L A BO R A T O RY M A N U A L

f
o O R G A N I C C H E M I S T RY

BY
HA R RY L I S H E R , Ph D
‘

f . .

I n s tr u c tor i n Or gan i c Chemis try , Col u mbi a Un i vers ity

N EW YO RK

J O H N W ILEY S ONS ,
I Nc .

LO N D O N : C H A P M A N H A LL ,
L I M I T ED
1920
 C op y righ t , 19 2 0

BY

HA RR Y L . F IS H E R

o mu nwo mu a 00 .

K MA NU FA CTU RERS
BOO
 P R E FA C E

b ook is th e ou tgrow th of a lm os t ten ye ars of in ten sive

"

T HI S
lab ora tory t e a chin g P ra c tica lly al l th e l ab o ra tory experi
.

m en ts in mim e ograph fo rm h ave b een in th e h an ds of three

, ,

diff e r en t cla ss e s of s tud en t s day n igh t an d summ e r e ac h y ea r

, , , ,

for o v e r fiv e y e a rs an d duri n g t his tim e h av e b e en r ep ea te dly

,

corr e c te d A s ou r cla ss e s gre w w e f ou n d it n e ce ss ary to k e ep

.

t o a d e fini te lis t of e xp e rim e n t s a n d al l ou r a tten t io n w a s d evo te d

t o th e s e . I n o rd e r to bridg e th e gap b e tw e en th e p ar ti c ul ar re ac
t i on s tudi e d an d a lli e d r e a c t i on s m a n y qu e s ti on s w e r e a dd e d
, .

Th e se qu e s tion s h a ve b een m ad e th e b a sis of l ab ora tory quizzi n g

a n d a re m e an t prim a rily f o r t h e s t ud en t t o u s e f o r his ow n ad

van ce m en t in th e subj e c t to aid him to b e com e his ow n tea ch e r .

A p or t i on of th e qu e s ti on s ar e on th e pr a c tica l w o rk in th e
l ab o ra tory th a t is on th e m e t ho ds of h an dlin g app ara tus e tc
, , ,
.

M an y of th e m will app e ar to b e p e rf e c t ly obvi ous Th e y are .

,

n e v e r t h e l e ss pu t in si n c e i t h a s b e e n n o tic e d t h a t it is th e m o s t
,

o bvi o us p o i n t which is m o s t o f t en o v e rl ook e d .

T h e e xp e rim e n t s are in g en e r a l th e usu al on e s fou n d in

, ,

lab ora tory m an u als ch an ge d o f cours e in a ccord an ce wi th our

,

e xp e ri e n c e an d th e y w e r e ch o s e n f or t h e ir t ea chi n g v alu e an d
,

for th e good all r ou n d pr a c t ic a l m an ipul a t i on i n vo lve d

-
Th e re .

a r e o n ly a f ew i nn o va t i on s M en th on e an d m en thon e oxim e
.

illus tr a t e t ypic a l r e a c ti on s e v en t h ough th e ir fo rmul a s may s eem

large to th e b e ginn e r G lycoco ll is prep ared by hydrolysis
.
,

thus li nk in g up th e ch emis try of th e pr o te i n s wi th th a t of

simple r comp ou n ds L im on e n e dihydrochlorid e h as trem en dous
.

te a chi n g v a lu e an d th e sy n t h e sis o f c a mph o r fr o m pi n en e give s

an o pp o r t u n i ty f o r s e l e c t w o rk in an e n t ici n g fi e ld T h e m e th ods .

d e scrib e d giv e good yie lds in m o s t ca s e s bu t th e yi eld w a s ,

n o t th e prim e r e a s o n f o r ch oo si n g an y e xp e rim en t .

I t wi ll be n o tic e d th a t th e r e a re n o dir e c ti on s for pr epa ri n g

iii
iv PR E F A E C
such subs tan ce s a s a ce ta ce tic e s ter m al on i c e s te r e tc Th e se
’

.
, ,

c a n a dv an t a g e ously be giv en in c on n e c t i on wi t h sp e ci a l a dv a n c e d

syn th e tic w ork for example m alon ic e s t er c an be prep ar ed as

, ,

th e s ta r ti n g p o in t in th e syn th e sis of v e r on a l (b a rbi ta l ) a ce t

—
,

a c e tic e s t e r a n d a ls o ph e n yl hydr azi n e in th e pr e p ar a ti on o f

a n t ipyri n e ,
an thr a n ilic a cid f o r m e thyl a n thr an il a t e o r i n dig o ,

e t hyl e ne c h l o rh y drin f or n ov o c a i n e (p r c i ) pyruvic cid

‘

o a n e a ,

f o r a toph an e tc ,
.

I n th e l a rge cl a ss e s of t o day th e b egi nn i n g s tud e n t d oe s no t

-

a n y l on ge r h a v e th e opp o r tu n i t y o f rubbin g elb ows wi th th e

o ld e r me n a n d l e a rn i n g fr om such c on t a c t m an y o f th e li tt l e

t hin gs ab ou t l ab o r a t o r y m an ipul a t i on which a id m a te ri ally in th e

succe ssful ou t com e of an e xp e rim e n t For this rea son th e .
,

firs t exp erim en t s in this b ook are wri t ten up in con sid e r able d e tail
wi th th e h op e th a t a f te r th e s tud e n t h as l earn ed h ow to s e t up
hi s app a r a tus in th e co rr e c t w a y h e will th e r e af te r follow this
,

pra c tic e For the m o s t p ar t this h op e h as b een r ea lize d in this

.

l ab ora tory All op e ra ti on s are d e sc r ib e d wh e re th ey are firs t

.

us ed in th e o rd e r o f th e exp e rim en ts an d a f te rwards th eir u se

, ,

o n ly is m en t i on e d s om e t im e s b e i n g cr o ss r e f e r e n c e d bu t a lw ays
,
-
,

fully i n d ex e d S p e ci al discussi on s are in clud e d on ly whe re it is

.

b e lieve d th e m ate ri al ca n n o t be fou n d in th e ordin ary b ooks which

th e s tud en t h a s a t his disp o s a l .

I t is a ssum e d th at b e fo r e b e gi n n i n g o rga n ic l ab or a tory

w ork s tud en t s h av e b e en pr ep are d wi th a lon g cours e in gen e ra l
ch emis try an d a sh or t c ours e in qu ali ta tiv e an alysis .

A sh o r te n e d o rg an ic c ours e is m en ti on e d b e low which h as b e en

d e sign e d e sp e ci ally f or pre m e dical s tude n t s A good grou n din g
-
.

in o rg an ic ch e mis try is h ow ev e r abs o lu te ly e ss e n ti al f o r th e

, ,

s tudy of m e dicin e an d th e lon g cours e should be tak e n wh en ev e r

,

p o ssibl . e A s t ud e n t g e t s much m o r e ou t o f his w o rk wh e n h e

prep are s ce r tain comp ou n ds an d has tim e to s tudy th ei r ch ar

a c t e r is tic s an d t hi nk ov e r his w or k th a n wh e n h e go e s t hr ou gh a
,

ve ry gre a t n umb e r of te s t tub e r e a c tion s which sup e r ficially are

-

ve ry much alik e an d th e r e fo re th e mo r e e a sily f o r go t t en .

T h e l on g c o urs e c on sis t s o f tw o af te rn oon s a w e e k fo tw o r

s em e s te rs an d comprise s for th e firs t seme s te r expe r im en ts

, ,
 P R E FAC E
No s .
7
1 9
—
5 7, 3
—1
, 1 s e c —2
on d s e m e s,t e r
an d
e xp e rim e n t
‘

s f or th e ,

— —
Th e s e a re
N os 2 4 2 9 ( ) 3 0 4 6 4 8 4 9 5 5 3 5 6 5 8 6 5 66
.
— —
I , , ,
1 , , , ,
.

a rr a n ge d in th e o rd e r o f discussi on f o u n d in S t o dd a rd s I n t ro
’

duc ti on to Organ ic Ch e mist ry T h e sh o r t c o urs e c on sis t s o f .

”

tw o a f te rn oon s fo r on e s e m e s t e r a n d c ompris e s e xp e rim e n t s ,

No s . 1, 2, 3 4,
,
28, 5 ,
1 0, 6, 24 , 1 2, 25, 2
9 ( )
r ,
16, 19, 2 2 , 0
3 , 8, 9,
26, 27 , 3 4 3 7 , 3 3 3 8 , 43 4 s , 4 6 , 5 13 5 3 , 49 ,
, , , ( p t i o n a l ) 13 O ,
in th e
o rd e r giv e n This diff e r e n t o rd e r is in a cco rd an ce wi th th e
.

discussion in M oo re s Ou tlin e s of Or g an ic Ch emis try

’
S in c e .
”

th e o rd e r o f b o t h cours e s is n o t th e s a m e s o m e o f th e e xp e rim e n t s ,

in th e l on g c ours e which a ls o o ccur e a rly in th e sh o r t c ours e ,

h av e b ee n wri t ten up in gre a te r d e tail th an would ordin arily

b e n e c e ss a ry fr o m t h e i r p o si t i on in th e lis t A lis t o f app a ra tus .

furn ish e d to e a ch s tud e n t an d lis t s o f th e ch emica ls use d in e a ch

c ou r s e will be f ou n d on p age s 3 1 2 3 2 3 I n ou r lab o r a to ry e a ch
— .

s tud en t re ce iv e s his compl e te s e t of ch emica ls an d app a r a tus

f or th e s e m e s te r wh e n h e s ta r t s w o rk a n d k ee ps th e m in his d e sk , .

E a ch d e sk in th e o r gani c l ab o r a t o ry a t Co lumbi a Un iv e rsi ty

is e quipp e d wi th ga s a ir bl a s t w a t e r ( 2 o u t l e t s i n cludi n g o n e ,

which c an be us e d f or suc ti on pump ) s team cup s te am ou tle t , ,

f or s te am dis t ill a t i on e t c dra f t pip e (d own w ard ) an d e l e c tric

,
.
, ,

fix ture o x r a ligh
f r e t t an d wi h a
t 2 0 — amp e r e c on n e c t i on It .

is e xp e c te d th a t in addi ti on a sp e ci a l h o t pla te will soon be -

in s ta lle d h avin g a s te am pip e ca s t in it an d a ls o h avi n g an o th e r

pip e ca s t in it which c an be con n e ct e d wi th th e air bl as t to
give h o t air wh e n d e sir e d A t th e a dj a cen t sin k is a goos e n e ck
.
-

o u t l e t f o r w a t e r a n d an o t h e r o n e wi t h a s t e a m mix e r a t t a ch e d

f or pr oduci n g w a t e r o f a n y d e sir e d t e mp e ra tur e T h e d e sks .

,

p hi c h a r e 6 f ee t l o n g c on t a i n th e F a l e
,
s t yp e o f cupb o a rds an d ,

a r e a rr a n g e d f o r t w o s t ud en t s t o w o rk o n a l t e r n a t e a f t e r n oon s .

Th er e a re n o sh e lve s o r r a cks b e tw e en th e d e sks an d on this

a cc o u n t th e r o om is li gh t a n d i t is p o ssibl e t o l ook a cr o ss th e e n t ir e

lab ora to ry a t an y tirn e T h e room is of course e quipp e d wi th.

fire e x t i n guish e rs b o t t l e s o f dry s o di um bic a rb on a t e f o r burn i n g

,

o il,
a n d bl an k e t s a t e a ch e n d o f e v e ry a isl e an d t hr ee ne e dl e
, ,

sh owe r b a ths in ca s e on e s clo thin g ca t ch e s fire

-
’
.

A b ook is n e v e r a thi n g by i t s e lf I t is a lw ays a grow th an d .

vi P RE FA C E
m an y f a c tor s an d influ en ce s from o the r work e rs con tribu te
l a rge ly in th e m aki n g of it T h e au thor is ve ry gl ad to m ak e .

a ck n o wl e dgm e n t f or a ssis tan c e of v a ri ous ki n ds t o such w o rks

a s th e f o ll ow i n g : B ar n e tt T h e P r ep a r a t i on o f Org an ic Co m
“
,

p ou n ds ; B Coh e n P ra c tical M e thods of Organ ic Ch em

”
.
,

is try ; E Fisch e r
”
. I n tr o duc ti on t o th e P r e p a r a ti on of Org an ic
,

Comp o u n ds ; G a t t e rmann P r a c t ic al M e th ods o f Organ ic

” “
,

Ch e mis t ry ; H en l e A n l e i tu n g f ii r d as o r gan isch p rapara tiv e

”
,

P r ak tikum H oll em an L ab or a t o ry M an u a l o f Org ani c

,

Ch e mis t ry f o r B e gi n n e rs L W J on e s L ab o r a tory Ou tlin e

“
. .
,

o f Organ ic Ch e mis t ry ; F J M oo r e E xp e rim en t s in Org ani c

”
. .
,

C h e mis t ry J F N o rris . E xp e
. rim en t a l O r g a,
ni c C h e mis t ry
W A N oy e s
. . Org an ic Ch e mis t r y f or t h e L ab o r a tory ; S u d
,
”

b orough an d Jam e s P ra c t ica l Organ ic Ch emis t ry ; an d U ll

,
”

m ann Org an isch ch e misch e s P r ak tikum

,
-
S p e ci a l r e fe r en c e s .
”

a r e giv e n h e r e a n d t h e r e l ar ge ly t o i n duc e s t ud e n t s t o ge t a c

q u a in t e d wi t h a r t icl e s i n t h e j our n a l li t e r a t ur e a n d t hus t o

s timul a te th e m toward acquirin g a goo d sci en tific a tti tud e to wa rd

ch emis try .

I wish to m ak e m os t ge n e ro us a ckn owl e d gm en t to my fri en d

a n d c o ll e a gu e P r o f e ss o r J o hn M N e ls on
,
T h e w o rk h e r e i n s e t . .

f or th w as b egu n wi th h im an d gre w u n d e r his con s tan t symp a

t h e t ic suppo r t an d ki n dly guid an ce H is s oun d a dvic e an d .

valu abl e su gge s ti on s call for my m os t cordi al th an ks .

I am a ls o i n d e b te d t o P r o fe ss o r Th os B Fr e a s an d his a ss o . .

ci a te s of th e s to ck room for m an y f avo rs an d to M r S J B all ard . . .

,

w h o m ad e m a n y o f th e d r awi n gs an d p r e p a r e d a l l f or th e pub

l is h e rs .M y si n ce re th an ks are a ls o given t o Dr Ge orge .

S ca t ch ard a n d M r Willi am E M o r ga n an d t o m an y s tud e n t s

. .
,

who s e fri en dly a dvice an d h e lpful c o op e ra t ion h as b een of th e -

gre ate s t a ssis ta n ce .

A sp eci a l f or e w ord con c e rn in g organ ic c ombus tion s whi ch

con s ti tu te s th e subj e c t o f th e s e con d p ar t of this w ork will be
f ou n d jus t pre c edin g th at par t .

H ARRY L FI SHE R .

C M
OL U UNB IA Y I VE RS I T ,

J un e ,
19 19 .
 CO N T E N T S

P AR T I

L A BOR AT ORY EX P E RI M E N S T
EXPT . NO .

G E NE RA L N OT E S AN D S U GG E S T I ON S
I N CAS E OF A CCID E N T OR FI R E .

D E TE R MI N AT I ON OF T H E BOI L I N G -
P OI N T A ND S TA N D ARD I Z A
I T H E RM OME T E R I N T H E OR DI N ARY D I S T I LLA
T ON OF T H E

T I ON APPAR AT U S .

*
2.FRAC T I ONA L D I S T I LLAT I ON ; FRAC T I ONAT I ON OF A M IX T U RE
OF E T HY L A L C OH OL AN D W AT E R 22

3.A B S O LU T E A L C O H O L . 26

4.T E S T S F O R C A R B O N A N D H YD R O G E N I N O R G A N IC COMP OU N D S 3 0
*
5.M E T HA N E F R O M C H L O R O F OR M A N D C H E M I CA L P R OP E R T I ES

OF P ARA FFI N HYD R OCAR B ON S .

6 P R E PARAT I ON OF E T HYL I ODID E F R OM E T HYL A L C OH OL

*
. .

7.P R E PA R A T I O N O F E T HY L E N E A N D E T HY L E N E D I BR OM ID E .

8 E T HYL E N E
*
.

*
9.A C E T Y L E N E

( I ) Fr om Cal c ium Ca rbi de

.

Fr om E thylen e D ib r omide
*
Io .A L C OH OL S R E A CT I cg s OF
,

I I
. T H E I D E NT IFICAT I ON OF AN AL C OH OL T H E M E T HYL —

E S T E R OF 3 5 D I N I T R OB E N Z OI C A CID
.
-

*
12 .D E T E R MI N AT I ON OF T H E M E L T I N G P OI N T -

P R E PAR AT I ON OF D I ME T HYL E T HYL CAR B I N OL ( G r ign a r d s

—
* -
’
13 .

R e a c ti on ) 69
I 4.P R E PAR A T I ON OF M E T HYL PH E NYL CAR B I N OL
- -
.
73
I 5 D I S T I LL AT I ON i n vac u o OR U N D E R D I MI NI S H E D P RE S S URE
. .
76
T he se ex e p ri men t s c on s ti t u te th e short c o urse , see p v
. .

v ii
 CONT E NT S

EXPT . NO .

A C E TAL D E HYD E (S olu tion )

*
16 . .

17 . P R E PARA T I ON OF A C E TAL D E HYD E AMMON IA

18 . AC E TAL D E HYD E F ROM A L D E HYD E AMMON IA .

*
19 . T E STS F OR
‘
A L D E HYD E S .

20 . M E T HYLAL . HYD R OLYS I S OF M E T HYL E N E D I E T H E R S

21 . FOR MA L D E HYD E : TEST F OR FOR MA L D E HYD E ,
AND P R E PA
R AT I ON OF H E XAM E T HYL E N E T E T RA MI N E .

A C E T ON E
*
22 .

P R E PARAT I ON OF l -
M E N T H ON E AND t-M E N T H ON E OX I ME .

P R E PARAT I ON OF A C E TYL
P RE PARA T I ON OF E T HYL A C E TAT E .

HYD R OLY S I S (SAP ON IFICAT I ON ) OF BU TT E R

L E CI T HI N P R OM E GG YOL K -
.

D E T E C T I ON OF N I TR OG E N S U L F U R T H E HAL O G E N S A N D , , ,

P H OS PH OR U S I N A N OR G AN IC C OMP OUN D
P R E PARA T I ON OF A C E TAM ID E

( )
I F r o m A
.
mm on iu m A c e t a t e a n d G l ac i al A c e tic Aci d .

( )
2 F r o m A mm o n iu m A c e t a t e in a S ea l e d Tu b e

ME T HYL AMI N E .

E T HYL I S OCYAN AT E
M E T HYL M U S TAR D OI L
P R E PAR AT I ON OF G LYC OC OLL P R OM H IPP UR IC A CID P UR I .

FI CA T I ON OF A N AM I N O A CID

HYD R OLY S I S OP S U C R OS E ( C AN E S U GAR ) A ND P R E PARAT I ON

OF P H E N YL G L U COS A Z ON E
P E N T OS E S . FU R F U R AL T E S T
P R E PAR AT I ON OF M U CIC A CID
C E LLUL O S E
BE N Z E N E : C H E MICA L P R OP E R T I E S
P R E PAR AT I ON E T HYL B E N Z E N E (Fit tig s R e ac tion )
’
OF .

P RE PARA T I ON OF D IPH E N YLM E T HAN E (F r i e de l C r af t s -

’
Re
ac t i on ) .

T R I P H E N YL M E T H YL .

P R E PARAT I ON OF BR OMB E N Z E N E
P R E PAR AT I ON OP BE N Z E N E SUL F O N IC A CID ,
S ODI UM S A L T .

P R E PARAT I ON OF N I T R OB E N Z E N E .

P R E PARAT I ON OF AN I LI N E
PR E PA A I R T ON OF AC E T - o- T O LU IDID E
P R E P ARAT I ON OF S UL FAN I L IC ACID
 C ONT E NT S
E m . NO .

48 . BE N ZIDI N E R E ARR ANG E ME N T

*
49 . D YE S : P R E PAR AT I ON OF M E T HYL ORAN G E
P H E N OL PHT HA L E I N
F L U OR E S C E I N
C R YS TA L VI OL E T
50 . P R E PAR AT I ON OF C RYS T A L VI OLE T
5 1 . P R E PAR AT I ON OF P H E N OL , A ND R E AC T I ON S OF P H E N OL S .

5 2 . P R E PARA T I ON OF A N I S OL E
BE N ZA L D E HYD E
*
53 .

54 . P RE PARAT I ON OF HYD R OCI N N AMIC A CID

55 . P R E PAR A I T ON OF p -
T OLU N I TR I L E .

56 . P R E PAR AT I ON OF A CE T A N T H R A N I L I C A CID
57 . P R E PAR AT I ON OF M E T HYL S AL ICYLAT E .

59 . P R E PARA T I ON OF L I MON E N E D IHYD R OCH L OR ID E

60 . C AMPH OR S YN T H E S I S : P I N E N E HYD R O CH L OR ID E .

61 . CAMPH E N E .

62 . I S OB ORN YL A C E TAT E
63 . I S OB OR N E OL .

64 . C AMPH OR .

65 . P R E PA RA T I ON OF A N T H RA QU I N ON E
66 . PYR IDIN E AND QU I N OL I N E

P ART I I

OR GAN I C C OM BUS T I ON S

D I V I S I ON A

Th e D e te rmi na ti on of Ca rb on an d Hyd r oge n

H I S T OR ICA L
I NT R OD U CT I ON .

L I S T OP APPARAT U S A N D C H E M ICAL S
T OPICAL OUT L I N E OF G E N E R A L M E T H OD OF P R O C E D UR E .

T H E APPARAT U S A N D H o w T O P U T I T T OG E T HE R ,
W ITH
N OT E S ON M AN IP ULAT I ON
T he ppa r a tus i a rr a g d i th foll w i g o r d r a d
a s n e n e o n e n

i d is c uss d i t h is sam
s e n rd r e o e

1 . Ta k o f C m
n p r sse d O yg wi th S ta d a d P r ssur
o e x en n n e e

Gauge s
 C ONT E NT S
PAGE

2 . B ubble Coun ter

3 . G a s P u r ifyin g App a r a tus in c ludin g th e ,
P r e h ea t e r
-
.

4 . a T h e E l e c t r i c Co mbu s t ion Fu r n a c e
.

b T h e Comb
. us ti T be a d H ow t Fil l I t on u n o

5 . Ab s o r p t i Tr i on a n .

a Fi r s t Ab rp ti B o t tle f Wa t er
. so on : or

6 S c o d A b s r p tio B tt l e f
. e n Ca r bo D io i d
o n o : or n x e

c Gua r d Tub e a d B tt le
. f P a lla d ious Ch l r i d
n o o o e

S l t io o u n .

M E T HOD OF R UNN IN G BLAN K D E T E R MI N AT I ON S

W E I G HIN G T H E A B S ORP T I ON BOT T LE S
W E I G HIN G T H E S UB S TAN C E .

T H E C OMB U S T I ON P R OP E R .

CAL C ULAT I ON S , AND D I S C U S S I ON OF R E S UL T S

S OME C OMM ON E R R OR S AND H ow To A V OID T H E M
C OMB U S T I ON S U B S T AN C E S
C ON TAIN I N G N ITR OG E N
OF

S ULP U R HAL OG E N S P H OS PH OR U S S ODI U M E T C

, , , ,

C OMB U S T I ON OF L I QU ID S GA S E S A N D E X P L OS IVE S UB , ,

D I VI S I ON B

D e te r min ation oi Nitr oge n

Th e

H I S T OR ICA L I N T R OD U C T I ON .

L I S T OF APPARAT U S A N D C H E MICAL S
T OPICAL OU T L I N E OF G E N E R AL M E T H OD OF P R OC E D U R E .

T H E APPARA T U S A N D H o w T O P U T I T TO G E T H E R W I T H ,

N OT E S ON MAN IP ULAT I ON
1 T h e Ca r b on D ioxi de G en e r a t o r
.

2 T h e M a n ome te r a c c o mpan y i n g S top c oc ks U—tub e

.
,
-
, ,

e tc .

3 . T he E le c t r ic C mb stio Fur ac
o u n n e

4 . T he Combus ti Tub e a d H w t Fil l I t

on n o o

5 . o T he
e e A o t m t r ( N i t r om t r )
z e e

V
. T H E F IN A L P R E PAR AT I ON OF T H E C U P R IC OX ID E
W E I G HI N G THE S U B S T AN C E .

TH E C OMB U S T I ON P R OP E R
C A L C ULAT I ON S , AN D D I S C U S S I ON OF R E S UL T S
T A B LE S FOR N I T R O GE N
 P AR T I

L A BO R A T O R Y E X P E R I M E N T S
L A BO R A T O R Y MA N U A L OF .
OR G A N I C
C H E MI S T RY

GENERAL N OT E S AN D S U G G E S T I ONS

E a ch pr e par ati on , if
liquid is pl a ce d in a squ are 1 5 cc
a , .

gla ss s topp e re d b o ttl e an d if a soli d in a 2 0 cc r oun d wid e

- 1
, , ,
.

mou th ed b ottl e an d n ea tly la b e le d wi th th e n am e of th e

1
,
‘

subs tan ce th e corre c te d boilin g p oi n t or m e l tin g poin t a s f oun d

,
- -
,

by you th e yi e ld of pure subs tan ce (a lwa ys in gr ams to th e

, ,

firs t d e cim al pl a ce as origin ally Ob ta in e d e ven th ough som e

,

m ate ri al may h ave b e en us e d for spe ci a l e xp e rimen ts) an d th e ,

n am e of th e s t ud e n t f o r e x ampl e :
,

E thyl e n e dibro mid e

B P . . 13 1
°
c or .

Yi e ld ,
gram s
J OHN S MI T H

T he yi e l d is the a m ou n t of pure produc t a c tu ally ob ta in e d .

T h e t h eo r e t ic a l yi e ld is th e a m o u n t which w ould be o b ta i n e d
“ ”

if the re a c ti on we n t e n tir e ly to th e righ t a ccordin g to th e ordi

n ary e qu a t i on in o th e r w o rds if th e s tar tin g m a te ri al w as
, ,

en t ir e ly c on ve r t e d in to the pro duc t d e sire d .

T h e yi e ld give n in th e e xpe rim en t s is th e a m oun t usu a lly

Ob ta i n e d by f o ll o wi n g ou t th e dir e c ti on s c a r e fully I t is n o t .

th e th eo r e t ic a l yi e ld .

1
Prac t i c a lly all th e prepara t ion s w ill give a moun ts that w ill be c on ta in ed by
bo ttl e s of th es e siz e s Ac e ta l deh yde ammon i a an d ac e t o toluid ide w ill be foun d
.
- -

t oo b ulky b u t it is e x pe c t e d th a t onl y a sa mpl e o f th e s e w ill be h a n de d in f or

,

in spe c t i on th e r ema i n d e r b e in g us e d f or prep a rin g a n oth e r su bs ta n c e

,
.
2 LABORAT ORY MANUAL
“

OF OR GA NI C CH EM I S T R Y
Only e n itfi ate a cqu ain tan ce m ad e in th e l ab o r
a to ry in th e c tu a l h an dli n g an d th e prep ara ti on an d pu rific a
a

t i on o f c omp ou n ds c an th e s tud e n t h op e t o ga i n a th o rough ,

comprehen sive kn owle dge Of th e prop e r ti e s an d r e a c ti on s of

o rg an ic subs t an c e s S tudy th e e xp e rim e n t s fir s t wi th th e aid
.

Of th e t e x t b o ok a n d a f te rw a rds c a rry th e m ou t in th e l abor a t o ry

-
.

A l w ays r ead through the en tire ex er i

p men t before begin n ing an y

w ork i n the l a bora tory . It is m os t imp or tan t TH AT YOU KN OW

W HA T YOU A RE D OI N G W HE N YOU ARE D O IN G 1T .

Wh e reve r possibl e save tim e by lookin g ah ea d an d workin g

on m o r e th an on e e xp e rim e n t a t a t im e .

N e atn e s s will b e i n sis t e d up on in all l abora tory work Set .

up y our app ara tus n ea t ly an d in good sh ap e an d do n ot all ow ,

u n n e ce ssa ry an d u n us e d app ara tus to co ll e c t aroun d it Ke ep .

t h e d e sk t op fr ee fr om dir t a nd Oil sp o t s T h e app ar a tus in .

t h e cupb oa rds Of th e d e sks S h ould b e cl e an an d n e a t ly a rr an ge d .

T h e d e sks will b e i n sp e c t e d by th e i n s t ruc to r p e ri odic ally .

All app a r a tus a n d ch emic a ls mus t b e pl a c e d wi thi n th e

d e sk a t th e en d of e a ch l ab orato ry p e riod Wh en eve r it is
n e c e ss ary t o l e av e a pp ar a t us on th e d e sk a p rmi ”
r ed ta t
g e

will be issu e d by th e in s tructo r I n such ca s e s do n o t l e ave .

ou t burn e rs or an y o t h e r disc on n e c te d pi e c e s o f app a r a t us

,
.

G ra d e s — T h e l ab or a tory gr a d e will b e b a s e d up on ( 1 )
th e qu a li t y an d yi e ld of pr ep ar a ti on s an d ( 2 ) th e g e n e ra l man ,

n e r in which th e s t ud e n t p e rfo rms his l ab o r a t o ry w o rk i n clud ,

in g his m an ipul a t i on n ea tn e ss kn owl e dge of th e e xp e rim e n t

, ,

while th e work is b e in g d on e as e viden ce d by repli e s to o ral

qu e s ti on s e tc This s ec ond part is given s everal times the w eight
,
.

of the firs t .

N ot e-b ooks is re comm en d e d th at e a ch s tud en t k eep

.
—I t

a n o t e b o ok
-
T w o p age s sh ould o rdi n a rily be a ll ow e d f or e a ch
.

e xp e r ime n t : th e l e f t h a n d p ag e f o r th e Typ e o f R ea c t i on th e
-
,

Obj e c t Of th e E xp e r im en t (f or e x ampl e th e P r ep a ra ti on of ,

E thyl e n e dibr omid e f r om E thyl e n e a n d B r omin e ) th e E qu a ,

t i on f or t h e R e a c t i on M a t e r i a ls t o b e us e d an y sp e ci a l n o te s
, , ,

an d r e f e r en ce s ; a n d th e ri gh t h a n d p a ge f or t h e M e th od o f
-

P rep ar a t ion B P or M P Of S ubs tan ce as fou n d Yi e ld Th e o

,
. . . .
, ,
~
 G ENE RAL N OT E S AN D S U G G E ST I ONS 3

r e t ic al Yie ld an d P e rc en tage c tu al yi e ld Y i e ld which is ,

‘

th e a

mul tipli e d by 1 00 an d divid e d by th e the ore tica l yie ld Ch emical ,

a n d P hysic a l P r op e r t i e s N o t e s an d an y o t h e r d a t a,T h e t opics ,

.

f or th e l eft h an d p ag e given a b o ve r e fe r p a r t icul a rly t o th e

-

“
prep a ration s For o th e r e xp e rim en t s u s e sp e ci al t opics as
.
”

n ee d e d M ak e th e M e th od of P r ep ar ation or P roce dure c on

.

c is e : d o n o t r e wri te th e dir e c t io n s a s giv e n in th e l ab o r a t o ry

dire c tio n s Us e con s ti tu ti on al formul as t hrough ou t T he

.
'
.

l e f t h an d p age should be wri tten up b e fore th e app ara tus is

-

a ss e mbl e d a n d th e e xp e rim en t s ta r te d T he righ t h an d p ag e .

-

should be wri tten up imm edi a tely a f ter the exp e rim en t is com
p l e t e d . Be br ief .

Amo un ts of Ch e mi c al s
ve ry c ase car e fu l ly w eigh or — In e

m ea sure ou t al l ch emicals re ga rdle ss of wh at amoun t may be ,

s tate d on th e l ab e l I f a ho rn pan b al an ce is us ed for w eigh

.
-

in g pl a ce p ap e rs in th e scoops
,
S om e t im e s th e e x a c t a moun t .

is n ot n e cessary as in the m e th an e exp e rim en t A l though the

,
.

lab oratory work in organ ic ch emis try is n ot c arrie d ou t wi th

th e s am e d e gree of a ccur a cy as for e x ampl e in qu an ti ta tive ,

a n a lysis th e b e s t r e sul t s are ob t a in e d o n ly wh en mol e cula r

,

qu an ti ti e s are use d an d th e s e are usu al ly given in the direc

,

t io n s . Ch emicals S hould g en e r a lly be w e igh e d t o th e firs t

d e cim al pla ce .

For a liquid th e s pec ific gr avity e qu a ls th e w e igh t di vid e d

,

by the volum e This simpl e e xpre ssi on S hould a lways be born e

.

in min d wh e n m akin g c a lcul at ion s wh e r e liquids are in volve d .

Cu tti n g S ti c ks of S ol i d S o di um or P ota s s ium Hydr o xi d e .

Caus tic alk ali sh ould n ot be h an dl e d wi th t h e fin g e rs Put .

th e s t ick on a pi e ce of fil te r p ap e r an d t urn up on e S id e a s a ,

bufler A comm on kn ife an d a sh a rp blow up on it will quickly

.

c u t off th e d e sir e d a m ou n t P ro te c t th e e ye s wi th goggle s . .

For a lk a li in th e ey e u s e ca s tor Oil (S ee p ,

. .

Rubb e r S toppe rs S hould n o t be l e f t in an y pi e c e o f app ara tus

which h as b een h e at e d Th e y S hould be re m ove d if p ossibl e.
, ,

as s oon as t h e h e a t i n g is disc on t in u e d Oth e rwis e th e s topp e r .

will b e m old e d to th e sh ap e of the open in g by th e con tra c ti on

Of th e gl a ss in c oo li n g .
4 LA BORA T OR Y M AN UAL OF OR G AN I C CH E M I S TR Y

L oos e n i n g G r ou n d G las s S toppe r s an d S top -c oc ks

— . The
followin g is ve ry Of te n e ffici en t in l oo s e n i n g gl a ss s toppe rs an d
s top co cks Give a s tou t pie ce of twin e on e o r tw o turn s ar oun d
— .

th e n e ck o f th e b o t t l e a n d h ea t th e gl a ss by dr a win g th e s t rin g
.

rapidly b a ck an d for th .

I n c a s e t his m e th od d oe s n ot w o rk c omp ar e Op e n i n g o f ,

bromin e b o ttle s N o te 3 p 3 3 , ,
. .

A n e xc e lle n t m e th o d of r em o vi n g froz en s top cocks is -

g iv e n by V C A .llis on (J.on r n I n d a nd E n g C h e m 11 . . .
,

T h e h an dl e o f t h e ke y is S lipp e d i n t o a s o ck e t in a bl o ck
o f h a rd w oo d whil e th e o p e n i n g o f t h e bl o ck r e s t s a s a c o l l a r

o n t h e sh ould e r Of th e b a rr e l o f t h e s t o p c o ck A plug o f w ood -

.

is pla ce d aga in s t th e o the r e n d of th e key a n d e a sy r e gul a r ,

p r e ssure brou gh t to b ea r by m e an s of a vis e D iff e re n t size s .

a re giv e n f o r t h e o rdi n a ry s t op c o cks in u s e T h e sch e m e is -

.

rapid an d it w orks "

F ollowi n g are th e n am e s of t hree c on cise an d valu able h an dy
b ooks which c on t a i n a l a rg e a m ou n t Of ch e mica l d a t a in com
p ac t r eady r e fe re n ce fo r m
-

Va n N o s tr a n d s Ch e mic a l An n u a l Ch emik e r
’
8v o ; ,

K ale n d e r ( Ge rman ) 2 vols 1 2 mo ; H an db ook Of Chemis try

,
.
,
“

a n d P hysics 7 t h E ,
d 1 9 9 publish e d by T
. h,
e C h e mic a l
1 R ubb
, e r
Co C le v e l an d O
.
,
2 mo ,
.
,
1 .

Coll e c ti on of L i qui d S pe c im e n s in th e P r e paratio n s ”

.

I n th e B oili n g p oi n t E xp e rim e n t (E xp e rim e n t N O 1 ) y ou will

-
.

Obs e rv e t h e i nfl u e n c e o f r a di a t i on sup e r h ea tin g e t c a n d this , ,

.
,

will give you an id ea as t o h ow e ven pu r e li quids b eh ave durin g

dis tilla tion in th e o rdin ary app ara tus W hen y ou a re m akin g .

pure sp e cim e n s th e b e h avi or of th e s e pur e liquids S hould be

k ep t in min d Th e re will be a sm all p o r ti on p assin g ove r wi th in
.

—
2 3
°
b e fore th e t emp e ra ture h as r ea ch e d th e prop e r b oili n g
p o i n t a
,
n d an o t h e r sm a ll p o r ti on n ea r th e e n d a s th e t e mp e r a t ur e

rise s 2 or U su a lly in o rdi n a ry l ab o r a t o r y pr e p ar a ti on

° “ ”

work th e se fir s t an d l a s t ru n n in gs are coll e c te d alon g wi th the

m aj or p or tion dis tillin g a t a con s tan t t empe ra tu r e an d the
e n t ir e a m ou n t w e i gh e d a s a sp e cim e n M a te ri a l b oili n g b e l ow .

o r ab ov e t h e s e limi t s sh ould b e disc a rd e d On th e l ab e l s t a t e .

 I n Ca s e of ACCI D E NT or FI RE

FIRE — F re e t i x i n gui s h e r s a re hu n g up all a roun d the ro om .

I n c a s e of burn in g o il u s e th e p owd e r e d s od ium b i c ar b on ate

in th e b o t t l e s on th e r a cks .

T h e bl an k e ts a r e f or wr appi n g r ou n d a p e rs on wh o s e cl o th
in g is on fire I f n e c e ss a ry u se th e n e e d l e s h owe r s
.
,
.

ACCI D E NT —
. On th e sp e ci a l S h e lf in th e l ab o r a tory ar e
B or i c a c i d s olu ti on s a tur ate d f or th e e ye s
, , .

( y
E e -
cups h a n g b e l o w sh e lf ) .

Ac e ti c ac i d 1 per c e n t s oluti on f or w a shi n g a lk a li from

, ,

th e skin .

Cart on oil (h alf li n s e e d Oil an d h a lf lim e w a t e r) f or all ,

kin ds of b urn s in cludin g alk ali an d a cid burn s on skin

, .

S h ake w e ll b e fo re usi n g .

Ca s tor oil f or e y e b ur n s e sp e ci ally alkal i in th e e ye , .

Th e re is a firs t aid ki t in th e in s truc tor s l ab orat ory ’

.

ACID S — On s ki n : w a sh wi th mu c h water imm e di a t e ly th en ,

wi th dilu te s odium bic arb on a te U s e c a rron Oil (on sh e lf) ; .

on c l oth i n g : w a sh wi th dilu te amm on ium hydroxid e

s olu ti on .

ALKALI E S .
—I n th e e y e : u se s atur a te d b o ric a cid on sh e lf if
in jury is sli gh t D rop c a s tor oil i n to th e e ye ; on s kin : wa sh
.

wi th much Wa te r the n wi th dilu te a c e tic a cid 1 pe r cen t

, ,

s olu t i on or sa tura t e d b oric a cid s olu ti on U s e c arron Oil ;

,
.

o n c l oth i n g : u se s om e w e a k a cid li k e a c e t ic o r b o ric w a sh , ,

an d t h en n e u t r a liz e a n r em ai n in g a cid wi th amm on ium

y

hydroxid e or amm on ium carb on a te .

BR OM I NE .
—
On S ki n : w a sh wi th a n y s o lven t lik e a lc oh ol , ,

b en z en e gas ol en e b en zin e c arb on te tra chl orid e or dilu te

, , , ,

s odium bic arb on ate Th en t rea t wi th c arron Oil or c ar

.

b ol a te d va s e lin e .

N OT E — Po s t a opy f th is sh t o th e bull e ti b oa r d a n d a ls o
c o ee n n

giv e t h e n a m e a n d t l eph o e e u m b e r o f t h e n
n e a r ens t p h ysici an an d

th e ne a r e s t h ospi tal .
 E xpe r im e n t N o 1 .
1

D e termin ati on of th e B o ii
l i
n g-p o n t an d S tan d ar d izati on of th e
T h e rmome te r in th e Or din ar y D i s til l in g Apparatu s

On e of ch ara c te ris tic physic a l c on s t an t s Of a liquid is

th e
i ts b oili n g p o in t an d a c o mp o u n d is g e n e ra lly c on sid e r e d pur e
-
,

whe n it dis ti lls a t a con s tan t b oilin g p oi n t u n d e r c on s tan t pre s

-
,

sure I t may a ls o aid in th e id en tific a ti on Of a comp ou n d

. .

I n r e gul a r l ab o r a to ry w o rk it is d e te rmi n e d by m ean s o f a t h e r

mome te r in a dis tilli n g fl a sk a n d th e te mp e r a t ur e of th e vapo r
e n t e ri n g th e o u t l e t t ub e is r e c o rd e d a S t h e boili n g p oi n t Of t he
‘

liquid Obvi ously in this m e th od wh en th e o rdin a ry lon g scale

.
,
-

3 6 0
°
t h e rm o m e t e r is us e d t h e r e a r e s,
e v e r a l e rr o rs o f whic h ,

th e foll o wi n g are m o s t imp or tan t : th e t ru e b oili n g p oi n t is n o t -

usu ally f ou n d b e cause th e e n tire c ol u mn Of m e rcury is n o t sur

rou n d e d by th e vap o r th e v ap o r is e a sily sup e rhe a te d an d
, ,

th e t h e rm om e te r may b e i n a ccu r a t e S i n c e th e b o ili n g p oi n t

.
-

Of e a ch l iquid c o mp ou n d pr e p a r e d in th e c o urs e mus t b e d e t e r

min e d wi th a f air a m ou n t of a ccura cy th e t he rm om e te r mus t ,

be s ta n d a r di z e d a t th e b e gin n in g an d in o rd e r t h a t an y c or
,

re c tion fou n d may apply in th e r e gula r wor k th e s am e gen e ral

f orm of app ara tus will be us e d in th e s tan d ardiz a ti on as in th e
re gular wo rk .

T h e e rr or du e t o th e c o oli n g of th e c olum n o f m e rcury which

e x ten ds ab ov e th e s t opp e r of th e fl a sk an d t h e r e f o r e ou t o f th e ,

vapor of th e b oili n g liquid Of te n a m ou n t s to 6 or 7 f or hi gh

,
° °

b oilin g liquids I t c an b e corre ct e d a s d e scrib e d in th e n ote s

.

a t th e en d Of th e e xp e rim e n t bu t th e m e th o d o f c o rr e c t i on is
,

op e n t o gr av e e rr o rs sin c e it is s e ld om p o ssibl e an d n o t a lw a ys
,

con ven i en t to ob tain th e r e quire d ave rage temp e rature of th e

1
H v y r d v r th s t i
a e ou ea o e ti tl d
e ecG r l N t s d S ugg sti
on e n e en e a? o e an e ons
”
8 LA BOR AT OR Y M A N UAL OF OR GA N I C CH EM I S T R Y
e xpo s e d m e rcury column Fu r th e rm o re thi s c o rr e c tion va ri e s .

a n d mus t b e m a d e e v e r y t im e a dis till a t i o n is c a rri e d o u t T his .

s o c a ll e d s te m co rre c ti on c an be obvi a te d by usin g a the r

“ ”
-

mome te r wi th a sh or t sca l e an d Of such a siz e th a t th e en tir e

c olum n Of m e rcury will be surrou n d e d by th e vap ors of th e
b oili n g liquid I n ord e r th a t th e ordin ary ran ge of b oil in g
.

p oin t s of comm on liquids may be cove re d you will u s e a se t .

Of thr e e t h e rm om e te rs ea ch on e Of which h as a sh o r t sca l e

1

wi th a t otal ran ge Of NO 1 1 5 to N O 2 9 5 to .
,
°
.
,
°

No 3 1 7 5 to .
,( S e e Fig I ) Th e s e th e rm om e ters
°
. .

ov e r l ap ea ch o th e r by a n d t his m ak e s i t possibl e t o choo s e

“ -
”

th e o n e which c an be e mpl oy e d t o th e b e s t a dva n t a ge P ure .

liquids will be us e d in th e te s ts an d a comp aris on exp e rimen t

will be m a d e in a t leas t on e i n s tan ce to S how th e e x ten t Of the
s tem corre c tio n by usi n g b o th a sh or t scale an d a lon g scale - -

t h e rm om e t e r w i th th e s a m e liquid (an i l i n e )
2
.

T h e e rr or d ue t o sup e rh e a tin g c an be m ad e a min imum by

prop e r h ea tin g o f th e liquid in th e fl ask
T h e t e mp e r a tur e which is ob t a in e d u n d e r co n di ti on s wh e re
th e e rr o rs m e n t i on e d ab o v e h av e b e en e limin a t e d or r e duc e d
to a fr a c t i on l e ss t h an th e e rr o r o f Obs e rv a t i on is ge n e ra lly
c on sid e re d a s th e c orrec ted boil in g poin t S uch a temp e rature -
.

when wri tten is followe d by the abbrevi ati on c or This dis “

.

tin guis h es it fr o m th e mul ti tud e o f u n qu a lifie d (m e ani n g g e n e r

a lly u n c o rr e c t e d ) b o ili n g p o i n t s which u n fo r t u n a te ly fill th e
-

li te ra ture an d t ex t b ooks M ore corre c te d b oilin g poin t s are

-
.
-

n ow b e in g r ep o r t e d th an e v e r b e f o r e an d this is a g oo d om en ,

f or fu tur e w rk I t is h op e d t h a t h en c e for th a n un qu alifi e d

o .

boilin g p oin t will m e an a corre c te d b oili n g p oin t I f th e c or

- 3 -
.

1 T h e ma rkin gs s oli d s tem th e rmome ters Of ten bec ome v e ry d im a n d d if

on

fic ul t t o rea d o n a c c o u n t o f t h e l o ss o f th e bl ac ke n in g from t h e fin e li n e s T hi s .

c a n b e re me d i e d b y ru bbi n g a li tt l e gra p h i te o v e r th e li n e s an d w ipi n g off th e

e xc e ss .

A method Of s tan dardizin g a long sc al e th e rmometer is desc ri bed in th e

2 -

n ote s p 2 0
,
. .

E v en th is book c o n ta i n s so me b o ili n g p oi n t s w h i c h a re u n qu a lifi ed si n c e i t

3 -
,

h a s n o t al w a ys bee n p o ssibl e t o fin d th e d a ta in th e li t e ra t ure o r t o Ob ta i n th e

pure ma t eri als e tc n ec es s ary ,
.
,
.
 4 — 2 75 °
—29 5 °

FI G . 1 .
— S h ort S c al e T he rmomete rs .

M a n u t a c t u re d b y E ime r A me n d , N Y a n d s ol
. d u n der the na me of F is h er Organ ic
T h er mome t er s
.

9
10 LABOR AT OR Y MANUAL OF OR GA NI C CH EM I S TRY

re c te d b oili p oin t is f or a pre ssure o th e r th an 7 60 mm th e

n g- .
,

pre ssure is pl ac e d as a subscrip t b e fore th e t emp e ra tur e f or ,

e x ampl e
“ ° ”
,
b p 7 3 5 9 9 c or
. . .

S e t up a dis t illi n g appa r a tus usi n g a 6 0 cc d is tilli n g flask ,

.
-
,

s tyl e B (Fig a n d a c on d en s e r
. wi th s traigh t i n n e r tub e 1
.

Cl amp t h e fl a sk s e cur ely bu t n ot t oo tigh tly a bove th e ou tl e t

, ,

tub e (why ? ) a n d if p o ssibl e jus t u n de r th e lip (W hy ?) .

S e l e c t th e th e rm om e te r which h as th e righ t t emp e ra tur e on

th e sc al e wh e r e i t will be surr ou n d e d by th e v apor of th e li quid

(w a t e r in th e firs t dis ti ll a ti on ) an d f a s te n it in th e n e ck of th e
,

fl a sk wi th a s ou n d w e l l b or e d c ork F a s ten th e ou tl e t tub e in

-
.

t h e l a rg e r e n d o f the c on d e n s e r T h e ou tl e t tub e sh ould p a ss

.

f ar e n ough i n t o t h e c on d en s e r th a t th e v ap ors will be d e liv e r e d

dire c tly i n to th e p ar t of th e con d en s e r th at is surrou n d ed by
th e w a t e r . C omp a r e upp e r sk e t ch in Fig 3 . .

T he bulb o f t h e th e rm om e t e r sh ou l d b e pl a c e d jus t bel ow

th e o u t l e t t ub e b u t n o t in th e bulb o f th e fl a sk a n d n e v e r in
, ,

t h e liquid (W hy ?) I t mus t n o t t o uch th e w alls o f th e tub e

. .

( W hy ? ) B e sur e th a t t h e c o rk d o e s n o t c o v e r up the th e rmom e te r

wh e re the d e gre e s mus t be s e en I n this e ven t r ais e or l owe r .

th e th e rm om e t e r or c u t Off a c ompl ete p o r ti on Of th e c o rk o r

,

e xch a n ge th e fl a sk W h en th e sh o r t scal e th e rmome te rs a re

.
-

us e d this difficul ty will s e l d om be e n c ou n te red .

S of te n th e s e l e c t e d c o rk by m e an s Of a c o rk pr e ss (Th e re .

a re c ork pr e ss e s on th e sid e w a lls o f th e l ab o r a t o ry ) Or wrap

°
.

i t in a fil t e r p ap e r a n d r oll i t u n d e r f oo t M ak e a h ole wi th a .

s ha rp c ork b or e r which h a s a sligh tly sm a ll e r di am e te r th an th e

-

d e sire d op e n i n g H old th e cork in th e h an d an d turn th e b ore r

.

gen tly by m ean s of th e r od which sh ould be i n se r te d through th e ,

h ole s in on e en d of th e b ore r I n orde r t o b ore the h ol e s traigh t .

it is o f ten fou n d c on v en i en t to kee p turn i n g th e c o rk in th e

le f t h an d a f te r ea ch sligh t twis t of th e b ore r an d n ot t ak e th e ,

righ t h an d from th e h an dl e of th e b ore r a t all I f th e c ork is . .

pla ce d on th e d e sk th e b ore r u n d e r e xce ssive pre ssu r e gouge s

,

ou t th e in sid e of th e c o rk a n d in a ddi tion plu n ge s thr o ugh t o

1
When th e w ord c on d en ser is used “
it o rdi n arily mea n s a c on den e sr wi th
w at e r j ac ke t ( L i e big c on den s e r) .
LA BORAT ORY E XP E RI M E NT S 11

OR D I N A R Y
D I S T/L U N G FL A 5 115

'

FL A s rrs

FI G . 2.
12 LA BOR A T OR Y M A N UAL OF OR GA N I C CHE M I S T R Y
th e h a rd surfa c e Of th e s ton e cove rin g an d its cu tti n g e dge is ,

ruin ed A s a rul e it is we ll t o pull ou t th e b ore r wh e n it is ha lf

.

t hr ough t h e c o rk an d push ou t th e c o rk plug i n sid e b e f o r e c on

,

tin u in g th e b o ri n g I n t his w ay a cl e an e v e n c u t is m a d e
.
,

thr ou gh ou t U s e a r a t t ail fil e t o en l a rg e t h e op e n i n g a n d m ake

.
-

it fit tigh tly P l a c e th e c o rk on th e d e sk an d run th e fil e b a ck an d

.

for th a lw ays pre ssi n g d own w a rds an d m ean while r ollin g th e

,

c ork T h e c ork sh ould slid e ove r th e tub e w ith on ly moderate

.

p r es s u r e N e.ve r tr y t o t h r u s t a tu b e thr ou gh a c or k of too s mall

ape r tur e ; a n i n jur e d fi n ge r or h an d is v e ry i n c on ven i en t if ,

n o t us e l e ss f or l ab o r a t o ry w ork
,
Tak e h old of the tub e n ear
.

the c ork an d twis t i t s l ow l y as i t is c a r e fully f o rc e d in I t is .

a dvis abl e t o u se n e w c o rks as much a s p o ssibl e in o rg an ic w o rk ,

a n d t h e r e f o r e a g oo d supply o f t h e d ifl e r e n t siz e s sh o uld a lw a ys

be ke p t on h an d .

A l w ays re move the s to pper from a f l a s k or c on den s er before

c han gin g p the os ition f
o an y g s s tu be
l a or ther mometer in the
hol e of the s topper .

S e t th ec on d en s e r a t a con ven i en t an gl e s o th a t th e c on d en se d
liquid will drop dire c tly i n to the re ce ive r which S h ould as a , ,

rule res t u pon the des k U s e a l arge c on d en s e r cl amp wi th

,
.
,
1

th e tw o pr on gs u n d e rn e a th a n d t urn th e h e a vy b a se Of th e s tan d
,

tow a rd y ou wh e r e i t will be u n d e r n ea th th e c on d en s e r T he .

b a se Of th e s tan d to whi ch th e dis tillin g flas k is a tta ch e d sh ould -

a ls o be u n d e r n ea th th e fl a sk a n d turn e d t ow a rd y ou I t is n o t .

a lw ays n e c e ss a ry t h a t th e dis t illin g fla s k b e a bs o lu te ly v e r t ic al :

-

T h e p o si t i on s o f th e fl a sk a n d th e c on d e n s e r c an c on ven i en tly
be arr an ge d b e fo r e c on n e c tin g an y p a r t s of th e app a ra tus by '

pu ttin g th e m in pla ce wi th the upp e r p ar t of th e c on d en se r in

li n e wi th bu t jus t b ehin d th e ou tl e t tub e of th e fl a sk Th en
, ,
. .

wh en th e app a ra tus h as b een a djus te d for th e prop e r an gle s ‘

th e c on d e n s e r c an b e slid d ow n t hr ou gh th e l a r ge cl a mp a n d
t h e n b r ou gh t up a r ou n d th e o u tl e t t ub e o f th e dis tilli n g fla s k -

a n d fa s te n e d .

I n c a s e it is d e sir e d to disc on n e c t th e dis tilli n g flas k wi th -

1 T he pro n gs O f al l c l amps sh o ul d be prote c te d i

w th w h t e i rubber t ubi n g
or s t ri ps of c ork or fel t .
14 LA BOR AT OR Y M A NUAL OF OR G ANI C CH EM I S T R Y

ou t chan gi n g th e cl amps an d adjus tm en t s it is easi e r to do this ,

by l oos eni n g th e s topp e r in th e upp e r p ar t of th e c on d en se r

a n d a ll owi n g th e c on d e n s e r t o slid e d ow n t hrough th e l a r ge

clamp before r em ovin g th e dis tillin g fla s k rath er th an to dis -

,

a rr an g e t h e s e t ti n g o f th e cl amps an d s t an ds by t aki n g aw ay

th e dis tilli n g flas k firs t

-
A f te r th e dis t illi n g flas k is r e a dy wi th
.
-
,

fi t ti n gs m ad e e t c an d clamp e d in th e origi n al p osi tion the

,
.
, ,

c on de n se r c an th en r eadily be re pla ce d an d con n e c te d wi th ou t

ch an gi n g th e an gle an d m ain p osi ti on of an y clamp .

T h e upp e r Out l e t for w a t e r fr om th e c on d en s e r Should b e

a bove th e j a ck e t s o as t o give th e m aximum c on d e n si n g sur

fa ce sin ce th e c on d en s e r will th e n be full Of w a te r I t sh ould .

be s om ewh a t S l an t e d s o th a t th e rubb e r tub e which c arri e s th e

w as te w a te r will n ot ki nk T h e rubb e r tub e s S lip on e a sily if
.

a dr op o f w a t e r is us e d a s a lubric an t or if m ois te n e d by m e an s

o f th e br ea th .

U s e a sm all E rl en m e ye r fl a sk as th e r e c e iv e r 1
.

A dd 1 5 cc of dis t ill e d w a te r to th e dis t illi n g flas k usi n g

.
-
,

a fu n n e l wh o s e s t e m r ea ch e s bel ow th e Op e n i n g o f th e o u tl e t

tub e an d dr op in s e v e r a l sm al l pi e c e s n o t dus t p ar ticl e s of

, , ,

p orous tile to pre ven t bumpin g H ea t th e fl ask dire c tly wi th .

?

a sm a ll blu e flame n o t ov e r 1 cm in h e igh t gi v i n g i t a r o t ary

3
.
,

mo tion a t firs t an d h old th e burn e r obliqu e ly s o th a t in ca s e

,

th e fl a sk bre aks th e h an d will n o t b e in d an g e r Wh en th e .

liquid dis till s re gul arly th e burn e r sh ould be s e t dire c tly u n d e r

n e a t h a n d w ith the f l a me touc hin g the f l as k D O n o t h e a t th e .

surf a ce ab ove th e liquid as this will sup e rh ea t th e vap ors A void .

draf t s ; u s e a con ical m e t al shi e ld chim n e y for th e burn e r or a

l arge wi n d shi e ld f or th e app ar a tus .

T h e t e mp e r a t ur e will ris e r apidly a t firs t u n til n ear th e

1
S uc h a re c e iver sh oul d ne ver be fa s te n e d to t he c on d en e sr by mea n s of a

s topp e r (W h y ? )
.
3

2
W h e n a l a rge r fla sk is use d as in some o f t h e l a t e r e xpe rimen t s it is pro
, ,

t ec t e d w i th a w ire ga u z e w h e n b e i n g h ea t e d T h is me t h od h o w e v e r gen era lly

.
, ,

t en d s t o sup erh ea t t h e v a p o r a n d t h e r e f o re giv e s h i gh re sul t s in d is t ill a t i on s .

3
S u c h a s ma ll fl a me c a n ea sily be Ob t a i n e d by c u t ti n g d o w n t h e supply of
a ir a t t h e s a me t ime t h a t th e ga s supply is l o w e r e d Al w ays regulate the gas sup
.

ply (oi th e T irrill burn e r) by mean s Of th e s e t s c rew at th e base .

 LA BORAT OR Y E XP ERI M E NT S 15

b oili n g p oi n t Of th e subs ta n ce a n d th en slowly u n til fin ally

-
,

i t will r e m ain pr a c t ic a lly c o n s t a n t Dis till ove r a t le a s t on e h alf .

-

o f th e liquid T h e c on s t a n t t e mp e r a t ur e wi thi n on e h a lf Of
1 -
.

o n e d e gr e e a t which m o s t if n o t a l l Of i t dis t ills is n o t e d as t h e

, ,

obs erved boili n g p o i n t Tow a rd the en d Of th e dis till a tio n the

-
.

t e mp e r a tur e may ris e sligh t ly o n a ccou n t o f sup e rh ea ti n g .

R e co rd the corr e c te d b arom e te r r eadi n g a ls o

2
.

N OTE : T he s al ien t p oi n ts in c on n ec ti on w ith c arry in g ou t a

dis till a tion a re a s ta bl e a nd w ell s et u p appara tu s , w ith r ec e iver

-

r es tin g u p
on the des k, the ther mometer p p
ro erl y pl a c ed ,
c or ks

w ell bored , an d a s m all -s ized f l a me u s ed i n the r ight w ay to p r even t

su p er hea ti n g .

Ne x t,
carry ou t an o the r dis till a tio n usin g th e s am e am ou n t ,

o f pur e a n ili n e c or u n d e r th e s am e ge n e ra l con di tion s

,
.
, ,

e xc e p t t h a t th e w a t e r c on d e n s e r is r epl a c e d wi t h an
“ ”
a ir c on

d en se r an d a s tyle C dis tilli n g flask (Fig 2 ) is use d i n s te a d o f

3 -
.

s tyle B A wa te r co n d e n s e r wi th n o wa t e r in it sh ould n ot be
.

use d in pla ce of th e air con d en s e r b e c aus e of th e d an ge r of

“ ”

cra cki n g a t th e j oin ts A fl a sk wi th a l ow ou tle t tub e is us e d

.

f or high b oili n g liquids in o rd e r to av oid t oo much c on d e n s a ti on

-

a n d on t his a cc o u n t e xc e ssiv e h e a t i n g which c a us e s a p a r t i al

d e composi ti on of th e subs tan ce T h e dis tillin g flas k an d c on .

-

d e n s e r mus t be cl ean an d dry an d fre sh p orous t ilin g sh ould be ,

use d as b e fore .

I n ord e r t o dry a pi e c e o f app ar a t us r apidly ri n s e it wi t h ,

a lc oh ol an d t h en wi t h e t h e r (k e e p a ll fl a m e s a w a y) T o r e m ove .

th e e th e r v a p ors c on n e c t a gl a s s tu be l e a di n g a lm o s t to th e
‘

b o ttom of th e fl a sk wi th th e suc tion or th e bla s t S in ce th e air .

from the bla s t is lik e ly t o be c on tamin a te d wi th iron dus t ,

1
T he e ff ec t sup erh ea t i n g up on th e t emp era t ure of t h e boili n g p o i n t c an be
of -

s een if all th e liqui d is d is t ill ed ov e r T he re is prac t i c ally n o d a n ger Of c rac ki n g

.

t h e fl a s k i it is ma d e o f P yre x gl a ss
f
.

2
For c orr e c t i n g t h e b a ro me t e r r e a d i n g s e e p 3 00 . .

3
A n a ir c on d e n s e r is a l on g s tra i gh t t h i n gl a ss t ub e o f
, ,
c m d i ame t e r . .

T h e i n n e r t u be of a L i e b i g w a te r c on d e n s e r ma ke s a v e ry c on v e n i e n t a ir c on
d e n s e r ( s ee Fig I t is us e d w h e n t h e su b s ta n c e b o ils a bo v e a bo u t 1 5 0
.

I f a su b s t a n c e s oli d ifi e s re a d ily it w o ul d c l og t h e c o n d e n s e r a n d is t h e re fore ,

c o ll e c t e d d ire c tly fro m t h e en d of th e o u tl e t t u be Co mp a re E xp t N O 5 1 p h en ol . . .

,
.
 LA BORA T ORY MANUAL OF OR GA NI C CH EM I ST RY

o il , m ois ture e tc it is b e t te r to u s e th e suc ti on T he w a sh

,
.
, .

a lc o h o l a n d e th e r c an b e us e d a ga i n an d sh o u l d b e pl a c e d in ,

b o t tl e s prop e rly l ab e le d an d k ep t f or this pu r p o s e A ce ton e .

may be us e d in s t ea d Of th e a lc oh ol e th e r c ombin a t i on -
.

T h e subs ta n c e di s till e d may h av e abs orb e d a li t t l e m ois ture

in th e h an d li n g e tc This will be e vid en ce d by a turbidi ty in
,
.

th e firs t ru n n i n gs 1
.

R e pe a t th e dis till a ti on wi th pur e a n ili n e bu t t his tim e u s e an ,

o rdi n a ry l on g sc a l e 3 6 0 th e rm om e t e r i n s t ea d of th e sh or t sc al e
°
- -

th e rm om e te r Comp a r e th e temp e ra tur e Ob tai n e d in ea ch c a s e

. .

S in c e th e b oili n g p oi n t v a ri e s wi th th e air pr e ssur e a c o rr e c tion

-

mus t be appli e d u n l e ss th e b arom e te r sh ows 7 60 mm For .

n on a ss o ci a t e d l iquids th e c orr e c ti on f or a diffe r en c e of every

- ?
,

1 0 mm in pr e ssur e in th e vic in ity o f 7 6 0 mm

.
,
may be f ou n d .
,

by dividi n g th e abs olu te t emp e r a ture of th e b oilin g poin t by -

8 5 0 th a t is
, ,

Corr e c t e d Obs e rv e d b p te mp of Ob s b p + .
-
. . . .
-
.

2 73 + t emp . o f Ob s . b p .
-
.
7 60 — c or . b a r om e tric r e adi n g
x
8 50 10

For ss o ci a te d liquids such a s alc oh ols a cids an d hydroxyl

a , , ,

c omp ou n ds ge n e r a lly divid e by 1 0 2 0 i n s tea d of 8 ,

Wa te r ,

is a n a ssoci a te d liquid an d an ilin e is a n on a ss oci ate d liquid ,

-
.

F o r a m or e c ompl e t e s t an d ardiz a t i on tw o t emp e r a t ur e s , ,

on e n ea r th e b o t t om a n d o n e s om e wh a t n e a r th e t op Of th e

sca le o f e a ch of th e three t he rm om e te rs sh ould be ch e ck e d ,

up T h e f oll owi n g c ombi n ati on s of liquids all of which a re

.
,

fou n d i n th e lis t give n b e l ow c an be u s e d : For th e rmom e te r ,

N O 1 chl or o fo rm a n d wa t e r ; f or N o 2 w a te r an d a n ili n e ;
.
,
.
,

an d f or N O 3 a n ili n e a n d q u i n olin e
.
,
.

T h e f o ll owin g is a lis t o f liquids which wh en pur e a r e sui t

3

a bl e f o r t e s t i n g t h e a ccur a cy Of t h e rm om e t e rs a t th e c orr ec ted

t e mp e r a tur e s f or 7 60 mm giv e n .

1
R ega rd i n g th e
s rp ti on of mois t ure by pure liqui d s w h en
ab o h an dl e d in o rd i
n a ry Op e ra t i o n s c omp a re Y o u n g a n d Fo r t ey Tr a n s Che m S oc
, ,
. . .
,
83 65 .

Al ex S mi th an d M en zi e s Journ A mer Chem S oc 3 2

2
.
,
. . . .
, 90 7 .

C omp a re Y o u n g Fra c t i on a l D is t ill a t i on

3 ”
,
10 , .
 LA BOR AT OR Y E XP E R I M E NT S
Ca rb on b is u l fid e 1

Chl o r of orm .

B e nz en e .

W a te r z
.

E thyl e n e dibromid e
Ch l orb en z e n e
B r omb e n z en e 3

Ani li n e
N i t r ob en z en e
N a p h th a l e n e
Q ui n o li n e .

a B romaph th al en e
-

B en z o ph e n on e
M e rcury

NOTE S ON BOI L I N G P OI N T -
A ND D I S T I LLA T I ON

1 . b oili g poi t of a liqui d is th a t t mpe ra t r e at which

T he n -
n e u

t h e s a tu r a t e d vapo r p r e ssu r e of th e li q i d b e c ome s e q ual t o th e ex t e r n a l u

p r essu r e a d usua lly thi s e te r n al p r ssu r e is th a tmosph r ic p r e s

,
n x e e e

sur e .

T h e t r u e b oili n g p oi t of a li q ui d is i de tical wi th t h c on den s

“ -
n n e

i g poi t of its vapo r u de r th e same p r e ssu r e p r ovi d e d th a t some

n -
n n ,

li q i d is p r e se t an d tha t the vapo r is n ot mix d wi th a i diff r en t

u n e n n e

g a s or v a p o r a d it is
, gen e r a lly
n mo r e c o v e i t t o m e a s u r e t h e n n en

co d n si n g poi t Of th e vapor than the boili g p i n t of th e l i q id

en -
n n -
o u .

T O d o this a o r di n a ry dis t il l a ti
n b lb is gen er all y e mpl oy d on u e .

Y ou ng: F r ac ti al D istill ti on p 6 a on ,
”
. 2 .

T h c rr c t b il i g poi t of a l iq i d a t a t mosph ri c p r e ss r e is
“
e o e o n -
n u e u

b s t d t r mi d by w r app i g c tt
e e e ne wo l o if the l i q i d a t tacks
n o on - o ,
r, u

th a t s bs t a c u a sb s t s
n r o d th e bul b of th th r mome te r B y
e, e o ,
un e e .

Ca rbo n bis u l fide v ery in fla mmabl rea t c a re mu s t be e xe rc ise d

'
1
S and g in h a n d
lin g a n d d is t illi n g it A ba th of w a rm . w a t e r c a n be u s e d f or h e a t i n g i t
bu t th e ,

vapor sh oul d n o t be supe rh ea ted .

2
W a ter is th e o n ly a ssoc i a te d liqui d in th is l is t .

3
Co n si de ra bl e d i ffic ul t y h a s be e n e n c ou n t e re d r ec e n tl y in o b ta i n i n g b ro mbe n
z en e Of t h e d e sir e d puri t y T h a t o n t h e ma r ke t is pro ba bly a l l pre p a r e d by d ir ec t
.

bromi n a t i on o f b e n ze n e w h i c h w a s n o t pro p e rly purifi e d P r e p a ra t i o n o n a ‘

smal l sc ale from pure a n ili n e by S a n dme ye r s reac ti on is rec ommen ded ’
.
18 LA BOR AT OR Y M A N UAL OF OR GANI C CH E M I S T R Y

th is pl an e e though the vapo r may be supe rh ated ye t th e liquid

,
v n e ,

i c tac t wi th th e t h r mom t e r bulb mu s t b e a t th e t r u e b oilin g

n on e e

poi t si ce it h a a fr e
n ,
n r fac e of evapo r atio s R amsay a d e su n . n

You g T n s Ch m S oc
n ,
ra 47 .
4 C e
o m p a r.e C o tt r l l .
, ,
2 . e ,

On t h e D t e r mi n ati on of B oili g p oi t s of S ol u ti s
“
e Jo n n -
n on ,
ur .

A me Chem S oc 4
r . 1 7 .
—
9 ; a d W a
. s h
, bu r a n d R ea d T h e 21 n n ,
“

L aws Of Co c t r a t e d S lu ti o s VI T h e G e e r al B oili g poi t

‘ ’
n en o n , ,
n n -
n

L aw ,
”
i bi d 41 .
—
7 9 4
,
Figu r e s of a speci al appa ra tu s a e 2 1 . r

g ive in b o t h na r tic l e s .

For th e de t r mi n a ti o of co rr e c t b oili n g poi t s a spe ci a l f o r m f

e n -
n o

appa r a t u s is sed i whi c h all possibl e rr or s f r m supe rh a ti g

u n e o e n ,

r adia ti o e tc n,a e p r ovi de d agai st Sh r t sc al e th r mom te r s

.
,
r n . o -
e e

wh ic h a made of n or mal gla ss a d whic h hav b p r oper ly s tan d

re n e een

a rdi d a e empl oy e d
ze r N o r mal gl a ss is a sp ci al gl ass th a t h a b
. e s e en

age d by sui ta bl e t r ea tme t Of h a ti g e t c til it s b eh avi o r on n e n ,

.
,
un

fur th r h eati g a d c li g h a b c ome ifor m S u c h th r mome t e r s

e n n oo n s e un . e

c a b e Ob tai ed w i th c e r tifica t e s sh ow i g th e r e su l t s f s ta da r di a ti on
n n n O n z

by c e r tai bu r eau s of diff e r en t gove r n men t s like th e U S Bu r eau

n , . .

Of S ta da r d s n .

A li q ui d o gh t t o b oil as soo a s its vap o r p r e ssu r e b e come s

2 . u n

sligh tly gr a te r tha a tmosph e ric bu t it is a wel l k ow fac t tha t

e n ,
-
n n

b ili g d o s ot e ce ssa r ily take pl ace

o n e n d e r th e s e c
n di ti o s M os t un on n .

l iqui d s c a r ea dily b e s p e r h a t e d
n T h e t r a n sf r ma ti o Of a li qui d
u e .
1
o n

i to th v apo r phase wil l h w v r t ak pl ac e i mm di tel y if th e

n e ,
o e e ,
e e a

vapor phase a y i e r t gas b i tr d ced b t t o th e rwis

— — n n e n o u ,
u no e .
2

Fo c mpa riso w e h ave th e s p r c ool i g of a li qui d w h i c h w ill s li d ify

r o n u e n o

a s s oo a a p a r ti c l e Of t h e s oli d ph as e is a dd e d f
n s e ampl e ic ,
or x ,
e

i s p r ol d w a t r
n u e co e e .

S p e r h a ti g c a o t t ake pl ace a t th e su r fac e f a li qui d si ce

u e n nn o n

t h e r e t h l i qui d is al w ays i c o ta t w i th t h e vap r ph a s

e I t a l w ays
n n c o e .

ta k s pl ce i th e i te r i o r a d sp ec i all y a t th b t t m w h r e t h
a e n n n e e o o e e

h ea t is appli ed I t is Of c ou r se t p o ssibl t g a n u li mi t d d is
. no e o o n e

ta c e i t th e me ta s tabl e sin ce th e fu r the r away w e g t “

ar ea
”
n n o ,
e

1
is of i n t ere s t to n ot e th a t c hl oroform w hi c h ordi n a rily bo il s a t
It h a s be e n ,

h ea t ed t o a t emp e ra t ur e o f 1 00 by s sp en d i n g t h e d ro ps in a zi n c c hl o ri d e s olu
°

u
t i o n Of t h e s a me sp e c ifi c gra vi t y a n d t ha t w a te r h as si mil a rly be en h ea t e d t o 1 7 0
°
,

by su sp e n di n g it in a mi x tur e o f o ils ( D ufo ur A rc h de l a B ibl u n iv ( 1 8 6 1 ) .

, . . .

P oggend orf A n n al en , 124

’
T XII ,
. 2 10 ; an d s
2
A i tk en ,
“
On b oili n g, c on d e n si n g free i n g
,
z mel t i n g Tr a ns R oyal S c ot
, an d , .

—8 7 ; D uh em,
“
T h e rmod yn ami c s a n d Ch em
ti s h S oc iety f
o A rts , 9 2 40

is t r y ,
”
t ra n s . by B urg ss e ,
—
3 65 8 .
 LABOR A T OR Y E XP E R I M E NT S
f r om e quilib r ium the gr ea te r is th e t d c y fo the sys tem t c me en en r o o

t o e quilib r ium Fi ally th is t de c y w ill b c om s o gr a t tha t the

. n en n e e e

s ys t m w il l b e a bl
e t o o e r c ome i t s r luc ta c e to a c h a ge f ph a s e
e v e n n o ,

vap r i a tio w ill th e tak plac e sudde ly a d som tim s wi th gr a t

o z n n e n n e e e

V i ol i o th r w o r d s b u m pin g oc c u r s S t i rr i g h lps t o p r e e t
c
en
— e n e . n
1
e v n
,

bu mpi g si ce th li qui d is thus e venl y h eat d a d vapor i a t ion

n ,
n e e n z

will tak plac e r a dily a t th e su r fac e a s me tion ed above T h e

e e , n .

be st mea s t o p r ve t bumpi g is to in t r oduc e the vapo r ph ase

n e n n

d i r e c t ly a d th is is d o e in s eve r a l ways
,
n ( ) B y pa ssi g a s t r eam of
n . I n

a ir bubbl s th r ough a c apil l a r y t ub e i t o th

e liquid ( e E p t N O 5 n e s e x . . 1 ,

Vac uum D is til la tio ) ( ) A th r m th od w h ic h is ve ry c ven i t

n . 2 no e e on en

f or a sh o r t p e r io d is t o pl a c e i th e li qui d a s mall gl a ss tub e ab ou t n ,

1 mm i d iam t e r a d s al d a t o
. n e en d I t sh ul d be l o g
n e ough e ne . o n en

t o s ta d up r igh t a d wh
n i po si tion th e op
,
n e d sh oul d b e a t t h e
en n en n

bott m O wa r mi g th e liquid the air in th e tub e e pa ds a d

o . n n x n n

bubbl s th r ugh th li quid I f the distilla ti is i t rr p t d a

e o e . on n e u e ,

n ew t ub m s t b i t r od uc e d (3 ) B y usin g pi e c e s of p or ous t ili g

e u e n . n

wh ic h c o tai s a l rg amou t of ai P umice can o t be used s o

n n a e n r . n

well S i ce it fl oat s i m st liquid s a d th e r efor e doe s n ot i tr oduc e

,
n n o n n

th e a i b bbl e s a t t h s a t of t h t r oubl e
r u Gl a ss b ea d s a d ma y
e e e .
,
n n

substa ce s wi th poi t s a e Of te us d to p r ev t bumpi g bu t

n
“
n
”
r n e en n ,

th e i r e ffici c y do s ot d p d up n t h e i r p i t s bu t upon t h
“
en e n e en o o n ,
e

a i wh i c h is a d s r b d
r t h e i r su r fac e s
o A S so
e a t hi s air h a b
on . on s s een

dr iven Off th ey a o l o ge r of a y s reu l ss th ey a e r mo e d

n n n u e, n e r e v ,

dri e d a n d h a t d b ef r e b i g use d a ga i Ev pla ti um t i 2 “

e e o e n n . en n r

a gl e s a f t r a t i me mus t b e r emove d h e a t d a d a ll ow d t l
”
n e c ,
e ,
n e o oo

in th e a ir b e fo r e b ein g in t r o duc e d agai 3

Fin e pa r tic l es of a y sub n . n

M rg
1
o T h E l m t s f P h ysi l Ch mis t ry
an ,
“
e e 5 th E d
en o ca e ,
.
,

Os t w l d L u th r h mis h M ssu g
“
( 9 )
”
P h y ik 3 A fl g
2
a -
e ,
s O c 9;
-
e c e e n en , . u a e, 1 10 21

L hme M l k l rph ysik

an n ,
“
o e II 5
u a ,
”
, 1 1 .

3
E K en dall in a rec en t n ote J ourn A mer Chem S oc 41
. C .
,
, 1 1 89 , . . . .
, ,

s tates th a t c arbon in c er ta i n f orms is a n exc e ll en t aid t o prod uc e ra pid boilin gg C ' 1

“

I t w as f o u n d h ow e v e r t h a t th e v a ri ous f o rms o f c a rbo n d ifl er grea tl y in th e ir

'
“
, ,

pow er to c a use ra pi d boili n g of a s olu t i on Whil e p ow d e red c h a rc oa l orc ke h a s .

‘

sl igh t po w er in th is re s pec an th rac i te c oal is w i thou t e xc e p t ion £113 v e ry be s t

substa n c e to bri n g abou t th e ra pi d boilin g of a s olu t ion T h e f orma t ion Of bu b .

bl e s d oe s n o t ta ke pl a c e on t h e sh a rp e dge s a n d c o rn e rs l on e but o v e r t h e h a rd
a , ,

smooth surfac e s of th e c oal mi n u t e bu bbl e s fo rm w ith f rea t rapi di t y a n d u n de r '

,

some c on d i t i on s a pi ec e of c oal 2 c a n b e r ais e d from th e bo tt om o f t h e .

fla sk by th e ra pid f orma t i on of bubbl e s on its surfac e I t ac t s in a simil a r man .

n e r in t h e ac i d ifi c a t i on of a c a rbon a t e o r s u l fit e s olu t i on I f th e c oa l is
5
ke p t un der w a te r i nd e fi n i tely I t bec omes l ess ac ti v e bu t h ea t i n g I n a n o v e n W i ll ,
20 LABOR A T OR Y M AN UAL OF OR GA N I C CHE M I S T R Y
s ta nc e r apidl y
lose th ei r a dso rb ed air an d the they i c r ea se th n n e

t e d e c y t o bumpi g i t ea d f d e c r ea si g i t
1
n n n ns o n .

T h s t m rr t i “
i d r s = + N (t —t
’
3 . c o c e o e g e e 54 e n, n e ,

wh e r e N = th a t po r tio of th m r cu ry col umn which is ot h ea ted n e e n

by th vapo r s r ead i d gr ees ; e ,

n e

t = obs rve d b oili g t empe r a tu r e ;

e n
'
t = a e age t mpe r a tu r e Of th e e p
v r e d colum o f me r c u ry
e x os n

a s f oun d by a s e co d th e r mom t e r h u g b sid t h e fir s t n e n e e

on e ;

c o effic e n t o f a i
ppa r e t pa si Of me r cu ry i gl ass n ex n on n .

4 S ta d
. a r d i a t i n
o f a l g szc a l t h r m o m
n ote r on -
e e e .

A l g sca l th e r m me t r is ta da r d i d by l o ca ti g c r tai
on -
e o e s n ze n e n

poi ts f u d by m a s f th e boili g p i t s of pu r e liquid su c h a s

n o n e n o n -
o n s

th o s o p e 7 n a d a .l o t
1 h f,
r e i ng p i t f w as t r a d teh b y e z n -
o n O e ,
n en

plotti g th s r sul ts n c o r di ate pape r the c rr e c tio f a y

n e e e o o- n o n or n

o e d e gr e may b
n e r ad off a t a y time T h e c rr c tio is Of c ou r s
e e n . o e n e

la rge r a s th e b ili g p oi t i c ea es a d Of ten amou ts to se v e r al

o n -
n n r s ,
n n

d egr s f ee h i gh e r b ili g li qui ds

or T h r s l ts a e applicab l e o ly
-
o n . e e u r n

f o th e pa r t i c ul a r d is tilli g fl a sks us d i Ob t ai i g th d a ta
r n e n n n e .

On a pi c f c r ss s c t i
e e milli m t r pap r
o o -
e X 3 00 mm on e e e ,
I OO .
,

ma r k o t h l w e s t h e avy h r i
n e o ta l l in a s t h ab scis sa th e d e gr e s
o z on e e e

o f t h th e r m m t e r
e ry o c e t i g a c h mil lime t r a s a d gr e
ev e ou n n e e e e .

T h c rr c ti s a e g
e o e r ally t o b a dd d a d a th r f r pl ott d
on r en e e e ,
n re e e o e e

ab ve t h
o mai li e I f a y mi us c rr t i s a e f ou d t h e h vy
e n n . n n o ec on r n ,
ea

h r i o t al li e c h
o z n mus t Of c ou r
n os enbe f a gh ab ove th e b o t
,
se, r e n ou

t om Of th sh t t allow spac f o th e pr op r co rr e c ti on s T h e
e ee o e r e .
'

a mou t f th c rr c ti t h a t is th d iff e r e c e b twe e n th e

“
n O e o e on , c o ,
e n e r

b e r d r a di g a d th e t ru e b ili g p oi t a t 7 6 mm
”
re c t d e O s ve e n n o n -
n 0 .
,

is pl t t d a p rp e di c ula r lin e s an o r di a t pp si t the m

o e on e n a n e, o o e nu

be o n th a b s i a c rr s p di g t o t h
r e c ss c rr e c t e d
o e bs rved r ea d
on n e o o e

a d c ou t i g e a h c e ti m t r a s a d gr e f r
”
i g
n ,
n n n c C c t th
n e e e e . on n e e ou

p i
o nt s t h us f o u d w i t h a s m o th
n c u r v d li F r o m t h is c u rv
o i t e ne . e

is ow p ossibl to t ll a t a gl c th e orr c tion f o a y d egr ee

n e e an e c e r n as

f ll w s a dd t th e c rr t d obs rv d r adin g th e di ff e r e c i
o o : o o ec e e e e n e n

d gr s b tw
e ee th e mai ab scissa a t t h poi t of th e c orr t d
een e n e n ec e

O b r v d r a d i g a d th e poi t wh e r it o r d i a te cu ts th e cu rve
se e e n n n e s n .

re s tore it s a c t ivi ty On e o r t w o pi e c e s
. o f a bo ut 1 c m . c ube a re be t t e r t h a n
man y small e r pi e c e s .

I a m i n d eb t e d t o a s emi n a r p a p e r o n
1
B umpi ng by Mr . H a ro l d L . S imons
f o r mo s t o f t h e ma t e ri a l pre s e n t e d in N o t e 2 .
 E xperime n t No 2 .

FRA CT I ON A L D I S TI L L AT I ON

Fr ac ti onati on of a M ixtur e of y
E th l Al c oh ol an d W ater

M e a sur es ep ar ate ly in a gr adu a te d cylin d e r 50 cc of e thyl .

1

a lc o h o l ( 9 5 p e r c e n t) an d 5 0 cc o f dis ti ll e d w a t e r a n d mix th e
.

t w o liquids in a b e a k e r N o te th e t e mp e ra tur e of th e mix tur e

.
,

c ool t o th e t empe ra ture of th e r oom by s e t ti n g th e b e aker in

w a te r an d th en m e asure its volum e again I s it e xa c tly 1 00 .

cc ? P la ce 1 cc of th e c ool e d liquid in to an e vap ora ti n g di sh

. .

an d appl y a fl am e momen tar il y D O n o t h e a t it .D oe s it ca t ch .

fire ? Tr an sf e r th e dilu t e a lc oh ol t o a cl e an dry 1 2 5 cc L a d e n -

.

burg di s tilli n g flas k add s eve ral sm all pi e c e s of porous tile

2
, ,

i n s e r t a th e rm om e te r an d c on n e ct th e ou tle t tub e wi th a c on
,
-

d en s e r h avin g a s traigh t in n e r tub e M ak e tw o fra c ti on a ti on s . .

—
Firs t Fra c ti on ati on T his will con sis t of four fra c tion s
. .

For r e ce iv e rs u s e cl ean dry E rl e n m e ye r fl asks t w o 1 2 5 cc ,

-
.

a n d tw o 6 0 cc -
a n d l ab e l t h e m fr om 1 t o 4
.
,
usin g th e l arger ,

on e s for th e firs t an d l a s t fra c ti on s Have corks r eady to fit . .

T h e te mp e ra t ur e in t e rv als a t which th e fr a c ti on s a re c oll e c te d ,

a s usu a lly t a k en a r e appr o xim a t e ly e qu a l

,
T h e n umb e r of .

fra c ti on s d ep e n ds on th e subs tan ce s an d th e d egree of s ep ar a

t i on d e sir e d . I n t his e xp e r im en t all ow al l th at c om e s o ve r up
t o 8 3 t o flow i n to th e r e c e iv e r l ab e l e d N O 1 Wh en th e tem
°
. .

r e b e gl n s t o e xc e e d 8 3 e xch an g e th e r e c e iv e r f or N O 2
°

p e r a t u .
,

an d c oll e c t th e fr a c t i on up t o simil ar ly for NO 3 .

,

to an d No 4 ,. to

1
Ordin ary l
a c oh o l is
yl al c oh ol
e th .

2
A ske t c h o f th e La de n burg d is ti l li n g fl a sk is given in Fig 2 I t c on sis ts . .

of a d is t illi n g fl a sk a n d a simpl e s t ill h ea d ( or fra c t i on a t i n g c o lu mn ) c omb i n e d .

For suppo r t i n g su c h a ro u n d bot tomed fl a sk w h e n u na t ta c h ed use a sube ri te

-
,

( pre ssed c ork) ri ng .

 LA BOR AT OR Y E XP ERI M E NT S 23

H e a t th e fl a sk firs t wi th a ro tary m otion of th e burn e r

'
.

U s e a sm a ll n on l u min o us fl am e n o t m or e t h an 2 cm l on g
-
. .

Wh e n th e liquid is dis t illi n g r e gul a rly s e t th e burn e r dir e c tly ,

u n d e r th e cen te r of th e fl a sk wi th th e fl am e tou c hing an d do

n o t r e m ov e it duri n g th e e n tir e dis t ill a t io n T h e drops of th e .

dis till a te sh ould form re gul arly an d a t such a ra te th a t th e y c an

e a sily b e c o u n t e d 9 0 1 00 a mi n u t e , Ke ep up thi s ra te by ve ry
-
.

gra du ally i n cre a si n g th e fl am e T h e dis till ati on tak e s abou t .

thir ty mi n u t e s Th e sl ow e r th e dis till a t i on th e b e t te r is the s ep

.

a r a t i on On a cc ou n t Of sup e rh e a tin g th e te mp e r a t ur e may go

.
,

sligh tly ab ove 1 00 t ow a rd th e e n d I t is n ot n e ce ss a ry to

°
.

dis ti ll ove r all th e r em ain in g p or tion A dd it t o r e c e ive r NO 4 .

’

.
,

cool un d e r ru n n in g w ate r an d t h en m ea sure th e am oun t at th e ,

o rdi n a ry t e mp e r a t ur e .

M e a sur e th e v olum e of e ach fr a c tio n an d tabul a te th e r e sul ts ,

a cc ordi n g t o th e foll owi n g sch em e :

Frac t ion I II III IV

T emp e ra t ure Up t o 83
°
to 89
°
to 9 6
°
to
Volume 20 c c .
31 c c . 8 c c .
40 cc

—
S e c on d Frac ti on ati on f T o m ake a fur th e r s ep aration dis till
th e fra c ti on s o n e a f t e r an o th e r a cc ordi n g t o th e foll owin g pro
c e du re : Cl ean ou t th e dis t illin g fla s k an d p o ur in t o it th e firs t -

fra c ti on A f te r a ddin g som e n ew p o r ous t ile dis till as ab ove

.
,

colle c ti n g th e dis till a te up t o 8 3 in r e ce ive r N o I A s th e tem °

. .

b gi s ris b v l h ugh h r will s ill

'

p e r a t u r e e n t o e a o e 8 a t o t e e t b e

som e li quid in th e fl ask in te rrup t the dis till ation by r em ovin g,

the burn e r Wh en th e fl a sk is co ol add t o it fr a c ti on No 2

. .
,

an d a g ain dis t ill u n til th e t e mp e r a t ur e jus t e xc e e ds 8 col

l e e tin g this dis till a te in th e s am e r e ce ive r NO 1 Now add ,
. .

similarly NO 3 a n d fin all y N O 4 c olle c tin g in e a ch ca s e all th at

.
,
.
,

dis tills up t o 8 3 in re ce ive r N O 1 A f te r No 4 h as b een adde d

°
. . .

do n o t s t op th e dis till at i on a t 8 3 bu t c on tin u e a s in th e firs t

°

fra c ti on ati on an d c olle ct th e dis til l a t e s in r e ce ive rs 2 3 an d 4

, , ,

a t th e s am e t e mp e r a t ur e in t e rv a ls a s b e f o r e .

T h e n ew r e sul t s will app ea r s om e wh a t a s fo llows

Frac ti on . I II III IV
T empe ra t ure . Up t o 83
°
to 8 9
°
to 9 6
°
to 1 00
°

cc . cc . cc ,
24 LA BOR AT OR Y M A N UAL OF OR GA N I C CH E M I S T R Y
Apply fl am e to f r a c ti on N O 1 D oe s it ki ndle n ow ?
a . .

A third f r a c t i on a t i on m a d e as d e scrib e d u n d e r th e s e c on d
fra c ti on a ti on would l ea d to a m ore tho rough s ep ar ati on b e c aus e
Of t h e a l t e r e d c omp o si ti on o f th e fr a c t i on s Fur the rm or e an y .
,
.

sin gle fra c t i on may be subj e c te d t o a simil ar pro ce ss of fra c ti on

a t i on by m e an s o f which i t s s e p a r a t io n in t o a lc oh o l a n d w a t e r

could be m a d e m ore n ea rly c ompl e te .

A mix tur e Of e t hyl a lc oh o l a n d w a te r c on tai n in g

p e r c e n t O f a lc o h o l by w e igh t h as a mi n imum b o ili n g p o i n t -
,

(7 6 0 mm ) s o t h a t i t is n o t p,
o ssibl e by dis t ill a t i o n a l o n e

t o m ak e a s e p a r a t i on b e y on d t his p o i n t P ur e a lcoh o l b oils .

at A lc o h o l Of p e r c e n t h a s th e s a m e b o ili n g p o i nt -

a s pur e a lc oh ol .

N OTE

T he r e sul ts
g iven i t h e t abl w e r b t ai n e d u de r th e c o di
n es e o n n

tio sn d e sc r ib ed
ab ve t h t is t h e d i till a t e a m ov r a t t h e r a t
o ,
a ,
s c e e e

o f ab ou t 9 07 00 d r ops a mi u t 1 U de r S imil a r c d i ti o s b t n e . n on n , u

usi g a o r din ary distilli g flask i t a d f th e L ade bu r g dis tilli g

n n n ns e O n n

flask t h e r e sul t s a e som w h t a f llow s : Fi r t f r c tio a tio

,
r e a s o s a n n,

12, 3 8 4
1,0 c c ,
an d s ec o d f r a c t.i o,
a t i : 4 0 0 a d 4 n cc n on ,
2, 1 n 1 .
,

r e spe ctively .

Re fe r e ce s n f or collate ral
r eadin g on th e f r a c ti on a tion of li quid s
wh ic h mix in all propor tion s : M o rgan T he E l emen t s of P hysic al
' “
,

Ch e mis t ry W l r r c i ysi l
”
5 t h E d ,
1 7 7 ; a ke I n t. o d u t on t o P h c a ,

Ch e mis t r y 7 th E d 84 6 ; Washbu r n P r in cipl e s o f P hysi c al

“ -
,
.
,

Ch emis t ry 1 80 1
,
— .

A l ex S mi th I n t r oduc tion t o I n o rgan ic Ch emis t ry

“
.
, New E d , .

f r ac tion at ion 5 8 7 8 ; alcohol an d wa te r 609 ; o th e r c on s tan t

—
, ,

boili ng mix tu i es , '

211
—2
,
2 73 , 2 79 .

F or th e b o ili g poin t c ur e Of mi tur e s Of e thyl alcohol a d wa te r

n -
v x n ,

s ee W . A . N y s a d Wa rf el J
o e nn Am Ch m S 23 ( 9 0 )
,
ou r . er . e . oc .
,
1 1

468 .

A s till h ea d desc r ibed by S F D uf t

-
. . on in an a r ti c l e on
“
T he
li mi ts f s pa r a tio by f ra ti al distilla ti
o e n c on on ,
”
J ourn S oc Chem I n d . . . .
,

38 4 5 is s aid to be u l l v ffici e
,
n usua e n t.
 LABORA T OR Y E X PE R IM E NT S 25

Q UES T I ON S

I . Ou t li n e th e th e ory Of fr a c ti on a l di s t ill a t i on
.

D iscuss th e fr a c ti o n a l dis tilla ti on o f th e three diff e r en t c as e s

Of liquids which mix in a l l pr o p o r t i on s .

E xpl ai n why pur e a lc o h o l is n o t Ob ta i n e d ( S ee N O .

Of a b ou t wh a t p e rc e n t a g e a lc oh ol d oe s th e fi r s t fr a c ti on of
’

t h e s e c on d fr a c ti on a t i on c on sis t ?
Why is th e burn e r n o t r e m ove d a f te r th e dis tilla tion h as
b e gu n ?
6 . Would th e firs t fra cti on be i n cre a s e d or dimi n ish e d if t h e
fl a sk w as prote c te d wi th a wire gauz e duri n g th e h ea tin g ?
Wh a t is a s till h e a d o r fra c tion a ti on app ara tus ? S ee
“ — ”

Fig 4 Why us ed ?
. .

FI G 4
. .
 Expe rime n t No 3 .

Ab s ol ute Al c oh ol

Th e pres en ce of w a ter in alcoh ol may be S h own by sh aki n g

3 C O .wi th a v e ry li tt l e whi t e anh ydr o us c opp e r sulf a te in a dry

w ell—s topp e r e d No 1 te s t tub e A f te r h alf an hour n ote an y

.
-
.

ch an ge in th e coppe r sulf a te E xpl ai n . .

I n th e f oll owin g e xp e rim en t o rdi n ary 9 5 per c en t e th yl ,

a lc oh o l is d e hydr a t e d o v e r quick l im e ( Ca O) I t is th e n di s .

till e d fr om th e s emi solid r e sidu e a n d c oll e c te d u n d e r an hydrous

-

co n di tion s .

T o a 1 000 cc fl ask a tta ch th e n a rr ow e n d of a sl an ti n g

-
.

con d en s e r wi th bulb e d i n n e r tub e ( reflux c on d en s er) ( Com

“ ”
.

p are Fig . T h e e n d of th e tub e S h ould p a ss en tir ely through

th e c o rk s o t h a t th e c on d e n s e d liquid will drop fr e e wi t h ou t
t ouchi n g th e c ork This is a g en e ra l rul e always t o be f ollowe d
.

u n d e r simil a r c on di t on s I f t h e r e is a sm all h ol e n e a r th e e n d
'

Of y o ur c on d e n s e r s e e th a t i t is b e l ow th e s t opp e r (Wh a t is .

th e Obj e c t Of this sm a ll h o l e ? ) A rr an g e th e a pp a ra tus S O th a t

th e fl a sk c an b e h ea t e d on th e s t e am b a th 1
P o ur 3 00 cc of -
. .

ordi n ary alcoh ol i n to th e fl a sk S l an t it an d a dd ab ou t 1 50 ,

gr ams of good quicklim e w e ll c r ush e d (I t S h ould n o t be ,

.

p owd ered ) Con n e c t an d h e a t f or an h our Duri n g this tim e th e

.
,
.

a lc oh ol will b oil g e n tly I f i t c on d e n s e s r apidly a n d th e liquid

.

ris e s in th e con d en s e r l owe r th e t emp e ra ture Of th e b a th sligh tl y

, ,

a n d if n e c e ss a ry p o ur w a t e r o v e r th e fl a sk Durin g th e h e a ti n g it .

is well to a t ta ch th e filled calcium chlorid e tub e m en ti on ed

b e low (Why ? )
.

1
If s t eam ba th is n ot han dy or in w orkin g order u s e a c on s tan t l evel w a ter
a -
,
-

ba th ( Fig . W h e n w orki n g w i th i n fl ammabl e liqui d s th e fl ame u n d e r t h e w a te r

ba th sh o ul d be e n c l o se d in a c h a mb e r surro un d e d by a w ire sc re e n in o th e r ,
“
w o rd s a sa fe t y w a te r bath sh o ul d be use d ”
-
.
,

26
 LABORAT OR Y E XP ERI MENT S 27

I f th e lcoh ol is allowe d to rem ain in con ta c t wi th th e lim e

a

f or tw o or thr ee d ays h e a ti n g f or on e h alf hour will be suffici e n t

,
-

b e fore th e absolu te a lcoh ol is dis tille d .

P r ep are a ca lcium chl orid e t ub e by fir s t i n s e r ti n g a l oos e

1

plug Of gl a ss wool Or cotton i n to th e bulb (n ot th e n arrow tub e)

an d th e n ahn os t filli n g t h e t ub e wi t h sm all lumps o f gr an ul a r

ca lcium chlorid e fr ee from dus t p ar ticl es an d coverin g this

, ,

Garvs TAN T LE VE L M44 T E R . BA TH

C R OS S S Ec r /ON

FI G 5
. .

an o th er p lug of gl a ss wool or cotton T o k eep th e con ten t s

.

in pl a ce an d als o to pr e v en t a n u n du e circul a t i on Of air i n s e r t

, ,

a cork c on t ai n in g a sh o r t pi e c e o f g l a ss t ubi n g op e n a t b o t h en ds .

I f th e app ar a t us is a ll ow e d t o s t a n d o ve r n igh t pl a c e th e c al ,

c iu m chl orid e t ub e in th e t op of t h e c on d e n s e r f a s tenin g th e

,

n arr ow e n d in a c o r k .

A ls o m ak e r e a dy a c on d e n s e r wi th s t r a igh t i n n e r t ub e dry ,

in sid e an d a b en t gl ass tub e f or con n e c ti n g th e fl a sk w i th th e

,

large r e n d of th e con d en s e r in the p osi ti on for dis till a tion .

Th e b en d o f th e tub e sh ould b e ju s t a bove th e cork s topp e r an d ,

th e tub e sh ould b e c u t Off jus t b e l ow th e s t opp e r ( Why ?

.
) F o r

th e r e ceive r atta ch a cl e an dry E rl en m e y er fil ter flask by m eans -

1
See Fig 3. .
28 LA BOR AT OR Y M A N UAL OF OR GA N I C CH E M I S T R Y
of a co r k to th e l owe r en d Of th e con d en s e r an d con n e c t its sid e
t ub e wi th t h e n a rr o w en d Of th e c a lcium chl o r id e tub e by me a n s
o f rubb e r tubi n g D O n o t cl o s e this t ub e wi th a s t opp e r duri n g
.

th e dis t ill a ti on (Why ? ) T h e r e c e ive r S h ould r e s t u pon th e

.

d e sk wh en th e app a ra tus is re a dy f or u s e .

B e n d in g G l as s T ubi n g H old th e dry tub e l e n g thwis e in

—

th e spr ea di n g e v en fl a m e of a w in g t op bur n e r d
I f th e wi n g
-
.

t op d oe s n o t giv e a n e v en fl am e it sh ould b e e xch an g e d o r

r ep ai r e d K e e p turn in g th e tub e u n til it is s o f t th en remove
.
,

it fr om t h e fl am e a n d b e n d to th e d e sir e d a n gl e T h e b e n d sh o uld .

be r ou n d a n d s t r on g n e v e r a n gul a r I f th e t ub e is thick o r l arg e

,
.

it mus t b e h ea t e d in th e sm oky fl am e A lw ays r ou n d th e

“
.

r ough e dg e s Of a ll gl a ss tub e s by h old in g th em in th e fl am e

u n til th e e dg e s h ave m e l te d This als o appli e s t o s tirri n g rods
.
-
.

A t t h e e n d o f th e h o ur c ool th e c on t e n t s Of th e fl a sk by all ow
in g a s t r e a m o f c o ld w a t e r t o p l a y u p on th e fla sk wh ich S h o u ld ,

b e r a is e d S ligh t ly in o rd e r th a t t h e w a s te w a t e r will ru n i n t o
th e b a t h Wh en th e alc oh o l c ea s e s t o b oil c onn e c t th e fla sk
.
,

a s o u t li n e d ab o v e f o r dis t ill a t i on an d dis till u n til n o m o r e dr ops

,

c om e ove r h e a tin g th e fl a sk on th e s t eam b a th Coll e c t th e

,
-
.

firs t 1 0 cc in a n op e n u n a tta ch e d t e s t tub e an d th e rem ai n d e r

.
,
-
,

in th e fil t e r flas k T e s t th e 1 0 cc p o r ti on a n d a p o r ti on Of th e
-
.
-
.

m ai n dis t ill a t e f or m ois tur e ( )

P T h e dis. t ill a t i on m a y b e

h as ten e d by cov e ri n g th e fl a sk an d b en t tub e wi th a t ow e l to

pre ven t r a di a tion S om e time s th e liquid bu mps furi ously
.
,

sin ce all th e air h as b e en driven ou t of th e lim e ( Comp a r e .

th e B oili n g p oi n t E xp e rim en t N o t e
- I n this c a s e c ool
,
.

t h or o ughly a dd a f e w pi e c e s Of p or ous til e th e n h ea t aga i n

, ,
.

K eep th e absolu te alcoh ol in a dry l ab el e d b o ttle I t will ,

.

b e n e e d e d f or l a t e r e xp e ri me n t s .

D O n ot emp t y t h e w a s t e lim e i n to th e si n k "

Q UE S T I O N S

1 .
Wh a t is f o rm e d in th e t e s t f or w a t e r in al c oh ol ?
2 . W h y is a bulb e d c on d e n s e r pre f er abl e to a s t r ai gh t con d en ser
for r e flux w o r k ?
 E x pe r i m e n t N O 4 .

T e s ts f or Car b on an d Hydr oge n i n Or gan ic Compoun d s

1 . E ff e c t of h ea t rg an ic subs ta n c e : a P l a ce a
a l on e on an o .

li ttle c an e suga r in a p orc el ai n e vap ora tin g dish an d h ea t gen tly

wi th a sm all blu e fl am e .

b R e p ea t th e ab ov e e xp e rim en t usi n g b en zoic a cid i n s t e a d

.
,

Of c an e sug a r B y usi n g a sm al l flam e a l l th e subs tan ce will

.

sublim e wi th ou t ch arri n g or l eavi n g a r e sidue (T h e fum e s

, .

produc e coughi n g wh en b r e a th e d ) .

2 . Ca rb on a n d H ydr og en c an be d e te c te d in org ani c com

p ou n ds by oxid a ti on :
I n a p o rc e l ai n e vapor a ti n g dish dry ab ou t 2 gr ams of cupric
Oxid e p owd e r by h e a ti n g t o dull r e dn e ss f or s e v e r a l mi n u t e s .

While it is co olin g h e a t a pi e ce of gl ass tubin g (6 mm ) ab ou t

, .

1 5 cm l on g in th e B u n s en fl am e a t a p oi n t 1 0 cm fr om th e en d
. .
,

a n d as i t s o f t e n s sl owly dr a w i t ou t an d s ea l i t I n tirn a te l y .

mix a very s mall am ou n t Of b en z oic a cid (fr om th e en d of a

k ni f e bl ad e) wi th h alf th e w arm cupric oxid e t ran sfe r this to ,

th e 1 0 cm s e al e d tub e a n d a d d th e r e m ai ni n g cupric oxid e

. .

T ap th e tu b e h oriz on ta lly on th e d e sk S O as t o m ake a

ch an n el ab ove th e mix ture an d cl amp it n ear th e op en en d
in a h o r iz on t al p o si ti on Con n e c t it w i th a s hort pi e ce o f
.

rubb e r tubi n g to an oth e r len g th of gl ass tubin g b en t a t righ t

a n gl e s an d l eadi n g jus t b e low th e surf a c e o f 3 cc o f cl e a r lim e .

w a te r c on ta in e d in a N O I te s t tub e N ow g en tly h ea t the

.
-
.

l ay e r of pure cupric oxid e an d th e n th e mix ture Wh a t e vid en ce .

is th e re of th e f orrri a tion of w a te r an d of carb on di oxid e ?

Q U E S T I ON S
Wh a t I s sublim a ti on ?
Why 18 th e gl a ss tub e n ot Se a l e d by s irn p
ly m e l tin g th e e dge s
her?
t oge t
Wh a t c aus e s th e r e dd ish br ow n co l o r in th e t ub e a f te r th e
-

h e a ti n g ?
H ow are c arb on an d hydr oge n d e te rmi n e d qu an ti tative ly ?
30
 Expe r i me n t No 5 .

FORMAT I ON OF A -
P AR AFF IN H YD R O CAR B ON BY R E D U C T I ON OF
A H A L OGE N D E R IV AT IV E
Me th an e fr om Chl orof orm an d Ch e mi c al P r ope rti e s of th e
P ar af fin Hydr oc ar b on s

Fa s ten a 1 2 5 c c E rlen m e ye r fl a sk uprigh t wi th a clamp

.
,

an d pl a c e in t o i t 1 0 gr ai n s o f zi n c dus t an d 1 5 cc o f a lc o h o l
1
.

an d 1 0 cc Of w a t e r . I n s e r t a b e n t gl a ss t ub e t hr ough a w e ll
.

b ore d t igh t fit tin g c ork an d con n e c t wi th a sh or t tub e l eadin g

-

t o a b ea k e r or sm a ll p a il of wa t e r a rr an ge d so t h a t th e gas th a t
is form e d may be c olle c te d by displ a cem en t N ow add to th e .

fl ask 5 cc of chloroform an d 2 cc of a m ola r s olu ti on Of c op

.
1
.
3 5

p e r sulf a t e T h e r e a c.t i on will s oo n b e gi n spo n t a n e ously I t .

may e ve n b e n e ce ss a ry to m od e rat e it by c oolin g th e fl a sk wi th

s om e wa te r Co lle c t t w o t e s t t ub e s of th e gas disc ardi n g th e
.
-
,

firs t on e an d th en in a ddi ti on fil l tw o glass s topp e re d b ottle s

,
2 -

of th e cap a ci t y of th e te s t tub e s -
.

a I gni t e th e ga s in t h e t e s t t ub e
.
(Wrap th e te s t tub e -
.
-

in a t ow e l b e f o re d oin g S O b e c aus e if th e m e th an e c on ta i ns
,

air an e xpl o si on migh t r e sul t of s u fli c ien t vi o l e n c e t o sh a tte r

th e t ub e ) .I mm e di a t e ly a f t e r th e ga s is burn e d a dd 2 cc of .

lim e wa te r s topp e r a n d sh ake Wh a t caus e s th e turbidi ty of

,
.

th e s olu t i on? Why do e s th e gas m ad e by this me th od b u rn

wi th a gre en fl ame ? I s thi s ch ara c te ris tic of pure m e th an e ?
b To a b o tt l e o f th e gas a dd 2 cc of br omin e wa te r an d
. .

sh ake = I s the re an y ch an ge in co l or ? E xpla in

. .

T o 5 cc Of b en zi n e ben zol e n e n o t b en z e n e s ee N ot e 1 )
”
c
. .
, ,

add 1 cc of a s o lu t i on o f 5 gr ams o f br omin e in 1 00 gra ms Of

.

1
regard in g w eigh i n g ou t c h emi c a ls p 3
S e e N ot e , . .

2
On e e xt ra in c a s c a s ec on d tri a l of o n e o f th e t e s t s is r e q uire d
'

, .

31
 LA BORAT OR Y M A NUAL OF OR G A NI C CH EM I S T R Y

c arb on te tra chlorid e D ivid e i n to tw o p o r t ion s s e t on e in th e

.
,

d a r k an d th e o th e r in di r e c t su n li gh t A f te r s e ve ra l min u te s .

c omp are th e m Wh a t h as h app e n e d in th e o n e e xp os e d t o s u n

.

ligh t ? B re a the a cross th e t op o f th e t ub e s Wh a t doe s the .

form a ti on Of a cl oud of vap or i n dica te ?

d S t abili t y o f pa r affin s t o wa rd r e a g e n t s
.

I Ad d s e v e r a l d r ops Of b e n zi n e t o 1 cc o f c on e sulfuric
. . .

a cid S h ak e I s t h e r e an y e vid e n c e o f ch e mica l a c t i on a pp a ren t

. .

by th e form a ti on Of he a t o r by d arke n in g? D oe s th e mix tur e

b e com e h om ogen e ous ? P our it slowly in to cold w a te r cool .

fur the r if n e ce ssa ry s t ir an d th en p our it i n to a s mall (NO I )

, , .

t e s t t ub e
-
I s a h om o g e n e ous s o l u t i on Ob ta i n e d ?
.

2 R ep e a t usi n g f u mi n g sulf uric a cid

.
,
B e c a r e ful wh e n .

p ou r in g th e s olu ti on in to w a ter D O s o drop by drop P our . .

up on ic e if p o ssibl e ( P) .

3 R e
. p ea t usi n g c o n c n i tric a cid
, ( P) . .

4 T o
. I cc o f a ve r y dilu
. t e s o lu ti o n O f po ta ssium pe rm an
g a n a t e ( jus t r o s e c o l o r ) a d d s e v e r a l dr o ps Of b e n zi n e S h a k e . .

( D o n o t u s e a c o rk s t o pp e r ) D O y o u n o t ic e a n y ch a n.g e ?
T h e ab ove g en e ra l r ea c t i on s wi th br omin e sulfuric a cid n i tric , ,

a cid a n d p e rm an g a n a t e a r e give n n o t o n ly f o r sh o wi n g th e
,

in er tn e ss of th e paraffin s bu t a ls o f or l ayi n g th e fou n d a ti on of a ,

g e n e r a l c o mp a ris o n o f t h e pr op e r t i e s O f o t h e r t yp e s o f hydr o

c arb on s as sh own by th e i r re a c t ion s t owa r d t he s e sam e re age n t s .

S Ee u n d e r e thyl e n e a ce tyl en e an d b e n z en e , ,
.

N OTE S

1 . T he b en i z ne used in the abov e s s is

te t a f rac ti on of p e t r o l e um
usually ta k b tw e 7 I t mus t
°
en d e e n t b 0 f o d d w i th
an no e c on un e

b e z e e C6 H 6 w h i c h boils a t
n n , ,
T h c mp u ds in p r b e i e e o o n u e nz n

w ill r a c t e ly y l w l y w i th fumi g sulfur ic c id a d th sulfo ic

on ver s o n a n e n

a c i d s f r me d a e o lik m t lf o ic ac ids s l bl e i w te r T he
r ,
e os su n , o u n a

or di n ary b e i s o m t i m s
nz ne C n t a i s i mp r i ti se p r b b ly
e u o n u e , o a
“
n

sa tur a t d hydr oc a rbo s f r m d i th e la rg sc a l d is till ti a d

e n o e n e- e a on , n

th e s sub s ta c e s a
e i
p y dnl a t t ac k d b y ve
re r aC o c sulfu r i c a i da d e e n n . c n

c h a rr e d Th s th i gs mu t b b r i mi d wh i te rp r e ti g
. e e n s e o ne n n en n n

th e r e sul t s i th is pa r tic ul a r ca s e
n .
 LA BOR AT OR Y E XP E R I M E NT S 33

S in c e b e zi n b o th p r o ou c ed the same c o
n e an d b e n z en e a re n n ,
n

fu i a to w h ic h is m a t Of t a r is s Th r f r it ha b w el l
s on s e n en e . e e o e s een

s gg s ted tha t th e t rm be l
u e whi c h c o rr spo ds t the
e n zo e n e ,
”
e n o

n igh b r i g f r a c t i ga s l e b u d i s te a d o f b i e “ ”
e o n on , o en ,
e se n en z n .

Op i g s al e d b ttl s
2 . en n W r ap a t o w l a r u d t h e b t tl e
e o e : e o n o ,

lea i g t h c k e p s d a d make a fil ma rk o th e ec k Th e
v n e ne x o e ,
n e n n . n

m l t t h e e d Of a s ti rr i g
e n d i t h fl a me a d i mm di a t ly t uch n ro n e n e e o

t h fil ma r k wi t h t h m l t e d gl a ss
e e G e r a lly th is c a us s t h gl a ss
e e . ne e e

t ub e t o c r a c k I f th i fails t h . d of t he c k may b e k oc k d Off

s e en ne n e

wi th a S ha rp bl ow Of th fil e I a y c ase the b o ttl e sh uld b h eld e . n n , o e

ove r a c a ss r o l o r b a ke r s o th a t if t h e b o t tl
e e e is ra c k d th c on e c e e

ten t s w ill d n o d amag T h fumi g a c ( I may b k p t f o a sh o r t

o e . e n e e r

t im f o lab o ra to ry u s i a s ma ll gl a ss — toppe r e d b t t l e
e r e n s o .

3 O p e
. n i g b r o m i b o t tnl e s T h e g l a ss s t
ne opp e r s i b r m i ne : n o

b o t tl s a e o f t e f r o
e r an d a d iffic ul t t r emove I f th e me th o d
n
“
ze n re o .

g iv e i
n t h g enr a l o t s ep 4 d
eno s o t p r o n ff c
e t iv e,
t h .c k ,
e n ve e e ,
e ne

o f t h e b o ttl e mus t b e b r oken Off Have r ea dy a fu e l la rge ough . nn en

t o h ol d th e e ti r e b o ttl supp r ted i a s ta d a d a o th e r b t tl e

n e, o n n ,
n n o

u d r ath r ady to r ec iv th e b r mi e al l e t n ea r the d r af t pipe

n e ne e e e o n ,
s .

M ke a fil e ma rk a r ou d th e c k wr ap th b ttl all o r wi th a
a n ne ,
e o e ve

tow l a d w h il e it is s c u r e ly h l d i a
e ,
n up r igh t p osi tio s t r ik th
e e n n n e e

t p a sh a rp bl w wi th th fil o
o osmall h amme r Ca r efully r mo e e r a . e ve

to w el p r o t c t t h h a d w i th a t ow l o gl ov
'

th e ,
e e an d p ou
n th e e r e, r

c te ts i t th fu l B su r that y u h ld th b ottle i uc h a
on n n o e n ne . e e o o e n s

w ay t h a t t h b r omi e w ill ot
e dow o y u r fin g r s a d h ol d
n n ru n n n o e ,
n

th e n t i r e b t tl e ve r th fu
e o el i o r d e r th a t n on e will
o e u ou t si de
nn n r n

S ee p 6 f o t r e a tmen t of b r omi n e bu r n s
. r .

Q U E S T I ONS
Wh a t is th e purp os e of th e c opp e r sulf a te s olu ti on ?
W hy is a lco h o l a dd e d t o th e mix tur e Of zin c dus t e tc ,

W hy is th e firs t t e s t tub e o f th e ga s disca rd e d ? -

W hy is c a r b on t e t r a chl o r id e us e d as a s olve n t f or b r omi n e

in t h e s e t e s t s i n s t e a d o f w a t e r ? (N o ye s a n d M ullik e n ,

Cl a ss R ea c t i on s a n d I d e n t ific a t i on o f Org a ni c S u b
“

s tan ce s 3 d E d ,
”
.

Wh a t is th e Obj e c t of p ouri n g th e mix ture of be n zo l en e an d

c o n e H zS O i n t o w a t e r ?
.
( C omp a r e pr
4 o p e r t i e s o f sulf o ni c
a cids ) W hy is a s mal l N O I t e s t t ub e us e d ? “ -
”
. .
, ,

6 . Ar e th e pa ra ffin s e ve r a c t e d upo n by H 28 04 o r H N Og ?
34 LA BORA T ORY M A NUAL OF OR GA N I C CH E M I S T R Y
G iv e tw o othe r gen e ral m e th od s (applic abl e to th e e n ti r e
p araffin s e ri e s) Of fo rmin g e th an e
.

Why mus t a cork s topp e r n o t be us e d wh en m aki n g the

p e rm an gan ate te s t ?
Wh at is th e m ain con s ti tu en t of th e b en z ol en e us e d ? Could
it be Ob t a i n e d pure by f r ac tion aLd is til l a tio n ?
Why d oe s th e gas as prep are d in this exp e rim en t burn wi th
a gr een fl am e ?
 Expe ri me n t N o 6 .

OR MA TI ON OF AN A L KY L HA L I D E BY TH E R E P L A CE ME N T
OF A N A L C OH OL I C H YD R OX YL GR OU P W I TH H A L OGE N

P r e par ati on of E th yl I odid e f rom E th l Al c oh l y o

To grams of red phosphorus an d 1 0 cc of abs olu te e thyl
2 .

a lc o h o l in a gl a ss s t opp e r e d b o tt l e a dd in sm a ll qu an t i ti e s 1 7
-

grams Of p owd e re d i odin e S h ak e an d c ool if n e ce ss ary af te r

.

e a ch a ddi t i on by imm e rsi on in w a t e r S topp e r th e bo t tle an d .

s e t i t a sid e for t w en t y f our h ours or l on g e r -

Th en tran sf e r .

th e r e a c ti on mix tur e t o a sm a ll rou n d b o t t om e d fl a sk ri n s e ou t

- -
,

th e b o t t l e w i th 2 3 cc of absolu te a lc oh o l an d a d d th e ri n si n gs
— .

to th e m a in solu t io n H ea t u n d e r a r eflux c on d ens e r on th e

.

s team b ath f or fif te en mi n u te s Th en cool an d dry th e ou t

-
.

side of the fl ask conn e c t wi th a s tr aigh t Wa te r con d en se r by

,

m ean s of a b en t gl a ss tub e an d dis t ill wi th care (wi th ou t usin g

1
,

a th e rmom e te r) u n t il n o m o r e liquid p a ss e s o v e r T h e mix tur e .

will bump som ewh a t an d this c an m ore or l e ss be avoid e d by

e fl a m e in m o t i on P u t th e dis till a t e in to a S quibb s
’
.

fun n e l add s om e w a ter an d t e s t wi th li tmus ( P)

2
,
.

dilu te s olu ti on Of s odi um hydroxid e s topp e r s e cure ly

3
,

an d a gi t a t e g e n t ly in th e foll owi n g m an n e r : I n v e r t th e fu nn e l ,

holdin g th e s topp e r in wi th on e h an d an d pl a cin g th e thumb

1
Use small flame E xc e ssive h ea t may dec omp ose th e phosphorou s ac id
a .

l formed in th e rea c t i on givi n g p h osph i n e

,
.

“
1
Fig 6
2
. Wh en in u s e th e s top c oc k sh ould be grea s ed wi th a good s top
.
-

c oc k lubri c a n t Vase li n e may be used bu t it is n ot rec ommen ded s in c e i t is t oo

.
, ,

thin a n d h as n o b od y Be sure t o c l ea n th e s e p a ra to ry fu n n e l be fore l ea vin g

“ ” “ ”
.

th e labora t ory s o th a t th e s topp e r a n d th e s t op c oc k w ill n o t s t i c k

,
I t is w e ll
- .

to kee p th e gr ou n d p a r t s s e p a ra t e d bu t t i ed w i th a pi ec e of t w i n e T h e s ep a ra tory .

funn el is c on ven i en tly suppor ted in a ri ng w hi c h is c lamp ed to a s tan d .

3
Col d d ilu te s odi um h ydroxi de s olu t i on c aus e s n o a pprec i a bl e h yd rolys is
un der th e s e c on d i tion s .
36 LA BOR AT OR Y M A N UAL OF OR GA N I C CH E M I S T R Y
o f th e h e r h an d on th e h an dl e Of th e s top co ck an d th e firs t
ot -

t w o fi n ge rs on th e o th e r sid e o f th e s t e m a n d s h ak e ,
. Whi l e
i t is Still i n v e r t e d op en th e s t op c o ck t o r e l e a s e th e pr e ssur e
-
.

( P) R e p e a t b o t h t h e s e o p e r a t i o n s s e v e r a l t im e s. Tur n t h e

fu nn e l righ t sid e up supp o r t it in a rin g an d a s s oon as th e

,

mix ture h as s ep ar a t e d in to l aye rs rem ove th e Upp e r s topp e r

1
, ,

( Why ? ) a n d t h en a ll o w t h e h e a vy l o w e r l a y e r O f e thyl i o did e

t o flow i n t o a cl e a n b e ak e r cu tt i n g Off th e s t r e a m wh e n th e upp e r

,

S E PA RA TI ON FUNNE L S E PA m roR Yf Z/NNE L

”M m”
(
GLOBE S HA P E )
FI G 6
. .

l y r fl ws through th e s top co ck T h e e thyl i o did e is usu a lly

a e o
-
-
.

t urbid on a cc ou n t Of th e pr e s e n c e o f w a te r I f th e bro wn c o l o r
.

( P) h as n o t b e en r e m ove d a n d if th e a qu e ous l ay er is n o t al k a lin e ,

t r e a t i t wi t h a s e c on d p o r ti on o f s o dium hydr o xid e s o lu ti on .

1
A lk a li n e s olu ti on s ome t ime s f o m d iffic u l tl y s e p arabl e emulsi on s I f th e
; r .

se p ara ti on is n o t c omple te w i th i n a n h o ur an d if it is i n c on ven i en t t o l e t it s ta n d

o v e r ni gh t ,a d d dilu t e ac i d u n t il th e mixt ure jus t r eac t s ac i d. T h is pro c e d ure
w i ll usu a lly b reak up a n o rd i n a ry e mulsi o n .
 LA BORA T OR Y M ANUAL OF OR G ANI C CH E M I S T R Y

Wh at is th e corre c ted b oili n g p oin t ? Calcul ate the th e o -

re tic al yi e ld on t h e b a sis o f th e a lc o h ol us e d a ls o Of th e i odi n e , ,

an d comp a r e wi th th e a c tu al r e sul t s W h a t is th e p e rc en ta ge .

yi e ld on e a ch b a sis ? T h e produc t b e come s d ark on s ta n din g ,

e sp e ci a lly in th e pr e s en c e o f li gh t A gl obul e of m e rcury pl a c e d .

in th e b ot tl e will k eep th e sp e cim en c ol orl e ss (Why ?) .

B o ttl e th e pr oduc t l ab e l a s di r e c te d in th e N o te s p , ,
.

a n d pl a c e in t h e pr op e r t r a y f or i n sp e c ti on by t h e i n s t ruc t or .

B e f ore h an din g in th e pr ep ar a ti on pe rf orm th e f o ll ow in g

e xp e r im en ts :

a Te s t th e a c ti on of silve r n i tra te s olu tion on a drop

.

e t hyl i odid e I s th e r e an imm e di a te pr e cipi ta te ? R ep e a t wi th

.

chl orofo rm .

b Diss o lve 1 gr a m of p o ta ssium hydr o xid e in 1 0 cc o f

. .

a lc o h o l U s e th e KOH m a rk e d purifie d by alc ohol TO

“ 1 ”
. .

1 cc o f this s olu t i on which is comm onl y kn own as alcoh olic “

.
,

p o ta sh a dd n i tri c a cid u n t il the s olu tion re a c t s a cid an d th e n

, ,

a dd dis till e d w a te r t o diss o lve an y pr e cipi ta t e T o t his .

s olu ti on a dd a drop of silve r n i tra te s olu ti on I s th e re an y .

pre cipi ta te or is th e s olu tion t urbid? (Why ? )

c B oil 1 cc of a lc o h o lic p ota sh c on ta in in g on e drop (n o
. .

m ore) Of e thyl i odid e for on e min u te Cool an d .

n i t ric a cid diss olvi n g an y pre cipi ta te

,
wi th di
I f an e mulsi on is f o rm e d a dd a lc oh ol or r ep e a t , ,

a m o u n t Of t h e h a lid e Th e n a dd a drop of silve r n i tra t e S O

.

I s th e r e an imm e di a t e pr e cipi t a te ? H ow d o y ou a cc oun t

fr Re e en c e f or th e p r ep r i
a a t o n Of a lkyl i did s o e in l a rge q u a t i tni e s ,

Ada ms a nd Voo r hee s ,

J ou r n . A mer Chem S oc
. . .
,
41 8 —8
7 9 9 .

Q U E S T I ONS
1 . Could y e ll ow ph o sph o rus b e us e d in pr ep a r in g e thyl i odid e ?
( S ee r e f e r e n c e t o A d a ms a n d Vo o r h e e S p ,
.

2 . Why is a gl a ss s topp e r e d b ot t le us e d ?
-

1
I i th is is
va ila bl e d issolve s ome ord in a ry s t i c k p ota ssiu m or
n ot a ,

h ydrox i d e in a b s o lu t e a l c oh ol a n d fil t e r fro m a n y c h l ori d e or c a rb on a t e .

a s olu t io n o f m e ta l l i c s o d iu m in a l c oh o l I n t h e l a tt e r c a s e o n ly c l e a n
.

s od iu m sh o ul d b e use d th e p a rin gs be in g re t urn e d t o th e bo ttl e

,
.
 LABOR A T OR Y E X PE RIM E NT S 39

Why is abs ol u te alco h ol us e d ?

W hy is th e r e a c t i on mix tur e s e t a sid e ove rn igh t ?
W hy is th e b o t t l e rin s e d wi th a s mal l a m ou n t of alc oh ol ?
A cc o u n t f or th e f orm a ti on of th e hydr oge n i odid e which is
e vid e n c e d by th e cl o ud Of v a p o r wh en th e r e a c t i on
mix ture is tran sf e r re d .

Why is a th e rm om e te r n o t us e d in th e firs t dis t illation ?

W h en is f u s ed c a lcium chlo r id e us e d f or d r yin g liquids ?
W h a t c a us e s th e brown colo r H ow is i t r em ove d ?
W ri te th e r e a c ti on s .

How d oes th e m e rcury k e e p th e sp e ci men c o l o r l e ss ?

G ive tw o o th e r m e th ods f or f o rmin g e t hyl i odid e .

W hy c an n o t e thyl i odi d e b e p r e p a r e d by th e dire c t a c ti on of

i odin e on e th an e ?
Comp a r e th e pr e p a r a t i on o f e t hyl i odid e a n d o f hydr oge n
i odid e .

Why is the h alogen in alkyl h alid e s n o t gen e ra lly pre c ipi

t a t e d wi t h silv e r n i t r a t e s olu t i on ?
Wh a t is th e qu ali ta tive t e s t f or h alid e ion in a qu e ous s olu
-

t i on ?
Wh a t is the brown pre cipi ta te form e d wh en n ot e n ough
n i t ric a cid h a s b e e n a dd e d t o m a k e t h e s o lu t i on r e a c t a cid ?

Wh a t w ould h app e n in (c ) if a qu e ous p o ta sh we re us e d ?

Try it .

W h a t is a ge n e ra l m e th o d o f d e te c ti n g th e h a l ogen s in organ ic
comp ou n ds ? Can th e s odium d e c omp osi ti on be us e d if
-

l n it ro en is ls o pr s e n ? m p r xp N
g a e t C o a e E . t O
. 28 .

W h a t impuri ti e s d oe s th e o r di n a ry p o t a ssium hydroxid e

A cidify a dilu t e s o lu ti on o f p o t a ssium hydr oxid e
'

l
c on t ain ?

Wi th n i tric a cid an d a d d silve r n i tr a te s o lu ti on .

H ow a r e th e h a l oge n s d e te rmin e d qu an ti ta t iv e ly ?
What is alkyl ati on ?
 x
E per im e n t NO 7.

F ORMA T I ON OF A N OL E F I N E H YD R OCARB ON

A ND

ADD I T I ON OF A H A L OG E N To A N OL E F INE H YD R OCA RB ON

P r e par a ti on of y
E th l e n e (E th e n e ) an d y
E th l e n e D ibromi d e
D ib
- r om -
e th a n e )

I n this xp e rim en t e thyle n e is pre p a re d by heati n g e thyl

e

a lc o h o l a n d ph o sph o ric a cid an d th e e t hyl e n e thus m ad e is

,

purifie d by p a ss age through con c sulfuric a cid an d th en ru n .

i n to br omin e which abs orbs it wi th th e fo rm a tion Of e thyl en e

,

dibr omid e Af te r the e thyl en e dibr omid e I S m ad e th e gas

.
,

i t s elf is coll e c te d an d s tudie d .

S e t up th e a pp a r a tus sh own in Fig 7 U s e rubb e r s topp e rs

. . .

Ca r e mus t b e e x e rcis e d in pu tt in g th e gl a ss t ub e s t hrou gh

th e rubb e r s t opp e rs B e sur e t o r ou n d th e e dge s o f al l t ub e s
.

in th e fl am e .
(S e e p U s e a dr op o f w a t e r or Of glyc e ri n e
.

a s a lubric an t Alw ays t ak e h o ld o f th e t ub e n ea r th e s topp e r

.

a n d t w is t i t sl owly as it is c a r e fully b e in g f o rc e d in N eve r .

,

f or e x ampl e gr a sp a l on g th e rm om e t e r a t on e e n d t o push th e
,

o th e r en d t hr o ugh t h e s t opp e r W i th th e s e p r e c au ti on s a cci

.

den ts re sul tin g in m o r e or l e ss s e ri ous cu t s w ould be avoid e d .

A S a rul e i t is n o t n e c e ss a ry t o e n l a rg e th e h o l e in a rubb e r
s toppe r I n ca s e a l arge r hol e is re quire d a cork b or e r c an be
.

use d I t mus t be m ois ten e d fre qu en tly an d on ly ve ry S li gh t

.
,

pre ssure is n ee d e d o the rwise a tap e ri n g hol e will be m ad e

,
.

T h e c on n e c t i on s wi th rubb e r t ubin g are ea s ily m a d e if y ou

breath e through th e rubb e r tubi n g b e fore pushin g it ove r th e
gla ss H e re aga in th e sh arp e dge s Of th e glass tub e sh ould b e
.

wel l r oun d e d in the fl ame .

 LA BORAT OR Y E X P ERI M ENT S 41

Fit a 2 50 r ou n d b o ttom e d Sh o r t n e ck e d fl a sk wi th
-
,
-

t hr e e h ol e d s t opp e r t hr o ugh which p a ss a th e r m om e t e r a b en t

-
,

t ub e wi th th e b en d n e a r th e s t opp e r
, a n d a n i n l e t t ub e ,
1

i n to a n a rrow tub e — 2 mm ,
in di a m e t e r wi t h th e .
,

e n d b e n t upw a rds a b o u t 5 mm T h e S iz e Of this tub e.

imp or tan t I f it is l a r ge r or sm alle r th an d e sign a te d it will

.

t d e li v e r t h e a lc oh o l pr op e rly T h e t ap e ri n g sh ould b egi n

.

D/dg / a m 0f 5 4pp fl f /U5

‘
‘ ‘

FI G .
7 .

ju s t s topp e r a n d th e tub e sh ould e x ten d alm os t to th e

bel ow th e
b ot tom Of th e fl a sk s o th a t th e a lcoh ol c an be d e live r e d we ll
,
’

b e low th e surfa c e o f the liquid Tu r n th e b e n d a wa y fr om th e

.

th e rm om e te r .

1
T he ppa ra tus shoul d be s o a rran ged tha t the a l c oh ol w h i c h c on den se s bel ow
a

th e firs t b e n d in t h e o u t l e t t u be w ill n o t d rip upo n t h e l o w e r p a r t o f t h e the r

mome t e r a n d c a us e it t o c ra c k I n Ord er t o a v o i d bac k flo w of an y c o n den sa t i on
.

liqui d sl an t th e o u tle t t u be a s sh o w n .
42 LABORATORY M ANUAL OF OR G ANI C CH EM I ST RY

To m ake th e i n le t tub e hea t e ven ly a pie ce of gl a s

,

h e ld len g thwi s e in th e flam e Of a burn e r pr ovid e d wi th

t op r o ta t in g i t an d m ovi n g it fr om l e f t t o righ t u n t il it
,

ve ry s of t th en remove it from th e fl am e an d slowly a t fir

,

t h en much mor e r apidly dr aw it ou t a s d e sir e d V e ry .

drawin g m ake s th e t ub e too n arr ow I t mus t b e m ad e .

h ea tin g A sm oky fl am e n ee d n o t be us e d as l on g a s th
.

is sl owly w a rm e d in th e blu e fl am e T h e n arrow tub e is .

broken wh e re a fil e m ark is m ad e I t is b e n t by s of ten i n g

.

tub e n ea r th e en d in th e fl am e an d quickly t o uchi n g th e e n d

h a rd surf a ce wh en it will b e n d v e ry re adi ly D O n ot fuse .

c apill a ry or ch an ge it s b o r e .

Conn e c t a dr oppi n g fu n n e l (Fig 6 ) wi th rubb e r t ubin g t o

-
.

upp e r p ar t of th e in l e t tub e ab ove th e s topp e r a n d w i ,

t i on s 1
. L ead th e gas ( I ) th r o ugh a n e mp ty 2
b o ttle as a s afe ty b o ttle usin g a three h ol e d
,
-

tub e s in thi s s t opp e r sh o uld b e c u t

I n s e r t a gl a ss s t op —c o ck an d a tta ch a pi e ce Of rubb e r
l e a d a way th e ga se s to th e draf t pip e From t his bo ttl .

g as t hr o ugh a l o n g hi gh gl a ss t ub e i n t o ( )
2 a 2 c m .

wi th sid e n e ck w h e ,

c on c sulfuric a cid This t e s t tub e sh ould be p r o vid e d wi th

. .
-

op en s a f e t y t ub e 3 0 cm l on g which S h o uld b e dr a w n ou t a n d b
.

sligh tly upwards a t th e b ottom op en i n g u n d e r th e surfa ce of

,

liquid T h e l on g high c on n e c tion is us e d in o rd e r th at

.

o p e r a t o r may b e a bl e t o s ee t h e c on c sulfuric a cid r i si n g i n

.

o f b a ck pr e ssur e in t h e a pp a r a t us a n d h a v e t im e t o pr

b e in g d r awn in to th e firs t b ot tl e by e qu alizin g th e

by op en in g th e s top c ock m om en ta r ily Th en (3 )
-
.

a n o th e r t e s t t ub e wi t h sid e n e ck c on ta i n i n g 7 cc o f b r
-
.

1 is rubber c on n e c t i on mus t be w ire d sin c e th e ru bb e r ab s orb s

Th al

s w e lls S O mu c h th a t t h e j oi n t bec ome s l oos e

2
N o t bromi n e w a t e r D O n o t a dd t h e bromi n e u n t il jus t b
.

men t is begu n I f t h e b romi n e is a ll o w e d t o s t a n d in t h e t u be

.

b e f ore th e e x pe rime n t is be gun i t a tta c ks th e ru bbe r s to pp e r

a re f o rme d w h i c h ru n d o w n t h e w a lls in t o t h e bro mi n e S in .
 LA BORA T OR Y E X P E R I M E NT S 43

with 1 0 cc Of w a te r T h e tw o tub e s l ea di n g th e gas

. .

sulfuric a cid a n d i n to th e bromin e sh ould be drawn

sm a ll op en i n g s o th a t the issuin g bubble s will be sm all .

ould ope n n ear the bottom of th e t e s t tub e s T h e -

.

be a rr an ge d an d supp or te d on
ttl e an d th e tw o t e s t t ub e s in -

5 full of cold w a t e r Fin ally (4) through a tub e op eni n g

.

ove th e surf a c e o f a n o rm a l s o dium hydr o xid e s o lu ti on c on

tain e d in a bo tt l e provid e d wi t h a v en t Or th e br omi n e v ap ors

.

may be a ds orb e d by p a ssin g th e gas t hrough a ca lcium chl orid e

t ub e fill e d wi t h a ds o rb e n t ch arco al I n e i th e r c as e l e a d th e g a s e s
.

fin a lly i n to th e dr a f t pip e .

I n to th e g en e r a t in g fl a sk pu t a mix tur e Of 40 cc of syru py .

phosph oric a cid (s p gr . .a n d 2 0 cc Of a lc oh ol A lm o s t fil l

. .

th e m a in bulb of th e dr oppi n g fu nn e l wi th a lc oh ol a n d in
-
,

ord e r t o displ a c e th e air in t h e t ub e a llow s om e of th e a lc oh o l

t o flow i n t o th e fl a sk H e a t th e fl a sk o ve r a wir e g a uz e u n til th e

.

th e rm om e t e r in th e mix tur e i n dic a te s On ly a sm a ll

fl ame is n e ce ss ary a f te r th e fl a sk is h e ate d through Duri n g .

th e pr e limi n a ry h ea t i n g h a v e th e s t op c o ck op e n Wh en th e ev o
-
.

l u tion o f e thyl e n e h a s w e ll b e gu n cl o s e th e s top c o ck a n d l e t -

,

owly a t such a r a t e (a b o u t o n e dr op a s e c on d )

will give a goo d c on s tan t s t r e am Of gas K e ep th e t e mp e ra .

’

re b e tw ee n 2 3 0 Dr a f t s cool th e fl ask an d c aus e such

— 2
°

b a ck pre ssure th a t th e sulfuric a cid a n d bromin e may be

dr awn i n to th e pre c e din g b ot tle s This b a ck flow may r e a dily
.

be av oid e d by op e n i n g th e s top c o ck a s m en ti on e d a b o ve
-
,
.

T h e liquid in th e fl a sk sh ould app ea r a s if fill e d wi th bubbl e s

an d will f o a m a s th e e t hyl e n e is r e gul a rly ge n e r a t e d T h e tem .

p e r a t u r e m ay ris e e v en a bov e 2 5 0 b u t sh o uld

°
n o t b e a ll o w e d t o

reach Con t in u e th e p a ss ag e Of th e ga s u n t il th e br o mi n e
h a s ch an g e d c ompl e te ly t o a s tr aw c olor e d liqui d -
This wil l .

th e h ood . If y ou ge t a n y on y o ur h a n d s w a sh it 011 i mme d i a te ly i

w th a c oh o l l ,

an d th en ru b in s ome c a rr o n Oil ( h a lf li n s e e d Oil a n d h a lf l ime w a t e r ) or c a rb o l a t e d

va s e lin e B en zen e an d ga solin e a re good so lven t s a n d may also be us ed f or remov
.

in gbromi n e S ee p 6
. . .

For open i n g br omine bottl es c ompa re No t e 3 un d er M eth an e p 3 3

, , , . .
 44 L ABOR A T OR Y M A N UAL OF OR G AN I C CH E M I S T R Y
ta k e ab ou t thir t y min u te s M uch more t im e will b e n e ce ss a ry .

if th e gas is n o t d e live r e d n e a r t h e b o t t om wh e re it will s tir

up th e b r omin e a n d be m o r e re adily a bs orb e d P urify it a ccord .

in g t o th e dir e c t i on s giv en b e low .

NOTE S ON T H E G E N E RAT ION OF E T HYLE N E

1 . Be s u re to Op e n th e s top c c k b f
-
o e o e r u r n i g ou t the flame
t n .

2 . T h e ge n e r a t io n of t h e gas may b e s t opped a d r esumed n

an y t i me .

3 c a.rryi Wh en n g ou t th is ex pe r imen t it is well to p r o te c t

e y s wi th goggl s
e e .

4 . DO bu rn th e ga s l eavi g the appa ra tus u l ess

n ot t ry t o n n

e n d of t h d li e ry tub e is d r awn i t o a c a pill ry p e i g

e e v n a o n n .

5 T h .m e t h d c a b e
e us e d f o p r e p a
o r i g f i rnly l a r g r n a e

Of thyl
e H w ve r th e ph o sph r ic a c id a tt c ks th e
en e . o e ,
o a

af t e r a b u t 6 h u r s r u i g t h i l t t ub is ge e r a lly
o 1
—2
0 o nn n e n e e n

Off a n d fi n a lly t h e fl a sk i t s e lf w ill l ak e .

A f t e r th e
c ol or Of th e br omi n e h as dis app ear e d discon n e c t
s e c on d t e s t tub e c on n e c t th e ou tl e t tub e of th e sulfu r ic a cid
-
,

wi th a tub e l e adi n g to a b e ak e r or small p ail of w at e r ,

t e s t t ub e o f th e gas c oll e c t e d o v e r w a t e r
-

25 0 cc n arr ow n e ck e d gl a ss s topp er e d b o ttl e s an d a 2 5 0 cc

.
-
,
-

o r difia ry wid e m o u t h e d b o t t l e wi t h t h e gas by displ a c e m e n t

-
.

a I n t o on e n a r r ow n e ck e d b o tt l e p our cc Of br omi n e w a te r
.
-
1 .

I n s e r t th e gl a ss s t opp e r imm e di a t e ly a n d sh ak e .

b T O t h e s e c on d n a r r o w n e ck e d b o t tl e a dd 1 cc Of a v
.
-
.

dilu t e s olu tion of p o tassium p e rm an gan a t e Cl os e wi th .

1

gl a ss s topp e r a n d sh ak e vigor ously .

c I g n i t e th e ga s in t h e wid e m ou t h e d b o t t l e (n e a r th e
.
-

pip e) an d imm e di a te ly a dd w at e r t o displ a c e th e gas I s .

fl am e dis t i n c tly lu mi n o us ? 0

R e p e a t th e ab o v e e xp e r im e n t s usi n g ci ty ga s Con clusion s . .

1
For t h e ox i da t i on o f e th yle n e ,
s ee S t o d d a rd Int rodu c ti on t o Orga n i c Ch
is t r y ,
”
p . 156 ; of o th e r Ol e fin e s , s ee M oo e r , Ou t li n e s Of Orga n
2n d E d .
, p
. 12
9 .
46 LA BOR A T OR Y M ANUAL OF OR GANI C CH E M I S TR Y

cul ate th e t h eor e tic al yi eld f rom th e am ou n t of bromi n e use d .

Wh a t is you r c or r e c t e d Obs e r v e d b o ili n g p oi n t ? -

R e p ea t t e s t s a a n d c a s giv e n u n d e r e t h yl i o did e (p wi th .

pur e e t hyl en e dibr omid e a n d c omp ar e th e r e sul t s wi th t h os e Ob

,

t ain ed wi t h e t hyl i o did e Wri t e th e e qu a t i on s

. .

NOTE ON T A K I N G AP A R T THE APPAR AT U S

l ss tub es Of ten stic k in th r ubbe r stopp r s I suc h ca se s

T he g a e e . n

d o n ot t y t pull o t t h e tub di r c tly W r k th r ubb r a w ay f r om

r o u e e . o e e

th e tub wi th th fi g r s a d a ll ow w a t r t fl w i a d m is t e i t
e e n e n e o o n n o n

a f a s t a s it is s pa r a t d
s e I n t h is ma
e . r th e tub e soon b e come s f r e e
nne

an d c an b e wi th d r awn a sily e .

Q U E S T I ON S
1 . Wh a t obj e c ti on is t h e re t o an i n le t t ub e wi th a di am e te r
le ss th an 2 mm ? G r e a te r th an 2 mm ?
. .

2 . Why mus t th e a lcoh ol be d e live re d b e l ow th e surf a ce of th e

liquid ? Why is th e in l e t tub e turn e d up a t th e b ot tom ?
W h a t subs t an ce s a re c a u gh t in th e e mp t y s af e t y b o tt le ?
A cco u n t f o r th e m I s t his th e onl y purp o s e o f t hi s
.

b o t tl e ?
Why mus t th e ga s be p ass e d throu gh c on c H S O4 ? Could
'

.
z

fumin g H 8 04 be us e d ? dilu te H S O ?
2 z 4

Why sh ould th e alcoh ol vap ors n o t b e a llowe d to go ove r

i n to th e bromin e ?
Why are th e b o ttle s surrou n d e d wi th c old w a te r ?
W hy is th e bromi n e c ove re d wi th a l a y e r Of w a te r ?
W h a t subs ta n c e s a re c a u gh t in th e s o dium hyd r o xid e s o lu
t i on ? A cc o u n t f or th e m .

Why is th e app a r a tus discon n e c te d b e fore ex tin guishin g th e

fl am e ?
Wh a t is th e brown p r e cipi ta te fo rm e d in th e p e rm an gan ate
te st ?
Wh a t u n s a tu r a t e d hyd r ocarb on s a re in th e ci t y gas ? Wh at
a re illumi n an t s ? N a me s om e .

H ow a r e th e u n s a t u r a t e d hyd r o c a r b on s in ill u min a t in g gas

e s tim a t e d ?

I S an a ddi t i on o r subs t i t u t i on pr o duc t form e d wi th amyl en e

an d sulfu r ic a c id ?
 LABORA TORY E XP E RI MENT S 47

I n th e purifica ti on of e thyle n e dibromid e why mus t the

s odium hydroxid e s olu ti on b e use d ?
W hy a vo id th e e mulsi on which w ould be f orm e d by V igo rous
sh aki n g ?
Why is a 2 50 cc S quibb s s ep a ra tory fu n n e l us e d i n s tea d of a
.
’

droppi n g fun n e l a l th ough th e volum e Of liquid is sma ll ?

-

( g
F i. 6 ,
p .

Why n o t dry the p roduct in a sm all dis tillin g fl a sk an d

dis t i ll dire c tly w ith ou t remov in g th e ca lcium chlo r id e ?
Why is gla ss w ool us e d in s tea d of a fil te r p ap e r in the
fu n n el ?
W h a t c omp ou n ds a re in th e a myl en e P
L ook up th e fo rmul a f or pi n e n e .

Why n o t u s e th e we igh t Of th e a lcoh o l i n s te a d Of th e bro

min e in calcula ti n g th e th e o r e tica l yi e ld ?
I s e thyl en e dibro mid e a s a t ura t e d o r u n s a t ur a te d c omp ou n d ?
Of wh a t hydr o c a rb on is it a d e riva t ive ?
Wh a t h app e n s wh en e thylen e dibr omid e is h e a t e d wi th alco
h olic s odi um hydroxid e ? Vi th aqu eous s odium hydroxid e ?
’
-

W h a t o t h e r m e th o ds c an b e us e d f or pre p a ri n g e thyl e n e ?
H ow did th e U ni t e d S t a t e s G ov e rn m e n t pr e p a r e e t hyl e n e in
la rge qu an ti ti e s f or th e m an ufa c ture Of mus tard ga s ”

( d i c hl o r di-
e t hyl s u l fid e ) duri
-
n g t h e w a r ? (R e f D o rs e y.

J ou rn I nd
. . an d E n g Chem , 11
. . 2 88 .
 Exp e rim e n t No . 8

F OR M A T I ON OF A N OL E FI N E HYD R OCA R B ON

E th yl e n e f r om E th yl Al c oh ol (f or S h o rt C o ur s e)

We igh dire c tly in to a l a r ge t e s t tub e (NO 4 gr a ms Of

-
.

ph o sph orus p e n toxid e Con n e c t th e te s t tub e by m e an s Of a

.
-

cl ose ly fi ttin g co r k wi th a refl ux a ir con d en s e r ; imm e rs e th e tub e

in c old w a t e r an d p our 5 cc o f e t hyl a lc oh o l sl owly t h r ou gh th e
,
.

con d en s e r T h e a lcoh ol sh ould be a dd e d c au t iously in sm a ll

.

p or ti on s an d th e t e s t tub e sh ake n u n d e r wa te r sin ce much h e a t

-
,

is e volve d wh en a lcohol com e s in con ta c t wi th ph osph orus

p en toxid e R em ove th e c on d en s e r supp or t th e te s t tub e a t an
.
,
-

a n gl e Of ab ou t 4 5 wi th th e d e sk t op by m ean s Of a clamp an d
°

con n e c t it wi th a d e live ry tub e a rran ge d to co ll e c t gas ove r

w a ter H ea t th e tub e ca r e fully u n til th e mix ture b e com e s
.

h om ogen eous ; th en m ore s tron gly u n til a s teady s tr eam Of gas

is e volve d Fill tw o 2 5 0 cc n arrow n e ck e d glass s topp er ed
. .
- -

b o ttle s an d a 2 5 0 cc wide m ou th e d b ot tle wi th th e gas ove r

.
-

w a te r by displa c em en t .

a . I n to on e n a r ro w n e ck e d b o tt l e p our 1 cc o f br o min e wa te r
-
. .

I n s e r t th e gl a ss s t opp e r imm e di a t e ly a n d sh ak e .

b T o th e s e c on d n a rr ow ne ck e d b o tt l e a d d 1 cc of a v e ry
.
-
.

dilu te s olu ti on of p o tassium p e rm an gan at e Clos e wi th th e .

gl ass s topp e r an d sh ak e vig o r ously

‘

c
. I gni t e th e gas in th e wid e m ou th e d b o ttl e (n e ar th e dra f t
-

pip e) an d imm e di a tely a dd wa te r t o di spla c e th e ga s I s th e .

fl am e dis tin c tly lumin ous ?

R ep ea t th e a b ove e xp e rim en t s usi n g ci t y ga s C on clusi on s
,
. .

Te s t amyl en e or pin en e f or th e d oubl e b on d as foll ows

Use 1 cc in e a ch ca s e
. .

a . A dd 1 dr op o f c on e sulfuric a cid .
( C a r e "
) R e sul t?.

48
 L A BOR A T OR Y E XP E R I M E NT S 49

b Add
. drop of c on e n i t r ic a cid (Ca r e "
1 .
) R e sul t
. ?
6 A d d a s o lu t i on o f br o mi n e in c a rb on t e t r a chl o rid e
. .

d A dd
. cc o f p o tassium p e r m an gan ate s olu ti on as ab ove
1 .

a n d sh ak e (D o n o.t u s e a c o r k s t opp e r ) .

Comp a re th e r e sul t s wi th th o s e Ob tai n e d wi t h b e n zin e ,

E xp t N O . p 31 . . .

Q UE S T I ON S
1. Comp a r e th e a c t i on o f e t hyl a lc o h o l wi t h t h a t of w a t e r on
ph o sph orus p en t oxid e Wr i t e s t r uc tu r a l f o rmul a s of th e
.

c omp ou n ds in e a ch c a s e a n d n ame th em .

2 W h a t is t h e a c t i on o f h ea t on t h e c omp o u n ds f o rm e d by t h e
.

a c t i o n o f e t h yl a lc o h o l a n d O f w a t e r r e sp e c tive ly on
, ,

ph osph orus p en toxid e ?

°
9
Wr i te th e e qu a t i on f o r th e r e a c t i on o f br omi n e an d e thyl en e .

2
{ W h a t h a pp e n s wh en e t hyl e n e is t r e a t e d wi t h dilu t e p o t a ssium
p e r ma n gan a te ?
5 W
. h a t is t h e br o w n ish p r e cipi t a t e f o rm e d i n t h e p e rm an

g a n a t e t e s t ?
6 D e fin e a n a ddi t i o n pr o duc t ; a subs t i t u t i on pr o duc t
. I llus
.

t r a te .

7 . Is hyl en e dibromid e a s a tura te d o r an u n s a tu r a te d c om

et

p oun d ? Of wh a t hyd r o c a r b on is it a d e r iv a t ive ?

8 . I s an a ddi t i on o r subs t i t u t i on pr o duc t f o r m e d wi t h a myl en e
a n d sulfu r ic a cid ?

9 . W h a t u n s a t u r a t e d hydro ca r b on s a r e in th e ci t y ga s ?
10 . W h a t a re illumi n an t s N a m e s om e .

11 . How a r e th e u n s a t ur a te d hydr o c a r b on s in illumi n a t in g gas

e s t im a t e d ?
 E xp e rime n t N o . 9

F ORMA T I ON OF AN A CE T YLE N E 1 . B Y H YD R OLY S I S OF AN

A C E T Y L ID E

Ac e ty len e f r om Cal c ium Car b i d e

Set up a gas ge n e ra to r c on sis tin g Of a fil terin g flas k an d -

droppi n g fun n e l I n t o th e dry fl a sk pl a ce s eve ra l lumps of

-
.
1

ca lciu m carbid e an d a llow w a te r t o dr op ve ry slowly up on it .

( C a r e "
) P a ss t h e g a s t hr o ugh an e mp t y s a f e t y b o t t l e a n d t h e n -

fil l wi th th e gas by displ a c e m e n t o v e r w a t e r a t e s t tub e tw o

.
-
,

n a rr o w n e ck e d gl a ss s t opp e r e d b o tt l e s
- -
a n d a wid e mou th e d ,
-

bo ttle in the ord e r n am e d .

a .I gni t e th e gas in t h e wid e m ou th e d b o tt l e h oldi n g it n ea r

-
,

th e dr a f t pip e N o tic e th e lumi n o si ty Of th e fl am e an d th e

.

a m ou n t Of c a rb on d e p osi t e d .

b T o on e n a rr ow n e ck e d b o t tl e a dd 2 cc of br omi n e w a te r
.
-
.

a n d sh ak e . Comp ar e wi th m e th an e p 3 1 an d e thyl en e ,
.
, ,

p 44 o r p 4 8
. . .

c .T o th e o th e r n arrow n e ck e d b ot tl e add 1 cc : of a v e ry
-

dilu te s olu tion of p ota ssium p e rm an gan ate S h ak e Are th ere . .

a n y sig n s t o d en o te u n s a t ur a t i on ?

d Dilu t e
. cc of silve r n i tra te s olu ti on to ab ou t 3 cc
. .

From a te s t tub e a dd this silve r n i t ra te s olu ti on to a te s t tub e

- -

o f th e ga s Wh at is th e whi te pr e cipi ta t e ? Fil te r wi th suc ti on

.

a n d l e t it dry on fi l t e r p ap e r E xpl od e it by h ea ti n g sm a ll pi e c e s
.

in th e flame 2
N o te th e pr e s e n c e of c a rb on on th e kn if e bl a d e
.

a f t e r th e e xpl o si on .

e . P r ep ar e a s olu ti on of cupr ous chl orid e a s follows : Dis

s o lve 0 5 gr am Of c opp e r sulf a te crys t als in a li t t l e w a t ef p add
.

1
The pow der is gen erally usel e ss sin c e it is mos tl y dec omp os ed .

2
D e s t ro y all t h e r ema i n i n g silv e r pre c ipi ta t e s be f ore l ea vi n g th e l a bo ra t o
e i t h e r by e xpl o si on o r b y w a rmi n g w i th d ilu t e h y d roc h l ori c a c i d .

50
 LA BOR AT OR Y E XPE R I M E NT S 51

of con c amm oni um hydroxid e an d

. gr am of h y droxyL
in e h ydro chl orid e . D ilu t e wi th wa te r t o a b ou t 2 5 cc I t may
.

k ep t c ol orl e ss by pl a ci n g it in a tigh tly c orke d b o t tl e c on

som e Copp e r turn in gs T h e bo ttle should be full in o rde r

.

o xid a t i on by a n a ir pr e s en t This will b e us e d in b o th

y .

t his e xp e rim e n t .

a c e t yl e n e i n t o 5 cc
. Of th e cupr ous chl orid e solu t i on .

Wh at is th e r e ddish br own pre cipi ta t e ? Fil te r th e s o lu ti on

-
52 LA BOR AT OR Y M A N UA L OF OR GA N I C CH EM I S T R Y
wi th suc ti on an d w ash th e pre cipi ta te L e t it dry o n th e fil te r .

p a pe r a n d th e n e xplo d e sm a ll p or ti on s o f it in th e fl am e Try
,

i t s s o lubili t y in dilu t e hydr o chl oric a cid s o lu ti on .

Fil tr a ti on wi th S u c ti on I n o r d e r t o fil t e r wi th suc ti on fit th e
— .
,

p orce lain B uchn e r fun n el Fig 8 p 5 1 tigh tly in to th e n e ck o f a

,
.
,
.
,

fil te rin g fla s k wi th a g oo d c ork o r rubb e r s t opp e r a n d c on n e c t

-
,

th e o u t l e t t ub e t o th e fil t e r pump wi t h h eavy rubb e r t ubi n g .

I n th e b o t t o m Of th e fu n n e l pl a c e a fil t e r p ap e r c u t s o t h a t i t
cove rs all th e h ol e s an d li e s fla t w i thou t bein g fol ded on the s ides .

M ois ten th e p ap e r w i th s om e o f th e liquid us e d s tar t th e suc ti on , ,

an d t h e n p our in th e mix t ur e Of t en tim e s wi th bulky m a t e r i a l

.

it is c on v e n i en t t o pr e ss it d ow n wi th a fla t topp e d gl a ss s topp e r -
.

A t th e e n d Of th e fil t r a ti on c a r e fully disc on n e c t th e tub e fr om th e

fl ask bef ore s toppin g th e suc ti on .

F or th e fil t r a ti on of sm a ll qu an t i t i e s s e e p 5 6 ,
. .

2 . BY THE A C T I ON OF A L C OH O L IC P OT A S S I UM H YD R OX ID E ON

AN A L KY L E N E D IHA L ID E

Ac e tyl e n e fr om
yl e n e D ibr omi de E th

T O a 1 00 cc fl a sk s e t on th e s te a m b a th a tt a ch an a ddi ti on
.
-

tub e wi th r e flux c on d e n s e r c on n e c te d wi t h i ts sid e op e n i n g .

1

From th e t op o f th e con d e n s e r ru n a tub e leadin g in to 5 cc .

of th e a mm on i a c a l cupr ous chl o r id e s o lu ti on H a ve a l l c on .

n ec ti on s tight Go od c o rks w e ll b or e d mus t be us e d

.
,
Col ,
.

l odion s om e tim e s may b e us e d t o aid in m aki n g a c ork ga s

*

t igh t bu t it is n o t a subs t i tu t e f or an e v e n ly b or e d c o rk
,
R ubb e r .

s topp ers may als o be us e d if d e sire d Hea t 2 grams Of p ota ssium .

hydroxid e pu r ifie d by a lcoh ol in 1 2 cc of alcoh ol in th e fl a sk

,
2
,
”
.

f or ab ou t te n min u t e s Coo l a n d a d d t hr ough th e a ddi t i on

.

t ub e 2 cc Of e thyl e n e dibr omid e

. H ea t a g a i n Wh a t is th e. .

pre cipi ta te f orm e d in th e cuprous chl o rid e s olu ti on ? A t th e en d

Of t h e r e a c t i o n diss o lv e th e pr e cipi t a t e in th e fl a sk by a ddi n g
s ome dis tille d Wa te r add ni tric a cid to a sm a ll p or ti on o f this
,

1
S e e Fig 3 ,.p 13 . .

e quiv a l e n t a mo u n t o f me ta l l i c s o d iu m in a l c o h ol C on n e c t t h e
2
Or u s e a n .

c on d e n s e r t o t h e fl a sk a f t e r th e s o diu m is a dd e d si n c e t h e a l c o h o l ,
b e c o me s h o t
a n d h y d roge n is giv e n o ff .
 x r
E pe ime n t N o . 10

Al c oh ol s , R e a c ti on s of

a . Add a sm all pie ce of brigh t s odium to 2 cc of e thyl a lcoh ol

. .

Wh at gas is e volve d ? W h a t is th e whi te s olid th a t s ep a r a te s

a s th e s o lu t i on c ools ? A dd m or e s odium if n o thi n g s ep a r a te s th e
firs t tim e I s this rea c ti on ch ara c t e ris tic Of all a lcoh ols ? H ow
.

do you n am e th e comp ou n ds form e d ?

b Add a f ew dr ops o f c on e sulfuric a cid t o
. . cc Of gla cial .

a c e tic a cid an d 1 cc Of e t hyl a lc oh o l

. Wa rm w i th sh akin g
.
, .

P our it on a l arge c ov e r gl a ss an d n e u tr a liz e w i th s odium c ar

b on ate T o wh a t is th e pl ea s an t Od or du e ? T o wh a t cl ass Of
.

o rg ani c comp o un ds d oe s i t b e l o n g ? 4
R ep e a t usin g is o a myl a lc oh ol
,
-
( s alc oh ol usu ally pro
T. hi
duce s coughi n g wh e n bre a th e d ) .

c
. M ak e a dilu t e s olu ti on of s odium dichrom at e add a drop ,

o r tw o of c on c sulfuric a cid an d th en s e ve ra l drops of e thyl

.

a lc o h o l .He at N o t ic e t h e o d o r Of th e vap ors

. Wh at is .

form e d ? Wh a t ca use s th e gre en colora tion ?

'
 E xp e r im e n t N O . 11

T H E I D E N T IFICA T I ON OF A N A L C OH O L

The M e th yl E s te r of - D in i tr o b e n zoic A c d i

It is s e ld om p ossibl e to id e n tify organ ic subs tan c e s in th e s am e

gen e ra l m ann e r a s in org an ic subs ta n c e s Cl a ss re a c ti on s .
1

are r e li e d up on t o t e ll t h e n a t ur e Of t h e subs t an c e th a t is its , ,

cl ass such as a hydro carb on an a lcoh ol e tc an d physic al c on

, , ,
.
,

s t an ts will Of t en sh ow wh a t m e mb e r Of t h e cl a ss th e subs t a n c e is .

Th en in ord e r t o m ak e ce r tai n th e subs tan ce is tran sf orm e d in to

, ,

a d e riv a tiv e whi ch c an r e a dily b e pr e p a r e d on a sm a ll sc a l e a n d ,

a physic a l c o n s t an t t a k e n up on t his On a cc ou n t Of th e diffi .

c u l ties in purifyi n g liquids in sm a ll a m ou n t s a s o lid d e riv a t iv e

2
,

is ch os en wh e n e ve r p o ssibl e T h e fo ll owin g e xp e rim en t illus .

tr a t e s this p oi n t in th e c a s e of th e l ow e r a lc oh o ls .

I n a sm all dry t e s t t ub e h e a t t o ge th e r gram of 3 5 dini tro

-
.
-

b en z oic a cid an d gram of ph osph orus p en ta chl orid e ove r

a l ow fl a m e Ke ep th e t ub e in m o tion an d fin ally a llow th e
.

mix ture to b oil gen tly f or a mi n u te Then while it is s till .

liquid p our th e produc t up on a sm a ll dry w a t ch gl ass Wh en th e .

a cid chl o r id e h a s s o lidifi e d r e m o ve t h e liquid by pr o du c t -

,
_

phosphorus oxychl orid e a dh e rin g t o it by pre ssin g ou t th e , ,

1
N oye s an d M ull ik en , Cl a ss R ea c t i o n s
ific a t i on of Orga n i c S ub
an d I d en t
s tan c e s a n d Cl a rke A Han dbook o f Orga n i c An alysis For a more exten d ed
, ,
“
.
”

w ork s e e th e t h r ee m o n u me n ta l v o lu me s by M ullike n
, I d e n t ifi c a t i on o f P ure ,

Orga n i c Co mp o u n d s
”
.

2
For a me th o d o f d e termin i n g t h e bo ilin g po i n t o f a ve ry s ma ll a mo un t of -

l i qui d se e M ulli ke n Vol I p 2 2 2 ; a lso A l ex S mi t h a n d M en zi e s J ou r n A mer

, , .
,
. . . .

Chem S oc . .
,
32 89 7 .
56 L A BOR A T OR Y M A N UAL OF OR GA N I C CH E M I S T R Y
mix ture wi th a p orce l ain sp a tul a o n th e smo o th sid e o f a pie ce 1

o f cl e an p or o us t il e
2
.

P u t th e dry m a t e ri a l i n t o a n o t h e r sm a ll t e s t t ub e a dd -
,

e igh t dr ops o f m e t hyl a lc o h o l s topp e r th e tub e an d S h ake ,

n ow a n d t h e n T h e r e a c t i on is s oon co mpl e t e an d a f t e r a f e w
.

min u te s th e e s te r c an be re crys tallize d T O do this pl a ce th e .

,

produc t in to a 60 cc fl ask u n d e r a r eflux con d en s e r a dd 2 0 cc

.
, .

Of dilu t e a lc oh o l (3 v o lum e s Of a lc o h o l a n d I Of w a te r ) a n d h e a t ,

t o b oili n g by h e a t i n g on th e s t ea m b a th or by imm e rsin g th e fl a sk -

in h o t w a t e r I f th e subs ta n c e d oe s n o t c ompl e te ly diss olv e a f te r

.

a sh o r t tim e a dd a li tt l e m o r e dilu t e a lc oh o l a n d b o il a ga i n .

Th e re may be s om e fo re i gn p ar ticl e s whi ch will n ot gO in to s olu

t i on . Fil te r th e h o t s olu ti on thr ough a small fil te r p ap e r in to a
b e ak e r an d allow th e fil t r a te to c ool T h e e s te r c r ys ta lliz e s in .

S hi ni n g l ea fl e t s S e p a r a te th e s e by fil te ri n g wi t h suc ti on
. .

Filtr ati on of S mall Q u an ti ti e s wi th S u c ti on U s e a Goo ch .

p e rf o r a t e d p o rc e l a i n pl a t e i n a N O I fu n n e l a n d pl a c e up on .
,

th e pl a t e a pie c e Of fil te r p ap e r jus t l a r ge en o ugh t o c ov e r it

a n d e x t en d t o th e w a lls Of th e fu n n e l F a s ten th e fu n n e l in a .

s topp e r in th e n e ck Of a te s t tub e wi th sid e op en in g M ois ten .

th e fil t e r p ap e r wi th dilu t e a l c oh ol s t a r t th e suc ti on a n d pr o c e e d , . ,

a s usu a l (S ee Fig 8 p 5 2 an d comp a r e p

. .
,
.
,
.

A ll ow th e crys t a ls to dry b e tw e en fil te r p ap e rs o r u n d e r
a w a t ch gl a ss on a p o r o us til e an d t h e n d e t e rmin e t h e m e l t i n g ,

p oin t a ccordin g to th e dir e c ti on s give n in E xp t N O 1 2 p 5 8 . .

,
. .

T h e pur e subs ta n c e m e l t s a t 0 7
°
1

Oth e r e s te rs o f t his a cid may b e e mpl oy e d t o id en t ify th e

3

c orre sp on din g alcoh ols Th e y may be pr ep ar e d a cc ordin g to .

th e di r e c ti on s giv e n ab ov e f or th e m e thyl e s t e r T h e e thyl .

e s te r m e l t s a t 9 2 1 pr opyl e s te r
°
I n o rm a l bu tyl
°
-
,
°
- -

e s te r is o bu tyl e s te r 8 3
° °
,
1 - -
,

1
In o rdi n a ry c a s e s w h e re n o c o rro si ve su bs ta n c e is presen t a s t ee l spa tul a c a n
be used . I t s h o ul d b e c l e a n e d pr e vi o usly w i th s oa p t o re mov e t ra c e s Of ru s t a n d

3
2
Aporous u n gl a e d t il e is good f or o n e dryi n g u n l e ss on ly
z , a p o r ti o n of th e
surfa c e h a s bee n use d Obvi ously it c a n n ot be w a sh e d
. .

M ulli ke n I den tifi c a t i on of P ure Orga n i c Compo u n ds

“
3
, , Vol . I
—
1 68 7 2 .
 LA BOR A T OR Y E XP ER I M ENT S 57

Q U E S T I ON S
1 . W hy is th e s olid s 3 5 d
e in i
te rt r obofen .o ic
-
a cid m a d e
z f or

th e id e n tific a t i on Of a n a lc o h o l i n s t e a d Of t h e liquid e s te r ,

f o r e x ampl e Of a c e t ic a cid ?
,

Wri te th e e qu a ti on s f or th e re a c ti on s for pr ep ari n g th e m e thyl

e s te r ( Comp a r e S t odd a rd I n t r o duc ti on t o Or ga n ic
“
,
.

Ch e mis t ry 2 d E d ,
p 3 5 4 la s t p a ra gr aph an d
. .
, ,

p 99 N O 3 n e a r b o t tom Of th e p age p 1 4 N O 2 a n d
.
,
.
, ,
. 1 ,
.

p 6 NO
. 11 ,

3 . Wh a t is th e Obj e c t Of th e p orous t ile ? Why n o t u s e fil te r

‘

p ap e r ?
 E xpe r ime n t No . 12

D e te rm in a ti on of th e M e l tin g p in t
- o 1

m e l tin g p oin t is the physical prop e r ty mos t gen era lly

T he -

use d as a cri te ri on of th e puri ty of a s o lid o rg an ic c omp oun d .

I t a ls o s e rv e s f or th e ch a r a c te riz a ti on an d r e c o g n i ti on of a
comp oun d On a ccoun t Of its sign ifican ce th e m e l tin g poin t
.
-

sh ould be very care full y an d a ccurate ly d e te rmin e d T h e m e th od .

empl oye d is t o h e a t a sm all am ou n t Of th e subs t an c e in a c apill a ry

tub e a t t a ch e d t o a th e rm om e te r in a sui ta bl e b a th un ti l th e sub

s tan ce b e com e s a cl e ar liquid a n d th e temp e ra ture a t thi s p oint
2

is re cord e d a s th e m e l tin g p oin t A subs tan ce is r ega rd e d as -

.

pure wh en it m e l t s wi thin of a d e gr ee
3
provid e d th at the ,

t emp e r a ture is k e p t as n ea rly c on s tan t a s p ossibl e an d if a f te r ,

rep eated crys ta ll iz a ti on it d oe s n ot ch an g e S low m e l tin g .

ov e r s e v e r a l d e gr e e s usu a lly i n dic a t e s a n impur e c ompoun d ,

provid e d th e ra te of h ea tin g is all righ t S om e pure subs tan ce s .

,

h oweve r e sp e ci a lly th os e of high m ol e cul a r w e igh t do n ot S how

, ,

a sh a rp m e l t in g p oi n t in th e o rdi n ary m e th o d (comp ar e ph en yl

-

luc s z xp p
“

g o a on e E t 3 4
,
.
,
.

S e t up a m e l t i n g p o in t app ar a tus lik e th e on e illus tr a te d in

-

Fig 9 I t con sis t s of tw o tub e s on e in sid e th e oth e r T h e ou te r

. .
-
,
.

on e is 3 2 mm in di a m e t e r a n d ab ou t cm l on g ; 4
. .

on e is 1 7 mm in di a m e t e r a n d 1 4 cm l on g a n d h a s a
. .
,

1
S ee GA M
. . en ge ,
“
A S tu dy M of e li
p oi n t D e te rmin a ti on s U t n g- , .

La borator y B ul l etin 7 0 ,
f o r a n e xc e ll e n t d e s c rip t i on a n d d is c ussi o n o f
me thod s of de te rmi n i n g me l t i n g po in t s c ommon e rrors e tc N OTE : T h is bu ll
-
, , .

is ou t of pri n t bu t ma y be c on sul te d in th e ge n eral li bra ry

,
.

2
Fre qu e n t ly t h e t e mp e ra t ure of d ec o mp o si t i on (o f t e n c oin c i d e n t w i th
me l t i n g p o i n t ) is taken bu t in th is c a s e th er e is t h e p o ssi bili ty of a grea t er a mo un
-
,

of d iv e rge n c e d u e t o ma n ipul a t i o n .

3
T h is e rror is a bo u t e qu a l t o th e e rror Of Ob s e rva ti on .

4 Th
e o u t e r t ube of a B e c kma n n fr e e z in g p oin t a pp a ra t us is suitabl e
-
.

58
 LA BOR A T OR Y E XP ERI M E NT S 59

h ol e s 1
n ot ove r 2 mm in diam r four a t e a ch h e igh t
. e te
— - 4

ic a t e d in th e figur e I n o r d e r t h a t t h e b e h a vi o r o f th e sub
.

c an be wa t ch e d th e re a re n o h ole s opp osi te th e bulb of

FI G 9
. .

h e rm om e te r
t . T he in n e r tub e c an be supp or te d in the ou te r
of a co r k a s sh own wi th a n a rrow ch an n e l c u t
,

an i n n e r t u be a ll p e rf ora ted is n ot a t h an d the h ol e s c an be bl ow n in

,

S e l ec t a t e s t t ube o f th e pro p e r d ime n si on s s to pp e r it w i t h a goo d

-
,

c a rri e s a gl a ss t u b e to w h i c h is c o n n e c t e d a pi ec e o f ru bb e r t u b in g

He a t a t i n y a re a of th e gl ass at th e d esired po in t w i th a fin e blas t

 LABOR A T OR Y M A N UAL OF OR G AN I C CH EM I S T R Y
l g the e dge t o a ll ow th e h e ate d vap ors t o e scap e or wh en th e
a on , ,

th e rm o m e t e r is in p o si ti on a n d s e cur e ly h e ld in a lign m en t by a
.

co rk it c an be supp or te d by h oldin g th e top of th e th e rm om e te r

,
1

in a cl amp .

T h e o u t e r t ub e sh ould b e supp or t e d by cl ampi n g it firmly bu t

n o t t o o t i gh t ly u n d e r th e lip A d d en ou gh c on c sulfuric a cid
. .

t o c om e up t o a h e igh t Of 6 cm fr om th e b o t t om o f th e i n n er .

tub e wh en it is in pl a c e T h e app a r a t us is h e a t e d wi th a s mal l

2
.

fl am e which sh ould b e pro te c te d wi th a m e ta l chim n e y T h e .

liquid in th e i n n e r tub e is r e gul ar ly h e a t e d an d s tirr e d m ai n ly

by m e an s of con ve c ti on curre n t s m a d e p ossible by th e s eri e s of
sm all h ol e s T h e liquid n e ar th e th e rm om e te r a lways sh ows an
.

e v e n d ow n w a rd flow a ll a r ou n d th e s t e m
3
M o r e o v e r th e i n n e r .
,

liquid c an be h ea te d u ni formly an d s tea dily si n c e it is n ot affe c ted

by o rdi n a ry dr af t s .

M ak e s e ve r a l c apill ary tub e s th e S O c all e d m e l ti n g p oi n t ,

- -

t ub e s a s f o ll ows : H e a t even l y a pi e c e o f gl a ss t ubi n g h e ld

’

l e n g thwis e in th e blu e fl am e of a burn e r pro vid e d wi th a win g

4

t op r o t a t i n g i t a n d m o vi n g i t fr o m l e f t t o righ t u n til it s of te n s
, ,

t h e n r emove i t f r o m th e fl a m e a n d dr a w i t ou t v e ry sl owly a t firs t

an d then a s th e gl a ss b e gi n s t o co o l a n d h a rd e n
,
much m ore ,

rapidly i n to a lon g s traigh t thin w all e d n arr ow tub e of ab ou t

, , ,
-
,

fl a me a n d w h en it mel t s rem
,
o v e i t from t h e fl a me a n d b l o w a b u bb l e n o t a h ol e , .

R e p ea t t h is a t e v e ry p o i n t T h e n c ompl e t e th e ma ki n g o f t h e h ol e s by me l t i n g
.

ea c h li tt l e b u bb l e or by b r e a ki n g t h e gl a ss w i t h a fil e a n d rou n d i n g t h e edge s “

of eac h h ol e w i th t h e fl ame R e me mbe r th a t t h e h ol e s s h o ul d b e n o t mo re t h a n

.

abo u t 2 mm in d i a me t e r . .

An a pp a ra t us like t h e on e d e s c ribe d a bov e b u t w i th o u t th e h ol e s in th e i n n e r

t u b e h a s bee n in u s e f o r ma n y y e a rs in d i ff e re n t l ab ora to ri e s I t is b e li ev ed h ow .
,

e v e r t h a t t h e perf orated i n n e r t u b e is n e w a n d is an a d va n t a ge si n c e it p e rmi t s

,

g oo d s t ir ri n g a n d mo r e r a pi d h ea t i n g a n d c o oli n g .

I f a l on g sc a l e 3 6 0 th e rmo me te r is us e d t h is c o rk s h o ul d h a v e a l on gi tud i n a l
°
1 -
,

s e c t ion c u t o u t t o form a c an al t h rough w h i c h t h e d egre e s of th e t h ermome ter

c a n ea sily b e r ea d a t t h is i n t e rv a l .

2
I f more a c i d is us e d t h e me l ti n g p oi n t t ub e is l ike ly t o d ro p Off in th e liqui d
-
,

sin c e t oo small a l e n gth o f it is h e l d by c a pill a ry a ttra c t i on .

3
T h e c urre n t s in t h e liqui d c a n be s e e n v e ry n i c ely if a li ttl e fi n ely d ivi de d
c a rb on is pu t in t h e a c i d .

4
A smoky flame n eed n ot be used provi ded th e tube is slow ly w armed in the
bl u e flame .
62 LA BOR A T OR Y M A N UAL OF OR GANI C
‘

CH E M I S T R Y
e n d of ub e dr op gen tly upo n th e d e sk R ep ea t un til a laye r
th e t .
1

3 mm d ee
. p is f o rm e d R u b Off t h e subs t an c e a dh e rin g t o th e
.

o u t sid e Of th e t ub e s o th a t i t will n o t b e ch a rr e d by th e a cid a n d

discol or th e b a th R em ove th e th e rm om e te r from th e app a r atus

.
,

a ll ow m o s t o f th e a cid t o d r a in Off a n d t o uch th e bulb t o th e

.

upp e r p ar t of th e m e l ti n g poin t t ub e thus le avi n g b e hin d a -

,

drople t of th e liquid P l a ce th e t ub e wi th .

a g ai n s t th e th e rm om e t e r s t e m a n d i t will

a tt r a c ti on T h e subs t an c e sh ould b e opp

.

t h e rm om e t e r R e tu r n th e th e rm om e t e r w i
.
,

t o th e app a r a tus T h e m e l ti n g p oi n t t ub e s h o
.
-

a s f a r a l on g th e th e rm om e t e r a b ov e th e liquid a s it d oe s in th e

liquid in ord e r th a t th e capill ary f orc e will be gr ea t en ough to

h old it to th e th e rm om e te r N ow b e gin t o h e a t th e liquid .

wi th a sm a ll flame T h e h ea ti n g may be f airly rapid un til

2
.

wi thin ab ou t 1 5 of th e m el ti n g p oin t (a lre ady kn own or approxi

°
-

m a te ly d e te rmi n e d in a p r e limi n a ry t ri al) an d th en s l owl y ,

a min u t e u n til th e subs tan ce m e l ts D o n ot gu es s a t the

°
3 ,
.

r a te ti me i t an d t h e n y ou will Ob t ai n c on sis t en t r e sul t s

, ,
S ub .

s tan ce s g en e ra lly s of ten an d con tr a c t an d Of ten b e com e di s ,

c ol o r e d b e fo r e m e l t in g .

I t is a bs o lu te ly e ss en ti al t o u s e a s mal l fla me an d h ea t ,

e sp e ci a lly wh en wi thi n m l i g poi ° °

r egu l arl y ,
0 1
5 O f th e e t n n t 1
— -
.

A l t e r n a t e h ea t i n g wi th a l a rg e fl am e n e v e r giv e s c on sis ten t r e sul t s .

T h e sm a ll fl am e c an e a sily b e o b t a i n e d if t h e a ir supply Of th e
burn e r is pr op e rly c u t d own Draf ts sh ould of cours e be avoid e d .

a s much as p o ssibl e .

T h e t emp e ra tur e of th e b a th c a n be c a rri e d up to ab ou t

2 80
°
if pure con c sulfuric a cid is us ed I f wa te r h as b een
. .

a bs orb e d th e dilu t e d a cid will b e gi n t o b o il a t a l ow e r t e mp e r a

1
sub stan c e doe s n o t dro p read ily t o t h e bo ttom of th e t ube t ry e i th e r
I f th e
Of th e f oll o w i n g me t h o d s : H o l d a pi e c e Of o rd i n a ry gl a ss t u b i n g a bo u t 6 0 c m , .

l on g o p en a t bo th en d s in a n uprigh t po si t i on on t h e d e sk a n d t ou c h i n g t h e d e sk
, ,

t op th e n l e t t h e me l t in g p o i n t t u b e w i t h s e a l e d e n d d o w n d ro p t hr o u gh i t
,
-
, R epea t , .

t h is s e v e ra l t ime s if n ec e ss a ry Or d ra w t h e fla t si d e o f a t ri a n gul a r fil e h o ri
.
,

z o n t a ll y a c r o ss t h e t u b e a li tt l e b e l o w t h e su b s t a n c e T h e p o w d e r l oo s en e d by .
,

th e vi bra t i on s e t up int h e gl a ss w ill qui c kly sli de d o w n t o t h e bo t t om

, .

2
I f th e burn e r is h e l d in th e ha n d h ol d i t in a n Obliqu e po si t ion in o rde r 0 a v o i d
,

ac c i den t in u a s e th e a p a ra t u s c ra c ks
p .
 LA BOR AT OR Y E X PE RI MENTS 63

e r a tu re s b egin s
. I f it
T h e b oili n g p o i n t of -

in cr ea s e d by boilin g it in a fl a sk or b e ak e r u n d e r

s d e te rmin ation are gen e ra lly du e to th e vari

thi
rmome te r r a t e o f h e a ti n g physical con di ti on
1
, ,

of th e c omp o u n d 2
an d
,
in di vidu al m an ipula ti on For an .

e x t e n d e d discussi on o f t h e s e e rr o rs th e s tud en t is r e f e rr e d to th e

bulle ti n m en ti on e d in th e f oot n ote ab ove T h e t ru e m e l ti n g

-
.

p oin t is ob tain e d by th e u s e of sh or t s t em n orm al s tan d ardiz e d -

, ,

t h e rm om e t e rs wh o s e m e rcury t hr e a d is e n t ir e ly imm e rs e d in
t h e b a th . S i n c e t h e s e are exp e n sive an d a r e n o t a lw ays av ail
a bl e ,
th e s e t Of t h r e e sh or t sc a l e t h e rm om e t e rs m en ti on e d in
-

con n e c ti on wi th th e B oili n g p o i n t e xpe rim e n t p 8 a n d F ig 1

-
,
. .
,

E xp e ri en c e in d e te rmi ni n g th e m e l ti n g poin t an d ch e cks on -

a ccur a cy Of t h e t h e rm om e t e r c an b e Ob ta i n e d by usi n g
“

s ta n ce s wh os e m e l tin g p oi n ts a re n ea r th e b ottom an d s om e
-

t n ea r th e t op o f th e sc al e in e a ch ca s e as m en ti on e d in ,

fi rs t exp e r im e n t T h e foll owi n g subs tan ce s are sui tabl e

. .

te mp e r a tur e s giv en a r e c or rec ted :

N aph tha l e n e
B e n z o ic cid
a

S a licylic a cid .

An isic a cid .

An t h r a c en e
Ca rb az ol
An thr a qui n on e

All th e s e subs tan c e s in addi ti on t o givin g go od m e l tin g

p oi n t s h av e a sp e ci a l a dvan ta ge in th a t th e y are e a sily Ob ta in e d
1
P robably more e rrors a re ma de in man ipul a t i on by i mpro pe r h ea t in g tha n in
a n y o the r w ay . T h e ra t e o f h ea t in g mus t n o t b e s o r a pi d t h a t a n a ppre c i ab l e ris e
o f t e mp e ra t ure oc c urs d uri n g t h e t ime n ec e ssa ry f o r t h e a t t ai n men t Of t h e sa me

t e mpe ra t ure t h rou gh ou t th e e n t ire ma ss Oth e rw ise t h e t e mpe ra t ure may ris e
.

sev era l d egre e s d uri n g the i n te rv a l be tw ee n i n c ipien t a n d c ompl e te mel t in g .

2
Co mp a re prec e d in g f oo t n o t e a n d f o ot n o t e
-
,
p 61 - 2
, . .
64 LA BORA T OR Y MANUAL OF OR GA NI C CH E M I S T RY
an d are r eadily purifie d by sublim ati on I t is s e ld om n e c e s s a .
1

t o u se a subs t a n c e m e l ti n g b e l ow n a ph th a l en e I f n ec ess a .

on e o f th e f o ll owi n g c an b e us e d : p t o luidi n e
— hy droc in ,

n ami e n aph thyl a mi n e o r diph e n yl ami n e

a -
, ,

Comp ar e th e r e sul t s wi th t h o s e Ob ta i n e d wi th th e s am e
th e rm o m e t e rs in th e b oi l i n g p oi n t e xp e rim e n t -
.

I f th e s e t Of thr ee th e rm om e te rs m e n ti on e d ab o v e is n o t a t
h an d an ordi n ary lon g sca le th e rm om e te r may be s tan d ardiz e d
,
-

f or th e c on di ti on s Ob tai n i n g in th e l ab or a t ory w o rk by d e t e rmin

in g th e m e l ti n g p oi n t s Of s om e o f th e pur e subs ta n c e s giv e n in
-

th e lis t f or e x ampl e n aph th a l e n e s a licylic a cid an t hr a c e n e an d

, , , ,

c arbaz ol Th en by plo tt in g th e re sul t s on c o ordin a te p ap e r a s

.
-
,

d e scrib e d in n o te 4 B oilin g p oin t expe rim en t p 2 0 the c or

,
-
,
.
,

r e c tion for an y on e d e gre e may quickly be r e ad Off a t an y time .

T h e in flu en c e o f ch an g e s in a tm o sph e ric pr e ssur e on the

m e l ti n g p oin t is n e gligible
-
.

T h e a bbr e vi a t i on c or is pl a ce d a f te r a corre c te d m e l tin g .

po in t I t i s to be n ote d th at ahn os t al l th e m e l t in g p oin ts given

.
-

in th e li te r a t ur e a n d th e t e x t b ooks a r e u n fo r tu n a te ly u n
c orr e c te d M e l tin g p oi n t s d e te rmin e d u n d e r u n corre c te d c on
.
2 -

d ition s c a n n o t a lw a ys b e duplic a t e d by o th e r w o rk e rs This .

is e sp e ci ally t ru e o f m e l tin g p oin t s ab ove ab ou t -

N OT E S

1 . Thi lT he e e mel tin g poin t

appa r a tus is sh own in Fig 0 It -
. 1 .

us s a small am u t f ac id a d c a b h a t d a d c l d qui kly

e o n O n n e e e n oo e c .

T h e fl a me is pl ac d u d e r th b d f th sid l o p a d th e li q id
e n e en o e e o ,
n u

is stirr e d by mea f o c ti u rr ts T h e hot u rr t h w

ns o c nve on c en . c en , o

eve r usu a lly g

,
s d w th side ea r the l op a d the r mai d r
oe o n e n o ,
n e n e

Of t h e li qui d is h ea t d ma i ly by c duc ta c eT h t mp r a tu r n on n e . e e e e

o f th e sul fu r i ac i d ba th c a b c rr i e d up t o abou t
c Th n n e a 2 e

th li qui d b e gi s t
e b il d bubbl s m tim s f r m r apidly a d
n o o ,
an es o e e o n

exe r t suc h p r ssu r i th arr ow sid lo p tha t th e tube may be

e e n e n e o

c r a cke d Ve ry good r sul t s c a be Obtai ed wi th th is appa ra tus

. e n n

1
F simpl m th d f sublim t i
or a e A th r qui
e o E pt 65 p
o a on , s e e n a n on e , x .
, . 2 10 .

2
T h e d a t a g e n in t h iv is book a re n o t a l l c orrec te d sin c e th ey c a nn ot a l w ays
“
,
”

be f u o n d in t h e te a t e li r ur an d v ery pure ma t eri al h as n o t been a va ilable .

 LA BOR AT OR Y E XP E R I M E NT S 65

th e h e a t i ng is p r p r ly
o e ca rr ie d ou t . It is quic kly a ff e c te d by

D isc olor a tion of th e sulfur ic ac id on ac c o u nt of c h a rr i ng of

Me/f /iy 1 0/hf

0

fl pp ur c l f c / S
FI G . 10 .

c matte r may b e p r ev t en ed to limi t d x t t by th e a ddition

a e e en

small amou ts of p n o ta ssium i tr a t s dium pe r ulfat

n e, o s e,

b e t r ea te d wi th co c n i t r ic aci d an d
"

n .
66 L A BOR AT OR Y M A N UAL OF O R G A N I C CH E M I S T R Y
boil d i e n a fl a sk or be ake r u n de r t h e h ood u til
n th e fum s e Of n i t ric
oxides a re n o l o n ge r ev o v ed l .

3 . A m i c ro -
b ur ne r is c o ve ie n n nt to use f or d e t e r m i n a t on i su n de r

4 . Wa te r c an a d va n ta geo usly be used f or d e t e r m i in g l ow

n mel t
in g poi ts
-
n .

5 A .s killful Op e r a t o r c a n a t t a c h s ev e r a l d iff r t m l tin g p o in t e en e -

tub e s t th e s a me th e r mom t r a d ma ke al l d t r mi a t io s by on e
o e e n e e n n

c n ti u us h e a ti g of th
o n o ba th n e .

6 Fo t e mpe r a tur e s b tw M ll ike r commen ds ° l

. r 0 a d e een 2 2 n u n e

a ba th p r ep ar e d by ca u t i ously b oili g t oge th e r f or 5 to mi ute s n 10 n ,

u de r a hood a mixtur e Of 7 pa r t s by weigh t of c o e sulfur ic ac id

n ,
0 n .

a d 3 0 pa r t s Of n eu t r a l p o ta ssium sul fa t e
n a d s t i rr i g u t il th e ,
n n n

sulfate is c omple tely diss lved ; or by imila r t r ea tm t of a mi tu r e o S en x

o f 5 5 pa r t s by we igh t Of th ac i d wi th 4 5 pa r t s Of a c id po ta ssium e

su lfa te Th e mix tu r e ha th e c o sist c y f glyc r ol doe s n ot fume

. s n en o e ,

ba dly a d is l ess c rr osive an d l e ss a sily d isc l o r e d by t r a c e s Of

,
n o e o

o rga ic ma t t er th a n sul fu r i c a ci d
n B y i c r ea si g th e p r por tion f . n n o O

ne ut ral sul fate f r om 3 0 to 40 per c e t this b a th may b e us d f n e or

t e mpe ra tu r e s up t o Th is mi tur e h weve r is s oli d a t th e x ,

o ,

o r di a ry tempe r a tur e
n .

t empe r a tu r e s b e twe fus zi c c l r i °

F or 3 7 a d e d en h o de 0 n n ,

f r e from dust may be mpl yed

e ,
e o .

Th s tude t is r f e rr e d t th e r ef r e c e ci te d f or th e me th od of
e n e o e n

h a dli g th e s e mix tu r e s
n n .

7 C e r
. ta in subs t a c e s w h i c h d e c o m p o s en a t h i gh t m p e r a t u r e s e

g ivi n g o ff w a t e r va p o r c a r b o n d i o i d e o a mm o
, i a g iv e b e t t r m e l txi g ,
r n ,
e n

p i ts wh en h ea ted in m l ti g p i t tub s seal d a t b th en ds

o n e n -
o n e e o .

C mpl e te da ta a s t o si e f tub e qua ti ty us d e tc a e ec ssa ry

o z o ,
n e ,
.
,
r n e

for c ompa r is on b e caus e th e y w ill va ry ma y d gr e e s w i th a c h a ge

,
n e n

i co di ti o s o a c c u t of th e diff e r ce s in th e gas p r e ssu r e s of

n n n n o n en

th e d c ompo si tio p r d uc t s
e n o .

S imila r ly sub s ta c e s w h ic h r ea dil y sublime a e s ome t ime s h ea te d

n r

in me l tin g p oi t tub s sea l e d a t b o th e d s

-
n e n .

8 I t is n o t a lw ays p ossibl e t o d e te rmi e th e mel tin g po in t a

. n -

second time o th same sampl p r ev iously mel t d i th tub e si c e

n e e e n e ,
n

i man y ca se s th e sub s ta c d e c ompo se s I t sh oul d a lso b me ti o d

n n e . e n ne

t h a t i s om ca s e s t h e subs ta ce u de r goe s a c h a g i i t s c ry ta lli

n e n n n e n s ne

con di tio bei g con ve r te d fr om a n u s tabl f r m i to th e s table

n, n n e o n

1 “
I den tific ation of P ure Organ i c Compoun d s , Vol . I, 2 1 8—9 .
 LA BORA T ORY E XP E RI M E NT S 67

l ike iodin mon och lo r ide , a n d ph o sph o r us

e For exampl e , .

il e or me ta s tabil e fo r m o f benz oph e n on e me l t s a t bu t

me l te d a n d a ll o w e d to s olidify , if h ea t e d a gain ,

at S ome t ime s t h e d iff e r en c e is muc h gr e a t e r

some time s it is ve ry muc h le ss T he Chan ge s .

o th e r ma y b e ve r y r api d o r ve ry sl ow I f th e .

11 ve r y sl ow ly t h e me ta s tabil e f o r m may b e

s table fo rm an d on ly th e mel tin g po in t of the -

f o rm m ay ha ve th e l ow e r me l t in g p o in t -
.

u s tabl me me l t s — °
ox i at 34 5 an d th e n e

is m r ic ot polymo rph ic o e ,
2
n

po s d to be s t r oisome r ic e e e .

f w k ow n c a se s wh e r e th subs ta ce e n e n

t e mp r a tu r e t o a milky li qu id wh ic h e ,

d l y b e com s c l a r a lso a t a d efin i te en e e

r v r s e se r i e s f ch a g s oc cu r s S in ce e e o n e .

h w p r op e r t ie s of b o th liqui d s a d 5 S o n

t l 3
T h e c rys ta lli e s t r uc tu r e s a s . n

t h e mic r o s c op e bu t is ,

c a t e d by th doubl e r e f r ac ti e h ib i t e d by th e li qui d an d by
e on x ,

f rmation f th figur e s c ha ract r is tic Of d uble r ef r acti g c rys

o O e e o -
n

betwee c r ossed Nicol p r isms i con ve rgi g ligh t

n n n .

S uc h a subs ta n c e is c all ed mon o tropi c . For a d is c ussi on of is ph en omen on

th ,

e R ul e 4th E d ,
”
.
—
46 9 ; an d Holl ema n Organ ic
“
,

trin i tro m c res ol ph th a lic a c id s t ilben e d ic hl orid e ben zoi n ma n de li c ac id c in

-
r
, ,
-
, , ,

h a mi c ac i d c a rb o s t yril me r c ury d ip h e n yl limon e n e t e t ra b romi d e e t c

, ,
-
,
-
, .

2
S ee Fi n d l a y T h e P h a s e R ul e
“
t h E d 8 —1 1 H o ll ema n ”
Orga n i c
, 4 2 0 ; ,
.
,

Ch emi s t ry 43 1 3 ; a n d S i dgw i ck T h e Organ i c Ch emis t ry o f

” “
4 th E d
-
, .
,

Ni trogen ,
”
1 18 .

3
For d isc ussi on s e e F in d la y T h e P h a s e R ul e 4th E d ,
—
5 5 8 ; an d , .

Holl eman Organ i c Ch emis t ry 4 th E d

,
“
408 Ch ol e s te ry l ben zoa te
,
. .

me l ts to a milky liqui d a t 1 4 5 5 a n d t o a c l ea r liqui d a t 1 7 8 .

°
Azo xyan isole .
,

azoxyp hen e tol e an d

p meth oxy c innamic ac id al so Sh ow a simil ar behavior
,
- - .
68 LA BORAT ORY M ANUAL OF OR GANI C CH EM I S T R Y

Q UE S T I ON S
1 D iscuss s om e o f th e e rr o r s in th e o r di n a ry m e thod Of de
mi n in g th e m e l tin g p o in t
-
.

2 . W hy is i t n e c e ss a ry t o h ea t sl owly wh e n th e t e mp e ra ture
n e a r t h e m e l t in g p o i n t ?
-

W hy sh ould th e subs t a n ce be p owd e re d ?

Wh a t obj e c ti on is t h e r e t o th e u s e Of a rubb e r b a n d f or h o
t h e m e l t i n g p o i n t t ub e t o t h e t h e r m o m e te r ?
W h a t a dva n t age d oe s c on c su l furic a cid h ave ove r gl y c e
.

a n d c o t t o n s e e d o il a s us e d i n t h e m e l t i n g p oi n t a pp a ra t us ?

(Comp a r e b e h avi o r on h ea t in g .

Wh a t b a th is use d for ta ki n g m e l tin g p o in t s ab ove

-

W h a t is t h e Obj e c t Of a ddi n g s om e t im es a c r ys ta l o f p o t a ssium

n i t r a t e o r s o dium p e r sulf a t e t o t h e c o n e sulfu r ic a cid b a t h ?
.

Giv e n t w o subs t a n c e s h avi n g t h e s am e m e l t in g p o in t if on e

-
,

is k n own h ow c an y ou te ll wh e the r th e o th e r comp ou n d

,

is iden t ical wi th t h e fi r s t by m ean s Of th e m e l tin g p oi n t -

d e te rmi n a tion ? E xplain .

W h a t a dvan tage h as w a t e r o ve r c on c sulfuric a cid f or d e te r

.

mini n g l ow m e l ti n g po in ts ? (Comp are sp e cific h e a t s )

-
.
70 LABORAT OR Y M AN UAL OF OR ANI G C CH EM I STRY
E th er D i s til l ati on h r mus t be k ep t away from fl am e s
.
—Et e
.

I t s v ap o r is he avi e r th an a ir a n d v e ry i n fl amm a bl e an d t h e r e f o r e ,

t h e h e a tin g f or th e dis t ill a t i on mus t b e d o n e wi t h s t ea m or

w a rm wa te r I n e th e r dis tilla ti on u s e an E rlen m e ye r suc ti on fl a sk
.

a s a r e c e iv e r c o n n e c t e d as in t h e A bs o lu t e A lc o h o l e xp e rim en t ,

p 2 7 bu t wi th a lon g rubb e r tub e a t t a ch e d to its ou tle t tub e an d

.
,

le a din g b e l ow th e l e ve l of th e d e sk t o c arry away th e fum e s .

W h e n sm all qu an ti ti e s a re dis t ille d a n o rdin a ry fl a sk may b e us e d

a s a r e c e iv e r a n d t h e sp a c e b e t w e e n th e c o n d en s e r t ub e an d m ou t h

o f th e fl a sk l oo s e ly plu gge d wi t h c o t t on t o pr e v en t th e circul a t i on

o f th e v ap o rs .

H a v e al l n e c e ss a ry c on n e c ti on s r e a dy b e fo r e th e e xp e rim e n t
is s tar te d .

T O a 2 5 0 cc fl a sk c on t a i n i n g 5 gr a ms Of dry m ag n e sium
.

t ur n i n gs a tt a ch a n a ddi ti on t u b e a n d r e flux c on d en s e r wi th i n n e r
t ub e dry I n s e r t a dr o ppi n g fu n n e l in th e a ddi t i o n tub e a n d
1 - 2
.

con n e c t a calcium chl o r id e tub e fille d h alf

a n d h a lf wi th s o d a lim e (t o r e m o v e c a rb on di o xid e) T h e s od a .

lim e sh ould b e n e x t to th e l arge op en en d Of th e tub e A dd 2 5 .

cc o f dry e th e r to th e fl a sk P l ac e a s olu ti on of 3 0 cc (44 grams)

. . .

o f dry e t hyl b r o mid e ( t wic e t h e th e o r e tic a l a m ou n t r e quir e d ac

cordin g t o th e e qu a ti on ) in 5 cc Of dry e th e r i n to th e bul b 1 .

Of t h e fu n n e l s t opp e r l o o s e ly a n d l e t t his
,

fl ask A Vigo rous r ea c t ion b e gin s a f te r

.

b ee n add e d Mod e r a te by 5 .

I f i t d oe s n o t s ta r t sp on ta n e o usly w a rm th e fl a sk wi th t h e ,

or a dd a crys t a l o f i o di n e S h ak e fr e qu en t ly . A f te r th e .

t i on is w e ll s t a r t e d a d d 5 0 cc Of th e d r y e th e r dir e c t t .

mix ture by p ouri n g it thr ough th e c on d e n s e r Wh e n p r .

all th e m agn e sium h a s dis app ea r e d c a u t i o usly a d d wi th sh aki n g ,

a n d good c ool i n g a s o lu t i on o f 5 cc, ( 1 2 gr a ms ) o f dry a c e t on e

1 .

a n d 1 0 cc o f dry e t h e r fr o m th e dr oppi n g fu n n e l E a ch dr op -
.
.

re a c t s wi th a hiss an d caus es a whi te pre cipi ta te which a t firs t

redisso lve s bu t l ate r s e ttl es d own a s a bluish gray visc ous m ass -
, .

1
S e e F ig 3 , p 1 3 . . .

2
T h e c onn ec t i on c a n some time s be ma d e i
w th a pi ec e of rubber tubin g in s tead
of a c o rk .
 LA BORA T OR Y E XP ER I M E NT S 71

r eac tion is comple te c au ti ously d e compose th e

te r t h e
on pr o duc t by a ddi n g from th e fu n n e l duri n g ab ou t
,

min u te s th e c alcul a te d am ou n t o f sulfuric a cid in 1 40 cc

,
1
.

Durin g this t r e a tm en t pl a ce the fl a sk in ic e an d sh ake

ly A flo c c u l en t whi t e pr e cipi ta te is f orm e d a t firs t
.

te r diss o lv e d S e p a r a t e t h e e th e r e a l s olu t i on which

.

t h e pr o duc t an d dry wi th fus e d p o ta ssium c a rb on a te

, .

t h e e th e r by dis t ill a t i on Obs e rvi n g th e pr e c a u ti on s

,

fra c ti on a te th e r e sidu e in a sm all dis tilli n g

e th e c a rbi n ol is v ol a t il e wi t h e t h e r c o ll e c t th e

th e f oll owi n g f r a c t i on s : 7 0
° ° °
95 1 0 5
re dis till e a ch c ollec ti n g th e p or ti on dis tillin g 00
,
1
°

s ampl e P ure dirn e th yl e thyl ca rbi n ol b oils a t 0 2

.
— -
1
°

r av i t y o f at Yi e ld 40 pe r c en t ,

th e t h eory .

'

Te s t th e firs t ru n n in gs of the dis till a te f or u n s a tu ra ted c om

ou n ds wi t h br omi n e in c a rb on t e t r a chl o rid e an d wi th di lu te ,

p o tassium p e rm an gan ate .

N OTE

M agn e sium tur n in gs f or u se r eac ti on mus t be

in th e G r gn a r d i
ep a r e d f r e sh o r kep t in a b l s k b een cove r ed w i th
o t t e w ho e c or h as
t e d p a r affin t o p r e ve n t th e e n t r a n c e o f mois tu r e Oth e r w i s e .

magn e sium b e come s c oa te d wi th th e h yd r oxide e tc a n d do e s ,

.
,

r e ac t well .

R E F E RE N C E S

Ga t te rman n , c ic al M
P ra t e th o d s of Or gan ic Ch emis t ry , 3d
—
E d , 3 5 0 4 ; Wr en ,
.
“
T h e Or ga n o me ta llic Co mp oun ds of Z in c
a gn e s iu m (Va n N o s t ra n d — ls
”
1 26 ,
—
7 9;
2 N e on a n d ,

E l ec t r omo tiv e fo r c e d e velope d in c e lls c on ta in in g n on

“

li quids ,
”
J ourn A mer Chem S oc
. . . .
,
39 82 .

Q U E S T I O NS
How d oe s m ois tur e c a us e t r oubl e in t his e xp e rim en t ?
W hy is abs e n c e Of w a te r u n i mp o r ta n t a f te r th e k e ton e
h as b e en a dd e d ?
1
Con e . sulph uri c ac i d Of s p gr . . i s approxima tely 9 6 %
c on t a n H28 04
i
w e gh t . Make sure of your e quation be f ore makin g th is c a l c ula ti on .
72 LABORA T OR Y M A NUAL OF OR GA NI C CH EM I ST R Y

Why is n t o rdin ary e the r us e d an d d r i e d dire c t ly wi th

’

ca lcium chlo r id e a s in t h e ca s e Of th e a ce t on e ?
W hy c a n n o t t h e a ce t on e b e dri e d wi th m e t a llic s o dium ?
W h a t o t he r s o lve n t b e sid e s e th e r c a n b e us e d f o r t his e xperi
m en t ? Why ?
Wha t re a c t i on s take pl a ce wh en e the r m a gn e sium an d , ,

e t hyl br omid e a re b r ou gh t t oge t h e r ?

Why is th e fl a sk c on ta in in g this re a c ti on mix ture k ep t in

c old wa te r ?
Why is th e a ce ton e a dd e d cau ti ously ?
Ca n th e a c e t on e b e a dd e d di r e c t ly wi t h th e e thyl br omid e
t o th e e t h e r a n d m agn e sium mix t u r e ?
-
( C o mp a r e D a vi e s
a n d Kippi n g J ou r Chem S oc
,
. . .
,
99 2 96

Wh a t w ould h app en if c arb on dioxid e c am e in con ta c t

wi th th e Grign ard re age n t ?
I s th e m agn e sium oxidiz e d o r r e duc e d in th e e xp e r im e n t ?
Wh a t w ould be f orm e d if on ly w a te r w a s a dd e d a t th e en d Of
th e r e a c ti on ?
W h a t is th e purp os e o f a ddin g a cid ? I S it a bs olu te ly
n e c e ss a ry ?

Co uld c on c H S O4 b e us e d in pl a c e of dilu t e a cid ?

.
z

Wh a t cause s th e bubblin g th a t of ten occurs a f te r a l l th e

dilu te a cid h as b ee n add e d ?
Wh a t migh t b e s om e o f th e impuri ti e s in th e cru de t e r t i a ry
a lc o h o l ? mp r pr p r i s fi s i s
“
( C o a e t h e o e t e Of t h e r t r u n n n g
o f t h e dis t ill a t e ) .

E xpl a i n wh a t is m ea n t by th e te rm vol a tile wi th e th e r .

( C o mp a r e fr a c t i o n a t i on O f liquids which mix in a ll pro

p o r t i on s ) .

Why u s e a sm all distillin g fl a sk in th e r e dis till ati on of

dim e thyl e thyl ca rbin ol ?
- -

H ow d o e s this p e n tyl (amyl) a lc oh o l diff e r fr o m th e is om

a lc o h o l o f c o mm e r c e ?

T h e a m o u n t Of e thyl br omid e (3 0 cc ) is t wic e th e a m ou n t

r e quire d by th e the ore tica l e qu a ti on Why is it n e ce ssa ry
.

to us e an e xc e ss ?
 E xpe rime n t NO . 14

RE D U C T I ON OF A KE T ON E To A S E C ON DA R Y A L C OH OL ( S OD I U M
A L C OH O L R E D U C T I ON )

P r e paratio n of M e th yl ph e n yl -c a r bin ol f ro m
-
Ac e toph e n o n e
(M e th yl ph e n yl ke ton e )
- -

Dissolve 1 0 gr ams ( 0 cc ) Of a ce toph en on e in 1 2 5 cc Of al

1 . .

coho l in a 5 00 cc flas k w ith an a ddi ti on tub e a t ta ch e d an d a

-
.
, ,

r eflux con d en se r con n e c te d with th e sid e tub e P r ep a re 1 0

g r a m s o f cl e a n m e t a llic s o dium
1
c u t in s t rips n a rr o w e n ou gh

t o slip thr o u gh th e v e r t ic a l t ub e e a sily A dd t h e s e s t rips t o th e .

alco h ol ic Ol u tion t hr o ugh th e v e r t ic a l t ub e a f e w a t a t im e a n d

l e t th e r e a c ti on ab a t e s o m e wh a t b e for e th e a ddi t i on Of o th e rs .

T h e r e duc t i on sh ould be s t r on g an d th e a lco h o lic s o lu ti on sh ould

b oil vigor ously bu t a t th e s am e tim e th e rea c ti on mus t be k ep t
,

in h an d .

Wh en al l th e s odium h as di ss olve d dis till Off as much as pos ,

sible of th e a lcoho l i n va c u o S in ce it is di fficul t to t ra n sfe r th e

,
.

rea c ti on mix tur e which is ve ry viscous an d sin ce th e re is a grea t

-
, ,

de al Of foami n g du r i n g th e dis till a ti on th e o r i gi n a l fl a sk is us ed ,

f or this firs t di s t il a t i on i n s t e a d o f th e C l a is e n fl a sk d e sc r ib e d in
th e a ccomp a n yi n g d r e c ti on s o r v a cuum d is ti ll a ti on E xp t
'

5 ,
. 1

p 7 6 S l an t th e fl a sk in o rd e r to a ll ow th e f oam to bre ak
. .

agai n s t th e w a lls a n d n o t p a ss ou t i n t o th e dis t ill a t e Con n e c t .

it wi th a b e n t t ub e l e a di n g i n t o a dis t illi n g fla s k which a c t s a s a -

re ceive r (Comp a r e Fig T h e r e ce iv e r n e e d n o t b e c o o l e d

.

in this c a s e ; l e t th e a lc oh o l v ap o rs p a ss thr ough u n con d e n s e d .

T h e r e c e ive r is us e d t o c a t ch a n y o f th e p r oduc t which s om e

tim e s dis t ills o r g oe s ove r wi th s om e f oam H e a t th e m a in fl a sk .

1
Us e a c o mmon kn ife or p e n -
kn ife
s od iu m an d dip th e bl a de
to c ut th e
frequ en tly i n to th e kero se n e w i th w h i c h th e so diu m is c ov e re d R e turn al l re si
du e s t o t h e o ri gi n a l b o ttl e o r d e s t roy t h e m w i t h a l c oh ol a s men t i on ed u n de r ,

D ime thyl e th yl c a rbin ol p 6 9

- -
,
. .
 L ABORA T OR Y M A NUAL OF OR G A NI C CH EM I S T RY
wi th w a t e r k ep t a t 5 0 a n d f r e qu en t ly sh a k e th e fl a sk
°

s om e wh a t t o ch an ge th e su r fa ce o f th e mix ture an d th us p e rmi t

r apid vap oriz a ti on T h e dis till a ti on r e qui r e s fr om on e to tw o
.

h ours A s it progr e ss e s th e mix ture b e com e s a d a r ke r brown

.
,

a n d p a s ty .

Wh en pr a c tica lly al l th e alcoh ol is dis till e d ove r a dd 5 0 cc .

o f w a t e r an d t h e n e x a c t ly n e u t r a liz e t h e s o lu t i on wi t h a c e tic

a cid . Dis till Off th e r e m a i ni n g a lcoh ol in vac u o from th e s am e

fl a sk an d in th e s am e m a n n e r a s b e f o r e .

E th e r E xtr a c ti on T r a n sfe r th e re sidu e to a s ep ara tory

.

fun n e l wi th th e a id Of w a t e r an d a li t t le e the r an d e x tra c t it wi th ,

e th e r a s f o ll o ws : A dd ab o u t 3 0 cc Of e th e r (a n d if n e c e ss a r y .

e n o ugh w a t e r t o diss o lv e a n y pr e cipi t a t e ) s topp e r s e cure ly , ,

in ve r t th e fun n e l h o ldin g th e s topp e r in wi th on e h an d an d pl a c

,

in g th e thumb Of th e o th e r h a n d o n th e h a n dl e Of th e s top c o ck -

a n d t h e fir s t tw o fi n g e rs o n th e o th e r sid e Of th e s t e m a n d sh ak e .

W hil e it is s till i n v e r te d Op en th e s top c o ck to r e l e a s e th e pre s -

su r e wi thi n th e fu n n e l Cl o ze th e s top co ck a n d S h ak e again

1
.
-
,

fre qu e n tly r e le a si n g th e pre ssure Turn th e fun n e l r igh t sid e .

up supp or t it in a ri n g a ll ow to s e ttl e draw Off th e a qu eous

, , ,

l aye r in to a b e ak e r a n d p ou r th e e the re al s olu ti on f r om th e top

,

Of th e fu nn e l i n t o a dry E rl e n m e y e r fl a sk R e tu r n th e a qu e ous .

l aye r to th e fun n e l rep e a t th e ex t r a c ti on wi th ab ou t th e s am e

,

a m o u n t Of e t h e r a n d a d d th e e th e r e a l s olu ti on t o th e fi r s t
, p o r

ti on in th e E rl e n m e y e r fl a sk .

I f s o m e o f th e p r o duc t w a s dis t ill e d o v e r i n to th e r e c e ivi n g

fl a sk th e m a t e ri al thus c oll e c te d S h ould b e ex t r a c te d wi th e the r
, ,

provid e d it con t ai n s pra c tic al y n o a lcoh ol a n d a dd e d to th e

’

m ai n e th e re al s olu ti on I f it c on t ain s much alcoho l it c an n o t

.

ve ry we ll be e x tra c te d wi th e th e r an d th e a lc oh o l mus t b e

e va p o r a te d Off b e f o r e e x t r a c ti on .

I f th e m ai n e th e r e x t r a qt is a cid t o li tmus n eu t r a liz e i t by ,

shak in g wi th a s olu ti on o f s o dium ca rb on a te .

Dry th e e th e re al s olu t on wi th fus e d p o ta ssium ca rb on

i

t r an sf e r it t o a Cl a is e n dis t illi n g fla s k r e m ov e th e e th e r -
,

1
I n this l abora t ory th ere a re tw o c a s e s on re c ord w h e r e th e s ep a
e xpl o d e d o n a c c o u n t o f c a re l e ss n e ss in d isr ega rd i n g t h is proc e d ure .
 LA BOR A T OR Y E XP ER I M E NT S 75

un d e r th e usu a l con di ti on s an d th en dis till the re sidu e

11

in a cc o rd a n c e wi t h th e di r e c t i on s giv en in E xp t 5 . 1 ,

thi s S om e e th e r will p a ss o v e r fi r s t th e t e mp e r a tur e

.
,

a n d th e c a rbi n o l dis t ills I t b o ils a t 1 1 8 a t 4 0 mm

°
. .
,

2 1 mm a t 1 5 mm A t a t m o sph e ric pr e ssur e

°
an d 9 8 .
,
.
,

b oils wi th p a r t i a d e c omp o si tion a t ab ou t T h e yi e ld

is ab ou t 40 pe r ce n t of th e th e or e tic a l am ou n t .

R E F E RE N C E S F OR E T H E R E X T RAC T I ON

Walke r ,
I n t ro d u c t io n to P h ysica l Ch e m t r is y , 7 th E d .

59
—
6 1 ; A le x . S m th , i “
In t r o du c t io n to I n o r gan ic Ch e mis y
tr , 3d
Ed . 1 89 .

Q UE S T I ONS
Why is a lcoh o l us e d in this exp e rim en t ?
I s a ll th e a lco h o l us e d up duri n g t h e r e a c t i on ?
Wh a t b e come s of th e s o dium e th oxid e ?
P o i n t ou t wh a t is r e duc e d a n d wh a t is oxidiz e d .

I s th e me t hyl ph e n yl —
— ca rbi n o l form e d a c te d up on by
s odium ?
Wh a t o th e r o r gani c comp ou n d is lik e ly to b e f orm e d ?
I s t his a hi gh e r l owe r r e duc ti on pro duc t o f th e
“ ”
or

k e t on e ?
Why is so dium us e d i n s tea d o f s o m e o th e r me tal lik e zin c ?
Wh y d o e s s o dium r e a c t wi t h a lco h o l whil e zin c d o e s n o t ?
W h e r e d o e s th e r e m a i n i n g a lco h o l co m e from ?
H ow c o uld y o u c a lcul a t e h ow much Of t his r e m a in i n g
a lc oh o l t h e r e w ould b e ?
Why is it n e ce ss a ry t o di s till Off th is a lcoho l b e fore ex tra c tin g
wi th e th e r ?
Why is th e e th e r e a l s olu ti on p oure d from th e top of th e s ep
a r a t o ry fu n n e l ?

Discuss th e e x t r a c tion o f a qu eous s olu ti on s an d mix ture s

o f o r gan ic subs t a n c e s wi t h immiscibl e liquids such as ,

e th e r chl o r o f o rm b e n z en e e t c
, , ,
.

Wh at is mean t by th e Coefficie n t o f P a r ti ti on or D is tribu

t i on ? (S ee r e fe r en ce s a b ov e ) .

W hy is it n e c e ss a r y t o dis t ill in a v a cuu m ?

W h a t is th e b o i l i n g p oi n t o f ace t oph en on e ?
-

How c ould t h e p r e s e n c e o f an y u n ch a n ge d a c e t oph e n on e

b e sh ow n in t h e pr o duc t ?
I s th e m e t hyl ph e n yl c a r bi n o l as pre p a r e d in th e l ab o r a tory
- -

o t ic a ll a c tiv e ? E x l ain
p y p ,
 E xp e rime n t N o . 15

D is till ati on in vac u o or un d e r D imi n i s h e d P r e s s ur e

Dis tilla ti on i n vac u o or u n d e r dimin ish e d pre ssure is a

re sor te d to if th e comp ou n d d e compo se s wh en h ea te d a t
p h e r ic pr e ssur e b u t ,
is v o l a t il e wi t h o u t d e c o mp o si t i o n a

p r e ssure s T h e app a ra tus empl oy e d is i n dica te d

.

a lly in Fig 1 1 . A Cl a is en dis t illi n g flas k is us e d si n c e

.
-

sid e arm which h e lps to pre ve n t an y liquid from b e i n g

up i n to th e ou tl e t t ub e if th e liquid should bump vi ole n
si n ce tigh te r j oin t s c a n be Ob tain e d by con n e c ti n g th
mome t er a n d th e capill a r y ex te n si on tub e wi th h e a vy
t ub in g ou t sid e t h an wh e n rubb e r s t opp e rs a re us e d .

a n o rdin a ry dis tilli n g flas k as th e r e c e iv e r wi t h a rubb e r 5

-

m akin g ce r tain th a t th e ou tl e t tub e of th e Cl ais en fl ask proj

i n to th e bulb of th e r e ce ive r in ord e r th a t th e vap o r s o f th e
'

til l a te may n o t b e c a r r i e d Off by th e suc t i on Durin g th e .

til l a tio n c ool i t wi th ru n n i n g w a t e r 1

S uppo r t b o t h fl a sks
.

cl amps I f th e temp e ra ture of th e dis till a te u n d e r th e dimin is h e

.

pre ssure e xc ee ds 60 th e rubb e r s topp e r in th e r e c eive r shoul

1
°

be ch a n g e d f or a g ood c o rk s topp e r R ubb e r s t opp e rs s o f t e n an .

g r a du a l l y m e l t a b o v e t hi s t e mp e r a t ur e A g oo d c o rk .

c a n s o m e t im e s b e m a d e a ir tigh t by c o a t i n g i t wi th c o ll o di on
-

a f t e r th e app ar a t us h a s b ee n fi tt e d up Con n e c t th e d e live ry .

t ub e Of th e r e c e iv e r by m ea n s of rubb e r pre ssur e tubin g t o a

m an om e te r an d a w a te r pump B y usin g gl a ss tubi n g an d shor t .

r ubb e r c o n n e c t i o n s o nl y a sm a ll a m o u n t Of t h e e x e n sive p r es
p
su r e tubin g is n e c e ss a ry A ll gl a ss con n e c tin g t ubin g sh ould
.

have sm ooth r ou n de d e n ds
,
.

1
T he lin g is ma de more
c oo e fi c ie n t if a pi ec e l
of c o th is w rapp ed arou nd th e
bul b Of t h e re c e ivi g fl a sk
n .
78 LABOR A T OR Y M AN UAL OF OR GAN I C CH E M I S TR Y
A good w ate r pump will give a p r e ssure
-

a s l ow a s th e v ap o r t e n si on o f th e w a t e r a t i t s p ar ticul a r

t u re I n wi n t e r wh e n t h e t e mp e r a t u r e o f t h e w a t e r In
p e r a .

a t whi ch th e v ap o r t e n si on o f t h e w a t e r is mm .
,

pre ssure wi thi n th e app a ra tus may approa ch 8 mm bu t in s .

,

me r wh e n th e t emp e r a t ur e o f th e w a te r may b e as high as

a pr e ssur e c a n n o t b e Ob t a i n e d l ow e r t h an 2 1 mm whi ch is .
,

vap o r te n si on o f th e w a te r a t th a t temp e ra tur e 1

.

T h e g e n e r a l c on n e c t i on s f or v a cuum dis t ill a t i on a re m

a s f o ll ows : Ou t l e t t ub e o f th e r e c e iv e r t o a n E rl en me y e
t i on fl a sk an d th e l a t t e r
T h e t ub e c on n e c ti n g th e s uc ti on
e x t e n d t o th e b o t t om o f th e fl a sk in o rd e r t h a t a n y w a te r which

may c om e ov e r on a cc ou n t of u n e qu al pr e ssu r e in th e
m ain will be suck e d righ t ou t as s oon as the gre a te r wa te
sure r e turn s A thre e h ole d rubb e r s topp e r is us e d in th e
.
-

Of th e suc ti on fl a sk Thi s pr o vid e s f or th e tub e to th e

.

jus t m en t ion e d f or th e tub e con n e c t in g th e

,

a gl a ss s t op c o ck which is us e d f o r e qu aliz in
-

n e c e ss a ry (or t his gl a ss s t op c o ck ma y b e
-

r e ce ive r an d th e s uc ti on fl a sk) .

pl a ce d jus t b e f or e th e pump I n s tea d .

fla sk as th e r e ce ive r it is Of te n c on v en i

Of high b o ilin g liquids or s o lids t o u s e a suc ti on ’

-

a t e s t t ub e wi t h a sid e ou t l e t t ub e
-
I n s om e c a s e s .
,

t ub e c a n b e pl a c e d i n sid e an d th en it will n ot b e n e ,

t r an sfe r th e dis til l a t e .

I n o rd e r t o pr e v e n t bumpi n g th e vapor ph a s e is i n tr o duce

1
For pressure s l ow er s
t h a n th e e , a good oil pump mus t be us ed . T h e n it i
po ssibl e t o go d o w n t o mm .

A t ab e l of th e v ap or pre ssure ( ten si on ) of w ate r at d iff e ren t t e mpe ra t ure s i

giv e n on p .
3 01 .

2
No t S ho w n in th e figur e . A
va c uu m valv e c on sis t s of a gl a ss t ube be n
in th e f o rm Of a n a rro w in v e t e d U w i t h e l on ga t i on s a t t h e e n d
r
'

purpo se s On e a rm c on ta i n s a fre e movi n g h oll o w gl a ss plun ge r

.
-

a t on e e n d t o fit i n t o a c o rr e sp o n d i n g gro u n d gl a ss s e a

Wh en th e pre ssure su ddenl y c h an ge s t h e plu n ge r mov

a n d c l o s e s th e t u be a u t oma t i c a lly a n d mo v e s ou t a ,

rev ers ed . I t s e rv e s t o kee p w a te r from b e in g d ra w n i n to th e a pp a ra tus ,

 LA BOR AT OR Y E XP E R I M E NT S 79
“

usin g pie ce s of p orous t ili n g in the liquid or b e tte r by1

,

sin g a rapid c on tin u ous s t r e am of tin y air biibbl e s th r ough

liquid (s e e discussi on in n o te 2 p 1 8 Of th e B oili n g p oin t,
.
,
-

t) . A n o rdin a ry gla ss t ub e is dr a w n ou t i n to a fin e
an d c u t Off a t th e p r op e r l en g t h T O th e wid e e n d is .

ash or t pi e c e Of rubb e r tubi n g wi th a scr e w cl amp a t

en d t o r e gul a t e th e bubb l i n g S om e tim e s th e capill a ry
2
.

fin e t h a t n o o th e r r e gul a t i on will be n ec e ss ary

this m e th o d is th a t i t i n t r o duc e s an e rr o r
b oilin g p oin t a s th e pr e ssure r e gis te r e d wh en air is
-
,

will be th e sum o f the p ar ti a l pre ssure s Of th e vap or

th e a ir .

dis tilli n g fla s k sh ould n ot be m or e th an on e third full I t

- -
.

d by m e an s Of a w a te r or a n Oil b a th a ccordin g t o th e
3 -
,

d G oo d r e sul t s a re Ob tain e d by imm e rsin g

.

b o f the fl a sk a t le a s t tw o thirds i n to th e b a th T h e vap o r

-
.

sup e rh ea te d s o much a s u n d e r o rdin a r y c on di ti on s on

a cc o u n t o f th e r a r e f a c t i on O f th e v ap o r a n d l e ss h e a t c on duc t

an ce . A t h e rm om e t e r is k e p t in th e o il a n d th e t e mp e r a tur e
o f th e Oil sh o uld n o t o rdi n a r ily b e m o r e t h a n 2 0 high r ° °
—
3 0 e

th a n th e t e mp e r a t ur e a t which th e liquid in th e fl a sk dis t i ll s .

T h e h ea ti n g is n o t b e gu n u n t il th e app a r a t us is e xh a us t e d .

t im e s i t is n e c e ss a ry t o pr e v e n t r a di a ti on by wr appi n g
o r a sb e s to s p ap e r a r o u n d t h e n e ck Of th e fl a sk b e l o w th e

g l os e s i ts eflfi i in a sh ort t ime probably bec a use

c ie n c y w th ,

u n d e r t h e red u c ed pre ssure .

s k is us e d i n s t e a d Of t h e Cl a is e n d is t illi n g fla s k -
,

p a c e e n ou gh f or bo t h t h e rmome t e r a n d t h e gla ss bu bblin g

t h e rmo me te r ma y be pl a c e d w i th i n t h e t u b e a n d a on e h ol e d -

Oil is good to u s e Pa ra ffi n o r pa rafi n oil smoke s a gre a t deal

. .

Oil a ls o s moke s s ome w h a t a t firs t a n d giv e s o ff a pu n ge n t o do r ,

r th re e h ea t in gs it d oe s n o t smoke s o mu c h I t c a n be c a rri ed up .

A me ta l ba th h a s the advan tage that it doe s n ot smoke a n d is n o t

Fo ll o w i n g a re a ll o ys
c a d miu m ,
80 L A BOR AT OR Y M ANUAL OF OR G ANI C CH E MI S T R Y

It is b e s t to t e s t th e app ara tus b e fore pu t ti n g in th e subs ta n c e

in o rd e r t o d e t e rmi n e wh e th e r th e gl a ss is p e rf e c t a n d th e j oi n t s
a re t igh t . I n t his w ay a l o ss o f m a t e ri a l ma y Of t en b e a vo id e d .

"Wh en ca rryi n g ou t a va cuum dis t illa t i on it is a dvisa bl e t o

prote c t th e e ye s wi th goggle s or u se a glass screen
'
,
.

A t th e e n d o f th e dis till a t i on th e s top c o ck sh ould b e gr ad -

u a l l y o p e n e d b e f or e th e w a t e r is t urn e d Off
'

is us e d b e twe en th e r e c e ive r an d th e suc ti on

i tse lf is gradu ally a n d c are fully rem ove d This a ll ows th e .

cury colum n t o se t t l e sl owly an d also pr e ven t s w a te r vap or

b e in g suck e d i n to th e app ara tus .

T h e M an ome ter . T h e m a nom e t e r c on sis t s Of a gl a ss

b e n t in such a w ay as to h old a co lum n of m ercury a ,

a n d a s ta n d f or a supp o r t a s sh o wn in th e figur e
,
T he .

le n g th Of th e gl a ss tub e sh ould be ab ou t 5 0 cm l on g an .

l on ge r le n g th 8 5 cm T h e l owe r b en d c an be
.

he a ti n g in a sm oky fl am e A f te r th e m e rcury h a
.

in i n s e r t a plug o f c o t t on t o k ee p ou t f o r e ign m a tt e r
,
1

a sm a ll t e s t t ub e o ve r i t
-
B y sl an ti n g th e m a n om e t e r wh e n th e
.

m e rcury is a dd e d a n y air bubble s will com e ou t re adily e sp e ci ally ,

if the tub e is tapp e d T h e gl a ss tub e sh ould be dry an d fre e from

.

dus t gr e as e e tc I f th e m e rcury d oe s n o t ru n free from bubbl e s

, ,
.

w ash th e tub e wi th a lcoh ol an d e th e r an d rem ove th

e th e r wi t h a curr e n t Of air T h e c olum n Of m e rcury is Of such a
.

h e igh t th a t Wh en th e app a ra tus is e xh aus te d th e l owe r an d uppe r

limi ts Of th e m e rcu r y will b e opp o si te s om e p oin t on th e scal e s
d e scrib e d b e l ow T h e gla ss tub e is con n e c te d wi th the suc ti on
.

fl a sk .

T o M ake th e S c al e S e l e c t an y p oi n t X n ot l es s tha n
.
, ,

3 8 cm .a b o v e th e l ow e s t b e n d in th e gl a ss t ubi n g a ,

n a rr ow s t rip s o f p ap e r ( Y a n d Z ) n ea r th e t op an d th e

th e s t an d in th e p o si ti on s sh own M ea suri n g from th e

.

m ark on th e p ap e rs n umb e rs sh owin g 2 8 to 3 8 em up a .

r e sp e ctive ly R ul e d ce n t im e te r p ap e r is v e ry c on v e ni
.

wh en this is us e d it sh ould n ot b e at ta ch e d u n til a

poin t Oppo si te a cen tim e te r li n e h as b e e n o ca te d l .
 LA BOR AT OR Y E XP E R I M E NT S 81

I n s te ad
h e s e sc al e s a m e te r s tick c a n b e fa s t en e d to th e
of t
s tan d an d th e diff e r e n t h eigh t s r ea d di r e c tly .

T o Cal c ul ate th e P r e s s ur e wi th i n th e Apparatu s Add th e .

figure s on th e l ow e r an d upp e r sca le s opp o si te th e top Of th e

merc u ry m en iscus in ea ch ca s e an d sub t r a c t th e sum of th e s e
i
1

numb e rs fr om th e b ar om e t ric r ea di n g R e co rd b o th th e b oili n g .

poi n t an d th e pre ssur e f or ex ampl e b p 22 ,

T h e t em . .

ra tu re Of th e b a th sh ould a ls o b e r e c o rd e d f o r r e f e r e n c e
p e .

I t is n o t a lw a ys p o ssibl e to ob ta i n e x a c t ly th e s a m e pr e ssur e
a t which t h e b o ili n g p o i n t is giv en in th e t e x t H ow e v e r th e
-
.
,
'

diff e ren ce in b oili n g p oi n ts a t th e given pre ssure an d th e pr e ssure

'
-

a c tu ally us e d c a n b e e s tim a t e d T h e dis till a t e is o f c ours e .

, ,

a lw a ys c oll e c t e d whil e th e t e mp e r a t ur e (an d pr e ssur e ) r e m a i n s

con s tan t .

The re is n o s e t rul e or ex a c t m e th od of calcul a ti on for fin di n g

th e b oili n g po i n t u n d e r dimi n ish e d pr e ssur e wh e n on ly th e
-

b oili n g p oin t a t 7 60 mm is k n own A f ew ge n e ral hin t s may be

-
. .

g iv e n A subs . t a n c e t h a t b o ils a r o u n d 1 00 a t 7 6 0 mm will °

.

b oil ab ou t 60 lowe r a t 2 5 mm an d on e th at b oil s a rou n d 2 00

°
.
,
°

a t 7 6 0 mm will b oil ab ou t 80 1 00 l ow e r a t 2 5 mm T h e ° °
—
. .

vari ati on in th e b oili n g p oin t b e c om e s gre a te r f or e a ch de gr e e

-

a t th e l ow e r pr e ssur e an d is v e ry mark e d a s th e pr e ssur e dr ops

,

3 o r 4 mm .

N OT E S

P u rific ati on o f merc u r :

y I f t h e me r cu r y is w e t o di r ty it c an be r

g i t t h r ou gh a d y fil t e r p ap e r wh ic h
r h a s a p i h ol e n

T h e i mpu r i ti e s s t ic k to t h e pape r w h i c h also abso r bs ,

S eve ral t r e a t men t s may b e n ec ssa r y wi th cl ea n fil te r s e

pu mp doe s n ot c atch a n d the wate r r un s ou t

at e r '
,

t r aigh t wi thou t c ausi g p pe r s u c t io h ol d t h e h a d c l os e to th e

'

s n ro n, n

bo tt m Of th pu mp wh ile th e wa te r is tu rn ed on an d cause a sligh t

o e

bac k pr s u r e u til the suc tion is all r igh t

e s n .

3 Ne e r u e a
. o r di n a ry fla t b o tt o me d fla sk in th e app a r a tus
v s n -

f vac uum dis tilla tion E plai

or . x n .

1
l a ss t ub in g be fo re
T ap th e g i
ta k n g th e read i n g in orde r to bri n g th e merc ury
to re s t a n d ov erc ome th e l ag
“ ”
.
 LA BOR AT OR Y M A N UAL OF OR GA N I C CH E M I S T R Y

4 . S ome t me i s f o r mo r e c o mpl e te co li
o ng a w a te r c o n de n e s r mu s
be pl ac e d b tw en th e dis tilli g fla k a d th e r e c eive r
e e n -
s n .

5 .A n a pp a r a t u f o l l e t i gsf r a t i s
r c owi tch o t i
n t c on u n err up t in

dis till at i on is de s c r ibe d by M T Boge r t J u n I n d . .

,
o r . . , an d
Chem , 7 .
785 6
-
.

6 . wa t e r sh ould splash i to th e oil th dis till a tion must

If n ,
e

s topped a d the w e t Oil r epl ace d wi th f r esh Oil I f this happ

n .

while the Oil is ho t it will foam ve ry much a d gr a t c a r e must be n e

u s e d t o p r ev n t a y of th e h o t Oil f r o m ge tti g o
e n yo r han ds e tc n n u , .

Oil wi th even a ve ry small amoun t of wa t e r in it is usel e ss .

Q UE S T I O N S
In va cuum dis till a ti on h ow is bumpi n g avoid e d ?
W hy sh o uld th e o u tl e t tub e of th e dis tilli n g fla s k ex t e n d -

i n to th e b u lb Of th e re ceive r ?
W hy sh ould th e dis tilli n g fla s k b e n ot m o r e th a n on e third
- -

full ?
Why is th e s t op cock op en e d b e fore the wa te r is tu r n e d Off ?
-

Why is th e tub e from th e suc ti on fl a sk t o th e pu mp ru n

d own to th e b o t tom of th e suc ti on fl a sk ?
Wh at a dvan tage s h as a Cl aisen fl ask in dis till a t i on i n
vac u o ?

W hy h ould an ordi n ary fla t b ottome d fl a sk n e ve r b e us e d

S -

in th e app a r a tus f or va cuum dis till a ti on ?

H OW l ow a p r e ssu r e c a n b e Ob t ai n e d wi th a w a t e r pump ?
Why is it n ot n e ce ss a ry t o h ave an abs olu tely defin it
volume of m e rcury in th e tub e ?
D O air bubbl e s a l on g th e w alls m ake a n y di ff e r e n c e ?
D o e s th e m e rcu r y d rop ex a c tly as f ar a s it ris e s ?
Wh ich r e a di n g on th e b a r ome te r sh ould y ou u s e f or ca lcu l a
t i n g th e pr e ssur e wi thi n th e a pp ar at us th e corr e c te d ,
“

or u n corre c ted
 E xpe rime n t N o . 16

OX I D AT I ON OF A P R IM A R Y A L C OH O L T o AN A L D E H YD E

P r e par ati on of a S oluti on Of Ac e tal d e h yd e

I n this e xp e rim e n t e thyl alcoh ol is oxidiz e d t o a ce tald e hyd e

m ean s o f s odium dichrom a te in dilu t e sulfuric a cid s olu t i on .

c e it is difficul t t o s e p a r a t e th e a c e t a ld e hyd e which b oils a t ,

th e impuri t i e s by fr a c ti on a t i on th e crud e a c e ta ld e hyd e

,

is usu ally abs orb e d in e th er an d con ve r te d i n to th e crys tallin e

ald e hyd e amm on i a which is ea sily purifi e d a n d t h e n us e d f or
, ,

m akin g pur e a c e tald e hyd e This is a l on g pro ce ss how eve r an d

.
, ,

require s e l ab ora te app a ra tus as d e scrib e d in E xp t 1 7

,
. .

For m aki n g a crud e pr o duc t which c an b e us e d in th e a ld e

ro c ee d a s f oll ows :

droppi n g fu n n e l to a 25 0 cc di s till i n g flas k c on

- -
.
-

wi th a lon g w a te r con d en s e r an d a rr an ge a r e ce iver s e t

,

On a cc ou n t o f it s l ow b oili n g p oi n t c a r e mus t b e exe r

-

ca t chin g th e dis tilla te A sm all E rl en m e ye r fl ask m ak e s

.

r e c eive r T h e e n d of th e c on d en s e r sh ould ex te n d i n to
.

as p o ssibl e an d th e fl a sk sh o uld b e e n t ir e ly surr o u n d e d

A dd a mix tur e Of o f c o n c sul furic a cid a n d

w .

ll th e droppin g fu n n éI Witl i a Sol u ti on of 2 0 gr ai n s gf

'

dichrom ate in 3 0 cc o f w a te r an d 2 5 c c of a lcoh ol an d

. .
,

th e c ours e of a b ou t fif t e e n t o t w e n t y mi n u t e s a llow this

sl owly i n t o th e fl ask H e at th e mix ture t o ge n t le boi l in g
.

ve ry sm all fl am e Af te r all th e s olu ti on h as b een a dd e d

.

th e ge n t l e h ea t i n g f or s e v e r a l mi n u te s R edi s til l very .

colle c tin g th e p or ti on b oili n g b e twe e n 2 0 a n d 4 5 in an ° °

e d r e c e iv e r A c e t a ld ehyd e b o ils a t
. T h e pr o duc t
n e e d n o t b e h a n d e d in ) c o n t a i n s s om e w a t e r b u t c a n b e ,

e n t s e n t i tl e d Te s ts f or Ald e hyd e s E xp t , .

83
84 LA BORA T OR Y MAN UAL OF ORGA N I C CH EM I STR Y
19 , p .
9 1 . F or s t udy , qu e s ti on s given u n d e r th e pre p a
use th e

ti on o f a c e t a ld e hyd e fr om a ld eh yd e a mm on i a E xp t NO 8 p ,
. . 1 ,
.

N OT E

Th is expe r imen t a nd th e t e tss i h f ll w sh ould if possible

wh c o o

carr i d o t du r in g o
e u ne labor a to ry p r i d Oth r w is xt ra p
e o . e e e

c auti on s must b e take n t o ke p t h e s olu ti n of t h e a l d h yde p r op e

e o e

s topp e r d a d cool d
e n e .
 86 LABORA TORY M A NUAL OF OR GANI C C HE M I ST RY
tight con n e c ti on s throughou t R ubb e r s topp ers may be use d
.

wi th a dvan tage .

I n to th e b o t t l e surr ou n d e d by ic e p our 1 00 cc of an hydr ous .

e th e r .T h e pip e tte S h ould Op en abou t 1 cm b e l ow th e surf a c e .

Of th e e th e r A dd a mix t ur e of 1 7 cc of c on e sulfuric a cid an d

.
. .

75 cc O
.f w ate r to th e fl ask an d durin g th e c ours e of thir ty
,

min u te s all ow a s olu tion Of 3 5 gr ams of s odium dichrom a te

in 60 cc of w a t e r an d 5 0 cc o f a lcoh o l t o dr op in sl owly
. . Durin g .

thi s tim e h e a t th e s o lu t i on t o ge n tl e b oili n g a n d a ll ow th e ,

wa te r to ru n very s l owly through th e con d en s e r R e gul a te .

th e h ea t an d w a te r flow s o th a t th e t e mp e r a tur e i n dica t e d by

th e th e rm om e te r in th e c on d e n s e r d oe s n o t r e gis te r hi gh e r t h an

( W h a t is t h e l ow es t t e mp e r a t ur e li mi t ? 1
Why mus t a
l arge fl am e n ot b e us e d ?) Af te r all th e mix tur e h as
con tin u e th e h eatin g wi th th e s am e pre cau ti on s f or a n
th ir ty min u t e s I f t h e e th e r s o lu ti on at an y tim e 5
.

hi gh in th e pip e tt e a d d a li tt l e m o r e Of th e s o lu t i on
, ,

h as all b een a dd e d simply op en th e s top c o ck Of th e -

fun n el m om en ta rily All th e ald e hyd e h as b een

.

wh en its pun gen t odor is n ot ve ry s tron g in th e fun n e l

for the te s t .

Wh en th e app ara tus is disconn e c te d n o te th e m os t pr on o

Odor fr om th e mix t ur e in th e fl a sk T0 wh a t is this du e ?
.

c an y ou a cc o u n t f o r it ?

Through a w ide tub e such as th e l arge p ar t Of a c

,

chlorid e t ub e or an ad ap te r or a fun n el p ass a s tr e am 0

, ,

hydrous amm oni a fro m a cyli n d e r in to th e e th e r s olu ti on

tain e d in th e wid e m ou th e d b o t t l e p a ck e d in ic e a n d s a l t
—

th e dr a f t pip e T h e s olu ti on will b e s a t u r a t e d in a b ou t

.

min u te s Fil te r Off th e whi te crys tals Of a ld e hyd e amm on i a

.

s uc ti on a n d dry t h e m u n t il a ll th e e t h e r h a s c ompl e t e ly

ra t e d . This c an be d on e con ven i en t ly in a va cuum d e si

T h e a ld e hyd e a mm on i a is s ome wh a t s olubl e in e th e r a n d a
crop of crys tals c a n b e Ob tai n e d by c on ce n tr a ti n g th e mo t

1
In w i n t e r t i me wa rm w a t e r sh o ul d be a dd e d t o t h e c on d e n e sr to b rin g
t emp e ra t ure w i th in t h e prop er l im i t s .
Y
R LAB OR A T OR Y E XP E RI M E NT S 87

D e termin e th e m e l ti n g p oin t Y i e ld 1 3 grams T h e -

.
,
.
1

de amm oni a Of te n b e c o m e s y e ll ow a n d br ow n on s t an di n g
llin e ch ar a c te r prob ably du e to sl ow r e si n ,

For t his r ea s on th e pr oduc t sh ould n o t b e all ow e d

r e m ai n in th e d e sicca t o r m o r e th an a d ay Th is ch e mic al .

ch an ge c an be n ote d by th e l ow e ri n g Of th e m e l tin g poin t -

.

N OTE S

I . case a a ddi ti u is
In n on t be t w o h ol e d s topp e r
n ot at h an d , u se a -

thr ugh wh i c h p a ss th s t r Of t h e d r ppi g fu

o e e n e l a d t h e s ma ll o n -
nn n

en d f a o ad ap t rn T h e c o d e s e r is th
e . n c t e d w i t h th e ad ap t r
n n en c on e e .

If a
2 . ammo ia c yli d r is n o t ava il abl
n n n th e d y a mmo ia
e e, r n

g as c an b e Ob ta i n e d by b ili g t h e o r di a r y c o c a mmo n iu m h y d no n . on r x

id e s l tio o u sp g n, a d pa ssi g th e vap r s th r ugh a d ryi g

. r . n n o o n

tow r co ta i i g ca lcium o id e c a r e b e i g t aken t ha t a w i de t owe r

e n n n x ,
n

is used .

3 V a
. c uu m d e sic c a t o r A v a cuu m d si c
. c a t o r is li ke a o r d i n a r y e n

d si ca t o r bu t h as a top c c k on a gr o d i s topp r i th e cov r

e c ,
s -
o un -
n e n e .

P u t s ome c al c ium c h l o r i d e or c o c sulfu r ic a cid in t h e b o t t om a d n . n

plac e th e watch glass c on tai i g th e sub sta c e on a suppor t suc h a s a n n n ,

perf orated po r celain disk o a wi r e gau e a c r oss the c st r ic ted pa r t r z ,

on

of th d e sic c a t o r
e G r ea se t h e s top coc k a d th e o t h r gr ou d su r fac e s
.
-
,
n e n .

suction with a h y r ubb e r tube ope the eav ,

n

1 5 3 0 mi n u t e s usua lly Cl os e th e
— fli c es su .

e t ub e b e f r e sh u t ti n g Off th e r o

Wh en r eady t o p th d sicca to r tu r th s top c c k o en e e n e -

o

t o l e t in th e a i sl o w ly t h e r w is th e r ush of a ir may
r , o e

par ticles about .

I t is well t in s r t a s to u t e mp ty bo t tl e i t he co
o e e c ti on b e tween n nn

th d si c c a to r a d t h pump
e e n Th if the r is a y ba ck p r e ssur e
e . en e n

a d th
n w a t e r b gi
e t flo w ba ck i t w i l l be ca ugh t i t h bo tt le an d
e ns o n e

y o u w il l h v e t i m t
a o d is c o e c t b
e e f o r e i t r e a c h e
nns t h de si c c a to r e .

N e r go a w ay a d all ow t he s top co c k t o r ema in open wi th the

ve n -

s uc ti n o o e sp ec i ally wh en a wa t e r p ump is us e d
n, T h chan ge in
-
. e

wat r p r essur e may ca us e the wa te r to be dr awn in an d flood the

e

desicca to r .

is amoun t is too bul ky f or th e usu al prep ara t i on bottl e Han d in a

1
Th .

sampl e s t a t i n g t h e t o t a l yi e l d o n t h e l ab e l a n d u s e t h e ma j or or t i on f or t h e
, p ,

prepara t i on of a c e tal deh yd e i t s e lf in th e n ext e xpe rimen t .

88 L A BOR A T OR Y M A N UA L OF OR GA N I ‘

C CH E M I S T R Y
L i qui ds will e vapor a te ab u t s i t s ve tim s fast
o x o e n e e r in a

de si c c a to r t h n in a n o r di a r y de si c
a to r a
n h wn r ca ,
s S o e c en t ly
W . E . M o r ga n .

T he e fli c ie n c yl vac uum d sic c a tor

Of the co ven ti
n on a e

i c r ea sed if it is p r ided
n c wi th a s
d i l t t b e w i th s t
ov e on n e u ,

a t ta c h e d i t h l ow e r p a r t f t h d i c c a t r
,
n e O e es o .

on, all w a i wh ic h is th r ughly dri d by passag th r ugh s me

o r, o o e e o o

t h sa me ki d of d ryi g ag t us d wi th in th e de sicca t o r t o e n
e n n en e ,

ve ry slowly thr ough th is i n l t tube e .

Q U E S T I ON S
1 . Wri te e qu a ti on s for al l th e chemical ch an ge s i nvolve d in th e
fo rma ti on Of a ce tic ald e hyd e from e thyl alcoh ol by th is
m e thod .

2 . P o i n t ou t in th e ab ove r e a c ti on s wh a t is oxidiz e d
is r e duce d .

Why can n o t a S imple w a te r s olu ti on of s odium di

b e us e d i n s te a d o f on e th a t h a s b ee n a cidifie d wi t h
f u ric a cid ?
Wh a t c aus e s th e gr een c ol or a ti on ? (Comp a re M e
M o d e r n I n o rgani c Ch emis try
Could hydr o chl o ric or a c e tic a cid b e us e d in pl a c e o f
i n ric a cid ?
Why is a droppin g fun n e l n e ce ss a ry ? Why n o t a dd
-

mix ture of dichrom a te an d a lcoh o l all a t on e t ime ?

Why n ot o mi t h e a tin g th e mix tu r e in th e r e a c ti on fl a sk 11
a f t e r th e a lc oh o l a n d t h e dichr om a t e h as a ll b e e n

Why is th e con d e n s e r a t t a ch e d to th e r e a c ti on fl ask h e ld in

a sl a n t i n g p o si ti on ?

Why is it imp or ta n t t o k e ep th e temp e ra ture Of th e c on d en s e r

a t ab o u t 4

Why is it n e ce ss a r y t o abs or b th e a ce tic a ld ehyd e in

drou s e th e r ? W hy is w a t e r n o t us e d in pl a c e Of
A lc oh ol ?
Why is it n e ce ss ary t o k e ep th e e th e r e a l s olu tion o f th
ald e hyd e c o ld ?

HOW d oe s a n h y dro us am mon i a re ac t wi t h a c e tic a ld e hyde

W ri t e e qu a ti on .

D O all a ld e hyd e s r ea c t I n a S i mil a r w a y wh e n t r e a t e d

a n h ydr ous a mm oni a ? Comp a r e f orm a ld e hy de an d
a ld e h yd e .

How d oe s w at er r e ac t wi th fo rm ald ehyde?

 E xpe rime n t No . 18

Th e P r e par ati on of Ac e tal d e h d e y fr om Al deh yde Ammon ia

From th e al de hyd e amm on i a (which S h ou l d b e en tirely fr ee

from e th er) p r ep ar e d in th e pr e c edi n g exp e rim en t pr ep ar e a ce t
a ld e hyd e a s f oll ows : P r ovid e a dis ti l li n g flask wi th a droppi n g
-

fu n n e l c on n e c t wi th a con d en s er an d a tta ch to th e l a tte r a tub e

,

l eadin g t o th e b ott om of a s e c on d dis ti l li n g flas k which

-

mix tur e of ic e an d s al t Diss ol ve 1 0 grams of ald eby

.

in 2 5 cc of w a te r an d a ll ow th is t o dr op i n t o a s ol u
.

o f c on e sulfuric a cid in 2 0 cc of w a t er in th e di
. .

h ea ted wi th boil ing w ate r Dry th e dis till a te wi th

.

chlorid e in the fl ask in which it w as coll e c te d by S h a

a f e w mi n u t e s ,
a n d th en dis till fr om this s ame fl a sk w i t

rem ovin g th e calcium chl orid e usi n g th e pr e cau ti on s n ote d ab ove

,
.

P u r e a c e ta ld e hyd e b oils a t 2 0 8 U s e th e pr oduc t in th e

°
c or .

fo ll owi n g exp erim en t s (K e ep th e produc t in a w ell s topp er ed

.
-

b ottl e in th e ic e box if it is n ot us ed on th e s am e day it is mad e )

-
.

Q UE S T I ONS
1 Wri te all e qu ation s for r e ac ti on s i n volved in the f ormati on
.

Of t h e al d e hyd e fr om i t s ald ehyd e am mon i a .

2 W hy sh ou ld th e ald ehyd e amm on i a us e d b e en tirel y fr e e fr om

.

e the r ?

3 Why. is t h e a ld e hyd e amm on i a diss olv e d in w a t e r b e fo r

b e in g add e d to th e di lu te su l furic a cid ?

S
4
W hy sh ould th e e n d of th e c on d en s e r be ex ten d e d to th
b ottom Of a sm all dis tilli n g fl ask ?
0
1
W hy is t his dis t illi n g fl a sk surr o u n d e d by a fr e e zi n g mix tur e

0 Why is i t n e c e ss a ry t o r e dis t ill th e ald e hyd e ?

“ Co uld a n y o t h e r dryi n g a ge n t b e si d e s c alcium ch l orid e

us e d f or dryi n g th e ace tic ald ehyde ?

0
0
W h a t a dvan t age h a s th e p or ous c alcium ch l orid e ove r fus e
s tick calcium chlorid e in t his cas e ?
9 W hy
. is t h e dryi n g age n t n o t r e m o ve d b e f o r e th e dis ti ll a tio

in t his c a s e whi l e in p r a c tic a lly a l l o th e r exp e rim e n t s

d r yin g agen t is r em ove d b efore th e di s till ati on ?
90
 E xpe rime n t N O . 19

T e s ts f or Al d e h y d e s

1 . S i l ver mi rror -
tes t . M ak e
mmon i acal sol u tion of an a

er n i t r a t e by t r ea ti n g 4 cc o f N / 1 0 silv e r n i t r a t e wi th 3 N
.

n ium hydr oxid e dr op by dr op u n t il t h e pr e cipi t a t e

w hich is firs t f o rm e d jus t r e diss o lv e s A dd a si n gl e dr op of th e .

a ld e hyd e quickly mix by sh aki n g a n d s e t t h e t ub e in th e r a ck

, ,
.

A d e p osi t o f m e ta l l ic silv e r will b e gi n t o f orm a t on c e a n d s oon

mak e s a b eau tiful mirr or I f th e te s t tub e is n ot p e rf e c tly
.
-

cl e an on ly a bl a ck p r e cipi ta t e Of S ilve r will be ob tai n e d I f .

n e c e ss a ry cl e an th e tub e with b oilin g s odium hydroxid e s olu

,

ti on .
1

S ome tim e s a v e ry sm al l amou n t o f di l u te s o dium hydr oxid e

solu ti on mus t be a dd e d in ord er to ge t t h e r e duc ti on Com .

p ar e B en z ald ehyd e e xp e rimen t p 8 2 A mix ture of s odium ,

. 1 .

hydroxid e an d silve r n i t r a te con s ti tu te s TOll en s r e agen t for ’

al d ehyd e s .

D O n o t h e a t th e si l v e r s ol u ti on or l e t it s t an d f or a l on g
e si n c e e xpl o siv e c omp ou n ds a re f orme d
, S ee S mi th In .
,

p 7 5 3 ; Alfred Ti n gl e Amm on ia cal S ilve r oxid e

.
,

J ou rn I n d an d E n g Chem 11
”
on , . .
379;
. a n d E J ,
. .

man n i bid 11 ,
.
, 8 9 3 ; a ls o n o te 8 8 4 , ,
.

2 .Redu c ti on of F ehl i n g s S ol u tion M ix 3 cc o f e a ch Of th e

’
. .

0 p or t i on s o f F e h li n g s S ol u ti on copp e r h al f a n d a lka
’

e t a r t r a t e h al f an d bri n g t h e c l e a r d e ep b l u e s o lu t i on t o a ,

N o te wh e th e r a pr e cipi ta te is fo rm ed I f n o t a dd a .
,

th e ald eh yd e a n d b oil f or a mi n u t e A y el l ow pr e cipi ta te .

Of cupr ous hydr oxid e is g en e r ally f o rm e d a t firs t an d this is

rapi dly con ve r te d i n to brigh t re d c u prous oxid e I f th e am ou n t .

of re duc ti on is sm all th e cuprous oxid e s om e tim e s can n ot be s een

a f t e r t h e s olu ti on h as b e e n a l l ow e d t o s tan d l o n g e n ou h
g
t o s e ttl e ou t Or th e s olu ti on c an b e fil te r e d
.
N o te th e .

duri n g th e b oili n g a n d c omp ar e te s t 4, .

91
92 LABOR AT OR Y M AN UAL OF OR GA N I C CH E M I S T R Y
F e hlin g s s olu ti on is k ep t in tw o p ar t s b e ca use it gradu ally
’

d e te ri or a t e s o n s t a n di n g a f t e r b e i n g mix e d .

3 .P o l y m e r i za ti on T O a li t t l e o f t.h e a ld e hyd e a d d a S i n gl e

drop of con c sulfuric a cid on a s tirrin g rod ( Care "

.
) Wh a t is .

form e d ?
4 .R es i n F o r m a ti on G e n tly h e a t a li tt l e a ld e hyd e an d a
.

f ew dr ops o f a c on c s olu ti on Of s o dium hydr oxid e . .

5 .S c h ifi s A l
’
d eh y de T es t S chi ff s a ld e hyd e r
. e a g e n
’
t c on
sis t s Of a v e ry di l u te s ol u ti on Of fuchsi n e d e col oriz e d wi th sul
f u rou s a cid I t is als o kn ow n a s
. Fu c h s in e sulfurous a cid -

r eagen t an d is furn ish e d r eady for u s e by th e s tockr oom

,
”
.

A dd a dr op of th e a l d e h yd e t o 5 cc o f w a te r a n d th en a dd .

a d r op o f th e r e ag en t T h e d e v e l opm e n t of th e o ri gin al r e ddish

.

vi ol e t col or of th e fuchsin e in dic ate s th e pre sen ce of a n ald e

hyd e .

S chi ff s r eag en t c an be pr ep a r e d by dissolvin g gr am o f

’

pur e fuchsi n e or ros ani li n e (in th e f orm Of th e hydro chl orid e or

a c e t a t e ) in 1 5 cc o f w a t e r a n d p a ssi n g in sulfur dioxid e u n
. til th e
s olu tion is s aturate d This r e quir e s bu t a f ew mi n u te s a n d .

th e s olu ti on will be co l or l e ss pr o vid e d pu re r o s ani li n e or i ts ,

s al t w e r e use d Th en dilu te to 2 00 cc I t S h ou ld b e k ep t in a
. .

d ark col or e d gl ass s topp ere d b o ttl e I f th e b ot tl e is n ot prop e rly

- -
.

s topp e re d th e liquid will gradu ally l o s e sulfur di oxid e an d th en

o f c ours e th e col or will r e tur n e v en b e f or e a n y a ld e hyd e is a dd e d .

D o n o t b oil the r eag e n t "W hy ? Wh a t w ould h app en if

a w eakly al k a li n e subs t a n c e w as a dd e d t o th e r e a g en t ?

T h e r ea c ti on s in th e S chi ff s Ald ehyd e T e s t ar e n ot c ompl e te ly

’

u n d e r s tood T h e m an n e r in which th e ald e hyd e r em ove s th e

.

sulfurous a cid is p r ob ably simil ar to th e r e ac tio n Of an a ld ehyd

a n d sodi u m bis ul fite S e e A c e ton e p 9 8 .
,
. .

Q U E S T I ON S
1 . Discuss th e re a c ti on s i n volve d wh en th e ac etic ald ehyd e i
m ix e d wi th ammon i a ca l S ilve r n i t r a t e .

2 . Wh a t is th e pu r p o s e of th e alk ali in this t e s t f or a ld ehyd e

( S t i e gli t z Q u a li ta t,
iv e
.
C h e m ic a l A n a lysis I 2 9 0 ,
”
,

I s i t n e c e ss a ry t o e mpl oy th e ni tric a cid s al t s for t his oxid

 x
E pe rime n t N o . 20

H YD R OL Y S I S OF M E T HY L E NE D IE THE R S (A C E T A L S)

M e th ylal 1

1 D oe s its Od or r e s emble tha t of the e th e rs ? T O wh at

.

a lc oh ols a r e t h e s e e t h e rs r e l a t e d ?

2 TO 3 drops of m e thyla l in a t e s t tub e a dd 2 drops of con c

.
-
.

sulfuric a cid H ea t gen tly ove r a sm all fl am e u n til the liquid

.

b e gi n s to b oil an d th en all ow to cool Wh a t is th e whi te s olid

,
.

t h a t is d ep o si t e d on th e w a lls o f t li e t ub e ? N o te t h e Od o r of th e
g a s e v o lv e d ( C a r. e "
) O u t li n e th e s t e ps in t h e r ea c t i on s o f
”

t his exp e rim e n t .

3 R. e p ea t t h e a b o v e e xp e rim e n t usi n g dilu t e sulfuric

,
a cid .

An y whi te s olid f o rm e d ? Od o r ?
4 Try
. t h e a c t i on O f dilu t e so di u m hydr o xid e solu t i on on

m e thylal .

5 W. h a t is an o r t h o e s t e r ? 2
W h a-
t is f o rm e d wh e n an

o r t h o e s t e r is w arm e d wi th an a lc o h o lic s olu t i on o f p o t a ssium

-

hydroxid e ?
6 D oe s m e thyl a l r e duc e F e hli n g s s o lu ti on or amm on i a ca l
’
.
,

S ilv e r ni tr a t e ? (S e e u n d e r A c e t a ld e hyd e p ,
.

Q U E S T I ON S
1 . Wri t e e qu ation s f or r e a c tion s i n volve d i n th e ch emica l
ch an ge p r o duce d by th e a c ti on of c on e sulfuric a cid on .

m e t hyl a l .

2 . Wh a t is p o lyme riz a tion ? S how by s truc tu r e h ow this p ol ym

e riz a t io n o f f o rm a ld e hyd e t o p a r a ld e hyd e diff e rs fr om a

p olym e riz a t ion like fo rm a ld ehyd e to fo r m os e .

M th yl l b ils t
1
e a o a

Ri c h te r s r isc h e Ch emi e ,
“
Au fla ge Vol I ,
2 ’
O ga n 11 . . 27
3 3
,
16.

94
 LA BOR A T OR Y E X PE RIM ENT S 95

Wh at is th e s truc ture of the form ald ehyd e in th e wa te r

s olu ti on Ob tain e d wh en sulfuric a cid re a c t s wi th th e
m e thyl al ?
How is m e t hyl a l fo rm e d ? T w o m e t h ods .

S h ow h ow i t is r e l a t e d t o e th e rs by its b e h a vi o r wh e n hydro
l yz e d .

Ca n di e thyl e th e r b e hydr o lyz e d by sulphuric a cid ?

Can a qu eous a l k a li ca us e hydro lysis of m e t hy l a l o r e t hyl e t h e r ?
Of wh a t a lc oh o l is m e thyl a l an e t h e r ? D oe s it e xis t ? Com
p ar e chloral hydrate .
 x r
E p e im e n t N o . 21:

Fo rm al d e hyd e
1. Dissolve 2 drops Of me thyl a lcoh ol in 3 cc of wa te r in a .

sm all te s t tub e (N o -
M a k e a c omp a c t spi r a l Of fin e copp e r
.

wi r e by W in ding it a roun d a gl ass rod T h e spira l should be ab ou t .

2 c m l on g a n d sh ould h a v e a s t r a igh t pi e c e a b ou t 2 0 cm l o n g
. . .

Oxidiz e th e spir a l by m ovi n g it r apidly t hr ough a B u n s e n fl a me ,

a n d plu n g e t h e re d h o t wir e i n t o th e a lc oh o l s o lu t i on R ep e a t
-
.

this Op e r a t i o n s e v e r a l t im e s .

P our th e s olu ti on fr om th e s olid p articl e s in to an o th e r sm a ll

t e s t t ub e a n d a d d 1 dr op Of a fr e sh 0 5 p e r c e n t s o lu t i on o f re
-
,
.

s o r c in ol Ca r e fully p our t his s olu ti on d own th e sid e s Of a s e c on d

.
1

t e s t tub e c on ta i n i n g a b ou t 5 cc of c on e sulfuric a cid

- . I f th e . .

se con d tub e is prop e rly i n clin e d th e mix ture will form a dis tin c t .

l aye r upon th e surfa ce of th e a cid .

A r e d z on e sligh t ly V i ol e t in c ol o r will app ea r a n d ab ov e th e

, , ,

z on e th e re will be a ligh t floc c u l en t pre cipi ta te This r ea c ti on .

is ch ara c te ris tic of f orm ald ehyd e ; o th e r a ld e hyd e s do n o t S h ow

t his b e h a vi o r T h e c o mp o si t i on o f th e c o l o r e d subs ta n c e a n d
.

Of th e pr e cipi t a t e is n o t w e ll u n d e r s t oo d .

( Repri nted wi th per mi s s i on f r om J on es A L a bora tor y Ou tl i n e of Organ ic

,

Chemi s try
”
p,
.

2E v ap o r a te 5 cc o f
. fo r m a lin .
( mm e rcia l 40 p er c en t
c o

s olu tion of f o rm ald e hyd e) t o d r yn e ss on th e w a t e r —b a th un d e r ,

th e h oo d Wh a t is th e r e sidu e ?
.

3 P r e
.
p ar a ti o n of H e x a m e th yl e n e t e tr a mi n e . In a roun d
b ottom e d fl a sk mix 2 5 cc Of fo rm a li n a n d .
“ ”
15 cc . of c on e .

1 re sorc in ol solu t ion is a ll ow e d t o s ta n d f o r some t ime it gra du a lly d e v e lops

I f th e
a b ro w n ish flo c c u l e n t pre c ipi ta t e a n d t h e n i t is w o r t h l e ss f o t h is t e s t
, r .

96
 E xpe rime n t N o . 22

Ac e ton e

1 . M ix 5 ccc . wi th 7 cc Of a s a tura t e d solu ti on of

o f a e t on e .

s odium bis u l fite S h ak e vig o ro usly N ote th e h e a t d eve l ope d

1
. . .

Wh a t is th e produc t th a t s ep ara tes ? H ow may a ce ton e b e

7
re gen e ra te d from it ? H ow is this r e a c ti on us e d in an alysis ?
D O a l l k e t on e s r e sp on d t o t hi s t e s t ? H ow d oe s K CN r e a c t wi th
l th e bisu l fite addi ti on produc t ?
2 Try the a c ti on of th e fuchsin e sulfurous a cid r eagen t on
.
-

a c e t on e .

3 D oe
. s a c e t o n e r e duc e F e hli n g s solu t i’
on or a n a mm o n i a,
ca l
solu tion of silve r n i t ra te ?
*
4 Wri t
. e t h e s t ruc t ur e o f d ib e nz a l a c e t o n e (d ib e n z
y

N a c e ton e ) ( C o mp . a r e P e rki n a n d Kippi n g “

O r g a n ic C h e mi
,

l
p . H o w c a n i t b e f o rm e d ? E xpl a i n th e r e a c t i o n

pr ep arati on Wh a t is its signi fican ce in organ ic an aly tical ch

.

i s t ry ?
5.H ow pr ep are i od oform from a ce ton e ? I s
c an y ou

r ea c ti on ch ara cte ris tic Of mos t k e ton e s whi ch con tain

CH 3 CO gr oup ?

1
Th esa tura t e d s olu t i on of sod ium bis u l fite is prepa red by mea n s of s od iu
h yd roxi d e s o lu t i on a n d sulfur d i oxi d e or by p a ssi n g sulfur d i oxi d e i n to a mixtu
,

o f s od iu m b i c a rb on a t e in t h re e p a r t s o f w a t e r u n t il t h e s o lu t i on s me lls s t ron gly

t h e ga s On l on g s ta n d i n g u n l e ss prop e rly s to pp e re d it is sl o w ly c on v e r
.

th e sulf a t e T h is c a n gen e ra lly be n o t i c ed by l o ss o f th e y e ll ow is h c ol or

.

sa tura te d solu ti o n a n d by th e pre se n c e o f a w h i t e s e d imen t I t w ill th en n o l on ge .

giv e t h e c rys ta llin e a dd i t i on pro d u c t w i th a c e t on e e t c

-
.
,

N e ed n o t be s t u d i ed by s tu d eift s in th e S h or t c o urse
“ ”
.
 E xpe rime n t No . 23

ORMA T I ON OF A KE T ONE B Y T HE OX ID AT I ON OF A S E C ON D AR Y
AL
Q H OL A N D T HE F ORMA T I ON OF A KE T OX IME

P r e par ati on of l s M e n th on e f ro m l -M e n th ol

P our 3 cc (
.n o mor e ) o f c on e sulfu
. r ic a cid i n t o 4 0 cc O f .

wate r a n d di ssolve 5 grams of sodium dichrom a te in thi s s olu ti on

{
.

Tran sfe r to a s mal l gl a ss s topp e r e d b ottle an d add 5 grams of

-
,

d r e d l m e n th o l S h k fr qu t ly duri g th x t h lf
gp ow e a e en n e n e a
-
e

{
.

hour an d l e t s tan d ove rni gh t or l on ge r Wh en th e m ix ture .

is all ow e d to s tan d th e s o lid lumps S h ould be in con ta c t wi th

liqui d an d n ot s tickin g to th e walls Of th e b ottle ab ove
liquid Th e s e d ark colore d i n soluble m ass e s pr ob ably c on
.
-
,

Oi th e e s te r o f m en t h o l an d chromic a cid which is firs t

an d th e y gr a du a lly dis appe a r l ea vin g a d ark b u t cl ea r

,

e m e n t h on e fl o a ti n g as an oil on th e sur f a c e .

tur e in a s e p a r a t ory fu nn e l wi th ab o u t 2 5 cc .

Fil te r th e e th e r s olu t ion in to a sm a ll w eigh e d b eake r

an d e v ap or a t e th e e t h e r by m e an s o f w a r m w a t e r S upp or t .

an in ve r t e d fu n n e l o v e r t h e b eak e r an d c on n e c t wi t h th e suc ti on

to c arry aw ay th e e th e r v ap ors . A s s oon a s th e fum e s of e th e r

are n o l on g e r e vid en t a s sh o wn by th e Od o r co ol an d th en ,

de te rmin e th e yi e ld of crud e m en th on e (ab ou t grams) I t is .

som ewh a t vol a tile a t th e o rdin ary temp e ra tur e an d pressure ,

an d th e r e f o r e it sh ould n o t b e h e a t e d t oo l on g .

An e xce ss of sulfuric a cid mus t b e av o id e d si n ce i t gr a du a lly

s th e le vo comp oun d in to th e d ex tro vari e ty M en thon e
- -
.

on e of th e chi e f c on s t i t u e n t s of th e Oil o f p epp e rmin t It .

a c ol orl e ss liquid b oili n g a t 1 09 a t 3 6 mm

°
.

I t n e e d n ot be fur th e r purifi e d for th e f oll owin g exp e rim en t .

99
100 LA BOR AT ORY M A N UA L OF OR G A NI C CH EM I S T R Y

P r e par ati on of l M e n th on e O i
- x me —
f r om l M e n thon e

Diss olve 2 gr ams Of th e crud e m en thon e in three tim e s its

w e igh t Of ab ou t 9 0 pe r ce n t a lcoh ol (s p gr approxim a te ly . .
,

in a sm all b eak e r (N O A dd an a m ou n t Of p o wd e r e d h y drox

.

l amin e hydr o chl o rid e e qu a l t o t im e s t h e t h e o r e t ic a l a m ou n t

y
re quir e d by th e e qu at i on I t will n o t all diss olve Th en
“

. .
,

durin g ten min u te s a dd in p or ti on s wi th s tirrin g sligh tly m ore

,
.

th an th e t h eo r e t ic a l qu a n t i t y Of s odium hyd r og e n c a rb on a te
r e quir e d to n e u t r a liz e th e hydr o chl o ric a cid o f th e firs t
s al t an d fre e th e hyd r oxylamin e L e t s tan d fo r thir ty mi n u te s .

wi th o cca si on a l s tir r i n g P our th e mix tu r e i n to 7 5 cc Of cold

. .

wa te r an d s tir vigo ro usly T h e oxi me s ep ara t e s .

as a n Oil o r a whi t e s e mi s o lid m a ss which s oon s o lidifie -

fur th e r if n e ce ss a ry t o h elp s olidific a t i on Fil te r wi th .

Diss olve the p r o duc t in h o t approxim a te ly 5 0 p e r cen t ,

5 0 cc f o
. r e a ch g r a m fil t e r whil e h o t if n e c e ss a ry t o
,

a n y i n s o lubl e p a r t icl e s a n d s e t a sid e f o r crys ta l l iz a t i on

,
.

s e ttin g a sid e cove r th e b eak e r wi th a wa t ch gl ass A f te r .

c r op o f crys t als h as b e en fil ter e d Off a s e c on d

Ob t a i n e d by l o n g e r s t a n di n g Whi te n e e dl e s Of a .

p e rsis t in g Od or ar e Ob t ain e d which m e l t a t

m ay b e dri e d by l e t t i n g i t s t a n d o v e rn igh t o n a cl
t il e c o ve r e d wi th a w a t ch gl a ss I n t his w a y t h e ir crys .

shap e is pre s e rve d Y i eld 8 0 per ce n t o f th e th eory

.
,

Try th e a c ti on Of a dilu te s olu ti on Of s odium hyd r oxid e

sm all am oun t Of th e oxim e .

NOT E S

1 . Wh en the xime is hydr oly d w i th dilut sulf ur ic ac id

o ze e

an gl e Of r o ta t io n
f th e r e ul ti g me th o e is c ha ge d
o s n n n n .

2 L ik mos t t e rp en c mpou d s me th o e
. e e ime is some o n n n ox

v latil a d th r efor e h uld ot b lef t in th p

o e n e S o i n e e o e n or n

d sic c a t o r u d r d imi ish d p r e ssu r f o a y l e gth f t im

e n e n e e r n n O e .
 x
E pe rime n t No . 24

F OR MA T I ON OF A N A CID CH L OR ID E F R OM THE A CI D

P r e parat i on of A c e t l Ch y l o ri d e fr om Ac e t ic Ac d i
T he pp ara tus in this exp e r im en t con sis t s of a 6 0 cc di s
a .

li n g flas k provid e d wi th a droppi n g fu n n el (Fig 6 p

-
,
-
.
,
.

ha t tac h ed to a c on d en s e r A s e c on d dis t illi n g flas k o f th e s am e

.
-

cap aci ty tigh tly con n e c te d wi th th e con d en s e r (if a good cork

con n e c tio n c an n o t be m ad e u s e a pi e ce of rubb er tu bi n g as y ou
,

w ould a b or e d cork ) s e rv e s as th e r e ceive r th e ou tl e t tub e b ei n g ,

con n e c ted to a cal ciu m chl orid e tub e Th e calcium chl orid e
1
.

in th e t ub e is pr o te c t e d a t ea ch en d wi th a plug of gl a ss
cot ton S in ce th e r e ce ivi n g fl a sk is us ed l a te r a s the d
.

fl a sk wi th ou t tran sfe r ri n g th e dis till a te a th e rm om e te r an ,

fi ttin g cork sh ould be r e ady b ef or e th e op er a ti on is s tar ted .

A ll th e app ar a t us mus t b e p e rf e c tly dry a n d th e c on n e c ti on sh ou l d

be s o m ad e th a t th e pr oduc t d oe s n o t c om e in c on t a c t wi th a n y
cork or rubb er U s e c ork s topp ers th r ou gh ou t e xc ep t as n ote d
.
,

ab ov e T h e e xp e rim en t mus t b e c arri e d o u t u n der a hood or th e

.
,

calcium chlorid e t ub e con n e c te d wi th a tub e op en i n g jus t

a bove th e surf a c e o f a dilu t e s o dium hydr oxid e So lu ti o n c on t ai n e d

in a b ottl e a n d th e fum e s th en l e d i n t o th e d r a f t pip e T he .

a c e tyl chl o rid e fum e s in th e a ir b e i n g d e c omp o s e d by m o is t ur e

,

in to a ce tic a cid an d hydro chl oric a cid Care mus t be exerc i s ed i n .

handl i n g both reagen ts a n d p r odu c t to keep them fr om the s ki n a n d

to avoid i n ha l i n g the
p va ors chl o
. rid ,
A c e tyl
e a tt a cks b o t h rubb e r

a n d c o rk ; t h e r e f o r e t h e a pp a r a t us sh o uld be disc on n e c t e d as s oon

a s th e e xp e rim e n t is c ompl e t e d a n d th e pr oduc t sh ould b e

,

1
Be r ful th a t
ca e th e l iu m c h l orid e t ube
ca c d oe s n ot bec ome s topp ed up du r
in g th e d is tillati on .
 LABOR AT OR Y E XPE RI ME NT S 103

kep t in s eal e d b ott l e i n s tea d of th e ordi n ary sp e cim en

a
1

b ot tl e a l th ough it c an be k ep t f or a f ew d ays in a gl ass

,

s topp er e d b ot tl e .

1 A c e tyl chl orid e h a s a high v ap or pr e ssur e a n d t h e r e f or e g oo d

corks mus t be us e d an d th e j oin t s m ad e tigh t o th e rwis e s eri ous ,

f oss es will o ccur I t is b e s t t o pl a n t o p erf orm th e exp e rim en t

.

duri n g on e l ab ora tory p eri od .

Add 1 2 cc o f g l a ci a l a c e tic a cid t o th e dis ti ll in g flas k which

.
-
,

is imm e rs ed in c old wa ter in a b e ake r Th en a dd sl owly fr o m th e .

dr oppi n g fu n n e l -
cc o f ph osph orus trichlorid e Wh en al l
. .

t his h as b e e n a dd e d mix th e l iqu ids by g e n t ly sh aki n g t h e

,

fl ask an d all ow t o s tan d f or ab ou t on e h our Th en w a rm th e .

’

w a ter to 40 5 an d c on ti n u e th e h ea ti n g a t this temp e ra

— 0 ° °

f or a sh or t tim e T h e l iquid which w as h om og en eous b e f or e

.
,

n
g fi n a lly s ep a r a t e s i n t o tw o l ay e r s ; th e upp e r l a y e r c on sis t s
,

l y of th e a c e tyl chl o rid e a n d th e l ow e r of ph o sph or o us

’

S l ow l y h ea t th e w a t e r t o b oili n g u n t il n o thin g fur th e r

ls T h e dis till a te con tai n e d in th e s am e dis till i n g flas k
.
-
,

provid ed wi th th e th e rm om e t e r is c a re fu l ly redis til l ed , .

ti on th a t dis ti l l s b e tw e e n 5 2 an d 5 5 in a r e c e iv e r
° °

pro te c t ed wi th a calcium chl orid e tub e or wi th abs orb en t cotton ,

on o f a ir .

is a c ol o rl e ss liqu id wi th a pu n g en t Od or i t ,

c on t ac t wi th m ois t air ; b p sp gr at . . . .

A f t e r th e y i e l d h as b ee n d e te rmi n e d p e rf o rm th e f o l l owi n g
t tub e e xp e rim e n t s :
-

NOT E

T he r e a c t i on s wi th a c tyl c hl ri de a e usually ve ry vigor ous

e o r .

re , wh n c a rryi g o t p r im t s w i th it a r should be
e n u ex e en c e

t e s t tub is h l d i
-
u h p i t i o t h a t it c o t t s
e e n s c a os n s n en

t i to t h e fac e of t h e e p e r i me t e r o of a yo e e ls e
n x n r n n .

1 . Add a f ew drops o f a ce tyl chl orid e t o ab ou t 3 cc of wa t e r .

a te s t tub e
-
. T h e a c e tyl chl orid e si n ks t o t h e b o tt om Of th e

1
A thi n -w a ll ed bo t t l e
sof t gl a ss w i th an of e xten d ed n ec k wh c i h c an be sea l ed
a s d e s c ri bed a t th e en d of thi s e xp e rimen t .
 104 LA BOR AT OR Y M A NUAL O F OR G AN I C CH E M I ST R Y

t ub e bu t on sh aki n g r apidly disso lve s a n d h e a t is e vo lve d

, ,

W h a t a r e th e p ro duc t s ?
2 . T o ab ou t cc of e thyl alc oh ol a dd cc of a c e tyl chl orid e
1 . 1 .

drop by d r op c oolin g the te s t tub e u n d e r th e t ap Th en add ;

,
-
.

a n e qu a l v olum e o f w a t e r th e t ub e b e i n g c o ol e d a s b e f o r e
, M ak e .

w eakly alk ali n e wi th s odium carb on a te s olu ti on an d a dd c omm on

s al t u n til n o m ore dissolve s Wh a t is th e pl e as an .

subs ta n ce th at s ep ara te s ou t as a m obile l aye r on th e

t h e w a t e r solu ti on ?

3 . To 1 cc o f a.n ili n e a d d 1 cc of a c e t yl chl o rid

. e

drop A vigorous r e ac ti on occurs an d a s olid s ep ara te s

.
, .

t h e mix tur e wi t h w a t e r an d a dd ab ou t fiv e t im e s i ts v ol
w a te r Wh a t subs tan ce is form e d ? Wh at is its t ra d e
.

R e crys t alliz e by diss ol vi n g it in h o t w a t e r an d a ll o wi n g th e

s olu ti on to cool I t is ob t ain e d in l e afl e t s which m e l t a t 1 1 4
.
°

c or . D e te rmi n e th e m el tin g poi n t ; s ee E xp t 1 2 p 5 8

-
.
,
. .

Wri t e e qu ati on s f or all th e ab ove r ea c ti on s .

P l a c e th e r em ain d e r Of th e pr o duc t in a s eali n g tub e or b ot tle

a n d s ea l Off t h e n e ck by m ean s o f a s mal l bl a s t l amp fl am e On ,
-
.

a cc o u n t o f th e v o l a t ili t y o f th e a c e t yl chlorid e th e low e r p ar t of

t h e s e a li n g t ub e mus t b e k e p t c o ol by m e an s of a clo th s at ur a te d
wi th ic e wa te r To tal yie ld 1 2 1 4 grams
.
—
,
.

N OT E

For xcelle t d isc ussion of the r eact ion be tween a ce tic ac i d

an e n

an d phosph orus t r ichl or i de s ee Br o ks J ou n A mer Chem S oc

,
o ,
r . . . .
,

34 —
49 2 9 .

Q UE S TI ONS
Wri te th e e qu ati on for t his rea c t i on .

Wh en is P Cl us e d t o r e pl a ce OH groups wi t h Cl ?
5

Wh at is th e p r oduc t remai n in g in th e fi r s t fl a sk ?
I s th e s e c on d e qu a t i on o n p 1 4 2 in G a tt e rman n c orr e c t ?
.

A cc o u n t f or t h e H Cl ga s .

Wh at tw o Obj e c t i on s ar e t he re to th e u se of P CI5 in c e r t ain

ca se s ?
Why doe s a ce tyl chlorid e fum e in th e air ?
 E xpe rime n t No . 25

F ORMA T I ON OF AN E S TE R F R OM T HE A L C OH O L A ND THE

P r e par ation of y
E th l Ac e ta te

To sm all dis tillin g flas k c on n e c te d wi th a con den s e r

a -

a mix t ur e Of 1 0 cc o f a bs olu t e e t hyl a lc o h o l a n d 1 2 cc Of c

. .

sulfuric a cid I n s e r t th e s te m of a droppin g fu nn e l in to

.
-

Of th e fl a sk an d l e t th e e n d r ea ch bel ow t h e surf a c e

H e a t th e fl a sk in an Oil b a t h 1
Wh en the tempe ra ture of th
-
.

re a ch es e o f 1 5 cc o f abs o lu t e a lc oh ol .

t o dr op sl owly i n t o th e liquid ,

a s s oo n as th e r e a c t i on pr o c ee ds r e gul a rly a dd th e mix tur e a t

a b ou t th e s a m e r a t e a t which t h e pr o duc t s dis till Ke ep th e .

t e mpe r a tur e a t a b ou t 1 4 5 — 1 50 u n til all th e m ix ture h as

° °

a dd e d Wh en n o m or e dis tills ove r t r ea t th e dis till ate in a b

.

O w ith a c on c e n t r a t e d s olu t i on o f s o dium ca rb on a te u n til t h e r e

n o fur t h e r e f f e rv e sc en c e s ep a r a te th e l aye rs in a s ep ara to

funn el an d wa sh the upp e r lay e r wi th ab ou t its ow n volum e
,

s a tura te d s al t s olu ti on S ep a ra t e a g a i n dry wi th

.
,

s odium sulfa te or fus e d p ota ssium ca rb on a te an d dis ti ,

a c e t a t e b oils a t i t s sp e cific gr a vi t y is at a n d it i

s oluble 1 p ar t in 1 7 p ar t s of w ate r a t 1 7 Y i e ld 1 1 gram .

,

slowe r the distill atio

T he n in th e fi r s t r e a c t i o n th e b e t t e r t h e

yi l d will b I t will be oti

e e . n c e d t ha t p r a c t i c ally n o thin g d is tills ove r
u til the t mpe ra tur e ha ah
n e s n os t r ea c h e d 14

H ydr o s is of an E s ter

f
sm all fl a sk wi th r eflux con d en s e r a t ta ch e d h e a t f or
In a

min u te s 5 cc Of e t hyl a c e ta te 50 cc Of wa te r an d 2 g r am
l
“
“f
1 . .
, ,

A sh ll w ir dish d r p s d il
1
a o on v i t f th is purp s
an a e - ee O a r e c on e n en or o e .

d is c ussi on o f h ea tin g ba th s , -
s ee f oo t n ot e p
-
, .
79 .

106
 LA BOR AT OR Y E X P E R I M E NT S
hydroxid e Th en di s till ove r ab ou t h alf the liquid
. .

e
d is t ill a t e f o r a lc o h o l wi t h p o t a ssium dichr o m a t e ( s e e

R ea c ti on s of A lco h ols p E mp t y th e r e m a i n d e r
“ ”
.
,

igin al s o lu ti on in t o a p orc e l a i n di sh a n d e vap or a t e t o

Diss olve the r e sidu e in water an d a cidify wi th sul
dor .

f or th e a cid by a ch e mic a l m e th o d ?
a d e riv a t iv e o f t h e a lc o h ol t o

y our qu ali ta tive fin din gs (c omp ar e m e thyl e s te r of 3 5 .

trobe nz oic a cid p ,

.

Q UE S T I ONS
I S it n e c e ss a ry t o u s e abs olu te a lcoh o l in th e pr ep a r a t i on
o f e t hyl a c e t a t e ?

Could hydr o chl o ric a cid b e us e d in pl a c e o f c on c sulfuric .

a cid ? dilu t e sulfuric a cid ? E xpl a i n .

Wh a t w ould b e t h e eff e c t if s om e w a t e r w a s a dd e d t o this

r ea c t i on mix ture ? or m e thyl a lcoh ol ? or e t hylen e ?
Would a n y e thyl a ce ta te b e f orm e d wi t h ou t th e pre s en ce Of
sulfu r ic a cid ? I f an y h ow much comp a re d to th e yi e ld
,

whe n sulfuric a cid is pre se n t ?

Wh at is th e Obj e ct Of ke epi n g th e t emp e ra tur e b e tw een 1 4 5 °

an d Wh a t h app e n s wh en th e t e mp e r a t ure is r a is e d ?
Would it m ake a n y diff e re n ce if a m ix t u r e Of 2 5 cc o f a ce t ic .

a cid a n d 5 0 cc Of a lc o h o l w a s r u n i n t o t h e r e a c t i on fl a sk
.

in s te a d of a mix tu r e of 2 5 cc of e a ch ? .

Wh y is this mix tu r e i n t r o duc e d t h r ou gh a dr oppi n g fu n n e l -

,

a n d l e d u n der n ea th t h e su r f a c e Of t h e s o lu t i o n ?

I s th e yi e ld of e t hyl a c e t a t e a ff e c t e d i n a n y w ay by dis
t illi n g Off th e e t hyl a c e t a t e a s i t is b e i n g f orm e d ?
Why is th e dis till a te t rea t e d wi th so dium ca rb on a te ? Could
s odium hydroxid e solu ti on be us e d i n s tead ?
Why is th e e s t e r w a sh e d wi th s a l t s o lu ti on i n s t e a d of w a te r ?
W hy cann o t o th e r dryi n g a ge n t s such a s c a lcium Chl o rid e
,

an d s o lid p o t a ssium hydr oxid e b e us e d f or t h e dryi n g o f

,

t h e e t hyl a c e t a t e ?
S o lve th e pr obl e ms o n p 1 6 1 in G a tt e rma n n
.
,
.

P oi n t o u t a l l th e c on di t i on s t h a t a re us e d t o give a m a ximum
yi e ld of th e e s te r .

Wh a t w o uld y ou e xp e c t t o h app e n wh e n m e thyl a c e ta te is

3

h ea te d wi th d r y hydrogen chlorid e ? wi th an a lcoh o li c V

s olu ti on o f hyd r oge n chlo ride ?
 E xpe ri me n t N o . 26

Hydr olys i s (S apon ific ation ) of B utte r

Dissolve 2 grams of s odium hydroxid e in 2 cc of w ater I n . .

p orce lai n dish such as a ca ss e rol e (n o t a gl ass b eak e r Why

, .

h ea t 1 0 grams of bu tte r u n til it m el t s add th e ,

s olu ti on of s odium h ydr oxid e an d c on ti n u e th e bea ti

,

wi th good s tirri n g u n til th e mix ture b e com e s of a

S is te n cy . P o ur i t i n t o 1 5 cc of w a t e r a n d t r an sf e r this s olu ti on
.

t o a dis til l i n g flas k

-
. A cidify wi th 2 0 cc Of dilu t e sulfuric a cid
.

( 1 p a r t o f a cid t o 4 o f w a t e r ) a n d
,
dis t il l o v e r a b o u t 1 5 cc .

a . Te s t th e rea c ti on of th e dis till a te wi th n eu tral li tmus .

b T o wh a t is th e Od or of th e dis til l a te ch i efly du e ?

.

c
. Of wh a t d oe s th e oil y r e sidu e in th e fl a sk con sis t ?
o

c ould y ou pr ove it ?
d R em ov e th e Oi l y l ay e r w a sh it s e ve r al tim e s wi th
.
,

a n d s ee if i t diss olv e s in dilu t e s o di u m h ydr oxi d e s o l

A dd a dr op of dilu te a c e tic a cid t o th e s olu ti o n t hus m a d e .

e
. T e s t a sm all p or ti on Of bu tte r f or u n s a tura te d r a dic al
wi th a solu ti on of bromi n e in c arb on te tra chlorid e .

Q UES T I ONS
Wh at is a f a t ? a f a tty Oil ? a mi n e ral Oil ?
W h a t a re s oa ps an d h ow a re th e y p r ep a re d ?
I n y our e xp e rim e n t wh a t s olu ti on c o n t ai n e d th e s oaps ?
Wh a t is th e by pr oduc t wh e n fa t s a re s apon ifie d ? H ow is i
-

purifi e d ?
Wh a t is ran cid bu tte r ? E xpl ai n .

Wh a t is mean t by th e s ap on ific a tion n umb e r

“
o

Wh a t a dvan tage h as an alcoh olic s olu ti on Of po ta ssium h

d r oxid e o ve r a n a q u e ous s o lu ti on in s apo n ifyi n g f a t s ?
H ow is th e n umb e r o f hyd r oxyl gr oups in a c o mp o u n d d e te
min e d ?
Not required f or s tud y by s tu den t s in th e sh or t co urse .

108
 E pe ri x me nt No . 27

I S OLA T I ON AN D S TU D Y OF A N A T U RA L P R OD U CT

L e c th i in from E gg-yo k l

Gri n d th e yolk of on e h ard b oil e d e gg wi th 50 cc of e the r -

. .

Fil ter an d w a sh th e s olid ma teri al twice wi th 1 0 cc of e th e r .

Discard th e sol id m a teri al E vap ora te th e combi n e d e th e r .

t r a c t s an d w a shi n gs on th e s t eam b a th E x tr a c t th is r e s idu -

.

twic e wi th h ot a lc ohol usi n g 1 0 cc e a ch tim e ,

P our off th . .

alc oh o l fr om t h e h ea vy Oil th r ou gh a sm all fil te r E v ap ora t .

Off th e alc oh o l fr om th e alc o h oli c fil t r a t e diss o lv e th e r e si ,

1 0 cc o f c ol d e th e r
. a n d a dd 2 0 cc o f a c e t on e
, S tir u n . .

p ar ticl e s of pre cipi ta te d le ci thin a dh e r e toge th er an d form a

b all D e scrib e its pr op er ti e s
. .

B oil ab ou t on e f our th of th e l e ci th in wi th a b ou t 1 0 cc o f
-
.

a 2 N s olu ti on Of s odium hydr oxid e N o te h e Od o r of th e gas

’

e v olv e d . Wh at is it ? Cool th e s olu ti on I s th e re an y e vid en ce .

o f th e f o rma t i on of a s oap ? Fil te r diss olve th e pr e cipi ta te in ,

w arm w ate r an d add dilu te hydrochl oric or a ce tic a cid to th e s olu

t i on . Wh at is pre cipi ta ted ?
Te s t a p ar t of th e l e ci thi n f or n i trogen an d f or ph osph orus
( S ee E xp t 2 8
. p ,
R e sul
. t s ?

R E F E RE N C E S

Mac L e an L ec i th i n a n d Allie d S ub s ta n c e s
,
“
, ( 1 9 1 8 ) (L on gman s )
L even e an d We s t L e c i th i n I — an d it s b e a r i n g
“
,
Hy d rol e c ith in ,
.

c onsti tu ti on of c p li e J ha n,
”
ou r n . Bi ol . Chem , 3 3 . 111
—
7
L eve n e a W st L c i thi — par ation pu r e le ci thin
“
nd e , e n, II P re
. Of

c omp o si ti a d s tabili ty Of l e ci th i ca dmium Ch l r i d

”
on n n o J ou n
e . r

Bi ol Chem , 3 4
. . 175
—8 6 .
 LABORAT OR Y E XP ERI MENT S 111

QUES T I ON S
Write th e s truc tura l formul a of le ci thin .

I s l e ci thin a n am e f or a si n gl e subs tan c e or is it a ge n e ric te rm ?

E xplai n.

Why is th e firs t e x tra c tion r e sidu e treate d wi th h ot a lcohol ?

Wh at are th e physical pr op er ti e s of l e ci thi n ?
Wh a t e lem en ts did you fin d pre s en t ?
Wh at o the r m e thods could be use d f or d e comp osi n g th e
o rg ani c m a tte r b e f o r e te s t i n g f or ph o sph a t e ?

W h a t is ch o li n e ? How is n e uri n e r e l a te d to i t ? M usc arin e ?

Be tain e ?
 E xpe rime n t N o . 28

D e te c ti o n N itr oge n } S ul f u r , th e H al oge n s

I
of an d P ho
in an Organ i c Compoun d

S upp or t cl ean dry h ard gl ass (P yrex) tub e (9 111m by

a , ,
-
.
,

m ) in a cl amp usi n g tw o pi e c e s Of c o rk a b ou t 5 mm
.
,
.

f or pro te c ti on or p a ss th e tub e thr ough a h ol e in

,

disc in s uch a w ay th a t the tub e is supp o r te d by th e fl

t op . P r ep ar e a sm all pi e c e of brigh t m e ta llic s o dium ,
1

t h an 2 c mm an d dr op it i n t o th e t ub e
. Apply a .

blu e fl am e cm lon g) n o w a n d th e n u n til th e s o

.

an d th e r e is a l ay e r o f s o dium v ap or I cm d e ep D . .

a m ou n t of th e subs t an c e to be t e s t e d
o r l e ci t hi n ) i n t o th e t ub e fr o m th e

a n d c o n t i n u e th e g e n t l e h e a t i n g whil e t h
-

progre ssin g b ei n g care ful n ot t o d rive th e v a

,

s tan ce ou t of th e t ub e by t oo s tron g h e a ti n g Fin ally .

m ass to red h ea t f or a min u te an d th en allow to cool to

t e mp e r a ture .

I n t h e m e an t im e (f or th e sulfur te s t) pr ep a r e ab ou t 2 cc Of .

dilu te s olu ti on of f e r rous sulf a t e an d als o a ve ry dilu te solu ti o ,

o f s odium n i t ro prussid e N a (N O) Fe (CN ) 5 by a ddi n g a s ma

, 2 ,

crys tal t o 2 cc of wa te r . .

T o th e co ol r e a c ti on tub e a dd tw o or t hre e drops o f al

-

t o d e s t r oy an y u n us e d s o dium U s e a s t irri n g r od to br
.
-

th e ch a rr e d m a ss Wh en th e e volu tion Of hydrogen h as

.

cau ti ously a dd a dr op or tw o of w a ter Wh en it is .

t h a t all th e s odium is d e s t r o e d a dd m o r e w a t e r Fil te r

y .

a sm a ll w e t fil t e r p ap e r a n d ri n s e ou t th e t ub e wi t h

four p or tion s of wa te r m aki n g th e t ota l v olum e u s e

,

3 cc T
. h e fil t r a t e sh o uld b e w a t e r whi t e I f i t is c-
o l o r e d .

th e d e comp o si t i on w a s n o t c ompl e t e a n d sh ould b e r e p e a t e d

1
R e turn a ll sod ium re sidu e s t o th e bo tt le .

112
114 LA BOR AT OR Y M A NUAL OF OR AN I
G C CH E M I S T RY
For th e h al ogen s th e fusio n is ca rri e d ou t in th e usu al m an n e r
a n d th e w a t e r whi t e fil t r a t e is a cidifi e d wi t h n i t ric a c id b o il e d
-
,

a n d t r ea t e d wi t h a f ew dr ops o f silv e r ni t r a t e s o lu t i on I f it
.

h as alr eady b een sh own th a t ni troge n a n d sulfur are abs en t it is

n o t n e c e ss a ry t o boil th e s olu t i on

For ph o sph orus u s e ab ou t 1 cc of the fil tra te fr om

,
.

sodium d e comp osi ti on in th e ni tr ogen tes t an d b oil thi s for

min u te wi th 3 cc of c on e ni tric a cid
. . Coo l th e s olu ti on
a dd t wic e it s v olum e o f amm o nium m o lybd a t e r eag en t .

th e tub e t o such a t e mp e r a t ur e t h a t it c an jus t b e h e ld in t h e

th en s e t a sid e . I f ph osph o rus w as pr e s en t in th e origi n al S
a y e ll ow crys ta l li n e pr e cipi t a t e of amm oni um ph o spho mol yb da
-

will form .

Q UE S T I ONS
1 . A t th e en d of th e s o dium d e c omp o si tio n in wh a t ch emic al
,

combin a ti on s a re th e n i tr oge n an d th e sulfur f ou n d ?

2 . How d oe s th e a lcoh o l d e s t r o y t h e u n a t t a ck e d s odium ?
W hy n ot u s e w a t e r a t firs t ?
Wri te e qu at ion s for th e r e a c ti on s in vo lve d in th e te s t
ni tr og en .

Why is the mix ture a cidifie d wi th sulfuric a cid ra th e r

wi th hydroc hloric a cid ?
H ow e ls e may sulfur be d e t e c te d ?
E xpl ai n th e f e rric chl oride t e s t
.

Can t h e s odium m e th o d be us e d f or d e te c ti n g a h a l og e n
S uppo s e a h a l oge n a n d ni t r ogen are b o th pr e s e n t.

How is ni t r oge n d e te c t e d a n d a ls o e s tim a t e d by th e s od

, ,

lim e m e thod ?
I n w h at combi n at i on is t h e ni t rogen wh en it c an o rdin a ri
b e d e te c te d by th e s od a lim e m e th od ?
-

Wh at is th e Kj e ld ahl m e t h od f or th e e s tim a tion Of

Wh a t is th e D um as or absolu te m e thod f or th e e
of ni trog en ?
 x
E pe rime n t No . 29

FORMA T I ON OF AN A CID A MI D E F R OM T HE AMMON I UM S A L T OF

TH E A CID

P re par atio n of Ac e ta mi d e f r o m Ammo n iu m Ac e tate

T he mm on ium a c e ta te us e d in this e xp e rim en t sh ould be

a

free from wa te r a s p ossible P re ss ou t th e m a te ria l on a .

rous til e if n e ce ss ary

1
.

F i rs t M ethod
Un d e r a r e flux con d e n s e r h e a t t o gen tl e boilin g a mix ture
I 5 gra ms of dry amm on ium a ce ta te an d a li tt l e more th an th e
a m ou n t o f gl a ci a l a c e t ic a cid f or t hr ee t o four hours Cool .
,

f e r th e liquid t o a Oo cc dis t illi n g flas k c on n e c t e d wi th a

-
.
-

n s e r a n d dis t i l l u n t il the t e mp e r a t ur e r e a ch e s
,

card thi s p or ti on (Of wh at d oe s it chi efly con sis t ?) R epl a ce

.

wa ter con d e n s e r by a sm all dis till i n g flask a llowin g th e ou tle t -

,

e of t h e firs t on e t o p a ss thr o ugh th e n e ck o f th e s e c on d on e .

a t th e dis till a t e will b e c oll e c te d in t h e bulb of t h e s e c on d

Con t i n u e th e dis t ill a ti on an d c oll e c t th e por ti on dis t illi n g

R e dis t ill t his S l owly a s pr e viously bu t f or a r e c e iv e r ,

t o th e ou tl e t t ub e o f th e dis tilli n g fla s k a sm all ordi n a ry -

r l arge te s t tub e which h as b e en w eigh e d an d w i th a cork

-
, ,

mg a ch an n e l c u t in th e sid e This t im e c olle c t th e .

dis tillin g 2 I o °
T h e pr oduc t s olidifie s to a whi t e
n e m a ss A t hird dis till a t i on may be n e ce ss ary if it
'

s olidify on coolin g P ure a ce tamid e boils a t 2 2 2 c or

.
0
.

1 0 gr a ms .

r u s e of po rous t il e c ompa re foot n ote p 5 6

, ,
-
,
. .

is n o t usually n ec e ssa ry to c ool th e rec e ivin g fla sk I f th is is don e h ow .

,

s t b e ta ke n n o t t o a ll ow t h e c on d e n sa t e t o so li d ify in t h e o u t l e t t ube

is t ill in g fla s k S i n c e it may c l og it a n d c a us e t ro u bl e
-
, .

115
116 LAB ORAT ORY MA NUAL OF O R GANI C CH E M I S T R Y
T he pe culi ar od or ch ara c te ris tic of mice e xcr emen t in t
crud e subs tan ce is du e to an impuri ty which c an gen e rally
rem ove d by re crys ta lliza t i on A ce t amid e is d e liqu e sce
-
.

vola tile a t the ordin ary tempe ra ture an d pre ssur e I t is .

s oluble in chloroform an d in alcohol an d diffic ul tly solu ,

e the r .

R e c ry s tall izati on of Ac e ta mi d e D e te rmin e th e w eigh t .

'

crud e produc t by w e ighin g th e r e ce iver ag ain A dd .

chloro f orm I cc f or ea ch gram to th e fl ask or tub e a t

,
.
, ,

r e flux con d en s e r an d h e a t to b oilin g by m e an s of w a rm

Chl or o fo rm b oils a t a n d a ll th e

wi thi n a f e w mi n u te s Discon n e c t an d .
,

s olu tion i n to a sm all b eak e r an d cove r

Wi thin a ve ry S hor t time the crys ta ls will c ommen
th e en tir e m a ss will quickly s et t o an app aren
th e sup e rc o oli n g an d e volu t i on of h ea t wh en ,

b e gi n s (E xplain ) Cool fur th er by pl a cin g th e b eake r

.

wa te r or ic e B reak up th e crys ta lli n e m a ss wi th a s tirr

°

a n d fil t e r r apidl y wi t h suc t i on usin g a 5 cm B uch n e r ,

.

( Fig 8. p o
,
r t h e.m e t h o d f o r suc t i on fil tr a t ion o
qu an ti ti e s p 5 6 I n th e l at te r ca s e u s e a 6 7 cm fu n n e l a
,
. .
—
.

m ois ten th e li ttl e fil te r p ap e r wi th chlor of orm b e for e turnin g

t h e pump P r e ss t h e m a t e ri a l d own sligh tly wi th a sp a t ul a
.

glass s topp e r On a ccou n t of th e v e ry hygroscopic n a tur e

.

a c e t amid e th e fil t r a ti on mus t n o
subs tan ce will liqu e fy Y i e ld 8 0 per c en t of crud e p .
,

I H ea t som e a c e t amid e w i th dilu te s odium hydr

.

s olu tio n Wh a t gas is e vo lve d ? A cidify wi th dilu te sul

.

a cid an d n o t e th e o d or
,
.

2 H e a t a s e c on d p or t i on o f a ce t amid e wi t h dilu te sul

.

a cid . Od o r of v ap ors ? N eu traliz e th e r e sul ti n g mix tur e w i

dilu te s odium hydroxid e .

NOT E

v
Sa e a on e -g a r m sample of th e a ce tamide f or th e me thyl am
exp r ime
e n t, p . 1 20 .
118 LAB ORAT OR Y MANUAL OF OR GANI C CHE M I S TYY

of th e t ub e an d h oldin g it th ere un til it b e com e s rigid

,
.

t h e n s ea l e d off s o a s t o l e a v e a capil l a ry ab ou t 4 cm l on g . .

capilla ry is n e ce ss ary as will be s een l at e r in op eni n g th e

S m oke t h e s eal e d e n d an d a llow th e t ub e t o s tan d wi th th e
e nd up u n t il c old Then r em ove th e s oot wi th fil te r p ap e r
.

cloth The in s tru c tor mu s t pas s on al l s eal ed tu bes before

.

are hea ted i n the fu rna c e .

H e atin g th e T u b e . P r o te c t
ye s wi th goggl e s th e e .

s eale d tub e is gen tly pu t i n to an ir on j a ck e t

a t the op en e n d (S e e i n.s t ruc t o r ) P l a c e .

furn a ce S O th a t th e Op en e n d of th e j a ck e t is
S li d e in th e gu a rd s ee th a t th e en d o f th e furn a c e
,

is r aise d an d prop e rly f a s ten e d an d t h en pl a ce a th e rm om e ter

,

in th e top of th e furn a c e Gradu all y t hir t y t o f o

.
,

rais e th e temp e ra tur e up to 2 00 a t which

°

th e b omb is h ea t e d f or thr ee h ours D o n o t a ll ow th e .

t ur e t o go high e r b e caus e an e xpl o si on w ill r e sul t The .

p e r a tu r e S h ould b e n o t e d a b o u t e v e ry t hir t y mi n u t e s .

h ea tin g c an be in te rrup te d a t an y tim e .

Ope n in g th e S e al e d T ub e s T h e t ub e s ar e a lw ays
.

t o coo l ov e r n igh t N 0 on e s hou ld en ter the c an n on room

.

w ea ri n g goggl es to r otec t
p the eyes . In no c a

a s eal ed tu be be ta ken ou t o f the i ron

an y othe r p ur p os e . When bei n g p
o e

pos i ti on tha t n ei ther the o er a tor n or a n yon e el s e c an

p be i nju red
c as e of bu rs ti n g . The tu be s hou ld be p
o en ed i n the c an n on r oo

I t s hou ld n ever be ta ken ou t i n to the l a bora tory u n o en ed

p .

T he con ten t s of th e t ub e are n ow l iqu id T h e .

p r o t e c ti
case of ir on con tain i n g th e tub e is r em ove d fr
, ,

a n d h e ld in a S ligh t ly in cli n e d p o si t i on t h e en d ,

b ein g high e r th an th e re a r e n d .

c apill ary of th e gl a ss tub e is caus

T h e e x tr e m e e n d o f th e c apill a ry is n ow
B u n s e n burn e r I f th e r e is an y in te rn al
.

th e gl a ss on b e c omi n g s of t will b e bl own

e sc a p e f r om th e op e ni n g t hus ma

e v en a t r e d h ea t (which s om e t im e
 LA BORA T OR Y E XP E RI M E NT S 119

th e en d may be broken Off by a sh arp bl ow wi th a fil e T h e gl ass .

tub e is n ow t ak e n ou t of t h e ir on j a ck e t A d e e p fil e m a rk is
.

m ad e in th e wid e p ar t of th e tub e ab ou t an i n ch b e low th e

should e r an d this is touch e d ligh tly wi th th e h ot en d of a
,
”

glass rod pr evi ously h ea te d to fusi on in th e bl a s t fl am e I f .

th e cr a ck c aus e d by thi s do e s n o t e x t e n d e n t ir e ly a r ou n d th e
t ub e th e e x t r e m e e n d of i t is e x t e n d e d by applyi n g th e h o t en d
,

o f th e gl a ss r o d a g ai n s o t h a t t h e c o n i c a l e n d may b e li f t e d ofl .

P urify th e product as in the fir s t m e thod above .

Q UE S T I ON S

Why mus t th e amm on ium a ce ta te be dry ?

E xpl ai n why th e a c e ti c a cid is us e d in t h e firs t m e th o d .

B y m ea n s of s t ruc tur a l f o rmul a s i n dica t e th e s te ps in th e

“ ”

hydr o lysis of a cy an id e .

How c a n a c e ta mid e be pr e p a r e d fr o m m e t hyl cy a n id e ?

Wh a t is th e a c ti on of ph osph o rus pe n toxid e on a ce ta mid e ?
Wh at o the r m e th ods are us e d f or f o rmin g amid es ?
H ow are th e subs t i tu te d amid e s pr ep a r e d ? E g a c e t an ilid e . .
, .

Wha t are th e ch e mica l pr op e r ti e s of th e a mid e s a s S h own by

t h e ir b e h a vi or t ow a rd ( I ) dry H Cl in e t h e r ( 2 ) br omi n e , ,

(3 ) br o m i n e a n d p o t a ssium hydr oxid e m e rcuric ,

o xid e (5),
ni t r ous a cid P C
,
l 5 (7 ) q
a H Cl
,
? (8 ) .

aq . KOH ?
Wh a t is an imid e ? H ow form e d ? E x succini mid e . .

W h a t is th e a c ti on of a l c KOH on an im id e ? Wh a t u s e is
.

m ad e of this r e a c ti on ?
L ook up th e s t ruc t ur e of ure a an d S h ow h ow it is r e l a t e d
t o th e a mid e s W h a t is its ch e mica l n am e ?
.

T h e se ques tion s are n ot required f or s tudy in th e “

s ho t r co urs e .
 x i
E pe r m e n t N o . 30

F ORM A T I ON A ND S T U DY OF A P R IM AR Y AMI NE

M e th yl amin e fr om
-
Ac e ta mi d e

In a cc dis tilli
60 . dissolve
n g- fla s k gr ams of s odium
hyd r oxid e in 6 cc o f dis tille d w a te r (amm on i a f r e e ) Coo l
. .
,

a n d th en (u n d e r t h e h o o d ) c a u t i ously a dd t hr o ugh a fu n n e l

I cc o f br omi n e (n o t br omi n e w a t e r )
. S h ak e a n d c ool Now
. .

a dd I gr a m o f a c e t a mid e s t opp e r wi t h a c o rk S l a n t t h e fl a sk a
, ,

li ttle an d a ll ow th e e n d o f th e ou tle t t ub e to dip jus t b e l ow th e

surf ace of 6 cc of dis till e d w a te r (amm on i a fr e e) con tain e d in a n
. .

op en t e s t tub e H e a t c a r e fully wi t h a sm a ll m ovi n g fl am e

- 1
.
,

u n til th e mix ture b e com e s cle a r an d vap ors are vigo rously
e v olv e d ; th en r e m o v e th e fl am e bu t r e sum e th e h e a ti n g a n d c on ,

t in u e f or s e v e r al mi n u t e s a f t e r th e m a in r e a c t i on h a s subsid e d .

I f th e w a te r in th e r e ce ive r b egi n s t o r u n b a ck r em ove th e

s topp er temp or arily .

1 .N o te th e o d or I s it e x a c t ly like th at of amm oni a ?

.

2 .Te s t th e r ea c tion of th e s olu ti on wi th n e u t ra l li tmus .

3 .A dd a dr o p o f th e s o lu t i on t o cc o f a v e ry d i lu t eI s o lu t i.o n

o f f e rric chl orid e R ep e a t wi t h dilu t e a mm on ium hydr oxid e

.

i n s tea d of th e amin e s olu ti on Comp a r e . .

4 .A d d a dr o p o f t h e s o lu t i o n t o I cc o f a v e ry dilu t e s o lu t i.on

o f cupric sulf a t e I f th e pr e cipi t a t e firs t f o rm e d d oe s n o t

.

diss olve a dd an oth e r dr op of th e s olu t ion R ep e a t usi n g .

,

dilu te amm on ium hydroxid e T0 wh at is the color in each

.

i n s t a n c e du e ?
5 .T o th e r e m ai n d e r of t h e s o lu t i o n in a n e v a p o r a t i n g dish
a dd co n c .hydrochloric a cid drop by drop wi th s t irri n g un til
1
S tron gly a lka lin e solu t i on s bump c on si derably .

120
 E xpe rime n t N o . 31

E th yl I s oc ya n ate

G rin d toge th e r e qu al p ar ts (abou t 0 5 gr am) of dry po tassium

.

or s odium cyan a te an d dry p ota ssium e thyl sulfa te P l a ce th e

1
.

mix ture in a dry t e s t tub e an d h e a t c are fully A liquid s oon

-
.

b e gi n s to di s till an d p ar ti ally con d en s e s on th e w alls of th e

t e s t t ub e
-
. N o t e it s o d o r .
( Ca r e " )
I Wh a t is its s truc tur al f o rmul a ?
.

2 . Why mus t th e r ea c tin g subs tan ce s be dry ? E xpl ain fully .

3 . Wh a t h app en s wh en th e liquid ob ta in e d ab ove is b oile d

wi th w a te r ?
4 . H o w d o t h e is o cy a n a t e s r ea c t wi t h a lc o h o l ? S h o w h ow

t his r e a c t i on c a n b e us e d in th e id e n t ific a t i on of a lcoh o ls ;

a ls o a mi n e s .

5 . G iv e th e r ea s on s f or a ssig n i n g t h e a cc e p t e d s t ruc t ur a l formul a

f or th e is o cy a n a te s .

6 Do e s te rs of cy an ic a cid i t s e lf e xis t ? Can y ou give a n y r e a s on ?

.

1
Not c ya ni de .
 E xperime n t N o . 32

M e th yl M u s tar d
. Oil ( M e th yl o i o c y a n at e )
I s th

In a s ub e mix a f ew crys ta ls of m e thyl amin e hydro

te t - t
chlorid e (E xp t 3 0 te s t 5 p
.
, ,
. on e dr op o f c a rb on b is u l fid e
,

a n d on e or tw o dr ops o f a s t r on g s o lu t i on o f s o dium hydr o xid e .

f e w s e con ds a dd a li t t l e w a t e r a n d sligh t ly m o r e t h an
S ilv e r n i t r a t e s o lu t i on (N 1 0) t o r e a c t wi t h t h e p o t a ssium

hydroxid e . B ri n g to a b oil T h e Od o r o f th e mus ta rd oil

.

will a t on ce b e com e pron ou n ce d .

Ou tli n e al l th e s teps in this re a c ti on .

D o a l l a mi n e s give this r e a c ti on ? Th e re fo re ,

wh a t u s e c an be mad e of th e r ea c ti on ?
H o w c a n y ou dis t i n guish ch e mic al ly be tw e e r: a n is o cy an a t e
3.

a n d a t hi o cy a n a t e ?

4. Which c o mp o u n d o f t his s e ri e s is f o u n d in t ru e mus t a rd Oil ?

D oe s th e n am e o f its hydr o ca rb on r a dical h ave a n y sig
n ific an c e in org ani c n om e n cl at ur e ?
 E pex rim e n t No . 33

H YD R OL YT IC P RE P AR A T I ON , S E P A R A T I ON A ND P UR I F ICA T I
OF A N A M I N O A CID

P r e parati on of G l yc ll (G lyc i n e ) fr om
oc o H ippuri c Ac i d

Hea t to sl ow b oili n g I gram of hippuric a cid an d I 5 cc o f .

con c hydro chl oric a cid in a 2 5 0 cc fl a sk u n d e r r e flux c on d en s e r

. .

f or t hir t y mi n u te s D urin g this tim e h ave a tub e c on n e c te d

.

wi th th e t op of th e con d e n s e r t o l ea d th e fum e s i n to a fl ask c on

t ai ni n g dilu t e s o dium hydr oxid e s olu t i o n T h e op e n i n g S h ould .

b e a bove th e surf a c e o f th e a lk a li n e liquid a n d th e fl a sk sh ould b e

l oos ely s topp e r e d wi th co tton T owa r d th e en d of th e hyd r ol
.

y s is crys t a ls a r e d ep o si t e d on th e in sid e w a lls o f th e c o n

d en s e r .

A f te r th e thir t y mi n u t e s h ea t i n g disc on n e c t th e app ar a tu s

’

a d d 1 0 cc o f w a t e r t o t h e m a i n r e a c t i on mix tur e an d c oo l wi th
.

ru n n in g w a te r Fil te r off th e crys ta ls wi th suc tion a n d s ave

.

b oth th e pr e cipi ta te an d th e fil tr a t e Dry th e whi te c r ys ta llin e .

produc t an d d e t e rmi n e its m e l tin g p oi n t Te s t its s olubili ty -

.

in e th e r Diss olve ou t th e d ep osi t in th e c on d en s e r wi th

.

e va p o r a t e th e e t h e r an d d e t e rmi n e th e m e l t i n g p o i n t o f t h -
,

re sidu e Comp are wi th th a t ob tain e d fr om th e h y dro c hl ori

.

a cid s o lu t i o n .

E va p o r a te th e fil t r a t e to dry n e ss on th e w a te r b a t h -
.

1 5 cc o f w a t e r a n d fil t e r o ff a n y i n s o lubl e m a tt e r
. N ou t r .

exa c tl y wi t h dilu t e s odium hydr oxid e s olu t i on usin g li tmus ,

p ap e r f or th e t e s t s Fil t e r aga in if n e c e ss ary A dd a b ou t

.
,
.

0 5 gr a m of b asic c opp e r c a rb on a t e a n d w a rm wi t h s t i r r i n g
. A .

de e p blu e c ol o r is ob t a i n e d which is ch a r a c t e r is t ic of t h e s o lu
,

t i on s o f t h e c o pp e r s a l t c ompl e x e s o f m a n y o f th e mon amin o

aci ds . Fil te r th e solu tion whil e s t ill h o t an d a ll ow th e fil tra te
124
126 LAB ORAT ORY MANUAL OF OR GANI C CH E M I ST RY

Q UE S T I ONS
Wh at is th e s t ruc ture of hippuric a cid ? P oin t ou t it s
ch e mic a l groupi n gs .

I n th e hydro lysis o f hippuric a cid wh a t compou n ds are

fo rm e d ? Wri te the ir s truc ture s .

Of wh a t d oe s th e d e p o si t in th e con d e n s e r c on sis t ?
Why is th e r e a c t i on mix ture dilu t e d ?
W hy is th e fil tr a t e e vap or a t e d t o d r yn e ss ?
W h at is l e f t a f t e r t h e e v apora tion t o dryn e ss ?
W ri t e th e r e a c t i on f or th e n e u tr a liz a t i on ( S ee a lso.qu e s
t i on N o.

Why n o t u s e copp e r sulfa t e f or pr e p a ri n g th e copp e r s a l t ?

Could i t b e us e d a t a l l ?
Wh a t a dvan ta ge h as a rou n d b o ttom e d crys tallizin g dish
-

ov e r a fla t b o t t o m e d on e
-
.

D iscuss th e s t r uc ture of amin o a ce t ic a cid (glyc o coll glyci n e )

-
, .

A cc ou n t f or it s hi gh m e l t i n g p oi n t -
.

H ow a re a mi n o a cids e s tim a te d ?
G iv e thr e e m e th o ds o f f o r mi n g glyc oc oll i n cludi n g its ,

pre p a r a t ion f or e x ampl e from ge l a tin e

, , .

H OW c an y ou pre p a r e hippuric a cid ?

W h a t is glycyl glyci n e ? I ts prep a ra ti on by tw o di ff e re n t
-

m e thods ?
Comp a r e th e s t ruc tur e of hippuric a cid wi th th a t of a
dipep tid e .

H ow a re p o lyp ep t id e s pr ep ar e d ?
. . H ow a re th e a mi n o a cids s ep ar a t e d an d id en tifie d in th e
mix tu r e ob tai n e d by th e hydro lysis of a pr o te in ?
18 . Give n am e s an d s truc tur e s of the impor tan t amin o a cids .
 E xpe rime n t No . 34

l ys i s of Can e S u gar an d P re par at i on of P h e n yl gl u c os azon e

grams of can e suga r in 2 0 cc o f w a t e r Te s t a

e 2 . .

drops of this s ol u t ion wi th F e hli n g s s olu ti on (mix 5 cc o f ’

.

p ar t b oil an d th en add the s olu t i on t o be te s te d) an d

, ,
‘

t e s t wi t h a mm on i a c a l S ilv e r ni t r a t e R e sul t ? A dd 0 5 cc . . .

hydrochl oric a cid to th e m ai n s olu ti on a n d pla c e th e ,

in w a t e r k ep t a t 7 0 f or fiv e mi n u t e s Cool u n d e r ru n n i n g
°
.

r E x a c t ly n eu tra liz e 2 3 cc wi th dilu te a mm on ium

.
— .

oxid e s o lu t i o n a n d t h en t e s t a g ai n wi t h F e hli n g s s o lu t i on
’
,

a ls o wi t h t h e a mm oni a c a l silv e r ni t r a te I f a ligh t .

pr e cipi ta te is ob tai n e d wi th th e silve r solu ti on add m or e

hydr oxid e u n til i t di ss olve s E xpl ai n all re .

e u tr aliz ewi t h amm oni um hydroxid e 1 0 cc of the hydro .

sugar s olu ti on m ak e up t o 2 0 cc wi th w a te r pl a c e th e s olu

,
.
,

n a l a r ge t e s t t ub e (N o an d a d d 2 cc o f p h e n l h dra
-
.

y y .

an d 3 c c of gl a ci a l a c e t ic a cid
. M ix w e ll S t opp e r . .

wi th a cork to pre ven t e vap or a t i on an d s e t th e tub e i n to ,

which h as b een brough t to b oilin g an d l e t s tan d f or

2

M a ss e s of fin e ye ll ow crys t als of th e o s az on e
ou t Cool fil t e r o ff th e o s az on e in a B uch n e r fu n n e l
.
, ,

wi th c old w a te r R e crys t alli z e as foll ows : Pl a ce th e

.

product in a 2 50 cc E rle nme ye r fl a sk an d add a mix tur e

.

cc of alcoh ol an d 6 0 cc o f w at e r a tta ch an uprigh t c on

. .
,

or c ov e r wi t h a sm all w a t ch gl a ss s e t th e fl a sk on th e s t ea m ,

h e a t u n t il al l or pra c tically al l th e subs tan ce is diss olve d .

h y d ra zme IS pms on ou s va p ors sh oul d n ot be brea th ed an d it

. I ts ,

be a ll o w e d t o c ome i n t o c o n t a c t w i th t h e S ki n si n c e i t pro d u c e s an

D ilu te a c e ti c a c i d w ill remov e ph en ylh ydraz i n e .

a f te r pla c in g th e t u b e in t o th e ba th oth e rw is e a da rk prod u c t

,
128 LABOR AT ORY MANUAL OF OR GA NI C CHE M I STRY

In rd e r to preven t crys talliz a ti on in th e fil te r th e s olu ti on

o
,

S h o uld b e fil t e r e d a t o n ce thr o ugh a flu t e d fil t e r in a

1
l ss fu n l
g a n e

s e t in a h o t w a te r fu nn e l usi n g a s t irri n g r o d to dir e c t t h e flow o f

-
,

th e h o t s olu t i on i n t o th e fil te r T h e h o t w a te r fu n n e l con sis t s of a

.
-

d oubl e w all e d c opp e r j a ck e t for a n ordi n ary fu n n e l wi th a sid e

-
,

t ub e f or h ea t i n g th e wa te r wi thi n (Fig S t ea m .

b e p a ss e d i n t o i t i n s tea d of usi n g w a t e r I f a bu r n e r is .

it mus t b e r e m ov e d wh e n y ou are fil te ri n g i n fl a mm abl e

FI G . 12 .

as in this ca se . The s te m o f th e gl ass fu n n e l should n ot proje c

m o r e th an 2
—
3 b e l ow th e n e ck of th e h ot w a te r -

1
A flu t fil t e r is ma d e by firs t fo l d i n g a la rge c irc ula r fil ter pa p er in
ed

n a ry w a y .T h en h a lf o p en it a n d bri n g o n e c o rn e r i n t o
,

c irc l e a n d c rea s e th e p a p e r B rin g bac k th is sa me c o rn er

.
.

jus t ma de an d c rea s e aga in Now fold th is bac k t o th e mi

, .

h e mi c irc l e R e pe a t w i th t h e o t h e r qu a dra n t
. T h is giv e s a n a l t
.

fol d s Wh en c ompl e tely o p en e d it w ill be n o ti c e d th a t th e re a re

.
,

th e p a pe r w oul d l ie fla t a ga i n s t th e w a lls of th e fu n n e l Fo l d ea c h .

h a lf fol d t o ma ke th e m simil a r t o th e o the rs A flu ted fil ter .

fil tra ti on (W hy ? )
.
13 0 L A BOR A T OR Y M A N UAL OF OR G AN I C CH EM I S T R Y

Q U E S T I ON S
Why w ould y ou e xp e c t c an e su ga r t o be s oluble in
I .

2 W h a t a e t e tw o m o o s a cch arid e s in i n ve r t su ga r ?
. r h n —

3 Wr i
. t e t h e s t ruc t u r a l f o rmul a s f or c a n

s tan ce s in in ve r t su ga r .

4 S h o.w by m e a n s o f i t s s t r uc tur e t h a t c an e S
5 W h .a t d o e s t h e b e h a vi o r o f c a n e su ga r

solu ti on an d amm on i aca l silve r n i tr a te

in it s s t ruc tur e ?
6 Why is th e i n v e r t suga r s olu t i on n e u t r a liz e d
.

hydroxid e s olu tion b e for e it is te s te d

s olu ti on ?
7 W h. a t is th e whi t e pr e cipi t a t e f o rm e d wh en

a mm on ium hydr oxid e is us e d in t h e silv e r mirr o r t e s

8 E xpl ai n why th e s am e c on c en t r a t i on o f a c e tic a cid

.

hydro chl oric a cid in w a te r w ould n o t hydrolyz e can e s u

as r apidly .

9 H o .w c a n y ou S h ow t h a t c a n e su ga r is a n a lc o h o l ?
10 E xpl ai n why i t is t h a t i n v e r t su ga r c a n b e oxidiz e d
.

Fe hlin g s s olu tion al th ou gh th e l arge r p o r ti on of

’

m on o s a cch arid e s in it a re kn own to be in th e la c t

-

form .

E xpl a i n h ow th e r e a c t i on b e tw ee n F e hli n g s s o lu t i
’
11 .

i n ve r t su ga r c an b e us e d a s a qu an t i ta tive me thod
e s t im a t i o n o f c a n e su ga r in th e p r e s e n c e of kn own

o f gluc o s e .

12 E xpl ain why i n v e r t su ga r yi e lds on ly o n e o s az on e

. .

13 For wh a t purp o s e is a c e t ic a cid a dd e d in th e fo rm at i on

.

th e gluc o s az on e fr om th e hyd r o lyz e d c an e S u ga r ?

14 Could s t r on g hydro chl o r ic a cid b e us e d in pl a c e of
.

g l a ci a l a c e tic a cid in th e f o rm a t i o n o f th e o s a z o n e?

15 Ca n i n v e r t su ga r f o rm h y d raz on es an d if s o wh at w ould
.

t h e i r ch e mic a l s t ruc tur e ?

16 E xpl a i n h ow th e h yd r a z on e s an d os az on es are of v alu e
.

th e a n a lys t in id e n t ifyin g su ga rs ?
*
17 Co uld an y o th e r hydr azi n e s b e sid e s ph e n yl hydrazi n e
.

use d f or the purp o se? A re th ey e ve r us e d an d why ? ,

*
18 Can y ou give an y r e a s on why th e h y drazon es o f gluc o s e a
.

m ann ose sh ould be diffe re n t

t w o m on o s a cch a rid e s diffe r
-

h ydro chloric a cid ?

 LABORA T OR Y E XP ER I M E NT S 13 1

How c an d -
glucose b e t r an sf o rm e d in to d
-
fruc tose ? in to
d m an n o s e ?
-

H ow c an d fruc to s e be t r a n sf o rm e d i n to d gluco s e ?
- -

Wh a t is m e thyl gluco sid e ? H ow prep ar e d ?

a -

Of wh a t d o e s th e B e n e dic t F e hli n g s o lu ti o n c on sis t ? Wh a t

-

a dv a n ta g e h as i t o v e r th e F e hli n g s o lu t i on in t h e t e s t

f or gluco s e in a physi ol o gic a l s olu t i on lik e uri n e ? (H awk ,

P r a c tic a l P hysi ologic al Ch emis try s t h E d ,

”
.

2 7 4 1 7 8 ; P l imm e r P r a c tic a l Orga n ic a n d B io ch e mis t ry

— -
, ,

Th ese q u e s tion s are n ot required f or s tu dy in the sh ort co urse .

 Expe rime n t N o . 35

P e n to s e s (Furf u r al T e s t)

A solu ti on of a pe n tos e is firs t m ad e by th e a cid hydrolysis

o f a pe n t o s an such a s gu m a r abic o r a n o r di n a ry c o r n c ob a n d ,

t h en t h e pr e s e n c e of th e p en t os e is S h ow n by th e c ol or e d c om
p oun d f orm e d by th e a c t i on o f th e d e comp osi ti on produc t of the
pe n to se wi th hydro chl oric a cid an d an ili n e a c e ta te .

M ak e up 3 0 cc of a s olu t i on of di lu te hydro chl oric a c id tsp gr

. . .

by mixin g 9 cc of c on e hydro chlo ric a cid an d 2 1 Cc of

. .
'

wa te r P our 1 0 cc of thi s di lu te a cid i n to a 1 00 cc fl ask an d add

. . .

a b ou t gram of gum a rabic S lowly bri n g t o a b oil ove r a

.

l ow fl am e an d b o il gen tl y f or fiv e t o t en mi n u te s Wi thdr aw .

t h e fl am e a n d whil e th e v ap ors a re c omi n g ou t pl a c e in th e m ou th

,

o f th e fl a sk a r o ll o f fil t e r p ap e r which h as b e en s o ak e d in a

s olu ti on of an ilin e a ce ta te an d fr om whi ch th e exce ss of th e

,

s olu ti on h as b e e n re m ove d by pr e ssi n g b e twe en fil te r p ap e rs ,

T h e t e s t sh ould b e m a d e whil e th e p ap e r is s t ill m ois t T he .

a n i l i n e a c e t a t e s o lu t i on is pr e p ar e d by mixi n g 2 cc e a ch o f .

a ni li n e ,
gl a ci al a ce tic a cid an d wa t e r A brigh t crim s on colo r .

on th e a n ili n e a c e t a t e p ap e r i n dic a t e s t h e pr e s e n c e o f fu r fur a l

from th e a c ti on of th e hyd r o chloric a cid on th e p en tos e .

R ep e a t th e abov e e xp e rim en t usi n g g r am of gr oun d

,

corn c ob .

S om e of th e h e x o s e s a ls o giv e a pin k c o l or in t his s am e t e s t ,

bu t th e c ol or g e n e r a lly is n o t s o pr on ou n c e d R e p e a t th e .

e xp e rim e n t usi n g t h e s a m e m ou n t o f c a n e su ga r an d comp a r e

, a ,

th e c ol o r pr o duce d wi th th a t fr om th e pe n t os e s .

R E F E RE N CE S

discussion is t est s ic lysis

“
of Sh e r man Or gan
’
Fo r a th s ee An a ,

an d f o r th e p r obable c ompo si tion of th e l

c o o ed c or mpoun d for me d on
13 2
 E xpe rime n t No . 36

OX I D AT I ON OF A S U GAR

M u c ic Ac d f i r om Lac t os e
In a p or c e l ain dish
cm in di
,
a m e t
13 e r —1
e v a4p o r a t e o v.e r a ,

fre e flame a s olu ti on of 1 2 grams of l a c to s e in 1 5 0 g rams of n i tric

’

a cid o f sp gr t o a v o lum e o f a b ou t 2 5 cc wi t h s tirri ng

1
. . .

t ow a rds th e e n d I n o rd e r t o r e m o v e t h e fum e s supp o r t a l a rge

.

fu n n e l ove r th e dish a n d con n e c t it wi th th e suc ti on pump D o .

n o t h ea t s o s t r on gly t h a t th e m a t e ri a l is ch a rr e d o n th e S id e s

o f th e e v ap o r a ti n g dish B r own fum e s . a r e e v o lv e d an d ,

th e m a ss fi n a lly b e c om e s t hick a n d p a s t y owi n g to th e s ep a r a

t i on o f mucic a cid Wh en c old dilu t e wi th wa t e r fil t e r wi th
.
, ,

suc ti on an d wa sh wi th sm a ll a m ou n t s of cold wa te r I n orde r

,
.

t o d e t e r mi n e th e yie l d o f crud e pr o duc t dry i t on a wat ch gl ass

/

on th e s t e a m b a t h o r in a n o v e n
-
.

T o purify diss o lve th e crud e dry m a t e ri a l in a c o ld s olu ti on

,

o f s o dium hydr oxid e an d r e pr e cipi t a t e wi th hydr o chl oric a cid -

;

On ly th e n e u tr a l s a l t is e a sily s olubl e in w a t e r a n d its s olubili ty ,

is d e crea s e d by exce ss of a lk a li I t is b e s t th e r e f o r e t o
.

calcul at e appr oxim a te ly the a m ou n t of N /2 s odium hydroxide

solu tion n e ce ss ary D O n ot ad d dr y s oli d s odi um hydr oxid e t o
.

th e w a t e r co n t a i n i n g th e mucic a cid — use

a c o ld s o lu t i o n Fil te r .

if n e ce ss ary I f th e s olu ti on is da rk brown de co loriz e by gen tly

.
,

wa rmin g wi th a n im al ch a rcoal or fil te r through a fu n n e l c on ,

t a i n i n g a ni m a l ch a rcoa l C o l a n d a dd th e e quiva l en t o f 5 N
o .

hydro chl oric a cid to s e t fr e e th e mucic a cid T h e hydro

2
.

1
T he l ul at i on s c an b e made from th e f oll ow in g data : Th e spec ifi c gravi ty
ca c

o f o rdin a ry c on c n i tri c ac i d is
.

N i t ri c a c i d c on t a i n s
,
HN 0 by w e igh t 3

N i t ri c a c i d c on t a i n s
. H N 0 by w e igh t 3
2
Con c h ydro c h l ori c ac i d s p gr
. c on ta in s 3 7 % H Cl by w e i gh t
, . .

13 4
 LAB ORAT OR Y E X P ER I M ENT S 13 5

cid mus t n ot be a dd e d whil e th e liquid is wa rm b e ca us e

ic a

of th e m ucic a cid may b e con ve r te d i n to the e asily s olubl e

e T o c ompl e te t h e crys t a lliz a t i on a ll ow th e liquid t o
.
,

th en fil te r wi t h suc t i on w a sh wi t h c o ld w a t e r a n d dry
, ,
.

gr ms D rmi m e l ti n g p oin t M ucic

'

4 a e t e. n e t h e -
.

on e p ar t in 1 00 o f w a t e r a t 1 4
°

Try th e a c ti on of F e hli n g s s olu tion on la c tose Wh at do e s

’
.

this i n dic a t e ?

NOTE

T h e t e rm mucic me s f r om th e L a t in
c o mucus mean wo r d “
,

in g mucus or slime
M uc ic a c id h as b een kn ow n f or man y ye a r s ,
.

h avi n g e a r ly b een p r epa r ed by th e a c ti on of n i t r i c a ci d on s ome plan t

muc ilagin ous ma te r i al w h ic h c on ta in ed gal ac tan s T h e G e r man .

n ame f or mucic aci d is S c hl e ims au re

”
.

Q UES T I ONS
1 . Wri te th e e qu at i on s for al l r ea c ti on s i n volve d in the pro
duc ti on of mucic a cid fr om l a c tos e i n dica ti n g th e va ri ous,

re a c tion s by m ean s of s te re o ch emic al s truc ture s .

E xpl a i n why it is n e c e ss a ry t o u s e ni t ric a cid of a bou t thi s

p ar ticul ar s t re n gth a n d give reas on s
,
.

Wha t is th e a c t ion of con c n i tric a cid on l a c tose ?

.

W h a t signi fic an ce is t he r e in th e f a c t th a t l a c to s e r e duc e s
F ehl i n g s s olu tion ?
’

Whi ch of th e tw o m on o s a cch a rid e s combin e d in th e l a c tos e

-

m ole cule con tain s th e fr ee c arb on yl gr oup ? H ow c an

t hi s b e S h ow n ? (T h e s t ruc tur a l f o rmul a of l a c t o s e in
S to dd a rd I n t r o duc ti on t o Orga ni c Ch emi s t ry
”
,
2d Ed , .
,

p 2 1 5 sh ould be r e ve rs e d ) Comp are Ho lle m an s

.
,
.
’

Organ ic Ch e mis t ry
”
.

6 . Wh a t b e com e s of th e s a cch aric a cid an d how d oe s i t diff e r

from mucic a cid s truc tu r ally ? I s it op tic a lly a c tive ?
Can y ou give a n y r e a s on why y ou w o uld e xp e c t mucic a cid
n o t t o h av e th e s a m e s o lubili t y a s s a cch aric a cid ?

I S t his a cid n am e d d l r a c e mic or m e s o mucic a cid ? G ive

, ,

r ea son s .

Wh at is th e s al t form ed wh e n s odium hydr oxi de r e a c ts wi th

mucic a cid ? N am e ?
Why is it n e ce ss ary t o n e u traliz e s o care fully w i th s odium
hydroxid e ?
136 LAB OR AT OR Y MANUAL OF OR GANI C CH E MI ST RY
Wri te th e s t ruc ture of th e l a c ton e of mucic a cid .

T o wh a t cl a ss of o r gan ic c omp o u n ds d o th e l a c t on e s b e l o n g?
Ar e c omp ou n ds lik e th e l a c t on e s o f te n f o rm e d by b o ili n g
w a te r ?
I n dica t e th e di ff e r en c e b e tw e e n an a cid l a c to n e an d a

suga r l a c ton e
.
”

Wh a t is th e chie f o rgan ic impuri t y re m ove d by th e r e

crys talliz ati on an d wa shin g ? I S thi s ob ta in e d fr om o th e r
s ug ar s lik ewi s e ?
 E pe x rime n t No 3 8 .

BE N Z E NE : C HE M ICA L P R OP E R TIE S

a To 2 cc of b en z en e l ab e le d thioph en e fre e a dd 0 5 cc
. .
, ,
. .

of a dilu te s olu ti on of bromin e in c arbon te trac hl oride D oe s th e .

color of th e bromin e disapp ear imm e di ate ly ? A t al l ?

b (H ood ) Add s e ve r a l dr ops o f br omi n e (n o t br omi n e
. .

wate r) to 5 cc of b enz en e Divid e th e s olu ti on in to e qu al

. .

p or tion s an d to on e add s om e iron p owd e r N o te th e diffe r

,
.

e n c e in th e v e l o ci t y o f th e r ea c ti on in th e tw o t ub e s B r e a th e .

a c ross th e top of th e m .

c Add s e ve r a l dr ops of b enz en e to 1 cc of c on c sulfuric

. . .

a cid . S h ak e I s th e r e an y e vid en c e of ch e mica l a c ti on app a r en t

.

by th e form ation of h eat or by d ark en i n g ? D oe s th e mix ture

b e com e h omogen eous ? P our it i n to 6 cc of co ld wa te r cool .
, ,

s tir an d th en tran sfer to a No 1 t e s t tub e I s a h om ogen eous

,
.
-
.

solu t i on ob tain ed ? Do e s b enz en e diss olve in h ot con c sulfuric .

a cid ?

d R ep eat c usi n g fumi n g sulfuric a cid

. .
, P ou r th e mix tur e .

drop by dr op i n to c old wat e r or b e t t er up on ic e R e sul t ? ,

.

(A s o lid subs t a n c e di p y
h e n,
l su l f on e m a y s e p a,
r a t e in t h e w a t e r
s olu ti on E xpl ain )
. .

e Add s e v e r a l dr ops o f b en z en e t o 1 cc
. of con c ni tric . .

a cid . S h ak e w e ll f or tw o mi n u te s An y h e a t f orm e d ? Th e n
.

a dd S l o wly w i th c ooli n g 1 cc of c on c sulfuric a cid S hake

‘

. . . .

An y ch an ge ? P our i n to c old wa te r a n d s tir w e ll Wh a t is th e .

-

h eavy y ell ow oil th at se ttl e s ou t in drOpl e ts ? Note th e odor .

I s b en z en e r ea c t e d up on by fumi n g n i tric a cid ? Try i t .

f .T o 1 cc o f .a v e ry dilu t e s o lu t i o n o f p o t a ssium p e rm a n

g an a t e in a sm a ll gl a ss s t o pp e-
r e d b o tt l e a d d I cc o,
f b e n z e n e .

thi oph e ne fr ee I s t h e r e a n y chan ge n otic e abl e ?

"

13 8
 LAB ORAT OR Y E X P ERI M E NT S 139

Comp ar e al l the b ove r e ac t i on s wi th b e n zi n e (in th e M e th an e

a

e xp e rime n t p 3 1 ) an d pi n e n e (in the E thyl e n e e xp e rim en t p

,
.
.
,

g D e
. t e rmin e th e f r e e zi n g p o i n t o f b e nz e n e by fr ee zi n g
-
s o m e

I n a t e s t tub e pl a c e d I n ic e an d w a t e r
-
S tir th e b en z e n e w i th a .

t h e rm om e t e r u n til i t s o lidifi e s N o t e an y sup e r c ooli n g a ls o .

-
.

T h e t ru e fr eezi n g p o in t of b en z en e is -
S ee R ich a rds
a n d S hi pl e y T h e F r e ezin g p o i n t of B e n zen e as a Fix e d P oi n t
,
-

try , J ou rn . A mer Chem S oc . . .

, 36 18 2 5 .

qu an ti ti e s of a rom a tic hydrocarb on s ar e con veni en tly

con ve r tin g th em in to s oli d ni tro d e riva tive s usu ally ,

c omp oun d an d d e te rmin i n g th e m e l tin g p oi n t

,
-
.

Mix 1 cc of con c sulfuric a cid an d 1 cc of con c n i t r ic a cid

. . . .

a dry t e s t t ub e an d a dd thr ee dr ops o f b e nz e n e

-
H e a t to .

ili n g an d boil f or thi r ty se con ds Cool an d p our sl owly i n to

'

1 0 cc o f w a t e r in an o t h e r t e s t t ub e
. S h ak e Fil te r off th e -
. .

bulky pr e cipi ta te wi th suc t i on colle c ti n g it upon a sm all fil t e r ,

1

an d w a sh u n t il th e w a shi n gs a r e n o l on g e r c o l o r e d Diss olve th e .

subs tan ce wi th sh aki n g in a b oili n g mix ture of 4 cc of a lc oh o l .

an d 4 cc of w a t e r an d s e t a sid e t o crys t a lliz e

. I t crys t alliz e s .

'

in l on g fin e n e e dl e s which ar e n e a r l y whi te Fil te r wi th suc ti on .

an d a ll ow t o dry up on a por ous t il e D e te rmi n e th e m e l ti n g .

e n e f orm e d which sh ould b e

2
c or ,
.

W ri te th e s t ruc tur e o f th e c omp ou n d f orm e d in t his r ea c ti on .

Can a S imil ar c omp o u n d o f t olu en e b e pr e p a r e d wi th th e s a me

kin d of a cid mix ture ?

H I S TORI CA L NOTE

Faraday , i n 1825 , d is c o ve re d a l iqui d h yd roc a rbon in mpre sse d c o c oa l gas -

wh ic h he lled bic arbu re t of h ydroge n si n c e it

c a
“
,
h a d th e e mpiri c a l formula
C2H (on t h e ba sis of th e a t omi c w e igh t of c a rbon b e in g 6 w h i c h w a s us e d a t th a t
t ime ) . M it s c h e rlic h 1 8 3 4 Obt a i n e d th e same h ydroc a rbon by th e d is t ill a t i on of
, ,

benzo i c a c id w i th sl ake d lime a n d t erme d it be nz i n H e a ssu me d th a t it w a s

“ ”
.

f ormed from th e ben zo i c a c id by th e remova l of C0 L i eb ig d en i e d t h is a dd in g 2 .

,

th e f oll o w in g e d i to ria l n o te t o M it s c h e rlic h s me mo ir in t h e An n alen ’

We “ ” “

ha v e c h an ge d th e n ame o f th e bod y ob ta i n e d by P ro f M it s c h e rl ic h by th e d ry .

d is t ill a t i on of benzo i c a c i d an d lime a n d t e rme d by him ben zi n in to benzol be c a us e , ,

1 fil tra ti on of small qu an t i t i e s w i th su c ti on
For , s ee p .
56 .

For th is me th od of pre p ara ti on se e M ullike n fic ati on of P ure Org n ic

“
2
, ,
I den ti a

Compo u n d s Vol I 2 00
”
.
,
.
,
140 LAB OR AT ORY MANUAL OF OR GANI C CH E M I S T RY
t he t e rmi n a tion in a ppears to d en ote an an al ogy be tw een s t ry c hn in e ( Ge rman
‘ ’
,

s t ryc h n in ) a n d qui n in e e t c bod i e s t o w h i c h it d oe s n o t bear th e sligh t e s t re sem

,
.
,

bl an c e w h ils t th e e n d in g in 01 c orresp on d s be tte r to it s pro pe rt i e s an d mod e of

‘ ’
,

prod u c t ion I t w o uld h av e been be tt e r p erh aps if th e n ame w h i c h th e d isc overer

.
,

Fa ra da y h a d giv en to th is bod y h a d b ee n re ta i n e d a s it s r e l a t i on t o be nz o i c ac id
, ,

a n d b e nzo yl c ompo u n d s is n o t a n y c l o s e r t h a n it is t o t h a t of th e ta r or c oa l from

w h i c h it is ob ta i n e d A W Hofman n in 1 845 isol a ted th e h ydroc a rbon from

.
”
. .
, ,

c oa l —ta r La te r th e n ame benzen e c a me in to u s e in ac c ordan c e w i th th e en din g of

.

u n sa t ura t ed h ydroc a rbon s .

For ma n y ye a rs h o w ev e r t h e en d in g 01 h a s b een used to d en ote an a l c oh ol

“ ”
, ,
'
or a p h e n o l T h e t e rm benzol is t h ere fore c on si d e red a h ybri d an d a mis n o me r
.
, , .

Un fortu n a tely th e pron u n c ia t ion of be nz en e is th e sa me as tha t of ben z in e— on e

o f t h e p e t rol e u m frac t i on s bu t th is c an be r emed i ed by usin g benzol en e in s tea d of
,

ben zi n e (s ee N ot e I p , .

R E FE RE NCE S

R o scoe a n d S c h o rl emme r , T r e a t is e on Ch emis t ry , Vol I I I , P t I I I

. .

“
64; an d Re o s lu t i on Co n c e rn i n g Organ i c No me n c l a t ur e , ”
J ou rn I nd
. . a nd E ng
.

Chem , 10
.
9 44 .
142 LA BORA T OR Y M ANUAL OF OR GA NI C CH EMI ST R Y
or eth er ove r s odium A dd 5 0 cc of dry e th e r an d r e .

a ss e mbl e th e app ar a t us s e t ti n g th e fl ask in a b eak e r I n

, .

tw e n t y t o thir t y mi n u te s th e e th e r which is v e ry hygr o sc op i c ,

an d c an n o t o rdi n arily b e k ep t dry will be dry e n ough an d ,

pr a c tically n o m ore bubbl e s wi l l be given off N ow p our .

through t h e a ddi ti on tub e a mix tur e o f 3 0 gr ams ( 2 0 cc ) of .

br omb en z en e an d 3 0 grams ( 2 0 cc ) of .

of th e th eore tic al am ou n t) an d l e t s tan d ove rn igh t I f th , .

b e gi n s to b oil vi gorously c ool by p ouri n g cold w a ter i

b e ake r I t sh ould be wa t ch e d f or ab ou t an h our b e fore
.

th e l abor atory D o n ot a ll ow th e w a te r t o ru n thr ough

.

con d en s er ou tsid e of l ab ora tory h ours "

Durin g th e r ea c ti on th e s odium is ch an ge d to a blu e pow
a n d an e th e r eal s olu t i on of e thylb e n z e n e is f o rm e d T h e n ex t .

day r emov e th e e th e r by dis t ill a t i on obs e rvin g th e o rdi n ary

pre cau ti on s T h e e th e r is pr ac tic ally al l dis tille d wh en n o m ore
.

drops com e ove r D ry th e ou tsid e of th e fl ask conn e c t it in an

.
,

i n clin e d p osi ti on wi th th e e x trem e en d of th e n e ck cl amp ed

,

l oos e ly t o an air con d en s e r wi th a d ap te r attach e d l eadin g i n to

,

a r e c e iv e r an d l oo s e ly plug th e ann ul a r sp a c e in th e m ou th o f

th e r e c e iv e r wi th c o t t on Dis till t h e crud e e thylb en z en e from

.

th e app ar e n tly dry r e sidu e by h ea tin g wi th a lumi n ous fl am e

which is k ep t in c on s tan t m oti on Toward th e en d of th e dis .

til l a tion th e h e a t may b e i n cr e a s e d S in c e th e e th e r is n ot .

e n t ir e ly r e m ov e d in th e firs t dis t ill a t i on c ar e mus t b e tak en in

l

thi s op e r a ti on an d th e e y e s sh ould be pr ote c te d wi th g oggl e s .

Then subj e c t th e crud e produc t to a t l eas t tw o fra c ti on ati on s .

U s e a sm a ll dis t illi n g fl a sk a n d pl a c e i n t o i t a pi e c e of pumic e

or t ilin g t o aid e bulli t i on C a r e fully h e a t th e fl a sk dir e c tly w i th
.

a v e ry sm all fl am e Coll e c t s ep ar a te ly t h e p o r ti on s b oili n g b e l ow

.

b e tween 1 1 5 I 40 an d ab ove
— °
R e dis till e a ch p or ti on
°

colle c tin g as th e s ample th e p ar t b oili n g b e twe en 3 3 1

°

T h e b oilin g p oi n t of pur e et hylb e n z en e is

-
( 7 60 mm ) 1
.

I t is Oi grea t a dv an t age in t his fr a c ti on a t i on t o u s e a

'
c or .

sm a ll rou n d b ot tom e d fl a sk surm ou n te d by a You n g four p e ar

- -

s till he ad s e e Fig 4 p 2 5 Yi e ld 8 gr ams

,
.
,
. .
,
.

1
I W R i h rd s
. . c d F B rry J
a an Am .Ch m S a 37 .
9 98
ourn . er . e . oc .
, .
 LAB OR AT OR Y E X PE RI M E NT S 143

re sidue in the origin al fla sk con tain s s ome s odium

s t b e h an dl e d wi t h c a r e R e m ove th e m a t e ri a l a n d
.

pi e ce s to e thyl a lcoh ol or a ce to n e in a b eak e r ,

odium in e a ch pi e ce h as b een d e s troy e d

an o t h e r
. Dilu te wi th wate r (Ca re " ) b e f o r e p o ur
n in t o th e si n k Rin s e ou t th e fl ask wi t h alcoh o l
.

a n y w a te r
.

crud e amyl alcoh ol is us e d for d es troyin g sodium

e rmor e globul e s of
,

f ten fou n d a t th e e n d of th e m ai n r ea c tion c oa t e d

a myl o xid e ,
an d t h e ir pr e s en c e is som e tim e s n o t

tice d un til a f t e r w a te r h as b e en a dd e d "

Q U E S T I ON S
Of wh a t d o e s t h e crus t on t h e s odium c on sis t ?
N am e s om e o t h e r liquids t h a t migh t be us e d t o co ve r th e
s odium in th e b ot tl e .

3 . W h y mus t t h e xyl en e b e r e m o v e d a f t e r m a ki n g t h e bird

sh ot s odiu m ?
”

4 Comp ar e th e m ol e cul a r a n d s t ruc t ur a l f ormul a s of e t hyl

.

b e n z en e an d th e xyle n e s .

5 . H o w c o uld y o u dis t i n guish ch e mic a lly b e tw e en t h e is om e rs

,

e t hyl b e n z e n e a n d m xyl e n e ?-

Why n ot a dd th e br omb e n z e n e an d th e e thyl br omide

s ep ara te ly ?
Why mus t y ou wai t u n til th e e th e r is dry b e fore proce e di n g ?
Wh a t tw o o th e r o r gan ic c omp ou n ds a re f o rm e d in this
r e a c ti on ? Wh a t b e com e s of th e m ?

I s th e r e a c t i on applic a bl e t o th e aliph a t ic s e ri e s ?
Wh at is th e obj e c t of th e e th e r ? Why is th e e th e r ove r
s odium us e d ? W h a t o th e r subs tan c e s could be us e d ?
Why mus t th e con d en s e r be p e rfe c tly ti gh t ?
Why d oe s n o t al l th e e the r c om e ove r in th e firs t dis till a ti on ,

si n ce it b oils a t
W hy is th e fl a sk dri e d a f te r th e dis till a t i on o f th e e th e r ?
W h y is th e fl a sk i n cli n e d ?
Wh a t is th e c ause of th e blu e c ol o r ?
W hy is th e lumi n ous fl am e k ep t in c on s tan t m o t i on ?
Wri te th e s t r uc t ure of th e comp ou n ds f o rm e d wh e n e thyl
a lc oh ol a n d s o dium an d a myl a lc o h o l a n d s o diu mr e a c t
, .

Ou tli n e a n app a r a tus f or h e a t i n g a r e a c t i on mix tur e ab ove its

b oili ng p oi n t in a fl a sk ( G atterman n p
i

-
. .
,
 x r
E pe ime n t N o . 40

S YN THE S I S OF AN
‘
AR OMA TI C H YD R OCAR B ON BY ME AN S OF

FR I E DE L -
CRA E T S
’
R E A CTI ON

P r e parati on of D iph e n yl m e th an e f r om B e nze n e an d Be nzyl

ri
Ch l o d e

A t ta ch an a ddi ti on t ub e an d dry re flux con d en ser to a dry

3 00 cc fl a.sk .C on n e c t t h e t op o f th e c on d en s e r wi t h a t ub e

l eadin g in to the draf t pip e P u t 60 cc of b en ze n e an d 1 7 cc

. .
,
.

of b en zyl chl orid e i n to th e fl ask We igh ou t 5 grams of fin el y

1
.

pul ve riz e d an hydrous al umi n ium ch lorid e in a dry te s t tub e

2 -

cl os e d by a cork an d add this in tw o p or tion s (th e s e con d a f ter

th e firs t r ea c ti on h as subsid e d ) t o th e mix tur e in th e fla sk Let .

s tan d u n til th e evolu ti on of hydrogen chl orid e h as n early s topp e d

( t hir t y mi n u t e s ) Th. e n disc o n n e c t t h e a pp a r a t us a n d a d d
4 0 gr a ms o f fi n e ly gr o u n d i c e S h a k e
. a n d a f t e r th e ic e
,

h a s m e l te d s ep a r a te th e l ay e rs in a s ep ara to ry fu nn e l
,
Th e .

upp e r l aye r of b en z en e con tai n s th e diph en ylm e th an e an d af te r ,

th e l ow e r l a y e r h a s b ee n dr aw n off p our th e upp e r l ay e r fr om

th e top o f th e fu n n e l .

I n ord e r t o r e m ov e th e b e n z en e m os t quickly a n d a ls o l e av e
th e cru d e diph e n ylm e th an e in a sm a ll fl a sk r e ady f or th e fin al
fr a c tion a tion th e s olu tion is f ra c ti on a te d in por ti on s un d er
,

dimi n ish e d pressur e or i n vac u o as follows : Con n e c t a 1 2 5 cc .

Cl ais e n a n d an o rdi n ary dis t illi n g flas k f or dis t ill a ti on i n vac u o

-

1
T he va p ors of ben zyl c h l ori de are ve ry irri ta ti n g to th e e ye s an d th e mu c ou s
membra n e s of th e n o s e a n d mo u th .

1
T h e s e a l e d bo t t l e s in w h i c h th e a n h yd ro us a lu mi n iu m c h l ori d e c ome s o f ten
c on ta in c on si d e ra bl e p re ssur e . Grea t c are is th erefore n ec e ssa ry in op en ing them .

U s e th e me th od d e s c ri be d on p 3 3 a n d c ompl e te ly w ra p th e bo t tl e in a t o w e l
.
,

be fore s trikin g th e n e c k a b o v e t h e fil e ma rk a bl ow w i th t h e fil e T h e a l umin ium .

c h l ori d e mus t b e in good c o n d i t i on or t h e expe rimen t w ill be a f a ilure .

144
146 L AB ORAT ORY MANUAL OF OR GA NI C CH E M I S T R Y
Wh a t o the r cla ss o f c omp ou n ds c an be m ad e by th e Frie de l
Cr a f t s r ea c ti o n ?
Diph e n ylm e t h an e on oxid a ti on wi th chromic a cid mix tu r e
y i e lds b e n z o ph e n o n e I s
. t his r e a c t i o n g e n e r a l wi t h
a r om a t ic hydr o c a rb on s ? Comp a r e t riph e n ylm e t h an e a n d
diph e n yl .

Wha t ki n d of h al oge n d e riva tive s are us e d in th e Fri ed e l

C r a f t s r e a c ti on a liph a tic or a r om a tic or b o th ?
, ,

Would th e re b e an y r ea c ti on b e tween b r omb en z en e an d

b en ze n e in th e pre se n ce of alu mini um chl orid e ?
H ow c ould y ou pr ep a r e t riph e n yl m e th an e ? -

From its s t r uc ture w ould y ou e xp e ct diph en ylm e th an e to

b e s o lubl e in b e n z e n e ?
Discuss th e u s e of th e a lumin ium me rcury coupl e in pl a ce
-

o f th e a lumi n iu m chl o r id e f or p r e p ari n g diph e n ylm e th a n e ,

e tc .
(J . B . C o h e n ,Or g a n ic C h e m is t ry f or A dv a n c e d
S t ud e n t s P t I 2 d E d
,
.
,
.
9 81; a n d N o rris ,
E xp e r i
m en tal Organi c Ch emis try p .
 E xpe rime n t No . 41

F ORMA TI ON OF A F RE E RADI CAL

i
T r ph e n l me th l y y
P l ac e 5 0 . gram of gr a m
t riph en y l c h l orme th an e of 1
an d 1

mm I n to a cl e an dry N o 1 t e s t t ub e ,
S e a l a gl a ss
,
.
-
.

o p en e n d s of t en t h e gl a ss n e a r t his e n d in t h e bl a s t
,

draw it ou t to a n a rr ow t ub e ab ou t 2 mm in di am e te r .

e s e a li n g of a b omb t ub e p Wh en c old p our in ,

.
,

cc of dry b e n z en e an d a f te r le ttin g it dr ai n w e ll s eal off

.
2

e e n d o f th e t ub e ( C a r e "
) S h a k
. e a n d a ll o w i t t o r e m a i n

a horiz on t a l posi t i on f or t w o d ays T h e h eavy br ow n oil .

5 o n th e b o tt om is a d oubl e c omp o u n d o f t ri

an d zi n c chl o rid e A t th e e n d of th e t im e sp e cifi e d

.

th e t ub e a n d quickl y divid e i t s c o n t e n t s i n t o tw o t e s t t ub e s -
.

re ady a s olu ti on of i odi n e in b en z e n e a n d imm e di a te ly t e s t

n s a t u r a t e d n a t ur e o f t h e c omp o u n d by sl owly a ddi n g th e

ion T h e o th e r p or t i on r apidly a bs o rbs oxyg en

.

th e a ir an d th e i n s o lubl e t riph e n yl m e thyl p e r oxid e is - -

re c ipita t e d .

R E F E RE N C E

Gomb e rg, xist e F re e icals A mer

”
T he E nc e of R ad , J ourn . .

S oc . 36 —
1 1 44 7 0 .
,

n yl c h l o rme th a n e m us t be kep t in s ea l ed bo ttl e s sin c e it w ill sl ow ly be

,

by mo is t ure in an o rd i n a ry c ork— s t opp er e d bo ttl e .

t beu is s o na rrow t h a t t h e be n z e n e d o e s n o t flo w d o w n rea d ily a l te r ,

c oo l w h en t h e liqui d ,

t w il l ru n d ow n ea s ily
148 LABORAT ORY M ANUAL OF OR GANI C CH E M I ST RY

Q UES TI ONS

1 . I s th r
e e an y o bj c i
e t on to th e u s e of a l rg r
a e s ub e
te t t -
in
e xp e rim en t ?
W hy mus t dry b en z e n e be us e d ?
E xpl ai n th e r e a dy abs o rp ti on o f i o di n e by t h e s o lu t i on .

W ri te th e f o rmul a f or th e comp ou n d f o rm e d wh en th e s olu

t i on is exp o s e d t o t h e a ir .

Comp a r e s om e o f th e hi gh e r h om ol ogu e s o f t riph en ylm e thyl

wi th t riphe n ylme thyl i ts e l f in r e gard to physica l an d
,

ch emic a l p r op e r ti e s (S e e J ou r n A mer Chem S oc 3 6

. . . . .
,

1 165

6 . Discu ss th e qu e s ti on of th e e xis ten ce of fre e ra dicals .

150 LABORAT ORY M ANUAL OF OR GANI C CH E M I ST RY
con sis t m a in ly of p dibromben zen e Diss olve this m ateri al in
-
.

—
1 0 2 0 cc o f h o t a lc o h o l a n d fil t e r t h e h o t s o lu t i o n
. I f the .

fil tr a t e is n o t wa t e r whi te d e co l oriz e by a ddi n g a n im a l Ch a rc oal

-
,

in sm a ll am ou n t s to avo id e xc e ssive f oami n g o f th e h o t liquid ,

cove r wi th a wa t ch glass h e at on th e s team b a th f or s eve ra l

,
-

m in u te s an d fil te r ag ain w hi le ho t S e t the b e ak e r a sid e f or

,
.

crys tall iz a ti on Fi n ally fil te r off th e crys tals of p dibrombenzen e

.
-

wi th suc ti on dry an d d ete rmi n e th e m e l t in g p o in t

,
-
.

a .R ep ea t e xp e rim e n t c u n d e r e thyl i o did e (p 3 8 ) u sin g .

on ly a p o r t i on o f a d r op o f br omb en z e n e R e sul t ? .

b R ep e a t th e s am e e xp e rim e n t usi n g b e n zyl Chl orid e

. .

c . R ep e a t th e ab o v e e xp e rim e n t s bu t u s e dis t ill e d w a te r,

in pl a c e o f th e a lc oh o l D o n o t mis t ak e an e mulsi on f o r a p re
.

c ip it a te Comp a r e r e sul t s wi th t h o s e wi t h th e a lc oh o lic s olu t i on

. .

Q UE S TI ON S

1 . Wh at is th e obj e c t o f the iron n ails ? Why n o t u s e iron

fil i n gs ? Un d e r wh a t c on di ti on co uld th e l a tt e r be us e d ?
2 . Wh a t dib r om pro duc t is ob ta i n e d in th e exp e r im e n t ? A re
a n y o f th e o t h e r t w o p o ssibl e dibr o m pr o duc t s f o rm e d a t

a ll ?

Why should th e r e a c ti on mix ture n o t be a llow e d to s ta n d

m ore th an on e or tw o d ays a f te r th e br omi n e h as b e en
a dd e d ?

Wh a t is th e r e ddish brown pr e cipi ta te s om e tim e s f o rm e d

-

wh e n th e s odium hydroxid e s olu ti on is a dd e d ?

How is b e n zyl br omid e pr e p a r e d ?
Wh at are a lph a an d b e t a b en z e n e h exab romides ? (J B
-
. .

Co h e n Or ga n ic Ch e mis t ry f or A dva n c e d S t ud e n t s
”
, ,

P t I I 2d Ed .
,
2 60
. H ow pr e p a re d ?
Wh a t advan tage s h as a s ep ara t ory fu n n e l ove r d e ca n ta tion ,

a n d d e c a n t a t i on ove r a s e p a r a t o ry fu n n e l f or w a shi n g ,

purp ose s ?
8 . Comp a re th e s t a bili t y tow a r d hydr o lyzi n g r e a ge n t s of th e
a ryl h ali d e s wi t h t h e a lkyl h a lid e s .

Wh a t comp oun d s if an y ar e f orm e d by th e a c tion of a lcoh olic

, ,

KOH on b e n zyl chl o r id e ; on 1 ph en yl 2 c h l orp r op a n e ; - - -

picryl chl orid e ; bromb en z en e ?

How c an br omb e n z e n e b e c on ve r te d in t o b e n z en e ? I n to
diph en yl ?
 LAB OR AT OR Y E XP E R I M E NT S 15 1

G ive s om e of th e mo dific a ti on s in th e m e th ods of usin g

b r omi n e f or b r omin a ti on s .

G iv e me th ods f or pr e p a r i n g Chl o rbe n ze n e fr o m an ili n e ;

f r om c h l orbe nz oic a cid ; an d f or b en zyl i odid e from b en zyl
ch l orid e .

H ow a re t h e i o d o d e riv a t iv e s pr e p a r e d ?
-

E xpl ai n th e a c t i o n o f t h e b on e bl a ck in d e c o l orizi n g the solu

ti on of dibromb enz en e .
 E pe i x r me n t No . 43

S U L F ON A T I ON OF A N A R OM A T I C H YD R OCAR B ON

P r e par ati on of B e n ze n e S ulf on i c Ac i d , S o d iu m S al t

To 5 cc
fu min g sulfu r ic a cid in a t e s t tub e a dd in small
. of -
, ,

p o r ti on s 3 cc o f b en z en e sh aki n g vigo r ously a n d coolin g a f te r

.
,

e a ch a ddi ti o n Wh e n th e b e n z e n e h a s a ll diss o lve d a n d th e liquid

.

is cle a r sl owly p our it i n to 2 0 cc of wa t e r in a fl a sk coolin g it

,
.
,

u n d e r ru n n in g w a te r Fil te r Off wi th suc ti on an y diph e n yl

.

sulfon e which s ep a r a te s P ar tly n e u t raliz e by a ddi n g 4 grams .

o f crys t a lli n e s o dium c a rb o n a t e t h en a d d 5 gr a ms of c omm o n ,

s al t W arm an d s tir t ill it diss olve s fil te r while h o t th r ough a

.
,

flu t e d fil te r p ap e r a n d c oo l S t ir w e ll wh e n th e s olu ti on is a lm os t
1
,
.

cold T h e s odium b e n z e n e sulfon a te s e p a r a te s ou t in a m a ss o f

.
-

whi te lus t r ous pl a te s I t may b e n e ce ss a r y t o s e t th e b e ak e r

‘

in ic e in o rd e r t o pr om o t e a n d c ompl e t e th e crys ta l l iz a ti o n .

Fil te r wi th suc ti on P r e ss as dry a s p o ssibl e whil e it is in th e

.

fu n n e l A llow to dry on fil te r p ap e r or pr e ss ou t on a p orous

.

pl a t e R e crys ta lliz e f r o m h o t a lcoh ol T h e pure s odium s al t

. .

m e l t s a t a b ou t S uch a me l t i n g p o i n t c a n n o t b e tak e n wi th -

th e o r di n a ry app a r a tus Y i e ld 4 grams .

,
.

N OT E S

1 . is l f l p d r i g th sulf tio Th is
A gr e e n h c o o r o ten d ev e o s u n e on a n .

usually i pp s d sa ear y lli ti f r m l h l

in th e r e c r s ta za on o a co o .

2 S m tim
. o t h ma t e r ia l d e s
e es t c rys ta lli
e ou f th a l c o o no ze t o e

h li c s lu ti ry w ll P ssibly a sol bl l c h l t simil r t “ ”

o o on ve e . o u e a o o a e a o

h yd r t i f rm d E vap r a ti t h r ugh c o oli n g an d s t i rr i g

“ ”
a a e s o e . o on , o o n
,

gen e r a lly ov e r c m t h d i f fic loty e e u .

1
S ee f oo t -
n ote , p . 1 28 .

15 2
 E xpe r i me n t N o . 44

NI TR ATI ON OF A N A R OMA TI C HYD R OCARB ON

P re parat i on of N itr ob e n z e n e

In fl ask car e fully mix 1 8 cc of con c n i t r ic a cid an d 1 8 cc

a . . .

o f c on c sulfuric a cid cooli n g u n d e r r u n n in g wa te r a f te r ea ch

.
,

a ddi t i on o f o n e a cid t o th e o t h e r Wh e n th e s o lu t i on h a s com e

.

t o th e r oom t e mpe r a tur e ad d i t sl owly fr o m a dr oppin g fu n n e l t o -

1 3 cc o f b e n z e n e c on t a i n e d in a n op en 3 00 cc fl a sk u n d e r th e
. .
,

h ood (D o n ot u s e a n y cork or rubb e r con n e c ti on ) S h ak e w ell

. .

an d c oo l fr e qu e n t ly u n d e r ru n n i n g w a t e r k e e pi n g th e t e mp e r a tur e
,

o f th e liquid b e l ow Wh e n all th e mix tu r e h as b ee n add e d ,

h alf imm e rse th e fl a sk in w at e r m a in tai n e d a t 50 by m ean s of °

s team or a burn e r k ep t burni n g l ow an d l e t it r em ain a t this

t e mp e r a t ur e f or thir t y mi n u t e s c on n e c t e d wi t h a t ub e l ea di n g
t o th e dr a f t pip e S in c e th e mix t ur e s e p a r a te s i n t o l aye rs on
'

s tan din g it mus t be sh ak en o cca si on a lly du r in g th e h ea tin g

,
.

T h e n i t r a ti on is c o mpl e te wh en a dr op which is a dd e d t o w a te r
si n ks t o th e b o tt om T h e pr e s en c e of an y u n ch an ge d b e n z e n e
.

will caus e it to fl oat I n p e rfo rmin g this te s t s tir w ell to m ake

.

c e r ta in th a t a n y drops on th e surfa ce are n ot h e ld up by surf a ce

t en si on a l on e .

P o ur th e c on t en t s of th e fl a sk in to ab ou t 5 00 cc of w a te r .

in an o th e r fl a sk sh ak e t h o r oughly c ool i t a n d s ep a r a te th e l ow e r
, , ,

t urbid y e l l ow l a y e r o f ni t r ob e n z en e by m e an s o f a s ep a r a t o ry
fun n e l R e turn it to th e fun n e l an d wa sh th e oil wi th s o dium
.

hydroxid e s olu t i on u n t il fr ee from a cid an d fin a lly w ash wi th ,

wa te r S ep a ra te a s c ompl e te ly as p ossibl e an d r e turn th e oil t o

.

a d r y s ep a r a t o ry fu n n e l A dd c a lcium chl o rid e a n d sh ak e

. If .

a n a qu eo us s o lu t i on o f t h e s a l t s e p a r a t e s r e m ov e i t a n d a dd fr e sh
,

ca lcium chlorid e R ep e at an d t hen t ran sfe r th e liqui d to a sm a ll

.
,

15 4
 LAB OR AT OR Y E X P E RI M E NT S 15 5

ye r fl a sk add se ve r al pi e c e s of fr e sh cal cium chlorid e

e , ,

s topp e r an d a llow to s t an d o ve rni gh t to compl e te th e dryin g

,
.

Be sur e to cl e an th e s ep a r a t o ry fu n n e l s o t h a t t h e s topp e r an d
s top co ck will n o t s t ick I t is w e ll t o k eep t h e p ar t s s ep a ra te d
-
.
,

bu t t i e d wi th a pi e c e o f t wi n e Wh en dry th e ni t r ob en z en e will
.

be cl ea r Fil te r t hrough a fu n n e l a s usu al con ta ini n g a plug

.

gl ass wool i n t o a d r y dis t illi n g flas k wi t h l ow ou t l e t tub e -

T h e s t e m o f th e fu n n e l sh ould r ea ch b e l ow th e op e n
o f th e d e liv e r y t ub e D is t ill Ca t ch th e firs t run n i n gs
. .
,

ch con sis t chi efly o f b en z en e an d tra ce s of wa te r dire c t from ,

o u t l e t t ub e Wh en th e cle ar ye ll owish ni t rob e n z en e b e gin s to

.

a dry a ir c o n d en s e r a n d dis t ill usi n g a dry w e i gh e d ,

t l e a s t h e r e c e iv e r D o n o t in an y c a s e a ll ow th e
.

a t u r e t o go m o r e t h a n 5 a b o v e t h e b o ili n g p o i n t :
°
th e -

e s o m e t im e s d e c o mp o s e s expl o siv e ly
1
Bp c or . . . .

eld 7 g r,
a ms
1 .

N OTE

N i t r ob en z en e is a poiso n . I ts vapo r sh ould n ot be b r ea th ed

c es s iv e l y a n d it sh oul d o t n be a ll ow e d t o r e ma in in con tac t wi th
e ski n .

Q UE S T I ON S

1 . Ca n i trob en z e n e be prep a red by addi n g b en z e n e t o th e a cid

n

mix tur e i n s t e ad o f th e a cid mix tu r e t o th e b e n z en e ?

,

Why is th e m e th o d us e d in t h e l ab o r a to r y p r e fe rr e d ?
2 . Wh a t comp ou n d is f o r m e d if th e t e mp e r a t ure is a ll ow e d
t o ris e much a b ov e
3 . W h a t is t h e Obj e c t o f t h e sulfuric a cid ?
4 . Wha t c ompoiI n ds ar e f o r m e d by th e n itron a tion 2
of

t o lu e n e ? U n d e r wh a t c on di t i on s d o e s t o lu en e yi e ld b en
z oic a cid wh en tre a te d wi th n i tric a cid ?
is is mo s t likely to h a pp en w h en th e produ c t c on ta in s pol yn itro de riva tive s
1
Th
a n d a ls o n i t ro d e riv a t iv e s o f h o mo l o u e s o f b e n z e n e if a
g go od qu a li t y of benz en e
w a s n o t us e d .

Th e w o rd n i tra t i o n
2
a t pre s e n t s ta n d s f or t h e f o rma t i on o f bo th a t ru e

n i tro d e riv a t iv e li ke n i t r obe n e n e a n d o f a n i tra t e like t h e c e llul o s e n i t ra te s

z T he .

t e rm n it o n a t ion is sugge s te d f or th e fo rmat ion o f a n i tro de riva t iv e jus t a s

“ ”
r
“
sulfo n a ti on s ta n d s for th e forma ti on o f a sulfo d e riva t ive in a similar manner
”
,
15 6 LAB OR AT OR Y MANUAL OF OR GA NI C CH E M I S TR Y
N am e s om e imp or ta n t cl a ss e s of n i tro comp ou n ds an d
-

i n dic a te th e i r use s .

W hy mus t n i t rob e n z e n e n o t b e h e a t e d a b ov e i t s b o ili n g

p oin t ?
H ow a re m o s t n i t r o c omp o u n ds pu r ifi e d ?
-

A re di ff e r e n t p r o duc t s o b t a i n e d wh e n ni t r ob e n z e n e is chl o
r in a t e d a n d wh e n Ch l o r b e nz e n e is n i t r a t e d ?

H ow a re t h e c o n di t i on s o f n i t r a t i o n v a r i e d ? Comp a r e th e
prep a ra tio n o f n i t r ob en z e n e a n d of n i t r oph e n ol .

Wh a t is th e ge n e r a l Ch e mica l i n fl u e n ce o f th e n i t r o gr oup -

H ow a r e th e a liph a t ic n i t r o c omp o u n ds pr e p a r e d ?
-

m e thods .

H ow is ph e n yl n i tr o m e th an e pr ep a r e d ? Why is
- -

s olubl e in alk ali ?

Comp a r e th e s t r uc t ur e of n i tr o c omp ou n ds a n d th e is om
-
e ri

n i t ri t e s
.

Wh a t a r e th e pro duc t s of th e r e duc ti on o f n i tr o comp o u n ds

-

an d o f n i t r i te s ?

Wh a t is a ps e ud o a cid ?-

H ow a re th e a lph a a n d b e t a m on o ni t ron aph th al en e s p e

- -
r

par ed ?
H ow c a n t h e thr e e di ff e r e n t cl a ss e s o f a liph a tic m on o n i t r o -

c ompoun ds be di s ti n guishe d ?
 LAB ORA T OR Y MANUAL OF OR GANI C CH E MI ST RY
wo r kin g wi th h e r t o k e e p aw a y fr om fr ee fl am e s "
et

at h a s a v e ry high v a p o r pr e s s ur e a n d is v e ry ,

Fi n ally d r aw off th e a qu e ous l aye r in to a fl ask T h e .

e x t r a c t s sh ould b e disc a r d e d .

(I f t h e e n t ir e e xp e rim e n t c a n n o t b e c ompl e t e d a t

i t sh ould b e i n te rrup t e d a t this p oi n t in o rd e r t h a t th e

z a tion wi t h s o dium hydr o xid e may b e dir e c t ly f o ll ow e d by t h e

s te am dis till ati on an d th e h e a t of n eu t r a liz a tion th e r eby

,

u tiliz e d ) .

T h e fr e e ami n e (an ili n e) is ob t ai n e d fr om th e d oubl e s al t in

th e e x t r a c t e d a cid s o lu t i on by a ddi n g gr a du a lly a s olu ti on o f
ab o u t 5 0 gr ams o f s o dium hydr oxid e in 9 0 cc o f w a t e r S t ann ic . .

a n d s t a n n o us hydr o xid e s f o r m a t firs t a n d p a r t i a lly di ss olv e .

T h e pr e cipi ta t e may b e e n t ir e ly diss o lv e d by a ddi n g m o r e s o dium

hydroxid e bu t this is n o t n e ce ss a ry T h e mix ture sh o uld h ave a
,
.

s tron gly a lk alin e r ea c ti on (Why ?) I f b oilin g o ccurs duri n g

.

t h e a ddi t i on o f th e a lk a li c oo l th e s o lu ti on u n d e r run ni n g w a t e r
,

b ef ore addin g m or e (Why ?) M os t of the ani lin e rise s to th e

.

t op as an oil .

T he anilin e could n ow be ex t ra c te d wi th e th e r bu t this is ,

n o t a dvis abl e sin ce th e a lk ali n e s olu ti on forms a dif fic u l tl y

,

s ep arabl e e mulsi on wi th th e e the r .

D i s t il l ati on wi th S te am 1
T h e fr ee a ni li n e is s ep ar a t e d by
.

s te am dis t illa tion usi n g th e app aratus sh own in Fig 1 3

, . .

S t eam is p a ss e d i n t o th e fl a sk thr ough a t ub e which is b en t

in such a w ay th a t it r ea ch e s ahn os t to th e b o tt om (Wh y ? )
wh en th e fl a sk is i n clin e d (Why is th e fl ask i n cli n e d ?) T h e
.

o u t l e t t ub e sh o uld b e c u t o ff jus t b en e a th th e s t opp e r an d

th e b e n d S h ould b e jus t ab ov e th e s t opp e r (Why ? ) T h e ou tl e t .

t ub e a ls o S h ould b e o f a l a rg e r di a m e t e r t h an th e i nl e t t ub e .

T h e fl a sk S h ould n ot be more than ha lf fu l l wh en th e dis till a ti on

is b egu n U s e a l on g w a t e r Co n d en s e r M ak e th e rubb e r c on
.

O
.

n e c tio n s a s sh o r t a s p o ssibl e a n d a t t a ch th e rubb e r t ub e t o th e

1
Re fe ren c e s f or th e prin c ipl e s i n volv ed in d is t ill at i o n w i th s t eam : M organ ,

T h e E l e me n t s o f P h ysi c a l Ch e m is t ry —8 S mi th
”
5 t h E d 1 77
, ; I n t ro d u c
.
,

t i on t o I n o rga n i c Ch e mis t ry 5 6 3 ; Walke r I n trod uc t i on t o

“
3d Ed ,
.
,

Ph ysic al Ch emis try 7 t h E d ,

”
87
. ,
 LAB ORAT ORY E X P E RI M ENT S 15 9

of fl a sk in such a w ay th at it c an e a sily an d quickly

th e
e d if o cc a si on d e m an ds S e t th e fl a sk i n to a B ab o
.

p o n a wir e g a uz e a n d h e a t
,
g e n t ly duri n g t h e op e r a

to wr ap a t ow e l a r ou n d th e upp e r p ar t of
fl ask I f th e s t e a m is p a ss e d i n to t h e s o lu t i on wh en c old
cra cki n g sou n d is Of ten h e a rd This dis app ears as s oon a s .

li quid b e com e s h o t .

T h e s te am o n th e d e sk c a n b e us e d as th e supply S in c e .

a lw a ys c on sid e r abl e c on d e n s a t i on w a t e r a 5 00 cc ,
.

D /a g r a m
‘
of fl pp a / w as

f or e d m
FI G . 13 .

be pl a c e d asr ap b e twe e n th e s te am n ozzl e a n d th e

a t
tu s . U s e a t hr ee h o l e d s t opp e r in t his fl a sk
-
T h e in le t .

t ub e s S h ould b e c u t Off jus t b e l o w th e s t opp e r I n to .

h ol e p a ss a gl a ss tub e l ea din g to th e b o t t om of the

t dow n w a r d s a b ov e th e s t opp e r a n d c on n e c t e d wi th a
_

u bb e r t ubi n g t o a c t a s a S iph o n U s e a sc r e w cl amp.

Wh en th e fl a sk is n e a rly fill e d wi th
th e w a te r will go ou t a n d it is n o t n e c e s
n duri n g t his t im e I f t h e scr e w cl amp .

nn el pa r t iall y lin ed w i th s t rips of a sbe s t o s ,

an d is
160 LAB OR AT OR Y MA NUAL OF OR GANI C CH E M I ST RY
is p ar tly op e n e d an d prop e rly adjus te d th e w ate r will p a ss o u t
r e gul arly wi th ou t r e quiri n g fur th e r a tt en ti on .

Or s te am c an b e gen e r a te d in an o rd in a ry t in oil c an p ro -
,

v ide d wi t h a s a f e t y t ub e 5 0 cm l on g ; t h e sp ou t is us e d f o r th e
.

o u tl e t . Or a fl a sk may be us e d wi th a s a fe t y t ub e an d o u tl e t
t ub e . T h e s a f e t y t ub e sh ould e x t e n d a lm o s t t o th e b o t tom ,

an d if a wid e on e is us e d such as a c on d en s e r t ub e it will a ls o

, ,

s e rve for p ouri n g in th e w a te r e sp e ci ally when the b oil e r ,

is h ot (al th ough in such a c a s e th e b o ile r mus t n ot be c on

n e c t e d wi th a n y app a r a t us wh e n th e w a t e r is b e i n g a dd e d

u n l e ss b oilin g w at e r is us e d ) .

T h e dis t ill a t i on is c on sid e r e d c ompl e te wh e n n o m or e o ily

drops c om e ove r in th e dis till a te ( 1 t o 5 h ours) R em ove th e rub 1 .

be r c on n e c t i on fr om th e m ai n fl a sk b e f o r e t urni n g off th e s t eam

or ex ti n guishin g th e fl am e Coll e c t ab ou t 3 00 cc of th e cl oudy
. .

dis till a te S om e of th e an ili n e s ep a rate s a s an Oil a t th e b o ttom

.

o f th e r e c e iv e r Towa rd th e e n d of th e dis t ill a ti on jus t af te r

.
,

th e oily dr ops h a v e ce a s e d t o c om e ov e r c oll e c t s ep a r a t e ly ,

2 cc of th e cl e a r dis t ill a t e a n d m ak e th e f oll o wi n g tw o t e s t s f or

.

diss olve d an ilin e .

T o on e p or t i on add s om e br omi n e w a t e r Wh at is th e .

whi te pre cipi t a te ?

T o a n o t h e r p o r t i on a dd a sm all am o un t o f a fil te r e d w a t e r
s olu t i on of good ble a chin g p owd e r .

E th e r E xtr a c ti on S a tur a t e t h e s t e a m dis t ill a t e c on t ai n e d

.

in a li te r s e p a r a t o ry fu n n e l wi th p owd e r e d s o dium chl orid e ,

2 5 gr a ms f o r e v e ry 1 00 cc o f liquid Th en ex tr a c t th e an ili n e
. .

wi th e th e r usi n g thr e e succe ssive p or ti on s of e th e r 5 0 cc a t firs t

, ,
.
,

th en 3 0 cc a n d 3 0 cc . Te s t a p or ti on of th e a qu e ous s olu ti on
.

a f t e r th e e th e r e x t r a c t i o n s t o s ee if a n y an ili n e r e m a in s in ,

s am e m an n e r th a t you te s te d th e s t e am dis till a te ab ove Dry .

th e c ombi n e d e th e r ea l s olu ti on s in an E rl en m e y e r fla sk by
a ddi n g tw o o r t hr e e sm all s t icks Of s olid s odium hydr oxid e
. .

S topp e r th e fl a sk wi th a c o rk a n d l e t s t a n d o v e r n igh t I f an .

a qu e ous s o lu t i o n o f s odium hydr oxid e f o rms a t t h e b o tt om ,

th e l a ye rs sh ould b e s ep ar a te d fre sh s odium hydr oxid e add e d

, ,

an d th e mix tur e a ll ow e d t o s t an d o v e r n i gh t iagain ( Ca l .

16 2 LAB ORAT ORY MANUAL OF OR GANI C CH E M I STRY

y ou ccou n t for the obs e rvation whi ch you h ave m ad e wi th

a

t h e s e s a l t s o lu ti on s ?
6 Diss olve tw o or thr ee dr ops of an ili n e in th e l e a s t p ossibl e
.

am ou n t o f di lu t e hydr o chl oric a cid Why d oe s ani lin e diss olve

.

e a sily in a cids whil e i t is s o lubl e wi th difli c u l t in w a t e r ? N u

y e

t raliz e wi t h s odi um hydr oxid e s olu t i on .

d T o f our or fiv e dr ops of c on c sulfuric a cid in a sm all

. .

p orcel ain e vap orati n g dish add a drop of ani lin e on a s tirrin g
ro d .Wh a t is th e whi te solid f orm e d ? N ow a dd tw o or three
drops of a wa te r s olu t i on of s odium dichrom a te an d s tir .

Comp a re H ol l em an Org an ic Ch emis try

, 4 th E d ,
”
.

e . or three drops of n i trob en z en e to 0 5 cc of

A dd tw o . .

a n ili n e N o t e th e d e e p re d col or th a t is f orm e d ( Comp a r e

. .

B iron a n d M orgul ev a Col o r of M ix tur e s of An il i n e s wi th

,

A r om a t ic N i t r o Comp ou n ds J ou rn Ru s s P hys Chem S oc

.
”
. . . . .
,

46 1 5 98 ; Chem A bs trac ts , 9
. 2 06 9 .

Q UE S T I ON S

Wri te th e e qu ati on f or th e re duc tion of n i trob en z en e .

E xpl a i n why onl y a li t t l e a cid is n e ce ss a ry in th e pr oduc ti on

o f a n ili n e c omm e rci a lly fr om n i t rob e n z e n e by m ea n s o f ir on

a s t h e r e duci n g a ge n t .

Why is n o t a ll th e hydro chl oric a cid a dd e d a t on e tim e wh en

th e n i t r ob e nz e n e is r e duce d by t in a n d hydr o chl oric a cid ?
Ca lcul a t e t h e a m o un t of hydr o chloric a cid n e c e ss a ry f or t his
exp e rim e n t .

Wh a t I s th e n a ture of th e s al t form e d from s tan n ic chl orid e

a n d a n ili n e hydr o ch l o rid e ? H ow w ould t his s a l t b e h av e
in a wa t e r s o lu t i on ?
6 . I S t h e r e a n y di ff e r e n c e b e tw e e n a d oubl e s a l t an d a c ompl ex
s al t ?
W hy is it n e c e ss a ry t o coo l b e f or e ex t r a c ti n g th e n i t ro
.

b en z en e wi t h e th e r ? Wh a t is th e prin ciple u n d e rlyi n g

e t h e r e x t r a c t i on ?

8 . W h a t d oe s th e e th e r e x t r a c t c o n ta in a n d why is it d e sir ab l e
t o p e rf o rm t his e x t r a c t i on ?
Co uld a n y o th e r m e th od be us e d in pl a c e of th e e th e r ex tr a c
t i on ?
 LAB ORAT OR Y E XPE RI M E NT S 16 3

H ow d oe s s odium hydroxid e re a c t wi th th e d oubl e s al t ?

Wr i t e a ll e qu a t i on s f o r t his ch e mica l ch a n ge .

S h ow h ow a n ili n e hyd r o ch l o r id e c a n b e c on v e r t e d i n t o
a n ili n e wri t i n g t h e e qu a t i on fr o m th e i o n ic s t a n dp oi n t
,
.

Why is it n e ce ss a ry to be ca re ful in a ddi n g th e s odium

hydroxid e s olu tion t o th e s olu tion of th e d ouble s al t ?
E xp l ai n why th e liquid b e c om e s h o t .

Wh a t is th e gr ay pre cipi ta t e th a t f orms wh en a l a rge exce ss

o f s o dium hydr oxid e h a s b een us e d ? A cc ou n t f or i t .

( R e f e r e n c e s ,
M e ll o
,
r M od e r n I n o rg a ni c C h e mis try ,

79 0 — 1
,
a n d D i t t e,
A n n .C he m
. P hy s . 2 7
Discuss fully th e p r i n cipl e s i n vo lve d in s t ea m dis tilla ti on .

H ow c a n y ou t e ll by ch e mic a l m ea n s wh e n all th e a n ili n e

h a s b e e n dis t ill e d ove r wi t h s t ea m ?
Why n o t con tin u e th e s te am dis till a t ion un til th e di s til la te
g iv e s n o t e s t f o r a n ili n e ?
D oe s a n ili ne r e a c t a lk a lin e toward li tmus ? I s it a t ru e
b ase ?
I n a S h or t t im e a f te r th e s te a m dis t ill a t i on h as b e gu n a
con sid e rabl e am ou n t of an ilin e coll e c t s in th e re ce ive r ,

a n d by t h e t im e th e dis t ill a t i on is c o mpl e t e d pr a c t ic a lly

a l l t his a ni li n e h a s dis a pp e a r e d .E xpl a i n .

Durin g th e s te am dis tilla t i on so m e of th e an ilin e colle c t s

a t th e b o tt om o f th e r e c e iv e r s om e fl o a t s on th e w a t e r
,
.

E xpl ai n .

E xpl ai n why an ili n e hydr o chl orid e is n o t v o l a t il e wi th

s te am whil e an ilin e is .

Would y ou exp e c t ph en yl a mm oni u m hydr oxid e to be vol a

til e wi th s t e a m ?
Wh a t is th e obj e c t of a ddin g s odium chlorid e t o th e s te am
di s till a te b e f or e th e e t h e r e x t r a c t i on ?
E xpl ai n why th e e t h e r s o lu t i on is dri e d wi th s o lid s odium
hydroxid e i n s te ad of c alcium chl orid e or anhydr ous
sodium sulf a t e Could th e l a tt e r be us ed ?
.

Why is n o j a ck e t n e c e ss ary f or th e c on d en s e r ; would it do

an y h a rm if a c o n d e n s e r j a ck e t w e r e us e d ?

P oin t ou t th e r e la ti on ship b e twe e n th e d oubl e s al t o f s tann ic

chl orid e an d an ilin e hydrochl orid e an d amm on ium chlor ,

pl atin ate .
 E xpe ri me n t N o 46 .

A CE T YL AT I ON OF A N A R OMAT I C A MI NE

P r e par at i on of Ac e t -
o -
to lui di d e fr om -
o To l u i d in e
T o 5 cc of a c e t ic . hyd r id e in a 1 2 5 cc E r l e n me y e r fl ask
an
1
.
,

a d d 2 dr o ps o f c o n c sulfu r ic a cid Th e n a dd S l o wly in s mall

. .

p o r ti on s wi th sh aki n g a n d c oo lin g u n d e r r u n n i n g wa te r a f te r e a ch
,

a ddi t i on 4 cc o f o t o luidi n e
,
.
-
A ll o w th e m ix t u r e t o s t an d a t
.

r o om t emp e ra tur e f or on e h a lf h ou r or l on ge r T h e e n ti r e p r oduc t

-
.

t h en a pp e a r s li k e a s olid m a ss I f i t d oe s n o t s o lidify sc r a t ch
.
,

t h e i n sid e w a ll o f th e v e ss e l wi t h a gl a ss r o d t o pr om o t e c r ys t a l
liz a t ion N ow a dd 3 0 cc o f w a t e r an d w a r m o n th e s t e a m
. .

b a th This l o os e n s th e p r o duc t an d wi th th e a id ( c a r e ful "

.
) a
o f
s ti rr i n g ro d disi n te gr a te a n d t r a n sfe r it to a 2 5 0 cc fl a sk M ak e
-
. .

t h e v o lum e up t o 6 0 cc usi n g s o m e o f this w a t e r to r i n s e o u t

1 .
,

t h e fl a sk N e u t ra l i e wi t h a mm on ium hyd r oxid e s o lu ti on

. z .

( W hy n o t N a O H ? ) H e a t t h e fl a sk o n t h e s t ea m b a t h u n t il -

s o lu t i on ta k e s pla ce G e n e r a lly a pi n k s olu t i on 18 ob ta in e d

. .

S om e t im e s t h e subs t a n c e m e l t s a n d c o ll e c t s a t th e bo tt om o f
t h e fl a sk S h ak e t o diss o lve it
. D e c o l o r iz e by a ddi n g in sm all
.
,

a m o u n t s t w o sp oon fuls o f a n im a l ch a rc oa l
,
Co n t i n u e t h e h e a t .

in g f o r a b o u t t w en t y mi n u t e s wi t h o cc a si o n a l S h aki n g th e n , ,

fil te r while h ot th r o ugh a l a rge flu te d fil te r in a h o t w a te r fu n n e l -

( s ee p . a n d s e t t h e s o lu t i o n a sid e t o c r ys t a lliz e I f t h e .

crys tals ob tai n e d are col or e d th e y sh ould b e re disso lve d a s b e f ore -

in h o t wa t e r a n d h e a t e d a g a i n wi th an im a l ch a rc oa l Fil t er .

o ff t h e n e e dl e lik e crys t a ls wi t h suc t i on by m e a n s o f a B uch n e r

-

fu n n e l an d l e t th e m dry b e twe en fil te r p a p e rs or in a d e sicca to r , ,

o r p r e ss t h e m o u t o n a p o r ous t il e Con c e n t r a t e t h e fil t r a t e on.

1
A c et ci an h yd ri de a tt a c ks th e skin an d th e mu c ous me mbran e s . Be f
c a r e ul

i n ha n dli n g it .
16 6 LAB ORAT ORY MANU AL OF OR GANI C CH E M I STR Y

Q UE S TI ONS
1 Comp a r e th e s truc tur e s of a c e t ic a n hyd r id e , a c e tyl chl o r id e ,
.

a n d a c e t yl sulfu r ic a cid H ow is th e a n hyd r id e pr e p a r e d ?

.

E xpl a i n th e u s e o f th e tw o d r ops o f c on c sulfuric a cid

”
2 . . .

3 Why
. is i t n e c e ss a ry t o n e u t r a liz e t h e s o lu t i on ?

I W. h a t pr o duc t is n e u t r a liz e d wi t h a mm o ni um hydroxid e ?

5 Wh
. a t o bj e c t i o n w o uld t h e r e b e t o t h e u s e o f s o dium h d rox
y
ide ? Co uld i t b e us e d a t a ll ?
6 W hy is a h o t w a te r fu n n e l us e d ? W hy mus t th e s te m o f th e
.
-

fun n e l n o t p r oj e c t m uch b e low th e m e t a l c olla r ?

7 B.y m e a n s o f s t ruc t u r a l f o r mul a s S h ow h ow a c e t o t o luidid e - -

diff e rs fr o m o t oluidin e a c e ta te
-
.

8 Wh a t w o uld b e ob t a i n e d by h e a t i n g d r y a mm on ium a c e t a t e ?
.

dry o toluidin e a ce t a t e ? Comp ar e N o 9

-
. .

9 T.o wh ‘

a t cl a ss o f o r g a n ic c omp o u n ds d o e s a c e t o t o luidid e - -

b e l on g?
*
10 Wh a t a dv an ta ge h as a ce tic an hydride ove r a ce tyl chlorid e
.

f o r a c e tyl a t i on ?
11 H ow is an ili n e a c e tyl a t e d c omm e rci a lly ? U s e o f produc t ?
.

D o 3 ami n e s r ea c t a t al l wi t h a c e tyl chl o rid e ? (

°
12 .
-
S e e

sp e ci al r e fe renc e s ab ove ) .

13 . W h a t is th e s truc t ur e o f dia c e ta n ilide ? H ow p r e p a r e d ?

14 . Of wh a t u s e in th e l ab o r a t o r y is th e a c e t yl a t i on o f a mi n e s ?

Th e s e q u es ti s a
on re n o t re quired for s tu dy in th e
“
S ho rt c o urs e .
 x r
E p e i me n t N o -
. 47

S U L F ON AT I ON OF A N A R OMA T I C A MI NE

P r e par at io n of S ulf an ili c Ac i d f r om An il i n e

P our 5 0g r a ms o f c on c sulfuric a cid i n t o a 1 00 cc

. r o u n d .

b ot tom e d fl ask then a tta ch a n air con d e n s e r an d th r ough it

, ,

add c a u t i ously wi t h m o d e r a t e sh aki n g 1 5 gr a ms o f ani li n e .

D o n o t sh ak e s o vig or ously t h a t t h e sulfuric a cid c om e s in c on ta c t

wi th th e upp e r p or t i on o f th e fl a sk o r th e l ow e r p ar t of th e air
con de n se r T he firs t r ea c ti on pro duc t
. d ep o si te d a t th e s e
pl a ce s is n ot easily go t d ow n i n to th e m ai n p or ti on H alf .

imm e rs e th e fl a sk in an oil b a th which c o n sis t s of a sh allow

-
,

iron di sh p ar tly fill e d wi th r ap e s e e d oil an d h e a t th e mix ture ,

1

o f a n ili n e sulf a t e an d sulfuric a cid a t a t e mp e r a t ur e o f 1 7 5

°

t h e rm o m e te r in th e o il f or thr e e h o urs,
P o ur th e p ar .

t ial l y c o o l e d pr o duc t wi th s t i r ri n g i n to a b ou t 2 5 0 cc o f c o ld .

w a te r wh e n th e sulf an ilic a cid will s ep a ra te ou t in crys ta ls

,
.

All o w t o s t a n d f or ab o u t t w e n t y f o ur h ours t h en fil te r 06 th e
-
,

produc t wi th suc t i on in a B uch n e r fu n n e l Wa sh on ce wi th a .

li t tl e co ld w a te r .

S usp e n d th e crys t als t hus ob t a i n e d in 1 00 cc o f w a te r an d .

diss olve t h e m by a ddi n g a 2 N s olu ti on of s o dium hydroxid e u n til

n eu tr al t o li tmus I f th e s o lu t i on is w a t e r whi t e fil t e r fr o m -
.

a n y I m puri t i e s o t h e rwis e h ea t t o b o ili n g d e c o l o riz e by h e a t i n g

, ,

f or ab ou t h alf an h our on t h e w a t er b a th wi t h t h e a ddi ti on of-

a ni m a l ch arc oa l (a dd e d in sm a ll qu a n t i t i e s t o p r e v en t f o ami n g)

an d fil t e r . P re cipi ta te th e sulf an ili c a cid in th e fil t r a t e by

a ddi n g th e calcul ate d amou n t of hydro chlo ric a cid (b as e d
1
Do n ot all ow a n y w a t er t o c ome in c on ta c t w i th th e h ot oil . It c a use s viol en t
foamin g .Comp a re n o t e 6 p 8 2 ,
. .

2 A h igh e r t emp e ra ture c a use s c on siderabl e dec omposi tion . T h e h ea t in g may

be i n t e rrup t e d a t an y t ime .
16 8 LAB OR AT OR Y MANUAL OF OR GANI C CHE M I ST R Y
on he or e tica l yi e ld) t o lib er a te th e a cid fr om its s o di um
th e t
s al t A llow t o s ta n d ove r n igh t fil te r wi th suc ti on w a sh wi th a
.
, ,

li t t le w a te r a n d dry th e crys tals b e twe en fil te r p ap e r L arg e

. .

rh ombic pla te crys t als may b e ob tain e d by dissolvi n g th e sulf

an ilic a cid in jus t th e su f fici e n t a m ou n t o f h o t w a t e r f or c om

p l e t e s o lu t i o n a n d a ll owi n g t o c oo l sl owly T h e
v
c r ys t a ls c on .

t a i n 2 m ol e cul e s o f w a t e r o f hyd r a ti on which is sl owly l o s t ,

in th e air an d th e crys t a ls f a ll t o a p o wd e r Th e y are solubl e .

in h o t w a t e r b u t n o t v e ry s olubl e in c old w a te r Yi e ld 1 5 gr ams .

,
.

I t h as n o d e fin i te m e l t i n g p oi n t bu t d e c omp o s e s 2 8 0 3 00
°
- — °
,

Q UE S TI O N S
What is th e whi te s olid fi r s t f o r m e d ?
2 . I f n e c e ss a r y h ow c o uld y ou fil te r th e h o t a cid s o lu t i on ?
,

3 . N a m e sulfan ilic a cid t o s h ow i t s ch e mic a l gr o ups an d t h e ir

p osi tion .

4 . T r a ce th e ch an ge s f r om th e comp ou n d firs t f o rm e d throu gh

t h e a mid e f o r m a n d th e r e a rr a n ge m e n t t o sul f a n ilic a cid
-
.

(S e e J B C o h e n
. . Or gan ic Ch e mis t ry f or A dvan c e d
,

S tud e n t s
”
P t I I 2d Ed
,
.
,
.

U
I
W hy mus t th e mix t ur e n o t b e h e a te d a b o ve
H ow c ould a t e s t b e m a d e t o S h o w t h a t a l l th e an ilin e h as
s
‘

b ee n con ve r te d i n t o th e sulfan ilic a cid ?

:
x W hy mus t a n e xc e ss of s o dium hyd r oxid e b e av oId ed ?
0
0 I f y ou h av e a dd e d an e xc e ss o f s o dium h ydr oxid e in t ryi n g
t o m a k e t h e s o lu t i on n e u t r a l h ow c ould y ou t r e a t th e s o lu
t i on in o rd e r t o o b t a i n a ll th e sulf a n ilic a cid ?
9 . A l th ou gh sulf a n ilic a cid is s o lubl e in h o t w a te r th e m a te ri a l
is b on e bl a ck e d in an a lk a li n e s olu ti on W hy ?
-
.

10 . E xpl a i n th e a c t i o n o f b on e bl a ck (a n im a l ch a rc o a l) .

11 . W hy mus t th e c a lcul a t e d am ou n t of H Cl be us e d ? Why n o t

S imply a d d H Cl t o a cid r e a c t i on ?

12 . Wh a t is n aph thi on ic a cid ?

13 . Comp a r e t h e ch e mic a l pr op e r t i e s of th e ami n o sulfon ic a cids
a n d t h e a mi n o c a r b oxylic a cids .

'
14 . Wh a t u s e is m a d e o f s u lf a rrilic an d si mil a r a cids ?
15 . H ow c a n th e m e t a c omp ou n d corr e sp on din g t o su l f a n ilic
-

ac id be pr ep are d ?
 x
E pe ri me n t N o . 49

DY E S

F ORMATI ON OF A N A zo D YE

P r e par ati on of M e th yl O ran ge

N OT E

Us e a moun ts as n ea r ly
possible c o rr e c t as .

M ak e r ea dy a s o lu t i on of gram of s odium hydroxid e in

1 0 cc o f w a t e r
. I n a sm all b e ak e r N o 0 diss o lv e
. gram of ,
.
,

sulfan ilic a cid in 5 cc of w a te r an d . cc ( 1 mol ) of th e s odium . .

hydroxid e s olu t i on S e t th e b eak e r in i c e an d di az otiz e by addi n g

.

firs t a s olu t ion of gram ( mol ) of s odium n i t ri te (which

1 .

sh ould be p owd ere d t o m ak e it diss olve r ea dily) in 2 cc of wa te r .

,

an d t h e n sl owly wi th s tir r i n g a s olu ti on of 0 5 cc ( 1 mol ) of

, ,
. . .

con c hydro chloric a cid in 2 cc of w a te r A r e ddi sh s olu tion is

. . .

of t e n ob ta in e d .

I n a s ep a r a te sm all b e ak e r or t e s t tub e mix gram (ab ou t -

2 0 dr ops ) ( 1 mol ) of dim e t hyl a ni li n e a n d gr am (ab ou t 1 3

1
.

drops ) ( 1 mol ) o f gl a ci al a ce t ic a cid A dd t his s olu ti on drop

1
. .

by drop wi th con s ta n t s tirri n g to th e di az otiz e d solu ti on

, ,
.

T h e dy e b e gi n s t o s epa r a te a t on c e a n d f orms a thick d ark re d ,

m ass Tre a t this wi th th e r e m ain i n g

. cc (3 mol ) o f th e . .

s odium hydroxid e s olu ti on a n d s tir we ll Fil te r Off th e r e ddish .

ye ll ow pr oduc t wi th suc ti on usin g a h ard en e d fil te r p ap er or

,
2

tw o o r di n a ry fil t e r p ap e rs in th e b o t t o m o f th e fu n n e l Re .

crys talliz e th e crud e m e thyl o r an ge from 2 0 cc of h ot w a te r . .

1
rom th e lip of a 1 0 c c gra d u a t ed c yli n d e r
F . .

2
A ha rden ed fil te r pa p er is on e w h ic h h a s been trea ted w i th c on c su lfuri c . ac id .

It is tough a n d smooth an d h a s n o l oose fibre s .

17 0
 LAB OR AT OR Y E XPE RI M E NT S 17 1

afle t s wi th a go ld en lus te r a re thus ob ta in e d . A ll ow t o dry

on fil te r p ap e rs Yi e ld
. gr ams ,
.

N OTE S

M e thyl o r an ge is sodium sal t of th e sulfon ic acid an d its

th e ,

aque ous s olu ti o h a s a y ellow col o r

n On t h e a ddi ti on of a n aci d th e .

f r ee sulfo ic a cid (Helia th in e) is ob tain e d wh ic h h a s a ed color in

n n , r

a queous s o lu ti o T h e u s e of t h e dy e a s an i di c a t o r in a c i dime t r y
n . n

a d a l kalime t r y d ep e d s up on t h is ch a ge i c ol o r (For fu r th e r
~
n n n n .

discussion of th is c ol o r ch an ge s e e Coh en
“
Or gan ic Ch emis t r y , ,
”

Vol I I .

S T UD I E S OF T R I P HE NYLME TH ANE DYE S

P h e n olph th al e in

Mix gram of ph th a lic an hydrid e an d gr am of ph en ol

in a te s t— t ub e a n d a dd 2 dr ops of c on c sulfuric a cid
,
Hea t . .

g en tl y o v e r a sm a ll fl a m e wi t h c o n s t a n t a gi t a t i on f or a b o u t tw o

mi n u te s T h e m e l t will b e com e d ark r ed a n d th e h e a tin g

.
-

sh ould n ot be s o s tron g th a t th e m a te ri al bl a ck e n s on a ccou n t

‘

o f e x t e n siv e d e c omposi t i o n Wh en cold tre a t wi th 5 cc of

. .

w a te r an d a dd very grad u al l y wi th sh aki n g a dilu te s olu ti on

,

o f s odium hydr oxid e u n t il a p e rm a n e n t pi n k c o l o r is ob t a i n e d

(n o m o r e ) Dilu
. t e a p o r t i on o f t his s o lu t i o n a n d t e s t t h e sui t
abili t y Of th e diss o lv e d ph en o lph t h a l e i n as a n i n dic a t or by a ddi n g

firs t a tra ce of a cid an d the n a tr a ce of a lk a li .

Fl u or e s c e in

M ix gr am ea ch
ph th alic an hydrid e an d res orc in ol in
of
'

a t e s t t ub e a n d a d d 3 4 d r ops o f c o n c sulfuric a cid H e a t

- — . .

ge n tly f or tw o min u te s A llow t o cool a dd 5 cc of w a te r

.
,
.
,

a n d m ak e a lk a li n e wi t h s odium hydr o xid e Tran sfe r a drop of .

this s o lu t i on t o a t e s t t ub e full of w a te r
-
Vi e w by b oth .

refl e c te d an d t ran smi t te d ligh t .

’

Crys tal V i ol e t
P l a ce gram of M ic h l e r k (pp me thy diamin o
l ;
’ ’
s e t on e -
t e tr a
b e n z oph en on e) , 5 drops of dim e thyl an ili n e ,
and 2 drops of
17 2 LAB OR AT ORY MANUAL OF OR GANI C CH E M I S T RY
ph o sph rus xychl r id o o s t tub e an d h e a t th e t ub e in
o e in a te -
,

b oili n g w a te r f or o n e h alf h our A dd 0 cc o f w a t e r a n d s ti r

-
. 1 . .

A dd a drop of liquid t o ab o u t 2 0 cc o f w a te r a n d n o t e
I . .

th e c ol o r .

2 Ad d s ev e r al drops t o 2 0 cc of w a t e r an d t r e a t wi th a
. .

li t t le amm on ium hydr oxid e s olu ti on L e t s tan d u n til th e col or .

h a s dis app ea r e d an d whi te fl ocks a re f ou n d in th e liquid (s e v e r a l

mi n u te s) E xpl ai n . .

T o a p o r t i on o f t his d e c ol oriz e d s o lu t i on a d d v e ry dilu te ,

hydrochlo r ic a cid u n til th e col o r r e turn s E xpl ai n . .

3 T o a
. s e c o n d dilu t e p o r t i on o f th e o r igi n a l s o lu t i on a dd
dilu te hydr ochl oric a cid W h a t m ak e s th e gr e en c o l o r which .

ch an ge s to y e ll owish ? (S e e E Q A d ams a n d L R o s en s te i n . . .
,

T h e C o l o r a n d I on iz a ti on o f C rys t a l V i o l e t J ou r n A mer ,
. .

Chem S oc . .
,
36 14
5 2

4 . hird
To dilua t e pt o r t i on o f t h e o ri gi n a l s o lu t i o n a d d a

sm all am ou n t o f zin c dus t an d w a r m f or a f e w mi n u te s W h y .

d oe s th e col or dis app e ar ?

5 A ll
. o w t h e r e m a i n d e r o f t h e o rigi n a l s o lu t i on t o s t a n d
o v e r n i gh t wh e n crys t a ls o f crys t a l vi o l e t which h a v e a gr ee n ish ,

lus te r will s ep ar a te ou t on th e w alls of th e t e s t tub e

,
-
.

R E F E R E N CE S

Ho ll e man , Or gan ic Ch e m t r is y , 4 th E d .
5 8
2 .

For rl di us i of l
c o o r an d st ru tu r e , C u r ti s ;
{l
a gen e a sc s on c s ee s

Re a
t
io n be tw e C ol o r a
en nd Co n t t t siui on ,
”
J ou r n . A mer Chem . .

S oc .
,
32 7 95 .

Q UE S TI ON S
M E TH YL ORAN GE
Wh a t is di az o tiz a t i on ?
W h a t is th e di az o s t r uc tu r e ? th e di a z on ium s t ruc tur e ?
W ri te th e s t r uc tu r e o f b e n z e n e di a o ic a cid ; o f b en z e n e z

di az on ium hydroxid e W h y a re th e s e f o rmul a s a ssign e d .

t o t h e tw o is om e r s ?
U si n g s t r uc t u r a l f o r mul a s a n d e quilibri a e qu a t i on s t ra c e t h e ,

cou r s e o f th e r e a c ti o n in th e fo rm a ti on of an a mi n o a o -
z

dye wi th th e si mpl e s t pr e p a r a ti on in th e s e r i e s p ami n o ,

-
17 4 LAB OR AT OR Y MANUAL OF OR GANI C CH E M I ST RY
*
21 . Wh a t is B ism a r ck b r own ? H ow is m ph en yl en e di ami n e -

hydro ch lo rid e use d in th e t e s t f or n i tri te s ?

P HE N OL P H T HA LE I N F L U ORE S CE I N
AN D

22 . Wh a t a re th e s truc tura l formul a s of ph en olph th al ei n an d

flu ore s c e in ?
23 Wh a t a re s om e o f th e d e riva tive s of flu ore s c e in ?
24 Wh a t I s th e th e ory f or th e co l o r ch an ge I n th e u s e of ph en ol
ph th alei n as an i n dica tor ?
CR YS TAL VI OLE T

Wh a t is th e s truc tural fo rmul a (quin oid ) for crys tal vi ol e t ?

Tra ce th e cours e of th e re a c ti on b egi n n i n g wi th th e a ddi t i on
produc t f o rm e d from M ic h l e r s k e ton e an d d ime th yl an il
’

i n e t hr o u gh t h e t a u tom e ric ch a n ge t o t h e t ru e b a s e an d
, ,

th e n th e f o rm a t i on o f th e dy e by n e u t r ali z a t i on wi t h
hyd r o chl o ric a cid .

P oi n t ou t a n y chr om oph o r e a n d aux o chr om e gr oups in crys

t a l vi ol e t .

W h a t is th e p a r e n t subs t an c e of th e fuchsin e s e ri e s ?
Wh a t is a c o l or b a s e ? I llus tr a te in th e c a s e of crys t a l
vi ol e t H ow fo r m e d ?
.

E xpl ai n th e ch an ge s t h a t t ak e pl a c e in t h e pr e s en c e of th e
a lk a li .

Wh a t is th e s t ruc tu r e o f th e l e uc o b a s e o f c r ys ta l vi o l e t ?
-

H ow f o rm e d ?

Wh a t h app en s wh en c r ys ta l vi ol e t is t re a te d wi th con c .

hydro chl oric a cid ?

H ow is M ic hl e r s k e t on e m an uf ac tur e d ?
’

Ar e all c ol or e d subs t a n c e s dyes ?

W h a t is a m o rd an t ? H ow us e d ?
W h a t is a l ak e ?
Wh a t is a v a t dy e ? H ow us e d ? E x I n digo . .

Wh a t is r o s an ili n e fuchsin e or m age n t a ? P a ra ros ani lin e ?

, ,
-

How us e d in S chiff s a ld ehyd e r eage n t ?

’

Wh at is mal a chi te gree n ? H ow pr ep a r e d ?

Wh a t I s a u r i n ? r o s olic acid ? H o w p r ep a re d ?
Wh a t I s i n di go ? S umm a r iz e th e s t e ps i n it s m an ufa c tur e .

W h a t I s a liz ari n ?
Wh a t is th e s t r uc tu r e of i n d an thre n e ?
( M o hl a u an d

Bu c h e re r , 225

T h e se q u s ti n s
e o a re n o t req uired for s t u dy in t h e Sho rt co urs e .
 Expe r im e n t No . 50

F OR MAT I ON OF A T R I P H E N YL M E T H A N E D YE

P r e parati on of r
C y s tal Vi ol e t f r om M ic h l e r ’
s K e ton e
an d D im e th yl An il in e

H ea t a mix tur e cc of dim e thyl ani lin e

of 6 .
g r a ms o f ,

Mic h l e r s k e ton e (pp te tr am e thyl di ami n o b e n z o ph e n on e) a n d

’ ’
- - -
,

2 cc o f ph o sph orus o xychl o rid e in a p

. o rc e l a i n e v ap o r a t i n g dish
,

f or 2 5 h ours on th e s team b a th Th en tr an sf e r th e blu e col ore d

-
.
-

mass to a fl ask wi th w a te r m ak e a lk a l in e wi th a s olu ti on of ,

sodium hydr oxid e (calcul a te d on th e b asis of th e am ou n t s of th e

produc t s of th e ph o sph orus oxychl orid e) a n d dis till ,

(s e e p 1
5 )
8 u.n t il n o dr ops o f t h e u n a t t a ck e d di
e p a ss ov e r (ab ou t t hr e e h ours ) A f t e r th e a ddi t i on .

111 hydr oxid e th e blu e c o l o r sh ould dis a pp e a r e i t h e r

o r s oon a f t e r th e dis t ill a t i on is b e gu n a n d a r e ddish ,

t e f o rm e d I f i t d oe s n o t a dd m o r e s o dium hyd r oxid e

.
,
.

th e c ol or ch a n g e ) A f te r c oo li n g fil t e r th e r e ddish
.
, ,

color b a s e r em a in in g in th e di s till a ti on fl ask fr om th e

-
“

1
a lk a li n e s o lu t i on w a sh wi th w a te r an d b oil wi th a mix ture off-
, ,

2 5 0 cc of w a t e r a n d 2 cc o f c o n c hydr o chl o ric a cid

. . Fil te r th e
. .

blu e s olu ti on whi le h ot fr om th e u n diss o lve d col or b a s e ; an d -

b oil th e l a t te r a gai n wi th a fr e sh qu an ti ty o f th e dilu te hyd r o

chloric a cid This op e ra ti on sh ould be r ep e a te d u n t il th e sub
.

s tan ce is a lm o s t en t ire ly diss olve d On coolin g an d s tan din g .

,

th e c r ys t a l vi o l e t s ep a r a te s ou t in b e a u t iful n e e dl e crys ta ls o f a
c olo r Fil te r an d dr y in th e air on fil te r p ap e r A
. , .

r th er qu a n t i t y ma b e o b t a i n e d by a ddi n g fi n e ly pulv e riz e d

y
l t t o th e fil t r a t e s a l t i n g ou t Yi e ld a b o u t 4 gr ams ,
.

M ak e a dilu te s o lu t i on o f th e c r ys ta l vi o l e t an d p e rf o rm
2 4 giv e n u n d e r crys t a l vi o l e t o n p 1 7 2
— . .

17 5
17 6 LAB OR ATOR Y MAN UAL A
O F OR G N I C C H EM I ST RY

Q UE S TI ON S
Wha t is a con d e n si n g age n t
Why mus t th e mix tu r e be b e fo r e dis tilli n g
s t eam ?
W hy mus t dil u te hydro chl o ric acid b e us e d f or pr e p ari n g
d ye ? W h a t h app e n s w h e n s t ro n ge r a cid is us e d ?
A n sw e r a ls o qu e s t i o n s 2 5 4 3 p
-
,
.
74
1 .
17 8 LAB ORAT ORY MANUAL OF OR GANI C CH E MI ST RY
et h e r may be l e f t in a sm all fl a sk f or th e fin al dis till a t i on th e ,

e th e r is dis t ill e d ove r in t h e m a n n e r d e scrib e d in t h e A n ili n e

E xp e rim e n t p 1 6 1 Dis t ill th e re sidue usi n g a sh or t wid e tub e

,
. .
,

o r a n a d ap t e r as a n a ir c o n d e n s e r Bp mp 4 2 T he . . . . .

sp e cim en S hould be whi te an d sh ould s olidify e sp e ci ally wh en th e ,

t ub e is pl a c e d in c old w a t e r I f it is c o l or e d r e dis t ill c a r e fully

.
-
.

Yi e ld 8 gr a ms
,
.

R ea c ti on s f
o P hen ol an d D eriva tives

a Te s t th e re a c t ion of an a qu e ous s olu ti on of ph e n o l wi th

.

n e u t r al li t mus p ap e r .

b A dd a li tt l e s o dium hydr oxid e s olu t i on t o 1 gr am of

.

phen ol N ow a cidify wi th hydrochl o ric a cid D o n o t u s e t oo

.
‘

much wa te r An y ch an ge ? .

Diss olve a drop of ph en ol in w a te r a n d add bromi n e

'

c .

wate r u n til it is n o l on ge r abs orb e d Fil te r off th e p r e cipi ta te .

an d w a sh i t wi t h a dilu t e s o lu t i o n o f sulfur di oxid e o r o f s odium

hydrogen s u l fite u n til t her e is a s tr on g od or of su l fur dioxid e .

Wa sh wi th w ate r Diss olve in ab ou t 5 cc of h o t alcoh ol fil te r

. .
, ,

a dd 1 0 cc of h o t w a t e r an d s e t a sid e t o crys t a lliz e

. Dry it on a,
.

p o rous tile an d d e te rmin e its m e l ti n g p oin t For wha t is this -

.

re ac ti on us ed ? Comp are wi t h the a c t ion of bromin e an d of

bromin e w a te r on b en z en e (p an d on amyl e n e (p 4 . .

N OTE

T he sulphur di o xi de con ve r t s an y Br3 C6 H2 0Br i n to t ribrom

phen ol Br3 C6 H20H

{
.
,

d To a dilu te solu tion of phen ol add a drop o f m ol ar fe rri

.

chlorid e s olu ti on .

e A dd a dr op o f f e rric chl o rid e s olu t i on t o dilu t e s olu t i on s

.

o f c a t e ch o l r e s o rci n ol s a licyl ic a cid a n d g a llic a cid

, ,
C om .

p ar e th e s truc ture s of the s e comp oun ds .

f .
Try t h e a c t i on o f f e rric chl o rid e on a s o lu t i on c on t a i n i n g

a dr op o f a ce t a c e t ic e s t e r an d on an o th e r c on t a i n in g a d r o p o f

a c e t yl a c e t o n e U s e a lc oh o l in e a ch ca s e t o m ak e th e s o lu t i o n
.

h omogen eous Wh a t is m e an t by th e en ol an d th e k e to fo rm ?
.
 LAB OR AT OR Y E X P E RI M E NT S 17 9

w h ic h on e is this c ol or r ea c t ion supp o se d t o be du e ? D o

hyd roxyl comp oun ds give c ol o r r e a c t i on s wi t h f e rric chl orid e ?
A ls o c omp a r e th e a c t i on o f f e r ric chl o rid e o n a r om a t ic
S (a n ili n e ) a n d o n a lph a hydr o xy a cids lik e t a r t a ric a cid
,
-
,
.

Q UE S TI ON S
H ow -
d oe s an ili n e diffe r f r om amm on ia ? Comp a r e th e a c t ion
o f n i t r o us a cid in e a ch c a s e .

Why is an ili n e firs t t r e a t e d wi t h sulfuric a cid ?

Wh a t comp o u n d is f orme d wh en an ili n e an d sulfu r ic a cid
r e a ct ?
Wo uld t h e r e b e a n y obj e c t i on t o usi n g t o o li t t l e s o dium
ni tri t e ? t oo much ?

Wh a t r ea s on is t h e r e f or h ea t in g th e di az o t iz e d s o lu t i on ?
Ca lcul a t e th e am o u n t o f sulphu r i c a cid t h e o r e t ic a ll y n e c e s
s ary f or c on ve r ti n g 0 gr a ms of a n ilin e i n to ph en ol an d
1 ,

c omp a r e wi th th e am ou n t us e d .

E xpl a i n t h e pri n cipl e o f s t e a m dis t ill a t i on .

W hy is s team dis t ill a t i on us e d in t his e xp e rim en t ?

H ow c a n y o u t e ll by ch em ic a l m e a n s wh en all t h e ph en o l
h as b e e n dis t ill e d ov e r wi th s tea m ?
Why n o t con tin u e th e s t e a m dis tilla ti on u n til th e dis till a te
g i v e s n o t e s t f o r ph en o l ?
Why I S th e dis t ill a t e s a t ura t e d wi th s al t b e fo re e x t r a c t i on ?
Wh a t a dva n ta ge is th e re in e x t ra ct in g th e s o lu t ion three
t im e s wi t h s ma ll a m o u n t s o f e th e r i n s t e a d o f on c e wi th
,

a l a r ge r a m o u n t o f e t h e r ?

How c a n a n hydr o us s odi um sulf a t e be u s e d a s a dryi n g

’

a g en t ?

Wh e re d oe s th e m ois ture t ak e n up by th e s odium sulf a te

c om e from ?
I s t his m e t h o d f o r th e f o rm a t i on Of ph e n o ls pr a c t ic a l ?
Can this m e th o d o f r epl a ci n g a n a mi n o gr o up wi t h hydr oxyl
b e us e d in th e c a s e o f a liph a t ic a mi n e s ?
Wh a t a dva n ta ge is t h e r e in di s t illin g th e e t h e r from a sm a ll
fl a sk ?
H ow c an ph e n o l b e pr e p a r e d fr o m b en z e n e sulph on ic a cid ?
3
19 . Comp a r e t h e b eh a vi o r o f e t hyl a lc o h o l a n d ph e n ol wh e n
t r e a t e d w i th b r omi n e
.

Comp a r e th e a c t ion o f th e h a l oge n s an d o f n i tric a cid on

phen o l an d on b e nz e n e .

Wh at is th e a c ti on of a ce tyl chlorid e ; an d of zin c dus t on ,

ph en ol ?
 E xpe riin e n t N o . 52

AL KYL AT I ON OF A N H YD R OX YL GR OUP

P r e par ati on of An i s ol e ( M e th yl p h e n l E-
th e y r) f r om P h e n ol an d

D ime th yl s ulf a te

P e rform this exp e rim e n t wi th app ar a tus con n e c te d wi th th e

d r a f t pip e D ime th yl s u l fa te h as n o odo r bu t it is ve r y p ois on
.
,

bu s to s om e p e opl e B e c a r e ful n o t t o br e a th e its v ap ors a n d

.

sin ce it is r ea dily abs o r b e d d o n ot all ow an y to com e in con ta c t

wi th th e ski n I f an y be spil t up on th e cl oth e s th e s e sho uld be
.

ch an ge d imm e di a te ly .

Diss olv e 2 grams o f ph en ol in a s ol u ti on of 1 0 grams o f

1
1

s o dium hydroxid e an d 00 cc of w a t e r P our thi s i n to a 2 50 cc

1 . . .

fl ask an d a dd S lowl y a n d wi th co n ti n u ous S h aki n g 2 5 grams of

_

d ime th y l su lf a t e 2
. P l a c e a th e r m om e te r in t h e mix tur e .

Th e r e is a sligh t ris e in t emp e r a ture which sh ould n ot be ,

a ll ow e d t o e xc e e d 40 (c ooli n g is usu ally n o t n e c e ss a ry) Th e

°
.

Cl e a r li quid b e c o m e s t urbid a n d in a f e w mi n u t e s a l a y e r o f o il

will fl oa t on th e surf a ce T h e r e a c ti on may be c on sid ere d c om

.

p l e t e wh e n t h e t e mp e r a t ur e n o l o n g e r ris e s a n d t h e pr o duc t s
c ool
T o d e s t r oy th e e xc e ss o f dime th y l s u lf a t e (dr y th e fl a sk if
it h as b e e n p l a c e d in w a te r ) a t t a ch a n up r i gh t air co n d en s e r
, ,

a n d h ea t t h e mix t ur e t o th e b oili n g p oi n t wi t h fr e qu en t sh aki n g

-
.

( H o w d oe s t his d e s t r o y t h e d im e t h y l s u l f a t e ? ) Fi n a lly c o o l ,

th e liquid , a d d a s o lu t i on of 6 gr a ms o f s odium hydr oxid e in 6 0

1
M l t it by pl i g th b ttl i w rm w t r I f ph l sh uld m i
e ac n e o e n a a e . e no o co e n c on

i
ta c t w th th e skin u s e d ilu te a l c oh ol i mme d ia tely .

2
Ope n in g s ea l ed b o tt l e s : W ra p th e bo t t l e in a t ow e l l e a vi n g t h e n a rrow ,

s ea l e d en d pro trud i n g a n d ma ke a fil e ma rk a ro un d th e t ub e n ea r t h e e n d H old

,
.

i t o v e r a b ea ke r in a sl a n t i n g p o s i t i on a n d kn o c k o ff t h e e n d w i t h a S ha rp bl o w of
th e fil e o r t ou c h th e mark w i th th e h ot fus e d en d o f a gl a ss ro d
, .

18 0
 E xpe rime n t N o . 53

B E N Z ALDE HYDE

P e rform foll owi n g r e a c ti on s

th e
1 S il ver mirror tes t
.
-
. M ak e an a mm on i a c a l s olu ti on of
S ilve r n i t r a t e as giv e n u n d e r A c e t a ld e hyd e p 9
, ,
an d a dd a dr op
. 1,

o f s odium hydr o xid e s o lu t i on . I f a pr e cipi ta te f orms diss olve it

wi th a li ttl e m ore a mm on ium hyd r oxid e A dd a sin gle drop .

( o r a l e ss e r a m o u n t ) o f b en z a ld e hyd e sh ,
a k e a n d l,
e t s t an d .

T he mirr or f orms v e ry sl owly

‘

2 Try th e a c ti on of th e fuchsin e sulfurous a cid r eagen t

.
-

( S chi f f s a ld ’
e hyd e r e a g e n t) p 9 2
.
,
on b e n z a ld e hyd e I f t h e .

dr op of b en z ald e hyd e is r u n d own th e sid e o f th e te s t tub e it -

will fl oa t on th e surf a ce of th e s olu ti on a n d will assum e th e

color of the fuchsin e wi th ou t co l ori n g th e e n tire solu ti on .

3 D oe s
. b e nz a ld e hyd e r e duc e F e hli n g s s o lu t i on ?
’
Try i t .

4 A dd . s e v e r a l dr ops o f b e n z a ld e hyd e t o 2 or 3 cc o f a .

s a t ura te d s olu ti on of s o dium bis u l fite an d sh ak e vigorously ,

.

Of wh a t do th e whi t e crys t a ls c on sis t ? Fil t e r wi th suc ti on a n d

th en w a rm wi th a s olu t i on of s o dium c a rb on a te .

5 A dd . a dr o p o f b e n z a ld e hyd e t o a s o lu t i o n o f a dr o p o f
ph en ylhydrazin e in 3 cc of di lu te a ce tic a cid ( I I ) Wh at is th e
. .

ye ll ow pr e cipi ta te ?
6 R u b a dr op of b en z ald e hyd e on a wat c h gl ass
. Wh at a re
.

th e crys t als t h a t f orm a f te r a sh or t ti m e ?

'
7 M a k.e a v e ry dilu t e s o lu t i on o f s o lubl e s t a rch an d a dd t o
i t a few drops of dilu te p o ta ssiu m i odi de s olu tion S prea d a
l

drop of b en z aldehyd e on a w a t ch gl ass wi th the aid of a s tirrin g

r od A ll ow it t o r e m ain f or a mi n u te or tw o a n d th e n a dd a
. .
,

f ew dr ops o f th e s ta r ch p o t assium i o did e s olu ti on

-
S e t th e
.

w a t ch gl ass ove r a fil te r p ape r a n d s tir wi th th e rod E xplai n

‘

, .

th e f o rm a ti on o f t h e blu e c o l o r (s e e Q u e s ti on 9 b e l ow) .

Which of th e ab ove r ea c ti on s are also ch ara c teris tic of

ke ton e s ?
 LAB ORAT OR Y E X P E RI M E NT S 183

8 . In s ub e th oroughly mix ab ou t
a t e t- t gra m o f c in
nami c a cid a n d a b o u t 5 cc o f a c o ld s t r o n g s olu ti o n o f p o t a ssium
.

pe rm an gan a te N o t e th e o d o r E xpla in
. . .

Wh a t typ e of u n s atura te d a rom a tic c ompou n ds wi th r e l a tion ,

t o th e p o si t i on o f th e d oubl e b on d u n d e rg o t his r e a c t i on ? ,

Ou t li n e th e c omm e rci a l pr e p a r a t i on o f v ani lli n fr om e ug en ol

an d o f pip e r on a l fr o m s a fr ol ( ll m Organ ic Ch e mis t r y ”
H o e a n .
, ,

4 t h E d .
4 8 2
—
5 ; S t o dd a rd “
I n t roduc t io n t o Org a n ic
,

Ch emis try
”
2 d Ed
, 3 47 .
,

Q UE S TI ON S
1 . D oe s b en z ald e hyd e r ea c t wi th F e hli n g s s olu ti on ? ’

2 . W ri t e e qu a ti on s a n d c ompl e te s t ruc t ur e s i n vo lv e d in th e
re a c ti on s b e tw ee n b e n z a ld e hyd e an d s odium hyd rogen
s u l fit e an d b e tw e e n t h e pr o duc t a n d s o dium c a rb o n at e
,
.

3 . Could a dilu t e s o lu t i on o f a cid s o dium s u l fit e be us e d i n s t e a d

o f t h e c on c e n t r a t e d ?

4 . Could a n y o th e r r ea g e n t be us e d in pl a c e o f th e sod ium c ar

b on a t e ?
5 . Wri te e qu a ti on s an d s truc ture s for th e re a c tion wi th ph en yl
hydr azi n e .

6 . Could 5 0 p e r c e n t hydr o chl o ric a cid b e us e d in pl a c e of

th e 5 0 p e r c e n t a c e t ic a cid ?
7 . Could ph e n ylhydr a zi n e hydr o chl orid e b e us e d ? Wh a t
m o difica ti on I S gen erally n e c e ss ary ?
8 . Coul d hydr a zin e i ts e lf b e us e d ? *
S e mic a rb azid e ? (P e r
kin a n d Kippin g Org ani c Ch e mis t ry
”
, N ew E d ,
.

( 191 1 ) 45 6
9 . Wh a t h appen s wh en b enz ald e hyd e is exp o se d to th e air ?
( F o r discussi o n of a u t oxid a t i o n s e e H o ll e m an
, O r ga n i c ,

Ch e mis t ry 4 th E d yliss P ri cipl s

”
, 4 2
. 8 ; a n d B a n e ,

o f G e n e r a l P hysi o l o gy

10 . E xpl a i n wh a t t ak e s pl a c e in th e exp e rim en t wi t h s tarch an d

p o tassium i odid e .

11 . W ri t e e qu a t i on s f or th e r ea c t i on s o ccurri n g wh e n ben zal d e

hyd e is t r ea te d wi th th e fo ll owin g re agen t s : (a ) ph o s
p h o r u s p e n t a chl o rid e ( b) mix t ur e,
o f n i t ric a n d sulfuric
a cids a t (c ) hydroxyl amin e hydr o chl orid e a n d s odium
c arb on a te (d) a ce ton e an d s odium hyd r oxid e s o lu ti on
,
*

(c omp ar e P e rki n an d Kippi n g ()

e a lc
,
o h o lic s *
o lu
ti on of p o tassium cy an id e f ) a mm o ni a (g) an ili n e
, ,
.

T he s e qu es tion s are n ot req uired f o s tudy i r n th e shor t urs e

co .
 x rim e n t
E pe No . 54

ADD I T I ON OF H YD R OGE N To AN E TH YLE NE D E R I VAT I VE

P r e par at i on of Hy d r oc i n n a mi c Ac d i (P h e n y p p on i c
l r O i Ac i d )
fr om Cin n amic Ac d i
T h e 3 p er ce n t s odium am algam us e d in this exp e rim e n t is
prep are d as foll ows : We igh ou t in a dry e vap o r a ti n g dish o r
ca ss er ole 1 4 5 g r ams of pu r e d r y m e r cu r y Wa rm on th e s team .

b a th to P r ep a r e 4 5 gr ams o f s odium f r e e fr o m crus t a n d

.
,

from th e liquid which c an be r em ove d wi th fil te r p ap e r Cu t off .

slice s an d imm e di a te ly pr e ss th em to th e b ottom of th e wa rm

m e rcury in r ath e r r apid succ e ssi on by m ean s o f a S h or t m o d e ra t ely
t hick gl a ss r od dr awn ou t t o a p oi n t a n d b e n t a t a sh or t ri gh t
,

a n gl e .U s e a p e s tl e if n e c e ss a ry in t h e a b ov e Op e r a t i on A f te r .

e a ch pi e c e is a dd e d a s om e wh a t v i ol e n t r e a c t i on t a k e s pl a c e If .

th e op e r a t i on is c on duc t e d quickly a ll t h e s odium c a n b e a dd e d

b ef or e th e m ass s olidifie s T his opera tion mu s t be c arri ed out
.

u n der the hood , u s in g the gl as s door a s a s hi el d; rotec

p t the eyes

w i th g gg
o l es a n d the han ds w i th gl oves . T hes e prec au ti on s are a b
s ol u tel y bec a us e piec es of
n ec es s a ry bu r n i n g s odiu m are often pro

jec ted in difl eren t di rec ti on s fr om the dis h . B r e ak up th e s emi

s olid am al gam at on ec an d t r an sfe r it to a t igh t ly s t opp e r e d

dry b ottle .

I n to a cc fl ask pu t 5 grams of Cin n ami c a cid 8 0 cc of

2 50 .
,
.

w ate r con t ai ni n g gr ams of s o dium hydroxid e an d 5 0 grams ,

1

o f s o dium a malg am (3 p e r c e n t) in sm a ll p o r t i on s S h a k e th e .

mix ture w e ll af te r e a ch a ddi ti on A t th e b egi n ni n g th e am algam

.

l iqu e fies r apidly v e ry li tt l e hydr o g e n is e v o lv e d a n d th e s o lu t i on

,

b e com e s warm Toward th e en d th e am algam d oe s n o t liqu e fy

.

a t al l r e adily a n d n u m e r o us bubbl e s o f hyd r o ge n a r e e v o lve d .

Add m or e w a t er if n e c e ss a ry t o diss olv e a n y pr e cipi t a t e

, ,
.

18 4
18 6 LAB ORAT ORY MANUAL OF OR GA NI C CH E M I S TRY

Q UE S T I ONS
Wh a t is Ci n n amic a cid ?
H ow is Ci n n amic a cid pr ep a r e d ? (P e rki n s r e a c t i on )
’
.

E xpl a i n why th e a m a l gam is us e d i n s t e a d o f m e t a llic s o di um .

P o in t o u t wh a t is oxidiz e d a n d wh a t is r e duce d .

Wh a t is th e whi te pr e cipi t a t e t h a t s o m e t im e s f orms t owa rd

th e e n d o f th e r e duc t i on ? E xpl ai n i t s f o rm a t i on .

I n th e t e s t f o r u n a t t a ck e d Ci n n amic a cid e xpl ai n why th e ,

s olu ti on mus t fi r s t be a cidifie d wi th hyd r o chloric a cid an d

th e n m a d e alk a li n e wi t h s odi um c a r b on a t e How e ls e .

could th e s am e con di ti on be ob tai n e d ? Wh a t eff e c t w ould

th e s o dium hydr o xid e h a v e o n th e t e s t ?
Could th e f o ll o wi n g c omp ou n d be r e duc e d wi th sodium
a m a l ga m in w a t e r : C 6 H 5 CH CH CH COOH ?
- -
z

H ow d o e s s o dium a m a lg am r ea c t in a n e thyl a lc oh o l s o lu ti on ?
G ive an e x ampl e ( P
. e rki n a n d Kippi n g Organ ic ,

Ch e mis t ry h is myl
”
,
N ew E d . 8
3 5 6 —
,
W en a

a lc oh o l us e d ? Wh a t a dva n t age is t h e r e in usin g a lcohol ?

Wh a t o th e r r e ducin g a ge n t s are use d f or r e duci n g the ol efin e
‘

b on d ?
H ow c a n b e n z en e b e r e duc e d t o cycl oh ex a n e ? (P e rkin
a n d Kippi n g 3 6 5 , ,

Discuss th e hydro gen a tion (r e duc tion ) of oils S ee C A . . .

E llis J ou rn I n du s tr i al an d E n g Chem 5
,
. . .
95
,
—1 0 6 ;
a n d his b o o k T h e H ydr ogen a t i on of Oils publishe d by ”
, ,

Van Nos tr an d .
 x rime n t
E pe No . 55

RE P LA CE ME N T OF A D I A z o G R OU P
-
BY CYAN OGE N ( S A N D ME YE R

RE A CTI ON )

P r e parati on of p o u n-i t r
T li l e (p T ol yl c y a n i
-
d e ) f r om p T o l u i d i n e -

P e rfo rm al l th e Op e r a t i on s u n der the hood D iss olv e 1 2 gra ms .

o f p owd e r e d c opp e r sulf a t e crys t a ls in 5 0 cc o f w a t e r in a 5 0 0 cc . .

fl a sk by h ea tin g on th e s te am b a th ; t h en a dd gradu a lly wi th

-
,

c on tin u ous h ea tin g a s o lu ti on of 4 grams of p owd e r e d p o ta ssium

,
1

cyani d e in 2 5 cc of wa te r S in c e c yan ogen i s evol ved the grea tes t

. .

c are mu s t be ta ken n ot to br ea the the va p or s .

While the p o ta ssium cuprous cy an id e s olu ti on is fur th e r

gen tly h ea te d on th e s te am b a th prep ar e th e t olu e n e di az on ium
-
,

chlorid e s olu tion as f ollows : Wa rm 5 gra ms o f p to luidi n e wi th -

a mix tur e o f 1 0 cc of c on c e n t r a t e d hydr o chl o ric a cid an d 2 5 cc

. .

o f w a t e r u n t il s o lu ti on t ak e s pl a c e Th en s e t the b e ak e r in
.

ic e a n d s tir in o rd e r th a t th e t o luidi n e hydro chl o rid e ma y

s ep a r a te ou t in as sm all crys t als a s p ossibl e T o this ic e .

cool e d mix tur e add gr a du ally wi th goo d s tirri n g a solu ti on o f

.

4 gr a ms of p owd e r e d s o dium n i tri t e (m or e th a n 1 m o l e cul a r

e quiv a l en t) in 5 1 cc o f w a t e.r u n t il a dr o p o f t h e r ea c t i on

mix ture give s a p e rm an en t blu e col or wi th s ta rch i odid e p ap e r - 1

,

o r u n t il y ou jus t n o t ic e t h e o d o r o f th e o xid e s o f n i t r o g e n f r om th e

e xc e ss o f n i t r o us a cid T h e t e mp e r a tur e o f th e mix tur e sh ould

.

n o t ris e ab o v e 0 a t a n y t im e P our t his di az o t iz e d s o lu t i o n

°
.
,

in sm a ll po r t i on s duri n g t en mi n u te s i n t o th e h o t cupr o us cy an id e
,

solu t i on wi th fre qu en t shaki n g A rap id e ff e rve sce n ce o ccurs

,
.
,

n i t r og e n a n d s o m e hydr o cy a n ic a cid b e i n g e v o lv e d Heat for .

ab o u t a qu a r te r o f an h o ur on th e s t e am b a t h Th en dis till o ve r
-
.

th e tolu n i tril e wi th s te am (s e e p I I f th e s o lid s ep ar a t e s

.

in th e c on d e n s e r tub e shu t off th e w a t e r an d a f te r th e m a t e ri a l ,

1
P re pared by soaki n g s trips of fi l te r p a pe r in a v e ry d ilu te s olu t i on of s ta rc h
an d po ta ssiu m iodi d e T h e pa pe rs a re dri e d a n d ke p t in a c l os ed bot tl e
. .

18 7
188 LAB ORAT OR Y MA NUAL OF OR GANI C CH E MI ST RY
m e l t s an d fl ows through s l ow l y t urn on th e wa te r a gai n This
,
.
,

o p e r a t i o n mus t a ls o b e c a r r i e d ou t u n d e r a h oo d wi t h a o d
g o

d r a f t a s n ot on ly is hydro cyan ic a cid lib e r a te d bu t a sm a ll

, ,

qu an ti ty of th e is on i t ril e which is f orm ed in th e re a c ti on p ro

duc e s a dis agreeabl e o d o r Con ti n u e th e dis till a ti on u n til n o
.

m o r e of th e oil p ass e s ove r T h e n i t r il e s olidifi e s in th e r e ceive r

.
1

on cooli n g a s a y e ll ow c r ys ta lli n e m ass Cool tho roughly .

,

d e ca n t off the w a te r an d pr e ss ou t th e subs ta n ce on a p oro us

,

t il e Dis till th e p r o duc t f r om a sm all fl ask usi n g a sh o r t tub e

.
,

a s a n a ir c o n d e n s e r B e s t r e sul t s a re ob ta i n e d by dis t illi n g th e

.

ni t r il e i n vac u o (p . I f t h e oil d o e s n o t s o lidify e x t r a c t ,

wi th e the r sh ak e th e e th e r e a l s olu ti on wi th s o dium hydr oxid e

,

s olu ti on to r e m ove th e c r e s o l an d t h en a f t e r s e p a r a t i n g a n d

dryi n g wi th an hydrous s odium sulf a te a n d e vap or a t i n g th e

e t h e r in a sm all fl a sk a s in t h e A n ili n e E xp e rim e n t (p dis .

t ill th e r e sidu e di r e c tly B o ili n g p oi n t 2 8 a t 7 6 0 mm a n d

°
.
-
,
1 .

a b o u t 1 03 at 2 1
°
mm m e l t i n g.p o,
i n t Y i e ld
-
gr a ms
, ,
.

Q UE S TI O N S
1 . G iv e e qu a ti on s to S h ow th e f o rm a tio n o f th e cuprous cy an id e ,

a n d o f t h e n i t r il e .

2 . Why is it a dvan t age ous t o h ave th e toluidi n e hydro chl o rid e

sep ar a te in sm all c r ys ta ls ?
3 . Why is th e s olu ti on k e p t c old du r i n g th e di az o t iz a ti on ?
E xpl a i n th e s t a rch i o did e t e s t f or f r e e n i t ro us a cid
-
.

5 . Wh a t is th e f o r mul a f o r th e is on i t r il e ?
6 . H ow c an y ou a c c o u n t f or th e pr e s e n c e o f a n y c r e s o l ?
7 . H ow is th e cr e s o l r e m ov e d ?
8 . Wh a t is t h e G a t termann m o difica ti on o f th e S an dmeye r
r e a c t i on ?
9 . Wh a t o th e r d e r iv a tive s c a n b e p r ep a r e d by m ean s o f th e
S an dme y e r r e a c t i on ?
10 . I s it n e c e ss a r y t o u s e cup r o us i o did e in o r d e r t o pre p ar e
ph e n yl i odid e f r om a n ili n e ?
11 . H ow is th e p t o lu n i t r il e c on ve r t e d i n t o p t o luic a cid ?
- -

G ive th e s t eps in th is r e a c ti on .

12 . H ow c an y ou pr e p a r e a c e t o n i t r il e (m e thyl cy a ni d e ) fr om
-

a c e t a mid e ? f r o m m e t h yl i o did e ?

1
3 . Wh a t is th e a c ti on o f s odium a n d a lcoh o l o n a ni tril e ?
1re si du e in th e fl a sk sh oul d
The n ot be e mp t i e d r
w h e e ac id mi gh t be a d d ed

a n d th us c a us e e v olu t i on of H CN .
19 0 LAB OR AT ORY MANUAL OF OR GA NI C CH E M I S T RY
Fil te r wi th suc ti on th e a c e tan th rani l ic a cid which is pre c ipi
off ,

t a t e d a s fin e wh i te n ee dl e crys t a ls a n d w a sh wi th a li t t l e Cold
,

wa te r Te s t th e fil t ra te f or c ompl e te pre cipi ta ti on by a ddin g

.

m ore sulfuric a cid M e l t in g p oi n t

.
-
,
Yi e ld 7 5 pe r c e n t
,

o f th e t h eo ry .

NOTE

b r ow s ta i s c a asily b r moved f r om
T he n n n e e e t h e h an d s an d

app ar a tus by me an s of a s olu t i o o f s dium bis u l fit

n o e .

Q UE S T I O N S

Wha t is th e sp e cific obj e c t o f th e m agn e sium sulf a t e ?

Why is it n e ce ss a ry th a t this obj e c t be a t ta in e d ?
W h a t b e come s o f th e p o t a ssium a n d o f th e m a n ga n e s e of
t h e p o ta ssium p e rm an ga n a t e du r i n g th e oxid a t i o n ?
4 . H ow c a n a n t hr a ni lic a cid b e pr ep a r e d fro m ac e t a n th ra n il ic
a cid ?

Why c an n o t an thran ilic a cid be fo rm e d by th e dire c t oxid a

t i on o f o t o luidi n e ?
-

Wh a t is m ean t by blo ckin g or pr o t e c t in g th e a min o

group ?
H ow c an an thr an ilic a cid b e ob t a i n e d fr o m i t s p o t a ssium
s al t ?
Wh at is th e b e s t m e th od f or purifyi n g an thran ilic a cid ?
( S am e as us e d f o r an y a mi n o a cid ) .

How is a n th r a n ilic a cid ob t a i n e d f rom ph th alic a cid ? Wh e r e

is this r e a c t i on us e d c omme r ci a lly ?
Wh at is th e e ff e c t o f hyd r o chlo ric a cid on an thra ni lic a cid ?
I s th e pro duc t s olubl e in w ate r ?
 E xpe rime n t N o . 57

F ORMATI ON OF A N AR OMA TI C E S T E R F R OM T HE A CI D A ND T HE
1
A L COH OL

P r e parati on of M e th yl S al i c yl ate ( O il of W i n te rgr e e n ) f r om

S al i c yl i c Ac i d an d M e th yl A l c oh ol
P l ac e 7 gr ams o f s a licylic a cid in a 2 5 cc r o u n d b o tt o m e d
1 1 .
-

fl ask a dd 3 0 cc o f m e t hyl a lcoh ol an d t h en g r adu a lly an d wi th

,
.

S h aki n g a d d 4 5 cc o f c o n c sulfuric a cid

,
. . . A dd a f e w pi e c e s o f .

p orous tilin g c on n e c t wi th an up r igh t or r e flux c on d e n s e r an d

, ,

h e a t on a s team b a th f or ab ou t 2 5 h ours Wh en th e r e a c ti on h as
-
. .

pro c ee d e d f or s om e t im e th e oil of Wi n te rgr ee n fo rm e d s ta ys

a t t h e b o t t om o f th e fl a sk a n d s om e t im e s wh en s t irr e d by t h e

b oilin g a n d drippin g from th e c on d e n s e r f o rms an emulsion

which re s embl e s a pre cipi ta te Dis t ill off th e m e thyl alcoh ol
.

ov e r t h e s t e a m —b a th in th e r e gul ar m ann e r t ran sfe r the r e sidu e ,

to a s e p a r a t o ry fu n n e l a dd ab o u t 40 cc of w a t e r sh ak e s ep a r a t e
,
.
, ,

the l ow e r l a y e r which is t h e m e t hyl s a licyl a te an d w a sh i t in th e ,

s ep a ra tory fun n e l firs t wi t h w a t e r t h en wi t h dilu t e s odium ,

ca r b on ate s olu ti on (Why ?) an d finally: wi t h dis t ille d wa te r .

S e p a r a t e fr om th e w a t e r dry ov e r a n hydr ous s o dium sulf a t e

, ,

a n d purify by dis t ill a t i o n u n d e r dimi n ish e d pre ssur e (p .

I f a n e mulsi on is f o rm e d in th e w a shi n g a ll o w t o s ta n d t hir t y ,

min u te s a n d if it d oe s n o t subsid e s ep a ra te th e l a y e rs as w e ll a s
, ,

possible an d th en dry ove r anh ydrous s odium sulfat e T h e

,
.

t urbid w a t e r l ay e r c o n t a i n s on ly a v e ry sm a ll a mo u n t o f pr o duc t .

All th e e s t e r dis t ills a t c on s ta n t t e mp e r a t ur e p r ov id e d t h e

pre ssure r em ai n s con s ta n t T h e b oili n g p o n t o f m e thyl s al ic y
'
-
.

la te is 2 2 4 a t 7 60 mm an d 1 1 5 (approx ) a t 2 0 mm I ts sp e cific
°
.
,
°
.

g r a vi t y is a t Y i e ld 1 7 gr a ms ,
.

1
Compa re e th yl ac e ta te p , . 1 06 .

19 1
19 2 LAB ORATORY MANUAL G
OF OR ANI C C H E MI S T RY

Q UE S TI ONS
D e fin e a n e s t e r .

W hy n o t u s e th e t e rm e th e r e a l s al t
W h a t is th e s truc tur e o f s alicylic a cid ?
E xpl a i n why c on c sulfuric a cid is us e d
. .

Co uld di lu t e sulfuric a cid b e us e d ?

Co uld c o n c hydro chl o r ic a cid b e us e d ?
.

Why is n o t me thyl sulfa te f orm e d i n s te ad of m e thyl salicyl ate

in th e e xp e r im e n t ?
Wh a t e ff e c t h a s a n e xce ss of m e thyl alcohol on th e yi e ld of
m e thyl s alicyl a te ? a n e xce ss o f s alicylic a cid ?
Ca lcul a t e th e t h e o r e tic a l a m ou n t s a n d c omp a r e wi t h th e
a mou n t s us e d .

W ould th e r e b e a n y m e thyl s alicyl a t e f orm e d if th e a lcoh ol

a n d a cid w e r e h e a t e d a l o n e ?

Why mus t th e m e thyl a lcohol be r em ove d b e f ore th e mix ture

is p ou re d i n to w a te r ?
Why is s odium carb on at e us e d in th e w a shi n g? Could
s odium hydroxid e be us e d ? Why ?
Can y ou su gge s t an y o th e r d r yi n g a ge n t s th a t c ould be us e d
in s tead o f a n hydrous s o diu m sulfa t e ?
Wh a t is E Fisch e r s m e th od of e s terific a tion ?
.
’

H ow is Fisch e r s m e th o d us e d in th e a n alysis o f p r o t e i n s ?
’

( P e r ki n a n d Kippi n g O r ga,
n ic Ch e mis t ry N e w E d ,
”
.
,

Ou t li n e t h r e e o th e r m e th ods o f p r e p a ri n g e s t e r s .

Co mp ar e th e physic a l p r op e r t i e s o f a cids a n d t h e ir e s te rs
(b oilin g p o i n t s olubili ty co n duc tivi t y
-
, , ,

S h ow by m e a n s o f s t ruc tur a l f o rmul a s t h e di ff e r e n c e b e tw e en

th e m ethyl e t h e r o f s a licylic a cid (m e t h yl s a licylic a cid )
a n d t h e m e t hyl e s t e r o f s a licylic a cid (m e t hyl s a licyl a t e ) .

H ow c ould y ou di ff e r e n t i a t e ch e mic a lly b e tw e e n th e t w o

comp ou n ds in N o 1 8 ? .

H ow c o uld y ou s e p a r a t e by ch e mic a l m e an s s ali cylic a cid

a n d m e t hyl s a licyl a t e ?

H o w is s a licylic a cid pr e p a r e d c omme rci a lly ?

Discuss th e ch emical combi n a ti on of oil of Wi n t e rgre en a s
foun d in n ature .
194 LAB ORA T OR Y MANUAL OF OR GANI C CH E M I ST RY

Q UE S TI ONS
Wh e re is t a n n in ob tain e d ?
I S t an n i n a t r u e o rgan ic ( c a r b oxylic ) a cid ?
Wh a t is Fische r s prop os e d formula f or t an n in ? (For an
’

e x t e n d e d discussi on o f th e subj e c t ,
s e e E mil Fisch e r ,

S yn th e sis of D e psid e s ; Lich e n subs t an c e s a n d Tann i n

-
,
”

J ou rn A mer Chem S oc 3 6
. . . .
,
1 1 70 For f o rmul a
.
,

rea d pp 1 93
. 1

Wi th le ad a ce ta te d oe s tan ni n pre cipi ta te le a d t an n a te or

,

a c ompl ex o f l ea d a c e t a t e a n d t an n i n ?

Comp are th e r ea c t i on wi t h ge l a t i n e t o th e u se o f t an n in in
ta n n i n g hid e s .A ls o wi t h th e r ea c t i on of milk in t ea .

Why is gu m a rabic use d in th e in k?

Wh at ch an ge s t ak e pl ace in th e in k on th e p ap e r a f t e r
s ta n di n g?
I n c omm e rci al in k h ow is th e fe rr ous s a l t k e p t fr om oxid a t i on ?
A S f ar a s y ou c an S h ow h ow th e d epsid e s are syn th e siz e d
”
.
,

( S e e Fisch e r’
s a r t icl e a b o v e ) .

How is tann i n u sed in dy e in g ?

 E xpe rime n t No . 59

AD DI T I ON OF A H AL OGE N A CI D T o AN OLE F I NE

P r e par at on i of T ran s - D ic hl or- te rpan e ( imon e n e

d L-

d i h y d ro c hl o ri d e ) f r o m d—Limon e n e

To a 50 cc dis tillin g fla sk wi th an air con d en se r a tta ch e d ad d

.
-

2 0 cc of crud e d lim on e n e a n d a sm a ll a m o u n t of brigh t s o dium

1 -
. .

Dis t ill an d co lle c t s ep ara te ly th e fra c ti on b e twe en 7 0 1

°

R e dis t ill this fr a c ti on usi n g a n o th e r sm all pi e c e of Cl ean s o dium

, ,

a n d c o ll e c t th e p o r t i on b o ili n g cl o s e t o t h e b o ili n g poi n t o f pur e -

d lim on en e 1 7 5 I t is n e ce ss a ry t o u s e pur e d lim on en e

°
- -
,

in the exp e rim e n t D e s troy th e s odium in the re sidu e s by t rea t

.

m en t wi th alcohol b e fore the app a r a tus is cle an e d wi th wate r .

Arr an g e an E rl en m e ye r suc t i on fl a sk wi th a dr oppi n g fu n n e l -

a s a g e n e r a t o r f o r hydr o chl o ric a cid gas P l a ce a b ou t 2 5 grams

2
.

o f s odi um chl o rid e in th e fl a sk a n d c o v e r i t w i t h c on c hydro .

chloric a cid From th e dr oppin g fu nn e l all ow con c sulfuric

.
-
.

a cid t o drip in to th e mix t ur e P a ss a sl ow s tr ea m o f th e gas .

t hr ough a n e mp ty s af e t y b o t t l e a n d t h en in t o a 2 5 0 cc wid e .

mou th e d b ottle through a tub e op e n i n g a bove a s olu ti on of 1 0 cc .

o f th e pu rifi e d d lim on en e in 5 cc o f gl a ci a l a c e t ic a cid

-
K e ep this . .

s olu tion cold by pl a cin g the b ottle in a fre ezin g mi x ture con sis ti n g
o f ic e a n d a sm a ll a m o u n t o f s a l t T h e u n us e d gas is n o t all ow e d .

t o c om e ou t i n t o th e r oom bu t is abs orb e d by a s o dium hydroxid e ,

s olu ti on in a third b ottl e as th e br omi n e vapo rs w e re abs orb e d ,

in th e exp e rim en t f o r pr e p ari n g e thyl en e dibromid e (p .

1
If on ve ry c rude oil is a vail abl e pLI rif y it firs t by dis til l in g w i th s team
ly a ,

d ryin g w i th c a l c iu m c h l o ri d e a n d sub j ec t in g t o a n o rd i n a ry d is t ill a t i on

, .

A ve ry c on ven ien t gen erat or f or preparing h ydrogen c hl ori de from c on c

2
‘
.

h yd ro c h l o ri c a c i d a n d c on c s ul furi c a c i d is de s c ribed by S w e e n e y J our n A mer

.
, , . .

Chem S oc . .
,
39 2 1 86 .
19 6 LAB OR AT OR Y MANUAL OF oRGANI C CH E MI ST RY
In a sh or t time th e liquid s olidifie s to a crys talli n e m ass Ab ou t .

f or ty fiv e min u te s is r e quir e d I t S hould n ot b e com e appre

-
.

c iab l y disc o l o r e d Tr an sfe r it t o a b e ak er wi th c old wa t er

. .

U s e a f ew cc of a lc oh ol t o diss olve ou t th e r e sidu a l p ar ticl e s an d

.

a dd this to th e m ai n p or t i o n Dilu te to 2 00 cc s tir w ell an d . .

, ,

fil te r Off th e s olid produc t wi th suc ti on in a B uchn er fun n el

(P
Diss olve the produc t in ab ou t 4 5 cc o f alcoh ol fil te r fr om .
,

a n y i n s olubl e p a r t icl e s a n d p our in a t hi n s t r e am wi th s tirri n g

, , ,

i n to 2 00 cc of cold wa te r T h e dic hl or terp an e s ep ar a te s imm e

. .

dia t el y in sm a ll whi te crys ta lli n e lumps Fil te r again wi th .

suc ti on an d pr e ss ou t wi th a sp a tul a on th e sm oo th sid e of 1

a cl ean p or ous t il e (p 5 6 ) t o r em ov e th e l a s t t r a c e s o f m ois tur e

. .

S i n c e th e subs tan c e e v ap or a te s v e ry sl o wly wh en l e f t in th e

op e n it mus t b e c ov e r e d wi th a w a t ch gl a ss if a ll ow e d t o s tan d
,

a n y l e n g t h of t im e b e f o r e it is b o t t l e d T ra n s dic hl or terp an e .
-

is a whi te crys ta lli n e s olid m e l ti n g a t I t c an b e re c ry s t al

,

l iz e d fr om wa rm a lcoh ol Yi e ld 3 0 pe r ce n t o f th e th eory
.
,
.

NOTE S

1 . S i n c e th e
p r oduct d e comp s s w h s ta dmg the p r e s c e o e
‘
en n In en

o f a ci d th e e xp e r ime t sh ul d b e c mpl e t e d i
,
n o o labor a to ry p r iod
o n ne e .

I f thi s is n o t p ossibl l t th e p r o du t r ma i in w a te r
e, e c e n .

T h e c i s f o r m of d ic hl o t e p e m l t s a t 5 a d is usually
°
2 .
- -
r r an e 2 n

liquid a t o r din a ry t mpe r a tu r s I f th is is ob t i d i t ad of the

e e . a ne ns e

solid t s for m it is p r ba ly
ran - b d u t ot h e f d —lim e th a t
e o u se o on e n

h s n o t b e n p r op e r ly pur ifi d or t o a ll win g th e t mp e r a tu r e t o go
a e e ,
o e

t oo h igh .

3 T
. h e sp e c ific g r a vi t y o f d lim o n e e is a t -
n

4 T
. h e subs t a n c e is a l o n am e d ds ic h l m t h a e dip en t n e -
or -
en n ,
e

dih yd r oc h l o r i d a d t s t rpi
e, n d i c hl or i de
r an -
e n .

5 If
. t h e d ic hl o t e p d rs r t c
an er ys ta lli e o
oe u t a f t e r b e i
non g z

pour ed i t w a t r c o l th e tir ma t r ial i ic an d th en r move the

n o e o e n e e n e e

l umps an d p r ss th em ou t on a p r ous t il I f th e r e is an y o f th e t n s
e o e . ra

for m p r e sen t it will gen r ally r emai on t p f te r t h e l i quid impur itie s

e n o a

h ave b een abso r b e d Th n r ecrysta lli e f r om al c hol tc

. e z o ,
e .

1
s teel spa tula is used it sho ul d a l w ays
If a be previ ously c l ean ed wi th soap to
re mov e tra c e s of d us t an d rus t .
 S YN TH E S I S OF CAM P H OR F R OM PI NE NE

(I NF I VE S TE P S )

E xp e rim e n t N o . 60

(1) Pin e n e h ydr oc hl ori d e f r om P i n e n e (R e c ti fie d Oil of T ur

p t ne
e n i )
P e rfo rm this xp erim en t u n d e r the h ood or conn e ct th e
e ,

o u t l e t t ub e wi t h th e suc t i on pump a n d l e t th e w a t e r r u n ver r

s l ow l y . I n th e l a tt e r c a s e p a ss th e g as e s t hr o ugh a t ub e op e n i n g
jus t ab ove th e surfa c e of a 2 N s odium hydroxid e solu ti on c on
t ain e d in a b o tt l e a n d th en t o th e pump
,
1
.

P r ovid e a 2 5 0 cc S h o r t n e ck r ou n d b o t tom fl a sk wi th a
.
-
,
-

t hr e e h ol e d rubb e r s t opp e r thr ough whi ch p a ss ( 1 ) a ga s i nl e t

-
,

t ub e r ea chi n g a lm os t t o th e b o tt om o f th e fl a sk ( 2 ) a c a lcium ,

chlorid e tub e (3 ) an d a the rm om e te r S a tur a te 2 00 grams of

,
.

pi n en e con t ain e d in this fl ask wi th dry hydr ogen chl orid e ,

which is g en e ra te d in th e f ollowin g app ara tus Fit up an .

o rdi n a ry li t e r fl a sk or b o tt l e wi t h a dr oppi n g fu n n e l a n d an o u tl e t -

t ub e i n s e r te d t hr ough a tw o h o l e d s t opp e r -
Con n e c t t his ( 1 ) .

wi th an emp ty w a sh b ott l e ( 2 ) wi th a Woulff b ot tl e or a 2 5 0 cc

,
2 -
.

wide m ou th e d b o ttle con tain i n g con c sulfuric a cid provid e d

-
.
,

wi th a s af e ty tub e 2 f ee t l on g (3 ) an o th e r wa sh b ot tl e a ls o c on
,

t a i n i n g c on c sulfuric a cid a n d (4) wi t h a n e mp t y w a sh b o t t l e

.
, ,

from which th e gas is l e d i n to th e pin en e fl a sk T h e emp ty wa sh .

b ottl e s ac t a s gu ards an d pre ven t an y d an ge r of s eri ous expl o

si on s in ca se th e re is b a ck pr e ssure in th e app ara tus U s e .

rubb e r s topp e rs an d gl ass tubin g through ou t j oi ni n g th e gl a ss ,

1
T e s t th e
pp a ra tus f or l eaks w i th th e gas u n der pre ssure before turn i n g
a on

th e w a t e r Oth e rw is e b u bbl e s o f a ir ma y be mis ta ken f or h yd rogen c h l ori de

. .

2
A w i de bottl e w i th thre e a pertures
 LABORAT ORY E X P ERI M E NT S 199

tubin g wi th as sh or t rubb e r con n e c ti on s as possible T he tw o .

wash b o t tle s wi th sulfuric acid are n e ce ss ary f or th oroughl y

dryin g th e gas .

T h e pi n e n e fl a sk is imb e dd e d in a mix tur e o f cr a ck e d ic e

a n d a sm a l l am o u n t o f c omm on s a l t A s th e r ea c ti on pr o c e e ds .

m ore s al t may be n e ce ss ary Wh en th e app a ra tus is all r e ady .

p u t 5 00 gr a ms o f c o mm on s a l t in th e g en e r a t i n g fl a sk a dd ,

e n o ugh c on c hydr o chl o ric a cid t o cov e r th e s a l t a n d t h en a ll ow

.
,

con c sulfuric a cid to drop up on this mix ture from th e droppin g

.

fu n n e l T h e gas sh ould be ru n in to th e pi n en e c on tinuou s ly

.

a t a f airly r apid r a t e (ab ou t tw o h o urs ar e n e c e ss ary ) c a re ,

bei n g ta ken tha t the tempera tu re does n ot exc eed T he re

a c tion d oe s n o t t ak e pla ce r eadily b e low T h e b e s t t em

p e r a t u r e is a b o u t S o m e t im e s i t is n e c e ss a ry t o t a k e

th e ic e a w ay in ord e r t o a ll ow th e t e mp e r a t ur e t o ris e a n d t h e
re a cti on to s tar t A f te r th e gas h as b e en p assin g in f or s om e
.

tim e th e t e mp e r a tur e may ris e t o This will do n o gr ea t

harm o th e r th an to c olor th e mix ture on a ccou n t of sligh t
,

d e comp osi ti on bu t the temp e ra ture sh ould n o t be a llowe d

,

t o s ta y up A high e r t e mp e ra tur e sh ould b e av

. o id e d A .

slowe r s tre am of gas an d fur th e r cooli n g will s oon bri n g th e

t e mp e r a t ur e d ow n T he s u c c es s of the experi men t depends u pon
.

the drynes s f
o the ga s an d the temper a tu re f
o the re a c ti on .

A f te r
b ou t tw o h ours wh en n o m ore gas is abs orb e d an d
a

th e pi n e n e h as b e e n t r an sf o rm e d i n t o a s e mi s o lid m a ss di sc onn e c t -

th e fl a sk an d cl o s e i t wi t h a g o od c ork or rubb e r s t opp e r Cool .

in a fr ee zi n g mix tur e c on sis t i n g o f a b ou t

° °
it to 10 to 15

tw o p a r t s o f cr a ck e d ic e an d on e o f s a l t an d l e t i t r e main f o r
'

thir t y mi n u te s or o v e r n igh t (in th e ic e b ox) I n c a s e i t is l e f t -

.

o v e rn i gh t c a r e S h o uld b e t ak en t h a t n o w a t e r fr om th e m e l ti n g
,

ic e will ge t i n t o th e fl a sk by f a s t e n i n g th e fl ask upri gh t wi th a

,

clamp On th e n ex t d ay it mus t b e p a ck e d aga in an d cool ed

.

f or an h our Fil te r off th e crys talliz e d pin en ehydroc hl oride wi th

.

suc ti on an d pre ss ou t on a p or ous t il e Cool th e fil tra te an d

1
.

thus ob t ain m or e of th e pr o duc t N ow diss o lve th e en tir e .

1
It is c on v en i en t t o u se a flat t opp e d gl ass
-
s topp er to press d own th e c a ke

in the B u c h n er funn el .
200 LAB ORAT OR Y MA NUAL OF OR GANI C CH E MI STRY
crude produc t in ab ou t 8 0 cc of wa rm a lcoh ol con tain e d in a .

b e ake r an d h ea te d on th e s team b a th I t will re m ain mil ky -

.

whi te Th en c ool t o. wi th s tirri n g to avoid th e f o rm a ti on of

a s o lid m a ss Fil te r an d pre ss ou t as ab ove Y i e ld 1 00 1 2 5 — .
,
.

grams T h e sn ow whi te crys ta llin e p owd e r which h as an o d or

.
-
,

r e semblin g camph or m e l ts a t 1 1 8 This produc t is

,
°

us e d f or th e n ex t e xp e rim en t I t is s om ewh at volat ile a t th e .

o rdi n a ry t e mp e r a t ur e an d pr e ssur e an d t h e r e f o r e sh ould n o t b e ,

l e f t u n cove re d f or an y l en g th of t im e .

N OTE S

1 . you r time s o tha t th e xpe r ime t may be s tar ted at

Arr an ge e n

t h e b gi i n g o f a l b o r a to r y p r i o d
e nn T h e p i e h y dr oc hl orid e sh oul d
a e . n ne

b r c r ys t a lli d f r m al c oh l th e same a f t r n o o o o th e f llow in g

e e ze o o e n r n o

d ay i c it de comp o se s S l ow ly o s ta di g
,
s n e I f it doe s n o t c rys talli n n n . ze

a f t r th e ga s h as b e
e r i fo h ou r s th e pi n e use d p r ob ably
en un n r ,
en

co tai e d moistur br w a oth rw ise impur e o th e tempe r atu r w as

n n e s e ,
r e

t oo l ow .

2 fe c tly pu r e a n d s t bl e p in en ehy droc hl oride which mel ts

. P er a

at 5
I 2 c a b e
°
b t i e d nb y c rys t aolli a t ia n f r m p t r o l u m e th e r bu t a
z on o e e ,

la r ge a mou t f th e subs ta c is los t by this m thod

n o n e e .

3 A t o
. e t i m p i e n e h y d o c hl o id e
e w a s k n onw a s r a r t ifi c i a l r n n

c a mph o r on a c c ou t
,
of its d r N w h w eve r th is is a
n o o . o , o ,

mis me r si c e ca mph r i ts lf c a b sy th si e d
no ,
n o e n e n e z .

4 R e c tific ati on of Oil of T urp e n ti n e

. P in e (b ili n g po in t . en o -
,

is th e c h ief c o sti tu t f th e Oil of tu rp ti n en I t is ob ta i e d

o en ne . n

fair ly pur e by distilli g th e Oil in a fl sk w i th m tallic s dium an d n a e o

usi g a You g s p a r f r a c ti a ti g c lum or s till h ad (Fig 4

n n
’
e on n o n -
e .
,

p . T h e p r ti g i g o v r b
o e t w e
one 5 4 a
o n d 6 0 c o e sis t s n 1
°
n 1
°
n

a l mo t e n t i r ly
s f pi en e e Fo th is e p r ime t u s e 3
o n . c c of c r u d e
r x e n 00 .

pi e a d ab ut 4 5 gr ams f sodium
n ne n o o .

5 T h e . b r w r si o us m a ss
o r nm a i i eg i t
n h e fl a s k is t r e a tede n n n

wi th al c h ol t o d st r y a y u tt ac ke d s dium b for w a te r is added

o e o n na o e e

a n d th t h fl a sk is l a
en e d c e ne .

6 S ave a sp c im f a t l ast r m f h f t h p r d u s in
'
. eg a o en o c e e o t 1 ea o c

t h e syn the sis of camph o r f r om pi n e n e an d h an d th em in , .

 E pex rime n t No . 61

( ) Ca
2 mph e n e f r om P in e n e h y dr oc hl ori d e

In a cc rou n d b ot tom e d fl ask m e l t 1 90 gr ams of ph en ol

400 .
- 1

a n d t h en add 7 5 gr a ms of p o t a ssium hydr o xid e (crush e d) T h e 2

.

mix tu re becom e s h e ate d sp on t an e ously an d th e al kali diss olve s .

S h ak e W a rm if n e c e ss a ry t o pro duce c ompl e te s olu ti on

.
, ,
.

N ow conn e c t th e fl a sk wi th a co n d en s e r f or di s t ill a ti on i n s e r t a ,

t h e rm om e te r wi th th e bulb in th e n ec k (n ot in th e liquid ) a n d ,

car efully hea t ove r a m e tal gauz e to di s till off the wate r f orm e d
in th e r e a c ti on A sm a ll a m oun t of ph en ol a lso g o e s ove r
. .

Af te r th e t e mp e r a tur e r ea ch e s 1 5 0 e xch an ge th e w a te r c on
°

d en s e r f or an air con d en s e r W h en all th e wate r h as b een

.

dis tille d Off an d th e temp e ra ture h as ris en t o a ll ow t h e

fl ask to cool s om ewh at discon n e c t an d a dd 1 00 grams of pin en e

, ,

hydrochlorid e in thr e e portion s th e s e con d an d t hird af te r

3
, ,

th e pr e c e di n g r e a c ti on h a s subsid e d A t t a ch an uprigh t air .

con d en s e r to th e fl a sk a f te r e a ch a ddi ti on an d he at care fully

a t firs t S i n c e t h e r e may b e a vi o l e n t r e a c t i o n Fi n ally keep th e .

mix ture b oilin g f or tw o or thre e h ours sh aki n g th e fl ask f re ,

qu en tly T h e vap ors mus t n o t be a ll owe d to ris e m ore th an

.

on e h a lf th e l en g th o f th e air c on d e n s e r
- If the heati n g i s very .

s tr on g, fu mes w i l l c ome ou t o f the top and thes e w i ll s ettl e down an d

bec ome i gn i ted . h e atin g is in te rrup t e d an d th e p otassium

I f th e
ph en ol a te is allow e d to s o lidify th e fl a sk mus t be cau ti ously
h e ate d a roun d th e S id e s u n til th e solid m a te ri a l m e l t s b e fore h e at
is appli e d a t th e b o tt om .

1
If ph en ol c ome s in c on ta c t w i th th e skin a pply a l c oh o l a t on c e
an y .

2
S o d iu m h y d rox i d e c a n n o t b e us e d on a c c o u n t of th e h i gh me l tin g po in t -
of

th e sodiu m ph en ol a t e .

2 Pr p r
e a e d in t h e pr e vi ous e xp e r ime n t .

202
 LAB OR AT OR Y E X P ER I M E NT S 203

Th en in ord e r to ob t ai n th e camph en e subj e c t th e mix ture

, ,

t o dis till a ti on in th e s am e m ann e r a s th e w a t e r w a s dis t ill e d

‘

ab ov e usin g an air con d en s e r u n til th e temp e r a ture of th e

, ,

vap or r e a ch e s 1 80 (th e b oil in g p o in t of ph en ol) A t firs t

°
-
.

pure camph en e di s til ls ( 1 50 l ate r it is c on tamin a te d

°

wi t h i n cr ea sin g am oun t s of ph en ol T h e dis till a ti on is s t opp e d .

wh en a drop o f th e dis till ate e n tire ly diss olve s in dilu te sodium

hydroxid e (Why ?) T h e dis t ill a te is th en sh ak en in a fl a sk wi th
.

dilu te s odium hydroxid e an d c o ol ed wi th ic e wh e r e by ,

th e c amph e n e s o lidifi e s in crys t a lli n e lumps I f th e c amph en e .

d oe s n o t crys talliz e ou t wel l from th e alka lin e s olu ti on w a rm , ,

s ep ara te an d then cool Fil te r wi th suc tion an d w a sh wi th ic e

.

w ate r r e tain i n g th e fil tra te f or r e coverin g th e ph en ol if d e sir e d

, ,

( s e e b e l o w ) I f a sm a
. ll a m o u n t o f a n o ily c on s t i t u e n t sh ould p a ss

thr ough th e fi l te r p ap e r s e p a r a t e it fr om th e r e m a i n d e r of th e
,

fil tr a te a n d a dd to th e m ai n p or ti on H e a t th e camph en e in a .

small fl ask on th e s team b a th u n til it m el t s Wh e n it is liquid a n d

-
.
,

a g oo d s ep a r a t i on c a n b e m a d e p our off from th e drops of w a te r

,

i n to an E rlen m eye r fl a sk an d a gain m e l t in th e s am e w ay wi th

a ddi t i on o f a f e w pi e c e s o f c a lcium chl o rid e d e c an t an d fi n a lly , ,

fra c tion a te in a r ou n d b ottom e d fl a sk surm ou n t e d by a good

:

fra c ti on at in g column such as th e app a ra tus of You n g (Fig 4 .

,

p . t o which is co n n e c te d a n a ir c on d en s e r P r o te c t th e .

dis tilli n g app a ra tus from e xce ssive r a di a ti on an d con s e qu en t c on

d e n s ati on by surr oun din g it wi th p ap e r or a tow e l Coll e c t th e .

fra c ti on dis tilli n g b e twe en 1 5 5 an d This s oli di fie s on

°

cooli n g to a colorl e ss crys tallin e m a ss Y i e ld 60 gr ams P ure

,
.
,
.

camph e n e m e l t s a t 5 1 5 2 an d b oils a t
— ° °

T h e pr o duc t S h ould b e chl ori n e fr ee Te s t for chl orin e -

.

a cc o rdi n g t o t h e di r e c t i on s on p 1 4 I f th e pr oduc t is n ot
. 1 .

chlorin e fr ee re dis till u n til th e dis till ate give s n o te s t f or h al ogen

-
, .

T h e r e sidu e in th e fl a sk c on t a i n s a sm a ll a m o u n t o f p i n en e
hydro chl orid e .

I f it is d e sire d th e s tud en t may r e c ov e r th e ph e n o l us e d

,

1
Us e on ly
is fra c t i on f or th e n e xt exp erimen t T h e l ow er boilin g fra c ti on
th .

(a ro u n d c on ta i n s o th e r h y d ro c a rbon s w h i c h if a ll ow e d t o r e ma i n a pp a r e n t ly
, ,

c aus es t roubl e in th e c ry s ta lli zat i on of th e is oborn eo l l ate r on ,

204 LAB ORAT OR Y MANUAL OF OR GANI C CH E MI ST RY
in this e xp e rim en t p ar t of which I s I n th e m ain r e sidu e a n d
,

p a r t in th e s o dium hydroxid e wa shin gs by m aki n g th e combi n e d

,

r e sidue s a cid wi th hyd r o chloric a cid an d t h e n e x t ra c ti n g wi th

e t h er
. Dry th e e th er solu ti on f or twen ty four h our s ove r a n hy
-

drou s s odium sulfa te d e c an t an d r e m ove th e e t h e r in th e o rdi n ary

,

w ay by di s t ill a t i o n a n d t h e n dis t ill th e ph e n o l usi n g a sh or t air

,

con d en ser B oili n g poin t 1 8 1 5 Yi e ld 1 50 1 60 grams

.
-
.
°
— .
, ,

QUE S T I ONS
Why is p o ta ssium ph e n ol ate use d i n s te ad of p ota ssium
a lc o h o l a t e ?

Why n o t u s e s odium ph en ol a te ?
H ow is th e c amph e n e s ep a r a t e d fr om th e ph e n ol ?
G ive tw o r ea c t i on s which S h ow t h a t c amph e n e is ch e mic a lly
d iff e r en t from b orn yl en e .

Wh at is f orm e d wh en c amph en e is oxidiz e d wi th chromic a cid ?

 x r
E pe im e n t N o . 63

( )
4 I s ob or n e ol fr om I s ob orn yl a c e ta te

T h e is ob orn yl a c e ta t e is hydrolyz e d (s aponi fie d) wi th po tas

sium hydroxid e an d con ve r te d i n to is ob orn e ol a s f oll ows : I n a
2 5 0 cc fl a sk diss o lv e 5 0 g
. rams of is oborn yl ac e ta te in a s olu ti on
1

of 1 00 cc o f a lc o h o l an d 2 0 gr a ms of p o t a ssium hydr oxid e an d

.
,

h eat to b oilin g f or thr ee h ours u n d e r r eflux c on d en se r on th e s team

b a th P our the s olu t i on i n to c old wa te r T h e is ob orn e ol s ep ara te s
. .

a s a whi t e o r ligh t y e ll ow s o lid I f it r e m ai n s a s a n oil or a .

s emi s olid m ass pl a ce th e b eak er in ic e an d s tir wi th a m e ch an ical

-
,

s tirre r f or 5 to 2 h ours T h e isob orn eol gra du ally b e com e s whi te

2 -
.

an d crys t alli n e I f it d oe s n ot crys t a lliz e bu t r e m ain s a s an oil

.
,

o r an o ily lump s ep ar a t e a dd fr e sh w a t e r a n d s tir a g ai n

, ,
B r e ak ,
.

up an y lumps Or c on tin u e th e hydrolysis wi th fre sh a lco

.

holic p ota sh f or 5 to 1 hour Fil te r off th e crys tals wi th .

suction an d wash wi th cold w a te r pre ss ou t an d dry on a p orous

, ,

til e .M e l ti n g p oi n t of t his crud e pr oduc t 2 03 2 0

- —
Yi eld , ,

35 gr a ms T h e is o.b o r n eol t hus o b t a i n e d is pur e e n o ugh f o r c on

version i n to camph or a s d e scrib e d in th e n ex t exp e rim en t

, .

Crys t alliz e d fr om p e t r ol e um e t h e r abs olu te ly pur e is ob orn eol ,

is ob tai n e d m e l tin g a t 2 1 2 (in a close d tub e s ee f oot n o te 7

,
°
,
-
,

p .

Q UE S TI ON S

Comp ar e th e pr e p ar a t i on o f glyc o l fr o m e thyl e n e dibromid e

’
1 .

t hr o ugh th e a c e ta t e .

2 . H ow c a n e thyl a lcoh ol b e pr ep a r e d fr om e t hylen e ?

1 E xp e ri me n t N o 6 2 . .

2
An e ecl t ri c mixe r su c h a s a r used a t soda w a ter f ou n ta in s is exc ell en t f or th i s
e

ur
p p o s e .
 LAB ORAT OR Y EX PERI M ENT S 207

Wh at ch e mical r e a c tion of isoborn eo l shows th at it is a

t e r t i a ry a lcoh o l ?
W hy c a nn o t a goo d m e l ti n g p oi n t of is ob orn e ol be t ak en in
-

a n op en t ub e ?

H ow d oe s ch an gin g th e w a te r aid I n th e crys t alliz a ti on of th e

produc t ?
I s a lc oh o lic KOH g en e r a lly us e d f or hydr olysis ? (Comp ar e
th e a n a lysis of f a t t y oils e t c )
,
.

How c an t e r t i a ry a lcoh ols be pr ep ar e d by th e Grign a rd

r eac tion ?
 E xpe rime n t No . 64

( 5 ) Camph o r f r om I s ob o r n e ol

P erform this ex p er i men t u n der the ho od or n ear the dr aft i

p pe .

M ak e mix tu r e of 60 gra ms of con cen tra te d n i tric a cid (sp gr

a . .

a n d 1 2 gr ams o f r e d fumi n g ni tric a cid (sp gr in a . .

2 5 0 cc fl a sk c oo l t o 2 0 a n d k ee pi n g th e t empe r a t ur e b e
°
.
,

t w een 2 0 cau ti ously a dd in sm all a m ou n ts 3 0 gr ams o f

°

is ob orn eol E a ch p or ti on of isob orn e ol dissolve s in th e a cid

1
.

wi th rise in t empe rature an d e volu ti on of n i tric oxid e s Durin g .

th e Op e r a ti on th e mix tur e mus t b e w e ll s t irr e d sh ak en a n d ,

coole d A t th e en d a comp ou n d of camph o r a n d N 05 s ep ara te s

.
, 2

as a sligh t ly c ol o r e d o ily l a y e r Con t i n u e th e s tirrin g an d .

S h aki n g as much a s p o ssibl e f or a b o u t thir t y t o f or t y mi n u te s ,

an d t h e n whil e S h akin g sl o wly p o ur o u t th e c on te n t s i n t o s om e

, ,

cra ck e d ic e in a b eak e r T h e Camph or s ep a ra te s ou t in whi te

.

lumps I f it doe s n ot m el t th e ic e s ep a ra te a n d add cold

.
, , ,

wa te r to th e ca mph or l ay e r I t will th en crys ta lliz e ou t e sp e .

,

c ia ll y o n c o o lin g Fil te r w i th suc t ion an d wa sh wi th ic e wa te r

. .

This c r ud e pro duc t m e l t s a t ab ou t 1 6 8 an d con tain s s om e °

o xid e s of n i t r o g en I n o rd e r t o purify th e camph o r t re a t i t in

.

a 5 00 cc fl a sk wi t h a dilu te s o lu t i o n o f 3 gr a ms o f s o dium h y drox

.

ide a n d 5 gr a ms o f p o ta ssium p e rm an g an a t e a n d th e n dis till ,

wi th s team throu gh an air con d en s e r in to a wide m ou th e d b o ttle

2 -

which is cool e d in cold run n i n g wa te r Dry th e purifie d pro .

duc t on a p orous til e I t sh ould b e p e rfe c tly whi te an d m e l t a t

.
,

172
°
Y i eld 2 1 gr ams Camph or is vol a tile an d ca re
,
.

mus t b e us e d to ca rry on all op e ra ti on s u n d e r goo d coolin g .

1
E x pe ri me n t 6 3 .

2
T h e c a mph or s e p a ra te s ou t in a w a te r c on den se r , an d th e re fore if on e is used
s i la t ion mus t be d isc on t in u ed n ow a n d th e n a n d
th e d i t l , th e c a mp h or push ed o u t

wi th a l on g rod Other w ise it w ill c l og th e c on d e n s e r

. .
 Exp e rime n t No . 65

D I RE CT OXI D A TI ON OF A H YD R OCARB ON
An thr a qui n on e f r om An th r a c en e

Con n e c t fl ask con taini n g 2 5 grams of an thra cen e wi th an

a .

a ddi t i on t ub e a n d a r e fl u x c on d e n s e r P our in 2 0 cc o f gl a ci a l
. .

a c e tic acid a n d h e a t o n th e s t ea m b a t h P r ep ar e a s olu ti on of

-
.

4 5
. gr a ms o f chr o mium t ri o xid e i n a li t t l e w a t e r a n d a dd 7 cc .

o f gl a ci a l a c e t ic a cid A dd this solu ti on in sm a ll a m ou n t s t o

.

t h e fl a sk a n d c on t i n u e th e h ea t i n g f or fiv e mi n u t e s a f te r th e
a ddi t i o n of th e l a s t p or t i on I t will n o t al l diss olv e P our ‘

. .

t h e gr e en mix tur e i n t o w a te r an d s t ir w el l ,
Fil te r off th e .

pre cipi ta te wi th suc ti on wa sh an d dry it R e crys talliz e as

, ,
.

f ollows : P our ove r th e dry produc t in a fl ask 1 1 0 cc of t olu en e . .

Conn e c t wi th an uprigh t c on d e n s e r a n d h ea t c a r e fully ove r a

wire gauz e to b oili n g f or se ve ral mi n u te s D o n ot u s e such a .

l arge fl ame th at s om e of the vapors com e u n con d en s e d ou t of th e

t op of th e c ond en s e r T h e V ap o rs a r e h ea vy a n d will s e t tl e
.

d own an d b e com e igni te d T h e solubili ty of an thra quin on e

.

is p ar t s in 1 00 p art s of toluen e a t I mm e di a t e ly a f t e r
disconn e c ti n g fil te r th e s olu ti on thr ough a flu te d fil te r p ap e r
,
1

in a gl a ss fun n e l s e t in a h ot wa t e r fu nn e l -2
usin g a s tirrin g ,

ro d t o dir e c t th e flow o f th e h o t s olu t i on i n t o t h e fil t e r Wh en .

fil te ri n g i n fl amm abl e liquids th e bur n e r u n d e r th e sid e t ub e

,

mus t a lways be r em ove d T h e an thraquin on e r apid ly crys tal

.

liz e s ou t I t is s ep arat e d w i th S uc tion an d al lowe d to dry

.
3

1
p 1 28
S ee . .

S ee p 1 2 8
2
. .

I f it is d e sire d t o c on c en tra t e th e t olu e n e s olu t i on dis t ill off th e t olu en e in t h e

2
,

usua l w ay from a d is tilli n g fla sk T h is h o w ever generally give s dark c ol ored

.
, ,
-
 A
LABOR T OR Y EXP ER I M ENT S 211

b e tween fil te r p ape rs L arge w ll f orm e d crys ta ls are ob tain e d

. e -

if the fil tra te is a llowe d to cool ve ry sl owly This c an be d on e .

by pl a ci n g th e b e ak e r in wa rm wa te r an d l e t t i n g all cool t oge th e r .

H owe ve r th e fin e r crys ta ls form e d by r apid c ooli n g are m or e

,

like ly t o be the pur e r produc t M el tin g poin t 2 8 5 . cor -

. .

Yi e ld 2 5 gr ams
,
. .

e a Sampl e of t h e an t hr a qui n on e a s f ollows : P l a ce

o u n t o f t h e m a t e ri a l on an 8 cm w a t ch gl a ss c ov e r -
.
,

an 8 cm fil t e r p ap e r which h as b een p e rf ora te d wi th a

-
.

e r of t i n y h ol e s a n d t h en p u t a n o t h e r w a t ch gl a ss o f th e
,

size con vex sid e up ove r t he se S e t on a wire g auz e

, ,
.

l a ce a ve ry sm all fl am e u n d e rn ea th L igh t y ellow crys ta ls .

-

n t o d ep o si t on th e c o ld surf a c e o f t h e upp e r w a t ch

th e p ap e r will pr e v e n t t h e m fr om f a lli n g b a ck t o th e
ne A n i n ve r te d fu n n e l c an b e us e d i n s t e a d of th e upp e r
.

gl a ss D e te rmin e th e m e l ti n g p oi n t of t his sublim e d

.
-

pl e as w e ll as of th e r e crys t a lliz e d pr o duc t .

Q UE S TI O N S

I s an thr a qui n on e a t ru e ch e mica l d e riv a t iv e of an thr a c e n e ?

Comp a r e a n t hr a ce n e a n d diph e n ylm e t h a n e in r e g a rd to
xid a ti on wi th chromic a cid
o .

D oe s an thra quin on e h ave an y aliph a tic c h arac teris tiCs ?

Comp a r e it W i t h p b enz oqui n on e -
.

E xpl a i n why y ou sh ould e xp e c t th e 9 an d 1 0 c a rb on a toms

o f a n t hr a c e n e t o b e m o r e e a sily oxidiz e d t h an th e o t h e rs .

Wh a t n a t u r a lly o ccurri n g d y e is r e l a te d t o a n thra qui n on e ?

T o wh a t is th e gr een c ol o r o f th e r e a c t i on mi x ture d u e ?
( C o mp a r e qu e s t i on 4 A c e t a ld e hyd,
e Amm oni a E xp t 1 7 ,
.
,

p .

W hy can n o t alcoh ol or w a te r be us e d in pl a c e of the a ce tic

a cid i n t his e xp e r im en t ?

Why is a flu t e d fil te r p ap e r us e d ?
Why a re th e fin e r crys ta ls mor e lik e ly to be pu r e r ?
E xpl a i n sublim a t i on .

D o e s a n th r a qui n on e c on t ain aux o chr om e or chr om oph or e

g r o ups ?
H ow c a n a n thra qui n on e be r e con v e r t e d i n to an thr a c en e ?
2 12 LAB ORAT ORY MANUAL OF OR GA NI C CH E M I ST RY
13 . Wh a t comp oun d is f orm e d wh e n an thraqu on in e is sh ak
wi th zin c dus t a n d s odium hydroxid e s olu ti on ? H
.

c an t his b e ch a n ge d b a ck i n t o a n t hr a qui n o n e ?

14 . Discuss qui n on e m on oxime r el a tive t o its s t ruc tur e a

m e th o d of pre p a r a ti on from qui n on e an d from ph en ol
, .

1 5 . Wh a t a r e th e n aph th o qui n on e s ? H ow prep a r e d ?

—
214 L AB OR AT ORY MANUAL OF ORG NI C CH E A M I S T RY

3 . To a h yd r o ch l o r ic
cid s olu ti on
a of qui n oli n e a dd a s olu
t i on of p o ta ssium dich r om a te .

Q UE S T I O N S

P YRI D I NE
1 . Wri te th e e qu a tion to S h ow th e subs tan ces form e d in th e
con di ti on o f e quilibrium wh en pyri di n e is dissolve d in
wa te r .

2 . E xpl a i n th e a c t i on o f th e a qu e ous s olu t i on of pyri di n e on

f e r r ic chl orid e Wh a t is th e p r e c ipi ta te ?
.

Wh a t typ e of subs tan ce is f orm e d by th e re a c ti on b e twe e n

pyridin e a n d m e thyl i odid e ? Wr i te its s t ruc tur e .

E xpl ai n th e a c t i on of s il v e r ni t r a t e on th e a qu eous s o lu
'

t i o n of th e pyridi n e io dme th y l a t e (or m e t hi odid e ) C om .

p ar e wi th e th yl ammon iu m chl orid e use d in a pre vi ous

e xp e rim e n t (un d e r M e t hyl A min e p ,
.

Wh a t is f o rm e d wh e n th e pyridin e io dme th yl a te is t rea te d

wi th p ota ssium hydroxid e ?
Wh a t is fo rm e d wh en th e pyridin e iodme th yl a te is h ea te d
a l on e t o Comp a r e wi t h th e pr ep ar a t i on o f o an d
p t o luidi
-
n e fr o m m e t hyl a ni li n e .

How c ould y ou t e ll e xp e rim e n t ally wh en a subs t an c e c on

t a i n s a t e r t i a ry n i t r ogen a t om as in pyri di n e a n d wh en it
con ta in s a s e con d a ry n i trogen a tom as in pyrr ole Con ii n e , ,

e tc . ?
8 . L ook up th e f ormul a s for ni co ti n e c on I I n e t r yp toph an e
, ,
an d

in di go Wh a t n i trogen h e terocycle s do the y con tai n ?

.

Q UI N OLI NE
Wri te the s truc ture s of th e comp ou n ds f orm e d when qui n o
lin e is t re a te d wi th hydro chlo r ic a cid an d this s o lu ti on ,

wi th p o ta ssium dichr om a t e .

Why d oe s th e qui n o li n e dissolve in dilu te hydrochloric a cid ?

H ow c an qui n o li n e b e pr e p a r e d s yn th e t ic a lly ?
H ow d oe s is o qui n oli n e di ffe r fr o m qui n oli n e ?
L ook up s ome a lk a l o ids which c on t a in th e qui n o li n e n ucl e us ;
als o th e isoqui n oli n e n ucl e us .
 P AR T II

OR G A N I C C O M BU S T I O N S
216b FORE WOR D

Wh e re h e has n o t b een v e ry f amili ar wi th a ce r ta in pro ce dur e or

wi th ce r tai n ki n ds of app ara tus h e h a s t ri e d to S h ow th a t l a ck
in th e w ordin g o f th e t ex t T h e d e scrip t i on s o rdi n a rily r e f e r t o
.

w ork on th e comm on o rgan ic comp ou n ds usu ally me t wi th in

l ab ora tory pra c tice .

I t is b eli e v e d th a t m an y of th e difficul ti e s in c arryin g ou t an

o rg an ic c ombus ti on a ris e fr om th e f a c t t h a t th e op e r a t o r a s is ,

ve ry n a tural is n ot t h oroughly f amili ar w i th th e app aratus an d

,

it s p o ssibili ti e s F or t his r e a s on th e app ara tu s h as b e e n v e ry

'

.
,

c ar e fully d e scrib e d an d m an y of th o s e li ttl e kin ks which are

,

ve ry h e lpful bu t n ot alw ays av ail abl e in wri tin g a re a lso a dd e d .

L e s t th e s tude n t l os e t r a ck o f his w o rk on a cc ou n t of th e l e n g th
o f s om e o i th e d e scrip t i on s a n d n o t e s h e is r e f e rr e d t o th e
'

imp or tan t Topical Ou tlin e o f Gen e r al M e th od of P r oce dur e ”

,

which is a co n cise summ ary o f th e n e c e ss a ry op e ra ti on s arr an ge d

t o s av e b o th tim e an d e n e rgy I t mus t b e r e m e mb e r e d th a t y ou
.

can n o t ru n a comb us ti on jus t by k e epin g a s e t o f dir e c ti on s -

b e sid e y our app ara tus You mu s t s tu dy the method in detail . .

Th en th e topical ou tli n e wil l h e lp brid ge th e gaps .

T h e au t h o r h a s t ri e d t o giv e du e cr e di t t o th e prop e r au th or i
t i e s in sp e ci a l c a s e s by n um e r ous r e f e r en c e s in appr opri a t e pl a c e s .

A ck n owl e dgm e n t s are h e r eby gl a dly m a de to such s tan d a rd

w orks a s
G a tte rm an n s P r a c tica l M e th ods o f Organ ic Ch emis t ry
7

W A N oy e s
. . Org a n ic Ch emis t ry f o r th e L ab o r a to ry
’

S udb or ough a n d J am e s P r a c t ic al Or g an ic Ch emis t ry

’

Co h en s P r a c tica l Organ ic Ch e mis t ry

’

F G B en e di c t s E l em en t ary Organ ic An alysis

. .
’

An l e i tu n g zur v e r e i n f a ch t e n E l em en ta ran a lys e

’
D enn s te d t s .

T h e a u t h o r a ls o wish e s t o e x t en d his gra t e ful th an ks f or m an y

h e lpful sugge s ti on s to his colle a gu e s e sp e cially P ro fe ssors Joh n ,

M N e ls on H T B e an s a n d-H a rold A F a l e s an d to his f o rm e r

.
,
. .
, .
,

s tud en t s a n d c o w ork e rs in th e o rgan ic l ab ora to ry a t Columbi a

-

U n i ve rsi ty w h o h av e b o rn e wi t h him in his e ff o r t s to s tan d a rdiz e

,

o r gan ic c ombus t i on s an d t o m ak e th e m mor e e a sy an d frui t ful .

H ARR Y L F I S HE R .

C M
OL U UN BI A T N W Y K
I VE RS I Y, E OR ,

J un e ,
1 9 19 .
 D I V I S I ON A

TH E D E TE RMI N AT I ON OF C AR B ON AN D H YDR OGE N

I . H i s to ri c al 1
I n tr o d u c ti on
I n th e y ear 1 7 8 1 L avoisi e r w o rki n g on th e th eory of c ombu s ,

t i on e s t a blish e d wi t h a f a ir d e gr e e o f a ccur a cy th e qu a n t i t a t iv e
,

r e l a tion of carb on an d oxygen to c arb on di oxid e an d of hydroge n ,

a n d o xyg en t o w a t e r a n d a ls o sh o w e d t h a t c a rb on di oxid e a n d
,

w a te r w e re th e sole pro duc t s o f th e combus ti on o f o rgani c sub

s tan ce s such as spi r i t of win e oil w ax sug ar an d re sin s
“
, , , ,
.

I n 1 7 8 4 h e burn e d W e igh e d p o r ti on s of s om e of th e s e org an ic

subs tan ce s in a kn own volum e of oxygen an d c ol le c te d th e
,
,

ga s eous produc t s in a b e ll jar ove r m e rcury Th e s e g a s eous -

.

pro duc t s h e an a lyz e d by volum e abs orbin g th e carb on di oxide ,

in a p o t a sh s o lu t i on a n d m e a suri n g th e r e sidu al oxyg e n

,
He .

t h en c a lcul a t e d t h e w e igh t of th e w a t e r i n dir e c t ly a n d in this w ay ,

h e w a s abl e t o d e t e rmi n e th e c omp o si ti on o f th e subs tan c e 2

F or .

t h e m o r e difli c u l tl y combus t ibl e subs ta n c e s h e us e d i n s t e a d o f fr e e ,

oxyge n gas m e rcuric o xid e a n d m an g an e s e di o xid e

,
which giv e ,

up oxyg en wh en h e a t e d Thus h e l aid the ve ry foun d a tion s of

3
.

e l e m e n t a ry o rg a n ic an alysis .

'
D e n n s te d t h a s give n us an exc e ll e n t d e t ail e d ac c o un t o f th e h is t o ri c a l d e v el o p
1

men t o f o rgan i c c omb us t i on s in h is a r t i c l e , D ie E n t w i c ke lu n g d e r o rga nis c h e n

E l e me n t a ra n alys e , ”
in Ahr en s ’
S a mmlu n g c h e misc h e r und c h e mis c h t ec h n is c h e r
-

V o rt rage ,
”
IV 1
—1 1
4 . T he a rt i c l e a lso c on t ai n s a ve ry c o mpl e t e bi bli og
rap h y .

2
L a de n b urg
H is tory o f Che mis t ry t ran s by D obbi n
, 2 89 ,
. .

E rn s t v o n M e y e r A History of Ch emistry tran s by G eorge M c Gow an

2 ”
.
, , ,

4 1 0 2 ; A rmi t a ge A History Of Chemist ry

E n glish e i t i on — ”
3d d , ,

54 . D e nn s t e d t o n pa ge s 2 a n d 3 o f hi s h is t ory men tione d abo ve give s a de tai l ed

, , ,

217
218 LAB ORAT OR Y MANUAL OF OR GANI C CH E M I S T R Y
Gay L uss a c Th en ard in 1 8 1 0 e x te n d e d L avoisi e r s
d 1 ’
-
an , ,

work an d m odi fie d th e m e th o d o f burn in g th e subs t an ce by

mixi n g it wi th a kn own wei gh t of p o tassium chlor a te T h e .

mix ture w a s w ork e d in to a p a s t e wi th w a te r an d form e d in to

p e ll e t s which w e re d ri e d in an air b a t h an d dropp e d in to a
,
-

h o t v e r t ic a l t ub e T h e g a s e s given off w e r e c o ll e c te d ov e r
.

m e rcury an d an alyz e d as in gas an alysis T he r e sul t s ob ta in e d .

we r e con sid e re d a s a ccura te a s th e b e s t min e ra l an alyse s kn own

a t t h a t t im e V io l en t expl o si on s o f te n o ccurr e d in this m e th od
.
,

a n d B e rz el ius in 1 8 1 7 m a d e a m ark e d impr ov e m e n t which

2
,

re duc e d th e p o ssibili ty o f an explo si on t o a min imum H e .

mix e d th e organi c subs tan c e wi th p o ta ssium chl ora te an d a

l arge amoun t of s odium chlo rid e an d th en gr adu a lly de c om ,

pos e d t his mix tur e by h ea tmg In a horizon tal tub e H e w a s .

th e fir s t t o p a ss th e g a s e s t hr ough a s t r a igh t t ub e c on t a i n
in g fus e d c alcium chl orid e an d t hus h e ob ta in e d dir e c tly th e ,

a m ou n t o f w a te r a bs o rb e d by w e ighi n g th e t ube b e f o r e a n d

a f t e r th e c ombus t i on H e als o d e te rmin e d th e c a rb on di oxid e

.

dir e c tly by w e igh t For this purp os e h e us e d s olid p o ta ssium

.

hydroxid e which w as con tain e d in a sm a ll gl ass ve ss el I t .

w a s w e igh e d b e f o r e an d a f te r s t an di n g in th e b e ll ja r f or tw e n ty
,
-

four h ours i t w as w eigh e d agai n I t w as n o l on ge r n e ce ss a ry

,
.

to t a k e i n to a ccoun t th e r e sidu al oxygen .

Cupric oxid e w a s i n t r o duc e d as th e oxidizi n g a gen t by

Gay L uss a c
- 3
in 1 8 1 5 a n d i t s g en e r a l u s e th en c e fo r th w a s
,

e s t ablish e d .

ac c o u t f th m th d i th illust r t i s f t h pp r t us us d by L v isi r
n o e e o w a on o e a a a ,
e a o e .

C mp r H M y r
o a e . A lys d K tit ti mi tt l g rg is h r V
e e ,
na e un on s u on se r e un o an c e er

bi n d un ge n , 2 . A u fla ge 14 6 —
53 .

A sh o rt h ist o ry o f organ i c c omb ust i on s is also give n in L a ssar Cohn s A rbe its -
’

me th od e n ,
A ll i
ge me n e r T e il V i e r t e A u fl a ge ,
2 74 5
— .

For e arly w o rk an d a n a lys e s s e e t h e fo ll ow i n g books by E mil T W olff w h i c h

,
.
,

a re re pl e t e w i t h e xa mpl e s a n d r e fe r e n c e s a l t h o u gh n o d e s c rip t i on o f t h e me t h o d s
,

is give n ,
Qu ell e n L i te ra t ur d e
“
r t h e o r is
e t c h o rga n i s h e r Ch e m i e 1 8 —26 ;
”

an d Vo l l s t a n d ige U e b e rs ic h t d e r E l e me n t a r an a ly t is h e n U n t e rsu c h u n ge n o rgan -

c

i s c h e r S ub s t a n e n z T h e a u th or is in d e b t e d t o P ro f F B D ai n s f o r
”
. . .

Wol ff s w o rk
’
.

1
D e n n s t e d t 9 ; A rmi t a ge 1 2 9
, ,
.

2
B e n n s t e d t 1 0 1 1 ; v on M e ye r 4 1 2
—
, ,
.

3
D e n n s te d t 2 ; v o n M e ye r 4 1 3 ; A rmi t a ge
,
1 13
9 , , .
220 LAB OR AT OR Y MANUAL OF OR GANI C CH E MI ST RY
h an ds of D en n s te d t I t r e qui r e s a d ouble in le t f or tw o ca r e fully
.
1

re gul a te d s tre ams Of oxyge n On e s t r e am goe s t hr ough a shor t .

i n n e r t ub e which con t ain s th e b oa t an d subs tan c e an d th e ot h e r ,

s tr eam goe s ou tsid e this tub e an d furn ish e s an abun d an t supply ,

o f oxyg en jus t a s t h e pr o duc t s o f c ombus t i on c om e ou t o f t h e

i n n e r tub e an d m e e t th e cat alys t Con sid e rabl e pr a c tice is .

n e c e ss a ry t o h an dl e th e op e r a ti on b u t i t giv e s e xc e ll e n t r e sul t s , .

T h e pl a t in um is p ois on e d by s om e subs tan c e s an d r e quire s ”

fre qu en t t re a tm en t wi th con c hydro chl oric a cid to a c tiva te it . .

A n o th e r m e th od which w a s b e in g d e v e l op e d a t ab o u t this,

t im e bu t which h a s n o t y e t s e en i t s full d e v e l opm en t is th e ,

c ombus ti on of th e subs tan c e in a b omb wi th oxygen un d e r

pre ssur e Th e re h ave b een m an y limi ta ti on s in exp e rim en ti n g
2
.

Wi th this m e th od bu t th e s e are gr a du ally dis app ea rin g wi th th e

,

p e rfe c t in g of th e b ombs f or calo rim e tric w ork an d th e pre sen t ,

a u t h o r f ee ls th a t th e d ay will s o o n c om e wh e n th e v a ri a ti on s in th e

burn in g of ea ch in dividu al subs tan ce will n o l on ge r c ause an y

difficul ty sin ce it w ill b e p o ssible to h ave a b omb in which an y
,

subs tan ce c an be burn e d wi thin a few s e con ds u n d e r th e s am e

g en eral con di tion s an d con n e c ti on s a rr an g e d for the abs orp ti on
,

o f b o t h w a t e r v ap o r an d c a rb on di oxid e in th e usu a l m ann e r .

T h e u s e o f pl a ti n um a s a c a ta lys t h ea t e d by a burn e r o u t sid e

a c o mbus ti on t ub e n a t ur a lly l e d t o th e e l e c t ric a l h e a t i n g o f th e

pl atin um Thi s m e th od h as b e en sh own to be r apid an d ve ry

.

e ffici e n t b u t th e app a r a t us is n o t g e n e r a lly a v a il abl e

,
I t w as .

firs t d e scrib e d by M ors e an d Taylor in 1 905 an d is given in

3
,

1
D t dt A l i t u g v r i f h t E l m t r lys
en ns e ,
n e n D ri tt
z ur e e n ac en e e n a an a e, e

Au fla ge
Als o, H . M e yer ,
A na lyse und K on s t it u t ion s e rmitt e l u n g o rgan is c h er Ver
b i n d un ge n ,
”
2 . A u flage 1 7
—
0 6 G a t t erman n
;
“
P ra c ti c al e th od s of
, M
r i
O ga n c Ch e m is t ry 3 d E n glis h e d 1,
1
—
3 2 9 ; a n d S udbo ro ugh a n d Jame s
”
.
,

P rac t i c al Organ i c Ch emist ry —

50 5 ,
.

B erthel ot Comp r end 114

2
, 3 1 8 ; 129. 1 00 2 ;
, Z ts c hr a n al . .

Chem 40 .
,
1 2 4 ; H e mp e l B er? 3 0 2 0 2 ; Z u n t z an d Fre n tz e l Ber
, , .
, ,

30 3 8 1 ; L a n gb e i n Z ts c hr a n gew Chem Y e a r 9 00, 1227 1 25 9 ; an d

. . .
,
1 , ,

Year 9 0 5 1 6
1 1 ,
.

T h e me t h od is als o d e s c ri be d in t h e c a t al ogu e of th e E me rs on F u el Ca l o ri me t e rs
‘

—2
1 7 3 .

3
M rs o e an d Ta yl or ,
A mer Che m . . Jour n .
,
33 (J u n e 1, 59 1 ; an d M o rs e
an d Gr y a ,
A mer Chem . . Jou rn .
,
35 45 1 ; and a lmo s t a t th e same time by
 OR GANI C CO MB US T I ONS 22 1

d e tail in Mors e s ’
E x e rcis e s in Q u an ti ta t iv e An a lysis , ( 1 90

—
53 7 45
All th e s e combus tion m e th ods r e quire from 5 gr a m o f —0 .

subs tan ce fo r e a ch d e te rmi n ati on Of ten ti m e s such an am ou n t is .

n o t a v a il abl e a n d on t his a cc o u n t P r e gl d evis e d a sch e m e by 1

, ,

which it is p ossibl e to m ak e a c ompl e te an alysis for ca r b on

a n d hydr oge n o n on ly gram of th e subs ta n ce P l a ti n um .

a s th e c a ta lys t o r cupric o xid e o n a sb e s t o s a r e us e d in a t ub e

ab ou t 2 0 40 cm l on g A sp e ci al b al a n ce is r e quire d T h e
— .
2
. .

m e thod is sp ok en o f a s micro c ombus ti on in con tr a dis tin c ti on -

t o th e o r di n a ry m e th od which is t e rm e d m a cr o c o mbus t i on ,
-
.

I n 1 9 1 3 B ekk 3
publish e d a m odific ati on o f D e n n s te d t s ’

m e th od usin g ce rium dioxid e a s th e c a ta lys t i n s t ea d of pla ti n um ,

an d by usi n g a l on g t r ai n o f th e c a t a lys t (3 0 cm o f th e tub e

‘
.

fille d wi th c e rium dioxid e d ep o si t e d on a sb e s to s) a n d by pl a cin g

th e subs t an ce in a sp e ci a l sm a ll t ub e i n sid e th e l a r ge r c om
bu s tion t ub e h e w a s abl e t o do a w a y wi th D e n n s t e d t s c om
’

plicat e d double i n le t H e cl aim e d e ven gre a te r r apidi ty for his .

m e thod ove r D en n s te d t s an d fur th e rm ore sh ow e d th a t th e ’

,

cerium di oxid e w as n o t on ly an e xce lle n t ca talys t bu t a lso th a t ,

it w a s much ch e ap e r a n d n o t p ois on e d by th e comm on

m ate ri als th a t d e s troy th e c a t aly tic a c ti on of th e pla ti n um .

Ca rra s c o A i A d d i L i i R m 14 I —
[ 5 j , , 6 08 1 8 Che m
,
tt R c c a
. e n c e o a. I ( D ec .
3, .

. 6 —
Cen tral , 1 9 06 ( ) , 9 9 7 0 1
I . S ee a lso Bre t au a nd L e o r ux , Comp . r end .
,
145
—
5 2 4 6 , Chem Cen tr al , 1 9 0 7
. .
(I I ) 1 6 5 3 ,
.

P regl D ie
1
,
qua n t i t ative M ikroel e men taran al y s e rga nisc he r S ub s ta nz e n
o
,

in Abderhalde n s ’
H an db uc h de r Bi oc h e mis c h e n Arbe i t sme thod en V ,
”

—
1 3 07 3 2 .

Oth e r rfr
e e en c e s on mi c ro -
c o mb us t i on s : D ubs ky , Chem . Z tg .
,
40
201 —
3; R in ke s , Che m . W eekbl ad 13 , 8 00—3 ; Fis c e ma n , R end . ac ad . s c i.

(N ap oli ) , 22
— an d N o o rd u ijn , l ri c furn a c e f o r mi c ro-e l e
31 8; An
‘

e ec t
ry
me n t a an a lysis C he m W e e
,
k
”
bl ad 1 4 —
1 13 1 5
.
, .

P regl d e s c ri be s th e Kuh l man n bala n c e use d by him in h is a r ti c l e men t i on ed

2

abo v e S e e a lso E mi c h
. M i c ro balan c e s a n d the ir appli c a ti on in c hemi c al
,
-

an a lysis N a t
,
u r w i s s en s haf ten 3 6 —
93 8
c
, .

T h a t a n o rd i na ry s e n si t iv e b a l an c e c an be us e d pro vi d ed th e i n v e s t i ga t o r c an ,

use a s mu c h a s gram o f sub s t a n c e h a s be e n sh ow n by L E W ise , . .

,

th od f or t h e d e t e rmi na t i on of c arbo n a n d .

39 2 05 5 .
222 LAB OR A T OR Y MA NUAL OF OR GA NI C CH E M I S T R Y

P r o f e ss o r M a r ie R e im e r ,
r ticl e e n ti tl e d On R apid 1
in an a ,

Or ga n ic Combus t i o n s in 9 5 c o mbi n e d th e go od p o i n t s Of th e
”
,
1 1 ,

o l d L i e bi g m e th o d a n d o f B ekk s m e th o d a n d s h o w e d t h a t c opp e r
’

o xid e an d c e rium di o xid e c ou l d b e us e d t o ge t h e r a dv a n t a g eously

f o r th e r apid d e te rmi n a t i on o f c a r b on an d hyd r o g e n T he .

2

t e ch n iqu e o f th e m e t h o d w a s imp r o v e d by L e v e n e an d B i e b e r 3
.

T h e c opp e r oxid e is a dd e d t o oxidiz e a n y p r o duc t s o f i n c ompl e te

c o mbus ti on like ca rb on m on oxid e if th e y h app en to ge t b eyon d
, ,

t h e c a t a lys t o r in c a s e t h e supply o f oxyg en is m om e n t arily

us e d up This is th e m e th od o u tli n e d in th e f ollowi n g p age s
. .

T h e u s e o f a lu mi n a a s th e abs o rb e n t f or w a t e r in pl a c e o f th e
4

t im e h on o r e d c a lcium chl o r id e h a s on ly r e c e n t ly b ee n d e scrib e d

-
.

I t is b e li e v e d t h a t it h as s ev e r a l a dv a n t a g e s ov e r c a lcium chl o r id e ,

f o r e x ampl e : ( ) i t is a b e t t e r a bs o rb e n t f o r w a t e r ( 2 ) wh e n it
I ,
5

h a s a bs o rb e d w a t e r i t d oe s n o t crys t a l l iz e a n d fr e ez e to th e
w alls o f th e abs o rp ti on b o tt le 3 ) it d oe s n o t r e quire so akin g ,

wi th C0 b e fore usi n g an d (4) th e s am e bulk o f m a teri al h as

2 ,

l e ss w e i gh t I t s chi e f a dvan tage ove r pho sph orus p en toxid e is

.

t h a t i t d oe s n ot liqu e fy wh e n i t a bs o rbs w a t e r ; a n d o v e r c on c .

sulfuric a cid th a t it is a s olid a n d th e r e fore r e a dily h an dl e d

,

a n d pr o duc e s n o a pp r e ci abl e b a ck pr e ssur e .

I n th e ge n e r a l d e sc r ip tio n which f o ll o ws i t is a ssum e d ,

t h a t th e subs t an c e t o b e a n alyz e d is a s o lid a n d c on t a i n s n o

o t h e r e l e m e n t s t h an c a rb o n h y d r o gen an d o xyg en Fu r th e r on ,
.
,

t h e m an n e r o f d e a li n g wi t h subs t an c e s c on t a i n i n g in a ddi ti on
n i t r o ge n th e h a l oge n s sulfu r ph o sph o r us e t c
,
is discuss e d , , ,
.
,
.

B e f o r e t aki n g up th e me th o d in d e ta il i t s ee ms n o t in appro
1Jou r n A mer Chem . . . 37 1 63 6
—8 .

2
T h e pre s e n c e o f t h e c o pp e r oxi d e ob vi o usly ma ke s i t i mp o ssi bl e t o e s ti ma t e
h al o ge n o r sulfur a t t h e s a me t i me a s t h e c a rbon a n d h yd roge n a s h a s bee n w orked ,

out by D e n n s t e d t .

3
J ou r n . A mer Chem S oc . . . 40, 46 0 .

4 P re se n t ed by t h e a u th o r a t t h e Cl e v e l an d me e t i n g o f t h e A me ri c an Ch emi c a l
S oc i e t y S e p t e mb e r 1 9 1 8
, ,
.

5
T h a t is a s c o mp a re d w i th t h e o rd i n ary
,
a n h y d ro us gran ul a r c al c iu m
c h l o ri d e Co mp are A T M c P h e rs o n
.
,
Gr a n u l ar c a l c ium c h l o ri d e a s a d ryi n g
. .
,

3 7 9 ; a n d D o v e r a n d M a rd e n
—
J ou r n A mer Che m S o 3 9
”
a ge n t ,
c. . 1 1 . .
, ,

A c omp arison o f t he e ffi c ie n c y o f some c ommon d e si c a n t s ibid 3 9

_

”
c
,

1 6 09 . Also B axt e r an d S tarkw ea the r i bid 3 8 2 03 3 ,

.
,
.
224 LAB OR AT OR Y MANUAL OF OR GA NI C CH E MI STRY
G l a ss tub e f or p a ll adi ous chl orid e b o ttl e (p 2 4 .

On e p o rc e l a i n o r qu a r t z b o at (p .

On e sp e ci a l w e ighi n g t ub e b o a t tub e piggi e (p ,

.

T w o qu ar t z dish e s 7 5 cm in di am e t e r (p
,
. or on e l a r ge
. .

on e cm in di am e te r d ep en di n g up on con di ti on s for
.
,

h ea ti n g .

Crucibl e t on gs .

On e p air of pli e rs .

D e sicca tor
S ix pi n e spli n te rs 5 t o 6 i n ch e s a s aids in fil li n g an d e m
.

,
p ty ,

in g t h e abs o rp ti on b o t t l e s (pp 2 40 (f o o t n o t e ) .
-
,

On e p air o f f o rc e ps (l on g a n d n a rr ow curve d n e a r th e e n d , ,

s om e wh at like t h o s e us e d in bi ol ogic a l w o r k ) f or h an dlin g

t h e c o t t o n a n d f or u s e in filli n g an d e mp tyi n g th e a bs o rb
,

t i on b o tt l e s (p .

Chemi c al s

35 gr a ms s o d a lim e 2 0 m e sh 2
p er c,e n t w a t e r (a b o u t o n e,fil l
in g o U tub e (p 2 2 9 ) an d a bs o rp ti on b o t t l e ) (p
f — . .

1 0 gr a ms s o d a lim e 1 2 m e sh 1 5 p e r c e n t w a t e r (ab o u t on e
,

2 .
, ,

filli n g of abs orp ti on b o t tl e ) (p 2 4 .

1 00 gr ams alumi ni um chl o rid e crys t a ls (Al C1 3 6 H O) (p 2 3 ,

.
z .

I o u n c e o f a bs orb e n t c o tt on .

5 gr a ms c e rium n i t r a t e (p .

1 2 0 cc pumic e 1 2 m e sh (pp
.
,
23 4 .
,

On e vi al s top c o ck gr e a s e E
-
A (p ,
. . .

Co n c sulfu r ic a cid f or bubbl e c o u n t e r a n d d e sicca tor

. .

1 00 gr a ms cupric o xid e wi r e f o r m (p 2 ,
.

2 0 cc p alladious chl o rid e s o lu t i o n (p 2 4

. .

T op i c al O tl u in e of th e G e n e r al M e th od of P r oc e d ur e
0

Set up th e e l e c t ric c ombus ti on furn a ce (p 2 .

S e l e c t t h e c ombus t i on t ub e ; an d if n e c e ss a ry c u t t o p r op e r
l e n g th a n d r ou n d th e e dge s (p
“
.

P r e p a r e t h e pumic e an d c e rium n i tr a t e mix tur e an d pl a c e

in th e t ub e (p .
 OR GAN I C CO MBU ST I ONS 225

4 Ge t
. r e a dy th e o xy ge n app ara tus h e a te r an d pu r ifyi n g , p r e -
,

t r a i n (pp 2 5 . 2

Co mpl e t e t h e p r e p a r a t i on o f th e c e r ium di oxid e o n pumic e

in th e t ub e (pp 2 3 4 .

6 . P r e p ar e th e gu a rd t ub e f o r pr o t e c ti n g th e c ombus ti on tub e
wh en th e abs orp ti on t rain is n o t a tt a ch e d (pp 2 4 6 .

P r ep a r e th e r o lls o f c opp e r g auz e (p th e c opp e r Wir e .

wi th h ook an d fill th e r em ai nd e r of th e combus ti on tub e

,

(p .

M ak e th e pr e limi n ary h e ati n g gl owin g ou t (p .

Duri n g th e pr e limi n ary h eati n g prep are the en tir e abs orp ti on ,

t r a i n (pp 2 3 6 .

R u n a bl an k d e t e rmi n a ti on (p an d w e igh ou t th e .

s ampl e o f dry subs t an c e (pp 2 5 0 .

T h e c ombus t i on pr op e r (p .

C a lcul a t e th e r e sul t s (p .

Ru n a ch e ck d e te rmin a ti on (p .

T h e Apparat us an d H ow to P u t it T oge th er with N ote s

on M a n ipul a ti on
1 T an k
. of C om pr e s s e d Oxyge n with S tan d an d P r e s s ur e
a uge s .
—T h e combus ti on is ca rri e d ou t in oxygen which is m o s t ,

supplie d in a t an k or cyli n d e r e quipp e d wi th th e ,

a n d supp o r t e d in an ir on s t an d (s ee Fig 1 4 p 2 2 6 .
,
.
,

p . T h e l a rg e g a ug e r e gis t e rs th e pr e ssur e
r an d th e sm all on e r e gis te rs th e pre ssure a t which
d e live r e d This d elive ry pre ssur e is r e gul a te d by
.

which h olds a sp r i n g in pl a ce up on an
di aphragm A sm all s top co ck is a dd e d b eyon d th is
.
-

o rd e r t h a t th e ga s supply c an b e r e gul a t e d fur t h e r or

quickly wh en n e ce ss a ry T h e op e r a ti n g pre ssure is

.

1 t o 4 p o u n ds bu t t his v a ri e s gr e a t ly wi t h th e
,

thr ough ou t th e c ombus t i on sys te m I t is .

b i g publish d P r f S W P rr h
e n e , d s ri b d
o . A dl . . a as e c e n ee e
228 LAB ORAT OR Y MANUAL OF OR GANI C CH E MI ST RY
AS s ta te d in con n e c ti on with th e pr e ssu re of oxygen un d e r
t h e pr e c e d i n g h ea di n g t h e r a t e o f gas bubbli n g sh o uld o r di n a r ily

b e s o f a s t t h a t th e bubbl e s c an jus t b e c o u n t e d t h r e e t o f ou r a ,

s e con d al th ough this r a te will vary m or e or l e ss wi th diffe r e n t

,

subs tan c e s .

T h e obj e c t of th e bubbl e c o u n te r is n ot on ly t o give on e

a n id ea a s t o h ow f a s t th e s is p ssi n g i n t o th e a pp a r a tus
g a a ,

bu t a ls o to S h ow a c omp aris on b e t w e e n t h e a m ou n t o f ga s e n te r
in g th e t r a i n an d th e a m ou n t o f gas l e a vi n th e sys te m th r ou gh g

t h e p a ll a di ous chl o rid e s o lu t i on (s e e N 0 5 0 p This will

.
,
.

b e discuss ed in d e t a il l a t e r (pp 2 4 5 .
,

T h e bubbl e c ou n t e r is c on n e c t e d wi t h th e gl a ss tub e in th e

p r e-
h ea t e r by m e a n s O f a g oo d re d rubb e r s t opp e r O n t h e .

sid e n e ar th e oxygen t an k it sh ould b e supp o r t e d wi th a cl amp

t o pr e v en t s aggi n g o f th e t ub e in th e p re h e a t e r wh en i t is h o t -
.

3 G a s P u rifyi n g Appar a tu s i n c lu di n g th e P r e h e ate r

.
,
- .

T he P re hea ter - —
T h e compr e ss e d oxyg e n g e n e r a lly c on tai n s
.

sm all am ou n t s of impuri ti e s an d it h as b e en f oun d th a t it is b e s t

a n d e a si e s t t o purify it by p a ss a g e o v e r h o t c opp e r oxid e o r c e rium

di oxi d e on pumice in a pre h e a te r b e fo r e ru n n i n g th e gas

-

t hr ou gh th e r e gul a r dryi n g t r a i n A f te r t his t r e a tm e n t bl an k

.
1

d e te rmin a ti on s will sh ow th a t th e app ara tus is r e ady f or u s e righ t

a f t e r th e pr e limi n a ry h e a t i n g o f th e c o mbus t i on t ub e Oth e r .

wise th e pe r c en tage of hydr ogen will be to o high .

R ou n d off th e e n ds o f a P y r ex c ombus t i o n tub e 3 6 cm ,

.

l on g an d 1 5 mm in sid e di am e te r in a bl a s t fl am e Th en pu t
.
,
.

i n sid e a 1 2 cm r oll of c opp e r gauz e o r a 2 cm l ay e r of coppe r

. 1 .

o xid e in wi r e f o rm T h e r o ll o f c opp e r ga uz e o r c opp e r

. spira l
a s t his is s o me ti me s c a ll e d is m a d e by tigh tly r olli n g a pi e ce
,

o f c opp e r gauz e (40 m e sh t o th e squ a r e i n ch ) 2 cm wid e a n d ,

1 .

a b ou t 1 8 cm l o n g a r ou n d a l e n gt h o f N o
.
,
6 c opp e r wir e a nd. 1
2

b e n di n g th e proj e c ti n g e n ds of th e wir e in to s hort l oops close to

th e g a uz e .

1
is h as bee n fo un d n e c e ssa ry w h e n th e oxygen is man ufa c t ure d by e l e c t rolysis
Th ,

a s d e mon s t ra t e d in o u r l ab o r a t o ry by M iss A li c e R T h ompson I t c on t ai n s

. .

small a moun t s o f hy droge n to pe r c e n t ) .

2
B ro w n S h a rpe gauge .
 OR GANI C CO MBU S T I ON S 229

This tub e is h ea te d t o dull r e d n e ss in a 2 0 cm (8 in ) el e c tric . .

furn a c e pr ovid e d f or this purp o s e I t con sis t s o f on e o f th e .

s e c ti on s of an e l e c tric c ombus tion fu rn a ce m ou n t e d lik e th e r e gu ,

l a r fu r n a c e i t s e lf wi t h t r o ugh a n d it s o w n rh e o s t a t f o r t e mp e r a
,

t ur e c on t r ol I n o rd e r t o p r e v en t th e gl a ss if it sh ould me l t
.
, ,

fr om a dh e rin g to th e t rough pl a c e u n d e r it a s t rip of a sb e s to s ,

p ap e r T h e e n ds Of th e gla ss t ub e are a ll owe d t o pr oj e c t m ore

.

t h a n usu a l b e yo n d th e fur n a c e si n c e a l l pr e c a u ti on s mus t b e ,

t ake n t o pr e v e n t th e rubb e r s topp e rs fr om b ur ni n g .

T he P u rifyi n g T ra i n — T h e o xyg e n mus t b e fr e e d fr om an y

p o ssible tra ce s o f carb on di oxid e a n d w a t e r an d th e r e for e it is ,

n e x t p a ss e d t h r o ugh a cm ( 5 in ) U tub e co n tai n i n g . .

- 1

s od a lim e ( 2 0 m e sh siz e an d c on tai n i n g 2 pe r c en t o f m ois tur e )

-

a n d t h en t hr ough an o t h e r U tub e c on t a i n i n g a lu mi n a pumic e

2 - -
.

Th e s e U t ub e s sh o uld b e fi tte d wi th grou n d gl a ss s topp e rs an d

- 3

sh ould h ave gl a ss bra c e s to giv e s t re n g th an d to preven t 4

br e ak age T he s topp e rs mus t be gr e a s e d wi th a g oo d s top

.

c o ck gr e a s e in such a w ay th a t th e y pre sen t a cl ea r surfa ce

5

sh owi n g g o od con t a c t T oo li t tl e gre a s e m ak e s a s topp e r s tick

.

o r l eak ; t oo much o f t en s t ops up th e o p e n i n gs a n d a ls o m ak e s

th e s t opp e r s o l oo s e t h a t th e ga s pr e ssur e m ay f o r c e it o u t o f
t h e tub e N e v e r t ur n a s top c o ck by usi n g o n ly on e h a n d
.
-
.

U s e th e o th e r h an d a t th e s am e t im e t o h o ld t h e U tub e th e n -
,

o u c an b e sur e t h a t t h e s t opp e r is in tigh t an d th a t t h e r e a r e

y
n o ch a n ne l s T h e s t opp e rs sh ould b e k e p t cl o s e d wh en th e
.

a pp a r a t us is n o t in u s e This appli e s p ar ticul a r ly t o th e a lumi n a

.

pumic e U tub e -
.

1
A small fu n n el of th i n gl a ss w i th a w i de st e m is ve ry use ful in filli n g t h e
a pp a ra t us .

2
S ee p 2 3 8 f o r pre p a ri n g t h e a l u mi n a pumi c e
.
-
.

2
Fa s t e n t h e s e s t o ppe rs l oo se ly w i t h w ire or t w i n e o t h e r w is e if e x c e ssive , ,

pre ssure is de ve l o pe d t h ey may be forc e d o u t a n d t he s t opp e rs broke n T h is

, .

c a us e s mu c h i n c o n v e n i e n c e D o n o t u s e rubb e r ba n d s
. On a c c o u t o f t h e ir . n

e l a s t i c i t y t h e y O f t e n al t e r t h e po si t i on o f t h e s t o pp e r a f t e r i t h a s be en s e t .

4
R N o wi c ki Che m Z tg 28
.
, 6 2 2 ; M c I n t ire J ou rn A mer Che m S oc
. .
, ,
. . . .
,

33 —1 (li ke t h e o n e s sh o w n in t h e fi ure F or o t h e r S i mil a r t ype s

45 0 g ) .
,

se e A b d e rh al de n s H an dbu c h de r B i oc h e mis c hen A rbei t sme t hod e n VI I I

’ ”
,

5
Do n ot u s eva se li n e si n c e th e s t oppe rs are li kely t o s ti c k E i me r
, . Am en d ,

N Y. .
, furn ish a good s t op c oc k grea se in h an dy sof t metal t ube s
-
.
23 0 LAB OR AT OR Y MANUAL OF OR GAN I C CH E M I S T R Y
P la ce a w ad of a bs o r b en t c o t to n on top o f th e m a te r i al in
e a ch a r m ub s k p s p co cks f r e e f r om dus t
of th e U -
t e t o e e th e t o —

p a r ticl e s .

Con n e ct
ub e s by m ean s of r ubb e r p r e ssure tubin g
th e —
U t .

I t is w e l l t o supp o r t t h e s e U tub e s b v me an s o f a cl amp a r o u n d -

t h e rubb e r c on n e c ti on This p r e ven t s an y s aggin g of th e tub e s

.

in b o th p r e h e a t e r a n d c ombus t i on furn a c e wh e n t h e y a re h o t
-
.

T h e pr e p a r a ti on of th e a lumi n ium o xid e on pumic e is d e

scrib e d in c on n e c ti on wi th th e abs o rp ti on b o ttl e f or w a te r
( s ee 5 a p 2 , T h
. e s a m e ki n d o f m a t e ri a l mus t b e us e d h e r e

f o r d r yi n g th e gas a s is us e d f or abs o rbi n g th e w a t e r in th e

a bs o rp t i on t r a i n o th e rwis e t h e r e will b e discr ep an ci e s in th e
,

p e rcen tage of hydrog en .

1

I n s t ea d o f th e U tub e s a n y v ari e ty o f abs o rp ti on app ar a tus

-

may b e us e d N o w e ighi n g is n e c e ss a ry an d t h e r e f o r e th e sh ape

.

d oe s n ot r e quire c on sid e r a ti on T h e s am e t yp e of abs orp ti on .

b o tt l e s as d e scrib e d in th e abs orp ti on t rain c an be us e d if d e sire d .

I f m a n y c ombus t on s a re to be ru n th e purifyi n g t r a in
i
,

should con sis t of m ore U tub e s or of l arge r app ara tus a ccordin g -
,

t o c on di ti on s .

4a T h e E l e c tri c Combu s ti on Fu rn ac e
.
— T h e mul tipl e u n i t .

t yp e o f e l e c t r ic c ombus ti on fur n a c e is th e m o s t c on v en i en t t o
u se . E a ch h e a ti n g s e c ti on is r e gu l a te d by its ow n rh eo s t a t
2

pl a ce d u n d ern ea th an d is fi tte d wi th r epl a c e abl e h e a tin g u n i t s .

T h e u p p e r p a r t o f e a ch s e c t i o n c an b e lif t e d a n d th e tub e e x
a min e d a t an y ti me duri n g th e c ou r s e o f th e c ombus ti on T he .

m aximum curr en t re quir em en t is from 1 2 to 1 8 amp e r e s de ,

p en din g up on th e m od e l T h e u n i t s are s o w ell i n sul a te d th a t

.

p ar t s o f th e tub e may be h e a t e d to r e dn e ss while o th e r p a r t s

r em ain c ool f airly cl o s e to th e u n i t This i n sul a ti on t o prev en t .

l o ss of h e a t is a b oon to th e m an ipul a tor also b e caus e it m ak e s it

po ssibl e to ru n c ombus ti on s in a sm all r oom e ven in summ e r tim e .

1
S ee , sal o , M o rs e
rc ise s in Qua n ti ta tive Chemist ry
,
E xe pp 3 40—2 .
,

—
3 53 4 ,
w h e re
d a t a a re giv e n t o illus t ra t e t h e d i ff e re n c e in t h e ab s o rp ti o n c a p a c i ty
o f w a r m a n d o f c ol d c a l c iu m c h l o ri d e a n d o f c o n c sulfuri c ac i d
,
. .

2
M ul tipl e un i t el e c tri c organ i c c o mbus ti on furn ac e T ype 1 2 2—S man ufa c t ured , ,

by t h e E l e c t ri c H e a t i n g A pp a ra t u CO N e w a rk N J is b uil t in ac c o rda n c e w i th
s .
, ,
. .
,

t h e spe c i fi c a tion s given in th is de s c rip t i on .

23 2 LAB OR AT ORY MA NUAL OF OR GANI C CH E M I ST RY
h emi an gl a ss sin ce i t doe s n ot v itre fy an d b e com e op a qu e a t th e
r e quire d high te mp e ra tur e S e le c t a combus ti on tub e of 1 5 mm .
1
.

i n sid e di am e te r an d of such a l e n gth (ab ou t 7 6 cm ) th a t it will .

e x t en d 3 4 cm b e y on d th e en ds of th e n ick el tr ough U su ally

— .
2 3
.

t his a m o u n t o f e x t e n si on is su ffi ci en t t o pr e v e n t th e bur n i n g o f

t h e rubb e r s t opp e rs T h e en d n ex t to th e abs o rp ti on t r a i n sh ould
.

n o t b e s o l on g t h a t much w a t e r c an c on d en s e S i n c e it is difficul t

t o driv e this w a t e r t hr ough .

R o u n d Off t h e e dg e s o f th e tube by g e n t l e h e a t ing firs t an d

t h e n w i t h a bl a s t fl a m e s o t h a t t h e y will n ot c u t th e rubb e r ,

s t opp e rs D o n ot ch an ge th e b or e o f th e tub e "

.

Cl e an th e co mbus t i on tub e a n d fill i t a s i n dic a t e d in th e ,

di agr am Fig 1 6 m akin g sure th a t th e p o si ti on s of th e m a teri als

,
.
, ,

e tc . a r e in pr op e r r e l a t i on t o th e s e c t i on s o f t he fur n a c e
,
The .

dim en si on s giv en are for th e 7 2 cm ( 2 8 5 in ) furn a ce E ve n . . .

if a l on ge r furn ac e is us e d th e p o si ti on s of th e ce rium di oxid e ,

a n d th e b o a t sh o uld b e r e l a tiv e ly th e s a m e a s d e scrib e d h e r e ,

t h e e x tr a l en g th b e i n g t ak e n up simply wi t h m or e c opp e r oxid e

W I re .

1
Wh ere man y c o mb us t i o n s are t o be qu ar tz t ube w i th a t ran sp are n t
r un , a

s e c t i o n w h e re t h e bo a t is p l a c e d is bot h a d v a n t a geo us a n d e c on o mi c a l Le ven e .

a n d B i e be r J ou r n A mer Chem S oc
,
. 40 460 . . .
,
.

2
A longe r e xten sio n is n e c e ssary w he n a gas furn ac e is us ed .

3
P yre x c omb tis t ion t ubi n g is c u t w i th a n arro w gri n d i n g w hee l T he ordi n a ry .

me t h o d s c a n n o t al w a ys be use d si n c e t h e e xp a n si on o f t h e gl a ss on h e a t i n g is s o
,

small S ome of th e se me thod s h ow e ve r d o w ork s ome ti me s a n d a re give n h ere

.
, ,

f or s ake o f c on v e n i e n c e .

1 . M ake a shor t fil e mark at the d e sire d len gth an d then h e at the t ube a t this
p oi n t by givi n g a pi e c e o f t w i n e t w o t urn s a t t h e mark an d dr a w i n g th e t w i n e up an d
d o w n ra pi dly s e v e ra l t i me s w h il e t h e t ub e is h e l d s e c ure ly by an o th e r p e rs on on t h e
d e s k w i th t h e e dge f or a gui d e T h e n i mme d i a t ely p u t t h e t ube u n de r c o l d w a t e r
.
,

or apply a w e t c l o t h .

2 . A sec on d me th od o f c utti n g the gl ass t ube is to make the fil e mark as above

a n d t h e n h e a t t h is m a rk v e ry c a re fully w i t h t h e s l an ti n g t i n y fl a me fro m a c a p il

l a ry t ube T h is t ub e c a n be ma d e o f gl a ss a l t h o ugh a me t al on e is o f c o urse pre f

.
,

e ra bl e A s soon a s a c ra c k is forme d follow it w i th the t i n y fl a me u n til it exten d s

.

c l ea r a ro u n d D o n o t p o i n t t h e fl ame d ire c t ly a t t h e t ube a l w a ys sl an t it o th e r

.
, ,

w is e t h e c r ac k ma y e x t e n d l o n gi t u d i n a lly :
1

3 A n o t h e r m e t h o d c on sis t s in w i n d i n g a pl a t i n u m or ni c h rome w i re a ro un d
.

t h e t ub e a n d t h e n h e a t i n g it t o re d n e ss by me a n s o f an e l e c t ri c c urre n t .

1
K H P k . .Jour n A mer Chem S oc 40
ar er , . 95 d . ib d A w gl . t .
, 1 , es c r e
“
ne ass c u

ti g t
n l
oo
— m ll g h t d i
,
"
a s fa w hi h has l im-
ll
ea e t
r on lt or c e c a s e xc e en re s u s .
OR GANI C MBU S T I ON S
CO 23 3
23 4 LAB OR AT OR Y MANUAL OF OR GANI C CH E M I ST RY
r ep ar e th e c e rium di oxid e firs t U s e en ough p um ice of
P .
1

1 2 m e sh siz e t o fill 5 6 cm o f t h e t ub e Diss olve 5 gra ms of

- — '
. .

pure whi t e crys t als o f ce rium n i t ra te in en ough wa te r (ab ou t

1 2 cc ) t o c o v e r th e pu m ic e in a qu a r t z o r p o r c e l a i n dish
. E v apo .

r a te this mix ture to d r yn e ss on th e s te am b a th wi th fre qu en t -

,

s tirrin g t o pr e ven t form a ti on of a c ak e Th en tran sfe r this .

impr egn a te d pumic e t o th e tub e an d pu t th e a sb e s to s wads in

pla ce by m ean s o f a l on g gla ss r od fl a tten e d a t on e en d T he .

a sb e s t o s w a ds sh o uld n o t b e ov e r 0 5 cm in wid t h an d th e . .
,

a sb e s t o s mus t n o t b e s o t i gh t ly p a ck e d t h a t th e oxy gen ga s w ill

n o t go t hr ou gh it This c an be rem e di e d wh en it is in pl a ce by
.

pu t t in g in t i n y h ol e s if n e c e ss ary wi th a l on g gl a ss rod drawn

, ,

o u t t o a p oi n t S upp o r t th e a sb e s to s w a ds in p o si ti on by usi n g
.

a r ol l o f c opp e r g auz e 0 5 cm in wid th ,

This pr e ven t s th em fr om
. . .

crumblin g an d fr om b e i n g m ov e d ou t of p o si ti on by th e f orc e
o f th e ga s e tc I t is imp o r t an t f or prope r h e a ti n g th a t th e
,
.

c e rium di oxid e b e pl a c e d in th e r e la tive p osi ti on S h own in th e

di agram (C) an d a ls o t h a t th e en d of th e b oa t be n o t m ore th an
2 5 cm
. dis tan t in o rd e r to pr e ven t th e form a ti on of e xplo sive
.
,

mix ture s of ga s e s Th e r e fo r e th e siz e o f th e a sb e s to s w a d an d

.

th e sh or t r o lls of c opp e r o xid e g a uz e mus t n o t be gr e a t e r th a n

m e n ti on e d ab ove Compl e te th e dryi n g by h ea tin g th e tub e
.

a t a l ow t e mp e r a t ur e an d a t th e s a m e t im e p a ssi n g a curr en t o f

pure dry oxyg en t hr ough th e t ub e A S s oon as n o m or e m ois .

tur e c o ll e c t s in th e c oo l en d o f th e t ub e gr a du a lly r a is e th e t em
t u r e whil e th e o xyg en is s t ill p a ssi n g a n d fin a lly c ompl e t e
p e ra

th e d e c omp o si t i o n o f th e c e r ium n i t r a t e a t dull r e d h e a t 2

.

A ll ow t o c oo l in t h e curr e n t o f d r y o xyge n o r a tta ch a dryi n g

t ub e t o th e o p e n en d of t h e c ombus ti o n t ub e Wh en ho t th e .
,

1
P umi c e is use d i n s t ea d o f a sbe s to s t h e n th e ma t e ri al d oe s n o t c ru mbl e a n d
,

Fish e r a n d W ri gh t J ou r n A mer Che m S oc 40

”
s ag .
,
. . 8 69 . .
, .

2
T h is pro c e d ure is us e d in a c c or d a n c e w i t h t h e sugge s t i o n o f L e v e n e a n d
B i eber Jou r n A mer Chem S oc 40
,
. . . .
46 0 w h o fo un d th a t w h e n t he de c om
, ,

po si t i on w a s c a rri e d o u t o ve r a ga s b urn e r t he o xi d e w a s n o t a l w a ys s o goo d a

c a t a lys t a s w h e n pre p a r e d as a bo ve .

I f t h e ma t e ri al is h e a t e d t o o mu c h a t firs t s o me o f it is d rive n o u t o f t h e pumi c e

a n d d e p o si t e d upo n t h e i n n e r w alls o f t h e t ub e w h e re it w ill re ma i n w h e n d ry an d
,

fo r m a n o p a que l a y e r N o sp e c i a l h a rm is d o n e if t h is h appe n s
. .
23 6 LAB OR AT OR Y MANUAL OF OR GANI C CH E M I S T R Y
u n oxidi z e d ga se s which may go b a ckw ard from ge tt in g b eyon d it
b e f or e th ey a re c ompl e t e ly oxidiz e d .

Th e in te rv en ing sp ac e of 2 cm b e tw een the roll o f gauz e

'

1 .

a t A a n d th e c e rium d i oxid e a t C is r e s e rv e d f or th e b oa t B .

As s t a t e d ab ov e (p th e b oa t sh ould b e pl a c e d wi thi n ab ou t
.

2 5 cm o f th e c e rium di o xid e
. . A g r e a t e r dis t an c e will a ll ow th e .

form at ion of e xpl osive mix tur e s of oxygen an d th e gas e s from the
subs t an ce .

Ordi n arily a p o rc e l a in or qu ar tz bo a t 7 cm l on g is us e d . .

Cl e an it wi th dilu te n i t ric a cid h e a t in a bl a s t fl am e an d all ow ,

t o c oo l in a d e sicc a tor A l on g e r b o a t is us e d f or v e ry ligh t

.

a n d flu ffy m a t e ri a ls A b oa t wi th li t tl e c omp a r tm en t s a ids

.

th e bur n i n g of a subs t a n c e which d e c omp o s e s r e a dily T he .

c omp ar tm en t s pre ven t th a t p or tion o f th e subs tan ce th a t h as

m e l te d from mixin g wi th th e unm e l te d p or ti on .

For w e ighi n g o u t s ampl e s ee p 2 5 0 ,

. .

B e y on d th e c e rium di oxid e in sp a c e D pu t a 2 3 cm l aye r o f .

cupric oxid e in wir e form an d k eep it in pl a ce wi th a shor t roll

1

o f c opp e r o xid e g auz e E Cupric o xid e is v e ry hygr o sc opic. .

T h e 1 2 cm sp a c e a t F is r e s e rv e d f or th e l ea d p e r oxid e
-
.

mix ture which is us e d wh en substan c e s con taini n g ni trogen an d

sulfur are burn e d (S ee p Oth e rwis e it may b e fill e d
. .

wi th c opp e r oxid e wir e .

5 T h e Abs or pti on T r ai n
.
— T h e abs orp ti on t r ain is m ad e up .

o f tw o abs orp t i on b o t t l e s th e firs t on e f or c o ll e c t i n g t h e w a t e r

,

a n d th e s e c on d o n e f or t h e c a rb on di oxid e an d a gua rd t ub e a n d ,
.

b o ttl e of p all a di ous chl orid e s olu ti on T he abs orp ti on app ara tus .

s e l e c te d sh ould be on e th a t is c ap able of b ein g r eadily an d

t h o r oughly cl e an e d e a sily fil l e d an d e mp ti e d h a n dl e d wi th ou t
, ,

diffi cul ty of a m od era te cap aci ty an d wh en fille d n o t w eighin g

, ,

o v e r 1 00 gr a ms F or c arb on di oxid e abs o rp t i on i t S h ould h av e

.
,

t w o ch amb e rs which c a n b e e n tir e l y shu t o ff on e fr om t h e o t h e r

’

wh en th e app ar a tus is n o t iIi a c tu a l u s e I t is b e li eve d t h a t th e .

1
C upri c i de w h i c h h as bee n used in t h e de t e rmi n a ti on o f n i trogen c an n ot
ox

b e use d f o r c a rb o a d h y d roge n si n c e it c o n t a i n s s o me c a rbon d i ox i d e u n l e ss it

n n
,

h a s bee n h ea t e d f o r s e v e ra l h o urs in a s tream o f o xyge n or in th e o pe n ai r Com .

p a r e fo o t n o t e
-
p 8
, 4 . 2 .
 OR GANI C CO MBU S TI ONS 23 7

a bso rp ti on b ot tle sh own 1

in Fig . 1
7 ,
fulfills t h e s e r e qui r e m e n t s .

Do tte d Li n e s
I n dic a te Gr o u n d
S ur f a c e s of Bo t

11 mm . i

'
5 mm .

FI G . 17
— F he
. is r Ab s o rp tion B o tt el .

1
Fishe r , U P a te n t
. S . T h e bott l e is ma n ufac t ure d by E i me r
81 A me n d N e w Yo rk
,
T h e f ore ru n n e r o f t h is p a r t i c ul a r b o t t l e h a d n o me a n s o f
.

S h ut t i n g o ff t h e t w o c h a mb e rs a n d t h e s t o pp e r w as gr o u n d in t o fit t h e t o
, p o f th e
i n n e r s t an di n g t ube i n s te a d o f th e bo t t o m S ee Fish e r A n e w f orm of a bs orp
.
,

t i on b o t t l e f o r u s e w i t h e i t h e r c a l c ium c hl ori de o r s o d a li me i n t h e e l e me n t a l a n a l

y s is o f c a rb on a n d h y d roge n in o rga n i c sub s t an c e s Jour n I n d a n d E n g Chem

,
. . . .

8 3 68 .

Ot h e r fo rms of ab o s rp t i on b o t tl e s an d u s
t be c an be fo un d in t h e a pp arat us
l us
c ata og e .
 LAB ORAT ORY MAN UAL OF OR GANI C CH E M I S T RY
T he b l is li te rally a U t ub e tu r n e d p ar ti ally i n sid e ou t
ott e -
.

T h e a v a il a bl e c ap a ci ty o f t h e s t opp e r a n d i t s e x te n si on t u be
is 2 5 cc an d o f th e o u te r ch amb e r o f th e b o tt le 2 5 3 0 cc
.
,
—
,
.
,

m akin g a to tal avail able c ap a ci ty of 50 5 5 cc B y w ay of —

.

c omp aris on it is of in te re s t to n o te th a t an ordi n ary 5 in ch -

U tub e h a s a to t al a vail abl e c ap a ci t y o f on ly 2 0 2 5 cc

- — .

a T h e Fir s t Ab s or pti on B ottl e A lumi n ium oxid e

.
— .

in a) is us e d f o r abs o rbi n g th e w a te r f o rm e d in th e c ombus ti on .

I t is mix e d wi t h pumic e t o m a k e it m or e p or ous T h e u s e of .

a lumi n a is d e scrib e d firs t F o ll owi n g this on p 2 3 9 is a de

.
,
.
,

scrip tion of th e u s e of calcium chl orid e f or the a bsorp ti on of

w a te r I t sho u l d be b orn e in min d th a t wh a tev er absorbin g
.

age n t f or w a t e r is us e d h e r e th e s am e on e mus t a ls o be us e d
,

in th e s o d a lim e b o tt l e an d in th e dryi n g t r ain (c omp a r e p 2 .

P r e parati on of Alumi n iu m Oxi d e (Alumi n a) f or th e Ab s orp

ti on B ottl e — Disso lve 5 0 gr ams o f hydra te d a lumi n ium Chloride
( A l C 13 6 H 0
-
) in 0 0 cc
2 o f w a rm
1 w a t e r. in a 1 1 5 cm qu a r tz . .

o r p orc e l ai n dish a n d s t ir in 5 0 cc (ab ou t 2 4 gr ams ) o f 1 2 m e sh .

-

pumice B oil d own this mixt ure ove r a wire gauz e or a sb e s to s

1
.

disk wi th a fre e fl am e S tir w e ll wi th a s tou t glass rod a f te r

.

m os t of th e wa te r h a s dis app eare d S in ce it foams a good d e al ,

a n d will als o f o rm a c ak e T h e p ar ticl e s o f pumic e S h ould be

.

k ep t s ep arate d as f ar as p o ssible Con ti n u e th e h ea ti n g an d .

s tir r in g un til th e re is n o d an ge r of la te r fusi on of th e hydr at e d

s al t an d agglom e ra ti on of th e sm all lumps o f impre gn a te d pumice .

Tran sfe r this m a t e ri al t o a 7 5 cm qu a r tz or po rce l a in dish an d

. .

h e a t in an el e ct ric mu ffle furn a ce to 7 00 7 5 0 un t il n o m ore

— 2 ° °

hydrogen chlo r id e is given off A hi ghe r t e mp e ra tu r e sh ould n o t

.

b e us e d Th e t im e c a
. n b e sh r
o t e n e d t o t hi r y f r y fiv e min
t t o o t —

u te s if a s tr eam of air is bl own o r dra wn through th e h ea ti n g

1
T he se a mo u n t s are fo r t he firs t ab o s rp ti on bo ttl e
D o ubl e the m or make up
.

a s ec o n d b a t c h in o rd e r t o h a v e e n o tI gh f o r a ll r e quire m e n t s On a c c o u n t o f t h e .

foami n g t h e e va p ora t i on is b e s t d o n e in t h is l a rger d ish T he fi n al h e a t i n g c an

,
.

a ls o be d o n e in t h is s a me d ish b u t i t is t o o l a rg e f or t h e o rd i n a ry muff l e fur n a c e

, ,

w h i c h h as a n o p e n i n g o n ly 1 0 c m w i d e . .

2
A ppr oximatel y t h e s e s ame c o n d i t i o n s c a n b e o b t a i n e d b y h e a t i n g t h e mi xt ure
in th e d ish o n a n i c h ro me ga uze a t t h e t ip O f a n o n lumi n o us fl a me 5 c m h i gh f or
-
.
,

I é t o 2 h o urs .
 LAB OR AT OR Y MANUAL OF OR GANI C CHE M I S T R Y
of a ir dri e d ove r ph ospho rus p en toxid e E ven this .
1

ma t e ri a l h ow e v e r which c on t a i n s s om e su r fa ce m o is
, ,

b e t te r t h an th e fus ed c alcium chlorid e .

e r a ll y c on t a i n s b a sic subs t a n c e s an d t h e s e abs orb ca rb on

On t h a t a cc oun t it mus t b e s a t ura t e d w hi l e in th e abs orp ti on

b o t t l e wi th ca rb on di oxid e by p a ssin g a s tr eam of th e dry ga s
t hr ough i t f or t w o h ours an d t h en displ a cin g t his wi th dry a ir
o r oxyg en 01 b e tt e r a f t e r d r ivi n g ou t all th e o rigin a l air
.
, ,

wi th dry ca rb on di oxid e (on e h alf h our) l e t it s tan d ove rni gh t -

, ,

a n d t h en displ a c e th e ga s wi t h dry a ir o r o xyg en

2
.

T h e a m ou n t o f m ois tur e abs o r b e d by ca lcium chl orid e v ari e s

wi th th e temp e ra tu r e e v en a rou n d th e t emp e ra ture o f ordi n ary
w orki n g con di ti on s This is s om e tim e s ve ry I mp or tan t sin ce
3
.

t h e t e mp e r a tur e of th e c a lcium chl o rid e in th e dryi n g t r a i n is

s e ld om th e s am e a s th a t of th e ca lcium chlorid e in th e abs orp ti on
t rain .

To fil l 4
the a bs orpti on bottl e: R e m ov e t h e s t opp e r an d its
e x t en si on t ub e P l a c e a fla t w a d o f co tton ov e r th e h ol e in
.

t h e i n sid e of th e s topp e r a n d r apidl y fill th e s t opp e r an d i t s

5

e x t en si on t ub e wi t h s om e o f th e a lumi n a pumic e P u t in a plug -

.

o f a bs o rb en t c o t t on n e a r th e e n d P l a c e this fil l ed p ar t of th e .

b o ttle imm e dia te ly in t o a d e sicca to r ove r fr e sh con c sulfuric .

Wi th ou t an y d e l ay pu t s om e co t ton a t th e b ot t om of th e ,

1
A . T . M c P hers on ,
Gr an ul ar Cal c ium Chl oride as a D ryi n g A gen t ,

A mer Chem S oc 39 13 1 7 —
. . .
, 9 .

2
M orse r c ise s in Quan t i ta t ive Ch emis t ry
,
“
E xe 3 40 ,

t h e se me t h od s a r e o p e n t o Ob j e c t i on s S i n c e t h e c on ve r
o n ly sup e rfi c i a l a n d w h e n t h e mo is t ure c ome s in n e w
,

a ls o s ta t e s t h a t c a l c iu m c h l o ri de ma y b e o b ta i n e d in a n e u t ral c o n d i t i on t h a t ,

free from oxi d e by e va pora t i n g a s olut i on o f t h e c hl o ri de w i th a mmon i um c h lori

,

a n d h e a t i g t h e re si d ue u n t il th e l a tt e r s a l t h a s been e x pe ll e d
n .

3
M orse i bid 3 40 ,
— .
,
1 .

4
A l on g n arrow p air of forc eps w i th sligh tly c urved e n d s suc h as are u se d ,

bi ol ogi c a l w o rk a n d a pi n e s p l in t e r w il l be f o un d v e ry c on v e ni e n t as a i d s in
, ,.

a n d als o e mp t yi n g t h e bo t t l e T h e pi n e spli n t e r is use d i n s t e a d o f a p i e c e o f

.

si n c e a s c rat c h o n th e i n si d e o f th e bottl e w ill a l mo s t i n va ri ably c a use a

S i mil arly a gl a ss r od w i t h a sh a rp e n d sh o ul d n o t b e us e d I f a w ire is us .

sure t h a t t h e e n d is pro te c t e d w i th c ot t on .

5
B u t d o n o t fill t h e e n t ire s t oppe r w i t h c o tt on si n c e t h e sp ac e is n e e d e d ,

d ryi n g a ge n t .
 OR GANI C CO MBU ST I ON S 241

a mb e r of th e m ain p ar t o f th e b o t tl e to k e ep p a r ticl e s fr om
t in g t hr o u gh th e h o l e s a n d ge tt i n g up on th e gr o u n d surf a c e .

s e r t a plug of co tton o r a co r k in th e t op o f th e in n e r s t an din g -

te r o f th e b o t t l e a n d t h e n qu i c kl y fill th e ou t e r
,

th e a lumi n a a sb e s t o s mix t ur e
-
P a ck in s om e .

b ove it n ea r th e top o f th e tub e This k eeps th e fin e .

fr om ge tt i n g up on th e groun d surfa c e s of th e s topp e r

fr om b ei n g bl own ou t i n to th e sid e arm T ak e ou t th e .

o r c o rk fr om th e t op o f th e i n n e r s t an di n g tub e quickly ,

a l l dus t p a r t icl e s fr o m th e gr o u n d surf a c e s in th e b o tt om

b ot t le an d a t th e t op by m e an s of co t t on h e ld in th e
ep s care fully gr e a s e wi th a good s top co ck gr ea s e an d
,
1 -

r t t h e s t opp e r D o n o t u s e v a s e li n e S i n c e i t h a s n o b ody
“
.
,

is too thi n an d caus e s s ticki n g of th e s topp e r T h e

, .

c e s wh e n p r op e rly gr e a s e d will a pp e a r cl e a r
,
sh ow
, ,

j oi n ts a r e gas t igh t Gr ea t c ar e S h ould be us e d in

.

l ow e r gr oun d j oin t T oo li t tl e gr e a s e will m ak e it

.

ch may clo s e th e h ole s I f this gr ou n d j oi n t .

t h e r e is l i t t l e h op e of b e i n g a bl e t o op e n th e
e c o t t on fr om c o min g in c on t a c t wi th th e

provid e d wi th a sm all groun d s topp e r

t to be 2

arm is th e on e t h a t is n e x t t o th e c ombus t i on

Th en wh en th e combus ti on is ove r an d th e rubb e r s topp e r

d th e groun d s topp e r is in s er te d an d an y wa te r th a t may
,

in th e arm c an n o t e vap or a te duri n g fur th e r m an ipul a

On ly a v e ry sm all am ou n t of gr e a s e if an y sh ould b e , ,

this s topp e r on a cco un t of th e d an g e r o f rubbin g it off

s c au s I n g l o ss of w eigh t .

T h e S id e a rms of th e b o tt l e are b en t sligh t ly upwa rd n e a r

1
S ee f o ot n o t e p 2 2 9
,
. .

c a s e t h e a b so rp t i on b o t tl e is provi de d w i th a small gro un d s topp er

'
2
In n ot ,

er u ing
t b a n d plu g up t h e o p e n e n d w i t h a pi e c e o f

e v a p o r a t i on o f a n y mo is t ure t h a t ma y

may va ry in w e i gh t u n de r t he d i ff e ren t
ov ed a n d th e a rm c a re f ul ly c l ea n e d b e f o re
242 LAB OR AT ORY MANUAL OF OR GANI C CH E MI S T RY
th e neck in o rd e r th a t an y dropl e t s of wa t e r th a t may colle c t will
r e m ai n in th e d e pr e ssi on an d n o t t en d t o r u n a l on g th e arm
durin g subs e qu e n t h an dli n g T h e sid e a rms sh ould be f r e e from
.

an y dus t p a r t icl e s which migh t b e l o s t du r i n g th e op e r a ti o n

a n d ch an g e t h e w e igh t T h e c o t t on i n sid e th e b o tt l e is us e d
.

p ar tly to pr e ven t an y p ar ticl e s fr om b ei n g ca rri e d by the gas

i n to th e s e sid e a rms .

Con n e c t th e a rm pr ep ar e d f or th e sm all s t opp e r direc tl y wi th

t h e c ombus t i on t ub e by m e an s of a g ood r ubb e r s t opp e r 1
In .

d oi n g this d o n o t gra sp th e b o t tl e i ts e lf tak e h old on ly of th e —

sid e a rm Oth e rwis e t h e arm may b e brok en off D o n ot u s e

. .

an y i n termedi a te tu be s in c e w a ter w i ll c ol l ec t in it a n d s tay there .

T he rdin ary rubb e r s t opp e r is a b ou t 2 5 mm l on g an d tap e rs

o .

con sid e r ably S in c e a s n u g fit is n e ce ss ary a n d sin c e pr e cau ti on s

.

mus t be t ak en in o rd e r t h a t th e r ubb e r s topp e r c an e asily an d

quickly b e r e m ove d fr om th e abs o r p ti on b o ttle a t th e en d of
th e c ombus t i on c u t off th e e n ds o f th e s t opp e r in such a w ay
,

th a t i t will b e a b ou t 1 2 1 3 mm l on g a n d t h a t i t will fit in th e
— .

t ub e wi t h ou t l e a vi n g a n y sp a c e s f or t h e c o ll e c t i on of w a te r
b e twe en th e s t opp e r an d th e tub e A l on ge r s t opp e r is ve ry .

di fficul t t o r e m ove fr om th e abs o rp ti on b o t tl e af t e r th e arm h a s

b een h e a t e d by th e h ot ga s e s R e d rubb e r s topp e rs
.

Th e y S h ould b e th or oughly cl ean e d an d all m o is tur e

will h e lp to r em ove an y sulfur .

b e p a ss e d t hr ough e i th e r th e in n e r
ch amb e r fir st » by ch an gin g th e p o si ti on o f th e l arge
\

S in c e s om e h e a t is e vo lv e d in t h e abs o rp t i on o f
b e t te r t o p a ss th e gas through th e ou te r ch amb er
subs e qu en t c ombus ti on s th e gas mus t b e p a ss e d i n
ma n n er o th e rwis e th e r e is t h e p o ssibili t y of th e ga s l e
,

b o t t le wi th s om e m ois tur e which it h as tak en up fr om th e p ar t

a l r e a dy m o r e o r l e ss s a t u r a t ed in a pr e vi ous ru n .

This abs orp ti on b ot t le an d th e on e d e sc r ib e d n ex t wh en ,

n o t in u s e S h ould b e k e p t in a b ox p a ck e d wi th c o tt on f or p
,

p r o te c ti on f r om b r e akag e an d dir t .

1
Car ef u l l y b re a t h e t h ro ugh t h e s topp e r fo r a mome n t an d t h en it w ill
u
t h e t be mo re rea dily . Do n ot a ll o w a n y e x c e ss o f m o is t ur e to re ma i n .
244 LAB ORAT ORY MANUAL OF OR GANI C CH E M I S T RY
wi th h ol e un d e rn ea th R apidly cl ean th e groun d surfa ce s
th e .
,

a n d gr e a s e an d p u t t og e t h e r as d e scrib e d a b o v e S e e t h a t th e
”

co t ton d oe s n o t ge t on th e gr e a s e d grou n d surfa ce s an d a ls o th at

t h e a rms a r e fr e e fr om p a r t icl e s T h e gl a ss s topp e r f or on e arm.

is of cours e n ot n e c e ss ary in th is b ottl e

, ,
.

Con n e c t t hi s abs orp t i on b o t t l e wi th t h e firs t abs o rp t i on

b ot t le by m ean s of to 4 cm of h ea vy w a ll e d rubb e r p r e ssu r e .
-

t ubi n g 1
H e r e a ls o d o n o t gra sp t h e b o ttl e i t s e lf b u t tak e
.
,

hold onl y of th e arm (comp are p I n o rd e r t o a v oid l o ss .

of gas th e a rms of t h e tw o b o t t l e s S h ould a lm o s t m ee t bu t c a r e is ,

n e c e ss a ry t o pr e v en t th e e dg e o f on e fr o m rubbi n g a ga in s t t h e

o th e r si n c e t h e gl a ss is e a sily chipp e d off wh e n th e y a r e b r o u gh t

t og e t h e r i n sid e th e h e a vy t ubi n g S om e t im e s it is a dvis abl e .

t o wir e t h e s e j oi n t s wi th N o 1 6 c opp e r wir e . .

T h e ga s mus t b e p a ss e d i n t o t h e ou ter ch amb e r firs t .

On e ch a rg e o f s od a lim e (ab ou t 2 0 gr ams ) is g o o d for tw o

combus ti on s S om e tim e s it c an b e us e d f or on e or tw o m or e
.
,

bu t t h en t h e r e is a lw ays a risk t h a t th e a bs o rp ti on may n o t b e

comple te S od a lim e wh en m ois t abs orbs ca rb on dioxid e ve ry
.
, ,
'

rapidly an d give s off c on sid e r able h e a t S om e t im e s th e sod a .

lim e is of a li gh t y e ll owish br o wn c o l o r which is du e t o th e -

p r e s e n c e o f s om e c omp o un d o f ir on fr o m th e p o t s in which i t is

pr ep a re d A S th e abs orp ti on progr e sse s th e colo r chan ge s to

.
,

whi te an d thus it give s a m e a sur e of h ow much s od a lim e is

b e in g us e d I t is n o tic ed t h a t th e color ch an ge s e ven ly as th e
.

abs o rp t i o n t ak e s pl a c e T h e pr e s en c e o f ir on a ls o h e lps by
.

a cc e l e r a t i n g th e r a t e o f abs o rp t i on a cc o rdin g t o Gu are s c hi

2
.
,

On a cc o un t o f th e h e a t g en e r a t e d durin g th e abs orp ti on ,

dr ople t s of wa te r will s om e tim e s colle c t on the walls in th e

upp e r p ar t of th e ou te r ch amb er This of c ourse wil l do n o .
, ,

li arrrL
cas e s wh e r e m an y c omh u s tion s are b e in g ru n an d e sp e ci a lly
In ,

wh er e ex tr em e a ccur a cy is r e quir e d it is d e sir able to a dd an oth e r ,

1
Car ef u l l y brea t h e th ro ugh t h e t ubi n g Comp are . n ote o n th e rubbe r s toppe r ,

p . 24 2 .

S upp a ll e n c ic l op e di a di h i mi c a , Chem A bs tr ac ts , 10
’
2
. a nn . c A ug .
,
19 15 , .
 OR G AN I C CO MBU S T I ONS 24 5

a bso rp ti on b ot tle fill e d like th e on e d e scrib e d ab o ve Wi th b o th

s o d a lim e an d a lumin a a sb e s to s This is we igh e d a ls o a n d it s
-
.

we igh t in dica te s wh e n th e firs t b o ttl e will n o lon ge r abs orb

c a rb on di oxid e comple te ly Or in s t e a d th e s e con d b ot t le of
.
‘

t h e t r a i n may b e fill e d on ly wi t h s o d a l im e an d th e third on e

o n ly wi t h th e a lumi n a a sb e s t o s
-
Wh e n th e bl an k ru n (p 2 4 6)
. .

is mad e wi th this la t te r c ombin a t i on th e t hird b o t tl e sh ould ga in ,

a s much a s th e s e c o n d b o tt l e l o s e s I n b o t h o f th e s e c ombi n a
.

t i on s t h e s u m of th e ga in s o f eac h b o t t l e a t th e e n d o f a c om
bu s tion r epr e s en t s th e t o t a l i n cr e a s e in w e igh t du e t o c a rb on
di oxid e .

N ote on emptyi n g the bottl e — T h e s o d a lim e b e c om e s h a rd

an d c a k e d on s t an di n g a f t e r t h e a bs o rp ti on o f c a rb on di oxid e

a n d c a r e mus t b e e x e rcis e d in r e m ovi n g i t A pi n e splin t e r 1

.

is us e ful in br e akin g up th e m a ss Of t en it b e c om e s n e ce ss ary

.

to m o is t en th e m a ss t o s o f t e n i t T o o much w a t e r mus t n o t
.

be us e d an d it mus t b e p our e d off a t on c e o t h e rwis e th e b ot tl e ,

may b e cr a ck e d on a cc ou n t o f t h e h e a t a n d e xp an si on o f th e m a ss .

Dilu te hyd r o chlor ic a cid will r e m ove th e p ar ticle s a dh e rin g to the

wal ls T h e a lumin a pumice mus t a ls o b e r en ewe d
.
— .

. c G ua r d T ub e an d P a l d i ou C l ori d e S ol u ti on
l a s h — T o t h e c ar .

bon di oxid e abs orp t i on b o t t l e a t t a ch an o r di n ary c a l cium chlorid e

t ub e which h a s th e sm a ll e n d b e n t a t an d which h a s b e e n

h alf fil le d wi th th e a lumin a pumice mix tur e k ep t in pla ce wi th

-

plugs of c ot ton A t th e wid e en d of th e tub e a rr an ge a sh or t

.

g l a ss t ub e ,
wi t h a n a rr o w o p e n i n g f o r l e a di n g t
, h e ga s i n t o a v e ry
dilu te s o lu tion of p a ll a di ous chl orid e B y l e avin g th e dryin g .

t ub e h a lf e mp t y w e h a v e a r e s e rv o ir f or a n y of t h e p a ll a di o us
,

chlorid e s olu t i on th a t migh t b e drawn b a ck an d thus it is pre ,

ve n te d fr om e n te rin g th e abs o r p t i on b o t t l e .

T h e p a ll a di ous chl o rid e s o lu t i on is us e d f or d e t e c tin g an y

carb on m on oxid e from an i n c ompl e t e co mbus t i on an d als o f or
in dica t in g th e r a te of abso rp t i on of th e produc t s of c ombus ti on
by comp a r i n g th e bubblin g he r e wi th t h a t in th e bubbl e c oun te r .

This will be discuss e d la t e r (s e e p T h e s o lu t i on is o f a

.

li gh t ye llow c olor an d is pr ep are d by mixi n g 1 c c of a

-
, .

1
S ee foo t n ot e ,
-
p . 2 40 .
 LAB OR A T ORY MANUAL OF OR GANI C CHE M I S T R Y

5 p e r c e n t s o l ut i o n o f p a ll a di o us chl o r id e wi th zoo cc o f dis .

t ill e d w a t e r . F r om th is ve r y dilu te solu t ion ca rb on m on oxid e

p r e cipi ta te s m e ta llic p al ladium whi ch app ea r s a s bl ack colloid al
,

p ar ticle s T h e s olu t i on sh ould b e pro t e c te d from an y carb on

.

m on oxid e in th e r oom e sp e ci a lly wh en th e l ab ora tory is sup

,

plie d wi th wa te r gas Wh en in u s e th e b o t tle sh ould h ave a

.

s topp e r through which p a ss e s th e gl a ss tub e an d whi ch h as a

c h an n e l c u t in t h e sid e t o a ll ow th e g a s e s t o e sc a pe .

T h e sh o r t gl ass t ub e m e n t i on e d ab ov e l e a din g i n to th e p al
l adiou s chl ori de s olu t i on sh ou l d b e d r awn o u t in t o a n arr ow
,

o p e n i n g lik e th e on e in th e bubbl e c o u n t e r in o r d e r t h a t th e ,

c omp arison of th e r a te c an be m ad e S i n c e th e visco si ty of th e .

sulphuric a cid is diff e r en t from tha t of th e p all adi ous chlo r id e

s olu t ion an d sin c e th e gas pr e ssu r e s are a ls o diff e ren t in e a ch
c a se th e ra t e of bubbl e f orm a t i on will n o t be e x a c tly th e s am e
,
‘

bu t a goo d id e a o f th e n o rm a l r a te s c an b e ob ta in e d by
“ ”

comp a r in g th e bubblin g b e f or e th e subs tan ce b e gin s to burn .

I n s t e a d o f t h e sm a ll b o t t l e f or th e p a lla di ous chl o rid e s o lu ti on

a bubbl e c ou n t e r c an b e us e d I n this c a s e th e dryi n g t ub e p re
.

c e din g it is pla c e d in a h oriz on ta l p osi ti on I t is difficul t t o .

cl e an th e bubbl e c ou n te r I f m e ta llic p alladium is pre cipi tated

.

i t c an be diss o lv e d in n i t ric a cid .

V M e th o d
. of R unn in g B l an k D e te rmin ati on s
S in c e t h e r e isp o ssibili t y of m an y e r rors in th e app ara tus
th e
a n d ch e mic a ls ; n o c o mbus t i on sh o uld b e r u n un t il t h e o p e r a t o r

is ce r tain th a t e ve ry th in g is al l ri gh t T h e on ly s atisfa c tor y .

m e th od o f fin din g this ou t is t o r un a blan k d e te rmin a ti on .

A f te r th e a pp a r a t us is a l l s e t up (wi t h ou t th e b o a t an d th e
a bs orp t i on t r a in ) h e a t th e combus ti on tub e t o th e s am e tem
,

r e t h a t will b e us e d t i t h e d e t e rmi n a t i on h
p er a t u
l r
a e n
.
t a t ,

is to a ch e rr y r e d an d p a ss in purifie d oxyge n gas a t th e p r op e r

, ,

ra te durin g th e cours e of ab ou t tw o h ours This p roc du r e . .

is s om e t im e s c a ll e d l wi firs m is u will
”
g o n g ou t A t t o .t r e ,

con den se n e a r th e op en e n d of »th e tub e Af te r this moi s tu r e

.
.

h a s dis app e a r e d a t t a ch an ordina r y c a lcium chl o r id e d r yi n g t u be

248 LABOR AT OR Y M A N UAL or OR GA NI C CH E M I S T R Y
In a la te r ch ap te r th e r e l a tive w e i gh t of th e sm all vari a ti on s
in th e blan k r u n s a re discuss e d (p .

VI . W e igh in g
b s orpti on B ottl e s th e A

I t h a s o f te n b e en f ou n d t h a t t h e gr ea t e s t of al l th e e rrors
li e s in th e w e ighin g o f th e abs o r p ti on b o ttle s T h e m e thod .

given h e r e is n o t cl aime d to be p e rfe c t bu t in ou r exp eri en c e it

give s e xce ll en t r e sul t s Wh en it is con sid er e d h ow m an y change s .

th e abs o rp t i on b o t t l e g oe s thr ough ch an g e s due t o th e p a ss a ge of ,

h o t g a s e s h an dli n g in m aki n g th e c onn e c ti on s d e p o si t s fr om th e

, ,

l ab ora tory a tm osph e re of dir t an d m ois ture e tc it is n o won d e r ,

.
,

th a t co n c o rd an t r e sul t s c ann o t be ob t ai n e d un l e ss gr ea t c ar e an d
con sis ten t tr e a tm en t is given .

I n th e firs t pl a c e th e abs orp t io n bo t t l e s sh ould be w eigh e d

,

e a ch t im e righ t a f te r b e i n g r e m o v e d fr o m th e c ombus t io n t ub e
1
.

Th en g en e r al con di ti on s w ill a lways be a s n early th e s am e as

pra c ticabl e T h e on ly al te rn ative would be to l e t the b o ttle s
.

s tan d for m an y h ours bu t this of cours e can n ot usu ally be d on e , .

T h e b o ttl e s mus t be scrupul ously cl ea n wh en b e in g w e igh e d ,

o th e rwis e surf a c e c on di t i on s w ould v a ry t oo much Wip e th em .

ve ry ca re fully wi th a cl ean dry cl oth which is free from sizin g

an d s t a rch A t ow el or h an dk e rchi e f which h as b e en w a sh e d
.

m an y tim e s is sui tabl e Good qu a li ty l en s cl oth is exce llen t for .

t hi s purp o s e I t sh ould on ly be us e d a f ew t im e s
. M ak e sur e .

t h a t a l l e xc e ss o f gr ea s e a r ou n d th e s topp e r is r e m ov e d by th e
firs t wipi n g in o rd e r t ha t l a t e r cl ean in gs will n ot ch an ge th e w e igh t
o n t his a cc ou n t Wip e ve ry t h o r oughly every part of th e b o ttl e 2
. .

Be c a r e ful n o t t o br e ak off th e sid e a rms I t may b e n e c e ss a ry .

t o rub h a rd a t firs t bu t a f t e rw a rds this sh ould n o t be d on e sin ce

,

rubbin g wi th a d r y cl oth in duce s a s tatic ch a rge of e l e ctricit y

a n d t his a pp a r e n t ly h a s much t o do wi th disc o rd an t re sul t s

wh en th e app ara tus is w eigh ed u n d e r th e s e con di ti on s 3

.

D u dl y d P s J Am Ch m S 15 54 ; L v d
1
e an ea e , our n . er . e . oc .
,
1 e en e an

Bi b r J
e e Am, Ch m S
ou r n 40
.
46 er . e . oc .
,
2.

A dis d v t g f m y ki ds f bs rp ti pp r t us is th t th y
2
a an a e o an t b n o a o on a a a a e c an no e

l
c e an e d pro p e rly .

3
H K M ill e r
. .
,
in an a rt i c l e o n E l ec t ri c al D is t urba n c e in We i gh i n g (J ur n o .

Amer Chem S oc . . .
,
20 s ta t e s th a t Ca re ful e xp e ri men t s l e d to t he
 OR G A NI C CO MBU S T I ONS 2 10

Achan ge of s e ve r a l milligrams is a comm on o ccurren ce I n .

o rd e r t o dissip a te t his s t a t ic ch a r ge s o m e a n a lys t s a ll o w t h e

a bs o rp t i on a pp a r a t us t o r e m a i n f o r a d e fin i t e t im e (f our mi n u t e s ,

f or e x ampl e on th e b a l an c e p an a f t e r wipi n g b e f or e t a ki n g
,

th e fin a l w e igh t ) H ow e ve r t h e r e is a qu e s t i on wh e th e r
1
,
.

th e co n di ti on s a re a lways th e s a m e si n c e th e wipi n g is n o t a lwa ys

t h e s am e T h e b ott l e c an n o t b e l e f t t oo lo n g b e for e w eighi n g
.
,

b e caus e as the ch arge is sl owly b e in g dissip a te d an d the app aren t ,

weigh t b e comi n g l e ss it Will b e gin to g ain on a ccoun t o f the

,

d ep osi t of m ois ture an d n o con s tan t weigh t will be f ou n d

,
2
.

An o th e r m e th od t o ob tain a c o n s tan t w e igh t a f te r th e wipi n g

is to p ass th e thumb an d on e fin ge r d ow n opp osi te sid e s of th e
b ottle at the s am e tim e an d th en imm e di a te ly s e t th e b ot tl e on
,

th e b a l an c e p an a n d w e igh R ep e a t th e a l t e r n a t e wipi n g a n d
.

p ass age of the thumb an d fin ger an d w e ighin g u n til th e w e igh t

is con s tan t or d oe s n ot va ry in tw o con s e cu tive w e ighi n gs by m or e
t h an gram This may r e quir e from four t o t en c ompl e te
.

rep e ti tion s P erh aps the u s e of th e fin ge rs on th e b ot tl e jus t

.

b e f ore w eighi n g is op en to qu e s tion bu t th e m e tho d give s such ,

good con cord an t r e sul t s an d is s o rapid th a t w e are willi n g to

re comm en d it T h e fin ge rs should be cle an an d are usu ally
.
,

c on c lusi on ipi n g t he fla sk it bec ame el ec tri fied an d th a t t h is s ta t i c c h a rge

th a t in w , ,

a c t i n g o n t h e fl oo r o f t h e b a l an c e i n d u c e d on i t a c h a rge o f o pp o si t e c h a ra c t e r
, ,

a n d t h a t t h e mu t u a l a t t ra c t i o n b e t w e e n t h e s e t w o c h a rge s o f e l e c t ri c i t y h a d t h e

e ff e c t o f a pp a r e n t ly i n c re a si n g t h e w e i gh t o f t h e fl a sk T h e p o t e n ti a l o f t he .

c h a rge w o ul d v a ry w i t h t h e a t mo sp h e ri c c o n d i t i o n s a n d w i th t h e ma n n e r o f w ipi n g

th e fl a sk B y usi ng a li n e n c l o t h in ve ry d ry w e a th e r it w a s fo un d p ossi ble

.
,

t o pro d u c e a c ha rge o n a 1 00 c c fl a s k w h i c h w o ul d re qui re

.
gra m a dd i ti on al
w ei gh t t o re s t o re e quili briu m A h igh c h arge li ke t his how e ver w o uld be rapidly
.
, ,

d issip a t e d an d t h e fl a s k w o ul d a pp e a r t o l o s e w e i gh t I t w a s fo u n d t ha t a c h arge
.

w h i c h a pp a re n tly c a use d a n i n c r e a s e in w e i gh t o f a bo u t gra m w o ul d be t e

t a in e d qui t e a l on g t i me a n d o n e mi gh t rea dily o v e rl oo k t h e e rro r w h i c h w oul d
,

t h us be i n t ro d u c e d I t w a s fur t h e r f o u n d t h a t a s mall c h a rge w o ul d be re t ai n e d

.

man y d ays o n a fl a sk ke p t in a de si c c a t o r I n d a mp w e a t h er a c ha rge w o uld .

re adily p ass off a n d n ot give rise t o a n e rror b u t on a very d ry d ay t he pra c t i c e o f

,

w ipi n g gl a ss w a re jus t b e f o re w e i gh i n g is l i a bl e t o c a us e s e ri o us e rro rs .

1
L E W is e J ou r n A mer Chem S oc 3 9
. .
,
. . 2 06 2
. . S ma ll a pp a ra t us in
,
.

c on n ec t i o n w i t h mi c ro a n a lysis w as us e d in t h is w o r k a n d t h e e rr o r is n o t s o l a rge
-
, .

2
S ee a ls r t i l b R ae a n d R e illy Ch e m N e w s 11 4 1 8 —
7 9 2 00 —
o a c e y , , 3 ,
.

P r of T W R i c h ard s h a s re c o mme n d e d t he us e o f ura n iu m oxi d e or rad iu m l o

. . . i

mi de in t he bal an c e c a se t o d issi pa t e t he se c h a rge s .

250 L AB OR A T OR Y M A NU A L OF O RGA NI C CH E M IS TR Y
sligh tly m ois t whil e h an dli n g the cl oth an d th e b ot tl e an d th e ,

ve r y sm all am oun t o f m ois tu r e an d gr ea s e from th e ski n th a t may

b e l e f t up on th e su r f a c e o f t h e b o t t l e is n o d oub t f a irly c on s ta n t
an d i n v o lv e s an e rr o r f a r l e ss t h an t h a t c a us e d by th e s t a t ic

ch arg e T h e b o tt le sh ould n et of cours e be t ouch ed by

.
, ,
‘

t h e fin ge rs e xc e p t a s dir e c t e d .

Diff icul ty is s om e tim e s exp e ri en ce d in ob tai nin g con cord an t

r e sul ts on d amp d ays bu t wi th prop e r pre cau ti on s good re sul t s
,
1

c an b e ob t ai n e d wi t h o u t much t r o ubl e .

S i n c e th e abs o r p t i on b o t tl e s a r e Of t en shu t Off a n d disc on

n e c t e d u n d e r di ff e r en t pr e ssur es o f oxyg e n it is w e ll t o r e l e as e ,

t h e pr e ssur e wi thi n th e b o ttl e by momen tari l y op eni n g th e s top

c ock b ef or e weighin g
,
.

A fin e an a ly t ic a l b a l an c e mus t of c ours e be us e d an d it ,

sh ould h ave a cap a ci ty of 1 00 gr ams f or a ccura te work T h e .

a bs o rp ti on b o t t l e s wh e n fill e d s e ld om w e igh much ov e r 9 0 gr ams

, , .

For an e xc e ll en t discussi o n o f an d c a r e ful dir e c ti on s f or

w ei ghi n g, ca libr a ti on o f w ei gh t s e tc y ou are r e f erre d to an ,
.
,

a r t icl e by R ae a n d R e illy in Chem N ew s 114 —

, 187 9 .
, ,

2 00 3
— an d t o th e f o r thc omi n g b o ok on qu an ti ta tiv e an alysis
,

by P ro fe ss o r s H T B e an s a n d H a r o ld A F a l e s of th e D ep ar t
. . .

m en t of Ch e mis t r y Co lumbi a Un ive rsi t y ,

.

A c ou n te rb al an ce w e i gh t o r b o t t l e is s om e tim e s us e d by s om e
a n alys t s in w e i ghi n g th e a bs o r p ti on a pp a ra tus A simil a r .

pi e ce of app ara tus is m ad e to we i gh a pp r o xim a te ly th e s ame by

a ddi n g l ea d sh o t a n d is k e p t b e sid e t h e a bs o rp t i on app a r a tus
,

a l l th e t im e an d t r ea t e d jus t th e s a m e in e v e ry w ay as f a r ,

a s possibl e .

VI I . W e i gh in g th e S ub s tan c e
S in ce
rgan ic subs t an ce s are gen e ra lly hygro scopic an d
o

si n ce it is n e ce ss ary t o ke ep al l m ois tu r e away from th e sub .

s tan ce u p to th e ve ry t im e it is pu t i n to th e combus ti on tub e ,

1
D udl e y an d P e a se J ou rn A mer Chem S oc 15
,
. .
5 40 s t a t e
. . I f w e may
, , ,

t rus t ou r e xp e ri e n c e it is al mo s t i mp o ssi bl e t o ma ke s a t isf ac t o ry c o mb us t i on s in

show e ry w ea th e r T h e se a u th ors jus t w ei gh e d t h e a ppa ra t us dire c t from t h e
.
”

furn ac e w i thou t w ipi ng T h eir c ombustio n c on sist ed of de termi n i n g c arbon in

,
.

s tee l .
25 2 LAB OR AT ORY MANUAL OF OR GANI C CH E M I S T RY
T he p orce lai n or qu ar tz bo a t prope rly cl ean ed h eated in ,
1
,

a n on lumi n ous fl am e a n d c o o l e d in a d e sicc a t o r is p l a c e d in

-
, ,

th e piggi e an d b o th weigh e d toge the r Th en the b oa t is .

r em ov e d wi th ton gs or f orc eps th e subs tan c e add ed an d al l , ,

weigh e d t oge th e r agai n T h e di ff e r en ce in w eigh t is th e r efor e

.

t h e w eigh t o f s ampl e us e d S i mil a r pr e c au ti on s sh ould be tak en

.

h er e in cl ean i n g th e ou tsid e of th e
a s giv en f or th e abs o rp t i on b o t t l e s s ee p 2 48 ,
. .

bo th th e b oa t tub e an d th e b oat should be k ep t

For w e i ghi n g o u t liquids s ee p 2 6 7 ,
. .

Ordi n arily th e am ou n t of subs tan c e us e d f or a

should be ab ou t gr am wi th an all owan c e of ab ou
,

abov e or b e l ow si n ce th e a c tu al w eigh t n ee d n o t
,

gram Wi th too sm all an am ou n t of subs tan c e th e pr op or

.

t ion al e rr ors a r e gr ea t e r a n d wi th a l a rg e r am oun t t oo much

t im e is c on sum e d in ru n n i n g th e c ombus ti on T h e w eigh t sh ould .

b e c ar e fully t ak en t o th e four th d e cim al pl a ce an d prop e rly ,

r e cord e d .

T h e subs tan c e should be p erf e c tly dry I f n e c e ss ary spr e ad .

i t up on a cl ean dry w e igh e d wa t ch gl a ss d e te rmi n e th e t o ta l ,

w eigh t an d s e t a sid e in a d e sicc a tor ove r fre sh con c sulfuric .

a cid f or a t l ea s t t w e n t y four h ours -

Th en w eigh again . .

w eigh t h as ch an g e d pu t th e subs tan ce b a ck again f or an o

p eri od T h e dryi n g c an be h as ten e d by firs t p l a ci n g it on
.

wa tch gl ass a s ab ove an d s e tti n g it in an oven h ea te d to 1 1 0

a n d a f te r s e v e r a l h ours a ll owi n g it t o c ool in a d e sicc a t or .

t r e a tm e n t c an n o t b e giv en to all org an ic subs t an c e s si n c e

sublim e m el t or d e comp os e a t th at temp era ture T h e
,
.

c an b e dri e d in a v a cuum ov en a t ab ou t or in

app ar a t us provid e d wi th a d ryi n g agen t an d k ep t a t th e tem

2

p e r a tu re o f b o ili n g a c e t on e

I n c a s e i t sh ould b e n e c e ss a ry t o d e t e rmi n e th e hydrogen

in a subs t an c e c on t ai n i n g m ois tur e wh o s e m ois tur e c on ten t is ,

1
S ee p . 23 6 .

2
Abd rh al de n s H an db uc h de r Bioc h mis c h e n A rbe i t sme thoden
e
’
, I ( 19 1
2 9 6 ; a lso in E i me r
,
Amen d N Y c atalogue un der th e name
, . .
, , , Va
D ryi n g A p pa rat us A bd e rh al d e n s
’ ”
,
,
 OR GANI C CO MB USTI ONS 25 3

t he hydrogen c an n o t be dire c tly ca lcul ate d to th e dry

ke th e c a r b on si n c e th e hydr o g e n h as b een ob tai n e d
total w e i gh t o f w a te r a bs orb e d in th e firs t b o t t l e .

th e a m o u n t o f w a ter in th e s ampl e mus t firs t b e

fr om th e w e igh t of w a te r absorb e d an d the hydroge n ,

in th e r e m ain i n g We igh t o f w a t e r T h e p e rc en t a ge .

t h en be ob tai n e d usi n g t h e w e i gh t o f moi s tu re free s ampl e -

.

VI I I . T h e Comb u s tion P r ope r

Af te r it h as b e en sh own by th e bl an k d e te rmin a ti on (p 246) .

a t t h e e n t ir e a pp a r a t us is a l l righ t t ur n o ff t h e h e a t in th e sm all
,

1 ) o f t h e fur n a c e a n d a ll o w t his en d o f t h e t ub e

a in t o c o o l t o r o om t e mp e r a t ur e R ais e th e .

A t th e s am e t im e push b a c k
n s in o rd e r t ha t t h e sp a c e f or t h e

cool turn Off th e oxygen shu t off

, ,

dryin g tub e disco n n e c t th e purify

,

t ub e a n d pull ou t th e r oll of
m e an s of th e c opp e r wir e wi th h ook
p urp o s e m a ki n g sur
,
e t h a t t h e r o l l is
cl e an surfa ce wh e r e it will n o t be in con ta c t
m a te ria l Th en ca r e fully r e m ove t h e b o a t
.

gh e d a m ou n t of subs tan ce f r o m t h e b oa t t ub e
ie by m e an s o f f o rceps p u t i t i n to th e tub e a n d
, ,

t b a ck wi t h t h e c opp e r wir e i n t o it s pr op e r p o si t i o n a b ou t
from th e ce rium di oxid e R epl a c e th e r o ll o f o xidiz e d
.

con n e c t th e pu r ifyin g tr ain an d l e t t h e oxyge n p a ss

,

gu ard tub e from th e o th e r en d o f th e c ombus ti on

th e en tir e a bs orp ti o n t r a i n (p 2 47 i n cludi n g f oo t
.
,

I f t h e subs t an c e is r ea dily di s t ill e d ou t o f t h e b oa t t h e

ti on t r a i n sh o uld be a tta ch ed before th e b oa t is p u t i n to t h e
A s a rul e t his is n o t n e c e ss a ry a n d it is e a si e r to a tta ch
,

so rp ti on t rain af te rwards .

tha t th e
25 4 LAB ORATORY MA UAL OF O GA N R NI C C HE M I STRY
bubbl s p ssi g hr ugh
e asulfu r ic a cid
n t bubbl e coun te r
o th e in t h e -

c a n jus t b e c ou n t e d — t h a t is a t th e r a t e o f a b ou t t h r e e t o f our ,

a s e c on d .

is ve ry di fficul t to d e scrib e in d e tail th e a c tu al m e th od

It
o f bu r n i n g a n o rg a n ic subs ta n c e sin c e e a ch subs ta n ce has its ,

ow n p eculi a ri ti e s an d t h e r e f or e on ly a g en e r a l d e scrip ti on c a n be

give n An id ea as to h ow th e subs tan ce b eh ave s on h ea ti n g

.

sh ould be gain e d b e for e h an d if su ffici en t is ava il able by g en tly , ,

h e a tin g it an d gradu ally burn i n g it ina b oa t o ve r a sm a ll flame 1

.

Gr a du ally m ov e the l a rg e h e a ti n g s e c ti on (No 2 ) a c e n t im e t e r .

a t a t im e t o wa rd th e b o a t u n til m o s t o f th e c e rium di oxid e

'

, ,

pumice is h e a te d t o r ed n e ss A t th e s am e t im e pro vid ed the .

,

subs tan ce is n ot t oo vol a tile turn on th e swi tch an d all ow the ,

.

sm all h ea tin g s e c tion (N o 1 ) to b e c ome w arm an d fin ally h ot .

,

bu t n o t t o r e d h e a t e xc ep t in sp e ci a l c a s e s A ls o h e a t up th e
,
.

l as t s e c ti on (N o 3 ) s o t h a t n o w a te r will con d en s e in t ha t en d of
.
*

t h e c ombus t i o n t ub e Th e s e op e ra ti on s o rdin arily r e quir e ab ou t i

.

t e n mi n u t e s Th en m ove th e la rge h e a tin g s e c ti on (No 2 )

. .

clos e r to th e b oa t u n til th e cerium di oxid e pumice is -

h e ated an d th e a sb e s to s pl a t e on th e e n d of
,

is ove r th e a sb e s to s plug b e tw een th e c erium

th e b oa t N ow very s l owl y jus t a li tt l e (0 5 c
.
,
.

t h e sm a ll h e a ti n g s e c ti on (N o ) towa rd a . 1

Wi th subs tan ce s t h a t sublim e r e a dily it mav ,

t o bri n g t h e sm a ll h e a t i n g s e c ti on (N o ) to a . 1

r a tu r e t o d r iv e a l l o f th e s a mpl v r t h c rium
p e e o e e e

pumic e Wi th an a c t ive ca t alys t th e forwa rd p oin t s o f

.

p g
r e n a t e d pumic e will gl o w 2
T h e gl o w c a n n o t a lw a ys .

o n a cc o u n t o f t h e a sb e s t o s W i th s om e subs ta n ce s th e .

p a r t o f th e pumice mix ture will app ear gray a s th e de c om

b e gin s This is pr ob ably du e to p ar t icle s of c a r
.

a r e l a t e r bu r n e d c o mpl e t e ly T h e burn i n g o f t h e .

o rdin a rily r e qui r e s fr o m t e n t o t w e n t y fiv e mi n u t e s -

,

upon h ow r apidly th e s ubs tan ce c an be dis ti ll e d an d

1W yl D i M th d d
e ,
rg is h Ch mi
e e o I en er o an c en e e,

J our n . A mer Che m S oc . . .

,
39 20 .

2
In so me
s s t h e li t t l e roll of c opp e r oxi de ga u e in fron t
c a e z

a pp e a rs t o a c t c a t a ly t i c a lly si n c e i t a lso gl o w s u n d e r c e r t a i n c o n d i t i o n s .
25 6 LAB OR AT OR Y MANUAL OF OR GA NI C CHE MI S T RY

ric oxid e c an s om e time s be e s tab l ish e d by th e

f ac t th a t th ey d o n o t dis app ear af te r pro lon g e d h e a ti n g L ate r .
,

wh en th e b oa t h as b e en r em oved th e proof c an be m a d e d e fini te

,

by s ee in g if th ey are solubl e in ni tric a cid I t sh ould b e n o te d .

h owe ve r th a t carb on p ar ticle s f orm e d un d e r ce r tain con di ti on s

,

a r e v e ry di fficul t t o bur n (s o c a ll e d gr aphi tic c arb on )

-
.

I f m ois tur e c o ll e c t s in th e c ombus t i on t ub e jus t in fr on t o f

t h e abs orp t i on app a r a t us an d p e rsis t s e v en f o r s om e t im e a f te r
'
th e subs ta n ce h as b een bur n e d i t sh ould be driv e n thr ough b y
,

slowly drawin g the tub e fur th e r in to the fur n a ce Con side r .

abl e c a r e is n e c e ss a ry f or t his gr a du a l h ea t i n g t o pr e v e n t th e bur n

in g of th e rubb e r s t opp e r a n d als o th e cr a cki n g o f the tub e 1

.

Aft e r th e t ub e h as b een swep t ou t f or the f or ty fiv e -

min u te s from th e dis app ea r an ce of th e l a s t p ar ticl e s of ca rb on

in o r a r oun d th e bo a t th e absorp ti on b o t t l e s a re cl o s e d dis
, ,

con n e c te d an d i mm e di ate ly we igh e d (p 2 Th e gu ard tub e

.

should be r epl a ce d an d th e combus tion app a ra tus is t h en r e a dy for

an o t h e r d e t e rmi n ati on wi th ou t fur th e r t r ea t m e n t .

T h e tim e fr om pu t ti n g t h e b oat i n t o th e t ub e u n til th e

a bs orp ti o n b o t t l e s a r e t a k en t o t h e b a l an c e usu ally is fr o m an

h our an d t en min u t es to an h our an d a h alf A li t tle expe ri .

e n c e s o on m ak e s it p o ssibl e t o c u t t his d o wn t o an h o ur or t o ,

for ty fiv e min u te s provid e d n o sp e ci a l diffi cul ty I S en coun te re d

-
,

in burn i n g t h e subs t an c e .

T w o c ombus t i on s sh ould a lways be ru n on th e s a m e subs tan c e

wh en e ve r p ossibl e an d t h ey sh ould ch e ck up wi thin n arrow
,

limi ts S ee discussion o f r e sul t s p 2 5 8

.
,
. .

N OT E

Ifc erium dioxi d is use d th e laye r of cup r ic oxide wi r e mus t

no e

be much l on ge r 40 7 c m a d th e sub s t a c e mus t b bu r n d v ry

—
,
0 .
,
n n e e e

1
If a furn ac e is e mpl oyed th e w a t er may be drive n o ve r by h ol di n g on e of th e
ga s ,

ho t t il e s u n d e r th e t u b e .S o m e o p e r a t o rs u se a s ma ll fl a m e bu t gr e
, a t c a re is

n e c e ss a ry t o pre v e n t c rac ki n g t h e t ube a n d b urn i n g t h e s t o pp e r .

 OR GA NI C COM BU S T I ON S 25 7

imu t s is r e qui r ed jus t f o the bu rn in g al n e

e r o ,

( 1 s ome sub s ta n c e s a e n o t c ompl e te ly oxi dize d eve n wh e n th e t im e

r

con side rably t e d dex n e .

I X Cal c u l ati on s ,
. an d D i s c u s s io n of R e s ul ts

S in c e t h e r a ti o of H 2 to H 20 is 1
which is e qu al to

1 1 19, we igh t of hydrog en in th e we igh t of w ate r fou n d c an

th e
calcul ate d by mul t iplyin g the we igh t of wa te r by
hydrogen is e qu al t o th e we igh t of hydrogen
li e d by 1 00 an d divid e d by the w eigh t of th e subs tan ce
Or th e fo ll owin g f o rmul a may be us e d

W e i gh t H 2 0 X X 1 00
P er cen t H
W e l gh t subs tan ce X 1 8 0 1 6

For logari thmic calcula tion

L og . wt . HzO
L og . 1 00

L og . IO

S ub t r ac t L og w t . subs
. .

L og .
p e r c en t H

S imil arly , sin ce r at io o f C t o C02 is H or f which is

the i
r,

e qu a l t o t h e w e igh t o f c a rb on in t h e w e igh t o f c a rb o n
di oxi d e foun d c an be calcul ate d by mul tiplyin g t h e w eigh t o f th e
di oxid e by f 01 { i
T h e p e rce n ta ge o f c a rb on
qu al to th e we igh t o f the c arb on mul tiplie d by 1 00 an d di vid ed
th e w e igh t o f th e subs t an c e us e d Or .
,

We igh t CO2 X 3 X 1 00
P er c en t C
We i gh t subs tan ce X 1 1

1
U si ng H=
25 8 LAB ORAT ORY MANUAL OF OR GA NI C CH E M I S T RY
Fo r logari thmic c alcul a ti on
L og w t C02 . .

L og . 1 00

L og .
-
10

S ub tr a c t L og . wt . subs .

L og p e r . cen t C
Fo r s in c alcul a t i on a t abl e
ea e four pl ac e l ogari thms is ,
of -

given on p age s 3 08 1 —
1 .

T h e figur e s sh owi n g th e p e rc e n t ag e o f c a rb on an d hydr oge n

‘

sh ould n o t be e x ten d e d b e yon d th e s e c on d d e cim al pla ce T h e .

figure s b eyon d the s e con d d e cim al pl ace in this w ork a re n ot

signi fican t .

L i mit of Err or — I n ord e r t o be abl e t o c omp ar e th e r e sul ts

.

o f an a lys e s t o s e e wh e t h e r th e y a r e wh a t th e y sh o uld be s om e ,

s tan d ard is n e ce ss ary f or th e limi t of e rro r T h e cri te rion for .

t h e limi t o f e rr o r in go od a n aly t ic a l w ork is on e p ar t in o n e

t h ous an d M an y e x ampl e s c an be given t o sh ow th at th e d e te r
.

min ation of carb on approa ch e s this limi t al th ough th e hydrogen ,

is n ot s o good T h e n umb e r of p ar t s pe r th ousan d e rr o r X

.
, ,

c a n be c a lcul a t e d by usi n g th e f o ll owi n g r a t i o : Diff er en ce of

p ercen tage s p ercen tage X 1 000 ; or
D iff . of p e r c en te ooo ,

p e r c en t
wh e re on e p e rcen ta ge o f ten th e t heore tica l is taken for the b asis
, ,

o f c o mp a r is on This is m ad e m or e cl e ar by m e an s of the ex am
.

ple s which foll ow

A s ampl e o f c an e su ga r ( C H 0 ) w a s an a lyz e d wi t h th e 12 22 11

followin g re sul t s : C T h e t h eo r e ti ca l
percen tage s for this subs tan ce a re C T he

T h is
1
lysis m d by M r R T F li i
ana w as aH is h k
e lysis w . . . e c an o . c ec an a as

C = 42 . I 4% an d H = 6 46 % . a nd S i mil a r re sul t s r
w e e obt a n e d o n i
t he same subst an c e by M r H R P y n e : C = 4 2 1 9 % . . . . a nd H=6 . 23 %
and Alumi n a asbe s tos mixt ure w as used in
-
t he fi rs t i s t n an c e , a nd

a lu mi n a pu mi c e in t h e s ec o n d
-
.
26 0 L AB O RAT OR Y MA NUAL OF OR GA NI C CH EMIS TRY
a b ou t llowe d e rror Corres p On din gl y if th e s am e gain
th e a .
,

of gr am is n o te d in th e ca s e of th e s e con d jabs orp tion

b ot tl e m ean i n g ab ou t
, gram for a c ombus ti on on th e ,

b asis again of a gram s ampl e this w ould be e quival en t t o ,

C an d supp osin g the C

, th e e rr or on t his a cc ou n t
'

a l on e would be 4 5 p a r t s t h d w h i h is l b d t h
p e r ou s an c. e y on e ,

ordin ary allowe d limi t of error An y o th er e rr or in th e ”

.

w ork w ould in e a ch ca s e pu t th e d e termin ati on w ay b eyond

wha t it should be .

T h e limi t o f e rr o r of gram in w eighin g alo n e would ,

u n d e r th e con di ti on s m en ti on e d ab ove be e qu al to p ar ts p e r ,
'

t h o us an d f or th e hydr og en an d p ar t s per th ous an d for th e

c a rb on .

Th e s e figure s are given in ord e r to sh ow th at th e gr ea tes t

c a r e a t al l tim e s mus t be e x e r cis e d in ca rryin g ou t th e w ork .

Tw o c ombus ti on s sh ould a lways b e ru n wh en eve r p ossibl e ,

an d th e y sh o uld ch e ck up wi thi n t h e limi t o f e rr or sp e cifi e d a b ove .

NOT E S

1 calculatin g th e hydr oge

. Fo r n in sampl e wh ich con tain s some
a

mois t r e a d w h s mois tu r
u te
n o e e c on n t is k ow n p 52 n , s ee . 2 .

T h pe r c
2 . t ag o f C a d H i
e en e n n a h y d r o c a r b on sh oul d a d d up t o

1 00 : l: 0 .
3 pe r c en t .

3 . p e r
T he
t a g o f o xy g n in a c mp
c en
ou d is f ou d b y d
e i ff r e o n n e

en c e .This m th d of c al c l ti g th r ws al l th rr r upon th e
e o u a n o e e o

figu r e f or th is el me t (Fo a m th d of d t r mi i g o ygen

e n . r e o e e n n x

d i r ec t ly s e B sw ll J ou n A m r Ch m S o
,
e o 35e ,
—
84 9 0 ; r . e . e . c .
,
2

36 127
—
3 2 )
4 . T he e mpi r i c a l
f or mula of a compou d is fou d by divi din g n n

th e pe r c t a ge o f ac h l m n t by t h a t mi c w igh t f th e l em
en e e e t e e o e o e en ,

a n d th r a tio is t h e xp r sse d i w h ol umb e r s by d ivi di g ea ch

e n e e n e n n

t e rm by t h l owe s t va lue r by s m simpl e f r a c t io n o f t h is alu e

e o o e v .

S i ce t h e se umb r s a s f u d by a alysis s l d om a e w h l n umb e r s

n n e o n n e r o e ,

t h e f rmula wh i c h h as b en f u d i
o th is w a y s h oul d a lways be e o n n

ch e c ked up by c al c ula ti g th e pe r c e tag composi tion of eac h n n e

e lem t f r m th e fo r m
en ula s ob ta i e d a d c mpa r i g th valu s w i th
o o n n o n e e

t h s e f u d e p e r imen ta lly
o o n Th ey should agr ee wi thin the limi t
x .

o f e rr o r s e t f r th ab ove o .
 OR GANI C CO MBU S T I ONS 26 1

T hemol ecula r fo rmula c a o ly be ob tai ed af te r a mole cular

n n n

weigh t d t r mi a tio h a b ee mad

e e n n s n e .

S ome t ime s t h e mpi r ica l f r mula ca n n o t b e s e l c t e d si ce th e

e o e n

r e sul t s a e t oo c lo s e to seve r al p o ssibili t ie s

r I n t h is c a se s ome .

de r iva t ive of t h e subs tan c e sh oul d be ma d e a n d th e n an an alysis

ca rr i ed u t o th is n ew p r oduc t U sually th figu r e s s o ob tain e d
o n . e

cas is th e d t e r min a tion e e

e G l ikin Ch mi d sFe tt e L ipoide

e ,
e e er ,

33 4
—
5 w h e r e R e in it e r s wo r k is quo t e d ,
z
’

f rom M ou t h f te 9 a s e ,

X S o me Common E rr or s
. an d H ow to Avoi d T h e m

M an y ofrrors h ave alre ady b e en discuss e d in c on n e ct i on

th e e

wi th di ff e r en t p ar t s of th e app a ra tus th e m e t h od of ru n n in g ,

t h e c ombus t io n e t c an d m an y e rr o rs a r e p e rf e c t ly Obvi o us
,
.
,
.

Ye t it h as b e en ou r e xp e ri en c e t h a t dir e c t a tt en ti on mus t o f t en
be drawn t o s om e e rr ors b e f or e t h e y a re c orr e c t e d an d it is ,

t h e mos t obvi ous e rror which is s om e t im e s c ommi tt e d Th e r e .

fore all th at h ave b e en n o t ic e d in a c tu al w o rk are m en ti on e d .

R e a d o ve r o n c e a g a i n L ie big s a dvic e which is quo t e d a t th e

’

e n d o f th e hi s t oric a l i n t roduc t i on (p .

T he A pparatu s

1 . Do n ot u s e much sulfuric a cid in th e bubble coun ter

t oo .

I t may suck b a ck or b e spl a sh e d o ve r an d c aus e t r oubl e

wi th th e rubb e r tubin g an d s topp e r (p .

2 . T h e pre h ea t e r sh ould n o t be h ea t e d t o such an e x t en t t h a t

-

th e gl a ss t ub e m e l t s Wa t ch th e te mp e r a ture (p
. .

U s e h ea vy w a ll e d -
pre ssure rubb e r t ubin g Oth e r kin ds .

a re n o t gas t igh t an d d o n o t fit s n ugly Wire j oi n ts if .

,

n ec e ss ary wi th No 1 6 copp e r wire an d u s e a p air of

,
.
,

pli e rs t o tigh t en th e m (p .

S e e t h a t th e gl a ss s t opp e r s are prop e rly gr e as e d (p .

A t t a ch a pi e c e of twin e t o pr e v en t th e m fro m b e i n g blown

ou t in c a s e o f e xc e ss of pr e ssur e (p 2 2 9 .
,

U s e r e d r ubb e r s t opp e rs an d cl e an t h e m w e ll i n sid e a s w e ll

, ,

as o u t (p .
26 2 L AB OR A TOR Y M A N U A L OF OR G A NI C CH E M ISTRY
6 . C u t th e rubb e r s topp e r pro pe rly f or c on n e c tin g th e firs t
a bs o r p t i o n b o t t l e t o t h e c ombus t i on t ub e
(p .

D o n o t u s e a pi e c e o f gl a ss o r r ubb e r t ubi n g t o c on n e c t th e
firs t abs orp ti on b o t tl e wi th th e combus ti on t ub e (p 2 4 .

D o n ot fil l th e s t opp e rs o f th e a bs o rp ti o n b o tt l e s wi t h c ot ton
'

8 . .

T h e sp a c e is n e e d e d f o r th e dryi n g a g en t e sp e ci a lly in ,

th e s od a lim e b o ttl e (p .

D o n o t a ll ow th e tw o abs o rp ti on b ott l e s to c om e s o cl o s e
'

th a t th e en ds o f th e a rms a re chipp e d (p .

S ee th a t th e r e is sp a c e pr o vid e d a b ove th e p a ll a di ous chl o rid e

solu ti on f or a n y e m e rgen cy in ca s e o f b a ck pre ssu r e (p .

T he Chemic a l s

1 . P urify al l o xygen by p a ssi n g i t thro ugh th e p r e -h e a t e r

(p .

2 . U s e th e spe cifie d s od a lim e f or b o th dryin g an d abs orp ti on

t r a i n s (pp 2 2 9
.
,
S e e t h a t it is of p rop e r S iz e an d
m ois ture con ten t .

U s e th e s am e dryi n g a g en t in th e dryi n g t r a i n t h a t is us e d
in th e abs o rp t i on t r a i n (p .

D o n ot e xp e c t th e m a te ri a ls in th e dryi n g tr ai n to l a s t f or
e ve r .

Ke ep th e s top co cks of th e U tub e s in th e dryin g train

- -

cl o s e d wh en n ot in u s e (p .

6 . S e e t h a t th e c opp e r spir a ls a re pr op e rly m ad e an d fit a ll righ t

(p 23 5)
Do n ot u s e cupric oxid e wir e f or c arb on an d hydr ogen th a t
h as b een us e d f or d e t e rmi ni n g n i t r o g e n u n l e ss i t h a s b e en
,

r e t r e a t e d (p
-
.

8 . D o n ot u s e a lumi n a t h a t h a s b ee n h e a te d t oo l on g or t oo
hi gh (p .

K eep th e p all adi ous chl orid e s olu ti on s topp e re d excep t

wh en in u s e (p .

We ighi n g
1 . Us e aprop e r an aly tic al b al an c e an d if y ou ,
u se a rid e r ,
s ee

th a t i t is th e ri gh t on e f or y ou r b a l an c e .
264 L AB OR ATORY MA NU AL OF OR GA NI C CH E M IS TR Y
rubb e r s topp e rs in t h e p re h e a te r or f orw ard en d of th e
-

combus ti on t ub e I f th e rubb e r s t opp e r n ex t to th e dry

.

in g t r a i n in t h e p r e h ea t e r t ub e is burn e d s om e of th e g a s e s
-
,

may go thr ou gh th e dryi n g t r a i n i n compl e te ly abs orb e d ,

an d t h en t h e y will b e bur n e d in th e c o mbus t i o n t ub e .

T h e rubb e r s to pp e r sh o uld n o t b e c om e sp on gy .

T he Combu s ti on

Som e of th e t roubl e s m en tion e d u n d e r th e previ ous h eadin g

a pply h e re a ls o .

1 D o n o t f a il t o pr ove y our app a r a t us by ru nn i n g a bl an k

.

d e te rmin a ti on .

2 K eep en ough oxygen in th e app ar a t us to supply th e n eeds

.

a l l t h e t im e . S ee t h a t it is a lw a ys bubbli n g thr ough th e

p a ll adi ous chlorid e s olu ti ( o n p .

3 Do
. n o t t r y t o bur n t h e subs t a n c e t oo fa s t b e f o r e you a r e fully
a cqu ai n t e d wi t h th e app a r a tus .

4 R. e m e mb e r t h a t t h e c o mbus t i on n ee ds a t t en t i o n a ll th e t im e .

Do n o t try t o d o t o o m an y o th e r thi n gs a t th e s am e t im e .

T o o much e ff or t will b e l os t .

5 B. l a ck p a r t icl e s in t h e bo a t n ea r e n d o f th e combus ti on may be

carb on or cupric oxid e (p 2 5 .

6 D o n o t l e t th e sm a ll s e c t i on b e com e t oo h ot e sp e ci a lly a t
.
,

th e b e gi n n i n g (p .

7 I.f y o u w e igh t h e a bs o rp t i on b o t t l e w i t h th e li t t l e s t opp e r

f or on e arm d o n o t f ail t o k e ep it s af e an d w e igh i t a g a i n

,

wi th th e b o t tle la te r .

8 I t is m o s t d e sir a bl e a s a rul e t o run a bl an k d e te rmin a tio n

.

b e twe en tw o con s e cu tive c ombus ti on s si n ce all th e m ois ture

,

an d c a rb on di oxid e ma y n o t h a v e b ee n r e m o v e d e sp e ci a lly ,

if th e t im e a f te r th e subs tan ce h as b een burn e d is c u t

'

sh or t .

9 I.f t h e p e rc e n t a g e o f hydr o g e n i n a d e t e rmi n a ti o n is high an d

th e c a rb on l ow t his ma y b e d u e t o th e fa c t t h a t th e g a s e s
,

h ave n ot b e en compl e t e ly driven t hrough th e firs t b ottl e .

A t ta ch th e a bs o rp t i on t r a in t o th e d r yin g t r a i n p a ss th e ,

o xyg e n t hr o u gh f or tw e n ty min u t e s a n d w e i gh a ga i n .
 OR GANI C CO MBU S T I ONS 26 5

XI . Comb u s ti on of S u b s ta n c es in in g
Con ta N itr oge n , S ulf ur ,
H a l og e n s , P h os ph o ru s S od ium
, , e tc .

Nitr oge n — Wi t h
c tive ca talys t an d pl en t y of oxygen
an a ,

th e n i t r og en is oxidiz e d t o n i t r o g e n di o xid e This is t r u e e ve n .

wi th subs tan ce s c on tain in g n i trogen in th e s o ca lle d u n oxi -

diz e d fo rm a s in a min e s amid e s e tc Ni t roge n di oxid e is

, , ,
.

abs o rb e d m o r e o r l e ss by th e dryi n g a g e n t a n d c ompl e t e ly

a bs orb e d by s od a lim e Th e r e fore it is n e ce ss a ry to k e ep it

.

from goin g i n to th e abs orp ti on t rain L e a d p e r oxid e (P bO ) .

z
1
,

k ep t a t 3 00 is th e b e s t m e a n s of fixin g th e n i trogen
° ”

di oxid e an d pre ven tin g it from l eavin g the combus ti on t u b e .

T h e t e mp e r a tur e mus t be t ri e d ou t a h e a d o f tim e t o fin d ou t

th e w orki n g c on di t i on s T o o high a t e mp e r a tur e (a b o v e
.

will caus e th e d e comp o si ti on of th e l ea d n i t ra te which is

‘

f orm e d an d a ls o will con ve r t th e P bO i n to P b O S in c e

, z u 4 .

w ate r vap o r a c t s up on l ea d n i t ra t e gi v i n g a b a sic n i tra te a n d

lib e ra tin g ni tric a cid which is n o t al l r e abs orb e d by th e l ead
p e roxid e it is n e ce ss a ry to mix an e qu al am oun t of P b3 04
,

( mi n ium ) wi t h t h e l ea d p e r o xid e S o m e P b 3 04 f o r u s e c an .

rea dily be ob ta in e d by h ea tin g s om e of th e l e a d p e roxid e in a

tub e or op en dish t o 400
°

T h e l e a d p e r oxid e mix tu r e ( 7 8 gr a ms) is pl a c e d in a tub e o f

—

h ard gl a ss Fig 1 9 wh ich fits th e combus ti on tub e sn ugly a n d

,
.
, ,

p u t in p o si t i on F a s sh o w n o n th e gen e r a l di a gr a m p 23
3 ( s ee ,
.

als o p . Or i t is pl a c e d in a l a rg e b oa t 1 4 cm l on g p r e f ,
.
,

e rabl y wi t h th e en d op e n (br ok en o ff ) t o w a r d th e c a ta lys t

?

L e a d p e r oxid e is v e ry hy gro scopic an d c a r e mus t b e us e d in

han dlin g it an d provi n g it in th e bl an k ru n I t mus t b e ve r y
F

pure fre e from an y o rgan ic p ar ticl e s such a s dus t fib e rs from

, ,

1 L p eroxi de w as used by L i ebi g a n d c on te mp ora ry w orke rs in o rga n i c

e ad

c omb us t i o n s t o ab s orb ac i d i c ga s e s a n d in 1 8 7 6 by K opf e r w h e n h e i n t rod u c e d t h e

, ,

c a t a ly t i c me t h od ( p b u t D e n n s t e.d t h a s d o n e t h e b e s t w o r k on h ow t o u s e

it. S e e h is An lei t un g zur vere in fac ht en E lemen taran alyse 3 Aufl ,

”
.

66—7 0 , 9 0 .

2 L e ven e an d Bi
r Jou r n A mer Chem S oc 40 e be ,
. 4 6 0 re c o mme n d
. . .
, ,

put t i n g th e l e ad pe roxi de di re c tl y i n t o t h e t ube w i th a l te rn a t e la yers of a mix t ure

of it w i th a sbe s to s ,
 26 6 LAB ORAT OR Y MANUAL OF OR GA NI C CH E M I S T R Y

fil te r p ap e r e tc I t mus t a ls o be f r e e from l e ad oxid e sin ce

, .

t his a bs o rbs c a rb on di o xid e a t a hi h t e mp e r a tur e 1

g .

T h e c ombus ti on mus t be r un sl ow e r th an wh en th e subs tan c e

c on tain s n o n i trogen ?

Cupric o xid e a ls o abs o rbs n i tr og en di oxi d e T h e copp e r .

n i t r a t e f o rm e d is on ly S l owly d e c omp o s e d a r o u n d an d if th e

l a t te r p a r t of th e cupric oxid e jus t pre cedin g th e le ad pe roxid e

mix tur e is n ot we ll h e a te d b e twe en combus ti on s th e n i tra te ,

ma y a ccumul a te t o such an ex ten t t h a t i t will e n ti r e ly bl ock

t h e c ombus ti on t ub e 3
.

7 215 5 F OR LE A D s on a E M/x r un z
FI G . 19

N OT E S

1 . l ctrolytic p r epa r a ti of th l ead p e r o ide y ou a e

For th e e e on e x r

r ef rr d t o D e
e e t e d t s b ook m ti d ab v p 6 5 a d t K i g
nns
’
en on e o e, . 2 n o n

sc o t t a d K igh t M thod s of Qua t i ta t iv Orga i c A aly is

n n ,
e n e n n s

35
2 . For o th e r me th o ds of c o mbus t in g o r gan ic subs ta c s o t ai n e c n n

in g i t r oge s e e G at t ma
n n, er nn ,
“
P r ac t i c a l M e t h d s f Or ga ic o o n

Ch mis t r y m r spe c ially F G B e dic t

”
e 3 d A ,
E d e . .
,
a d n e ,
. . en ,

E l e me t a r y Or ga i A a ly is
n 5 9 64
n c n s
—
.

3 F. o e t i m art i g c a r
s b o h y d r g an d i t r ge si mul ta e usly n, o en , n n o n n o ,

s ee D e te d t a d H a s l r B
nns 41n 77 8 s e ,
er .
,
2 .

S ul f ur F o r d e te rmi n i n g c a rb on an d hydr og en by th e c a tal y

.
—

t ic m e th od wh e n th e subs t a n c e c on ta i n s sulfur th e s am e p r o ,

c e d u re 15 us e d a s a b ov e wh e n n i t r o g e n is p r e s e n t Th e sulfur
.

is fix e d as l e ad sulf a te .

1
L ss r C h Arb i t sm th d Allg m i T h il 4 A fl
a a -
o n, e 86 e o en , e e ne e ,
u . 2 .

2
R e me i r ,
“
On R a pi d Orga n i c Comb us t i on s ,
”
Jour n . A me r . Chem S oc
. .
,
37
1 6 3 6—8 .

3
Fish e r and Wri gh t ,
J ou r n , Amer Chem S oc . . .
,
40 8 68 ,
26 8 LAB ORAT ORY MANUAL OF OR GANI C CH E MI S T RY
fil e m ark an d the bulb a n d th e pi e ce a re pu t in to th e
,

in such a w ay t h a t t h e t ub e will r e s t o n t h e e n d o f th e
n ea r th e c e rium di oxid e an d imm e di a t e ly pla ce d in ,

combus ti on tub e I t is sl owly dis till e d ou t an .

usu a l m ann e r P ar t c l e s of gl ass in th e bulb aid i

'

t ill a tion (sugge s t e d by M s E M S l o cum ) T he . . . .

sh ould n ot of cours e be allow e d to be c arb on iz e d

, ,

bulb .

'
A sm a l t hi n w a ll e d gl a ss bulb 3 5 mm in
.
1 — -
,
.

as is of ten e mpl oy e d f or m ole cul ar w e igh t

by th e vap or d e n si ty m e th od is use d I t is ,
.

it wi th th e op e n c apill a ry t ub e dippi n g i n to th e liquid

an a lyz e d c on t a i n e d in a dish i n sid e a v a cuum d e sicc a t o r
,
T he , .

suction is the n turn ed on an d a f te r a f ew min u te s air is allow e d

t o r e e n t e r th e d e sicc a t o r This caus e s th e liquid to be drawn
'

-
.

i n to th e bulb T h e bulb sh ould be w eighe d b e fore an d a ga in

.
,

a f t e r s e a li n g .

Ve ry l ow b oilin g liquids mus t be driven in t o th e c ombus t i on

-

t ub e s om e wh a t a s in th e c a s e wh en a gas is an a lyz e d They .

o f t en f o rm e xplosiv e mix t ur e s .

R E F E R E N CE S

B en e dic t l oc c i t ,
. .
,
—
73 9 ; Cl a r k e , No t e on th e combus tion of

volatile or gan ic li qui d s .

”
J ou r . A mer Chem S oc
. . .
,
34 7 46
-
7 .

G as e s . S in c e
gas e s form e xpl osive mix ture s wi th oxygen ,

th e oxyge n mus t a lw a ys be in v e ry gr e a t e xc e ss wh en t h e ga s is
sl owly b e in g driven in t o th e combus ti on t ub e T h e ga s is he ld .

in a ga s bur e t te in which it is m e a sur e d an d sl owly s e n t thr ough ,

a c apill ary t ub e in t o th e c o mbus t i on t ub e A l on g cupric oxid e .

spiral n ea r th e e n tran ce h e lps to caus e th orough mixin g an d t o

pr even t b a ck firi n g “
.
”

1
T h is s mall b ul b foll ow s : He a t an d d ra w ou t a pi e c e of ordi n ary
c an be ma d e as

gl a s t ubi n g a n d c u t o ff on e e n d o f th e n a rro w t ube a t t h e s h o ul d e r T h e n softe n

s
.
,

in th e fl ame t h e e n d w h i c h h a s be e n c u t off an d w i t h t he o t he r en d a s a mo u t h , ,

pi e c e bl ow a bulb I t is c ompl e te d by c utti ng th e n arrow tube a t the de sired

,
.

le n gth .
 R GA NI C C OM B USTI ONS
O 269

x lo s ive S ub s ta n c e s Th e s e are we igh e d ou t a s usu al in a

E p .

o a t a n d t h e n mix e d wi t h t hr e e o r f o u r v o lum e s o f cupric oxid e

( which is fr e e fr o m m o is t ur e e t c ) o r qu a r t z s an d ,
. .

D I VI S I ON B

THE D E T E RMI N A TI ON OF NI TR OG E N

I . H i s tori c al I n tro d u c tio n 1

Gay L uss a c -
Th en ard ( 1 8 1 0) we r e th e firs t to d e term i n e
an d

n i t r o g en in o rg an ic subs t an c e s Th e ir m e th od con sis te d in burn .

in g th e subs t an c e in th e pr e s e n c e o f p o t a ssium chl o r a t e an d

a n a lyzi n g th e g a s e s e volv e d (c omp a r e c a rb o n a n d hydr o g en ,

L a t e r ( 8 1 5 ) cup r ic o xid e w as in tr o duc e d by t h e m

1

is s till us e d up to th e pr e s e n t tim e L i ebig us e d this .

s am e m e th od imp r ovi n g it s o tha t h e could colle c t an d we igh

,

t h e w a t e r an d c a rb on di o xid e an d m e a sur e t h e n i t r og e n a s a ,

g a s . Dum a s bur n e d t h e subs t a n c e I n a n a t m o sph e r e o f c a rb o n

2

di oxid e pr ep are d fr om l ead c arb on a te in th e en d of th e cl os ed

,

t ub e an d c o ll e c t e d th e n i t ro g en in a e udi om e t e r o v e r m e rcury
,

a n d a s o lu ti o n o f p o t a ssium hydr oxid e t o abs o rb th e c a rb on

di oxid e H e a ls o us e d r e duce d c opp e r to r e duce an y oxid e s of

.

n i t r o ge n which ma y b e f o r m e d Thus h e la id th e compl e te .

fou n d a ti on of th e m e th od which is th e m o s t gen e ra l an d wh en ,

prop e rly c arri e d ou t a s a ccur a te for n i trogen a s an y ye t d e vis e d

,
.

E rdm ann a n d M arch a n d 3

us e d an ou t sid e ge n e r a tor f or th e
carb on di oxid e an d H ugo S chiff d e vis e d th e az otom e te r
4
,

which h as b e en such a gr ea t h e lp in h an dli n g th e gas e s I t is .

o f c on sid e r abl e i n t e r e s t t o n o t e h ow th e a z o t o m e t e r w as d e ve l o p e d

an d m o difi e d T h e r e f e r en c e s f or th e di ff e r e n t f orms (an d e a ch

.

re fe r en c e con tain s a sk e t ch of th e app ar a tus f or which th e

a u t h o r is sp on s o r ) are f o u n d in D e n n s t e d t s his t o ry p 40 a n d
’
.
, , ,

1
D t dt
enn s eD i E t w i k lu g d
,
rg is h E l m t r lys Ahr
e n c e n er o an c en e en a ana e,
’
en s

S mmlu g h mis h r d h mis h t h is h r V r trag

”
a n c e c e IV
un c9 e c -
ec n c e o e, 2 .

A n n Chi m phys h is t o ry , p
’
2
. . .
,
2 198 ; D e nn s t ed t s .
35 .

3
J pr Chem , 14
. . . 2 13 .

4
Z e its c hr . a n al . Chem , 7 .
43 0 .
27 0 LAB OR A T OR Y M A NU AL OF OR G ANI C C H E M IS T RY
.

R ich te r s Organ isch e Ch emi e M

’
Au fl I 7 a,g 11 .
, .

n e s it e (m a gn e sium c a rb on a te ) l a te r displ a c e d th e l e a d a n d o th e r

c arb on a te s an d is m os t gen e r ally us e d wh en th e subs tan ce is

burn e d in a clo s e d tub e 1
.

M an y o rg an ic subs tan c e s wh en h e ate d e xp e ci ally in th e pr e s ,

en c e o f s o d a li me giv e up t h e ir n i t r o g en a s a mm on i a o r s om e
, ,

simple a min e This m e th o d w a s us e d for th e d e t e rmin a tion of

.

n i t r o gen by Varr e n t r app an d W ill in 1 8 4 1 T h e a mm on i a 2

.

f orm ed is abs orb e d in a kn own am ou n t of s tan d a rd a cid an d the

e xc e ss o f a cid t i t r at e d b a ck wi t h a lk a li From this th e am oun t .
,

o f a cid n e u t r a liz e d by th e a mm on i a is o b t ai n e d a n d th e a mm on i a

a n d n i t r o g e n c an th en be c a lcul a t e d This m e thod is n o t .

a pplic a bl e t o subs t an c e s in which th e n i t r og e n is in such c om ~

bi n ati on as in th e n i t r o group azo group e t c -

,
-
,
.

S o me f o r ty y ea rs l a te r in 1 88 3 Kj e ld ahl br ough t f or th an
3
, ,

o th e r m e t h o d which on a cc ou n t of i t s e a s e o f m an ipul a ti on an d

applic abili t y t o m an y subs t a n c e s which a r e a n a lyz e d f o r n i t r o ge n

in gr e a t n umb e rs h a s b e en o f i n e s tim abl e s e rvic e

,
T h e Kj e ld a hl .

m e th o d con sis t s of h e a tin g th e subs tan ce wi th con c sulfuric .

a cid usu a lly in th e pr e s en c e o f a c a t a lys t such a s a m e rcury s a l t , ,

p o tassium p erm an gan a te or cupric sulfa te This pro ce dure .

con ve r t s th e ni trogen in to a mm on ium sulfa te T h e mix ture is .

t h en dilu t e d m ad e s t r on gly a lk a li n e wi th s o dium hydr oxid e

, ,

a n d dis t ill e d T h e s olu ti on o f a mm on i a which c on s ti tu te s th e

.

dis till a te is colle c te d in a d e fin i te a m oun t of s tan d ard a cid an d

th e a n a lysis c ompl e t e d by b a ck t i t r a t i on e t c a s o u t li n e d in ,
.
,

t h e pr e vi ous p a r agr a ph S om e subs t an c e s e sp e ci a lly th o s e wi th

.
,

th e ni t r ogen in th e ri n g a re n o t c ompl e t e ly d e c omp o s e d by th e

m e t h o d Oth e rwise by diff e r en t m o difica ti on s for i n crea si n g
.
,

th e t e mp e r a tur e by a ddi n g p o t a ssium hyd rogen sulf a t e by ,

r e duci n g ni tro comp ou n ds jus t pre vi ously e t c th e m e thod

-
,
.
,

h as f ou n d wid e applic a t i on .

Wi thi n ve ry r e ce n t ye ars micro m e th ods for de term1mn g -

1
T h is
is me th od o u tli n e d in Ga tt e rman n ,
th e P ra c t i c a l M e th o d s of Organ i c
Ch e mis t ry
”
3 d m,
e r E d A 9 0 . . .

2
A n n Chem P ha r m , 3 9
. . 25 7 . .

3
Z e its c hr a n al Che m 22
. .
3 66 . .
27 2 LAB OR AT OR Y MAN UAL OF OR GANI C CH E MI S TRY
R ubb e r pre ssure tubin g (p .

On e U -
t ub e wi t h g r o u n d gl a ss s topp e rs
, ,
12 .
5 cm (5
. i n ch e s )
( p .

G l a ss b ea ds f o r th e U t ub e (p -
.

On e p orc e l ai n or qu ar tz b oa t (pp 2 84 .
,

On e sp e ci a l w e ighi n g tub e b oa t tub e piggi e (p 2 ,

.

Az o t om e t e r 5 0 cc gradu ate d to
,
cc a n d r e se rvoir
.
,
.
,

(p .

Carb on di oxid e g en e r a tor (p con sis tin g m ain ly of .

a E rl en m e ye r fil teri n g fl a sk 7 50 cc
.
,
.

b Dr oppi n g fu n ne l 2 00 cc
.
-
,
.

c S tou t s a fe ty b o t tl e ab o u t 2 00 cc
.
,
.

d B ulb e d t e s t tub e 6 i n ch e s
.
-
,
.

e Capill ary t ub e
. .

S even s top c o cks -

.

E rl e n m e y e r fil te ri n g fl a sk (in c on n e c ti on wi th m an om e te r)

( p .

M an om e te r s tan d (p .

On e l e n gth of gl a ss t ubi n g f or m an om e te r ab ou t 1 40 cm , .

Wa t e r pump or oil va cuum pump (p .

Th e rm om e te r (p .

Crucibl e t on gs .

On e p air o f pli e rs .

D e sicca tor .

—
M e rcury 4 50 500 gr ams (pp 2 7 5 2 8 1 .
, , ,

On e t e s t t ub e o f P yr e x gl a ss f or th e r e duc e d copp e r spir a l

-
,

(p
Gl a ss w oo l or a sb e s to s f o r th e a b ov e (p . 28

S t op c o ck gr e a s e E
—
,
. A .
(p .

Chemi c a l s
0

1 . 1 00 gr ams of cupri c ox1de w i reform , .

2 . P u r e s o d ium bic a r b on a t e 00 gr a ms f or e a ch d e t e rmi n a t i on ,

1 .

3 . Con c sulfuric a cid f or u s e in g en e r a to r a n d U —tub e

.
, .

T ho se pi e c e s o f a pp ara t us w h i c h a re s t arre d a re t h e sa me a s on th e lis t

for th e c arbo n an d h y drogen d e t ermina ti on a n d iv pp —
g en on 2 2 3 4 , . .
 OR GANI C CO MBUS TI ONS 27 3

P o tassium hydr oxid e ( 1 00 gra ms d iss olve d in cc wate r

1 00 .

m ak e s a s olu ti on which is good f or t w o d e te rmin ation s) .

I II . T o pi c al Outl i n e of G e n e ral M e th o d of P r o c e d ure

S et up th e e l e c tric combus ti on furn ace (p .

S e l e c t th e c ombus ti on t ub e a n d if n e ce ss ary c u t to prop e r

,

l en g th an d roun d th e e dge s (p
“
.

Fill th e combus tio n tub e (p .

A ss e mbl e th e c arb on di oxid e g e n e r a t or (p th e m an om

.

e t e r (p . an d a ccomp an yi n g s top cocks an d U t ub e - -

( p .

Cl ean a t t a ch an d t e s t the azo tom e te r (n i trom e te r) (p 2 8

, ,
.

P r ep a re th e c arbo n a t e mix tur e an d I I sulfuric a cid for th e

g en era tor (p . an d th e m e rcury a n d th e 1 1 p o tas

s ium hydr oxid e so lu t i on for th e a z o to m e t e r (pp 2 86 .

P r ep ar e th e cupric oxid e wir e in th e c ombus t i on t ub e by

h ea tin g it u n d er dimin ish e d pr e ssur e an d a ll owi n g it to
”

cool in a n a tm osph e r e of c a rb on di oxid e (p .

Te s t th e en t ir e appar a tus (p .

P r ep a r e th e r e duc e d c opp e r spir a l an d a ll o w it to c ool (p 2 8 , .

We igh ou t th e subs tan c e (p .

Th e c o mbus ti on p r op e r (p . th e fur n a c e c an b e cold or

h o t a t th e b egi n n in g (p .

a I n s e r t th e b oa t c on ta i n i n g th e subs tan c e (pp 2 94

. .

b I n s e r t th e r e duc e d c opp e r spir a l (pp 2 9 4

. .

c Con n e c t up th e e n t ir e a pp ar a tus e va cu a te an d flood

.
, ,

wi t h c arb on di oxid e (p .

(1 H e a t th e r e duc e d c opp e r spir a l t o r e d n e ss f or ab ou t

.

fiv e mi n u te s in ord e r t o driv e ou t occlud e d g as e s

6 T e s t wi th azo tom e t e r full o f th e potas s iu m hydr oxid e

.

s olu t ion to s e e if a l l n on abso r b abl e ga s e s h ave

-

b e e n r em ov e d f r om th e app a ra tus or r e duc ed to ,

a mi n i mum (pp 2 9 5 .

ea t th e l ay e r o f cupric o xid e wir e t o r e d n e ss b e i n g

f H .
,

c ar e ful n ot to burn th e subs t an c e (p an d a t .

th e s a m e tim e
27 4 LAB OR ATOR Y M AN UA L or OR G A NI C CH E M IS TRY

g R
. e duc e t h e flow o f c a rb on di o xid e t o such an ex ten t
t h a t i t will jus t k ee p th e p r o duc t s o f c ombus tion

m o vin g towa rd th e az otom e te r usin g th e s topp e r ,

in th e U tub e f or r e gul a t i n g th e gas (p

-
.

an d a ll owi n g th e e xc e ss o f c a rb on di o xid e t o e sc ap e

thr ough NO 2 (p . .

h S l owly h ea t th e oxidize d c opp e r spir al an d th en com

.
,

bus t th e subs tan ce (p .

i Drive ove r al l th e r e m a i n i n g n i t r o g en gas wi t h c arb on

.

di oxid e by gra du a lly i n c r e a sin g its flow (p .

j .C l o s e s t op c o ck N o 6 (b e t w ee n th e a zo t om e t e r a n d
-
.

th e c ombus ti on t ub e ) w a sh th e gas in th e azo t om

,

e t e r wi th o n e p o r ti on o f t h e p o t a ssium hydr oxid e

s olu ti on whil e th e r e s e rv oir is in th e l ow p osi ti on

,

( I ),
a n d t h e n w a sh wi t h c o ld dis t ill e d w a t e r which ,

h as b e e n r e c e n t ly b oil e d t o driv e ou t diss olv e d air ,

u n til al l th e p o ta ssium hydroxid e s olu ti on is ou t

o f th e a z o t om e t e r a n d th e r e s e rvo ir (p .

k.L e ve l th e liquid in t h e r e s e rv oir an d th e az o tom e t e r ,

pl a ce a the rm om e te r in th e wa te r in th e top of th e
a z o t om e t e r an d a f t e r t w e n t y t o thi r t y mi n u t e s
,

r e cord th e volum e of th e gas by r eadin g the l owe r

m en iscus th e tempe ra ture an d th e corre c te d
, ,

b a rom e te r r e adin g (p .

l Calcul a t e th e p e rc en t a ge of n i trog en (p
. .

ord e r to h ave th e tube r eady f or an oth er combus tion

'

In ,

r em ove th e r e duce d copp e r spir a l draw air th r ough th e

,

t ub e whil e it is s t ill h o t in o rd e r t o oxidiz e th e c opp e r th a t

h as b ee n r e duc e d in t h e c ombus t i on t h e n fl oo d th e app a
,

r atus wi th c arb on dioxid e Now it may b e us e d aga in

.

a t o n c e o r i t c an b e cl o s e d 03 a n d th e cup r ic o xid e a ll ow e d
,

to cool in th e a tm o sph e r e of c a r b on di oxid e (p .

27 6 L AB OR A TORY M AN U A L or OR GANI C CH E M I S TRY
grams) of m e rcury This a c t s a s a s af e ty ou tle t for th e e xce ss
.

o f c a rb on di oxid e Ge n e r a lly th e tub e fr om th e s t op c o ck sh ould -

.

d ip ab ou t 3 5 4 cm in to th e m e rcu r y
—. . T h e bulb in th e te s t
.

tub e pr e ve n t s th e m e rcury fr o m spl a sh i n g o u t o f th e t ub e. T h e

f
t op o th e t e t s t-
ub e S h o uld b e l oo s e ly p a ck e d wi t h c o tt on t o

preven t fin e p ar ticl e s of m e rcu r y from b e in g thr own ou t T h e .

e mp t y b o t t l e s e rv e s a s a s a f e t y b o tt l e t o pr e v e n t a n y of th e

me r cu r y fr o m b e i n g dr a w n i n t o t h e g e n e r a t o r in c a s e t h e s t op
c o ck is n o t cl o s e d a t th e p r op e r tim e W h en e ve r c a r b on di oxid e
.
 OR GANI C CO MBU S T I ONS 27 7

is b e in g p a ss e d through th e app ar a tus u n d e r its ow n pre ssur e ,

s top cock N o 2 sh ould always be l e f t op en in ord e r th at an y

-
.

e xc e ss of pr e ssur e c an b e t ak e n c ar e o f .

A c apill a ry t ub e 1 mm i n sid e di am e t e r b en t upw ards a t th e

,
.
,

l ow e r en d is at ta ch e d t o th e s te m of th e dr oppin g—funn el } an d
, ,

is arran ge d t o d e live r th e a cid b en e a th th e surf a ce of th e bicar

b on a t e mix ture This in sur e s a m ore e ven ge n er ati on of carb on
.

dioxid e an d b e tt e r c on tro l th an wh en th e a cid is all ow e d t o drop

from th e s te m T h e upwa rd b en d pr e ven ts th e carb on di oxid e
.

from goi n g up th e s t em of th e dr oppi n g fun n e l M odificat ion s -

.

will of course sugge s t th ems e lve s t o e a ch op e rator for his c on

, ,

v e ni en c e .

On e hu n dre d grams of pure s odium bicarb on a te an d 1 00 cc of .

re cen tly boil e d an d cool e d w ate r are us e d a s a si n gle ch arge for th e

g en e r ator This is n o t en ough w a te r t o dissolve all th e bic a r
.

b on a te bu t is su ffici en t for the purp os e The bi c arbon a te mixtu re

,
.

s hou l d be re moved an d fres h ma teri al pu t i n after eac h co mbu s ti on .

Oth e rwis e th e supply of carb on di oxid e may fail a t a cri tica l tim e
wh en th ere is n o p ossibili ty of m aki n g th e ch an ge On e hun dre d
‘

an d fif t y cc o f a mix t ur e o f o n e p a r t o f c on c sulfuric a cid an d

. .

o n e p a r t o f d is t ill e d w a t e r in th e dr oppi n g fu n n e l will s e rv e f or -

a t l ea s t tw o c ombus ti on s .

S o dium bic arb on a te an d w a t e r r e a c t t o giv e c arb on di oxid e

e v e n at th e o rdi n a ry t e mp e r a t ur e a n d a t e l e v a t e d t e mp e r a t ur e s
,

th e bic a r b o n a t e is r apidly c on v e r t e d in t o th e n o rm al ca rb on a t e .

R e duc ti on of th e pr e ssur e pr o duc e s th e s am e r ea c t i on a t l o w e r

t e mp e r a t u r e s as will b e n o t ic e d durin g th e op e r a t i on
,
.

P o tassium c a r b o n a te dvan t age ove r s odium bicar

h as an a

b on a te a s a s o u r ce o f CO in th a t it c an be us e d in a f a irly c on
2

c e n t r a t e d s ol u ti on T h e s o lu ti on o f th e c a rb on a t e is m a d e up
.

wi th a sp e cific gra vi ty ( 1 4 5 s om e wh a t g r ea te r th an th a t
o f th e sulfuric a cid a n d t h e c a rb on a t e s o lu t i o n is pu t i n t o

th e dr o ppi n g fu n n e l i n s t e ad of th e fil t e r fl a sk o f th e ge n e r a t o r
-

d e scrib ed ab ove T he carb on ate s o lu ti on of sp gr

. . .

1
The j oi n t s sh ould be w ired si n c e
, th e rubbe r gra d u ally sw ells an d bec ome s
27 8 LAB ORAT OR Y MANUAL OF OR GANI C CH E M I ST RY
c on t ai n s 43 4 7 p er c en t of po ta ssium ca rb on a t e an d is prep are d
—

by di ss olv in g ab ou t 8 5 9 0 g r ams o f dry pu r e n o rm a l po ta ssium

—

ca r b on ate in 1 00 cc o f r e cen tly b oil e d w a te r an d th e sulfuric

.
,

a cid s o lu t i on is pr e p a r e d by mi xi n g 00 cc o f c on c sulfuric a cid 1 . .

an d 1 00 cc of w at er T h e re l a t ive sp e cific gravi ty of th e

. .

c a rb on ate solu ti on wh en c old c an be t e s te d if a hydr om e ter is

, ,

n o t a t h an d by se e in g if a dr o p o f br omb e nz en e

o r o f chl o r o f o rm si nk s an d a dr op of e thyl br omid e

j us t fl oa t s in it provid ed o f cours e th e in flu en ce of , , ,

su r f a ce ten sion is gu ard e d agai n s t by s tirri n g S in c e th e c ar .

b o n a te s olu tion diss olve s c a r b on di oxid e wi th th e f orm a ti on

o f th e bic a rb on a t e which is much l e ss s o lubl e t h a n th e n o rm al

c a r b on a te a n d crys ta lliz e s ou t a n d si n c e this abs o rp ti on produce s ,

a p a r t i a l v a cuum th e su r f a c e o f t h e s o lu t i on sh o uld b e c ov e r e d
,

wi th a thi n l aye r o f p e trol e um oil to pr e ven t a cce ss of th e 1

c a r b on di oxid e to th e li quid .

A g e n e r a t o r wi t h a spe ci a l s t op c o ck f o r dr oppin g th e liquid

2 -

a rr an g e d f o r e qu a lizin g t h e pr e ssu r e a b ov e an d b e l o w t h e o u t l e t

in th e s t op c o ck is sh own in Fig 2
— T h e e qu a lizi n g is d on e . 1 .

t hr o ugh a c on n e c t i on m a d e by m e an s of th e a n n ul a r gr oove
in th e ke y o f th e s t op c o ck N O m a t te r whi ch p o si ti on th e
-
.

ke y o ccupi e s t h e r e is a lw ays c ommun ic a ti on b e tw ee n th e a tm o s

h r e in t h e l o w e r fl a sk a n d t h a t in t h upp r fl sk O
p e e e a n e .

a rm o f th e s t o p c o ck is e x te n d e d un t il it op en s a b o v e t h e liquid
-

in th e upp e r c on t a in e r N o ou tsid e c onn e c ti on is n e c e ssa ry

. .

T h e liquid e n t e rs a t a n a p e r tu r e in th e l ow e r p a r t o f th e e x
t e n d e d arm a n d is d e liv e r e d t hr ough a sm a ll gl a ss t ub e s ea l e d in
a t t his op e n i n g T w o s tyl e s o f s t op c o cks a re sh own i n th e
.
-

di agr am usin g th e s am e ge n e r al p r in cipl e in ea ch

,
.

I f t h e fl a sks a re us e d a s sh o wn th e y mus t b e s e cu r e ly f a s t e n e d
by cl amps cl o se to th e lips T h e upp e r fl a sk c an b e fil l e d th r ou gh .

1
Co mpa reWa t so n S mi th Jr Qua n t i ta t ive d e te rmi n a t i o n o f t h e c a rbo n yl
,
.

gro up in Al de h yd e s K e t o n e s e t c
,
Che m N ew s 9 3
,
8 3 ; w h e re p a ra ffi n o il
. .
,

is use d t o pro t e c t Fe h li n g s so lu t i o n fro m a b so rb i n g c a rbo n d i o xi d e

’
Al so give n .

in H M e ye r An alyse un d Kon s tit u tionse rmit tel un g o rgani sc he r Ve rbi n d un gen ”

.
, ,

2
F heis r Jou
,
rn . I nd . a nd E n g Chem , 10 . . 1 0 14 .
280 L AB OR A TORY MANUAL OF O R GANI C CH E M IS T RY

FUR TH E R N O T E S AN D R E FE R E N CE S

F . B l au 1
used th e p o ta s s ium c a r bon a t e an d s u lf u icr ac i d a s de
s c r ib e d a b ov e . He f ou n d th a t 5 —
0 1 00 c c . of th e c a r bon a t e s o u t on l i
w as n e e de d to dr i
ppa r a tus a d ly ab ut c c
ve th e a ir o u t of th e a n on o 20 .

w as n e e d d f o t h e c ombus t i o
e p r p r Thi s la tt r am t in a
r n o e . e ou n

bla k n yi ld d o ly
ru n e c c f u ab s orb d ga i th a o t om
e n . o n e s n e z

e te r a th o r s e xp e r i e c e h as b ee simila r B lau r marks

’
a d th
,
n e u n n . e

th a t it is n t e c e ssa ry t o boil t h
o n on c n t r a t e d c a r b a t e s lu t i on e c e on o

si c it abs rbs a muc h small r a m t of ai th an an e q al volume f

n e o e ou n r u o

wa te r a d o ly a small volum is us d H a dds th a t a mor e dil te

n n e e . e u

solution c a o t be us d w i th out h avi g b en boil d si c it abs rbs

nn e n e e ,
n e o

a l a r ge a mou t f ai an d mor eove r gr a t e r a moun t s f th e s olu ti on

n o r e o

mus t b e se d u .

Y u g a d Cau dw l l
o n used potassium c a rb ate also in th ei r
n e
2
on

g e
ne r a t r T h eoy f u .d t h a t t h e c a r b o o d i o i dn f r m e d in t h is n x e o

ma nn e r d e s o t c t ai o c c n f ai p 5
on li t r s w h i c
n h m a n s a n . o r er e ,
”
e

impur i ty of less tha pa r t i (c mpar b low a d p

n 1 n o e e n .

Fi l d
e a d T ayl r
n er us d th is me th od a d s ta t th at th r e w as
n o
3
e ,
n e e

little difficulty i c l r i g th l d tube f a i s th a t th C0 w a s n ea n e c o o

_
r o e 2

c ompl e t ly abs r b e d a d y e t in r eply t o a l tt r f r om th e a u th o r

”
e o ,
n e e ,

D r Fiel d e said th a t th y t r i d th r sampl s of p ta ssium ca rb on

. n r e e ee e o

at e b efor th ey ob ta i d c arb o di id th a t gave o ly a min imum

e ne n ox e n

of t i y bubbl s wh i c h w r e
n v r t ta lly abs rb d
e e ne e o o e .

T h e pu r e s t c a r b d i i d th a t h a v r b e Ob ta i d an d
on ox e s e e en ne

a c c u r t ely a aly d a d r c o r d d w s p r p r e d by Br a dl y a d Hal e 4

a n ze n e e a e a e n

in c c ti
on n e w i th w o r k o on physic l c sta ts of th gas They n a on n e .

us d sodium bi a rb t i th f r m f a paste a d c c sulfu r ic

e c on a e n e o o n on .

ac i d I .
gua r d i g a g i t imp u r i t i s f r m t h a i th y f u d it
n n a ns e o e r e o n

ev e n e c e ssa r y t o pl ac e m r c u ry jac k t s a r ou d al l r bb r c on e c
n e e n u e n

t ion s si c e a i d iffus e s i as w ll a c a r b
n r d io i d e di ffus s ou t th r ough
n e s on x e

t h e r ubb r I th i r a r t i c l o th r r c r de d a t t mp t s t p r p a r e pu r e
e . n e e e e o e o e

C0 a 2 g i re a d d is c uss e d
v en n .

S dium b i c a rb a t e i t h e f rm f dry p ow de r h a s b en use d

‘

o on n o o e

in co ec ti nn w i th it r oge d t r mi a tion s i th e ope tub e me th od

on n n e e n n n -
.

1
M on ats hef te f u r Chemi e , 13 27 7 .

2
App r us f or
a at th e S upply of Ca rbon D i oxi de in th e D e t e rmi n at i on of
Ni t rogen in Orga n i c C o mpo un d s by t h e Ab solute M e thod Jou rn S oc Chem ,
”
. . .

I nd .
,
26 1 84 .

3
Jou rn . I nd . a nd E n g Chem , 7
. . 1 09 .

4
J ou r n . A mer Chem S oc . . .
,
30 1 09 0 .
 OR GANI C C O M B U S TIO N S 28 1

It is h ea te d in a s ep r
a a te tu b e . D en n s t e d t 1
s lec ted
e th i sub
s s ta n c e

f or his wo rk . G a t t e r ma n n 2
a lso d sc r ib s h w e e o to u se it . Ho w e v e r ,
it is diffi l t t ha dl a d c u o n e n c on a n t i s oc c lu d d a i e r .

Th di h m d W a kl y r c ommen d mi tu r f potassium
u c u
3
an n n e a x e o

bi h r oma t a d sodi m c a r bo a t f or yiel di g c rb di id by

c e n u n e n a on ox e

d i r c t h a ti g
e e n .

M ag si t (M gCO ) is us d a th e sou r c f C0 i th e c l s d
ne e g e s e o 2 n o e

t ub m th d p usu y i s s m a ll a m u t s
1
( b i ll
‘
e ee o u t t a sec ta . on n o n

of c c lu d d
o i e a r .

Ca rb d i ide f r m a Kipp g
on ox r a t r ca o t b e u d o w he en e o nn se e v en n

t h e ma r bl e lumps h av e b e boil d w i th w t r o ac c u t f t he e n e a e n o n o

o c lud e d a i
c r .

T h t ks f li q i d C0 a
e an b t i d o th m r k t
o u ta i c on 2 s o a ne n e a e c on n

s id a bl
er a mou t s o f a i a d t h e r e f r
e c a
n t b e us d r n o e nno e .

2 .
—
T h e M an om e te r Ac c om pan yi n g S to p c oc ks U tub e e tc , ,
-
, .

— S i n ce dimi n ish e d pr e ssur e s a r e us e d in t h e n i t r o en d e t e rmi n a

g
t i o n i t is n e c e ss a ry t o h a v e a m a n om e t e r in c on n e c t i on wi t h
,

t h e a pp a r a tus in o rd e r th a t th e op e r a to r wi ll b e a bl e t o u n de r
s tan d wh a t to d o T h e U f orm is r e comm e n d e d as sh own in th e .
-

g e n e r a l di a gr a m (p I t is m a d e o f o r di n a r y gl
. a ss t ubi n g
a n d is a t t a ch e d t o a w o o d en s t a n d pr o vid e d f o r thi s purp o s e .

Th e l on g arm sh ould b e a t l ea s t 8 2 cm in l e n gt h an d th e sh o r t a rm .

a t l e a s t 5 5 cm T h e sh o r t a rm is surm o u n t e d wi t h a n i n v e r t e d
.

sma ll te s t t ub e wi th a plu g of c o t t on a t th e b o t tom t o pre ven t dus t

-

p a r ticl e s from ge t ti n g i n t o th e tub e an d t o p r e ven t m er cury from

spl a shi n g ou t Wi th th e o rdi n a r y gl a ss tubi n g of ab ou t 5 mm
. .

b o r e approxim a te ly 2 5 0 gr am s o f m e rcu r y is r e quire d T h e

,
.

column of m e r cu r y wh e n a t r e s t sh ould e x ten d in e a ch a rm

4 40
-
cm f r
1 o m t h e l o w e
. r b en d I f it is much hi gh e r t h an this .
,

it ma y b e dr awn o ve r th e t op wh en a g oo d v a cuum is b e i n g
ob tai n e d A m e t e r s t ick may b e a tt a ch e d t o th e b oa rd t o
.

m e a sure th e diff e r e n ce in h e igh t s o f th e tw o c olum n s if th e a c tu a l 5

B1
st d t A l i t u g
en n e v r i f h t E l m t r lys 3 A fl g
,
n e n
9z ur e e n ac en e en a a n a e, u a e, 1 2 .

G tt m
2
a P r ti l M t h d s f Org i Ch mis try t r s by S h b r
er an n , ac c a e o o an c e ,
”
an . c o e

an d B b i i a 3 d Am r E d
as n an , p e . . . 101 .

3
J ou rn . Chem S oc . .
,
22 293 .

4
p 94
G a t t e r ma n n , l oc c it .
,
. .

Or sh o rt p a pe r s c a l e s c a n b e us e d
5
S e l e c t a n y p oi n t x n o t l e ss t h an 3 8 c m .
, , .

abov e t h e l o w e s t ben d in t h e gl a ss t ubi n g a n d a t t ac h a n arro w s t rip o f p ape r n ear ,

28 2 LAB OR ATOR Y MANUAL OF OR GANI C CHE M I S T RY
pre ssure is d e sire d T h e p r e ssure wi thi n th e a pp ara tus may b e
.

c alcul a te d by sub t ra c ti n g t his diff e r e n ce in h eigh t from the

b a rom e te r r eadin g a t th e tim e .

T h e m an om e t e r is c on n e c te d wi th an E rl en m e ye r h e avy
walle d fil te rin g fla sk a n d this is pro vid e d wi th an ou tle t s top
c o ck (No 9) an d an oth e r s t op cock (No 1 0) lea din g to a sui table
.
-
.

pump Wh en a w a te r pump is us e d th e con n e c ti on is m ad e

.

t o go t o th e b o tt om o f th e fil te ri n g fl a sk in o rd e r t h a t a n y w a t e r
which may c o m e ove r on a cc ou n t o f u n e qu al pre ssure in th e
w ate r m ain will be suck e d righ t ou t a s s oon a s th e gre a te r wa te r
pre ssure re turn s A good w a te r pump will give a pre ssure in th e
.

app a r a t us a s l ow a s th e v a p o r t en si on o f th e w a t e r a t i t s pa r

t ic u l ar t e mp e r a tur e I n wi n t e r wh e n th e t e mp e r a t ur e of th e
.

wa te r may be a t which th e va p o r t en si on o f th e w a t e r is

mm th e pr e ssur e wi thin th e app a ra tus may app roa ch 8 mm

.
,
.
,

bu t in summ e r wh e n th e t e mp e r a tur e o f th e w a t e r may b e as

high a s 2 3 a pre ssure ca nn ot be ob ta in e d l owe r th an 2 1 mm
°
.
,

whi ch is th e vap or t en si on of th e wa t e r a t th a t t e mpe ra ture .

A g ood oil pump c an b e subs t i tu t e d f or th e w a t e r pump wi th

much a dva n tage .

T h e ou t l e t of th e E r l e n m e ye r fil t e ri n g fl a sk is c on n e c t e d by
m e an s of a s top c o ck (No 8 ) t o a T t ub e which j oi n s th e gen e r a
-
.
-

t o r a n d a U —t ub e wi th gr o u n d s t opp e r s T h e U t ub e is fill e d .
-

wi th gl ass b ea ds an d jus t e n ough c on c sulfu r ic a cid is a dd e d to .

m ak e a s ea l a t th e b ot tom a n d n o m o re Th e gl a ss b e a ds s e rve .

t o pr e v en t th e a cid fr o m b e i n g spl a sh e d up on th e s t e p c o cks -

.

T h e a cid a t ta cks t h e gr e a s e a n d c a us e s l e a k a g e a s w e ll as s ticki n g

o f th e s t opp e rs T h e a cid is us e d t o pr e ve n t a n e xc e ss o f m ois t u r e
.

from th e c a r b on di oxid e from ge t ti n g i n to th e combus tion tub e

a n d it a ls o sh o ws which w a y th e ga s e s a r e fl o wi n g T h e a m o un t .

th e t op r th e bo tt om o f th e s t an d M ea suri n g from t h e poi n t x ma rk

an d on e n ea .
,

o n t h e p a pe rs n umbe rs s h o w i n g 2 8 to 3 8 c m u p a n d d o w n re sp e c t iv e ly
.
, T he
.

n u mbe rs may v a ry a c c o rd i n g t o t h e p o si t i o n s o f t h e p a p e rs R ul e d c e n t i me t e r
.

p ap e r is very c on ven i e n t a n d w h en t h is is use d it sh o ul d n ot be a tta c h e d un t il

,

a d e fi n i t e p o i n t o pp o si t e a c e n t i me t e r li n e h as b een l oc a t e d I n o rd e r t o c a l c u l a t e
.

t h e pre ssure w i t h i n t h e a pp a ra t us a dd t h e n u mb e rs on t h e l o w e r an d uppe r s c a l e s

,

o pp o si t e t h e t op o f th e me r c ury me n is c us a n d sub t ra c t th e s um o f th e s e n umbe rs

from the barome te r readin g a t th e t i me .

{
284 LAB OR AT ORY MAN UAL OF OR GANI C CH E M I S T R Y

NOTE
u

Wa te r f r me d in th e r a ti n some tim c oll c ts i n the e d of

o e c o es e n

t h e c mbus t io tub n a r t h a t me t r
o n e sp iall if a e tr a l g
e e zo o e ,
e ec y n x on

e t
x en s s us d S i
i on 1 th w at r i
e . t eed d
nc e p r ovisi is
e e s no n e no on

ma d f e g t t
or i g i d f
e i t nH w e v e r rif i t iso a ll o w d
. t o c o ll c to i t ,
e e ,

will ca us m mb ti n t b s to r a k I n r d r to k ep it
e so e c o us o u e c c . o e e

f r m fl w i g b c k al g t h h e t d p r ti
o o n a on f t h e tub a d ca usi g
e a e o on o e n n

t h t ub t c r a k t h t ub
e e o ma y be sl a t d s m w h a t by bl ki g
c ,
e e n e o e oc n

up th th r d f t h f r a c e 3 c m ab v th l v l o f th d sk
e o e en
—o e u n 2 . o e e e e e e .

4 T.h e C o m b us ti on T ub e a n d H o w t o Fi ll I t —
T h e c o m .

bu s tion t ub e i t s e lf sh ould b e th e s am e in e ve ry w ay a s th e on e
d e sc r ib e d in c o n n e c ti on wi th th e d e t e rmi n a ti on o f ca rb on a n d
hyd r ogen (pp 2 3 2 .

T h e m e th o d o f filli n g is i n dic a t e d in th e g en e r a l di a gr a m
( p . A n 8 cm r o ll o f cup r-
ic o xid e g .a uz e ( s e e p 2 3 5) is p re .

p are d a n d pl a ce d a t A n e ar th e en d t o which th e U tub e is c on ,

-

n e c te d I t s e rv e s th e s am e purp o s e as th e on e in th e c a rb on
.

an d hydr oge n c o mbus t i o n t h a t is m a i n ly as an o xid a t i o n

, ,

buff e r in pre ve n ti n g a n y gas e s which may go b a ckward f r om

ge tti n g s o f ar b a ck th a t th e d e te rmin a ti on is sp oile d (s e e p 2 3 .

A b o u t 2 5 cm f r om t his s ame e n d o f th e c ombus t i o n t ub e pl a ce

.
,

a sh o r t r o ll o f c o pp e r ga uz e fi tti n g sn u gly ; fo llow this wi th a ,

l aye r of cupric oxid e in w ire f orm an d k e ep this in pl a ce wi th 1

,

a n o th e r s n u gly fi t ti n g sh o r t r o ll o f c o pp e r ga uz e This e n ti r e .

l aye r in cludi n g th e sh or t spi r a ls should m e a sure approxi

,

m a te ly 2 6 cm T h e op en sp ac e B b e tw e e n th e l on g cupric
.
, ,

o xid e spira l an d th e lo n g l aye r of cupric oxid e is r e s e rv ed f or ,

t h e b o at .

For th e f a r e n d o f th e c ombus ti on t ub e which is h ea t e d by

s e c tion N o 3 pr ep a r e a 1 2 cm roll o f copp e r ga uz e D This i s
.
,
-
.
,
.

a lw a ys us e d in t h e r e duc e d c o n di ti on in o r d e r t h a t a n y o xid e s

o f ni t r o g e n t h a t m ay b e f o rmed will b e c o n ve r t e d i n t o e l e m en ta l .

1
Cup ri c i de w h i c h h a s b e en use d fo r th e d e te rmi n a ti on o f c arbon a n d h yd ro
ox ,

gen ,
c a n b e us e d f o r t h e d e t e r mi n a t i on o f n i t ro g a l th o u gh t h e o ppo si t e is n o t en ,

th e c a se on a c c o u n t o f t h e p o ssi bl e r e t e n t i on o f c a rb o n d i o xi de u n l e ss it h a s b e e n .

h ea t e d in th e o p e n f o r a l o n g t i me a d all o w e d t o c ool in th e a ir T h e c e rium

n .

d i o xi d e c a t alys t c a n n o t be use d in t he n i t roge n d e t ermi n at i on .

 OR GANI C 285
i

CoM Bus TI ON S
’

r g b e f ore p a ssi n g i n to th e az ot om ete r T h e re d uc ti on is

ni t o en .

car r i e d bu t a s fo llows : S e l e c t a P yr e x t e s t tub e o f such a siz e ' '

-

th a t th e r o ll o f c opp e r gauz e will fit i n i t l oo s e ly P la ce a w a d .

o f a sb e s t o s o r gl a ss w o o l a t th e b o t t o m a d d n o t m o r e t h an ,

1 cc of m e t hyl a lc oh o l an d supp or t i t in a s tan d

. H ea t th e
,
.

t o r e d n e ss ov e r a M e k e r bur n e r o r in a v e ry l a rge bl a s t
b

I n o rd e r to a v o id m e l ti n g th e c opper th e l ow e r e n d o f th e ‘

is Sl owly sw u n g to a n d f ro whil e the u ppe r en d is secure ly

'
“

held in its p o si ti on by th e l ittl e l Oop wi th a pai r o f t on gs I n

'
f
.

t his w ay th e en t ir e ga uz e is e v e n l y h e a t e d Th en quickly d rop .

i t i n t o th e t e s t t ub e a n d ign i t e th e issui n g v ap o rs
-
,
D o n ot .

br ea th e th e fum e s sin c e th e y c on sis t l arge ly of fo rm al de hyd e

,
.

I f th e h ea t i n g h a s b ee n d on e pr op e r ly th e c o pp e r s oon l o ok s ,

b eau tiful in th e r e duc e d con di ti o n Wh en th e fl am e di e s d own .

a n d jus t as i t r e c e d e s i n t o th e t ub e pu t in th e c o r k l oo s e l y an d , ,

s e t a sid e u n t il i t b e c o m e s c o ld b e f o r e pl a ci n g t h e spir a l i n t o th e

combus ti on tub e I f th e tub e is n o t s t opp e r e d th e ho t spira l

.
,
‘

will be r e oxidiz e d a s air f oll ows th e fl am e d own t h e t u be .

5 T h .e A z ot o m e t e r T h e n i t r o g e n is c o ll e c t e d an d m e a sur e d
.
1—

in a S chiff a z o t om e t e r I t is illus t r a t e d in th e g e n e r a l di agr a m

?

on p 276 .a n d a s sh o w n i t c o n sis t s o f a gr a du a t e d t ub e sur

,

m ou n te d wi th a s top —co ck a n d e x ten si on c ap a n d n ea r th e b o tto m ,

a r r a n g e d a s i n dic a t e d f or a ga s i n l e t pr o t e c t e d by m e rcury an d a

1
rm a zo t ome te r is use d i n s te a d o f n i trome t e r as th e a pp a ra t us
T he t e ,

is so me t i me s c alle d si n c e t h e l a tt e r re f e rs more d ire c t ly t o t h e me a suremen t

,

o f ni t ri c o xi d e f o rme d in t h e a n a lysis o f n i t ri c a c i d by r e d u c t i on w i t h me rc ury

in pre s e n c e o f sulf uri c a c i d w h il e a o t ome te r li t e ra lly mean s th e n i t rogen me a sure

,
z .

( Fre n c h a z o t e ; G re e k u p
,
S c h iff sp ea ks o f it in h is o ri gi n a l ar t i c l e
,
‘
er ov ,

Z eit a n al Chem 7
. .
4 3 0 as a n
.
,
a zo t o me t e r L u nge Ber 11 ( 1 8 7 8 )
,
.
”
,
.
,
.

4 3 4 n ame d his n i t romet e r fro m t h e f ac t t h a t h e d e sire d it f or a n alyz i n g n i t ro se

1

, ,

w h i c h is d e fi n e d by P a tt e rs o n in h is G erma n E n glish D i c t ion ary for Chemist s -

as a s olu t i o n o f ni t ro sylsul furi c a c i d in sulfuri c a c i d f o rme d in th e l e a d c h a mbe r ,

-

proc e ss T h is ma t e ri a l is kn ow n in E n glish a s
.
”
n i t r o us vi t ri o l a n d d e s c ri b ed

in t h e Ce n t ury D i c t i o n a ry a s s tron g sul furi c a c i d c h arged w i th ni tro sul phoni c

a c id . I t ru n s o ff from t h e bo t t o m o f t h e G a y L uss ac a b s o rb i n g t o w e r in t h e ma n -

u f a c t u re o f sulfuri c a c i d by t h e l e a d c h a mbe r proc e ss L u n ge also men ti ons-

.
”

G a y L uss a c T h u rrn saure ( G a y L uss a c t ow e r a c i d ) Co mp a re a lso L un ge ,

.

- - - -
.

T e c h ni c a l M e th od s o f A n a lysis t r a n s by K e a n e
”
Vo l I P t I 1 2 5 a n d
,
. .
,
.
,

13 1 .

2
S c h ifI , Z ’

e it a n al
. . Chem , 7 .
43 0 .
286 LAB OR ATO RY MANUAL OF OR GA NI C CH E M IS TRY
con n e c ti on by m e a n s o f a rubb e r t ub e t o a r e se rvoir which hol ds
th e s olu ti on o f p o t a ssium hyd r oxid e A n a djus t a bl e r i n g (no t .

shown in th e di agram) is a tta ch e d f or h oldi n g the r e s ervoir in

a n y p o si t i on d e sir e d T h e t ub e pr op e r sh ould be a b ou t 7 8 mm
.
— .

i n sid e di am e te r 48 cm l on g (m e a sure d from th e r e s e rvoir ou tle t

,
.

t o th e s t op c o ck ) wi th a c ap a ci t y o f 5 0 cc o f ga s an d gr a du
-
.

a t e d in on e t en t hs -
E n ough m e rcury (ab ou t
. 0 cc or 1 3 5 1 .

g r a ms ) sh o uld b e p u t i n t o t h e b o tt o m t o m a k e a g o o d s e a l f o r

th e i n l e t t ub e b u t n o t e n ough to spl a sh o v e r i n to th e t ub e l e a d
1

in g t o th e r e s e rvoi r T h e dis t a n c e b e tw e en th e s e i n l e t an d
.

o u t l e t t ub e s sh o uld b e n o t l e ss t h a n 3 cm Fur th e rm ore th e i n l e t .

t ub e sh ould b e b e n t upw a rds t o such a n e x te n t (a b ou t 8 c m ) .

t h a t th e m e rcury will n o t r u n o v e r wh e n th e r e s e rvo ir full o f KOH

s olu ti on is rais e d to th e t op o f th e az o t om e te r .

S om e azo t ome t e rs a re m a d e wi th ou t th e cup s ea l e d on t op ,

bu t h a v e a n a rr o w t ub e f or c on n e c t i n g wi th a e udi o m e te r f or
t r a n sf e rri n g th e gas A cup c an b e p u t on on e of t his typ e
’

by a tta chi n g a wid e tub e by m ean s of a rubb e r s topp e r S om e azo .

t ome t e r s a re pr o vid e d wi t h w a t e r j a ck e t s bu t it d oe s n ot app e a r ,

n e c e ss a ry t o u s e t his f o r g en e r a l w o r k .

T h e s top c o ck sh o uld be w e ll g ro u n d an d all dir e c ti on s given

-

f o r h an dli n g s top c o cks sh ould b e us e d in h an dli n g t his p a r t

-

o f th e a zo t om e t e r (s e e pp 2 2 9 an d B e; sur e t h at al l
.

p ar t s of b o th ke y an d b arre l a re dry b e f or e pu tti n g on th e

g r ea s e E xc
. e p t wh e n t h e a pp a r a t us is a c t u a lly in u s e t h e k e y
o f th e s t op c o ck sh o uld n o t b e a ll ow e d t o r e m ai n in i ts pr op e r
'
‘

p osi ti on sin ce i t is ve r y like ly to b e com e fr oz en e ven on

,
“ ”

s tan di n g ove rn i gh t if th e r e is an y of th e p otassium hydr oxide

s olu ti on in th e gre a s e A t ta ch it wi th a pi e ce of twi n e ?
.

1
D t d t i hi
enn s e A l i tu g v r i f h t E l m t r lys 3 A fl g
n s n e n z ur e e n ac en e e n a an a e, u a e,

1 25
—8
,
d e sc ri be s a mod ifi e d a z o to me t e r i
pill ary i n l e t t ube e n di n g in an
wh c h h as a c a

i n t ern al proj ec ti on w h i c h d elive rs a fin e s t re am o f ga s a n d w h i c h also h as a n e n ,

l a rge d p or t i on be l o w t h e gra d ua t e d p a r t t o s e rve a s a re s e rv o ir in c a s e a l a rge

amo un t o f gas is su dd e n ly d e liv e r e d i n t o t h e az o t o me t e r .

2
A n e xc e ll en t me th o d o f re mo vi n g froze n s top c o c ks is give n by V C -
. .

Allison Jour n I nd and E n g Chem 11

, . .
46 8
. T h e h a n dl e o f t h e key is
.
,
.

slippe d i n t o a so c ke t in a bl oc k o f h ard w ood w h il e t h e op e n i n g o f t h e bl o c k re s t s

as a c o ll a r on t h e sh o ul d e r o f t h e ba rre l o f t h e s t o p c o c k A plug of w ood is pl ac ed -
.

a ga i n s t t h e o t h e r e n d o f th e ke y an d ea sy r egul a r pre ssur e bro ugh t t o be a r by

,
‘

288 L AB ORATORY MAN UAL OF OR GANI C CH E M IS TRY

V . T h e Fi nal P re par ati on of th e C pr u ic Ox id e 1

Cupri c xid e wh e n h e ate d an d c oo le d

o in an at mo sph e re of

o xyg en o r a ir a ds o rbs som e o f th e s e g a s e s . T he cupric oxide thus

N N R 1
OTE S A D E F E R E N CE S

C up ri c i de has be e n used in organ i c c ombus ti on s for t h e d e te rmi na ti on o f

ox

c a rb o n a n d h y d r ogen a n d n i t r o ge n si n c e 1 8 5 ( s e e p a n d t h e me th od f or 1 .

d e t e rmi n i n g n i troge n s e p a ra t e ly w a s w orke d ou t e sp ec i a lly by D u ma s in 1 8 3 1 ( se e

p . T h a t c upri c ox i d e a b s o rb s ga s e s a n d giv e s th em up on h e a t i n g w a s n o t i c ed
a s e a rly a s 1 8 4 2 w h e n E rd ma n n a n d M a rc h a n d J f u pr a kt Ch m 26 — ‘

r
, 7 ,
. . e .
, ,

w o rki n g On t h e a to mi c w e i gh t o f h yd rogen sh o w e d t h a t 1 00 grams o f c u p rit: ”

,

o xi d e w h e n h e a t e d in a n a t mo sp h e r e o f c a rb o n d i o xi d e a f t e r pure c arbo n i c a c i d “

h a d be e n p a sse d th ro ugh t h e t ube f o r ma n y h o urs ga ve c c o f a ir u n a b so rbe d ,

.

by p o t a ssium h y d ro xi d e so lu t i o n In 8 6 8 Fra nkl a n d an d A r ms t ro n g in a n . 1 ,

arti c le On t h e A n alysis o f P o t a bl e Wa t e rs J Chem S oc 21 89 an d 9 3 ,

. . .
, ,

d e s c ri bed t h e ir me th o d o f d e t e rmi n i n g c a rb o n a n d n i t r oge n in v e ry sma ll a mo u n t s

o f o rgan i c ma t e ri a l by b urn i n g it in a c o m b us t i o n t ube a f t e r c o mpl e t e e v a c u a t i on

w i th a S pre n ge l p ump an d a n a ly z i n g t h e ga s e s e v olv e d T h e y s tat e C upri c .

,

o xi d e pre p are d fro m t h e n i t r a t e sh o ul d o n n o a c c o u n t b e us e d s i n c e e ve n a f t e r , ,

be i n g ac t u ally fus e d i t e v olv e s c on si d e ra b l e qu a n t i t i e s o f c a rbo n i c a n h yd ri de an d

,

n i t roge n w h en i gn i t e d i n vac u o E i gh t y e a rs l a t e r T h u di c h um a n d Ki n gze t t

”
.
,

J Chem S oc 3 0
. . .
3 6 3 c o n firme d t h e s e fi n d i n gs in ge n e ral
, ,
Hil di t c h .
,

Che m N ew s 49
.
,3 7 me n t i on s t h e f a c t t h a t c upri c oxi d e oc c lud e s ai r an d
, ,

M orl ey A mer J S c i 41
,
. 28 1 sh ow s t ha t c upri c o xi de sl ow ly give s off
.
, ,

gas in a v ac uum T W R i c h ard s in re visi n g t h e a t omi c w e i gh t of COp pe r P r oc

. . .
, , .

A mer A c ad A rts
. . a nd S ci ,
26 2 8 1 , an d Z ei t . a n or g . Chem , 1 . 196 ;

proved t hat se veral o f th e formerl y a c c e p t e d re sul t s w e re i n c orre c t on a c c o un t of

t h e e rror i n v olv e d d u e t o gas a d s orb e d by t h e c upri c o xi d e w h i c h h ad bee n us e d f or
t h e d e t e rmi n a t i on s I n his l a t e r sys t e ma t i c w o rk on t h is p ar ti c ul a r sub j e c t
. On ,

t h e Ca us e o f t h e R e t e n t i o n a n d R e l e a s e o f G a s e s oc c lu ded by t h e Ox i de s o f
M e tals A mer Chem J 20
,
”
.
7 0 h e s t a t e s (p a ge
. Wh en t h e im 1, ,

prison ed ga s (in c upri c oxi de ) h a s o n c e begun t o be s e t free at t e mp e ra t ure s a bo ve ,

t h e t i me is a n e ss e n t i a l fa c t o r a n d t h a t w h e n su ffi c i e n t t i me has been a ll o w e d

, ,

t h e e xpul si on o f t h e gas is al mo s t c o mpl e t e F ur th e rmore (p T w o gra ms . .

of c upri c oxi d e w h ic h h a d b een i gn i t e d f o r a l o n g t i me in pure a ir un t il c o n s t a n t

‘

i n w e i gh t w e re f o u n d t o e volve a ga s s t e a d ily w h e n h ea t e d in a v a c uum t o a bo u t

,

t h e me l t i n g po i n t o f c o mmo n s a l t
-
pro vi d e d t ha t th e ga s w as remo ve d by
a S pre n ge l pump a s f a s t a s it w a s f o rme d C upri c o xi de begi n s t o l os e s t ru e
”
.

t ura l o xy gen e v e n in t h e a ir a t a b o u t b u t t h is is abo ve th e me l t i n g po i n t

” -

o f t h e h a r d gl a ss us e d C upro us ox i d e w as f ou n d in t h e re si d ue
. T h e ob s e rv a t i o n .

is th en made (p 7 2 8 ) .
I

S i n c e c upri c o xi d e is sli gh tly d isso c i a t e d by h e a t p e rc e p t i bl e amo un t s o f ,

o xygen sh o ul d b e re mo v e d by h e a t i n gi t inn i t rogen jus t a s c arb o n i c a c i d is r e mo v e d ,

from li me s ton e by h eat i n g it in a c urre n t o f air T his dissoc i at i on o f c upri c o xi d e .

mus t h a ve its e ff e c t on a n y proc e ss i n volvi n g th e i gn i t i on o f c upri c o xi de i a n

vac uum o r in an i n ert gas T h e de t e rmi n a t i on o f organ i c ni t rogen by me a n s o f th e

.

S pre n ge l pump f or e xampl e mus t be aflec te d by it

,
T h e use of c arbon d i ox i d e
,
.
 OR GANI C CO MBU S T I ONS 289

prep are d on b ein g h ea te d again s l ow ly g ive s off th e a dsorb e d ga s .

S i n ce t h e ga s which is sl owly giv en off is n o t a bs orb e d by th e

as a d ispl a c i n g me d iu m in t h eD uma s me t hod probably disp o se s o f th e e rro r , ,

h ow e v e r f o r c a rbon d i oxi d e is i t s e lf d iss oc i a t e d by h ea t a n d it u n d o ub t e d ly fur

, ,

ni sh e s e n o ugh ox ygen t o d i mi n ish gre a t ly t h e d e c o mp o si t i o n o f t h e c upri c o xi d e

”
.

(NOTE I t sh o ul d be e mph a si ze d th a t t h is l a t t e r s ta t e me n t re fe rs on ly t o
—

th e li be ra t i o n o f ga s fro m t h e a c t ua l d e c o mp o si t i o n o f th e c upri c oxi de a n d n o t

to t h e li be ra t i on o f oc c lud e d ga s e s ) .

T h e gas oc c lude d in th e c upri c o xi d e is o nl y sl ow ly giv e n o ff by h e a t i n g t o

redne ss an d th e e rror i n vol ve d in the n i troge n de t e rmi n a t i o n a mo u n t s t o
,
to

pe r c e n t
1
( usually n e are r t h e higher fi gure ) w h e n gra m o f t h e s a mpl e is
use d D i mi nish i ng t he t i me of t he c omb us t i on o f c o urse di mi n ish e s t h is e rror
.
,

a n d usu a lly t h e re a re c o mp e n s a t i n g e rro rs w h i c h v a ry a gre a t d e al in ge n e ra l , ,

prac t i c e w h i c h al so some t i me s kee p th e fi n al e rro r do w n t o t h e ord i n ary a mo u n t ,

t h a t is , p er c e n t Wh e n a sub s t an c e w i th a hi gh c on te n t o f n i troge n is a n alyz e d

.

the p e rc e n tage error is o f c o urs e d e c re a se d b u t w i th a l ow c on t e n t of n i troge n ,

it is v e ry se ri o us N o n e o f t h e t e xt boo ks o n pra c t i c al o rgan i c c h e mis t ry t o w h i c h

.
-

o n e w o ul d o rd i n a rily go f or a d e s c rip t i o n o f t h e D u ma s me th od su c h as t h o s e by ,

G a tte rman n W A N o ye s a n d J B Coh en s a y a n y t h i n g a bo u t t h is e rro r

,
. .
,
. .
, ,

Ne i t h e r is i t me n t i o n e d by Cl a rke A H an dbook o f Organ i c A n alysis ; Ki ng

,
”

sc o tt a n d K n igh t Quan t i t a t ive Organi c A n alysis ; n or e ve n by L a ssa r Coh n

,
-

Arbe i tsme thod en allgeme i n e T e il 4 Au flage

, a n d W e yl D ie M e t h od
, ,

en d e r o rga n is c he n C h e mi e a ll ge me i n e T e il ,
”
All th e se a uthors d o
ge n e rally sp e ak of t he mi n i mu m a mo u n t o f f oam th a t a l w ays c oll ec t s in t h e
t op o f t h e azo tome t e r a n d w h i c h T h u d i c h um a n d Ki n gze tt J Chem S oc 30 , . . .
,

3 6 6 c h a rac te ri ze d a s tha t obs ti n a te bu bbl e i n the gas tu be w hic h ha s puzzl ed -

,

so man y of the bes t exper i men tal is ts .

”

In 19 1 5 Fie l d n e r an d T a yl o r , J . I nd . a nd E n g Chem , 7 . . 1 0 6 , a tt e mp t e d
n i t roge n ,
m ad e
od si n c e is
“
it

smal l a mo un t s of n i troge n app roxi ,

t h e ir a pp a ra t us a n d me t h o d as giv e n in ,

oun d w h t man y o t h e rs h a v e als o f o u n d a

o ff f o r e x a mpl e c c a f t e r s ix h o urs
, ,
.

w a s re h e a t e d t h e n e x t d a y T h e y t he n -
.

in h is A n alys e u n d Ko n s t it u t io n s e rmit
187 T h e c h i e f so urc e o f ,

fin e c o pp e r o xi d e from air an d ,

are t oo h i gh by to p er c e n t A lso in“Fre .

”
,

Ch e mi c a l A n a lysis 6 th E d II 68 T he ,
.
, ,

a t t oo h i gh v iz b y a bo u t t o 0 5 pe r c e n t
,
.
,
and .
,

e x p e ri me n t w i th su ga r t h e qu a n t i t y o f u n a b so rb e d ga s sh o u l d
c c .H N M orse E xe rc ise s in Qua n ti t a t ive Chemist ry
”
. .
,

in p a r t fo r th e d i ffic ul t y by h ea t i n g bo th c o a rs e a n d fin e c up ri c
s at ful l re d h ea t in a c urre n t o f o xyge n w h i c h is follow ed wi th out ,

1
F B l a u M on ats c hef te 13 ( 1 8 9 2 ) 2 7 7
.
, , .
29 0 LAB OR AT OR Y MANU AL OF OR GANI C CH E MI ST RY
p o ta ssiu m hydroxid e solu ti on in th e az o tom e te r it cause s a .

s e r i ous e rror in th e d e te r min a ti on of n i t r ogen .

T o pr ep a r e th e cup r ic o xid e f or th e a n a lysis it mus t be ,

h e a te d s t ron gly to a go od r e d h ea t jus t a s in th e c ombus ti on ,

i t s e lf in a va cuum f or a b ou t six h ours th e g as e s b e in g r e m ove d

, ,

a n d r e pl a c e d by fl oodi n g th e app a ra tus tw o or thr e e t im e s

wi th pure ca rb on dioxid e Fi n a lly th e cupric o xid e is a ll owe d to .

c ool in an a tm osphe re o f pu r e c arb on di oxid e I n this m a n n e r .

t h e ga s a ds o r b e d is on e t h a t will c a us e n o t r o ubl e in th e a n a lysis .

A f t e r th e e n ti r e a pp a r a t us is s et up a n d th e g en e r a tor 1

prop e rly fille d a cco r din g t o th e d e scrip ti on in Ch ap te r I V p 2 7 5

, ,
.
,

s e t t h e s t op c o cks a s f o ll o ws : N o s
— 2 6 a n d 9 cl o s e d an d . 1, , ,

3 , 4 5 7
,
8 1 0 a n,
d 1,
1 o p e n ;,
t h e n t ur
,
n o n t h e pump a n d a ls o ,

b e gi n the h ea tin g I t is n o t n e ce ss ary th a t th e h ea tin g be d on e

.

wi th ou t i n te rrup t i on bu t if it is in t e r r up te d th e cupric oxid e

,

mus t be allow e d to c ool in an a tm osph e r e of c a rb on di oxid e ,

o t h e r wis e li t t l e will h a v e b e e n a cc o mplish e d .

S o on a f te r th e a pp a r a t us h as b e e n e v a cu a t e d o cclud e d an d ,

c oo li n g ,
rbon di oxi de for an hour or more a n d the oxi de is all ow e d to c oo l
by c a ,

in C0 F i n ally in a n o b s c ure j o ur n a l n a n a r t i c l e pu blis h e d in 8 9 8 by F C

2. ,
I 1 . .

P hillips on t h e Fluc t ua ti o n in t h e c omp o si ti on o f N a t ura l G a s P roc E n g S oc

, ,
”
. . .

Wes ter n P a 14 2 9 9 t h e y fo u n d an a c c o u n t o f si mil a r d iffic ul t i e s o ve rc ome : I n

.
, , ,

begi n n i n g a se ri e s o f d e t e rmi n a t i o n s s e v e ra l d a ys w e re o f t e n re quire d f or t h e purpo se .

T h e p orc e l a i n t ub e w a s s t ron gly h e a t e d w h il e a sl o w s t rea m o f c a rbon d i ox i d e w as

,

ma i n t ai n e d ; th e C u O w as n o t c o n si de re d t o b e in pro p e r c o n d i t i o n u n t il t h e
e s c a pi n g C 0 w a s a b so rb e d w i t h o u t r e si d u e
2 I t w a s fo u n d t h a t t h e C u O w h e n
.

o n c e i mpre gn a t e d w i t h CO w h il e s t r o n gly h e a t e d c o u l d be re o x i d i e d by a ir c ur
2, ,
z

ren t w i t h li ttl e t e n de n c y t o o c c u l s ion of a ir bu t if t h e c opp er oxi de w a s allow e d t o

,

c oo l in c o n t a c t w i t h a ir mu c h t i me w a s l o s t in re mo vi n g t h e a ir by c a rbo n di o xi d e

e v e n w h en s t ro n g h ea t w as a ppli e d Fie l d e r a d T a yl o r t h e n pro c e e d e d t o

”
. n n

sh ort e n t h e t i me f o r t he fi a l pre p ara ti on o f the c upri c o xi de by h ea t i n g it i n

n

I t is w ell w o r t h o n e s w h il e t o go o ve r t h e ir re c o rd e d e x p e ri me n t s a s
’
vac u o .

g iv e n i n t h e ir o ri g i n a l a r t i c l e m e n t i o e d a b o v e Tnh e y c on c lu d e d t h a.t E rr o rs i n ,

t he D u ma s me t h od d ue t o n i troge n fro m t h e C u O w e re mi n i m i e d by pre vi o usly z

h e a t i n g t h e o xi d e f o r s e v e ra l h o urs i n vac u o c ooli g it in CO a n d usi n g w ire ,

n 2,

fo rm oxi de p ul ve ri e d to p a ss t h ro ugh a 40 me sh s c re e n a n d remai n on 1 00 me sh

z - .
”

T h e s e re sul t s a re i n c o rpo ra t e d in t h e pre s e n t w ork .

1
T h e bo a t fill e d w i th C u o w ire s h o ul d be in pl a e (p b u t th e re d u c e d c .

c opp e r spir al sh o ul d o f c o ur se n o t b e in t h e t ube d uri g t h e pr e li mi n a ry h e a t i n g

, ,
n

( pp . 2 94 A ls o i t is n o t a b s,
o lu t e ly n e c e ssa ry t o h a ve t h e az o t o me t e r a tta c h e d

a t t h is t i me .
29 2 LAB OR AT ORY MANUAL OF OR GANI C CH E M I ST RY

go i
n g o u t hrough the m ercury trap p ar ti al ly op en s top co ck
t ,
-

N o 3 w a t chi n g t h e o v e rfl ow a l l th e t im e
.
, A s s oon as th e .

m e rcury b egin s to ris e in th e ou tl e t tub e cl ose s top co ck N o 3

'

-
.
,

a n d th en gr a du a lly op e n i t a g ai n Fr e qu en t gl an ce s at th e .

m an om e te r will S h ow h ow th e op e ra ti on is goi n g on I n this .

w ay th e app a r a tus will s oon b e fill e d wi th c a rb on di oxid e an d

th e g e n e r a t o r a lw ays k ep t u n d e r pr e ssur e an d fr e e fr om c on
t amin a tin g air .

A f t e r th e cupric oxid e h as b een h ea te d an d cool ed in CO 2,

it c an be h a n dl e d in th e op e n bu t n o t wi th ou t a ds o r bi n g air t h a t
will ca us e a sm all e rro r F or ex ampl e Fie l dn e r an d Tayl or
.
,
1

f ou n d th a t wh en 00 gr ams o f th e cup r ic oxid e w a s subj e c te d

1
“

t o a l t e r n a t e va cuum a n d c a r b on di o xid e f or s e v e ra l h ou r s a t
8 5 0 C u n til n o fur t h e r n i t r o ge n w a s e volv e d an d w a s th e n
°
.
, ,

coole d in CO exp o s e d to air an d a gain he a t e d the 40 1 00

2,
—
,

me sh wire o xid e gave off on ly 0 7 0 9 cc of n i tr ogen whil e

‘ ’ — .
,

t h e 2 00 m e sh m a t e ri a l ga ve off cc ”
-
.

Wh en a c ombus ti on h a s b e en ru n it is n e ce ssa ry to r eoxidiz e

s om e of th e c opp e r a n d h ave i t r ea dy f or an o the r d e te rmin a ti on
,
.

B e for e t urn i n g off th e h ea t (or a f te r a ll owi n g to c ool in C0 ) 2 ,

r em ove th e r e duc e d c opp e r spi r a l an d whil e th e t ub e is h o t p a ss ,

a ir o r o xy gen t h r o u gh i t u n t il a ll t h e c opp e r h a s b e e n o xidiz e d .

Th en whil e th e tub e is s till h ot re pl a ce th e air or oxygen wi th ,

pur e CO2 in th e usual ma n n e r k e epi n g up th e p a ss age of th e ,

ca rb on di oxid e for a n h our a n d a llow to c oo l in th e a tm osph e re

,

o f CO whil e th e t ub e is cl o s e d
2 I t is n o t n e c e ss a ry t o h ea t a gai n
.

f o r six h ours a s is th e c a s e wh e n th e cupric o xid e h a s b een c ool ed

VI . W e igh in g th e S ub s tan c e
Th e subs tan ce is w eigh e d in a p orce lain or qu ar tz b oa t i n sid e
th e sp e ci a l b oa t t ub e piggi e a n d a l l pr e c a u t i on s as t o
“

m ois t u r e s ta te of di v isi on etc m en ti on e d in c onn e c ti on wi th

, ,
.
,

w ei ghi n g th e subs tan c e f or th e ca rb on an d hydrogen d e te rmin a

t i on m us t b e obs e rv e d in t his c a s e a ls o (s e e p A f te r th e .

subs tan ce h as b ee n we igh e d an d th e weigh t r e cord e d it is n o t , ,

1 Journ . I nd . a nd E n g Chem , 7
. . 111 .
 OR GANI C CO MBU STI ONS 29 3

e ss en ti al m o s t ca s e s th a t m ois ture b e s o r igidly e xclud e d a s

in
fo r th e c a rb o n a n d hyd r oge n d e t e rmi n a t i on H o w e ve r i t is .
,

u n f or tu n a t e f or on e to l e t d own on th e goo d p r a c tice of k e e pin g

m ois tur e from we igh e d s ample s a n d thus sp oil a go od h abi t ,
.

T h e a m ou n t o f subs t a n c e us e d sh o uld o rdi n a rily be a b ou t

gram I f th e n i tr oge n con ten t is appro xim a t e ly known
.
,

u s e e n o ugh subs ta n c e t o giv e a b o u t 1 5 2 0 cc o f ni t r o g en S om e

— . .

subs tan ce s h a ve a high p e rcent a ge of ni t rogen an d gram ,

would give m or e n i t rogen th a n th e az otom e t e r c ould h old Then .

t h e a m ou n t o f s ampl e sh o uld be c u t d own a cc ordi n gly Cor .

r e s p on din gl y t h e a m o u n t o f s a mpl e o f a subs t a n c e wi t h a v e ry l ow

,

con ten t of ni tr oge n sh ould be i n cr e a s e d e ve n to 0 5 gram if ,

.
,

n e c e ss a ry a n d p r o vid e d this much c an b e sp a r e d

,
.

VII . G e n e r al M eth o d of P r oc e d ur e f or th e Comb u s ti on P r e pe r

T e s ti n g th e Appar a tu A f te r th e cupric oxid e h as b e e n

s —

pr ep a r e d an d th e t ub e fil l e d wi th ca rb on di oxid e a s a lre ady

d e scrib e d (p t e s t ou t th e en tir e a pp a r a t us t o s e e if th e
.

cup r ic oxid e is all righ t th e c arb on di oxid e is pure en ough , an d

,

al l j oi n t s a re in g o o d c on di t i on H a v e a l l o f th e app a r a t us c on
.

n e c t e d a n d h e a t th e c o mbus t i on t ub e a s f o r a r e gul a r c ombus ti on .

P a ss c arb on di oxid e t hr ough i t a n d i n t o th e azo t om e te r f or fiv e

to t en mi n u te s 1
I n o rd e r n o t t o e xh aus t th e p o ta ssium h y d rox
.

ide s olu ti on drop th e r e s e rv oir t o p o si ti on I a n d h a v e s top c o ck

,
—
,

N o 7 in th e azo t om e t e r op en
. A t th e en d o f th e t im e sp e cifi e d
.
,

whil e th e ga s is s till p a ssi n g c are fully ra is e th e r e s e rvoir to p o si

,

ti on I I wh e n th e s olu t i on will flow thr o ugh th e s t e p c o ck an d -

i n to th e cup on t op N ow clo s e th e s top co ck an d sl owly l ow e r

.
-

th e r e s e rv oir t o i t s f o rm e r p o si ti on in o rd e r t o r e duc e th e pr e s
sure agai n s t th e in flow in g gas P a ss th e gas th rou gh a t a fair.

r a te f or ab ou t fiv e mi n u t e s T he bubbl e s sh ould n o t be s o l a rge

.

an d c o m e s o f a s t t ha t t h e y fill th e en t ir e a z o t om e t e r t ub e a n d f o rc e

a l l th e p o t a ssium hydr o xid e s o lu t i on i n t o th e r e s e rv oir A f te r .

th e fiv e mi n u t e s n o te wh e th e r th e v o l u m e o f u n absorb e d gas
which colle c t s a t th e t op is m ore th an cc I t is di fficul t to .

1
In rd er t o t ake c are o f a n y exc e ss of pre ss ure in the gen era tor
o ,
be sure to have
s top c o c k N o 2 o p e n ( s e e p
-
. .
294 LAB ORAT ORY MANUAL OF OR GANI C CH E M I S TR Y
fo rmul a te an y rul e for h ow much u n abs orb e d gas sh ould b e
a ll ow e d si n c e th e r a t e v a ri e s e t c
,
bu t if much ga s c o ll e c t s then
,
.
, ,

t h e s t op c o ck (N o 7 ) sh o uld be op en e d a g ai n t o l e t th e s olu ti on
-
.

flow d ow n a n d c a rb on di oxid e ru n t hro ugh fr e ely f or an o th e r

fiv e mi n u t e s a n d a s e c o n d t ri al m a d e f or ahn os t c ompl e t e ab
,

s o rp ti on a s b e fore I f th e gas is n ot p a ssi n g t oo rapidly th e bub

.

ble s di mi n ish t o th e size of pin poin ts a s th ey fl oa t upw ard I f -

.

much u n abs o rb e d gas is coll e c te d again e i th e r th e cupric oxid e

h as n o t b e e n pr op e rly pr e p a r e d or th e g en e r a t o r an d j o in t s l ea k
or th e c a rb o n a t e is impur e an d th e s e mus t b e a t t en d e d t o
, .

This op e ra ti on sh ows th e chi e f e rror i n vo lve d in th e d e te rmin a ti on

o f ni t r oge n an d t h e r e f o r e th e e rr o r in th e fin al r e sul t will b e in

a lm o s t dir e c t r e l a t i on t o th e amou n t o f gas u n absorb e d in th e s e

blan k t e s t s .

I f t h e r e is a n y d o ub t a s to th e pr ope r co n di ti on of th e app a r a
t u s a c ompl e t e bl a n k ru n sh ould be ca rri e d ou t usi n g f or e xa mpl e , , ,

gram of sucros e (ca n e sugar) in pl ace of a n i trogen ous sub

s ta n c e .

Wh en th e te s t is s atisfa c t ory l e t th a t p ar t of th e combus ti on

t ub e which is to c on t a i n th e b oa t an d s e ve r a l c e n tim e t e rs e a ch ,

sid e of it c ool d own t o r oom tempe ra ture Du r in g th e coo li n g

,
.

r e duce th e ra te of th e carb on di oxid e or clo s e s top cocks Nos 5 ,

-
.

an d 6 t o pr e v e n t an y o f th e po ta ssium hydr oxid e s o lu t i on fr om

b e in g drawn i n to th e combus ti on tub e I f a combus ti on is n ot .

'

t o b e m ad e imm e di a t e ly l e t th e e n tir e tub e c ool d own in an

,

a t m o sph e r e o f c a rb on di oxid e (s ee p .

Th e Comb u s tio n T h e f oll o wi n g a rr an g e m en t s a re m ad e

.
-

f or b e gi n n in g th e c ombus t i on prop e r d ep en din g up on wh e th e r

th e furn a c e is c ol d or hea ted in p a r t :

a .
1
furn a ce is c ol d disc on n e c t b oth en ds of th e c om
I f th e ,

bu s tion t ub e c a r e fully r e m ov e th e cupric o xid e spir a l

, ,

i n s e r t th e b oa t con tain ing th e subs t an ce ? r epl a ce th e cup r ic

b . o xid e spir a l an d th en in s e r t t h e c ol d r e duc e d c opp e r spir a l
,

se l e t te rs in t he margi n re fe r to th e c o rre sp on d i n g p art s in t he T opi c al

1
T he
Out li n e s e c t i on 1 1 p 2 7 3
, ,
. .

I f t h e sub s t a n c e b urn s w i th difli c ul ty it s h o ul d be c o v e red w i th so me of the

2

C upri c oxi de w ire alre ady pre p ar e d f or th is p urpo se (p .

29 6 LAB OR AT ORY MANUAL OF OR GANI C CH E M I S TRY
u n absorb e d gas is a t a min imum a s d e scrib ed at the be ,

gin n in g of this ch ap te r .

I t mus t b e b o rn e in min d th a t th e s e pr e limin ary ope r a

t i on s sh ould be v a ri e d in a cc ord an c e wi t h th e pr ope r t i e s
.

o f th e subs t an c e I f it h a s a high va po r p r e ssur e a n d sub

.

lime s r e a dily or is e a sily m e l te d th e t im e fa c tor mus t be,

r e duce d th e h e a ti n g r e gul a te d e tc Fur th e rm ore it

, ,
.
,

cann o t be ove r emph a siz e d th a t go od judgm en t an d famili a r ~

ity wi th th e m e th o d a r e a lw a ys v e ry n e c e ss a ry t o give r e li abl e

re sul ts .

As s oon a s it h as b ee n f o un d th at th e am ou n t of un
abs o r b e d gas h a s b e e n r e duc e d t o th e pr op e r mi n imum

a m ou n t r e duc e th e flow o f c a rb on di oxid e t o such an ex t e n t

,

t h a t it will jus t k ee p t h e pr o duc t s o f c ombus ti on m ov i n g

t ow a rd th e a z o t om e te r usi n g th e s t opp e r (N o 5) in th e
,
.

U t ub e f or r e gul a t i n g th e gas an d a ll owi n g th e e xc e ss o f

-
,

carb on di oxid e in th e g en e ra to r t o e scap e r e gularly through

s top co ck N o 2 a n d th e s a fe ty b o t tle
-
. .

R a is e up th e r e s e rv oir a n d wh e n it is opp o si t e th e s top

co ck (No .o p e n th e s t op c o ck t o a ll o w t h e sm a ll am oun t o f
-

u n abs orb e d gas th a t may h ave c oll e c t e d t o p a ss ou t care ,

fully cl os e th e s top —co ck l ea vin g s om e o f th e s olu ti on in th e

,

cup ab ove a n d l ow e r th e r e s e r voir t o p o si ti on I I f th e r e

,
.

h as b e en a n y i n dic a t i o n t h a t th e subs t a n c e h as b e gu n t o
d e comp o s e th e n th e sma ll a m ou n t of un abs orb e d gas should
n o t b e driv e n o u t o f th e a z o t o m e te r l e s t s o m e n i tr og en fr om

th e subs t an c e b e driv e n ou t t oo .

N ow gr a du a lly h e a t m o r e o f th e cupric oxid e by dr awin g

th e l on g h e a t i n g s e c t i on (N o 2 ) t ow a rd th e b oa t a c en ti
.

m e te r a t a tim e an d a t th e s am e tim e b e gi n to h e a t sl owly

,

th e cupric oxid e spi r a l o th e o t h e r sid e of th e b oa t wi th

p
s e c ti on N o I . .

A s m en ti on e d in c on n e c ti on wi t h th e ca rb on an d hyd r o
d e te rmin a t i on (p i t is v e ry di fficul t t o d e scrib e
g en .

in d e ta il th e a c tu a l m e t h o d o f burni n g th e subs tan c e si n ce ,

e a ch o n e h a s i t s ow n p e culi a ri t i e s a n d th e re fo r e o n ly a
,
 OR GAN I C CO MBU S T I ONS 29 7

g en e ra l d e scrip ti on c an b e given H e re a ls o an id ea as t o
.

h ow th e subs t an c e b e h a v e s on h e a t i n g sh ould be g ai n e d
b e f or eh a n d if suffici e n t is a vail able by h ea tin g it an d
, ,

gr adually burn in g it in a b oa t ove r a sm all fl am e N o tic e .

wh e th e r it gra du al ly burn s sublim e s or sudd en ly de c om

, ,

p os e s
.

T h e subs tan c e is sl owly burn e d by gr adu all y dr awi n g

th e tw o a dj a c e n t s e c t i on s cl o s e r an d cl o s e r in a l te rn a t e t urn s
t ow a rd th e b oa t . Wh en the l arge h ea t in g s e c ti on (No 2 ) .

is ove r all th e cupric oxid e do n o t draw it an y fur th e r U s e .

th e sm a ll h e a t i n g s e c ti on (N o I ) to h e a t an d sl owly a n d c om
.

p l e t e l y d e c o mp o s e t h e subs t a n c e in th e b oa t S i n.c e th e
subs tan ce ch ars an d th e c arb on is n o t compl e te ly bu r n e d in
th e pr e s en c e of c a rb on di oxid e th e am oun t a n d a pp e ar
,

a n c e o f th e bl a ck d e p o si t d o e s n o t giv e a v e ry g oo d i n di c a

ti on of th e c o urs e o f th e c ombus ti on Bu t t h e a m o u n t o f
.

g a s wh i ch e n t e rs t h e a z o t o m e t e r an d,
p a ssi n g
,
upw a rd is ,

on ly p a r t i a lly a bs o rb e d d oe s giv e a g o o d id e a a s t o h ow th e
,

c ombus ti on is progre ssi n g T h e gas sh ould n o t com e

.

thr ough s o f a s t th a t th e bubbl e s will b e v e ry l arg e an d

rapidly fill th e a zo tom e te r tub e si n ce th e r e is d an ger th a t
,

all th e p o t a ssium hydr oxid e s o lu t i on will be driv en o v e r i n to

th e r e s e rv oir a n d t h e n th e ga s will f o ll ow "

Af te r ab ou t tw e n ty mi n u te s the subs tan c e will a l l b e
d e compo s e d an d th e ra te of th e gas e n te ri n g the az otom e te r
will th en d e cre as e to th a t of th e ca rb on di oxid e i t s e lf .

Now drive o v e r th e r e m a i n in g n i t r og en wi t h c a r b on di oxid e

by gr adu ally i n cre a si n g th e flow of th e l a tte r a n d con ti n u e ,

this u n til th e bubbl e s o f u n abs orb e d ga s ar e v e ry ti n y just

as w as n o t ic e d b e f o r e th e c o mbus t i on w a s b e gu n I f th e
.

volum e of n i tr ogen in th e azo tom e te r is l arge th e bubble s

will n ot h ave ve ry much liquid through which to t rave l
an d on this a cc o u n t i t is s o m e tim e s n o t s o ea sy t o m a k e a

prop e r comp aris on I n such a ca s e th e gas is ru n through

.

f or ab ou t te n mi n u te s a f t e r i t app e ars th at all th e ni tr og en

h a s b een d r iv e n o v e r .

Th en c lo s e s top c o ck N o 6 (b e twe en the azotom e ter and

-
.
29 8 LAB ORA T OR Y MANUAL OF OR GAN I C CH E M I S T R Y
th e combus ti on tub e) a n d w a sh th e n i trog en in th e a o
, z

t ome t e r wi t h o n e p o r t i on o f t h e p o ta ssium hyd r o xid e s ol u

ti on . This is d on e whil e th e r e s e rv oi r is in th e l ow p o si ti on
(I ) th e s t op c o ck b e i n g c a r e fully a n d p a r ti ally op e n e d to
,
-

a ll ow th e s o lu t i on t o r u n e a sily d o w n t h e i n sid e w a lls t o

a bs orb an y t r a c e s o f c a r b on di o xid e t h a t m ay b e pr e s e n t ,

a n d cl o s e d b e f o r e al l th e s olu t i on h as l e f t th e cup N ow .

wa sh th e gas in a simil a r m an n e r wi th succe ssive p o r ti on s

o f c old dis till e d w a t e r which h as b e e n r e c e n t ly b o il e d t o

drive ou t diss olve d air u n til al l th e p o ta ssium hyd r oxid e

1
,

s olu ti on is ou t o f th e az o tom e te r a n d th e r e s e r voir also .

A lw ays k e ep s om e liquid in t h e cup W hil e th e w a shi n g is

.

b e i n g d on e do n o t l e t th e p o ta ssium hydroxid e s olu ti on o ve r

flow . I t sh o uld be p o u r e d ou t a n d s a v e d f or a s e con d
c ombus ti on u n l e ss i t is sp en t a n d wh e n y ou p our it o u t
,
”

b e sur e n o t t o p our a l l o f it a t a t im e si n c e a ir may ge t ,

i n to th e rubb e r tub e a n d th en i n to th e azo tom e te r "

R a is e up th e r e s e rv o ir u n t il th e liquid in i t is on a l e v e l
wi th th e liquid in th e azo tom e te r in o rd e r th a t th e n i tr og en
will r e m ai n a t a tm o sphe ric pr e ssu r e thus pre ven ti n g an y ,

e rr o r fr o m l e a k a g e e t c ,
an d cl amp th e h o ld e r o f th e r e s e r
.
,

voir in this p o si ti on P l a ce a th e r m om e te r in s om e wa te r in
.

th e cup ab ov e o r h an g i t b e sid e th e a z o t o m e te r an d a ll ow
, ,

th e app a r a tus t o r e m a i n u n t o uch e d in a r oom o f u ni f o rm

t e mp e r a tur e f or a t l e a s t tw e n ty t o t hir t y mi n u t e s Th en .

re cord th e v olum e of th e ga s as r ead by th e b o ttom of

,

th e m e ni scus th e t e mp e r a t ur e a n d a ls o th e b a r om e t ric
, ,

r eadin g an d th e te mp era tu r e o f th e b a rom e te r .

Fr om th e se r e sul ts a n d th e w ei gh t o f cc of mois t 1 .

ni t r og e n (giv en in milligr a ms ) a s f o u n d in t h e a cc o mp an yi n g

t abl e s f or th e pr op e r t e mp e r a tur e an d pr e ssu r e y ou c an

, ,

calcula te th e w e igh t of n itrogen ob tain e d an d th en th e p er

c en ta ge o f ni tr oge n in th e subs tan c e (s e e s e c t ion on Cal
c u l a tion s p 3 00)
,
.

1
Oth e rwi s e t h is a ir will b e li be ra te d w h e n the w a t e r mi xe s w i th th e po ta ssium
hyd ro xi d e solu ti on w hi c h doe s n ot disso lve as mu c h air as w a t e r d oe s .
3 00 L AB ORA T OR Y MANUAL OF OR G ANI C CH E M IS TRY

G E N E R A L N OT E S

1 . substan ce s give ff ga se s such a me th an e wh ic h a

S ome o ,
s , re

n o t o idi x d by th e cup r i
ze i d i th ab se c f o yge ga s Th se
c ox e n e n e o x n . e

mus t b e mixe d wi th c a r s ely p w d r e d l e a d c h r oma te o r f r shly

o o e e

p r e c ipi ta t d c up r ous c hl r i de a d th e lo g laye r of cup r ic oxi de

e o ,
n n

r eplac e d wi th l a d c h r ma t e o e .

2 I s om c a se s th e
. n e t i r e spa c e o ccupi e d b y th e b oa t mus t b e
en

filled wi th cup r ic oxide mixed wi th th e substan ce in or de r t o ge t

in tima t e c o tac t n .

3 I.f a y n i tnr ic o i d N O h as e scxap e d t

e,h e a c t i on o
,
f t h e r e d u c d e

c ppe r spi r al it s p r e se ce c a be sh ow by th e b r ow n fume s f or m d

o n n n e

wh th e n i t r og ga is allow d t o c om u t i to th e air Ni t r og
en en s e e o n . en

as n i t r ic o i d oc upi s on ly h al f th e volume of th e same amou t f

x e c e n o

n i t r oge n in t h e f r e s t a te e .

VIII . Cal c ul ati on s , an d D i s c u s s io n of R e s ul ts

vi n g a sce r tai n e d th e volum e of th e ni trogen V its tem

Ha , ,

p er a t u r e t a n d ,
th e b,
a r om e t ric r e a di n g an d t h e t emp e r a t ur e o f

t h e b a r om e te r (p c orre c t th e b arom e tric r eadin g to z e ro

.

by usin g th e fol lowin g formula an d tabl e 1

.

Ho k at

wh ere H0 corr e c te d r ea di n g ;
h obs e rv e d r e a di n g ;
5
:

a coeffici en t ;
t te mp e ra t ur e ;

Th is t abl e give s th e c orre c t i on f or

1
a b ra ss
s c ale T he c orrec t i on is a pprox
.

ima t el y 8 pe r c e n t gre a t e r fo r a gl a ss s c al e I t is v e ry c on ven i e n t to pl ac e a

. .

co py of th is t ab le fo r re ady re fe re n c e in t he c a se surro un di n g th e b aromete r .

 O R GANI C C OM BUSTI ONS 301

The w e i gh t o f the n i t roge n c an n ow be f oun d by th e fo rmula

W t in r ms = 0 00 1 2 0 X V X (Ho fi
x
-“
2 73
.
g a 5 7
.

7 6 0

wh e r e is th e w eigh t of 1 cc of pure dry n i tr ogen

5 7
0 .

n o rm a l t e mp e r a tur e a n d pr e ssur e ;
V = v ol ume o f n i tr oge n in cubic c en t im e te rs ;
H0 co rr e c te d b a r om e t ric pr e ssur e ;
= v ap o r pr e ssur e of w a te r a t t :
°
p
t te mp e r a t ur e .

T ABL E OF VA P OR P RE S S U R E OF W AT E R 1

mm . mm . mm . mm.

w ei gh t of n i tr og en c an m or e r e adily be ob tai n e d by
T he
usin g th e a cc omp a n yi n g t abl e s (p a g e which give th e
w eigh t o f 1 cc o f moi s t n i t r og e n a t di ff e r e n t t emp e r a t u r e s an d
.

pr e ssur e s .

T h e p e rc en ta g e o f ni trog en in th e subs t a n c e will b e

W t ni t ro ge n X 1 00
P er c en t N
.

W t subs ta n ce
.

Fo r l ogari t hmic c alcul a ti on 2

1
rom S c h eel an d Heu s e A n n
F , . P hys i k , 3 1
.
73 1 , as giv en in th e
’

S m i th s on i an P h ysi c a l T abl e s T h ird , R e prin t of S i xth R e vis ed E di ti on

I S4 S '
“

2
A t ab le of four pl ac e l ogari th ms is given
-
on p .
3 08 .
3 02 L AB OR A TOR Y MAN UAL OF OR GA NI C CH E M IS TR Y

L og w t . . 1 cc . N at t
°
an d H0
L og V .

L og w t t o t al n i t r og e n
. .

L og . 1 00

S ub tr a c t
L og w t . . subs tan ce
L og p e r . cen t N
Th e L imi t of E rr or .
— This
calcul ate d in the s am e may be
g en era l w ay a s given on p 2 5 8 For r e sul ts of an alysis ob tain e d . .
,

by th e m e th od d e scrib ed th e all owe d e rr or sh ould ordin arily ,

n o t be m o r e th a n 1 0 p a r t s p e r t h ous an d an d n e v e r m o r e t h an 2 0 ,

p ar ts per thousan d Ch e ck r esul ts sh ould also com e wi thi n th e s e

.

figure s .

T h e f o llo w in g r e sul t s are giv en as b e in g typic a l o f th e p o ssibili

t i e s in th e m e th od : p ni tr o to lu e n e ( C7 H 7 O N ) w as an a lyz e d
- -
2

f or n i tr og en by M r S L H an dfo r th wi th th e f o ll ow in g r e sul t s
. . .

( on ly t w o a n a lys e s m a d e ) N
: th eory c a lls
f or N T h e e rr or h e r e is an d p ar ts p er th ous an d ,

re sp e c tive ly T h e s am e subs tan c e w as a ls o an alyz ed by M iss

.

S ophi a S c h ulrn an , e rr o r ,

( )
l o w ,
a n d ( )
l ow p a r t s p e r t h o us an d ; an d a ls o by M r .

H R P yn e N =
. .
,
e rr o r (l ow ) p ar ts per , ,

th ous an d M r T C Tayl or ob ta i n e d f or n i trog en in diph en yl

. . . .

a mi n e ( C 1 H 1N ) 2 1 ,
th eo ry on e ,

r e sul t is qui te f or tui tous th e e rr or in th e o th e r is ,

p ar t s
p e r t h o us a n d M r G. eo H W a.ld e n ob t a i n e d f or a c e t an ili d e
. .

( C gH QO N ); N a r o 3 2 % . t h e o ry ,
e rr o r is ,

( )
l ow a n d
,
p a r t s p e r t h o us an d T h e g r e a t e s t di ff e r .

e n c e in th e r e sul t s in a n y o f t h e s e t s of d e te rmi n a ti on s me n

tion e d is (M r P y n e ) a nd t
. h e e rr o r b a s e d on ,
t h e low e r ,

figu re is ,
p ar t s pe r th ous an d .
3 04 WE I G HT OF ONE C UB I C CE NTI M ETE R OF M OI ST
G
NI T R O EN I N M I LLI GRAM S
b 7 12 7 16 7 18 720 7 22 7 24

7 16 7 20 7 22
 W E I G H T OF ONE C U B I C C E NTI M E T ER OF M OIS T 3 05
N I TRO G E N IN M I LL I GR AM S
b 732 7 34 736 7 44

7 36 73 8 7 40
3 06 WE I G HT OF ONE CUB I C CE N T I M ET E R OF M OI ST
G
NI T R O EN I N M I LLI G RAM S
b 75 2 754 756 7 58
t L O GA RI THM S 3 09

7 443 7 45 1 7 45 9 7 46 6 7474
7 5 29 7 5 28 7536 7 5 43 755 1
7 59 7 7 69 4 761 2 7 6 19 7627
767 2 7 679 7686 7 69 4 7 79 1
7 7 45 7 75 2 7 7 69 7 767 7 7 74

78 18 7825 7 83 2 7 83 9 7 846
7 8 89 7 89 6 7 9 03 79 19 79 1 7
7 9 59 7966 79 73 7989 7987
8028 8 03 5 8 04 1 8 04 8 8 05 5
8 09 6 8 102 8 1 09 8 1 16 8122

8 162 8 1 69 8 1 76 8 18 2 8 1 89
8 2 28 8 23 5 8 24 1 8 248 8 2 54
8 293 8 299 8 3 06 83 1 2 83 1 9
83 5 7 8 3 63 83 7 9 83 7 6 83 8 2
8 4 29 84 2 6 8 43 2 843 9 8 44 5

8 48 2 8 488 8 49 4 8 5 00 8 5 06
8 5 43 8 5 49 85 55 856 1 85 67
8 6 03 8 6 09 86 1 5 86 2 1 86 2 7
8 6 63 86 6 9 86 7 5 868 1 8 686
87 22 87 27 8 733 8 73 9 8 7 45

8 7 79 8 785 8 79 I 879 7 88 9 2
883 7 88 4 2 8 8 48 8854 88 5 9
88 9 3 8 8 99 8 9 04 89 1 0 89 1 5
8 9 49 8954 89 60 89 6 5 89 7 1
99 9 4 9 9 9 9 901 5 99 29 902 5

99 5 8 99 63 99 69 99 74 99 7 9
9112 9117 9122 9 1 28 9 13 3
9 165 9 1 70 9175 9 1 80 9 1 86
921 7 9222 9227 9 23 2 9 23 8
9 269 9 2 74 9 2 79 9 2 84 9 289

9 3 20 93 2 5 93 39 93 3 5 9 3 49
93 7 9 93 7 5 93 89 93 85 93 90
94 29 94 2 5 9 43 9 9 43 5 9 449
9 46 9 947 4 947 9 9 48 4 9 489
9518 9 5 23 95 28 9533 9538

9 5 66 95 7 1 95 76 958 1 9 5 89
96 14 96 19 9 6 24 9 6 28 9 63 3
966 1 9 666 96 7 1 96 7 5 9 68 0
9 79 8 9 7 13 9717 97 22 9 7 27
9 7 54 9759 9 7 63 9 7 68 9 7 73

9 8 00 9 8 05 9 8 09 98 14 98 1 8
9 845 9 8 59 9 854 9859 9 8 63
9 89 0 9894 9 899 9 99 3 9 99 8
99 3 4 99 3 9 99 43 9 9 48 99 5 2
99 7 8 99 8 3 9 98 7 999 1 9996
3 12 L IS T OF A PPA R AT U S FOR GE NE RAL OR G AN I C CH E M IS TRY

LI S T OF AP P ARA T US FOR G E N E R AL OR GAN I C

CH E M I S TR Y 1

Box I — AT R I CLE S RE TUR NA BLE

A d di t i on u
t be
1

f Beake r , lipp e d G riffin s l ow form , 50 c c

’
,

B eake r lipp ed G rifli n s l ow form

, , 1 00 c c
’

1 B e ake r lippe d G ri ffi n s l ow f orm

’
, , 1 50 c c ,

B eaker lipp ed (Pyrex ) G ri ffin s l ow form 2 5 0 c c

, ,
’
,

I B e a ke r lipp e d G ri ffin s l ow f o rm
’
, , 400 c c ,

I B ea ke r lipp e d G ri ffi n s l o w f o rm
’
, , 6 00 c c ,

1 B e ake r li pp e d G riff i n s l ow f orm

’
, , 8 00 c c ,

1 B e ake r lipp e d G rifli n s l o w fo rm

’
, , 1 000 c c ,

6 B o tt l e s s q G S fo r h a n di n g in liqui d pre p a ra t i on s 1 5 c c
,
.
, . .
, ,

6 B o t tl e s w i d e —
,
mo u t h e d gl a ss s t opp e red ro un d 1 0 c c fo r h a n di n g
,
-
, ,
.
,

in s oli d pre p a ra t i on s
2 B o ttl e s t i n c t ure n a rr o w mo u t h G S
, ,
250 c c ,
. .
,

3 B ottl e s w i de mo u th 2 5 0 c c
, ,

1 C a l c i um c h l o ri d e t ube 6 i n c h ,
-
.

1 Con de n s e r s e a l e d j o i n t s b ul be d i nn e r t ube 1 2 i n c h e s l on g

"
, , ,

I Co n de n s e r s t ra i gh t i n n er t ube
, . .

1 Con den s e r i n n e r t ube a ir c on d en s e r 1 5 in c h

“ -
, , ,

1 Wa t c h gl a ss 3 — i n c h ( c ove r gl a ss)
,

1 Wa t c h gl a s s 4 %i n c h ( c o v e r gl a ss )
,
-

1 B o tt l e s e a li n g t ub e
, 15 c c ,

1 Cyli n de r gra d u a t e d 1 00 c c
, , .

1 C yli n de r gra d u ét t e d
'

, 10 c c , .

1 E va p ora t i n g d ish p o r c 6 c m d i a m ( Coo rs),

.
,
. .

2 Fl a s ks d is t illi n g r o u n d b o t t o m
, , 3 0 c c ( P yre x ) ,
. .

2 Fl a sks dis t illi n g B

, C ro u n d bo t to m 5 0 c c ( P yre x )
,
. .
, ,
.

2 Fl a sks d is tilli n g B
, C ro u n d bo tt om
,
25 c c
.
( P yre x ) .
, ,
1 .

1 Fl a s k di s t illi n g B
, C ro u n d bo tt om 2 5 0 c c ( P yre x )
,
. . .
, ,

2 Fl a s ks E rl e n me y e r 1 5 0 c c
, , .

2 Fl a s ks E rl e n me y e r
, 50 c c ,

1 Fl a s k” E rl e n me y e r 2 5 0 c c ,

1 Fl a sk h e a vy gl a ss f o r fil t e ri n g w i t h si d e n e c k 5 00 c c
, , , ,

1 G l a ss e v a p o r a t i n g d ish 5 c m -
,

1 F l a s k r o u n d bo t t o m
, 1 25 c c ,

I F l a s k r o u n d bo t t o m
, 2 50 c c ,

1 Fl a sk ro u n d b o tt om sh ort n e c k
, 3 00 c c , .
,

1 Fl a sk r o u n d bo t t om
, 5 00 c c ,

1 F l a s k r o u n d bo t t o m
, 1 000 c c ,

1 F un n e l 4 c m di am, .

S p f p v
1 ee re ac e , . .

Th giv f t h k f v i
2
e s e a re ly en or e sa e o c on e n e n c e on .
 LI S T OF AP PARAT US FOR G ENE R AL OR GANI C CHE M I STR Y 3 13

1 u n n el 7 5 c m di am sh ort stem spe c i al

F ,
. . .
, ,

1 F u n n e l d roppi n g 6 0 c c
, ,

1 F u n n e l , se p ar a t o ry S qui bb s 2 5 0 c c
’
, ,

1 F un n e l B u c h n e r po rc e l a i n 5 c m d i am
, ( Coo rs), ,
. .

1 G oo c h p e rf o r a t e d pl a t e

1 S e t o f t h r e e t h e rmome t e rs sh or t s c al e w i t h c a s e ( Fish e r) , ,

1 Th e rmome t e r mil k gl a ss sc a l e 3 6 0
°
, C , ,

6 T e s t t u be s 4 X 1 ” ”
.
,
"
1 2 T e s t t u be s 6 X ; ,

3 T e s t t ube s 8 X I
-
”
.
,

2 T e s t t u b e s si d e n e c k 6 X I
-
, ,

1 M e l t i n g p oi n t a pp ara t us .

1 H ard gl a ss t e s t t ube P yre x sp e c i al 1 0 c m X 9 mm , , , .

1 M o r t a r gl a ss l i p e d 2 i n c he s
, p , 4

1 P e s t l e f o r ab o v e gl a ss ,

1 S p a t ul a a n d s o o n c o mbi n e d p o r c c m
p 1 ,
.
,
2

1 G l a ss s t o p c o c k 2 mm-
,

B ox I I A T
R I CLE S RE T U NA R BLE

2 B ur ette c l a mp s yiron
2

1 Bu r c h i mn e y :
rn e .

1 B urn e r s ta r supp o rt f or c h i mn e y
,

2 Con d e n s e r c l a mps ir o n l a rge , ,

2 Co n de n s e r c l amps iro n me d ium , ,

4 C l a m p l
h o de rs f o r i i n c h r od s , fi
-

1 S e t o f ri n gs f o r s t e a m b a t h

1 Fil t e r pu mp w i t h sp e c i a l C o lu mb i a c o upli n g m e d iu m 4 5
1 i n c he s E A 5 6 24 ,
. .

1 Oil b a t h ir on 6 — ,
i n c h modifie d ,
E A 6 16
,
: . .

2 R i n g s t a n d s me d iu m ir on mod ifi e d in s h o p
,
E A 6 5 40
, ,
. .

1 R i n g f o r ir on s t a n d 2 i n c h e s ,
E A 6010 .
-
. .

1 R i n g f or ir on s t a n d 3 i n c h e s ,
E A 60 10 . . .

S e t c ork b or e rs N o s 1 9 bra ss (Ol d Ca t )

—
,
E . A 2 841 . . .

1 S c r e w c l a mp
1

.E A 2 08 0 . .

1 T e s t t ub e r a c k COpp e r
-
,

1 T ri p o d 4 2 i n c h e s d i am E 81 A 7 000
'

. .
,

1 Wi n g t o p f o r bur n e r E .A 1616 . .

1 S e t w e i gh t s r e n t a l 7 5 ( Co lumbi a S t yl e B )
,
.

T h e f oll o w i n g pi e c e s o f app ara t us a re t oo l arge t o go i n t o t h e p a c ki n g box ,

b u t t h e s t u de n t w ill n e e d t h e m i mme di a t e ly t h e re fore h e sho ul d go t o t h e

l
,
l l l l

R i n g s t an d s , large i ron xtra h e a vy mod ifie d s h op

0 0 0 0 0 0 0 0 0

2 , ,
e ,
In . .

T he foll o w i n g an d ot he r a pp ara t us may be i

ob t a n e d a t r
t h e S toc k oo m at an y

t i me as n e e d e d

M an o me t e r s t an d P or c e l a i n c a sse ro l e s
Ho t -
w a t e r f unn e l E v a por a t i n g d ish e s
3 14 L I ST OF A PPA RAT U S FOR GENERAL OR GANI C CH EM I S TRY
F un n els Nos 5 an d 6 ( 1 2 c m an d 1 5 c m )
,
. . . S p e c i a l dis t illi n g flas ks -

E l ec t ri c mo t or I n s t rumen t s
S t irri n g a pp arat us Gl a ss stop -
c oc ks
De si c c ato rs L arge c on d en e s rs , bul bed or s t rai ght i nn er

E tc .

Box —
I I ARTI CL E S NON-RE TURNABLE

4 L
e n gt h s gl ass t ubi ng 6 mm bore 2 f t ,
.
,
11
2

2 Len gt h s gl a s s rod 4 mm bo re 2 %ft ,

.
,

3 P o ro us t il e s
1 Fil e ra t t a il 5 i n c h e s
, ,
.

H Fil e ra t t a il 7 i n c h e s
, ,
.

H Fil e t ri an gul a r 5 i n c h es,

H Wir e ga uz e 4 i n c h e s sq u a re
,

H S t ee l sp a t ul a 7 5 c m ,
.

H S o d i um kn if e ( c ommon kn if e )

H T e s t t ub e b rush sp o n ge e n d
-
,

H T e s t t ube c l ea n e r
-

1 P a c ka ge fil te r p a p e r 1 2 %c m Wh atman NO 2 ,
.
, .

2 B o xe s ma t c h e s

1 T e s t t ube h o l d e r n i c ke l
-
,
.

1 S p o n ge

1 Box l abe ls sq u , a re

2 T o w e ls

8 Fe e t bl a c k ru bbe r t ubi n g 333 i n c h I D ,

.

1 2 F ee t w h i t e rubb e r t ub i n g i n c h I D h ea vy w a ll ed , . .
,

1 P a ir go ggl e s w ir e ga uze pr o t ec t ors

,

2 D oz en a ssor t e d c o rks si ze s 1 —1 5 ,

1 S ube ri t e ri n g 2 %i n c h e s I D
,
.

1 Ca ke F ummo so ap .

1 T in p a il

N Loc ks w i th ke ys E a gl e Lo c k Co ,

H V i a l li t mus p a p e r n e u t ra l S qui bb s
’
, ,

H P o c ke t rul e r

H R ubbe r s t opp e r N o 7 3 h ol e s t o fit 2 5 0 c c bo t t l e .
, ,
-
.

H R u bbe r s t opp e r N o 5 1 h ol e t o fit t e s t t u be w i t h si d e n e c k
.
, ,
-
,
.

H R ubb e r s t opp e r 3 h ol e s t o fit 2 5 0 c c sh o r t n e c k R B fla s k
,
-
. . . .

H R ubbe r s t opp e r N o 5 2 h ol e s t o fit t e s t t ub e wi th si d e n e c k
, .
,
-
.

H S c is so rs

H Co rk s c r e w W ill i ams on “
,
f i re Novel t y Co

R ubbe r w a sh e r .

H P erf e c t i on s a n d p ap e r h o l d e r H . 81 S .

1 P ac kag e sa n d p ap e r
1
,

F k p i g Al b d kt p l i or ee n e ren e es o c ean .
 3 16 LI S T OF CHE M I CAL S . FOR LON G CO R S E U
L I S T OF CH E M AL SIC F OR LON G U —
CO R S E Con ti nu ed

FI RS T S E ME S TE R

N a me an d Sp ec i fi c a t io n . Am o u n t .

Di -
n i t r obe nz oic ac id (1 3 5)
E th e r M er c k s,
’
.

E th yl bro mi de .

Feh li n g s so lu t i on
’
A 1

Fe h li n g s solut i on
’
,
B
F orma l in .

G l ss w a oo l .

G ly r l c e o .

Hyd roc hl ori c ac i d c o n c ,

H ydro xyl ami n e h y droc h l ori de

I od i n e
Li me w a ter .

M agn e si um ( G rign ard s) ’

M en t hol .

M e thylal .

M ethyl al c ohol .

Nap h th al e n e p ow de r f o r M P d e te rmi , , . . 7

na t i o n

P hen olph thal e i n sol ,

Ph osph ori c ac id (1 7 )
Phosphorus pe n tac hlo ri de .

Pho sphorus re d , :
.

P in en e
-Poro us t il e gran , .

P ot a ssium c arbo n a t e fused ,

P ota ssium h ydroxi de .

Po ta ssium h ydroxi de purifie d by al c ohol ,

.

P o ta ssium p e rman ga n a te
Qui n oli n e ( syn th e t i c ) for BI P de termi n a .

t i on .

Ra p e s ee d o il .

S al i c yli c ac i d po w de r
, ,
f or d e t e rmi
n a t on i gm .

58 S c hifi s
’
a l deh yde re age n t (f uc hsi n e s ul furr

.
‘

ou s ac i d) G . S . B .

59 S o da li me dry , .

60 S o d ium b i c a rbo n a t e

1 The g r ou n d p a rt of the gl as s s top p e r of the b o t tl e c on t a in in g the al k a l in e h lf a of

h g
F e l in
’
s s o l u t io n is d ip p e d in m e l t e d p a r a f n fi bf b e o re e in g used . h
T is p r e v e n t s t h e s t op p e r

fro m b ec o m in g f “
ro ze n C o r a n d ru
. er k bb t p p s o e rs c a n n o t be use d .

2
S . T =sea
. l d e tu b e .
 LI S T OF C H E M I CAL S FOR LON G COU R SE

LI S T OF CH E M I CAL S FOR L ON G CO U
R S E — Con tin u ed

FIR S T S E ME S TE R

N a me an d S p ec i fi c a t io n . Amo u n t .

S od ium bis ul fite , sa t . so l :

S od ium rbon ate dry

ca ,

S od ium c h l o ri d e sa t s o l ,
.

S od ium h y droxi de
S od ium me t a lli c
,

S ulfuri c i d c on c
ac ,

S ulfuri c ac i d f u mi n g ,

Zi nc duS t . 0 o
"
0 0 0 0 0 0 0 0 0 0 0 0 o o o o o o o o o o o o o o
3 18 LI ST OF CHEMI C ALS FOR LONG COURSE

L I ST OF CHE M I CAL S FOR LON G o

C U S
R E l

S E COND S E ME S TE R

N a me an d S p ec i fi c a t io n .

A c et c i ac id (gl ac i al ) 75 c c .

A c e ta c e t c i e s te r
A c e to n e

Al miu ium c hl o ri de (anh yd )

n

Amm on i u m a c e ta te ( d ry) .

Amm on iu m h yd rox i de c on c ,

Amm on ium moly bd a t e rea ge n t

A n i mal c h a rc oa l
A n th rac e n e

B t h i ph
e nz ene , fr o en e ee

B l d h yd
e nza e e .

B yl h l ri d
en z c o e

B l hi g p w d r
e ac n o e

B r mi
o ne .

B r mi o t r ne w a e

B r mi i CCl 5 %
o ne n ; ,

B utt r e .

Ca n e suga r .

Ca rbon dis u l fid e
Ca t e c h o l
Ch l o ro form , U S P . .

Ch romiu m t ri oxi d e
Ci n n ami c ac id
Co ppe r rbo n ate (ba si c )
c a

Co ppe r sul fa t e N
Corn c ob (gro un d )
Co t t on (a b so rbe n t )
D i me th yl an ili n e
D i me th yl su lfate .

D iphe n yl —thi ourea .

E gg .

E th e r ( M e rc k s)
’

E th e r ( o ver sod ium

“

E th yl a mmoni um c h lori de

1 S ee foot-n ote s . p .
3 15 .
3 20 ‘
b
LI ST O F CHE M I CAL S FOR L ON G fiCOURS E
.
’

LI S T OF CH E
'

M I CAL S F OR L ON G COUR S E;
'

Con ti hzZed
S E C OND S E ME S TE R

N a me an d S p ec i fi c a t ion . Am ou n t .

Con t a i n e r .

79 S ilve r n i t ra t e ,
N /10 10 c c . A mb . G . S B .

80 S od ium, me ta lli c . 12 gms . WM , G ~S. . B .

(in c an ) "

S od ium bis ul fite , sa t . s ol

S odi um rbo n a te c rys t

c a ,
. .

S od i um c h lo ri d e c omme rc i a l,

S o d ium c h l ori d e sa t sol , .

S od ium d i c hro ma t e
S od ium h y droxi de
S odium n i t ri te
So d ium n i t roprussi de
S ta rc h so lubl e
,

S ulfan ili c ac i d
S ulfuri c ac i d (fumi n g)
T an n i n ( ta n n i c a c i d )
T in gran ul a t e d
,

T oluen e c omme rc i al
,

T olui di n e (orth o)
T riph e n yl c h l or me th an e
- -

Xylen e c omme rc i al
,
.

Zi n c c h lori de N ,

Z in c d ust c ommerc i al
,
 LI ST OF CH E M I CAL S FOR S H OR T CO RS E U 3 21

LI ST OF CH E M I CAL S F OR S H ORT COUR S E l

N a me an d S pec i fi c a t io n . A mo u n t .

A i
c et c ac i d gl ac i al
,

A c e ti c a n h yd ri d e

A c e t ac e t i c e s t e r .

A c e t on e

Amm on ium h ydroxi de ,

c on c

Amm on i um mo lyb d a t e ,
s ol

Amyl a l c o h o l ( iso )

A ili
n ne I
A i li
n ne from sulf at e ,
for B . P d e t e rmi n a

A n i mal c ha rc oal .

A n t h r a c e n e p ow d e re d
, ,
f or M P de te rmi
. .

n a t i on

B e nze n e , 80
°-
82
°

B enz e n e ( th i oph en e free)

B i
e nz n e 70
° —8 0 °

B i
e nz o c a c id
Bl e a c h i n g po w d e r

Br omi n e

B r mi
o ne , 5 % in ca rbo n te t rac h l ori de
B utt r e

Cal c ium c h l ori d e , a nh ydrous ,

.

Ca n e suga r
Ca t ec h ol
Ch l oro fo rm
Ci nn a mi c a c i d
Copp e r c a rbo n a t e ba si c ,

Cop p e r oxi d e p o w de r ,

Copp e r s ul fa t e a nh yd ,

Copp e r sulf a t e c ryst ,

Co pp e r sulfa t e N so l ,

Coppe r w ire , N O . 16

Co tto n , ab o s rbe n t Vi a l

1 S ee p re fa c e p ;
. v. a n d al s o f o ot -n o t es , p .
3 15 .
3 22 LI ST OF CHE M I CAL S FOR S H ORT CO R S E U
LI S T OF C HE M I CALS FOR SH OR T CO R S E—Con tin ued U

Na me an d Sp ec i fi c a t io n .

D i me thyl a n ili n e .

D iphen yl th i o ure a
-

E th e r ( M er c k s )
’

E th yl mmon ium c hl o ri de ,
a so l

E th yl e n e d i bro mi de .

Fe h li n g s solut i on A
’
,
“ ” 1

Fe h li n g s solu t i on
’
B ,

Fe rri c c h l o ri d e }; mol a r ,
e

Fe rro us sulfa te
Fe rro u s sulfid e
G alli c a c i d
G l a ss w ool
H ydroc h l o ri c ac i d c on c ,

H ydroxyl ami ne hyd roc h l o ri de

L dea ac e ta t e , N so l

Lim w e a ter

M ic hle r s ket o n e
’

M on o me thy l an ili n e .

N a ph t h al e n e , p ow dered ,
f or M . P . d e te r
mi nat i on
Ni t ri c ac id ,
c onc

N i trobenzene , co mmer c i al
N i trobe nze ne , f or B . P . de t e rmin a ti on .

P h th ali c an hy dri de
Ph en olphth alei n sol
Ph en yl hydrazi n e

Ph o sph orus pe n toxi de

Ph o sph orus oxyc h l o ri de
Ph o spho rus t ri c h l ori de .

P i n en e
P oro us t il e small broken piec e s
,

Po t a ssium c arbo n at e a nh yd , .

P o ta ss ium h ydroxi de
Po t a ssium h ydroxi de puri fied by al c ohol , .

1 See f oot -n ot e . p .
3 16 .
 G E N E R AL IND EX

N OTE — S u b s ta n c e s i
w th a pre fi x su c h a s l me n thon e p tolun i tril e
-
,
-
, e tc .
, a re

in dexed un der th e n ame of th e subs ta n c e regardl e ss o f the pre fix .

A Addi ti on u t be . . 13

Abs rp t i on
o bo t t l e s , h o w t o fill ,
f or Al h l
co o a bs olu t e pr e p a ra t i on of
, , 26

w a te r bo il in g—p o i n t . 24

Abs orp ti on bo t t l e s , h o w t o fill ,

f or f or d ryi n g a pp a ra t us 15

C02 . 2 43 frac t i on a t i on of mixture 22

A bs rp t ion bot t l e s w ei gh i ng
o , 2 48 s ec on dary pre p ara t i on of , 73
t ra i n . 23 6 t er ti a ry pre p a ra t i on of
, 69
Ac c iden t in c a se oi , . . 6 A l c oh oli c p o ta s h f or h a l oge n t e s t , . .
38
Ac e tac et ic e ster f e rri c c hlori de , A lc oh ols iden tific a t ion of
, 55
reac t i on s of 54
A ldeh yde pre p ara t ion from
c e ta , Al dehyde ammon ia s ee Ac etal de ,

a l d e h y d e a mmo n i a 90 h yde a mmon i a .

o f a s o lu t i o n o f 83 Aldeh yde s te s t s f or , 91
a mmon i a pre p a ra t i o n o f , 85 Alkalie s ac c i den t s
, 6
Ac e tals .
9 4 A l kyl a t i on o f a n h y d roxyl group . . 1 80

Ac eta mide pre pa ra tion of ,

1 15 Alumin a pre pa ra t i on of
, 23 8

se ale d t ube me th od 117 Alumin ium c h l ori de in Fri edel ,

o Ac e t a min O benz oi c ac i d pr e p a ra Cra f t s rea c t i on

’
- -
,

t i on of 1 89 op e n i n g s ea l e d b o t t l e s o f

A c etanilide forma tion of ,

.
3) mer c ury c o upl e re f e r en c e f or , . .

Ac e ta n th ra n ilic a c i d pr e p a ra t i on of ,
1 89 oxi d e pre p a ra t i on o f
, .

A c e t i c a c i d f or a c c i d e n t s ,
. 6 Amin o a c id prep ara tion an d prop
,

A c e t on e c h e mi c a l pr o p e r t i e s of
, 98 e r t ie s .

f or dryi n g a ppa r a t us 15 -
ac e t c i ac i d prep ara t i on
, of .

Ac etoph en on e redu c tion of , 73 Amyl en e , in t e s t s f or d oubl e

Ac et o toluid ide prep a ra t i on of
- -
,
1 64 bon d f
’

Ac etylac e tone f erri c c h l oride t es t ,

. 178 Anili n e,pre p ara t ion of
Ac etyl ation w i th a c e tic a n h ydride , 1 64 A im
n a l c h a rc oa l f o r d ec ol oriz i n g

ac et yl c h l o ri d e 1 0 —
3 4 . . .
,
1 65 Solu ti on s 1 25 I 5 0 1 64 , , , 167

Ac etyl c hlori de prepa ra tion of , . 102 An isole prepara tion of

,
1 80

reac t ion s 1 03 An thraquin on e pre pa ra tion of , . 2 10

Ac etyl en e from c a l c iu m c arbide

, . .
50 A tomi c w eigh t s table of , .

e th yl e n e d i br omi de 52 I n s ide ba c k c over .

prop ert i e s of 50 Au t i dat i on o f ben zal deh yde

ox 182

Ac etyli des c uprous , 51 A t

z o ome t e r f or n i t rogen c ombu s
,

t i on
A c ids , ac c id en t s t e s t in g
 3 26 GENERAL I ND EX

Cal c ul a ti on s f or c arbon and hy

B a bo funn el d rogen .

B a rome t e r ta bl e of c orr ec t i on s f or
,
.
f or i trogen
n 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

B a th s f or h ea t in g me ta l ,
.
Camph en e prep a ra t i on of
,

Ca mph or pre para t i on of

, .

B i Can e su ga r h yd rolysis of
en d n g gl a ss t ubi n g .
,

B en za l d eh y de r e ac t i on s .
Carbon d e te rmi n a t i on of
,
,

B e n z e n e c h e mi c a l pro p e r t i e s 13 8
t e s t s f or . O O O O O O O O O O O O O O O O O O

h is tor i c a l n o te 139 Ca rbon d i oxid e ge n e rat or f or nit ro

sulfon i c a c id s odi um salt prepa , ,

ra t i o n o i Ca rron o il i de n t s
f or ac c .

B en zi di n e rea rran gemen t Ca s t or o il f or a l ka li in th e ey e

B en zin e prope r ti e s C a te c h ol f er ric c h l ori de t e s t
,
,

Benz ol e n e n a me f or b e n z i n e Cellul o se a c e tat e f orma t i on of ,

,

B en zyl c hlori de in Frie del Craft s -

’ C eriu m d i oxi de prep a ra t i on of ,
,

reac t ion Ch emi c als amou n t s , .

l is t s s ee L ist Of Ch emi c a ls
.

t e s t f or h a l ogen in , .

B lank de termin a tion s method of ,

3
2 46
Ch romi c ac id , ox i da t ion w i th .
5 4, 8 3 , 8 5
Bl an ke t s ,
f o r fire 99 , 2 10

B oa t , f or orga n i c c ombus tion s 23 6 .

Cin n ami c ac id , d ec omp osi t i on 1 83

t u be piggie 251
reduc ti on t o h y droc inn ami c
ac id
B oilin g d isc ussion of
,
.

B oilin g poi n t c orrec t

-
1 7 18
Cl aisen d ist illing fla sk
,
.
,

c orr ec t i on f or c ha nge in a ir Combus t i on of ga se s .

e xpl osi v e su b s ta n c e s
pre ssure .

B oilin g p oin t de fin i tion

-
,

d e te rmi n a t i on of subs tanc es c on ta n ing i mer

liqui d s f or de te rmi n i n g
B omb tube h ow to seal C ombu s ti on of s ub s tan c es c on tain
“

-
,

B oric ac id for ac c id en t s
B rombenzen e prepara t ion oi . .
C ombus ti on u bs tan c es c ontai n of S
,

B romin at ion of an aroma tic h ydro in g ph o sph oru s

C ombus ti on of S ubs t an c es c ont ain
Br omi n e , ac c i de n t s
b o tt l e s , me t h od pen in g Co mb u s t i on of subs tan c es c on ta in
‘

of O .

B ubbl un t e r
e c o
in g sul u f r
B umpi n g c a us e s a n d me th od s C ombus tion prope r , f or c arbon and
‘

,
of

pre ven t ion 19

.

B u tte r h ydrolysi s of 1 08 C ombus ti on prope r ,

f or nit oge n r . 293
,
-
tube , f or th e de te r mi n a tion of

rbon and h ydr ogen

ca
C
C ombu s t i on t ub e f or n i t r ogen
“

,
.

Cal c ium c hl or i de f or ab o s rbin g

f or d ryi n g liqu i ds ,
s ee Dr y
in g s
a ge n t .

Ca l c iu m c h l ori d e t u be fillin g ,
3 28 GE NE RAL I ND EX

E t h yl prepa ra ti on of
ac e ta t e , 1 06 G
E th yl a min e h ydroc h l o ri d e in t e s t , . 121 G lli c ac id f erri c c hl ori de tes t
a , 1 78
E t h yl a mm on ium c h l o ri d e in t e s t , 121 G a s purifyi n g a pp a ra t us . 0 0 0 0 0 0 0 0 2 28

E th yl ben z e n e pre p ara t i on o f , 141 G ela ti n e prec ipi ta ti on w i th tann in

, 1 93

E th yl ene c h e mi c a l pro pe r t i e s
, 44 . .
, 48 G la ss t ubin g ben din g , . 28

p ie p a ra t ion fr om a l c o h o l a n d G lyc in e preparation Of

, 1 24

ph OS ph oric a c i d G lyc oc oll preparation of

, 1 24

E th yl en e pre p a ra t i on from a l c oh ol
, G rade s laboratory
, . 2

a n d ph osp h orus p en tox i d e . .

48 G rease for s top c oc ks -
2 29

E th yl en e d ibr omi de pre p a ra t i on

.

of , 40 Grign ard s reac tion ’

. 69
prope r t i e s of 45 G uard tube in organ ic c ombusti on s , 2 45

E th yl i od i de pre p a ra t i on of ,
.
35
prope r t i e s 38
H
i soc yan a te f orma t i on an d prop , H al ogen s det ec t i on w i th sod ium
,

e rt ie s . d ec ompo si t i on
E x trac t i on w i th r Hal oge n s t e s t f or w i th a l c oh o li c “
e th e ,

E y e, a lkali in pota sh e t c ,
”
38 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
,
1 50

Harde n ed fil t e r p a p er . 1 70
F H eli an th i n e . . 171

Feh li n g s s olu t i on re du c t i on of
’
, , H e teroc yc l e s n i trogen ,
2 13

w i th a l de h y de s 9 1 182 , H exame th yl en e te tramin e prepara ,

Feh li n g s s olu t i on r e d u c t i o n of t i on of
’
, , 0 0 0 0 0 0 0 0
96
w i th su gars H ippuri c ac i d f or glyc oc oll e xperi ,

Fil te r flu t e d
,
men t .

h ard en e d H is tori c al in trod u c t ion f or th e de

F ire in c a s e of
,
t e rmin a t i on of c arbon a n d h y .

e xti n guish e r drogen .

Fittig s syn th e sis of a n a roma t i c

’
H is toric al i n trod u c t i on f or th e d e
h ydroc a rbon 1 41 t e rmi n a t i on o f n i t rogen 26 9
Fl a sks Cl a is e n
, 76 H ydroc arbon paraffin ; prope rt ie s , 32
d i st illi n g 11 H ydroc in n a mic a c i d prep ara ti on of , 1 84

E rl en me y e r 1 3 14 ,
H ydrogen d e te rmi n a t i on of
,
0 0 0 0 0 0 0 217

Laden burg 11 22 ,
in organ i c subs ta n c e s t e s t f o r , .
30
Fluore s c e i n f orma t i on of ,
171 c h l ori de pre p a ra t i on of
,
195 . . .
, 198

Flu ted fi l t e r . 1 28 H ydrolysis of bu tter 0 0 0 0 0 0 0 0 0 0 0 0 0 1 08

Formal d eh yd e re a c t i on s 96 e th yl ac e t a t e 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 06

re s o r c i n o l t e s t 96 h ippuri c ac id 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 24

Frac t i on a t ion a ppa ra t us o r c olumn 25 is obo rn y l a c e ta te 0 0 0 0 0 0 0 0 0 0 0 206

Fri ed el Cra f t s re a c t i on
-
’
1 44 l ec i th i n 0 0 0 0 0 0 0 0 1 10

Fu c h s in e sulfuro us a c i d rea gen t f or

-
me th yl a l 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
94
H y droxyl amin e hydroc hl ori de ,
f or
Funn e l , B a bo 159 pre parin g an oxime
Bu h c ne r 51 52 c upro us c h l ori de 0 0 0 0 0

36
h o t w a te r 1 28

se pa rat ory S quibb s ,

’
36
sh a pe d -
.
36 I soborn e ol pre para t i on o f
, . .

F urfural te s t f or pen to s es ,
13 2 I s ob orn yl ac e ta t e p r e p a ra t i o ,
n o f .
 GE NE RAL I ND EX 3 29

K '
M e th yl al h ydrolysis of, .

Ke t on e . r e d u c t i on to s ec on dary al M e t h yl a mi n e f o rma t i on an d pro p

e r t ie s 1 20
c ou o l
.

M yla n ilin e in t e s t f or 2 a m1n e

e th ,
°
-
. 1 65

L 2 M e t h yl bu ta n o l 2 pre p a ra t i on of
- - -
, 69
L M eth ylen e d i e thers h ydrolysis of
'

ac se oxi da t i on t o mu c i c ac id
to ,
.
, 94
L ea d pe ro xi d e f or organ i c c orn ,
M ethyl e ster of 3 5 din itrobenzoic .
-

bus t ion s ac i d
.
55
isoth ioc yan a te f orma tion o f , 1 23

mus ta rd oil f orma t i on an d prop

d L im
-
o n e n e -
dih ydroc h l ori de pre p
, er ties 1 23

r i
a a t on o f r pre parat ion of
o an ge , 1 70

List of ppa ra t us f or gen era l or

a — ph en yl c arbin ol pre para tion of
-
, 73
ga n i e c h e mis t ry phen yl eth er 1 80
-
.

List of appara tus for the de te rmin a salic yl ate prep a ra t i on of , 19 1

t i on o f c a rbon a n d h yd rogen . M ic hl er s ke t on e f or c rys ta l vi ol e t

’
,

List of a ppara tus for th e de termin a I 7 1, 175

t i on of n i tr ogen Mi ro c ombus t i on f or c arbon an d

c -

L ist of c hemi c als for the de te rmin a h ydroge n . 0 0 0 0 0

t i on of c a rbon a n d h y d rogen . M i c ro c ombus tion for n i trogen

-
,

L ist of c hemic a ls f or the determin a M uc i c ac id prepara tion of , .

t i on of n i t roge n M us ta rd gas referen c e ,

List of c hemic als f or labora tory ex

pe rime n t s l on g c ours e,
“ ”
.

List of c h emic als f or labora tory ex Ni tra t i on of a n a o r mat i c hy droc ar

p e rim e n t s s h or t c o urs
,
e
”
bon . .

Logari thms table of ,

N i trobe n zen e , prepara t ion of
N i t rogen d e t ec t i on of
M
,

h e t e ro c y c l e s . O O O O O O O O O O O O

M agn esiu m f or G rign a rd s reac t ion ’

e s t i ma t i on of by a b s olu te ,

M an ome t e r f o r d is t ill a t i o n i n
,
me th od
vac u o N it rome ter
M an o me t e r , f or n i t rogen co mbus N itron a tion 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

ion
t N o t e-books 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

M el tin g p oin t a pparatus

-
,

ba th f or h igh t emp e ra t ure s .

c h a n ge s in Oil ba th s
-
79
de t e rmin a ti on o f r in
w a te O O O O O O O O O O O O O O O O O O O O 82
sub s tan c e s f or s ta n da r diz in g Oil of t urp en t i n e r e c t i fic a t i on of , 2 00

t h e rmo me te r W i n te rgree n pre p a ra t i on of , . 19 1

T h i e l e a pp ara t us Ol e fin e f o rma t i on 40 4 8 0 0 0 0 0 0 0 0 0 0
, , 202

2 Or th o e s t e r re fe ren c e s
-
, .
94
M
l- pre p ara t ion of
e n th o n e , Ox i da t i on of an ac e t yl en e tripl e
ox ime pre p a ra t i on o f
,
bon d
M erc ury purific a tion of
, Oxi da t i on of a 1 -
a c oh ol l to a n a l d e
M eth an e from c hloroform
,
hy d e m 5 4, 83 . 8 s
M ethod of run n ing blan k de te rmi Oxi d a ti on of a 2
°
-
a c oh ol l t o a ke
na t i on s
3 30 GENE R AL I ND EX

Oxid ation of a h ydroc a rbon R

Ra p e seed oil f or oil bath
-
,
-

13 4
w a t e r in . .

a n o l e fin e
“
doub l e bon d . .
44 , 4 8 R e du c t i on o f a h a l oge n d e riva t iv e .

i
w th c on c en t rat ed n i t ri c ac id . 20 8
ke ton e t o a 2 a l c o h ol
°
-

d ilu te n i tri c ac i d 13 4
an a roma t i c n i t ro c ompormd -
.

po ta ssium pe rma ngana te l

o efine bo n d
44 , 48 , so i
w th s o di um ama lgam a n d w at er
Oxida t i on w i t h potassium pe rma n s odiu m an d al c ohol
t in and h yd roc h l o ri c ac id
”

i
w th c h romi c ac id 5 4
.
, 8 3 , 8 5 , 99 , 2 10
zin c -c oppe r c ou pie 0 0 0 0 0 0 0 0 0

Ox ime forma t ion R eflu x c on d en s e r .

Oxy gen , f e r the det erminati on of

R e si n formation o f a l d ehyde s ‘

0 0 0 0 0

R es orc i n ol f e rri c c h l ori de t e st

,

f or fluores c ein f o rma tion .

P in t e s t f or f ormaldehy de
R u bb e r s t oppers bor ing h ol e s in
Pall adious c h lo ri de solu ti on ,

mol ded
P en to s e s furfural te s t
,
. .

Perman gan a t e oxi da t ion in n e u tral

solu t ion 1 89

Ph e n ol pre para t i on of
, 177 .

S alt i n g ou t of a dye
re ac ti on s of
.

178

Ph en olph thal e in fo rma t i on o f , 171

P h en y l gl u c os a zo n e pre p a r a t io n of 1 2 7
,
S a po n ififc a t ion , see Hydrel ys is
.

Ph en ylhydrazin e f or o sa zon e f or
.

S c h if f s a l de hyde ve st
, ’
9 2, 182
ma t i on
.

S eal ed bo tt le s, me th od ai Openi ng 33
f or h yd ra zon e f orma ti on
S ealin g tube s , d irec t i on s f or
.

117
Ph e n y l pro pion ic a c i d
S e pa ra t ory fu n n el gl obe s h ap e d
-
36
Ph osph orus d e t e c t io n o f ,

36
,

P in en e t es t s for doubl e b'J n d in 45 48

,
“ ”
,
S ilv er -
mirror t es t fo r al d e hy des gfr, 182
purific a tion of f or pin en eh y dro ,
S od a lime s rb i n g ca rbm
f or ab o
c h l ori d e
d i oxide in O rga n i c c ombus t i on s 2 43
P in en e hy droc hl o ride pre para ti on ,
S odium a ma l ga m pre p a ra ti o n o f 1 84
,
of

P olymeriza ti on of a c et al deh yde .

formal deh yd e .

S od ium, b ird s h o t
-
14 1
P orous t ilin g t o pre ven t b umpin g
, . 19
— b isu l fite ,
e
reage n t fer al de hyde s ,
P ota ssium hydroxi de c u t t i ng s ti c ks
98
,

S od ium bis u l fite , prep arat io n of

P re-h ea ter , for organ c i c ombu s

S od ium bis u l fite , f or re movmg

Preparation s , co ll ec tion of liquid .

S odiu m h ydro xi de, Cu tting s t i c ks of 3

re sidu e s tre a tment of 5 69 , D43
P yridin e rea c ti on s of , ,
. .

2 13
,
S ta rc h p o ta ssium iod id e pape r
-
. 18 7

Q .
1 58

Quin olin e ,
rea c tion s 2 13 S t em c o rre c tio n f or th e rmome t e rs 8 20
 I NTE RNATI ONA L AT OMI C WE I G HT S 1920
, .

A t o mi c
b
S ym ol . w eigh t .

Al umini um A1 Ne od ymium
An t i mon y . Sb Ne on .

3 9 -9 Ni c kel
As N i t on (radium
e man at i on )
B1 Ni t rogen
B Os mium
Br Oxyge n
Cd Palladium
CS P hosph orus
Cal c ium Ca 40 07 P l ati n um
Carbon C 12 00 5 P ot assium
Ce ri um Ce 1 40 25 P raseod ymium
Chl ori n e Cl 3 5 46 R ad i u m
Chromium Cr 52 0 R hod ium
Cobal t C 58 97 R ubi dium
Columbi um 93 1 R u th en ium
Coppe r Cu 63 5 7 S amarium
D ysprosium ” Dy 162 5 S c an d ium
E rbium Er S el e nium
E uropium ” Eu S ili c on
Fluori n e F S ilve r
G adoli n ium . Gd
G llium
a Ga S tron t i um
G rm i um
e an Ge S ul f ur
Glu i um
c n . G1 T an t alum
G ld
o Au T e llurium
H elium He T erbium
H ol mium H0 1 63 5 T h alli um
Hydrogen H T h orium
I n d ium In T h ulium
I od i n e I T in
I ri d ium Ir T i tanium
I ron . Fe T un gs te n
Kryp ton Kr Ur anium
Lan than um La 1 39 0 . V a n adium

Le ad . . Pb X e n on
Lith ium Li Yt terbi um
L u t ium
ec Lu 2
( Neoyt terbi um)
M g sium
a ne . . Mg Y ttrium
M g s
an an e e Zinc

Merc u ry 2 00 26 Z ir ium
c on

Molybd enum .