glycerine- its production, uses and examination .pdf

8/10/2019 Glycerine- Its production, uses and examination .pdf

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GLYCERINEITS I'IIODUCTION, USES AND EXAMINATIOI?:

I:OR

C1-1EMISTS, 113 RFUMIslis, S0AI' MA I< II RS, 1'1-1A11MAC ISTSAN I) EX

I'L

0SIVES T ECI-IN0L0Ci ISTS

?

13

Y

s.w. KOPI 'E


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:LREFACE

TO SECOND GERMAN EDITION.

II b

n

I

~ + L Y C ~ 3 J ? I N I 3

belongs to those substances which areiiiacle

extensive use of in numerous branches ofa h c ~ n ic a l eclinology. It is not only the r a w materialtor

the production of nitro-glycerine, but is alsoc w p l o y e d in very considerable quantities, increasingyoar by year, in many other industries, The soap-I lliblicr and perfumer, t h e cheniist and druggist, thetlycr,

and many others use this substance for their1)iirpose3.

T h a t it therefore occupies a very im-pottant position needs no further explanation.

The necessity for a new edition of thisbook

givesthe author t he welcome opportunity to include an;Lacount of all the n e w processes proposed for the

production, purification, and extended use of glycer-ine. T h e book is therefore anew a compendium of

all

worth knowing on t h a t subject, wherein is also

Inlly

described the employment and the productionof derivatives or glycerine, especially the preparationol nitro-glycerine, the examination of nitro-glycerine-oon t a i n i ng explosives, the use of glycerine in thex i mnuhc t u re of toilet soaps, in perfumery, etc.lCwh

scct ion has been re-written to correspond tothe r c c e n t developments, and especially is describedtlic exaiuiiintion of glycerine, and its determinationin wine, beer, etc.

%lie author wishcs and hopes that the second

cxlitiori of his work will meet with t h e saim appro-l )a , t ion that the first enjoyed.

8 . w. KOPPTI;.

_ .

.


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vii


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GLYCERINE.

INTl1OI)UCTION.

G~J.;CICR,IEE

elongs

to those substances which havelorig heen

known

-

it was discovered by Scheele in1 7 7 D - b ~ t it has only found extensive application11101'e recently, as it only then became possible to pro-clucc IC on 5 large scale, it having previously been

regitrded 5s a by-product of but little importance.The close study of glycerine produced in the pure

statu, shows that this body possesses properties which .~*cnde~ -it particularly suitable for the production oftoilet preparations, a.; well as for many medical pur-

poses. The properties possessed by the substance

obtained by the nitration of glycerine are-Ethnically

of the greatest importance, since these sewe for theprodnction of the most powerful exphsives yet

-

known.

In addition to the last-named purpose, glycerine isnctually used in large quantities in the manufactureof

fine soaps and toilet preparations, and on accountof its action on the slciii it is a toilet article of t h efirst r w k .

By far the largest quantity is used for t he Pro-1


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2 GLY

C

1I:RINR

duction of nitro-glycerine, and thence the prc-paratioa of explosive products; it is also used, in

the second place, in the manufacture of soaps andperfumery.

The

discovery of glycerine took place, as has d-ready been mcntioned, in the year 1 7 7 0 , and thecredit for its discovcry belongs to the clieiiiist Sclieclc,since lic caiQried out a close investigation o n t h osubstance

Poriiicil by Lhe t rca t inent

of

lath

withlitharge. Scheclc already recognized one o i the

charactcristic

properties of this newly discoveredbody, viz. its intensely sweet taste, and called i t onthat account i i swect oil ; it was also occasionallyspoken of as

( (

f a t -w ga r .

The naiiie y l y c c ~ i i z cderived lrom the Greek word~ X V K V ~= sweet, was first employed by Chevreul

in the year1 8 1 4 ,

and thischcniist

also studied in

was known, nor any application for the substanceitself.

,.


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IN'VRODUC'VION 5

liniitients, salves, injections, for keeping moist pillmil tablet

niasses, Tor

court-plaster, and gelatinecapsules, as solvent for m e d i c i n d substances, as

r e lne dy

foi.

cliap1)ed

~ 1 ~ 1 ,

or.

eamclie,

for

skill-

tlisteascil, c tc .


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CHAPT1I:R 11.

COMIOUNUS

d N D

UEUOMPOSITION

UL

YCEBINJL

IRODUCILS Ql?

the substancesHIS relotionship of glycerine withknown as

(alcohols is proved by the fact t lmtglycerine

f o m s

coinpounds which are similar incoinposition to those of other alcohols. Ordinarya1cc)Iiol (ethyl. alcoliol) can

be

cliaiiged into e thy lether by abstraction of water ; under siiiiilar con-ditions glycerine gives glycerine ether (ester) ; ethylalcoI101

foriiis with acids certain definite coiupounds ;

glycerine behavesin

quite a, similar way.Th.e

ConipoLinds

of glycerine are of practical inter-est, in so far as possibly t he one or the other inayappear as an interriiediate l)roduct in the productionof

glycerinct on the large scale, e.g. the oompoundwliicli glycerine forins with sulpliuric acid.

In thc pi*odnotion of this coinpound, one mixestwo parts by nioiisure o l concentrated sulphuric acidwith one piut of concentrated glycerine, with con-iiiiiuoiis stirring, whereby the mixture becomes in-tensely hot ; afteiwards the in i s tu re is cooled to the

/ i n \


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12

GLYCERINE

acid in t he so-called ( g acid saponification " ; whilstfrom the glyceride,e.g. tristearin, stearic acid is foriiicd,the glycerine in the iiiornent of its libera,tioii uiiilcswith the sulphuric acid. But in t h e decoinposilion

o l fats by acid,liigher

temperatures areeiiiploycd,

sothat the glycero-snlphuric acid-is iinniediatcly

agaiii

decomposed into glycerine and sulphuric acid, alii1this latter is once inore available for llie dccomposi-tion

of fresh fa t .

GLYCEIZINE

TI-IER.

As is well known, ordinary alcohol f o ~ i i i s ,wlienwariiied with sulpliuric acid, a coiiipouncl, etliyl-sul-

'

phuric acid, which i s a coiiipouiid coinpletely anal-ogous to gl3iceriiie-sulplii~ricacid ; by heating al,ovc140' the ethyl-sulpliuric acid decoinposes into ethylether aiid sulpliuric acid.

By treating very concentrated(anhyilrous)

gly-cerine at a high temperature, with coneelitratedsulpliuric acid, not only is the first-farmed gl.ycerine-sulphuric acid decoinposed iiito its constituents, h u twater is also re ivoved from the glycerine, aiid acro-lein is proiluced, owing to the great i l e l ~ y d ~ i ~ toction of sulphuuic acid, wliicli is iiot esliaustctl even

by the hydroxyl g r o u p of glyceriiie :

-C,,I,(OH),,

= C,R,O + 2H,OXI p cw ine

:tcrtrlcili \v , i tw

.We shall have to return later to t he p r o p r t i e s ofacrolein itself, since it is one of the frequently appear-ing decomposition products of glycerine, aiid is 01.practical iriiportaiice in the study of fats.


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16 GLYCERINE

place of hydrogen i n one of the methyl groups.The following

f o r i n u l ~

willinalre

this relationshipclear :-

There is also anotherc.ompound

which nieybe

re-garded as an in ter inediate product in the above sub-stitations, viz. epichlorhyclriii, It is obtained whendic ilorhydria is treated with aqueous potash solution.This is a liqnicl boiling at 118" C., which by treatt-

11

inent wi lh

hydrochloric acid is again changed intodichlorhydrin. dI

p-By treatment of glycerine with hydrobromic acid,

t x

phospliorus Iiroiiiide,

broilline

dc~iva ,

tives:we

oh-

chlor ine-de~ivatives. These are as follows:- i

tained

which nresiiiiilair

in constitution to the ! .


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i


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i.8 C:r,TciWN

i:

8parts iodine in carbon bisulphide. and 1 part ofphosphorus,

sild

after distilling off the carbon bi-sulphide, anhydrous glycerine is added iiz sniall quan-tities t o the phosphorus iodide remaining. The two

-

bodies react on each other with greet violence, andfrom the resulting

mass o n e

obtains, by distillation,propylene, water, and allyl iodide.

The crude allyl iodide is brown colourcd ; it itlaybe decolorized by shalcing with caustic soda solu-tion, rectified over caluiuni chloride, ani1 is l;lieiiobtaiued as a colourless liquid, boiling at 102' C. ,

which has tlie sp.gr.

1 . 7 8 9 ,

and

a

stronggarlic-lilce

odour. The propylene passing over as a by-product,by strong cooling andpressure, condenses to a c01oui:-less,peculiar-smelling liquid.

Glycerine is, as already stated, an alcohol, but itis a trihydric alcohol, whilst from the combination,

C,H,, that is the radicle propenyl, one obtains aiiioiioliydric alcohol, allyl alcohol. This is then aproof that the radicle

C,,H,,

which is coiitnined inglycerine, is not quite identical with tlic radicle allyl.It may be quite readiIy distinguished by its difl'ei:e,ntatomicity from the latter, to wliich, however, in riiaiiy

points it stands very near.

It is, moreover, possible to directlyproilucc

allylalcohol from glycerine in the following

n1aiiner

:

When one heats glycerine with oxalic acid up to110 C., formic acid and carbon dioxide are produced ;out of the diluted liquid, formic acid may be obtainedby distillation. As regards coinbination of the formicacid with the glycerine, this is only induced at a


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liquid s e p r e t e s , which possesses the cmipos i t ionC,,H,Cl(0 . NO,)$ = i l in i t ro i i ionocl~lor~lycer i i ic cn:C,H,CI,(

0 .NO. , ) niononi tPodic l i lo~~lycer ine .Ainoiig the numeyow compormds pmciuced from

glycerine by substitution processes, u p till now onlyone has attniiiecl tecliiiiclzl iiiiportance, aiid this isthe nitroglyceride ester (erroneously lmowii as nihro-glycerine) ivliicli is distiiiguislied by t h e propei:tytha t

it is decoiiq~oscdbyCL

blow with a violencewhich exceeds liy far that of othei. explosive sub-stmices. In consequence of this p~opei:i;y,the 00111-pound ~ e f e m d

,o

is e l i q h y e t i in technical explosivesin eve]: increasing tlays, md its ninnufnctnre foriris aspecid

inclus try ,


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3u ~ t r ; c i l : R r ~

3

line earths, as for esainple with qLllClili111c, 1mrcrarely with caustic a l l d i , as in the older

procssei;

for stenrine production, or by saponii icat lo~lwltllsufficient lime, which is a far less coii i ino~l .11~tl10(1,

toforin cnlciuin

soap, with thes i m u l t a n e o u ~

i q ) l o y -

inent of high pressure stewu.Other inethods for the separation of h t t y acids

from glycerine-incorrectly termed sapoii i f ic~-~tiprocesses-are those in which the decomposition olthe fat is effected by ineaiis of acid, inore cipcojallyby sulphuric acid; finally there is the use of even

water itself in place of acids,t he

sqlonif icni ion

being brought about with either superhca tcd WiLiCYor superheated steam.

These methods are all certainly adapted for tlicproduction of Tatty acids for cinployment in themanufacture of stearine candles ; they are not, how-ever, equally suitable when, as at yresent in allworlis of this lilnd, it is a question of the prodnctionnot only of fatty acids, but also of glycerine,

-

thus,for

esaniple,

in Clie process of saponification withmuch acid and at high temperatures, t h e glyocrinr

is entirely destroyed. It is for this reason t h a t t I i (1process of saponification has to be modified, in ordc>i

to ensure that so w l u s b l e asnbstance

LLLS

glycc1i*inois not lost.The present work has for its object tho dcscri1)-

tion of glycerine and its applications. It lies, C h ( w -fore, outside its scope t o occupy ~ u i ~ s e l v e scyvclosely w i t h tlie reactions which t ake place in t h e

various processes iiientioned above. We must c011-


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TIrIt

PROD11C'L'LON OF GLl"CII:IZINE 31

tine ourselves then to iiierely outlining these pro-cesses in all brevity,

and

indeed only in sol a r as

theyIiave rei'eiwice

tot h e pi-oduction

of glycerine

itsclf.The

reactions involved in thevni ious

methods for

car ry ing oiit this ~ ~ i " x s se tlicoi*ctionllyas ioI1o.yt.s:-( ( I ) In tlic i ; : ~ ] ~ ~ n i f i c n t i o niLh alknlics, e.g. witli

lllne

:-

Since in I ' I L I ; ~in addition to stcarin, lnhn i t in anclolcin axe : h o l ) i :cwnt ,

these glycerides are also cle-

c o i ~ i l ~ ~ din the mi l i eway

as

stearin,

as givenabove

; one obtoins thcrel 'ore

a,

m i s t w e of

the limesalts of stearic acid, 1)alinitic acid, and olcic acid-Iiiiie soaps insoluble in water--and a solution ofglycerine.

( b ) Inthe snpn i f ica l icm

withacids,

e.g,

withsulpliuric

: x id

:

-


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40GE"i'CE:Ltl"

k2

Tlie sulphuric acid, diluted by the coiideiisedsteam, is then drawn off, aiid t he fat t ranslerred t othe splitting Vizt, wliere oiie inixes it with aboutO , 3 per cent of tlie previously meiit8ioiied coinbintz-tion of

sulpho-oleic acid and na lh tha lene , adds G0per cent water, and boils by iiitrocluctioii oil steani.The splitting vat is i m d c of pitch-pine woo&-ironor lead would ~ e t a r dthe deconiposition. The con-ducting pipe for the steaiii is inacle of brass.

W h e n the i nass has boiled slowly for twenty-foul:hours, as a rule 8 5 per cent of the f a t will be split.At this stage, in ordei: to exclude the fatty acids f rom

contact with air, whereby theybecoillo

cliscoloured,

one allows steam t u blow on to the s ~ r l a ~ e1: t h cliquid. T h e n the r ims is 1d;t :Lt rest for tlie glycer-ine water t o settle. This, tlio so-called first water,"is drained off, m d fresh water ~ ~ d i l ~ c l .h e whole isthen boiled further, with addition, if necess:ti:y, of a,little inore sulphuric acid, until in all


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THII;

PRODUCTION O FGLYCISRTNII: 45


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4st

GLYC1I:RINJi:

salt ~ n a s swas freed froni alcohol by warming up tol o o a C. in a distillation plant, and one obtained asresidue in the retort a syrupy liquid of yellow to

brown colour-impure glycerine.

Glycerinem a y

be recovered from the lyes oft he

soap-boiler in a less costly way, by evaporatingthe neutralized lyes in shallow open pans over afirc

until its boiling-point reaches 109 C., like ihcboiling-point of a concentratcd solution of co1iiinoiisitlt. The i icutralization is absolutely necessary,

and indced is so carried out that neither an excessof alkali nor acid reniains in the liquid, 8s the

prcs-

ence of either causes t he glycerine to be badly con-taminated by the f'ormetion of' decomposition pro-ducts.

During

t h e

evaporation, salt continuously separ-atcs out from tlie liquid, and this is removcd by

pan, lifted up, and brought into a basket which

the salt can drop back again into the pan.The teimperature. o l 109 C. is finally reached,

when one allows the liquid to run off into a distilla-

lion apparatus,in

which it is furthcrconcentmted,

until t h e t h e m o r n e t o r , which is i n ~ m e i * m lin t heliquicl, reaches

exactly 193"

C. : the heating by fireis then stopped, and a stream of superheated steairiled through tlie liquid, the flow of steam being soregulated that the teiii1)erature does not fall bclow

193" C., and does not rise niuch above thih point, asin the first case no glycerine would distil ovcr, aind

f

ineans of suitahly forrued rakes a t the edge of ihc

hangs over the pan, so that the l i c p d mixed with

i

EI


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50 GLYCISJAINI;:

and the evaporator, and establishcs only a coniiexioiibetween this and t he part of the box to be foundunder the sieve-bottoin. The vacuuin prevailing inthe evaporator is thus transmitted Ih i thc r . If oiienow allows air to pass into the u1q)cr part 01

tlle

box, t hen the atmospheric pressure lorccst he

liciuid

contained 111 tlic salt along, and finally into tlicevaporation apparatus, whcrcupon onc covcw yct withsteani, in older to obtain all the glycci.inc: out oI tlicsalt.

Thc salt inass oiiebrings

finallyin to

acc1ltyif'ugc,

where it is c x t r w t e d with wttter uiitil it only contains0.25 pcr cent glycerinc. With the help o l thisapparatus, one is able t o produce I m n lyes crud0glycerine of 80-84 per cent glyccrol arid 9-1 0 1)crcent ash.

I


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5 2 GLYCERINE

charcoal; this accomplishes the first, but iiot thesecond, object, and the glycerine absorbs, in con-sequence of its large solvent power for lime salts,considerable q~ianbi t iesof these out o the bone-charcoal.

Itwas not until the introdnction of aqueous saponi-fication that the perfecting of the production oi pureglycerine on a manufacturing scale was satisfactorilyaccomplished so that there is in existence in coni-iiierce true glycerine, which can bc regaided as

clieniically

pure and coiisists really only01

glycerineand water.

The empluyinent of absolutely pure fats m a y bercgarcled as t h e main condition for the productionof pure glycerine in this way, because otherwise theforeign matters remain behind in the glycerine sol-

ution, and cannot be quite completely removedfroiii

The fats to be employed therelore-

more es-pecially in the case of animal tallow-niust, beforcthey are ready for saponification, be purified with theutmost care, and this is accoinplished by treatniciitof the saine with very dilute snlphuric acid or soc1:t

lye, withsi innltaneous heating. All membranous

park, which are mixed with thc tallow, are t1iercl)ydestroycd,

and the dccoitiposition 1"lucts arising dis-solve in the c~ciilor alkaline liquid, on which

fi11:1,1Iy

floats the pure iiielted fat, which is eithcr It ioii l t l(~t1into bloclrs, or iinincdiately brought into t h c (le-

c o i n p s i t i o n

vessel.The decoinpositi6n of t h e Iats is coiuplctely d-fected

in this decoinl~osit ionapparatus, and witli t h c

~

it.


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56 GLYCERINE

vapours reach several cooling tubes, staii(1iiig sidcby side, and made of copper, f rom whose undci. milsthe condensed liquid c a n be drawn off t h i m ~ g l i licsiphon-shaped bent tubes. Those vapours, whichhave passed even through the last cooler n n c o n -densed are still furt l ier cooled by means of colt1water. The distillate collected in I h c ltast of I h c s ccoolers consists then iiierely of water.

F I G . 1.

The temperature of the cntering steam rcitdlehivostly

360" -200" , the temperature in tho still200"-220" . The glyccrine which is obtaiiied i'i*oiii

the first receiver contains oiily about 1 0p e r

cont

water, corresponding to 28" 13. I n t h c followingreceivers collects more and inorc dilute glywrinci.The distillation procecds continuously, glyccrinc flow-ing out of I3 into the mass as it evaporates. l ~ ' i i ~a l l y ,hoxever, there collects a large mass of iioii-vol:~t,ilc.residue in the still which is decomposei1 by hoat ,

and contaminates the distillate. Acrolein is formcd,and further, the glyceriiie becomes colourcd ycllow.


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60 GLPCISRINE


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64 GLYCERINE

the risk of the for ina t ion of colouring substniiccsis decreased the lower the temperature at which dis-tillation takes place.

The filtration of glycerine over bone-charcoal isa very lengthy and tedious operation, therefore dc-

coloration is also carried out by heating the r a wglycerine to 100"by steaming it in a boiler fi t tcdwith a stirring device,

addiiig a b l e a c h i i i ~ ocn t, suclias black spodium powder, etc., and then carcfullystirring it. Generally 3-15 pe?- cent bleachinginateria l sufice s, and within o n e to ;.couple of lioiirssufficiently thorough bleaching is

oblained.

Thislias the further adveldage that the glycerine thenonly absorbs very small qua.ntities of lime

froixi

tlici

charcoal, so that subsequelit deliiiiiiig can be dis-pensed with. In t h e case of glycerine bleaclieclin

the

batteries already mentioned, however,del im-

i ng is absolutely necessary. The bleached glycwiiio.'is finally placed i n a va c uum apparatus and broughtt o the requisite concentration.

Deliming

of glycerine can be carried out in sucli Rinaniier that the dissolved lime is converted into :LI~insoluble coinpound which can be reinoved by Rltua-tion. To this end sodium carbonate, sodiuin osa la tc ,or acid sodium pliospliate is addcd to the hoa tcdglycerine, which causes the l'orination or inso1lil)lccalciuin carbonate, oxalate, or phosplinte.

b h


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TM

E113C E~ICRTISS ( )F ( 2 LY C lt1ZTN 15.

T H ~glycerine used inconiiiierce,

apart l'roiii its watercontent, which according to

t h e

variety generally

fluctuates between 2 and 12 p e r c m t , is practi-cally chemically pure and can be obtained entirelyfree from water if it be left for a few days in flatdishes over concentrated sulphuric acid.

Glycerine free from water is a liquid as clcar aswater, of remarkably strong light-refracting properticsand of a syrup-like consistency without any siiicllwhatever and of an intensive burning swcct tastc ;in

themouth

ax well as on the skin of the hotly itcauses a strong sensation of waxiiith,

bccausc

it

a,h-

sorbs water very powerfully. Exposed to t h e air,all concentrated' glycerine absorbs a great deal oi

water therefrom, and further absorption onlyceasos

when the water content of glyceciiic has viscn t oabout 50 per cent. The specific gravity of glyceriricis

1.264

andclecreases

when water is added.Thc

table given below shows the relation bc twcen thcwater content of the glycerine and the specific

gravity of the productiii

question,and,

thercforc,6

3


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'PIil3

PROPERf1'I13S05'

GLYCERIN13

71

in 60 parts, morpli ine hydrochloride in 19 parts,tartar emetic in 50 parts, a i d potassium sulphide in10parts of glycerine.

Glycerineitself

isinisciblc

in all proportions withwaier a n d :~lcohol'or with a i n ix t~z rcof alcohol andc the r , but

irisoltlblc in pure ether, benzol, carbonbisnlldiicle, aird chlomform.


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7s

GLYCERINE

certainly less dangerous than that of fulminatingmercury or of gun cotton.

From

th e in an y worlrs

written on the manufacture of nitro-products, par-ticularly on the subject of

gun

cotton, itseeins

pretty probable that the spontaneousdecoi nposi

tionof the preparations takes place especially whcrv tlicnitric acid employed is not pure, but contains rlc-composition products of the nitric aci(1, aiid in par-ticular nitrous acid. Thercfore in t hc pro(1iwttioii o rnitro-glgcerinc it is not snificicnt to employ LL vcry

pure glycerine, but great care inustbc

1mid to theconstitutioii

of the nitric acid t o be usoil, i m i Cor thisreason manufacturers nowadays only use 1)crfcctlypure nitric acid, which before being employed isseverely tested as to the absence of nitrous acid.As is well known, nitric acid easily dccoinposcs whenthe temperature increases ; as a result of tlic cheui ic ;~ l

reaction which takes place by bringingtogct,liei*

amixture of nitric acid and sulphuric acid with glycorinca considerable amount of lieat is liberatcd, am1 t l icrc-upon it may happen that durinn the reaction de-composition products of nitric acid inay be fO~lJlCtlwhich in their turn react on the glycerinc, resulting

in the formation of easily disintegrated compounds.Therefore in the practical production of nitro-glyccrincall the factors above inentioned must bc most CWCI-fully taken into consideration, and in addition to theexclusive use

o i

pure glycerine, and pure nitric acid,the temperature

niust beprevented froin rihing :d)ovea certain limit by means of a well-regulatctl systcln

of cooling.

9


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GLPCERINE

i

I

i


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1

c


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98 GLYCERINE

d am p 01coal dust, and are used in mines u n d c r t h o

name of Wetter dynamite.I n the second caseby the production of explosive

gelatinee,

the duration oft h e t im e

of gasificationi s

extended, which at thesmne

timercsultq in

I i c t ~ tlosses ; whether this loss iscounIci~balanc:c(l

y

tliofact that the nitro-cellulose coiriplctcly burns t h cnitro-glycerine at the espense o l thc snrpli~s sygcnmust for the time being remain in d icysnce .

I n the technics of explosivesnitro-glyccriiic

has

been applied in several ways; the first esplosivc

preparation used by Nobelwas

constructed in such amanner that cartridge cases of sheet zinc, the dia-meter of which was

soinewliat

smaller then that OIthe bore hole, were filled with gunpowder and somuch nitro-glycerine was poured on it as woultifind room between the grains or powdcr. Whenthe cartridges had been suiik into the bore h o lc thcy

were covered with a layer of powder22

min. high.The charge was ignited by

i n e m s

ofa quick

1n:Ltch

or percussion cap.


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U \'NAMl'P 15

THE manifold drawbncks coiinectcd with I h c uscof nitro-glycerine in tlie liquid s t a i e , ant1 particu1:wly

also the endeavour to rendert h e

manipulation of theexplosive oil less fraught with danger by mixing itwith a non-active solid comlmiient, hitve resulted intlic explosive oil being al .mrbcd by p o r o u ~ ,solid sub-stances, and being employcd in this new form underthe name of dynamite.

Fori i ier ly under the t lcsignat ion dynaii i i le only

that preparation wasundarstoocl

thatw m

obtainedb y tlie absorption of explosive oil by I i i~e lgnhr(kieselguhr dynaln i tc No. I ) .

At 1)rescnt i lynainilc applics to :my csl)losivc snL-stance impregnated with nitro-glyccrinc, the nii t l lrcof the absorption substancc being irnuiatcriel .

Kieselguhr is erroneously designated infusor.in1

c a r t h , as formerly the diatoiris of which it consistswere considered to bc infusorial plihtcs, whereas t h ysl ) r ing lroiii a gcnus of p h n t to wliicli algae belong.They are surronndctl w i t h

a

vcxy strong siliciciLcid

coating, end under t he mic rowope tlic lo rm is thatof & , d i s h , 1~ boat, or a pipe. The appca renco ol'

ins


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DYN4MIT

E101


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jDYNAMI C E 105


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106 GLYCERINE

tuiiately ncciden ts are not s n exception in coiinectioilwith this operation. I t m a y , however, confide11tly

be said that thegreater

iiuiiiber o l the esplosions

would not have occurred hadth e nccessary

carebeenexercised. I t is just the 1-clatively great lack 01danger with which dynaiiiite may be handled thatonly too easily inspires t h e ignorant worlaucii witlia.

leeling of security. Only too frequently dynaii i i te

is handled witli theutmos t

carelessness, orrathei.

inis-

handled, and it is really wonderful that eslilosions arenot more nuinerous. Only the most careful enliglit-ennient as to the explosive characteristics ol dyna-mite, the niost accurate instructions as to itsmanipulation, and absolute severity in case of anyinfringement will in future help to lmvent Chcscesplosioas.

THE

P ~ O P P I ~ T I E S

F D r ~ n i w r ~ r ~ : .

Dynamite is a dough-like, plastic n i m s 01 1.4specific gravity of a yellow reddish colour, and greasyt o the feel, and odourless. It consists ol about 7 5

parts of nitro-glycerine and 25 parts liiesclguhr.Dynamite can only be made t o explode by nieans

of explosive substances, percussion caps, red-liot

metals, sudden heating to a high d e p e , or by a,violent blow or shock. Conling into c o n t w t withlight, a niatcli or b u r n i n g fuse, it burns without ex-

ploding just l ike damp paper. The reason lor thisis that d j G m e in comiiion with all nitro-glycerine

preparations belongs to the indirect exylosive snl)-


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DYNAMlT IC iix)


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119 GLYCICRINE

in its action is practically similar to kieselguhr

dynamite.Krebs' lithofrakteur contains

iii 1 0 3

parts 5 5parts of nitro-glycerine, and although this is 6 0

parts less than inkieselgnhr

dynamite, yet;,i n

spite of this, the explosivc power o l 1ithofml;tenr isgreater than

o l dynatiiite No. I on account of t l i c bentire burning of the nitro-glycerine and the presc t iccof other iiiutually reacting clic iiiicel subst tm ccs, wh io11inan explosion dcvelop a vc3i.y high icnil3cmture iLntI

EL

l a ~ g e

quantity oi' highlyc q m i d i n g

g l ~ scs . Owingto the nature of these substances and thecoiiiplutc:

burning ofthe

nitro-glycerine int h c

litl1ol'riikt(>ll~,

these gases consist only o l carbonic acid, hydrokcn,

water gas, and a trace of sulphurous acid; they i%1*0free froni

steam-vapour

and in noway

injurious b ohealth, neither do they

iliin the

light of thel t t iups

in the mines.The 45 parts other than nitro-glycerin0 wliicli

coiiipose litliofrakteur contain only21

parts 01infusorial earth and 2.1 pauhs of' olhe r absorbingsubstances which not only

liccp

tlicnitro-glycwin

c

in suspension, but in the casc of an explosion w o

almost entirely converted into gases of hight c m p c pature and dilation.

These substances arecmbon,

prepared h m , p c -pared sawdust,

bar ium

nitrate, sodiumsesqui-carbon-

ate, manganese, and sulphur. They arechoscu

in suchproportion that in an explosion they develop tlichighest temperature and largest quantity oi' gas,

a11d

the following points of view are considered : Cht~r-

4


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116 CLYC

ERINE

cartridges, must therefore be attributed to the otheradded substances, whereby evidently

l i thofrakteur

isdistinguished

f rom

dynamite.

More oftent h a n

noti t

has been observed thatdynamite cartridges, particularly when they are long,only esplode partly so that the lower part which isfurther from the percussion cap remains unburnt ;or in blasting operations without D, bore hole with

loose tamping,p u t

of the cartridge is hurled awaywithout exploding and is, therefore, withouteflect.

Thishas

not been found to occur in the case oflithofrakteur owing to the easily inflariiniable sub-stances dispersed throughout the whole mass, andits not too rapid combustion.

A furthcr advantage of lithofrakteur over dyna-mite is that in daiiip and rainy weather, when ex-

plosive materialm u s t be used without casing, it can

always bemade

explode whereas in a siiiiilar casedynamite

sonietiiiies

fails.

Another coinpositiono l

l i tho frttkteu r is

6 '

e n

asi'ollows :

-54.5 parts nitro-glycerine, 14.75 parts bariumnitrate,

2

partsmangancse , 2 par ls soda, 2 parts

boring dust, 1part bran, 7 parts sulphur, a n d11j.76

parts kieselguhr.2. Iiolonial

Potoder.-In

t h e same way as litho-f rakteur m a y be considered as a kiesc lguhr dynmi i tcmixed with

ingredientB of gunpowder, so liolonialpowder is

a

somcwhat

modifiedforin

of black powdermixture impregnated with nitro-glycerine.

Kolonial

powder was introduced intocoinmercial


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DYNAMITE 129

Gelatine dynamite :-

I. 11.

Explosive oil . . 38.5 25

Magnesium sulphate . . 42.5 64Soda . . 1 1

A drawback, however, of a11 these dynainites con-sists in the fact that Ihr.ough the addition of soda,that is, owing to the water ol crystallisation in thesoda having to be vaporized, t h e explosive action issomewhat lessened. Such dynamite might, therefore,

be too expensive in coinparison w i t h ordinary strongdynamite, the use of which as a rule offers the samesecurity.

Zumic powder . . 18 10

Antnbo7agelntine dynamite contains :

-

Nitro-glycerine . . 25-30per centCollodion cotton .

1

,,

Flour (meal) .10 ),

Aintnonium

nitrate . . 40-45 ,,

These dynamites are much in use, and by the ad-dition of cooking salt the security against ignition isincreased,


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CHAPTER IS.

L ICAD GLYC 14 RlD 3 ; (GL YC ICRIN 5 UEM k;NTj.

IT?

as

been known lor some t h e that glycc>,rinewhich has been in t imate ly mixed with protoxidc oflead (litharge) results in a mass which, after a shorttime, beconies as hard as stone and can h e iiiployedfor many useful purposes, but particuliLrly for the pro-duction of very resistant cements. It was firstascertained by experiments carried out by Morawskithat glycerine with protoxide of lead foriiicd a coin-

bination

of a definite constitution

-

lead glyceride.The lead glyceride which results from th.e rriising ofglycerine with protoxide of lead, is of the followingcoiiiposition C3135(FIPl>OJ

-I-

H,O and is crystalline.The crystals can be obtained in quite ;I p-ire f o r m ,tlittt is, in the shape of very siiiall nexdles, if to ;I

solution of protoxide of lead in potash-lye glyccrineis added.The behaviour of glycerine cement o n treatment

with cheiuical reagents wa,s tried in such a, nianiierthat pa~al le l ip ipedsof 3 m i n . thickness were iiiadeof the ceinent and submitted to t he action of differ-

ent reagents. Concentratednnd

diluted acetic acideasily dissolved the c e m e n t after three hours action ;i

/ \ l

.i

I


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LEAD GLYCERIDE 139

The glycerine cement is a yellow or brownishm i w , which, pressed into moulds and left in these forsoiiw days, fills out the finest hollowings of the mould,

: ~ n d

s, thcre forc,

very suitable for coin impressions orrolieis, wliich are more solid t h a n plaster or cementcusts.

T'hc ccineiit is pa,rticularly suitable as foundationsi ' o ~objects which are of considerable weight, and

which are, therefore, constantly subjected t o blows,lor this cement, in spite o i the hardness it gains inccnirse o i time, never loses all its elasticity. Founda-tions

of stcarri engines, stamping machines, etc.,h o v e

thercfore been made of lead-glyceride which is: d h o u w d for cementing stones. I n order to cementstones, t h e spaces in question should be smeared over

with concen tmted glycerine, then litharge should bepowcleucil 011 to them, and the stones tightly pressedone on

i h e other a n d for some days kept under pres-


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..._

...

_ _

..... ..

..... ..

CHAPTER S

Owma to itshigh

boiling-point,glycorinc in

belongs t o those substances which ova,L)or:Ltegreat

di6cul ty

; but i t also possewt ;considetxhlo

Iiy-

groscopic

qualities, that is it absorbs water I ' T X J I ~ ~ t h oair

or

from those bodies with which it isbrotigl1t

in contact.Tlierefore, if

a widew ise1

containingglycerine is exposed to

the

air,t h c

liquidIh(:r-oin

is increased because glycerine draws wator S r o i uthe air.

If, then, a substance which, wlien exposed to tlio

air on drying beconies hard and brittle,i h

iiiixatl

witlia suitable quantity of glycerine, it c m 1 ~ :


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136 GIG YCEHINF:

In most cases people are content with rubbingthe flesh side of the

f'ur

witha l u m

and cooking salt,

and accordingly give i t a superficial white tanning.Furs treated in this manner have, however, two

drawbacks

-

the skin, in spite of the fact thati t

isnot very thick, is brittle, because softening thereof

by mechanical nieans (lulling) c a n not be resortedto, owing to the care with which the hair side m u s tbe treated ; or it cannot be proceeded with in such amanner as to render t h e skin quite supple. The

second drawback, which in the case of some f u r sis noticeably unpleasant, is the smell peculiar to theanimal from which the fur is obtaincd.

Both drawbsclis can be reiriediedin a very simplemanner, if the preservation of the fu r is acconiplislied

by nieans ol glycerine, and this is carried out in thefollowing nianner :-

The skin is first placed in water in order to renderi t supple, and is then washed in either a soap or sodasolution in order to remove fa t or dirt and to con-serve the hair side in all its b e a ~ i l y . After thistreatment the fur i s repeatedly rinsed in water andis then placed, the hair side downwards, on a table

and the flesh side is then manipulated with the in -s t ru inen t s

as used by tanners lor this purpose a n dall particles of flesh and all hard lurnps in the skinrernoved. I

After coiiipletion 01 this work, the skin is rubbedon the flesli side with concentrated glycerine, in which

boric acid has been dissolved ; this rubbing is repeatedtwo or three times and the skin is then hung in a

room

1

I


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GLYCERIN E AS SOliTENING SUBSTANCE131

to dry. By means of the washing process, the skinis thoroughly soaked through and through withwater; as soon as the concentrated glycerine isapplied to the flesh side

of

the fur, the action of

osinosis sets in and the whole skin is thenimpreg-nated with a diluted solution of glycerine correspond-

ing to the water contents thereof.If the skins hang in dry air, then the water is

allowed to evaporate until the glycerine is so con-centrated that no

more

water escapes; the wholetissue of the skin is now so impregnated with glycer-

thoroughly protected against decay by the strong

In order to mask the faint smell which some furseven after repeated washing do not lose, instead ofordinary glycerine, such glycerine should be used asis slightly perfumed wi th a not too volatile sweet-

smelling substance such as ambergris or nutmeg oil.The fur treated in this manner, on the flesh side

has the a p p e a r m x e of a fresh skin ; i it isdesired toimpart to

it

the appearance of tawed leather, thiscan be accomplished in a very simple manner byspreading over it a cold solution

o

a l u m

or

a lumin ium

sulphate, leaving it to dry and then dabbing it over

with a sponge dipped in ammonia. I n this waythe

aluniiniuin

hydroxide is separated from the fleshside of the skin, which thereby has t h e appearance oftawed leather.

In the same manner as for furs can be treatedthe skins of animals, which are to be stuffed, such

ine that it will always remain supple, and is

antiseptic action of the boric acid.

III

I

I


143/255

as birds, and this process is particularly valuable fornaturalists when travelling, who are not able tostuff iiiiiziediatelv

the skins of animals and birdscaught. If the fresh skins are treeted with glycerine

in which for this purpose salicylic acid instead ofboric acid

has

been dissolved (onitccount

of its power-ful preserving action) then

t h e

skins or birds can,as soon as they are dried, be l ) d i e d in bosos and leftthere as long 8s desired. Ii t he bird is to bc stuffed,then it is quite supple

and much trouble is savedwhich would be otherwise occasioned by

t h e

soften-ing of the dried and stif? skin.

Glycerine is also ofi iupor tance

to thena tura l i r tfrom

onotlzer

point of view, andtherefore we tonch un

its value lor natural history purposes. It is knownt h a t soine aninia ls preserved in alcoliol 1,ecoiiie ir-recognimble

int l x c o u r s c

of tinie, becauset h e

alcohol dissolves thef a t in t he body and ilcstroys

the colour. This isperticularly

noticeable in t h e

case ofsonie

beantilully colou~ed

wit

worins

andf i i h

which shrink in alcohol andontirely

lose theircolours. We have

h u n d

that glycerine which issutliciently

diluted withw a t w , in order that tho

verywatcry bociics of woriiis end otlicl: niolluscs as

well as ofiishes

should nots h r ink

by the absorp-tion of the

watcr ,

iseiiiiizeiitly itila1)tttblo

for

the


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142 GL Y C ERIN 3

grating it. The grease is divided into very finedrops which float about in t'he liquid and give it amilky appearance.

By repeated treatment with degras, a certain de-gree of suppleness is given to c l imio i s leather, anti

presence of alkaline substances provents any specificodour due to rancidity, as t h c lree fatty ttcids uesiilt-ing therefrom are at once bound. I n spi te o l t l i l s ,

chamois leather has a characteristicsiiiell,

very1 ~ 0 1 )ably due to small quantities o l volatile fatty x i d s

which cannot be bound by the alkali.As the application of degras only results in the

suppleness of the leather, this preparation can beentirely substituted by glycerine : one application

of glycerine to the chamois leather (it must berubbed in as long

as

the leather is wet) quite doesaway with the treatment with degras ; t h e leather ishereby rendered supple, without after

soiiie

time as-suming a strong odour or darkening, as is illore or

less the case withleahher

which has been treatedwith degras.For this and other similar ~ " y ) s e s there is 110

need, ILS will be seen, touse

highly purified glycerinewhich is absolutely colourless and o(hiir less, but a

product m a y be used that has siniply becn obtainedby means of distillation, and which does not need tobe colourless and odourless. With ray-lard to thelatter quality, it must be remarlied that there shouldbe no sniell of acrolein, as this substance evcm whenlargely diluted has a very objectionable odour.

In the manufacture of tawed leather, so-called


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144 GLYCERINli:

During this t i lne the

glycerine is evenlyihbSOrbCd

by the whole mass of the leather and a tta ins therebythe highest degree of suppleness. During the process

of dyeing by painting or by means of d i p p i n g , t h eskins lose part of their suppleness, and,

the re fo rc , apreliminary

esperiii ient

should beiiiadc

in ordcr toascertain in how far tlic glycerinc should bc tlilixtcdso that the leather

inay attaiiz

tlzcnccessiLr.y

clc:gr.cc

of suppleness.It is, moreover, possible, aftert h c

y7acd

l c a thec

hies

been dyed, by rubbing glycerine in on tlicnon-clycd

side to give it the necessary ilegrce o ls i i p p l c n c s ~ ,

and it needs only a simpleexperimcnf;

in order todetermine the quantity of glycerine which is I'LCCCS-

sary to impart to the leather lastingsuppleness

ani1

elasticity .Glycerine is also of value to

manu lac tn reus of

tanned leather because it imparts to this p w t i c u l n rleather a high degree of suppleness. The vn inps o l

boots which owing to faulty tanninga r e

bonicwlxbtbrittle, can be very muchimproved

in qudityt~nd

rendered quite supple. To this endthc

leather.nccd

only be spread with glycerine on one mdo,md,

ifnecessary, this operation can be repeated

onco

or

twicc .

A heavy red tanned leather such as i h iisctl lor

belts possesses the drawback that it htts very l i t t losuppleness ; a considerable portion of the

~ m w c r iseil

to drive machines with belts is lost bccausc tlicbelts

only turn round the wheels with stiffness.'1'1-1~

edges also easily fray and aftera tiriic

split.

These drawbacks can best be remediedby i m y r c g -


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GLPCERINli: AS SOFTENINGSUBS'J'ANOE

143

nat ing the belts with glycerine, which can be ac-complished by repeated applications of glycerine, and

by this means even very thick straps without inthe least losing their firinness can be iiiade 50 supple

and durable tha ttliey

even ru n round wheels of veryslight diameter, without fraying or necessitating any

particular expenditure of lorce as regards bending orstretching.


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PREPSRArPIONS

O F GLYCERINE AND GLUE 147

glue can be used for quite a nuniber of differentpurposes. According to the end in view, glue ofdifferent degrees of purity can be used; the mostcoinnion

joiner's glue and the finest colourless gelatineresult in preparations of fairly siniilar qualities and

only differ strongly from one another in colour.The production of glycerine glue is best proceeded

with in such a manner that the glue is first allowedto soak in water and the cakes are transfornied intosoft flaky inasses, which on lifting can easily be torn,the water is then poured off, the steeped glue care-fully melted

and

boiled when all thescum

which ap-pears during boiling floats on the surface and is

removed.After this the necessary aniount of glycerine is

added, and by stirring is intiniately mixed with theglue solution.

manner does not show sufkicient firmness on cooling,then this is aproof tha t the mass contains too much

I

can be reiiiovcd. The only precaution necessary totake in this connexion consists in constant stirringas soon as tlie ma ss begins to thicken in order toavoid burning, which easily takcs place where theflaine touches

t h c

vessel. If evaporation does nottake place over an open fire but on tlie hob dangerof burning is much less. Burnt glycerine glue has

a dark colour and a peculiar sweet sort of smell.If the evaporated mass is sufliciently firm, it is

immediately poured into shapes ready to receive the

I If a sample 01 glycerine glue prepared in this

water, and by careful evaporation the excess of water

I

I

i

1


153/255

148 G L Y C E R I K I ~

inass, and they are left for a time until the entireinass is so hard that on touching it with the fingerit does not stick.

If it is a case of making a light-colouredglycerineglue from dark glue, then, on soaking, the glue m u s talso be cleaned. I n the place of plain water, waterto which a percentage of strong vinegar h a s beenadded iiiay be used, and the first water is poured on

to the glue only three hours later, the second :tiidsubsequent (4-6) waters at intervals of two hours.

Owing to this water containing vinegar, osinosisextracts from the glue 3, considerable number of saltsaiid colouring niatter, and in this way it is possible

to ilianufacture f ro in an evil smelling, practicallyblack glue, glycerine glue which is the colour of(lark amber.

GLYCELZINEGELATINE,

This preparation, which isein inent ly

suitable fort h e preservation of delicate microscopic preparations(see p.

140), is obtained as ollows: The purestcolourless geliitiiie is steeped in water iol: so longthat, after the water is poured OB,on heating i t justmelts at 100". The steeped geletine is placed in a

glass, which isput in water and heated until it boils.As soon

as

the gelatine has inelted, concentratedglycerine is dropped into the liquid and mixed bystirring with a glass rod, the inass is then pouredinto a cliina cup and left to congeal.

The addition of glycerine is so proportioned tha tthe congealed mass o n heating becoines liquid at


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154 GLYCICRINR

mass (that is containing more glycerine) m o re copiescan be taken, the last ones of which, however, showfainter outlines.

According to certain prescriptions for the prepara-

tion of hectograph masses, a powder-like substanceof a white colour should be added to the glycerineglue in order to obtain a milk white mass, whichshows up the writing more c1e:trly. Such substancesare, for example, finely ground heavy sl)itr andzinc white: but there is not much object in thisbecause it is not a question ol reading t h e writing

transmitted to the hectographs but oi reading thecopies talcen from it.

Moreover, the addition of such substances hascertain drawbacks as to the clearness of the copies.Under all

ci rcun is tances

the clearest and iiiost n i x "ous impressions are obtained when the

hcctograph

inass is composed of glycerin0 and glue only. Wewill now give

soiiic

formulae for theiiialiing ol these

hectograph. masses :-

A.

Size . * 100 g.Glycerine at 28" Beauin& . . 500 ,,

13.

Size . . 100 ,,Glycerine at 28" BeibumB . . 400 ,,V ate r

200 ),


160/255

are hectograph inasses with additions of white

substances which enable the writing to stand out

more clearly, and also facilitate the washing awayof the characters. I l e a v y s p a r must be used eitherin t lw for in of the finest powder, or, stillbetter, veryfinely divided barium su lpha t c should be used, whichcan be obtained by i i ieans of precipitation o l a solu-tion of bariruri chloride with sulphnric acid a n dwashing thc dcposit .

A .

Size . . 100 g.Barium

su lpha tc

(wet) . . 0.5 1.Dextrin . . 100g.Glyccrino . .

1000-1800

g.

Dextrin andbizc

are

clissolved togctlier,

then theglyccrine, mcl finally bariuin sulphate added, and theinass is pourcd into rnoulcls. If an insuf:licic?ntnuinbcr

o l copies results, or if the wri t ing can onlybe washed of1 with d i l h u l t y , thcn a inass of theproper ( l d i t y CiLn be o1)tained by xiiclting it againand adding glycerine.

13.

Size . . ' 100g.Baryta precipitntc . . 0.5 1.Glycerine . .

1800

4.


161/255

156 GLYCEiRINIC

C.

TheF r e n c h

Ministry forPuldic Works rcw11~-

mends

the following :-

Glue . . l o o $Glycerine . . 500 ) ,Finost powdered

hcavy s p : ~1 c l ~ ~ i i s c i l

kaolin . . 26 ,,Watcr . 375

HEUTOC~ILWI-IA i S ~ ~ 3 SVCOI{) I N ( ~ 10 \vOJ{rlll i

Gelatine . 100g.Dextrin . . i o o ,,Glycerine . . 1000 c.crY1.B,ir ium sulphate . 80 g.

Hectograph sheets which arcintcndcci

to bcnsctl

only once can bc obtaincd by pouring the l iquidhectograph mass on to a smooth horizontally placcdglass plate, and

t r ens ie r r ing

it to porous papcrbelore

hardening, by pressing ita n d

avoiding ilic

formation o l air bubbles.Pi~pcr

m 1

J ~ ; L S S

coiii-

bine and can bc drawn off. Thc s u r f w c ol thesoliectograpli sheets is very

s ~ n o o t l i ,mil

Ithisr w s o n

it is eminently suitable for thc trunsinission ol wi-i -ings,

drawings, ctc., with vcry finc l incs.


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158 GL'lfCI~~RINI4

power exercised by the hectograph nia& on t he inkis just as strong as that exercised by the paper, and,therefore, no further copies can be taken.

I n order to obtain good hectograph inli, two points

must be taken into consideration

-

the colouringmatter contained in the ink must be very intcmseand the inli should never altogether dry up asotherwise the mobility of the particles is paralysed.Therefore, for the production of thcse inks the strong-est colouring matter is used; these are so-called

aniline dyes (fuchsin, methyl violct, water-soluble blue,iodide green, etc.), in the forin o l concentrated solu-tions to which glycerine is added in order to prevcntdrying up of the inli.

Glycerine incorporated with t h c hectograph inknot only serves to keep the characters soft, but alsoacts as a solvent for the colouring i i ia t ter itsell', be-

cause only a few aniline colouring substances aredirectly soluble in water, but they easily

dissolvc

inglycerine, particularly when it is warmed.

Therefore, in the production of hectograph inks,the best method is to place the weighed-out coloiiringmatter in a china

mor ta r ,

pour over itthc recjuisitc

amount of glycerine, andmix

theco lo u ~ in g llibtt(+r

with the glycerine byinems

ol' thepestle.

RI'ter

this has been done for some time, so thiht no grainsare noticed in the mixture, the iuortttr is heatc:tlto 50 -60' C. and thereby the colom-ing Inattcr isbrought into thorough solution, as w a r m glyccrincdissolves far more of it.If aniline colouring matter so lu l~ lcin WiLtel., lor


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A P P L I E D 10 CHE MANUFACIIJRE OF 1 K S 159

instance water-soluble blue (alltaliblue), is used, thento the thick solution of the dye in glycerine so muchwater is added that a liquid results, th e consistencyof which is similar t o that of a thick ink, and then

the hectograph ink is ready.If an aniline dye, insoluble in water, is used,

for instance niethyl violet, then the thick liquidsolution in glycerine is diluted with wiLter to the ex-tent that it becomes as thick as syrup, and so muchalcohol is then added as is necessary to produce anink of suitable consistency. An excess ol alcohol

should be avoided lort h e

reitson that inks contain-ing too niuch alcohol thicken so n i u c h in the processof writing, owing to the volatility

of

the alcohol,thai,

it is not possible to write fine charac tc rs with it.

PRESCRIPTIONSPO13 V A E I O U t ; COLO

Ul3I3D FIlNTV )C+IIAllW

I

Water-soluble blue . 10 g.Glycerine . 1 0 ,,Water . . so-100 ,,

Thin blue id


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162

GLYCISRINE

For violet inks . Methyl violet and crystal violetFor green inks , Brilliant green and malachite greenFor red inks . FuchsinFor yellow inks . Aummin

2.

C o i w m

INKS.

Copying inks are thosc inks which allow at Icastone very clear copy to bc taken

of tlic doculucn twritten with them ; these inks are i i i ~ s t l y n s o d in

business, in those cases wlierc only one copy of tlicdocument is needed.

The preparation of copying inks has beenlooliedupon as very

d iEcu l t

ofacconipl is l iment

; at the pre-sent moment, however, such successful at tempts have

been made that in a short time practically everyink can be t r ans formed into

a

copying ink. Agood copying ink should possess the propcrty of dryingslowly and when, after a time, a damp and poro ix

sheet of paper is placed 011 tlic document, should sosoften again that part o l t h c ink is absorbed by t hcpaper.

Formerly, copying inks wereiiinde

by i i i is ing withthe ink, extract of

logwoocl

and grape sugar, twosubstances with very strong water-attracting

qual-

ities. This hygroscopic quality prevented cn t i rc

clrying

of the characters, and therefore after at inic

a good copy of the writing could be talien.By the application of glycerine, the production of

good copying inks has been rendered a vcry siinplcmatter, and every ink by t h c addition of glycerinecan a t oncebe turned into copying ink. Th e amoun t


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164 GLYCERIN +:

has only a slightly thickening eflect on the ink ; thisdiffers, therefore, advantageously froin other inks inthat very fine characters can be written with it, as

it is sufficiently thin. In spi te of this quality,copies can frequently be taken, as it penetratesvery deep into the paper and re i l ia ins damp forsome lime.

Bottgers composition for a copyingink

isgivon

as follows :-

L o ~ w o o dextract . 64 g.Soda . 16 I ,Potas j ium

chromate . 9 I ,Glycerine . 64 ,,Gum . 1 6 I ,Water . . 270 ,

The logwood extract is dissolved a t the same limeas the soda in water, glycerine and gum are itddedand, finally, potassium chromate, dissolved in a

v e i y

little water (hot), is added to the liquidand stiri*cd,

and it can at once be taken intoUSC.

This copying ink is01

such a capacity that wewere able without using a prcss to t ake three copiesof the original document simply by pressure

o l

thehand; in the copying press, that IS under strong

pressure, another two good copies worc obtained.


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CHAPTEIZ SIII.

Jr

.-....

GLYCERlNII:

AS ASOLVICN'I .

THEproperty of glycerine easily t o dissolve a largenumber of substances which are only dissolved with

difficulty otherwise, renders theappliciLtion

o l glycer-ine of great use in inany trades. As has alreadybeen iiientioned, when describing the qnal i t ies o lglycerine, it possesses the propcrty ol' dissolvirigeasily so-called aniline dyes, which arc iiiostly onlysoluble in strong alcohol, and this property findsextensive application in dye works as well as in

printingtvorlrs.If, for ins tanae , in printing works aniline dyes m e

to be used which are only dissolved in alcohol, certaindifliculties,

which are due to the volatility of thesolvent, must be overcome, as owing to the volatilityof alcohol the colour easily thickens, and then darkershades result than were originally intended.

This drawbackc m iiiiiiiedia te ly

be1-emedied,

by

substituting glycerine for the alcoholas t h e

solvent ofthe aniline dye. I n order to dissolve the colouriiigmatter , first of all a siiiall amount of glycerine shouldbe poured over it in order to pmvent the i inc ly

,

i

i 2 \


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GLYOISRINE AS A SOLVENT 167

divided dye scattering as dust, so unpleasant in thecase of v c i y deep dyes, and the dye should be mixed

w i t h the glyceyine to an even paste. This should bestirred constantly and as m u c h glycerine added as is

n m es s s r y

to effect the solution, and then this solutiono m by stirring be in t in la te ly mixed with the thiclr-cning su1)stanco whether dextrin, gum solution,i~'Lgi~ca1ltl lmucilage, etc., which is used for the pro-duction of the colour, and a printing colour resultswhich in addition to the advantage of remaining the

bailie on drying, neither dries norcruinbles,

and en-ables the printing of the particular dye on the tissueio be accoinplished with great facility.

Prescriptions in connection with colour printing,consisting of dissolved aniline dyes, are very n u -itieroiis and vary according to the shade of colour onewishos to obtain. An example of aniline pink is

the following :

- I.

Fuchsin . . 0.12 kg.Glyccr i i ic

. .1.00

,,wLt 1?1 . 1.00 ,,Guruiiii w eb icu n i . . 0.84 ,,

TI.

. 3.50 kg.

.3.50

,,

I n dyeing works in which either yarns OY alreadyfinished t ex tu res are to be dyed with aniline dyes,

the dye is brought into solution by boiling with


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alcohol, and these solutions are usedfor

dyeingin

suitable dilution.1

G L Y C E R IN EOE THE EXTRACTION OF PEROUBIES.

A very important application of glycerine is inobtaining certain substances used in porfumcry ;the iiiost important ingredients in per lunie ry are, asis well linovvn, the essential oils lound in sweet-smelling plants. T h e quantities O ethereal oilsfound in plants are so small in the case ol the mostvaluable, and the separation of t h e m accompaniedwith so i i iany difficulties, that these oils belong tothe inost expensive substances known. Althoughcertain plants containing these elliereal oils

are

ex-tensively cultivated in certain

di,tricts (for instancein the south

ot Prance, in tlie surroundings of Cannes ,

Nice, etc.), thedeii iand

for genuine ethereal oils(violet, i i i ignonet te oil, orange flower oil, acacialarnesiana oil, etc.) obtained from flowers is so greatthat the exceedingly

h i gh

prices wliicli are aslied forthese oils aye still rising.

Glycei-ine is ail excellcnt i i ieans of obtaining

sweet-smell ing

substances fromblossoms of the mostvaried kinds, and particular stress should here be laidon t he fact that glycerine is eininent ly adapted forthe extraction of all swcet-smell ing substances Proiii

parts ol' plants whether flowers, roots, wood, or fruitpeels, because it is a, solvent lor all these perfumes.

The method used for the extraction of perfumesfrom flowers by nieans of glycerine coiisists in thefollowing :-

t


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172

GLYCERINII:

By a careful addition of water t o this perfumesolution in glycerine, t he former can be diluted to acertain extent, without the liquid losing anything 01its clearness

;

but if this addition of water goes be-

yond a certain extent the liquid coiiiiiieiices to opalesceand o nadding

more waterbecoiiies soriietiiiies

quiteniuddy ;

the essential oils and other substances whichare extracted from

t h e

flowers are only soluble in aliquid which contains a certain quantity of glycerine,aiid are therefore separated when too

inuch wate,r

isadded.

Solutions ofaroiiiatic

'substances in glycerine,diluted with water to a point approaching that atwhich turbidity sets in, still retain the fresh

siiiell

of

the flowersa'nd

can be used for very fine toiletwashing water. I n order to proceed further withthe dilution than is possible with.

w a t w

alone, assoon

as

the turbidity point is reached, stronglyc1ilui;eil

methylated spirits at10-15

per cent, which niustbe

free from fusel oil, is added and this preventsseparation of the essential oils.

Rut iniuany

cases it is n question ofolitaining

these aromatic substances in an absolutely pure st;tte,and in this connection the glycerine

solntions

are

treated in the following manner :-

The glycerine which has been drawn. off froin theflowers nnd filtered is placed in large glass bot t les ,closed with corks which are

most

carefullyfitted into

the necks of the bottles. Before the glycerine isplaced in these bot,tles, so muchpure benzol isplacedin

t h e m

until they are filled wi th it to about one


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174 GLYCISRIN14

mat ic substances of the plant world can be obtained,and for this reason glycerine deserves the considerationof all those interested in the production of pcrl'umeiand p.articularly in obtaining essential oils froin frcsli

flowers. It is a lact, Iiowevcr, tliai this plroccsswhich, under certain circuinstanccs, is so liiglily to berecoiuiiiended, is hardly r c so l r td l o ;Lt : ~ l lin pr;Lct1c(i.

GLYCIJIiIN1:

U U X ) IN T l I l i ; ~ ' M : I ]

COSMIWUS.

Ainong the nuii ierouspreparations sold to t h e publicunder

t h e n a m e

of beautifiers or cosineticsby

per-fumery manufacturers, glycerinc ranks :LS onc of thefirst, as, i iproperly applied, it possesses tlic q u t l i t y olimparting to the skin brilliance, softness,

a n d

delicatecolour.

The

proper method of application of glyccriac in

connection with the care oft h e

skin is not in a con-centrated forin, but diluted w i i h a suitable quantityof water. If concentrated glycerine is brought incontact with parts o l the body which arc covcseclwith delicate slii1l-for instaiicc, the lips or fingcrtips, there is immediately a strong sensation ol'warni th

due to absorption by glycerine oft h c

water

inth c s li in .By the sudden absorption of this water,

t h e

skin iseasily injured, the soft cells lo rming the t issue of ihclip skin arc killed, thcy shrink an d pee l oil' ;I,S soon ;isa fresh layer of skin is formed undcmeath. As,therefore, by the application of conccntratcd gly-cerine the skin is not preserved but so to say


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GLPCICRESIC AS A SOLV12hT 179 ,

The tincture of cantharides is prepared by di-gesting 50 g. of powdered Spanish fly ( L y t t a -vess icator ia) with 1 1. of strong alcohol. The causticammonia has the same cleaning and degreasing ac-tion as potassiuiii carbonate ; glycerine imparts to theha i r softness and suppleness. The whole composi-tion is very well coii ibined, inasmuch as it has a

cleansingeEect

on tho hair and a t the saiiiet i m e

imparts softness.Preparations which have been in use for yeltrs are

glycerine jellies. These have t h e advantage overlanoline that they a r e niore econoiiiical, but on theother hand possess the drawback of not being soquickly absorbed. Ei the r tubes or glasses are filled

with these preparations ; in any case the latter arepreferred a4 they are more e:wy t o manipulate.

A good p e s c r i p t i o n lor t hesc glycerine jellies is aslollows

:-

Fiuest white t mga c a n t h powder . 80 g. darnped withAlcohol . . LOO ,, andGlycerine . a00 ,)

and t h o ~ ~ ~ u g h l ylialicn ; then quickly mixed with( j50 g. of water ( w a r a n d distilled) and o p i nshaken. Ini i i i (x1i :~tdyI, t r snsparer i t jelly i s iornieilwhich can at; once be bottled.

(?rLYURltIPUIG C ILl~:AMS.

A. Glycerine cream :--Almond oil . 1 Irg.

fipermaceli . . 70 9 1Wax . . 70 g.


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180 GLYCERINE

G u y " m

CREAMS-(CO~L~. )

Glyoerine . . 200 g.Bergamot oil . . g o , ,Lemonoil . . 20 I ,Geranium oil . . 20 , I

Neroli oil . . 1 0 ICinnamon oil . . 10 1,Rose-water . , 600 ,,

Almond oil .1 kg.

W B X * . 130 #.Spermaceti . . 130 ,,Glycerine . . 250 ,,Rosa oil . . 10 , ICivet . 2 1 ,

B. Glycerine cold cream :-

P l %I . ,P A R A T I O X O F &UIt h . l ' R O L l C U M .

For the prepzra t ion of hair petroleum the follow-ing prescription is given :-

Best petroleum (American Kaiser oil).

6kg.Tincture of nettles (obtained I'rom 2 ltg.

of uettle root, 7 Irg. of tLlcoho1, and 3ltg.

of distilled water) . . 10 I ,Glycerine . . 6 ),Alcohol . . 4 8 ,,Distilled water . . 40 1 ,

Essential oil for perfuming . . '2 ,,The petroleuiii which has prcviously bcen pcr-

fumed is niixed with alcohol at I6 per cent, end bot11are heated almost to boiling temperature in order toobtain thorough mixing end solution. AEter this,

distilled water is added to the solution and the


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GLYCIFRINE z\S A 80LVII:NT 181

remaining ingredients are added in the properorder.

Hair petroleumeffects

the solution of the fattysubstances of tho hair, t u x 1 also

loosens tlie th rown-off epidermis in the forin of d;~iidmfY,and imparts to

the hair brillianceand

suppleness.


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184 GLYCERINE

Xow hardly any transparent soaps arc iiiaclc inthis manner, but for this purpose glycerine is CX-

clusively

used, which also possessesthe advari tagc

that by dissolving the colouring niatter in the gly-cerine i t imparts nice colours to the

t r ans pmcn t

soap.If to heated glycerine, which hasbeen diluted with

about one thirdof

its voluiiie of water, asniuclz

finely

cut soap is added as can be dissolvedtherc in , withoutthe niass on cooling becoining hard, a, product is t h c

result which in the trade is known under thenaiiic

of Liquid Glycerine Soap or GlycerineCr:e:tm

and, coloured and scented in variousmanners , Fornis

a very valuable toilet adjunct.

If in the process of soapniaking

pureglyccnnc

is replaced by a glycerine which contains differentmedicinal substances in solution, then in this mannersoaps can be obtained which can be designated

as

cosmetic-medicinal soaps as theybeauti ly

thesliln

and also act medicinally.The solvent action of glycerine on scents

a n d

colouring matters can be made use of by dissolvingthese substances in suitable quantities in

th c glyccr-

hie,

andniereIy

combining this solution with soap.In order, however, t o obtain the bc t t e r qtialityglycerine soaps, there is a special process,

and

this iscarried out either by adding end stirring

tho

ap1)ro-

priate quantity of glycerine and sugar solution intot h e

soap after it has been boiled and then letting it coolin moulds, or by

mel t ing

ready-made soap and adding

glycerine, or, finally, by preparing a solution of


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VARIOUS APPLICATIONS. OF GLYCERINE 187

in its receiver. T h e colouring matters to be usedare at once dissolved in the glycerine (for the casein question soluble colouring matter must be used, as

by using non-soluble colouring i m t t e r the soaps will

not be t ransparent), and to the glycerine is addedthe aromatic substance for scenting the soap.

In order that the misture of t he solution ofcolonring matter and aromatic substances with theglycerine should be thorough, part of the glycerincis placed in a china bowl, heated up to about 60"-80" C. m d the colouring ina t t e r (fuchsine rccl, methyl

violet, iodide green, ctc;.) in solid fo rm is added ;by stirring with n, pestle it is s p r L a d throngh t heliquid, ; t i id solution follows in a very short tirne.After the glycerine has cooled again, the aroinaticsubstances a re added, and the liquid poured into theglycerine receiver. The dish is rinsed out withglycerine a n d the solution in the glycerine receiver

iss t i r rcd

with a glass rod and mixed with thereiunni ing glycerine.

T h e n so much lye is placed in t h e pan t h a t itsts nd s aboiit a hand high, and iC is heated to aboutLOO' C., when the f n b is added, and by the movciiientoC the stirring device it iiielts on the hot liquid.When all the f a t is melted, all the lye is poured in in

a L h i n stream and constantly stirred,a n d

this heating;md stirring ore continued for so long until the soalpshows t he requisite qnali ty. II too thick, owing tostrong evaporation of t h e water, this canbe remediedb y adding and stirring in the qecessmy quantity of

hot water,

. .


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IS8 GL YCER'INE

The soap still undertho

process ofs t i r~i11gs a l lowcd

to cool as much as possible without it thickening,and then the glycerine, that is t hc so lntio n ol' cmlour-

ing matter and perfume in glyceriiic, isfilowly

pom*cd

in and mixed with the soap by oonstan t stirring.The whole work

is

easy ofacco i~ ip l i s l~ i i i c~n l~ ,l'cmc is

taken that the stirring apparatus~ n o v c s asily iLnd

is

in good working order, as otherwise const :Lnt st~i .r ing

is certainly a very tiring proccss.The soap, now finished, is plimccil i n oiLl


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VARIOWS

APPLICBTIOPIS

O F GLYCERIKE 189

in all directions. Jus t the same thing occurs withsoap crystals.

Snow sodden in water is very transparent be-

glycerine- its production, uses and examination .pdf

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