e U sually t he tw o .

edge runners are mounted at di fferent distan c es fr o m the c entral shaft 8 0

-

that one works the oute r part of the charge a n d the o t her t h e inner but their ,

paths overlap There are two ploughs of w o o d co v ered with lea t her w hi c h
.
,

are fi xed to the shaft a nd travel round wi t h it These con t inually pu sh .

the charge away from the centre and the curb respec t ively and b ri n g it ,

under the ed ge ru nner s again The mill s make 7a or 8 rev o lutions per minute
-
. .

1 P. a 51 , v o l iii 18
. .
, p . .
78 E XP L OSIVE S

In t he Gruson mill (Fig 7) t he iron runners do not rest on the bed but are
.

s uspend ed a short dista n c e abo ve i t so that there is no danger of a very thi n

,

lay er of po w der being subj ec t ed to great fri ction The bearin gs a r e s o sus .

pended t ha t ei t her runn er ca n t r a vel upwards independently of the other

when an ext r a t hi ck porti on of charge comes un derneath it The f a rmers .

w eigh about 5 } t o ns ea ch a n d ro t a te equi di sta ntly roun d the m a in vertical

shaft The plough s are made of phosphor b r onze and each r unn er i s als o
.
,

p r ovid ed wi th a sc r aper to prevent the charge bein g thr own o fl the bed The ’
.

drive is by mea n s of a large bevell ed gea r wheel which may b e arranged either
-
,

a bo v e t he mac hi ne or below it .

In Germany iron runn ers are not allowed to work on an iron bed plate -

unl es s t hey a re suspend e d as in the Gruson mill If they a c tually rest upon
, .

the b e d it must be m a de of wood faste ned down with b r ass screws

, .

By the acti on o f the runn ers the in gredi ent s are c rushed and ground to
gether very inti mately wi thout subj ecting the mi xture to any violent action .

U suall y about s ix incorporating mil ls a r e arranged in a row and driven from

a common shaf t actuated b y a s ingle wate r wheel or steam engin e Each mi ll - -
.

is sepa r ated from the next by a strong masonry wall E x plosions in these mill s .

a re fairly frequent in spite of every precaution but as a rule no very se r ious ,

damage is done In 1 90 7 there were nine such explosions in E ngla nd but

.
,

onl y one man w a s in j ure d in 1 90 8 there were fi v e explosions and two men
were in j ur ed in 1 90 9 there were seven e xplosions and no men were inj ur ed .

The re ason w h y there are so few men kill ed or inj ured in these accident s is
tha t as a rule there is no one in the m ill house afte r the charge has bee n
s t a rted the man in atte ndance goes on to see to other mill s and onl y c omes
occa sionally to see that all is right and to add a li ttle wate r to the charge if
n e ce ssary In Fran c e there i s less than one explosion in
. milli ng
ope rations .In Ge rmany no workm an is all owed to rem ain in the bui l di ng
‘

w hil st t he mi ll i w orking a t ful l sp e e d

s .

A charge consi sts of 60 to 8 0 lb s the time of incorporation varies with the

.
,

descrip t ion of the p owder the longer the incorporation the faste r th e powder
bu r n s Cann on po w ders we r e usually m ill e d for thr ee or four hours rifle
.
,

po w ders eight and sportin g powders as much or more The charge when
, .

plac ed in the mi ll conta ins 2 to 3 per cent of moisture It mu st be kept moist

. .

t he whole time for thi s purpose the mill man adds wate r from t ime to time -
,

p r efe r ably condensed wate r from a ste am t r ap Formerly urin e was f r e quen tly .

u s ed inste a d of water For fi n e grain p owders i t to 3 per cent of m oisture

. .

shoul d b e pre sent in th e fini shed mill cake for larger siz es 3 to 6 per cent
-
, .

In F r ance mil ls s imil ar to the G r uson mi ll a r e u sed bu t the charge is onl y ,

20 kg or 25 kg in the c a se of mini ng p owder

. . I t conta in s 8 per cent moistur e
. .

when int r o du ced and 2 to 4 per cent at the fi nish The mi ll makes 1 0 r evo
. .

1
Ven n i n cl C he s nea u ,
p . 33 3 .
 MAN U FACT U RE OF G U N P OWD E R
lutions per minute and requires 7 horse p ower The following table -
.

the times of m ill ing and the densities of the mill cake : “

Tim D n s i ty e e

Mil it ary r ifl e p w d er F
o ,
2 2% h o ur
3
— s

Sp o r t in g p o w d e r o rd inary
,
ll
s t ro n g 5
D us t r w o r k e d
e

Mini n g p o w d e r

The density i s of importance because in France the powder is not pressed .

The density can b e i ncreased by milli ng slowly half a turn per m inute with , ,

the outer plough removed 1

.

In Germany the charge i s generally ab out 75 kg and the mi ll makes about .

nine revolutions per m inute The time of milling is .

Mi lit ary p ow de r 232 3

1—
h ur s
o .

Sp o in grt
Mini g n

FI G . 8 . D renchin g Ar rang e me n t s fo r P o w d er Mill s .

Before the charge i s removed the mill i s r un slowly for a time to increase the
densi ty b ut the p owder un de r g o e s a pressin g op eration also except in the case
, ,

of minin g p owder 2
.

In order to prevent the e xplosion in one mill being comm u ni cated to the
other mill s of the group each one i s provided in E ngland with an automatic
,

drenching arrangement (s ee Fig Thi s consists of a li fting board I provided

.
,

wi th a counterpoise weight There i s also a tank 15 fu ll of water supporte d

.
,

on a hi nge and a leg at one end that rests on a proj ection from the li fting
board When the latter i s lif ted the leg is released the tank tip s forward
.
, ,

and the water is poured over the charge in the mill The a xle a is common . .

1
Ven n i n cl C h es n efr u , p 3 32 . .

2
Vo igt , H e rs te llu ng der S p r eng s tofi e , i .
, pp . 55 , 56.
 E X P L OSIV E S

t o a ll the lif t in g b o a r d s o f t he gro up o f mills s o t ha t i f t here be an explosion ,

in one of t he m ills the c o rre s p o n d ing b o ard I is ra i s e d t aking wi t h i t all t he ,

o t her s imilar b o ar d s a nd a ll t he c harges i n t he gr o up are dren c he d a nd s o

.

rendered unexplo s i v e In order to make the me c hanism s u fli c ie n t ly s en s i t ive

.

it is imp o r t an t t ha t t he b o ard s be n o t to o s mall a n d n o t to o near the roof and ,

t hat t hey be d ir e c tlv o ver the mill s The s e c o nd p o in t is es s en t ial be c ause if

. . .

t he b o ard be v e r v near t he roof a reflected

w ave o f pre s s ure rea c hes i t almost imm e
d ia te ly af t er the d ire c t w ave and bef o re the
me c hanism has h a d time to act .

The mill cake o f t en b ec o mes c aked o n

-

t o t he b e d v e r v fi rmly N au v ac c i d en t s
.

h a v ing been cau s ed by remo v i ng this wi t h

me t al t o o ls H M Inspec t o r of E x pl o sives
. .

i s s ued a letter on De c ember 27 1 8 8 3 p r o , ,

p o s ing t he adop t ion of the f o llo wi ng spe c ial

rule in all black po w der w orks :
t e ne v e r it ma y bec ome nece s sar y in
mill s or o t her buil ding s to rem o ve a u v
p o w der incrustations (w he t her fr o m the
ma c hiner y o r el s e w here ) w hi c h canno t be .

e a s ily b r u s h e d o
v

fl su c h rem o v al is to be
,

e ffe c t e d w i t h o u t the u s e of any metal t ool

w ha t e v er t he har d p o w d er is t o be rem o ved
b y mean s of w ater supplemen t e d if n e e d
, ,

be w hen t he w h o le i n c rus t a t i o n ha s been

,

thor o ughly s a t ura t e d b y a s ui t a b le w o o den

.

”
instrumen t gentl y applie d .

The mill cake i s next re d u c e d to a r ough

-

po w der by hand o r b y passing it t hro ugh

gun me t al roll s in a m ach i ne s ome w ha t
-

resembling the granula t ing ma c hine bu t 9 G mp o w d e r P r

, , l ess .

s impler .

Pres s ing . Then the mix t ure i s s ubj e c te d t o high pre s ure in a p re s s Thi s c onvert s s .

i t in t o a har d mas s the c o ns t i t uents of w hich have n o t en dency t o s e parate

,

again from one another a n d also in c rea s es the densi t y of t he po w der

,
.

Formerly the po w d er w a s c ompre s sed in a very strong box bu t t hi s is no ,

longer done on account o f the dangerou s fri c tion against the si de s .

For moul de d p o w ders and blasting c artri dge s s pecial p resse s are used ,

w hi c h wi ll be described later Granulate d po w ders are p re s s e d i n pre s ses of

.

t he t ype sho w n in Fig 9 The mill cake is built up o n a s mall t r o lley first
. .
-

a plate of copper br o nze or ebonite i s put d o w n and a temporary frame put

, , ,
 MAN U FACT U RE OF G U NP OW D E R 81

round it then a layer of the mill c ake about g inch thick is carefully spread
,
- -
,

then another plate and another layer of p o w der unti l about 1 0 cwt of m ill cake , .
-

has been built up with abou t t w enty pla t es The temp o rary frames are th en .

removed and the troll ey is w heeled on to the press and the pressure i s gradually ,

applie d The am ount of c ompression requi r e d varie s w ith the amount of

.

m oisture in the mill cake a nd the density t o be attain ed in the finished po w d er

-
.

For a mixture containing about 3 per cent of m oisture it is necessary to apply .

a pressure of about 400 lb per square inch of plate surface for 1 % to 2 hours
.

t o obtain a density of 1 7 The amount of c ompression is measured by the

-
.

motion of th e press rather than by the hydr auli c pressure this motion may be
24 or 3 0 inches according to the di mensions of th e press etc The pressure , .

is usually released and reappli ed several times to obtain a satisfactory result .

E bonite plates are sometimes preferred to metal because they keep their
shape better and yet give su ffi cien tly to transmit the pressure evenly If the .

cake be very dr y the ebonit e may become electrifie d however and so produce , ,

very dangerous sparks In Germany th e use of eboni te plates i s forbidden

.
,

and cloths are laid between the plates and the p o w der The four columns of .

the press should be made of mild steel wi th an ample margin of strength even
if the whole pressure is b orne by only tw o of them They may with advantage .

be c overed with leather It w a s recommended by H M Inspector o f E x p lo

. . .

s iv e s
1
th at the press should not be worked d irectly o fl the hydr a ul i c pump ,

but from an ac c umulator and that the dr ive of the pump should not be positive
, ,

but by friction .

The explosion of a press house is more destructive than that of any other
-

bui ldi ng in a black p owder works as might b e exp ecte d considering that
, ,

there i s about half a ton of p ow d er in one mass strongly c ompressed The .

house sho u ld therefore b e speciall y well isolated from other bui ldi ngs by moun ds ,

etc In some works th e workmen are not all owed to be in the press house
.
-

whilst the pressure i s on the powder the pressure can be appli ed and controll ed
from another compartment where there i s also an indicator sho wi n g the position
,

of the platform of the press .

When suffi ciently pressed the pressure is released a n d the trolley is w h eeled
a w ay and the press cake rem ove d from it by hand or wi th w o oden tools The
,
-
.

outer portion of each slab i s rej ected as it i s n o t sufficiently c ompresse d it is

adde d to a later press ing .

Blasting powder i s sometimes c ompressed between rollers .

The broken u p press cake i s put i n barrels and taken to the granulating
- -

or co m ing house Here there i s a machine having three or four pairs of gun
.

metal rolls through which the p ress cake is passed a n d a number of automatic
,
-
,

sieves which sort out the grains of th e required size (s ee Fig

, The top .

pair of roller s u s ually h a s pyrami dal tee t h : fr o m t hi s the material pa s ses

1
Sp i l R p r t N 1 38 ec a e o o . .

V OL . I .
 E X P L OS IV E S

o v er a s ie v e t o t he ne x t pai r of rolls w h ich has smaller t ee t h The lo w es t

,
.

pa ir a r e p lain The piec e s tha t a re no t fine enough a r e pa sse d t hrough t he

.

machin e again po w d er shor t and

FI G . 10 . Co rnin g Ma c hi ne ma d e
. b y M
a s c hin e n u
ba A G
.
-
. G
o lze r n G rimma
-

pres s ed again The bearing s o f o ne o r b o t h rolls o f ea c h pair are pro v id e d

.

wi t h s p ri ng s o r w eigh t s t o keep t hem in p o si t ion a nd a re n o t ri gi d l y fi xed

.
.

Con equen t ly if an ex t ra hard piece o f c ake pas s e s t hr ough t he rolls it i s no t

s

s ubj ec t ed to grea t v iolence t h e r o ll s gi v e w a y and t he piec e passes t hrough .

Thi s t yp e of g ranula t in g mac hine w a s in v en t ed in 1 8 1 9 by Colonel Con greve ,

 MAN U FACT U RE OF G U N P OWD E R
and is the one in most general use Variou s other types have been tried but
.
,

none produces such a good angular grain .

In France the granulation is carried out in a horizontal drum covered with

metal sheet perforated with fi ne holes of a size suited to th e sort of powder that
i s to be produced The broken down mill cake is pl a ced inside this drum to
.
-

gether with pieces of hard wood which are caused by longitudin al strip s to fall
,

continually on to the powder and break it up A charge of 20 kg is granulated . .

in ten to twelve minutes and yields 3 5 to 55 per cent of grains of the size required . .

P owders made with dog wood charcoal produce a lo t of d us t in the corn i ng

-
t
D us in

FI G . 1 14 Co rnin g Ma ch in e wi th D us t -
R e mo v e r

process and it i s best to rem ove this by passing the powder through a dusting
,

reel This i s simply a cylindrical reel set at an angle of about 4 to the hori
.
°

z o nta l and covered with fine woven wire of copper or brass It i s op en at .

both ends and rotates on its axi s making about forty revolutions per minute
,
.

The p owder is simply passed thro u gh thi s a n d caught again in a barrel .

The glazing operation i s carried out in wooden drums which rotate on Gl zi ng ? ) ,

a

their axis about thirty times a minute Cannon p owders receive an ad di tion
.

of a small pr o portion of graphite and are glazed for two or three hours Rifle .

and sporting powde r s and others that are require d to burn qui c kly do n o t
, ,

r eceive any graphite but are glaze d longer

,
.

The s tove ma y be heated either b y forcin g hot air th r o u gh it or by arranging 1 “ 0 1 3

2
7 0‘
,
 E X P L OSIV E S

h o t w a t er or s t e am pipes in i t The ea sie s t a nd m o s t ec o nomi c al me t ho d is

.

t o dr y wi th ste am a n d a s bla ck po w d er is n o t very s en s i t ive a n d i s no t li able

,

to sponta neou s d ecompo s i t ion t hi s me t ho d i s u s uall y ad o p t e d

,
Only low .

pres s u re s te a m s h o uld be used t he exhau s t be ing open to t he a ir The p o w d er

. .

i s place d on c an v a s t rays suppor te d on w oo d en ra cks Inl e t s and ou tle t s are

.

pr o vi de d for t he a ir a n d t he te mperatur e i s kep t a t ab o ut 40 C ( 10 4

,
°
.
°

The t ime requi red to dry t he po w der varie s from one to four h o ur s a c c or ding
t o the s ize of gra in .

Fini s hing a nd To remo v e t he la s t t r ace s o f d u s t a n d gi v e t he p o w der a goo d c o l o u r

b lendi ng
i t is n o w trea t e d for some t w o hour s in t he fi nishin g reel w hich is c o v ered wi t h
.

fine can v a s a n d fin all y t horoughl y blended in to large uni form bat c he s The
,
.

las t operation i s p e r forme d a t l Va lth a m Abbey b y pouring i t in t o a h o pper ,

w hi c h is provided wi t h four delivery shute s s o tha t t he con t en t s of the hopper

,

are di vi ded int o fo u r equal portions By repea t in g this opera t ion in a

.

systematic ma i ni e r t h e des ired o bj e c t is at t a ined v er y eff ec tua ll y .

C ut p ow ders . P o w der for c a n o n of large size 6 t o 1 2 inch bore w a s ma d e b y cu t t in g

,
-
,

t h e pres s c ake i nto cubes

-
The slab s from t he press w e re p a ssed 1mde r a roll
.

arm ed wi t h l o ngi t udi nal kni ves w hereb y th e c ake w a s cut in t o strips a n d t he s e
, ,

w ere t hen passe d mi der ano t her simi lar roll in t he o t her direction and so c u t

i n t o c ube s . The glazin g s t o vi n g finishin g and blen di ng w ere v ery much a s

, ,

for granula t e d po w d er ex c ep t t ha t t he s t ovi ng had t o be con t in ued for about

,

thir ty hours at 55 C These cu t p o w ders are bu t li t t le ma d e n o w a s t hey

°
’

.
,

have b e en displaced by smokeless po w d ers .

The foll o wi n g Table gives particul a rs of some of t he po w ders made formerly

a t Wa l t ham Abbey 1

Moul ded Moul ded p o w d ers also are but li t tle u s ed for t he me rea s on bu t much the
sa ,

s ame pro c e s s i s u s e d for maki ng moul ded cart ri dge s o f min ing po w d er and also ,

1
Tr ea tis e o n S e r v ic e E x p lo s ives 1 90 7 c d
, .
, pp . 1 23 , 1 24 .
 MAN UFACTURE OF G UN P OWD ER 85

pellets for time and percussi on fuses and fo rother ammunition The general .

form of all these articles is practically the same a hexagonal or round cylinder

FI G 1 2
. . H y draulic Au t o ma t ic P ress fo r Mo u ld e d P o w d e r s a n d a t ing Car tridg e s
Bl s

(Ma s ch ine n b au A .
-
G . G o l ern G rimma )
z -

with a central perfo ration The po w der is pressed granulate d d usted and
. .
, ,

blended as already describe d a n d then taken to the mouldin g house Two

,
.

di ff erent ty pes of press are u s e d worked by hydraulic and mechanical pressure

,
86 E X P L OSIV E S

respe c t i v ely (s ee Figs 1 2 and

. The general principle is ho w ever t he same , , .

The gran u lar pow d er is pu t in t o a hopper a n d flows from t here in t o a measure

t ha t au t o ma t icall y measures off t he righ t quan t i t y whi c h t hen pa s s es into t he ,

di e . The di es are arranged in ro w s in a pla t e so t hat w hi lst one r o w i s bein g

,

fi lle d ano t her is being presse d The pressure is usually app lied s imul t aneously
.

from above a n d belo w by t wo

di ff erent plun gers The cen .

tral hole is formed by m ean s

of a pin whi ch passes through
the lower plun ger and into
th e other Hydr a u li c presse s .

are safer but mechani cal ,

ones m ore rapid in the ir

action For blastin g car .

t ridg e s ma chi nes are also ,

made wi th rotat ing ta bles

conta ini ng a number of di es
each operation filli ng press , ,

ing rem oving is performed , ,

at a difl e r e n t position of the

ta ble Such machi nes are .

qui te au tomatic and requi re

very little atte ntion .

B oth black and brown

p owders have been moul ded
into prism s w hi ch are usua lly
2 5 mm high a n d 40 mm
Me ch ani ca l Pr M r
'

F re j l 3
. .

f ld d P ‘
. . ess u or o w d
o
I
e e s .

wi de meas u red across the

etc (F K r p p A G G r u o n w k )
. . u .
-
. s er ,

c orners of th e hexagons .

The foll o wi ng Table gives the detail s of t he E ng li sh and German powders

1
Ve r mi n et C he s ne a u ,
pp . 3 22, 3 4 1 .
 MAN U FACT URE OF G U N P OWD E R 87

P P C
. . has seven holes all the others E n gli sh a n d German only one The
. 68 ,
—
, ,
.

val u e of the brown straw charc oal i s that un der th e high pressures it flows
and holds the mi x ture together making it into an impervious mass which,
.
,

can only burn at the surface whereas black powders have slight pores th rough
,

FI G . 14 . A me rican B la c k B la s t in g P o w d e r s (Mi mr o e a nd H a ll )

which—the flame can penetrate This m ay be seen by examining th e p o w ders

.

under th e microsc ope

“
1
.

The usual c omposition of black blasting powders has a lr e a d v been s tated

(p . The vi o lence of the powder can be varied by altering the c o mp o sition ,

the density or the size of th e grains the p o w der is ma de sl o wer by diminish

ing the percentage o f saltpe t re c o mpressing to a higher density or making
,

1
S C ro n q u i t 1 90 6 p 53
ee s , , . .
88 EX P L OSIVE S
t he gr a in s c oa rser In France t he mi nin g po wders manuf a ctured in the State
.

mill s are inc orpora t ed no t un der e dge runn ers but in c opper dr um s wi th
,
-
,

wood en and bronz e ba lls a n d t he granu la t ion is a l so e ffected in dr u ms w ith

,

t he aid of a spray of w a t er .

In Ameri ca enorm ous quan t i t ies of blasting po w der a re used c on t a ining

sodi um ni t ra t e (Chili sa l t pe t re ) in t ea d of t he p ot a s si u m sa lt This b urns
s .

more slowly t han ordi nary g un p o w der bu t is more po w erful as i t evolves , ,

a grea t er vol u me of gas and more hea t bu t i t s principal ad vantage i s i t s low ,

p r i ce for i t is us ed for many purpose s w here in E u rope hand la bo ur woul d

,

b e employed A c c ordi ng to Chalon t he c omposi t i o n va ri e s bet w een t he

.
,
1

follo wi ng li mi t s

The usua l pro p or t ion s in t hi s blac k bla s t i ng po w der are given by Munr oe
a nd Hall
1
‘

a s 73 : 1 1 16 The incorporation i s no t so thorough as in the

.

ca s e of ordi nar y blac k po w der and t h e charc oal i s generally ob t a ined from
,

c oa rser grained w ood s As t he s o di um ni t ra t e is hygrosc opic ca re must be

-
.
,

t aken no t t o e xpose t he po w der t o damp air more t han ca n be helped The

.
.

follo wi ng are t he size s of American bla ck bla sting powders

D ia me t
e rs o f ro u nd h o le s i n sc r ee ns in (
1
7
th inc h e s

Th ro u g h w h ic h g ra ins O n w hi c h g ra ins
pa ss co ll e c t

40 32
36 2
4
18
12
7
3
2

The follo wi ng bla s t ing explosives resemb ling black po w der in composition
a re mad e in Germany and are a llo w ed to be sen t a s good s in u nli mited qua nti
,

t ie s a s t he v a re c ons ide r e d sa fer t o handl e t han ordi na r y b lac k powder

Spren sa l p e t er (blas t ing sa l t p et r e ) is a mi xt ure of s odi u m ni trate
g
,

sul phur a nd brown c oa l in a b o u t t he pro po rt i on s 75 1 0 1 5 a nd is very ,

la rgely use d in t he St a s s fur t sa lt mi nes w he r e t he sof t and brittle nature of the

-

s al t s s uch as ca m a llite requi re an e xplosive t ha t i s mi lder than or di nary

,

bl a t ing po wder I t po s se sse s t he advan t a ge of being cheap and not giving

s .

r ise t o p oi s onous fume s Harder m a t erials such as s v lv in ite and rock s alt
.
,
-
,

1
Le s E r p lo s ij s J l od e r nes 3r d cd
, 1 9 1 1, p ., . 264 .

3
P r i me r o n E
x p lo s i ves fo r C 0 0 1 J l i ne rs , 19 1 1 ,
p . 1 6.
 MANUFACT URE OF G UN P OWD E R
are blaste d with a c ombine d c harge of nitro glycerine e x plosive a n d Spreng -

salpeter .

C a h u e c it was invented by R Gahn o s ome f orty years ag o and was .

C a h uecit.
manufactured at one time at Dartford under the name of Safety Blasting
P owder or Carb oazotine It h a d the composition : .

Sal t p e t r e
Sul p h u r
Lamp b la c k
B ar k o w o o d p ulp
r -

to which was added 1 to 5 per cent of sulphate of ir o n Af ter mixing the . .

ingredients roughly in a dru m they were introduced together with a

c onsiderable bulk of water into a steam j acketed pan w here the mixture was -

heated with c onsta nt stirring until almost dry The mixture was im .

perfect in c onsequence of the tendency of the soluble salts to crystallize out 1

.

It is still manufactured in Germany and has been found good for blasting ,

basalt 2 The official German definition is a compressed mi x ture of not more

.

than 70 per cent saltpetre 8 per cent lampblack about 1 2 per cent flower s
.
,
.
, .

of sulphur at least 1 0 per cent cellulose and a small quantity of ir o n

,
.
,

sulph ate .

P e tr o kla s tit (H a lo kla s tit ) has appro x imately the follo wi ng c o mposition Petr okla s tit

u ni t rat e
So d i m
P o t a iu m n i t ra t e
ss

Sul p hur
C o al t ar p i t c h
P o t as s iu m b i c h ro ma t e

Its strength and sensitiveness as compared wi th black blasting powder are 3

Tr a u z l t e s t Fa ll in g w e i g h t
P e tr o k la s tit 1 57 1 00
B lac k p o w d e r 10 8 65

Its o fficial definiti o n is : a compressed mi xture of sodium nitrate sulphur , ,

c oal tar pitch saltpetre and not more than 1 per cent potassium bichromate
-
, ,
.
,

als o with an a ddi tion of not more than 1 0 per cent charc o al It has been ‘
. .

used in stone quarries and p o ta s h mine s .

In E nglish coal mines the most largely use d expl o sive h a s been Bobbinite
“

-
,
B o b b inite .
which is a bla ck pow der mixture With an additi o n of the sulph ates o f c opper
and ammonium or of starch a n d p a r a ffi nw a x
,
It is th e o nly e x plosive of -
.

this class that was able to pass the Wool w ich test fo r P ermitted E xp lo
s iv e s it d oes not pass th e C o ntinental and Rotherham test s In 1 9 0 6 a .

1
G u tt mann , Al a n u / a c tu r e '

, vo l i
. .
, p . 273 s ec a ls o C un d ill a nd T h o ms o n p 1 42
, . ,

2 3
S S . .
, 1 90 8 , p . 97 . Zs c h o kk e , pp . 42, 5 7 .
 90 E X P L OSIV E S

Departmental Committe e was hel d at the H o me Offi ce to inq u ire whe t her
thi s explosive sh o u ld be removed from the li st This has not been done but .
,

by the Explosives in Coal Mines Order of Se p te mb er l 1 9 1 3 i ts use has been

l

-
, ,

restricte d to mi nes that are not gassy or dusty In these its use i s permitte d .

for a peri od of five years from J anuary 1 1 9 1 4 The foll o w ing is its c omposi ,
.

tion acc ording to the offi cial defini tions and an analysi s made by Hall and .

Ho w ell 1

O ffi c ia l d e fi n i io n s t

Fi r s t Se c o n d

N it rat e o f po t a s iu m
s

C har co a l
Sulp h ur
Sul p hat e o f a mm o ni u m
Sulp hat e o f co
p pe r
Ri c e o r Ma ize s t ar h c

P araffi n wa x

Mo is t ur e 0 -0 2-5

In 1 9 1 4 more t han a mil lion lbs of B obbi nite w ere used in British mines .

a n d quarri es .

Wa te r -s o lu
b le Rasc hig pr o poses to make a cheap blasti ng powder c onsisting of 65 per
po w der . cent sodium ni t ra te a n d 3 5 pe r cen t sodi um cresol s u lph onate These are
. .
-
.

di ssolved i n water a n d the solu t ion i s evaporate d very rapi dl y on a rotating

drum heate d b y high pressure ste am It is claime d t hat the expen s ive a n d
-
.

dangerous operation o f in c orporation is thus d o ne away wi th It is necessary .

t o select a c ombustible constituent like the cresol sul phonate that has a high -

solubility of the same or der as the nitra te other w i se there w o ul d be a te ndenc y ,

for the substances to separate during the evaporation Safety e xplosives .

c ontaini ng ammoni um nitrate instead of the sodi um salt have been registe re d
under the name of
The products formed on the explosion o f gunpo w der w ere investigate d
by B unsen and Schi s c h ko fi Li nck and Karol y i but the m ost c omplete
3 4 5
, , ,

series of experiments was carr ied out by Noble and Abel 6

Debu s sh o wed
7
.

ur u Mi n e s
'

1 B u ll
US . B ea o f , . 15 , 1 9 12 ,
p . 1 79 .

2 S ee A ny 1 9 1 2 p 1 1 9 4 ; G e r P a t Ap p R
. , . o f S S 1 9 12 p 29 2
. . . . . .
, , . .

3
P o gg A nna le
. n 10 2,
1 8 5 7 p 321 4
, A n na le n d e r C he mle 1 0 9 1 8 58 p 5 3
, . . , , , . .

5
. , r
P o gg A n na le n Ap il , 1 8 63 ; P h il l 1 a g . Se r 4 No 26, 1 8 63 p 266 . . . . , .
, . .

6
P h i l Tr a ns
. 1 8 75 4 9 , , .

7 P r oc . Roy . S oc . 30 , 1 8 8 0 , p . 1 9 8 ; P h il . Tr a ns . 1 8 8 2, p . 523 .
, ,
 MAN UFACTU RE OF G U NP OWD E R 91

that they had made an error in giving potassium hyposulphite as a primary

product of the explosion Noble and Abel accordingly corrected their results
1
. .

The mean percentages from E L G P owder were : . . .

G as e s
So lid s
W a t er
G a se s , p e r ce n t . by v o lu me So l id s , p e r ce n t . b y w e ig h t
C arb o n d io x id e Po ta s s ium c arb o na t e
C arb o n mo no x id e P o t as s iu m s u lp ha t e

H y dr o ge n P o t a s iu m
s s u lp h id e .

Me t hane P t a iu m
o ss s u lp h oc y a nid e
N it r o ge n P o t a s s iu m nit ra t e
Su lp hur e tt e d H y d r o g e n Sulp hur

From 1 g of the powder 271 3

. of gas were produced measured at 760 mm -
,
.

and 0 C and the quantity of heat li berated was 70 0 7 calories

°
.
, .

The products obtained from mining powder have been given by J Harger 2
.
,

and the analysis of the gases from American blasting powder h a s been pub lished
by C M Yo u ng .
. .
3
Hall and Howell 4 have investigated the products from
B obbinite .

1
P hil . Tr a n s
1 8 8 0 , p 20 3
, . .

2
J S o c C h em I nd
. . 1 9 1 2, p 4 1 5
. . .

3
B u ll A m M i n E n g , 1 9 1 0 , p p 63 7 662 ; A ng
. . . . .
—
.
, 1 9 1 1, p . 1886 .

4
U S B u r ea u o f M in es B u ll 1 5,
.
p 1 79 . . .
P A RT I I I

A CI D S
 C H AP TE R VI I

L
SU PHURI C ACID

Manu fa c tur e P ur ifi ca t io n C o n ce n t ra t io n Me lt in g p o in
-
ts Sp e c ifi c g ra vi t ie s
C al cul a t io ns Supp lies in w a r - t
ime

TH E manufactur e of sulp hur ic acid is treated fully in special works such as Ma nufa ctu e r .

L i mg e s Su lp hu r ic Acid a n d Alka l i Here o nl y the general prin ciples can

’
.

be dealt with and those special features whi ch are of importance to the
manufactur er of exp losives .

U ntil the end of the last century or the beginni ng of this practicall y a ll
, ,

the sulphuri c acid was made by the chamber process Now very large .

”
quantities are produced by the contact process In both processes the .

first stage is to bur n sul p hur or a sulphur ore such as zin c blende or pyrites
,
-
,

in an excess of air thu s producin g a gaseou s mi xtur e consistin g mostly of

,

oxygen nitrogen and sul p h u r di oxide I t is necessary now to make the s ul

, ,
-
.

ph ur di oxide combin e with a further quantity of oxygen In the chamber

-
.

process this is done by mixin g a small proportion of o x ides of ni trogen with

'

the gases and water in the form of spray or steam Various intermediate .

”
products are formed but the final product i s chamber acid containi n g about
, ,
”
70 per cent sul phuric acid and 30 per cent water or
. Glover tower acid .
, ,

containin g about 8 0 p er cent acid . .

In the contact process the s ul phur di oxi de is made to comb ine with o x ygen
-

to form the trioxide S0 by p assin g the gases over a heated contact sub stance
3
, , ,

such as platin um or iron oxi de The b u rner gases are p urified by washi ng
.

wi th water and sulp huric acid but afterwards no steam or spray of water i s
,

introduced and consequently it i s not necessary afterwards to concentrate

,

the acid to bring it up to a hi gh strength as i s the case with the chamber ,

process On the contrary the s ul phur tri oxide has to be absorbed in weak
.
-

sul phur ic acid so as to obtain an acid of conveni ent strength Very great .

di fficul ties were exp e ri enced at first because after a short time it was found
that the spongy platinum used as the contact material ceased to be active It .

was di scovere d however that this was due to the presence in the gases of tra c es
, ,

of impurity such as arse nic which p oisoned the platinum W hen these
, ,
.

are entirely remove d the contac t material reta ins its ac tivi ty for a long time .

The p rinci pal motive of the in v entors in wor king out the cont act p rocess w a s -

95
 E X P L OSIV E S

to pr o d uc e at a rea s o nable c o s t a fuming aci d for use i n t he manufa c ture of

artifi c ial in dig o but large quanti t ie s o f stro ng aci d are al s o require d i n the
,

e x plo s ive s in dustry a n d some explo s ive s works have in fact erecte d contac t
,

plants of their o w n .

In the burner s pyrites is generally burnt but s o metime s b lc n de The , .

burnt pyrites or blen d e is af t er w ard s sent to smelting works w here the metal ,

i s extracted S ulphur (brim s t o ne ) is u sed only in localities w here there are

.

n o s melting w orks a v ailable .

t
Pu r ifi ca io n. Fo r the manufacture o f explosi v es a hi gh d egree of purity i s genera lly
required of the sulphuri c aci d especially free d om from ar s enic Aci d made , .

by t he c ontac t p rocess al w ays has sufficient purity as arsenic a nd o ther foreign ,

s ub s tances are ne c e s sarily remo v e d i n the c our s e of manufa c ture Sulphuric .

acid made from pyrites by the chamber p rocess generally c o ntain s a c o nsi der
able am o unt o f arseni c a n d o ther impurities The s e c a n be remove d by .

trea ting the acid wi th sulphuretted hydrogen and all o wing it to s ettle bef o re
con c entrat ing it .

C o ncent a ti on
r . Acid o f 70 per cent strength c a n oft e n be c o ncentrated up to 8 0 p e r cent
.
-
.

by passing it d o w n a Glo v er to w er W here thi s is not available the coneen .

t ration is generally c arried out i n lea d pans heated either by a fire u n de r neath
or by s team c oils lai d in the bottom of the pan Ab o ve this s trength lead .

pans c annot be u sed as they are atta c ked too much by the h o t aci d For .

t he production of pure w ater white concentrated sulphuric aci d the further -

c on c entrati o n may be c arried out in glass or platinum st ill s heate d from below .

The greater part o f the water i s thu s distilled o ff together wi th a little acid .

The glass still s ho w ever are liable to break a n d the consumption of fuel i s
, ,

c onsi d erable P latinu m i s very expensive and has risen in price consi d erably
.

o f late years The platinum is sometimes coated with gol d to di minish the
.

loss In neither glass nor platinum can sulph u i c acid of the highest strength
.
r

h e pro d u c ed to obtain thi s a further c oncentration in cast iron pans is necessary -

.

Th e s e works that have a contact sulphuri c aci d plant c a n use the ir recovered
aci d to ab s orb the s ulphur tri o x i d e and so bring it up to any required strength
-
, .

In fac tories w here the a c id i s purchased the s ame obj e c t c a n be accomplished

by mixing the w eak recovere d acid with fuming aci d 1
c ontaining 20

o r 60 per cent anhy d ri de Bu t in s ome pro c e s se s of manufac ture as for

. .
,

i n s tance the di s pla c ement proces s fo r gun cotton su c h large quantities of

,
-
,

w eak a c id are pr o du c ed that rec o ncentration i s nece s s ary Su c h r e c o n c e n tr a .

t ion is nearly al w a y s carrie d out in the explosives works themselves as it ,

d o e s n o t pay to t ransp o rt s uch a material back w ards a n d forward s by road

o r rail .

1
Th e co mme r c ia l t rm f
e o r u lp hu i
s id f 92 t
r c 90 pa c o o er ce n t . t n gt h ( g
s re s . .

is (c o n c e nt t d
ra e o i l f v it r i l ) t h t f t h fu m in g
o o . a o e a c id c o n t a in in g n hv d
a r id e

is (No rd ha u s e n o il o f v itr i l ) Ol um o o r e .
 S U L PH U RIC ACID
Ca sca de D18
The c oncentration is carried out either in a cascade plant or by di rect
contact with hot gases In the cascade plant the acid i s made to flow in turn
.
.

through a large number of beakers or basin s each one of which is at a sli ghtly ,
‘

lower level than the last These are all heated from below by means of a .

suitable furnace Formerly the vessels were made of glass or porcelain but
.
,

much trouble was caused by the continual breakages Now basins of fused .

si lica ware or special iron are used and breakages are comparatively rare .

A type of plant u sed very extensively in the explosives industry is that Kessler s ’

of Kessler the principle of which i s to bring a current of hot gas from a gas pla nt
,
.

producer in contact with the acid in a plant constructed of volvic stone which ,

i s only very s lightly attacked by the hot c oncentrated acid Fig 1 5 shows . .

an early form of the plant whi ch has since been m odi fied in some details The
, .

hot gas from the producer enters by the tube 0 into the s a tu r e x S where ,

i t passes down the channels q and is caused by ba ffl es to rush over the surfac e
,

of the acid in to the channels q l

From here it passes up through the pla .

'
te a u x A B C D where the inverted cup s cause it to bubble through the
, , , ,

acid which passes down from one plateau to the other by means of the over
flow pipes n The acid thus receives a preliminary concentration and the
.
,

gas is partially cooled down before it goes through the dome Z and the pipe P
to the condenser The weak acid is introduced on the top plateau and the
.
,

concentrated acid flows out of the s a tu r e x through the pip e m into a lead tank ,

where it is cooled by means of a coil through which water flows The arrange .

ment of th e ba ffles in the s a tur e x has now been altered they run transversely
to the di rection of flow of the gas and acid and the hot gas passes under each ,

o f them in turn .

The gas passing away thro u gh P carries with it a considerable amount of

sulphuric acid mostly in the form of very fine mist w hi ch is very di ffic ul t
, ,

to remove and is very inj uri ous to the surroun di ngs The gas is therefore .

passed through a condenser consisting of a large lead t ank packed wi th care

fully graded c oke Formerly the gas was drawn o ff by means of a steam inje c
.
‘

tor in the pipe P but thi s was very extravagant in steam a n d caused the
,

condensed acid to be very di lute Now a fan i s u sed instead Water is . .

sprayed i nto P to assist the condensation of the acid The general arrange .

ment of the plant is shown in Fig 1 6 Careful regulation of temperatures . .

and dr aughts is necessary to ensure the best results .

In decidi ng what strength of oleum it is best to use one of the properties Melting
p o ints
that must be carefully considered i s that of the melting p oints of the acids In -
.
.

Fig 1 7 (pp 1 0 4 5) are given the values as determined by Kn ie ts c h and publi shed
. .
-

by him in the important paper on the contact process which he read before the ,

German Chemical S ociety in October It will be seen that there are

1
Ber .
, 190 1 , 40 9 3 ; C h em I nd
. .
, 1 902, p . 6
.

V OL . I .
 Se c io t na l E le va t io n

t n
Se c io a l P la n
FI G . 15 . K e s s le r Co n nt r t r
ce a o
 S U L P H U RIC ACID 99

EL é V Ar lo n

P LA N

FI G . 16
. Ar ran g e me n t o f Ke rs
s s le
’
an t
Pl fo r t h e
Co n ce nt rat io n of Sul p hur ic Ac id
 E XP L OSIVE S

ma x ima a t t he p oints corresp onding to H O) (H H

( SO . z , 2 .

and (S 0 ) and m in ima a t in t erm edia t e p o ints A s tre ng th that is much used
3 ,
.

i s one con ta ini ng 1 8 t o 20 per cen t a nhydri de it has the ad v anta ge that it is
.

li quid a t a ll o r dina r y tempe r a t ures Wi t h an increa se of strength t he mel t ing

.

poin t rises r apidl y un t il wi t h 4 5 per cent anhydr i d e i t reaches a tempera .

t ur e a t w hich i t i s ver y inconveni ent t o dea l wi th an acid that gives o ff den s e

fumes e v en a t t he o r di na ry t emperat u r e and boil s below From here
t he mel t ing po in t falls aga in u n t il wi t h a st r ength of 60 to 65 per cent a n hy
-
.

di i de an a ci d is obt a ined w hich i s li qui d in summer a n d can be easily melte d

a t a n y t im e of t he y ea r The choi ce of acid to be used therefore res t s be t ween
.

C O Y a nd
. . . containi ng 1 8 to 20 per ce nt a n d 60 t o 65 per cent a n hy . .

dr ide The decision mu st depend on the pri ce at whi ch the acids can be
.

ob ta in ed a nd t he facili t ies for rec oncentra t ing or usin g the weak a c i d s produ c ed
in manuf a c t ur e “ h ere such facili ties are d eficient it i s bette r to u s e the
.

s t r onger oleum Ve r y little w aste acid wi ll then be produced O t herwi se

. .

mos t w orks p r efer to use t he 20 per cen t ole u m C O V is n e w li t tle used . . . . .

in explosi v e s w orks for revi vifyi n g w aste acids .

One of t he di sadvan t ages of t he 20 per cent oleum is that i t atta cks iron .

muc h mo r e s t rongl y t han either C O V or the 60 per cent oleum 1

On the
. . . . .

o t her han d t he v apo u r t ension of t he wea ker oleum i s considerably smaller

t han t ha t of t he s t ronger l Vh e rea s C O V conta inin g 9 8 5 per cent H SO .
.
-
. . .
-
.
g

boil s a t 3 1 and 1 0 0 per cent a c id at about 20 per cen t oleum boils

.
.
.

a t a b o u t 140 a n d 60 per ce n t at 60 C °
. .

Table s of t he sp e cifi c gravi t ies of mi x t ure s of sul phuri c acid and water
have been publish e d by v arious investigato rs There are sli ght di fferences .

be t w een t he best of t hem du e p ri n cipally to the difficul ty of d eterminin g the

s t r eng t h of t he a cid wi t h a v ery hi gh degree of acc uracy and perhap s part ly ,

to t he p resen c e of t rac es of i mp u rity in the mate ri al The Tables of Lun ge .

and hi s cc w orkers N a ef a n d Isler are much used but up on the whole the
-
,

figures of Pickerin g seem to be the best Many of the Tables are not di rectly .

compa r able bec ause t he s p ec ific gravi t ies have been t aken at di ff eren t te mpera
t ur es or are refe r red to w a t er a t d ifferent te mperatures ; in som e cases the
g r avi t ies a re corr ected for a ir di pla c ement and in others not For general
s .

w ork i t is bes t to w eigh both t he aci d and wate r at the ordi nary temperature

and not to corr e ct for a ir di splacemen t for t he introduc tion of small cor r ee ,

tions is no t onl y t rouble s ome but is liable to lead to error Pickering s figures .
’

w e re t herefo r e ca lcul ated by me to thi s basi s 2

a n d a re given in the follo w ing ,

Ta ble
1
See Kni e t s c h . lo c . c it .
2
J . S oc . C he m I nd . 1 90 3 .
 S UL P H URIC ACID 10 1

G R AVI TI E S SU L P H U R I C AC I D m AI R
“

°
SP E C I F I C or AT 15 C . .
10 2 EX P L OS I V E S
SUL P H U R I C Ae rD
°
SP E C I FI C G n a v r r rrzs or AT 15 C . IN AI R— co nti n u ed
 S UL PHURI C ACI D 10 3

For co ncentrated acid the determin ation of the specific gravity is not of
much value as an in di cation of its strength because the density reaches a ,

maxi mum at about 9 7 5 p er cent-

.

The following Table gives the corrections to be appli ed to the specifi c

gravi ties if the temperature va ri es from 1 5 1 °

For the e ff ect of impurities on the spec ific gravity of sulphuric acid s ee
Marshall J So c C hem I n d 1 9 0 2 p 1 50 8 Fig 1 8 (p 1 0 6) gives the specific
, . . . .
, , . . . .

gravities of a number of trade samples of some of which had becom e

c ontaminated wi th traces of ni tric acid also some acids that had been used
,

and reconcentrated several times in a Kessler plant The curves corresp ond .

ing to the Tables of P ickering and Lun ge are also given for compa ri son .

Kni e tsc h has determin ed the spec ific gravi ties of fuming acids (lo c ci t ) . .

His figur es are to b e foun d in the foll o w in g Table :

To ta l SO3 C o r r e s p o n d in g
H 2SO4

(ma x )
.

(ma x )

The strength of the fumin g acid is generally exp ressed a s per cent free . t
Calcul a i o ns

S0 b ut sometimes as total S0
3, W hen determ ini ng the strength by analysis
3.

it i s most conveni ent to express it first as per cent H SO a n d there are other .
z 4,

advantages i n expressing it thu s A figure i s of course obtained which is

.
, ,

greater than 1 00 but it gives at once the quantity of sulphuric acid that will
,

be forme d if 10 0 parts of it be ad ded to a mixture and if 1 00 be de ducted from ,

it the rema inder i s the amount of water that will di sappear from the mixture
,

to form this sulphuric acid Thi s remain der m ultipli ed by 8 0 ./ H p

.

1
L un g e a n d H u t r A lka l i Ill a ke
'

r e , P o cket b o o k
-
r s -
.
 SUL PHURI C ACI D

FUSI ON C RVE U
MEL TI NG POI NT CURVE
‘

C RYSTALL I SATI ON C RVE U

MEI / PI NG U
PO I NT C RVE
ETC . OP OL E UM NOT
YET POLYME RI SED

FI G . 1 7. Me lt ing -
nt s
Po i o u huric
f S lp
 60 ° C

UM
OLE

s o}
, fr e e

4 8 °C

Ac id a nd Ole um (Kn ie ts ch )
 EXP L OSIV E S

Per Ce nt H
.
zS O‘
FI G . 18 . Sp e c i fi c G ra vit i es o u h u r ic
f S lp Acid

/
80 1 8 Z gives
4 44 )
-
the percentage of free S0 The percentage of 11 8 0 3. 2 ,

multipli e d by 0 8 1 63 ) gives the total SO Si milar rul es m ay be 3.

ma de for converting any of these three exp ressions into any other
F be the percentage of free SO 3

T total SO ,

H H SO 2 4

F 4 4 44 (H 1 00 )
5 4 44 T 444
0 8 1 63 H
0 1 8 3? F 81 -
63
F + 1 00
1 2 25 T

The conversion can also be effected by means of the scales at the base of Fig 1 7 . .

All cou ntrie s d u ring the war are suff ering more or les s fr o m a shorta ge of
sulphuric aci d due to the enormous demands and the di s turbances in the
supply o f the raw materials In Ge rm any the cessation of the imp o rt s of
.

pyrites from over seas appears to have caused considerable t r o uble i n spite of
—

the fact that they have the Belgian acid works at their di sp o s al a s well as
their own and that ores can be obtaine d from Norway H ungary a n d Styria
,
1
, .

They are sai d to be making sulphuric aci d from calcium sulpha te (gyp s um )
and magnesium sulphate (Kie s eri t e ) 2
.

1
S ee F .Do nG , N a tu re , M c
. n an 23 ar h , 1 9 16 p , . 82
.

2
C h em Tr a de J o a n , No v 27, 1 9 1 5
. . .
 C H AP TE R V III
NI TRI C ACI D

Manu fa c t ur e R e co very nitro us fume s St o ra ge Th e dis tilla tro n Nit re

of

c a ke : N i t r ic a c id fr o m t h e a t mo s h er e : D ir e c t o x id a t io n : C y anamid e r o ce s s
p p
:

Se p e k s p r o c s s
r
’
e Hab e r s p r o ce s s Os t w ald s p r o ce s s P ro p er t ies Sp e c ifi c
’ ’

g ra vit ie s Fr e e zi ng p o in t s B o ilin g p o int Vap o ur p r e s s u r e

s s
- -

N I TRI C acid i s usually made by di stilling C hi li saltpetre with sulphu ri c acid Manuf actur e .

in large iron retorts Formerly these were made of such a si ze as to take a

.

charge of about half a ton of sulphuric acid and the same quantity of nitrate
now they are genera lly made to take twice as much or more Fig 1 9 shows . .

a retort somewhat simil ar to those used for the Va len tiner system To take .

a ton of ni trate the retort should be about 6 feet in di ameter and 6 feet hi gh
it must not be too small on account of the danger of frothi ng over or priming .

Horizontal cylindrical still s are also used .

At one time nitric acid wa s o nly made of about 60 per cent strength but .
,

when a large demand for stronger acid arose for the manufacture of exp losives
i t was found that there was no re al di ffic ul ty in obtaining nearly the whole
of the acid of 9 2 to 9 4 per cent strength By the recovery of nitrous fumes
. .

acid of 60 per cent strength is still produced formerly it was sometimes con
.

c e n tr a te d by di still ation with sulphuric acid but now it can be utilized directly
,

mixed with G O V or oleu m. . . .

The nitric acid vapours were formerly c ondensed by a ir cooli ng by lea di ng

-
, C ondenser s.
them through a large number of stone ware j ars connected by stone ware - -

pipes but this system was inefficient and requ ired much plant and space
, .

The reason for its adoption was that metal condensers coul d not be use d because
they were attacked by the acid and stone ware condensers cooled w ith water
,
-

would have cracked with the changes of temperature B ut with the improve .

ments that were made in the manufact u re of earthen and stone ware thi s has —

been altered The Guttmann condensing battery has been much use d (Fig
. .

It consists of a number of vertical stone ware pipes immersed in a tank through

-

w hi ch water circulates ; at the b ottom these pipes are connecte d by cross

pieces in such a way that whilst the fumes have to pass up and d own the pipes
one after the other the con d ensed acid flows along from one cross piece to
,
—

another through in verted siphons and finall y to the storage tank .

1 07
 EXP L OSIV E S

In t he Va lentine r plant (Fig 21 ) s t o ne w are coils are use d and these are
.
-
,

also a d op ted now by many w h o do no t w o rk by Va le n tin e r s system t e n

'

first introduced there were frequent breakages especially at the upper ,

extremi ty where the c oil ente red th e w ater The coils coul d be repa ired by
.

the ad di t ion of a piece of le a d pipe j oine d on for t he s t ro ng a c i d has but little

,

FI G . 19 . N it r ic Ac id St ill

action upon it S uch breakages are not so frequent n o w they c a n be avoided

.

to a large exte nt by not immer s ing the fi r s t c o il in water but coo ling it by ,

runn in g wate r over clo t hs laid on t he c oil Coil s can now be o btained ma d e
.

of fuse d silica or v i tr e o s il as much as 2 in c he s in diameter and 60 feet long .

These are much more resistant than s tone w are a nd can be repaired whe n -

broken .

t
Val en in e:
The principal peculia ri t y of Dr Va le n tiner s system is that the di stillation
.
’
 NIT RIC ACID 10 9

is carried out in va cu o At the end of the series of condensers and jars shown
.

in Fig 21 there i s a vacuum pump w hich w ith every stroke draws in some
.
,

caustic soda solution to prevent the acid fumes attacking the metal of the

G u ttma nn C o nd e ns in g B a tt e r y fo r N it r i c Ac id
’
FI G . 20 . s .

pump too much The large number of small washing j ars is also to absorb
.

the aci d fumes as far as possible before they reach the pump The a d vantages .

claime d for the system are that the time of working a c h a rge is much shortened
by the use of a vacuum that th e process is under better co ntrol a nd that
, ,
 NIT RIC ACID
there i s less breakage of coils because the temperature is lo w er also that the ,

acids are pur er The plant i s well designed and made and consequently
.
,

the users have generally found i t satisfactory but some who have tried worki ng ,

both wi th and without vacuum state that they can achi eve equally good results
at the ordi nary pressure and with less comp licated app liances
, .

In the Skoglund process the gases and vapours from the stil l are made to
pass up a reaction to w er and then up a condenser instead of down The .

result of this is that the oxides of nitrogen are removed almost completely
from the c ondensed nitric acid The plant is used in many explosive s factories
.

in North America and in several French dynamite works 1

.

P rocesses for the continuous or semi continuous manufacture of nitric -

acid have also been tried 2

.

In the retort a cer tain proportion of the nitric acid is always reduced Rec overy Of
mtmm u mes
through vari ous causes to lower o x ides of nitrogen Some o f thi s is dissolved .

by the strong acid in the condensers and i s an obj ectionable impurity In .

order to p revent this solution taking place air is sometimes dr awn over the
acid w hi lst it i s still warm and thi s carries away the greater part of the lower
,

oxides Whether thi s i s done or not there is always some nitrous gas that
.
,

is not condensed in the coils and thi s must be recovered not only because ,

it is valuable but al so because it would cause a nui sance After passing

, .

through the condensing coils therefore the residual gases are made to pass, ,

up a series of towers filled with Lunge Ro hr mann plates or Guttmann B ohr - -

mann balls A j et of air is also intr o duced partly to draw the gases along
.

better and partly to o xi di ze the nitrous gases These consist principally .

of ni tric oxide and nitric peroxide NO and N 0 the former is rapidly c o n ,

verted by free oxygen into the latter so that then there i s only NO which , 2,

when it comes in contact with water form s a mixture of ni tric and nitrous
acids
2N0 + H 0 H N 0 + H N0 2 2 3 2

But nitrou s acid is only sparingly soluble in water or weak nitric acid and ,

consequently it is given o ff again as a mixture of ni tric oxi de and peroxide

2H N0 2
2 NO + N0 + H 2 0
2 .

In the presence of oxygen and water the cycle of changes then recommences .

Although the combination of the ni tric oxide with oxygen i s rapid the reaction ,

w ith water is rather slow and c onsequently a considerable amount of tower

,

space i s necessary for the almost c omplete absorption of the fumes .

Nitric acid of 90 to 9 5 per cent strength can be stored either in large stone fifi
fgfficfij
’
.

S ee A F O o , S S , 1 9 0 6, p 325 ; E W o lff , ib id , p 3 73 ; O
1
. . tt . . . . . . . G utt mann , ib id .
,

p 3 76
. a
ls o G
L i m ge , S u lp hu r i c A c id a n d Alka li , 4t h e d , v o l i p 1 78
. . . .
, . .

2 S ee L n e u
g , lo c c i t , p 1 54. . . .
 E X P L OSIV E S

ware vessels or in iron tanks line d with chemical lead The action of the .

acid on the lead i s very slight and such tanks last for years before they require
,

to be reli n e d For weaker aci d stone ware and glass are practically the only
.
,
-

ma t erials that are available The maximum theoretical strength of acids

.

running from a to w er o f this ki nd is that o f the constant boiling mixture of

nitric acid a n d water which contains 68 per cent of the former and has a
,
.

s pe c ifi c gravity of 1 4 1 (4 2 but genera lly it is considerably weaker than

°
-

this and h a s a spe c i fi c gravity o f about 1 3 8 corresp o n ding to 61 per cent -

, .

H NO If a series of to w ers i s i nstalled the weak acid from one should b e

3. ,

raised continuously and ma d e t o flow down the next in the opposite direction
to that of the gases .

The nitrate i s d rie d by being sprea d on iron plates on the top of a retort ,

w hi lst a p revious charge i s being worked It is passed in through the man .

hole in the top of the retort sulphuric a c id i s run in and the lid of the man
, ,

hole i s close d and luted down with clay or a mixtu re o f asbestos powder a nd
water glass Theoretically
-
. parts of s O are required to convert 1
, 4

part of N a N0 into Na H SO 3 in practice i t i s usual to add rather less 1 0 4

4 ,

to 1 0 8 parts so that the nitre cake contains about 20 per cent of the neutral
0

, .

sulphate Na SO To u se too much acid w ould not only involve a waste of

z 4.

thi s s ubstance but would make the bi sulphate too soft a n d acid and therefore
, ,

di ffi cul t to handle It i s al w ays well to add a little weak nitric acid to the
.

charge o r some weaker sulphuric acid or waste acid from the manufacture of ,

nitro cott o n In this way not only i s some of the weak acid w orked up but
.
,

the yield of good nitric acid i s increased If the charge is practically free from .

w ater some of the nitric acid in the retort is converted into ni tric anhydride
, ,

which breaks down very readi ly into nitric peroxide and oxygen and produces ,

a dark acid The charge having been introduced the fire is li t and the retort
.
,

i s gradua lly heated If worki ng in va c u o under a pressur e of 7 inches of mer

.

cury acid beg ins to come over at about 1 00 C if at atmospheric pressure

,
°
.
,

some w hat higher As the distill ation becomes m ore active the heat must be
.
,

mo derated to prevent priming The fir s t runnings are liable to contain a .

considerable proportion of hy d rochloric acid and other impurities as well as

mu c h nitrou s acid Therefore if acid of good qua lity be requi red the first
.
,

p ortion should be collected separately and not added to the main bulk or a ,

current of air should be dra w n over the still warm acid as mentioned above .

The last runni ngs are li able to be rather weak so that if aci d of the highest ,

strength be required they also should be collected separately .

To work o ff a charge of nitri c acid takes ab out ten hours b ut it is claimed ,

that in the latest Va le ntine r plant it can be done i n four and a half h ours .

Nitr e c a ke
. Wh en the charge i s fi nished and w hilst the c ontents of the retort are ,

still hot the plug in the opening at the bottom i s removed and the residue
, ,

in the retort i s allo w ed to run out through a rem ovable gutter into a tro lley
 NIT RIC ACID
or a shallow cast iron trough Th e latter is preferable as the nitre c ake
-
.
,
-

is easier to break up if it is in a thin layer This i s done by means of a .

crowbar or sledge hammer and the broken cake is removed to a convenient

-

place of s torage until it can be di sposed of Nitre cake consists mostly of .

-

sodium bisulphate with some neu tral sulphate a fair amount of moisture ,

( especially if it has been exposed t o the atmosphere long or has been rained
on ) a little nitric acid and other imp ur ities
, , .

It i s generally used either for making superphosphate manure or hydro

chloric acid and sodium sulphate ; in out o i the way di stricts its di sposal
~ - — -

i s often a matter of di ffi culty as its value is small and i t i s troublesome to ,

‘

transport on account of its corrosive quali ties At the present time (1 9 1 6) .

these di ffi culties are much accentuated by the enormous increase in the

manufacture of nitric acid for the pro d uction of military explosives and ,

fresh outlets are bein g sought for this b y product 1

J C r o s s ma nn has
2 -
. . r

w orked out a process for treating the nitre cake wi th calcium s ul phite and -

lime and so converting it into caustic soda and sodi um sulphate As there .

is a great demand for sulphuric acid nitre cake solution i s being u sed for ,
-

many purposes where formerly oil of vitriol was employed Apparently it .

is being used successfull y in the wire making industry and for variou s purposes
in connexion with te x tiles 3
P rop osals to use it for the manufacture of.

ammonium sulphate have been adversely criticised 4

Other use s are .

acidi fying the phenolates ob tained i n the working up of coal tar aci di fyi ng ,

soap stock preparing sulphates treating rubber scrap and pickli ng iron and
, ,

steel .

During the last ten years great advances have been made in the manu Nitric acid
fro m th e
fac t u re of nitrogen comp ounds from the nitrogen of the atmosphere U ntil a tmosph e e .
r ,

recently the materials thu s made were used almost entirely as fertilizers :
for the manufacture o f explosives Chile saltpetre remained alm ost the sole
source of nitrogen After the outbreak of war i n August 1 9 1 4 the Central
.

E uropean P owers were cu t o fi from Chile a nd in Germany energetic step s ,

were taken to develop the manufacture of ni trates and nitric acid from the
atmosphere Rapid development of this industry was possible as the pioneer
.

work had already been done .

Many different processes have been proposed and several are in actual
operation on a large scale They may be divided into two classes : those .

in w h ic h the oxygen and nitrogen are made to combine together di rectly ,

and those in which ammonia i s first f ormed and then oxi di ze d to nitric acid
by Ostwald s method The advantage of the latter process lies in the fac t
’
.

1
J S o c C h em I nd 1 9 1 5, p
. . . . . 1 1 21 , 1 9 1 6, p . 77 .

2
I b id , 1 9 1 6, p 1 55
m I nd
. . .

3
C h em . Tr a de J o u r .
, Jan . 8 , 1 9 1 6, J . S oc . C he . .
, 1 9 1 6, p 1 0 9
. .

4
C h em . Tr a de J o u r ., Ma r . 4, 1 9 1 6, Ma r . 1 1 , 1 9 1 6, p p . 23 3 , 23 5 .

VOL . I .
 E X P L OS IV E S

t ha t a mm oni a i s m ore ea sily p r odu c ed t han nitric o xide a s it is formed , w ith

evolu t ion of hea t w herea s ni tric o xi d e is an endothermic compoun d
,

N2 + 3H 2
= 2NH 3 + 24 Cal o ries
Nz + O, = 2NO —
43 -2

And t he o xida t ion of t he ammoni a is al s o an exothermic rea ction as t he ,

con v ersion of the h y dr ogen into w ater supp lies the necessa ry heat .

P ro c e s s e s fo r the di rec t o x idation of nitrogen were those first w orked

out commerciall y Th e s e requi re t e mpera t ures of several thousa nd degrees
.
,

w hi ch ca n onl y b e obta ined by means of an electric arc Air i s passed through .

t he arc and then r apidl y cooled t o prevent the ni tri c oxide decomposing
aga in in t o o xygen and ni trogen About 2 per ce nt of ni tric oxide is obta ined
. .
,

and t hi s is converted i nto dil ute ni t r ic acid by pas s ing it up towers do w n

w hich w a t e r i s fl o w ing The variou s processes di ffer in the means taken
.

to pa s s a s u ffi cien t ly large v olume of a ir thr ough the arc and then cool them .

In t he Birkeland E yde fu rnace an alternating arc i s made to spre ad out fan

- .

wi s e by m e ans of elec tro ma gnets In the P aul in g furnace the arc i s V shaped
-
.
-
,

due t o the use of long elec t rodes incli ned to one another at an angle And .

in t he Sc h fi nh e r r furnace a s p iral flame is obtained by blowing air t h rough

incli ned holes in a tube forming one of the elec trodes
.
.

The consumption of energy in these processes i s about 60 kilowatt hours -

per kilogramme of nitrogen fixed Consequently they c a n only be worked

.

at a profi t w here t here i s a v e r y la r ge supply of cheap water power and No r way ,

is t he p r incipal seat of the indust r y The emerging a ir contains about 2 .

per cen t of ni t ri c oxide and t hi s i s mostly c onverted into weak ni tric acid
.
,

by pa s s ing it up to w ers d o w n whi ch w ate r i s fl o w in g .

The 40 per cen t ni t r ic acid t hu s obtain e d coul d be concentrated by di still a

.

t ion w i t h sul phuric acid but as ni tric aci d i s difficult to transport it is usua lly
,

conve rted into calcium ni t r ate by neu traliz ing i t with lim esto ne and mi lk
of lim e and evaporating down The product thu s obta ine d i s known as
.

No r w egian saltpetre a n d is used a s a fertil i zer Ammonium nitrate is also .

m a d e by neut r ali zing wi t h ammo n ia li quor And sodium nit r ite is obtained .

in t he las t sc rubbing t o w ers by runni ng so dium c arbonate solu t ion do w n

t hem I t is s ai d tha t a t a S w i s s w orks c ontrolled by the Elektro c hemische
.

in Bi t te rfeld t he ni t ric oxide i s all owed to oxidi ze to peroxi de which ,

is r ecovered in t he form o f sno w by s t rongly cooli ng t he a ir 1

This is then to .

b e all o w ed to mel t and sent into German y in tank wagon s and there made ,

in t o ni t r i c acid by treatment with air and wate r Nitric peroxide freezes .

at abou t 1O C and boils a t about 26 C it i s far less c orrosive than ni tric acid
.
°
.
°
. .

The manuf a c t ure o f calcium cyana mi de w a s worked out by Frank and

Caro and is n o w t he basis of a whole series of importa nt chemi ca l industries
,
.
.

1
Bad e r ma nn S S , . 1 9 14, p . 3 27 .
 NIT RIC ACID
m
I t i s made from calciu carbide which is manufactured by heating lime ,

and anthr acite coal together in an elect ri c furnace at ab out 3000 C The °
.

carbide is p owdered and placed in a retort which can be heated e x ter nally
by means of a gas or electric furnace and nitrogen is passe d in The nitrogen , .

is now generally obtained by liquefying air and fractionally distil ling it .

Ca C 2 N2 C a N zC C
C a lciu m ca r b i d e Nitr o g e n C a lc iu m c y a na mi d e G r a p h ite

The reaction starts at about 8 00 C and proceeds with the evolution of °

.

heat The temperature must not be allowed to rise ab ove 1 40 0 C or some

.
°
.
,

of the cyanamide will be reconverted into carbide The cyanamide i s used .

on a large scale directly as a manure and also as a source of ammonium ,

sulphate which i s appli ed for the same p urpose I t i s also converted i nto .

cyanides guanidin e di cy a ndia mine and other comp ounds For the con
, , .

version o f cyanamide into ammonia it is treated in a closed tank with steam

u n der pressur e in the presence of water and alkali The reaction is exothermic .

and proceeds for a time after the steam has been shut o fl W hen the steam .

has been applied three times the yield is almost theoretical 1

The cyanamide .

process i s apparently the one which the German Government is developing

m ost largely for the production of nitric acid for the manufacture of explosives .

The consumption of p ower i s considerably less than in the direct oxi dation
methods : about 24 kilowatt hours per kg of fi xed ni trogen as compared
-
.

with 60 and the raw m a terials required coal lime nitrogen and steam are
, , , ,

all cheap Consequently the process can b e worked wherever p ower can
.

be produced at a mo derate cost

"

In thi s process bauxite a natural crude alumina is converted into

, ,
Serp ek
’
s

p r oces s .
al u min ium nitride by heating i t with c oal in an atmosphere of nitroge n in
an electric fu r nace at 1 700 to 1 800 C ° °
.

A1 20 3 3C N2 2AlN 3C O -
243 Calories
P roducer gas a mi x ture of nitrogen and carbon m onoxi de is used as the
, ,

source of ni trogen .

The nitride i s then treated with a solution of caustic soda which converts ,

it into ammonia and sodium alum in ate

AlN 3Na OH NH 8 Na 3 A10 3.

Many of the impurities of the bauxite are eliminated during these operations
and conse quently the aluminate can be used for the manufacture of aluminium .

The p ower required i s only about 1 2 kilowatt hours per kg of fi x ed nitrogen -

.
,

but bauxite being a comparatively e x pensive material the process can onl y
b e used in combination with aluminium works .

1 S ee W . S. L an d i s, J . I nd. En g . C h em .
, 1 9 1 6, p . 1 5 6.
 E X P L OSIVE S

P rofessor Haber w orked out his meth o d for the direc t produc t ion of
ammonia from ni t rogen a n d h v dr o ge n by a t horough study of t he physical
chemi s t ry of t he r ea c t ion The proce ss has been taken over and d evelope d
.

commercially by t he powerful Badi sche An ili n un d Soda Fabrik The mi xtur e .

of g a s es is passed at high tempe r ature and pressure over a soli d contac t

substa nce w hi c h promote s the reac t ion Osmi um and uranium are some
, .

of t he ma t e rial t ha t have b e en use d for t hi s pur p ose but apparen t ly iron

s
,

i s mo r e sa t i s fa ctory in some respect s The temperature is main ta in ed at -

.

500 to 700 C and t he pressur e at about 200 atmospheres The gases are
°
. .

c ir c ul a t ed roun d a closed circui t wi th heat a n d c ol d regeneratin g applian c es ,

fi rs t over the hea t ed contac t sub sta nce and then t hr ough a c ooler where ,

t he temperature is redu c ed to 60 or 70 C whi ch causes the ammonia

° °
.
,

to separa t e as a liquid In e a ch c ircuit about 6 per cent of ammoni a is forme d

. .

a n d li quefied Thi s process i s said to requi re power o nl y to the e x tent of

.

2 ki l o w att hours per kg of fixed ni trogen but very great di ffi c u lties had
-
.
,

to be o v ercome before plant could be ma d e to work satisfacto r ily at the

enorm ous press u re requi red The low cost for power i s also compensated
.

to some e xtent b y t he compara t i v ely hi gh cos t of hydr ogen It i s obta ined .

ei t her b v the elec t roly s is of wate r or from producer gas by li quefy ing out
t he carbon mono xi d e a n d p u rifying it H aber s process i s apparently bein g .
’

developed b y t he German Govern ment in a ddition to the cyanami de process .

If ammoni a t oge t her wi t h oxygen or air be passed over a suita ble contact
, ,

subs ta nce i t is conver t ed into oxi d es of ni t rogen from w hi ch nitri c aci d can ,

be ob t a in e d Thi s has long been kn o w n bu t abou t 1 900 P rofessor Ostwald

.
,

commenc e d t o in v e s tigate the m ost favourable condi t ions for the reaction .

He foun d t ha t pla t inum was a sui ta ble cata lyzer but it should not be in too ,

fine a con di t ion and t he ga s es sho ul d be passed over it v ery rapidl y othe r wi se
, ,

t he o xides of ni t rogen formed are f u r t her decomp osed i nto ni t rogen and
o xygen So long as the ammoni a w a s pra c ti c all y only a b y pro d uct in the
.
-

dest r uc t i v e di s t ill a t ion of coal t he am ount available w a s to o small and the

, ,

other d eman d s for i t to o great to make this process very suc c essful or
,

rem u nera t i v e But wi t h the introduction of synthetic ammoni a made by

.
,

t he c y a na mide and H aber s pro c e sses t h e c ondi t ions w ere altere d e n tir e lv
’

.
,

The amm oni a mixe d wi th 1 0 volum es o f air is passed t hr o ugh a plug

of p la t inum s ponge 2 cm t hi c k at a t emperat u re of 300 C at su c h a velocity
.
°
.

t ha t i t remains in conta c t w i t h t he pla t inum only 0 00 2 secon d s Ab o u t .

8 5 per cen t of t he ammoni a i s oxi di zed not to ni t ric acid w hi ch c annot

.
, ,

e xis t a t t hi s tempera t ure bu t t o nitric o x ide w hich promp t ly comb ines

, ,

wi t h furt her ox y gen to form ni t ric pero x ide The gases pass up a tower .

w here t hey mee t ni t ri c acid : here t he w ater f o rmed in the reaction

2x 11 , zx o 3H ,o + 106 8 Calories
 NI T RIC ACI D 117

is conde nsed and with the nit r ic p er o x i de a n d further oxygen yields ni tric
'

acid which i s obtained from the tower w ith a strength of ab out 58 per cent
, .

Instead of platinum other catalyzers have been proposed a mixture of ceria ,

and thoria by Frank and Caro burnt pyrites by F Bayer C o etc ,

. .
, .

The development of these processes for the synthetic production of nitric

acid has been of great value to Germany in the war in fact she probably , ,

could not have continued the struggle without them for the stocks of Chi le ,

saltpetre must have been e x hausted after about a year .

The concentrated acid has very little action up on metals The more Prope ties . r
nit ic a ci d
di lute acid acts energetica lly on all the common metals if the acid be quite r

free from nitrous acid there is no action but as commercial acid always ,

c ontains some nitrous thi s is not a matter of great practical i mportance The .

concentrated acid is not very stable and tends to decompose into NO oxygen 2,

and water The ni tric p eroxide di ssolve s readi ly in the strong acid w hi ch
.
,

consequently always has a more or less reddi sh colour In weaker acid the .

solub ility is less and nitric acid of 1 4 specific gravi ty di ssolves very li ttle
,

of the peroxide .

The Tables of Lunge a nd Re y superseded the earlier inaccurate ones but

mvm
,
g es
the more recent determination s of Veley and Manl ey are more numerous
'
1
.

The figures have been interp olated graphically those above 63 per cent ,
.

by Veley and Manley those below by myself and are given in the Table, ,

on p 1 1 8 . .

The influence of ni tric peroxi de on the specifi c gravity i s considerable

and has been ascertain ed by Lunge and Ma r chle w ski for an aci d having
2

the spec ific gravity 1 4 9 6 .

Pe r ce n t . N2 0 4 Pe r ce n t . N20 4 Al t er a ti on o f sp .
gr .

1
P hi l . Tr a n s . A .
, v o l. 1 9 1, p . 3 65 a nd P r oc . Ro y S o c
. .
, 1 90 1 , p . 8 6, a nd J .

S oc . C h em . I nd 1 90 3 , p . 1 227 .

2
Ana , 1 8 9 2, p . 10 .
 E XP L OSIVE S

The figure in t he second c olumn is t o b e subtracte d from the s p ecifi c gra vity
-

be fore ascer t a ining t he s t rengt h of t he ni t ric a cid by mea ns of the s pec ific
gra vi t y Table The amoun t of lo w er
.

oxide is ho w ever of te n ca l cula t ed a s

, ,

nitrous a ci d Th e figures in t he firs t

.

colum n of t he a bove Table mus t b e

m ul t ipli ed by 5 1 9 to give t he cor
-

r esp onding amoun t s of ni t rous acid

in acco rd an ce w ith t he equati on :

N 20 4 E QO H NO 2 H NO a .

The free zin g po ints of mix t ur e s

-

t
p o in s. of ni t ric acid a nd w a te r a re sho w n
in Fig 22 w hi ch i s based on t he
.
,

d e t er minations of Kus t e r a nd Kre

mann .
1
I t w ill be seen tha t a ll mix o w 20 30 70 so 90 f ao fi oli
'

HMO,
t ures soli di fy a t t emperatures con F I G 22 . F r
e e zin
g po in
-
ts of N itric Ac id
si de r ably below t he free zing po int
.
.
-

SP E C I FI C G na v r r r ns o r N I T R I C A CI D A T 1x V AC I '

1
Z . a no rg . C 1 90 4 ,
p .
 NI T RIC ACID 1 19

o f
water I n the first portion of the curve ice separates out in the second
.
,

cry s tals of H NO 3H 0 in the third H N0 H 0 and in the last solid

2 , 3, 2 ,

nitri c acid .

P u re ni tric ac id boils at about 8 6 C under atmospheric pressure and

°
.
, B o iling p oi

at 21 5 under a pressure of 24 m m
°
W hen water is added to the aci d .

the boiling point increases until it reaches a maximum at about 68 per cent
-
.

H NO and then falls again If acid either stronger or weaker than this
a, .

be evaporated or fractionally di stilled the composition tends to approach ,

this percentage and when it is reached the mixture di stils unchanged The
, .

compositio n of the constant boil ing mi x ture depends upon the pressure ,

however ; i n va cu o a mixture contai ning 66 3 molecular per cent H NO .

3

boils at givin g a di st illate of the same composition ; un der 73 5 mm .

pressure the constant boiling mixture contain s 68 0 per cent and boils at .

2
1 0 under 1 0 mm the comp osition i s
22 68 6 per cent 1
. .

Sa p o s h n iko ff has made a few determinations of the vapour pressures of

nitri c acid at 1 5 C 2 °
.

Va p p r e s. .
°
15 C . Pe r ce n t N in
.

v a po u r

With reference to the third column of the above Table it is to be borne in Va p our
”m m “
mind that H NO contain s 222 per cent N It i s therefore evident that
3 . .

the vapours from the nitric acid contain nitric p eroxide or nitric anhydride ,

which have 30 6 and 25 9 p er cent N respectively . .

1
Ro s c o e L i eb A n
, . . 1 8 60 , p p 1 1 6, 20 3
, . . S ee a ls o H J M C r e igh t o n a nd J H G it h n
. . . . . e s

J F r a n klin I n s t , 1 9 1 5, p 1 61 . .

Z .
p lay s , C .
,
1 9 0 5, p p . 53 , 225.
 C H A PTE R I X

MI XED AND W ASTE ACID S . MANIP ULATI ON

Mi x ed a c id Mi x i ng t h e a c id s P ro pe rt ies of mi x ed a c id s Sp e c ifi c r a i ies G vt
a ur p res s u es
V po r : ac id : G un -
co t t o n w as te a c id : Nt
i r o g ly ce in e -
r
w a st e a c id N it ro
: -
co mp o u n d w a st e a c id D ni t r a t io n an
: e
p l t : M ni p la io a u t n
of a c id s : Ma t e ria ls : Rai ing a c id
s Oleu m

N I TRATI O N w he t her of glycerine or co t t on or an aroma t ic compo u nd such ,

a s t oluene is always carried o u t w i t h a mix t u re of sul phur ic a nd ni t ric

,

acids and not wi t h ni t ric acid alone for even t he stronges t ni t ric acid does
, ,

no t act we ll by i t se lf On e of t he main func t i ons of t he sulph u ric acid is

.

to c omb ine w i t h t he water t ha t i s formed during t h e reaction and prevent i t

dilu t ing t he ni t ric acid bu t i t appears probable tha t i t a l o t akes an ac t ive part
,
s

in the rea c t ion and t hat t o some ex t en t a t any rate it combines fir s t w ith t he
,
-

subs ta nce t o be ni t r ated t o form a s ul phuric es t er or sulphoni c ac id and t hat it ,

is t hi s w hi ch is af t er wards ac t ed upon by t he ni t ric acid In t he presence of .

s ulphuric a cid t he ni t ra t ion i s no t onl y more complete but al o more rapid s

.

Mix ing th e The t wo acid s are mixed t oge t her in ir on t a nk For work on a mode r a t ely s .

large scale old s t eam boilers ca n be u s ed for t hi s purpose t h e fire t ubes being
-
,

removed and t he openings closed by ri ve t in g on pla t es For work on a large .

scale i t is be t t er to have s pecial t a nks buil t large enough to hold s everal ,

d ays suppl y of mi xed aci d

’
The be s t form is a c ylin der w i t h its a xi s ver t ical
.
,

t he heigh t b eing s ome w ha t less t han t he diame t er P ass ing t hrough t he .

cover t here shoul d b e a shaf t t o whi ch arms a re a t t a ched so tha t by ro t a t ing

.
,

t he shaf t t he c on t en t s of the t a nk ca n b e s t irre d “ h e n t he mi xi ng is carri ed .

ou t in small bo iler s t he a gita t ion of t he li q uid usually has to be e ffec t e d by

blo w ing a ir t hrough i t whi ch cau se s a s ligh t l o ss of ni tric a cid
, .

t
Pr oper i es 01 “ hen ni t ric acid is ad ded in s mall quan t i t ies t o sul phuric acid t he sp e c ific
7
,

gravi t y a t firs t ri se s s ha r ply in spite of t he fa c t tha t ni tric a ci d has a lower

densi t y t han sul phuric The specific gravi t y at t ain s a ma xim um and t hen
.

falls again as is shown in Fig 23 and in the Table on p 1 Sa p o s hni ko fi

'
2
,
1
2 . . .

1
Mar s ha ll , J . S oc . C he m I nd . .1 90 2 p 1 50 8
, , . .

2
Z e its ch . P h y s i lca l . C he m .
, 1 90 4 p p 4 9 , 69 7 ;
, . 1 90 5, p p . 5 3 , 225.

120
 MI X ED ACID 1 21

FI G . 23 . Sp e c ifi c G ravit ie s of Mix e d Ac id s (Mar s hall )

Sp .
gr .

i n a ir i n a ir
 ITKPL OSFWES
'

Q
I

Ho l e cu l a r Pe r c e n t a ge Su l p h u r i c Ac i d
FI G . 24 . Va po ur P r e s s ur e s o f Mi x t u r es o u
f S lp h ur ic Ac id wi t h N it ric
A c id s o f Va r io u s St r e n gt h s

St r e n g t h o f t
n i r ic a c id , pe r ce n t .

C ur v
e B v w e i gh t Mo le cu la r

9 80
85 w
o
! l

fl ~ o
3 1

8 ‘
0

$6
 MI X ED ACID 1 23
.

has obtained s imilar resul ts The following are two maximum specifi c gravities
.

observed by h im with mixtures containin g di fferent am ounts of water

Sp .
gr . l 8 8 10
'

Sul p hur ic a c id 8 9 -32 p er c en t . 8 9 94 p er

-
c en t .

N it ric a cid 1 0 -1 3 6-57

-
28 3 -49
Ox id e of ni tr o g en .
'
27

The second of the above i s almost identical both in composition and density
with the maximum obse r ved by Marshall From the results of his measure .

ments of the vap our pressures Sa p o s h niko ff came to the conclusion that
there is little or no combinati on of the two acids to form complex molecul es ,

and he ascribed these high spec ific gravities to the formation of nitric
anhydride N 0 ,
B ut as t hi s substance has a specific gravity of o nl y 1 6 4
2 5. ,

the e x p lanation does not appear sufficient It seems possible that the hi gh .

densities are due to some reversible reaction taking place between the
sulphur ic and nitric acids .

Sa p o s h nik o fl s determin ations of the vap our pressur es of mixed acids are Va p our
’

°ssm°s
sho w n in the curves in Fig 24 in whi ch mm of pressur e are plotted again st
.
,
p
.
r °

the molecular perce ntage of sulphur ic acid in the mixtur es The sudden fall .

at the left end of cur ve I is due to the fact that the nitric acid used contained
about 0 9 per cent of ni tric oxi de w hi ch is very volatile as c ompared with
-
.
, .

ni tric aci d When a li ttle s ul ph ur ic acid was added it combin ed w ith t hi s

.

to form nitro sul phu ri c acid w hi ch is not volatile Through the greater part
, .

of its course thi s curve i s practically straight : if the acids had been quite
anhydrous and free from impurities it would probably have been straighter .

W ith acids c ontaining water the additi on of s ul phuric acid increases the
vap our pressure because it combines with the water and decomp oses the
,

c omp o un d of nitric acid and water The pressur e is at a ma ximum when .

there is nearly a molec ul e of sulphuric acid for each one of water : then it
falls again . These vapour pressur e curves are also given in another form
-

in Fig 28 whi ch shows the connexion between the vap our pressure and the
.
,

degree of nitration of cotton That there should be such a connexion might

.

have been anticipated as the acti vi ty of a substance in solution generally

,

in creases when the vap our tension in creases but mixtures with equal vapour ,

pressures do not by any means always produce nitr e cottons with equal -

amounts of nitrogen as a careful examination of the diagram wi ll show

,
.

W ASTE ACI D
The waste acid from the manufacture of n itro cotton i s usually r ev iv ifi e d tt
G un-c o o n
“ Ste a c‘ a
by the ad di tion of strong sul phuric and ni tric acid and used again but if , ,
‘

the whole quantity were strengthened up in this way each time the quantity
 E X P L OSI VE S

w ould steadily increase It is t herefore nece ssa ry to di scard some o f the

.

was te acid The quanti t y of was te acid pro duced in t he di spla c emen t process
.

for t he manuf a c ture of gun co t to n is mo r e than in t he ol d er me t hods fo r t he

-
.

recovery of the waste acid i s much m o re comple te and some of i t becomes

dil ute d with the wate r u sed fo r t he di splacemen t I Vh e n n i t r ate d by t he .

Abel process or in centrifugal s a considerable amoun t of acid remain s in t he

gun cotto n after the b u lk h a s been rem ove d in t he centrifugals If oleum
-
.

of 60 to 70 per cent be used to ge t her wi th ni t ri c acid of about 9 3 per c en t

. .

strength the fresh aci d d oes n o t bring t he v o lume of aci d much above it s
,

original b u lk for it does not m uch ex c eed w hat is lost in t he manner j ust
,
.

mentioned together wi th t he ni t ric a c i d ac tuall y c onsum ed in the ni tra t ion

, .

In small factories w hi ch do not p ossess t he plant fo r workin g up the waste

,

acids again thi s is a great a dvantage be c ause onl y a very inadequa t e price
,

can be obtain ed for the waste acid if it ha s to be sold Whe r e the ni tric .

acid can be recovere d on t he spot i t i s more u s ual to u s e oleum of 20 to 25

per cen t str ength
. .
-
fl

These r e v iv ifi e d acids a r e little if at all less efficient than n e w a c id at

,
.
, ,

any rate for the manuf ac tur e of the m o re insoluble varie t ies of ni t ro ce llul ose -
.

The o rganic impurities formed in t he ni t ration process apparen t ly ei t her pass

away in t he nitrate d product and so eventuall y into the wa t ers used for the
purifica t ion or else are o xi dized c omple te ly away by the acid if t hey have
,

passed into solu t ion The quantity of o rganic imp u rity in t he aci d s remain s
.

s ma ll t herefore ; but Will foun d nitro sugars in the aci d s -

.

The portion of the w aste acid t hat is not r e v iv i fi e d can genera ll y b e u t iliz e d
t o some exte nt for the man u facture of ni tric acid The remain der if a n y . . ,

mus t be reconverted into the separate acids ni tric a n d sul phur i c The ,
.

greate r part of the nitric acid can be di st ill ed off in a re t ort and i s t hus .
,

obtained as c oncentrate d acid again Some w eak ni t ric acid can be adde d .

t o t he charge in the retort at t he same t ime and so be w orke d up again It ,

.

is not prac t icable to di stil off the last traces of ni t ric acid in t hi s w a y and ,

consequen t ly it i s necessary to pass t he residual sulphu r ic aci d do w n t he

denitra t ing t ower before reconcentrating i t in a Kessler plant In many .

work s 11 0 atte mpt is made however to rec over any o f t he ni t ric acid in c on
, ,

c e n tr a te d form and all the w aste acid to be t reate d is passe d a t once do w n

.

t he denitrat ing to wer .

The waste acid from t he manufac t ure of nitro gl y cerine al w a y s c on t a ins -

some of t h is subs ta nce or mono or di ni t r o glycerine in soluti o n When

,
- -
.

the waste acid is hea te d this d ec omposes wi t h t he production of c onsiderable

quantities of t he lower oxides o f ni t rogen For t his rea s on i t is difficul t . .

to obtain strong ni tric acid of good quali ty dir ec t ly from it It cann ot b e .

r e v iv i fi e d either because the organi c ma t t e r in solu t ion woul d be liable to

,

decompose when the acid was heate d by the addi tion of strong sul phur ic
 MIX E D ACID
acid Moreover there wo ul d be some nitro glycerine formed which w oul d
.
,
-
,

separate out in the storage tanks and other places and give rise to accidents .

The w hole of the nitro glycerine waste acid has therefore to be denitrated
-
.

The waste acid from the manufacture of nitro aromatic compounds can Nit o com -
r -

p oun d w a te s
often be utili zed after r e v iv ifi c a tio n for the nitration of a further charge acid .
.

In some cases it is used in a lower stage of the nitration Some further .

i nf ormation ab out this is given in Chapters XIX and X X .

The denitratio nof the waste acid is carried out in a tower down which D enitration ,

p la nt
the acid runs at the bott om ste a m or hot air or both are blown in The , , .
.

nitric an d nitrous acids are thus removed from the liquid and pass u p the
tower a s v a p o u r and gas respectively These towers are frequently made
, _
.

of volvi c stone cemented together wi th water glass and asbestos powder -

,

and fi lled with pieces of broken stone ware and glass They are often as -
.

much as 1 0 feet high a nd 1 8 inches i n di ameter to deal with some 1 50 0 lb .

of acid per h our but a much smaller plant w ould deal with this quantity
,

equally effectively A sh ort denitration to w er has the advantage that the

.
'

gases are not heated so long and conse quently there is less loss of nitric acid ,

by formation of nitrogen and ni trous oxide It is of course important .

, ,

that the li qui d and gases be well di stributed and brought into intimate and
repeated c ontact wi th one another In E ngland it is usual to de ni trate with .

steam o nl y : it is thus easy to drive the ni tric acid c ompletely out of the
weak sulphuric This is facilitated by the dilution which the sulphuric acid
.

undergoes from the condens a tion of the steam for weak sulphuric acid does ,

not retain nitric and nitrous acids so obstinately as when it is c oncentrated .

In Germany the stea m is often made to inj ect heated air with it into the
base of the denitrating tower : 1
a somewhat stronger sulphuric acid is
thus obtained containing 78 instead of 70 per cent but as it has to be
, .
,

reconcentrated in any case this is not a matter of great practical importance , .

Moreover the stronger acid retains nitrous acid very obstinately in the form
of nitros osul phuric acid H SNO In E vers s patent plant steam an d h o t
, s.
’

,
p

air are inje c te d a t four di fferent places in the t ower (see Fig 25) th e h e a t .
“ ‘

of th e s ul p h u r ic acid flo w ing from the base of the tower is utili zed to heat
the air Supe rheated steam is also used sometimes
. .
2
.

The gases esc aping from the top of the tower c onsist of nit ri c acid water Recove y of
'

.
,
r
nit ic acid r
vapour and ox i des of ni tr o g en ; a n d if air has been inj ected nitrogen and
'
.

oxygen also some carbon mon o xide and di oxide from the decompositio n of
,

the organi c matter i n th e w a s te acid In order to condense the nitric acid

‘

it is necessary to cool the gases Formerly this w a s done by air cooling the .
,

gases being led through a number of earthenware j ars or to u r ils in the “

1
S ee Ru de lo ff , 1 9 0 7, p . 24 7.
2
S ee H . Le m i a tr e, V
ZI o ni teu r s c i e n ti fi qu e u es n ev i lle ,
Q 1 9 1 3 , pp . 21 7 23 1 —
S S ., 1 9 14,
.

30 a nd 48 :
pp
-

.
1 26 E X P L OS IVE S

E vers plant (Fig 25 ) a ir c ooled earthenware pipe s are used the sur face being
.
-
,

inc r eased by sub di vi ding the pipe s at intervals into a large num ber of small
pipes The b e st meth od of c ooli ng i s h o w ever t o t ake the gas es t h rough
.
, ,

pipe s i mmerse d in a t rough o f w a t e r s o arranged t hat the c o ndensate can

fl o w away in t o receivers Before c ooling t he gases t hey sh oul d be mi xed
.

w i t h a ir if it has not a lready been inj ected in suffi cien t quan t ity
, T hi s .

oxi dizes any nitric oxide to peroxide and if wate r be present it converts ,

part of it into ni t r ic acid .

From t he condenser the gases pass t o absorp t ion t owers w here they meet ,

a stream of w ate r and the remain i ng ni t ric oxi de is c onver t ed into ni tric acid .

It is essential that an excess of oxygen be present in the gas t o effect the

c onversion in acc ordance wi th the e qua t ion stNO 0 2H O 4H NO 3 2 2 , .

Whe t her the c on densation is c omplete c a n be seen by t he appearance of t he

gas e s cap ing from t he la s t to w er it sho u ld not be red nor give much fume
w i t h t he air \Vh e th e r t here is an excess o f oxygen in the gases c an be
.

ascer t aine d by analysis : a sample of t he gas i s firs t shaken wi t h di stil led

w ater un t il there i s no f u rther absorption t hen wi th caustic a lkali to absorb ,

any carbon di o x i de a n d fin ally with alkaline pyrogall ol w hen there sh oul d

,

be a di s t inct f urther di mi nution of volume .

The absorption towers are of stone ware a nd sh o u ld be filled wi t h some -

a c id re s ist ing material so as thoroughl y t o di s t ribute both the ascending gas

-

and t he descending li quid and bri ng t hem repeate dl y into intimate conta ct
,

wi th one ano t her a n d cause them to mi x The Lunge pla t es do all t hi s very
.

e fficien t ly if t hey are in perfect w or king order bu t if t he plates are not quite
.
,

true or if t hey get slightly out of the level t he li qui d all runs down one side
, ,

of t he tower and the gas ascends on the o t her and very li t t le absorp t ion t ak e s ,

place If one lays one s hand on a L u nge t o w er t ha t is worki ng one wi l l

.
’

of ten find t hat at one part of the cir cumference t he s hell i s quite hot whilst
the rest is cold sh o wi n g t hat action i s onl y taking place in a porti on of the
,

to w er G u ttma nn s holl o w s t one ware ba lls give a very good result and
’
-
.

have the merit that no s p ecial c are is required in filling them into the t ower .

There are many other forms of stone ware filling for towers proc urable In -
.

order t o eff e c t c omplete absorp t ion of the oxi des of ni t rogen two or thr ee
to w ers are necessary A slow stream of w ate r is run in t o the last one and
.

di s tri bute d uni formly over the c ross sect ion of the to w er A weak nitri c
-
.

acid runs out at the botto m of the to w er and is raised from there by means
of a contin uously acting appliance to t he top of th e nex t one As weak .

ni t r ic acid attacks a ll the common me t als glass and stone w are are the onl y ,
-

ma teri a ls that can be used for the cons t ruction of the pipes and vessels For .

raising the liq u id to the tops of the t o w ers s mall Kes t ner automatic eggs
made o f s t one w are can be u sed but as t he quan t ity is very small it i s b etter
-
,

to use a sma ll app liance whi ch c a uses the acid to r a ise itself and wor ks o n
“

,
 E X P L OSIVE S

t he w ell kno w n p ri nciple o f maki ng the ascendi ng c olumn o f li q uid lighte r

-

t han a de s cendi ng o ne by mi xi ng i t wi t h air 1

From the base of a to w er a .

glass t u be descen d s a di s t ance equal t o abou t ha lf t he height of the tower .

I t t hen turn s t hrough and a s mall di s ta nce beyond t he bend c ompressed

air is inj ec te d in t hr ough a number of small holes When once the rate of .

admi s s ion of t he air has b e en adj uste d the appliance works c ontinuously and
requir es ver y li t t le atte n t ion The mi xtur e of acid and air sh ould be d elivered
.

in t o t he t op of the t o w er below the c over so that the air cannot c arry a w ay ,

par t of t he acid fum es Thi s a ir also serves a useful p u rpose in that it rene w s
.
,

t he s upply of oxygen w hich has been partially e x hausted by the o xi dation

,

of t he ni t rou s g a ses The greate r part of the absorption of the gases takes
.

pla c e in the m i ddl e t o w er or t o w ers : in the first to w er the acid is

ip sli ghtly t o near the li mi t theoretically pos s ible namely
‘

s t r eng t hened t , ,

68 per cent HNO . In the last t ower t he last traces of fume are absorbed
, .

The acid from the c ondenser generally has a speci fic gra v i t y of 1 4 1 t o -

1 42 and c on tains 67 to 69 per cent H NO

-
that from the to w ers i s somewhat
.
3

w ea ker.

MANIPUL ATI ON OF ACI D

So far as p o s sible aci d s of a ll sort s should be c onveyed about the w orks

i n pi pe s a n d no t in t anks carboys or bottles In a factory which makes
. .

i t s o w n a c ids and rec oncen t ra t es them there i s no reason w h y t hese vessels

sh oul d ever be u s e d at a ll except in case of emergency t e r e v e r it is feasible .

the a c i d s shoul d run from one place t o another by gravity but of c ourse ,

thi s is only p o s sible t o a li mite d e xtent a nd w hen the acid has c ome down ,

to the g roun d level it is necessary t o raise i t again .

For s trong sul ph uric mi x ed and w aste acids tanks pipes and other
, , ,

appli ances of either iron or lead can be used and last for a very long time .

Iron is cheaper in fi rs t cost bu t lea d can be sold for a good price after it h as
,

b ee n used ; iron has the further advantage that it can be fitted up by any
skill ed w or k man whereas lead can onl y be j oined by a lead burner Special
, .

sorts of iron are made suc h as ta n tir o n duriron and c o r r o s ir o n w hich resist
, , ,

acids particul arly w ell so that they can even be u se d for c oncentrat ing
,

s u lph u ri c acid and c ondensing nitric acid These metals are very ric h in .

sili con and are c onsequen t ly more brittle t han or di nary c ast iron Ordi nary .

2 inch w rought iron s te am piping ful fil s most of th e p u rposes of an acid factory

- -
.

Storage ta nks c an also be made of iron or steel b oiler p lates Strong nitric .

acid has lit t le action upon iron but the dil ute acid di ss olves it rapi dl y Th e
, .

vapour th at ri ses from the surface o f the acid i s muc h m ore di lute than the
1
S ee P . 6! S vo l . v ii ., 1 8 9 4, p . 9 1.
 FI G . 26
. K e t ne r
s Au t o ma t ic E le va to r or Egg
V OL . I .
 1 30 E X P L OSIV E S

acid i t s elf and where this c ondenses it is liable to attack ir on strongly

,
.

Conse quently it is bette r to use vessels and pipes of lead for thi s acid .

Stone ware is also used very largely with

-

ni tric aci d Fused silic a w are such as

.
,

v i tr e o s il is ho w ever better especially w here

, ,

h ot acids are dealt wi th as its c oe fficient of ,

expansion is very small and c onsequent ly

there is very littl e tendency t o crack For .

u s e at high te mp e r a ti u e s a proportion of
'

zirc onium or titani um o xide is added to

prevent de v i tr ifi c a tio n of the sili ca Con .

de n s e r s for nitric acid basins of casc ade ,

plants for the c oncentration o f sulphuric

acid caps for Kessler plants and many
,

other articles are made of this material .

Alumi nium is also sometimes used as a

material of c onstruction for acid plant but ,

i n most cases possesses

no advantage over i ron
o r lead .

Ra is ing acid. Wh ere acid is runni ng

i n a c ontinuous stream
one of the best appliances
to use for raising it is an
automatic egg such as
that of Kestner the c on ,

struction of w hich is
shown i n Fig 26 The . .

li qui d i n the feed ta n k A -

, ,

runs by gravity into the

body B of the elevator
, ,

or egg As soon as the

.

body i s full the li qui d

raises the float Y w hi c h , ,

by means of the rod C , ,

closes the air e x h aust

valve and opens another
valve which admits c om
pressed a ir The pressure FI G 27 K t n r Aut ma t ic E le va t r f r N it ric Acid
, . . es e o o o .

closes the valve M and , ,

f o rces the liqui d up the pipe T into a high level tank The air after , ,
-
.

deli vering the li q u id e xhausts through the same pipe causing the pressure
 MIX E D AC I D
to fall and the valves to resume their former positions the cycle o f opera
tions then repeats itself automatically in the same manner These egg s .

can be obtained made of iron w ith or without a lea d li ni ng or of earthen

, ,

ware Fi g 27 shows one type of the appliance specially devised for nitric
. .

acid . It can be fitted with a meter which automatically registers the

,

quantity of liqui d that has been raised A type of elevator is also made
.

with a double body so c onnected up as to give a continuous stream of

'

acid Acid c an also be raised by means of a centrifugal pump driven either

.

electrically or by a belt .

Where the aci d has to be raised o nlv occasionall y a non automatic egg ,
-

can be used This is simply a strong vessel made of one of the materials
.

j ust mentioned and fitted with three pipes one for the admission of the li qui d
, ,

one f o r de livery and one fo r air The inlet and the air pipes are provided
, .

wi th valves which a r e Operated by the attendant .

Wh en acids have to be transferred from b ottles carboys or dr ums to a ,

storage or mixi n g tank they can be tipped in through a funnel placed higher
,

than the top of the tank and connected with it by a pipe In the case of .

oleum c ontaini ng 60 to 70 per cent anhydr ide there is some di fficulty in

. Oleu m.

c onse quence of the great volumes of most obj ectionable fumes that it gives
off especiall y as the acid has to be warmed to keep it li qu id The producti on
, .

o f fumes can be almost entirely avoided by the following devi ce The dr um

of acid is raised to a platform ab ove the level of the tank to which it is to be
transferred and a pipe i s inserted through the bung hole the other end of
,
—
,

the pipe going to the b ottom of the tank A vacuum is then produced i n .

the tank by means of a steam j et worki ng through an ej ector : as soon as

-

there i s sufficient vacuum the oleum starts to flow over and will then siphon ,

over by itself without any further assistance from the ej ector These ej ectors .

can be obtained made of special aci d resisting alloys but those made of ordi nary
-
,

iron withstand the mixture of steam and acid fumes quite well .

Oleum is kept and transported in wr ought iron dr ums cast i ron i s liable
- -

to burst in consequence of the oxidi zing action of the acid on the carbon .

Metals are attacked by 60 per cent oleum considerably less than by 20 per
.

cent .oleum .
 P A RT IV

N ITRI C ESTERS O F C A R BO
H Y D R AT ES
 C H AP TE R X

TH EORY OF NI TRATI ON OF CELLULOSE

St age s o f ni tra t io n o f c e llul o s e H ighe s t a tt ainab le nitra t io n S lu b ilit y o

So lub le ni t ro c e llul o s e Quant it y o f a c id

-
C o n s u mp t io n o f a c id E ff e c t o f
nit ro u s a cid Temp era tur e a n d t ime o f n itra t io n Na t ur e o f th e c o tt o n
N it ro c o tt o ns o f lo w nitra t io n P y ro x y lin C o llo dio n
-

C EL L U L O SEbeing a non volatile c oll oid all the or i nary metho ds of determin Stag es of
d
-
,

ing its molecular weight are inappli cable and it i s o nl y possible to deduce it “
3312
“
22 ,

from a study o f the c ompounds that it forms At first the simplest possible .

formul a was assumed for cell ulose C H 0 and gun cotton of high nitrogen , 10 5,
-

percentage and low solubili ty in ether alcohol was supposed to be formed -

by the sub stitution of thr ee N0 2 groups for hy drogen atoms C H 0 (N0 ) , G 7 5 2 3,

and was c onsequently c all ed tri ni tro cell ul ose The less nitrated product -
.

soluble i n ether alcoh ol was si mil arly supposed to be the di ni tro cellul ose
- -

0 6H 8 0 (N0 ) Later worker s obtaini ng e v idence of intermediate stages

5 2 2.

of ni tration proposed to increase the formula of cell ul ose : E der doubled

1

it Viei e quadrupled it and Men delée ff octupled it giving 48 atoms of

,
ll 2 3
, ,

carbon to each molecule and hydr ogen and oxygen in proportion A nitro ,
.

cell ul ose h aving the c omposition o i the ab ove mentioned trinitro compound - -

wo ul d c ontain 1 4 1 4 per cent ni trogen Q u ite as much as this has never Hi g h e t . .

s

been found by the analysis o f any product that has ever been obtained but attaina b le ,
mtra tw n
vari o us investigators by ni trating with mi xtures of ni tric acid and phosphorus ‘

pentoxide or with c oncentrated sul phur ic and n itric acids and e x tracting
,

the product with ether alcohol have obtained percentages between -

and
Lun ge and Bebie found that w ith mixtur es of sul phuric and ni tric
5

acids the highest percentage of nitrogen was attained not with anhydrous ,

acids but with mi xed acids c ontai ni ng 1 1 or 1 2 per cent of water : wi th a

, .

mi xture i n which the proportions H SO H NO H O were 633 5 25 3 1 g 4 3 z

0

1 1 3 4 they produced a ni tro cotton c ontai ni ng 1 3 9 2 per cent N but this -

.
,

1
B er .
, 1 3, p . 1 69 .
2
P . et S .
, p . 2; C R
. .
, 9 5, p . 1 32 .

ll/I o m teu r
3 ’

s c i e n ti fi qu e , 1 8 9 7, p . 5 1 0 .

4
S ee E r de , Vie ille , lo c . cit H o it s e ma A ng 1 8 9 8 p 1 73
, .
, , .
; L un g e a n d “ f
e in t r a u b ,

An g .
, 18 99, p . 1 44 .
5
A ng 1 90 1 p 5 1 4
.
, , . .

135
13 6 E X P L OSIV E S

was not s ta ble Af ter k e eping i n t he we t s ta te i t w a s r e analyzed a n d found

.
‘ -

to conta in then o nly 1 3 5 per cent N and other ni tro c ottons nitra te d almost .
,
-

as hi ghly w ere found to decompose rapi dl y un t il the sam e composition was

reache d even though the mate ri al wa s kep t un der w ate r This corresponds
, .

very closely wi th t he formul a 0 11 0 e n de k a nitro cellul ose 24 39

- -
.

Hen c e t he auth ors c onclu de tha t the m olecule with 24 atom s o f carbon fits
t he fac ts s uffi ciently well bu t point out th at thi s is o nl y the l o wer li mit of .

t he po s s ible si ze of t he cell ulo s e m olecule a s t o the real magnitude of which ,

t here i s li t t le or n o evi dence .

Hake a n d Bell by nitrating fi lte r paper wi t h a mi x t ure o f concentrate d

.
-

s u lph u ric and nit ri c acids i n the proportion 3 : 1 for several days obtained ,

a percen t age o f ni t rogen as high as 1 3 9 6 bu t their pro duc t w a s washed only ,

wi t h c o ld wate r whereas Lunge and Bebie washe d theirs for several days
,

wi t h ho t w ate r 2 .
.

l Vith t h e possible exception of thi s e n de ka ni tro ce llulose no defini te - -

nitro celluloses wi th every p ercentage

fi

s t ages o f n itr a tio n can be rec ogni ze d -

o f ni t rogen from 7 to 1 3 5 and m ore can be pro d u ced and t hose of the same ,

d egree of ni t ration may be soluble to very different extents i n ether alc ohol -
.

To charac t e rize a ni tro c otton it i s better to Specif y t he percentage of ni trogen -

and the solubil ity rather than to state the number of NO groups that it 2

is supposed to c ontain in each m olecule The follo wi ng Table shows the .

pe rcentages of ni trogen and the volumes of gas evolved in the nitromete r

by t he di ff erent i ntro cellul oses of the C series The figures have been
-
24 .

calc u la t ed using the latest ato mi c weights .

Fo r m u l a C . c . NO pe r 1 g . Pe r ce n t . N

D o d e ka ulo se
-
ni tr o -
ce ll

E n d e ka ce ll ulo se
-
ni t ro -

D e k a mi t o ce ll ul o e r - s

E nn ea ni t r o ce llul se
- -
o

O kt ni t r o
o -
ll ul o -
ce se

H p to ni t r ce ll ul o se
e -
o -

H a nit o ce llulo se
ex -
r
- -

P e n ta ~
n it r o ce llul o s e ~

Te t r a -
ni tr o c e ll ulo se

Nitr o cellulose c onta ining up to 1 2 7 per cent N can be obtained by

-
.

1
I t i o f in te r t to n t t ha t t h e v lo c it y o f ni t ra t io n f ar o mat ic c m p u n d d i
s es o e e o o o s s

so lv d in ul p hu i a c id i a t a ma im um w he n t h m l cu lar p ro p o r t io n o f s ulp h u ric

e s r c s x e o e

a c id to w at r i 1 0 7 o b o ut 1 1 4 p c en t H O b y w e ight (Mart in n Z p h y i k
e s r a -
er .
Q . se . . s .

C 1 90 4 , 50 , p .

2
S ee J . S oc . C he m . I nd 1 90 9 , p . 45 7 .
 TH EO R Y o r N I TR AT I O N o r C E LL U L OS E 1 37

ni trating with nitric acid alone but only wi th di fficulty and the structure of , ,

the fibres is much damaged In practice mixtures of sulphuric and nitric acid .

are alway s used Variou s investigators have made numerous experiment s

.

to ascertain the effect upon the product of altering the c omposition of the
acid mi xture The results publi shed by Br ul ey Lunge and Bebie (lo c ci t )
.
1
, .
,

and Sa p o s h niko ff have been c ollected together by the last name d a n d plotted
’
-

on triangular co ordi nates the best method of representing the composition

-
,

of ternary mi xtures 2
The numbers on the central line running from each
.

c orner (Fig 28 ) represent not the percentages by weight b ut the molecular

.

percentages obtained by di vidi ng the percentage by weight of each of the

,

three constituents by its molec ul ar weight adding together the figures thus ,

obtained and working out the percentages afresh On the same figure .

Sap o s h ni ko ff has a lso given the vapour tensions which have already been ,

presented in another form in Fig 24 It will be seen that for equal percentages . .

of nitric acid the vapour tension is a maximu m on the li ne j oining the points
marked H NO and 11 0 H S0 or s lightly to the left of it
3 2 This sh ows
, 2 4, .

that whe n water is present in excess it combines with the nitric acid to form
a less volatile c ompound but on the addition of sulphuric acid this removes ,

the water from the combination and combines with it instead There is no .

evidence of any combination of the sulphuric wi th the ni tric acid The three .

curves I II and III indi cate the degree of ni tration of the cotton the space
, , , ,

inside c u rve I is the region of the e n de ka ni tro cottons (about 1 3 5 per cent N ) - -
.
,

that between I and II the region o f the deka nitro cottons (1 2 8 per cent N ) - - -
.
,

and between II and III that o f the lower ni trates with nine to si x nitro groups
(1 2 to 9 per cent N ) beyond curve III nitration is inc omplete
. It will be .

seen that the ni tration curves foll ow a c ourse simil ar to th at of the vapour
press u re curves : it seems that the c ompound H N0 H 0 has little action 3, 2

on cell ul ose and that the presence of sulphuric acid is required to set free the
ni tric acid from this comb ination before it can act .

The percentage of ni trogen i n a nitro cellul ose is the pri ncipal factor i n -
Solub ilities .

determi ni ng the amount of energy that wil l become available when it explodes
hence the importance of attaini ng a high degree of ni tration A very large .

proportion of the ni tro cellul ose manuf act u red is afterwards converted into
-

a dense colloid by treatment with a solvent whereby the original fibrou s ,

struct u re of the cellulose is destroyed The properties of this colloi d and .

the nature of the solvent to be employed depend upon the solubility of the
nitro cellul ose : hence the importance of determini ng this property The
-
.

solvent used for the determination is almost invariably a mi xture of two

parts of ether and one part of alcohol The series of experiments by Br ul ey .

and Lunge and Bebie included determinations of the solubilities of th e

1
P . et s , v o l. Vfi i ., 18 95 -
18 9 6 .

2
Re p o r t of 7th I nt e r . Co g n re ss App lie d C h e m .
, t
Se c io n I I I B .
, p 4 1
. 1 90 9 , p 44 2
. .
 E X P L OSIVE S
’

ni t r o c o t t o n s Their r e s ul t s a re s ho wn in Fig 29 t o ge t her wi t h Sa p o s h niko fi s

-
.
.

ni t ra t ion c urve s in s i de t he inn er U sh ape d d o t t ed c urve is t h e re gi on of t he

-

H2 0 , H, SO,
FI G . 28 . D eg r
ee of N it ra tio n o f N it r o - co t to n a Fu n c t i n o f t h M lec u la r
a s o e o

Co mp o s it io n of Mi x ed Ac id a nd the Va p o ur T n i n e f th
s o N it ri Aci d
o e c

c ollo di on c o t to ns c omple te ly or alm o s t c omple tely s oluble ether alcoh ol in -

.

The ni tro c o t to ns bet w e en the tw o c u rve s h ave an in t e rme di a t e d e g ree of

-

solubil ity 1 0 to 90 per cent

,
t h ose ou t si d e th e ou t er one a re a lm o s t insoluble
.
.
 TH EORY o r NIT RATI ON o r C E LLU L OS E 1 39

It will be seen that the molec ul ar percentag e of water in the mixed acid i s
the principal factor in determi ning the solubility This diagram
. be of

H - O - H - SO
. _
 E X P L OSIV E S

carrie d o u t under very diff eren t con di t i o n s fr o m t h o se t hat prevail in the

works .

The co t t on u s ed fo r t he s e e x periment s w a s generally cotton wool which -

,

is di fferen t in many re s p ec t s to t he c o t t o n w aste mostly use d on th e large

s cale : i t is o f much m o re o pen t e x t u re each fibre being s epara t e d fr om the ,

o t her s s o t ha t t he acid can s oak in v ery readil y t hus facili ta t in g the ni tra t i o n
, ,
.

Bu t a s a re s ul t t he ma t erial is very bul ky and for this reason inconvenient ,

t o u s e on a man u facturing s cale as it re quires a very large proportion of mixe d

,

acid C o t t on w ool h a s o f t en been subj ec t e d t o a very drastic bleachi ng and

.
-

s c ou ri ng proce s s w here b y the properties of t he cellulose and of the resulting

,

ni t r ellu e are inj uriou s ly aff ected

o c
-
l o s 1
.

So lu b le ni t ro Wi t h aci ds c ontai ning a very large proportion of w ater or sulph uric acid
c ell ul o s e.
nitra t ion proceeds very slo w ly and i s never c omplete By raising the .

t emperature of nitration this can be overc ome t o some extent bu t t hen other ,

reac t ions also take place : o x y cellulose and ni tro oxycellul ose are f o rmed -
,

and a c onsiderable propor t ion of t he cell ulose is broken do w n altogether and

pa s ses into solution Thus Lunge and Bebie obtained the resul t s s h o w n
.

below wi th an acid of the c omposition :

So l u b l e th e r
t ti t gfggfipl t
r
T ime o f n i ra on Te m p e r a t u r e Pe r ce n . N Y ie ld p e r ce n .

4 H o ur s

1 H uro

The nitration w a s prac t ically c omplete i n four hours at the or di nary

te mpera t ure t here w a s o nly a sli ght i ncrease in the n itration solubility a n d ,

yield w hen t he t ime w a s e xten de d t o twenty four h our s Increa s e o f t h e

,
-
.

te mperature to 40 di minished the y iel d some w hat sho wi ng t hat t he c e llulo s e

°
,

molecule i t self w a s being at t acke d At 60 in f o ur hours thi s action w a s .

°

so s t r o ng that the fibres were entirely de st r o yed and t he nitro cell ulo s e coul d -

I
S ee K i lm r
e , J . Soc . C he m . I nd . , 190 4 .
p . 9 67 .
 TH E ORY OF NIT RATI ON OF C E LLU L OS E
onl y be recovered by pouring the acid mixture into water W hen the time .

was cut down to a quarter of an hour this destruction of the fibre was much
reduced Lunge and Bebie found that with increase in th e proportion of
.

water there was an increase in the effect on the structure of the fibre U p .

to 1 5 per cent of water by weight in the acid mixture the structure appeared
.

to be unaltered ; but from 1 8 per cent upwards the fibres were somewhat .

drawn together a n d the characteristic twisting of the c otton fibre disappeared .

W ith a further increase in the percentage of water the structure was destroyed
almost c ompletely the lumen was torn open and the fib res disintegrated into
, ,

small particles which were felted together forming little lumps With 23 to .

25 per cent of water this destructive action attained a ma x imum

. with still
more dilute acids the fibres remained intact again but on prolonged action ,

they were broken down into smaller portions By nitrating cotton with a .

mi x ture of H S0 3 46 per cent H NO 3 5 45 per cent H 0 1 8 20 per

5 4
2 4 .
,
—
.
, 2
—

cent in the proportion o f 30 of acid to 1 of cotton at a temperature of 40

.

C la e s se n obtains a ni tro cotton entirely soluble in alcohol (9 6 per cent by

-
.

vol ) suitable for the manufacture of celluloid (Germ P a t

. of . . .

1 90 4 )
Me n delée ff and other Russian investigators have adopted a formula of the
followi ng form to express the effect of nitrating with acids of any particular
c omposition if the c omposition be w r itten 2H NO a H SO cH O then 3 g 4 z ,
”
the characteristic is m which i s e qual to (1
“
a Acid mi xtur es
,

w ith m > 0 were supposed to give p roducts of high nitration and low
solubility those with m , O soluble ones Those in which the value of m .

e xceeded 1 by onl y a little give soluble nitro c ottons with a maximum of -

nitrogen If m lies between

. and 0 3 the solubility is uncertain If -
.

Fig 29 be examined with reference to this formula it will be seen that acids
.
,

with e qual values of m lie on a series of straight lines a ll p a ssing through the .

point marked H 0 H SO i n the centre of the base li ne I f m

2 , 2 4 l the .
z

locus of the points is the line runni ng from the centre of the base li ne to the
point H NO H 0 These acids c ontain the same number of molecules of
3, .

water as of sulphuric and nitric acids together It wi ll be seen that this is .

indeed the locus of ma x i mum solubility but that the degree of ni tration may ,

vary considerably on this li ne Apparently in order to get a product perfectly

.

soluble in ether alcohol it is necessary to have enough water not only to c onvert
-

all the sulphuric acid into H S0 but also all the nitric aci d into H NO 4 5, 3 4.

For m 1 the locus of the points lies on the straight line going vertically
z

upwards from the centre of the base to the apex .

Nitration is a ff e c ted to some e x tent by the proportions of acid to cotton ,

because during ni tration nitric acid i s used up and w ater i s formed so that ,

the composition no longer remains the same If the proportion of acid to .

cotton be very great the composition onl y alters slightly o f course In , .

 E X P L OSIV E S

the experiments on which Figs 28 and 29 were based the proportions were
.

generally 50 or 1 0 0 l and the c onse quent alteration in positi on on the

,

diagrams w oul d onl y c o rr e s p o n d t o 0 5 to 1 5 molecular per cent -

As a .

m o lecule of w ater i s formed for every m olecule of nitric acid use d up the ,

molecular percentage of the sul phur ic acid remains unaltered and the point ,

representing the molecul ar c omposition descends at an angle of 60 para llel °

t o the li nes marki ng the percentage of sulphuric acid .

t
Co ns ump io n To produce a ni tro ce llul o se with 1 2 9 6 per cent N exactly one part b y
- -
.
,
o f acid.
w eight of n itric acid is use d up for each part of ce ll u lose and 1 71 parts of the ,
-

n itr o ce llul ose should theoreticall y be obta i ned

-
In practice the yiel d is as
.

a rule very nearly equal to the theoretical More generally the connexion
.

between percentage of nitrogen and c onsumption of acid i s given by the

equations

w here x i s the nitric acid used up in the nitration of one part of cellulose and ,

y the percentage of nitrogen in the ni tro cell ul ose formed and z i s the ma xim u m
-
,

theoretical yield from 1 00 parts of cotton These equations apply e qua lly
.

w ell to all nitration processes whether of hydrocarbons such as toluene or

, ,

alcohols such as gly ce

Lun ge w ith his c o workers Weintraub and Bebie investigate d the effect
-
, ,

of u s ing ni tric acid containi ng a c onsiderable proportion of nitrous acid .

They found that nitri c acid c ontaining as much a s 6 per cent H NO gave .
2

as good yiel d s as high ni trogens and a s low solubilities as acid free from thi s
,

impurity E ven when the proportion of nitrou s acid was higher than t h is
.
,

the effect was only sli ght Lunge and Bebie also examined the stability of
.

the products by determining the e xplosion point s and the Abel heat te sts .

They came to the conclusion that the nitro cotton made with acids containi ng
-

nitrou s acid i s as stable as that made with acids free from it but their results ,

hardly bear thi s out The tests were in all cases rather unsatisfactory showing
.
,

that the products had not been stabili zed sufficiently : the Abel te sts were
n o w orse fo r the nitrous products than for the others but with the explosio n ,

test the former gave slightly worse results in every instance The true stabili ty .

o f a ni tro cell ul ose i s ve r y difficul t to determ ine with certainty

-
u nl ess it i s ,

very h a d indeed it can only be ascertained by storage trials under variou s

con di tions extendi ng over m onths or years The evide nce such as it i s
.
, ,
 TH E ORY OF NIT RATI ON OF C E LL U L OS E
indi cates that nitrous acid has a sli ghtly bad e ffect on the stab ility If the .

products had been thoroughly stabi lized perhap s the evil eff ect woul d have
bee n eliminated .

Lun ge and W eintraub studi ed the influence of temperature and time of

ni tration of c otton wool with a mixture of concentrated s ul phuric and nitric
acids in the proportion 3 l and found that w ith a rise of temperature the
,

velocity of the action increases considerably 1

.

Pe r ce n t . lo ss
Te mpe r a t u re Pe r ce n t . N Y ie ld p e r ce n t .

of c e llu l o s e

It will be seen that at high temperatur es the ni tration proceeds rapi dl y

to a maxi mum and then the yield falls again the cell ulose i s first converted
quantitatively into nitro cellul ose and if the acti on of the acids be prolonged
-
,

the product di ssolves partly and the yield is consequently di mini shed The
, .

part which i s not di ssolved i s also attacked with the consequence that the ,

percentage of nitrogen i s reduced In the case of acids containin g a .

considerable prop ortion of water thi s is demonstrated by the Table on p , .

1 20 and is confirmed by the fo llowing figur es w hi ch were obtained by ni trat in g

, ,

with concentrated acids at 32 °

Tim f n i t ti n e o ra o

5 Mi nu t e s
15
30
60

1
S ee a ls o L un ge , J . A me r . C h e m S oc
. .
, 1 9 0 1 , 23, p . 527
.
1 44 E X P L OSI VE S

F u rt her Tables sho w t h e i nfluen c e of t ime wi t h m ixtur es of concentrate d

ni t ri c and sulphuric ac i d s in d iff e r en t p r oport ions

These resul t s in di ca t e t ha t w hen the p r o port ion of sul phuri c acid is in c r ea s ed

t he v eloc i t y of a c t ion is dimin is h e d This appli es no t onl y to the ni t ra t i o n
.

p r oc e s i t se lf bu t al s o to the s ub s idi a r y a c t ions The y s ho w t hat i t i s not

s
,
.

onl y cheaper bu t als o be t t er to ni t ra t e wi t h a mix t ure con t a ining a con s idera ble
p r opo rt ion of s u lphuri c a cid p r ovi d ed t hat t he a cid ca n be a ll o w ed t o a c t on
,

t he co t t on for s ome hou r s but t hat if it be des ired to ob t a in a high degr ee o f

,

1
25 4 u n ni t ra t e d ce u
ll l o se .

2
Th e u nn i t r a te d ce ll ulo se w a s de t r min ed b y tr ea t ing t he p ro d u ct wi t h so di u m
e

et hy la te so lu t io n . Th e au t ho rs u set h e t rm
e una l te red ce llul b u t the w rd
o se ,
o um

ni t ra t ed is p re fe ra b l
e. b e ca us e t h e ce llul i n o t n a lt red a lt ho u gh it h
o se s u e ,
as n o t b ee n

ni t ra t ed to an a p p recia b le e xi e n t .
 TH E ORY OF NIT RATI ON OF C E LLU L OS E 1 45

nitration in a short time as when nitrating in centrifugals for instance the

,
-

, ,

proportion of nitric acid must not be too small _

.

H ake and Bell found that the course of the nitration i s greatly aff ected
1 ’

by the physical form of the cellulose If thi s be very dense the acid cannot .
,

readily penetrate it and the partly exhausted acid can only di ff use away
,

and be replaced very slowly Thus fi lte r paper is much slower in attaining .
-

its maximum degree of nitration than cotton wool and the thicker and denser -
,

the paper i s the more i s the nitration delayed A larger proportion of sulphuric .

acid also co mb in e s w ith the more dense material

‘

Time t ti
o f ni r a on t
C o to n w o o l

Pe r ce n t . N

5 m in u t e s

The acid used was a mi x ture of concentrated sulphuric and nitric acids in
the proportion 3 1 the product s were not stabili zed but merely washed in
c old water .

In order to make s u re that the cotton wool whi ch they used for their
experiments di d not give different results from other sorts of cotton Lunge
m
,

and Bebie carried out comparative nitrations with these di fferent aterials .

The acid used had the following c ompositi on by weight : H SO 63 8 4 per z 4

cent H NO 1 6 9 6 per cent H 0 1 9 20 per cent

.
, 3
-
the results were
.
, 2 .

P nt N e r ce .

C o tt o n w o l he mically p ur e
o , c 1 17 6
Am e ric an o tt o n (midd lin g fair )
c 1 15 6
Am e ric an c o tt o n (Flo rida )
E gy p t ian c tt o n w hit e (Ab a s i )
o , 1 1 69 s -

E gyp t ian c o tt o n n at ur al y e ll w q ualit y

,
1161 o .

There is very little difference between the results with the di ff erent cottons
1
J . S oc . C hem. I n d .
, 1 90 9 , p . 460 .

V OL . I.
 E X P L OSIV E S

the di ff erence in t he percentage of ash w i ll acc o unt for a large proportion o f

what diff erence there is The cotton w ool contained onl y 0 0 5 per cent ash
. .
,

t he other c ottons about 0 5 per c ent The nitro cottons were all completely .
-

soluble in ether alcohol The v isc o si t y of the solutions was not determine d
-
.

in t hi s respec t there w ould no doubt have been differences .

The above w ere all normal c ell ul oses of good quality it i s when abnormal
ce lluloses are nitrate d that di fferences are found in the yields and nitrogen
pe rc en ta ges .

L u nge and Bebie (lo o oil ) by ni trat ing with acid of the composition
. .

H NO 3 7 1 7 per cent H SO 3 4 4 1 per cent H 0 28 42 per cent by weight

,
-
.
, Z 4
-
.
, 2 .

ob ta in ed a ni t ro cotton c ontain ing only 6 50 per cent N but the large amoun t
- -
.
,

of basic dye stuff tha t it ab sorbed indica ted that it was to a large ex te nt
-
:

nitro oxycellul ose l Vith ni tric acid alone of specific gravity 1 4 (34 8 mol per
-
.
-
.

cent H NO ) a produc t was obtained of which 62 9 per cent w a s u nni tr a te d

.
S , .

fibre as dete r m ined by treatment with sodium ethylate : allowing for thi s
the nitrated portion conta ined 4 0 0 per cent N It conta ined littl e or no . .

oxyce llul ose or ni tro oxycell u lose W hen 5 per cent of sulphuri c acid wa s
-
. .

added to the ni tri c a product was again obtained w hi ch contain ed a large

,

proportion of oxycellul ose or nitro oxycell ulose there w a s ab out 58 per cent -
.

u nni tr a te d fibre and the ni trated p ortion c onta ined 5 1 2 per cent N
, Crane . .

and J oyce have nitrated c otton with acids containin g little ni tri c acid and
1

much s ul phuric and water With an acid of the composition : .

B y w e ig h t

they obta ine d a produc t c ontain ing 3 5 1 per cent N I t w a s insoluble in . .

acetone ether alcohol a n d all the other u sual solvents for nitro cellulose
,
-
,
-
,

but soluble in strong aci d s caustic alkali s and phenol U ltimate analysis , ,
.

gave res u lts agreeing with the formula C u H 0 NO 2H 0 It contained , 38 20 , 2 2 .

0 3 4 per cent sul phur and must therefore have been unstable
. The composition .

indi cate s that it was a nitro hydro cellul ose - -

.

Py r ox y lin
.
Soluble ni tro cell ul ose or pyroxyli n i s used very largely outside the
-

explosives industry for the manufacture of varni shes photographi c fi lms , ,

artifi cial si lk celluloid etc For practica lly all these purposes ready solubili ty
, ,
.

is essential and high viscosity generally a di sadvantage

, Therefore the .

ni tration i s usually carried out at a fair ly hi gh temperature but it should ,

not be too hi gh else the c ohesion of the material i s inj uriously a ffec ted and
, ,

this i s one of its m ost important properties According to figures g iven by .

1
J . S oc . C he m I nd
. 1 9 10 , p . 540 .
 TH E ORY OF NIT RATI ON OF C E LLU L OS E
Worden Hyatt prepares the material fo r high class celluloid by nitrating
,
1 -

tissue paper with acid of the composition :

The nitration i s carried out at a temp erature of 55 and lasts a half to one °

hour ; there are 22 lb of a c id per lb paper

. The product c ontains 1 1 0
. .

to 1 1 2 per cent N and about 0 1 per cent ash the yield i s 1 40 per cent
. . .

For commoner qualities a smaller proportion of nitric acid is used .

Collodi on is much used to seal surgical wounds for appli cation to cuts ,

and abrasions and as a vehicle for the appli cation of drugs to the
,

ski n when prolonged local action is required The pharmacop oeias of the .

vari ous c ountries contain di r ections for the preparation of the pyroxylin for
these collodions but satisfactory or uniform products are not likely to
’

be obtained by followin g them .

If the coll o di on cotton be of a sui table quality and it be di ssolved in Collodi on

ether alcohol together w ith camphor and castor oil the solution on drying will
- -
,

leave a film which does not contract In this way incandescent mantles are
,
.

coated with material which enables them to bear transit If the film were .

to contract on drying the mantle would be crushed and when the collodion ,

was burnt o ff the mantle would fall to pieces .

1 N i tr o cellu lo s e I nd u s tr y p
, . 113 .
 C H AP TE R X I

CELL U OSE L
N a t ur e o f c e ll ul o se L ig t io n f
no - c e ll ul o se C o mp o un d ll ul ce o ses Rea c s o

cel lul ul p hur i a c id

o se ni t ri
s ed c tt n Vi c a id M r e ri
c e c z co o s

co s e C llul b n oa te A t at
o se Sc hw e z H y d a t ce ll u
es cc - es e it r r ag n t
ze
'

s e e r e

lo se O x y ce llul N it ro-
llul tc
o se Vi co it y O v r b l a ch e d
-
o x y ce o se, e . s s e e

c tt n
o N itrate d m rc e ri e d t t n Eff t f dil ute alk li Co t to n u ed in
o e z co o ec o a s

m nu fac t ur
a llul e A t i n o f b c t ria St ru c t u
ce f co tt o n fi b r
o se c o a e re o e

D ad c tt n e o o

C O MP L E TE kno w ledge of t he nature o f t he pro c es s of nitration a n d the s tability

of ni t ro c ellulo s e woul d requ ire a t horough ac quainta nce wi th the structur e
-

of t he cellul ose molec ule but in spite of numerous inves t igations there is still
,

much that i s unkn o wn about the c hemistry of this substance There are .

fe w substances w hi ch are m ore c omplex or about which i t i s m ore di ffi cul t ,

to arrive at a defini te c o n c lusion Thi s i s partly due to the fact that ce llul o se .

compri ses who le series of alli ed substance s whi ch are kn o w n by thi s name , ,

and these are no t all di stinct from one ano t her but are liable to m odifications , ,

w hich c ause one v ariety to merge graduall y into another Cell ulose may be .

converted by reagent s into pro d u c ts such as o x y cell ul ose and hy dr o cellulose ,

- -

w h ich are very similar to the original s ubs t ance in appearance and properties ,

a n d only differ from i t v ery slightly in elementary c omposition They a re

-
.
,

however some w hat m ore reactive m ore liable to be atta c ked by chemical
, ,

reagents But true cell ulo s e obta ine d from diff erent sources also sho w s
.

considerable v a r ia t ions although n o di ff eren c e c a n be d ete c te d in the

,

comp o s ition E ven t he best cotton c on ta ins a proportion of mate ri al which

.
,

c an be removed from i t by treatment w ith bleaching powder and a lkali ,

but the s epara t i o n can ne v er be carrie d to completion because the trea tment ,

also attacks the t rue ce llulose although to a less exte nt The chemical .

behavi ou r o f cellulose cannot be repre s ente d by a fo r m ula c o n ta inin g 24

or any other number of carbon atom s in t he ni t ration no defin i te s ta ges or
-

well charac te r i zed ni trate can be di stin gui s hed on the c ontra ry t he nit r ation
-

appears to be a continuous process from 6 up t o 1 3 5 per cent N Cros s -

. .

148
 C ELL U L OS E
and Bevan e xplain all thi s by the theory that cellul ose c onsists of a solution
”
aggregate that it is a so li d solution i n w hi ch substances of simil ar but not
,

i dentical constitution are di ssolved in one another Others consi der that the .

uni on of these di ff erent c onstituents i s more intim ate a n d i s chemica l rather ,

than physical ; that the cellulose mole c ul e c onsists of a large number of

smaller group s comb ine d together a n d t hat these group s may di ffer sli gh t ly
,

from one another in c onfig u ration and even in composition The w hole .

subj ect of the c hemistry of the coll oids of w hich class cellul ose i s such an ,

important member ab oun ds with difficul ties a n d it is only r e ce n tlv that a n y

, ,

considerable effort has been made to sol v e its problem s .

Ce ll u lose i s the principal c onstituent of the framework or ce llul ar tissue

of plants c otton a n d linen are almost pure cellul ose b ut can be f u rther puri fied ,

by j udi cious treatmen t and are then characterized by their resistance t o

,

chemi cal ac ti on as c ompared not o nl y w i t h m est other organi c materials

,

but also with the alli ed cellul osic substances such as li gno cell ulose p e c t o ,
-
,

cellul ose and the products obtained by the action of reagents on cellulose
, ,

such as o x y cellul ose and hy dro cell ul ose

-
Cellulose has the empir ical
-
.

formul a C H 0 G 10 5.

Of the li gno cell ul oses j u te fibre may be taken as a representative

-
It .

differs from cellulose by ha vi ng a hi gher ratio of carb on to oxygen :

H

6 36
-

0 1 5 8—

By treatment w ith chl orine the non cell ulose can be remove d but even -
,

then the residual cellulose is m ore reactive than normal c o t t on cell ulose and
c onta ins a c onsiderable proportion of O C H groups It i s suppose d t ha t —
.
3 .

cellul o se is fi rst formed i n the plant and i s af t erwards converte d int o ligno
,

cellulose Wi t h the e x cep t ion o f a few materials such as c ot t on hemp and

.
, , ,

to lesser extent rami e practicall y all the vege t able fibres c ontain a consi dera b le
,

prop o rtion of the non cellulosic sub stance pectose

—
In w o o d fibre t he “
.

lig ni fi c a tio n has proceeded f u rther than in j ute By t reatmen t wi t h alkaline .

sul phi tes a fairly resistant cell ul ose can be prepared a n d this i s n o w manu ,

fa c tur e d on a very large scale for paper maki ng but the mate r ial thus obtained
-
,

is more reactive than c otton cell ulose It has been used to a consi derable .

extent for the manuf acture of sporting s mokeless po w der for w hi ch ,

pur pose a high degree of nitration is not s o impor t an t as a thorough

c ontrol o f the rate of burni ng Nitration e x perimen t s w i t h j u t e w ere
. .

carried o u t by lll iihl h a e u s e r using various mi x tures of t he c oncentrate d

1
,

aci d The fibre was purified fir s t b y b oil ing w ith 1 per c ent caus t ic s oda
. .

soluti o n
.

1 ’
D i n g/ e r s P01 J . o ur 18 9 2 ,
28 3 , p . 8 8 .
 Lign ce ll ul oses gi v e a num ber of char acteri tic reac t ions
o— Salt s of s .
‘

a niline c ol o ur t he fibre a d e ep golden yello w P hl o r o glu c ino l di ssolv e d in

- -
.
,

h y dr oc hloric ac id g i v es a dee p magenta c oloration I odin e i s ab sorbed in

,
.

la r e quan t i t y c o lo u ri n g the fibr e a d e ep brown The fibre r eadi ly c ombines

g
.

wi t h c hl o rine as sh o w n by t he char a c t eris t ic magenta c oloration developed

,

o n t he subse quen t ad di t ion of s o di um sulphi t e

. Very characteristi c is the .

rea c tion wi t h ferric ferri cyani de obta ined by mi xing equi valent proportions of
po t a s si u m ferricya ni de and ferric chl oride t he fibre is sta in e d a d e ep blu e
a n d t akes up a co n i de r able qua n t ity o f pigment
s .

Ma t t he w s cla s sifi e s t he co mpound cell ulose s as foll ows :

2 -

P e llul oses rela t ed to the pecti n com ound s of vegetable tissues

( )
a ec to c -
,
—
p
re p r esented amon t he fi b re s by raw fl a x r e solve d by hydr olysis in to pectic
g

r(b
) Lign o ce ll ul oses formi ng the main c on ti tuent of w oody tissue and
-
,
s

r ep re se nted am o n the fib r es by j ute resolved by chlorination into c ell ul ose

g

and chl orin a t ed deriva t i v es of aro ma t ic c ompoun ds soluble in al kali s .

(c) Adi po c e llul oses formi ng t he epidermi s or cuti cular tissue of fibres
—
,
—
,

lea ves e tc ,
resolved by oxi dati on wi th ni tric acid into derivative s simil ar
.

t o t h ose of th e o xida t ion of fats and cell ulose .

The fibres o f c o rk a n d o t her barks b e long to the l ast class but all such ,

ma te ria ls c onta in als o la rge pr o po rti ons of oils and waxes ta nn ins lign o , ,

c ellul o se a n d ni t r ogeno u s subs ta nces Adip o cell ul ose (or cute c ell ul ose ) .
- -

c o n t a i ns a la rger pe r centa ge of c a r b on th an pur e c e llul ose ; p e c to cellulose -

,

on t he o t her ha nd h as a hi h proporti on of oxy gen

,
g .

Rea c ti ons of B es ides the ni t ro cellul oses pr oduce d by the a cti on of mi xt ures of sul phuric
-

a n d ni t ric acids ea c h of t hese a cids al one yields products Co n ce ntrated

i
W th ml , .

sulph uri c a c ids c h ars ce ll u l o se a n d di ssolves i t formi ng de xtri n e and fin all y , , ,

gluc o s e a n d o t her produc t s o f a c omparatively s imple nat ur e If the a cid .

b e dilu t ed fir s t wi t h a t hird of i t s w eight of wate r the cellul ose di ssolves ,

wi t h o u t c harring wi t h t he for ma t i o n of hydr o ce llul ose sometimes -

call e d a myloid a n d c ellulose s u lph u ric ac id C

, O (SO
-
if the m “

1
All e n
’
s Com . Or g . A na l , 4t h cd .
, vo l i .
,
p . 4 34 .
2
i
Tex t le F ib res , 1 90 7 p , . 221 .
 C E L L UL OSE 1 51

act ion be only allowed to proceed for a sh ort time and the cell ulose be then
washed the surface is c onverted into a gelatinous non fi b r o u s fil m In thi s
,
-
.

way vegetable parchment is made Cellulose c ombines very readi ly with .

sulphuric acid of m oderate strength but the c ompound formed undergoes ,

further changes very rapidly There is reason to believe that in the ordi n .

ary nitration process the cell ulose first c ombines w ith the sul phuric acid ,

and that the product then reacts with the nitric acid to form ni tro c ellu -

lose.

Hake and Bell found however that a proportion of sul phuric acid always Mi ed estc
, ,
x

remains c ombined with the nitro cellulose and that the amount does not 25 11
1 8313 -
,

di mini sh below a certain amount when the time o f nitration i s increased a cids . ,

From this they c oncluded that in normal ni tration the ni tric acid reacts
di rectly with the cellulose and that the formation of the mixed esters is due
,

to the absence of a su fficient amount of nitric acid and the c onsequent inter ,

v e nt o n of some of the sulphuric

i But the e vi dence i s inc onclusive as the
1
.
,

c ompound fir st formed when cell ulose is immersed in sul phuric acid is probably
qu ite di fferent from the mixed esters (Fo r further di scussion of these mixed .

esters s ée p .

With concentrated nitric acid nitro cell ulose is obtained Vieill e found W ith nit
2 -
.
r ,

a m"
the following percentages of nitrogen in the products yielded by acids of
di ff erent strengths
Mo le c u la r per ce nt
. H N O3 Pe r ce n t . N
12 7
1 1 -5
1 0 -2
90 d i s s o lve s in a cid , r e p r e cip it a te d w ith w at e r .

friab le mas s .

With acid weaker than this very little nitration takes place ; Sa p o s h niko ff ,

with an acid containing 34 7 molecular per cent H NO obtained a product -

.
s,

c ontai ni ng only 1 46 per cent N Hake and Bell wi th concentrated nitric

-
. .
,

acid obtained ni tro cellulose with as much s 1

, a 3-
5 per cent N 3
. .

Knecht found that when cotto n is i mmersed in weak nitric acid it swells
4
La b il e mi
up and forms a labile nitrate from which the ni tric acid c an be removed ,

again by washing with water if the c otton be i n the form of yarn a c ontrae ,

tion of length takes place To estimate the amount of acid retained by the
.

c otton Knecht squeezed it out and then let it stand for several days in a
vacuum desiccator over quicklime then immersed it in water a n d titrated ,

the acid remove d The following are some of the results that he obtained
.

with acids of di fferent strengths :

1
J . S oc . C h em I n d
. 1 90 9 , p . 4 57 .
2
C omp t Ren d . .
, 1 8 62, 9 5, p . 1 32 .

3
J . S oc . C h em . I nd .
, 1 90 9 , p . 4 58 .
4 B er .
, 1 90 4, p . 54 9 .
 EX P L O SIVE S

H N0 3 re at i n ed b y
ce ll u lo se

Sp
Pe r ce n t .

.
gr .

If cell u lose be heated wi th acids of these strengths it i s c onverte d int o oxy

cellul oses which c on t ain a higher pro po rtion of o x y gen than cell ulose does
, ,

and perhaps a lo w er propor t ion of hydrogen 1

.

Xy lo idine .
As mentioned above Vieill e found that cellul ose was di ssolved by acid
,

con t ai ning ab o ut 57 molec u lar per cent nitric acid This mat ter ha s been . .

more ful ly investigated by J e ntg e n who found that the most suitable streng t h
2
,

for the preparation of these xyloidi nes at a te mperatur e of 1 8 i s 5 8 2 t o ° -

63 7 molec ular per cent (1 469

-
1 4 79 s p YVh e n solution i s complete
.
- — -
.

it should be poured into a large volume of c ol d wate r P roducts were t hu s .

obtained con t aining 6 2 and 7 2 per cent N they were insoluble in ether
-
.

alc ohol amyl acetate and acet one ethyl acetate c old acetic acid and acetic
, ,

anhydride only cau s ed them to s w ell up but h ot glacial acetic acid di ssolved ,

them With sli ghtl y stronger acid a some w h a t higher degree of nitra t i on is
.

a t taine d and t he products are more soluble A similar p ro duct may be

, .

obtained by di ssolvi ng cellul o se in sulphuric acid and pouring int o ni t ric acid ,

or by di ssolving in ni tric acid and pouring int o sulph u ric ’

.

The formati on of the labil e ni t rate o f cellulose i s ver y simi lar to that of
the c o mpound wi t h caustic soda If c otton be i mmersed in a solution of t hi s .

alkali it absorbs some of i t formi ng a c o mbinati o n in the proportion C H O

, , G 10 5,

Na OH the c ott on s w e lls up and if i t be under te n s ion it ac quire s a lustre .

resembli ng t ha t of s ilk The soda i s removed again on w ashing w ith w a t e r

. .

bu t t he c otton i s foun d to have change d in its properties it s tens ile s t reng t h ,

h a s be c o me greate r and it can be dye d more eas ily This process i s k no w n .

”
as merceriza t ion and is muc h u sed indus t rially ; fo r an i nves t iga t ion of
,

i t see Hubner a nd P ope 1 9 0 4 p 40 4 N auv o t her reagents be s ides

, , . .

causti c s o d a a n d nitric acid produce much the same re s ul t s although n o t ,

t o the same e x te n t as soda e g soluti o n s o f sodium s ulphi d e p o t a s s ium mer

,
. . .

c u r ic iodide bari um mercuric iodide and s t r o ng hy d ro c hl o ric acid

, Sul phuric .

1
S L E Kn ht
ee a nd AsoL ip h it
. J S
ec C h m I nd 1 9 14 p 1 1 6
a . sc z. . o c. e . .
, , . .

2
A ng . . 1 9 1 2, p . 9 44 .

3
H a e u s s e r ma nn . S S
. . , 1 90 8 . p . 30 5 .
 C ELLUL OS E 1 53

a nd phosph oric acids of certain strengths also react in the same way but at ,

the same time gra dually di ssolve the cellulose .

Cellulose treated i n this way i s much more reactive than untreated cotton Visco e . s .

If to the mi xture o f cellul ose and caustic soda solution carbon bisulphide be
added the material graduall y swells up and eventually goes into solution
, ,

forming sodium cell ulose xanthate This solution can be made into fine .

threads by passing it through narrow j ets and if these threads are tre ated ,

with alcohol and other reagents the soda and carbon bisulphide are removed ,

and a cellulosic material is regenerated This is the basis of the Visc ose .

artificial silk process .

If the alkali cellulose be treated with benzoyl chloride cell ulose benzoates C ll l o e , e u s

b en o a tes
are obtained Of these two a r e known : the mo n o b e n z o a te (C ) retains the
.
s
z .

form o f the original cellulose ; the di b e n z o a te is a structureless amorphou s

powder s oluble in acetic acid and chloroform .

Cellulose acetates are formed by the action of acetic acid and acetic a n h y A eta tes c .

dr ide on cellulose that has been converted into hydro cell ulose by the action -

of strong acids or alkali With unchanged cellulose there is little or no action

. .

In this respect the formation of all other cellulose esters i s essentially di fferent
from that of nitro cellulose for which the most resistant cellulose is best
-
, .

The triacetate (C ) has recently c ome into use on a large scale for making
6

films for cinematographs etc It is soluble in chloroform acetone and

,
.
,

phenol A te tr a ce ta te and other still higher derivatives were formerly supp osed
.

to e xist but the supposition was apparently founded on erroneous analysis

, .

Cellulose di ssolves in a solution of c opper hydroxide in a queous ammonia Sch w eit e z r s

’

reag ent
known a s Schweitzer s reagent If the ammoni a be neutralized a cell ul osic
’
.
,
.

substance i s regenerated P auly s artificial silk process is founded on this .

’

solubi lity Cellulose also di ssolves in a solution of zinc chloride and hydro
.

chloric acid and in va ious other salt solutions

,
r 1
.

The cellulose regenerated from any of these soluti ons differs from the Hy d a te r

c ll lo e
untreated material in being more reactive and in containing a larger propor ,
e u s .

tion of hydrogen and oxygen : the elementary c omposition agrees with the
formula 0 H 0 H 0 or some mi xture of this with normal cellulose The
12 20 10 , 2 , .

treatment of cellul ose wi th acids and alkalis yields very similar pr o ducts ,

and those obtained by the hydr olysis of nitro celluloses and other esters have -

the s a me c h a r a c te r is tics There are c onsiderable differences h o wever between

‘
.
, ,

celluloses which h ave been treated by the di fferent processes Cellulose .

,

which has been mercerized and washed out or has been converted into visc ose ,

and regenerated i s not so reactive with Fehling s soluti o n for instance as

, ,
’

cellulose that has been treate d with acid Cr o ss and Bevan have proposed .

the name hydrate cellulose for the former ; whereas the latter is called
“

”
hydr o cellulose
-
Hydrate cellulose gives off its extra water at a tempera
.

1
S D e nn ing J A m r C h m S c
ee 19 1 1 p 1515 , . e . e . o .
, , . .
 EXP L OS I VES

t u re o f 1 20 w he r ea s hydr o cellulose r e t a ins its w a ter o b s t ina t e ly a n d -

,

a t t hi s t empera t ure give s 0 3 less t han un t rea ted ce llul ose ‘

.

By t rea tment wi t h w ea k ni tr ic a c id po t as si um pe r mang a n a te bromi ne , , ,

a nd o t h e r o xidi zin g agen t s a ce r t ain a moun t o f o x y gen is ca us e d to co mbine

wi t h t he cellul ose produc ing o x y ce llulose whi ch als o is m o re rea c ti ve

,
-
,

t han normal ce llul ose .

The eff ec t upon t he ni tr a t i on o f t he pre se nce of t hes e var i o us a bnormal

cellul ose s has f o rm ed t he subj e c t o f a num be r o f inves t igati on o f re cent years s .

“ i c h e lha us and Vi e eg w 2
foun d t ha t me rce r iz a t i on d oes no t a fi ec t t he per -

cen t a ge o f ni t ro en bu t c onsidera bl y inc r ea se s t he so lub ili t y in e t her alco h ol

g ,
-
.

Berl and Klay e have t re a t ed ce llul ose wi th vari o us re a gents ni tr a ted ,

t hem a n d exami ned t he produc t s before and a fter ni tr a ti o n

,
’
The f o llo wi n g .

a re t he ma t eri als t hey experimen t ed wi t h :

I Co t t o n w o ol tr ea t ed wi t h 2 per ce nt soda solu t i o n t o r em o ve fat and

. .
,

w ashed wi t h h o t di t il led w a t er un t il t he r e w a s no al kali ne rea c t ion

s By .

combu s t i on analy si s i t w a s fo und t o c o n t ain 44 3 8 per cen t C a n d 6 3 5 per -

.
-

cen t H ca lcul a t e d on t he as h fr ee ma t eria l : cal cul a t ed for

. 44 42 - -

p e r cen t C and 6 2 3 p e r ce n t H
.
-
. .

I I H y dr o cell ul o se made b y dipping t he a b o ve in 3 per cent solutio n

.
-
.

o f s u lphuric acid dr yin g and hea ti ng for t hr ee h o ur s a t 70

, in a c lo md ves s el °
.

Foun d 4 75 pe r cen t C 6 43 pe r cen t H ca lcula t ed for 3C H .O

2 -
. H O -
.
, , s ,

4 8 6 per cen t C 63 5 per c e n t H

2 -
.
, . .

I II H y dr a l c ell ul ose : 1 5 g ce llul ose di gest ed wi t h 30 c c of a 30 per

.
-
. . .

cen t so lu ti on of h y drogen peroxi de for t hir ty da ys Fo u nd 43 24 per cen t

. .
-
.

C 6 25 per c en t H calcula t ed for

-
. H O 4 3 24 per cen t C 6 30 ,
-
.
,
-

pe r cen t H . .

IV KMnO Ox y c ellul o se : 32 g cell ul o se tr ea t ed wi t h a solution of

.
-
.

30 g p ermangana t e in 300 c c water for t hi rty s ix ho u rs wi t h fre quent sha k

. . .
-

ing .Then de c olo r iz ed wi t h sulphurous a cid and di ges ted wi t h dilute sulphur ic
ac id Dis olved in 1 0 per cen t ca u tic soda so luti on and re p rec ip ita ted
.
s .
s

wi t h acid Fo u nd 4 3 61 per ce n t C 6 30 per cen t H ca lc u la t ed for 4C H .

.
-
.
-
.
¢ , 5

C H .O 4 3 5 8 p e r c ent C 60 5 per ce n t H
, ,
-
.
, . .

V B r Ox y c ellul ose : 25 g cellulose a ll o w ed to st a nd for a da y wi th

.
- -
.

a mi xt u re o f 5 g br omin e 75 g c a lcium ca rbona t e and 40 0 c c wate r The

.
, . . . .

b r o mi ne w a t hen dr iven o ff on t he wa te r ba t h 50g b r o mine a nd 75 g

s -
, . .

calci u m c ar b o n a t e a ga in adde d a nd t he mix t ur e sha ken in a m a c hi ne Fo u nd .

4 3 8 3 pe r ce n t C 63 1 pe r cen t H ca lcul ated fo r

.
,
C H" .
‘

4 3 9 6 per ce n t C 6 1 1 per c en t H
-
.
,
-
. .

VI . Ox y c ell u lose : 5 g ce llul ose a llo w e d to s t a nd for a

- — .

wee k wi t h 22 g c a lcium pe r ma ng a n a t e and 1 000 c c wa t e r deco lo r ize d wi t h

. . .
,

1
Se e Os t “ e st ho ff So c C he m b ut 1 909 . p
’
a nd C Z 1 90 9 19 7 J 325
. . . . , p . ; . . .
, . .

2
Be r .
, 1 90 7. p . 44 1 . S S . ., 1 90 7, p 38 1
. .
 CELLU OS E L 155

sulphurous acid and washed The permanganate was added gradually .

.

Found 43 5 2 per cent C 5 20 per cent H ; calculated for 3 C H O C H O6 .

,
'
-
.
G IO , e S

43 51 per cent C 5 74 per cent H

-
.
,
-
. .

VII H NO Ox y cell ul ose : 50 g cellulose heated on a water bath

.
a
- -
.
-

for two and a half hours with 3 50 c c nitric acid of s p gr 1 3 Found . . .

“

.
-
.

43 1 7 p er cent C 5 9 5 per cent H ; calculated for 20 11 0

. C H O ,
.
6 10 , fi s 6

4 3 03 per cent C 5 9 8 per cent H

-
.
, . .
M

VIII KClO Ox y cellul ose : 30 g cellulose heated to 1 00 with a

'

°
- -
.
s .

sol ution of 1 50 g chlorate in 30 00 c c water and 1 3 5 c c hydr ochloric acid

. . . . .

(2 0
°
B ) gradually added
. Found 4 3 3 4 per cent C 63 9 per cent H c a l cu . .
, .

lated for 3 C H 0 C 6H O 43 3 7 per cent C 60 2 per cent H

G 10 5 10 6
-
.
, . .

I X Bleaching P owder Ox y cell ul ose

. cellul ose allowed to stand in the - -

air with a solution of bleaching powder of 10 B washed with slightly acidi fied °
.
,

w ater di ssolved in 1 0 per cent c austic soda solution and precipitated with
,
.

acid Found 43 62 per cent C 63 6 per cent H ; calculated for 4C H 0

. .
,
.
G 10 5

+ C H GO 4 3 58 per
IOcent C 6055 per cent -
H .
,
. .

These products were examined also as to the c o lo r a tio n s th e y gave with

various reagents but these were affected to a considerable extent by the
“

di fferent physical structures of the materials .

C o lo ra tio n w ith

I s o4 I +Zn0 12

I . C e ll u lo s e No rm a l .

II .
’

H y d ro -
ce ll u l o s e Fib re s
p a r ly t a tt a c ke d ,
t w is e dt .

III . H y dra l —
c e llu lo se S t t
r uc u r e in e d , i n re t a

t e r fe r e n c e c o lo u r s .

IV . K Mn O 4 C / c —
. G r a nu la r p o w d e r .

V . B r— O / c . t t
S r u c u r e a lm o s de t
t
s r o y e d , i n e r fe r e n ce t
c o lo u r s .

C a (Mn O 4 ) 2 O / c —
.
p a le b ro w n b lu e t t
S r u c u r e l i l e c h a ng e d , tt
t
s r e n g h s ma ll t .

VI I . H N O3 C / c —
.
y e llo w is h t t
S r u c u re le s s , h a rd

VI g r a in s .

II . K C l Oa C / c
-
. 9 -5 y e llo w
-
b ro wn b lu e B r o ke n d o w n , i n e r t
fe r e n c e c o l o u r s .

IX . B le a c h . Pow O/ c .
p a le b lu e G r a nu l a r p o w de r .

These products were nitrated wi th acid having the composition °

P n t b y w ig h t M l l e r ce e o e cu a r e r ce n t
p .
.

4 6-22 26-5

}
42-0 3
25
1 1 50 -
3 7
5 -
156 E X P L OSIVE S

fo r t w en t y f o ur h our s a t a t em p era t ure of ab o ut

-
af t er w hich t hey w ere
w a s hed fo r t hr ee da y s fi rs t wi t h c ol d a n d t hen
, wi t h ho t w ater U l t ima t e .

a nalys es e t c w ere m a de of t he ni t ro ce llul oses

,
.
,
-
:

Ni t ro
ge n b y Ato mi c ra ti os fro m
a na ly se s

t
Ni ro D u ma s C H N 0
m t e e r

1 3 29-

1 3 -2 8

Th e follo wi ng we re t he results of t he mi crosc opic exami nation

I Fib r es in t ac t in polari zed ligh t steel blue
.
, .

1 1 In polarized ligh t g rey fibres as w ell as s t eel blue

. .

III S t ruc t u re reta ined in pola ri ze d li gh t s t eel blue

.
, .

IV I n polari ze d light blue

. .

V In pola ri zed ligh t blue t oge t her w i t h many grey fibres

. .

VI Fibres nea rly in ta c t in p o lariz e d ligh t blue

.
, .

VII Grains resolved by high m agnifica t i o n in t o separate fibres in polar

.
, ,

ize d ligh t blue and t ran s lu c en t a t t he e d ges

. .
.

VIII I n po la r ize d light blue wi t h vi o le t t inge

. .

In t he ca s e of No VII t he a to mic ra t io i s calcul ate d from the ni t r o gen

.

de t ermi na t ion by t he Dumas meth o d The au t hors do n o t consider t hat a n y . .

c onclusions can b e dr a wn from t he di fferences in t he ni t rogen deter mi na t ions

b y t he t w o me t ho d s b ecause t he quan t i t ies t aken for analysis w ere in s o me
,

ca s es ver y s mall The in c r e a se in t he solubili t y in e t her alcohol is no more

.
-

t han mi gh t have b e en expec t ed from t he lo w er per c en tage of ni t r o gen The .

hi gher ra t io of ox y gen to carbon w hi ch w a s to b e observe d in t he u nni tr a te d

,

pr o duc t s af t e r t r ea t men t di sap p ears in the ni t ra te d products The absorp t ion

,
.

of basic d y e is hi gher t he viscosi t y much lo w er in t he ni t ro oxy cell ul oses

,
- -
,

e tc. t h an in the nitro cellulose

,
The v i s c o si t ies w ere de t ermin e d wi t h 2 per
-
.

c en t solu t ions in ace t o ne by t he me t h od of C o c hin s For c ompari s o n a

. .

num b er of ni t ro c ell ul oses w ere prepared by ni t ra t ing c o t t o n w i t h mixtures

-
 C E LL U L OS E 1 57

of equal weights of sulphuric a nd nitric acids to ,

‘

Which differen t propor

tions of water were ad de d : 1

Pe r ce n t . wa t er in Pe r ce n t N in
. Me th y le n e b lu e V is c o s i yt
m ix e d a c id pro d tuc a b so rb e d

X y lo idi 1 2-40
Ac e t o ne

The xyloi di ne was made by dissolving in sulphuric acid and pouring into nitric
acid .

The great fall in the viscosity of the solutions of ni tr o oxy cellulose as - -

c ompared with nitro cotton indicates that the size of th e molecules has been
-

much reduced .

In a later commu n ication Berl return s to the q uesti on of the e ffect of

2
,

various treatment on the viscosity Cotton which had been mercerized was .

nitrated with mi xed acid of practically the same c ompositi o n as that used
by himself and Kla y e ; the product c o ntained 1 3 5 per cent N This was -
. .

dissolved in acetone a n d the viscosities were c ompared with similar solutions

,

from unmercerized c otton :

Nit tt f m ro -
co on ro

Me r c e r i z e d U nm e r c e r i z e d
co tt on co tt on

1 p er cent . so lut io n 14 s e cs .

2 p er cent . so lu t io n 1 22

Merely heating the nitro cotton reduces the viscosity -

:

G u n c o tt o n unhe a t e d
-
,

he a t e d fo r 3 h ur a t 1 30 o s
°

Heating th e c otton before nitrati o n has a similar effect especiall y if o x ygen ,

b e present .The f o ll o w ing were the vi scosities of 1 per cent s o lutions of the .

nitro cottons in a c etone

-

C o tt o n d rie d b u t n o t he a t e d 23 30 e s s c .

h a t d 60 ho u a t 1 00 in a t mo s p h r f y ge n
e e rs 4 63
°
e e o ox

h y dr o g n 1 0 63 e

c arb n d i id 1 1 10 o ox e

1
S ee a ls o T . C h a n d e lo n , B u ll . Soc . C luim . B e lg .
, 1 9 14, 28 ,
p . 24 .

2
S S . .
,
1 90 9 , p . 81 .
 E X P L OSI VE S

These matters are of some pr a ctica l import ance a s different degrees of Vi sc osity
are required for diff e r en t pur poses .

The e ff ec t pr o d uced by hea t in g in a c urr ent of dry oxygen indi cates tha t
oxida t ion t akes pl a ce Cunni ngham and Dorée found tha t ozo ni zed oxygen
.
1

has a v ery po werful e ff ect on moist c otton at t he ordin ary temperature form ,

ing a p eroxide of cellulose w h ich w hen b oiled wi th w ater ga v e an oxy ce ll ul ose

,
-

wi t h a c opper value of 1 5 to 1 7 .

Ov er-b lea ch ed The ni t ra t ion of co t t on t ha t has been o v er bleached has been studi ed by
“
‘
-

P ies t as also t ha t of c o t t on t hat has bee n merce ri ze d and heated to a high

2
,
-

t empera t ure The experi ments we r e done on a manuf ac t uring scale and the
.

ni tro cellul oses w ere te s t ed for s t ability The resul t s of the bleachi ng were
-
.

as follo w s

me n t
T re a tm n t
e

St a ndar d \ or ma lly p r e pa r ed co tt o n
24 ho urs wi t h b lea chin g po w d e r so l u
t io n o f 3 % B
°

4 8 ho ur w i t h b l a hi n g p o w d r
s e c e so l u
t io n o f 3 73
°
B .

8 da y s wi th
ut io n o f sol 27} k g .

b lea c hi n g p o w d r in 50 l e .

8 d v s w it h
a lu t io n o f 5 k g
so . b lea c h 85
-
10 -4

Of t hese materials Ia a n d l b w ere w hi t e ; I I a was yello wi sh white and the -

fibres w ere shor t I I b w a s yell o w ish and c onsis t ed of part icles adh ering tightly
t o one ano t her The y w ere ni t rated wi t h acid of the c omposition
.

B w ig h t y e

P nt e r ce .

20 -5
69 0 -

10 5 -

The t ime of ni t ra t ion had t o b e v aried in order to ensure tha t t he acid had
pene t ra t ed t o t he in t erior of t he fibres in all cases Af t er ni t ra t ion the .

ma t erial w a s w a s hed firs t wi t h c old and t hen w ith successi v e lo t s of h ot water

in a hollan der .

1
Tra ns . C he m . S oc 1 9 1 2, p p . 49 7 5 1 2 —
.
2
A ng .
, 1 90 9 , p . 1 21 5.
 C E LLU L OS E

So lu b i li y int
S t
a t
b il i y

t
E he r -
a lc o h o l a f ter

Ab a o
lu e t w a sh e s

Fir s t c o ld La s th o t a lc o h o l

w a sh w a sh

St andard

The number of hot w a shings requi red to obtain a satisfactory stab ili ty was
much higher in the case of the bleached c ottons but as j udged by the Berg ,

mann Junk test none o f the nitro celluloses was really stable except the
- -

last for the o ffi cial limit in Germany is 3 c c and a good gun c otton does not
,
. .
,
-

give more than 2 .

Si milar experiments were carried out with mercerized c otton and cotton Ni tra ted me:
that had been heated at 1 50 in a cur rent of C 0
°
2
° “ med °°tt°

VVo o d Co ppe r
t
Tre a me n t m
u v a lu e
g

Sta nd ar d N o rmall y pre p ar e d c o tt o n

IV . Me r ce rize d 20 mi nu t e s w i t h 1 8 5 p er -

c ent s o d a ly e
.

H ea t ed 1 0 h o ur s in C O a t 1 50 2
°

H e at e d 1 00 h o ur s in C O a t 1 50 2
°

The heated cottons were yello w ish white and yell ow respectively -
. The
foll owing were the res ul ts of ni tration :

t
So l u b ili y i n

w a sh e s

H ou r
 E X PL OSI VE S

Merce riza t ion re d u c e d t he p ercentage of

nitr o gen only to a slight ext ent ,

bu t greatly increased the solub ili ty i n e t her

alc ohol and impaire d t he stability —

i t also increase d th e quantity of u nn itr a te d material as d ete rmin ed by treating

the ni tro cell ulose wi t h sodium sulphi de solution In the nitrated mercerized
-
.

cot t on this amounte d to 1 8 per cent w hereas in all the other of the ab ove -
.
,

produc ts it v aried bet w een 0 6 and 0 8 per cent Hea t in g the cotto n in carbon - -
.

dio x i de ma de very little di ff erence t o the ni tro c otton but it was some w hat -
,
.

more di fficul t t o sta b ili ze .

The general c onclusion from t hi s investigation i s that both over bleac hi ng -

and merceri zation have a very bad effect on c otton intended for the
manuf acture of nitro cotton -
.

P iest has also investigated the action of alka lis and ammoni um s u lphide
solution on nitro cellul oses prepared from normal o v er bleached and mer
-
,
-

c e r iz e d c otton He found that the material from over bleached c otton

l -
.

wi thstood these reagents le ss w e ll than ordinary gun cotton but that the -
,

material from merce ri zed c otton withstood them some w hat bette r The ‘

regenerate d cellulose had a much hi gher copper value than the ori ginal c ottons ,

w hence P iest c oncludes th at it has been converted into oxy cellul ose but -
,

does n o t c onsi der whether it may not rather be hydr o cellulose Vign on 2 -
.

s imi larly found that ni trated hydr o cell ul ose w a s more attacked by caustic -

pot ash solution than normal ni tro cellulose and ni trate d oxy cell ulose still
- -
,
-

more .

Vignon c onsiders t hat ordi nary gun c ott on is reall y ni tro oxy cell ul ose
3 - - -
.

He prepare d the pro duct of ma xi mum ni tration acc or di ng to Lunge s dir e c ’

tions and made an elementary anal y si s of it The resul ts w ere in accord .

with the formul a 3C H (N0 ) O 6But thi s view is not

7 2 3 5

generally ac ce pte d The cell ul ose c ould only be o xidi zed by the ni tric acid
.
,

some of whi ch woul d be reduced to ni trous acid w hereas there i s practicall y ,

no formation of nitrous acid in the nitration process Moreover there are .

,

di stinct differences bet w een the ni tration product s of normal and oxy
cell u lo s e .

Eff ec t of dil u te As regard s the eff ect up o n c otton of treating i t w ith di lu te c austic soda
lye s of di ff eren t strength s and at di ff erent t empera t ur e s some c urious ob serva ,

t ion ha v e been made by Sch w albe a n d Ro b n o ff

s i 4
They tried the e ff ect upon '

pure c otton cell ulose w hich had been prepared by Tamin s method by b o il
‘
5

ing wi th a s olution of re s in s oap and alkali withou t pressure washin g hot ,

a nd bleaching v ery carefu lly ; in this w a y the y obtained a mate rial which
h a d a copper value of o nl y 0 0 42 -
.

1
A ng 1 9 10 , p
. . . 10 0 9 .
2
C R 18 98, p . 1 658 .

3
C omp t Re nd . 1 38 , 1 90 4 ,
p . 8 08 . 1 9 1 1, p . 256 .

Re v ma t
. . ed . , 1 90 8 ,
p . 3 1 3.
 C E LLU L OS E

C o p p e r va lu e s
So d a

ce n t .
Te mp

When an over bleached cotton is heated with water under

-

temperature ab ove 1 50 there is a great increase in the c opper

°

T mp t e era C pp
u re v l o er a ue

°
20
°
100
°
1 20
°
1 35
°
1 50
1 65
°

°
1 79
°
21 3

The authors conclude that the strength of the soda used for the purificati on
of cotton should never be all owed to fall below 5 per cent and should be made .

up from time to time to this strength if necessary also that temperatures ,

above 1 50 should not be employed They also found that the acid for sub
°
.

sequently acidifying need not be of greater strength than 0 1 per cent with -
.

weaker acid the cotton is even whiter but the copper value is higher .

It has been found by Trotman 1 that the addition of neutral salts to soda
lye considerably reduces the loss of weight of c otton boile d in it and hence he ,

c oncludes that the purification o f the c otton is interfered wi th by the presence

of these salts .

Von Lenk for his gun c otton used c otton in the form of hanks of yarn
-
.

When Abel had di scovered the very beneficial eff ect of pulping the gun c otton -

there was no longer any obj ect in using such an expensive variety of raw
material and he used instead c otton waste the residual cotton from the
, ,
t
Co to n w a s

spinni ng mi lls In the early days of the industry there was little demand
-
.

for t h i s material and the c otton waste supplied to the explosives industry
was generally o f good quality but in c ourse of time the demand for cotton
,

1 J
S oc C hem I nd 19 10 p 249
. . . ., , . .

V OL . 1 .
 E X P L OSI VE S

wa te not onl y for the manufac tur e of ni t r o c o t to n bu t al o for o t her p u rpo s es

s - s

gre w and i t is n o w difficul t to ob t a in a r ea ll v sa tisfac tory c otton waste More

, .
;

o v er a special indu s try has sprun g u p t he c o t ton w aste indu try w hi ch

,
— - s —

coll e c t s t he w as t e from all the mil ls and p r epares i t for various purposes .

The obj e c t of t he supplie r s of c otton waste is t o produ ce a ma t e r i a l that wi ll

pa s a specification ra t her than to suppl y a real ly good c ott o n w hi ch ca n be
s .

made in t o stable gun c otton a matter about w hi ch of c ourse the y kno w little
-
,

or no t hi ng Co t t on w aste for ni t rat ing is mad e l a rgely from the s w eepings of

.

t he c o t ton mill s i t c on t a ins s ome sp u n t hr ead but i t is liable to c on is t

-
"

,
s

largely of fly t he fluff y material w hi ch escape s into the air during the

,
‘

various mechanical o p era t ions Thi s fl y is the leas t resi tant porti on of
.
s

t he co t t on a s i t is suppli ed to t he mi lls The presence of a very la rge p r o .

p o rt ion of dir t and oil and a ll m a nn er of foreign matter makes i t nece s sa ry

t o submi t t he co t t on w as t e to a v e r v dra t ic sco u r in g and ble a chi ng proces s s
,

and t his as mav be seen fr om t he precedin g pages mu t ine vitabl y produce

, ,
s

a c onsiderable proport ion of oxy cellulose and o t her m odi fications of the -

normal resis t a n t co t t on cellul ose At the sa me t ime more and more demands
.

a r e being made upon t he stability of t he ni tr o c otton especial l y t hose used - s ,

for t he manufac t ure of smokele s s po w ders for milita ry and naval p u rposes .

Consequen t ly t he explosi v es w orks h a v e bee n obliged to give more attention

t o the ques t ion of t he ir supplies of c otton A few of the larges t obta in t heir .

c o t t on w a s t e u n p ur ifi e d and uncleans ed from the mill s and purify i t t hem

sel v es a nd un do u b te dl v thi s is t he bes t me t h od w here i t i prac t icable
,
s .

i Va s te f rom w e a v mg mi lls migh t a lso b e used for ma king ni t r o c o t t o n -

,

bu t it is liable to be con t a min ated wi t h s t arch w hi ch is applied t o the w arps ,

to increase their s t rengt h S t arch on ni t ra t ion gives an uns t a ble ni t ra t ion

.

prod uct and conse quen t ly mu s t be removed from the cott o n b y sui t able
,

t reatment Ne w c ot t on can al o be u sed t he onl y obj ection t o i t bein g i t s

.
s
,

high price i t s employ ment for t he manuf ac ture of smokeless po w der w ould
onl y involve sligh t al t era t ion to the dies e t c s
,
.

The co t t on is subj ected t o v ariou p u rifica t ion proc e ss es before i t can be

s

used . To remo v e t he grea t er pa r t of t he o il and fatt y ma t t er i t is ex

t rac t ed wi t h a vola t il e sol v en t in a n ex t rac t ion ves el The sol v en t af t er s .

i t h as soa ked t h rough t he c o t ton flo w s in t o a ch a m b er w here i t is boil e d by

means of s t eam pipes ; t he v a po u r is c onde nse d and again flo w s t hr ough
the c o t t on I Vhe n t he e xtraction is fini shed the sol v ent is di s t il l e d o ff in t o
.

a r eceiver and the last po rtions of i t are re moved from the c o t t o n by blo w
ing s t eam t h rough i t As a solvent benz in e or benz ol can be used bo t h are
.

very i n flammable and some w ha t po i onous and preca u t i ons sh ould be taken s

a c cordi ngly Carbo n bisul phi de is s till m or e in flamm a ble Ca r bon t e t ra

. .

chl ori de and o t her chlorina t ed c ar b o n c om p o u nds a re not imfl a mma b le b u t

are mo re p oisonous t han be nz in e or benz ol The choi ce of t he solvent wi ll .
 C E LL U L OS E
depend on the price and the local con di tion s After e x traction the c otton .

is b oiled in a kier with a weak solution of caustic soda or so di um carb onate ,

and well washed w ith water either in the kier or in a poacher Af ter this it .

is generally bleached w ith a weak solution of bleaching powder or sodi um

hypochlorite This operation is often carried out in stone cisterns but if
.
,

the bleaching solution be very weak iron vessels can be used Next it is .

treated again with dilute alkali to destroy the bleach and then washed again
thoroughly The bulk of the water is then removed in a centrifugal machine
.

and the c otton i s finally dried and made into bales It is important that .

c otton whilst alkaline be not exposed to air at a hig h temperature .

For the removal of the fatty matters soaps especially resin soaps ca n , , ,

be used The whole purification process can be varied in many di fferent

.

ways and must be adapted to the sort of c otton that is to be treated It is

,
-
.

required to remove all matters e xcept normal resistant cellul ose without ,

inj uriously a ff ecting the character of the latter Although the methods of .

treating or di nary c otton goods have formed the subj ect of numerous investiga
tions the preparation of c otton for nitration h a s not received the attention
,

which its importance call s for

B S Le vi ne recommends treating the cotton with bacteria instead o f
. .

bleaching He claims that the impurities are thus removed more c ompletely
.
1
.

For the man uf actur e of c ollo di on c otton for blasting gelatine c op b ottoms -
Cop -b ot to
are generally used This is spun thread in a tangled c on di tion the last portion
.
,

left on the spindl e This undoubtedl y is a very good class of material but
.
,

is usually c onsidered too expensive for the manu facture of smokeless powder .

”
After the long staple fibres o r lint have been removed by the fir st gin ni ng “
,
Lin te s
r .

there is on American upland cotton seed still ab out 1 0 per cent o f short fibre .

”
c otton which is recovered by a sec ond process and is kn own as linters
, ,
.

From sea island c otton which is grown near the c oast and E gyptian
-
, ,

cotton long staple fibres only are obtained and c onsequently these varieties ,

yield no linters This woul d form quite good material for the man uf act u re
.

of ni tro cotton if it c ould be freed mecha ni cally from the a dh erent resin and
,

a ll particles of seed husk but this does not appear to be possible and c o n s e
, ,

quently the linters have to be submitted to a very dr a stic chemi cal trea tment ,

which damages the cell ulose Moreover the seeds often remain for a long .

time b efore the linters are removed and during this time they undergo a certain
amount of fermentation and the fibre is attacked 2
When ni trated li nters .

consequently give some w hat low nitrogens and hi gh solubili ties in ether alcohol -
.

They are however used on a considerable scale in America and Germany

, , ,

but not so much in E nglan d .

For the m a nufacture of collo di on for high class lac quers and celluloid -
,
Tissue p a p er

cellulose is use d in the form of tissue pa p er Alth ough this is somewhat .

1 J I nd E ng C h m 1 9 1 6 p 29 8
. . .
2
ePie s t A n g
.
,
1 9 1 2 p 39 6
, . . , ., , . .
 E X P L OSIV E S

e x pensive it has grea t advantages fo r thi s c la s s o f w ork : by in s pection of

,

t he sheets i t is p o ssible t o detect and then to rem ove every pa r t icle of foreign
matter Moreover these thi n shee t s are ni trated c ompletely in a very sh ort
.
,

time The paper must of c ourse c on s ist of pure ce ll ulose and sh oul d n o t
.
, ,

be calendered .

Schultze spor t ing po w der has al w ays been made from pu r ified wood fibre ,

a n d the makers claim that thi s gives a po w der w ith the r ight rate o f burning

m ore readily than cotton Other makers of bul k sh ot gun p o w ders have .
-

also used nitrate d wood ce llulose .

Wood cell ulose or chemica l wood pul p is ma d e by three diff erent metho d s
-
,
-
,

called the sulphite soda and sulphate processes In all of these finely ground
,
.

w o o d pulp is boiled with a solution w hich d estroys the non cellulo s e In the -
.

sulphi te process a solution of calcium or so di um bis ulphite is u se d i n the so d a ,

process c aus t i c s o d a and i n the s ulphate process a solution of caustic s o d a

,

a n d sodium sulphide .

A number of wood a nd straw cellulos e s and ni t ro c ellul o s e s prepare d fr o m ,

-

them have been examined by Nitz e lna de l

,
The w ood celluloses w e re pre .
1

pared by the sul phite process the straw celluloses by the sulphate process , .

None o f the latter pro v ed satisfactory but one of the sulphi te ce lluloses gave ,

a good yield of nitro cellulose w hich c oul d be rendere d stable C B Sch w albe
-
, . . .

and A Schrimpf have also prepared nitro cell uloses in the laboratory from
.
2 -

woo d celluloses made by diff erent processes from various w oods They .

obtained ni tro ce lluloses of a high degree of nitration and satisfactory sta bility
-

so far a s the tests c o ul d show For the preparation of high class smokeless .
-

po w der for ri fled fi r e arms it w ould be necessary to purify the w ood cellul ose
-

very carefully a n d to make it into thinner sheets than is usual U nder normal .

condi tions this must make the wood ce llul o se almost if not qui t e as e x p e n , ,

sive as the c ott o n w aste generally employed and as the true stability of the ,

smokeless powder can onl y be ascertained by keeping tri als ex t ending over
many years it i s easy to understand that most of the P o w ers have not used
,

it for their po w ders The J apanese h owever are said to be using wood ce ll u
.
, ,

c s e from Sakhalin a n d it is probable that the Germans are using it since

‘ 3
, ,

they can n o longer import c otton .

Cell ulose is attacked by various bacteria especia lly if it be mixed with ,

substances whic h pro vi de food that favours the ir development The methane .

w hich rises from marshes is apparently d erived principall y from the fermenta
t ion o f cell ulose t he i ntestines of ani mals also c ontain bacteria a n d ferment s ,

w hich attack cell ulose E ven pure c otton c ellulose ca n be thus ent irely
.

destr o ye d ; Hoppe Seyler found that S w e di sh fi lte r paper w a s c ompletely

‘ - -

1 2
a s 1 9 1 2, p p 25 7, 30 1 , 3 3 9 38 4 a n d 40 9
.
, . 19 1 4, p . 002 .

3
A . n
B u is s o , L e P r o b le me des P o ud r es , P is , 1 9 13
‘

ar ,
pp . 1 75, 1 77.
Z . h
p ys io l C h , 1 0 , p 40 1 .
. . .
 C ELL U L O S E 1 65

resolved into gaseous products in the presence of river mud He c onsidered .

that cellulose w a s fir st hydrated C H mO H 0 C H O and was then G 5 2 G I Z G,

c onverted into methane and carbon di oxi de C H 0 30 0 3C H , , 1 2 6 2 4.

Omelia n s ki found two di fferent ferments in river mud one of which produce d
1
,

hydrogen and the other methane

,
2
The bacteri a were anaerobic but aerobic .
,

organi sms capable of destr o ying cotton and linen have been f o und by Herson .

If cotton be stored for a long time under u nf avourable con ditions as regards
heat a n d moisture it i s liable to be affected inj uriously In extreme cases
, .

it may become quite friable a n d dusty but even before this stage i s reached ,

it is unsuitable for the production of stable ni tro cotton probably on account -

,

of the formation of hydr ated cellulose If such a material be nitrated and store d .

for some time in a warm place it undergoes decomposition with the forma
tion of a c onsi derable amount of w ater and other decomposition products .

The micro photogr aphs (Fig 30 ) repro duce d from a paper by de Mosenthal 3
-
.

sho w very c learly the structure of the c otton fibre In No 1 the characteristic St ctu e 0 . .
ru r

t w i sting of the fibre is seen No s 2 3 5 reveal the pores thr o ugh the o uter otton fi b re .
, ,
c

cuticl e No 4 a longitudi nal section o f the fibre is almost uni que on account
. .
, ,

o f the e x treme d iffi c ul ty of obtaining such a view it clearly sho w s the inner “

and outer cuticles and the matter in the centre of the tube The material .

f o rming the greater part o f the walls of the tubes consists of true ce llulose .

It is granul ar in structure and is held in position by t he inner and outer cuticles ,

which exert so much pressure on it t hat the fibre is seen to be doubly refract
ing when e x amined in polarized light If one of the cuticles be removed so .

as to relieve the pressure colours are no longer seen under the p o larizing
,

microscope When treate d with dilute soda and bleaching solution the
.
,

c ompound cellulose of the outer cuti c le is no doubt attacked t o a c onsiderable

e x tent but the inner cu t icle and the matter in the interi o r of the tube c ann o t
,

be reached so we ll by the solutions and conse quently must escape treatment , .

De Mosenthal observed that a single fibre has no c apil lary action but when ,

several are bun dl ed together liquids are dr a w n up bet w een the m This .

i ndi cates that there is no free passage up the centre of t he fibre that the tube
is obstructed at intervals The material in the centre of the fibre probably
.

gives rise to u nstable products on ni tration and it is perhaps the function of ,

the pulping process to render it possible to remove these partly fr o m the

nitro cotton
-
.

When treated with cuprammonium s o lution (S c hweitzer s reagent ) the ’

cuticle dissolves mu c h less readi ly than the bulk of the fibre (s ee No 5 Fig .
, .

a n d the same thing oc curs when nitro cotton i s di ssolve d in acetone or other -

solvents When pa s s e d through a P asteur filter these particles of cuti c le

.

1
Co mp t B end
. , 1 21 , 1 90 5, p 65 3 . .

3
S ee a ls o La fa r s H a nd b u ch de r tech n is ch en 11] y ko lo g i e , E d . 3, K a p . 9 .

3 J . S o c C h e m I nd , 1 90 4
. . .
, p . 29 2 .
 1 . Na t ural Co tt o n Fib re x 30 0

2 . Po rt io n of s a me Fib re 10 0 0

Po r t io n of (2) Fo cus s ed to S ho w S t o ma t a x 1 0 00 4 . Lo ngit ud inal t n

Se c io of Co tt o n Fib r e x 1 0 00

5 . Po rt io n o f a Fra gme n t o f C tt o n o 6 . Gra nule s fro m a 65 p er ce nt . So lu t io n

C u t ic le fro m a So lu t io n in C u p a mmo r o f N it ra t e d C o tt o n x 1 500
nium X 1 1 00
a indi ca t e s t h e St o ma t a

7
. Po r t io n of a N itra t ed Co tt o n Fib re x 300

FI G . 30 . Mic ro p ho t o g ra p h s of Co tt o n (d e Mo s e n t ha l ) ,
 CEL L UL OSE 167

a re remove d from the s olutions to a gr ea t e x te n t For the manufacture of .

artificial si lk such fil tration is necessary because other w ise the orifices of the
,

silk worm s get stopped up It i s somewhat remarkable that the molecules

-
.

of ni tro cellulose which must be very large can pass through the minute
-
, ,

pores of a P asteur filter whi ch stop the molecul es of many organic dye stuffs
,
-
.

It can only be e xplained on the assumption that the cellulose m olecule is in

the form of a long string The molecules of nitro cellulose will not pass through
.
-

a di alyzer 1
.

W hen cotton i s nitrated the pressure exerted by the cuticle i s released ,

wi th the consequence that the twists of the fibres di sappear (s ee No and .

the interference colours become much less brilliant Similar changes i n .

appearance occur when cotton i s mercerized or submitted to other actions

of a like nature .

All cotton contain s a proportion of immature fibres called dead or unripe ,

D ea d

cotton These have very thi n walls and either no central channel or a very
.

flat one They are weak and consequently liable to break during the spinning
.

operations Therefore they constitute a large prop ortion of the fly which

.

passes into the cotton waste It i s less easily nitrated or acetated than ripe
.

cotton It generally has a small er t wi st but the fibres retain this twist on
.
,

treatment with an 1 8 per cent solution of caustic soda It behaves di fferently

. .

with dye stu ff s also -

.

If the cotton bolls b e allowed to remain on the plant for some time after
they are ri pe the cotton acqui res c haracters very similar to these Cotton .

i s liable to form in p ortions of the length of the fibre solid parts whi ch do not ,

take up dye properly . Thi s i s usually at the tip which i s conse quently brittle ,

a n d breaks o ff du ri ng the spinn ing processes In the body of the fibre this .

s tructure is seldom found excep t in the coarser varieties such as Surat and ,

P eruvian 2
.

1
De Mo se n t ha l J S o c C hem I nd 1 9 0 7 p
, . . . .
, , . 447 .

2
F . H B o w ma n S tr u ctu r e o f th e C o tto n F i b r e
. , , p . 113 . S ee a ls o C h em Z e it , Se p t ,
 C H A P TE R X I I

MANUFACTURE OF NI TRO-CELLU OSE L

n
P ic ki g t h e t to n Tea ing D ry in g N it rat in g Ab e l s p ro ce
co s C n t rifu ga l
’
ss e

r
p o ce s s D i r e c t d ipp in g D is p la c e m n t p ro eH y a tt n it ra t o r r H igh n it ro ge n
ce s s

gu n o tt nc P a t ia lly
o r lub le ni t r c o tt ns
so So lub l
o n i tr c o tt n s
o Py e o o r o
- - -

c o llo d io n C llo d io n fo b la t in g ge la t in e
o r s C o ll d io n fo t he r p rpo se
o r o u s

WH E N t he raw mate rial use d is pur ified cotton w aste i t i s necessary to pick ,

i t over fi r st by hand in order to remove a ll string pieces of woo d and metal , ,

hard kn o t s of cotton and all o t her ma t te r whi ch would not nitrate sa tisfacto ril y .

This w ork i s generall y done b y women .

_ J
Next the mate rial must be opened out by means of a te asing m achi ne .

Th e simplest form of t hi s c onsists of a rapidl y rotati n g dr u m armed wi th

numerous iron te e t h a n d a pa ir of feed ro llers t hat grip th e un te ased cotto n
-

firmly and gra dually feed it up t o t he drum w hi c h tears i t o ff in small por t ions ,

and thro w s i t ou t at t he o t her side of t he machi ne The whole shoul d be .

enclosed to prevent t he fine cot t on dus t flying about .

t r y ing . The co t ton as supp lie d generally c on t ains about cent of mois t ure .
,

and i t i s des irable to re d uce t hi s t o about 0 5 per cent This ma y be effec te d .

in any ordi na r y form of s t ove The sim ples t type i s a cupb oar d wi t h a number
.

of perforate d shelve s 0 11 w hich t he c otton i s placed and ste am pipes under ,

-

nea t h S ui t a ble openings a llow ho t air t o circ ulate through the cotton and
.

escape at t he top of the cupboar d The disadvanta ge of thi s form is tha t

.

the co t ton i n the lower trays gets much hotter and dryer t han that in t he
top ones Inste ad of having the ste am pipes un dernea t h they may be in a
.
-

separa te hea ter through which a ir i s forced b y means of a fan and then t hrough
t h e stove bu t the utili zation of the heat i s not very good as the air i s cooled
, ,

down before i t can take up more than a small p roporti on of water In the .

m os t econ o mical stoves these tw o m eth ods of hea t ing are combined th a t i s ,

to say t he air i s blown through a heater into the stove w hi ch i s pro vi de d wi th ,

a number of s team pipes w hi ch ma intain the temperat u re at abou t 90 C

-
,
°
.

The c o tton should be ma d e to pass c ontinuou sly t hrough t he stove by mea ns

of trave lling bands The d r ying takes about three quar t ers of an hour Over
.
-
.

heating o r too p rolonged drying should be avoided .

1 68
 MANUFA C T UR E OF NIT RO C ELL UL OS E
-
169
The method of nitration worked out b y Baron von Lenk was described Nit a ting r .

at length in the paper published by Abel in the P r oc Roy Se a 1 8 66 p . .

, , .

This was only slightly modified by Abel and was followed at W alt ham Abbey ,
-

and in other factories until recently the principal difference ma d e being the ,

use of cotton waste instead of the skeins of yarn used by von Lenk The .

method as carried out at W altham Abbey until 1 90 5 was described thus by

Sir F L Nathan :
.
2
.

The nitrating acid was composed of three parts of sulp huric acid of 9 6 Ab el s p oc ’
r

per cent m ono hydrate to one p art of nitric acid of 9 1 per cent m on o hy d rate
.
-
.
-
,

thoroughly mixed and cooled This acid w a s run from the store tanks into .

cast iron dipping pans holding about 220 lb each the pans being supp orted
-
, .
,

in an iron tank through which cold water circ ul ated to keep the temperature
below 70 F The di pping pans were provi ded at the back with gratings
°
.
,

on which to press o ut some of the acid from the charge The charge of cotton .

waste weighed 1 lb 4 o z and on rem oval from the cooli ng b ox was passe d
. .
,

from the back through an earthenware pipe i n the partition running along
the back of the p ans and raked by a dipper as rapidly as possible into the
, , ,

acid After remaini ng in the acid bath for about eight minutes the cotton
.

was removed to the grating and a p ortion of the acid squeezed out by means ,

of an iron lever having an iron plate attached to one end After a charge .

had been rem oved from the di pping p an ab out 1 3 2 lb of the mi x ed aci d was 7 .

run into i t to replace the amount removed with the charge The charge .
,

now weighing wi th the adhering acid about 1 5 lb was place d in an earthen .

,

ware pot provided with a cover and transferred to the cooli n g pi ts through ,

which a stream of cold water flowed and where it remained for twelve hours , .

During thi s period of di gestion the c onversion of the cotton into gun c otton -

wa s completed The contents of the pots were now emp tie d into a centrifugal
.

wringing machine and the bulk of the waste acid extracted The gun cotton
-
, .
-

was then rem oved from the cent ri fugal machine and placed in galvanize d
iron pans with long handles These pans when filled were carried quickly .

across to the immersing tank and the gun cotton thrown into a large bulk ,
-

of water the workmen stan di ng by the tank and pushin g the gun cotton at
,
-

once under th e water with a stout wooden paddle The immersing had to .

be done as quickly as possible as if the gun cotton were allowed t o come , ,

-

gradually in contact with water i t was liable to fume off The immersing , .

tank was fi tted with a perforated c opper plate to allow the water to overfl o w ,

so that fresh water w a s constantly passing through the tank The gun cotton .
-

was k ept well stirred by means of a wooden paddle W hen 2 cwt had been . .

1
h
T is p p e a r a nd Ab e l
’
at r o n
s l e e on tab ilit y f G un co tt o n (T n R y S e a
th e S o -
ra s. o .
,

1 8 67, p . 18 1) a re o ut o f p r in t n d n a o t a lw a y a cce s ib l s b t t he y ha v b
s e, n t ra n s la t d
u e ee e

t G rman
in o e b y D r B P le u s s a n d
. .
p ub li h e d b y Fr ie d land e r B e r lin 1 9 0 7
s , , .

2
J Soc . . C h em I nd
. 1 90 9 p 1 8 0 , . .
 EXP L OS I V E S

immersed the infl ow of water wa s stopped and the tank d rained down
, .

When all the water had been run o ff the tank was fill ed u p agai n with
fresh water Thi s was repeated si x times or until the gun cotton no
.
,
-

longer taste d acid W hen thi s stage had been reached the gun cotton
.
-

was wr ung i n a centrifugal machine water from a hose pipe being t u rne d 0 11 ,
-

the gun cotton for one minute d uring the wringing and it was then ready
-
,

for boili ng .

This process although it undoubtedl y produced a good gun cotton

,
-
,

had certain disadvantages and the amount of lab our re qu ired was very great
, .

The plant although in dividual item s were not expensive very rapidl y de te r i
, ,

orate d and the cost of renewals and replacements was heavy P ower was
, .

requi red to drive the centrifugal machines large quantities of water were ,

use d both for coo ling and immersing and decomp ositions i n the pans pots , , , ,
”
a n d acid centrifugals were by no means infrequent
, .

In or der to save the lab oriou s and unpleasant operations of transporting

the nitrating pots from the di pping pans to the cooling pits a n d from there ,

to th e acid centrifugals and the transfer of the aci d and c otton from one
,

vessel to another a method has been adopted especially i n Germany of nitrat , ,

ing in the centrifugal itsel f A centrifugal machine u sed in thi s way lasts
.

much longer than might be expected for several years in fact with only occa ,

s io n a l repairs The firm whi ch has had the wi dest experience in b uildi ng
.

thi s plant Se lw ig and Lange of Bruns wi ck has intro d uced several improve
, , ,

ments in it The basket of the centrifugal i s fi tted with a secondary driving

.

gear w hi ch can cause it to rotate slowly during the period of nitration thu s
, ,

maki ng the acids circ ul ate and their temperature can be kep t at any desired
,

point by means of a water j acket .

The nitrating centrifugal i s not very suitable for maki ng g un cotton of -

low solubility i n ether alcohol because u nl ess the cotton u sed i s of go o d quali ty
-
, ,

parts of it will not be c ompletely nitrated in the short time that i t remains in
c ontact with the acid .

The method of working i s as follows First the acid i s run i nto the centri ,

fugal by turni ng on the cock on the pipe communicating with the supply tank .

Then the cotton i s immersed i n the acid a little at a time until there i s about
1 part of cotton to 50 of acid The li d i s then shut down and the nitration
.

i s all owed to proceed u sually for a quarter to three quarters of an hour accord
,
-
,

ing to the sort of ni tro cotton that i s being ma de Then the acid i s allowed
-
.

to dr ain away by a cock communica ting with the waste acid tank The -
.

centrifugal i s then rotated slowly a t fi r s t and gradually more rapidly until

,

the proportion of free acid i n the cotton has been sufficiently reduced .

When making in solu b le gun cotton by thi s p rocess i t i s generally desirable

-

to leave not less than 1 1 parts of free acid to every part of gun cotton because -
,

if the wringing be car r ied further there i s danger of the charge fuming o ff or ,
 MANUFACTU RE OF N I TRO C ELLU L OS E -
1 71

even exp loding W ith nitro cotton of lower nitration the wringing can b e
.
1 -

carried somewhat fu rther .

W hen the cent ri fugal has been stopped the nitr o cotton i s taken out by -

means of tongs made of iron or aluminium and removed to tanks where it i s ,

immersed in running water Selw i g and Lange have introduced an auto .

matic hydraulic c onveyor the entrance to which i s j ust by the centrifugal ,

and may be seen at the back of Fig 3 1 A ring of water j ets di rected d own . .

wards j ust below the opening imme di ately immerses the nitro cotton as it i s -

introduced and the stream of water carries it along to a tank where the washing
,

with cold water i s c ompleted The somewhat dangerous operation of carrying .

the acid cotton i n wooden boxes or other receptacles i s thus avoided and ,

there i s also a saving of labour .

During the operations of introducing the cotton into the acid and of r e mo v
ing the acid cotton after nitration a considerable amount of acid fum e i s given ,

o ff and it i s therefore necessa ry to provide the machi n e with a draught to

,

draw the fumes away P rovision for doing this i s shown on the left side of
,
.

Fig 3 1 where an upright earthenware pipe may be seen c om municating with

.
,

the interior of the c entri fugal This is intended to be connected by means .

of earthenware pipes with a stone ware fan I have found however that -
.
, ,

the draught produced in this way was very inadequate and that the men ,

who did the nitrating suffered much from the fumes which were not drawn
away A better arrangement w a s to make the li d of the centrifugal open to
.

one side and run a wooden shaft about 1 8 inches square along the back of
,

the row o f centrifugal mac hi nes with an opening j ust by each machine that
_

could be closed with an aluminium door At the other end of the woo den .

shaft there was an ordi nary propeller fan with aluminium blades driven from
a shaft This created a much better draught with a smaller e x pen d iture of
.

power and the cost of the arrangement was much less than that of the stone
,

ware fan etc The woodwork had to be renewed from time to time but this
, .
,

was far less e x pensive than the repairs to the stone ware fan had been -
.

Information about the various types of nitrating centrifugals will be found

in a paper by G r iin dli c h 2
.

At Nobel s factory at Ar deer a method was adopted known a s direct D i ect dippi
’
r

di pping ”
Accor di ng to a commun ication by Mr Lun dholm to Sir F L
. . . .

Nathan the process was as follows :

The insta llation consi sts of para llel d ouble rows of long iron tanks known
as coolers Iron p ots terme d dippers in which nitration i s carried out
.
’
, ,
’

1
At t h e K . B . P u lv e r fa b r i k a t I n g o l t ad t s nt en t s f a n itra t ing c en t rifu gal
th e co o

ex p lo d e d on ,
J u ly 1, 1 9 1 1 , k illin g o ne ma n a n d in j ur in g ano t h r Th e ma c h in e w e . as

n t
b e i g e mp ie d a t t h e ime t . I t is s up p ose d t ha t it h d b n p un to o l n g A a rul
a ee s o . s e

t h e co e nt nt
s me e l
y f me r u o ff . 1 9 12, p .

2
1 9 1 0 , No s . 1 8 , 21 , 22, 23, 24 .
172 EXPL OS I VE S
stand in the coolers sixty two t o each cooler S liding wooden covers r est
,
-
. .

on the coolers t o gui d e t he fumes from t he clippers in t o ea rthenware pipes

wi t h openings at inte r vals t hrough w hi c h t he v are d rawn by exhaust fans
, .

Fl o . 31 . N it r a ng
ti n r fu g
Ce t i a l wi t h H y dra u lic Co nv ey o r fo r t h e N it r
o -
co t t n
o

(Se l w ig nd L a ng
a e ) .

The mixe d acid ei t her c o o led o r w armed a s neces s ar y is carried b y lead pipes
, ,

placed between each row of coolers and i s supplie d to t he di pper s t hrough,

earthenware cocks at intervals .

N i tra tio n The wate r in t he coolers i s kep t at 1 5 C The dippers °

. .
,

ha v ing been placed in po s i t ion in the c oolers are ea c h fi lle d wi t h 1 27 lb of ,

.
 MAN UFACT URE OF N I TRO C E LL U L OS E -
1 73

mixe d acid by measurement from the aci d tap s ; 4% lb of cotton w aste are
‘

steeped in each dipper To minimize decomp ositions ea c h charge of cotton

.

waste i s added in about ten instalments The w ooden covers are only removed .

to allow steeping to be d one and are then at once replaced The tempera
, .

h ue s of nitration are Initial temperature of mixed acid 1 5 C maximum °

.
,

after steeping 25 C temperature at end of nitration 20 C The duration

,
°
.
,
°
.

of the nitration varies according to the outpu t requi re d from the plant On e .
,

tw o or three shifts may be worked per twenty four hours and the time of
,
-
,

nitration may therefore be t w enty four t w elve or eight hours respectively -

, , .

The average composition of the mixed acid for a twelve hours immersion ’

i s as foll o w s : Sulphuric acid 75 0 per cent ; nitric acid 1 5 75 per cent ;

, .
,
-
.

nitrou s acid 1 3 0 per cent w ater 7 9 5 per cent For an eight hours immer
,
.
,
-
.
’

si o n a higher perc entage of nitric acid a n d less water i s used for a twenty
four hours immersi o n less nitric and more water The average composition
’
.

of the waste acid for a twelve h ours immersion i s Sulphuric acid 77 8 per ’

cent ; nitric acid 1 1 0 per cent ; nitrous acid 1 5 per cent ; water 9 7
.
,
.
, .
,
-

per cent .

Reco ver in g the w a s te a c id When the nitration is complete the di ppers ’

.
, ,

c overed with light aluminium lids are place d on barrows wheeled to the cen , ,

tr ifu g a l s situated at the end of the coolers and the whole contents tilted ’

out into the centrifugals Four dippers are loaded into e a ch c e ntr ifu ga l
.
‘
,

and the g u n cotton having been uniformly spread round the basket the centri
-
,

fugal i s run for s ix min utes t o remove waste acid At the end of that t ime .

ab out 1 lb of waste acid i s still adhering to each p oun d of gun cotton T h e

.
-
.

centrifugal c over made of light aluminium i s not fixed to the centrifugal

, ,

in any way so that a s little resistance as possible may be offered when there
,

i s a decomposition Thi s i s the usual arrangement in the case of acid centri

.

fu g a ls . The cone of the centrifugal proj ects through a circular opening in the
centre of the lid and i s covered by a small loose aluminium box Small holes .

are cut in the sides of t hi s box and are of servi ce in warnin g the workmen
,

when there is a de c omp osition as fumes are generally seen to issue there first
, .

D r o w nin g the gu n co tton When the waste aci d has been removed the
-
.
,

gun cotton i s qui ckly lifted out of the centrifugals and thrown un der the
-

revolvi ng paddl es of the dr o u ming tanks which imme diately immerse it , .

The men who do th e discharging are pro v ided with rubber gloves and wear
thick flannel hoods which completely cover the head arms and breast The
, , , .

hoods a r e fitte d w ith strong glass windows and are connected by light rubber ,

tub ing to a supply of pure compresse d air .

P r e w a s hi n g
-
After a given quantity of gun cotton has been drown ed
.
-
,

the water in the tanks i s run off a n d the gun cotton thrown on to draining -

tables forming part of the dro w ning tank It i s then loade d into the pre .

wash ing centrifugals the acid water wrung out a nd washed fo r a few minutes
, ,
 E X P L OSIV E S

with cold w a t er from a ho s e t o remove a dh eri ng a c i d No special p reca u t ions .

,

ho w e v er are ta ken t o remove a ll ac id a t t hi s sta ge The bul k of t he w ater

, .

h a vin g been r emoved t he gun cotto n is load ed from t he cen t rifu gals into
,
-

bogies a n d conve y ed t o t he bo ili ng house -

.

The si x t y tw o clippers in each cooler form a charge

-
E ight charges .
’

are w ork e d by each s hif t The yiel d is 1 5 9 per cent of dry gun cot t o n on
. .
-

t he dry ca r ded co t t on The ou t pu t per shif t consi t ing of seventee n men is

-
.
s

t he r efore : 4 5 X 1 59 X -
X 8 j 1 00 3 54 9 lb - z .

F1 6 . 32 . Se c t io n o f D is p l a ce ment App a r a t u s (fro m A r ms a nd E x

p lo s i ve s ) .

D is pla c emen t Gun c otton ha s been ma d e at l Va lth a m Abbey by Nathan a n d Thom

-

p r oces s
s on s di s pla c emen t pro c es s s ince August 1 90 5
’
The insta ll ation consists of a
. '

num ber of unit s of four pan s w orked t o ge t her The pans are of eart henware 1 .

and circul ar 3 fee t 6 inches in di ameter and 1 0 inches deep a t the si d e of the ,

pan the bo t t om has a fall of 2 inche s to the o utle t w hi ch i s ift in ch in diamete r ,

-
.

They are s uppor t e d on ea r t hen w are pedesta ls about 1 foot 1 0 inches above
the floor le v el The four pans are connecte d to ge t her by lead pipes and these
.
,

are a gain conn e c t ed t o the ni trat ing acid supply pipe t o the strong and weak ,

w a s t e acid pipes a n d t o a w as t e w a t er pipe thr ough a gauge box w he r e th e

, ,
-
,

1
Pa ns o f a c id r -
e s is t in g ir o n a re a ls o b e in g t ri ed . AM
. 1 9 1 6.
 MANUFACT URE OF NIT R O C E LLU L OS E
-
1 75

rate of flow i s determined whilst the waste acids are being run o ff Gravities .

of the acids are also taken in this box The process proceeds as follows .

A small perforated plate i s placed over the outlet of each pan and four ,

A U n it of Fo ur P an s (fr o m Ar ms a nd Ex p lo s iv es ) .

perforated segment plates making a complete disc ab out 1 inch less than the
inside diameter of the pan are placed on the bottom Aluminium fume
,
.

hoods which are conne c ted to an exhaust fan having been placed on the four
, ,

pans the stone ware co o k on the acid supply pipe i s opened and the acid
,
-
,

FI G . 34 . Vie w s h o n
wi g Ar rang e me n t o f U ni ts in Ro w s (f ro m Arms a nd E x p lo s i v es ) .

allowed to rise in the pans to the proper level The nitrating acid i s c ooled .

in summer and warmed in winter so as to maintain the same temperature

,

of final nitration a ll the year round The composition of the ni trating acid
.

i s 70 5 per cent sulphuric acid 21 per cent nitric acid 0 6 per cent nitrous
.
, .
, .
1 76 E XP L OSIVE S

acid and 7 9 per cent w a t er : t he quanti t y in ea ch pan a b ove t he bo t t om

,
-
.

pla t e s i s 60 0 lb and below t he pla t es is an a d di t ional 50 lb A cha r ge of

.
, .

20 lb of co t t on was t e i s t hen immersed in t he a cid handful by handful alu

.
, ,

mi nium dipp ing forks bein g u se d fo r t he pur pose “ h e n all t he co t ton w aste
-
.

ha s been pushed under t he surfa c e of the acid perfo r a t ed pla t e s in segment s ,

a re placed on t he t o p of i t ca r e bein g t aken t ha t a ll c o t t o n w as te is below

.

FI G . 35 . u n
Pl mb i g I ns t llat io n
a fo r D is p la ce me nt P la nt (fr o m A r ms a nd. Ex p lo s ive s ) .

the surfa ce of t he acid and a fi lm of w a t er a t a t empera tur e from 5 C to 8 C

,
.
°
.
°
.

i s run very gradually on the surfac e of the plates t hrough a di stributor The .

film of w a te r prevents t he esca pe of ac id fumes and the fum e h o ods are then ,

removed The t ime requi red for di ppin g a charge is a quarter of an hour
. .

The nitration is all o w ed to proceed for tw o and a half hour s At t he .

expirati on of t hi s perio d the c ock leadi ng to t he gauge box i s open ed a nd -

,

the was t e acid all owed to run o ff a t t he rate of a bo u t 1 7 lb a m inute \Va t er .

. .
,

c o ol e d if neces sa ry is run on t he top o f the pe rfo r ated plate s thr ough the
, , ,
 MAN U FACTURE OF NITRO C E LL UL OS E
-
1 77

distributor at an equivalent rate l Th e maj or portion a m

, ounting to about
.
,

8 0 per cent of the total waste acid i s returned to the acid store tanks to be
.
,

r e v iv ifi e d with Nordhausen sulphuric and new nitric acids The c omposition .

of thi s waste acid is 72 70 per cent sulphuric acid 1 7 30 per cent nitric acid .
,
-
.
,

0 65 per cent nitrous acid and 9 35 per cent water

.
, The remaining 20 per . .

cent of the waste acid is sent to the acid c oncentration factory for denitration
.

and c oncentration The quantity of acid thus dealt with amounts to about
.

4 lb for every p ound of gun cotton

. Its composition i s 61 0 per cent sul
-
. .

h u r ic acid 1 7 3 5 per cent nitric acid 0 5 5 per cent nitrous acid and 2 1 1 0
- -
p , .
, .
,

per cent water A small proportion of the water which follows the recover
. .

able waste acid is slightly acid to the extent of 0 1 lb for every pound of gun .

cotton made This is the total quantity of acid that i s lost during the process
. .

In the di rect dipping and nitrating c e n tr ifu g a l p r o ce s se s the quantity of waste ‘

acid left in the gun cotton i s at least equal to th e weight of the gun cotton
‘

- -
.

The whole of the acid i s displaced in three hours and the water which , ,

shoul d fill the pan i s run through the gun cotton the gun cotton drained
,
—
,
-

”
down and sent over to be boiled These operations occupy about an hour . .

The following Table gives the principal figures in c onnexion with the four
nitration processes described

N O TE Th e o u t p u t w it h n it ra t ing
—
ce nt rifugals is no t gi ve n in th e o r ig inal p ap e r . It
is ap p r o x imat e ly a s s t at ed .

The fo llowing are the principal advantages which the displacement process
p ossesses over the Abel process and over the di rect dipping and nitrating ,

centrifugal processes where they are similar to the Abel process

(1 ) The displacement process takes the place of the processes of dipping ,

squeezing out excess aci d digesting in pots acid ce ntr ifu g a ling immersing
, , , ,

and water c e n trifuga ling .

V OL . I.
1 78 E X P L OSI VE S

( )
2 The actual di pp ing of the cotton waste is a very much less laboriou s
opera t ion t he heavy labour of squeez ing out the excess acid i s done a w ay
—

w i th the absence of fumes makes the work much healthi er and inj u ries to ,

w o rkmen from acid splashes are almost unk nown .

( 3 ) Loss of gun cotton due to decomposition

-
in the di ges t in g pots and
aci d centrifugals and consequent inc onvenience and danger t o w orkmen
,

fro m nitrous fumes are done a w ay with and the heavy loss from breakage s
, ,

o f p o t s and lids i s saved Thr ee and a half years e xperience ha s proved that ’
.

the earthen w are pans are very last ing .

(4 ) Fumes during dipping loadi ng and unl oadi ng acid centrifugals and
, ,

immersing are avoided ,

.

( 5 ) The quantity of acid lost is very much reduced Th i s reduction .

means also very mu c h less p ollution of the escaping w ashing water .

( 6 ) The recovere d waste acid i s very much cleaner a matter of the great ,

est importance from the p o int o f view of r e v i v ifi ca tio n and concentration .

( )
7 The mechani c al loss of g un cotton in the acid and w
-
ater c e n t r ifu a lin
g g
pr o cesses and in the immersing process i s saved
, , .

(8 ) A more thorough pre liminary wash i ng of the gun cotton i s obtained -

wi th an e x penditure of about one fi fth of the quantity of wate r and less -

,

bo iling a n d c onsequently less ste am i s required in order to reach a given

, ,

standard of purity .

(9 ) Great sa v ing in p ower is ga ined by the abolition of the acid and water
centrifugals and by the reduction in the quantity of w ater w hi ch has to be
,

pumped .

(1 0 ) Rene w als of plant and repairs to plant and buil din gs are exceedin gly
,

( )
1 1 The number of hands employed fo r any given output i s much less
the total cost of labour being reduced by tw o thirds -
.

( ) The y ield is improved ; it averages 1 70 per cent

1 2 .

( 1 3 ) Fina l ly a more stable gun cotton of m ore uni form c omposition i s

,
-
, ,

produced It i s also far cleaner and conta ins notably less mineral matter
. .

The last claim especia lly has proved to be amply j ustified Cordi te made .

from gun c otton manufactured by the di splacement process sho w s p romise

-

of lasting about twice a s long under adverse cli mati c c on ditions a s that i n ,

w hich the Abel proces s was used in spite of the fact that the latter woul d
,

compare favourably with any other gun c otton made excep t by the di splace -

ment process .

Thi s improved stabi lity i s probably connected with a cur ious fact which
has been o bserved by Ma c D o na ld 1
He found that as the di splacement .

pr o c eeds the percentage of nitri c a c id i n the w aste aci d after falling sli ghtly
,

ha s a distinc t rise and then falls again (s ee Fig The ratio of ni t r ic to .

1
J S o c C h m I nd 1 9 1 1 p 251
. . e . .
, , . .
 MAN UFACT U RE OF NIT RO C E LL U L OS E
-

sulp huric acid also after a very slight fall , rises steadi ly until the end of the
,

displacement and washing This can only be due to a partial denitration of

.

the gun cotton and evidently the more unstable products a r e decomposed
-
,

to a greater extent than the normal stable gun c otton -

.

The recovery of the w aste a c id i s far more complete than by any other
process but on the other hand it i s di luted somewhat with the water used
, , ,

for the displacement Consequently a considerable plant is requ ired for

.

Ti me in Mi nu t e s
FI G . 36 . t
C o m p o s i io n o f D is p l a ce d Ac id s .

worki ng up the acids again and reconcen tratin g the m According to Ma c .

D onald the loss of acid i s only 0 0 8 lb per p ound of gun cotton produced .
-
,

but hi s own figures as has been p ointed out by Delpy indi cate a very much
,
1
,

higher loss .

In a ll the p rocesses e x cep t that of displacement there i s liability of the

charge fuming o ff either i n the p ots or centrifugals Thi s i s especiall y the .

case i n hot weather or if the cotton has not been su ffi c iently pur ified from
grease etc o r has hard lump s in it which the acids can onl y penetrate slowly
,
.
,
.

Acc o r ding to W o r den 2 t i s sue paper fo r lac quers i s nitrated in Ame ri ca Hy a ttnitr t
,

in pots whi c h are placed on a rotating table about w hi ch are arranged inlets
, ,

1
S S .1 9 12
p 23 7 , .
2
N itr
,
e ce llu lo s e I nd u s t y p 1 1 0 - r , . ,
 E X P L OSI VE S

for acid a st irring appara t us and a mechanism for tippin g t he p o t s into a

, ,

c entrifugal The plant must be some w hat cum bersome and expensive a n d
.
,

i s not likely to be a d opte d for the manufactur e o f exp losives .

Hig h nit og en
r The de tail s gi v en by Sir F L Nathan refer to t he manufa c t u r e o f gun . .

g un cott n
- o
c o t ton c o n t ai nin g abou t 1 3 per c ent N If it be desire d to o b t ain a produc t
.

. .

w ith a higher percen t a ge of nitrogen i t i s necessary to in c rease t he p ropor t ion ,

o f nitric acid in the mixed acid

(s ee Figs 28 but it i s not very of t en t hat .
,

i t is required to obta in a perc entage much hi gher than 1 3 because such ,

produ c t s are less sta ble a n d are m o re e xpensi v e to manufactur e I t ha s .

been sho w n by Lun ge and Bebie that beyond 1 3 5 per cen t the prod ucts are .

qui t e unsta ble (see p .

Par tia lly For t he manufactur e of various smokeless p o w ders nitro cot t o ns p a rtially -

s olub le
ni tr o cotto n
- s.
s o luble in ether alcohol are used The acid mi x ture to be emplo y ed depends
-
.

upon t he sort of c ell ul o se and the metho d of nitration .

So lub le For a nitro c otton to tall y soluble in ether alcohol there shoul d ac cordin g
- —

nitr o-cott o n
,
s.
to Fig 29 be a mole c ule of water for every molecul e o f acid whe t her ni t ri c
.
, ,

or sulphuric but in prac t ical manuf act u re a smaller proporti on of wa t e r i s

,

genera lly use d especiall y if a high percentage of nitrogen i s required At

, .

o n e time i t was thought to be impossible to prepare a to ta llv soluble produc t

conta inin g m ore than 1 2 per cent N Me n de lé efi however w h o w orked . .

, ,

at this subj ect from 1 8 9 1 t o ab out 1 8 9 5 produced a soluble ni t ro cotton w ith ,

-

abou t 1 2 5 per cent N a n d he pointe d out that a product with 1 24 4 per cen t
.
, .

conta ins j ust enough oxygen to con v ert all the carb on into C O a n d a ll the
Py m coll e
-

lio n
.
hydrogen into water Thi s material which has
. been ca lled p y ro coll o di on ,
-
,

was a d opte d as the basis of the Ru s sian mili ta ry smokeless powder and later ,

the U ni ted S tate s adop ted a powder made from a pyro collodi on conta inin g -

about 1 2 5 to 12 7 per cent N This i s produced by nitrating at a c ompara . .

t e y high temperature
i v l Accordi ng to Worden in Pica ti nn y Arsenal the
1
.
,

nitra t ion i s now carried out in Thom son s di splacement plant The acid ha s ’
.

the composition

The temperature i s 3 0 a n d the charge in each pan consists of 20 lb

°
.

c otton a n d 70 0 lb acid . .

A high degree of nitration i s al s o desirable for the coll o di on used for t he

manufa c ture o f blasting gelatine and other s imil ar hi gh exp losi v e s but the ,

nitro gly c erine con tains an excess of oxygen and the propor t ion of c oll o di on
-

cot ton is s ma ll s o t hat high p o w er is not of the same impor ta nce as in the ca se
-
,

of a mi litary p owder The great essential is that the coll odion cotto n shall
.

1
N itro c e ll ulo s e I nd us try p , . 9 7.
 MAN UFACT URE OF NI T RO C E LL UL OSE-
181

give a good s tifi colloid with the nitro glycerin e Other things being e qual -
.

a cotton of high ni trogen will give a s tifi e r gelatine than one of low but it
'

will di ssolve more slowly with the result that the material will become sti ffer
,

o n prolonged storage and less sensitive and t hi s may cause mis s fi r e s The
,
.

percentage of nitrogen in collo di on cotton for blasting explosives is usually

between 1 1 5 and 1 2 per cent The o fficial definition of H M Inspectors of
. . .

E xp losives gives an upper limit of 1 2 3 per cent It i s of great importance

0
.

that the cotton before nitration shall not be submitted to drastic treatment
either wi th chemicals or heat for this breaks dow n the molecules of cell ulose
,

and makes the blasting gelat ine soft For the same reason the nitrated .

product i s not boiled as i s done in the case of gun cotton but it is treated
,
-
,

for some days with water at a temperature of about The pulping also
i s not carried so far .

For the manufacture of artificial silk and lac quers etc a collodi on i s ,
.
, C oll odio x
f or o th e
required that shall be as li ttle vi scous as possible so that only a comparatively ,
p ur p o s e s
small proport ion of solvent i s requir ed A high degree of ni tration i s o b je c
.

tio n a b le
. Consequently the pr o cess of manufacture di ffers in many respects
from that of collo di on for blasting gelatin e The nitration may be carried .

out at a hi gh temperature 40 say for several hours with a mixed acid con
,
°
,

taining about 1 8 per cent water and about 20 per cent ni tric acid
.
1
For . .

other purp oses such a s the preparation of collo di on solution for dipping
,

i ncandescent mantles a collodi on of interme diate vi scosity is requ ired

,
.

1
S ee T . C h a n d e lo n , B u l . S oc . C h im . B e lg 1 9 1 4, 28 , p p . 13 , 24 .
 C H A P TE R X I I I

THE STABILI ZATI ON OF NITRO- CE LL UL OSE

Ea rly me t ho d s B o ilin g Pu lp in g R mo val o f fo re ign b o di e e s P o a c hin g
B l ndi n g
e Ad di t io n o f ca l ium c ar b o na tc Mo uldin g e t c e , . Th e b ea te r
Alka lin e m t h o d f t a b ili a t io n
e o s Sul p hu i e st r s
z V lo c it y
r c e e o f hy dro ly sis
o f ni t r o ce ll ul o se
-
US Ordn a nce me t ho d
. C e ll ulo se ni t it e s r P ro d u ct of
s

d e c o mpo si t io n “ a hi n g c o ll o d i o n co tt n
s o

THE gu n co t ton that w a s manufact u red in t he early days was pur ified by
-

w ashing in c ol d wate r onl y and it is principally t o thi s very inadequate

,

treatmen t t hat t he n u merous catastrophes of those ti mes are t o be asc r i b ed .

On e of von Le nk s most important improvemen t s w a s the i ntroduction of a

’

b oili ng of fif t een minutes with a potash solu t ion of specific gravi ty 1 0 2 Sir .

F Abel tried pulpi n the g un c o t t on wi t h t he obj ect of ob t aining i t in a more

.
g -

c omp a ct and c onvenient form In hi s pa t en t s p ecifica t ion No 1 1 0 2 of 1 8 65

.
, .
,

he says
Now my invention has fo r its obj ect to assimil a te t he physical c ondi t ion
of gun co t ton as nearly as possible to t ha t of gunpowder by me c hani cally
-

c onverting it i nto a solid c onglomerate s t a t e and impar t ing t o i t ei t her a .

gran ul ar or other suitable form t hat wi l l present t he ex a ct am ount of s m fa c e '

and c ompactness requir ed for obtaining a cert ain rapi di t y or in t en s ity of

c ombustion .

I fir st convert cotto n wool by the proce s ses now well kn own into gun
c otton For this purpose I prefer t o use t he cotton in the form of a loose
.

roving W hen the gun co t ton has been p uri fied from acid by washing in
.
-

ru n ning water and in very dilute alkali I trans fer it to a b eating en gine of ,

the description commonly used in the manuf act u re of pape r where i t is reduced ,

to a pulp which is t hen converte d int o soli d m a sses

,
.

B olling . P rolonged boil ing w i t h w ater whi c h is an es sential feat ure of t h e m od ern
,

process of stab iliza t ion was not in tr oduced un t il c o nsiderably later Sir
,
.

F L Na t han remarks t hat

. .
1
B o iling as n o w under s tood di d not form part
of the proc ess of g un cotton manufacture when manuf acture was started at
-

l Va lth a m Abbey early in 1 8 72 Abou t the mi ddl e o f 1 8 73 h o w ever boili ng

.
,

1
J . S oc . C he m I
. nd 1 90 9 ,
p . 18 0 .

18 2
 TH E S TA BI LI ZATI ON OF NIT RO -
C ELLU L OS E 183

vats were put up at Waltham Abbey but no records exist unfortunately

, , ,

about the details of the early b oili ng processes In the o fficial No te s o n Gu n

’

p ow der a n d Gu n co tto n
-
published
,
by the War O ffice in 1 8 78 it is stated that ,

gun cotton manufact u red at Waltham Abbey underwent two b oil ings by
-

steam in wooden vats fo r eight hours each the water being extracted after
,

each boiling by wr inging for three minutes in clean water centrifugal machines .

The same b oili ng process was in use i n 1 8 8 8 accor di ng to a later e di tion of the
,

same b ook E v e years later each b oiling was extended to twelve hours
. ,

and the boili ng lasted for five days and ni ghts that is the gun cotton received
—
,
-

ten b oilings of twelve hours each In April 1 8 9 4 thi s system of boiling was
.
,

replaced by a system characterized by short b oili ngs at the c ommencement

of the process the time of successive b oilings being gradually increased The
,
.

scheme of b oiling was as follows

This system of b oiling was continued with but slight modifications until
August 1 9 0 5 On the introduction of the di splacement di pping process it
.

was found as alr eady stated that gu n c otton made in thi s way w a s brought
, ,
-

to a c ondition of stabili ty by the b oili ng process then intu se and j u st referred ,

to at an earlier stage than gun c otton made by the Abel proce s s A probable
,
-
.

explanation of this fact i s that during the displacement process a zone of

acid li quid at a comparatively high temperature somewhere ab out 40 C —
°
.

passes through the whole of the gun cotton i n the dipping pan The action
-
.

of thi s hot acid liqui d may be to oxi di ze certain organi c impurities which are
certai nl y present and to cause the brea king down of u nstable ni trogen c om
,

pounds into soluble or non reactive b o di es Systematic experiments were

-
.

therefore carried out i n 1 9 0 5 to determine the most suitable and most e c o n o

, ,

mical meth od o f purification by boi ling for displacement process gun cotton -
.

In the principal experiments two types of b oiling were employed one i n which —

long boili ngs were used at first followed by short b oi lings the o th e r a
,
in which
sh ort boi lings were used at first foll o wed by long boi lings The following
,
.

deductions were made from the results obtained i n these experiments

( )
1 P u rification of gun cotton -
obtained by means of long b oi lings at
th e beginni ng followed by shorter b oilings later is superior to that obtained ,
184 EX P L O SIVE S

w hen t he re v erse con di t ion holds This is substantiated by t he follo wi ng .

c onsi dera t ions E xami na t ion of the w a t ers sho w ed that neu t rality is ob t ained
earli er ; t hat less d ec omposi t i on of the gun cotton takes place ; that the .
-

s tabili t y as sho w n by t he various s ta b ili t y te s t s is greater a n d th at a stable

, ,

c ondi t ion is a t tained ear lier .

(2) A di splacemen t washi ng af t er a long acid boiling at an early stage

is a beneficial tr a t men t
e
1
This t reatmen t is probably responsible for the
.

early a t t ai nment of neu t rali t y .

The syste m of boiling de t ermined on as a res u l t of t hese experiments

was as follo w s :

wi t h a c old wate r di splacement wash af t er t he fir st two b oili ngs A full .

a c c ount of t hese investigations was given by Dr Robert son in a paper on .

-

t he p u ri fica t ion and stabili zation of gun c o t t on 2

Thi s sys te m of b oili ng i s -
.

s t ill in use a t t he Royal Gunpowder Factory .

The ques t ion of how the purificati o n o f gun c otton c an best be effected -

c annot however be c onsidered as set t led nor can t he sys te m which has j ust
, , ,

b een descri bed although it un d oubte dl y gives an excellen t gun cotton at the
,
-

Royal Gunpowder Factory be applied t o gun c o t ton made by other processe s

,
-

at other factories without full inves t iga t ions as t o it s s u t ability Ano t her
,
i
.

mat t er whi ch must be taken in t o account in conne xion wi t h t he puri fica t ion
of gun cotton by boili ng i s t he nature of t he wa t er available The water
-
,
.

at W al t ham Abbe y is very hard a n d its alka lini ty may be an impor t ant ,

f a c t or in t he success of the boi ling trea t men t i n use t here This que s t ion .

i s perh aps c onnecte d wi t h ano t her one and t ha t is t ha t t he boiling o f gun , ,

c o t ton can b e carrie d to o far The eff ect of boili ng w hil s t i t no doubt breaks
. ,

down impuri t ies al s o n o d o ub t breaks down t he s table e s t er i ts e lf I t is

, , ,
.

well known t h at if gun c o t to n i s boiled fo r a suffi c ien t ly prolonge d pe ri od

-
,

t he percenta ge of s oluble ma tt er w il l ri se and t he nitrogen content wi l l fall -

.

The breaki ng d own of es ter will be a c compani ed by t he forma t ion of a c id

1
A g o o d me t ho d is to r un in co ld wa te r a t t h e bo tt o m o f t h e v a t , w hic h r ma in e s

fu ll of w at e r t h e w h o le t ime . Th e co nt e nt s t h n d e o no t s e tt le d o wn t o a co mpa c t ma ss .

3
J . S oc . C he m I nd
. 1 90 6, p . 624 .
 TH E STAB ILI ZATI ON OF NIT RO C ELL U L OS E
-

bo di es and the presence of alkali in the w ater will neutralize them and pre
,

”
vent them from reacting on the gun cotton -
.

Since the ab ove was written it has b een foun d possible to reduce the time
of boili ng still further with out affecting inj uriou sly gun cotton made by the -

di splacement process .

On c ompletion of the bo iling process the gu n c otton is transferred to P l p ing - u .

a beating eng ine somewhat similar to that employed for pulping the raw
material used in the manufactur e of paper It c onsists essentia lly of a large .

iron roll er armed w ith steel knives and a bed plate also provide d with knives ,
-
.

The roller revolves and as the gun cotton passes between the two sets of
,
-

kni ves it i s reduced to pulp of any des ired fineness As the pulping process
, .

proceeds the roller is graduall y lowered nearer to the bed plate

,
-
.

Since the introduction of a thorough system of purification by b oili ng ,

Abel s original idea that the p ul ping and washing the gu n c otton received
’
-

in the p ul ping process had a very material e ffect on its p u ri fication no longer ,

holds good to the same extent At the same time there i s no doubt that the .

very long staple gun cotton before pulping retains in its tubes unstable b odies
-

which no reasonable amount of b oiling w ill remove The eff ect of pul ping .

i s to reduce materially the length of the fibres and at the same time to pro , ,

duce a certain amount of crushing in them This allows of impurities of an .

acid character i n the tubes being removed either mechanically or by diff usion ,
.

Af ter p u lping it i s now customary to treat the gun cotton in s o me Remo a l 0

,
-
v
f o e g n b od
mechani cal way in order to remove from it particles of metal grit and for
, , ,
r i

e ig n b o di es of a similar character At the Royal Gunpowder Factory thi s .

i s effected by runni ng the gun cotton pul p suspended in a large volume of -

,

water through gr it traps placed at intervals i n a long shallow trough the

, , ,

b ottom o f whi ch i s c overed with blanket The foreign bodies being almost .
,

entirely heavier than the gun cotton pul p are retained i n the grit traps and
-
, ,

the fine sand also present i n some quantity i s caught by the wooll y blanket
, ,
.

An electro magnet in the last grit trap removes any magnetic particles passing
the ordinary grit traps It is surprising what a large quantity of foreign
.

bodi es are removed by these arrangements In addition to grit traps and .

troughs some factories use wh at is known as a knotter the f u ncti on of which

, ,

is to remove small knots and any large pieces of gun cotton which may have -

escaped complete pulping .

Washing the gun cotton during the pulping i s e ffected i n some factories Poa ch ing
- .

by the use of drum washers fixed to the beating engine i n the Royal Gu n
p owder Factory and other factories this washing i s done in separate vessels
termed poachers ‘
The poachers in use at Waltham Abbey h ol d about 10
.
’

cwt o f gun cotton a n d 1 10 0 gall o ns o f water a n d are fitted with p o wer

.
-
,

dr iven paddles for agitation purposes The gun cotton receives at least .
-

three washings ; it is all owed to settle down af t er each w ashing and the ,
 E X P L OSIVES

w ashi ng w ater is removed by a ski mmer The wash ing wate r c onta ins in .

sus p e nsion foreign b o di es of a lo w er spe c ific gravi t y than gun c o t ton a n d in -

,

the case of the earlier w ashing w ate rs there i s always presen t a sc um c on ,

.

taini ng ni t ro bodi es of low s t abili t y

-
.

“
A f u rther p u rpose served by poaching is the t horough blendi ng of a
number of di ff erent b atches This is a final blending but a t t he Royal Gun
.
,

p o w der Factory there e x i s t s a regul ar sys te m of blendi ng ri gh t t hrough t he

wh o l e of the manufacturing processes This syste m i s b ri efly as follows
’

The c ot ton w aste reac hes t he fact ory in c onsignm ent s from di ff erent con
tract ors The w as t e is drawn from t he s t ore in propor t ion t o t he quan t i t ies
.

on the c ontracts and is mi xed and passed thr ough t he t easing mac hine in
,

these proportions .

“
The next process where blendi ng is possible is in c harging t he bo ili ng
vats Tw o vats are fil led sim ul taneously from a number of se t s of pari s
.

two pans of each set of fo u r going into one vat t he o t her two of t he set into
the o t her va t On c ompletion of th e b oilin g four va t s are emp t ie d s imul ta
. .

n e o u s ly in to t hirty tw o beaters
- This ensures t he gun c o t t on fr om the four
-
.
-

vats being blended together in th e beatin g process .

On t he c o mpletion of t he pul p ing the bea t e rs are r un alternate ly in to

the poachers in such a manner t h at t he c ontent s of t he t h ir t y tw o b ea t ers -

are blended int o eight poachers The gun cot t o n in the eight poachers is
.
-

t herefore uniform t hrough out .

The sys t em produces gun c otton of very un i form ni t rogen conte nt

- -
.

In 1 9 0 7 1 90 8 29 1 t e s t s represen t ing 60 0 t o ns of gun c o t t o n ga v e t he foll o w

—
.
,
-
.

in n i t rogen resul t
g

Ma x imu m Min imu m Me a n

From t he poacher t he pul p passes t o a stuff chest or large tank pr o vided —

wi t h stirri ng arms Abou t t hi s stage if the gun c ot t o n is to be m a de in t o

.
,
-

c ompressed blocks for blas t ing stabili zing ma t t ers are a d ded u s u ally c alcium
, ,

carbona te If the water u sed be hard a c onsi derable amo u nt may be p r e c ip i

.

t a te d on the fibres by the addi tion o f lime wa t er If t he w ate r b e s o f t o r . .

the quantity of calcium carbonate to be adde d be large it m ay be ad d ed in ,

the form of whi t ing .

B o nldinx . oh . To remove t he great b u lk of t he wa ter the pul p may now b e pa s s ed int o .

a centrifugal machine li ned wi t h fi n e c anvas The damp mass t hu s ob tained

, .

still conta ins 40 or 50 per cent of wate r I t may be sen t a w ay from t he gun
. .
 TH E S TABILI ZATI ON OF NITRO C ELL U L OS E
-

c o tton factory in this form or it may be moulded fir st into blocks This i s

, .

done by loadi ng it into a hydr aulic press where it is subj ected to a pressure
,

of 3 0 or 40 lb per square inch P resses are also ma d e which di spense with

. .

the preliminary wringing in the centrifugal machine These have h ollow .

plung ers c overed wi th fine wir e gauze and the b ul k of the water is drawn
,

o ff through these by the application of a vacuum The hydr auli c pressu r e .

i s then applied whereby the gun cotton is moulde d into a block or cylinder
-
,

which can be handled c onveniently .

An important p o int concer ni ng the beating engine is t o secure a very Th e b ea ter .

good circulation of the water In the machines used in the paper I ndustry
.

FI G . 37 . Be at er u
fo r P lp in g G un -
co tt n
o .

the rotation of the drum causes the w ater to move round so fast that the
fibrous cellulose material cannot settle but is carried round and roun d so, ,

that it c omes repeatedly u nder the kni ves until it has been reduc ed to the ,

required degree of fineness and the mac hi ne re qui res very little attention
, .

But if the same machine be u sed to pul p ni tro cotton it is found th at the -
,

soli d material tends to settle down at the b ottom and it i s necessary for a ,

man to attend the machine and help the material round with a wooden paddl e .

This is not due en t irely t o the increase of the specific gravity for that of ,

nitro cotton i s o nly 1 67 whilst that of c ott o n is about 1 6 1 but i n the nitra
- -
, ,

tion the weight of each fibre has i ncreased about 70 per cent The length .

has not bec ome greater probably it has diminished some w hat c onsequently
, ,

each fibre has become much stouter as may be seen clearly on comparing
,

micro ph otos 1 a n d 7 Fig 3 0 There is therefore much more weight for the
-
, . .
 EX P L OSI VE S

sa me amount of s u rface and con s equentl y t he ma t e r ial is bo rne along by ,

t he water w i t h g rea t er diffi c u l t y .

A good form of bea te r is t ha t o f H o yt in w hi c h t he mate ri al is m a de t o ,

circula t e vert ically ins tead of horizon t a lly The dru m c a r ri es t he w a t er and .

pulp right over af t er which t hey des c en d a s t eep inclin e t hen ano t her u nder
, ,

t his slop ing in t he opposi t e dir ec t ion t o t he lo w e s t poin t of t he kn if e dr um .

The fixed kni ves un d er the ro t a t in g drum requi re t o be sharpe n ed fr e

quen t ly and it is usual t o have a dupli ca t e se t The kni fe blades on t he
. .
-

drum also req u ire sharpeni ng from time to t ime They t hus be c ome gr a duall y .

shorter and t hi s causes t he circul ation of t he pulp t o become w orse

, .

The kni ves are some t imes made of phosphor bronze a s i t has bee n foun d ,

that particles of iron have a deleterious effec t on t he s t abili t y of t he ni t ro

cellul ose but they have t he di s advantage t ha t t hey w ear fas t er tha n s t eel
,

kni ves .

The development of t he me t hod of s t abili za t ion t ook a somewhat di fferent

c our se in some factories ; a boili ng proces s has been introduced aft er t he ,

pulping and w a s carried out in large ir on t a nk s fi t t ed wi t h s t irri n g gear and

,

valves for r u nni ng o ff t he water at di fferen t level The w ater h ad t o b e s .

kept alkali ne thr ough o ut t he O perations els e t he a cid developed by t he ni t ro ,

cot t on would at t ack t he iron of t he vesse l A t fir s t s ight i t appe ars as though s .

the boili ng in the pulpe d sta t e m u t p u rify t he ma t e ri al mu c h m ore e ffe c tu a ll v s

t han when the ma t erial is c ompac t bu t experience has proved t ha t t hi s i s ,

not so Robert son has shown tha t t he most import an t par t of t he purifica t ion
.

is the b oili ng wi th dilu t e acid and in t he alkali ne me t hod t hi s is omi t t ed ,

altoge th er Actual tests and trials have sho w n t ha t t he g i m c o t t on s t a bil i zed

.
-

by t his process is di s t inc t ly inf erior t o t ha t prepared b v t he ll a lth a m Abbey

'

proce ss .

Sul p h uric The reason for t his or at least one rea s on w a s revealed by t he observa t ion
,

of Cross Bevan and Jenk s t ha t mi xe d e s t ers c on t aini ng bo t h sul phur ic and

, , ,

ni t ric ac id residues are liable t o be formed w hen cell ulo s e is i mm ersed in t h e

mi xed acids 1
The observa t ion w a c onfi r me d by Hake and Le wi s and
s .
2

was f u rt her investiga t ed by Hake and Be ll 3

Wh en t he s e produc t s are a llo w ed .

to stand t hey gradually become acid in c on equence of t he forma t i o n of fr ee s

sul phuric a cid which ma y u l t ima te ly lead t o t h e s pon t aneou explo s ion of
,
s

t he gun c otton Hake and Le wi s sugges t ed t ha t t he di s a s t rou s e xplo s ion

-
.

at S t owmarket in 1 8 71 w a s probably cau s ed b y t he pre s ence o f sul ph u ric

este rs .

It was sho w n by Robert son t hat t he s ul ph uric e s t er s are decomposed

4

hydrolyt icall y by boili ng wi t h acid w a t er much m o r e rapidly t han wi t h a lka line

1
B er .
, 1 90 1 ,
p . 24 9 6 ; Re s ea r c he s on C e ll u lo s e , vo l . ii .
,
p . 51 .

2
J . S oc . C he m . I nd . . 1 90 5 ,
pp . 3 74 a nd 9 14 .

3
J . S oc . C he m I nd .
, 1 90 9 , p . 45 7. 4
J . S oc . C he m . I nd .
, 1 90 6, p . 624 .
 TH E STABILI ZATI ON OF NIT RO C E LL U L OS E —

water in fact treatment w ith alkali s seems t o fi x the sulphuric group fir mly
into the product This behaviour is very similar to that of the cellulose
.

aceto sulphates which have been in v estigated by Cross Bevan and Bri ggs
—
,
1
, , .

They found that even under the action of c old di stilled w ater the sulphuric
acid residue of these mixed esters was gra d ually split o ff but much more ,

rapidly in boili ng w ater whereas on treatment with alkaline solutions the whole
,

of the acetic acid residue c oul d be eli minated by s a p o ni fi ca tio n whil st the ,

c ombination between the cellulose and the sulphuric acid remained intact
i n the form of a cellul ose sulphate This behaviour was explained by the .

fact that the sulphuric acid residue in these esters e x ists in the form of SO H 4 ,

which is readi ly hydrolysed by the action o f water or acids but become s ,

SO M in the presence of alkalis towards which it is remarkably stable It

2
.
4 ,

has been possible to study the aceto sulphates more thoroughly than the -

ni tro sulphates because a larger proportion of s u lphuric acid can be made

-

to c ombine in the former case .

It was sho w n by Robertson that the sulphuric esters are eli minated
3

more rapidly from the gun c otton if the fir st boilings are long that is not -
,

less than twelve hours each than if they are sh ort The reason is that under ,
.

these condi tions the material is in c ontact with h ot di lute acid for a c onsiderable
time whereas if the water be renewed constantly the alkalini ty is restored
, ,

each time and this impedes the s a p o nifi c a tio n of the sul phuric esters
,
.

Although the s u lphuric esters are hydrolysed so much more rapi dl y by

acid than alkali the reverse is the case with the nitric esters The velocity .

with which a nitro cell ulose c o ntaini ng 1 28 4 per cent N is hydrolysed by

-
.

solutions of barium hydrate at a temperature of 3 9 was measured by Silb e rr a d °

and Farmer 4
They found that the velocity is given by the equation
.

( (s
1 v) in which 9 is the quantity of ni tro cellulose in grammes per -

400 c c of the solution 7) is the ob served velocity with which the alkali ni ty
. .
,

of the s olution di mi ni shes measured i n gramme e qui valents per li tre per —

hour 8 i s the limi ting velocity for a solution saturated with ni tro cellulose
,
-
,

and k is a c onstant Further as the velocity is proportional to the concentra

.
,

tion of the baryta the e quation may be wri tten : ,

e ga
’
k 9

0 being concentration of the baryta in gramme equivalents per litre

th e —

8 0 1 68 and k 265 .

For hy drolysis by means of nitric acid the values found for these constants
were 3 0 0 00 3 4 7 and k 32 1 Hence w hen the pr o portion of nitro c e ll u
2 .
-

lose t o li quid is high as it is i n the b oiling vat s hydrolysis i s about 48 0 times

, ,

1
B er .
, 1 9 0 5, p p . 38 a nd 1 8 59 .
2
r
B igg s , J . Soc . C h em . I nd .1 9 0 6, p 626
, . .

3
J . S oc . C h em. I nd .
,
1 90 6 p , . 624. 4
Tr a n s . C h em Soc . 1 90 6, p 1 75 9 . .
 E X P L OSIV E S

as rapid in a n al kali ne solu t ion as in an a cid soluti on of e qual strength For .

t his reason i t is un a d vis able to use s t rong a lka li for the stabili za t ion ca ustic s

alka lis shoul d be avoided and sodi um carbona t e should only be used when
the w a t er o t her wi se c on t ains no alka li Hard wa t er po ssesses s ufficient .

a lkali in t he form of c alcium bic a rbona t e wi t hou t any a d di t ion and this is ,

the mos t s u i t able for s t abiliz ing ni t ro cell u lose Moreover t r eatment wi th -
.
,

s t rong alka li is lia ble t o convert t he ni t ro cell ul ose in t o un stable dec omp osition -

products .

The t w o me t hods of sta bili za tion are of t en c ombin ed that is to sa y aft er , ,

t he ni t ro co t t on ha s bee n boiled and p u lp ed i t is a ga in boil e d The ins tr u c

-
.

t ions of t he U S Arm y Ordn ance Depa rtmen t a s revised up to Ap r il 1 8 1 90 8

.
, ,

a re for instance :
O dna nc e
r
N itra ting C ellulose of sta nda rd qual it y shall b e dried at a tempe ra ture
—

meth od .

not excee di ng l l h e n c old thi s co t ton sha ll be ni tr ated in mi x ed nitric

'

a n d sul ph u ric acids Af t er ni t r a t ing t he ni t r o cellulose shall b e washed in

.
,
-

w ate r before b o ili ng .

P r elimina r y b o iling The ni tro cell ulose shal l be bo il ed a t lea s t forty

.
— -

hours and wi th not les than four changes of water in tub s so con tructed
,
s
,
s

that the ni tro cellul ose shall not come in c on t ac t wi th t he steam at a tempera
-

tur e gr ea t e r than -
The r e shall be complete ebul lition or boilin g over
t he en t ire sur face of t he t ubs No a lkali shall b e u sed in thi s p relimin ary .

p u rification .

P ul pin g The ni t ro cell ulose shal l then be pul p ed in fr esh water t o

— -
,

w hi ch sha ll be added j us t enough so di um carbonate to p r ese r ve a sli ght a lkali n e

reaction to phenol phthale in solution t he proc ess is con t inued un til the
-

mate rial is t horoughl y and evenl y p ul pe d to a sa ti factory degree of finenes s s

,

and sho w s a c lean break when a handf ul is s quee zed and broken into parts .

Dur in g t hi s proce s s t he w ater shall b e changed to such a n extent a s may be

nece s sa r y to remove t he impuri ties .

“
P ou ch in A ft er pul ping t he ni t ro cellul o se pulp s h a ll be r un to the
- —
.
,
-

poac hers s et t led and t he water d e ca n t ed The ni t ro c ellul o m sh all then

, ,
.
-

b e boil ed s ix hours in fresh water and dur in g t hi s t ime not mo r e than 1 0 ,

ga l o ns of carbonate of s oda s olution for each 200 0 lb dry ni t ro cellul ose may
'
.
-

be added a t in t e r vals This solu t ion sh a ll con t a in 1 lb c a rbonate of soda

. .

per ga llon Dur ing t hi s and all o t her bo iling in t he poachers the pul p shall
.

b e t horoughly a gi t a ted by mechanical stir r ers Af t er boiling t he nit r o ce ll u .

-

lose s hall be a llo w ed t o set t le a nd the clea r w a t er decanted a s completely

as pos ible The t ubs sha ll then be fill ed wi t h fr esh water bo il ed t wo hour s
s .
,

settled decan t ed a nd re fi lled wi th fr esh w a t er The boiling sha ll then be

, .

”
c ont inued for one hour and t hi s p r oce s s re p e a t ed t hr ee t imes ,
.

Thi s makes a to t al of t w elve hours b o iling wi t h fi v e changes of wate r ’

viz 6 2 1 1 1 l l Vith only the fir s t of these is a n addi tion of soda a llowed

.
, , , , , .
-
.
 TH E STABILI ZATI ON OF NIT RO C E LL U L OS E-

After boili ng the nitro cellul ose shall h a ve ten cold water washes each
-
,

washing to consist of agitation by mecha ni cal means for half an hour in a

sufficient amount of fresh water thorough settli ng and decanting the clear ,

w ater at least 40 per cent of the total contents of the poacher shall be dr awn
.

off A sample shall then be taken for subj ection to the various tests prescribed
.

for nitro cell ulose Should the nitro ce llulose fail to meet the required heat
-
.
-

test it must be boiled again w ith two changes of water the time of actual
, ,

boiling being five hours without the use of alkali and then it must be given ,

ten cold water washes in the manner prescribed for the regul ar treatment .

On e of the di sadvantages of boili ng the p u lp in ir on hollanders is that it

may be necessary to a dd alkali to neutrali ze the acid formed It is better .

to add it in the form of finely di vided calcium carbonate (whitening ) than

so di um carbonate Another di sadvantage is that the water cannot be rem oved
.

nearly as c ompletely as when the unpul ped nitro cotton i s boil ed in wooden -

vats from which the water can b e all owe d to drain very thoroug hl y If the
,
.

pul p be all owe d to settle in the ho llander too long it form s a dense mass at ,

the bottom w hi ch prevents the rotation of the stirring arms and it may be
, ,

necessary to dig it out .

An other class of unstable p r oducts that may be present in nitro cellulose 0 11 10 6

3
5 2
5
es
is that of the nitrous esters These are apparently formed m the hydr olysi s
.

of ni tro cellul ose on treatment with dilute alkali or acid the cellulose residue
-

becomes oxidized whil st the acid residue i s reduced The nitrites of cell ul ose .

are so unstable however that they are never present in a normal product
, ,

to any considera b le extent N c o a do t and Chertier succeeded in preparin g

i l r
1
.

them by the action of nitrou s acid on vi scose cellulose suspended in di lute

nitric acid A certain amount of ni trate i s forme d at the same time but thi s
.
,

can be separated from the nit ri te by dissolving it in acetone It can also .

be made by passing nitrous gases through a mixture of acetic acid and acetic
anhydr ide in which vi scose cell ul ose or ramie fibre is sus pended The products . .

thus prepared are of a grey c o lour gelatinous when moist brittle when dr y , , ,

insoluble in water alcohol ether acetone chloroform and ethyl acetate

, , , ,
-
.

The percentage of nitrogen as determined by Sc hlo e s ing s method could not

,
’

be obtained hi gher than 26 per cent that is to say the hi gher n itrites de co m .
, ,

posed before they coul d be analysed In the Lunge ni trometer they gave .

no evolution E ven those with 2 5 per cent gradually evolve nitrous fumes
.
-
.

at the or dinary temperature and water and strong acids sp lit the nitrous
,

acid o ff rapidl y but acetic acid has little effect It is p ossibly the presence
, .

of these nitrites which causes unstab ili ze d gun c otton to give low results -

when tested in th e nitrometer It is found that on b oili ng the nitrogen as . ,

d etermine d by the nitr o meter goes up whi lst that as determined by the ,

Sch lo e s ing (Schultze Tiemann ) metho d goes down

—
Although ni trites o f .

1
C o mp t Ra nd . 1 9 10, 1 51 , p . 71 9 .
 1 92 E X P L OSI VE S

cell ul ose ar e pr o bably fo rmed to s o me exte nt in t he ni tra t ion process their ,

presence is to be asc ri be d m ore to t he decomposi t ion of t he ni t ric esters .

Their pre s ence must be a cause of ins t abili t y .

Pr oduc ts of de
The in t e rm edi a te produ c ts f o rm ed in t he de c o mposi t ion of ni t r o ce ll ulose -

co mp os iti on
.

have engage d t he a t te n t i o n of va r ious investigato rs w h o ha v e hope d t o ob ta in ,

e v i den c e a s t o t he cons t i t u t ion of t he cellul ose molecul e Thu s Ke r kh o fi .

d e t e c t ed t ar t ari c and ci t ri c a c ids among t he pr o d u c t s o f s a p o nifi ca t io n and ,

Ha d o w foun d o x ali c a c id a n d ammoni a a n d an a c i d s im ilar to sa c c haric

2
.

Divers foun d in t he de c omposi t ion produc ts a c ids w hich from the ir reac tions
3

b e iden t ified as pec t ic and para a n d meta pe c tic a c ids Abe l confirmed
‘
,
-
.

t he presence of these in g un cot tons that w ere badl y de c omposed ; he also -

f o un d formic and oxali c aci d s a n d cyanogen a n d w hen the ma t erial w a s ,

heated wi th pota sh amm o nia was gi v en o ff Fermenta ble carbohy dr ates ,

.

w ere onl y forme d in a fe w inst a nces Silb e r r a d a n d Farmer extra c ted wi t h

5
.

w ater 1 0 0 kg of gelatinize d nitro cellul ose po w d er w hi ch h a d been hea t e d

.
-
,

for t w enty t hree w eeks at -

In the extra c t t hey de t e c te d eth y l nitrite ,

ethyl nitrate ethyl alcohol (these evidently deri v e d from t he al c ohol used
,
-

for the gelat inization ) ni tric a n d nitrous acids ammo ni a formic a c e tic , , , , ,

butyric di hydroxy butyric oxali c tarta ric i so sa ccha r ic and hydroxy pyru vi c
,
-
, , ,
-

acids Carbohy drate s w ere found to be present by the fermenta tion te st

.
,

a n d some other compoun d s were obtained but c oul d not be identifi e d by ,

reason of t he complexi ty of the mixture and thei r m inute quantity Hydroxy .

pyruvi c aci d C H O ha s also been found by Wi ll and Vignon am ong t he

, 3 4
6
4,
7

products of the alkali ne s a p o nifi c a tio n of nitro cellul ose and ni t ro oxy c e llulo se - - -

respecti v ely Berl a nd Smith obta i ned it (ca lled by them oxy pyruvic a cid )
.
8 -

by the alkaline hydrolysis not onl y of ni tro cellulose but also of the ni trate s -

of glucose and le v ul ose sho w in g the intimate relationshi p of cell ulose wi t h ,

these other c arbohydrates From starch nitrate a sim ilar bu t not identica l .

acid w a s obta ined They also found that hydr oxy pyruvi c acid is very .
-

susceptible to oxi dation and fermentation and consequently may b e the ,

”
substance which others have described a s fermentable carbohydrate s “
.

Berl and Fodor found that the relative proportions of the di ff erent acids
9

formed vary accordi ng to the c oncentration of the alkali u s ed a dilu t e solu tion ,

yiel di ng compo u nds conta ini ng 4 to 5 carbon atoms whi lst wi t h c oncentra ted ,

alkali acids w ith 1 to 3 carbon ato ms predomin ate d In addition to hy droxy .

pyruvic acid they dete cte d malic trihydroxy gluta ric maloni c ta r t roni c ,
-
, , ,

oxa lic glyc o lli c and dihy droxy butyric acids

,
-
.

p m kt C C he m
1 2
J . . .
, 1 8 4 7, p . 28 4 . J . . S oc . 1 8 54 , p . 20 1 .

3
J C he m S oc
. . . . 1 8 63 p . . 91 . P h il . Tr a ns , 1 8 67. p 18 1 . .

6
5
J C he m S o c
. .
, 1 90 6 p , . 1 182 . B er 189 1 ,
p p 400 . 3 8 3 1
. .

C he m I nd
8
7
C o mp t c d . .
, 1 90 7, p . 8 72 . J . S oc . . .
, 1 90 8 ,
p . 53 4 .

9 S S . .
, 1 9 10 , p p . 29 6, 3 1 3 .
 TH E STABILI ZATI ON OF NIT RO C E LL UL OS E-

Berl and Fodor have also examined the nitrogenou s residues left on
1

treatment with alkali A solution of collodion cotton was shaken for sever a l
.

weeks with a dilute solution of sodium carbonate At the surface between .

the two li quids a fl o cc u le n t substance separated out which was found to ,

contain 8 4 per cent nitrate nitrogen as determined by the nitrometer and

.
,

9 0 per cent total N by the Dumas method

-
. The same substance was .

separated from the ether al c ohol solution after the unchanged n itro cellulose
- -

had been removed by pre c ipitation with water When the aqueous liquid .

thus obtained was acidi fied a precipitate was obtained (also a s light smell of
prussic acid ) and this was purified by dissolving i n 9 6 per cent alcohol and
, .

r e r e ci ita tin
p p g with water The action of caustic p otash on collodion c otton
.

in solution also yielded the same substan c e It was soluble in alcohol but .

insoluble in ether ; on analysis it gave results agreeing with the formula

O H 0 (N0 )
Z4 3 3 a nd may
21 therefore be considered as a penta nitro oxy
2 5,
- -

cellulose It differed from normal penta nitro cellulose in having two hydro
.
- -

gen atom s replaced by one oxygen Its solutions showed little viscosity .
,

and mole c ular wei ght determinations gave results agreeing fairly well w ith
the formula The authors gave the substance the name c ello n ic acid nitrate
. .

Besides this another substance w a s obtained which was soluble in ether , .

This was c onsidered to be c e llo n ic acid nitrite The ce llo nic acid n itrate .

was not very stable ; it exploded at

W ill and Lenze considered that the instability of some samples of nitro
2

cellulose may be due to the formation of sugars from the cell ulose and the ,

c onversion of these into nitrates They accordi ngly prepared and examined .

various nitrates of the carbohydrates (see next chapter ) which they found to ,

be all more or less unstable Sugar nitrate cannot be formed in the nitration .

of cellulose however unless the sugar be present beforehand as the nitration

, , ,

is a much more rapid reaction than the formation of sugar from cellulose and ,

although sugars are apparently formed sometimes in the decomposition of

nitro cellulose they are among the products of the ultimate breaki ng down
—
,

of the material and they are no longer nitrated The presence of these foreign
, .

carbo hydrates should be excluded from the cellulose used for n itration ;
-

starch i s the one that is m ost likely to occur .

Coll odion cotton for the manu facture of blasting gelatine is not boiled W a shing ,
c ll o dio n o
because the power of forming a stiff colloid would thereby be much reduced cotton .
.

It i s washed repeatedly wi th hot water sli ghtly below the boiling point -
.

1 2
S S . .
, 1 9 10 , p p . 254, 269 . B er ., 1 8 9 8, p . 68 .

V OL . I .
 C H AP TE R X I V

NI TRI C ESTERS OF OTHER CARBOH YDRATES

N it ro tar c h -
s : N it ro ugars
-
s

ta rch
Nik o-s . NI TRo -
STARC H has been
own even longer than ni tro cotto n for it was fi rst
k n -
,

prepared by B r a c o nn o t in 1 8 33 by di ssol v in g sta rc h in strong nitric ac id

1

and p our ing the vi scou s tran s lucent liqui d into wate r The resul ting ch e esy .

”
w hite sub sta nce was called by him x y loidi ne a name whi ch i s now app li ed ,

generall y to any product that i s made by di ssolving a carbo hydrate in nitric -

acid and p our ing into w ater or sulphur ic a cid or by di ssolvin g in sul phuric ,

acid and pouri ng into nitric Nitro starch was afte rwards in v e stiga t ed by
.
-

Pélo u s e 2
Liebig B ui j s Ba llot Gerhard B echamp and Reicha r dt In spite
, ,
-s
, , , .

of the cheapness of the raw mate ri al sta rch it has never b ee n able to di sp la ce , ,

ni tro cotton
-
thi s i s partly due to the in stabili ty of ni tro starc h and partl y -
.

to the me c hani c al di ffi c u lties in ni tratin g and p u rifyi n g i t If t he s t a rch be .

introdu c ed into the mi xed aci d s in the same way that cotto n is i t form s clots , ,

which are n o t th oroughl y acte d upon and are d i ffi c ul t to puri f y sub s equently , .

Hence in a ll the early atte mpt s to manuf actur e the sub stance the s t a r ch wa s
di ssolve d in nitric a c i d a n d poured into s ul phuric acid Such for in s ta nce . . ,

was the metho d of the Au strian engi ne er offi cer [ c h a tiu s The process of
l
4

t he Vienn e s e Nobel C o mpany con s i ste d in di ssolvi ng groun d sta rc h in ni t r ic

5

aci d (specifi c gravity 1 a n d then in j ecting it as a sp r ay into the w a ste

acids from nit r o glycerin e (H NO 1 0 per cent H S O 70 per cent H O 20

-
3 .
, g , .
, ,

per the temperature being kept d own to 20 to The ni t r o sta r ch °

-

was then filte re d o ff on a fil te r of g un c otto n washed wi th wate r and trea ted -

,

for t w enty four h ours with 5 per cent sod a It was then g r ound to a pa ste
-
. .

and washed in a centrifugal or fil te r press and imp r egna ted wi t h anili ne wi th -

the obj ect o f making it sta ble U nt il it was r e quired for fur ther u se i t w a s
.

kept wet conta inin g about 33 per cent wate r and l per cent aniline
, . . .

1
A nn . ch i m
p lay s , 52, p 290
. . .

p 3 8 ; C o mp t
2
Ann p ha n n , 1 8 3 9 ,
. . . . Re nd 23 . p . 893 .

ch i m p hy s , 1 8 62,
3
An n . .
p 311
. . .

4 ’
D ing le r s P o ly . J
o u r n , 1 8 61 ,
p 1 4 6.. .
5
Ge rm . Pa t .

19 4
 NITRIC E ST E RS OF OTH E R CA RB OHYD RATE S 1 95

H ough s process di ff ers from previous ones in that he injects powdered

’
1

starch by means of a j et of air into mixed acid containin g an excess of sulphur ic

anhydride which excess i s maintained during nitration by the addi tion of
,

more oleum The nitrated product is filtered o ff and treated with hot
.

ammoni a He claimed thu s to obtain a stable product containing about

.

1 6 5 per cent N These claim s have been investigated by Berl and B ii tle r
. .
2
,

only they di d not treat the product w ith alkali as t hi s could only have an ,

inj urious eff ect on the stabil ity : they treated it with water only They .

foun d that the products w ere very unstable the heat tests low as als o the , ,

ignition p oints and they contained 0 50 per cent combined sulphuric acid
,
. .

The percentage of nitrogen also was very much lower than as stated by Hough
in no case was it more than ab out 1 3 4 per cent which was the same as nitro .
,

c otton contained when it was nitrated in the same manner .

The Nobel and other methods were simi larly investigated by Muhl h auser 3
.

The principal res ul ts are coll ected together in the followi ng Table :

t
So lu b i li y i n

Me th o d of P r e p a r a io n t Pe r ce n t .

Re ma r ks

Alc o h o l

P p td . wi th N/ G w a te a cid
s M , No b el p ro c ess

w at er
p ts . 11 28 0 4 i n s o l.

I n j e c t io n . W hea t s tar ch d if . sol.

Po ta t o
Ric e
So l b le u

M me ans i nv s t iga te ed by Miih lh a us e n ; B b y Be l r a nd B ut l e r .

None of these were stable except the first two w hi ch contained only 1 1 ,

and 1 0 5 per cent N respectively but on the other hand W ill and Lenze
-
.
4
, , , ,

by treatment wi th solvents obtained a stable product with 1 4 0 4 per cent ,

-
.

N To prepare this they di ssolved the dried starch in concentrated nitric

.

acid (spec ific gravity whi ch was kept cool and after twenty four hours ,
-

sulphuric acid was gradually added The product was washed w ith water .
,

then extracted first with cold alcohol and afterwards twice with hot alcohol .

1
US . P at s . of Fe b ruary 2, 1 90 4 ,
a nd of Ma y 23, 1 90 5 .

2
S S
. ., 1 9 10, p . 82 .
3
D in gle r
’
s P o ly t . Jo u r ., 1 8 92 p . 37 . B er .
, 1 8 9 8 , p 68
. .
196 E X P L OSIV E S

It was di ssol v e d i n a mi x t ure of a c etone and alc o hol and the acet o ne evaporated
off thereby pre c ipitating t he ni t ra t e a s a w hite p o w der Thi s wa s then
, .

boiled with al c ohol w ashe d wi t h w ater a nd dried The product pu rified in

, .

thi s w a y igni t ed only a t a n d af t e r keeping at 50 fo r six months w a s

°

still quite stable Such a pro c ess i s of course quite un s ui t able for use o n
.
, ,

a commercial s c ale but i t s eem s to in dicate that nitro starch its elf is fairly
,
-

sta ble i f i t can be s eparate d fr o m impuritie s .

Nitro s tar c h d issolve s rea dily i n acetone and eth y l a c etate The s olu
- -
.

b ilitie s i n al c oh o l and ether alcohol are given in the ab o ve Table

-
That made .

by the N o bel process d i s solve s very rea dily in nitro glyceri ne but doe s no t -
,

gelatinize i t a s co llo dion cott o n d oe s Thi s is in a c c ordance w ith the lo w .

vi s c o s ity o f the solutions in acet o ne Berl and B iitle r o bta ined the foll o w ing
.

v is c o s i t ie s for soluti o ns o f p o tato star c h nitrate d by H ough s method and ’

fo r nitro c o llu lo s e nitrated in t he same way both c ontaining 1 3 4 per c ent N

-
, . .

Po ta to s tarc h n itrat - e

Ce l lu l
ose nit ra t e

Ot her varie t ie s of starch gave even lo w er vis c osities The molecul a r c o m .

ple x i t y is in fact small ; Sa p o s h n o

i k ff 1
determined the molec ular weight in
a Be c kmann apparatus w ith b oiling acetone fo r two different produ c t s ea c h
c o ntaining 1 3 4 per c ent N and obtaine d results agreeing w i t h a C formula
.
, 3 , .

On e o f the disa d vantages o f nitro starch as c ompare d with nitro cotton — -

lies in the fact that i t absorbs a mu c h larger amount of m oisture from the
air j ust as starch i s more hygroscopic than its homologue cellulose Thus
, , .

W ill fo u n d that the materi als after being dried in an oven at 40 t o ok up

z °

the following amoun ts in an atm osphere nearly saturated with moist u re at

°
25

a ndthe correspon ding figures for the nitrate d products w ere fo und by Will
and Berl and B ii tle r to be
1
J . Russ . P h ys . C h em . Soc 1 9 0 3, p
.
, . 126 ; J . C h em S o c
. . Ab s , 1 90 3, p . 402.
2
M i tt . a . d . C en tr a ls tc lle , No . 4 .
 NIT RIC E ST ERS OF OTH E R CA RB OHYD RAT E S

Per ce n t . N H y g r o s c o p ic i y t

Nitro starch has never come into general use in E urope pri ncipally because
-
,

of its unsatisfactory stability in spite of the efforts of U c h a tiu s and the Austrian
,

Nobel Company to make smokeless p owders w ith it It is not authorized .

for manufa c ture or importation into E ngland In America however it is .

, ,

used as a component of high explosives .

By the action of nitric acid on variou s sugars products can be obtained Nitr o -s ug a r
containing 1 6 to 1 7 per cent N They can be exploded by friction and go . .

o ff with great violence Attempts have therefore been made to use them
.

for percussion caps but they have hi therto proved too sensitive too hy g r o
-
, ,

scopic and too liable to sp ontaneous decomposition A number of these

,
.

substances were prepared a n d examine d by Will and Lenze 1

The general .

method of preparation was to dissolve the sugar in nitric acid add sulphu ri c ,

aci d separate wash with ice water and purify by recrystalli zation from
, , ,

alcohol The following Table g iv e s th e principal results :

.

°
L o ss a t 50

Mo n o s a o o n a n rn ns
Pe nt o s es , 0 511 10 0 5
Rh a rnn o s e t t ranitrat e
e 1 6-0 8 1 -2% in 30 d y s a
Ar a b in o s e 1 6 75 1 -5 % in 1 d a y
40 % in 40 d y s a
X y lo s e
H ex o ses , 0 611 1 20 6 Al d o s e s
G luc e os
p e n t anit rat e 1 6-9 6 38 % in 1 d a y
G ala ct o se 4 2% in 1 0 d y s a
1 70 8 42 % in 1 d a y
Ma nno s e 46% in 1 d a y
Keto s es

Le vu l o se r n t rat
t i i e 14 1 2 0 in 1 8 0 d y s a
1 38 3 1 3%
—
in 8 d y s a
So rb in o se 1 4 -0 4

1
B er .
, 18 98 , pp . 68 — 90 .
19 8 E XP L OSIV E S

The pro d uct from levul ose app ears to be t he m os t s t a ble t hose from mal t o s e
and lac t o se also di d not decomp ose very rea dil y .
N IT RI C ESTE RS O F G L Y CE RI N E
 C H AP TE R X V

GLY CERI NE

Sour ce o f g ly cerine a
So p b o ili g P n ur ifi cat io n o f p en t ly e C o n ce nt ra t io n
s

Au t o c la ve p r ce s o s n
C o mb i e d p o c e ss r Tw it ch e ll p r o ce s s Fermen t p r o ce ss
D is t illa t io n

G L Y C E RI N E C H O i s a b y product i n the manufacture of soap and stear ine

, s s a,
-

candles from oils and fats w h ich consist almost entirely of the glycerides of
,

the fatty acids comp oun ds formed by c ombini ng three molecules of a fatty
,

acid stearic acid for instance C H CO H wi th one of glyce ri ne a n d e limin a t

, , I7 35 g ,

ing three m olecul es of water When the o ils or fats are heate d with solutions
.

of caustic alkalis or aci d s or even with water alone the glyceride i s sp lit up
,

3E 20 C 3H 5(C I 7H 0 0 2) 3 3C 1 7H 0 0 2H
W a te r
35
Tr is te a r ine G ly ce r ine
35
Ste a r ic d
a ci

If caustic soda has been used it combin es wi th the acid to form a soap such
,

as sodi um stearate , Stearin e can dl es on the other hand are , ,

made from the free fatty acid and p rin cipally from stearic and palmitic aci d s .

The soap i ndustry is of course a very old one but i t i s only in modern
, , ,

t imes that the recognition of the advantage s of c leanliness has cause d it to

assume really large dimensions Formerly the glyce ri ne was either left in .

the finished s oap or was a llowed to run to waste It i s only since the develop
, .

ment of the in dustry of ni tro glycerine e x plosives that there has been a large
-

demand for the product The demand for glycerine fo r the manufacture of
.

exp losives is now so great that it often ab sorb s a ll the available supplies .

The E u ropean production is estimated at or tons per annum .

It now pays the s o ap maker to recover a much larger proportion of the glyce ri ne
—

than formerly .

The s implest method of making soap is to boil the o il with caustic soda So a p -b o ili
solution in open tanks kettles whi c h usually hold 4 0 to 50 tons The .

s a p o n ifi c a tio n i s starte d with a weak lye of specific gravity 1 0 5 per cent .

Na OH ) and when the action is well started stronger lyes are added
, When .

the action i s alm ost complete salt i s ad ded to render the soap insoluble in
,

the wate r Two layers are thus obtained an upper o n e of s oap a n d a lower
.
,

one of brine containing the glycerine di ssolve d in it The soap is separated .

,

20 1
 20 2 E XP L OSI VE S

the sa p o nifi ca tio n is c ompleted by the addi tion of a little m ore soda a n d i t ,

is submi t t ed to such f u rt her proce sses as a re n e ce ssary to produ c e the class

of soap requ ired .

The r e are a num ber of o t her p rocesses of sp li t ting up the fats with separa
t ion of t he fa t ty a cids a s such a n d t hese ac i d s ca n sub se quently be comb ined
,

wi t h soda to form soap s . These methods have bee n us ed largely in Germany

fo r s oa p maki n g b u t the m anufa c t ur e of soap is t hus rendered much mo r e
-
,

diffi cul t t he soa p is oft en da rk in c olour and is apt to grain on keepi n g

, ,

a n d in many c ases bec om e s rancid Th es e di s advantages m ore than c o mp e n

.

sa t e for t he fa c t that t he recove r y of t he glycerin e is ea sier In E ng land .

mp o nifi ca ti o n wi th soda i s p r ac t i cally uni versal a n d i t i s t he p r ocess most ,

us ed in Am eri c a The te ndency in Germany i s also to r eturn to thi s meth od

.

for t he manuf a c ture of soap .

P ur ifi ca ti on of The spent lye co nta ins besi de s glyce r ine and much water a large amoun t
, ,
s pent ly e
,
of s odi um chlo ri de and va ri ous imp urities organic and in organic It is
, , .

firs t nece ssa ry to remove some of the impuri ties The free alkali i s fi rst .

neu t ra li ze d wi th sulph u ri c or hydrochl o ri c ac id and if impure soda has been ,

us ed ferri c or a l um i ni um chl o ri de is ad ded as long as a precipita te is formed

,

to fr ee t he li qui d from hyp o sul phi t e s

-
sulphi des cyani des sulpho cyani des
, , ,
-
,

. e tc The p r ecipita t e which is allowed to settle conta ins P russian blue and
, ,

fa t t y mat t ers whi ch are re c overe d Other meth ods of p urifi ca tion are also
,
.

a dopte d a c co rdi ng to th e comp osition of the lye .

C oncentr a ti on The next ste p is to c oncen t r ate the lye Duri n g t hi s operation considerable
.

quan t i t ies of salt separate and c au s e t rouble by coatin g the solid surfac es
a n d p r eventing t he t ransmi ssion of heat Various t ypes of pla nt have been
.

de fi s e d for ca rryi n g out thi s Operation such as that of L Droux of P a r is

, .
, ,

consi sting of a s t e a m hea ted dru m revol vin g in a shall ow t ank filled with th e
-

li qui d ; th e removal of the salt is easy with a pla nt of this kind At the .

p r esen t ti me the co nce ntration is usually carri ed out in sin gle or multiple
effe c t v a cuum evap o r ato rs in which the li quid is kept cir c ulatin g r api dl y
, ,

so tha t solid deposits may not be form ed on the hea ting surfaces .

If t he fa t t y ac i ds a re to b e u s e d for the manufacture of can dl es other ,

proce sse s of t r ea t in g th e oil or fa t ca n b e us ed as the acids have to be di still e d

,

i n va c uo in a n y c a s e in order to r em ove the da rk coloured impuri ties

,
It -
.

is a ls o nec es s ar y to r emove f r om t hem oleic a cid whi ch has a melting po int of ,

-

onl y and would con se quen t ly make the mate ri al too soft ; t he meltin g
poin t s of s t earic and pa lmi t ic ac i ds are 4 8 a n d 62 resp ectively Thi s is ° °
.

e ffec ted partly by filtr ati on a n d part ly by di stilla t ion .

The me t h o d whi ch was fi rs t used for t he manuf actur e of s tea rin e was to
saponif y wi t h an excess of milk of lim e sepa r ate t he gly c erin e from the lime
,

soap and d e compo se th e la tter wi th s ul phuri c a cid The consumption of li me

, .

and sulphuric ac id was co nside r able however and t he proce ss was trouble
, ,
 G L Y C ERI NE 20 3

some Then it was found that a much smalle r proportion of lime would suffi ce
.
,

if the operation were carried out at a high temperature and pressure The A tocla e .
u v
treatment is eff ected at a pressure of about 120 lb per square inch in an auto p ce . ro s s.

clave pro v ided with a mechanism for stirrin g A little zinc oxide is also
, .

added sometimes to hasten the reaction Accor ng to e w o w its ch the

di L k l
.

yield o f s a p o nifi ca tio n crude glycerine of specific gravity 1 2 40 by this

process is ab out 1 0 per cent .

It is p ossible to do away wi th the lime entirely and resolve the fat into ,

acids and glycerine by merely heatin g with water in an autoclave but the ,

temperature required is high and the time long and consequently there i s ,

much decomposition w ith the resul t that the yields are bad and the products
,

impure But instead of alkaline substances such as caustic soda and lime
.
,

many other material s may be used to accelerate the s a p o nifi ca tio n On e of .

these is sulp huric acid which i s much used for the production of candle stearine
, .

The fat i s heated to about 1 20 and mixed intimately with 4 to 6 per cent °
.

of G O V The yield of glycerine by this process i s only 8 or 9 per cent the

. . . .

acids are very dark in colour but a large yield i s obtained of material suitable
,

for candle maki ng 61 to 63 per cent as against 45 to 47 per cent by the auto
, . .

clave process This is due to the action of the sulphuric acid upon the oleic
.

acid which is converted into iso oleic and hydr oxy stearic acids stearo lactone
,
- -
,
-

and other bo di es havin g comparatively high melting p oints Unfortunately -

.

some o f these are broken down again in the subsequent distill ation .

The advantages of both processes can b e comb ined by first heating in an C o mb ined
p o ce r ss.
autoclave with a small proportion of lime and subsequently treating the fatty ,

acids with concentrated sulphuric acid According to L e w ko w its ch the 2

yields from 1 00 parts tallow a r e then

C an d le mat erial
Ole ic a c id
C ru d g ly c erin e
e (s g. .

Pi t ch a n d lo s s

In the Twitchell process the fat is treated with a reagent ma de by the

3

action of s ul phuric acid on o leic acid di ssolved in an aromatic hydr o carbon -

,

such as naphthalene Thi s reagent greatly accelerates the hy drolysis of the

.

fat but it i s not known how it acts The fat mixed w ith to 1 per cent of
, . .

the reagent and some water is boiled for twelve to twenty four hours with -

live steam in a tank closed to prevent access of a ir which would make the ,

acids dark The fatty layer now contains 8 5 to 9 0 per cent of free fatty
. .

acids The contents of the tank are allowed to settle and the aqueous layer
.
,

containing the glycerin e is dr awn o ff A sma ll quantity of water i s then a dde d . ,

1 2
Oils , F a ts a nd W a x es , 4th c d ., v o l. iii .
, p . 1 78 . L o c. c it , p . 18 8 .

3
Ame r . Fa t , 60 1 , 60 3 , Mar ch 29 , 1 8 9 8 .
 20 4 E X P L OSIVE S

and t he boili ng is con t inue d for ano t her t w elve to t w enty four ho u rs The
'

-
.

conversion is t hen 9 7 to 9 8 per cen t Ba ri u m carbonate i s then a d ded unt il .

the w ater i s neu t ra l t o me t hyl o ran ge a s t he p r esence o f s trong aci d s ca uses

,

the ma t e ri al t o di s colour Thi s pro c es s is mu c h u s ed in Am erica for t he

.

manufacture of candl e mate ri al .

Another ca ta l y tic agen t t hat i s use d t o accelerate the sa p o nifi c a tio n of

fat s is the enzyme con t a in e d in cas to r oil s eeds The reagent is prepa r ed -
.

by d ecorticating t he s eed s grin din g t hem up w i t h wa t er a n d al lowing them

, ,

to ferment A creamy emul s ion ri se s t o t he s urfa c e c on ta in ing some 4 per

.

cen t of album enoi d substances whi ch con s t i t u t e t he a c t ive agen t The o il

.
, .

to be sa p o nifi e d is mi xe d wi th abou t 40 per cen t of water a n d stirred to an .

em u l ion by means of air 5 to 8 per cen t of fermen t are a dd e d and 0 2

s
, .
,
-

per cent of manganese s ul pha t e which grea t ly a s sists t he ac t ion The whole
.
, .

ma s s is kept a t a suita ble t empera t ure whi ch shoul d n o t be abo v e , but

mus t of course be hi gher than the mel t ing poin t of t he fat In t he ca s e of
, ,
-
.

fat of high mel t ing point i t is necessary t o mix it w ith o il The fermen t a t i o n
-
.

is allo w ed to proceed fo r one or tw o days a n d if t he emul s ion sho w s s igns of ,

se t t lin g out i t is s t ir red up again w i t h a ir I t is n o t prac t icable t o a t t a in

,
.

much more than 8 0 per cen t conve r sion by t hi s proce ss When it is finished a
. .

lit t le sul phuric acid i s added to cau se t he emul sion t o separa t e a n d t he t em

r e i s raised t o about 8 0 d es t roy t he enzymes S ome c ulty i s
°

p e ra t u to diffi .

caused by t he slo w ness wi t h which t he emul s ion s eparates out t he inc o m

le te n e s s of th e conversion i s al s o an obj ec t ion The ad v antages of t hi s
p .

and t he T wi t che ll pro c ess are t ha t t he plan t requi re d i s very s imple a n d in

e xpensive a n d t h e colour o f t he a c id s i s good The lo s ses by either ma y
,
.

be heavy however if t hey are mishandled

, , .

t t
Dis ill a i on: Glycerine t ha t i s t o be u s ed fo r t h e manufacture of ni t ro glycerin e has t o -

be pu r ifie d b y dis t illa t ion A t o n e t ime t he di s t ill a t ion w a s c ar ri e d o n? a t

.

a t mospheric pre s s ure w i t h superhea t e d s t eam i n a s t ill heate d by a fire U n der .

t hese c o ndi t ion s mu c h of t he gl y c erine w a s de c o mp o s e d and p o ly gly c e ri ne s

were forme d Dis t illa t ion w i t h sa t ura t ed s t e am i n va c uo did not gi v e goo d
.

re s ul t s be cause t he t empera t ure of t he s t eam w as re du c ed too much by t he

,

expan s ion The dis tilla t ion i s now generally carried out wi t h superhea t ed
.

s te am i n va cuo There i s no grea t di ffi c ul t y in s eparating t he glycerine from

.

t he w ate r in t he di s t i lla t e a s t he boiling poin t s are v ery far apart

,
-
a nd

1 0 0 respec t ively a t a t mo s phe ri c pre s sure ) bu t t he di s t ill a t i o n mu s t b e c ar ri ed

°
,

ou t wi t h proper care to ob t ain t he gly c e ri n e in a satisfac t ory s t a t e of pur i t y .

The gly c erin e is genera lly condense d in a se r ies o f meta l pipes co o le d b v ex

p o s u r e t o t he air In t he fi rs t t ube s pra c t icall y anh y d rous glycerine c o n
.

denses in t he la t er ones t he c on d ensa te is s o mewha t di lu t e The former o nly .

is used for th e manufa c t ure of nitro glycerin e t he la t t er for a vari e t y o f pur

-
,

poses su c h as fi lling ga s me t er s t he manufa c t ur e o f in k and s i ze s for t ex t il es

,
-
,
.
 GLYC E RIN E 20 5

Fig 3 8 shows a distillation plant of the typ e m ade by George Scott and Sons
. ,

London and very largely used in E ngland Over the v erti c al still sho w n in
,
.

the background is a catch pot in w hich high boiling impurities such as poly
-
, ,

glycerines are condensed and material su c h as salt that i s carried along

, ,

FI G . 38 . t a t io n
D is ill Pl an t fo r G ly ce rin e

mechanicall y by the vapours i s held back Af ter passin g through the

,
.

cooled battery shown in the foreground in w hich the gly c erine is c on densed
, , ,

the vapour passes to a condenser coole d wi th water where the w ater is ,

con densed and then to a vacuum pump The cost of distill ation is stated to
, .

b e about £ 1 per ton.

 C H AP TE R X V I

MANUF ACTURE OF NI TRO- G LYCERINE

Ea r ly n j e t r M d e rn p la n t N it ra t o r Se pa ra to r : P e w a h
m e t ho d s : I c o : o : : r -
s

t nk
a : Fil t r in g Wa s h w a t e r e Afte r s p ra t io n R ce n t im
-
s -
e a e

pro v e m nt Ab li t io n o f c o c k
e s o Fum e ho d P lu g s fo a ir ho l s : So fte n
s : o s r -
e

in g t h w hing w t rs
e a s a
p e ra tio n s
e L a b y rint h s N it ra to r se par a
O -

to r C lin g c iloo P r e v nt io n o f a ft e r s p ara t io n

o s e D r o w n in g rran ge m nt s
- -
e a e

Ac id a n d yi ld
s T im e o f s e p ara t i n
e s C o n ve y an o f ni t r gly ce r ine
o G utt e rs ce o -

Lo a t i n f f t v
c o o Air s up p ly
ac o r Li mi t b o ard
: -
Th u nd r s t o rms
: G e ner al s : e -
:

p r e ca u t io n Se ns it iv e ne s s s.

I N the early days nitro glycerine w a s made on qui te a small scale by han d
—
.

The mixed acids w ere placed in a p ot of iron lea d or earthenware surrounded , , ,

by a trough c ontai ning cold water The glycerine w a s then pour ed in slowly .

w h il e the li qui d was st irred b v means of a rod of iron or gla ss The yield .

obta ine d was sometimes as much as 2 lb of nitro glycerine from 1 lb of .

-
.

glycerine but w a s frequently considerably less Af ter all th e glycerin e had

,
.

been added the st irrin g was cont inue d for a fe w minutes longer then the li quid
, ,

w a s a ll o w ed to stand and the nitro glycerine wa s skimmed from the surface -

and pour ed into wa ter w ith w hich it was agitate d F inally it was separate d
, .

from the wate r by means of a separating funnel IVith the develop ment of .

the dynamite industry t he demand for ni tro glyceri ne gre w enorm ously -
,

and mechani cal appli a nces w ere gradua lly intr oduced to enable larger quantities
t o be dealt wi th a t a time thu s saving labour a n d improving the y ield De
, .

s c ri tio n s o f the s e are to be found i n the older text books such as th ose of
p
-
,

Guttmann a nd Chal o n .

A few year s after the di scover y of dynamite by Nobel in 1 8 66 m ost of the

essential fea tures of the m ode r n plant had been introduced The nitrat ing .

vessel w a s a large c y lin drical leaden tank with an oute r woo den casing form ,

ing a j acket through w hich cold w ater w a s c irculated 1

In the ta nk there .

were also c o ils through w hich c old water ran Agitation was eff ec ted by .

means o f compre s s ed a ir led in through lead pipes and in the earli er pla nts ,

me c hani c al agita t ion w a s also employe d The glycerin e w a s r un in from a .

tank placed above t he ni tra t or t hrough a c ock b y m eans o f which the infl ow
1
S ec N t han n d Rin t ul J S oc C he m I nd
a 1 90 8 p 1 9 4
a o , . . . , . .

206
 MANU FACT U RE OF NIT RO -
GLYC E RIN E
was controlled The fumes passed away through a glass pipe w hi ch enabled
. ,

the man in charge to observe their colour He also watched the temperature .

by means of a long thermometer the scale of which was above the cover ,
O
,

whilst the bulb was in the acid mixture Below the nitrator a large tank .

was provided containing water into which the charge could be run if the
temperature rose beyond control On completion of the nitration the whole
.

of the charge of waste acids and nitro glycerin e was r un slowly into a large -

tank of water which was kept in agitation by means of wooden paddles operated
,

by hand or mechanicall y The ni tro glycerine was all owed to separate out
.
-

at the bottom of thi s tank and was then drawn off into smaller vats and
,

washed several time s with soda solution and w ater until neutral .

This system involve d the loss of the whole of the waste acids and if the ,

rate of flow into the water was not controll ed very carefully a dangerous ,

amount of heatin g w a s liable to occur In any case much ni trou s fume was .

forme d and there w a s some loss of nitro gly c erine through decomposition —
.

For these reasons the separatin g tank was introduced towards the end o f the
’
seventies The charge was run into thi s through a c o ok at the bottom of
.

the nitrator and the nitro glycerine being lighter than the acids separated
,
-

out at the top and was transferred to the washi ng tank

,
.

In America iron nitrators are st ill used These have double walls within .
,
Mo dern pla nt
whi ch cold water circulates and are provided with mechani cal agitators instead
,

of or i n addi tion to c ompressed air In E urope however such plant has

, ,
.
, ,

long ago been superseded by lea den vessels in which the li quids are agitated by
j ets of air The water before being p assed through the coils is generally
.

cooled by means of refrigerati ng plant to a temperature only a few degrees above

its freezing p oint T hi s enables the nitration to be carried out more rapidl y
-
.

and at a lower temperature The outer water j acket has been done away
.

with The nitrator has frequently been made in the form of a wooden tank
.

lined with lead but the best modern practice i s to construct it of lead only
, ,

sheet being used of su fficient thickn ess to stand without support .

The form that the ni tro glycerine plant had generally assumed by the
-

end of the ni neteenth century may be seen from the diagram of the factory
that wa s erected at W altham Abbey in 1 8 9 0 (Fig The nitrator was of . Nit a to
r r.

the form that has j ust been described The top consiste d of a d ome of lead .
,

which was cemented on and provided with glass inspection windows The .

a ir pipes the pipe for the mixed acids and the inlet and outlet pipes for the
, ,

cold w ater coils all passed through h oles in the cover ; in the centre of the
cover was a man li d w ith an acid lute and in the centre of that again was
-
,

a hole for the inserti o n of the glycerine inj ector Thi s hole was closed by a
'

loose lead plug when the inj ecto r was removed The air used for the agitation .

was allowe d to escape through a fume pipe fitted with a glass cylinder to enable
-

the man in charge to observe whether red fumes were being dev eloped The .
 20 8 E X P L OSIV E S

bo t t om o f t he ta nk w a s pr o vi d ed w ith t w o earthenware cocks both of which ,

w e r e ava ilable if i t shoul d be nece s s a ry t o d rown the c harge o n e of them w a s

used for r unnin g t he c o n t en t s of t he ni t ra t o r in t o t he separa t in g t a nk thr ough

a movable lead be nd .

The mi x e d aci ds ha ving been run into t he nitrat o r the glycerine inj ec to r
w a s in t r o d uc e d t hr o ugh t he hole in t he man li d a n d the glyce ri ne wa s sp rayed -
,

by mea ns of air p re s s ure under t he surface of the acid During ni t ration c old .

w a t e r w a s pas s e d t hrough the c o ils and the c ontents of the nitrator w ere ,

kept in a sta te of vi o lent agi t ation b y means of numerous j et s of comp ressed

a ir . The in flo w of glycerine w a s regulated so a s to keep t he te mperature of
t he charge a t or belo w 22 C all the gl y ceri ne had been added the
°
.
,

A tt er se pa ra ti n g h ous e t i gh Ni ra t n Se pa ra ting h o us e W a s hing ho u s e W ei gh i ng a nd W a sh wa te r

W t
ouse
d k MA Mi d i d t k t t li
G G ly
W A a s e ac i ta n an S s e pa ra mix ing h o us e set n g h o us e
W W
. . . x e ac . o r.
t k t k t k k
.

D D
A S A ft e r se pa ra ti ng i cer ne an ST Sa fe ty an W T a s hi n g an F T Fil te r ta n W W S a sh wa te r
W
. . . . . . . . . . . .

k k
. .

t
.

D T D w i g t
b o t tl es . N Ni . tra o r . D T . . ro w ni n g ta n . D T . . ro w n in g t
an . Sca les
. . se t tling

. . ro k nn an . P W . . Fr o w n ta n k. ta n k .

FI G 3 9 . D i g ra m
. a o f Old N it r o -
g ly ce r in e P la nt a t “al th m a Ab b e y .

inj ec to r w a s remove d t he charge cooled do wn t o about

. and then r un
o ff i n to t he s epara t o r In fac t orie s w here ref ri gera t e d w ater i s not available
.

i t is no t al w ay s pos s ible t o ni t ra t e a t such a lo w tempera t ure : the Germa n

o ffi cial reg ula t ions lay d o wn t ha t t he te mpera t ure shall never exceed
and t he c harge mu st n o t be r u n into t he s eparato r until it ha s been reduced
to
For introduc ing t he glyce ri ne in t o the acid s a n ingeni ous form of inj ector
w a s used by Nobel a nd w a s adop te d in many facto ri e s
, It consi s t s o f two .

meta l tube s one w i t h i n the other t he o u te r one is for the gly c e ri ne and th e ,

i n ner o ne for compre s e d air a n d t here are tw o fle x ible diaphragm s so arranged

s
,

tha t if the a ir pressure fa il or if it ri s e too hi gh the supply of glycerine is cut

, ,
 MANU FACT U RE OF NITRO GLYC E RIN E -
20 9

off The air c arries the glycerine in the form of a fine spray into the mixed
.

acids Formerly thi s appli ance was made of iron but it i s n o w generally bui lt
.
,

of aluminium Its one disadvantage i s that it requires constant a tte n tio n to

.
‘

keep it in good working o rder and for this reason many prefer to use a simpler
,

appliance consisting merely of a rose of lead or aluminium h a ving a large

number of h oles Through this the glycerine i s forced from a closed tank
. .

by means of air pressure and falls as a fine rain on the surface of the acid
, ,

w ith whi c h the globules are caused to mix at once by the violent agitation .

At Waltham Abbey the separator was situated in the same buildi ng as Sep a to ar r.

the nitrator and the preliminary washing tank but in many other factories ,

the nitrator i s in a building by itself and the separator and preli minary washing
,

tank in another The separator at Waltham Abbey was a square lead tank
.
,

the bottom of w hich sloped down from all four sides to a central hole fitted
with a vertical glass cyli nder A hori zontal lead pipe with branches in four
.

directions was connected to the lower end of the c ylinder and each branch ,

was provided with an earthenware cock U nder the separator was a lead .

lined tank for the p urpose of catching the contents of the separator in case
the glass cylinder should break The separator was provided with a skeleton
.

frame cover filled in with glass the sides sloping up to a pipe which carried
,

off the fumes ; air pipes were led into the separator through the cover so ,

that if there should be any sign of spontaneous heating in the nitro glycerine -
,

it co uld be stirred up and mi x ed again with the waste acids whi ch woul d ,

reduce the temperature once more A thermometer passed through the lid .

of the ves sel with its bulb in the nitro glycer ine and its scale ab ove the lid -

so that any rise of temperature could be seen at once On the side of the .

separator there was a glass inspection window also an earthenware cock ,

situated about 4 inches below the surface of the nitro glycerine W hen the -
.

separation was complete the bul k of the nitro glycerine was run o ff through
,
-

t hi s cock into the prelim in ary washi ng tank The waste acid was then run .

away through one of the branches of the bottom pipe to the after separating -

house .As soon a s the rest of the ni tro glycerine was seen coming down -

into the glass cylinder the c ock leadin g to the after separating house was
,
-

closed a n d the one leading to the pre wash tank was opened and the
,
“
-
,

remain der of the nitro glycerin e run into this tank Of the other two cocks
-
.

at th e bottom of the separator one was use d for running t o the w ash water -

settling house any thick sludge that separated at the surface divi di ng the
,

acid from the nitro glycerine and the other was connecte d to the dro w ni n g tank
-
,
.

In some facto ri es an open separator was used instea d of a close d tank ,

and the nitro glycerine as it separated was removed by hand with a metal
-

ski mmer generally of alum inium a n d transferred little by li ttle to the pre
, ,

wash tank .

P o wa h r - s
The old patte r n o f preli minary washing tank usually called the p r e ta nk ,

V
.

OL. I . 14
 E X P L OSI VE S

w ash t a nk w a s fi t t e d wi th t w o ea rt hen w are c o c ks an U ppe r one for runni ng

, ,

o ff the w ashi ng wa t ers and t he lower one to ru n t he ni t ro gly c e ri n e to the

,
-

washin g house The air pipe for agi t a t ing the charge w a s lai d loosel y on
.

the botto m ; another pipe w a s le d i n to t he bo t tom fau ce t d o wn t he in si de

of t he ta nk ; t he ta nk w a s o pen a t the to p The obj e c t of p r e w a shi n g .
-

is to remove t he bul k of th e acid from the ni t ro glycerin e a s qui c kly a s possible -

,

a n d ren d er i t a lmos t neutral before i t is s ent do w n to t he w a s h i ng h o u se .

To do t hi s it is agita te d for a fe w minute s wi th abou t four di fl e re n t lo t s of

'

w ash w a ter a n d t hen wi t h a weak solution of so di um carbona t e

-
.

W a s hing . The washi ng ta n k w a s s imilar to thi s and was p r ovided wi t h c oc k s one

a t t he botto m for rtu n i in g o ff the ni tro gly c erine and one or mo r e ski mmi ng -
,

c ocks at di ff erent levels An alte rnative arrangemen t for r tmning o ff t he

.

w ash w ater was a skimm er

-
a saucer shaped funn el at ta ched to a rubber
,
-

pipe w hich led th rough the side of th e tank to th e wash wate r g ut t er The
,
-
.

early form of ski mmer was of lea d supporte d by mean s of a rope a n d coun ter
w eight Late r patte r ns were made of lighte r mate ri al such as brass co v ered
.
,

wi th rubber cloth .

The fil tration of the w ashed ni tro glycerine i s generally ca rried ou t in —

the washi ng house in a leaden ta nk Formerly i t was fil te red th rough dr y .

,

coarse graine d salt containe d in a fla n nel bag supporte d on wi re gau z e The

-
.

greate r part of the water in suspension in t he ni tro glyc erine was ab sorbed -

by t he salt whilst the nitro glycerin e flowed in to t he ta nk Thi s had an

,
-
.

eart henware c ock by means of whi ch the nitro glv ce rin e was run into a rubber -

bucket sta ndi ng on the pan of a pair of scales so that th e correct quanti ty ,

could be weighe d out for a charge of the exp losive th at w a s to be made At .

the end of t he day s work or ofte ner if necessary th e salt b ag was renewed
’

, , ,

and the salt w a s di ssolved in w arm wate r to recover a n y ni tro gl y cerine it -

mi ght c onta in .

The fil tration is now carried out at Walth am Abbey not in the washin g
‘

bu t in the mixi n g h o u se s The nitro glycerin e runs down a gutte r to t he

.
-

mi xi ng house and from there into a plain lead ta nk wi th a fals e botto m of

,

perforate d lead on w hich li es a lay er of sponges sewn up in fl annel The

,
.

nitro glyce rine filte rs through the sponges which reta in the moist u re and
-
,

fl o c c u le n t m atte r The nitro glycerin e i s dra w n o ff from the ta nk by mea ns

.
-

of a rubber tube through which it fl ows to the mea surin g vessel (s ee p 30 6)

,
.

w hich i s placed j ust below i t .

W a s h-wa te rs . All t he waters used for was hi ng the ni tro glycerine and plant are run do w m -

”
lead gu t te rs in t o a large ta nk in t he wash water settling house a n d t he -
,

c on t ent s of th e ta nk are kept agi ta te d by mea n s of c omp ressed air A t t he .

end of the d ay s work the air is shut o ff and any ni t ro glyce ri ne i s all ow e d
’
-

to s et t le out Thi s i s dra w n o ff from the botto m oii t he ta nk and r et urned

.

to the pre wash ta nk -

The r esidual mud consists mostly of lea d sul phate
.
 MAN U FACT U RE OF N I TRO GLYC ERINE -

mixed with wate r and nitro glycerine and some sand wool etc It i s ren dered
-
, , .

alkali ne with so da solution and filtered a n d washed with warm water in the
,

mud hut Thi s converts most of the lea d sulphate into carbonate and
.
,

renders the material much less dangerous The mu d i s subsequently wrun g .

out in flann el to remove u s much nitro glyce ri ne as possible and finall y it -

,

is mixed with kerosine and burnt At Waltham Abbey the wash waters are .
-

finall y run into a small pon d in whi c h a c ouple of dyn amite cartridges are
,

exploded every week so as to destroy any ni tro glycerine that may still be —

present .

The waste acid from the separator carries wi th it some nitro glycerine Ait er sep a ra -
,
-

which i s present in it in three form s there are some min ute globules which ti on .

have not had time to separate out completely there i s some in solution i n ,
”
the acids and there is some which may be called potential nitro glycerin e
, ,
-
,

which has not actually been formed but is present as mono and di nitro ,
—

glyceri ne and may be converted into tri nitro glycerine on s ta n din g s o causing
,
- -

a further separation at the surface of the acids In order to avoid the great .

danger that woul d be caused by the separation of ni tro glycerin e in any part -

of the acid plant the waste acid i s generally allowed to stand first for several
,

days in an after separator (German Na c h sc h e ide r

-
T hi s consi sts
of a large cylin drical lead tank with a c onical top sur mounted by a glass cyli nder .

It i s fill ed until the surface of the li quid i s vi sible inside the glass An y nitro .

glycerin e that separates i s removed by the attendant with a small aluminium

scoop and washed wi th wate r in a small lead tank and then carried over
, ,

by hand in a rubber bucket to the washi ng hou se The after separatin g .

-

house c ontain s a number of after separators so that it can hold several days -
’

supply of waste acid .

R cent i m
D urin g the first years of the present century a number of important im o ment e
r ve s.
p
p r o v e me n ts were introduce d at the Royal G u npow d er Factory W altham ,

Abbey into the methods of manufacturing ni tro glyce ri ne as also into the
,
-
,

other processes carried out there Those relatin g to the manufa c ture of .

gun cotton have been mentioned in Chapters XII and XIII Maj or (now
-
.

L t Col Sir ) F L Nathan was the S uperintendent and Mr J M Thomson

.
-
. . .
,
. . .

the Manager and the nitro glycerine plant was un der the charge of Mr W
,
-
. .

Rintoul The far reac hi ng alterations have been dealt w ith by the first two
.
-

named of these in the J o u r na l o f the Society o f C hemica l I n du s tr y 1 9 0 8 p 1 9 3 , , . .

The operation of was hi ng the nitro glycerine would appear to be a compara W a h ing
-
s .

tiv e ly safe one as the material is neutral or alkaline and it is only subj ecte d ,

to agitation by means of compressed a ir yet there have been a considerable

number of fatal accidents i n washing houses H M Chief Inspector of E x p lo . . .

s iv e s in hi s Special Report No 1 62 on the e x pl o sion at F a v e r s h a m on November

.

9 1 903 gives a li st of nin e which had occurred in Great B ritain alone and
, , , ,

there w a s anot her one at Ha yle on January 5 1 9 0 4 (S pecial Report No as , ,

 E X P L OSI VE S

we ll a s a co n s i de r able num be r in o t her co untries One po s s ible ca us e of some of .

t h es e c a t as t rophes w a s t he p r esence of t he loo se a ir pipe which wa s s imply -

,

laid on t h e b o t t om o f t he t a nk : i t is qui t e con c eivable tha t t he j a r ring of

t hi s pipe on to t he bo t t om of t he t a n k migh t in ex c ep t ional c irc umsta nce s
ca u s e a n e xplos ion The a ir pipe is n o w ca rr ied down t he outside of t he
.
-

t a nk from above t he level of t he li qui d and is bur nt on t o t he un der sur fac e

o f t he bo t to m of the t a n k Holes a re pie r ced t h rough at interval and the r e
.
s
,

is a hole in the e n d of ea c h b r an c h of the a ir pipe so arr anged t h a t any ni tro -

gl y c e ri n e t ha t h a s lodg ed in t he pipe wi l l be blown out a gain into a shallow ,

dep r es ion w hi ch slope s down t o t he outlet

s .

The w ooden c a sing of t he wa hi ng t a nk has also been done away with s s .

It w a s al w a y s po s ible t ha t a sm a ll leak mi gh t be formed t hr ough whi ch ni tro

s

gl y ce rin e w oul d pass and soa k into t he w ood and the r e se t up a dangerou s
dec ompositi on and ni t ro glyce ri n e w a s a lw a v s lia ble to get spilt or splashed
,
-

on t o t he wood .

Ano t her po ssible source of danger w a s t he p r esence of the numerou s c ocks

through w hi ch t he ni t r o glyce rine had to p a s s Fr ic t i on migh t be ca used
-
.

if the coc k s t uck or if t he ni t ro gl y cerine fr oze in or aroun d i t ; al o if t he

,
- s

hole t hr ough the ke y of t he c oc k w ere not quite s t r aight there might be a ,

p o cke t in hi ch ni tro glyce r in e c oul d lodg e and set up d ec omposit on Soft

w - i
.

r ubbe r t ubin g h a s n o w bee n substitu ted for the c oc k a rranged a s i s shown s

,

in Fig 40 w hi ch ho w ever still shows a w ooden casing to the tank

.
,
The .

w it rubbe r t ube d i fixed o v er t he outle t lead pipe and is kept closed by

,
s
,

sli pp ing i t o v er t he hollow lea d plug e through which a small current of air i s , ,

pas ed w hils t t he ni t r o glyceri ne is bein g w a hed “ h e n the charge i s rea dy

s - s .

t o be r un o ff t he ai r is shut d own and t he rubber tube kinked in the hand ,

a n d p ull e d o ff t he plug The fl o w of the nitro glycerin e can be c ont r olled

.
-

by p inc hing t he t u be wi th the hand The skimming tube 6 rs also of soft .

, ,

r ubbe r t he ha rd and hea vy s kimmer ha s been done a way wi th Thi s ski m .

min g t ube has since been improved by widening i t at the mouth funn el wi se -

and p r ovi din g it wi th a rub b er handl e .

It has bee n suggested t hat t he e xplosions in w a s hi ng tank s may have been

caus ed by t he gene ra tion of elect ri ci t y b y the f ric tion of the a ir w hen p a sin g s

t h r ough t he j e t s in t he air pipes Bu t air or other g a s cannot p r oduce elec

-
.

t r ic ity by f ri c t i o n a s w a s shown by F a ra d a y l
It is only w hen t he air ca r ries .

wi t h it pa r ti c les of so li d m a tter or li qui d globul es th a t any charg e is formed ,

a nd t hen onl y if t he solid or liquid m a t ter be i t self non c onduct ing The -
.

nit r o gl y ce ri ne is surroun ded on a ll sides by conducto rs on i t s upper s u rfa ce

-

by sod a solu t ion a n d eve r yw he r e el s e by le a d so that a ny charge woul d b e ,

r apidl y disc ha rg e d especi a ll y a s t he ni t ro glycerine i s kept in m otion and i s

,
-
‘

1 E x p e r ime n ta l Re s ea rc h es in E le c t r ic it y .
"
r
Se ies X VI II , P h il . Tra ns " Ja nuar y
1 84 3 .
 S EC T I O NAL EL E V AT I O N

PL A N

FI G . 40 . N it r o -
g ly c e irn e “a s h in g
an k T

a , Air p ip e
-
c Skimm in g t b
, u e fo r w as h w a t r
-
e s

( 1, O utl te
p ip e fo r n it r o - r
g ly c e in e e, H ll w l ad p l
o o e ug fo r e nd of d
/f H
, o le s in e d sn o f b ran c he s o f a i p ip r -
e
 E XP L OSIVE S

mix ed wi t h dr op s of t he s oda solu ti on E xpe rimen t s carri ed ou t a t Arde er .

fai l e d to d e t ec t a ny charge of elect r ici t y 1

.

Fume h oods. Th e p re was h t ank i s con t r uc t ed in t he sa me way as t he final wa hing

- s s

t a nk ; t he princip a l difi er e n ce lies in t he a rr angements made for co nduc tin g

away the fumes The ai r ri ing from the p re wa sh ta nk ca r ries so me ni tr ic
.
s -

ac id with i t as well as fum es of t h e ni tric e ste rs of gly ce ri n e t he tank ha s

a fi xed lea d cover wi th an o p ening whi ch is kep t co vere d wi t h a smal l r ubber
,

flap and t he r e is a fum e pipe t hr ough w hi ch t he fumes a re dr awn b v mea ns

,

of a j et of a ir or ste am From t he washi ng ta nk the a ir ca rries away onl y

.

vap our of w ate r and nit r o glyce rine consequen t ly the lea d top i s un nece ssa ry
-
,

it is merely provided wi th a h o od of rub ber cloth shaped li ke a large inver t ed

fun nel the ste m of w hi ch p as ses out through the roof a n d is p rovided wi th
,

j et t o kee p a c u r rent of air going in an upwar d di rec tion during the

whole of t he ti me of t he washi ng The rem oval of the fum es of ni t ro gly ce rin e
.
-

makes the work much les s tt ryi ng to the workm en In t he p r e wa h ta nk the .

s

air holes in t he botto m a re h u s h ed wi t h sm all perforated eboni te plugs to

-

prevent the ra pid enla rgement of the holes but in the fin al wa shing t a nks ,

t hese small plugs a re unnec es sa r y as t he wea r is very slow .

A very ha r d sto ny dep osit c o n sisti ng mostly of calcium carbo na te us ed

to be formed on the i nside surface of the washi ng tank due to t he acti on of ,

the soda solution on the hard wate r employed Thi s w a s another p o s si ble .

source of da nger The formation is now prevented by softeni ng the water

.

before u se There is a large ta nk in the c harge house above t he level of t he

.

ni t r at i ng hous e and in thi s sufficient water is tr ea ted ea ch da y to suffi ce for

,

a ll the washin g operati ons of the next da y E nough lim e and sodi u m car .

bona te is ad de d to pre cipitate the bi carbona t e and su lpha t e of calcium a n d

the magne sia and the wate r is well agita ted and al lowed to settl e over ni ght
, .

Washi ng tanks shoul d be mad e wi de and s h all ow beca us e a red uc t ion in ,

the dep th of the liqui d grea t ly dimi ni shes the time re quir ed for t he se pa ra t ion
of the ni t ro gly cerine from t he water At the Ro yal Gun powder Fac t o ry
-
.

c ompara t ive tr ials were car r ied out wi t h two di ffere n t de s ign of ta nk t he s
,

propor tion of wate r to ni t ro glyce ri n e and a ll other con di tion s be ing kep t
-

consta nt The depth of liqui d onl y was vari ed by havi ng the ta nk of difi ere n t
. s

di ameters The resul ts we r e

.

T t l d p th f liq ui d
o a e o M n t im f p a ti n ea e o se ar o

27i in . 34 g 28 1!
. se cs .

1 8 g in . 10 9}

In the p re wash ta nk the ni t r o glyce r ine i s u sually wa shed about four t imes
- -

at a te mpe r ature of abou t 1 8 C The firs t t hr ee w ashi ngs are wi t h w a t er only

°
.

but the last with some soda so a s to r emove a ll bu t a sma ll qu a n t i t y o f t he

,

a cid .The nit r o glyce r ine is then sent down a gu t t er to t he w a s hi ng house

-
,

1
S ec S R . .
, 1 56 p, . 8 .
 MANU FACTU RE OF NITRO GLYC ERIN E -
21 5

where the final was h in g i s carried out The number and durati on of the .

washin gs vary considerably in di fferent works but the followin g scheme is ,

a good one
1st was hi ng 15 minutes wi th dilute soda (3 % per cent Na .
l C0 3)
2n d 30
3r d 45
4th 15 with softened water only
5th 15

Temperature of washing 30 C prop ortion of soda solution or water to n itro

°
.
,

glycerine 4 : 1 0 by weight .

All the wash waters from the pre wash and final washing tanks are run La b y inth
‘

- -
r s.

through labyrinths b e fore they pass to the wash water settlin g tank and from -
,

the latter they agai n pass through a labyri nth before they reach the pond .

The labyrinth consists of a long lead tank open at the top and provide d with
a number of transverse partitions so arranged that the water has to fl ow
alternately over one and under the next The bottom i s inclined gently to .

a central channel w hi ch run s the whole length of the vessel ; there i s also
,

a fall towards the exi t end Most of the globul es of ni tro glycerine collect
.
-

in thi s central channel and can be dr awn o ff thr o u gh a rubber tube arranged
,
'

i n the same way as the deli very tube of the washin g tan k S ince the in tr o du c .

tion of these lab y rinths at W altham Abbey the amount of nitro glycerine —

that i s recoverable from the wash water settlin g tank i s o nl y 1 % per cent -
.
,

whereas formerly it w a s about 4% per cent .

In those parts of the plant where the ni tro glycer ine i s mixed with strong Nit ato -
r r

ep a r a t o r
acid i a the ni trator and separator it is not p oss ible to make use of delivery
,
. .
,
s .

tubes of rubber such as have been substituted for cocks in a ll other parts of
,

the ni tro glycerine plant Yet cocks are speciall y dangerou s here as the
-
.

acid nitro glycer ine is more liable to spontaneous decomp osition than when
-

it is neutral or sli ghtly alkali ne In January 1 9 0 1 t hi s danger was brought

.
,

home at the Royal Gun powder Factory in a very forcible manner : shortly
after the charge had been r un out of the ni trating apparatus an explosion
occurred in one of the earthen w are c o cks lea di ng t o the dr o w ni ng tank If .

the apparatus had conta ined the charge a seri ous accident must inevitably ,

have occurre d Thi s led to the idea of removing the nitro glycerine at the
.
—

top of the nitrator instead of at the bottom a method the accomplishment

of which was ren d ered more easy by the fact that the nitro glycerine separates -

out at the top of the charge The simplest way to e ff ect this was to raise
.

the whole of the contents of the apparatus so that the n itro glyce rine w o uld ,
-

flow over a suitable arrangement i n the cover and run by gravity into the
pre wash tank a n d the best method for rai sing the level was to introduce
-
,

waste aci d from a previ o us charge at the bottom of the vessel

-
.
 E X PL OSI VE S

The fo rm O f plant a d op te d t o carry out thi s p r inciple i s shown in Fi g 4 1 .

,

and i s prote c ted by E ngli sh P atent NO date d August 8 1 90 1 ta ken .

, ,

out in t he j oint names O f Nathan Thomson and Rintoul The sep a ration , , .

Of the ni t ro glycer ine from the aci d s takes place in the s ame vessel a s the
-

”
ni tration a nd for thi s reason the inven t ors ca ll i t a nitrato r separator
,
-
.

It cons ists Of a cylindrical lead vessel a with a bottom sloping in one direction, , ,

a n d c onta ining cooli ng coils and a ir pipes the number of which depends on -
,

the size O f the vessel The cooling coils enter and leave through the sides
.

j ust below the surface O f the ni trating acid as also d o the air pipes g The ,
-
, .

c ooling water i s le d in and out again through one main pipe c ontro lled by
a sin gle c ock and the coils h branc h away from thi s main pipe inside the
, , ,

vessel The supp orts for the c oils are of lead and are formed by loading
.
,

up between the tur ns ; this arrangement obviate s the use of lead covere d -

iron supports and entirely does away with inte rstices i n which nitro glycerine
,
-

or sulpha te can lodge The cover i s conical a n d is burnt on to the cyli ndr ical
.
,

portion it terminates i n a cyli n d er e of small diameter Open at the tO p and , ,

provided wi th glass in spection windows f the only o t her fitting in t he cover ,

i s a gland through which the thermomete r 8 passes A pipe k opens out

, , , .
, ,

O f one side O f the cylin der and from this another pipe m branches for carry ing
, , ,

away the fumes suction being pro d uced by means O f an air j et At a lit t le
,
-
.

dis tance beyond this fume pipe 1c opens ou t to a gutter lea di ng d ow n at an

in clin e to the pre wash tank The pipe d for i ntroducing the mixed acid
-
.
, ,

into the apparatus a s well as the was te acid for the di splacement enters t he
, ,

vessel at t he bottom In order to prevent any nitro glycerine gettin g in to

.
-

t he acid supply pipe it is carried vertica lly do w nwards below the bottom O f
the vessel and rises aga in i nto it There are two branches b c leading out
.
, , ,

Of this pipe ea c h w ith an earthenware cock ; 1) lea d s to the waste acid egg
,
-
,

and c to the dro w ning tank .

The w aste acid from the previou s charge havi ng been r u n out Of the vessel ,

the cock on the nitrating acid tank is Opened and the aci d i s allo w ed t o run
-
,

into the nitrator separator by opening the cock on the a cid supply pipe (1
-
, .

As soon as the acid has all run in the cock on the nitrating acid tank is c losed
,
-

as well as that on the acid supply pipe a n d the acid h a ving been brought to ,

the des ired te mperature by means O f the cooli ng coils the in j ec tor i s i nserted
through the open top O f the apparatu s and the nitration i s commence d The ,
.

temperature O f the c ooling water which flows through the coils is regula t e d
,

so that the total time of nitration for any given charge i s kept consta nt wi t hin
fairly narrow limits both winter a n d summer To enable t his t o be d one .

the wa ter i s refrigerated when neces s ary The advantages O f using refrigerated .

water are that nitration i s complete d in a rea s o nable time loss O f ni t ric acid ,

d u e to volatili zation is reduce d and t he time O f ni t ra t ion being c onsta nt t he

,

Operati o ns O f the fa c t o ry can be c arrie d ou t in a syste ma t ic manner The .

FI G . 41. N it ra t o r -
Se p ara t
o r fo r th e Ma n u fa c t ure Of N it ro -
r
g ly c e in e (fr o m
 21 8 E X PL OSIVE S

volatilized nitric acid is c arried away to a Guttmann con d ens ing to wer pro
v ided wi t h a c i rc ulatin g arrangemen t for t he li qui d the fumes are t hus con
de n s e d and about 1 8 lb Of nitri c acid of spec ific gravity 1 3 2 are recovere d per
.

ton O f nitro glycerine produce d VWie n nitration i s complete d the inj ec t or is

-
.
,

rem oved and the nitro glycerine i s all o w ed to separate for a few minute s
,
-
.

The cock lea ding fr o m the di spla cement waste aci d tank i s then opened and -

was te acid i s allowe d to enter the apparatus a t the bottom by Openin g the aci d
supply pipe The rate Of inflow Of the di splacing acid can be regul ate d with
.

the utmost nicety so as to allow of the nitro gly c e ri n e flowing over thr ough
,
-

the gutter to the pre wash tank as it separates The di vi d ing li ne between the
-
.

clear ni tro glyceri ne and the acid is w a tc h e d thr ough the in spection windows
-
.

The ni trator separator i s left f u ll O f waste a cid until it i s requi red for the
-

ni tration O f another c harge The result O f this i s that no part Of the inte ri or
.

O f the apparatus i s exposed to aci d fum es and its life is greatly increase d , .

In the Old form of plant in which thi s c oul d not be d one and the c oils entere d
, ,

through the cover it was necessary to rem ove the c over and the c oils as O fte n
,

as once in every three m onths to repair them The new form of apparatus .

was in u se for two a n d a quarter years wi thout being opened up and then ,

the whole of the interior inclu di ng the c oils and a ir pipes were fo u nd to be as -

good a s new and no repairs O f any kin d were required As a precaution the
,
.

coolin g coils are tested every week by air press u re before c ommencing work
any leak woul d be detec ted at once by the escap e O f air bubbles through the
was te acid .

Coo ling c o ils . It i s well to arrange the exit pipe from the c oi ls so that the water in them
i s un der a sli ght vacuum If a small leak does develop the acid wi ll then
.
,

enter the coils where it will be drowned by the large volum e O f water and ,

the defect w il l be sho w n by a rise in the temperature Of the water leaving

the coils In Germany several exp losions have been asc ri bed to the burst ing
.
-

O f the c o ils but no such accidents appear to have occurred in E ngland It

, .

ha s been proposed by the E xplosive W orks Dr R Nahnsen and C O O f Ham , . . .

burg to use chloroform carbon tetrachlori d e or other s imilar chlorin e deriva

, , ,

t iv e s for circul at ing through the c oil s ’

but this doe s not appear to be necessary ,

pro v ide d that reasonable precautions are taken .

The afte r separatin g house has for some ti me ceased to e xi st at the Royal
-

Gunpowder Factory Its aboli tion was rendered possible by the fact that
.

the addi tion O f water to the waste acid not Only prevents the formation O f
more nitro glycerine but also absorb s any that e x ists as minute globules
-
,

in the waste acid 2

Origin ally o n ly 2 per cent O f water was ad d ed to the
. .

waste acid as thi s quantity was f o und to be su fficient at the normal tempera
,

ture O f storage 1 0 to 1 5 C to prevent any further s epara t i o n B u t on

,
° °
.
,
.

1
Ge r P t Amn
. a July 6 1 9 10 ; S S 1 9 12 p 3 0
. .
, . ., , . .

2 N a t han Th ms o n n d Rinto ul E n g P t 30 20 F b r u ry 9 1 90 3
o a e a
, a , . . , , .
 MAN U FACTU RE OF NIT RO GLYC ERIN E
-
21 9

J anuary a fatal acci dent occurred with a drum O f nitro glycerine

1 5, 1 9 0 6, -

waste aci d which was part Of a c o nsignment sent by the E xplosives and
,

Chemical P roducts L td to Messrs F W Berk a n d C O In consequence O f

.
, . . . .

this further e x p eriments were carried out at Waltham Abbey which are
, ,

given in detail in Special Report NO 1 74 Of H M Chief Inspector O f E x p lo

. . .

W ATU I I AN h

ACIO mm

PRSWASN I ANK

W AYEfi

NASH AU O f cc$

F1 G . 42 . W a lt ham Ab b e y N it ra t ing H o u
-
se Pl an t

s iv e s . It was then found that in order to prevent further separation Of nitro

glycerine when the temperature Of the waste aci d is re du c e d to 0 C it i s
,
°
.

necessary to add 5 per cent O f water The fact that when the temperature
. .

i s reduced the solubility o f nitro glycerine i n waste aci d i s c onsi derably di min
-

is h e d should be kept c onstantly in mind In Germany where large va riations

.
,

O f temperature are more liable to occur than i n E nglan d there have been ,

several accidents due to the further formation O f nitro glycerine on the surface -

of acid that had been subj ected to after separation for a c onsi derable time -
.

H owever the waste acids are treated they shoul d not afterwar d s be allowe d
,

to fall to a very low t emperature and the denitration should take place as
,
 E X P L OS IVE S

soon as po s ible If after sepa ra tion ha s ta ken pla ce wi thout the addi tion
.
-

of wa t er t he a cid sho uld af t e r wa rds b e kep t a t a higher tempe r ature t h an

,

tha t at w hich t he aft er sepa ra t ion w a s eff ec t ed -

.

The me t hod adop t ed for dealin g wi t h t he was t e a cid in t he ni t r a t or sepa s -

ra t or is a s follows The was t e acid is all ow ed t o remain in t he ve s sel u n t il t hi s

i s re qui red for ano t her ni t ra t ion a n y ni t ro glycerin e separa t ing in t he inte r val
,
-

be ing di p laced in t he usual way in t o t he p re w a s h t a nk Furt her mp a ra tio n

s -
.

is promoted by c oo lin g down t he wa s t e acid “ h e n t he ni t ra t or is t o be .

Sta te “ o r 0 0 m g

t
Nitr a ing H ous e Filte r in g a nd Mix in g H o us e W W
a sh a ter Se ttlin g H o us e

MA . d d
Mi x e Aci
T k
G G
ly c er ine Ta n k W T . W a sh in g Ta n k P 31
“

. Fil te r Ta n k W W S
. . . W a sh W a te r Se tt li n g
k
. .

D D
an S itn tor Se pa ra to r L h b yr in th B . B ure tt e Ta n
k k
.

D T ro wni ng Ta n D I . ro wning Ta n
A id T k k
. . .

c an P W Pre m h Ta n
. .

12 . Egg a b yr in th L
FI G . 43 . a a
Di g r m o f N it ro ~

g ly ce r in e P la nt a t I Va lt ha rn

emp t ied eve r y trace of ni tro gl y cerin e is removed from t he surface of t he acid
,
-
,

and t he quan t i t y O f was t e acid re qui r ed for t he disp la ce men t O f a sub se quen t
charge is then r u n ou t of t he ni t ra t or in t o an egg and blo w n i n t o t he di spla c in g ,

ac id ta nk in t he charge house To t he remainder o f t he w a s t e a cid in t he .

ni t r a t or 2 per cent of wa t er is t hen added t he c on t en t s of t he ni t r a t or

.

being s t rongly a gi t a t ed mean w hile b v mean s of a ir The w a s t e acid is .

t hen sen t i n to an egg and blown up t o a t a nk in t he deni t ra t ing house .

As a f u rt her p r ecau t i o n a ll w a s t e acid is kep t a t a t em p e ra t ur e O f a b ou t

15 C
°
.

The new lVa lth a m Abbe y plan t is sho w n di a g ra mm a t ically in Fig s 42 43 .

,
.

One grea t advan t a ge O f t he plan t is t ha t t he ele v a t ion of t he ni t ra t o r a b ove t he

wash wa t er se t t li ng t a nk is les s t han ha l f w h a t it w a s wi t h t he old s t yle of
-
 MAN U FACT U RE OF NIT RO GLYC E RIN E -

plant vi z , feet instea d O f 3 3 % fe et

. 16 Th e s eparating and after separating .
1 —

house s are dispense d w ith w i t h the r e sult t hat th e facto ry occupies less space , ,

and there are fe w er piec e s of apparatus .

The safety O f the manufa cture is increa sed by the absence O f c o c ks and ,

by the removal of the n itr o gly c e r ine from conta ct wi th th e acid as soon as s

i t has separated from it Thi s i s an especially great improvement over th e .

r o ce d tu e in the factories w here the separator is in a diff erent house to the

p
nitrator for there the aci d nitro glycerine has to fl Ow d o wn a long gutter
,
-

from one house to the other The presence Of cooli ng coils during the separa .

tion is also an advantage As fe w er men are req uir ed to w ork the plant the .

risk to personnel is corresp o ndi ngly reduced .

The di minution of danger during separation is a matter Of considerable

importance as th er e h a v e been a number Of di sastrous e x plosions in ni tro
glycerin e separators On February 1 8 1 90 4 the separator at the Cliffe
.
, ,

Fact o ry sta rted to fume vi olently and then exploded causing the death Of ,

four men and much structural d amage At Avigliana in Italy a si mil ar .

2
, ,

accident occ u rre d in April 1 9 1 2 and although the men in the h o use w ere able ,

to escape before the e x plosion it c aused another house to blow up and tw o , ,

men w ere thereby kill ed In July 1 9 1 2 a fe w days after the separating house
.
,

had been rebuilt it ble w up again Thi s time the nitro glycerine caught
,
.
-

ali ght but again the men in the house w ere able to escape before the remainder
,

O f the charge explo d ed no one w a s killed but the material damage amoun ted ,

to £ 8 00 0 Similar cases Of charg es taking fir e in the separator have occur red

.

in Mexi co An e x plosi o n due to vi o lent decomposition of ni tro glycer ine

.
,
-

in a separator took place on March 1 1 9 1 1 at the factory at U mbog intwini

, , ,

in South Af rica it w a s ascribe d to the use Of defective glycerin e made locally

from whale Oil In 1 90 7 a German nitro glycerin e factory w a s destroyed by
.
-

an e x plosion Originating in the separator .

The drowning cock is contr o lle d by means Of a l o ng r od termi natin g in Dro wni ng
a handl e si tuated on t he O pera t ing platform By t u rning thi s handle through “ a ng e“
.

”
r

a quarter Of a cir c le not onl y are the conten t s Of the ni trat o r separator allowed -

t o run into the dr o w ni ng tank but at the s a m e tim e com presse d a ir is tur ned ”
,

o n t o agitate the c ontents of the tank a n d w ater is also a d mi t ted The dro w n ,
.

ing tank is al w ays kept full Of w ater and i s pr o vi d ed wi t h an overflo w This , .

dro w ning arrangement has the a d vantage O f simplicity a n d the continu o u s ,

1
I t h a s b e n p ro p d t e r du t h e n ry f ll in t h n it r g ly rin f c t ry
o se o e ce e c e s sa a e o -
ce e a o

s t ill fu t h r b y au s in g t h nit ro gly c r i n t r i fr m t h b tt m f t h w a hing t a n k

r e c e -
e e o se o e o o O e s s

t h ro u gh rub b r t ub e s b y t h w igh t f a u ffi ie n t ly h igh o lumn f w at r int ro d u ce d

e e e O s c c O e

ab v (I Vh to n Sh ckl d y a n d C rt i n d Ha rv y O to b e r
’

o e ar , a a Lt l E ng P t u s s a e , c .
, . a . c

Me r C ur t i n d H ar v y ha v e re ct d p l n t w it h ll t h v l f
’
14 , ss s. s s a e e e a a a e es s e s or

t h d iff r n t O p ra t io n s in t h
e e e e a me b u ild ing t ha t t h p ra t in g w
e h ing fi lt rin g
s ,
so e se a , as , e ,

a nd m a e in g f th e n it ro gly r in in t b
s ur O n b a ri d t w it h o u t runn ing it
-
ce e O o x cs ca e c r e ou

d wn l n g gu tt e r t
o o o th r b u d
i l i n
g s o
2
S e S R N 1 67 s . ec . .
,
O. .
 E X P L OSIVE S

s upply O f co ld w a te r keeps d o wn t he te m pe ratur e due to t he mi xing of a large

v olume of a c id wi t h t he w ater and als o a llo w s of a small er dro w ni ng ta nk
,

bein g u s ed t h a n w o u l d o t her w i se be n ec e s s ary .

The regul a t i o n s of t he German Tra d e G u il d 1 0 ) are s o me w hat s i milar .

It is there laid d o wn t ha t t he dro wn i ng tank mus t have a c apacity equal to

a t lea s t fi v e t imes the v o lume O f t he a c i d a n d is to be provid ed wi t h stirring
,

arrangement s and a w a t er inl e t a t t he bot t o m O f the ta nk Of s uch a s ize that

.

t he acid w i ll be rapi dl y di splaced and no h eat ing Of th e ni tro glyceri ne wi l l take -

pla c e The dro wn ing ta nks mu st al w ays be kept wi t h t he pr o per quantity Of

.

w a te r in them . The w ater inl et a n d the air for stirring must be tur n e d on simul
ta n eo u s ly w i t h t he dr o w nin g cock o r must be so arranged t hat they can be
,

o perated from a p la c e O f safety o utside the traverse In some c a ses these cocks .

are so arranged that th ey are all o perated simul tan eously by c ompress e d a i r ,

w hich can be t u rned on from several points 1 but it is not a d vi sable to make such
,

arrangement s to o c o mplex a s they are not onl y li able to fail but t h rough some
, ,

combination Of peculi ar circum stances they may ac t w rongly in an emergency ,

a n d so w hilst preventing an e x plosion in one house cause one in ano t her , .

Before O leum c o ul d be O btained at a reasonable cost it was usual to use ,

an acid ma d e by mi x ing about 5 parts Of G O V w ith 3 parts Of concentrate d . . .

ni t ri c acid (s p gr 1
. . At Wal t h am Abbey 8 parts O f the mi x ed acid were
use d t o ni trate 1 Of glycerine b u t in some other w orks a smaller amoun t of acid
,

w a s employe d O fte n 75 part s to 1 Of gly c eri ne

,
.

Theoreticall y 1 00 part s of glycerine sh oul d give 246 7 parts Of ni tro glycerine - -

,

but for several reasons this y ield i s never attained in practical man uf a cture .

The a v erage yi eld at the Royal Gunp o w der Factory over a series of eight yea rs
w a s 21 4 2}per cent but after the introduction Of the ni trat or separat or and other
.
,
-

improvements it was 220 2 per cent as an average Of tw o years w orkin g wi th

.
’

the proportions j ust mentioned There is practicall y no oxi dation of the gly c er
.

ine c o nsequen t ly th e rea ction may be represented by the follo wi n g Table

,

Be fo re n i t ra ti ng Af te r n i ra t ti ng

Pe r ce n t . Pe r ce n t .

H ZSO ‘

65 3 3

1
S ec L es se r , 1 90 7,
p . 48 .
 MAN UFACTURE OF NIT RO GLYC E RIN E
-
223

The w ater present in the nitrating acids performs no useful function . It

might b e eli minate d and acid used as follows : ,

B e fo r e n i ra t t in g Af te r t ti
ni r a ng

Pe r ce n t . Pe r ce n t .

H ,s o ,

50 9 -5 1 00 0 3 62 8 1 00 -0

But it is more usual to use an acid containing 1 to 2 per cent water . . The
followin g results have for instance been recorded by : , ,

So dd y C h a lo n H o fw i mme r

P ro p o rt i n
o Ac id G ly c r in e e

Y ie ld

The res ul ts given by Soddy were O btained with a nitrator separator at a -

factory in Me x ico 1
those by Chalon in a sim ilar plant in the dynamite works
o f B o ce da in Italy H o fw immer s figur es were O btained from laboratory
’
?
,

experiments in whi c h the proportion Of acid to glycerine w a s varied through

a wide range 3
the maximu m yield was Obtained with the proportion 6 3 1 ,

but the most remunerative proportion at the prices O f materials assumed

was 5 3 1 At W altham Abbey with a proportion 6 1 3 1 the yield for a
-
.
,
-
,

period O f nearly two years was 229 per cent .

The di fl e r en c es bet w een the yields generally Obta ined and the theoreti c a l ly
possible yield Of 246 7 per cent i s d u e to the influence Of various factors The
-
. .

practical yiel d s are generally calcula te d upon the glycerine as nit rated w hereas -
,

t hi s glycerine d oes not usually contain m ore than 9 7 per cent O f glycerol . .

1
A r ms a nd
Ex p Ma c 1 9 1 1
, r h .
2
E x p lo s i/ s mo der n es , 1 9 1 1 , p 222. .

3
C h em . Z
e i t , 1 9 1 1 , 3 5,
p 1 229 . . H o fw imme r h a s g ive n t h e r e s ul t s Of fu r t he r lab r o a

t r
o p r nt
y e x e ime s in S S , 1 9 1 3, p . . . 3 6.
 E X P L OSIV E S

The w a s t e aci d produced on ni t ra t ion absorb s a fur t her quan t i t y Of t he

ni t r o glycerin e the pr o p or t ion absorbed d e p ending upo n t he com p osition
-
,

O f t he w a s t e acid A s t il l fu r t her quan t i t y Of t he ni t ro glyce r ine di sa ppe a rs

.
-

i n solution in the w ash w aters from the pre w ashi ng and w ashi ng opera t ions -
.

The solubili t y of ni t r o glyce r ine in acids O f varyi ng composi t ion formed

-

t he subj ec t Of numerous exp erimen t s a t t he Ro y al G u npo w der F a cto r y l

.

“ h e n ni t ro gl y cerine is ad d e d t o a mi xed ac id it fir st di ssol v es u ncha n ged

-
, ,

bu t pa r t of i t is at once decom posed wi t h the formation Of o t her es t ers such ,

as glycerol t risul pha t e t he production of w hich m ay be r epresen t ed by the

,

r evers ible reac t i on C H (OXO 3 H ,S O

, F C H (SO H )
3
, 3HX O , , 5 4 , 3.

The ni t ro glyce r in e di s ol v ed as such w a de t ermi ned b v shaking out rapidly

- s s

wi t h chloroform and t he ni tro gl y ce r ine deco m po sed w a s es t ima t ed by differ

-

ence Fig 44 sho w s t he amount Of ni t r o gl y cerin e taken up b y a cid c ontaining

. .
-

w a t er and ni t r ic ac id in t he co n t an t ra t io 1 and varyin g percent a ges

s

O f sulphur ic acid I t will be seen t ha t por t io n O f the c ur v es are represented

. s

b y shad ed lin es Thi indi ca t es t ha t on at t empting t o sa t ura t e ac ids in t his

.
s

z o ne o xida t ion of t he gl y ce r ine radi cle occur red and t he r esul t s w ere vi t iated ,
.

An uncon t rolla ble reac t ion w o u ld se t in if special precau t ions w ere no t t a ken
no acid Of a com posi t ion in or nea r t hi s zone should ever be allow ed to come
i n con t a c t wi th ni tro gl y cerine in a manuf act u ring ope ra t ion Fig 4 5 shows
-
. .

t he resul t s t ha t w ere O b t ained wi t h acid in w hich the ratio i s ul p hur ic acid s

t o w ater w a s kep t cons t an t a t 5 8 and the ni t ric acid w a s vari ed In Fig 4 6

-
. .

the ra t io of sulph uri c to ni t ric acid w a s kep t co ns t an t a t 1 0 4 and t he w ater -

,

w a s va ri ed Fig 47 w a s O b t ained wi t h mix t ur e s Of sul ph u ri c ac id and w ater

. .

onl y here again o x ida t i on took place wi t h a cids Of 50 t o 8 5 per cent st ren gth . .

All t hese solubili t y de t ermina t ions w ere c ar r ied ou t a t 20 C It w ill be seen °

.

t hat all t he curves wi t h mi x e d aci d sho w a di s t inc t minim um w hi ch poin ts s

to t he fa c t t ha t t here mus t be a cert ain composi t ion O f acid w hi c h wi l l be the

most e conomi cal t o use .

Ti me o f The t im e t ha t t he ni t ro glycerine t akes t o separa t e from t h e acid is lia ble

-

t o vary wi t hi n wi de limi t w hen t he separa t ion i ca r ri ed out in a spec ial s

separa t or i t ma y be an yt hin g from a quart er of an ho u r up t o se v eral hour s

, .

Long separa t i ons are v ery inconveni ent a s they di sorganiz e t he w hole Of t he
w o rk of t he fac t ory I n t he early da y s O f t he indu t ry t he y w ere generally
. s

a t tri bu t ed t o imp u ri t ies in t he glycerin e and probabl y wi t h j us t ice In t he ,

.

B o u t my s y s t em O f m a nufac t uring nitr o gl y cerine t he gl y c erin e w a s di s olved- s

firs t in s ulph u ric acid t he solu t ion w a s cooled and t hen a mi xture of ni t ric and
.

su lphuri c aci ds w a s added Bu t a s a resul t Of the acti on Of t he concentra t ed

.

sul phuric acid on t he gl y cerine and t he impuri t ies in i t produc t s were for med , ,

w hi ch grea t l y imped ed t he separa t ion no ni t ro glycerine w a s t aken Off un t il -

tw e n t v four ho rns had elap s ed a n d t h en t he acids were t ransferr e d t o c a rb oys

-
.

1
S ee N a t ha n a n d Rin t o ul Ioc c it , . .
 MANUFACT U RE OF NIT RO GLYC E RIN E
-

or other vessels where further separation occur red and might contin ue for a
,

month 1
.

Since the introduction o f good di stilled glycerine one cause of long separa ,

]
i ll
I
m
m u’
u

£533as m 3°
'5 2° 25 35 4° 45 5°
0 a s so 55 0 0 65 70 75 so as 90 9 5 I OO
SULP HURI C AC ID P ER CENT N'
I R 'C A C ‘D FER CENT

FI G . 44 FI G . 45

0 z 3 4 s c 7 e . 0 50 7o
10 20 3 0 40 50 1 90 100
W ATER PER CENT SUl PHURIC ACID PERCEN
T

FI G . 46 FI G . 47

FI G S. 44 47
—
. u t
So l b ili ie s o t ro
f Ni -
r
g ly c e in e in Acid s

tions has been eliminated and the source of the trouble is to be sought now
,

rather in the acids A large amo u nt of suspende d matter in the acids causes
.

the formation of numerous small dr ops of nitro glycerine which do not readily -
,

p ar t i c ulars o f t h is p r o ces s a nd it d i sa d vant a ges s ee 48 January 1 8 8 3

1 Fo r full s .
, ,

V OL . I . 15
 E X P L OSIVE S

coales c e and con s equently take a very long time to separate Hence the
,
.

impor t ance o f a llo w ing the a c ids t o stan d for some d ays af t er mi x in g in order
to allo w time for t he in s o luble impurities t o se t t le ou t These consist mos t ly .

of t he s ul pha t e s of lead iron and alu mini um But d u rin g the ni tra t ion proces
,
. s

a f u r t her quanti t y is precipitat ed mostly lead s ulphate whi c h is considerably , ,

less soluble in dil ute aci d t han in concentrated a n d t hi freshl y formed p r e c ip i

s ,
s

ta t e is pr o bably more inj urio u a s i t has not had time t o be convert ed int o s
,

larger aggregates The time o f separation in c reases wi t h in c rease in the

.

per c entage of w a t er in the w as t e aci d ; thi s is no doubt due par t l y to the

larger am o u nt of lea d s ulphate precipitated b ut ma y al o b e cau s ed part ly ,
s

by the retarda t ion of t he nitration reac t ion b y the pres ence o f t he w ater .

Just the s ame trouble wi t h long separati o ns is li able to oc c ur wi th the ni trator

s eparator or any other form of pla nt It is due to the format ion of an emul ion .
s

o f the one li quid in t he o t her and is in timatel y connec t ed wi th t he phenomena

,

o f sur fa c e t en s ion but t he ma t ter has not b een inve s tigated s uffi cien t ly to
,

a llo w of a f u ll and sati s factory explanation The forma t ion of an em ul ion .

s

can be prevent ed by t he addi t ion of vario u s substances t o t he charge ; t hus

y
R Moeller in Ger P a t
. . claimed the addi t ion of 0 0 5 to 0 2 per cen t
. .
- -
.

o f the w eigh t of glyce ri ne of va ri ous fa t t y s ubstances such as para ffin v ase line
.
, ,

t he higher fat t y acids and the ir esters The slo w separa t ions have a l o b een .
s

as c ribed t o t he presence o f sili ca t es a n d especiall y gelatin ous sili c ic aci d a n d ,

t he ad di tion of 0 0 0 1 per c en t of sodi um fluo ri de has been proposed to des t r o y

.

t hem 1
. The lVes tfa lis ch An hal t ische Sp r e ngs to fi A G in t heir Ger Applica
-
. . . .

t ion o f December 2 on the other hand claim the addi tion of a

,

small quan t ity of a sili cate such as kaoli n or t al c and t he Rheini sche Dynami t
, ,

fabrik ad d s both sili ca and hy dr ofluoric acid or SOdl l ll l l silico fluoride 2

The -
.

addi t ion of either pu ri fie d petr o leum or so di u m flu o ri de u ndoubtedl y accelerates

the separation and t he use o f these substances is e x tendi ng
,
.

C on ey a nc e of
v Before t he in v en t ion of dy namite and blas t in g gelat ine ni tro glyceri n e -

“ i tf fl ly cef ine was sent long di stances in the li quid s t ate The dangers involved led to .

numerous acciden t s as w a s inevitable I n Ameri ca Mo w b r a y froze the

, .
‘

materi al for the pur poses of transport but t hen i t had t o be tha w ed aga in ,

before use as it is too i ns en itive in the frozen state In E urope li quid nitro
,
s .

glyceri ne is now no longer used as such but in America i t is employed for ,

blo w ing o il w ells for w hi ch p u rpos e it has to be sen t by road as t he rail w ays
-
,

will not ca r ry it In t he w orks the pri nciple is ad opted of mi xin g i t wi th a

.

soli d substance at as early a stage as pos ible so t hat the quan t ity of liquid s
,

ni t ro glycerine is reduced to a minim um but u n t il i t has been full y w ashed

-
,

and mi xed it mus t o f co u rse be conve y ed fr om one ho u e to ano t her in t he

,
. s

liq u id state Thi s is somet imes done in closed t rucks or tr o lleys (see Fig
. .

1
Ea t n D yn a mite C o G e P t
s er C L Ree se A m P t r. a . . . , . a .

2 En
g P at. f J u.n e 1 2 1 9 1 2 ; Ge rm P at
o o f O c to b e r 10 1,
9 1 2 . . , .
 MAN UFACT U RE OF NIT RO GLYC E RIN E
-

In Germany the tendency is to revert to troll eys on account of the danger

of explosions being communicate d from one house to another by gutters
or pipes Where small quantities only have to be transferred as from the
.
,

after separating and wash w ater settling houses to the washing house covered
- - -
,

buckets of in dia r u b b e r gutta per c ha or papier ma c h é are used and these

—
,
—
, ,

are carried in the hand In E ngland the bulk of the nitro glycerine is how
.
-
,

FI G . 48 . ruc k
T fo r C o n ve y an c e of L iq u id N it ro gly c e rine -
, R e p a un o , U SA. . .

(B y p e r mis s io n o f E J d u P o n t d e N e mo ur s
. . Co ) .

ever caused to run from one house to another through open gutters which
, , t
Gu ters .
are usually m ade of lead P ipes are not suitable on account of the imp o s s i
.

b ili ty of inspecting or cleaning them properly All wash waters are also .
-

sent down open gutters to the wash water settling house as they carry globules
- -
,

of ni tro glycerine The fall of the gutters shoul d not be less than ab out 1
-
.

in 65 they should be free from sharp turns and from a ll inequalities in which
ni tro glycerine can lodge At the Royal Gunpowder Factory they are j oined
-
.

by butt weldi ng as thi s gives a much smoother surface than lap weldin g In
-
,
-
.

order to prevent the nitro glycerine from freezing in cold weather the gutter
-
,
228 E X P L OSIV E S

c o nnec t ing the ni tra t ing h o use w i t h the wa s hing hou s e is provi ded with an
o uter j a c ket (s ee section in Fig and w arm water is circulate d in this w hen
.

the o utsi de temperature is lo w The gutter i s pr o tecte d by mean s o f a c anvas

.

c o vering fi x ed along one e d ge a n d la c e d d own on the o ther s o that it can easily ,

be turne d ba c k fo r cleaning purpo s e s After a charge has been run d o w n .

,

the gu t ter is w iped along it s w hole length with a flannel in th e d irec tion o f
t h e w ashing house to remove any trace s of nitr o glycerine -
.

\Vhen the nitr o glycerine h a s been mi x e d with suffi cient gun c ott o n o r
- -

o t her ab s orbent material to ren d er it n o n liquid it is comparatively s afe

-
.

F1 0 . 49 . Eur o
pe a n N it r e -
g ly c e i rn e H ill s . Fo r c it e at B a e le nl Ve
-
ze l

(Fr b m F a b r i ca tio n des E pl x f

os i s , B ru s s e ls , 1909 )

Mi x ed material for the manufacture of cordite has been transported in

very large quantities over considerable distances without mishap W hen .

the ni tro glycerine factory at l Va lth a m Abbey near London was destr o ye d
-
, ,

by an explo s ion on Ma y 7 1 8 9 4 supplies were obtained from th e Nobel Fa c tory

, ,

at Ar deer in Sc otlan d i n this state until a new factory was bui lt Gun
, , .

c otton in the wet state was sent from l Va l th a m Abbey to Ardeer and was ,

there d ried and mixe d with the requi s ite quantity of nitro glycerine and -

ret u rned by sea and so the manufa c ture of cor dite at l Va lth a m Abbey was
,

n o t br o ught to a s tandsti ll Similarly w hen the nitrating h o use at Curtis s ’

.
,

and Harvey s w orks at Cli ff e in Kent was bl o w n up o n February 1 8 1 9 0 4

’

, , , ,

gun c o tton was sent from there to Waltham Abbey and was there converted
-
,

i nto mixed material and se nt back Messrs C urtis s a nd H arvey w ere thus . .
’
 MANUFACTU RE OF N I TRO G L YC ERI N E
-
229

enabled to carry out their Government contract for cordite which was urgently ,

required fo r the South Af rican War The D iin e b er g Factory nea r Hamburg
.
,
’

which makes the nitro glycerine smokeless powder for the Germany Navy
-

obtains a ll its mi x e d material from the neighbouring dynamite works at

Kr ummel which was the fir st nitro glycerine factory erecte d by Nob e l outside
,
-

Swe d en
.

Nitro gy lee r ine factories are often built on rising ground in order to pro
-

vide a fall from each house to the next with o ut having to make the nitrating

FI G 50 Am e rican N itr o g ly c e r in e
- -
H ill Ha s k e ll , US

mA
. . .
,

(Fro JV
’

p p leto n s I a ga z i n e )

house of great height With the nitrator separator however the di fference
.
-
, ,

of level between the top of the nitrator and the bottom of the wash water -

sett ling tank need not be more than 1 6 feet w hi ch can easily be pro v ided ,

for on a flat site One great disadvantage of placing a nitro glycerine fact o ry
.
-

on the top of a hill i s that it i s very likely to be struck by lightning a n d if ,

that occurs it does not seem that any sy s tem of lightning conductors however ,

c o m plete will prevent the explosion of the ni tro gly c erine and the c o n s e
,
-

quent total destruction of the buil ding There have been numerous cases .

of such c a tastrophes in Germany and South Africa In conse quence of .

this the d anger buil dings of the H o ppe c ke dynamite factory have been
 230 EX P L OSIVE S

buil t undergroun d in a hi ll and Bichel has put f rward simi lar proposa ls
, o .
1

That par t of the works in whi ch are situa te d t he buildin gs for t he manu
fact u re of ni t ro gly c eri ne a n d o t h er specially dangerou s opera t ions sh o ul d
-

be s epa ra te d from the rest by a fen c e a n d no one sho u l d b e a llo w e d wi t hi n ,

t he da nger area unless his duties ta ke him there .

P rovi sion must be made for the s t irrin g of the conte nts of t he ni t ra t or
Air s u pp ly . a n d the washi n g ta nks e tc in case t he air c ompressor shoul d fail Thi s
, .
, .

c a n b e done by having a la rge reservoir for compressed air wi t h an automa t ic

inl e t valve so that the c onte nts cannot e s cape in the direc t ion of t he c o m
,

pres s or A cylinder of hi ghly c ompresse d carbon di oxide or ni t rogen c a n

.

also b e used as a rese r ve it shoul d be pro vi ded with a reduc ing val v e a nd
a manometer or other appli ance t o show how much it c o nta ins
, , .

If a thunder storm pa ss over the factory all work must cease in dryin g
-

and mi xing houses and the men must retire to the mess room or other p la ce
,
-

of s afe t y In the ni t rating house no fresh charge shoul d be s ta r te d w hil s t

.

t here is a thunder s torm anywhere near All men mu s t leave t he building

-
.

e xcept one to look after the separation and one for t he ni t rator if a charge ,

be in the process of nitration If the sto rm becomes very t hrea t eni ng th ese
.
,

also shoul d leave afte r stopp ing t he operations Charge s in t he w ashi ng .

tanks may be left with the a ir tu rned on In Germany it is laid down t ha t .

t he electric light and power wires are to be di sc onnec t e d .

E very nitro glycerine house lik e a ll other danger bui ldin g s mu s t have
-
, ,

Li mi t b o ar ds .
a board in t he en t rance sho w ing t he maxi m u m num ber of wor kmen and t he
grea te st quan t ity of explosives t hat may be in it a t one t ime In Germany .

t he follo wi ng are t he greate st numbers of men a ll o w e d ex c lusi v e of c ar ri ers ,

N itra ting h u s e o

Se p ara t ing h us e o

ho us e
Afte r ~
se p a r a t in g h o u se

“ a sh w ate r ho us e
-

D e ni t ra t in g h us e o

t
Us e-lis s .
At the Royal Gunpow d er Factory l Va lt ha m Abbey U s e lis t s are a ls o , ,
-

pos te d up sho wi ng t he t o t al number of loose ar t i c le s t ha t are a llo w e d in

,

ea c h house This is a very valuable ins ti tution as there is no d oub t tha t

.
,

many acciden t s ha v e been c aused by the droppin g or fallin g o f s o me hea vy

implemen t o r by t he use of some u n s ui table t ool I t h a s been foun d po s s ible
, .

to limit t he n u m b er o f loose ar t i c les t o t hose w hi c h appear in t he Table gi ven

below These onl y are allowed
. .

I t nee d scarcely be sai d t ha t t he mos t s crupul o us clean line s s and t i din ess

1
19 1 0 , p . 18 2 ; C he m!a ch e I nd us trie
-
, 1 9 1 2, p . 139 .
 MANUFACT URE OF N I T RO GLYC ERIN E
-
23 1

must be observed in all ni tro glycerine houses An y nitro glycerine that -

.
-

may be spilt should be wiped up immedi ately with a flannel .

The men in the nitro glycerine section should have special clothes of a -

di ff erent colour from those of other danger bu ilding men There must be .

no p ockets The boots must be changed on entering a danger buil di ng ;

.

those worn inside must have no nails or others parts made of iron Keys and .

other implements that have to be brought near the buildings are to be made
, ,

of gun metal or other soft material

-
.

To destroy spilt ni tro glycerine H M Inspectors of E x plosives r e c o m -

. .

mend the use o a solution of 1 1b caustic soda in , 1b water to which is

f 1 1
. .

added a gallon of wood spirit or failing that methylated spirit 1

,
.

Nitr e glycerine can be exp loded readily on iron or steel by an iron imp le
- Sensitivenes:

ment but with som e difficulty only with a brass one or on brass with an
, ,

iron o n e Contrary to what might have been anticipated it is more di ffi cult

.

to explode a thin film than a layer of moderate thickness such as that formed ,

by a small drop It is very di fficult to exp lode nitro glycerine on sheet lead
.
-

placed on stone by iron or steel implements either by a di rec t or a glancing

blow .
2

U SE L I STS AT W
-
L
A TH A M AB B E Y .

W a s h in g W a sh - w a t er t
Fil e r in g a n d
H o u se H o use Mi x in g H o u s e

a
B gs , bbe ru
r
tt
B o le s , g u tt a p e r cha -

B uc k e t rub b e r
s,

C o v e r s b u c k e t g u tt a
, ,
-
pe r cha
Flann e ls
Gau nt le t s rub b r , e

G aun t le t s le a t he r ,

O v e rs h o es rub b r , e

So c k s
hr
T e mo me t ers

1
1 90 4, p . 62 .
2
AR . 1 9 0 2, p . 25 ; 1 9 0 3, p . 25 .
 C H A PTE R X V I I

LOW -FREE ZI NG NI TRO-G LYCERINE

Fr ee zin g o f t
ni r o - g ly ce r in e ex
p lo si ve s Eff ec t of a d di tio n s S peu r co o lin g
-

ni r o t di g ly
-
ee r in e D ini t r o z
g ly eo l Nitr o is o b u t y l g ly -
ce rin e nit ra te

ONE of the grea te s t dr awbac ks a t t a chin g to ni tro glycerin e explosives i s t he -

liabili t y of ni t ro glyce rine t o go soli d a t m odera t e ly low t empera t u res The

-
.

mel t ing p o in t of pur e ni t ro gly ce r in e i s 1 3 3 C or 56 F bu t it ca n often

- -
°
.
°
.

be kep t even in la r ge quan t ities for c on iderable pe ri o d at te mpe r atures muc h s s

below t hi s wi t hou t solidi fyi ng for i t sho w s in a hig h degr ee the phenomenon ,

of su p er c o oling In t he solid s t a te it is muc h les s s ensitive to t h e de t o native

-
.

eff ec t of ful mina t e and t hi s is a g rea t sour ce of da nger for frozen cart ri dges
, ,

a re liable to rema in in t he b o re hole part l y or en t irely un exploded and i n t he -

,

sub sequen t ope r a t ions t hey are very likely to be fired by a blow wi th di sastrou s
r esul t s \Vh e t h er fr oze n ni tro gl y cerin e i s more sensi t ive to blows than when
.
-

li qui d t he evi dence i somewhat con t r ad i c t ory H M Inspectors of E xplosives z

s . . .

t ried t he eff ec t of a fallin g w eigh t of 5 lb on li t t le cyli nder s of dynami t e Q inch .

d ia me t er and é in c h hig h pla c ed bet w ee n g un me t al di sc s and foun d t hat ,

-
,

where a s t he unf roze n ma t e r ia l w a s some t i me s expl od ed wi t h a fall of 30 inches ,

t he fr o zen dy nami te w a s never e xpl o ded wi t h a s ingle blow of the weight

fallin g 4 8 inches bu t a feeble explosion w a s pro duce d a t t he sec ond blow
,
.
.

La t er on fur t her e xperimen t s were ca r ri ed o u t w i t h o t her ni tro gly ce rine -

e xplosives ’
Thi n s lice s of t he explosive a bou t t he size of a shillin g and about
.

0 2
2 i nc h t hi ck were pla c ed be t ween b rass pla te s 1 inch square and inc h
t hick The sli ce t h u s s and w iched was place d on an anvil and a 58 lb weight
.
,
-
.

w a s a llo w ed t o fall on t he upper b r ass pla t e The c ri t i c al or p robable explodi ng .

po in t s un der t h e se c o ndi t ions we r e found to b e a b out a s foll ows

U nfr o ze n Fro ze n

B la s ti n g ge la ine t 12
'

,
4 to 8
f
I

The fi gur e s give t he n u m ber of fee t of fall of t he weigh t whi ch ca u s ed explosion .

Ka s t Hi b b e rt 8 t h 1 m C o ng
1
, S S . 1 90 6 p 225 ;
.
, , . Na u c kh o fi , S S . .
, 19 1 1 ,
p . 1 24 ; , .

Ap p . C ha n ,
vol iv p 3 7
. . . .
z
1 8 79 . AR . .
, 1 8 8 9.
 LOW F REEZI NG NI T RO GL YC ERIN E
- -
23 3
5

Th e dynamite was in slices about the thi c kness of a Sixpence It s iz e a nd

‘

was also found that frozen dyn amite was very liable to detonate when it was
ignited whereas the p la s tic material merely burnt away un der the same
condi tions S ome hard frozen blasting gelatine laid on a sloping board a n d
.

fired at with a rifle at 20 yards range detonate d p owerful ly whereas unfrozen ’

,

cartridges under similar condi tions di d not e x plo d e and cartridge s of the ,

explosive frozen only slightly were merely scattered .

On the other hand Wi ll 1

in falling weight and shooting experiments , , ,

found the frozen nitro glycerine explosives less sensitive in all c a se s The -
.

di fferences i n the case of the falli ng weight experiments were probably due
to the u se of very much smaller quantities of explosive by Will It i s the .

increase d resistance offered by the frozen explosives that makes them more
d angerous to ma ni pulate If a very thi n layer be used it i s the resistance .

of the supporting surface that comes into play and not that of the e xplosive ,

and when fired with a detonator also the hardness of the material has but ,

li ttle influence But miners have to do with whole cartridges o f explosive

.
,

a nd that these have special d angers i s shown by the accidents that occur in

spite of the warnings that have been issue d repeatedly and the regulations that
require the use of pr oper warming p ans Thus in the annual report of H M —
.
, . .

Inspectors of E xp losives for 1 9 1 1 the follo w ing cases are cited ,

'

No . 2, J a n . 4 . Ma n inj u
t ramming ho m a fr n c harge o f g e li gni t e r ed w hi ls e o ze .

No 32 J a n
. 16 A m n in e r t e d an iro n s p i k e in t o a c art rid g
, . . f Sa ms ni t e
a s e o o

p r p ara t o ry t
e a tta hi ng th e d e t o nat o r Th cart rid ge w a s p ro b ab ly fr n Tw
o c . e o ze . o

in j u e d
r .

No 3 5 Jan 3. M n inj u d b r e akin g a fr o n cart rid ge o f Sa m o ni t in t w b y

, . . a re ze s e o

hand .

N 66 J n 4
o . A lab o u r e r w
, a . ab o u t t harg e a h t h l w h n h f ll a nd kno k d
. as o c s o -
o e e e e c e

th e ex
p lo ive a g ain t t h e r c k
s App ar e nt ly t h g lig nit
s h d n o t b e n t haw e d u ffi
o . e e e a e s

c ie n t ly h d b e c o me hard a ga in
or a M n in j u e d . a r .

No 92 Ma . 22 A ma n w a s in th e a c t f b r e a king a fr e n g ligni t e car trid g wi t h

, r. . o oz e e

hi s hand s w he n it e x p lo d e d Tw o in j u d . re .

No 10 6 Ma . 10 W hi ls t a min r w a s hand lin g a o n g ale d g e ligni t c art ridg e it

, r . . e c e e -

ex p lo d ed a nd i n jur ed him .

No . 1 1 7, Ma r 25 A mine r
. . d ro pp ed a hard ge li g ni e t ca r tridg e on a tram ra il -

a nd it exp lo d e d . On e in j u re d .

No . 1 1 9 , Ma r . 25 . A charg o f un d o u b t d ly hard fr e n Sa m o n it e e p l d e d w hil t

e e o z s x o s

b e in g ra
mm e d o me h w i t h a w o o d en a mm e r Tw o in j ur e d r . .

N o 1 58 Ap r 1 1
.
, . . A charg e man w ma k in g a h l f a d t nat r in a Rip p ite c rt
a s o e or e o o a

r hn
id g e w e it e x p lo d e d . App a n t ly t h c ar trid g e h a d b n ath r h ard a n d h r t d
re e ee r e , e es e

it o n t h e g r o rui d a n d w a s
pr ing kn
ess kin g t h p int d
o r nd f th t l n ipp
oc in t o e o e e o e s ee ers

it . On e i j ed. n ur

Similar c ases have occurred i n other years but not always with the same ,

1
Ze its . B erg .
, H ittten -
u. S a li n en w es en , 1 90 5 .
23 4 EX P L OSIV E S

fortunate absence o f fatal inj ur ies C Herlin has carried out exp eriments . .

in which the con di tions of some o f these accident s w ere repro duce d more
c losely He d ropped ball s of explosive weighing 40 t o 1 1 0 gramme s from
.

v a ri ou s heights up to 1 2 3 metres on to an ir o n plate Fr o zen e xpl o s ive s .

w en t o ff every time if the quantity and the length of d rop w ere suffi cient ,

but partly thawed balls never exploded and presumably t he unfr o zen materi al ,

did not either 1

.

The following Table sh ows h ow certa in classes of ac c ident are much more
frequent at those t imes of the year when ni t ro glycerine i s li able to be frozen -
.

Onl y those acci d ents i n whi c h an e x plosive c o n t ain ing o ver 1 0 per cent of .

nitro glycerine was involve d are shown here

-
.

J a n Fe b
. . Ma r Ap r Ma y J u ne
. Au g Se p Oc t No v
. . . .

Ra mm i n g or s t e mmin g harg
c e 4 1
r nt
B o i ng i o i ni e x
p lo d e d c h rg a es 2 1 2 1 1
tr un
S i ki n g ex
p lo d e d c harg in es

r m vin g
e o d e b is r 1 1

To t a lofab o v aue c ses , 1 9 14 2 2 2 3 1 2 1

To t a l in p a s t 1 4 y ea r s 75 91 94 58 39 29 16 26 21 34

In a ddi t i o n to t hese there were up to the end of 1 9 1 4 1 1 0 accidents in thawing

cartri dges o f frozen n itro glyce ri ne e x pl o sives c ausing d eath to 8 5 persons
-

and inj u ri es to 1 43 other s It i s true that all e x cep t one of t he s e a c cident s

.

would have been av o ided if the explosives h a d been t ha w ed i n t he regulati o n

,

manner The one exception was due to the thawing o f s o me unstable e x p lo

.

sive the heat test of which h a d been masked by the addition of mercuri c
,

chlori de .

The s e s pecial danger s a nd the tr o uble i n having to keep the e x pl o sives

in heate d magazines d uring cold w ea t her or of tha w ing them and keeping ,

them thawe d up to the time of u sing them as well as the great d i fficulty in ,

preventing t he workmen thawing them i n an irregular manner has cau se d ,

endeavours t o be ma d e t o manufa c t ure nitro glyce ri ne e x plo s ive s whi c h will -

not freeze so readi ly Fo r thi s purpo s e u s e is ma d e o f t he fact that when a

.

substance is di s s olved i n a li qui d t he freezing point is depres s ed i n ac c ordance -

1
S S
. .
, 19 1 4, p . 3 90 .
 LOW FREE ZI NG -
N I T RO GL YC ERI NE
-
235

wi th the e quation A r: E in which A is the d epression of the freezing

point produced by the addi tion of m grammes of a substance of molecular
weight M to 1 00 grammes of the solvent and E is a constant which represents , ,

the depression produced by 1 gramme molecule I t can be calculated by the -

.

2
fo r mu la E :
is the gas constant ( T the absolute
i n which R z

temperature of the freezing p oint and W the latent heat of fusion As early -
.

as 1 8 8 5 Nobel p atented the lowering of the freezing p oint of nitro glycerine — -

by dissolving other substances in it 1

.

The behaviour of nitro gly c erine when cooled was investigated b y Nauck -

hoff and was found by him to be quite normal He determined the latent
2
, .

heat of fusion as 23 1 cal per gramme and hence E

3
70 5 The following .
,
-
.

Table gives some of the depressions of the freezing point observed and c a lcu -

lated by Na u c kh o ff :

D e p r e s s io n of Fr e e z in g
p o in t
S ub s t a nc e D is s o l ved

Ob s e r v ed C a l c u la t ed

Nit ro -
b e n ze n e

D rn itr o b -
e n e ne
z

r
T in i t r o b e n ze ne -

D ini t r o t o lue ne
-

D ini t r o nap h t hal ne

-
e

Na u ckh o ff also determined the freezing ,

or rather melting p o ints of a -

number of mixed explosives

F re e zin g -
po i nt

r e n ch P a t o f Ju ly 24
1 F 18 8 5
.
2
A ng , . .
, 1 9 0 5, p p . 1 1 , 3 5 .

3
H H ib b r t a n d G P Ful l r fo u nd th la t n t h a t to
. e . . e e e e b e 33 2 c a l . p e r g ra mm e or

7-54 ca l
p . mo l (J Am C h m S o
er 19 13 p
. . . e . c ., , .
93 6 EXPL OS I V E S

N it r o g ly c e r in e
-
50 50 50
N it r o c e ll ul o se

Am mo ni u m N it ra t e 35 40 34 40 40
N it r o b n n-
e ze e

D ini t r b n n o -
e ze e

o N it r
-
t lu n o - o e e

p N it r t l no o ue c
- -

N it r n p h t h l n
o -
a a e e

o Nit
-
p h n
ro l -
e o

An ilin e

F r ee zi ng -
po i nt 64
°
4
°
6
°
14
°

Th e freezing p oint o f t he nitr o gly c e ri ne u s ed fo r these exp e ri men t s w a s ab o u t

- —

Ta king in t o acc o un t t hi s fac t a n d t hat t he la w of t he depre s s i o n o f ,

t he freezing poin t i s s t rictly true only fo r di lu t e s o lu t i o ns t he figur e s f o un d

-

agree fairly well wi th those c alculate d The lo w freez ing p o int of t he o riginal .
-

ni t r o glyceri ne w a s du e of c our s e to t he pr e s ence o f some imp uri t y in t he

-

ni t ro glyce ri n e pr o bably dini tro gly c erine of w hi c h abou t 8 p e r cen t w oul d

-
,
-
,
.

be require d to produce thi s depr e ssion Na u c kh o ff consi de rs t hat 1 0 5 i s .

-
°

t he normal freezing point of c o mmer c ial ni t ro glycerine but t hi s no doub t

- -
,

depends upon the c o mposi t ion o f t he a ci d u s ed a n d the propor t ion of aci d

t o gl y c erine There is no doub t t ha t much of t he ni t ro glycerine manuf a ctured
.
-

alm o s t pure t ri ni t ra t e a n d freezes n ear

The mel t ing poin t s of ni t ro glycerine dini t r o c hl o r h y dr in and mi x tures
- -
,
-

o f t hem w ere d e t ermine d by Ka s t : 1

Me lt in g -
p o in t
Ni t ro -

g ly ce r in e t
D in i ro -
c h l o r h y d r in

Ob s e r v
ed

Kast also g iv e s th e freezing p o int s but as the li qui d s were c o o led c on -

.

si derably bel o w th e t rue freezing p o int s b efore being i no c ul a te d w i t h a -

cry s t al t he c o m po s iti o n h ad been al tered by t he s eparati o n o f c rys t alline ni t ro

,

glyceri ne before t he t empera t ure rose to a m a x i mum a n d t hi s c o nsequen t ly ,

1
S S 1 90 6. p . 225 .
 V FRE EZI NG
L OV -
NIT RO GLYC E RIN E -

di d not correspond with the true freezing point w hich is of course identical -
, , ,

w ith the melting point Kast observe d that nitro glycerine c a n also crystal
-
.
-

”
li ze i n another or labil e form the melting point of which is more than
“
,
-

1 1 below that of the sta ble f orm Freezing point determinations were also
° -
.

carried out w ith mixture s inoc u lated wi th crystals of this form

Me l t in g -

p o in t
N i tro g ly c e r in e
-
D in i t ro -
e h lo r h y d r in
Ob se r v ed C a lcu la te d

A di fferent sample of di nitro chlo r h y dr in was used for this series -

.

Nitr e gly c erine preparations do not necessarily go soli d when the tempera
-
Sup e r
c o oli ng
tur e is reduced below the freezing point on the contrary they can often be -
,
.

kept for months at a te mp er a tm e considerably lo w er wi thout solidifyi ng ‘

This propert y of super cooli ng is intimately connected w ith a slow rate of

—

crystalli zing w hen solidi fication does start and this aga in appears to b e
, ,

related to high vi scosity Th e rate of crystallization of a given substance

.

depen ds also upon the te mperat ur e ; as this is reduced below the freezing -

point the rate increases at fir st reaches a max imum a n d then falls again , .

Na u ckh o ff gives the follo wi ng Table 1

Su b t
s a n ce Te mp e r a t u re Su p e r -
c o o l in g
Ra t e o f crys a t t
ll i z a io n
per m in

G ly cerine
N it ro gly ce
-
r me

ma x im

The rate of crystalli zation is further re d u c ed ,

if t he n itro glycerine is
—

1
An g .
, 1 90 5, p . 1 6.
 E X P L OSIVE S

gela tini z ed w ith c oll o di on but if it is absorbed i n kieselguhr its tendency to

,

crystall ize is increased When a cartri dge of a nitro glycerine e x plosive has
.
-

once been frozen it has a much greater tendency to become h ard agai n as
,

soon as th e te mp e r a tu r e fall s below the freezing point Thi s i s probably due -

.

to the separati o n of gl o bul es of practi c ally pure ni tro glycerine which onl y -
,

mi x again with the impurities and other con s tituents very s lo w ly .

The first attempts to reduce the freezing point of ni tro glycerine were - —

w ith nitr o benzene

1 -
and nitro t luene
o
2
U nfortunately they not o nl y reduce -
.

the sen s itiveness of the expl o sive a diffi c ulty tha t can be overcome by the ,

use of a stronger detonator but also di minish the power and the velocity of ,

d etonation For blasting har d rock these dr a w backs are of the greatest
.

importance but fo r safety explosives for u s e in coal mines etc far less so
,
-
,
.
,

i n fact it is necessary to reduce the po w er and the velocity of detonation in

order to make the explosive safe and for blasting soft rock too high a rate ,

of d etonation is undesirable Hence various nitro hydr ocarbons are used .

-

as constituents of many safety explosives In o r der to reduce the freezing .

p o int to any great extent it is necessary that the proportion of di ssolved

substa nce to nitro glycerine sh o uld be fairly high and the greater the m ole
-
,

c u la r w eight of the ad dition the larger mu s t be its proportion B ut sub , .

stances o f very low molecular w eight cannot be used because they are volatile .

Therefore in order not to reduce the efficiency o f the explosive too much it
, ,

is desir able to add some substance that is almo s t a s eff ective an explosive as
nitro glycerine There are a number of substances closely a llied to trinitro
-
.

glycerine whi c h can be used

,
.

0
Methods for the manufacture of dinitro glycerine have been devised b y -

Mi kolaj czak 3
and the Zen tra ls telle 4
Will has pointed out that di nitro .

glycerine i s liable to go so lid at quite moderate temperatures and that it ,

has the further di sadvantage that it combines w ith water of crystalli zation ‘

i s soluble in water and acids and some w hat hygroscopic To what extent .

these troublesome qualities disappear when it is mi x ed w ith several times

its weight of trini tro glycerine there is no published evi dence to show but
-
,

the results of experience with this substance in France do not appear to have
been very favourable 5
.

Dini tro chlo r h y dr in is easier and cheaper to prepare and pur ify and i s
-
,

no w used to a con s iderable extent for reducing the freezing point of -

e x plosives It mi x es wi th trinitro glycerine i n all proportions and gelatinizes

.
-

c o llo di on cotton equall y we ll As regards power Ro e w er found that there .

,

1 u r
B d b e g , Sw e d P a t , Ap il 30 , 1 8 66. . r .

2 n
Vo l e y , Am P a t , M c 5 1 8 72 ; V a h le nb e r g
.
V
. ar h , a nd un d tr o m Sw e d
S s , . Pa t . 1 8 77.

3
Am P s . ato f Se.
p e mb e 1 1 , 1 90 6 e is s e t r , r u o f Jul y 2 1 90 7 , , a nd 8 30, 90 9
of January 26, 1 90 9 .
4 G er . P ats . an d .
1 75, 75 1 .
5
S ee Ve nn i n , P o ud rcs ct E x p lo s ifs , p . 3 67.
 L OW FRE E ZI NG -
N I TRO GLYC E RIN E -

wa s li ttle di ff erence between explosives made with ni tro glycerine alone and -

tho s e made w ith a mi x ture i n whic h 20 per cent o f the nitro glycerine had .
-

been replaced by dinitro c hlo r h y dr in In the foll o wing Table the columns -
.

marked A are those obtained with the nitro glycerine e x plosives and B those -
,

with the mixtures of nitro glycerine and dinitro chlo r h y dr in - -

G uh r d y na m i t e t
B la s in g g e la in e t G e l ig n i t e

Tr a u z l Te s t , c .c. 30 1 555 54 1
a t
B llis ic P e n d l m uu , kg . m . 75 9 1 1 1 -4 1 1 1 -4

The calorimetric figures calc u lated for 65 per cent gelatine dynamite .

(63 per cent n i tro glycerine.or mixture 2 per cent

~
collo di on c o tton 26 per , .
,

cent so di um nitrate and 9 per cent cell ulose ) also give simil ar res ul ts
.
,
.

H eat e vo lv d e p e r kg .

Te mp e ra t u re of x E
l
p o s io n
G p r o d u ce d
as p er kg .

Dinitro c h lo r h y dr in is a constituent of the follo w ing explosives authorized D init o

-
r

chl o h y drin r
fo r transport by rail in Germany : Gelatin As tr a lit Gelatin W e tter a s tr a lit
.

, ,

G elatin Donarit Gelatin W e s tfa li t and P e r ili t

, , .

In order to make a mixture o f nitro gly c erine and nitro c h lo r hy dr in the - -

,

c h lo r h y dr in can be mixed w ith the glycerine and the mi x ture ni trated and ,

washed i n the usual way .

Di n itro c h lo r h y dr in is practicall y insoluble in acids and water and is not

-
,

hygroscopic but has the di sadvantage that on e x plosion it gives o ff hydr o

,
"

chlori c acid which makes it unsuitable fo r use un d erground unless suffi cient
, ,

of an alkali nitrate or other c o mpoun d be added to convert a ll the c hl orine

into an inorga ni c chlori d e This di fficulty d o es not occur if the third o x ygen .

atom in th e glycerine molecule be c o mbined w ith the radicle of an organic

acid instead of c hl orine Vender has found that the acetyl a n d formyl deriva
.

tiv e s mono acetin and mono formi n can be ni trated and give a good yield
,
- -
, ,

provi ded that the mixed aci contains more nitri c than s phuric acid
d ul 1
.

Dini tro acetin -

,
he says can be obtained wi th a D initro ,

etm
yield of 9 5 per cent by nitrating 40 parts o f acetin with a mixture of 1 00
.
ac ‘

part s nitric a c id and 25 of 25 per cent o leum Dinitro formin may be made Dmitr i)
- -

“ mm
. .

b y heating 1 0 0 kg glycerine w ith 50 kg o x ali c acid first at 1 0 0 and then

° “

. .

1
G er . P ats . of Ap ril 27 1 90 6 , , a nd S S . .
, 1 90 7, p . 21 .
 E X P L OSI VE S

at t o 1 50 and t hen ni t r a t ing The product has a specific gravit y of

14 0 .

1 57 con t ai ns 1 5 7 pe r cen t N and c onsis t s of 3 3 per ce n t dini t ro formi n

-
,
. .
-

and 67 per cen t ni t r o glycerine I t is unf r ee za ble a n d gela t ini zes coll o di on
.
-
.

a s w ell as if not b e t t er t han ni t r o glyce r in e -

.

By t rea t in g i t in various w ays glycerine can be condens e d to di glycerine -

2C H O 3 H O s , ) O and t hi
, on ni t r a t ion yields 2 , . s

a t e t ra ni t ra t e O-
whi ch r educes t he freezing poin t of ni t ro glycerine
‘ 13,
- —

j u t as t he o t her subs t a nc e s t ha t have been men t ion e d The form ation o f

s .

di gly c eri ne w a s s t udi ed in t he Ze nl ra ls ld le and it w a s found that t he co n

-
1
,

ve r ion w a s bes t e fl ec te d by heat al one By hea t in g gl y cerin e for seven or

s .

eigh t hour s a t 290 to 29 5 some 60 per c en t o f di gl y cerine is form ed t o ge t her .

-

wi th 4 t o 6 per c en t of p oly gl y ce rines The con t ituents ca n b e se pa r a te d by

.
-
.
s

di s t ill a t ion a t a pres u re of 8 t o 1 0 m m According t o E ng P a t s . . .

of Oc t ober 24 1 9 1 0 t aken ou t b y Nobel s E xplosi v es Co Rin t o ul and

'

. . .
,

A G Inn es t he c o nversion i bes t eff ec t ed b y heati ng at a temperature o f

. .
,
s

4 5 t o 250 in a cur ren t of in ac t i ve gas such a s ca rbo n di oxi de whi ch carri es

2 ° °
,
,

a w a y t he w a t er form ed and keeps t he liqui d in a s t a t e of agi t a tio n , .

C la es s e n in Eng P a t 9 572 of 1 9 0 8 claims t h e u e of a small proport ion

. . .
,
s

of alkali : b v hea t ing t o 275 t o 28 0 wi t h 0 5 per cen t the co nversion is ° ° -

.

effec t ed in a compara t ivel y shor t t ime .

P u re di gl y cerine boil a t 24 5 t o 2 5 0 1mder a pres ur e of 8 m it is °

- s s .

a colour les s w ee t li quid read il y soluble in w a t er i t s spec ific gravi t y is 1 3 3

s
,
-

and i t is ele v en t imes more vis cou t han glycerine Te tr a ni tr o di glyce rin e s . f
- -

v ery s imil ar t o ni t r o gl y cerine A mi xt ure of glycerine wi th about 25 per

-
.

cen t di gl y cerin e ca n be ni t ra t ed in t he sa me w a y a s gl y cerine al one and

.
-
,

t he produc t is un freeza ble Guhr dynami t e m a d e wi t h such a ni t r o gly ce .

-

prod uced a s grea t an e fi ec t in t he lea d block a s o r din a rv dv na mi te .

Di ni t r o gl y col CH N O CH NO is used b v t he Socié t é anonyme d E x p lo

'

-
, ,. , ,
sh eo l.
sifs e t de P r o d ui t s chi mi ques 3
I t s po w er ac cordi ng to c al c u la t ion is 4 per .

cen t g rea t er t han t h a t of ni t ro gl y ce r in e In t he calor imetric bomb t he

.
-
.

resul t s ob t ained in di ca t ed a superiori t y of 8 t o 20 per cen t accordi ng to t he .

me t h od of in t erpre ti ng t he res ul t s b v t he lead block t e t t he resul t s were '

a bou t equ a l The Socie t e s t a t e t ha t a t the pres en t hi gh pri ce of glyceri n e

'

ni t ro gl y col can b e made a t a cos t no t much grea ter t han that of nitro
-

glycerine I t is more vola t ile t han ni tr o gly cerine ; its specific gravity is
.
-

1 49 6 a t 1 5
-

If ni t r o me t h ane b e mi xed wi t h 4 pa r t s of 40 pe r cent for mal dehyde and

-
. ,

a li t t le po t as s i um c a rbona t e or bicarbona t e b e a d ded co ndensa tion t a kes ,

t t
ni ra e. pl a ce wi t h t he form a t ion of ni t r o isobu t y l gl y cerine NO C H 3 E CO B - -
z , .

NO C (C H 2 a cry s t a lline subs t ance rea d ily soluble in w a t er and alcohol

.

1 2
Sec “ i ll , 1 90 6, p . 23 1 . P . “ S 1 6, 1 9 1 1 1 2 p —
, . 72 .
 L OW FRE EZI NG NIT RO GLYC E RIN E
-
24 1

but less soluble in ether It melts at 1 58 to . I f this be purified

° ‘

by recrystall ization and then ni trated with mixed acid the trinitrate ,

is formed a li quid of specific gravity 1 68 and very low

2
,
-

freezing point At present it is not of practical importance on account of

-
.

the high price of nitro methane but if an inexpensive method of makin g this
-
,

could be devised it could b e used commercially

, .

1
H n ry C omp t
e , . Ra nd 1 8 9 9, I p 1 1 54
.
, . .

2
F E Ma tt he w s
. . , rt
B i . P a t 6447 o f 1 9 14 H o fw imm er ,
. 1 9 12, p .

VOL . I .
 P A RT V I

N IT R O A R O M A T I C
-

CO M POU N D S
 C H AP TE R X VI I I

BY-PROD U CTS OF C OAL DI STI LL ATI ON

Ar o ma t ic co mp o un d s t a t io n o f c o al C o al t ar N o me n cla t u r e
D is ill -
Be n zo l

f ro m ga s t a t io n
D is il l of co a l t ar T o lu n e fr o m p e t r o le u m
e C ar b o lic Ac id
P he n o l fr o m b e n e n e z Nap h t hale n e Y i ld s e

VE R Y great and increasing use is made of the nitro derivatives of aromatic A o ma ti —

r c
c o mp o un d s
substances as e x p losives and in the preparation of composite explosives .

The principal but not exclusive source of the aromatic compounds is the
, ,

destructive distill ation of coa l .

When comple x organic materials are submitted to destructive di stillation D i till ti n s a o

f coa l
they yield as a rule three classes of products soli d liquid and gaseous Of
‘

O .
.
,

the products from c oal the gas and solid (coke ) are used a s fuel The li quid .

products are ammoniacal li quor and tar obtained on cooling the gas and ,

scrubbing it U ntil recently ammoni acal liquor was almost the only source
.

of ammonia but it is now meeting severe competition from synthetic ammoni a

, ,

fo r whi ch see Chapter VIII .

The quantity and composition of the tar naturally depends up on the Co a l ta - r.

sort of coal carbonized an d the temperature a n d t y pe o f the retorts The .

higher the temperature the greater is the yield of gas but if the temperature ,

be very high the y ield of tar is less a n d there is in it a smaller proportion of

,

the simpler aromatic c ompounds such as benzene toluene and phenol In , , .

the large gasworks there has been a tendency to carbonize at higher tempera
tures than was formerly the practi c e a n d consequently the tars pro du c e d ,

have not been of as great value as those from small country gasworks The .

mo dern continuous vertical retort however yields a consi derable quantity , ,

of goo d tar The quantity of tar varies from about 4 to 1 0 per cent of the c oal
. .

and averages about 5 per cent it contains generally less than 1 per cent
. .

each of benzene and toluene The composition of coke oven tar is similar
.
-
,

but varies between wide limits .

Coal tar is a thick black li quid of specifi c gravi ty 1 1 to 1 3 It is a very -

.

complex mixture from which va r iou s valuable constituents can be separated

by fractional d istillation combined with treatment wi th c hemi c als Ow ing .

t o the complexity of the mi x ture only those substances are as a rule separate d , ,

in a state of c omparative purity on the c ommer c ial scale whi c h are present
i n the large s t pr o porti o n s or which pos s ess some physical or chemical pro
,

perty which facilitate s their i solation Of these sub s tances the mo s t i mportant
.

245
 E X P L OS I VE S

a re the aroma t ic hy drocarb o ns be nzene t o luene naph t halene a n d ant hra c ene
, , , ,

a n d t he aroma t ic alc o hols phen o l o r c arb o li c a c i d and c re s o l o r c resyli c a c i d

, , .

All t hese are use d in the manufa c t ur e o f s yn the t i c dy e s t u ffs d ru gs e tc -

, , .
,

a n d to luene benzene phenol a n d naphthalene are al s o u s ed in the manufact u re

, ,

of ni t ro e x pl o si v es especia lly t oluene and phenol Hen c e t he demand for

-
, .

t hese s ubs ta nce s is somet ime s di ffi c ul t to mee t espe c ia lly in t he ca s e o f t oluene

-
, .

Benzene and naph t halene o n t he con t rary are o b t ained in abun dant
quan t i t ies The followin g are t he mel t ing and boili ng poin t s o f t he p rin c ipal
.
-

subs t a nces in coal ta r :

Su b t
s a n ce

No mencla tur e
. The aromatic hydrocarbon C H 6 w a s formerly called benzol or benz o le but
,
~
t, , ,

in scien t ific E nglish i t s name is n o w benzene the termination o l being rest r icted ,
-

t o bo dies of the nature of an al c oh o l and contain ing a h y dr oxyl group (OH ) The .

name be nzol is applie d commerciall y to volatil e di s t il la te s obtained b y t he de -

s t ructi ve di s t illation of c o al and rec t ifie d so as t o boil bet w een abou t 8 0 a n d

°

The nex t hydr ocarb o n of t hi s s eries C H C H has similarly had its name al t ered
, S S. 3,

from t oluol t o t oluene Di fferent gra de s o f benzol are di s t ingui s he d b y t he per

.

c en ta ge whi c h di s t ils o ver belo w 1 00 C from a plain s till or re t or t w i t h o u t a

°
.

dephlegma t ing c olum n t hu s 9 0 per cent benzol is a li qui d of w hich 9 0 p e r c en t

, . .

di s t il s o v er be lo t he b oi ling p oin t o f w a t er Acc o r ding t o Kraemer

w -
a n d Spilker
.
1

t he fo llo wi ng are the mean c ompo s ition s of t he benzols u s e d in c o lour w o rks

90 pe r ce n t . 50 p e r ce n t .

Be n z o l Be n z o l

1
Mus p r a t t , H a ndb uc h de r te ch n is c he n C he mac 4t h -
, ed .
, 8 , pp . 33 c l s eq .
 BY PROD U CTS OF -
C OAL DISTILLATI ON
Benz ine is a volatile distil late from petrole um having about the same range
of boili ng points as benzol It consists mostly of hy d ro c arbons of the paraffi n
-
.

and o le fi ne series In German benzene i s still calle d benzol ; in French it

.

i s sometimes called benzine .

The alcohol correspondi ng to benzene is p henol C H OH U n like ordinary , G s .

alcohol it has deci d e d aci d properties a n d i s often called carbolic ac id but

this ter mlike benzol i s more generally applied to c ommercial products
,

”
.
, ,

containing other sim ilar substances and impurities as well as phenol .

The quantities of benzene and toluene contained in the tar are however , ,

small compared with what is carrie d away in the state of vapour in the gas .

Thus Bunte found that at the Karlsruhe Gas W orks the products from the
di still ation of 1 00 kg of coal contained : .

Con t a in in g

P r im a r y P r o d u c t s
Be n z e n e To l u e n e

Very large quantities are now recovered from coke oven gas especially in -
,

Germany by scrubbing it w ith creo sot e or ant h racene oil The removal of
, .

the benzene a n d toluene from coal gas destroys its illuminating p ower when
burnt i n a fi s h tail burner and reduces its calorifi c power If these hy d ro
-
, .

carbons b e rem oved from gas for town suppli es it is necessary to reintro duce
the greater part of the benzene By usin g a mml mu m of washing oil it i s .
,

however p ossible to remove a c onsi d erable amount o f the toluene with very
,

little benzene w ithout seriously interfering w ith the quality of the gas The .

volatil e products are di sti lled off from the washing oil by means of live steam
or by heat alone The distil late is separated fr o m the accompanying water
.

and fractionated .

The tar is first freed as far as possible from ammon iacal li quor a n d is
1
,

then fractionally disti lled from an iron boiler fired directly the products being ,

separated either into four or five fracti o ns The fol lowing are the fractions .

Cr ud e nap h t ha
°
I u
p t 1 10 o

II Li gh t o il 1 1 0 21 0 —

III C arb lic o il o 210 240 —

I V H a vy o r o t il
e 240 270
r c e so e o —

V An t h ra ce ne il ab v 270 o o e

1 h a cco u n t
T is o f al t ar d i t illati o n i t a ke n ma in ly fr m Th rl l
co s s o e /
a n u a c tu r e o f Or ga n i c
D ye —
s tu fis , by A . i Va h I t ran s la te d b y F W Att a c k (B e ll
,
. . So ns ,
 E X PL OSI VE S

up to 1 50
°
t
d e n s i y less t ha n 1
1 50 210 —
mo re 1
210- 28 0
a bo v e 300

The resi due remaining in the s till i s pitc h a t hi ck bla c k ma s s which sets
,

pra c t ically t o a solid The naphtha is separate d from the wate r whi c h pa s se s
.
,

over with it and i s agitate d fi rst wi t h dilute sul phuric acid to remove basi c
,

substances and then wi th concentrate d sul phuric acid to resi nify the un sa t u
,

rate d hydr ocarbons a n d absorb the sul ph ur c omp ounds such as t hi ophen , .

Af te r washi ng twice with caustic soda and then wi th water the li q ui d i s again
fractionally dist ill ed preferably t h rough a good dephlegmatin g col u mn similar
,

t o that s hown in Fig 69 (p givin g b enzols and solvent naphth a On

. . .

redi still in g t hese give more or less p u re hydrocarb ons : ben zene t o luene , ,

x ylenes , e tc w hi ch generally have still to be further purifi e d

.
, .

The light oil i s di stil led a n d separated i nto two portions : the frac t i o n
up to 1 70 is added to the naphtha and the other is added t o t he c arboli c
°

oil which i s worked up for phenols and naphthalene

,
.

The heavy oils are u sed for i mpreg natin g wood burning fo r heating purp o s e s , .

for lighting a n d for the production of lamp black etc They are also hea te d -
, .

for the production of illumi natin g gas a nd o f more valuable

hydr ocarbons On leaving to crystallize anthracene oil gives crude anthr a
.

cene and on redi st illing the oil gi ves a f u rther yiel d of anthracene Thi s i s
, .

pu ri fied by pressing washin g w ith creosote oil subliming and re c rysta ll izing , .

I t is used for t he manufa c t ure of numerou s dye stu ffs -

.

A c c o r ding t o Lunge the distillation of a t on o f coal tar yi el d s on an average

Amm o ni aca l li q uo r
Nap ht h a
Lig h t il o s

H a vy o ils
e

Pi tc h

The treatment of the tar i s outlined in the di agram on the next page .

Tolu ene fr o m Aromati c hydr ocarbons are present in petroleum s obtained i n variou s
t
p e r o l e u m.
parts o f the world but the publi shed inf ormation about thi s i s some w ha t
,

contradi ctory It has been demonstrated by W F Rittman a n d T J

. . . . .

Twomey of the U S Bureau of Mines that if petroleum be heated under

. .

pressure to temperatures of 550 C and upwards c onsi derable quan t i t ie s o f

°
.

aro mati c hydro carbon s are formed T o luene and xylene are apparently .

u c e d m o s t easily Benzene requires m ore strenuou s crac ing a n d its

'

p r o d . k ,

f o rmation reaches a ma x imum at a point w here toluene and xylene have

a lready fa llen o ff con s i derably Naphthalene begins to form at abou t t he
.
 EXP L OS I VE S

p oin t w here the toluene and xylene conte nt is at a ma ximum indi cat ing that ,

i t is probably fo rme d by the c on den s a t ion o f t w o m o le c ul es of a mono c yc lic

hy d rocarbon Anthr acene is f o rmed under similar c o n ditions t o naph t halene
.
,

but requi res even more severe hea t in g The pr o d uc t ion of t oluene was in .

s o me cases 4 per c ent of t he original pe t roleum a n d 1 8 per cen t of t he cracke d

. .

o il .U n d er manufac t uring con d i t i o n s i t w o u l d perhaps be p os s ible t o obta in .

c o nsiderably be t ter yiel d s Thi s pro c e s s is being d evel o ped commer c ially
1
. .

W A Hall heats pe t roleum pro du c t s t o about 60 0 C in o rder to obtain

. .
°
.

m o tor sp irit It has been fo un d t hat t he product s o me t ime s c o ntains a s

.

mu c h as 1 0 per cent of toluene a n d 8 per cen t of benzene 2 . . .

Ca r b o lic acid
. The fra c tion collecte d as c arboli c oil con s is t s mainl y of naph t halene and
phenoli c substances The oil is r u n into t anks and a llo w ed to c o ol do w n
.
,

whereup on 25 to 30 per cent of naphthalene crysta llizes o u t The oil sepa . .

rate d from thi s has a specific gravity of about 1 0 0 25 and contain s 25 to 30

per cent of phenols It i s first concentrated by r e di s tilli ng it preferably
. .
'

through a d ephlegmating c olumn F irst some cru d e benz o l comes over then .
,

a mi x ture of benzol and water t e n t he di s t ill ate n o longer separate s int o .

two layers the receiver i s changed and it is collec t ed as crude carboli c aci d , .

A further fraction may also be collected consis t ing largely o f cre s o ls and
naphthalene The resi d ue accordi ng to its qua li t y i s either run into the
.

creosote oil tank or used for softenin g pitch .

The rect ified carboli c oil i s next treated with w eak c a us t ic soda t o separate
the acid from the neutral hydrocarbons For thi s purp ose a lye is use d wi t h .

specifi c gravity not greater than 1 0 75 to 1 1 0 a s a s t ronger li qu o r w oul d di s -

,

solve some of the naph t halene If pure phenol be aime d at fracti o nal ex t ra c .

tion w ith caustic so d a is generally a d opted : a quantity of the carb o li c oil

i s mixe d thoroughl y with a quantity of cau s t i c solu t i o n m ore than su fficien t
t o extract a ll the phenol so that it al s o takes up a small proport i o n of t he
c resol The a que o us soluti on is then d ra w n off and mixe d wi t h a further
.

quantity of the carboli c oil w hen an inter c hange takes p la c e t he so di u m , ,

cresylate being c onverte d into so di um carbola t e Thi s method is rendered .

possible by the fact that phenol has a con s i derably grea t er affinity for t he so da
t han the cresols and o t her homologues in o ther w o rds i t i s a s t ronger aci d , .

The solution of phenate c r carbolate o f so da is purified by boiling and

bl o wi ng in steam whi ch removes a n y naph t halene a n d v a r i o us other impu r ities
, .

It is fi ltered if necessary and then treated w i t h a c id to release t he phenol .

Fo r this purp ose carbonic acid i s n o w generally u e d but a li t t le s ul phuri c s ,

a c id is a dde d to c o mplete t he proce s s The s o lu t ion o f so dium carbonate .

thu s obtaine d is re c onverte d into one of caustic s oda by t reating it wi t h lime .

1
J . I nd . E ng . C he m .
, 1 9 1 6, p 20 . Fo r . d e s c ip io r t n
of
p la se e nt Rit t m a n D utt o n ,

a nd De an , i b id .
, 1 9 1 6, p . 351 . S ee a ls o G . Eg lo ff a n d T J Tw o me y
’
. . , J . P hy s . C he m .
,

1 9 1 6, p . 1 21 .
2
S ee C . F . C hand l r e , ib id .
, p . 75 .
 BY PROD U CTS OF C OAL DI STILLATI ON
-

Thus not only i s the soda saved and used again but the carbolic acid remain
ing in the solution passes into the process again The cru d e phenol separates .

a s an upper layer on the acidified li quor it is drawn o ff a n d further purified

by fractionating through a dephlegmating column At first the distillate .

consists of water c ontaining only a small percentage of phenol then practically ,

pure phenol c omes over 1

at the e n d of the distillati o n cresols are obtaine d .

The phenol can be further purified by allowing it to crystallize and pressing

out the liquid residue .

Cresol can be separated and i n a similar manner from the fractions from
which the phenol has already been removed and it can be purified in the ,

same way But as a rule cresol and the other similar b o dies are used with
.
,

out exhaustive purification for the preparation of disinfectants etc The , .

alkaline washings obtained by treating benzol w ith caustic soda soluti on are
worked up for phenol or crude carbolic acid in the same way .

Before the war Germany depended largely on En glan d for the supply
of carbolic acid as the coke oven tars made there contain comparatively
,
-

little of it and its e x traction consequently c ou ld n o t compete very su c cess

,

fully with the E nglish product made from gas tar For the rectificati o n of .

the carbolic oil from coke oven tar F Raschig recommends that it be frac -
,
.

tio n a te d i n v a cu o through a very tall dephlegmating column 1 4 metres long , .

This c olumn he fills with small hollow rings of sheet iron 1 inch long and 1 ,

inch in diameter with walls of 3 7 inch thick These o ffer a very large
1
,
.

surface for the interaction o f the vap our and condensed liquid and c o n se ,

quently improve the fractionation and o ffer little resistance to the passage
of the vapours a n d so do not diminish the vacuum , The distillation i s .

c arried out at about 1 20 C At first an oil passes over c ontaining no phenol °

.
,

and is shown by the fact that if a p ortion be shaken with caustic soda its
volume is not re d uced After a time the phenol co n tent rises rather suddenly .

to 30 or 40 per cent It remains at this for some time and then falls to 20 .
,

or 25 per cent and naphthalene then crystallizes out fr o m the distillate on

.
,

cool ng The di stil ation is now stoppe d

i .l 2
.

When the demand for phenol is so great that i t cannot be met by the Ph e nol fr o t
b enz ene”
amount obtained from coal tar the consequent rise i n price makes it remu ,

n e r a tiv e to manufacture phenol from benzene by sulphonation and fusion with

soda A H Ney has described the process with considerable detail in a

. . .

lecture in New York : the fo llowing description gives the methods briefly
3
.

The sulphonation kettle is a cast iron vessel fitted wi th a lid and a condenser -
,

1
vap o ur p res sur o f
Fo r t h e es mi x tur es o f p he n o l a nd w a t er s ee F A
. H . . Sc h reine
mak er P r o c K A ka d W t n s ch
s, . . . e e .
,Ams t e r dam 1 90 0 , , p 1 . al o
s A . Mar h alls , J . C h em .

S oc .
, Tr a n s .
, 1 9 0 6, p . 1 3 65 .
2
An g .
, 1 9 1 5, i .
p 409
. .

3
R e p r o d u ce d in C h em Tr a de J o u r . Oc to b er 16 a nd 23, 1 9 15 ; lso a M et . a nd C h em .

E ng .
, 1 9 1 5, p . 68 6 .
 E X P L OSIVE S

to condense v ap our of be n zene and r eturn it to t he ket t le I t has a g o od st irr er .

a nd a j acke t for hea t ing i t E ight parts by w eigh t of c on c en t rated sulph uri c
.

a c id are place d in it and three p arts of benze ne are ad d ed wi t h c ons ta n t

,

st ir ring t e n t he t emperat u re c ea ses to ri se hea t is applied a n d i t is ma in

.
,

ta in e d near t he boiling po int of benzene Afte r five to ni ne hours t he sul

-
.

phona t ion i s c omplete and the con te nts of the kettle are run in to a lead lin ed -

t a nk and dilute d wi th an equal volum e of w ate r Then m ilk of lime is added .

,

which c o nverts the ben zene sulphoni c aci d into the calcium sal t w hi c h ,

remains in solu t ion and t he excess of sul ph u ric a cid into calcium sulp ha t e
, ,

which i s precipi ta te d The la t te r is fil te r ed off in a fil te r press and w ashed

.

the solution is mi xe d wi th s o di um carbona t e (soda ash ) which p r ec ipita t e s ,

the cal c ium a s carbona te and leaves so di um sul phonate in solution Thi s is .

evaporate d d own and the dry sal t is hea ted w ith fused caustic soda In a .

cas t iron vessel are placed 10 parts of c austic soda and a little wate r Thi s
-
.

is melted a nd heate d to about a n d 1 0 parts of the sul phonate are gradu

ally adde d The te mperature is t hen raised to a bout

. the sulphonate
i s t hu s c onverte d in to sodi um phenate a n d sul phite
C-GH s SOs Na 2J a OH z C GH SONa Na 2S0 3 H gO .

The melt is la dl e d out allowed to soli di fy broken up crush e d and dissolve d

, , ,

in wa te r Then d ilute sulphuric a c i d is r un i n un til there is a copious e v o lu

.

t ion of sulphur di oxi d e and the li berate d phen o l is allowe d to separa te out
, .

I t i s freed from sulphur di oxi d e by blo wi ng air through and is re ct ifi ed by ,

di s t i lla tion
t
Na p h h a l ene. The naph t halene whi ch crysta lli zes ou t from the carb oli c o il a n d various
other frac ti ons is subj ecte d to a number of opera t ions to purif y i t Afte r .

allo w ing i t t o drain i t is heate d a n d pres s e d in a powerful pre ss to r emove

the bulk of the oil Then it is washed wi t h caus t i c so d a solu t i o n to dis s olve
. .

out carbolic acid and t hen wi th h o t w ate r Next it i s heate d wi t h s u lphuri c

,
.

acid of about 1 8 spe c ific gravi ty w hich abs o rb s va r i ous imp u ri ties Then , .

i t is washed again wi th hot w a te r a n d afte rwar d s wi th wea k a lkali and , ,

fin ally it i s fractionall y distill e d It i s thu s obta ined as a whi t e c r y s ta llin e .

solid having a characte risti c smell .

Yie lds . The quantities o f the di fferent p rodu c ts obta ined na tu rally vary a c co rd
ing to the nature of the tar and t he processes a do p t ed bu t th e v are usuall y ,

w it hi n the fo llowing li mit s 1

B e n ze n a n d t lu n
e o e l t e1 5 pe ce n t o
-
r .

An thr a c ne e 0 25 to 0 4 5 - -

Ph n l
e o 0 4 to 0 5 - -

C r es o l 2 to 3
N p ht ha l n
a e e 6 to 10
H a vy il
e o 25 to 30
P it h c 50 to 60
1
Me ye r un d J a c o b so n , Or g a n i s e /7c
’

C he nn c , vo l ii p a
. . rt 1, p . 93 .
 C H AP TE R X I X

NI TRO-DERI V ATI V ES OF AROMATI C H YDROCARB ONS

N it o b n e n e C H N O A id n t D in itr o b e n n C H (N O ) Tri nitr

r o
e z ,; 5 2 cc e s -
ze e G 4 , 2
o

b n n
e C H (N 0 )
ze e , N it r o t lu n C H N O D in it r o t lue n C
3
, 3 2 3
-
o e e, 7 7 2
-
o e,

Trin it r o t o lu e n C H N O W a t e a c id s
e , 7 P u rifi a t io n
,
‘ 3 6
f t rin it r o t l n s c o o ue e

Th e t rin it r o t o lue n s Ac id e nt
-
P r o p e r t ie s D n it y M n n it r o na p h t ha l n
e c s
- e s o o - -
e e,

C H NO
10
D ini t r o nap h t hal n G w H N 0
7 2
-
Tr in it r nap h t hale n e C H N 0 6
e e , 6 2 4 o- , IO 5 3
:

Te t ranit r o nap h t hale ne C H N O -

, 10 4 4 8

B E N ZE N E is nitrated on a very large scale as a stage in the manufacture of

anili ne whi c h is used in the preparation of m any dye stuff s The process
,
-
.

of n itration does not di ff er in principle from the manufacture o f nitro glycerine -

but the mi x ed acids are generall y r u n into the benzene instead of the benzene
into the acids and as mono nitrobenzene is not e x plosive the same precaution s
,
-
,

are not necessary Fig 5 1 shows a plant capable of nitrating 500 gall ons
. .

or tw o tons of benzene in one c harge It consist s of a cast iron pan F having .

-

a total capacity of 1 60 0 gallons It has a strong lid through which passes .

,

a shaft bearing the two propeller agitators H the lower of which i s surrounded ,

by a cyli nder to increase the upward motion of the acid On the top of this .

cylinder is a grid K supporting the lead coils J the inlets of which are shown ,

at N 0 and the outlets at L M These coils are each 2 inches in di ameter

, , , .
,

and 1 50 feet long Through these cooling water can be circ ul ated or hot
.
,

wa te r or steam if it be requir ed to raise the temperature of the conte nts of

the pan Into the acid mi xing tank A are run 50 00 lbs of nitric acid of spe cific
. .

gravity 1 4 3 through the pipe D and through C 660 0 lb of concentrated , .

sulphuri c acid They are then mixed together by blowing air through the
.

perforated pipe B but in some works large quantities of acid are mixed at
a ti me in capacious tanks and allowed to settle The benzene is introduced .

int o the pan and the agitators are revolve d at about 60 revolutions per minute ,

and then the acid i s run i n in a thin stream the temperature not being all owed to ,

r i se above 60 C After the whole of the acid has been introduce d agitation
°
.
,

is c ontinued for a further 4% hour s to c omplete the nitration The waste .

acid should then contain less than 1 per cent of nitric acid The c ontents . .

of the pan are then allowe d to settle and the waste acid i s run into the egg ,

X and blown up through the pipe V to the w aste aci d tank by admitting com
,

pressed air through U The nitro benzene i s similarly run into X and blown
.
-
,

up through the pipe S into the wash pan R where it is washed first w ith -
,

253
254 E XP L OSIV E S

soda solu t ion a n d t hen wi t h w a t er a ir be in g blo w n in t hr ough the pipe P t o

,

a gi t a t e t he liq u i d s Afte r se t t ling t he ni t ro benz ene i r u n t o a s t o ra ge t a nk

.
,
- s .

The ma xim um t heore t ica l yi eld from 1 0 0 par t s of be nze ne is 1 576 and the ,

FI G . 51 . B e nze n e N it ra t in g P la n t .
(Fr o m Tho r p e
'

s D ic t io na r y o f C he mifi r y )

ac t ua l yi el d shoul d no t be les t h a n 1 54 5 The ni t ro b enz ene ca n b e further

s -
.
-

p u r ifi e d b v di t illa t ion in me tro

s .

Ni t r o b e nz ene ,
is a p a le v e ll o w o il s ligh t ly v ola t ile a t t he ordin
.

a r y t e mpe ra t u re a n d h a vi ng a ch a ra c te ri s ti c od our I t is s ligh t ly pois ono u s

.
,

”
b u t is us e d for p e r fu me r y a n d fl a v o ui i n g un d er t he n a me of o il of mi rba ne .

Under a t m os phe r ic p r e s ur e i t b o ils a t 20 9 C i t free zes wi t h s ome difi ic ul ty

s . ,
 NIT RO D E RIVATIV E S
-
OF A ROMATIC HYD ROCA RB ONS 255

and melts at Although its use has often been proposed as an ingre
di ent of va ri ous e x plosives it has not been so use d v ery e x tensively as its ,

v o la tib ili ty i s obj e c tionable and there are other nitro compoun d s available
,
-

which have more decided explosive properties It has however been used .
, ,

as an ingredient of Sprengel explosives and to reduce the freezing point of —

nitro glycerine It i s practically insoluble in water but soluble in alcohol

-
.
,

ether and other organic solvents .

W ith ordinary care the nitration of benzene i s quite a safe operation ,

ts
Acciden .

b ut in February 1 9 1 4 there was a severe accident at Rummelsburg in the

,

works of the Aktiengesellschaft fiir An ilin fa b r ika tio n whereby eleven people
were killed and fourteen inj ured The catastrophe seems to have been caused
.

by allowing the acid to run into th e benzol without starting either the stir
ri n g gear or the c ool ing water After a time such an energetic action set i n
.

that the top was blown o ff the pan and large quantities of benzol vapour ,

es c aped mixed with the air and exploded Similar accidents occurred at
, .

Mannheim in 1 9 0 7 and Moscow in 1 9 1 1

, .

After the Rummelsb ur g catastrophe a committee of chemical ma nu fa c

t u r e r s assembled in W iesbaden to c onsider the step s to be taken to avoid
the recurrence of such ac c idents and subsequently the P russian Minister
1
,
“

for Trade and Industry passed regulations somewhat similar to those in

force in explosives factories namely ,

. 1 Accumulations of material and persons are to be avoided as far as

p ossible .

.2 Ar rangements must be m ade to prevent large quantities of raw materials

interacting on one another at one time The nitration plant should be exam .

in e d every time before it is started ; accidents may be caused by the inad

v e r te n t presence of acid .

.3 It is undesirable that the plants should be in c ommunication with

one another .

.4 The nitrators are to be so erected that if large v olumes of hydrocarbon

vapours are evolved they will be discharged above the roof by an outlet o f
su ffi cient size .

.5 Arrangements must be made that acid cannot be run in before the

stirrer has been started .

.6 There must be a devi c e to sho w w hether the liqui d i s in motion .

.7 These rules may be moderated somewhat in the c ase of continuous

processes .

At the meeting of the Wiesbaden Committee W ter Meer described a , .

continuou s nitration plant whi ch he has used in his works

,
2
This consists .

of a cylin drical vessel of 3 cubic metres capacity provi ded with two inlets
at the bottom end for benzol and acid respectively Do w n the middl e of .

1
C hem I nd 1 9 14 p 33 7 2
G erm P a t o f Jul 24 1 90 9
. .
, , . .
y . . , .
256 E X P L O SIVE S
the cyli n der passes an axl e carrying a num ber of st ir rer bla d es The path .

of the li quids is prolonged by a num be r of di aphr a gms exte n di n g nearly

across t he c yli n der and fixe d al te rnate ly t o the walls and to t he axle The .

c ylinder i s pr o v i d e d w i t h a wate r j acket and an outlet at t he to p

-
The benzol .

is intro duce d at the rate of 30 0 kg per hour t o gether with t he re qu isite

.
,

quan t ity o f mi xed a c id ab o u t 8 0 0 litres i n all They ta ke nearl y fo u r hours

,
.

to pass t hrough the nit r ato r a n d in a t w elve ho u r shi ft 4 % t o ns of good ni t ro

,
-

b enzol a r e obta ine d .

Neumann describe d a simi lar p lant i n w hi ch t he rea ct ing liqui ds a re m a d e

t o traver s e an annular space bet w een a fi xed and rotatin g cylin d er bo t h ,

carry ing s tir rer bla des a n d c oole d or heate d locally or entirely as re qui re d .

Ku b ie r s c hky s plant is on a di ff e r ent s yste m i t h a s no mechani c al stirrers

’

a n d t he benz o l and acid a r e m a de to pass in opposite di r e c tions thr ough a

t o w er
. It is sho w n di agramma t ically i n Fig 52 The benzol flows from the
. .

ta n k A into t he nitratin g to w e r I at the point a nea r the botto m The mixe d .

ac i d flo w s from B i nto t he same to wer nea r the to p at b : in c onsequence

of i t s hi gher gravity it sinks d o w n gradually nitra t i ng the b enzol a s i t goes
, .

At the bo t tom of the t o w er the w aste acid separate s from the ben zol and flo w s
into the tank 0 The nitrate d product flo w s from the to p of the to w er t h rough
the pipe d and t he v isible o v erflo w D to the washing tower I I where it m eets
, ,

a stream of w a te r flowing up t he to w er a n d is thus free d from a cid The

,
.

fl o w from the bottom of I I i s regulate d by the c ock 6 : the ni tro benzol is -

prehea t ed in E and then flo w s at f into the top o f the c olumn I I I U p to

, .

thi s point the nitro benz o l contain s abou t 1 0 per cent of unchanged b enzol
-
.
,

an e x ces s havi n g been used to prevent t he formation of dini tro ben zol In -
.

I I I t hi s benzol is removed by means of live steam at g The pur ified nit r o .

benzol t hen fl o w s through the cooler G and the visible overfl ow to the separato r
,

K w here it is freed from w ater carried along mechani cally

,
.
,
The di stillate .

fr o m I I I is c on densed in E and F and i s separate d in ] into benzol and wate r

, .

The con s tru c tion of column I is shown in Fig 53 The arrows in the . .

l o w er p o rtion sho w the way the benzol circul ate s and passes i n a finely divided
s t a t e t hrough t he a c id w hich i s movi ng in the opposi t e di re c tion The nitric .

a c id is t hus v ery f u lly utili zed The te mperature i n t hi s col u mn is r e g ulate d

.

by mean s of t he c oils The nitration process is followed by ta ki ng r e a d in gs

.

of t h e d en s i t y of the c ru d e nitro ben zol by a hydromete r in D and the fl o w

-
,

o f ben z o l and a c id is regulate d accor di ngly The c o l u mn I I is o f s im ilar

.

c onstruc t ion to I Thi s plant is said to work we ll .

Dinitro ben zene is manufact u re d in the same way as mono ni tro be nzene
- — -
,

excep t that twi ce as mu c h aci d i s used The nitration is generall y ca rri ed

.

out in tw o sta ges the bulk of the w aste acid from the first s ta ge be ing r un
,

a w ay befo re the sec o n d lo t i s run in For the secon d sta ge the a cids may
.

with a dvanta ge be somewhat stron ger and t he c o nte nts o f the ni tr a t in g p a n -

 NIT RO D E RIVATIV E S -
OF A ROMATIC HYD ROCA RB ONS 257

are heated finally to near the boiling po int of water The waste acid from
,
-
.

the second stage may be r e v i v ifi e d by the addi tion of strong nitric a c id and
used for the preliminary ni tration of a further charge of benzene Of the .

three isomeric di nitro benzenes the meta compound is that prin c ipally formed
- -
,

mixed with only small quantities of ortho and para dinitro benzene I t is - -
.

FI G . 52 . K u b ie r s c h ky
’
s Nitrat ing Pl ant . FI G . 53 . K u b ie r s c h ky
’
s Nitrat in g To w e r .

separated from the waste acid and washed first w ith cold water and then ,

w ith h ot As it i s sli ghtly soluble in the latter the final wash wat er sho ul d
.
,
-

be kept and used agai n for the cold washing of a later charge .

P ure m di ni tro benzene melts at

- -
whereas the meltin g p oints -

of the o and p compounds are 1 1 8 and 1 72 respectively Good commercial

-
° °
.

dinitro benzene melts at 8 5 to

-
and is in the form o f long shinin g needles
°

V OL . I.
 258

of li gh t yello w c olour It sho uld co nta in no ni t r o benz ene and shoul d be .

-

o d o urless I t i re a dil y soluble in a l co hol benze ne and other organi c solvent

.
s
, ,

a n d ca n b e pur ifi e d by r ec ry sta llization fr om t hem It ca n o nl y b e detonate d .

wi t h gr ea t diffi c ul t y a nd c onsequ ently is not u sed an an exp losive by its elf

, ,

but it has be en us ed as a co ns t ituent of co mplex exp losives such as the ,

amm oni um ni tra te explosives Belli te and Ro burite and low freezin g ni tro , ,

glyce rin e explosives The r e h as been a tendency of r ece nt yea rs to substi tute
.

di a n d tri nit ro toluene for thi s substa n c e but the p r esent scarcity of toluene
~ ~

is likely to ca us e thi s p r ac ti ce to be reversed The density o f m dini tro .

-

benze ne is 1 3 69 a t
By a fur ther ni t r ation of din it r o b enz ene it ca n be converted partly in to -

t rini tr o be nz ene but it is neces sary to u se very st r ong ac ids m a de w ith ole um
-
, ,
’

and to ca rry out the ni tr ati on at a hi gh te mpe r atur e and for a long time .

Thi dr a stic trea tment c au ses the destruction of much of the materia l by
s

oxida ti on and con sequently the y ield is p oor I t is ob tain ed mor e ea sily
,
.

fr om t r in itro to luene : t hi s is oxi di zed by sulphuric acid and bichromate

-

of p ota sh to trini tro benz oic ac id which is re duced to t rin itro benz ene by -
,
-

boilin g wi t h water In either case the manuf a ct ur e is expensive and t r ouble

.

s ome so that although it is a slightly m ore p owerful explosive t han either

,

tr ini t ro to luene or picric a cid it has never come into general us e

-
.

The r e are thr ee po ssible t r in itro ben zenes bu t the one that i s ob ta in ed -
,

al most exclusively is the sym met r i cal or 1 3 5 co mpoun d .

I t mel t s at 1 21 C its exp l o sive p roperties have been investigate d by Daut

°
.

r iche Th e 1 2 4 c ompound is also kn own

l
. .

l itr o to lnene . Toluene i s ni tr ated in the same way as benzene but the nitr ati on p ro ,

0 73 71 0 ,
c ee d s s ome w ha t more r apidly ; also less acid i s requi red because the mole
c u la r w eight i s grea te r Of the thr ee ni t r o to luenes o nl y 2 to 4 per cent -
. .

of the me ta com p ound is form e d about 3 8 p e r ce nt of the para and 60 per

-
,
.

ce nt . of the ort ho the p r opor ions var yin g somewhat a cc ording to the con
,
t

di tio n s of ni t r ati on ’ The yield is about 1 40 p arts from 1 0 0 parts of to luene

.
,

w herea s ac c o r din g to th eo r y the r e shoul d b e 1 49 The p roduct has a specifi c .

gr avit y of a bout and i s li qui d a t the ordin a r y te mpe ratur e By c ool .

ing it to a b o u t 1 0 C p a rt of the pa r a nit r o to luene ca n be m a de to separate

°
.
,
- -

o u t a n d fil te r ed o ff on a co ol e d fil ter p late but to eff ec t a separ ation o f the ,

1
P . at S
1 6 p 27.,
, . .

3 Se e A F . . H
o llema n , P w e . K . A loud . “ Me ns ch , Ams ter da m 1 90 8 , , v o l. x i , p . 248 ;
Rec Tmr
. . ch m ,
1 9 1 4, p 1 . . H . w . F isc he r , z Ele ktmc
. .
, 19 10 p 1 61, . .
 NIT RO -
D E RIVATIVE S OF A ROMATIC H YD ROCA RB ONS 259

constituents of the li quid residue i t i s nec essary to submit it to fractional

di still ation in va cu o The ortho comp ound di stils over first ; when the
.
-

greater part of it has passed over the di still ation i s interrup ted and the residue
i s run out and cooled whereup on it dep osits the greater part of its para
,

nitro toluene The fo llowi ng are the principal physical properties of the
-
.

nitro toluenes
-

O r tho Me t a P ara

Sp e c ifi c g ra v it y 1 1 63
-

Melt in g p o in t
-
3 85 — - °

B o ilin g p o in t 22 3 3
-

The mono ni tro toluenes are not explosive in themselves and are not used
- -

as c onstituents of comp osite exp losives but they are formed in the first stage ,

of the formation o f di and tri ni tro toluenes and para ni tro toluene i s used - -
,
- -

extensively for the manufactur e of dye stuffs -

.

On fur ther nitration p ara ni tro toluene gives a lmost exclusively 2 4- -

din itro toluene and the ortho derivative gives mostly the same comp oun d
-
,
-
,

but also some 2 6 di ni tro toluene The meta derivative i s present o nl y in

- -
.
-

small quantity and ni trates much les s rea di ly and c onsequently remain s ,

un changed to a considerable extent Consequently the principal product of .

the di rect ni tration of toluene to the second stage i s 2 4 dinitro toluene mixed - —

with small quantities of other di nitro comp ounds some mono ni tro toluene -
,
- -

(meta and para ) and trini tro toluene The mono ni tro toluenes are only
-
.
- -

separated from one another before ni tration if the para comp ound is required -

for the manu factur e of dye stuff s in thi s case the crude ortho ni tro toluene
- - -

i s taken fo r ni tration When the ni tration i s complete the crude dini tro toluene
.
—

i s allowed to separate from the waste acids in the warm On cooling it sets .

to an oil y solid T hi s is often p urified by warming it to ab out 40 C and allow

.
°
.

ing the more easily fusible p ortion to flow away The purified product i s .

u sed for the manufacture of dye stu ffs and sometime s for the preparation o f -
,

composite explosives such as Cheddite The more fusible residue i s kno w n .

in Germany as Bini tr o tr o p fo l and i s used for the man uf acture of trini tro
,

toluene From the waste acids o n cooling there separates out a fur ther small
.

quantity of ni tro product which floats on the surface from which it is s kimmed
-
,

o ff . The waste acid has a spec ific gravity of 1 75 to 1 77 and contains from - -
,

3 to 4 per cent of nitric acid whereas the waste acid from the manufact ure
.
,

o f mono ni tro toluene has a specific gravity o f 1 66 to 1 67 and contains

- - - -
, ,
 E X P L OSIV E S

accordi ngto R E scales

1 to 1 5 per cent nitric acid
. If the ni trati o n be , . .
1

properly condu c ted the yield of di nitro toluene is not far short of the theo -

r e tic a l .

There are s ix p o s s ible di nitro toluene s a n d all of them have been prepar e d -
,

either by ni tration of t o luene o r by more in direct metho d s .

2 4
Me lt in g
}
°
70
p o mt

Of the s e the first is the only one that i s of any c ommercial imp o r ta n c c o rtho
ni tro toluene however gives a little of the 2 6 compound
-
,
Meta nitro
,
-
.
-

toluene gives 3 4 mi xed w ith smaller quantities of 2 3 and 3 Commer

c ia l c rude dini tro toluene c ontains therefore a ll the above six compounds
-
, ,

except the last but the first pre d ominates The statement th at the 3 5
,
.

derivati v e i s also formed i s doubted by

3
All excep t the 2 3 and
3 5 compoun ds have been found in a b y product from the purification of
- -

di nitro toluene -
5
.

In e xplosive properties a ll these substances are very similar ; they can

onl y be detonated with great diffi culty and are decidedly insensitive The , .

2 4 compound is used a s a constituent of composite blasting exp losives

-
,

notably cheddi te They possess the di sadvantage that they are very poisonou s
.

and are liable to aff ect inj uri ously those w h o han dl e them From the p u r ifi .

cation o f the crude material a complex mixture can be obtained which i s ,

li qui d at the or di nary temperature This dissolves c ollodi on cotton and .

,

is thereby converted into a thick j elly which is used in the manufacture of ,

plastic blast ing explosives .

T r ini t ro t o luene may be made by the nitration either of B in itr o tr o p fo l

-

or cru de ortho ni tro toluene or from toluene by successive nitration in tw o

- -

or three stages w ithout the separation of any of the nitro bodies In any case -
.

i t is best to c on duct the conversion of di into tri nitro toluene as a separate - -

O peration as it requires a stronger mixe d acid a n d if a large volume of str o ng ,

mi x ed acid be used to ni trate t oluene or m ono nitro to lu e n c directly to trinitro - -

N itr o s p r en g s to fi e p 1 42
1
, . .

2
A F H o lle rn a n a n d H A Sir ks P r o c K A ka d lVetens c h Am s t e rd a m 1 90 6
. . . .
, . . . .
, , ,

p 28 0 ; C he m S oc A b s tra 1 90 7 i
. .
p 28 0 . , , .
, . .

3
H a usse r ma nn a n d G re ll B er , 1 8 9 5 p 2564 B er , 1 9 1 3 p 558 .
, .
, . .
, .

5
E Mo lin ari a n d M G ina Re nd ico nti de l B ea le I s titu to di Sc ie nze c L ette re 1 9 13 v o l
. . , , , .

46, No 1 1 ; S S , 1 9 1 4 p 23 9
. . . , . ,
 NI TRO D ERI VATIV ES OF A ROMATI C H YDROCA RBONS
-
261

toluene the yield wi ll be low i n c onsequence of its s o lubil i ty in the waste aci d ,

and b y reacti ons due to the oxi di zin g action of the acid
-
The mixed aci d .

may be made by adding nitric acid cautiously to o leum of 20 per cent strength . .

Accor di ng to F Langenscheidt the quantities are 1 1 25 kg of 20 per cent

. . .

oleu m and 30 5 kg nitric acid of s p gr 1 500 kg of b initr o tr o p fol are place d

. . . .

in the nitrating pan and melte d a n d the mixed acid i s run in slowly at a tem
p e r a tu r e of 70 to 75 C When all the acid has been a dde d the mi x ture is °
.

warmed gradually until at 9 0 to 1 00 the reaction sets in and the tempera ° °

ture rises to about At this temperature it is a llowed to remain for

an hour and then cooled to W ater is added to the charge to di min ish
the solubility of the trinitro toluene in the acid and the contents of the
2 -
,

nitration are run o ff through a steam heated cock and kept hot until separa -

tion i s complete The trinitro toluene may be soli di fie d in a suitable state

.
-

of di vision by runni ng i t on to a j et of air over water Toluene is nitrated .

with considerably greater ease than benzene but it i s necessary to use strong
3
,

a c ids at a high temperature to make the trinitro derivative and there i s an -

,

appreciable loss by o x idation w ith the result that the yiel d is lower th a n ,

the theoretical Accordi ng to Will trin itro benzoic acid and tetranitro
.
-

metha ne are liable to be formed the latter may sometimes be r e cognized

4
,

in the factory by its intense smell The o x i di zing action is said to be increased .

by the pre s ence of metalli c salts sodi um nitrate and esp e ciall y ammonium
5
, ,

nitrate bu t the formation of nitro benzoic aci d under manufacturing con di

6
,
—

tions has been deni ed by F Langenscheidt 7

Accor di n g to C o p is a r o w phe noli c . .
,

comp ounds are liab le to be formed by the action of the acids on the metal
of the nitration vessel producin g hydrogen and sulp hon i c acids if the quan ,

tity of nitric a c id present be in su ffi cient .

The waste acid contains up to 4 5 per cent of nitric acid and nitrous -
. t
W as e a cids,

aci d s and a considerable amount of trinitro toluene and various b y pro

8
,
- —

ducts in solution It may w ith advantage be r ev i v i fi e d and used for the .

manufacture of mono o r di nitro toluene or the nitric acid is di stille d off

9 - - -
,

after di luting to density of 1 3 8 and the residue is further di luted to 1 21 ,

-

to precipita te the nitro bodies It i s not advi sable to use the waste acid for -
.

t he manufacture of ni tric acid from sodium nitra te because the nitro

1
S S . ., 1 9 12, p . 425 .

2
S ee G e r m Pa t . of J u ly 1 5, 1 90 9 , al so Ve n ni n et C h nea u
es , p 261 . .

Fo r m e a s u r me n t s v e lo c i ti f ni tr t i J P Vl ib a u t Rec Tr a v ch i n a
’
of th e
3
e es o a on s ee . . , . .
,

1 9 15, p . 9 50 ; J
S o c C he m I n d , 1 9 15, p 241
. . . . . . 1 9 1 4, p 70 7.
4
B er .
, .

5
M . ( o p is a r o wy C hem N ew s , 1 9 1 5, v o l 1 1 2, p 247
‘
. . . J .S o c C he m I n d , 19 1 5 p 1 1 68
. . .
, . .

6
A . Vo ig t , S S . .
, 19 1 4, p . 225 .
7
S S , 1 9 1 5, p 23
. . . .

8
S ee L . J 1 9 1 6, p 149
. S oc . C he m . I nd .
, . .

M u t a
_

9
S ec F . . Vas q e z ll l cmo r ia l de A r ti lle r ia , Se p
, 1 9 10 ; S S 1 9 1 1 , p 30 2 i ls o . . ., .

E ng Pa t
. . o f 19 1 4 b
y C a ig Ro b e s o , F m e a n d Ro tt e
, r
A r ms a nd E r p lo s ir cs
, rt n ar r r ,

1 9 15 , p . 1 39 .
 E X P L OSIV E S

exp losives pass unal tered in to t he nitro cake and may ca u s e e xplosion s -
.
l

Or it may b e d eni t r ate d in a deni t ra tion to wer but in thi s ca se a large pro ,

portion of the ni t ro c ompoun ds pass over with the ni trou s ga ses and ca use
-

stoppages 2
The foll o wi n g are the compositions of two waste ac id s given
.

by M C o p is a r o fi
.
3
in the second one an insuffi cient qu anti ty of ni tric a cid
has been u sed :
Co lo u r b ro w n
N itr o u ac id s

Nit ri acid c

Sul p huric ac id

Su lph o mc a c id s

W Mc H u tc hi s o n and
. R . Wright ‘
gi ve the following a s t he composition
of a waste acid :

Sp ecifi c g ravit y . 1 8 50 a t
°
17

On mixi ng with th i s an e qual vol u me of water reducin g the specifi c gravit y ,

to trinitro t oluene separate d equ ivalent to 5 8 per ce nt by weigh t

-
,
-
. .

The ad di tion of 4 more volumes of water only increa sed thi s am oun t to
6 2 per c ent
-
The authors recommend that the waste acid be added to the
.

water and not vice versa so as to r ecover the trinitro to luene in a conveni en t
, ,
-

form .

The ni tro comp oun ds can also be extracte d from the waste a cid by agitatin g
-

i t wi t h toluene or by revi vi fying the acid and using i t for the manufacture
,

of mono or di ni tro toluene In either case the to luene used to ext ra c t th e

-
.

ni tro body is eventuall y converte d into t r initro toluene

- -
.

t
Pur ifi ca ion The crude product is freed from acid either by boili ng it w ith wate r or by
tolu ne
e
washi ng it in a gran ul a r con di tion with warm wate r with the addi tion of a
little sodi um bicarb onate It is then dried and p u rifi e d ei t her by w a shi ng
.

with alcohol of 9 5 per cent st r ength or by rec rysta ll ization ei ther from
5
.
,

alcohol or ben zene Accordi ng to Langenscheidt te c hni cal al c ohol c onta in

.
6
,

1
Ve nn in et C h nea u
es , p . 260 .
2
F . L an ge n h sc e id t . 19 1 2 p , . 4 26
.

C he m N e w s
.
, 1 9 1 5, p 24 7 ; . J . S oc . C he m I nd . .
, 19 1 5 , 1 1 68 .

J . S oc . C he m . I nd 1 9 15 p , . 78 1 .

5
Ve rmin et C hes neau , p . 261 .
3 19 12 p , . 427 .
 NIT RO DERIVATIVES OF A ROMATIC HY DROCA RBONS
-
263

ing about 9 0 per cent C H OH dissolves at the boiling p oint one ninth of its
.
z a
- -

weight of tri ni tro toluene and gives 9 0 per cent of it up again on cooling
-
. .

Benzene di ssolves 1 7 times its weight at the boiling p oint and about 78 per
- -
,

cent of it crystall izes out again on cooling But the best solvent i s alcohol
. .

mixed with 5 to 1 0 per cent of pure benzene In a double walled iron vessel . .
-

are placed 230 0 litres of this solvent and 500 kg of trinitro toluene The , .
-
.

liquid is stirred and boiled the vapour formed being condensed and returned ,

to the vessel W hen solution is complete the li qui d i s filtered and allowed
.

to cool The crystals are freed from mother liquor by centrifuging or fi lte r
.

ing o ff in a vacuum press If the material be recrystallized more than once .

the m other liquor from the second recrystallization is used for dissolving up
a further quantity of crude substance and so on The last m other liquors , .

are concentrated in a still and give on cooling some trinitro toluene of inferior -

quality and on further concentration a still more impure material i s obtained

, ,

which may be liquid at the ordinary temperature and m ay then be used for ,

making plastic explosives .

Trinitro toluene may also be purified by recrystallization from sulphuric

-

acid Thi s method i s used in France for the preparation of material for the
.

manufacture of mining explosives After thi s recrystallization it i s wa shed .

methodi cally with warm water neutralized with a dilute solution of sodium ,

carbonate and then rinsed with pure water The product obtained h a s a .

melting point of 77 to 7
-
Vender has patented a process for recrystalli zing
°

it from strong sulphuric acid preferably of 1 00 per cent strength After , . .

dissolvi ng at 8 0 to 1 00 the acid i s cooled and may be diluted It is claimed

° °
.

that this process gives a large y ield of material of good quality 2

.

Another proposal is to use nitro toluene as a solvent 3

The trinitro -
.

toluene is heated with a third of its weight of nitro toluene allowed to cool -
, ,

filtered o ff and washed with alcohol to remove the nitro toluene The nitro —
.

toluene containing the i mpurities is used for the manufacture of a further

quantity of trinitro toluene The obj e c tion to this process is that the
-
.

nitro toluene must be nearly as di ffi cult to eli minate as the natural

-

impurities .

Liquid trinitro toluenes are naturally very variable in composition an

-
,

average sample may contain 8 0 per cent trinitro toluene consisting of the .
-
,

6 compound with one or more other isomers together with several

-
,

dinitro toluenes and only a very small quantity of mono nitro toluene
- 4 - -
.

Other sub stances are probably also present Nobel and Co of Hamburg . .

have patented a method for i ncreasing the degree of nitration of this product
1
Ve rmin e t C he ne au p 261 s , . .

2
V V nd e r E n g P a t
. e , o f 1 90 9
. G rm . , e . Pa t .

3 G erm P a t An n o unc m n t 8 729 1 2 Au g

. . e e ,
0 , . 28 , 1 9 1 3 .

4
See 8 t h I nt e rn C o n g App l C he m
. 1 9 12 . . .
, , v o l. 27, p . 44 .
264 EXPLOSIVES
wi t hout ca us ing i t t o soli di fy a t t he ordin ary te mperat ure For t h is p ur .
1

pose t hey u e an ac i d rich in sul phuric a cid and p oo r in ni t r ic The fo llowing

s .

exa mple i s given : 1 00 kg of a residue from purifica t ion con ta in in g abou t .

,

1 5 per ce n t ni t r ogen are hea ted for a long t im e a t a t empera t ur e of 8 5 to

°
.
,

1 00 C wi t h 1 8 5 kg of mixed a cid con ta i n i ng 8 5 per c en t a n d 1 5 per

°
. . .

c ent .H NO The resul t in g pr o d uct was 8 7 kg of li qui d t r ini t ro toluene

, . .
-

s o li df y i n
g at con t a ining 1 66 to 1 7 2 per cent ni t rogen and giving a Tra n zl -
.

t es t of 250 to 270 c c w hereas dini t ro t oluene conta ins 1 5 4 per cent ni t ro

. .
,
-
.

gen and t rini t ro t o luene 1 8 5 per cen t and gives a Tr a n zl t e st of about

,
-
.

290 c c . .

Ligh t has been t hrown upon the low meltin g points of these products -

by M Giua who has dete rm ined the melting p oint curves of vari ou s binary
.
,
-

m ix t ure s of ni t ro to luenes 2
In each case examined he foun d t hat a c omplex
-
.

c o mpound i s form ed havin g a melting point about 30 lower than that of -

°

ei t her cons t i t uent These c omp oun ds only exi st in the soli d state when
.
,

mel t ed t hey dissoc iate ent irely Mi xtures conta in i ng t hree or more con .

s t it u e n t s w o ul d show a st ill greate r depression of the meltin g point -

.

There are s ix p ossible trini tro t oluenes and ac cording t o M C o p isa r o w 3 -

,
.

t hey are a ll kn o w n and have the foll owi ng mel t ing points : -

As a lrea dy sta te d commercial dinitro toluene consists almost en t irely of the

,
-

2 4 co mpoun d and t hi s on further ni t ra t ion g ive s onl y 2 4 6 tr in tr o

'

- -
,

t oluene w hich co nsequently c ons t i t ute s the bulk of crude commercial tro t yl
, .

I t co n tains ho w ever small quanti t ies of 2 3 4 and 2 4 5 trinitro toluene

, ,
- -
,

t hese bei g formed from t he products of meta nitro toluene

n “ 5
2 : 5 di nitro - -
.
- -

t o luene give s t he 2 4 5 c ompound and 2 3 t he 2 3 4 compoun d 3 4 - -

,

a mix t ure of a b ou t 75 per cent 2 4 5 and 25 per cen t 2 3 4 I t is doub t . .

ful w he t her 3 : 5 dini t r o toluene is amongs t t he pro d uct s o f ni t ra t ion but

- -
,

1
Ge rm . Pa t . f Se p 1 4 1 9 10
o t .
2
B er
, 19 1 4 p 1 7 18 . .
, , . .

3
Lo c . c it. “ 1 “ i ll B e r 1 9 1 4, p 70 7
, .
, . .

5
K om r e a n d A C o n ta r di ni . A ll i R A cca d L i nce i 19 1 5. i
.
p 888
.
, .
, . .
 NI TRO D ERI VAT I V ES or A ROMAT I C HYDROCA RBONS
-
265

it can be prepared indi rectly ; Will found ho wever that it could not be further , ,

nitrated to a trinitro toluene : it either remained unchanged or was oxidized -

to dinitro benz oic acid Only the first three of the ab ove s ix trinitro
-
.

toluenes are therefore known to be formed by the nitrati o n of toluene ,

and of these the first i s by far the most important It has not hitherto been .

found p ossible to make tetra ni tro toluene - -

.

Trin itro toluene was made in the laboratory by Hepp as long ago as
-

and in 1 8 9 1 C H au ss e r ma nn together with the Griesheim Chemical Factory

.

took up its manufacture 2

E xperiments were carried out with it by the .

German military authorities in the late eighties and early nineties and in ’
,
’
,

1 9 0 2 they adopted it for filli ng she ll and other purpose s In 1 9 0 1 the manu .

facture was taken up by the Carbonite C c and other explosive firm s soon .
,

foll owed Other countries soon followed suit Italy in 1 90 7 and Russia shortly
.
, ,

after .

It has been given many names mostly a bbreviations of its scientific ,

one In the E ngli sh service it was formerly known as

. but now
as trotyl ; in Italy it i s called tritolo Other names are trinol and .

trilite .

It has largely di splaced picric acid for filling high explosiv e shell because -
,

although it i s not qu ite so p owerful or violent it has a lower melting point ; ,

-

i s not so sensitive and does not tend to form dangerous metalli c salts It .

has replaced pic ri c acid and gun cotton for filli ng submarine mines and torpedo -

war heads over gun cotton it has the advantage of greater violence and a -

higher density It h a s been substituted for di nitro benzene in blasting

.
-

e xplosives because i t is not only more p owerfu l but also less poisonous I t .

i s used in the manufacture of detonating fuse and composite d etonators and

many o ther explosive accessories .

The melting p oint of the p ure substance was at one time stated to be
-

but this is too hi gh Accor ding to Gomey it i s Molinari .

and G ina as Rintoul as and E scales as 8 0 6 or °

-

T r initro toluene i s one of the most stable explosives when heated it does
-

not ig ni te until a temperature of about 300 is reached and then t does not °

explode E ven at 1 50 there i s no perceptible d ecomposition but at 1 8 0

.
°
,
°

there is a steady though slow evoluti o n of gas 8

On June 1 1 1 9 1 0 an Order .
, ,

1
S ee A n na len , 21 5, p 3 61 v o l. . .

2
S ee C H au s s e r ma nn , Z e i ts ch a nge w
. . . C h em ., 1 8 9 1, p . 50 8 ; J . Soc . C h em . I nd .
,
1 8 9 1,

p . 1 0 28 .

3
I Vilb r a n d , Ann a le n , 1 28 , 1 8 63 p 1 78 ; , . J . Ru d e lo ff S S , . .
, 19 0 7, p . 4 .

a-
A M C o me y J I nd E ng C he
. . 1 9 10 , . . .
p 10 3
, . .

mB end B ea le I s t S cie nze L et

. . .
, 4 6, 1 9 1 3 ; S S 1 9 1 4 p 242
. .
, , . .

mJ S o c C he m I nd 1 9 1 5 7 N i tr o s re n s to e 20 29 3
o
. . .
p , . 60 .
p g fi , pp .
, 1 55, .

Ve r o la P et S v o l. 1 6, 1 9 12, p 40
c
, . .
, . .
 266 E XP L OSIV E S

in Council was i ssued un d er sec ti on 50 of t he E xplosives Act 1 8 75 exempting , ,

it from be ing deemed to be an exp losive durin g manufac t ure a n d storage ,

u ncondi t i ona lly and when conveyed and imp or t ed provided it is prope rly
,

packed .

ts
Acciden .
Nevert heless it m u st no t be forgot t en t hat it can explod e and in fa ct it ,

has c a used a num ber of dis asters In 1 90 6 a fi r e at the Robur i t e Fac t o ry .

at Wi t t en led t o t he explosion of the st o re roo m containi n g t rinitro toluene - -

a n d amm o ni um nit r ate ; the detonati on w a s so vi olent t hat the fac t ory wa s

almost en t irely des t royed and forty tw o people we r e killed and many in j u red l
,
-
, .

In 1 90 8 an explosion occurred at J IV Lei t c h and works a t H u dde r s . .

field whereby five men were inj ur ed The ac cident was caused by pla c ing
,
.

a pipe containi ng trini t ro toluene in a boil er fire to clear the pipe by mel t ing -

ou t t he content s In 1 90 9 s everal men were ki ll ed by an explosion in th e

.

c rysta llizin g house at Alle ndo rfi s fac t o r y at Sc h iine b ec k Thi s ac ciden t ’

i s somewhat pu zzlin g a s the effects seem e d to be t oo great to be due onl y ,

to an explosion of vapo ur and yet not nearly so g rea t a s woul d have been ,

cause d by the exp losion of even a small proportion of the t rin itro toluene -

p rese nt in the buildin g 2

In 1 9 1 2 1 00 kg exp lod ed from some unknown .
, .

cau se in a ca sk in the washi ng house of a Germ an facto r y whereby four men ,

we r e kil led and fo u r se v e r e lv inj ur e d It wo ul d seem t hat the substan ce is .

liable occ a sionally to conta in some imp ur i t y whi ch rende r s it much more ,

da ngerous To a ca use of thi s s o rt is a c r ib e d a fatal e x plosi on that occ urred

.
s

in 1 90 7 in a vacuum still from whi ch mono ni t ro toluene wa s di sti lled 3

Dupre - -
.

found t hat the addi tion of a li tt le causti c pota sh ca us ed t rini tro t o luene to -

explode when hea ted to

B and 7 tr ini tro toluene are however somewh at less stable t han th e
- - -
, ,

a compoun d Their behavi our with a lkal i wa s investigated by W I Vill

- 5
. .
,

who fo u nd that the B and 7 compound when trea ted with a lkali even an - s
,

al kalin e ca rbonate whether in the presence or abse nce of alcohol are c on

, ,

verte d into salts of dini t ro cresol and these have much the sa me propert ies -
,

as picra te s Thi s change even takes pla ce when they are hea ted wi t h
.

lea d oxi de in the prese nce of alcohol lead c re s y la te s bein g form ed The .

a comp ound on t he other hand is not att a c ked by heatin g wi t h lea d

,
,
,

o xi de and alcohol and by 1 per cent soda solution a t 9 5 to 1 0 0 i t , .

° °

is onl y a t t a cked a t hird a s rapi dl y as t he other tw o Al kali alone .

conver t s t he u compoun d in t o r ed colo u r in g matte rs and in t he presence

-
,

of a n oxidi zing agent gives he x a nitro di b e nzyl w hi ch i s c ompa r a tively -

,

s t able .

1
Se e S S . .
, 1 90 7, p p 333 . , 4 1 3, a nd 4 16 .

2 3
Se e S S . ., 190 9 , p 21 3 . . S S . .
, 1 90 8 , p . 298 .

1 90 3, p 26 . .

5
B er .
, 1 9 1 4, p 7 1 1 . see a lso M . CO p is a ro w , Che m N e ws .
, 1 9 1 5, vo l 1 12 p . 28 3
. , .
 NIT RO D E RIVATIVE S
-
OF A ROMATIC H YD ROCA RB ONS 267

CH 2
_
CH 2

NO 2 + a lkali a n d NO, NO Z
ox n
i d izi g !
ag nt e

mp
. . 80 6
°
mp . . 21 2
°

alkali alka li

mp
. . 1 12
°
mp . . 10 1
°
mp . . 10 4
°
mp
. . 74
°

E xcep tas regards the melting p oint the physical properties of the three p ope ties
-
r r ,

i someric trinitro toluenes are simi lar They have about the same specific
-
.

gravity of about 1 6 2 the same temperature of ignition 29 0 to

,
the same ,
°

heat of combustion of about 3 660 Calories give the same resul t i n the Tr a u zl ,

test and are about equally sensitive under the fa lli ng weight alth ough the
, ,

a comp ound i s slightly less sensitive than the

7
-
.

Trinitro toluene which has been melted has a dens ity of 1 57 to 1 60 D en ity
-
, ,
-
s ,

when p owdered and c ompressed D a u tri c h e found that it had the following

whence it i s concluded that the limiting density for the compresse d mate rial
i s about 1

NI TRO-XYL ENES ETC , .

The next homologue of the benzene seri es 1 s xylene of which there are ,

three isomers all of which are present i n coal tar and have boiling points
, ,
-

close together between 1 3 7 and It is not practicable to separate them

°

1
P . et S .
, v o l. 1 6, 1 9 1 2, p . 28 .
 EXPL OS I V ES
m
on a com er c ial s c ale Nitro xylene i s a c o nstituent of some blasting e Xp lo
.
-

s iv e s,
Mo n a c h it for insta n c e but fo r t hi s purpose the crude mi x ture i s used
1
,

w hich is obtained by nitrating the mi x ture of the thr e e xylenes As th ese . .

are nitrate d w ith different degree s of di ffi culty a mi x ture tri di and even mono
nitro xylenes i s obtaine d a n d in c onsequen c e of t h e complexity o f the mixture
-
,

i t is o f t en liquid If the c ru d e xylene c ontain other substan c e s as well the

.
,

nitro pro duct w i ll of course be sti ll more complex The liquid products
-

, ,
.

c a n be u s e d li ke li q u i d tri nitro toluene

, for the manufacture of plasti c e x p lo
-
,

s iv e s,
the liquid being thickened by di ss o lving some collodion c otton in it .

Some i nventors have proposed to nitrate w ide fractions of coal tar naphtha .

Thu s C Distler E Blecher and C Lopez nitrate the fraction boiling between
.
, .
2
.

1 3 0 and
°
and O Silb e r r a d that between 20 0 and
3
. There is no °

publi s he d information as to the chemical stabi lity of the s e c omplex mi xtures

o f nitro compounds
-
.

NI TRO-NAPH TH ALENES
This substance is made by nitrating naphthalene w ith a mi xed acid con
taining only slightly more than the theoretical amount of nitric acid The .

acid is place d in a nitration pot provided w ith a stirrer and the naphthalene
a dded a little at a time the temperature being kep t below , Then the
liqui d mi x ture i s heated to 60 for an hour A c onsiderable amount of red °
.

fumes i s evolved in conse quence o f secondary reactions involvi ng the forma

tion of phthali c aci d and other oxidation products On coo ling the nitro .

naphthalene c rystalli zes out on the surface of the a c id which is then ru n off , .

The produ c t i s centrifuge d washed wi th water and di lute so di um carbonate

,

solution then with water again and d ri ed at

, It may be purified by
recrystallization from alcohol or benzol The yi eld is about 1 1 0 per cent . .
,

whereas theoreti c ally i t should be 1 3 5 per cent .

There are two mono nitro naphthalenes but under ordinary c o nditions
- —
,

of nitration the u compound only i s formed -

The melting p oint of this i s .
-

gi ven variously as 58 5 and but the c ommercial product not being quite
°
,

pure melts at about

, It i s a neutral body insoluble in water but s o luble , ,

i n ether alcohol carbon bisulphide petr o leum ether e tc As an explosive

, , , , .

i ts po w er is small but it i s used in che d dite as a combustible and aggl o merant

, ,

its softne s s helping to bind the p o wder together Its sp e cific gravity i s 1 3 3 1 .

at 4 °

1
S ee S S . .
, 1 90 9 , p . 10 6 .

2
r
G e m P ts . a . r n hP
F e c a t . E n g . Pa t . o f 1 90 7
3
Eng . Pa t s. a nd o f 1 9 12 .
 NIT RO D E RIVATIVE S -
OF A ROMATIC H YD ROCA RB ONS 269

If nitro naphthalene be further nitrated i n the same way a mixture of two

-
D ini tro
na p h th a len
dinitro naphthalenes i s obtained
-

NO 2 N0 2

0. or 8
,
or

mp . . 21 7
°
mp . . 1 70
°

or nap hthalene may be n itrated directly to the dinitro comp ound if a su fficient -

quantity of acids of suitable strength be used The commercial product .

melts at about Both isomers are used for the manufacture of dye stuffs -
.

To separate them advantage i s taken of the fact that the a compoun d is almost -

insoluble in many organic solvents whi c h dissolve the B comp ound with ease ,
-
.

The cru de product i s washed with water treated with carbon bisulphide to ,

remove nitro naphthalene and then with acetone to dissolve B di nitro n a p h

-
,
- -

th a le n e But for the manufacture o f exp losives it is not necessary to separate

.

the isomers Dinitro naphthalene is a constituent of G ri s o u n ite s made in

.
—

France of Ammonite and some other similar explosives It is decidedly

,
.

insensitive and not at all p owerful as an e xplosive .

This i s m ade by nitrating mono or di nitro naphthalene w ith moderately T init o — - r r

na ph th len a
strong mixed acid A mixture of several isomers is obtained melting at ab out 0 H N3 0 6
.
10 5 '

This is washed and heated in copper crucibles to a temperature above

,

the melting p oin t until no more gas is evolved

-
The molten mass is then .

p oured into water p owdered centrifuged and dried ,

It i s used in the same ,
.

classes of explosives as dinitro naphthalene and has also been added to -

,

smokeless p owders as a stab ilizer 1

.

This i s made by nitrating di nitro naphthalene with a mi xture of nitric T t a nit - e r ro

n p h th l m a a e
aci d and oleum It is a mixture of several isomers and melts at about
.
c H N0 lO 4 4 8°

It has been but little used in explosives probably because the y ield is small ,
.

M P atart has in the laboratory nitrated naphthalene with a large n u mb c r

.

of different a c i d mixtures using the acid in the prop ortion of 30 parts to 1 of ,

naphthalene ? The results have been plotted by Sa p o s h niko ff on a triangular

diagram similar to that on p The curves showing the degree of nitration .

attained take a very similar course to those for nitro cotton In practical -
.

manufacture th e prop ortion of a c id use d is very much smaller than P atart

employed but the results may be of value as indicating the comp osition that
,

the waste aci d s should have .

1 Ve nni n et C he neau s , p 268

. .

2 38 ; v o l i
P . ci S .
, v o l. ix .
, p . .
p 1 47
x .
,
. .

3 J . Ru ss , P hy s C he m S ea
. .
, 19 14, p 1 10 2 C hem S oc A b s tr
. . . ., 1 9 1 5, i ., p . 39 3.
 270 E X P L OSIVE S

P OIS ONING BY AROM ATIC C OMP OU ND S

The a r oma t ic h v dr o c a r b o n s have a decided to xic ac ti on ; the vap our s o f
be nze ne a n d toluene p r od uce giddin ess a n d fi nally in s ensibil ity when inhaled .

W orkers w h o a re c on t antl y exp osed to the fumes may suff er seve r ely in
'

hea l th Ade qua t e fan shoul d t herefor e be p rovided when these volatile
.
s

liquid a re e xposed in open ves se l

s s .

The nitro derivati ves of the se hydr ocarbo ns a r e mo r e p oisonous than

-

t he v a re t hemse lves but a re n o t so vola t ile Dini tr o be n zene and di ni tro

, .
-

t o luene a re speciall y poi onou and their use in exp losives i s t her efore s s
,

obj ec t i onable E xp losives c onta inin g them should not be handl ed with the
.

ba re hands and durin g all manufactur ing ope r ations p r ecautions mu t b e

,
s

taken to p r event w orkers inh alin g the du t and fi mi es 1

A French Commis ion s . s

whi ch r eport ed on thi subj ec t in 1 9 1 2 foun d that

2 s

1 The w orke rs m ost frequently aff ected a re gene ra lly young people who
.

have not been wor king long in the factory .

2 Most of these worke r s are dr in kers

. .

3 Se r iou atta c k are most fre quent in Jul y and Augu st and esp ecially
.
s s
,

when the wea t her is t hun de rv the vap ours being libe rated to a grea te r exte nt
the hi gher the te mpe ra ture .

The s y mpto ms a re dr o w sin ess someti mes goin g a s far a s unc on sciousness , ,

gas tr ic tr oubles e x ce ma a n d fronta l hea dac he In mi ld ca se s a fe w hours

, , .

in the open air may c ure the patient Seve r e ca s es may end in death Mo r ke r s
'

. .

w h o sho w si gn s of bei ng a ff ected should at once be t r ansfer red t o ot her work

at a n y ra te for a ti me .

Tr ini tro benze ne and toluene are generally considered to be much less
- -
,

poi onou than th e dini tr o compoun d

s s There have however been some -
s .
, ,

ca se s of fata l poi oni ng b y t ro t y l but these may have bee n due rea lly to
s
,

the p res ence of di nit r o toluene -

.

Pic r ic acid h a s a disa g r eea ble bitt er t a s te but is not very poi sonous The , .

chl or nitro c omp oun d on t he other hand are more dangerou s than those
- - s
, ,

not c on t a ini ng chlorin e Some of the other ni tro derivatives such a s .

-
,

tet ry l and hexa nitro di phenyla mine have been foun d to b e de cidedl y
- -
,

p ois onou s .

The curative mea sur es ad opted in Ge r many a re : immedia te removal

fr om the fa c to ry a rti ficial respirati on and inh alation of o xy gen and non
, ,

a lc oholic sti mul ants As p reventa t i v e mea sur es al cohol is forbidden during
.

working h o u rs and only m od e ra te qu a nti t i es a re allowed at other times The

, .

worke r s should w ea r lea t her gloves and clot hes fitti ng tightly at the n e ck -
,

wris t s a n d a nk les Their b oots should have wooden soles and they shoul d
.
,

1
Sec Re po t to r the Ho m e Secr e ta ry b y D u pr é a nd Smit h , 1 8 9 3.
2
P e: S , v o l
. . . x v i , p . 1 44 .
 NIT RO D E RIVATIVE S
-
OF A ROMATIC HYD ROCA RB ONS 27 1

put c otton wool in their ears and when necessary they should wear respirators
, .

Meals must not be taken in the working rooms and before eating the worker ,

must wash his face and hands with soap and water and clean hi s nails with a
nail brush and rinse his mouth out with a 2 per cent solution of t incture of
-
,
.

myrrh The workers have daily a douche bath and once a week a tub
.
1
.

1
R . E c ale
s s, N i tr o s p re ngs tofi e, p . 21 1 ; s ee a ls o S S
. ., 1 90 8 , p . 259 .
 C H AP TE R XX
OTH ER NI TRO-AROMATI C COMPOUND S

De i r va t iv es o f An ilin e

An ilin e C 6H 5NH
’

h ny la m in (C H ) NH
2
D ip e H e a n ite d ip he ny la mi ne
6 5 2 x ro -

(C 6H 2N 3 0 6) 2NH
‘
N it r nilin N itr o me t h y l n il in c s Manufa c t ur e o f t e t ry l
o -a es -
a

P r p rt i
o e o f t tr y l
es H igh r n it r o d riva t iv e o f m t hy l anilin e P i ric a c id
e e -
e s e -
c ,

C H N O
3 3 s
Pro p rt i s
7 H igh e r n it r o p h n o ls St y p hni c a c id C H N 0
e e -
e
6 3 3 3

Tr in it ro c re s o l-
,
P ic ra t e s a nd t rin it ro c e s y la te s -
r

Trin it ro an is o le C H OC H n
-
, ) : K in e t ic s o f n it ra t io n
e z z 3

A N I L I N E i s made from ni tro benzene by treating it w ith iron b orings and

-

C CH b NH 2
hy drochlori c acid The nascent hydrogen replaces the oxygen W hen
.

. .

reduction is c omplete the a ni lin e i s distill ed in a current of steam allowed ,

to settle and pu r ified by di st ill ation in va cu o For details of the processes

,
.

s ee Tho r pe s D ictiona r y o f Ap p li ed C hemi s tr y vol i p 260

’
. . .
, ,

Anili ne when pure i s a c olourless liquid wi th a specific gravity of 1 0 25 at

, ,

and boiling at It i s u sed very extensively for the manufacture

of syntheti c dyes and some of its derivatives are used in the explosives industry
, .

The substa nce itself has been u sed as a stabili zer in smokeless p owders but ,

its strongly basic character and its volat ility are seri ou s objections : i t has
now been replaced for this purpose by other substances nota bly di p h enylamin e , .

Thi s is made by heating a nili ne and ani line hydroc hlori de together in
an autoclave for thirty to thirty fi v e hours at 220 to The product -
°

i s e xtracted wi th hot dilute hydrochlori c acid w hi ch dissolves the un ,

c hanged anili ne hydrochloride whilst the di phenylamine fl oats on the surface

a s free base The yield i s 60 to 70 per cent of the a nilin e u sed It i s a
. . .

H
 OTH E R NIT R O A ROMATIC C OMP OU NDS -
273

crystalline solid melting at 54 and boiling at It i s almost insoluble °

in water soluble in alcohol benzene and ether and onl y feebly basic It is
, , , .

used as a s ta b liz e r in mili tary smokeless powders and also for the manufactur e ,

of dyes .

”
One of these dyes i s the h e x a nitr o derivative known as Aurantia -
, ,
Hex a n itr o

which is made either by nitrating di phenylamine or by other synthetic methods 1 .

I t is a p owerful e x p lo s iv e b u t does not appear to be used much for this purpose , ,

(C eH eNsO e lz

nor is it any longer used much as a dye It is acid in character and somewhat .

p oisonous Its colour i s lemon yellow and it melts at

. It i s more sensi ,

tive to blows than tetryl 2

.

O —
NH —

O
The direct nitration of anil ine is liable to give low yields because b v reactions Nitr ,
-
o

a nil m s e
set in Therefore it i s often combined first with acetic acid to form acetanili de
.
,
’

which i s nitrated and then heated wi th di lute acid or alkali to remove the
acetyl group In this way ortho and p ara nitro anil in e can be made
.
3
The - —
.

meta co mp o u n i s obtained by the partial reduction of meta di ni tro benzene

- - -
.

Various other indi rect methods can be used The m ono and di nitro anilines .
- -

are readil y nitrated further Thu s ortho nitroanilin e gives 2 4 6 trin itro .
- -

a nili ne or p icr a mide w hi ch however i s more easily made by the action

, , , ,

of a m moni a on trini tro chl or benzene This i s a p owerful e x p lo s iv e b u t has - -

.
\

n o t been used on a large scale .

Similarly meta ni tro ani line gives tetra ni tro anilin e and Flur s ch eim has
4 - - - -
,

proposed to u se thi s as a c ommercial explosive as it i s m ore p owerful than

5

any substance at present in use He make s the nitro anilin e by treating .

-

c ommercial di ni tro benzene wi th sodi um bis ul p hi de and water The product

-
.

thus obtain ed without previ ous purifi cation i s nitrated with mixed a c id at
, ,

ab out 70 or lower The nitration proceeds rapidl y The crystals of tetra

°
. .

nitro aniline are filtered o ff from the undil uted waste acids washed with
-
,

water and dried In this way c ommercial dinitro benzene yields almost its
.
-

own weight of pure tetra nitro an iline whereas theoreticall y it should yield - —
,

1 5 3 times its weight Tetra nitro anili ne i s a yellow soli d with a specifi c .
- -

gravity of 1 8 67 It cannot be melted without dec omposition ; if heate d

.

1
S ee S S , 1 9 10 p . . , . 16; al so T C e . ar t r , S S . .
, 1 9 1 3, p . 20 5.
2
F L . an n h t S S
g e s c e id , . 1 9 1 2, p 446 . .

3
Fo r t h e p ro p r t io n a n d
o s y ie ld s s ee A F . . H o lle man , J . C . Har t o
g a nd T . v . d Lin d e . n ,

B er ., 1 9 1 1, p . 70 4 .

4
B Fl ur s c h e im
. a nd T Simo . n , P r o c C hem S oc . 1 9 10, p 8 1 .
. , .

5
Eight h I nt ern C o g Ap p l C . n . . he m .
, 1 9 1 2, v o l iv , p . 3 1 S S . . . .
, 1 9 1 3, p . 1 8 5. Eng .
P at s . 3 224 a n d 3 90 7 o f 1 9 10 ; e G rm P a t s . . a nd

V OL . I .
 °
5 mi nute i t melts at a bout
3 It is cla imed for it that it is not more
se nsi t ive than tet r yl a n d t hat it is s t a ble but on bo ili ng w ith water it is
, ,

converte d in t o t rini t ro a min o phenol and the sa me substa n ce i obtain ed

- -
,
s

in tan t a n e ously a t th e o r dina ry tempe r a t u re by th e ac tion of an e q ueo us

s

solu t ion of sodi um aceta te .

mp . . 1 74
°
—
1 75
°

Me th yl ani li ne i s mad e by h ea ti ng a nlin e hydr ochl oride or sulphate with

-

methyl alcohol On nitrati on fo u r NO group s ca n b e made t o enter t he

.
2

molec ul e wi t hout any grea t diffi cult y th r ee c ombini ng with the ca rbo n a tom s ,

of the be nze ne ring and one w ith the ni trogen Thi s substa n ce is ofte n call ed .

tet r ani tro anili ne but stric tly spea ki ng its scient ific name is trinitro phen y l
-
,
-

ni t ra mi ne c ommercially it is called t etryl or te t ralite I t w a s fi r st desc ribed .

by Ro mb u r g h in and is ob ta ined al o on ni tra ting dimethyl anili ne s -

,

which is made in a s imila r manner to methyl anili ne -

.

x 0 ,

The follo wi ng is t he method of manufac ture a s desc ribed by F La ngen .

oi tetr yl
.
scheidt 2
The dim e thyl a n ili ne u sed shoul d be of a high deg r ee of p urity ;
-

9 5 per cent of it shoul d di til over withi n a ra nge of 1 or 1 1 C Its sp ec ific ° °

.
s .

gra vi ty is 0 9 567 at and i t s boili n g point l 90 (a t 760 mm Acco rdi ng to -

°
.

the Tables of La ndolt B iirn s te in 1 9 12 t he spec ific gra vi t y i 0 9 555 a t

-

, ,
s

and t he bo iling poin t 1 9 3 1 at 760 mm ) The ni tr ation ves sel consi ts o f a n

- -
°
.
- s

e namelled pot p r o v ide d with an enamell ed sti rrer and a j ac ket thr ough whi ch ,

water or steam ca n be pa ssed In i t 1 00 0 kg of colo u rles s lea d free sul phur ic . .

-

ac id of 9 7 to 9 8 per cent st reng t h are pla c e d the stir rer i s sta rted and 10 0 kg
.
,
.

of the di methyl a nili ne is slowly r un in : thi takes abou t tw o hour s The

- s .

ac id in di ssol v in g the di methyl aniline becomes colour ed li ght b r own but -

,

t he colour mu t not be so dark tha t one ca nnot see thr ough a la yer 5 cm
s .

t hick A da rk c olour is gene r ally due to ins uffi cient c ooling or too ra pid
.

1
Rec . l ra v. ch i m ., vo l . ii .
, p . 10 8 .

2
SS
. .
, 1 9 12, p . 44 5 . S ee a ls o F . M . V as q u e z , SS . .
, 1 9 1 1, p . 30 2 .
 OTH E R NI TRO A ROMATIC
-
C O MPO UND S 275

ad diti on of the di methyl aniline The s ulp huric acid solution should be
-
.

ni tra ted wi thout unn ecessary loss of time other wi se there may be darkeni ng, ,

and the dark colour cannot be removed from the fin ished tetryl .

The ni tration i s carried out in the same or a simil ar vessel In it are placed .

first 430 kg of ni tric acid of 47 B (sp gr 1 4 8 3 8 7 3 per cent H NO ) and

.
°
. . .
,
-
.
a

heated to 40 C and the sul phuric acid solution i s r u n in in a thi n stream

°
.
, .

At first the te mperature must not be allowed to rise above but when
t w o thir ds have been r un in the temperature may be allo w ed to rise to
-

The addition takes eight or ni ne hours ; after it i s fini shed the te mperatu re
i s maintained for another two hour s at 53 to 55 to c omplete the ni tration ° °
.

The oxidation of one of the C H group s causes the contents of the vessel to
3

froth c onsiderably t e n the nitration i s c omplete the mixture i s cooled

.

to the ordi nary temperature and allowed to stand over night The te trani tro .

methyl ani li ne sepa rates out on the sur face in fine crystals provided that
-
,

the ni tric acid used i s not stronger than a s stated ab ove If stronger aci d .

be used the crystals are larger and cannot b e washed properly Next mornin g .

the waste acid i s r u n off it has about the follo w in g c omposition

74 -0 4
1 10 5
2-58
02 4
\V ate r (b y diffe rence ) 12 19

Sp e c ifi c g rav i t y

Afte r drainin g o ff the waste acid the soli d product is washed by means of
dil ute sul p huric acid on to the plate of a vacuum filte r where it is washed ,

with more di lute s ul p huri c acid Then it i s removed to another fil te r where

.
,

it i s washed with wate r un til it i s neutral To test for thi s 1 5 or 20 g o f the

. .

wet substance equivalent to about 1 0 g dr y are boiled w ith 50 c c wa te r

, .
, . .
,

cooled fil tered and washed the fil trate should not require more than 0 2 c c
,
-
. .

N 1 0 caustic soda solution to render it neutral to p henol phthalein Thi s .

amoun t i s p rincipall y due t o the fa int acid character of the p u re te tryl The .

substance i s then dr ied It now has a meltin g point of 1 26 to

. and the -
°

yield i s about 21 0 kg whereas accordi ng to theory there sho u ld be 23 7 kg

.
, .

from 1 00 kg of di methyl anili ne

.
-
.

It is necessary fu rther to p urify the tetryl by recrystall ization as small ,

amounts of impurity se ri ous ly affect its stabil ity For thi s p urp os e 500 kg . .

are dissolved by boi lin g in 1 8 50 kg of pur e benzene and allowed to crystallize

.

out fi fte r e d off and dried The benzene i s rec overed from the mother li quor
, .

by di stil lation but some water i s a dded to the stil l to prevent heatin g the
,

solid residue above About 1 3 per cent of the crude tetryl i s lost by .
276 E X PL O SIV E S
this proce s s a nd remains in the still As this residue is unstable it i s destroyed .

by burning There are also oth er metho d s of purificati on in use

. .

P ure te t ryl looks li ke flour wi th a faint yello w c ol o ur The melting point .

-

of t he pure substance i s 129 to that of a good c ommercial mate rial °

1 27 5 to l 28 2
-
o °
°
.

Tetryl is a m ore po w e r ful explosive than trotyl or picric acid but it is ,

also somewhat more sensitive without however being dangerously so w ith , , ,

or dinary precauti ons This makes i t very sui table for u se a s an intermedi ate
.

detonating agent It is used in conj unction wi th ful minate as a fi lli ng for

.

detonators and as a p ri mer for hi gh explosive shell Detonating fuse has

, .

also been fill ed with it Acc ordi ng to Langenscheidt it gives a Tr a n zl test.

of 4 60 to 48 0 c c a nd i n the falling weight test i t re q uires a weight of 5 kg

. .
, .

fa lling 30 to 40 c m to explode it I t is somewhat p oisonous and should

. .
,

not be han dled m ore than is necessary a s it is liable to set up skin irrita tion .

It i s a component of some ammonium nitrate explosives such a s Fo r te x ,

but its c o mp a r a tiv e y high cost of manufacture prevents its extensive use
'

for thi s purpose .

S till higher ni tro derivatives of methyl anili ne have been prepared but
— -

are unsta ble Tetranitro phenyl methyl nitramine i s a substance melting

.
- - -

at 1 46 to °
on boiling w ith water one of the nitro group s i s replaced -

by OH and nitric aci d i s formed

O th er reagents produce mil a r changes

'

1
s .

CH , No 2

The correspondi ng penta ni tro derivative i s a ye ll o w crystalli ne s ubstance - -

which melts at 1 32 and e xplo des at a higher temperature 2 °

.

1
Ro mb ur g h Rec tr a v ch ina 1 8 8 9 p 1 0 8
, . . , , . Ro mb ur g h a nd Sc he p e r s , P ro c . K A ka d
. .

W etens ch A ms t e rdam 1 9 1 3 p 3 69
.
, , , . .

2
J J B la n ks ma P r o c K A ka d l Vete ns ch
. . . . . . .
, Ai n s te r d a rn l 9 0 2 p 43 7
,
_
, . .
 OTH E R NIT RO A ROMATIC C O MPO UNDS
-

NI TRO-PH ENOL S
P henol(carbolic acid ) i s nitrated very easily even by di lute nitric acid
yielding a mixture of ortho and para nitro phenol and these on fur ther ni tration - -
,

give 2 4 di nitro phenol which may also be obtained by the direct ni tration
- -

of phenol with mixed acid These compounds are not however used as . , ,

explosives although they c a n be detonated w ith some di fficu lty

,

P icric acid or 2 4 G trinitro phenol has however been used on a very

,
- -
, , ,

large scale as a military explosive and is still in spite of the fact that trotyl , ,

is generally preferred .

This substance is the final product of the action of nitric acid on a large
number of substances c ontaining a benzene nucleus j ust as oxali c acid i s the .
,

result of the oxi dation of many b odi es of the fatty series P ic r ic acid i s .

obtainable from indigo aloes gum resins wool sil k etc but the c ommon , ,
—
, , , .
,

idea that the yellow c olour produced by nitric acid on animal tissues such ,

as skin wool etc i s due to the production of picric acid i s erroneous it is

, , .
,

due to the formation of xanthoproteic acid .

P icric acid was formerly prepared by the di rect action of nitric acid on
phenol but i s now made by first di ssolving the p henol in strong sulphuric
,

acid and then acting on the res ul ting phenol sulp honi c acid with excess of —

nitric acid Mono and di nitro phenol may result if the action i s not carrie d
.
-

far enough P icric acid separates from the acid mixture as an oily liquid
.
,

which soli difies on cooling .

A H Ney in a lecture delivered before the National E xhibition of American

. .

Chemical Industries in New York has given the foll owing information about
the manufacture of pic ri c acid 1

The technical production of picric acid is to day carried out by two di stinc t -

processes
1 The first and older method which even to day is employed almost
.
,
-

exclusively c onsists in treating phenol with concentrated sulphuric acid at

,

about 1 0 0 to 1 1 0 until the odour of phenol has di sappeared and the reaction
° °

product i s completely soluble i n water and nitrating the sulphuric acid thu s ,

o btained with an excess of nitric acid preferably in the presence of an excess ,

of sulphu r ic aci d .

1
J M . . e t. a nd C he m E n g . ., 1 9 1 5, p . 68 6 ; C hem Tr a de
. J ama , 1 9 1 5, p . 38 5
. S ee a ls o

S S
. .
, 19 10 , p . 15 .
278 E X P L OSI VE S

2
. The sec ond and m ore m ode r n method employs as sta rtin g mate rial
chl orbenzol w hi ch i s di ni trated to din itro c hl o r b e n z e n e ; thi s pro duct i s
,
-

separate d from the spent ni trat ing mi xture the chl orin e atom r epla ced by ,

hydroxyl by heat ing w ith caustic soda and the result ing din itro phenol is ,
-

nitrated .

The possibili ty of a third c ommercial method for the production of picric

acid is sugges te d by an o ld publication by H e pp who claim s to have obta ined
l
, ,

w i t h an exce llent y ield pic ric acid by o x i d iz ing trini tro ben zene in a lkaline
,
-

solution w ith potassium ferric cyani de th e use of other mifd o x i di zing agents ,

being also suggeste d .

In view of the difficul t y in obtai ning trin itro ben zene wi th anythi ng li ke -

a satisfactory yield the c ommercial feasib ili ty of such procedure i s open t o

,

grave d oubt although the wri te r has p rivate information that a small plant
,

is at the present time producin g picric acid to some exte n t by a process p ur

por tin g to be base d upon thi s method .

The chemical a n d tech ni cal li terature contains many suggestions and

several descripti o ns for the manufact u re of pic r i c a c id all of them ho w ever , , ,

being obsolete Chemically the preparation of p ic tic acid i s very simple

.
,

and easy and as a matte r of fact it woul d seem alm ost impossible for any one
, , ,

placin g phenol and nitric acid together in some form and manner not to , ,

ob tain picric acid Techni cally however the manufactur e in volves several
.
, ,

difficul t problems mainly due to the fac t that the handlin g o f u nmixe d ni t ric
,

acid i s a di ffi c ult and dangerous operation e xclu di ng th e use of mate rials for
recepta cles e tc usually employed in the chemical i nd ustry and the s o mewhat
, .
, ,

exaggerate d fear of contamination by inorganic salts detrimenta l to th e ,

stabili ty of the product The d rying and pulverizin g of the materi al is a

.

very dangerous operation whi ch however i s now sel d om requi red in c hemi cal
, , ,

factories the Ordnance w orks u sually requi ring deli very of t he wet crystals
,

with a moisture c onte nt of approxim ate ly 20 per cent .

The manufac ture o f picri c a c i d i s c arri ed ou t a s follows :

A large sulphonation kettle of the u sual c o n s truction preferably lea d ,

lined wi th ste am j acket bottom di scharge and agita to r i s charged wi th

, , ,

one part phenol and four parts sulphu ri c acid 9 8 per cent The mixt u re i s , .

heated un d er agita tion u ntil a sample appears c omplete ly sulph onate d

that i s soluble in wate r without turbidity and having n o odour of p h enol
, ,
.

The c on tent o f the sulphonation ket t le i s now di vided into the ni trators ,

whi ch are rec eptacles suspended in a space adapte d to have h ot or c o ld wate r

c irc ul ated therein To the conte nt of each kettle an equal pa r t of sul phur ic
.

acid i s added and af ter re ducing the te mperature to bel o w 20 the nitra t in g
,
°

acid is r un in Thi s is prefe r ably a usual mi x ture of equal part s o f s ul phu r i c

.

i c id a nd nit ri c aci d o f 62 per cent s tr e ng th b u t o ther pr o porti o n s may be . ,

1
A n na l e n 21 5 , p . 344 .
 OTH ER NI T RO AROMATI C -
C OM P OUND S 279

u sed Instead of the three molecul es requi red by the theory fo u r molecul es
.
,

of H NO are added ; the temperature i s kep t below 40 whi le the fi rst 30

3
°

to 40 per cent ni tric acid is run in and th en gradu ally in creased t o 70 or

.
,
°

hot water be ing circul ated towards the e n d of the operation and one to
two hour s af terwar ds P roper ventil ation must be provided Ai r may be
. .

blow n through the ni trators before removi ng their conte nt in order to remove
the nitrous gases forme d The conte nt i s now removed into an acid proof
.
-
,

non metallic receptacle and di luted with water about equal volumes having
-
,

been foun d to give the best results After c ooling the picric acid which .
, ,

separa te s usually in large crystals i s filtered by means of n u tch e s or ,

cent r ifuges and washed The yi eld i s somewhat less than the theoretical
, . .

The formation of too large crystals and ca kin g should be prevented It .

i s now usually of sufficient pu ri ty but t o obtain it still pur er it may be fused

, ,

in a steam j ackete d enamell ed kettle from which it i s run if desired t hrough

-
, , ,

a sieve of platin um or gold into a wooden tank with water It i s then filtere d
, .

o ff again The method suggeste d in the li teratur e of di ssol v ing i n alkali

.
,

and aga in precipitatin g i s irrational and dangerous and has never been
, ,

practised by manufacturers .

The material of w hi ch the nitrators are made may be cast iron if the -

strength of the acid is always kep t ab ove 8 2 8 5 per cent otherwi se earthen —
.
,

ware o r enamel receptacles are in di spensable After the nitration the mi xture .

i s dilute d and for all fi nal operations c ontact with metals other than precious
, , , ,

must be avoided 1
Coatings of a pure a sp h a ltu rn varni sh have given satis
.

faction . P roper agitation devices and ready means for di scharging the
nitrators and fill in g the same open a w ide field for the in genuity of th e con
structional en gineer .

The largest manufacturer of picric acid in the world (Hauff in Fu e r b a c h )

uses an interesting and hi ghly efficient fil terin g devi ce It c onsists of a filtering .

”
b ox or n u tc h wi th vacuum below and ab ove and is adap te d to be used
, ,

as both fil ter and dr yer The crude picri c acid is placed on the filtering
.

surface (a p orous stone plate ) and suction i s app lied After the bulk of the .

a dherin g waste acid has been removed alcoh o l is sprayed on the m aterial ,

and received in a separate c ontain er from which it i s at once rectified a n d ,

recovered The filte r b ox i s then c overed wi th a speciall y c onstructe d lid

.

and vacuum appli ed ; the dr yin g proceeds very rapidl y and the resulting ,

product i s very pure due to the fact that it has been washed w ith alcohol
, ,

which is an e x cellent solvent for the resinous products always forme d duri n g
high ni tration .

P icric acid forms pale yellow crysta lline needl es or scales of an intensely
, ,
t
Pr o per ies .

bitter taste and specific gravity l 767 at The pure acid melts at 1 2 2
'
°

a n d the c ommon at a lower temperature t o a bro wn ish yellow o il which at ,

-
,

1
Tin nd lu mini um m y b u ed A M
a a a e s —
. .
28 0 E X P L OSIV E S

a hi ghe r te mperature par t ially sublimes and bo ils with formation o f yellow , ,

bi t ter s uff ocatin g vapours The lo w er meltin g point of impure pic ri c acid
, .
-

i s probably due to an a dmix t ure of dini tro pheno ls or of a nitro cresol Hence - -
.

t he mel t ing point of pi c r ic acid is a te st of its pu r ity

-
.

When strongly heated pi c ri c acid burn s rapidly wi t h forma t i o n of an ,

inte nsely black sm o ke It does not explo de when hea t e d under o r dina ry .

con di tions but it can be made to explode by a llo w ing it to fall into a tube
,

heate d to a red heat 1

P icric acid c a n be d etonate d by means of other vio lent
.

explosives ; a charge of 1 g of mercury fulminate suffices to de termine the .

e xplosion under favourable con di t ions Meta llic picrates especiall y that o f .
,

lead or even an imperfect mi xture of picric acid with t he o x ides or nitrates

, ,

wi ll detonate vi olently when heate d or submitte d to a m oderate blow and ,

the e xplosion wi ll induce the detonation of neighbourin g quantities of pic ri c

acid or picrates even though they be w e t In spite of the comparative
,
.

insensitiveness of the pur e substance these properties have led to a num ber ,

of serious accid ents of whi ch the foll owing were particu larly disa strou s ,

Heron Chemical l Vo r ks Lancaster June 7 , , ,

Roberts Dale a nd Co s Works C o r n b r o o k near Mancheste r , Jun e 22

’
.
, , , ,

Rheinau near Mannheim Jun e 27 , , ,

Read Ho lliday and S ons Huddersfield Ma y 30

, , , ,

G ri eshe im E lektron near Frankfort a Ma in April 25 1 9 0 1 t w enty four

-
,
.
, , ,
-

killed and one hun dred and seventy eight i nj ured 6 -

.

“W oolwi ch Arsenal J une 1 8 1 9 0 3 sixte en killed and fou r te en inj ured , , ,

7
.

For the histori cal development of the use of pi c ri c acid a s an expl o sive ,

see Chapter III pp 44 49 It i s n o w used onl y as a m ili tary explosive either

, .
,
.

alone or mixed with a nitrate or wi th o t her ni t ro c o mp oun d s It i s not -

.

itself used much a s a dye now but it i s use d in the manufacture of m o re c omplex ,

c ompoun ds which are valuable dy e stuff s ,

-
.

The sensitiveness of pic ric acid can be reduced by mixing i t wi th inert

substa n c es U nder Or d ers i n Council Nos 20 and 20A it is not c onsidered
.
,
.
,

a n e xplosive when mixed with ha lf its w eight of wate r or w i t h three times

its weight of the foll owi n g substances anhydrou s sulphate of soda crysta lliz ed ,

sulphate of so d a when in hermeticall y closed packages or p otash alum 8

It ,
.

i s al s o not considere d an explosive if in a quantity of not ex c eedi ng 20 0 0 lb .

1
M . Be rt h e lo t , A nn C h im P hy s
. . .
, 18 89 , v o l. x v i .,
p 23 . P . et S 1 90 0 , v o l. x .
, p 28 0
. .

2
S R . .
, 8 1, p . 20 , H o me O ffi ce a
P pe rs A ,

a
S R . .
, 31 .
4
A R . .
, 1 8 90 , p . 48 .
5
S R . .
, 1 39 .

6 A ng 1 90 1 , p 459 ; C he m Z e zt Ma y C he m Tr a de J oa Ma y 18 a nd
'

.
, . . .
, 1 , 1 90 1 . n ,

25, 1 90 1 (C h e mic a l o es ) N t .

7 A R . .
, 11 0 3 , p . 51 ; C he m . Tr a de J a ur ., Jul y 4, 1 90 3 .
8
S ee C a io e to the E x p lo s i ves A ct p p , . 20 4 20 6. —
 OTH ER NIT RO A ROMATIC -
C O MPO U ND S

p acked in sub stantial barrels or cases w here it i s not liable to come in

contact with any metal other than aluminium nor with the oxides or other ,

c omp ounds (other than sulphates ) of lead iron potassium barium calcium , , , , ,

sodium zinc or copper nor w ith any chlorate nitrate or other oxi di zing agent
, , , ,
.

Other trinitro phenols are known but they are not made so eas ily and
-
, ,

are probably less stable Higher nitro phenols have also been prepared
.
-

thus J J B la nk s ma
. .
1 by nitrating meta nitro phenol with mi x ed acid i n - -

the cold obtaine 2 5 tetra nitro phenol which melted at 1 40

‘

r and - - -
,
°

exploded at a higher temperature but accordi ng to R Nie tz ki this compound

2
,
.

melts at often with a somewhat violent explosion In a simil ar manner .

B la n ks ma obtained p e n ta ni tr o phenol from 2 4 dinitro phenol These — - -

.

substances are not very stable and are converted by boiling with water into
trinitro resorcinol a nd trinitro phloroglucinol respectively
— -
.

Styp hnic acid or 2 4 6 trinitro resorci nol is made by nitrating resorcinol Sty ph ni
- -
c
a id c
or some of its deri vatives Resorcinol or meta di hydroxy benzene can be c H N O
.
,
- -
,
G S S S.

made from benzene in the same way as synthetic phenol but its derivatives ,

occur in many gum s and wood extracts and these can be made to yield styp hnic ,

acid directly by appropriate treatment with nit ri c acid 3 B ottger and Will .

obtained a yield of 1 8 per cent from Brazil wood extract (Fernambukholz .

extrakt ) 4
.

S typ hnic acid is a fairly strong di basic acid and its salts are more violently ,

explosive than those of picric acid Its use as an expl o sive was patented by .

Hau ff in 1 8 9 4 and in 1 8 9 7 it was e x amin ed b y the French Commission des

,

S ubstances E xplosives who found that it was less powerful and more expen s ive
5
,

than pic ri c acid over which it posse ssed no advantage It does not appear
, .

ever to have been used commercially as an explosive but is worthy of notice ,

1
P r oc . K . A ka d . W ete ns ch .
, Ams te r dam , 1 902, p . 43 7 .

2
B er .
, 1 8 9 7, p . 1 8 1.
3
S ee S t e nh o us e , An na le n , v o l. cx i v .
, p . 224 .

4 A nn a len , v o l. v
l iii .
, pp . 269 , 29 8 .
5 P . et S .
, v o l. ix , p . 1 39.
 E XP L OSI V ES

in onse quence of i t s formation

c di rectly from natura l products . Its melting
po in t is

In commercial cres ol obta in e d fr om c oal ta r t here are three creso ls present

in abou t t he foll o wi ng prop or t ions

Pr o p o r t io n

Me ta

Mono and di ni tro compounds ca n b e ma d e from a ll of t he se but only

- -
,

meta cresol gives a t rin itro de r ivative the o th ers on con t inued ni t ration
- -
,

be ing o x i di z ed to oxalic acid etc It i s nece s sa ry t herefore to u se meta

, .
, ,

c resol a s p ure as practica ble for the manufacture of t rini t r o cresol The - -
.

o rtho c ompound can be eli min ated by fractional dis t i lla t i o n wi t hout gre a t
-

diffic u l t y but the others boil at almos t the sa me temperature Never t heless
,
.

it is sa id that t he meta compoun d ca n be o b t a in ed a lmos t pure by frac t ional

-

dis t illation 1
The separati on can als o b e effected by sul phonation wi t h
.

oleum whereby meta cresol is c onvert ed in t o a li qui d sulphoni c acid and

,
-

t he para compound into a s oli d one For o t her me t ho d s of separa t ion s ee

-
.

Th o rpe s D ictio na r y o f App lied C he mis tr y vol ii p 1 64

’
, . .
, . .

Trinitro cres o l i s ma d e in t he sa me w a y a s pi c ri c acid bu t t he ni t ra t ion

-
,

pro ceeds wi t h g rea t er ea se The y ield from me t a cre s ol is sa id t o b e 1 50 per

.
-

cen t t he t heore ti cal be ing 225 per c ent

.
,
.

Trini tro cresol or t r ini t ro cresy lic ac id is a very simil ar substance to pic ric
- -

acid but is less p owerful as an explosi v e a s it cont a ins a smaller prop ortion
,

of e x y ge n I t has bee n use d in France under the name of Cr es ylite for fillin g
.

1
Ve nnin et Ch es n ea u , p . 280 .
 OTH ER NIT RO A ROMATIC C OMPO UND S
-
28 3

shell in admixture with picric acid A mixtur e of 60 parts with 40 parts of .

picric acid (mélin ite ) melts at 8 5 and is plastic at 65 or ° °

The comp osition and temperatur es of ignition of a large number of metallic Pic ates an r

picrates were investigated by Silb e r r a d and P hillip s and the formation and c e yla tes
1
,
r s .

exp losib ili ty of vari ous picrates and tri ni tro cr e s y la te s by Kast 2
The picrates -
.

of lead calcium barium potassium and C opper explode when heated the
, , , , ,

lead c ompound being much more violent than the others The picrates of .

sodium zinc silver magnesium and iron explode with considerably less
, , ,

v iolence those of ammoni um mercury and alum inium like picric acid itself
, , ,

do not exp lode when heated in the ordin ary way .

The trinitro cr esy la te s behave very sim ilarly to the correspondi ng picrate s
-
.

The lead salts are also by fa r the m ost sensi tive to blows being about as ,

dangerous in this respect as nitro glyce ri ne blasting gelatine a n d dry gun -

,

cotton The salts o i the other heavy metals such as c opper sil ver iron
.
, , , ,

calcium and barium are also somewhat sensitive more so than picric aci d
, .

The salts of sodi um potassium and ammoni um are less sensitive and those
, ,

containing water of crystalli zation are less so than the dried substances .

The ac tion of solutions of picric acid and trinitro cresol upon di ff erent -

metals was investigated by Kast P lates of metal 5 X 1 0 cm were placed . .

in mixtures of 50 g picric aci d or trinitro cresol and 20 0 g water for four

.
-
.

weeks It was then found that the followin g quantities of the metals had
been dissolved

Le da
I ro n
Zin c
C o pp e r
ra
B ss
Al um ini um

t ri ed the effect of molten picric acid on metals under c ondi tions

Sa p o s h niko f
more nearly resembling those that prevail in a shell that i s fi lled wi th the
melted exp losive 3
On e gramme o f the finely di v i d e d metal was placed in a
.

beaker wi th 2 g o f picric a c id and kept at a temperature of 1 25 for eight

.
°

and a half to nine hour s The weights of metal that had been di ssolved were
.

0 2 79 8 g .

0 -1 530 g .

0 20 4 6 g
0
.

0 -1 754 g .

0 0 48 8 g
-
.

g .

1 T ran s
, 1 90 8 , p 4 74 . .
2
19 1 1, pp . 7, 3 1 a nd 67.
3
J . Sa p o s h niko f, S S , 1 9 1 1 , p
. . . 1 8 3.
 28 4 E XP L OSIVE S

P ic ra te s ere at one ti me much favour ed by inven t ors a s in gred i ents of

w
explosives b u t very fe w of t h e se mi x t ure s achieved any p rac tical su c ce s s .

De s ig no lle s p owder co nsi te d of po ta s si u m picrate and sal t petre and somet imes
s

c ha r c oa l and w a s made for a ti me in F r an c e a s a c a nnon p owder B r u g ere s

’
.
,

po w der c o n s i t ed o f 54 pa r ts of amm oni um pic r a t e and 4 6 of saltpet r e and

s
,

was sa i d t o give g o od r es ul t s in t he Chasse p ot rifle A mi xt ure of 43 part s .

a mm o ni u m pic r a t e a n d 57 sa l t pe t re is us e d as a de t o na t ing agent in lyd di te

shell under t he na me of picric powder It is m ad e by in c orpo r a tin g the

,
. .

t w o i ngr edi ents t oge t her in a ba ll mill .

Anis o le is made b y condensi ng phenol or sodi u m phenate wi th methyl

c a mera
,
chl or ide or methyl al c ohol in variou s ways E xperiments on nit r ating it .

ha ve bee n ca rried o u t by A L B ro a d be nt and F Sparre who found th at.

1
. .
,

t here is a tendency for t he acid to atta c k the side cha in and c on s e quently
gi ve low yi eld s By co mmencing t he ni tr ation wi t h mi xed ac ids at
. however ,

t hey ob t ain e d a yield of 8 5 per cent of the theoreti cal When one ni t r o group . .
-

ha s b ee n in t ro du ce d in t o the molecul e the r e is no longer any tendency to

a t ta c k t he side c ha in .

An other po s si ble method of manufa c t u re is from ni tro phenol P henol -

.

i s ni tr a te d in t he co ld wi th di l ute ni tr i c ac id yieldin g ortho and para ni tro ,

-

phenol and so me ta r The o rt ho c omp ound is dist il led off w ith ste a m and
.
-

use d fo r t he manuf a c t ure of dyes e tc The pa r a ni tro phenol is pur ified by , .

- -

c r v s ta lliza ti o n from xylene ; it is use d for the ma nuf ac tur e of phenacetin

and so me o t her synthetic compo und but th e demand for it is le ss tha n for s
,

t he ort ho co mpound Co nse quently there is sp are mate rial which ca n be

—
.
,

use d for t he manufac ture of e xplosive s By trea tment with ca u s tic soda .
,

s o di u m ca r b onate me t hyl alco h ol and methyl chlo ri de under pre ssure it ca n

be converted into ni t r o ani ole whi ch on nit r ation gives trini tro ani sole
2 -
s
,
-
.

Trini t ro anis o le is a yellow crystallin e substa nce with a melting point of

- -

64 to 65 and a spec ific g r avity of 1 4 0 8 at

°
It has the sa me composi t ion
as t r ini t r o c reso l bu t i s fr ee fro m ac id charac te r and c o nse quently much
-
,

sa fer but unfortu nately it is slowly hy d rolysed by water to pic ri c acid It . .

is mo r e difficul t to deto na te t h an t rotyl 3

It ha s bee n u w d by the Ge rmans .

fo r fil lin g bo mb s In Dec em be r 1 9 1 4 th e Ge rman Ra il w ay Com mission

.

admi tted i t to G roup Al b of their cl a ssifi ca tion enabling i t to b e s ent i n ,

1 E igh t h In t e rn. C o ng . Ap p l C he m
. . , vo l iv. . .
p . 15 .

3
2 See L . P a u l, A na , 1 8 9 6, p . 5 8 7. A . Ste t t b a c h e r , S S . .
, 1 9 1 4, p . 3 56 .
 OTH E R NIT RO A ROMATIC C O MPO UNDS
-

unlimited quantities as or dinary goods P revious to that date it had not .

been mentioned in the classification .

It is evident from what has been said above that on nitration the NO groups 2

tend always to take up the meta position with respect to one another and that -
,

when so placed they are more stable than when in the ortho or para position -
.

Consequently in all the important trinitro compounds the three group s are -

arranged symmetrically round the benzene ring W hen the N O group s are .
-
2

next to one another (ortho position ) there i s a tendency for one of them to be dis
-

placed with ease and when three of them are together the middle one splits o ff:
,

very readily On the other hand the NO group s tend to take up the ortho or
.
, 2
—

para position with respect to substituting group s such as CH OCH OH and

-
3,

NH and the presence of these group s makes the nitration m ore easy and rapid
2, .

The ki netics of the nitration reaction have been investigated by H Martin .

sen who h a s found that in sulphuric acid the velocity of nitration of nitro
,

benzene i s proportional both to the quantity of nitric acid and of nitro benzene -

present 1
It i s trebled for a rise of temperature of
. and is at a maximum
when the m olec ular proportion of sulphuric acid to water i s 1 0 7 as i s shown ,

by the follo w ing figures

Pe r ce n t . b y w e igh t of H 20 or $0 3 in a c id Ve l o c i y t a t 0
°
Co ns t nta a t 2 5
°

The velocity of ni tration i s much m odified by the presence of other atom s

or group s in substitution for the hydrogen of benzene Martinsen gives the .

following scheme
No , > s o ar 01 CH , < o crr , < oc ,H , < o rr

Cl sometimes accelerates and sometimes retards nitration ; those on the

right accelerate the further they are to the right the more they accelerate
,

th ose on the left retard NO most of all The latter cau t e the NO groups
, 2 .
z
-

to take up th e meta position and those on th e right th e o rtho and para

-
,

positi o ns 2
J P .W ib a u t gives the following velocities of ni tration :
3
. .

B e n e ne z 0 0 0 25 t 25 a
°

C hlo r b e n z c n e 0 0 0 20
-

Bro mb n ne e ze 0 -00 1 3
T luene
°
o 0 0 080 a t 0

1
Z p hy s ika l C he m , 1 90 4, v o l
e it. . . . l .
, p . 385 .

2
I b id , 1 90 7, v o l li x , p 60 5
. . . . .
3
Rec . tr a v. ch i n a ,
1 9 1 5, p . 24 1
28 6 E X P L OS I V E S

Mart insen foun d that when para ni tro anili ne i s nitrate d two nitro group s
- -
,
-

are i ntro d u c ed at nearly the same rate givin g p icr a mide 2 4 6 trinitro a n ili ne ,
- -
.

The rate of nitration of a ni tro naphthalene i s greate r than that of nitrobe nzene
- -
.

If para nitro ani sole be freshly di ssolved in sulphuri c acid and nit r ic acid
- -

be then added one molec ul e of the latter i s taken up in stantaneously with

,

t he formation of din itro ani sole But if the sul ph u ric acid be a llo w ed to
-
.

s tand for a day before the ni t ri c acid i s added nitration i s slow This i s .

asc ri bed to the gradual formation of the sul phoni c acid whi c h is muc h more ,

diffi c u lt to ni trate S ulp honation of para ni tro toluene i s much slower than
.
- -

ni tration but i s more rapid the stronger the acid In oleum conta inin g
, .

25 per cent 8 0 the velocity constant is 0 00 3 and in absolu te H SO , 0 0 00 4

.
3 z ,

and in acid conta inin g a lit tle water much less 1

.

In a queous solution the ni tration proceeds in qui te a di ff erent way to

that i n sul phuri c acid solution I t c ommences very slo w ly and then the
.

velocity increases be in g accelerate d by the production of ni trou s acid in th e

,

c our se of the reaction The velocity o f nitration is increased by the addi tion
.

of sulph u ri c acid or potassium ni trate and t o a less exten t by sodi um or ,

strontium ni trate A min ute quantity of sodi um nitrite at the commencement

.

of the reaction accelerate s it c onsiderably 2

.

1
Ze it p hy ikn l
. s . C he m , 1 9 0 8 ,
. v o l . lx ii .
, p . 7 1 3.
2
H hla r t in se n
.
, ib id ., 1 90 4, v o l. l .,
p . 38 5 .
 P A RT V I I

S M O KE L ESS P O W D E RS
 C H AP TE R X X I

SL OW -BURNI NG SMOKE ESS POW DERS L

r
D y in g th e n itr o c llulo Al c h o li in g I n c r p o ra t i n
e se o z Sha p in g t h o o e
p o w der
u r
Po d e B Ru ia n p o w d rss Ru m n i n p w d e r
e : B lg ian p o w d e r
a a o : e : Ame icr an
r n h o w d er s t it t n t G rman
p o w d e : S p a i p s B l li : F i lia So l i e : e : e e : e
p o w d rs e :

C o r d it e W igh in g th e gun c o tt o n
e Me a u i ng th e n itr o g ly e rin
-
s r -
c e Mix in g
I n c o rp o ra t in g P r e s s in g D r y in g Jap n p o w d r Sp o r t in g rifl e a es e e
p o w de s r
Ax itc : Mo dd ite

AL L smokeless p owders that have been manufacture d up to the present have

one imp ortant feat ure in common : every one of them consists largely of
nitro cellulose in some form and many of them contain only small proportions
-
,

of other substances They may be divided into two principal classe s : slow
.
‘

burning p owders for u se in rifled fi r e arms and fast burning for use in sh o t -
,
-

guns etc Of the former there are two main di visions those that c ontain
, .

nitro glycerine the nitro glyceri ne p owders and those that do not contain
-
,
-
,

it which are called nitro cellul ose p owders although all the p owders contain
,
-
,

this substance P owders for rifled fi r e arms are re quired to burn at a uniform
.
-

rate and not too fast this is achieved by converting the nitro cellulose into -

a uniform and dense colloid by mixing it with a solvent Sporting shot gun .
—

powders on the other hand are required to burn very rapidly and as a rule
, , ,

are only partially gelatinized For nitro glycerine p owders the solvent .
-

generally used i s acetone as it readily di ssolve s all nitro cellulose even of

,
-

the highest degrees of nitration but if the pow der contain no nitr o glycerine ,
-

the colloid yielde d by acetone is too hard and brittle Cons e quently for .

n itro cellu lose powders eth er alcohol i s generally used and the nitro cellulose
- -
,
—

must be of such a description that it can be gelatinized by this solvent .

The nit ro cotton or other form of nitro cellul ose com s in the wet state
e n i g th e fl
mm ceuu's
- -

‘
o
from the fact o ry where it is made For safety s o me 30 per cent or more . .

of water is left in it until it is necessary to dry i t fo r further use The .

nitro cellulose may either be in l o ose form as i t i s taken from the c entrifugal
-
,

in which the greater part of the water has been e x tracted o r it may be moulded ,

into blocks slabs or cy linders by c ompressing i t in a hydraulic press with a

,

mo derate pressure The adva ntage of moulding it i s that less dust is formed
.

V OL . 1 . 28 9 1
9
 29 0 E X P L OSIV E S

in th e drying s t o ves a nd dur ing the o pera t ion o f w eighing the ni tro cellulose -
.

The d rying is eff e c ted by bl o w ing air by mean s of a fan t hr o ugh a s te am

hea te r a n d t hen in t o the s t o v e The te mpera t ure o f t he air ente rin g the
.

s tove s houl d n o t ex c ee d 60 n o r the te mperature in s ide the s to v e

°
C .
,

The be s t arrangement of the i nle t pipe s is to pr o vi de th em wi t h a num b er of

o rifi c es near the t o p o f th e buil di ng and to di re c t the air o n t o the c e ili ng .

The o u t le t s s h o uld be ne a r t he fl o or a n d s h o ul d h a v e a larger area than the

i nlet s The reas o n fo r blo wi ng the h o t air in a t t he top o f the s t o v e is that
.

w hen t he air take s up w ater v ap o ur from the nitr o c ell ulo s e it bec o me s hea v ier -

a n d ten d s t o s ink ; al t hough t he water vapour itself i s li ghte r t han the air ,

t he c o o ling pr o du c ed by the c o nversion o f t he wate r into v ap o ur is s o great

that the ai r afte r taking up the wa ter i s c on s i derably denser Thus suppose .

1 c ubi c m etre of dry air at 40 C on c oming in c ontac t w ith the w e t g u n cotton

°
-
.

t o take up 1 gramme of water The late nt heat of w ater vapour at t hi s

.

temperature i s 573 calories per g the cubic metre o f air weigh s 1 127 5 g.
,
-
.

and it s s pecific heat i s 0 23 7 calories per g Consequ ently the reduction of

-
.

5 73

1 1 27 X 2 3 7
to 993 2 li t res The gramme of w ater vapour o ccupies a space of 1 4 litre
-
.
-
,

and therefore the 1 1 28 5 g of the damp a ir occupies 9 9 4 6 litre s and a c ubic

-
.
-
,

metre of it wei ghs 1 1 3 4 6g H ence by taking up thi s small amount of moisture

-
.

t he density of the a ir has been increased 0 63 per cent ; the evaporati on -

.

o f m o re w ater wi ll lea d t o a furth er in c rease of d ensity I t i s important .

that the inlets and outlets be well d istribute d ro und the ceiling and floor
respectively to a v oi d the formation o f d ead corners in w hich the g rm cotton -

wi ll not be d ri ed properly If the air i s blo wn in at the bo t t om as i s of te n

.
,

the case th e fresh dry air ten d s to rise at once to the top a nd esc ape through
,

th e outlet s bef o re i t has d o ne as muc h d r y ing as it sh o uld The stove shoul d .

n o t be unneces s arily tall inside it shoul d be lined t h roughout wi th zin c sh e e t

wi th soldered j o int s or other sui table material i n order t hat there sha ll be ,

no cracks in w hi c h d ust may a c cumul ate a n d s o that the s t o v e can be w a s hed

,

ou t th oroughly from time to time If the nitr o cell u l o s e has been m o ul ded
.
-

into blo c ks these sh o uld be s tood on racks wi th air s pa c es be t w een the blo c ks
,
-

t o facili t ate d rying If t he ma t erial i s in th e form of l o o s e fi bres i t shoul d

.
,

be lai d o n trays preferably of copper wi re In ei t her case the racks or trays

, .

s houl d be s o arrange d t hat they are c onne c te d elec t ricall y t o earth as dry ,

nitro c ellul o se i s very li able t o be c o me electrifie d a n d a s park may s e t the

-

p o w dery material alight The s t o ve s s houl d n o t be v er y near o ther buil dings

. ,

a s t here is a l w ays a ri s k o f o n e c a t c hi ng fi r e The s tove s are generall y .

c o nstru c te d of light material If th e ni t ro cellul o s e be i n l o o se fi br o u s form

.
-
,

it may be dried in t w enty four hours bu t if it be m o ul de d it wi ll take several

-
, ,

days The greate st care mu s t be exercised not to subj ec t the dry ni tro
.
 SL OW -
B URNING S MOK E L E SS P OW D E R S 29 1

cell ul ose to friction or blows especially if it be still warm The whole stove
, .

should be a llowed to cool down thoroughl y before it i s unl oaded .

In most instances when an accident has oc c urred in a gun c otton stove

,
-
,

the explosive has merely burnt away extremely fiercely but w ithout explodi ng ,

FI G . 54 . Al c o h o l D is p la c e m e n t P la n t (Ma s ch in e nb au A G . G o l er n
z -
G r irn m a )

but on March 10 and 28 1 9 1 3 severe exp losions took place in stoves situated
, ,

respectively at Ar deer i n Scotland and P itsea in E ssex

,
1
In both cases
, , .

the stoves were being unloaded and the presumption i s that some of the
,

gun cotton mu st have been subj ected to blows or friction by the workmen
-
.

In the former case it i s supposed that the explosion was brought about by
upsetting one of the racks on whi ch the gun cotton primers were placed The -
.

exp losion caused three oth er similar stoves in the neighbo ur hood to exp lode
a ls o
,
wi th th e result that al togeth er seven men were killed and te n inj u red .

1
S .R .
, N o s 20 6, 207
, .
 E X P L OSIVE S

The expl o si o n of t hese o t her s t o ve s w a s pr o bably c au s e d b v t he buil di ngs

being shaken a nd w re c ked and perhaps by t he ra c k s being t hro w n d o wn in
,

t hem also From t hi s acci d en t t he d e du c t ion may be dra wn that th e se a nd

.

a ll o t her buil ding s fo r s en s i t ive expl o si v es

shoul d be s o s t rongly con s t ru c t ed t ha t t he
e xplosion of a neighbouri ng buil di ng wi ll no t
w reck t hem The r acks should be fi xe d rigidl y
.

t o t he fl o or .

Alco h o lizing .
In t he c ase o f po w ders t ha t a re gela t inize d
wi t h ether alcohol t he t roublesome and danger
-

ous opera t ion of d ryi ng t he ni t ro cellul ose can -

be di spense d wi t h a s the w a t er c a n be di s ,

pla c ed by means o f alcoh ol The w e t gun .

c o t t on i s pac ked in t o a cylinder Fig

(s ee .

a nd t hen alc o hol i s for c e d t hrough i t by

means of c ompresse d air Firs t water flows .

a w ay a n d is r u n to w aste t hen w eak alcohol ,

whi c h i s r e r ec tifi e d s o t hat i t can be

-
,

used again and finall y fairly s t rong , ,

al c o hol w hi c h i s use d again for the pre

limin ary di splacement of ano t her c ylinder
of ni t ro c e ll ul ose
-
The alcohol i s al w ays
.

intro duce d a t t he top of t he cylinder a s

it is li ghter t han t he w a t er ; fir st alcohol
from the final di splacement in another
c y linder .a n d t hen strong al c ohol The .

displa c emen t takes t hree to s ix hours .

\Vhen t he w ater ha s been displaced t he ,

su r plus al c ohol i s removed from t he ni t ro F ro 55 p r e fo Al c o ho li ze d N it ) . . ss r “

cellulose by mean s o i a hydraulic press A c e l lu lo se .

t y pe of press much use d fo r t hi s pu r pose in

G e rm a n v is sho wn in Fig 55 It ha s t w o c y lin ders which s wi ng ro u nd
. .
,

t oge t her on one of the c olumns so that w hil st t he c ontents of one are be ing
presse d t he o t her can b e emp t ied and fill ed again “ ashi ng wi t h alcohol
l

h a s t he furt her a d van t age t ha t i t rem o v es the u nstable impuri ties t o some
ex te n t A c c ordi ng t o Gu t t mann t hi s device of di s placing water by alcohol
.

w a s use d in Austria in 1 8 9 1 but t h e invention has been claimed for Mes sier, ,

Ingéni eur de s P ou d res c t Sa lp é tr e s in 1 8 9 2 In t hi s year a pate nt was a lso , .

t aken out for i t in E ngland by Durnf ord 1

.

t
I nco r po r a i on. The ni t ro cell u lo s e is inco r pora t ed wi t h t he solvent in a machi ne whi c h
-

/ E x p los i
1
aJ I n u/ c t u a rc l ii p 23 9
o V nn in P
ves d , t E p lo i/
v o
p 39 4 ;
. .
, . . e , ou r es e x s s , .

B ui s o n P o b leme d
s , r P o d e p 37 esB r it P a t
u r o f No
s, 1 7 1 8 92
. . . . v .
, .
 SL OW B U RNI NG S MOK E L E SS
-
P OWD E RS 29 3

is constructe d on th e same prin ciples a s the k nea ding machi nes used in bakeries
( s e e Figs
. 5 6
,
It consists of a trough in w hic h t w o
, curved bla d es r o ta te
.

i n opposite dir ections one t wi ce as fast a s the other both g o ing d o wi rw a r ds

‘

, ,

in the centre of t h e trough and up w ards b y the w alls First some o f the .
,

solvent i s poure d in to moisten the axles a n d bla des th en the ni t ro cellulose ,

-

and other m aterial s and finally more solvent The inc orporator is t hen
,
.

started a n d kept running for some hours until consti tuent s of the po w der

56 . n c o rp o r a t in g
I Ma ch ine in P o s iti o n

(\ V rn r P fl e id
e e ,
e r er a nd r
P e kin s , L t d ) .

are thor o ughl y mixed the trough meantime being kept covered to prevent
,

loss of sol v ent The trough i s then tilted up a n d the blades are made t o
.

rotate in the opposite di rection The dough falls int o a box or other receptacle
. ,

and is taken t o the b u ildi ngs where i t is pressed into cor d s tubes or s t ri p , ,

o r i s r o lled into sheet according t o the form that it i s requi re d t o give t o

,

the finishe d pow der .

If the in c o rpora t o r be dri v en by an electri c m o t or thi s sh o ul d be place d

,

s o tha t vap o ur of t he s o lven t cann o t p o s s ibly be igni t ed by s parks of t he

c ommu t a t o r
. The m o t o r s houl d be provi de d w ith an au t oma t ic relea s e to
p revent danger o f the e xp l o sive being fire d b y t he appli c ati o n of t oo much
p o w er The lid o f t he inc o rp o ra t o r is be s t ma d e o f aluminium d o me d s o me
.
.
,

w ha t s o as t o a ll o w o f m o re ma t erial b eing pla c e d i n t he ma c hi ne The .

 294 EXP L OSIV ES

al u mi ni u m may be s urroun ded by a w ooden frame hel d down to t he rim o f

t he incorpo r ato r by but te r fly nu t s .

The d ough i s ne x t forme d in t o t he d esire d shape Formerly it w a s in .

ma n v c ases rolled in to shee t s by passing i t repeate dly t hrough rolls resembli ng

FI G . 57 . I n c o rp o ra t in g Ma c hi n e . r o u gh
T Til te d ,
s h o w in g B la d e s

a paper maker s calender The sheets were cut into strips whi ch were again
-
’
.
,

cu t t ransversely s o a s to form cubes or flakes No w i t is m o re usual t o press .

t he dough t hrough a di e in a press which is an a d aptation of the machi ne ,

u s e d for making macaroni It is thus obta ined in the form of cords strips or
.
, ,

t ubes if des ire d these can then be cut in to flakes of any required thi ckn ess .

Po udre B. P o u dre B whi ch was invente d by Vieill e a n d adopte d by the French

,

Gover nmen t in 1 8 8 4 for use in the Lebel rifle was the first smokeless p owder ,

to achieve success in a rifle d fi r e arm It i s named afte r the first lette r in

-
.

t he name o f General B oul a nger who was Mini s ter of W a r at the t ime A c cor d
,
.

ing to an analysis made by Lieu t \Vi s ser U S N its c o mposi t ion was : .
,
. .
,
1

In s o u
l b le ni tr o -
c e l lu o se
l 68 2 pe r
-
ce nt .

u
So l b le 9
2 8-

Paraffi n 20 -

1
N itr e -
ce llu lo s e I nd us try , p . 9 62 .
 L
S OW BU RN I NG -
S MOKE L ESS POW DERS 295

Apparently it was gelatinized by means of acetic ether The c o mposition .

was m odi fied several times the pow der kn o wn as P ou dre B N c onsisted of
I n s o lu b le n it r o -
u
c e ll lo s e 29 1 p e r ce nt . 38 7 p e r-
cen t .

u
So l b le 41 3 33 -2
ar u nit ra t e
B i m 19 0 -
1 8 -7
P o t a ium n it ra t e
ss 8 0 -
45
So d a
Vo la t ile ma tt e r 13

N stands for N o uvelle Instead of soda tann in was sometimes use d The
.
, .

p owder was gelatinized with ether alcohol ; the first analysis w a s giv e n by —
.

Neumann the second by Weaver

1
,
2
.

All other soli d c onstituents were subsequently abolished a n d the powder ,

c o nsisted only of a mi x ture of soluble and insoluble nitr o c o ttons gelatini zed -

with ether alcohol In or der to improve the stabil ity an a ddition of

—
.

amyl alcohol was introduced in 1 8 9 6 1 8 9 7 first 2 per cent a n d afterwar d s

— —
,
.

8 per cent These p owders received the names B (AM ) an d B (AM )

.
2 8

respectively Now di p h e n y la mme 1 8 added instead

. .

Various processes of nitration are in use in the French Government

factories : the Abel process nitrating centrifugals and at Angoul eme there , ,

i s a displacement plant on Thom son s system Two sorts of nitro cotton ’

.
-

are made called GP and C P respectively C P i s a gun cotton of high

, 1 2 . 1
—

nitration givin g 20 5 to 21 5 c c N 0 per gramme in the nitrometer ( about . .

z

1 3 per cent N ) and having a solubility in ether alcohol of less than 1 5 per
.
-

cent in practice it gives 20 9 to 21 4 c c NO a n d has a solubility less than

. . .
,

1 0 per cent C P is a soluble nitro cotton giving 1 9 0 to 1 9 8 c c NO per

.
2
—
. .

gramme ( abou t 1 2 per cent

2 and having a solubili ty of over 9 6per c ent . .

Limits are also set to the vi scosity of the solution in ether alcohol and to -

the percentage of matter soluble in alcohol .

The proportions of GP and C P are varied accor di ng to the sort of p ow der

1 2

that is to be made For rapid p ow d ers such as BF 20 to 25 per cent of

.
, ,
.
.

soluble nitro cellul o se are used and in the slowest p owders 50 to 55 per cent
-
,
.

C P is not only a more powerful explosive than C P

1 but as the fibres are 2,

not gelatinized by the solvent but only c overed with the s o lution of C P ,

it burns more rapidly .

The nitro celluloses are b o iled and pulpe d and mixed in the pr o per
-

proportions and are then dehy drated with alcohol and pre s sed If the
,
.

pressure be 3 00 kg per sq c m (2 tons per s q in ) the alcoh o l left in the bl o ck

. . . . .

amounts to about 20 or 25 parts per 1 00 o f nitro cotton It is then place d -

.

in the incorporat o r with the solvent which consists of 1 volume o f alcohol ,

to 1 9 volumes ether
-
all o wance being ma de for th e alcohol already
,

p resent The quantity o f s o lvent varies accor ding to the sort of pow der
.

1
S S 1 9 10 p 4 5 1 . 111 l it
.,
y E p l i s p 1,
35 . .
2 '
1
'

a r x os ve , . .
296 EX P OS I VES L
from 1 40 to 1 50 parts per 1 0 0 parts nitro c o tton Th e alcohol used is o f -
.

9 5 per c ent streng t h by v o lume (9 25 per cent by weight s p gr

. .
, . .

the e th er is o f 0 5 B a u mé (s p gr °
a n d the mixture i s of 5 6 Baum e
. .
°

( gr In the s o lvent i s di s s o l v e d the stabili zer di phenylami ne

'

sp . .
, ,

1 5 to 2 per cent of t he ni t ro cellulo s e

-
. The incorporation lasts from o ne
-
.

t o three hour s a n d then the dough i s placed in air tight boxes and allowed
,
-

to ripen .

By means of a pres s it i s now squirte d through a die whi c h form s it into

a s t rip Ab o ve the d ie is placed a filter of fine wire gauze to retain impu rities
. .

The s trip is received on an endl ess band Its width varies according to the .

typ e o f pow d er from 20 to 1 50 mm and its thickness from 0 6 to 8 mm .

, .

The st rip s must n o t be d ried to o rapidly at first else they will c url up , .

As t hey c o me fr o m t he pre s s they have j ust sufficient tena c ity to a ll o w o f

t heir being su s pen de d from bars Thus suspen ded they are intro d uc e d int o
.

a c hamber w here they fir s t m e et with air partly saturated w ith v a p our o f

e t her alcoh o l The bars can be moved in the opp osite direction to the c urren t
-
.

o f air s o that t he P oudre B meets air ever less saturated with solvent vap our
,

The air may be c irculated in a close d circuit after leaving the dryi ng chamber
it passe s thr o ugh a heat regenerator then th r o ugh a cooling plant which , ,

is als o constructe d on the regenerative principle and in which the temperature ,

is reduced to 20 to 5 C so as to condense most of the solvent vapour

° °
— —
. .

Af t er this the air passe s through the heat regenerator agai n then through ,

a heating coil and then i s d riven by a fan back into the other end of the dryi ng
chamber The powder after this preliminary drying contains 1 5 to 20 per
.

cent o f s o lvent mostly al c oh o l

.
,
.

It is n o w o u t to the right size Artillery p owders are merely cut into . .

leng t h s usuall y o f 1 0 0 to 40 0 mm Rifle pow d er is cut into small flakes

, .
,

1 5 t o 2 mm s quare and ab o u t 0 5 mm thick : the strip s are fi r s t cu t by

.
-
.

r o t a t ing c irc ular cutter s int o narrower strips and these are then c u t tran s ,

v e r s e ly Irregular grain s are sorted out by means of aut o ma t i c sieve s and

.

r e incorporate d with a fre s h c harge

-
.

The c u t powder is then d ried i n stoves heated not above It is next

immer s e d in water at or slightly below 8 0 C fo r a peri o d vary i ng fro m a °
.

few h o ur s up to forty eight hour s for powders of the large s t size Finally
-
.

it is d r ie d again in a stove fo r one to four days to remove the water a n d redu c e

the v o latile matter w ithin the li mit s fi xed fo r each sort o f p o wder 0 8 to 2 .
,

per c ent The w ater immersi o n i s carried out at such a high temperature
.

i n or der to re d u c e t he time A re d uction of 1 0 i n the temperature would

.
0

render i t n e c e s s a r v t o d o uble the time o f immer s i o n and a reduc t i o n of 20 ,

°

t o qua d rup le it .

The p o wder s are given le t ter s acc o rding t o the pu rpo s e fo r which th ey
are intended : t hu s B F and BNF are s mall arm p o wder s from the words -
 SL OW BURNING S MOK E L ESS
-
P OWD ERS 29 7

fusil a nd nouveau B C i s po w der for fiel d guns the celebrated

, ,
” ”
soixante qui nzes fr o m
-
campagne ,
B SP po w der for siege howitzers
“
,
”
from si ege e t place and B G C po w der for the larger m ilitary guns from
,

gros calibre P ow d ers for na v al ordnance have the letter M (marin e )

“
.

with an inde x figure accor di ng t o t he s ize

C a l ib re P o w d e rs
mm .

1 00 a nd 1 38 6 -

1 64 -7
1 94
240 a nd 274 4
30 5
3 40

In addi tion l e tters a n d indi c e s a r e use d t o in dicate the s t abili zer a dde d a n d
t he percentage : thu s AM means 8 p e r cen t of amyl al c ohol a n d D 2 per
8 .
-

, 2

cen t of di phenylamine Ot her le t ters sho w t he place a n d da t e of manufac t ure

. .

of the p o w der and t he c artri dg e s For instance EM AM 0 1 SM B 2 2 .

, , , ,

a naval powder w ith 8 per cent amyl alcohol formi ng part of t he 4th lot of .
-

1 9 0 1 made at Sain t Mé da r d and put into cartri dges a t Brest i n February ,

1 9 0 2 P o u dre B C is made in stri p s measuri ng 8 0 mm X 40 m m x 0 7 mm

. the . .
-
.

wi d th of the largest naval po w d ers i s as mu c h as 1 50 mm and the t hi ckness .

,

8 mm Na v al p o w ders are blen de d in t o unif orm lots of 1 0 0 tons each P ou dre

. .

BN F in use with the D bul let is drummed and g r a p hite d t o restrain t he

3 , ,

initial rate of ignition On the other hand B C B SP a n d B M to BM are

.
, , I 5

striate d to increase the rate of burnin g .

The presence of num erou s fibre s of un gelat inized ni t ro cotton probably -

fac ilitates the o x idation and consequent d eterioration of P oudr e B The .

e xtent to whi ch it is porou s is in di cate d by the density whi ch i s onl y about ,

1 5 2 whereas that of ni tro cotton is

, In former years a number of
-

spontaneou s ignitions occur red w ith P o udr e B o f whi ch those on the battleship ,

J én a in March 1 9 0 7 and on th e L i b er té i n September 1 9 1 1 attracte d mu c h

.
, ,

attention a s both occurred in Toulon harbour and destroy e d the ve ssels in

the sight o f th e w hole t own Formerly amyl al c ohol w a s a d ded t o the pow der
.
-

to improve its stab ility but this substance has no great power of abs o rbing
,

nitrogen oxi des a n d the final pro d ucts are aci d a n d c onsequently inj u r i o u s
, .

Old po w ders w ere soake d in a mix t ure of e t hyl and amyl alcoh o ls t o res t ore -

”
their stabili ty This proce dure calle d r a do u b a g e w a s unsound and w a s
.
, , ,

”
iven up after the J é n a di s a s ter i n fa v o ur o f r e ma la x a e w hi h n s is t e d
g g c c o ,

o f reincorp orating the d oub t ful p o w d er wi th e t her al c ohol c o n t aini ng amyl -

alc o hol Further i nvestigation h o w ever sho w e d t ha t t he stab ili t y o f t he

.
, ,

nitro cellul o se w a s not really re s t o re d by t his pro c ess a n d a fe w years ago

-
,

i t als o w a s aboli shed No material i s now re w orke d e x cep t qui t e n e w cu t t ings

.
,

etc .
 E X P L OSIV E S

The c o st of production of P oudre B in 1 9 1 2 was Fr 6 40 per kg . .

The ques t ion of sm o keless pow ders was referred by t he Russian G o vernment
to t he great chemist Me n de lée ff w h o s t arte d work upon t he problem in 1 8 9 1 ,

together with a ban d of able assi s t an t s i n t he s cient ific laboratory of the

navy w hi ch was founde d spe c ially fo r t hi s pur pose Me n de le e ff foun d t hat
’

.
,

it was possible to make a ni tro cotton t ota lly soluble in ether alcoh o l w hi c h - -
,

had as h igh a percentage of ni t rogen a s the mi x ture of s o luble and in soluble

nitro cot t ons used by the French (s ee p
-
Thi s w hich he call ed p y ro .
,

c ollo dion w hen gelatinize d wi t h e t her al c ohol give s a much more uniform
,
-

c o lloid than a po w d er like P ou d re B as may be seen in t he micro phot o graphs ,

-

reproduced in Fig 5 8 . .

P y m c o llo di on c onta ins about 1 2 44 per cent N and therefore has enough
-
.

o x ygen t o c onvert a ll the carb o n into C O and a ll the hydrogen into wa t er ,

bu t a s a matter of fact some C O and C H are always f o rmed and some of 2 4

the hydr o gen i s evolved a s such Accor di ng t o B uisson Rus s ian p o w der .
,

con t ains 1 per cent of di phenylam ine The general metho d s of manufacture. .

are similar to those for P oudre B As the productive power of t he Ru s s ian .

factories was insu fficient powder was often obtain ed from France before ,

the war 1
.

In Rumani a a powder resemb ling P oudr e B is made from a mix t ure

of tw o ni tro cottons c ontaining 1 3 and 1 2 5 per cent N respectively At
-
. .

a factory at D u de s ki a p owder is made containin g 1 per cent of diphenylamin e .

and 4 per cent of c e ntr a lite w hi ch i s a substance used to gelat in ize the surf ace
.
,

of the pow der and so restrain the ini t ial rate of igni tion 2
.

The po w der made by C o o p a l e t (Li e at Caulille was also of the same t y pe . .

I t c ontained 40 to 60 per cent of soluble ni tro cotton gelatiniz ed by means .

o f e t her alc o hol in the proportion of 1 1 25 parts b y w eight to 1 00 0 part s of

-

ni t ro co t t o n The dough was not presse d t hrough a di e bu t r o lled in t o s hee t s

-
.

be t ween r o ll ers double d over a n d rolled several times The shee t s w ere
,
.

t hen c u t in t o s t rips or fl akes 3

.

The Ameri cans afte r e xperimenting w ith vari o u s sorts have adopte d a
,
4
,

1 P r o b le me des P ou d r es , p 2 I b zd
‘ ’

. 70 . I b id p .
, . 59 .
3
.
, p . 63 .

4
a
Th e M x im Sch iip p ha u s p o w d e -
r t ha t
s we r u e s e d in t h e Ame ic a r n se r vic es h ad t h e
f n
o llo w i g c o mp o s i io s t n
Pe r ce n t . Pe r ce n t
G un tt o n
-
co

S lub l ni t r o
o llule -
ce o se

N it o g ly rine
r ce

T h e
y we r e t
g e la in ize d b y me a s n o a t n
f ce o e .

Th e p o w d e r fo r t h e l s m ll a na va a -
r m o n i te d o f nitro c ll ul
s c s s -
e o se a nd the n it r a te s o f
ba ru
i m a n d p o ta ss i m , u t ha t fo r t h e m ilita ry m ll a m c o n ta in
s a -
r s ed al
so n it ro -
g ly ce i rn e

a nd a de te rr n t e . il l i li ta ry 1 90 6, p .
 SL OW B URNI NG SMOKEL E SS P OW D ERS
-
29 9

p yrocollo dion p owder for all kinds of guns

-
In the U nited States the powder .
1

is made up into the form of sh o rt cylin ders which are pierce d longitudi nall y
with small perforations usually seven The plant and methods of manu , .

facture are described by W orden The soluble nitro c otton wi th 1 26 to .

-

1 28 per cent N is made as described o n p 1 8 0 and boiled to render it

. .
,

P y r o x y lin e P o w de r . P y r o - c o llo dio n P o w d e r

Mix t u r e o f So lu b l e a n d I n s o l u b l e

N itr o ce llu lo se
-

FI G . 58 . Mic r o p h o t o grap hs of Sm o k e le s s P o w d e rs (Sa p o s h n iko ff , S S . .

, 1 90 7, p 1 63 )
t
Se c io n s 0 0 5 mm . t h ic k . Ma gn ifi c a t io n 1 50

stable The greater part of th e water is wrung out in a centrifugal and

.
2
,

the remainder is di sp laced by alcohol in a hydraulic press P ressure up to .

3 500 lb to the square inch i s the n appli ed so as to produce a block weighi ng

.

about 3 8 lh of which 1 0 1h is alcohol of 8 8 per cent strength These blocks

.
, . . .

are bro ken up with wooden mallets and three of them are loaded into an ,

incorp orating ma c hine which 1 s run for about fifteen minutes before any ether
,

is added in order that the lump s may be broken up to a fine p owder Then ;

4 8 4 lb of ether are added and 6 oz of di pheny lamine to act as a stabili zer

. . ,

so that the charge c onsists altogether of :

N it r o -c o tt n o

Al c o h o l
W ate r
E th r e

D ip h ny la min e
e

The incorporator i s kept c overed to prevent loss of solvent and i ncorporation ,

i s continued for fo r ty fi v e minutes The white finely comminuted materi al

-
.
,

1
S ee Sc h u p p h a u s , J S o c C h em I n d , 1 8 9 5 p
. . . .
, . 55 6 ; H ud s o n Ma x im , i b id .
, 1 8 9 7, p .
49 5 ; a
As p in w ll , i b id , 1 90 0 , p 3 1 5 . . .

2
N i tr e cellu lo s e I n d u s tr y , p p 90 2 9 26
-
.
—
.
300 E X P L OSIVE S

is then conver t e d in t o a c ompac t mass by subj ecting i t to a pressure o f 3 500 1b .

to t he s quare inch in a h y drauli c pres s B v means of ano t her p ress i t i s .

fil t ered t hrough a 30 mesh iron wi re sieve to remove gross imp u ri t ies Then
-
.

i t is compac te d again in a t hi rd press and by means of a fourt h i t is s quirted ,

t hrough a di e which forms i t into a long mul t i perforate d cord The d ough
,
-
.

so stiff i n consequence of t he small prop o rtion of s o lven t u sed t hat a

FI G A me r ica n P V I r (fr o m A p p le to n
’
. 59 .
‘
O P o w de s s J I a ga z ine )

c onsi d erable amou nt o f heat is generate d in passin g t hr o ugh the di e bu t b v ,

means of a w a t er j a c ke t the te mpera t ure is kep t do w n t o 30 or °

i s n o t a d vi sable t o redu c e the te mpe r a t ure belo w 3 0 becau se a t lower °

t emperature s t he cor d b e c omes too hard to be cut i nto short leng t hs in t he

nex t operation In ord er t o prevent fall of t emperature and evapora t ion o f
.

e t her from the warm colloid the cord i s passe d at on c e t o t he powder cut t er
, ,

w hence the gra ins dr op into a closed recepta cle This i s remove d t o a dryi ng .

house where the drying i s car ri ed ou t slo w l y a t first in order not to di sto rt
,

t he grains too mu c h or make them crack The te mperature of dryin g doe s .

not exceed 44 and t he process i s a long one for large grain po w ders i t lasts
°

four or five mon t hs Qui ck dryi ng me t h od s are said not t o give a unif orm
. .

po w der .
1
The fin i s he d pow d er i s s ubj ec te d to special physical te s ts to
ascer t ain that it is not brit t le the ends of the grain are cu t o ff even an d
perpe ndi cu lar t o t he a x i s and t hen i t is subj ecte d t o a slo w p re ssure : the
,

leng t h must dim ini s h 45 per cen t befo re t he grain begins to cra c k 2
If kept
. .

for long t here mus t however be a gradual though sl o w loss of s ol v en t w hich

, .
,

wi ll make t he grain har d er a n d more bri t t le If t he po w der gra in s break up .

in t he gun hi gh pres s ure s are generate d a n d t he gun m av be inj ur e d o r even

, ,

1
R Ea r l J u
. e , o r. U S . A r tille r y . Se p t . Oc t .
, 19 1 4 .

2
Sc huh m a c h r e , S S . .
, 1 90 7, p . 82 .
 SL OW B URNING S MOK E L E SS -
P OWD E RS

burst It i s stated that there have been numerous cases of such accidents in
.

the United States but this has bee n officially denied 1

Very large quantities
, .

have however been r e worked w ith fresh solvent and an ad d ition of di

, ,
-

phenylamine ; thus at the pow der works at In dian Head in1 9 1 3 lb , .

o f new pow d er were ma d e a n d lb were r e worked at a c ost 3 5 ,

.
-

per cent of that of the new p owder Altogether nearly

. 1h had been . .

r e worked up to the end of

-
The quantity of solvent in the ordnance
pow ders when new varies from 3 per cent i n that fo r the 1 p r up to 68 per . .
,

cent in that for the 3 0 c m 40 c alibre gun The specific gravi ty of the p owder
. .
-
.

is and the cost of production 23 4d per 1h To the c ontractors 1 2 lb . . . .

of alcohol i s supp lied for every 1 lb of p owder accepted In the finished . .

grain the length i s two and a quarter times the d iameter which i s ten times ,

the diameter of the holes 4

.

The French Russian and American Navie s are the only imp ortant ones
, ,

that use nitro cellulose p owders for their large calibre guns The other P owers
-
.

are of the opinion that for this purp ose p ow ders c ontaining nitro glycerine -

o ffer decided advantages but for the comparatively small fi eld guns and for ,
-

small arms every P ower excep t Great Britain and Italy uses nitro cellulose
- -

p ow der Nitr e cellulose p owders are mostly made of soluble nitro cotton
.
- -
,

because ether alcohol gives a less brittle colloid than acetone The p owders
-
.

di ffer somewhat as regards the degree of nitration also as to the form of the ,

grains some being rolled into sheets and then cut into small square flakes
, ,

others being pressed into cords o r tubes and cut o ff into short lengths some
are c oated with graphit e and some are not
—

The Spaniards after trying a nitro cellulose p owder made at the Rottweil Spanish
,
-

Pow de r'
works in Germany c ontaining about 1 per cent of camphor and a small ,
.

p r o p o r tio n e f a urea de r ivative now make their own p owder whic h also is , ,

of the nitro cellulose type For small arms it i s made in the form of flakes
-
.
-
,

for arti llery in lon g tubes but they have also experimented with p owder ,

in strip form 5
.

In 1 8 8 7 a few years after the invention of P oudre B Al fred Nobel invented Ballistit
, ,
e.

a smokele ss p owder in which the fibrous structure of the nitro cotton was —

destroyed not by the u se of a volatile solvent but by dissolving it in another ,

explosive nitro glycerine This sub stance to which he gave the name
,
—
.
,

ba llistite is indeed blasting gelatine wi th the prop or tion of nitro cellulose

,
-

largely increased 6
At first benzene was added to facili tate the solution
.
,

1 2
S S . .
, 19 1 1, p . 1 36 . S S 1 9 1 1, p 1 9 7
. .
,
. .

3 Sc huh ma ch r
1 90 7, p 8 2 e , S S . .
,
. .
4
u n
B i s s o , P r o b le me des P o u d r es , p 50
‘

. .

5
S ee S S , 1 90 8 , p p 1 54, 24 8 , 28 3 ;
. . . 1 9 1 0 , p p 1 61 , 1 8 8 , 4 1 6 ; 1 9 1 2, p 4 79 ; f o m
.
. . r
M emo r ia l de A r tiller za , Fe b a n d Ap r 1 90 8
’

. . Ju ly , Se p t .
, Oc t .
, No v .
, 1 90 9 ; July 1 9 1 2,
B u is o n s , P r o b leme des P o u dr es , p 67 . .

6 Fr . P s at Of 18 8 7, a n d
. of 1 8 8 9, a nd E ng . Pa t . 147 1 -
of 18 8 8 .
 E XP L OSIV E S

a nd . was af t e r ward s e v a p o ra t e d o ff A be t te r me th od of inco rp ora tion w a s .

di sc o v ered by Lun d h o lm and Sayers 1

w h o place t he soluble ni tro cot to n and ,
-

nitro gly c erin e i n h o t w a te r a n d s t ir i t by mea ns of c ompressed air U nder

-
.

t hese c ondi t i o ns t he ni t ro c otto n gra d uall y di s s olve s in the ni tro glyce r ine or
- -
,

perhaps i t w oul d be more corre c t t o s a y t hat t he nitro glycerine dissolves in -

t he ni t ro c o t t o n The d o ugh t hu s produce d is then passed be t w een rolls

-
.

hea t ed t o 50 or 60 C wh er eb y t he w ater i s pressed ou t a nd t he exp losi v e

° °
.

i s ma d e in to a sheet Thi s i s fo lded o v er ,

:

a n d pa s s e d t hrough t he r o lls again a n d ,

t he o p e ra t i o n is repea t e d un t il t he
mate rial h a s been c onvert e d in t o a u ni
form c o lloid I t is t hen cut in t o s quare
.

flakes generall y c oate d wi th graphi te

, ,

and fina ll y i t i s blended Various addi .

ti o n s ha v e been made a t di ff erent times

t o make t he po w der more s t able or to
improve its physical properties The .

firs t E ngli s h patent mention ed camphor ,

but t hi s w a s dropped o n account of its FI G 60 Am e rica n R ifl P o w d e r .

. . e

v olatili t y : di phenylamine a nili ne and (Th om e r S S 1 90 7 p 425)

, , . .
, , .

c al c ium carbonate have also been u sed

muc h for t hi s purpose T h e p owder genera lly c onta in s 40 to 50 per cent
. .

of c oll o di on cotto n a n d 50 to 60 per cent of nitro gl y cerin e It ha s the

'

—
. .

ad v anta ge that the plant req u ire d for it s production i s c omparati vely simple ,

bu t it causes very severe erosion in the gun s .

Balli stite wa s adopte d b y the Ita lian Governm ent s oon a fter its in vention ,

bu t instead of using it in flake form it w a s drawn out in to cords wi th the aid

”
of a solvent a n d hen c e w a s g iven the name Filite
,
Ita lian ball istite “
.

generally consist s o f equal p a rt s of ni tro gl y cerin e and collodi on cotton together -

,

with 0 5 to l per cent anil ine or di phenylami ne for mi cro photo s see P a te m o
-
.
-

and Tr a e tta Mosca S S 1 9 1 0 p 1 45

-
. .
, , . .

In consequence of the severe erosi o n that balli stite causes in the gu n the ,

I t a lians reduced the percenta ge of nitro gl y cerin e t o 33 per cent It then ‘

-
.

became nec es sa ry to u se acetone to a ss i t the gela t in i zation and the presence s

,

of t hi s s olvent made i t p ossible to use a nitro cellul o se only pa rtly soluble -

in ni tro glycerin e or e t her alcohol From 1 t o 3 per cent of a li ght coloured

- -
. .
-

mineral j e lly w a s also inserted so that th e p owder, whi ch is called S oleni te , .

d oe s not di ff er ver y much from Co r di te The ni tro cotto n used conta ins .
-

1 24 to 1 2 6 per cen t N and abou t 50 per cent o f it i s soluble in ether alcohol

’

- -
. . .

It i s pre s sed int o tube s w hi c h are cu t in to shor t length s The gra ins thus
, .

1
En g . Pa t . of 1 8 8 9.
 S LOW B URNING S MOK E L E SS -
P OWD E RS 30 3

o btaine d are translucent and of a li ght b rown colour and look somewhat ,

li ke glass b e e d s .

The Germans adopted ballistite for their navy in 1 8 9 8 under the name G er ma n
p ow der s.
W P C / 8 9 it had the same c omposition a s the Itali an Fili te but was made
. .
,

up in the for m o f square flakes or cubes W P stands for W iir fe lp ul v e r . .

,

i e cube p o wder ;
. . In 1 8 9 7 and 1 9 00 other p o wders were introduced less .

erosive to the guns These are blacki sh grey in colour and in composition .
-

they appear t o b e much the same as Solenite or Cor di t e M D except that a'

. .
,

little diphenylamine is added as a stabil izer as well as mineral j elly The .

powders are mad e i n tubular form an d ar e called R P C / 9 7 and . .

R P stands for Roh r e np ul v e r i e t ube powder

. . The Germans use nitro , . . .

glycerine p owder fo r their large naval guns and fp r their howitzers as they -
,

c onsider that t hey give more regular ball istic s in these weap ons th a n
.
,

nitro cell ulose p owders For their small arms and 77 mm fiel d guns etc
-
.
-
.
, .
,

they u se nitr O c ell ul o se powder of comparatively high nitration containing

‘
L

di phen y lam ine as a stabili zer and sometimes some camphor as an au x iliary ,

gelatinizing agent Th e p owder for field guns i s made in the form of tubes
“

. .

They have also introduced a progressive p owder with the surface gelatinized
by means of C e n tr alite 1
.

The follo w ing partic ul ars as to German military p owders are given by -

Berlin
N tit e llu lo s e p w ders
r -
ce C o lo ur g r e y i h y e llo w o r b r o w n r
o mb lin g g lu
. s , es e e.

SP Fla k p o w d e r fo r r ifl e 9 8 n d c arb in
"
. e 98 a e .

P 1 P P (P la t p a t r o ne n p ulve r )
. . . B lan k p o w d r f z am e w a p o n -
. e or s e s .

G e c h B l P (G e ch ii t B l att ch e n p ul e )
s . . Fla k e p o w d e r f o t h 9 c m g un 73
. s z- v r . r e . s ,

n d t h e he a vy 1 2 c m
a
g un . .

Ge s ch B l P 0 3 P o w d r s m ad e b y r e w o kin g G e h B 1 P a n d G B l P t o ma k
. . . e f
r sc -
. . r . . . e

G e ch B l P s t he m mil de r a n d m r e t ab le
. . . o . s .

G B l P 0 3 (G r o b es B l att c h e n p u lv e r )
r. . : L ar g e fl a k e p o w d e r f o u in th e 1 5 m r ing . r se c .

c ann o n a n d 21 e m do . .

G r Bl P . Mad e b y r e w o r ki n g th e ab o ve
. .
-
.

R G 96
Tub ular p o w d e r s f o u s e in t h e fi e ld gi m 9 6 n / a (1 27 mm l o n g )
. .

r
R P 05
. .

. .

F o r u e in t h e var i us 10 c m g u n s (3 8 0 mm l o n g )
.

R P 9 7 a n d 9 9 (R oh r e n p ul e r )
.
-
v . s o . . .

RP . 07 . Fo r th e 1 3 g unc m . ..

Ma n R . . P .
(Ma n ov er -
Rin gp u lv e r ) . Bl an k rin g p o w de r fo r fi e ld g u n s.

N i na gly cer in e p o w der s

-
C o lo ur b la c k d u e t o .
, , co i gat n of g p i era h t .

VV P (é) (W iir fe lp u lv e r )
. . C u b ic p o w d e r e d g e .
, of c ub es mm fo r th e 3 .
-
7 r e v o lv r e

c a rin o n .

\V P . .
(2 X 2 X i) . Fo r t h e 5 c m .
g un .

W P
'

. .
(4 x 4 x F o r t h e lig ht h o w i t er
fi e ld z .

Fo r t h e h av e
y f ie ld h o w it r a n d 21 c m b r o n e m o rtar
ze . z .

( 10 X 10 x Fo r t h e h ea vy fi e ld h o w it r 0 2 a n d 1 5 c m ho w i t e r ze , . z , a nd th e
21 e m . b r n ze
o m o r t ar .

1
B is s o u n , P r o b leme
‘

des P o ud r es , p . 71 . 2
H a nd b u ch de r W a fi en leh r e .
 E X P L OSI VE S

(12 X 12 X F o r t h e 2 1 c m m o rta r . .

R g P (Rin g pu lv e r )
. . Sh o r t t u b u la r p o w d e r fo r m o rta r s
. .

Ma n St P (Ma n ov e r Ste r n p u l v e r ) A p o r o u s p o w d e r e a s il y ign ited ma d e in t h e

. . .
-
.
,

fo r m o f s ta rs c o lo ur g re y wi t h y e llo w s p o t s fo r b la n k ca r t rid ge s fo r ma n oeu vr e s

, , .

te
Co rdi . Ab o u t t he t ime o f t he di c o ver y o f P o u dre B t he E ng li s h Gove r nments ,

appointed a c o mmi t te e t o in v e s t iga t e and report upon t he subj e c t o f a sui t a ble

sm o kele s s p o w der fo r the B ri t ish s ervi c e Samples were ob tained of balli s ti te .

and all o t her a v ail able p o w der s b u t t he c o mmi t te e w a s no t s a t i s fied with ,

any of t hem a n d finally devi se d a n e w one to w hi c h the name C o rdite w a s

, ,

given fr o m t he fa c t that it w a s ma d e in t he form of cord s The composi t i on .

di ff ere d from tha t o f ba lli s t ite in that gun c otton w a s use d insoluble in -
,

ether al c o hol and thi s w a s incorporate d wi th ni tro gl y c erine by means

-
,
-

o f a c e t one w hi ch w a s af t er w ar d s e v aporate d o ff
,
Mi neral j e lly a s e mi soli d .
,
-

pe t roleum produ c t w a s a d ded wi th the i dea of lubri cating the barrel It

, .

doe s n o t have thi s eff ec t as it is of cour se ent irely c onsumed in t he expl o sion
,
.
, , ,

bu t it w a s a m ost fortunate ad di tion as it exercises two mo s t important ,

functions in the po w der Firstly i t di mi nishes th e te mperatur e of t he exp losion

.

and s o reduces th e amoun t of erosion of the barrel At the same t ime i t .

increases the v o lume of gas given o ff and so does not reduce the power of
the po w der to any great extent Secondl y it absorbs the ni t rous gase s whi ch .
,

are gradually given o ff w hen the pow d er i s stored and so prevents them ,

fr o m increasing the rate at which the p owder decomposes ; in thi s way the
mi neral j elly ad d s grea t ly to the chemical stabili ty of the p ow der It als o .

p r event s t he ac c ess of the air to the gun cotton and ni tro glyce r ine and so - -
,

r educes t he amount of deterioration due to o x i dati on .

The experimental w ork in conne xi on wi th the inven t ion of c o rdi te w a s

mai n l y carri ed out in Sir F Ab e l s la b o r a tory in l Vo o lwi c h Arsenal mu c h
.
’
- -
,

of the most importan t work being done by Dr I V Ke lhi e r w h o af t e r wards . .

,

succee de d Abel as “ a r Department Chemi st

f
P ate nts No 561 4 of April . .

2 1 8 8 9 a n d No
, ,
of July 22 1 8 8 9 w ere taken o u t on behalf of the
.
, ,

Government by Sir F Abel a nd P rofe s sor (now Sir ) J De w ar who w ere

.
,

members of th e c ommitte e and the same year t he manufa c t ure of cor di te ,

w a s commenced at the Ro yal G u npo w d er Fac tory “ a l th a m Abbey

l

. .
,

C o rdite must be considere d one of the most succes s ful s m okeless po w der s
,

for af ter a quarte r of a c entury du ri ng w hich i t has been subj ecte d to far
.
.
‘

more drastic treatment in all parts of t he B ri t i s h E mpire than the powder

of any other P o w er i t i s still gi ving sa t isfac t ion The Germans meantime
,
.

have ad o pte d and aband o ned a number of di ff e r ent po w ders and for their ,

na v al guns have finall y de c i ded up o n a po w d er of the same type as c ordite .

The t w o w o r s t d efec t s o f c ordite are t ha t i t erodes the guns badl y especia lly ,

t hose o f large cali bre and that w hen s t ore d at a hi gh te mpera t ure its life
,

is a li mi ted one The erosion i s not so s evere as that caused by the use of
’

.
 SL OW B U RNING S MOK E L E SS
-
P OW D E R S

balli stite because the mineral j elly redu c e s the temperature of the gases
,

considerably Nevertheless the wear of the gun s was so bad in the South
. ,

African War that after w ar d s the c omp osition w a s modi fie d in order to reduce
the temperature further The proportion of gun cotton in the powder wa s
.
-

increas ed and the e x plosive thu s altered w a s given the name Cordi te M D
,
. .

(t e modi fied )
. . .

As regards the c hemical stabili ty it i s not p ossible to say whether there i s

any other p o w der which w oul d be more satisfactory as 11 0 other one has been ,

subj ecte d to adverse cli matic con di tions in such immense quantities It i s
.
.
,

however certain that all foreign P o w ers find it necessary to exercise constant
,

vi gilance over their smokeless po w der especially if it has to be stored at a ,

hi gh temperatur e if the vigilance be relaxed catastrophes inevi tably fo llow ,

sooner or later .

A large producti o n of the cor di te for the British services i s made in the
R oyal Gunpow d er Factory at W altham Abbey and i t was there that the ,

metho d s of man uf a c ture w ere worked out U nder the superintendence of .

Colonel Sir F L Nathan R A a great many improvements were e ffected

. .
,
. .
,

in e v ery part of the manufacture whereby the safety of the workmen w a s ,

increased the stability of the e xplosives wa s improved and the c ost of

, ,

production w a s reduced Many of these methods have now been adopt c d by .

-

th e p rivate contra c tors w h o also supply c or di te to th e Government

, .

When the stove in w hi c h the gun cotton has been dr ied i s quite cool
’

-
, , ,

the men go and un load it The g u n cotton i s weighed out in the porch of .
-

the stove These operations requir e to be carried out with th e greatest care
.
,

as dry gun cotton i s very sensitive The men wear nothi ng on their feet
-
.

but socks formerly the gun cotton was weighed out into brass lined w ooden
,
- -

bo x es but now waterproof indi a rubber bags are used Several explosions
,
-
.

have been ascribed to th e j ar or friction of the e dges and corners of such

heavy b o xes one aga inst the other especia lly w hen the boxes have contain e d ,

nitr o g ly ce r in e f Such accidents can be guarded against to some extent by

-

co v ering the edges w ith rubber o r leather but it i s be tter to avoi d this danger ,

b y u s ing rubber bags ; but i f nitro glycerine i s t o be p oured int o them it -

i s essential that they should be absolutely w ater tight and they sho uld be -
,

inspe c ted frequently t o ensure thi s The scales are of such a design a s to .

reduce friction between the knife edges to a mini mum the w eights are either -

attache d to the scale s o a s to fo rm an integra l part of it o r they are ma de ,

of gutta percha bottle s fill e d wi th the re quisite quanti t y of lead shot The
-
.

quantity w e ighed out into e a ch bag is t hat w hich is re q uir ed for a charge of
V OL . 1. 20
 E X P L OSIV E S

the incorporator o r if thi s be o f great size an integral fraction of it The

, , .

ne c ks o f the bag s are tied up a n d they are transported by boat or trolley

,

to the mi x ing h o use .

Formerly the ni tro glycerine was weighed out i nto in dia rubber buckets
- —

and then poured on to the gun cotton in the bras s li ned boxes Now however
- -
.
, ,

it i s measured out i n a spe c ial burette made of lea d which holds the exact ,

quantity require d and i s fi xed to the floor It is a small cylindr ical vessel
,
.

w ith a c oni cal top ending i n a narro w ne c k the bottom slopes down to one
si de w here there i s an orifi c e t o which a rubber tube i s attached the other ,

end of w hich can be passed over a lead plug near the top of the burette when ,

it is n o t being emptied Round th e outsi d e of the neck i s a channel to catch

.

nitro glycerine that overflows a n d this i s conducted by a pipe into a rubber

-
,

bucket so that it can be returned to the fi lte r tank The burette i s filled
,
-
.

by means o f the rubber pipe attached to the fi lte r tank until it is quite full -
, ,

and then the burette i s emptied by means of the similar rubber tube attached
to i t int o one of the rubber bags containi ng dr y g un cotton -
.

The next operation i s to mix the gun cotton and nitro glycerine roughly - -

together and reduce the large p ri mers of the former to the f o rm of powder
, .

At one time thi s was done by rubbing the material through a é inch copper —

wi re sieve but now a special lead table i s made for the purpose
,
This is .

pear shaped and sli ghtly di shed out At one end are a number of é inch
-
.
-

h o les and underneath i s a sort of neck on to which a bag can be attached

, .

The contents of a bag of gun cotton and nitro glycerine are placed on the - —

other and larger part of the table then a man wearing leather gloves transfers
a li ttl e at a time to the end where the holes are and rub s it through into the
bag below No unnecessary v io le n c e mu s t be u sed
'

. .

”
I nco r p o r a ting
. The c or d ite paste thus obtaine d i s next taken to the i nco rp orating
house .The interior of th e incorp orator (s ee Figs 56 57) is thoroug hl y .
,

m o istened with acetone the c harge of paste i s added and the rest of the
,

acetone and the ma c hine is run for three and a half h our s th en the mineral
, ,

j elly i s added a n d the knea ding i s continued for another three and a half
hours The quantity of acetone used i s about 56 per cent o f the weight of
. .

the gun c ott o n -

.

Pressin g . The cor d ite d o ugh thus obtained i s ne x t pressed through a die whic h ,

form s it int o a cord The type o f p re s s u s ed depen d s upon the size o f c o rdi te
.

that i s to be made The small er s izes such as 3 2whic h is u s ed fo r rifles are

.
,
-
,

pressed in a small press with only a single orifi c e and the c ord as it emerges ,

i s woun d o n to a small d rum w hi c h i s then taken to the cordite stove for

,

d rying The larger sizes are made i n large presses whi ch have several orifices
.
,

and the large c o r d s as they emerge are cut by hand to the lengths require d ,

a c c ording t o the size of the cart ri dge s to be made these sticks are then laid
upon trays which are conveyed to the stove Inside the press cyli nder
,
.
 SL OW B URNING S MOK E L E SS
-
P OW D E RS

above the die i s place d a piece of fine wire gauze through w hi ch the dough ,

i s made to pass in or der to remove from it a ll foreign material as far as possible .

The dough i s rammed into the press cylin der by means of a wooden rammer .

There i s o nl y one pressin g operation whereas the Ame ri can m ul tiperforated ,

nitro cellul ose pow d er undergoes four

-
.

For pressing cor di te in the ordi nary round form the die has of course , ,

a s imple ro u nd hole For making tubular cor di te a pin i s inserted in th e

.

c entre o f the hole In the case of tubul ar cor di te of small size it is found
.

that the tubes have a tendency to c ollapse in consequence of the di ffi c ul ty

th e air has to pass through a great length of narrow tube To overcome .

this di fficulty Lloyd and Curtis s a n d Harvey Ltd use a perforated pin ’
.

c om mu n i catin g through the side of the di e with the open air 1

.

Occasionally the cordite ignites as it emerges from the press As a rul e .

n o serious damage i s d one but on Sep tember 1 7 1 9 0 9 an igni tion took place
, , ,

at Waltham Abbey whilst pressing c ordi te Mk I size 20 which wrecked the .

,

press and damaged the buil din g Tw o men w ere inj ured by broken glass .

from the wi ndows whi ch were shattered The fire was accompani ed by two
,
.

e xplosions probably of acetone vap our as well as some cordi te The first .

apparently destroyed the di e seatin g and released the di e the burnin g then
continued and the second explosion occur red in the cylin der ?
,

The cordi te stove consists merely of a b uil di ng pro v ided w ith sui table Dry ing .

racks and heated by means of steam pipes to a m oderate temperature whi ch ,

depends up on the sort of cor di te that i s to be dri ed Cordi te Mk I size 3 2 . .

—

gives o ff its moistur e so rea di ly that art ificial heat is not necessary i n the
summer time All that is re quir ed i s to keep the reels in the stove at a
.

temperature of about 1 5 C for a few days °

The larger sizes are dried at
. .

temperatures from 3 8 to 43 C for periods ranging up to a fortni ght Cordite

° °
. .

M D gi ves off its moisture muc h less readily than Mk I and c o nsequently
. . .
,

requi res to be kept in the stove several times as long in the case of the largest
sizes the sto v in g occupies months and is one of the greatest difficul ties that
,

have to be c ontended with in the manufactur e The moisture in the .

cordite Mk I must not exceed 0 4 to 0 6 per cent accor di ng to size but the
.
-
.
,

percentage a llo w ed in M D i s considerably more The size of c ordi te i s given

. . .

by a figure which i s the approximate diameter in hun dredths of an inch of

,

the di e through whi c h the c ordi te has been pressed Thus cor dite size 50 has .

been pressed through a die about inch in di ameter The thickn ess of the .

cord is ho w ever somewhat less than thi s as it shrinks considerably in dr ying

, , , .

Various particul ars about the di ff erent sizes of cor dite will be foun d in the
Tr ea tis e o n S er v ice E x p los i ves Appen di ces V and VI , .

It i s u sual n o w to recover as much as p ossible of the acetone that i s given

o ff d ur ing the drying The c ordite sh o uld th erefore be placed in an air tight -
.

1 En
g Pa t
, , f N ve m b r 28 1 9 10
o o
2
S e A R
e 1 90 9
,
p 3 3 ,
e . .
, , .
,
 E X P L OSIVE S

re c ep t a c le as s o o n as po s s ible afte r p r ess ing a n d th is sho ul d b e ta ken to th e ,

s t o v e wi thou t unn ec essary lo s s of t ime .

The Japanese Governm en t formerly bought cordi t e fo r i t s na v al o rdnan c e

from pri v ate firms in E nglan d but af t er t he s p o ntaneou s igni t i o n on t he
,

J l ika s a in 1 0 5 i t re olve to make i t s own po der

. 9 s d w 1
P owder s fo r field a n d .

mo u nta in g u ns c apt u red by the Rus s ians during the Ru s s o Japane s e w a r -

were foun d to be ni tr o cell u lose pow d ers wi th 40 to 47 per c en t s oluble in

-
.

e t her alcohol and 1 25 per cent N

-
1
They were i n st ri p a n d flake fo rm
. .

re s pectively The Japanese are sai d now to be nitr at ing wood cell u lose
.

ob tained from the i sland of Sa kh a lin e ?

The smokeless powders used for sporting rifles are pra c t i c ally t he s ame
a s t hose used for m ilitary small arms Ball istite of a sui table s i ze is employe d
-
.

to a c onsiderable e x te nt as th e erosion is not so very severe in these weap o ns

, .

Cor di te is very largely used most of the p ri n c ipal exp losives manufacturers i n
Englan d make cordite for the Governm ent and c ons equently have all t he pla nt ,

a n d e xp e ri ence required Se v eral slight modifi ca t ions of cordite are also ma d e

. .

Thus Ky n o c h Ltd in a xi te have replaced a p ortion of the gun cotton by

.
-

mean s of pota ssium nitrate or o x alate s of p otassium and bari u m A sample .

tha t I exami ned some years ago had the following compo s i t ion :
N it r o g ly ce rin -
e 29 7 p ce n t
-
er .

G un c o tt o n-
63 1 -

Mine r l j e ll y a n d o il
a 5 1
Vo la t il ma t t r e e 02
P o ta ss iu m ni t ra te 1 9 -

100 0

It was made in t he form of flat strip s The pa t en t s No s 1 8 92 of June 22 . .

2
,

1 90 5 ,
a nd of Jul y 26 1 90 5 cover th e use o f o li v e oil , ,
-

in a ddi t ion to vase line or mineral j e lly of flake s and s t rip s w ith vari ous form s ,

of ribs a n d knobs to facili ta te ignition a n d th e a ddition of carbonate s A x i te , .

i s al s o s ometimes made of a composition re s embling t hat of c or dite Mk I wi t h .

part of t he gun c otton replaced by potassium ni trate It is cla imed t ha t

-
.

a x ite ero d es t he r ifl e less than cordi t e a s t he temperature of explosion is

'

l o wer and that it does not cause the barrel to ru s t so much becau s e the
, ,

re s i d ue remaining in t he bore is alka line .

Moddi te . E ley Bros also manufacture a variety o f c o r dite w hi c h t hey c all Mo ddi te
. .

A s ample w hi c h I examine d had the c o mp o s i t i o n

, ,
'

N it r g l y ce rin
o -
e

N it ro llul c e o se

Min r l j lly e a e .

V o la t il e I rra t te r

B ui s s o n P r o b leme des P o u d r es , p 2
'
1
, . 1 75 . Sa p o s h ni ko fi , S .S .
, 1 90 6, p . 69 .
 SL OW B URNING S MOKE L E SS
-
P OWD E RS 30 9

Of the nitro cell ulose 3 4 5 per cent was soluble in ether alcohol It was
- -
.
-
.

made in the form of strip .

Nitro cellulose pow ders are also used in sporting rifles They are generally
-
.

made of soluble nitro cellulose containing 1 2 to per c ent N gelatinize d

.

with ether alcoh o l S ometimes a few per cent of some other c onstituent
-
. .
,

such as resin i s ad ded U sually the p o wders are ma d e in the form o f flakes
, . .
 C H AP TE R XX I I

REQUI REMENTS OF A SL OW -BURNI NG SMOK ELESS POW DER

Ra te of b urnin g : Fo rm o f p o w d r P r o gr s s ive p o w d e r E r o s io n N it ro
e : e : :

r
g ly c e in e v.n it r o ce llul o s e p o w d e r
-
B c kfl a h : Mu le fl am e Pro du c t s o f
s : a s zz :

e x p l o s io n Te s t in g p r o p llan t s E ffi c ien cy e .

IT i s required of a powder for rifles or ordnance that it shall give a hi gh muzzle -

velocity with m oderate pressures that it shall not cau se too much erosion ,

of the bore and that the ba lli stic s shall be regul ar i e di fferent round s fired
, , . .

with similar ammuni tion must give practically the same velocity to the
proj ectile The speed ac quired by the bull et or shell i s due to the pressure
.

of the p owder gases on its base as it travels down the bore of the fi r e arm ,
-

and it i s important that the p owder shall burn i n such a manner that the
pressure i s suitable d uring the whole of the time until the proj ectile leaves the
muzzle Two of the most important facts in conne x ion wi th the study of
.

internal ballistic s are (a ) That the grains of c ompletely gelatinized powders

burn away uniformly from the surface so that they retain their original shape , ,

but get thi nn er until entirely consumed ; and (b ) that the ra t e of burning
varies directly with the pressure From the results of experiments i n close d .

vessels Vieill e d educed that the rate of burning 9) could be calc u late d from an
e quation of the form t} cp where p i s the pressure and c and a: are con s tants
’
, .

For o rdinary black powder a: 0 5 for highly compressed black prism powder z :
,

0 3 3 for brown prism p ow d er 0 2 5 for P ou d re B 0 67 and for p ow d er con

, , ,

taining 50 per cent nitro glyce ri ne Manse ll 2 and P e ta v e l 3 prefer an

.
-

e quation of the form 7) a ap where d i s the rate of burning when there

o , o

i s no pressure and a i s the rate of increase of burning per u ni t of pressure

, .

For cor di te d 0 5 c m per sec and a

o 0 0 1 8 c m per sec per atmosphere
-
. . . 2 . . .

That the burni ng proceeds uniformly by layers i s shown by the fact that
if a gelatinized powder be fired from a gun which i s too short to allow o f the ,

total c onsumption of the explosive the remain s of the grains thrown from ,

the muzzle are found to be in every way s imilar to the original grains ex c ept ,

that the di me ns ro n s are reduce d .

1
Ve n n in , P o u dr e s ct E p x lo s i s , f p . 72 .
2
P h il . Tr a n s , 1 9 0 7, 20 7A , p . 24 3 .

3
P roc . RS
. .
, 79 A , p . 277 ; S S . ., 1 90 8 , p . 1 66 .

3 10
FI G . 61 . Pro j e c t ile a n d P o w d e r C h arge fo r Ame rican 1 6 in ch -
G un ;

We igh t o f C ha rge 666 5 lb n it r o c l lul o

, .
-
e
po wd r
se e

(Fr o m S mi th s o n ia n Rep o r t, 1 9 14 , p . 256)

 EXP L OSI VES
For m o f The resul t of t hi s is tha t wi th a po w der mad e in the form o f cords or cubes
t here i s a dim inu t ion of t he burnin g s u rfac e a s t he c ombu t ion of t he c harge s

p r oc eeds and c onse quen t ly t he p r e ssu r e falls o ff rapidl y a s t he proj ec t ile

,

approa c hes t he muz zle al t hough no t so mu c h as w a s t he case wi t h bla ck

,

po w der w hi ch be ing porous di d n o t b ur n en t irely by parallel surfac es In .

o r d er t o ove r come t his obj ec t ion o t her forms a re of t en adop t e d for t he gr ains

of po w der I f a s t rip or flake be u se d t he wi d t h of whi ch is great compared

.
.
.

wi t h t he t hic knes st he a rea of surface r emain s p r ac t ica lly c onsta nt until th e

,
.

ma t e rial is en t irel y c onsum e d I t ha s be en foun d however t ha t po w ders

.
, ,
.

made up in t hese fla t form s a re liable to give irregular balli stics a n d t hi s has ,

been as c ri b ed to t he obs ta cles i n t he w a y of regul ar ignition when t wo gra ins ,

li e fl a t agains t one ano t her Messrs Ky no c h have proposed to remedy thi s

. .

defec t b y providin g t he s t rip s or flak e s wi t h ri b s or knob s .

Cons t a n c y of t he area of sur fa c e c a n a lso be a t t a ined by making th e p owder

in t he form of t ube s There i s t hen no di fi c ul ty about the ign i t ion bu t
.
,

t h e pressure in si d e t he t ube i s al w ays some w ha t greate r th an out side because ,

t he gas es canno t escape ver y rea di l y a n d t hi s exc e ss of pressure may be come

,

sufficien t ly grea t t o split t he t ube s If t hi s o c c ur t he ba llis t ics be come .

,

un reli able pa r t ly on acc oun t of the sudden re lief of p re ssur e and p ar t ly b e

, ,

cau s e t he s u rfac e is inc r ea sed in an er r a t ic ma mre r If t he gra vimetric densi t y .

of t he po w der in t he c ham ber be hi gh t he general p re ssur e is in crease d and th e

,

di ff e r en c e be t w een t he p ressure insi d e a n d ou t si d e t he tube s i s di min i shed .

If in t ea d of onl y one pe r fo r a t ion t he r e b e se v e r al as is the ca se wi th the

s

Ame ri can mul t iperfora t ed p owder t he pressure inc reases as t he bur nin g ,

pro c eed and con se quen t l y t he pressur e i s ma in t a i ne d a t a hi gher level w hil s t

s

t he p ro j ec t ile is t r ave lling t hro ugh the forward porti o n of t he b o re Thi s shoul d .

no t b e c arried to o far b ecause it is no t p r a c t icable t o have great thi ck ness

.

of me t a l near t he muzzle To preven t t he grains spli t t in g in con s equence of

.

t he gre a t p r es s u r e in s i d e t hem t h e v are c u t in t o shor t leng t hs .

The t hic k ne ss or diame t er of a pow d er sh o ul d be such t ha t i t is entirely

c o nsum e d shor t l y before t he proj ec t ile reache s t he mu z zle .

The rela t i v e ra t e of burn ing of th e po w der charge a t di ff erent instan t s -

can al s o b e r e g u l i te d by submi t t i ng t he e xplosive t o an o pe r a t ion whe r ein ,

t he su rf a c e la y e r of t he ma t e rial i s modi fied Su c h progre ssive p owder .

is ma d e a t Ro t t w eil by t rea t ing t he g r ains of ni t ro c ell ul ose powder wi t h -

an alcoh o lic s olu t ion of C e n t ra lite (dime t hyl phenyl u r ea ) t hi s ca u se s th e - -

ou t er lavers of t he gra in s to burn mo r e slo w l y and so causes t he cham ber ,

p re s s ure t o b e le s a nd t ha t fur t her do w n t he bo r e t o be higher The sa me

s
,
.

me t ho d is b eing t r ied in F r ance 1

Ano t her me t h o d is t o trea t t he powder i n
.

a d rum wi t h a s o lu t i o n of 0 1 to l pe r c en t o f p a r a flin w a x di s s olved in b en zole.

‘ -
.

Flake p o w ders fo r s ma ll a r m s a re some t imes c o ated wi t h graphi t e Thi s

-
.

1
eeS Flo n t in S S
re , 1 9 13 p 32 ;
. .
, l B is so n P ro b lem d
, . P ud
a so p 40 u , e es o res , . .
 E XPLOSI V
ES

no t onl y r est r ains t he ini tial veloc i t y of igni tion but al s o fa c ili ta te s t he loadi ng
- .

from loadi ng mac hi nes .

nitro -
slycer
The r e ha s bee n cons ide r able c on t r oversy as t o th e relative advanta ge s and
d i sa d v an t a ges of ni tr o ce ll ul o s e and ni t r o glyce r in e powders The ad v anta ges
- -
.

claimed for ni t ro gly ce rine po w d ers are t h a t t hey give mo r e r egula r ball i s t ics
-

do no t give ba c k fl a s h w hen fire d a re mo r e powerful are c heaper to manu

-
, ,

fa c t ur e lea v e les s residue in t he gun and have a t least as good che mi cal
, ,

s ta b ili t y as ni t r o ce llul ose po w de r s Their g r ea t disa dvan t age i s th at t he

-
.

t empe ra t ure of explosion is hi gh and conse quently th e e ro s ion of th e bore ,

of t he g un i s very severe .

In spi t e of t he fac t t ha t t hey erode the gun s m ore most of t he P owers ,

.

use ni t r o glycerin e powde r s in t heir la rge gun s and t he principal re ason for
-

t hi is t ha t they give mo r e regular balli stics It is impossible to d ri ve the

s . .

w hole of t h e so lven t ou t of a c o ll o ide d nitro cellul ose powder ev e n though -

,

t he dryi ng be grea t ly p rolonged a n d in d eed i t is advisable to leave seve r al ,

p e r c en t i n t he powder be ca u se o th erwise i t is to o b r i tt le
. But t hi s resi d ual
,
.

s olven t is a so u rc e of u ncer t a i nt y be ca u s e i t gradu a lly di ff u s e s from t he cen t r e ,

o f t he g r ains or s t rips e tc a n d evapo r a t e s even t h o ugh the p o wder be s t o r ed

, .
, ,

i n clo s ed re ce p t a c les The lo ss of t hi s c ombustible m a t te r makes t he powder

.

mo r e po w erful but wha t i s m ore se ri o u s is tha t th e m a te ri al b e c omes harder

,

a n d mo r e b rit t le and it may brea k up when fi re d and conse quen t ly gi ve high

, ,

p r ess u r es and irr egul ar velocities .

The a d di t ion of a c onside r able proportio n of ni t r o gly c erin e to a powder -

makes i t give up i t s vola t ile ma t t er much more r eadil y Apparen t ly th e .

“

re sidual s olven t p a sse s from the par t icles of g un cot t o n to t he ad j acen t on e s -

.

of ni t r o glycerine and di ffu se s t hr ough t he la t te r to t he ou t s i d e of t he s t ick

-
,

or fl a ke much mo r e r apidly than it ca n t hrough t he c o lloi d al ni t ro ce llul o se -

.
l

The r e s ul t is t ha t t he p e rcen t age of volat ile m a t t e r c a n be r educe d wi t h o u t

di ffi c ul ty to 1 pe r c en t o r a li t t le more a n d i f a frac t ion of thi s af t e r wards
.
,

esc ape s i t doe s not al te r t he composi t ion of the p o w der ma te r ia llv and e ven
,
.
.

t h e lo s s of t he w hole of i t does no t aff ec t t he physi cal pro per t i e s o f th e ma t e ri al .

.

The p r ese nce of t h e ni t ro glyce rine cause s i t to remain al w a ys a tough or -

s ligh t l y pla s t ic ma ss ac cordi ng to th e pe rcenta ge Ni t r e glycerine p owders .

-

a re als o c onsiderably le ss hygroscopi c Thu s N L Hansen foun d t hat i n . . .

.

a ni t r o ce llulo s e powder in s t rip form 0 78 mm t hi ck f r eely e x p os e d t he moisture

'
-
.

vari e d from to 2 3 5 per ce nt ac cording to t he t ime o f year a n d t he amoun t .

of m o is t u re in t he a t m o s phe r e and i n a t ubular ni tro cell ulo s e powde r 3 70 ,

-

m m th ick from 0 56 to 1 3 6 per cent

.
?
“ i t h a ni t ro glycerine powder t he
- - -

1
I t ha s b e e n fo u n d b y H . Be c hh o ld a nd J Zie gl r tha t w h rea s in dil ut ge ls diffu
. e e e

s io nis p r a c t ica lly t h e s me a

in t h e p r e as u so lve n t in ve ry t iff g l it is mu h m ll r
, s e s c s a e ,

a n d ma y b e e it h e r in c r ea s ed o r d im in is h ed b y t h a d d it i n f t h r s u b s ta n
e (Ze it h o o o e ce s sc .

pluy s ika l . C he m .
, 56, 1 90 6, p .
2
S S . .
, 19 1 1 , p . 4 61 .
RE QU I RE ME NTS OF A SL OW B U RNING S MOKE L ESS P OW D ER -
3 15

amoun ts of water ab sorbed and the variations woul d have been much smaller ,

as the nitro glycerine waterproofs the p ow der

-
.

The smaller bulk of nitro glycerine p ow ders is o f some advantage on board

-

ship where magazine room i s limited The lighter weight of t h cartridges

,
.

also makes them rather more easy to handle .

The question of erosion w a s in v e s tig a te d by Vieille who showe d that th e te m

l 1 Ems“
,

e r a tu r e pr o duced in the e xplosion was the principal factor He fire d charges

p .

of vari o u s explosives in vessels ,which were closed ex c ept for a small o rifice
dril led through a metal plug whi c h w a s weighed before and after the exp eriment
,
.

He found that the erosion increased w ith in crease of length of the o r ifi ce with ,

decrease of the di ameter a n d with i ncrease of the volume of gas and the pressure
,
.

The influence of the nature of the exp losive i s show n by the foll o w ing Table .

This clearly shows the influence of the temperature of the e xplosion gases .

The lower the melting point o f the metal the more it is ero de d the following
-

res ul ts were o btaine d by firing charges o f 3 55 grain s of ballistite using plugs ,

of di fferent metals
P la t i nu m 59 1 ub mm -
c . .

P la t in m ir id ium
u -

Ir n
o

C a nn o n t e e ls

Ch o m
r t e e l (3 5 p r ce n t )
e s -
e .

C o pp e r
N ic k l s t e l (24 p
e e nt ) er ce .

C a t ir o n
s

Silve r
B r o n ze
B ra ss

Zin c

1
P . et S v o l. 30 1 90 2, p . 1 57 .
 3 16 E X P L OSIV ES

I t wi ll be seen th a t t he mel t ing point a ffec ts the ero s i o n far more th an the -

har d nes s of the metal Si milar e xperiments have been carried out in Ame ri ca 1
.
,

w here charges of sm o keles s po w d er w ere fi red in an armour piercing she ll -

,

clo s e d wi t h plugs of di ff erent m etals w hich were d rille d w i t h holes mm , .

i n diame t er The erosion w a s measured b v th e number o f time s the area of

.

t he o ri fice w a s enlarged '

l Vr o u g h t i r on

Ma r t i n s tee l

3 pe r ce nt
t n g s e n s te e l
. u t
‘
r
Ma t in s t e e l w it 3 p e r c e h nt . t un g t n s e

3 7} p e r c ent n ic ke l s e e l . t
20 p n t ni k
er ce . c el s te e l

Ma ng n br na ese o ze

The erosion i s to be ascribed t o t he fusion o f the surface of the metal which ,

is t hen swept a w ay by the rush o f gas As regar d s the influence of pressure .

Vieil le found t hat up to a pressure of 1 00 kg / c m the erosion w a s only s light

2
. .

i t increa s es very rapi dl y wi th rise of pressure from 9 0 0 to 2000 kg / cm and 2

. .
,

t hen remain s practically c onstant from 2000 to 40 0 0 kg .

Noble carried out an elaborate series of ex periments with cordite s specially

manufac t ure d wi th varying prop o rtions of nitro glycerine 2
These were tested -
.

i n t he calorimetric b o mb and also fired fr o m the gun The resul ts are shown .

i n Fig 63 I t w ill be seen that w hen th e percentage of nitro glycerine i s

. .
-

in c rea s e d from 1 0 to 60 per cent the quantity of heat in crease d 60 per cent .
, .
,

but th e ero s i o n wa s grea t er by nearly 500 per cent .

W hen only s mall charges are u s ed the ero s ion i s not very severe fo r , ,

both the t emperature and pressure i n the cham ber a re mu c h l o wer It is .

largely fo r this reason tha t p ractice wi t h large guns i s m ostly carri ed ou t

wi t h re duced charge s It i s reckoned that the w ear of the gu n due to a proof
.

roun d i s equal t o t hat of tw o full charges a n d that a f u ll c harge of p o w der i s ,

equi valen t to f o ur ! ch arges or si x teen charges or sixteen blank c harges -

.

One r o und o f c o rdi t e Mk I is equivalent to several of cor di te M D pro ducing

. . .

the s ame balli s t ic s It is i n large or d nance firing very heavy charges of

.
,

p o w der i n or der to o b tain a high mu zzle velocity that th e erosion is m o s t ,

s evere i n s maller guns i t is c omparatively trifling By properly pr o portioning .

t he c hamber a nd the length o f th e gun and making the powder of the righ t ,

s i ze a n d s hape t he er o si o n c a n be reduced s ome w hat but naval guns of large

, ,

s i ze require r e lining af ter they have fi re d a fe w hun d red full charge s

- .
.

l Vit h s m o kele s s p o w der t he er o s ion m o s t ly c o n s ist s in w a s hing the s u r face

o f t he me t al sm o o t hly a w ay “ i th high charge s o f b la c k p o w der w hi c h
.
,

genera t e d t emperature s o f t he s am e o rder the me tal w a s s c o re d in t o deep ,

ru t s a n d t hi s h a s been a s cribed to t he me c hani c al a c t i o n of t he s o li d par t icles

.

1
S ee S S . .
, 1 90 7, p . 21 1 .
2
A r tille r y a nd E r p lo s ir e s , p
'
. 5 34 .
RE QU I REME NTS OF A SL OW B U RNING S MOK E L E SS P OWD E R
-
317

in the products of e x plosion With smokeless powder there is some sc o ring

.
,

but not nearly so much .

E rosion is most severe not i n the p owder chamber but j ust in front of
, ,

it where the powder gases r ush past between the copper band of the pr o j ectile
,

Pe r ce n t N it r e
.
-
r
g ly c e in e

FI G . 63 . N o b le s E r o
’
s io n E x
pe r im en t s

and the bore of the gun Further d own the bore the wear is much less as
.
,

the pressures are less the copper ban d s fit the r ifl ing better and the proj ectile
, ,

is travelling so rapidly that the escapes of gas have little time to d o harm
,
.

The inner tubes of guns also occasionally split This is apparently caused .

by the alternate heating and cooling of the inner surface of the metal combined
with the compression to which it is subj ected The result is that the surface .

layer o f metal i s in a state of tension .

Yarnell has shown that j ust as nitro gly c erine powders c ause m ore erosion
-

than those that only contain nitro cellulose so nitro cellulose powders of high
-
,
-

ni tration are worse in this respect than those of low nitration in spite of the ,
 E X P L OSIV E S

fa c t t hat a s ma ller c harge is requir ed Like Viei lle he found that the erosion .
1

i s prac t ica lly in d ependent of the pressure if i t exceed 20 00 atmospheres .

Yarnell als o tried the effect of a d ding considerable quantitie s of water or

para ffin to the charge The erosion was greatly re duced thereby a n d the
.
,

pre s sures w ere increased Such ad di tions have been advocated frequently bu t
.
,

apart fr o m the difficul ty of carryin g them out under war c ondi tions the ,

presence o f cooling material in the lump so to speak must render the ba lli stics , ,

uneven . Any addi tion should be inco r pora ted with the powder during
manufacture The mineral j elly in c or di te reduces the temperature of the
.

products several hundred degrees and in fact cor dite M D has a temperature , . .

o f explosion w hi c h i s but l ittle higher than that of s o me nitro cellul ose

,
-

powders An ad di tion suc h a s thi s does not di minish the ballistic efficiency
.

of th e p owder to any great extent because the reduction of temperature i s ,

partly compensated by the i ncrease in the volume of gas fo rme d .

Vieille (lo o c i t ) showed the e ffect of adding nitro guanidi ne to powders :

. .
-

E r o s io n p e r g r a m m e

Ni t r e - c e llu l o s e
C o r d i te tt
B a ll is i e
P o w de r

Alo n e
30 p e r ce n t n it r o
.
-
gu an id in e

50

The difficulty is to find a substance that can be in c orporated with the p owder
i n su ffi cient quantity w ithout affecting inj uriously any of its qualities Nitro .

guanidi ne for insta nce ma kes it brittle

,
2
, .

BM k flaSh
'
o With a low temperature of explosion i s always associated a low percentage
of oxygen in the p o wder and consequently a large pr e portion of carbon ,

monoxide in the products W hen large guns are fired the c o mbustible powder .

gases are li able to catch light at the muzzle and burn d o wn the b o re and ,

on the breech being o pene d this flame may emerge e s pecially if the gun be ,

pointing to wind w ard In France where nitro c ellul o se p o wder o nly is u sed
.
,
-
,

a nu mber of di s asters have been cau se d by such flames emerging and setting ,

light to cartridges in the turret or stan di ng near the gu n Similar accidents , .

h a v e oc c urred in the U nited States where also nitr o cellul o se powders are ,
-

employed exclusive ly This danger i s also present with cordite although not
.
,

to the same extent and mu st be guarded against , .

1
J ou rn. A me r . S oc . N a va l E ng in ee r s , Ma y 1 9 10 ; S S
. .
, 1 9 1 1,
p . 1 9 3.
3 B rav ttae , S S . .
, 19 12 p , . 49 3,
RE QU I RE MENTS OF A SL OW B URNING S MOK E L E SS
-
P OWD E R 31 9

When cannon are fired flames appear at the muzzle due to the ignition
,
Muzzlo fl a
of the c ombustible gaseou s products Thi s i s obj ectionable because at ni gh t
.
,

it reveals the position of the guns The flame can be di minished or even .

abolished in some c ases by adding a few per cent of so di um resinate or other .

sodium or potassium salt but the quantity of smoke is thereby greatly

1
,

increased and t hi s will reveal the position by day and will obstruc t the ,

g rmn e r s .

Muzzle flame is due to hi gh temperature of the gases as they emerge from

the gun as well as to their comp osition With a large charge of powder it .

i s much m ore di fficult to keep this temperature below the ignition p oint of
the gases The problem of doing away with it has much in common with
.

that of the preparation of coal min e exp losives .

Numerous analyses of the products from the explosion of c ordi te and Pr o dfl QtS of
ex plosw n
Rottweil nitro cellul ose powder have been publi shed by Noble The powders
'
- 2
.

were exp loded in a calori metric b omb at va ri ous densities of loa di ng but ,

only the figures for the lowest density 0 0 5 are reproduced here as they , , ,

probably represent most nearly the composition of the gases evolved in the
gun .

The temperatures were calculate d with very low values for the Specific heats
and are c o nsequently hi gh and have only relative value .

1
S ee Sc h ild e r ma nn , S S
. .
, 1 9 1 3, p
. 1 26. 2
P roc . Roy . So c .
,
76A, 1 90 5, p . 3 8 1.
 E X P L OSIV E S

Macnab and Leight o n c arried similar e x periments w ith c o r dite The o ut .

1

relative temperatures o f e x plosion determine d with thermo c ouples a s c ompared

w ith the sporting powders given o n p 3 27 were 1 9 1 and 1 68 for Cordite Mk I . .

and M D re s pectively
. . .

A c cordi ng to Schumacher 2 American multiperforated powder fired at a ,

den s ity of 0 0 53 gives 664 4 c c o f permanent gas per gramme having the . .

c o mposition

Sir A Noble has also given the follo w ing figures in

.
.
E n g in eer in g

\ 0 l . Gas Hca . t Vo l . Hea t

10 0 0

90 9 9

9 60 4

When a new explo s ive i s being investigated all the usual characteristics
of an explo s ive may with advantage be determine d such as the power , ,

in fl a mma b ility residue v o lume and composition of gases

, , The recoil and .

erosion of the gun may also be measured and the temperature of combustio n ,

calculated A determination may also be made of the law of c ombustion

.
,

t e the rate of ri s e of pressure with time by means of a spring manometer 3

. .
, .

Fo r current supplies of pow d er th e principal te s ts are d etermination of

the compo s ition by c hemi c al analysis stability test s measurements of the , ,

muzzle velo c ity by means o f an ele c tri c chron o graph and o f th e maximu m ,

pre s s u re i n the c hamber of the gun by means of a cru s her ga u ge The mean .

and greatest di fferen c es of series o f these last tw o are also taken i nto con
siderati o n .

E mciency . Of the t o tal energy of the p o w der from 1 5 to 40 per cent is actually utili zed .

a s kineti c energy o f the pr o j e c tile Of the remainder th e greater part remains

4
.

1
J . Soc . C hem . I nd .
, 1 9 0 4, p 300 . .
2
1 9 0 7, p . 8 4.
3
Ve n n in et C h n au
es e , p
. 1 42 et s e
q .
4
I b id .
, p . 147.
RE QU I RE ME NTS OF A SL OW B U RNING S MOKE L E SS
-
P OWD E R 321

inthe p owder gases a s heat and kinetic energy bu t the barrel also absorb s ,

a considerable proportion a s heat An investigation car ri ed out with the .

German ri fle M 9 SS gave the followi ng di stri bution :

.
1

H a t in g b a rr l
e e

B u ll t v e lo c it y n r gy
e , e e

r o t a t io n n r gy e e

Re c o il
Ga s es , ca r t r id g e ca s e

1
C . C r n
a z a nd R . R e t ir e , S S
. .
, 1 90 8 , p . 30 3 .

VOL . I .
 C H A PT E R -
XX I I I

FAST-BURNI NG SMOKE ESS POW DERS L

S ho t g un po w d e r s C o nd e ns ed p o w d r s B u l k p o w d r s In gredient Ma nu
- e e s

fa c tu r o f b ulk po w d e r
e Am e ri ca n me t h o d 33 gr a in p o w d r :
s : 30 g ra in : -
e s -

p o w d er F r n ch p o w d r
s G e rm a n p o w d r s
e Am e rica n p o w d e
e s Aust ria n e rs

o w d e rs R e q uir me nt s : T e st in g s h o t g m p o w d r s :
e P o w d e rs f o
: t nc h-
r e r re
p
h o wi t ze rs B la nk po w d e s : r

t
Sh o -g un TH E sho t g un i s dis t inguished from the rifl e not o nl y in not having a rifl ed
-

bo r e bu t al o in be ing genera ll y of considerabl y greater cali bre To produce

,
s .

a w ea pon eas y t o handle i t is necessa ry to make the forward portion of the

ba r rel ver y light and t herefore th ere must be but little pressure excep t nea r
,

t he breec h The di tri b uti on of the shot in a u ni form mann er i e th e

.
s
, . .

formation of a good patte rn see ms to requi re th at compa r atively li ttle ,

p r es u r e be e xer t ed on the shot in the forward p ortion of the barrel For

s .

the se reasons a shot gun p o w der must b u rn much more rapidly than a ri fle
-

po w der and t here fore there mus t b e more surfac e exp osed These powders
,
.

are of two ki nds : the condensed and bul k type s “

.

In the c ondensed po w ders th e ni t ro cell ul ose is comp lete ly gela tiniz ed -

the y are made in much the sa me w a y a s ri fle powders but are formed into ,

qui t e small g rain s or ve r y t hin flakes C a nn o ni te Shot gun Rifl e ite and .
,
-

Spo r ti ng Balli stite are of thi s type but the fir st two of these are no longer ,
.

manufac t u r ed the ir composi t ion i s given in the Table on p 3 27 C a nn o ni te . .

w a s made in t he form of small g ra p hi te d g rai ns t he process of manuf ac t ure

w a s desc ri bed by Sanford in the fi rst edi t ion of hi s N itr o E r p lo s ire 18 96 - s
, ,

p 1 8 2 S hot gun Rifl eite w a s in the form o f thi n flakes ; Sportin g B allisti t e
. .
-

is a l o a flake p o w der
s The ad v ant a ges c la imed for these p o w de r s are t hat
.

t he y leave ve ry li t t le so lid residue when b u r nt and a re c onsequen t l y f r ee from ,

”
smoke and blo w bac k and leave but li t tle foulin g in the bore t hat they
-
, ,

a r e no t much a ff e c ted b y exp osur e to moi t air are very quick and give li ttle s
,

rec o il On t he o t her hand they re qui r e special ca rt ri dg e c a ses with a c one

.
,

of pas t eboard fil lin g up pa rt of t he b a se beca use otherwi s e th e ca se woul d ,

no t b e en t irely fil led and al o t oo m u ch of t he po w der w oul d be e xp osed t o

,
s

t he flash of the cap In cons e quence of the smal l spac e oc cupied by the
.

powder charge ve r y slight va ria t ions in the strength o f the cap and othe r
 FAST B URNING S MOK E L E SS
-
P OWD E RS

condi tions produce great variations in the pressures generated and the gun ,

may therefore be strained dangerously and di ffi c ulties are sometimes ,

e xperienced in extracting the cartridge cases These p ow ders are also more .

di fficult to manufacture than those of the b u lk type .

Bulk p owders are so made that the charge for a 1 2 bore gun occupies Bulk powa -

the same space in the cartridge as the standard charge of 8 2 grains of black
powder occupying a spa ce of 3 li quid drams e qual to 1 0 6 5 c c The first . .

successful smokeless p owder was that of Captain E Schultze of the P russian .

,

Ar till ery who made it from nitrated wood

,
1
Th is was first cut into thin .

veneers from w hi ch small cylinder s were punched and then it was purified by
, ,

boili ng with soda bleachin g and washing After nitration the nitro li gnin was
, .
-

b oiled with soda and washed with cold water and afterwards impregnated
, , ,

w ith the nitrates of barium and potassium In the course of time variou s .

modifications have been made in the process of manufacture The wood .

fibre now used i s thoroughl y purified by drastic chemic a l treatment and ,

is formed into grains by manipulation with solvents after nitration The .

treatm e nt wi th solvent also hardens the grains and makes them more water
proof For further information about the early development o f Schul tze
.

powder s ee a n te p 4 7 also Guttmann P r o gr es s p 3 8 and Appendi ces and

, .
, , , .
,

Gri ffith s P atents 3294 of 1 8 77 and

’
of 1 8 8 4 Most of the other p owder
, .

manufacturers use nitro cotton instead of nitro lignin but the Schul tze
- -
,

Company have adhered to wood fibre as they c onsider that a p owder made ,

with it is less sensitive to variations of loa di ng and gives m ore satisfactory ,

results under adverse climatic conditions .

Bulk p owders fre quently c ontain a small proportion of substances such as Ing edients , r

vaseline or para ffin wax whi c h serve to moderate the action Starch also i s
, .

sometimes used it helps to hold the grains together Camp hor i s somewhat .

obj ectionable as it i s volatile and escapes on long storage The mono and
, .

dinitro derivatives of benzene and toluene are present in some powders ;

-

like camphor they have the property of assisting the gelatinization of the
fibres Other materials that are added sometimes are lamp bla c k wood
.
-
,

meal various gums and potassium ferricyanide In order to complete the

, .

oxidation of suc h added organi c matters and also to make the rate of burning ,

more unif o rm nitrates of barium a n d potassium are added : the ba ri um

,

salt has th e advantage that it pro d uces c omparatively little smoke and i s
not hygros c opic On the other hand it leaves a residue in the gun which
.
, ,

i s difficult to remove Therefore it i s customary to use a consi derable

.

per c entage of barium ni trate together with a small pr e portion of potassium

nitrate A small quantity of an iline dy e is also added in many c ases to colour
.

the po w der Other po w ders are coate d with graphite whi ch renders them
.
,

less liable to become ignited by electrification alth o ugh there is little dange r ,

1
Se e E ng . Pa t . 9 00 of 1 8 64.
 E X P L OSIV E S

of thi s i n p o wders that c ontain mineral salts G r a p h iting also reta rds the .

igni tion of the po w der a n d so acts as a m oderating agent The nitro c ellulose .
-

use d generally c ontains 1 2 5 to 1 2 8 per cent nitrogen and is partially s o luble-

.
,

in ether alc oh ol The addition of calcium carbonate improves the stability

-
.

of t he p o wder by neutralizing any acid that i s given o ff but it should be ,

very intimately mixed with the nitro cellulose and such intimate c ontact i s -
,

bes t pro duced by precipitating the carb onate in the fibres by using hard
water for the b o ilin gzo f th ezni tr o cellulose -
.

The incorporation of the ingre di ents i s i n many cases performed under

'

edge r u n ne r s xs imila r to th o s e used for the mi lling o f b la c k powder The wet

-
'

nitro cellulose c ontaining some 40 per -

,

cent of water is roughly mixed with the .

,

other ingre di ents and these are ground ,

together in the mill water being added ,

from time to time to keep the mixture

m oist The duration of the milli ng and .

the amount of water are regulated accord

ing to the gravimetric density re quired
in the finished product The longer the .

milling and the higher the proportion of

water the greater the gravimetric density , .

F I G 64 .En gli h B lk P o w d r
. s The material is then passed through a
u e

(Th fi m S S 19 0 7 P 424 ) sieve w ith meshes somewhat larger than

‘
el ,
. .
, ,

the finished grain i s to be The m oist .

grains thus formed a re then d ri ed in a stove by means of a current of hot

air the powder being spread on trays to a depth of not more than 3 inches
, .

\Vhen dry the material should be allowed to c ool down in the stove before
it i s m o ved The dust and large lump s are then removed by passing the
.

po w der thro u gh sl o pe reels .

The next operation is the important one of hardening the grain by treating
i t with solvent This i s frequently done by sprayi ng i t with the solvent
.

i nside a drum which can be closed hermetically and r o ta te d a b o u t its axis

,
'

After a few minutes rotation the grains a r e thoroughly m o ist The p owder
’
.

i s then allowed to steep for some time either in the same ve s sel or another
o ne , and then it is dried The preli minary drying may be carried o u t in a
.

s ol v ent re c overy plant consistin g o f a rotating dru m provided w ith a s team

j acket and a h o ll o w a x le whi c h is c onnected through a c ondensing c oil wi th

,

a va c uum pump The coil pump etc are placed in a separate compartment
.
, ,
.
,

from the dry ing d ru m which i s i solated by means of a wa ll ha v i ng n o

,

openi ng s in order to minimize the danger of fire A considerable proporti o n

, .

of the s o lvent is rec overed i n thi s way and after redi s tillation may be u sed ,

again but in order to obtain a satisfactory recovery it i s necessary to cool the

,
 FAST -
BURNI NG S MOKE L E SS P OW D ERS 325

coi l by means of refrigerated brine to a t emperature c onsiderably below the

freezing point of water The drum i s fitted with rib s inside to prevent the
-
.

powder simply sli ding round in a cake The exit i s c overed with wi re gauze and .

c otton wool to prevent dust being drawn into the condenser The man hole .
-

li d fits air tight and can be held on by means of thum screws but during
-
,
-
,

the drying these screws are removed so that the li d is held on by the vacuum
only If pressure arises at any time during the dryi ng the lid will at once
.

fa ll off and relieve the pressure The tempera ture of the powder should .

never exceed about 50 O (122 The powder as it comes from the drum s
°
.
0

conta ins 3 or 4 per cent of water and solvent The drying i s completed on
. .

trays in a drying stove W h en dry it is sifted so as to remove the grains that

.

are too large or too small these are added in small proporti on to a further
charge in the m illing operati on Fin ally the powder is tested for stabili ty and .
,

ballistics and carefull y blended wi th other batches so as to obtain the standard

,

results But before the final tests are made the p owder should be kep t fo r a
.

m onth or two i n order that it may take up the normal amount of moi sture .

In case of necessity it can be aged artific ially by e x posin g it for a few

hours to a hot moist atmosphere but natural ageing is more satisfactory , .

Thi s scheme of manufacture has been varied in many ways The inc orp ora .

ti on for instance can be performed in drum s with li gnum vit ae ba lls The
, , .

mass can then be pressed and broken up into grains of the desired size much
a s is done w ith black p owder Granulation can also be effected by sprinkling
.

the p owdery material with water and then rotating in a drum Vari ou s .

solvents have been used by di fferent p owder makers mixtures of ether and -

alcohol acetone and alcohol and acetone and ether have been employe d
, ,
‘

E ther i s very volatil e and conse quently the losses are consi derable .

E ther alcohol o nl y partially gelatinizes the nitro ce llulose unless the degree
- -

of nitration is low Benzol is sometimes added to m oderate the action

. .

A cor di ng to O
c E M un roe the following method i s adopted in America
1
. .
,

for the production of shot gun p owder wi th fibres entirely gelatinize d The
-
.

manufacture is conducted in a stationary still of copper about 5 feet i n di ameter

with c onical ends A shaft extends downwards through a stuffing box in the
.

top to a point near the bottom At intervals of about 8 inches h o rizontal .

arm s are attached to thi s shaft ; they extend almost to the walls o n either
si d e Five of these are square i n cross section and about 1 inch thick but
.
—
,

the sixth bar which i s the top one i s flattened out so as to form pad dl es
, ,

whic h slant in the direction of motion of the shaft in such a way as to smooth
down the surface o f the c ontents of the still The height from the bottom .

t o the t o p s t irrer blades is about 6 feet 3 inches .

The o rifice at the bottom of the stil l having first been c losed the vertical ,

shaft is set i n rotation at a speed suffi c ient to maintai n the particles of gun
1
US B u ll 9 2, 1 90 8 , p 84
l
. . ( en s u s .
, . .
 EX P L OSIV E S

c o tton in me c hani cal suspensi o n in t he s o lution thi s rota t ion is maintain ed

during t he whole o f the process l Va te r in whi c h 5 per cent of barium nitrate
. .

a n d 2 per c ent o f p o t assium nitra t e have been di ssolve d i s then pumpe d into
.

t he s t ill and finely pulped g un cott o n i s t hr own in through an opening i n the

,
-

upper part In all 450 lb of fresh g un c otton and some 250 lb of d us t and
. .
-
.

fine grain s from pre v iou s granulations are i ntroduced Mo re of t he nitrate .

soluti o n is pumped in a n d finall y t he openi ng is c lose d and an emulsi o n is

, ,

pumpe d in consistin g of 25 t o 50 per cent amyl aceta t e in ni tra t e s o lu t ion .

-
.

The surface of t he li quid should n o w be up to the top stirrer blade s .

The mate ri al n o w begin s t o granul ate and the progress of t he granul a t ion ,

is observed by w i t h drawin g a li t t le of the mi x ture through a small orifice

near the bottom of t he stil l t e n granul ation has been e ff ected throughout
.

t he mass whi ch i s wi t hin five mi nu t es of the t ime when the introduction of

,

t he emulsion into t he still was c ommenced ste am is t u rned into the j acket ,

sur roundi ng the lower portion of the still Heating i s c ontinued for fi ve or .

six hours b y whi ch time practica lly all the amyl a c etate has been di stilled
,
-

o ver together w ith some of the water Thi s is c on densed and the amyl acetate
.
-

is separa te d A gate valve in the b ottom of the still i s now opened and the
.
,

mi x t ure of water and granul ated powder is d rawn o ff into a drainin g tank .

Af te r dra inin g it i s dri ed sized blended and packed The strength and
, , .

amount of the em ul sion used depend up on the amount and quality of the
gun cotton t he best proportions are ascertain ed by expe ri ence The finished
-
.

pow der i s coloure d t o sui t the t aste of customers .

The ol der p o w ders Schultze and Ambe ri te are 42 g rain powders that is
, ,
-
,

to s a y the charge requi red for an or dinary 1 2 bore ca rt r i dge i s 42 grains and -
,

thi s quanti t y o ccupies t he same space in the cartridge as 8 2 grains of black

sporti ng po w der Other 42 grain powders are Ruby Fe li x i te P rimrose
.
-
, ,

Smokeless C o o p p a l No 1 and K S Some of these are still used extensively

, . .
,

but t here is a growing demand for pow ders of whi ch sma ller charge s are
required t he principal advantage o f which is that they gi v e a decidedl y
,

li gh t er re c o il for t he powder produ c ts are ej e c te d from t he mu zzle of the gun

,

wi t h hi gher velocity than the shot It is also claime d that they are qu icker
. .

Re d uc t ion of charge is eff ec t ed by u s ing a nitro cell ulose of higher nitrogen —

c o n t ent and re d u c in g t he pr o p o rti o n of t he other c o ns t ituents These changes

, .

in c rea s e the rate of burni ng so in order to preven t t he pr o duc t i o n of dangerou s

,

p re s s ure s in t he gun it is necessary t o gelatini ze t he nitro cellul o se more -

completely A 3 3 grain po w der can be ma de in much the same manner as i s

.
-

t t
Thir y - h r ee d e s c ri b e d ab o v e e x c ept tha t af t er t he grains have been f o rmed a n d hardene d
,

g r ain p o w der .
a p o r t i o n o f t he ni t rate s i s wa s he d o u t by s t eeping the material s i n wa t er .

A w ell kn o w n 3 3 grain p o w der o f E ng lish manufac t ure is Sm o kele s s Diamon d

- -

H e n r ite i s an o t her o f t hi s cla s s both t he s e are i n the f o rm o f black grains .

E C No 3 is a 3 3 grain p o w der t o o
. .
-
i t is c o l o ured yell o w w i t h am i ne Ot her .
 FAST B URNIN G S MOKE LE SS
-
P OW D E RS 3 27

33 grain p owders are E mpire

-
L ightning Re d Star Stowmarket , , ,

Smokeless Viemos a n d E merald

, .

By taking a further step in the same di rection the charge ca ntb e reduce d
to as li ttle as 30 grains The nitro cellulose i s mixed wi th a small proportion
.
-

of reducers and several times its weight of barium a n d potassium nitrates .

It is then inc o r porated in a W erner and P fl eide r e r machine with suffi c ient
acetone or other suitable solvent to gelatinize it entirely The d ough i s then .

formed i nto small cubes or prisms by processes similar to those employed

for rifle powde rs and after dryi ng the mineral nitrates are diss o lved ou t as
, ,

c ompletely as possible with warm water Only about 5 per cent are left in . . .

S chultze Cube P owder is an instance of a 30 grain powder produce d by a -

process of manufacture of t hi s sort .

a r
C lo ie s p e r g .

r an n t
Pe m e ga s ,
c c . .

Aq vap o ur c c p
.
g , . . er .

To ta l ol g s N TP
v . a . . .

C m p u p e rm n n t g
o . a e as
p . c.

Re la t ive t e mp e ra t ur e
 EXP L OS I VE S

The above Table publishe d in 1 90 4 by Macnab a n d Leigh t on l gives the

, .

c o mposi t i o n o f t he prin c ipal shot gun p o w d ers at t ha t time in u se in E nglan d -

t oge t her w i t h the am o un t of hea t ge nera ted in t he c alorime t ri c b o mb and the

c omp o s ition of the produc t s of e x plosion Of these Shot gun Rifl e ite Spor t in g .
,
-

Balli s t i t e a n d C a nn o ni te w ere con d ensed po w ders SS Shot gun Rifl e ite . . .

,
-

and C a nn o ni te are no longer made .

Spor t ing ballistite is ma d e in much the same ma n ner a s rifle balli stite ,

ex c ept t hat after the sheets have been rolled out acet o ne is a dde d and the ,

r o lling is repea te d so that the fini shed sheets are onl y ab o ut 0 0 0 5 inch t hick
,

and look like oiled silk These are cut into small flakes The normal charge . .

of a 1 2 bore cartri d ge is only 26 gra ins

-
.

In France the manufacture of spor t ing p o w ders form s part of t he S t ate

mon o p o ly of explosives The foll o w ing Table gives t he c ompo s i t i o n of the
.

p o w ders made

P o u d re

N it r o -cot t on

B ar i t rat
u m ni e

P ta
o iu m n itra te
ss

A m b i h mat
. c ro e

P t
o iu m b i h r o m a t
a ss c e

B in d in g m a t e ia l r
Mo is t ur e

r
P ic e

The following d e tails o f manufac ture are gi ven in P e t S 1 9 1 2 x v i pp . .

, .
, .

9 9 1 00 a n d Ve n n in e t Cheneau P o u dr e s c l E a p lo s i/ s pp 4 3 4 4 3
'
—
, , , ,
. 4

Po u d re S The ni t ro c ot t on c onsi s ts of 3 7 par t s of G P a n d 28 o f C P

.
-
, ,.

The ma t erial s are incorp orate d under light e d ge runners d rie d a n d par t ly ,

gelatini ze d wi t h 3 5 per cent of ether alc o hol The dough which is no t ver y .
-
.
,

c o herent is forme d int o grains by simply passing i t thr o ugh a s ie v e The

, .

grain s are d rie d sif t ed hardene d if necessary w ith ether al c ohol a n d again
, ,
-

d rie d and sif te d 2

.

P oudre J A mixture of ni t ro c ottons is u sed c on ta i ning 30 per c en t

.
—
.

soluble in e t her alc o h o l Thi s is dehydrate d w i t h al c o h o l a n d mixe d w i t h

-
.

t he bi c hro mate s in an inc o rp ora t or Then 14 per cen t of e t her al c ohol . .

-

(5 0 B s p g r 0 760 ) is incorp o rate d in and t he re s ul t ing d o ugh is p r essed

°
. .
, ,

1
J . Soc . C he m . I nd
1 90 4 , p 29 8
.
, . .

2 Fo r ea r lier h
m e t o d s ee P a t S , 1 8 90 . .
, v o l. iii .
, p . 13 .
 FAS T BU RNI NG -
S MOK E LE SS P OWD ERS 3 29

into strips whic h are cut into cubes These are t hen converted into .

grains of irregular shape in a granulator c onsisting o f grooved c ylin ders ,

and then the po w der i s drummed sif ted and dried w ith col d air The , .

finest siftin gs are used for pistols and practice ammunition The presen c e .

of bichromates makes the p ow der sensitive and unpleasant t o manu

facture It is c heaper than P oudr e M The gravi metric density i s 0 65 to
. .
-

0 70
-
.

P oudre M The nitro c otton used has a solubili ty of only 1 5 to 20 per

.
-

cent After drying to 5 per cent moisture it i s gelatinized with 50 per cent
. . .

of ether alcohol o f 56 B T hi s ai ded by the camphor causes a superfi cial

-
°
.
, ,

gelat ini zation and coats the nitrates The mass i s ground under edge runners .

weighing 500 kg with the addi tion of water and alcohol c oloured ye llow with
.

auramine Then it i s granulated and d rummed During the latter process

. .

the grains are spraye d wi th ether alcohol c ontaini ng 1 per cent of c ollo di o n -
.

c otton and 1 to 2 per cent of camphor whi ch causes a fur ther gelati ni zation .
,

of the surface The powder i s then dri ed and r e drummed several times
.
-
,

if necessary until the re qui red balli stics are obtained It i s sif t ed and only
, .

the grain s between 1 4 and 0 65 mm are retained There are about 3 500 - -
. .

of these to a gramme The gravi met ri c den s ity is 0 465 to 0 48 5 Thi s i s

. .

the m ost u sed of the French sp orting p owders .

P oudre T G un c otton C P 1 i s c ompletely gelatini zed wi th acetone 2 per

.
-

cent of saltpetre being added The dough i s pressed into strip s 1 5 mm

. . .

t hi ck whi ch are then rolled down to 0 1 5 mm and cut in to small squares

,
-
.

of 1 5 m m side The powder i s then steeped in water and d ried li ke P ou dre

-
. .

BF and finally drummed with a little gum and graphi te to make it more
,

progressive There are about 400 fi a ke s to the gramme and the gravi metric
.
,

density is 0 55 to 0 5 8 This p owder is supe ri or to the other Fren c h sporting

- -
.

powders but m ore exp ensive .

The follo wi ng are the normal charges of a 1 6 bore-

gun :

P o w de r C h ar ge
Bl ac k 45 g r a mm e s .

J 26
M 2 1
T 1 9 -

Dissatisfacti o n has been expressed with regar d to these Fren c h sp o rting

powders a n d i n 1 9 0 8 the Minister of l Va r instructed the Commi t t ee o f t he
,

servi c e of P oudres e t Sa lp é tr e s to compare them wi t h foreign p o w ders .

Comparative e x pe ri ments were c arried ou t with Po u dre T Sporting Balli s t i t e ,

and the German c ondensed pow der Mu ll e r ite and i t w a s a d mi t te d t ha t t he ,

re sults from the French powder w ere m o re i rregular The s ales o f P ou dre T .

am ounte d to kg in 1 9 0 9 a n d in 1 9 1 0 . .
 EXP L OSIV ES

The foll o wi n g a r e s o me of the p ri n c ipal German shot g un powders :

‘

po w ders .
Ro t t w e il . S qua re flakes wi t h me ta lli c lus t re Charge 2 22 g (3 4 3 . .
-

grains ) .

Sa xonia S quare flakes bl ui sh green Charge 1 9 0 g (29 4 gra ins )

.
,
. . .

Mul le rite Thi n s qua r e flak e s green Charge abou t 3 5 grain s

. Con ,
. .

ta in s no inorgani c s al t s .

l Va ls r o de S mall grain s
. gre y i s h w hi t e a n d gre yi s h green mixe d
.
- -
. .

Charge 2 27 g (3 5 0 grain s ) . .

A dl er Marke Small c yli nders grey Charge 2 0 0 g (30 9 grain s )

-
.
,
. . .

1Vo lf Marke
—
Grains w hi te a n d ye llo w mi xed
.
, , .

Fa sa n (P heas a n t ) Grain s gre y ish yell o w Charge 26 5 g (40 9 grains ) .

.
,
-
. .

Tiger. Grai ns blue black No lust r e Charge 2 73 g (42 1 grain s )

,
-
. . . .

The Ameri can e x plosives in dus t ry i s largely i n t he hands of t he E I du . .

P ont de Nem our s P owder C o who make the follo w i ng

.
,

Condensed po w d ers : Inf alli ble a n d Sportin g Balli stite .

Bul k powders : Du P ont Sm okele s s E C Improve d Ne w Schul tze ,

. .
, ,

E mpire a n d L e s mo k .

Au tr ia n
s . In Aus t ria there is a S t ate mon o poly of e xpl o sives Information about .

the spor ting powders is gi v en in S S 1 9 0 9 p 4 1 3 bu t t heir quali ty ha s bee n . . .

,

decried .
1

Req uir e m nts

e .
The requir ements o f a good shot gun po w der are : (a ) That it shall b e -

reliable a nd c ons ta n t in it s quali t ies t hi s is a s imp or t an t as in t he case of

o t her gun po w d ers a n d some w ha t more di fficul t t o a tta i n ;
. grea t care in
manuf a c t ure and t horough blendi ng are necessa ry (b ) It sh o ul d b urn clea nl y .
,

lea v ing li t t le re s idue in t he gun and w hat residue t here is shoul d be alk a line
,

in reac t ion and easily rem oved (0 ) I t shoul d give good resul t s even when
.
,

loaded into chea p cartridge cases wi th in di fferen t wad di ng and light sho t ,

charges (d ) I t shoul d be quick in ignition : a delay of a fe w t housan d t h s

.

o f a s econ d in t he tim e t hat elapses bet w een p ul lin g t he t ri gger a n d t he s ho t

lea v ing t he muzzle makes a c on siderable di ff erence in the a c c u r acy of t he

sho o t ing ; sm o kele s s p o w ders burn considerably faster t han black (6) I t .

s hould not be grea t ly a ff ec t e d b y e x posu r e t o ho t or m ois t air

(f) I t shoul d .

o c c upy about t he same sp ace as t he e qui valen t charge of blac k p o w der in

t he manuf ac t ur e of c art ri dge s the charge s are measured a n d n o t w eighed ,

and if the po w der be very dense t here is c on s iderably great e r danger of a n ,

ex t ra large c harge being in t rodu ced accidenta lly .

To t e s t s h ot g u n p o w ders t hey are loaded into car tri d ge s t he bal li s t i c s

-
,

of w hi c h are then mea s ured The vel o ci t y of t he shot is de t e rmined usua lly
.

over a range o f 20 yar d s from t he mu zzle by mean s o f an elec t ric chro n o g raph .

One o f t he c urren t s pa s ses t h rough a wire before t he mu zzle of t he s t an dard

gun a n d t he o t her through a wi r e sc reen or a s pring c o n t a c t on t he back
,

1
S ee S S . .
, 1 9 10 ,
p . 3 20 .
 FAST -
B U RNI NG S MOKEL ESS P OWD ERS 33 1

R o tt w e il Ad le r -
Mar ke

Sax o nia W o lf Mar k e

-

VVa ls r o d e Fa s a n
FI G . 65
.
G r ma n
e Smo ke le s s Sh o t G u n P o w d e
~
rs h o rn r
(T e , S S
. .
, 1 90 7, p .
332 E X P L OSIVES

of an i ro n t a rge t A n a d v an ta ge of t he sp ring contac t i s t hat t he second

.

c u rr en t ca n no t b e in t e rrupte d prema t ure ly by one or t w o shot going ahead

of t he bulk of t he c harge .

The p r e ss u res a re meas u red by fir ing cartridge s in a spe c ial gun of soli d
c ons t r uc t i on A t 1 in ch a n d 25 inches or 6 inches from t h e bre a c h there
.

a re plugs pa ssin g t hrough t he wall of t he g u n ; on t hese plugs are placed s

c r ushers w hi c h a re held down b v sc r e w s In E ngland le a d crushers are .

gene r ally used for tes t ing shot gun po w ders instea d of t he c opper c r ushers -

u s e d w i t h slo w bur ni ng powder a s t hey are foun d to give m ore sa t isfacto ry

-
s
,

resul t s wi t h t he very va ri able p r e ssur e s o b ta ined The subjec t of pressure .

meas u remen t s wi l l be deal t wi th m ore ful ly in Chapte r x xi x .

The pa t t e rn of the shot i s de t e rmi ned by firing car t ri d ges from a gun
of s t a ndar d choke at a whi te was he d iron plat e genera lly a t a range of 40 -

v a r ds Th e marks of the shot shoul d be fairly evenly di stribute d and about

. .

t w o t hi rds of t he shot shoul d b e wi t h in a c ircle of 30 inche s diam ete r

- 1
.

The pene t r ation of shot c an be mea su r ed by fi ring under s ta ndard con di tions
a t a n u mbe r of pi e ces of c ardboard placed one behi nd the o t her and counti n g

t he num ber of pellets that penetrate t he di fferen t cards .

The r ecoil of t he sta ndard gun c a n also b e mea sured and form s a u seful
check on t he o t her dete rmi nati ons especially the veloci t y In Fig 66 is , . .

shown t he F ield proo f g un for ta kin g simul ta neously t he recoil and the press ur es
a t 1 in ch and 6 inche s from t he breech The velocity a n d pattern can also .

b e t a ken a t t he mme time The gun w eighs 50 lb and is suspended 5 feet

.

belo w i t s suppo r ts ; it i s fired b y means of a pneum a t ic b ul b in order not

to di s t urb t he gun Wi t h t hi s g u n num erou s investiga t ion s have b e en carried
.

ou t on behalf of t he F ield newspaper

The cart ridges for the 1 2 bore a n d most of t he oth er shot guns are 24inches
- -

long T he ba e and th e powder usuall y o c c upy j us t 1 in c h so t ha t t he hole

.
s
,

bo r e d t o a d mi t t he powder gases t o t he base o f t he pr e ssure plug is bisec te d

by t he fi rs t wad Over t he powder i s placed a t hi n card w a d t hen a gre a sed
. .
.

fel t w a d t hen another thi n card t hen t he c harge of sh o t a nd finally a t hicker

, , .

ca r d w a d The spac e above t he sho t w a d should be abou t 1 inch t his is

.

tu r ne d over inwards by means of a sp e cial m a c hine so as t o hold t he shot

w a d in place and a p ull of about 50 lb shoul d b e require d to e xtrac t it The . .

cart ri dges a re usually ad j u s t ed to give a veloci t y over t he 20 yards range

of 1 0 5 0 to 1 0 80 fee t pe r second wi t h a cham ber pressu r e of 3 to 3 3 t on s per .

s q u a r e inch If t he veloci t y be higher t han t hi s t he sho t are d eforme d and

.

s ca t t e r e d to o much if lower t he killi ng p o w er of t he pelle t s i s reduce d ; i t is

, ,

h o w ever b e t t e r for t he veloci t y to fall bel o w t hese li mi ts t han to ri s e above

,

t hem a s s hooting is genera lly at shor t ranges If t he pre s s ure be t oo low

,
.

a n ly in g
pa t t n V n n in t C h nea u
1
F p c ia
or l pp lia n
s f
e a ces or a P ud et s er s ar e e e es , o r es

E p lo if p 1 49 a l 0 Ma re ts c h S S 1 9 1 5 p 261
x s s , .
, so .
, . .
, , . .
 F i e ld P ro o f G un

ro m
F A r ms a nd E x p lo s i ves , 1 9 1 1 , p . 5 Sc o tt )
333
 E XP L OSIVE S

t he pa t t erns a r e b a d i f to o hi gh t he gun may b e spoilt or even b urst The

, .

r ecoil of t he spor t sman s g un shoul d b e abou t 1 6 feet per second whereas

’

t ha t of an express rifl e i s u suall y about 1 7 fee t per second and that of a mi lita ry ,

rifle w hi ch i s fire d much more rap idl y is 1 0 feet per second 1

The French
, .

smokeless po w ders onl y gi v e a veloci t y of 755 feet per second over a range of
1 5 me t re s ya rds ) in a 1 6 bore g u n wi th the sta ndard lo a ding
-
.

The pre ssur e i s inc r e a sed by u ing felt wa ds th at a re harder or sli ghtly
s

larger in di a me t er or b y having a longer or harder turnover The velocity .

is a l o incre a se d sli gh t ly by t he same alte r a t ions

s The opposite changes o f .
,

c ourse produce the opp osite eff ect s The balli stic s are a ff ecte d also by the
, .

s t re ng t h and natur e of t he cap in the cartridge case If by adj ustin g these .

elemen ts i t is no t possible to produce t he desired resul t i t is nece ssa ry to

alte r t he w eight of powder or shot or both .

The propell an t for a t r ench ho wi tzer has t o ful fil muc h t he same

re qui remen t s a s that for a shot gun : a heavy proj ectile has t o be given
-

a c omparati v el y low m uz zle velocit y and the gu n canno t wi t hsta nd a hi gh

-

p ressure The difficul t y i s to ob t a in consta nt balli stic s wi t h thi s lo w pressure

.

i n t he cham ber It is overcome b y using p owders of the same types as those

.

for shot guns -

.

Bla nk p owders are u sed for firin g time and other signals for man oeuvres ,

a n d di spla y s such as fe ux de j o ie : in all ca ses in fact w here it i s required

, , ,

t o make the noise of fi rin g w i t hout ej ecti ng a proj ectile D iffic ul ty is caused .

b y t he fac t t hat there is no hea vy proj ectile to off er resista nce to the exp ansion
of t he po w der gases : conse quen t ly as soon as the envelope conta ining the
po w der is burst the p r essure fall s a lmost to nothing Wi th bla c k po w der thi s .

d o es not mat te r v e r v much a s the rate of burni ng is not affected to the same
e xte n t b y the p ressure ; gunpo w der can be used indeed for thi s p u rpose
whi ch is not g o od enough for ordinary ca r t ri dges The rate of b ur ni ng of .

ni tro powder on t h e o t her hand is grea t ly affecte d by the pre s sure : there
-
, ,

i danger therefore if t he en v elope offer a li ttle too much resistance or the

s

p rimer be too s t rong t hat danger o us p ress u res m ay be set up in the g u n

,

a n d i f t he res i t a nce or the igni t ion b e t oo weak the report will b e i nsu ffi ciently
s

lou d.

As in t he c a se of sh o t gun p o w ders the rapidi ty of bur ning i s attained

-

ei t her b y u ing a pa rt iall y ge lat ini zed materi al or a c omplete ly gela t in i zed
s
,

one in a fi ne sta t e of di v ision In the B ritish service t he small arm blank

.
-

ca rt ridge s ha v e a charge of 20 grai ns of c or di te size 20 SC SC sta nds for . .

s li ce d and t his po w der i s made by passin g strands of cor di te about 0 20

.
‘
-

in c hes i n di ame t e r t hrough a m achi ne in whi ch it is cu t transversely by ,

r a pidl y rota t ing knives in t o small di s c s havin g a thic kne s s of about 0 0 0 55

inch For ordn ance ho w e v er bla c k po w der i s s t ill used generally In France
. .

1
A r ms a nd E r p lo si w s , 1 90 8 , p . 8 .
 FAST B U RNING S MOK E L E SS
-
P OW D E RS 33 5

a specia l p owder is manufactured known a s P o u dre EF w h ich is made o f

'

nitro cotton and bin ng material in much the same way as oudre
-
di P M 1
In .

Spain a nitro cell ul ose flake powder i s u sed for small arm blank amm u ni tion
- 2 -
.

In order to o ff er greater resistance to the p ow d er gases the cartridge is

often provided wi th a mock shot made of hollow wood or other suitable
material which breaks up at the muzzle of the gun A disadvantage of these .

i s that they are liable to lead to accidents men being shot at short range ,

during man oeuvres In Germany a large proportion of the wounds thus

.

caused formerly proved to be fatal because the patients developed tetanus .

The source of this di sease was however traced to the felt wads used under
, ,

the mock shot T hi s danger is no w guarded aga inst by sterili zing the felt
.

wads .
3

Blank p owder for rifles is ca lled in Germany G e w e h r p la t a tr o n e np ul v e r

( Gew . P l
. B B ) and t hat
, for machine guns M a s c h in e n g e w e h rp la t zp a tr o n e n

p ul ver (M Gew Pl P B ) The latter i s more vi olent in order to give sufficient

. . . .

recoil to work the Maxi m gun and with the same obj ect a piece is fi xed,

to the m uzzle with a narrower b ore In order to p revent accidents an appli ance
.

i s sometimes fi xed on to the muzzle to break up the mock bullet and deflec t
i t In Austria blank cartridges are called E x e r z ierp a tr o ne n
. .

1 2
P . at S .
, 1 6, 1 9 1 2, p 10 0 .
. S S . .
, 1 90 8 , p . 28 4.
3 E N um an
. e n , S S , 1 9 15, p
. . . 220 .
 C H AP TE R XX I V
SOL V ENTS

So l ve n t s ava il ab le E t he r l h l N t u r o f c o ll o id
: -
a co o Ma nu fa c t ure o f a c e
: a e s :

t o ne P e rman ga nate t s t I mp u it i e A t o n fr o m t ar ch r Ace t o ne fr o m

es ce e s

a t y le n : Re v r y o f o lve n t
ce e co e Ac t o ne r e c o ve ry
s V o la t ilit y o f ni t ro
s : e :

g l y rin ece V a p ur e p lo io n
: T o x i c it y o f v a p o u s
o x s s : r

IN the p owders fi rst in troduced Sch ult ze E C P ou dre B the sol v ent used
, , . .
, ,

was a mi xt u re of ether and alc ohol which had bee n employed in makin g ,

collo di on solutions for many years W h en the E ngli sh Go v ernment in tro

.

d u c e d c or di te in 1 8 8 8 they adop t ed a solvent w hich had been but li ttle used

, ,

previou sly excep t in the laboratory namely acetone Thi s poss e sse s the , , .

ad v antage that it can di ssolve g u n cotton even of the hi ghest deg r ee of -

ni t ration .

In t he lac quer and cell uloid industries various s ol v ent s for nitro cellul ose -

are u s ed i n order to obta in di ff erent specifi c e ff ects Amyl acetate especiall y .

-

i s much employed in the preparation of lac quers It s grea t value lies in the .

fa c t t hat it boil s at a high te mperat u re ; c onsequen t ly the sur face does no t

become c ooled by rapid evap oration and so condense wate r from t he ai r , .

Moreover from a mix t ur e of amyl aceta te and w ate r the la t te r evaporate s

,
-

prop ortionall y m uch faste r than the former Consequen t ly the solution of .

ni t ro cellul ose graduall y set s to a clear solid fil m as the amyl aceta te e v a p o

-
,
-

rate s wherea s if onl y very volatil e solvents such a s ether and al c ohol a re
,

used wate r a c cum ulates more and m ore until it precipita tes the ni t ro cellulose
, ,
-

in an o paque form .

In the manufact ure of mil itary and rifle powders there a re no t many
di ff erent sol v ents used If g un cotton wi th some 1 3 per cent of nitrogen
.
-
.

be t h e base either a c etone or ethyl aceta te is u sed gener all y the fo rmer
,
-
,
.

”
If a soluble ni tro cotton be the base e t her alcohol i s usua lly empl o yed
. -
,
-
.

In P oudr e B amyl alcohol w a s formerly add e d for a p ur p ose some w ha t s im la r

-

to t hat for w hi ch amyl acetate is used in lac quers For sport in g sh o t gun
-
.
-

p o wders a somewhat wider range o f solvents is in use a n d they a re of te n ,

mixed in order to produce certa in spec ific effects .

The subj ect of the solubili ties of nitro celluloses in the variou s simple and -

mixed solven t s has never been thoroughly investigated al t hough it is of ,

 S OLV ENTS
considerable practical and theoretical importance De Mosenthal gave a .

long list of solvents that have been mentioned in patent s p e cifi c a tio n s but
1
,

in the absence of information as to the sort of nitro cotton or the conditions -

un der which it is dissolved the list i s not of great value ,

.

Gun cotton c ontaining about 1 3 per cent nitrogen only dissolves to a

-
.

small extent in ether alcohol but is totally dissolved or gelatinized by acetone

-

and other ketones by aldehydes such as benzaldehy de and furfurol by esters

, ,

such as ethyl acetate (acetic ether ) by acid anhydrides such as acetic a nh y

—
,

d r ide and by some nitro c o mpounds such as nitro toluene

, On the other - -
.

hand it is not dissolved by nitro benzene nitro p henol or organic acids

,
-
,
-
,

such as acetic or formic E x cepting nitro toluene all the above solvents .
-

for gun cotton c ontain the group : CO c onnected wi th two other radicles other
-

than hydroxyl OH ,
—
;

Soluble nitro celluloses are di stinguished from gun cotton by the fact
- -
Eth a n-0 0 11 0 1
that they are soluble in a mixture of ether and alcohol : of any ether and
any alcohol ; whereas they are practically insoluble in the ether alone and
onl y di ssolve with diffi culty in absolute alcohol From determinations of .

the vi scosity of mixtures of various alcohols and ethers F Baker finds 2

.

evidence of the formation of compound molecules such as Os O O H 0 , 4 10 ,

and it i s these apparently which have the property of dissolving the nitro
cellulose but Bingham has pointed out that the evidence is not conclusive 3
.

An alternative theory i s that the ether only plays a passive part in causing
the associated molecules of alcohol (R OH )n to split up into simple molecules .

R OH which latter dissolve the substance

.
, But this theory is inconsistent .

with some of the facts other li quids which are known not to combine with
the alcohol such as benzene cannot be substituted for ether ; then again
, ,

the most associated alcohols methyl and ethyl alcohols have the greatest ,
-
,

solvent p owers when mi x ed with ether also the solvent p ower of a mi x ture
of ether and alcohol is increased by reduction of temperature 4
All these .

facts are c onsistent with the theory that it is the c ompound molec ul es of ether
alcohol that have the solvent power but not that this property resides in ,

the unassociated molecules of alcohol The solubili ty in various mi x tures .

has been investigated by Stepanow who found that the ma ximum solubility
5
,

i s obtained when the prop ortion of ether to alcohol is 3 2 t e when the two , . .

li quids are mi xed in about equi molecular proportions The addi tion of -
.

solvents such a s acetone or ethyl acetate increases the solubility in ether —

,

alcohol but indi fferent substances such as benzene toluene p yrid ine phenol
, , , , ,

1 J . S o c. C h em . I nd .
, 1 90 4, p 29 5 . .
2
J . C h em S o c . .
,
1 0 1 , 1 9 1 2, p . 1 40 9 .

3 J . C h em . S oc .
, 10 3 , 1 9 1 3 , 9 64 .

4
W . Ma cnab s uc ceeded in v h ighly n it rat ed in s o lub le
d is s o l in g g un -
co tt o n in
e t h e r a lc h o l
-
o by e r du
c in g t h e t e mpe ra t u r e t o t ha t o f s o lid carb o n d io x id e .

5
S S . .
, 1 90 7, p 4 3 . .

V OL . I .
 3 38 E X P L OSI VE S

chl o rofo r m di m inish the solubili ty the dim inution be ing proport ional to t he ,

quanti ty added Other substa nces such a s wate r and acids also a ffe c t t he
.
, ,

solubili ty but not proportionall y

, .

Soluble ni tro cellulose or c ollodi on c otton is also di ssolved by ni tro glycerine

- -

acetic aci d etc In the cellul oid industry use is made of the solvent po w er
, .

of camphor and there are a num ber of other substances solid at the ordi nary
, ,

te mperatur e which have the same property : the dissolution i s grea t ly pro
,

mote d by the addi tion of alcohol It has been sta te d by B e r n a do u that a t .

a lo w temperatur e nitro cell ul ose is di ssolved by ether alone -

.

L u nge and Bebie found that a ni tro c otton c ontain i ng about 1 1 per cent
1 -
.

N was soluble in absolute alcohol but insoluble in 9 5 per cent alcohol E nn ea , . .

ni tro c ellul ose (1 2 per cent N ) o nl y di ssolved to the ex tent of 70 per cent
-
. .

in absolute alcohol w hi lst a deka ni tro cell ul ose (1 2 75 per cent N ) although
,
- - -
.
,

c omplete l y soluble in ether a lcohol onl y di ssolved i n absolute alcohol t o the -

,

extent of 1 3 per cent W ith a nitro cotton contain ing 1 1 5 per cent N
0
.
-
.

the followi ng resu lts were obta ined wi th the ether and alcohol in varyin g
proportions
E th e r Alc o h o l E th e r Alc o h o l
1 3 v r a d ily
D is s o l es e

1 6 Le r ad il 9 3 per
ss e y , ce nt . a ft re 6 1 D is s o l ve rs e a d ily .

t rea t in g t w ice .

9 1 Less r ea d ily 9 5 p e r ce nt
, .

1 12 Mo re r d il y 9 6 p ea , er ce n t a ft r
. e 12 1 92 1 p e r c e n t d is o lved . s .

t rea t in g o n ce .

1 24 9 56 pe ce n t r . 27 1

Similar exp eriment s have been carried out by A Ma tte o s ch a t wi t h a .

n itro cellulose o f me di um solubil ity conta inin g per cent ni trogen ?

-
12 9 5 .

The solvents used c onsiste d of pure ether and pure alcohol c ont a ini ng varyi ng
percentages of water mixed in diff erent propor tions To p revent surface .

gelat ini za tion of the nitro cellulose the alcohol w a s added fi rst and then the -

ether The follo wi ng were the solubil ities foun d

.

St n g t h f Al h l b y V l m re o co o o u e

99 5% -
9 5 96 90 %
32 4 -

28 7 -

- -
40 5 53 9
25 o

I t will be seen that in mixtures rich in ether the solubili ty is inc rea sed
by the addi t i o n of a moderate proportion of w a ter T Ch a n de lo n has foun d . .

that the ad di tion of water also di minishes the viscosity o f the solution of
ni tro cellulose in ether alcohol and that it makes n o d iff erence w hether wet
- -
,

2
1
Ang .
, 1 90 1 , p . 53 7. S S . .
,
1 9 1 4, p . 10 5 .
 SOL VENTS

n itro cellulose be dissolve d in water free s o lvent o r dr y nitro ce llulose in

- -
,
-

ether alcohol contain ing water pr o v ided that the fina l composition of the
-
,

solution be the same 1

.

The di ssolution of a coll oidal substance such as nitro cell ul ose di ffers Na t re of ,
-
,
u
c llo ids o
fundamentally from that of crystalline substances such as sugars or the ,
.

ordi nary mineral salts Strictly speaki ng colloids do not form solutions
.
,
”
but wi th suitable liquids they form what are termed sols whi ch are inter ,

medi ate between solutions o n the one hand and suspensions and emulsions
on the other The latter consist of small particles of soli d or li qui d respect
.

iv ely suspen ded in a liquid medium the par ticles being of such size that they ,

can be seen under m o derate magnification In a true solution the di ssolved .

substance consists of individual molecules floating about in the solvent .

No sharp line of distinction can be drawn between sols and solutions on the
one h and and emulsions and suspensions on the other A molecul e has a .

diameter of abou t a ten milli onth of a millimetre in the case of the simplest
c omp ounds up to rather more than a mi lli onth in the case of very complex
substances The extreme limi t o f visibility through a microscope i s about
.

a ten thousandth of a m illimetre The si ze of the di sperse particles in a

-
.

sol may be considered to be comprised between the li mits of a tho usandth

to a m illi onth o f a millimetre If not smaller than about 5 milli onths they.

can be detected as bright spots when il luminated by a p owerful beam of light

against a dark ground in the ultra microscope On e of the properties of -
.

particles of this size is that they show a continuous oscil lating movement ,

kn own as the Browni an movement when observed un der the microscope or ,

ul tra microscope Colloid substances are divided into two classes suspens
-
. ,

c ids and emul soids accor di ng as the i r sols resemble suspensions and emul sions
,

respecti vely Colloidal metal sols belong to the former class ; si licic acid
. ,

gelatine and other organic colloids in cludi ng nitro ce llu lose belong to the ,
—

emulsoid c lass W hen a colloid of the latter class is immersed in a suitab le

.

li quid it swell s up Thus hide substance when soaked in water swells up

.

wi thou t passing into the li qui d phase and in di a rubber behaves similarly ,
-

in ether Gelatine swells up in water in a similar manner but if the mi x ture

.
,
”
be heated a sol i s obtained which on c ooling sets again to a gel Un v u l .

c a nize d rubber i n chl oroform or benzene s w ell s up and at the same time forms

a sol a n d nitro cellul oses behave similarly with solvents W hen a co lloid
,
-
.

swells there is always evolution of heat and the vo lume is always small er
than the combined volume of the colloid and the li quid before the swelli ng
’
took place From this it may be deduce d a c cor di ng to le C h a te lie r s theorem
. ,

that heat must hinder swe lling whilst cold and pressure fav o ur it There i s .

a considerable rise of temperature when acetone or ether alcohol is a dde d to -

gun cot ton but only a slight rise w ith alcoh o l alone and none with ether It
-
,
.

1 B u ll . Soc . chi m B e lg
. .
, 1 9 1 2, no . 1 1, S S. .
, 1 9 1 4, p . 1 9 4.
 E X P L OSIVE S

is s upp o se d tha t t he s o ] o f an em ul s oid c on s i s ts of t w o li qui d pha s es di ff e r ing

from one another c onsiderabl y in compositi on b u t as t he t e mpe r a t u r e is r ai sed .

t he c omposi t i o ns o f t he t w o phase s appro a c h one another as is t he c a s e wi t h .

pa rt iall y mi scible li qui ds Many gels when exa mi ned un der the mic r osco p e
.

sh o w a cell u lar or webbe d structure whence i t i s c onclu d ed t hat t hey al o

,
s

c onsis t of tw o phases but thi s struc ture has onl y b ee n observ ed in gels ob ta ined
,

by c oagul a t ing sols by hea t or t he a ddi tion of some other subs ta nce When .

t he gels a re p r epared by c ooli ng the gel or evaporating o fl t he solvent t hi s ‘

s t ruc t ur e i s not ob served and it is wi t h such gels as t hese t hat w e a re con

,

cerne d in the c ase of smokeless powders and blas t ing gela t ine Wh en a gel .

i s subj ec t ed to pressure un der such condi tions that the solvent alone can escap e ,

some of the solvent escapes the amoun t dependi ng upon t he p r es sur e appli ed
,

and t he comp osi t ion of the gel the larger the qu antity of solvent p re sen t the
more ea s y it is to ex press part of it The last portion of solven t is however
.

very diffic ul t t o remove by p ressure or even by hea t and t hi s diffic ulty i s ,

in c rease d by t he fac t that di ff usion i s very slo w in a stiff and c once nt r ated
gel although in a sol conta inin g much solvent i t is almost as r apid as in the
,

pure li qui d .

Acetone is made by the dr y di s t illation of aceta te of lime w hich in tur n

t
o f ac e o ne.
,

i s a product of the dry distill ation of w o od Bee ch birch and t he American .

,
.

maple are the trees most c oncerned as t hey yield compara t ivel y large quan
,

t i t ies of a c e t ic acid on di stillation Conif erous trees t he fir and p ine on the

.
, ,

other han d yi eld li ttle acetic acid ; t he most valuable product from t heir
di stil la t ion is t u rpentin e E ven from the most suitable w o o ds t he yield of
.

acetone is small o nl y 8 to 1 0 5 parts of aceta te of lime of 8 0 per cent strengt h .

are ob t aine d from 1 00 of dr y wood and t hi s in t urn onl y yields abou t 20

,

per cent of acetone Moreover fresh felled bee ch or maple c onta i ns a b out
. .
,

40 per cent of m ois t ure

. Consequen t ly it re quir es from 8 0 to 1 00 t o ns of
.

wood t o pro d u c e 1 t o n of acetone and the man u facture is dependent on t he

,

supply of very large quanti t ies of wood Atte mpts have been made to m anu .

fac t ure aceta te of lim e and other products by the distil la t ion of s awdust ,

waste w ood and other w oody mate rials but m ost of these underta kin gs have ,

hi ther t o proved un rem u nerative The charc oal obta ined from t hes e was te
.

ma te rials i s genera lly of li ttle value and the yield of acetate and w ood ,

spi ri t is c onsiderably less than from good new wood .

Grignon the residuum left after p re ssin g the oil from olives is no w
, ,

di s t illed on a large scale in Spain It yields about 4 per cent of a ceta t e of

. .

lime and 1 2 per c en t of crude w ood spi ri t

-
O t her w aste produc t s consis t ing
.

principall y of cell ul ose a n d li gni n might b e utili ze d s imilarly ; co ffee husks ,

for instance and t he wood from which ta nnin and dye e x t r ac ts have been
,

made such as quebracho c hips In course of t ime t hese m a te rials w ill no

, .

doubt be u t ilize d but onl y where very large suppli es o f them a re a vaila ble
, .
 SOL VE NT S 3 41

The first ne c essity of a wo o d di sti llation plant i s a plentiful supply of wood ,

the sec on d i s a ready market for the charc o al As a rule a plant will not be .

remunerative u nl ess the selling price of the charcoal c overs the c ost of the
,

wood used 1
. The value of the b y products acetate woo d spirit and tar -
, , ,

then o nly has to pr o vide the cost of working interest and profit , .

Charc oal although it weighs only about one third as mu c h as the original
,
-

wood occupies nearly as much space More o ver it i s de c ide dly brit t le and
, .
, ,

if it has to be transported very far by road or rail a large proportion of it i s ,

converted into p owder which has a c omparatively small value Therefore

, .

a wood dist illation p lant should be situated where there i s a plentiful supply
of suitable wood a ready market for the charc oal a n d good means of com
, ,

mu ni ca tio n . The b y products acetate cru d e wood spiri t and tar are c om
-
, , ,

p a r a tiv e ly light and can be transported over considerable di stances to a central

chemical factory to be worked up .

These con di tions are present in many parts of In di a Nevertheless char .

c oal is still produced there in small kiln s and the valuable b y pro d ucts are -

allowed to escape The reason i s that tech ni cal kn owle dge is defi c ient and
.
,

capital i s n o t available through w ant of ente rprise Most of the a c etate of .

li me and acetone are manufactured in the U nited States but there are also
2
,

large plants for their production in Hun gary Sweden Russia and Canada , , , .

By the destru c tive di still ation of wood three di ff erent classes of pro d ucts
are obtained solid liqui d and gaseous The soli d charc oal rem a ins i n
,
.
, ,

the ki ln or oven the li qui d crude pyr o ligneous acid is recovered from the
, ,

mi x ture of gas and v apour by means of a sui table c ondenser and the gases
pass on and may be used either for heating or to drive a gas engine but a ,
-
,

further quantity of methyl alcohol and acetic acid can first be recovere d from
-

them by scrubbing with water in a tower By di still ation and treatment .

'

with milk of lime the crude pyr oligneous acid is further separate d into tar ,

acetate of lime and commercial wood spirit .

The acetate of li me is not as a rule worked up further at the carbonization

works but i s sent to a chemical factory where large quantitie s are collected
,

and w o rked up into acetone acetic aci d and various acetates and deri v atives
, ,

of aceti c aci d There are tw o varieties of c ommer c ial acetate of lime bro w n
.
,

a n d grey ,
whic h di ffer from one another in that grey acetate has had the
tar removed as far as practicable and the brown has not Brown acetate , .

i s not ma d e now on a very large scale as it gives very b a d yiel d s of acetone ,

and a c etic acid Grey acetate generally c ontains 8 0 to 8 2 per cent o f calcium
. .

ace tate a s determined by analysis and 4 to 7 per cent o f w ater the remain der , .
,

being ma d e up of various impuri ties Of the 8 0 to 8 2 per cent ho w ever . .

, ,

sever a l per cent c on s ist of formate propi onate a n d salts of o ther organic a c i ds
.
, .

1
K lar H l k h l n g e c n d d p 0 2
, o zr e r o u ,
s o c .
, . .

F t ti t i orJ Ss a C h m I nd
s 1 9 14 p 3 4 5
cs s ee . o c. e . .
, , . .
 E XP L O S I VE S
The c onversion int o acet o ne i s eff ecte d by s imply heating the acetate a t
a te mperature of abou t 3 0 0 C w hen t he fo llo wi ng rea c t ion t ake s place
°
.
,

C a C O + CH C O CH
s 3 . bu t t he o t her organ ic c alcium sal t s
3 .

reac t in a s imilar mann er formic aci d yi elds al dehydes propi o ni c a c i d yi e fds .

me thyl e t hyl ke t one a n d diethyl ket o ne a n d t he higher hom o l o gues t he

- - -
,

c orrespon di n g hi gher ke t one s .

The di s t ill ation of the aceta t e

of li me is usuall y car r ied out in
a shallow c ircular re t ort heate d
by di rec t fire Fig 0 7 is a view . .

o f a re t or t at t he Ro yal Gun

po w der Factory l V a l t h a m ,

Abbey ; it i s provi ded wi t h a

s t irrin g arrangemen t B a nd , ,

m an h o le s A a n d C for fill ing

-

and emp t yi ng The t ubes for.

t h e gases and v a p o ru s have ro d s ‘

K t o remove a n y ob s t ruc t i o n of
, .

t ar c o ke o r du s t The charge
, .

of such a reto rt i s from 300 t o

00 lb Af te r fastenin g do w n
.

t he m an hole t he s t i r r i n g
-

mechanism i s star t e d and the

retort is grad uall y heate d up ,

care being t aken t o avoid over

hea t ing a s far as possible a s i t ,

causes the formation of ta r a nd

coke and a c orresp o n ding di
,

minu tio n of t he yiel d of acetone .

I t i s n o t pr a cticable t o d r y the
w hole of the moi s ture out o f the

Ac ta t o f
e e acetate before charging it in to
t he reto rt a s acetone begins to
,

be given o ff even at a m oderate temperature Consequently the first run .

ni ng s of the retor t consis t of w ater w i t h only a li ttle acetone The de c o m .

p o si t ion o i the aceta t e does not become active until t he tempera t ure
reaches about 3 8 0 C °
t h e bul k of t h e di s t ill ate comes over bet w een 3 80
.
°

and 400 C A t t he end of t he distilla t ion steam i s blo w n through to rem o ve

°
.

t he las t p o r t i o n o f t he di s t ill a te and t o render the resi due i n the re t or t non

,

inflammable .

A t te mp t s ha v e been made t o hea t t he re t o rt s in a ba t h o f lead in o r der

to make t he hea t ing m o re u niform and so impr o ve t he yi el d bu t t rou ble wa s ,
 SOLVEN TS 343

cau sed by the o xi dation of the lead with th e consequence that heat was lost
, ,

a n d the special obj e c t of the ba t h was not atta ine d Hea t ing in a stream .

of superheate d ste am has also been t r ied : a better yi eld i s thus obtained ,

bu t t he consumption of fuel by this process i s consi d erably greater ; more

over it i s only possible to work sif te d dust free acetate which makes i t
, ,
-
,

very expensive Another .

pro c ess that ha s been

,

t ried and aban done d w a s ,

the c onversion of the

acetic acid of the crude
pyr oli gneous acid di rectly
into acetone wi t hout the
prelimi nary formation of
acetate . Thi s was done
by passing the acid over
hea t ed baryt a or li me .

A plant was erecte d on

this principle in Woolwich
Arsenal but it di d not
,

prove successfu l and was ,

soon abandoned .The

y l e ld s b y b b l s Proc e ss w e re
F I G 68 F H M ve r P la n t f
. . th e D . D is t il lat i n
. e
’
s or ry o

very poor ; the cru d e A e t t e o f L ime c a .

acetone wa s mi xed with

muc h un changed acetic a c id which had to be rec overed a n d work e d o ver
,

aga in .

Recently an improvement has been e ff ected by heating the acetate in t hin

layers that are not in direct contact with the hot w all s of t he retort Fig 68
, . .

shows a retort on this principle made by F H Meyer of Hanover The tray s . .

, .

of acetate are placed on trolleys two of w hi ch are w heele d bo dily into t he

,

retort The latter i s heated a s uni formly as p ossible by means o f a number

.

of fires W hen the charge i s fi ni she d the trolleys are wheeled o u t and tw o
.
,

fresh ones are r u n in at once Thu s loss of heat i s avoided a n d t he di s agree

.
,

able operation o f drawing the very dusty spent lime from t he retort is mu c h
i mproved .

From the retort the vapours are le d to a con denser w hi ch mus t be s o ,

constru c te d that the tubes can easily be cleane d a s t hey are li able t o b e c o me ,

choked w i t h tar and dust The crude distillate separate s into t w o layers
.
,

the heavier of whi ch consists mostly of wate r and a ce t one wi th some me t hyl
ethyl ketone and other impurities the lighte r one of methyl e t hyl ketone
-
,
- -

and ta rry matte r with impurities such a s d u ma s in and t here i s so me w ater ,

and acetone di ssolved in it The mi x ture is pumpe d into a tank rendered

.
 al ka lin e t h ca u t i c so da a n d a l lo we d to se t t le The h ea vi er la yer is t he n
wi s .

r un o ff a n d t he lig h t er is w a hed se ve ra l times wi t h w a te r

.
s These c ollec ted .

li qu o rs a re t hen p u mpe d in t o a s t ill s u c h a s t ha t shown dia gra mma t ica lly ,

in Fig 69 . The ( s se n tia l fea t u re o f t his is t ha t pa rt of the vapour is co n

de ns e d i n t he t ubula r c o ndense r D a n d re tur ned to the co lumn C w here it , , ,

flo w s o v er a num be r of pe r fo ra t e d pla te The s .

pa s sa ge o f t he va p our t hr ou h e a c h of th e se g

pla t e s i eq ui valen t to a fres h fr a c tiona tion

s .
.

The r ema in de r of t he va pour p a s se s down t he

t u be F to t he co ndense r D
, , F r om thi s th e
, .

li qui d fl o w s t hr o u h t he stil l w a tc her H to a

g -
, ,

drum o r o t her re c eiver Co ntinuous w orkin g .

s t il ls a re ma de o n t he sa me p rincip l e .

mth s u ch a di til lin g pla nt there is no

s

diffi c ul t y in ge t ting t h e a c e t one fre e from

w a t er bu t t he re mo v al of the other i mp uri ti es
.

ca us e s c o n i de ra ble troubl e
s As the dis tilla te .

ru ns t hr o u h t he st ill w a t c her co ntinuous o h

g -
,

se r v a ti o n of t he s pe c ific gra v ity a r e ta ken

s

by mea n s o f a h v dr o mete r fl oa ti ng in the

li qu id : a ll t ha t sho w s a higher gra vi ty t ha n
8 00 i r u n in t o a se pa ra t e re ce p t a c le for i mp ure
s

a c e t one bu t i t is a fte rwards re dis t illed to t e

,

c over t he g o od a ce to ne .

Per m “ :
One o f t he p rincip a l tes ts appli ed to a ce to ne
i t he
s pe r mang a na te te s t a c co rdi ng to the
F rc 69 St ill fo . . r
s pec ifi ca ti o n of t he E n lis h Go vernm ent 1 c c
g
Ac e to n e o Al co h o L . .
r

o f a 0 1 p e r ce n t
-
so lu t i o n o f pota s s ium per
.

m a n ga na t e i s a dded to 10 0 c c o f a ce to ne and the c ha ra c te ri s ti c c olour

. .
,

o f t he pe rm a n ga na t e mu t pe rs is t for at lea st ha lf a n hour

s Only the .

middl e po r t i o n o f t he di sti lla te will s ta nd this t e st The so da a d ded to the .

c r ude a c e t o ne co m bin es w i t h a ll free a c id so tha t t h e di s tilled a c eto ne co n ,

t a ins no a c id ex ce p t a li tt le c a rbo n di oxi de The gre a ter p a rt of the a ldehyde .

is a ls o rem o v ed b v t h e so da a s i t c o nve r ts it into re sin o us bodi es which a re ,

n o t v o la t ile and co nse quently re ma in in the stil l ; t he di s ti lla te only co n

.

t a ins t r ac es o f a l de hyde .

Th e r e a re o t her impuri ti es ho w ever w hi c h p a s s o ver a nd gre a tly a ff ect

, ,

t he pe r ma ng ana t e t e s t Mo re over i t is fo un d t ha t ace to nes which pa s s the

.
, ,

t es t w i t h ca se w hen qui t e fre s h fa il a f t e r ha vi ng be e n kept s o me time The

, .

fa ll o f t he t es t is o f te n ve ry ra pid a t first but b ec omes slo wer a fte r a time , ,

bu t even aft e r v ea r s t he fa ll ma y s t ill co ntin u e The fa ll of the pe r ma ng a n

.
.

a te t es t i s gene ra ll y a cco m p a ni ed by a n a l t e ra t ion in t he co lo ur of the a c eto ne ,

 SO LV EN TS
wh ich assumes a brown c o lour in s tead of remaining colourless Such deter .

io r a te d acetone i s c onsi dered unfit for t he manufacture o f cor di te and similar

explosi v es a nd has to be redisti lled before u s e As the Engli s h Government
, .

maintains a large reserve of acetone amounting to several years consumption ,

’

this re di still ation became a seriou s mat t er not o nly on account of the actual
c ost of re di st illation but also be c ause there was a c onsi derable loss of acetone
,

d uring disti llation and in the first and last runnings

, The cause of the .

deterioration was therefo re i nvestigated and wa s f o und to be intimately

associate d with the pre s ence of basic substances such as methylamine in the
acet o ne If after the first di stillation i n the presence of so d a the ace t one is
.

di stilled again but this time w ith the a ddition o f a small e x c ess of sulphuric
,

aci d to the li qui d in the still all basic substan c es are entirely removed the
,

redi stilled acetone give s a muc h better permanganate test whi ch m oreover
-
, , ,

fa lls o ff little or not a t all even after storage for several years 1
.

Of the various amines that may be present in acetone the primary and Amines , .

secon dary amines are t hose that have the most delete rious e ff ect on the keep
ing p owers of acetone e g methyl amine ethyl amine butyl amine amyl
,
. .
-
,
—
,
-
,

amine ; dimethyl amine diethyl amine On the other hand ammonia and
-
,
-
.
,

te rt ia r y a mine s such as trimethyl am ine have little or no eff ect upon it The
'

-
.

principal amine p resent in acetone that has not been di still ed over aci d i s ,

mono methyl a mine together with some ammonia and the amoun t i s usually
-
,

between O OOO5 and 0 0 0 5 per cent Al though these quantities are small
'

.
,

they are sufficient in the presence of quantities of aldehyde of the same order
to cause a decided deterioration of the acetone Ammonia and the primary .

amines form more or less stable compounds wi th acetone which are only ,

gradually dec omposed again dur ing di still ation with the result that the amine ,

c omes over in vary ing quantities in all parts of the distill ate instead of only
i n the first runnings It i s not the formation of these compoun d s ho w ever
.
, ,

that cau ses the deterioration of the acetone but the action of the amines ,

on the traces of aldehyde and other impurities or p e r h a p s s imu lta ne o u s ac t ion ,

on these substances and acetone .

The acetate of li me c ontains a considerable proportion of calcium formate Ald h y d ,

e es

and thi s in the dry di stillation gives ri s e to al d ehydes Ace t aldehy d e i s .

probably t he principal one but there are also fo rmaldehyde propi o ni c al de

, ,

hyde and other higher members o f the series Formal dehy de rea dily c hanges
, .

int o a mixture of methyl al c oh o l and formi c a c i d during t he d r y di s t i lla t ion

-
,

and also d uring the di s tillati o n with so d a The formic a c i d of c our s e remains .
, ,

in the still a s so di um fo rma t e but the methyl alcoh o l passes over in t o t he

,
-

distillate and i s found espe c ially i n t he first runnings

, Acetal dehyde when . ,

acted upon by the alkali i s largely c onverted into al d ol and o ther high boili ng
,
-

c ondensa t ion pro du c ts and i nt o resinou s b o di es which remain in the still ,

.

S Ma r ha ll J S
1
C h m I nd
ee 1 90 4 p 645
s , . oc. e . .
, , . .
3 46 E XP L O SIV E S
P ropioni c and oth e r alde hyde s be have ve ry much i n the sam e w a y as a c e ta l de
hyde Th e de str uction of th e alde hyd e s is not co mpl e te howe ve r and con
.
, ,

se qu e ntly s ma ll trac e s a re to b e foun d in t he ace to n e e ve n afte r se ve ral

Th e p re se nce of small trac e s of al de hyde can b e de te cte d in ace ton e by

t he app lica tion of Sc hifi s re age nt Ace to n e it se lf give s a purple coloration
’
.
,

bu t if th e re b e 0 0 0 5 p e r ce nt of alde hyd e or m e thylal in it t he c olour is

.
,

di s tinctly strong e r .

Me thyl alcohol as h a s alrea d y bee n po inte d out is produc e d from t he

-
, ,

fo r ma lde ly de Th e re a r e many oth e r re acti ons by which it can b e form e d

.

fr om the con titu e nts of c rude pyrolig n e ou s acid As m e thyl alcohol has a
s .
-

boiling po int-
c onside rably hig h e r than t hat of ace to n e
,
and ha s ,

p rac ti ca ll y t h e sam e spe c ifi c gravity 0 7 9 6 it m ight b e thoug ht that t he , ,

alcohol woul d p ass ove r in t he la st runni ngs of th e di stilla tion and that its ,

p re se n ce would not a ffe ct t h e sp e cifi c gravity of t h e ac e ton e Th e r e ve rs e .

i s how e v e r t h e c ase
, ,
VVh e n t he two li qui ds a re mix e d to ge th e r th e re is
.
,

a contrac ti on an d c onse qu e ntly the mix tur e is more de nse than th e con
,

stitu e nts More ove r mi x ture s c onta ini ng much ac e ton e boil at a lowe r te m
.

e tur e than ace to n e its e lf t h e mix tur e of mini mum boil in g point conta ins
p ra -

8 65 pe r c e nt of a ce to n e and 1 3 5 p e r ce nt of m e thyl alc ohol and boils

.
,
.
-
,

at Thi s mi xtur e h a s a sp e cific g ravity of 0 79 9 7 it cannot b e se par -

a t e d into its c onstitu e nts by fractional di still ation on t h e c ontrary it be have s

much a s a simple li qui d More ove r as its boilin g p oint is so n ea r to that
.
,
-

of ace ton e t he c onstant bo ilin g mi xtur e cannot b e e ntir e ly se parate d from

t h e ac e t on e Conse qu e ntly m e thyl alcohol oc c urs m ostly in the first runnings
.
-
,

b u t i s al so p re se nt thr oughout t h e di sti ll ation It is possibl e that m e thyl .

alcohol may hav e a de le te rious e ffe c t upon t h e stabil ity of e xplosive s w ith
which i t is mix ed t hrough its li abil ity to be c om e o x idiz e d to formalde hyde
, ,

but a s th e re i s no m e thod kn own for the re ady de te rmination of t h e amoun t

of i t in ac e ton e nor any pro ce ss for s e parating it on a manufa c turing scale
,

without grea tly incre as ing t h e cost of the solve nt no particul ar atte nti on has
hi th e rt o bee n paid to t h e matte r .

Be sides the se i mpuri tie s t h e firs t run nin gs also c ontain som e substanc e s
that a r e insoluble in wate r : if thi s a c e to n e b e mi x e d with twic e its bulk of
wa t e r th e se se parate out partly Th e li quid thus obtain e d i s a c ompl e x
.

mixt u re w ith a spe cifi c gravi ty of about 0 78 and b oil ing ove r a range of 50 -
°

t o 1 1 0 i t appare ntly c ontain s various hydr o carbons satura te d and u nsa tu r

°
-

a te d and als o subs tance s such a s furan C .H .O and sylvan ( H Q Furan ‘

, S G

would b e form e d by t he dry distilla tion of t he calcium salt of pyromucic acid ,

o n e of t h e consti t u e nts of t h e crud e pyro lign e ous acid .

The e ffe ct of t h e se substa nc e s upon t he p e rmanganat e te st i s v e ry simil ar

1
P t t it J u Ph y C h m 1 8 9 9 3 3 49
e - ,
o r. s. e .
, , , .
 SO L VE NTS 3 47

to that of ald hyde but not n arly so gre a t

e ,
e of 0 2 p e r c e nt
. Th e ad di tion -
.

r e duc e s th e p e rmanganat e t e st of pur e ac e ton e from many hours to about

1 0 0 minut e s and i n t h e pr e s e nc e of basic substanc e s th e re is a furth e r slow
,

fall which howe v e r is not n e arly so rapid as in the cas e of alde hyd e s If
, , , .

0 2 p e r c e nt b e pr e s e nt th e ac e ton e b e com e s cloudy on th e addition of two

.

volum e s of wat e r Thos e impuriti e s can b e s e parat e d by a sp e cial proc e ss of

.

di st ill ation for whic h s ee P art X I I

, Th e re a r e also ch e mical re actions by
.

which th e s e substanc e s can b e de t e ct e d and e stimat e d : such as t he iodin e

t e st give n in P art X I I which e nabl e s o ne to e stimat e th e amount of th e
substanc e s to within 0 0 0 2 p e r c e nt Comm e rcial ac e ton e s usuall y c ontain .

from 0 0 2 p e r c e nt to
-
p e r c e nt ave rag e 0 0 4 p e r c e nt
. Th e re app e ars
.
, .

to b e no r e ason to think that th e s e small quantiti e s can have any appre ciabl e
e ffe ct on t h e stability of e xp losiv e s e ith e r b e n e ficial or oth e rwis e
, .

Th e pr e s e nc e of th e s e substanc e s insolubl e in wat e r is not confin e d to th e

first runnings th e re is almost as much of th e m in the last runn ings and e ve n ,

th e middl e fractions contain u suall y to 0 0 4 p e r c e nt as may b e as o e r -

.
,

ta in e d by th e app lication of t h e t e sts j ust m e ntion e d

W h e n th e main bulk of th e ac e ton e has di still e d ov e r t h e t e mp e rature .

of th e still h e ad and th e sp e cific gravity of th e distill at e comm e nc e to ris e

-

aft e r a short tim e th e t e mp e ratur e r e ach e s about 73 5 and th e sp e cific gra v ity °

and th e r e th e y r e main st e ady for som e tim e Th e di still at e now con .

sists almost e ntire ly of a mixture of wat e r and m e thyl e thyl k e ton e the - -
,

n e xt homologu e to ac e ton e in th e p roportion of 1 1 4 of wat e r to 8 8 6 of k e ton e

, .

Thi s mixtur e distils u nchange d and t h e wat e r can o nl y b e s e parat e d from it

,

by tr e atm e nt with a d e hydrating age nt such as calcium c hl oride or solid caustic

soda In th e int e rm e di at e fracti ons wh e n th e boili ng poi nt and th e gravity
.
,
-

a r e rapidly alt e ring th e distill at e contains much impurity substanc e s insolubl e

, ,

in wat e r and p e rhap s e thyl alcohol Aft e rwards wh e n th e boiling p oint

-
.
,
-

b e com e s constant th e constant boili ng mixture c om e s ove r in a stat e of

,

c onsid e rabl e purity Th e n aft e r a time th e boiling point ris e s again and
,
.
-
,

a di still at e is obtain e d which st ill s eparat e s out into two laye rs the light e r ,

of whi ch c onsists mostly of high e r k e tone s with a small proportion of wat e r

an d impuriti e s and t h e low e r larg e ly of wat e r
,
.

Me thyl e thyl k e ton e wh e n fre e d from wat e r g e latiniz e s gun cotton as

- -
, ,
-

w e ll as ac e ton e and has no bad e ffe ct upon it It would b e p ossibl e to add

,
.

a c onside rabl e prop ortion of it to ac e ton e without causin g it to fail in any

of th e usual sp e cification t e sts but it is m ore usual to s e ll it s e parat e ly for
,

d e naturing spiri t and dissolving r e sin s Th e h e avi e r ac e ton e oils a r e also .

us e d for making lac qu e rs e tc but do not command a v e ry good pric e

, .
,
.

It has b e e n discove re d by F e rnbach that starc h can b e submitt e d to a Ac t ne fr e o o

“m m
proc e ss of fe rm e ntation wh e re by i t is conve rt e d i nto a mixture of fus e l oil “

and ac e ton e and it has b ee n propos e d to c onve rt t he fus e ] oil into artificial
,
 348 EXP L OSI VES

rubbe r whilst the b y produc t ac e ton e is p urifi e d and p la c e d on the marke t

,
-
.
l

It has bee n sta t e d that from 1 0 0 parts of dry po t ato substa nce a yi e ld of 22
par t s of rubbe r and 14 of ace t on e can b e ob t a in e d .

Acetone fro m Ac e to n e can al o b e made from ac e t yle n e a nd t hi s m e th od h a s b ee n

s

sugge s t e d in Ge rman y dur ing t h e l Va r 2

If ac e tyle n e b e led into sulphuri c .

ac id of abou t 44 p e r c e nt stre n gth and t he p roduc t b e boil e d wi t h wate r .

, ,

it is conv e rte d into alde hyde 3

Th e chang e is al o e ff ec te d by pas in g t he . s s

ac e t y l e n e t hrough boil ing sulphur ic aci d of thi st re ngt h Th e re a c t ion i s s .

assi te d by the p re se nce of a li ttl e m e rc uric oxi de

s
‘
Th e ald e hyd e may th e n .

b e o xidi ze d to ace tic acid whi ch i s conv e rte d into ac e to n e by h e ating ba rium
or calcium ace tate or by passing th e vapo u r ove r hea te d barium o xide
, .

As but littl e of t h e solve nt is al lowe d to re main in t h e fini s h e d p owd e r ,

i t i s advisabl e to re cov e r as much as possibl e in ord e r t hat it may b e use d a ga in .

A consid e rabl e proportion is lost durin g t h e op e rati ons of formi ng th e dough

into c ords strips tube s or flak e s and hi t h e rto t h e re has be e n li t t l e atte mpt
, , ,

to re cov e r thi s portion as t h e di ffi cul ti e s introduce d into th e ca rryi ng out

,

of t he ope rations woul d absorb to o much of the p ro fit on th e re c ove ry It .

only from t h e drying sto ve s that re c ove ry i s atte mpte d as a rul e “ h e n .

t he solve nt is e th e r alcohol difii c ul tie s a re in troduc e d by t h e g re a t volatil i t y

-

of t h e e th e r by dr a w in g th e air away from the sto ve s t hrough c oo lin g coil s

only alcohol is re c ove re d ge n e rall y A grea te r bulk of cond e nsa t e ca n b e .

obta in e d by using re frige rate d wate r or brin e but if the te mpe ratur e of t he ,

c oil s b e re duc e d muc h be low 0 C th e re i s da nge r of th e coil s be ing choke d °

.

with ice In th e manuf ac ture of artifici al silk by Chardonn e t s p roc e ss atte mp t s

'

have bee n m a d e to re cove r th e solve nt by passin g t he air up t o we rs w h c re it ,

i s scrubbe d with a mixture of sulphuric acid and wate r or with oil T han . .

de lon p ropos e s to u se the chlorin e bromi n e or nitro de rivative s of ali phatic ,

-

or aromatic hydrocarbons for t he re c ove ry of e th e r and alcohol from air 3

.

In Spain sul phuric acid i s u se d 6

It has also bee n propo se d to comp re ss c oo l .

and re e xpand the air in a re ge n e r ative mac hi ne as is don e i n Linde s plan t

’

- .

for th e manufac ture of li qui d air but wh e th e r re cove ry of t he solve nt by .

such a proce ss would prove re mu ne rative se e m s doub t ful .

7

At t he Fre nch Gove rnm e nt works at Sain t Me dard t he solve nt is re cove re d -

from P oud re B by t he followi ng m e th od : A trolle y cha rge d wi t h s t rips of

powde r is run ove r a m e ta l cham be r a door ope ns i n t he top of t he cham be r
j u s t large e nough for the troll e y to p a ss through it i s le t do vm and t he doo r
1
P rkin J
S ee e , . S oc . Ch e m I nd . .
, 19 1 2, p . 61 6 ; l o
a s J un e 29 , 1 9 1 2 .

2
F G Do mi a n
. . , N a t u re ,
M rch a 23 ,
1 9 1 6, p . 83 .

3
L a g e r ma r k a nd E lte r k o w , B er .
, 1 8 77, p . 63 7 .

4 E rdma nn a nd K ot hn e r , Z e fts ch . A no r y . C he m .
, 1 89 8, p . 48 .

5 Gem) . Pa t . of F brua ry e 22 , 19 12 .

6
S S
. .
, 1 9 1 3, p . 39 5 .
7
S ee pp . 4 9 2— 1 9 6.
 SOL VENTS

is clos e d and the vapours of alcohol and e th e r a r e give n off in the air tight
,
-

chamb e r Th e y a r e drawn off by a st e ady curr e nt of air cond e ns e d by

.
,

r e frig e ration and colle ct e d W h e n th e drying i s su ffici e nt the trolle y is .

r e move d It is stat e d that th e r e c ov e ry is satisfactory

.
1
.

A high e r yi e ld of r e cove re d solve nt can b e attain e d if th e air aft e r passing ,

through the conde ns e r i s r e turn e d to t h e stove so that it pass e s c onstantly ,

round a clos e d circuit The e volution of solve nt i s rapid at first but b e com e s
. ,

slowe r and slow e r as the powd e r g e ts dry e r larg e si z e d powd e rs for h e avy -

ordnanc e may have to r e main in the stov e for months during the gre at e r ,

part of which tim e the quantity of solve nt vapour give n off is hardly a p p r e
c ia b le In laying out works it is advisabl e to plac e a fe w stov e s fitt e d with
.

r e c ov e ry plant n e ar th e pre ss hous e s so that th e powd e r can b e transfe rre d -

to th e m e xp e ditiously and dri e d th e r e for a fe w days Aft e r this pr e liminary

,
.

drying t he powd e r can b e transfe rre d to oth e r stove s situat e d at a distanc e ,

wh e re no att e mpt is made to r e cove r the solve nt W h e re conside rabl e quan .

titi e s of powd e r of larg e siz e a r e mad e th e are a cove re d with stov e s may ,

e xt e nd ov e r many acr e s and to conn e ct th e m all up with a r e c ove ry plant

,

woul d b e ve ry costly .

For t h e re cove ry of ac e ton e from cordit e and oth e r mat e rials R ob e rtson Ac t n e o e

and R intoul have take n advantage of th e fact that th e vapour is v e ry re adily e°° e y r v r °

absorb e d by a solution of sodium bisulphit e with which it form s a c ompound , ,

C 11 0 Na H SO
3 6 ,
2
A ve ry simpl e and satisfactory m e thod has b e e n work e d
3. .

out by which practically the whol e of the ac e ton e in th e air of t he stove i s

,

r e c ove r e d in a v e ry pure c ondition Th e air is drawn away from the stove .

through wide zinc pip e s to the r e c ove ry hous e wh e r e it is caus e d to pass up

a s e ri e s of towe rs down which a 30 p e r c e nt solution of th e bisulphit e i s flow
,
.

ing Towe rs w e re de sign e d sp e cially for this purpos e and th e y have prove d
.
3
,

v e ry succ e ssful not onl y for this but for many oth e r purp os e s also such as , ,

purifyi ng air (s ee Fig as th e y afford a maximum surfac e of contact b e twe e n

.

t h e air and th e liquid and offe r a minimum of r e sistanc e to th e passag e of

,

th e form e r Th e tow e rs a re squar e in s e ction and lin e d with l e ad : insid e

.

th e r e a r e fram e s which a r e wound with strands of wool zig zag fashion At

,
-
.

th e top of th e tow e r e ach strand clip s into a trough which i s k e pt supp li e d ,

with bisulphit e solution Th e top of the towe r i s clos e d by m e ans of a glass .

plat e and th e r e is also a glass window n e ar th e bottom so th e action of the

, ,

towe r can b e watch e d Th e re a r e of cours e various pumps or e ggs and .

, ,

tanks so that th e solution can b e rais e d again a n d pass e d down th e sam e

,

t o we r again or the n e xt o n e n e ar e r t h e stove W h e n the solution is n e a rly

,
.

saturat e d with ac e ton e it i s transfe rre d to a still wh e re it i s simply h e at e d to ,

1
P . et s , 1 6, 1 9 1 2, p . 10 8 .

2
E ng . Pa t . of 1 90 1 ; U S
. . Pa t . of 1 90 3.
3
E ng , Pa t . of 1 90 1 .
3 50 E XP L O SIVE S
'

dri ve t he a c e to ne o ff aga in a s it ha s b e e n fo u nd that practi cally t he whol e

,

of t he ac e t on e can b e di st ill e d o ff be fore t h e bisul phi te b e gin s to d e compos e .

FI G . 70 . S crub b ing T ow rs
e (R obe rt son a nd R in t oul
’
s P t nt )
a e .

A li ttl e sodi um carbonat e or caustic soda is adde d howe ve r to di mini sh th e, ,

amo u nt of sul phur di oxi de that pass e s ove r and to c omb in e with any free
,

sul phurous acid t hat has be e n form e d by the oxidation of the bisul phite ,

and t h e conse qu e nt form ation of sodium sulphate Th e crude di st ill ate thus
.

obtain e d i s mix e d with wat e r and a littl e sodi um carbonate and di still e d again ,

from a still such as that sho w n in Fig 69 It is thus obta in e d in an e xtre m e ly

. .
 SOL VENTS

pure stat e it c o n ta ins no de t e ctabl e quantity of any impurity e xc ept som e

'

e thyl m e thyl k e ton e

-
which is harmle ss and a trac e of carbonic acid Th e
-
, , .

Pe r Ce nt . Ac e t on e b y W igh t
e

I d 4 0 m 60

‘
0 0 01 6

00 0 1 2

0 0 00 8
'

°
0 00 0 4

J o Jo

Per C n t Ni t ro glyc e r in e b y
e .
-
W e igh t .

FI G . 71 . Va po u r P r s sur e s of M ix t ur e s of
e Ac e t on e a nd Ni t ro glyc ri n
-
e e a t 18
°
C .

bisul phit e solution i s pr e pare d b y passing sulphur di oxide into a solution

of sodi um carbonat e the sul phur dioxide b e ing made by burning sulphur
,

i n a small burn e r in a curre nt of air .

Anoth e r r e ason for not att e mpting to r e cove r the ac e ton e from the last V l a til ity 0
m
o

stage s of the dry ing of a nitro glyc e rin e powde r i s that nitro glyc e rin e is give n cgi
Sf
'
- -

o ff much mor e r e adily wh e n th e gr e at e r part of t h e ac e ton e has b e e n r e m ov e d .

Fig 7 1 shows how rapidly th e vapour t e nsion of th e nitro glyc e rin e ris e s wh e n
.
-

t h e p e rc e ntag e of ac e ton e i s v e ry small 1

In th e cas e of cordit e th e proble m
.

1 M a rsh ll Tra ns C h m S oc 1 9 0 6 8 9 p 1 3 50 ; P o c 1 9 1 3 p 1 57
a , . e . . , , . r . , . .
 E X P L O SIVE S
is complica t e d b y t he pre se nce of g un co t ton and t h e va p our pre ss u re s of -
,

mi xt ur e s of gun c o tto n a nd ace t o n e have no t be e n de te rmi n e d It is p roba ble

-
.
,

ho w e ve r t ha t in t h e fres hl y p re sse d co rd co ntaini ng a fai rly la rge pe rce nta ge

.
s
,

of ace t o n e a co n s id e r ab l e p ropo rtion of i t i s di ssolve d in t h e nitro glyce rin e

,
-
,

t hu re ducin g t he va p o ur p re s sur e of t he la t te r but wh e n t he pe rce nta ge of

s
,

a ce t o n e has b e e n re duce d to a small a m oun t by dr yin g n ea rly t he whol e of ,

i t is di ssolve d in t h e g u n co tton so t hat t h e ni t ro glyce ri n e e x e rts n e arly its

-
,
-

full vapo u r p re ssure The r e sul t of thi s i that in the ea rly sta ges of the
.
s

dr ying t h e re is li t t le or no da nge r of ni tro glyce rin e be ing de po sited in t h e -

pip es l ea di ng from th e sto ve to t he re c o v e ry house but in th e late r sta ge s it ,

wil l b e de p o s i t e d Ca re must b e ta k e n t h e re fore in la yin g th e pipe s that th e

.

ni t r o gl y ce rin e will onl y acc um ula t e in pla ce s from whi ch it can b e dra wn o ff
-
.

A t a ll t h e lo w e t po in t s of t he pipe r i m small dr ainin g tubes m ust b e provi de d

s
-

t h es e c a n b e close d wi t h rub be r cork so tha t t he ni t r o glyce ri n e ca n b e drawn

s
,
-

off da il y in t o a rub be r or gutta pe rc ha bottle or be ak e r

.
-
.

Anoth e r dange r t hat h a s to b e gua rde d agai nst is t he communi cati on of

fi re fro m o n e sto ve to anoth e r thr ough t h e pipe lin es In R obe rtson and -
.

R in t oul s s y s t e m protec ti on i afford e d by t he introduction of t r ap s in which

’
s
,

fi n e wi re ga uze is in t e rpo se d to pre ve nt t h e fur th e r t r av e l of t he flam e Th e y .

a re so arra ng e d tha t a ga s e xp losion in t h e pipe will blow out a di sc of thi n

ma t e ri a l and s o re li e ve t he p res sur e .

I t is not onl y in the pip e lin e s that th e e xplosibility of mi xtures of vapour

-

and a ir ha s to b e g uarde d again t bu t wh e re ve r combustible and volatil e

s
,

li qui ds a re use d ; in th e incorpo rating and pres s house s sto ve s maga zi n e s , ,

a nd so lve n t s t ore hous e s grea t ca re m ust b e ta k e n tha t no flam e or spark

-
,

ma y i gni t e a mi xtur e of air and vapour The followin g Table giv es the .

e xplosiv e lim i t s for a n u m be r of vola ti l e li qui d s as d e te rmi n e d by K u b ie rs c h ky

1

P rce n t g s
e a e b y V O N DZO Pe r c n t by
e .

cor sp n d in g t
re o o

Lo w r L imi t
e f p p e r L im it 1 p t by V
e r ce n . o l .

Pe n t a n e

1
A ng .
, 1 90 1 , p . 1 30 .
 S O LVE N TS
If th e p e rc e ntag e of vapour fall b e low th e low er limit or ris e above th e upp e r ,

t h e mixtur e i s no long e r inflammabl e but th e s e li mits d e p e nd upon t h e ,

c on di tions und e r w hich the e xp e rim e nt i s carri e d out In a larg e flask the .

limits a r e wide r than in a narrow tub e and a small spark oft e n wi ll not ignit e ,

a mixtur e th at can b e caus e d to e xplode by th e app lication of a po w e rful spark

or a flam e l
. Th e limits a r e much narro w e d by th e introduction of carbon
dioxid e or oth e r indi ff e re nt gas It has b e e n shown by O li e that the intro
’
2
.

duction of a j e t of st e am wi ll e xtinguish a larg e quantity of fi e rc e ly burning

alcohol i n a fe w minut e s and it is r e comm e nd e d that buildi ngs conta ining
,

c onsid e rabl e quantiti e s of inflammable li quids b e fitt e d up so that a fi r e can b e

e xtinguish e d by this m e ans It must not b e forgott e n that vapours may b e
.

ig nit e d by e l e ctric sparks g e n e rat e d by the f ri ction of driving b e lts and p r e ,

cautions should b e tak e n to dissipat e any charg e s that may b e thus form e d .

E ve n th e e mpty dr um s which hav e contain e d li quids may give ris e to

s e rious accide nts if the last trac e s a r e not r e move d O n March 30 1 9 0 4 a .
, ,

drum that had c ontain e d ac e ton e e xplode d kill ing two me n and in j uring ,

s e ve ral oth e rs at P rinc e s Dock Glasgow Th e drums wh e n e mpti e d shoul d

’
, .

b e l e ft without th e ir bun gs and shoul d b e plac e d upon racks in th e op e n for

a fe w days wi th th e bunghol e s downwards if at the e n d of that t im e it i s
found that th e sm e ll of th e solv e nt i s still p er c e ptibl e in th e drum th e last ,

trac e s can b e r e move d by di re cting a j e t of c ompr e ss e d air into the drum for
a minut e or so r e lying on the ab s e nc e of sm e ll as an indi cation that th e r e moval
,

i s compl e t e Th e bungs should th e n b e r e plac e d and scr e w e d up so tightly

.

by m e ans of a ke y that it i s imp ossibl e to r e move th e m by hand or for th e m ,

to work loos e during transit 3

.

Th e vapours of many of th e li quids us e d as solv e nts a r e in j urious to th e T x icity o

vap our s.
h e alth of thos e e xp os e d to th e m B e nz e n e i s v e ry poisonous but is not us e d
.
,

much for maki ng smok e l e ss p owde rs Ac e ton e has no v e ry s e riou s e ffe ct . .

That of th e alcohols incr e as e s with th e mol e cular we ight ; amyl alcohol i s -

d e cide dly th e worst of thos e g e n e rally us e d It has b ee n found that th e .

foll owi ng dos e s a r e fatal p e r kg of animal : 4

.

M e t hyl lcohol -
a

Et hyl
P ropyl
B u t yl
Am yl

A mixtur e of th e vap ours of e th e r and alcohol i s mor e p oisonou s than that

of e ith e r of th e substanc e s s e parat e ly For thi s r e ason also buildin g s in w h ich .

amyl alcohol or e th e r alcohol vapours may b e pr e s e nt shoul d b e w e ll ve ntilat e d

- -
.

1
S ee a ls B un te J j G h 1 9 0 1 p 1 8 3 5 ; J S c C he m I nd 1 90 2 p 33
o , . . a s , , . . o . . .
, , . .

2 P
.t s 1 5 1 9 10 p 1 60
e , , , . .

3
A R 1 90 4 p 9 4
. .
, ,
4 P
. et S
. v ol x v i 1 9 1 2 p 1 28 . .
, . .
, , . .

V OL . I . 23
 C H AP TE R X X V

RO
NI T -
G LYCE I NE R HI GH P
EX L O SI VES

K i e s lg hr
e M a nufa c t ur of dyn m i t e P rop e r t i e s of dyn mi t e Fr nch
u : e a : a : e

dyn m i t s : Ame ric a n d yn a m i t e : L ig d y n Am m onia dyn m i t : J udson

a e : a e

powd r Dyn a m i t e N o 2 a n d 3 G e l a t in iz e d e xplosi v e s B ox s for j e lly

e : s. : : e

Di mi nu t ion of s e nsi t i v en s s a n d s t a bili t y : E xud a t ion G e ligni t e : G e l t in e

e : a

dyn a m i t e W r a pp rs 40 p e c e n t d yn a m i t
e Am e ric a n ge l a t in dyn mi t s
r . e a e

Forci t Fr e nch g l a t iniz d e xplosi v e s L o w fr e zing e xplos i v e s Sa f t y

e : e e : e : e

e xplosi v s con t a inin g ni t ro glyc e rin e

e C b o n ite -
ar s

TH E first att e mpts to u se li quid nitro glyc e rin e for blasting prove d so dis -
Kieselg u

astrous that it b e cam e n e c e ssary to find som e m e ans of c onv e rting it into
,

a solid unl e ss its wonde rful pow e r was to b e lost to th e world Many of
,
.

t h e principal countri e s had ind e e d pass e d law s forbidding th e u s e of nitro

glyc e rin e wh e n in 1 8 66 Nob e l discov e r e d that it could b e r e nd e r e d compara
,

tiv e ly saf e by absorbing it in ki e s e lguhr This at onc e gav e a gr e at imp e tus .

to th e high e xplosive s industry and laid th e foundations of the gre at fortun e ,

which Nob e l aft e r wards incr e as e d by oth e r inve ntion s and by h is financ ial
ab i lity Ki e s e lguhr or guhr is a fi n e silic e ou s e arth c onsisting of th e r e mains
.

of diatoms and oth e r microscopic animals It should hav e th e p owe r of .

absorbing thr ee tim e s its w e ight of nitro glyc e rin e and should b e fr e e from -
,

gritty particl e s It i s found in th e L ii ne r b u r g e r H e ide to th e north of Hanov e r

. , ,

also in Austria Scotland Norway and Australia The fo llowing analys e s

, , ,
.

show its composition :

F ro m O b e r lo h e (H a n o ve r )
D ri ed Ca l cin ed

To p S tr tu m
a

(G o d y ) (G o d y ) (Sa nfo rd ) (H a g e n )

744 8

24 -4 2
3 58 E X P L O SI VE S
A sample of th e guhr us e d at Ar dee r in 1 8 8 4 was analys e d by Dupr e (S R 61 ) . .

it was of pal e re d c olour and passe d e n t ire ly t hrough a 20 m e sh si e v e ; it -

cons iste d of
S olubl e sil i ca o xi d of iron
, e

In s oluble sili ca sa nd nd gr i t ,
a

L o ss on igni t ion
M ois t u r e

100 -00

In cons e qu e nc e of t h e c e ssation of suppli e s from G e rm any and Austri a .

ste p s a r e be ing take n to de v e lop d e posits in Vic tori a and Ne w South Vi ale s
’

Those at Lillic ur north we st of Ballarat a re said to b e suitabl e for t he manu

,
-
,

factur e of dy namite 1
.

Guhr is de cide dl y hygroscopic and cannot b e dri e d e ffe ctive ly e xc e pt at a

h igh te mp e ratur e it is n e c e ssary to calcin e it at a low r e d h ea t Th e organi c .

matt e r is thus de stroy e d also Som e tim e s how e ve r th e guh r is onl y charre d .
, , ,

in whi ch cas e a consid e rabl e p e rc e ntag e of carbonac e ou s matte r will r e main .

Th e guh r may b e mix e d wi t h som e oc h re mica talc or barium sulphate w ith , ,

out impa iring its absorptive powe rs O chr e give s th e dynami t e a unif orm .

r e d colo u r Carbonat e of a mm o n ium sodi um mag ne sium or calcium is

.
, ,

adde d up to 2 p e r c e nt of t he fini sh e d e xplosive in ord e r to n e utralize th e

.
,

acid form e d by th e de comp osition of th e ni tro glyc e rin e on storage The -

.

carbonate s of mag ne sium and calcium a r e b e st as th e oth e rs hav e a dec o m ,

posing action on th e e xp losive .

Th e carbonate and o t h e r addi tions should b e mi x e d ve ry in timate ly with

t he gu h r whi ch i s th e n pass e d through a 30 m e sh si e v e to re mov e a ll fore ign
,
-

bo di e s Th e mate ri al i s th e n w e igh e d out i nto a l e ad brass or copp e r lin e d

.
,
-

box or a rubb e r bag and nitro glyc e ri n e is pour e d on in the proportion of

, ,
-

not more than 75 parts by w e igh t to 25 of t he absorbe nt Af te r stan ding for .

a tim e t h e mate rial is k ne ade d or mi xe d by hand in much th e sam e way as

is don e w ith cord ite paste The mixt ure i s th e n conve ye d to a cartridge .

hut in which a r e e re cte d two to fo u r but pre fe rably onl y two cartridge , ,

machin e s E ach of th e s e consists of a brass pl u nge r workin g ve rtically

.

through two slee ve s or guide s (Fig It is work e d by m e ans of a hand .

l e ve r and is shod at t h e lowe r e n d with lignum vit ae or ivory Thi s low e r

, .

e n d works i n a t h in brass tub e of t h e sam e diam e te r as t h e finish e d ca rtridg e

i s to b e Th e upp e r e nd of the tub e forms the ap e x of an inv e rte d con e or

.

hopp e r of soft l e ath e r (not sho w n i n t he illustration ) havin g a capacity of ,

about a po u nd of dy nami te th e upp e r e dge s of thi s hopp e r be ing conn e cte d

,

by t hr e e or more cords to a boss high e r up on the plung e r The plung e r works .

e asily thr ough t he guid e s so a s to mini miz e t h e friction and t h e r e is a good

, ,

C h m Tra de J o r n
1
M y 1 3 1 9 1 6 p 426
e . u .
, a , , . .
 NIT R O -
G LYC ER INE H IG H E XP L O SIVES 3 59

cl e aranc e b e twe e n it and the tub e Som e t im e s it carri e s an inve rt e d b e ll

.

to pr e ve nt th e e xplosive wor king up into the lowe r guid e To work th e .

apparatus a girl wrap s a pap e r cartridg e wra pp e r round the outside of th e

tub e l e avin g suffici e nt pap e r at th e bottom to
,

turn in and clos e th e e n d H olding this in

.

position with o ne hand s h e works th e pump

handl e wi th th e oth e r ; the e ff e ct of e ach up
ward strok e is to j e rk t h e soft l e ath e r hopp e r
by m e ans of th e cords and caus e the contain e d ,

dynamit e to fall into the tub e wh e nc e it i s ,

forc e d by th e e nsui ng downward strok e into

‘

th e pap e r wrapp e r at th e low e r e n d

of thi s tub e ; thi s is r e p e at e d until
t h e cartridg e is of t h e r e quire d
l e ngth wh e n it i s r e move d and the
, ,

upp e r e n d of the pap e r i s fold e d in .

Th e op e ration of making th e s e cartridg e s i s

a dang e rous o ne and th e gre at e st car e should
,

b e take n to minimiz e th e dang e r 1 Th e r e shoul d .

b e no nails in th e machin e ; t h e mouth of t h e

tub e should b e b e ve ll e d and fac e d w ith l e ath e r
so fitt e d that an untru e pl u nge r ca n not strik e
th e e dg e of th e tub e th e di am e t e r of th e body
of th e plunge r shoul d b e l e ss than that of its
workin g e n d ; and the tub e shoul d b e slightly
coni cal afte r the first short distanc e O n no .

account should any att e mpt b e mad e to work

th e e xp losiv e wh e n it i s froz e n and work should ,

b e susp e nd e d altog e th e r if t he t e mp e ratur e insid e

th e hut i s b e low O nl y a sma ll quantity
of e xplosive shoul d b e allow e d in the hut at o ne
tim e th e r e mainde r b e ing k ept in a cupboard
,

Dyn
a m it C r t ri d g
e a e
outsid e T h e
. huts should b e at l e ast 40 yards
Ma chin e . o ne from anoth e r and surroun de d wi th good
,

mounds .

Th e mat e rial thu s mad e is a plastic mass varying in colour from bu ff to Pro perti es 0

r ddi sh brow
e n. Dire ct contact with wat e r cau se s th e nitro glyc e rin e to yn mit D - a e,

s e parate from it ; th e r e fore gre at care must b e e x e rcis e d w h e n using it in

w e t plac e s
. It fre e z e s som e what m ore r e adi ly than li quid nitro glyc e rin e -
.

W h e n igni t e d i n small quantiti e s it simply burns away fi e rc e ly but fatal

'

accid e nts hav e a ri s e n i n c onsid e rabl e numb e r from p e rsons supposing that ,

1
S S J ? 61 Nos 1 4 5 nd 1 8 4
ee , . a .
360 E X P L O SI VE S
as i t is rea sonably sa fe to ignite a fe w ca rt ridge s of un froze n dynamite it i s ,

e qually saf e to warm i t upon a shov e l i n an ov e n in a tin ov e r a fi r e or in , . ,

”
various oth e r ways whi ch usually l ea d t o a ve r di ct of Accide nta l D ea th
, .

Froz e n dynamite is muc h more su sc e ptible to e xplosion by simple i gni t ion ,

but it i s l e ss s e nsitive to de tonation as also to a blow or friction un de r som e ,

c ondi tions but th e annals of e xplosive s a re full of insta nc e s of th e fa ta l

,

un e x p e cte d e xp losion of fr o ze n nitr o glyc e rin e e xplosive s which had not -

,

be e n t re a te d w i t h prope r re sp e ct The de nsity of dynamite i s stat e d to b e .

1 4 to
-
but I hav e fo u nd it to b e about 1 62 If th e re w e re no air spac e s .

in i t t h e d e nsity woul d b e 1 77 Th e te mp e ratur e of ignition is giv e n a s

.

Th e followi ng a r e analys e s ni ad e b v Dupr e in 1 90 1 of two sa mpl e s from

Ni t ro glyce rin e
-

Ki e s e l guhr
Am m oni um ca rb on t a e .

Ot h r solu b l e m a tt r
e e

M ois t u r e

1 00 0 0 100 0 0

Con ta ini n g sa nd ca lcula t e d on d y n a i t

, m e

Ki es e lgu hr
B oth s ampl e s w e re of a li ght brick r e d colo u r and gav e h e at te st s of ove r
thi rty m inut e s .

This m ate rial i s call e d in Grea t Britain Dynamite No 1 or Ki e se lguhr .

,

Dynamite or simply Dynamite and in G e rman y th e nom e nclatur e i s much

, ,

t h e sa m e but in Am e rica it i s call e d Giant P owde r and t h e te rm dynamite

, ,

i s usually appli e d t o a mix t ur e of ni t ro glyc e ri n e wood p ulp and sodi u m .

—
,

ni t ra t e which i s not autho ri z e d in E ngland at all Dy namit e No 1 i s not

,
. .

mad e ve ry e x te nsive ly now as i t has be e n re plac ed by vari ous g e latini ze d ni tro

,

glyc e rin e m ixture s but it poss e sse s t h e advantag e that it is m ore stabl e wh e n
,
.

sto re d at high t e mp e rature s as t h e acid products of de c omposition a re imme

,

di a te ly n e utrali z e d by t h e carbonate pre s e nt I hav e e xamin e d dy nami t e .

t hat had bee n stor e d for a conside rabl e num be r of ye ars at Ade n and could ,

find no signs of instabili ty wh e rea s a ge latini z e d e xplosive und e r th e s am e

,

condi tions would hav e give n a v e ry low h ea t te st .

B e sid e s infusorial ea rth oth e r s ili c e ou s m ate rials hav e bee n u se d for t h e
man u fact u r e of dynamite in Franc e for instanc e a mate rial call e d Ra n da ni te , , ,

whi ch is found in Auve rgn e and has bee n form e d by t he w ea t h e ring of ,

fe l d par
s . B e rth e lot propose d th e u s e of a sp ec ial a rt ificial sili ca m ad e by .

d e compos i ng sil icon fluoride w i t h wa te r and ha ving a v e r y h igh absorp tiv e

powe r Nobe l in hi s pate nt sp e cificati ons m e ntion e d a num be r of mate ri als
.
, ,

C h lo n p 30 2 ; V nn in
1
a t C h sn ea u
,
p 3 65
. e e e , . .
 NI TR O GLYC ER IN E HIGH E X P L O SIVES
-

such as p owd e re d brick dry clay and plast e r During th e si e ge of P aris

,
.

coal ash e s we r e us e d and i n Am e rica magn e sium carbonat e has found som e
-
,

favour .

Form e rly a numb e r of sp e cial mixture s of this kind w e r e made in Franc e 1

,

but now t h e onl y nitro glyc e rin e e xplosive with in e rt bas e us e d th e re larg e ly
-

i s dynamit e No 1 containing 75 p e r c e nt of nitro glyc e rin e and 25 p e r c e nt

. .
—
.

of guhr Mor e rare ly dynamit e s Nos 2 and 3 a r e e mploy e d containing 3 5

. .

and 25 p e r c e nt of nitro glyc e rin e r e sp e ctive ly

.
2
Dynamit e s a r e not allowe d
-
.

t o b e transporte d in Franc e if th e y a r e mor e than twe lve months old 3

.

As nitro glyc e rin e contains an e xc e ss of oxyg e n e ve n aft e r all t he carbon

-

has b e e n conve rt e d into dioxide the id e a natur ally occurr e d to mix it w ith ,

an organi c absorb e nt c ork charcoal has a v e ry gr e at absorptive powe r but ,

th e mat e rial that has b e e n us e d most is wood pulp Th e Atlas P owde rs .

introduc e d from Am e rica by the F e nians in 1 8 8 3 and 1 8 8 4 for th e ir cri minal

att e mpts w e r e of thi s typ e Two of t h e sampl e s analys e d by Dupr e had th e
.

following c omposition
N it o glyc e rin e
r -
N it glyc rin e
ro -
e

W ood s a d t sligh t ly ch a rr d in
S e W ood s a wdu s t a n d a li tt le ch a l k
pa rt s
M ois t ur e M ois t u re
But th e s e mixture s contain e d an e xc e ss of oxidizabl e matt e r It is more .

e c onomical to add anoth e r oxyg e n carri e r In Am e rica sodium nitrat e is .

us e d v e ry e xt e nsive ly for thi s purpos e In th e Bur e au of E xplosive s R e port .

No 2 B e is tle giv e s th e r e sul ts of th e analysis of a large numb e r of Am e rican

.
,

dynamit e s w hich a r e summariz e d in t h e following Tabl e :

,

G r a de N i t ro g l yc rin e e “b od Pu l p So d iu m N i t r ta e Mo is t ure

It will b e s e e n that th e variations in comp osition in e ach grade a r e consid e rabl e

t h e figur e s for t h e 50 and 30 p e r c e nt grad e s a r e bas e d on two analys e s e ach .

only but thos e for th e oth e r grade s on a c onside rable numb e r Many of t he
,
.

dynamit e s e vid e ntly c ontain e d a fe w p e r c e nt of som e oth e r constitu e nts .

1
Se e lst ed i t ion of t h is w ork p , . 28 1 .

2
Ve nn in e t C h sn
e u p
ea , . 3 63 . S ee a Lso P . cl S v ol x v ii
.
, p . 158 .

3 V mi n
er e t Ch sn
e u p
ea . . 3 65 .
 EXP L OSI VE S
unde te rmin e d but t hos e in whi ch t he re was a consid e rabl e de fici t have b e e n
,

e xclud e d from t h e abov e sum mary Th e following a r e two e x a mpl e s of .

Am e ric a n 40 p e r c e nt dynami te s : .

St ig h t d y m it H rcu l s ra na e e e

Ni t ro gly ce rin e -
40
\ Vo o d pul p -
1 1 75 -

S odi m ni t r t u 4 7 25
a e -

Ca lci u m c r b on t a 1 a e

M a gn sium ca rb on t e a e

S odiu m c hl ori d e

M o ist ur e

Hall and H o w e ll g iv e th e foll o wi ng as th e compo sition of ty pical Am e rican

straight dynamit e s 1 °

25 p e r 30 pe r
St r e n rf t h
c nt
e .

0 25 30 35 40 45 50
Co m bus t ibl m t ri l e a e a
2 9 18 17 16 15 14 14
Sodi u m ni t r t a e 0 56 52 48 44 40 35
C a lcium or m g n i m ca r b on a t
a es u e 1 l l 1 l 1 1

10 0 1 00 100

A sim ilar e xp losiv e is manufactur e d in South Africa und e r th e nam e of

L ig dy n Th e 40 p e r c e nt grad e has t h e comp osition
:

. .

Ni t ro glyc rin
-
e e

“ b od m l - ea

S od i m nit r t
u a e

“h eat fl our
Th e cart ri dge s a r e mad e in th e Qui mau packing machi n e which works on t he ,

sa m e p rincipl e a s t h e hand mac hin e shown in Fig 72 but i t is op e ra te d by .

,

po w e r and mak e s t hir te e n to fif t e e n cartridge s at o n e t im e O n January 3

,
.
,

1 9 1 3 t he cont e nts of o n e of th e s e machin e s e xplod e d and kill e d nin e p e rsons

,

and in j ure d t wo o t h e rs .

In Am e rica Am monia Dynami t e s a r e also mad e in whi ch a larg e propor t ion ,

ite
dyn a m s.
of t he ni t ro glyc e rin e is re plac e d by amm o nium ni t rat e
- .

1 ur u of M i n s B u ll tin N o
B ea e , e . 48 .

2 Cons is t in g of w ood pulp fl our -

, ,
a nd sul phur for grad s b low e e 40 pe r c nt
e w o od

pul p onl y for o t h r gr d s e a e .

 NI TRO GLYCER IN E HIG H
-
E X PL OSl VE S 363

Th efollowing Tabl e shows th e compositio ns of typical ammonia dynamite s

of various grad e s 1

t ng t h
S re 30 p e r c nt e . 35 p e r c nt
e . 40 p e r c nte . 50 p e r c nt
e . 60 p e r c nte .

N it ro glyc rin e
e

Amm onium ni t r a t e .

Sodi u m ni t r a t e

Co mbu s t i b l e m t ri l
a
2
e a

C a lc i u n ca rb on t or zinc
i a e

oxid e

An xplosive of a som e what difi e r e n t typ e which is also us e d e xt e nsiv e ly

e .
,

in Am e rica is Judson P owd e r which was pat e nt e d in 1 8 76 by E Judson

, ,
. .

This i s made with p e rc e ntag e s of nitro glyc e rin e varying from 5 to 20 p e r -

c e nt Judson P owd e r E R P has th e composition

. . . .
'

N it o glyc e rin e
r

Sodium ni t r t a e

Sul phur
C a rme l co l a

N it o glyc e rin e
r

Sulphur co a l a n d r sin
,
e

Sod ium ni t r a t e

Th e so dium nitrat e is mix e d with th e combustibl e s and the mixture is h e at e d

b e yond th e m e lt ing p o mt of th e sul phur and r e sin The slightly porous mass .

thus form e d is coat e d with nitro glyc e rin e which acc e l e rat e s t h e e xplosion -
,

of the mixtur e and so mak e s it conside rably mor e vi ol e nt 3

It is r e ally a .

sort of crude g u npowd e r containi ng a littl e nitro glyc e rin e It is fire d with —
.

a prim ing cartridg e of dynamit e .

Th e gr e at ob j e ction to th e s e mi xtur e s i s that so di um nitrat e is d e cid e dl y

d e li qu e sc e nt and ammonium nitrat e still more so e ve n from a mod e rat e ly
,

dry atmosph e re th e y tak e up moistur e and b e com e li quid and t he solution ,

thus form e d displac e s the nitro glyc e rin e and caus e s it to e xude thus gi v ing
-
,

ris e to a v e ry s e rious dang e r For this r e ason such e xplosive s have not b e e n
.

authori z e d in E ngland It i s not e worthy that for th e work on t he Panama

.

Canal in which many mil lions of tons of dynami t e have b e e n us e d th e

, ,

Isthmian Canal Commission o nly acc e pt e d e xplosive s containing potassium

1
H lla a nd H ow ll e , lo o . c i t.
2
Consis t ing of w ood pul p fl o u r -
, ,
a nd sulphur .

3
B ur u of h iin e s B ll ti n No
ea , u e . 48 , p . 6
.
 E XP L O S I V E S
nitrat e and fre e from so di um ni trate magn e si u m salts and oth e r impu ri ti e s
,

whi ch woul d mak e t h e mate ri al hygroscopic Tw o sampl e s of Atlas P owd e r .

us e d in t he c onstruction of th e Panama Canal we re analys e d by Still m an and

had t he comp ositi on :

D yna m ite Th e arly de mand for an e x plosive that w a s milde r and slowe r than
e
Nos 2 a nd 3
. .

D ynamit e No 1 was me t i n E ngland by t he manuf actur e of Dynamite No 2

. .
,

w hich was r e comm e nd e d for work in coal min e s and quarri e s Thi s c onsiste d
-
.

of not mor e than 1 8 p e r c e n t of nitro glyc e rin e mi x e d with som e 1 0 p e r c e nt

.
-
.

of charc oal and 72 p e r c e nt of saltp e tr e and som e tim e s a little paraffin It

.
, .

was practically gunp owd e r in which nitro glyc e ri n e had be e n substitute d for -

sulphur Dyna mit e No 3 was a m ore pow e rful e x plosive and consiste d of
. .
,

a mi xture of e qual pa rt s of ki e se lguhr dynamite and a mi xtur e of sal t p e tre

and wood m e al
“

-
.

In 1 8 75 Nob e l made a fur th e r advanc e of th e ve ry first importanc e by

x l iv
e p os es ,
hi s di scov e ry that by di ssolving 7 or 8 p e r c e nt of c ollodion c otton in nitro .

glyc e ri n e it is c onve r te d into a g e latinou s solid The di scove ry arose from .

t h e fact that Nob e l had cut his fing e r and collo di on had b ee n us e d to cov e r
t he woun d whilst th e inve ntor was e xp e rim e n ting w ith nitro glyc e rin e som e -
.

of it got mi x e d with the collo dion In th e foll o wi ng y e ar pat e nts w e re grante d

.

i n t h e principal industrial c ountri e s prot e cting t h e inve n t ion but it was som e ,

y e ars b e fore t he di ffi culti e s of manufactur e had b e e n ove rc om e In Gre at .

B rita in t h e manufactur e was lic e ns e d in 1 8 78 and in 1 8 8 0 t h e manuf actur e ,

was comm e nc e d on a large scal e in t h e Contin e ntal facto ri e s of t h e Nobe l

Syndi cate but c onsid e rabl e di ffi c ulty was found in fu lfi lli ng th e r e quire m e nt s
,

of H M Insp e ctors of E xplosiv e s Th e first products e xud e d ni tro glyc e rin e

. . .
-
,

and manufacture w a s susp e nd e d for som e y e ars afte rwards w h e n thi s ,

difficulty had b e e n ov e rcom e the blasting ge latin e s fail e d t o pass t he h e at

,

te s t and it was not until 1 8 8 7 that th e manufactur e wa s i n full s wi ng i n Gre at

,

B ri tain A gre at d e mand for t he mat e ri al sprang up at onc e in conse qu e nc e

.

of i t s e normous po w e r and c onve ni e nt nature For blasting hard rock i t ha s .

prove d ve ry s e rvic e abl e e sp e cially wh e n as in t u mi e lling i t is not n e c e ss a ry

. , ,

to ge t the rock out i n larg e pi e c e s .

Ma nufa c ture . Th e c ollodion cott on i s thoroughly dri e d and r e duc e d to a fi n e sta te of

d ivi sion It shoul d not conta in m ore than 1 p e r c e nt of wate r A w e igh e d
. . .

quantity is plac e d in a bra s s lin e d box and t he r e qui site quantity of ni tro
-
,
 N I TRO GLYC ER IN E HIGH E X P L O SIV E S
-
3 65

glyc e rin e i s poure d on The mat e rials a r e mix e d tog e th e r by hand and allowe d
.

to stand for som e hours or ov e rnight Th e box is th e n tak e n to th e mixing .

hous e wh e r e th e mat e rial i s h e at e d to about 50 C and g e ntly mix e d until

,
°
.

solution i s compl e t e which tak e s about an hour At first the mixing was
, .

don e e ntire ly by hand with woode n stirr e rs but now th e final mixing is g e n e r ,

ally p e rform e d i n incorporating machin e s similar to t hos e us e d in the manu

facture of smok e l e ss powd e rs (s cc Figs 56 At the Ard ee r Factory of .
,

Nob e l s E xplosive s Co and som e oth e r works Mc Ro b e r ts s machin e is us e d

’
.
’

(Fig . This has a numb e r of narrow stirre r blad e s m ount e d on two v e rtical
spindl e s which a r e drive n from ab ov e Th e trough containing the e xplosive
,
.

mixture is wh e e l e d in b e low and rais e d by m e ans of suitabl e g e aring Th e re .

a r e stop s to pr e v e nt th e bottom of th e trough coming in contact with t h e

stirre rs Th e trough has a doubl e wall through which hot wat e r can b e
.
,

FI G . 73 . P l n of Mc R o b t Incor
a er
'

s s FI G . 74 . C r t rid g M a c h in e for G l t in iz e d
a e e a

p o ra to r for B la s t in g G e l a t in e E xplosi v e s

ci rc ulat e d from a tank outsid e th e b u ilding maintain e d at a t e mp e rature of

50 C Th e actual t e mp e ratur e of th e mixtur e is 40 to Aft e r about an
° °
.

hour th e trough is r e move d and th e g e latin e i s allow e d to stand to g e t cool and

b e com e stiffe r but not too stiff In 1 9 1 4 and 1 9 1 5 two s e ve r e e xplosions
, .

occurr e d in th e mixing hous e s of th e Nob e l Co at Arde e r Th e y may have . .

b ee n caus d by dropping a l e ad apron into the mix e r

e
1
It is advisabl e that .

t h e machin e ry b e not running whilst t h e trough is b eing fi ll e d If th e stirr e rs .

a r e driv e n e l e ctrically th e r e should b e an automatic cut out to th e motor -

to pr e ve nt th e u s e of too much forc e .

Starting from th e th e ory that blasting g e latin e has a w e bb e d structur e ,

W A Hargre av e s Insp e ctor of E xplosiv e s in South Australi a has arri ve d

. .
, ,

at the opinion that it do e s not poss e ss suffici e nt s e nsitive n e ss u nl e ss th e re

b e a consid e rabl e amount of liquid nitro glyc e ri n e b e tw e e n t he w e bs He -
.

h e nc e c onclud e s th at the g e latin e is b e st made by first mixing t h e nitro cotton -

thoroughly in t he c old with par t of th e nitro glyc e rin e and th e n aft e r g e latin -
,

iz a tio n adding the re s t of th e nitro glyc e rin e It is claim e d that in this w a y

-
.

1 S ec S RR
. . Nos . 20 9 , 213 .
 Re fle c t e d light

T r a ns mi tte d ligh t

FI G . 75
.P ho t ogra phs o f B la s t ing Ge la t in es
(From Re po r t t o Pa r lia me n t of W Aus t ra lia by A E Ma nn )
. . .
 FI G . 76 . P ho t ogr a p hs of G e ligni t es
(Fro m Re por t t o Pa rlia me n t of W Aus t r a lia by
. A
. E M a nn )
.

FI G . P ho t o g ra phs of Sou t h Af ric a n Ge ligni te s

77
.

(Fro m Re po rt t o Pa rl i a me n t o f W Au s t ra l ia by A E Ma n n )
. . . .
 3 68 E X P L O SI VE S
blastin g g e latin e has b e e n manufactur e d w hich i s l e ss liabl e e ith e r to b e com e
in s e nsitiv e or on the oth e r hand to e xud e 1
.

Blasting g e latin e m ay b e mad e i nto cartridg e s i n t he machin e shown i n

Fig 72 or t he s au s ag e machin e i llustrat e d in Fig 74 may b e us e d for this
.
,
.

and o t h e r g e la t inous e xplosiv e s that a r e not too stiff Th e g e latin e i s fe d in .

t hrough t he hopp e r b whil st t he handl e is turn e d Th e Archim e de an scr e w

, , .

forc e s th e mat e rial forward and out of t he nozzl e the di am e t e r of w hich ,

c orre sponds w ith t he si z e of cartridg e to b e produc e d It i s n e c e ssary that .

t he j e lly should b e w arm during this op e ration a s oth e rwis e it bre aks up , .

Th e fo llo wi ng is t he approximat e output of cartridg e s of g e li gnit e g e latin e ,

d y nami te or blasting ge latin e in a day of hours by a gang of four

girls o ne worki ng th e cartridge machin e and th e oth e r thre e rolling car
,

tr idg e s

S iz e o f c r t ridg
a e

a re .

5 2 .

15 4 .

Th e re a r e groove s insid e t h e body to pr e v e nt the mat e rial rotating In all .

machi n e s us e d for w orking th e s e substa nc e s i t is e ss e ntial that only bronz e

or oth e r suitable all oy b e us e d and all b e arings must b e so arrange d that ,

t he nitro glyc e rin e cannot g e t in to th e m “ h e n th e nitro glyc e rin e i s hot

7
- -
.

it is d e cide dly m ore s e nsitive than wh e n c old .

B xes i o j elly
o r .
Th e box e s for conv e yi ng th e mixtur e of nitro glyc e rin e and c o llodi on c otton -

a r e usually mad e of wood lin e d wi th copp e r brass l e ad or rubb e r or of h e avy , , ,

copp e r tinn e d insid e and provide d with rubb e r rims Th e y should b e so .

constructe d as to pre ve nt as far as p ossibl e thos e surfac e s whi ch a r e liabl e , ,

to have e xp losive on th e m from c oming in conta ct with o ne anoth e r or with ,

th e support s on the b ogi e on which th e y a r e car ri e d Th e box e s should b e .

cl e an e d thoroughly at fr e q u e nt int e rvals An e xplosion that occurre d at .

Arklow on August 4 1 9 1 1 is ascrib e d to the n e gl e ct of th e s e p r e c a u, ,

tions 2
.

D i minuti n of
o
Aft e r manufactur e bla sting g e latin e c onti nu e s to stiff e n for a c onsid e rabl e
s n it iveness
e s ,

tim e and unfort unat e ly as it g e ts stiff e r it b e c om e s l e ss s e nsitiv e to de tonation

, , ,

so that old blas ting g e latin e may giv e a miss fi r e Thus Soddy found that .

g e lati n e s w hic h gav e r e sul ts of 570 to 600 c c in th e l e ad block wh e n first . .

te ste d aft e r k e e ping for a y e ar gav e only 340 to 420 c c wh e n fire d with a
, . .

No 6 d e tonator but gav e normal r e sults again wh e n a No 7 d e tonator was

.
, .

us e d 3
Inde e d it i s not e asy to produc e a c ollodion c otton which has th e
.
,

1
J . Soc . C he m I nd . .
, 1 9 1 4, p . 3 37
.
2
S R . ., No . 20 1 .
3
A . a nd E .
, 1 9 1 2, p . 22 .
 NIT R O GLYC ER IN E HIG H E X P L O SIV E S
-

right d e gre e of g e latinizing pow e r and i s at th e sam e tim e suffi ci e ntly stabl e and stab il ity .

to stand transport through the tropics to Australia for instanc e In 1 9 0 9 , , .

lb of g elignit e w e re cond e mn e d in W e st e rn Australia alon e on

.

ch e mical grounds .

Diminution of s e nsitive n es s of the g e latin e is accompani e d by in

cre as e o f stiff n e ss but the r e ason of th e s e chang e s is not w e ll und e r
,

stood . H a r g r e a v e s s th e ory has b e e n m e ntion e d above but it is not by

’

any m e ans c e rtain that a ge l such as blasting g e latin e has a we bb e d or

c e ll ul ar structur e Th e alt e ration must of cours e b e du e to som e chang e
.

i n th e structure of the particl e s but th e r e is no dir e c t e vi de nc e to show

,

what this structure is It is howe ve r a g e n e ral prop e rty of g e ls to s e t

.
, ,

slowly and sti ff e n gradually wh e n coole d again aft e r b e ing h e at e d and ,

th e long e r and strong e r th e h e at ing th e slow e r is th e s e tting in many ,

instanc e s Th e h e ating caus e s a diminution in the siz e of th e particl e s

.

and prolong e d storage in the cold may produc e th e r e ve rs e chang e Th e .

sti ff e ni ng may th e r e for e b e du e to incr e as e in th e si z e of th e particle s ,

or i t may b e du e to m or e p e rfe c t absorption or adsorption of th e nitro

glyc e rin e .

W h e n a colloid sw e lls up by imbibition of a liqui d it can b e made to e x e rt Exudati on .

gr e at pr e ss u r e on th e walls of th e containing v e ss e l Conv e rs e ly if suffici e nt .

,

pr e ssur e b e appli e d unde r such c onditions that th e li qui d can e scap e part of
it will b e e xpr e ss e d until e quili brium is again e stab lish e d This shows that .

th e imbibition is a r e v e rsibl e proc e ss but do e s not throw much light oth e r ,

wi se o u th e proc e ss Th e pr e ssur e re qui re d is small wh e n th e ge l i s v e ry

.

swolle n Som e blasting g e latin e s r e quir e so littl e pre ssur e to d e prive th e m

.

of som e of th e ir ni tro glyc e rin e that th e w e ight of th e cartridg e s i s suffici e nt

-

to caus e som e of it to e xude into or e v e n through th e wrapp e r of v e g e tabl e

, ,

parchm e nt .

B lasting ge latin e may c ontain anything up to 1 2 p e r c e nt of coll odion .

cotton but usua lly 7 or 8 p e r c e nt To incre as e its stability 1 or 2 p e r c e nt

, . .

of calcium or magn e sium carbonat e may b e adde d or a fraction of a p e r c e nt ,

.

of vas e lin e .

For most purpos e s blasting g e latin e is conside re d too e xp e nsive and is G lignite e ,

too viol e nt and local i n its action and c ons e qu e ntly e xplosive s a r e us e d i n
,

which it i s r e nd e re d mild e r by th e addition of oth e r mat e ri als G e li gnite is .

an e xplosive which i s ve ry large ly e mploye d it consists of 56 to 63 p e r c e nt .

of nitro glyc e rin e thick e n e d wi th nitro cotton to a thi n j e lly and mix e d with
- -

p otassium nitrat e and wood m e al with t h e addi tion som e tim e s of calcium
-
,

carbonat e or min e ral j e ll y .

G l tin
G e latin e d y namit e is a mixtur e ve ry sim ilar to g e lignit e e xc e pt that it dyna mite e a e
.

contains a larg e r proport ion of blasting g e latine : th e re may b e from 70 to

77 p e r c e nt of nitro gly c e ri n e in it
.
-
.

VOL . 1 .
 E X PL O SIV E S
Th e foll o w ing Table shows typical c ompositions for th e s e thre e standard
g e latini z e d e xp losive s

B l s t in g
a Ge l t in
a e

Th e wood m e al us e d f o r th e manufacture of th e s e e xplosiv e s should not b e

too fi ne oth e rwis e th e re i s di fficulty in obtaining compl e t e de tonation In
,
.

som e factori e s it is only sifte d through a m e sh of e ight hol e s to th e lin e ar

inch but in oth e r factori e s it i s fin e r Appare ntly th e air v e sicl e s in th e
,
.

coars e m e al assist t he de tonation and at the sam e tim e re duc e the de nsity
,

of the e xplosive Th e saltp e tr e and oth e r ingre di e nts if any a r e ground

.
, ,

mor e fi n e ly to pass a 50 or 1 00 m e sh si e ve Th e mixture should c ontain

,
-
.

s u ffici e nt oxyge n to c onve rt t he whol e of th e carbon pr e s e nt int o carbon

di oxid e so that non e of th e poisonou s carbon monoxide shall b e form e d to
,

W r a p p ers . foul th e air in min e s It has b e e n shown by Mann (R e port to t he W e st e rn

.

Australian P arliam e nt 1 9 1 1 ) that if the pap e r wrappings on the cartridge s

,

a r e r e mov e d v e ry littl e carbon m onoxid e is form e d not more than 2 p e r c e nt .

of th e carbon i s c onv e rt e d into this gas but with th e wrapp e rs on from 7 to 1 4 ,

p e r c e nt is form e d
. In Gr e at Britain wrapp e rs of parchm e nt pap e r a r e us e d
.
,

but on t he Contin e nt and in Am e rica th e y a r e oft e n of p a r a ffi ne d pap e r A wrap .

ping o f m e tal foil would have far l e ss re ducing action but th e fin e ly divide d ,

m e ta llic oxide would its e lf have a poisonous action Impre gnation of the pap e r .

with nitrat e s or simil ar m e ans would mak e th e cartridge s consi de rably more
inflammabl e For the avoidanc e of this dange r of poisoning with carbon mon
.

oxid e th e most e ffe ctive m e ans is undoubt e dly e ffici e nt v e ntilation of the min e s .

rt
Fo y p e rc ent
Dynamit e No 4 or 40 p e r c e nt dynamit e i s a som e wh a t similar mixtur e
t
. .

dyna mi e.
i t c onta i ns not mor e than 3 9 5 r c e nt of n i tro glyc r i n e g e lat i n i z e d w i th
p e e —
.

not l e ss than 0 7 5 p e r c e nt of nitro cotton and mix e d with sodium nitrat e

.
-

and not l e ss than 1 6 5 p e r c e nt of dry wood m e al and a littl e magn e sium

.
-

”
carbonat e It is som e tim e s sold und e r the nam e of Farm e r s Dynamit e
.
“ ’

for b re aking up sub soil making hol e s for tre e s and oth e r agric u ltural pur
-
,

pose s for which an in e xp e nsive e xplosive is r e quir e d It diffe rs from the

, .

ordi nary Am e rican 40 p e r c e nt d y namit e in that the nitro gly c e rin e is ge latin
.
-
 NIT R O GLYC ER IN E HIGH E X P L O SIVE S
-
3 71

and a larg e r proportion of wood m e al is us e d th e dange r of e xudation

i ze d -

is thus gre atly r e duc e d .

th e s e e xplosive s a r e call e d g e latins or g e latin dy namit e s ; ric

Ame an

1
th e y g e n e rall y have c ompositions approximating

35 p e r 40 p e r 50 p e r 55 p e r 60 p e r 70 p e r
c nt c nt
e . c nt c nt
e c nt
. c nt
e . e . e . e .

s t r n g t h s t r ng t h s t r n g th s t r n g t h s t r n g t h s t r ng t h s t r n g th
e e e e e e e

Ni t ro glyc rin-
e e

Ni t ro c e llulos
-
e

Sodi u m n it ra t e
Co m bu s t ibl m t e ri l 2
e a a

C lciu m c rb on t
a a a e

10 0 0 -
10 0 0 1 0 0 -0 1 00 0 10 0 0 1 00 0

A sampl e of 40 p e r c e nt ge latin e dyn amit e anal y s e d by . Cop e was found

to contain
Ni t ro glyc e rin e -

N it o c e llul os r -
e

Sodium ni t r a te
W ood m a l ’
-
e

Sulph u r
Zin c oxid e
M ois t u e r

1 0 0 00-

To pre ve nt th e formation of poisonou s gas e ous products of e xplosion Munro e

and Hall advis e th e omission of th e sulphur 3
Th e y r e comm e nd th e follow .

ing as a w e ll balanc e d formul a °

N it o glyc rin e r e

Ni t ro c llulos e -
e

S odiu m ni t t ra o

Flour
C lciu m c r b on t a a a e

ur u of M i n s B lletin 48
1
B ea e ,
u .

2
“ b o d pulp is us d in 60 n d i n 70 p
-
c n t s t r n g t h g l t in dyn mi t e Sulph u r
e a er e . e e a e a .
,

flour wood pulp

,
n d so m t ime s r s in a
-
,
u s d i n o t h r gr d e s So m m nuf c t ure rs
a e e re e e a . e a a

r pl c e s m ll p rc e n t g of t h e ni t ro glyc ri n in t h s e gr d s wi t h a n qu l moun t
e a a a e a e -
e e e a e e a a

of mm oniu m ni t r t
a T his r pl c m n t h ow v r off rs li tt l if a n y d v n t g o t h r
a e. e a e e ,
e e ,
e e , ,
a a a e e

tha n r educ in g t h cos t of m nuf c tur

3
e B ur u of M in s B u lle ti n No 8 0 p 27 a a e. ea e , .
,
. .
 E X P L O SIVE S
Thena m e F o rc ite is a lso e m ploy e d som e t im e s for ordi nar y g e lignite s
c on t a ini ng p o t a s i u m or sodium ni t ra te and wood m e al bu t som e tim e s also
s -
,

for mi xt ure s in v a ri ous p r opo rt ions of a t hi n blastin g g e lat in e wi t h an

a bsorbe n t ha vin g t he c omposi t i on :

In Be lgium Fo rc ite s w e re manufac t ur e d at Bae l e n sur N et h e , h avin g t h e

followin g compo siti ons :

Th e y a l so mad e wi t h co rr e sp on di n g pe r ce nta g e s of po t a ssium ni t rate

a re .

In Fran ce e xplosive s con t a inin g ni t ro gl y ce r ine a re e xc e p t e d from th e Sta te -

mono p ol y a la rge num be r of di ffe re n t compo i t ion have bee n au t horiz e d for s s

manuf ac t u re in t he p riva t e work Th e fo llo w in g a re som e e xample s (C hal on )

s .
1

D yn a m i te gc-mme
-
G ela t ine

l ni t
G e ig e

So ude A

92 93 82 83 82 83 64 5 m)
l !

— — —
C

6 5 6 5 3 v 0
1

- —
I

P ot a ss iu m ni t tra e

An y ni t ro gl y ce rin e e xplosive s can b e mad e wi t h low free zing ni t r o

of t he - -

glyce r in e (see Chap t e r X VI ) The m e t h ods of incorpo r a t ing t he e xplosive s

.

a re t he sa m e as if o r d ina ry ni t ro l ce zi ne w e r e use d In E n land wh e re g

g y
-
.
,

1 Ve nn in et Ch n ea u p
es , . 3 69 . S ee a Ch a lon p
l so , . 29 5 . For s im ila r e xpl o s i ves ma d e
in Sw i t ze r la n d se e B . Zs c h o kk e , S S . ., 1 9 09 pp 1 4 3
, .
,
1 44 .
 NI T R O GL YC E R IN E HIG H E XP L O SIVE S
-
3 73

th e wint e rs a r e not so v e ry s e ve r e r e li anc e is plac e d rath e r on k ee pin g th e ,

magazin e s warm than on making ad di tions to th e e xplosive mixtur e s but ,

on th e Contin e nt and in Am e rica a conside rabl e numb e r of such e xp losive s

a r e in u s e
. In G e rmany and Switz e rland s e v e ral sp e cial blasting g e latin e s
and g e lignit e s a r e mad e containing a p e rc e ntag e of li qui d nitro tolu e n e or -

oth e r nitro aromatic compounds or glyc e rin e e st e rs In Austria the follow

-
, .

ing a r e manufacture d :
D yn m i t I a

s c h w e r fr ie r b a r

Ni t ro glyc r in e -
e

Ni t ro c e llulos -
e

N it o t olu e n e
r -

VVo o d m e l -
a

R y e fl our
Sodiu m ni t r a t e
L a m p bl c k -
a

C pu t m or t uu m
a .

Sodiu m c a b o n a t e r

following i s a Fr e nch e xplosive this class

N it o glyc e r in e
r

Ni t ro glycol -

Ni t ro co tt on -

P o t ssium ni t r a t e
a

W ood me a l
In Am e rica low fre e zin g dynamit e s a r e mad e which di ffe r from th e corr e
-

“
s p o n di ng straight dynamit e s in that about a quart e r of th e nitro glyc e rin e -

i s re plac e d by nitro substitution compoun ds 1 -

Th e Re d Cross dynamit e s .

mad e by th e E I du P ont de N e mours Co a r e e xplosive s of this class

. . . .

Th e following a r e th e compositions of typical low free zing dynamit e s a s -

give n by C E Munro e and C H all :

. .
2
.

30 p e r 35 p e r 45 p e r 50 p e 55 p e r 60 p e r
S t r ng t h
e
c nte . c nt e . c nt
e . c nt
e . c nt
e . c nt
e .

Ni t ro glyc e ri ne
N t o su b s t i t u t ion c o m p o md
i r r s

Co mb u s t ibl e m t e ri l a a

Sodiu m ni t r t e a

C a lciu m or m g n siu m c a rb on a t
a e e .

The c omposition of c ombustibl e mat e rial is similar to that in

th e corre
“
s p o n di n g straight dynamit e s .

1
S ee H ll n d H ow ll B ur a u of M in s B ll 4 8 p 7
a a e , e e ,
u .
, . .

2 B ur u of M in e s B ll tin No 8 0 p 22
ea ,
u e .
,
. .
 E XP L O SIVE S
Th e of th e se low free zing ni tro gly ce rin e e xplosive s dimini sh e s the
u se - -

da nge r of solidi fi cati on but doe s not ove r c om e it e ntire ly If th e we ath e r

, .

b e ve ry cold it is sti ll n e c e s sa ry th e re fore to mak e u se of thaw house s and -

wa rmi ng pa n s to pre ve nt acc ide nt

-
.

Th e re a re a num be r of e xplosive s mad e which co ns ist practically of ge ligni te

in whi ch part of th e pota ssium nitrate ha s be e n re pla c e d by amm onium
o xa la te or a co mpoun d conta ini ng much wate r of crysta lli zation such
,

as m a gnes ium su lphate so a s to slow down the e xplosion and r e duc e

,

t he te mpe r a tur e of t h e flam e Th e se a re mostly use d for blasting coal Th e

. .

mos t la rg e ly us e d of a ll th e Per mi tte d E xp losive s in Grea t B rita in w a s

a t o ne ti m e Saxoni te m a de by Nobe l s E x plosive s Co Th e consumption
,
’
.

in 1 90 7 unde r the Co al Min e s Re gu lation Act wa s —

lb B ut in 1 90 9 .

it fa il e d wh e n t e te ste d in th e te sti n g gall e ry and was re move d from th e lis t

—
.

It was p r omptly re place d by Samsoni te in whi ch th e limi ts of c omposition ,

a r e consid e ra bly na r row e r and of whi ch lb w e re u se d in 1 9 1 0

, . .

Saxoni t e is still u se d howe ve r wh e re pe rmi tte d e xplo sive s a r e not compulsory

, ,

and in 19 1 1 t he consumpti on w a s lb .

Sa x o ni t

Nitr o glyce rin e

-

Ni tr o c o tto n
-

“b od - me a l

Amm oni um oxa la te

W hils t t h e T e st wa s in forc e a num be r of oth e r e xplosive s ve ry

'

li o o lwi c h

s imila r to Sam s onite w e re on the Pe rmit te d List : Ar kite Ripp ite Sto wi te , , ,

Co rnish P owde r Sw a li te amongst oth e rs

, ,
.

To pas s t h e more se ve re R oth e rha m Te st i t h a s bee n found n e c e ssary

to re duce t h e pe rce nta g e of nitro glyce r in e and increa se t h e am ount of ni trate
-

and o xala te Th e following a re on t he Pe rmitte d List

.
1

Ar k i t N 2 D it e , o . ux e

32 32
l l
27

Amm oni um oxa la t e

M ois t ur e
M a xim u m c h a rg e, oz .

P o w e r (s w in g of bal .
pe nd .
)
1
In t he E r p lo e i ree i n C oo l M i ne e Orde r s t he l m i t
i s of co mpo si t ion a r e p u bl ish ed .

H r onl
e e y th e a ppro ima t e m ea n s a r e s t a te d
x t h e w ood m a l t be in g gi ve n in t h e
,
-
e ,
e c .
,

na t ur a l dr y s ta t wi t h a bo u t 1 0 pe r c e n t of it w igh t of m ois t ur e
e . s e .
 NI T R O -
GLYC ER IN E HI GH E XP L O SIV E S 3 75

Th e following have pass e d th e B e lgian t e st an d a re on th e list of e xplosifs

G r is o u t ite

Ni t ro glyc e rin - e

C llul os
e e

Sodiu m sulph a t e
M g n sium s ulph t
a e a e

Ch a rg li mi t e e

E qu i v a l e n t dyn a m i t e N o
, . 1

Th e r e i s also Grisoutin e II which is practically the sam e as Dynamit e Anti

,

grisout e us e V .

On e of th e e arli e st and m ost succ e ssful safe ty e xplosiv e s was Carbonit e ,

r it e
Ca b o n

w h ich was made by Bich e l and Schmidt first about 1 8 8 5 and aft e r und e r ,

going som e mo di fications gave satisfactory r e sults at the N e unkirch e n t e st

ing station in 1 8 8 7 It c onsists of nitro glyc e rin e about 25 p e r c e nt
.
-

, .
,

absorb e d in wood m e al and mix e d with nitrat e s Th e proportion of wood

-
.

m e al is so high that a large proportion of th e carbon i s only oxidi z e d to

mo n oxid e

Th e composition has b e e n vari e d by th e substitution of oth e r nitrat e s for

thos e m e ntion e d and of r y e starch and oth e r carbo hydrat e s for wood m e al
,
- -
.

Th e c omposition has b e e n imitat e d by many oth e r manufactur e rs Th e .

fo llowing a r e som e of th e e xplosiv e s of this typ e that pass e d the W ool w ich
t e st :

Ca r boni t e Tu to l K o la x

Ni t ro glyc e rin
-
e

P o t ssiu m ni t r t
a a e

B riu m ni t r a t
a e

“ b od m l -
ea

St a rch
Sulphur tt d b n z n e
e e e e

C lciu m c rb on t
a a a e

S o d iu m c rb on t
a a e

Sod iu m b ic rb on t a a e
376 E XP L O SIV E S

Th e re a re a num b e r of e xplosive s of thi s type on th e B e lgian li st of

e xplos ifs

Ni t ro gly c e rin
-
e

P ot ssiu m ni t ra te
a S od ium ni t r a t e

B a riu m ni t r t a e Di ni t ro t olu n e
-
e

Flour 39 5-
Amm o ni mn sul pha t e

T n m l
a -
ea C llulos
e e

S od a 0 5-
“ b od m -
l ea

Ch rg li mi t
a e e Cha rg lim i t
e e

E qui v l n t a e E q ui v a l n t e

Mi ne r ite and Coli mit e a n tigr is o u te u s e hav e t h e sam e c omposition as K ohl e n

carbonite and Se c u r o p h o r e III onl y di ff e rs from it in havin g 1 p e r c e nt w ood
,
.

m e al instea d of tan m e al : it s charge li mit e i s 8 50 gram s e quival e nt t o

-
“

5 48 gram s Dy na mi te No 1 I n g e li te i s ide ntical wi th Antig e l de s ur e t e

' '

. . .

To pass th e R oth e rham t e st it has bee n foun d n ec e ssary to add a c oo ling .

ag e nt such as a mmonium oxalate :

S u p r Kol
e -
a ):

C a m b r it e

Ni t ro gly r in
-
ce e .

C oll od ion c o tt on
P o t siu m ni t ra t
a s e

B riu m ni t r t
a a e

St rch
a

A mm oni um ox l t a a e

C lcium r b o n t
a ca a e

M xim u m cha rg oz
a e , .

P wo ( w in g of b a l p nd ul
er s . e u m , in ch s )
e

Som e ammoni um ni trat e e xp losive s also hav e a small p e rc e nta ge of ni tro

glyc e rin e add e d to re nde r th e m l e ss inse nsitiv e and t o mak e it possibl e to com ,

pre ss th e m t o a h igh e r d e nsity w ithout maki ng th e m too di ffi c u lt to de to na te .

Th e s e a r e d e alt wi th in Chapt e r X X VI I Th e pota ssium pe rc hl orate e x .

plosive s d e alt wi th in Chap te r XX VI also ge n e rall y con tain ni tro glyc e rin e -
.
 C H AP TE R X X VI

H
C LO R ATE EX L O SI VES P
Chlor a t e d a nge rs : S pr e ng l e xplosi v e s P o m é t h ée or 0 3 : Ra c k a roc k
e : r - -

Ch eddi t e : Ste e lite : S il e si a : P o t s s ium pe rc h lor t e e xplosi v e s

a P e r m o n ite a

Al k a ls it : P ol ri t a a MB powd e r . Amm oni um p e rchlor a t e e xpl o s i v e s

:

Y o n c ki t e B la s t i ne

TH E substitution of potassium chlorat e for saltp e tre in an e xplosive mixt ur e Ch l o r a te

da ng r
i ncr e as e s its pow e r and vi ol e nc e but also it s s e nsitiv e n e ss A favourite , .
e s :

mi xt ur e has b ee n whit e g i mp o w de r for w hi ch the follo w ing proportions ,

hav e b ee n r e comm e nd ed :
A g nd Poh l R v l y u e re a e e

P o ta ssiu m chlor a t e 50 49 48
P o ta ssiu m f e rrocy a ni d e 25 28 29
Su ga r 25 23 23

Mi xtur e s of chlorat e and sulphur or a sul phi de a r e sp e cially s e nsitive H e nc e .

t h e e arly att e mpts to mak e gunpowd e r with chl orat e le d to di saste r Such
"
.

mixtur e s a r e us e d for p e rcussion cap s and for oth e r p urp os e s wh e r e a ,

high s e nsitive n e ss is r e quir e d Th e y hav e also b e e n use d for th e manufactur e .

of colour e d lights and oth e r sim ilar fi r e works but in E ngland thi s i s now -
,

forbidde n Me ans hav e b e e n found howe ve r to mak e blasti ng e xplosive s

.
, ,

c ontaining chlorat e which a r e not mor e dange rou s than oth e r e xp losive s
,
.

Th e p e rchlorate s a r e much l e ss s e nsitiv e than th e chlorat e s and as th e y a r e ,

now manuf acture d at mod e rate c osts th e ir u s e in e xplosive s is e xte nding ,

rapi dl y Mi x tm e s conta i ning sodi um c hlorat e a r e more dange rous than

.
'

those c ontaining potassium c hlorate 1

.

U nd e r ordin ary cir cumstanc e s chl orate of potash wh e n unmi x e d w ith ,

combustibl e matte r is not dang e rous bu t on Ma y 1 2 1 8 9 9 a larg e quantity

, , , ,

of it e xp lode d during th e progr e ss of a fi r e at th e works of th e Uni t e d Alka li

Co at St H e l e ns and di d an e normou s amount of damag e
. .
,
2
This le d to a .

mor e thorough e xamination of th e b e haviour of potassium chlorate wh e n

h e ate d B e rth e lot showe d that if i t b e sub j e cte d to a blow c omb in e d wi th
.
3

1
S ee A R . .
, 1 9 0 4, p . 28 .
2
S R . .
, No . 1 35 .

3 P . et S ., v ol . x .
, 1 90 0 , p . 28 0 ; C o mp l . Re n d .
, 18 9 9 , v ol . 1 29 , p . 9 26 .

3 77
 3 78 E X P L O S I VE S
sudde n inte nse h e at it e xplode s ; he de vi se d th e followin g e xp e rim e nt : A
glass tube 25 to 3 3 mm in di am e te r close d at o n e e n d is supporte d in a n ea rly
.
, ,

ve rt ical posi t ion and h ea te d in th e flam e of a larg e gas burn e r u nti l th e

,
-
,

low e r part ha s a t tain e d a p e rce ptibl e r e d h e at A glass rod i s dr awn out to .

th e t hi c kn e ss of a c oars e thr ea d th e n introduc e d into a quantity of pur e ,

pota s i u m c hlora te whi ch has bee n m e lt e d in a p orc e lain crucibl e wi thdra w n

s , ,

and allowe d to c ool unt il th e salt be gins to solidify The ope ration is r e pe ate d .

s e ve ral tim e s u ntil a fe w d e cigra mm e s of soli di fi e d salt a r e accumulate d in the

form of an oval lump on the e n d of th e glass thr e ad “ h e n the glass tube .

is qui t e re d the glass rod i s introduc e d un til the potassium chlorate i s with in
,

about 10 mm of t he bottom car e b e in g tak e n that it do e s not touch th e tube

.
,

anywh e re Afte r a short time th e chl orat e m e lts and falls drop by drop on
.
, ,

to th e r e d hot botto m of t he tube E ach d rop e xplod e s at th e insta nt that

-
.

it c om e s in contact with t h e glass producing a v e ry dist inc t soun d and a ,

cloud of whi t e smoke .

Dupr e showe d th at h ea t alon e suffic e s to e xplod e th e c hlorate if it b e

1
,

app li e d wi t h suffici e n t sudd e nn e ss A b e ad of p ota ssium chlorat e supporte d .

,

in a loop of thi n platinum w ir e can b e made to e x plode by h e atin g it rapidly ,

e i t h e r in a gas flam e or by m e ans of an e l e ctric cur r e nt .

Sinc e the St H e le ns di saste r th e r e have b ee n s e ve ral oth e r instanc e s in

.

whi ch conside rabl e quantiti e s of pota ssium chlorate hav e e xplode d in the
cours e of c o n fl a gr a tio n s O n July 27 1 9 0 8 an e xplosion of thi s sort occ u rr e d
.
, ,

on t h e pre mis e s of a carrying company in Manch e ste r 2

and on Jul y 21 1 9 1 0 , ,

ano th e r at t h e match w orks of Me ssrs Bryant and Ma y at S e aforth n e ar

-
.
, ,

Live rp ool 3
In 1 9 1 2 an e xplosion took plac e dur ing re pa irs to a di y i ng
.

mac hine fi v e me n be ing kille d 1

Although potassium c hlorate i s not classifi e d
.
‘

officiall y a s an e xplosiv e y e t wh e r e larg e quantiti e s a r e store d th e y sho ul d b e

,

k e pt in an u ni nfl a mma b le buil din g s e parat e from all combustible mate ri als , .

Th e in te ns e in fla mmabili t y of wood a nd oth e r organic matt e r wh e n ,

impr e gnate d w i th c hlora te shoul d b e born e in mind ,

Th e e xp losibil ity .

of chl orate i s caus e d by the fac t that h e at i s li b e rate d wh e n it de c o m

pose s into pota ss ium chl oride and oxyge n It doe s not e xplod e wi t h gr e at .

viole nc e .

Chl orate e x plosive s may b e r e nde re d re asonably safe by adop ting th e

de vic e of Spre nge l and i ssuing t h e chlorate s eparate ly from th e c ombustibl e
matte r The pota ssium chlorat e i s mad e up into porous ca r tridg e s and a
.
,

liquid c ombustibl e i s u se d ; t h e form e r i s dipp e d into t he latte r j us t b e fore

u se. Th e s e e xplosiv e s a r e not all ow e d i n Gre at B ritain as t hi s di pping op e ra ,

t ion is c onsid e re d t o c ons t itute a proc e ss of manufac tur e and cons e qu e ntly ,

may only b e carri e d o u t in a dul y lic e ns e d factory .

1
J S . C h m I nd
oc . 190 2 p 2 ]
e . .
2
S R
, 18 5
, . . .
, .

3
19 10 p 4 1 , . .
4
A R 1 9 13 p 3 9 . .
, , . .
 C H L OR AT E E XP L O SIV E S 3 79

A Spr e nge l e xplosive i s mad e i n Franc e un d e r th e nam e of E xplosif O3 Pr o mé th é e

or
or P r o me th e e e i th e r t h e oxyg e n carr i e r or t h e c o mb u s tl b le can b e var i e d
I I 0 0 0 0

P o t ssiu m chl or a t
}
a e .

O xyge n c rr r
a ie 9 2 1 0 8 7 per ce nt
M n ga n s d ioxid
a e e e
.

Co m bus t ibl e 8 to 13

Any c ombination of a b or c with 1 or 2 can b e us e d Th e e xplosive is sold , .

at th e pric e of Fr 3 p e r kg Th e amount of li quid combustibl e tak e n up by

. .

th e so lid oxyg e n carri e r may vary from 8 to 1 3 p e r c e nt This irre gularity .

i s a s e rious d e fe ct and may caus e incompl e t e d e tonation 1

.

Th e r e i s also a factory for P rom e th e us e xplosive at Sant E us e bio n e ar .

,

G e noa in Italy wh e re a s e ve re e xplosion took plac e on Ma y 1 0 1 9 0 9 kil li ng

, , , ,

th e manag e r h e ad for e man a customs o ffic e r and e ight w o r kme n j a n d in j uring

, ,

thre e oth e rs 2

R ack a rock which has b e e n us e d ve ry e xt e nsive ly in Am e rica Sib e ria R ck

.

-
- -
a a -r oc
, , ,

and China consists of cartridge s of chlorat e of potash which a r e dipp e d j u st

, ,

b e fore u se into a combustible o il For this purpos e ni tro b e nz e n e i s use d or .

-
,
”
d e ad oil which c onsi sts chi e fly of hydrocarbons from coal tar or a mixture
, ,

of t h e two The chlorat e cartridge s a r e e nclos e d in small bags of cotton :

.

b e for e u se th e s e a r e plac e d in a wir e bask e t susp e nde d from a spring balanc e

and dipp e d into a pail containing the liquid until a quart e r to a third of th e ,

w e ight of th e chlorat e has b ee n tak e n up Th e chl orat e som e tim e s contains

an addition of a fe w p e r c e nt of iron oxide Consid e rabl e quantiti e s of R ack
.

. .

a rock w e r e i n stor e at P ort Arthur and Da lny at th e comm e nc e m e nt of t he

—

R usso Japan e s e W a r and we r e us e d i n th e e arly op e rations

- 3
, .

P r o mé thé e is similarly issu e d in th e form of compr e ss e d cart r idg e s and ,

t h e Fr e nc h Gov e r n m e nt has re fus e d to mak e it i n th e form of grains as t h e ,

dang e r of ignition by friction during manufactur e and u s e would b e gre atly

incre as e d 1
Th e Gov e rnm e nt has also r e fus e d to issu e it r e ady impr e gnat e d
‘
.

with th e combustibl e as it would th e n poss e ss no advantag e ov e r Ch e ddit e ,

6
.

1 Ve n ni n et h sn e u p 3 50
C e a , . .

2 AR . .
,
1 90 9 p 35 , . .
3 S S . .
,
1 90 8 , p 19
. .

1 P . et S v ol x v 1 9 10 p 130
.
, . .
, ,
. .
5
P . ci S ., v ol x v p
. .
,
. 148 .
 3 80 E X P L O SIVE S
An e xplosive of thi s sor t has how e ve r be e n introduc e d rec e ntly in G e rm a n y , ,

in ord e r t o ec onomiz e nitrate s dur in g the war 1

.

If a charge of Spre nge l e x p lo s iv e b e fir e d with a prim e r of black powde r ,

it shoul d b e so mad e up that admi xtur e i s impossibl e : a compre ss e d p e lle t

of blac k powde r wrapp ed in impe rm e abl e pap e r may b e us e d for instanc e .

Th e pri m e r of blac k powd e r should b e not l e ss than 1 0 p e r c e nt of t h e w e ight . .

of th e charg e w ith a mi nim um of 25 g (say 1 .

ite
Ch edd . It was di cov e re d b y E A G Stree t of t he fi r m of B er g é s Corbin e t Ci e
s . . .
, , ,

t hat t h e dang e rous s e nsi t iv e n e ss of chlorate mi xture s c oul d b e r e duc e d by

coat ing the chlorate wi th an oil y mate ri al such as castor oil thi ck e ne d by ,
-

havin g a nitro hydr o carbon di ssolve d in it 2

-
E x plosive s made on thi s p
-
.

c ip le hav e bee n e xamin e d from t im e to ti m e by th e Fr e nch Commission de s

P ou d res e t Sa lp é tre s and th e manuf acture of se ve ral has b e e n unde rtak e n

,

by t h e Sta te 3
Th e y a r e call e d Ch e ddi te s from Ch e dd e th e plac e in Hau t e
.
,

Savoi e wh e re t h e above nam e d fi r m manuf actur e s chl orate s by e l e ctrolytic

,
-

m e t hods I t has b e e n fou nd n e c e ssa ry to k ee p t he proportions of t he various

.

consti tu e n t s within c e rta in li mi t s in ord e r t o produc e an e xplosive that shall

poss e ss the right de g ree of s e nsitive n e ss and shall not b e li abl e to e xude oil .

It was also found that th e v e locity of d e tonation of Ch e d di t e vari e s c onside r

ably w ith t he de nsity to whic h it is compre ss e d : with i ncr e ase of de nsity
th e v e locity of d e to nation ris e s until it r e ach e s a ma xi mum and th e n falls
r apidly T hi s fall is du e to th e fact that th e e xplosiv e b e com e s v e ry ins e nsitive
.

to d e to nation wh e n t h e d e nsity e x ce e ds a c e rtain critical valu e and thi s ,

diffic u l t y can onl y b e ove rcom e to a slight e xte nt by th e u s e of a strong e r

d e to nato r S om e of t he ea rli e r pre parations w e r e fou nd to incre as e in d e nsity
.

on k ee ping and c ons e qu e n t ly to di minish in s e nsitiv e n e ss but thi s was trac e d ,

to t he s e of d nitro to
u i l u e n e whic h had b ee n i ns f ici e ntly pu ifi e d
u f r - 4 -
Th e .

ni tro body shoul d n o t m e l t b e low 60 e ls e th e r e is dang e r of e xudation

- 5 °
.

The e xplosiv e s a r e e a sily compr e ss e d and th e r e fore th e re i s dang e r of di min ,

is hi ng th e s e nsitiv e n e ss t o o much if charg e s a r e ramm e d hard i n t h e bore

hol e .

Variou s att e mpts hav e be e n made to produc e a satisfactory Ch e d di te in

whi ch th e pota ssium chl orate is r e plac e d by th e ch e ap e r sodi um salt which ,

c onta in s a large r p e rc e ntag e of oxyg e n bu t th e mixtu r e s first made we re ,

foun d to b e too ins e nsi t ive wh e n th e de nsity e xc e e d e d quite a mod e rat e ,

amount and v e ry compr e ssibl e More ove r sodi um c hlorate is v e ry h yg r o

, .
,

sc opic and wh e n ground gi ve s rise to a gre at d e al of dust which mak e s t he

, ,

1
S S . .
, 1 9 1 5, p p . 55 , 5 6 .

2 En g . Pa t . a nd of 1 8 9 7 ; G er. Pa t . of 1 8 9 7 .

3 P . e! S .
, v ol xi p 22 ; . . , . v ol xii p 1 22
. . . .
, 1 30 ; v ol xi ii
.
, pp 29
. , 1 44 , 28 2 ; v ol
xi v p
.
, . 33 ; v ol x v pp 212
. .
, .
, 24 7 .

1 P . ci S .
, v ol p 33 . . .
5 P . ct S .
, v ol x iii
. .
, p . 1 4 4.
 CHL OR AT E E X P L O SIV E S 38 1

work e r s clothing and similar mat e rials v ery infl a mma b le

’
Th e work e rs .
1

with thi s substanc e in t h e powd e r w orks at Vo ng e s a r e oblig e d not only to

chang e th e ir cloth e s but to hav e a compl e t e bath wh e n th e y l e av e off work
,
?

How e v e r it was found that a mixture cont a ining 1 6 p e r c e nt of di nitro

,
.

tolu e n e and no nitro naphthale n e could b e fire d up to a d e nsity of 1 65 and

- -

wa s mor e pow e rful than th e oth e r typ e s 3

Th e fo llo w ing Ch e ddit e s a r e .

authori z e d in Franc e

0 1
T yp 60 b is T yp 60 b is M '

P o t ssiu m c hlor a t
a e

Sodiu m chlor t a e

C s t or o il
a -

Mo n o n it r o -
na p h t li a lc n c
D ini t ro t olu n -
e e

Pa r a ffin
P ric e , Fr .
p er kg .

Th e Ch e ddi t e s most mad e in Franc e a r e 0 2 (oth e rwi s e Ch e ddit e No accord -

.

ing to formula 60 bis M and 0 5 (oth e rwi s e Ch e ddi t e No ,

-
.

In making Ch e ddit e th e nitro compounds a r e first di ssolve d in th e castor -

Ma uufac tur
oil at 8 0 C and th e fin e ly powd e r e d dry warm chlorat e i s th e n add e d gradu
°
.
,

ally whilst th e mass i s stirr e d with a wood e n rod Th e inc orporation of a

, .

charg e of 25 kg lasts about ten minut e s Th e mat e rial is th e n carri e d to

. .

anoth e r buildi ng wh e r e it i s furth e r mix e d on a wood e n board in a half cold

,
-

c ondition for anoth e r te n minut e s so as to g e t it in a sui tabl e granular con ,

dition E a c h p a r tic le of chlorate should b e e ntir e ly coat e d with th e o ily

. .

mixture Th e mat e rial is n e xt sift e d and what i s too fi ne i s add e d to a lat e r

.
,

charg e That which i s of th e c orre ct siz e i s made into cartridg e s by ramming

.

it into woode n moulds from which it i s transfe rr e d to pap e r cas e s If th e

, .

e xplosiv e c onta in sodium chlorat e th e cas e s shoul d th e n b e dipp e d into ,

molt e n para ffi n to pr e v e nt the absorption of wat e r If the p e rc e ntag e of .

moisture ris e abov e 1 p e r c e nt t h e e xplosibility i s impaire d .

, .

Ch e ddite is a soft y e llowish mat e rial of fi ne grai n but i s som e tim e s arti ,

fi c ia lly coloure d In cons e qu e nc e of its plasticity it can e asily b e compre ss e d

. .

It i s g e n e ra lly put up into cartridg e s 22 cm long and 2 5 cm diam e t e r Ch e d .

-
. .

1
P . et S .
, v ol xi v p 26 ; v ol x v p
. .
, . . .
, . 1 35 .

2
Ve nn in e t C h sn u p 1 23
e ea , . .

3
P . et S .
, v ol x v i p 66
. .
, . .
 E X P L O SIV E S
di te 4 1 is a slow mil d e xplosive which spli ts rocks rath e r th an shatt e rs the m , .

Ch e ddi te 60 is more vi ol e n t and t h e Sodi um Clorato Ch e d di te 0 5 still more , , ,

so Th e v e loci t y of d e tonation of Ch e d di te 0 was m e a s u r e d by Lhe ur e

. 6 1

and foun d to b e 3 1 75 m e t re s p e r s e c about half of th at of picric acid blasting .

, ,

g e la tin e and oth e r v e ry high e xp losive s and that of 0 2 2750 m e tre s p e r

, ,

?
sec

Man y o th e r mi xt u re s on sam e principle a s ch e d di te have bee n t ri e d the

in Franc e and e ls e wh e re such as 0 4 a mixtur e of 9 0 parts pota ssium chl orate ,

and 1 p a ra fli n wax
0 3
Sé b o mi te conta ini ng tallow and di nitro be nz e n e or.
-

ni t ro to lu e n e ‘ 0 6 or min éli te c onta ini ng h ea vy p e trole um mi n e ral j e lly and

-
,

pa ra ffin wax
'

St ee lite c onsists e ss e ntially of pota ssium chl orate th e particle s of which ,

a re e nv e lop e d in o xi di ze d r e s in which is mad e as fo llows 9 parts of groun d ,

colophony a re mix e d w i t h 1 part of starch and to this mi xture ni tric acid ,

of 1 4 ] sp e cific gravi ty (67 5 p er c e nt H NO ) is adde d at th e ordi nary te mp e ra -

.
a

t u re wi t hout th e addi tion of any s ul p ln ui c acid A n oxi di z e d y e llow amor

,
.

phons mass is thus form e d whi ch floats on th e top of the acid Thi s is broke n ,
.

up wash e d wi th wate r dr i e d at a mode rate te mp e ratur e and groun d up

, , , .

I t is not e xplosive w ithout th e addi tion of chlorate and onl y burns with ,

diffi cul ty I t is mi x e d with th e ground chl orat e and oth e r constitu e nts in
.

a dr um w th lignum vi t ae ba lls Th e mi xt u re i s spre ad on a zi nc sh e e t i n

i
.

quantiti e s of 1 to 5 kg and sp ri nkl e d with m e thyl alcohol whilst it i s ra ke d .

-
,

about so t hat a paste or dough may not b e form e d It is k e pt i n g e ntle motion

,
.

wi t h a wood e n tool u nt il it is dr y .

S e ve ral sampl e s of Stee li te w e r e e xamin e d by th e Fr e nch Commission

de s Substanc e s E xplosiv e s but it was de cid e d n ot to un de rtak e its ,

manuf act u re on t he gro u nd that it poss e ss e d no advanta g e s ove r

Ch e ddite than whi c h it wa s mor e s e nsitiv e and l e ss d e ns e
,
6
Colli e ry .

Ste e li te c o n ta in ing a sma ll p e rc e nta g e of caste r o il pass e d t h e W oolwich

‘

t e s t for s afe ty e xplosive s and was form e rly on th e E nglish p e rmi tte d “

li st .

In G e r many t hi s e xplosiv e i s call e d Sil e sia u noxi di z e d re s in is

appare n tly us e d in it som e t im e s and to mak e i t pass th e Cont in e ntal ,

t e s t s for sa fe t y e xplosive s a c on s ide rabl e proportion of sodi um chlo ri d e

i s adde d Th e follo w ing a r e som e of t he compositions that hav e b e e n
.

m a de
1
P . cl S .
, v ol xii p 1 1 7. .
, . .
2
Ve m in e t Ch e sn ea u p 3 59
r , . .

3
S ec P .
cl S v ol x v pp 2 1 2
.
, . . .
, 24 7, a ls o l st ed . of t his work p 29 8 a n d Ve nn in
, .
, et

C h sn u p 3 5 9
e ea , . .

4
P ct S v ol xiii p . .
, . .
, . 28 0 , a ndv ol x v p 1 36 . .
, . .

P t S v ol x v p V m in e t Ch sn u
O

5
. c .
, . .
, . 212 ; er e ea ,

9 P t S v ol x v p . c .
, . .
, . 1 8 1,
 CHL OR AT E E X P L O SIV E S

C o ll i ry St
e e e l ite No . 3 No . 5 S i l si
e a I v 22

P o t a ssiu m Chlor a t e
O xi diz d r e si n
e

C a s t or oil-

Al u mi n iu m
Sodi u m chlori d e .

M ois t ur e

Th e Sil e sia e xplosive has a large e xc e ss of chlorat e and th e gas e s produc e d ,

contain 1 4 2 p e r c e nt of fr ee oxyg e n 1
.

In Austria a chlorat e e xp losive ca ll e d C h lo r a tit h a s b e e n sanction e d for

r
u s e i n coal min e s du ing th e war
?
It give s ris e to bad fum e s and i s h y g r o
scopic .

Chlorat e s should n e ve r b e mix e d with ammonium salts as ammonium ,

chlorate w ould b e form e d and thi s i s liable to e xplode spontan e ously Mi x

, .

ture s with picric acid or trinitro cr e sol also shoul d not b e made as th e y a r e -
,

v e ry s e nsitiv e .

P O TASSI UM P ER CHL O RATE EX P L OSI VES

Th e p e rc hl orate s poss e ss th e advantag e ove r the chl orat e s that th e y ,

a re mor e stabl e and l e ss s e nsitiv e although th e y contain a larg e r pro ,

portion of oxyg e n Cons e qu e ntly e xplosive s containi ng p e rchlorat e s do

.

not r e quire to hav e e ach particl e e ncas e d in fatty matt e r a s is t he ,

cas e w ith chlorate e xplosiv e s Sinc e th e introduction of e l e ctroly tic

.

m e thods of ma n u fa c tu ii ng p e rchl orat e s th e s e e xplosive s hav e b e e n us e d ,

e xte nsiv e ly A c e rtain amount is obtain e d a s a b y product in w or king up

.
-

Chili ni trat e : 5 5 tons of potassium pe rchlorat e w e r e e xport e d from Ch il e in

19 14 .

E xp losiv e s containing p otassium p e rchlorate and ammonium nitrat e Per mo nite .

tog e th e r with trinitro tolu e n e starchy matt e r and wood m e al a re mad e by

-
,
-
,

”
t h e Spr e ngstoff A G C a r b o n it und e r t h e nam e of
-
.
-
. P e r mo n ite On e of .

”
th e s e compositions was form e rly on th e E nglish p e rmitt e d list and anoth e r “
,

i s on the B e lgian li st of E xplosifs S G P G e st e ins Pe r mo ni t is us e d i n potash . . .

-

and o r e min e s Th e following a r e the compositions tog e th e r w i t h oth e r

.
,

particulars as stat e d by th e mak e rs '

1
S ee E sc l sa e , C h lo r a ts p r e n gs to fl e , 19 10 , p . 1 43 ,

2
S S . .
,
1 9 15 ,
p . 29 4 ,
 P e r mo n i t I
or Ge s t ns P rm0 nit
e e

( P rm i tt d L i t )
ei
e e s

P ot ass u i m pe r c hl o r a te 31 —
34

11 —
13

15

0 25 -

0 c c 0

Veloc it of y de t ona t ion

Se n i t i v e n e
s ss , 2 k g w igh t
. e 20 c m .

10 k g .

Th e cha rge li mi te of P e r m o ni te S G P. . . is 900 g .

, e qui va l e n t t o a b ou t 5 70 g of
.

d n a m i te No 1
y . .

Th e j e lly is a mixt u re of 1 part glyc e ri n e and 3 5 parts g e lat in e th e

in flu e nc e t e s t c onsi t s in a sc e rt a i n ing t h e di stan ce ov e r which d e to na tion is
s

c onv e y e d from o n e 3 0 cm ca rtridg e to anoth e r lyin g on t h e groun d

. Anoth e r .

Ge rman e xplosiv e s imila r to Pe r mo nit but not so pow e rful is IVe tte r Pe r sa li t , ,
-
.

An oth e r v e ry s im ilar e xplosiv e mad e in G e rman y i s Alk a lsit P o la r ite .

,
Po la r ite,
a non fr ee zin g e xp losive of hi gh pow e r is use d in E ngland a s a substitute
-
,

for Ge li gni t e .

S e v e ra l e xplosive s conta inin g p o t a ssium pe rchlora t e have passe d th e

R o t h e rham t e s t and a r e on t he E nglish Pe rmitte d Li st Th e y diff e r from th e
. .

P e r mo ni te s in t ha t th e y conta in a larg e r proportion of nitro glyc e rin e and -

wood m ea l and t h e a mmoni u m nit-rate has be e n re pl a ce d b y oxalate so that

-
, ,

t h e y a re not hyg r osc opic The re sul t i s that inste ad of an e xc e ss of avail abl e
.

oxyg e n t h e y con t a in a sli ght d e fici t .

Th e g e n e r al m e t h od of m anuf ac turi ng t h e se e xp losiv e s i s as foll ows Th e

o xa la t e pe rc hlo r ate and wood m e al a re a ll s ifte d and plac e d in a pan and
,
-

mi x e d t oge t h e r roughly by hand Th e ni tro glyce rin e whi ch ha s bee n par

.
-
,

tia ll y g e la t ini ze d wi t h t h e co llodi on co t-to n t h e day be fore i s pour e d on to p , ,

t h e la s t port ion of j e lly be in g wi pe d out w i t h som e wood m ea l whi ch ha s bee n -

k e p t bac k for t hi s purpo se The composition i s th e n incorpo r ate d in a g e la tin e

.

incorpo ra t or for a bout an hour at a te m pe rature not hi g h e r than

 CHL OR AT E E X P L O SIV E S

D yno b e l Ne o n a l Aj a x S w l a e

Pow d r e Pow d r e

P o t ssiu m p rchlor t
a e a e

Ni t ro glyc rin e
-
e

Collodion c o tt on
D i a n d t ri ni t ro t olu n - -
e e

Ai mn o n i m ox a l t u a e .

I Vo o d m l-
ea

M xi mu m ch rg
a a e

P ow r ( w m g of b a l p e n d
e s .

Th e addi tion of nitro tolu e n e s r e nd e rs th e e xplosive s l e ss liabl e to fr ee z e

-
,
.

A diffe r e nt typ e of p e rchlorat e e xplosive is r epr e s e nt e d by M B P owde r . . wder

po

(Modifi e d Black ) which consists of black p owd e r in which part of th e salt

,

p e tr e has b ee n r e plac e d by potassium p e rchlorat e It i s made in much th e .

sam e way as Safe ty Blasting P owd e r was that i s to say the ingre di e nts aft e r , ,

a pre liminary mimn g a r e inc orporat e d toge th e r in a st e am j ack e t e d pan

’

-
.
,

O n Nove mb e r 25 1 9 1 1 a s e ve r e fi r e occurr e d in th e hous e wh e r e this op e ration

, ,

was b e ing carri e d out wh e r e by thr ee me n w e r e kill e d and o ne was in j ur e d

,
.

It was ascrib e d to friction on dr y cak e d mat e rial in the st e am h e at e d incor -

p o r a t o r Anoth. e r similar e xplosiv e i s R os li n Giant P owd e r .

AMMO NI UM P ER CHL O R ATE P

EX L O SI VES

As a constitu e nt of a n e x p lo siv e ammoni um p e rchlorat e p oss e ss e s th e ’

advantage that it c ontains a high proportion of availabl e oxyg e n and only

produc e s gas e ou s products but unfortunat e ly th e s e include th e poisonous ,

gas h ydrog e n chloride Th e formation of this can b e pre ve nt e d by adding

.

an e quival e nt quantity of som e substanc e such as sodium nitrat e which will ,

yi e ld a bas e to combin e with the chlorin e In 1 9 0 6 th e Fr e nch Commission .

de s Substanc e s E xplosive s inv e stigat e d two Ch e ddite s containing ammon

i um p e rchlorat e and although it was de cide d not to unde rtak e th e ir ma n u fa c
,

tur e som e of the e xp e rim e nts a r e ins tructive 1 The e xplosive s had the .

compositions

Ami n o n iu in p rchlor t e a e

D i ni t ro t olu e n e
-

Sodium n i t r t a e

Ca s t or oil -

xi v pp
1

1
P . at S .
, v o l. .
, . 1 9 2, 20 6.

V OL 1.
386 E X P L O SI VE S
No I bur ns “ i th dang e r ous rapidi ty wh e n ignite d but II i s quite sa fe in
.
,

t hi s re sp e ct Fab rics M p re g na te d wi th ammoni um pe rchl orate a re m ore

.

i nflammabl e than w h e n potassium chl orat e i s us e d but not so much so a s ,

wi th so di um chl orate Ammoni u m pe rc hlorate is a mil d e xplosive by it se lf

.
,

200 0 0 50

0
o 02 0] 05 03 1 00 n o 1 20 130 LSD A

F1 0 . 78 . De t ona t ion of Amm o ni mn Pe r c hl o ra te Ch ed dit e a

’

t D ifl e r e n t De nsi t i e s

but i s onl y e xp lod e d w ith diffi cul ty and i ncomple te ly at ordi nary te mpe ra
tu re s i t is sta bl e but at 1 50 d e composition s e ts in afte r a tim e and p r oc ee ds
°

NH .CIO . C 1 O
,

according to t he e quation N 2H 0 (ga s e ous ) 2

cal T h e re action i s app a re n tly a uto cata lytic

.
1
It is ve ry im porta nt
-
.

that amm o nium p e rchlorate b e k e pt quite s e para t e from the chl orate s of
.

sodium and pota ssium as dang e rou s doubl e d e c ompositions a r e li a ble to

,

1
S ec G ira rd and La roch e M o n item
,
- s c ie mifiq ue , Apr il , 1 90 9 ; S S
. .
, 1 9 10 , p . 1 34 .
 CHL OR AT E E X P L O SIV E S
occur Ammoniu m p e rchlorat e has about th e sam e d e gre e of s e nsitive n e ss
.

to impact as picric acid : a 5 kg w e igh t falling 50 e m caus e s e xplosion

. .

som e tim e s As in th e cas e of oth e r Ch e ddit e s the ve locity of de tonation

.

ris e s w ith incre as e of d e nsity to a maximum aft e r which it falls i n cons e qu e nc e

,

of the di minution of the s e nsitiv e ne ss to d e tonation This i s cl e arly shown .

by th e curve s i n Fig 70 which give s the ve lociti e s of d e tonation and the

.
,

w eights of f ulminat e r e quir e d to d e tonat e e xplosiv e I wh e n loade d into ,

cartridge s at di ffe re nt de nsiti e s .

A numb e r of e xplosive s of this typ e w e re made i n B e lgium unde r th e Yo nckite.

nam e of Y o n ckite s One of th e s e No 10 bis i s on th e Be lgian list of E xplosive s

. .

No 1 3 is of a more brisan t typ e

.

Amm oniu m p e rchlor a t e

Ammoniu m ni t r a t e
Sod iu m n i t r a t e
Ba riu m ni t r a t e
T rini t ro t ol u e n e
-

Sodium chlorid e

Th e charg e limit e of 1 0 bi s i s 9 00 g e quival e nt to 540 g dynamit e No 1

.
,
. . .

To mak e th e s e e xplosive s th e p e rchlorat e and nitrat e s of sodi um and barium

a re mil l e d tog e th e r as also a r e th e ammonium nitrat e and trinitro tolu e n e
,
-
.

Th e two mixtur e s a r e th e n incorporat e d tog e th e r i n a Pfl e ide r e r machi n e .

Th e s e e xplosive s w e re e xamin e d by th e Fr e nch Commission de s substanc e s

e xplosiv e s but it was d e cid e d that th e y poss e ss e d no mark e d advantag e o Ve r
,

th e C h e ddi t e s 1
.

An e xp losiv e which is now b eing us e d e xt e nsive ly is Bla s tine in which ,

Bla s tine .

ammonium p e rchlorat e and sodi um nitrat e a r e mix e d with th e c ombustibl e

matt e rs dinitro tolu e n e and paraffi n wax
,
-
.

1
P . et S .
, v ol x v i i p
. , . 1 70 ; Ve nn in ct Ch e sn e a u p
, . 3 62
.
 C H AP TE R X X V I I

AMMO NI UM NI TR ATE EXP L O SIVES

Fa v i e r xplosi v s
e e : G r is o uni te s : Ammon a ls : Sa bul i te G ri ou t in
s e

A TT E N T I ON was first dra wn promi ne ntly to t he u s e of ammoni um ni trate as

a constitu e nt of e xplosive s in cons e qu e nc e of th e num e rous e xp losions of c oal
damp and du st in min e s Th e low t e mp e ratur e of e x plosion of mi xtur e s
.

conta ining larg e proportions of ammonium ni trate in dicat e d its u se for thi s
p u rpos e Ammoni um nitrate e xplosive s a r e us e d now v e ry e xte nsive ly not
.
,

only in c oal m i ne s but also for g e n e ral blasting work and th e introduction
, ,

of synth e tic m e thods for th e manufactur e of ammonia and ni tric acid i s li k e ly

Fa vi e r ex p lo to l e ad to furth e r d e ve lopm e nts in this di re ction In 1 8 8 4 and 1 8 8 5 Favi e r .

i
s vas.
took out pate nts for mi xtur e s of ammonium nitrate w ith mo no nitr o naphtha -

l e ne paraffi n and re sin

,
1
Th e man u factur e w a s soon aft e r w ards un d e rta k e n
.

by th e Fr e nch Gov e rnm e nt and is still c ont i nu e d und e r th e nam e of E x plosifs

N or E xp losifs Favi e r or P oudr e s de s fi r e té
, ,
.

Ma nuf acture . Th e ammoni um nitrate i s first dri e d and th e n gro u nd in a mill t h e pan ,

of w h ich i s h e ate d by ste am or hot wate r Th e nitro naph thal e n e is t h e n .

-

adde d and the incorp oration i s carri e d on for an hour or two in a warm dr y
,

room Th e mass i s th e n allowe d to cool and is ground to a powde r afte r whi ch

.
,

it i s loade d into cartridg e s 2

In som e cas e s th e cartridg e s a r e form e d un de r
.

conside rabl e pre ssur e but in that cas e it i s n e c e ssary t o re m ov e th e core and
,

introduc e a prim e r of t h e powde r e d e xp losiv e b e caus e if th e d e nsity b e to o .

hi gh th e e xp losiv e i s ve ry diffi cul t to d e tonate In oth e r cas e s the c artridge s

, .

a r e form e d und e r a mod e rate pr e ssur e onl y such as that produc e d by a n ,

Archim e d e an scre w working against a s light r e sistanc e Th e cartridg e s a r e .

conta in e d i n wrapp e rs of m e ta l foil or pap e r r e nd e re d w ate rproof by dipping

-

in a bath of paraffin wax Accordi ng to t he G e rman re gulations for the

-
.

manufactur e of ammoni um ni trate e xp losiv e s th e te mp e ratur e of th e w a x

bath must not e xc ee d 1 00 C W ate rproofin g i s absolute ly n e c e s s a ry be caus e
°
.

ammoni um nitrate i s e xtre m e ly hygroscopic .

l
Ex p o sifs N o r Th e c omposition of t h e Favi e r e xplosiv e s m ad e in Franc e ha s be e n vari ed
Gr is o uni tes .
1
Ge r . Pa t . of M y 27 a , 1884 ; En g . Pa t . 21 3 9 of F bru ry e a 1 6, 1 8 8 5
.

2
S ee l
a so P . et S .
, v ol i v p . .
, . 1 59.
 AMMONI U M NIT R AT E E XP L O SIV E S 38 9

from tim e to tim e Th e foll ow ing w e r e th e authoriz e d compositions of

.

E xplosifs N accordi ng to Ve nn in e t Ch e sn e au pp 345 562 , .

, .

m ine s
G r sou
i
fre e fro m
te t r y l i te fi re d a mp
-

couch e
e tc .
,

Amm oniu m n i t ra t e
P o t ssiu m ni t r t e
a a

D in i t ro n a ph t h l e n e
-
a

T rin i t ro n a ph t h a l n e
-
e

T t ryl
e

Th e Gris o u nite s couch e s a r e us e d in th e coal s e ams as th e y hav e th e or e tical te m

-

p e r a tu r e s of e xplosion of 1 500 or l e ss but N a has b e e n r e plac e d to a consid e rabl e

°
, 1

e xt e nt by N ; th e s e a r e b oth colour e d with m e thyl e n e gr e e n B

4 Th e G r is o u n ite s .

roch e s have th e or e tical t e mp e ratur e s of e xplosion of 1 9 00 or l e ss and a r e for °

,

u se in th e rocks in coal min e s ; N b i s dy e d ros e colour and N c pal e y e ll ow

l , l .

Th e s e nsitiv e n e ss of th e s e e xplosiv e s di mini sh e s rapidly with incr e asing

d e nsity ; thu s for the d e tonation of an e xp losive c ompos e d of 90 p er c e nt .

ammonium nitrat e and 1 0 p e r c e nt mo n o nitr o naphthal e n e de tonators

.
-

containi ng th e follo w ing w e ights of ful minat e w e r e r e qui r e d 1

D nsi t y f xp l osi v
e o e e W ig h t f fu l m in te e o a

0 9 -
g .

10 l
11 2
1 -2 5
b ov 1 2
a e mi s fi r s e

Th e foll ow ing a r e som e of th e principal e xp losive s that pass e d th e W oolwic h

t e st and so obtain e d a plac e on th e P e rmitt e d List

1
G ody p
, . 59 4 .
3 90 E X P L O SI VE S
In orde r to pass t he R oth e rham te st in whi ch t he e xp losiv e is fir ed w i t hout
,

ste mmin g in to t h e gas mi xt ur e t h e c ompositions have had to b e m odi fi e d

,

s om e what

I n B e lgi u m t he foll o wi ng a re on the list of E xp losifs SG P . .

Pou d re

D e n s ite Fa vi r
e D e n s ite bl nch
a e Fa vi r
e
te r i te
4 3 b is 3 C o n il
r 2 b is
1 b is

Amm oni u m ni t ra t e
P o ta s si u m ni t a te r

S odi um ni t r a te
P o ta ssi u m pe rm n g n a te a a

Lea d c hro ma te
T r in i t ro t olu e n
-
e

T rin i t ro na ph t h a l n
-
e e

D ini t ro n a ph t ha l n e
-
e

Flour
Amm oni um ox a l a t e

Amm oni u m c h l orid e .

B a ri u m ca rb on t a e

Ch rg l im i t g
a e e .

E qui va l n t D yu
e ,
i . No .
 AMMO NI U M NIT R AT E E XP L O SIV E S

Th e following a re th e r e sults giv e n by som e G e rman safe ty e xplosiv e s

t e st e d at th e G e ls e nkirch e n t e sting station : 1

R o b uri t

AI I I

Amm oni u m n it ra t e
P o t a s s ium ni t r a t e
P o t a ssiu m p e r m a ng a n a t e

D ini t ro b e n z e n e
-

D in i t ro t olu e n e
-

T r in i t ro t olu e n e
-

W o e d mea l
-

Flour
F e nn e l
Am m onium chl orid e
Sodium chl orid e
M a g n e si t e
Copp e r ox a l a t e
L im i t ch a rge g , .

T a n l test c c
r z , . .

O th e r G e rman Favi e r e xplosive s a re :

D orfi t
W e tte r
D a h me n it Ald o r fi t Fu lme m t
Fu lme n it

An nn o n iu m ni t r a t e
P o t a s s iu m n i t ra t e
P o t a s siu m b ichro ma t e

G un co tt on
-

T rin i t ro t olu n e
-
e

P a r a ffi n oil
Ry e flour
N a ph t h a l e n e
Ch a rco a l
Sodiu m chlorid e

L i m i t ch rg g a e, .

T u l test c c
ra z , . .

1
S S
. .
, 1 9 0 7, p . 13 .
39 2 EX P L O SIV ES

O f th e s e Al do rfi t and Fulme ni t a re not in te nde d for u se in dange rous coal

mi n e s D o r fi t and W e tte r Fu lme ni t di ff e r fr om th e m in c ontainin g conside r
.
-

able p e rc e n ta g e s of sodi u m chl oride whi c h re duc e s th e te mp e rat u re of e xp losion .

Mo na c hit c onta ins c rude trinitro xy l e n e mad e by nitratin g a fraction of -

be n zol Th e ni tro product may b e solid or li quid but must not conta in more
.
-
,

than 60 p e r c e nt of t rinitro bodi e s .

-

Mo na c h it l Mo n a e h it I Id
t ra te
Amm oni um ni 81 64
P o ta ss ium ni t ra te 5
3
So dium n i tr a t e
T r ini tr o xyl n e -
e 12
Coll odi on c o tt on 1
Flour
Ch a r c oa l
Al k a li chl orid e

Mo na c hi t I I d ha s a limit charge of mor e than 500 gra mm e s .

‘

U nde r t he nam e of Ra sc hi t R aschig has re c e ntly i ntroduc e d a num be r of

,

e xplosiv e s conta ini n g a mmoni um nitrate and hi ghl y solubl e organi c substa nc e s

such as ammoni um mo n o ni tr o cr e sol sulphonat e so di um cre sol sulphonate - -

,
-
,

or th e r e sidu e obtain e d in th e manufactur e of wood c e llulos e Th e i ncor .

p o ra tio n i s carri e d out by di ssolvi ng th e c onstitu e nts in wate r and e vaporating

t h e solution rapi dly on a ro ta ting ste am h ea te d d r u m -
.

A n a mmoni um ni trate e xplosiv e manufactur e d in D e nmark un d e r th e

nam e of Aer o lit ha s th e c omposition :
Amm o nium ni t ra t e
P o ta ssium ni t r te a

Fa t (be e f s uet )
Sa go flour
M a n ga n es e dio xi d e

R e s in

1 00

Th e sulphur fat re sin and mangan e s e dioxi d e a r e m e lte d tog e th e r and th e

, , ,

pota ssium nitrate and flour stirre d in and t he ma ss i s allo w e d to c ool and i s ,

powde re d Th e n th e a mm oni um ni trate is add e d and th e mi xtur e is again

.

m e lte d c ool d and p owde re d

e,
2
.

The Austrian Gov e rnm e nt manuf ac tur e a s saf e ty e xplosive s :

D y n mm \ V tt r D y nm n a on e e -
n a1 o

Amm oni um ni t r a t 87 88 e . 94 —

P o ta s s iu m ni t ra te 2
C ha rc o a l 4

De ns i t y 08 5

1
S S
. .
, 1 90 9 , p . 10 6 . For t he v l oc i t y of d e t on t ion of M on t
e a a I , s ee H K. as t ,

S S
. .
, 1 9 1 3 , p . 1 3 6. 2
D a n is h P a t . S S 1 90 5 p
. .
, , . 29 5.
 AMMO NI UM N I T R A TE E X P L O SI VE S 3 93

Th ei de a of uti lizing th e gre at amoun t of h e at e n e rgy that is lib e rat e d in Ammo na l .

th e o xidation of aluminium has form e d th e sub j e ct of pat e nts tak e n out by

G R oth of Vi e nna and mixture s of ammonium nitrat e aluminium and
.
,
1
, , ,

oth e r sub stanc e s hav e b e e n brought on th e mark e t mostly unde r th e nam e

of Ammonal In spit e of th e h igh t e mp e rature produc e d by th e oxidation
.

of alumin ium thr e e of th e s e compositions we r e abl e to pass th e W ool w ich t e st .

Amm on l a B

Ammoniu m n i t ra t e 84 87—
92 9 5
—

Ch a rco a l
T r ini t ro t olu e n e
-

P o t a ssiu m b ichro m a t e
M ois t ur e

Fer safe ty in coal min e s it is n e c e ssary to k ee p down t h e p e rc e ntag e of

-

aluminiu m In R ipping Ammonal th e safe ty is incr e as e d by the addition

.

of p otassium bichromat e and cons e qu e ntly th e prop ortion of aluminium can ,

b e incr e as e d ?
For or di nary bl asting purp os e s compositions such as th e
followin g a r e us e d :
Amm oni um ni t r a t e
Ch a rco al
T rin i t ro t olu e n e -

Ammonal is an e xplosive of conside rabl e powe r Th e v e locity of d e tonation .

3

of an Ammonal was foun d by B ich e l to b e 3 450 m e tr e s p e r s e cond Th e .

aluminium powd e r us e d for making ammonal should not b e too fi ne 4

Th e .

d e nsity of ammonal i s usually about 1 or slightly mor e .

Two e xp losive s of thi s class a r e manufactur e d in G e rmany und e r th e nam e

of G e st e ins W e s tfa lit B and C : B contains di nitro b e nz e n e and C dinitro
- -

tolu e n e R oth s Ammonal pat e nt has b e e n cont e st e d in G e rmany but on

.
’

Jun e 24 1 9 1 1 it was confirm e d by th e Courts

, , .

In Switz e rland an e xp losive similar to G e st e ins W e s tfa lit C is mad e unde r -

th e nam e of Te lsit A .

1
G er . Pa t of J un e 28 1 900 ; E ng P a t
. of S p t m b e r , . . e e 1 3 , 1 9 00 .
2
E ng . of 1 90 5 W M a cn b n d Ai mn o n a l E xplosi v s L td
Pa t .
,
"
. a a e .

3
S ee B ich e l A n g 1 9 0 5 p 1 8 8 9 a lso S S
, 1 9 0 6 p 26 ; R u d olph K i
.
, , . . .
, , .
, r egs te c l m i s he
Z e it c h r ift 1 90 7 p 233 ; B r a v tt a S S
s , , 1 9 0 6 p 1 9 9 a nd 1 9 0 7 p 1 3
. e , . .
, , .
, , . .

4 P
. H e ss An g 1 904 p 551
, .
, , . .
3 94 E X P L O SIV E S
Am monals ma nufacture d at the F e li xdorf P owd e r W orks
Th e i n Austria
(G R oth A G ) hav e th e following c omposition
. .

Am m oniu m n it ra t e

Ch rco a l
a

Ammonal i s not allow e d to b e us e d in fi e ry min e s but only wh e r e dynamite ,

woul d b e p e rmitt e d 1
.

Th e e ff e c t of addin g alum ini um to an ammonium ni trat e e xplosiv e was

inve stigat e d by Bich e l wh o obtain e d th e follo w ing r e sults
2
,
°

Dy mm n Ammon l na o a

E xp losi ve
Amm oniu m ni t r t e a

Alu m iniu m .

Ch rco a l ( d )
a re

D e nsi t y
Ve loci t y of d t on t ion m/ s e c
e a , .

H ea t of e xplosion in c a l ori me t e r
P rodu c t s of e xplosion
Ca rb on d ioxid e 13 14
C a rb on m onoxid e
l
“ a ter
O xyg e n
N i t roge n
M et ha ne
H ydroge n
Al u m iniu m oxid e

V olu me of p e r ma n e n t g a s N T P , . . .

w t r v a pou r
a e

T o t a l v olu m e

E xplosion pr ss u r e (c lcul a t d )
e a e 9 425 kg / s q . c m .

Tr a n l t e s t
z 329 cc . .

Bich e l c onsid e rs that th e r e sults of th e Tr a n zl t e st a r e misl e ading b e caus e ,

t h e gre at h e at of th e e xplosion i n t h e cas e of t h e aluminium e xplosiv e m e lts

t h e surfac e of th e l e ad and so mak e s th e appar e nt e xpansion of th e h ol e gre at e r .

Th e F e lixdorf P owd e r l Vo r ks cont e n d how e v e r that ammonal is a v e ry , ,

p ow e rful e xplosiv e wh e n e xplod e d on top of a small l e ad cyli nd e r it com ,

.

pre ss e s i t c onside rably m or e than a g e lignit e containing 05 p e r c e nt nitr e .

1
S S 1 9 10 p 54
. .
, ,
2
A u g 1 90 5 p 1 8 8 9
. . .
, , . .
 AMMO NI UM NIT R AT E E X P L O SIV E S 39 5

glyc e rin e and it br e aks up a sh e ll m or e than an e qual w eight of cast picric acid
,
.
1

Th e Fr e nch Commission de s Substanc e s E xplosiv e s found that th e addition of

alumini um do e s not gr e atly incre as e th e us e ful e ffe ct on rock but it mak e s ,

t he e xp losiv e e asi e r to d e tonat e e v e n if only 3 p e r c e nt b e pr e s e nt ?

.

A som e what similar e xplosive is Sabul it e w hi ch contains calcium silicid e S b ul it a e.

and trotyl with or wi thout th e addi tion of p otassium ni trat e and ammonium
c hloride th e latt e r c onstitu e nts b e ing adde d to mak e it safe in c oal min e s
,
.

O n the Belgian list of E xplosifs S G P 18 . . .

°

S bu l it n t ig is t A a e a r ou e u se

Ammoniu m ni t r a t e 54
P o t a s s ium ni t r a t e 22
C a lciu m s ili cid e 5
T ro t yl 6
Amm onium c hlorid 13

Ma xi mum ch a rge 9 00 g .

E qui v a l e n t t o 5 9 6 g dyn a mi t e No 1 . . .

Th e only e xplosiv e s allow e d in th e mor e dang e rous Fr e nch coal min e s Gri outin -
,
s e.

in addition to th e G ri s o u ni te s a r e the G ris o u tin e s (oth e rwis e Grisou dynamit e s )

,
—
,

which consist of ammonium nitrat e mix e d with blasting g e latin e As th e .

Stat e monopoly do e s not e xt e nd to e xplosive s containing nitro glyc e rin e -

,

th e s e a r e mad e by privat e firm s but th e c ompositions a r e r e gulat e d by th e

,

S tat e In 1 9 1 1 th e Commission de s S ubstanc e s E xp losiv e s r e solve d that

.

th e compositions should b e u ni fi e d as follows

C ouch e R och e

Th e calculat e d t e mp e ratur e s of e xplosion of th e G r is o u tine s Couch e a r e b e low

thos e of the G r iso u tin e s R och e b e low Th e addition of 5 p e r
c e nt saltp e tr e inst e ad of th e sam e quantity of ammonium nitrat e has bee n
.

fo u nd to incr e as e th e safe ty probably b e caus e th e potassium compounds

,

form e d a r e dissociat e d and vap oriz e d at the t e mp e ratur e of e xplosion and ,

aft e rwards give up again the e n e rgy th e y have absorb e d so that the e ff e ct ,

i s not ve ry much l e ss It i s e stimat e d that the e xplosiv e s with 5 p e r c e nt

. .

potassium ni trat e a r e about 5 p e r c e nt w e ak e r than the oth e rs 3

. .

A numb e r of e xplosive s similar to th e se pass e d th e W oolwich t e st and

1
1 9 0 6 p 26 l o R ud olph K gs l ch n i ch Z i t c h r ift 1 90 7 p 28 7 S S
'

S S . .
, S , . . ee a s , r ze e s e e s , , . . .
,

1 90 7 p 3 1 4
, .
2
V n n in e t Ch sn ea u p 3 14
. e
3
S e P e t S x v pp 1 8 9 1 9 0
, . . e . c .
, .
, .
, .
396 E X P L O SIV E S
w e re form e rly on t he Pe rmi t te d Li t s . Mo no b e l , o ne of t he p r incipal on e s
had the c omposi tion :
Ni tr o gly ce ri n e
-

Amm oni u m ni tr a t e
“ b o d mea l
-

To pa s s t h e more s e v e re R o t h e rham t e s t it ha s be e n fo u nd n e c e ssa ry in

most ca se s to a dd sodi u m chl o r ide or a mm oni u m o x alate :

On t he Be lgia n li s t of E xp los ifs SG P

. . . a re t he fo llow ing :
 AMMO NI UM NIT R AT E EX P L O SIV E S 3 97

Th e re i s also C o li n ite a n tig r is o u te u s e B which , a g e lignite containing

ammonium nitrat e and oth e r c onstitu e nts
Ni t ro glyc e ri ne
-

Collod ion co tt on .

Ammoniu m ni t r t e a

P o t a ssiu m p e rchlor a t e .

T r ini t r o t ol u n
- -
e e

C e llul os e n d fl o u r a

M a gn siu m sulph t
e a e

Ch rg li mi t
a e e

E qu i v a l n t Dyn No
e , . . 1

O f G e rman G r is o u tine s th e followi n g may be m e ntion e d

T re m o n it D on ri t
a

Ni t ro glyc r i n
-
e e

Dini t ro glyc e rin e

-

Collo d ion co tt on
Amm oniu m Ni t r t e a

P o t ssiu m ni t r t
a a e

D i ni t ro t olu n e
-
e

T rin i t ro t olu e n e
-

Sodium chl orid e

C a rb ohydr a t e s
Co a l du s t
Ch a rge li m i t e
T a n l t est
r z

Ni t ro glyc e r in e
-

Am m oniu m ni t r a t e
Sodiu m chlorid e

T rin i t ro t olu n -
e e

“ b od m l-
ea

Ch rco la a

P r ffi n oil
a a

G e latin e VVe s tfa lit i s a low fre e zing s a fe ty n itro glyc e rin e e xplosive containing
- — -

not mo r e than 50 p e r c e nt dinitro c h lo r h y dr ine and 5 p e r c e nt nitro glyc e rin e

.
—
.
-

g e latiniz e d with a small proportion of collodion cotton and containing ammon ,

ium nitrat e not mor e than 1 0 p e r c e nt saltp e tre tog e th e r with hydrocarbons
,
.
, ,

ve ge tabl e m e al n e utral salts and nitro compounds

,
-
.
39 8 E X P L O SIVE S
In A ustria a n e xplosiv e
.
l d
ca l e P a nn o ni t is ma de
Ni t ro gly c e rin e 25 -5
Coll odi on co tt on 15
Amm o ni u m ni t r a t e 37
4
3
Ni t ro to lu n e
-
e 5
Al ka li c hl orid e 24

A caput mortuum is adde d a s colo u ring matte r and th e e xplosive is ,

fi r e d with a sp ec ial d e to na to r conta ining trotyl 1

It re pla c e d a form e r e x p lo
.

sive consisting of ammoni u m ni trate a nil in e hydrochloride and som e tim e s

,

ammoni um sul p hate ?

1
a s 1 9 1 3 p 39 8
, . .
2
S S 1 90 7 p 1 1 2
. .
, , . .
 I ND E X 0 1 NAM E S
1

AB D A LLA H I BN AL -B AY TH AR, disco v ry e of Ch sse p ot r ifl e 38

a , ,

s l t pe t re 14 a , Ch rt i r c llulos ni t ri t s 19 1
e e , e e e ,

Ab l Si F cordi t e 304
e , r .
, . Cl us sulphur re co v ry 70
a ,
e ,

d e composi t ion o f ni t ro c llulos 1 92 -

e e, Congre v e Colon l w r rock e t , e ,
a , 33
gun co tt on 40 -
, Coop r Key M a j or insp e c t ion
e -
, , of e xplosi v es ,

ni t r t ion o f co tt on a , 47
s t bili z a t ion o f gun co tt on 1 8 2
a ,
-
,
Cr n ni t ro c llulose f lo w ni t r t ion
a e, -
e o a , 1 46
Ady e M j or h a nd gre n a d e s 32
, a ,
-
, Cross c llulos 153
,
e e,

c ell ulose sulphur i c e st e rs 1 8 8

A ON
,

B C ,Rog e r di sco v e ry o f gunpowd e r, 1 5 ,

Be bi e , ni t ra t ion of c e ll ul os e 1 45 , D AW , c pp d c a r tridge s 37
a e ,

ni t ro c e ll ul ose of high ni t r t ion 1 36

-
a , de M os e n t h l s t ruc t ur o f co tt on 1 65 a , e ,

s olubili t y of ni t ro c llulos e 1 37 -
e ,
D e w r cordi t 304
a ,
e,

B e ll c e llulos e sulph t s 1 51
, a e , Di v rs d composi t ion o f ni t ro c e llulos e
e , e -
,

ni t ro c e llul os e 1 36 145 -
, , Di v ine Spr nge l e xplosi ve s 43
, e ,

B e rl ni t ro s t rch 1 95
,
-
a , D e y e br e ch lo di ng r ifl
r s ,
38 e -
a e,

B ert h e lo t in ve s t ig t ions 44 56 , a , , D u h m Rog r B con 1 7

e , e a ,

ni t r t e forma t ion 56 a , Dupre At l s powd e r 361

,
a ,

po t a ssiu m chlor t e 377 a , dyn a mi t e 360 ,

B e rt ho ll e t di sco v ry of chlor t e 35 , e a , ,
ki s e lguhr 358e ,

B e v a n c e llulos , 1 53 e, po t ssiu m chlora t 378a e,

c ellulos e s ul phuric e s t e rs 18 8 ,

B ich e l a mmon l 394 , a , EG G , J ful min a t e p 37 ca ,

c a rboni t e 45 ,
Eve lyn G J gunpowd r monopoli es
, . e , 23, 55
B ickf ord fus e 38 , ,
Eve rs d e ni t r t ion o f cids 126
,
a a ,

B ingh m R W a Indi n s l t p t re indus t ry 57

, . .
, a a e ,

B ingh m vi scosi t i s 337

a , e ,
F AR MER d composi t ion o f ni t ro c llulos e 1 92
, e -
e ,

B ott ge r gun co tt on 39 ,
-
,
F a v e Chin s fi r works 14
,
e e e ,

B ourn e rly t es t fo gunpow de r 27

,
ea r ,
F v i r mmoniu m ni t r t xplosi v s 38 8
a e , a a e e e ,

B ox e r Colon e l r ifl c r t ri dg 38
, , e a e, F ernb ch c e t one fro m s t rch 347
a , a a ,

B co nn t ni t ro s t rch 1 94
ra o ,
-
a ,
Flore n t in progressi v powd e r 3 12,
e ,

B riggs c e llulos e sulphuric e s t rs 1 8 9

, e , Forsy t h d e t on a t or lock 36
, ,

B rown E A d e t on a t ion o f gun co tt on 4 1

, . .
,
-
,
Fra sch sulphur produc t ion 71
, ,

B rul y ni t r t ion o f c e llulos e 137

e , a ,
Fr born t i me fus 38
ee ,
e,

B ii tle ni t ro s t a rch 1 95
r,

G I B B ON disco ve ry f gunpow d r 22
-
,

,
o e ,

a u c , c a h u ee i t, 89 G ilb ert ni t r t consu mp t ion 56

,
a e ,

C llini B e n v nu t o gunpowd r
e , e , e , 28 G ir a rd a mmoniu m p erchlor t 38 6
,
a e,

Ch a nc sulphur r co v ry 70
e, e e ,
G i ffit hs Schul t z e powd r 48
r ,
e ,

Ch rdonne t a rt i fici l silk 4 1

a ,
a , G iindlic h ni t r t ing c e nt rifug ls 1 71
r , a a ,

399
 a m IND E X O F NA ME S
,

G u tt m nn b ll t w rs 1 1 1
a , a o e , Knie ts c h ol um 9 7 , e ,

cond e nse rs 109 , Sp gr of ol e um 103

. . ,

ea rly m nuf c t u re of gun powd r a a ,

e , 19 , 24, Ko tte r in v n t ion of rifles
, e , 28
26
L AR O C H E mmoni um pe rchlora t 38 6
, a e,

H A ER syn t h sis of
B , e a mmonia , 1 16 La wes ni t ra t cons ump t ion 56
, e ,

H ae uss e rma nn xyloidi n 152 , e,

Lea t he r India n sa l t pe t re indus t ry 57 59 60
, , , ,

s olubil i t i es of sa l t pe t re e t
H k c ll ul o se sul ph tes 151 18 8
a e, e a , ,
64 , c .
,

Le f u c he ux ca ppe d ca rt r id e s 37
ni t ro ce llul ose 1 36 1 45 -
, ,
a ,
g
,

H ll bo bbini te 90
a , ,
Le w is ce llulose sulph u ric e s t e rs 188
, ,

dyna mi t 363 e,
Le w ko w it h glyce rin 20 3
sc , e,

H nry ni t ro iso b u tyl glyc rin 24 1

e ,
- -
e e,
L i big fulmi na tes 37
e , ,

H ib b e rt fr zing po in t of ni t ro glyc rin 235

, ee - -
e e,
L ind o y liq u it 44
e, x ,

H im Colon l G r k fi 12
e, e , ee re ,
L un dholm ba llis t it e 302 , ,

rly proj c t il s 30
ea e e ,
di re c t di pping proc e ss 1 71 ,

dis co v ry f g u npowd r 1 7 e o e ,
L u ng e xpa nsion of sul phuric cid 103
e, a ,

inc ndi a ry mi ssil es 30

e ,
ni t ra t ion of c ll ul os e 145 e ,

rock t s 33 e ,
ni t ro ce llulos e of high ni t ra t ion 1 36
-
,

H fw inn r
o ni t ro is obu t yl glyc r in ni t ri t
e ,
- -
e e e,
solu b ili t y of nit ro c llulose 137 -
e ,

24 1 spe c ific gra vi t y of ni t ric id 1 17 ac ,

H o itse ma ni t ro ce ll ulos of hi gh ni t r t ion

M A C D ON ALD w s te cid fro m dis pla c e me n t
,
-
e a ,

a a
1 35 ,

India n s l t pe t re indus t ry 59
H ee pe r , a ,
proc ss 1 78 e ,

H oppe S y l c t ion of b c t e r ia on c ll ulose

-
e cr, a a e ,
M cn b w t r t mp ing 44
a a , a e a ,

1 65 Mc Ro b e r t bla s t ing ge la t in e 3 65
s, ,

H ough nit ro s t rch 1 95

,
-
a ,
Ma j ndi inspe c t ion of e xplosi ve 46
e e, s ,

H ow ll b obbini t 90
e , e,
M nley spec ific gr vi t y of ni t ric cid 1 1 7
a , a a ,

dyna mi te 363 ,
M r hle w s ki spe c ific gra vi t i es of ni t ric a cid
a c , ,

H ubn r me rce riz e d cott on 1 52

e , ,
1 18

H utm nn H nnin g dri lling m chi ne

a , e , a , 34 M rco P olo s l t pe t re in Chi na 1 4
a , a ,

H y tt c ll uloid 4 1
a , e ,
M rcus G ra e c u s fir e works 1 7
a , ,

py roxylin 147 ,
M rsh ll A c et on 345
a a , .
, a e,

ni t ra t or 179 ,
spe cific gr vi t ies of mix ed cid 121 a a s
,

S pe c ific gr vi t i of sulphuric a cid a es , 1 00 ,

1 03
J E NKS , c llul os sul phu ri c t 188e e es e rs ,
v ola t ili t y of ni t ro glyc rin 35 1 -
e e,
J ntg n xyloid in 152
e e ,
e,
M tt h ws cl ssific t ion of c llul oses
a e a a e 150
J o h ns on D s mok l ss powd r 48 , .
, e e e ,
M rci r C p t in f us 32
e e
,

a a es
,

J oin vi ll wild fi 13
, , ,

e, re ,
M oorso m p rcussion f u 38 e se,
J oyc F ful min t
,

e, p 37 .
,
a e ca ,
M uk rj Indi n s lt pe t ind us t ry
e ee, a a - re 59 , 61
J oyc ni t ro c llulos of low nit ti on
,

146
e, e e ra
solubili t y of s l t pe t re tc 64
-
.
a , e .
,

K A S T din i t ro hl hy d in 236
,
-
c or r ,
NAH NS E N coo ling liqui d for ni t ro glyc rin
,
-
e e

fr e zing poin t of ni t ro g lyc rin 236

e -
e e, ni t r tor 218 a ,

K lln r cordi t 304

e e , e, N t h n Col Sir F cordi t 30 5
a a , . .
, e,

K ssl r conc e n t ra t ion f sul phuric cid

e e , o a m n ufa c t u of gun co tt on 1 69
a re -
,

K es t n r cid g 129e , a e , m nuf c t u re of ni t ro glyc rin

a a 21 1 -
e e,
‘

Kla r wood di s t i ll t ion 34 1

, a ,
s t bili za t ion of gun cott on 18 2
a -
,

Kl y ni t ro
a e, y ll ul o s e t 154 -
ox ce a , e c ., Na u kh o ff fr ee zing po in t of ni t ro glyc rin 236
c ,
- -
e e,

Kn ch t l bil e c llul o s nit r t e 15 1

e , a e e a , N w t on Chi l ni t r t ind us t ry 62
e , e a e ,
 I ND E X OF NA ME S 40 1

Nieo la r do tc llulos ni t ri t es 19 1 , e e , Sch mid t c rboni t 45 , a e,

Nob l A b lli s t i t e 49
e , .
, a , S h tinb in gun co tt on 39
c e ,
-
,

bl s t ing g l t in 43 a e a e, Schul t z M j or s mok l ss powd r 47

e, a , e e e ,

d t on t or 4 1 e a , Schw rt z B r t hol d d i co v ry O f fi
a , r ms 1 9e ,
s e re - a ,

dyn mi t 357 a e, Sco tt G Sons di s t ill t ion O f glyc rin

, .
, a e e,

nit ro glyc rin m nuf c t ur 20 8 -

e e a a e, S p k
er lu miniu m ni t i d 1 15
e , a r e,

N b in
orr mmoniu m ni t r t e xplosi v s
, a a e e , Sh w J ful min t
a ,
37 a e,

Ny rly t s t for gun pow d r 27

e, ea e e , Sh pn l L i u t sh ll 3 1
ra e ,
e .
,
e ,

Silb d hydrolysis f ni t ro c llulos 192

ON
err a , O -
e e,

O H LS S nit r t e xplosi v s
, a mmoniu m a e e , 42 Sni d r r ifl e 38 , e,

Omeli n ki c t ion O f b c t ri on c llulos

a s , a a e a e e, 1 65 S b
o o ni t ro glyc ri n
r er 41
,
-
e e,

O t hy d ro c ll ulos e 1 54
s ,
-
e , Spre ng l xplosi ve s 43 49
e , e , ,

St p now solub ili t i s in t h r lcohol 337 e a

P A T ER NO b llis t i t 302
e a , e e -
.

,
a e, St r t ch d di t e 38 0
ee , e ,

F louz
e gun cott on 39 e, -

T H O MS ON Ca p t in J
,

P rkin c t one fro m s t rch 348

e ,
a e a ,
,
a . H .
, insp ct ion O f e ex
p lo
P tt i t mixt ur
e , O f a c t on nd m thy l es e e a e
s iv es , 47
lcohol 346 a , T ho mson J M , . . ma nufa c t ure O f ni t ro glyc rin -
e e,
P ick ring S pe ci fi c gr v i t y o f sulphuric cid
e ,
a a , 21 1
1 00 T urpin picric a cid , ,
49
P i s t o v rbl a ch ed cott on 158
e , e e , T w i t ch ll glyc rin e ,
e e, 20 3
Pope m rc riz d cott on 152
, e e e ,

P n h n ni t ric cid
u s oxplosi v -
a e e, 43
.

U C H ATI U S, ni t ro s t a rch -
, 19 7

R E ID
I V F s mok e l e ss powd e r 48
, . .
, ,

Re ina n d a nd P a v é Chin es e fire works 14 , ,

VAL E N TI N E R, ma nuf a c t ur e O f nit ric cid a ,

Rin t oul ma nuf a c t ure o f ni t ro glyc e rin e 21 1

,
-
,
1 10

r co v ry o f c t on 349
e e a e e,
V l y S p c ific gra v i t i s O f nit ric ci d 1 1 7
e e , e e a ,

Rob rt son r co v ry of c t on 349

e , e e a e e,
V nd r unf r z bl ni t ro glyc rin 239
e e , ee a e -
e e,

s t a bil i t y O f ni t ro c llulos 18 8 -
e e, Vi ill ni t ro c llulos s 1 5 1
e e, -
e e ,

Robins b llis t ic p ndulu m 28

, a e ,
P oudr B 49 e .
,

Ro w e dini t ro h l hy dr in xplosi v s 238

er , -
c or e e ,
Volkm nn s mok l ss powd r 48
a ,
e e e ,

Rosco bo ilin g poin t f ni t ric cid 1 19

e, -
o a .
V oln y lo w fr zing ni t ro glyc rin 38
e ,
-
ee -
e e
2

Ro t h a lu miniu m xplosi v s 39 3
, e e ,
Vo n L nk ni t r t ion O f co tt on 39 1 69
e ,
a , ,

Rudolph mmon l 393 , a a ,

s t b ili t ion O f nit ro c llulos 1 82
a za -
e e,

SAP OSHN I KOFF, ni t r t ion Of c llulos 1 51 a e e, “7 A LE N ERG low fr zing ni tro glyc rin
H B ,
-
ee -
e e, 23 8
ni t ro s t rch 1 9 6 -
a , l Ve intr a u b O f nit rous cid , e ii ec t
“

a , 1 42
S p c ific g n ti O f mix d ci ds 1 21 t i t h n h nd gr n d s 32
’

e ra cs e a ,
e or e, a -
e a e ,

v po u r pr sur s O f mix d cids 123

a es e e a , W ill ni t ro sug
,
19 7 -
a rs ,

v pour pr ssur f ni t ric ci d 1 19

a e es o a ,
ni t ro st rch 1 95 -
a ,

Sa y rs b lli st i t 30
e , a e,
2
W righ t E G ful min t , p 37 . .
,
a e ca ,
 I ND E X O F SU B J E C TS

EA E
AC T T O f li me 340 , Ba c t ri c t ion O f n c llulos 1 64
e a, a , o e e,

Ac e t on e 340 ,
B llis t i t
a 49 30 1 322
e , , ,

ma nuf a c t ure 340 3 48 , ,

B t r f r ni t ro co tt on 18 7
ea e o -
,

r co v ry O f 349
e e , B lgi n s mok l ss pow d r 29 8
e a e e e ,

t st s 3 44
e , B lli t
e 38 9 390
e, ,

Aci ds m nipul t ion O f 128

, a a ,
B nzo t s O f c llulos
e a e 1 53 e e,

Adipo c llulos 1 50
-
e e, B nzol 247
e ,

A roli t 39 1
e e, B isulphi t proc ss f r co v ry f c et one
e e or e e o a , 3 43
Af t r s p r t ion pr v n t ion o f 218
e -
e a a , e e ,
B l nk powd e r 334
a ,

Af t r s p r t or f
e -
ni t ro glyc rin 21 1
e a a or -
e e, B la s tine 38 7 ,

Ag ing S port ing powd r 325

e e ,
B l s t ing xplosi v s 357
a e e ,

Aig supply f ni t ro glyc rin m nuf c t ur or -

e e a a e, 23 ) B l s t ing g l t in 3 64 3 70
a e a e, ,

Aj x pow d r 3 8 5
a e , B l s t ing pow d r 8 7
a e ,

Alcoholizing ni t o c llulos 29 2 r -
e e, fi rs t u 33 se,

Ald hy d s in c t on 3 45
e e a e e, B l nding gun co tt on 18 6
e -
,

Aldo rfi t 39 1 , gunpowd r 8 4 e ,

Alka ls it 38 4 , B ob b ini t 89 e,

Alu miniu m E Xp lo s iv e 39 3 ,
B oiling gun co tt on 1 8 2 -
,

Amb e ri t e 327 , B r ito n ite , 3 76

Ame ric a n g e l a t in e dyn a mi t e s 3 71 ,
B rown ch rco l 69 a a ,

Ame ric a n s mok e l e ss pow de rs 29 8 , , 3 30 gunpow d r 72 e ,

Amin e s in a c e t on e 3 45 ,
B ulk s mok l ss powd rs e e e , 323
Ammon a l 39 3 ,

Ammon c a r b oni t e 39 6-
, C Al l U E C I T, 8 9
Ammoni a dyn a mi t e s 3 62 C lciu m c rbon t e s ta biliz r
'

,
a a a as e ,

Ammoni t e 3 8 9 3 9 0 , , C a mb r ite , 3 76
Ammoniu m ni t ra t e 3 8 8 , C nnon d v lop m n t O f
a , e e e , 29
xplosi v s 42 38 8
e e , , C a nno n ite , 322, 327
p rchlor t 38 5
e a e, C a pp d c rt ridg s 3 7
e a e ,

Anilin 272 e, C a rb olic Acid 250 ,

An t ig l d eté 3 76 e s u rc , C a rboni t 45 3 75 e, ,

Ar b sa ly fir w orks 1 7
,
ea r e , C a rt ridg s c pp d 3 7
e , a e ,

Arki t 3 74 e, C e lluloi d 41 ,

Aro m t ic co mpoun ds 245

a , Ce llulose 135 1 48 , ,

As tra litc 39 7 , Ac e t t 1 53 a e,

At l a s pow de r 364 , att ck by b c t ri 1 64

a a e a,

Aus t ri a n s mok e l e ss powd e rs 330 ,

b nzo t 153
e a e,

Au t ocl a v e proc e ss fo r g ly c e r inc 20 3 ,

nit r t l bil 15 1
a e, a e,

Axi t e 30 8 , ni t r t s 15 1
a e ,

ni t rit s 19 1 e ,

B A C K- F LA S H, 3 18 sulphuric s t rs 150 e e ,
 I ND E X . OF S UBJ E CTS 1 40 3

C llulos t h e ory f ni t r t ion f 1 35

e e, o a o , D t on t ion inco mpl t
e a , e e, 6
C n t rif ug l ni t r t ing pl n t 1 70
e a a a , D t on t or lock 36
e a ,

Ch rco l 67
a a , D t on t ors 3 6
e a ,

brown 69 , D in itr o a c e tin, 239

co mposi t ion O f 69 , Dini t rob nz n e e e, 256
m nuf c t ur O f 67 a a e , D in itr o c h lo r hy dr in, 239
C h ss e po t r ifl
a 38 e, D initr o fo r min, 23 9
Ch e ddi t e 46 38 0 , , Dini t ro glyc rin 238 -
e e,

Chile ni t ra t indus t y 62 e r , Dini t ro glycol 240 -

,

Chin s disco ve ry O f s l t pe t re 14
e e a , Dini t ro n ph t h a l en e 269
-
a ,

fire works 1 4 , Dini t ro t olue n 259 e,

Chlor t disco v ry O f 35
a e, e , Diphe nyl min 272 a e,

e xplosi v e s 377 , s t a biliz e r 272

as ,

Chlor t O f po t ssiu m 35
a e a , Dir c t dipping proc ss 1 71
e e ,

C hlo r a tit 38 3 , Displ c m n t proc ess 1 74

a e e ,

Co l dis t illa t ion of 245

a , , Dis t ill t ion of c e t one 344
a a ,

mine d ng rs 44 a e , glyc e rin 204 e,

t a r , 245, 247 ni t ric a cid 1 12 ,

C o llo din, s mok el ss powd r 48 e e , Don ri t 39 7 a ,

Collod on co tt on 147 180

i , , D o r fi t 39 1 ,

w sh ing 1 93 a , Dre nch ers a u t o m t ic for gunpowd e r mills

,
a , ,

Colloids n t ur O f 339 , a e , Drowning gun co tt on 1 73 -

,

Co mbin d proc ss for glyc rin 20 3

e e e e, ni t ro glyc rin 221 -
e e,

Co mbus t ibl cons t i t u n t s of xplosi v s 5

e e e e , Drying co tt on 1 68 ,

Conc n t r t ion of glyc rin e 20 2

e a e ,
gunpowd r 8 3 e ,

O f sulphuric cid 9 6 a , ni t ro c llulos 28 9 -

e e,

Con v y nc Of ni t ro glyc e rin 226

e a e -
e, s mok l ss powd r 30 7 e e e ,

Cooling coils for ni t ro glyc erine ni tr t or - a , Dus t ing gunpowde r 8 3 ,

C o p bo tt o ms 1 63 ,
D u x ite 3 74 ,

Cordi t 304 e, Dyn ami t e 358 ,

in v e n t ion 49 a mmoni a 3 62 ,

Cornil poudr bl nch 390

, e a e, Ame ric a n 3 61 ,

Coming gunpowd r 25 8 1 e , , a ntig r is o u te u s e , 3 75

Cornish powd e r 374 , 40 p e r c e n t 3 70 .
,

Co tt on 1 61 , prop e rt i s 359 e ,

d d 1 67 ea , D y na mmo n , 3 9 2
m rc e riz d 1 52 159
e e , , D y no b e l, 38 5
o ve r bl a ch e d 1 58
I M R O ED powd r
-
e ,

pre p r t ion o f 1 68 a a , E C . P V e , 326

purific t ion Of 1 62 a , EC. powd e r 48
.
,

s t ruc t ure of 1 65 ,
Effi cie ncy Of propell n t s 320 a ,

w s t 1 61 a e, E gg for a cids 129 ,

G O V (see a ls Sulphuric a cid ) 9 6

. . . o ,
E l e va t or a u t o ma t ic for a cids
, , ,

Cu t powd ers 8 4 ,
E ndo t h r mic compounds 6
e ,

Cy n mide 1 14
a a ,
E rosion 3 1 5 ,

Et h e r a lcohol 337
-
,

D AHM E NI T 39 1 ,
E xplosifs N 38 8 , .
,

D fini t ion O f ex plosion 1

e ,
E xplosion d efini t ion f 1 ,
o ,

D ni t r t ion of c ids 125

e a a
,
E xplosi ve d fi ni t ion o f 1 ,
e ,

D e ns ite, 390 E xplosi ves cons t i t u e nt s o f 2 , ,

 40 4 IND E X O F S U BJ E CTS
E xud t ion a of ni t ro glyc rin -
e e, 3 69 G un co tt on 39 1 35 1 68
-
, , ,

d isco v ry 39 e ,

FAC TO RI E S d sign O f 229 e

w ighing 305 e ,

F r m r s dyn mi t 370
a e
'
,

a e,
,
G unpowd r 1 1 23 e , ,

F t s 20 1
a
brown 72 ,

F v rsh m P owd r 390

a e
,

a e
co mposi t ion O f 73 ,

F vi r xplos if 38 8 390
a e e
,

rly m nuf c t ur 23
ea a a e,

F r m n t proc s f r glyc rin

e e es
,

o
,

e e, 20 4
t st s 27 e ,

m nuf c t ur O f 73
Fil t ing nit ro glyc rin 210
er -
e e.
a a e ,

Fili t 30 2 e,
pro duc t s O f xplosion 9 0 e ,

Fini shing gunpowd r 8 4 e

G utt rs fo r nit ro glyc rin 227
e -
e e,
,

Fire r ms d v lop m n t O f 28
a e e e
HARDE NING sport ing powd r
-
, ,

in v n t ion O f 1 8 e ,

Fir works 32
e ,
H t f lib r t ion 1
ea O e a ,
e

d v lop m n t O f 32
,
H x nit rodiph nyl min 273
e a e a e,

H igh xplosi v s 357

e e e ,

Fl m muzzl 3 19 e e ,

H ist ory O f p l i 1 1
a e, e,
ex o s v es ,
Fla mmi v o r e , 39 6
Flour 3 72 H yd t c llulos 1 53
ra e e e,

Forci t 372
, ,

H ydroc rbons 246 a ,

H yd oc llulos 153
e,

F t it 390 39 6
ra c o r e, ,
r e e,

Fr zing O f ni t ro glyc rin 232

I GNI T ER S 36
ee -
e e,

Fr nch s f t y e xplosi ves 3 72

e a e
,

s mok l ss powd rs 328 e e e

,

Inc e ndi ry missil s e rly 30

a e , a ,

mixtu r s e rly 1 2
,

e a
F u l me n it 39 1 , ,

Incorpor t ing ch ddi t 38 1

,

u in t s d isco v ry 36
F lm a e e
a e e,

Fu m hoods 214 e
, ,
gunpow d r 24 e ,

Fu m s r mo v l O f 214
e e
,

a
s mok l ss pow d rs 29 2 30 6 e e e , ,

In di n lt p t r 1 5
, ,

Fus s d v lop m n t O f 38
e e e e
a s a e e,

l nf n l m chin s 32
, ,

s f t y 38 a e
er a a e ,
,
l nf u i l rt h 357
so r a ea ,

Inj c t or f glyc rin 20 8

e or e e,

G AS , v olu t ion O f 1
e , Insp c t ion O f xplosi v s 46
e e e ,

G l t in d y n mi t
e a 3 69 3 71
e a e,

J A P A N E S E s mok l ss powd r
,

G l t iniz d xplosi v e s 3 64
e a e e , e e e , 308
G ligni t 369 3 70
e e, , J u dson pow d r 363 e ,

G rm n s mok l ss pow d rs 363

e a e e e 330
K E T ON E S 347
, ,

G s t ins W tf li t 393
e e -
es a , ,

G l zing gunpowd r 8 3
a e , Ki s lguhr 357
e e ,

G liic ka uf 39 1 , Kin t ics O f ni t r t ion

e a , 285
G lyc rin 20 1e e, Ko hl e n ca r b o nit 3 76 ,

G r nul t ing gunpowd r (

a a l Corning ) e s ee a s o , K o la x 3 75 ,

G r nul t ing s mok l ss powd e r 325

a a e e , Ky n o c h s s mok e l e ss powd e r 327
’
,

G r k fi 12
ee re ,

G r n d s 32
e a e , L A B Y R IN T H S fo r nit ro glyc erine w a sh w t e rs
- -
a ,

G rign on 340 , 215

G ri n ding in g r di n t s o f unp owd r 75
g e e e , L d wi t h cids
ea a , use Of , 1 28
G i souni t
r 38 8 e, L ig dy n , 3 62
G risou t in 45 39 5 e, , L ignoc llulos e e, 1 49 , 1 50
G r is o u tite , 3 75 L i mi t bo rds a ,
230
G uhr , 3 57 L int rs 1 63
e ,
 IND EX O F S U BJ E CTS 40 5

Lo w fr zin g nit ro glyc rin

-
ee -
e e, 232 Ni t ro c llulos 135
-
e e,

xplosi v s 3 72
e e , drying O f 28 9 ,

L yddi t e 5 1 320 , , hydrolysis O f 1 8 9 ,

m nuf c t ur Of 1 68
a a e ,

MD POW DER 38 5
of high ni t r t ion 1 80 a ,

O f lo w ni t r t ion 1 46
. .
,

M li nit (
e l P icric cid )
e s ee a s o a 49
a ,

M l t ing poin t f ol u m 10 5
e -
o e
,
powd e rs 28 9 ,

M erc riz d co tt on 1 52
e e
,
produc t s o f d co mposi t ion e ,

M et hyl lcohol 341 a

,
solubili t y o f 1 37 ,

in c et on e 346a
,
solubl 1 40 1 8 0 e, ,

M et hyl min in c t on 345

a e
,

a e e,
s t bili z t ion f 1 8 2
a a o ,

M et hyl t hyl k t on 347 e e e,

Ni t ro glyc erin 20 6
-
e,

d isco ve ry O f 41
M ill ing gunpowd r 76 e
,

Minite 376
,
high xplosi ve s 357 e ,
,

Mino lite a ntig ris o ute us e 390

fr zing O f 232 ee ,

m nuf c t ur 20 6
,

M ix e d cid 120 a
a a e,

me suring 30 6
,

fo r ni t r t ing co tt on 1 77
a ,
a

glyc rin 222 e e,

,
powd e rs 28 9 ,

m nipul t ion Of 1 28
a a
v ol t ili t y O f 351
a ,

M ixing a ci ds 120
,
Ni t ro isobu t yl glyc rin ni t r t
- -
e e a e,

ingre di n t s of gunpowd r e
,

e 76
Ni t ro m thy l n ilin 274
-
e a es ,

ni t ro glyc rin e xplosi v s-

e e e
, ,

30 6
N it n ph t ha l n 268
rO- a e e,

Mo ddite 30 8
,
N it y c llulos
ro -o x 1 54
-
e e,

Mo na c h it 392
,
Ni t ro ph nols 277 28 1
-
e , ,

Mo na r kite 39 6
,
Ni t ro s t rch 19 4
-
a ,

Mo no b e l 39 6
,
Ni t ro sug rs 1 9 7
-
a ,

M oors e rly u O f c a nnon

,

a se 19
Ni t ro t olu n 258
-
e e,

o
,

M ulding gun co tt on 1 8 6 -
,
Ni t rous fu m s r co v ry 1 1 1 e , e e ,

M oul d d powd rs 84
e e
,
Ni t ro xyl n s 267
-
e e ,
,
9 6, 9 7, 10 3 , 1 3 1
M uzzl fl me 3 1 9
e a
ma ni pul a t ion 1 3 1
,

NAP I I TH AL E N E 252 , O3 E LO S I
XP F, 379
Negro powd r e , 39 0 O leu m , 9 6, 9 7, 1 03, 1 3 1
Ne o na l 385 , ma nipul a t ion 1 3 1 ,

Ne u W e s tfa lit 39 1
-
, O xy c e llulos e 1 54
-
,

Ni t r t e r s e p r t or 215
a -
a a , O xyg e n c a rri e rs 3 ,

Ni t ra t ion O f c llulos e t h ory of 135 e , e , Ox y li q u it 44 ,

co tt on 1 68 ,

kin t ics of 28 5 e P AN N ONI T, 39 8

Ni t re c k 1 12 a e, c e llulose 150
P e c tO -
,

Ni t ric cid 10 7 a , P rchlora t e e xplosi v s 38 3 38 5

e e , ,

m nuf a c t ure of 10 7 1 12 1 1 3
a , , , o f a mmoni 38 5 a ,

prop rt i s 1 1 7 e e , o f po t h 38 3 as ,

spe ci fi c gr v i t i s 1 1 7 a e , P rcus sion c ps 3 7

e a ,

s t or g 1 1 1 a e, P rm ng n t t es t for c t on 344
e a a a e a e e,

Nit ric s t e rs 5 1 9 4
e , , P e r mo nite 38 3 ,

Ni t ro nilin s 273
-
a e , P e tr o kla s tit, 8 9
Ni t ro a roma t ic co mpounds 5 243
-
, , P he nol 250 ,

Ni t ro b e nz e ne 253
-
, P ic king co tt on , 1 68
 IND E X O F S U BJ E CT S
Pic te O
raf a mmonia 283 , Se pa r t or for ni t r o glyce rine
a -
, 209
S h lle , 30
Picr ic id 44 49 277
ac , , , ea rly , 30
Poa c hing gun co tt on 18 -
,
5

fuses 3 1 38 , ,

high e xplos i v 3 1 e,

P oudr e B 29 4 .
,
shra pn l 3 1 e ,

P oudre J M S T 328 9
, .
, .
, .
, .
,
—
Sho t gun powd e rs 322
-
,

P ow der s mok les s 6 28 9

s , e , , t es t ing of 330 ,

P res ing gun p owd r 26

s e , r ifl e ite , 322
mo k la s powd r 30 6
s e
‘

e , S hra pn l she ll 3 1 e ,

Pr e w h t nk for nit r o glyc rin 209

-
as a -
e e, S il es ia 38 2 ,

Pr oduc t s Of xplosion 3 19 e , Smok l es s powd rs 6 47

e e , , ,

P rogre ssi v s mok l es s powd r 3 12

e e e ,
co nd nse d 322 e ,

form of gra ins 3 12 ,

P ro met hee , 3 79 pro gres s i ve 31 2 ,

Prope lla n t s t es t ing of 320 , , t o f bur ning 3 10

ra e ,

Pulpin g gun co tt on 1 85 -
, Soa p 20 1 ,

P yroc ollodi on 180 , Sodi u m ni t t 62 ra e ,

P yroli gne ous cid 341 a , indus tr y in Chile 62 ,

Pyr o xylin 146 , Sol e ni te 30 2 ,

Solubili ti s of ni t ra tes a nd chlorid es of s od i um

e -

Rx c x a a o c x 43 3 79 , , a nd po ta ss iu m 6 3 ,

Ra sc hi t 39 1, Solubili t ies of ni t ro ce llul o se 1 37 -

s,

Rec o ve r y of ni t rous f u me s l l l , Sol v n ts for ni tr o ce llulose 33 6

e -
,

sol ve n t s 349 , S ol v e n t re co v ry 348 e ,

Rifl e d v lop m n t of 29
, e e e , , 38 S pa nis h s mok e l es s powd rs 30 1 e ,

in v n t ion Of 28
e , S pe cific gr a vi t i es of mi x e d ac ids 121 ,

s mok e les s powd r for e , 28 9 ni t ric id 1 18 ac ,

Ripp ing mmon l 39 3 a a , 106

sul phur ic a c id 10 1 ,

Ro bur i t e 389 390 39 1

, , , Sport ing powd e rs 322 ,

Roc ke t s w a r 33, , rifl e po wde 30 8 rs ,

Ro tt w e il powd e r 3 19 , S pre nge l e xplos i v es 43 , , 3 78

Ro uma nia n s moke l ess powd e r 29 8 ,
S p ng sa lpe t r 88
re e ,

Rus sia n s mok e less powde r 29 8 , St bili t y 7 3 69

a , ,

St mp mi lls ea r ly 24
a , ,

Strw furt s l t d posi t s a e , 63

Sa f t y e xp los i ves 374
e , Stee lite , 38 2
in t H e le n s powde r 39 3
’
Sa , Sto w ite 374 ,

Stra igh t dyna mi te 362 ,

Sa l t pe tr e 13 53 , , St yphnic a c id 28 1 ,

India n indus t ry 57 , Su lphur 69 ,

ma nufa c t ure of by co n v ers ion , , 63 Sul phur ic a cid 9 5 ,

re fini ng 61 65 , , co nce n t ra t ion 9 6 ,

Sa ms oni t e 3 74 , ma nipula ti on of 128 ,

S xoni te 374
a , p uri fica t ion 9 6 ,

Sch u l tze s moke les s p owd r 47 327 e , , spec ific gr a vi t i es 10 1 ,

Schw e i t ze r s rea ge n t 153 Sul phuric es te rs in ni t ro ce llulose 1 8 8

'
-
, ,

Se ns i ti v e nes s 2 23 1 3 68 , , , Supe rco oling o f ni t ro glyce rine 23 7 -

,

Se pa ra t ion of ni t ro glyce rine -

, Supe r ~
e x ce llite , 39 6
 TNDEX O F S UBJ E CT S 407

V A P O U R explosions 352 ,

V pour pr ssur o f ni t ric ci d 1 19

a e e a ,

mix d aci d 1 22 1 23e , ,

V loci t y f xplosion 6
e o e ,

T AR 245
,
V iscos 153 e,

T sing cott on
ea ,
1 68 V iscosi t y o f solu t ions f ni t ro c llulos o -
e e, 1 56
T t r li t 274
e a e, V ol t ili t y f ni t ro glyc rin 35 1
a o -
e e,

Te tr a n itr a nilin e , c ll d 274

AL RO DE
se -
a e ,

T t r ni t ro dig ly
e a -
c e r ine , 240 W S pow de r 327 ,

Te tr a nitmp h e ny hn e th y ln itra mine 276 , W a r rock e t 33 ,

T t r ni t ro n pht h l n 269
e a
-
a a e e, W shing ni t ro c llulos 1 69 1 71 1 73 1 77
a -
e e, , , ,

T t ryl 274
e ,
ni t ro glyc rin 210 21 1 214
-
e e, , ,

T hun d rs t or ms 230
e ,
W sh w t rs fro m ni t ro glyc rin 210
a -
a e -
e e,

T issu p p r 1 64
e a e , W s t cid 1 23
a e a ,

T ow rs fo r cond nsing fu m s
e e e , 1 11 fro m displ c m n t proc ss 1 79 a e e e ,

v a p o u rs , 349 ni t ro glyc rin m nuf c t ur 124 -

e e a a e,

T oxici t y f p u of sol v n t s us
o va o rs e ed t ri nit ro t olu e n m nuf c t ur 261
- -
e a a e,

plosi v s in d us t ry 353 e ,
W t r solubl pow d r 90
a e -
e e ,

Tr e mo n it, 39 7 W t r f w shing ni t ro glyc e rin 214

a e or a -
e,

T r nch mor t rs powd r

e a , e fo r , 3 3 4 W ighing dry gun co tt on 305
e -
,

T rini t ro nisol 28 4 -
a e, W s t f li t 38 9
e a e,

T rini t ro b nz n 258 -
e e e, W tt re t lit
e -
39 7
a s ra e,

T rini t rocr sol 28 2 e ,

W tt r dyn mm n 392
e e -
a o ,

Tr i nitr e cr e s y la te s , 28 3 W tt r f lm nit 39 1
e e -
u e ,

Tr initr o n a p h th a le nc , 269 W il d fi 1 3 -
re,

Tr initr o p h e ny lnitra mine , 274 W ood c llulos 1 64 e e,

T rini t ro t olu n
e e , 50 26 0 264 , , dis t ill t ion f 68 a o ,

puri fi c a t ion 262 ,

S piri t produc t ion ,

T ro tyl 50 260 264

, , ,
W r pp rs 3 70
a e ,

Tu to l, 3 75
T wi t ch ll proc sse e fo r glyc e rin e, 203 XY LOI D IN E , 1 52

U SE -
LI STS in ni t ro glyc rin hous s -
e e e ,
230 Y ON C K I TE 38 7 ,

l
But e r 6: T a nne r Fro me an d Lo ndo n