A ME R IC A N

C HE MC A L J O UR N A L

E DI T E D B Y

IR A R E MSE N

PR O F E SSO R OF C H E MI ST R Y IN T HE J O H N S H O P K IN S U N IV E R SIT Y

VOL XXVII . . 1 0
9 2 .

BA L TI MO R E : T H E E D IT O R .

TH E C HEM IC A L P U B LI SH I NG CO .
, P R I N TERS ,

E A STO N ,
PA .
 N O . I .

MET HY L D ER IVATIV ES O F IN D IGO . By M . K u b a ra an d M . C h ik a

s h i ge

TH E MO L E C U L A R W E I G H T S O F C ERTA I N SA LTS I N A C ETO N E By .

H arry C J o n es
'

T H E L O W E R IN G O F T HE F REEZ I NG P O I NT O F A Q UE O US H Y D R O G E N
'

D I O XI D E B y H a y C J o n e s J a m e s B ar ne s a nd E d w rd P
. rr .
, ,
a .

Hyde
A ST U DY O F T R I B R O MP H E N O L B R O MI D E B y J H K astl e . . .

SO LU B ILITY O F MI XT URES O F SO D I U M SU L PHA T E A N D SO D I U M

C H L O R I D E B y Ath e r t o n Se id e ll
.

O N T HE P REPARA TI O N O F B R O M O F O R M B Y EL E CT R O LYS I S B y Pa u l .

C o u g hli n
NOTE ON T HE
R A T E O F H YD RA TI O N OF METAPH O SPHO R I C A C I D .

B y J C a n d F C B l ak e
. . . .

NO T E S .

R ad i o - L e ad

O n th e E xis ten c e O f A m m o n i u m
R E V I EW S .

D i e h e tero g e ne n Gl e i c h g e w i c h t e v om Sta n d p u n k te d e r P h asen leh re .

78
J ah r bu c h de r E le k tr oc h e m ie 79
T h e E le m e n t s Of Q u a l i t at i v e A na l y sis 80

N O . 2 .

CON TR I B UTI N S FRO M T HE C HEM IC A L LA B O RA TORY O F T HE MASSA

O

C H U SE T T S I N S TIT U T E O F T E C H N O L O GY

XXX V The A l l oy s f L e ad a n d Te ll u i um
. By o r .

H e n ry Fay a n d C B G il l so n . .

XXX V I l e A lloy s of A nti m ony a n d Te ll ur i um

.
-
.

B y He n ry Fay a nd H arr iso n E ve re tt A sh l e y

C O N T R I B UTI O N S FRO M T HE SHEFF I E L D L A B O RATO RY O F YA LE UN I
V ERS ITY
XC E le ctr a A 175 n z ly as a B asi sfor l lze S
'

y stem a tzz a l z on
’

— -
.

f I n o rg an i c Co mp oun ds
o y J m e s L oc e . B a k
C O N STIT UTI O N O F P HE N YL U R A ZO L E . By S . F A c re e
.
iv Con te n ts .

THE CO N V E R S I O N O F O R T H O P E R IO D IC A C I D I N TO N O R M A L P ER I O D I C
A C I D B y A rt h u r B LA M B
A SI M P L E A PPARAT US FO R D E M O N ST RA TI NG T HE MA NU FA CT URE
.
.

O F W A T ER GA S B y C E Wate rs
E
. . .

C O NT R I B UTI O N FR O M T HE C HE M IC A L L A B O RATO RY O F P UR D U
UN IV ERS ITY
D i ck lora ce ty l P hosplzi de . By P . N . E va n s a n d C E Va n
. .

d e rk l e e d

R EP O R TS .

O n t h e P re se nt St ate o t h e S ud y o A l bu m i n f t f
T h e D i sso c i at i n g P o we r o L iq u id Hyd roc y an i c A c id f
R E V I EW S .

A L abo rat ory G u ide to t he St u dy o f Q ual itat i ve A na l y si s

T h e P ra c ti c a lMeth od s o f O rg an i c C h e m istry
L eh rbu c h d e r a n org a n i sc h e n C h e m i e fii r St u die re nd e , an U n i ver
s i t at e n u n d t e c h n i sc h en H o c h sc h u le n

N O .
3 .

ON THE FO R M ATIO N D E CO M PO S ITI O N A ND G ER M I C I D A L A C TI O N O F

, ,

B E NZO Y L A C ETY L A ND D I A C ETYL P ERO XI D ES By P a ul C .

Freer n d F ed r ic k G N v y
a r e . o

C O N TR I B UTI O N SF R O M T HE C HE M I C A L LA B O RA TO RY O F H AR V AR D
C O LL E G E
C XX I X 0n 6 N i tropy omuci c A ci d B y H en ry B H i ll
.
— - r .

a nd Ge org e R Wh i te
.

TH E Q UA N TITATIV E SEPARATIO N O F H YD R O C H LO R I C A ND H YD RO
C YA N I C A C I D S B y T h od Wil li m R ich rd an d Si d n ey
. e o re a a s

K e nt
'

Si n g e r
ON T HE N A TURE OF MER C UR I C I O DI DE I N SO L UTI O N . By J . H
R tle an d J e w ett V R e e d
as .

C O N T R I B UTI O N S FRO M T HE SHEFF I E L D L A B O RA TO RY O F YA L E U N I

V ERSITY
XCI . 0n B e nz oy l be nz y l u r e a , B e nz oy lp ara toly l u re a , a n d
-

the Co rre sp ond i ng P se udoe tlzy l ur e as A Co rr e cti o n

B y Henry L Wh e el e r
. and T reat B J oh ns
. on

R EP OR TS .

Th e M o l e c u l ar Weig h t o f Sul p hu r
Su l p h u ric A c i d an d I t s P re pa rat io n by t h e Co n tact Met hod
R E V I EWS .

An I n tro d u c t i o n to C h e m ic a l A n a y s is forl St u de n t s o f M e d ic i n e
P h a r m ac y , an d De n t i s t ry
 Con te n ts .

K urz e A n l e it u ng z u r q ual it at i ve n A n a lyse

H i g h Te m p er atu re Meas u re m en t s
D ie N o r malele me n te u nd i h re A n w e nd u n g i n d e r elek tri sc h en
Messtech n i k
Sm ok e l e s s P o wder N it roc e ll u l o se a n d T h eo ry o f t h e
, , C e ll u l o s e
M o lec u le
O utl i n es o f E lec troc h e m i s try
O n t h e C o m p o s i t io n o f Du tc h B utter
The L aborat o ry C o m p ani o n t o Fat s a nd O i l s I n d u s t r ie s

NO .
4 .

THE ST RU CT URE SU B S T A N C ES OB TA I N E D BY TH E A DD ITI O N

O F T HE

OF O R G A N I C O XY G E N C O M PO U ND S A N D A L U M I N I U M H A LI D ES
By E l m e r P K oh ler
FRO M T H E SHEFF I EL D LA B O RAT YA LE
.

C O N T R I B UTI O N O RY O F UN I

V ERS ITY
XCI I . Ou the A cti o n of P he ny l hy dr az i n e on A cy l thi ocar
—

ba mi c a n d A cy l i m i dothi ocar bon i c e ste rs : Py rr o a , fl’ -

D i a z ole D e r i va ti ve s By He nry L Whee l er a n d A l l i ng

. .

P . B ea r d s l e y
X C II I .
—
0n the M le cul o ar R e a rr ang e me n t of Unsy mm e t
r i ca lA cy l thi ou re as a nd A cy lp se u dothi ou r e as to [so
me r i c S
y m me tr i ca l D e ri va ti ve s By H en ry L Wheeler
’

. .

XCI V .
—
On Some D ou ble Sulpha te s of Tha l l i c Thall i um
a nd C a e si u m . By J a me s L ock e
THE SU LPHA T ES OF B I S M UTH . By F . B . A ll a n
C O N TR I B U T IO N F RO M TH E N O R T H C ARO LI N A E XPER I M E N T STA
TI O N
The Sol ubi l i ty f
o B ari um Su lp ha te i n Fe r ri c Chl or i de ,
A l u m i n i u m Ch l ori de , and Mg n a e si u m Chl ori de . By
G S Fr a p s
FA TT Y O
. .

I . AN I N V ES TI G A TI O N O F T HE I L CO N T AI N ED I N T HE SEED S
OF L I ND ERA B E NZ O I N . I I L AUR I C A C I D A N D SO M E O F ITS
.

D ER IV A TIV ES . By C h ar l e s E . C as p a r i

R EP O R T .

T h e O xyg e n B a se s

N O .
5 .

LC U LATI O N O F ATO M I C W E I G H T S By F W C l ke
TH E C A . . . ar

R ESEAR C HES O N T H E O XI D ES O F T U NG ST E N B y E T A ll en . . . a nd

V H G otts ch al k
. .
vi Con te n ts .

C O N T R I B U TI O N S FRO M T HE C HEM ICA L L A B O RATO RY OF W ES LEYA N

UN IV ERS ITY
A Che m i ca l M thod f
e or Obta i ni ng Vacua . B y Fr a n c is G
Be n edi ct M a n n in g
an d Charl otte R .

C O N T R I B UTI O N S FR O M T HE SHEFF I E L D L A B O RATO RY OF YA LE

U N IV ERS IT Y
X CV I On the
.
—
M
i x e d Cry stals of Si l ve r Chlorate a nd
Sod i u m Chlor a te , a n d the i r Sol u ti on s yH Foote 345 . B . W .

TH E EL E CT TI RO M O V E FO R E O F ME A S N SO U O N S O F CY A
C T L I L TI
NIDE B y S B
. . . C hristy

R E V I EW S .

The E e e t l Study of Gases

xp ri m n a

Th e E le m en ts o f P hy si c al C h em i stry
Sam ml u n g chem i sch e r un d chemis ch tech nische r Vort -
ra
ge
P h ysi k ali s che C hem i e fii r A n fang e r

N O . 6 .

CO NT R I B UTI O N S FR O M T HE C HE M ICA L L A B O RA TO RY O F T HE R O SE
PO LY T E C H N I C I N STITUTE
XX C a mp hori c A ci d B y Wi ll i am A N oy es a nd A u st i n
.
—
. .

M P atterso n .

T H E L O W ER I NG O F T HE F REEZ I NG P O I N T O F W A T ER P R O D U C E D B Y -

C O N C E N TR A TD SO L U TI O N S O F C ERT A I N EL E CT R O LY T ES A ND ,

T HE C O NDU CTIVITY O F SU C H SO LUTI O NS B y Harry C J o nes

_
. .

a n d Fr e d e r i c k H G e t m a n .

A CTI O N O F P H O SPH O RUS P E NT A C H L O R I D E O N A N ILI N E By J .

E l li ott G i l p i n
CO N TR I B UTI O N S F R O M T HE SHEFF I EL D L A B O RA TO RY O F YA L E U N I
VERS IT Y
X CV . The P e r i odi c S
y ste m a nd the P r ope r ti e s of I norg a n i c
Comp ounds . IV . The Solu bi l i ty of D ou ble Su lp ha te s
o f the F or m ul a By J a m e s L o c k e 45 5
TH E I N A CTI VIT Y L I PASE
TO W AR D S THE SA LTS O F C ERTA I N A C I D
OF

ET HERS C O N S I D ERE D I N T HE LI G HT O F THE T HEO RY O F EL E C

T R O L YT I C D I SS O C I A TI O N B y J H K tl . . . as e

R EP ORTS .

R ecen t W k n t h De ri
or o tive of A l k li n d A lk lin E rth Met l
e va s a a a e a a s 48 7
A N e Method for the P reparation O f U nsaturated Hydrocarbo n s
w .
494
B ari um Sul p hate i n Gravimetri c A n aly sis 49 5
Grav i m e tri c De termi n atio n o f Sul ph uri c A c id i n th e P resen ce o f I ro n .

I ndex 5 05
VO L . XXV I I .
J A N U AR Y , 1 90 2 . N o . I

A ME R IC A N

C HE MC A L J O UR N L

M E T H Y L DER I V AT I V E S O F I N D I G O .

BY M R U H A R A A N D M C H IXA SH I G E
. . .

I E N ERA L C O N SI D ERAT I O N S
’

. G .

In our last article it was show n that Fli mm s sy n thesis of ‘ ’ 2

i n digo which co n sists of the fusio n of bromaceta n ilide Wi th

,

dry caustic potash m ay satisfactorily be explai ned by as ,

s u mi n g the formatio n of d ip h e n y l d i k e to p i p e raz in e as a n ih

te rm e d i ate product si n ce i n fact i n digo c an be formed from , , ,

the latter as well as fro m bromaceta n ilide .

I f our V iew be correct those substi tuted brom or chlor , .

aceta n ilides which are so co n stituted as not to be able to

form the piperazi n e ri ng would n ot yield the substituted i h
digos A ccordi n g to Fl i mm i n digo is formed from brom
.
,
3

aceta n ilide by molecular rearra ngeme n t through the i nter ,

me d iate stage O i p se ud o i nd o x y l H euma n n believed that

4
.

p h e n y l g ly c oc oll bromide a nd the n p se udo ind ox y l are first

formed If this be true a substituted bro m or c hlorac e ta n il
.
,

ide such as me thy lc hlorac e tan i li de ought to yield dimet hyl

, ,

i n digo i n which the methyl groups have replaced the hydro

g e n atoms o i the imido groups as will be assu med ,

1Th i s J O U R N A L 2 4 , , 16 7 .

1 B d c he m G
e r . . . e s .
, 2 3, 57 .

3 L oc . ci t .

'
4 Ibzd 2
.
, 3 , 3045 .
 '

K u ha ra Chzhashzge
’

2 a nd .

C H —
N
< CO C H C 1
.

C H8

H C C

or C sHs —
N C sHs —
N
C 50 ; OE
B , § CI C H, C O C I.

C, H , N .
6 4
H

C H, COO H
.

C z c / \ C
0
\C O / .

N ow , in
order to decide the poi nts i n questio n the authors ,

have specially prepared me thy l c hlorace t anilide ,

c , H,

which is co n sidered to be c hlorace tan ilid e i n which th e hydro

g e n O i the imido group has bee n replaced by methyl a n d ,

he n ce it c an n ot form the piperazi n e ri n g It was the n .

subj ected to fusio n with caustic potash and fou n d to de c o m

pose e ntirely not givi n g a trace of i n digo derivatives Its
,
.

deportme n t towards the fused potash was appare ntly differ

Fli mm also states
I
e nt from that of ordi n ary c hlo race t a n il id e .

that phe n y lc hlorac e tani lide ,

prepared from diphe n ylami n e an d c hlorace ty l chloride did not

give phe nyl derivatives of i n digo at all u nder similar treatme n t .

The authors repeated his experime nts and obtai n ed the same
results which must be due as they believe to the i mpossi
, , ,

bility of the formatio n of the piperazi n e ri n g .

There is a nother fact which may support the author s V iew ’

.

1 L o: c it .
 Mthy l De e r i va ti ve s o f In dig o .
3

H ausdorfe r claims that he obtai n ed phe n y lg ly c ocoll by treat

l

i ng d ip he ny l d ik e top ip e raz in e with alcoholic potash ; we fol

lowed his method with d iorthotoly ld ik e tO p ipe raz ine and suc
c e e de d getti ng a very small qua n tity of orthotoly lg ly co
in
coll . Now we mai ntai n that p he n y lg ly c oc oll m ay be formed
from d i ph e n y l dik e tOp i pe raz in e by the actio n of fused caustic
potash j ust as it is whe n alcoholic potash is used and that in ,

digo is formed by its further actio n .

O n exte n di n g this pri n ciple to the formatio n of the deriva

t iv e s of i n digo we succeeded i n getti n g the di ffere n t methyl
,

derivatives The experim e nts were co nducted with chlor

.

acetyl derivatives O f ortho m eta and p aratoluid i ne s as well ,

as with diortho and d ip aratoly ld ik e tOp ip e raz in e s d ime thy li n ,

digo bei n g obtai ned in each case A nd also with c hlorac e t .

u n sy m me t ax y lid e a nd c hlorac e tp se u do c u mid id e

.
-
an d with ,

their correspo ndi ng d i ary ld ik e tO p ip e raz ine s tetra and hex a ,

me thy li n d ig os were O btai n ed .

For desig n ati n g the positio n s of methyl groups i n di ffere nt

m e thyl i ndigos we propose to n u mber the carbo n atoms in
,

the two be n ze n e n uclei of i n digo as show n i n the followi ng ,

formula

—
N H N H

\ / s

A s o nly one d i me th y li nd i g o
is possible from either d iortho
t oly ld i k e tO p ip e r az i n e ( or c hlorac e tort hotol uid e ) or dipara
toly l d i k e tO p ip e raz i ne ( or c hlorac e tp aratol u id e ) we believe ,

that the d im e thy lin d ig o from the former has the structure
C H,

-
NH N H

1 Be r. d . c he m . Ge s .
, 2 3 , I 80 2 .
 K u ha ra
'

a nd Chzha shzgé
’

an d we call it -
dimethyl i n digo while from the latter we get
,

—
N H N H

which is d i me th y lind ig o .

Three isomeric forms are possible fro m d i me t atoly ld ik e to

piperazi n e ( or c hlorac e t me t atol ui d e )

—
N H N H

Di m e t h y 1i n di g o
’
5 5 .
- .

—
N H N H

3 3 D i m e t h y 1i n d g o
.
’-
i .

-
N H N H

-
D i m e t h y l i nd i g o .

We must decide which O fthese three formulas correspo n ds

to the d i me thy l in d ig o O btai n ed by us fro m c hlorac e t me ta
toluide B ased upo n the rules of orie n tatio n u n iversally ac
.

c e p t e d the C O group e n ters the para positio n

, with refere nce ,
 Mthy l D e e ri va ti ve s o f In digo .
5
‘

to the C H, group more readily tha n the ortho positio n and , ,

he n ce the d i me thy lin d ig o of the formula or 5 5 dimethyl .

’
-

i ndigo may be the pri n cipal product O fth e reactio n

, .

Tetra an d he x am e thy lind ig os formed respectively fro m ,

d i u nsy m me t ax y ly ld ik e top ipe raz ine or c hlorac e t u n sym

-
.
- -
.

m e tax y lid e and d ip se udOc umy l d ik e t op ip e raz ine or c hlorace t

, ,

p se udoc umid id e must evide ntly possess the followi ng struc ,

t ures :

-
T e t r am e t h y l i n di g o .

—
N H N H

H e x ame t h y 1i n dig o
-
.

On referri ng to the literature we fi n d the di ffere n t methyl ,

d erivatives of i ndigo which are already k n ow n Di me thy l in .

digo O btai ned by Fli mm from bromace tp aratohii de and by

l
,

2
E ck e n roth from c h lorac e tp aratolu id e the SO called p di ,
- -

me thy lin d ig o lately prepared by K u n c k e ll from p methyl o

3
,
- -

a c e t y l a mi d oc hl orac e tO p he n on e and d ime th y li nd ig o made ,

-

by the authors from d ip aratol y ld i k e top ip e raz in e are all ide n

tical SO called m e tame thy l ind ig o w as also prepared at
.
-
‘

Farbe w e rk e vorm Meister L ucius an d Bru n i n g fro m ortho .

,

n it ro me t ame thy l be nz al d e hy d e b ut i ts co nstitutio n is quite ,

1 Be r . d . c he m . Ge s .
, 2 3 , 59 .

2 I bzd 4 , 693
’

.
, 2 .

'
3 Ibz d .
, 3 3 , 2 6 48 .

4 I bi d .
,
I6 , 8 x7 (Be r . u .
 K u ha ra a nd Chiha shzge
’
6 .

obscure because though it sho uld b e ide ntical with either

, ,

or d im e thy lin d ig o i n terpreti n g its form atio n from

-
,

the theoretical sta n dpoi n t it shows a n e ntirely di ffere nt spec ,

tru m fro m either O f the other two a n d co n seque n tly must pos ,

sess a di ffere n t structure Fli mm o n ce tried to get a n iso .

meric d ime t hy lin d igo from c hlorace torthotoluide by the potash

fusio n b ut havi n g bee n u nsuccessful he ascribes the failure
, , ,

to the prese n ce of o ne of the ortho positio n s previ ously occupied

by a methyl group B ut the substa n ce like i n digo O btai ned .
, ,

fro m o rtho toly l gl y c ocoll by the potash fusio n at the B adische

A n ili n u n d Soda F abrik may be ide n tical with our
1
-
di -

m e th y l in d ig o prepared from d iorthot oly ld ik e tO p i p e raz ine or

c h l ora c e tort h otol u i d e A n d a n i n digo derivative O btai n ed .

also at th e B adische A n ili n u n d Soda Fabrik from m e t ax y ly l -

2

glycocoll an d t e tra m e th v l i n d ig o O btai n ed by us from

-

di u n sy m m e tax y ly ld ik e t 0p ip e raz in e or chlorace t u n sy m

-
.
- o
n

m e t ax y li de may possibly be ide n tical

,
.

B esides the formatio n of i n digo or its methyl derivatives as ,

the pri n cipal reactio n s from d ip h e n y ld ik e top i p e r az ine or di ,

t ol y l d ik e top ip e raz i n e s we have O bserv ed the pro d uctio n of ,

p h e n y l i s o n i t r i l potassiu m carbo ,
n ate a n d primary a n d sec ,

o n d ary ami n es j ust as i n the case O f H e um ann s sy n thesis

’
, .

W e thu s have further proof that d iary l dik e t0p ip e raz i n e m ay

break dow n i n to ary l g ly c oc ol l which i n tur n wo uld u n dergo , , ,

cha n ges as i n H e u m ann s process ’

.

II . ME T H YL C H L O R A C E T A N I L I D E ,

O, H , -
N
< C O C H, C1 .

This substa n ce h as n ot bee n k n ow n hitherto A t first .

m ethyla n ili n e was prepared accordi n g to H e pp s method O n ’ 3

.

m ixi n g it with chl orac e ty l chloride each i n well cooled ,

-

ethereal sol utio n m e th y l ch l orac e tan il id e was O btai n ed i n the

,

form of a crystalli n e powder I t crystallizes fro m hot water .

,

o n cooli n g i n the form of fi n e n eedles but sometimes i n larg e

, ,

1 Be r . d . c he m . Ge s .
, 2 5 , R e f 4 88 .
( Be r . u
2 L oc . cit .

3 Be r d
. . c he m . Ge s .
, l o, 32 7 .
 M thy l D e e ri va ti ves ofInd ig o .
7

p risms fro m its dil ute solutio n It sub lim es whe n heat e d .

a n d a t ta cks the ski n to some exte n t The mel ti n g po in t of .

-

the crys tals is Th e crysta ls d ried be t we e n th e folds of

fi lt e r paper or kept i n a desiccator for a few days gave o n
-
, , ,

a n alysis the follo w i n g resul ts

,

I . gra m substa n ce gave gram C l .

II . gram substa n c e gave gr am C l .

C al c ul a te d fo r u
F o nd .

A fter the crys t als had bee n kept i n a desiccator for more
tha n a w e ek they were agai n a n alyze d .

gram substa n ce gave gram C l .

C l ul t d f a c a e or
P o nd u
1 9 -35

Me thy lc hlo whe n fuse d with causti c po tas h be

r ace ta n ili d e , ,

haves quite d i ffere n tly from chl orace tan ilid e or c hl orac e tto lui de
It never yields substa n ces related to i n digo but d e c omw
e n tirely .

III . DI ME T H YL IN D I GO S .

The c h lor ace torth otol u id e used i n the expe rim e n ts was pre
pared acco rdi n g to the dire ctio n s give n by A be n i us an d Wid
m an whose proc e s s co n sists i n mi xi n g 1 molecule chl orace ty l
,
1

chloride with 2 molecules o rthotoluid i n e ea c h i n well cool e d ,

ethereal solutio n P Meyer reco mme n d s benz e n e as a sol

’
. .

ve n t i n stead of ether We have however fou n d it more ad .

, ,

v an ta g e o u s as we believe to use the ethereal so luti o n s of the

, ,

tw o substa n ces c oo led with i ce so as to give the th eoretica l ,

yield of the prod uct .

C hlo race t me t atol u id e has n ot be e n described in the liter a

ture hitherto For its preparati o n ex actl y the sa me p roces s
.

as abo ve give n was u se d The substa n ce w as p urified by .

repeated r e cry stallizatio n from hot wa ter an d dri e d over cal

c i u m chl oride an d its chlori n e was determi n ed,
.

J p t t Ch m
. ra 38 99 . e .
, 2 .

Be r . d . c h m
e . Ge s .
, 8, 1 1 54 .
8 K a ha ra a nd Chi ha shig é .

I . gram substa n ce gave gram Cl .

II . gram substa n ce gave gram C1 .

C l ul t d f a c a e or u
Fo n d .

I .

It melts at It is somew hat volatile eve n at ordi n ary ,

temperatures a nd sublimes whe n heated , Its property O f at .

tacki n g the ski n its solubility an d other properties are Simi , ,

lar to those of the o rthotol uid e .

1
C hlorace tp aratolui d e was prepared by Tommasi by E cke n ,

roth a nd Do nn er an d by Meyer 3
It was also prepared i n ,
2 '
.

the same way as the isomeric toluides .

From c hlorac e torthotol ui d e an d C h lorac e tp aratol ui d e dior

tho an d d ip aratol y l d i k e t op ip e raz i ne s were prepared re Sp e c ,
‘
t iv e l y by the process suggested by A be ni us
,
We were .
,

however n ot able to get d i me tatol y ld ik e top ip e raz i ne si n ce

, ,

o n ly a few grams of chlorac e tme t atol ui d e were at ha nd .

These d i ary ld ik e topip e ra z i n e s readily yield d im e thy l in d ig os .

1 .
-
Dime th y 1in d ig 0 ,

C H,

N H

was easily formed from d iorthotoly ld ik e top ip e raz i n e as well as

from c hlorac e to rtho tolu id e by fusi n g with caustic potash .

Fli m m states that he failed to get d i me thy l i n d ig o from

c h l o rac e torthot ol u i d e by fusi n g with caustic potash but o n , ,

the co n trary we fou nd that it could be formed from chlor

,

a c e tort hotol u id e an d also from its correspo n di n g d it ol y ld i

,

k e t O p i p e r az i n e with a tolerably good yield ,

W e m ixed .

c h lor ac e t orth o to l u i de with an equal volume of dry powdered

caustic potash and heated the mixture in a test tube or fl ask,

-
.

1 Bull . s oc h im
. c . . I9 , 400 .

2 Be r . d . che m G . e s .
, 2 3 , 325 7 .

3 I bid .
, 8, 1 15 4 .

4 I bi d . 2 1 , 1 6 65 .
,
 M thy l D
e e r i va ti ve s o f In dig o .
9

The mixture i nsta n tly ass umed a reddish yellow color whe n -
,

the potash bega n to fuse the n tur ned pale yellow and reddish
,
-

brow n and fi n ally ch a nged to gree n ish yellow o n cooli n g The

,
-
.

mass was n o w treated with water and fro m the sol utio n di ,

m e thy li nd ig o precipitated immediately o n exposure to the air .

Its productio n was Show n to be depe n de n t wholly upo n the

n ature of the caustic potash used Whe n co n tai n i n g p otas
.

sium carbo n ate it was fou n d to give th e best result an d after

, ,

several trials the followi n g proportio n s o f the materials were

fou nd to be most f avorable
C hlo rac e torth o tol uid e 1 00 parts

Dry powdered caustic potash 17 5

P otassium carbo n ate 25

Without mixi n g an y potassium carbo n ate i n te n tio n ally the

yield of the d im e thy l in d ig o was very poor or O fte n n o n e Its .

actio n is however n ot quite certai n b ut its prese n ce may

, , ,

probably keep the mixture fro m bei n g e n tirely fused whe n

heated thus avoid i n g the free access of air and also preve nt
, ,

i ng too viole n t a n actio n of the potash which would i n t h at ca se , ,

be destructive The use of a glass vessel should be avoided

.

for the fusio n si nce it is rapidly corroded by the melted pot

,

ash Thus a n ickel crucible was substituted with the follow

.

i n g precautio n s : A s q uare box of asbestos board havi n g a -

,

hole at its bottom j ust large e nough to allow the crucible to

rest over it was co nstructed an d a cover of the same material
, ,

was m ade to fit A gas flame was applied from below so as

.
,

to heat directly the bottom of the crucible We at first .

thought it best to pass n itroge n gas i nto the box i n order to

preve n t the oxidatio n of the product but soo n fou n d it n u ,

n ecessary to do so i n co n seque n ce of the evolutio n of heavy

vapors which fill the box an d exclude air The reactio n s .

proceed smoothly .

For the purificatio n of the d i m e thy l in d ig o so obtai n ed

several methods were tried and at last we fou nd it most ad
,

v ant ag e o u s to filter the precipitate of d i me thy li n d i g o a n d to

wash successively with hot w ater an d alcohol the latter com ,

p l e te ly dissolvi n g out the resi n ous matter For a n alysis we .

h ad to sublime it u nder 3 5 to 4 0 m m pressure accor d i ng to .

,
Io K u ha ra a nd Chi ha shigé .

Sommarug a l
The sublimate was agai n washed with alcohol
.

a n d ether to get rid of heavy hydrocarbo n s which may possi

bly have bee n formed by the d ecompositio n of the dimethyl

i ndigo P recipitated d ime thy li nd ig o c an also be purified by
.

washi n g with alcohol the n dissolvi n g i n hot chloroform and , ,

removi n g the residue fro m the solutio n This process is most .

co nve n ie n t for purifyi n g from silica which is derived from the

glass vessels used .

Sublimed d i me thy lind i g o was a n alyzed by D umas method ’

.

1 . gram sub sta n ce gave cc nitroge n at 1 4 C .

°
.

an d mm pressure . .

11 . gram subst a n ce gave cc n itroge n at 2 0 C .

°
.

an d mm pressure . .

C l ul
a c at e d fo r u
Fo n d .

0 0
C 6 H3 CH 8 ~ I
/
. .

N H

9 53
-
Di me thy 1i n d i go
is a p owder whe n precipitated but ,

w he n subli med it crystallizes i n prisms very closely resem ,

bli n g ordi n ary i ndigo i n appeara n ce It gives a bright violet .

vapor with partial decompositio n whe n heated Its charac .

'

t e rist ic property is its solubility i n various solve n ts O ne .

gram of the substa n ce is soluble in about 2 000 cc alcohol and .

‘

i n 5 00 cc chloroform It i s more or less soluble in ether

. .

a n ili n e be n ze n e n itrobe nze n e oil of turpe n ti n e fused chloral

, , , ,

hydrate para ffi n li n seed oil acetic acid and fumi ng sul

, , , ,

p h uri c acid an d is i n ge n eral more sol u ble tha n ordi nary

, , ,

i n digo The colors of the solutio n s i n these solve n ts vary

.

from reddish violet to gree n or blue We observed the ab

-
.
,

sorptio n ba n d of the chloroform solutio n accordi n g to the

stateme nts of K r ii ss an d O e conom id e s seeki n g for the posi ,
2

tio n of maxi mum dark n ess Whe n the solutio n is highly .

co n ce ntrated or its l ayer is thick the absorptio n takes place ,

from ora n ge to gree n while with ordi n ary i ndigo the ra n g e is ,

much less The results of our observatio n s are give n at the

.

e n d of the paper .

1 Be r . d . c he m . Ge s I I , 135 5 .

2 1bid .
, 16 , 2 05 1 .
I2 K u ha r a a nd Chi ha shig é .

isomers i n the absorptio n ba nd as will be see n fro m the , an

n e x e d table .

3 .
-
Dim e t hy 1i n d ig o ,

—
NH N H

was formed fro m d ip aratol y ld ik e t O p ip e raz in e

also from a nd

C hlorac e tp aratol u id e u n der the same co nditio n s as the meta

compou n d Ir was fou n d to be ide n tical with the dimethyl

.

i n digo already k n ow n as explai n e d in the precedi n g part o f

,

the paper Its solubility i n chloroform is almost the same as

.

that of d i me thy 1i n d i g o -
.

IV . TE TR A ME T H Y L IN D I GO .

- T e t ra me th y 1i n d i go ,
C H,

—
N H

was formed from fro m di

c hlo rac e t- u n sy m .
-
m e tax y lid e a nd

u n sy m m e t ax y l d ik e to i e raz in e by fusi n g with caustic pot

-
.
p p
ash Its properties are Similar i n m a n y respects to those
.
, ,

of the other methyl derivatives of i n digo Its solubilities a n d .

the positio n of the absorptio n ba n d are give n i n the table be

low .

C hlorac e t u n sy m me t ax y li d e was prepared by mixi ng 1 00

-
.
-

grams of u n sy m m e t ax y l id i n e an d 5 0 grams of c hlorac e ty l

.
-

chlori d e each dissolved i n be nze n e The yield was almost

,
.

theoretical It crystallizes i n Silky n eedles from be nze n e a nd

.
,

does n ot attack the Ski n Its melti n g poi n t is The .

-

substa n ce was a n alyzed with the followi ng results

1 . gram substa n ce gave gram C l .

11 . gram substa n ce g ave gram C l .

 M thy l D
e e r i va ti ve s o f In dig o . I3

C l ul
a c a te d fo r u
Fo n d .

I3) z
—
. I .

C1
It produced di u n sym me tax ly ld ik e top ip e raz in e by treati n g
-
.
-

with alcoholic potash as i n the preparatio n of other d i ary ld i ,

k e tO p ip e raz in e s It crystallizes i n colorless n eedles and mel ts

.

at
V . H E XA ME T H YL I N D I G O .

C hlorac e tp sé d o c umi d id e u
was prep ared from p se ud oc u mi
"

di n e and c hlor ace ty l chloride It crysta llizes i n n eedles and .

m elts at 5 Its a nalytical results are as follows

.

C l ul t d f a c a e or
Fo n d u
IG .
79
Dip se ud oc u my ld ik e tOp ip e raz in e
formed from the above sub
sta nce crystallizes i n colorless nee d l es an d melts at 2 2 5 .

A correspo n di n g methyl derivative of i ndigo or ,

h e x ame t hy 1in d ig o ,
’
. 6 -

CO

OH , 3

was obtai ned from c h lo rac e t p se udoc u m id id e as well as from

d ip se u doc umy l d ik e t op i p e r az in e ,
but o n ly in small qua n tity .

Posi ti on s of the M xi m um D a a rk n e ss i n the A bsorp ti on B a n ds f

o

the Mthy l i ndig

e
‘

os .
( Chloroform Solu ti on ) .

N a me .

Ordi n ary i n digo

- D i me th y 1in d ig o
5 5 .
’
-
Di me th y li nd ig o
-
Di me thy 1i nd ig o
Tetramethyl
-

i n digo
1 Kr u ss a n d O e c onom i d e s gi ve AI P ”
M fo r o r di n a r y i n di go .

2
 M thy l D
e
f
e r i va ti ve s oIn di go
. I S

O v-Q

c v-q

-
E
m
8 M
.

E 6
E
U 8 a
Z 0 B fi
O
w 3 2 L v

E
5 M e
0
T HE M O L E CU L A R WE I G H T S O F C E R TA I N SA L T S
I N A C ETO N E .

B Y H A RR Y C J N E S . O .

l
Dutoit and Frid e ri ch stated i n 1 8 9 8 that we have fou nd , ,

by the boili n g poi n t method th at the followi n g salts N H4C N S

-
, .

H g C l N aI L i C l C d I dissolved i n aceto n e have the n ormal

, ,

molecular weights They do n ot give any data but state .

,

that their results will b e published later A n exami n atio n of .

the literature up to the prese n t fails to Show that any such

results have bee n published thus far .

A year later this work was cited by Kahle n berg and L i n

”
c ol n ,
who poi n ted out that such solutio n s co n duct the curre n t
to a co n siderable degree .

Facts such as these are of special i n terest t o day i n the ligh t

of the moder n theory of solutio n s If a salt d issolved i n a ny .

solve n t should give a n orm al molecular weight over a wide

ra n ge of dilutio n an d at the same time Show a large m ol e c u
,

lar co n d uctivity which would i ncrease with the dilutio n it ,

would i n dee d be awkward for the theory of electrolytic dis

, ,

sociatio n in its prese n t form H owever before ame n di n g or .

,

suppleme nti n g a theory which has correlated hu n dreds of ,

appare n tly isolated facts and which has probably do n e more ,

towards placi n g C hemistry upo n an exact basis tha n any other

theory which has ever bee n propose d it is n ecessary to ex ,

ami n e very carefully the experi me n tal evide n ce beari n g u po n

Si n ce D utoit an d Frid e ric h h ave give n n o accou n t of the

experime n ts a n d have no t eve n published the data upo n
,

which their co n clusio n is base d 1 determi n ed to study the ,

molecular weights of some of the above substa n ces i n aceto n e ,

by mea n s of m y modificatio n of the boili ng poi n t m ethod of

3
-

Beckma nn I proposed to determi n e the molecular weight at

.

various dilutio n s to see whether a n ormal molecular weight

,

1 Bull oc c h i m
. s . . 19 , 334 .

2
J P h y Che m 3
. s . .
, , 32 .

3 Th i s J O U R N A L ph y s C h e m
19 , , 5 81 Z ts c h r . . .
, 3 1, 1 19 .
 Ml o e cu l a r We ig hts of Ce r ta i n Sa l ts in A ce ton e . 17

w ould
be obtai n ed at an y dilutio n an d if so whether it would , ,

be obtai n ed over a co n siderable ra n ge of dilutio n .

Before we c an determi n e the molecular weight of any sub

sta n ce i n an y solve n t it is n ecessary to k n ow accurately the
boili ng poi n t co n sta n t of the solve n t The co n sta nt for ace
-
.

1
to n e is give n by Biltz as It however seemed d e si ra , ,

ble that this should be redetermi n ed .

The aceto n e w hich I used i n this work was a very pure

sample which was carefully freed from water Its boili ng
,
.

poi n t u n der n ormal pressure was

, . to ,

B oili ng Poi n t Con sta n t

f A ce ton e -
o .

I n or d er to determi n e th e bo ili n g poi n t co n sta n t of a sol -

ve n t it is n ecessary to select a substa n ce which will not be

dissociated by the solve n t a nd which will not act chemically ,

upo n it It is also desirable that the dissolved substa n ce

.

should n ot have a very large molecular weight i n order that ,

the rise i n boili n g poi nt should be fairly large

-
Naphthale n e .

was Selected as the dissolved substa n ce Si n ce it fulfilled these

co n ditio n s an d further could be obtai n e d i n a high degre e
, , ,

of purity Fo ur determi n atio n s of the boili n g poi n t co n sta n t

.
-

of n aphthale n e were m ade an d the results are give n below

‘

R i se i n
N a ph t h a l e n e . boi in l gp - oi n t . Co n s ta n t .

G m
ra s

Mea n , 17 2 5
The co n sta n t fo r aceto n e is take n as the mea n of the above
four val ues a n d 1 7 2 5 is used in all the followi ng calculatio n s :
,

Ml o e cu la r We ig ht of Ca dmium Iodide in A ce ton e .

ight determi n atio n s of the molecular weight of cadmium

E
iodide in aceto n e were m ade at dilutio n s ra ngi n g from less ,

tha n to more th a n n ormal The results i n the order .

,

of in c reasi n g co n ce n tratio n are give n below : ,

1 “ P r ac ti c a l Me th od fo D e te rm in in g Mo l e c ul
r ar W e i gh ts ,
”
p . 1 7 9.

2- 27
18 jon e s .

G ra m s C d I, i n 1000
g ra m s l e n t
so v .

6 4 -7 99

94 -2 6 9

These results Show i n the first place that the molecular , ,

weight of cadmiu m iodid e i n aceto n e is not n ormal for any of

the above dilutio n s It does not eve n approach the value 3 6 6
.
,

which correspo n ds to the formula C d 1 They show further 2

.
, ,

that the molecular weight is n ot a co nsta n t but varies with ,

the dil utio n used The ra n ge of the dilutio ns studied is about

.

as great as was possible by the boili ng poi n t method More -

.

co n ce ntrated solutio n s were n ot employed because the laws of

dilute solutio n s do not hold at great co n ce ntratio ns It would .

have bee n of i nterest to study more dilute solutio n s to see how

far the molecular weight would ha ve decreased a nd whether .
,

it would have appro ached the n ormal value a nd have re

mai n ed co nsta nt as the dilutio n was still further i n creased ;
but it is obvious that the rise i n boili n g poi n t would be too -

small to measure .

The facts the n Show that the molecules of cadmiu m iodide

are polymerized to a very co n siderable exte nt i n aceto ne eve n ,

i n the most dilute solutio n s which were used the complex ,

molecules gradually breaki ng dow n i nto simpler molecules as

l
the d il ut ion i s i n creased B ut D utoit and A sto n fou n d that .

cadmium iodide i n aceto n e had an appreciable co n ductivity .

They give the followi n g values

C admiu m v 4 8 16 32 64 128 25 6 .

iodide Jug

The co nductivity is n ot large and we should not expect it ,

to be very great si n ce the co n ductivity of cadmium iodide i n

,

water is ab normally small These co nductivity values are .

1 Co mp t . re n d .
, 12 5 , 2 42 .
20 jon e s .

Ml o e cula r We ig ht of Me rcuric Chlor ide in A ce ton e .

Two determi n atio n s were made at di ffere n t dilutio n s with ,

the followi n g results

H g C lg. G ra m H g C l i n 1000 C onc
s g R ise in Mo l e c ul a r
ms g a m c e t n e n rmal l gp gh t
.

G ra . r s a o . o b oi i n - oi n t . we i .

The molecular weight fou n d agrees closely with that c al c u

lated for the formula H g C l which is an d this value

does not cha nge appre ciably with the dilutio n It is obvious .

that the co n ditio n of this salt i n solutio n is very di ffere n t from

the two already co n sidered There is n o Sig n of poly me riz a .

tio n of the molecules an d co n seque n tly n o molecular com

, , ,

plexes to break dow n as the dilutio n is i n creased The mole .

c ul e s o f mercuric chloride exist the n i n solutio n in aceto n e

_ , ,

I n the Simplest possible state .

The questio n as to whether solutio n s o f mercuric chloride

i n aceto n e co nduct the curre n t is of Special i n terest i n the ,

light of the above facts It would be very remarkable ih .

,

deed for a salt to give n ormal molecular weight which did

,

n o t cha n ge with th e dilutio n a n d have a n y marked power of ,

co nducti n g the curre n t .

We could say at o n ce that it is highly improbable that me r e

curi o chloride in aceto n e should h ave an y co n siderable c on

d u c t iv ity si n ce mercuric chloride i n water the stro n gest dis
,
—

s oc i at i ng solve n t co n ducts to o n ly a slight exte n t But we

—
.

are fortu nate i n havi n g the data beari n g upo n this subj ect .

l
L asz c z y nsk i has measured the co n ductivity of mercuric chlo
ride i n aceto n e a nd gives the followi n g results
,

Mercuric v
chloride
The co nductivity is thus exceedi n gly small j ust as would, , ,

be expected .

Ml o e cula r weig ht of Sodi um Iodide in A ce tone .

Five determi n atio n s of the molecular weight of sodium

l L oc . c it .
 Ml o e cula r We ig hts of Ce r ta i n Sa lts i n A ce ton e . 2 1

iodide i n aceto ne at very di ffere nt dilutio ns gave the followi n g

, ,

res ults
N I G m N Ii C a Ri i M l ul ra s a n 1 000 onc . se n o e c ar
l g p oi nt gh t
.

G ra ms . g ra m s ace to n e . n or m l
a . b oi i n -
. we i

The molecu lar weight of sodiu m iodide is n ot n ormal

( 1 49 9 ) at an y of the dilutio n s employed I t is less tha n n or .

m al eve n i n the most co nce n trated solut i o n employe d and ,

gradually dimi n ishes as the dilutio n of the solutio n becomes

greater and greater This substa n ce di ffers from the first two .

studied i n that its molecular weight is al w ays less tha n the

n ormal while i n the cases of cadmium io d ide an d ammo n ium
,

sulphocya n ate the molecular weight fou nd was always greater

tha n the n ormal .

It is impossible to say at prese nt what the co n ductivity of

sodium iodide i n aceto n e is at the above dilutio n s The c on ? , .

d uc ti vit y of sodi um iodide i n aceto n e at much greater dilu

l
tio ns has bee n measured by C arrara It was fou n d to be quite .

la r ge an d i ncreased rapidly with i n crease in dilutio n A t a

, .

volume of 2 5 6 the most co n ce n trated solutio n whose c Ond uc

,

t iv it y was measured the molecular co n ductivity is ,

while at a volume of 5 1 2 the molecular co nductivity is ,

Fro m these data the molecular co n ductivity at a volume of 1 0 ,

would be somewhat less tha n 1 00 We propose to measure .

the co nductivity of sodium iodide i n aceto n e at greater con

c e nt rat i on s i n co nn ectio n with an i n vestigatio n no w i n prog
,

ress in this laboratory For the prese nt we c an o n ly say that .

it is very probable that son i u m iodid e also represe nts a co n di

tio n i n which there is both pol ymerizatio n and dissociatio n .

It Should be stated i n co n nectio n with the work with sodi um

iodide that the solutio n s i n aceto n e were colored deeply yel
,

low I supposed at first that this was d ue to the liberatio n of

.

iodi n e but a test w ith starch paste showed that no free iodi ne
,

1 G az z . c hi m . i ta l .
, 2 7 , I, 2 13 .
22 j on e s , B arn e s , a nd Hy de .

was prese n t The yellow color m ay be due to som e reactio n

.

betwee n the aceto n e a nd sodium iodide an d I am i ncli n ed to ,

‘

lay less stress upo n these results tha n upo n those with the
other three compou n ds .

I i n te n ded to determi n e also the molecular weight of lith

ium chloride i n aceto n e but fou nd that it was n o t su ffi cie ntly
,

soluble for the purpose .

Of the five substa nces which Dutoit an d Fri d e ric h claim to

give normal molecular weights i n aceto n e I have studied four , ,

an d fi nd that o n ly o n e gives an y approach to n ormal values .

over a co n siderable ra n ge of dilutio n a n d this on e mercuri c , ,

chloride has practically n o co ndu ctivity The fifth substa n c e

, .

I could n ot i n ves tigate on acco u n t of its small solubility

These substa n ces i n stead o f prese n ti n g any exceptio n to the
,

theory of electrolytic dissociatio n fall directly i n li n e with the ,

theory as so ma ny similar cases have do n e I n deed it i s

, .
,

extremely i n terestin g to see ho w ma n y appare n t exceptio n s to

the theory of electrolytic dissociatio n disappear as e xp e rime n
tal methods become more refi n ed a n d experi me n tal work ,

more accurately carried out The amou nt of evide n ce for the .

ge n eral correct n ess of this most fruitful ge n eralizatio n is at

prese nt so large that a n y appare n t exceptio n will be accepted
o n ly after it has bee n very thorou ghly substa n tiate d by re
p e a t e d experime n ts This S hould however. n o t debar o n e , ,

from tryi n g to discover exceptio n s si n ce there is more i nterest ,

i n o n e well established exceptio n tha n i n m a n y facts which

-

co uld all have bee n predicted before an y work was do n e

’

Further work alo n g the li n e i ndicated by this paper will be

co n ti n ued i n this laboratory
C H E MI A L A R A R
C L BO TO Y
J O H N S H O P K IN S U NI V
May , 190 1 .

T HE L O W E R I N G O F T H E FRE E Z I N G P O I N T OF
A Q U E O U S H YD R O G E N D I O XI D E .

B Y H A RR Y C J O N E S J A ME S B A R N E S A N D E DW A R D P H Y D E
.
, , . .

Aumber of attempts have bee n made to fi n d a solve nt

n

whose dissociati n g power was greater tha n that of water A .

large n umber of solve n ts have bee n studied i n this co n n ectio n ,

 Fr e e z ing Poi n t of A gue ous Hy dr og e n Di ox ide . 23

with the result that of all the liquids i n vestigated water has ,

the m aximum io n izi ng power .

1
A fter exami n i ng all the work which has bee n do n e it ap
p e are d to us n ot i mprobable that hydroge n dioxide might
z
have a higher dissociati n g power tha n water J J Thomso n . . .

poi nted out some ti me ago that i n terms of the theory of elec
t roly tic dissociatio n a relatio n should exist betwee n the disso
c i at in g power of solve n ts an d their dielectric co n sta nts
.
A .

3
similar relation was recog n ized a little later by Ner n st T he .

dielectric co nsta nt of a mixture of hydroge n dioxide and water

4
h as bee n determi n ed rece ntly by C alvert From this he has .

calculated the dielectric co n sta n t of pure hydroge n dioxide to

be at while the dielectric co n sta n t of water at the
same temperature is 8 1 .

That hydroge n dioxide should have a high dissociati ng

power was suspected by Bruhl a n umber of years ago H e
5
.

regards the co n stitutio n of hydroge n dioxide to be

H —
OE O -
H
It is therefore in a high degree an u n saturated compou n
‘
, ,
d , ,

an d Si n ce accordi n g to Brii hl dissociati ng power depe nds

, ,

upo n the prese n ce of tetravale n t oxyge n upo n the u nsat ura —

ted co n ditio n hydroge n dioxi d e Should have a very high

—

io n izi n g power Bruhl expressed the O pi nio n that if the dis

.
-

so c i ati n g power of hydroge n dioxide could be measured it

would probably be fou n d to be greater tha n that of water .

We u n dertook this work with the hope of bei ng able to de

termi n e d irectly or i n directly the dissociati n g power of hy
, ,

droge n dioxi d e .

P u r ifica ti on f
o H y d r og e n D i ox ide .

We at first attempted to purify hydroge n dioxide by the

method describe d by Bre d ig an d von Ber nec k 6
Marcha n d s .
’

commercial hydroge n dioxide was distilled on a water bath -

1 A umm a y b y H C Jo n e s Th i s J O U R N A L
s r . . .
, 2 5 ,
2 32 .
2 P h i l Ma
g 36 3
. .
, , 20 .

3 Z ts c h ph y s C h m 13 5 3
r. . e .
, , 1 .

4 A n de
n .P h y s 1 483 r , , .

5 Be d ch e m Ge s
r. . 2 8 86 8 . .
, , 2 .

5 Zt c hs ph y s C h e m 3 1 7
r . .
, 2 1.
24 fon e s ,
Ba r n e s , a nd Hy de .

u nder a pressure of about 8 0 m m of mercury u n til a very .

,

small residue remai n ed P ure barium hydroxide was added

.

to the distillate u n til it was Slightly alkali ne and the n pure ,

carbo n dioxide was run i nto the solutio n to co nvert the excess
of bari um hydroxide i nto carbo n ate The solutio n after fil .
,

teri n g was distilled u nd er dimi nished pressure a slow cur

, ,

re n t of air bei n g allo w ed to flow through the liquid duri n g the

distillatio n A fter about on e third of the liqu id had distilled
.
-

over the remai n der was filtered to remove the barium car
,

bo n ate which had bee n formed fro m the acid barium carbo n ate
'

i n solutio n by boili n g The remai nder of the solutio n was

.

the n distilled u n d er dimi n ished pressure usi n g a ne w distill ,

i ng flas k so as to avoid the prese n ce of a scratched surface .

We fo un d that duri ng this process the loss of hydroge n di

ox i de by decompositio n was very great The acid barium .

carbo nate is not all decomposed by boili ng in the earlier

stages of the distillatio n but gradually separates out as the
,

distillatio n proceeds The decompositio n of the dioxi d e

.
,

which takes place very rapidly i n the later stages of the d is

t illat ion is probably caused by the solid bariu m carbo n ate
,

which has separated or by the acid carbo n ate still rem ai n i ng i n

,

the solutio n O n accou n t of the great loss of m aterial we

.

aba ndo n ed the above method i n favor of the followi n g which ,

we fou n d to be far more satisfactory .

The commercial hydroge n dioxide was treated with zi nc

oxide and allowed to remai n in co ntact with the oxide over
n ight . By this mea n s any hydrochloric or other volatile acid
prese n t was co nverted i nto the zi n c salt The solutio n was .

the n filtered to remove the excess of zi nc oxide a n d distilled ,

on a water bath u nder a pressure of from 6 0 to 9 0 m m of

-
.

mercury The distillatio n was allowed to proceed slowly

.
,

the temperature bei n g kept as low as possible The first third .

of the distillate was discarded Si n ce it co ntai n e d compara

t ive l y little dioxide The d istillatio n was co nti n ued u n ti l
.

o nly a few cubic ce ntimeters remai n ed in the flask The last .

two thirds of the distillate co n tai ned the material used i n this
-

work .

The adva ntage of this method over the o ne i n which barium

 F re e z i ng -P oi n t f A q ue ans Hy drog e n D iox ide
o . 25

hydroxide was employed is probably to be fou n d i n the fact ,

that the zi n c chloride formed is so very soluble that it does

n ot separate fro m the solutio n duri n g the distillatio n u nti l

n early all of the liquid has bee n distilled o f

f If an attempt .

is m ade to distil the last few drops out of the flask a Vigor ,

ous decompositio n of the dioxide sets i n probably due to the ,

separatio n from this co n ce ntrated solutio n of some solid m a

t e ri al .

The aqueous S olutio n of hydroge n dioxide thus purified was

co n ce n trated by placi n g it i n a n e w a nd u n scratched evapora
ti n g dish which was very ge n tly warmed on a water bath
,
-
.

The temperature of the solutio n of hydroge n dioxide should

n ot be allowed to rise above an d it is better if the e v ap o

ratio n oi water from the solutio n took place at a lower tem

p e ra tu r e especially after the co n ce n tratio n of the solu tio n
,

has become co n siderable We at first attempted to conce n .

trate the sol utio n of hydroge n dioxide by allo wi n g its tem

as Wolfe n ste in had do n e t ak
° l
p e ra t u re to rise to 7 0 or ,

i ng the precautio n reco mme n ded by him of allowi n g o n ly a

small part of the evaporati n g dish to come i n co ntact with the
water bath A t these elevated temperatures the loss i n hy
-
.

droge n dioxide by decompositio n was so great that m uch

lower temperatures were e mployed .

A n A tte mpt to A pply the Con ducti vi ty M th d

e o .

H avi ng obtai n ed pure hy d roge n dioxide by the above

method i n an y qua n tity desired we tried to determi n e the
, ,

co n ductivity of solutio ns of salts i n aqueous hydroge n d iox

ide It was obvious at th e outset that the ordi n ary plati num
.

plates could n ot be used for electrodes si n ce the dioxide '

would be decomposed by them We h ad our plati n um elec .

tro d es very highly polished by a Silversmith a nd we worked ,

at zero degrees B ut eve n a t this lo w temperature the d iox

.

ide was sufli c ie ntly decomposed by the metal to cover the

plates with oxyge n before a readi ng could be m ade The .

aqueous solutio n of dioxide used co n tai n ed o nly from 6 to 1 0

per ce nt yet eve n at such d ilutio n s the decompositio n was
, , ,

sufli c i e nt to preve nt us fro m measuri n g the co n ductivity of

the solutio ns .

1 Be r. d . c he m . Ge s .
, 2 8 , 3309 .
26 jon es ,
Ba rn e s, a nd Hy de .

We the n tried a large n u mber of other metals to see if o ne

could be fou nd which would not decompose the dioxide A ll .

of the metals tried decomposed the hydroge n dioxide to such

a n exte n t that they could n o t be used for electrodes We .

were therefore compelled to aba ndo n the co nductivity method

( for the prese n t ) as a mea n s of measuri n g the dissociatio n of
electrolytes in aqueous hydroge n dio xide .

The o nly method at our disposal was that based upo n the
loweri n g of the freezi ng poi n t of solve n ts by dissolved sub
-

sta n ces .

A pplica ti on j
o the Fr e e z i ng - Poi n t M th d
e o .

It seemed probable that by compari n g the loweri n g of the

freezi ng poi n t of aqueous hydroge n dioxide with the loweri ng
-

of the freezi n g poi n t of water p r od uced by the same sub

-

sta n ces we could form some idea as to the relative dissocia

,

ti ng power of water and of hydroge n dioxide The loweri n g .

of the freezi n g poi n t of water produced by solutio n s of p ot as

-

sium chloride pota ssium carbo n ate an d sodium carbo nate of

, ,

various dilutio ns was studied i n the usual ma n n er The

, .

solutio n s were prepared from pure recrystallize d salts by , ,

dissolvi n g weighed qua n tities in water i n ca l ibrated me asu r ,

i n g flasks I n every case the n ormal solutio n was prepared

. .

by weighi ng the salt dissolvi n g it a n d diluti n g to a k n ow n

,

volume The more d ilute sol utio n s w ere made from the nor
.

mal solutio n by diluti n g measured volumes in measuri n g

flasks .

The sol utio n s i n aqueous hydroge n d ioxide were prepared

i n exactly the same ma nn er The n ormal solutio n s were .

m ade by dissolvi n g weighed qua n tities of the salts in the di

oxide in a measuri ng flask an d diluti n g with the dioxide to
, ,

the required volume Duri ng the solutio n of the salt both

.

the salt and solve nt were kept at zero degrees by surrou ndi n g
the flask with ice i n order that there might be n o appreciable
,

deco mpositio n of the dioxide The more dilute solutio n s .

were prepared fro m the n ormal solutio n by addi ng a meas

u re d volume of the latter to a 5 0 cc measuri ng flas k an d di .

luti ng to volume with the solutio n of the dioxide The solu .

2 8 fone s ,
B a rn e s , a nd Hy b e .

These results show that the molecular depressio n of p otas

sium chloride i n aqueous hydroge n dioxide is much less tha n
i n water .

The followi ng results were obtai n ed with sodium n itrate

Sodiu m N i tr a te i n Wa te r
Mo l e c ul a r l ow e r
O b s e rv e d o w e ri nl g i ng of f re e z in g
f
o f r e e z i n - oi n t gp . p oi n t .

1 62 I
8 39

Sodi u m N i tr a te A q ue ous Hy drog e n D iox ide P e r Ce n t) .

C ton c e n ra t i o n Mo l e c ul a r l o w e r
m m l e c ul e s l ow e rin g
.

G ra - o O b s e rv e d ing f
of re e z in g
p l i te
e r r . f
o f re e z in g p oi n t
-
. p oi n t .

1 .
5 90
0
o . 80 8

the seco nd series of experime nts the solutio n s were pre

In
pared from e ntirely ne w material .

Sodi um N i tra te Strong e r Hy drog e n Di ox ide ( 7 P e r Ce n t ) .

M l ul l w
o ec ar o e r
O b s e rv e d o w e ri n l g i ng f fo in gre e z
f
o f r e e z i n - oi n t gp . p int o .

O
I 57 1 .

O
o -7 9 4

The results obtai ned with sodium n itrate i n aqueous hydro

g e n dioxide li k e those O btai n ed with potassium chloride are
, ,

smaller tha n the correspo ndi ng results i n water as the sol

ve nt To test still further the e ffect of the hydroge n dioxide
.

o n the freezi n g poi n t loweri ng a more co nce ntrated solutio n

-
,

of hydroge n dioxide i n water was used The loweri n gs ob .

t ai n e d i n th e latter case were still smaller tha n whe n the more

 F r e e z ing Poi nt
-
of A q u e ou s Hy d rog e n D iox ide . 29

dilute hydroge n dioxide was emplo y ed We would h ave used .

solutio n s of hydroge n dioxid e of greater co n ce n tratio n but ,

the freezi n g poi n t of such solutio n s would be so low that some

-

refrigerati n g age n t other tha n salt and ice would have to be

employed and it is diffi cult to regulate the temperature s of
s uch very cold mi x tures .

The results with potassium n itrate are eve n more striki n g

tha n those with sodium n itrate The freezi n g poi n t loweri n g
.
-

o f this salt i n w ater a n d i n two solutio n s of hydroge n dioxide

, ,

was measured .

Pota ssi u m N i tra te i n Wa te r

O b se d
rve low e i n g r
f
o f re e z i n g p oi n t
-
.

56

77 1

Pota ssi u m N i tr a te i n A q ue ous Hy drog e n Diox i de 5 3 P e r Ce n t) . .

Mo l e c ul a r l ow e r
O bs e rv e d l w ri n g
o e ing of f re e z in g
oi f r e e z in g p oi t
- n . p oi n t .

1 64 2 . 164

66 7
1 90 2 .
3 80
627 2 .
5 08

Pota ssi um IVi tra te i n Strong e r Hy drog e n Di ox i de( 7 P e r Ce n t) .

M l ul l w
o ec ar o e r
O b s e rv e d l ow e i n g r i g ff
n o i g re e z n
f
Of re e z in g p int
-
o . p i t o n .

0
I I 95 4
I . 05 7 2 . I 14

5 70

The loweri ng of the freezi ng poi nt of water by potassium

-

n itrate is very m uch greater tha n the loweri n g of the f re e z

i n g poi n t of aqueous hydroge n dioxide

-
The loweri n g be .

comes smaller as we wo uld expect whe n the qua n tity of di

, ,

o xide prese n t is i n creased .

I n all o fthese experime n ts the amo u n t of the hy d roge n d i

o xide prese n t was determi n ed after the salt had bee n i n tro
30 l an e s ,
B a rn e s , an d Hy de .

to see whether any appreciable decompositio n of the

d uc e d ,
d ioxide had bee n effected by the salt In no case was any .

appreciable ch a n ge i n the co n ce ntratio n of the dioxide de

t e c te d .

The e ffect of the prese n ce of hydroge n dioxide i n water is ,

the n to dimi nish the loweri ng of the freezi n g poi nt produced

,
-

by a dissolved salt The questio n which n aturally arises is .

,

why is this the case The simplest expla n atio n seems to be

th at the h ydroge n dioxide either decreases the dissociatio n
which has bee n effect ed by the water or acts as a polymer ,

izi n g age n t upo n the u ndissociated molecules prese n t i n th e

solutio n .

I n the case of potassium n itrate it i s di f

fi cult to see how the
results obtai ned can be accou n ted for on the basis of poly
m e riz at io n I ndeed the decrease in the molecular loweri ng
.
, ,

produced by the prese n ce of the hydroge n dioxide is so great ,

i n this case that we would suspect some co mbi n atio n had

take n place betwee n the potassiu m n itrate an d the hydroge n
dioxide This poi nt we propose to i n vestigate
. .

This is but a prelimi n ary i nvestigatio n Further work on .

the loweri n g of the freezi ng poi n t of aqueous hydroge n d iox -

ide will be do n e i n this laboratory .

C H E MIC A L L A B O R AT O RY
J O H N S H O P K IN S U NI V
,

F b u a ry 19
e r ,
01 .

Several mo nths after the above paper was writte n an ac

cou n t oi an i n vestigatio n on H ydroge n D ioxide as an A cid ,

was prese nted to the G erma n E lectrochemical Society by ,

l
Bre d ig This has bee n rece ntly described more fully by
.

2
C alvert .

Two facts brought out i n this i n vestigatio n are of Special

i nterest i n this co nn ectio n It is shown that electrodes of .

iro n covered with t in do not deco mpose dilute al k ali n e hy , ,

droge n dioxide an d c a n be used to measure the co nductivity

,

of such solutio n s We shall try such electrodes i n an exte n

.

sio n of the above li n e of work .

1 Z ts c h r .
E l e k tro c h e m .
, 7 , 622 .

2 Z ts c h r . ph y s C h e m
. .
, 3 8 , 5 13 .
 Tr i bromp he n ol bromide .
31
'

It has also be e n show n by C alvert that a n umber of the

stro ng al k alies c an combi ne with hydroge n dioxide formi n g ,

defi n ite compou nds with it This ren ders it no t impossible .

that our suggestio n that potassiu m n itrate may have com

bine d with so me of the hydroge n dioxide is the true expla n a ,

tio n of the results which we O btai n ed It at least makes it .

highly desirable that this poi n t Sho uld be tested by direct ex

p e ri m e n t .

J O H N S H O P K I N S U NIV .
,

D e c e mb e r , 1 90 1 .

A ST U DY O F T R IB R O MHE
P N O L BR O MIDE .

BY J . H K A ST L
. E .

The compou nd called tribromph e nol bromid e was d is c ov

ered by B e nedik t i n H e Obtai n ed it i n the form of
°
beautiful yellow crystals which were fou nd to m elt at 1 1 8 C ,
.

°
O n heati n g it t o 1 2 5 C it was fou n d to decompose evolvi n g .
,

o n e atom of bro mi n e a n d givi n g a n a morphous derivative ,

which Be n edi k t called he x abromph e noq u inone Be n edik t, .

m ade the further i nteresti n g observatio n that on heati ng the

compou nd u n der sulphuric acid it u nderwe n t a molecular re
arra ngeme n t whereby i t was tra nsformed completely and
qua ntitatively i n to t e trabro mp h e nol B e n edikt further i n ve s .

t i g ate d the actio n of tr ibro mp h e nol bro mid e o n alco ho l ti n and ,

hydrochloric acid a n ili n e an d phe n ol In every case he ob

, .

t ai ne d ordi nary tribromphe n ol as a fi nal product H e was .

therefore led to assig n to the com pou nd the followi ng stru c

tural formula as that best comporti ng with the ge neral be
havior of th e substa n ce vi z

Inother words he loo k ed upo n t ribromph e nolbromide as a

,

derivative of tribromphe nol in which the hydroxyl hydroge n

of the l atter had bee n replaced by bromi ne .

It Seemed to the writer therefore to o ffe r a fruitful field for

further i n vest igatio n especiall yas the co nstitutio n of the co m
,

pou nd as determi n ed by Be nedi k t seemed to rest upo n very

, ,

1 A nn C . he m .
( L i e bi g ) , 19 9 , 12 7 .
32 K astle .

sle n der li nes of evide nce and i n asmuch further as no satis ,

factory expla n atio n was o ffered for the remarkable molecular

rearra n geme nt which the c o m p o u n d u n d e rg oe s u n der sul
'

p h uric acid This i n vestigatio n was begu n i n 1 8 99 U n for

. .

t u n at e ly it has bee n i nterrupted at various times by other

,

work of a more pressi n g character an d is eve n yet inco m ,

p le te . It is believed , however that certai n results already ,

reached are of sufli c ie n t i n terest to warra n t publicatio n in

their present form The work has bee n do n e i n coll aboratio n
.

with certai n of the adva n ced stude n ts of the chemical depart

me n t here via A S L oe ve nh art R osa Speyer and J W
, , . .
, , . .

G ilbert .

P RE P ARAT I O N AN D P R O P ER T I E S OF T R I B R O MP H E N O L B R O
M ID E C O N D U C T O F T R I B R O MP H E N O L B R O MI D E T O WAR D S
.

HEA T A N D L I G H T A C T I O N O F T R I B R O M P H E N O L
.

B R O M I D E O N WA T ER P O T A S SI U M I O D I D E A N D , ,

Z I N C ET H YL B E H AVI O R O F T R I B R O M
.

P H E N O L B R O MI D E T O WAR D S BR O M IN E
A N D I O D IN E .

BY A . S L OB V E
_. N HA R T .

T ribro mp he n olbromid e was prepared esse n tially accordi ng

to B e n edikt s method by addi n g an aqueous solutio n of phe
’

n ol to o ne of bromi n e co n tain i n g the bromi n e Slightly i n ex

cess of the amou n t required U su ally a solutio n co ntai n i n g

.

grams of phe n ol was add ed to bromi n e water co n tai ni n g

1 3 cc . of bro mi ne an d the mixture thoroughly shake n an d
,

allowed to sta n d for several hours U n der these co n ditio n s .

the t ribromph e nol brom id e separates as a yellow gra n ular pre

c i p it a te altogether di ffere n t i n appeara n ce from tribro m
,

phe n ol It h as bee n fou n d best to filter the substa nce through

.

fi n e cotto n cloth A fter washi n g with water the compou n d

.

was tra n sferred to fi lte r pa per and allowed to dry i n the air
-
,

i n the dark and at ordi nary temperatures Tribromphe n ol .

bromide is thus obtai n ed i n the form of a bu ff colored po wder -

.

O n a n alysis it was fou nd to co ntai n 1 9 per ce nt of easily re

placeable bromi n e A s observed by Be n edikt the compou nd
.
,
 Tr i bromp he n olbr om ia e
’
.
33

c an be obtai n ed i n beautiful crystalli n e co n ditio n by crystal

l iz ing fro m hot chloroform O n cooli n g it separates from its
.
,

solutio n in chloroform in the form of beautiful lemo n yellow -

°
plates or prisms melti n g at 1 1 8 C U p to a certai n limit the .

crystals become lighter i n color the ofte n er the compou n d is

recrystallized from chloroform For reaso n s to be discussed .
,

i n a subseque nt part of the paper the compou n d is best pre ,

served ih O pe n vessels an d n ot i n tightly stoppered bottles .

The molecula r weight of the compo u nd was determi ned by

the freezi n g poi nt method usi ng ethyle n e bromide as the sol
-
,

ve n t . A n average of three co n corda n t determi n atio n s gave

as the molecular weight The calculated molecular .

weight of the compou nd is 4 1 0 .

Con duct o f Tr i bromphe n olbr om ide Towa rds He a t a nd L ig ht .

A ccor d i n g to Be n e d ikt whe n tribromph e nol bromi d e is

,
°
heate d it melts at 1 1 8 C to a re d dish liquid If the tempera
. .

°
ture be raised to 1 2 5 C the compou nd begi n s to decompose
.
,

evolvi n g free bromi n e If the compou n d be h eated for some

.

time at 1 30 C i n a curre n t of carbo n dioxide it loses 1 ato m

°
.

of bromi n e for each molecule of the compou nd decomposed ,

a n d there is left beh i n d a reddish substa n ce havi ng much the

appeara n ce of molte n sul phur O n dissolvi n g this gum my .

mass i n ether an d addi n g a l cohol to the solutio n a white

amorphous substa n ce is obtai n ed which accordi n g to B e n e , ,

d ik t is h e x abromph e n oq ui n on e
, ,

C , H, Br, O

In the hope of throw i n g so m e further light on the c o nsti tu

tio n of this substa n ce an d thereby lear n i n g someth i n g more
,

of the n ature of tribro mp h e n ol bromi d e itself the attempt was ,

made to sy n thesize he x abromph e noq u inon e from tri brom

p h e n olbromi d e an d Silver tri brom ph e n ol at e i n the followi n g
ma n n er : T e n grams of fi n ely powdered tribrom phe n olbro
‘

mide were place d i n a flask together with 30 cc af chloroform .

an d grams of silver tribrom ph e nol ate were added

gradually The reactio n too k place at o n ce at ordi n ary tem
.

p e r ature s an d after sha k i n g thoroughly an d S

, ta ndi ng for
some time it was filtered fro m the Silver bromide The resi .

3 2 7
-
34 Ka stle .

d ue was fou nd to co n sist e ntirely of Silver bromi d e O n the .

additio n of alcohol to the filtrate it was fou n d to yield a white

fl occ ule nt precipitate which proved to be ide ntical i n every
,

respect with B e n edikt s he x abro mp h e n oq ui non e

’
.

On the A cti on of Su nlig ht on Tr i bromphe n ol br omi de i n Solu tion

i n Ca r bon B i sulp hi de .

AS already stated i n the above tri bro mphe n olbromid e in ,

pure co n ditio n has i n the solid state a beautiful yellow color

, , .

Whe n dissolved i n carbo n bisulphide i t imparts a yellow color

to the solutio n and if kept i n the dark such solutio n s retai n
,

their yello w color u n altere d for almost any le n gth of time .

Such solutio ns however have bee n fou nd to cha nge Slowly

, , ,

eve n in di ffused light an d i n the direct su nlight they rapidly

,

assume the characteristic color of free bro mi ne i n solutio n in

carbo n bisulphide Such havi n g bee n fou n d to be the case it was
.
,

decided to follow the decompositio n in direct su nlight colori

metrically by compari n g the sol utio n s of t ribromp h e nol bro
mide which h ad bee n exposed to the light for a give n time
with freshly prepared solutio ns of bromi n e i n carbo n bisul
p h i d e of k n ow n stre n gth A N 1 0 solutio n of tribromphe n ol
.

bro mide was m ade up i n the dark and the n exposed to direct
su n light portio n s bei ng removed from the flask from time to
,

time for compariso n with the sta n dard solutio n of free bro
mi n e The color compariso n s w ere made i n small Nessler
.

cyli n ders of 30 cc capacity and all havi n g the same i nter n al

.

diameter Whe n the solutio n of tribromp he nol bromide had

.

become too deeply colored to make accurate compariso n s pos

sible aliquot portio n s were removed from the flask an d dilu
,

ted to a give n vol ume so as to get more accurate results The .

color compariso ns were always made o n volumes of 1 0 cc .

The fol lowi ng are the results obtai n ed

Pe rc e n t a ge de co mp os i ti n
o
l ul
ca c d for 1
a te a to m o f
T me
i m
b ro i n e :
36 Ha stle .

crystalli n e co nditio n and he nce its co nstitutio n has

, n ot ye t
bee n settled defi nitely .

The A ction ry ‘
Wa te r on Tr i bromphe n ol bromi de .

In V iew of the ease with which de t ribromp h e nolbromi d e

composes both whe n heated in the solid state and i n soluti o n
,

i n orga n ic solve n ts it occurred to us that it might prove of

,

i nterest to try its co n duct toward s water at high temperat ure .

A ccordi n gly 5 grams of tribro mp he nol bro mid e were heated

,
°
i n a hard glass tube with 5 cc of water for t e n hours at 1 00
.
, ,

C A fter a few mi n utes heati n g o n the water bath the tub e

’
.
-

was observed to co n tai n some bro mi n e vapor which however , , ,

shortly disappeared A t the co nclusio n of the experime n t the

.

substa n ce i n the tube was fo u n d to be i n a molte n co nditio n ,

but solidified o n cooli n g O n O pe n i n g th e tube it was fou nd

.

that n o pressure had developed The super n ata n t liquid c on .

t ai n e d o n ly a trace of bromi n e but was fou n d to co n tai n l arg e

qua n tities of hydrobromic acid The solid mass was fou n d to .

co n sist of a mixture of tribromphe n ol an d te trabrom q ui n on e .

H e n ce the reactio n must i n all probability h ave take n place

, ,

accordi n g to this equatio n

2H, O
2 C H 2 B1 3 ( O H ) C , Br, O 2 H Br H, O
‘

2 .
6

A ction o fP ota ssi u m Iodi de on Tr i br omp he n ol brom ide .

T ribro mp h e nol bromid e was fou n d to b e capable of setti n g

free iodi n e fro m solutio n s of potassi um iodide It occurred to .

us i n this co n n ectio n that it mig h t be possible to prepare

, ,

ribro mp h e n o lio d i d e by mea n s of this reactio n In order to

t .

test this poi n t 8 grams of tri bromp he nolbro m ide were gro u n d
,

to a fi n e powder an d mixed with a slight excess of potassium

iodide The mass tur n ed brow n i n color at o nce i ndica ti n g
.
,

that the reactio n betwee n these two substa n ces had beg un
eve n i n the solid state Before the reactio n had proceeded
.

far however 30 cc of chlorofor m were added a n d the flask

, , .

sealed an d allowed to sta n d several days O n O pe n i n g the .

fl ask it was fo und that the solutio n co ntai n ed a large amou n t

of free iodi n e thereby i n d icati n g that the reactio n had n ot oc
,
 Tr i bromp he nol bromide .
37

c urred i n the ma nn er hoped for O n a d di n g alcohol to so me

.

o f the solutio n obtai n ed i n the above a precipitate of hex a ,

bromp he n oq uinon e was obtai n ed The reactio n of potassium

.

i odide on tribromph e nolbromid e is therefore i n all probability , ,

to be represe nted by the followi n g equatio n

KI C6 H BrSO O BrSH C6 j K Br + BrI
2
—
2
-
.

It should be observed however that this reactio n proceeds

, ,

i n this ma n n er o n ly i n th e abse n ce of w ater as may be see n ,

fro m the followi n g experime n t gram of tribromphe n ol

bro mide were dissolved i n 1 0 cc of carbo n bisulphide and 2 5 .
,

cc . of water were added an d an ex cess of potassium iodide .

The free iodi n e was titrated with N / 1 0 thiosulph ate solutio n .

The a mou nt of thiosulphate solutio n required was fou n d to

vary betwee n 9 an d 1 0 cc accordi n g to t h e relative amou n ts
.
,

o f water carbo n bisulphi d e a nd potassium iodide prese n t

, , .

Further the super n ata n t aqueous solutio n gave whe n acidi

, ,

fi e d a C O p iou s precipitate of tribromphe n ol

,
In aqueous solu .

t io n therefore the actio n of potassium iodide on tribro m

'

, ,
;
p h e n olbrom ide takes place accordi n g to the followi ng e q ua
t io n s

2 KI 2 C 6 H Br 0K
r: Er I 2 3 z

a nd Br + 2 K I
,
2 K Br 1 2
.

This would accou n t for the double amo u nt of iod i ne set free .

We see thus that t ribro mp h e n olbrom id e decomposes p ota s

sium io d ide by V irtue of the easily replaceable bromi n e which
it co n tai n s and also for the reaso n that it is a n oxidizi ng
,

age n t It will be observed further that i n solutio n in or

.
, ,

a n i c solve n ts t ri bromp he n ol bro mi d e te n ds toward the pro

g
d uctio n of h e x abromp he n oq u i non e whereas in aqueous solu ,

t io n s it te n ds towards the productio n of tribromphe n ol .

fZi nc E thyl
A ction o on Tri bromphe n olbromide .

If the co n stitutio n of tribromph e n olbro m id e is correctly rep

r e se n ted by Be n edikt s formu l a on e would
’
,

n at urally expect to obtai n ethyl tri bro mphe n ol ate ,

C, H, Br, ( O C, H5 )
by treati ng it with zi n c ethyl . In order to test this poi nt ,
38 K a stle .

equivale nt qua ntities of tribromp he nol bro mide a nd zi n c ethyl

were brought together i n absolute ether A V igorous re ac .

tio n occurred but i n stead of obtai n i n g ethyl tribromph e nol ate

,

an d zi n c bro mide we obtai n ed ethyl bromide a n d the zi n c salt

,

salt of tribromphe nol In other words the reactio n betwee n

.
,

these two substa n ces occurs in a ma nn er exactly the reverse

of what on e would n aturally expect if Be n edikt s V iew of th e ’

co n stitutio n of the compou n d is correct The sig n ifica n ce .

of this result will be discussed i n a subse q ue nt part of the

paper .

f Iodi n e on Tr i bromp he n ol bromide

A ction o .

In the h O p e o f bei n g able to prepare tribro mph e n oli od i d e it

occurred to us to try the actio n of iodi n e o n tri bro mphe n olbro
mide With this i n V iew 5 grams Of tribro mp h e n olbromi d e
.
,

were dissolved i n carbo n bisulphide and to this solutio n th e ,

calculated amou n t of iodi n e grams was added and the

, ,

solutio n well sh ake n It soo n became evide nt that some re

.

actio n had take n place for the carbo n bisulphide solutio n soo n
,

lost its V iolet color a nd assumed a brow n ish ti n t i n stead .

A fter sta n di n g about two a nd a half hours the solutio n was .

distilled at the lowest possible te m perature the distillate ,

showi ng the same brow nish color as the solutio n itself T h e .

d istillate was tested both for bromi n e an d iodi n e with the re

sult th at both were fou nd to be prese n t The residue left i n .

the distilli n g bulb was dissolved i n chloroform an d th e s ol u

tio n precipitated with alcohol The amorphous white pre.

c ip i t at e thus obtai n ed was Show n to be h e x abro mp h e n oq u i

n one . The actio n o f iodi n e o n tri bro mp h e n olbromi d e c an

therefore b e represe n ted by the followi n g equatio n
2 C GH2 Br, ( O Br ) + 1, C 6 H2 B rsO —
O B1 3 H2 C 6 -
i 2 Br I .

The Ca ta ly sis o f T r i br omp he n ol bromi de b

y B r om i n e Vap or .

It was observed that tribrom p he n olbro m i d e coul d not be

preserved as well i n tightly stoppered bottles as by freely ex
posi n g it to the air This seemed to i ndicate that the traces
.

of free bromi n e resulti n g from the Slight decompositio n of the

compou n d at ordi nary temperatures if n ot removed acted by , ,
 Tr i bromp he n ol bromide .
39

catalysis to greatly accelerate the deco mpositio n of the rest of

the compou n d I n order to test th is poi n t the followi n g ex
.

p e r i me n ts were tried Four tubes were prepared each c on ,

tai n i n g gra m o f p ure tribro mph e nol bro m id e I nto two .

of these small amo u nts of bromi n e vapor were i n troduced

, .

These tubes together with the two co n tai ni n g no bromi n e

, ,

were the n sealed Two of the tubes o n e co ntai nin g bromi n e

.
,

vapor an d the other without were kept i n the dark for four ,

days A si milar pair of tubes was exposed to the d irect s un

.

light for eight hours O n exami ni n g the tubes that had bee n
.

exposed to the direct su n light the n ext day it could be , ,

easily see n that the greatest decompositio n had occurred

i n the tubes co n tai n i ng the bromi n e va por Th e tubes .

were the n ope n ed and the vapor of bromi n e removed by a cur

re n t of air The m aterial i n the tubes was the n carefully
.

washed out with chloroform an d an excess of an aqueous solu

tio n O f potassiu m iodide added an d the free iodi n e titrated ,

agai n st N / 10 thiosulphate solutio n If n o n e of the compou n d .

h ad decomposed it would have required , cc of th iosul .

~

ph ate A S a matter of fac t the tube co n tai n i ng the tribro m

.
,

h e n o l brom i de without bromi n e required cc of the thio

p .

sulphate correspo n di n g to a d ecompositio n of

,
per ce n t ,

while the tube co ntai n i n g the bromi n e vapor required o n ly

cc correspo n di n g to a decompositio n of
.
,
per ce nt .

I n other words by mea n s of a trace of bromi n e the d e c o mp o

,

sitiou of t ribromp he n olbro m id e had bee n accelerated n early

fourfol d . The seco n d pair of tubes was allowed to remai n
i n the dark four days whe n they were ope n ed an d the bro
,

mi ne vapor removed by a curre n t of air The residues were .

titrated with sodium thiosulphate after the additio n of p o tas

sium iodi d e The tube which did n ot co ntai n bromi n e vapor
.

origi n ally required , cc of thiosulphate correspo ndi n g .

,

to a decompositio n of per ce n t while the tube co n tai n i n g ,

the bromi n e vapor origi n ally required 1 cc of thiosulphate

, .
,

correspo n di ng to a decompositio n of 30 5 per ce n t In this case . .

the decompositio n of tribro mph e n olbromide had take n place

eight times faster i n the prese n ce o f bromi n e tha n without .

The great acceleratio n of the deco mpositio n of this compou nd

40 Ka stle .

by a small amou nt of bromi ne vapor is a very remarkable a nd

n oteworthy fact .

THE C O N ST I T U T I O N O F T R I B R O MP H E N O L B R O MI D E T HE .

P RE P ARAT I O N A N D P R O P ER T I E S O F T R I B R O MP H E N YL
SU LP H O N AT E T H E C O N V E R S I O N O F T R I BR O M
.

P H E N O L B R O MI D E I NT O ME T A D I B R O M
QUI NO N E .

BY RO S A S E Y E R
P .

A fter some tim e the i n vestigatio n of t ri brom p he n olbro mid e

was resumed at this poi n t for the reaso n that the co n stitutio n
,

of the compou n d co uld n ot yet be looked upo n as defi nitely

settled ei ther i n favor of or agai n st B e n edikt s V iew The ’
.

peculiar Co n duct of the compou n d towards zi n c ethyl as ,

poi nted out i n the precedi n g paper still left the matter i n ,

doubt although the formatio n of zi nc salt of tribromphe n ol

,

rather tha n its ethyl ether would seem to i n dicate that Be n e

d i k t s formula is i n correct an d that t ribromphe n olbrom i d e is
’
,

by n o mea n s as Simple as he represe nted it to be In order to .

throw further light upo n t his subj ect it occurred to us that it ,

might be well to attempt the prep aratio n of the tribromp he ny l

ether of be nz e n e sulpho n ic acid b y two disti n ct methods the ,

first bei n g by the actio n of be n z e n e s ulp hon c hloride o n

sodium tribromp h e nol ate the seco nd bei n g by the actio n of
so d ium be n z e n e su lp hin ate o n tribro mp h e n olbromi d e Should .

both of these reactio n s yield the same sulpho n ic ether it ,

would probably be regarded as tolerably certai n proof of the

corre c t n ess of B e n edikt s formula for this compou n d
’
.

Tri bromp he ny l B e n z e n e sulp hon a te ,

This ether is readily prepared by the actio n of sodium tri

brom p he n ol at e on be nz e n e sulp honc hlorid e The s ulp hon .

chloride is dissolved i n absolute ether an d to this Solutio n ,

fi nely po wdered a nhydrous sodium tribro mph e nolate was

added i n small qua ntities at a time an d with co nsta n t
,

Shaki n g u n til a co n siderable excess had bee n added

, The .

solutio n was the n filtered and the clear filtrate allowed to evap
 Tr i bromp he nolbromide .
41

orate Spo nta neously at ordi n ary temperature whe n the sul ,

pho n ic ether was obtai n ed A still better method for the

‘

preparatio n of the ether is the followi ng The sodiu m salt of

tribromphe nol is dissolved i n absolute alcohol an d to this ,

solutio n th e re is added the theoretical qua n tity of be nz e ne sul

p h o n c h lor i d e an d the solutio n heated to boili ng O n filteri ng .

from the sodium chloride an d cooli ng the sulpho n ic ether ,

crystallizes out It may be purified by disso lvi n g i n alcohol

an d treati n g with a n imal charcoal The ether crystallizes .

from alcohol in the form of colorless gliste n i ng rhombic , ,

plates It melts at 9 9 C ( unc orr ) It is i nsoluble i n water

.
°
. .

a n d cold alcohol It is readily soluble however i n hot alco

.
, ,

hol be n ze n e carbo n bisulph ide aceto n e an d ethy l ether

, , , ,
.

From hot co n ce ntrated solutio n s i n alcohol it freque n tly sepa

rates as a n oil whi ch solidi fies o n cooli n g to a white crystal
, ,

li n e mass The n ature of the compou nd thus obtai n ed was

.

was determi n ed by s ap on ifi ca tion with alcoholic caust ic soda .

To sapo n ify gram of the ether 5 c c of N / I o caustic , .

soda were required Theory for .

5 cc N / ro .

N aO H .

U n like most of the sulpho n ic ethers k now n to us at pres ,

this compou n d has bee n fou n d to be rem ar k ably stable

e nt ,

towards water a n d other hydrolyzi n g age n ts .

A ction f Sodi u m B e n z e n e sulp hi n a te on Tr i bromp he n olbr om ide

o .

In order to determi n e whether t ribro mphe ny l be n z e n e s u l

pho n ate could be formed from tribromphe nol bro mi d e a qua n ,

tity of be n z e n e sulp hi n ic aci d was prepared by G att e rm an n s ’

method and co n verted i n to the sodium salt A small qua n .

tity of tri bro mph e nol bromi d e was the n dissolved i n carbo n bi
sulphide an d to this solutio n th e theoretical amou nt of fi n ely
,

powdered sodiu m be nz e n e sulp h in ate was added an d the mix ,

ture thoroughly shake n A fter sta n di n g for an hour the

.

solutio n was filtered The white residue was fou nd to c on

.

sist of sodium bromide O n allowi n g the filtrate to evaporate

.

Spo nta neously a reddish gummy substa n ce was obtai n ed to

, ,

gether with a smaller qua n tity of an oily product havi n g the

ch aracteristic odor of a sulp hon chlorid e or bromide The .
42 K a stl e .

gummy substa nce was ide n tified as B e n edikt s he x abromphe ’

n oq u i nOne H e nce the reactio n betwee n the sodium be n

.

z e ne su l hi n ate a n d t ri bro m he n ol bro mi d e does n t result in

p p o

the formatio n of a sulpho n ic ether but takes place i n the se nse

of this equatio n
2 C, H , Br, O C6 H5 S02 N a

N a Br C GHSSO , B1 .

A ction o fSil ve r N i tra te on Tr i bromphe n ol bromide .

Beyo nd provi n g the i n correct n ess of B e n edi k t s formula for ’

t ri bromp he n olbro m i d e but little ta n gible evide n ce of the real ,

n ature of the compo u n d has bee n obtai n ed up to this time .

It occurred to us i n this co nn ectio n however to test th e c on , ,

duct of silver n itrate towards t ribromph e n ol bro m id e On .

boili n g a solutio n of Silver n itrate to which some t ribromp h e ,

n ol bro mi d e h ad bee n added it was observed that a crystalli n e ,

precipitate was throw n dow n This was filtered off and puri .

fi e d by dissolvi ng i n alcohol an d re pre c i p it at i n g with water ,

whe n the substa n ce was obtai n ed i n the form of yellow irides

ce n t lami nae The compou n d was still further purified by
.

°
sublimatio n It was observed to melt at 1 3 1 C
. The com .

pou n d was ide n ti fie d as m e t ad ibromq u i none by compari n g it

with some of this compou n d prepared by the method of L evy
an d S
l
chultz A bout the time this observatio n was made
.
,

Thiele a n d E ic h we d e also obtai n ed m e t ad i bromq ui n on e from 2

tri brom ph e n ol bro mi d e by treati n g the l atter substa n ce i n

acetic acid solutio n with lead acetate These observers came to .

the co n clusio n therefore that tri bro mp he nolbromide has a

, ,

qui n o n e str ucture an d that its chemical beha vior c an best be

,

i n terpreted by the follow i n g graphic formula

CO

1 A nn . Ch m e .
(L i e b i g ) , 2 10 , 1 5 9 .

9 Be r d
. . c he m . Ge s .
, 3 3 , 67 3
44 K a stle .

tribro mp h e nol bro mi d e was mixed with co n ce ntrated sulphuric

acid at ordi nary temperature It was observed that the com
.

pou nd u nderwe n t a cha n ge of color and gradually became

perfectly white The acid was the n poured O ff a nd the co m
.

pou nd washed with water a nd purified by crystallizi n g fro m

alcohol to which an equal volume of boili n g water had bee n
added The substa n ce was fi n ally obtai n ed i n the form of
.

°
white felt like n eedles which were fou n d to melt at 1 0 9 C
,
-
, .

This compou nd is te trabro mp he nol a n d the fact that it i s ,

formed u nder these circumsta n ces certai nly goes to Show that
the molec ular rearra n gemen t of tribro mp h e nolbro mide is d ue
to the sulphuric aci d an d not to an elevatio n of temperature .

I n order to determi n e whether the molecular rearra n geme n t

could be brought about by other substa n ces the co n d uct o f ,

tri bro mp h e n ol br omi d e was tried towards the followi n g re

age nts P arafli n e d ibro mbe nz e n e glyceri n e co n ce n trated
, , ,

hy d rochloric acid glacial acetic acid dilute sulphuric acid

, , ,

be nz e n e sulp h o n ch lori d e be n z e n e sulph on i c acid a saturated

, ,

solutio n of iodic acid sodium acid sulphite carbo n tetra

, ,

chloride potassium bromide and potassium chloride

, , .

Nearly all of these substa n ces were fou n d to decompose tri

bro mp h e n olbro m id e especially at high temperatures but i n
, ,

n o case was the molecular rearra n geme n t brought about .

That it is n ot d u e to acids i n ge n eral may be see n from the

followi n g : A qua ntity of t ribro mphe nolbromid e was allowed
to sta n d for on e week u nd er co n ce ntrated h ydrobromic acid .

A t the e n d of this time the compou nd was fou n d to have lost

its color an d to have become white The substa n ce was fil .

t e re d fro m the hydrobromic aci d washed with water an d re

, ,
°
crystallize d It was fou n d to melt at 9 1 C and was fou n d to
. .

be ide n tical i n every respect with tribromphe n ol That u n .

dissociated acids ih ge n eral do not bri n g about the molecular

rearra ngeme n t was proved by dissolvi ng tribromph e nol bro
mi d e i n a co n ce n trated solutio n of hydrochloric acid i n chloro
form Some of this solutio n was heated i n sealed tubes after
.
,

which th e chloroform was allowed to evaporate o ff whe n tri ,

bromp he n o lbro m id e was obtai n ed i n u n altered co n d i tio n .

These results leave practically no room for doubt that the

 Tr i bromphe nol bromide .
45

molecular rearra n geme nt of tribro mph e nolbromid e is ae com

p l ish e d solely by the actio n of co n ce n trated sulphuric acid .

Tri chlorp he n ol br oi ni de .

In this co nn ectio n however it should be n oted th at it is

, ,
“
stated i n Watts C hemic a l D ictio n ary an d Be il ste i n s
’ ’

“
Orga n ische C hemie ”
that tric hlorph e n olbromi de an a n al
, ,

o g o u s compou nd is tra n sformed by heati ng u nder water i nto

,

a n isomer probably t ri ch lormon o bro mp he n ol

,
I n V iew there .
,

fore of what had bee n obs erved co n cern i n g the molecular

,

rearra n geme n t of t ribro mp he n ol bro mi d e it was thought ad

visable to repeat this experime n t .

A ccordi n gly t ric h lorp h e n ol bromid e was prepared i n the

,

followi n g ma nn er : T ri c hlorph e n ol was co n verted i n to the

so d ium salt by treati n g with the required amou n t of caustic
soda Five grams of the sodium salt thus obtai n ed were dis
.

solved i n 5 00 cc of water To this solutio n 3 cc of co n ce m

. . .

t ra te d hydrobromi c acid were added Th e pasty m ass thus . .

obtai n ed was immediately poured i nto a saturated solutio n O f .

bromi n e c ont aing 5 cc of bromi n e The mixed solutio n was. .

thoroughly shake n an d allowed to sta n d for some time Tri .

c hl orp h e no lbro m id e separated from this solutio n i n the form

of a light yellow gra n ular precipitate alto gether si milar i n

-
, ,

appeara n ce to tri bro m ph e nol bro m ide The Compou n d was .

purified by crystallizi n g from hot chloroform I n pure co n di .

tio n it was fou n d to melt at 9 7 C L ike t ri bromph e nol bro °

.

mide this substa n ce is lemo n yellow i n color but more soluble

,
-

in chloroform tha n the former The amou n t of easily re .

placeable bromi n e i n t ric h lorp h e nolbromi d e was determi n ed

by reduci n g it with sodiu m acid sulphite an d titrati n g with
N / I O silver n itrate gram of the compou n d was take n
.

for a n alysis .

C l ul t d f a c a e or
T ri c h l o r p h e n o l b r om id e . Fo un d .

Some of th is compou n d whe n grou n d to a fi ne powder an d ,

melted u nder water was fou nd to decompose with evolutio n of

,

bromi n e It was not tra n sformed however i nto the isomeric

.
, ,
46 K u stle .

t rich lormonobro mp h e nol the other ha nd t richlorphe nol

. On ,

bro mide is readily tra n sformed by sulphuric acid i nto t richlor

m onobromph e n ol In order to Show this. gram of tri ,

c h lorp he n olbro mi d e was heated u nder sulphuric acid O n .

cooli n g the acid was poured off an d the residue washed with
,

water The residual acid an d washi n gs were tested for bro

.

mi n e with silver n itrate with n egative result The tric hlor .

monobromph e nol formed i n this experime n t was fou nd to

weigh whe n air dried
,
gram It will be observed
-
, .
,

therefore that it is the sulphuric acid and not the water which
,

e ffects the co n versio n of tric hlorp h e nolbrom ide i nto tric hlor
monobromp h e nol .

In V iew of these results therefore there be no do ubt , , c an

that the co n versio n of tribromph e nolbromide i n to te trabrom

phe nol is brought about by mea ns of co n ce ntrated sulphuric
acid .

The questio n n aturally prese n ts itself ho w can sulphuric ,

acid accomplish this cha nge ? I n a ns w er to this the follow

i ng expla n atio n has suggested itself i n the light of Thiele a nd
E i chw e de s formula for t ribro mp h e nol brom id e wh i ch ,i n V iew
’
,

1
of the former s ideas of partial vale n ce may be writte n as fol
’
,

lows

From what we k now of the ma nn er i n which sulphuric acid

dissociates as an electrolyte it would seem probable at least , , ,

that in its actio n on tribromphe nolbromid e the hydroge n ion

would add itself to the q ui no n e oxyge n of the compou nd ,

thereby co n verti ng it i nto a phe n ol hydroxyl group The .

1 Th i l Z u K ntn i
e ed u g tti g t
r V bin d u ng n A n C h m ( L i bi g )
e ss er n e sa en e r e . n . e . e ,

3 06 , 1 29 .
 Tr i bromp he n ol bromide .
47

H SO4 ion could the n u n ite with either of the u nsaturated

groups i n the meta positio n i n the ri ng . This cha nge may be
represe n ted graphically as follo ws :

O —
H

H so,
/
.

Br Br
11 .

If now from compou n d I I hydrobromic acid were to be

, ,

Split of
f an d there is every reaso n for supposi n g that such a
,

decompositio n might o ccur there would remai n a compou nd

,

havi ng the n ature of an acid ester sulphate thus ,

O H
-
O —
H

From what w e k now of the ease with wh ich acid ethyl s ul

phate C H, H SO l s decomposed by hydrobromic acid to form
, ,

ethyl bromi d e and sulphuric acid it would seem logical to ,

suppose that the hydrobromic acid resulti n g from the de com

positio n of compou n d 11 would at o n ce act upo n compou n d
.

I I I with the productio n of te trabro mp h e nol an d sulphuric

.
,

acid thus
,
48 Ka stle .

H , SO 4
H SO 4 H Br

It will be observed that like ma n y other catalytic pro

,

cesses the cha n ge i n questio n is of a cyclical character It is

, .

believed further that all cha nges brought about by elec

, ,

t ro ly te s o n t ribro m p h e n ol bro mi d e can be explai n ed by the

suppositio n that the hydroge n or positive i o n e n ters i nto com
bi n atio n with the qui n o n e oxyge n of the compou nd th ereby ,

co nverti ng it i n to a phe n ol or one of its salts The n egative .

i o n probably e nters i n to combi n atio n with one of the meta

groups i n the ri ng an d fi n ally as the result of cleavages oc
, ,

curri n g betwee n the atoms or groups i n the meta an d para

positio n s the e n d products of the reactio n are produced
, For .

example as show n i n the above tri bro mp h e n olbrom ide is re

, ,

d u c e d to tribromphe n ol by mea n s of hydrobro mic acid It is .

believed that the cha n ges taki n g place c an be represe n ted as

follows
O —
H

H Br

Br Br
O —
H

H H
 Tr i bromphe nol bromide .
49

In the same way we c an explai n the actio n of potassiu m

iodide on tribromp h e no lbromid e as may be see n from the fol
,

lowi n g
O —
K

Br Br
O —
K

B rI
H H

B
O
an d ,similarly we c an accou nt for the actio n of zi n c ethyl
, on

this compou nd thus,

O -
Zn

Z fl gc2II 5
‘

H
H

Br § Br
O —
Zn ,

C , H5 B r
H H
50 K ustle .

On the other ha nd with electro negative eleme nts such as

,

bromi n e and iodi ne which as we have see n also decompose

, , ,

t ri bromphe nol bro mi d e an d which h ave little or no affi n ity for

,

the qui no n e oxyge n the case is somewhat di ffere n t H ere the

, .

additio n probably ta k es place o n o ne of the groups in the meta

positio n i n the ri ng with the productio n of an u n stable i n ter
,

mediate product which as the result o i seco n dary cha nges o c

,

curri ng betwee n the atoms or groups i n the meta and para

positio n s ,gives the fi n al products of the decompositio n Thus
‘
.
,

i n the catalysis of tri bro mph e nol brom id e by mea n s of bromi n e

vapor we probably h aVe the followi ng cha nges occurri ng
,

O O

H
H

Br :
Br

Br H Br Br H Br

Br H H Br
an d ,i nasmuch as more and more bromi n e is produced the
lo nger the reactio n proceeds we c an readily u ndersta n d how ,

Th i l Z u K ntni d u g ttig t n V bi nd u n g n A n n C h m ( L i b ig )
1
e e r e ss er n e sa e e r e . . e . e .

3 06 . 1 33
 Se zde ll
'

52 .

clear u ndersta ndi ng of this compou n d and its relatio n to tri

bromphe nol bro mide .

The loss of 2 atoms of bromi n e from the compou nd which ,

occurs on the exposure of a carbo n bisulphide solutio n of tri

bro mp he nolbro mi d e to light is m uch more di f fi cult to ex ,

plai n H ere also the product of the reactio n is amorpho u s

.

an d exceedi n gly stable an d in fac t shows ma n y poi n ts of re ,

sembla nce to h e x abromphe noq ui n one L i k e this compou n d .

,

it probably co n tai n s two be nze n e residues and te n tatively a t , ,

least we may represe nt its formatio n i n the followi ng ma nn er

,

2 0

O 2 B r2

Br H
A further study ofth is compou n d is n ecessar y however to .
, ,

a better u nd ersta n di n g of the decompositio n of tribromphe n ol

bromide by light .

ST T E C LL E G E
A K E N TUC KY O OF
L E X N G T N K Y Jul y
,
I 9 O , ,
1 01 .

SO LU B I L IT Y OF MIXT U R E S O F SOD I U M SU L
P H AT E A N D SOD I U M C H L O R ID E
1
.

BY A T HE R T O N SE I D E LL .

The solubility i n water of mixtures o f se v e ral pairs of elec

trol y te s i n which one member of the pair is relatively much
,

less soluble tha n the other has lately bee n i n vestigated i n th i s ,

2
l aboratory by Dr Fra n k K C amero n a n d the author . In . .

co n n ectio n with th is work the results prese n ted i n this paper ,

were obtai ned o n mixtures of a pair of salts yieldi n g a com

,

m on io n presumably an d havi n g the ad d itio n al feature that

, ,

ubl i s h e d by p e rm i sion of th e Se re t ry f A g ri ultu re

1 P s c a o c .

So lu tio n s tu di o f a l t o u rri n g i n lk a l i soi l s Bull e ti n

2 e s s s cc a , 1 8, D i v i s i on of Soi l s ,
U S D e p rtm e n t of A g ric ultu r
. . a e .
 Sodz u m Sulpha te Sodi um
'

a nd Clzlor zde
'

.
53

both members of the pair are readily soluble A good deal of .

work of this descriptio n has bee n do n e in rece n t years but so ,

far as I a m aware this pair of salts h as no t previously com

,

m e nded itself to i n vestigators owi n g probably to the well

‘

k n ow n te n de n cy of sodium sulphate an d its hydrates to form

s upersaturated solutio n s which are d ifii c ul t to ha ndle
,
a nd

to the further fact that salts which separate i n the solid phas e
,

without water of c rystallizatio n have hitherto appealed to i n ,

ve st ig ators o n accou n t of the readi ness with which the total

a mou nt of salt i n solutio n may be determi n ed by evaporatio n

a n d dryi n g th us a f
, fordi ng obvious a nalytical adva n tages in
d eali n g with them .

'

In a few i n sta n ces more tha n one i nvestigator has work ed

with the same pair of salts but a compariso n of the results
,

o btai ned w as n ot possible si n ce the results w ere expressed i n

,

the one case i n terms of grams of salts dissolved i n a give n

“

weight of solve nt and i n the other in terms of the grams of

,

salts dissolved i n a give n volume of solutio n and si nce the ,

weights of the solutio n s were not give n there is no satisfac ,

:

tory way by which the results may be calculated to the same

basis .

A recog n itio n of the above fact is very importa nt i n all such

work upo n mutual solubility e ffects and in order that the re ,

s u lt s may be of the greatest useful ne ss they should be pre

s e nted i n both ways .

E XP E R I ME N T A L WO R K .

Before proceedi ng to a discussio n of the results a short de ,

s criptio n will be give n of the ma n n er i n which the e xp e ri

me n tal work was carried o n In the maj ority of cases studied

.

by other i n vestigators the salts with which they worked are

,

s uch as crystallize without water of crystallizatio n he nce it

was possible for these i n vestigators to make determi n atio n s of
the total grams of salts i n solutio ns by evaporatio n an d the n ,

b y a determi n atio n of on e of the co nstitue nts to obtai n the

o ther by d iffere nce In the case u nder co n sideratio n how
.
,

ever i t was fou nd n ecessary to m ake th e d etermi n atio n of

,

e ach of the salts i n the weighed portio n of the solutio n The .

s odium chloride w as determi n ed by calculati n g from the re

 Se z a e ll
'
’

54 .

s ults of titra tio n s with N /

I O solutio n of silver n itrate an d th e

sodium sulphate by calculati ng fro m the grams of bariu m

sulphate obtai n ed by precipitatio n i n the usual way
, .

The series of solutio ns were ma de up i n bottles and so pre

pared that the amou nt o i sodium sulphate should be i n e xce ss
i n the bottles with the lower n umbers the amou nt of sodium ,

chloride gradually i n creasi n g from the seco n d bottle o n In .

the bottles with the higher n umbers the sodium chloride w a s

i n excess and the amou nt of sodium sulphate gradually di
,

mi n ished The first bo ttle co ntai ned o n ly sodium sulphate i n

.

solutio n the last on ly sodium chloride C are was exercise d

,
.

i n the determi n atio n s made at the several temperatures to

have more tha n on e bott le co n tai n i n g both salts prese n t as
solid phases in order that the poi n t of i ntersectio n of the
two curves represe nti n g the solubility of each salt i n solu
t io n s of the other should be accurately determi n ed The .

bottles thus prepare d and stoppered tightly were placed in

a co n sta nt temperature water bath i n which they were
- -
,

rotated i n a m a n n er causi n g thorough agitatio n of the solu

tio n s for periods of eightee n to twe nty four hours A fter -
.

the period of agitatio n the bottles were allowed to remai n u p

right i n the bath lo n g e n ough for the solid material to subside
a n d leave the super n ata n t solutio n clear A 5 0 cc portio n o f . .

each sol utio n was withdraw n by mea ns of a pipette an d tra n s

ferred to a weighi n g bottle a n d the weight of the solutio n
-

take n This amou n t of solutio n was the n washed i nto a larger

.

graduated flask an d after diluti n g sufficie ntly aliquo t por

, , ,

tio n s were take n for a n alysis as already described .

The results of the a nalyses at the various temperatures are

give n i n the accompa n yi n g tables In each case the weights
.

of a gi ve n volume of the solutio n s are give n i n the first col

umu The grams of N aC l an d N a sO, prese n t i n this volume
.
,

are give n i n the seco n d a n d third colu m ns The grams of

'

sodi um chloride a n d sodium sulphate prese n t i n 1 00 grams of

water are give n i n the fourth a n d fifth col um ns a n d fi n ally ,

the gram molecules of sodium chloride an d sodium sulph at e

-

per liter of solutio n are give n i n the si xth a nd seve nth col
umus The curves plotted i n the diagram are o n the basis of
.

the results give n i n the fourth a nd fifth colum n s givi n g the ,

 Sodi um Sulp/
za i e a nd Sodi um C/
zl or i de .
55

grams of each salt prese n t i n 1 00 grams of water at the various

temperatures These figures were selected simply because
.

they yield a di agram which is no t so crowded and is therefore , , ,

clearer tha n if the results were plotted on any other basis .

The n ature of the curves is i n no wise di ffere n t an d the p e c u ,

liar iti e s they prese n t are as clearly see n as they would be if

plotted on any other basis .

Ye mpe m l ure
°
Ta ble 1 . 10 C .

'

2
z : 3

8
£5 65 5

4 -5 9

33 7 6
Ta ble —
Te mpe r a i u r e 5 C .
56 Se ide ll .

Te mp e ra ture
°
25 C .

Ta ble I V Te mpe ra tu re
°
. 2 7 C .
58 S '
e i ae ll .

Ta ble VIZ Te mp e ra tu re 3 5
°
—
C .

D I SC USSI O N OF R E SUL T S
Fro m Mulder 5
results on the solubility of sodiu m sulphate ,

quo ted i n C om e y s D ictio n ary of Solubilities

“ ’ ”
page 4 5 2 it , ,

appears that the figure give n for the solubility of sodiu m sul
phate at 5 is somewhat too low Mulder fou n d that at .

5 C there was co n tai n ed

. parts of so d ium sulphate per
1 0 0 parts water while the results here show o n ly
, parts .

This di ffere n ce is possibly due to an error in the temperature

observatio n i n the prese n t case It appears that at C . .

Mulder obtai ns the same figures that are give n here for 5 ,

co n seque ntly it may well be that the temperature at which th e

work here described was do n e may have bee n 2 i n stead of
5 The thermometer used was graduated o nly to whole
degrees an d moreover had not bee n calibrated so that such
, ,

a n error might easily be thus accou n ted for Similarly for .

,

the results obtai n ed at other temperatures a correctio n may ,

be applied by compari ng with Mulder s results an d there ’

,
°
wo uld be obtai n ed 2 i nstead of 2 5 C i n stead of
i nstead of i nstead of 33 For how
e ver a similar correctio n ca n not well be allowed si n ce Mul
, ,

der fi nds for 3 parts dissolved agai nst o nly i n th e

prese n t case .

A n i n spectio n of the diagram will show that there are pres

e n t two disti n ct classes of curves o n e class represe n ti n g re ,

1 “ S
che i k un d i g e V e r h a n d e l i n g e n O n d e rz o e k i n g e n , " e d i te d by Mul de r , R otte r

d am , 1 85 7 - 6 4 . T he o ri gi na l i s n ot ac c e s sibl e to me .
60 Se ide ll .

represe nti ng the mutual solubility of these two salts i n solu

tio n s of each other it is necessary to remember the peculiarity
,

exhibited by sodiu m sulphate i n regard to its solubility alo ne

i n water at various temperatures It is well k n ow n that at .

°
about 3 3 sodium sulphate cha n ges from its characteristic t e n
hydrate crystalli n e form to the a n hydrous salt C o nseque ntly .

at this tem p erature and above the curves represe n t the sol u
, ,

biltie s of two simple n o n isomorphous a n hydrous salts so

, ,
-
, ,

d i u m sulph ate and sodium chloride with one homoge neous ,

solid phase except at one poi nt the poi nt of i n tersectio n This

, , .

behavior is i n strict accord with the phase rule an d the cases ,

described here appear to be perfectly n ormal .

Below however a di ffere nt st ate of affairs e xists as

, ,

will be see n by referr i n g to the diagram The solubilities of .

°
various mixtures for an y give n temperature below 3 3 and
°
above a temperature in the n eighborhood of 1 7 C are see n to .

be expressed by fl am e curves i ntersecti ng i n two poi nts .

The lowest curve represe n ti n g the solutio n s i n which sodium

chloride is prese nt i n excess lie close to and prese nt the same
, ,

ge n eral features as those curves represe n ti n g the same mix

tures at higher temperatures The middle curve i n each case .

i s practically parallel to the curves obtai n ed at higher temper

atures whe n the solutio ns were in co ntact with solid a uby
d rou s sodium sulphate A n d as will be prese n tly poi n te d
.
,

out the solid phase co ntrolli ng these middle curves is i n fact

,

the a nhydrous salt n otwithsta n di ng that they represe nt c on

,

d it io n s existi n g below
The upper curve is the n ormal solubility curve for the deca
hydrate of sodium sulphate i n solutio n s of sodium chloride .

A s will be see n from the diagra m the ge n eral n ature of the ,

solubility curve for the decahydrate is quite differe nt from

that for the a nhydrous salts A nd certai nly at the lower .
, ,

temperatures it prese nts the u n usual feature of a mi n imu m

poi n t A t a temperature below
. the solid phase i n co ntact
with the solutio n is probably the heptahydrate O ne curve .
,
°
for 1 0 C was determi n ed a nd as the diagram shows it is
.
, , ,

e ntirely similar to the solubility curve for the decahydrate .

C o nsideri n g further the cou rse of the curves obtai n ed at

 Sodi um Sulp ha te a nd Sodi u m Cblori de . 61

temperatures below it is see n th at i n each case as the

origi nal directio n of these curves causes them to come i nto the
regio n of the curves for a n hydro us salt ( that is the curves for ,
°

3 3 an d above ) the directio n of the fo rmer is ch a n ged and

,

becomes parallel to the latter curves itself a stro ng argume n t ,

for the V iew that the solid phase i n co n tact with the solutio n
was the s ame i n all such cases i e the a n hydrous sodiu m
, . .
,

sulph ate I f the curves for the decahydrate co n ti n ued their

.

d irectio n a n d crossed the curves for the a n hydrous salt i n

-

order to meet the li n e represe nt in g the solubility of sodiu m

chloride i n sodium sulphate exte n ded it would m ea n th at ,

solutio n s would be obtai n ed which would be supersaturated

with respect to the a n h ydrous sodium sulph ate In ord er that .

the solutio n could have bee n supersaturated with respect to

a nhydrou s sodium sulph ate it would be n ecessary that
,

n o n e o f the solid a n hy d rous salt should be i n co n tact with

°
the solutio n The temperature bei n g below 33 would or
.

d in arily i n sure the prese n ce of n o a nhydrous sodium sul

phate co n seque n tly it is to be expected that su ch poi nts in
,
°
the field beyo n d the 3 3 curve should be obtai n e d I n no .

case however were they realize d an d we are agai n led to

, , ,

the co n clusio n th at a n hy d rous sodiu m sulphate was really i n

°
co n tact with the solutio n s eve n at temperat u res below 3 3 C .
,

an d thus th at a n i n versio n of th e decahydrate to the an h y

d rous salt takes place at various temperatures below de

pe n di n g u po n the amou nt o fsodium chlori d e co n tai n ed i n the
solutio n i n co ntact with the solid sodium sulphate .

I n order to more satisfactorily demo n strate this the follo w

i n g experimen t was performed : T wo test tubes each c on -
,

tai n i n g a thermometer were im mersed in a large beaker of

,

water In the first test tube was placed a saturated solutio n

.
-

of sodium sulphate an d also several large well formed crystals ,

of the d ecahydrate In the seco n d test tube was place d a

.
‘

solutio n saturate d with respect to both sodium chloride and

s odiu m sulphate and also several large , well formed crystals
,
-

of the decahydrate The temperature of the water i n th e

.

°
beaker was slowly an d gradually raised A t abo u t 2 8 the .

crystals of the decahydrate i n the seco n d test tube bega n to -

 62 Se ide ll .

cloud become O paque arou n d the edges and as the tem

an d ,

p e ratu re was mai n tai n ed co nsta nt this process co nti n ued n u ,

til the whole m ass was completely tra nsformed from clear ,

tra nsluce n t crystals of the decahydrate to an opaque m ass o f

a n hydrous salt The crystals i n the first test tube remai ned
.
-

u n altered Thus it seems quite evide n t that the tra n sforma

.

tio n of the decahydrate to a nhydrous sodium sulphate at tem

p e ratu re s below is quite possible whe n the crystals are i n
co n tact with co n ce n trated solutio n s of sodium chloride .

The cha n ge i n th e i n versio n tem perature at which the deca

hydrate goes over to the a n hydrous sodium sulph ate ; i n the
prese n ce of a third substa n ce i n sol u tio n which h as j ust bee n ,

described is a n alogous to a nother case which has received at

,

V an t H o ff a nd A rmstro n g
‘
t e n tio n i n this laboratory
’
.
,

2 3
Vater an d Zu n i n o have rece ntly called atte n tio n to the fact
,

that gypsum the dihydrate of calcium sulphate was tra n s

, ,
l

forme d to the hemihydrate a t various w idely di fferi n g tem ,

p e r a t u re s depe n di n
,
g upo n the n ature of the solutio n with
4
which it was i n co n tact C amero n I believe was the first to .
, ,

call atte n tio n specifically to this poi n t H e i nvestigated this .

case experime ntally by a method similar to the o n e described

i n this paper u si n g a n umber of solutio n s of various salts an d
, ,

various liquids T he facts brought o ut in this paper stre ngthe n

.

the V iew put forward regardi n g this phe nome n o n an d i ndi ,

cate the probability of its bei n g fou n d agai n i n futu re studies

of this n ature .

I n co n clusio n I wish to ack n owledge the assista n ce and ad ,

vice of Dr Fra n k K C amero n i n carryi ng out this i nvestiga

. .
,

tio n an d i n the i nterpretatio n of the results .

B U E U S LS U 8 D E T M E N T
R A OF OI , . . PAR
OF A G C U L TU E W SH m G
R I D C R , A r ON , . .

1 Si tz un g s b e r K . P re u ss. A k ad . Wi ss .
, 2 8, 559
L oc . ci t 8 . 2 69
2
2 Gaz z . c hm
i i t a1. .
, 30, 1, 333
4 Bull e ti n 1 8, p g e 37 D
a , i vi si o n of Soi l s , U . S
. D e pa rt me n t of A g ri c ul tu re .
 ON T HE P R E P A R A T I ON B R O MO FO R M B Y
OF
E L E C T R O L Y SI S .

BY P U L C U G H L N
A O I .

In 1 884 Scheri n g took out a pate n t ( D R P 2 9 7 7 1 )

E . . . .

for the preparatio n of iodoform bromoform and chloroform , ,

by electrolysis The pate nt Specified that the respective halo

.

'

g e n salts of the alkalies o r a l k a l i earths should be electrol yzed

i n the prese n ce of al cohol aceto n e or ald ehyde i n a w arm , ,

aqueous solutio n C arbo n dioxide was to be passed co nti n

.

u o usl y i n to the electrolyte duri n g the electrolysis .

E lbs an d H erz in 1 8 9 7 published the results of their i n

l
, ,

v e st i g ati o n of the process c overed by this pate n t i n regard to

the preparatio n of iodoform from alcohol an d aceto ne I n re .

gard to the preparatio n of bromoform they say E qually

”
u n su ccessful ( referri n g to their lack of success with aceto n e )
was an experime n t on the electrolytic preparatio n of bromo;
form i n which the a n ode solutio n co n sisted of 6 grams sod a
,

an d 1 0 gr a ms potassium bromide i n a m ixture of 2 0 cc alco .

hol an d 1 00 cc water ; the a n ode de n sity was 0 5 ampere p e r

. .

square decimeter ; the temperature A fter 1 5 ampere .

hours the solutio n co ntai ned n o bromoform .

I repeated the foregoi n g experime n t with the same result

'

that they obtai ned R eplaci n g the sodiu m carbo n ate by caus
.

tic soda did no t cha n ge the result n or was it cha n ged whe n ,

aceto n e was used i n stead O f alcohol a n d the two experime n ts ,

repeated .

H avi ng fo u n d previously that a temperature of 7 5 was

°

n ecessary to obtai n the best yield of iodoform from alcohol I ,

tried this temperature i n prepari n g bromoform from alcohol

and aceto n e In order to mai n tai n this temperature the elec
.

t rol y tic cell was placed i n a water bath an d to preve n t loss -

,

of aceto ne or alcohol by evaporatio n the a node com partme n t

a porous cup was fitted with a reflux co n de nser The ex
—
.

p e r i m e n ts with alcohol a n d carbo n ate alcohol a n d caustic , ,

1 Z ts c h r . E l e k tro c h e m .
, 4 , 4 , A ug . 2 0 , 1 89 7 .
64 Coug /
zl i u .

aceto ne and carbo n ate and aceto n e an d caustic were t e

, ,
°

p e ate d at 7 5 and the n at but all resulted n egatively .

The co nce ntratio n of the solutio n was varied a n d the n the ,

proportio n s of the various substa n ces in the electrolyte but ,

without success In ma ny of these experime nts an exceed

.

i n g ly pe n etrati n g highly disagreeable odor showed the forma

,

tio n of brom aceto n es To preve n t this as m uch as possibl e

.
,

the aceto n e ( or alcohol ) was allowed to r un i nto the electro

lyte gradually duri ng the electrolysis Several of the former .

experime n ts were repeated with this modificatio n but in no ,

case could any bromoform be detected .

The next attempt was with the electroly te at room tempera

ture The electrolyte was 1 0 grams potassium bromide and
.

1 5 grams sodium carbo n ate i n 7 5 cc water a n d 2 0 cc ace . .

to n e the a n ode an d cathode bei ng separated by a porous cup

, .

A small dro p of bro moform resulted from this electrolysis .

H avi n g succeeded i n obtai ni n g a small yield of bromoform

I e ndeavored by systematic variatio n of the co nditio n s that
,

might a ffect the yield to i n crease it to the maximum

, .

I n all the followi n g experime n ts the apparatus used c on

sisted of a beaker of 2 5 0 cc capacity i n which was suspe nded
.

a porous cup of 1 1 0 cc capacity The porous cup was made

'

. .

the cathode chamber a nd i n this was put a solutio n of 1 0

,

grams sodium carbo n ate i n 1 00 cc water ; the cat hode was .

a n iro n w ire gauze of about 6 0 sq cm

- superficial area o n a
. .
-

side The beaker co n tai ned the a n ode solutio n and the a n ode
.

of plati n um foil which h ad an area of 5 0 sq cm o n each side . . .

U sually two of these cells were co nn ected i n series an d i n ,

every case a copper voltameter was put i n to the circuit E x .

cept whe n temperature co nditio n s were tried the cells were ,

placed i n vessels of col d water so that the temperature varied

,

but little fro m 2 The tim e of the experiments was so

varied that the amou n t of curre nt used might be ap p ro x i
mately the same for each experime nt .

The formatio n of bromoform from aceto n e is expressed by

the followi ng equatio n
6 Br C H Br, C H, C O O H 3 H B r .

The prese n ce of acetic a cid i n the electrolyte could readily

be detected by the ethyl ester test -
.
 Prep a ra tion f B romofor m
o by E le ctroly sis . 65

The bromoform was measured by bei n g washed i nto a

graduated tube an d ce ntrifugalized The weight was fou nd .

by co n sideri ng the specific gravity to be A fter so me

qua n tity had bee n collected 1 0 cc was distilled an d prac ti , .

°
cally all passed over betwee n 1 40 and
In the first experime nts the aceto n e was added to the elec
t roly te i n equal qua n tities at i n te rvals of te n mi n utes duri ng
the electrolysis an d the e ffect of varyi ng th e a mou nt of sodium
,

carbo n ate was tried ; caustic soda was the n substituted for
-

the carbo n ate The results are show n i n the followi ng table :
.

5
‘

.
a
°
3
w
as
‘
5 a
3
“
3 f
lu is
W
. 5

2
‘
a. a . a
: t: s
.
6
£ 8 a 8 3 33 6 5 as
° 0
as a «

Se i0 0s 88 8 8 “a
‘ ‘

3 ss 9' 8
M0
~

m MD M
o
o '

2 «1 8 38 0 0 1 é .
°
1 12 12 90 1 25 2 19
2 12 12 90 5 25 2 11
'

3 12 12 90 2 2 4 25 2 2 1 30
4 12 12 90 3 2 25 2 2 1 1 33
12 0
5 12 90 1 2 25 2 2 9
6 12 12 90 2 2 5 25 2 2 drop 2

7 12 12 90 5 2 25 2 2 0
8 12 12 90 2 4 25 2 2 36
At the e n d of the electrolysis i n each case where the yield ,

was very large the electrolyte was colo red by free bromi n e
,

a n d had to be treated with c austic alkali or carbo n ate to free the

bromoform of bromi n e The limit of the yield with these co n di

.

tio n s was soo n reached ; an experi me n t i n which all the aceto n e

was ad d ed at the begi nn i n g of the electrolysis showed the same
yield that was obtai n ed whe n the aceto n e was a d ded gradually .

The fact that the yield decreased whe n e nough carbo n ate
was added at the begi n n in g to keep the electrolyte clear an d ,

that otherwise free bromi n e was pre se nt suggeste d that it ,

wo uld be better to add the carbo n ate at i n tervals Whe n this .

was do n e a marked i n crease i n the yield w as show n In the .

succeedi n g experime n ts the carbo n ate was add ed at such a rate

that the electrolyte remai n ed barely colored by free bromi n e .

In some of the first experime n ts the carbo n ate was added i n

solutio n but later that the electrolyte might remai n at c on
, ,

sta n t volume the solid was used with the sam e result
, .

5
-
27
66 Cbug /di n .

The e ffect of temperature o n the yield is show n by the fol

lowi ng tables the first havi ng bee n m ade before the other
,
.

co nditio n s n ecess ary to a maximum yield had bee n discovered

i s o E
“
.

a °
o 0 (3 g
-

as
5 3
. . £53 8 2 i;
s
it o n g ,
«a ? g
gi
8, tat 88 a a 25 an
MO m
.

< 0 0 0 0 a an
: 4 >0 .
°

9 12 15 90 3 5 2 2 o .
53
10 12 15 90 3 15 2 55
11 12 15 90 3 25 2 2 24.
59
12 12 15 90 4 35 2

13 25 10 75 6 10 1 15 ,
82
14 25 10 75 6 I5 15

15 25 10 75 6 20 1 : 15 99
16 25 10 75 6 25 1 16 1 00

17 25 10 75 6 30 1 : 15 1 00
18 25 10 75 6 35 1 : 20 90
19 25 10 75 6 40 1 : 15 2 .
4 3 . 08 81
20 25 10 75 6 3 5 .
50 2 .
4 3 . 08 81
de n sity is a co n siderable factor i n determi n i n g the
C urre n t
yield but i n a modified way This is see n by the followi ng
, .

ta ble T he first four experime n ts were made usi ng a plati n um

.

gauze of 5 0 sq cm superficial area on a side or a total

. .
,

of about 1 00 sq cm In the last four the foil 5 x 1 0 cm was

. .
,
.

used These experime nts would seem to i n dicate that the

.

amou nt of curre n t in proportio n to the volume of the electro

lyte has much to do with the result
5
68 Bla ke
’

no case w as the curre nt yield greater tha n 10 per ce nt o f

theory .

E LEC T R OC HE M IC A L L A BO R A T O R Y
ND N
.

I IA U n rv n xs rr v ,
A
M ay 2 5 , 190 1 .

N OTE O N TH E R A TE O F H Y D R A TION O F ME T A
P HO SP HOR IC A C ID .

BY JC
. . A N D F . C B LA KE
. .

It is well k n o wn that a water solutio n of metaphosphori c

acid slowly cha n ges to either pyro or orthophosphoric acid at
th e ordi na ry temperature accordi n g to the amou n t of wate r ,

prese n t The rate of this cha nge was i nvestigated by Saba

.

tier who employed the methods of acidimetry We have re

,
l
.

i n vestigated the same reactio n accordi n g to o ne O f the meth

2
ods rece ntly outli n ed by D ua n e In his words In thi s .

Fi g . I .

method the basis of the measureme n t is the ch a nge i n the i n

dex of refractio n of the system a n d it is applicable to thos e ,

chemical systems o n ly that are tra n spare n t It is s u bst an .

t i ally the followi n g : R ays of light from an illumi n ated slit S

( Fig I ) passi n g through a lo n g focus le n s L and the tube a

.
,
-

b e d form a dista n t image SI of S The slit S is p e rp e n .

d i c ul a r to the pla n e of the diagram which represe nts a hori ,

z o nt al sectio n of the apparatus The tube a b c a has pla n e ’

.

glass e nds a b an d e d an d a pla ne glass plate a e divides it i n to ,

two wedge shaped compartme nts The e n ds a b an d e d are

-
.

n ot quite parallel to each other so that if the two compart ,

m e nts are filled with liquids havi n g the same i n dex of re frac
tio n there will be a slight resulta n t refractio n of the light ray s
that pass through the tube The rays of light that pass out .

side of the tube will therefore form an image S a little to , , ,

1C mp t d 1 6 6 3 ; 1 8 7 38 8 4
o . re n .
, 0 , 0 , , 0 .

2 A m .
J . Sc i .
, May ,
1 90 1 .
 Hy dra ti on of Me tap lzosp/
zori e A d d . 69

o ne side of S, It is evide n t that if the li q uid in one com

.

p a rt m e nt ( the wedge a e d for i n sta n ce ) is u ndergoi n g a chem

ical ch a n ge its i ndex of refractio n i n ge n eral will vary and

t he image S, will move sideways The d ista nce that S has .
,

moved will be a measure of the cha n ge that has ta k e n place

i n the i n dex of re fractio n and therefore of the amou n t of , ,

s ubsta n ce i n a e d that has rea cted The displaceme nts of S, .

c a n be determi n ed by compari n g its dista n ces from S which 2

remai ns statio n ary .

In order to O btai n a complete record of th e positio n of S,

a photographic p late S S is placed i n a vertical positio n at
, , ,,

t he images S and S an d j ust i n fro n t of it is a scree n A n ar

"

, ,,
.

row horizo ntal slit cut i n the scree n allows a small p art of the
"

light o n ly to pass through A t any i n sta n t of time there .

,

fore there will be two small spots of light o n the plate at the
,

i n tersection s of the two vertical images S and S with the , 2

proj ectio n of the slit o n the plate A system of cog wheels .

-

al lows the p hotO g rap hic plate to fall slowly duri n g the re ac
tio n so that two li n es are draw n on it one of them straight
,
—

d ue to the fixed i mage S a n d the other curved due to th e2, ,

movi ng image S The curved li n e represe n ts the reactio n in

,
.
,

t hat the abscissas are proportio nal to the i ntervals of time and
the ordi n ates represe nt ( but are n ot proportio n al to ) the qua n
tities of the substa nce that h ave reacted A fter the reactio n .

is completed the plate is draw n up a nd allowed to run dow n

,

agai n the image S now traci n g a nother li n e that is p rac ti

, ,

cally straight This li n e may be take n as the zero li n e [the

.

axis of x ] and the dista n ces betwee n it and the curved o ne

,

are ( at least i n some cases ) proportio nal to the amo u nts of

th e origi n al compou nds left i n the solutio n [at the correspo nd
i ng times] .

P ractically the applicability of the method is quite limi te d

, ,

owi ng to the co n dition s of the experime n t The re frac to m .

eter is a co nve n ie nt i n strume n t to use i n determi n i n g whether

the cha n ge i n the i ndex of refractio n of any give n system be
su fii c ie n tly large to yield good results ( methyl acetat e and

w ater were rej ected o n this accou n t ) as well as to ascertai n ,

approximately the n ecessary stre ngth of the solutio n O f .

70 B la ke .

course no i n gredie n t c an leave the field i n the form of a gas

,

or a precipitate The use of a catalytic is permissible The

. .

method would seem to be especially serviceable for those t e

a ctio n s whose co n stitue n ts m ay hardly be gauged by che mical

m ethods such for example as those i nvolvi n g molecular re

, , ,

arra n geme n t .

A suitable reactio n havi n g bee n decided upo n a measured ,

amou n t of the solutio n is allowed to react completely a nd i s

the n placed i n on e énd of the tube The same amo unt of a .

fresh sol utio n is the n mixed an d the clockwork started at ,

the same i n sta n t T he positio n of the plate while at rest was

.

recorded by a fl ash light whereby an im age of th e horizo ntal

-
,

slit was photographed on the plate which correspo n ds i n ,

positio n to the ordi n ate at the begi n n i n g of the reactio n ( th e

axis of y ) The fresh solutio n is the n placed i n the other e n d
.

of the tube an d after adj usti n g the focus the plate is ex

, , ,

posed . It might be o f practical importa n ce to add th at co n

si d e rabl e diffi cult y was experie n ced i n a d j usti n g the focu s ,

due to the fact that the fresh solutio n j ust i n troduced i nto th e
tube is n ot e n tirely homoge neous especi ally where it comes ,

i n co n tact with the glass to which traces of the fo rmer solutio n

always adhere If the focus is n ot readily adj ustable so m uch
.
,

of the best part of th e curve is lost that the plate is practically

worthless Therefore after ma n y failures the follow i n g
.
, ,

m ethod was adopted P lace i n each e n d of the tube a solu

tio n that has already reacted and adj ust the l en s so that the
beam through the solutio n will be in focus on the plate If .

this causes the side light to blur too much to give a disti nct
-

image at S a separate le n s or a separate source of light will

, ,

h ave to be i n troduced for this purpose A fresh solutio n i s .

the n i n troduced i n to on e e n d of the tube an d the plate ex

posed It will usu ally appear to the eye th at the beam
.

through the solutio n is no lo nger i n focus but experie n ce

teaches that it will n evertheless ma k e an impressio n o n a n
, ,

”
extra se n sitive plate as a fi n e li n e becomi n g eve n fi n er as
-
,

the fresh solutio n becomes more homoge n eous T h e plat e .

herewith represe nted is n ot one of the best so far as the focu s

is co n cer n ed but the i mproveme nt in this respect may readily
,

be observed .
 Hy dra tion of Me taplzosp boric A cid .
7 1

We call atte ntio n to the followi n g precautio n A fter hav

i n g bee n o n ce set up the apparatus must remai n absolutely
fixed n ot o nl y duri n g the few days n ecessary to complete o ne
,
“

reactio n but duri n g the time n ecessary to complete the whole

,

series of reactio ns especially those of the whole solutio n and

,

the correspo n di n g partial solutio n s The ordi n ary p re c a u .

tio n s are n ot suffi cie nt to gu ard agai nst this source of error ,

si n ce the pla n of the apparatus is such that the slightest

motio n of the slit the le n s or the tube is mag nified m a n y
, , ,

times on the plate Ma n y plates were spoiled owi n g to this

.

sou rce of error without appare n t expla n atio n In order that .

two plates may be comparable the li n e traced by the side ,

-

light on the one m ust overlie the correspo n di n g li n e on the

other wh en th e plates are superimposed in order to sho w that ,

the vertical slit an d the le n s have n ot bee n moved the li n e

traced by the beam through the solutio n after the reactio n is
completed ( the axis of x ) o n the one must overlie that of the
other i n o rder to prove that the tube co n tai n i ng the solutio n
,

has not bee n moved sidewise or tur n e d about a vertical axis ,

an d in order to prove that the t wo fresh solutio n s were of t h e

same stren gth ( this applies especially to partial solutio n s )

a n d of course the side light o n a ny o n e pl ate must be re p re
, ,
-

se n ted by o n ly a si ngle li n e n o matter how ma n y times the

,

plate has bee n exposed i n order to prove further that the

,

plate has not bee n moved .

In worki n g with metaphosphoric acid owi n g to the re ,

m arkable deliquesce n ce of the substa n ce each specime n of ,

the acid had to be prepared afresh an d the weighi n g could be

accomp lished with o n ly approximate exact n ess O ne speci .

m e n prepared by dissolvi n g the a n hydride in water an d heat

,
‘

i n g i n a plati n u m crucible u n til the liquid re mai n ed quiet

over an ordi n ary Bu n se n bur ner except for the escap e of
white fumes co n tai n ed
,
per ce n t of metaphosphoric acid
although other specime ns may have co ntai n ed an amou n t of
phosphorus correspo ndi ng to more th a n 1 00 per ce n t of meta
phosphoric acid as is usually the case owi n g to the prese n ce
, ,

of a n hydride The customary d ifi c ulty Was experie nced i n

.

obtai ni ng an acid sumc ie ntly free from alkalies to be freely

s oluble i n wa ter .
7 2 Bla ke .

The plate figured herewith represe nts the curve O btai n ed

as above desc ribed whe n 4 grams of metaphosphoric acid wer e
dissolved in 5 cc of water at the temperature bei n g
.

kept n early co n sta nt u ntil the reactio n was over A bout n i n e .

mi n utes were re q uired for solutio n The seco nd li n e fromZ th e .

top is the record left by the side light showi ng that the ap -
,

paratus was not moved The other four horizo n tal li nes are .

the record of the reactio n duri ng four successive n ights the ,

lowest o n e represe nti n g the e nd reactio n ( the axis of x ) it ,

havi n g bee n previously determi n e d th at the reactio n is com

p le te d i n four d ays This was d o ne by allowi ng the plate to
.

ru n dow n a fifth n ight the li n e thus traced bei n g ide n tical ,

with the li ne traced the fourth n ight That the reactio n was .

completed i n the ti me specified is further show n thoug h not ,

with the same degree of precisio n by the fact th at the li n e for ,

the fourth n ight an d the li n e traced by the side light are -

measurably p arallel The vertical li n e at the right was due

.

to the fl ash light a nd represe nts the positio n of the plate at

-

the begi n n i n g of the reactio n ( the axis of y ) The di sta nce .

betwee n this li n e an d the begi n n i ng of the pri n cipal curve

represe n ts the time ( nearly half a n ho ur ) n ecessary for i ntro
d uc i ng t he solutio n i nto the tube an d adj usti ng the focus By .

havi n g the focus pre a dj usted as i n dicated above this i nter

-
,

val was much reduced The ordi n ates were draw n with the .

the dividi n g e n gi n e and represe nt i n tervals of thirty mi n utes

,

each .

Two le n ses L and L were used i n stead of o ne L bei n g

, 1 , , , ,

betwee n the tube and the plate an d very n ear the tube i n ,

Order n ot to n eutralize the dis persio n The dista n ce SL .

,

cm L L .
,
cm L S 2
2 1 4 cm a b cm ; .
2 ,
.
r: .

a d : cm L , a . cm d L = 8 cm The width of .
,
.

the vertical sl 1t S was mm the width of the horizo n tal .

sli t i n fro n t of the plate was mm an d its dista n ce from

'
-
.
,

the plate was cm In order to improve the focus still

‘

. .

furthe r the e nds of the tube were covered with a black cloth
,

havi n g a vertical Slit 0 2 7 cm i n wi d th The width of this

.
. . .

slit might adva n tageously be still further reduced The .

source of light was an ordi n ary i n ca n desce nt electric bulb .

74 N ote s .

We gratefully ack nowledge our i ndebted ness to Dr Wm . .

D ua n e for assista n ce an d advice throughout the course of the

work .

H L E P HY S
A LL T Y IC A A BOR A OR
UN VE S T Y O C LO D
I R I F O R A O .
,

In a n ote whic h appeared in the last volu me of this J OU R

l
N aI .,atte ntio n w as called to the importa nt results obtai ned in
the course of rece n t i nvestigatio ns on radio active substa n ces -
.

Brief me n tio n was made of the active lead salts obtai n ed by

H ofma nn an d Strauss fro m a n umber of ura n ium mi n erals
" ’

'

such as brOg g e rite cleveite pitchble n de alvite samarskite , , , , ,

euxe n ite an d ura n ium mica Si n ce that time these authors

, .

have p ublished the results of further i n vestigatio n s alon g the

3
same li ne It now appears that these salts co ntai n a n e w
.

eleme n t closely related to lea d .

~
B y appropriate methods they are able to separate from the
mi n erals or from ura n ium residues chloride of lead mixed
, ,
”
with radio lead chloride a n d the chloride of still a nother
-
,

n e w eleme n t which appears to be very closely related to

ruthe n ium as we sho uld expect from its approximate atomic
,

weight It is probably the homolog ue of m a n ga n ese

,
.

It was n ot fully i n vestigate d .

From th e more soluble portio n s of the mixed chlorides the y

obtai n ed besides the above me n tio n ed eleme n t the stro ngly
,
-
,

active radio lead Its sulph ate was a n al y zed an d fou n d to

-
.

co n tai n about per ce n t S0 I f the metal be bivale n t i n 4

.

the sulphate this would i n d icate an atomic weight of ,

so that it might be regard ed as the homologue of ti n R a d io .

lea d c an be precipitated from slightly aci d solutio n s by hy d ro

g e n sulphide its sulphate is i n soluble i n dilute sulph uric
,

acid its salts dissolve i n caustic potash and can be precipita

,

t e d by hydroge n sulphide The nitrate is soluble in water .

,

an d from this solutio n it i s almost completely precipitated by

ammo n ium carbo n ate U n like lead its chromate is not de .

,

composed by sulphuric acid Its chloride is more soluble .

tha n lea d chloride an d its sulphide is at o n ce decomposed by ,

fumi ng hydrochloric acid L ead sulphate gives a blue light .

whe n u n der th e i nflue n ce of the cathode rays radio lead sul -

phate gives a bright blue light a n d is afterwards phospho -

1 Th i J U N L 5 7 7
s O R A , 2 ,

Be r d . . c he m . Ge s . , 3 3 , 3 12 6
3 I bi d .
, 3 4 , 8 , 90 7 , 3033 Se e a sol Ho fm an n , K or n , u . St rau ss Ibid .
, 3 4 , 407 .
 N ote s .
75

re sce nt T he active sulphate has an i nte n se rose color whe n

.

heated i n the air to The chlori d e ofte n has a similar

color .

R adio lead sulphate acts on the photographic plat e through

-

g lass alumi n ium caoutchouc paper an d air an d much more

, , , , ,

stro ngly tha n polo n ium obtai n ed at the same time from the
same mi n erals It discharges th e electroscope but not as
.
,

rapidly as polo nium salts E ve n whe n exposed to direct day .

light for two mo n ths there was n o cha n ge in its photographic

activity From this an d fro m its actio n through alumi n ium
.

it di ffers fro m the phosphoresce n t sulphide s of the alkali n e

earths The sulphate emits Becquerel rays It was show n
. .

th at radiu m an d polo nium purposely m ixed with lead salts

could easily be sep arated by the method u sed i n prepari n g
ra d io lead sulphate an d the resulti n g lea d sulphate was i n ac
-
,

tive Further ra d io l ead is u n li k e rad i um polo n iu m and

.
,
-
, ,

acti n ium in that its sulphate alo n e acts photographically .

The sulphide chloride iodide chromate carbo n ate and

, , , , ,

oxide made from stro n gly active sulphate are i n active but ,

regai n their power when cha nged back i n to the sulphate .

Si n ce the activity ceases after some mo n ths it is evide nt that

*
radium is abse nt The re n ewal of activity u n der the i n fl u
.

e n ce of the cathode rays shows that polo n ium i s n ot pres

e nt .Whe n the sulphate is partly cha n ge d i nto sulphi d e by
heati n g with sulphur it becomes i n active The activity is , .

°
greatly i n creased by heati n g to 4 5 0 for fiftee n hours a n d a lso ,

b y evaporati ng with sulphuric an d n itric acids .

It was fou n d that the sulph ate sulphide chloride iodide , , , ,

chromate an d carbo n ate are alike in their actio n o n the elec

,

t ro s c op e .

Whe n equal amou n ts of ra d io lead sulph ate a n d of lead sul -

phate co ntai n i n g radiu m were place d on the glass side of a

photographic plate it was see n that the radium had acte d o n
the farther side of the gelati n layer but the rad i o lea d acte d ,
-

o nly on the si d e n ext to the g lass .

Si n ce o n ly the sulph ate acts photographically while all the

salts discharge the electroscope it is evi d e n t the photographic ,

rad i atio n is n ot the same as that which produces the latter

e ffect H avi n g i n m i n d the latest work on thorium radi atio n
.

a n d the discharge of electroscopes i n the higher strata of the

air on e might imagi n e that a te n uous almost impo nderable

, , ,

substa n ce adheres to ra d io active substa n ces an d by its grad -

,

ual escape discharges the electroscope an d seco n darily pro , , ,

duces photographic e ffects B ut this is not i n agreeme nt .

°
w ith the fact that heati n g to 45 0 i n creases the radio activity —
.
76 N ote s .

It is probable that there is withi n the atoms some activity that

causes the emissio n of rays of di ffere n t wave le n gths and -
, ,

co n seque ntly of di ffere n t properties It was at first thought

, .

that the activity m ight be due to positive charges du e to the

cathode rays If this were the case the a node rays should
.
,

destroy this effect but it was fo u nd that they produced a ,

slightly greater activity Neither c an they be cathode rays .

,

for they pe n etrate glass or a layer of air 1 cm i n thick n ess .

witho ut appreciable weake ni n g of e ffect .

This work of H ofma n n a n d Stra uss has bee n severely c riti

l
c iz e d by G i e se l who first poi n ted o ut that it would be very
,

d i fi c ult to ob t ai n n e w radio active substa n ces i n p ure co n di -

tio n fro m such small qua n tities of the earths as 1 00 grams .

He was of the O pi n io n that the e ffects n oticed must be due to

the prese n ce of very small qua ntities of the i nte n sely active
substa n ces already k n ow n or else to i n duced activity More , .

2
rece ntly he takes up the discussio n a new an d repeats the ex ,

p e ri m e n ts with two sa m ples of radio lead sulphate prep ared by

-

Hofma n n a n d Strauss H is results are i n some respects i n .

, ,

direct co n tradictio n to theirs H e fi nds that the sulphate .

“

does not lose its Becquerel radiatio n i n three fourths o f a year

- - -
,

a n d it is not caused to give n e w or i n creased Becquerel radia -

tio n by the cathode rays A ll the compou n d s a n d n ot th e .

,

sulphate alo n e act o n the photographic plate The appar

, .

e ntly co n tradictory result of H ofma n n a nd Strauss is ex

plai n ed by their arra n geme n t of the experime n t which does
n o t exclude a seco ndary actio n of phosphoresce n t light .

R adio lead sulphate emits a mixture of Becquerel rays an d

-

”
light rays which are produce d co n sta n tly by the former .

Whe n the plate is wrapped i n black paper the actio n of the

light rays is preve nted an d on lo n g exposure the B ecquerel
rays fi n ally act R adio lead sulphate a n d the carbo n ate
.
-
,

chloride and sulphide prepared from it produced exactly the

,

same e ffect u n der these co n ditio n s H e was able to detect a .

very fai n t phosphoresce nce in the sulphate .

H ofma nn an d Strauss fou n d that the radio lead rays acted -

o n the bromide of silver layer o n the side n ext to the glass ,

but the ra d iu m rays acted o n the farther side This is d ue to .

the fact that the light rays from the radio lead sulphate are n ot -

able to pe n etrate the se n sitive film as readily as the Becquerel

rays .

R epeati n g the experime nt of mixi ng radium an d lead salts a nd

the n separati n g the t wo he obtai n e d an active lead sulphate ,

1 Be r . d . che m . Ge s .
, 33 , 19, 35 69
Be r d . . che m . Ge s .
, 3 4 , 37 7 2
in which rad ium could not be detected chemically T his was .

do n e by allowi n g the mixed solutio n s to sta n d for eight days

before the separatio n This was a n alogous to his previous .

l
experime n ts with bismuth The sulphide of lead so obtai n ed .
,

an d the iodi d e made from it were both active He is of the , .

O pi n io n that H ofma nn an d S trauss have n ot yet prove d the

existe n ce of a n e w radio active eleme n t in radio lead - -
.

2
The ne w u nn amed substa n ce which acts chemically ,

like lead an d was d isco vered i n u ra n ium mother liquors -

,

shows n o dimi n u tio n of its i nte n se activity after sta ndi n g a

year I n this respect it resembles radium an d acti n iu m
. .

P olo n ium materi al shows a slight activity after two years

'

Fresh preparatio n s lose their activity rapidly but the rate of ,

loss co n ti nually decreases especially i f the polo n iu m be mixed ,

with a large proportio n of lead chloride .

H e was able to show that the water of crystallizatio n dis

tilled fro m radium barium bromide is stro ngly active That .

this is n ot due to ra d ium carried over with the steam is show n

by its loss of activity after a few days Nearly all colorless or .

slightly colored solids became lumi n ous u nder the i nflue nce
of the radium rays an d the same is true of l iquids such as ,

water an d especially petroleum The lumi nous zo n e does not

, .
,

exte n d far i nto th e liquid C E w . . . .

f A mmon iu m
O n t/
ze E x i ste n ce o .

The evide n ce i n favor of the metallic n ature of ammo nium

a
was summed up i n a n ote i n the last volume of this J oU R N A L .

L e Bla n c s work o n ammo n ium a m algam formed by the elec

’ '

t roly si s of ammo n ium salts at a low temperature seemed to

have removed the last experime n tal evid e n ce agai n st th e
” ‘
metallic n ature of am mo n ium Q uite rece n tly Otto R u ff .

attempted to obtai n ammo n iu m by the electrolysis of ammo

n ium iodide dissolved i n liqui d ammo n ia A tube so mewhat .
,

like an i nverted Ywith electrodes f used i nto the lower e n ds ,

was partly filled with potassium iodide It was the n cooled .

with liquid ai r and alcohol an d dry ammo n ia was co n de n sed

i n it . O n passi n g a n electric curre n t through it iodi n e was
set free at the positive pole and at the n egative pole were ,

see n drops of a light mobile copper colored liquid with a , ,

-

metallic appeara n ce These rose to the top and dissolved .

,

formi n g a solutio n of an i n te nse blue co lor The substa n c e .

w as shown to be potassium ammo n ium K N H , , . .

l Ve r h d . . ph y s G e s 5 Ja n u ar
. .
, ,
1 900 .

9 Be r . d . c he m G e s
.
3 3 19 35 7
.
, , , 0
3 Th i s JO U R N A L 2 5 , , 43 1
4 Be d che m Ge s
r. . . .
, 34, 2 604
78 Re vie ws .

The electrolysis of ammo n iu m iodide was ne x t u nde rtak e n ,

but eve n whe n the solutio n w as coole d dow n to its freezi ng

poi nt n othi n g but hydroge n wa s formed at the n ega
,

tive pole a nd n ot a trace of blue color was see n i n the solu

,

tio n It was thought that some ammo n ium might be formed

.

at high pressures an d the experime n t was repeated with the

,

upper e nd of the tube sealed and the whole cooled to ,

A fter the curre nt h ad passed for five hours an d an estimate d ,

pressure of 6 0 atmospheres had bee n obtai ned there was still ,

no evide n ce of the formatio n of ammo n ium There was also .

n o ammo n iu m amalgam formed whe n mercury was used as the

cathode .

The author thi nks that ammo n ium may possibly be ob

t ai n e d by work i n g at still lower temperatures a nd with greater
pressures A suitable solve n t for these co nditio n s is un
.
,

k now n A mmo n ium is not to be regarded as a true a n alogue

.

of the alkal i metals but res e mbles the easily dissociated ,

alk ali ammo n ium compou n ds such as K N H, N a N H and

-
.
, .

Li N H It should be Writte n H N H3 i n stead of N H

’

. . .
, ,
.

C . E . W .

V I E WS
RE .

DI E HE TE R O G E N E N G L E I C H G E W I C H TE M STA N D P UN K TE D E R VO
P H A SE N L E H R E , v o n D R . H W BA K H U I S R O O Z E BO O M P ro fess or a n
. .
,

d e r U n i ve r si t éit A m s rd a m te E rs tes H eft , D I E P H A SE N L E HR E SYS

-

M
.

TE ME A U SE I N E R K O MP O N E N TE i t 5 4 e i n g ed r u c te n A bbi l d u ng e n
. k .

Dr u c k u n d V erl ag v o n Fr ied r i c h V iew eg u n d S oh n , B rau n sc hw ei g ;

1 90 1 .
pp . 22 1 .

There are few subj ects i n physical chemistry which are dis
cussed more freely to day tha n the phase rule and fe w the -
,

mea n i n g of which is less clearly u n d erstood There are thos e .

perso n s who tell us that the phase rule is the o ne ge neraliza

tio n of i mporta n ce i n physical chemistry an d that everythi n g ,

i n physical chemistry not to say i n chemistry should ce n ter , ,

arou nd it .

O n the other ha n d there are those who will h ave very littl e
,

to do with the ph ase rule eve n as applie d to physical chemis

try and amo n g this n u mber c an be me ntio ned some who
,

sta n d i n the very fro n t ra n k of physical chemists .

The i ntermediate stage is however represe nted here as i n so , ,

ma n y other fields Those who belo n g to this class regard t he

.

phase rule as an i mporta nt ge neralizatio n which co rrelates ,

a large n umber of more or less isolated facts already estab

l ish e d an d which also suggests n e w li n es of i nvestigatio n
,
.

They regard the phase rule as o ne of the three or four impor

 Re vie ws .

ta n t ge neraliz atio n s that have bee n reached by moder n physi

c al chemistry an d upo n which it is based ,
The author of the .

book i n questio n belo n gs to this class .

It should be poi n ted out that m uch of the most i mporta nt

experime ntal work beari ng upo n the ph ase rule has bee n do n e .

by R oozeboom and his pupils The book is therefore writ .

, ,

te n by on e whose k n owledge o f the phase rule has bee n ap

plied i h the laboratory .

The p art of the book which is at ha n d deals o nly with sys

tems co n tai n i ng on e compo ne n t A brief historical i ntrod uc .

tio n i n cludi n g homoge neous and heteroge neo us equilibri um

, ,

the phase rule n on varia nt mo n o di and poly v ari ant sys

,
-
,

tems is followed by a discussio n of th e various systems with

,

o n e compo n e n t These i n clude equilibrium betwee n a liquid

.

a n d a gaseous phase equilibrium betwee n a soli d an d a gas ,

eo n s phase equilibrium betwee n a solid and a liquid phase

, ,

a n d equilibriu m betwee n two solid phases T he triple .

”
poi n ts i n the cases of solid liquid an d gas solid solid and , , ,

gas solid solid and liquid ; and solid solid and solid are
, , , , ,

co nsidered at some le n gth and in such a clear and co n cise ,

m a n ner that the reader c an scarcely fail to grasp their sig nifi
ca n ce .

A s far as o n e c an j u d ge of a boo k from the appeara n ce of

th e fi rst third of it th e work i n ha nd is by far the clearest and
,

most i ntelligible that h as thus far bee n writte n on the phase

rule It is safe to pre d ict that the comp l eted work will c on
.

tribute m uch to a better u n dersta ndi n g of this i mporta n t g e n

e raliz at i o n which has bee n freque n tly disregarded because of
,

the u n n ecessary complexity i n which it has bee n shrouded .

The seco nd portio n of the boo k will deal w ith systems of

two compo ne nts and the third with three and more com ,

p on ents . H . C .
J .

J A H R B UC H DE R E L E K T R O C H E MIE , B E R I C H TE B E R D I E FO R TSCH R ITTE U

DE S JA H R E S 1 900 U n ter M i tw i r u n g d e r H E R R N P R O F DR K
. k . . .

E L E S, G ie s se n , P R O F F W K USTE R , C l a u sth a l , u n d P r i v a t d o c e n t
'
-
. . .

D R H D A N N E E L , A ach en
. . He rau sg eg e be n v o n D R W N E R N ST , 0
. . . .

P ro fe s so r a n d e r U n i v e rs i t at G Ott i n g e n , D i re to r d e s I n st i t u t s i ti t k
ph y s i a l i sc h e C h em i e u nd E l e tro c h e m i e u n d D R W B O R C H E R S 0
k k . .
, .

P r o fe s so r a n d e r T e c h n i s c h en H oc h sc h u le A a c h en , V o rst a n d d e s
L abo ra t or iu m s fii r M
e t a l lh ii t t e n k u n d e u n d E le t r o m et a ll u rg i e v ii k .

Jah rg a ng Verl ag v o n Wi l h el m K n a p p , H a lle , A S 1 90 1

.
p p 5 96 . . . . .

The Jahrbuch der E lektrochemie co ntai n s as is well ,

k n ow n a brief survey of the work of the ye ar i n e le c troc he m

,

i stry This subj ect has two disti nct phases the scie ntific and
.
,

the practical an d each has acquired the greatest promi n e nce

,

i n the last few years E ach side of the subj ect is represe nted .
80 Re vi e w s .

by o ne o f the ables t me n of the day and this i nsures a mas ,

t e rly treatme n t of the whol e subj ect The collaborators of .

N er n st an d Borchers are me n of high sta ndi ng both i n t he

scie n ce and applicatio n of chemistry .

For the co n ve n ie nce of those who use the book the material
has bee n beautifully systematized The scie n tific portio n .

treats first of such ge n eral matters as lecture experi me n ts ,

books which have appeared d escriptio n of methods appara , ,

tus whic h h as bee n devised etc The broad subj ect of c o n , .

d uc ti v ity is take n u p a n d its applicatio n s to special problems ,

such as the dissociati n g power of solve nts the co n stitutio n of ,

i n orga nic an d orga n ic compou n ds the electrical co n ductivity ,

of solids an d th e like O n e o f the most i n teresti n g sectio n s

, .

i n this part of the work is that which has to do with e le c t roly

sis a nd polarizatio n The theory of electrolysis adva nced by
.

L e Bla n c a n d n ow ge nerally accepted as well as his own ,

beautiful i nvestigatio n s o n polarizatio n have brought the ,

whole subj ect very much to the fro n t i n the last fe w years .

Si n ce the work of N er n st on the electromotive force of primary

cells few i nvestigatio n s i n the field of electrochemistry c an be
,

compared i n importa n ce with it a n d this is shown by the ,

amou n t of work do n e yearly i n this field .

The material i n applied electrochemistry is also well sys

t e m a tiz e d u n der the ge n eral heads of productio n of electrical
e n ergy electrolysis i nclu d i n g the productio n of the non
, ,

metals the metals i norga n ic co mpou n ds an d orga n ic com

, , ,

pou n ds This is followed by a discussio n of forms of apparatus

.

devised for w e i n ap plied electrochemistry .

The boo k s u seful to all who are i nterested i n an y phase of

.

electrochem i stry b ut especially to those who do n ot h ave ac

,

c ess to the c urre n t literature of th e subj ect 11 C J . . . .

TH E E L E ME N TSO F Q U A L ITA TIV E A N AL Y SIS . B y WM . A . N O YE S , PH D ,

. .

r r o f C h e m istry i n th e R o se P o l y te ch n ic I n sti t ute

P o fe s so t . Fi f h
t re v i sed N e w Yor k He n ry H o lt C o 1 90 1
e d i i on , . . . .

P rof N oyes book is well k n ow n as on e of the best brief

’
.

laboratory ma nu als i n use In the prese n t e d itio n he has re .

vised the scheme for the systematic detectio n of acids em ,

ployi n g in the mai n the methods suggested by A begg an d

H erz .

A few pages of the i ntroductio n are give n to a brief sketch

of the theory of solutio n s .
82 Fay a nd Gillson .

in studyi ng the n ature of alloys have bee n the determi natio n

of the fusibility curves an d the study of the structure by ,

mea ns of t he microscope These two methods gi ve resul ts .

which e ntirely corroborate each other By the older methods .

of i n vestigatio n such as studies of the heat of formatio n heat

, ,

of sol utio n electrical co nductivity etc the differe n t methods

, , .
,

n ot o n ly did n ot give defi n ite co n clusio ns with regard to the

co n stitutio n of the alloys but i n most cases led to di ffere nt , , ,

co n clusio n s The problem was u ndoubtedly much more

.

complex tha n the study of ordi n ary ch emical compou nds ,

si n ce i n the latter case it was possible to use solve n t s which

woul d not a ffect the n ature of the substa n ce whe n dissolved ,

whereas for alloys there was no solve nt which would not e n

, ,

tire ly cha nge the chara cter of th e substa n ces T he work of .

L e C hatelier G autie r H e y c oc k an d N eville Stead and

, , , ,

others has led however to defi n ite co nclusio n s an d the fusi

, , ,

bility curves establishe d by them have bee n fou n d to be eu

t i re ly a n alogous i n character to the curves fou n d for mixtures
of simple chemical substa n ces .

With the aid of the microscope the results obtai n ed in the

determi n atio n of the fusibility curve have bee n co n firmed -
.

The microscope gives an approximate a nalysis of the differe n t

co n stitue n ts co ntai ned in the alloy an d i n m a n y cases a cl ue , , ,

to the order of solidificatio n of the several co nstitue n ts .

Various alloys composed of two metals have bee n fou n d to

give curves of fusibility which fall u nder o n e of the three fol ,

lowi n g classes illustrated i n the diagrams Figs I I I an d

, , .
, ,

II I
1 . Two metals which form soli d solutio n s give a straight
li n e curve co n n ecti n g the two freezi n g poi n ts ( see Fig -
.

R oozeboom has show n that this curv e may have a m aximum

1

or a mi n imum poi nt but these poi n ts may readily be disti n ,

g u i sh e d by ,
mea n s of the m icroscope from maximum poi n ts ,

represe n ti n g compou n d s and mi n imu m poi nts correspo ndi n g ,

to eutectic alloys .

2 . Two metals which form n either solid solutio n s n or co m

2
pou nds give a curve of two bra n ches meeti ng i n a eutectic ,

1
J P h y C h m 3 385
. s . e .
, 0, .

2 T he e u te c ti c
‘
is t h at a lloy , o fd e fi ni t e co mp osition an d c o n s t an t m e l ti n g p oint
-
, in
 Tbe A lloy s o
fL e ad a nd Te ll u r i u m .

Fi g . I .
—
Di a g ra m
ho w i n g m e l tin g p oi n t s f gol d s i l v e r ad mi um si l v e r a nd bi
s - o -
, c -
, s

mu th an ti mon y lloy s (T h ord i n t s re p re s e n t d g re e C th e ab sc i s s e p e

- a . e a e e s . a ,
r

n t g e s o f t h e tw
ce a c on s tit u nt s of a c h a ll y ) o e e o .

the freezi n g poi nt of which is lower tha n the freezi n g p om t of

- -

e ither metal ( see Fi g .

3 Two metals whi ch form o n e or m ore compou n d s give a

.

c urve the n umber of bra n ches of which is depe nd e n t upo n

,

t h e n umber of compou nd s formed In this class o n e of the .

c o mpou nds may form a solid solutio n with o n e of the pure

m etals or with a n other compou n d ( see Fig

, .

The examples of these cl asses of alloys together with their ,

fusibility curves sho wn i n Figs I I I a n d I I I are o f

-
fered ,
. .
, .
, .
, ,

w h i c h th e o n ti tu n t re i n qu i l i b ium t l l te mp e tu
c s e s a It m e l ti n g p oi n t i s
e r a a ra re s . s -

l o w e r t h a n th m l ti n g p i n t s o f i t s c n s ti t u n t
e e n d i t s c o mp o i ti o n i
-
o n ot a l t
o ed e s, a s s e r

d u ri n g o l i d ifi ti n
s T h e u t e ti c a ll oy m y b e c o mp o e d f tw o m t l s tw o
ca o . e c m a s o e a , co

po u n d o tw o ol id olu tion s ; a m e t l an d c omp o u n d a m t l n d a sol id olu

s, r s s a a ,
e a a s

tion or , o mp u n da cn d a sol id s o lu ti o n
o a .
84 Fay a nd Gillson .

no t as a complete summary of the work actually accomplished ”

i n this field but merel y to illustrate the n ature of the work

, .

Ma n y of these curves have bee n plotted from G autier s work " ’

,

a n d have n ot bee n experime n tally co n firmed .

In Fi g II the mi n imum poi n ts correspo n d to the eutectic

. .

mixtures in Fig I I I the maximum poi n ts i n the curves cor

. .

respo n d to defi nite compou n ds and the mi n imum poi nts to th e ,

eutectic alloys .

The study of the microstructure of these thre e c l asse s o f ~

alloys co nfirms very d ecisively the fusibility curves In t h e -

.

first class i t is k n ow n that the solve n t and d issolved substa n c e

separate out together The m icrostructure of metals which .

form solid solutio n s shows a homoge n eous mass i n which it i s ,

di fficult if not i mpossible to disti n guish betwee n the two c on

, ,

st i t u e n ts The alloys of gold and silver cadmiu m an d Silver

.
, ,

a n d a n timo n y a nd bismuth would Sho w o n microscopic exa m

'

i n a ti on to be composed o f homoge n eous mixed crystals of th e

two co nstitue nts I n the seco n d class where the freezi n g
.
,

poi n t of the pure metal i s co n si d erably lowered by the a d ditio n .

of the other metal we k n ow that there is first a separatio n of

,

pure solve n t an d that as the temperature of the solutio n i s

, ,

lowered the pure metal co n ti n ues to separate u n til the c o n

,

ce n tratio n of the resulti n g solutio n h as reached that of the

eutectic alloy whe n the mass soli d ifies as a whole T h e
, .

m i c rosc O p ic co n stitue n ts co n seque ntly should be the pure , ,

metal an d the eutectic the amou n t of each d epe n d i n g upo n —

the proportio n of the two metallic co n stitue n ts A s the e ute c .

tic is the alloy i n which the two co n stitue n ts are mutually

saturated an d as the two separate simulta n eously we Shoul d
, ,

expect to fi nd a structure made up of altern ate layers of th e

two metals This is actually fou nd to be the case and th e
.
,

structure for all eutectics is very characteristic resembli n g ,

the fi ne li n ed m arki ngs of the huma n thumb The eutecti c

-
.

may co n sist of two metals of metal an d a compou n d or o f , ,

two compou nds but i n all cases its structure is very charac
t e ri sti c a n d easily recog n ized This class of alloys may be .

illustrated by taki n g as a n example the fusibility curve of t h e -

t i n bismuth alloys
- Fig I I The bra n ch of the c urve be
, . .

1 u
G a ti e r : Bull . So c d E
.
’
n c o u ra g e m e nt , I , 12 93
 T be A lloy s fL
o e a d a nd Te llu ri um .

1 100
“

6 00

100 90 so 70 60 50 30
D 10 20 30 40 50 70

F ig II
. .
—
D i a g ra m s h ow i n g m e l ti n g p oi n ts o fg o l d lc o p p e r
-
lumi ni um i n c anti m ny
, a - z , o

le ad , z mut h c ad mi um i n c
i n c - bi s ,
-z
, ti n - z i n c , t i n - l e ad a n d ti n b i smut h a lloy s
,
-
.

(T he o di n ate
r e p e s n t d g re e s C
s r r e e th e ab s c i s sa e p e c e n ta g e s o f th tw o c on
, r e

s titu e n ts f e a h ll oy )
o c a .

twee n 45 an d 1 00 per ce nt represe nts the separatio n of of ti n

“

tin a nd the eutectic O an d bi s m uth t he amou n t of each

f tin , .

d epe n di n g upo n the compositio n A s by i n creasi n g the per .

,

ce ntage of bismuth we approach the compositio n of the e ute c

,

tic alloy 4 5 per ce n t t in more a n d more of the eutectic struc

,
.

ture will appear u n til the whole mass co n sists of the e utectic
alo n e The additio n s of bismuth to ti n have successively
.

lowered its freezi ng temperature u n til at 5 5 per ce n t of bis

-
,

m uth the lowest freezi ng temperature has bee n reached and

,
-
,
"

both metals separate simulta neously from solutio n With the .

further additio n of bismuth the freezi n g temperatures begi n ,

-
86 F ay and Gi llson

to rise an d the bra n ch of the curve betwee n 5 5 an d 1 00 p e r

,

ce n t of bismuth represe n ts the separatio n of bismuth ( which

is n ow the so lve n t ) an d the eutectic alloy the relative qua n ti ,

ties of each bei ng depe n de n t upo n th e perce n tage co m posi

tio n A s the compositio n approaches that of th e pure metal
.
,

there will evide n tly be a n excess of the pure metal over th e

eutecti c The prese n ce of com p ou n d s of the third class i s
.

usually recog n ized by their crystalli n e form the forms of som e ,

of them bei n g very characteristic such as is the c ase for the com ,

pou n d SuC u3 Whe n however a compou n d forms a soli d sol u

.
, ,

tio n the detectio n of the two co n stitue n ts is much more d ifli

,

cult To illustrate the third class of alloys we may take as an

.
,

example the alloys of n ickel an d ti n givi n g a three bra n ch

, ,
-

curve of fusibility as d etermi n ed by G au t ier which is n othi n g

, ,

more tha n a combi n atio n of classes 1 an d 2 The first class i s .

represe nte d in th e bra n ch of the curve betwee n the maximu m

poi n t at 6 7 per ce n t correspo ndi n g to the compou n d N i Sn an d
, ,

1 00 per ce n t of t i n The microscopic co n stitue n ts betwee n thes e

.

two poi n ts co n sist of ho moge neous mixed crystals of the com

pou n d Ni su an d pure ti n Th e compou n d forms a eutecti c .

alloy with n ickel Whether we co n sider the compou n d Ni su

. -

or pure n ickel as the solve n t the freezi n g poi n t of each i s ,

-

lowered by additio n to the other u n til they are mutually sat

u rat e d We the n have the eutectic alloy melti n g at the low
.
,

est possible temperature at which it is possible for a mixtur e

of these two co n stitue nts to melt .

The microscopic co n stitue nts of the bra n ch betwee n 6 7 and

1 00 per ce n t of n ickel co n sist of pure n ickel a n d the eutectic

of n ickel an d the co mpou n d Ni s u betwee n 6 7 an d 3 3 p er

ce n t of the compou n d an d the eutectic .

Tbe Pr ep a ra tion f
o P u r e Te ll u r i u m .

The metallic tellurium required was extracted from th e

slim e which is the waste product of the electrolytic proces s
employed at the B altimore C opper Works i n the treatme n t of
copper m attes from the West This residue after the removal .
,

of silver an d C Op p e r co n sists pri n cipally of the sodium salts of

,

silicic sele n ous a n d tellurous acids the last n am ed bei n g i n

, , ,

large excess The process by which the n ecessary liqui d

.
 Tbe A lloy s o fL e a d a nd Te ll u ri u m .

100 90 70 60 50 40 30 20 10 0
0 10 30 40 50 60 70 80 90 100
F i g I II
. .
—
Di a gr a m s h ow i n g th e m e l ti n g p oi n ts of n i c k e l
lumi n i um n ti - ti n , si
- lv e r -a ,
a

m o n y c o pp e i n c an ti m n y l e a d c o pp e l e ad a lumi n i um a n d b i s mut h c opp

- r, z - o ,
- r, -
,
- e r

a lloy s ( T h e o di n ate s r e p e e t d g s C t h e b c i e p rc e n t ge s of th
. r r s n e re e . a s ssa , e a e

tw o c o n sti t u e n ts o fe c h a ll y ) a o .

solutio n is secured a n d the copper is refi n ed has bee n de ,

scribed by Whitehead a n d the separatio n a n d preparatio n of

‘
,

2
pure tellurium has also bee n rece ntly described It will suf .

J A m Ch m S
1
.
7 8 848. e . oc .
, 1 , 2 0, .

Th i JO U N L 2 3 5
2 s R A , , 10 .
88 Fa r a nd Gi llson .

fi ce to say here that the method co nsists i n the precipitatio n

of the metal an d its co nversio n i n to basic tellurium n itrate ,

T e O, ( O H ) NO
,
. This fi n ely crystallized salt serves as an
.
,
.

excelle n t mea n s of obtai ni n g pure tellurium The basic ui .

trate is decomposed by heat the oxide thus obtai ned is dis

solved ih hydrochloric acid and from this solutio n the metal ,

is re pre c ipitate d by mea n s of sulphur dioxide C rystallizatio n .

of the basic n itrate fro m a n itric acid solutio n removes sele

n iu m completely fro m the tellurium a n d also fur n ishes a very ,

co n ve n ie nt m ethod for the separatio n of other metals .

Tellurium thus prepared is a black amorphous powder .

A fter fusio n an d cooli n g however it is decide d ly crystalli ne , , ,

resembli n g a n timo n y very mark edly i n this respect but i n lus ,

ter bei n g n early as bright an d white as Silver It is capable of .

taki n g a high polish but on accou nt of its brittle ness it is

, , ,

diffi cult to get an e n tirely smooth surface Its freezi n g poi nt .

-

°
is 4 46 C an d its specific gravity

f tlze A lloy s
Tbe Pr epa ra tion o .

H avi n g obtai n ed i n this way about 2 5 0 grams of pure tel

l uri u m we made 1 7 alloys , varyi n g i n compositio n from 9 8
,

per ce n t lead and 2 per ce n t telluriu m to 5 of lead an d 9 5 of

tellurium .

The lead used i n the experime nts was fro m two di ffere n t
sources but both sampl es w ere as pure as could be obtai ned
, .

°
The freezi ng poi nt of both samples was fou n d to be 3 2 2 C
-
.

In mixi n g the alloys gra n ulated tellurium was a d ded to ,

molte n lead co n tai n ed i n a porcelai n crucible In every case .

it was fou n d n ecessary to add fro m 2 to 5 per ce n t more tha n

the amou n t theoretically required i n order to secure the com : ,

positio n desired A fter the metals h ad bee n brought together

.

the molte n m ass was thoroughly stirred an d the heat con ,

t i n u e d for a few mi n utes i n order to i n sure complete fusio n

,
.

The mass was allowed to cool i n the smoky flame of the

bur ner I n all cases whe n the two metals were brought to
.
,

gether i n the crucible there was an evolutio n of light a nd ,

heat an d the mass solidified to a hard cake which i n som e

, , ,

cases was melted o n ly with the aid of the blast lamp This
,
-
.

hard mass as will be show n later was lead telluride

, ,
.
90 Fay and Gi llson .

Throughout the operatio n the fuse d met als were protected

from oxidatio n by a layer of fi n e ly powdered ch arcoal spread -

over the surface .

Tbe A na ly si s f
o til e A llo s
y .

To obtai n samples for a n alysis a vertical sectio n on e eighth

,
-

i n ch thick was sawed out fro m the mass of each alloy on e ,

h alf bei n g used for a n alysis a nd the other half for micro
SC O p ic al exami n atio n
. A s the alloys varied co n siderably i n
hard n ess it was possible to p ulverize some of them while from
, ,

others the sample was obtai n ed by fili ng .

No reliabl e procedure was k n ow n for the determi natio n of

either lead or tellurium i n the prese n ce of the other and ma n y ,

methods were tried without much success It was thought .

that tellurium might be separated by taki n g adva ntage of th e

i n solubility of its basic n itrate in stro n g n itric acid but c on ,

corda n t results were not obtai n ed It was also fou n d i mp os .

sible to remove the lead as sulphate a nd to precipitate the ,

telluriu m from the sulphuric acid filtrate .

The method fi n ally employed for the a n alysis of all of the

alloys co n sisted in volatilizi n g the telluriu m as chloride i n a ,

curre n t of chlori n e gas and weighi ng the residue of lead chlo

,

ride It was fou n d that by keepi n g the temperature n ear the

.

fusi n g poi nt of lead chloride all of the telluriu m chloride

-
,

c ould be distilled o f f without loss of lead This m ethod was .

fou n d to be very co n ve nie n t accurate an d rapid Table I

, ,
. .
,

showi n g the tabulated results of the a n alyses gives the per ,

ce n tage of lead as fou n d by a n alysis and that of tellurium as ,

calculated by di ffere n ce .

Tbe De te r mi n a tion o
f tlze Fre e z i ng Poi n ts -
.

A ll determi n atio ns of freezi n g poi nts were made with a L e

-

C hatelier therm o electric pyrometer The electric couple of .

this pyrometer co nsisted of a pure plati n u m wire and a wire of

plati n um alloyed with 1 0 per ce nt of rhodium These wires .

were soldered to copper wire l eads co n necti n g them with a

-
,

galva n ometer of the d A rsonv al type which reflected a beam

’
,

of light upo n a millimeter scale The j u n ctio n was ca librated

.

by n oti n g the deflectio n s correspo ndi ng to the followi n g

k n ow n poi n ts stated i n ce ntigrade degrees
,
 Tbe A lloy s fL
o e ad a n d Te llu r i u m .
91

B oi l i n g p
-
o in t s . F re e z i n g - p oi n t s .

Water 1 00 A l umi nium 660

N aphthale n e 2 18 G old 107 2

Sulphur 44 5 C opper 1 095

The defl ectio n s were such that by rea d i n g to te n ths of a

°
m illimeter o ne could estimate the temperature withi n 2 C .

Si nce both lead and telluriu m al loyed very readily with

either plati n um or plati n um rhodiu m it was fou n d n ecessary
-
,

to protect the j u n ctio n This was satisfactorily e ffected by

.

threadi n g the wire through a p iece of hard glass tubi n g of -

small diameter be n t i n to a lo n g n arrow U

, , .

I n determi n i n g the freezi n g poi n t of a n alloy the j u n

-
ctio n ,

was pla c e d i n a molte n mass co n tai n ed i n a po rcelai n cruci

,

ble an d readi n gs were ma d e every te n seco n ds duri ng the cool

,

i n g In this way the freezi n g poi n ts give n i n Table I

.
-
and .
,

show n graphically in Fig IV were determi ne d . .

,
.

Tbe Mi crosco p ica l E x a m i n a ti on

f tbe A lloy s o .

E ach sample for microscopical exami n atio n was on e half of -

the vertical cross sectio n one eighth i n ch thick which had b e e n

- -
,

sawed from the ce n ter of th e mass of each alloy the oth er half ,

of the sectio n havi n g bee n u sed for a n alysis The surface .

w as fi rst smoothed with a file an d then by rubbi n g u n der ,

l .
—
Fre e z i ng Poi n ts a n d P e rce n tag e Composi tion
-
o fL e ad

Te ll u ri u m A lloy s .

( Show n graphically i n Fi g I V ) . .

L w f o er re e z H i gh e r
T llu i um i g p i t f e r . n - o n . re e z i n gp - o i n t.
P nt D g C e r ce . e . . e g . C .

oo o 32 2
665
6 95
7 43
7 75
80 5
85 9
9 17
82 8
65 6
5 50
44 5
40 0
42 7
4 33
44 6
92 Fay a nd Gi llson .

water on sto n e The fi n al polish was ac co m

an A rka n sas .

p l i sh e d by rubbi n g very lightly o n rouge placed o n chamois .

The surfaces were all etched with very dilute hot n itric acid ,

which brought o ut the structure satisfactorily T he alloys .

co ntai n i n g n ot more tha n 3 8 per ce nt of telluriu m could be

100
T llu ium
e r O 10
- 20
'
30 40 50 60 70 80 90 100 P e r C e nt
.
‘

L e ad- 100 90 80 70 60 50 40 30 20 10 0
Fig V . .
—
D i a g ra m s h owi n g the p e rc e n ta g e of e a c h c o n s ti t u e n t i n v a ri o u s
l e ad t e llu i um a ll oy s
- r .

etched by polishi n g i n relief but the process was laborio us ,

a nd had n o particular adva n tage over etchi n g with n itric acid .

A ll the photographs from which Figs VI to X I I h ave bee n . . .

made were take n at 9 5 diameters mag n ificatio n and have

,
’
,

bee n reproduced by the e n graver at 8 0 diameters .

D iscu ssion ofRe sults .

U po n i n spectio n of the freezi n g poi nts give n i n Table -

I .
,

and show n graphically i n Fig I V it is see n that the fre e z . .

,

i ng poi n t of pure lead is raise d to a remarkable exte n t by the

-

additio n of small amou n ts of tellurium Fo r example i n alloy .

,

No 2 the additio n of 6 per ce n t of tellurium has caused a rise

.

°
i n the freezi n g poi n t of over 300 C but the further additio n
-
.
,

of telluriu m has n ot caused a proportio n ate elevatio n of the

freezi n g poi n t The maximum freezi ng poi n t 9 1 7 C was
-
.
-
,
°
.
,

reached whe n the composi tio n of the alloy correspo nded to

t ha t o f lead telluride P bT e The form atio n of lead telluride
, .

explai n s the evolutio n of light an d heat an d the rapid rise in ,

the freezi ng poi n t caused by bri n gi n g together the two metals

-
.

The metallic lead very easily becomes supersaturated with the

lead telluride an d the latter separates out of the solutio n
, .

A s the cooli ng is carried further the excess of lead separates , .

This separatio n of the two co n stitue nts is well show n i n the

free z i n g poi n ts of alloys Nos 3 4 and 5
-
The lead poi nt .
, , .
,
Fi g V I II .
—
A ll oy N o .
9 . L e ad te llu rid e and e ut e c ti c .

( 80 D ia m e te rs .
)

Fi g . IX .
—
A ll oy N o . 10 . L e ad te llu ri d e a n d e u te c ti c .

( 80 D i a m e te rs .
)
Fi g . XII .
—
E ute c ti c a n d te llu ium
r .

80 Di a m e te rs ) .
94 Fay a nd Gzllson

dark is lead telluride With 3 8 per ce nt of tellurium the .

,

whole mass should co nsist of lead telluride and this is Show n ,

i n Fig V I I fro m a photograph of alloy No 8

. .
,
The e ffect of . .

a n i n crease i n the amou n t of tellurium we fi n d i n alloy N o 9 .

( 8 0 per ce n t of lead tell uride a n d 2 0 of the eutectic ) This is .

n icely show n i n Fi g V I I I where a small amou nt of the

. .
,

eutectic has made its appeara nce betwee n the large gra n ules
of lead tell uride Fi g IX represe n ts a photograph from
. . .

alloy No 1 0 co ntai n i n g 4 6 per ce n t of eutectic a nd 5 4 of lead

.
,

telluride The latter is s how n as dark crystallites embe d ded

.

i n the eutectic A lloy No I t co n sists of 6 8 per ce nt of e u te c

. .

tic a n d 3 2 per ce n t of lead telluride A mixture of these two .

substa n ces i n this proportio n is show n i n Fig X Fig X I . . . .

shows a photograph take n fro m the pure eutectic made by ,

allowi ng about two thirds of o n e of the alloys to solidify and

-
,

the n pouri n g off the still liquid mass A mixture of the e ute c .

tic a n d a n excess of tellurium is show n i n Fig X II The . .

photographs do n ot represe n t exactly the perce ntages of each

co nstitue nt but o n ly approximately O n accou nt of the lead
, .

telluride bei n g much lighter tha n lead a marked segregatio n ,

was fou n d i n the alloys composed of these two co n stitue n ts .

L ead telluride a nd the eutectic have n early the same Specific

gravity an d co nseque ntly Show a more homoge n eous stru c
,

ture .

It will be see n from the photographs a n d from the diagram , ,

Fi g V that lead telluride is a co n stitue nt commo n to all of

.

the alloys Its amou n t gradually i n creases as telluriu m is

.
,

added to lead u n til the whole mass is lead telluride an d the n

, ,

it gradually decreases u n til the whole mass is pure tellurium .

Telluriu m forms a eutectic alloy with lead telluride but the ,

l atter d oes n o t form a eutectic alloy with lead The form of .

the curve seems to i n dicate an isomorphous mixture betwee n

l ead a nd lead telluride a nd the m icrostructure of the alloys ,

very low i n telluri um seem to poi nt i n the same directio n .

But the t wo co n stitue nts differ so widely i n fusibility that

there is no d efi nite mea ns of k n owi n g whether or not they are
really isomorphous The isomorphis m of these two sub .

sta nces seems all the more probable whe n we take i nto c on
sideratio n the fact that the mi n eral altaite P bT e crystallizes , , ,
 The A lloy s f A n timony
o a nd Te llu r i u m .

in the isometric system and it is well k now n that lead crys ,

t alliz e s i n that system .

The hard ness of the alloys i n creases with the amou nt of tel
l uriu m prese n t The alloys co ntai ni n g over 5 0 per ce nt of
.

tellurium are very brittle .

It is proposed to co nti n ue th i s study with other tellurium

alloys .

X XXV I .
—
T H E A LL O Y S O F A NTI MO N Y A N D T E L
L U R IU M
.

BY H E N R Y FA Y A N D H A R R I SO N E VER E TT A SH L EY .

The study of an e ntirely ne w series of alloys may be u nder

take n from a desire to obtai n k nowledge applicable to the per
fe c tio n of i n dustrial alloys or merely to test certai n the ore t i ,

cal co n sideratio n s In the c ase of a n timo ny tellurium alloys

.
-
,

the theoretical side o nly is at prese nt importa nt but it is ,

hoped that the results of this i n vestigatio n may have some i n

d ustri al value at least i n directly by fur n ishi n g on e more e x
, ,
»

ample for compariso n whe n studyi ng commercial alloys .

The stateme n t is fou n d i n variou s places that a n ti mo n y is

isomorphous with arse nic bismuth and tellurium but very , , ,

little experi me n tal evide nce has bee n o ffered i n support of

this assumptio n A ll four metals crystallize i n rhombohedra
.
,

a n d the ratio of the axes a z e is approximately the same

which see ms to i ndicate but does n ot prove their isomorph , ,

ism The close associatio n of these m etals i n mi n erals also

.

seems to i ndicate that t hey are isomorphous There are how .

,

ever certai n di ffere n ces i h their properties which re n der this

,

co n clusio n somewhat doubtful an d it is therefore desirable ,

that i ndepe n de n t evide n ce be fou n d to decide the questio n .

l
I n a paper o n lead telluriu m alloys it has bee n show n that
-

two metals which are isomorphous give as a fusibility curve ,

-
,

a straight li n e co nn ecti n g their melti n g poi n t s The best ex -

.

amples of this class of alloys are the alloys of gold an d silver ,

gold an d plati n um a n d bismuth an d a n timo n y In each of

,
.

these cases the properties of the alloys are a mea n betwee n

the properties of the t wo metals The isomorphism of gold .

1 Se e p re c e din g a rti c e l .
96 Fay and A shley .

an d silver and bism uth an d a n timo n y might be co n firmed by

mea n s of t he microscope but so far as we k now no work has
, , ,

bee n p ublished o n this sid e of the problem The mic rostruc .

ture of bi n ary alloys of iso morphous m etals should show an

i n timate mixture of the two metals without an y evide n ce of
compou n ds or of a eutectic mixture In co nn ectio n with some .

work o n the isomorphism of sele n iu m an d tellurium we had

occasio n to prepare several bismuth a ntimo n y alloys in which -
,

we fou n d the microstructure to co n sist o fa very homoge neous

mixtur e of the two metals .

It was hoped that by ta k i n g adva ntage of the fusibility

curve which could be established by determi ni n g the freezi n g
poi nts of a series of alloys an d by a study of th e m ic rosc Op
,

ical appeara nce of etched specime n s of these alloys we might ,

be able to form some idea i n regard to the isomorphism of tel

l u ri u m an d a n timo n y .

With regard to the more practical side of the problem it ,

might be said that tellurium an d a n timo n y are so Similar i n

their physical properties that the former might replace a nti
mo n y i n some of its alloys If this should be fo und possible
.
,

it would O pe n up a field of useful n ess for the large qua n tities

of tellurium which now go to waste The e ffect of eve n small .

qua n tities of a n ti mo n y on malleable metals such as copper ,

an d gold is most i n j urious m aki n g them hard a n d brittle ;

, ,

but o n the other ha n d it gives the n ecessary hard n ess to the

, ,

lead of type metal an d produces valuable alloys with ti n in

,

Brita nn ia metal for decorative obj ects a nd with tin zi n c a n d , , , ,

cop per B abbitt metal for beari n gs With lead its 1 2 per
, .
,

ce n t alloy the eutectic mixture of these two metals possesses

, ,

valuable properties an d is used o n accou n t of its power to re

,

sist the actio n of sulphuric acid for maki ng the so called -

”
lead chambers for the ma n ufacture of that acid .

Telluriu m li k e wise possesses the power of harde n i n g other

metals This harde n i n g power is very mark ed i n the alloys
. .

with l ead an d R oberts A uste n has fou nd that it dimi nishes

,
-

the te n acity of gold an d copper So far as we k now no ter

.
,

n ary alloys co n tai n i n g tellurium an d correspo n di n g to Brita n

,

n i a or B abbitt metals have bee n prepared

, .
98 Fay a nd A shley .

order to protect the j u n ctio n from alloyi n g with the

In
vapors of a ntimo n y and telluriu m the two wires were passed ,

through two very s m all hard glass tubes and these tubes -
,

were the n placed in a larger piece o f hard glass tubi ng of -

about 5 mm diameter . .

To determi n e the freezi n g poi nts the alloys were placed i n -

,
°
a B attersea a nn eali ng cup a n d were heated to about 1 00
above their melti n g poi n t The molte n mass protected from
-
.
,

oxidatio n by a layer of fi n ely divided charcoal was thor ,

oughly stirred to i n sure complete a d mixture of the c on stit u

e n ts The j u nctio n w as placed vertically i n the alloy a n d
.
,

readi n gs of the gal va n o meter were take n every t e n seco n ds ,

u n til the temperature had falle n to The begi n n i n g of

the various poi n ts of retard atio n was take n as the freezi ng
poi nt The results of these determi n atio n s are give n i n Table
.
‘

I and are Show n graphically i n Fi g I

.
, . .

Ta ble l .
—
Fr e e z i ng -P oi n ts f A n ti mony Te llu ri um A lloy s
o .

H i gh f L w f e r re e z o e r re e z
A n ti mon y T llu i um
e r i n g t mp
. i n g t mp -
e -
e .

D g C D g C
. .

Per c e nt P
“

. nt
e r ce . e . . e . .

6 24
623
5 99
5 68
5 47
55 1
561
5 99
629
6 13
5 26
4 34
42 1 e

45 5
446

It appears from Fi g I i n which or d i n ates represe n t tem

.

p e rat u r e s a n d abscissae perce n tage compositio n that the a n ti -

,

mo n y tellurium alloys belo n g to th e class i n which occur on e

-

or more defi n ite chemical compou nds a n d i n this respect are ,

similar to the lead telluriu m alloys The compo u nds i n this

-
.
 The A lloy s oj A n ti mony a n d Te ll u r i u m .

class of alloys are always i n dicated by a maximum poi nt i n

t he fusibility curve a nd by a u n iform field whe n exami n e d
-
,

u n d er the microsco pe I n this case it will be see n that the

.

m axi mum poi nt i n the curve correspo n d s to a freezi n g poi n t

'
-

of .
a n d a compositio n of per ce n t of tellurium and
of a n ti mo n y which i nd icates the compou n d Sb T e
, , ,
.

This com pou n d a ntimo n y telluride forms a eutectic alloy

, ,
°
v
c o n t ain i n g 8 7 per ce n t of tellurium a n d melti n g at 4 2 1 with ,

tellurium an d IS Isomorphous with a n timo n y co n seque ntly

, ,

does n ot form a eutectic with it This latter fact places the .

a n t i m o n y tellurium alloys i n the sub class of the third ge n eral

z - -

c l ass of alloys i n which on e of the compou n ds is isomorphous

w ith on e of the eleme n ts The p ortio n of the curve which .

c o n n ects the freezi n g poi n ts of a n timo n y an d a n ti mo n y tellu

- -

r ide is approximately a straight l i n e and co nsidered by i t

“

, ,

s elf represe n ts a n isomorphous mixture

, .

I n that part of the curve which is i n cluded betwee n 38 and

1 00 per ce nt of a ntimo n y we should expect to fi n d a nd do , ,

fi n d homoge n eous mixe d crystals of the pure a ntimo n y and '

, l 1

a n ti m o n y telluride The microscopic field bet wee n these two

.

poi nts for all alloys exam i n ed is very similar except where
“

t he perce ntage of a n timo n y is very high i n which case there

.
,

i s s ome te n de n cy for the telluride to segregate out i n masses .

The isomorphism of these two substa n ces seems all the ,

more probable whe n we co n sider the fact that the mi n eral

t etradymite B i T e crystallizes i n the rhombohedral system
, ,
.

It is more tha n likely that the a nti mo n y telluride if it occurred ,

a s a mi n eral would likewise be fou n d to crystallize i n that

,

system A lthough telluriu m crystallizes in the h exago n al

-
.

system also its cleavage i n dicates that it is n ot isomorphous

,

wi th a n timo n y an d co n seque ntly n ot with a ntimo n y telluride

,
.

T he questio n might arise as to the existe n ce of a compou n d

o f t he compositio n correspo n di n g to the formula S bT e A ll .

we c an say at prese n t is that there is n o evide nce in favor of

such a compou n d There are n o a p r i or i reaso n s why it
.

sh ould n ot exist an d it is e ntire ly possible that it Should ex

,

ist an d form an isomorphous mixture with a ntimo n y and

.
a n timo n y telluride S b Te If it were formed in this mixture
, ,
.
,

w e should expect a more marked evolutio n of heat i n the

1 00 Fay a nd A shley .

alloys correspo ndi n g to this compositio n but the amou nt of ,

heat evolved i n the alloy correspo ndi ng to this compositio n

was not above the average for the other alloys .

O p p e nh e im makes the stateme n t that a n timo n y forms eithe r

l
’

iro n gray SbT e or ti n white Sb T e 3 The o n ly evide n ce

-
, ,
-
, 2
.
,

however i n favor of the compou nd was that the iro n gray

,
-

mass was homoge n eous an d had cleavage pla n es The as .

sumptio n seems to have bee n b ased on a very small amou n t o f

evide n ce for the result of o ur work shows that with thes e
,

proportio n s an alloy is formed which although brittle homo , ,

g e ne o u s an d crystalli n e is merely a n isomorphous mixtur e

, ,

o f a n timo ny and a nti mo ny t rite ll u ri de .

Fro m an i n spectio n of the freezi ng poi n t curve it seems to -

be evide n t that a n timo n y an d telluriu m are n ot isomorphous ,

as has bee n ge n erally supposed a nd that co n seque n tly they , , ,

do n ot mix at the temperature of fusio n as such O n the .

co n trary telluriu m and a n timo n y telluride form a series o f

,

alloys which i n all respects is si milar to the class of alloys of

which the lead ti n an d Silver copper alloys are good exam
- -

ples In other words the freezi n g poi n t of either a n timo n y

.
,
-

t rite llu rid e or of telluriu m is lowered by the prese n ce of th e

other n o matter which o n e we co n sider as the solve n t They
, .

are mutually soluble a n d mix i n all proportio ns .

Pe r ce n tag e Composi ti on of the Con sti tu e n ts .

To express approximatel y the compositio n of a ny p artic u

l ar alloy a diagram Fig I I has bee n co n structed which , . .
, ,

wil l Show at a gla n ce the perce n tage of each co n stitue n t .

The abscissae represe n t the perce n tages of a n timo n y an d tel

l uriu m a n d the ordi n ates the divisio n of the total 1 00 p e r
,

ce nt of the alloy i n to perce n tages of tellurium an d eutecti c

alloy a n timo n y telluride and eutectic alloy or isomorphou s
, , ,

mixture of a nti mo n y an d j a n t i mo n y telluride For i n sta n ce .

,

a n alloy whose chemical compositio n is 4 0 per ce n t telluriu m .

a n d 6 0 per ce n t a n ti mo n y is made up of a mixture of 3 5 per

ce n t a n timo n y and 6 5 per ce n t a ntimo n y telluride A gai n if .

,

we wish to obtai n an alloy co n tai n i ng 34 per ce n t of eutecti c

a nd 6 6 per ce n t of a n timo n y telluride it is readily see n th at i t ,

1
J p k t Ch m 7
. ra 77 . e .
, 1, 2 .
102 Fay a nd A shley .

Bo de k e r an d as to G iesecke
at For the al loy :

co ntai ni n g 6 0 per ce n t of telluri um we obtai n e d Th e

results for the other alloys were as a w hole v e ry u nsati sfac , ,
.

tory an d the values give n i n the followi n g table are o n ly ap

,

proximate Som e of the alloys were so crystalli n e that it w as

. .

i mpossible to obtai n them free from air spaces I n certai n .

cases large drusy cavities were fou n d i n the ce n ter of an i h

,

got after weighi n g This te n d e ncy to form i ntercrystalli ne

.
’

cavities was especially m arked i n the alloys co n tai n i n g fro m

0 to 4 0 per ce n t of tellurium Beyo n d this poi n t there was a .

te n de n c y for the eutectic alloy to fill up these spaces as i s ,

show n i n Fig V where the eute ctic has flowed i n bet wee n
. .
,

the lo n g parallel crystals of a n timo n y telluride The crys

, .

tals i n this case are colored d ark o n accou n t of superficia l

oxidatio n but ord i n arily are almost silver white
,
-
.

Ta ble [L Sp e cifi c Gra vi ti e s of the A lloy s f A n ti mony and

’

—
o

( Show n graphically i n Fig I II ) . .

W e i gh t of p i me n T llu i um
s e c Sp e
. e r . cifi c g r avi ty .

G m ra Pe se nt
. r c .

1 1 00

1 90
o .
7 03 80
80
1 80
70
60
50
40
4 . 2 6 80 30
7 -7 4 4 5 25

20
2 .
5 0 14 10

( P u re an t i m o ny .
) 0

As the perce n tage of telluriu m approaches the amou n t

n ecessary for the eutectic alloy the structure is somewhat ,

micaceous some of the pla n es of fracture Showi n g a matt e

,

surface This micaceo us st ructure is respo n sible for a tur n

.

i ng over of e d ge a nd is very evide n t whe n o ne attempts to

,

pulverize a pie c e i n a mortar Most of t he other alloys show .

1 Th re e s p e ci me n s f o m on r e in g ot .
 fA n l i m on Te llu ri um
’
Tlze A lloy s o
y a na .

a rema rkable crystalli n e cleavage the surfaces of which are ,

very brillian t .

Both a ntimo n y a nd tellurium an d all their alloys have ap , ,

proximately the same degree of hard n ess somewhat above ,

2 5 ( mica ) an d decidedly lower tha n 4 ( fluorite )

. From 0 to .

2 0 per ce n t of tellurium the alloys closely resemble a n timo n y ,

.

Mi cr osco p i ca l E x a m i n a ti on of ! be A llo
y s .

The preparatio n of satisfactory samples for microscopic ex '

ami n atio n prove d to be very d ifii c ult O n accou n t of the .

highly crystalli ne character of some of the specime ns there ,

was a great te n de n cy for small fragme nts to split out alo n g

cleavage pla nes thus leavi n g a pitted surface By careful ,
.

treatme n t a fairly satisfactory surface could be obtai n ed by

21) m
Pe r l
4 0 Te lu rium 60
80 m om 60 W W
Fi g . I .
—
F re e z in gp
-
oi n t c ur v e o f th e a ll o y s o f a n ti mon y and te llu ium
r .

Te 0 10 30 80 90 100
‘
-
'
20 40 50 60 70
S
B 100 90 80 70 5° 50 40 30 20 10 0
Fi g II —
D i a g ra m s h ow i n g c o mp o s i t i o n o f c on s t i t u e nts o f th e a ll oy s o f a n ti m on y
llu um
. .

a n d te ri .
1 04 Fay a nd A shl e y .

first rubbi ng o n an oil sto n e u nder w ater the n polishi ng

-
,

lightly on a wheel with a mix ture of rouge and stearic acid ,

and fi n ally o n a piece of chamois stretched o n a woode n

block .

The process of etchi ng was likewise diffi cult H ydro .

chloric and n itric acids an d iodi n e were all u sed without a ny

appreciable e ffect The best results were fi n ally ob tai n ed by
.

electrolysis i n either dilute hydrochloric aci d or ammo nia .

The specime n to be etched was attache d to o n e of the poles

of a battery and a curre nt of about ampere was allowed to
pass for a fe w mi n utes The structure was brought out by
.

this mea ns but there was co nsiderable superficial oxi d atio n

,

which produced beautiful colored effects on the surface .

This dark e n i n g effect is well show n i n Fig V where the . .

,

crystals of s T e have bra n ched out through the eutectic al

3

loy Before etchi n g the whole surface was brillia n tly white
.
, ,

but after etchi n g the crystals were colored a bea u tiful blue
, ,

which i n some cases revealed the structure to the n aked eye

, , .

The alloys fro m o to 6 0 per ce n t of telluriu m w ere all richly

colored and showed u nder the microscope a u n iform crystal
,

li n e fiel d with th e si n gle exceptio n of the alloy co n tai n i n g 5

per ce n t of tellurium which was composed of ro u nded gra n
,

ules of a ntimo n y telluride e mbedded i n pure a ntimo n y A .

cross sectio n of a ny of t he se alloys showed bra n chi n g crystals

exte n di n g fro m the b ottom to the top of the i n got .

The alloy co ntai n i n g 6 1 3 7 per ce n t of tellurium prese n ted

.

an absolutely u n iform appeara n ce bei n g composed e n tirely of ,

the compou nd Sb T e an d is sho wn i n Fig IV The dark

,
. .

spots i n the photograph show the cavities produced as a re

sult of the crystallizatio n With a n i n crease i n the perce n t
.

age of tellurium beyo nd this poi n t the eutectic alloy of a n ti ,

mo n y telluride and telluriu m bega n to show I n alloy No . .

11, Fig V this is show n very clearly

. .
,
In this alloy lo n g .

crystallites of a ntimo n y telluride appear throughout the mass ,

and the space betwee n the separate crystals is filled with the

eutectic In this case the crystals are dark o n accou nt of the

.

superficial oxidatio n produced i n etchi ng .

Fig V I sho ws the appeara n ce of the eutectic alloy as i t

. .
,

was usually fou nd i n the allo ys co ntai n i ng from 6 0 to 90 per

 A ll Da r k ll it f n t i m n y t llu i d l i gh t
o e r e
Fi g V —
oy N o 11 c ry s ta es o a ,

( M gnifi d 95 d i m
. . . . ,

e ut e c ti c o f a n ti m on y te llu ri d e a n d t e llu i um
r . a e a e

te rs .
)

E u t e c ti ll Sl ow l y l h h hyd hl
c oo e d e tc e d w it ro c o ri c
Fig . VL — c a oy .

a c id . ( Ma g ni fi e d 9 5 di a m e t e rs .
)
ce nt of tellur i um In slowly cooled alloys the structure was
.

i nvariably the same but more rapid cooli n g produced an e n ,

t i re l y di ffere n t appeara n ce Fig V I I represe n ts a photograph . . .

of the pure eutectic prepared from several other alloys by ,

pouri n g off the still liquid m ass after a p art h ad soli d ified .

The photograph represe n ts a surfac e which had bee n cast on .

glazed porcelai n an d was ta k e n j ust as it appeared after cool

,

i ng without any further treatme n t

,
The light backgrou n d is .

tellurium and the dark portio n s are a n timo n y telluride The

, .

latter was probably brought out i n such great co ntrast on ao

cou n t o f its extreme te nd e ncy to ox idize .

Fi g VI I I sho w s the u sual appeara n ce of the all oys c on

. .

sisti ng of the eutectic a n d an excess of tellurium .

It is proposed to study in the same m a n n er other bi nary

alloys of tellurium an d subseque ntly some of the ter n ary al ,

loys .

C ont rib t i ons frou m t he Sh e l

ffi e d L aborat ory of Y al e U niv e rs i t y .

XC '
.
—
E L E C T R O A FFI NIT Y A S A B A SI S FO R T H E
-

SY ST E MA TI Z A TI O N O F I N O R G A N I C C O M
P O U ND S .

BY JA M E S L ooms .

1
In article published a short time ago A begg an d
an ,

“ ”
Bod land e r develop the co n ceptio n tru e electro affi n i ty -
,

which they defi n e as the stre ngth of u nio n betwee n an i o n and

electro n or the i nte nsity with which an i on holds its charge
,

of positive or n egati ve electricity

'
They the n attempt to .

sho w th at certai n properties a n d reactio n s of i n orga n ic salts

are directly depe nde nt upo n the electro amn itie s of the re Sp e c -

tive n egative an d positive io n s These properties are e s .

,

p e c i ally ( 1 ) solubility an d the te n de n cy to form complex ( 2 )

, ,

positive and ( 3 ) n egative io n s

, .

( 1 ) Solu bilifi The authors assert as a ge neral law that

.
—
, ,

the greater the electro afi n ity o f a positive or n egative ion -

,

the greater will be the solubility of its salts The state .

me nt is modified however by the additio n al law that whe n

, , ,

the electro affi nity of on e of the io n s is very great and that of

-
,

g C h m 2 0 45 3
1 Zt h nsc r . a or . e .
, , .
1 06 L oche .

the other small the i n flue nce of the first will overcome that of
,

the seco n d and the salt of the two will be soluble

, In c on .

formity with these la w s salts yi eldi n g sodium io ns the elec

, ,

tro afli n it y of which i s very great are i n almost every case

-
,

soluble i n water Salts yield i n g silver io ns which have a very

.
,

low electro affi nity are on the other ha n d ge n erally i nsolu

-
, , ,

ble B ut silver n itrate i n asmuch as the electro afli n ity of th e

.
,
-

N i o n is exceptio n ally high dissolves readily I n cases , .

,

ho w ever i n which the electro afli n ity of both the positive an d

,
-

n egative io ns is high the reverse order seems to be fol

,

lowe d an d the salts become i n such cases less soluble tha n

,

whe n the value for o nly o n e of the io n s is great That this .

would n ecessarily be so is i ndicate d i n the fact that for io ns of

very small electro affi n ity the i n flue n ce of the latter upo n th e
-

sol ubility i n creases more rapi d ly tha n do the electro affi n it ie s -

themselves A s a n approximate measure of the electro a mn i

.
-

ties we may take the decompositio n voltage of the salts

, .

The effect of cha n ge i n electro afi ni ty may the n be see n i n a -

compariso n of the de c ompositio n voltage values for zi n c an d

silver For si lver i n volts it is
.
, (H o) for zi n c it
, ,

is +o 7 4 The i n crease of
. . volts i n passi n g from silver ,

to zi n c i ncreases the solubility of the chlorides by the mil

,

lio n fold
-
The decompositio n voltage of sodiu m is about
.

a nd at the same rate of progressio n therefore the solu , ,

bili ty of sodium chloride would be somethi n g like

gram molecules per liter Si n ce work c an be gai n ed on the
-
.

dissolvi ng of a salt i n water a salt of such solubility would ,

have too great a supply of e n ergy to be stable at all T he a u .

thors assume th erefore that it passes i n to a modificatio n with

, ,

far less e n ergy which accordi n gly does n ot admit of compar

, , ,

iso n with the zi n c an d silver salts This is an exceedi ngly .

i mporta n t hypothesis witho ut which the theory coul d n ot

,

sta n d for an i n sta n t .

( )
2 F or m a ti on f
o Comp l e x Ion s A begg a n d B o d l a n d e r de .

fi n e a complex compou n d metallo ami n es double salts etc — -

, ,
.

as follows
C omplex compou nds are those i n which o ne of the io n oge n ic
co n stitue nts is m ade up of a si n gle i on capable of i n depe nde n t
108 L ocke .

these exte nsio n s of the theory I will retur n at a later poi nt .

The properties of the sodium salts may be briefly summa

r i z e d as follows

1) S olubility i n water .

( 2 ) N on e n tra n ce i nto the n egative complexes of double

-

salts .

3 ) N on e n tra n ce i n to complex catio n s such as metallo

-
,

ami n es .

( 4 ) Stability o n ig n itio n or passage thereo

,
n i n to a n other
salt n ever i n to the oxide
,
.

These collective properties apply to almost every sodium

salt k now n a n d by their applicatio n the behavior of each s in
,

gle salt is roughly described For i nsta n ce si n ce sodium .

,

does n ot e n t er i n to complex a n io ns its chloride is less sol ,

uble i n hydrochloric acid tha n i n water P otassium salts .

,

like those of sodium are soluble i n water a nd si n ce

, ,
»

i n showi n g this o ne property they exhibit i n about the same

,

degree all the others commo n to the sodium compou nds it ,

must be co n cl uded that these properties are not i n depe n de nt

of o n e a n other but correlated an d due to o ne an d the same
,

ultim ate cause The same is true of the silver a nd cuprou s

.

compou n ds I n so far as they are capable of existe n ce th e

.
,

cuprous compou n ds i n exhibiti n g a si n gle ge n eric property

,

commo n to silver compou nd s co n form to the latter i n all their

,

ge n eric reactio n s exclusive of those of oxidatio n

, .

A n y theory which bri n gs to the fro nt a cause to which these

properties m ay be d ue m ust be of the greatest service to the
,

scie n ce This the theory of A begg an d Bod lan d e r i n part at

.

tempts for it refers each of the properties e n umerated i n di

, ,

re c tl y that of stability o n ig n itio n as well as the others to t h e ,

ap proxim ately equal val ues of the electro afli n i tie s of the -

metals i n the sodium group an d silver group respectively .

But as a direct seque n ce of the th eory these properties shou l d

always go ha n d in ha nd with o ne a nother E xceptio ns i n .

regard to the solubilities of a few i n dividual salts c an be ex

plai ned as the authors have explai ned the relative solubility
of sodium chloride an d zi n c chloride B ut an y i n sta n ce i n .

which one ge neric property of let us say silver salts is show n

, ,
 E l e ctr a- A tii n i ty .

2 72 e x te n soby the compou n ds of a metal whe n they have not ,

the remai n i n g ge n eric properties of silver salts must be r e ,

garded o n ly as a flat co n tradictio n of the theory an d re n der ,

its admissibility at least very doubtful This is especially .

true i n a case i n which the electro a fli n ity of the metal ap -

ro x i m at e s that of silver
p .

The electro afli n ity of thallous thallium is very small and

-
,

this fact is used by the authors to explai n the slight solubility

of thallo us hal ides In additio n to the iodide the sulphide .
, ,

chromate dichromate sulphocya n ate va n adate hy p 0p hos

, , , ,

phate ferrocya n ide an d other compou n ds are practically in

, ,

s oluble i n water These are also the most d iffi cultly soluble
.

silver salts The sulphite thiosulphate triorthop hO Sp h ate

.
, , ,

chloride bro mide an d ma n y others dissolve o n ly slightly

, , ,
.

The solubility in ge n eral is somewhat greater tha n that of

, ,

silver salts but less tha n that of zi n c a nd cadmi um com

,

pou n d s ; an d thallium i n accorda n ce herewith has a much , ,

lower electro affi n ity tha n have these metals Now both zi n c
-
.

a n d cadmium yield do uble salts i n which they form p art o f

‘

the n eutral compo n e n ts They form metallo ami n e s complex .

- —

positive io n s in great ple n ty a n d of much stability Ho w

—
.

much more readily therefore should such salts be formed by , ,

thallium which i n the m atter of electro a ffi n ity is n earer

, , ,

silver an d which like the l atter m etals forms spari n gly sol
, , ,

uble salts Not a si n gle metallo ami n e of thallous thallium

.
-

h as ever bee n prepared Thallous chlorid e is far less soluble .

1
i n chloride solutio n s the iodide i n iodide solutio n s tha n in , ,

water Were it not for a complex thiosulphate and sulpho

.

cya n ate we might j ustly say that the power of thallium to

,

e n ter i nto double salts is absolutely n i l A double salt of .

thallium with on e of the weakest a n io n s S ca n n ot be o b ,

“

t ain e d eve n i n the dry way .

We have here therefore two of the three ge n eric properties

, ,

of salts of a m etal with lo w electro afli n ity almost e n tirely ab -

se n t the formatio n of complex catio n s an d complex a n io n s

—

while the third spari n g solubility is prese nt in full force N or

, ,
.

is this the o n l y refractory case There are almost as ma n y .

others as there are eleme n ts an d on e or two of these I m ay ,

1 N y o Zt h
es : ph y C h m 9 6 6
sc r . s. e .
, , 0 .
 L ocke .

touch upo n briefly I t will be see n that while the salts of .

metals of the same vale nce can almost always be divided i nto
groups accordi n g to their ge neric properties as above we do , ,

n ot n ecessarily fi n d the same properties i n correlatio n A .

te nde n cy to do uble salt formatio n does not i n the least n e c e s

sitate a te n de ncy to form complex catio n s nor does ge n eral
slight solubility i n water n ecessitate the formatio n of either
1
a n io n s or catio ns of complex n ature .

Dividi ng the metals i n to groups accordi n g to their vale n ce ,

the authors state that their electro afi n itie s lie i n ge n eral i n -

, ,

the same order as the positio n s of the eleme n ts i n the periodic

system In the d i ffere nt families the electro affi n ities i n crease
.
-

with i n creasi n g atomic weight The series C u A g A u an d .

‘
, ,
‘
,

Zn C d H g
,
“
follow the reverse order While direct meas
, , .

u re m e n ts are i n most cases wa nti n g this arra n geme n t is obvi ,

ous fro m the solubilities stre ngth of acids and ge neral chem , ,

”
ical behavior A s has bee n stated the electro afli n it ie s may
.
,
-

be roughly measured by the decompositio n voltage of the

metals To show the relative mag n itudes I i n clude some
.

of these values i n the followi n g table

Li Be F
P
K Ca As
Rb Sr Sb (
Cs Ba

Furthermore , for members of the eighth family we have ,

Fe n
Ni Co +o . 22

The decompositio n voltage of the alkali n e earth metals has

n ot bee n determi n ed but it is u n doubte d ly higher tha n that ,

of mag n esium an d less tha n that of so d ium ,

.

Th at th e e l e t o
1 c h e o y re qui r th i s o l ati n n e v rth l e i s s h w
r -
‘
a i n i ty t
fl r e s c r re o , e e ss , o n

b y A b e gg a n d Bod l an d e r t h e m s l v e s T h e i n s t n c e f pl a ti ni c pl ati n um i s c i t e d a s
e . a o

a n e x c e p ti on i n t h t w h i l e y i e l di n g d o u b l e
a l ts in bu n d an e i t f r m s m ta llo m sa a c o e -a

i n e s w i t h di ffi ul ty Th e y e xpl ai n t h i s by th e ass ump tion t h t th e pl ti nic i o n s so

c . a a i

w a k th a t i t
e n h d l y e x i t e v e n w h n s t r n gth e n e d b y t h e a d d i ti on f N H Sm l
ca ar s e e o o e

c ul e sTh i s d i ffi ul ty h ow e r m y a i l y b e o e rc o m e b y c n id e i n g n l y c s s
. c , e v , a e s v o s r o a e

i n w h i c h t h e m e t a ll ic i on s r e e as i l y c p ab l e o f i n d e p e n d e n t e x i s te nc e e g Ba +
a a — . .
,

Z n+ e tc .
1 12 L ocke .

the compou n d A mmo n ia ad d itio n products c an -

be obtai n ed o n ly i n the dry way an d these break dow n com ,

p l e t e l y i n to salt a n d ammo n ia i n prese n ce of water .

The solubilities of the salts of mag n esium ma n ga n ese fer , ,

rous iro n nickel cobalt copper a n d cad mium are qualita

, , , ,

t iv e l y almost exactly the same as those of zi n c compou nds ,

though i n the matter of d ecompositio n voltage the metals

ra n ge from to + o 2 2 H ere i n the matter of solu . .
,

bilit y we have qua ntitative data which c a n be compared di

,

re c tly with the electro a fli n i t i e s or with the decompositio n

-
,

voltage values which ro ughly measure the latter The sol

, .

u bilit i e s of the n itrates M( N at

,
expressed i n
gram molecules per liter of solve nt are as follows
-
,

Sol ubil
l tl e S
Volt
age
There c an be n o questio n here as to whethe r a relatio n ex
i st s betwee n solubility a n d d ecompositio n voltage Mag ne .

sium n itrate i n stea d of bei n g the most soluble is w ith o n e

, , ,

exceptio n the least so C upric n itrate is the most solubl e

, .
,

with on e exceptio n an d copper has by far the lowest d e com

,

positio n voltage an d electro afli n i ty -

.

I have determi n ed the solubilities of the isomorphous double

sulphates of the formula with similar c on
t rad ic to ry results Not o n ly is the ord er differe n t from that
.

of the decompositio n volt age values but from that of the n i ,

trate sol ubilities as well For the ammo n iu m salts at .

,

the solubilities are as follows

Mg . Cd .

+o .
33

For the discussio n of these figures su ffi ce it to poi n t out ,

that the solubility of the n ickel salt is one third that of the -

mag n esium compo und while the di ffere n ce betwee n the de

,

compositio n voltages of th e two metals is about the same as

that which causes the differe n ce i n solubility of zi n c chloride
Fu k g Ch m n
1 h
Ztn n sc 393 f f
r. a or . e .
, o. , . .
 E le c tr a A gfi n i ty -
.

an d silver chloride ( see above where the stateme nts are a more ,

or less literal tra nsl atio n of the author s words ) an d that a l

’

thoug h the coppe r salt by a n alogy should be about as solu , ,

ble as silver chloride it too is three times as soluble as the ,

n ickel salt .

In spite of the fact that the salts of these metals are i n ,

ge n eral more soluble in w ater tha n those of the alkali n e

,

earths and the latter e n ter i n to n o complex io ns we have i n

, ,

this group stable o r u nstable co mplex io ns of either positive

or n egative n ature The double cya nides of all except mag .

n e si u m are i n fact very stable i n deed Double chlorides .

,

bro mides iodides exist i n great abu n da nce Stable complex

, , .

ami n es are k n ow n of all th e heavier metals of the group and ,

i n co n ce n trated ammo n iacal solutio n mag n esium probably

1
forms them to a marked exte n t as well These metallo .

ami nes however show like the double salts n o gradatio n i n

, , , ,

accor d a n ce with electro affi n it i e s a fact observe d an d com -

,

m e nte d upo n by D awso n an d Mc C rae

2
These i n vestigators .

fou n d fro mmeasureme n ts of distributio n co n sta n ts on ammo

n i ac al solutio n s co ntai n i n g salts of n ickel copper zi n c a n d , , ,

ca d mium that the te n de n cy to form complex io n s is ab out

,

the same for all although the decompositio n voltage of the ,

metals ra nges from to

The thallous salts as has bee n see n show the spari n g sol , ,

u bi l i ty which is i n co n formity with the l o w electro affi n ity of -

thallium while i n other resp e cts they approach the salts of

,

the alkali metals an d have properties ex actly the reverse ,

of those which we woul d expect The zi n c salts o n the .

,

other ha n d althou gh the electro afli n ity of zi n c is likewise

,
-

low are mostly very soluble ; but the n they co n form to its
,

mag n itude i n yieldi n g both positive an d n egative complex

i on s To touch briefly upo n the trivale n t m etals the salts of
.
,

alumi n ium and iro n with wea k acids so far as they have bee n ,

obtai n ed are as a rule ; i n soluble bo d ies They also form

, , .

double salts with read i n ess i n co n formity with the low elec ,

tro afi n itie s of the metals B ut n o positive complex io ns of

-
.

these metals are k n ow n A mmo nia simply precipitates the .

1 U pu b l i h
n s e d e xp e ri m e nt s o f th e a u th or .

2 Z tsc h r . a n o rg . Ch m 2 6
e , 99 .

8- 2 7
1 14 L oche .

hydroxides T here may be a few cases in which the three

.

properties called for by the theory go ha nd in ha nd and these ,

A begg an d Bodland e r have sought out and used with great

dexterity But i norga n ic chemistry is not the chemist ry of
.

sodi um and silver alo n e .

Double Sa lt For ma ti on F0r the purpose of discussio n we .

-
,
1
may divid e double salts i n to three classes 1
A . Salts the complex io ns of which are not appreciably
,

decomposed i n solutio n .

B Salts the n eg ative io n s of which dissociat e to a very

.
,

marked exte nt but which are obtai n ed by crystallizatio n fro m

,

solutio ns co ntai n i n g equivale nt qua ntities of their molecular

co n stitu e nts .

C Salts almost completely dissociated li k e the last but

.
, ,

which form o n ly whe n on e of their co n stitue nts is prese nt i n

excess .

A ccordi n g to the vie w of A begg a n d Bod land e r the weaker ,

the an io n of a double salt is the more readily will it see k to ,

stre ng the n i tse lf b y the a ddi tion of a n e u tra l compon e n t Re .

ferri n g for the mome n t o nly to the double salts the si ngle ,

io n s of which are u n ivale n t w e see that i n the compou nds of ,

class A this seems to be true The most freque n t doubl e .

salts of this class are the complex cya nides the n eutral com ,

p on e n t s of which are i n soluble i n water This latter fact is .

i n accord with that part of thei r theory which states that the
s trong e r the a n i on i s the more sol u ble w il l be the salt B ut the .

authors seem to have absolutely lost sight of this feature of

their theory i n its applicatio n to the u nstable double salts of
class B the existe nce of every member of which is i n direct
,

co ntradictio n to it If the a n io n of a chlori d e is stre n gthe n ed

.

by the additio n to it of a n eutral chloride the n the resulti ng ,

double salt should be more soluble tha n the simple chloride

itself P rofessor H L Wells and his c o workers in this
. . .
,
-

laboratory have fo u nd i n lo n g i n vestigatio n s of do uble caes

, ,

ium halides that hardly a si ngle such salt if any at all is

, , ,

more soluble tha n caesium chloride alo n e I have fo u n d that .

2
i n the case of the alums where the electro affi ni ty of the ,
-

1 W ll eTh i J O U N L 6 389
s s R A , 2 , .

2 Ibi d . 2 6, 1 66 .
,
 L ocke .

of the solubility product is therefore due e ntirely to this fact

-
, , ,

an d the solubility of the u ndissociated alum correspo n di ngl y

small .

The same co n clusio n must be reached if we regard th e

double salt as resulti n g from the prelimi n ary formatio n of its .

complex io ns for the co nce ntratio n of the latter an d there ,

fore the solubility product as well must h ave at least an ex

-
, , ,

tre me l y low value .

But while the caesium double salts are probably i n every ‘

case less soluble i n water tha n the simple caesium salts i n ,

co n tradictio n to the theory the relative solubilities of do ubl e

,

salts of this metal as compared with iso morphous compou n d s

,

of the remai n i n g alkali metals an d ammo n ium and thalliu m ,

show no strict regul arities I n the case of the double halides

.
, .

it has ge n erally bee n fou nd that the Solubilities decrease from

potassium to caesium B ut with double sulphates n o defi nit e
.

order is retai n ed throughout di ffere n t salt series This is illus .

t rate d for i nsta n ce i n a compariso n O f the alums an d doubl e

, ,

sulphates of the type at 2

M C r ( SO 4 ) 2 1 2 H20
l .

K Cs
N H, N H4
TI K
Rb Rb
Cs Tl
There c an be n o thought here of a co n formity to an y on e o f
the laws proposed by A begg an d Bod lan d e r The relati vely .

great solubility of the thallium alums i n Spite of the low ,

electro affi n ity of thallium is O pposed to them i n the o n e i n

-
,

sta n ce an d i n the other absolutely n o suggestio n of grada

tio n accordi n g to the theory c an be fo u nd .

The further exte nsio n of the theory is so i n defi n ite a n d

faulty that on e c an hardly tell where to begi n stil l m or e ,

where to leave off i n criticizi ng it The authors go beyo n d

, . .

th e defi n itio n of complex compou n ds cited above i n i n c lu ,

d i n g amo n g t h ese the acid salts ou the on e ha n d an d basic

salts o n the other In these cases the n eutral compo n e nts are
.

replaced by the io n oge n ic compo n e n ts H + an d ( O H ) As ,

a n i n sta n ce of the stre n gthe n ed n ature of the resulti n g c om

 plex i on the i n crease i n solubility of acid salts over n eutral
,

s alt is cited e g bariu m acid s ulphate barium acid phos

. .
, ,

p hate barium acid carbo n ate etc

, The metallic io n s i n , .
,

a n alogy must be str e ng the n e d by the additio n of hydroxyl

,

groups A re basic salts the n more soluble tha n the normal

.
, ,

c o mpou n ds ? It is diffi cult to u n dersta n d how any on e who

has ever partially n eutralized a copper n itrate solutio n or
.

w h o has eve n ever see n a reaso n abl y old solutio n of ferric

chloride c an make such a n assumptio n
, .

A great ma n y compou n ds are cited with refere nce to on e ,

p roperty or a n other by A begg and Bo dlan de r A t least as,

.

m a n y as o n e half their examples if observed with refere nce to

-
,

-
a n y other properties th a n those chose n would be flatly c o n ,

t r a d ic tory to their views For i n sta n ce the chlorate i on .

, ,

C 105 is the chlori n e ion C l stre ngthe n ed by oxyge n as a ‘

, , ,

n eutral c o mpo n e n t Ma n y chlorates are therefore more sol

.
, ,

u ble tha n the chlori d es The periodate i on is the iodi n e ion

.

s tre n gthe n ed i n the same ma n n er P eriodates must there .

,

fore be more soluble tha n io d ides !

, The very weak ion
H g + stre n gthe n s itself by the additio n of a n other H g thus ,

formi n g the much stro n ger mercurous io n A re

the n the mercurous salts more soluble tha n the mercuric
The physical chemist is n ot the o n ly one who regrets the
more or less tardy accepta n ce of the n ewer theories by the
teachers of i n orga nic subj ects There are ma n y of us whose .

li n e of study lies wholly i n i norga n ic fields who are willi n g ,

a nd a n xious to do such missio n ary work as we c a n for the

e xt e n sio n of those theories But the publicatio n of such .

speculatio n s as the above by me n promi ne n t in the physico ,

~

c hemical world does n ot materially assist toward that e n d

, ,

for it n aturally raises doubts as to the accuracy and ra nge of

o ur colleagues k n owledge of practical chemistry It is as a
’
.

p rotest i n the n ame of that practical experime n tal chemistry , ,

z t h a t the above criticisms are submitted .

N E W H A VE N , D e c e mb e r , 1901 .
 C ON STIT U TIO N o r P H E N YL U R A Z O L E

BY S. F A GR
. E E .

l
P he ny l uraz ol e
was first m ade by P inn e r and several deriv ,

atives have bee n described si nce the n but the co n stitutio n o f ,

n o n e of these compou n ds has bee n determi n ed Various for .

mul as have bee n suggested for phe n y luraz ol e itself and i t ,

m ust have o ne of the followi ng ,

0, H, N —
N C 6 H5 N —
N c , H, N -
N H

HO C COH

(I) (2 )
C , H, N —
N H c, H, N -
N H

(9 00 C O H o)

It will be show n that formula V is the o n ly on e that h ar .

mo nizes with the results obtai n ed .

In desig n ati n g the positio n of the groups attached to the

urazole ri n g we shall make use of the system n ow in vogue ,

n umberi n g the five atoms i n the ri n g as follows ,

( 1) (2 )
CsHsN —
NH

( 5 ) 0C CO H (3 )

A substa n ce with this formula has the ame 1 phe nyl 2

n - -

hydro -
3
-
hydroxy -
5
-
o x y u raz ole . A substa n ce with the for
mula
1 P inn e r : Be r d
. . c he m . Ge s .
, 2 0 . 2 36 0 ;
120 A cre e .

H e n ce formula IV is excluded .
, and p he ny lu raz ole has the
formula V .
,

C , H, N —
N H

00 00 11 ,
V7
\

or is 1 phe n yl 2 hydro 3 hydroxy 5 ox y u raz ole

- - - - - - -
.

The silver salt beyo n d questio n has the formula

, ,

0, H, N —
N H

00 C OA g .

Whe n treated with ethyl iodide in absolute ether in the cold ,

it gives the 1 phe n yl 2 hydro - - -

0, H, N -
N H

00

i n soluble i n alkalies The imide = N H group of a urazole or

.

triazole ri n g is not acid e n ough or does not give e nough hy ,

-

droge n io ns to form n eu tral salts i n a water solutio n The

, .

n eutral salts of these u raz ole s have the metal combi n ed with

oxyge n formi n g the group

, an d o n ly whe n

we have an imide group n ext to a carbo n yl group as

—
N H —
CO —
N _

l
can we have these n eutral salts formed Wheeler has made .

the isomeric compou nd with the ethoxy group at 3 a nd it is ,

soluble in al k alies as we should expect formi ng the salts

, ,

0, H, N —
N

MO C

an d is precipitated by stro ng acids . Whe n the isomeric

1 W h e e le r : J . A m C h e m So c
. . .
, 1 900 , p .
37 7 .
 Consti tu tion o f P he ny l u ra z ole .

5-
ethoxy compou n d is ma d e it will doubtless have a ci d prop
e rt ie s formi n g the salts
,

0, H, N —
N

0, H, 0 —
0 CO M .

Whe n the sodium or silver sal t of is treated p h e ny l uraz ol e

with methyl io dide i n alcohol at derivative °
1 00 C a N methyl .
-

° °
havi n g the melti n g poi n t 1 8 3 to 1 8 5 is formed which is not
-
,

affected by evaporati n g with co n ce n trated hydrochloric acid .

This compou n d is doubtless i d e n tical with the m e thy lp he n y l

urazole m elti n g at 1 8 3 to
, made by B usch an d H ei n
°

1
richs by the actio n o f n itrous acid o n 1 phe n yl 2 methyl 3 5
,
- - - -
,

oxy 4 aminou raz ol e These writers ascribed the isomeric u ra

- -
.

zi ne formula ,

0, H, N -
N
\00 0H
H —
N —
N —
H
to this ami n o body but this is clearly wro n g for two reaso n s
, , .

First such a urazi n e should be soluble i n alkalies while their

, ,

compou n d w as i n soluble this we should expect if it had the

above urazole formula Seco n d ly it co uld n ot be a m ethox y
.
,

”
derivati ve for both their so called urazi n e an d the phe n yl
,
-

m e thy lu raz ol e made from it are very stable to w ards acids

( hydrochloric acid ) .

The isomeric 1 phe n yl 4 m e thy l uraz ole was made by a

- - -

method which co uld n ot give the 2 methyl co mpo u nd Whe n -

.

p h e ny lse mic arbaz id e i sheated with m e thy l ac e ty lure a to 2 00 C

°
.

the reactio n may be represe n te d by the followi n g

0, H , N

C H , C O N H § CO 00

C HsN
' '

ii N H
g ,

°
This compou nd melts at 225 a nd is stable to ward co n ce n tra
ted hydrochloric acid at So ph e n y luraz ole upo n alk y la ,

1 Bu s c h and H e i n ri c h s Be r d. . c he m . Ge s .
, 3 3 , 45 5 .
12 2 A cre e .

tio n by mea n s of potassium hydroxide an d methyl iodide ,

gives 2 alkyl derivatives a nd we shall use this method to

-
,

prepare other homologues .

It might be thought surprisi n g that i n the alkylatio n of

p he ny l uraz ol e by potassium hydroxide and methyl iodide n o
methylatio n takes place at 4 .

0,H, 1 H
0, , c / 5
A gI
\O A g \0
.

Here we have alkylatio n on the n itroge n which is doubly

li nked to the = C O M group and this reactio n was formerl y 3
,

thought to depe n d upo n the additio n of methyl iodide to the

double bo nd and a subseque nt lo ss of sodium iodide
N H C H,

6 6
C Hsl CsHsC —
I

ON a

N H CH
6 5

4
N et has rece n tly show n that in all cases of methylatio n by
1 Wh l Th i J U N L 2 5 6
ee er s O R A , 0, a.
9 Wh e e l e r I bid .
, 2 1 , 1 85 .
1 N e t A nn . Ch me .
( L i e bi g ) , 2 66 , 62 2 80, 2 87 .

4 N t I bid 12 6
e : .
, 3 09 , .
124 A cre e .

From the be n ze ne sol utio n there is obtai n ed an oil havi ng the

co n stitutio n
0, H, N —
N H

00000H, .

This on boili n g with alcohol a few mi n utes or on sta ndi ng

, ,

i n water solutio n gives pure p h e ny l uraz ole melti ng at

, ,

The iso meric 2 ac e ty lphe ny l uraz ole is formed by the actio n of

-

acetic a nhydride on p h e n y l uraz ole an d is purified by crystal

l iz at i on from water and alcohol and the n eutral di acetyl ,
-

1 p h e ny l u raz ol e is so se n sitive to the actio n of water that it

-

must be crystallized fro m some solve nt like be n ze n e Whe n .

crystallized fro m hot water it loses the O acetyl g roup at 3 to -

1
give the aci d 2 N acetyl 1 ph e n y l uraz ol e
- -
This is a fi n e ex
- -
. «

ample showi ng how much more stable the N ac y ltri az ole s

,
-

u raz ol e s etc ,
are tha n the O derivative s Bailey an d A cree
.
,
-
.

showed that most of the 3 hydroxy 5 alk y ltriaz ole 1 propio n ic - - - - -

acids have the e n ol structure With diazometha n e they give .

m e thox y tri az ole s which give methyl chloride whe n treate d

,

with co n ce n trated hy d rochloric acid H e n ce we shoul d ex .

pe e t their O acetyl an d be n zoyl derivatives to be readily hy

-

d roly z e d by hot water an d this is i n deed the case , Whe n .

the 3 o x y a c e ty l 5 sty ry ltri az ole 1 propio n ic acid melti ng at

- - - - -
,

or ethyl 3 ox y ac e ty l 5 p h e n y 1tri az ole I propio nate

- - - - -
,

which melts at is boiled o ne hour with 7 5 per ce n t alco

hol an d the so lutio n is cooled there is obtai n ed a precipitate ,

of the pure 3 hy d roxy 5 sty ry ltri az ol e 1 propio n ic acid which

- - - - -
,

melts at or ethyl 3 hydroxy 5 p he ny ltri az ole 1 prop ion - - - - -

ate which melts at

, respectively showi ng that there is ,

co mplete hydrolysis of these acyl derivatives .

°
R upe an d L abh ard t fou n d that 1 phe n yl 5 ox y ac e ty ltri - - —

azole by evaporatio n with alcohol loses the acetyl group and

gives the 1 phe nyl 5 ox y tri az ole
- - -
,

1Th i l nd S h l u
e e a A n n C h m ( L i bi g )
c e ss n e r :
95 7 . e . e , 2 , 1 1 .

2 B i le y nd A r e B
a a c e e r. d, ch e m G e s 3 3 15
. .
, , 20 .

3 R up e a n d d c h e m G e s 3 3 2 33
L b h dt a ar : Be r . . . .
, , .
 Con sti tution o f P he ny lu r a z ole .

C GHsN — m
N

°
which melts at 1 7 8 to without doubt the acetyl was
j oi ned to the oxyge n at 5 .

l
B ain s attempted to prepare i so ac y l u re as of the type

RN
COCOR

by the additio n of acetic acid etc to o c arbod itoly li mide ,

.
,
-
.

I n stead the product of hydrolysis o car btol uid e

, ,
-
,

w asobtai n ed as the i ntermediate isoac y lu re a is too easily

,

hydrolyzed N be nz oy ldiph e ny l ure a

.
-
,

C 6 H5 C O

0, H, N
on the other h a n d is very stable toward alcohol an d water
, .

”
Dr J H R a n som of P urdue U n iversity writes me that
. . .
, ,

whe n he boiled N be n z oy l c arbo n y l o ami n ophe nol for on e

- - -

hour with water the u n cha n ged body which melts at

, ,

was recovered .

—
CO
In ace ty l isat i n I the acetyl is so firmly
CO

—
C OC H,
’
bou n d to the n itroge n that it gives ace t y li sat ini c acid ,

—
COC OOK

-
N H 000H ,

1 D ai n s : J . A m . Ch m
e . So c . , al , 1 36 .

1 R an s o m Th i s JO U R N A L
: , 2 3, 2 0.
3 B ae y e r and O e k onomi d e s : Be r . d . c he m . Ge s .
, 15 , 2 100 .
126 A cre e .

whe n treated with potassiu m hydroxide solutio n r Be nzoyl .

-

a pyrido n e whe n boiled with hydrochloric acid

-
,
gives ,

C GHSC O N H C H CH —
C H z C HC OO H .

From these facts it is evide n t that the N acyl derivatives of -

u raz ole s triazoles etc or an y compou nds with the group

, ,
.
,

—
CO —
N H —
N

are much more stable tha n the O acyl derivatives the latte r -
,
‘
bei n g readily hydrolyzed gby alcohol or water as most other ,

acid a n hydrides are .

'

The p he n y l u raz ol e used for this work was prepared by the

actio n of alkalies o n the d icarbe thox y ph e n y lse mic arbaz id e ,

which substa n ce was obtai n ed directly i n two modificatio n s .

O n e modificatio n has the melti n g poi n t the other the -

,

melti n g poi n t -
Whe n the product melti n g at 1 7 2 is re °

crystallized from water several times the melti ng poi n t is lo w -

ered to a n d this form whe n coole d melts agai n at , ,

°
A sample of this pro duct melti n g at 1 5 4 was mixed with a
°
sample of the pro d uct melti n g at 1 5 4 which was obtai ned di
re c t l y but there was no cha n ge i n the melti n g poi n t
,
-
.

Whether we have her e the e nol and keto tautomerism

described by C laise n Wislic e n us G utzeit B ailey and
3
,
1
,
2
,
4
A cree a nd others must be decided by further work
, , .

Work is now bei ng carried forward o n urazole and thio

urazole I propio n ic acids with Dr J R B ailey of Texas an d
- -
. . .
, ,

o n 1 phe n yl
- d i thio uraz ole s an d 1 phe n yl 3 ( or 5 ) thio 5
- - - -

( or 3 ) o x y u r a
-
z ol e s i n this laboratory We shall especially .

i n vestigate the molecular co nductivities of these compou n d s

a n d their salts We ask that this work be left to us
. .

E XP E R I ME N T A L .

P he ny lse mica r ba z ide This substa n ce was prepared accord .

—

i n g to Wi d man s method
5
To 2 0 grams phe n ylhydrazi n e ’
.

°
a n d 1 5 grams acetic acid i n 2 5 0 00 water kept at 5 was added
‘

—
.

C l i n A n n C h m ( L i bi g ) 7 7 88 ; 9 5
1 a se . e . e , 2 , 1 2 1, 2 .

Wi s l i c e n u s
'
2 I brd 2
: .
, 9 1, 147 .

3 u
G tz e it : Be r . d . c he m . Ge s .
, 2 6, 2 7 95 A nn . Ch m e .
( L i e bi g ) , 61, 1 08 .

4 B ai l e y a n d A c r e e Be r d c . . he m . Ge s .
, 33, 15 20 .

5 Wi d m a n : [bi d 26 2 6 13
.
, , .
128 A cr e e .

i s d iffi c ultly soluble i n cold water an d ether but rea d ily solu ,

ble i n hot alcohol With an alcoholic solutio n of ferric chlo

.

rid e it gives a dirty violet color which proves the prese n ce of ,

’

a n e n ol group It is a stro n g mo nobasic acid givi n g a sharp

.
,

reactio n with one molecule of caustic potash usi n g phe n ol ,

phthale i n an d formi n g mo no silver an d barium salts -

.

gram p h e ny l uraz ol e required 00 N / 7 caustic

soda i n stead of the calculated 00 .

Silve r Sa l t This is made by addi ng the calculated amou n t

.
—

of silver n itrate to the n eutral s od ium salt an d boili ng the

solutio n The precipitate is the n easily filtered
. It is very .

stable toward light is easil y soluble i n ammo n ium hydrate

, ,
°
but i n soluble i n dilute n itric acid It melts at 2 5 2 with de .

co mpositio n givi n g o ff fumes h a vi n g a stro n g isocya n ate

,

odor
gram sil v er salt gave gram silver .

C l ul t d f a c a e or
C 3H 6 N 30 2A g . Fo un d .

Ag
B a ri um Sa lt B y titrati n g 0 5 gram p he ny l uraz ole with 2 9 5
—
. .

00 N /
. 1 0 barium hydroxide usi n g phe n olphthale i n as i n dica ,

tor an d evaporati n g n early to d ry n ess an d cooli ng the barium

, ,

salt crystallized out i n plates which were washed with alco ,

° °
hol an d dried i n the air It decomposes at 2 80 to 30 0 with .

out ch arri n g There are 2 molecules of water of c ry st alliz a

.

tio n .

°
gram substa n ce heated five hours at 1 2 0 lost
gram .

gram salt required 00 N / 1 0 potassium sulphate .

a nd N / 1 0 potassiu m bichromate to precipitate the bariu m an d

give a yellow solutio n .

C l ul t d f a c a e or
( C 3H 6 N )
8 0 2 2B a 2 H20 .

(1 8 6

C 6 H5 N —
N GH
I -
Phe ny l -z me thyl 3 hy d roxy ura z ole
- - -
,

OC CO H
 Con sti tu tion f P he ny l u ra z ole
o .

substa nce was first made by Busch and H ei nrichs by the 1

ac

tio n of n itrous acid on 1 phe n y 1 2 methyl 4 ami n ouraz ole

- - - - -
,

CJ L N —
N GH,

00 CO

N —
N H,

( see theoretical part ) By heati n g p he n y l uraz o le i n alcoholic

.

potash with on e molecule of methyl iod id e three hours with a ,

retur n co nde nser evapo rati n g o ff the alcohol an d acidifyi ng

, ,

a precipitate of fi n e n eedle s which melt at is obtai ned , .

The substa n ce is re adily soluble i n alkalies ether an d alco ,

hol a nd is somewhat soluble i n cold water By evaporati n g

, .

to dry n ess twice with co n ce n trated hydrochloric acid the body ,

which melts at 1 8 3 is recovere d u n cha n ged showi n g th at

°

the methyl group is attached to n itroge n an d does n ot form

the methoxy group as Busch an d H ei nrichs supposed This
,
.

same methyl derivative m ixed with p he ny l uraz ole is ob , ,

ta i n e d by boili n g the silver salt of p he n y l uraz ole with a n alco

holic solutio n of methyl iodide with a retur n co n de n ser for
'

fi ve hours The substa nce is a mo n obasic acid givi n g a

.

sharp reactio n with 1 molecule of sodiu m hydroxide ( phe n ol

phthale i n ) an d form
, i ng a mo n o silver salt -
.

gram substa nce required cc N / I O sodium h y .

d rox id e i n stead of cc calculated .

, .

A n alysis
°
gram substa n ce ga ve 00 n itroge n at 2 4 a n d .

7 3 6 mm .

C l ul t d f a c a e or
C gH gN go g u
Fo n d

Si lve r Sa lt This is made by addi n g silver n itrate to the

.
—

solutio n of th e sodi um salt and boili n g The precipitate is .

the n readily filtered an d whe n dry melts at ,

givi n g ofl
stro n g fumes of an isocya n ate The s a lt is very soluble i n .

ammo ni um hydrate but i nsol uble i n dilute n itric acid Whe n

,
.

heate d fiftee n mi n utes with hydrochloric acid filtered from ,

1 Bu sch n d H i i c h B d h m G 3 3 45 5
a e nr s er c e es
. . . .
, , .
1 30 A cre e .

the silver chloride and eva porated crystals of the , , 1- phe nyl
2 me thy l u raz ol e
-
which melts at are obtai ned , .

A n alysis
gram silver salt gave gram silver .

C l ul t d f a c a e or
C gH sN go gA g . Fo nd u

C GHsN -
N
I -
Phe ny l n me thy lu raz ole
- -
, N —
This was made
OC C OH

N C H3

by a method which could n ot give the 1 phe n y 1 2 me thy l u ra - - -

zole Whe n molecular proportio n s of p he ny l se mic arbaz id e and

.

m e th y l ac e ty l ure a are melted together a n d heated two hours to

am mo n ia an d acetic acid are evolved and the mass beco mes
pasty By d issolvi n g i n warm dilute alcohol cooli n g and
.
, ,

filteri n g 2 0 per ce n t of 1 phe n yl 4 me thy l uraz ole is obtai ned

,
- - -
.

Its melti n g poi nt is -

The compou nd gives a violet color
with alcoholic ferric chloride and gives mo no sodium an d sil -

ver salts B y repeated evaporatio n wi th co n ce ntrated hydro

.

chloric aci d the melti n g poi nt is not cha n ged A s the methyl -
.

group i n this compou n d c an o n ly be at 4 it is evide nt that ,

the methylatio n of phe n y lu raz ol e by mea n s of methyl iodi de

an d alkalies tak e s place at 2 the hydroge n at this place seem ,

i ng to be replaced more rea d ily by methyl acetyl etc , , .

A n alysis
°
I . gram substa n ce gave 00 n itroge n at 2 8 C . .

a nd 7 30 mm .

°
II . gram substa n ce gave cc n itroge n at 2 7 C . .

an d 7 3 2 m m .

C l ul t d f F u d a c a e or o n .

C 9 H 9N 3 0 2 .

Silve r Sa ltThis was made by addi n g the requisite amou n t

.
—

of silver n itrate to a solutio n of the n eutral sodiu m salt and ,

boili ng U po n filteri ng an d dryi n g there is obtai n ed a stable

.
,

silver salt which melts at , with decompositio n givi ng an ,

isocya n ate odor .

1 32 A cre e .

A n alysis
°
gram substa nce gave 00 . n itroge n at 29 C . an d

7 32 m m .

C l ul
a c at e d for
c l oH u N aO g . u
Fo n d

20 .
59
Ce HsN —
N
I -
Phe ny l -
z - hy dro-3 -oxy ace ty l u raz ole ,
OC C O C OC H ,

This compou n d was made by allowi n g acetyl chloride to ac t

upo n the silver salt of ph e ny l uraz ole i n be nze ne solutio n i n
the cold By filteri n g o ff the silver chloride a n d evaporati n g
.
,

of f the be nze n e an d acetyl chloride a n oil w as obtai n ed th at ,

would n ot solidify .

A n alysis :
°
gram substa nce gave 00 n itroge n at 2 2 C a n d . .

7 2 4 mm .
.

Ca l ul at
c e d fo r
C 10H 9 N 3 0 3 . Fo und .

Whe n it was d issblve d i n boiling dilute alcohol an d heate d

for a few mi n utes or if the water so l utio n was allowed to ,

evaporate i n a desiccator o n ly the ph e ny luraz ole melti n g at ,

H ot acids a n d alkalies sapo n ify the bod y

°
2 6 3 was obtai n ed .

almost i n sta ntly By its method of formatio n this compou n d

.

must be the 1 phe nyl 2 hydro 3 ox y ace ty l uraz ole a nd the iso
- - - - -
,

l
meric N d e ri v ati ve which melts at
-
must be th e
,

1 phe n yl 2 acetyl 3 hy d rox y u raz ol e while the d i ac e ty lp h e n y l

- - - - -
,

urazole melti n g at , must be the 1 phe nyl acetyl 3 oxy - - - -

a ce ty l u ra z ole By boili n g with water it loses as we shoul d

.
,

expect the O acetyl at 3 givi ng the 2 N ace ty lp he ny l uraz ol e

,
-
,
- -

melti ng at
Whe n 3 oxy ace ty l 5 sty ry ltriaz ol 1 propio n ic acid which
- - - - -
,

melts at is boiled t wo hours with a return co nde n se r

with 5 0 per ce nt alcohol 3 hydroxy 5 sty ry ltri az ole r pro ,
- - - - -

pio n ic acid which melts at ,

precipitates Ou t on cooli n g .

Th i l1 d S hl u
e A n n C h m ( L i bi g )
e an c 95
e 7 ; Cu C t bl
ss n e r : 89 8 . e . e . 2 , 1 1 ne o : e n r .
,
1

I .
, 38 .

2 B ai l e y and A c re e Be r . d . c he m . Ge s . , 33 , 15 2 0 .
 Con sti tu tion of P he ny l u ra z ole .

Whe n the ethyl 3 o x y ace ty l 5 phe n y ltri az ole 1 propio n ate

-
‘

- - - -
,

w hich melts at is treated i n the same way there is ob ,

t ai ne d the ethyl 3 hydroxy 5 ph e n y lt ri az ole 1 propio n ate

- - - - -
,

w hich m elts at Si n ce these acetyl derivatives have

b ee n proved to be oxy compou n ds this easy hydrolysis is to ,

b e expected .

The compariso n of the relative amou nt ofhydrolysis of the

i someric N and O acyl derivatives of isati ne p h e n y lu raz ole
-
, ,

phe n yl mo n o and d ithiouraz ole s and of urazole fatty acids ,

Iw ill be take n up and studied qua ntitatively and we wish to ,

h ave this work left to us .

D ip he ny luraz i n e Work was started to determi ne the con

.
~ -

s t i t ut io n of d iphe ny l u raz ine This compou nd was first made .

b y P i nn er by heati ng ph e ny lse mic arbaz id e an d the n by He l

1
,

2
l e r by heati n g p he n y lc arbaz ini c ester P i nn er ascribed to .

'

t his compou nd the symmetrical co n stitutio n

0, H, N —
N H —
00

00 —
NH —
N -
0, H,

Such a compou nd should be a dibasic acid and give a d isilve r

s alt .B ut d iphe ny luraz ine is a mo nobasic acid givi ng a vio ,

l e t color with alcoholic ferric chloride c ombining w ith 1 mole ,

c ule of caustic soda a n d formi n g a mo nos ilv e r salt a lthough

, ,

g ivi n g a diacetyl derivative He nce we seem to have a com .

p ou n d with a n u n symmetrical co n stitutio n and it c an be o n ly

C sHs —
N —
N —
H C sHs —
N —
N

CC C OH or II C OH.

C sHs —
N —
N OC —
N —
N H C, H5
.

3
Rece nt work by R upe an d G ebhardt seems to co n firm for
m ula I an d we will not co nti n ue this work
, .

P i n n er states that d i ph e ny lu raz i ne which melts at is ,

c ha n ged by boili n g alkalies i nto a n isomeric form whi ch ,

m elts at This is a mistake Whe n boiled with a n ex .

1 P in n e r : B e r . h e m Ge s 2 1 12 5
d . c . .
, , 2 .

9 H e ll e r A n n C h e m ( L i e b i g ) 2 6 3 38
. . , , 2.
3 R up e an d G e b h a rd t Be r d c h e m G e s: . . . .
, 32 , 10 .
1 34 L a mb .

cess of caustic potash for on e hour and acidified o n ly p ur e ,

d iph e ny l uraz i n e melti ng at was obtai n ed, .

Dip he n y lu raz ine does n ot titrate sharply agai n st one mol e - 1

cule of sodium hydroxide ( phe n olphthale i n ) .

gram substa nce required cc N / 7 caustic potash .

,

i n stead of cc calculated .
, .

gram substa n ce required cc N / 7 caustic pota sh .

,

i nstea d of cc calculated .
, .

Sil ve r Salt Whe n silver n itrate is added to a solutio n o f

.
—

the sodiu m salt of d i p he n y lu raz ine an d boiled an amorph o u s ,

precipitate of the monosilve r salt is obtai ned This is fairly .

°
stable toward light a n d whe n heated darke n s at 1 8 8 an d de ,

composes at givi ng off isocya n ate fumes .

A n alysis
gram substa n ce gave gram silver .

C l ul t d f a c a e or
C 14 H 11N 40 2 A g

UN VE I R SI TY OF A UT H ,

De c e m b e r 1 , 19 01 .

T H E CO NV E R SION O F O R T H O P E R IO D I C A C I D INT O '

N OR MAL PE R IOD I C A C I D .

BY A R THU R B . L A M B .

While perchloric acid its a n hydride mo nohydrate an d di , , ,

hydrate are k n o wn o n ly the d ihydrate of periodic acid has a s ,

1
yet bee n described Be ng ie sse r to be sure states that th e .
, ,

crystalli n e acid Hl loses its water of crystallizatio n at

,
°
1 60 an d does n ot deco mpose i n to oxyge n an d iodic a n hy
°
d ri d e u ntil a temperature a i 1 9 0 is reached In other wor d s .
,
°
he states that periodic a n hyd ride is formed at 1 6 0 and re
m ai n s u ndecomposed at a temperature as high as
2 °
L a n glois fou n d that o nly at 2 0 0 is all the water elimi n ated ,

i odic a n hydride a n d oxyge n bei n g formed at the same time .

3
R ammelsberg however studied the effect of hea t on th e
, ,

acid most carefully an d arrive d at quite differe n t results H e . :

1 A n Ch m P h
n . m 7 54 e . ar .
, 1 , 2 .

1
J p l t C h m 3 6 36
. ra z e .
, , .

3 Mid , 10 3 , 2 81 .
1 36 L a mb .

A portio n of the acid had bee n tested with silver n itrate and

nitric acid but o nly a trace of iodic iodi ne h ad bee n fo u nd

,
.

Taki n g samples of this acid usi n g water i n the vapor j acket ,

of the dryi ng apparatus an d a pressure of 1 2 mm a co n sta nt

,
.
,

weight was i n ge neral secured after heati n g fro m twe nty to

twe nty fi ve hours The dryi n g process was i nterrupted whe n
-
.

the loss after several hours a mou n ted to but a fractio n of a

, ,

milligram This was n ecessary si n ce sublimatio n became ap

.

pare n t upo n the walls of the dryi ng chamber after te n or

twelve hours of heati n g an d experime n t showed that such
,

slight losses would co nti n ue i n defi n itely .

Su b s ta n c e h e a te d .

ra m .

Mea n ,

Pe r c e nt
l

C alculated loss for H IO 5 ,

H IO
I 2 07

These n umbers poi n t with certai nty to the compositio n “

H IO , .

Q ualitative tests of this dehydrated acid showed the pre s

e nce of sli g htly more iodic iodi ne tha n was prese nt i n the
origi nal acid To co nfirm the above co n clus io n s based on
.
,

the loss of weight a n alyses from samples of the above d e hy

,

d rat ion experime n t I II

,
were made .
,

Iodi n e l ib r
e a te d .

G am
r

Mea n ,

Pe r c e nt .

C alculated per ce n t of iodi n e i n HS 3

IO 5
H ( t ( C
H IO ‘
I “0
 Con ve r si on f Orthope ri odic A ci d
o .

A n alysis therefore co n firms the co n clu sio n that the acid

formed by the dehydratio n method u nder the above co ndi
tio n s was the compou n d represe nted by H I O ,
.

This n ormal periodic acid was white or slightly yellowish

in color Whe n dropped i nto water sufli cie nt heat was g e n
.
,

er s ted to occasio n audible hissi ng .

H igher temperatures were now tried i n the hope of secu ,

ri n g periodic a n hydr ide Tolue n e boili n g at

.
,
was sub
stituted for water 3 31 the dryi n g apparatus Sublimatio n he .

came more appare n t on the walls of the dryi n g chamber but ,

no loss i n weight occurred beyo nd that evide n tly due to this

cause Tests i ndicated the prese n ce of somewhat more iodic

.

iodi n e tha n was prese n t in the acid dried at

Substituti n g xyle n e boili ng at
,
mark ed sublimatio n
occurred accompa nied by a rapid loss i n weight L arge
, .

amou nts of iodic a n hydride were now fou nd to be prese nt .

This agrees with the state me nt of R ammelsberg quoted above .

To determi ne whether a vacuum had any detrime ntal e ffect

at these high temperatures a sampl e of the norm al acid w as
,

treated at atmospheric pressure i n the dryi n g apparatus usi n g ,

tolue n e i n the vapor j ac k et The acid lost rapidly i n weight

.
,

and much iodic a n hydride was formed A fter thirty hours

.
’

h eati ng the loss i n weight i n dicated that if partial decomposi

tio n had ta k e n place i nto iodic a nhydride oxyge n an d water , , ,

approximately 4 0 per ce n t of the resulta n t mixture should be

iodic a n hydride A n alyses were made by B u nse n s method
.
’
,

and the relative amou nts of iodic a n hydride a n d n ormal

periodic acid were calculated o n the assu mptio n that n othi n g

else was prese nt .

I
. gram liberated gra m iodi n e per
ce n t of
II . gram liberated gra m iodi ne per
ce nt of I, O5
The perce ntage amou nts of iodi n e i n iodic a n hydride a nd
i n n ormal periodic acid are so n early the same per ce nt
an d per ce n t res pectively ) that the slightest di ffere n ce
,

i n the amou n t of iodi n e liberated was m ag nified ma n y times

i n the calculatio n .
 L a mb .

Inadditio n to heat se veral other mea n s were employed to ,

dehydrate n ormal periodic aci d but without success A cetyl , .

chloride added to the acid reacted viole ntly eve n at 2 0 if —

°

the aci d was added to the chloride the reactio n was less e n er
getic A clear cherry red solutio n was obtai n ed in either
‘
-
.
,

case which added to water showed complete reductio n to

, , ,

the iodic co n ditio n If acetyl chloride were added to a solu .

tio n of the n ormal acid i n g l ac 1al acetic acid a white fl oc c u ,

le n t precipitate appeared This also wh en filtered off and .

,

washed showed complete reductio n to the iodic co nditio n

, .

°
Whe n d rie d i n a vacuum at 1 0 0 a nd a n alyzed the followi n g ,

n umbers w ere obtai n e d .

gram liberated gram iodi n e .

C l ul t d f a c a e or
12 0 5 . u
Fo n d .

76 . 1

A ceti ca n hydride also reacts with the acid vigorously at

ordi n ary temperatures but slowly i n the cold E volutio n of , .

a gas takes place an d the reacti on product s howed on the ad -

,

ditio n of water complete reductio n to the iodic co n ditio n

, .

A n hydrous per c hloric acid also decompose d the acid eve n ,

at low temperatures .

R epeated attempts were also made to secure the i n te rm e

diate hydrate HSIO5 by dryi n g , , .

°
1 A t a temperature of 6 7 a nd a pressure of 1 7 to 1 8 mm
A t a temperature of 5 5 to 6 4 a n d a pressure of 2 7 m
. .

m 1 ° °
2 . .

° °

3 A t a temperature of 44 to 49 a n d a pressure of 2 4 mm
. .

I n all three experime n ts the poi nt correspo n di n g to the h y

d rate H, IO was passed without the least i n dicatio n of the
,

formatio n of a d efi n ite compou n d though in the two latter ,

experime n ts the rate of dehydratio n was exceedi n gly g radual

in the seco n d fifty hours i n the third o n e hu n dre d hours be
, , ,

i n g required to pass the poi n t i n questio n It appears i mp os .

sible to secure this i n termediate hy d rate by simple dryi n g .

The author wishes to tha n k P rof A Michael for his sug . .

gestio n of the research an d valuable assista n ce i n its e x e c u

tio n .

Tu s C LL E G E M SS
E T O , A .

1 I n th e se c on d a n d h xp e i m e nt s a w ate r b th w as u se d a s jac k e t for th e

t i rd e r - a

de hy d ra ti o n v e s s e l w h i c h l atte c ontai n e d b e si d e s th e s u b ta n c e a t h e r mom e te

, r , s . r

an d a m a no m e te r .
 Wa te r Ga s A ppa ra tus .

coke and fi n ally } to ! i n ch pieces of coke are poured i n at the

,
1 w

top u ntil the large pipe is n early filled The upper cap is re .

placed and the whole is the n supported on a sta nd usi n g o ne ,

small ri n g at the bottom an d a larger on e at the m i ddle It is .

well to use a clamp at on e of the upper pipes also It is placed .

close to the e nd of a combustio n furn ace and at such a height ,

that the horizo ntal tube will lie i n the trough whe n screwed
i nto place The E rle n meyer flask is placed i n positio n an d the
.

water heated to boili n g by a small fla m e The furn ace should .

also be lighted Whe n all is ready the fuse is lighted a slo w

.
,

curre n t of oxygen is passed i n thro ugh the tube at the bot

to m the lateral tube is screwed i n place an d all co nn ectio n s
, ,

“
are made Fo r the hot blast the hole i n the side of the
.
”

upper tube should be ope n A n i n creased curre n t of oxyge n

.

is passed i n u n til the outer layer of asbestos becomes very

‘
hot The n the oxygen is shut ofl the upper O pe n i n g closed
.
, ,

a n d by adj usti n g the pi n ch cocks steam is passed through the

-

horizo ntal pipe which should be heated n early to red n ess

, .

A s soo n as this superheated steam reaches the hot coke ther e »

is quite a rapid evol utio n of gas which is collected i n c y lin ,

ders In a few mome n ts no more comes over an d the steam

.
,

is to be shut off from the fur n ace and the outer pi n ch cock is -

O pe n ed ; the upper o utlet is reope n ed a n d oxyge n is ru n i n ,

as before The O peratio n c an of course be repeated u n til

.
, ,

the coke is co n sumed .

The gas is at first clouded but soo n becomes clear It ,

.

burn s with a pale blue flame It is a simple matter to e n rich

‘
-
.

it by causi n g it to bub ble through be nze n e or some similar ,

hydrocarbo n co n tai n ed i n a wash bottle

, Work i n g o n such -
.

a small scale it is n ot to be expected that the gas would have

,

the same compositio n as that made commercially A n alysis .

showed that it is true water gas a n d n ot simply carbo n mon

-
,

oxide forced over by the e n teri n g steam To ma k e sure that .

the hydroge n was not forme d i n the superhea t i n g tube we ,

raised the temperature of this tube still further and passed .

the steam i nto water The gas which was collected gave n o
.

evide n ce of co ntai ni n g hydroge n .

142 E va n s a n d Va n de rhle e d .

A n a ly si s o f Wa te r -
Ga s
I .

These figures become more n early comparable whe n recal

c ul ate d o n the basis of a mixture from which the carbo n di

oxide has bee n removed .

I .

0 .
3

3 2 -5 49 -5

The oxyge n which was used was fou nd to co ntai n about 8

per ce n t of n itroge n The varyi n g proportio ns of carbo n .

mo n oxide an d hydroge n may be d ue to the co nsiderably

greater sol ubility of the former i n water which would make ,

quite a differe n ce whe n o nly small qu a ntities of the water gas -

are ma d e .

JO H N SH O P K I N S U N I V E R S1T Y
D e c e mb e r 1901
,

, .

C o nt ri b u t io n f m t h ro e C h e m i l L ab
ca o ra t o ry o fP u due U niv e
r rs it y .

D IC H L O R A C E T YL P H O SP H I D E .

BY P . N . E VA N S A N D C .
E . VA N DE R KL E E D .

In a ge n eral survey of the classes of orga n ic compou nds o n e

is struck by the fact that i n spite of the recog n ize d a n alogy
i n properties betwee n the ami n es an d phosphi n es refere n ce to ,

the phosphorus derivatives correspo n d i n g to the acid ami d es

is e n tirely lacki n g i n most text books presumably o n accou nt -
,

of the very sm all number of represe ntatives of this class

k n ow n A ppare n tly o n ly two of these bodies which may ap
.
,

r
p pO r i at e l y be called h
p p
os hi de s h ave bee n prepared a n d ex ,

am in e d n amely
, mo no c hlorac e ty l p h 0s ph id e an d t ric hlor
,
1

2
acetyl phosphide .

The purpose of the work here prese n ted was to add to our
k n owledge of this class of compou n ds .

1 Ste i n e r : Be r . d he m Ge s
. c . .
, 8, 1 17 8
1 C l oe z : A nn . c h i m ph y s . .
, 17 , 309 .
1 44 E va n s a n d Va nde rhle e a ’
.

Pota ssi u m D ichlora ce ta te hu n dred and seve nty grams

.
—
O ne
potassiu m ferrocya n ide an d 1 1 5 grams chloral hydrate were
dissolved in 5 00 00 water i n a flask with reflux co n de n ser
.
,

an d heated u ntil the color of th e ferrocya n ide disappeared

( about two ho urs ) a gree n precipitate of a double cya n ide of

,

iro n and potassiu m , separati ng and bei n g filtered

o ff fro m time to time to preve nt bumpi n g Whe n the re ac .

tio n was complete the mixture was cooled an d filtere d an d ,

the n heated to prove that n o further precipitatio n occurred .

T he filtrate was the n evaporated to dry n ess on the water bath -

a n d the potassi u m d ic h l o rac e t ate extracted from the p ot as

si um chloride with about 4 5 0 cc stro n g alcohol in several por .

tio n s the alcoholic extract was evaporated to dry n ess on the

water bath and th e residue dried at
-
The reactio n is
represe n ted by the equatio n
2 K, Fe ( C N )6 3 C C l, C H O H, O .

3 C H C 12 C OO K + 2 K Fe ( C N ) 3 + 6 H C N
3KCl .
,

a n d the yield was about 7 0 per ce n t of the theoretical .

Dichlor a ce tic A cid The dried potassi um d ic hlorac e tate was

—

place d i n a piece of ordi n ary combustio n tubi ng held n early

horizo ntal an d co nn ected by a lo n g adapter at its lower e nd
with a dry flask a curre n t of dry hydrochloric aci d gas was
passed through from the upper e n d an d the tube ge ntly heated
till the gas escaped from the flas k the n the temperature was
raised till all the dichloracetic acid boili ng at had dis ,

tilled i n to the flask The yiel d was about 7 0 per ce nt of the

.

theoretical .

D ichlora ce tyl Chlor ide Fifty grams of dichloracetic aci d

—

a n d 30 cc phosphorus trichloride were warmed together with

.

reflux co n de n ser as lo n g as hydrochloric aci d was evolved ,

a n d the n the d ic h lora c e ty l chloride boili n g at distilled,

'

off . The yield was about 6 0 per ce n t of the theoretical .

Ga se ous Hy drog e n P hosp hi de Two hu ndred a n d fifty grams

.
—

potassium hy d roxide were dissolved i n 5 0 0 00 stro ng alcohol .

a n d placed i n a liter flas k a n d 5 0 grams yellow phosphorus

,

added after displaci ng the air i n the flask with illu mi n ati ng
gas a ge n tle heat was applied a nd the gas about 2 0 liters
, , ,

co n ducted i nto a gas holder for use P repared i n this way it

-
.
 D i chlora ce ty l Phosp hide .

is n ot Spo n ta n eously i n flamm able an d co ntai n s about equal

volumes of the phosphide an d hydroge n .

f D ichl orace ty l Phosphi de

Prep a r a ti on o .

The hydroge n phosphide after bei ng dried by passi n g through

,

a tube about a meter lo n g filled with soda lime was passed -

,

slowly through the d ic hlorac e ty l chloride co n tai n ed in a small

flask for several hours the liquid becomi n g somewhat yello w
,

an d more a n d more viscous u n til the gas n o lo n ger passed

through i n bubbles but formed a cha nn el Whe n this co n di .

tio n was reached several times the volume of a n hydrous ether

, ,

free from alcohol was added O n sta n di n g so me hours with

, .
,

occasio n al shaki n g the gummy mass was cha n ged to a yellow

,

ish white powder which was filtered off washed with ether
-
, , ,

dissolved i n a very small qua n tity of alcohol agai n filte r ed a nd ,

re p re c ip it at e d with te n or more volumes of ether bei ng allowed ,

to sta n d several hours The fai n tly yellow powder was fi l

.

te re d o ff washe d with ether dried i n a vacuum desiccator

, , ,

a n d fi n ally at

A ttempts to prepare the phosphide by passi n g the gas i n to

a solutio n of the acid chloride i n ether and in be nze n e gave
the pro d uct as a suspe nded powder but the v i e ld was poorer ,

tha n whe n the solve n ts were not employed .

A na ly s i s o f the P r oduct .

A qualitative exami n atio n sho wed charri n g on heati n g with ,

evolutio n of a substa nce with a phosphorus like odor and on -

,

ig nitio n with copper oxide a bluish gree n flame coloratio n -

,

i ndicati n g the prese n ce of carbo n phosphorus an d chlori n e , ,

.

Q ua ntitative estimatio n s of phosphorus a n d chlori n e were

made to co n firm the supposed formula C H C l C O P H which , ,

correspo nds to phosphorus a n d chlori n e per ce n t .

P hosphorus was estimated by the C arius method a n d satis

factory figures o btai n ed but the same method for the simul
t a n e ou s estimatio n of chlori n e gave variable results in all ,

cases lower tha n the proportio n required by the formula so ,

the method O f ig niti ng i n an ope n tube with lime was em

ployed with satisfactory results
, .

I n the phosphorus estimatio n the material ( about ,

gram )
10- 2 7
 E va ns a n d Va n de r hle e d .

was heated i n a sealed tube with fumi n g n itric acid an d silver

°
n itrate ( fo r the chlori ne ) to 2 00 for eight hours the silver ,

chloride filtered out the remai n i ng silver precipitated with

,

hydrochloric acid a nd removed the n the phosphoric acid pre ,

c ip it ate d with ammo n ium molybdate a n d fi n ally with mag ,

n e s ia mixture an d weighed as p e pho sph at e .

gram substa n ce gave gram corre

Sp on d in g to per ce nt phosphorus A seco n d a n alysis .

gave practically the same result .

In the chlori n e estimatio n the substa nce ( about gram )

was mixed with lime an d heated i n a combustio n tube for an
ho ur or more the n the mixture dissolved i n dilute n itric acid
, ,

filtered and the chlori n e precipitated as silver chloride with

,

Silver n itrate .

gram substa n ce gave gram A g C l correspo n d ,

i ng to per ce n t chlori n e an d gram substa nce

gave gram A g C l correspo n d ing to per ce n t chlo
,

ri ne .

These figures while n ot as exact as desired leave hardly a

, ,

doubt as to the ide n tity of the product exami ned .

Prop e r ti e s ofthe P hosp hide .

D ic hlorac e ty l
phos phide is a fai n tly yellowish white crys -

t alli ne powder with a Slight odor resembli ng the free acid and
hydroge n phosphide appare ntly due to slow decompositio n
,

due to moisture H eated to 2 00 C it chars without melti ng

.
°
.
, .

It is n early or quite i n soluble i n ether be nze ne chloroform , , ,

an d petroleu m ether ; i n soluble i n cold water but soo n de ,

composed by it with evolutio n of hydroge n phosphide very

soluble i n stro ng alcohol the solutio n acquiri n g after a time
, , ,

a fruit like odor probably d ue to a decompositio n resulti n g

-
,

i n the for matio n of the ethyl ester of the acid ; i n absolute

alcohol it is very soluble without appare nt decompositio n .

The preparatio n of other acid phosphides by similar re ac

tio ns is bei ng carried out successfully and will be reported i n
a later paper .

L A F YETT E
A , I N D TA N A .

D e c e mb e r ,
1 90 1 .
 1 48 Repor ts .

hydrochloric acid on albumi n s and obtai n e d urea This led , .

1

him to believe that ly satine is the substa n ce from which gua n

i d i n e is formed i n the oxidatio n of albumi n B ut H edi n .

showed that ly satin e co n si sts of a rg i n i n e an d ly si n e E . .

Schulze a n d his pupils have sho wn that argi n i n e which oc ,

curs i n n ature i n certai n sprouts yields urea an d a compo u n d ,

of the formula whe n treated with baryta water .

Whe n the compou nd C 5 H N O is treated with cya n am ide ,, , 2 ,

argi n i ne is rege n erated The compou nd C 5 H1 N O tur n e d .

2 , 2

out to be or n i thi n e a substa n ce that had lo n g bee n k n o w n

,

as a product of a n imal metabolism O rn ithi ne has b ee n .

show n to be d i amid ov ale ric acid -

Q uite rece n tly E . .

d i a m idov ale ri c a cid

1
Fischer has succeeded i n prepari ng a -

that is evide n tly the i n active form of or n i thi n e The r ela .

t io n s betwee n creati n e argi n i n e or n ithi n e an d putresc i n e

, , ,

are represe n ted by the followi ng formulas

N H2
CZ N H
\N H . C H2

00 0 11
is
011 ,
0H N H .
,

00011
Cre at in e . r
A gi n in e .

L ysi ne has bee n show n by Drechsel to be a

,
e- diamido ~ ~

ca proic acid an d the same chemist has fou n d d i ami doac e t ic

,

acid amo n g the decompositio n products of albumi n Fi n ally .

,

hi stidi n e a substa n ce of the formula

, belo n gs to thi s
sam e group of basic cleavage products of albumi n .

The n ext group of cleavage products of albumi n is th at o f

the mon am id o acids The simplest compou n d of this group .

is glycocoll which is very freque n tly met with The n ex t:

, .

member of the group of amido acids a la n i n e or a amid op ro , ,

-

pio n ic acid has bee n fou n d amo n g the decompositio n prod

,

n ots of fi broi n from silk B ut the derivatives of this acid .

,

formed by oxidatio n or by the i n troductio n of sulphur or , ,

by the additio n of a n aromatic group are of greater importa n ce ,

:

tha n the acid itself A mo ng these are se ri ne obtai n ed fro m

.

silk a n d cy ste i n e obtai n ed from cy stin e

,
The relatio n s be .

twee n these substa n ces have bee n clearly established The y .

are represe nted by the followi n g formulas

1 Be r d c
. . he m . Ge s .
, 3 4 , 45 4
 R epor ts .

1 N H,

C —
S S
—
C

C OO H COO H C OO H
C y st e i n e . C ys t ine .

R ece n tly , M ‘
or ner has show n that whe n hor n is treated
w ith h y d roc t ric acid two cysti n es are formed , a l ae voro ta
s
‘

tory a nd a dextrorotatory variety .

Other d erivatives of am i d O prO pionic acid that are obtai ned

from albumi n co n tai n a n aromat i c n ucleus P he ny la la n i n e .

( phe n yl a am i d O p rO p ion ic aci d ) which was first fou n d i n

- -

"
Sprouti n g pla n ts , a n d later as a product of the cleavage of
v egetable albumi n s , is o ne of these A nother is tyrosine , .

which was d is c overed by L iebig i n 1 84 8 , and has si n ce the n

bee n regarded as a characteristic cleavage pro d uct of albu
mi n s Tyrosi n e is a laevorotatory p hy drox y p he n y l a a m ido
.
- - -

p ropio n ic acid The relatio n betwee n phe n ylala n i n e and

.

"

tyrosi n e is show n by the formulas

C 6 H5 C H , C H ( N H, ) COO H , P he nylala n i ne
.

OH
p C -
.m< C
H, C H ( N H , ) C O O H Tyrosi n e
.
, .

A n am i d o bu t y ri c
acid an d an am ido vale ri c acid have bee n
fo u n d amo n g the cleavage products of albumi n but le uci n e , ,

w hich is the laevo rotatory a ami do isobuty l ac e tic acid is -

,

m uch more com mo n ly an d abu nd a ntly met with an d together ,

with this a compou nd called le uci n e i mia e This

,
’
.

is to be regarded as a derivative of diacipiperazi n e formed by

the combi n atio n of two molecules of leuci n e

C H N H, .

COOH

L e uc i n e .

“l
Z ts c h r
-
. ph y siol C h e m
. 2 8 . 5 95
15 0 R epor ts .

E mil Fischer has rece n tly fou n d active pyrrolidi ne - a -

car
bon ic acid amo n g the decompositio n products of case i n
N H

c: H 00 0 H
I
.

. l
H, C —
C H,
P y rrolidi n e - a- c a r bo n i c a c id .

To the above named amido acids an d their derivatives m ust

-
,

be added aspartic aci d an d ,

glutamic acid , as amo n g

the cleavage products of albumi n .

C arbohydrates have repeatedly bee n obtai ned as prostheti c

groups That carbohydrate residues occur i n the molecule s
.

of albumi n appears probable from evide nce f ur n ished by i n

l
v e st ig ati o n s of U d ran sk y This chemist has show n tha t .

whe n pure albumi n s are distilled with sulphuric acid furfuro l

is obtai n ed The formatio n of furfurol was regarded by him
.

as evide n ce of the prese n ce of a carbohydrate group i n albu

mi ns The c ause of the formatio n of the furfurol has how
.
,

ever not yet bee n determi ned

, .

Whe n other chemical age nts besi d es dilute acids or alka

lies such as e nzymes oxidizers fusi n g alkalies are used for
, , , ,

the purpose of breaki n g dow n the alb umi n molecule ; product s

are obtai n ed that are esse n tially the same as those already
me n tio n ed or they are such as c a n be formed by further tra n s
,

formatio n of these Thus the fatty acids that are forme d .

,

whe n albumi n s are treated with fusi n g potassium hydroxi d e

have their origi n i n the amido acids ; p araox y be n z oic acid
comes from tyrosi n e and be nzoic acid from that co n stitue n t
of albumi n that yields phe n ylala ni n e .

It is evide n t that all the atomic groups co n tai n ed i n the

albumi n molecule ca nn ot be detecte d by hy d rolysis by mea n s
of acids an d alkalies More e n ergetic hydrolysis destroy s .

that group which gives the biu re t reactio n a red coloratio n —

caused by 00 p p e r sulph ate i n the prese n ce of caustic soda

. .

The first decompositio n products which are similar to the ,

origi n al albumi n s give this reactio n very stro ngly B y

,
.

further ac tio n of the hy d roly z m g age n t the reactio n d i sap

pears a nd we c an therefore disti n guish betwee n pro d ucts tha t
,

give the biuret reactio n an d pro d ucts that d o n ot give th e

biuret reactio n .

Just as the biuret formi n g group disappears so also o n e -

,

aromatic group of the albumi n molecule d isappears u n der the

1 Zt h ph y i l C h em
sc r 389
. s o . .
, 12 , .
other substa n ces with the greatest ease O f speci al impor .

ta n ce is the fact that they combi n e with o ne a nother This .

makes it appear probable that most of the albumi n s that have

bee n isolated from a n imal tissues are complex compou n ds of
several Simpler albumi n s A n umber of facts go to Sho w that .

whe n the large molecule of albumi n is broke n do wn by h y

d roly si s oxida t io n or the actio n of e nzymes it yields ( 1 )
, , ,

several smaller molecules ( a lbumose s) which the n break dow n

i nto 2 ) still smaller biuret formi ng atomic complexes p ep -

ton e s i n the moder n se n se ) a n d fi n ally i n to ( 3 ) t he a bove ,

n amed pro d ucts that do n o t give the biuret reactio n .

O w i n g to the great difficulties e n cou n tere d i n the i nvesti

g a t i o n of typical complex albumi n s the author has tried to
'
,

get light on the problem by seeki n g i n n ature for simpler

albumi n s Such substa n ces are the protami n es that are fou n d
.

i n the spermatozoa of fish The first mem ber of this class was
discovered thirty years ago by Miescher i n the sper matozoa
.

of the salmo n H e d escribed it as a substa n ce of the formula

.

1
Kossel later fou n d basic compou n ds i n the sper
matoz oa of other fishes These resemble the protami n e of the .

salmo n or sa lmi n e but are not ide ntical with it Such are , .

2
stur i n e from the testicles of the sturgeo n an d clupe i n e from ,
f
the testicles of the he rring ’

The protam i n es are co mpou n ds of stro n g basic properties .

They have a high molecular weight at least the free bases —

do n o t raise the boili n g poi n t of water H ydrolysis has show n

’

-
.

that there are several groups of these protami n es The sim .

p l e s t salmi
, n e a n d clupei n e brea k do w n i n to argi n i n e amido , ,

valeric acid an d a residue the n ature of which is not yet

, ,

k n ow n The qua ntity of argi n i n e obtai ned from salmi n e is

.

per ce nt from clupei n e it is ,per ce n t of the prota

mi n e take n A cco rdi n g to this . per ce n t of the total ni ,

troge n i n sal mi n e a nd per ce n t of that i n clupei ne is i n

, ,

the form of argi n i n e .

E ach of the three protami nes above n ame d therefore co n tai n s

three of the characteristic groups of the albumi n s the urea —

formi n g complex d i am id ov al e ric acid and ami dov ale ric acid
, ,
.

That these groups are arra nged in the protami n es i n a way

similar to that i n which they are arra nge d i n the complex
albumi n s appears probable from the fact that the protami nes
Show the biuret reactio n The p rope p to ne s and pepto nes as .
,

has bee n poi n ted o ut are i n termediate products that are ,

1 V e rh a n d l d . . n at u r for sc h . G e se ll . in B a se l , VI .
,
f
He t 1, 5 5 . 1 3 8— 2 08 P i c ard Be r .

d . c h m
e Ge s , 7 ,
. . 1 7 14
3 Z tsc h r . ph y s io l C h e m . .
, 2 2 , 17 6 .

3 1bi d .
, 2 5 , 1 65 .
forme d whe n the origi n al albumi n s are broke n dow n i nto the
abiuretic substa n ces ( substa n ces that do n ot give the bi uret
reactio n ) Similar i ntermediate products are formed fro m
.

protami n es These are calle d p roton e s The protami n es like

. .
,

the typical albumi ns have colloidal properties a nd they c an , ,

easily be salte d out A s they pass over i nto the proto n es .

these properties are gradually lost as is the case i n the pep ,

t o n i z ati o n of the albumi n s .

In all attempts to bri n g the group of albu mi n s i nto a chem

ical system the fact must be kept i n mi nd that the molecule
of albumi n is composed of several like or u n like parts the ,

albumoses or pepto n es a k nowle d ge o f which must be the ,

first obj ect of the i n vestigatio n In order to get a ge n eral .

co n ceptio n of the co n stitutio n of th e albu mi n molecu le it will ,

be desirable to fix our atte n tio n upo n some o n e group c on

t a i n e d i n the albumi n s a n d to regard the albumoses a n d pep ,

to n es as forme d by the additio n of di ffere n t groups to this

n ucle us We must of course for this purpose sele c t as this
.
, , ,

n ucleus a group that is co n tai n ed i n all albumi n s or i n as

ma n y as possible eve n i n the protami nes A rgi n i n e a n swers
—
.

these co n ditio n s best I n this light the simplest biuret form .

,
-

i ng co mplexes the proto n es a n d the protami n es are to be re

, ,

garde d as forme d by the a d ditio n of a mon a mido acid ami d o ,

valeric acid an d of a nother substa nce still u n k n ow n to the

,

argi n i n e group In the case of the higher protami n es there

.

is of course greater complexity of the molecule

, , .

The d i ffere n ces i n the relative qua n tities of the various

groups that go to make up the albumi n molecule would su f
fi c e to explai n the existe n ce of a large n u mber of albu mi n s .

P ossibly other di ffere n ces may be due to the arra n geme n t of

the co n stitue n t groups i n space A t all eve n ts it is clear .
,

that the co n ceptio n of albumi n as a factor of co n sta n t

value as always Sig n ifyi n g the same thi n g is u nj ustifiable
, ,
.

It has bee n poi nte d out that i n the tissues an d secretio n s ,

of a n imals and pla n ts the albumi n s freque n tly occur i n com ,

bi n atio n with other groups The physical properties of these .

p r a te i a s are
’
esse n tially those of the albumi n s a n d hy drolysis ,

is ge n erally n ecessary to determi n e whether these substa n ces

co n sist of two co n stitue n ts an albumi n or at least a biuret , ,

formi n g compo u n d ( pepto n e ) an d the prosthetic group ,

.

The u nio n of the albumi n ous co n stitue n t an d the prosthetic

group may be more or less firm H oppe Seyler for example .
-
,
1
,

has show n that i n the yolk of eggs le c ithine is combi n ed with

albumi n very loosely the compou n d bei ng broke n dow n eve n ,

by hot alcohol In other cases e n ergetic actio n is required to

.

1 “ P h y i l gi h C h mi B l i 87 7 8 p 7 8
s o o sc e e e ,
”
e r n, 1 -
1, . 1 .
1 54 R e
por ts .

e ffect this separatio n of the prosthetic group from t he albu

mi n .

In a few cases it has bee n possible n ot o n ly to decompose

the proteid i nto its co n stitue nts but also to cause these con ,
l
s t i t u e n ts to combi n e to form the proteid A ltma n for exam .
,

ple has show n that the prosthetic group of ma n y n uclei n s

, ,

n ucle i c a cid gives with albumi n a precipitate that h as the

,

properties of the origi nal protei d n uclei n , .

The prosthetic groups are of m a ny ki n ds A n i n orga n ic .

group a phosphoric aci d for example may combi n e with the

, , ,

biuret formi n g complex i n other cases a complicate d orga n ic

-

group may be u n ited with the albumi n '

.

The g l y 00p rote id s have o f l ate attracted the atte ntio n of

ph y siological chemists These are made up of a c arbohy .

d rate group combi n ed with albumi n an d i n vestigatio n s are ,

n ow i n progress i n volvi n g these substa n ces .

In the so called n uclei n s the carbohydrate co m plex appears

-

to be u nited with a large n umber of other atomic groups In .

the n ucleic acids at prese n t k now n di ffere n t carbohydrates ,

are u ndoubtedly co n tai n e d The other groups thus far fou nd .

i n the n ucleic acids belo n g esse ntially to the pyrimidi n e group .

The i nvestigatio n s of the last twe nty years have show n that
the derivatives of pyrimidi nes play a very i mporta n t part i n
the fu n dame n t al vital p h e nome na Kossel has fou n d them i n .

the place where the sy n thetical processes the phe n ome n a of —

growth take place that is to say i n the cell n ucleus

—
, ,

The Dissoci a ti ng P ow e r u id Hy dr oc a n i c A ci d
o
f L i q y .

2
Apaper has j ust appeared by C e nt ne rz we r describi n g an
i n vestigatio n o n the dissociati n g power of liquid hydrocya n ic
aci d This i n vestigatio n was carried out u n der the gui d a n ce
.

of P rof Wal d e n whose work on n o n aqueous solve n ts is so

.
,
-

well k now n A fter showi n g that liquid cya n oge n has pr s c

.

tically no dissociati ng power it seemed desirable to study i n , ,

this co nnectio n liquid hydrocya n ic acid an d especially for

, ,

the follo wi ng reaso ns

First The n itriles C HSC N C H, C N etc have stro ng dis , , , .
,

s o c i at i n g pow e r .

Seco n d In homologous series such as H O H C HsO H , ,

C H, O H or H N H C H, N H C H5 N H the first member has

, , , , ,, ,

much the stro n gest d issociati ng power .

Third : H ydrocya nic acid bei n g the first member of the

1 A rc hi v . fu r A . n at u. . P h y s io l g i e ( ph y s i o l . A b th e i l u n g ) , 1 889 , p .
5 24 .

2 Zt sc h r . ph y s . Ch e m .
, 39 , 2 17 .
156 Repor ts .

t ivi ty determi n ed A part of the solutio n was the n poured

.

out through the stop cock and replaced by the pure solve n t
-
, .

The co nductivity of the ne w solutio n was the n determi n ed

an d this process repeated u ntil the most dilute Solutio n was
reached .

The co n d uctivity of the solve n t w as fou n d to vary some

what the purest specime n havi n g the value X 5 in
—

,
1 0

reciprocal Sieme n s u n its ’

.

The co n d uctivities of potassium iodid e and trimethyl sul

p h o n i u m iodide i n liquid
,
hydrocya n ic a c id were determi n e d , .

T h e molecular co n ductivities at the di ffere n t dilutio ns to ,

gether with the molecular co nductivities of these same sub

sta n ces i n water are give n below
,

Ml o e cula r Condu cti vi ti e s of K ] at Ze r o .

In l i qui d H C N . In H gO .

v. ” v.

8 241

16 2 48

32 255
64 262

128 268

256 276

5 12 2 82
102 4 2 89

Ml o e cu l a r Con ducti vi ti e s f
o

In l i qu i d H C N .

v. ” v.

16 2 59
32 274

64 2 85

128 2 94

2 56 300
5 12 30 7
102 4 311
It is obvious from the above results that the co n ductivity of
these substa n ces i n liquid hy d rocya n ic acid is several times
greater tha n that i n water at the same dilutio n s an d it is very ,

probable that the dissociati n g power of this solve n t is eve n

greater tha n that of water B efore this co n clusio n could be ac
.

c e p te d as fi n al the values of u
, for the salts i n hy d rocya n ic acid
, 0°

must be accurately determi n ed This co n clusio n however is .

, ,

m ade probable by the fact that the m olecular co n ductivity i n

creases very ! slowly with i n crease i n dilutio n for the more
 Re vi e w s . I5 7

dilute solutio n s studied i ndicati n g that the value of [t had , oo

bee n very n early reached i n the most dilute solutio n s used .

C e n t ne rz w e r co n cludes his paper with the observatio n that the

dissociati ng power of this solve n t together with the high ,

value of its dielectric co n sta nt fur n ishes a ne w co nfirmatio n ,

of the Thomso n Ner nst l aw of parallelism betwee n d issocia

-

”
ti n g power and d ielectric co n sta n ts .

This i nves tigatio n is of Speci al i n terest i n that it m akes it

very probable that a solve n t has bee n fou n d which has a
greater dissociati ng power tha n water A n umber of attempts .

have bee n made to fi nd such a solve n t an d while it is possi ,

ble that hydroge n dioxide may be a stro n ger dissocia n t tha n

water this is far from proved
, .

That this solve n t co n forms to the Thomso n N er n st hypoth -

esis is also of i n terest but it should be n ote d that while ,

this hypothesis ac cord s very beautifully with the theory of

electrolytic dis sociatio n it is n ot a n ecessary co nsequ e n ce of
,

the theory If solve n ts therefore did not co n form to the

.
, ,

hypothesis i t woul d n o t a ffect in the slightest the vali d ity of , ,

the theory of electrolytic dissociatio n H Y C J NES .

AR R - O .

RE VI E W S .

A L A B O R A TO R Y G UI DE To TH E STU DY O F Q UA L ITA TIV E A N A L Y SI S B y .

E H S B A IL E Y
P H D , P r o fe s s o r o f C h e m i s tr a n d H A MI L T O N P
. . .
, . .

y , .

t t
C A DY , A B , A ss i s a n P o f s so o f C h m i s
. . r e r e try in t h e U niv si er ty o f
K an s a s Fo u h d i io n
. rt e t
P h i ad p hi a : P . l el . Bl ak i s t o n s So n
’
Co .

1 90 1 2 34
.
pp . .

The obj ect which the authors had i n mi n d i n prepari n g

this work c an be clearly see n by quoti n g a paragraph from
“
their preface : A t the prese nt time there seems to be a n
opportu nity to broade n the metho d s of i nstructio n i n Q ualita
tive A n alytical C hemistry an d to teach not o nly the facts a n d ,

the mecha n ical methods of carryi n g out th e various opera

tio ns of a nalysis but also to re n der them more i ntelligible
,

a n d i n teresti n g to the stude n t by a proper applicatio n of the

theory of E lectrolytic D issociatio n a n d of the Mass L aw In

,

the past we have had to be co n te n t w ith a bare state me nt of

facts which were largely u n related but the d issociatio n
, ,

theory of A rrhe n ius an d the law of mass actio n as e n u n cia ,

ted by G uld be rg an d Waage have furn ished us with a mea ns ,

”
of correlati n g a n d i nterpreti n g chemical phe n ome n a .

The aim of this work is u n doubtedly i n the right directio n .

The theory of electrolytic dissociatio n the l a w of mass a c ,

tio n the phase ru le and similar epoch ma k i n g ge neraliza

, ,
-
15 8 R e vi e ws .

tio ns have bee n freque ntly regarded as importa n t i n physical

chemistry but it has bee n held by ma n y that it would be i m
,

possible or at least u n desirable to i ntroduce them i n to ele

, ,

me ntary courses i n i n orga n ic chemistry In the last year or .

two a great cha n ge has bee n experie n ced In 1 9 00 the .

“ ”
G ru ndli n ie n der a norga n ische n C hemie by Ostwal d ap
e re d which showed how certai n physical chemical c on c e p
p a ,

tio ns c an and ought to be i n troduced i nto ge n eral chemistry ;

“
a n d i n the same year the L ehrbuch d e r a norga n ische n
C hemie by H ollema n was published The work of H olle
, , .

m a n goes farther i n certai n directio n s tha n that of Ost w ald ,

a nd together with the latter marks a n e w epoch i n the

, ,

developme n t of I n orga n ic chemistry .

That the pri n ciples which lie at the fou ndatio n of these
works are fi n di n g practical applicatio n i n the laboratory i s
show n by the appeara n ce of a ma n ual like the o ne in ha n d .

P erhaps a little di f fere n t treatme n t of certai n subj ects and a

little fuller treatme nt of others would have bee n adva ntageous ,

but these are mi nor poi nts This book will u n doubtedly .

co ntribute its share toward s the applicati o n of physical chem

ical ge neralizatio n s to i n orga n ic chemistry .

The book is o nly about half the Size that would be i ndica
ted by the n umber of pages si n ce half the pages are left bla n k ,

for stude nts notes ’

H C J
. . . .

T H E P R A CTI C A L M E TH O D S O F O R G A N I C C H E MIST R Y By L D W I G . U
G A TT E R MA N N , P H D , P ro fes so r i n t h e U n i v ers ity o f Fre i bu rg
. . .

T ra nsl ated by WIL L I A M B SC H O B E R , P H D , I n s t ru c t o r i n O rg a n i c

. . .

C h e m i s t ry i n L e h ig h U n i v e r s i t y T h e s e c o n d A me r i c a n fro m t h e .

fo u rth G er m an e di t i o n N e w Y or T h e M ac m il l an C o
. 1 900 k . . .

1
The first editio n of this book was reviewed i n this J O UR N A L
a n d atte n tio n was called to its excelle n ce as a laboratory

guide combi n i n g as it does n ot o nly a very exact a n d thor

,

ough treatme nt of the d etails of the preparatio n of typical

substa n ces but also i n each case calli n g atte ntio n to the
,

ge n eral pri n ciples i n volve d an d the ge n eral reactio n s of th e

substa nces and the beari n g of each case o n others I n this
, .

editio n a n umber of ne w preparatio ns h ave bee n i n troduced ,

some of which have bee n d evised si n ce the last editio n was

publishe d The p reparatio n of acetyle n e and acetyle n e tetra
.

bromide have bee n o mitted i n this editio n no doubt owi n g to ,

the fact that calcium carbide is n ow so accessible for the

preparatio n of acetyle n e This book should be i n the ha n ds .

of all who are teachi n g orga n ic chemistry or are maki ng or

Th i J U N L 9 7 9
1 s O R A , 1 , .
1 60 R e vie w s .

seem to fall n aturally i nto the co nt e nts of the work an d in ,

other cases it i s a questio n whether these physical chemical -

ideas have no t bee n carried a little too far Take the chapter .

o n thermody n amics as applied to chemistry This is so far .

above the level of the average reader of a book on i n orga n ic

Chemistry that it will make but little impressio n u po n him .

B ut eve n here the questio n arises whether everythi n g i n a

book should be writte n o n the level of the average reader or ,

should the reader be require d to m ake some effort to over

come d iffi culties which at first sight seem i n surmou n table ?
The se are however mi n or p oi n ts T he mai n obj ect of the
, , .

work is excelle n t . It ai ms to i n troduce simple mathematical

ge n eralizatio n s i n to i n orga n ic chemistry which is the first ,

step toward placi n g chemistry upo n the basis of a n exact

scie n ce It is u ni versally recog n ized that chemistry is much
.

less fully developed tha n physics a n d this has be en attri bu

,

ted chiefly to the n ature of chemical phe n ome n a These as .

,

a whole are more c o mp l e x t han physical phe nome n a a n d

'

, , ,

further chemical reactio ns freque n tly proceed i n steps on e

, ,

part of A combi n in g with o ne t wo th ree parts of B

, , Both .

of these i n flue n ces have ma d e it far more d ifli c ul t to deal with

th e phe n ome n a of chemistry by the o n ly exact method viz , .
,

the mathem atical .

It i s o n e of the c rown i ng glories of physical chemistry that

t hese diffi culties have bee n at least i n part overcome an d
, , ,

ma n y of the phe n ome n a which twe nty years ago were n e ce s

s ari ly treate d as empirical facts c an n ow be dealt with by
,

rigi d metho d s an d their mea n i n g an d sig n ifica n ce see n

,
.

The book in ha n d together with Ostwal d s G ru n dli n ie n

,
’
,

u n do ubtedly marks a ne w epoch i n the d e velopme nt of the

scie n ce of i norga n ic chemistry . H 0 J . . .
VO L . X X VI I . MA R C H , 1 90 2 . N O .
3 .

A ME R IC A N

ON THE FO R MA TION
D E C O MP O SITION A N D ,

G E R MI C ID A L A C TION O F B E NZO Y L A C E T Y L
A N D D I A C E T Y L P E R OX ID E S .

B Y P U L C F EE D F EDE KG N vA . R R A N R R IC . o v .

H o it se m a has show n that the amo u nt of hydroge n dissolved

1

in palladium is withi n certai n limits directly proportio n al to

, ,

the pressures exerted but if these are very small the n the , ,

qua ntity is proportio n al to the square root The co n clusio n .

to be reached is therefore that u n der these co nd itio n s the

, , , ,

hydroge n is prese n t i n the form of i n divi d u al atoms The .

formatio n of water fro m hydroge n and oxyge n u n d er ord i ,

n ary co n ditio n s takes place with u n measurable slow n ess

, ,

but is i n crease d to measurable rapidity by the prese n c e of cer

tai n substa n ces so that with fi n ely divided metals such as
, ,

p lati n u m or palladium Spo n ge the rate of cha n ge is ofte n so ,

rapi d that explosio n may occur U n questio n ably i n these .

,

cases th e metal has a specific actio n but the i nt e nsity of this

, ,

is i n creased by i n creasi n g the surface The gases i n these .

cases are perhaps best co nsi d ered as bei n g i n solutio n in the

, ,

solids an d the dissociati ng actio n of solve nts would produce

,

1
Zt h ph y i k C h m 7
sc r . s . e .
, 1 , 1
.

1 1— 2 7
16 2 F re e r a nd N av
y .

the mo n atomic co n ditio n made appare nt by Hoitse m a Mo nd .

,

R amsay a nd Shields have show n th at palladium foil spo nge

‘
, , ,

or black take up equal qu a ntities of hydroge n so tha t the ,

solubility of the gas is i n depe nde nt of the surface The h y .

droge n i n these solutio ns has the characteristics of a metal ,

a nd observi n g the a n alogy betwee n this a nd fluid solutio n s o f

o n e metal i n a n other it also seems probable that the hydro ,

,

g e n is i n the form of i n d ividual atoms The i ncreased ac .

t i vity c a n be explai n ed n o t o n ly by the greater co n ce n tratio n

of hydroge n i n u n it Space but also by the dissociatio n which ,

has take n place The resista nce to the oxidatio n of gaseous .

hydroge n may rest upo n the slow rate at w hich the molecules
are Split i nto atoms a n d this dissociatio n takes place more ,

rapidly i n metallic solutio n thus accou n ti ng for the i n creased ,

rate of oxidatio n The same must be true to a greater or less .

,

exte n t of all surfaces alt h ough n ot all have the same solve n t
, ,

or dissociati n g power for hy d roge n .

I n the case of oxyge n there i s n o such marked absorptio n .

by metals so that i n sta n ces i n which oxyge n is u nd oubtedly

,

re n dered active by the prese n ce of catalyzers are n ot freque n t .

The cha n ge from sulphur dioxide to sulphur trioxide by the

actio n of plati n ized asbestos or plati n um is u n questio n ably an
2
example The oxid atio n of mixtures of be n zaldehyde a n d
.
‘

acetic a n hydride whe n spread o n sa nd a n d exposed to the ,

air produces accordi ng to the co n ditio ns either be nzoyl per

, , ,

3 4
oxi d e or be n zoyl acetyl peroxide These reactio n s were .
,
'

i n our O pi n io n also cases i n which the catalytic actio n of the

,

solid surface brought about the oxidatio n so that while n u , ,

d e rt ak i ng some bacteriological studies on the actio n of orga n ic

peroxides we also st u died the i nflue n ce of catalytic age n ts o n
,

the formatio n of this class of bo d ies .

Nef has shown that the formatio n of be n zoyl acetyl p e ro x

ide ( accompa n ied by that of b en zoyl acetyl oxide a nd be n zoic
aci d ) is much more rapi d whe n the mixture of be nzaldehy d e
,

an d acetic a n hydride is spread upo nsa n d tha n whe n it is ex

posed to the air i n glass vessels this acceleratio n i n his ,

1 P ro c R . oy . So c .
, 62 , 2 90 .

2 Fo r an e x te n d e d h s ubje c t
re vie w oft is s e e Bo d l a n d e r s
’
A h re n s Vortra ge , 3 , 385 .

3 H E . r l e n me y e r J r B r d c h m G e
, . e . . e . s .
, 2 7 , 195 9 .

4 N et : A n n C h e m ( L i e bi g ) 2 9 8 2 8
. .
, , 0.
164 Fre e r an d N avy .

o nly a trace of acetic aci d A large qua n tity of acet i c acid

.
,

therefore has n o i n flue n ce i n i n creasi n g the rate of actio n

, , .

but o n the co ntrary it seems to d i mi n ish it If Nef s assu mp .

’

tio n that the formatio n of be n zylide n e diacetate is due to a

previo us additio n of acetic acid separatio n of the latter to ,

form n asce n t be nzaldehyde a nd subseque n t ad d itio n of aceti c

,

a n hyd ride is correct ,

C 6 H5
\C/ s 5
C O
H / \ O C O CH ,

C6 H 5 C O C Hs O C O CH 3

> < ><

6 5
C —
O O C
H C O C H, H O C OC H,
,

The n the i n crease i n the co ncen tratio n ofthe acetic acid should ‘

accelerate rather tha n retard the rate of reactio n .

I n order to test whether substa n ces other tha n acetic acid .

would also a ffect the rate of formatio n of be n zyli d e n e d i ac e

tate 1 0 grams of aldehy d e an d 1 0 grams of re frac tio n e d
,

acetic a nhydride were place d i n a tube with a strip of plati n u m

foil 1 cm wide and 5 cm lo n g a nd dry air was run through
,
. .
,

for twe nty hours The curre nt was very slow so as to secu r e
.
,

m erely an agitatio n of the liquid A t the e n d of this time .

grams of be nzylide n e diacetate had bee n formed c al c u

lated grams By far the greater portio n of this diacetate
.

was prod uced i n the first hour an d the tube at the begi n n i n g,

became quite warm sho w i n g that u n der these co n ditio n s t h e

,

additio n of ac e tic a n hydride to be n zaldehyde is much accelera

ted although o nly a trace of acetic acid could be prese n t
,

O n repe ati ng the above experime n t all co n d itio n s bei n g the ,

same except that the tube was co ole d to the formatio n o f

the diacetate was retard ed so that the cha n ge was not co m
p l e t e for three d ays The same mix ture
. sealed i n a tube a n d , .

p laced In the Shaki ng m achi n e soli d ified completely form i n g , ,

be n zylide n e diacetate after seve n hours so that agitatio n by ,

'

mea n s of a curre n t of air d id n o t accelerate the reactio n . .

Other metals have eve n a more marked e ffect Z i n c and t in .

,

whe n placed i n tubes co n tai n i n g the mixture of aldehyde a n d

a n hydri d e effect the cha nge i n about half an hour with a
, ,
 Be n z oyl A l
’
D zace ty l Pe rox i de s
‘

ce ty a na .

l o w c urre nt of air passi n g through and with iro n the re ac

s ,

t i o n prod a cts become heated at o n ce an d the additio n i S c om ,

p l e te after a f
e w mi n utes .

Various metals therefore exert a mark ed catalytic actio n , ,

o n the for m atio n of be n zyli d e n e diacetate i n depe n de n tly of ,

the amou n t of acetic acid which may be prese n t A cetic acid .

,

however may act as a catalytic age n t i ncreasi n g the velocity

, ,

o f the reactio n but n ot alteri n g the fi n al equilibrium

, Ih .

d eed i n accorda n ce with N e f 3 results we have fou n d that

’
, ,

a cetic a n hydride which had bee n freed from acetic aci d by

s ta n di n g over sodium a n d the n distilli n g did n ot form be n ,

z y li d e ne diacetate i n apprecia ble qu antities with iro n and a ,

s low curre n t of air u n til t h irty six hours h ad elapsed A nd

,
-
.

p robably as i n Nef s case m ixtures of be nzaldehyde and

,
’

a cetic a nhydride purified i n this m a nn er if simply sta ndi n g i n

, ,

a closed flas k would react with such extreme slow n ess that
,

a mou n ts of be n zylide n e diacetate su fli c i e n t for isolatio n woul d

n o t be produced for mo n ths We have n ot completed our

‘

work o n the actio n of cat alysis i n the formatio n of be n zylide ne »

d iacetate as very slight variatio n s i n the purity of the mate

,

ri als or of the catalyzers produce such mark ed variatio ns in the

rate of formatio n that co n corda nt results are d ifli c u lt to ob
t ai n Neither have we d etermi n ed whether a mixture of
.

be nz aldehyde an d acetic a n hydride purified by sta n di n g O Ve r ,

sodium will eve n tually produce be n zylide n e d iacetate but

, ,

the work has go n e far e n ough to demo n strate that various

s ubsta n ces have differe n t e f fects on the rate of additio n and ,

that eve n traces of acetic acid are j ust as effective as the

l arge amou n ts used by N e t .

The co n clusio n therefore is th at the actio n of acetic anhy , ,

d rid e o n be n zaldehyde is purely one of additio n an d that the ,

course of the reactio n is simpler tha n the on e proposed by

N ef .It is n evertheless probable i n view of the work of ,

l
B aeyer an d V illig e r on be nz op e rac id an d o n the oxidatio n of
fi be n z ald e hy d e as well as the other a dd itive reactio n s i n which
,

be n zaldehyde takes part that a methyle n e derivative , ,

H —
O
1 Be r. d . c he m . Ge s .
, 33 , 15 8 2 .
 Fr e e r a nd N avy .

takes part i n the reactio n Ma n y cha n ges which aldehyde s .

u ndergo c an best be explai n ed by the ex iste n ce of an e q uilib

riu m betwee n the two i somers

CZ O

O n ly a trace of the e n ol for m ( I I n eed be prese n t to start

reactio ns A S soo n as form I I is re move d the equilibrium i s
. .
,

restored by a re n ewed cha nge from I ( k eto form ) to I I ( e n ol . .

form ) an d so o n u n t i l reactio n is complete The ease with

,
.

which the cha n ge c an be brought about would determi n e t he

rate at which a give n aldehyde would react The existe n c e .

of a n equilibrium betwee n keto a n d e n ol form i n acetoaceti c

ether is n o w extremely probable i n V iew of the work of Schiff ‘
, ,

as well as the large m ass of moder n literature o n desmotropi c

forms of substa nces which seems to Show that an equilibriu m ,

betwee n the two forms exi sts i n ma n y liquid aldehy d es an d

keto n es This view n ee d o n ly be exte nd ed to ordi n ary al d e
.

R
hydes of the form
H> C: O to have a ratio n al expla n atio n of

the various reactio ns of this class of bodies C atalyzers as i n .

,

the above case of the formatio n of be nzylide n e diacetate ,

would the n simply a ffect the rate of cha n ge of keto to e n ol
form on ex actly the same pri n ciple as we suppose that cata
,

l y z e rs c an i n crease the rate of d issociatio n of the hydroge n

molecules i n to atoms i n the formatio n of water The relative .
2

i n activity of the carbo n yl oxyge n ato m i n the carboxyl group

ve rsu s

R
\C
O /
would thus be explai n ed by the mere fact that two disti n ct
forms o ne of which is the i n te nsely reactive u nsaturated
,

form an d the co n seque n t equilibrium are n ot possible and

, ,

1 Be r . d . c he m . Ge s .
, 3 1, 2 05f ll ow i n g
, a nd o .

2 B o d l an d e r U e be r l n g m e V rb e n n u n g
a sa e r , A h re n s V ortra g e , 3 , 439 .
16 8 F re e r an d N avy .

C l ul a c a te lum
d g as vo e
for 1 m o l e c ul e g a s p e r
G ra m p e roxide u se d . m o l e c ul e s p e rox d e
2 i .

199 74

As will be see n from the above 1 mo lecule of gas is devel ,

oped for every 2 molecules of peroxide and the method is ,

su fli c ie n t ly accurate for all purposes of measureme n t No ga s .

whatever is obtai n ed on heati n g pure be nzaldehyde or a mix

ture of be n zaldehyde and acetic a nhydride or an y other mix ,

ture n ot co n tai ni n g peroxide u n der the above co n d i tio ns as ,

we have proved to our satisfactio n The gas collected over .

potash much to our surprise proved to be metha n e

, , .

The gas collected from 5 grams of be nzoy l acetyl peroxide

was allowed to sta n d over stro n g potash solutio n for twe n ty
four hours an d was the n a nalyzed by combustio n .

C l ul t d f C 11 a c a e or 4
0
.

A gas a n alysis ki n dly carried out by Mr White of thi s

, .
,

laboratory by the usual methods co nfirmed the combustio n

, ,

a n d proved the gas to be metha n e The gas does not reduce .

a solutio n of pallad ium chlo ride he nce n o hydroge n is pres ,

e nt .

If the gas give n o ff by heati n g be n zoyl acetyl peroxide is

collected over mercury the n the volume is equ al to that cal
,

c u l a te d for 4 molecules of gas for every 2 molecules of p e ro x

ide d ecomposed and of these four molecules three are carbo n

,

dioxide .

I . grams substa n ce i n 4 0 cc of xyle n e were d e c om .

°
posed by heati n g to 1 0 5 i n a n oil bath the temperature bei ng -
,

gradually i n creased to a n d the total gas collected over

mercury The gas was the n passed through a potash bulb

.

by mea n s of a curre n t of air free fro m carbo n dioxide an d , ,

the carbo n dioxide weighed Fou n d gram C O .

,
.

II . grams substa n ce i n 2 0 cc of xyle n e were d e co m .

 B e nz oy l A ce ty l a nd D iace ty l P e rox i de s .

°
p osed as above care bei n g take n ,
n ot to heat above 1 10

Fou nd gram CO ,
.

C l ul
a c a te d for 3 m le o
c ul e s C 0 2 to 2 m leo u
Fo n d .

c ul e s p e ox id r e .

The perce n tage of gas obtai n ed is slightly low but the d e ,

compositio n is almost qua n titative A very mi n ute qua ntity .

of be n zoyl acetyl peroxide therefore decomposes d i ffere ntly , , .

The volume of'm e t han e o btai n ed also varies slightly from the
calculated The volume of gas n ot absorbable by potash
.

varies somewhat if the peroxide is very slowly decompose d

i n xyle n e but is fairly co n sta n t as show n above if the sub
, , ,

sta nce is heated over a free flame .

Two molecules of be nzoyl acetyl peroxide therefore de , ,

compose i nto 3 molecules of carbo n dioxide I of metha n e , ,

an d a liquid residue The empirical equatio n would be

.

2 09 11 8 0 . 3 C O1 C H. C A H I l oz
-

The high boili n g resi due was exami n ed as follows : The

-

xyle n e was distilled u n der dimi n ished pressure from the resi
due obtai n ed by heati n g 5 grams The remai nder was the n .

take n up i n ether an d extracted with sodium carbo n ate O n .

acidifyi n g the carbo n ate gram of a n acid was isolated ,

.

This acid has not bee n ide n tified The ether was the n dis .

tilled o ff an d the n o n acid remai nder boiled for six hours o n

-

a water bath with 2 grams of alcoholic potash The alcohol

-
.

w as the n distilled off an d the whole take n up i n water The .

n o n s ap o n ifl able portio n was carefully extracte d with eth e r

-
.

The alkali n e solutio n whe n acidified gave gram of be n

, ,

zoic acid The n on s apon ifi able po r tio n was fractio n ed at 1 8

.
-

mm pressure Two grams we n t over betwee n 1 6 0 an d

°
. .

an d about a n equal weight of high boili n g resid ue which -

,

would n o t distil up to remai n ed The distillate is .

° °
colorless a nd boils betwee n 2 6 0 an d 2 8 5 at ord i n ary pres
sure It ca nn ot be crystallized No co n sta n t boili n g prod
. .
-

u c t could be obtai n ed from it A n a n alysis showed this re .

m ain de r to be a mixture of high boili n g hydrocarbo n s -

.

Weight of substa n ce
170 F re e r a nd N avy .

Fo und .

G ra m Per c e nt

The hydrocarbo n s h ave n ot as yet bee n ide n tified The , , .

2
g rams of high boili n g resi d ue fi n ally passe d over whe n
-

heated with a free flame leavi n g practically n o resi d ue whe n

, ,

the thermometer fi n ally rose to This high boili ng por -

tio n is not a hy d rocarbo n .

The result sho ws that while the gaseous products are re

,

lated to the origi n al bo d y i n a very simple ma nn er the liquid ,

remai n der is by n o mea n s as simple A large portio n co n sists .

of hy d rocarbo n s of high boili n g poi nt so that the result of -

,

the decompositio n has bee n the coupli n g of th e residues . .

The s ap on ifi abl e portio n which yields the be nzoic acid is

, ,

probably phe n yl be n zoate H itherto the amou nt of substa n ce

.

at our disposal has bee n too small to follow out this i n terest
i n g decompositio n i n such a w ay as to ide n tify the liquid por
tio n but we i nte n d to return to this questio n i n the n ear
,

future an d clear up the m echa nism of this c ha n ge as well as

,

the d e compositio n of other peroxi d es by heat for the reactio n ,

may be ma d e on e of great sy nthetic importa n ce The Si m .

p le st cha n ge ,

C 6 H5 C O OO C O C H,
. .

C, H OO C O EC H3

0 0 00 2
011 ;
by which diphe nyl an d etha n e would be produced does n ot ,

take place an d it is a remarkable fact that the metha n e

, ,

which m ust u n questio n ably be produce d from one of the

methyl groups by reductio n of a seco nd methyl group should ,

result at all i n prefere n ce to etha n e The further study of

, .

the decompositio n products will probably d o m uch to clear up

-

the co n stitutio n of orga nic aci d peroxides .

The above results havi n g fully est ablishe d the feasibility of

determi n i n g the qua n tity of be n zoyl acetyl peroxide which
ca n be produce d by passi n g air through a mixture of be nzal
17 2 Fr e e r a nd N avy .

the first portio n of the series but the gradual decrease of ,

peroxide prese nt the lo n ger the tubes were allowed to sta n d

before determi n i ng the gas giv e n off makes it evide nt that de ,

compositio n oi the peroxide takes place an d becomes evide n t ,

as soo n as the curre nt of air ceases A S a co n seque n ce we .

repeated the above series placi n g the tubes i n the curre n t of ,

air successively after a give n i n terval of time the n allowi n g ,

each tube to be subj ected to the actio n of air for the same
le n gth of time twe n ty two hours an d forty mi n utes removi n g
,
-
,

each i n the ord er i n which it was placed in series and deter ,

mi n i n g the gas at o n ce E ach tube therefore stood the same .

, ,

le ngth of time as all of the others .

Ab lu t qu tity so e an
Tub C nt nt G d li d fl x d
a
e . o e s . as e v e re . o c ro i e .

1 A lu mi n um
2 E xtracted fi lte r p aper -

3 Bla nk
4 Mag n esium 63 2 .

5 Iro n
6 C opper
7 T in
8 P lati n um

D uri ng this reactio n the iro n grams ) lost

gram the alumi n um
,
gram fro m grams a nd the ,

C O pp e r gram fro m grams The copper was de .

c i d e d l y attacke d therefore whereas all other metals were

, ,

o n ly altered if at all to a slight exte nt In ord er to test

, ,
.

whether the fact that the metal was attacked would i n the ,

case of copper reduce the yield we carrie d out a series of e x

, ,

p e rim e n ts with copper alo n e .

P ieces of copper of equal size previously completely re ,

d u c e d i n a curre n t of hydroge n were place d i n the tubes an d ,

the followi ng results obtai n ed

Ti me of de mi tion fte
te r na a r C0 . ofg a s o b
fi rs t a d m i t ti n g a i r t ai n e d
H u
. .

o rs .
 B e n z oy l A ce ty l and Dia ce tyl P e r ox i de s .

It i s evide n t from this that i n the case of copper the form a

tio n of peroxide rapidly i n creases to a maximum the rate of ,

d ecompositio n the n exceeds that of formatio n u n til a practical

equilibrium is reached after twe n ty four hours The metal is -
.

attacked in all cases but the cause of the decompositio n is n ot

,

to be fou n d i n the copper acetate produced because a tube ,

co n tai n i n g copper acetate o n ly gave 00 gas after fiftee n .

hours This peculiar d ecompositio n of copper will be the

.

su bj ect of future i n vestigatio ns .

The above results Show beyo nd a doubt that the rate of

, ,

formatio n of peroxide is depe n de n t upo n the surface actio n

of substa n ces comi ng in co n tact with air and the mixture of
be nzaldehyde an d acetic a nhydri d e at the same time for the ,

bla n k tubes i n each case produce no greater qua ntity of per

, ,

oxide tha n would n aturally be expected from the surface of

glass exposed Of all substa n ces used mag n esium seemed to
.
,

have the greatest e ffect so that this metal was use d i n an ex

,

e ri me n t carried out with the purpose of determi n i n g whether

p
absolutely dry air c a n form be n zoyl acetyl peroxide with a
m ixture of absolutely dry be nzaldehyde a nd acetic a n hydride .

The apparatus co n sisted of a dryi n g trai n co n sisti n g of a

worm tube with sulphuric acid a tube 3 feet lo n g filled with
,

glass wool dusted over with phosphorus pe ntoxi d e a nd s tube ,

4 feet lo n g fille d with freshly glowe d soda lime a reactio n

-
.
,

tube with the e n tra n ce tube for air Sealed i n and surro u n ded
by a Spiral of pure mag n esium ribbo n an d the exit tube sealed ,

to the side an d co n n ected to the aspirator by mea n s of a tube

'
3 feet lo n g filled with glass wool a n d phosphorus pe ntoxid e
, .

The exit tube of the reactio n flask was co nn ected by mea n s of a

T with two distilli n g flasks which were so adj uste d that the first
,

a nd last portio n s of the d istillate could be r un o f

f through side
stop cocks while any qua n tity of liquid n ecessary coul d be
-
,

i n troduce d i nto the reactio n flask A l l parts of the apparatus

.

w ere sealed together so as to form a co nti n uous piece of glass .

The acetic a nhydride used was allowed to sta n d over sodium

for several weeks ; the be nzaldehyde was distilled several
times The appar atus was heated for several hours at
.

with a curre n t of air passi n g through the acetic a n hydride ,

a nd be nzaldehyde were the n placed i n the distilli n g flasks an d

17 4 Fr e e r a nd N avy .

distilled over i n to the reactio n tube the first portio n of the ,

distillate bei n g rej ected i n each case a n d the tube co nn ecti ng ,

with the apparatus was the n fused off A slow curre n t of air .

was the n passed thro u gh for twelve hours .

T e n 00 of m ixture gave 1 2 cc of gas correspo ndi n g to

. .
,

gra m of peroxide The prese n ce of moisture is .

,

therefore n o t n ecessary i n the formatio n of be n zoyl acetyl

,

peroxide In this ex perime nt

. grams of mag n esiu m
were used which lost o nly ,
gram duri n g the tim e of the
reactio n and this loss i s probably e n tirely d u e to the forma
,

tio n of oxide duri ng the heati n g an d dryi n g which was re

, ,

m oved duri n g the process of clea n i n g The mag n esiu m is .

,

therefore not acted o n duri n g the twelve hours of the e x p e ri

,

me nt altho ugh acetic acid must be produced accordi ng to an y

,

view which we c an take of the formatio n of be n zoyl ace tyl

p eroxide fro m mixtures of acetic a nhydride an d be n zaldehyde .

The same result was obtai n ed i n other cases whe n air was
ru n through the mixture for a sufli c ie nt le n gth of time to pro

duce acetic acid e n ough to more tha n dissolve all the mag n e
siu m prese n t Nef s view of the formatio n of be n zoyl acetyl
.
’ 1

peroxi d e supposes that i n the prese n ce of water be nz al de , ,

hy d e adds the latter to form d iox y tol ue n e

C , H, C H O HO H

which agai n separates as follo ws

5
\C H2 0
/
.

Ho
The latter substa nce the n agai n acts on water to form ortho
be n zoic acid an d hydroge n

2 HO H 2 H .

The hydroge n the n forms hydroge n peroxi d e with mo le c u

lar oxyge n while the be n zoic acid forms be nzoyl acetyl oxide
,

with acetic a nhydride Fi n ally hydroge n peroxide is sup .

,

A1 C h m ( L i bi g ) 9 8 8
nn . e . e , 2 , 2 0.
 F re e r a nd N avy .

poi nts to w ard a symmetr i cal structu re so that this questio n ,

must be a subj ect for future i nvestigatio n The above results .

are i n accord with those obtai n ed by B aeyer an d Vi llig e r o n l

the oxidatio n of be n zaldehyde The views of E rle n meyer .

,
3 4
J orisse n an d E n gler an d Wild are all based on the sup
,

positio n that be n zoyl peroxide is the result of the oxidatio n of

a mixture of be n zaldehyde an d acetic a n hydride a n d are c o n ,

seque n tly to be rej ecte d because be nzoyl peroxi d e is o n ly a

seco n dary pro d uct of the reactio n for we have co nvi nced our ,

selves that acetic a nhy d ride ca n not co n vert be n zoyl peroxide

i n to be n zoyl acetyl peroxide The suppositio n of E rle n meyer .
,

that possibly an a d ditio n produ ct of be n zaldehyde ( be n -

z y lid e n e d iacetate ) is first forme d which latter substa n ce i s ,

the n oxi d ize d to a substa n ce which is co n verted by the mix

ture i n to be n zoyl peroxide an d acetic acid is also n o t correct ,

for be nzylide n e d iacetate ca n not be oxi d ize d to a peroxide

either by air or by hydroge n peroxi d e The same V iew i n re .

gard to the me c ha n ism of the reactio n was adva n ced by Bod

l an der an d by Michael both of whom assumed the existe nce
6 7
,

of be nz op e rac id ,

before its discovery by B aeyer .

The a bove experime n ts also prove co nclusivel y that the

formatio n of peroxides is remarkably accelerate d whe n cer
tai n surfaces are prese n t as catalyzers a n d that this i n flue n ce ,

varies with the n ature of the surface In order to prove that .

the exte n t of liquid surface exposed is n ot of i n flue n ce a mix ,

ture of equal qua n tities of be n zaldehy d e an d acetic a n hy d ride

was placed in a Fer nbach flask so that the bottom was covered
to a depth of abo ut 3 mm The flask was allo wed to sta n d .

for twe n ty four hours at the e n d of which time o n ly a very

-
,

small qua ntity of peroxide had bee n formed The same mix .

ture forme d i n a large flat watch glass an d the n drai n ed o ff ,

-
, ,

1 Be r . d . c he m . Ge s .
, 33, 1 5 82 .

2 I bid 2 19 6 1
.
, 7 , .

3 Zt s c h r . ph y si k C h e m . .
, 22 , 58 .

4 Be r . d . he m Ge s 3 0
c . .
, , 16 7 7 .

5 [bi d 1 96 1 .

6 A h re n s V ge 3
o rt r a , , 47 1 .

7
J .
p ra k t . Ch e m 6 0 .
, , 75 .
 B e n z oy l A ce ty l a nd Di a ce tyl Pe rox ide s .

so that a very thi n layer was left so thi n that direct co n tact of ,

the air with the glass surface was possible was completely
.
,

oxidize d to a mixture of be n zoic acid a nd be n zoyl acetyl per

oxide withi n five mi n utes .

These results prove co n clusively th at the oxid atio n of mix

tures of be n zaldehyde a nd acetic a n hydride ca nn ot be referred
i n an y great measure to a partial dissociatio n of the ordi n ary
oxyge n of the air as is supposed by v an t H o ff,
A s this ac
’
.
l

c e leratio n of the rate of oxidatio n is brought about by a variety

of surfaces such as sa nd p aper cloth cotto n and various

, , , , ,

metals it seem s probable that the oxyge n of the air whe n

, ,

occluded by an y surface is re nd ered chemically more active , ,

a n d this i n creased activity is du e to a partial dissociatio n of

the occlude d oxyge n molecules

0 2 0 2 O —
0 .

This V ie wis of great importa n ce from a biological sta nd poi nt ,

as for example the ease with which hemoglobi n is cha nge d

, ,

to ox y hemoglobi n i n the lu n gs can be referred to the large

surface of tissue exposed If the assumptio n of an equilibrium.

betwee n the keto and e n ol forms is correct the n the differe n ce ,

between the activity of various surfaces c an be explai n ed by

the assumptio n that the substa n ces i ntroduced i n to the mix
tures of aldehyde an d a n hydri d e have di ffere n t e ffects on the
rate of cha n ge fro m the keto to the e n ol form whereas the ,

surface actio n o n the oxyge n remai n s alike in all .

The above experime n ts clearly i n d icated to us the best

mea n s of procuri n g an y d esired qua ntity of be nzoyl acetyl
peroxide .

A mixture of equal weights of be n zaldehyde a n d acetic an

hydride is prepared the mixture placed upo n strips of filte r
,

paper or musli n hu ng i n a large glass j ar with a cover a n d

, ,

dry air gradually run through C are m ust be take n not to .

place too ma n y strips i n the j ar at on e time as C o ntact com ,

bi ne d with the rapid formatio n of peroxide will in a very fe w

mi n utes bri n g about local heati ng to such an exte n t that the
paper chars an d may eve n take fire A fter the odor of be n z
, .

aldehyde has disappeared the paper or cloth is extracted with ,

1
Zt h ph y i k C h m 16 4
sc r. s . e .
, , 11 .

12- 27
17 8 F re e r a nd N avy .

low boili ng petroleum ether the solutio n washed with a little

-
,

’
soda solutio n u ntil the washi n gs j ust become alkali n e the n ,

the petroleum ether is partly distilled off from a bath of l uk e

warm water ( the bath must n ot exceed 80 in temperature °
,

otherwise explosio n m ay result ) and the solutio n is the n ,

placed i n a freezi ng mixture C rystals of be nzoyl a cetyl per -

.

oxide soo n separate a nd c an be filtered o ff a nd recrystallized

m
,

fro the same solve n t O n co n ce ntrati n g the petroleu m ether .

further crops of crystals somewhat less pure are obtai n ed , ,

.

The yield ofte n reaches 6 8 per ce nt of the theoretical I t .

varies with the temperature rate of admissio n of air thor , ,

o u g h n e ss of dryi n g a nd a m ou n t of su nlight Be n zoyl acetyl

, .

peroxide thus obtai n ed is ide ntical with that described by

Nef Whe n pure it c a n be kept appare ntly i n defi n itely pro
.
,

v id e d n o moisture comes i n co n tact with it I n the prese n ce .

of impurities such as moisture traces of alcohol ether or

,
“

, , ,

acids it gradually decomposes becomi n g liquid and the n

, ,

slowly depositin g crystals of dibe nzoyl peroxide The lique .

factio n seems to be due chiefly to a loweri n g of the melti ng

poi nt brought about by the formatio n of impurities either
, ,

diacetyl peroxide or be nzoyl hydroge n peroxide for the ,

melted portio n co n sists for the most part of be nzoyl acetyl

peroxide Tubes sealed up the co nte nts of which had lique
.
,

fi e d as above showed n o pressure so that oxygen is not give n

, ,

of f These cha nges will be the subj ect of future i n vestiga

.

tio n The melti n g poi n t of pure be n zoyl acetyl peroxide is

.
-

°
40 to
P ure be n zoyl acetyl peroxi d e is not a n oxidizi ng substa n ce ,

”
n or has it a n y odor a fact which was also observed by B aeyer
,
.

The followi n g experime nts will make this clear .

Twe n ty grams of be n zoyl acetyl peroxide were dissolved i n

2 00 cc of absolute ether an d the n 1 0 grams of a n ili n e were
.
,

added and the well stoppered flask allowed to sta n d i n ice

,
-

water for twelve hours A t the e n d of this time 3 5 grams of . .

a solid which proved to be aceta nilide had crystallized o ut

, ,
.

1 B ut m a ll mou n t of b e n oi c i d i s p od u e d Th i s p ove s th at u n d e r
a v e ry s a z ac r c . r

t h s e c o n di ti on s b u t l i tt l e b e n oy l a e ty l o x i d e i s for me d f r t h i s s u b s t n c e i s h y
e z c ,
o a

d ro l y e d b y m i s t i
z a n d t h e r e s ul ti n g b e n o i c ac i d w o ul d
o a r, pp e a r i n th a lk a l i n e
z a e

s o lu ti o n .

2 B r d c h e m Ge s
e . .
3 3 15 7 4
. .
, , .
1 80 Fre e r a nd N avy .

peracid can be isolated A t the e nd of the reactio n if a n ex .

,

cess of a n ili n e is used the n a n ili n e be n zoate appears

, .

P ure be nzoyl acetyl peroxide does n ot p roduce an y marked

effect o n hy d roqui n o n e i n be n ze n e for forty eight hours if -
,

water is excluded after this time oxidatio n gradually sets in

with the productio n of qui nhydro n e That a cha n ge fi n ally .

sets i n is probably d ue to the fact that a mi n ute qua n tity o f

wa ter which ca nn ot be excluded in seali n g up a flask grad
, ,

u ally causes hydrolysis with the formatio n of be n z op e ra c i d ,

while the l atter oxidi z es the hy d roqui no n e to qui nh ydro n e an d

'

water so that the reactio n o n ce begu n would go o n with in

, , ,

creasi n g velocity .

A lthough pure be n zoyl acetyl peroxide is n ot capable o f

oxidizi n g actio n the aqueous solutio ns are for the y promptly
, ,

liberate iodi n e fro m potassiu m iodide This di ffere n ce be .

twee n the norm al so l id a n d the solutio n is d u e to hy d rolysis .

This cha nge was followed out qu a ntitatively i n the followi n g

ma nn er :
T e n flasks with n ecks dra wn out for seali n g were filled
, ,

with 2 grams each of be n zoyl ace tyl peroxide a nd 1 0 0 cc o f .

water The co n tai n ers were the n filled a n d placed i n a shaker

.

°
kept at 2 6 i n a thermostat The flasks were ope n ed i n th e .

order give n in the followi n g table the co nte n ts filtered an d , ,

the active oxyge n i n solutio n d eterm i n ed by mea n s of acid

potassium iodide an d titratio n with N I2 O sodium thiosulphate .

In a certai n n umber of flask s the solid residue was weighed

to determi n e the poi n t at which equilibrium if any w as , ,

reached
Be n y l zo
A c ti v e o x y a e ty l p e r
c
T h i os u l g e n in o xi d e r e e r
Ho u rs .
p h a te . so luti o n . s e n te

18
24

30
48
72
96
‘

120

1 44
2 16

4 04
1 Sl i gh t p re u re i n tub e
ss on o p e n in g .

2 P u re b e n oy l p e r o x id e
z .
 B e n z oyl A ce ty l a nd D ia ce ty l Pe rox ide s .

C alculated total active oxyge n in 2 grams of be nzoyl acetyl

p eroxide ,

The solid after twe n ty four hours melted for the most part
,
-
,
;

°
a t 3 9 to o n ly a small portio n havi n g a higher melti ng
p oi n t the amou n t of be n zoyl peroxide gradually i n creased
,
°
u n til after o ne hu n dred an d forty four hours it melted at 1 0 6
,
-

°
t o 1 0 7 sharp a nd was pure be n zoyl peroxide , Before this .
-

ti me the resi d ual S olid was a mixture of be n zoyl peroxide an d

u n cha n ged be n zoyl acetyl peroxide so that as the relative , ,

proportio n s were u n k n ow n it was impossible to calculate the ,

a mou nt of active oxyge n rem a i n i ng A fter all had bee n c on .

ve rted to be nzoyl peroxide as was the case i n the last three ,

e xperime n ts it was possible to calculate the active oxyge n

,

remai n i n g in the soli d an d add it to that fou n d i n titrati n g the

s olutio n a nd the sum of these two qua ntities determ i n es
,

w hether active oxyge n is lost duri n g the hydrolysis A s will .

b e see n fro m the last colum n n o such loss took place u n til ,

four hu nd red a n d eight hours were reached whe n the tube ,

s howed slight pressure o n O pe n i n g T h e total qua ntity of .

a ctive oxyge n prese n t i n the be n zoyl acetyl peroxide therefore

remai n s after the hydrolysis .

Be nzoyl acetyl peroxide at room temperatures is slowly , ,

a ttacked by n ormal caustic soda or caustic potash givi n g o f f ,

o xyge n a n d depositi n g be n zoyl peroxide which latter is quite ,

S table i n the cold a fact which was also observed by Ne i , .

l

Baeyer demo n strated that the aci d sodium salt of be nz 0p e r

a cid also rapidly gives o f f oxyge n an d leaves sodium be nzoate
2
a n d be n zoyl peroxide a nd to explai n this cha n ge he assumes ,

t hat 3 molecules of be n z o p e r ac i d form on e of be n zoyl peroxide

a nd o n e of a n oxyge n ated be nz op e r ac i d which l atter the n de ,

c omposes i n to oxyge n an d be n zoic acid

C6 H5 C O O O H . .

C6 H5 C O O EO H . . C6H 5 C O
Hz O
C 6 H5 C O O
,

If this same reactio n were to take place i n aqueous solutio n ,

t he n as there is no loss of oxyge n i n the above experime nts

, ,

1 A C h m ( L i bi g ) 9 8 85
nn . e . e , 2 , 2 .

1 Be r d . . c he m . Ge s .
, 33 , 1 5 7 0.
1 82 Fr e e r a nd N avy .

we would have to assume that the oxyge n ated be n ZO p e rac idi

is stable except i n the prese n ce of alkalies a nd that the pri ,

mary result is the hydrolysis of be n zoyl acetyl peroxide to be n

z 0p e ra c i d an d acetic acid It will be shown that this is n ot
.

correct .

If Baeyer s equatio n is correct the n the 2 grams of be n zoy l

’
,
»

acetyl peroxide hydrolyze d above should whe n equilibriu m

”

is reache d leave , gra m of be nzoyl peroxi d e as an i nsolu

'

ble remai n der a nd the solutio n shoul d co ntai n

, 1 4 3 gram .

of active oxyge n However as will be see n from the table

. .
, ,

the complete cha n ge to be n zoyl peroxide whe n all be nzoyl ,

“

acetyl peroxi d e has disappeared results after o ne hu n dred ,

a n d forty four hours a n d the n leaves o n ly

-
,
gram ap prox i ,

mately of be nzoyl peroxide an d

,
gram active oxyge n i n ,

solutio n This would more nearly represe nt a cha n ge i n

.

which o n e fourth the active oxyge n had separated as be n zoy l

-

peroxide .

A n other view of this cha nge was a p ri or i n o t u nre as on a , ,

’

ble n amely that be nz oyl acetyl peroxi d e su ffers gaseous dis

, ,

sociatio n i nto the a n io n s of be n zoic an d acetic acids ,

C , H, C O O .

an d that the two be nzoic aci d io n s the n u n ite to form the i n

soluble be n zoperoxi d e leavi n g the acetic acid a n io n s as th e
,

active co n stitue nt This V iew is n o t te n able however be

.
, ,

cause
1 The amou n t of be n zoyl peroxide formed would the n c on
.

tai n on e half the active oxyge n Two grams of be n zoyl acetyl

-
.

peroxide i n the above experime n t should yield if all the be n ,

z oy l was co n verted i nt o be n zoyl peroxide grams of the ,

latter i n stead of 5 gram as fou n d .

2 .B e n zoyl peroxide is produced from the clear solutio n ,

after filteri n g .

3 Dilute solutio n s of be nzoyl acetyl peroxide i n absolut e

.

ether or petroleum ether eve n after sta n di n g t hirtee n days , ,

d eposite d u ncha n ged peroxide on evaporatio n .

4 The molecular weight determi n atio n i n be n ze n e eve n at

.
,

great dilutio n gave n umbers so n ear the theoretical that no

,
1 84 Fre e r a nd N avy .

zoic acid is i ndicated by its crystallizatio n from cooled c on ,

ce n t rate d hydrolyzed solutio n s A ttempts to produce be n zoyl

.

peroxide by the actio n of be nzoic acid upo n be nz ope rac id gave

n egative results .

The amou n t of be n z o pe rac id in the fully hydrolyzed solu

tio n will vary with the co n ditio n of hydrolysis Obviously if .
,

the reactio n ( 3 ) is retarded it will result i n the formatio n of

an exces s of be nZ O p e ra c i d over a n d above what is n ecessary to

co mbi ne with the u nhydrolyzed peroxide U n der such con .

d itions the solutio n m ay co ntai n 1 0 to 2 0 per ce n t of the active

oxyge n i n the form of be nz op e rac id O n the other h a nd c o n .
,

d itio n s which haste n reactio n 3 ) yield solutio n s co n tai n i ng

little or n o be nz op e rac id It is evide nt therefore that the
.
, ,

chemically an d bacterially acti ve co n stitue n t in the hy d rolyzed

s olutio n of be n zoyl ace tyl peroxide is ace t op e ra c i d either ,

alo n e or associated with small but va riable amou n ts of be n zo

peracid .

The use of solutio ns of be nzoyl acetyl peroxide as germi

cides re ndered a determ i n atio n of the solubility i n water n e c e s
sary The best method of arrivi n g at accurate results was to
.

decompose the substa n ce with N / 2 0 potassium h y d rox id e a nd , .

to titrate the excess of alkali with N / z o hydrochloric acid If .

a weighed qua n tity of be nzoyl acetyl peroxide is treated with

an excess of N / 2 o potassium hydroxi d e, an d at o n ce warmed

o n a water bath u ntil all be nzoyl peroxide has d isappeared ,

-

the results i nvari ably sho w the n eutralizatio n of more tha n

the calculated qua ntity of cau stic potash by 1 or 2 per ce nt .

If on the other ha nd the peroxide is allowed to sta n d i n the

, ,

cold with the alkali for twe n ty four hours u ntil the be n zoyl
-
,

acetyl peroxid e is completely co n verted to be n zoyl peroxi d e ,

a n d the solutio n is the n warmed o n the w ater bath the results -

,

are very accurate and correspo n d exactly to those calculate d

for the productio n of 2 molecules of acid .

gram substa n ce treated with 7 0 cc N / 2 0 potassium .

hydroxide required cc N / z o hydrochloric acid to n e u

.

t raliz e . C alculated , cc .

gram substa n ce treated with 7 0 cc N / 2 0 potassiu m .

hydroxide required cc N / z o hydrochloric acid to n e u

.

tral iz e . C alculated , cc .
 l and D za ce ty l P e rox zde s
’ ’

B e nz oy l A ce iy .

H avi n g established the accuracy of the method we carried ,

o ut the followi n g experime n ts

The peroxide purifie d by several recrystallizatio n s was
, ,

fi nely pulverized and the n shake n with water at The

amou n t of peroxide use d did n ot a ffect the results but the ,

t ime of sha k i n g did It was n ecessary to shake for two or.

three mi n utes un til a maximum solubility was reached The .

i n crease i n the a mou nt i n solutio n with le ngth of shaki n g is

due to the cha n ges show n i n the table give n above and as , ,

i n dicated the rise is a slow one ,

C ha n ges of temperature of .
,

course materially a ffect the result ;

,

Three te n ths gram substa n ce was shake n with 1 1 0 cc

-
.

water at 2 filtered quickly through asbestos with suctio n

, ,

a n d 5 0 cc removed a n d treate d with 1 0 cc

. N/ 2 o caustic pot .

ash A fter warmi ng o n the water bath for several hours the
.
-

excess of caustic soda was titrate d .

N z o t h i o s ulph a t e
/
C u a s ti c p ot h as u se d to d e t e r i n e m
re qu .

i re d . a c tiv e o y en x g .

5
10

15

20

30
40

The above table shows that for 1 molecule of peroxide i n

solutio n there is 1 atom of active oxyge n for the n umber of ,

c ubic ce n timeters of N /2 o caustic potash a nd N /2 0 t hi o s ul

phate are the same an d 2 molecules of caustic potash i n form

,

i ng 2 molecules of salt from 1 of peroxide are equivale n t to 2

molecules of thiosulphate in reduci n g io d i n e This fact c on .

firms the view that the first cha n ge is hydrolysis with the pro
1
ductio n of peracids as i nd icated above i n equ atio n s 1 a nd 2
,
.

The solubility after five mi n utes is therefore the e q u iv a

, ,

le n t o f cc caustic potash i : 1 per ce n t which correspo nd s

.
,

to gram per liter This wo ul d represe n t gram .

active oxyge n per liter A 1 per ce nt hydroge n peroxide .

solutio n would co ntai n grams active oxyge n per liter , or

1 E l u c tivi ty m a s u r m n ts f so lution s o f b e n oy l a c e ty l p e ro xi d e
e c t ri c c on d e e e o z

s h ow e d t h t a p id h y d o l y s i t k pl W i th o hm s e i ta n e t h e b ri d g
’
a r er r s s c e
s a e s ac .

re a d i n g s f ll f m 85 to 340 i n t w l
e ro m i n u te s
0 e ve .
1 86 F re e r a nd N avy .

eighty times as m uch Nevertheless as will be show n be

.
,

low these d ilute solutio n s of be n zoyl peroxide have a much

,

greater germicidal actio n tha n eve n moderately co nce ntrated

o n es of hydroge n peroxide The reaso n for this is a p ri ori .
, ,

n o t appare n t for in th e o n e case we h ave a substa n ce of the

,

formu l a H 0 0 H an d i n the other

. . . Th e germ
i c id a l actio n is therefore n o t due exclusively to the absolute,

qua n tity of act i ve oxyge n i n u n it space so that som e other ,

cause of which we ca n n ot at prese n t fur nish an expla n atio n

, ,

must be at the bottom of this remark able fact H y d roperoxide .

,

whe n pure is practically odorless be nz o p e rac i d an d ac e top e r

, ,

acid both of which have the same i nte n se germici d al actio n

, ,

h ave most pe n etrati n g o d ors resembli n g hypochlorous acid , .

This latter fact suggests a study of hypochlorous acid from the

sta n d poi n t of a p eroxide A ll of these facts
,

poi n t to a differe n ce betwee n hydroperoxi d e a n d the orga n ic

acid peroxi d es which are germicides which must be a subj ect ,

of future i nvestigatio n .

The decompositio n of be n zoyl acetyl peroxi d e with so d ium

ethylate gives be n z op e rac i d a n d a ppare n tly n o ace tO p e rac id , , .

Seve n an d a half grams of pure be n zoyl a c etyl peroxi d e were

dissolved i n 2 00 cc absolute ether an d coo le d to
.

gram of so d ium dissolved i n alcohol an d cooled to

the n slo w lv a dde d care bei n g take n to allow n o rise i n tem
,

p e r a tu re The solutio
. n i n sta n tly forms a precipitate which

almost solidifies the e n tire mass The precipitate was allowe d .

to sta n d for te n mi n utes d uri n g which tim e it gave off some

,

oxyge n Two h u n d red grams of ice were the n added an d

.

shake n u n til all the solid we n t i n to solutio n The ether was .

the n separated an d the remai n d er after a dd i n g froze n d ilute ,

sulphuric acid was extracted five times with ethyl c hloride

, .

O n evaporati ng the ethyl c hlori d e a solid remai n e d havi ng ,

the i n te n se odor of be nzoyl peroxi d e This whe n treated .

,

with sulphuric acid a n d alcohol yiel d ed o n ly be n zoic ester , ,

a n d no acetic ester The solid is therefore a mixture of be n

.
, ,

z o e r a c i d a n d be n zoic a cid
p It m ay be possi ble by special .
,

methods to isolate ac e tO p e r ac id
,
.

A C E T Y L P E R O X DE I .

A cetyl peroxide is best prepare d as follows : C om mercial

1 88 Fre e r a nd N avy .

GE R MI C I D A L A CT ON I .
‘

It has bee n poi nted out that certai n peroxides are chemically
i ndi ffere n t while others are active oxidizi ng age nts The .

chemical behavior i n this respect o ffers a very good i n dicatio n

of the actio n of these bodies upo n bacteria Those peroxi d es .

which are chemically i nert are also g e rmic id ally i n active an d ,

vi ce ve r sa Before proceedi ng i n to a detailed co nsi d eratio n of

.

this aspect it may be well to obtai n a ge n eral view as it

, ,

were of the peroxides heretofore me ntio n e d

,
.

H ydroperoxide H 0 0 H , . . .

Be nzoyl peroxide C6 H5 C O ,
. O O COC
. . H
A cetyl peroxide ,

Be nzoyl acetyl peroxide ,

It will be see n from the above formulas that the three or

ga mic compou n d s possess a symmetrical structure similar to
‘

that of ordi n ary hydroge n peroxide The latter substa n ce as .

,

is well k n ow n is a fair germicidal age nt especially whe n

, ,

stro n g solutio n s are employe d O n the other ha nd be n zoyl .

,

peroxide is d iffic ultly soluble does n ot u ndergo hydrolysis , ,

has n o oxi d izi ng actio n a n d is wholly without effect upo n ,

bacteria Whe n compared with acetyl peroxi d e an d be n zoyl

.

acetyl peroxide however a remarkable di ffere n ce is observe d

, , .

The last two compou n ds may also be looked upo n as chemic

ally an d biologically i n ert but u n like be n zoyl peroxide they , , ,

readily u n d ergo hy d rolysis with the productio n of i nte n se

oxi d izi n g a n d actively germici d al bo d ies The hydrolysis of .

these bodies has already bee n discusse d an d it is sufficie n t in ,

this co nn ectio n to i ndicate that the active peroxides resulti ng

from the hydrolysis of the i n active forms are
B e n z op e rac i d , C 6 H5 C 0 0 O H . .

A c e t0 p e rac i d ,

These perac ids possess it will be note d a n asymmetrical , ,

structure an d as stated above they are extremely active n ot

, , ,

o nly chemically but also g e r mic idally In fact whe n solu .

,

tio n s of these peroxides are tested upo n bacteria an d the effect

1 T h e b a c te ri o lo gi c l w o rk
a in e x te m o wi l l a pp e ar i n the Jou rn al ofE xpe r i me n tal
Me d i ci ne , rgo z .
 D za ce éyl P e raxzae s
'

e e zy l a nd
’
’
B e n z oy l A ‘
.

produced is compared with that caused by a solutio n of h y

d roge n peroxide of like oxyge n co n te n t that is of e q ui mole c , ,

ular stre n gth it will be fou n d that these orga n ic peroxides

,

are at least seve ral hu n dre d times more active tha n hydroge n
peroxi d e I n asmuch as the active oxyge n co n te n ts i n such
.

solu tio n s is the same it is diffi cult to explai n the di ffere n ce i n

,

e ffects by mere refere n ce as has bee n the case heretofore to

, ,

n asce n t oxyge n E it he r the active oxyge n does not d irectly

.
r

participate i n the reactio n or else we m ust assume that it is

,

l iberated from the orga n ic peroxides with an e n ormously

higher pote n tial e n ergy tha n is the case in hydroge n p e ro x
ide It shoul d be n ote d i n passi n g that whil e hy d roge n per
.

oxi d e loses its available oxyge n readily an d eve n viole ntly o n ,

co n tact with e n zymes bloo d a n d other orga n ic flui d s no such

, ,

rapid dise n gageme n t is observable w ith the peracids I n d ee d .

,

the additio n of be n zoyl acetyl peroxide to blood while it causes ,

i n time the d estructio n of hemoglobi n yet it d oes so without ,

visible evolutio n of gas .

The simplest expla natio n of th e d i ffere n ce in a c tio n betwee n s

the peracids an d hy d roge n peroxide appears to us to be base d

upo n the behavior of the acid io n s The acetyl an d be nzoyl .

io n s j ust as th e sulphuryl i o n i n C aro s aci d are to be c on

,
’
,

s i d e re d as the active groups which by their avidity for pro ,

t e i d s a n d other chemical substa n ces i n duce the pro n ou n ced ,

germici d al an d oxidizi n g effects .

The activity of the hydrolyzed solutio n of d iacetyl perox i d e

is d ue to ac e top e rac id while that of be n zoyl acetyl peroxi d e
,

is due at times wholly to a c e tO p e rac id more ofte n ho wever , , ,

to this peracid plus variable a m ou nts of be nz op e rac id as has

alrea d y bee n explai n ed .

Be n zoyl peroxi d e m ay be d ismissed i n a few wor d s Si n ce .

it does n ot hydrolyze it does n ot exert a n y germicidal actio n

whatever This is most clearly see n by the fact that the ex
.

t re me l y weak cholera vibrio is wholly u n a ffected by be n zoyl

peroxide .

The hydrolyze d solutio n s of ace tO p e rox i de and be n zoyl

acetyl peroxid e by co ntrast exhibit remarkable germicidal
effects Thus solutio n s co ntai n i n g
.
, a nd eve n per
ce n t active oxyge n are cap able of destroyi n g withi n a mi nute
1 00 Fre e r a nd N avy .

all k now n disease produci n g bacteria i ncludi n g the spores of

-
,

such extremely resista n t forms as the potato bacillus .

The methods of testi n g these solutio n s n eed not be c on

sid e re d here i n asmuch as they are give n i n d etail i n the paper
,

referred to It will n ot be out of p l ace however to prese n t a

.
, ,

few tabulated experime n ts which will serve to sho w at a gla n ce

the results obtai n ed I n these tables i ndicat e s that a
.

growth resulte d i n other words that disi nfectio n d id n ot oc

, ,

cur O n the other ha n d

. i n dicates that n o growth o c ,

curred a n d he n ce the germicidal actio n is ma n ifested It .

should be stated also that co ntrol experime n ts were i nvari a

, ,

bly m a d e to test the viability of the cultures used for each ex

p e ri m e n t .

H ydrolyzed A cetyl P eroxide ( 1 per ce nt ac

tive oxyge n .

Min u te s .

B p y oc y an e us
.

B coli.

B typhosus
.

B d iphtheri a
.

V ib choler ae
.

S p y og aureus
. .

Strept pyoge n es
.

Spores a nthrax B .

hay B .

potato B .

The acetyl peroxide for this experime n t was prepared ac

cordi n g to the method previously give n It will be seen from .

the above table that the relatively weak sol utio n possesses
e n ergetic germicidal powers E ve n a weaker solutio n will .

produce practically the same results which i n that case are , , ,

comparable with those give n i n Tables I I an d I I I . .

A compariso n with Table IV will show that a hydroge n .

peroxide solutio n co ntai n i ng twice the amou n t of active oxy

g e n is n evertheless
, a very feeble germicide ,
I n deed to pro .
,

d uce like results it would be n ecessary to use a hydroge n

,

peroxide solutio n co n tai n i n g 1 00 to 2 00 times as much active

oxyge n as that co ntai n ed i n the p e racid solutio n Table IV . .
1 92 F re e r and N avy .

see n is i n a cc ord with those give n by the hydrolyzed solu

,

tio n s of acetyl peroxide an d be n zoyl acetyl peroxide .

Ta ble I V .

H y d r o g e n P e i-o i d e , x P he n l o .

(l )
per c e n t a c ti ve o x y ge n 5 pe r c e nt
Mi n u t e s Mi n u te s
. .

. .

1 .
3 .
5 . 10 . 15 .
30 . 60 .
5 . 15 .
30 . 60 .

B py oc y a n e us
m
.

R
B typhosus
.

B d iphtheri ae
.

V i b cholerae
.

S m% w m s
Strept pyoge n es .

Spore s an thrax B .

l w B
“

mw a
The results record ed i n Table IV serve for compariso n .

with those give n i n the precedi n g table Thus it will be see n .

,

that while the hydroge n peroxide solutio n co n tai n s te n times

as much active oxyge n as the be n z op e rac i d solutio n used in
Table I I I the germicidal effect is e ntirely d iffere nt .

These few examples serve to illustrate the i n teresti n g fact

which we have brought out n amely that while the sy mme tri , ,

cal orga n ic peroxides are i n ert the asymmetrical peracids ,

easily ra nk amo n g the most p ow erful germicidal age nts

k n ow n For a more exte n d ed accou n t of these bodies it will
.

be n ecessary to refer the reader to the paper which deals

espe c ially with their germicidal behavior .

The results g i ve n i n this paper are by n o mea n s complete ,

but as one of us expects to be away fro m his work for a year

or more we thought it best to publish the results obtai n ed up
,

to this time The work i n this i nteresti n g and large field

.

will be co n ti n ued i n the future an d as we hope ma ny of the , ,

doubtful poi nts cleared up The b act er iological work will .

also be co nti n ued with this an d other bodies of the same class .

L O TAB ES G E N E L C HE M ST Y
R A OR I OF R A I R

D n H Y G E N E U m v n n sx v
AN o M I , r OF I011

G N A An n c n I A , N N so , .
 C t i bu t i
on r o ns fro m th e C h m i a l L ab o
e c rat ory of Ha rv ard C o lle ge .

C XX IX .
—
ON d N IT R O P Y R O
-
MU C IC A C ID .
1

BY H ENR Y B . H 1L L A N D GE O R G E R Wa r n s . .

In 1 888
“

H ill
fo un d that d s ulp hO py rom u c ic
a nd P almer
2
-

acid was decompo sed by co n ce n trate d n itric aci d with the

formatio n of the d n it rop y ro mu c i c acid which had bee n oh -

"
t ai n e d by K l i n k ha rd t a few years previously by the actio n of
n itric a c i d upo n dehydromucic acid They also fou n d that a .

n eutral body was formed at the same ti m e which appeared to ,

b e a d i n i tro fu rfur an but the material at their d isposal did n ot ,

e n able them to study it i n d etail From th e fi bromfi i sulp ho .

-

a n d the fl y dibrom d su lp hO p y ro mu c i c acids they obtai n ed

,
- - -

the correspo ndi n g brom i n e derivati ves of t he d n itrop y rom u cic -

aci d a n d they further isolate d the fl fi dibrom a cit d i nitro fu r

,
- -
,
-

fura n Si milar acids were obtai n e d a few years later by H ill

.

”
L J ackso n a n d by H ill a n d H e ndrixso n from th e
‘
an d L . .
,

c h lors u lp h o p y ro m u c i c aci d s .

It seemed to us that the material n ee d ed for an exte n d e d

study of the d n i tr0p y ro mu c ic acid could be m ade most c o n
-

v e n i e n t l y from 6 s ulp h0 p y ro m u c i c acid si n ce the metho d s

-
,

which were the n k n ow n for the preparatio n of dehydrom u cic

aci d i n volve d a great expe n d iture of ti me an d labor Most .

of the n it r0 p y rom uc i c aci d which we h ave use d was ma d e i n

this way but co nve n ie n t m ethods have re c e n tly bee n de
,

6
scribe d for m aki n g dehy d romucic acid i n large qua n tities ,

an d the method of K l i n k h a rd t is n o w much more eco n omical .

Our stu d y of th e n i tr0 p y ro m uc ic aci d was no t far adva n ced

whe n it was i nterrupte d by the removal of one of us from
C ambr i d ge an d its progress has si n ce bee n d elayed by cir
,

c u m sta n c e s beyo n d our co n trol Si n ce further collaboratio n .

seems to be out of the questio n we have thought it best to ,

1 T h e w or k de s c ri b e d i n th e fo ll ow in g p p e f me d a p a r or a rt of a t h e si s p re s e n te d
to th e Fa cul ty o f A t n d Sc i n o f H v d U n i e i ty i M y 1 89 6 b y G e org
r s a e ce s ar ar v rs , n a , , e

R n t ul W h i t
a o c did t e for t h e d g re e o f D o t r o f P h i l
e , an a ph y e c o o so .

Th i s J OU R N A L l o 38 ; P r A m A c ad 2 3 195
3
‘

, 0 oc . . .
, , .

J p k t Che m
3 . ra 25 5 , 1.

Th i s J O U R N A L u 1 6 ; P oc A m A d 2 4 36
4
, , 2 r . . ca .
, , 1.

Th i J O U R N A L 15 149 ; P
5 s Am A d 25
, ,83 ro c . . ca .
, , 2 1 .

H i ll B e r d c h e m G e s 3 2
0 : . .
; P h e lp s nd H l . Th i s J O U R N A L 2 5 45 ;
.
, , 12 2 1 a a e : , ,

Y de n d T ll n B d h m G
o r a o e 3 4 3 44 6
s : e r . . c e . es .
, ,
.

I 3— 2 7
1 94 H i ll a nd White .

publish i n their prese n t i n complete form the results which we

have obtai n ed .

C o n ce ntrated n itric acid acts upo n d sulph O p y romuc ic acid -

at ordi n ary temperatures and th e reactio n is completed o n

ge n tle warmi ng The reactio n proceeds simulta n eously in
.

two directio n s but we have bee n u n able to determi ne the

,

co nditio n s favorable to the formatio n of either pro d uct N i .

t rO p y ro muc ic acid is formed by the replaceme n t of the sulpho

group a n d at the same time a nitrofurfuran sulp ho nic acid t e
,

s u lt s from a similar replaceme n t of the carboxyl The former .

is Spari ngly soluble i n cold water while the latter c an be iso

,

lated through its spari n gly soluble potassium salt Both of .

these bodies are the n co nverted i nto d i n i trofurfuran by the

co nti n ued actio n of fumi n g n itric acid although the nitr0py ,

ro mu c i c acid is but slowl y attac k ed u n less sulphuric acid is

prese nt in co nsiderable qua ntity .

HC —
C —
C OO H

HC z C —
C OO H H =O —
N o, HC : C —
N O,
\0
HC z C —
S0, 0 H H C =C —
N O, HC Z C —
N O,

i ro s o —
so, or1

Whe n d ehy d romucic acid is treate d with 1 0 parts of n itri c acid

an d 1 part of sulphuric acid as recomme n ded by K li n k h a rd t
, ,

but little d in itro fu r fura n is forme d .

We have also fou n d that n i tr0p y romu c ic acid m ay be m ade

by the actio n of nitric acid upo n a solutio n of pyromucic acid
i n fumi n g sulphuric acid without isolati n g the sulpho n ic acid .

A savi n g i n time and labor is thus e ffected but great care ,

must be take n to avoid any co n siderable rise i n temperature

a n d c o nse q u e n t id e stru c ti v e oxidatio n .

N it ropy romu c ic acid forms stable salts but it is rapidly de ,

compose d by an excess of an alkali n e hydrate With baric .

hyd rate three equivale n ts were fou n d to be i nvolved i n the re

actio n baric n i trite bei n g formed and at the same time a
, ,
1 96 H ill an d W/zi le .

A cti on o f tric A ci d
N i p
u on d — Sulplzapy r amuczc A ci d .

The d -
s u lp hO p y ro m u c ic
acid was prepared by exact p re c i p i
tat io n of a solutio n of its barium salt with sulphuric acid .

The filtered solutio n was co n ce n trated on the water bath and -

,

the acid the n thoroughly dried in a d esiccator over sulphuri c

aci d The fi n ely powdered acid was the n slowly a dd ed wit h
.

co n sta n t stirri n g to three times its weight of co n ce n trated u i

tric acid the specific gravity of which was at least
,
care
fully cooled with ice The solutio n was allowed to sta n d ove r
.

n ight at ord i n ary temperature the n warmed for a short time , ,

an d a part of the n itric acid drive n o f f at a ge ntle heat T he .

crystalli n e mass which was obtai n ed on cooli n g was treate d .

with a small amou n t of col d water drai n ed well with the ,

pump an d washe d with a littl e cold water This crystalli ne

,
.

product is d n itrO p y rom u c ic aci d mixed with varyi n g amou n t s

-

of d i n itro fu rfura n while the aqueous solutio n co ntai ns n itro

,

furfuran s u lp ho ni c acid A lt hough n itrO p y rom u c i c acid a n d

.

d in i trofu rfu ra n m ay be separated p arti ally by the use of sol

ve nts we have usually preferre d to n eutralize the n i tr0p y ro
,

mucic acid i n dilute solutio n with sodic carbo n ate a n d to re ,

move the d in i tro furfuran completely by extracti n g the feebly

alkali n e solutio n with ether The n itr0p y ro mu c i c acid is the n
.

extracted from the acidifie d solutio n with ether an d f urther

purifie d by recrystallizatio n from hot water The n i trofur .

furan s ul p hon ic acid c a n easily be isolated from the acid

'

mother liquor by n eutralizi n g it with potassic carbo n ate T h e

-
.

hot solutio n is a deep red brow n a n d o n cooli n g a highly col

-
,

ored potassium salt separates i n abu nda n ce The color m ay .

be removed by treatme n t with bo n e black a n d the potassi c -

,

sulphate by recrystallizatio n from hot w ater A certai n amou n t .

of the salt may be recovered from the mother liquors by add -

i n g baric acetate i n qua n tity sufficie n t to co n vert all the p ot as

sic sulphate i n to acetate an d co n ce n trati n g the filtered solu
“

tio n The yiel d of these th ree products has varied greatly i n

.

successive preparatio n s and we have no t bee n able to deter

,

mi n e the precise cause of this v ariatio n The maximum yield .

of each of the three pro d ucts n ecessarily i n differe nt prepara ,

tio ns was about 2 5 per ce nt of the s ulphop y romuc ic aci d

,
 O n d N i l r apy ramucicA ci d
-
.

T ake n ordi n arily however the amou nts obtai n ed were m uch
, ,

maller
s .

The preparatio n of the dry d sulp hopy romu c ic acid was a -

s imple matter but we thought that the time i n volved might,

be save d by allowi n g the n itric acid to act directly u po n a

s olutio n of pyromucic acid i n fumi n g sulphuric acid A t first .

we fou n d great d ifli c ulty i n mai n tai n i n g a su ffi cie ntly low

t emperature e ve n i n experime n ts co n ducted o n a small scale
, ,

b ut by usi n g a thi n seamless iro n dish set i n a freezi n g mix , ,

-

"

ture the reactio n coul d easily be co n trolled The iro n d ish

, .

w as hardly attacke d by the co n ce n trate d acids use d O ne

“

p art of pyromucic acid was dissolved in 3 parts of fumi n g sul

p h u ric acid the temperature n ot bei n g allowed to rise above
“

O n the followi n g day 3 parts of fumi n g n itric acid of ,

s p g r 1 5 1 were slowly added with co n sta n t stirri n g the tem

. . .
,
°

p e rat ure bei n g kept belo w 4 0 by mea n s of a freezi n g mixture

-
.

The product was kept i n the freezi n g mixture for at least an -

h o ur an d was the n allowed to sta n d at ordi n ary temperature

,

o ver n ight The d i n itro furfuran a n d n itr0p y romuc ic aci d

.

were the n extracted by ether from the d iluted sol utio n and ,

s eparated by mea n s of a dilute solutio n of sodic carbo n ate as ,

b efore By this method 1 00 grams pyromucic acid gave 1 7

.

g rams of n it r0p y rdmu c ic acid an d from 6 to 1 2 grams of di n i

t ro furfuran but no n itro furfuran sulp hon ic acid could be iso
*
,

l ated .

N i trafu rfu ra n su ¢lzam c A cid

°

A s y e t we have succeeded i n maki n g the n it rofu rfu ra nsul

-
pho n ic aci d o n ly by the actio n of n itric acid on the d sulpho -

pyromucic acid and we have n o t bee n able to prepare from , ,

‘

the spari n gly soluble potassium salt by mea ns of which w e

“

i solate d it an y other salts by double decompositio n

,
.

Pota ssi c N i l rafmfu ra n su/ p /zan a te This salt is ,

—

v ery spari ngly soluble i n cold water readily soluble i n hot ,

water and as the solutio n cools it is deposited i n brillia n t

, ,

l o ng flat recta n gular prisms which are a n hydrous

‘

.
, , ,

I . gram air dried salt gave gram K SO -

, ,
.

II . gram air drie d salt gave gram K SO , -

,
.

I II gram air d ried sal t gave

. cc N over K O H -
.

°
a t 27 a nd u n der a pressure o f 7 6 4 mm .
1 98 H il l a nd l iie .

Whe n treate d with twice its weight of co n ce ntrated n itri c

acid the potassium salt yields d i n itro fu rfuran i n abu n da n ce
, .

O n heati ng with distillable hydrobromic acid i n a sealed tube ,

at it was completely decomposed The diluted solutio n .

,

whe n extracted with ether yielded a crystalli n e acid which ,

°
melted at 1 6 0 to after recrystallizatio n from a small
qua ntity of water an d co n tai ned the perce n tage of bromi n e
,

required by a bro msucc in ic acid .

gram substa n ce gave gram A g Br .

Q ualitative tests showed that sulphuric acid had bee n

formed an d at the same time the solutio n reduce d cupric ox
,

ide vigorously i n the col d The body therefore appeared to .

have bee n d eco mposed accordi n g to the equatio n

,

K c , H , N so, 3 H, O + H Br C4 H5 BrO , K H so, + N H, O .

a ,
a D i n i i rafu ifu ra n
-

A ll the material which we have used was made from pyro

mucic acid by the methods j ust described Din itrofu rfuran is .
.

forme d however i n small qu a n tit y by the actio n of n itric aci d

, ,

upo n d ehydromucic acid a nd the amou n t is appare ntly in

,

creased if sulphuric acid is also added It may be ma d e fro m .

n i tr0p y ro m uc i c acid without d i fli c ulty by warmi n g it to 6 0

‘ °

with co nce ntrate d n itric acid to which a n equal volume o f

sulphuric acid is added The crude product which we ob .

t a in e d by extracti n g the alkali n e solutio n of n it r0p y ro m uc i c

acid with ether was recrystallized from hot alcohol .

I . gram substa n ce gave gram C O an d ,

gram H O ,
.

II . gram substa nce g ave cc N over K O H .

at 5 an d u n der a pressure of 7 8 0 mm .
2 00 H i ll a nd Whi te .

molecule in th e two cases O n co nce ntrati n g the aqueous

.

solutio n a barium salt separated in flat obliquely tru n cated

, ,
-

n eedles which appeared to be ide n tical i n form an d habit

,

with baric maleate ; i n the mother liquor was baric n itrite i n -

abu n da n ce The weights of the baric maleate obtai n ed cor

.

respo nded to and molecule respectively The .

amou nt of nitrite formed was determi n ed with separate por

tio n s of d in itro fu rfuran a nd as the mea n of two determi n atio n s
,

it was fou n d that per ce n t of the n itroge n had bee n c on

verted i nto ba ric n itrite The baric maleate was decomposed
.

by d ilute sulphuric acid taki ng care to leave a trace of barium

,

in solutio n and the solid obtai n ed by evaporatio n was the n

,

extracted with ether The aci d thus obtai n ed was readily

.

soluble i n ether a nd very soluble i n cold water It melted at .

°
13 1 to s ublim ed readily betwee n watch glasses an d the -
,

°
last portio ns of the subli mate melted at 5 2 to O n evap
oratio n with hydrochloric acid a spari n gly soluble acid was ,

obtai ned w hich had all the characters of fumaric acid I n .

additio n t he barium salt was show n to have the compositio n

,

of baric maleate .

gram air dried salt lost at-

gram H O , ,
.

C l ul t d f a c a e or
B 8 C 4H 2 0 4 . H 20

gram salt dried at , gave gra m B asO , .

u
Fo n d

d -N i l rapy r am uaic A cid .

The ni trO p y ro muc i c acid used was recrystallized from hot

water and agreed i n properties with the descriptio n of Kli n k
,

hard t In the preparatio n of salts of the acid we n oticed that

.

a n excess of an alkali n e hy d rate immediately brought about

a ch a n ge of color an d that decompositio n soo n set in at or d i

,

n ary temperatures The cha n ge of color to a reddish yellow

.
-

is sufi c ie n tly well marked to serve as an i n dicator in the titra

tio n of the acid In two successive trials
. gram of the
acid require d an d cc of a baric h y d rate solutio n 1 . ,
 O n d N i i r apy r amucic A ci d
-
.

cc of which was equivale n t to

. cc N / 1 0 hydrochloric .

acid the calculate d amou n t is With an excess of

baric hy d rate a dark brow n fl oc c u le nt precipitate is slowly
-
, .

formed at ordi n ary temperatures an d the same decompositio n ,

takes place at o n ce on bo i li n g i n either case exactly 1 5 .

molecules of baric hy d rate are i nvolved i n the reactio n Baric .

n itrite is forme d i n abu n da n ce but we have n o t succeeded i n , |

d etermi n i n g the n at ure of the i n soluble product .

If ethereal solutio n s of n itr0p y romu c ic acid an d a n ili n e are

mixed a n ili n e n itr0p y rom uc ate at o n ce separates i n colorless
, ,

clustered leaflets The salt is very spari n gly soluble i n ether

.
-

or i n cold alcohol bu t it dissolves freely i n boili n g alcohol

,
.

O n exposure to the air it rapi d ly tur n s d ark i n color The .

salt dried i n a desiccator gave the followi n g results

I . gram substa n ce gave gram C O an d ,

gram water .

II . gram substa n ce gave cc N Over K O H at .

°
25 and u n der a pressure of 7 5 4 mm .

Fo und .

0 0 0 . 11 0
53

This a n ili n e salt is spari n gly soluble in cold water and may
be r e crystallized from hot water A n aqueo us sol utio n at .

ordi n ary temperature is slowly decomposed with the p re c ip i

tat ion of brow n ish flocks If a n ili n e is added to the aqueous
.

s olutio n or better a n ili ne acetate the reactio n is accelerated

, , , ,

an d a volumi n ous brillia n t red precipitate is formed after the

,
-

lapse of a few hour s This body may be prepared more c on

.

v e n ie nt ly by addi n g rather more tha n 2 molecules of a n ili n e

hydrochloride to nitr0p y rom uc ic acid dissolve d i n a sol u tio n

of sodic acetate The solutio n should n ot co n tai n more tha n
.

1 5 per ce n t of the n i tr0 y ro m u c i c acid i n order that n o an i

.
p
li n e salt may separate The solutio n soo n grows turbid and
.

gradually deposits the red body at the same time carbo nic
dioxide is slowly evolved A fter sta nd i n g for forty eight .
—

hours at ordi n ary temperature the reactio n is i n great part

complete d but the filtered solutio n agai n grows turbid an d
,
2 02 H i ll a nd l i le .

co nti n ues for several days to deposit small amou nts of the col
ored product The reactio n may be accelerated by heat but
.
,

the color of the product is the n n ot so brillia n t The weight .

of the precipitate whe n dried was usu ally about 2 5 per ce n t

mo r e th a n that of the n i trO p y ro m u c ic acid take n O n closer .

exami n atio n the substa n ce prove d to be a mixture of two

bodies which could easily be separated by mea n s of chloro
form Whe n thoroughly extracted with chloroform an ora n ge
.

yellow bo d y was left which a mou n ted to about 80 per ce nt of

,

the mixture taken while the dark red chloroform solutio n

,
-

co ntai ne d a crimso n substa n ce .

The yellow body proved to be very spari n gly soluble or i n

soluble i a all ordi n ary solve n ts except glacial acet i c acid i n , ,

which it was not freely soluble eve n on boili n g A s the solu .

tio n cooled the body separated i n n early recta n gular four ,

poi nted stars which were d eep red i n color but gave a yellow
,
-

powder The material thus purified gave the followi n g re

.

su lts i n a n alyses I V an d V I the substa n ce was washed. .

with alcohol an d water

I . gram substa nce gave gram C O and ,

gram H O ,
.

II . gram substa n ce gave gram C O an d 2

gram H O ,
.

III .gram substa n ce gave gram C O and ,

gram H O ,
.

IV gram substa n ce gave

. gram C O an d 2

gram H O ,
.

V . gram substa n ce gave cc N over K O H at .

°
15 an d u n der a pressure of 7 6 9 mm .

VI gram substan ce gave

. cc N over KO H at .

°
17 an d u n der a pressure of 7 7 3 m m .

C l ul
a c a te d for Fo u nd .

0 0 0 0 0 0 0 .

Whe n quickly heated the substa n ce melted at but this

melti n g poi n t was lowered several degrees by slow heati ng
- .

The body was i ndi ffere n t to aqueous acids or alkalies but it ,

2 04 H i ll and White .

Fo nd u .

0 0 0 .

This body is spari n gly soluble i n alcohol or ether but is ,

readily soluble i n chloroform be n zol or hot glacial acetic , ,

acid From the latter solve n t it cry stallizes i n flatte n ed crim

.

°
s on n ee d les which melt a t 2 1 8 whe n slowly heated but de
, ,

compositio n appare ntly sets i n at a lower temperature We .

have not yet succe eded i n prepari n g serviceable derivatives of

this body .

W e have also made the correspo n di n g derivatives of para

tolui d i n e The properties of these bodies are almost id e n ti
.

cal with those o f the a n ili n e derivatives an d they were ma d e ,

a n d purified by the same methods The yellow toluidi n e .

compou n d crystallized from glacial acetic acid i n clustered

°
prisms which m elted at 2 5 0 when quickly heated .

I . gra m substa n ce gave gram C O, a nd

gram H ,
O .

II . gram substa nce gave cc N over K O H at

.

°
2 1 an d u n der a pressure of 7 5 0 mm .

C l ul t d f a c a e or Fo n d u .

C ISH 17 N 30 .

74 . 16

On reductio n with co n ce n trated acetic acid an d zi n c d ust

it gave ammo nia paratoluidi n e a nd a bo d y which melted at
, ,
°
1 5 3 to a n d ha d the perce n t age compositio n of a tolyl

succi n imi d .

I . gram s ubsta n ce gave gram C O an d ,

gram H O ,
.

II . gram s ubsta nce gave cc N over K O H at .

°
17 a n d u n d er a press ure of 7 6 9 mm .

C l ul
a c d fo r
at e Fo und .

CHHHN OQ .

5 86
0
O 0 0 0

7 44
0 - 0 0 0 0
 Sepa ra ti on of Hy drochl or ic and Hy dr ocy a n i c A cids . 2 05

The crimso n co mpou n d crystallized from glacial acetic acid

i n fi n ely felted n eedles which were decomposed on heati n g , .

Whe n w ashed with water an d dried over sulphuric aci d it

gave the followi n g results
I . gram substa n ce gave gram C O and 2

gram H 0 2
.

II . gram substa n ce gave cc N over K O H at .

°
1 8 a nd u n der a pressure of 7 6 0 mm .

C l ul t d f F u d a c a e or o n .

0191117 17 3 0 3

THE Q U A NTI T A TIV E SE P A R A TI O N O F H Y D R O

C H L O R I C A N D H Y D R O C Y A N I C A C ID S .

B Y THE D E W LL M R C H D S D S DN EY K E N T S N G E
O OR I IA I AR A N I I R .

In the course of som e rece n t work which i nvolved the use

of very pure potassic cya n ide th e lack of a co n ve n ie n t method ,

for determi n i n g the amou n t of chloride prese n t in this salt be

came ma n ifest A ccordi n gly Miss G race E De nn ett an d
.
, .

Miss Selma H u n t adva n ced stu d e nts of chemistry at R ad ,

cli ffe C ollege teste d a n e w metho d at the request of o ne of

, ,
'

us U n fortu n ately lack of t i me preve n ted them fro m per

.
,

formi n g all the details n ecessary for the fi n al j udgi n g of the

metho d but their results were so promisi n g that the matter
,

seemed worthy of further pursuit This e nd we h ave acc om .

p li sh e d an d the prese n t paper co n tai n s a detailed descriptio n

,

of the method .

I n seeki n g to effect an y separatio n o n e n aturally utilizes an ,

operatio n which bri n gs i nto pl ay som e property possessed by

the two substa nces to be separated in as di ffere n t a measure
as possible Now the most striki n g d i ffere n ce betwee n hydro
.

cya n ic aci d an d hydrochloric acid is the di ffere n ce i n the de

l
gree of their io n izatio n A ccordi n g t o Walker an d C ormack .

“ ”
the dissociatio n co n sta n t of a te nth n ormal solutio n of hydro -

chloric acid is about n i n e thousa n d times as great as that of

equally co n ce ntrated hy d rocya n ic acid Both u n dissociated .

1
J Ch m S
. e L nd .
7 7 5 oc .
, o on , ,
2 06 R iclza r d: a nd Si ng e r .

acids are very volatile hydrochloric acid bei ng the more so , ,

but io n s have little or no te nde ncy to leave an aqueo us solu

tio n with steam H e n ce it seemed possi ble that by evapora
.

ti n g a dilute solutio n of the mixed acids with co n ti n ual ad ,

ditio n of water all the hydrocya n ic acid might be expelled

,

without the loss of a n importa n t amou n t of hydrochloric acid .

Si n ce some experime nts of R ichards an d Malli nc k rod t as ,

yet u n published sho wed that a te n th n ormal solut io n of h y

,
-

d roc hloric acid emits o n ly a n egligible amou nt of hydrochloric

acid with its vapor , the solutio n s were kept at this dilutio n by
the freque n t additio n of water The evaporatio n was effected .

i n vessels of various shapes all of which gave fairly satisfac ,

tory results T he chief disadva ntage of an O pe n dish on th e

.

steam bath was the da n ger of absorbi n g hydrochloric acid

-

fro m the air of the crowded laboratory duri n g the protracted

evaporatio n an d the chief disadva ntage of a com mo n flask or
, ,

of a large beaker with a fu n n el over it was the d a n ger of loss ,

of liquid i n the mi n ute drops caused by rapid ebullitio n We .

fi n ally decided upo n the use of a commo n un tu bul ate d retort

of 5 00 cc capacity with its n eck directed upwards at an a n gle
.
,

of In this vessel all the a n alyses give n belo w except ,

Nos 5 6 an d 1 5 were boiled A large beaker with an i n

.
, , , .

verted fu nn el over it was used i n the three cases named as ex

c e pti on s I n every case the p r ecipitatio n was effected i n a
.

large beaker .

E xperime n ts with perfectly p ure hydrocya n ic acid sh owed

that t wo hours boili n g was e n ough to expel every perceptible
’

trace of the acid The cooled solutio n gave no cloudi n ess.

with arge ntic nitrate .

In the n ext place a series of experime nts was executed with

”
C P. potassic cya n ide of commerce as the starti n g poi nt
.
-
.

A large volume of solutio n was made up a nd for each an aly ,

sis a qua n tity co ntai ni n g grams of the salt was take n .

This material was diluted to the bulk of about 4 00 cc an d to .

,

it were added 5 cc of sulphuric acid The mixture was sub . .

m itte d to active ebullitio n with the additio n of water i n such ,

measure as to preve n t t he volu me from ever falli n g below 300

cc A t the e nd of a prearra nged time the ebullitio n was
.

stopped an d the remai n i n g chloride was precipitated with arge n

 Si ng e r
'

2 08 R zcll a r ds a n d .

N o . of We i gh t K Cl W e i gh t A gCl W e i gh t A g C l
e xp e ri m e nt . a dd e d . ca c l ul a te d
. f ou n d (corn ) . E r ro r .

G ra m G ra m G ra m . Mi lli g ra m s .

9 +32 7
-

10

1 1

12

13

14

15

16

17

These results bri n g out several i nteresti n g poi nts In the .

first place two hours boili n g which amply s ufli c e d whe n lit
,
’
,

tle or n o potassic chlorid e was a dd ed is n ow e n tirely i n ad e ,

quate to expel all the hy d ro c ya n ic acid Thus somethi n g i n .

,
.

the solutio n must te nd to hold back this acid But the o n ly .

i mporta n t additio n to the solutio n is the chlori n e i o n he n ce ,

the chlori n e iou must te nd to form a complex with hydro

cya n ic acid The te n d e n cy of this i o n to form complexes
.

with various other un dissociated groups has bee n n otice d be

‘
fore especially by R ichard s a n d A rchibal d so that this be
, ,

havior is n ot startli n g but it is n ev e rtheless a matter of i n ter ,

est which will receive further atte n tio n i n this laboratory .

Of more d ire c t beari n g upo n the imme d iate obj ect of the
prese n t research is th e fact that after eight or n i n e hours pro ’

lo nged boili n g this complex seems to be e n tirely broke n up by

progressive dissociatio n due to the stea d y volatilizatio n of on e
of its compo n e n ts a n d that this volatilizatio n is effecte d with
,

out loss of hydrochloric acid Thus it is shown that the .

m ethod really a ffords a co n ve nie n t an d adequate mea ns of

separati n g qua ntitatively the two acids in questio n P roba .

bly hydrobromic acid could be separated as easily as hydro

chloric .

While the hydrocya n ic acid might be collected a n d d eter

mi n ed i n the distillate it would probably be easier to deter ,

mi n e the amou n t by di ffere n ce precipitati n g both i n o n e por ,

tio n as arge n tic salts and the n precipitati n g arge n tic chloride
,

alo n e i n a n other portio n which had bee n evaporated i n the ,

ma nn er described in this paper The silver salts are so easily .

1 P ro c A . m . A c ad .
, 37 , 347
 N a tu r e of M e r cu ri c Iodide i n Solution .

weighed that this i ndirect method would not lead to serious

error .

The outcome of this paper may be summed up as follows

A simple method is described for the qua n titative a n alysis of
mixtures of chlorides a nd cya n ides an d evide n ce is give n ,

which i ndicates a te n de n cy on the part of hy d rocya nic acid to

add to the chlori n e ion .

C M DG E M s J
A BR I 7 9 , A s .
, an . 2 , 1 02 .

ON THE N A TU R E OF ME R C U R I C IO D ID E I N SO LU
TI ON .

BY J . H K A sr L
. E AN D J EWE TT V R . EE D .

A bout two years ago it was show n by K astl e a nd C lark 1

that solutio n s of mercuric iodi d e i n o rga n ic solve n ts have a

yellow color an d that from such solutio n s the yellow form of
the iodide a n d n ot the red separates o n crystallizatio n The .

e ffect of heati n g the red mercuric iodide with a m yl alcohol ,

keepi n g the io d i d e i n excess was also tried It was observed , .

that a yellow solutio n of mercuri c iodide was always obtai n ed

and that i n variably a thi n film of the yellow variety or a littl e ,

mass of yellow crystals was fou nd on top of the u n cha n ged ,

red io d ide The view was adva n ce d therefore that whe n

.
, ,

equilibrium is reached i n such solutio n s there are as m a n y

molecules passi n g out of the solutio n as are passi n g i n an d ,

that both are molecules of the yellow variety of this com

pou n d That the red iodide is n ot e n tirely cha n ged to yellow
.

by first passi n g i n to solutio n an d the n crystallizi n g out is

probably d ue to the fact that by co ntact with a certa i n amoun t
of the red variety remai n i n g i n the tube the yellow is rapidly ,

cha n ged to red as it separates from the solutio n We should .

,

t he re fo re h ave the solve n t co n sta n tly cha n gi n g the red iodide to

,

the yellow the n dissolvi n g it and agai n precipitati n g it i n the

,

yellow form This last however would te nd to pass back to

.
, ,

the red modificatio n as soo n as removed fro m solutio n It .

will be observed therefore that the e ffect of solve n ts o n the

, ,

red iodide of mercury i s esse n tiall y th e same a s that produced

by heat ; an d that i n the act of dissol v i n g the tra nsitio n tem ,

p e rat ure of the iodide is greatly lowered .

1 Th i J U N L 2
s O 47 3 4 84
R A , 2 , , .

1 4— 2 7
2 10 K a stle a nd Re e d .

Inthis co nnectio n it occurred to us to d etermi n e whether

the yellow form of mercuric iodide could exist in equilibriu m
with its solutio n at temperatures below its tra n sitio n poi nt -
,
°
vi a ,
128 C With this i n V iew tubes were prepared co ntai n
.
,

i ng amyl alcohol an d red mercuri c io d ide the latter i n excess ,

of that required to form a saturated solutio n at the give n tem

These tubes were h heated the air ove n at 1 5 0 °

p e r a t ur e . t e n i n -

C u ntil a saturated solutio n of the iodi d e i n amyl alcohol was

.

obtai n ed an d u n til the excess of the iodide had bee n tra n s

formed to the yellow mo d ificatio n The t ube s w e re the n placed .

i n the vapor of boil in g glacial acetic acid 1 1 8 C

°
For so me , .

time after putti n g the tubes i nto the vapor of the acetic acid
the yello w crystals of the iodide showed n o alteratio n In .

about te n mi n utes ho wever red spots bega n to appear amo n g

, ,

the yellow crystals i n dicati n g that n o equilibrium was possi

,

ble betwee n the yellow variety of mercuric iodide and its

°
saturated solutio n i n amyl alcohol eve n at 1 0 below the tra n
sitiou temperature of the compou n d These experime n ts were .

repeated several times with li k e result in every case .

A re Solu ti on s of M ui e rc r c Iodi de Sa tu ra te d w i t/
t tlz e Ye llow or

Re d M difi o ca ti on o f the Comp ou n d 9 .

was poi nted o ut in our previous co mmu n icatio n the

As ,

color of solutio n s of mercuric iodide is such as to i n dicate that

they are saturated w it h respec t to the yellow variety of this
compou n d o nl y With the view of throwi n g still further light
.

o n this questio n which fro m a theoretical sta n dpoi n t is o n e

, , ,

of great importa n ce the attempt was made to prepare super

, ,

saturated solutio n s o f th e iodide i n certai n of these solve n ts ,

with the view of testi n g the co n d uct of such solutio n s towards

crystals of the red an d yellow variety of the compou nd C on .

'

si d e rabl e d i fli c u l t y i n th e se l e c t io n of a solve n t was e n cou ntered

at the ou tset i n co n seque n ce of the great te n de n cy o n the part

of the iodide to crystallize A mo n g the first solve n ts to be .

tried was amyl alcohol It was fou nd however that as soo n

.
, ,

as the supersaturated solutio n s of the iodide i n this solve n t

were placed i n tubes in order to make the n ecessary observa
tio n s a rim of yello w crystals separated o n the top of the solu
,

tio n thereby putti ng a stop to the experime n t It was fou n d

,
.
2 12 Ka stle a nd Re e d .

glyceri n bath was k ept at 1 40 C

-
Whe n everythi ng h ad °
.

bee n thus arra n ged the glyceri n bath was quickly lowered a n d -

a bath of boili n g water put i n its place This bath co n sisted .

of a large beaker about two thirds full of boili n g water an d so -

arra n ged as to keep the level of the water al w a s above that y

of the sol utio n i n the tubes In about three mi n utes from th e

.

time the tubes were immersed i n the boili n g w ater they h ad

°
reached a temperature of 1 00 C an d n o mer c uric iodide had .
,

as yet crystallized out of the solutio n A few crystals of t he .

°
red mercuric iodide which had also bee n heated to 1 00 C
, .
,

were n ow carefully d roppe d i n to the solutio n i n o n e of the

tubes care bei ng take n n o t t o j ar or shake the tube i n a n y
,

way No crystals of either variety of t he io d ide separated o n

.

the ad d itio n of the red crystals A fe w crystals of the yello w .

°
iodide which had bee n heated to 1 00 C were the n dropped
,
.
,

i n to the seco n d tube whe n a large cr0 p of yellow crystal s

,

separated from the solutio n at o n ce whereas i n th e tube to ,

which the red crystals were first a d ded n o crystals of an y

ki n d had separated up to this tim e A few yello w crystals .
,
°
warmed to 1 00 C were the n put i n to this tube whe n a larg e
.
, ,

crop of yellow crystals sep arated imme d iately D uri n g all .

this time the t ubes co n tai n i ng the solutio n of mercuric iodid e

were so immersed i n the boili n g water as to keep the level of
the water always above that of the solutio n in the tubes .

Th e se experime n ts were repeated several times with exactly

the same results in every case H e n ce we must co n c lude that .

the solutio n of mercuric iodi d e i n n aphthale n e is sup e rsatu ra

ted with respect to the yellow io d ide of mercury an d n ot with
respect to the red That such is the case is bor n e out by th e
.

color of the solutio n It was also observed that fi n ely and

.

coarsely powdered glass an d powdered calc spar heated to ,

°
1 00 C caused the separatio n of yellow crystals from thes e
.
,

supersaturated solutio n s of mercuric iodide i n n aphthale n e ,

an d a col d particle of almost a n y ki n d or o n e heate d belo w ,

°
1 00 C was fo u n d to do the same In V iew of the great te n .

d e n c y o n the part of the mercuric iodide to crystallize it oc ,

curred to us that the separatio n of crystals of this compou n d

from its supersaturated solutio n s by the powdered glass a nd
calc Spar might i n reality have bee n brought about by a low
 N a tu r e of M e rcuri c Iodi de i n Sol ution . 2 13

e ri ng of the temperature of the solutio n by the solid particles

rather tha n by the actio n of a truly isomorphous substa n ce on
t h e solutio n U p to this time the substa n ces to be added to
.

the supersaturated solutio n s of the iodide h ad bee n heated i n

s mall test tubes o n the water bath
-
In the last series of ex -
.

p e rim e nts o n this phase of wor k th e substa n ces i n te nded to

be put i nto the supersat u rated solutio n s of the iodide were
heated in a small test tube surrou n ded by a steam j acket and
-
,

so arra n ged as to bri n g the mouth of the small test tube di

.
-

r e c tl y over the mo uth of the larger tube co n tai n i n g the solu

tio n of mercuric io d ide In this way a ny cooli ng of the crys

.

tals was preve n ted The followi ng substa n ces were tried
.

u n der these improved co nd itio n s

The yellow an d re d io d ide of mercury Icela n d spar sodiu m , ,

n itrate hematite siderite celestite fl u or spar carboru n dum

, , , ,
-
, ,

a n d fi n ely powdered glass coarsely pow d ered glass gypsum , , ,

a nd dolomite The red an d yellow io d ide of mercury were

.

a dded i n the form of small crystals the other substa n ces i n the ,
”
form of coarse powder Of these substa n ces the followi n g.

were fou n d to throw out crystals of the yellow iodi d e of mer

c ury from the supersaturated solutio n s of mercuric io d ide i n

n aphthale n e The yellow iodide of mercury fi n ely powdered ,

glass I cela n d s par so d iu m nitrate siderite hematite celes

, , , , ,

tite fl uorsp ar a nd carboru ndu m O n the other ha n d the red

, , .
,

io d i de of mercury coarsely powdered gl ass gypsum and

, , ,

dolo mite caused no separatio n of crystals of an y ki n d fro m the

supersaturated f sol ut i on s of the iodide It is i nteresti ng to .

n ote i n passi n g that of those substa n ces that precipitate yel

low mercuric iodi d e from its supersaturate d solutio n a n u m

ber of them are rhombic i n crystal form like the yellow iodide
o f mercury itself The fact however that the yellow io d ide
.
, ,

i s also thro wn out of its solutio n s by substa n ces of di ffere n t

c rystal habit a nd eve n by sharp poi n te d fragme n ts such as -
,

glass woul d seem to i n d icate that the precipitat io n of the yel

,

l o w iodide from its supersaturated solutio n s is n ot n ecessarily

bro ught about by the actio n of isomorphous crystals but also
by the distu rba n ce of an u n stable co n d itio n of equilibrium i n
t h e supersaturated solutio n s of the io d i d e That s u ch is the .

c ase woul d also seem to be i n d icated by the fac t that eve n

 Ka stle a nd R e ed .

those substa n ces of the same crystal form as the yello w iodid e ~

of mercury such as calc spar si d erite an d hematite are i n

,
-
, , ,

soluble l n n aphthale n e an d therefore probably i n capable o f ,

acti n g as true isomorphous substa n ces o n the solutio n of th e

yellow io d i d e of mercury H owever this may be the fact re .
,

mai n s that the yellow iodide of mercury an d n o t the red variet y

of this compou nd precipitates the yellow iodi d e from super
saturated solutio n s o f mercuric iodid e i n n aphthale n e an d it ,

is further i nteresti n g to note that th e yellow iodide is the o n l y

form of the compou n d ever precipitated from its sup e rsat ura ~

te d solutio n s by an y substa n ce E ither the yellow iodide i s .

throw n out of these supersaturated solutio n s or n oth i ng at all .

These facts therefore stro n gly support the co n clusio n alread y

, ,

adva n ced i n the former commu n icat io n on this subj ect viz , .
,

that solutio n s of merc uric iodide really co n tai n the yellow

modificatio n of this compou n d a n d not simply molecules of t he
iodide H g I which may arra n ge themselves i n the yellow or
, 2,

red form of the compou n d ac c ordi n g to the n ature of the crys

1
tal which is first prese n ted to them It would seem there .
,

fore that re d mercuric iodi d e cha n ges to yello w i n the act of

,
-

passi n g i nto solutio n In this co nn ectio n it has bee n o b .

serve d repeate d ly that the yellow iodide seems to d issolve

more rea d ily an d rapidly i n orga n ic solve n ts tha n the red In .

order to determi n e whether such was really the case the rat e _

o f solutio n of the yellow a n d red iodide was t ried i n n aphtha

le n e i n the followi ng ma n n er
,

T wo portio n s of n aphthale n e of 1 5 grams each wer e , ,

weighed out and put i nto two glass stoppered bottles of th e -

same size an d shape These two bottles were clamped firm ly .

together a nd place d i n a bath of boili n g water Two equa l .

portio n s of mercuric io d ide were the n weighed out the qua n ,

tity take n bei n g i n excess of that which 1 5 g rams of n aphtha

°
le n e would dissolve at 1 0 0 C O ne of these portio n s was the n . .

ge ntly heated so as to co nver t it i n to the yellow modificatio n

1 In t i s h c o nn e c ti o n c e r ta i n r e c e n t ob s e rv ati on s of We g s c h e i d e r an d K a ufl e r ou

th e llot o py of ph ph o u s a re w o rt h y of n te A c o din g to th e s e b se rv e rs a
a r os r o . c r o .

s tu
a t d so lu t i on f y ll ow ph os p h or u s i n c a b n d i ulph i d e s w n w i t h e d ph o s
ra e o e r o s o r

p h o u s h ow s n
r s p c e p ti bl c h n ge n d on l ow e ri n g th e te mp tu re y e llow
o e r e a , a , e ra ,

ph ph u s s e p a te Th e y h e r c h d th e c on c lu sion t h e e fo e t h t th e se tw
os or ar s. av ea e , r r , a 0~

f m s o f ph os ph ru
or e n ot p l y m o ph o u s b ut c h e mi c a ll y difl e e n t ( Mona t h
s ar o or , r s .

C h e m 2 2 7 7 06
. , , 00-
2 16 R a stle a n d Re e d .

the yellow iodide obtai ned by crystallizatio n from ethyl iodi de

cha nges rapidly to red if allowed to remai n u nder the solve n t
-

whereas if removed from the solve n t an d dried in the air it is

o nly slowly cha n ged to red In o ne batch of crystals thus.

prepared and allowed to sta n d in the air a n umber of yellow

o n es were fou nd after two an d a half days O n the other .

ha nd u nder ethyl butyrate the yellow iodide is very stable

, ,

whereas the same crystals whe n exposed to air an d n ot in

,

co n tact with the sol ve nt were fou nd to alter very rapidly

, .

There are do ubtless ma n y peculiarities co n nected with the

actio n of various solve nts on the labile form of this compou n d
which as yet ca n n ot be satisfactorily explai n ed O n the other .

ha n d i n studyi ng the stability of the yellow iodide u nder

,

di ffere n t solve n ts it soo n occurred to us that its stability n u

,

der the solve n t i n creases with the viscosity of the latter .

That such is the case is re n dered e vi d e n t by a compariso n of

its stability u n d er ethyl an d amyl alcohol be n ze n e and n ap h , ,

t h al e n e
, respectively It w as also observed that light ao
.

c e l e r ate s the cha n ge of the yellow iodi d e i n to the red u n der ,

all solve n ts It therefore occurred to us that the yellow iodide

.

could be preserved u n cha nged for a co n siderable time pro

v i d e d it were cryst a llized from a very viscous solve n t and kept
i n the dark . The followi ng experime n ts were therefore tri e d
'

i n order to determi n e whether such was really the case

Very co n ce n trated solutio n s of mercuric iodi d e i n glyceri n
°
were prepared by heati n g the iodide i n glyceri n to 2 00 C i n .

perfectly clea n test tubes O n cooli n g these sol utio n s de

-
.
,

posited very mi n ute crystals of the yello w iodide The tubes .

were the n place d i n the dark room The first tube thus p re .

pared showed n o trace oi the red compou n d u ntil o n e week

after it h ad bee n made A t the e nd of two weeks the red
.

iodide was pretty well d i ffused throughout the tube A nother .

tube prepared i n exactly the same way showed n o trace of the

red compou n d for two weeks an d at the e nd of five weeks ,

there was o n ly a thi n layer of re d crystals on the surface of

the yellow o nes Two tubes of the yellow iodide in glyceri n
.

were the n prepare d by pouri n g a hot solutio n of the iodi d e i n

glyceri n i n to cold glyceri n In this way the yellow iodide .

was precipitated in eve n smaller crystals tha n by cry stallizi n g

 N a tu r e o fMe rcu ri c Iodide i n Solu ti on . 2 17

from the hot solutio n These tubes remai n ed u n cha nged for
.

two wee k s at the e n d of which ti me crystals of the red io dide

,

were see n di ffused thro ughout the mass of the ye l low com
pou nd It was thought that possibly th e frictio n of the yel
.

lo w crystals agai n st the walls oi the test tube might have -

caused the cha n ge of the yellow to red In order to do away .

with this if possible a solutio n of the iodide i n glyceri n con

, , ,

tai n i n g the fi n e y e l lo w crystals i n suspe nsio n was poured i n to ,

small cups mad e of p aramn U n der these co n ditio n s the yel .

lo w iodide remai n ed u n cha n ged for two w e e k s at the e nd of ,

which time red crystals bega n to make their appeara n ce It .

will be observed therefore that the p arafli n vessels o ffered no

, ,

p articular adva n tage over the test tubes -

.

The n ext solve n t tried was a very thic k co n ce n trated solu ,

tio n of ca n e sugar U nder this solve n t the yellow iodide re

-
.

mai n ed u n cha n ged for several d ays after which the mass of ,

yellow crystals gradually became red In this co nn ectio n it . .

should be observed th at u n der water the y ellow iodide of mer

cury is very u nstable so that the ca ne sugar by i ncreasi ng 0
,
-
,

the viscosity of the solutio n greatly i n creases the stability of ,

the yellow io di d e .

Th e co n d uct of the yellow iodide under vaseli ne was n ext

studied Mercuric io d ide was dissolved i n boilin g v aseli n e
.

a n d the solutio n allowed t ocool The yellow iodide separa .

t e d ou cooli ng a n d the vaseli n e became gelati n ous O ne tube .

prepared i n this ma nn er a n d placed i n the dark room showed

absolutely n o trace of red at the e n d of n i n e weeks A t the .

e nd of this t i me a few of the yellow crystals tur n ed red but ,

eve n n ow o n e year an d seve n mo n ths si n ce this tube was

,

prepared probably n o t more tha n 2 5 per ce n t of the yello w

,

cry stals have cha n ged to red A n other tube c o n tai n i n g the .

yellow iodide an d vaseli n e was prepared o n the 1 4 th of A pril ,

1 9 00
. T o day Nov 1 2 1 90 1 this tube shows n o red crys
, .
, ,

tals except in the upper part of it where a little of the solu ,

t io n stuck to the walls of the tube whe n it was poure d i n .

Otherwise the yellow iodide u n der the vaseli n e remai n s n u

cha n ged an d is as pure yellow n ow as it was the day that it
was put i n the tube Y ello w mercuric iod id e zi s more stable
.

i n co n tact with vaseli n e tha n a ny solve n t thus far studied .

 l e e le r and j olz n son .

The fact that the yellow iodide is m ore stable i n co n tact with
viscous solve n ts tha n with those that are very mobile is in
harmo n y with the ge n eral co n duct of th ese two cl asses of sol
ve nts an d c an therefore be rea d ily explai n ed In viscous
, , .

solve n ts all chemical and physical cha n ges are slow su d de n ,

cha n ges of temperature are practicall y impossible a nd the ,

motio n and r ubbi n g of suspe nd ed p articles but slight Whe n .

t hese facts are kept i n mi n d an d we co n sider also the ge n eral

relucta n ce o n the part of all substa n ces to form n e w phases ,

we c an rea d ily u n dersta n d why the yello w mercuric iodide re

sists alteratio n i n viscous solve n ts .

ST T E C LL E G E
A O K E N TU KY OF C
L E X N GT N N
,

I 9 O , ov .
, 1 01 .

C ont ri but ions f om t he Sh ffi ld L

r e e a bo rat ory o f Yale U niv e rs it y .

XC I .
—
O N B E N ZO Y L B E N Z Y L U R E A ,
B E N Z O YL P A R A
T O L YL U R E A AN D T HE C OR R E SP O NDIN G
P SE U DO E T H Y L U R E A S: A CO R R E C
TI ON .

BY H EN R Y L . W HEE L E D T E T B J HNS N
R A N R A . O O .

In o ur article on the behavi or of acy lth ion c arbami c esters

with alkyl iodides and ami n es we described products obtai n ed l

by the actio n of be nzyl ami ne an d paratoluidi n e on ethyl be n ;

z o y lt hio n c a rbam at e which fro m our a n alytical data were

, , ,

co ncluded to be be nz oy lbe n z y l an d be n z oy lp ara toly lu re a .

°
The compou n ds melted at 8 9 an d respecti vely The .

fact that these are ab normally low melti n g poi nts for be n zoyl -

ureas escaped our notice u ntil rece ntly whereupo n on mak , ,

ng a reex ami n atio n of t he products it was fou n d that they

i ,

are n ot normal but p se u do ure as .

P ure be n z o y lp se u d oe th y lp arat oly lure a ,

c, H, CO N
°
prepared from ethyl be nz oy li m id oth ioc arbon ate boili ng at 1 0 4
at 1 6 mm pressure is a solid that can be repeatedl y re c ry s
.
,

t all iz e d from stro n g alcohol an d it melts sharply at 7 ,

Whe n this is treated with dilute hydrochloric acid ethyl chlo ,

ride is evolved an d the material is smooth ly tra n sformed i nto

1 Th i J U N L 2 4 8 9
s O R A , , 20 , 20
 R E P O R TS .

The Ml o e cula r We ight of Sulp h ur .

That at high temperatures sulphur vapor exists as the mole

cule S has n ever bee n doubted si n ce the work of Troost
B in e a u a n d of V a n d C Meyer
,
z ,

E specially has the work

2

of Victor Meyer alo n e an d in compa n y with Biltz established

. . .
,
"

the existe n ce an d co n sta n cy of this mo l ecule S betwee n the ,

° °
temperatures 9 00 and 1 7 0 0 C .

For a lo n g time also based u po n the measureme n ts made

by D umas Mits c he rli c h an d V an d C Meyer the d e n sity
,
6
.
, , .
,
° °
of sulphur vapor at temperatures betwee n 4 9 0 a n d 5 30 was
place d at about The m ea n of the various determi n atio n s
are
D umas
Mits c h e rl ic h 6 57
V a n d C Meyer
.

. .

These lead to a molecular weight of 1 9 2 That is the sul .

phur molecule exists as S ,

.

The first to cast doubt o n the existe n ce of the six atom -

8
molecule was Biltz i n 1 8 8 8 although L iebig previous to 1 8 40 , , , ,

had d etermi n e d the molecular weight of sul phur by D umas ’

metho d but had fou n d such large di ffere n ces In his values that
he had n ever publishe d them This fact remai n ed u n k n o wn
u n til after th e publicatio n of the correspo nde n ce of L iebig a nd
Berzelius .

Biltz determi n e d the de n sity of sulphur vapor at various

° °
temperatures betwee n 4 6 8 an d 6 0 6 by both the D umas an d
the Victor Meyer metho d Most of h is determi n atio ns were .

°
made at 5 1 8 an d usi n g the vapor of phosphorus pe n ta
sulphide an d zi n c chlori d e as the heati n g age n ts B etwee n
,
.

° °

4 6 8 a n d 6 06 the vapor was fou n d to vary in de n sity fro m

to 3 5 by the Victor Meyer method and betwee n
. an d ,

by the D umas m etho d

The values obtai n ed by the method of V Meyer were al
.

ways lower tha n those obtai n ed by the D umas metho d at the

same temperature These discrepa n cies Biltz explai n s as due .

to the n itroge n used as the gas to be dis p laced i n th e Victor

1 A nn h i m ph y s
. c 58 57 . .
, , 2 .

” but [ 3] 5 9 45 6
h m G e s 12 1 5
.
8 Be d r . . c e . .
, , 11 .

4 Zt h sc
p hy C he m 4 6 6
r . s .
, 2
h m ph y s 5 0
. .

5 A n n c 78 ; 1 .
, 1
“ P o gg A n n 2
. .
.

9 17 , 2
d ch m Ge
.
, .

‘'
l
B e r 11 2 5 9 e s , 2
ph y C h e m
. . . .

Bl b d z Z t sc h r s 2
. . .
, 920 .
Meyer method H e fou n d that whe n the qua n tity of sul .

phur used i n his experime n ts was i n creased an d whe n pre ,

cautio n s were take n to preve n t the rapid di ffusio n of the sul

phur vapor i nto th e n itroge n the d e n sity approached more ,

n early to that obtai n e d by the D umas metho d .

A s the result of his work Biltz co n clu d ed that there was n o ,

grou n d for the ass umptio n of the existe n ce of the molecules

s. S or 8 10 an d tha t the i n crease i n de nsity observed as the
, ,, _ ,

temperatu re of the experime n t was lowered was n ot d u e to an

associatio n of the simpler molecules but that at the lower ,

te mperat ures the d eviatio n s from the gas laws show n by the
vapor were very m uch greater tha n at higher temperatures .

H e also co n cluded that the d e n sity correspo n di n g to the mole

cule S was the o n ly o n e which remai n e d co n sta n t over an y
,

co n si d erable ra n ge of temperatu re .

B i ltz s co n cl usio n that h e h ad proved the n on existe n ce of

’
-

the molecule S6 was soo n challe n ged R amsay poin ted out .
l
]

that B lltz s results h ad n o t proved to him at least the n o n

’
, ,

existe n ce of a sulphur molecule co n tai n i ng 6 atoms .

Biltz i n reply a d mitted the possi bility of the molecule S

,
2
, , ,

but state d that he had n ot worke d over a sufi c ie n t ly large

ra n ge of temperature to prove its existe n ce The existe n ce of .

the molecule S he would n ot admit 6

.

3
R iecke use d B il tz s results as a grou n dwork to deduce a
’

law gover n i n g d issociatio n by steps as well as to show math ,

e ma t i c a l ly that the sulphur molecule passes from S to S with

8 ,

the i n termedi ate formatio n of the molecule S6 accordi n g to the

e q u afi o n
SS : S6 + S

Ner n st an d Ostwald i n their text books have also e mp h a

‘
,
5
-
,

Si zed the fact that the n o n existe n ce of the molecule S 6

had -

n o t bee n proved .

C Schall usi ng a method devised by himself for m e as u r

6
.
,

I ng d e n sities u n der d i mi n ished pressure a n d he n ce at lower , ,

temperatures gives the value S an d co n clu d es with Biltz , e,

that the m olecule S6 is n o n existe n t -

Krause an d V Meyer have also give n the value S8 at tem

.

’
.

p at u re s below the boili n g poi n t of sul phur u n der atmospheric

e r -

8
pressure Neuberg has also arrived at the same co n clusio n
. .

Zt l h h Chm 3 6 7
1 5 214 3 3 3
sc r . s .

2 1 2 .

3
[bi d 6 43 0.
,

L h bu h d
4 e ll g m i
r C h mi ud E d
c V l I p 88 e r a e e ne n e e
”
z o 21
h C h mi
. .

Th d Ed p 4 5
.
, .
,
5 ti e ore ”
sc e e e 2n 1
h m G
, .
, . .

B 6 d er .
3 9 9
.
7 c e . es . , 2 , 1 1 01
ph y C h m 6 5
,

Zt 7 h sc r s
. . e ,

Be r . d . c he m . Ge s .
, 2 4, 2 544
 222 Reports .

I
P ater n o N a si n i were the first to determi n e the mole e n
and
lar weight of sulphur in solutio n by the cryoscopic method .

They thought that they had established the existe n ce of the

molecule S, i n be n ze n e as a solve n t .

2
B eckma nn u si n g carbo n bisulphide as a solve n t m ade it , ,

very probable that the molecule S d oes exist although h e , ,

could n ot with certai n ty exclude the existe nce of S, .

H ertz usi n g n aphthale n e obtai n e d a valu e S for the mole

, , ,

cule By the boili n g poi n t method H e l ff with carbo n bi

.
, ,

sulphide as a solve nt reached the same co nclusio n as Beck ,

ma n n .

Sakurai an d B i ltz usi n g n itrobe n ze n e obtai n ed a mole c u

5 6
, ,

lar weight bet wee n S7 an d S, L ater Or ndorff a nd T e rasse .

,
7

i n boili n g n aphthale n e xyle n e an d phe n etol an d i n freezi n g , , ,

diphe n yl fou n d the value S but i n freezi n g n aphthale n e the

, , ,

value S, while i n sulphur mo nochlori d e they obtai n e d S an d

, ,,

i n boili n g tolue n e a nd car bo n bisulphide fou n d the molecule S ,

.

8
G loss has give n for the d i ffere n t modificatio n s of sulphur
values betwee n S an d S worki n g with n aphth ale n e by the , , ,

freezi n g poi n t method -

.

°
B ar n es worki ng i n carbo n bisulphide has obtai n ed the
, ,

value S ,
.

T he work of O r ndor ff an d T e rasse has bee n completely c o n

t rad i c te d by A ro n stei n a n d Me i h u iz e n who worke d with ,

solutio n s i n tolue n e xyle n e n aphthale n e and carbo n bisul , , ,

p hi d e both above a n d
,
belo w the tra n sitio n poi n t of rhombic -

to mo n ocli n ic sulphur a n d above a nd belo w its melti n g poi n t ,

-
.

They obtai n ed a co n sta n t value S ,

.

It seems the n to be settled that at high temperatures sul, ,

phur exists as S while at low temperatures an d i n solutio n it ,,

exists as the molecule S B ut this questio n still remai n s to ,

.

be settle d H o w does the molecule S, break dow n Does it

p ass at o n ce to the molecule S or d o we have a n i n termediate ,

formatio n of S, as h as bee n ge n erally accepted ,

In the last year or two two importa n t papers bea ri n g o n ,

th i s poi nt have appeare d .

“
Bleier a n d Koh n have u se d in their experime n ts a mo d ifi
catio n of the method of Victor Meyer i n which i nstead of , ,

measuri n g the volume of gas d isplaced by the substa n ce whose

1 Be r d c e h m
G e s , 2 1 , 2 15 3
ph C h m
. . . .

Z tsc h r ys e .
, 5 , 7 6 . .

3 I bzd , 6 , 35 8
mm
. .

4 1 , 12 , 2 00

Ch m
.

0
J e Soc , 1 89 2 , 9 89 - 1002
ph C h m
. . . .

6 Z tsc h r ys e 19 , 4 2 5
Th J U N L
. .
, .

7 is O R A ,
3 P hy C h e m 2 45
}bid
s . .
,
1.
9
3 , 15 1
k ad m m J ul y
. .

1° V e r h d e r K o n i l
g . . A . Wi s s .
, A s te r d a , ,
1 89 8 ; C e n tr bl .
, II .
,

1 1 94 ( 1900 ) 3 z I
M
,
11 o n a t s h C h e m q 2 0 , 5 05 , 9 09
. 2 1, 575 .
2 24 Repor ts .
in a small tube at f The stop cock 6 bei n g Ope n the whole
.
-
,

apparatus is pu mped out to the desire d pressure while the ,

liquid i n the j acket surrou n di ng A is boiled The stop cock .

-

h is the n closed The substa n ce is allowed to drop to the bot

.

tom of A whe n it is vaporized A s soo n as the ma n ometer

, .

becomes co n sta nt the differe n ce in the level i n the two arms is

rea d This gives the necessary data for the calculatio n of p
.
,

an d he n ce of m the molecular weight

, , , .

U si n g this method Bleier an d Koh n have established the

,

dissociatio n isothermals of sulphur vapor over co n siderable

ra n ges of pressure at the temperature of boili n g d iphe n yl
,

ami n e amyl be nzoate qui n oli n e ethyl

be n zoate an d dimethyla n ili n e

The de nsit y of the sulphur vapor i n creases regularly with -

i n crease i n pressure The followi n g table shows the lea st an d

.

greatest de n sities obtai n ed at th e various temperatures

P re s s u re in mm
T e mp e u u
.

r at re . of m e r c ry .

3 10
°

3 10
°
262
°
262
°
2 36
°
2 36
°
2 14
°
2 14
°
192
°
192

From their results an d from the curves which they h ave

,

plotted from these results it is see n that the values for the ,

de n sities gradually approach the value 8 an d in the pr e ssure

de n sity curve become asymptotic to th i s value From this .

they co n clude that the u n dissociated sulphur molecule is S, .

I f the molecule S exists as R iecke had co n cluded fro m a

, ,

theoretical co n sideratio n of B il tz s results as has alrea d y bee n ’

,

me ntio n ed it would be expected that the de nsity 6 woul d be

,

fou n d to remai n co n sta n t over a co n si d erable ra n ge of pres

sure In the results obtai n ed at
. the o n ly temperature at
which de n sities were fou nd lower tha n 6 no trace of a n y such ,

co n sta n t value was observed a n d the curves show no te nde n cy

to depart from their regular form These results would poi n t .

to the n on existe n ce of the molecule S, but Bleier an d Koh n

-
,

co n clu d e that to settle thi s poi nt defi n itely dissociatio n iso

, ,

thermals at higher temperatures are n ecessary as well as to

 R p
e ar ts

obtai n de n sities lower tha n the lowest obtai n able at the

highest temperature at which they worked .

l
Biltz an d P re un e r have completed the proof n ecessary to
completely exclude the molecule S, by a series of experime nts ,

usi n g the D umas method u n der dimi n ished pressure .

The pri n ciple of their apparatus is i n ge neral that of H aber

2
m ann but special modificatio n s have bee n i n troduced to meet
,

the d ifli c ultie s of their experime n ts Their determi natio ns .

were made at the temperature of sulphur boili n g u n der atmos

p h e ric pressure a nd at pressures varyi n g betwee n
, an d
mm of mercury . .

The greatest care and a high degree of accuracy are show n

in the work The sulphur used was subj ected to five distilla
.

tio n s before use A s the qua n tity used i n an experime n t was

.

very small especially u nder the lower pressures a n alytical

, ,

methods for determi n i n g the amou n t of sulph ur i n the D umas

b ulb were employed i n order to avoi d the errors due to weigh
i n g very s m all amou nts I n all thirty two determi n atio n s .
,
-

were made which show a gradual rise i n de n sity with i n crease

i n pressure No evide n ce of the existe n ce of the six atom
.
-

molecule was fou n d as is see n by a study of the followi n g ,

curve N ot the slightest te nde n cy for the curve to straighte n

.

out or show irregularities is n oticed i n the n eighborhood of

de nsity 6 .

P re ss u re in mi ll i m e t e rs o f me c u r ry .

In co n clusio n it has bee n show n that at the lowest te mp e rf

,

atures at which sulphur c a n be vaporized it exists as S A s ,

.

the temperature rises this comme n ces to break dow n i nto the ,

molecules of S while at temperatures above 9 00 sulphur ex

,,
°

i st s solely as S In solutio n s it exists as S

,
.
,
.

C H L E S F L ND S Y A R . I A .

M t h Ch m
1 on a s 6 7 ; B. d h m G
e 43 49 ; Z t h
2 2 ph y C h m
, 2 er . . c e . es .
, , 2 0 sc r . s . e .
,

34 3 3 2
A nn C h m ( L
’ °

2 b g). 8 7 34 ( 87 7 )
e . 1e 1 , 1 , I 1
2 28 R ep or ts .

of copper and iro n in the abse n ce of oxyge n were reduced b y

, ,

the sulphurous acid with the formatio n of sulphuric aci d t he ,

latter bei n g forme d as lo n g as there was an y oxide to oxidiz e

the sulphurous acid while with the oxide of chromi um which
, ,

was n ot reduced n o sulphuric a c id was formed u n less oxyge n

,

was prese n t These a nd similar ex perime n ts e n abled them to

.
«

explai n the phe nome n a an d formed the basis of the later work
of L u nge and that described i n this paper A n umber o f .

pate n ts were gra n ted d uri n g th is perio d for the use of a variety
of substa n ces as catalytic age n ts but fumi n g sulphuric acid ,

could n ot be made by an y of these methods at a price which

, , ,
:

would e n able it to compete with that made by the d istillatio n

of iro n sulphate .

We come n o w to the tur n i n g poi n t to the work of C lem e n s

-
,

Wi n kler A s a result of experime n ts Wi n kler co n cluded that

.
,

o n ly a stoichiometrical mixture of two volumes of sulphurous

acid an d one volume of oxyge n would form sulphuric flac id ,

a n d that the prese n ce of a n y other gas eve n a n excess of o x y ,

g e n would
,
retard a n d decrease the actio n H e obtai n ed t h e .

n ecessary mixture by heati n g sulphuric aci d formi n g water , ,

oxyge n an d sulphur dioxi d e an d co n de n si n g the water

, , .

The oxyge n a n d sulphur dioxi d e i n the prese n ce of the c o n ,

tact mass u n ite to form sulphur trioxide This work was o f

, .

great importa n ce an d led to the m a n ufacture of the fumi n g acid

by a method which could compete with the ferrous sulphat e
metho d which had had a mo n opol y of the field T e n years
, .

later a process was devised for the use of air i n stead of pure
‘

oxyge n the retardi ng i n flue n ce of the n itroge n bei n g over

,

come by carryi n g on the actio n u nder pressure No n e of thes e .

methods however e n able d them to use the fur n ace gases or

, ,

to compete with the chamber process for maki n g dil ute acid .

A lthough it was co n sidered i mpossible to use the fur n ac e

gases the great importa n ce of a cheap method for the ma n u
,

facture of the pure acid le d the B adische A n ili n u n d Soda

Fabrik to u nd ertake a thorough i n vestigatio n of the subj ect .

A s the residual gases i n the chamber process co n tai n 6 per

ce n t of oxyge n by volume an d as the fur n ace gases after be
, ,

i n g in co ntact with the co n tact mass also co n tai n an exces s ,

of oxyge n it was di ffi cult to u ndersta n d why there was a n i n

,

co mplete form atio n o i acid E xperime n ts made on the smal l

.

scale with pure gases showed that with eve n stro n gly dil uted
gases the yield was almost qua n titative and the dilutio n if
'

a n ythi n g i n creased the yiel d

, .

This observatio n disproved the results of W i nkler regard

i n g the retardi n g actio n of d iluti n g gases a nd led to an ex
hau st i ve stu d y of the co n ditio n s i nflue n ci n g the reactio n .
 Th e same experime nts were carried out with the n atural fur
‘

n ac e gases which were co n ducted i n to the laboratory through

,

l o n g lead pipes
r
These pipes served the purpose of collecti ng
.

t he solid particles A fter the gases had passed through.

sev eral vessels of sulphuric acid they were brought in c on ,

t act with the catalytic age n t an d an excelle nt yield of acid ,

was obtai n ed the mass seemi n g to retai n its full power eve n
,

a fter several days Whe n similar experime n ts were made o n

.

the large scale ho w ever the co ntact mass rapidly became i n

, ,

a ctive eve n though the gases i n a d ditio n to bei n g subj ected

, ,

to other methods of purificatio n were filtered through coke ,

a n d asbestos filters a nd were as pure as is possible o n the

,

l arge scale A n exami n atio n of the fur n ace gases showed

.

that while the actio n o n the co n tact mass was due partly to
,

t h e prese n ce of a n timo n y bismuth lead zi n c a nd other sub , , , ,

s ta n ces i n small qua n tities the most i nj urious substa nce ,

w as arse n ic which was able whe n prese n t o n ly to the exte n t

, ,

o f I to 2 per ce n t to poiso n the mass a n d re n der it e ntirely i n ac

,

tive The removal of the small amou n t of arse n i c trioxide

.

p rese n t i n the gases as a mist was a problem which had bee n

studi ed by m a n y chemists but had n ever bee n successfully ,

s olved .

A fter the expe n diture of an imme n se amou n t of time ,

p atie n ce an d mo n ey a method was devised by which through

, ,

cooli ng an d washi ng and other processes the exact details of ,

which are n ot give n the gases were a bsolute ly freed of all im

,

p urities especially those i n the solid co n ditio n It was fou nd

,
.

that the ease with which the solid particles could be p re c i pi

"

t at e d depe n ded largely u po n the rate of cooli n g slow cooli n g ,

greatly facilitati n g it A lthough it was supposed that acid of

.

a co n ce n tratio n of 9 0 per ce n t would n o t act o n iro n or if so , , ,

would form sulphur dioxide the decrease i n power of the c on ,

t act mass which o n ly bega n to appear after weeks or mo n ths

, ,

was show n to be due to the formatio n of hydroge n from the

iro n an d sulphuric acid an d the actio n of this on an arse n ic
co mpou nd to form arsi n e E ve n the trace of arsen ic c on .

t ai ne d i n the small amou n t of sulphur which passed through ,

u n precipitated was suffi cie n t to i nj ure the co ntact mass B ut

,
.

this was easily removed as was also the sulphuric acid which ,

was formed i n the fur n ace an d which before had acted on the
iro n a nd the arse n ic compou nds by Sprayi n g the gases afte r ,

they issued from the fur n ace where the pyrite was burn ed .

In the tech n ical preparatio n of the fumi n g acid very little

atte n tio n had bee n paid to the heat evolved whe n sulphur di
o xid e a n d oxyge n co mbi n e although it amou n ted to ,

cal It was show n that the commo n ly accepted idea of the

.
n ecessity of heati n g the co ntact mass very high i n order to ,

produce the combi n atio n whe n the diluted fur n ace gases were
used was i ncorrect and that both the yield and the life of th e
, ,

mass could be i n crease d if the tubes co ntai n i n g it were cooled

i n order to carry off some of the heat ge n erate d in the chemi
cal combi n atio n of the two gases A form of fur n ace was de
.

vised somethi n g like a tu bular boiler placed on e n d an d t he

, ,

co ntact mass arra n ged i n the upright tubes of the furn ace i n
such a way that the pressure a nd amou nt of surface of th e
mass exposed in each tube was the same U nd er these c on .
~

d i ti on s the process is a co nti n uous on e a n d the mass retai n s

its full power for a year or more .

The ord i n ary method of absorbi n g gases by p assi n g through

a series of vessels co n tai n i n g water or dilute acid would n ot ,

e ntirely remove the sulphur trioxide eve n whe n a n umber of

the absorbi n g flasks were used but o n e vessel co n tai n i ng
acid of 9 7 to 9 8 per ce n t sulphuric acid absorbs it i n sta n tly
a n d e n tirely .

I n order to keep the co n ce n tratio n at this poi n t the excess

of sulphur trioxide is removed from time to time or water i s
added By the method j u st d escribed the experime n ters were
.

able to obtai n aci d of an y co nce n tratio n an d mixtures of t he

acid an d sulphur trioxide i n all proportio n s A careful stud y .

of the properties of acids of differe n t co n ce n tratio n showed n ot

o n ly i n teresti ng facts regardi n g the variatio n s of the sa m e
property with acid of di ffere n t stre n gth but also that the dif
,

Me l ti n g p oi n t c u rve
- .

B ili n g p i nt c u rv e
o - o .

V a p t e n s i on at
o r-

Fi g I . .
2 32 Rep or ts .

co ntai n i n g 8 5 per ce n t sulphur trioxide a maximu m is reached

°
at 2 7 ( Fig I This applies however o n ly to freshly
. .
, , ,

prepared specime n s as after sta n di ng they polymerize a nd n o

, ,

lo n ger melt but sublime at a higher temperature With

, .

further dilutio n it reaches with an aci d co n tai n i ng 6 0 to 6 5 ,

°
per ce n t of the trioxide a melti n g poi nt of 0 to a n d risi n g
,
-
,

agai n reaches a maximu m at

, the acid correspo ndi n g to
the formula H SO + SO , This poi nt is of Special i nterest
, ,
.
,

as it coi n cides with the poi n t of greatest pressure the greatest ,

Fi g I II . .

viscosity an d a brea k i n the curve of capillarity With

, .

°
further dilutio n we fi nd at 1 2 a n acid which will attack the —

iro n at + 1 0 one represe n te d correspo ndi n g to the mon ohy

,
°

drate at 3 5 the acid 2 H SO

,
—
°
H O and at + 8 the aci d , , , ,
°

H SO4
, HO ,
.

The author also showed the results obtai n ed fro m a study

of the Specific heat heat o f solutio n capillary rise and vis
, , ,

c os ity of acids of all co n ce n tratio n s In the case of the vis .

co sit y which i n creases as the co n ce n tratio n of the acid i n

,

creases u ntil an acid co n tai ni n g 5 0 per ce n t oleum is reached

, ,

whe n it begi n s to decrease agai n ; the values for water and

pure sulphur trioxide were fou n d to be ide ntical .

Fur n ace gases which co n tai n ed besides n itroge n a sto ic h io , ,

metrical mixture of oxyge n an d sulphur trioxide whe n brought ,

i n Co n tact with the catalytic mass at di ffere n t temperatures

a n d at di ffere n t rates of flow n ever gave more tha n 7 7 to 9 1 ,

per ce n t of the theoretical yield but if o ne of the gases was ,

prese n t i n excess the other was completely removed The

,
.

curves S an d S i n Fig I V represe nt the results with the

’
. .

stoichiometrical mixture .
 R ep orts . 2 33

The tech n ical fur n ace gases formed by the roasti n g of

pyrites co n tai n about 7 volumes of sulphur dioxide 1 0 vol ,

u mes of oxyge n a n d 8 3 volumes of nitroge n

, . If this mixture
is passed through a n empty porcelai n tube there is a small

40
0 5 00
° °

Fi g . IV .

yield of acid ( Fig IV P ) but if a co n tact mass as plati n u m

. .
, , ,
°
asbestos is placed i n the tube eve n at 2 00 the gases begi n
, ,
°
to combi ne the yield i n creasi n g up to 400
, where 9 8 to '

9 9 per ce n t of the theoretical yield i s o bt ai n e d A s the tem .

°
p ature rises higher the acid is decomposed the yield at 7 00
e r
°
,

to 7 5 0 bei n g o n ly 6 0 per ce n t an d at 9 00 to 1 000 becomi n g ° °

practically zero .

If the amou nt of co n tact mass is d imi n ished or what is th e ,

same thi n g the rate of fl o w i n creased th e results represe n ted

,

i n curves 1 2 3 4 and 5 were obtai n ed

, , , While these are i n
, .

ge n eral parallel they still Show a te n de n cy to diverge as they

approach the poi n t of maximum yield a n d the n approach o ne
°
a n other reachi ng the zero poi nt at about 9 0 0 to
, A s the
ra t e of flow i n creases n ot o n ly d oes the yield decrease but the ,

temperature at which the maxi mum yield is obtai n e d becomes

greater as is i ndicated by the dotte d li n e E xperime n ts with
, .

empty tubes through which the sulphur trioxi d e was passed

showed that i n the abse n ce of fi n ely divi d e d solid matter the
, ,

sulphur trioxide was very stable a n d was n ot fi n ally d e c o m

posed u ntil a temperature of 1 2 00 was reached ( curve B ) °
.

If however the tube was filled with an y solid matter the sub
, ,

sta n ce was deco mposed at a lower t emperature as Show n by

curve E .

If the results obtai n ed i n such a process are plotted as i n

Fig V we c an by refere n ce to the chart determi n e what
. .
, , ,

amou n t of co n tact mass will give the best yield at any give n
 C o n tac t m a s s or ti me .

Fi g . V .

° ° °
temperature The regio n s below 2 00 an d above 9 00 to 1 000
.
'

c an be regarde d as re ac t io n le ss while the be st y i e l d is o b ,

°
t a i n e d betwee n 2 0 0 an d 4 A lthough th e amou n t of prod
u c t formed is n o t directly d epe n de n t upo n the n atur e of the
co n tact m ass yet the latter must be on e which will give the
,

greatest e fficie ncy at about 4 A ll substa n ces which reach

their highest e fli c i e nc y above this temperature will n ever
cause a qu a ntitative yield no matter how lo n g the gases may
,

be kept in co n tact as they will be partly rege n erated if the y

,

have first co mbi n ed The o n ly substa n ce which fulfils these

.

co nd i tio n s is plati n um eve n members of the sam e family n ot

,

showi n g an equal e fli c ie nc y The i ntroductio n of this method

.

has e n abled the B adische A n ili n u n d Soda Fabrik to i n crease -

the yield of the a n hydri d e from to n s i n 1 88 8 to 1

to n s i n 1 9 00.

A t the close of the paper the author calls atten tio n to the
fact that such a piece of work coul d n ot have bee n carried out
by a n i n dividual It required the imme n se resources of such
.

a compa n y as the B adische A n ili n u n d Soda Fabrik directed -

,

by the far reachi n g k n owledge of H ei nrich Brii n ck the ex

-
,

p e r i e n c e of G ustav Jacobse n an d the valuable ,

aid of i n ge nious

mecha nics to carry it to success J E LL TT 0 m m

.
IO .
2 36 Re vi e ws .

the fact that the low boili ng substa n ces such as oxyge n air
-
, ,

n itroge n a n d hy d roge n c a n be obtai n ed in the liquid form i n

,

an y qua n tity desire d The measureme n t of very high tem

.

p e rat ure s has however n ot bee n disregarded as is show n by

, , ,

the appeara n ce of a volume like the o n e i n ha nd The author .

takes up the gas pyrometer the calorimetric pyrometer the , ,

electrical resista n ce pyrometer the thermoelectric pyrometer , ,

the heat radiatio n pyro meter the lumi nous radiatio n p y rome
-
,
-

ter the co n tractio n pyro meter fusible co n es a nd recordi n g

, , ,

pyrometers .

The i mporta n ce of high temperature measureme nts is -

obvio us to an y o n e who has followed the work of Moissa n L e ,

C hatelier an d R oberts A uste n By mea n s of the electric fur

-

n ace M
.
,

oissa n has ope n ed up a n e ntirely n e w field for i n or

ga ni e chemistry an d it is highly d esirable to k n ow at least
, ,

approximately the temperatures at which these tra n sforma

,

tio n s take place L e C hatelier h as studied the electrical re

.

s is ta nce of metals at very high temperatures also their dilata ,

tio n an d allot rO p ic tra n sformatio n s H e has shown that ma n y .

n e w co mpou n ds probably exist at the more elevated tempera

tures A n umber of allotropic mo d ificatio n s of iro n an d other
.

eleme nts have also bee n sho wn to exist by the work of R oberts
A uste n The applicatio ns of these extremely high tempera
.

tures have proved of i n calculable service also in the i ndus

tries .

The work n eeds no other comme n datio n tha n that it was

writte n by L e C hatelier The E n glish of the tra nslatio n .

could however have bee n easily improved

, ,
H C J . . . .

DI E N O R MA L E L E ME N TE U N D I H R E A N W E N D N G I N D E R E L E K TR I SC H E N U
M E SSTE C H N I K Vo n DR W A E GE R , K ai se rl P ro fe ss or , M itg l ied
. . . J .

k
d e r p h y s i a l isc h tec h n i sc h e n R ei c h s a n s t alt i n C h arl o tte n bu rg
-
Ve r .

l ag v o u W i l h e l m K n a p p , H al l e A 8 p p 13 1 1 90 2 . . . . .

The i nformatio n co n cer ni n g n ormal eleme nts is so scattered

that it is ofte n d ifli c ult to fi nd what is desired The problem .

is further complicated by the fact that suc h wi d ely di ffere n t

results have bee n obtai n e d with the same eleme n t by differe n t
experime n ters In the prese nt vo l ume we have the best that
.

is k n ow n co n cer ni n g this importa n t Class of cells .

The author takes up the theory of the n ormal eleme n t dis ,

cussi n g the relatio n s betwee n the i n tri n sic e n ergy of the cell
a n d its electromotive force the depe n de n ce of the e le c t ro mo ,

tive force upo n the co n ce n tratio n s of the solutio n s the tem ,

p e rat ure coe fficie n t and the osmotic theory of the normal ele
,

m e nt .

The several n ormal eleme nts are the n studied i n detail .

These i n clude the followi ng

 R e vi e w s . 2 37

D a niell Flemi n g eleme nt Z n Z n SO C u sO C u

-
4 4
.

C lark eleme n t Z n Zn SO H g SO4 Hg , , .

G ouy eleme n t Z n Z n SO , H g O Hg .

H elmholtz Ostwald eleme n t Zn Z n C l H g C l

-
H , , 2

Warre n de la R ue eleme n t Z n Z n C l A g C l A g 2
.

Westo n eleme n t C d C d SO H g SO H g 4 , ,
.

The book co n cludes with a chapter on the measureme n t of

the electromotive force of sta n dar d eleme n ts a nd the use of ,

such eleme n ts The electromotive force of the C lark eleme n t

.
,

as measured by the silver voltameter on the assumptio n that

o n e amp ere i n a seco n d separates fro m silver n itrate 1 18

gram of silver is
19 (t (t volt .

The work comes fro m the best source i n the worl d viz the , .
,

R eichsa n stalt a n d its author has co n tributed much to the

,

subj ect upo n which he is writi n g It will cer tai n ly fi n d its .

way i n to every laboratory where measu reme nts of e le c tro mo

tive force are ma d e H C J . . . .

SMO K E L E SS P OW DE R ,
N I TR O C E L L U L O SE ,
AN D TH E O R Y O F TH E C E L L U
L O SE M OL E CUL E . By JO H N B BE . R N A DOU, L i e u te na n t U n i t e d St ates
N av y . N e w Yo r k : J o h n Wi l e y So n s ,
1 90 1 12 mo.
pp v i ii . .

2 00 . P r i c e , $2 5 0 . . e

A s state d i n the preface the author For purposes of com ,

p a r a t i ve study has brought together i n the prese n t

volume a series of papers by various i nvestigators upo n the , ,

compo sitio n of cellulose and the properties of explosives pre

pare d therefro m H e has suppleme n ted thes e with a n ac
.

cou nt of experime nts made by himself a n d from the whole ,

has dra w n certai n co n clusio n s as to the possible ultim ate

”
chemical compositio n of cellulose an d the n itrocelluloses .

A ge n eral idea of the co n te nts of th e book c a n be obtai n ed

from the table of co n te n ts C hapter I Origi n Nome n clature .
, , ,

an d Defi n itio n s C hapter I I E arlier Views as to N i tro c e ll u .

,

lose C ompositio n and C o n stitutio n ; C hapter I I I The C on .

,

ce p t io n of P rogressio n i n R elatio n to C ompositio n a n d C o n sti

t u t io n C hapter IV Solutio n s of N itrocellulose Theory of the
C ellulose Mole cule
.
, ,

In the appe n dices the author has l n

.

clude d tra n slatio n s of papers by Viei lle an d Bruley on The

o n e by M
“
N itration of C otto n e n d e l ée f
f on P yrocollodio n
Smokeless P ow d ers a nd a sketch of his o w n work on the ,

d evelopme n t of smokeless powders .

O n accou nt of the u n certai n ty regardi n g the exact compo

sitiou of cellulose an d its n itro compou n ds great c o n fusion h as
arise n from the use of the same n ame for di ffere n t substa n ces ,

or di ffere n t n ames for the same substa n ce The author gives .

exact defi n itio n s of the terms use d by differe n t writers and a

2 38 Re vie ws .

table of the sy no nyms In traci ng the historical developme n t

.

of the subj ect he shows how the i nvestigators have bee n led
to the co n clusio n that the cellulose molecule is more complex
tha n had formerly bee n supposed a nd the ge neral course ,

wh ich the search for satisfactory smokeless pow d ers has take n .

Vieille has obtai n ed eight n itrocelluloses by worki n g u nder ,

di ffere nt co n ditio n s which differ i n their solubility an d sta

,

bi l i t y .

The author has drawn co n clusio n s regardi ng the composi

tio n and structure of cellulos e fro m the actio n of solve nts o n
the n itrocelluloses It has bee n poi nted out that the reactio n s
.

of cellulose i n the cuprammo n ium thiocarbo n ate an d mer

, , ,

c e riz atio n processes lead to the co n clusio n that the h ydrox y l

,

groups exist i n both acid an d basic form an d that the solu

bi lit y of the substa n ce i n a mixture of ether and alcohol at
ordi n ary temperatures while it will n ot dissolve i n o n e alo n e
, ,

except at very lo w temperatures is due to the di ffere n t ways ,

i n which the two solve n ts act upo n the hydroxyl groups o n e ,

acti ng upo n the basic a nd the other upo n the acid hydroxyl
groups A cti n g upo n this suggestio n the author sho w s how
.
,

a type u n it of c ellulose represe n ted by th e compositio n

,

which has four free si n gle carbo n bo n d s coul d be ,

writte n a n d ho w the more complex poly meric forms coul d be

,

built up of combi natio n s of differe n t n umbers of these u n its .

There i s n o limit to the possible n umber of such co mbi n atio n s ,

a n d the author suggests that by this assumptio n the d efi n ite

chemical co mpositio n of the cellular form i n the pla n t stru e
ture c an be accou n te d for H e says that the molecule n eed
.

n o t be limited i n compositio n to th e simplest collectio n of the

low e st p ossi ble n umber of ato ms capable of e n teri n g i nto com
bi n atio n but may be built up fro m a very great n umber of the
,

eleme ntal particles take n together i n their proper ratios Such .

a molecule wo uld i n crease i n amplit ud e accordi n g to the

n umber of eleme ntal particles e n teri n g i nto its compositio n
a n d the thought therefore suggests itself that p rog re ssi ve
va ri a ti ons i n the a mpl i tude o
f the mole cula r r i ng i s a cha ra cte r
i stic of org a n ic life or co n versely that we m ay seek for the
, ,

begi n ni n gs of orga n ic life at least i n pla n t life i n the p ol y m

— —

e ri z ati o n of the carbohy d rates

”
H e poi nts out how by the
.
,

suggested structure the polymerizatio n n itratio n me rc e riz a

, , ,

tio n an d c o lloid at ion c an be ex plai ned The p ap e rs i n the

appe n dices by Me n d e lée ff Vieille and the author who have
.
,

, , ,

bee n i n strume n tal i n d evelopi n g the smokeless powders i n use

i n the n avies a nd armies of R ussia Fra n ce an d the U n ited , ,

States respectively give the ge n eral nature of the e x pe ri

, ,

me n ts o f these ex perts and fur n ish a valuable summary of

.
,

results which have bee n d ifli c ult to obtai n o n accou n t of

 R e vie ws .

eve n the mathematical theory of liquid cells bei n g worked out

in some d etail The moder n theories of electrolysis could
.

have bee n made Clearer if d iscussed subseque nt to pote ntial

differe n ces at metal liquid j u n ctio n s The book fills how
-
.
,

ever a real n eed an d c an be heartily recomme n d ed to the class

, ,

of readers for whom it is i n te nded It is u n fortu n ate that the .

publishers h ave n ot see n fit to give it a more attractive form .

It is to be hoped that the awkward size an d arra n geme n t of

the page may b e corrected i n a later editio n .

H . M
. G OO DW N I .

O N T H E C O MP O SI TI O N O F D T C H B TT E R B U U . yJ J . L V A N R Y N , D i re c
. .

t o r t o t h e R o y a l A gri c u ltu ra l E x p e r i me n t Stat i on a t M a astric h t .

L o nd o n . 1 90 2 .

Owi n g to the fact that D utch butter the origi n of which ,

placed its ge n ui n e n ess a nd p urity beyo nd doubt has bee n ,

wro ngly declared by foreig n chemists to be a mixture of but

”
ter an d margari n e the Netherla n ds gover n me n t u n dertook a
,

careful study of the case an d especially the co n d itio n s i n the ,

latter mo n ths of the year as the trouble seemed to arise at that

ti m
,

e A very careful a n d exhaustive st u d y of the co nditio n s

.

was carried out a n d it was fou n d as here re ported that t he

, , ,

co n ditio n s of feedi n g an d pasturi n g or stabli n g had a , ,

marked i n flue n ce on the results an d showed that a n alytical ,

results which are ge n erally co n si d ered evide n ce of adultera

tio n could be obtai ned from Specime ns of p ure butter u n der
,
'

certai n c on d ition s of feedi n g etc J E G ,

. . . .

T H E L A BO R A TO R Y C O MP A N I O N To FA TS A N D O I L S I N D U ST R I E S
‘

BY J
M
. . .

L E WK O W ITSC H , A , F I C . M ac m ill an C o 1 90 1
. . . . L on d o n . .

“
T his book by the author of the well k n ow n work C hem
,
-

ical A n alysis of Oils Fats a n d Waxes is almost exclu

, ,

s i ve ly d evoted to tables which are of great value to a n y o n e

worki n g with fats a n d oils as the i n formatio n regardi n g these ,

substa n ces has bee n collecte d an d tabulated i n a very c on

v e n i e n t form The d i ffere n t values give n i n the literature
.

have bee n carefully scruti n ized a nd o n ly the most reliable

o n es give n .
J E G . . .
VO L . X X VI I . A PR IL , 1 90 2 . N O .
4 .

A ME R IC A N

T HE ST R U C T U R E SU B ST A N C E S O B OF THE
T A IN E D B Y T H E A D D ITIO N O F O R G A NI C
OX Y G E N C O MP O U ND SA N D ALU MI N
I U M H AL ID E S .

BY E LM E P K H L E R . O R .

It is well k n ow n that the h aloge n compou n ds of alu

mi n ium combi n e with ma ny orga nic compou n ds an d that
the resulti n g additio n products play an importa n t part i n some
-

of the reactio n s i n which alumi n ium compo unds are used as

catalysts Very little i s k n ow n however about the proper
.
, ,

ties of these products an d there is no experime ntal basis for,

the structural formulas that have bee n proposed for them .

The obj ect of the experime n ts described i n this paper was to

as certai n whether the compositio n an d properties of an i mpor
ta n t class of these additio n products c an be represe n te d by -

vale nce formulas and whether there is a n y relatio n betwee n

these substa nces and salts with water of crystallizatio n .

That alumi n ium hali d es combi n e with orga nic oxyge n

l
compou nds was discovered by G ustav son who fou n d that ,

alumi n iu m chloride combi n es wit h ethyl be n a te to form a

1 Be r d. . c he m . Ge s .
, 13 , 15 7 .

16 — 2 7
substa n ce whose compositio n is represe nted by the formula

Shortly after wards C ombes obtai n ed a substa nce with the 1

compositio n as o ne of the products of the rea o

tio n betwee n alumi n iu m chlori d e an d acetyl chloride a nd ,

Wi nog rad o ff worki n g u n der G ustavso n obtai ned the sub

,
2
,

sta n ce as a seco n d product of the same re ac

3
tio n L ater L ouise and P errier succeeded i n isolati n g a
.
,

crystalli n e substa n ce with the compositio n

from the products of the reactio n betwee n alumi n iu m chlo

‘
ride mesityle n e an d be n zoyl chloride This le d P errier to
, , .

u n dertake a systematic study of the reactio n betwee n alumi n

i um chloride an d orga n ic oxyge n compou nds P errier fou n d .

that alumi n ium chloride co mbi n es with acid chlorides keto n es , ,

esters phe nols bor n eol a n d camphor Of the additio n prod

, , , .
-

n e ts obtai n ed by P errier the most i n teresti n g are those with ,

acid chl orides an d keto n es si n ce they represe n t successive ,

stages i n the sy n thesis of keto n es by the Frie d el and C rafts

'

reactio n It is doubtful whether the compou n ds with phe n ols

.

are formed by direct additio n as claimed by P errier si n ce , ,

C laus an d Me rc k lin fou n d that hydrochloric acid is evolved

5

whe n alumi n iu m chloride an d phe nols are brought together in

a n i n di ffere n t medium To the product of the reactio n betwee n .

alu mi n ium chloride an d resorci nol they give the formula

i n stead of the formula

give n by P errier .

A ll the additio n products of orga n ic oxyge n co mpou nds a n d -

alumi n ium chloride that ha ve hitherto bee n a n alyzed with the ,

1 A nn . ch i m ph y s . .
, 12 , 199 .

9
J .
p ra k t Che m . .
, 37 , 1 10 .

8 C mp t
o . re n d .
, 1 14 , 137 7 .

4 I bi d 11 6 , 1 140 ; 1 16 , 1 2 98 ; 1 19 , 276.
5 Be r. d . c he m . Ge s .
, 18 , 2 934 .
2 44 Kohle r .

01
0, H, 0 -
01 C , H, C —
Cl 11 01 ;

01 01

01 O, H,
/
—
01 -
01 H CI .

O A IC I, O A l C l,

In a paper o n the molecular weight of alu mi n ium com

pou n ds I Sho w ed that these ad d itio n products have doubl e -

the molecular weight that is usually assig n ed to them and ,

that the two halves of the molecules are li n ked together b y

the haloge n atoms derived from alumi n ium chloride Thi s .

fact may be represe nted by writi ng the G ustavso n Kro nber g -

formula ,

01 01
01 : 01
0, H, 0 —
01 u
O —
Al —
Cl Cl —
Al
—
O

This formula c an be tested by experime n t If it is correct .

,

the n o n ly those o xyge n compou n d s which have at least o n e

doubly li nked oxyge n atom c an combi n e with alumi n iu m
-

chloride The results described i n this paper Show that thi s

.

is n ot the case si n ce e thers of all ki n ds combi n e with alu

,

mi n ium chloride an d alu mi n ium bromide The products are .

crystalli n e substa n ces whose co mpositio n an d molecular weigh t

are represe n ted by the formula They are i n ,

eve ry respect exactly like the correspo n di n g substa n ces ob

,
'

t ai n e d fro m acid chlorides a n d keto n es The formulas o f .

G ustavso n and Kro n berg are therefore wro n g , ,

.

This leaves two possibilities either these additio n product s -

co n tai n oxyge n that has a higher vale n ce th a n two or els e ,

their formatio n does not depe n d upo n th e oxyge n atoms i n th e

orga n ic substa n ce I f the former is true the n the composi
. ,
,

tio n of the ad d itio n products ought to vary with the n umber

-

of oxyge n ato ms in a molecule of the orga n ic compou nd It .

is d ifli c ult to test this with alumi n iu m chloride because of i t s

i n solubility i n liquids that do no t combi n e with it ; but th e
1 Th i J U N L 4 385
s O R A , 2 , .
 O rg a n i c Oxyg e n Comp oun ds an d A lu min i u m H a lide s . 2 45

r esults obtai n ed with alumi n ium bromi d e are co n clusive It .

was fou n d that the additio n products with substa nces that
-
,

h ave I atom of oxyge n to the molecule i n variably co ntai n

”
2 molecules of the oxyge n compou n d to 1 double molecule
”
o f alumi n ium bro mide while the additio n products obtai n ed
,
-

from substa n ces that h ave two atoms of oxyge n ge n erally

“
c o n tai n o n ly o n e molecule of the orga n ic compou n d to o n e
d o uble molecule of alumi n ium bromi d e .

T e re p h th aly l chloride for example forms the compou nd

, ,

while the correspo n d i n g mo n o acid chlo -

r ide forms Similarly d i ac e ty l me sity le ne ,

forms while the correspo n di n g

m o no k eto n e combi n es with on e half as much of the bromid e
- -

1 0 form the compou n d These

c ases an d ma n y similar o n es
,
sho w that a substa nce that
,

c o ntai n s 2 atoms of oxyge n to the molecule c an combi n e with

t w ice as much alumi n ium bromide as a substa n ce that co n

t ai n s but o n e
.
The combi n atio n therefore probably takes
.
, ,

p lace through oxyge n .

A ll the facts that have bee n prese n ted c an be represe nted

*
b y the followi n g f ormulas
R
\ —
_
O
R /

L \ 0/
R / \01

Formula
I is n ot in harmo n y with the behavior of ma n y
.

o f the additio n products whe n they

-
are heated A cetyl .

a ceto n e for exam ple combi n es with alumi n ium bromide to

, ,

fOr m a compou n d with the compositio n This

d ecomposes at ordi n ary temperatures accordi n g to the equa
tio n
2 H Br .

The product of this decompositio n combi n es with more

acetylaceto n e formi n g a ne w additio n pro d uct which also
,
-

decomposes on hea t i n g a n d the process of a d ditio n and de

,

c ompositio n c an be repeated u n til the fi n al product is pure

2 46 Kohle r .

alumi n ium acetylaceto n e a substa n ce a n alogous to alu —

mi n i um hydroxi d e The ad d itio n products with ethers and .

-

phe n ols behave i n the same way Thus H artma n n an d G at .

,

t e rmann fou n d that the substa n ce de co m

l
,
°
po ses at 1 2 0 accordi n g to the equatio n

an d Merz an d Weith fou nd that whe n alumi n iu m chloride

2
is
heated with phe nol the fi n al product is alumi n ium phe n olate .

A ll of these reactio ns are easily u n derstood if the structure ,

'

of the additio n products is re p re se n te d by formula I I T he

-
.

decompositio n of the double compou n d with a n isol for exam ,

ple ta k es place as follows

,

A 1( 01, ) A 1

C H3 C1 C1 C Hs
2 C H, C l

It is remarkable that 1 molecule of an alu mi n iu m hali d e

n ever co mbi n es with more tha n 2 molec u les of a n orga n i c

oxyge n compou n d while it combi n es with 6 molecules of an

aro matic hydroc arbo n ”
Si n ce ma n y of the colored additio n .

products described i n this paper cha n ge color whe n dissolved

i n be n ze n e it is probable that these substan ces also combi ne
,

with aromatic hydrocarbo n s A fter ma n y attempts at isol a .

ti n g such additio n products I fi n ally succeeded with a nthra -

q ui n o n e which forms the compou n d

,

This suggests as a possible expla n atio n of the Friedel and

,

C rafts reactio n that the alumi n ium halide combi n es with both
,

the acid chloride an d the hydrocarbo n formi n g a complex ,

molecule which subseque ntly u n dergoes a rearra n geme n t

similar to that observed i n the case of the additio n pro d uct -

with acetylaceto n e Such a me c ha n is m would explai n why

.

the reactio n takes place o n ly wit h aromatic hydrocarbo ns .

It has bee n fou n d quite rece n tly that the compositio n an d , ,

properties of a n umber of substa n ces c an be explai n ed by the

assumptio n that they co ntai n quadrivale n t oxyge n Si n ce .

1 Be n d c
. . he m . Ge s .
, 2 5 , 35 3 1 .

2 I bi d . 1 4 , 1 89 .
,

3 G u s ta v s o n J ou r . R uss . P hy s C he m
. . So c .
, 10 , 305 .
2 48 K ohle r .

crystalli ne compou nds with aromatic ethers were purified an d

a n alyzed .

1 . P he ny l E the r a nd A lumi n i um B romide ,

—
A lumi n ium bromide dissolves i n phe n yl ether with e vol u
tio n of heat but it is d ifli c u lt to isolate a pure substa n ce from
,

the solutio n It is better to bri ng the substa n ces together i n

.

carbo n disulphide solutio n and precipitate the product with

low boili ng petroleu m ether I f the ether is carefully strati
-
.

fi e d o n top of the solutio n the product crystallizes slowly i n

[

large lemo n yel low plates that are easily purified

-
The .

preparatio n s used i n the followi n g experime nts were washed

with a mixt ure of petroleum ether an d carbo n disulphide and
dried i n a curre nt of dry air .

T o determi n e the amou n t of phe n yl ether co ntai n ed i n the

Substa n ce a w eighed q ua n tity of the latter was decomposed
,

with ice the resulti n g liquid extracted with pure ether the
, ,

ethereal solutio n dried with a little fused calcium chloride ,

an d evaporated i n a weighi n g tube The alumi n ium was de .

t e rmi n e d as oxide by decomposi ng a weighed q ua n tity with

ice water evaporati n g the solutio n and ig n iti n g the resid ue
-
, , .

I . gr am s substa n ce gave gram

II . gram substa n ce gave gram A l O , ,
.

u
Fo n d .

The substa n ce is readily soluble i n be nze n e an d carbo n di

sulphide i n soluble i n ligroi n It is less stable tha n the cor
,
.

respo n di n g additio n products with acids a n d keto n es Whe n

-
.

heated by itself it begi n s to decompose below a nd the fol

lowi n g molecular weight determi n atio n shows that it is also

partly dissociated i n boili n g carbo n disulphide

Su b s tan c e E l e v a ti o n o f Mol e c ul a r
m b oi l i n g p oi n t gh t
.

G ra s. -
. we i .

4 -34 30 6 0 6 -7
C alculated for
 Org a n ic Oxyg e n Comp ounds a nd A lumi n i u m H a li de s . 2 49

The followi n g determi n atio n m ade by the freezi ng poi nt -

method usi ng be n ze n e as solve nt shows that the substa nce

, ,

h as the formula give n to it

D e p re ssion of Mo l e c ul ar
f re e z in g p oi n t . wei gh t .

Mea n ,

C alculated for

2 . Phe ny l E the r a nd A lu mi n i um Chlorz de ,

-
The substa nces were brought togethe ri n c arbdn disulphide
a nd the product purified and a n alyzed li k e the correspo n di n g

compou nd with alumi n i um bromide .

The a n alysis gave the followi n g results :

I grams substa n ce ga ve
. gram ( C, H
II gram substa n ce gave
. gram A l
III gram substa n ce gave
. gram A g C l .

C l ul
a c a te d fo r Fo un d .

A 12C 13 . II .

Al
C1

The substa n ce crystallizes i n pale yellow plates which are -

,

very readily soluble i n be nze n e a n d carbo n disulphide .

3 . A n i sol a n d A l u mi n i u m B romide ,
E quivale n t qua n tities of
a nisol and alumi nium chloride
were brought together i n carbo n disulphide solutio n The .

solutio n was cooled with ice water an d the product precipita -

ted with petroleum ether U nless the ether is added very .

slowly to the well cooled liquid the product separates as an

-

oil .

I . gram substa n ce gave gram A l, O , .

II . gra msubsta n ce gave gram A g Br .

C l ul t d f
a c a e or Fo n d u .

A ln o 2 C3H 5 O C H3
. .
 The substa n ce crystallizes i n compact pale yellow prisms ,
-
.

It is very readily soluble i n carbo n disulphide be n ze n e a n d , ,

a n isol The same product is obtai n ed wh ether alumi n ium bro

.

mide or a n isol is used i n excess .

4 . A n i sol a nd A lu mi n i u m Chlori de ,
Freshly distilled alumi n iu m chloride was d issolved in an ex
cess of a n isol the solutio n diluted wit h carbo n disulphide
, ,

a n d the product precipitated with petroleum ether .

I . gram substa n ce gave gram A l O , ,

.

II . gram s u bsta n ce gave gram A g Cl .

C l ul t d f F u nd
a c a e or o .

A 12C 16 . 2 C 6 H 5 0 C H 3.

AI 1

Cl

5 . M thy l n p h nyl
e e e e e ne E the r a nd A l um i n i u m B romi de ,
A
saturated solutio n of the ether i n carbo n
—

disulphide was added d rop by drop to a boili n g solutio n of , ,

alumi nium bromide i n the same solve n t The p roduct sepa .

rated o n cooli ng i n the form of fi n e yellow n eedles It was

, , .

washed with a small qua ntity of cold carbo n disulphide an d

recrystallize d from a mixture of carbo n disulphide an d low
boili n g petroleum ether .

I . gram substa n ce gave gram ether .

II . gra m substa n ce gave gram A l O, ,

.

C l ul t d f F und
a c a e or o .

A IQB I GJ C mH mO
'
.

I,

The substa n ce is very soluble i n carbo n d isulphide and

° °
be n ze n e almost i n sol uble i n petroleum ether A t 9 0 to 1 00
, .

it loses approximately 2 molecules of hydrobromic aci d The .

residue o n cooli ng solidifies to a resi n ous mass which could

, , ,

n ot be obtai n ed i n crystalli n e form Water decomposes it .

i nto m e thy le ne p he n y le n e ether an d alumi n iu m hydroxide .

II . Comp oun ds w i th K e ton e s .

I . A ce to p he n on e a nd A l u mi n i um B romide ,
A l, B r, .
—
E quivale n t qua n tities of the substa nces
were brought together in carbo n disulphide an d the solutio n
25 2 K olzle r .

C l ul
a c a te d fo r Fo u nd
A 12 B5C
7 .
0H I .

Al

The substa n ce was obtai ned as a fi n e reddish yellow pow ,

-

der but the color is probably due to some impuri ty as the

, ,

correspo n di n g additio n product with d ic hlorace ty l me sity l e ne

-

is almost colorless The substa n ce is i nsoluble i n carbo n di

.

sulphide slightly soluble i n boili n g be nze n e It dissolves

, .

fairly re adily i n a stro n g solutio n of d i a ce ty lme sity le n e i n car

bo n d isulphide a nd crystallizes out u n cha n ged o n cooli n g .

A ll e fforts to get the substa n ce correspo n di n g to the additio n

products with mo nok e tone s ,

faile d .

4 . Chlorae e lyl m e si iyle ne a nd A l u m i n i u m B r omide , A lz Bre .

C hlorac e ty l me s ity le n e
forms o nly
o n e compou nd with alumi n i um bromide The same substa n ce .

was obtai n e d i n all of the followi n g experime nts : ( a ) e q u iv a

le n t qua n tities of the substa n ces were brought together i n
carbo n disulphide solutio n ; ( 6 ) a solutio n of the keto n e i n
carbo n disulphide was gra d ually added to four times the cal
c u late d amou nt of th e bromide d issolved i n carbo n disulphide

( o) a solutio n of the bromi d e was a d ded to four times the cal

c u l at e d a m ou n t of the keto n e dissolved i n carbo n disulphi d e

( d ) a solutio n of the keto n e i n be n ze n e was added to an ex

cess of the bromide likewise d issolved i n be nze n e ; ( e ) the
subs ta n ces were brought togeth er i n n itrobe nze n e a n d the
pro d uct precipitated with petroleum ether The substa nce . .

crystallizes well a n d is easily obtai n ed i n a pure co nditio n .

I . grams substa n ce gave gram keto n e .

II . gram substa n ce gave gram A 1 03 2

.

C l ul
a c a te d fo r Fo n du
A l gB r5 . 2 C 5 H 2 ( C H 3 ) 3 C 0 C H 3C 1

C GH, ( C H3 ) 3 C O C H2 C 1
Al

5 . D ie /
zlora ce ly l me sz /le n e
b a nd A lu mi n i um B rom ide , A lz B rs .

solutio n of t he keto n e i n carbo n

-
A
disulphide was slowly a d ded to a boili n g solutio n of alu
mi n ium bromide i n the same solve nt The precipitate was .
 Org a n ic Oxyg e n Comp ounds a nd A lumi n i um Ha li des . 253

washed with boili n g carbo n disulphide an d dried in a curre n t

of air .

I . gram substa n ce gave gra m keto ne .

II . gram substa n ce gave gram £ 1 1 03 2

.

C l ul t d f a c a e or Fo und
I .

33 5 6
Al

The substa n ce crystallizes in small pale yellow plates It ,

-
.

is Spari n gly soluble i n boili n g carbo n disulphide an d boil

i n g be n ze n e .

6 . D i be n z a lace ton e a nd A lumi n i u m B r omide ,

C H ) , CO
qua ntities of d i .
—
E quivale nt
be n zalaceto n e and alumi n ium bromi d e were brought together
i n carbo n disulphide solutio n The additio n product separa .
-

t e d imme d i ately as a red crystalli n e precipitate .

I . grams substa n ce gave gram keto n e .

II . gram substa n ce gave gram A 1 03 2

.

C l ul t d f F u d a c a e or o n
A l gB r6 . 2 ( C 6 H 5 C H : C H ) 2C O

( C6 H5 C H CH),CO
Al

The substa n ce i s o n ly very slightly soluble in carbo n d is nl

p h i d e Whe
. n prepared as described above its color is ex ,

a c tl y like that of the hydrochloric acid additio n produc t -

which is obtai n ed on pouri ng fumi n g hydrochloric acid o n di

‘

be n zalaceto n e It dissolves slowly i n boili ng be n ze n e and

.

crystal lizes out agai n on co oli n g in large bloo d red prisms

, , ,
-
.

In the boili n g solutio n the substa n ce is probably almost c o m

p l e t e l y dissociated s i n ce at this
, temperature the solutio n is
almost colorless The color d eepe n s as the temperature falls
.

u n til at the ordi nary temperature the color of the solutio n

, ,

is the same as that of the additio n product which crystallizes -

out .

7 . A n l/
z ra gu i n on e a nd A l u mi n i u m B romide , A l2 Brs .

CO
\O H
C 6 H4
< 00 /
—
A solutio n of a n thraqui no n e in boili ng

carbo n disulphide was added ,

in small portio n s to a boili n g ,
solutio n of alumi n ium bromide i n the same solve nt The .

produc t separated as a fi n e brick red crystalli n e powder ,

-
, .

This was washed with boili ng carbo n disulphide drie d and , ,

a n alyze d .

I . gram substa n ce gave gram a n thraqui n o n e .

II . gram substa n ce gave gram A 1 03 2

.

C l ul t d f F u nd a c a e or o .

A l gB r6 C 14 H 9 0 2
. .

The additio n product is i n soluble i n carbo n disulphide It

-
.

d issolves slowly i n boili n g be nze n e to form a deep blood red -

solutio n A similar solutio n is obtai n ed whe n alumi n i um

.

bromide an d a n thraqui n o n e are brought together in boili n g

be n ze n e O n cooli ng the solutio n a n e w substa nce crystal
.
,

lizes out i n blood red n eedles The substa n ce co n tai n s 2

-
.

molec ules of be n ze n e which it slowly loses at ordi n ary tem

,

p e rature s passi n g back i n to the brick red powder d escribed

-
,

above To d etermi ne the amou n t of be n ze ne the substa nce

.
,
°
was heated to 5 0 i n a curre n t of dry air .

I . grams substa n ce lost gram .

II . grams substa n ce lost gram .

II I . grams residue after he ati n g gave gram , ,

A 1203 .

C l ul
a c at e d fo r u
Fo n d .

O
A l 2 B r6 C 6 H 4/
.

\C O > C6 H 4 . 2 C6 H6 .

7 30,

The substa nce is extremely u nstable Whe n poured i nto .

carbo n disulphi d e or petroleum ether it i mme d iately loses all

its be nze n e passi n g i n to the brick red compou nd witho ut
,
-

goi n g i n to solutio n .

8 Xa n i lzon e a n d A l u mi n i u m B romi de
.
,

E quivale n t qua n tities of xa ntho n e an d alumi n ium bromid e

were dissolve d in boili ng be nze n e The product separated .
,

on cooli ng i n lo n g yellow n eedles

,
A fter recrystallizatio n
,
.

fro m be n ze ne it was washed with cold carbo n disulphide an d

,

dried i n a curre n t of air .

256 K ohle r .

rates i n pale yellow plates The same substa nce is formed

-
.

whe n c hlorac e ty l chloride is added to an excess of alumi niu m

bromide dissolved in carbo n disulphide The substa n ce was .

recrystallized from carbo n disulphide It is so exceedi ngly .

se n sitive to moisture that it is almost impossible to d rv it

without loss .

I .gram substa n ce gave gram A l os ,

.

II . gram substa n ce gave gram A g C l ( Br ) .

C l ul t d f F un d
a c a e or o .

A l z B r6 . 2 C H2 C 1C O C l

2 . Te rephi ha ly l Chlor i de a nd A lu mi n i u m B r omi de , A lz Brs .

of te re p h t haly l chloride in carbo n

—
A solutio n
disulphi d e was slowly a dd ed to an excess of alu mi n ium bro
mide an d the liquid boile d for an hour The additio n prod .
-

u c t separated as a very fi n ely divided pale yellow po wd er It -

.

was repeatedly washed with boili n g carbo n disulphide dried , ,

a n d a n alyzed .

I . gra m substa n ce gave gra m terephthalic

aci d .

II gram substa n ce gave

. gram A l 03 ,
.

III gram substa n ce gave

. gram A g C l ( Br ) .

IV gram substa n ce gave

. gram A g C l ( B r) .

C l ul t d f a c F u d
a e or o n

0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 0

The substa nce is i n sol uble i n carbo n disul phide It dis .

solves i n a s tro n g solutio n of te re p ht h aly l chloride i n carbo n

disulphide but crystallizes o ut u n cha n ged as show n by the
, ,

a n alysis ( I V ) of a preparatio n obtai n ed i n this way

. .

3 . Te rephzhalyl Chlor i de
‘
a nd A lu m i n i u m Chl ori de , A I, C I, .

Freshly
prepare d alumi n ium chloride was
—

suspe nded in carbo n disulphide a nd te re p hthaly l chlorid e

added to the boili n g liquid u n til all the alumi n ium chloride
 Py r ro a , fi -
Dia z ole De ri va ti ve s .

dissol ved It took a little more th a n 2 molecules of tere

.

phthalyl chloride to dissolve 1 molecule of the salt O n cool .

i ng the solutio n the ad d itio n product separated i n large tra n s -

,

pare nt plates .

I . grams substa n ce gave gram terephthalic

acid .

II . gram substa n ce gave gram A l O s ,

.

C l ul
a c at e d fo r Fo und .

C ont ri bu t i o ns fro m t he Sh e l
ffi e d L a bora t ory of Ya l e U n iv e rs it y .

XCII .
—
ON T HE A C TI O N O F P H E N Y LHY D R A Z I N E
ON A C YL T IIIO C A R BA —
MIC A N D A C Y L I MI DO
T H I O C A R BO NI C E ST E R S: P Y R R O
a fl D I A ZO L E D E R IV A TIV E S
,
’
-
.

B Y H E N Y L W H EE E D A LL N G P BE
R D SL EY
. L R A N I . AR .

A cetoacetic ester a n d ac e ty lu re th an e are attacked by

phe n ylhydrazi n e i n a n a n alogous m a nn er In both cases the .

acetyl group a n d not the c arbethoxy group is the poi n t of

, ,

attack by the ami n o N H ) group of the hydrazi n e —

,
.

The ri n g formed compou n ds that the n result are derivatives

-

of di alk y lp y raz ole an d

-
d i alk y l py rrod i az ole re s e c
p
-
,

t i v e ly .

It might be expected that the be n z o y lthiol t hi ou re th an e s —

,

thio n and dithiocarbamates would behave i n a similar way

,
—
.

We have fou nd however that the uretha n es co ntai n i n g sul

, ,

phur react with phe n y lhydrazi n e i n precisely the O pposite

ma n n er that the N II group of the hydrazi n e reacts with — —

the ester group an d not W ith the be n zoyl group H ydroge n .

sulphide or mercapta n is evolved a nd 1 5 d i al k y lp y rro d i az ole ,

-

( t riazole ) derivatives result i nstead of the isomeric com

pou n ds E xam ples of the reactio n s of four types of ac y lu re
.

tha n es are tabulated below They illustrate more defi n itely .

the above stateme n ts and they show that four d iffere nt series ,

of pyrro a 3 diazole derivatives result i n the reactio ns i n ques

,,
’
-

I7 “
27
258 Whe e le r a nd Be a rdsley .

tio n The products in I I I an d I V may n aturally be rep

. .
, .

rese n te d as havi n g the tautomeric C O a n d C S structures

C H, c —
N = 00 H

H, N N H C6 H 5 N N C 6 H5
06 H 5 00 N H co s c , H, . C GH5 C Z N —
COH

C sHsN H -
N H, 06 H5 N -
N
06 H5 00 N H c s oc , H, . c 115 ( zz n —
c o c H5
I
C6 H5 N H ~
N H2 —
N

06 H5 00 N H cs s c , H, . c H5 c z n —
os n

C sHsN H —
N H, c, H, N

The product in
reactio n I was first obtai n ed as above by .

l
A n dre occ i a nd the above co n stitutio n
,
i e 1 phe n yl 3 , . .
,
- -

methyl 5 ox y triaz ole was assig n ed to the compou n d This

- -
, .

2
was prove d to be correct by B amberger an d de G ruyter an d ,
3
by Widma n .

The product obtai n ed by us i n reactio n I I proved to be .

ide ntical i n every respect with the o x y tri az ole prepared by

, ,

Y ou ng fro m p he ny lse mic arbaz ide be n zaldehyde and ferric

4
, ,

5
chloride ; a nd by Widma n by warmi ng be nz oy lp h e n y lse m i
carbazide with alkali .

The reactio n represe n ted by equatio n III was i n vestigated .

“
by Wheeler and Joh n so n i n the case of methyl be nz o y lthion ,

carbamate an d the product was shown to be 1 5 diphe n yl 3

, ,
- -

me th ox y tri az ol e by boili n g with hydrochloric aci d where , ,

upo n the triazole of Y ou n g a nd Widma n w a s obtai n ed ‘

The proof that the m e rc ap t otriaz ole formed i n reactio n IV .

is 1 5 diphe nyl 3 me rc a ptotri az ol e follows fro m the fact that

,
- - -

the same co mpou n d results by warmi n g alcoholic solutio n s of

h e n l t h i o se mi c arbaz i d e be n zaldehyde a n d ferr ic chlori d e
p y , , .

This product is e n tirely differe n t from the isomeric di -

1 Be r . d . c he m . Ge s .
, 22 , R .
7 37
2 I bi d . 2 6, 2 3 85 .
,

8 2 6, 2 6 17

4
J . Ch m e . So c .
, 67 , 1 06 3
5 Be r. d . c he m . Ge s .
, 2 9, 19
51
6 Th i J O U R N A L
s , 2 4, 198
2 60 Whe e le r a nd B e a rdsley .

OC s
c.H.C O N = C
06 11 5 0: N —
COC.H5 C .H5 3 H
SC H52

C GHsN —
N
C e HsN H _
N Hz
We have fou n d that the reactio n takes place as i ndicated ,

that mercapta n an d water are liberated and that 1 5 d iphe n yl , ,

-

3
-
e t h ox y t ri a z 0 1e is formed I n this case it was easy to sho w
.

that the reactio n takes place i n two stages Whe n ph e ny lhy .

d raz rn e was mixed with be nz oy l i mi dot hi oe t hy l carbo n ate i n

be nze n e mercapta n alo n e was evolved an d the product Oh
'

, ,

t ai n e d was be n z oy lp se ud oe t hy l ph e ny l se mi c arbaz i d e ,

C 6 H5 C O —
NH —
N H C 6 H5 .

This i n termediate product c an be crystallized fro m alcohol an d

is stable below at which temperature it loses water a nd
is smoothly co n verted i nto d iphe n yl 3 e t hox y tri az ol e - - -
.

The stability of this product is especially sig n ifica n t as it ,

a ffords a n i ndicatio n of the mecha n ism of the above reactio n s .

If the ac y l u re th an e s are represe nted as havi n g the pse u d o

form , or
'

etc the n th e se as well as the ac y lim id oc arbon i c esters c o n

.
, , ,

tai n a double u n io n O = C an d p he ny l hy d r a
,

1
zi n e might be expected to add to these compou n d s accordi n g ,

to Thiele s theory i n the ’

positio n as represe n te d by for
, ,

mula VI I This sort of reactio n would appear to satisfac

.

t o rily explai n the above triazole forma tio n s were it n ot fo r ,

the fact that i n the prese n t case it is di fficult to reco n cile the
stability of the i ntermediate product with this formula .

O C .H.
-
c c , H, CO —
N 11 —
c
sc , H,

c , H, N H 0, 11 5 N 11 N 511
VI I I .

compou n d with an e n ol structure such as V II would

A , .
,

separate water an d form the triazole more readily tha n the

1 Th at th e a c ti on o f a mi n e s on th e a c y l thi on c a r b a m i c e s te r s ta k e s pl ac e by a d di

ti on h a s l
a r e ad y be e n s h ow n in a p . r e vi o u s pap e r. Th i s JO U R N A L , 2 4, 1 89
 "
Py rr o -
a
, , 6 Di a z ole D e r i va i i ve s . 261

k eto form V I II an d therefore the latter better represe nts

, .
, , ,

t he course of the reactio n .

The fact O bserved by Wid man that be n z oy lp h e ny lse mic ar

4

b a z i d e C 6 H 5 C O N ( C 6 H5 ) N H C O N H
,
is not tra n sformed i n to
a triazole by heati n g with aci d chlorides acid a n hydrides or , ,

by stro ngly heati n g alo n e is probably to be explai n ed by the ,

a bse n ce of hy d roge n a d j ace n t to the be n zoyl group Whe n .

,

however this compou n d is treated with alkali it readily gives

,

-
d iphe n yl 3 o x y tri az ol e I n other words it appears to us
- -
.
,

t hat an u n stable alkali additio n product is formed as has fre -

,

q ue n tly bee n O bserved i n th e case of acid amides n amely , ,

—
N c, 11 , —
N H CO N 11
a nd as this a ffords the n ecessary e n ol co nditio n the material ,

t he n rea d ily u n dergoes co nde n satio n .

Now with this expla n atio n we were co n fro n ted w ith what
, ,

a t first appeared to be a serious d ifi c u l t y i n accou n ti n g for

t he ease with which the ac y l t hioc arba mat e s directly form tri
a zoles For if the actio n of phe n ylhydrazi n e on be n z oy ld i
.
,

t hiocarbamates C H5 C O N H C S SR results i n the form atio n of

, 6
.
,

a compou n d a n alogous to V I I I the n by separatio n of mer .

,

c apta n be n z oy lp he ny lth iose mi c ar baz i d e C 6 H 5 C O N H C S

, ,
—

N H N H C H 5 must be the i n terme d iate product

—
2
.
6 ,

A compou n d that is represe n ted as h avi ng thi s structure

3
h a s bee n prepare d by Dixo n by combi n i n g phe n ylhydrazi n e
with be n zoyl rhod an id e This however does n ot melt eve n .
, ,

at while the m e rc ap totri az ole melts at 1 8 7 an d is easily °

forme d at the temperature of the steam bath -

.

In our first experime n ts we heated the be n z o y lth io c arbam

a tes with a slight e x ce ss of phe n ylhy d razi n e a n d u n der these ,

co n ditio n s n o i n termediate pro d uct was observed This sug .

gested the thought that the slight excess of phe n ylhydrazi n e

e mployed might have acted by catalysis o n the i n terme d iate

products like alkali in the above case The e n ol co nditio n

, .

t hus prod uced would the n readily give rise to co nde n satio n .

A cti n g on this suppositio n we thereupo n carried out the re ,

a ctio n with be nz o y l d ith io e t hy l c arbam ate i n a cold di lute al , ,

1 L it
oc S . l Y u g d A nn b l J C h m S 7
c . e e a so 4 o n an a e . e . oc . , 1, 2 0
2 O u me
r a ta to ric fo mr .

3
J Che m S
. . oc . 55 , 304
262 Whe e le r a n d B e a rdsley .

c oh ol i c solutio n mercapta n almost immediately made its

prese nce k n ow n an d after sta ndi n g some time a beautifull y
,

crystallized mass of material separated which proved to be ,

the desired i ntermediate product .

The curious fact was the n observed that this compou nd

°
melted at 1 3 6 an d w as therefore differe nt from the expected , , .

be nz oy lp he n y l th ios e m i c arbaz id e of Dixo n Whe n our ma .

t e ri al was heated above its melti n g poi n t it gave off water a n d -

,

passed smoothly i nto 1 5 diphe n yl 3 me rc ap totri az ole a re ac ,

- - -
,

tio n showi ng the substa n ce to have the structure which Dixo n

has assig n ed to his compou n d The expla n atio n of the struc .

ture of the latter compou n d which n ow does n ot immediatel y ,

1
co n cer n us will receive atte n tio n at a later time
, .

The catalytic effect of phe n ylhy d razi n e o n o ur be nzoyl

p h e n y l thiose mic arbaz id e at th e temperature of boili n g alco ,

hol proved to be precisely what was expected The sub

, .

sta n ce can be repeatedly crystallized fro m alcohol withou t

alteratio n If a couple of drops of phe n ylhydrazi n e are
.

added however an d the boili n g co n ti n ued the material is

, , ,

qua n titatively co n verted i nto the me rc ap totri az ole The sam e .

tra n sformatio n takes place i n the cold with alkali .

The above exp erime n ts co n clusively show that i n these 1 4 ,

u n saturated compo u n ds a a n d n ot a ad d itio n or at

,

tack takes place This is i n all probability due to the fact

.

that the form C O N H is more stable tha n —

C O H= N —

a n d that hydroge n has a greater te n de ncy to attach itself t o

2
n itroge n tha n to oxyge n .

E XP E R I ME N T A L PART .

M thy l
e B e n z oy ll hi olca r ha ma l e , C 6 H5 C O N H CO SC H a nd

P he ny l hy dra z i n e .
—
Molecular qua ntities
of the carbamate an d
phe n ylhydrazi n e were mixed in a little alcohol an d warmed
for several hours o n the stea m bath A fter the evolutio n o f
'

-
.

mercapta n h ad ceased the alcohol was evaporated and th e ,

resi d ue was treate d with warm dilute alkali whereupo n on , ,

1 Si n c e th e a b ov e w a s w ri t te n D r . T B J hn s
. . o on has e x mi n d t h i s p od u t nd
a e r c a

f u n d th
o at it i s - di ph e ny l5
- -
m e rc a p tot ri az ol e . Se e e xp e i m e nt l p art o f th i s
r a

p pe n
a

Fo r ot e rh e x c e ptions se e Th i e l e : A nn . Ch m e .
( L ie big ) 3 0 6 , , 1 05 ( 1 899 ) 3 19 ,
12 9
2 64 Whe e le r a nd B e a rdsle y

oxide From its solutio n i n ammo n ia silver n itrate p re c ip i

.

tates a bul k y white amorphous silver salt which is n ot de

, ,

composed by boili ng .

A n attempt was made to prepare the me rc aptotri az ole from

l
-
diphe nyl 3 c hlortri az ole but it was fou n d that this chlo
- -
,

ride could be fused with potassiu m hydrosulphide a nd re co v

ered u n altered .

E thy l Be n z oy ldi thioca r ha ma te C 6 H5 C O N H C SSC H5 a nd , 2 ,

P he ny lhy dr a z i n e Seve n grams of the former a n d

.
—
of the
latter were mixe d i n 2 5 cc of alcohol and allowe d to sta n d for
;
.

several hours Mercapta n made its prese n ce k n ow n almost at

.

o n ce and fi n ally a mass of colorless six sided plates or tables

, ,
-

separated th at had every appeara n ce of bei n g pure This ma .

°
t e ri al melted at 1 3 6 showi n g sig n s of melti n g at
a n d three crystallizatio n s from alcohol failed to alter the melt

i n g poi n t O n rapidly cooli n g the alcoholic solutio n s the ma

-
.
,

t e ri al cry stallized i n lo n g sle n d er prisms which to the n aked , ,

eye appeare d as n eedles A n itroge n determi n atio n agreed .

with the calculate d for be nz oy lp h e n y lthiose m ica rbaz id e ,

C , H 5 C O N H C SN H N H C3,,H5 —

C l ul t d f a c a e or
C 14H 13 0 N 3 S.

I S-49
Whe n this substa n ce was heated above its melti n g poi n t it -

effervesce d vigorously at 1 7 0 to
°
O n crystallizi ng the n
°
from alcohol it me lted at 1 8 7 an d was fou n d to have bee n
tra n sformed i nto d iphe n yl 3 m e rc ap to tri az o le
- - -
.

O n e gram of the material was d issolved in alcohol an d 2 or

3 drops of phe n ylhydrazi n e were added o n evaporati n g to
dry n ess a n d crystallizi n g fro m alcohol i n w hich the material ,

was the n mu c h less readily soluble it was fou n d that the sub ,

sta n ce h ad bee n co nverted i n to the above triazole .

A portio n was dissolved i n cold dilute so d ium hydroxi d e a nd

immediately precipitate d by dilute hy d rochloric acid where ,
°
upo n without further purificatio n it melted at 1 8 7 to
, 5 ,
.

I J D iphe ny l l ri a z ol e j m on osu lphide

- -
Three »-
,
—

grams of the me rc ap totriaz ole an d 2 0 grams of a n ili n e were

° °
heated i n a closed tube at 2 7 0 to 300 for twelve hours O n .

1 Cl B d
e ve :h m G er .
9 67 . c e . es .
, 2 , 2 2
 Py r ro -
a 8
,,
’
-
Di a z ole De r i va ti ve s . 2 65

cooli n g o n ly slight pressure was fou nd i n the tube due to hy ,

droge n sulph i d e The co nte n ts of the tube were dissolved i n

.

alcohol a nd precipitated with d ilute sodium hydroxide The .

i n solubl e part was crystallized from alcohol whereupo n bulky ,

n eedles of a pi n kish brow n shade were obtai n ed which melted

-

at
This compou n d was also obt ai n ed by heati n g the mercapto
°
tri azole with paratoluidi n e at about 1 80 for thirty hours .

Sulphur determi n atio n s gave

C l ul t d f F und
a c a e or o .

n H goN GS . I .

S 7 . 29

D m
'

I 5
,
i
-
phe ny l t a z ol e 3 d i su l
p hi de ,
The mer
- —

c a p tot ria z o le was d issolved with o n e molecular proportio n of

sodium ethylate i n alcohol an d somewh at over the calculate d

qua n tity of iodi n e was added The alcoh ol was the n e v ap o .

rated an d t n e residue was crystallized fro m alcohol where ,

upo n small colorless pyramids or sharp poi n te d crystals like

,
-
,

arrow heads were obtai n e d which melted at

-
,
The m a ,
n .

te ri al was free from io d i n e an d a n itroge n d etermi n atio n ,

gave :

I ,5
Dip he ny l 3
-
propor —
Molecular
tio n s of m e rc ap to tri az ole sodi um ethylate an d be n zoyl ch lo, ,

ride were mixe d i n alcoholic solutio n the alcohol was t h e n

evaporated the residue washed with water an d crystallize d
, ,

from alcohol whereupo n beautiful colorless n ee d les melti n g

, , ,

at 5 were O btai ned

,
A n itroge n d etermi n atio n gave
.

C l ul a c a te d fo r
C 21 H 15 0 N 3 8 . Fo un d .

Dip he ny l 3 m e thy lme rcap totri a z ole

- -
was prepare d fro m
-

be nz o y l im id o d i th io me t hy l carbo n ate an d
phe n ylhy d razi n e ( by
Dr T B Joh n so n ) an d also by methylati n g the mercap t o
. . .
~

triazo le by mea n s of sodium ethylate an d methyl iodide In

.
.

bo th cases beautiful colorless tab les or six sided plates m elt

,
-
,
°
i n g at 1 0 2 to were obtai n e d on crystallizi n g from alcohol .
266 Whe e le r a nd B e a r dsley .

A itroge n determi n atio n was made from a specime n obtai n ed

n

by the first method .

C l ul t d f a c a e or
C 15 H 13 N 3 3 . u
Fo n d .

I S-7 3 I S7 9
-

Stro n g aqueous potash has n o e ffect o n this compou nd .

Whe n fuse d with potassiu m hydroxide it di ssolves a n d on ,

aci d ifyi ng the m e rc a pt otri az ole m elti ng at 1 8 7 i s obtai n ed

,
°
.

-
D ip he ny l 3 - -
e thy l me rcap totr i a z ole was obtai ned by e thy l a

ti n g the m e rc ap tot riaz ol e by mea n s of sodiu m ethylate and

ethyl bromide O n crystallizi n g from alcohol it forms lo n g
.
,

sle n der colorless prisms melti n g at

, A n itroge n deter
mi n atio n gave
C l ul t d f a c a e or
C 16 H 16 N 3 S
~ u
Fo n d

,5
I Dip he ny l 3 e thyla ce ta te m e r cap totr i a z ole was obtai n ed from
- -

the me rc ap totri az o le prepared from p h e n y l thi ose mic arba z id e ,

as well as from that prepare d by mea n s of be nzyl be n z oy ld i
t hio c arba m ate a n d phe n ylhydrazi n e In both cases beauti .

ful colorless prisms were O btai n ed which m elte d at

,

Whe n the samples w ere mixed the melti n g poi n t was not low -

ere d A n itroge n determi n atio n gave

.

C l ul t d f a c a e or
C 13H 17 0 2N 3 8 . u
Fo n d

I ,5
D ip he ny l 3 he n zy lm e rcap totr i a z ole
-
This was obtai ned .
—

i n three ways It was first prepared by warmi n g molecular

.

qua n tities of be n z oy l imid od i thi obe n z y lc arboni c ester a n d

phe nylhydrazi n e o n the steam bath The mercapta n evolved -
.

was removed by distilli n g u nd er dimi n ishe d pressure an d the

resid ue was crystallized from alcohol whereupo n beautiful , ,

flatte n ed colorless prisms clustere d i n the form of balls were

, , ,
°
obtai n ed These melted at 1 00 to
. a n d a n itroge n de

termi n atio n was made with the result give n belo w .

This c o mpou n d was also obtai n ed by treati ng the m e rc ap

t otri az ole with alkali a n d be n zyl chloride .

C l ul t d f a c a e or
C oi H u N a S u
Fo n d
268 Whe e le r a nd B e a r dsley .

B e nz oy li mi domon othi oe thylca r bon a te , C e HsC O N =C

<S C 2H,S
a nd P he ny lhy dr a z z n e
Whe n molecular qua n tities of the
’

—
.

above substa n ces were dissolved i n be n ze n e the odor of mer

capta n was soo n noticed an d o n sta n di n g several hours a mass
,

of crystals separated O n crystallizi n g these from alcohol

.
,

radiati n g groups of fi n e n eedles were obtai n e d w h ich melted

at with e ffervesce n ce d ue to the esca pe of water A n i .

troge n d etermi n atio n agreed w ith the calculated for be n zoyl

p se u d oe thy lp h e ny lse mi c arbaz id e C H5 C O N H C ( OC H5 ) , 6 ,

N N I C , H5
-
I-

Fo nd u

Whe n the calculated qua ntities of the above carbo n ate and
phe n ylhydrazi n e were mixed and heated i n a bath at
mercapta n an d water were evolved an d on cr y stallizi n g the ,

residue from dil ute alcohol fi n e n eedles were o btai n e d which

,

melted at You ng gives the melti n g poi nt of 1 5 di

1
-
,
~ ~

phe nyl 3 e thox y tri az ole as

- - We therefore prepared this
m
substa n ce by his ethod and fou n d that it also melts at
a nd that o n mixi n g the two products n o reductio n i n
melti n g po i nt took place
-
.

O ne gram of the p se ud ose mic a rbaz id e was dissolved i n alco

hol a n d 3 drops of phe nylhydrazi n e were added The mix .

ture was evaporate d o n the steam bath an d after about an -

, ,

hour crystallized from alcohol whereupo n it was fou n d tha t

, ,

the m aterial had bee n co n verted i n to the e thox y tri az ole

which melts at
Dip he ny l 5 me rcap totma z ole This me rc ap to triaz ole iso
'
- - - -
.
,

meric with the o n e obtain e d fro mthe be n z oy l d ith iocarbamate s

and phe n ylhydrazi n e was prepared as follows
,
Five grams
of fo rm y lph e ny l hy d raz ine a n d 6 of be n z o y lrhod an id e were
mixed a n d heated suffi cie ntly to melt the mixture The ma .

t e ri a l was the n allowed to remai n o n the steam bath for a -

n umber of hours It was the n treated with cold dilute sodium

.

hydroxide filtered from i n soluble material a n d the triazole

, ,

1 L o a ¢nL
 Py rr o a , 13 Di a z ole Der i va ti ve s

precipitated by dilute hydrochloric acid The precipitate on .

,

crystallizi n g fro m alcohol formed pure white hair like , ,

-

°
b u n ches of n eedles which si n ter a n d the n melt at about 2 4 8
,

to The followi n g results were obtai n ed on a n alysis

Ca l c ul a te d for
Ca N S
a o

The materia l i n soluble in alkali was crystallized from alcohol ,

whereupo n lo n g n eedles or thi n prisms were obtai n ed which

°
melted at 1 1 9 to This formed the larger part of the
above reactio n product The a n alytical results agreed with
-
.

the calculated for a co n de n satio n of equal molecules of be n

o rmy l p h e n y lh y d raz in e mi n us water
z oy l rh o d a n i d e a n d f .

C l ul t d f a c a e or
C 15 H 110 N 3 8 . Fo un d

A portio n of the material was boiled with dilute alkali ;

n early all dissolved a nd a n odor of a n ili n e or phe n ylhydrazi n e

was n oti ced O n addi n g dilute hydrochloric acid be n zoic

.
,

acid was precipitated Be n zoic acid was also O btai n ed on

.

warmi n g with dil ute hydrochloric acid These ex p erim e nts .

show that the material is easily decomposed From this it is .

improbable that the compou nd is a triazole an d therefore at , , ,

'
prese n t we are i ncli n ed to the view that it is a be n z oy l i m id o -

C H5 N N 6

fl p he n y lth iobiaz olin e

-
,

C 6 H5 C O N C S CH 2 - —

e mf Ca r he thox yphe ny lse m ica r ha z zde ,

—
N HCON H
was prepared from phe nyl
semicarbazide an d a n excess of c h lorc arbon i c ester by warm
i n g o n the water bath It was crystallized from a mixture of
-
.

alcohol a n d be n ze n e ( 2 volumes of alcohol an d 3 volu mes of

be n ze n e ) .R apid crystallizatio n produced bu n ches of very
fi n e hair like n eedles while slow gave compact bu n ches of
,
-
,

small prisms It melts at 1 7 1

. a n d a n itroge n determi n a .

tio n gave
2 70 Whe e le r .

This substa n ce is d iffic ultly soluble i n be nze n e quite sol u ,

bl e i n alcohol a n d it may be crystallized from water With ,

.

sodium hydroxide sodium ethylate a n d acetyl chloride , , ,

n g c hlorcar
°

p h e n y l u raz ol e melti n g at 2 6 3 is formed Boili

bon ic ester h as no effect on the compou n d while if it is m
.

elted ,

it decomposes Whe n warmed with phe nylhydrazi ne On th e .

,

‘
water bath it remai n ed u n altered
-
,
.

N W H VE N C NN
E F b 6 A
9 , O .
, e .
, 1 02 .

X C I II .
—
ON N G E ME NT
T HE MO L E C U L A R RE ARRA
O F U N SY MME T R I C A L A C Y L T H IOU R E A S -

A N D A C Y L P SE U DO T H IO U R E A S TO
I SO ME R I C SY MME T R I C A L
D E R IV A TIV E S .

B Y H E N Y L W HEE L E R . R .

The i n teresti n g observatio n was ma d e by H ug e rshoff that 2

by the actio n of acetic a n hy d ride o n mo nO p he ny lthio u re a an

u n stable ac e ty l ph e n y l thiou re a first results which melts at ,

O n heati n g this substa n ce above its melti n g poi nt a -

molecular rearra n geme n t takes place an d the material is ,

tra n sforme d i n to an i so meric ac e ty lp he n y lthioure a melti n g at

The latter is ide n tical with the product obtai n ed from
’
a c e ty l i so th io c y an a te a n d a n ili n e These isom ers are sharply .

d isti n guished by their properties a n d especially by their be ,

havior with mercuric oxide a n d with alkali H ug e rshoff .

fou n d that the labile acetyl derivative melti ng at is ,

readily d esulphurize d by mercuric oxide yiel d i n g acetyl ‘

p h e n y l u r e a w h ile the stable d erivative

, obtai n ed by heati n g ,

I th F b u
1 n y n um b
e f th i J U N L A
e r d ibar th i mp u n d di er o s O R A , c re e e sc r e s s co o as

c a rb e th ox y p h e n y l s e h y d ge n d t e mi ti n s re
m i c arb a z id e a nd tw o c a rb o n a n d ro e r na o a

gi e n i n upp o rt o fh i s v i e w T h e m o u n t of rb on for a m ono n d d i a b th oxy

v s . a ca a c r e

d i v ti v di ff rs b y o n l y
e r a e p e c nt w h i l t h t o f h y d ro g e n i s th m e O n th ee r e .
, e a e sa .

ot h e r h an d t h at o f n i t o g e n d i ff e rs b y
, p r c nt W t h re fo e p r p ar d th e
r e e . e , e r , e e

co mpo u n d b y A c re e 's di tion s n d ob e ve d th at th e m ate ia l m e l te d t

re c an d a s r r a

w h n m i x d w i t h u s t h e m e l t i n g p oi n t w s n ot a l t e e d
e e o r A nit ge n d te r min ti on -
a r . ro e a

g v
a e
C l ul te d fo r C l ul at d for
a c a a c e
C 3H 17 0 5 N 3 C 10H 130 3 N 3
1 .F und . o .

N
T he m p u n d i th e e fore a m on c rb th x y d ri ati v e A c re e
co o s r o a e o e v . s ta te s t h at on

c ry s t ll i i n g h i s m a t
a z i l f o m w t r t h e m e l ti n g p o i n t i s l o w e e d
e r a r a e -
r . O ur m a te ri a l
w a s f o u n d to b h v i n t h e a m e m a n n e r
e a e s .

2 Be r d c h m G s
.
3 2 36 49
. e . e .
, ,

Mi qu e l : Bull Soc C h i m
3 2 5 25 . . .
, , 2 .
2 72 Whe e le r .

it was show n by Wheeler a nd Joh n so n that dimethyl acetyl 1

i m id o dit hioc arbon ate reacts with a n ili n e givi n g symmetrical ,

a ce t y lp h e ny lp se u d o m e thy l th iou re a ( I ) The positio n of the .

acetyl group i n the resulti n g ac y lp se u doure a is show n by its

method of formatio n

<
3

011, 00 N =0

N H Q H,
C H, C O N : C

Now by careful treatme n t of p he ny lp se udome t hy l th io ure a ,

H N
"

,
with acetyl chloride a product c an
be obtai n ed iso meric with the above ace ty lph e n y lp se udo
m e t h y lt h io ure a Si n ce o n ly two structurally differe n t acety l
.

derivatives are possible this reactio n must take place as fol ,

lows : The acetyl chloride u n ites with the tertiary phe nyl
i mido group an d the n separates hy d roge n chloride givi ng nu ,

symmetrical ace ty lp he ny lp se u do me thy lthioure a ( I I ) and the ,

hydrochloride of p he n y lp se u d ome thy lt hio ure a ' 2

N O6 H5
0100 011,

6 5

N H CGHS

<
00 011
HN : C

This u n symmetrical acetyl derivative has basic proper ties ,

si n ce o n treati n g i n ether with dry hydroge n iodide it gives

, ,

an immediate precipitate of a hydroiodide or additio n product -

,

which c an be repeatedly crystallized fro m alcohol This .

melts at
1 Th i J U N L 6 4
s O R A 2 12
, ,
9 T h e Sc h
B a um an n m e th od h as b e e n u s e d w ith s u c c e ss for th e p re pa ration
o tte n -

of t h e c o r s p n d i n g u n sy mm t i c l b e n oy l ox y g e n p se u d o u r e a s b y S
re o e r a z ti gl it a n d e z

Me K e : Th i s JO U R N A L 2 6 2 30
e I n t h e p e s n t c s e ow i n g to th e u n sta b l e
, , r e a ,

n tu re o fth e p rod u c t s t h i s m e t h od c o ul d n o t b e e mpl o y e d

a , .
 Ml o e cu la r Re a r r a ng e me n t . 27 3

c 5 / s 5
/
q
C O C Hs CO CH3
1 11 . HN = C 11 1 0
\sc r1 ,
1/ \s011 ,

Fi n ally , H u g e rhoff s
labile urea o n sta n di n g a few hours ’
,

with methyl iodide gives a methyl iodide additio n product,

-

that is ide n tical in melti n g poi n t i n properties an d i n fact in -

, ,

every respect with the above hydroiodide T he additio n i n

, .

this case therefore takes place as follows

1v . 11, N -
0s -
N
00011 ,
e 5

\ 0/ \ 00 011,

1 5 011 ,

On the other ha n d the hydroge n iodide a d ditio n product ,

-

obtai n ed fro m symmetrical ac e ty lph e n y lp se udom e thy lthi ou re a

melts at about 1 a n d i t has e n tirely differe n t properties from

th ose of the product O btai n ed by methods I I I an d IV The . .

followi n g therefore represe n ts the formatio n an d structure

, ,

of this salt :

N H C , H5
V C HaCO N : C /
\ SC H
.

C HsC O N H N H C 6 H5

The fact that these two salts are differe nt shows that a
molecular rearra n geme n t does n ot ta k e place in their prepa
ratio n an d it exclu d es the possibility that the labile an d stable
,

forms are stereochemical isomers Were this latter ass u mp .

tio n true on e an d the same hydroiodide would be formed by

,

all three methods .

The ide ntity of the products forme d by addi n g hydroge n

iodide to our u n symmetrical ac e ty lph e ny lp se udo me thy lth io
u rea on the o n e ha nd an d methyl iodide to H ug e rho f fs ’
, ,

1 8— 2 7
27 4 Whe e le r .

labile derivative o n the other therefore proves that the series ,

of labile thioureas h ave the aryl an d acetyl groups attached to

the same n itroge n atom It follows from this that the mo le c .

ular rearra ngeme nt which takes place whe n these labile u reas
'

are heated is as follows

vr . H, N —
OS H

011 , 00 N 11

or v 11 .

011, 00 N 11

A ccordi n g to VI the acetyl group an d hydroge n si m ply . .

cha n ge place ; or if the ace ty lthioure as have t h e pseudo ,

form the rearra n geme nt may i nvolve a migratio n of the acetyl

,

group a n d shifti n g of the do uble bo n d as shown i n formula ,

VI I A t a n y rate u n symmetrical ac e ty lth iou re as are tra n s

.
,

forme d i nto symmetrical i somers o n heat in g .

This i n teresti n g molecular rearra n geme n t is not co n fi n ed to

the ac y lthiou re a series Dr Treat B Joh n so n an d I h aVe . . .

fou nd that the same behavior is met with i n the case of n u

symmetrical acetyl a n d be nz oy lp se udoth iou re as For ex am
“
.

ple the above u n symmetrical ac e ty l p he n y lp se ud ome thy lth io

,

urea I I simply on melti n g is tra n sformed i n to the sta ble

, .
, ,

symmetrical a c e ty lp he n y lp se ud o me thy lthioure a I It fOl ,

.

lows from this that the sulphur ato m ta k es n o part i n these

‘
rearra ngeme n ts .

The melti n g poi n ts O f the isomeric ac e ty lp he n y lp se ud o -

m e th y l th i o u re as di ffer by o n ly a n d curio usly the stable ,

H owever
°
form has the lower melti n g poi n t vi z 8 2 to -
, .
, ,

The1 h e fo e p re se n t e x am pl e o f u n y mm t i c a l m idin e s u n d e r g
se c as e s , t re r , s s e r a o

i ng a m t t ti c c h n g i n to s y mm t i c a l a m idi n
e as a a n d th e a u t h o b e l i e v e s w
e an e r e s, a r e c

d r w th e c on c lu s i n th t w h e n b u t o n e f
a m f a t u t m e i s u b t n c e i k n ow n
o a or o a o r c
”
s a s .

i t c o re s p on d to th
r s t a b l e f r m w h i h i s p od u e d b y h e ti n g th
s e l bi l e c y l o
o c r c a e a a r

a lk y l d e i v ati e T h e n o ma l l k y lth ioc y a n te u n d go a m l e c ul a re a rran g e

r v . r a a s e r o r

m e n t i nt i s th i c y n te s N C SR H R N C S t h e e f e th io y a n i a id h as th e s t uc
o o o a a . r or c c c r

t u re H N C S T h e i m i d o te s
. e t n s f m e d i n to l k y l mid e s th e a mid e s a d
e s r ar ra or a a re e

ri v ati v e s o f th e k e to f m or , O CN <—
( W i s l i c e n us an d Go d sc l hmi dt : Be r h m . d . c e .

Ge s .
, 33 , Si n c e th e i so n i t ri l e s a on v e rte d i n to ni tri l e b y
re c s s i mpl e m o l e c ul ar

g me nt h y d r g n y
r e a r ra n e , o e I n t h t ran fo
c a n i d e s h ul d ho th tr u c t u re H C N
av e e s . e s r

m tion f th e s ub sti tu te d mi di n o r a c y l p e u dothi u e a s th e s t b l e fo rm i s s h o w n

a o a es s o r a

to b e H N g a n d t h r f ore th e qu s ti o n o f th e s t u c t u re o f m n p h n y l
, e e , e r o O e

b e n e n y l n d i mi l r m i d i n e s s h o ul d b e d e id e d i n f
‘

z a s a o o f th e a b ov e i n s te a d o fth
a c av r , e

fo m H N =C ( R ) N H CoH , ( P e k m nn B e r d c h e m G e s 3 0 1 7 8
r —
Th i s
c a . . . .
, , 1

v i e w w i ll e c e i fu rth e atte ntion at a l te r ti m e

r ve r a .
2 76 Whe e le r .

N H C H3 C O C, H, N .

OH
KSO
C H,
N 0, 11, . 0011, HN
IX . X .

We also wish to determi n e whether or this molecula r not

rearra n geme n t c an be accomplished in the case of other u n sy m

metrical thiourea derivatives with radicals other tha n the ,

acyl group a nd w e ask that this work be left to us

, .

E XP E R I ME N T A L PART .

U n sy m me tr ica l A ce ty lp he ny lp se udome thy l thi our e a ,

This was prepared by —

dissolvi n g 1 5 grams of p he ny lp se ud om e thy lt hioure a i n a lit ‘

tle over 1 5 0 cc of pure dry ether a nd the n slo wly d rO p p ing in

.
,

3 5 grams of acetyl chloride i n 3 0 cc of ether

. D uri n g th e . .

operatio n the w hole was cooled i n a freezi n g mixture -

.

P he ny lp se u d o me th y lth i ou re a hydrochlori d e se parated as a

white m ass a nd the reactio n was complete a s soo n as th e
,

acetyl chloride was all added O n filteri n g the n an d e v ap O .

rati n g the e the r spon tan e ou sly beautiful colorless prism s

‘

, ,

separated These were about the size of grai n s of rice T he

. .

°
melti n g poi n t was fou n d to be 8 5 to
-
a n d a n itroge n de

termi n atio n gave

C l ul t d f a c a e or
Clo ON S
g . u
Fo n d

Whe n this material was stirred with

B e ha vi or w i th A lk a l i .
—

cold dilute alkali it immediately decomposed becomi n g oily , ,

a n d the O dor of methyl thiocya n ate was n oticed O n filt e ri n g .

a n d crystallizi n g the i nsoluble material from water plates of ,

pure aceta n ilide melti n g sharply at were obtai ned

,
.

Whe n this was mixe d with aceta n ilide the melti ng poi n t was - .

n o t cha n ged C arbo n dioxi d e whe n passed i nto the alkali n e

.
,

filtrate produced no precipitate ( abse n ce of isomer )

,
.

B e ha vior on He a ti ng Some of the material was warme d o n —

the ste a m lbath for several hours It was the n treated wit h .

alkali whe n n early all dissolved an d on passi ng car bo n d i

, , ,
m

1 B e rt r a m Be r d . . c he m . Ge s .
, 2 5 , 49
 Ml o e cul a r R e a r r a ng e me n t .

o xide i nto the alkali ne solutio n a mass of colorless n eedl e , ,

“

l ike prisms separated w hich proved to be symmetrical acetyl ,

p h e n y l p se u d o me t h y l th ioure a ,

C H, C O N H
°
m elti n g at 82 to 83

B e ha vi or w i th Hy dr og e n Iodi de
Dry hydroge n iodide passed .
—

i n to t h e ethereal solutio n gave an immediate precipitate .

T his was d if fi c u lt ly sol uble i n cold alcohol but readily i n hot ; ,

i t separated o n cooli n g i n the form of colorless four and six

, , ,

°
s ided tables a n d prisms an d it melted at 1 5 2 with stro n g ,

e ffervesce n ce formi n g a clear red liquid A n itroge n deter

, , .

m i n atio n gave

This material is therefore u nsymmetrical , , ac e t y lp he ny l

p se udo me thy l thi ou re a hydroiodi d e ,

U n sy mm e tr i ca l A ce ty lp he ny lthiou re a a nd Mthy l
e Iodi de .

fiH ug e rhoffs
°
labile acetyl derivative melti n g at 1 3 9 was pre
’

p ared accordi n g to his directio n s It was fi n ely pulverized

‘

a n d the n suspe n ded i n a large excess of methyl iodide a nd

allowed to sta n d for twe nty four hours ; the material d id n ot

.
-

d issolve but n evertheless the reactio n was complete at th e

, , ,

e n d of the above time O n crystallizi n g from alcohol it .

formed the same characteristic tables as the a bov e hy d ro ,

iodide and melted sharply at

, with effervesce n ce to a red ,

liquid Whe n mixed with the above hydroge n io d ide a dd i

.

tio n product the melti ng poi nt or temperature at which e ffe r

-
,
-

v e sc e n c e bega n was n ot altered .

Both these products moreover sho wed the same behavior , ,

with aqueous alkali In the cold the material is imme d iately .

d ecompose d aceta n ilide an d m e th y lth i oc y an ate bei n g formed

, .

There c an therefore be n o doubt that the compou n ds are

, ,

.ide ntical A n itroge n determi natio n gave

.

Wh l 1 nd J h n n Th i J U N L 6 4
e e er a o so s O R A , 2 , 12
2 78 Whe e le r .

Sy mme tr i ca l A ce tylphe ny lp se udome thy l thioure a a n d Hy drog e n

l odi de The sy in m e ti c al p se u d othioure a was prepared from
.
—

dimethyl ac e ty lim id od ithioc arbonat e I n regard to the prep .

‘
aratio n of this it was stated i n our article that o n l y on e hal f -

of the reactio n product of dimethyl ace ty l dithioc arbamat e

-
,

sodium ethylate a n d methyl iodide co n sisted of the ester

, .

This was due to the fact that the actio n was carried out at
ordi n ary temperature If co nducted ho wever at a tempera
.
, ,
°
ture n ear 0 the e n tire pro d uct almost fro m the first to th e ,

last drop boils at 1 4 8 at 2 4 m m press u re This material

,
°
. .

was mixed with a n ili n e i n a little alcohol whereupo n o n ’

, ,

sta n di n g symmetrical ac e ty lp he n y lp se u d ome thy lth io ure a

,

° °
melti n g at 8 2 to 8 3 was obtai n e d This was dissolved in .

ether and hydroge n io d i d e gave a bulky precipitate which

, ,

Was thoroughly washed with a n hydrous ether It melted at .

about with effervesce n ce O n attempti n g to crystalliz e .

from alcohol it was fou n d that the material was much more
soluble tha n the isomeric hy d roiodide an d o n boili ng the alc o
'
,
o

holic solutio n t he salt was decomposed It could be pr e c ip i .

fated from its alcoholic solutio n by ether A n itroge n d et e r .

mi n atio n gave

T h e behavior of this salt w ith alkali served to disti nguish i t

sharply from the isomer In dilute alkali it imme d iate ly dis
.

solved to a clear solutio n and o n passi ng in carbo n dioxide a

, ,

well crystallized mass of n eedle like prisms se p arated which -

,
° °
melted sharply at 8 2 to 8 3 ( symmetrical ace ty lp he ny lp se ud o
m e thy lt h iou re a )
Sy m m e tr i ca l a ce t l
y p he ny lthi ou r e a a n d methyl iodide did n ot
react u n der the same co n ditio n s as the u n symmetrical deriva

Unsy m me tri ca l B e nz oy lp he ny lp se u dome thy lthiou re a . Te n

grams of p h e ny l pse udo me th y l th i oure a were dissol ved in 1 00

1 Wh e e l e r an d Joh n son Th i s JO U R N A L ,
2 6, 19 2
2 80 L ocke .

°
z oy l h e n y l se ud o be nz melti n g at 1 1 6 to was y lthi oure a ,
p p
obtai n ed A n e n tirely di ffere nt result was brought about
.

whe n the p se ud ou re a was treated with be n zoyl chloride i n

ether an d the et h er allowed to evaporate spo n ta n eously
, .

The material thus obtai n e d o n washi ng with cold alcohol , ,

°
melted at 9 2 to 5 A n itroge n determi n atio n gave .

C l ul
a c a te d fo r
Cn l gO N g S .

Whe n this was tr e ated with alkali be n za n ilide an d be n zyl ,

thiocya n ate were obtai ned .

Whe n heated or crystallized from boili ng alcohol the m a ,

t e rial was tra n sformed i nto symmetrical be n z oy lp h e n y lp se u d o

be n z y lth io ure a which d issolved u n altered i n alkali and was
,

precipitated by carefully addi ng hydrochloric acid The .

stable urea dissolves i n an excess of hydrochloric acid The .

stateme n t previously ma d e by us that the ac y lpse ud othio

, ,

ureas appear to have n o basic properties w as fou n ded o n the

fact that their be nze n e solutio n s gave n o precipitate with h y
droge n chloride The salts w hich are formed u nder these
.

co n ditio n s are soluble i n be n ze n e .

N E W HA V EN , CO NN .
, Fe b r u a ry , 1 902 .

X C IV .
—
ON SO ME D O U B L E SUL P H A T E S O F T H A L
L IC T H ALL I U M A N D C A E SI U M .

BY JA M E Sl .o c .

mo n g the most characteristic compou nds formed by mem

A
bers of the first sub group i n the third fami ly i n the periodic -
Q

system are the alu ms A l l three of the lighter eleme n ts of the .

group alumi n iu m gallium an d i n dium yield them ; an d in

, , , ,

strict a n alogy to its prototypes therefore thalli c thallium , ,

should form salts of the same n ature The ge n eral impres .

sio n does seem to exist in fact that thallic alums have bee n , ,

prepared partly owi ng perhaps to the ge n eral te n de n cy of , ,

chemists to assume off ha n d a stro n g a n alogy betwee n all ,

-
,
‘
the members of a family a nd partly to a paper by L epsius ,
.

This i n vestigator obtai n ed a do uble sulphate of thallous a n d

1 V b e r . N atu r fo r s c h . u . A e rz te , 63 , [2 ] 1 03 C e nt rb l ,
1 89 1 , I .
, 69 4 .
 Dou ble Sulpha te s of Tha llie Thall i um a nd Ca e si um .

thallic thallium of the formula , which h e says , ,

is to be regarded as an a n hydrous alum a n d this .

expressio n has crept i nto the ha ndbooks .

There is certai n ly no more reaso n why an a nhydrous double

sulphate of thalliu m should be regard ed as an alum tha n should a
similar salt of cerium or iridiu m or any other trivale nt metal , , .

That it is so called is a very good i n sta n ce of the arbitrary

ma nn er i n which a n alogy is ofte n fou nd i n the system whe n
it happe ns to be m ore n eeded th a n self evide nt The d ouble -
.

sulphates of thallic thallium with sodiu m an d potassium are

likewise a n hydrous and so far as is k n ow n t h erefore abso , , ,

l ut e l y n o i ndicatio n of power o n the part of thall i c sulphate to

form alums has bee n observed .

I n view of the positio n of the eleme n t i n the system how ,

ever such compou nds would O f course attai n co nsiderable

, , ,

i mporta n ce a nd at my suggestio n therefore Mr D avid E

, , , . .

Brei n ig has u n dertake n to ascertai n whether u n der perh aps ,

more favorable co n d itio n s o ne could n ot be p repare d It has‘ , .

‘
bee n show n by P icci n i that caesium yiel d s alums far more
readily tha n do an y of the other u n ivale n t metals My o w n .

experie n ce also has show n that while the sulphates of some

, , ,

of the trivale n t metals e g iro n i n dium etc u n ite with , . .

, , , .
,

most of the alkali sulphates to form salts co n tai n i ng less tha n

1 2 molecules of water ofte n more readily i n fact tha n they , , ,

form the alums not o n e of the alum form i n g trival e nt metals

,
-

yields with caesium more tha n the on e hydrated salt .

2

The failure of the sulphate of a give n trivale n t metal to

u n ite with caesiu m sulphate to a compou n d of the type
1 2 H O may therefore be take n as a n almost posi
,

tive i n d icatio n that such eleme n t has n o alum formi n g power -

whatsoever This we have fou n d to b e the case with thallic

.

th alli um Its sulphate was crystallized with caesiu m sul

.

phate u nder the most varied co nditio n s from both hot a n d ,

cold solutio n s and u n der n o circ umsta n ces could the forma
,

tio n of the isometric crystals O f an alu m be O bserved Two .

differe n t hy d rate d d ouble salts were O btai n e d an d possibly a ,

third But th ey all co ntai n ed much less water tha n is called

.

g Ch m
1 Zt h
sc r . a n or7 35 5 t
. e .
, 1 , , e c .

2 Th i J U N L 6 66
s O R A , 2 , 1 .
 2 82 L ock e .

for by a co mpou nd of the alum series A lthough as far as its .

mai n purpose is co n cern ed therefore the results of our i nv e s

, ,

t ig a tio n were e n tirely n egative except i n that they establish

,

the stro n g improbability that thallic al ums are capa ble of ex

i st e nc e if it may be well to describe the salts ob tai n ed duri n g
,

our experime n ts as a slight co ntributio n to the literature of

,

t h e thallic compou n ds in ge n eral .

The thall ic sulphate used was prepared by treati n g the

freshly precipitated hydroxide with the c alculated qua ntity o f
co n ce n trated sulphuric acid an d addi n g first the desired qua n
tity of water an d the n e n ough more sulphuric acid to bri n g
,

the salt i n to clear solutio n To this the requisite amou nt of

.

a co n ce n trated solutio n of caesi u m sulphate was added O n .

mixi n g eve n a small proportio n of the latter with a fairly c on

c e ntrat e d cold sol utio n of the tha l lic sulphate a compact ,

white precipitate at o n ce separates out which is very ,

spari n gly soluble i n col d w ater but dissolves readily ,

u po n applicatio n of heat R ecrystallizatio n of a product

.
.

obtai n e d with equivale nt qua n tities of caesium sulphate

a nd thalli um sulphate yielded small well formed ,
-
,

prismatic crystals which probably belo n g to the rhombic

,

system See n u nd er the microscope they were almost

'

colorless a n d of a characteristic h e mi morp hou s habit ;

The same crystals were obtai n ed with varyi n g qua ntities of
°
caesium sulphate at all temperatures fro m 4 0 to
,
The
products were in all ca ses perfectly homoge n eous n o isometric ,

crystals at all bei n g observed A qua n tity of this salt was

.

recrystallized from sulphuric acid solutio n an d after washi n g ,

with more dilute acid and dryi n g as perfectly as possible was ,

submitted to a n alysis The various co n stitue nts were deter

.

mi n ed i n separate portio n s The thallium was weighe d as

.

iodide a nd the caesium as sulphate after removal of the thal ,

lium by mea n s of ammo n i um sulphi d e The water was esti .

m ated directly by ig n itio n i n a tube co n tai n i n g lead oxide

,
.

The results correspo n d fairly well with the formula

The some what high perce n tage of sulphuric acid fou nd is d ue

‘
to the di fficulty of removi n g the latter from the recrystallized
2 84 A lla n .

could the formatio n of an alu m be observ ed Sulphuric .

acid was the n ad d ed i n the hope that mixed chromate ,

an d sulphate alu m crystals might be obtai n e d this havi n g ,

‘
bee n show n by R e tg e rs to be a most delicate test for the iso
mo rphism o i two compou nd s o n e of which is colored The , .

Small octahe d ro n s of caesium alumi n ium alum wh ich were

deposite d however proved to be perfectly colorless and e n
, , ,

t i re ly free fro m chro mium It would seem therefore that at .

, , ,

least withi n ordi n ary limits of temperatur e chromic acid as , ,

well as thalli c thalliu m has n o te nde n cy at all to e n ter i n to ,

alums .

N W H VE N C NN F b u
E y 9 A , O e r ar , 1 02 .

T HE SU L P H A T E S O F B I SMU T H .

B Y F B A LL N . . . A .

Aacid sulphate of bismuth

n with 1 3 7 or , , , ,

1 0 H O has rece n tly bee n described by A d ie H e O btai n ed 2

, , .

it by crystallizatio n from sulphuric acid of greater c on

ce n tratio n tha n 5 2 pe r ce n t the
amou n t of water in th e salt depe n di n g on the co n ce n tratio n of
the acid a nd o n the temperature It has also bee n described .

3
by L eist .

has bee n obtai n ed by heat i n g the acid sulphate

( Schultz Se llac
‘
O n ly d ouble salts co n tai n i n g it
-
,

have bee n obtai n e d i n the wet way .

5 B i O ,
1 1 8 0
, 3
I 7 H O crystallizes
. from sulphuric acid of c o n
.
,

ce n tratio n ( 4 7 5 per ce nt ) to 2 .

( 3 1 per ce n t ) [
2 A die] .

an d crystallize fro m d i
lute sulphuric aci d ( L e ist H ein tz L ud de c k e R u g e )
6 7
, , ,
e
.

is forme d by the actio n of water o n

( H ei ntz R uge H e n sg e n ) , ,
.

Zt 1h ph y C h m 3 49 7
sc r . s . e . , , .

P 2 Ch m S
ro c 899 p. 6 e . oc .
, 1 , . 22 .

A 3 C h m ( L i bi g ) 6 9
nn . e . e , 1 0, 2 .

4 Be r . d . he m G
c . e s .
, 4, 13 .

5 R ec . tra v c hi m
. .
R a y s- B aa , 4 , 399 .

6 Po gg . A nn .
, 6 3 , 55 .

7 A nn . Ch m e .
( L i e b i ) , 14 0 , g 27 7 .

3
J .
p ra k t Ch m . e , 9 6 , 1 38
. .
 Sulpha te s of B i sm uth .

was prepare d by L eist by the repeated

washi n g of the acid sulphate with water H e nsg e n could n ot .

obtai n this salt .

is obtai n ed by heati ng a solutio n of bis

°
muth n itrate with sodium sulphate i n a closed tube at 2 00 to
°
2 50

In this research acid bismuth sulphate or the basic salt pre

pared by stirri n g the acid sulphate with 1 0 per ce n t sulphuric
acid was stirred with sulphuric acid solutio n s of di ffere n t
,

co n ce n tratio n s till equilibriu m was reached The apparatus .

used was the same as that described i n this J O UR N A L 2 5 , ,

30 7 For that part of the series n ear the poi n t at

which both basic sulphates are prese n t the reactio n was very ,

slow a n d required six weeks for completio n Where the .

liquid co n tai n e d little sulphuric acid the co mpositio n of the ,

solid p h ase w as de d uced from the cha nge in the liqui d but ,

the solids in equilibrium with the stro n ger acid solutio n s were
a n alyzed directly after bei n g rubbed betwee n porous plates
, .

G reat d iffi culty was fou n d i n freei n g the salt fro m the ad he r
i n g sulphuric acid and the a n alyses as a rule show values
, , ,

for sulphuric a n hydride which are slightly too high .

In the follo w i n g table the seco n d col um n co n tai n s the com

,

positio n of the liquid phases i n the differe n t b ottl es at e q ui lib ,

ri u m expressed i n perce n tages of sulphuric acid or with

, ,

refere n ce to a n ormal solutio n The third colum n shows the .

compositio n of the solid co nte nts

9
9
12 1 11 z
8
5 Bi, O , . 1 I SO ,

B i, O , . SO3
Tem perature
C mp t
1 d
o 3 . re n .
, 10 , 17 1 .
2 86 A ll a n .

Co mp os ition o f li quid . in so l id .

Per c e nt H 25 0 4 .

1 -
43

1 45
0

I -4 7

0 -5 5 5 -7 7
0 -3 6 5 -7 7

These results may be represe n ted i n two d iagrams i n each of ,

which the compositio n of the solid co nte n ts is represe n ted by

o n e axis an d the compositio n of the liquid by the other but
, ,

i n the seco n d which i n cludes N 08 1 3 to 2 2 a di ffere n t scale

, .
,

is used in represe n ti ng the compositio n of the liquid phase

2 88 Fraps .

2 . is no t acted on by water at
The salt
3 . described by A die was n ot

O btai n ed .

C HE M C L L I A T OR Y UN IVE R
A BO R A
TO R O N T O J a n u a ry 1 90 2
,

se OF , , .

C
u t ion f o m t h N t h C a o l ina E xpe ri m nt St t i n
o n t ri b r e or r e a o .

[C o mmu n i c ate d b y W A Wi th e r s ] . . .

T H E SO L U B I L IT Y O F B A R I U MSU L P H A T E I N FE R
R IC C H L O R I D E A LU MI NI U M C H L O R I D E , ,

A ND MA G N E SI U M C H L O R I D E .

BY G . S
. FR A P s .

In worki n g
the determi n atio n of sulphuric acid i n on

soils Mr C B Williams assista n t chemist to the North

,
. . .
,

C aroli n a D epartme n t of A griculture fou n d th at co n siderably ,

more barium sulphate was obtai n e d whe n the iro n an d alu

mi n iu m h ad bee n previously precipitated from the soil solu
‘
tio n This led to the followi n g work
. .

The latest determi n atio n s of the solubility of barium sul

phate which have bee n made are those of R Frese n ius an d .

E H i ntz i n which the solubility was determi n ed i n pure

‘
.
,

water 2 5 and 1 0 per ce n t a mmo n ium chloride 2 5 per ce n t

, .
, .

sodiu m chloride 1 0 per ce n t n itric acid an d 1 0 per ce n t hy , ,

d ro c hlori c acid alo n e an d i n the prese n ce of an excess of , ,

sulphuric acid or barium chloride .

I n regard to the e ffect of ferric salts alumi n iu m salts an d , ,

mag n esium salts upo n its solubility we have few data , .

Frese n ius states that its solubility in water is i n creased by the

”
prese n ce of mag n esium chlori d e a n d L u n ge states that it is ,

soluble i n ferric chlori d e A s the precipitatio n of barium sul .

phate sometimes tak e place i n the prese n ce of these salts the ,

k n owledge of its solubility is i mporta n t i n a n alytical work .

f Worle M th d e o o .

The metho d used was simil ar to that adopted by R Frese .

‘
n i us barium chloride bei n g used i n place of barium hydroxide
,
.

1 His re s ul ts a e n t y e t pub li s h e d
r o .

2 Z ts c h r . an l C h e m a3 5 17
. .
, , 0
‘

8 I bz d . , 19 , 43 1 .

4 L oc . ci t .
 Sol u bili ty of B a ri um Sulp ha te . 2 89

A solutio n of barium chloride was prepared cc of which ,

1 00 .

was fo u n d to give an d gram barium sulphate ,

i e
. 1 00
.
,
milligram B a SO, A solutio n of sulphuric
. .

acid was prepare d 1 00 cc of which gave an d

'

.
,

gram barium sulphate or 1 00 was equal to milligrams

, .

barium sulphate .

P relimi n ary tests were the n made upo n solutio n s of ferric

chloride alumi n ium chloride a n d mag n esiu m chloride 4 00
, ,
.

cc of the solutio n s were placed i n precipitati n g j a rs a n d sul

.

h u ri c acid an d bariu m c hloride solutio n wer e added i n the

p
proper proportio n s to m ake 1 0 milligrams barium sulphate .

The solutio n was allo w ed to sta n d twe nty four hours an d if -

,

n o precipitate appeared 1 0 milligrams more of barium sul

phate were added and so on u ntil a precipitate appeared

,
.

More exact tests were the n made based upo n the results of ,

the prelimi n ary tests In m aki n g these tests the solutio n

.
,

was allowed to sta n d forty eight hours i n stead of twe n ty four - -

,

as it was fou n d that precipitates sometimes appeared duri n g

the seco n d t we n ty four hours Much smaller q u a n tities of
-
.

barium sulphate were added each time a n d the very fai n test ,

trace O f appeara n ce of barium sulphate was watche d for It .

was fou n d that if the stirri n g ro d was rubbed agai nst th e -

sides of the vessel the barium sulphate separated nout at this

poi n t more rapidly and more rea d ily tha n elsewhere an d ,

could be easily see n In maki n g up the solutio n s of the .

various salts allowa n ce was m ade for the qua ntity of water
,

which would probably be added w ith the barium chloride and

sulphuric acid .

The solubility of n asce n t bari um sulphate i n the solutio n of

chlori d es of di ffere n t co n ce n tratio n s is give n i n the followi n g
table Neither barium chloride n or sulphuric acid was prese n t
.

i n excess in an y case .

1 9— 2 7
2 90 f r ap s .

Solu bili ty of B a ri u m Sulp ha te .

B a so, d i l d p r l i te r
s so ve e .

Mi lli g am s i n
r
Fe C l s
. A 1C 13 . Mg C lg .

58
72
1 15

123

15 0
1 60

170

Solu bil i ty Cu r ve s B a ri um Sulpha te .

C ompari n g these figures with the results of Frese n ius with

other salts we find that barium sulphate is much less soluble
,

i n 1 0 per ce n t ferric chloride or al umi nium chloride tha n in

, ,

1 0 per ce n t n itric acid or hydrochloric aci d

, It is also more .

readily soluble in a 1 0 per ce n t solutio n of ammo n ium chlo

ride tha n i n ferric chloride or alumi n ium chloride of the same ,

stre ngth though less soluble in 2 5 per ce nt ammo n iu m chlo

,
.

ride .

Sol u bil i ty i n Pre se n ce of B a ri u m Chlori de .

The solubility of bariu m sulphate i n ferric c hloride an d

2 92 Ca spa r i .

the higher members of the fatty acid series o n ly those occu r

i n n ature which co n tai n a n eve n n umber of carbo n atoms .

This ne w acid di ffers quite markedly from the isomeric u nde

c y li c aci d , obtai n ed by Kra fft H owever very lit .
,

tle is k n ow n about u mbe ll ulic acid as n o work has bee n do n e ,

o n it si n ce the publicatio n of the article referred to above .

It w as thought possible that si n ce the L i n de ra B e n z oi n be ,

lo n gs to the same family as the C alifor n ia bay tree it might ,

also co n tain u mbe llulic acid or some acid closely relate d to it ,

an d it was with th is possibility i n mi n d that the prese n t i nv e s

t i g a t i on was u n d ertake n .

While it has n ot bee n possible to i sola t e u m be ll u li c aci d or

i n d eed any acid co n tai ni ng an u n eve n n u mber of carbo n atoms ,

n evertheless some i n teresti n g results have bee n obtai n ed

, .

L i n de ra B e n z oin also k n ow n as B e nz oin odor ife r u m an d

,

L a u r us B e n z oi n an d commo n ly called Spicewood Spicebush

, , ,

or feverbush is a bush growi ng to the height of 2 0 feet fre

, ,

que n tl y much lower a n d is i n d ige n o us al l over the U nited

,

Sta tes It is fou nd chiefly i n damp regio n s alo n g water

.

courses an d is quite ge n erally used i n the southern states by

,

the cou n try people as a remedy agai n st fever an d measles .

It has a stro n g O dor of spices a nd co ntai n s an ethereal oil i n

‘
all of its parts .

The O il of its bark and twigs has the odor of wi n tergree n ,

°
boils betwee n 1 7 0 an d has the sp gr an d c on . .

tai n s 9 to 1 0 per ce n t of methyl salicylate The O i l from th e .

berries co n tai n s about 4 per ce n t of an oil with a campho

r ace o u s O d or the sp gr ,
to which boils from. .

°
1 6 0 to The leaves co n tai n about per ce nt of an O il
havi n g the odor of lave n d er an d th e sp gr . .

I n this i nvestigatio n o n ly the O il from the berries has bee n

dealt with In the n eighborhood of Baltimore where the
.
,

material was collected the berries ripe n i n the mid d le or lat ,

ter part of September a n d must be gathered very soo n afte r ,

they ripe n otherwise they will fall to th e grou n d an d be lost

,

i n the u n dergrowth .

Whe n ripe th e berries have a bright red color are oval in -

,

shape an d are about a half i n ch lo n g A half bushel of thes e .

1 R e po rt of Sc h i mm e l 81 C o .
, O c tob e r , 1 885 ,
p . 27 , an d O c tob e r , 1 890 , p .
49 .
 L i n de r a B e n z oi n . 2 93

were collecte d i n H oward C ou n ty Maryl a nd an d were , ,

s teeped in water for several days u n til the outer flesh or pulp

bega n to softe n an d decay It was the n comparatively easy

.

t o O b t ai n the i n n er ker n el e n tirely free fro m the softer pulp .

The ker n els were allowed to dry completely i n the air The .

h alf bushel of berries yielded about grams of ker n els .

The i n vestigatio n is d ivide d i n to two parts : first the ex ,

a mi n atio n of the O il from the berries an d seco n d,

a thorough ,

i n vestigatio n of laur i c aci d which was fou n d i n the oil as a

,

g lycerid e a n d of some of its derivatives

,
.

E x a mi n a tion f
o the O i l Con ta i n e d i n the B e r r i e s of the L i n de ra

B e n z oi n .

A few grams of the ker n els were thoroughly macerated ,

m ixe d with ether an d extracte d for several ho urs i n a Sox h

'

l e t extractor The ether wa s evaporated from the solutio n

.
,

the resi d u e mixed with water a n d subj ected to d istillatio n

with steam A n extremely small amou n t of O i l distilled over
.
,

which co n tai n ed all the odorous material of the O il si n ce the ,

r esidue after distillatio n was e n tirely odorless H owever the .

,

a mou n t of volatile oil was so very small that it w as i mp ossi

ble to obtai n e n ough of it from the amou n t of material at ha n d

for i n vestigatio n and so the w ork was co n fi n ed to that por
,

t io n O f the oil which is n o t volatile w ith water v apor It is .

hope d at some later d ay to complete the exami n atio n of the

volatile oil .

A qua n titative determi n atio n of the O il co n tai n ed in the

s ee d s gave the followi n g result

grams seeds yiel d ed grams O il which is equiv ,

a l e n t to per ce n t .

This result is a trifl e too high ; because it was impossible to

preve n t a small amou n t of the fi n ely divi d ed p ulp from filte r
i n g through the paper thimble of the Soxhlet extractor a n d ,

this pulp was the n weighed with the oil but the error is o n ly ,

a very small o n e .

Some d iffi culty was experie nce d i n obtai n i n g a satisfactory

m ethod for extracti ng the oil fr om the see d s .

It was first attempted to extract all the material with ether

i n a Soxhlet extractor but this metho d was u n satisfactory
,
2 94 Ca sp a r i .

for two reaso n s I n the first place some of th e pulp was al

.
,

ways prese nt i n the oil a n d it was practically impossible to

,
,

filter it off; a nd i n the seco n d place the extractors at ha n d ,

were so small that it would have e ntailed a great loss of tim e

to h ave extracted all the seeds in that way It was the n at .

tempted to moiste n the macerated p ulp with ether an d ex ,

press the r n ass i n a ha n d press which was available Thi s .

method gave the oil free from pulp but the yield was o n l y ,

about 6 0 per ce n t of what it should have bee n Fi n ally P ro .

,

fe ssor R emse n wrote to Messrs Fritzsche Brothers i n G arfield

-
.
, ,

New Jersey aski n g them whether they would extract th e

,

seeds for us They very ki n d ly co n se n ted to d o so an d I tak e

.
,

this opportu n ity of tha n ki n g them for their ki n d n ess They .

expressed the see d s a nd the n extracted the expressed mas s

,
°
with petroleum ether boili n g at 40 to A fter evaporati n g
the petrole um ether the extracted an d expressed oils wer e
,

distilled with steam for several hours but the amou n t of vola ,

tile oil w a s so small that the y d id n ot co n sider it worth t he .

trouble of isolati n g it Fro m 2 1 30 grams of the seeds were

.

O btai n e d

7 3 5 grams per ce n t of expressed oil ,

2 3 7 gram s 1 1 1 per ce n t of extracte d oil

. .

Total : 9 7 2 grams per ce nt .

The product obai ne d from Messrs Fritzsche Brothers w a s .

a soli d fat It was yello w a n d quite crystalli n e throughout

. .

its str ucture It melted at

. The fat is very soluble i n
ethyl alcohol be n ze n e gasoli n e and aceto n e but is mor e
, , , ,

d ifli c ult ly soluble i n a n hydrous methyl alcohol Its solutio n .

i n ethyl alcohol reacts n eutral towards litmus .

grams fat require for sap on ifi c at ion gra m

caustic potash H e n ce 1 g ram fat req uires
. milligram s
caustic potash for sapon ifi c a ti o n .

Vola tile a nd Sol u ble A ci ds The sap on ifi e d material O b

.
-

fai n ed i n the above determi n atio n was used for this determi n a *
tio n The alcohol was evaporate d and the potassium salt s
.

were dissolved i n water The fatty acids were set free by d i

.

lute s ulphuric acid A fter diluti n g with water the mixtur e

.
,

was distilled so that 1 1 0 c c of distillate were obtai ne d i n a .

2 96 Ca spa ri .

From the above a nalytical results it would seem that the

acid was lauric acid which is d iffi c ultly volatile with water
,

vapor an d which is i n soluble H owever through subseque n t .

,

work this co nclusio n was show n to be wro n g an d the expla n a ,

tio n of the above results will be give n further o n .

To make sure that the barium salt me n tio ned above was a
salt of lauric acid alo n e it was subj ected to fr actio n al crystal
,

l iz a tio n from water i n which it is quite i nsoluble

, .

T wo or three grams of the barium salt were boiled with two

liters of water A portio n of it dissolve d and was filtered
.
'

boili n g hot I mmediately crystals bega n to separate out an d

.
,

after about fiftee n mi n utes these were filtered o ff dried an d , ,

a n alyzed .

gram salt gave gram B asO ,

.

C l ul t d f a c a e or
B a ( C 12H 230 2 ) 2 . u
Fo n d .

Whe n the above filtrate had cooled to the t emperature of

the room more crystals had separated out These were fi l
,
.

f drie d over calcium chloride an d a n alyzed

t e re d o f , , .

gram salt gave gram Ba sO ,

.

C l ul t d f C l ul t d f C l ul t d f
a c a e or a c a e or a c a e or
B a ( C 12H 280 2 ) 2 1 B a ( C 11H 21 0 2 ) 2 B a ( C 10H 19 0 2 ) 2 .

The filtrate fro m the seco n d crop of crystals was co n ce ntra

ted co n siderably by evaporatio n a nd whe n the solutio n had ,

cooled crystals agai n separated o ut A fter dryi n g over cal .

clum chloride they were a n alyzed .

gram salt gave gram BaSO, .

C l ul t d f a c a e or
u
Fo nd

N ext the crystals which were fou n d to co ntai n

,
per
ce n t of barium were d issolve d i n boili n g water and the solu ,

tio n was allowe d to cool to the temperature of the room The .

crystals which separated out were drie d an d a nalyze d .

gram salt gave gram Ba sO ,

.

C l ul t d f a c a e or
B a ( C 12 H 23 0 3 ) 2 .
 L i nde ra B e n z oi n . 297

The filtrate from these cry stals was evaporated dow n a n d , ,

upo n cooli n g a seco n d crop of crystals separated out These

, .

were likewise dried an d a n alyzed .

gram salt gave gra m Ba so ,

.

C l ul t d f a c a e or
B 8 ( C 10H 19 0 3 ) 2 . Fo u nd .

Fi n ally ,that portio n of the origi n al barium salt which was

i nsoluble i n boili n g water was boiled with more water an d
we n t completely i n to solutio n It h a d n ot dissolved before .

b ecause there had n ot bee n e n ough water prese n t A lmost as .

soo n as boili n g ceased crystals bega n to separate out quite

rapidly an d these were fi ltered O ff while the solutio n was still
,

quite hot A fter dryi n g over calcium chloride they gave the
.

followi n g result upo n a n alysis :

gram salt gave gram B a sO , .

C l ul t d f a c a e or
B 8 ( C 12 H 23 0 2 ) 2 . u
Fo n d

2 5
0

The filtrate from these crystals whe n cooled d ow n to the ,

temperature o fthe roo m did n ot d eposit e n ough crystals for

,

an a n alysis an d whe n co n ce n trated co n siderably by evapora

,

tio n an d cooled n ot e n ough material for a n alysis separated

, ,

out.

This fractio n al crystallizatio n of th e bariu m salt o ffers very

stro n g evide n ce in favor of the fact that the material which is
volatile with steam an d i n solu ble i n water O btai n ed whe n the ,

mixed acids derived from the fat are distilled with steam c o n ,

sists n ot of lauric aci d alo n e but of lauric an d capric acids

, .

Of the first three fractio n s obtai n ed the first o ne approximates ,

very closely to b arium laurate the third o ne to barium caprate , ,

while the seco n d on e gives an a n alysis which agrees very well

with that dema n d ed by barium u nd e c y l ate but ,

the seco nd o n e whe n redissolved an d subj ecte d to fractio n al

,

crystallizatio n c an be resolve d i n to two salts whose barium

,

co n te n t agrees very well with that of barium laurate and barium

caprate Fi n ally that portio n of the origi n al barium salt
.
,

which remai n ed u n d issolved whe n it was first boile d with,

water dissolved completely whe n more water was a d ded and

, ,
2 98 Ca sp a ri .

upo n crystallizatio n yielded practically o n ly barium laurate .

This c an be explai n ed o n ly i fbariu m laurate a nd barium caprate

were origi n ally prese n t The first tim e the barium salt was
.

boiled with water a large part of th e bari um laurate an d all

,

of the barium caprate we n t i nto solutio n because bariu m ,

caprate is much more soluble i n water tha n barium laurate ,

an d the residue which dissolved completely whe n boiled agai n

with water co n sisted e n tirely of barium laurate an d did n ot ,

d issolve at first on accou nt of its great i n solubility i n water .

It no w seems clear why the lead a n d barium salts described

o n page 2 9 5 gave a n alytical results agreei n g so wel l with those

of barium laurate an d lead laurate E vide n tly i n each case

.
, ,

lead acetate an d barium acetate had bee n ad d ed i n qua n tities

in su fli c ie n t to precipitate the acids completely O n ly the lead .

a n d bar i um l au rate s crystallized out with perhaps a very little

of the caprates because the caprates are so much more solu

,

ble tha n the la u rate s i n alcohol as well as i n water

, .

The fractio n al crystallizatio n of the barium salt O f the mixe d

acids an d the subseque n t liberatio n of the free acids from their
,

separated salts does n ot O ffer a very expedie n t method for the

separatio n of the pure acids beca use su ch an e n ormous amou n t
,

of water is required to dissolve the origi n al barium salts .

H e n ce it was thought best to sapo n ify the fat liberate the ,

free acids a n d subj ect them to fractio n al distillatio n u n der

,
.

dimi n ishe d pressure In this way it is possible to separate

.

the i n d ividual acids quite thoroug hly .

A ccordi ngly about 2 5 0 gram s of the fat obtai n ed from

,

Fritzsche Brothers were sap on ifi e d with an alcoholic solutio n of

potassium hy d roxi d e ( 6 6 grams to the liter ) A fter the alco .

hol was distilled from the sap on ifi e d material there was left a ,

dark brow n pasty mass which co n siste d of the potassium

“

-
, ,

salts of the fatty acids together w ith any glycerol which

,

might have bee n prese nt i n the fat i n the form of glycerides .

This dark residue was dissolved completely i n cold water an d ,

from this solutio n the free aci d s were precipitated by mea n s

of dilute sulphuric acid They are soli d at ordi n ary tempera
.

tures an d float o n the aqueous solutio n The e ntire mass

,
.

was heated o n the water bath u n til the acids had melte d an d
-

had collected completely at the surface U po n cooli n g the .

,
300 Ca sp a r i .

third fractio ns co n tai n ed approximately equal volumes while ,

the volu me of the i ntermediate fractio n was much smaller tha n

that of the first or third These three fractio n s were colorless
.

whe n liquid an d white whe n solid with a decidedly crystal ,

li n e structure The barium salts of the acids i n the first an d

.

third fractio n s were made by bri n gi n g together a boili n g alco

holic solutio n of the acid with a co n ce n trated boili ng solutio n
of barium acetate i n about 5 0 per ce nt alcohol A fter bei n g .

washed with alcohol an d with water a n d dried in the air ,

these salts were a n alyze d for barium with the followi n g re

s u l ts
° °
Fractio n boili n g from 15 4 to 15 7 u n der 12 to 14 mm pres .

sure .

I . gra m salt gave gram B a s O, .

II . gram salt gave gram B asO, .

C l ul t d f a c a e or u
Fo n d .

B a ( 0103 19 0 2 2 )

° °
Fractio n boili n g from 166 to 1 87 u nder 12 to 14 mm .

pressure .

I . gram salt gave gra m B aSO

II . gram salt gave gram B a SO
C l ul t d f a c a e or u
Fo nd .

B a ( C 12H 230 2 ) 2 .

From these results the co n clusio n may be draw n th at the

° °
fractio n boili n g from 1 5 4 to 1 5 7 co n sisted mai nly of capric
aci d with perhaps a very little lauric acid an d that the frac ,
° °
tio n boili n g from 1 6 6 to 1 8 7 co n siste d of quite pure lauric
acid .

In order to obtai n a purer capric aci d the fractio n boili n g ,

from 1 5 4 to 1 5 7 was re d istilled together with the i nt e rme

° °
,

diate fractio n me n tio n ed above which u n der the same pres , ,

°
sure boiled fro m 1 5 7 to
,
From this distillatio n three
° °
fractio n s were O btai n e d the first boili n g from 1 5 6 to 1 5 7 u n
,
° °
der 1 5 mm pressure the seco n d boili ng from 1 5 0 to 1 5 4 u n
.
,

°
der 1 0 to 1 1 mm pressure and the third from 1 5 7 to 1 6 9
.
,
°

u n der 1 3 mm pressure The first fractio n had by far the

. .

largest volume While the seco n d a n d third fractio n s each had

,
 L i n de ra B e nz oi n .

a volume which was much smaller tha n that of the fractio n

° °
boili n g from 1 5 7 to 1 6 6 u n der 1 0 to 1 2 m m pressure These . .

facts show that this last me n tio n ed fractio n was composed of a

-

l ower an d a higher boili n g portio n The a n alyses below show .

that it co n siste d of a mixture of capric an d lauric acids .

The barium salts of the thre e n e w fractio n s were made ex

a c tl y as those described above a n d upo n a n al ysis gave the ,

followi n g results for barium

° °
Fractio n boili n g from 1 5 6 to 1 5 7 u nder 1 5 mm pressure . .

I. gram salt gave gram Ba sO ,

.

II . gram salt gave gram Ba SO ,

.

C l ul t d f
a c a e F u d
or o n .

B a ( C i oH 19 0 2 ) z I .

2 8 64 1

Frac tion boil in g

° °
from 150 to 15 4 u n der 10 to 11 mm pres .

sure .

I . gram salt gave gra m B asO

II . gram salt gave gram B a SO, .

C l ul t d f
a c a e or u
Fo n d .

B a C 1011 19 0 2 ) 2 B a ( C 12H 23 0 2 ) 2 ~

° °
Fractio n boili n g fro m 1 5 7 to 169 u n der 1 3 mm pressure . .

I . gram salt gave gram Ba SO, .

II . gram salt gave gram B a SO

C l ul t d f
a c a e or Fo und .

B a ( C i oH 19 0 2 ) 2 B a ( C 12H 230 2 ) 2 .

Thus the first fractio n co n sists of practically pure capric

,

acid the seco n d fractio n of capric acid with a little lauric

,

acid a nd the third fractio n of lauric acid with a very much

,

smaller amou n t of capric acid From this it appears evide nt .

that n o acid of the formula was prese n t a co n clusio n ,

also arrived at from the evide n ce prese n ted by the fractio n al

crystallizatio n of the barium salts of the mixe d acids whe n ,

the barium salt co n tai n i n g per ce n t of barium the per ,

ce ntage of bariu m i n the bariu m salt of bei n g

was resolved i nto barium caprate an d barium laurate .

°
A small portio n of the residue boil i n g above 1 8 5 u n der 1 1
to 1 5 mm pressure was dissolved i n chloroform and treated
.
30 2 Casp a r i .

with bromi n e water The color of the bromi ne disappeared .

i m m ediately showi n g the prese n ce of some u n saturated acid

, .

T o test whether this acid was formed duri n g the distillatio n by

decompositio n from lauric and capric acids some of the origi ,

n al fat was treated i n solutio n i n chloroform with bromi n e

water and agai n the color disappeared immediately sho wi n g

, ,

that the u nsaturated compou n d was prese nt as such i n the

origi n a l fat The high boili n g residue was distilled u nder 1 0
.
-

°
mm pressure
. U p to 2 1 8 very little distillate was obtai n ed
.
,

a nd this was doubtles s i mpure l a u ric acid as it solidified al ,

° °
most immediately From 2 1 8 to 2 2 5 a very appreciabl e .

°
amou nt of a clear liquid distilled over a n d above 2 2 5 the ,

m ass carbo n ized The distillate which came over bet w ee n

.

° °
2 1 8 an d 2 2 5 melted at the melti n g poi nt of oleic acid be -

i n g give n as A hot alcoholic solutio n of the acid which ,

d id n ot re dd e n bl u e litmus paper a n other characteristic of ,

oleic acid was treated with ammo n ium hy d roxide an d barium

,

chloride and filtered hot U po n cooli n g a volumi n ous white

, .
,

crystalli n e precipitate separated out which upo n a n alysis , , ,

gave the followi ng results

I . gram salt gave gram B a sO, .

II . gram salt gave gram B aSO ,

.

C l ul t d f F u nd a c a e or o .

B a ( C i sH 330 2 ) 2

These results poi n t to the co n cl usio n that the acid boili ng

° °
from 2 1 8 to 2 2 5 u n der 1 0 m m pressure is oleic acid Kra fft . .

‘ °
a n d Nor d li n ger give 2 2 3 as the boili n g poi nt of oleic acid -

u n der 1 0 m m pressure A nother piece of evide n ce also

. .

showed that oleic acid is co n tai n ed in the fat It is well .

k now n that lead oleate is sol uble i n ether w hile the lead salts ,

of the saturated acids are n ot A ccord i n gly the potassiu m .

,

salts of the mixed acids fro m the fat were treated i n aqueous
solutio n with a solutio n of lead acetate A copious white .
, ,

creamy precipitate was i mmediately throw n down and was ,

'
filtered off an d dried as well as possible i n the air It was .

the n extracted with ether several times an d the solutio n i n ,

ether was evaporated do wn co nsiderably whe n a yellowish

1 Be r. d . c he m . Ge s 2 2 , 8 19 .
 3 04 Ca sp a r i .

pich uri m bea n s fro m South A merica H is acid m elted at .

A few years later G orgey duri ng an exte n siv e i nvesti

1
,

g a t i o n of cocoa n ut oil fou n d that it co ntai n ed lauric acid , .

C apric an d caprylic aci d s w ere also prese n t an d he separated ,

the three acids by fractio n al crystallizatio n of their barium

salts H e described lauric acid very much as Marsson and
.

Stha me r had d o n e and said it melted at 4 2 to H ei ntz

° ’
,

obtai n ed lauric acid which melted at fro m whale fat , .

O ude m an s fou n d lauric acid as a co nstitue n t of

3
In 1 86 7 ,

Fa ng k all ak fat obtai n ed from the Cy li codap hn e se bife r a O fJava , .

O u d e man s f i n 1 8 6 3 prepared an d described several of the ,

salts of lauric aci d H e did n ot state th e source or the melt .

i n g poi nt of his acid a nd si n ce m a n y of his results di ffer c o n

-
,

s i d e ra bly from those obtai n ed with the lauric a ic id from the

see d s of L i n de r a B e n z oi n it is questio n able whether Oude ,

ma n s was deali n g with perfect ly pure lauric aci d A s most .

of the work on lauric acid was do n e more tha n forty years

ago it seemed desirable that so me of the work shoul d be re
,

e a t e d with the aid of moder n improveme n ts i n ch emical

p
methods .

The method O f obtai n i n g lauri c acid from the seeds of L i n

de ra B e n z oi n has already bee n described The acid melts at .

4 2 an d boils at 1 6 6 u n der 1 0 to 1 1 mm pressure

°
It is very °
. .

soluble in alcohol from which it c an be crystallized i n warty ,

crystals which have a sati n luster It is practically i n so lu

,
.

ble in water In alcoholic solutio n it tur ns blue litmus paper

.

red . U po n a n alysis the aci d gave the followi n g results

I . gram acid gave gram C O an d ,

gram H O ,
.

II . gram acid gave gram C O and ,

gram H O ,
.

C l ul t d f F u d a c a e or o n .

(212 11 240 2 I .

C
H
In order to be sure that this acid is ide ntical with that 0b
1 A C h m ( L i bi g ) 6 6 9
nn , e . e , , 2 0
.

2 I bid .
, 92 , 2 94 .

3 Z tsc h r Ch m
. e .
, 1 86 7 , p . 256 .

4
J .
p ra k t Ch m. e .
, 89 , 2 06 .
 L a u ri c A cid .
30 5

‘
t ai n e d by Krafft from laurel oil from whose results those ,

here give n d i ffer some what a h alf kilogram of laurel O il was ,

purchased from Do d ge a n d Olcott i n New Y ork which , ,

yielded about 1 0 per ce n t of lauric acid by sap on ifi c ation a nd

distillatio n u n der dimi nished pressure This acid melted at .

° °
4 2 an d boiled at 1 6 6 u nder 1 1 mm pressure an d was i n all .
,

respects ide ntical with that O btai n ed from the seeds of the
L i n de ra B e nz oin Kra fft said that his aci d m elted at .
5 .

Of the sources of lauric acid thu s far discovered the seeds ,

of the L i nde r a B e n z oi n yield it most abu n da ntly an d with

com paratively little difficulty .

2
The Chlor i de of L a u ri c A cid The chloride ,
—

of the acid was made by treati n g the melte d acid with a little
more th a n the calculated amou n t of phosphorus trichloride
an d heati n g the mixture o n the water bath for fiftee n or -

twe n ty mi n utes u ntil the actio n was complete In this re ac

, ,
.

tio n o n ly the chloride O f the aci d an d phosphorous acid are

formed The latter si n ks to the bottom of the dish as a rather
.

viscous liquid SO that the c hlori d e c an be po u red from it very

,

easily In order to purify this crude chloride it was subj ected

. ,

to d istillatio n u nder dimi n ished pressure a n d after o n e d istil ,

latio n it yielde d the followi n g a n a l ytical resu lts :

I . gram chlorid e gave gram A g C l .

II . gram chloride gave gram A g C l .

u
Fo n d .

The chloride is decomposed Slowly by the moisture in the

air an d must he nce be well protected fro m the air It is also
, .

?’
decomposed very quickly by alcohol A ccordi n g to Kra fft it .

boils at 5 u n der 1 5 mm pressure an d melts at .

°
That which gave the above results boiled at 1 4 5 u nd er 1 8
mm pressure an d rem ai n ed liquid whe n cooled dow n to
.
,

The A m i de of L a u r ic A ci d The amide of ,

—

lauric acid was made accordi ng to the method for the ge n eral
‘
preparatio n of acid amides recomme n ded by A scha n It was .

1 Be r d . . c he m . Ge s .
, 12 , 1 66 4 .

2 l bi d .
, 3 1, 2 344 .

3 I bi d . , 17 , 1 37 8 .

4 I bid .
, 3 1, 2 344 .
306 Ca spa r i .

his method that was used i n maki ng the acid chloride The .

chloride was added drop by drop to a n excess of a well , ,

cooled co n ce ntrated solutio n of ammo nia which was c on

, ,

st an tl y stirred The amide was precipitated out immediately

.
,

as it is i nsoluble i n water It was crystallized several times .

from 5 0 per ce n t alcohol u ntil its melti n g poi n t remai n ed c o n -

sta nt after three crystallizatio n s The amide c rystallizes i n .

very fi n e feathery white n eedles which whe n dry have a

, , , , ,

very fluffy appeara n ce with a sati n luster It melts sharply .

°
betwee n 9 8 and U po n a n alysis it gave the followi n g t e
s ults :

gram amide gave gram C O, an d gram

H, O .

Fo und

gram amide gave gram N .

C l ul a c a te d fo r
C 11H 23 C O N H 2
. . Fo und .

The n itroge n was determi n ed as ammo n ia by the Kj eldahl

method .

The amide of lauric aci d has bee n made o n ly o n ce before ,

an d the n by Kra fft H e does n ot give any a n alyses of his

.
‘

product n or does he say how he purified it H is amide melte d .

at
The A n il ide ofL a u ri c A ci d This was ,
—

made by addi n g the chloride drop by d rop to an emulsio n i n , ,

water of twice the calculate d amou n t of a n ili n e require d .

The pro d uct of the reactio n was crystallize d several times from
5 0 per ce n t alcohol a n d fi n ally it melted co n sta ntly before a nd
,

after two crystallizatio n s at The a n ili d e crystallizes quite

well i n lo n g feathery fluffy white n ee d les resembli ng fi n ely
, , , ,

shredded asbestos It was a n alyze d for n itroge n by the Kje l

.

d ahl method with the followi n g res u lt

'

gram an il id e g av e gram N .

C l ul t d f a c a e or
u
Fo n d

5 . IO

1 Be r . d . c h m
e . Ge s .
, 15 , 17 29.
30 8 Ca sp a r i .

is as i n soluble i n water as barium laurate an d n early as i n sol

uble in alcohol It decomposes without melti n g at abou t
.
, ,

2 40 an d co n tai n s 1 molecule of water of crystallizatio n

°
.

I .gram salt gave gram H O ,

.

II .gram salt gave gram H O ,

.

C l ul t d f
a c a e or Fo n d u
SY( C H 0 )
.

12 H
23 2 2 20 .

36 7

I . gra m a n hydrous salt gave gram SrSO ,

11 . gram a n hydrous salt gave gram SrSO

C l ul t d f
a c a e or Fo n d u .

Sf (012 H 23 0 2 ) 2 o 1

Ca lciu m L a u ra te , laurate H, O .
—
C alcium
was made like the bariu m an d stro n tium salts It i s .

much more soluble i n alcohol tha n either of these salts a nd

crystallizes i n very Short delicate white n ee d les which c an, , ,

n ot be disti n ctly see n without the aid of a pocket le n s T he .

crystals co nta i n on e molecule of waterof crystallizatio n an d mel t

°
at 1 8 2 to
I . gram S alt gave gram H O ,
.

II . gram salt gave gram H 0 .

C l ul t d f a c a e or
C 3 ( C 12 H 23 0 2 ) 2 H eo I

2 39 4 3 -49

This salt is e ffl ore sce nt an d this fact accou n ts for the some
,

what l o w results obtai n ed i n the deter m i n atio n of water o f

crystallizatio n .

1 gram a n hydrous salt gave

. gram C aSO ,
.

II gram a n hy d rous salt gave

. gram C aSO 4

C l ul t d f F und
a c a e or o .

C 8 ( C 12H 230 2 ) 2 . I .

Ca 9 12 9 . 2 1

A ci d Mg a n e si u m L Thi s
a u ra te ,
—

salt was obtai n ed by treati ng a hot alcoholic solutio n of lauri c

acid with a hot n eutral alcoholic solutio n of mag n esium ace
tate It was expecte d that the normal mag n esium laurat e
.

woul d be formed but i n two i n sta n ces the acid salt was ob
,

tain e d a n d it was impossible to obtai n the n ormal salt

, Thi s .
 L a uri e A cid .

c ase of mag n esium formi n g an acid salt seems to be an isola

ted on e The salt is the most soluble salt of lauric acid with
.
,

t he exceptio n of potassium an d sodium l aurate s It crystal .

liz es most readily from 5 0 per ce n t alcohol in very fi n e white ,

°
n eedles which melt at 7 4 to
, A n alyses for mag n esium
g ave the followi n g results
‘

I . gram salt gave gram Mg SO, .

II . gram salt gave gram Mg SO ,

.

C l ul
a c a te d fo r u
F o nd
Mg
.

3 -9 1

. O ude ma n s described the n ormal mag n esiu m la urate

‘
,

a n d said it co n tai n ed 3 molecules of water of

c rystallizatio n Stra n ge to say this salt melted at

. the ,

m elti n g poi n t of the acid salt described above

-
O u d e ma n s .

d id n ot state how he prepared his mag n esium laurate

«
.

Z i nc L a u r a te Zi n c laurate was ma d e as the

,
—

p revious salts were It is moderately soluble i n alcohol

. a d
n p
,

c ry stallizes i n delicate white n eedles arra nge d in the form of ,

r osettes It also has a pearly or sati n luster like that of the

.

b ari um salt .

I gra m salt gave gra m Zn O

’

. .

II . gram salt gave gram Zn O .

u
Fo n d .

This salt was dried i n the air and co n tai n ed n o water of crys
O ud e man s describes a zi n c laurate to which he
2
t alliz at ion .

gave the formula Zn This melted at

Th e sal t d escribed above melts at
Coppe r L a ura te C opper laurate was made
,
—

just as the previously described salts were It s eparates as a .

light bluish gree n microscopically crystalli n e powder

-
,
It is .

v ery d ifli c u ltl y soluble i n alcohol an d i n soluble i n water .

Whe n heated it gradually tur ns d arker a n d fi n ally assumes

, ,

a dark gree n color .

1 L oc . ci t .

3 L oc . ci t .
310 Ca spa ri .

I . gram salt gave gram CuO .

II . gram salt gave gram C uO .

C l ul t d f
a c a e or Fo nd u .

C 11 ( C 12H 280 2 ) 2

O u d e m an s
‘
described a copper laurate ,

which he said melted at while the above described sal t -

does n ot melt whe n heated to

L e a d L a u r a te L ead laurate was made lik e
,
—

the other salts It i s i nsoluble i n water but may be crystal

.
,

l iz e d from alcohol It crystallizes i n delicate white n eedles

.
,

which have a pearly luster They melt at Oude . -

ma n s described his lead laurate as bei ng amorphous wh il e

2
,

the salt h ere describe d forms d efi nite crystals with compara

t i ve l y little difficulty .

I. gram salt gave gram P bSO , .

II . gram salt gave gram P hsO ,

.

C l ul t d f a cF u nd a e or o .

P b ( C 12 H 230 2 ) 2 . I .

M a ng a n e se
r L a u a te laurat
, e —
Ma n ga nese
was prepared as the other salts were It is i n solubl e i n water .
,

but is soluble i n alcohol I t separates out from its solutio n .

as a very pale pi n k microscopically crystalli n e powder , .

The crystal form could n ot be determi n e d It melts at .

O ud e m an s de
3
a n d co n tai n s n o water of crystallizatio n .

scribed a ma n ga n ese laurate melti n g at a n d co ntai n i n g or

molecules of water o f crystallizatio n .

I . gram salt gave gram Mn SO ,

.

II . gram salt gave gram Mu sO ,

.

C l ul t d f F und
a c a e or o
MD ( C 12H 230 2 ) 2
.

C oba l t L a u ra te , laurate w as H, O .
—
C obalt
made as the other salts were an d is quite soluble i n alcohol ,

b ut i n s oluble i n water It forms delicate pale red n ee d les .

,
-
,

w hich melt at a nd the n assume a dark violet color T he -

.

1 L oe . a t .

1 L oc . ci t .

3 L oc . ci t .
312 Repor t .

d i me thy l p y ro n e These salts are compared with those of di

.

me th y lp y rid on e , a n d the co n clusio n draw n that the oxyge n

atom i n the pyro n e must play the same part as the n itroge n
atom i n the pyrido n e This assumes the quadrivale nce of .

oxyge n an d also that certai n of its compou n ds have a basic

,

character due to its prese n ce Such compou nds are a n alo

,
.

gous to the ammo n iu m phospho n ium sulpho n ium and iodo , , ,

n iu m bases a nd may be calle d oxo n ium bases

, They are de .

ri v a t iv e s of the hypothetical oxo n ium hy d roxide O H, O H , .

In favor of this hypothesis the authors me n tio n the fact that

ethers freque n tly form so called doubl e compou nds with the -

haloge n acids such as dimethyl ether hy d rochloride diethyl

, ,

ether hydriodide an d they also put in this category ethyl per

,

oxide .

‘
A few mo nths later a paper by Kehrma nn on the c o n s tit u ,

tio n of the oxazi n e d yestu ffs was rea d before the G erma n
C hemical Society I n it the author makes use of the s u g g e s
.

tio n of C ollie a n d Tickle to accou nt for the structure of the

d i am i nO p h e nox az in e and d ia mi n op he nt hiaz i n e salts The .

structure of these compou n ds would therefore be re prese n ted , ,

by the followi n g

Cl
Di a m i n o p h e n az o x o n i u m D ia mi n o p h e n az thio n i u m
l
c h o r id e . c h l or i d e .

It is of co urse co n ceivable that it is the n itroge n atom

, , ,

rather tha n the oxyge n a n d the sulphur atom which plays ,

the part of the base but a compariso n of these co mpou n ds

.
,

with d i am id op he n y lp he naz ine as to color an d absorptio n spec

tra seems to re n der this improbable Several a n alogous az ox o .

”
n ium an d azthio n ium salts have bee n described by Kehrma nn
duri n g the prese n t year .
‘

The co ntributio n to this subj ect which has attracted the

most wide sprea d atte n tio n of chemists is the notable paper by
-

3
Baeyer an d V illig e r o n the basic properties of oxyge n , ,

which appeared i n the B e ri chte for September 2 8 th A fter t e .

1 Be r d . . c he m . Ge s .
, 32 , 2 60 1

2 l bid 16 2 3,
.
, 34, 4 17 0
3 I bid 2 67 9
.
, 34,
viewi n g various classes of compou n ds of oxyge n which have
bee n n oted i n the p ast as formi n g compou n ds with aci d s ,

which seem to be O f the n ature of salts an d referri n g to the ,

work of C ollie and Tickle as bei n g in every particular veri

,

fi e d by them they a nn o u n ce as a ge n eral propositio n that the

,

simple oxyge n atom i n every form in which it appears

,

throughout orga n ic chemistry is capable of formi n g salts ;

,

that no t o n ly i n specially favorable circumsta nces as C ollie ,

an d Tickle thought is it possible to O btai n well characte rized

,
-

salts but with a few exceptio n s i n every case provi d ed o n ly

,

that the proper acids an d the appropriate co n ditio n s are se

l e c te d
. Th e acids used i n the preparatio n of the salts of
B aeyer an d V illi g e r were ge n erally hydroferrocya nic hy d ro ,

ferricya n ic a n d hydrocobalticya n ic
, In a few i n sta n ces
.

phosphotu ng stic and c hlorpl ati n ic acids were use d While . .

a few oxyge n compou nds gave well characterized salts with -

the simpler acids i n almost all cases far better a n d surer re

,
'

s ul ts were obtai n ed with the complex acids The cya n ic a cid .

reage n ts were prepared by precipitati n g the potassium salts

with co n ce n trated hydrochloric aci d a n d filteri n g off the p ot as
siu m chloride Salts were forme d with various members o f
.

the followi n g classes O f oxyge n compou nds ethers ethyle n e ,

oxide an d ci n eol primary seco nd ary an d tertiary alcohols

, , , , ,

esters aldehydes keto n es of all classes N o compou nds with

, , .

acids were obtai n ed though o n e of ace t ic acid is k n ow n

, .

P erhaps the best results were O btai n ed with ci neol a n d with

the keto n es .

That these salts are not compou nds of bivale n t oxyge n i n

the ord i n ary se n se of the vale n ce theory was show n by a care
ful study of the hy d rochloride of d i be nz al ac e to n e which is n ot ,

a c hlorh y d rin e of the formula

C , H, C H . C H C , H5 ,
.

but has rather the formula

011 00 011

In favor of the theory that the oxyge n bases are to be ex

plai ned by the quadrivale nce of oxyge n B aeyer cites the fact ,

that the same i nflue n ces which i n crease or d imi n ish the
basicity of n itroge n a ffect similarly the basicity of oxyge n ,

a n d the same i s true to a limited exte n t of sulphur This is .

show n by the followi n g table

3 14 R p or t
e .

N H8 O H, SH 2

base n eutral aci d

S( C H 5 ) . 2

stro n g base weak base n eutral

very stro n g base hypothetical base base

While the e n tra n ce of a positi ve group like alkyl re n ders
the oxyge n of the neutral water basic this is n ot the case ,

with n egative groups like phe n yl P he n ol be nzophe n o n e .

, ,

a n d similar compou n ds represe n t a class of O xyge n compou nds

which form n o salts : This is i n complete accord with the

character of n itroge n compou n d s for i n triphe n ylami n e the ,

basic quality of n itroge n has e ntirely d isappeared The basic .

character of oxyge n is most n ot i ceab l e i n those compou n ds i n

which there is a double li n kage betwee n oxyge n an d carbo n .

This raises the questio n which B aeyer does no t attempt to ,

a nswer as to whether these compou nds are n ot to be ac

,

cou n ted for by the theory of residual a ffi n ity usi n g ideas ,

‘
wh ich have bee n suggested by A rmstro ng Nef Thiele and , , ,

others .

I n the n umber of the B e ri chte followi n g that i n which .

2
B aeyer a n d Villig e r s article appeared Wer ner takes up the
’
,

work of K ehrma nn but d evelops it by avoidi n g the prese n ce

,

of n itroge n atoms in the molecule The simplest compou n ds .

prepared were the perbromi d e a nd the ferric chlorid e double

salt of xa n thydrol forme d by the reductio n of x a n tho n e
, .

X a nthy d rol he co nsiders to be a p se ud ox anthox on iu m base ,

0 11

whi le its salts are derived from the true x anthox o n i u m base ,

1 P roc C. h e m Soc
. .
, 1 901 , 2 46 .
1 Be r d
. . c he m Ge s
. .
, 3 4 , 3300
3 6
1 R epor t .

O Br
-

,
Zn B r, .

C O —
Br
\
O é
Os 4

D i x an t h y l e n e . Zin c b ro m ide d ouble sal t o fd i

x a n t h ox o n i u m bro m i d e .

Wern er also prep ared similar derivatives co ntai n i n g sul

phur i n the place of oxyge n a n d gives to these two classes
c arbox o n i u m c a rbo thio n i u m
” ”
the n ames of a nd salts .

Wern er looks upo n the pyro n e salts as bei n g of a n alogou s

‘
co n stitutio n differi ng here somewhat from Baeyer and C ollie
,
.

A ccordi n g to Wer n er these are p araox y p y rox o ni u m salts ,

OH

X
H e also sho w s that pyro n e itself is capable formi n g salts of .

In the same n umber of the B e ri chte R ose n heim and Stell ,

2
ma n n d escr i be a n umber of double compou nds of a n timo n y
pe ntachlori d e i n clu d i n g several with di ffere n t classes of oxy
,

g e n compou n ds Such are SbC l C H , C H O . .

,

an d 2SbC l, 3 C H, C O N H In the light of the oxyge n bases

, .
z
.

these compou n ds possess a peculiar i n terest especially i n vie w ,

of the fact that R ose n heim fou n d that a n timo n y chloride also
forms double compou n d s with the orga n ic acids which is n ot ,

the case with the complex i norga n ic ac ids with which B aeyer
an d V ill ig e r worked .

”
In the n ext n umber of the B e ri chte B aeyer a nd Vill ig e r ,

1 Be r . d . c he m . Ge s .
, 3 4 , 36 12
2 I bzd
‘

.
, 3 4 , 337 7 ( 1 901 ) Cf l . a so R u st I bi d .
, 30, 2 82 8
 R epor t .

take exceptio n to the formula which Wer n er proposed for the

pyro ne salts on the grou nd that there is no evide n ce of the
,

prese n ce of a hydroxyl group H e also expresses doubt as to .

whether the oxo n ium bases really correspo n d to the ammo

n i um compou n ds or are to be rather co n sidered as molecular
,

compou n ds H e calls atte ntio n to the resembla n ce which the

.

salt formi n g character of the oxyge n compou n d s i n ge n eral

-

bears to that of the n itriles wh i ch are ordi n arily co n si d ered ,

to have n o basic properties This is however not strictly .

.
, ,

the case for the n itriles n ot o n ly form compou n ds with t in

,

tetrachloride a nd Similar chlorides but B aeyer shows that ,

with the cya n ic acids most of the n itriles tested form well d e - é

fi n ed compou n ds which closely resemble those formed u n d er

Similar circumsta n c e s with the oxyge n compou n ds .

‘
In a late n umber of the B e richte K ehrma n n an d We ntzel ,

apply the i d eas i n the previous papers of Kehrma n n to the

co n stitutio n of G omberg s triphe n ylmethyl co n sideri n g it as ’
,

d ip h e n y lph e n y l e n e me th a n e i n which the para carbo n atom of ,

the phe n yle n e group is bivale nt and like oxyge n u n der simi , ,

lar circumsta n ces plays the part of a base Whe n this carbo n
, .

atom u n ites with the eleme nts of hydrochloric acid it becomes ,

quadrivale n t and there is formed the isomeric yellow tri

,

p he n y l c h lorm e th an e If this diag n osis is correct we have

.
,

here an i n sta n ce of a carbo n ium base ‘ ’

.

—
C Cl

H Cl
C o l orless t r i p h e ny l c h l or m e t h an e . Yell ow t ri p h e n y l c hl o r
m et h an e .

1 Be r. d . c he m . Ge s .
, 3 4 , 3 815
318 Rep or t .

G o mberg ’
s triph enyl m et hyl , a c ar
bo n i u m base ”
.

In the same n umber of the B e ri chte H ewitt utilizes the ,

‘

oxo n i um theory as a prop to his theory of the cause of fl uo

re sc e n c e .

Still more rece n tly Walker has made an exami natio n of ,

2

dimethyl an d te tram e th y l py ron e by physico chemical meth -

od s . Measuri n g their catalyzi n g e ffect upo n methyl acetate ,

he fi n ds that their basicity is practically the same as that of

urea d i me th y lp y ro ne bei n g a little stro nger base an d tetra
,

me thy lp y ro n e a little weaker H e also fi n ds that the hydro .

chlorides of these compou nd s are hydrolyze d i n aqueous solu

tio n to about the same exte nt as the hydrochloride of urea .

H e further Shows however that co n trary to the stateme n t of , , ,

ma n y text books ethyle n e oxide is by no mea ns a stro n g base

-
, ,

but that its property of precipitati n g iro n alumi n ium an d , ,

mag n esium hydroxi d es from solutio n s of their chlorides is due

to the te n den cy of these salts to hydrolysis in aqueous sol u
tio n .

Of the latest co n tributio n s to the subj ect the most impor ,

2
ta n t i s th at of Walde n who after a historical revie w of the , ,

earlier work gives the results of a series of physico chemical

,
-

experime nts upo n d i m e th y lp y rone ( 1 ) Violuric acid d i s .

solved i n a soluti o n O f d i m e th y lp y ron e shows no immediate

i n crease of colored io ns showi n g that i n this case di ,

m e thy lpy ro n e has no d ecid e d te n de n cy to form a salt or ,

that its salt with V ioluric acid is completely hydrolyzed .

( 2 ) From the i nflue n ce of d i me t hy l p y ro n e upo n the birotatio n

of grape sugar it appears that if basic at all it is a decidedly
-
, , ,

1 Be r
’
. d . c he m . Ge s .
, 3 4 , 38 1 9
2 I bzd 3 4 , 4 1 15
.
,

3 W et . 3 4 . 4 1 85
32 0 Re vie ws .

were o n ly accepted after a prolo n ged co n test The idea of .

the qua d rivale n ce of O xyge n is logical is thoroughly i n har ,

mo n y with the properties of the oxyge n group an d yet it will ,

be ge n erally accepted by chemists o n ly whe n it is recog n ized

as bei n g the o n ly possible way of accou n ti ng for m a n y d i ffe r
e n t compou n ds .

We cli n g to the theory of vale n ce because we reco g n ize that

there is tr uth i n it but at the same time we recog nize its i n
,

suf fi c ie n c y by m ak in g o n ly a limited use of it It accou n ts .

satisfactorily for the structure of most of our simpler com

pou n ds it has bee n a wo nd erful an d tolerably safe guide i n
,

the do mai n of o rg an ic c h e m istry yet eve n i n these two cases

’

it is applicable with strict n ess o n ly to gases where we k n o w

the weight of the molecule In liqui d s we ca nn ot be sure of .

it i n solutio n we k n ow n ot what becomes of it whe n the io n s

are d issociate d i n soli d s we c a n use it o n ly by a n alogy It .

is i n solids too that the co n ceptio n of vale n ce most c o n sp ic u

, ,

o u s ly breaks do w n Betwee n ammo n iu m salts d o uble sal ts

.
, ,

such stable compou n ds as the plati n um tetrammi n e bases a n d ,

the e fli ore sce nt d ecahy d rate of sodium carbo n ate we c an ,

bridge every step with i n termediate compou n d s In a limi .

te d field vale n ce represe n ts a qua n titative truth i n a larger

field it is lik e a scaffold which more or less closely keeps to ,

the outli n e of the structure and is correspo n di ngly useful d i d ac

,

tically i n gai n i n g a co n ce ptio n of the structure itself We are .

yet lacki n g i n k n owledge of the chemical afi n i ty of the atom

from a qua n titative sta ndpoi n t .

The importa n ce of the oxyge n bases does n ot lie i n the

questio n of the p o ssfl le quadrivale nce of the oxyge n atom ,

but rather i n that oxyge n is brought still more closely i n to

li n e with n itroge n phosphorus sulphur and io d i n e i n the de
, , ,

v e l o p me n t of base formi n g properties whe n u n ited to n ega

-
,

tive orga nic groups J S L EW S H WE

.
A I O ~

W SH N G T N
A I O D L UAN V E E N 1
L EX N G T N V
I O , A .
,

D e c 30 .
, 1 90 1 .
VO L . X XV I I MA Y , 1 90 2 .

A ME R IC A N

T H E C A L C UL A TI O N O F A TO MI C W E I G H T S .

BY F . W . CL KEA R .

In t he ordi n ary d iscu ssio n of ratios relative to atomic

weights d i ffere n t results may be Obtai ned by varyi n g the
,

method of computatio n This is due to the fact that the ratios

.

as measured are not absolut e but subje ct to er rors which , ,

should be but are n ot u sually distributed

, I n m ost cases, .

the te nde n cy gi s to accumulate all errors acci d e ntal or sys ,

t e m ati c up o n the co n sta n t which is last determi n e d a p ro ce

'

, ,

dure which is O bviously u nscie ntific Take for example the .

, ,

ratio
C a F2 C a SO

upo n which our k n owle d ge of the atomic weight of fluori n e

chiefly depe n ds In the actu al measure me n t certai n errors of
.

observatio n occur ; the data are redu c ed with assum e d values

for the atomi c weights of calcium sulphur an d ox y ge n , , ,

which are themselves to a greater or less e xte n t i n exact

, , ,

an d all of these i n accuracies are brought together i n the fi n al

result of calculatio n If oxyge n be take n as the sta n dard of

.

atomic weights an d therefore not subj ect to error the atomic

, ,

Weight of fluori n e will co n tai n the error of the experime nt ,

2 1- 2 7
32 2 Cla rk e .

plus the errors i n the atomic weights of calcium an d sulphur

a n d whether these compe n sate o n e a n other or n ot we have n o

mea n s of k nowi n g Moreover each error exerts its maxi .

,

mum effect whose exte n t c a n h ardly be estimated

, .

It is ge n erall y agreed with but few disse nti n g voices that , ,

the work of Stas upo n some of the more fu n dame ntal atomic
weights is as accurate as the prese nt resources O f e x p e ri me n
,

tal chemistry c an make it A nd yet eve n here discrepa n cies .

, ,

exist which the ordi n ary method of calculatio n fails to reco n

cile The ratios measured by Stas have bee n discussed by
.

various writers especially by Stas hi mse lf by O stwald by

, , ,

Thomse n an d by Va n der P laats an d the results of the

, ,

several computatio ns vary with the method of calculatio n .

Van der P laats i n particular has illustrated this fact by

‘
, ,

maki n g two calculatio n s givi ng the ratios equal weight i n ,

o ne ( A ) a nd weight i n ve rse l y g
, p rop o rtion al to the squares of
their probable errors i n the other ( B ) I n the followi n g table .

the various results of the reductio n s appear

l
O s tw a d Th om s e n

The di ffere n ces thus show n are slight but i n the case of ,

bromi n e they amou n t to more tha n two i n the seco n d decimal

p lace a n
,
u n certai n ty greater tha n is commo n l y recog nized .

It is an u ncertai nty which affects all other determi n atio n s de

pe n di n g upo n the atomic weight of bromi n e as an a ntece d e n t
factor an d whi ch ought to be appreciably d imi n ished With
,
.

sulphur and n itroge n the diverge n cies are proportio n ately eve n
greater .

Now beari ng i n mi n d that the so calle d d etermi n atio n of

,
-

1 C mpt n d 6 36
o . re .
, 11 , 1 2 .
32 4 Cla r ke .

all determi n atio n s of the ratios i n questio n ma d e up to 1 8 9 7 , ,

are i n clu d ed in the discussio n i n ord er that the effect of such

,

a combi n atio n may dis ti n ctly ap pear T h e basis of calcula .

tio n the sta n dards of refere n ce are 0 z 1 6 a n d H

, ,

these values bei n g take n as k now n P erso nally I prefer th e .

,

hydroge n u n it as a starti n g poi n t but in the prese n t case the ,

results are to be compared with those of other computers as ,

previously cited .

To show th e method of cal c ulatio n let me first take o n e o r ,

two ratios separately For i n sta n ce the ratio

.
,

Ag Br 1 00

may be writte n 1 00 Br A g whe n the symbols Br

:
,

a nd A g represe n t the t w o atomic weights respectively So .

,

also the ratio

,

K C IO 3 O, 1 00

becomes in li n ear form

K C1 2
”

From 3 0 equatio n s of this ki n d the 7 n ormals are co n structed ,

each ratio co ntributi n g toward the establishme n t of each

atomic weight represe nte d i n it I n this way errors of meas .

u re me nt are d ivided up a n d distributed an d eve n systematic ,

errors fin d their i n flue nce d imi n ishe d .

If all of the 30 ratios were equal i n value a n d importa n ce ,

the formatio n of the n ormals woul d be a comparatively simple

matter but such is n o t the case Some are very exact others
, .
,

are more tha n doubtful a n d weight must be assig n ed accord

,

i n g ly The rigorous rule is to give each measureme nt weight

.

i n versely proportio n al to the square of its probable error an d ,

as the latter is give n i n every case the rule has bee n applied , .

O nly i n stead of multiplyi n g each equatio n by its weight

, ,

which woul d give coeffi cie nts of excessive size I have d ivi d ed ,

them by suitable factors an d so reduced the c oe fli c i e nts to

ma n ageable dime n sio ns The pri n ciple is u n c ha n ge d but its
.
,

mode of applicatio n is some what u n usual The same result .

,

ho wever is reached i n the e n d a n d the eleme n t of perso n al

, ,

j u d gme n t is e n tirely elimi n ated fro m the discussio n E ach .

 The Ca lcula tion f A tom ic We ig hts
o 32 5

ratio weights itself regard less of an y p re fe re n c e s upo nmy

’

part .

Now taki n g the regular method of least squares the 30

, ,

equatio n s after weighti n g re d uce to the followi n g n ormals

, , ,

seve n eq u atio n s co n tai n i n g the seve n u nk n ow n qua n tities :

(1) Ag C1 Br I
N Na K 2

(2) Ag Cl Br I
+4 7 1 80 3
- N Na K 4 1 30 2 9 7 8
( 3) Ag Cl Br + I 5 6 2 5 O N .

Na K
(4 ) Ag C1 I K

(5 ) Ag Cl Br N
35 1 4 34 Na K —

7 6 8 7 2 -8 5
(6 ) Ag Cl Br N
Na 2

(7 ) —
44 r 7 7 1 6 7 A s
. C1 +2 7 7 2 Br +0 5 5 36 1
-

33 7 7 7
4 0 N + 7 -5 7 3
6 4 8 K
A gla n ce at these eq u atio n s is e n ough to i n d icate some df
their deficie n c ies The first t wo o n ly are complete ; i n the
.

others eight terms are missi n g In the fourth equatio n .

,

which represe n ts io d i n e the terms correspo n di ng to sodium

, ,

bromi n e an d n itroge n are a bse n t a n d eve n potassium is rep

, ,

rese nted by a coe ffi c ie nt which is ri d iculously small Ma n y .

.

other coe ffi c ie n t s are smaller tha n they should be an d this ,

i ndicates the i n a d equacy of some of the d ata To be r eally .

satisfactory n o o n e of th e 4 9 coe fficie n ts should be wa nti n g

, ,

a n d all shoul d be reaso n ably large Moreove r every c oe ffi .

,

cie nt should represe n t data draw n from more tha n o n e ratio ,

a n d i n too ma n y i n sta n ces this is n o t the case Were Stas .

’

data alo n e co n si d ere d the n ormals woul d be still more i nc o m

,

p l e t e eve
,
n though th e outcome of the solutio n might be c o n

s i d e re d bet ter .

U po n solvi n g the 7 n ormal equatio n s the followi n g values

are O btai ned
A g 10 7 9 5 2 5
.

7 9 -9 6 8 7
3 6
2 Cla rk e

These except i n the case of chlori n e are co n siderably

, ,

higher tha n an y of the values give n i n the table of re d uctio n s

derived from the work of Stas an d yet they are not so i nc on ,

siste n t with the latter as they might appear to be at first sight .

From the n e w atomic weights we c an compute the value of

each on e of Stas ratios an d so compare the result with the
’
,

measureme n ts which he actually made This is do n e i n the .

followi n g table which gives i n each case the lowest and high
,

est determi n atio n by the great Belgia n .

Sta s .

R ati o . C l ul
a c a te d

K C lO, O3
A g C lO, O3
A g B rO , : O ,
A g IO , : 0,
: Cl

A g Br
Ag I
A g KCl
A g K Br
A g N aCl
A g N a Br
A g N H4C 1
A g N H Br
A g A g NO 3
A g N O, : K C l
K C 1 : K N O,
N a C l N aN O ,

In t e n cases out of the seve ntee n the calculated ratios

fall withi n the limits of variatio n show n by the experime nt s
of Stas ; in six cases they are lower tha n his lowest an d i n ,

o n ly o ne case is the result too high In n o case is the diver .

ge n ce l arge an d in most i n sta nces it is remark ably small

, .

My co n clusio n fro m all of these co n si d eratio n s is that al ,

though the n e w figures should not replace the accepte d values

for the several atomic weights they are n ot to be lightly dis ,

regarded They serve to exemplify the ultimate method of

.

calculatio n a nd to show that the data n eed rei n forceme n t by

,

additio n al determi n atio n s which should complete the n ormals ,

1 E ar ly w or k uppl
, s a n te d by l a te r a n d b e tte r m e a s u r e m e nt s .
32 8 A lle n a nd Gottscha lk

supply the 2 4 a n d to improve th e 1 8 is the experime n tal part

of the problem and this is not so grea t a tas k as it might ,

seem to be at a first gla n ce For example suppose that the .

,

ratio A g C N S A g I were capable of measureme n t Its errors .

of o bservatio n would be divided betwee n 5 eleme nts 8 miss ,

in g c oe fli c ie n ts would be supplied an d 2 5 c oe fi c i e n ts i n all ,

would be a ffected Merely to fill the gaps i n the equatio n s .

,

therefore is easy to fill them properly is a more weighty

,

questio n To this e n d 40 or 5 0 n e w ratios ought to be care

.
,

fully d etermi n ed givi n g a system of ratios co n tai n i n g from ,

80 to 1 0 0 i n all Fo r o n e chemist so great a labor would be

.

hardly p ossible but by cooperatio n bet wee n several workers

,

the task mig ht be performed an d i n somethi n g like re ason a ,

ble time The metho d s of ma n ipulatio n the precautio ns to

.
,

be O bserved the d ifli c ultie s to be e n cou n tered are all well

, ,

k now n an d that co n si d eratio n helps to simplify the problem

, .

Stas a nd Marig n ac h ave laid the fou ndatio n s and with their ,

recorded experie n ce to guide us we should be able to build

the structure hig her wi thout excessive d ifi c ulty .

RE SE A R C H E S O N T HE OX ID E S O F T U N G ST E N .

BY E . T . A LL E N A N D V H G TT SC H L K
. . O A .

Of all the di ffere n t oxides of tu n gste n which n ave bee n de

scribed o nly two WO a n d WO are of establish e d composi , ,

tio n For mulas for at least half a d oze n others have bee n
.

proposed Th us , Malaguti prepare d a blue substa n ce to

.

which he ass ig n ed the form ula W O by heati n g tu ngstic , , ,

‘
oxide i n dry hydroge n by mea n s of a n al c ohol lamp Von .

U ls ar asserted that the co m pou n d obtai n e d by heati n g tu n g

s t i c trioxide stro n gly i n hy d roge n was W 08 G meli n o b 3
.

t ai n e d a blu e compou n d by redu c i n g tu n gstic trioxi d e i n a

curre n t of carbo n mo n oxide to which Vo n U lsar assig n ed the ,

formul a though D esi was u n able to get a homoge n eous

3
pro d uct i n this way .

By oxidizi n g metal lic tu n gste n with stro n g sulphuric acid

1 A nnh i m ph y
. 60
c 7 . s .
, , 2 2

2 G h m O tto L h bu h d
ra a -
: e r c er C h mi e e ,
”
Vo l I I. .
, p . 1 16 1 .

3
J A m C h m So 19 2 3
. . e . c .
, , 0 .
 R e se a rche s on the Ox ide s f
o Tu ng ste n .
32 9
‘
u nder various co n ditio n s Desi obtai ned several substa nces ,

which he co n sidered chemical i n d ividuals havi n g the formu

l as WO W 03 W O, an d W5 O9 These substa n ces like all
, 4 , , , .
,

the oxides previously referre d to were blue or bluish i n color , .

It was i n the hope of cleari n g up s ome of these u n certai n

ties that the prese nt i n vestigatio n was u ndertake n No n e of .

the products u n d er co n sideratio n c an be sublimed or other

wise p n rifie d co n seque ntly there is d a n ger of bei n g misled by
,

mixtures The rapid oxid atio n to which those which are pre
.

pared by g w e t metho d s are subj ect co n stitutes a n other d ifli c u lty ,

i n their i n vestigatio n Fi n ally so far as k n ow n n o n e of , , ,

them forms salts therefore the formulas have to be d educed ,

from a n alysis A nd si n ce the rati o betwee n tu n gste n an d

.
,

oxyge n is large ( 1 84 the di ffere n ce in the perce n tage of

the eleme n ts dema n ded by such compo u nds as W m O n a nd
Wm + O + 3 is correspo ndi n gly small We have overcome
I n .

these d ifli c u l t ie s i n part by usi n g pure materials washi ng , , ,

the products out of co n tact with air a n alyzi ng them without ,

.
dryi ng a n d usi ng pretty large portio n s for a n alysis Such
,
.

mixtures as result fro m i ncomplete reactio n s we have avoided

by treati n g our pro d ucts with successive portio n s of reage n t .

In establishi n g our formulas we have also bee n aided by

certai n theoretical co n sideratio n s Thus far we have ex .

p e r i m e n t e d o n ly o n the actio n which re d uci n g age n ts exert

o n tu n gstic aci d This compou n d is much more d iffi cult to
.

reduce tha n chro mic or molybdic acid In alkali n e ( tu n g .

2

state ) solutio n it may be boiled with grape sugar hydroxyl ,

ami n e or eve n metallic alumi n um witho ut u n dergoi n g an y

3
, ,

reduct io n Suspe n d ed i n hot co nce n trate d hydrochloric acid

.
,

it is stable to w ard hydroxyla mi n e oxalic aci d or alcohol , , .

°
E ve n i n sealed tubes at 2 0 0 C the last n ame d reage nt c i ,
-

fe c te d no ch a n ge i n the appeara n ce of the tu n gstic a c i d but ,

yielde d o n ly ethyl chloride A Solutio n of sulphurous acid .

,
°
saturated at a lo w temperature m ay be heate d to 2 00 C i n ,
.

1
J A m Ch m S
.
9 3
. e . oc . , 1 , 21 .

1 R e g a rd in g the re d u c t io n of t u n g sti c ac id i n th e d r y w a y , se e E h re n fe l d t : J .

Am . Ch e m Soc . . , 17 , 38 1 .

8 H y d ro y x l mi n f o m s a
a e r co mp u n d t
o o b e d e s c rib e d l a te r .
3 30 A lle n a nd Gottscha lk

sealed tubes with tu ngstic acid without reduci ng more tha n

, ,

‘
traces i n the upper surface layer .

N asce n t hydroge n liberated from acids by the actio n of ,

metals reduces it but si n ce the fi n al product seems to be

, ,

metallic tu n gste n this reage n t did no t seem to promise well ,

for the preparatio n of a pu re oxid e I n sta nn ous chloride .

an d hydriodic acid ho w ever we fou n d reage nts w ell adapted , ,

to our p urpose .

Re du cti on of Tu ng stie A ci d w i th Sta n n ous Chlor i de .

Sta n n ous chloride reduces tu ngstic acid to a fi ne dark ,

blue i n soluble substa n ce The tu n gstic acid merely requires

,
.

to be heated on the water bath with an excess of aci dified -

sta nnous chloride solutio n u n til the color i n dicates that the
cha n ge is complete In o ur earlier experime nts we poured .

off the reage n t at this stage an d repeated the reductio n but ,

a n alyses of the substa n ce showed that this was u n necessary .

Three or four grams of tu ngstic acid is easily reduced by 2 0

to 2 5 cc of sta n n ous chloride solutio n which m ay be pre
.
,

pared by dissolvi n g 8 grams t i n i n 2 5 cc co n ce n trated hydro .

chloric acid A 1 00 cc E rle n meyer flask closed by a o n e

. .
,

hole stopper provided with a B u n se n valve is a co nve n ie n t :

,

reactio n vessel si nce it serves to keep the substa n ces out O f

,

co ntact with air The product must b e washed i n hydroge n

.

or carbo n dioxide A cyli nd er was made by cutti n g O ff the .

lower third of a wide mouthed bottle about 2 3 i n ches i n diame -

,

ter an d gri n di ng dow n the edge The smaller e n d was

,
.

closed by a perforated stopper through which passed the ,

stem of the fu n n el which was e nclosed by the cyli n der .

Through a seco n d hole i n this stopper passed the co n ducti n g

tube for car bo n dioxide ( hydroge n if used should of course , ,

be i n troduce d at the top ) The top of the cyli n der was close d .

by a o ne hole stopper which supported a small droppi n g fu n

-
,
-

ne l .To preve n t a ny diffusio n of air i n to the apparatus the

‘
,

stem of the fu nn el o n which the filtratio n was made dipped ,

1
J A m Ch m S
. 9 3.6 It i
e i d n t t h t D i mi i t p t d t h
. oc .
, 1 p , 22 -
22 . s ev e a es s n e r re e e se a

r ati on of s ulphu r h e r e , si n c e s ulph u ou s ac id a l on gi v

r e e s th e s a me re sul t .

1 T hi s a p p a ra tu s is s i m i l ar to t h at d e sc ri b e d b y H . N . Sto k e s , B ull U
. . S G e ol
. .

Su rv . 1 86 .
33 2 A lle n a nd Gottscha lk

The a n alyses i n Table I I were made as follows : A s soo n .

as the t in was completely washed out of the blue compou n d

the l atter was rapidly tra n sferred from the filter i nto a meas
u re d excess of titrated chromic acid by mea n s of a wash bot ,
-

tle fille d with air free water The mixture was the n boiled
-
.

for about fiftee n mi n utes or u n til c Omp le te oxidatio n was ac ,

complished A fter cooli n g the excess of chromic aci d was

.
,

titrated by ferrous sulphate i n the usual way The tu n gstic .

acid does n ot i n terfere a n d the loss of the same by dippi n g

,

out is negligible Si n ce a loss of 2 0 millig rams w he n

,

3 grams substa n ce is used occasio n s a n error of o n ly ,

per ce n t i n the oxyge n absorbed A fter the titratio n the .

,

tu n gstic acid is filtere d washe d with dilute hydrochloric a c i d

, ,

a n d burn ed in a plati n um cr ucible to a co n s ta n t weight As .

soo n as the filter is charred the cover of the crucible i s r e ,

move d The bl ast should not be used

. .

Ta ble 11 .
—
A n a lysis o f B lue H ydroxide We t ) .

Fo und
t a k e 11
( CC ) .

Fe SO, used i n ,

terms of K C r O 7 , ,

15 7
-

A vailable oxyge n
i n K , C r, O 7 re
quire d i n oxi d a
tio n 0 o o 0 0 0 o
WO ,
fo u n d
Bl ue oxi d e aub y ,

d ro u s calculated
,

from VVO 0 3

P e r ce n t of oxyge n
absorbed by blue
'
oxi d e 1 -
39

f
R e duction o Tu ng sti e A e i d by Hy dr i odie A e i d

I n these experime n ts the tu n gstic acid was heated with the

°
reage n t i n sealed tubes at a bout 2 0 0 C A bout grams .

WO 3 was u se d to about 1 0 c c of fu mi n g hyd rio d ic acid .

 R e se a r che s on the Ox i de s f
o Tu ng ste n .
333

( about the heati ng was or d i n arily co n ti n ued

sp . a nd

several hours We obtai n ed i n this way the same i ndigo blue

.
-

substa n ce which we got with sta n n o us chloride n or d id re ,

p e a t e d treatme n t with the reduci n g age n t appear to exercise

a ny i nflue n ce o n the fi n al product Weak acid did n ot give .

a complete reductio n an d very co n ce ntrated reage n t i n lar g e

,

excess gave i n o n e i n sta n ce a mixture co n tai n i n g besides

, , ,

the blue oxide a black substa n ce which seemed to co n tai n

,

co n si d erable io d ide It was n ot i n vestigated A ll the prepa

. .

ratio n s made with hy d riodic acid were a n alyzed accordi n g to

the method des c ribed on page 3 3 1 a n d a compariso n of the ,

results will Sho w that the y agree closely w ith those of Table I .

Ta ble [11 .
—
A na ly si s of Bl ue Hy drox ide P r ep a r e d w i th Hy
dr i odie A ci d .

C l ul
a c ate d
A ve r fo r W5 0 14 .

I II . ag e . H20 .

Dr in g i n
Dr i ng i n D ing i n by rog e n,
hy ro g e n, hy ro g e n, a b ut
o 1
1- 2 h u
o rs , 1- 2 h u
o rs . h u
o r,
at a b o ut a t a b ou t at

P ortio n I .

L oss o n heati n g
P erce n tage loss
P ortio n I I . 0 -7 9 33 1 -0 4 3 2

Water fou nd
P erce n tage water
'

1 55
P e r ce n t oxyge n
absorbed

P rope r tie s of the B l ue Hy drox ide of Tung ste n .

This compou nd is a deep blue powd er a little brighter than -

,

i n digo an d purplish in reflected light It is i n soluble i n

, .

water co n tai n i n g a little hydrochloric acid while i n pure ,

water it may assume a very fi ne state of divisio n appare n tly ,

formi n g a colloidal solutio n as tu ngstic acid does The blue .

hydroxide of molybde n um rece n tly i n vestigated by G uichard ‘

, ,

shows this property to a degree far more marked .

The tu ngste n compou nd oxidizes i n the air especially when ,

moist and if heated cha n ges to tu n gstic trioxide almost i n

,

5 A nn . c h i m ph y s
. .
, 2 3 , 5 19 .
334 A lle n a nd Gottse lza lk

sta nt ly Bleachi ng powder hydroge n peroxide perma nga n ic

.
-
, ,

acid and chromic acid all oxidize it but n ot very rapidly i n

, ,

the cold H ot co n ce n trate d sulphuric acid oxidizes it slowly

.
,

a n d co n ce n trated n itric acid rapidly C o n ce n trated hydro .

chloric acid has no effect on it Stro n g cold caustic alkali .

, ,

solutio n s if they cha n ge it at all do so very slowly

, H eate d , .
,

they form alkali n e tu n gstate a nd evolve a gas cc of . .

this gas was d iluted with air an d passed over palladium as

be stos The latter glowed brillia ntl y
. The total co nde n sa .

tio n was 1 6 cc which i n dicated cc hy d roge n A mmo

.
, . .

n i a also reacts with this compou n d A mmo n i u m tu n gstate .

passes i n to solutio n a n d a very co n si d erable brow n resi d ue

remai ns No gas is evolved A mmo n iacal silver s olutio n is
. .

reduce d by it .

It is this blue substa nce which is formed i n the well k now n -

test for tu ngste n by n asce n t hydroge n B ut n asce n t hydro .

g e n causes a further reductio n to W0 a nd fi n ally to the

metal so that it would be more ratio n al to employ a little

,

stro ng sta n nous chloride i n stead A s this test is ordi n arily .

'
performed o n e may overlook a very little tu n gste n because
, ,

with t in or zi n c and acid the blue color is tra nsitory .

Tize B ron z e Hy drox ide of Tu ng ste n .

Whe n the blue hydroxide which has j ust bee n described is

warmed with co n ce n trated ammo n ia a part of the tu n gste n ,

goes i n to solutio n as ammo n iu m tu ngstate a n d there forms , ,

as above stated a residue which looks brow n an d o n ly slightly

,

lustrous while covered by the solutio n but whe n washed a nd ,

dried it appears dee p purple with a fi ne bro n ze luster i n t e

-
,

fl e c te d light .

P r ep a ra ti onThe blue oxide prepared as described pre

—
,

v io u sl y is washed quickly i n to the flask which served i n the

,

formatio n of the blue compou nd by a j et of stro n g ammo nia ,

water The flask is the n filled n early full of ammo n i a a nd

.

corked with the B u n se n valve It should the n be ge ntly .

warmed a nd put aside to settle Now the liquid is removed .

and the treatme n t repeated To do this without allowi ng the .

33 6 A lie n a nd Goii se /mlk

C l ul
a c a te d fo r
A ve r W30 8 . W4 0 u .

ag e . H 20 . H 20 .

Time of dryi n g
( hours )
Weight take n
( gram )
L o s s o n h e at i n g
P erce n tage loss
W at e r c o l l e c t e d
P e r ce n t water
Oxyge n abs b d ’ ’

Oxyge n i n a n
hydrous sub
sta n ce ( per
ce n t )

Pr op e r tie s color this compou n d appears purple with a

—
In ,

fi n e bro n ze luster in refle c ted light I n the d ry state it is

‘

very beautiful Its chemical properties are similar to those

.

of the blue hydroxi d e It is Oxidized by the same reage n ts .

,

but more readily It c ha n ges first to the blue compou n d an d

.

the n to the yello w tu n gstic acid It is i n soluble i n hydro .

chloric acid but seems to go i n to solutio n som ewhat i n pure

,

water like the blue oxide an d tu n gstic acid Hot caustic

, .

alkalies form alkali n e tu ngstate an d hydroge n Desi obtai n ed .

a n a n hydrous substa n ce which a n alyses i n dicated to be ,

W308 by heati n g ammo n ium me t at u n g s tat e ( N I13 W O

, ,
-

i n closed vessels to a bright red n es s H e describes it as a .

beautifu l purple substa n ce with a yellow metallic reflex i n ,

” 2
soluble i n water acids a nd alkalies , , .

It is i nteresti n g to compare the actio n of ammo n i a on the

blue oxide with the results which Desi obtai n ed with those
,

oxides which he prepare d by oxidizi n g me tallic tu n gste n with

stro n g sulphuric aci d A ll of them accordi n g to him give .
, ,

m etallic tu n gste n whe n treated with stro n g ammo nia ,

Now .
,

co n ce n trated sulphuric acid oxidizes th e blue compou n d pre

pared by u s to tu ngstic acid a nd it may perhaps be possible ,
\
1 T h e l ow re s ul t s a re re ad i ly e xpl ai n ed by o xid a tio n . It w i ll b e n ot e d t h at th e
gu l l h i gh e t h n W4 O n d m p i te xid
'

fi re s a re a r a e an d s , i n s of o ati o n .

2
J . Am . C h e m S c 19 2 7
. o .
, , 2 .
 R e se a r che s on M Ox id e es o f Tu ng sze n
‘
.
3 37

that Desi s pro d ucts were mixtures co n tai n i n g u n cha nged

’

metal .

I n additio n to the evide n ce already prese n ted for the two

formulas W5 0 H O a n d V 308 H O we may i n sta n ce the
V
, ,4
.
,
.
, ,

fact that G uichard who has rece n tly i n vestigated the blue ,

oxide of molybde n um prepared and a n alyzed by metho d s ,

di fferi ng fro m o urs co n cl udes that the true formula for t he ,

same is The properties of this substa n ce re

semble those of It is however completely solu , ,

ble in pure water though n ot in dilute hy d rochloric acid a n d , ,

soluble also i n co n ce n trated hydrochloric acid , The result is

a gree n solutio n which accordi ng to G uichard co n tai n s , , ,

M0 C 14 Such a gree n solutio n is i n fact obtai n ed whe n di

.
, ,

lute solutio n s o fa molybdate are treated with sta n n ous chlo

ri d e while from a tu n gstate one gets the blue oxide
, .

H 0 di ffers from M0 5 0 6 H O also i n its behavior with ammo

2 14
.
2

n ia the latter givi n g M

,
00 2
.

WSOS H O fi nds its a n alogue amo n g the oxi d es of ura n ium

.
,
.

The latter in its hydrous state is describe d as a dark gree n

, ,
-

powder but a n other form appears to exist closely rese mbli n g

, ,

i n appeara n ce the tu n gste n compou n d Berzelius sometimes .

obtai n e d a purple brow n precipitate by precipitati n g w ith am -

,

mo n ia a solutio n of U SO 8 i n aci d s a n d E be l me n says that

, ,

whe n light decomp oses ura n yl oxalate a hydrate d form of

1
U 30 sepa rates i n vio let brow n fl ak e s
8
-
.

Very rece n tly H allopeau has revised the work on the ,

2
tu n gste n bro n zes There are two series of these i nteresti n g .

compou n ds The first is prepared by reduci n g the tu n gstates

.

at a red heat i n dry hydroge n They possess the ge n eral for .

mula W O S M0 where M Na or K These bodies possess

3
.
2 , .

a metallic luster an d the potassium compou n d is described as ,

a violet red subst an c e with a copper reflex recalli n g W 0,

-
, 3
.

H O i n a striki n g way
,
The members of the seco n d series .

( with exceptio n of the bariu m compou n d ) are made by redu

ci n g the molte n tu n gstates with metallic ti n They possess .

the ge n eral formula where M Na K L i or 2

, , ,

G m li K
1 u t H d bu h d C h mi
e n- 38 :ra : an c e r e e , 2
2 A nn . c h i m ph y s . .
, I 9 , 1 06

2 2— 2 7
3 38 . A lle n a nd Gottsclt a lk

} Ba , are all dark blue i n color li ke

an d So far
-

as co mpositio n goes the n the two compou n ds described i n

, ,

this paper are the mother substa n ces of the tu n gste n bro nzes -
,

though it remai ns to be proved that the co nn ectio n c an be ex

p e ri me n t all y ma d e .

A ssumi n g our formu l as to be correct the reductio n of tu ng ,

sti e trioxide by sta n n ous chloride an d hydrochloric acid or ,

by hydriodic acid co n sists i n the additio n of hydroge n

,

5 W03 + 2 H W0 5 ,5
H2 .

The study of colloi d al tu ngstic acid i ndicates a molecule much

more complex tha n WO, and other facts are i n harmo n y with ,

this It is easy to represe n t such a molecule by a ri n g struc

.

ture accordi ng with the vale n ce hypothesis an d ri ng stru e ,

tures usually go with chemical stability Tu ngstic acid at .

a n y rate sho ws a much greater stability tha n its chrom ium an d

molyb de n u m a nalogues an d it is n ot impossible that i n the ,

above reductio n a si ngle complex molecule is re d uced like

m a n y orga n ic compou n ds where oxyge n becomes hydroxyl .

The actio n o f ammo n ia on W5 015 H may be represe n ted thu s 2

W0 5 , 5
H2 4N H40 H ( N H4 ) 2 WO 4
2 W309H 2 H20 2
.

Tli e A ction n
o droxy la mi n e on a Solu ble Tn ng sta te .

Whe n hy d roxylami n e hy d rochlori d e is i n troduced i n to a

solutio n of sodium tu ngstate a white precipitate is obtai n ed ,

which is fai n t yellow o n dryi n g It does not appear to be .

crystalli ne I n water it is mo d erately soluble so that the

.
,

wash in g which is n ecessary i n its preparatio n is quite waste

ful Our preparatio n s were washed with very cold water till
.

chlori n e was removed the n with alcohol an d ether an d dried , ,

i n the air The compou n d d ecomposes rather viole n tly but

.
,

without deto n atio n whe n it is heated The a n alyses agree

,
.

closely with the formula

4N H2 0 H
‘

.
3 WO ,
.
55112 0 ,
-

i ndicati ng simply a hydroxyl ami n e tu n gstate There appears .

to be n o other tu n gstate of this type the ammo n iu m salt , ,

me n tio n ed by G meli n Kraut really -

,

1
possessi ng a nother formula .

1G m lin K ut H d b u h d C h mi
e -
ra : 5 ;
an A nn h i m ph yc69 3 er e e , 11 se e . c . s .
, , 2 .
 B e n e dict a nd M a nn in
g .

duces tu n gstic acid to an i nsoluble i n digo blue hydroxide -

,

WsO s O It is readily oxi d ized by the air a nd oxi d izi n g

.

age n ts an d dissolves i n ho t caustic alkalies with evolutio n of

,

hy d roge n It fi n ds an a n alogu e i n the blue hy d roxi d e o f

.

molybde n um ,
a n d may be co n sidere d as the

mother substa n ce of o ne of the series of tu n gst e n bro n zes

-

havi n g the ge n eral formula W5 O l M0 I t is this c ompou n d 4

.
2
.

which is forme d by n asce n t hydroge n i n the well k n ow n test -

for tu n gste n .

3 Whe n the abov e compou n d is acted upo n by stro n g a m

.

mo n i a water a part of the tu n gste n d issolves out as amm on i um

,

tu n gstate an d there rema i n s a brow n residue which dries to a

,

beautiful purple powder with a deci d e d bro n ze l uster Its .

formula is W 08 H O Its chemical properties are sim ilar to

3
.
,
.

those of the blue compou n d A mo n g the oxides of ura n ium .

we fi n d the a n alogous U SO x H O a n d the series of tu n gste n B

.
, ,

bro n zes of the ge n eral for mula W O S MO m a y be looked , ,

.
Z ,

upo n as its derivatives .

This work is publishe d i n an u n fi n ishe d co n d itio n because

the authors w e re oblig e d to separate I t is the i n te ntio n of .

o n e of u s to carry o n further stu d ies i n this field .

MISSO U R I ST A T E SC H OO L
O F MI N E S .

C on t r i b ut i on fro m t h C h m ic l L
e e a a bo r a t ory o f W e s le y a n U ni v e rs i t y .

A C HE MI C A L ME T H OD O BT A I NIN G V A C U A FO R .

BY F N S G BE N E D T D C H L TT E R M NN N G
R A CI . IC AN A R O . A I .

The productio n of a goo d vacuum espe c i ally i n desic ,

cati n g apparatus is frequ e n tly required in the chemi c al labora

,

tory Mecha n ical air pumps so successfully used i n the e x

.
,

h au st io n of i n ca n des c e n t light bulbs are obviously i mp ra c t i c ,

able for ord i n ary laboratory use an d the valve pump of the ,

physical lecture table is i n ge n eral the m ost available form ,

“

o f pump for pro d uci n g a vacuum I n the chemical labora .

tory o ne has as a rule to be co n te n t with the vacuum o h

, ,

t ai n e d by mea n s of o n e of the m a n y forms of water pumps u n

less as is occasio n ally the c ase a mercury pu m p is at ha n d
, , .

The le n gth of ti m e required to exhaust a vessel by mea n s of

the mercury pump is co n si d ere d so great a n obj ectio n to its
 ze m i ca l
A C/ M t/ d fe co or O bta i n i ng Va c ua .
34 1

every d a y use that the apparatus is commo n ly allo w ed to be

come dirty and ulti mately i n operative awaiti ng a special and ,

pressi ng nee d before bei n g put i n worki ng order .

Though water pumps are almost u n iversally adopted as the

most practicabl e i n strume n t for pro d uci n g vacu a i n the labora
tory their use is atte nde d with n umerous diffi culties chief of
, ,

which is the irregularity i n water pressure resulti ng i n a too ,

”
freque n t sucki n g back of water especially towar d s the e nd ,

of a n exhaustio n Where great i n equalities i n water pressure

.

are commo n it is customary to i n sert an empty bottle betwee n

,

the pump a nd the vessel to be exhauste d to colle c t an y water

that may i n adverte n tly be sucke d back This bottle while .
,

servi n g its origi n al purpose obviously i n creases the volume ,

of air to be remove d a n d co n seque n tly the ti m e required to

,

co m plete the operatio n .

With co n sta n t an d high water pressure an d otherwise ideal

co n d itio n s few if a ny forms of water pump will give a vacuum
, , ,

correspo n di ng to a mercury pressure of less tha n 1 0 mm .

It is more freque n tly the case however that the w at ei , ,

p ump available at an y particular time falls far short of this

e fli c i e n c y an d i ndee d by bei n g so i n ferior materially delays
, , , ,

the dryi n g operatio n that is d epe nde n t o n a good vacuum .

So far as we are aware the use of che mical m ea ns for oh ,

tai n i n g vacua has n ever bee n ge n erally adopted The ab .

sorptio n of a gas or vapor filli n g a space by m ea n s of some

suitable n on volatile absorbe n t is however capable of yield
-
, ,

i ng vacua of the highest degree of perfectio n .

R eg n ault i n some of his experime nts on hygro m etry made

1
, ,

use of the absorbi n g actio n of co n ce n trated sulph uric acid to

wards aqueous vapor to produce a vacuum H e exh au sted a .

large glass globe i n which a few gra ms of water had bee n

pla ced u n til all the water had vaporized thereby expelli n g ,

the air By shaki n g the globe he was able to break a sm all

.
,

glass bulb which h ad previously bee n filled with co n ce ntrated

sul phuric acid hermetically sealed an d i n serte d i n the large
,

globe The co n ce ntrated acid rapidly absorbed the water

.

vapor thereby produci n g a very perfect vacu um

h i mph y s
.
,

1 A nn . c . . , I s , 1 90
34 2 B e n e dict a nd M anni n
g .

The absorptio n by potassium hydroxide of residual carbo n

dioxide i n a vessel previously filled with the gas a n d the n ,

1
parti ally exhausted was first used by A n drews , .

2
B ru n ner substitute d calcium hydroxide for potassium hy
d ro x i d e an d made use of the fact that dry calciu m oxide will
,

n ot absorb dry carbo n dioxide i n establishi n g the co n ditio n s

u nde r which the operatio n is best co n ducted A t the e n d of .

the prelimi n ary exhaustio n by the water pump or air pump ,

the calcium oxide is moiste n ed with a small qua n tity of water .

The c arbo n dioxide i s absorbed the aqueous vapor resu lti n g ,

bei n g fi n ally absorbed by co n ce n trated sulphuric acid i n a

dish at the bottom of the vessel to be exhauste d I n two .

hours a n early perfect vacuu m was thereby obtai n ed i n a half

liter vessel of Special co n structio n .

H e further suggests the use of ammo n ia i n the place of car

bo n dioxide absorbi n g the gas by co n ce n trated sulphuric
,

acid .

3
N e w th h as a d opted this suggestio n i n a very striki n g lec
ture experime nt though t he practi cability of this method as a ,

laboratory age n t i s very d oubtful .

4
P fl u g e r demo n strated very clearly the age n cy of water vapor
i n removi n g air fro m a vessel duri n g the process of exhaustio n .

I n a n apparatus of special co n str uctio n he vaporized water

by exh austi n g the air by mea n s of a water pump O n i ntro .

d uc i n g co n ce n trate d sulph uric acid he was abl e to lower the

te n sio n of the residual gas to 1 or 2 mm of mercury H e su g . .

gests the i ntrod uctio n of co n ce n trated sulphuric acid i n to

vacuum d esiccators after an d n ot before exhaustio n though , , ,

n o descriptio n of a practical apparatus i n volvi n g the use of

this pri n ciple is i n clude d i n his article .

Other applicatio n s of chemical reactio n s in obtai n i n g vacua

with speci al refere n ce to perfecti n g the Torricellia n vacuum
5
i nclu d e those of G ass io t who used metallic sodium i n a rare r ,

6
fi e d atmosphere of pure oxyge n a n d applied A n d rews method
’
,

1 P hil M g 85 . p 4; A a P hy u d Ch m
.
,88 3 9 1 2, . 10 nn . s . n e .
, , 0
2 A P hy
nn u d Ch m
.
94 5 3 s . n e .
, , 2

3 “
C h mi l L tu E xp i m n t L n d
e ca 89 p 58 e c re e r e s,
"
o on , 1 2, . .

4 A h i v f di e G e
rc . . s . P h y s i ol og i c , 3 8 , 3 11
5 P hi l T ns
. 14 9
ra .
, , 1 47

0 L oc . ci t .
344 B e n e dict a nd M n n i ng
a .

chemical mea ns for securi ng the desired dimi n utio n i n pres ,

sure was ultimately used .

We have fou nd that after expelli ng the air i n the d e sicc a

,

tor with ether vapor the residual vapor is e ntirely absorbed

,

by the sulphuric acid i n the upper chamber yieldi n g a re ,

m ark ably good vacuum .

The exact co n ditio n s u n d er which the operatio n is best c on

ducted are as follows
Fresh co n ce n trate d sulphuric acid ( about 1 5 0 cc ) is placed
, .

i n the previously clea n ed a n d dried upper compartme nt of the

desiccator A fter i ntroduci n g the material to be dried ( i n
.

appropriate co ntai ners ) an d j ust before the cover is put i n

,

pl ace 1 0 cc of pure a n hy d rous ether are d elivered from a

,
.

pipette upo n the bottom of the desiccator i n such a m a nn er as

n ot to come i n co n tact with the material to be dried The .

cover is the n carefully put on the gl ass stop cock bei n g left ,
-

ope n Immediately the water pump is co nn ected with the

.

tube i n the cover and the exhaustio n co nti n ued u ntil the
m a nometer shows from 40 to 6 0 m m pressure The stop . .

cock is the n closed the tube co nn ecti ng with the water pump
,

removed and the desiccator allowe d to sta n d I n a very few

, .

mi n utes a vacuu m of fro m 4 to I ( or eve n less ) m m is o h .

t a i ne d With the desiccators i n use i n this laboratory thi s

.
,

degree of exhaustio n is obtai n ed i n from eight to twelve

mi n utes after p utti ng the cover o n the d esiccator .

A fter the water p ump has bee n disco nn ected the absorp ,

tio n of the ether vapor may be co n sid erably accelerate d by so

rotati n g the d esiccator held i n the ha n d s as to agitate the acid
a n d moiste n a l arger surface of glass i n the top compartme n t .

Obviously this procedure c an o n ly be carried out with due

care for the stability of the dishes i n the d esiccator .

I n the size of apparatus use d i n o ur experime n ts the lower

compartme n t represe n ti n g the effi cie n t space for desiccati ng
, ,

co ntai n s 2 1 0 0 cc this together with the 1 4 00 cc of space

.
,
.

i n the upper compartme n t whe n co ntai n i n g 1 5 0 cc of acid .

,

gives a total gas volume o f 3 5 liters to be exhausted . .

Obviously a d esiccator of the He m pel type is especially ad

v an ta g e o u s for use i n co n n ectio n with this method for obtai n
 Mix ed Cr y sta ls of Si l ve r Chl or a te a nd Sodi u m Chlor a te 345 .

i ng vacua as the ether vapor completely fills th e lower com

,

p a r tm e n t expelli n g the lighter air before the sulphuric acid

,

i n the upper compartme nt e ffects a n y great absorptio n of the

ether vapor I n d ee d it is d oubtful if the metho d c a n be use d
.

with a n ythi n g lik e this degree of e ffi cie n cy with desiccators

of a ny other type We h ave fou n d these d esiccators to be
.

remarkably tight vacua of about 1 m m pressure bei ng u n

, .

cha n ged at the e n d of two weeks .

We have n o d ata as to how ma n y charges of ether 1 5 0 cc .

of sulphuric aci d will absorb ; but t h e same aci d has bee n

used i n the operatio n of exhausti n g the desiccator three
times with n o n oticeable d imi n utio n i n the e fi c i e n c y of ab
sorptio n .

This metho d is especially adapte d for use i n the chemical

laboratory for ( 1 ) the apparatus required is that already i n
,

u se i n ma n y laboratories ( 2 ) the time requireme n t to secure ,

a good vacuu m is reduce d to a mi n imum an d ( 3 ) no or d i n ary ,

'

metho d will permit of so complete a rare fic at io n of the gases

i n the desiccator .

The applicatio n of this method i n obtai n i n g high vacua

other tha n i n d esiccators has more to do with the physicist
tha n the chemist the o n ly obj ect of this paper bei ng to pre
,

se n t to the chemical laboratory a simple an d ra p id mea n s for

obtai n i n g a good vacuu m .

M DD L E T W N C NN
I O , O .

C on t rib u t i on s f o m t h r e She ffi e ld L a bora t ory o f Yal eU niv e rs it y .

X C VI .
—
ON THE MIX E D C R Y ST A L S O F SI L V E R
C HL O R A TE AN DSOD I U M C H L O R A T E , AN D
T H E I R SO L U TION S .

BY H . W . F oo r E .

1
In a previous article it has bee n show n that whe n two
salts crystallize from aqueous solutio n depositi ng mixe d crys ,

tals of two crystalli n e forms the compositio n of the crystals ,

at the mixi n g li mit should i n ge n eral cha n ge with the cha nge , ,

of temperature E xperime n ts to prove this were carried o ut

.

1 Th i J U N L
s O 6 4 8 R A 2 1
, ,
34 6 f oote .

with mixed crystals of copper and zi n c sulphates I n the .

prese n t i n vestigatio n o ne of the obj ects has bee n to show that

the compositio n of mixe d crystals of silver chlorate a n d sodiu m
chlorate at the mixi n g limit cha n ges with cha n ge of tempera
t ure .

1
R e tg e rs has show n that silver chlorate a n d so d iu m chlorate
form mixed crystals very rea d ily H e fou n d that sodium .

chlorate crystallizes i n cubes co n tai n i n g up to 1 1 molecular

per ce n t of silver chlorate while silver chlorate cryst allizes i n ,

the tetrago n al syste m co n tai n i ng as mu c h as molecular ,

per ce n t of sodium chlorate The temperatu re of the e x p e ri .

me n ts was the ordi n ary roo m temperatu re A s will be show n .

later these values are slightly below the real mixi n g li mits
,

for that temperature .

In the experime n ts to be describe d pure so d iu m chlorate ,

a n d silver chlorate w ere require d The former was prepared .

by recrystallizi ng the commercial product which co n tai n ed a ,

small amou n t of chloride Barium chlorate was the starti n g .

poi nt for silver chlorate To a solutio n co n tai n i n g a kn ow n .

amou n t of the barium salt a calculated qua n tity of sulphuric ,

acid was ad d ed j ust suffi cie n t to precipitate a ll th e barium as

,

sulphate The precipitate was removed by filtratio n an d th e

.
,

filtrate co ntai n i n g practically pure chloric acid i n sol u tio n

, ,

was saturated with silver carbo n ate prepared by precipitati ng ,

silver n itrate with sodium carbo n ate The solutio n of silver .

'

chlorate w as filte re d from the excess of silver carbo n ate e v ap o ,

rated a n d silver chlorate obtai n ed by crystallizatio n The

,
.

p roduct was p urifie d by repeated crystallizatio n It was .

fou n d on a n alysis to be pure

, ,
.

In determi n i n g the mixi n g limits of the two forms solutio n s ,

were used havi n g a volume of 300 to 4 0 0 cc A small qua n .

tity of crystals formi n g fro m this volume of solutio n would

alter the compositio n of the mother liquor but very slightly -
.

The relative proportio n s of the two salts i n sol utio n were

varied u ntil both cubes an d tetrago n al crystals formed at the
same time i n approximatel yequal amou n t The two forms of .

crystals were so u n like that they could be disti n guished at a

1 Zt s c h r . ph y s . C he m .
, 5 , 438
348 Foote .

T t ra g o n a
e l C ub es Mo l e c ul a r p e r
M l ul Mo l e c ul a r p e r
. .

o e c ar p e r c e nt N a C 10 3 in
c e n t of c e nt of Mol s N a C 10 3 : Mo l s . A g C 10 3 d i s so l ve d
m ol m l h lo
.

N aC lO s . N aC l O 3 . I oo s . 11 20 . 1 00 o s H2o . c ra te s .

9 7 -35

7 5 -9 6
7 4 -7 7
0 0 O O 0 0 0 0

The results especially those for the cubes vary co n si d era

, ,

bly amo n g themselves as a very slight cha n ge i n the compo ,

sitiou of the solutio n s produces a very large cha nge i n the

mixed crystals The average values for each temperature are
.

give n i n Table I I a n d it is believed that these represe n t

.
,

very n early the true mixi n g limits .

Ta ble 11 .
—
A ve rag e s Comp u te d fr om Ta bl e 1 .

Mo l e c ul a r
T gon l
e tra a Cub e s p e r c e nt
M l ul Mo l e c ul a r
. .

a o e c ar N aC lO s in
pe r ce nt of pe r c e n t of Mo l s N a C 10 3 : Mol s A g C 10 3 : d i s so v e d l
mo l s m l hl
. .

N a C 10 3 . N a C l O3 . I oo . H2 0 . 1 00 o s . H gO . c o ra t e s .

12
°
25
°

35
°
50 47 -1 0

The results i n Table I I are show n graphically i n Fig I . . .

,

where the temperatures are plotted as ordi n ates and the

molecular perce n tages of sodiu m chlorate at the mixi ng limit
as abscissas It is quite evi d e n t that the mixi ng limit varies
.

with the temperature though in the case of the tetrago n al ,

crystals the cha n ge is very slight The c urve A B represe nt .

,

i n g the varyi n g compositio n of the cubes at the mixi n g li mit ,

i s a straight li n e If c o n ti n ue d dow n ward it would i nter

.
,
 Mix ed Cry sta ls o fSilve r Chlora te a nd Sodi u m Chlora te .
34 9

M01Perce nt NaC/Of .

F ig . I .

°
sect the temperature axis at about that is at 30 ,

sodiu m chlorate i n cubes shoul d be u n able to form mixed

crystals with silver chlorate This woul d make it appear very
.

probable that the crystalli n e form of sodium chlorate cha n ges

at this temperature The curve CD shows that as the tem
.

p e ra t u r e is lowered tetrago n al sil v er chlorate c a n take up i n

creasi n g amou n ts o f so d iu m chlorate It thus seems most .

probable that sodiu m c hlorate w o uld assume the tetrago n al

form belo w a n d be co mpletely isomorphous with silver

chlorate If this i n terpretatio n of the results be correct it ln

.
,

d ic at e s a method of d etermi n i n g the tra n s i tio n temperature

of a salt by mea n s of its mixed crystals .

A seco nd obj ect of this i n vestigatio n has be e n to d etermi n e

the relatio n s existi n g betwee n the salts i n solutio n a n d the
m ixe d crystals In what follows I shall use the followi n g
.
,

symbols : y represe nts the molecular perce n tage of the mo re

soluble salt as so d ium chlorate i n the total amou n t of d i s
, ,

solve d salts an d x the m olecular perce n tag e of that salt i n

,

]1
the mixed c rystals R oozeboom has show n that whe n mixed
.

crystals form i n two d iffere n t crystalli n e mo d ificatio n s as is ,

the case with so d iu m a nd silver chlorates the solutio n s from ,

whic h the two form s are deposite d are of two classes as re

gar d s the mixe d crystals
lZt sch ph y C h m 8 5 4
r . s. e .
, , 0
35 0 Foote .

I The value of y whe n th e solutio n deposits both forms of

.
,

crystals lies betwee n the values of x for the tw o forms at the

,

mixi n g limit ( C ase I V of R oozeboom ) . .

I I The value of y is greater tha n either of the values of

.

x at the mixi n g limit ( C ase V of R oozeboom ) . .

‘
R oozeboom i n vestigate d solutio n s of potassium an d thallium
ch lorates a nd the mixed crystals formed from them a nd fou n d
, ,

they belo nged to C lass I as is evide n t from the followi n g

values
y 2 x 2 and

In this case y represe nts the perce n tage of potassium chlo

rate i n the d issolved chlorates and x the perce ntage of p otas ,

siu m chlorate i n the two crystallized forms at the mixi n g

limits It will be n oticed that y lies betwee n the two values
.

of x Similar results have bee n obtai n ed by Muthman n an d

.

'

2
Ku n tze with the perma n ga n ates of potass ium an d rubid
3
i um an d by Fock with the followi n g pairs of salts
, Botas
si um a n d ammo n ium chlori d es p otassium a nd ammo n ium ,

bromides potassium an d thallium n itrates an d copper and

, ,

n ickel sul phates In this class solutio n s depositi n g .

,

crystals of o n e form o n ly whe n co n ce n trated cha nge their , ,

proportio n s of salts till they reach a co n ce n tratio n where both

forms of mixed crystals are d eposited together O n further .

evaporatio n the compositio n of the s olutio n remai ns fixed

a n d both forms crystallize together as lo n g as an y solutio n t e

mai n s It will be n otice d by refere nce to Table I I that th e

.
,
.
,

value of y represe n ti n g the molecular percentage of sodium

,

chlorate in the solutio n s is greater tha n either value of x the , ,

molecular perce ntage of so d ium chlorate in the mixed crys

tal s E vide ntly this example belo ngs u nder C lass I I tho u gh
. .
,

4
R oozeboo m was i n cli n ed to believe from the work of R e tg e rs , ,

that the salts belo n ge d i n the first class behavi n g like thal ,

li um a n d potassium chlorates I believe o nly on e example of .

this class has previously bee n d escribed that of the mixed ,

double chlorides of cop per with am m o n ium an d potassium by

1 Zt h ph y C h m 8 5 3
sc r . s . e .
, , 1
9 Z ts c h r . f . K ry s t .
, 2 3 , 36 8 .

8 I bzd
‘

.
, 2 8 , 33 7 .

4 Z ts c h r . ph y s C h e m . .
, 8 , 5 28
35 2 Foote .

Mol e c ul a r p e r
T e t ra on a l Cub es c e n t o f N aC l O s
Mol e c u Mol e c ul a r Mol s Mol s
. .

ar er er . N a C 10 3 : A g C l O a: i n d i s so l ve d
mol mo l h lo
.

c e n t o fN a C 03 . c e n t ofN a C 03 . 1 00 s . H 20 . I OO s . H QO . c ra te s .

xl . x2 .
y .

It will be n oticed that for all temperatures the values of y

are greater tha n the correspo n d i n g values of x that is the , ,

proportio n of sodium chlorate i n the solutio n s is always

greater tha n i n the mixe d crystals which are d eposited from
them .

In Fig I I the values of x a nd y take n from Table I I I are

. .

plotted as abscissas a nd ord i n ates respectively for the tem , ,

°

p e rat u re s 2 5 an d From the d iagram it is evi d e n t that

as the temperature rises the values of x a n d y beco me more
n early equal that is the compositio n of the mixe d crystals
, ,

will approxi mate more n early to the compositio n of the solu

tio n s from which they form .

The followi ng co n clusio n s may be draw n fro m the res ults

as regards obtai ni n g the pure salts from the mixe d c rystals
by recrystallizatio n Silver chlorate could be obtai n ed p rac
 Mix ed fSilve r Chlora te
C ry sta ls o a nd Sodi um Chlora te .
35 3
V

Fi g II . .

tically pure by recrystallizi ng as the proportio n of it i n the

,

crystals is al ways greater tha n i n the solutio n O n the other .

h a n d to obtai n pure sodium chlorate by recrystallizi n g the

,

mixed crystals would be impossible eve n though the mixed ,

crystals at first were n early pure sodium chlorate The re .

crystallized product would always co n tai n more silver chlo

rate tha n the mother liquor In this case a purer product
-
.

would be obtai n ed by evaporati ng the mother liquor tha n from -

the recrystallized product Silver chlorate could be obtai n ed

.

more readily i n a pure co nditio n if the recrystallizatio n were

carried o n at a lo w temperature for the proportio n of silver
,

chlorate i n the mixed crystals deposited from a give n solutio n

is greater the lower the temperature
, .

Sum ma ry .

1 The compositio n of mixed crystals o f sodium and silver

.

chlorates at the m ixi n g limit ch a n ges with a cha n ge i n tem

p e ratu re .

2 The perce n tage of sodium chlorate i n the total amou n t

.

of dissolved chlorates i n a solutio n is greater tha n i n the

mixed crystals from the solutio n .

3 A s the temperatu re is raised the perce n tage of so d ium

.

chlorate i n the total amou n t of dissolved chlorates becomes

35 4 Chr i sty .

more n early equal to the perce ntage of this chlorate i n the

mixed crystals .

4 Silver chlorate may be obtai n ed pure by recrystallizi ng

.

the mixed chlorates .

5 Sodiu m chlorate ca nnot be obtai n ed pure by re c ry st al

.

l iz i n g the mixed chlorates for the recrystallized prod uct c o n , ,

t ai n s more silver chlorate tha n the mother liquor -

.

THE E L E C T R O MOTIV E FO R C E OF ME T A L S IN
SO LU TION S O F C YA N I D E .
1

BY 8 B C H ST Y . . R I .

In reviewi n g my paper O n the Solutio n an d P recipitatio n

of C ya n ide of G old ”
Mr E B Wilso n co nte nd s that in “
,
2
. . .
3

the solutio n of gold by mea n s of alkali n e cya n ides the

various reactio n s are determi n ed as to their order an d i n te n
sit y by the relative positio n s of the eleme n ts co n cer n ed i n the
”
electro c hemical series or series of voltaic te n sio n , .

In a mo d ified form this statem ent is probably true That .

is to say the di ffere n ce of electrical pote n tial i n a ny closed

,

electrical circuit de termi n es the n ature of the reactio n s which

e n sue But the matter is n o t so simple as Mr Wilso n as
. .

sumes R ece n t i n vestigatio n s show that the order of the

.

metals in the electrochemical series d epe n d s n ot o n ly on the

n ature of the eleme n ts themselves but also o n the chemical ,

compositio n of the sol utio n i n which they are placed its de ,

gree of co n ce n tratio n its temperature a nd i n the case of , , ,

gases o n the pressure

, .

U nless all these co n ditio n s are take n i n to accou nt i n fer ,

e nc e s draw n from the electrochemical series are likely to prove

more misleadi n g tha n useful The series as quoted by Mr .

, .

Wilso n from Gore is as follows ,

3 P otassium 2 8 A n timo n y

4 Sodium 29 Tellurium
8 C alcium 31 G old
9 Mag n esiu m 37 C arbo n
1C mmu i t d by th uth n d b d up n ti l i t h T
o n ca e ti f
e a or a as e on a ar c e n e ra n s a c on s o

t he Am e ri c an u
I n s ti t t e of Mi n i n g E n gi n e e r s , Vol 30 . .

2 T an r s . A m I n st
. . Mi n . E ng , 2 6 , 7 35 .

3 I bid .
, 2 7 , 82 1 .
35 6 Ck ris ty .

he showed that the order depe nds on co n ce n tratio n an d tem

p e rat ure and that accordi n g to these co n ditio n s gold may
, , ,

be more or less electro pos itive tha n silver -

.

The variatio n s thus discovered in the relative positio n of the

metals i n the electrochemical series at o n ce cast a cloud on its
useful ness for predicti n g chemical reactio n s ; a nd though a
great m ass of experime n tal data was accumulated an d the ,

most acute mi n d s of the ce n tury were brought to bear on the

problem n o expla n atio n of these a n omalies was fou n d for
,

ma n y years .

It is o n ly withi n the last decade that a n ythi n g like a clue

to the mystery has bee n detected ; an d this result has bee n
made possible o n ly through the combi n ed efforts of a n umber
of me n who approached the subj ect fro m what may be almost
terme d its purely speculative side without a ny thought of ,

practical applicatio n s
M th d
e o s Use d i n This In ve stig a ti on .

In loo k i n g about for some mea n s of d etermi ni n g the relative

afli ni t ie s of the metals for cya n ide so l utio n s I lo n g ago came ,

to the co n clusio n that the determi n atio n of the relative elec

t ro mot iv e forces of the metals i n solutio n s of d i f
fere n t stre n gths
was the si mplest rea d iest a nd most certai n th at co uld be se
, ,

l e c te d . For properly Co n sidered it shows the actual te n

, ,

d e n c y of the metal to go i n to solutio n My first experime n ts .

were made i n this directio n i n A ugust 1 8 9 6 I ma d e at that , .

time a large n umb er of prelimi n ary d etermi n atio n s the re ,

s ult s of which were prese n ted i n a lecture give n February 1 ,

1 897 ,
before the C alifor n ia A ca d emy of Scie nces i n San ,

Fra n cisco .

The results of these experime nts have filled me with c o n

sta nt surprise whe n I have n oticed what appare n tly slight
,

causes were capable of maki n g great cha nges i n the electro

motive force of the same metal The great delicacy of the .

method proved to be the chief source of d ifli c u lty i n its ap p li

catio n while at the same time i t reported faithfully the facts
,

as they exist i n n ature .

T wo metho d s have bee n used i n these d etermi n atio ns the ,

”
first bei n g what I h ave for brevity called the ,
D eflectio n ,
 The E le c tromotive For ce o fMe tals .
35 7

method a n d the other the

, C ompe n satio n or Zero
method of P ogge ndorf .

I n each cas e a n electrolytic cell is co n structed with two

electrodes each immersed i n a separate solutio n O n e c on
, .
,

sisti ng of the metal to be tested was held i n the poi n ts of a ,

plati n um tipped pair of forceps electrically co n n ected with a

-
,

galva n ometer a n d was immersed i n a vessel co n tai ni n g the

,

cya n i d e solutio n of the give n stre n gth The other was i n all .

”
cases the n ormal electrode of P rof Ostwal d co n sisti n g o f .
,

mercury ele c trically co nnected with the galva n ometer by

,

mea n s of a glass coated plati n u m w ire The surface of the

-
.

mercury is covered with a layer of mercu rous chloride a ,

couple of i n ches thick a n d a solutio n of chlori d e of potassiu m

,

of I gram molecule -
( i n th i s c a se also a n ormal solut i o n ) .

The purpose of the n ormal electrode of Ostwald is to h ave

a n o n polarizable electrode i n a solutio n of k n ow n stre n gth
-

an d electromotive force This is fixed at 0 5 6 0 volt That

.
—
. .

is i n the case of the n ormal electrode the mercury io n s te n d

, ,

to precipitate themselves o n the surface of the mercury an d ,

the sol utio n is therefore n egative to the metal by volt .

That is the positive curre n t te n ds to flow th rough the solu

,

tio n to the mercury which becomes positively electrified

, ,

while the solutio n itself becomes n egatively electrified .

If we n eglect the slight electromotive force due to the c on

tact o f the two solutio n s the resulti n g electromotive force of
,

the combi n ed cell is the algebraic sum of the e l ectromotive

forces active at the two electrodes H e n ce if we subtract .
,

0 5 6 0 fro m the electromotive force of the cell we have the

.
,

electro motive force of the metal u nder co n sideratio n The .

algebraic sig n i ndicates the d irectio n of the positive curre n t .

The Defl e cti on M th d

This method is much the most con
e o —

v e n i e n t for such i n vestigatio n s particularly i n the first rough ,

i n g out of a large amou n t of material With proper p re c au .

tio ns it gives results no t less reliable tha n those obtai n ed by

the zero metho d a n d it has the great adva n tage over the lat
,

ter that the rapi d cha n ges of electromotive force m ay be fol

lowe d almost a s they occur .
35 8 Ckris ty .

The method is illustrated i n Fig I B is the cell co ntai n i ng . .

the cya n ide solutio n an d the metal M to be tested N E is ,

O stwald s n ormal electrode R is a resista n ce which varied i n

’
,

the tests from to oh ms G is a Wiedem a nn re ,

fl e c t ing galva n ometer K a make and brea k circuit key an d

, ,
- -
,

C a commutator .

DE FL E C TI O N M E T HO D .

B Ce ll Contai ni n g Cy ani d e Sol uti on ; R, R e si sta nc e of fr om to Ohm s ;

M
,

, Me tal to be Te st e d ; G, Wi e d e ma nn ’
s R e fl e c ting Gl a v an om e te r ;

O st w al d ’s N or m al E l ec t ro de ; K , Mak e and B reak Ci rcui t Ke y .

Fi g . I .

The galva nometer was calibrated by replaci n g the cells B

an d N E with a C lark cell prepared accordi n g to the d ire c ,

tio n s of Ostwald and noti n g the deflectio n produced by its

,

voltage through the give n resista n ce of to

ohms The voltage was take n as electromotive force
.

° °

(t 15 C ) volts -
. .

Most of the co n ce n tratio n s of potassium cyan ide were

(on e gram molecule 6 5 grams per liter or

-
p er ce n t ) or
, , ,

fractio n al multiples of this in te n ths Thus the series used

was freque n tly
M M M M M
1 10 1 00
36 0 Ckris ty .

the slight electromotive force due to the co n tact of the solu

1
tio ns ) .

Thus , if agai nst the

, n ormal electrode alumi n um , in a
solutio n of potassiu m cya n ide gives a n electromotive force
+ 1 5 5 volts that is if the curre nt flows fro m the alumi n um
.
,
—
,

to the merc ury the same as i n the case of mercury it fol

, ,
—

lows that the electro motive force of the alumi n u m in

potassiu m cya n ide will be + 1 5 5 0 5 6 0 volts .

—
. .

A gai n if a strip of amalgamated zi n c u nder similar circum

,

sta nces gives a voltage of volts the electromotive force ,

of amalgamated z i n c In a potass i um cya n i d e solut i o n W i ll

T
be +o 9 3 volt . .

In maki n g the determi n atio n s it must be evide nt fro m the ,

formula that if there are few io n s of the give n metal prese n t

,

i n the solutio n at the start the i n troductio n of a very few ,

more will make great cha nges i n the value of the e l e c tromo
tive force .

P
For In log it must be evi de nt that as P the solut i o n
7
.

te n sio n is co nsta n t ( for a give n temperature ) the value will ,

.

depe n d e n tirely upo n p the osmotic pressure an d the smaller , ,

p is the greater will be the e ffect due to slight cha n ges i n p

, .

H e n ce it will be impossible to get co n sta n t values for the

,

electromotive force u n less the value of p is nearly co n sta n t,

that is whe n the solutio n is saturated with io n s at the give n

,

temperature That is the case with the n ormal electrode

.
,

where the m ercury lies i n a saturated solutio n of mercurous

chloride The mercury is thu s i n equilibrium with its io n s
.
,

a n d a co n sta n t electromotive force results .

To get perfectly co n sta nt results with cya n ide s olutio ns it ,

would be n ecessary to have the solutio n saturated with th e

cya nide of the metal i n questio n But while this would give .

us a very satisfactory electromotive series it would n o t give ,

us a measure of the actio n of the u n saturated cya n ide solu

1 Th i s, e x e p t i n c s s o f g e at d i ff e n c e i n t h e n e ntr tio n f t h e so lu tion s
c a e r re s co c a o ,

h as b e e n s h w n t c u se n e rro o f On l y fe w th o u s an dth s o r hu n d re d t h s of a v ol t
o o a a r a .
 The E le ctromotive For ce o fMe tals .
36 1

tio n j ust as it acts on the ores

, We must therefore be con .
, ,

te nt with results that are n ot e ntirely co n corda nt and ta k e ,

the bes t of a large n umber of determi n atio n s .

The strips used were always freshly bur nished with sa nd

paper cooled an d touch ed to a grou nded plati n um wire to
, ,

d ischarge a n y electricity with which they might have bee n

charge d i n burn ishi n g .

Pr e li m i na ry R e sul ts w i th the Defl e cti on Me thod The fol —

lowi n g prelimi n ary results were obtai n ed i n O ctober to De

c e mbe r 1 8 9 6 with some of the commo n metals an d mi n erals
, , .

The metals were good commercial articles such as are i n use ,

i n the arts except i n the case of gold silver an d mercury

, , , ,

which were chemically pure In the case of some of the min .

e r al s ,such as z in c ble n de stib n ite etc the electrical re sis

, , .
,

ta nce was probably so high i n compariso n with that of the i a

t e rc al at e d resista n ce th at the results m ay be somewhat low .

Nevertheless they give at o nce some importa n t relatio ns

,

which must exist whe n ever the cya n ide process is applied in
the treatme nt of ores
Ta ble I .
—
E le ctromoti ve Force o f Me tals i n Cy a n i de Solution s .

Defl e cti on M th d
e o . Pr e li m in a ry E xpe r i me n ts .

l
O s t w a d ‘ s n or ma l e le ct ro d e

?
1
KCN l K CN KCN
é
. . .

+ o 40
’
A lumi n ium .

Zi n c amalgam ated + 0 -7 o +0 4 4
‘
,

+0 5 9 + 9 39
‘
Z i n c commercial Not determ
, .

+o 37 +0 1 6
’
C opper .

’
C admium +9 5
C ad m i u m a malg ama d + 0 5 5
,
’
.

Tin + +0
’
0 45 . 06

+0
’
Born ite
C opper amalgamated +0, .

Gol d +0 3 7
‘
.

’
Silver + 0 33
—
o os.

’
C O p p e r G la n ce -

‘
L ea d +0 1 3 .

T i n amalgamated N ot determ
,
—
0 12

L ea d
Mercury
,
" -
o og —
. 0 01 o 11.

G old amalgamated
,
 Ckris ty .

l
O s tw a d ’s n o r m l e le ct
a rod e
MK KCN
CN
T
. .

Vo l t
“

*A ntimo ny
’

A rse n ic
Bismuth
Niccolite
*Iro n
C halcopyrite

*P yrite
G ale n a
A rge n tite
Berthierite
Sp e isc obalt
M g ne t
a o p y rite

Fahlore

*
A rse nopyrite
P lati um n

*
C prite
u

*E lectric light carbo

Ble de n
n

Boula ngerite
Bour n o n ite
C oke
R uby silver ore
Stepha n ite
*Stibn ite

The electromotive forces of the metals a n d mi n erals mark ed

with an asterisk i n the above table have bee n plotted in Fig .

II The Y axis shows the pote nti al i n volts the X axis th e

.
,

co n ce ntratio n i n gram molecules and also i n perce n tages of

-

potassium cya n ide .

It will be noticed that in most cases the curves ap prox i

mate quite closely to th e logarithmic curve which theory
would give supposi ng the Osmotic pressure of the metallic io n s
,

prese n t to be i nversely proportio n al to the co n ce n tratio n of

the free potassium cya n ide prese nt but they have differe n t ,

origi n s .

It will be n oticed that the electromotive force of com mer

c i al sheet zi n c is i n creased by amalgamatio n probably by r e
-
,

d uc i ng local actio n with so me of its impurities by which some ,

of the curre n t produced is short circuited In all the other

-
.
36 4 Ckris ty .

metal which put a stop to further actio n W ith C opper an d

, .

iro n it was also possibly due to a te n de n cy of the metals to a

cha n ge of vale n cy wh i ch is accompa n ied by a cha n ge i n the
,

electrical state With plati n u m a n d g as carbo n it was not

.

i mprobably due to a varyi n g co nte n t of absorbe d gas .

In testi n g the mi n erals it was i n all cases d i fli c u lt to get a

,

complete electrical co n tact betwee n the tips of the plati n um

forceps an d the rough surface of the mi n eral fragme nt so that ,

the results are o n ly provisio n al particularly as the resista n ce ,

i n some of these cases was very high Nevertheless the re .

,

sul t s are ver y i n teresti n g They show for i n sta n ce that not
.
, ,

all copper mi n erals have a stro n g actio n on the curre n t P ure .

c h alcopyrite for i n sta n ce has hardly more actio n tha n pure

, ,

pyrite while born ite an d copper gla n ce have a very decided

,
.

te n de n cy to go i n to solutio n C uprite is also appare n tly very .

little acted on though this m ay be due to its high resista n ce

,

rath er tha n to a lack of te n de n cy to dissolve The soluble .

salts and mi n erals of copper co uld n ot be tested i n this m an

n e r owi n g t o their n o n co n du c tivity
,
-
.

It is plai n however that pure chalcopyrite gale n a arge n

, , , ,

tite m ag n e top y rite fahlore arse n opyrite ble n de boula n ge

, , , , ,

rite bo ur n o nite ruby silver ore stepha n ite a n d stib n ite

, , , , ,

whe n free from their oxid atio n pro d ucts are appare ntly very -
,

little acted o n by cya n i d e solutio n s .

It is also plai n that a particle of metallic gol d i n co n tact ,

Wi th a part i cle of pyr i te forms a galva n i c couple

,
in —

per ce n t potassium cya n ide solutio n equal to +0 ,

65 volt ,
in

or per ce n t po t a s s m m cya n i de solut i o n ,

volt ,
0

an d i n or per ce n t p ot as s m m cya n i de sol ut i o n ,

1 00

volt With zi n c , u n der the same circumsta nces ( if

we take for potassium cya n i d e solutio n the figures for
a malgamated zi n c ) taki n g the zi n c as the more e le c tro pos i
,

tive metal an d subtracti ng the pote n tial of gol d we have d if

, ,

fe re nce s of +0 5 6 volt + 0 5 4 Ev olt

. an d volt In
,
.
,
.

short these figures would measure the te nde n cy of the zi n c to

,
 The E le c tr omotive For ce ofMe tals .
36 5
'

dissolve or of the gold to precipitate i n potassium cya n ide

,

solutio n s of these stre ngths .

A ccordi n g to these figures the prec i pitati n g power of the ,

zi n c see ms to hol d u p quite well for the dilute solutio n s The .

actual failure to precipitate the gold sometimes met with i n ,

dilute solutio ns is n o doubt due to films of cya n ide or hy

,

drate of zi n c which form i n crustatio n s on the surface of the

,

zi nc and thus preve nt co n tact The fact that the use of a .

small amou n t of fresh cya n ide or of caustic potash i n the z m c

boxes starts precipitatio n agai n seems to fa vor this expla na ,

tio n .

The Ze r o M e thod This method is show n i n outli n e i n Fig

—
.

I I I N E i s the Ostwald n ormal electrode B is the cell con

. .

E CE L L

P O GGE N DO R F S COM P E N SA TIO N M E T HO D

’
.

B , Ce ll Con tai ni ng Cy ani d e luti

So on ; R, Re si st an ce Grad u
at e d into P art s ;
Me tal to be Te ste d ; V M ,
l
ov ab e Contac t;
O st w ald ’s N ormal E l e c t rod e ; G, Wi e d e mann ’
s R e fl e cting Gal van ome te r .
Fig . II I .

tai ni n g the cya n ide solutio n in which as before is immersed , ,

the metal Mto be tested A t G is a galva n ometer A t R is . .

a resista n ce gra d uated i n my experi me n ts i nto

, ,
parts , .

A storage battery of 2 volts and the combi n atio n cell N E B —

are so co nn ected that their positive poles are both co n n ected

at the same e nd of the resista n ce R The n egative pole of the .

storage battery is attached to the other e nd of the resista n ce

R so that the whole curre n t of the storage battery discharges
,
36 6 Ckris ty .

co n sta ntly through R The latter shoul d be great e nough to

.

avoid heati n g an d to m ai n tai n a co n sta nt pote ntial betwee n

,

the e n ds of R The other termi n al of the combi n atio n ( the

.

n egative pole ) is the n moved alo n g the resista n ce R till some

d ista n ce a is reache d at whi ch the electromotive force of

, ,

N E B is exactly bala n ced by the electromotive force of the

—

storage battery for that fractio n of R represe nte d by a In .

this case there is no deflectio n of the galva n ometer ; at other

po i n ts th e gal va nometer will be deflected either to the right or
l eft ac c ord i n g as too m uch or too little electromotive force is
,

used to bal a n ce N E B The electromotive force of the stor

-
.

age bat t ery is of course first calibrate d by compari n g it with

, ,

a sta n d ard C lark cell placed where N E B is ,

—
.

This m e thod o f determi n i n g the electromotive force of a cell

‘

is deservedly co n sidered o n e of the most reliable With non .

polarizi n g cells it certai n ly leaves n othi n g to be de sire d

, .

B ut i n i n vestigatio n s of this ki n d with cells that are easily

,

polarized accurate results are obtai n e d o n ly by a lo ng n u m

,

ber of very tedious approximatio n s whic h re nder the work ,

almost i n termi n able For it is of course impossible to hit

.
, ,

the right bala n ce at first an d if the co n n ectio n is made at an y ,

poi n t except the right o ne the metallic elec trode will receive ,

either a positive or n egative charge from the storage battery ,

a n d a tru e readi ng will be thus ma d e impossible It is a c ces .

sary to cha n ge the e n tire sol utio n i n B put i n n e w electrodes ,

at M drive out the di ffuse d cya n ide solu tio n fro m N E and
, ,

so o n un ti l the se O peratio n s have bee n repeated perhaps a doze n

,

times If this is n ot do n e the results are very u n reliable

. .

With the deflectio n method on the other ha nd the observa , ,

tio n s may be made very rapidly an d though there is a te n ,

d e n c y for the readi n gs to be a little lo w u n less they are quickly

m a d e still with a high i n tercalated resista n ce an d a delicate
, , ,

reflecti n g galva n ometer this metho d seems to be reliable for ,

these quickly polarizi n g electrodes .

A s I have already stated a n d as was first poi nted out by ,

Ostwal d strictly co n cord a n t results are possible o n ly w he n

,

the electrode is s u rrou nded with a mediu m already saturate d

with its io ns .
 The E le ctromotive Force o fMe tals .
36 9

1
I shall speak of the probable cause of these di ffere n ces later .

In order to make ic le are r th e mea n i n g of P rof von O e t .

ti n ge n s results I have plotted them i n Fi g IV as mi n e are

’
,
. .
,

plotted i n Fig I I In the figures x is m ade to mark the . .

,

molecular co n ce ntratio n
M M M the y axis shows
, ’ ’
1 10 1 00 1 000

1 Th e e a e r r so me ot h e r p ote n tia l di ff e re n c e s gi ve n by P ro f . von O e tti n ge n w h i c h

I i n c lu d e h e e r

Hg
H g 28 0 4
— o. 99 v o l ts .
( O s tw a l d ) so lution s .

Zn
+ 06 2 4
Z n SO 4
Mg ‘
+ 1 3 43 18 C
Mg SO 4
.

Cd
C d SO ,
Pb
P b ( C2 H 3 0 2 ) 2
- o 089 v o
. l ts .

Cu
5 82
— o
C U SO 4
.

Ag
A g 28 0 4
Hg
m a l e l e c t od ) l
.

-
o s6 o ( O s tw a d ’
s n or r e .

H g C 12
.

P rof v on O tti n g e n h i m s e lf d e te r mi n e d t h e fo ll ow i n g a l so ( al l at 2 5
°
. e C ).

Au
I 6 4 to v o l t s v a i ab l e
—
.
,
r .

A uCl on e (c
Au
M A uCla vo lt s .

vo ts . l
—
o. 2 6 to +o o3 , . v e ry v a r i a b e l .

— o .
36 , va r i a b le vo t l .

— o .
4o vo t l .

KC N S

vo lt .

vo lt .

vo lt .

o to vo lt .

vo lt .

vo lt s.

vo l ts .

2 4— 2 7
37 0 Ckris ty .

the pote ntial i n volts The desig n atio n Zi nc 1 m ea n s that

.

this was the first value obtai n ed with z i nc the desig n atio n ,

Zi n c 2 the fi nal value etc It will be n oticed that sometimes

, .

the first value is higher tha n the seco n d an d sometimes vice

ve rsa but the results are no t co n siste n t throughout some
, ,

times c rossi n g each other .

The first curves of each metal except mercury ap p rox i , ,

mately follow the logarithmic l a w ( on the assumptio n that the

n u mber of metal io n s is i nversely proportio n al to th e
p ot as
sium cya n ide co n ce n t r atio n ) E vi d e n tly the curves will cross
.

the X axis at di ffere n t poi n ts an d n ot usually at a molecular,

co n ce n tratio n Mz 1 u n less it should acci d e ntally happe n that

,

z 1 for M
2 : 1 . The seco n d curves of zi n c copper gold , , ,

an d silver also approximately follow it B ut the seco nd

, .

curves of mercury cobalt n ic k el an d iro n depart co n sidera

, , ,

bly fro m it It is possible that these d epartures are due to

.

polarizatio n e ffects as already explai n ed The irregularities

, .

are much more marked tha n with the deflectio n metho d .

With that method provided a sufli c ie n tl y large re sista n ce is

,

used the first deflectio n is the greatest an d i s take n as the

, ,

readi ng n earest to the truth The deflectio n the n gradually

.

falls ( ofte n quite rapi d ly if there is a formatio n of gas o n the

,

face of the electrode ) but the electromotive force n ever rises

u nless the first effect of the curre n t is to pro d uce a film of gas
or i n soluble cya n ide which puts a stop to the curre nt either ,

by s etti n g up an opposi n g electromotive force or by preve n t

i ng or re d uci n g co n tact by i ts resista n ce In this case sha k .
,

i ng the solutio n or j arri ng the electrode usually gives an i a

crease of the electro motive force by destroyi n g the fil m i n
part but if the metallic surface is u n tar n ished to begi n with
, ,

the electromotive force rarely rises agai n to its first value .

N e w Me thod of P lotti ng R e sul ts The method of plotti ng .

—

results hi therto use d while it shows very well the n ear ap

,

proach of the curve to the true logarithmic curve has the dis ,

adva ntage that o n ly three o r four values for the te nth ratio
1 as we
c an be plotte d . If however i n stead of maki ng
, ,
x
$
5
,
37 2 Chris ty .

}
5 volts the curve be c ome s a straight li n e passi n g through
,

the origi n at 0 . For x r: o, y z 0 .

The cur ve is plotted i n Fi g . V for values of

. x : log
P
from + 1 3 to -
12 , which gives voltages from to
P
an d the table shows values fro m x log m i n us
7
i nfi n ity to 40 . It shows that an e n ormous cha n ge i n the value
P
is n ecessary to produce a very mo d erate cha nge in the
7
voltage . Thus to produce a cha n ge o f
, volts a ch a nge
,

P
in the rat i o ( or te n to the fort i eth power ) is meces

sary .

In our experime nts of course we do , ,

no t k now the value of
P
but as a first approx i mat i o n we may assume i t in versely
15
proportio n al to the molecular co nce ntratio n MX I o n .

O n the axis of x is plotted the logarithm of the m olecular

co n ce n tratio n expressed i n the powers of 1 0 Thus x log .
,

M log 1 0 i The y axis gives the ele c tromotive force i n

n
.

volts For compariso n the theoretic formula of Ner nst is also

.

give n .

If we plot P rof von O e ttig e n s results as i n Fi g V I on

.
’
, . .

this pla n they become at o n ce more i n telligible We see at

, .

o n ce that all the curves do n ot remai n straight l i n es The .

zi n c follows alo n g very n early i n the theoretic straight li n e .

The copper starts well but soo n falls quite rapidly due prob , ,

ably to i n creasi n g dissociatio ns The gold a n d silver ap p rox i .

m ate fairly well also but the rest depart fro m it co n siderably
, , .

Comp a rison of the Defl e ction a n d Ze ro Me thods Si n ce the .

—

results of P rof vo n O e tt ig e n were p ublished I have thought

.
,

best to try the zero method as well as the deflectio n method ,

a nd to compare the results so far obtai n ed with each other .

I have also decided to plot the results by the same method as

sho wn i n Fig V as it e n ables us to compare t he results over
. .
,

a wider ra nge o fdilutio n tha n the former method of tabula

tio n would cover .
 The E le c tromo tive Force o fMe tals
.

A fter the foregoi n g descriptio n and discussio n of the various

methods employed in this i n vestigatio n the reader will be able
,

to study i n tellige n tly the tabulated results of the tests herei n

after stated.
 C hrzs ty .

02
0

09
0

— 1o
s

E . MF . . O F M E T A LS IN C YA N I DE SO L U T IO N S .

P rof . v. Oe tti ng e n of L e i p z ig .
(J Che m
. . an d Me t . Soc B
. . A Fe b
. .

Fig . VI .
 Ckris ty .

8 8
8 8
+ +

.
.

0
0 0 b
0
%w
.

. mw 0 m
e
m
A

z
.

3 0
?
.

s
0
? >
.
0 a
fi
m
0
Q Q m
0
o
a 0
a w
s
m

0
.
.
$
u 0 0 0 0

m 0 3
3 ? m 8
0
M0 95 >
.

a Q 0

.
o 0
.
D 0
E 0
n
9w 0

E
c
o
0 a
n
>
Q D

0
m
N
.

0
H
m 0

6
5
m
a
a
a
5 I «
0
0
0
u5 0 0
s 0
0
o
0 o 0
0 2 O
s
0
s 2
I
o H
0 0 5 s
O
s O 0 0 2 0
s 2
0
fi
.
0
m 4. H
;
2
H
0 5 w
m
0
3 e 0 ;
m0 3 m 0
m
/
0 0
2 Q 2 m 0 m: 0
 The E le c tromotive Force o fMe tals .
37 7

VO L TS

E . MF . . O F ZIN C IN KC y . SO L S .

Fi g V II
. .
—
O n th e h o ri z on t a l (x ) axi s a re l ai d o ff th e lu va e s of l og M= l og on
th e v e r ti c a l (y ) a xi s th e ac tu la ltvo s .

with d istilled water were very u n certai n probably because of ,

the formatio n of i n soluble films of oxi d e of zi n c an d o cclu d e d

hydroge n which preve n te d th e accurate rea d i n g of the n ee d le
, .

In my results with the deflectio n method I have always ,

take n the highest reliable readi n g as the most probable re

sult It was ofte n quite d i fficult to m ake sure of the proper
.

readi n g as a slig ht i n soluble film of cya n ide of copper forme d

,

almost i n sta n tly an d this lowered the pote n tial almost before
,

a readi n g could be take n O n agitati n g the copper so as to .

bri n g it i nto co ntact with fresh solutio n the pote n tial woul d ,

gradually rise to a maxi mum after which o n bei n g left at , ,

rest it would agai n fall o ff more gradu ally It is possible

, .
,

also that the te n de ncy of copper to form cupric as well as

, ,

c uprou s cya n ide may i n part explai n the discorda n t results

, ,

such for i n sta n ce as that obtai n e d by P rof v o n Oetti n ge n

, , .

p ot ass m m cya n i de solut i o n . H e says in a foot -

n ote
I OO
 C kris ty .

per ce n t whe n it brea k s off sharply and ru n s alo ng

,

fi at agai n j ust as the zi n c curve did

, .

O n plotti n g the gold curves as has bee n do n e i n Fig I X , .

,

it is evide nt that the gold follows the logarithmic law fairly

M
well as far as —
or per ce n t potass i um cya ni de A
Ego
.

co n siderable fall of pote ntial occurs accordi ng to my e xp e ri

M
,

M
me n ts betwee n,
1 00
or per ce n t p otass m m
cya n ide i n d icati n g a n i n crease of osmotic pressure probably
, ,

due to a n i n creasi ng dissociatio n of the potassium auro us

cya n i d e This poi n t seems agai n a critical poi n t i n the curve
.
,

which beyo nd it ru ns o ff more flatly i n dica t i n g a n approach

, , ,

to a co n sta n t osmotic pressure of the gold io ns .

GO L D IN KC y .

Fi g . IX -
O u th e h ori z onta l (x ) a x s a e l aid o fi t h e v lu s
i r a e of l og M l og t o“ ; on
l ( y) a x i s t h e a t u a l v o l ts
.

t he v e rt i c a , c .
 ’

384 Chrzs ty .

VOL T8

— 5 - 4 —
3 — 2 — 1

E . MF
. . O F GO L D IN KC I A N D KHO SO L UT IO N S .

F ig . X .
—
O u th e h ori z o n ta l (x ) a x i s e l
ar ai d o f
f th e va lu e s ofl og M l og 1 0“ on th e
v e ti c a l (y ) a x i
r s, the ac t u a l v o l ts
.

is exactly the same ( at a give n temperature ) whether the ,

gold is i m mersed in either potassium cya n ide potassium chlo ,

ride or potassium hydrate But the n umber of gold io n s i n

,
.

each solutio n an d he n ce the resulti n g osmotic pressure is

, ,

very di ffere n t A ccordi n g to this theory it is least i n pot as

.
,

si u m cya n ide much great e r in potassium hydrate an d great

, ,

est oi all i n potassium chloride C o n seque n tly the electro .

,

motive force varies i n versely as accordi n g to the ratio

P

p
The curves i n both cases ru n rather flat i ndicati ng an ,
ap

proach to a co n sta n t osmotic pressure for high dilutio n s .

 The E le c tr omo tiv e For ce o fMe tals .
385

Ta ble V11 E leci romoti ve Force f Sil i n P oza ssi u m

‘
.
—
o ve r

Cu rv e .
(0 ) (b ) .
(c ) .

N otebook B 1 p ,
.
7 1 170 P ublished
D ate Oct ’
A ug ’
J an ”
’
20, 96 19 , 99 99
Method
. .

De fi e c t . Zero . Zero
R esista n ce ohms ,
°
Temperature 23 C .

O bserver C hristy .

Ii hl l? Il ol t .

(N E .
2

C o n c e ntrat n K C N
’
.

M
1
+0 32 6 +0 34 5 +0 3 40 +0 30 6

if )
+0 15 2 +0 1 94 +0 1 80 +0 2 18

M
1 00
+0 05 8

L4
- 6 C) - <3 8 4 3 “ 41 4
3 3
—

1 , cxx3

0 0 0 0
_
O ,
4I7 o 0 0 0 0

ha
0 0 0 0 0 0 OO 0 O
M
- 0 0 0

I ’OOO ’O O O

M
( 2 H 2O ) _
O .
57 2 o oooo
o o o 0 0 0 0

Ta ble VII] . E le ctr om ol i ve For ce f

o L ead in Potassi um
Charn i de .

Cu rv e .
(a ) .
(b ).

N otebook B 1 p 68 1 83
’

.
,

Date Oct Sept

Method
. .

De fl e c t . Zero
R esista n ce ohms ,
o o o o o o

°
Temperat ure 23 C .

Observer C hristy
MF
.

E Volt .

(N E . .
—
o56l .

C on c trat
’ ’
n KC N
M
+0 125 +0 2 00 +0 16 4 co n st .

25 0
27
 C u rve .

+0 05 0 +0 15 8 +0 12 8

+0 00 6 +0 . 112 +0 . 120

+0 07 0 +0 1 20

0 0 0 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0
+O . O 4O 0 0 0 0 0 0

+0 040

( I HZO ) + 0 0 40

—
3 —
2

E . MF . . OF SIL VE R IN KC y .

Fi g . XI .
—
O u th e ho ri z o n t a l (x ) xi
a s a re l ai d oft th e lu e s
va o f l og M l og on

th e v e r ti c l a (y ) a xi s , th e ac t u l v o l t s
a .
388 Ck ris ty .

-
0
.
.
0 0m .

0 0 0 0 a
0
. 00
0
n 0 0 0
0 N u 0
0 3
0 >

b
.
. .

0 0 0 m
.

3
5
0 0
0
0 o
0
0 N f0
0 0
m

0
.
0
0
0
0
0 0
.

0 m
0
3 8 0
0 0 o
0
.
0
0 5 >
0 0 0
0
0
 The E le c tromotive Force o fMe tals .

V0L T S

—
5 -
4 - 3 — 2 - 1

E . MF . . O F M E R C U R Y IN KC y SO L U TIO N .

Fi g . X III .
—~
O u th e ho ri z on ta l (x ) xi s re l
a a ai d of
f th e v a l u e s of l og M l og on

th e v e rti c a l (y ) xi a s, th e act u l v l ts
a o .

an d potassium chloride A s he did not use th e same stre n gths .

that I h ave fou n d most co n ve n ie n t I have h ad to plot his re ,

a nd i n terpolat e the re
1
s ul ts re d uce them to zero pote ntial
, ,

s u lt s for the stre n gths I have used The results so o btai n ed .

are compared with the res ults obtai n ed by P rofessor O etti n ge n

a n d myself with the n ormal electrode The results obtai ned .

by us for potassium cya n ide are higher tha n B ra n de nbe rg s ’

,

but show the curves to be of the same g en eral n ature They .

are show n i n Fig XIV . .

3 O n th e s upp o s i t i on t h at has a p ote n ti a l of — o .

98 i n s te ad of - o .
5 6 o for
 Chris ty .

VOL T8

—
09
0

—
4 - 3
Q UI C KSI L V E R
Me rc u ry De p o la riz e r /Hg SO4 /Hg .

Th e R e su lt s of Bran d e n bu gr , &c ) .

P l otte d , Int e r p olate d , R e p l ott e d an d R du

e ce d to 0 P ote nti al , by SB Chr ist y
. . .

To w hi ch a r e a dd e d , for com p ar i son , c u r v e s w i th N orm al E l e ct r od e s.

Fi g . XIV .
—
o u th he o ri z on t a l (x ) xi s a e l
a r ai d o ff th e v a lu s
e of log M l og 1 011 on

th e ve rti c a l (y ) a xi s, th e a c t u a l v o l ts .

In order to bri n g out more clearly the n ature of the rela

tio n s existi n g betwee n the electromotive force of the d i ffere n t
metals I have combi n ed fro m the plotted curves of each
, ,

metal what appear to be the most probable values for each

,

metal The results are co ntai n ed i n Table X I

. .
 Ckris ty .

— 01
0

02
0

— 5 — 4 - 3 —
2

E . MF O F I R O N IN KC y SO L UT I O N
. . .

F ig X V o u th —
e h ori z on ta l ( x ) a xi s are l a id off th e v a lu e s of l og M l og 10
“

t h e v e rti c a l (y ) a x i s t h e a c t u a l v o l ts
. .

.
.

Ta ble XI .
-
E le ctr omoti ve Force of e ta ls i n M a Sol uti on ofCy a n ide
o P ota ss i u m
C on c e n t ra ti o n
f C m bin ti n f m
o a o
.

o os t p ro b a b e v al lu e s
M
.

Zi C pp l Si l v e r
.

L og Go d
M
1 00 . I On . nc . o er . . .

10 0 +0 94 5 + 0 9 30 +0 420 +0 340
M 10
—
I -
1 +0 8 7 0 + 0 6 80 +0 265 +0 195

M : 2 +0 7 7 5 +0 4 30 +0 0 90 +0 05 5

Mz 10
—
3 —

3 +0 4 1 5 -
o .
340
—
4 + 0 38 5
—
o z 5o
Mz
.

—
5 +0 35 5
M —
6 +0 3 30
—
o 2 80
.
—
o .
4gs
Dist water .
—
cc
+0 2 80 -
o .
3z o
L e ad . I ro n .

+ 0 2 00
+0 1 6 0
+0 1 1 0 —
c . 12c

+0 0 7 0
+0 0 5 0
+ 0 0 40

+0 0 40
 The E le c tromotive Force o fMe tals .
39 3

VO L TS

"
QZ

08
0

"
Q4

4 —
3 2
— —

E L E C T R OM O TIVE FO R C E O F M E T A L S
IN P O T A SSIUM C YA N I DE .

Combina ti on of Most: P robabl e Val ue s

.

F QL }CVL

These results have bee n plotted i n Fig XVI These . .

curves all show critical poi n ts at either log M 2

3 or
— —

Most of them show the greatest amou nt of i n flectio n at

, ,

4.

log M —
3. I n fact most of them seem to cha n ge in char
,

acter at this poi nt A ccordi ng to the N er n st Ost wald theory

. -
,
3 94 Ckris ty .

this would be explai n ed by the assumptio n that below say

M KCN ,
the dissociatio n of the complex io n co ntai ni n g th e
metal i n poi nt is practically complete so that th e os motic ,

pressure p of the give n metallic io n s i n the dilute solutio n s

becomes practically co n sta n t below this poi nt so that as the ,

is n early co n sta nt so its logarithm , ,

an d he n ce the
voltage becomes also n early co n sta n t as is show n i n the ,

fig ure .

The curves for lead an d iro n are very remarkable at first

quite lo w they mai ntai n themselves at a higher level tha n
,

either of the other metals e x c e p t z i nc This is explai n able ‘

o n the suppositio n that the values of P for lead a n d iro n are

for these metals rather low but that th e values of p reach a ,

n early co n sta n t value soo n er tha n for the other metals so that ,

the resulti n g curves flatte n earlier .

These curves also sho w a n umber of re m arkable crossi ngs .

C opper which starts at a voltage slightly less tha n that of

,

zi n c rapidly falls o ff crosses the curve of lead a little below

, ,

log M 2 5 an d that of iro n a little before log M

—
.
, 3 5
—
.
,

an d the n remai n s perma n e n tly belo w these metals The gold .

curve crosses the curves of mercury silver and iro n at j u st , ,

about log M
'

2 5 G old an d silver both cross mercury

—
. .

agai nat about log M 3 5 G old fi n ally crosses mercury —

. .

agai n at a poi nt beyo n d log M

- 6 an d remai n s perm a -
,

u e n tly below it after that .

It will be observed that the metals cha n ge their se q ue nce

from that of zi n c copper gold silver lead mercury iro n
, , , , , , ,

wh ch they possess
i 111 a —
or 6 5 . per ce nt p otass m m cya n i de
I

solutio n to the order zi n c lead iro n C opper silver mercury

, , , , , , ,

gold i n distilled water which is the usual electrochemical

, ,

series i n acid solutio ns quoted by Wilso n except that iro n is ,

placed above lead The determi natio n of iro n in my e x p e ri

.

men ts was n ot e ntirely satisfactory by reaso n appare ntly of , , ,

the formatio n of films a n d the results are probably too lo w ,

.

Water also appears to act like a weak alkali

, , .
39 6 Chris ty .

Re la ti on be twe e n the Stre ng th of Cy a n i de Sol uti on s a nd The i r

D issolvi ng Powe r .

It has already bee n show n by Mac l a urin that the d isso l v l

i n g power of a cya n ide solutio n saturated w ith oxyge n i n ,

creases with its stre n gth u ntil a stre n gth of 5 or 1 0 per ce n t is

reache d an d dimi n ishes agai n as the stre n gth i n cya n i d e i n
,

creases beyo n d that poi n t But so far as I am aware n o on e .

, ,

has proposed the questio n A t what poi n t of dil utio n does

”
t he cya n ide solutio n cease to act on the gold ?
A ccordi n g to the Ner n st theory gold should cease to dis ,

solve i n cya n i d e solutio ns provi d ed n o force acts except its ,

o w n solutio n pressure at th e poi n t at which its electro m otive ,

force is zero for the n its solutio n pressure will be j ust bal
,

a n c e d by the osmotic pressure of the io n s alrea d y i n solutio n .

A t this poi n t ( provide d n o other force acts ) the solutio n of

the gold sho uld cease .

It se e me d i nte re stin g to ascertai n if there w as s u c h a poi nt

. .

I n order to d o so it was n ece ssary to expose the gold to the

cya n ide solutio n i n the prese n ce of air u n d er circumsta nces
, ,

most favorable for rapid solutio n H e n ce I devised a rotati n g .

apparatu s co n sisti n g of three pairs of rollers drive n by a small

, ,

P elto n water motor o n which a couple of 2 5 liter bottles ; ,

.

such as are used for holdi n g n itric acid could be laid and ,

rotated about their lo n g axes The n umber of revolutio n s of .

the middle axis bei ng recorded the d ista n ce travele d was ,

k n own This precautio n was take n to be able to allo w for

.

the irregularities of the m otor .

Sta n dard strips of fi n e gol d were prepared by re peate d pre

c ip it at io n with sulphurous acid from a diluted chlori d e solu

tio n These were rolled o ut thi n a nd cut to a sta n d ard size

.

of 2 i n by i i n They weighe d from 2 5 0 to 3 30 milligrams

. .
,

accordi n g to their thi c k n ess The str i ps were boiled i n sul .

p h u ric an d muriatic aci d s washed a nd ig n ite d before use , , .

The first set of experime n ts was u n dertake n with 2 liters of

solutio n an d 0 5 liter of air the bottles bei n g stoppered The
.
,
.

weighed gold strips were the n a d d ed the bottles were rotated ,

for twe n ty four hours an d the strips were the n washed and
-
,

1
J Ch m S 6 3 7 3
. e . oc .
, , 1 .
 The E le c tromoti ve Force o fMe tals .
39 7

dried and weighe d agai n The n umber of rotatio n s made in .

twe nty four hours ra n ged from

-
to a n d as the i n

te r ior d iameter of the bottles was 4 5 i n ches t he d ista n ce .

,

traveled i n th i s time by the gold strip was fro m 1 to 6 miles .

It was i mpossible to get a u n iform rotatio n rate owi n g to co n ,

sta n t cha n ges i n the water supply B ut so lo n g as the solu .

tio n was kept ge n tly agitated these variatio n s did n ot seem to

1
h ave any appreciable effect on the result .

Table X I I I shows the results of these experime n ts The

. .

first pair were u n dertake n with distille d water to see if there ,

was a n y loss due to erosio n T he appare n t loss o f0 0 1 milli . .

gram was almost at the limit of a c curacy of the bala n ce but ,

seemed to show the possi bility of a slight loss due to that

11
cause . I t will be observed that up to
2 7 2 00
, or per
ce n t the gold loss is merely no mi n al n ever more tha n
, ,

milligram ofte n zero an d the results vary i n the most i rre g u

, ,

lar ma n ner . No . 1 8, with or per c e nt gave a . ,

M
loss of zero , an d No . 20, W i th , or per ce n t o n ly ,
00 0

milligram . It is believed that these smaller losses belo w

were chiefly mecha n ical . It was n oted that while most
of the bottles used were perfectly smoot h i nside some seemed ,

to have small sharp grai n s of sa n d or slivers of glass proj ect , ,

i n g above the smooth i n n er surface I n ma n y cases it was .

impossible to detect these without breaki n g the bottles The .

loss i n No 1 2 which was n ot rotated ca n n ot be set dow n to

.
, ,

this cause The expla n atio n i n this case an d perhaps i n

. ,

some others may have bee n a n imperfect mixi n g of the solu

,

tio n The solutio n s were made up by addi n g the proper vol

.

ume of stro n g solutio n to the proper amo u n t of distilled water .

In case the mixture of the solutio n s was no t thoroughly made

before the gold strip was added the gold would at first lie i n ,

a l ayer of stro nger solutio n that might have a slight solve n t

1 In m a k i n g th e s e so lu bi li ty e xp e ri m e n ts I w s ai d e d b y my fo m e a s i tant a r r s s ,

n ow A s i s t a n t P o f e sso
s E A K e r am
r I wi s h a l o t
r, . c k n ow l d g e t h e a i d o f m y
. s . s o a e

p re s e nt s i stant Mr G e o E Y u n g i n th e p e p tion of th e stan dard so lu tion s

a s , . . . o ,
r a ra

u se d i n th e s e xp ri m e nts a n d of th e i llu s tr ti on s
e e , a .
39 8 Ckris ty .

Ta ble X11] —
Sol u bili ty of Gold i n Cy a ni de f
o Va y
r gi n Stre ng th .

Intw e nty fou r h o urs

- Go l d
tri p s standard s iz e Fi ne g ol d 2 i n
s

. l iter bo ttles 4 %
. .
, .
,

X;
1 in
,
Weig h t 2 5 9 t o
.
, 330 m g 2g . i n i n di a meter , .
,

m ak i n g to re v o l u t i o n s i n t w e n ty fo u r h o ur s a n d c o n t a i n
-
,

i n g 2 l i ters c ya n id e so l u t io n a n d } l it er ai r 7 .

R e v ol u g l
L o ss o d
Stre n g th of ti o n s i n in 24
c y an i d e . 24 h ou rs . h uo rs . R e m ar k s .

Mi ll i g r m s
a .

N ew strip

0 00 00 6 5

0 000 0 6 5 £1? of milli

gram the loss
,

i n 4 6 hours

0 000 1 0 9

0 00 0 1 6

0 000 2 1 6

0 00 0 2 1 6 Not 1

rotated
0 0 00 2 1 6

0 000 3 2 5

0 00 0 3 2 5 -

%
2 of loss
hours
in 4 5

0 000 3 2 5 Same as above

400 C kris ty .

here the loss has rise n to milligram , and beyo nd this it

14
rapidly i n creases the strips , in the
1 0 0
or 5 per ce n t solu
tio n bei n g eate n through i n twe nty four hours -
.

The n ext set of experime n ts was devised to show the effe ct

of a smaller volume of cya n i d e solutio n an d an u n limited sup
ply o i air The sam e bottles as before were used but they
.
,

co n tai n e d o n ly 5 00 cc of solutio n an d were left ope n to the

.
,

air so that the latter was free to e n ter The results as show n .
,

i n Table X IV are i n ge n eral the same as before

.
, No ap .

ra bl e loss occurs to
M
p r e c up , but at that poi n t an d for
d
,
2 00 0
greater stre n gths the loss rapi ly i n creases fi n ally risi n g a
, ,

little higher tha n before In experime n ts Nos 4 an d 6 the . .

e n tire solutio n was filtered an d the washed filter was sc ori fie d

a n d cupelled In No 4 where the gold loss wa s
. .
,
n o ne -

was fou n d In N o 6 ( the loss bei n g

. .milligram ) ,

milligram of abraded gold w a s fou nd Whether the rest was .

fi ne e n ough to pass the filter or was dissolved before the stro n g

so l utio n was diluted is a co n j ecture , .

The n ext experi me n ts were m ade without agitatio n a n d in

the followi n g ma nn er : The gold strips were suspe n ded i n
perforated glass tubes j ust below the surface o fthe solutio n ,

so that although the solutio n was at rest circulatio n by c on ,

vectio n was possible The volume of the solutio n was 2 5 0 cc

. .

The time of actio n was i n each case forty eight hours The -
.

losses are given i n Table X V ; they are somewhat smaller .

11
tha n before ,
and agai n n egligible below
1 2 00
In this case

was not determi n ed . The adva n tage of the positio n

n ear the surface n ear the air is well show n i n co mpari n g N os .

5 a n d 8 W he
. n the gold was suspe n ded n ear the surface of a

solutio n ,
the loss was milligrams i n forty o
e ig ht

hours or n early
,
milligram per hour whe n the strip was
put at the bottom of the same volume of a similar solutio n ,

the total loss i n the same time was o nly milligram or ,

hardly o n e third as much -

.
 The E le ctromotiv e Force o fMe tals .
4 01

7 a ble Xl V —
Sol n bi li iy of Gol d in P ola ssi n m Cy a n ide of Va ry
i ng Stre ng ths i n Twe n éy Fou r H ou r s -
.

St a nd ard fi n e g o l d str i p s 2 i n X i i n , . . Wei g h t ,

250 t o 3 30 mg . 27 }
l i te r bottles 45 i n dia m e te r m ak i ng
‘

, .
, to evo l ut io n s i n
r

t w en ty fo u r h ou rs
-
. H a l f a l it e r cy a n id e so u l tio n , 2 l i ter s air Free l y
.

o p e n t o ai r .

R e vo lu ti on s in Go d l lo s i n 24 s
St re n gth of c y an id e . 24 h o u sr .
“
hou r s.

Mi lli g m s ra .

Hz O ) 10

Hz o ) 10

( 1)

0 0 04

150 54

1 In ord e r to se e w h e th e r o
h e s e l os se s m i gh t n ot be d ue i n p ar t or w h olly
r n ot t , ,

t o ab r i on th e solu ti on w a s fi l te r e d a n d th e fi l te
as , sc ori fi d ! an d c up e ll e d
r e N o go l d .

w a s f u n d i n t h e fi l te r
o .

2 Th i s s lu ti on wa s a l so t re a t e d a s ab ov e an d
o m i l l i g ramtof ab ra d e d go l d w as
, ,

fo u nd
40 2 Ckris ty .

Ta ble XV Solu bili ty of Gold i n Pota ssi um Cy a n ide oj Va ry

.
—

i ng Stre ng th i n For ty E zg iz t H ou rs A t Re st -
. .

St and ard fi n e g o l d strip s 2 i n X ! i n We ig h t 2 5 0 to 3 30 m i l l ig ra m s.

c .
, .

Su s p e n ded i n o p e n g l as s t u be s n e ar s u r fa ce o f 2 5 0 cc C y a n id e so l u
, , .

t io n at re st bu t s o t hat c o n ve c t i o n c urre nt s w e re p oss ible

, .

Stre n g th o fc y a n i d e .

0 0 00 0 6 5

42 7 9

A ll t h eseresults have bee n plotted together with the volt

age of the gold i n curves a b e and d in Fig XVI I A c , , , , . .

cor d i n g to the voltage curve the voltage becomes zero for a

cya n ide solutio n of M or about per ce n t an d it , ,

is a curious fact that this is very n ear the limit of stre n gth
that practice has so far j ustified Nevertheless solutio n s as .
,

low as per ce n t a n d eve n less have bee n employed i n , ,

practice and my experime n ts show th at the solutio n acts per

,

ce p t i bl y dow n as low as or per ce n t , and per

2

M
haps to , or per ce nt p otass mm c y a n1d e .

4 000

A n A ppa re n t Con tr a diction

lthough it will be see n that .
-
A
the solubility curves follo w very closely the voltage curve the ,

fact that actio n does n o t cease for the zero of pote n tial of gold
i n potassium cya n ide solutio n seems to co n tradict the Ner nst
1 8 . A si mi l a
xp e i m e nt w it h s m e c on diti
r e r a on s as to s tr e n gt h an d vo lum e of
s o lu ti n a
o N o 5 o n l y t h t t h e s t i p o f g l d e s te d
s .
, a r o r at t h e b otto m of t h e ve ss el g e a
, av

gol d l os s of on l y m i lli g m s ra .
404 Ckris ty .

there must be on e with an equal n egative charge H e n ce .

,

whe n a positive ion appears a n other positive io n must d isap

pear or else a n egative on e m ust also appear simulta n eously
, .

( In the case of io n s with varyi n g vale ncy an i on havi n g a ,

double or triple vale n cy is of course equivale n t to two or

, ,

three O ppositely electrified u n ivale n t 1o ns .

For i n sta n ce i n my experime n ts for determi n i n g the e l ec

,

t ro mot iv e force of gold i n potassium cya nide solutio n agai n st

'

t h e nor mal electrode the couple is composed of

,

G ol d KCN
K C l , Hg C l Hg
Whe n the gold dissolves the positive gold io n s travel fro m
,

the gold with their positive charge a n d in order that the solu
,

tio n may co n ti n u e a similar flow of positive io n s m ust c on

, ,

ti n n e by me an s of potassium io n s through the solutio n to the

mercury The potassium io n s fi n ally drive out some of the
.

mercury io n s which precipitate i n to the mercury formi n g th e

electrode at the same time givi n g up their charge of positiv e
,

electricity to i t Simulta n eously ther e is a correspo n di n g flow

.

of n egative io n s in the O pposite directio n Thus ; first chlo .

ri n e a nd the n cya n oge n move i n the opposite directio n to meet

the gold a nd the latter forms with the cya noge n the complex
,

n egative ion Thus :

CN (
'

The actio n of this couple will go o n so lo n g as the electro

motive force of the combi n atio n is greater tha n zero and as , ,

we have see n i n my experime nts lo n g after the electromotive

,

force of the gold i n the dilute cya n ide solutio n has becom e
zero For the te nde n cy of the mercury io n s to discharge i n to
.

the mercury electrode c an o n ly a ffect its purpose an d cause a

,

curre n t by the simulta n eous solutio n of the gold That is .

,

the t e n de n c v of the positively electrified io n s of mercury to

discharge themselves c an cause the gold to dissolve lo n g after
its ow n electromotive force has ceased .

f the Oxyg e n of the A i r the Sufi ei e n t

The E le ctr om oti ve Force o

Ca use of the Soluti on of Gold i n Cy a n i de Sol u ti on s .

We have a nother substa n ce at ha n d with a great te nde n cy

 The E le c tromotive Force o fMe tals .
40 5

to form n egative io n s This is the oxyge n of the air In the . .

prese nce of w ater the molecule of oxyge n 0 te n ds to as , ,

sume the io n ic state combi ni ng with water to form four n ega ,

t i ve l y electrified io ns thus ,

O r as has bee n suggested by Traube whe n metals dissolve

, ,

i n the prese n ce of oxyge n a molecule of the latter combi n es ,

'

directly with 2 atoms of pote ntially n asce nt h y droge n thus ,

0 2
2H H 0 L ater the peroxi d e of hy d roge n disso
2 2
.
,

ciates i n to two n egative hydroxyl io n s which e n teri n g the , ,

solutio n with their n egative ch arges of electricity te n d to ,

pro d u c e a curre n t i n the same directio n as the positively elec

t rifi e d mercury io n s do whe n they leave the solutio n That .

is oxyge n c an play the same part i n causi n g the solutio n of

,

th e gold as the mercury 1on s d i d i n the n ormal electrode above

cite d .

The co n trolli n g importa n ce of a n abu n da n t supply of oxy

g e n is well show n by the curves i n Fig XV I I In curve e . .
,

although there is o n ly o n e fourth as much cya n i d e prese n t as -

i n curve b the amou n t of gold dissolved is greater except ibr

, ,

the very dilute solutio n s The evide n t reaso n that the aera .

tio n is greater The cya n ide supply bei n g am ple i n both

.

cases the oxyge n supply determi nes the rate of solubility

, .

Fo r dilute solutio n s the amou n t of dissolved oxyge n bei n g ,

su m c i e nt i n b the greater volume of cya n i d e is the d e t e rm i n

,

i n g factor an d the amou n t dissolved i n b is in this case greater

,

tha n i n e .

I n teresti n g co n firmatio n of these views is fou n d i n Mac

lauri n s experime n ts o n the solubility of gold i n a soluti on of
’

cya n ide of potassium saturated with oxyge n H e co n du cted .

1

two sets of experime n ts with gold strips i n solutio n s of di ffer

e n t stre n gths The first set was left at rest for three hours
.
,

the seco n d set was agitated The losses are give n in the fol .

lowi ng table
Ta ble X VI —
M a e la u r i n s
’
Ta ble fL
o osse s o f Gold i n P ota ssi um

Cy a n ide Sa tura te d w i th Oxyg e n .

At re s t in so luti on satu rate d w it h oxy ge n Ti m e t h r . , e e h o u rs .

KC N per ce nt 1
, 5 10 20 30 40 50
G old loss m g , .
a

1
J Ch m S 63 7 3
. e . oc . , , 1 .

9 C u A F i g X VI II
rv e , . .
406 C k ris ty .

A gi t a te d fo r tw o h ur
o s in so lu ti o n s at u r a te d w it h x y ge n
o .

KC N per ce n t
, 1 39
G old loss mg
1
.
,

Maclauri n deems the results in the seco n d table more relia

ble tha n those i n the first In both it will be see n that there .

is a rapi d i n crease of the dissolvi n g power up to about 5 or 1 0

per ce n t potassium cya n i d e the n it gra dually falls o fftill at ,

5 0 per ce n t the solubility of the gol d is less tha n at 1 per ce n t .

The importa n ce of the rem arkable relatio n th us d iscovered

by Maclauri n has I thi n k n ever before bee n appreciated , Is , .

it n ot a little remarkable that the s tro n g cya n ide solutio n

should dissolve less gol d tha n a weak o n e while the electro ,

motive force of the gol d goes o n steadily i n creasi n g ?

B ut i n the light of the n e w th eory the reaso n is n ot far to
seek for at n o ti m e does the ele c tromotive force of th e gold
,

rise high e n ough to d isplace without exter n al aid a ny other

positive io n s such as those of the potassiu m i n the cya n i d e or
,

the hy d roge n i n th e water a n d u n less this is d o n e the gol d ,

io n s ca n n ot co n ti n ue to form n or the gold to d issolve For , .

this reaso n ( as Maclauri n myself a n d others have show n ) , , ,

i n the abse n ce of oxyge n or some equivale nt age n cy gol d ,

does n ot dissolve i n cya n ide solutio n s In other words u n ,

.
,

less some n egative i on like ( O H ) ( Cl ) or ( Br )

is added or some other positive io n as
,
etc is re .
,

moved by some exter n al source of e n ergy the actio n ca nn ot go ,

on . Ordi n arily the oxyge n of the air fur n ishes this e n ergy
,

as we have see n above it dissolves in the solutio n an d fur ,

n ishes the n egative io n s n ecessary to cause the solutio n of the

gold .

A gai n Maclauri n has fou nd the key to the a n omalous ac

,

tio n of stro n g cya n ide solutio n s It is in the fact which he .

demo n strated th at oxyge n is less soluble i n stro n g tha n i n

,

weak cya n ide solutio n s The followi n g results for the sol u .

fi c ie n t of oxyge n i n potassi um cya n i d e are plotte d

bi li t y c oe f
-

fro m the curves by i n terpolatio n

1 Cu B Fi g X V II I
rv e , . .
 Ckris ty .

VOL TS

50 PE R C E N T KC y

SO L U BI L ITY O F GO L D A N D O XYGE N IN KC y ,
Fr om e xp e r i me n t s of Mac la uri n . (J C he m Soc
. . . 1893, pg . M)
R e p l otte d , a nd G o ld Vol tag e C u rv e A d d e d .

F ig . X V III .
 The E le c tromotiv e Fon e o fMe tals .
40 9

As far as I am aware this i n verse relatio n betwee n the ,

electromotive force of gold and that of oxyge n i n cya nide solu

tio n s of varyi ng stre ngth as a co n trolli n g factor i n d e te rmi n
,

i n g the solubility of gold i n su c h solutio n s has n ever bee n ,

brought o ut before In a certai n se n se it is a tur n i n g poi nt i n

.
-

this d is c ussio n a n d he n ce merits a little close atte n tio n

, .

The io nizi n g te n de n cy ofoxyge n has bee n measured by a

cell c on t ai n in g a plati n um electrode made absorbe nt for oxy
g e n by coati ng it with plati n um spo n ge Wh en this is i m .
1

me rse d i n oxyge n at atmospheric pressure an d the e n d of the ,

e e IS i mmersed in ~
sulphur i c ac i d , a nd the latter 15 c on
I

n e c te d with the n ormal electrode the mercury dissolves an d , ,

a positive curre n t flows through the solutio n from the mercury

to th e plati n u m with a pote n ti al of + 0 7 5 volt .

This curre nt moves i n the O pposite d irectio n to that d ue to

the electromotive force of the mercury w e 0 5 6 0 volt ; ,
—

c o n s e q u e n t l v the electromotive force of the oxyge n a t atmos

0

p h e ri c pressure in co n tact with plati n um Spo n ge i n sul

1

h uric acid is equal to the sum of these or volts It is

p , .

n egative or ,
volts si n ce n egative io n s are produced , ,

a nd th e solutio n is n egatively electrified by th e m .

I f the above determi n atio n is correct it follows that if i n , ,

stead oi the n ormal electrode i n the above combi n atio n we ,

place a vessel co n tai n i n g a gold electro d e an d a solutio n of

cya n ide of potassium so weak that the pote n ti al of the gold is
n o t merely zero but as low as that of the mercu ry vi sa
, , ,

—
0 5 60 it is pla i n that a similar voltage of + 0 7 5 should ex
,

ist but i n this case the go ld would dissolve i n stead of the

mercury and the positive curre n t would flow through the solu
,

tio n from the gold to the plati num as before In this fc ase it , .

would be of course n ecessary to in terpose an _

M sol u t 1o n of
, ,
1

K , SO K C I, or some other n eutral salt bet wee n H SO , and , , ,

the K C N , to preve nt their direct actio n with each other from

i nterferi ng with the mere tra n sfer of electromotive forces at
the e n d of the li n e which we wish t o effect .

1 L e B l anc :
“
E l e c t roc h e mi s try , p . 2 2 1.
4 10 Chris ty .

Now gold does n o t absorb an d io n ize oxyge n as readily as

plati n um does but it acts similarly though to a much less
, ,

exten t In order to test the correct n ess of these views I took

.
,

T USFOR SHOWIN G T HE
A P PA R A

L O C A L E L E C T R O L YT I C A CTIO N
IN VOL V E D IN T HE

SO L U T IO N O F GO L D IN
A E R A T E D C YA N I DE SO L U T IO N
Fig . XIX .

two small porcelai n cups B a n d 0 Fig X IX in which were

, , . .
,

immersed the two electrodes b a n d 0 These w ere gold strips

held i n plati n u mtipped forceps co n n ected i n series with a re
.

-
,

fl e c ti n g galva n ometer G of ohms resista n ce i n clu d i n g ,

that of the cell an d a resista n ce R of

, oh ms T he .

solutio n in either vessel is co n n ected electrically by the liquid

i n the sipho n C .

It is very diffi cult to prepare an d impossib l e to keep a c y a

, ,

n ide solutio n e n tirely free from oxyge n u n less it is hermetic ,

412 Ckris ty .

clea n ed with gasoli n e a n d ether from the oil and solutio n an d ,

it was fou n d that the electrodes had lost weight as follows

b lost mg . 0 lost mg .

The solutio n s co n tai n e d i n the vessels B and O an d i n the

sipho n C w ere also assayed with the followi n g results :
B co n tai n ed milligrams O co n tai n ed , milligrams ,

a n d C co n tai n ed milligra m of gold .

The total loss of the electrodes was milligrams a n d that ,

fou nd was milligrams The di ffere n ce of

. milligram
”
was probably lost i n the washi n gs of the electro d es which
were not saved .

This experime n t corroborated by m a n y others shows

, ,

clearly that the positive curre n t flows from the deoxyge n ated
to the oxyge n ate d cya n ide j ust as theory would i n dicate
, .

The fact that more gold has dissolved in the oxyge n ated tha n ‘

i n the deoxyge n ated cya n ide d oes n ot militate agai n st the i n

,

d ic at ion of the galva n ometer .

The solutio n of the gold i n the vessel O is evide n tly due to

the we l l k n ow n phe n ome n o n of local actio n
-
The curre nt
that flows thro ugh the sipho n has to overcome a resista n ce of
from to ohms while local actio n c a n go o n i n the
,

vessel O w herever a n O H ( io n co mes i n co n tact with gold

a nd potassium cya n i d e H ere it forms a
. short circuit an d ,

it completes itself o n the gold strip 0 at a n y poi n t free from

oxyge n without havi n g to pass through the e n tire exter n al
,

circuit .

It might be obj ected that the fact that milligrams of

gold had d issolve d i n O as agai n st i n B o n ly we n t to
prove that some oxyge n h ad bee n co ntai n ed i n B though less ,

tha n in O an d that the solutio n i n each had bee n simply in

,

proportio n to the oxyge n prese n t But this does n ot accou n t.

for the absolute verd ict of the galva nometer which shows that
'

the positive curre n t flo w s d uri n g the e ntire experime nt fro m

strip b through the solutio n to the strip 0 The o n ly e xp l a .

n atio n that remai n s is the o n e which I have sugges ted There .

is n o doubt that co n si d erable local actio n we n t on i n cell 0 .

That this was the case is also evide nced by the fact that the
actio n was more u n iformly distributed over the surface of b ,
 The E le c tr omotiv e Fore e o M
f t e als .
413

while the strip 0 was n ot u n iformly acted o n but was eate n ,

i nto i n a remarkable ma nn er These strips an d particularly .

,

some of those to be described later ( with peroxide of hydro

ge n ) , were n ot corroded most upo n the edges where on e ,

would n aturally expect it but alo n g vertical li n es ru nn i n g up

,

an d dow n the middle of the strip In some cases they were .

eate n through alo n g these li n es i n such a ma n n er that n oth

i n g remai n ed but a thi n film like gold lace
-

It appeared that .

local actio n started i n alo n g these li n es rather tha n at the

e dges owi n g to di ffere n ces of pote n tial due to the distributio n
,

of the oxyge n an d that whe n it had o n ce set i n it was able to

,

mai n tai n itself .

It is probable that i n all cases of the solutio n of gold i n

the aerated cya n ide solutio n s the process as in the above case , ,

is o n e of local electrolytic acti on though as it is impossible , ,

i n such a case to apply the galva n ometer it would be diffi cu lt ,

to prove this propositio n except by i n fere n ce .

In all such experime n ts i t is importa n t to be certai n that the

gol d strips are i n the same phys i cal state si nce the existe n ce ,
*
of micro scopic films or u n weigh able traces of occluded gas
cause an appreciable di ffere n ce of pote n tial i n appare n tly
similar gold strips This is best tested by comp ari n g the
.

strips i n the same solutio n They react s i milarly if they are

.

carefully clea n ed with boili ng aci d a nd are the n w a shed with ,

distilled water a n d ig n ited to red n ess side by side i n the mu f

fi e or over a bu ns en flame i n a small porcelai n dish B ut if .

they are heated i n differe n t parts of the same bu nse n flame ,

they freque ntly show quite appreciable differe n ces of pote n tial
due to occluded gases .

f Hy drog e n Pe rox ide

The E fl e et o .

The peroxide of hydroge n used was Marcha n d s medici n al ’

,

co n tai n i n g per ce n t of available f p e ro x i d e as d etermi n ed ,

by titratio n with perma n ga n ate of potassium A ccordi ng to .

the n e w theory the H O ( ,

takes up from the gol d strip 0
, , ,

which becomes positive t wo u n its of n egative electricity an d

,

dissociates i n to 2 ( O H )
1I
In the first experime n t —

l KCN solutio n co n tai n i n g the

4 14 Ckris ty .

usual amou n t of absorbed oxyge n was used and 1 0 cc of this , .

solutio n was placed both i n B an d 0 G ol d strips b an d 0 .

were the n placed i n B an d O a n d th e sipho n was i nserted , .

Both strips sho w ed themselves of the same pote n tial The .

sipho n was removed an d 5 cc of water was a d ded to B a n d 5 .

cc of hydroge n peroxide to 0 O n i n serti n g the sipho n a nd

. .

the electrodes 6 proved to be electro n egative that is the solu

, , ,

tio n i n B was electropositive by + 0 6 6 volt in other words ,

the positive curre n t flowed through the solutio n fro m b to 0 .

A n other experime n t was made wit h boiled water with

per ce n t potassi um cya n ide that had bee n kept u nd er 3 ; i n ch
of oil for a week B a nd 0 were each fille d with 1 0 cc of
. .

this solutio n a nd the gold strips an d sipho n were i n serted

, .

The strips proved to be of the same pote n tial The sipho n .

was the n removed an d to B was ad d ed 2 cc of distilled water

, .
,

a n d to O 2 cc o f hydroge n peroxide
. A fter mixi n g o n re .
,

placi n g the sipho n the voltage rose to + 0 5 7 volt That is

,
. .
,

the positive curre nt flowed through the solutio n from b to 0 .

To exclude the air a layer of p arafli ne oil about i n ch thick

,

was floated o ver each solutio n before i nserti ng the sipho n .

The resista n ce of ohms was the n cut out leavi n g ,

o n ly t h a t of the galva n ometer oh ms ) an d the n eedle ,

which had previously show n a deflectio n of scale d ivisio n s

was throw n o ut of sight ( The li mits of th e scale used were
.

2 1 scale divisio n s ) A fter bei n g thus s h ort circuite d for an

.
-

hour a n d a half on throwi n g i n agai n the

, ohms resist
ance the voltage of the c ombi n atio n showe d itself to be still
,

i n the same d i rectio n +0 6 3 volt The,

ohms were .

agai n cut out a n d the co mbi n atio n was agai n short circuited -

over n ight In the mor n i n g some bubbles of gas from th e

.

actio n of the peroxi d e had colle c ted i n the upper part of the
sipho n an d ha d n early c u t o ff the curre n t B ut o n removi n g .

a n d refilli n g the sipho n the voltage still showed itself to be i n

the same directio n + 0 5 5 volt The resista n ce of

, .

ohms was agai n cut o u t an d that of the galva n ometer o n ly

left i n a n d after five a n d a half hours more the electrodes
,

were take n out clea n e d an d weighe d

,
Total time t w e n ty
, .
,

three hours .
4 16 Ckris ty .

ha s dissolve d i n the ve sse l con ta i ni ng n o ox i di z e r tha n i n the on e

con ta i n i ng the ox id i z e r .

In some other experime n ts with peroxide of hydroge n there

was more local actio n i n O an d the o strip lost as m uch and , ,
»

in some cases eve n twice as much as the b strip The exact , .

co n ditio n s govern i n g this local actio n are still u n der i n vesti

g a t i o n . B u t i n the se ca se s , a lso, the g a l va n o me te r show e d tha t
the posi ti ve cu r re n t w as still flow i ng throug h the sol u ti on f m ro

the str ip b to the str ip 0 in co n ta ct w i th the cy a n i de con ta i n i ng

the ox i diz e r , a n d the n ce back throug h the g old strip 0 back ag a i n

to b, the pla ce of beg i n n i ng .

The course of the n egative curre n t m ay be traced from the

gold strip 0 immersed i n the oxyge n ated cya nide to the strip ,

b i mmersed i n the u n oxyge n ated cya n ide i n two w a y s as fol , _

lows
A ccordi n g to O stw ald the reactio n O, + 2 H , O 4O H
l
1 .

produces 4 X 2 13 000 calories A ssumi n g this to be true the .

,

oxyge n molecule 0 forms with the water four n egative h y 2

drox y l io n s 4 ( O H ) ( ,these assumi n g a n egative charge ,

fro m the electrode 0 cause that e n d of the gold electrode to ,

be positively electri fied Now these n egative io ns travel .

through the solutio n displaci n g at the other e n d of the li n e ,

four n egatively electrified cya noge n io n s 4 ( C N ) ( which ,

give up their n egative charge at the other gold electrode b ,

an d thus e n able four positive gold io n s to go i n to ,

solutio n there formi n g with eight cya noge n io n s four complex

,

n egative io n s ,

The water prese n t may be regarded as n ot dissociated ap

re c i abl y a n d the dilute solutio n of cya n ide of potassium as
p ,

e n tirely so Maki n g these assumptio n s the pri n cipal re ac

.
,

tio n s may be expressed as follo ws

But this is equivale n t to the so - called E llsne r reactio n

02 + 2 H, O 4A u SK ON 4K O H ,

which Maclauri n has proved to be qua n titatively correct 2

.

C h mi h E n gi p
1 “
e sc e er e ,
”
.

J Ch m S 6 3 7 8
3 . e . oc .
, , 2 .
 The E le c tromotiv e For ce o fMe tals .
4 17

2 The other V iew followi ng Traube has bee n urged by

.
, ,

Bod l ae nd e r of the C lausthal Be rg a hade mi e

,
H e shows first . .
1
,

i n agreeme n t with Maclauri n and myself that the reactio n ,

H, O 2 Au 4 K ON 2 KA u ( CN ) 2 2 KO H +H

proposed by Macarthur to explai n the solutio n of cya n ide of 3

gold i n cya n ide solutio n s is i n correct Next he claims that , .

,

the so called E l lsne r reactio n really proceeds in two stages

-

( a ) The hydroge n which is not formed accordi ng to Mac ,

arthur s reactio n is i n the prese n ce of cya n ide of potassium

’
, , ,

water gold a nd oxyge n pote ntially nasce n t an d a molecule

, , ,

of oxyge n co mbi n es directly with 2 atoms of n asce n t hydro

g e n formi
,
n g hy d roge n peroxide while 2 atoms of gold dis ,

solve thus :
02 2 H, O 2A u
( CN ) 4 KC N 2 KA u 2

( b) N ext the hydroge n peroxide gradually dissociates i n to

,

hydroxyl a nd causes the solutio n of two m ore atoms of gold

, ,

thus
H, O, 2 Au 4KC N 2 KO H .

The sum of these two reactio n s is of course the same as , ,

that of the E llsne r reactio n which correctly expresses the e n d ,

result .

Whe n gold was rapidly dissolved in an aerated cya n ide

solutio n Bod lae n de r was able to detect as much as
, per
ce n t of the hydroge n perox ide required by reactio n ( a ) and ,

as reactio n ( b) had probabl y already set i n this re nders th is ,

expla n atio n extremely probable .

E xpressed in terms of the io n s reactio n s ( a ) and ( b) be ,

come :

(a )

(5 )

The flow of io ns through the solutio n is the same as i n the

first case O n the whole the seco nd seems the more proba
.
,

1
Zt h ng w C h m
sc 896 5 83
r . a e . e .
, 1 , .
4 18 Ckris ty .

1
ble expla n atio n though either agrees wit h most of the facts , .

A ccordi n g to either of these views the n e w theory agrees

qua ntitatively with the results of experime n t but o ffers for ,

the first time a co n siste n t expla natio n o f its occurre nce It i s .

due to the sup e ri or e le ctromoti ve force of the oxyg e n or i n ca se , ,

they a re p re se n t to some othe r e l e ctron eg a ti ve i on s a s ( OH ) , ,

Cl Br ( e tc tog e the r wi th the capa ci ty of the g old for .

,

for m i ng comple x i on s wi th cy a nog e n .

If i n stead of havi ng the two e nds of the gold strip i m

,

m e rse d i n two sepa r ate cya n ide sol utio n s the strip is i m ,

me rse d in the same solutio n co n tai n i n g some dissolved ox y

1 Wh i le
h p p e r w a s i n p re a p p e r o n F r i w i ll i g e O x y d ation ( A uto oxi
t is a ss , a e
" -

d a ti on ) b y D r M n c h ot o f G o e tti n g e n h as a pp e a re d i n w h i h h h
, . a e x mi n d th e
, , , c e as a e

o x i d at i o n o f a l g n umb of ph n l d e ri a ti ve s u c h s t h o e u e d s d e e lo p e rs
ar e e r e o v s, a s s a v

i n ph oto g ph y O n of t h e d e iv ati v e s ox an th an l w s p a rti c ul a l y w ll

ra . e se r , r o , a r e

ad p te d to g i v
a q u n t t ti r s ul t a nd h e w
e ab l e to p
a e t h t fo e e y m l e c ul e
1 a ve e s, as rov a r v r o

of o x y ge n b be d m l e ul of h y d o g n i n th e ox nth ran l w a s oxi d i e d and a

a so r a o c e r e a o z ,

m ol e c ul of h y d oge n p e ox id e w s fo m e d
e r r a r .

R p re s e n ti n g t h e o g n i c r di
e l by R an d th e oxan th r n l b yR HQ h e as s ume s
r a a ca , a o ,

t h at t h e r e c tion t k e pl c e a s f ll ow :
a a s a o s

11 1-12 02 R 11 20 9 .

The or g
l i f u n stab l e i s f r qu e n tl y sti ll fu rth e r ox i di e d i n a s e c on d
a n i c rad ic a , , e z

re ac ti on b y t h h y d o g n p r xid t hu s f r m e d
e r e e o e o

I t w o ul d a pp e th t i mi l ac ti n n s u e i n t h e r u ti n g of m e ta l s i n d a mp i
ar a s ar re o s e s a r.

T h r u s ti n g of i on
e in c e t c i s w o rt h y of t h o ough st u d y i n t h e l i gh t o f th e n e w
r , z , r

i de as .

It w o ul d se e m t h at
m od n e l troc h e mi l vi e w s n c e itate a r e tu rn i n
th e er e c ca e ss ,

p rt at l e st to th i d a f B e e li u s n d S h oe nb e i n Th e y s uppos e d th t th s a me
a a . e e s o rz a c . a e

e l e m n t w a s a t ti m s p o i ti v l y
e nd t ot h r ti m s n e g a ti v l y e l c t i fi e d
e s Th i s a p e , a a e e e , e r .

p e a s to b e a on se qu e n c e of th e n w i e w a l so For i f w e re g a rd th e o xy ge n m ol e
r c e v .

c ul e 0 2 ( : t ) a l c t i a ll y n e u t a l t h is c n n l y b e th e c s e w h n n e f its to m s
s e e r c r , a o a e o o a

h a s a d ou b l e p os i ti n d t h e o th n e qu a l n e g tiv e c h a r g e
ve a B th tt a tio n of e r a a . y e a r c

th se c h a g e t h m l e c ul e m y b r g a d d s b i n g h e l d to g e t h e
e r s e o Its r l c om a e e r e a e r. e a

p sition t h e n w oul d b e 0 (
o O (+ O n t h e ot h e h a n d t w to m o f x y g e n r , o a s o

i n th e e l e m n t l s tate w o ul d b e i mi l l y e l t i fi d w it h n g tiv e e l e c t i ity t hu s

a e s ar ec r e e a r c ,

O( 0( an d w o ul d c n se qu n t l y re p e l a h ot h e H e n e to c h a n g e n o e e c r. c , a

o x y g e n m ol c ul e i n to tw o o x y g e n a to m s w o ul d r e q u i r e f u r u n it o f n e ga ti v e e l e c
e o s

t r i c i ty .

O n the h e r h a nd th e h y d o g e n m ol e ul e w o ul d b e c o mp o d a follow s
ot , r c se s

n d to c h a n g e i t i n to tw o h y d o g e n ato m s
a nd w o ul d re r a

qui re tw o u n i ts oi p o iti e l t ri ity s ve e c c .

I t w o ul d a l s o se e m n e c e a ry to s s m e t h at t h e r e i s
u n i n h e r n t t n d e n c y i n th e
ss a a e e

ox y g n m l e c ul e (d u p h a p s to so m p ul i a ri ty f h p or o lum e ) to as s um e
e o e , e r , e e c o s a e v

n e g ti e an d i n t h e h y d rog e n m o l e c ul
a v . to s um e p o i tiv e e l e t i i ty i n d i sso i a e a s s c r c c

ti n g .

I t w o ul d a l so a pp r a s i f a di ff e e n t re s ul t o ugh t to b e p od u e d w h e n n e u t a l
e a r r c r

h y d og n m ol e c ul e s c mbin e w i th a n e ut l o xy g n mo l e c ul f o m th t w hi c h re
r e o ra e e . r a

s u l ts f o m t h e c m bi n a t i n o f p o i ti v e l y
r o l e c t i fi d h y d g n tom w ith a n e u t l
o s e r e ro e a s ra

ox y g e n m o l e ul e Th i s m ay b e th e k e y to th e fo m tion ofwate r i n t h e on e c a se a n d
c . r a

h y d og e n p e r xid e i n th e ot h r
r o e .
420 Re vie ws .

called selective a ffinity O f dilute cya nide solutio ns for gold ,

the o nly commo n metal that shows any i ndicatio n of such

favorable actio n bei n g copper
6 It is probable that i n the abse nce of exter n al e le c tro mo
.
,

t 1ve forces an aerated c y a n 1d e sol ut1o n less tha n

,
T ’

per ce nt is without actio n o n metallic gold

, .

7 That for all practical purposes an aerate d cya n ide solu

.
,

tio n of less tha n per ce nt is without actio n on metallic ,

gold .

This study has led appare n tly far afield fro m the practical
side O f the cya n i d e process yet I hope that it may be of ser
vice i n at least calli n g atte n tio n to the work of others who
have toile d for ma n y years i n attempti ng to clear up some of
the most subtle questio n s that have ever taxed the huma n
mi n d for I am firmly co n vi n ced that i n the lo n g r u n such
, , ,

work is always of the greatest practical service In these .

days the wor d s of Ostwald have certai n ly come true

,

The scie n ce of to d ay is the practice of to morrow -

.

RE VI E WS .

T H E E P E R I ME N TA L ST DY O F G A SE S A n ac c o u n t o f t h e e x p e r i m e n
X U .

t a l m e t h o d s i n v o l v e d i n t h e d ete r m i n at i o n o f t h e p ro p e r t ie s o f g as es
a n d o f t h e m o re i m p o rt a n t r e s earc h e s c o n n e c ted w i t h t h e s u b ec t
j .

By M O R R IS W T R A V E R S; D SC
. M ac m i ll an C o 1 90 1
. . . .

We are but j ust begi n n i n g to realize the existe n ce of mat

ter devoid of che mical pro p erties which seems to have bee n ,

predesti n ed fro m the begi n n i n g of thi ngs n ever to e n ter i nto

combi n atio n T hese eleme n ts for eleme nts they see m to be
.
, ,

whi c h we n t i n to the d iscard so to speak d uri n g the pro , ,

cess of cosmical evolutio n have either remai n ed free i n the ,

earth s atmosphere or else h ave bee n locke d u p as mecha n ical

’
,

i n clusio n s i n certai n mi n erals .

Those which have bee n discovered up to the prese n t time

are all gaseous but there seems to be n o reaso n why we may
,

n ot suspect the existe n ce of i n ert substa n ces which are either

solid or liquid u n d er ordi n ary co n d itio n s P ossibly the mi n ute .

traces of i n soluble residue which are left over i n certai n m i n

”
eral a n alyses and d escribed as probably silico n or doubt
,
”
less rho d ium w ill bear looki n g i nto It was the small i n .

soluble residue i n a certai n gas reactio n that fur n ished the

 Re vie ws .
42 1

first c lue to the existe n ce of this i n teresti ng class of eleme n ts .

T he separatio n an d puri ficatio n of substa n ces of this n ature

must clearly be accomplished by physical mea n s a n d the two ,

physical processes ge n erally made use of for the sepa

ratio n of dissimilar s ubsta n ces are crystallizatio n and frac ,

t io n al distillatio n Fortu n ately the great adva n ces which

.

have bee n ma d e d uri n g the last te n years i n the methods of

g etti n g extre mely low temperatures make the applicatio n to ,

gases of the process of fractio n al d istillatio n a n d eve n crys

Mr
,

t al l iz ati o n almost as simple as it is i n the c ase of liquids

, . .

Travers has give n us a very satisfactory ha n dbook o n the sub

j c e t of the experime n tal stu d y of gases which will be fou n d ,

extremely useful to every chemist an d physicist It is pro .

fu se ly illustrated a n d an u n usually large amou n t of sp ace is

,

give n to ma n ipulatio n a circumsta n ce whi c h will make every

,

experime n ter grateful to the author .

N early 1 00 pages at the start are devote d to mercury

, ,

p umps sto p cocks various forms of apparatus use d i n stor

i n g tra n sferri n g a ii d measuri n g gases metho d s of prepari n g
, ,

, ,

pure gases a n d the devices n ecessary to the ha n dl i ng of

,

small amou nts of rare gases to th e best a d va n tage .

The chapter on the measureme n t of volume an d the o ne ,

followi ng i t o n gas a n alysis will be fou n d of especial i nterest ,

to chemists The author recomme n ds the use of the sipho n

.

burette u n less a large n umber O f a n alyses are to be made .

With this piece of apparatus which a n y o n e with a rud i me n ,

tary k n owledge of glass blowi n g c an co n struct fo r himself the

-
,

complete a n alysis c an be ma d e the reage nts bei n g kept in ,

ordi n ary bottles i n stea d of i n the somewhat complicated

pipettes d escribe d by H empel an d others The method seems .

to be especially a d a p te d to laboratories provide d with a limi

t e d equi p me n t .

In brief i t co n sists i n the i ntro d uctio n i n to a tube fille d

,

with mercury an d i nverte d over a j ar of the same fluid of a ,

small qua n tity of t he gas absorbi n g reage n t The gas is the n

-
.

allowed to bu bble up i nto the tube from the graduated sipho n

burette A fter the absorptio n the residue is d raw n back i n to
.

the pipette a n d its volume recorded The same process is .

the n repeated with the other reage n ts the fi n al explosio n be ,

i n g made i n the same i n strume n t by m ea n s of eudiometer

electrodes seale d i n to the top of the gra d uated tube The .

simplicity of the method is its stro n g recomme n datio n al ,

though as the author says the O e tte l pipettes will probably

, ,

be fou n d more co n ve n ie n t i n the case of commercial a n alyses .

Followi n g this we have a n i n teresti n g accou n t of the i n ert

gases heliu m argo n n eo n krypto n an d xe n o n and the
, , , , ,
42 2 Re vi e ws .

methods by which they were isolated This subj ect is treated .

very explicitly if the experime nter wishes to collect a small

amo u n t of argo n to fill a vacuum tube or prepare a large -
,

qua ntity for the i n vestigatio n of its physical properties the ,

best method for each case is give n .

The author n ext takes up the determ i n atio n of gas d e n ~

sity a n d the relatio n s betwee n temperature pressure a n d

volume Followi ng this comes the subj ect of the liquefactio n
.

of gases i n which the developme n ts are traced fro m Faraday s

,
’

be nt tube to the rege n erative machi n es of L i nde and H amp

so n for the liquefactio n of air This chapter co ncludes with a
.

very complete descriptio n of the apparatus used by the author

for the liquefactio n of hydroge n and O fthe precautio n s which ,

m ust be take n i n its use A chapter follows o n the manip u

.

latio n of liquid gases their fractio n al d istillatio n an d their

, ,

use i n the mai ntai n i n g of co n sta nt low temperatures .

The author throws out freque n t suggestio n s to those e n

gaged upo n research work poi nti ng out ma ny of the gaps i n
,

our k nowledge which require filli n g such for example as the , , ,

e ffect of pressure on the compositio n of the distillate passi ng

over at a defi n ite temperature This questio n has bee n i nv e s
.

tig ate d i n the case of water and certai n orga n ic fluids but ,

p ractically nothi n g is k n ow n of the behavior of mixtures of

liquefied gases This is a questio n of vital importa n ce i n the
.

separatio n of g ases by physical processes .

The last part of the book is d evoted to the determi natio n s

of vapor pressure and the critical co n sta n ts the specific heat
-
,

of gas e s and the phe nome n a of e ffusio n tra n spiratio n an d

, , ,

di ffusio n the closi n g chapter deali n g with the subj ect of spec
,

trum a n alysis with i nstructio n s for . the co n structio n filli ng

, , ,

and use o f vacuum tubes which will be fou nd helpful

, If .

on e h as but a cubic ce n timeter of a pure gas an d will fill a

vacuum tube with it an d the n recover all but the mi n ute trace
left i n the exhausted tube without co n tami n ati ng it with i m
,

purities in the mea n time it is importa nt to k now beforeha n d

,

exactly how to proceed an d exactly what precaution s to take

, .

The boo k co n tai ns a vast amou n t of i n formatio n and is ad

mirably adapted to the requireme n ts of stude n ts both as a ,

text book and as a guide to work i n the laboratory whether

-

eleme ntary or adva nced .

Sufli c ie nt space is give n to theory and experime nt to mak e

it i n teresti ng readi ng while the very large amou n t of i n for
,

matio n regardi ng ma nipulatio n makes it i nvaluable i n the

laboratory as a refere nce book
Me ntion should be made too of the admirably executed dia
.

grams We no n e O i us ever q uite get over the early co n tracted

.
424 Re vi e w s .

co nt ributi n g largely to the i n terpretatio n of phe n ome n a h ith

erto n ot u n d erstood It has throw n light o n so ma ny prob
.

lems i n chemistry that it has n o w become a n i n tegral part of

that scie n ce A n d it is recog n iz ed that n o chemist to day
.
-
,

scie n tific or tech n ical c a n omit physical chemistry without

,
”
losi n g a n esse n tial p art of his trai n i n g .

SA MML UN CHE MI SC HE R UN D C HE MI SCH TE C H N I SC HE R VOR TR XGE

G -
.

H e ra u sg eg ebe n v o n P R O F E SSOR DR FE L IX B A HR E N S VI Ba n d ;
. . .

1 2 H e ft U e be r fes te L Osu n g e n v o n Dr G u i sep p e B r u n i P ri v at d o

.
, .
,

c en t a n d e r U n iv e r s i tat B o l og n a D e u t s c h y o u D r E E B asc h
Wien Mi t 4 A bbil d u ng en 1 90 1 p p 5 5 Verl ag v o n Ferdi n an d
. . . .
,

. . . . .

E n k e St u tt g a rt
, .

This mo n ograph begi n s with a d iscussio n of the origi n O f

the co n ceptio n of solid solutio ns an d the n takes up th e ,

methods by which so lid solutio n s c an be forme d A very .

brief sectio n is devoted to the state o f molecular aggregatio n

of substa n ces i n the so lid co n ditio n an d the phase rule is then ,

applied at le n gth to the subj ect of solid solutio n s .

The seco n d portio n of the mo n ogr aph i s d evoted to the t e

l at ion s be t wee n the chemical co n stitutio n of s u bsta n ces which
c a n form solid solutio n s wi th o n e a n other This comprises .

both i n orga n ic an d orga n i c compou n ds an d discusses the ,

beautiful i n vestigatio n s of P icci n i G are lli C i am ic i an Ferra , , ,

ti n i an d others
, .

It is to be regrett e d that o n e of the most i mpor ta n t i nvesti

g a tio n s o n soli d so lu tio n s has n ot fou n d i t s way i n to this mo n o
graph K ii ste r has sho w n how it is possible to determ i n e the
.

molecular weights of p ure soli d s by mea n s of solid solutio n s ,

an d has furn ishe d us with the o n ly me t h od available for de

t e rmi ni n g th e molecular weights of solids This is i ndeed the .

most importa n t scie ntific applicati o n of the ideas worked out

by v an t H o ff co n cern i n g the existe n ce an d n ature of solid
’

solutio ns .

The author has i n creased the valu e of his work b y g ivi n g

refere n ce to the literature of his subj ect H c J . . . .

P a v srx a msc a a C HE MI E FU R A N FX N GE R V o n D R C H M VA N DE
M
. . . .
_

VE N TE R it e i n em V o rw o r t v o n P R O F DR H VA N T H O FF J
’
. . . . . .

Zw ei te A ufl ag e , bes o rgt v o n D R E R N ST C O HE N . A m s terd a m : 8 . .

L V a n L oo y ; L e i p z ig : Wil h el m E n g el m ann
. 1 90 1 p p 1 68 . . . .

The ap peara n ce O f the first editio n of this book has already

bee n n o ticed i n this Journ al ( Vol 19 . The tra n sla .
,

ti o n i n to E n glish was subseque n tly revi ewed ( Vol 2 1 .

,

a n d it n o w o n ly rem ai n s to call atte n tio n to the fact that the

s e co n d G erm a n ed itio n has appeared H c J . . . .

VO L . X XV I I JUN E , 1 90 2 . N o .

A ME R IC A N

Co n trib ut i on fro m t he C h e mi l L
s ca a bo ra t o ry of t h e Rm l
P o y t e c hni c Inte ri m

MP H O R I C
.
XX .
—
CA A CID .

[E L E VE N T H PA PE R ]
C ON F R I MA T I O N OP B R E D T S FO R
’
MUL A SO ME D E R IVA T IV E S
OF I N A CT I VE C A MP H O R I C A C I D .

BY WIL L MA N
IA . o r ri s A N D A U ST N M P TT E SON
I . A R .

Some time ago prepared syn thetically the 2 3 3

on e of us
1
.
,

t rime t h y lc y C IO pe n t an o n e an d proved it to b e ide n tical w ith a

keto n e prepared fro m d ihydro fi campholyti c acid This was - -
.

the first sy n thesis of a cycli c derivati ve of camphor a nd con ,

fir me d th e vi e w previously expresse d by Bla n c as to the stru c

ture of fl campholytic a cid I n the sam e co nn ec tio n the
-
.
,

O pi n io n was expre ssed that the relati o n betwee n a c a mp h0

’
-

c is t ra n s c a mp h o l y t i c aci d ) a n d fl campholyti c
”
lyt i c acid -

c i sc a mp ho l y t i c acid
”
acid ) is o n e of stereo isomerism .

L ater fu rther ev i d e n ce po i n ti n g i n the same d irectio n h as

,

R esults obtai n ed however by K e rs hbau m

3
be e n furn ish e d .
, ,
1 Thi J UR N L 3 3 s O A , 2 , 1 0 .

L oc . cit , p . 1 34 .

N oy e s an d P h i lli ps Th i s J O UR
: N AL . 2 4, 2 85 ; N oy e s a n d Bl an c h a rd : Ibid .
, 26 ,

27- 27
42 6 N oy e s a nd Pa tte rson .

l ”
an d T ig g e s
by Bla n c a n d by L apworth are quite i nco nsi s
, ,
2

te n t with this co nclusio n and poi n t to the followi ng relatio n

betwee n the two acids

c c co, H C Hs C c o, H
lH
— — —
C: —

C ,
C H,
I
C H, —
C= CH \C
3
-
GH 2
C H,
a -
C a m p h o lyti c ac id . B C a m p h olyt i c
- a c id .

A ccor d i ng to these formulas the tra n sformatio n of the a to ,

the fi acid is accompa n ied by a tra nsfer of a methyl group

-

from the a to the fl positio n as well as by a shifti ng of the -

,

double u nio n A n e w and appare n tly a very decisive proof

.
, ,

that such a tra nsfer occurs has n ow bee n obtai n ed .

‘
I n the last paper the preparatio n of dihydro a campholytic - -

acid was d escribed This aci d has n ow bee n carried through .

the same series of tra nsformatio n s which w ere some time ago
applied to the dihydro fl campholytic acid ( d ih y d roc isc am
5 “
- -

p holy t ic acid or d ih y d ro isol au ron ol i c These

tra n sformatio n s are
CO, C , H5
C8H15 C 02 H H H

C, H ,, O H

It seems u nn ecessary to repeat the details of the vario us

steps as they were all carried o ut esse n tially as with the iso
meric acid The sha ki ng of the ester of the a bro md i hy d ro
.
-

campholytic acid with an aqueous solutio n of barium hy

°
d ro x id e was co n ti n ued for t e n days at a temperature of 40 to
a n d the decompositio n was the n still far fro m complete .

The sap o n ific atio n a nd decompositio n were fi n ally completed

by boili n g the mixture with an upright co nde n ser for some
1 Be r. d . c he m . Ge s .
, 33, 2 9 38 .

3 C mp t
o . re n d .
, 13 1 , 803 .

3
J Ch m
. e . So c ( L on do n ) 7 9 ,
.
,
1 2 84 .

4 Th i s J O U R N A L , 2 6, 2 88 .

5 I bid 22 262
.
, , .
42 8 N oy e s and Pa tte rson .

group i n the tra n sformatio n of either campholytic acid i nto

the other This leads to the followi n g formulas for the ne w
.

k eto n e and for a c amp holy tic acid ~

c: o OH c o, H

C H3 C H OH, — —
OH, c == C H
3 Tr i me t h y l c y c l o p e n t a n o n e
-
.
a- C am p h o lyt ic ac i d .

This result fur n ishes as has bee n stated a ne w and ver y , ,

positive co n firmatio n of Bre d t s formula ’

.

Befor e leavi ng this part O f the subj ect it seems worth while
to poi n t out that the work do n e with the campholytic acids
has brou g ht o ut certai n facts which ca nn ot be readily ex
plai n ed by the curre nt stereochemical theories an d which
seem i n part at varia n ce with those theories
, , .

First the additio n of hydrobromic acid to a campholytic

,
-

acid should give rise to two co n figuratio n s accordi n g as the '

acid adds itself o n the one side or the othe r of the pla n e
of the ri n g In o n e of these the bro mi n e an d carboxyl
.

” ”
would be cis i n the other tra ns B ut it has bee n
, .

show n m a previous paper that a si n gle co nfiguratio n is al

1

most or quite exclusively formed This m ust be the cis

”
form if camphoric acid has the
,
cis co n figuratio n as is ,

usually supposed Seco n d the tra n sformatio n s of a campho .

,
-

lytic acid to fl campholytic acid an d vi ce ve rsa are supposed

-
, ,

to occur through the followi ng steps

H H

C H, —
c -
c —
c o, H C H, —
c C —
C O, H

C H, C H, C H, C H,

C H, —
c C H, -
C

Br
a -C a m p h o l y t ic ac id H y d robro m id e o f a -c a m
’

p h o l y t ic ac id .

,
1 Th i s JO U R N A L , 2 4, 29 1 .
 Ca mphori c A cid .
42 9

C H, —
c c -
cO , H C H, —
C —
C —
C O , II
—

C H, C H, Br C H,

C H, —
. c OH , —
c

C H,
H y d robr o m i de o f fi c am -

p h ol y t i c ac i d .

C H, —
c c -
co, H

C Hs —
C

C H3
B C am p h olyt ic
-
a c id .

A exami n atio n of these formulas shows that the bromi d e

n

a nd carboxyl of the hydrobromide of fl campholytic acid are -

ci s whe n it is derived i n this ma nn er fro m cit campholytic acid -

,

while they should be tr a n s if derived directly fro m the fi cam -

p holy ti c acid A ssu mi n g camphor a n d camphoric acid to

.

have the cis co n figuratio n n o co n siste n t expla n atio n of the ,

facts alo n g such li n es seems possible .

While the stereochemical theories have bee n very success

ful i n explai n i n g O ptical isomerism a n d i n predicti n g the nu m
ber of possible i so mers they occasio nally brea k dow n co m ,

p l e te ly whe n the attempt is made to apply them logically to

questio n s of the above des c riptio n .

T he work here describe d was already practically complete

1
whe n an article by Bla n c appeared i n which he describes the
preparatio n of a keto n e through the followi ng series of co m
pou nds :
H C SH MC H 2 C O , H C , H, 5 C H B1 C O, H
a -
C a m p h o l e n ic
ac i d .

1 Bull . So c . C him .
,
2 7 , 7 1.
4 30 N oy e s a nd Pa tte r son .

° °
The oxime of this keto n e melts at 1 0 7 to 1 0 8 a nd is di ffer
e nt fro m the oxime O f the keto n e fro m dihydro fl campholytic - -

acid an d on this fact Bla n c bases the co n clusio n that it must

,

have a di ffere n t structure But the a c amp hole nic acid is O ptic .
-

ally active and if that activity co nti nues through the series the
,

k eto n e obtai n e d by Bla n c might be so far as the evide n ce ,

goes simply o ne of the active compo n e nts of the racemic

,

keto n e O btai ned from dihydro B campholytic acid The proof - -

.

is therefore i n co n clusive while the evide n ce give n here is

, , ,

based o n work with racemic compou n ds throughout a nd leads ,

to a co n clusio n which seems to be very positive E xcept on .

the suppositio n that Bla n c s keto n e was i n reality active it ’

,

seems d iffi cult to reco n cile the fact tha t his oxime melts at a
1 ° °
temperature 3 to 4 higher tha n ours .

I n previous papers the O pi n io n has bee n expressed that

a campholytic acid has a stru c ture i n which there is n o as m
y
-

m etric carbo n atom and a stereomeric structure which would

accou n t for its O ptical activity was p rO p o se d This form ula .
2

5,
of course no lo n ger te n able , .

f In a cti ve Ca mphor De r i va ti ve s o .

A short time ago the atte n tio n of o ne of us was called to

the fact that the A mp ere E lectro C hemical C ompa n y of New -
,

York has bee n prepari ng to ma n ufacture artificial camphor

, .

The details of th e process are n ot yet public but the starti n g ,

poi nt is of course turpe n ti n e Through the ki n d n ess of the

, , .

compa n y we have bee n fur n ished with about 4 00 grams O f

their product It is ge n ui n e i n a cti ve camphor It melts at
. .

° 3
17 6 a n d is O ptically i n active O n oxi d atio n with n itric acid .

it co n ducts itself i n the same m a nn er as ordi n ary camphor

an d yiel d s i camphoric acid melti n g at a n d this by
-

1 Si n c e w ri ti n g th e mpl of th i o xi m w h i c h D r
a b ov e we h av e re c e iv e d a sa e s e , .

Bl n c h as v e y k i n d ly n t us W e fi d th t i t m l t a b o u t 3 h i gh e th n ou o xi m e
a r se . n a e s
°
r a r ,

b ut t h t m i x t u e fth e t w o m e l ts p ti ll y at t h e m l ti n g poi n t f our o xi m °

a a r o 3 ar a e -
o e , 10

to W n t w a e t h a t a n y on e h s e
e a re o d e d ob e
a rat i n s s to th m e l ti n g; a r cor s r v
o a e

p in t o ft h e m i x tu e of a r m i o mp o u n d w it h n e o fi ts ac tiv e o mp e n ts b ut it
o r ac e c c o c on ,

w o ul d e e m t h at t h e e b s
s ti n g b t w it h th e s uppo iti on th t D Bl n c s
s o e rv a o s a re e e s s a r . a
’

o xi m e i c ti e w h i l e o u s i s
s a v ac m i c I t i s l o p o i bl e t h t o u r i s n ot qu i te pu e
r r e . a s ss a s r
.

D r Bl n w i te u s th t h e w i ll e p e t th e p e p r ti n of hi s k e ton e s ta rti n g w ith

. a c r s a r a r a a o ,

i n ac ti e mphv ca or .

Th i J O U R N A L 2 4 2 87
2 s , , .

3 I bi d 16
.
, , 5 01 .
43 2 N oy e s a nd P a tte r son .

asbestos , an d precipitati n g by dilutio n with 2 or 3 volumes o f

water .

i -
fl Ca mphora midic
- a cid , (3,,H 1 prepared as d e
C O N H,
scribed crystallizes i n n ee d les which melt at
,
The ac
tive isomer melts at 1 8 2 to gram of the acid °

re q uired for its n eutral izatio n cc O fN /

1 0 potassium h y .

d rox i d e Theory requires . cc .

i D ihydroa mi n oca mp holy tic

-
a ci d , C SH 14
< N H2
was prepared

by exactly the same process used in the preparatio n o f th e

2
active isomer It c rystallizes i n leaflets an d so closely resem
.

bles the active bo d y as scarcely to require a n e w descriptio n .

The chlor opl a ti n a te is easily soluble The a n hy d r i de .

,

8
melts at the same temperature as the melt
3
i n g p oi n t
o
of the a n hy d ride of the active acid .

i D i hy dr ohy dr oxy ca mp holy tic A ci d

-
Whe n the ami n o acid is —

treated with 0 5 mol e cule of s ul ph uric acid an d 1 molecule o f

so d ium n itrite it d ecomposes i n a ma nn er exactly simil ar to
‘
that of the decompositio n O f the active bo d y yieldi n g i d i by ,
-

d roh y d ro x y c amp hol y ti c acid an d racemic a campholytic acid -

.

The hydroxy acid melted at The melti ng po i n t was -

give n i n our last paper as but a specime n of the O l d acid

was n ow fou n d to melt at a n d a mixture of the t wo acid s

melte d at exactly the same temperature The ide ntity of t he .

two is therefore beyo n d questio n The melti ng poi n t her e .

-

give n was corrected by checki n g the thermometer with boil

i n g a n ili n e
The ti er ca mpholy ti c a cid was obtai n ed i n small amo u n t as a
-

liquid Its a mide melted at

. the same temperature fou n d
for the melti n g poi n t of the ami d e of the acid prepared from-

fi cam pholytic acid as described i n o ur last paper an d a

-
, ,

Th i J U N L 6 3
1 s O R A , 1 , 1 0.
1 Ibi d .
, 16 , 5 03 .

3 I bi d .
, 16 , 5 04 .

4 I bi d .
, 17 , 42 4 .
 F re e z i ng p oi n t -
o f Wa te r 4 33

mixture of the two amides melted at the same temperature .

‘

W armi n g with dilute sulphuric acid ( I 1 ) co nverts the acid

i nto fi campholytic aci d
-
.

TE R R E H A UT E IN D
A p il 2 19
,

r ,
02 .

T HE L OW E R IN G O F T HE FR E E Z I N G P O I N T
WA T E R P R OD U C E D BY C O N C E NT R A T E D
SO LU TI O N SO F C E R T A I N E L E C T R O
L Y T E S A N D T H E C O N DU C ,

T IV IT Y O F SU C H
SO L U TION S .

B Y H A R R Y C J O N E S AN D F R E D E R IC K H G E T M A N . . .

We had hope d to carry this i nvestigatio n much farther be

fore publishi n g the results O btai n ed but a paper which has ,

2
j ust appeared by W Biltz beari n g upo n the same subj ect , .
, ,

makes this prelimi n ary publicatio n n ecess ary Sin ce the .

mi n imum i n the molecular loweri n g O f the freezi n g poi n t of -

’
water pro d uced by a large n umber of electrolytes was dis
, ,

covere d for most of these substa n ces i n this laboratory and ,

systematically stu d ie d for th e first time by Jo nes and C ham

3
bers it seemed reaso n able to e x pect th at we would be give n
,

a fai r amou n t of time to exte n d our i nvest igatio n s i nto this

fi el d which we h ad e n tered This seeme d all the more prob .

able i n that Jo n es an d C hambers st ated at the close of the 4

first i n vestigatio n of this problem that we propose to exte n d

this i nvestigatio n to a much larger n umber of hygroscopic
s ubsta n ces to ascertai n whether there is a n y relatio n bet wee n
,

this property a n d ab norm al freezi n g poi nt loweri ngs such as -

,

”
those recor d e d i n this paper .

5
A nd C hambers an d Frazer worki ng with Jo n es co n cluded , ,

their paper as follows : It seems to us quite possible that

work of the ki n d here described may help if o nly a little , ,

1 Bl n c gi t h m e l tin g p i n t a s
a ve s O u r a m i d e i s e v i d e n t l y n ot qu i t e pu re
e - o ,

b ut w h e n m i x e d w i th a s mpl of D Bl n s mid e w h i h h e k i nd l y s e n t us th e
a e r. a c
’
a , c ,

mi x tu re m e l t d at T h tw r t h e e f o e i d e n ti c a l
e e o a e , r r ,

1 Z t sc h ph y s C h e m 4 0 85
r . . . , , 1
3 Th i s J O U R N L 2
3 89 A , ,

1 Ib d p 15
z
’

.
, . 0 .

5 I bid 2
.
, 3 , 5 20
434 jon e s a nd Ge tm a n .

towards the u ndersta n di n g of co n ce n trated solutio n s an d we ,

may thus be able to fi nd out why it is that the laws which ob

tai n for dilute solutio n s do n ot hold in the m ore co n ce n trated .

It is with this hope in mi n d that further work alo n g the above

”
li n e will be do n e .

The i nvestigatio n of which a prelimi n a ry accou n t is here

,

recorded has for its obj ect the stud y of a large n umber of
,

electrolytes i n water to determi n e whether the mi n imum i n

,

the molecular loweri n g of the freezi n g poi nt was a ge n eral -

phe nome no n or whether it was m a nifested o n ly by certai n

,

substa n ces We also desired to measure the freezi n g poi n t

.
-

loweri n g produced by solutio ns of electrolytes of su ch great

co n ce ntratio n that the ordi n ary Beckma nn thermometer could
n o t be employed We therefore had two large Beckma nn
.
, ,

°
therm ometers co n structed O n e of these had a ra n ge of 1 2 .

a nd was divided i n to fi f t ie t hs of a degree a n d the other had a ,

°
ra nge O f 2 5 an d was divided i n to twe ntieths of a degree .

The former was used for the more d ilute solutio n s the latter ,

for the more co n ce ntrated The apparatus employed was e s .

s e nt i all y that devise d by B eckma nn The freezi n g mixtures .

-

used i n this work were sodium chloride an d ice an d calcium ,

chloride and ice Several acids o n e base an d a n umber of

.
, ,

salts have bee n studied as w ill be see n from the followi n g re ,

su lt s .

C olu m n I co ntai n s the co n ce n tratio n s of t he solutio n s i n

.

terms of gram molecular n ormal I I is the observed lower

-
.

i n g of the freezi n g poi n t of water I I I the correctio n due to

-
.
,

the separatio n Of ice IV the corrected loweri n g of the .

,

freezin g poi n t a n d V the molecular l oweri n g of the fre e z

-
.
,

i n g poi n t
-
.

I n some cases two i n oth e r cases three determi n atio n s of

, ,

the freezi ng poi n t of a solutio n were made The mea n of the

-
.

several values is give n i n every case .

4 36 [ones a nd Ge tm a n .

N i tr i c A cid ( Con ti n ue d )
II . I II .

0 0

Mea n ,

Mea n ,

4 -5 5 7

4 -6 5 9

Mea n ,

Sulp hu r ic A ci d .

H SO
.
, 4
III .

Mea n ,

Mea n ,

Mea n ,

39 7 0

Mea n ,

Mea n ,
 F re e z i ng p oi n t o f Wa te r .
43 7

Sulphuri c A ci d ( Con tin ue d ) .

II . III . IV .

Mea n ,

7 -44 2
7 4 44
7 4 42

Mea n ,

Mea n ,

Pota ssi um Hy drox ide .

KOH 56)
I II .

Mea n ,

Mea n ,

3 -8 7 5
3

Mea n ,

39 7 5
39 7 7
5 9 65

Mea n , 39 7 6
4 38 j
on e s a nd Ge tma n .

Pota ssi um Hy drox ide ( Con ti n ue d ) .

11
. I II . IV .

Mea n ,

1 4 -5 4 6

4 4 98

Mea n ,

Ca lci u m Chlor ide .

C aC l, (1
II I .

Mea n , 54 73

Mean ,

7 -5 4 7
7 -
5 3 1

Mea n ,

17 9 73

Mea n ,

Stron ti um Chlor i de .

SrC l ,
III .

Mean ,
 j
on e s a n d Ge tma n .

Sodi um N i tra te ( Conti n ue d

11. 111 . IV .

O 00 2

Mea n ,

3050

Mea n , 3 -5 3 2

34 97

Mea n ,

3 -3 7 2
3 -3 7 0

Mea n ,

1 . 669

3 -34 8

Mea n , 3 8 45

3 -1 9 7
3 1 99

Mean , w as
0 00 1

Mea n ,
13

30 7 3

3 -0 5 5

M an
e ,
 Fr e e z i ng poin t qf
-
Wa te r .
44 1

Sodi u m N i tr a te ( Con tin ue d ) .

11
. 1 11 . IV .

Mea n ,

Pota ssi um N i tr a te .

KN O

0 0 0 .

Mea n ,
e

Mea n ,

38 7 0
3 -34 5

Mea n .

M7 7

Mea n ,

3 -1 7 5

3 -1 4 5

Mea n ,
44 2 [on e s a nd Ge tma n .

Pota ssi um N i tra te ( Con ti n ue d ) .

Mea n ,

Mea n ,

'

An e xa mi natio n of
the above tables will Show that a mi n i
m u m exists i n the molecular loweri n g of the freezi n g poi nt of -

all the acids the base a n d all the salts studied with the ex
, ,

c e p tion of two . In potassium n itrate an d so dium n itrate t he

molecular loweri n g decreases with the co n ce n tratio n from the
most dilute to the most co n ce n trated solutio n studied show ,

i ng n o trace of a mi n imum at an y dilutio n These facts will.

be show n more clearly whe n the results are plotted as curves ,

which will be do ne whe n the work is published in full

—

H avi ng fou n d a mi n imum in the molecular loweri ngs of the

freezi n g poi n t of water as produced by such a n umber of elec
-

t rol y t e s we determi n ed to study the molecular co n ductivity

,

of co n ce ntrated solutio ns of these substa n ces especially at ,

'

those co n ce ntratio n s where the fre e z in g poi n t mi nimum ma n i

-

fe ste d itself .

The resista n ce to the passage of the curre n t ofi e re d by such

co nce n trated solutio n s is so small that a Special form of c e ll
was co n structed i n which the plates were not large an d
, ,
,

placed a co n siderable dista n ce ap art This cell will be de

.

scribed more i n detail i n a later publicatio n .

The results obtai n ed are give n in the followi n g tables 0 .

represe n ts the volume of the solutio n th e molecular

co nductivities of the solutio n s at zero degrees
4 44 Gilp i n .

We Shall n ot discuss these results i n this co n n ectio n but ,

reserve an y th eoretical co n si d eratio n s for a later and fuller

p ublicatio n .

We w ish to state that we are exte ndi n g these i n vestigatio n s

to a much larger n umber of electrolytes and to a n umber of ,

sol ve n ts alo n g the li n es which we have bee n i n vestigati n g i n

,

this laboratory .

C HE M L L IC A T Y A BO R A OR
JO H N SH O P K I N S U N Iv
,

.
,

A p r1l , 19 02 .

A C TIO N OF P H O SP H O R U S P E N TA CHL O R I D E ON
ILI NE AN .

B Y J E LL TT G . IO IL P 1 N .

In a previous paper i n this J O U R N A L several products

l

formed by the actio n of phosphorus pe n tachloride on a n ili ne

an d its salts were d escribed It was Show n that phosphorus .

pe n tachloride a n d a n ili ne hydrochloride whe n heated to ,

gether formed a compou n d whose compositio n could be re p re

,

se n ted by the formula P C 13 ( C GH5 N ) while the substa n ce ,

for med whe n the chloride is treate d with a n ili n e itself at ,

ordi n ary temperatures was The amou nt of

,

carbo n i n the latter com p ou n d could n ot be determi n ed by the

usual method as the substa n ce whe n heated was partly
, , ,

cha nged i n to a black mass which still co ntai n ed carbo n but ,

i n an extremely stable form E fforts h ave bee n made to de .

termi n e the exact n ature of this sub sta n ce but the results oh ,

t ai n e d lead to the co n clusio n that it is n ot a si n gle defi n ite

substa n ce but a mixture Whe n the compou n d .

is heated it is decomposed formi n g a n ili n e and other products ,

which escape as gases an d a black porous mass resembli n g ,

coke If this black residue is heated red hot i n a porcelai n

.
,

crucible it slowly volatilizes with decompositio n but the

, ,

mass shows n o te n de n cy to melt eve n at that temperature , ,

a nd the separate particles remai n dry a nd retai n their i n d i

vid ual form .

1Th i J U N L 9 35
s O R A , 1 , 2 .
 A cti on of Phosphorus P e n ta chlor ide on A n ili n e .

Wh e n the crucible w as heated

directly in the flame of the
bur n er so that the gases prese n t in the flame e nveloped the
crucible a flam e similar to that of burn i n g phosphorus was
,

observed aro u nd the e d ge of the crucibl e an d a cover placed ,

o n it soo n became covered o n the i n si d e with an oily liquid

,

which proved to be phosphoric acid Further experime n t .

showed that the oxi d e of phosphorus formed by the bur n i ng

,

of the phosphorus which had bee n set free combi n ed with the ,

water vapor i n the flame to form the acid fou n d In order to .

avoid co n tact of the gases i n the flame with the co nte n ts O f

the cruci ble the latter was placed i n a circular ope n i n g in an
,
’

asbestos bo ard which allowed the substa n ce to be he ate d with

out bei ng e n veloped in the flame This led to a more thor
.

ough study of the substa n ce and its decompositio n products -

,

in the course of which it was show n that besides phosphorus ,

n itroge n hydroge n an d carbo n were also prese n t

, , but that ,

specime n s of the same origi n al substa nc e whe n heated for ,

differe nt le n gths of time sho wed lack of u n iformity and di ffer

,

e n ce of compositio n .

Whe n the substa n ce was heated i n a small porcelai n tub ;

i n a stream of dry n itroge n ammo n ia an d a volatile substa n ce
, ,

with an odor very similar to that of isocya n ides passed off as ,

gases wh ile a very light yellow pow d er which was pure phos
,
-
,

ph orus collected i n the fro n t e n d of the porcelai n tube and i n

,

the co n de nser co nn ected with it Similar products were also

.

formed whe n dry carbo n d ioxide gas was used i n stead of

n itroge n although appare n tly n ot so readily
, .

The phosphorus coul d be determi n e d qua n titatively by

oxidatio n with potassium hydroxide an d potassium n itrate
a n d precipitatio n as ammo n ium mag n esium phosphate an d ,

the n itroge n by the G u n n i n g modificatio n of the Kj el d ahl

method The perce n tage o f n itroge n dro pped from
. to
an d the n to per ce n t i n successive specim e n s take n
after heati ng the previous on e for from fiftee n to twe n ty
mi n utes .

Besi d es the substa n ces me n tio ned above two co mpou nds ,

whose compositio n c an be expressed by th e formulas

4 46 Gi lp i n .

a nd

have bee n obtai n ed by th e actio n of a n ili n e on phosphorus

pe n tachloride u n der differe n t co nditio ns .

A ll e fforts to repl ace the last chlori n e atom i n the pe n ta

chloride by the a n ilide group to form h ave
failed U p to the prese n t ti me no co nditio n s have bee n fou n d
.

u n der which all five of the chlori n e atoms could be replaced

by a n ilide residues nor could the chlori n e atom i n

be replaced by the an ili n e residue There was no actio n .

whe n the was heated i n a sealed tube with

a nili n e alo n e or with a n ili ne an d some substa n ce which would
combi n e with the chlori n e Jackso n and Me n ck e met with a
.

si milar diffi culty i n their i n vestigatio n of the actio n of phos

p h or u s trichloride o n a n ili n e a nd were also u n able to replac e

the last chlori n e atom .

The relatio n ship to phosphorus pe n tachloride of the sub

sta n ces thus far described can be expressed by the followi n g
formulas
P Cl

H CGHs)
'
Prepa ra tion f
o N

A bout grams of a n ili n e were dissolved in 2 5 0 cc of be n

10 .

ze n e and a n e q ual qua ntity of be nze n e was saturated at the ,

ordi n a ry temperature with phosphorus pe n tachloride Both

, .

solutio n s were the n well cooled a n d were kept SO while the

solutio n of the pe n tachloride was slow ly added to the a n ili n e
solutio n A fter sta n di ng for some hours the a n ili n e hydro
.
,

chlorid e w hich had separated out was filtered O ff and the

, ,

product obtai ned by the slow eva poratio n of the be n ze n e was

, ,

w ashed with boili n g water i n which it is e ntirely i n soluble to

, ,

remove any soluble phosphorus compou n ds a n d most of the

be nze ne an d the n crystallized from alcohol The substa nce
, .

thu s obtai n ed formed clear well d efi n ed crystals which c on

, ,
°
tai n no water of crystallizatio n an d melt sharply at 2 0 8 to
 Gi lpi n

gram substa n ce gave 0 0 3 2 84 5 gram N .

gra m substa n ce gave 0 0 34 1 2 7 gram N .

gram substa n ce gave 0 0 33 5 0 3 gram N .

gra m substa n ce gave 0 0 5 88 gram Mg P 2 2

07 .

0 187 1 gram substa n ce gave gram

gram substa n ce gave 5 gram
gra m substa n ce gave gram
C l ul t d f
a c a e or u
Fo n d .

1 . 11 1 . v .

A s the same di fficulty was e n co u n tered i n e fforts to deter

,

mi n e the amou n t of carbo n an d hydroge n as i n the other case ,

me ntio n ed above the compositio n as calculate d from the re

, ,

s u lts of the determi n atio n of n itroge n a nd phosphorus was ,

co nfirmed by d etermi n atio n s of the molecular weight made by

the boili ng poi n t method usi ng alcohol as a solve nt
-
, .

Su b s ta n c e
ms
.

G ra

Mea n ,

C alculated for 30 5

P r ep a ra ti on f P Cl ( N H
o ,

By the method used for the preparatio n Of the c hlo rphos

t e t ra n il id e which co n sisted i n a dd i ng phos
p h or u s pe n tachloride to a n ili n e at the ordi n ary temperature ,

washi ng the product wi th boili ng wate r an d after dryi n g , , ,

extracti ng a ny easily soluble m atter with cold alcohol a fe w ,

well d e fi n e d crystals were O fte n obtai n ed wh e n the solutio n

-

was allowed to evaporate Slowly These crystals had bright.

faces a n d sharp a ngles wh e h first removed fro m the solutio n ,

but upo n exposure to the air rapidly became dull a nd fi n ally ,

crumbled to a po wder A lthough a n ili n e a n d phosphorus

.
 f
A cti on o Phosp hor u s Pe n ta chl or i de on A n i l i ne .

pe ntachloride h ave bee n brought together in various propor

tio n s and u n der di ffere nt co n ditio n s of temperature in order ,

to produce this substa n ce i n qua n tity it has so far bee n i m , ,

possible to fi n d an y co nditio n s u n der which it is formed as

a nythi ng more tha n a by product i n very small qu a n tities
-
.

l; he best yield is obtai n ed whe n phosphorus pe n tachloride

’

is added to boili n g a n ili n e as lo n g as an y actio n takes place ,

but eve n the n the yield is very sm all o nly a few crystals be
,

in g formed whe n as much as 5 0 grams o f a n ili n e are used .

A s the formatio n of this substa n ce has n ever bee n n oticed

whe n phosphorus pe n tachloride acts o n the a n ili ne i n a cold
solutio n but o n ly whe n the actio n takes place at high tem
,

p e rature s it would suggest the possibility of the actio n bei n g

,

more complete if the substa n ces coul d react at high temper

atures A s however phosphorus pe n tachloride act s o n a ni
.
, ,

li n e to form P C 1( N HC GH5 ) , as soo n as they come i n co ntact ,

a n d further treatme n t with excess of ei ther substa n ce pro

duces n o actio n the possibility of co n trolli n g the co n ditio n s

,

so a s to i n crease the yield of the desired pro d u c t s eems very

slight .

A fter the solid formed by the actio n O f the phosphorus

,

pe ntachloride 0 11 the boili n g a n ili n e has cooled it is broke n

,

up an d boiled with water to remove all excess Of phosphor u s

co mpou n d s or a n ili n e The powdered a n d dry substa n ce i s
.

the n treated with a little cold alcohol which if it is allowed to ,

act for o n ly a short period dissolves out all of the easily solu
,

ble by product but o nly a small amou n t of the other pro d uct
-
, ,

which is prese n t i n very large excess .

The crystals which are formed by th e slo w evaporatio n of

this solutio n are picked out washed with alcohol a n d dried
, , .

It is n ecessary to pick out each crystal an d wash it wit h alco

hol to remove the other subst an ce w hich separates out firs t
,

a n d ofte n sticks to the large crystals O ne extractio n with

.

cold alcohol serves to remove all of the substa n ce prese n t i n

the mass The crystals must be kept i n a closed vessel over
.

alcohol i n order to preserve the luster of the faces as a few

mi n utes co n tact with the air so meti mes ma k es them dull
’
,
45 0 Gi lp i n .

owi ng to the loss of the alcohol prese nt as alcohol of crystal

l iz atio n . The powder O btai n ed by drivi n g out the alcohol
°
melts at 1 9 2 to The substa n ce c ry stalliz e s i n the mo no
cli n ic system an d exhibits a hemihedral habit The follow .

i ng co n sta n ts were calculated fro m the i n terfacial a ngles of

the u n it hem i pyramids an d u n it prisms
-

,
3 87 a b c
P la n es O bserved

p (111 ,
_
P ) 1

o (111 , P ) ,

a ( 1 00 ,
oo PE ) ,

b (0 10 ,
oo P do ) ,

m ( 1 10 , )
oo P ,

(2 2 1 , 2 P ) probably ,

z ( 1 2 0 oo Rz ) probably
,
.

It exhibits a perfect cleavage parallel to the orthopi n acoid ,

? ( 1 00 ) a n d an imperfect on e parallel to an orthodome

oo P o ,

probably P e n etratio n twi n s were obse rved i n a

n umber of cases the twi nn i n g pla n es bei n g either the cli n o
,

prism oo P 2 ( 1 2 O ) or the orthodome 2 P oo

The table on opposite page represe n ts the results O f a nu m
1
ber of meas u reme n ts
The followi ng figures illustrate the differe nt habits and
twi n n i ng laws observed o n the crystals

F ig . II .

1 I a m i n d e bte d to Mr . A . C Sp. e nce r fo r t h e c ry s ta llog ra ph i c me as u re me nts .

45 2
_ Gi lpi n

Fig . II I . Fi g I V
. .

F ig . V . Fi g VI
. .

Fig . v 11 . Fi g . V III .
 A ction o f Phosphor us P e n ta chlor i de on A n ili ne .
45 3

Fig I shows the combi natio n of the t wo hemi pyramids

. .
-

with the cli nopi n acoid while Fig I I co n tai n s i n additio n the
, . .

orthopin acoid The equal developme n t of t he pyramids p in

.
,

ac oid s a n d prisms gives a combi n atio n closely resembli n g i n

,

appeara n ce the rhombic dodecahedro n of the regular system .

Figs I I I an d I V represe nt crystals which are alike i n type

. . .

but di ffere n t i n habit Fig V represe nts a crystal which is

. . .

tabular parallel to the cli nopi n acoid an d i n which the faces b

an d a are very slightly developed In some cases as i n Fi g .
, .

V I a faulted appeara nce is n oted an d sometimes on e half is

.
,

smaller tha n the other an d i s place d o n the face ( a )

I n Fi g V I I i n dividuals twi n n ed parallel to the cli n oprism
. .

oo P 2
( 1 2 o ) are represe nted a n d i n Fig V I I I a proj ectio n of
, . .

a twi n with the orthodome 2 P 55 as the twi nn i n g pla n e .

A n alyses of a n umber of specime n s Of the substa n ce gave

the followi n g results
gra m substa nce lost o n heati ng gram , ,

per ce n t .

gram substa n ce lost o n heati ng gram , ,

per ce n t .

0 2 0 2 6 gram substa n ce lost o n heati ng gram , ,

1 0 6 1 per ce n t .

gra m substa n ce lost o n heati n g g r am ,

2
,

per ce nt .

0 4 8 7 3 gram substa n ce lost o n heati n g gram , ,

1 0 5 4 per ce n t .

gram substa nce lost on heati ng gram , ,

per ce n t .

°
gram substa n ce gave cc N at 1 9 an d .

mm pressure
. .

gra m substa n ce gave cc N at and .

mm pressure
. .

gra m subs ta n ce gave cc N at 1 1 and 7 6 3 mm .

°
.

pressure .

gram substa nce gave cc N at an d 7 5 5 .

mm pressure
. .

gra m substa n ce gave cc N at a nd .

mm pressure
. .
45 4 Gi lpi n

gram substa nce gave gram A g C l .

gram substa nce gave gram A g C l .

gram substa n ce gave gram A g C l .

0 1 5 7 1 gram substa n ce gave gram A g C l .

gram substa n ce gave gram A g C l .

gram substa n ce gave gram

gram substa n ce gave gram
gram substa n ce gave gram
gram substa n ce gave gram
gram substa n ce gave gram
0 0 88 2 gram substa n ce gave gram C O .
2

gram substa n ce gave gram C O 2

.

gram substa n ce gave gram C O ,

.

gram substa n ce gave gram C O 2

.

gram substa n ce gave 0 0 7 4 7 gram H O ,

.

gram substa n ce gave gram H O ,

.

Fo und .

4 -34
68 66
6 0 21 0 0 0 .

C l ul a c at e d fo r
P gC l N H C 5 H 5 ) 7 + 2 C 2H 5 0 H u
Fo n d .

C 2 H5 0 H 10 54
The low results obtai n ed i n the determi n atio n of the loss of
alcohol O f crystallizatio n were probably due to loss while the
crystals were bei n g dried a n d powdere d for heati n g as they ,

lose the alcohol very rapidly i n co n tact with ai r That the .

substa n ce give n o ffwas alcohol was clearly Show n by collect

i ng the liquid and testi n g for alcohol .

While this material is easily dissolved out of the origi n al

mixt ure by a little cold alcohol the pow d er obtai ned by de ,

hydrati n g the crystals is o n ly very slightly soluble i n cold

alcohol an d from the experime nts made appears to cha n ge to
, ,

P C I( N H C,,H 5 ) 4 whe n boiled with alcohol so that it is i mp ossi

ble to purify the substa n ce by recrystallizatio n .

JO H N S H O P K I N S UN IV
A p il
.
,

r , 90 1 2 .
45 6 L oche .

3 The relative solubility of compou nds of an eleme n t ( T 1)

.

the positio n of which is i n every respect far removed from

those of its a n al og u es an d
4 The relative beh avior of the compou nds of a complex
.

radical .

A similar i n vestigatio n of th e alums of alumi n iu m va n a ,

d i u m chromium an d iro n touched so far as the trivale n t

, , , ,

metals were co n cer n e d o n ly the seco n d of these poi n ts It

,

was fou n d that there was n o steady i n crease or decrease i n

solubility with asce nd i n g atomic weights The ord er of i n .

creasi n g solubilities was the same for the salts of all the u n i
vale nt metals a nd ran ,

Cr H

while that of the atomic weights is

v e . ,

A mo n g the alkali metals proper , the order o f solubility ,

Cs H H K H

was u n infl ue n c e d by the n ature of the trivale nt metal but was ,

the reverse of that of the atomi c weights This however .

, ,

did n ot exte nd to the compou n ds O f thallium which i n its ,

positio n i n the system is far removed from th e alkali metals .

The thallium salts all fell betwee n those of potassium and

rubidium i n stea d of at the e n d of the series
,
The ammo .

n ium salts too lay betwee n those of rubidium a n d potassium

, , ,

so the low molecular weight of the N H, radical fi nds n o ex

pr essio n i n the sol ubility of its salts The complete order .

fou n d for M was I

H F —b H H H
4

P otassium s o c uu m
alums could be obtai n ed o n ly with
an d ,

such trivale n t metals as yield the most spari n gly soluble

alums The compou n ds Na Fe Na G a N a In K G a a nd
.
—
,
—
,
—
,
—
,

K In do n ot exist
-
The questio n arises as to wheth er this is
.

d ue Simply to the fact that such compou n ds would be tO O sol

uble to permit of their isolatio n or to an actual differe n ce be ,

twee n these metals and caesium etc i n their power to e n ter , .

,

i n to such compou n ds A d i ffere n ce i n the te nde n cy of di ffer

.
 P e r i odi c S
y s te m .
45 7
e nt metalsof a group to e n ter i n to compou nds of the same
ge neral formula has n ot bee n ge n erally recog ni zed i n the liter
ature an d whe n n oticed it has u sually bee n regarded as due
, ,

simply to differe n ce i n solubility There c an be n o doubt .

,

however but that such te n de n cy is Specific a n d plays a very

,

importa n t part i n the formulas of the compou nds of a n alogous

eleme nts I n the do uble sulphates with the bivale n t metals
.
,

as will be see n it c a n be very sharply traced

, .

The order of solubilities i n this series sta n d s eve n more i n

co n fl ict with the periodic system tha n does that fou n d for the
alums In a n swer to the above me n tio n ed poi nts the data in
.
-

d i cate that
1 . The compou nds of metals i n the same family of the
periodic system do not follow the same or the reverse order of
their atomic weights This is true in each of the three
.

n atur a l groups of metals co n tai n ed i n the series .

2 . No correlatio n c an be fou n d betwee n the solubilities of

”
the ma n ga n ese and cupric salts an d the adj ace n t positio n s
,

of these eleme n ts i n the system .

3 The solubilities of the thalli um salts ca n n ot be i n ter

.

re te d thro ugh a co n sideratio n of that eleme n t s positio n which

’
p ,

is far removed from those of the alkali metals .

4 The i n flue n ce of each alkali metal upo n the solubility of

.

its compou n ds is Specific and retai n ed throughout all of them .

The same is true of the salts of ammo n ium While co n form .

i ng n either to the atomic weights O f the eleme nts n or to the

molecular weights of the co m pou n d s the solubilities sta n d i n
,

simple mathe matical relatio n to o n e a n other a n d that of any ,

compou nd c an be calculated from the co n sta n ts represe n ti n g

the specific i n flue n ce of the two metals which it co ntai n s .

This bei ng also true for the ammo n ium salts it follows that ,

i n a ny system by which the i n orga n ic compou n ds are to be

'
exactly classified the basis mus t be somethi n g which is as
,

applicable to the salts of a compou n d ra d ical as to an eleme n t ,

a n d which therefore ca n n ot be the atomic weights for these ,

are limi ted to the eleme n ts alo n e .

I n drawi n g this co n clusio n I do n ot wish to appear to at

tach too mu ch importa n ce to so simple a property as solu
bility n o r as suggesti n g that an y system of classificatio n be
,

2 8— 2 7
45 8 L oche .

based upo n such a property alo n e My results are simply an .

i n dicatio n i n a field which except i n crystallography has

-
, ,

bee n left almost u ntouched The i norga n ic lite rature does .

n o t to day co n tai n a si n gle i n sta n ce i n wh ich complete co m

-
,

parable data are at ha n d for all me mbers of a series of ho molo

gous compou n ds i n measureme n t of sol ubility degree of , ,

dissociatio n melti n g poi nts stability or an y oth er property

,
-
, , .

If we have an y u n derlyi n g distrust of the perio d ic system it ,

ce rtai nly does not appear to a marked exte n t i n the literature ,

for except i n rearra n geme n ts which leave the vital d i sc re p an

cies as co nspicuous as before there has bee n n ot on e attempt ,

to correct it To day we k n ow almost absol utely n othi n g of the

.
-

gradatio ns of properties i n ho mologous i n orga nic series except ,

“

i n the way of merely qualitative O bse r v ati o n s from as ma n y dif

fe re n t sta ndpoi n ts as there have bee n i n vestigators of the sub
je c t There is the n n o real possibility O f exte n di n g the
.
, ,

periodic system or of obtai n i n g a satisfactory n e w basis of

,

classificatio n u n til qua n titative data are at ha n d by which to

,

j udge its applicability In the d esire to a scertai n how exactly .

gra d atio n c an be traced I have u ndertake n this series of i n ,

v e sti g at i o ns an d ha ve chose n solubility as the first property

,

to be exami ned simply because it is the most easily deter,

m i n ed There IS probably n o other o n e property however

.
, ,

from which more i n formatio n c a n be d erived For if a sim .

ple relatio n exists bet w ee n the solubilities i n a homologous

series O f hydrated d ouble sal ts the n it probably follows that ,
.

the same is true of the vapor te n sio n of their crystals of th e -

,

degre e of their molecular d issociatio n of the io n ic dissocia ,

tio n of their a n alogous co nstitue n ts an d of other properties ,

upo n which solubility presumably depe n ds .

The methods employe d for de termi n i n g the solubilities was

that described i n my first article on the alums The satura .

ted solutio n s were evaporated to dry n ess at a n d the n

° °
heated to 1 5 0 to 2 00 u ntil the weight of the residual salts re
‘

m ai ned co n sta n t This usually required about four hours . .

The accuracy of the method was first ascertai ned on a large

variety of salts In some cases the results were further c on
.

firmed by sulphuric acid determi n atio n s or i n the case of the , ,

ammo n iu m salts by ig n itio n The ferrous salts were estima

, .
46 0 L oche .

C omparative researches upo n this series of salts h ave up to

the prese n t time bee n co n fi n ed almost e n tirely to the study of
thei r crystallography A few solubility determi n atio n s have .

bee n m ade upo n i n dividual compou nds of the series at differ ,

e nt temperatures but o n ly o n e approximately thorough i n ,

ve st ig a t io n of the subj ect is recor d ed This was the work of .

1
Tobler who to quote h is ow n words wished to ascertai n
, , ,

the e ffect cause d by the substitutio n of an alkali sulphate

for the seve n th molecule of water i n the vitriols ,

Nee d less to say no relatio n betwee n the solubilities of the,

simple salts a nd double salts coul d be traced A careful ex .

ami n atio n of T oble r s work shows that his results are not very ’

trustworthy H e fi n ds for i nsta n ce that the double salts

.
, ,

co ntai n i ng ammo n ium are i n every case less soluble tha n the
correspo nd i ng potassium compou n ds My ow n results very .

positively sho w the reverse O ur results for the ammo n ium .

salts do no t di ffer to an y great exte n t a n d his error seems to ,

lie more especially i n those for the potassium salts I n some .

cases he fi n ds the solubilities three or fOu r times greater tha n

my d etermi natio n s i n dicate them to be .

K Co

T . P arts per liter

6 ‘ C
L .

It is d ifli c ult to accou n t for s uch discrepa n cies eve n whe n ,

the fact is take n i nto co n sideratio n that Toble r s work was ’

do n e lo n g before the n ewer methods for determi n i n g solubili

ties were k n ow n A n other i n sta nce O fthe u n reliability of his
.

results is see n i n the fact that he obtai n ed a very regular sol

°
ubi l ity curve for potassium ferrous sulphate bet w ee n 0 a n d ,

2
although K ii ste r a n d Thiel have Si n ce show n that at
°
about 3 0 there is a sharp break represe n ti n g the tra n sitio n ,

2 H, O .

In additio n to the bivale n t metals me n tio n e d above co m ,

3
pou nds O f this series are also formed by chromium an d va n a
d i u m but these are too u n stable to permit of accurate d eter
4
,

1 A n C h m ( L i bi g ) 9 5
n . e 93 . e , , 1 .

g Ch m
1 Zt sch r . a n or6 . e . 2 1, 1 1
, .

3 P é l i g ot : A nn . c h i m ph y . s . 12 , 5 46 .

4 P i c ci n i Z t sc h r . a n o rg . Ch m e .
, 19 , 2 04 .
 Pe ri odic Sy em
st .
46 1

mi n atio n Fro m the remai n i n g eight bivale nt metals forty

.
,

salts are theoretically obtai n able a nd all but two of these , ,

the K Mn an d K C d compou n ds have bee n described

—
,
-
, .

These thirty eight salts have all bee n i nvestigated by me al

-
,

though o n ly the compou n ds the solubilities of which are ln ,

cluded i n the above table yield data that are suitable for ,

1
compariso n The caesi um salts of all eight metals are easily
.

o btai n e d although they are far more soluble tha n those of

,

a ny other alkali metal A n i ndicatio n of the m uch greater .

readi n ess of caesiu m to e n ter i n to salts of the series as com ,

pared with potassium for i nsta n ce is see n in the fact n oted , ,

2
by Tutto n that while several of the potassiu m salts are
,

O paque the caesiu m co mpou n d s of the same metals are almost

,

i n variably tra n spare nt This is especially true of the cupric .

s alts E xcept in the case of the ma n ga n ese a nd ca d mium com

.

pou n ds furthermore n o special precautio n s are require d

, , ,

with the caesi um salts to preve n t the formatio n of salts with ,

less water of crystallizatio n The salts with 6 molecules of .

water result withi n quite a wide ra n ge of temperature .

In the case of potassium this is true o n ly of the compou n ds ,

o f n ickel cobalt Copper a n d zi n c

,
The salts of the other , ,
.

metals form o n ly a t low temperatures an d with ma nga n ese ,

a nd cadmium where the caesi u m compou n ds are obtai n ed ,

with d iffi culty they do n ot exist at all SO far as I k n ow ,

.
,

this is the o nly i n sta n ce yet n oted i n which the very marke d
te n de n cy of caesi um to e nter i n to double salts as compared ,

with potassium ca nn ot be referred to the fact that the caesiu m ,

com pou nds are the less soluble an d it is of particular i nterest ,

for that reaso n In the case of double hali d es a large n u m .

ber of caesium compou n d s have bee n prepared by Wells an d

3
o thers for which no a n alogues of potassium c a n be obtai n ed
,
.

B ut i n all such cases I believe the caesium sa lts are very , ,

d ifli c ultl y soluble The fact that the same phe n ome n a occur .

whe n the caesium salts are the more soluble i ndicates that a ,

specific te nde n c y for each metal m ust be tak e n i n to co nsidera

‘
1 The ot h e rs are p a rt i a lly d e c omp ose d b y w a te r , w it h p re i pitation of on e
c of t he i r

u e n t s l ts
c on s t i t a .

2
J C h m Soc
. e . . 1 893 , 337 .

3 A S a n i n s ta n c e m ay b e c i te d the sa l t o f qu l
a d ri v a e n t a n ti mony , C sz s l s; We ll s
a nd Me t ge r : Th is JO U R N A L
z . 2 6 , 268 .
46 2 L ocke .

tio n which is not to be co nfused with ease of isolatio n a n d

, ,

does not i n v a lue solubility at all This is more or less i nc on .

siste n t with the assumptio n by which th e io n ic hypothesis ex

plai n s double salt formatio n For to take a n i nsta n ce which .
,

fully satisfies that assumptio n the formatio n of the compou n d ,

K A g ( C N ) would proceed thus 2

Ag + CN CN A g (CN ),
“

In other words it should make n o di ffere n ce whether the

,

alkali cya n ide solutio n co n tai n s potassi u m io n s or caesiu m

io n s for these tak e no part i n the reactio n O nly provided the
, .

solubility products of the caesi um compou n d s were lower tha n

those of the potassium salts should there be an y di ffere n ce i n
the readi n ess with which they are obtai n ed We fi n d i n the .

double sulphates a very pro no u n ced di ffere n ce however al , ,

tho ugh the caesium salts are i n almost every i n sta n ce twice as
sol uble i n gram molecules as those of potassium
,
-
,

Mg F . C Cu e . o . .

Cs
K
The solubility O f the K Mg salt here give n d oes n ot admit ,

°
of strict compariso n with the others for at 2 5 the salt is ,

parti ally decomposed by water separati n g a small proportio n ,

of its potassium sulphate A n observatio n to this effect had .

already bee n made by Sch w arz a n d was co n firmed by a de

l
,

termi n atio n o f the ratio of potassium to mag n esium i n th e

residue of the saturate d solutio n
grams residue gave grams
C alc u late d ,

R atio K : M g 2 ,
2:

N o attempts were made to prepare the potassium com

pou nds o f ma n ga n ese an d cadmium The fact O f their n o n .

2
existe n ce seems to have bee n fully establishe d by Tutto n .

N o reliable determi n atio n s furthermore coul d be made o n the , ,

potassium ferrous salt That a cha n ge of some sort takes ,

.

place i n this co mpou n d at 2 5 is i n d i c ated i n the fact that °

after s aturatio n is com plete a fi n e sedime n t c a n be see n mixe d

with the crystals provided the latter have n ot bee n very thor,

1 Di n gl e r , 19 8 , 1 5 9 .

2 L oc . cit .
46 4 L ocke .

The salts resulted with all the bivale nt metals but those the ,

data for which are give n are the o n ly o n es on which deter

m in a tions could be made With the mag n esium ma n ga n ese
.
, ,

iro n an d c admium compou n ds the separatio n of thallium sul

,

phate begi n s as soo n as water is added and proceeds u ntil all ,

the sulphate of the heavy metal has passed i nto solutio n .

The cobalt salt is o n ly partially decomposed eve n o n pro ,

lo n ged d igestio n In o ne experime n t with the salt the fou n d

.

solubility was O I 4 3 g ram molecule a nd the residual u n dis

.
-
,

solved Salt was mixed with about on e fourth its bulk of thal -

l ium sulphate .

The ammo n iu m salts o n the other ha n d sta nd n ext to

, ,

caesium i n their solubility although the molecular weight o f ,

the complex ( N H, ) is lower tha n the atomic weight of an y

alkali metal i n the series They are also m uch more readily
.

formed tha n the potassium salts although more soluble com , ,

pou n ds bei n g obtai n able with all the bivale n t metals T he .

cupric salt alo n e is partially decompose d by water .

I n vie w of the fact that the solubilities of the salts eve n o f ,

th e alkali metals proper do n o t co n form to the ato mic weight s

,

of the latter i n their order it would O bviously be idle to spe e n

,

late upo n the behavior of the compou n ds of thallium from the

sta n dpoi n t of that metal s positio n i n the periodic system
’
.

Neither its positio n n or its atomic weight c an be brought i nt o

correlatio n with these solubilities The o n ly co n clusio n .

'

which c an be draw n without prej u d ice is that the efie ct ofe a ch

,

u n i va le n t m e ta l up on the sol u bi li ty o
f the s p fi
a lts i s a s e ci c on e ,

re ta i n e d thr oug hou t a ll i ts comp ou n ds i n the se r ie s a n d tota lly ,

indep e n de n t of i ts a tomi c w e ig ht .

The same is true of the bivale n t metals In the seco n d .

family for i n sta nce we fi n d the ord er to be n ot

, , ,

Mg H Zn H
as in the atomic weights , n or the reverse but ,

Zn »

1 Zn
 Pe r i odic S
y ste m .
46 5

For the members of the eighth family also the order is dif ,

fe re n t from that of the atomic weights The n ickel com .

pou n ds are more spari ngly soluble tha n those of any other
bivale n t metal i n the series and the cobalt salts sta nd be
,

t wee n these a nd the ferrous compou n ds .

0
579

A dj ace n t to this group is ma n ga n ese on the o ne ha nd cop ,

pe r On the other The ma n ga n ese salts are i n ge neral less

.
, ,

A to m ic w i gh ts M“
e .

Fig . I .

Soluble tha n those of iro n the cupric compou n ds more soluble

,

t ha n those O f cobalt For the caesium salts for i n sta n ce we

.
, ,

h ave

Obviously no rule c an be laid dow n by which the solubili

,

ties can be explai n ed by the positio n s of the bivale n t metals .

Nor c an an y gradatio n be O bserved accordi n g to i n creasi n g

atomic weights of all the eleme n ts The perfect i n depe n de n ce of
.

the solubilities from the atomic weights througho ut is forcibly

Show n i n Fi g I where the data for the caesium salts are
. .
,
46 6 L oche .

plotted with the atomic weights of the bivale n t metals as ab

sc iss ae .

A s i n the case of the u n ivale n t m etals ,

the i nfl u e nce f
o the
bi va le n t me ta l i s sp e cifi c, a n d i ndepe n de n t f
o i ts a to mi c w e ig ht
and o f i ts posi ti on i n the sy ste m .

Similar co nclusio n s had pre vio usly bee n reached i n th e

case of the alums It was there possible to calculate i n d i
.
,

re c t l y a co n sta nt which expressed this specific i nflue n ce for

,

each metal that of o n e metal of the same vale n ce bei n g take n

,

as the sta n dard C alli n g the di ffere n ce betwee n the solubili

.

ties oi the alums of a give n trivale n t metal with two alkali

”
m etals the solubility i n creme n t for the latter ( thus I n cr
, , .

A l m m ) it was fou n d fro m the experime n tal d ata that th e

—
a 1 ,

ratio bet w ee n the correspo n d i ng i n creme n ts for two trivale nt

m etals is approximately the same n o m atter w hic h alk ali ,
\

metals m and 111 represe n t The i n creme n t ratios

, 1
.
,

ling— m1

mg —
ml

for i nsta nce , are as follows

Ta bl e
R a ti o

The ratios betwee n the i n creme n ts for alumi n iu m an d th e

remai ni n g trivale n t metals are co n sta n t to about the sam e
degree If we adopt alumi n ium as a sta n dard ( the sta n dard
.

will below be de n oted as the i n i tia l metal ) these ratios give ,

directly the e ffect produced by the substitutio n of the other

trivale n t metals for alu mi n i u m i n the salts of the latter A s .

s umi n g that the variatio n s i n the ratios are due to e x p e ri

me ntal error i t follows that as soo n as the solubilities of two

,

correspo n di n g salts of each trivale n t metal are k now n th e

others c an be calculated I thought it probable that the sam e
.

would be true of the salts of the bivale n t metals but fou n d ,

46 8 L ocke .

That is a is the average rate of ch a nge of the i n crem e nt

,

ratios .

The co n sta nt 2 b is the limit to which the i n crem e n t ratios

approach In the equatio n ( 2 ) it i s give n as the i n creme n t
.

ratio mi n us the product of a i nto the sum of the solubilities of

the two salts of the i n itial bivale nt metal If a is zero the n .
,

the i n creme n t ratio beco mes 2 b an d is therefore co n sta n t , , ,

.

This was the assumptio n tacitly made i n the m athematical treat

me n t of the solubilities of the alums The i n creme n t ratio .

approaches more closely to 2 b furthermore the less the solu , ,

bilit ie s of the two salts of the i n itial eleme n t ( y y ) are t h e , , ,

correctio n i n that case bei n g very small It is probable .

,

therefore that in salt series O f which the members are very

,

Spari n gly soluble the ge n eral relatio n would hold a pp rox i

,

mately true

2b .

If in the equatio n
"
as z by c,

we set y 0 the n ,
c whe n ce it follows that c w ould be
,

the solubility of a salt of the seco n d bivale n t metal whe n th at

of the correspo n di n g compou n d of the i n itial m etal is zero .

In the tables give n below the values for c were calculated,

from the equatio n

’
5 : y YI
_
l

For the derivatio n of the values of these co nsta n ts three

solubilities must of co urse be k n ow n for each bivale nt metal
, , ,

a nd a fourth is n ecessary to test their validity U n fo r tu .

n ate l y data ca n be obtai n ed for four or more salts o n ly i n the

,

case of n ickel cobalt copper and zi n c With these salts th e

, , , .

agreeme n t betwee n the values of each co n sta n t whe n derived ,

from di ffere n t solubilities is remarkable In the followi n g

, .

tables n ickel has bee n retai n ed as the i n itial bivale n t metal

througho ut n ot o nly because the solubilities of its salts with
,

all the u n ivale n t metals could be measured but because be , ,

i n g the least sol uble Of all their determi n atio n was the least
,
 Pe r i odic S
y ste m 46 9

subj ect to experime n tal error U nder y , y y , are give n the .

, ,, ,

various co mbi n atio n s of salts by which the co nsta n ts are de

rived The values for c are expressed in thousa n dths of gra m
.

molecules per liter The colum n s i give the i n creme nt

.

ratios as observed an d as calculated from the equatio n s

,

usi n g for a an d b the values marked by asterisks The ob .

served i n creme n t ratios are u n certai n by on e or two u n its i n

th e seco nd decimal an d the differe n ce betwee n the O bserved
,
'

an d calculated values for them are therefore well withi n the

limit of error .

Ta ble V —
N iche l Coba l t .

i
1. O b s e r ve d .

—
2 43 I 26
.

—
2 44
—
2 47
o 0 0 0 0
_
2 39

2 40
0 0 0 0 0 0 2 37 2 0
55

Ta bl e VI —
N i che l Copp e r .

C .

+ 14
+ 16
"
I .
5 2 I
><
+ 13
+ 15
+ 13
Ta ble VIL
'
—
N z che l - Zi n c .

i
yr .
ya . a . i . O b s e rv e d .

Cs N II4 K O 00 1 6
* 26
— —
.
—
1 12 1 12

CS N H4 TI _
0 00 I
. 6 o 0 0 0 0 0 0 0

Cs K Tl —
0 00 1 6 —
26

N H, K Tl 25
’
Cs TI 26

N H, Tl —
26

K Tl —
27

The most reliable v alues for the three co n sta nts are those
marked by asterisks the i n creme n ts y y and y y , bei n g
— —
, l , z
47 0 L ocke .

there the largest a nd co nseque n tly the least i n flue nced by

,

experime n tal error A dopti n g these values we h ave as the

.
, ,

expressio n of the relatio n which the solubil it1e s of the salts of

cobalt copper a n d zi n c bear to those of n ickel the equatio n s
, , ,

’
Ye o y
—
o 00 3 2
.
.
y —
o z s9
.
;
y r: u y +0 O OO 5 y
2
+0 0 13 ;
’—
yZn y
—
o 00 1 6
.
y 0 02 6 .

The value for a it w ill be see n is in each case very smal l

, , ,

an d i n the n ickel copper series where it is o nly +0 000 5 the

-
, ,

i n creme n t ratios approach very closely to the value of 2 6

itself .

Si n ce thes e equatio ns are satisfied by the solubilities of

the salts of any alkali metal all that is n ecessary to O btai n a,

measure for the i n flue n ce of any alkali metal upo n its com
po u nds is to adopt the n ic k el salt of o ne O f these as a sta n dard -

a nd substitute for this val ue of y the product my where m is ,

.

the ratio bet w ee n the solubilities of the sta n dard salt a nd

seco n d salt of n ickel In the form .

am y + 2 bmy + c ,

the n th e ge neral formula would give by the substitutio n of

, ,

correspo ndi n g va l ues for the u n ivale n t and bivale n t metals ,

respectively the solubility of any salt in the series A dopt

, .

i n g caesium n ickel sulphate as a sta ndard the values for m ,

are
N IL . R b .

These co n sta nts give the followi ng solubilities i n the cobalt ,

copper a n d zi n c series U n der D is give n the differe n ce from

, .

the observed solubilities

Ta ble VII] .

D . D .

Tl +0 00 1
Rb —
O OO 2
.
+0 0 34
K + 0 00 2 -
0 00 1
N H,
Cs —
O OO 2
.
+0 00 5

There is but on e i nsta n ce that of the zi nc rubidium salt

,
-
, in
47 2 L ocke .

Cs —
Rb
Cs —
Tl
C s—
N H,
_ —

CsT R b —

Cs —
N H,
C s —
Tl
Cs —
K
Cs —
Tl

The agreeme n t betwee n the calculated an d observed i ncre

me nt ratios for the d iffere nt bivale n t m etals as give n i n Tables ,

V to V II is very much more exact tha n that fou n d i n the

. .
,

case of the alums Table IV whe n the ratio was assume d to ,

.
,

be co nsta nt This led me to test the solubilities of the alums

.

by the above quadratic equatio n I n my previous article as .

,

h as bee n stated the tacit assumptio n had bee n made that a

,

here equals zero i n which case the i n creme n t ratio is c o n

,

sta n t an d equals 2 6 It was fou n d that a somewhat more ex

,
.

act expressio n for the solubilit i es i n this series as well was ,

obtai n ed by the n e w formula although a is i n fact much ,

.

smaller i n each case tha n for the double sulphates of an y

of the bivale nt metals except copper It will suffi ce here .

to give the values for a b and e for a si n gle o n e of the alum , ,

series In that of alumi n ium va n a d ium alum i ni um bei n g

.
-
,

take n as the i n itial trivale n t metal these values are as fol ,

lows
X A l a mz n z a m Va n a di um
' '

Ta ble —
.

yl .
Y2 .
y3 . a. c. 1.

N H, Tl Rb —
o 0 0 09
.
—
2 6
N H4 TI Cs —
o ooo o
.

N H, Rb Cs —
o 00 0 8
.
—
29
Tl Rb Cs o 000 7 29
*
— —
.

N H, Cs —
2 5
TI Cs —
29

Rb Cs 34 7
—
25

1 The h e e re d u e
v a ri a ti o n s r a to t h e l i gh tl y ab no m l so lub i lity o f th
s r a e z i nc
r u b i d i um sa l t U si n g f th e l tte
. or a r th e ca c l ul ate d so lub i l i ty ( T b l e VI II ) t h e a . ra t i o s

i n to w h i c h t h i s s l t e n te rs a re a

C S— N H 4
C s— R b

in l
c os e a g re e m e n t w i th th e r a ti os fo r t h e ot he r sa lts .
 Pe ri odic Syste m .
47 3

U si n g the equatio n
2
yv 3 -5 4 y 0 0 00 9 y

the calculated solubilities for the va n adium alums are as fol

lows
Rb .

Fo r
the alumi n ium chromium -
a nd alumi n ium ferric series -
,

similarly the equ atio n s

,

’
ye r :
y y
2
yp e y y

form a much more exact expressio n for the solubilities of the

chromium and ferric alu ms tha n did that previously derived .

The relatio n s discussed above i n dicate very co nclusively

that i n a g roup of i somorp lzous compou n ds the efe ct of a
g i ve n e le me n t up on the sol u bil i ty o f i ts co mp ou n ds i n the
se r i e s is con sta n t t/ The
z roug /
z ou t a ll the se co mpou nds .

g e n eral formula for its calculatio n is the same fo r the salts of

‘
both bivale n t an d trivale n t metals a n d i n all probability , ,

therefore we have before us the worki ng i n two i n sta n ces of

, , ,

a ge n eral law which after developme n t i n other series may

, , ,

be of very great importa n ce i n the systematizatio n of i n orga n ic

compou n d s .

The ge n eral applicability of an equatio n of the form

'=
+ +
z
y d y 2 by c

shows that if the solubilities be p l otte d with the salts of the

i nitial eleme n t as or d i n ates and those o f the seco n d metal as ,

abscissae a parabola al w ays results Fig I I gives its form

, . . .

for the alumi niu m va n adium series a mo n g the alums and for
-
,

the n i c kel cobalt n ickel copper an d n ickel zi n c series i n the

-
,
-
,
-

other group It w ill be see n that i n the al u mi n i u m y a n ad i um

.

a nd n ickel copper series where the values of a are extremely

-
,

small a nd respectively ) the parabolas ,

very n early approach to bei n g straight li n es .

This metho d of prese n tatio n is of peculiar i n terest because ,

i n it n o accou n t whatsoever is take n of the atomic weights .

T he latter do n ot e v e n e n ter i n to the values of a an d b which ,

47 6 L ocke .

Si n ce the equatio n
’ ’
(5 ) y ay 2 6y c

' '
is also satisfied by y d y, y Ay ,

'
(6 ) y dy ’
a (y 26 (y Ay) 6 .

A fter subtracti n g therefore ,

(7 ) 2 ay 2 6 ad y .

N ow let the two li n es in questio n approach coi ncide n c e .

A s Ay approaches zero ,
from becomes 2 ay 2 6 .

Substituti n g this value in the poi n t ( X Y ) , ,

h
X 6
1

z—
ay c

becomes the poi n t of co ntact of the li n e j oi ni n g

'
( 6 + h y ) with th e curve touched by all li n es j oi n i n g corre
,

'
spon d ing values of y an d y or correspo ndi ng solubility ,

poi nts The equati on of this cu rve which is an hyperbola

.
, ,

may be fou n d by elimi n ati n g y i n This gives

( 9 ) K (x 4 uh ( X )Y
’
2h (1 26 ) (X )
'
6 6
2
h o,

where
K
2
( I —
4a c .

I —
26
The ce nter is the poi n t an d the asymptotes are
K (x
+ 2 6) Y
2
x ‘

o, 2h( 1 4a h
—

The ta nge n ts parallel to the x axis touch at the poi n ts -

h 26 K
)
1
i
k ’
25
an dfrom these data the curve may be located an d by as ,

ma ny poi nts located thereo n as we wish .

In the cases before us the hyperbolas are all very thi n

,
A .

peculiar fact i n the series n ic k el cobalt and n ickel zi n c is

,
— -
,
 Pe r i odic S
y ste m .
47 7

that the li nes co nn ecti n g the caesium salts are ta n ge n tial to

o n e bra n ch of the curve those for the remai n i n g salts to the
,

oth er In both these series the upper bra n ch lies to the

.

right of the n ickel perpe n dicular In the n ickel copper series .

-
,

o n the other ha n d the upper bra n ch lies to the l eft a n d all

, ,

the li n es are ta nge n tial to this Th is case is represe nted i n .

Fi g I I I
. .

Ni Cu
Fi g . I II .

A co n sideratio n of this figure bri n gs o ut o ne very impor

ta nt poi nt n ot show n by the first and simpler method of plot
,

ti n g and for the purpose of illustrati n g which therefore this

, , ,

method has bee n retai ned In the n ickel copper series all th e
.
-

li n es are ta n ge n t to the curve at poi n ts lyi n g o n the same side

of that at which it is touched by the horizo n tal ta n ge n t and ,

the cu rve lies outside the two perpe n diculars A ll these li nes .

are therefore i n cli n ed upward an d the solubility of each

, , ,

cupric salt accordi ngly is greater tha n that of the correspo n d

, ,

i ng n ickel compou n d This however is by no mea n s n e ce s

.
, ,

sa rily the case If the hyperbola or that part of it i n cluded

.
,

betwee n the poi nts of ta n ge n cy lay betwee n the two p e rpe n ,

d i c ul ars the n ( Fig IV ) if the successive solubilities of the

, . .

salts of the i n itial eleme n t r a n A B C those of the seco n d H H

,
47 8 L ocke .

would l ie i n the order C B l l

r»
AThe order of solubility
,
.

would be reversed throughout . The most soluble compou nds

Fi g I V
. . Fi g . V .

for the i n itial eleme n t would be th e least soluble for the

seco n d This is the most complicated case an d has n ot y e t
.
, ,

with certai n ty bee n observed, .

With the hyperbola lyi ng outsi d e the perpe nd iculars sec ,

on d ly let us assume i ts p os it io n to be such tha t the y value

,
-

of the horizo ntal ta n ge nt is i n termediate betwee n the ex

tremes of solubility for the compou nds of the i n itial elem e n t .

The n ( F ig . for a ll p oi n ts ly i ng 6e lozo the hor iz on ta l the

,

solu 6i li ti e s for the se con d e l e m e n t w i ll 6c le ss tha n for the

fi r st a n d
, f or those a 6 ove i t th ey w i l l 6e g r e a te r In the figure .

we have A A B B but C C T w o i n sta n ces are 1

.

show n by the compou nds of the bivale n t metals i n which this

i nteres ti n g relatio n occurs : i n both the extreme solubilities ,

for the i n itial eleme n t are i n the on e case less i n the other ,

case greater tha n those for the seco n d In the zi nc copper

, .
-

series we fi nd
Zn T l -
29 C u Tl —
22

Zn C s —
Cu Cs —

In the zi n c cobalt series

-

Zn R b —
C o—
Rb
Zn C s —
Co Cs —

E xami n ed alo n e , these figures appare n tly sta n d at utter

varia nce to one a n other , a n d seem to for bid all possibility of our
4 80 L oche .

ac t it ud e almost n othi n g co n cer ni ng gradatio n i n the proper

ties oi i n orga n ic compou nds B ut if the i nflue n ce of an ele
.

me n t upo n its compou nds of a series is co n sta n t throu gho ut ,

as from the above work appears to be the case i n the matter

of solubility the n the thought o f an exact system is n ot very
,

visio n ary To attai n it h0 w e ve r an al og o us compou n ds must be

.
, ,

give n co n siste n t comparative study an d qua ntitative data be ob

,

t a in e d co n cer n i n g them In each series of compou n ds studied

.
,

furthermore it is of prime importa n ce to i n clude as ma ny

,

represe n tatives of the variable eleme n ts or groups as possible .

The relative solubilities of the thalliu m an d caesium d ouble

sulphates of zi n c a n d copper an d of the rubidium a nd caesiu m
,

salts of zi n c an d cobalt show that n o defi n ite i n formatio n c an

,

be gai n ed of the i n flue n ce of an eleme n t upo n its compou n ds

u n til at least three salts of each metal have bee n exami n ed .

A fourth or a fifth must be exami n ed to prove the validity o f

the d e d uctio n s drawn o n the basis of the data thus obtai n ed .

To day so far as I c an ascertai n there is n o t a si ngle i n

-
, ,

sta n ce i n the i n orga n ic literatur e where a p r0 p e rty like solu

x

bilit y has bee n accurately determi n ed for the fourth salt i n

such a series There are almost n o cases where comparable
.
,

a n d reliable d ata for three are at ha n d The most esse ntial .

features of the periodic system have h ardly ever bee n tested

by qua n titative measureme n ts .

The co n clusio n s draw n in this paper regardi n g the ind e p e n

de n ce of the solubilities from the atomic weights is O pe n to
criticis m upo n on e poi n t which arises i n this co nn ectio n To
, .

ascertai n the i n flu e n ce of a give n bivale n t metal upo n th e

double sulphate w e must k now the sol ubility of at least three
,

salts of both this a n d the i n itial metal B ut the data th us de .

rived are i n a measure comparable with those which would be

obtai n ed from a co n sideratio n of the salt s with asi n gle alkali
metal for i n the S02 group we are adheri n g to o ne re p re se n
,
“

t ative of a n other varia ble co n stitue n t It is barely possible .

that after a similar exami n atio n of the corres po n di n g se l e

n ates ,
a co mbi n atio n of the co n sta n ts obtai n ed i n the t wo
series which would thus give the i n flue n ce of the metal upo n
,

an y of its compou n ds i n the series would

bri n g the metals i nto the order of their atomic weights .
 In a cti vi ty o fL ip a se .
48 1

U n fortu n ately except i n the , on e compou n d ,

R is represe n ted o n ly by sulphur an d sele n ium an d for ac ,

curate compariso n three substitue n t eleme n ts are n ecessary .

Two much more suitable series for the i n vestigatio n of this

poi n t w ould be the salts of the ge n eral formulas an d

i n which all three symbols have several rep

re se n t at i v e s The seco n d formul a shoul d theoretically be c o n
.

formed to by 1 9 2 d i ffere n t salts These t wo series I should .

like to reserve to myself for future study .

My tha n ks are d u e to P rofessor P ercy F Smith of the .

,

Sheffield Scie ntific School for m a n y suggestio ns embodied i n ,

the mathematical part of the above work .

N E W H A VE N A p il
, r 2 , 1 9 02 .

THE I N A C T I V IT Y TOW A R D S T H E . OF L I P A SE
SA L TS O F C E R T A IN A C ID E T H E R S C O N
SI DE R E D I N T H E L I G H T O F T H E
T H E O R Y O F E L E C T R O L Y TI C
D I SSO C I A TIO N .

BY J . H K A ST L E
. .

While studyi n g the ki n etics of lipolytic hydrolysis a sub ,

je c t that has bee n u n d er i n vest i gatio n i n this laboratory n o w

for some time it was thought desirable to try the effect of
,

varyi n g amou nts of water on the hydrolysis of ethereal salts

by lipase In ord er to accom p lish thi s satisfactorily it was
.

f ou n d n ecessary to employ a very soluble ethereal salt and on e

which the ferme n t could readily hydrolyze O n accou n t of .

the solubility of certai n salts of som e of the acid ethers it

seem e d probable that these substa n ces might be employed to
adva n tage i n the i n vestigatio n of this particular phase of the
problem Such a substa n ce is sodium ethyl succi n ate The
. .

fact that diethyl succi n ate is rea d ily hydrolyzed by lipase fur
n i sh e d a n additio n al reaso n for usi n g sodium ethyl succi n ate

i n the prelimi n ary experime n ts While this salt was n ever .

obtai n ed i n as satisfactory a co n ditio n of purity as could be

desired it was observed that lipase could n ot effect its
,

1 G rai li c h , A . W .
, 2 7 , 17 5 . The p ot a s si um c ompo u n d c ry sta ll i z e s w it h 2E 20 .
482 K asi l e .

hydrolysis This seemed the more remarkable in vie w of the

.

ease with which the diethyl succi n ate is hydrolyzed by the

lipol ytic ferme n t .

In V iew of this somewhat remarkable an d i nteresti n g result

it seemed advisable to test the co n duct of lipase towards the
salts of other acid ethers an d also by way of compariso n its , , ,
1
actio n o n the correspo nd i n g neutral ethers U p to the pres .

e n t the actio n of the ferme n t o n the mo n o a n d diethyl ethers

of eight di basic acids has bee n studied The followi n g re .

su lt s were obtai n e d

Fu ma ra te s Diethyl fumarate is very readily h y d rol v z e d by

.
—

lip ase This has bee n d emo n strated by n umerous e x p e ri

.

me n ts O n so d iu m ethyl fumarate on the other ha n d lipase

.
, ,

is without actio n i n tw en ty four hours at 40 C -

,
°
.

Ox a la te s D iethyl oxalate is so easily hy d rolyzed eve n by

.
-
,

pure water that it was fou nd d iffi cult to d etermi n e whether

,
°
lipase accelerated the hydrolysis By worki n g at 0 C how . .
,

ever it was observed that the active ferme n t accelerates the

,

hydrolysis .

O n potassium ethyl oxalate lipase h as n o actio n or if a n y , , ,

it retards the hyd rolysis Tubes co n tai n i n g small amou n ts .

of this salt an d stro n g u n filtered hepatic extracts an d the ,

boiled co n trols showe d n o d iffere n ce i n aci d ity i n twe n ty four -

°
hours at 40 C O n the other ha n d with clear weaker solu
.
, ,

tio n s of hepatic lipase a n d this salt the boiled co n trols showe d ,

°
a sl i ght acidity after twe n ty four hours at 40 C whereas the -
.
,

tubes co n tai n i n g the active ferme n t remai n ed n eutral .

P htha l a te s D iethyl phthalate is slowly hy d rolyzed by

.
—

lipase This has bee n proved i n n umerous experime nts O n

. .

the other ha n d it is not acte d o n by pure water at ordi n ary

,
.

°
temperatures or at 40 C i n twe n ty four hours .
-
.

1 g th e c on d u c t o f l i p e tow ard t h e v io u s e th e s e mploy e d i n th i s i n

I n t e s ti n as s ar r

v e s ti g ati n t h o f llow i n g m d o f p c e d u re w s g e n ll y ado pte d Tub e s w e re

e o o e ro a e ra .

p e p re d ontain i n g 5 c c of t h e c ti e a n d boi l d n y m e T o t h
r a c . a li tmu s w a s
v e e z . e se

a dd d t g t h r w i t h s m a ll
e ,
o e e mou n t s f th e e th e t b e t t d nd a s m a ll qu a n ti ty of
a o r o e s e a

t lu n e
o e a n ti e p ti c
as T h e t u b e s w e e t h e n k e p t t th
s . p o p e te mp e tu r f th e
r a e r r ra e , or

d i re d i n t rv a l a n y h y d o l y s i s b e i n g i n di c at d b y th c h a n g e i n c o l o o f t h e l i t mu s
es e , r e e r .

T h e a c ti i ty o f a l l li p
v e x tr t a n d s lu ti o n s e mpl y d i n th e i n v e s ti g ti n w s
as e ac s o o e a o a

r p
e e a te d l y d t r m i n e d b y m
e e n s o f t h y l b u ty t e d u i n g t h e p o g re s of t h e w o k
e a e ra r r s r .

T h e olu ti n
s n d e x t ac t s e mpl y e d w e e f o u n d to h y d ol y e
o s a r o to g ra m o f
r r z

e t h y l b u ty rate i n fi fte e n m i n u te s at 4 C w h e n 5 c c o f t h e solu ti on o r e x tr c t w e e

°
0 .
,
a r

a ll w e d to a t o n
o c g ra m of th e e th e re a l sa lt .
4 84 K a stle .

always bee n fou n d to be i n active toward s these salts The .

co n d uct of the ferme n t toward s d iethyl sulp hate has n ot

bee n tested .

From these observatio n s o n e might get the impressio n

that possibly the salts of these various acid ethers are toxic
to lipase an d that they thereby preve n ted its actio n That .

such however is n ot the case has bee n proved by addi n g

, ,

small amou n ts of ethyl butyrate to the co nte n ts of the tubes

before the co n clusio n of the tests
. I n every i n sta n ce the .

tubes co ntai n i n g the active ferme n t showed a marked hy d rol

y si s in a few mi n utes after the additio n of the butyrate whereas ,

the co n trol experime n ts gave n o evide n ce o f a ny hy d roly

sis I n this way it was show n that eve n after remai ni n g in
.

co ntact with the salts of these acid ethers for twe nty four -

hours or eve n lo nger the ferme n t was capable of hydrolyzin g

, ,

1
ethyl butyrate .

This wo ul d seem to i n dicate th at the failure on the part of

the lipolytic ferme n t to h y drolyze the salts of aci d ethers
ca n n ot be ascribed to the toxicity of these substa n ces but ,

must be due to some other cause A ppare ntly the expla n a .

,

tio n of the differe n ce i n the co n duct of lipase to wards the n e u

tral an d aci d ethers is to be looked for n ot i n a n y specific e f
fe c t which either of these substa n ces may exert to ward the
ferme n t but rather i n some fu n d ame ntal chemical di ffere n ce
,

i n the n ature of the two classes of ethereal salts In this p e c u .

liar co n duct on the part of lipase we are remi n ded at least to ,

some exte nt of the remarkable behavior of glucose an d emul

,

si n e towards a an d fl me thyl glucoside I n order to accou n t -

.

for the remarkable di ffere n ce i n the co nd uct of the two fer

me n ts to these compou n ds it has bee n fou n d n ecessary to refer
it to a correspo n di n g differe n ce i n th e stereo c o nfi g urat io n of -

the t w o glucosides so i n the same way it would seem logical

to assume that the differe n ce observed i n the co n duct of lipase
towards n eutral ethers a n d the salts of acid et hers is due i n all
1 It i s n ot i n te nde d to con ve h
y by t i s t h at
lts o f t h e ac id e th e s a e a l to
th e sa r r

g e t h e n n t x i c to l i p
r o - o k l e v e n i n c lu din g s u c h s ub s tan c e s a s sod i um
ase . L i e a l l s a ts ,
a n d p ot s i um c hl ri d
a s th y h o e b e e n ob
e s, e r v d t o b e s m e w h t to xi c i n t h i r
av se e o a e

e ff c t up n th e f e r m e n t ; b u t i n n o
e o as h a s t h e e b e n a n e n ti e l o s s f l i p l y ti c a c
c e r e r o o

ti i ty o n th e p a rt f a n y sol uti o n o f l i p s e mpl oy e d i n t h

v o a e e xp e ri m e n t s a s t h e t e
e e s .

s ul t o f t h e p oi so n o u s a ti o n o f t h e s u b s t a n c
c b in g te st d e e e .
 In acti vi ty f L ipa se
o .
485

probability to some i n here nt chemical d i ffere nce in the n ature

o f these two classes of compou n ds .

In the l ight of our prese n t co n ceptio n s the mos t ch aracter

i st ic differe n ce betwee n the d iethyl ether of a dibasic acid and
a metallic salt of the monoe thy l ether of the same acid so far ,

as thei r chemical co n duct is co n cer n ed is that i n aqueou s ,

solutio n the latter is io n ized whereas the former is n ot This .

d iffere nce is quite as fu ndame ntal as a structural on e Might .

it n ot accou n t therefore for the di ffere n ce i n their co n duct

, ,

towards lipase
In view of this it became a matter of i n terest to test the con
duct of lipase towards certai n derivatives of the m on oe th y l
ethers that are chemically i n di ffere nt A ccordi ngly ethyl .
,

ox amate an d ethyl p s ulp h a mi n e be n z o ate were prepare d and

-

their co n duct towards lipase tested i n the usual m a n ner .

Both of them were fou nd to be hydrolyzable by the actio n of

the ferme n t Briefly the n the facts as they are k n ow n to us
.
, ,

at prese n t are these

First lipase has bee n fou nd to hydrolyze a large n umbe r df
,

n eutral ethers A mo ng those whose co n duct towards the fer

.

me nt has bee n tested in this laboratory may be me ntio n ed the

followi n g E thyl formate ethyl acetate ethyl butyrate ethyl , , ,

propio n ate ethyl isobutyrate ethyl be n zoate methyl butyr

, ,
"

ate amyl acetate amyl butyrate diethyl succi n ate diethyl

, , , ,

oxalate diethyl fumarate diethyl tartrate diethyl phthalate

, , , ,

Seco n dly lipase has bee n fou n d to be i n active towards the

,

salts of acid ethers the followi n g h avi n g bee n tested with the
,

ferme n t : Sodium ethyl succi n ate potassium ethyl oxalate , ,

barium ethyl sulphate potassi um ethyl sulphate barium ethyl

, ,

phthalate potassiu m ethyl phth alate barium ethyl p sulpho

, ,
-

be n zoate sodi um ethyl f umarate barium ethyl p n itro sulph o

, ,
-

be n zoate potassiu m ethyl p n it ros u lph obe n z oate

,
Not on e of -
.

these compou nds was hydrolyzed by the ferme n t .

Thirdly lipase h as bee n fou nd capable of hydrolyzi n g

,

chemically i ndi ffere nt derivatives of certai n of the monoe thy l

ethers such as e thy l ox am ate an d ethyl p sulphamin e be nz oate
,
-
.
4 86 K a stle .

In the light of these results o n e is n atu r ally led to co n nect

the i n activity o n the part of lipase towards the salts of acid
ethers with the electrolytic dissociatio n of these substa n ces i n
aqueous solutio n an d upo n the assumptio n that the hy d roly
sis of a substa nce by mea n s of a ferme nt is always preceded
.

by the combi natio n of the hydrolyte an d the e n zyme the re ,

s u l ts above described may be co n strued to mea n that lipase

ca nn ot form combi natio n s with io n s but o n ly with molecules .

It is i nteresti n g to n ote i n this co n necti on that by far the

greater n umber of substa n ces capable of bei n g hydrolyzed by
e n zymes are fro m the sta nd poi n t o fthe theory of electrolyti c
,

dissociatio n i n di ffere nt or n on io n izable substa n ces These

,
-
.

substa n ces are so well k n ow n that they do n ot require me n

/

tio n i ii thi s co n n ectio n O n ly a few substa n ces of salt type

.

c an be hydrolyzed by ferme n ts Such s ubsta n ces are pot as .

sium myro n ate an d ammo n ium hippurate To what exte nt .

these substa n ces are io n ized i n aqueous solutio n is at prese n t

u n k n ow n to the writer if i n d eed it has ever bee n determi n ed
, , .

In V ie w of the very thorough a n d exhaustive treatme n t

which the whole subj ect of electrolytic dissociatio n has received
i n rece n t years it would seem at first sight that quite a n umber
,

of methods wer e available for further testi ng the correct n ess

of these assumptio n s U n fortu n ately ho wever such is n ot
.
, ,

the case for as freque n tly happe n s i n i n vestigatio n s of this

, ,

ki n d the i n stability of the e n zyme an d its extreme se nsitive

,

n ess to its chemical e n viro n me n t simply make it impossible to

impose co n ditio n s which ord i n arily are simple e n ough .

E n ough has alrea d y bee n d o n e to make it appare n t that a

great ma n y practical d ifli c ul ti e s will have to be overcome before
a n y additio n al evide n ce either for or agai n st the vie w s herei n

adva n ced is to be obtai n ed A s soo n therefore as the O pp or .

, ,

t u n i ty prese nts itself I hope to make a thorough an d e x h a u s

tive study of the questio n s suggested by these observatio n s .

ST T E C LL E G E
A O K E N TU KY
op C
L EX N G T N A p l
,

I O 9, ri , 1 02 .
488 Rep or ts .

escapes quietly leavi ng a fused amalgam i n the boat A t , .

°
1 0 00 all mercury has escaped A higher heat volatilized the .

barium It adheres to the iro n boat and i n removi n g it with

.
,

a chisel it was somewhat oxidized as his a n alysis showed

Mercury and bariu m hydroxid e were abse n t P ure barium
, .

is sil ver white an d soft as lea d it d ecomposes water an d ah

-

solute alcohol The yellow color ascribed to the alkali n e earth .

metals by earlier observers is caused by prese n ce of n itride .

Stron ti u m H e n ri G autier worki n g i n Moissa n s laborato

.
—
,
1 ’

obtai n s by the actio n of zi n c an d of ca d mium on stro n tium

'

ry,

io d ide a zi n c alloy c ont ai n in g 1 8 per ce n t stro n tiu m an d a

,
/

ca d mium alloy co n tai n i n g 4 5 per ce n t cadmium By heati n g .

this last alloy in a curre n t of hydroge n at re d heat he obtai n s

stro n tium hydri d e .

2
G u n tz in co n seque n ce of G autier s p u blicatio n describes his
’
, ,

i n complete work o n stro ntium H e obtai n s stro n tium from its .

amalgam by the method which he used for barium but has ,

n ot yet succeeded i n getti n g it quite free of mercury .

The n itri d es of bariu m an d stro n tium were first isolated '

by the actio n of n itroge n o n heated impure bariu m a nd stro n

tium a n d stu d ie d by Maq u e n n e
,
3
While his specime n s .

were not quit e pure he establishe d their chief properties an d ,

their compositio n Ba3N an d Sr N The calcium n itride is

described fully by Moissa n i n his treatise o n calcium L ith
.
, 2 3 2
‘
.

"
ium n itrid e was first m ade from impure lithium by Ouvrard
a n d its ge n eral properties n oted I t may be sai d of the ui .

t r id e s of all of thes e four metals that they are bro nze colored -

solids that bur n i n air are readily acte d o n by chlori n e phos , ,

p h or u s sulphur a n d n otably by water which d ecomposes

, , ,

them qua n titatively i nto ammo n ia an d metal hydroxi d e and ,

by dilute acids which give salts of the m etal a n d a mmo n ium ,

.

6
G u n tz made pure lithiu m n itri d e from pure lithium by h eat
r ,

i n g it i n a curre n t of n itroge n H e co n firms the compositio n .

L isN give n by O uvrard H e says that whe n heate d in hydro .

g e n the followi n g reactio n takes place

L isN 3H, 3L iH N H
while if the hydride of lithium is heated i n n itroge n this re ac
tio n is reverse d
3 L iH N L isN N H, ,
.

Moissa n shows that this is n ot true of the calcium compou nds ,

1
9
C mpt nd 3 3
o 5 . re .
, [ , 100 .

1bi d . 13 1 2 09 .

h m ph y s
,
3 A nn i 2 2 15
c 9,
JO U R N A L
.

Th
. . .
,
4 I bid 1 8 , 2 89 ; is , 2 4, 1 .

C mpt
.
,
5 o . re n d . H 4 , 12 0 .
,
6 I bi d 12
, 3 , 99 5 .
 R epor ts .
4 89

for calcium nitride C a, N heated to a red heat yield s hy , ,, ,

d rid e while the reverse does n ot occur whe n the hydride is

,

heated i n n itroge n .

Mt e a l- A mmon zums .

The fact that potassium an d sodiu m are soluble i n liquid

ammo n ia formi n g blue solutio n s has bee n noticed by ma n y
chemists Joa nn is was the first to make a careful stu d y
.

of the subj ect an d ma n y articles by him are i n the Comp te s

,

R e ndu s i n the v olumes betwee n 1 0 9 an d 1 1 7 ,

i nclusive , .

The date of these articles is too early to i n clude them i n

this report but it may be said that Joa nn is believe d i n the
,

formatio n of u nstable compou n ds of the compositio n K N H,

an d N a N Hs while S eeley an d other observers thought the
,

so called so d ammo n iu m a n d potass ammo n ium to be merely

- - -

solutio n s of the metals i n liquid ammo n ia “

Moissan has settled this questio n an d shown that Joa nnis

.

was right To determi n e the temperature limit at which the

.

substa n ces could form and whether i n deed the metals would , , ,

act o n gaseous ammo n ia he brought the metals potassium ,

~

sodium lithi um an d calcium i n to co n tact with a curre n t of

, ,
°
dry ammo n ia gas at a temperature of 1 00 a nd at atmospheric
pressure By gradually loweri n g th e temperature he co uld
.

obs e rve the poi n t at which the ammo n ia gas attacke d t he

metals H e fou nd that in all cases a compou n d was formed
. .

The results were

°
Dry ammo n ia gas combi n es with lithium at + 7 0 with lique
factio n .

D ry ammo n ia gas combi n es wi th calcium at + 2 0 without °

liquefactio n .

°
D ry ammo nia gas combi n es with potassium at 2 0 with —

liquefactio n .

D ry ammo nia gas combi n es wit h so d ium at 2 0 with lique —

°

factio n .

A t a n y temperature above these the compou n ds break d ow n

i nto metal an d ammo n ia If the liqui d co mpou n ds are kept .

for a time at these temperatures the excess of ammo n ia escapes ,

an d the solids K N H S N a N H an d L i N H remai n These , s, 3

.
,

as well as the soli d calcium am mo n ium C a ( N H3 ) are stable -

, 4,

at temperatures below those give n H e mo d ified his e xp e ri .

°
me n ts an d proved that solid a m mo n ia at 80 does not act on —

a n y of these metals but as soo n as the temperature rises to ,

the liquefactio n poi n t of ammo n ia the metals are at

-
,

tacke d a n d all except calciu m dissolve .

Common Prope rti e s of the Me ta l A mm on i u ms A l l four ex .

-

c e p t i n g calcium give d ark blue solutio n s i n a n excess of liquid -

1 C mp t d
o 7 685
. re n .
, 12 , .
490 Repor ts .

ammo n ia Whe n this excess is eva porated bro nze colored

.
,
-

soli d s remai n If an y of the four metal ammo ni ums are al

.
-

lowed to sta n d e ither in solid form or d issolved i n liquid am

mo nia at temperatures so mewha t below the ir decompositio n
temperatures they give off hydroge n a n d form the metal
,
.

amide
L i N Hs z L i N H 2 H .

The amides of the metals are tra nspare n t crystalli n e sub

sta nces little soluble i n liquid ammo n i a The solid metal am
, .
-

mo n iu ms are all decomposed by water an d take fire in the air .

Further proper ties of this class of compou n d s have o n ly bee n

published i n the articles by Joa n n is Moissa n promises a n .

exhaustive article o n the whole field A s to the vale n ce of

Moissa n says : it may be regarde d as
.

calcium i n -

tetravale n t or it may be that calcium am mo n ium is

,
-

2 N H3 H e i n cli n es d e c i d e d ly to the former

.

v i e w t hi n k i n g that the behavior of the substa n ce do e s no t war

,

ra n t the latter .

B a ri u m A mmon i u m
1
G u ntz says that barium dissolves i n
-
.
-
r

liquid ammo n ia formi n g a bro n ze colored liquid ,

-
.

Stron ti u m A mmon i u m G u n tz says that stro ntium d oes

-
.
—
2

n o t form this co mpou n d as readily as barium at least liquid

ammo n ia d oes not cha n ge color i n co n tact with stro n tiu m .

A m mon i um A ma lg a m Moissa n reviews the history of .

—
3

ammo n ium amalgam an d decides to determ i n e the exact vol ,

umes of ammo n ia a nd of hydroge n give n o ff i n the d e co m p o

sitiou O n accou n t of the solu bility of ammo n ia i n water he
.
,

d eemed it n ecessary to avoid its use a nd used liquid ammo ,

n i a as solve n t H e first prove d that sodium amalgam is n ot

.

attacked by liqui d ammo n i a at temperatures below On

addi ng dry ammo n ium iodide the reactio n N H I N aH g 4 n
I

N aI N H4 Hg takes place without escape of gas th e n e w n ,

amalgam bei n g more fluid A fter thorough shaki n g wash .

,

i ng a n d deca n ti ng with liqui d am mo n i a to remove sodium

,
°
an d ammo n iu m io d ides the amalgam is coole d to 8o be ,
—
,

comi n g very hard A fter washi ng with ether saturate d with a .

hydrogen at the metal is place d i n a gl ass tube with

grou n d glass stopper an d co nn ected with a mercury pump .

The tube 18 e xhausted at 80 an d the temperature allowed —

°

° °
to rise l w ly A t 4 0 the mass begi ns to liquefy at 30 .
—
,
—

swells an d at + 1 5 almost fills the tube occupy i ng thirty

,
°
,

times its origi n al volume D uri ng this decompositio n heat is . ,

1 87 2 .

2 I bid 13 3 1 2 09 .
.
, ,
3 1 6 id 13 3 803
.
, , .
49 2 Rep or ts .

on the ammo n i um metals as it might be possible that the re ,

actio n 2 ( L i N H, ) , HS L i s + 2 N H , might occur at , , ,

low temperature A s a m atter of fact ammo n ia and .

hydroge n are give n o ff at In this exper i me n t too ,

the beauty an d i nge n uity of the experime ntal work com

ma n d admiratio n Moissa n co n cludes the article with these.

words : A mmo n ium which i n fact o n ly represe n ts a theo , , ,

re t ic a l co n ceptio n i n te n ded to u n ify som e formulas does not ,

°
s e m to exist at 7 3 i n the prese n ce of liqui d hy d roge n sul
p ie
—

”
ide .

U n til rece n tly little was k n ow n of compou nds of the

alkali a n d alkali n e earth metals with hydroge n H au .

te fe u i lle a nd Troost i n 1 8 7 4 studied the actio n of hydroge n , ,

o n potassiu m a n d sodium a nd fou n d that these metals ab ,

sorb hydroge n as does palla d ium an d that substa nces of metal ,

lic appeara n ce are formed to which they assig n ed the com

positio n K H an d N a H Wi n kler ? i n 1 8 9 1 stu d ied the ac
, ,
.
,

tio n of mag n esium o n oxides of calciu m barium an d stro n , ,

tium heated i n a curre n t of hy d roge n an d believe d fro m the

, , ,

behavior of the resulti n g mixtures toward w ater that hy d rides ,

of barium stro n tium and calcium were formed of the ge n eral

compositio n Me H The u n ivale n ce of these metals corre
, ,

.
,

s p o n d i n g with the se m iv a le n c e i f this term c an be u se d i n — —

the hydri d es of sodium and potassium Me H , ,

.

The first ray of light o n this subj e c t came from the fi n e work
‘
of G u n tz o n lithium an d its d erivatives I n a n a rtic le o n lithium .

hydri de he co nfirms Troost a nd H au te fe ui lle s observatio n ’

that below re d heat lithium absorbs seve n tee n times its vol
ume of hydroge n without cha n gi ng appeara n ce but he fi n ds
that if lithium is heated rapidly to a bright red i n an iro n -

boat i n a curre n t of hydroge n it takes fire a nd bur n s form

, , ,

i n g a fuse d very hard white m ass which a n a lysis proved to

, ,

be lithiu m hy d ride of the c o mp 03 1tion L iH The fused hy .

d rid e is n ot deliquesce n t ; is scarcely atta c ked by cold air ;

heate d i n air it gi ves L i O H 0 ; it decomposes water L 1H , ,

HO,
:L iOH H H eated 1n n itroge n it yields n itride and ,
.

ammo n ia The subj ect was n o t further i n vestigated u n til

1 8 9 0 whe n M
.

2
,
oissa n made calcium hydride from pure cal
oium It is muc h more active tha n lithium hydride Its
. .

properties were very carefully studied It has bee n already .

described i n this J O UR N A L .

B a ri u m hy dr ide was made i n 1 8 9 1 by G u ntz by heati n g , ,

1
3 16 i d .
, 12 7 , 29 ; A nn . c h i m ph y s . .
, 1 8 , 2 89 ; Th i s JO U R N A L , 2 4 , 96 .
 Rep or ts .
49 3

barium amalgam i n a curre nt of hydroge n at It is a

grayish w hite fused crystal li n e mass of the compositio n
-
, ,

B aH ,
It was n ot quite pure as he fou n d it impossible to re
.
,

move traces o i mercury an d of iro n from the boat Whe n .

heated i n n itroge n it decomposes at bright red heat formi n g -

,

n itride as d oes the hydride of lithium while calcium hydride

, ,

i s n o t attacke d by n itroge n .

Stron ti um hy dride was first ma d e by G autie r i n 1 90 1 The

I
.

a n nou n ceme n t was brief T wo weeks later G u n tz published .

2

his u n fi n ished work o n stro ntium a n d its hydride which h e ,

obtai n ed fro m stro n tium amalgam but as yet quite i m ,

pure Two weeks after this G autier publish ed a nother arti

.

3
cle i n which he describes pure stro n tium hydride he ob
t ai n e d it fro m a cad miu m stro n tium alloy by heati n g very -
,

s lowly i n a m ag n esia boat i n a porcelai n tube i n a curre nt of ,

d ry pure hydroge n
, The hydride w as a white fused solid . .

Its reactio n s are similar to those of calcium hy d ri d e .

P ota ssi u m Hy dr i de Moissa n rece n tly made potassium hy

"
.
—

d rid e by heati n g potassium i n a curre n t of d r y hy d roge n i n an

iro n boat i n a glass tube so that the u n der si d e of the tube is ,

at while the upper side is cooler The hy d ride sublimes .

a n d co n d e n ses as a ta n gled mass of s now white crystals on -

t h e cooler si d e of the tube Whe n e n ough has collected the tube .

is coole d i n a curre n t of hydroge n the boat slid back an d the , ,

part of the tube co n tai n i n g the hy d ri d e fused at both e nds .

Thus a tube of hydride is n ee d ed for every experime n t as it ,

is so rea c tive that it c an scarce be remove d from the tube It .

d eco mposes water takes fire i n cold oxyge n cold air cold , , ,

fl uori n e an d in col d chlori n e It is a viole n t red u ci n g age n t

, . .

It does n ot act on liquid ammo n ia but if heated with gaseous ,

am mo n ia yiel d s ami d e K H N H3 2 K N H H A n al y , 2 ,
.

ses prove the absolute purity of the hy d ri d e .

H e makes potassium form ate qua n titativel y by u n io n of p o

s

t ass i u m hy d ri d e a n d carbo n dioxi d e at or d i n ary temperature .

H e makes etha n e an d metha n e qua n titatively by actio n of

6
,

potassium hy d ride on ethyl iod i d e a nd o n methyl chloride .

Sodi u m Hy dri de Moissa n made so d i um hy d ride in the

"
.
—

same way as the potassium hydride which it resembles in ap ,

p e arance a n d react i o n s The best tem perature is He .

°
fi n ds that if t he boat be kept for some t i me at 3 6 0 the sodiu m
1
3
C mpt
o d 33 5 . re n .
, 1 , 1 00 .

16 1d , 13 3 , 1 2 09
. .

I bzd , 13 4 , 1 00
. .

4 1 6 141 8
, 13 4 , 1. .

5 I bi d , 1
3 4 , 261
. .

6 16 d 13 4 . 3 89
7 I bi d 13 4 , 7 1
. .
4 94 Reports .

in the b oat absorbs a n d dissolves some of the hydride for i f ,

the sodium is dissolved i n liquid ammo n i a a white substa n c e

remai ns u n dissolved which proves to be the hydride though ,

n ever quite pure as i n spite of all precautio n s it always c o n

,

tai n s traces of sodium oxide Obtai n ed by the sublimatio n .

method it is quite pure E R EN UF . . O .

A N ew Mth d f e o or the P repa r a tion f

o Un sa tu r a te d Hy droca r ’

6on s .

1
rece n t n umbers of the B e ri e hte W I p at ie w describes the
In .

results of a stu d y of the pyroge n etic d ecompositio n of al co

’

hols Whe n the vapor of the alcohol was passed through

.

tubes heated i n a combustio n fur n ace it was decomposed t h e ,

products de pe n di n g upo n the n ature of the tube or the foreig n

substa n ce placed i n it T he decompositio n s c an be expressed
.

by the followi n g equatio n s

( 1 ) C H, O H ,
C , H, H, O
( 2 ) C, H5 O H C H, C O H H, .

If a glass or iro n tube was used the amou n t of the u n sa t u

rated hydrocarbo n forme d was small The i n tro d uctio n of .

stick zi n c i n to the tube caused a co n siderable i n crease i n t he

amou n t of aldehyde for m e d amou nti n g in some cases to a ,

yiel d of 80 per ce n t Whe n o n the other ha n d powd ered .

, ,

zi n c wa s use d the yield of h y d ro c arbon w as i n crease d .

This suggeste d the possibility of securi n g some substa n ce

which would i n flue n ce the reactio n as much i n favor of th e
formatio n of the hydrocarbo n as stick zi n c does i n favor of the
aldehy d e .

'

E xp e rime n t sho we d that impure graphite such as is used ,

for crucibles would gi v e the d esired results If the vapor of

, .

the al c ohol was passed throu g h a glass t ube co n tain i n g the

scraps of broke n cruci bles whic h were heated to an ,

e n ergetic d ecompositio n took place with the formatio n of the

hydrocarb o n an d water The results obtai n ed i n several e x .

p e ri m e n ts will give a n idea of the yiel d O n e hu n d red an d .

fifty grams O f ethyl alcohol were passe d through the tube in

thirty mi n utes an d about half of the alcohol was decomposed .

The ethyle n e was absorbe d i n bromi n e and 1 6 0 grams of pure

ethyle n e bromide was o btai n ed O nly about 1 gram of alde .

hy d e was formed In a nother experime nt 1 2 7 grams of propyl

.
'

alcohol was used and i n a n equal time 1 6 0 grams of propyle n e

,

bromi d e was O btai n e d .

1 Be r d c
. . he m . Ge s .
, 3 4 , 35 7 9 ( 19 0 1 ) 35 , 1 04 7
49 6 R epor ts .

cerium salts by Marig n ac to bariu m chlori d e by E Siegle ,

‘
.
,

to potassiu m chlori d e ( a nd chlorate ) by H R ose to alumi n a

ium salts by A Mitsc he rlic h to plati n um salts by C laus

.
,

“ 4
.
, ,
6
to lithium salts by K Diehl to alkali n e chlorates an d nitrates .
,
7
by Frese n ius to mixtures of alkali n e chlori d es an d sulphates ,

by Kre tsc hy to ammo n iu m an d sodium sulphates and to

8
,

va n adium compou n d s by H R ose to potassium chloride by

°
.
,

B Sc hu ltz e to zi n c chlori d e by J a nn asc h and R ichards t o

.
l 11
,
o
,

sulphuric acid by H R ose to phosphoric aci d by Scheere r .

,
12

a n d by S
3 “ 1
a n d R ube piller to orga n ic acids by J an n asc h a nd ,

R i c har d s .

Substa n ces are k now n that i n hibit th e precipitatio n C hro .

6 1
mium salts m ay e n tirely preve n t it an d ferric salts i n hot ,
"
solutio n s behave i n a n a n al ogous way but quite feebly , .

Tartaric an d racemic acids restrai n it slightly an d alkali n e ,

8 1 19
citrates very markedly N itric acid ( u n der certai n peculi ar .

20 21
co n ditio n s ) an d metaphosphoric an d metaboric aci d s i nter ,

fere similarly .

A h d S ph y t t 8 65 ; l A
1 rc C h m ( L i bi g ) 6 8 6 es c s e na , 2 a so nn e e 21
J p k t Ch m 6 9 4 C mp H R
. .
,
P gg A
. . .
,
2 ra 3 6 7 ( 86 ) e 1 2 o a re os e o nn 11 2 1 1
Ma r :
.
, , ,

B g
. . .

hi n y
. .
,

A m .
J . Sc i .
, 4 1 , 2 88 ro w n i n : 1 bi d 4 5 , 403 P n e
l h e ti l e s i llu m bl
.
,

I 6 zd , 45 , 47 1 T he as t t re ar c s t r a te a d i ra y h o w one m y be a
s f m h u Ri h k Ch m 8
.

mi s l e by e r ro r d d P Zt h n ro t is so rc e c ar s an ar e r sc r. a or e ,

Th i s ti l t s f t h th e e s ul ts f a c e ful s t u d y o f t h d i ul ti a n d
. .

1
4 3 ar c e se or r o ar e c es
th e b e t w ay f d s l i n g w it h t h e m o e a
3 P gg A n n
.

o1 13 6 7 . .
, , 2

J 4 ak t C h m 8 3 45 5 r e
p ,

l J a h e sb e i c h t 1 86 p 3 3
. . .
,
5 Ib d 85 9 ( 86 ) z , 12 1 2 a so r r 1, 2
A n C h m ( L i e bi g ) 12 1
.
, , . .

5 n 8
9 5 287 )
e .
,

o mp a e G l d di g : J A m C h m S c
.
,
7 Zt c h n l Ch m s r . a a . 16 398e .
, , 2 1 0 c r a n . . e . o .
, ,
1 894 )
3 Zt ch n l Ch m s 10 39 6 r a a e ,
H n d b A n l C h e m 6th E d pp 368 45 6
. .

9 a a
0 Wag p 64
.
. .
, .
,
1
J h b n h t 88 ’
ne r s a re s e c 1 2 2

J p k t C h m 14 7 3 mp e Th i e l : Z tsc h n o g C h m 2 2
, . . .

11 ra e 21 co ar r a r e
. . .
, , . .
,

4 4 ( 9 )
2 1 00
H n d b A n a l C h m 6 th E d I I p 45 5
12 a . . e .
, .

J p k t Che m 7 5
.
,
13 ra 11
3 ,

C h m N w 10 9 ; a l J h r b i h t 864 p 69 5
. . . ,

14 e e s. 21 so a e s e r c 1
,

J p k t C h e m 1 4 7 3 5 ( 889 ) m p e Spil l : J C h m S c ( L on d n ) 10
. , , . .

5 1 ra 2 1 co ar e r e o o
.
, . , ,

( 85 8 ) G l d d i n g J A m C h e m So d Th i l Z t c h
. . . .
,

1 10 1 16 39 8 ; K ii t
a no g : c , s e r an e : s r a r .

C h m 19
. . .
. .
,

e , 1 01
h i m ph y [7 ] 4 49 4 ; W h itn e y Z t h ph y s C h m 2 0 40
.
,

6 R c u
1 A nn e o ra c s , sc r . . e .
,
, ,

C h m 19 5 3 L u n ge
.

e nius n l
. . .

17 F Zt re s h Ib d 19 1
: 4 9
sc r a a e , : z , ,

G l ddi n g J A m C h m S c 1 6 39 8 c mp O s tw l d Z t c h ph y C h m
. . .
.
,

a . . e . o .
, , o a re a s r . s . e .
,

3 9 34 °
18 Sp i ll e
1

J C h m Soc ( L n d on ) 10 0 r
:

e o , 11
S h On e P o gg A n n 1 12
. . . .

19 E c : 21
4
2 0 M t ph
,

ph o i c id c ll fo a m d tai l e d c n id ti n R e n t l y W i e s
. .
.
, .

e a os r ac a s r ore e o s e ra o . ec

g Che m 2 8 c ll d th e f t th t h e h d n o
,

le r (Z t c h n s 98 r a t t n ti n t
or 1 a e a e o o ac a a
difi u l ty i n an l y i n g b i um m t ph o ph ate w h r h m h d t t d th t t hi s
.
. . , ,

c a G z ar e a s e e as ra a a s a e a
a i d p rt l y p t t h e p e i p i t ti o fb i um ulph t T h
.

c a re v e n s i w e r h s n ot r c a n o ar as s a e . e re v e a

y t f und th i t t m nt i n G h m p p e s ; i n h i w e ll kn w n t i c l e e d b e fo e ’
e o s s a e e ra a s a r s - o ar r a r
t h e R y l S i ty tw o a n ly f b a n um m ta ph o s ph t
oc e e de ri b d b u t b ot h
o a a se s o e a e ar sc e

y i ld d p i p it t th t w h y ( P h i l T n 833 pp 5 3 t 84 ; l s P ogg
,

e e t
re c a e s a e re oo e av ra s 1 2 o 2 a o .

C lub R p i n t N o
. . , , .

A n n 3 2 6 9 ( 834 ) n d A l mb i 1 T h s t t m e nt t b e f u d a e c e r s, e a e s o o n
g d i n g t h i m tt ( F e se ni u A n l i t u Q u nt A n l 6 th
,

t xt b o k
. .
,

i n th e e -
o s re ar s a e r r s : e z r a a
p 5 ; H R e H an d b A n a l C h m 6 t h E d I I p 55 5 ; Me n s h ut k i n
. . .

E d I 1 2 os : e .
, , . c
A n l C h e m ( t an s b y L o k ) 3 9 )
. . .
,

b se d up n th e xp e i m e n t s o fS h e
. .
, . .

a r e r and c e 0 a re a o e r c e r
R ub e ( J p w hi c h c l l y h ow d t h e d i fii u l t y f c om
. . .
,

k t Ch m 7 5 3 ra e .
, 11 e ar s e c o

p l te p c i p i t t io n i n t h e p e s n c e f m t ph s ph i c cid ; thi w n fi m e d by
. . .

e re a r e o e a o or a s as c o r
Sp i ll e w k ( C h e m N e w s 10 9
r s
’
or It m i gh t b e ugg t e d i n e xpl n a t i o n .
, 21 s e s a
 Repor ts .
49 7

these cases there is more or less reaso n for the belief in

In
”
t he formatio n of do u ble salts or of complexes i n the solu ,

tio n s i n which compou n ds the barium or the sulphuric acid

, ,

o r both a re i n volved , .

If it is possible to disti ngu ish betwee n such cases an d those

w here other substa n ces i n solutio n ( i n some simpler way ,

p erhaps ) merely i n crease the solubility of the barium sulph ate ,

w e c an disti n guish a third class of substa n ces whose pres

e n ce at least i n an y co n si d erable amou n t
, is to be avoided ,
,
1
where barium sulphate is to be precipitated Nitric an d hy .

2 ‘ 3
d roc hlo ri c acid alkali n e an d ammo n ium n itrates belo n g
,

here U n der the co n d itio n s of most a n alyses however barium

.
, ,
5 6
s ulphate is very i n soluble ; so also i n water , ,
.

In order to pre c ipitate bariu m sulphate qua n titatively an d ,

i n a form easily filtered a n d washed a n d at the same time ,

least impure it is best to have the solutio n s which are to be

,
7 8
mixe d d ilute an d hot to mix them very slowly and with ,
°
c o n sta n t stirri n g an d to h ave the precipita n t prese n t i n c o n
,

h p
t a t rob a bl l m
y W i e s e r h a d c o nv e rt e d a l l o f h i s h f
e t a a c i d i n to t h e ort o a c i d b e ore
the p p b um ulph
r e c i i t a ti o n o f a r i m
s p ll f u
a te w a s h ph ph
a d e , fo r S i e r o n d or t o os o ri c
a c i d toh u h
a ve n o s cu h
i n fl e nc e u m h
B u t Sc e e r e r a n d R b e ’s s ta t e e nt t a t t h e p r e c i p i
f lu g ph ph
.

t a te s o r m e d i n s o t i o n s c o n t ai n i n m e ta os o ri c a ci d d o no t c o n ta i n i t , b ut th e
h fu g h xpl
o rt o a c id , i s c o n sin to t i s e ugg
a n a t i on A s e c on d s m e s ti o n o f a n e x p l a n a ti o
f m f h l l g h
.

a ri s e s ro th e a c t t a t W i e s e r w a s a na y z i n a t r i m e ta p h o s p h a te , w e r e as t h e
h f l g
o t e r s r e e r r e d to w e r e a n a y z i n u h hl M
h e x a m e t a p h o s p h at e s F rt e r , w i e ad d re l l
Ch m
.

(A nn e g ( L i e bi ) , 6 1, 5 3 l g um
m e n ti o n s n o di fli c u l ty i n a n a y z i n b a ri di
m ph ph h g h ulphu
. .

e ta os at e b y e ati n w i t c o n c e n t r at e d s ri c a c i d , L u d e rt ( Z t s c h r a n o r g
h u f ul h ppl m
. .

h m
C e , 5 , 33 o b t ai n e d r at e r n s a ti s a c to r y r e s ts w e n h e a i e d th e sa e
h l m xp f ul
.

m e t o d to h e x a m e ta p h o s p h a t e s I f F e i t a n n e e ri e n c e d di fi c ti e s i n t h e a n a l y
b um h m g g l g u l h
.

s e s o f a ri m e ta bo r a t e s , h e a v oi d e d t e b y d i e s ti n t h e fi n e y ro n d sa t w it
a solu um
ti o n of so d i g
c a r bo n a te ( P o g A n n , 7 8 , 36 1
D p
. .

2 1 H o rn i s s e r ta t i o n , 52
Cm p gg
.

1 a n d 2 P i ri a : I l i e n to , a n n o V 25 7 ( 1 84 7 ) H R o s e : P o A n n , 9 5 , 1 09
hl M
. .

C l C m p l h l
. . . .

( 185 5 ) a v e rt : he G az 1 85 6 , 5 5 ; a so P i ag , 1 1 , 39 0 ( 1 85 6 ) N ic o
hl M
. . .

J Ch m
. , .

so n a n d P ri c e : P i ag , 1 1 , 1 69 ( 1 85 6 ) N oa d : e So c ( L o n d on ) , 9 , 1 5
Ch m h m
. .

gl J
. . .

( 1 85 7 ) Si e e p ra k t e , 6 9 , 1 4 2 ( 1 85
6) G a tk o w s k y : B e r d c e Ge s , 5 ,
M
. .

l g J
. .

m Ch m
. . .

3 30 ; E r d a n n a n d Ji tte n z w e y p ra k t e , 7 5 , 2 4
1 ( 1 85 8 ) G a d di n : Am .

Ch m
. . . .

e Soc 16 , 39 8
u l Ch m
.

3 Fr e s e ni s Zt s c h r a na e , 9 , 5 2

m M
. . .

4
E rd an n a n d i tt e n z w e y L oc c i t
u p qu lu p
. .

5 F r e s e n i s : L ac c i t O ne a rt r e i r e s fo r i t s s o ti on a rt s o f w a te r .

l Ch m full k
. .

u
F re s e n i s ( Z t s c h r a n a e 3 0 , 45 5 c are y r e p e a te d h i s w o r an d
f u p qu lu p g
.
, . .
.

o n d on e a rt r e i re d for i t s so ti o n ar t s o f w a t e r ( co n tai n i n p e r ce nt
h hl
y d ro c o ri c a c i d a n d ulphu p e r c e nt s ri c a c id )
M u C mp pl lu l p
.

0 a r g e r i tt e ( o t r e n d , 3 8 , 308 h ad a c e d th e s o b i i ty a t 1 ar t 1n
p hl C l pl p
. .

a rt s o f w a t e r , w i e a v e r t ( L oc c i t ) a c e d i t at 1 a rt 1 n 8 0 000 a rt s o f
0,
C l ul f m l l u xp m
. .
.

w a te r a c a te d ro e e c t ri c a c o n d c ti vi t y e e ri e n t s , i t s s ol ub 1 11tv 1 n w a t e r
C
.

p
i s 1 a rt i n p a rt s o f w a te r a t p p or 1 a rt i n a rt s o f w a t e r at
g ll m
C , a c c o r d i n to H o e ph C h m
a n ( Zt s c h r y s p
e , 12 , 13 1 O ne a rt d 1s s o l v e s
g hl u h ph
. . .

p
.

in a rt s o f w a t e r a t 1 9 C , a c c o r d i n to K o an d R ose ( Z t sc h r
°
ra sc ys . .

Ch m
.

e 12 , 2 4 1
Bu l Ch m mm h h l
.
,

7 n s e n ( Z ts c h r a n a e 10 , 39 6 re c o e nd e d t at e ac 1 00 c c y i e d .

g m um ulph l Ch m p
. .

ra o f b a ri s ate H R os e H and b A n a . e , II , 4 5 4 ( 1 87 1 ) th e . . . . .

p p u h ugh l h p p f m u
.

c o c e n t r a te d so
r e c i i ta te r n s t r o t h e fi te r w e n r e c i i ta t e d ro
n l ti on s .

h k Ch m
R i c a rd s a n d P a r e r : Z t s c h r a n o r g m e lu
, 8 , 42
1 th e or e d 1 l u t e t h e so ti o n th e
l um hl l p p ulph
. . .

e s s b a ri c o rid e i s e n c o s e d b y t h e re c i i t a te d s a te .

8 H R os e l Ch m
H an d b A n a e , II ,
pu
p 45 5 ; h f m
t h e p r e c 1 p 1tate i s re r w e n or ed
lu h h mp u M l
. . . . . .

i n h ot s o ti o n s t a n i n t o se at 0 rd 1n a r y t e e ra t r e s e n sc h u t k i n A na .

m ph u u h ugh
.

Ch m e k p
( t ra n s b y L o c e 39 t h e p re c i i tate i s a or o s a n d r n s t ro th e
lup
.

l h
. .

fi te r w e n i t h a s b e e n o rm e d i n c o 1d s o ti on s .

p
9 H R os e : L o c ci t h k
R i c a r d s a n d P a r e r : L ac c it , th e p r e c 1p i
mx p
45 4 . .

l m um hl h lu
. .
, . .

t a te s e n c o s e o r e b a ri c o rid e w e n t h e so ti on s a re i e ( q u 1c k l y .
49 8 Rep or ts .

1
sid e rabl e excess i n the resulti n g mixture The solutio n of th e .

barium salt should always be ad d ed to that of the sulphate or

sulphuric acid and if it is permitted to flow d ow n the wall of ,

the beaker i n which the sulphate solutio n is co ntai n ed a n d ,

thus meet the latter i n a broad thi n film the precipitate is , ,

2
less impure tha n i f the solutio n be a d de d d rop by d rO p It is .

3
customary to have prese nt some hydrochlori c acid to aid i n
‘
co n vertin g the precipitate e n tirely to the crystalli n e form .

It is usual also to d igest the mixture some time over a low

fl am e a n d to filter o nly after the mixture has become col d
5 6
.
,

Various in e thod s for re movi n g the substa n ces which bariu m

sulphate has carried do w n w ith it have bee n suggested .

Treatme n t with hydrochloric acid was tried an d aba n d o n e d by

7
Berzelius as i n e fli c ie n t an d it has su c cee d e d little better i n ,

the ha n ds of other c he m ists B rii g e l ma n n however re c o m

9 f
’
, ,

me nds it as an aid i n p art i ally ove rc o mi n g the errors d u e to

e n closed substa n ces Solutio n of the impure precipitates i n .

co n ce n trate d sulphuri c aci d an d reprecipitatio n by d il uti n g

these solutio n s w as a d vised by A Mi tsc he rl i c h but it i s
,
0 1
.
,

self evide n t that such a proce d ure is useless where barium

-

11
salts co n stitute all or part of the impurity ; yet this method
B l i u L h b d C h m i III p 5 ; w h
1 e rz e lu ti n t i i n g qu i
s: l nte r e r e e 10 e n so on s c o a n e va e s
i um hl i d nd p t i um ulph t mix d t f th b i um
.
, .
, .

ofb ar c p or e a o ass s a e a re e e r ce n o e ar
u d m i u p i pit t d C mp N t f th i p t J ul i A
,

se re a ns p 495 n re c a e o a re o e 12 o s re or o n nn
h i m ph y s 74 ; w he n lut i n s on t i i n g b i um h l i d a n d s di u m
.
, .
, . .

c 30 , 2 so o c a n ar c or e o
s ulph t e a t N / d i lu ti on re m i x d l t s re m i n u d mp e d fte
. . .

a 5 f th e
000 a e o sa a n e co os a r
t w e n ty f u h u ; on l y f te f u d y i t h p e i p i tati n mpl e t H R se
,
- o r o rs a r o r a s s e r c o co e o
n ex f b i um s l t h mpl t p e c i p i t ti on R i c h d n d
. .

L c o t ;
. a a te n ce ss o ar a as s co e e r a ar s a
k r L c t p 4 9 ; a n x s of b i um c hl o i d d i mi i h t h e s lub i li ty o f
.

P ar e : oc . z . 1 e ce s ar r e n s e s o
c i p i t te m u n t of b ri um c hl i d e n c l d
.
,

th e re nd d s n ot i n c e th
a a oe re a s e a o a or e os e
pR i c h d s n d P r k p 4 0 ; th e w i e t h e qu a n tity f b i um c hlo
.

Lar c t a a e r : oc z . 2 o r s o ar
g t p 45 5 i f t h e ulph t p a t i n
. .
,
b

ri d e i e d d ow n
c arr H Ro L a t 13 re a e r . se oc . s a e se ra e s
l i qu i d w h i c h ont i n n b i um c hl id i n x lmo t f e f m b i um
.
, .

a c it i a s o ar or e e ce ss s a s re ro ar
c hl o id e Comp
r w i th th f ll ow i n g w h e e t h e e e se d e is f ll w d an d
a re e o r r v r or r o o e
re o mm n d d M r B ow n in g n d P h i n n y N ote p ge 496 of th i s p t Th e i r
.
,

c e e a , r a e 2 a re or .

p i p i t t s n tai n e d b a i um l t i mpu i ti b u w h n pu i fi d by olu

, , ,
”
re c a e co r sa s as r e s, e ca se e r e s
ti n i n
o nce nt t d s ulphu i
co c id nd e i p i t ti n t h y w i gh e d m
ra e e th n b e r c a a re r c a o e e or a
fo re M xpl ai n e d th i s s d u e to ar e i ual n t m i n ati o n a re s co a .
”

an l C h m 9 5 ( 8 7 ) i f mu h h y d c h l i c ac id i s p e s
3 F r s ni u
.

Z ts h
e e s c r a e , 2 1 0 c ro or r
e n t i t mu t b e r e m p atio n b e c u e it h a g t l n t ti n n b ri um
. . .
,

e d by s ov e va or a s s re a so ve ac o o a
s ulph t R ich k e L c t p 4 ; th p e e n f mu h f hyd o
,

a e d nd P ar s a ar r : oc z 20 e r s ce o c re e r
c hl o i m ou l y i m ou n t f b i um c hl i d e n l s d
. . .

"
idr c ac n th e or s n c re a s e s e a o ar or e c o e
O s tw l d Sc i n ti fi c F o u n d t i n f A n l y ti c l C h m i s t y ( t b y Me
.

4 a e a o s o a a e r ran s .

G ow n ) 2 2 1 9 7 a ,
5 R i h a ds L oc i t p 4 6 ; b ou t n h u r
, .

”
n d P rk e r
c r a a c 1 a a o
C omp a N t 6 p 497 f t h i s re p t
.
, . .

5 re o e o or
p 49 5 f th i s re p t
, .
, .

7 L c i t N te
o . c o 1 0, o or
t e t m e n t w i th h y d o hl i c c id i s u e le s
, ,

L o ci t p 45 5
. . .
,

H R 3 e os c. r a r c or a s s
”

an l C h e m 16 2 ; ft h e ti n g i n c r u c i bl th e p r c i p i tate i s
. . .

9 Zt c h s r. a , 2 a e r a a e e
t e t d w ith 3 o 4 d p s f m d e t e ly t r n h y d c hl i c c i d th lump o f t h e
.

r a e r ro o o ra s o ro or a , e s
p e c i pi t te b i n g b o k n up w it h gl s ro n d th m i x tu e w a m e d tw m in u te
r a e r e a a s a e r r o s
w i t h o u t b i l i n g ov g fl m
o T he lu tion ob t in d i s p u d th ough s m a ll
e r a as- a e so a e o re r a
fi lte a nd t h e n t h w h o l e p p te d s e a l ti m s u nti l th e fi l t d l i qu i d
.
,

r ti n e o e ra o re e a ve r e e re
r e m ins a l e w h n t e te d w i t h ulphu i c a c id Th n th nti e p i p i tate i s
c ar e s s r . e e e r re c
b ro ugh t up n th e fi l t w h d w i th b i l i n g w te r d i d h e t d an d w e i gh d
o e r, as e o a , r e a e e .

r k t Ch m
, ,
10
J p
1 T h s w a s p i n te d o u t
8 3 4 5 8a e ,

t t h e ti m ; se e Ja h b e i c h t 86 p 845 f t n t ;
. .
. ,

1 1 o a e re s r 1 1, oo - o e
C mp e R i h d s a n d
.

an l C h m
.

a l so l t niu
,

by F e
a e r Zt h 9 5
r se s : sc r a e 2 o ar c ar
k e r L oc ci t p 4 3 a l M r P h i n n
.
,

n d B ow n i ng
. .
,

P ar . .
,
L oc ci t. 1 so a , ey , a r . .
5 00 Repor ts .

red heat O ver a blast lamp it will lose i n weight as much as

.
-

1 per ce n t i n thirty fiv e mi n utes It is the n alkali n e i n -

.

reactio n the loss havi n g bee n d u e to the escape of sulph u r

,

trioxide .
‘
D W H N . . OR .

Gra vi m e tr ic De te r mi n a ti on ofSulphu ri c A cid i n the Pr e se n ce of

The precipitatio n of barium sulphate qua n titatively and i n ,

a pure form is probably n o where else of so great i n d ustrial ,

importa n ce as i n the a n alysis of pyrites The fact that iro n .

salts i n terfere at times if no t alwa y s i n such a n al y ses is a ,

matter of great sig n ifica nce to t ho se c on c e rn e d therei n an d ,

o n e of i n terest to all chemists as a special an d probably th e ,

”
best k n ow n case of occlusio n of impurities by a p re c i p i
tate Berzelius first observe d this fact an d was of th e O pi n io n
.

( which it is believed th i s report co n firms ”

) that it is n e c e s
2
sary to begi n by removi n g the o x i d e ( of iro n ) .

Four d i ffere n t ways of avoi d i n g the d i f fi cu lties i n cide n t to

such a n alyses fi n d expressio n i n the methods which are re c om
me n ded i n the literature
1 The separatio n of the iro n an d sulph ur by fusio n with
.

some oxidizi n g flux .

2 The separatio n of the iro n as hydroxide by mea n s of

.
,

ammo n ium hy d roxide from the solutio n i n which the sul ,

p h u r i c acid is to be determi n ed .

3 The re d uctio n o f the iro n i n the solutio n to the ferrous

.

co n d itio n before precipitati n g the bari um sulph ate

,
.

4 The rete n tio n of the iro n i n the solutio n by the a d d itio n

.

of orga n ic acids before the precipitatio n .

3
The first pri n ciple is i n volve d i n the Frese n ius method by ,
‘
which the pyrites are fuse d with a mixture of potassium n i
trate an d alkali n e carbo n ates a nd the sul phuri c a c i d d eter ,

mi n e d i n the filtrate obtai n e d by extracti n g th e melt with cold

water after removi n g from it all n itric a ci d The m ethod h as .

5
bee n repeatedly tested an d seems to have becom e the criterio n
by which other methods are j u d ged .

B u i g ul t C mp t
1 o ss n d 64 5 9 ( 86 7 )
a Zt h n l Ch m: 7 44 ;
o m re n 11 1 sc r a a e .
, , 2 co
C h m (L i bi g )
, , . .

p Bu n
. .

ar e A se n 6 nn e e 111, 2 2
h i m ph y
. .
.
2
A nn 4 37 6
c s 1
u Qu
,

l F ni u l 6 th
. . .
,

zt s h n 1 h m 6 339 ( 87 7 ) A n l it t A
gf
sc r . a a e 1 , 1 a so re se s e . z r an . na .
,

p
q
.

Ed ll 45 3 ( 1 89
he g
mp i ti n h e b e e n o mm n d d L i m e n d s d b y
.

4 Ot r re a e n ts or de co os o av re c e e a o a,
H ye s A m
a C h mi t 5 7 u ti p ot h n d b rom i n w te r by Il : B e
e r e s 2 1 ca s c as a e a e s r.
k J S c C h e m In d 885 p 3 9
, ,

by C l
.

che m Ge s an d m g n
.

. 1 1 1 8 7 ; sod .
, i , 1 a a e s a, ar . o . . . ,
1 , . 2 .

5 F e se n i u sr L oc c i t Zt hr n l C h e m 1 9 5 3 ( 88 L u n g e I bid 19 4 9
: sc a a 1 0 : , 1
°

Fo th e e x t n aly i o f
.
,

d R ic h
. .
,

k t C h m 14 7 333
. . .
,

J an n a h ds J p
‘
sc an ar ra e r ac a s s

p y i te F e n i u m th d f fu io s u e xp i m e n t s i n d i t i th b t d on l y
. . .
, ,
’
r s, re s s e o o s n a o r e r ca e s e e s an

J p k t C h m 1 4 8 4 1 ( 889 ) Z t h n g e w
.

o r e c t m e th od
,
”
c r L un e nd O b g i a re a ra e , 2 1 sc r . a .

C h e m 889 47 6 G l d i n g J A m C h e m S c 16 4 1 ( 894 ) C h e m N e w s 7 0 1 8
. .
. .
.

1 a o 0 1 , 2
n d Mi s li n
.
.
, . .
, ,

L un g g C he m 2 1
. . . .
,
Zt c h n
e a 98 s : s r . a or . .
, , 1
 Rep or ts .
501

It has bee n criticized as troublesome and tedious Further .

1
,

the oxidizi n g flux attacks the crucible an d the dissol ved

plati n um may i n terfere with the subseque n t iro n determi n a
2
tio n an d where coal gas is used i n the burn er over which t he
,

fusio n is accomplished the sulphur it co ntai n s may give rise ,

“
to co n siderable errors .

L u n ge devised a method i n volvi n g the seco n d pri n ciple

“
already me n tio n ed The origi nal L u n ge method co n siste d i n .

5
dissolvi n g the pyrites i n aqua regia eva porati n g this solutio n ,
“
repeate d ly with hy d rochloric aci d to get rid of n itric aci d d i ,

luti n g the residue an d determi n i n g the sulphuric acid in this ,

solutio n as usual B ut th e barium sulphate precipitates thus .

obtai n ed are always re ndere d impure by th e prese n ce of iro n

7
compou n d s an d weigh too mu c h or too little accor d i n g to , ,
“
the heat to which they are subj ected before weighi ng To .

“
avoid this L u n ge mo d ified his metho d i n troduci n g the pre
, ,

c i p it at io n of the iro n as hydroxi d e by ammo n ium hydroxide

a n d determi n i n g the sulphuric acid i n t he filtrate therefrom .

O n e c a n obtai n excelle n t results by this mo d ifie d L u n ge

metho d but m a n y a n alysts have experie n ced d iffi culties i n
,

so d oi n g o n accou nt of the formatio n an d rete ntio n of some

,

basic iro n sulphate i n the ferric hydroxi d e precipitate A a .

result of this the method has ofte n bee n co n dem n ed an d as ,

“o l
ofte n vi n dicate d .

Because of this diffi culty an d to do away with the tedious

washi n g of the ferric hydroxide G lad d i n g mo d ified the ,

L u n ge method i n that he d irecte d i n stead of washi n g out ,

all sulphuric acid from the ferric hydroxide to dissol ve the ,

precipitate i n hydrochloric aci d and the n add barium chlo

ride collecti n g the sulphate obtai n e d o n the same paper as
,

L unge : Sulphu ri c lk a l i p l he m
1 “
c id an d
"
A A I 5 5 ; Z ts c h r an a C 19 , 4 19;
G l a d di n g J
. .
,

Ch m Che m
, .
, . .

: . A m . e . So c 16 ,399 ( 1 894 N e w s, 7 0, 1 82 .

Ch m
.

2
J an n a s c h : J .
p ra k t . e .
, 14 7 , 334
3 P ri c e Z ts c h r an a l Ch m
. e .
, 3 , 483
u p
.

4 H a n d b d e r Sod a I n d s
”
I , 96
he rh v b l P um i e n i t i c a c i d F e s e n i u s c o mm e n d e d
.
, . . .

5 Ot so v e n ts a Su l e e en re r r

p h uri A c i d n d A lk li a i d a n d b o mi n e G l ddi n g J A m Che m p 5

,

n i t ri ”
c I a a 2 c c r a
C h m N e w 7 0 18 ; l o L u n ge : J A m C h m So 1
. . .
, .
, .
,

So 1 6 39 8
C h m N w s 7 1 3 ; n d G l d din g : J A m C h e m Soc 1 7 397 ( 8953
c .
, , e . s, , 1 se e a s . . e . c .
,

18 1 e e , 1 2 a a . .
, 1 .

C a u6sti s d olu ti n n d b om i n e D ow n C h e m N e w s 4 3 89 ( 188

.
, . .
,

c o a s o a r , r . , , 1
C o mp e F se n i u s Zt h a n l C h e m 9 5 2
ar re sc r a
m a e L u n g e 1b d 19 4 19
,
e n i u s : Z ts h n l Ch e m
. .
.
,

7 F re s 1 9 5 3 ( 88 ) c r a a 1 0 co r i .
, , .

J n n asc h a n d R i c h a d s J p a k t C h m 14 7 3 1
. . .
, ,
8 a r r e 2
,
9 L ung Zt s c h r a n a l C h e m
. . .
,

e : 19 4 9 . .
, 1

J n n c h n d R i h d s J p k t C h e m 14 7 333 ( 1889 ) 1 b d 14 8 2 36
.
, 0

10 a as a c ar ra i
, .
, ,

C h e m 889 p 47 3
. . .
,

L un B b e at an d O b
e ar gi ] bi d z148 39 ; Z t s c h ng w re a : 2 r. a e , 1 . .

G l a d i n g J A m C h m So
. .
, , , ,

C h e m N w s 7 0 8 1 L un ge J A m
. .

: 1 6 39 8 ( 189 4 ) e c e , 1 . : .

C h m N e w 7 1 3 G l d din g J A m Ch e m S c 17
. . .

C h e m S c 17 8
. .
, , .
,

o 1 1 e s, 1 2 a : o , ,

L u n g and
. . . .
, ,
C h e m 1 9 45 4
.
, .

L un g
. .

39 7 I b d 17 7 7 e : Zt hr no g i 2 sc a r e
M ss l i n I b d 2 1 98 ( M i n e k Z t c h a n a l C h m 3 8 5 ; I b d 3 8 35
. .
, , . . .
, ,
’

i i 1 1 e e : s r e , 21 i , 1.
C h e m 2 1 2 00 ; P tti n on J So C h e m In d
.
.
, , . .
, ,

L u nge n d Be bi e
.

a Zt c h a n rg s r. o a s : c . .

1 885 p 3 9 ; 1 bi d 1 890 p 2 1
.
. .
, ,

, . 2 .
, , . .
5 02 Repor ts .

’
that used i n the first filtratio n L u nge protested vigorously . .

The G laddi n g modificatio n as such has probably n ever

come i nto ge n eral use but is n ow used i n a form proposed by ,

K ii ste r a n d Thiel which co n sists i n omitti n g the collectio n of ,

the ferric hydroxi d e on a filter but d issolvi ng it as did G lad , ,

di ng with hy d rochloric acid after an excess of barium chlo

,

ride has bee n a dd e d to th e a m mo n iacal solutio n from which

the iro n was precipitated but i n which it is still suspe n de d , .

2
This method has come through n umerous tests an d attacks .

The idea of reduci n g the iro n to the ferrou s co n ditio n origi

n a t e d with J ann asc h a n d R ichards i n a n a n alogy to tita n ic ,
“
acid It seemed possible that ferrous salts woul d not be car
.

ried do w n by barium sulphate as were ferric salts B ut after .

“
tryi n g this pla n usi n g zi n c and hydrochloric acid for the re ,
‘

ductio n they aba n do n ed it because th e precipitates still c on

,

t a i n e d n ot o nly iro n but also zi n c compou n ds A detailed , .

5
study by Thiel co n firms this a n d i nd icates a further d ifli c ul ty
arisi ng from the excess of zi n c retai n i n g some of the sulphuric
aci d O n the other ha n d H eide n rei c h Mei n eke an d L u n ge
.
“ 7
, , ,
“
a nd Bebie have gotte n excelle n t results by this metho d The .

expla n atio n of this appare nt co ntra d ictio n will o n ly become

appare n t probably whe n n ot results alo n e but also e x p e ri me n
, ,

tal details are published by those who use this method suc
u l ly
ce ss f .

The fourth last method was likewise applie d first by an d

° 10
J an n asc h a”n d R ichar d s The orga nic acids they u sed to .

keep up the iro n were formic acetic an d citric but , , , ,

n evertheless the bariu m sulphate precipitates co n tai n ed iro n , .

1 1
L ater G laddi n g trie d a n d aba n do n ed this pla n usi ng citric
, ,

acid K ii ste r an d Thiel used oxalic an d tartaric acids with

.
12

G l dd i g J A m C h m S
1 a 16 4 4 4 ; Ch m N w
n 7 : 8 . L u g . e . oc , 01 , 0 e e s, 0. 1 2 n e

J A m Ch m S 8 ; Ch m N w
.

7 e 7 3 L u g
. d K l
oc J Am 1 , 1 1 e e s, 1, 1 2 n e an von e er :
Ch m S g w Ch m
, .

l Zt h 89 5 pp
. . . . . .

e 7 83 86 ; oc 1 , C l d di g J A m
1 —
1 a so sc r an e e 1 a n
Lu g
. .
, . . . . .

Ch m S
,

e 7 99 oc 1 bi d ,7 7 75 1 , n e : 1 ,

Th i l Z t h g Ch m Lu g
. . .
,

K ii t
8 n s e r a 9 98 I bi d 9 45 5 e : sc r a nor e 1 n e 1
d Mi l i n I bi d
. .
, , ,

L u g
.
, .

K ii t d T hi l 16 i d 73s e r an 98 e : 2 1, n e an ss : 2 1, 1
Mi k
.

l C h m 3 8 9 5 Ib d 3 8 35 L u g
.
, ,

Zt h e ne e : d sc r an a e 20 21 i 1 n e an

g Ch m
.
, ,
B bi Z t h
. .
, , .
, .

e e sc r . an or e .
, 2 1 , 2 00
J p k t Ch m 4 7 3
.

3 ra e 1 22
,

u d oth e d u i n g g nts l o m e ta ll ic a lumi ni um h

. . .
,
4 a n n as c h a n d R ic a rd s se r re c a e a s :
m e t l i c m g n i um n d d um m lg m B ut t h e p i p i tat lw y i m
,

a a e s we e a so i a a a re c e s r a a s
pu e Si n c e t h n J h n s n ( C h m N w 7 0
,

p o p d s d i um h y p 0 p h s
.

r e o o e e s, , 2 12 r os e o o

p hi te a s t h e e d u n g g t b ut L u n g e ( J A m C h m S
. .

r 17ci 1 8 7 ) h as s h o w n t h t a e n , . e oc , a
Jo h n son s l i m s f th m th od a n ot b n o ut b y e xp e i m n t
. . .
,
’
c a or is e re or e r e

g C h e m 2 2 44
.

5 Zt hr n sc a or 1
. .
,
8
[bi d
7 Z ts h r an l C h e m c 38 9 35 . a .
, , 20 1

g Ch m 2 1
.
,
8 Zt h an sc r or e 2 00
. .
,

p ak t Ch m 1 7 3 5
_
9
J r e , 2
gan i c ac i s p e e n t c o mpl e te p e i p it tion Sp i ll e r J C h e m Soc
. . .
,
1 0 S me
'

o or r v r c a . : . . .

( L on d o n ) 1 0 , 1 10
A m C h m So
,
1
J 1 . 1 6 339 . e . c., ,
1 2 Z ts c h r a n o
g C h e m 19 1 1 . r . .
, , 0
5 04 Rep or ts .

all the iro n i nto n eutral ferric sulphate the perce ntage of iro n
,

i n the precipitates becomes practically co n sta n t with a value ,

of about per ce nt Further the mass of fe rric sulphate

.

i n the precipitates beyo n d this limit i n creases directly as the

mass o f barium sulphate Whe n a co nsta n t amou nt of barium
.

sulphate is precipitated i n the prese n ce of varyi n g amou nts of

iro n i n equal volumes of solutio n experime n t proves that an
,

excess of ferric sulphate is without i nflue n ce after the barium

sulphate has o n ce reached its m aximum ability to retai n iro n .

A ccordi n g to Sch n eider these experime n tal results clearly i n di

cate that we have here to deal with a solid solutio n the ,

bariu m sulphate bei ng able to dissolve ferric sulphate but

.
, ,

like any other solve nt o n ly able to dissolve it up to its o w n

,

poi n t of saturatio n a perfectly co n sta n t proportio n no m atter

—
,

how great the excess of ferric sulphate prese n t .

To o ne who has followed these matters carefully

”
through the literature either the Frese nius method or the
,

L u n ge method i n the fi nal form give n it by K ii ste r an d

”

Thiel recomme nds itself as reliable for the determi n atio n of

,

sulphur i n the prese n ce of iro n The zi n c reductio n

.

”
method ca nn ot be co n sidered as trustworthy at pres ent a nd ,
”
the orga n ic acid method is u n reliable A s to an expla n a.

tio n of the appeara n ce of iro n i n barium sulphate precipitates ,

it seems u n j ustifiable to go beyo n d Sch n eider s co n clusio n s’

u n til fu rther experime n ts have bee n carried out D w H N . . . OR .

 I N DE X TO VO L . XXVI I .

A U THO R S .

A CR E E , SF . . C on s ti t ution of p h e ny l u ra z ol e

A l la n , F B . . Sulph ate s f bi s mu t h
o . .

A l le n , E T . . an d Gottscha lk , V H . . R e s e ar c he s on th e o xid e s of

R e d u c ti on o f tu n g sti c ac id ; th e b lu e n d a b ron z e h y d ox i d e s ;
r

ac ti on o f h y d ox y l m in e o n so lu b l e t u n g s t r a a te .

A sh ley , H E . . Se e Fay , H .

BA I L E Y , E . H S . . and Ca dy , H P . . L a b o r a to ry gu id e to qu l i ta a ti v e a na l y si s
( R e vi e w )
B a r n es j Se e /on e s H C, .
, . .

B e a r dsley A P Se e Whee le r , . .
, 11 L . .

Be n ed ic t M n n i g C R A h e m i c a l m e th o d f obta in i n g v a c u
, F G . . an d a n , . . c or a.

B e n a d ou f B
r Sm k e l e ss p ow d e n i tr oc e llul os an d th o y o f t h e Ee l l ul
, . . o r, e , e r ose

m o l c ul e (R e vi w ) e e

Bl ke j C an d F C R at f h y d ti n of m e ta ph os ph o ri c
_ a , . . . . e o ra o

Borche rs W , Se e N e r ns t PV
.
, .

B ou dou ar d , 0 Se e L e Ch a te lie r H
.
, .

B r u n t, G . U e be r fe s t e L os ung en

C A DY , H P . . Se e Ba i ley , E . II . S .

Casp a r i, C E . . I . I n v e s ti g a ti o n o f t h e fatty oi l i n th e se e ds o fL i n de r a Be nz oi n .

II . L a ur i e a c i d a n d i ts
'

Ch zkash zgé M . Se e K u h a ra , M .

C k ri sty , S B . . The e l e c t ro moti ve fo rc e o f m e t l s in solu tion s of c y

a a n id e . .

Cl a r ke , F . W . T he ca c l ul a ti o n o f a t o mi c

Coug h li n , P . P re pa r a ti o n o f b ro m o fo m b y e l r e c t ro ly si s

E VA N S P , . N . and Va nd e r kle e d , C E . . Di c h l orac e ty l

FA Y H ll oy s of an ti m ny an d te llu rium
an d A sh ley , H E . . A o .

T h e ll oy s o f l a d n d Gi ll son , C B . . a e a

F oote H W , O n th mi x e d y t l f i l e c hl o r te n d sodi um c h l ate

. . e cr s a s o s v r a a or

n d th i s lu ti n a e r o o s.

F raps G S So l u b i l i ty o f b
, .i um s ulph te i n f r ri c h l o ri d e a lumi n i um c hlo
. ar a e c ,

r id e n d m g n e i um , a a s

F P C a n d N vy F G
r ee r ,
. O n th e for ma ti o n d e c mp os i ti n
. d g r mi c id l
o , . .
, o o , an e a

c ti on f b e n oy l a c e ty l n d d i c t y l p ro x i d s a o z a a e e e .

G A T T E R MA N N L P ac t i c l m e t h od fo g a n i c c h e m i s try ( R e i e w )
, . r a s o r v

Ge tm F H
an , Se j nes H C . . e o . . .

G1t6 e rt, j PV Se e K as tle ] H

’

. . . .

Gi ll son , C B Se e F ay , H . . .

Gilp i n , j E A c t io n o f os . . ph ph oru s p e nt hl ac o r id e o n a ni lin e .

Sulphu ri c c id n d i t p e p a a s r a r a ti on b y th e c o nt a c t m e t h od (R e
p o rt )
Gottsch alk , V H . . Se e A ll e n , E . T .

H IL L H B , . . and Wh ite , G R . . O n (ll-n i t rO p y rom u c ic ac i d .

H olle ma n , A . F . an d Ma n chot W . L e h rb u c h de r a no r ga n i c h e s n C h mie e (R e

vie w)
Hy de , E . P . Se e J on es H C , . .
5 06 In de x .

JA E GE R , W . D ie N m a l e l e m e n te u n d i h
or re A nw e n d n u g i n d e r e l e k tri sc h e n
Me s s te c h n i k ( R e v i e w )
j h nson B Wh e e le r H L
°

o , T . . Se e , . .

jone s H , . C . D i s s oc ia ti n g p ow e r o f l i qu i d h y d roc y a n i c a c id ( R e p ort )

l m n ts f ph y si c a l c h e m i s t y
The e e e o r

Mol c ul a w e i gh t f l t s i n ac e t n e
e r s o sa o

O u tl i n of e l e ct c h e mi s t y ( R e i e w )
e s ro r v

B n s j a n d Hy de E P L ow e i n g o f th e f e e i n g p oi n t of a qu e
ar e , .
, , . . r r z -

u s h y d rog n diox id e o e .

an d G t m a F H L ow e i n g f f e
e i n g p oi t o f w t r i n on e n
n, . . r o r e z - n a e c c

t te d s lu ti o n s o f e l c t o l yt e s a n d th e c on d u c ra o e r ,

ti i ty o f s u h so lu ti o n s v c

K A ST L E , J H T h e i n ac tivi ty of l i p e tow d s th e s a l t s f c e tai n ac i d

. . as ar o r

th on i d r d i n t h e l i gh t o f t h e t h e o y of
e e rs c l trol yti c s e e r e e c

di s soc i a ti o n
L oe ve n h a rt , A S . .
, and Spey er ,
R and Gi l be r t, j W . . A st u d y of
t ri b ro m p h e n olb rom i d e
an d R e ed, j . V . O n th e u e of m e c u i iod i d i n o lu ti on
n at r r r c e s

K oh le r E , . P . A ddi ti o n - p ro d u c t s o fo r g i c o xy g n omp oun d s a n d a lumi ni um

an e c

K uha r a M a n d Ch h h g é M Me th y l d e iv ati v s o f i n di go
, . z as z , . r e .

L A MB A B C n v e s i on o f rth op e iodi c a id i n t n o m a l p e ri odi c a c i d

, . . o r o r c o r

L Ch a t l i
e H n d B u dou
e d O H i gh t e mp e t u
e r, m u e m nts ( R e . a o ar , .
- ra re e as r e

L e w k ow i tsch , j
l b o ratory o mp a ni n to f t n d i l s i n d u st ri s ( R e vi e w )
. T he a c o a s a o e

L i n ds ay , C F Mo l ul w e i gh t f s ulphu r (R p o t )
. . e c ar o e r

L ocke , J . D u b l e ulph t s of t h ll i c t h lli um n d c e i um

o s a e a a a a s .

E le t fii n i ty a a b a s i s fo t h s y s te m ati a ti on of i n
c r o -a ga n i c co m s r e z or

T he pe r i odi c s y s te m and th e p op r e r ti e s o f g an i c c mp u n d s
in or o o .

IV . T he so lu bi l i ty of d ubl o e s ulph at e s of t h e fo mul M 3M ( $ 002

r a 1 11 .

6 11 20
L oe ve n h ar t , A 5 . Se e K astle , j . H .

MA N C H O T , w . Se e H olle ma n A F , . .

Ma n ni ng C . . R . Se e Be ne di ct F G , . .

Me di e u s L , . K ur z e An l it u n g
e qu a l it ti e n A n a l y e ( R e vi e w )
z ur a v s

N ERNS T W , . , an d Bor che rs , W J a h b u c h d r E l k troc h e m i e

. r e e

N avy , F G . . Se e F r e e r P C , . .

N oy e s W . A . E le me n ts of qu l itati v e a an a l y s i s ( R e vi e w )
an d P a tte rson , A M C on fi . r m tion f B d t s for mul a ; m e
a o re
’
so de
r i v a ti v e s o f i n ac ti ve c a mph ori c a c id .

PATTE R SO N , A . M . Se e N oy es , IV A . .

REED J V , . . Se e R a st le , j . H .

R e mse n , I . h e mi try of a l b umi n ( R e p ort )

O n th e p r e se n t st a t e o f t h e c s

R n ouf E
e A lk li nd l k lin e
, t h m e t l ( R e p o t)
. a a a a e ar a s r .

R i ha ds T W n d Si ng
c r S K T h e qu n ti tati e se p a ati on ofh y d oc hl ori c
, . . a er, . . a v r r

an d h y d o y n i c ids r c a ac .
,

R ochw ood E W I n t od u ti n to c h e m i c l a n l y i f
, . s t u d n t s o f m e di c i ne
. r c o a a s s or e ,

ph a m ac y n d d n ti stry r . a e

R oo e boom 11 W B
z D i e h te og e n e n G l e i hg w i c h te vom tan d p u n k te d e r
, . . . e r c e

Ph e n l h e (R e i e w ) as e r v

SE I D E L L A So lub i l i ty f mi x t u e o f o d i um s ulph te a n d s odi um c hlo ri d e

, . o r s s a

Sang e r S K Se e R i ch ards
, . .
, T . W .

Spey e r R Se e K as tle J H
, . , . .
5 06 In dex .

JA E GE R , W . Di e N or male l e m e n te u n d i h re A nw e n d u n g i n d e r e l e k tri sc h e n
Me s s te c n h ik (R e vi e w)
joh n B Se e Wh e e le r
'

s on , T . .
, H L . .

jon e s, H C . . Di s soc iati n g p o w e r of li qu i d h y d roc y a n i c ac id ( R e p ort )

l e m e n ts f ph y i c a l c h e m i st y
T he e o s r

M l e c ul w e i gh t of a l ts i n ac t n e
o ar s s e o

O u tl i n of e l c t c h e m i t ry ( R e i e w )
e s e ro s v

Ba s J a n d Hy d E P L w e ri n g f th e f e i n g p oi n t of a qu e
rne ,
.
, e, . . o o r e z -

o u s h y d r g e n diox id e o .

an d G tm F H L ow e i g of f re
e i g p oi t o f w te r i n c on e n
an , . . r n e z n - n a c

t t d o lu ti n o f e l e c t o l y t e s a n d th e c on d u e ra e s o s r ,

t i vi ty f s u c h so lu ti o n s o

K A ST L E , J H T h in c ti vi ty f l i p e t w d s th e sa l ts f c e rtai n a i d
. . e a o as o ar o c

e th s c on sid e d i n t h e l i gh t o f t h
e rth e o y of l t ro l yti c e r e r e ec

d i s soc i a ti o n
L oe ve n ha rt , A S . .
, and Spey e r , R an d Gi l be r t , j W . . A st u d y of
t ri b ro m p h e n ol b r o m i d e
an d R e ed , 1 V . . O n th e n a t u e of m e c u i i od i d i n oluti on
r r r c e s

K oh le r , E . P . A ddi ti o n - p ro d uct s o fo r g n i c ox y g n omp ou n d s an d lumi ni um

a e c a

h al d e s i

M a n d Chihash g é M M th y l d e i v ati s o f i n d i go
K uha r a , . z , . e r ve .

L A MB A B C n v e si n of orth p e iodi c a c id i nto n o ma l p e ri odi c a c id

, . . o r o o r r

L e Ch te l i e Ha n d B ou dou a d 0 H i gh te mp e r t u
r, m e s u e m n ts ( R . a r , .
-
a re a r e e

vi e w)
L e w k ow i tsch , j l b o at y o mp i to f t n d i l i n d u s tri s (R e vi e w )
. T he a r or c an on a s a o s e

L i n ds a y C F Mo l e c ul w e i gh t f s ulphu ( R e p t)
, . . ar o r or

L ocke , j D o u b l s ulph ate s o f th a lli th ll i um n d c e i um

. e c a a a s .

E l c tro fii n i ty a b s i f t h e s y s te m ti a ti n o f i n
e g n i c c om
-
a s a a s or a z o or a

The p e ri od i y te m n d th e p p ti e s o f i n o g n i c o mp u n d
c s s a ro er r a c o s.

IV . T h e o lu b i l i ty o f d u b l e s ulph te s o f t h e fo mul M M11 ( SO ) 2

s o a r a 1
2 4 .

6 H20
L oeve nh a r t, A S Se e K astle
.
, j . H .

MA N C H O T W , . Se e H olle m a n A F , . .

M an n i n g . C R . . Se e B e ne di ct F G , . .

M die cu s, L . K ur z e A n e it n l u g qu l it tiv n A n a l y se
z ur a a e ( R e vi e w )
N ERN S T W , . , and Bor che rs , W J h b u c h d e E l e kt
. a r r r oc h e m i e

N ovy , F G . . Se e F re e r , P . C .

N oy e s , W . A . E le m e n ts o f qu li t tiv e n a l y si s (R e vi e w )
a a a .

an d P a tte rson , A M C on fi m a ti on o f B e d t s for mul . r r

’
a ; so me de
i v ti v e s o f i n c ti v e c mph ori c r a a a ac i d .

PA TT E R SO N , A . M Se e N oy es, PV A
. . .

R E ED J V , . . Se e K a stle j H , . .

R e mse n , I . O n th e p re s e n t s t a t e o f t h e c h e mi st y of a l b umi n ( R e port ) r .

R e n ou f , E . A lk a l i an d a lk l i n e a e a rt h m t l s ( R p o t) e a e r .

R i cha r ds , T . IV . a nd Si ng e r S K , . . T h qu n ti t ti e s e p
e ti on ofh y d o hl ori c
a a v ara r c

a n d h y d oc y a n i c a c id s r .

R ock w ood , E . W
u c tion t . I n t r od o c h e m i c l n l y i f s t u d e n ts f m e d i c i n e
a a a s s or o .

ph m c y a n d d e n ti t y ar a , s r

R ooz e boo m, H W B D i e h e t e o g e n e n G l e i hg e w i c h te vom 3St n d p u n k te d e r

. . . r c a

P h se n l h (R e ie w ) a e re v

SE I DE L L . A S lu bi l i ty f mi x t u e of so d i um s ulph te a n d sodi um c hlo i d e

. o o r s a r

Si ng e r S K Se e R i ch ar ds
, . .
, T . W .

Spey e r R Se e K astle j H
, .
, . .
 I n de x .
5 07
TR A V E R S M W , . . T he e xp e ri m e nt l t ud y ofgas a s e s ( R e vi e w )
VA N DE R K L E E D , E C . . Se e E va ns P N , . .

Va n L O n th e . c om p o s i toi n o f D u tc h b u tt e r ( R e v i e w )

WA T E R S , C . E . ppa ratu s for m a k i n g w ate

A r

Whe e le r , 11 L . . O n th e m ol e c ul a e r n g e m e nt f u n y mm t ri l ac y l th io
r r a ra o s e ca

u s n d a y l p e ud th i ou e s to i om e i c s y mm e tri c a l d e
re a a c s o r a s r

ri v a ti v e s

a nd Be a rds ley , A . P . A c ti o n o f ph e ny lh y d r az in e o n a cy l th i o c a r

ba mi c an d ac y li m id ot h i o c a r bo n i c e s te r s ;
py r r o-a ,
'
B diaz o-
le d e ri v a ti v e s
and jh
o n son , T . B . On be n z oy l b e n z y l u r e a , b e n z oy l p a r a to l y l
u re a , an d th e c or re s p on di n g p s e u d oe th y l
u r e a s : a c o r re c ti on O Q O O O Q O O O O O O O O O O O C O O D O O O O O

Whi te , G R . . Se e H ill H , . B .

SUBJ E C T S .

A B SO R P TIO N B A N D So f m th y l i n d i g s M K uha n d M Ch i h hig é e o . . ra a . as .

A c t ni li de
e a P C F n d F G N ovy
. . . re e r a . .

A c e ton e m o l e c ul a w i gh t o f c e t i n l t s i n H C j es
'

, r e r a sa . . . on .

B oi l i n g p oin t c n s tan t ; d mi um i di de ; a mmon i um ulph y nate

-
o ca o s oc a ;
m e c u ri c c hl id e ; sodi um iodid e
r or .

A c e to p e ra c id . P . C Fr e e r
. a nd F G N. . avy .

ph lum ini um b m i d
'

A c e to e no n e a n d a ro e . E . P K ohle r
. .

A c e ty l c a e ton e a n d a lum i n i um b o m id e r . E . P . K ohle r .

A ce ty l d i t hi o c a r b am i id e th y l e ta te
c ac , ac d e ri v a ti v e of . H . L . Wh e e le r an d A .

A cety l m e si ty l e n e a n d a ini b ro lum um mid e . E . P .

A c e ty l p h e n y l p s e ud o m e t h y l t h i o u r e a H L Whee le r
. .

A ce t y l p h e n y l p s e u d o m e t h y l th i o u r e a H L Whe e le r . . .

hl
H y d ro c o ri d e a nd hy d roi o d id e ; be ha v io r w it h lk a li ;
a be ha v i or on

h ti n g
ea .

A cety l p h e n y l t h i o u r e a H L . .

A c e ty l p h e n y l t h io u r e a ( u nsy m ) . an d m e t h y l iod id e H . . L . Whe e le r .

A c y l i m i d o t h i o c a r bo ni c e s t e r s , a c ti o n of ph n y lh y d e ra z i ne on . H . L . Whe e le r

A c y l p se u d oth i o u r e a s , r e a rra n ge m e nt of u n sy mm e t ri c a lt o sy mm e t ri c a l i so

A c y l t h i oc a r b a m i c e s t e r s , a c ti on o f ph e ny lh y d r az in e on . H . L . Wh e e le r an d

A c y l t hiou r e as , r e a r r a n g m e e n t of u n y mme t s ri c a l , to sy mm e t ri c a l i s me o rs . H .

A d d i ti o n - p ro d u c t s of org a n i c o xy g e n co mpo u n d s w i t h lumi n i um h l id e s a a . E .

C mp u
o o n ds w it h e th e rs , k e ton s e , a n d a c id c hl o id e r s .

l um i n on t h p re se n t st t
A b , e t y I R m e a e o f t h e c h mi e s r o f ( R p or t) e . . e s n.

A l b umo s S e l b um i n
se . e a

A l k l i a n d a l k a l i n e e r t h m t a l s re c e t w o k o n ( R e p o t)
a E R
a uf e ,
n r r . . e no

A ll o y s o f n ti mon y a n d te llu ri um
a H F y n d H E A hl y . . a a . . s e

F re e i n g p oi n t s p c i fi g a i ti e m i c o t u t u e
z -
s e c r v s r s r c r .

A ll oy s o f l d n d t e llu ri um
ea H F y n d C B G ll n
a . . a a . . i so .

P re p a atio n n l y si s f re e i n g p oin ts mi c rost u c t u e

r a a z - r r .
5 06 In de x .

JA E GE R , W . Di e N m l e l m e n te u n d i h re
or a e A nw e nd n u g i n d e r e l e k tri sc h e n
Me te c h n i k ( R v ie w )
ss e

B Whe e le r
'

joh nson , T . . Se e , H L . .

jone s H C, . . D i s s oc ia ti n g p ow e r of l i qu i d h y d roc y a n i c ac id ( R e p ort )

l me n ts f ph y i a l h e m i stry
The e e o s c c

M l e c ul w i gh t of l t i n c t ne
o ar e s sa s a e o

O u tl i n e s o f e l c t h e mi s t y ( R i e w ) e ro c r ev

Ba n e s j a n d Hy de E P L w e i n g f th e f e i n g poi n t of aqu e
r , .
, , . . o r o r e z -

u hy d g n d i xi d e o s ro e o .

an d G t m n F H
L ow e i n g o f f e e i n g p i n t o f w at
e a , . i n c on e n . r r z -
o e r
_
c

t r te d lu ti on s of e l e t o l y te s n d th e c on d u e a so c r , a

t i i t y of s u h lu tion s v c so

K A ST L E , J H T h e in c ti vi ty of l i p a t w d s th s al ts o f rt i n c i d
. . a se o ar e ce a a

t h e s on s id d i n th
e l i gh t o f t h th o y f e l e t o l yti c
r c e re e e e r o c r

di s so c i a ti o h
L oe v e n h a r t , A . S .
, a nd Speye r , R .
, a nd Gi l be r t, J . W . A st u dy of

t rib r o m p h e n ol b r o m i d e
an d R e ed, j . V . O n th e n a t u o f m e u i i d i d i n lu tion
re rc r c o e so

K oh le r , E . P . A ddi ti o n - p ro d uct s o fo r g n i c xy g n c o mp ou n d s a n d a lumi ni um

a o e

K u ha r a , M . an d Ch zk as h ig é, M Me th y l d go e r i v a ti v e s o f i n di .

LA MB, A . B C
on v e r s i o n o f o rt h o .
p ri d i id i t n
e m a l p e i od i c a c id
o c ac n o or r

L e Ch a te li e r , H a n d B ou dou a r d , . O H i gh t e mp e
. tu m u e m e n ts ( R e - ra re e as r

vi e w )
L e w k ow i tsch , J l b o tory o mp a n ion to f t a n d i l s i n d u tri s (R e vi e w )
. T he a ra c a s o s e

L i n dsa y C F Mo l c ul w e i gh t f s ulphu (R p t )
, . . e ar o r e or

L ocke ,
j D ubl e s ulph at of th lli th lli um n d c e i um
. o e s a c a a a s .

E l t o a fii n i ty a a b i f th e c ry t m ti ti on of i n o g n i c c o m
- s as s or e s s e a z a r a

The pe ri odi c s y s te m and p p th e ro e r ti e s of g n i c c omp u d s

in or a o n .

IV . The so lu bi lity of d o u b l e s ulph at e s of th e fo mul M 2M 1 ( SO 4) 9

r a 1 1 .

6 H 20
L e
o ve n h ar t , A S Se e Kasi le
.
, j . H .

MA N C H O T W , . Se e H olle ma n A F , . .

Mn a n i ng"
. C . R . Se e Be ne di ct F G , . .

Me d icus , L . K ur ze An l itu n g
e qu l it ti e n A n a l y se
z ur a a v ( R e vi e w )
N ERN S T W , .
, an d Bor che rs , W J ah b u c h d r E l kt
. r e e r oc h e mi e

N avy , F . G . Se e F re e r , P . C .

N oy e s W . A . E le me n ts of qu l i t ti n l y i s (R e vi
a a ve a a s e w)
an d P a tte rson , A M C on fi m a ti n f B . r o o re d t ’s formul a ; so me de
r iv a ti v e s ofi n a c ti v e c a mph ri c a o ci d

PA TT E R SO N , A . M . Se e N oy es, IV A . .

R E E D J V , . . Se e H .

R e mse n , I . O n th e p r e s e n t s t a te o f t h e c h e mi t y f l b u mi n (R e p rt ) s r o a o

R e n ou f , E . A k l a li an d a l k li ne a e a t h m t l s ( R e p o t)
r e a r .

R icha rds , T . W . an d Si ng e r S K , . . T h qu n ti t ti e s e p a ti on ofh y d oc hl o i c

e a a v ra r r

a d h y d oc y n i c
n cid s r a a .

R ock w ood , E . W u ti n t . I n t ro d c o o c h e mi l n l y i s fo st u d n ts f m dic in e

ca a a s r e o e ,

ph m c y a n d d e nti t ry ( R i w ) ar a , s e v e .

R ooz e boo m, H W B D i e h t og e n e n G l e i hg w i c h te v om 3Stan d p un k te d e

. . . e e r c e r

Ph e n l h e (R e v i w ) as e r e

SE I DE L L , A So lu bi l i ty fm i x tu r s o f o di um s ul p h ate a n d sodi um c hl o ri d e
. o e s
'

Si ng e r S K Se e R i ch ar ds
, . . , T . W .

Spey e r R Se e K as tle j H
, .
, . .
5 08 In de x .

A lum i n i um b ro mi d e add ition p od u c ts E P - r . . .

W i t h ac e to ph e n on e a e ty l a c e ton ac e ty l m e i ty l e n e a n i sol an th ra , c e , s . ,

qu inon e c h l r ty l c h l orid e c h l a c e ty l m i ty l e n e d iac e ty l m e si ty

, o ac e , or e s ,

l e n e d i b n alac ton e di h l c ty l m e si ty l e n e m e th y l e n p h e ny l e n e
, e z e , c or a e , e

e th ph e n y l th e t p h th al y l c hl ri d e x a n th n e
e r, e r, e re o , o .

A lumi n i um c hl id e d d i ti o n p r d u ts E P K h le
or a - o c . . . o r

Wi t h n i s l ph e n y l e th r t a p h t h l y l c hl i d e
o , e , e re a or .

A lum i n i um hl o i d e so lu b i l i t y o f b a i um s ulph a t e i n
c r G S F ap s , r . . . r

A lum i n i um h l id s d di t io n p od u t s o f w ith o g n i c x y g e n c o mp u n d s
a e , a E - r c , r a o o . .

A m i do ac id s . Se e
A mmon i um n th e e x i te n c e of ( N t )
,
o s o e

A mm n i um n d mm o n i um m a lg m ( R e p o t )
o a a a a r

A mmon i um ulph y n t e m o l e ul a w e i gh t o f i n
s t on e
oc H G jon a a . c r , ac e . . . es

A n ly a A n l i t u n g u qu l i ta ti
se , en Me di (R vie w ) z r a ve . an s e .

A n a l y i s c h m i a l fo r t u d e n t
s ,
e R h d (Rc i w) , s s . oc a/aa ev e .

A n i li n e ti n o f ph o ph
, ac u s p ta hl o i d n J E Gi lp i
o s or e n c r e o . . . n

A n i li n e n i t p y mu t H B H i ll n d G R Whi te
r0 ro ca e . . . a . .

A n i so l n d lumi ni um b
a m i d e E P K hl
a ro . . . o er.

A n o g an i s c h e n C h mi
r L e h r bu h d H ll m nd M e hot e , c e r . o e an a a ne

A n th qu inon an d lumi n i um b m id e E P K h l
ra e a ro . . . o er .

A n ti m n o ll oy o f an d t e llu i um H F y n d H E
y , a s , r . . a a . .

A to mi c w e i gh t s c l c ul ati o n o f F W C la k e , a . . . i

A ox y b e n
z n P C F e a n d F G N vy
z e e . . . re r . . a .

B A C T E R IA c ti n of p e xid e s on P C F
, a nd F G
o ro . . . re e r a . .

B ri um mmon i um h y d ri d e n i t rid n d m e t lli

a - a , , e , a a c

B a ri um c hl o id e f e e i n g p i n t l w e i n g nd c on d u c ti vi ty of c n c e nt
r , r z - o o r a o r at e d
so lu ti on s o f H an d F H . . .
443
B a ri um m a l t H B H i ll an d G R White a e . . . . . e . z oo

B ari um s ulph ate i n g av i m e t i an l y i ( R p o t ) D W H r r c a s s e r . . . or n

Bari um ulph te solubi lity o f i f ri c h lo i d e a lumi n i um hlo i d

s a , , n e r c r , c r e , an d

m a gn e si um c hl ori d G S F ps e . . . ra .

B e n z op e r a c i d .
P , C Fr e e r . and F G . .

Be n z oy la c e ty l p e ox i d e r . P . C Fr e e r
. an d F G N . . avy

F or ; de co m o s i ti o n ;
a ti on e r i c ida mp g m l a c ti on .

Be n z oy l b e n z y l u r e a , on , b e n z oy l p a r a to l y l u r e a , an d th e c o rr e s po n d in g p se u do
e t h y l u r e as a co r r e c ti o n . H L . . Whe e le r an d T . B .
joh nson .

B e n z oy l di th i o c a rb a m i c H L e th y l a c e ta t e . . .
Wh e e le r a n d A . P . Be a r ds ley
Be n z oy l i m id od i th i o m e th y l c a r b o n at e H L . . .Whee le r an d T B johnson . . .

B e n z o y li m id o m on ot h i o e th y l c a r b on a te H . . L Whe e le r an d A P Be a r ds ley
. . .

L Whe e l e r a n d A P Bea r d sl ey
' '
a - B e n z oy l i mi d o B p h e n y l t hi o b i a z ol i n e
-
H -
. . . . . .

B e n z o y l p ar a to l y l u r e a , on , b e n z oy l b e n z y l u re a , and the c orre s pon di n g

p s e u d o e th y l u re a s : a c or r e c ti on H L . . . Whe e le r an d T B . .
J oh ns on
B e n z oy lp
e ro i d e x
P C F ree r a n d F G N avy . . . . .

Be n z oy l p h e n y l p s e u d ob e n z
y l thi ou r e a H L Whe e le r . . .

B e n z oy l p h e n y l p se u d ob e n z y l t h i o u re a ( u n sy m ) H L Whee le r . . .

Be n z oy l p h e n y l p se ud om e th y l t h i ou re a H L . .

B e n z oy l p h e n y l p s e ud o m e t h y l t hi o u re a ( u nsy m ) H L . . .

Be h a vi o r w it h alk li a , an d o n h e ati n g .

Be n z oy l p h e n y l thi ose mi c a rb a z id e . H L . . Whe e le r an d A . P . 2 64

Be n z oy l p s e u d oe th y l p h e n y l s e m i c a r b az i d e . H L . . Whe e le r an d A . P . Bea rdsley 2 68

B l
e n z oy r h o d a n i d e W
H L hee l e r a n d A P . . . . . 2 68

B e n y l b n oy l di th ioc a b m ate H L Wh l n d A P B ds ley

z e z r a . . . ee e r a . . ear . 2 63

B e n y l id e n di t t P C F
z e aa d F G N vy
ac e a e . . . re e r . a . . 163

B ry ll i um
e 487
B i s muth s ulph ate s of F B A ll n
, . . . a 2 84

B e d t s fo mul a c on fi r m a ti on o f ;
r
’
r om e d i v ti v e s of i c a mph ori c
, s e r a -
ac i d . W.

A N y an d A M
. o es .
 In de x .
5 09

B o m o form p re p aration o f by e l e c t l y s i s
r , , ro . P . C oug hli n . .

B ro m s u c c i n i c ac id . H . B . H ill an d G R . . Whi te
C A D MI U M IO D I D E m l ul w igh t f i t ,
o ec ar e o , n ac e on e . H . C .

C i um d ub l ulph t f t h ll i t h ll i um d
ae s , o e s a e s o a c a an .
J . L ocke
C l i um mm i um h y d i d n i t i d
a c -a d m t ll i on , r e , r e . an e a c (R po t) e r

C l i um hl i d f i n g p i t l w i n g n d
a c c or e . re e z - o n o e r a co n d u c ti i ty of c on c e n t v r a te d
so lu ti on s o f . H C J . . on es a n d F H . .
438 ,
a and BC a m p h o l y ti c
~
a c id s . W . A . N oy es an d A . M . P a tter son .

i -
a- C mph l y ti
a o c a c id . W N oy e s . A . a nd A M P a tte rson . . .

C mph a or , d e r i v a ti v e s ofi n a c ti v e W A . N oy e s a n d A M P a tte

. . . . r son

i -B-C a m p h or a m i di c a c id . W . A . N oy e s a n d A M P a tte son . . r

i -
C mph
a o ri c a c i d , s o me d e ri v ati v e s of . W . A . N oy e s a nd A . MP . a tte r son .

C a p ri c ac id . C .

F ro m oi l o fL i n de r a B e n z oi n .

c u-C arb e th ox y p h e n y l s e m i c a r b a z id e H L Wh e e le r an d A . . . . P .

C h l o ra c e tm e ta to l u id e K u ha r a a n d C hi has hzgé . M . M .

C h l o r ac e t- u n sy m -m e ta x y l i d e M K u h ra n d M C hih hig é
. . a a . as

C h l ora c e t p se u d o u m i d id e M K u ha a n d M C hi ha hig é
c . . r a . s .

C hl o ra c e ty l c hl ori d e nd lum i n i um b mid E P K ohle a a ro e . . . r .

C h l or a c e ty l m e s i ty l e n e a n d lumi ni um b m i d E P a ro e . . .

C h l o r p h os t e t ran i l id e .
J E . .

C on d u c ti v i ty o f c o n c e n t r a te d so lu tion s of e l e c t ro l y te s . H C J on e s . . an d F . H .

C pp l t m ti f
o e r, e e c ro o ve o r c e o f, p t s si um c y n i d s olu ti n S B
in o a a e o . . . C hr i sty
C y t l mix d f i l
r s a s, e , o s ve r a n d s di um c hl o t s o H W ra e . . .

C y i d l t m ti f
an e , e e c ro o ve or c e of m e t l s i n olu t i on s o f S B C h i ty
a s . . . r s .

D I A C E T Y L ME SI T Y L E N E a n d a in i bro lum um m id e . E . P K ohle r .

lp
D iac e ty e ro i d e P C F ree r a n d F G N avy x . . . . .

Fo r m ati
mp o iti n ; g e mi id l ti n
on ; de co s o r c a ac o .

D i a ry l d i k t p i p M K u ha
e o n d M Chih e hig é
ra z i n e s . . ra a . as u

D i ph e n y l di t l y l di xy l y l d i p s e u d o u m y l di k e t p i p e o c o r az in e s .

Dib n l c e tOn a n d a lum i n i um b o m i d e

e z a a e E P K hl r . . . o er .

D i ( b e n z o y l i m i d o d i t h i ob e n z y l ) e t h y l e n e e ste r . H L . . Whe e l e r an d A . P . Be a r ds

Di c a rb e th ox y p h e n y l s e m i c a r b a z i d e . SF . . A cr ee

Di c hl o rac e ti c a c id . P N . . E v a ns a nd C E . . Va n de r hle e d
D i c h l o ra c e t y l c hl o ri d e . P N . . E v a ns a n d C . E . Va n d er k le e d . .

D i c hl o ra c e ty l m e s i ty l e n e and a lum i ni um b omid r e . E . P . K ohle r

D i c h l ora c e ty l ph os ph id e . P N . . E va ns a n d C E . . Va n de r hle e d
i -D i h y d ro am i n oc a m p h ol y ti c acid . W . A . N oy es a n d A P a tter son . M . .

i -Di h y d r oa m i n o c a m p h ol y ti c an h y d ri d e . W A N oy e s a n d A . P a tte rson . . M . .

i - D ih y d r o h y d ro x y c a m p h o l y ti c ac i d . W . A N oy es a n d A . P a tte rs on M . .

Di m -m e ta x y l y l d i k e to p i p e r a z i n e
-
u n sy . M K u hara a a sh i g é . . n d M Chi h . .

D i m e th y l i n d i g os M K u ha r a a n d M . . .

an d -d i m e t h
y 1i n di g o .

’
a a -D i n i t rofu r fu ra n
. H B H i ll an d G R Whi te . . . . . .

5 D i p h e n y 1 3-b e n z oy l m e r c a p totr i a z o l e
- -
H L Whe ele r a n d A P Be a rds le y . . . . . .

i , s-D i ph e n y l 3 b e n z y l m e r c a p t o t ri a z o l e
- -
H L Whe e l e r a n d A P . . . . .

x s D i ph e ny l -3-e th ox y t ri a z ol e
,
—
H L Whee le r a n d A P . . . . .

r , 5 -D i ph e n y l -3 e th y l a c e t a t e m e r c a p to t r i a z ol e
-
H L Whe e le r a n d A P B e a rds . . . . .

Di ph e n y l 3 e t h y l m e r c a p totri a z ol e H L Whe e le r a n d A P Be a r ds le
r, 5 - - - . . . . .

r 5 D i ph e n y l 3 m e r c a p to tr i a z o l e
,
- - H L Whee le r a n d A P Be ar ds ley
-
. . . . . . .

r 3 D i ph e n y l s rn e r c a p tot ri a z o l e
,
- -
H L Whee le r a n d A P Bea rdsley
-
. . . . .

i s D i ph e n y l 3 m e t h y l m e r c a p tot ri a z o l e
,
- - -
H L Whee le r a n d A P . . . . .
5 10 In de x .

r, 5 -Di p h e ny l t ri a z o l e - ulph i d e H
3-d i s . . L . Whe e le r an d A P . . B e ar dsley
r, s-D i p h e n y l t ri az ol e -
3 m on s ulph id e
— o H . L Whee le r an d A
. . P . Be ar dsley
D i p h e ny l ura z i n e . S . F A . c re e

D i p h e n y l u ra z i n e , l
si ve r sa l t of . S . F .

D i p s e u d o c u m y l di k e to p i p e ra z i n e M K u h r n d M C hik ash gé
. . a a a . z .

D i to l y l d ik e to p i p e r a z i n e s ( o r t o a n d h p r ) M K u h a n d M C hi k hig é a a . . ar a . as .

E LE C T R O A F FIN IT Y - as b a s i s fo s y s te m ati ati on o f i n o g n i c c mp u n d s

r z r a o o .

J L ocke.

Solub i l i ty
f o m ation of mpl e x ion ; r co s .

E le kt h e m i J h rbu h d
ro c N n t W n d Bo
e , h W (R ie w )
a c e r. er s , . . a rc e rs , . ev

E l t ol y i s p p
e c r ti n o f b
s m f m by P C oug hli
, re a ra o ro o or . . n.

E l c t ro l y ti d i s i t io n n d i ts b
e c i g n th s c ti vi t y f li p
oc a J H a e ar n o e a o as e . . . K as tle
E l e c t ro m ti f o c of m e t l i n lu ti n o f c y an id S B
o ve r e a s so o s e . . .

E t h l b e n oy l d i t h i c b m t
y z H L Wh l a n d A P B a d l y o ar a a e . . . e e er . . e r s e

E th y l h l c b n t e c H L Wh l a n d A P Be a dsley
or ar o a . . . ee e r . . r

E th y l o x m a t e a ti n f l i p e o n J H R tle
a , c o o as . . . as

E th y l p s u l p h m i -
b n t t i on f l i p n
a J H K tl ne e z oa e , ac o a se o . . . as e .

F E R R I C C H L O R I D E so lu b i l i ty f b i um ulph t i n G S F aps , o ar s a e . . . r .

F or m y l p h e n y l h y d ra z i n e . H L . . Wh ee le r an d A . P . Be a rdsle y
F re e z i n gp - oi n t l ow e ri n g o f c o n c e n t ra t e d so lu ti on s . H C J . . on es a n d F . H Ge t .

F um a r a t e s , a c ti on o f l ip a s e on s od i um th y l e a nd die t y h l .
J H K a stle
. . .

G A SE S , th e e xp e i m e n t l s tu d y
r a of . Tra ve r s (R e vie w)
l
G yce ro l . C E . . Casp a r i
m oi l o fL i nd B n i
Fr o e ra e z o n .

G ol d e l e ct o m oti v e f o e f i n p t
,
r rc o , o a s si um c y a id n e so lu ti n S B C h i ty o . . . r s

A l so i n p t i um hl ri d o ass c o e a n d h y d r xi d o e so lu bi l ity of g l d in p otas o

s i um c y n id a e .

H E XA BR O MP H E N O Q U I N O N E J H K astle a n d A S L oe ve n ha r t . . . . . .

H e x a m e th y l i n di g o M K u ha r a a n d C h i ka s hig é . . M .

H y d ri d e s o f a a i a n d a a i n e e a r t lk l
e ta s ( R e o rt ) lk l hm l p
H y d ro c a rbo n s n e w e t o d fo r re a r a ti o n o f
,
n s at rate d ( R e o r t) m h p p u u p .
J . E .

H y d ro c hlori i d fr in gp
c ac , e ez -
oi n t l o w e ri n g a n d c on d u c ti vi ty o f c o n c e n t ra t e d
solu tion s f H C J o . . . on es a n d F . H Ge tm a n . .
435 , 443
H y d ro c hl o i c a id qu n ti t ti
r c , a a ve se pa ra ti o n o f, a n d hy d roc y a n i c ac i d . T . W .

H y d ro c y an i c a c id , di sso c i a ti n g p ow e r o f l i qu i d ( R e po r t ) H . C . J on es .

H y d ro c y a n i c ac id , qu a n t i t a ti v e se p a ra t i o n of hyd ro c hl o ri c acid a nd . T . IV .

H y d ro g e n d io id e x , th e l ow e rin g of th e f re e z in gp -
oi n t o f a qu u s eo . H C J . . on es ,

P um c hl o i d
o ta s s i r e a n d n i tr a te , so di um n i t r a te .

IN DIG O e r v , v e s of M K a hara a n d M C hi kashzgé

m t h y l d e i ati . . .

Me th y l c h l ora c e tani l i d e ; d i m e th y l t e tr a m e th y l a n d h e xa m e th y li n
di go s ab so r p ti o n b an d s ; so lub i li ti e s .

L A U R IC A C I D and i t s d e ri v a ti ve s . C E . . 2 91 , 303
hlo ri d m i de an i l id e t luid B a Sr C a Mg Z n C u
“

The c e , a , ,
o- o e .
, , , , , , P b,
Mn C o s l ts , a .

Le d a A ll y s f a n d t e llu ri um
. o H F y n d C B Gill
o , . . a a . . son

L e a d e l e t r m oti v f o rc e o f i n p o t s i um y n i d
, c o S B C h i sty e , a s c a e . . . r .

L i d a B e nz i
n er t h e f tty i l n t i n d n th e
o n eed f C E C p
, i a o co a e i s s o . . . as ar .

L i p as e i n c ti i ty o f to w a d s c e ta i n c i d e th e s J H R a tl
, a v , r r a r . . . s e .

S di um e t h y l s u c i n a t
o fum te s ; x l te ph th a l t p n i t c e a ra o a a s a e s - ros u l

p h ob e n o t s p u l p h ob e n o t s s ulph t s z a e -s z a e a e .

L i t h i um a mm n i u m h y d i d e mo no m e t h y l a mi n e n i t ri d e ( R e p o t )
- o , r ,
- -
, r .
5 r2 Inde x .

P h y sic a l c h e mi st ry th e e l m e n t of J o es ( R e vi e w ) . e s . n

P ot ss i um a mm n i um an d h y d ri d e ( R e v i e w )
a -
o

P ota s i um c hl o i d e ; m o l e c ul ar l o w e i n g o f f e e i n g p oi n t i n w t r a n d h y
s r r r z - a e

d g e n di ox id e s lu ti o n
ro H C J es J Ba es an d E P Hy d e o . . . on , . rn , . .

P ota s s i um h y d x id e f r i n g p oin t l ow e ri n g n d c o nd u c ti i ty o f c o n c e n t a
ro , e e z -
a v r

t d s lu ti n o f H C J
e o an d F H o s .
43 7 . . on es . .
, 443
P ot s i um n it ate
a s m o l e c ul l ow e i n g f f e e i n g p i n t i n w t r n d h y d o
r ar r o r z - o a e a r

g n d i o xi d e so lu ti n s
e H j Ba nes nd E P Hy d o . . . r , a . . e

P otas si um n i t te f re e i n g p i n t l w rai g n d c on d u ti i ty
, f c o n e n t a te d
z -
o o e r n a c v o c r

s lu ti n o f H C J n ond F H s o . .
44 t
. o es a . .
, 443
P ot s s i um n i t fu fu a n s u l p h n t
a H B H i ll a d G R
ro r r o a e . . . n . . 19 7

P o p p to n e s
r e Se e a l b um i n . . . 1 47

n -P ro p y l b e n z oy l di t h i oc a rb a m a t e . H L . . Whe e l er an d A . P . Be a r dsley 2 67

P h e ti c g o up s Se e a l b umi n
ros t r . 1 47

P rote id s S .l b umi n e e a . 1 47

P roton e S s lb um i n
. e e a 1 47

P y rro B d i o l e d e i ti v e
—a -
’
- H L Wh l a n d A P Bea dsley
az r va s. . . ee e r . . r 25 7

Q U A L ITA T IV E A N A L Y SI S l abor tory gu i de t o Bai l y an d C , a . e a dy (R e v i e w ) . 15 7

Q ua l ita ti e n al y si s N oy
v a . es 80
Q ui n h y d o n e P C Fr an d F G . . . re e r . . 18 0

R A DI O e L E A D (N ot e ) .

R e po rts
A l k a l i nd a l k l i n r th m e t l
a a e e a a s

B i um ulph t i n g a i m t i an l y si s
ar s a e r v e r c a

C h e mi t y of a lbumin s r .

D i s oc i ti n g p ow e f li qu i d h y d o y a ni c i d
s a r o r c ac

H y d c b o n s p e p a a ti n o f u n t u t d
ro ar , r r o sa ra e . .

Mo l c ul w e i gh t of s ulphu
e ar r.

Sulphu i a i d n d i t p p a ti o n b y th e o n ta c t m t h od
r c c a s re ar c e .

Sulphu i c a i d d te mi n ti on of r c , e r a .

T h e ox y g e n
R e vie w s
An l e itu n g u r qu a l itati v e n A n a ly s e M di us
z . e c

C h m i c l n l y i s fo s t u d e n t
e a a a s r s.

C o mp o i ti o n o f D u tc h b u tt
s va e r . n

Di e h e te g e n e n G l e i c hg w i c h te v m St n d pu n k te
ro e o a de r P h ase n e l h re .

E l e m e nt qu l i t ti e an l y si s N y
s of a a v a . o e

Fa t s a n d o i l s i n d u s t ri s L w k ow i t h e . e sc .

H i gh t e mp e at u re m e s u e m e n t s L C h t l i e r n d B u d u a d
- r a r . e a e a o o r .

Ja h rb u c h d E l e ktr c h e mi e N n t a n d B h s
e r o . er s or c er

L b a to ry gu i d e t qu l i ta ti v e a n a l y s i s
or a B a i l y a d C dy o a . e n a .

L e h b u c h d e a n o g an i s h e n C h e m i e
r H oll m n a n d Ma cho t
r r c . e a n .

N orm l l m e n te u n d i h e A n w e n d u n g i n d e e l e k t i sc h e n Me ss te
a e e r r r ch

O u tl i n e s o f e l e t ro h e mi try Jo c c s . ne s

P a c ti c a l m e t h o d s o f g an i c h m i t y
r G or c e s r . a tte r ma n n
Sm o k l s p o w d e n i t o llul se a n d th e
e e s r, r ce o , o ry of th e ce llulo se mo l e
l e m e n ts o f ph y i c l h e mi stry J o es
T he e s a c . n .

T h e e xp e ri m nt l t u d y o f g es T v e a s as . ra e rs .

U b e r f e te L ii u g e n
e s s n .

SIL V E R C H L O R A T E m i x e d c ry s t l s o f a n d sod i um c hl o t H IV , a , ra e . . . Foote .

Si l v e e l e c t ro m oti v e fo c e of i n p ot s s i um c y a n id
r, S B C h i ty r , a e . . . r s

So di um mmon i um a n d h y d ri d e ( R p o rt )
-a e

Sodi um b n e n e u l p hi n t a tion n t ib ro m p h e n l b ro m id e J H R
e z s a e . c o r o . . . as tle a n d

Sodi um c hl o ra te m i x e d c ry s ta l s o f s i l v e r c hl ora te a n d H IV
, . . . F oote .

Sod i um c hl ori d e so lu bi l i ty of m i x t u re s o f s odi um s ulph at e an d

, . A . Se i de l l
Sodi u m e t h y l s u c c i n a te , ac ti on of l i p a s e on J H R astle . . .
 In de x .
5 r3

Sod i um i o d i d e mol e c ul ar w i gh t of i n a e t n I] C J o s
, e , c o e . . . ne

Sod i um n i tr ate mo l e c ul l w e ri n g of f i n g p o i n t i n w te r a n d h y d g e n ar o re e z -
a ro

di ox i d e o lu ti on H C J n s J B n nd E
s P Hy d . . . o e , . ar e s, a . . e .

Sodi um n i t a t e f e i n g p oi n t l w e ri n g n d n d u c tiv i ty f c n c e n t a te d l u
r , r e z -
o a co o o r so

t i n s o f H G jo s n d F H
o . . . ne a . .

S d i um s ulph te solub i l i ty f m i x t u e s f n d s d i um c h l i d e
o a , A S i d ll o r o , a o or e e . .

M K u ha n d M Chi k as h ig é
. .

So lu b i l i ti e f m e th y l i n d i g o s
s o . . ra a . .

So lu bi l i ty f b i um s ulph te in fo i c c hl id e
ar lum in i um c hlori d a nd m ag a e rr or , a e ,

2 88

So lub i l i ty o f th e ubl e s ulph a t s o f th e f mul

do e or a J L ocke
.
45 5
So lu b i l i ty o f mi x t u r s o f s d i um s ulph t e a n d h lo i d
e o a c r e . A . Se i de l l 52
So lu ti on s , f e in g p i n t l w e ri n g a n d on d u c tivi ty f c
r e z - o o c o o n c e n t ra t e d so lu ti on s .

H C J . . on es an d F H . .

Stro n ti um -a mm o i um h y d i d e m e t lli c a n d n i t id (R e p o t )
n , r ,
a . r e r

Stronti um c hl i d e f e e i n g poi n t l ow e i n g n d c n d u c t i i ty of c on
or ,
r z - r a o v c e n tr a t e d
lu ti o s f H C J n n d F H
so n o . . . o es a . .
438 , 44 3
Su c i n n i l H B H i ll a n d G R Wh i te
c a . . . . . 2 03

Sulph a te s ti o n o f l i p e n,J H ac as o . .
483
Sulph t s th e olu b i l i ty o f d u b l e o f t h e f mul
a e , s o , or a J .

p Sul p h o b e n z oa te s
-
, ac ti o n of li p a se on m o n oe t h y l and b a ri um e t y h l .
J . H .

3 Su l p h 0 p y rom uc i c
- a c id . H . B . H i ll and G R . . Whi te .

Sulphu r th e m o l e c ul a r w e i gh t o f ( R e p o rt ) C F L i n dsay
, . . .

Sulphu ri c a c i d d e te r m i n a ti o n o f i n p r e s e n c e o f i r on ( R e p o r t ) D W H or n
, , . . . .

Sulphu ri c a c i d f r e e z i n g p oi n t l ow e r i n g a n d c o n d u c tiv i ty of c on c e n t ra te d so lu
,
-

tio n s of H C J on e s a n d F H Ge tm a n . . . . .

Sulphu ri c a c i d an d i ts p r e p a r a ti o n b y t h e c o n t ac t m e th o d ( R e p o r t ) J E . . .

Gi lp i n

T E L L U R I U M ll oy s t n ti mo y a n d H F y , a a a n . . a and H E . . A shley
T e llu i um ll oy s f l e ad n d H F y an d C B
r , a o a . . a . . Gi llson
T e e p h t h al y l c h lo id e a n d a lumi n i um b
r mi d e r ro . E . P . K ohle r .

T e re p h th l y l c hl id a d lu m i i um h l ori d e or e an a n c . E . P K ohle r
. .

T e t r a b ro m p h e n o l .
J H K astle a n d J W Gi lbe r t
. . . .

T e t r a b ro m q ui n o n e .
J H K astle a n d A S L oe ve n ha r t
. . . . .

T e tr a m e th y li n d i g o . M K u ha n d M Ch i k as h ig é
. ra a

Th a lli um , do b u le s ulph t s o f t h a lli c an d c ae si um

a e , .
J .

Th ioac e ti c aci d . H . L . Whe e l e r a n d A P . .

T h i oc y a n e t h y l a c e t a t e . H L Whe e le r a n d A P Be a r d sley
. . .
'

H
T ol y l s u c c i n i m i d e . . B H i ll a n d G R Whi te
. . .

T ri b ro mph e nol J H K astle a n d A S L oe ve n h a r t . . . . .

T ri b ro m p h e n Olb ro m id e a s t u d y o f J H K a stle , . . . .

Se e a l s o ] H R astle a n d A S L oe ve n ha r t . . . . . .

J . W .

A c ti on o f h e at l i gh t w te r p otas s i um i d id e i n c e th y l i odi n e b ro
, , a , o , z , ,

m in e , e tc c on s ti t u t i on
. mo l c ul re a n ge m e n t ; t ri c h l o p h e n ol e ar rra r

b om id e
r .

T ri b ro m p h e n y l b e n z J H R Spey e r
'
e n e s ul p h on a te . . . a s tle a n d R . u n .

T ri c hl o r m o n ob ro m p h e nol J H K astle a n d j W Gi lbe r t

. . . . .

T ri c h l o r p h e n o l b rom i d e J H K astl e a n d J W G i l be r t
. . . . .

M P a tt
.

- T ri m e th y l c y c l o p e n ta n o n e . W . A N oy e s a n d A
. .
'
. e r son

Tu n g ste n th e x id e s of E T A ll
,
o . . . en a nd V H . .

V A C U A a c h e mi c l m e th od fo r obt i ni n g F G B ne d i t n d
, a a . . . e c a C R . . Man n i ng .

WA T E R G A S a pp a r at u s fo d e mon st ati n g m an ufa c tu e of

-
,
r r r . C E . . Wa te rs .
5 14 In de x .

XA N T HO N E an d a lumi n i um b o mi d e E P Kohl r . . . er

Z IN C e l e c tro moti
, v e forc e o f i n p ot s i um c y a n id e
, a s so lu tion . SB . . C h r i sty .

FO R MUL A S .

Cr GR O U P .

C H4 . Me t h an e . P . C F re e r
. an d F G N . . avy

F ro m be n z oy l ac e ty l p e ro xi d e .

I II .

C H B ra . B omo f r m P Coug hli

r o . . n

P re p a ati o n b y e l e t o l y s i
r c r s .

C r GR O U P .

Q H40 3 . A c e to p e r a c i d . P . C F r ee r
. an d F . GN . avy

2 III .

C QH O C IS . Di c h l o ra c e ty l c hl o ri de . P N . . E va ns a n d C E . .

C gH gO gC l g . Di c hl o rac e ti c a c id . P . N . E va ns a n d C E . . Va n de r k le e d
C QH 4O S . Th ioac e tic ac i d . H L . . t 8 16 7 ’ a n d A . P . a o t o 0 0 0 0 -0 0 0 0

2 IV .

C QH O QC IQK . P ot as s i um d i c h l ora c e ta te . P N . . E va n s a n d C E . . Va n de r k lee d

C2 H 30 C 12 P . Di c h l o r a c e ty l ph ph id e os . P IV E
. . v a ns an d C E . .

c R ou p .

C 3H 80 3 . G l y C C rOI . C E . . 0 0 0 0 0 0 0 0 0 . a a Q Q O O Q O O O O O O O Q O O O

C aH sogCl . Et y h l c h l o rc a r b o n a te . H . L . Whee le r a nd A . P . B e a rds ley . .

C 4- G R O U P O

(2411 5 0 4 . D i ac e ty l p e roxid e . P . C Fr e e r
. an d F G N . . avy .

C 4H 2 0 5 N 2 . a,a
’-
Di n i tro fur fu r an . H . B . H i ll and G R . . Whi te . .

C HO
4 7 4N . E t yl h x a m te
o a .
J H K astle
. . .

A c ti on o f l i p s e on a .

C 4H 5 O 4B r . B ro m s u c c i n i c a ci d . H . B .H i ll a n d G R . . Wh ite . .

C 4H 5 0 4K . um e th y l o xa l ate
P ot a s s i .
J H K a stle
. .

A c ti o n o f l i p ase on .

C 4H 2 0 4Ba B a i um m a l e ate H B
. r . . . H i ll a nd G R . . Whi te

C 4H 30 0N S . N i trofu r fu r an s u l p h on i c ac i d . H . B . H ill and G R . .

C 4H 30 6 N SK . P ot a s s i um n it ro fu r fu r a n s u l p h on at e . H . B . H ill a n d G . R . Whi te 1 97

C4I-I4 03C 14B r6 A l g . C h l o ra c e ty l c hl o ri d e a n d a lumi ni um b ro mid e . E . P Kohle r

. 25 5
5 16 In de x .

8 III .

C 8H 10 2N 3 . P h e n y 10 r 3 2 0 1e . o a o o o o o o o a o o o o

C BH QO N . A ce ta ni i d e l . P . C F re e r
. and E G .

8 IV .

C 8H 5 0 N S . Be n z oy l rh od n i d H L Whe a e . . . e le r a n d A . P .

C 8H 6 0 2 N 3 A g . Si l e r s a l t of p h e ny l u
v ol ra z e . S . F A . cr e e

8 V .

C 3 H40 2C l z B r6 A l g . Te re p h th a l y l c hl ori d e an d a lumi n i um b romide . E . P K oh

.

c R o up .

C 9H 9 0 4 . B e n z oy l
l p e o xide P C F e
ace ty r . . . r e r an d F G N . . avy

C gH u o g . a a n d B C a mph o l y t i
-
ids W A c ac . . . N oy es an d A . M P a tter son
C 9H 1402 . i -a - C mphol y t ic id IV A N y
a ac . . . o es an d A . MP . a tte rson

C gH mO s . i D ih y dr oh y d rox y c a m p h ol y tic
-
acid . W . A . N oy e s a n d A . MP a tte r .

C gH ’O gN a . h ny l z m t h y l 3 h y d roxy u ol e S F A c
r-P e - -
e - -
ra z . . . re e

C gH gogN a . x P h e n y l 4 m e th y l u
- l SF A
- - r az o e . .
_
. cr e e . .

C 9H 15 0 N . i D ih y d ro am i n o m p h l y ti
- n h y d id e W A ca o c a r . . . N oy es a nd A . M .

P a tte r son
C 9H 17 0 2 N . i Di h y d roa m i n o c a m p h ol y ti c
-
ac id . W . A . N oy e s an d A . M . P atte r
so n

C ol-1100 5 8 . Monoe th y l p s ulph ob e n - z oate .

J H K astl e. . .

A c ti on o f li pas e on .

C gH wO N C l . C h l o rac e tm e ta to l uid e . MK . u ha r a a n d M C hik . as h i gé .

A l s o o rt ho and p a r a-t o lu i d e s .

C gH mO N C l . Me th y l c h l ora c e ta n i l i d e M K u ha r a an d M .

C 9H 9 0 2N S . Me th y l b e n z oy l thi ol c a rb a m ate H L Whe e le r an d A . . . . P . Bea r dsley

Cn oo N gs . S
ym .
- H L
A c e ty l p h e n y l t h i o u re a . . .

C QH IOO N Q S . Unsy m A c e ty l p h e n y l th io u r e a H L Whe e le r

.
- . . . . .

C 9H 110 4N S .
E t h y l p s u l p h a m i n e b e n z o a t e J H K astle
- . . .

A c ti on o f l i p a e on s .

C 9H 302N 3A g . Si l v e r s l t o f p h n y l m t h y l h y d o x y u r ol e
a SF
e e r az . . . A cr e e .

C .H 802 N 8 A g . Si l v e r s a l t o f p h e n y l m e th y l u ol e S F A cr e ra z . . . e

C 9H 30 7 N SK . P ota ss i um e th y l a ni t ros ul p h ob e n z oa te . I H K as tle

. . .

A c tion o f l i p a se on .

C GR O U P .

C mHmO . i- C mph a o r, d e r iv a ti v e s of . W . A . N oy es a n d A . MP . a tte r son .

C 10Hgo02 . C up i r c acid . C E . . C aspa ri

 In de x .
5 17

10 III .

Cn O gN . Su c c i na ni l . H . B . H i ll and G R . . Whi te
c l oH 9 0 3 N 3 . r- P h e ny l h y d -
z- ro-3-oxy a c e ty l u ra z ol e . S . F A . cr e e

C l oH u O gN s . r P h e ny l
- hyd -
z- ro -3- e t h o x y u r a z ol e . S . F A . c re e .

C mn O aN a . c u- C a rb e th o x y p h e n y l se m i c a rb a z i d e . H . L . Whee le r an d A . P .

C l oH a N . i -fi- C a m p h o ra mi di c a ci d . IV A . . N oy es a n d A . MP . a tte rson

C 10H 9 0 4K . um e th y l ph th l
P ota s s i a a te .
J H . . R a stle
A c ti on o f l i p a s e on .

no I‘l .

C m ON Cl . C h l o rac e t-u n sy ni .
-
m e ta xy l id e . M . K u h ar a and M .

C l oH u O N 8 2 . h l
E t y b e n z o y l d i thioc a r b a m at e . H L . . Whee le r an d A . P B e a r ds
.

C mH n O N Sg . B e n z oy l i mi d od i t h i om e t h y l c a r b on a t e . H . L . Whe e le r an d T B . .

C 10H 13 0 N gs . Sy m .
-a c e ty l p h e n y l p s e ud o m e th y l t h i o u r e a . H L . .

A l so th e h y d ro io di d e .

C 10H 120 N gs . Unsy m .

-
ac e ty l p h e n y l p s e u do m e t h y l thi o u r e a . H L . .

A l
h y d roc hl ori d e an d h y d oi did
so r o e .

C 10H1 0 4 B r6 A 12
6 A c e ty l a c e ton e a n d lumi n i um
. a b ro mi d e . E . P K ahle r
. . .

C u H mO 4 . B e n y li d e n e z d i a c e ta te . P . C Fr e e r . an d F G N . . avy

11 III .

C 11H 100 5 N 2 . l
A n i i n e n i tr 0 p y r o m u c a te . H . B . H i ll an d G R . . Whi te
C H H u O gN . T ol y l s u c c i n i m i d e . H . B . H i ll and G R . . Whi te
11 Ill .

C u Hu O N C l . C h l o rac e tp se u d o c u m idi d e . M K uh . ar a a n d M .

Cq sO N S
j . n - P ro p y l b e nz oy ld i t h i o c a rb a m a te . H . L . Whe e le r a nd A . P .

C 11H130 7 N S . D i e th y l fi n IITO SU Ip h O b e n Z O ate

-
. j . H K a stle . . ooo o a aooooaaaao oa a o o 0

A c ti on o f li p a s e on .

(3
C 12H 100 4 . Q ui hy d n r on e . P . C Fr e e r
. an d F G N . avy

c l gH u O ‘ . D i e t h y l ph th a l a te . j . H K astle .

A c ti o n o f lip a s e on .

C u H 240 3 . L au ri e a c i d . C E . .

12 III .

C u H mO N g . Axy b e n e n e P C F ee r a n d F G N avy
zo z . . . r . .

C mH 35 0 N . A mid e o f l u ri c ac i d C E Casp a i
a . . . r “

C 13 H230 C I . C h lori d e f l a u ic ac id C E C asp a i

o r . . . r

C mH 40 2B r 4 . F ro m t i b ro m p h e n l b ro m i d e b y ac t i on o f s u n l i gh t
r o .
J H K a stle
. .

and A . S . L oe v e nha r t
Cm mO gB rs. H e xab ro m p h e noq uino n e .
J H K astle
. . an d A . S L oe ve n ha rt
.

12 I\I .

C u n l soaN Sg . B e n z oy l d i th i oc a rb a m i c e th y l ac e ta t e . H . L . Whe e le r an d A . P .

C u H mO QN S . B e n z oy li m id om o n oth i oe t h y l c a rb on a te . H . L . Whe e le r an d A . P .

C 13H 7 O sSB r3 . T ri b ro m p h e n y l b e n z e n e s u l p h o n a te .
J H K a stle. . and R . Spe ye r
5 18 In de x .

C GR O UP .

C 13 H17 O 5 N 3 . Dic arb e th oxy p h e n y l se m i c a r b a z id e . S . F A . cr e e

13 I\l .

C u H mO gB re A 12 . Di a c e ty l m e s i ty l e n e an d a lum i ni um b romid e . E . P K ohle r

.

I3 V .

C 13H 140 2c 12 B I 6 A 12 ’

. Di c h l o ra c e ty l m e s i ty l e n e and a lumi ni um b ro m ide . E . P .

c 14H 100 4 . Be n z oy l pe r O XId e . P . C Ffl

. t f an d f
‘

. G .

14 II I .

C I4H 120 2N 4 . D i p h e nYIu r a Z i n e .

Ca N S
g . r , 3- D i ph e n y l 5 - -
m e r c a p totri a z o l e . H L . . Whee le r an d A . P . Bea r ds

Ca N S
s . r, 5 - D i ph e n y l 3 m e rc a p tot ri a z o l e
- -
. H L . . Whe e le r a nd A . P . Be ar ds

14 I‘l .

C MH l aO N aS . B e n z oy l p h e n y l t h i o s e mi c a rb a z i d e . H . L . Whe e l e r an d A . P .

C 14H 11 0 2 N 4A g . Si l v e rl t of d i p h e n y l u i n e S F A
sa raz . . . cr e e

C 14H 16 0 2C 16 A 12 . A ni ol n d s lumin i um c hl o id e E P K ohle

a a r . . . r

C MH SO gB rGA l g . A n th a qu i n o r nd lum i n i um b mi d e E P
ne a a ro . . . K ohle r
C 14H 16 0 2 Br6 A 12 . A ni l an d lum i ni um b o m id e E P K ohl
so a r . . . er

C m- G R O U P .

C 15 H 140 2N 2 . B e n z oy l p a ra to l y l u r e a . H L
. . Whe e le r an d T . B .

C 15 H 140 2 N 2 . Be nz oy lb e n z y l u re a H L Whe e le r a n d T B
. . . . .
J ohnson
C 15 H 13N as . r .s- D i ph e n y l -
g-m e t h y l m e r c a p tot r i a z ol e H L . . . Whe e ler an d A . P .

C 15 H 13 N 3 5 . I - P a r ato l y l -5 - ph e n y l 3 m e - - r c a p t o t r i a z ol e . H L . . Whe e ler an d A . P .

I s- IV O

C l sH u O N as . a
'
- Be nz oy 1i m id o -
'
B-p h e n y l t h i ob i a z o l i n e . H L . . Whe e le r an d A . P .

C 15 H 130 N SQ . B e nz y l b e n z oy l d i t h i oc a r b a m a t e . H . L . Whee ler and A . P .

C 15 H 14O N 28 . S
ym . b e n z oy l p h e
- n y l p se u d o m e th y l t h i o u r e a . H . L .

C 15 H 140 N QS . Unsy m -b e n z o y 1p h e n y l p s e ud om e t h y l t h i ou re a
. .
H L Whe ele r
. .

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C l e H mO N a. Su b s ta n c e fo r m e d b y t h e a c ti o n o f a n i lin e o n n i t r 0 p y ro mu c i c a c id .

H . B . H i ll an d G R
. .

C 13H 17 0 2N 3 . i , s D i ph e n y l 3 e t h o x y t ri a z o l e
- - -
. H L . . Wh e e le r an d A . P . Be a r dsle y 2 68

C 15 H 17 0 2N 3 . Be n z o y l p s e u d oe t h y l p h e n y l s e m i c a rb a z i d e . H L . . Whe e le r an d A .

Cu N aS . x, 5 - D i ph e n y l 3 e th y l m e r c a p totri a z ol e
- - . H . L . Whe e le r a nd A . P .
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 C GR O U P .

C n Hfi O QN Q . H e xa m e th y l i n d i g o M K u ha r a a n d M C hi k ashig é . . .

n n oz N g . D i p s e ud oc u m y l d i k e to p i p e ra z i n e M K u har a a nd M Chik ashig é . . .

” JV .

C QQH 280 3 B I
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6 A 12 . A c e ty l m e si ty l e n e an d a lu m in i um b om id e r . E . P K ohl er
.

22 V .

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1 B I
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. C h l o ra c e ty l m e s i ty l e n e a nd a lumi ni um b ro mi d e . E . P .

C GR O UP .

C4 4H 46 0 4B a . B a ri um l a u r te a . C E . C aspa r i
C g, H 4GO 4C u . Co pp r l u te e a ra . C E . . C asp ar i
Cfl H Q O 4P b . L e ad l a u rat e .

C MH Q O Q MI] Ma n g an e s e l a u ra te
. . C E . .

C34H46 0 4Z n . Z i n c l u a te C Ea r . .

C24H 48 0 5 C a . C a l ci um l u rate C E C p a . . . as ar i

C 94 H 48 0 5 C o . C b l t l u ate C E Caspa
o a a r . . . ri

C24 H48 0 5 Sr . Stron ti um l a u at e C E Caspa r . . . ri

u JV .

C24 H 200 2C 16 A 12 . Ph e n y l e th e n d lumi n i um hl i de

r a a c or . E . P K ohle r
. .

C9 4H 200 2 8 r6 A 12 . P h e n y l e th e r a n d lum i n i um b o mi d e a r . E . P Kohle r

.

C Q4H 24 N 4C IP . C h l or p h os te t an i l i d e j E Gi lpi
r . . . n

C GR O UP .

C 26 H 16 0 4B r6 A 12 . X an t h on e lumi i um b omi d e E P
an d a n r . . .

C ge H goo gB re A l g . Me th y l e n e p h e ny l e n e th e a n d a lumi i um e r n b ro mi d e . E . P .

O2S- G R O UP .

n H z oN GS . r , 5 - D i p h e n y l t ri az ol e -
3- m o no s ulph id e . H . L . Whe e ler and A . P .

Be ardsley
n H goN ss g . r , s- D i p h e n y l t ri a z ol e -
3-d i s ulph i d e . H . L . Whe e le r a nd A . P .

C GR O U P .

n H230 2N 28 4 . D i ( b e n z o y l i m id od it h iob e n z y l ) e t h y l e n e e s te r . H . L . Whe e le r

Cu -GR O U Pr
.

Cq gog B rcA l g . Di b e n z a l a c e to ne an d a lumin i um b ro mi de . E . P .

C 3°H 7 00 6 Mg . A cid m a g n e i um la us ra te . C E . .

C GR O UP .

C Q H42N 7 C 1P 2 . Sub st a n c e for m e d f ro m a n i li n e an d ph ph o u s p os r e n ta c hlo ri d e .

J . E . Gilp i n