E SSE N TI A LS

OF

V O L UM E TRI C AN AL Y SI S
AN I N TRO D U C TI O N TO TH E S U BJ E C T, A D A P TE D

TO TH E N E E DS OF S T U D E N TS O F P H AR
M A C E U TI C AL C H E M I STR Y

E MBR A CI N G TH ES U BJ E CTS A LK A I ME TR Y ACI D I ME TR Y P R CI PI

OF L , ,
E

A N A S I S X I D I ME TR Y I N D I R E C T O XI D ATI O N I OD OM
.

TA TI ON LY ,
O , ,

E TR Y A SS A Y
,
R O C E SS E S O D R U G S E S TI MA TI O N OF AL
P F R ,

KA L OI D S PHE N O L
,
S U GA R S THE O R Y A PPLI CA
, , ,

TI ON AN D DE SCR I P TI O N OF I N DI CATO R S

H E N RY W . SC H I MP F , PH G . .
, MD . .

P rof essor o
f A nalyti cal C hemi s try i n the Brooklyn C oll ege of Pharmacy

l lus tr ateh

E DI TI ON —
RE WRI TTE N AN D E N LA RGE D
TOTA L I SS U E , S E VE N TH OU SAN D

N E W Y OR K

JO H N WI L E Y SON S ,
IN C .

LON DON : C AP MAN H HALL ,

L I MI TE D
 PREFACE TO THE THIRD E DITION

TH E exhaustion of the s ec on d edition and the app earance

of the new United States Pharm ac opoeia as w ell as the increas
ing dem and for the book have n ecessitated a compl ete r evision
“
of E ss entials of V olum etric Analysis and its issu ance as a ”
,

third edition .

The book has b een consid erably improved by the in troduc

tion of many new assay process es among Which may be men
,

ti oned the assays of m ercuric s alts p hos ph at es and hyp0phos

,

p h i tes by m eans of st an dard sulphocy an at e solution ; ass ays of

chlorates p erborates chloral aceton e r esorcinol ph enyl
, , , , ,

sul phonates ars enat es and alkali cacodyl at e

, , .

The “
has b een r ep l ac ed by mil and in oth er re ”

sp ects ch ang es are m ad e to accord with the new Ph arm acopoeia .

HE N RY W SCHI MP F . .

N E W Y ORK C I TY ,

Oct obe r , 1 91 7 .
 PRE FAC E TO THE FIRS T E DITIO N

THE growing n eed for a short t xt boo k which will make

e -

the princi p l es of volum etric an alysis r eadily avail abl e without

going t oo d eeply into d etailed and discursive d escription has
led to the preparat ion of thi s el em entary treatis e .

In the following p ages the aim is to pres ent the principl es

of thi s interesting and important subj ect in a form readily
intelligibl e to stud ents and avail abl e for l ecture room and -

laboratory work The ess enti al p oints a e condens ed within

. r

the limits of a sm all book with the int ention of furnishing

.

an outlin e which may s erv e as a practic al guid e as w ell as

an introducti on to the mor e advanc ed and voluminous works

on the subj ect .

If pres ented in a suitabl e mann er volumetri c analysis

rarely fails to prove int eresting to the stud ent b ecause it gives
,

hi m a cl ear conc epti on of the quantitativ e signi fi c anc e of

ch emical equati ons and thus affords practical proofs of chemical
l aws ; it furth erm ore trains the stud ent to make careful obser
v ati ons to form h abits of accuracy in m anipul ation and S in c e
, ,

the proc ess es are easily c arri ed out en abl es hi m to arriv e

,

readily at a d efin ite num erical conclusion .

The subj ec t m att er in thi s book is syst ematic ally arranged

-

as far as can be and t r eat ed as concis ely as is consist ent with

,

cl earn ess of expression The proc ess es are group ed under

.

fi e h eadin gs : N eutralizati on Precipi tation O xi dation Indirec t

v , , ,

Ox d ation and Iodom etry The princi p l es un derlying each

i

, .

v
v1 P REFA C E
group are d efinitely in dicat ed and th eir application illustrat ed
,

by num erous practical exampl es O th er subj ects tr eat ed

.

include m ethods of c alibrat i on and of the accurat e reading

of graduated instruments the calcul ation of the results of
,

an alys es
, the prep arati on and s t an dardiz ati on of volum etric
s olutions The indicators their s el ec t ion for sp ecial cases
.
,

and the i onic th eory r egardin g t h eir acti on as w ell as assay

,

p roc ess for p h enol sug

, ars an d v eg et abl e drugs als o r ec eive

sp eci al t reatm en t
. The au t h or hop es th at he has pr ep ared
a bo ok which will pr ov e s ervic eabl e to thos e for whom it was

wri t t en and that it will b as gen erously rec eived as w ere the
e

four editions of his Text book of V olumetric An alysis

'

-
.

HE N RY W
. SCHI MP F .
 C O N TE N TS

L I S T OF EL M E E N TS WI TH THE I R A O MI C WE I GHTS
T

T AB E L OFM UL L
TI P E S OF A T OMI C WE I G H TS A N D C OMBI N ATI O N S .

CHAP T E R I

I NTR OD UC TI ON

CH AP T E R II
G E N E RA L PRI N CI P A L S OF CH EMI CA L C OMB I N ATI ON U P ON WHI C H
VO L U ME TRI C A L
N A YSI S I s BAS E D

CHAP T E R III
VOLU ME TRI C O R S DTA N A RD S OLU TI ON S
To Titr ta e . R sid e ua l T itr t i a on .

CHAP TE R I V

The I oniz ation Theory . I ni ti n Th ry f Indi t rs

T he o za o eo o ca o .

AG uide for the Selec ion t of Indi t ca ors .

CH AP T E R V

A P P AR AT US U SE D IN VO LUM R
ET I C A L
N A Y SI S

CHAP TE R V I
ON TH E U SE OF AP PA ATR US .

O n the R eadi ng of I str

n umen ts . C alib r ti
a on of Instrum nts
e .

v ii
vi ii CONTENTS
CHAP TER VII
M E THOD S OF CALCU LATI G R SU L S N E T

Tabl f N mal Fa tors t f Alkali s

e o or c ,
e c .
,
o e ,
Aci d s and Alk ali
E art hs O S t at ing R s ults
. Tabl f M ln e . e o o ecula r W ights and
e

N rmal Fa t ors fo th most C mm n O i ds

o c r e o o x .

CHA PTE R VIII

A N A LY S I S BY N R L TO E U T A I ZA I N .

Al k lim tr y P r p r t i n f S t nd r d A i d S lut i n s
a e . e E st i
a a o o a a c o o .

m t i n f Alk li Hydr ids

a o o E st im t i n f Al k li C rb n t s
a ox . a o o a a o a e .

Mi d Alk li Hydr id d C rb n t
xe a E st i m t i n f Alk li
ox an a o a e . a o o a

B i rb n t s wh n Mi d wit h C rb n t s S di um B rat
'

ca o a e e xe a o a e . o o e .

S di um C
o dyl t S di m G ly r p h sp h t
aco a eE st i mat i n
. o u ce o o a e . o

of O rg ni S lts f th Alk li s
a c T bl f N rm l F t rs
a o e a e . a e o o a ac o ,

t
e c f th O rg ni S lts f th Alk li s
.
,
o e E st im t i n f S lts
a c a o e a e . a o o a

of th Alk li E rt h M t al s
e E st im t i n f Mi d Hydr i d
a a e . a o o xe ox s

a d C rb n t s
n af Alk li E rt hs
o a e A i di m tr y o E st i m t i n a a . c e . a o

of A i ds P r p r t i n f S t and r d Alk li S l t i n s
c . e a a T bl
o o a a o u o . a e

Sh wing Q ant i ty t b t ak n f Analys i s in D i r t P r nt ag

o u o e e or ec e ce e

E stimationsf

CHAPTER IX

A N A LY SI S BY P R C ATI O E IPI T N .

Pr p r t i n f D in m l Sil v r N i tr t D in r m l S dium
e a a o o ec or a e a e, ec o a o

C hl ri d a d D i n rm l Sulp h y n t
o ,
n E st im t i n f S lubl
ec o a oc a a e . a o o o e

H l id S lts
ao M hr s M t h d wi t h Chr m t Indi at r Ti
a . o
’
e o o a e c o .

t ti
ra Wi t h ut
on Indi at r E stim ti n f H l id A ids
o an c o . a o o ao c .

Ass ay f Ph s p h ri A i d
o E st im t i n f Cy n g n
o o E st i
c c . a o o a o e .

mat i n f Silv r S lts

o o E st i m t i n f M t alli
e Silv r
a d . a o o e c e an

Sil r All ys
ve Ass y f M r uri S lt
o . Tabl f Sub t ana o e c c a s . e o s ces

E st imat d by Pr ip i t at i n
e ec o .

CHA PTE R X
AN ALYS S B OX D AT O A D R DU T ON
I Y I I N N E C I .

P r p ar at i n f D in r m l P t ss i um P rm ang nat
e o o ec o a o a e a e .

Volumetri c A nalyses by Means of P otassi um P ermanganate .

On the U se of E mp i ri cal Perm a ga at e Solut i o yp i cal n n n T .

n n n
A alyses by Perma ga at e D i r ect i tr atio s E st i mat i on of . T n .
 CONTENTS
PA G E

rr st t n tt Ir n
Fe ous Sal s E ima io of Me allic o in Ferrum Reduc
.

tum st t n
E i m a io of Ox ali c Aci d an d Oxala e
. ts
E ima io st t n .

of C alci um st t n r n r
E im a i o of Hyd oge Di oxi d, Ba i um D ioxi d,
.

r rt
and Sodium Pe bo a e st t n rr
E i ma i o of Fe i c S al ts
E im a st . .

tion f N itrous A id a d N itri t s R sidual Ti trations E st i

o c n e . e .

mat i n f Hyp p h sp h r us A i d and Hyp p h s p hi t s

o o o oE st i o o c o o e .

mat ion f C al i um Saltso E st im at i n f L ad A t at and

c . o o e ce e

Suba t at ceE st im at i on of Mangan s

e . Dio id E st imat i on e e x .

of N i trat s Chl r at s C hr omat s a d Chr omi c A i d

e ,
o E st im a e ,
e ,
n c .

t ion of Tin E t imati on of Copp r

. s e .

Volumetri c A nalysi s by Means of P otassi um Di chromate .

n
Pr ep ar at i o of D eci or mal Pot ass ium D i chr om at e E st i m a n .

n
t io of Ferrous Salts able of Subst a ces E st imat ed by . T n
n n
Perma ga at e or D i chr omat e .

A nalysi s by I ndi rec

t Oxidation r t ion of D inormal . P r ep a a ec

I odin St ar h S lution On th U f Sodium Bi arbonat

. c o . e se o c e

i Ti tr at i ns wi t h I di n
n o E st i m at i on f Ars n us C m p unds
o . o e o o o .

E st im at i on f Ant im ny C mp unds o E st i mat i n o f Sul o o . o o

p hu o
ru A i d sa d S u l pchi t s E st i m a t
n i on f So di u m T h i o ul e . o s

p ha t e H y d
. r g n Su l p h i d a nd S ul
o ep hi d s T a b l o f Su b st a n . e ces

E st imat d by M an of I odi n Solut i on

e e s .

E ti mati n f S ub tan
s o R adily R du d
o I odom try E sti
s ces e e ce . e .

mat ions Inv lv ing th U f S di um T hi s ulp hat V S

o e Pr p se o o o e . . e

ar at i on f D in r mal Thi s ulp hat V S

o ec o E st i m at i n f F r o e . . o o ee

I odin Indi r t I d m tri E sti mat i ns E st im at i n f Fr

. ec o o e c o . o o ee

Chl rin o Br min

o r E st i mat i n of Av ailabl C hl rin
o . E st i o e o .

mat i n f Hydr g n D i id D i st illat ion M t h ds

o o o e E st i m a ox . e o .

ti n f Mangan s D i i d Chr mi A id and Chr mat s

o o e e ox . o c c o e .

E st im at i n f Al kali I dids
o o D ig st i n M t h ds E st imat ion
o . e o e o .

of Chl r at s oB r mat s and I dat s E stimat i n f F rri

e ,
o e o e . o o e c

Salts E st im at i n f Chr mat s Ars nat s An t i m oni S alts

. o o o e ,
e e , c ,

Copp r and M r ury

e ,
e c .

Chlorometry, Reducti on Methods ,

I nvolvi ng the Use of Arsenous
A cid S oluti ons . r p arat i n f St andard Ars n us A i d V S
P e o o e o c . .

I odiz ed t ar h S c T st Pap r E st imat i n f Fr Hal g ns

e e . o o ee o e .

E st i mat i n f o o Av ai labl Chlorin Chlor om trieAss ay of . e c

Mangan s D io e e xi d .
 PAG E

E stimation of I r n by o Means of S t ann us o C hlo i d r . E s ima t

t i n of M r uri Salts
o e c c .

PA RT II
C H AP TE R XI

E ST MA O N O A LKAL O D
I TI F I S .

Tabl f Fa t rs f Alk l i ds G
e o c o or ao . ordi n s
’
Modi fi ed Alkali
m tri M t h d f Ti tr at ing Alk l ids
e c e o or ao .

CH AP TE R XII
A SS A YI N G V GOF E P
E TAB E RA O L D RU G S AN D T HE I R R E PA TI N .

S p ar at i n
e f Alk o d U of I mmi s i bl S lv nts ao l i ds a n se o c e o e .

K ble M di fi t i n f th K ll r M t h d Ass y f G al ni al
er s
’
o ca o o e e e e o . a o e c

Pr p ar at i ns Ll yd s M t h d K at s M t h d
’ ’
e o . o e o . z e o .

C HA PTE R X III

E ST MAT O S I VO LV G U O D C ORM
I I N N IN SE F E IN AL BR OMI N V S .

P r p ar t i n f D in m l B r min
e a o o ec or a o Solu io t n . A ss ay of

Ph n l R s r in l
e o Ph nyl ulp h at
. e o c o . e s on es .

C HAPTE R XI V

S OME TE CHN I CAL M THOD S E F OR FATS , OL I S AN D WAX E S

The Aci d Value . The S ap onifi cati on N umbe Vola ile r . t
tt
Fa y Acid N umbe r . Rei che s N umbe
’
rtThe R ei cher r . t
ss
Mei l N umbe Hubl s N umbe
’
r . r . Hanus ’
N um be r . Aci d
N umbe for Re r sin s .

CHAP TE R XV
E STI MAT O O S GARS
I N F U

P r p ar at i n f F hlin g s S lut i n D t rminat i n f th

’
e o o e o o . e e o o e

E nd point - E st imat i n S t ar h ft r Inv rs i n

. E t im at i no c a e e o . s o

f Malt s i n M alt E tr a ts
o o e E st imat i n f D i a t a i Valu x c . o O s sc e

f Mal t E tr a t
o x c .
 CON TENTS xi
CHA PTE R X VI
E STI MATI ON OF FO RMA LD HYD E E

Th Ammoni a M t h d Th Amm ni um Chlori d M t h d

e e o . e o e o .

O i dat i n M t h d by M an s f Hydr g n Di o i d Th I od
x o e o e o o e x . e o

m t i M t hod Th C yani d M t h d Ass ay f Pa af mal

e r c e . e e o . O r or

d hyd and A t on
e e ce e.

CHAP TE R X VII
E STI MAT O O A LCOH O L I T C U R S A D B VE RAG S
I N F N IN T E N E E

Al oh lom tri Tabl

c o e c e .

PA RT III
CHAP TE R X VIII

The Law of C ha le r s . The L aw of B oyle .

CHA PTE R XIX

ASS AY O F N I TRI TE s
Sp i i rt trous E th r
of Ni e . Amyl N i tri t e . Sodi um N i ri t t e
.

N i tri A id i n N i tr at s
c c e .

CHA PTE R XX
H YD R O GE N D D I OXI .

U of N i tr om t r
se e e . U se of Ur
r t us Th Hyp o ea App a a . e

hlori t M t h d
c e Th e o . e Hyp obr mi t t oTabl Sh wing
e Me hod . e o

W ight i n Milligr ams

e of H0 rr sponding to on
2 2 co of e e cc .

Moi t O yg n
s x e .

CHA PTE R XXI

E STI MAT O N I OF S O LU BLE CARBON AT E S BY THE U SE O F THE N I TR OM
E TE R .

CHA PTE R XX II
E ST MI ATI ON OE U RE A IN URI N E .

r
The D o emu s Ur ’
eome e tr . The Hi d D o em un s —
r s Ur eo me tr e .

Sq ui bb s Ur rat us
’
ea Ap p a .

APPE N D I X
DE SCRI PTI ON or I D CATOR S A LPHABE TI CALLY ARRAN GE D
N I
A L I ST O F T HE M O RE C O M MO N E L E M E N TS WI T H TH E I R
S Y M BO L S AN D A T O M I C WE I G H T S

N am e .
W
b d O
as e
gh
At o m i c m W
ei
b d H
on
ght * A to i c
= 16 . as e on
ei
= I
t
.
A pp ro x i m a t e
A t o m ic W ghei t .

O O O O O O O O O O O O O O O O O O O O

o o o o o o o o o o o
o o o o o

o o o o o o
o o o o o o o o o o

I ntern ati on a A t omi c l W ei g ht s, 19 16 .

A
T BLE OF MULTI PLE S OF SOME ATOMI C WE I GHTS AN D
C OMBI N ATI ON S I N F R E Q UE N T U S E .

2 . 0 16 3 02 4
.
4 . 03 2 . 04 8 7 . 056 . 064 9 07 2
.

32 .
48 . 64 . 80 . 1 12 . 12 8 .

.
34 . 0 16 51 4
. 02 68 . 03 2 85 . 04 8 1 19 . 0 56 136 . 064 1 53 . 07 2

36 03 2 .
S4 04 8 72 . 064 90 . . 0 96 1 2 6 . 1 12 14 4 . 12 8 162 . 14 4

2 8 . 02 42 . 03 56 04 .
70 . . 06 98 . 07 1 12 . 08 12 6 . 09

34 064 51 . 102 68 . 12 8 85 . 2 04 119 . 2 38 1 36 . 2 72 1 53 .

3 06
3 6 0 84. 54 . 12 6 72 . 168 90 . 2 52 12 6 . 2 94 14 4 336 . 1 62 . 378
92 . 02 138 . 03 1 84 . 04 2 30 . 06 312 . 07 3 88 0 8 .
4 14 . 09

N 03 12 4 . 02 1 86 . 03 2 48 . 04 3 10 . 06 4 34 . 07 4 96 . 08 558 . 09

24 .
48 . 60 . 84 . 1 08 .

88 . 13 2 . 176 . 220 .
308 .
35 2 39 6 .

120 . 2 40 .
300 .
420 .
4 80 .
S4 0 .

52 . 1 04 . 04 1 30 . 05 1 82 . 07 2 08 . 08 2 34 .

Cl 70 . 14 1 . 84 177 . H
C 2 12 . 2 48 . 2 2 2 83 6 8
. 3 19 .

Br
. 1 59 . 3 19 68 39 9 O .
4 79 52 .
5 59 4 4 6 39 3 6 .
7 19 .

I 2 53 .
50 7 . 68 634 . 6 761 .
52 8 8 8 -4 4 10 15 .
36 1 14 2 .

S 64 . . 2 1 12 8 . 1 60 .
35 2 2 4 49. 2 56 56. 2 88 .

80 3 1 60 . . 2 1 32 0 .
4 0 0 -3 5 4 80 4 2 .
5 6 0 -4 9 64 0 56 .
720 .

804 192 . . 2 I 4 80 3 5 .
5 86 4 2 . 67 2 «
49 7 68 56 . 86 4 .

P04 190 . . 12 3 80 475 . 20 5 80 . 665 .

7 60 3 2 . 85 5 .

P2 0 5 . 2 4 56 8 . 7 10 .
40 85 2 .
994 . 1 1 36 . 64 12 78 .

Na 92 . 1 15 . 138 . 16 1 . 1 84 . 2 07 .

I( . 2 0 1 17 .
30 1 56 . 1 95 .
50 2 34 . 2 73 .
312 . 80 35 1 .

I A . 88 2 0 . 82 2 7 .
34 .
70 4 1 .
48 .
55 52. 62 .

Ca 80 . I 4 12 0 0 2 1 160 . 2 00 -3 S 2 40 4 2 . 2 8 0 -4 9 3 2 0 56 .
360 .

Ba 2 74 . 74 4 12 . I I 54 9 . 6 86 8 5 .
7 6 1 59 . 89 8 9 6 . 1 0 36 .

2 15 .
76 3 2 3 64 .
431 52 . 539 4 0 .
7 55 16 86 3 . 04 97 0 9 2 .

111 . 68 16 7 .
52 2 2 3 36 . 2 79 . 2 0 3 3 5 -0 4 390 . 88 446 7 2 50 2 .
56
401 . 2 80 2 .
4 1 6 04 8 . 1 80 5 .
4
 A BBRE VI AT I O N S AN D

c ubic c en t im et er
gramm e ,
grains

at . wt . . t mic w eight
a o

volum etric s ol ut ion

. t es t s ol uti on .

U ni t ed St at es Ph arm ac op oei a .

n ormal .

decin orm al .

c en t in orm al .

100

s mi normal
e -
.

2
—
or 2 N do ub normal
le -
.

millili ter .
TH E E SSEN TI ALS O F VO LU M E TR I C
A N A LY SI S

C H APTE R I
I N TR O DU C TI O N

IN a ch emic al an alysis the ai m is to d etermin e the n ature

of the ch emic al subst anc es c ontain ed in a giv en c ompoun d

or to asc ertain th eir qu antiti es In the form er c ase the

.

an alysis is a quali tati v e in the l att er a q uanti ti v e one

, , .

The qu antitiv e an alysis of a subst anc e may be mad e

eith er by the g av i metri c or the v ol umetr i c m ethod
r .
,

The Grav imetri c Met ho d consists in s ep arating and

w eighing the constitu ents eith er in th eir n atur al stat es or in
the form of n ew and d efi nit e compounds , the composition
of which is kn own to the analyst From the w eights of
.

th ese new compounds the an alyst can c alc ul at e the quantiti es

of the original constitu ents .

E x ample . To d et ermin e the qu antity of silv er in a solu

tion by the gravim etric m ethod we proc eed as follows
T en grams of a solution cont aining silv er in the form of
silv er nitrate (AgN O 3) is pl ac ed in to a b eak er and aft er , ,

slightly acidul ating with nitric acid is treat ed wi t h hydro

,

chloric acid drop by drop until no furth er precipitation

, ,

occurs The pr ecipitat e whi ch consists of silver chlori d (AgCl)

.

is th en s ep arat ed by filtration thoroughly wash ed dri ed and

, ,

w eigh ed Its w eight is found to be

. gm The calcu
.

lation is th en made as follows : gms of silver chlorid

.
2 THE E SS E N TIAL S OF V OL UME TRI C ANAL YSIS
r epres en t s gms . of silver or gms of S ilv er nitrate
.
,

as the equ ation sh ows

AgN 0 3 + HC 1= AgC 1+ HN 0 3 .

14
3 -34

T h erefore , gm . of silv r chl orid will r epres ent

e

X 0 69 = . 0 .
5 9
1 gm . of silver ,
I 4 S-34

X 0 69 = . o . 81 7 gm . of silv er ni trat e .

I -
4 S 34

The V olume i c tr Metho d

his m ethod dep ends upon the . T
use of solu t io ns (standard soluti ons) which are of known s t r ength

an d p ayin g at t enti on to the v alum e of such a s olu t i on which

m us t be add ed t o the subst anc e und er an alysis to p erform

wi t h it and compl et e a c ertain r eac tion Thus if we c on duct .
,

an an alysis by m eans of such a solution an d can exp r ess by ,

a ch emic al equ ati on the r eaction which t ak es p l ac e we can ,

readily and accurat ely c alc ul at e the quantity pr es ent of the

subs tanc e un der an alysis .

E x ampl If a silver s olution is to b an alyz ed by this

e . e

m eth od i t is tr eat ed with a stan dard s ol ut ion of s odium c hl ori d ,

ad ded slowly from a burrette un til n o mor e Silv er chl ori d is

precipitated E ach mil of this s tandard s olu ti on will p ecip

. r

i tate a c er t ain w igh t of silver as S ilver chl orid and h enc e

e ,

by no ting the numb er of mils us ed to c om pl t e the pr cipitati on e e

the w eigh t of the silv er in the solu t ion an alyz ed is easily

asc ertain ed .

N
The
3
1
sodium chlorid s olution is g en erally us ed for t his
p urp os e is mad e by dissolving of the m ol ecul ar w eight
. It 1
1 11

of the s alt (in gr ams ) gms ) in suffi ci ent wat er to .

m ake 1 0 0 mils 0 mils of this solution will p recip i tat e 7 5

. 1000 1

of the atomic w eight of S ilv er (in grams ) and

 C H APTE R I I

G ENE RAL P RI NC I P LE S O F C H EM I CAL COM BI NA TI O N

U P O N WHI C H VOL UME TRI C ANAL Y SIS I S BA S ED

1. WHE N substanc es unit e ch emic ally un ion always

the
t akes pl ac e in d efinite and invari abl e proportions Thus wh en .

silver nitr ate and sodium chlorid are brought tog eth er ,

p arts (by w eight) of S ilver nitrat e and p arts (by w eight )

of s odium chlori d will r eact with each oth er pr oducin g ,

p arts of a curdy whit e precipitat e (silver chlori d) .

T h es e subst anc es will r eact with each oth er in th es e pro

portions only .

I f a gr eat er proportion of S ilv er nitrat e than th at abov e

stat ed be added to the sodium chl orid only the above pro
,

portion will react the exc ess rem aining unch ang ed
, .

The s am e is tr ue if sodium chlorid be add ed in exc ess

of the abov e proportions F or inst anc e if 2 00 p arts of silver
.
,

n itr at e be mix ed with p art s of sodium chlorid ,

p arts only will react wi t h the sodium chlorid whil e ,

p arts of silv er nitrat e will rem ain unchang ed Again wh en .

,

potassium hydroxid and sulphuric acid are mix ed potassium

sulph at e is form ed , p arts of potassium hydroxid and
p arts of sulphuric a cid b e ing r equir ed for compl et e

n eutralization Th es e two substanc es unit e chemically in th es e

.

proportions only .

The equ ation is

ZKO H H2 80 4 K 2 80 4 2 H2 0 .
 G EN E RA L P RI NC I PLE S OF C H EM I CAL COM BI NA TI ON 5

In oth er words p arts of K O H will n eu tralize

,

parts of H 80 and cons equ ently

2 4, p arts of H S O will Z 4

n eutraliz e p arts of K O H .

O xalic aci d and sodium c arbon at e r eact upon each oth er

in the proportions shown in the equation

H2 C2 O 4 2 H2 0 + N 3 2 C O 3 N a2 C 2 0 4 l C0 2 + 3H2 0 ‘"
.

10 6

p arts of crystalliz ed oxalic acid are n eutraliz ed by

1 0 6 p arts of anhydrous s odium c arbon at e .

2. D efinit e ch emi c al compounds always cont ain the s am e

el em ents in ex actly the s am e p ro p ortions the proportions ,

b eing thos e of th eir atomic w eights or som e multipl e of thes e ,

w eights .

T hus sodium chlorid (N aCl) cont ain s 2 3 p arts of m et allic

sodium and p arts of Chlorin th es e b eing the ato mic ,

w eights of sodium and Chlorin r esp ectively .

Pot assi um sulph at e (K S O ) cont ains twic e z 4

p arts of potassium p arts of sulphur and four tim es

, ,

p arts of oxygen .

Pot assium hy droxid (K O H) cont ains p arts of p otas

sium 6 p arts of oxyg en and one p art of hydrog en Hydro
,
1 , .

chloric acid (HCl) contains one p art of hydrog en and

parts of Chlorin .

Upon th es e f acts the volum etric m ethods of an alysis are

b as ed .

It has b een S hown th at gms of sulphuric acid will .

n eutraliz e gms of potassium hydroxid It is th er efore

. .

evid ent if a solution of sulphuric acid be m ad e cont aining

gms of the pure acid in 1 0 0 0 mils that on mil of t his

.
, e

solution will n eutraliz e gm of potassium hydroxid . .

I n esti m atin g alkali es with this acid solution the l att er is ,

6 THE E SS E N TI AL S OF VO L UM ETRI C ANAL YSIS
added from a burette in sm al l porti ons un t il the alkali is
, ,

n eutraliz ed as Sh own by it s reacti on wi th s om indicat or

,
e .

E ach mil of the aci d s olu t i on r equir ed b efore n eutrali ati on z

is compl et e in dicat es gm of K O H and the numb er .

,

of mils used multipli ed by gm gives the qu an ti ty of .

pure K O H in the sam pl e analyz ed .

O ne mil of the s am e solution will n eutraliz e gm of .

sodium hydroxid (N aO H) gm of anhydrous sodium

, .

c arbon at e (N a C 0 ) etc 2 3 , .

If a solu t ion of crystalliz ed oxalic acid be m ade by dis

solving gms in sufli c i ent wat er to m ak o m ils we
. e I co ,

will h av e a norm al s oluti on the n eutralizing pow er of which

,

is exactly equival en t to the ab ov e m en t i on ed normal sul phuric

acid solution .

The str ength of aci ds is estim at ed by alk ali v olum etric

solutions A n ormal soluti on of p otassium hydroxid c ontaining
.

gms in the lit er will n eutraliz e exactly lit er of the

. I

norm al acid soluti on ; mil of this norm al alkali ill neutrali e

I z

gm of HCl . gm of H C 0 or
,
gm.
2 2 4 , .

OI 112 80 4 , etc .
 CH APTE R I I I

V OL U ME TRI C OR STANDAR D S O L U TI O NS
AN Y solution employed in volum etric an alysis for the
purp os e of estimating the str ength of substanc es that is any , ,

soluti on the ch emi c al pow er or tit er of which has b een d et er

min ed is d esi gn ated a standard or volumetri c solution Such
,
.

“
a solution is s aid to b titr t r nch or
”
d = i l
e a e (F e ti tre t t e

p ow er ) an d,
is som e tim es also c all ed a set solution or a stand

a di
r zed soluti on It may be normal d ecin orm al empiric al
.
, , ,

or of any str ength so long as its str ength is kn own

,
.

Wh en volum etric an alysis first c am e into use the solutions

w er e so m ade th at each substanc e to be estimat ed had its
own sp eci al vol um etric solution and thi s was usu ally of such
,

str ength as to give the r esult in p erc ent ag es Thus a c ertain .

str ength of standard acid was employ ed for pot ash anoth er ,

for soda and a third for ammoni a and in t esting the acids
, , ,

each had its own sp eci al st and ard al k ali Th es e soluti ons
.

w ere known as norm al solutions ; th ey are still to som e extent

in use and sinc e solutions now d esign at ed as norm al are of
,

an entir ely diff er ent ch aract er it is import ant th at no miscon

,

conc eption should exist when a normal solution is spoken of .

N ormal S oluti ons are th os e which cont ain one lit er (1 000
mils) the mol ecul ar w eight of the active r eagent express ed in
,

grams and r educed to the val ency corresponding to one atom

,

of repl ac eabl e hy drogen or its equival ent In oth er words .

,

t hose which con tain in mils in any given reac t ion the
1 00 0

ch emical equival ent of one gram of hydrogen The now ac .

ce ted
p b asis for the atomic w eigh t s O = I 6 m ak es a slight
.
8 THE E SS ENTI AL S OF VOLUMETRI C ANALY SIS
change in the quan tity of reagen t in a normal s olu tion i e , . .
,

it will contain in mils the exact equivalent of 8 gms of

1 00 0 .

oxygen .

T h us in unival en t or m on obasic c omp oun ds the full m ol c e

ul ar w eight in gr ams is c ontained in a lit er of the n orm al solu

ti on .

E x ampl Hydrochl oric aci d HC l h avin g on e replac eabl e

e .
, ,

hydrogen atom i t s n orm al s oluti on woul d c on tain the full

,

mol ecul ar w eight gms in a li t r A normal solution of

,
. e .

p otassium hy droxi d sh ould con tain gms of K O H in a .

liter whil e th at of s odium hy droxid shoul d contain 4 0 gms of

,
.

abs olut e N aO H .

N orm al solu t i ons of bival en t o dib asic c omp oun ds contain r

in 1 000 mils one half the m ol ecul ar weight in grams Thus

-
.
,

oxalic acid H C 0 2 H 0 , 2 2 5 h aving

4 tw o r epl aceabl e H
2 ,

a toms on e h a
,
lf of its-
mol ecul a r w eigh t in gr ams = 63 0 is . 2

contained in a lit er of its normal solu t ion For the s am e .

reason a lit er of a normal s olu t i on of sulp h uric acid contains

9 8 I
gms and a lit er of a n ormal s olu tion of s odium
°

.
,
2
106
c arbon ate N 3 C O c on ta ns 2 53 gms wh l e I n the c as e
2 3 i .
,
i

of t riv al ent or trib asic com p oun ds on e t hird of the mol ecul ar
-

w eight in grams is contain ed in a li t er of the n ormal sol ution .

Thus it will be s een th at one m i l of any norm al aci d s olu t i on

will n eutraliz e one mil of any norm al alkali solu t ion b ecaus e ,
'

on e m ol ecul e of a univ al ent aci d will n eu t r aliz e on e m ol ecul e

of a univ al en t alk ali o a h alf a m ol ecul e of a biv al ent alk ali

,
r .

This is shown by the equ ations

HCl N aO H = N aCl + H2 0 ,
46

2 HCl N azC O g 2 N aCl H2 0 C0 2 .

53
 VOLUME TRI C OR STANDA R D S OLU TI ON S 9

The value of a reagent as express ed by its hydrogen

equival ent is r eadily s een in the c as e of aci ds and alk ali es

by r eferenc e to the ch emical formul a bu t in such st an dard ,

solutions as potassium dichr omate potassium p ermangan at e , ,

s odium thiosul phat e and oth ers the particul ar r eac t ion in
, ,

any giv en an alysis must be t ak en into acc ount in m aking a

normal solu t i on ; for instanc e wh en K C 0 is to be us ed , 2 12 7

as a p r ecipi t at ing ag en t its r eac t ion is as f oll ows

,

2 B& (C2 H3 0 2 ) 2 K 2 CI 2 O 7 '

H2 0 2 BaCr O 4 i ‘ '

2 K C 2 H3 O 2
+ 2 HC 2 H3 0 2 .

I t is thus s een t h at one m ol ecul e of K Cr O will c aus e z z 7

the p r eci p i t ati on of two atoms of b arium in the form of

C hr om at e E ach atom of b ari um is ch emic ally equival ent to
.

two at oms of hy drog en ; th er ef or e on e fourth of a mol ecul e —

of K C 2 0 ‘
I 2is equival ent to one atom of hy drog en An d
7 .

th er efor e a normal s olution of this s alt wh en us ed as a ,

precip i tat ing agent must contain in one lit er one fourth of
,
-

i t s mol ec ul ar w eigh t in grams ; gms .

If K C1 0 is to be us ed as an oxidizing agent the three

2 2 7 ,

at oms of oxyg en which i t yi elds for oxi dizing p urpos es must

be t ak en int o account Wh en this s alt oxidiz es it splits up

.

int o K 0 + C1 0 + O The three atoms of oxyg en combin e

2 2 3 3 .

wi t h and oxidiz e the s alt act ed up on o t h ey combin e with

(
,
r

an equiv al ent qu an t i t y of the hydr og en of an aci d and lib er at e

the aci dulo us p art which th en combin es with the s alt

, As .

the equ ations S h ow ,

OF e O K 2 C1 2 0 7 K zo (31 2 0 3 3F 6 2 0 3 01
°

( GO Q ) 3
F e

OFCS O 4 K 2 C1 2 0 7
‘
7 H2 S O 4

7 H2 0 K 2 8 0 4 i C1 2 (S O 4 ) 3
“
3F 6 2 ( O4 ) 3 ,
S

7 H2 80 4 K 2 CI 2 0 7
'

38 0 4 7 H2 0 Ks 4 C1 2
10 THE E SS EN TI AL S OF VOLUMETRI C ANALY SIS
Ea ch of t h es e at oms of o yg en a e equival en t to two atoms x r

of hydrogen Thus O is eq uival n t t o H

.
3 e 6 .

Henc e a li t er of a norm al s olu t i on of K C1 0 wh en us ed 2 2 7,

as an oxi dizing ag ent con tains one sixth of i t s m ol ecul ar -

,

w eight in grams .

The sam e may be s ai d of potassium p erm angan at e wh en

us ed as an oxi dizing ag en t .

2 KMn O has fi e at oms of oxyg en which a e av ail abl e

4 v r

for oxi dizing p urpos es and each of t h es e is c apabl e of t aking

,

two atoms of hydrog en fr om an acid and lib erat ing the acidulo us
p art The hydrog en equival ent of t his sal t m ay t h erefor e be
.

s aid to be one t enth of the w eight of KMn O and a n ormal

-
2 4 ,

solution of this s al t c ontains gms in a lit er . .

S odium Thi osulp hate (Hy p osul p hit e) N a 8 0 is anoth er

'

, 2 2 3,

instanc e The m ol ecul e of this s alt has two atoms of sodium

.
,

which h ave r epl ac ed two atoms of hydrog en of t hiosulp huric

acid .Thus i t would s eem th at a norm al solution S h ould
contain one half of the mol ecul ar w eight in grams But the
-
.

p ar t icul ar r eacti on of this s alt with i odin is t ak en into acc oun t .

O n e mol ec ul e r eac t s wi t h on e atom of iodin as s een in ,

the equ at ion

2 N a2 82 0 3 i 12 ‘ ‘
2 N aI N a2 84 0 6 .

Sinc eio din is unival ent a m ol ecul e of the s al t is equival ent

,

to one at om of hydr ogen .

A norm al s ol uti on of this s alt th er efor e con t ain s the

mol ecul ar w eight in grams in a lit er .

orm
D ecin al S ol u i o t ns , ar e on e- e t nth the s tr ength of
normal s olutions .

t orm al Solut i on s
Cen in ,
ar e on e- hundredth the strength
of normal solutions .
12 THE E SS ENTI AL S OF VOLU ME TRI C AN ALYSIS

mils used in any sti m ati on must

e be multi pl i ed by i
04

or and th en by the normal fac t or for the substance ,

analyz ed .

It is a goo d pl an to have the factor marked on the l abel

of the bottl e con taining such an em pirical so lution In this .

case it would X 96 5 norm al

be 0 1 = . .

S tan dard solu tions for use in volum etric an alysis are usually
s olutions of acids b as es or s alts and in two cas es el em ents
, , , ,

n am ely iodin and bromin

,
‘
.

A st and ard solution of a b as e is usually us ed for the esti

'

m ation of free acids .

A st and ard solution of an acid is usu ally us ed for the

estim ation of a fr ee b as e or the b asic p art of a s alt the acid
, ,

of which can be compl et ely exp ell ed by the acid us ed in the

stand ard solution E xampl e c arbon at es
.
, .

A st and ard solution of a s alt may be us ed as a pr ecipit ant ,

or it may be us ed as an oxidizing o r educing agent r .

Th at p art of the r eag en t in a s t an dar d s oluti on which

r eacts with the substanc e und er analysis is the activ e con
sti tuen t of the solution As Ag in AgN O is the activ e con
.
3

sti tuent of the st an dar d solution of silv er nitrat e ,

AgN 0 3 N aC l AgC l N aN O g ,

or CI in N aCl is the ac t iv e c ons t i t u ent of the stan dard solution

,

of sodium chlorid .

If the r eag ent is a b as e as K O H the b asic part K is the

, ,

ac t iv e cons t itu ent I f the r eag ent is an acid the activ e consti t
.
,

uen t is the acidulous p art as 8 0 in H 80 , 4 2 4 .

If the action of the r eagen t is oxidizing th en that p art ,

of the r eag ent which produc es the oxidation is the active

constitu ent .

The v al enc e of an acid is shown by the numb er of r epl ac e

 VOL U ME TR I C OR ST ANDA R D S OL UTI ON S 13

a bl e hydrogen atoms it contains Thus HCl I S un ival ent .

'

H 80 is biv al en t which m eans th at a mol ecul e of HCl is

2 4 ,

ch emically equival ent to one atom of hydrog en and a mol ecul e ,

of H S O is ch emic ally equival ent to two atoms of hydrog en

z 4 .

The val enc e of a b as e is shown by the numb er of hydr oxyls

it is combined with As K O H is unival ent Ca(O H) is
.
, 2

bival ent .

The v al enc e of a s alt is shown by the equiv al ent of b as e

whi ch has r epl ac ed the hydrogen of the corr espon ding acid .

Thus N aCl in which N a has r epl ac ed H of HCl is uni

, ,

val ent .

K 80 4 in which K has r epl ac ed H of H SO is bival ent

2 , 2 2 z 4, .

Pr eparatio n of V o lumetr i c S o lutio n s In prep aring volu .

m etric solutions i t must be born e in min d that most s alts wh en

dissolv ed in wat er c aus e a cond ensation in volume through ,

reduction of t emp erature whil e som e substanc es as for in stanc e

, ,

sulphuric acid and alk ali hydroxids caus e a ris e in t emp era ,

ture and a cons equ ent incr eas e in volum e It is th erefor e .

n ec ess ary aft er m aking a solution to set it asid e for a short

, ,

tim e in ord er to allow it to attain the prop er t emp eratur e

.

b efore m easuring it .

It is always the b est pl an to tak e a w eigh ed qu antity of ,

the s alt slightly gr eat er th an th at r equir ed by th eory and

, ,

to dissolv e it in l ess wat er than i s n eeded for the finish ed

solution This solution is titrat ed its str ength d et ermin ed
.
,

and th en dilut ed to the prop er m easur e .

Aft er dilution it S hould be again c ar efully titrat ed and

its titer v erifi ed
All volum etric solutions should be m
.

ad e with distill ed

wat er and with r eag ents which are of a high degr ee of purity .

Standar d Temper atur e A cubic c entim et er is the volum e

.

occupi ed by one gram of distill ed w at er at its m aximum d ensity

4
°
C (39. T hi s how °
ev er i s no t the
, cubic c entim et
, er
14 THE E SS ENTI AL S OF VOL U METR I C ANALYSIS
us ed in volum etric an alys is I t is conv eni en t to use n an alys es
"

. I

of this sort a cubic c en t im et er whi ch rep e en ts the v olum e of

'

r s

on e gram of dis t ill ed w at er at a t em p erat ur e which is easily

at t ain ed an d m ain t ain ed at any s eason of the y ear .

The t emp eratur e at which m easuring instrum ents ar e

graduat ed is the t emp eratur e at which vol um etric s olu t i ons
sh ould b prep ar ed and at which all volum etric op erati ons
e ,

should be conducted 4 C is a t emp erature at which i t is

.
°
.

obviously impossibl e to work exc ept during on e or two m on t hs

of the y ear F or this r eason the t emp eratur e of 6 C

°
. F ) 1 . .

has b een t ak en as the st an dard T he cubic c entim et er us ed .

in vol um etric an alysis un der this s tandard is the v olum e

, ,

occupi ed by on e gram of distill ed w at er at the l att er t emp era

ture .

The employm ent of this st and ar d of t em p erat ur e though ,

l ong in vogu e is jus t ly criticiz ed as too low In order to ob tain

,
.

accur at e r esults the t emp eratur e of the atmosph er e in which

the titration is p erform ed must not be too much at v ari anc e

with the t emp erature at which the instrum ents a e graduat ed r

an d the solu t ions m ade A t emp eratur e of 1 6 C is on e

°
. .

which is exc eedingly difficult to maintain in the warm months

of the y ear th erefore it has b een sugg est ed to t ak e a high er
,

t emp erature as the standard .

The U S P VI I I r ecomm ends the emp loym ent of 5 C

°
. 2 .

(7 7
°
F.
) a s th e st an dar d T his whil e b et t er t.h an the low er ,

t emp eratur e is r egarded by m any as b eing t oo high and the

,

use of 2 0 C (68 F ) as the st an dard is now b eing v ery

° °
. .

favorably considered t his b eing n ear er the av erag e t emp eratur e

,

of the atmos p h er e in l ab oratori es through out the y ear Wh at .

ev er t emp eratur e is adopt ed it is at thi s t em p eratur e that ,

the wh ol e set of m eas uri ng instrum ents mus t be gradu at ed ,

an d all t i t r ati ons c arri ed out It w oul d be obvi ously improp er

.

to use a bur ett e gradu at ed at 1 6 C an d a fl ask or c ylind er

°
.
 VOLUME TRI C OR STANDA R D S OLUTI ON S 15

graduat ed at 5 C o to empl oy s olu t ions at a t mp ratur

2
°
.
,
r e e e

which is differ en t from th at at which th y a e m ade e r .

Mil Th t erm cubic c en tim et er (cc ) has b een r ep l ac d

. e . e

by the w ord m i l in th U S P I X and in m any o t h er r ec ent e . . .

,

b ooks The U nited Stat es Bur eau of Standards decl ared that
.

the t erm cubic c entim et er was a misn om er th er e b eing a slight ,

di fferenc e b et w een the t h ous an dth p art of a lit er and the

cubic c entim et er as one li t er was determin ed to be equiv
,

alen t to cubic decim eters Hence the w ord mil .

,

an abbr evi at i on of millili t er was adopt ed an d r epres ents the ,

thousandth par t of a liter .

The U S P lit er is the Volum e occupi ed by

. . . gms .

of dis t ill ed w at r w eigh ed in air with brass w eights at a tem

e .

per atu re of 5 C an d b a2r om et ric

°
p r essur e
. of 7 60 mm .

To Titrat e a subs t anc e m eans to t est it volum etric ally

for the am oun t of p ure subs tan c e i t con t ains The t erm is .

“ “
us ed in pr ef er en c e to t es t ed or an alyz ed b ec ause th es e ” ”
,

t erms may rel ate to quali tat ive examin at ions as w ell as
qu an t i tat ive wh ereas t itrati on app li es only to volum etric
,

an alysis .

Resi dual Ti tr atio n Re t i tr at i o n s om et im es c all ed Bac k

,
-
,

Titrati on consists in t r eating the subst anc e un der ex amin a

,

tion with stan dard s olution in a quantity known to be in

exc ess of th at actu ally r equir ed; the exc ess (or r esidu e) is
th en asc ertain ed by residual t itration with anoth er standard
solution .

Thus the qu antity of the fi rs t solution which w ent into

combin ation is found .

E x ample mm onium c arbon at e is treat ed first with T

. A

H2 80 4 in exc ess and the exc ess th en found by titration with

,

K OH .
16 THE E SS ENTI AL S OF VOLUME TRI C ANALY SIS
1
The quantity of the ! KOH us ed is th en deduct ed from
3
i
the quan t ity of
; H2 80 4 added, whi ch gives the qu an t ity of
the al tt er which was n eutraliz ed by the ammonium carbon at e .

Ti trati ons may be c arri ed out i n fl asks b eak ers or in , ,

white porc el ain evaporating dish es Flasks of the E rl enm eyer

.

p att ern see Fig 2 4 having a short narrow n ec k and a broad

,
.
,

fl at bottom are v ery desirabl e for this purpos e ; th ey admit

,

of shaking th eir con t ents With out danger of loss and p ermit ,

r eady observation of color changes If a flas k is us ed the .

tip of the bur ett e sho uld ext en d w ell into its n ec k in ord er
to p r ev ent any loss of the r eag en t T he fl ask should be .

rotated aft er each addition of the reagent and wh en the end ,

of ti trati on is n ear any of the solution adh ering to the sid es

,

of the flask should be wash ed down wi t h dis t ill ed wat er .

A whit e porc el ain til e or a sh eet of whit e p ap er p l ac ed un der

,

the fl ask or b eak er ai ds m at eri ally in the obs erv ation of the
,
.

color change .
 C H APTE R IV
I ND I CA T O RS .
*

IN volum etric an alysis the substanc e to be analyz ed in

the st at e of solution is pl ac ed in a b eak er an d the st an dard
solution is add ed from a burette until a c ertain reaction is
produc ed The exact mom ent wh en a suffi ci ent quan t ity of
.

the st and ard solution has b een add ed is known by c ert ain
V isibl e ch ang es whi ch diff er according to the substanc e an alyz ed
,

and the s t and ard solution us ed Wh en such a Visibl e Change .

occ urs the end reaction is reach ed -

.

The end r eaction m anif ests its elf in various w ays as

-
,

follows :
I C ess ation of pr ecipit ation
. .

2 First app earanc e of a pr ecipitat e

. .

3 C
. h ang e of color .

In som e c as es how ev er the additi on of the standard

, ,

solution to the substanc e und er an alysis do es not produc e

ei t h er a pr ecipit at e or a ch ang e of color ; in such c as es we
must r esort to the use of an indicator .

A n i ndi cator is a subst anc e which is us ed in volum etri c

an alysis and which indic at es by ch ang e of color
, or som e ,

oth er Visibl e S ign the exact point at which a given reaction

,

is compl et e .

G en erally the indic ator is add ed to the substanc e und er

ex amin ation but in a few c as es it is us ed alongsid e a drop
, ,

of the substanc e b eing occ asion ally brought in contact with

a drop of the in dic ator .

* r
A m o e detai led de s ripti
c on of the t rs
i ndi vi dual i n di ca o is g iv
en in
the Ap p endi x .
18 THE E SS EN TI AL S OF VOLU ME TR I C ANALYSIS
Thus in es t imating an alkali wi t h an acid v ol um etric s olu ~

tion the alkali is hown to be c omp l t ly n utraliz d when

S e e e e

the litmus t inc t ur which was added b ec om es fain t ly ed or

e r

the p h en ol p h t h al ein c ol orl ess Again wh en h al oi d s al t s are

.
,

es t im at ed wi t h ni t rat e of S ilv er s olu t i on C hr om at e of

p otas ,

sium is added as in dic at or A whit e p reci pi tat e is pro duc ed

.

as l ong a any h al og en is pr es ent to combin e wi t h the silv er

s ,

and wh en all is p r eci p i t at ed the Chrom at e of p ot assium acts

up on th silv er ni trat e forming the d silver Chr omat e t his

e ,
re ,

color thus sh ow ing th at all the h al ogen has b een precip i tat ed .

I N D I CATO R S C O MM O N LY U S E D

The p rincip l e in dic at ors us ed a e r

i t re of Li tmus which sh ows aci di ty by turning ed

T nc u , r

and alk alinity by b ec oming blu e .

Pheno lp ht hal ein S o l ut i on which is c olorl ess in aci d s ol u

,

tions an d red in alkalin e s olutions but is not reli abl e for ,

alk alin e ph os p h at es bic arb on at es or amm oni a

, .

Methyl oran ge So l ut i on t urns red wi th acids and y ell ow

-

with alk alies I t is not aff ect ed by c arb onic aci d and is
.
,

therefor e adap t ed for th ti trat i on of alkalin e c arb on at es

e .

Ro so li c aci d Sol ut i on is y ll ow wi t h aci ds and Vi ol et red

- e -

wi th alkali es It is v ery s ensi t iv to amm onia

. e
.

Ti nctur e of Turm er i c t urns brown wi t h alk ali es and the ,

yell ow c olor is restored by acids .

Co chin eal So lut i o n t urns V iol et wi t h alkali es an d y ll owish e

wi th acids It is us ed chi efly in the p res enc e of ammonia

.

or alkali earths .

E o sin S o lutio n is red by transmitt ed ligh t an d sh ows a ,

strong green fluoresc enc e by r eflect ed light Aci ds destroy .

thi s fluoresc enc e and alkali es r estore it .

Br az il woo d Test so lu t i o n t urns purp lish r d with alkali es

- - —
e

and y ellow with aci ds .

20 THE E SS ENTI AL S OF VOL UMETRI C ANALYSIS
The di ssoci ation of c omp oun ds i n to i ons wh en diss olved
in wat er is illustrat ed in th fol lowing lis t
e

S od ium chl ori d in t o (N a an d (C l

Po t assium ni t rat e in t o (K (N 0 3
hydroxid into (K (O H
ac etat e in t o K
( (C 2 H3 0 2
S ulphuric acid int o (H (HS O ,
or H
( +) (H + ) d (S O 4 )
an

The xt ent of this diss oci at i on dep ends up on the n at ure

e

of the substanc e and the degr ee of dilution ; the gr eat er the

dilu t ion the more compl et e the diss ociat i on Furth erm or e .
,

strong acids and b as es diss ociat e r eadily even in comp ara ,

tiv ely conc entrat ed s olu t ions whil e the w eak er aci ds and b as es
,

are mor e o l ess un diss ociat ed Wh en diss olved i e th ey are

r ,
. .
,

not r eadily sp lit up into ions Th eir s al t s how ev er are

.
, ,

imm ediat ely and c omp l et ely ioniz ed Th erefor e upon n eu .

,

trali i ng a w eak aci d or b as e an i oniz abl e s alt is form ed

z ,
.

According to the t h eory of Arrh eni us the r eactions of an aly t ic al

,

ch emistry are chi efly r acti ons b etw een ions and not b et w een
e

atoms .

Strong aci ds b as es and s alts exist in solution not as

, ,

mol ecul es but chi efly in the form of ions The form ation .

of Sil e chlorid by the reaction b etween silver nitrat e and

x r

sodium chlori d takes p l ac e according to the foll owing equation :

Ag/N O gAq + N a/ C 1Aq . . AgCl ( solid) + N a/N 0 3Aq .

The stat e of diss ociat i on b eing d enot ed by the vert ic al

lin e b etw een the ions of the mol ec ul es .

Thi s th eory als o expl ains why K / C 10 wi th Ag/ N O do es 3 3

n ot form AgCl in t hat the r eaction involv es the ion C10 3

,

and n ot the atom Cl .

 I N DI CATO RS 21

.
Theo i es
r I n of
di cator s In c onn ec t i on wi t h th
. use of e

in dicat ors in n eutraliz at ion analys es the ques ti on as to the ,

caus e of the color ch ang es is one of c onsid erabl e in t eres t .

T wo dis t inct vi ews are h eld O f th es e the I oni zati on .

Theo y of Ostwald has r ec eiv ed almost univ ers al acc ep t anc e

r .

According to this th eory the col or ch ang es ar e ascrib ed to a

change in the indic ator from a m ol ecul ar to an ionic condi t ion .

As ex emplified in the c as e of ph enolphth al ein the colorl ess

mol ecul e
O C O C 6H4 C (c a non)2

is dissociated into the r ed n egativ e ion

O CO C 6H4 C (C 6 H4 O H) C 6H4 O .
(I I )
In the oth er l ess known vi ew on this subj ect (the
and

C hromoplwri c Theory) the s ensitiv en ess of the indic ators

and its color ch ang es is ascrib ed to a ch ang e in the cons t i

tuti on of the indic at or involving a chromophoric group und er

, ,

the influ enc e of hy drog en and hydroxyl i ons According to .

t his Vi ew the color ch ang e is due (in the c as e of ph enol

ph th al ein ) to a ch ang e of constituti on from the colorl ess l actoid
()I with no chromo p horic group to th e c ol or ed quinoid ( )
I I I
,

wi t h a quinon e chromophore .

(N aO O C C 6 H 4 )(HO C 6 H4 ) C ZC 6 H4 1 O ,

and th at ionization of the s odium s alt is m erely a c orn

the

c idence an d not the c aus e of the color ch ang e .

Which ever of thes e vi ews is the correct on e r em ains for ,

fu t ure investigat ions to prov e That of O s t wal d b eing most .

,

gen eral ly acc ep ted at the pres ent tim e is treat ed mor e fully ,

below .

Sec j ul ius t g
S i e li tz ,
J r
ou . Am . C h em So c
.
,
XXV, 111 2
22 THE E SS ENTI AL S OF VOLUMETRI C ANALYSIS
The I on izatio n Theory of In t r T he indic ators us ed di ca o s * .

in alkalim etry and aci dim etry are comp oun ds of f eebl e acid
or b asic ch arac t er an d h enc e n ot p r on to diss oci at i on in
,
e

s ol ut ion bu t wh en n eutraliz ed the s al t form ed i oniz es the

,

instant of its format i on ; the i ons so lib erat ed giv e ris e to

c ol ors which diff er from t h os e of the original c omp ounds .

Any f eebl e acid or b as e m ay be u t iliz ed as an in dic at or

if its i ons h av e a c ol or different from t h at of the um i oniz ed —

c omp ound Strong acids 0 b as es a e not sui t ed as in dic at ors

. 1 r
,

b ecaus e th ey i oniz e whil in a free stat e on dilution and thus e ,

give no col or wh en n eu traliz ed .

A soluti on i n which H i ons pr edomin at e has an acid reac

'

tion whil e one in which O H ions pr edominat e r eacts alkaline

, .

Ph enol p hth al ein is a f eebly acid in dic at or and in its ,

undissociat ed state is c ol orl ess I t d oes no t dissoci at e readily .

unl ess n eutraliz ed but wh en sodium hydroxid is added to

, e

i t s solution a s odium salt of p h en olphth al ein is form ed which

,

imm ediately ioniz es and the i ons lib erat ed impart t o the s oluti on
a brilli ant ed color r If now som e acid is added the s odi um
.

s alt is dec omp os ed and the aci d ph en ol phth al ein again set
free and the s olution b ec om es c ol orl ess
,
.

If a few drops of p h en ol phth al ein s olu t ion be added to

an aci d s olu t i on ioniz at i on of the form er is prevent ed by ‘
,

the pr es enc e of the str ong er aci d; if n ow s om e s odi um hydroxi d?

soluti on is ad ded the O H i ons of the l att er unit e with the
,

H ions of the aci d an d wh en the aci d is comp l et ely n eu t raliz ed

,

the firs t drop of exc ess of alk ali uni t es wi th the p hen olphtha
l ein forming a s al t which imm edi at ely ioniz es and produc es
,

the ch arac t eris t ic ed col or which shows the end of the r eaction
r .

In the ti trati on of a feebl e acid the end p oint is often -

stw ld s L hrb h d A llg

See O a
’
e uc er em ei n en C hem i e, 18
91 , and S ci enti fi c

s f A lyti l C h mi stry s W
al o al ek rs
’ “I nt r
Fo und ti a on o na ca e , 1 900 ; oduction to

Physi l C h m i st ry
”
ca e 899 ,
1 .
 I ND I CATO R S 23

indis tin ct and is l ac king in sharpn ess ; thi s is b ecaus e the

in dic at or us ed has a great er t end ency to ioniz e than the acid
i t s elf In t his c as e the H i ons p res ent just b efore the com
.

l eti on of the r eaction are not in su ffi ci ent amoun t to fully

p
r etard the ioniz at ion of the indic ator and h enc e the l atter
“

diss oci at es p artly b efor e n eutraliz at ion is compl et e and giv es

ris to an indefinit e end re action Th eref ore it is n ec essary
e -
.

wh en ti trat ing a feebl e acid that an indicator should be s el ect ed

wh os e alkali salt i oniz es with the production of a distinc t
c ol or change and whos e tend ency to i oniz e is l ess th an that
,

of the aci d Ph en ol p hth al ein is a suitabl e indic ator in this

.

c as e pr ovided a strong alkali be us ed for t itrating

,
.

Fix ed alkali es r eadily yi el d ioniz abl e s alts wi t h ph enol

phthal ein but ammonia do es not The l att er b eing too weak
,
.

a b as e to yi el d with so f eebl e an aci d a s alt which can wit h ,

s t and the hydrolytic action of the water in dilut e solutions ,

an d as a c ons equ enc e a l arg er exc ess of the ammoni a mus t

be us ed to ov ercom e this Th us is acc o unt ed for the imp erf ec t

.

c ol or chang e of ph en olphthal ein wh en ammonia or its s alts

are p r es ent an d why the col or b ecom es Visibl e o nl y aft er a

l arge exc ess of the al kali is add ed .

Paran i trophenol is als o an acid indic ator ; it exists in

s olution in the form of un dissociat ed c olorl ess mol ecul es yet ,

i t s el ectro n egativ e ion is intens ely y ell ow in color Thi s com

-
.

pound has a slight t end ency to dissoci ate in dilut e solutions ,

but the pr es enc e of a trac e of a strong er acid will overcom e

this t endency and the solution r emains colorl ess If an al kali .

is how ever add ed a s alt of paranitrophenol is form ed which

, , ,

immediat ely ioniz es and exhibits the int ens e y ellow color of
i t s lib erat ed i on .

O th er indic at ors exhi bit a color in both the ioniz ed an d

the non i oniz ed s tat e but the colors in both conditi ons a
-
, re

diff er ent as in the c as e of litmus l acmoi d an d m ethyl orang e

'

, ,
.
24 THE E SS ENTI AL S OF VOL U METR I C ANALYSIS
Methyl r nge is b oth an aci d and a b as e and will form
o a

ioniz abl e s al t s with eith er acids or alkali es ; i t s in dic ator

ch aracteristics are h owev er due ess en tially to i t s b asic char
, ,
-

act er .

The s al t which m et hyl orang e f orms wi t h aci ds diss oci at es

into red ions ; this up on the additi on of an alkali r et urns to
, ,

i t s un diss ociat ed s tat e which is yell ow Bec aus of i t s w eak

,
. e

b asic charac t er its c omp oun d wi th acids is readily d c omp os d e e

by alkali es but it tak es a strong aci d o a r el at iv ely l arge

,
r

qu antity of a f eebl e acid to diss ociat e i t in i t s non i oniz ed -

stat e h enc e thi s indic ator is v ery s ensi t iv e to alkali es and

, ,

much l ess so to acids .

With r efer enc e to the acid ch aract er of the indicator the

expl an ation of its action is th at the n on ioniz ed indic ator is -

r ed whil e its i on is y ellow

,
Acids l ess en its i oniz ati on and
.

produc e a red color whil e alk alies pro duc e a highly i onizabl e
,

sal t and h enc e a y ellow c olor Wh en a w eak but slightly .

i onizabl e acid is added to the m ethyl orange s oluti on the H ,

'

i ons of the acid giv en up in exc ess of the am oun t r equir ed for
n eutraliz ation are no t su ffi ci en t to yi el d en ough of a non
ioniz abl e s alt to prod uc e a deci ded red c ol or h enc e a l arge ,

quantity of such a w eak aci d is r equir ed to giv e an acid

in dic ation Thi s w oul d exp l ain why m ethyl orange is not
.

suitabl e as an in dicat or for w eak acids and why i t is v ery ,

s ensi t iv e to alkali es .

L itmus is an acid indic at or whi ch sligh t ly diss oci at es in

s olution Its non ioniz ed mol ecul es are red but i t s n egativ e
.
-
,

i ons are blue If it is add ed to an alkali a s alt is form ed

.
,

which at onc e ioniz es and giv es a bl ue c ol or If add ed to .

an aci d ioniz ation is p r ev en t ed and the r ed c olor of the non

,

I onr ed m ol ecul es app ears

z .

From the abov e expl an ations it will be s een t h at indic ators

cann ot be in discrimin at ely us ed and th at n o on e indicator ,
 I ND I CATO R S 25

will be suitabl e for every t itrati on Henc e the i ndic ator must .

be s el ect ed to suit each c as e Thi s s el ecti on is facili t at ed by

;

referenc e to the cl assific ation of in dic ators acc ording to F , .

G l as er Z tchr f a Ch em 1 899
,
. . . .
, ,

Gr oup I I n di cators F orm in g Fairl y S t abl e Sal t s

. The .

m emb ers of this group c omp ris e such indic ators as are ( ) of I

a s t rong acid ch aract er and which r eact r eadily with w eak

b as es or (2 ) of a feebl e b asic charact er and which require

,

a s t r ong acid to form a st abl e s al t Henc e th ey will b f ound . e

to be v ery ensi ti v e to alkali es an d are us eful in the titrati on

s ,

of w eak b as es as ammoni a and the amin e b as es as w ell as

, ,

strong b as es and aci ds The indic ators of this gr oup are .

the f oll owing arr ang ed in the ord er of th eir s ensitiv en ess
,

t owards alkali es :
()I I o d eo si n R e s azurin
, ; () T rop ae olin O O L2 u teo l ; (3) ,

Methyl and E thyl O range ; (4 ) Cong o Red; (5) C ochin eal ;

(6) L acmoid .

Gr oup I I I n di cators Po ssessin g Fai nt Aci d Propert i es an d

.

Yi eldin g S al t s w hi ch a e V ery U n st abl e r T h es e are r eadily .

dec ompos ed by r el at iv ely f eebl e acids an d are in cons equ enc e ,

ver
y s e n s i ti ve t ow a r ds a ci ds slightly so t ow ,
ards a lk ali es .

Th ey are () R osolic I a cid ; () C urcum a ; (3) P h enol 2

p h t h a l ein ,
F la e sc inv; (4 ) A lph a n ap hth o lb en e i n -
z .

G oup I I I In di cator s Occup yi n g a Pl ace Mi dw ay between

r .

the Ot her Two Gr oups Th ey are s om ewh at strong er acids

.

than t hos e of G roup I I but feebl er th an thos e of G roup I

, .

Th ey are f airly s ensitiv e tow ards both aci ds and alk ali es ,

bu t are m ore s ensitiv e t ow ards acids th an t h os e of Group I ,

an d l ess so tow ards alk ali es Th ey are '

.

( ) luoresc ein Ph en ac etolin ; ( ) Haem at oxylin G allem

1 F ,
2 , ,

Aliz arin ; (3) L itmus ; (4 ) Parani trophenol .

This division of indic ators in t o gr oup s as abov e facili t at es , ,

the s el ec t ion of an in dic at or s u i t a bl e for the work in h and .

26 THE E SS ENTI AL S OF VOLU ME TRI C ANAL YSIS
For in stanc e for t i trat ing w eak acids a gl anc e at the group s
, ,

will S h ow th at the m emb ers of G roup I I a e b est adap t ed r

for this p urp os e Again w eak b as es will be b es t t itrated by

.
,

the indic ators of G rou p I St r ong acids or b as es may be

.

t i trat ed by m eans of any of the indic at ors .

The q uan t i ty of in dic ator t ak en in a titrati on is a m att er

of c onsi derabl m om en t The small est qu antity which wi ll
e .

p r oduc e a distinc t c o l or sh oul d be t ak en bu t i t is equ a lly ,

imp ort ant th at the quanti ty be not too small fo the volume r

of liqui d ; for in high dil ut i ons the hy dr oly t i cac t ion of w at er

ass erts its elf an d int erm edi at e tin t s will r es ul t which int erf er e
, ,

with the sh arp n ess of the end c ol or .

If too much of the in dic ator is us ed the s ensi tiven ss is , e

l ess en ed b ec aus e aci d o alkali mus t be added to c onv ert the

,
r

in dicator in t o a s al t o wh en form ed to dec ompos e i t ; i e

,
r . .
,

a minimum of exc ess of the ti t rating flui d w oul d r eac t with

a sm all p or t i on only of the in dic at or an d int erm edi at e t ints

w ould be p roduc ed until su ffi ci ent of the titrat ing s olu t ion

,

has b een add ed to n eut raliz e all of the in dic at or p r es ent This
'

is esp eci ally tru e wh en using c en t in orm al s olu ti ons dr op s . 20

of litmus added to 0 mils of water r equire from 0 to I 4 drops

1 1

of a cid or a lkali s ol ut i on to p roduc e a change of C o

l or .

100

Thus the indicator i t s elf t akes up som e of the standard

soluti on and h enc e the n ec essi ty fo usmg as small a quantity
,
r

of the in dic ator as p ossibl ; usu ally from 3 to 5 d ops of the e r

i ndi cator may be taken to each 50 or I OO cc of the fl ui d ti trated . .

The degree of di luti on of the substance titr t d is ls a

a e a o

m att er of c onsiderabl e mom ent In v ery conc entrat ed solu .

t i ons i onizat i on do s n ot so r eadily occur whil e too great a

e ,

dilu t i on diminish es the r eactiv e abili ty of the ions b ec aus e

of t h eir gr eat er s ep arat i on an d als o b ec aus e of the hydro
,

lytic dissociation of wat er i t s elf into H and O H i ons which '

28 THE E SS ENTIAL S OF VOLU M E TR I C ANALYSIS
FO R I N O R GAN I C A CI DS FO R O RG A D
AN I C CI S

H ZS O ” H cl, H N 0 3 . Ph lp ht h l i
eno a e n( ll) a Rs o oli c

Phe nolp h th alei n L it m s R s

,
u ,
o oli c A id (
c t
ex ce
p t i
ace c, i tr ic c an d

A ci d, Methyl O ra
nge . t t ri ) G ll i
ar a c ,
a e n .

H 3F O 4 .

Phe n olp hth alei n (neutraliz ed to

Na
Methyl O r ange an d Cochi neal
(each neutraliz ed to N aH 2P 0 4 ) .

H 25 O 3 .

R s
o oli c A cid an d Me hyl O t r ng
a e .

H 3BO 3 .

Phe nolp h th l i (aft r dditi n

a e n e a o

of glyce rin) L itmus a d T ur m ri

,
n e c

a
p p e r .
 C H APTE R V

A PPA RA T U S U S ED IN VOLUME TRI C ANAL Y S E S

The Bu r ett e is a graduat ed gl ass tub e which hol ds from
2 5 to 10 0 mils and is gradu at ed in fifths or t enths of a mil .

an d pr ovid ed at the low er end wi t h

a rubb er tub e an d p inch cock -

The .

use of this instrum ent is to accurat e

ly m easur e quantiti es of st and ard

solutions us ed in an analysis It is .

in an upright p osi t i on wh en in use ,

and the flow of the s ol ut ion can be

r egul at ed so as to run ou t in a
stream or fl ow in drops by pressin g
the p inch cock b etw een the thumb
-

and for efin g er The qu anti t y of

.

s olution us ed can be r ead from th e

graduat ion on the ou t sid e of the

t ub e Thi s is the simp l est and m os t
.

common form of b urett e and is ,

known as Mohr s (Fi g ) ’

. I .

The use of the pin ch cock in -

Mohr s bur ett e may be disp ens ed

’

with by introducing into the rubb er

FIG 1
tub e a sm all p i ec e of gl ass od r ,

which must not fit too tightly By

. .

firm ly squ eezing the rubb er t ub e surrounding the gl ass rod a

small c an al is op en ed t hrou gh whi ch the liquid esc ap es A
,
.

29
30 THE E SS ENTIAL S OF VOL U METR I C ANALYSIS
very delic at e ac t i on an in this way be obtain ed and the fl ow
c ,

of the liqui d is c omp l et ely under the c on trol of th op erator e .

(See Fi g .

The great est drawb ack to this burette is th at i t c ann ot

be us ed fo p erm ang an at e or ot h r s olu
r e

tions that act up on the rubb er .

This def ec t can be ov erc om by the us e e

of a bur ett e h aving a gl ass s t op c ock in C -

l ose d
pl ac e of the rubb er t ubing and p inch
cock This f orm has the addi t ion al ad an
. v

tag e of b eing c apabl e of deliv ering the s oluti on

in drops whil b oth h ands of the op erat or a e
e r

dis engaged (Fi g .

Anoth er good arrang em en t is that in

which the tap is p l ac ed in an oblique p osi t i on ,

so th at it will not easily drop out of p l ac e

Fi
( g 4)
.

h s gl ass st op cock buret t es sh ould be

T e e -

emp t i ed an d w ash ed i mm edi

at ely aft er use esp ci ally if so da

,
e

or p otass a s olu t ion has b een

us ed ; for th es e act upon the
gl ass and of t en c aus e th st0p e

er to s t ick so fir mly t h at it
p
c ann ot be t urn ed o r em oved r

wi th out d anger of breakin g

the ins t rum ent .

The m ost s at isf ac t ory f orm

of gl ass s t op c ock is t h at sh own
-

F 3
IG .
in F
.
i g 5 . °
F 4 IG

Wh en a numb er of es t ima
tions are to be m ade in which the s ame volum etric s olu ti on is
employ ed the arr ang em en t sh own in Fi g 6 is v ery s ervic eabl e
,
. .
 APPA RAT U S USED IN VOLUM ETR I C ANAL YSIS 31

A T sh ap d
—
e gl a ss t ub e is ins er t e d b etw e n th e l ow r e ned e

of th b
e u r ett e a n d th e p inch cock a n d c o
-
nn e c t e d by a r u b

b er t ub wi
e t h a r e s erv o ir c on t aining th e v o l u m e tric s o l u t i on .

T h e t u b e w hich c o mmunic at es wi t h th e r es ervoir is p r o vi d ed

wi t h a p inch c ock which wh en op en all ows the s ol ut i on to
-
, , ,

fl ow in t o a n d fill th e bur e tt e in so gr ad u a l a m a nn e r that

FI G .
5 .
FI G 6 . .

nob ubbl es are f orm ed . The burette is mp ti ed in e the usu al

mann er .

E . 69 °
A . his is us ed for
A utomati c Bur ette i
( g
F . T
the s am e p urp os e as the for eg oing I t is p rovi ded with a .

side t ub e for c onn ecti on wi t h r s erv oir and has an overflow e ,

cup which prevents i t s b eing fill d to abov e th z ero mark e e .

The thr ee way stop cock is so arr ang ed t h at if t urn ed on e

- -
way the inl et is op en ed and the liquid from the r es erv oir flows
in t o and fills the b uret t e If turn ed the o th er way the inl et
.

is cl os ed and the ou t l et is Op en ed and the bur ette may be

FI G .
7 . FI G . 8 .

empti ed If
. h n dl
the a stop c ock is t urn ed h alf way
e of the - -

roun d b oth op enings are clos ed

,
.

Th er e are m any oth er f orms of aut om at ic bur ett es .

Wh en working wi th s olu t i ons whi ch a e r eadily alt er ed

r

by contact wi th air as for exampl e stanno us chlorid potas

, , ,
 APPA R AT U S US ED IN VOLU ME TR I C ANALY SIS 33

sium sodium or b arium hydroxid or ammonia an arrange

, , ,

m en t like t hat d epicted in Fig 8 is v ery s ervic eabl e In t his

. .

the u p p er end of the b ur ett e is

conn ect ed with the r es ervoir by
m eans of a rubb er tub e thus ,

making an air tight combin ation -

b etw een the bur ett e and the res er

voir Its utility may be furth er
.

enh anc ed by providing the r es er

voir with a sod a li m e t ub e or som e -

oth er suitabl e absorption tub e .

Anoth er form of app aratus is

shown in Fig 9 I n this both . .

the bur ett e and the r es ervoir are

provid ed with tub es containing
sod a lim e t o insur e a prot ecti on
-

ag ainst the admission of C 0 2

and moistur e from the air .

Pinch coc k s us ed with M ohr s

’
-

burett es are of various kinds .

See Figs 0 and . 1 ,

11 12 .

The scr ew pinch cock * Fi g —

, .

12 is a very us eful devic e ; it

,

may be us ed lik e the ordin ary

pinch c ock by pressur e with the -

fi ng ers up on a a wh en a rapid —
,

flow is d esired or the nut screw ,

-

b
() m ay be so ad j usted as to
FIG 9 . .
allow a slow er flow or to d eliv er

the s olution in drops thus giving the op erat or the fr eed om

,

of both h ands for oth er work .

Bur ett e sup p orts are of various forms O ne of the b est .

W B rg d rf
. V . e en o .
34 THE E SS ENTI AL S OF VOLU ME TR I C ANAL YSIS
for one or two burett es is sh own in Fi g 1 3 It is mad e of . .

iron can stand firmly up on an un even surfac e and d oes not

, ,

easily ti p ov er The bur ett es are f ast en ed to i t by m eans

.

of cl amp s ill ustrated in Figs 4 and 1 5

,
. 1 .

A r evolving bur ett e hold er for eight burett es is shown in

-

FI G . 11 .

Fi g . 16 . supports are also made wi th whi t e porc el ain

Burrette -

b as e which en abl es the op erat or more r eadily to see the change

,

of color in the liquid titrated .

Pip ett es are of two kinds thos e which are m ark ed to —

deliver one quantity only and thos e which are graduat ed on

,

the st em lik e bur ett es Th eir use is to m easur e out portions

.

of solutions with exactn ess .

36 THE E SS EN TI AL S OF VOL UMETRI C ANALY SIS
A very c onveni en t form of p ip ette is one which has attach ed
to i t s u p p er end a p i ec e of rubb er t ubing in t o which a sh or t
,

pi ec e of gl ass rod has b een ns ert ed By squeezing the

I .

FI G . 16 .

rubb er surroun ding the gl ass od firmly b etw een the fingers a
r ,

c anal is op en ed and the liq uid can be drawn up in t o the

pip ett e by suc ti on with the lip s and run out again By re .

movi ng the pressure the c an al clos es and the flow of the

liquid is st opp ed at any p oin t (Fi g .
 A P PAR AT U S U S ED IN V OLU METRI C AN AL Y SIS 37

is v ery c on eni ent f or m eas uring small

The N i pple P i pette v

qu ntiti s liq i s such as o mils (F ig

a e of u d , I r 2 .

Wh en a v ol atil e or highly p ois on ous soluti on is to be

m easur ed i t is not advis abl e to suck i t up with the mouth .

50 mi l s

FI G . 1
7 . FI G . 1 8. FI G . 1
9
.

The pip ett e in t his c as e is fi ll ed by dipping it into the liquid

c ontain ed in a long n arrow v ess el until the liquid r each es
, ,

the prop er m ark on the p i p ett e th en closing the up p er op ening

,

and wit hdrawing Wh en thi s is don e the liquid which

.

adh er es to the outsid e of the p p ett e should be dri ed 0 1 i1

b efore the m eas ur ed liquid is deliv er ed .

A Fr ench firm has in t r oduc ed p i p ett es pr ovi ded wi th suction

38 THE E SS ENTI AL S OF VOLUMETR I C ANALYSIS
pumps shown in various forms by Fig
,
which p oss ess . 2 1,

the advant ag e ov er the ordin ary forms provi ded with a com

p r essibl e rubb er bulb t h a t the liqui,d c an wi t h p erf ect eas e

be drawn up t o the d esir ed p oint on the sc al e and with ,

abs olut e accur acy m ain t ain ed at the s am e h eight as long as

may be d esir ed .

The Measurin g fl ask is a v ess el m ad e of thin gl ass h avi ng

-

FI G . 20 . FI G . 2 1 .

a n arrow n eck and so c onstructed as to h old a definite amount

,

of liquid wh en fill ed up to the m ark on the n eck T h es e .

flasks are of vari ous siz es holding 1 00 2 50 50 0 1 0 0 mils

, , ,
0 ,

etc .but are gen erally c all ed Li ter F lasks

,
F i
( g .
”
.

L it er fl asks are us ed for m aking volum etric solutions .

T hos e which h av e the m ark b elow the middl e of the n ec k

are to be pr ef err ed b ec aus e the cont ents can be mor e easily
,
 APPARA TU S U S ED IN VO LU ME TR I C ANALY SIS 39

it er flasks are som etimes mad e wi th two m arks on the

L
n eck v ery n ear togeth er ; the low er one is the li t er mark If .

the fl ask is r equir ed to d eliv er a lit er it m ust be fill ed to the ,

upp er mark the differ enc e b etw een the two m easures b eing
,

FI G . 2 2 . FI G . 23 . FI G . 2 4 .

the quival ent of the liquid whi ch rem ains in the flask adh ering
e

to the sid es .

The Test m i xer or Graduat ed Cyl in der (Fi g

-
, 3) is for . 2

m easuring and mixing small er quanti t i es of solu t ions Th ey .

are m ad e of d iff er ent siz es holding 1 00 2 5 ,50 0 and 1 00 0 ,

0,

mils and gradu ated in fifths or tenths of a mil

,
.

Ti trati on F lasks Ti trati ons may be c arri ed out in fl asks

.

of any usu al sh ap e or in b eak ers or evap orating dish es but

, , ,

the fl as k il lustrated in Fi g 2 4 is to be pr ef err ed

. .
 C H APTE R V I

O N T HE U SE O F A PPARA T U S
IT important th at all ap p aratus us ed in v olum etric
IS

an alysis be p erf ectly C l ean E v en new apparat us shoul d be

.

cl eans ed by p assing dilu t e hydrochl oric aci d t hrough th em

an d th en rinsing wi t h distill ed w at er .

If the burette p ip ett e or oth er instrum en t is ev en sligh t ly

, ,

greasy the liquid will n ot flow sm oothly and drop s of the

, ,

liquid will r emain adh ering to the sides thus l eading to ,

in acc urat e r es ul t s .

G r easin ess may be r em ov ed wi t h dil ut e s oda s ol ut i on .

If this fails the instrum ent shoul d be all ow ed to remain for

some lit t l e t im e in a s oluti on c on t aining s ul ph uric aci d and
potassium dichr omat e which will radic ally r em ove all trac es
,

of gr eas e .

The bur ett e or oth er m easuring ins t rum en t s shoul d n ev er

be fill ed with volum etric s olu t i on wi t h ou t first rinsing ev en ,

if the bur et t e be p erfectly dry .

It is w ell t o wash the inside of the ins trum en t wi th two

or three small p ort i ons of the s ol uti on wi th which it is to be
fi ll ed
.

The bur ett e may be fill ed wi t h the ai d of a fun n el the ,

st em of which S hould be pl ac ed against the inn er wall of the

bur ett e so th at the solution will fl ow down the si d and t h us
,
e

prevent the formation of bubbl es .

The bur et t e should be fill ed to ab ov e the z ero m ark and ,

the air bubbl es if t h ere are any r emov ed by g en t ly t app ing

-
, ,

wi th the fin ger .
 ON THE USE OF APPA RA T U S 41

A portion of the liquid sh oul d then be allow ed to run out

in a s tream so that no ai bubbl es r emain in the low er p art
r -

of the bur ett e In the gl ass tap bur et t e i t can be easily s een
.

if any air is pres ent but in the pinch c ock bur ett e i t is some
,
-

tim es n ec ess ary to t ak e hold of the rubb er tub e b etw een the
thumb and for efing er and gently strok e upward Or the .

gl ass nip at the low er end of the bur ett e may be p ointed upw ard ,

and the p inch c ock ope n ed Wid e so th at a str eam of the liquid
-

will p ass through and forc e out any aI r th at may be inclos ed .

If the t itrat ion is to be conduct ed at a high t emp erature ,

as in the estim ation of c arbon at es wh en litmus is us ed as

,

the in dic at or or in the estim at ion of sug ar by c opp er solution

, ,

a long rubb er tub e should be att ach ed to the l ow er end of

the b ur et t e The boilin g can th en be don e at a littl e distanc e

.
,

an d th ex p ansi on of the liquid in the bur ett e avoid ed

e The .

p inch -
c ock is fix ed a bout midw ay on th e tub e .

Hart c alls att enti on to the fact that if the fluid in a bur ett e
or p i p ett e be un out r ap idly at on e tim e and slowly at anoth er
r ,

di ffer ent am ounts of fluid are obt ain ed “

.

This is due to the adh esion of the fluid to the inn er sid es
of the instrum ent an d r eading b efor e it has s ettl ed do wn
, .

I t is th erefore advis abl e always to d eliver burettes slowly ,

as mor e const ant r esults are th en obt ain ed .

Solutions which are m easur ed by m eans of pip ett es should

be dilut e sinc e conc entrat ed s oluti ons adh er e to gl ass with
,

diff er ent d egrees of t en acity and h enc e the amount of fluid

,

deliv er ed is slightly l ess than th at m easur ed .

The t emp eratur e of the s olutions m easur ed should be

tak en int o account sinc e all liquids are aff ect ed by ch ange
,

of t emp er atur e exp anding an d contr actin g as the t emp er a

,

ture is increas ed or r educ ed .

This ch ang e of v olum e in the c as e of stan dard soluti ons

do es not exactly corr es pond to th at in pur e wat er ; in fact ,
42
'

THE E SS EN TI AL S OF VOLU M E TR I C ANAL YSIS

some of th em difi er widely The correction of the volum e .

of a s t and ar d soluti on for the t em eratur e by the exp ansion

p
co effi ci ent of wat er is not entirely s at isfactory but in the case ,

of very dilute solutions this may be don e .

Casamaj or (C N xx x v 60 ) giv es the foll owing figur es

. .
, ,
1

sho wing the relativ e contraction and exp ansion of water b elow
and abov e 1 5 C :
°
.

D gr s C e D gr s C
ee . e ee .

8 . 000 590 17

9 . 00 0
550

10 . 000 4 92

11 . 000 4 2 0

12 . 000 334 2 1

13 . 000 2 36 2 2

I 4 . 000 1 2 4 2 3
1 5 normal 2 4
2
5+ . 00 1 9I 9

By m eans
of th es e numbers it is easy to c alcul at e the volume
of liquid at 5 C c orr esponding to any volume obs erv ed
1
°
.

at any t emp er atur e b etw een 8 C and 2 5 C If 2 5 cc of ° °

. . .

solu tion had b een us ed at 2 0 C the tabl e shows that 1 cc °

.
, .

of w at er p assing from 5 to 20 is incr eas ed to 1 cc° °

.

Th er efor e by dividin g 2 5 cc by
,
the quoti ent .
,

C C is obt ain ed which r epr es ents the volume at 1 5 C corr e °

,
. .

sp ondin g t o 2 5 cc at 2 0 C
°
. .

Th es e corr ec t ions are of valu e only for v ery dilut e soluti ons
and for w at er but us el ess for conc entr at ed soluti ons
, Slight .

vari ations of atmospheric pressur e may be disregarded .

ON THE RE AD IN G O F I N S TRU ME N TS

n arrow v ess els the surfac e of liqui ds is n ever l ev el

In .

This is owing to the c apill ary attrac t ion ex ert ed by t he si des

of the v ess el upon the li q uid drawing the edg e up and forming ,
44 THE E SS EN TI AL S OF VOLUMETRI C ANAL YSIS
r
E dmann s Fl o at F i g
’
8 is an el ong at ed g lass bulb which
, . 2 , ,

is weight ed at i t s l ower end wi th m erc ury to k e p i t in an,

e

upright posi tion wh en floating It is of suc h diam et er th at

.

FIG 8 FIG 2 F I G 30
. 2 . .
9
.
. .

i t will S li de easily up and down i nsid e of a buret t e Th er e .

is a ring at the top by which i t can be lifted in or out by

m eans of a b ent wire Aroun d i t s c enter a lin e is mark ed
. .

At t his lin e inst ead of at the m eniscus the r eading is

taken .
 ON THE USE O F AP P A RAT U S 45

hes e floats a e s om etimes provided wi t h a th erm omet er

T r ,

and t h ey t h en r egist er the t em p er at ur e as w ell as the v olum e .

O t h ers a e p r ovi ded with p roj ecting p oints al ong the si des
r ,

FI G 31
. .
FI G 3 2 .

the obj ect of which is to prev ent it from adhering to the walls
of the bur ett e (See Fi g
. .

For the p urpos e of f acilit ating the r eading s p eci al forms,

of bur ett es ar e c onstruct ed which a e pr ovid ed wi t h a d ark

r

longi t udin al s trip e on a whit e enam el ed b ackground (Fig .

the r efl ection of the dark stri p e with the m eniscus p ro

duc es the p ec uli ar app ear anc e shown in F i g 3 .The n arrow est
1 .

p oint is at th e mi ddl e o f t he m enisc u s an d

, by r eading fr om
this p oint v ery accurat e measur ements ar e obtained T he .
46 THE E SS ENTIAL S OF VOLU M ET RI C ANALYSIS
s am e effect can be produc ed by hol ding behi n d an ordinary
burette a white fl exibl e c ard h aving a h eavy black longitudin al
strip e about one eighth inch in width
,
-
.

Anoth er form of bur et t e d esign ed for the purpos e of

facilitatin g r eading is that p rovid ed wi t h whit e en am el ed
'

si des l eaving a strip of cl ear gl ass in front and b ack (Fi g

, .

This form is esp ecially ad apt ed for use with d ar k

color ed liquids such as iodin and p erm anganat e
, .

CA LI BRA TI O N O F I N S TRU ME N TS

Bur ett es m ade from tub es of n early uniform width

are .

Th ey are fill ed with distill ed w at er at 1 5 C (59 ) to the

°
* F .
°
.

0 m ark and t h en 2 5 50 or 1 00 cc run ou t and anoth er m ark

, ,
.
,

m ad e at the surfac e of the liquid The distanc e b etw een .

thes e two marks is then divided into 2 5 50 or 1 00 equal ,

p arts and the spac s again subdivided into fifths and t enths
,
e .

N ow i t is v é y rar ely possibl e to obtain tub es of ex actly the

r

s am e c alib er throughout and the divisions made as abov e ,

do not always repres ent exactly what t h ey are int end ed to .

If the tub e is wid er at one p oint the divisions at th at

point will contain more and if it is n arrow er th ey will contain ,

l ess than th ey should .

Henc e b efor e usin g a new bur ett e or in fact any oth er ,

m easuring instrum ent it is ess ential that the error if afiy , , ,

should be d e t ermin ed This is don e as follows : .

Fill the bur ette to the 0 m ark with distill ed w at er at 1 5 °

C (59 F ) and run out 1 0 cc at a tim e into a small w eigh ed

°
. . .

flask and w eigh after each addition of 1 0 cc

,
.

E ach 1 0 cc sh oul d w eigh exactly . 0 gms and every 1 .

,

I n tead s of 1 5
°
C .
(59
°
t mp r t r 5 C (7 7
F .
) t he e e a u e 2
°
.
°
F .
) is r ecom m en ded

becau s e thi sm r rly

o e nea app r h s th r di ry t mp r t
oac e e o na e e a ur e of the atmo p he s r
e

in tempera e t lim s
c e .
 ON THE U SE OF APPA RAT U S 47

devi ati on foun d shoul d be not ed and tak en I nto consideration

in using the instrumen t .

E x ample
w eigh ed grams .

+ 10 cc .

+ 2 0 cc .

+ 30 cc .

+ 4 0 cc .

0 cc
5 .

Thus the I st 0 cc w eighed

1 . grams .

2 d 1 0 cc .

3 d 1 0 cc .

4 th 1 0 cc .

th 1 0 cc
s .

Having obtain ed th es e d ata a tabl e like the following may

,

be construct ed and k ept in som e c onv eni ent pl ac e wh er e it

can be r eadily consult ed w hen ev er the bur ett e it r epr es ents

is b eing us ed It is not n ec essary to carry the fi gur e b eyond

.

the s econd d ecim al pl ac e .

48 THE E SS ENTI AL S OF VOLU METR I C ANALYSI S
Th er e should be no great r deviat ion than cc Ae .

bur ette which d evi at es m or is b est not us ed In the e .

foregoin g tabl e th ere is a devi at i on of cc at one p oint . .

In ord er to t es t the accuracy of a pip ett e fil l to the m ark ,

with distill ed wat er at 5 C 59 em p t y into a p r eviously

° °
1 .

w eigh ed flask w eigh again and thus determin e the w eight of

,

the w at er m eas ur ed O he gram is equ al to

. cc 1 .

L it er fl asks are t est ed as f ollows

The fl ask p erf ec t ly dry and cl ean is coun t erp ois ed on a
, ,

b al anc e c ap abl e of t urning wi th 0 5 wh en c arrying ab out . 0

2 00 0 gr ams ; it is th en fill ed t o the m ark wi t h dis t ill ed w at er

at 1 5 C (59 F ) and the incr eas e in w eigh t sh oul d be ex actly

° °
. .

the numb er of grams as the cc in dic at ed at the mark . .

Wh en very accurat e d et erminations are required various ,

factors shoul d be taken into account nam ely atmos pheric , ,

p r e ssur e t,
h e t emp er at ur e of the a i r an d t h at of th e w at e , r,

which shoul d be the s am e Atmosph eric humidity shoul d be.

of a definite degree and the w eights us ed should be m ade of

,

sp ecified m aterial .

The c alibration of a bur ett e which is gradu at ed in mils , ,

at 2 5 C
°
is con ducted as follows
.
,
:

Fill the burette to the 0 m ark with distill ed wat er at 2 5 °

C . The air shoul d be h alf s aturat ed wi t h moisture and of ,

the s am e t emp erature as the w at er The b arom etric p r essur e .

shoul d be 760 mm The w eigh t s us ed should be of brass a nd

.
,

the c oun t erpois e of the fl ask shoul d be of the s am e kin d of gl ass

as t h at of which the fl ask is m ad e Run out 1 mils at a t im e . 0

into the small coun t erpois ed flask and w eigh each 0 mils , 1 .

E ach 1 mils S houl d w eigh exactly

0 gms and every .
,

deviation found should be noted and tak en into consid eration

in using the burette .
 ON THE U SE O F A PP A RAT U S 49

E x ample

I st 10 mils w eigh ed gms . d

( viat ion n egligibl e)
e

2 d 10

3 d 10 9 954 3
-

4 th 10

sth 10 9 -97 53

rom th ese dat a a tabl e lik

F e the following may be con
struc ted and c onsulted wh en ever
,
the b urette it repres en t s is
b eing us ed .
 CHAPTE R VI I

M ET H O D S OF CALCULATI N G R E S U L TS
N
E ACH mil of a —

I
unival ent volum etric solution contains
fi
l
of the mol ecul ar w eight in grams of its reagent and
—
og ,

will n eutraliz e fi m of the mol ecul ar w eight of a unival ent

l

substanc e or fi m; of the m ol ecul ar w eight of a bival ent

,
l

substanc e .

Ea ch mil of a —

I
bival ent volum etric solution contains
“ n of
I
mol ecul ar w eight in grams of its r eag ent and will
the ,

n eutraliz e or combin e with fi m; of the mol ecul ar weight of

l

a biv al ent s alt or n o( of the mol ecul ar w eight of a unival ent

i
,
—
y

s alt .

A 15 only a l, the str eng t h of a norm al solution and will

l
B
n eutraliz e only fi r the quantity of s alt etc , .

N orm al and d ecinorm al solutions of acids should n eutraliz e

norm al and decinormal soluti ons of alkalies volum e for vol ,

ume D ecinorm al solution of silv er ni t rat e and d ecinorm al

.

solution of hydrochloric acid or sodium chlorid shoul d combine ,

volum e for volume etc , .

Rul es for Dir ect Percen t age E st imatio ns : With normal I .

soluti ons or 1 (according to its atomici ty) of the molec

1
7 5
1
5 ,

ular w eight in grams of the substanc e is weigh ed for titration ,

and the numb er of mils of the V S r equir ed to produc e the . .

d esired reaction is the p erc entage of the substanc e whos e

mol ecular w eight has b een us ed .
52 T HE E SS ENTIAL S OF VOLUME TRI C ANALY SIS
stan dard solution sh oul d repres ent one p e c ent of the s ubstanc e r

upon which it ac t s the rul e is t o take for an alysis as much

,

of the subs tanc e as is represen ted by 1 mils of the stan dard 00

solu t ion.

In the c as e of subs tanc es whos e p erc entage of p urity is

high it is advis abl e to t ak e small er quanti t i es in order to
, ,

av oi d the use of exc essiv e qu an t iti es of st an dar d s olu t ion .

Th us sul p huric aci d which con t ains , p er c ent o f abs o lu t e

su lphuric acid would require under the abov e conditions 9 5

,
2 .

mils of normal alkali solution .

In the cas e of t his acid if gms a e taken for analysis ,

. r ,

each mil of a norm al alk ali s olution woul d r epr es ent one p er

cent of 11 50 2 4 .

If half of this qu anti ty i e gms are tak en for , . .

, .

an alysis each mil of the norm al alk ali will r epr es en t two p er
,
‘

c ent of H SO and thus l ess of the standard s olution wil l

2 4,

be required Again if .
gm b e t ak en, e ach mil of th e .
,

standard alkali will represent per cent of H SO 10 2 4 .

In the cas e of liquids where it is not always convenient

to w eigh off the exact quanti ty required fo titration by the r

direct p ercentage metho d the liquid is diluted to a conveni ent ,

d egree with water and th en a qu antity of this dilu ted liquid

,

(r epr e s enting th e w eight required of the substance) is m easured

for analysis .

E x ample A sulphuric acid solution of s p ecific gravi ty

.

is to be analyz ed Two mils are accurately m easured .

and dilut ed to 1 00 mils and th en mils of this solti tion

(r e pr es e ntin g gm of the acid ) ar e t ak en for
. an alysis .

N
Ea ch mi l of 1
N aO H V S . . requ r ed i In the ti trati on re
p
1
res en t s 1 0 per c ent of absolu te H SO . If
5
N aO H V S z 4
5 . .

is employed each mil will represent one per cen t To de

,
.
 ME T H OD S OF CALCULATI N G R E S ULTS 53

termin e the amount of the dilu ted liquid to be taken we

proc e ed as f oll ows
Two mils of sul phuric aci d s p ecific gravity w eigh ,

gms t h erefore the .

, mils of dilu ted acid contain this
100

w eigh t and 1 mil of the sam e c on tains

, gm .

If gm a e contained in mil th en
. r gm are 1 , .

contained in how m any mils ?

gm mil gm
’

. .

0 36 52 : x,

mils x = .

Factor s or Coefli ci ents for Cal cu lat in g the An alyses It .

frequ ently occurs that from the n ature of the s ubstanc e or ,

from its b eing in soluti on this p erc entage m ethod c annot be ,

conv eniently follow ed .

The b est way to p roc eed in such a c as e is to fi nd the

factor .

The first st ep in all c as es is to wri t e the equ ation for the

reacti on whi ch t ak es pl ac e b etw een the substanc e und er
an alysis an d the solu t ion us ed .

For instanc e a solution of c austic p otash is to be ex amin ed

, ,

a
—

I
s olu tion of sulphuric acid b eing us ed .

2 K OH HzSO 4
-
K 2 SO 4 2 HzO .

N
5 6 49 1 000 mil sT aci d
.

gm . 1 mil —
aci d
.

The fac t or for K O H wh en 1

solution is us ed is . 0 6
5 gm .
,

that b eing the quanti ty n eutraliz ed by each mil of the

1
a cid .

If 3
4
0
a ci d were us ed the fac t or would be
.
. 0 0 56 gm .
54 THE E SS EN TI AL S OF VOLU METRI C ANAL YSIS
numb er of mils of the acid used to produce the desired
The
result when multiplied by the factor gives the quantity in
, ,

grams of K O H in the solution tak en .

E x ample If 10 grams of caustic potash solution w ere

.

taken , and 40 mils of —

1
a cid w ere required , the 10 gms of.

solution contain ed 0 56 gm . . gms of pure K O H

. .

To find the p erc ent age the following formul a may be

used :

Q qu
the antity of pur e subst anc e found by c alcul ation ;
W = weight of substanc e t ak en .

If the above exampl e is taken we hav e ,

c alcul ation may be mad e by proportion

0 1 the .

The qu antity of the substanc e t ak en is always the fi rst

t erm and the qu antity of pure s ubstanc e found the s econd
, ,

t erm .

The foll owing rul e is easily r em emb ered : As the q uanti ty

u
taken i s to the q anti ty found, so is 1 00 to x, the percenta e
g
f
o pure substance i n the sa mple .

hree t erms of the equ ation b eing giv en the fourt h is

T ,

found by multiplying the m eans and dividing the prod uct by

the giv en extr em e By applying this rul e to the abo ve c as e
.

we h av e

10 1 00 : x .
 METH OD S OF CALCULATI N G RE S UL TS 55

A
T BL E S H O WI N G THE N O RM A L F AC T O R S ,
E TC .
, OF T HE
A L KA L I E S ,
A L KA L I E A R T H S , AN D A C I D S .

Q u an ti t y of
b
S u s t an c e
to be t ak en ?

b l Mo l l N or m a l 5 0 t h at e ac h
Su s tan c e F orm u
W ghe c u ar .

a
ei F ac t o r lq
. .

t . .

m i l of -V S . .

l l in d i
i
wi ca te
1 p er c en t .

Sodi um hyd oxid r

Sodi um ca bo n ate r
Sodi um bica bo n ate r
t ss
Po a i um hyd o xi d r
ts
Po a si um ca bo n ate r
t ss
Po a i um bi ca bon ate r
Amm oni a (gas )
Am moni um ca bo n ate , no m al r r
C alci um hyd o xi d r
C alci um ca bo n at e r
r
N i t i c aci d
r
Hyd ochlo i c aci d r
S ulp hu i c acidr
O xali c aci d, c y talli zed rs
Aceti c aci d

h
T i s i s t he c oe ffi ci en t by whi h c t he n u m b e r of mi l s of n or ma l l
so ut i on u se d is
t o be l
m u ti pl i e d i n or d er b i
t o o t a n t he q u ant i t y of pu re su b st an c e p re sen t i n t he
l d
m at eri a ex am i n e .

1 Thi i h q s i y f
s bt e b k i di p
u an t t go im i su st ance to e ta en n r ect er cent a e e st at on s .

E h mil f E i d l k li V S m pl y d will h i di
ac o
1
ac or a a i h . . e o e t en n cat e 1 p er ce n t ; n t e case

of m y f h
an o b i wi ll h w v
t ese su b b k m ll
st an c es q i i t , o e e r, e e t ter to ta e s a er uant t es s o

h l
t at f h
ess od d l i b q i d Th i f
t e s t an h lf h q
ar i y b
so ut o n e re u re . us o n e- a t e u ant t e

tak h 1 f h Y V S W il l p
en e ac
N
1111 o if
t e h f h q
. . i yb re re se n t 2 p er c ent , o n e-t e n t o t e u ant t e

tak h mi l wi ll p
e n e ac If h w v
1
rel i
resen tb d d 10 p er c en t . , o e er ,
0
so u t on s e u se an on e

h f h q
t en t o i y i di
t e d i h bl b k
uant t h mil wi ll i di
n cat e n t e ta e e ta en eac n cat e 1 p er cent .

O n S tating Results In reporting the results of volu .

m etric work i t is customary to state the qu antity of pure

,

substanc e found ; thus in the case of salts the qu antity of ,

the anhydr ou s salt is r epor t ed It is how ever often r equired .

, ,
56 THE E SS ENTIAL S OF VOLUME TRI C ANAL YSIS
to state the res ult s according to the dualis t ic formul ae of .

Berz eli us th at is the m et als a r p ort ed as oxi ds and the

’

, ,
re e

aci ds as anhy dri ds Thus if so di um c arb on at e is an alyz ed

.
,

a s t at em en t of r esul t s by t his m et h od will giv e the q uan t i ty

of N a O spok en of as the b as e s oda If we l ook up on

z , , .

s odi um c arb onat e as N a O C o we é an readily see 6 gms ‘

z z, 10 .

of the anhydrous isalt c ontain 6 gms of N 0 2 . 32 .

By r efer enc e to the foll owing e quat i ons we see th at

gms of sul p h uric acid will n eutraliz e 6 gms oi N a O or
. 2 .
.

1 6 gms of N a O C O
0 .
z z .
.

N az O H2 S O 4 N a2 80 4 112 0 .

N
31 gm s .
gm s .
= 1000 mil s -
I
VS . .

N a2 O CO 2 + H2 S O 4 N as 4 + H2 O CO 2 .

N
5 g
3 m s . to 1 00 0 mil s Y VS . .

N
Thus one mi l of HZ SO 4 W ll r epres ent
i gm of
T
.

N azO an d gm of N a O C O .
z z .

In the c as e of s odi um bic arb on at e (N aHC O ) two m ol ec ul es g

contain one m ol ec ul e of the b as e s oda as here sh own , , .

2 N ELHC0 3 N 3 2 0 , H2 0 (CO Q ) 2 .

A ccording to this 6 gms of N a O r epres ent two m ol ecul ar

2 .
z

w eigh t s ( 68 gms ) of N aHC O In the cas e of ferrous sul

1 .
3 .

p h at e on e m ol ec ul e (
,
F eSO ) cont ains acc o r ding to t his sys t em 4 , ,

F eO an d 80 In the s ame way f erric s al t s c on tain F6 0

3 .
, 2 3 .

In stat ing the r esul t s of analys es of acids acc ording to this

syst em the quan ti ty of acid anhydrid foun d is rep ort ed not
, ,

the qu antity of the wh ol e aci d Thus if su lp huric aci d is .

an alyz ed the q uan t i t y of 80

,
is r ep ort ed In the c as e of 3 .

phosphoric acid the quan t i ty of P 0 is s t at ed etc 2 5 , .

 ME TH OD S OF CALCULATI N G R E S UL TS 57

T A BL E S H O WI N G T H E M O L E C U L A R W E I G H T S AN D N O RM A L
FAC T O R S FO R T H E M O S T C O MM O N O XI D S .

N am e .

Lithi um o xi d

o o o o o o o o o o o o o o o o o o o o o o o o

o o o o o o o o o o o o o o o o o o o o o o o o o o

o o o o o o o o o o o o o o o o o o o o

Fe rri id
c ox

S i lv r
e o xi d

r
S ulp hu i c anhyd i d r
s r
P ho p ho i c an hyd i d r
r
N i t i c an hyd i d r
r
C a bo ni c an hyd i d r

A pp r ox i m at e .
 CHAPTE R VII I

AN AL YSIS BY NEU TRAL I ZA TI ON

b as ed up on the fact that wh en an acid and an

THI S is
alk ali r eact each l os es its individu ality and a n eutr al s alt is

form ed i e a body which has n eith er the character of an

, . .
,

acid nor th at of an alk ali Thi s mutual n eutralizati on of

.

acid an d a lkali is the r esult of a union of the H '

ions of the

acid and the O H ions of the al kali forming non ioniz ed wat er
'

,
-

(H O H ) .

An acid is a compoun d w hi ch in aqu eous solution disso

ciat es (ioniz es) into positive and n egativ e ions the positive ,

ion b eing H Thus hydrochloric acid in an ioniz ed state is

.

H “
Cl '
. cid ioniz es into H+ H (80 )
Sulphuric a
'

An alk ali is a b asic com p ound which ioniz es into positiv e

and n egativ e ions and in which the n eg ativ e ion is (O H)
, .

The r eaction b etw een hydrochloric acid and potassium

hydroxid in accordanc e with this th eory is illustrat ed by
.
,

the foll owing eq uati On :

Ancid is gen erally r ecogniz ed as such by its color reac

a

tions with c ertain subs tanc es kn own as indic ators ; for exampl e ,

it turns blu e li t mus ed and dec oloriz es a red p h enolphthal ein

r ,

soluti on Al kali es are r eco gniz ed by th eir turning red litmus

.

58
60 THE E SSE N TLAL S O F VOLUME TRI C ANAL YSIS
tion of p ar t s by w eigh t of the form er and

p arts by w eight of the l atter as the equ ati on shows , .

2 N aO H H2 C2 O 4 2 112 0 N a2 C 2 0 4 + 4 H2 0 .

2 N a= 4 6 6H
'

2C = 24 . 000

H 6 O = 96
'
2 . 00 0

mmonia wat er unites with hydrochloric acid

A as p er the
equ ation ,

N H4 O H + HCl N H4 C1+ H2 0 .

05
5 5-

Sodium carbon at e with hydrochloric aci d ,

H CI N c l l H2 O
’

‘
N 3 2 C0 3 2 2 ‘"
C0 2 .

10 6

U pon c areful p erusal of the foregoing equati ons it will

a

be s een th at sinc e definit e w eights of aci ds n eutraliz e defi nit e

w eights of alkali es the quantity of a c ertain alkali in olution
, s

can be easily det ermin ed by the qu antity of an aci d solution

of known strength r equir ed to n eutraliz e it and vi ce v rsa ,

e .

R ef erring to the first equ ation we see th at gms .

of H S O n eu traliz e
z 4 gms of K O H If we prep are . .

a norm al solution of H SO we tak e h alf the m olecular w eight

Q 4 ,

gms to 1 0 0 mils Half the mol ecul ar w eight

.
,
0 .

is t aken b ec aus e sulphuric acid is a bival ent acid 0 00 mils . 1

of this solu t ion will n eutraliz e gms of K O H ; h ence .

1 mil will n eutraliz e gm of K O H . .

Thus if gms of a solution of K O H be treated with

10 .

the above norm al solution of H SO and it is foun d th at z 4,

2
5 mils of t he aci d solution are r equir ed to n eutraliz e the

alk ali solution the l at t er c ontains

, gm of .

p ur e K O H .

Sinc e the acid and alkali as w ell as the n eutral s alt which
 ANAL Y SIS BY NEU TRAL I ZA TI ON 61

is form ed are colorl ess and no visibl e change tak es p l ac e

,

during the reaction it is n ec ess ary t o add some substanc e

,

whi ch by change of color will show wh en the n eutraliz ation

is compl et e Such a substanc e is kn own as an in dicat or
. .

In the c as e of sodium hydro xi d with ox alic acid (see the

s econd equation ) we fin d that gms of crystalliz ed .

oxalic acid n eutraliz es gms of N aO H O xalic aci d

. .
,

like sulphuric is bival ent th eref ore a normal s olution of it

, ,

contains half the mol ecul ar w eight in grams i e gm s , . .

, .

in 1 000 mils .

1 00 0 mils will n eutr aliz e 4 gms of N aOH ;

0 .

1 mil will n eutrali e zgm of N aO H .

Theneutraliz ing p ow er of all norm al acids is exactly the

sam e b ecaus e they all contain in 0 0 0 mils the mol ecul ar
,
1

w eight in grams of the acid in the c as e of unival en t acids ,

and h alf of the mol ecul ar wieght in grams of bival ent

acids .

Thus 1 mil of any norm al aci d will n eutraliz e gm .

of K O H or gm of N aO H or fi m of the mol ecul ar

.
l '

w eight of any oth er unival ent alkali or 7 6 3 of the mol ecul ar

1
,
—
0

weight of an alkali earth the l atter b eing bival ent In like

,
.

mann er all d ecinormal solutions h ave a lik e n eutralizing

p ow er th eir
,
n eutr alizing equival enc e is on e t enth th at of -

normal solutions .

T hus 1 mil of a decinorm al aci d wi ll n eutra liz e

gm of K O H or
. gm of N aO H etc .
, .

A lk ali m etry

P r epar at i o n of St andar d Aci d Solutio ns It is possibl e .

to carry ou t the t itration of most alkali es by m eans of one

s tand ard aci d s olu t ion but the sam e standard acid is no t
,

e uall a plic abl e in all c as es ; furth rmor the st and ard

q y p e e ,
62 THE E SS ENTI AL S OF VOL U METRI C ANALY SIS
a cids are frequ ently em pl oy ed for oth er volum etric op erations
than n eutraliz at ion and th erefore i t is advis abl e to have a
,

vari ety .

The stan dard ox alic acid solution is pr ef err ed by some ,

b ecaus e of the eas e with which it may be prep ared provided ,

a pur e ox alic acid is to h an d It do es not how ever keep .

, ,

v ery l ong is unreli abl e for use with m ethyl orange and is
, ,

in applicabl e fo the t i tration of alkali earths because it forms

'

r ,

in solubl e comp ounds wi t h th es e m etals Standard hydrochloric .

acid is the most d esir abl e for alk ali earths b ec aus e it forms ,

solubl e c ompounds with th em ; its disadvantage h ow ever is , ,

in its vol atili ty and its cons equ ent us el essn ess in hot ti trations .

Stand ard sulphuric acid is p r ef err ed by most an alysts as

b eing the b est gen eral stand ard A pure acid can be gotten .

without difli culty and the standard solution mad e from it is

un affect ed by boiling and can th erefore be us ed in hot as
,

w ell as in cold titrations ; it reacts sh arply with the indicators

and it k eeps its ti t er ind efin i t ely It is how ev er not suit ed .
, ,

for the titration of alkali ear ths b ecaus e it forms insolubl e ,

compounds with th em which precipitate and are v ery annoying

,

to the op erator In the prep aration of standard solutions the

.

greatest c are should be exercis ed in order that the product

be absolut ely accurat e The slight es t in accuracy in the
.

str ength of a standard solution will r esult in r el ative errors

i n the an alysis It is customary to prep are one standard
.
‘
solution and then from this to adjus t various others For
, .

ex ampl e a norm al oxalic acid may be m ade fi rst

, and by ,

m eans of this a normal alkali solution which in turn may ,

be utiliz ed for the adjusting of oth er standard acid solu

tions .

N ormal Oxali c Aci d V S . .

(H
2 C 2 0 -
4 2 H2 0 ——
VS . .

gms in
. 1 000 mils) . D issolve gi n s of puri fied
.
 ANAL YSIS BY N E UTRALI ZATI ON 63

x
O alic acid * in enough dis till ed water to make , at or n ear
25 C e
°
x ac t ly
.
,
0 mils 10 0 .

Tenth N ormal - O xali c Aci d V S . . VS . .

= gms .

in mils )
1 00 0 .

D issolve gms of purifi ed oxalic acid in su ffi ci ent .

distill ed water to m ak e at or n ear 2 5 C exactly 1 000 mils ,

°
.
,

Of solution 0 1 b etter dissolve . gms of p ure crystal

,
: .

li ed ox alic acid in sufli cient distill ed w at er to m easur e 000

z 1

mils Th en into a flask accurat ely m easure 5 mils of a freshly

. 2

standardiz ed tenth norm al potassium hydroxide V S dilute - -

. .
,

with an equ al volum e of distill ed water add 3 to 5 drops of ,

phenolph thal ein T S and h eat it to boili ng From a buret t e . .

gradually add the oxalic acid s olution (which is too concen

trated) until the ed t in t of the alkali s olution fails to re
r

ap p ear aft er vig orous sha king an d boiling N ot e the num .

ber of mils of the oxalic aci d solution consum ed and th en ,

dilut e it so that equ al volum es of this and of the t enth

norm al potassium hydroxid V S n eutraliz e each oth er at . .

s tandard t emp eratur e ( 5 This solution det eriorat es

°
2

on standing h ence must be frequ ently ren ew ed or restand

,

ardiz ed .

his solution is in every resp ect equival ent in n eutralizing

T

p ow er to any o t h er t en t h norm al acid V S with eith er litmus -

. .

or ph enolphthal ein T S as indicator but not with m ethyl . .

,

orange Its S p ecific use in the U S P how ever is in stand

. . . .
, ,

ardi i ng or det ermining exc ess of t enth norm al

z potassium -

p ermanganate V S . .

Pu i rfi ed oxali c acid rl ss tr sp r t un ffli s i n the fo m

d r of colo e an a en , e oresce

li rh mbi
c no ryst ls s l bl i
o c c p rts f ld w t r i
a , b t 3 p rts f
o u e n 10 a o co a e , n a ou a o

b ili g w t r
o n di p rts f l h l
a e an T gm wh
n ig it d p a
p l t i o a co o . en s . en n e u on a

nu m f il l v s o t m r th ea e gm f r si du
no I f m r r si d
o e i l ft an . o e e . o e e ue s e

th id s h ld b p ri fi d by r ryst lli ti
e ac ou e u e ec a za on
64 THE E SS ENTI AL S OF VOL U ME TRI C ANALY SIS

N ormal Hydrochl ori c Aci d V S . . VS

. .

gms in . 1 00 0 mils ) M ix
. mils of hydrochl oric acid
1 10

of S
p . gr . wit h enough water to measure at or near ,

2
5
°
C .
, 1 000 mils .

FIG .
33 .

this liquid (which is still too concentrat ed) m easure

Of
carefully at 2 5 G in to a flask or b eaker
,
°
, mils add 2 0 10 ,

mils of distill ed wat er and a f w drops of methyl orange T S

e ,

and th en gradu ally add fr om a bur ett e sufli ci ent r ec en t ly pre

p a er
d and standardiz ed T p o a t ssium or sodium hydroxi d
 AN ALY SIS BY NEUT RAL I ZATI ON 65

at the same temp erature to just produc e a p ermanent faint

y ellow tint .

N
N ot e the numb er of mils of alkali s olution consum ed
—

and th en dilut e the aci d s olution so th at equ al volum es of

g
it and alkali n eutraliz e each oth er It is usu ally advisabl e .

to mak e two or three titrations as just describ ed b efor e , ,

dilution t akin g an averag e of the res lts

,
.

E x ample Assumin g th at the 0 mils of the acid solution

. 1

required 1 2 mils of the al akli each mils of the acid

—
,
10
I

must be diluted to mils or the whol e of the r em aining acid

12 ,

in the sam e proportion .

Af t er the dilution a new trial shoul d be m ade 0 mils . 1

of the acid V S shoul d r equir ed exactly mils of the alkali

. . IO .

This m etho d is fairly s atisfac t ory if an accurat ely stan d

ardi ed norm al alk ali hy droxi d solu t ion is at h an d ; the l att er
z ,

however always contains a sm all q unati ty of carbonate h ence

, ,

methyl orange is most desirabl e as an in dicator .

S t n d a d i a t i n by M
a r z n o f S di u m Ca b n atea Pure
s o o r o e.

anhy dr ous s odium c arb on at e m ay be obtain ed by h eating

to dull r edn ess a few grams of pure so dium bic arbon ate for

about t hirty minut es The r esulting c arbon at e is practic ally

.

free from im purity .

The so dium bicarbon at e los es on ignition one half of its -

carbonic acid gas

N aHC O + Heat N a C 0 3 C 0 + H O
2 3 2 2 2

The bic arbon at e shoul d how ever be t est ed b efor e igniting

, , ,

and if mor e th an trac es of chlori d sul ph at e or t hi osul hat e

p , , ,

are foun d th es e m ay be r emoved by washing a few hun dr ed

,

grams first with a saturated solution of sodium bicarbonate

, ,

and af t erw ar d with distill ed wat er .

66 THE E SS ENTI AL S OF VOL UMETRI C AN LYSIS A
gm of the pure anhydrous so dium carbonate is
.

accurat ely w eigh ed and dissolved in abou t 2 00 mils of di s

t ill ed water in a fl ask an d a few drop s of m ethyl orange T S . .

ad ded as in dic ator The aci d t o be set of . standardi ed z

is t hen run into the sodium c arbonate solution until a per

man ent light red color is produc ed I t shoul d requir e exactly
-
.

N
10 mils of the a cid solution .

If 8 mils of the acid solution are consumed to bring about

the r equir ed r esult th en every 8 mils must be dilut ed t o
, 10

mils or the whol e of the r emaining solution must be diluted

,

in this prOpo tion r :

N a2 C 0 3 2 HCI 2 N aCl H2 0 C0 2 .

N
53 gms . 1 00 0 mil s VS
. .

0-53 gm . 10 mil s 1

Instead of at t em pting to w eigh x actly 0 53 gm of the an e . .

hy drous so dium c arb onat e i t is b etter to tak e a l arger qu antity

,

( ab out gms
2 ) w eigh ed.a ccur a t ely D issolv e this in mils . 1 00

of distill ed water add 2 or 3 drops of m ethyl orange T S

, .

and run in t o it lit t l e by littl e from a bur et t e the aci d s oluti on

, ,

t o be stan dardiz ed reducing the flow to drop s toward the nd

, e

until a pink color is obtain ed Make 2 or 3 trials and take .

,

the av erag e numb er of mils consum ed .

O ne gm of pur e anhy drous so dium c arbon at e r equir es

.

for exact n eutr aliz ation mils of normal acid V S . .

Assuming th at gms of the anhydr ous carbonate were .

t aken and this required

,
mils of the tri al acid Th en .

X mils .

1 00 :x . x = 88 2 6. .

N ow djust the acid by m easuring

a mils and dil ut
ing with distill ed wat er to m ak e 1 00 0 mils .
68 T HE E SS ENTIAL S OF VOL U ME TRI C ANAL Y SIS
is mat ter of som e importanc e Phen olp h thal ein or litmus
a .

may be emp loy ed bu t i t is t h en advis abl e to b oil the solu

,

ti on whi l e t i trat ing in order to drive off the lib erat ed c arbon
,

dioxid b ec aus e the l att er gives an acid r eac t i on wi th ph en ol

,

phthal ein and litm us and thus c aus es an end reac t ion t in t to -

app ear b ef or e n eut r aliz ation is compl et e It is b ett er usu ally

.
, ,

to em p l oy an in dic at or which is not aff ec t ed by c arb on di o i d x .

Methyl orang e is m ostly p r ef err ed ; c ochin eal and Congo red

a e also us ef ul
r Th es e in dic ators are es p eci all y s ervic eabl e
.

in the pres enc e of c arb on at es in that th ey a e no t aff ec t ed by r

c arbon di oxid and can th erefor e be employ ed in direc t titra

,

t i ons wi th out the use of h eat .

T he qu anti ty of c arb on at e in a r ec ent s ampl e of s odium

or p otassium hydroxi d is so small usually that it is customary
to disregard it and to rep ort the to tal alkalinity as hydroxid .

A defini t e qu antity of the s amp l e (from gm to gm . 1 .

of the s olid or an equival ent of a soluti on) is tak en for an alysis ,

diss olv ed in 30 to 5 mils of w at er in a whit e p orc el ain dish or

0

a b eak er pl ac ed ov er a whit e s urfac e a n d a few drops of a

,

s ui tabl e in dic ator add ed .

The v ess el is t h en p l ac ed b en eat h a b ur et t e cont aining

the st an dard aci d s oluti on and the l att er un in drop by drop r , ,

un til the l ast drop j ust c aus es the c ol or to Chang e The .

solu t ion shoul d be rotat ed or stirr ed after each addition of

the s t an dard acid .

The alkali hy dr oxi ds a e so exc eedingly hyg osc0 p i c th at

r r

th ey t ak e up wat er from the air whil e b eing w eigh ed; it is

ther efore difli cult to mak e a dir ect w eighing with any d egree
of acc uracy .

The b est way is to t ak e a sm all p i ec e of the s ampl e (ab out

1 pl ac e it immediat ely in a t ared stopp ered fl ask and
tak e the w eight acc urat ely I t is th en diss olved in wat er
.
,

transferr ed to the p orc el ain dish o b eak er and titrat ed

r .
 A
AN LYSI S BY NE UTR ALI ZATI ON 69

Potassium Hydroxi d ( O
K H = ccurately w eighed An a

portion (preferably l ess t han is pl ac ed in a small b eaker

1 ,

dissolved in 50 mils of w at er t hr ee drops of m et hyl or ang e ,

ad ded , and the titration b egun wi th _

I
sul phuric acid and

continu ed until the y ellow color of the s oluti on is changed to

p al e red T.h en the bur ett e is c ar efully r ead to see how much

of the acid solution was used The numb er of mils of the .

l atter are multiplied by the norm al factor for K O H

and the r esult is the qu antity of pur e K O H in the s ampl e

taken for an alysis

‘
.

The following equ ation illustrat es the r eaction

2 KOH H2 SO 4 K 2 80 4 2 H2 O .

N
gms .
5 gms .
, quanti ty in 1 0 00 mils of acid V S . .

gm .
(the fact or for K OH) quanti ty neutraliz ed by
,

1 mil of acid .

N
Thus 1 0 00 m i ls of Y H SO V S contai n ngz 4 . . i gms ,

of absolute H SO will n eutraliz e

z 4 gms of K O H . . Th er e
N
fore each mil of H 80 V S will n eutraliz e 2 4 gm of
. . .

pure K O H .

‘
E x ample In the above analysis let it be assumed that
.

gm of p otassium hy droxi d w ere taken and th at

.

mi ls of the stand ard aci d w ere r equired to n eutraliz e it th en ,

g m th e qu antity of pur e K O H in
.
,

the gm taken . .

The p erc ent ag e is th en c alcul at ed in this way

1 00 x; x =
93 8 + p er c ent . .
70 THE E SS ENTI AL S OF VOL U M ETR I C ANAL YSIS
The fix ed l kli hydroxids a e rarely free from carbonate
a a r ,

through absorp ti on of carbon di oxid from the ai r .

In the foregoing m ethod the c arbonate is calcul ated as ,

hydroxi d h enc e the assay is fall acious The m etho d of the

,
.

U S P I X s ep arates the c arbon at e by pr ecipitating with b arium

. . .

chlorid filtering and ti trating the filtrate wi t h normal hydro

, ,

chloric acid VLS using p h enol phthal ein as indicator The

.
, .

use of st and ard sul p huric aci d V S is inadmissibl e in this . .

m ethod b ecaus e it reacts with b arium chlorid producing a ,

p r eci p it at e of b arium sul p h at e .

The U S P Me tho d is as follows

‘
. . .

Tak e about 1 gms of p otassium hy droxid accurately

0 .
,

w eighed in a gl ass stop per ed w eighing bottl e dissolve in 2 50

-
,

mils of distill ed w ater which has b een previously boil ed and ,

cool ed (to expel carbon dioxi d) add 30 mils of b arium chl orid ,

T S and t h en dilut e with distill ed w at er to 500 mils

. Thor .

oughly agitate the liquid and filter it through a dry filter into
a dry fl ask Rej ect the first 2 mils and titr at e 2 00 mils of
. 0 ,

the cl ear filtrat e with norm al hy drochloric acid V S using . .

,

phenol phthal ein T S as indic ator . . .

S odi um Hydroxi d T his is estim at ed in

ex actly the s am e m ann er as describ ed for potassium hydroxi d ,

the following equ ation b eing ap p li ed

2 N aO H H2 80 4 N azSO 4 2 H2 0 .

N
40 gms .
gms = 1 000 mil
. s ‘‘

I
VS . .

I— I
. 04 0 gm . 1 mil
I VS . .

tr The fac o .

The o ffi ci al solutions of potassium and of sodium hydroxid

are estim at ed in this s am e m ann er 1 0 mils may be tak en for ,

an alysis dilut ed with 2 0 mils of w at er

,
.

Ammonia Water T hr ee mils of ammonia

water are put into a stopp ered w eighing bottl e and the w eight
 ANALYSIS BY N E UTRAL ZA I TION 71

taken . F orty mils of water are th en added and the solution

titrated with T sulphuric acid As indicator litmus m ethyl .
, ,

orange or rosolic acid may be used Ph enol phth al ein is use .

l ess for titrating ammonia and even m ethyl orange and rosolic
,

aci d are unsuitabl e in the pr es enc e of much s alts of ammo

nium Becaus e of the vol atil e ch aracter of ammonia its solu

.

tions readily lose str ength upon exposure It is therefore b est .

t o m easur e a qu antity into a w eighing bottl e and find its

w eight as directed for potassium hydr oxid If the sp ecific .

gravity of the ammonia solution is known the w eight of a ,

given volum e is easily c alcul ated it b eing only n ec essary to

,

multiply the volume in mils by the sp gr Thus if the sp gr . .

, . .

of an ammoni a solution is and the volum e t ak en is

3 mils th e,w eight of the 3 mils is 3 X 0 9585 = 2 87 55 gms . . .

In titration with T sulphuric acid each mil of the

the

l atter represents gm of N H3 as shown by the equ ation

.
,

2 N H3 Hzo H2 80 4 H
( 4 ) 2 80 4
N 2 H2 0 .

N
1 7 gms
.
gms = 1 000 mil
. s -

I
VS . .

1\I
1 mil __ vs .

If mils of T acid w ere r equired in the above assay ,

then gm th e qu a ntity of pur e N H

.
, 3

in the 3 mils 5 gms ) of ammoni a w at

. er t ak en .

The p erc entag e is found as follows

If 3 mils of ammonia w at er w eighing gms contain .

gm of N H3 1 00 gms of ammonia water will contain

.
, .

X gm . Of N H3 ,

er
p c ent .
‘
estimat ed in the s am e mann er .

t
E s i mati o n of A l k al i r nat
C a bo es

Wh n c rbon t s
e a tr t wi t h ci ds c arbonic acid gas
a e ar e ea ed a —

is lib erat ed This gas shows an aci d r eacti on wi th most

.

in dic ators and the r eacti on will s eem to be comp l et ed b efore

,

the alk ali is entir ely n eutraliz ed .

To avoid this the titration may be c onduc t ed at the boiling

,

t emp erat ur e (hot way) in ord er to driv e off the c arb on dioxid .

The s t an dard acid b eing add ed until two minu t es b oiling fails
’

to r estor e the color indic ating alk alinity If th t itrati on is . e

con duct ed at a boiling t emp erature it is advis abl e to at tach ,

to the lo wer end of the bur ett e a long rubb er tub e wi t h a

pinch cock fix ed ab ou t mi dway on the tub e
- .

The boiling can th en be don e at a li tt l e dis t anc e from

the bur ett e an d the exp ansi on of the st an dard s olu t ion t h er ein
thus pre ent ed
v .

An oth er m ethod is to add t o the c arb on at e a m easur ed

exc ess of the s t an dard aci d an d th en aft r b oiling to driv e
,
e

off the c arbon di oxi d an in dic at or is added

,
an d the exc ess ,

of st and ar d aci d det ermin ed by t i t r ati on wi t h a st an dard

alkali ( res i dual ti trati on way) The qu an t ity of the l at t er

.
,

deduct ed from the qu anti ty of the s t an dard aci d tak en gives ,

the qu antity of the l at t er which r eact ed with the c arbon at e?

S till anoth er m etho d is to t i trat e the c arb onat e direct wi t hout ,

h eat (cold way) using an indic at or which is not aff ect ed by

,

carbon dioxid The b est of the in dicat ors which a e not so

. r

aff ect ed is m et hyl orang e ; oth ers are cochin eal and C ongo red .

Wh e n em ploying m thyl orang e as an in dicat or s tan dard oxalic

e

aci d solu t ion shoul d not be us ed as the end r eac t i on is very

,
-

in defin ite and unreliabl e .

The end r eac t i on wi th this in dic at or is at all events not a

-

cl early m ark ed one and c onsiderabl e p actl e and an eye for

,
r c

col or is r quir ed to d tec t the p oin t at which y llow ch anges to

e e e
 ANAL Y SIS BY NEUTR AL IZATI ON 73

p alepink I t is a good pl an to have on the b ench two vials

.
,

one c on taining an aci d and the oth er an alk ali t in t ed with

m t hy l orang e wi t h which com parisons an be m ad e

e , c .

F I G 34
.

i
r onat e
Potass um Ca b Weigh c arefully
on egram of the sal t pr eviously dried to constant w eight at
,

D issolve in 2 5 mils of distill ed w at er in a b eak er

°
18 0 C .

or fl ask add a few drops of m et hyl or ang e T S

,
an d titr at e ,

with normal sulphuric acid until a faint orange red color -

app ears .

K2 €O 3 H2 80 4 K 2 80 4 H2 0 00 2 .

m = mi ls
N VS
gms .
g s 1 000
.

T . .

N
Ea ch of T H S0 th erefore rep resents
mil 2 4, ,gm .

of ur e otassium c arbon at e
p p .

If m ils of the n orm al aci d are r equir ed the s alt contai ns

74 THE E SS EN TI AL S OF VOL UMETR I C ANALY SIS
X0 0 691 . gm of pure K C0 or
gm .
=0 .
9881
3 .
2 3

p er c ent If it is
. desir ed to u se litmus or p h enol p hth al ein ,

it will be n ecess ary to boil the s olu t ion as describ ed ab ove .

O th er alkali c arbon at es are estim at ed in exactly the same

mann er as described for potassium carbon ate .

P otassium Bi carbo nat e (K HC0 3

2 K HC O 3 H2 SO 4 K 2 80 4 2 H2 0 C0 2 .

= 1 00 0 mils
N VS
gms gms
— ~
. . . .

Ea ch mil of —

I
a cid V S . . gm of KHC O 3
. .

Previous to weighi ng this salt should be dried to constan t ,

w eight in a desiccator over sul phuric acid .

S odium Carbonate (crystalliz ed) (N a C0 o O 2 3 r

N 3 2 C0 3 . IO H2 0 “"
i H2 80 4 N azSO 4 I I HzO C0 2 .

m = mils
N VS
gms g s 1 000
T
. . . .

Ea ch mil of —

I
a cid =0 1
43 . gm crystalliz ed sodium
.
car

bonate .

S odi um Carbonate (anhydrous ) ( 2 C0 3

N a

N a2 C0 3 HZS O 4 N a2 80 4 Hzo CO 2 .

mils
N
53 gms .
gms . 1 00 0 VS . .

E ach mil of a cid = 0 0 53 gm . . N azCO g .

S odium Bi carbonate (N aHC 0 3

2 N aHC0 3 H2 80 4 N azSO 4 2 H2 0 2 C0 2 .

84 gms = 1 000 mils

N
gms
_
. . VS . .

Ea ch mi] of -
a cid = 0 0 84 gm . . N aHC 0 3 .

I
 l

or gm of N H The U S P salt shoul d contain b etween

.
3 . .

30 and 3 p e
2r c en t of N H 3 .

If in this titration mils of the stan dard acid are required

th en the two grams of amm onium c arb on at e c ontain ed
gms of th s alt . e .

2
p er c ent .

If rosolic aci d is us ed as in dic ator heat m ust be appli ed

to exp el c arbon di oxid The estimat i on of the c arb onic aci d
.

may be eff ect ed by p r eci p i t at ing a defini t e w eigh t of the s alt

with b arium chlori d c oll ecting the pr ecip itat ed b arium car
,

bonat e dissolving i t in a m easur ed exc ess of n ormal hydro

,

chloric acid and reti t ating wi t h normal alkali

r .

The m eth od usu ally em p loy ed by skill ed an alysts (the

resi dual ti trati on m thod) is to add a m easur ed exc ess of the
e ,

standard aci d solu t ion and t hus c onv er t the ammonium car
,

bon at e into the l ess v ol at il e ammoni um s ul phat e ; t h en g en t ly

boi l to get id of C 0 and t i trat e b ack with a standard alkali
r 2 ,

V S (using m ethyl orang e as an indic at or) un t il the exc ess of

. .

aci d is n eu t raliz ed The qu anti ty of free aci d t hus f oun d

.
,

wh en deduc t ed from the am oun t of aci d first added gives the ,

quan tity which was r equired to n eutraliz e the ammonium

carbonate .

Thus 2 gms (in solution ) of ammonium c arbon ate are

.

N
treated wi th 50 mils of —
s O4 V S . .
, which is more th an
I

suffi cient to neutraliz e it ; the solution is then g ently boil ed

to drive off C0 a few drops of litmus tinctur e add ed and
2, .

th en ti trated wit h 7 K O H V S un til the li tmus no longer . .

shows an acid reaction and the s olution is n eutral I f m ethyl .

orange is used as an indic ator h ere boiling is not n ec essary , .

 ANAL YSIS BY NEUTR AL I ZATI ON 77

L et us assum e t hat mils of the

3
KOH V S . . w ere
used By deducting the
. mils from the 5 mils of acid 0
-

first added we find 3 7 3 mils of the acid w ent int o combin ation
,
.

wi t h the ammonium s al t the c alcul ation is th en m ade as ,

d escrib ed ab ov e .

r id and Ca b nate
Mi x ed A lk al i H yd ox r o

If it is d esired to asc ertain the proporti on in whic h thes e

exist in a mixt ur e we proc eed as follows : ,

First d et ermin e the tot al alkalinity by m eans of norm al

hydrochloric acid using m ethyl o rang e as an in dic ator
,
Th en .

dissolve a lik e qu antity of the mixtur e in 1 5 mils of w at er 0

and add su ffi ci en t b arium chl ori d to p r eci p itat e all of the

c arbonate as b arium c arbonate and t h en add water to m ak e ,

200 mils and set aside to s ettl e Wh en the sup ern atant liquid .

is cl ear tak e one fourth (50 mils) of it and titrate with norm al
-
,

hydrochl oric acid using ph enolph t hal ein as in dicator The

,
* .

numb er of mils mul ti plied by 4 will be the qu antity of norm al

acid r equir ed by the c austic alk ali The di ff er enc e b etw een .

this and the numb er of mils representing the total alkalinity

is calcul ated as c arbonate .

E x ample Assuming that we are an alyzing a mixtur e of

.

sodium hydroxi d and c arbon at e .

Two grams of the subst anc e are dissolved in w at er and

titrat ed with norm al acid solution mils of the l at t er a e . r

requir ed Anoth er
. gms is dissolved treat ed with b arium
2 .
,

chlorid as direct ed and one fourth of the cl ear s olution titrated

,
-

The li h s g t rr r whi
e rs i thi s m th d b s th v l m f th
o ch occu n e o ecau e e o u e o e

p r i pi tat i i l d d i
ec e s th m s ur d li q i d m y b
nc u e n v r m by si g
e ea e u , a e o e co e u n

the en ti q ti ty f li qui d i ludi g th p r ipi t t (i st d f taki g

re uan o ,
nc n e ec a e n ea o n on e

f rth f i t)
ou o d ti tr ti g wi th
,
an li i d V S i th p r s
a n f ph l oxa c ac . . n e e ence o eno

phth l i
a en O li
. id i v ry dilut s luti s d s t r t wi th lk li
xa c . ac n e e o on oe no eac a a
78 THE E SS ENTI AL S OF VOL UME TRI C ANALY SIS
it norm al acid
w h mils are required ; th en
.

mils repres enting the s odium hy droxid

, .

mils t otal alkalini ty ;

gm so dium hydroxid . .

X 53 gms s odium carb on ate

. .

Anoth er way is to fi lter the mix ture after b arium chlorid

has b een add ed titrat e the filtrat e wi t h n orm al aci d to fi nd
,

the qu an t ity of hydroxid th en dissolv e the p r ecipit at ed b ari um

,

c arbon ate in normal hydrochloric aci d in exc ess and eti t ate , r r

wi th normal alkali thus ascertainmg the amoun t of c arb o

,

nate .

When the alkalin e c arbon ate is pres ent in v ery small

qu an tities the m ethod of L unge m ay be emp l oyed .

A few drops of ph en ac et olin s oluti on are add ed to imp art

a sc arc ely p erc eptibl e y ell ow to the liqui d N orm al aci d .

solution is th en run in until a p al e ros e tint app ears in dicating ,

that all the alkali hydroxid is n eu traliz ed ; the volum e of acid

is not ed and the ti tration c ontinu ed; the red c ol or is inten
,

sifi ed an d wh en the c arbon at e is entir ely decompos ed a

,

gold en y ellow c olor r esults

- .

Consid erabl e practic e is r equir ed with s olutions of kn own

composit on to accustom the eye to the changes of col or
i .

Mix ed r n r
A lk al i Bi ca bonate s an d C a bo ates

Thompson s Method Tak e grams of the s alt and dissolv e

’
. 2

in 1 00 mils of wat er D ivi de the s olution in t o two equ al p arts

.

an d titrat e on e portion with normal aci d solu t i on using m et hyl ,

orange as indicator and no t e the quantity required We will

, .

assum e 3 mils 1 .

Th en tr eat the s ec ond p ortion with a m easur ed exc ess

( y 5
sa 2 m il s ) of norm al sodium hydroxid solution fr ee from
 ANAL YSIS BY NE UTRAL IZATI O N 79

C0 2 . his conver t s the bicarbon ate into carbonate N ow

T .

add an exc ess of pur e n eutral b arium chlori d solution in

order to p recipitate all the carb onate as b arium carbonat e ,

and th en ti t rat e with norm al aci d using ph enol phth al ein as

' '

indicator to determine the excess of sodium hydroxi d 1 5

, .

mils are required Thus .

2 5 1 5 mils
10 th e e quiv a l en
,
t of bic arbon a t e ;
and 13 10 =
3 mils th e equival ent of c arb on at e ;
,

84 0 gm so dium bic arbon at e ;

. .

3 3 gm so dium c a rbon a
. t e .

S odi um Borate (Bo rax) (N a2 B4 O 7 10 H2 0 Dis

solve 5 gms of the s alt in 00 mils of distill ed water and titrat e
. 1

the solution with norm al hydrochloric aci d V S using methyl . .

,

orange T S as in dic ator

. . .

N 3 2 B4 O 7 IO HzO 2 HC1= 2 N aCl 4 H3 BO3 SHzo .

Ea ch mil of normal HCl V S corr esponds to gm . . .

of crystalliz ed borax or to gm of anhy drous borax . .

S o di um Cacodylate This salt

is assayed by titration with normal HCl V S in the presenc e . .

of m ethyl orang e E ach mil of the acid V S corresponds to

. . .

gm of the salt
. .

Thi s s alt is occ asion ally slightly aci d in r eacti on ; if so it

’

shoul d be carefully neutraliz ed to ph enolphthal ein b efore

titrati on is b egun .

S odi um Glycerophosphate (N a C3H5 (O H) PO 2 2 4

This s alt is ti trat ed with h alf normal hydrochloric acid V S -

. .

in pres enc e of methyl orang e .

N
E ach mil of — ~
a cid VS . . corresnonds to gm oi .

s lt
the a .
80 THE E S SE N TIAL S O F VO LU ME TRI C ANAL YSIS

E s t i m ati on of n
O rga i c S al ts of th e A l k ali es

The tartrat es ci trat es and ac etat es of the alkali m tals a e

, e r

conv erted by igni ti on in t o c arb on at es the wh ol e of the b as , e

rem aining in the form of c arb on at e .

E ach m ol ec ular w eigh t of a n orm al t ar t rat e giv es wh en

igni t ed on mol ecul ar w eigh t of c arb on at e
e

K 2 C 4 H4 O G = K 2 C O 3 .

Ev ery two m olec ul ar w eigh t s of an ac etat e or an ci d

a
tartrat e giv on e m ol ec ul ar w ight of c arb on at e
e e :

2 K C2 H3 0 2 K 2 CO 3 ;
2 K HC 4 H4 0 6 K2 C0 3 .

very two m ol ec ul ar w eight s of

E a n ormal ci t rat e give
three m ol ec ul ar w eights of carb on at e :
2 K 3 C 6H5 0 7 3 K 2 C 0 3 .

Th es e re ac t i ons a e taken advan tage of in v olum et ric

r

an alysis an d th t artrat es citrat es an d ac et at es of the alk ali es

,
e ,

a e in dir ec t l y estim at ed by c alc ul at ing up on the qu an t i t y of

r

carbon at e form ed by burning th em the quan ti ty of c arb on at e ,

b eing foun d by titrat i on in the usual mann er .

The P roc Bef or e igni t ing the s al t to be examin ed

ess .
,

should be t h oroughly dri ed in a desiccat or ov er c alci um chl ori d

or in a drying ov en the l att er only fo s uch s al t s as hav e no
,
r
.

wat er of crys t alliz ation in th eir compositi on If the w eight .

is t ak en b efore and aft er the amoun t of moist ure pres en t is ,

det ermin ed O n e or two grams of the dri ed s al t is w eigh ed

.

accur at ely p l ac,

ed in a p orc el ain crucibl e an d h eat app li ed ,

gradually un til dull r dn ess is reach ed and whi te fum es c eas e

,
e

to b giv en off
e U p on app l ying h eat to the s al t the l att er
.
,

sw ells fus es and th en b oils and if the h eat is app li ed too

, , ,

rapidly at this p oin t t h er e is ap t to be a consid erabl e loss

,
 ANAL YSIS BY N E UTRALI Z ATI ON 81

of material t hrough Sput t ering The flam e of the burn er .

must no t come in con tac t with the c arboniz ed mass The .

compl etion of the ignition is known to be r each ed wh en the

bl ack cont ents of the crucibl e is dry and crisp The crucibl e .

is th en allowed to cool its contents disin t egrat ed wi t h the

,

aid of a st out gl ass rod and th en tr eat ed with boiling w at er to

dissolve out the alkali c arbon at e and the solution filt er ed ,

t hrough a small w etted filter into a flask or b eaker The

,
.

fil trate shoul d be p erfectly colorl ess I f it has a yellow or .

brownish c ol or it indicat es incomp l et e ignition and shoul d be

rej ect ed and a fresh qu antity of the salt subj ect ed to ignition
,
.

The cont ents of the crucibl e and the filt er shoul d be w ash ed
with s everal sm all p or t ions of w at er until the w ashings no

longer sh ow an alkalin e r eaction The fil trate mix ed wi t h the .

wash water is now titrat ed wi t h stan dard sulphuric o hy dro r

chloric acid using m ethyl orange as the indicator From the

,
.

qu antity of carbon at e foun d in the filtrat e the equival ent ,

‘

am ount of the organic s alt may be c alcul at ed The qu antity .

of st and ard aci d em p loy ed is mul t i p li ed dir ect by the f actor

for the original salt The residual titration m ethod usmg an

.
,

exc ess of h alf norm al sulphuric aci d V S

-
boiling and r eti trating . .
, ,

with h alf normal potassium hydro xi d V S is r ecommend ed

-
. .
,

in the U S P .

I n th e c s of organic salts of the al kali earths r esidu al

a e l
,
><

ti tration shoul d always be resorted to The r esidu e in the .

crucibl e b eing dissolved in standard hydrochloric acid and ,

reti trated with st and ard alkali .

L ithi um salts b ec aus e of the sp aring solubility of the

,

c arbon ate in water should also be titrated by the residu al

,

method .

P otassium Tartrate Two grams of

O rg ani c s lts
a of k
the al ali rths subj t
ea ec ed
“
t g t
o i ni i on as abo v e are
r
educed pa rtly t o oxi d s .
82 THE E SSE N T ALS OF I V OLU ME TRI C AN AL Y SI S
the sa lt is pl ac ed in a p l atinum or porc el ain crucibl e and h eat ed
to redn ess in con tact wi th the air until com p l etely charred ;
that is to say until n othing is l ef t in the crucibl e bu t c arb onate
,

an d fr ee c arbon .

The crucibl e is now cool ed and i t s c ont ents tr eated with ,

boiling water which diss olv es the p otassium carbon ate the
, ,

c arbon b eing s eparat ed by filtrat ion In order to obtain .

ev ery trac e of c arbon at e it is w ell t o w ash the crucibl e with

s everal small p or t ions of hot wat er and add the w ashings ,

to the r est of the filtrat e through the filter .

If the s alt is c ompletely carboniz ed the fil trat e will be

colorl ess but if the carbonization is not comp l et e the s olution
,

will be more or l ess colored and sh oul d be rej ect ed and a ,

fr esh quantity of the s alt subj ected to i gni t i on .

To the fi ltrat e which contains p ot assium c arbon at e add

, ,

N
a few drops of m ethyl orange and ti trat e with T sul phuric ,

acid V S until a light orang e red c ol or ap p ears an d the car

. .
-

bon at e is n eutraliz ed .

The foll owing equ ati ons will expl ai the r eac t ions : n

K2 C 4 H4 0 6 K 2 C0 3 C2 C0 2 H2 O

K2 C O 3
1 38 2
HgSO ‘
. K2 S O 4 H2 O C0 2

th erefore
K2 C 4 H4 0 6 K2 C0 3 112 80 4
N“
gm s .
gm s .
gm s = . 1 000 mil sI VS . .

N
and ea ch mil of 1
HQ S O 4 r epres ents gm of potassium
.

tartrate .

E x ample . Two grams of potassium treat ed as d escrib ed

84 THE E SSE N TIAL S OF VOL UME TRI C AN AL Y SI S
with a wat ch gl ass and boil the conten ts for thirty minutes .

Th en filter the s olution and wash the r esi du e wi t h hot dis t ill ed
water until the washings c eas e to redden blu e li tmus paper .

N ow determ in e the r esidu al aci d in the cool ed fil trat e by titra

tion with h alf norm al K O H V S using m ethyl orange as
-
. .
,

in dicator .

Subtract the numb er of mils of half norm al alkali V S ~

. .

used from 50 mils (the qu an tity of half normal acid V S

.
-
. .

taken) The r em ain der repres ents the qu antity of half normal
.
-

sulphuric acid V S which react ed with the c arbonate in the

. .

N
h rred mass This multip li ed by
c a . factor for roch ell e
,
2

salt represents the w eigh t of the l atter in the am ount taken

,

for an alysis The for egoing equ ations show the n ormal fac tor
.

for anhydr ous rochell e salt to be 5 5 g

0 m h e nc e the h al f .
,

normal factor for the sam e is gm .

Henc e if in the abov e ass ay 2 mils of h alf normal K O H

,
2 -

V S w ere us ed this q uanti ty d educt ed from 50 mils l eav es

. .
, ,

2 8 mils the qu anti ty of h alf n orm al sul p huric aci d which was
,
-

taken up by the alkalin e carboniz ed mass ; th en 0 5 53 X 2 8 . 0 2

gm of K N aC H 0 6 in the 2 gms of roch ell e s alt

. 4 4 .

taken for analysis = p er c ent .

Potas si um Bitar trate (Cream of Tar

tar) . The estim ation of this salt is aff ect ed in the sam e way
as the t ar trat e .

The bitartrat e h avi n g but one atom of p otassium in its

m ol ecul e it tak es two mol ecul es to form one mol ecu le of car
,

bonate .

2 KHC 4 H4 0 6 K 2 C0 3 H2 80 4
N
gms .
gms = 1 00 0 mil
. s __
1
VS
. .

N
Ea ch mil Of I
H 2 80 4 V S . .
=D . I SS I gm . O fs KHC4 H4 0 6 .
 AN AL S S BY N E Y I UTRALIZATI ON 85

An oth er way of stimating bitartrate is to dissolve a w eighed

e

quantity of hot water and t itrat e wit h p otassium hy droxi d —

un til n eutral an d thus the am ount of t artaric aci d existing

,

as bi t artrat e is foun d The bitartrat e is aci d in r eaction

. .

I n detail the m etho d is as follows

Two grams of the bitartrat e are dissolved in 1 00 mils of
hot water a few drops of phenol phth al ein T S added and
,
. .
,

N
then titrated with K O H V S until a faint pink col or indi
-—

I
. .

cates that all of the acid has b een neutrali ed N ot l ess than z .

mils of the normal al akli shoul d be required correspondin g ,

to p er c en t of p ur e s alt .

The follow ing equation will show the r eaction

KHC 4 H4 0 6 "
l
'
KOH K 2 C 4 H4 0 6 H2 O .

ET
1 000 mil s of
l
K OH V S . .

N
Ea ch mil of —

I
K OH V S . . repres ents gm of .

KHC4 H4 0 6 .

If mils are requir ed for neutraliz ation th en ,

gms
p er cent .

o
P tassium C itrate (K 3 C 6 H 5 O 7
=
30 6

2 K 3 C 6 H5 O 7 3 K 2 C O 3 3 H2 S O 4 .

N
gms .
gms . 1 000 mil s1 aci d.

Thus ea ch mil of cid repres ents

a gm of pure
1
.

potassium citrat e an d each mi l of a cid repres ents gm

,
2
.

P otassium Acetate In stimating p otas

e

s ium acetate the salt is ignited and the resi du e treated in

86 THE E SSE N T AL S OF I VOLU ME TRI C AN AL YSI S
x ctly the same mann er as in
e a the stimation of
e the citrates
and tartrat es b efor e m ention ed .

2 K C2 H3 0 2 K2 CO 3
2

= mils
N
gms 1 000 . H 80
1
2 "
N
E ach
mil th erefore of H2 SO 4 corresponds to
1
gm of potassium ac etate
. .

S odi um Acetate (N aC 2 H30 2 3H2 O .

2 (N aC2 H3O 2 3112 0 ) N a2 C 0 3,

N
Ea ch mi l of 2 H SO 2 4 VS . . represents 0 0 680 4
. gm of crys.

talliz ed sodium ac etat e .

S odi um Benzoate (N aC 7 H5 O 2 =

2 N aC7 H5 O 2 N a2 C 0 3 .

ch mil of
Ea
! H2 SO 4 V S . . represents gm of so dium
.

benzoate .

S odi um S ali cylate

2 N aC7 H5 0 3 N a2 CO 3 .

N
Each mi l of —

2
H2 SO 4 V S . . represents gm of sodium
.

salicylate .

Lithium Citrate stated b efore As ,

the organic s alts of lithium and thos e of the alkali eart h

metals are b est titrat ed by the r esidu al m ethod after ignition , ,

b ecause the carbonates form ed are insolubl e in wat er It is .

likewise b est to use standard hydrochloric instead of standard

sul phuric acid The proc ess for lithium citrate h ere given
.

ex empli fi es the m ethod .

Two grams of the salt is thoroughly ignited in a p orc el ain

crucibl e as d escribed for potassium tartrate The residue of .

lithium carbonate is then dissolved out of the crucibl e by add (

88 THE E SSE N T AL S OF I VOLUME TRI C AN AL Y SI S
using ph enolphthal ein T S as indicator Subtract the numb er
. . .

of mils of half norm al p otassium hy droxi d V S used from 2 0

—
. .

mils (the qu anti ty of half n orm al sul phuric acid taken) and —

the r em ain der will be the qu antity of the l atter whi ch r eact ed
with the s odium bicarbonate .

The calcul ation is as follows

2Na HC 0 3 H2 SO 4 N a2 SO 4 2 H2 0 2 C0 2 .

2 )
gms in . 1 00 0 mil s of hal f-no mal V S r . .

Ea ch mil of h alf n ormal

-
acid gm . of

N aHC 0 3 .

Assuming t hat 8 mils of h alf norm al potassium hydroxid -

w ere consum ed in the ass ay th en mils of h alf normal sul 12 -

p huri c acid r eact ed wi t h an d h enc e r epr e s ent the sod

,
i um
bicarbonate present .

Henc e 5 0 4 gm or p er c ent . .

Th A ssay]fo Roch lle S alt Tak e

e r gms of the contents
e . 2 .

of the blu e p aper used in the pr ec eding assay pl ace it in a ,

porcel ain crucibl e and carboni e i t as describ ed under potas z

sium and so dium tar trate The differenc e b etw een the num .

ber of mils of h alf norm al sul p huric aci d V S consum ed

-
. .

in this assay and in the pr eceding assay for sodium bicarbonate

multiplied by repr esen t s the roch ell e salt .

Thus , mils of H2 SO 4 V S . . taken

16 .
5 mils of g KOH V S . . required for neutralizati on
N
33 .
5 m i ls of
—

2
H2 SO 4 consumed
mils —
12 mils = mils representing roch ell e salt;
,

gm or p e
.r c ent of crystalliz ed

roch ell e salt .

 AN AL Y SI S T
BY N E U RAL Z A I TI ON 89

Ammoni um Benzoate and Amm 0

ni um S ali cylate (N H4 C 7 H5 0 3 = 15 It is evident that
because of the vol atility of ammonia, th ese salts c annot be
.

assay ed by the m etho d employ ed in the c as e of org anic s al t s

of the fixed alkalies The offi cial assays of th ese salts d ep ends
.

upon the lib erati on of the organic acid by the addition of ,

sul phuric acid and its ex traction with an immiscibl e solvent

, .

The solution so obtain ed is evaporated and the org anic aci d

residue dissolved in n eutr aliz ed diluted alcohol and titrated
with tenth normal b arium hydroxid V S The m etho d in
-
. .

detail is as follows D issolve ab out: gm of the s alt pre .

vi ously dri ed in a desicc ator ov er sulphuric aci d and accur at ely ,

weigh ed in 1 0 mils of distill ed w ater in a s eparator Add

, , .

to the solution 5 mils of diluted sulp huric acid and extr act
the lib erated org anic aci d by sh aking out with thr ee succ essive
portions of 2 5 1 5 and , ,mils resp ectively of chloroform
10 ,

p assing the chloroform solution through a fi lter previously

moistened with chloroform and removing any of the organic
,

acid adh ering to the st em of the funn el with a few mils of

chloroform E vaporate the chloroform solution at a very

.

low t emp erature to 5 mils add 2 5 mils of dilut ed alcohol

, ,

N
which has b een previously n eutraliz ed with 1B
KOH V S . . in
the pres enc e of ph enolphth al ein .

Titr at e
this solution with 2 b arium hydroxid VS ,. . u i s ng
phenolphthal ein as indicator .

1
E ach mil of the 1 Ba (O H) 2 V S . . represents b enzoic acid ,
10

salicylic acid gm , .
; a mmonium benz o at e
m
g , . and ammo nium s alicyl at e 55 08
gm.
90 THE E SSE N TI AL S OF VOLU ME TRI C AN AL Y SI S
TABLE SHO WI N G THE N O RMAL T RS E TC OF
FAC O ,
.
,
THE
O RGAN I C SALTS OF THE ALKALI M E TAL S .

Mol ecu l ar
%q i gh
u i v al e n t N orm a)
Su b st an ce . F or m u la .

W i gh e t in
e t .

C ar b o n at e .
F act or .

L1thi um benz oa t e . . L i C7 H50 2

Li3 C6H50 7
s li yl t
a c a e Li C7 H50 3
S di m
o u tt
ace a e N 3 C2 H302 3H2 0
t
.

b enz oa e N aC7 115 0 2

s li yl t
a c a e N aC 7 H50 3
P t ss i m
o a u tt
ace a e K C2 H30 2
bi t rtr t a a e K HC4 H4 0 6
i tr t
c a e K3 C 6H50 7 H2 O
t rtr t
a a e K 2 C 4 H4 0 6 %H2 O
d s di
.

an o um
t rtr t a a e . K N aC4 H4 0 3 4 H2 O

E s ti m ati on of th e S al ts of th e Al k ali E arth s

St andard solution of hydrochloric or of nitric acid is pre

ferred by m any op erators fo the ti tration of hydr oxids or r

carbon at es of the alkali earths Th es e acids poss ess the .

advan t ag e ov er most ot h er acids of forming solubl e s alts .

The hydrox i ds m ay be es t im ated by any of the indic ators ,

but as th ey readily absorb CO out of the air th ey are gen erally 2

contaminated wi th more or l ess carbonate and the r esidu al ,

m ethod shoul d be us ed i e a known excess of standard acid, . .

,

shoul d be added the mixture boil ed to expel any trace of CO2

, ,

and titr at ed with stan dard alk ali .

The ca bonat s are of cours e estim at ed in the s am e way

r e ,

as are also the organi c salts of the alkali a th af t er ignition e r s, .

As an exampl e :
O ne gram of calcium c arbon at e is mixed with 5 mils
of wat er An exc ess of normal hydrochl oric acid V S is
. . .

now ad d d e and the s olu t i on b oil ed to drive off the C O 2

, .

Th en a few dro p s of ph en ol ph t h al ein T S a e added and . . r ,

92 THE E SSE N T ALS OF I VOLUME TRI C AN AL S S Y I
A w eigh ed quan t i ty of th s alt is diss olved in w at er e ,

c autiously n utraliz ed if i t is aci d o al kalin e p h en ol phth al ein

e r ,

is added the mi t ur e h eat ed to b oiling and s tan dard s olu ti on

,
x ,

of s odium c arb on at deliv er ed in fr om t im e to t im e wi t h

e ,

c ons tan t b oiling un t il the ed c olor is p erman en t r .

T hi s p ro c ess depen ds up on the fac t t h at s odi um c arb on at e

forms wi th s ol ubl e s alts of th es e b as es ins ol ub le n eutral ca r

bon ates .

C aC l 2 N 8 2 C0 3 CaC 0 3 2 N aC l .

Ba (N O 3 ) 2 N a2 C 0 3 BaC O g 2 N aN O g .

As x mp l e of the proc ess : Tak e of c alcium chl orid

an e a

on e gram diss olv e i t in a sm all qu an t i t y of w at er n eut raliz e

, ,

the sol ut i on if it is aci d or alk alin e h eat to b oiling add a , ,

N
few d rop s of p h en ol p h t hal in e , an d t i trat e wi th T
s odi um
c arb on at e d liv ered c aut i ous ly whil e b oiling until
,
e the red
c olor is p erm an en t .

CaC12 N 3 2 C0 3 Cfi C O g J
r 2 N aCl .

m m or 1 0 0 0 mil s
N VS
g s .
53 g s . . .

l
Each mil oi N a C0 V S r epr es en t s
.

? gm of2 3 . . .

CaC l 2 If 7 mils a e used the salt c on tains

. 1 r

gm or 96 p e c en t . r .

N ormal S o dium Carbo nate V S (N C O a = 6) c ontains . . 2 g 10

53 gms in li.t er T his s oluti on is m ade by diss olving

1 .

53
gms of pure s dium carbonate (anhydrous) previously ignited
. o

an d cool ed in distill ed w at er and dilu t ing to liter at 5 C 0

, ,
1 2 .

If a pu e salt is no t at hand the s olu t i on may be m ade as

r

follows :

About 85 gms of pur e s odium bicarbon at e fr ee from

.
,

thiosul phate chl orid etc a heat ed to dull r edn ess (not to
, ,
.
,
re
 AN AL Y SI S BY N E U TRALI Z ATI ON 93

fusion) for about thirty minut es to exp el one half of the CO ; -

2

it is then cool ed under a desiccat or When cool 53 gms .

, .

are dissolv ed in distill ed w at er to m ak e 1 lit er at 2 5 C (7 7

° °
.

N
his solution shoul d n eu traliz e I acid V S volum
T -
. . e

for volum e .

The alk ali earths may also be estim at ed by dissolving

th em in wat er precipitating the b as e as carbon ate with an
, ,

exc ess of ammonium carbonat e and som e free ammonia .

T he mixtur e is t h en h eat ed for a few minut es and the car ,

bonate sep arated by filtration t h oroughly wash ed with hot ,

wat er till all s olubl m atters a e r em oved and th en titrated

e r ,

with normal acid V S as directed for carbonate

. . .

CaBr2 C aC O 2 H2 SO 4 .

-5 2 2 ) oo 35 ~

N
gms .
gms .
4 9 gms or . 1 000 mil s7 "
VS . .

N
Ea ch mil of 1 acid thus repres ents gm of . CaBr2 .

A noth er m etho d for the estim ation of s alts of the alkali

earths consists in pr eci p it ating th em as ox al at es out of an

ammoni ac al or w eak ac etic aci d s olution The pr ecipitat ed .

oxal ate is th en aft er thorough w ashing titrat ed wi th t enth

, ,

normal potassium permanganat e V S O r the excess of oxalic . .

aci d in the filtr at e may be titrat ed with standa d p ermanganate

‘
r

V S This m etho d is how ever es p eci ally ap plic abl e to c alcium

. .
, ,

es t im ations b ec aus e of the compl et en ess with which this m et al

may be precipit at ed as ox al at e .

Magnesium Carbonate O ne gm of m agn esium c arbon . .

ate is dissolv ed ln 3 mils of n orm al sul phuric acid V S and

0 . .
,

the exc ess of the l att er det ermin ed by ti t ration with norm al

p ot assium hy dr oxi d V S using m eth yl or ang e as in dicat or

. .
, .

Magnesium O xi d and Magn esium Hydroxi d are estimat ed in

94 THE E SSE N TIALS OF V OL U ME TRI C AN AL S S Y I
x ctly the sam e m ann er The abs ence of calcium oxi d must
e a .
,

how ever be assured or if present it s qu antity determin ed

, , , , .

This is don e by pr ecipi t ation wi t h ammonium ox al at e in

the p r es enc e of ammonium chlori d and ammonium hy droxi d .

The pr ecipitat e is incin erat ed and the r esidual c alcium oxi d

weigh ed .

Al k ali metri c Assay of Z inc S alts Z i nc Ox i d D igest about . .

1.
5g m of zinc oxid
. a ccur a t ely w eigh ed with 5 mils of norm al
, , 0

sul phuric acid V S until solution is comp l ete Then titrate

. .
, .

the exc ess of sul phuric acid with norm al potassium hydroxi d

V S using m ethyl orange as indicator

. .
,
.

2 110 H2 SO 4 Z II S O 4 H2 0 .

inc carbonat e and zinc s t earat e are assayed in the s ame

Z
m anner In the case of the l atter boiling for ten minutes
.
,

may be n ec ess ary in ord er to compl et ely dissolve th s alt e .

E ach mil of norm al sulphuric acid V S corresponds to 5 . .

gm of zinc oxi d
. .

The E s tim ati o n of Mix ed Hydroxi ds and Carbonates of

Alkali E arths This may be don e as d escrib ed under esti
.

m ation of mixed alkal i hydroxids and carbonates p age 77 , ,

exc ep t th at in this c as e it is unn ec essary to pr ecipitat e the

carbonate by b arium chlorid in that the alkali earth carbonates

are already insolubl e .

Assay of Chl oral Hydrat e D issolve an accurat ely w eighed .

qu antity (about 4 gms ) of chloral hydrat e in 1 0 mils of dis .

till ed water add 30 mils of n orm al p otassium hydroxid V S

, .

and let the solu t ion s t an d about two min ut es Th en add .

p h e nol p hth al ein T S and a t onc e titr at e the exc ess

, of alk ali
by m eans of norm al sul phuric acid V S . .

This r eaction must tak e p l ac e in the cold or at l east at

ordin ary tem perature o th erwis e the alkali will attack the ,

chloroform which is form ed and yi eld too hi gh resul t s The .

96 . THE E SSE N T AL S OF I VOLU ME TRI C AN AL Y SI S
is reversed alkalin e s ol ut ions of known power b eing used in
,

det ermining th s t r ng t h of aci ds and of aci d s alt s

e e T hus the . .

p r oc edur e is an alog ous to t hat of the alkalim etric m et ho ds .

The choic of the in dic at or wh et h er li t m us p h en ol p h t h al in

e , ,
e ,

or m et hyl orang e dep en ds up on the part ic ul ar aci d to b

,
e

estim at ed .Ph en ol p h t h al ein is em p l oy ed fo the organic aci ds r

an d boric aci d an d is p r f err ed fo p h os p h oric aci d; ewhil r e

m ethyl orang e and litmus a e usually emp l oy ed in the t i trat i on r

of the in or g ani c aci ds .

The s t an dard alkali us ed may be ei t h er an hydroxi d or

a c arb on at e the f orm er is how ev er usu all y p r ef rr ed b ec aus e
, , ,
e ,

the c arbon at e wh en br ough t in c on t ac t wi t h an aci d gi v es

off c arbonic aci d gas (C O ) which int erf er es to a gr eat ext ent 2

with most in di c ators On the oth er han d it must be r em em

.
,

ber ed th at the alkali hydroxi ds a e v ery pron to abs orb carb on r e

di oxid from the atmosph er e th er ef or e th eir s oluti ons of t en ,

contain som e c arb on at e the pres enc e of which even in small ,

quantiti es will occ asion errors wh en us ed with most indicators ,

es p eci ally with litmus an d p h en ol p hth al ein It is th erefor e .

advis abl e ,
wh en using t h es e in dicators or o t h ers which a e r

aff ect ed by c ar b on di oxi d to employ g en t l e h eat t ow ar d the ,

cl os e of each titrat ion in ord er to driv e off the lib erat ed gas
, .

Methyl orang e is n ot affect ed by thi s gas and t h er efor e h eating ,

is not n ec ess ary wh en this in dic ator is us ed In fact it is .

,

imp erati ve that h eat shoul d not be emp l oy ed wi th thiS .

in dic at or.

I n ac i dim etri c al op er ati ons Wh en m ethyl orang e is us d e

as in dic at or r esidu al titr at ions m ay be adv an t ag eous ly don e

, ,

b ec aus e the chang e of color from y ell ow t o red which is

brought about by the acid is much mor e r eadily s een than
that from red to y ellow .

In the U S P s tandard sol uti ons of b ot h p otassium an d

. . .

sodium hy droxid are ofli ci al The form er how ev er is pr ef .

, ,
 AN AL Y SI S BY N E UTRAL IZ ATI ON 97

erable, b ecaus e it attacks gl ass l ss en erg etically and also e ,

foams much l ess than does the s odium hydroxi d s olu t ion .

The n eutrali ing p ow er of b oth is how ev er the s am e

z , S tan dard ,
.

solutions of alkali hydroxid shoul d be pres erved in small vials ,

p rovi ded wi t h w ell fi ttin g rubb er sto p p ers

-
or b ett er still th ey , ,

sh oul d be pr ovided with tub es fill ed with a mix ture of so da

and lim e which abs orbs CO
,
an d p r ev n t s i t s acc ess to the
2 e

solution A vess el of this descri p tion is illustrated in Fig 35

. . .

An improv em en t u p on t hi s is sh own in Fi g 36 sin c e i t .

,

allows of the bur et t e b eing fill ed witho ut r emoving the sto pp er ,

and cons equ ently without any acc ess of C D wh at ev er 2 .

Wh ere a s eri es of titrations of the s am e ki nd hav e to be

m ade with the s am e alkali standard s olu t i on the arrang em ent ,

sho wn in Fig 9 may be us ed both th r es erv oir and the

.
,
e

bur ett e in this c as e b ein g provid ed wi t h soda lim e tub es -

.

r
P rep a ati o n of n r
S ta da d A lk al i S olu i o t ns

N ormal Potassium Hydroxi d V S . . VS

. .

gms in 1 0 mils) Potass um hydroxid b eing prone

. 00 . 1

t o absorb c arbon dioxid out of the ai the p ur e articl e is not r

readily obtained in c omm erc e I f pure potassium hydroxid .

were easily ob tained i t woul d only be n ec essary to dissolve

gms in suffi ci ent wat er to make
. mils But sinc e it always
1000 .

contains som e CO and H 0 it is n ec essary to take a sligh t

2 2 ,

exc ess and dilu t e the solution to the p ro p er v olum e af t er h aving

determined its str eng t h .

The stand ardiz ati on may be effect ed by m eans of any of

the standard acid solutions .

A s atisfactory m et h od for the p r eparat i on and s t andard

i ation of this soluti on is as follows
z

D issolve 7 5 gms of potassium hy droxid in su ffici ent r ec ently

.
98 THE E SSE N T AL S OF I VOLUME TRI C AN AL YSI S
boil ed distill ed water to make about 1 0 50 mils at 2 5 C (7 7 °
.
°

and fill a bur ett e with a portion of thi s solu t i on .

D issolve gm of pure oxalic acid in about 0 mils of

, 1

water in a b eaker or flask add a few dr ops of ph enolphthal ein

,

TS , and th en c ar efully add from the bur ette the p otassium

hydroxi d solution agitating frequ en t ly and regul ating the flow

,

to drop s towards the end of the o peration until a perman ent

p al e pink color is obt ain ed N ot e the numb er of mils of the
.

alkali s olution consum ed and th en dilut e the r emain der so

,

that exactly 0 mils of the diluted liquid will be required to

1

n eutraliz e gm of oxalic acid Ins t ead of w eighi ng off

. .

gm of the acid 0 mils of its normal solution may be

.
,
1

us ed .

E x ample Assuming th at 8 mils of the strong er potassium

.

hydro xi d solution had b een consum ed in the trial then each ,

8 mils must be dilut ed to 1 0 mils or the whol e or the r em aining,

solution in the s am e pro portion Thus if 8 mils must be .

diluted to 0 mils 0 0 0 mils must be diluted to 1 2 50 mils

1 ,
1 .

8 : x x = 2 50 mils 1 .

It is always advisabl e to m ake ano th er trial after diluting .

Ten mils shoul d th en n eutraliz e gm of pur e oxalic acid . .

S ta n d a r d i z a ti o n by M ea n s f P
o o ta ss i u m B i ta r t r a t e .

T his m etho d is b ased upon the reaction

K HC4 H4 0 6 KOH K 2 C 4 H4 0 6 HzO .

l
A
1 0 0 0 mils of
l
K O H cont ains gms of K OH and .

will react with gms of potassiu

m bitartrate 2 5 mils . .

l
?
of K O H will th erefore react with gms of potassium
.

bitartrate .

A solution of potassium hydroxid , 75 gm s in

. 1 0 50 mils , is
100 THE E SSE N TIAL S OF VOL U ME TR I C AN AL Y SI S
S ta n d a r d i z a ti on by M ea n s o f P o t a ss i u m Bi -i o d a t e . *

P otassium bi io dat e is an aci d salt and may be dir ec t ly

-

ti trated with potassium hydroxid using ph enolphthal ein as ,

in dicator .

O ne mol ecul e of the bi io dat e is equival ent to one mol ecul e -

of potassium hydroxid as shown by the equation , ,

K H (I 0 3 ) 2 KOH 2 K I 0 3 + H2 O .

standardiz e a potassium hydroxid solution w eigh accu

To -
,

ratel
y gms of pot a ssium bi iod at.e dissolve it in about -
,

2
5 mils of w at e r ad d a fe w dro p s of
, ph enolphth a l e in an d t h en ,

run int o this from a b urett e the hydroxi d solution which is

, ,

to be standardiz ed until a p al e pink color app ears N ote , .

the numb er of mils us ed and dilut e the solution so that ex actly

1 0 mils of it will n eu t raliz e gms of the bi iodate .

—
.

E x ampl Assuming th at
e . mils had b een consum ed ,

th en each mils must be diluted to 1 0 mils or the whol e ,

of the r em aining solution in the sam e proportion .

The advantag es of this s alt as an ultim at e stand ard are

() 1th a t it m ay b e p rocur ed in th e m ark et in a st a t e of absolut e

p urit ”
y ( )
L
t h at i t is
2 p e rm an ent b eing n eith er d eliqu e sc ent ,

nor effl orescent ; (3) that it an be dri ed at 1 1 0 C wi thout c

°
.

decomposi t ion ; (4 ) t hat the r esults obtain ed with it are quit e

accur at e an d (5) t h at i t m ay be em p loy ed for st and ardizin g
,

mos t of the volum etric solutions comm only found in the

l aboratory .

S M i k Ch m Z tg XIX
ee e n ec e, Al s C sp ri Pr
e . A Ph A
.
, . 2 . o a a , oc . . . .
,

TAcco din r g s r
to C a p a i , the salt m ay be r
eadily pr r
epa ed as follow s : See
A Ph A
. . .
,
1 90 4 , 390 s luti wi th an
. Po t ssi
a um bi ca bona r t e i s mi xed in o on

eq iv l t m u t f i di
u a en id
a d t th n utral s l ti
o n o i add d an
o c ac , an o e e ou on s e
am t f i di id qu l t th qu tity first us d Th s lutio i th
oun o o c ac e a o e an e .
e o n s en
ev p r t d til rystalli ti b gi s a d th first r p f rystals r j t d
a o a e un c za on e n , n e c o o c e ec e
Th s whi h s p r t ft r th s l ti h
.

led t 5 lm st p ur
°
o e c e a a e a C e e ou on as coo o 0 are a
.
o e
and wi ll b r d r d bs lut ly pur if r rystalli d
e en e e a o e e ec ze .
 AN AL Y S S I BY N E U TRAL I Z ATI ON 101

S ta n d a r d i z a ti on by M e a n s of N o r m a l A c i d V S 2 0 mils . .

of a strictly norm al aci d V S . are p l ac ed in t o a b eak er , 2

.

dr o p s of m et hyl orang e T S a e added an d the p otassium

. . r

hydroxid solution delivered in to it un t il the red liquid just

turns yellow If the alkali hydroxi d solution is strictly n ormal
.
,

there will be consum ed exac t ly 0 mils If l ess is c onsumed 2 .

the solu tion is too s tr ong an d must be so dilu t ed wi t h dis t ill ed

wat er that equal volum es of it and the norm al acid will exac t ly
n eutraliz e each oth er Thus if 8 mils of the alkali are con
. 1

sum ed th en each 8 mils must be dilut ed to 2 0 mils

,
1 .

N ormal S o di um Hydroxi d V S (N aO H =
4 ; V S =
4
. 0 . 0 . .

gms in
. 1 000 mils ) D iss olve 54 gms of s odium hydroxid in
. .

enough r ec ently boil ed distill ed w at er t o m ak e ab out 1 5 0 0

mils of solution fill a buret t e wi th a p or tion of this and Ch eck

, ,

i t wi th n ormal acid or a w eigh ed qu an ti ty of oxalic acid or

,

potassium bi tar trate in exac t ly the s am e mann er as describ ed

,

for norm al potassium hydroxid .

O th er str engths of stan dard alkali V S are h alf norm al . .

-

F if t h norm al
-
Ten t h norm al
, Tw enti eth -

norm al F ifti eth norm al -

Hun dredth -
n orm al
T hese are all prepared by properly diluting the norm al V S . .

and th en ch ecking the str ength of the pr oduc t .

O th er stan dard alkali soluti ons in fr equ ent use a e n orm al r

sodium carbonate norm al and oth er s treng ths of am m onia

, ,

and t en t h norm al b arium hydroxid

-
.

Tenth N ormal Barium Hydro xi d V S . .

N
18
gms i n 1 0 0 0 m ls ) D ss olv e about 8
. i . i 1

gm s . of crystalliz ed b arium h ydr o xi d in 0 mils of r ec ently 100

boil ed distill ed water and if n ec ess ary fil t er the solution

, , ,
102 THE E SSEN TIAL S OF V OL U ME TRI C AN AL Y SI S
Introduc e 5 mils of t nth normal hydrochloric acid V S
2 e -
. .

into a flask add 3 drops of ph enol phthal ein T S and run in

, .

the b arium hy droxi d solution from a b ur ett e p rovi ded with ,

a sod a lim e tub e r educing the flow t o dro p s toward the end
-
,

until a pal e pink color is obtain ed which does not disappear

on shaking the liquid for ten s econds N ote the numb er of .

mils c onsumed and if the solution is too conc entrat ed dilute the ,

r emainder with freshly boil ed and c ool ed distill ed water so that ,

equ al volum es of the b arium hydroxi d solution and of t enth nor -

mal hydrochloric aci d V S at 2 5 C exactly n eutraliz e each oth er

°
. . . .

N OTE This solutio n absorbs C O from the air v ery rap idly
. 2 ,

and th er eby los es its tit er It sh oul d th erefore be preserved

.

in rubb er stopp ered b ott l es provided with a soda lim e tub e

-
’

-
.

(S ee F i g 3 . T his s olution must b e st and ardiz ed each tim e

b efore using .

E s t im at i on of th e I n organi c A ci ds

To weigh off direc t ly a definite quantity of a fluid acid is ,

not a v ery easy matt er It is always a b etter plan to measure

.

a sm all q uantity of the acid an d w eigh i t accurat ely in a t ar ed

and sto pp er ed w eighing fl ask ( Fi g th en to add .

wat er and t itrat e with the standard alkali in the

pres enc e of a suitabl e indicator If the sp ecific gravity .

of the acid is known or can be easily tak en i t is ,

suffi cien t t o m easure a c ertain quantity of it by

FIG 37 .
m eans of a p ip ett e and th en d et ermin e its w eigh t
,

by multiplying the volum e in cubic c entim et ers by

.

the sp ecific gravity It must be r em emb ered how ev er that

.
, ,

the liquid must be m easured at the s am e t emp eratur e at

whi ch the sp ecific gravity was taken Thi s m ethod is .

ap p lic abl e to the dilut ed acids as w ell as to the conc entrat ed

acids of comm erc e as hydrochloric nitric and sulphuric

, , .
104 THE E S SE N TIAL S OF V O LU ME TRI C AN AL Y SI S
The q uan ti ty of acid to be taken (in m os t cas es) shoul d
be such as will r equir e fo n eutraliz ation from to 50 mils r 20

of the stan dard alkali In the cas e of c oncen trated inorganic

.

aci ds , or 3 gms may be t ak en whil e in the cas e of the dilute

2 .
,

aci ds from 6 to 8 gms

, .

Any of the in dicators m ay be em p loyed for the inorganic

acids but b ec aus e of the usu al p r es enc e of c arb on at e in the
,

standard alkali m ethyl orange is preferred

,
.

Hydrochl ori c Aci d About mils of hydro 2

chl oric acid (sp gr 55) a re

. intro duc ed in
. t o a t ar ed w eighing
flas k and its w eight accurat ely t ak en (The w eight is foun d .

to be gms ) Fifty mils of wat er a now added foll ow ed

. re ,

by drops of m thyl orange and the s olu t i on car efully titrat ed

2 e ,

wi th n orm al p otassium hydroxi d until the reddish c olor of

the solu t ion is ch ang ed t o y ell ow .

Assuming t h at mils w ere r equired th en mils X ,

g m =0 6
7. gm of a bsolu
. te hy dr o chl
1 oric aci d in.th e

gms taken . .

To fi n d the p e c n t app ly the pr op or t ion

r e

gms . gm . 1 00 x . x =
3 1 .
9 p er cent .

The quation is
e :

HC l KOH K Cl H2 O .

gm s = 6
5 . . 1 gms = 1 00 0 mil
. s? VS . .

i
. 0 36 4 7 gm . 1 mil
; VS . .

S ulphun c Aci d b ou t mil of the con

(H2 SO 4
=
98 A 1

ci is w eigh ed in a tared w eighing flask and found

cen trated a d

to w eigh g m s F if t y mils of w at er ar e
. added an d th en
2 dro p s of m t hyl orang e and the t i trat ion with norm al p otas
e ,

sium hydroxid b gun and c autiously continu ed until the

e ,
 AN AL YS I S BY N E UTRAL IZ ATI ON 105

yello wish c ol or of the solution in dicat es the compl etion of

the o erati on N o t e the numb er of mils of alk ali solu t ion us ed
p .

and app ly the equ ation

H2 80 4 2 KO H KSO 2 4 2 112 0 .

N
gms .
gms = 1 000 m i l
. s _
1
VS . .

Thus ch mil
ea of norm al K OH V S . . repres ents
gm of pure H.
2 SO 4 .

Aromati c S ulphuri c Acid his is an alcoholic solution . T

containin g free sulphuric acid and ethyl sul phuric together
with a vol atil e dil The l atter as w ell as the alcohol present
.

n eu traliz es alkali hydroxid and must therefore be removed ,

by h eating b efore ti trat ion of the acid is undertaken The .

U S P m ethod is as foll ows Pour ab out

. . . mils of arom atic : 10

sulphuric acid into a tared flask stopp er and w eigh transfer , ,

to a small flask using 6 mils of dis t ill ed w ater to rinse the 0

weighing fl ask and h aving connect ed the flask wi t h a reflux

-
, ,

cond enser boil the liqui d for six hours ; wh en col d dilute it
, ,

with distill ed w ater to about 0 mils and titrate with norm al 10 ,

potassium hydroxid V S using m ethyl orange as indicator . .

, .

Calcul at e as in pr ec eding assay .

Phosphori c Aci d In the assay of phos

p h ori c a cid by dir ect n eutr aliz ation with sta n dar d K O H ,

the acid is conv ert ed in to first K H P O th en K HPO , , 2 4, 2 4,

and fi n ally into the norm al K 3PO We have no indicator 4 .

which reliably shows the com p l etion oi the n eutralization

'

i e the form ation of the trib asic K 3P O

. .
, L itmus c ann ot 4 .

be us ed as indic ator h ere for the di p otassic or disodi chydr i c

p hos p h at e (K HPO or N a H P2O ) which4 is form ed is 2 4

S lightly alk alin e tow ards litmus ; the s am e is tru e of most oth er

indicators .

Thompson however has d emonstrat ed that this acid may

, ,
106 THE E SSE N T AL S OF I VOL U ME TRI C AN AL S S Y I
be ccuratel y titrated by s tandard alkali when using either
a

m ethyl orange or ph en olph th al ein or bo th successively , ,

.

If methyl orang e is used the c olor changes upon the com

letion of the form ation of monob asic phos ph at e K H P O as
p , 2 4 ,

er the following equ ation

p

H3 PO 4 KO H K H2 P O 4 HzO

If phenol phthal ein is us ed the col or changes u pon the com

,

leti on of the form at ion of the dib asic p h os p h at e K H P O

p , 2 4 ,

H3 PO 4 ‘
l
‘
2 KO H K 2 HPO 4 i " “
Z H2 O .

As an ex a w eigh ed qu antity of the acid is diluted

mple: A
with w ater to m easur e 2 mils and suffici ent pure sodium
0

chl ori d added to saturate the solution Four dr op s of m ethyl .

N
orange are then introduc ed and the titrat ion with 1 K O H
.

b egun and c ontinu ed until the red color ch anges to yellow ,

indicating the form ation of the monob asic phos ph ate

H3PO 4 K OH KH2 P 0 4 112 0 .

gms .
gms . 1 00 0 mil s 1? V S . .

Ea ch mil of KO H gm of H3PO .
4 .

The of sodium chlorid in this assay is to decrease the

use

ioniz ation of the acid salts pro duc ed in the reaction .

Anoth er p ortion of the aci d is tr eat ed in lik e m ann er ,

ad ding so dium chlori d and titrating but using p h enol phth al ein ,

as the in dic ator T he ti tr at ion is con t inu ed until a faint

.

p erm anent pink col or app ears It is advis abl e to use heat .
,

or b ett er still a standar d alkali solution which is quite free

,
108 THE E SSE N TIALS OF V OL UME TRI C AN AL Y SI S
sam e way as the foregoing bu t it is usu ally preferred to
.

the ,

es t im at e th em by pr eci p i t at ion an alysis T his is also t ru e of .

phosphoric acid Sulphurous acid is b est assayed by oxi da

.

tion with io din .

Bori c Acid T his acid is estim ated by

neutraliz ation with N aO H in the pres enc e of a l arge

—

qu antity of glyc erin (Thompson s Method J S C I XI I

.
’
,
. . . .
, ,

The addition of su ffi ci ent glyc erin to a boric acid

solution so th at no l ess than 30 per c ent be pr es ent thr oughout
,

the titration dev elops the aci dity of boric aci d with r eg ard
,

to ph enolphth al ein to a gr eat d egree and en abl es on e to ,

titrate direct with standard soda solution O ne gm of boric . .

aci d is dissolved in 50 mils of w at er ; to this is added an equ al

volum e of glyc erin th en a few dr op s of ph enol phthal ein and

, ,

the t itration with norm al sodium hy droxi d b egun and con

ti nued until a pink color app ears .

Ea ch mil of N aO H = 0 . 0 62 0 2 gm of H3B0 3
. .

H3B0 3 N aO H N aH2 B0 3 H2 O .

N
4 0 gms . in 1 000 s TVS
mil . .

ml
N
gm 1 iVS
1
. . .

E sti mati on of th e O rgani c A ci ds

As theindividu al organic acids r equire di fferent indic ators ,

the tabl e on p ag e 2 8 S houl d be consulted in the s el ecti on of

an indic ator for a p ar t icul ar org anic acid Ph enolphth al ein .

is however the most suitabl e for organic acids generally

, , .

Aceti c Aci d Mix 3 gm s of the acid .

with 50 mils of wat er add a few dr o p s of ph enolphthal ein

,

TS and titr at e wi t h norm al p ot assium hy droxid V S until

, . .
 AN AL YSI S BY NE UTRAL IZATI ON 109

a p erm anent p al e pink color is obtained , and a pply the fol

lowing equation :
HC2 H3 0 2 KO H = K C2 H3 0 3 112 0 .

1
Thus mils of } KOH V S will n eutraliz e gms ‘
1 00 0 . . 60 .

N
of ac etic aci d; th erefore each mil oi K O H V S represents . .

gm of a
.c et ic acid .

If 8 mils are required to n eutraliz e 3 gms of the acid it

1 .
,

contains 1 8 X 0 0 6 = .gms of absolu te ac etic acid

. .

X 1 00 —
6
3 p er c ent .

Tartari c Aci d gms of D issolve 2 .

tartaric acid in 50 mils of dis t ill ed w ater add a few drop s of ,

p h enolphth al ein and t h en p ass int o the solu t ion from a bur ett e

1
potassium hydroxid V S until a faint p ink t int is acquired
. .

by the solution and ap ply the equ ation

,

H2 C4 H4 0 6 2 KO H K 2 C 4 H4 0 6 2 112 0 .

N
75 gms = 1 0 0
. 0 m il s _
I
V‘S '

Cl tl lc Aci d ( 3 C 6 5 7
'
H H O = 1 92 .

H3 C 6H5 O 7 3K O H K 3 C 6 H5 O 7 H
4 20 .

N
gms .
= 1 000 mil s “

i
VS . .

Ea ch mil of 2 KO H repres ents gm . of citric acid .

Tri chloraceti c Aci d (C C13 C O O H =

C C13 CO O H KOH C C13 C O O K + H2 0 .

1 63 -
3 9
1 10 THE E S SE N TI ALS O F VOL U ME TRI C AN AL Y SI S

E
E ach mil of
j KO H V S . . represents gm . of tri
chlorac etic acid .

The oth er organic acids are ass ay ed in ex actly the s am e

m anner as t hat describ ed for the foregoing wi th the exception
of b enz oic and salicylic acids .

Benz oi c Aci d (HC7 H O ) and S ali cyli c Aci d (HC7 H5 0 )

5 Z 3 .

T h es e aci ds a e ass ay ed as follows

r D issolve gm of the : .

aci d p r eviously dri ed to c onst an t w eight in a desicc ator over

,

sul phuric aci d in 2 5 mils of diluted alcohol which has b een

,

pr evi ously n eu traliz ed wi th t en t h norm al potassium hydroxid -

V S ph enolphthal ein T S b eing us ed as in dic at or

. .
,
. Titr at e
. .

this solu ti on with tenth norm al b arium hydroxid -

using
ph en ol ph thal ein as indicator .

The r eac t io ns a e r

2 HC7 H5 0 2 Ba (O H ) 2 Ba (C7 H5 0 2 ) 2 2 H2 0 .

N
1 2 2 0 5 = to 1 000
. mi l s B B (OH) a 2 VS
. .

N
Ea ch m l of T Ba(O H) V S represents
i
0 g m of
2 . . .

b enz oic acid and 8

3 5
0 gm of s
00 1alicylic acid . .

Lacti c Aci d A defi nite w eight is

treat ed with an excess of norm al p otassium hydroxid VS . .

and b oil ed for tw enty minu t es The boiling solu t i on is th en .

ti trat ed with norm al sul phuric aci d V S The qu an tity of the . .

l att er consum ed deducted from the qu an ti ty (in mils) of n orm al

p o ta ssium hy dr oxi d V S origin a lly add. ed giv
. es the qu antity ,

of the alk ali solution which r e r es ents the l actic aci d b eing
p
ass ay ed .

S ee p a g e 10 1 .
1 12 THE E SSE N T ALS OF I VOLU ME TRI C Y I
AN AL S S

stanc es of low perc entage strength as for instance lim e water , ,

so small a volum e of s tandard solu t i on is r equired as to be

unr eadabl e mil) It is th erefore advisabl e to take for .

an alysis a sm all er qu antity of hi gh p erc en t ag e substanc es and

a l arg er qu antity of such subst anc es as cont ain a low p erc ent

age . It is usu ally b est to so adjus t it that no l ess than 1 0

nor more than 30 mils of the standard solution be required .

For exampl e : In the c as e of citric acid inst ead of tak ing ,

for analysis 7 gms it will be b etter to tak e one fourth of this

.
-

qu antity th en each mil of the standard solution used will

,

r epresent 4 per c ent and only one four t h as much will be ,

-

r equir ed i e mils in st ead of

,
. .
, mils Again in the .
,

c ase of lim e water if gms are taken instead of ,

.

N
gms , . mils of the —

1
standard solution will be required ,

whi ch is b etter than mil but in this cas e it will be still

,

b etter to use a d ecinorm al solution th en

, gms of .

lime wat er woul d require for n eu tralization just 14 mils of

0
cid
1
VS a . .

If half the quantity indicated in the tabl e is taken then ,

each mil of the stan dar d s olu t i on w ould r epr es en t 2 p er c ent .

If one tenth the qu an t ity is t aken each mil will r epresent 1 0

-

r c ent If doubl e the qu antity is tak en each mil will r epres ent
p e .

o 5 per c ent etc

.
, .
 CHAPTE R I X

AN A L YSI S BY PR E CI PITATI O N
gen eral princip l e of this m etho d, is th at the det er
THE
min ation of the quan t i ty of a giv en s ubs t anc e is eff ect ed by
the f orm at ion of a pr ecip it at e u p on the addi t i on of the ,

s t andard solu t ion to the s ubstanc e under examination Th ere .

a e thr ee w ays of det ermining the en d r eaction in p reci pi

r -

tati on an alys es
1 . By addi ng the standard soluti on unti l it ceases to roduce
p
any more preci pi tate ,
as in
stimation of silv er by s t an dard
the e

s odium chl orid and the es t imat i on of hal oi d s alts and acids
,

by means of stan dard silver ni trat e The app lic ation of t his .

en ding is alm os t limit ed to th e abov e estim ations b ec aus e ,

in th es e only can acc urat e resul t s be ob tain ed The silver .

halids form ed a e no t only quit e insolubl e but th ey h ave a

r ,

t en dency to c urdl e clos ely up on shaking (esp eci ally in aci d

s ol uti ons) and t hus l eav e a cl ear supern atan t liquid in which
,

any fur t h er p r eci p i t at ion can r eadily be s een Most of the .

ot h er pr eci i t at es s u ch a b a rium s ul p h at e c a lcium ox a l at

p , s e, ,

etc . al t h ough h eavy and ins ol ubl e a e so fin ely divi ded and
, ,
r

p ow d e ry t h a t t h ey d o n ot r ea d ily subsi d e .

2 By the u of an i n di cator as in the estimat i on of h al oi d

. se ,

s al t s by m eans of stan dard silv er nitrate s oluti on using n eutral ,

p ot a ss i u m chr o m at e a s th e in d ic ator T he l a tt e
. r is add e d to
the h al oi d solu t ion (which must be n eutral ) and the silver ,

ni trate V S delivered int o the mix t ure until a p erm anent red
. .

color (silver chromate) is produced Silver nitrate reacts by .

prefer ence with the halogen and do es not react with the chro
,

113
114 THE E SSE N T ALS OF I VOLU ME TRI C AN AL Y SI S
mate until the hal og n has b e n en t ir ly precipitated Hence e e e .

the p roducti on of a p erm an en t ed c ol or in the pr eci p itat e r

marks the com pl et ion of the precipi tat ion of the h alogen .

Anoth er illustration is in the estim ation of silv er by sul

h n ate s olu t ion u sing f erric alum a indic ator T h
p ocy a s ,
e .

s ulph ocyanat e produc es with the silv er a whit e pr eci pi t at e

of silv er sulph ocy n at e but wh en the pr eci p i t ati on of silv er
a ,

is comp let e the sulphocyan at e r eacts with the f erric alum

pres en t an d a red ferric sulphocyan at e app ears and marks the
end p oint
-
O n the oth er h and the indic at or may be us ed
.
,

ext ern ally i e alongsid e of the liqui d b eing an alyz ed a drop

,
. .
, ,

of the l att er b eing brought in contact with a drop of the in di

cator at frequ ent int ervals in the c ours e of the titration as in ,

the estim ation of p hosphoric acid by m eans of uranium nitr at e

s oluti on in which potassium ferrocyani de is us ed as in dicator
, .

3 B y a d
. di ng the standa rd soluti on unti l the fi rst appearance

f
o a preci pi u u
e , a s stimation of cyanog en by silver in the e
nitrat e solu t ion and the estim at ion of chlorin by m ercuric
,

nitrate V S In th es e estim ations the standard solution is

. .

add ed to the solutio n of the subst anc e und er an alysis until a

p r ecipit at e app ears .

P reparat i o n of Deci n o rmal Sil ver Ni trate (AgN 0 3

1
2; VS . .
= gms in . 1 00 0 mils) . D issolve
gms of pure silver nitr t in suffici en t wat er to mak e:at
. a e*

or n ear 2 5 C (7 7 ex ac tly 1 00
°
mils O ne li t er of this
.
°
0 .

soluti on thus contains TT, of the m ol ecul ar w eight in grams of I

silver nitrat e It is th erefore a decin orm al solution

. .

If pure crystals of silver nitrate are not readily obtain abl e ,

and pur e s odium chl ori d is at h and a soluti on of the silver ,

*
Thi s sh ld b p lv ri d ou e u e ze and r
d i ed at 1 2 0
°
C for half
. an hou r in a
v d ru ibl b f r w ighi g
co ere c c e e o e e n .
1 16 THE E SSE N TI ALS OF VOL U ME T R I C AN AL Y SI S
residu e in sufficient distill ed water to m easure exactly
mils at 5 C 2
°
.

N N
D ecinormal S o dium Chlori d VS
I
. .

10 S

gms in 00 mils) D issolve

. 1 0 gms of pure . .

sodium chlorid in enough wat er to m ake exactly 1 0 mils 00

at the stan dard t emp eratur e .

C h eck this solution wi t h decinorm al silver ni trat The e .

two solutions shoul d correspon d volum e fo volum e ,

r .

P ure S odi um C hlo i d may be pr ep ar ed by p assing in to

r

a s aturat ed aqu eous solution of the pur est comm ercial s odium

chlorid a current of dry hydrochloric acid gas The crystal .

line precipitate is th en s eparated and dried at a temp erature

suffi ciently high to exp el all traces of free acid .

The m ethod of standardizing N aCl solution is as follows

15
gm of silver nitrate is dissolved in
. 10 mils of dis
N
till ed water , solution c arefully ti trated with 5 N aCl
and the

V S until preci pitation c eas es

. . Tw enty mils of the stand ard .

solution shoul d be required .

AgN 0 3 N aCl AgCl N aN O g .

gms .
gms .
, or 1 000 mi l s N aCl V S . .

ch mil of
Ea the standard solution represents gm .

of pure AgN O g .

X 20 o .
3397 8 gm .

X 1 00
1 00 p er c ent .

Thi s
solution may als o be stan dardized by residual
tion with V olhard s solution ’
.
 AN A LYSI S BY P RE CI PITATI ON 1 17

N
r
D eci no mal
7
1 )
Po tassium S ulph o cyanate (V olh ard s Solu
’

tion) 13
gms in 000 mils) . 1 .

D issolve 1 0 gms of pur e crys talliz ed potassium sulphocyan at e

.

(thiocy an at e) in 1 0 0 0 mils of w at er .

This solution which is too conc entrat ed must be adjus t ed

, ,

so as to correspond exac t ly in str ength with decinormal silver

nitrat e V S
. . F or this p urp os e in tro duc e into a fl ask 2 0 mils
N
of 13 AgN 0 3 VS 3 mils of amm onioferric sulphate solu tion
, ,

and 5 mils of dilut ed nitri c aci d ( p er c ent a n

10 d fr ee from
nitrous compounds) .

D ilut e the liqui d wi t h 7 5 m i ls of distill ed w at er and titr at e ,

it with the sulp hocyan ate s oluti on .

At first a whi t e pr ecip it at e of silv er su lp hocy an at e is

produc ed giving the fluid a milky app earanc e and th en as
, ,

each drop of sul p h ocy an at e f alls in it is s urr ound ed by a deep

brownish red cl oud of ferric sul ph ocyanat e whi ch quickly

-
,

dis app ears on sh aking as l ong as any of the silv er nitr at e

,

rem ains unchanged .

Wh en the p oint of s at urat i on is r each ed and the s i lv er

has all b een pr ecip i t at ed a singl e drop of the s ul p hocyan at e
,

solut ion produc es a faint brownish red col or which do es not

-
,

disapp ear on shaking .

N ot e the numb er of mils of the sul p hocy an at e solution

us ed and dilu te the whol e of the remaining s olution so that
,

equ al volum es of t his and of the decinorm al silver ni tr at e

will be r equired t o produc e the p erm an ent br ownish red tint -

.

(T h e s am e tint of brown or r ed t o w hich th e v olum etric solution

is adjusted must be attained wh en the solufi n is us ed in o

volum etric t esting ) .

Assuming th at 9 mils of the s ul ph ocyan at e s olu t i on w er e

1
118 THE E SSE N TIALS OF VOL UME TRI C AN AL Y SI S
required to produce the r eaction t hen each 9 mils must be ,
1

dilut ed to m ak e 0 mils or the whol e of the r em aining solution

2 ,

in the sam e proportion .

Always m ak e a new tri al aft er the diluti on to see if the

N
solutions corr esp ond , e .
g .
, 50 mils of 5 silver ni trat e a e taken r ,

and 5 mils of ammoni oferri c 5 mils of pur e nitric sulphate ,

acid and 2 00 mils of w at er are added and th er e sh oul d be ,

r equired exactly 50 mils of the p otassium sulphocyanat e solu

tion The s am e dep th of r eddish brown tint shoul d be ob
.
-

tained in all ass ays by this m etho d as is obtain ed in stand ard ,

i ing the solution

z .

E sti mati on of S olubl e Hal oi d S alts

T he stimation of th es e salts is b as ed up on the p owerful

e

afli ni ty existin g b etw een the h alog ens an d silv er an d the ,

ready precipitat ion of the r esulting chl orid bromid and i odid , .

S tan dard solution of silv er ni t rat e is us ed for this p urp os e ,

and for the sak e of ex actn ess and c onv eni enc e is m ade of ,

decinorm al str eng t h In some c as es it is advisabl e to use

.

c enti norm al solutions .

Mo hr s Metho d with Chro mate I ndi cator This m ethod

’
.

is the best to use if the h al oi d s al t s a e in n eutral s olution

,
r
,

and s alts of l ead bismu t h , b arium or iron a e absent If , r .

the solution is acid the in dic at or is in admiss abl e in t h at aci ds ,

h av e a solv en t action upon silv er chromat e and thus p r event

the en d r eac t i on from b eing cl early and accurat ely obs erv ed
—
.

If the abov e m ention ed m et als are pres ent the in dic at or is

-
,

likewis e us el ess as th es e b as es form ins olubl e highly c olored

, ,

comp ounds wi th the chromat e The n eutral p otassium chr o .

m at e (y ell ow chromat e) whic h is us ed as the indicator must be

12 0 THE E SSE N TIALS OF V O LU ME TRI C AN AL Y SI S
gm of
. the s alt) is taken , a few d rop s of n eutral potassiu m
chrom at e solu t ion added, silver solution
and th en the
10

deliver ed from a bur tt e with const ant s t irring or shaking

e

until the chlorid is entir ely preci pitated as evidenc ed by the ,

format ion of a p erm an ent red color (silver chrom ate) The .

equ ation is

N aCl AgN 0 3 AgCl N aN O g .

N
gm s = 1 000 mi l
. s1 6
VS
. .

Thus ea ch mil of VS . . r epr es ents gm of . N aCl .

10

If in the above assay 1 7 mils of the silver solution w ere re

quir ed then 1 7 X 0 00 584 6 gm = o9938 gm or
,
.

p er c ent . 0 . 2 .
.

X 10 0
p er c ent .

0 1
0

Ti trat i o n without an In di cator Gay Met ho d I n — -Lussac ’ s .

this m ethod n o in dicat or is us ed the st andard solution ,

b eing added until it c eas es to p roduc e any f ur t h er p ecipi r

tati on . This m ethod is applic abl e to acid s olu t ion of the

h aloid s alts and to the h aloid acids hydrochloric hydro
,
—
,

bromic and hydriodic ; also to the estimation of silver by

standard solution of sodium chlori d The m et ho d is c arri ed .

out in hot solutions sligh t ly acidul at ed with nitric acid in

, ,

order to facilitate the precipitation of the silver h alid The .

h aloid acids are n eutraliz ed with an alkali and th en sli ghtly

acidul at ed with nitric acid b efor e the t itration is b egun The .

c alc ul at ions are precis ely lik e thos e in the foregoing assays .

V olhar d s o Sulpho cyan at e Met hod Thi s m et h od dep ends

’
r .

upon compl et ely pr ecipi t at ing the h al og en in the pres enc e of

nitric acid by a m easur ed exc ess of s tan dard silver ni trate
,

solution and th en estimating th exc ess of silver by retitrating

,
e
 AN A LY SI S BY P E C P R I ITATI ON 12 1

wi th standard s ul ph ocyan at e s olution using f erric alum as ,

an indic ator .

The sul p h ocyan at e has a gr eat er affin ity for silv er th an

it has for iron and th erefor so long as any silv er is in solu
,
e,

tion the s ul phocyan at e will combin e with it and form a p re

,

cip i tate of silv er sul p hocy an at e .

As soon as the silv er is all t ak en up the sul p hocy an at e ,

will combin e wi th the f erric alum and strik e a brownish red -

color .

The sul p h ocyan at e s olution is to be m ad e of such s t r eng t h

that it c orr esp on ds wi t h the silv er s olut ion v olum e for ,

volum e .

The diff er enc e b etw een the v olum e of silv er s ol ut i on origi

n ally added and the v olum e of sul p hocyan at e soluti on us ed ,

will give the volume of silv er sol ution equival ent to the haloid
s alt pres ent .

Thi s m ethod has the advant ag e ov er the dir ect m eth od

for haloids wi t h chr omat e in dic ator in t hat it may be us ed ,

in the pr es enc e of nitric acid I t thus en abl es on e t o estimat e

.

the h aloids in the pr es enc e of phosph at es or oth er s alts which

precipitat e silver in n eutral but not in aci d sol utions and als o ,

in that the pres enc e of b arium bismuth l ead iron and oth er , , ,

m etals do not int erfere as th ey do with the chromat e in

,

Mohr s m ethod The pr es enc e of m ercury how ev er ex erts

’
.
, ,

a disturbing influ enc e u p on the en d r eacti on The nitric aci d -

.

aci dul at es the s ol ut ion an d thus f acilit at es the p r ecip it ation

of silv er by the halog ens and pr events its pr ecip itat ion by
,

oth er substanc es The quantity of nitri c acid emp loyed is of

.

no gr eat import anc e exc ept in the cas e of io di ds (b ec aus e

,

silv er i odid is slightly solubl e in nitric aci d) U sually suffi .

ci ent of the acid is add ed to just r emove the col or produc ed

by the indicat or A v ery l arg e exc ess of the acid w ould
.
,

how ever int erfere with the prop er det ermin at i on of the end
,
122 AN AL S S Y I BY OXI D ATI ON AN D RE D U CTION
reaction in that it to a slight ext ent pr ev ents the formation
,

of ferric sulph ocyan at e In the es t imati on of iodids by this

.

m ethod the ni t ric acid should be add ed aft er the standard

,

silver solution whil e in the c as e of the oth er h aloid s alts the

,

acid may be add ed b efor e .

The indic ator also should be add ed aft er the st and ard
silver solution wh en estimating iodids b ec aus e b eing a ferric
, ,

s al t it is like nitric acid cap abl e of lib erating i odin

, , .

The solutions r equir ed for thi s m ethod are

(I ) Decinormal S ilver N itrate (pag e
(II ) D ecinormal P otassium S ulphocyanate (p ag e
III
( ) F e rr i c Al u m S o luti on ( he in dic ator )
T . .

This is a p er c ent aqu eous solution of f erric ammonium

10 -

sul phat e F eN H (SO ) 1 2 H O

, 4 4 2 z .

I
( )V N itri c A ci d T his must be fr ee from nitr ous
acid If it or any of the low er oxi ds of nitrogen are present
.

they may be removed by diluting with one fourth part of -

water and boiling until colorl ess .

The proc ess is ex em p lifi ed in the following ass ays

E stimati on of Potassi um Br omi d D issolv e about g m . .

of the salt accurat ely w eigh ed in 2 5 mils of distill ed water in

a gl ass sto p p er ed fl ask
-
Add 50 mils of t enth norm al silver
.
-

nitr ate V S th en add mils of amm onio ferric sul phate T S .

. .
, 2 -

and 2 mils of nirti c aci d sh ak e w ell an d fin ally det ermin e the

,

exc ess of the silver nitrat e V S by ti t rating with t enth norm al . .

-

p ot a ssium sul p hocy an a t e V S until a p erm an ent r eddish tint

. .

p erv a d e s th e sup ern at ant liquid .

The di ff er enc e b etw een the numb er of mils of t enth norm al -

silver nitrate V S added and the numb er of mils of t enth

. .

norm al potassium sul phocyanat e us ed multip li ed by ,

g m . gi
, esv th e w eight of pur e K Br i n the
q ua n ti ty of salt ta k en
'

for analysis .
124 THE E SSE N TI AL S OF VO LU ME TRI C AN AL Y SI S
mils of the potassium sul ph ocyan at e s oluti on r equir ed by 2

an d subtract t his figur e fr om 5 (the numb er of mils of t enth0

norm al silver ni trat e V S added) Th di ffer enc e multipli ed

. . . e

by the decin orm al factor of s odium chl orid gm , .

,

gives the w eight of pure N aCl in the amount of salt tak en for
an alysis .

“
t t n
E s im a i o of H al oi d A cids

Thes e acids n amely hydrochloric hydrobromic and

, , ,

hydri odic may be estimated by G ay Lussac s m eth od ab ove

,
- ’

describ ed or th ey may be es t im at ed by Mohr s Met ho d

,
’
.

using n eutr al pot assium chr om at e as an in dic at or In this .

c as e it is n ec essary to c arefully n eutraliz e the acid with

ammonia an d th en t i trat e w i th 10
silver ni trate solution ,

using a few drop s of chrom at e as in dic at or in the mann er ,

describ ed i n -the for eg oing ass ays Th ey m ay also be esti .

mat ed by V olhard s Met hod in which an exc ess of the standard

’
,
'

silv er nitr at e solution is us ed in the pr es enc e of nitric acid

, ,

an d the amoun t of the exc ess d et ermin ed by r esi du al t itr ation

wi t h potassium sulphocy an at e using f erric alum as the indi

,

c ator This m ethod is esp ecially us eful fo iodids an d hydri

. r

odic acid in th at the ni t ric acid n eed not be added un t il aft er

,

an exc ess of silv er nitrat e solu t ion is us ed an d th us lib er at ion ,

of iodin by the nitric acid av o ded 1 .

The estim ation of the h aloi d acids may also be eff ect ed
by n eutraliz ation wi t h s t an dard alkali in the s am e way as ,

oth er acids but sinc e hydrobromic and hydriodic acids a e

,
r

now fr equ ently prep ared by the m ethod of Fothergill in ,

which potassium bromid or p otassi um io did (acc ording to

the acid to be m ad e) is brought in cont act with t art aric acid

(a s shown in the e qu ation ) an exc ess of the l att er acid is

,
 AN A L Y SI S BY P R E CI PITATI ON 12 5

un avoidably pres ent ,

and h enc e the n eutralization m ethod is
in applic abl e .

KI K HC 4 H4 0 6 + 1 11
P o t as si u m Tart ari c ac i d P o tas s i u m Hyd i di
I o d1 d B i tar t rat e A id
r o
c
c

K Br HBr

Assay of Hydrobromi c Aci d, U si n g Chrom at e Indicator as .

Ten gms of hy drobr omic aci d are dilu t ed wi t h su ffici en t di s

.

till ed water t o m ake mils Ten mils of this solution

100 .
,

repres enting gm of the acid is exactly n eutraliz ed wi t h

1 .
,

dilut ed ammonia w at er (using litmus solution as in dicator) ;

3 d rops of n eutral pot assium chrom at e solution are added ,

and then the

16
silver ni trate run in from a burette until the

soluti on acquir es a p ermanent r ed tint . The following equa

tion is th en ap plied
HBr AgN 0 3 AgBr HN O 3 .

gms . 1 00 0 mil s VS . .

If the assay is to be m ade by the direct p ercentage m ethod

:

mils of the solu t ion ( gms in mils) (representing

10 . 100

gms of the acid) shoul d be t aken in which c ase each

.
,

mil of the standard silver solution consum ed will at onc e indi

c ate 1 p er cent .

Hydri odic and hy drochl oric aci ds may also be ass ay ed

by this m eth od .

Assay of Hydrio di c Aci d by the S ulphocyanat e Method .

Intro duc e int o a mil st opper ed flask gms of the acid

2 00 -
2 .
,

add 50 mils of distill ed w at er and 5 mils ( accurat ely m easur ed) 2

of decinorm al silver nitr at e sh ak e thor oughly and t h en add

, ,

3 mils o f nitric aci d and h eat on ,a w at er b at h until th e pr e -

12 6 THE E S SE N TIALS O F V OL U ME TRI C AN AL YSI S
ci pitate brigh t y ll ow color Th en c ool and add 2 mils
has a e .

of the ammonio ferric sul phat T S and finally the decinorm al

-
e ,

potassium sul phocyanate run in sl owly from a burette un t il ,

a p erm an ent r eddish brown t in t is p ro duc ed

-
N ot e the num .

ber of mils of sul phocyan at e s oluti on employ ed .

D educt this from the 5 mils of silver s olu t ion added and
2 ,

multiply the rem ainder by the fact or for HI which is ,

HI AgN 0 3 AgI HN O g .

n .
gms .
= 1 00 0 mil s “
—

I o
VS
. .

N
0 0 1 2 7 93 gm of HI = 1 mil VS
To
.
. . .

III . 2 FeN H4 (SO 4 ) 2 6K S CN

2 Fe (SCN ) 3 i ‘ ‘
N
( H4 ) 2 S O 4 + 3K Q S O4 .

The r eddish brown color which m arks the end reaction

- -

is due to the form ation of Fe (SCN ) ferric sul phocyanate 3 .

Assuming th at in the abov e t itration mils of decinorm al

sulphocyanate w ere employed th en 5 mils mils , 2 .

X gm .

x 100

2
p er cent .

Assay of S yrup of Hydri odi c Aci d

mils of . Tw enty -fi ve
the s yrup are in tro duc ed in t o a stopp er ed fl ask 00 mils of , 1

distill ed w at er are added f oll ow ed by 4 mils of decinorm al

,
0

silver nitrate and the m ixture th oroughly sh ak en Five mils .

of dilut ed nitric aci d and 3 mils of the ferric alum solution

are now added and af t er ag ain sh aking the mixtur e it is
,

titrated with d ecin orm al potassium sul phocyanate until a per

m anent reddish brown tint app ears
- .
12 8 THE E SSE N TIAL S O F V OL UME TRI C AN AL S S Y I
the n eutraliz ed phosphoric acid and the r esidu al silver s olu tion ,

det ermin ed by t i tr at i on with stan dard sul ph ocy an at e .

The proc edure is as f ollows : An accurat ely w eigh ed qu antity

of the ac1d ( about gm ) is dilut ed with 1 0 mils of d ist
. il l ed
water in a 1 00 mil flask O ne drop of ph en ol ph th al ein T S
,
-
. .

is added and the s olution c arefully n eutraliz ed with special

,

potassium hydroxi d s olu t ion i e one free from chlori d ,

. .
, .

F ifty mils of t enth norm al silver ni t rat e V S are n ow added

- . .
,

the mixtur e agitat ed an d zinc oxi d (fr ee from chlorid) gr adu ally
added in sm all p orti ons at a t im e until the liqui d is n eu tr al ,

to litmus pap er It is th en diluted wi th su ffici ent dis t ill ed

.

water to m easure mils again th oroughly agi tated and

100 ,

filtered through a dry fil t er c oll ec t ing 5 mils of fil trat e To , 0 .

this 5 mils of filtrate is added mils of ni tric acid and 2 mils

0 2

of ammonio ferric sul ph at e T S and th en t itrated wi th tenth

—
.

norm al potassium sul ph ocyan ate V S to the production of . .

a p erm an ent red color .

The numb er of mils of the l att er mul t i p li ed by is sub 2

tracted from 5 mils (the qu anti ty of t enth norm al silver

0 -

nitrate V S added) and the di ffer enc e is the quan ti ty of the

. .

l att er which r eac t ed with the phos phoric acid .

E ach mil of t en t h n orm al silv er nitrat e V S r ep r es ents

-
. .

gm of H3PO .
4 .

N OTE S The n eutrali ation of phos p h oric aci d by potas

. z

sium hydroxi d in the presence of ph enol ph thal ein is repre

s ented by the equ ation

H3PO 4 2 KOH K zHPO 4 2 112 0 .

An xcess of K O H mus t be avoided as this r eacts with silver

e ,

nitrat e .

The reaction b etw een silver nitrat e and the dipotassic

p hosph at e is us ually r ep r es ent ed by the following equ ation ,

 AN AL YSI S BY PRE C P I ITATI ON 129

which for the purposes

, of thi s assay ,
may be considered suf

fi ci ently accurat e

K 2 HPO 4 A
3 gN O 3 Ag3 PO 4 2 KN 0 3 HN O g .

N ormal silver phosphate b eing pr ecipitat ed .

It is very probabl e that the su pern atant liquid in this reac

tion contains also some free phosphoric acid but that s eems ,

to be imm aterial .

3K 2 HP O 4 l OAgN O 3
‘ ‘
2 Ag3P O 4 OK N O g H3PO 4 .

The zinc oxid is add ed in this assay for the purpose of

n eutralizing the acid or acids lib erated in the int eraction .

This is n ec ess ary b ecaus e silver phos phat e (Ag PO ) is solubl e g 4

in dilute nitric and ph osphoric acids Too l arge an exc ess .

of zinc oxid must be avoided as it acts u p on silver nitrat e , ,

p r eci p it ating Ag 0 if l e
gft in cont act too l ong It is a d vis abl e .

for this reason to filter as soon as possibl e af t er the addition

of zinc oxid .

If as is claimedf that p hosphoric acid is lib erat ed by the

,
l <

int eraction of dipotassic ph osphat e and silver nitrat e the ,

zinc oxid will form with i t zinc phosphat e which in a n eutral

,

solution is transp os ed by the silver ni trate into sil er phos phat e v ,

an d zinc nitrat e thus conv erting all of the phosphoric aci d

,

into Ag PO 3 4 .

Z inc oxid app ears to be the most suitabl e substanc e avail

abl e for this n eutr aliz ation b ec aus e its action up on silv er nitrat e
,

is very sl ow and insignific ant if not in l arge exc ess , .

Assay of S odium Pho sphate This may be p erformed by .

the s am e m etho d .

Into a 00 mil gradu at ed fl ask introduc e an accurat ely

1 -
,

weigh ed qu antity of the s alt (about dissolve it in

J R si J
. a n, . A C S
. . .
, Vol .
3 3, p a g e 1 1 03 .
130 THE E S SE N T ALS OF I VOLU ME TRI C AN AL S S Y I
10 mils of distill ed water add 50 mils of t enth normal silver ,
—

nitrat e V S and shake well Then add gradu ally pur e zinc
. . .

oxi d in small p ortions until the liquid is n eu tral to litmus,

.

D ilu t e the mix t ure with distill ed w at er to m ak e 0 0 mils 1 .

Shak e th or oughly and filt er through a dry fil t er Rej ec t the .

firs t 2 0 mil s of fil trat e Coll ect 50 mils add t o it 2 mils of

.
,

ni tric acid and 2 mils of ammonio ferric sul ph at e T S and -

. .

ti trate wi th ten t h n ormal p otassium sul ph ocyanat e V S to

- . .

the pr oduc t ion of a p erm an ent ed c ol or r .

E ach mil of t en t h norm al silver ni trat e V S us ed corr e

-
. .

S onds to
p 35 gm of N a HP O T he ca lcul at ions
. a z 4 . re

as giv en in pr ec edi ng assay .

Assay of Hyp opho sphi t es This is p erform ed by the m et ho d .

jus t described for ph osphoric acid and sodium phosphat e .

T he hyp o p hosp hi t es b eing first oxidiz ed to p hosp h at s D is e .

solve about 1 gm (accurately w eighed) of the sal t in 0 mils

. 1

of distill ed water and 0 mils of nitric acid and evaporate 1

the solution to dryn ess on a wat er b ath T h en add 5 mils

’
-
.
,

of ni tric aci d and ag ain evap orat e it to dryn ess on a w at er

b ath D issolve the residu e in 0 mils of dis till ed w at er add a

. 2 ,

dr op of p h en ol phthal ein T S and su ffi ci ent speci al potassi um ,

hydrox i d T S (free from chlori ds) to produc e a p al e p ink

. .

col or and th en dilu t e the mix ture to exac t ly 0 mi ls with

, 10 ,

dis till ed water Transfer 0 mils of this s olution to a 00

. 1 1

mil flask add 5 mils of t enth normal silv r ni trate V S and

, 0 -
e . .

proc eed from this p oint as directed under assay of sodium

phosphate .

E ach mil of t enth norm al silver nitrat e V S corr esponds to

-
. .

gm of Ca(PH 0 .
2 2 )2 ;
gm of K PH O .
z z;

gm . of N aPH2 0 2 .
132 THE E SSE N TI AL S O F V OL UME TRI C AN AL YSI S
of silver h alid is form ed un t il aft er all of the cyanog en pres ent
has b een conv er t ed in t o a doubl e s al t This fact is t ak en .

adv an t ag e of in the p r oc ess es fo hy dr ocy anic aci d and alkali r

cyanid in which p otass um odid is empl oy ed as in dicator

1 l

in the p r es enc e of amm onia w at er The l att er prevents the .

precip itat ion of silv er cyani ds and t h us allows the silver iodid
to pr ecipitat e al on e .

1 mil of AgN 0 3 gm CN ; .

gm HCN ; .

gm N aCN ;
.

gm K CN
. .

T itrati o n with S tandar d S ilver S ol ution U sing Chromate ,

In di cator Vi elhaber s M etho d

—
T his m etho d is es peci ally
’
.

r ecomm ended for th assay of w eak s ol ut i ons c on taining

e

hydr ocyani c acid as bi tter alm on d oil bi t ter almon d water

, , .

ch erry l aur el water etc bu t i t may also be em ployed for

,
.
,

alk alin e c yani ds .

A sufli ci en t qu antity of an aqu eous su p ensi on of m ag s

nesium hy droxi d I to m ak e the solution o p aqu e and distinc t ly

><
‘

alk alin e is add ed ; this is foll ow ed by a few drops of pot assium

chromat e in dic ator and t hen the 5 silver ni trat e deliv er ed

into the mixtur e from a burett e un t il a p erm an ent ed ti n t r

ap p ears as in the t itr ation of h aloid s alts

,
The m et ho d is .

a v ery s atisfactory on e if chlorids ar e abs ent .

The r eactions in t his m eth od a e the s am e as in the for e r

goin g but the end reac t i on (the pro duc t ion of silver chromat e)
,
-

do es no t occur un t il the doubl e cyani d is comp l et ely decom

C l i d m g s i tri t r t d wi th w t r
a c ne a ne a u a e a e .
 ANAL S S BY PRE C P TA Y I I I TI ON 133

p os ed a
,t which p oint the addition of a noth er drop o f silv er
solution reacts with the chrom ate and produc es the red p e r

cipi tate (silver chromat e) .

The equ ations are as follows : Sodium is us ed in the

equ ations in st ead of m agn esium in ord er to m ak e the exp l an a

tion cl ear er .

()
a 2 N aCN + AgN 0 3 AgCN , N aC N N aN 0 3 (
2 H C N );
b
() AgCN , N aCN AgN 0 3 2 AgCN N aN O g .

Th es e qu ations show th at it r equir es two mol ecul es of

e

silv er nitrat e to compl et ely pr ecipitat e t wo m ol ecul es of cyani d .

gms of AgN O is equival ent to

. gms of HCN g .
,

whil e by L i ebig s m ethod gms of AgN 0 is equival en t

’
.
3

to gms of HCN . .

1
N
mil AgN 0 3 gm CN ; .

i B

gm HCN ; .

gm N aCN ; .

gm K CN . .

E x ample gms of the diluted acid is mixed with

. .
,

enough w at er and m agn esi a t o m ak e an o aqu e mixtur e of

p
ab ou t 1 0 mils Add to this 2 or 3 dro p s of p otassium chr om at e
.

solution and th en from a bur ette deliver the decin orm al silver
nitrate V S until a red tint is produced which does not dis
. .

app ear by sh aking .

This method i s exemplifi ed in the U S F I X A ssay of Oi l

'

. . .

f
o Bi tter A lmon ds .

T itration with S tandard S ilv er S ol utio n U sing P otassi um ,

I odi d as I ndi cator T his m etho d e m pl oyed in the A s ay of.

,
s

Di lute H yd o yani c A ci d U S P I X is c on duct ed as f oll ows

r c ,
. . .
,

Into a 00 mil flask c ontaining 5 mils of distill ed water

1 -
2

and 5 mils of potassium hy droxid T S which has b een tared . .

, ,
134 THE E SSE N T AL S OF I VOLUME TRI C AN ALY SI S

p our about 5 mils of the aci d an d w eigh it accur at e

,ly T h e n .
'

add 3 dr ops of potassium io di d T S and titr ate wi t h t en t h .

norm al silver nitrate V S to the production of a sligh t pe

. . r

manent precipitate .

E ach mi ] of t enth norm al silver ni t rate V S us ed corr e

-
. .
,

s onds to gm of HCN T he slight pr ecipit at e which

p . .

is produced in this ass ay and which m arks the end reac tion ,

is silver io did (AgI ) .

The precipi t ate of silver iodi d do es not appear until the

cyanid has b een entirely converted into the doubl e salt

t on of P otassium Cyani d
E s imati O ne gm .

of potassium cy anid is dissolved in su ffici ent distill ed w ater

t o m ake 1 00 mils th en , mils of this solution mixed wi th
5 mils of ammoni a w at er and 3 dr op s of p otassium i odid

solu tion are titrated with AgN O s V S . . ntil

u the app ea a r nce
of a p ermanent preci pitate . Ea ch mil indic at es 2
p er c ent .

N
gm
C

1 mil of 10
AgN O g . K CN .

E stimati on of S il v er S al ts

Solubl e silver salts may be est im ated by direct titration

with standard so dium chlorid the proc ess b eing exactly the ,

convers e of the precip itation m etho ds for halogens The stand .

ard sodium chl ori d solution is added t o the solution of the

silver salt until precipitation c eas es ; or the titration may be

done in the pres ence of chrom ate indicator the end point ,
-

b eing th en kn own to be r each ed wh en the red color of the

,

silver chrom ate disappears The first of th ese m etho ds is im

.

pr actic abl e too

, much tim e b eing c onsum ed in w ai t ing for

the preci p itate t o s et tl e so as to ren der the su p ern atant liquid

 136 THE E SSE N T AL S OF I VOL UME TRI C AN AL S S Y I
h eated suffi ci ently to drive off all traces of nitrous acid The .

solu tion is th en dilut ed with abou t mils of dis till ed w ater 1 00

and ass ay ed by on e of th m et h ods describ ed un der the ass ay

e

of silv er nitrat e The sulphocy anat e m etho d is the pr ef err d

. e

one .

Assay of bout 0 5 gm is dissolved in 3

S i l ver O xi d . A . .

mils of ni tric acid and 5 mils of distill ed water 2 mils of ferric

0 ,

ammonium sul ph at e T S are added and the mixtur e ti tr at d

. . e

with a s tan dard sul ph ocyanate solu tion .

Assay of M ercuri c S alts by Di r ect Titr ati o n wi th S ulpho

cyanat e S o luti o n This m et h od is ap p lic abl e to most m ercuri c
.

compoun ds in the abs enc e of h alog ens (esp eci ally chlorin )
( .

It consis t s in titrating the m ercuric salt in the pr esence of

nitric acid and a l arge volum e of distill ed water with a standard
sulphocyanat e solution .

F erric ammonium sulph at e is us ed as indic ator The ass ay .

is carried ou t as foll ows :

Assay of M ercuri c Oxi d

,
D issolve an accur at ely w eigh ed
.

quan t i ty (about 0 5 gm ) of the m ercuric oxid in 0 mils of

. . 1

dis t ill ed w at er and 5 mils of nitric aci d Th en fur t h er dil ut e .

the soluti on wi t h 50 mils of dis t ill ed w at er

1 T o this add . 2

mils of ferric amm onium sul ph at e T S and ti trat e with t en th

—
.

norm al potassium sul phocyan at e V S to the produc tion of a . .

p erm an en t y ellowish red c olor E ach mil of the sulphocyanate

—
.

solution used corr esponds to gm of HgO . .

HgO 2 HN 0 3 2 K CN S Hg(CN S) 2 2 KN 0 3 + H2 0 .

This proc ess whil e not strictly a precipitation analysis is for

, ,

the s ak e of conveni enc e inclu ded und er this h eading The .

m ercuric sulphocyanate form ed in the proc ess is so sparingly

solubl e in water that if a high dilution of the salt b eing titrated
is not m ade a h eavy white precipitate woul d be produced
,
.
 TA B L E or SU B S TA N C E S E STI M A TE D BY P RE C I PI TAT I O N
F orm u l a . F ac t or .
*

Acid hyd , r bro om i c AgN 0 3

hyd r oc hlo ri c AgN O 3 47

hydrocyanl c HC N AgN O 3
19
h
w i t ou t
d
i n i c a t or

HC N AgN O 3
I ;
h
wi t c ro m at e h
d
i n i c a t or

HC N AgN O 3
I S
h dd
wi t i o i
d
i n i c a t or

r
hyd iodi c AgN 0 3

A llyl-i so - thi ocyan a e t

Amm oni um b om id r
chlo i d r
iodi d
C alci um b om id r
chlo i d r
rr s r
Fe o u b om i d
iodi d
Lti hi um b omi d r
t ss
Po a i um b om id r
chlo i d r
cyan id

KC N AgN O 3
1 ;
h h
wi t c r om at e
d
i n i c a to r

KCN AgN O 3
16
hd d d
wi t i o i
i n i c a t or

h
T i s i s th e c oe ffic i en t b y w hi h h mb c t e nu er o f cc u se d of t he d i ml
ec n o r a so u l
i m pl d b i y pp b
.

t on i s t o b e m u l t 1 p 11e d i n or to o ta n the q u an t i t of u re su i
s t an c e n t he
sa e an a ly zed It re p er
h w i gh
r es en ts t f e e t o b
t h e s u s t an ce i i d by
p ta te cc
i
re c 1
l
. .

of t h e dec m o r m al so ut o n .

Q
138 THE E SSE N TIAL S O F VO L UME TRI C AN A L YS I S
TAB LE O F SU B STAN C E S ES TI MATE D R
BY P E C I PI TATI O N
C onti nued

F o rm u l a . F ac t or .
*

Pota ssi um iodi d AgN 0 3

s t
ulp hocyan a e

vr
Si l e (metalli c) N aC l or

KSCN

r
nit ate

o xi d

Sodi um b r mid
o AgN O 3

chlo ri d
iodi d
r
S t onti um b omi d r
i odid
r
Z i n c b omi d
chlo i dr
i odid
14 0 THE E SSENTI AL S oF VOL UM ETRI C A N ALYS IS
from a bur ett e until it is no longer dec oloriz ed th iron salt
, ,
e

is kn o wn to be compl et ely oxidiz ed wh en th p erm angan at e ,

e

is no long er reduc ed The r eaction is as foll ows

.

I O FC O 2 KMII O 4 = 5F 6 2 0 3 Q MI I O K zo
d
.
'

F err ous ox rd F er ri c ox i

The oxid at ion of ferrous oxid by p ot assium dic hr om at e

is shown by the followin g equation :

OFC O l K 2 C1 2 0 7
“ “ '

3F 6 2 0 3 GI Q O 3 + K 2 0
’

As b efor e s t at ed an oxid ation is always accomp ani ed by

,

a r eduction the oxi dizing ag ent b eing its elf r educ ed in the
,

op eration As sho wn in the abov e equ ati ons the mangamc

.
,

comp oun d is r educ ed to a m anganous and the chromic to ,

a c h omous
r whi l e the f errous s alt is oxidiz ed to a ferric
,

con dition .

In the sam e way any substanc e whi ch r eadily yi elds oxygen

in definit e quantity or is susc eptibl e of an equival ent acti on
which involv es its r eduction to a l ow er quantival enc e may ,

be estim at ed by asc er t aining how much of a r educin g ag ent

of kno wn pow er is r equired for its compl et e r eduction .

E x ampl The avai labl e chlorin in bl eaching powd er may

e.

be accurat ely asc ert ain ed by tr eating it wi t h a st and ard solu

ti on of ars enous oxid and from the volum e of the solution
,

required for the comp l et e reduc tion of the chl orin the qu antity ,

of the l at t er p r es ent is foun d or in oth er w ords , from the .

quan t ity of ars en ous oxid (AS O ) oxidiz ed to ars enic oxidQ 3 ,

(A s
o O ) t
5he w eight of the chlorin p r es ent is asc ert ain ed .

The p rin cip l e subst anc es which are us ed as oxidizin g

ag ents in volum etric an aly s is are potassium p erm anganat e
, ,

potassium dichr omate and iodin The l atter c ontains no .

oxyg en but it abstracts hydrog en from accomp anyi ng wat er

,

and lib erat es the oxyg en which do es the oxidizing h enc e iodin ,

is known as an in dir ect oxidizing ag ent The oth er two .

 AN A L YS I S BY O XI DATI O N AN D R E D U C TI O N 14 1

contain availabl e oxyg en whi ch t h ey r eadily give up when

brought in c ontac t wi t h an oxi diz abl e subs tanc e .

The p rincip al r educing ag ents or deoxi diz ers which are

us ed in v ol um etric an alysis a e s odium t hi osul phat e sul r , ,

p hu rous acid o xalic acid ars enous oxid s tannous chlorid

, , , ,

ferrous oxid hydriodi c acid hydrosulp h uric acid m etallic

, , ,

zin c and m agn esium

, .

P reparat i o n of Dec in ormal Po tassi um Pe rm anganate

( KMn O 4
2 =
10
VS . .
= gms in . 1 lit er) . Abso

lutely p ur e p ot assium p erm ang an at e c ann ot be obt ain ed ,

th er efore the p r ep arat ion of a d ecin ormal s ol ution of t his
s alt cannot be effect ed by simply dissolving the r equisit e
p roportion o f th e mol ecul ar w eight in the w at er T he p r es enc e .

of oxidiz abl e m att er in the wat er us ed the con tact of dust ,

and exposur e to light have a t en dency to d ecompos e the

,

s alt and h enc e w eak en the stand ard solution It is th er efor e .

advis abl e to use b oiling distill ed w at er and to p r es erv e the solu ,

tion in amb er gl ass bottl es provid ed with ground gl ass stopp ers
,
—
.

It will th en r etain its strength for s ev eral weeks but should

,

n ev erth el ess be ch eck ed by titration imm edi at ely b efore usin g .

It is not n ec ess ary and it is usually un desirabl e to mak e

, ,

the solu t ion an ex act d ecin orm al on e It is preferabl e to .

fix the t it er of the solu t i on and empl oy it as it is .

P l ac e gms of pure crystalliz ed p otassi um p erman

.

an at e in a fl ask add 0 0 0 mils of di st ill ed w at er and b oil

1
g , ,

until the crystals are diss olv ed ; put a plug of absorb ent
cotton in the mouth of the flask and set i t asi de for two days
so that any susp end ed m att er may d ep osi t Af ter the l aps e .

of this time pour off the cl ear solution into a gl ass stopp ered -

bottl e and wh en wanted for use standardiz e by eith er of the

,

following m ethods
14 2 THE E SSE N TIAL S O F VO LU ME TRI C AN A L YSI S
S ta n d a r d i z a ti on by hin ann eal ed
M ea n s of I r on . T
binding wire fr ee from rust is one of the pur est forms of iron *
-
, , .

gm of such iron is pl ac ed in a flask which is provid ed

.

with a cork thr ough which a pi ec e of gl ass tubing p ass es ,

to the top of whi ch a pi ec e of rubb er tubing is attach ed ,

whi ch has a vertical slit about one inch long in its sid e and ,

which is closed at its upp er end by a pi ec e of gl ass rod (this

arrang em ent is known as the Bun s en (S ee Fi g .

D ilut ed sulph uric acid is add ed and g entl e h eat appli ed .

The iron dissolv es and the s t eam and lib erat ed hydrog en esc ap e
through the slit und er sligh t press ur e The air is thus pre
‘
.

vent ed from entering and the ferrous sol ution prot ect ed from
oxidation .

A b ett er form of app aratus in which to dissolv e the iron

an d avoid oxid ation through admission

of air is shown in Fig 4 2 A 00 mil . . 1 -

flask is fi tted with a rubb er stopp er and

a sh ap ed glass tub e ; in t o this
fl as k is pl aced 2 0 mils of dilu ted sulphuric
acid and th en or 3 crystals of 2

FI G .
41 . FI G .
4 2 .

pure sodium c arbon at e ; this c aus es an evolution of c arbon

dioxi d whi ch exp els the ai from flask The r gm of iron . .

This contai n s er cen

p t of i r on,
144 THE E S SE N TIAL S O F VO LUM E TRI C AN A Y S S L I
which s ol uti on is dil ut ed pr vi ously b oil ed in ord r to drive
the e e

off any diss olv ed fr ee oxyg en .

1 0 F eSO 4 2 K Mn O 4 8H2 SO 4
I 6 06
100 ) 3 .

N
gm s .
gm s . or 1 00 0 mil s5 VS . .

SFC Q S O
( 4) 3 K Q SO 4 2 MI I S O 4 + 8H2 0 .

T his equat i on ,
etc .
, shows that ch mil
ea of p er man
gan ate r epres ents 5582 gm of m etallic iron
. .

S t a n d a r d i z a ti o n b y gm
M e a n s of Ox a li c A ci d . .

of the pure crystalliz ed acid is w eigh ed (or mils of deci 20

n orm al oxalic acid car efully m easur d) and pl ac d in a flask e e

wi t h 3 mils of sul phuric acid C P and dis t ill ed w at er to m ak e . .

1 00 mils The solution is warm ed t o 85 C and the p erm an

.
°
.

ga n a te solu t ion d eliver ed in from a bur ett e .

The action is in t his c as e l ess decisiv e and r ap i d t h an in

the t i t rat i on wi t h ir on an d m ore c ar e sh oul d be us ed
,
The .

col or dis app ears sl owly at firs t bu t aft erw ards m ore rapi dly , .

N ot e the numb er of mils of the p erm angan at e s olu t ion

used and th en dilute the rem ainder so that equ al volum es
,

of it and of decinorm al oxalic acid solution will exactly corre

sp ond .

E x ample ssuming that

. A mils of the p erm anganate
solu tion are r equired to pro duc e a p erm an ent pink t in t in the
ab ove t es t t h en the p erm angan at e solu t i on mus t be dilut ed with
,

distill ed w at er in the p r op or t ion of 8 5 mils of the p erm angan at e 1 .

solution and 5 mils of wat er or 850 mils to 50 mils

1 .
,
1 1 .

After diluti on a new tri al shoul d be m ade in which 50 ,

mils of the diluted p erm anganate solution shoul d requir e

N
exactly 50 mils of 1 oxalic acid V S
9
. .
 L I
AN A Y S S BY O XI DA TI O N AN D R E D UCTIO N 14 5

The reac t ion b etw een p otassium p erm anganat e and oxalic
aci d is ill us t r at ed by the following equ at ion :

2 K MII O 4 + 5 (H2 C2 0 4 . 2 11 2 0 ) + 3H2 80 4

K Q SO 4 2 MII SO 4 I O CO 2 I 8H2 0 .

S t a n d a r d i z a ti o n by th e his I od o m e tr i c M eth o d . T
m ethod whi ch was propos ed by V olhard is the most accurate
, ,

and r ap i d for the s t an dar diz ati on p erm angan at e I t is b as ed .

up on the fact t hat p otassium p ermangan ate r eacts wi th p otas

sium i odid in soluti ons acidul ated with eith er hydrochloric or
s ulphuric acid and lib erat es an equival ent quantity of iodin
, ,

which may be es t imat ed by standard solution of sodium

thi osulphat e The r eactions are illustrat ed by the equations
.

()
a 2 KM n O 4 8HzSO 4 I oK I

2 MII S O 4 6K Q S O 4 8H2 0 1
5 2;

b
\) 12 2 (N a2 S2 0 3 511 2 0 ) ZN EI N a2 S 4 0 6 IO HQ O .

Thus i t is s een that 2 KMnO gms ) containing 4 .

fiv e at oms of avail abl e oxyg en has the p ow er of lib erat ing

, ,

i t s equival ent of io din , i e atoms or gms (se

. .
,
10 . e

equ ati on a) and t h at gms of so dium thi osulphat e .

will r educ e gms of iodi n (see equati on b) Henc e

. .

1 00 0 m1ls
19
so
of dium t hiosul ph at e (containing gms ) .

will reduce and t h erefore be equival en t to

, gms of .

iodin which in turn r epres en t s

, gms of po tassium .

p erm ang an at e T h er efor .e mil of t he

I
thiosul
1 p h at e repre
G

sents gm of iodin and . gm of potassium .

p erm ang an at e which l att

, er is the qu antity of pot a ssium p er

N
manganate pres ent in I mil of its 1; V S . .
 Theproc ess is con duc t ed as follows Into a 2 00 mil flask : -

pl ace about gm of po tassium iodi d and 1 0 mi ls of dilu ted

.

sulphuric aci d add to this (sl owly from a bur ett e) exac tly
,

1 0 mils of the perm angan at e solu t i on to be s tan dardi zed and

dilu t e the mixture (which is brown in c ol or because of the ,

liberat ed iodi n ) wi th dis til l ed wat er to about 50 mils Th en I .

sl owly ti trat e (wi th constan t s t irrin g) wi th an accurat ely s tan d

N
a di ed
r z
19
so dium thi os u l p hat e un t l the color of the solu t on l i

is a faint yell ow th en add a few dr ops of starch solu ti on and

,

continu e the ti t rati on un t il the col or is discharged N ote the .

n umber of mils consum ed an d dilu t e the p erm angana t e wi th

di til l ed wat er so that equal volum es of the two solu ti ons

s

correspond to each oth er .

E x ample If 1 3 mils of the thiosul phat e solu tion w ere

.

requir ed th en each ,0 mil s of the permangana t e solution mus t

1

be dilu ted to 3 mils I .

S ta n d a r d i z a t i o n w i th F er r o us A m m on i um S u lp h a te

(hf ohr s
’
gms o f t h s
(N II 4 ) Q S O 4
i -6 HQ O ) . .

salt contain gms of ir on gms c on tain .gm of . .

iron ) .
g ms of t h e sal t a e accurat ely w eigh ed out an d
. r

dis solved in sufli ci ent rec ently bo i l ed di t ill ed w ater to m ak e s

2 50 mils Fi f ty mils of thi s solu tion contain ing

.
gm o f .

iron are transferred to a small flask 1 0 mi ls of dilu t ed sul ,

h uri c aci d add ed an d t h en the perman gan at e solu tion to

p ,

be stan dardized is run in slowly un ti l a fain t p ink ish tiri t

ap pears Whatever number of mils is c onsum ed th 1 num ber
.

represen ts g m of ir on and mus t be dil ut ed t o

. m il
, s
to make the solution exac t ly decinormal .

Volum t i c A nal yse by M eans of P otassi um P ermanganate

e r s

Wh en p otassium permang anat e soluti on is added to a solu

ti on of any r eadil y oxi di zabl e subs tan c e s trongly acidu lated

with sulphuric acid it un dergoes reducti on as shown in the

, ,
14 8 THE E SSE N TIAL S O F VO LUME TRI C AN A Y S S L I
in contact wi th a ferrous salt o oth er oxi diz abl e substanc e r ,

it is dec ompos ed and decoloriz ed Henc e wh en t itrat ing wi t h .

a st and ard s olu t ion of this s al t it is dec oloriz ed so l ong as an

oxi diz abl e substanc e is pr es ent As soon how ev er as the .

, ,

oxi dation is c ompl et ed the st an dar d solu t i on r et ains its col or

wh en add ed to the substanc e and the firs t app earanc e of a ,

faint ed col or is the end r eaction and the oxidation is kn own

r -
,

to be c omp l et ed .

In titrat ing wi th p otassium p erm angan ate it m ust be

r ememb er ed that exc ess of free acid (preferably sulphuric)
shoul d always be pres ent in the sol uti on ti trat ed in or der ,

to k eep the r es ulting m ang ano us an d m ang anic oxids in solu

ti on ; th es e forming a dens e brown precipitate would m ak e
, ,

i t difli cult if not quite im p ossibl e to r ec ogniz e the pinkish

c ol or of the end r eac t i on Sulphuric acid al on e if in l arg e
-
.
,

exc ess has a r educing eff ect up on p otassium p erm ang an at e

, .

N i tric and hy drochloric aci ds a e pr ej udici al and shoul d r

be av oi ded; th ey are h ow ev er frequ ently p r es ent in s al t s

, ,
.

whi ch are to be an alyz ed and in such ev ent sh ould be ,

remov ed by converting th em into s ulphate By ad ding a .

small exc ess of sulp huric acid and ap p ly ing h eat until hydro ,

chloric acid or nitrous vapors a e no long er evolv ed the r ,

chlorid or the ni trat e is conv ert ed into sulphat e and the ,

del et erious eff ect of th eir p r es enc e ov erc om e Hydrochl oric .

aci d un l ess p r es ent in v ery sm all qu antiti es

,
and the ti t r a ,

t ion con duct ed at a low t emp erat ure will vi t i at e the analysis ,

t hrough i t s action up on the p erm angan at e wh ereby chl orin

is lib erat ed t hu s
*
,

K Mn O 4 + 8HC l = K Cl + Mn C12 + 4 H2 0 5c1 .

* Thi s d ecom p o siti f th p rm g

on o e by hydr hl ri
e anid i an ate oc o c ac s due
to th p r s
e e en ce o f f rri s lt w hi h l tt r s m s t
e c a ,
tc t lyti lly f
a e ee o ac ca a ca ,
o r o x ali c

aci d may be accu a e r t ly ti t r t d with p rm g t v i th p r s

a e e an an a e e en n e e en ce of

r
hyd ochlo i c ac r id,
no hl r i
c b i g giv
o n ff T h s th d
e n m p siti
en o . u e eco o on of

r
t he p e m angan at i
e t d
s no t th hydr
ue hl ri
o id le oc o c ac a one.
 AN AL S S BY O X D A Y I I TI ON AN D RE D U CT I O N 14 9

very c onv enient way of obvi ating the irr egul ari t ies due
A
to the pres enc e of hydrochl oric acid is to add a few grams '

of manganous sulphat e to the s ol uti on b efor t i trat ing i t e .

M ercuric sulphate i and m agn esium sulph at e may also

be us ed with s atisfactory r esults .

Pot assium p erm ang an at e b eing so r eadily d ecompos ed by ,

contact with organic m att er should be prot ect ed from such ,

con tact It sh ould n ever be filt ered through p ap er (gl ass

.

wool or guncotton may be us ed ) nor should it be us ed in ,

a Mohr s bur ett e or in any oth er ap p ar atus in which it is

’

in contact with rubb er or cork Furth ermore all substanc es .

,

of an oxidizing or r educing n atur e aside from that b eing ,

an alyz ed must be exclud ed from the solution

,
Among such .

s ubstanc es may be m en ti on ed hydri odic acid sulphuret ed ,

hydrog en ni trous acid and the low er oxids of nitrog en phos

, ,

p h oro us and hypophosphorous acids thiosulphuric sulphurous , , ,

and all the oth er acids of sulph ur exc ep t sulphuric also ous ,

s alts and the m et allic suboxids and p eroxids .

Burett es and oth er app aratus w hich h av e b een us ed for

K ssl r
e e an d Z im m e m ann r s gg st si g
u e u n 20 mil s of a s l ti
o u on of man
g ano u s s lph tu a e (2 00 gm s p er . lit r ) e .

I C ady R andd ig r (I A ue C S X
e I X 57 5) . . l d d fr m th f ll wi g
. .
, ,
co n c u e o e o o n

g r l pri ipl s th t it i p ssi bl t tit r i r wi th p rm g

ene a nc e a s o e o i h ate on e an an ate n t e

p r s
e e nce o f h ydr h l r i i d i
oc f o ss
c ac f m r r i s l p h
an exce b d d d t o e cu c u at e e a e o

th s l ti
e o u on M r ri h li ds i s l i
. e cu c i i
a n r m ly s light
o ut o n t on z e to an e x t e e e x ten ,

whi l e h m r ri s l s f
t e e cu yc i d s
a t r o d i ly i i
o x ac d si mp are ds f ea on z e ,
n ce co o un o

s light i i ti on z a lw ys r s lt wh
on a a h ir e u stit t i s m ; m r ri en t e con uen on ee t e cu c

h li ds
a are alw ys p r d ad wh o m r ri s l
uce f en a y i d i dd de cu c a t o an o x ac s a e to a
s l ti
o u t
o n co n aI nI ng h l g i s T h r
a o en f r w h on m .r r i s lp h s l t
e e o ei en e cu c u ate o u on

an d hydr hl ri oc id o m i d i i ti
c ac are f b h xe ,rs d h m r ri
on z a on o ot o cc u ,
an t e e cu c

io sn i
un te wi h h hl ri i
t t s d p r d m r ri hl rid whi h i ly
e c o n on an o uce e cu c c o c s on

v er
y s li g ht ly i i d I t h
on z e p r s. f n l rg e ss f m
e en ce o r r i s lp h t a a e e x ce o e cu c u a e,

th m r ri i
e e cu s r s lti g fr m i di ss i i dim i i sh h i i ti f
c on e u n o ts oc at on n t e on z a on o

th m r
e ri hl rid ti l i t i p r ti lly i l T h s
e cu c c o un s hl ri i
ac s wi ll b
ca n . u no c o n on e

p r s
e en t i t h
n s l ti t i d
e o u don m p si ti
o n uce f th p rm g eco t o on o e e an an a e .
150 THE E SSE N TIAL S O F VO L UME TRI C ANAL YSI S
p ermanganat e should be empti ed and rins ed imm ediat ely
,

aft er use and any m ang anic oxi d whi ch may be adh ering
,

to the gl ass sh oul d be r emov ed by m eans of hydrochl oric

acid and boil ed w at er .

N ot only oxi diz abl e s ubst anc es but r educibl e substanc es

may be estimat ed by m eans of p otassium p erm angan at e .

In the estimation of oxidiz abl e substanc es the standard

potassium p erm anganat e is added dir ectly to the acid ul at ed
solution of the substanc e b eing analyz ed The comp l etion of .

the oxid ati on b eing th en kn own by t h e ap p earanc e of a faint

pinkish tint This is the direct metho d
. .

In the estimat ion of r educibl e substanc es oxidizing

substanc es) the i ndi rect or the resi dual method is employed .

In this an acc urat ely w eigh ed 0 1 m easured quantity of

the substanc e is brought tog eth er with an exc ess of a third
subs t anc e having r educing pow er and which is simil arly ,

eff ect ed by the p erm ang an at e an d by the subst anc e an alyz ed .

Aft er comp l eti on of the r eac t i on the exc ess of the r educing
substance is foun d by titrat ion with stan dard p erm anganat e .

The diff er enc e b etw een the qu antity so found and th at origin ally
add ed gives the qu anti t y which r eact ed with the s alt und er

an alysis and from this the c alcul ation is m ad e

, .

On the U se of r
E m p i i cal Pe rmanganate t
Solu i on s .

A . If
t ndardiz ation of the solution i s don e by m eans
the s a
of iron as d escrib ed on p age 1 4 2
, gm of iron wir e,( p
re re .

sentin g gm of pure iron ) will requir e

. mils of the
p erm a ng an at e solution if the l at t er is ex ac t ly decinorm al .

I f l ess than this qu antity of s olution is us ed (say mils)

it indic at es that the solu t ion is stronger than decinormal ,

and m ay ith er be diluted so that each 1 7 5 mils will m easur e

e .

or it may be us ed as it is This l atter is in most cas es

.
152 THE E S SE N TI AL S OF VO LUME TRI C AN AL Y SI S

strength of the form er s olu tion is t herefore as compar ed

with a decinormal solu t ion .

In titrating with this solution the numb er of mils consum ed

8
7 4 1
are to be multi p li ed by and t h en by the tru e decinorm al
75 1 0

factor for the substanc e b eing analyz ed .

E x ampl F orty mils of the s oluti on are consum ed

e . .

I n the case of f errous sulphate the deci

normal factor the w eight of f er ous sul ph at e r epres ented r

by 1 mil of a tru e decinorm al s olution) is 8

5 9 gm 00 1 1 .

gm . gm .

I n the case of ox ali c aci d (H2 C 2 0 4 ,

2 112 0 the d eci
norm al factor is gm .

1 7 84
gm . gm .

1 750

I n the case o f hydrogen di ox i d (112 0 2 :

the decinorm al
factor is gm .

1 7 84
><0 . 00 1 7 gm .
= 0 06
93 . gm .

I 75 0

C .If the standardizat ion is don e by m eans of oxalic acid ,

as describ ed on p ag e 1 4 4 in which mils of a strictly d eci

, 10

norm al oxalic acid s olution are t itrated with the p erm angan ate
solu tion which is b eing standardiz ed exac t ly 0 mils of the , 1 .

l att er will be consum ed if i t is of decinorm al s tr ength If .

in the tr ial how ever it is foun d that only

, , mils a e con r

sum ed it indicates that the solution is s tronger than decinorm al ;

1
2
i t s str ength bein g express ed by 62 If on the other h and , ,
9
 AN AL YSI S BY O XI DATI ON AN D RE D U CTI ON 153

more than 0 mils of the solution are consum ed (say

1 m ils)
0 10
the solution is b elow dec inorm al str ength n am ely , , '

10 4
In using a solution of the firs t str eng t h the numb er of mils
0 10
of i t consum ed i n any t i trati on i s to be multi pl ed by and i
‘

96
then by the decinorm al factor for the substance examined .

In the c as e of the w eaker solution the num b er of mils con

sum ed i s multiplied by 3 and th en by the d ecinorm al factor
3
for the substanc e b eing an alyz ed .

E x am ples . F errous sul

p hate (FeSO 4 = I
5 1 89) is titrat ed
with the stronger so lution , 4 0 mils of the l atter b eing consum ed .

1 00
40 X
6
gm .
= 0 62 8. gm .

Ox ali c aci d (H2 C2 0 4 2 H2 0 40 mils are consumed .

OO

6
X O 0 0 63
. gm .
=0 . 2 60 gm .

H ydrogen di ox i d H
( 20 2 =
40 mils are consum ed .

1 00

6 gm .
=0 0 0
7 3
. gm .

D If the ch ecking of the p erm anganat e solution is done

.

by the io dometric m ethod (page 1 4 5) and it is found th at

1 0 mils of the p erm ang an at e r equir es the use of 3 mils of 1

decinorm al thiosulph at e solution the tit er of the solution

,

is expressed with reference to d ecinorm al as g In using .

a solution of this s tr ength the numb er of mils of it consum ed

,

in an a a n lysis is multiplied by 3 and th en by the d ecinorm al

factor for the subs t anc e analyz ed .
154 THE E SSE N TIALS OF V OL U ME TRI C AN AL S S Y I

TYPI CAL AN A LY S E S W I TH P E RMAN G AN ATE

A D i rect Ti trati ons

a . rous S ulphate
E sti mati on of Fer
O ne gm of f errous sul ph at e is diss olved in 2 5 mils of w at er
.

and the solu t ion s trong ly aci du lat ed wi t h sulphuric aci d D ec i .

norm al potassium p ermanganat e is t hen delivered from a

buret te until a p erm anen t pink tin t is obtain ed indicating ,

the compl et e oxi dation of the ferrous s alt .

The r eaction is as follows

(I OF S O 7 H O ) 2 K Mn O 4 8H2 SO 4
9 4 z

N
g s
in .
gm = 1 00 0 mi l
. sI 5
VS . .

gms .

gm .

5Fe2 O
( 4)3
S K 2 50 4 2 MN SO 4 7 8HzO .

Thus gms of p erm ang n t

. a a e = 2 7 80
gm s of crys .

talliz ed ferrous sul phat e which equ als , gms of m etallic

.

iron . O ne mil of To p erm anganate solution th erefore repre

sents gm of.F eS O + 7H O or 4gm ofzFe . .

In the analysis 35 mils of the ID p erm anganate w ere con

sum ed The gm taken th en contains
. 1 .

gm or
.
p er c ent .

If i t is desir ed that each cc of the p erm anganate solution .

shoul d represent a c ertain p erc entage of pure salt a mol ecul ar ,

qu antity of the salt shoul d be tak en for analys s i nstead of i

1 gm F or exam p l e if
.
g n s be tak en each mil of the
,
r .
,

decinorm al solution consum ed will corr es p on d t o p e c en t 1 r ,

b ecaus e gms is the w eight of crystalliz ed f errous sul

.
156 THE E S SE N TIALS O F V OL UME TRI C AN AL Y SI S
i t cool to room t em p ratur and again fill to the mark
L et e e .

Sh ak e w ell an d af t er a few m inutes fil t er and coll ec t mils

'

,
20

of filtrat e Add to this

. mils of dilu te sul phuric acid and
20 ,

imm ediat ely ti trat e wi t h t en th n orm al p otassium p erm anganat e -

V S un t il a p erm an en t p ink c ol or is pr oduc ed

. . .

E ach mil of the p erm angan at e solu t ion r epres ents 58 2

gm of m etallic iron
. .

1 0 Fe 80 4 2 K M II O 4 811 2 80 4

gms .
gm s = .
1 00 0 mil s VS . .

gm .
gm .

5F 6 2 (SO 4)3 K 2 50 4 2 Mn SO 4 8H2 0 .

Ti trati on wi th . an E mpi ri cal P ermanganate S oluti on . A

solu tion of perm angan at e which is foun d u pon standa di a , r z

t ion t o b of a s trengt h in which mil is equival en t t o

e 1

gm of Fe is to be used
.
, .

E ach mil of this solution is equival ent to the following

qu an t i ti es

F CSO 4 + 7 H2 0 .

F6 C 0 3
F C CIQ .

t m at i on of Oxal ic Aci d and Oxalat es w i th Potassium

c . Es i
Per man gan ate S o lut i on Hn O 4

The estim ation of ox alic aci d m ay be accurat ely

m ade ei th er by n eutraliz at ion wi th a stan dar d alkali o by r

oxid ation wi t h st and ard p erm ang an at e The l at t er m ethod .

is h ow ev er the one t o be emp l oy ed in the c as e of oxal at es

, , .

The oxidim etric estim ation of ox alic acid is c arri ed out

as follows :
 AN AL Y SI S BY O XI DATI ON AN D RE D U CTION 157

O ne gm of the acid (accurately w eighed) is dissolved in

.

suffi cient wat er to m ake 1 0 mils O f this solution 0 mils 0 .

, 1

r
( p e r es enting gm of the aci d) is t ak e n.for an alysis Two .

mils of diluted sulphuric acid are add ed the solution is h eat ed ,

to b etw een 4 0 C and 60 C and keeping it at about this

°
.
°
.
,

t em perature is titrat ed with decinorm al potassium p erman

,

g a n ate, agit ating const antly until a f aint ros e tint m arks
,

the com p l etion of the r eaction .

E ach mil of the perm angan at e solution consum ed repre

s ents gm of crystalliz ed oxalic acid
. .

The r eaction is as follows :

5 H
( 2 C20 4 Q HQ O ) 311 2 80 4 2 K Mn O 4

gms .
gm s = 1 000 mil
. s T VS 5
. .

K 2 80 4 2 Mn SO h + 1 8HzO 1 0 CO z .

D i rect P ercentage Ti trati on . gm of crystalliz ed oxalic

.

acid is oxidiz ed by 100 mils of p ermanganate Th erefore .

11 of the acid is taken for analysis each mil of

gm .
,

p ermanganate will repres ent 1 per c ent .

Ti t ati ng wi th an E mpi ri al S oluti on

r If the p ermanganate c .

is ch eck ed with iron we tak e into consid eration that 2 K MnO

, 4

will oxidiz e 1 0 atoms of iron p arts) and on the oth er ,

hand 5 mol ecul es of oxalic acid p arts) If the titer of .

the p erm angan at e be found on exp erim ent to be 1 mil = 0 00 6

5 9 .
,

whatever numb er of mils of this solution is consum ed is to

63
be multipli ed by 6
5 9 a n d th en by
5
E x ample gm of oxalic acid r equires for oxidation
. .

4 0 mils of a p erm ang an at e solution whos e tit er is 1 mil = 0 00 569 .

gm Fe the c alcul ation is m ade as follows

.
,

é
x 69 gm x — l 6 gm
4 0 . .
15 8 THE E S SE N TIA L
S OF V OL UME TRI C AN A L Y SI S
gm is the qu an t ity of ur e crystalliz ed ox alic acid
.
p
pres en t in the gm t ak en
. for an alysis Thi s is p er .

c ent .

1 00

If the stan dardizat i on of th p rmangan at e is d on e by e e

m eans of a decin orm al oxalic aci d o by the i odom etr ic m eth od ,

r ,

the c alcul ati on is as describ ed on p ag s 52 1 53 e 1 —

.

Ox alat ar e es t im at ed in the s am e m ann er ;

es a much

l arg er quan ti ty of s ulphur ic aci d is h ow ev r required This ,

e ,
.

s erves to lib erat e the o alic aci d from i t s c ombin at i on

x .

The p r es enc e of p r ci p i t at s of s ul p h at es of c alci um b ari um

e e , ,

or l ead d oes n ot in t rf er wi t h the r ec ogni ti on of the end

e e

p oint .

E ach mil of p o t ass i um p erm anganat e represents

O xalic cid anhydrous (H C O )
a 2 2 4 gm .

O xalic aci d crys t alliz ed (H C O z z 4 l

— —
2 H2 0 )

d Es . timat i on of Hydro gen Di oxi d and Bariu m Di o xid w i th

S tan dard Potassi um Perm an gan at e Hy drog en dioxi d (H yd a . r

ge n p er ox i d) H y d rog en di oxi d and

p ot ass i um
p erm ang a n a t e th ough bo
,
t h oxi dizing ag en t s will wh en mix ed , ,

in an acid solu t ion r educ e each oth er The r eact ion which
, .

occ urs is prob ably primarily an oxidation of the H 0 to a 2 2

high er oxi d (H 0 (P) ) whi ch h ow ever imm ediat ely breaks

2 4 , ,

up with the lib erati on of oxygen The m ethod of ass aying .

hydrog en di oxid by m eans of p erm anganat e is app lic abl e n ot

only to this s ubs t anc e bu t also to the estimation of b ari um
dioxi d and the s olubl e alk ali p er oxi ds The m eth od is usu ally .

c arri ed out by adding the permanganat e s ol ution to the di oxid

in a s olu t ion aci dul at ed with sulphur ic acid Imm ediat e .

d ecolori zation of the perman ganate occurs as lon g as any ,

160 THE E SSE N
-
TI AL S OF V OL U ME TRI C AN AL Y SI S
The D i rect P ercentage Method g s of the solu tion is . Ten i rl .

dilut ed wi t h w at er to m easur e 00 mils Seven t een mils of t his 1 .

dilut ed s oluti on (cont aining g n s of hydrogen dioxid) is acid i .

ulated wi t h sul phuric aci d an d t i t rat ed wi t h d cin orm al p erm an e

g a n ate a
,s ab ov e d scrib ed eE ach mil o f th e p erm angan at e s olu
.

t i on c onsum ed will r epres ent p e c ent by w eight of H 0 r 2 2 .

Ti t ati on wi th an E mpi i al S oluti on

r A p erm angan at e
r c .

s olu t ion is on hand which is foun d upon s tandardiz at ion wi t h

iron o b I mil o 569 gm Fe To use this solu t ion as
t e = . 00 . .

i t is we take int o c onsideration th at K MnO =

,
L 2 4 10

atoms of Fe and also 5 mol ecul es of H O 2 2

gms KMn O . gms F e

4 , 17 gms H o .
, .
z g .

What ever numb er of mils of this p ermangan ate s olution is used ,

7 I
mul t ip lied by gm and th en by .will give the
5
weight of H 0 present in the sampl e analyz ed
2 2 .

E ti mati on of Volume S t ngth

s L et us l ook at the ab ov e
re .

e qu at ion in a d ff er en t light
i .

We see that wh en p otassi um p erm angan at e and hy dr o

g e n d i oxi d r eac t 1 a t oms
,
of oxyg en a e lib erat ed
0 r .

The p erm angan at e i t s elf wh en dec omp ose d lib erat es fi ve

at oms of oxyg en Th er efor e of the abov e ten at oms on ly

.

fi v e com e from the hy dr og en dioxi d .

511 2 0 2
:
5112 0 0
5 ;
2 K MII O 4 + 3HQ S O 4 KQSO4 2 MII SO 4 311 2 0 50 .

In order to find the fac t or fo vol um r e of a a v il abl e oxyg n e ,

see the f oll owing eq uat i on et ; ,

c .

5H2 0 2 2 K M II O 4 + 3HQS O 4
= K Q SO 4 2 MnSO 4 8H2 0 50 50 .

N
gm s . or 1 0 0 0 mil s I? )
VS . .
gm .

1 mi l
g vs . .
gm .
 AN AL Y SI S BY OXI D ATI ON AN D R E D U CTI ON 16 1

Thus it is s een that each mil of I p otassium perm anganate G

VS . . represen t s gm of oxygen But we requir e to

. .

find the volume of oxyg en not the w eight r epr es ent ed by

,

1 of I S perm angan ate

mil .

1 00 0 mils of oxyg en at 0 C and 7 60 mm pressur e w eigh

°
. .
,

n T h er efor e .if g ins m easure 1 00 mils

,
. 0 ,

gm wil l m easure
. mil .

The factor th en for volum e of oxyg en lib erat ed wh en

, ,

hydrogen dioxid is titrated wi th p o t assium p e rm anganate ,

is 57 0 .
,numb e r
andof mils
the of th e p ot assium p erm an -
—

I0

g an ate consum ed in t he ti t rat i on giv es the v olum e of oxyg en

lib erated by the qu antity of hy drog en dioxid taken .

T hus if 10 mils of the VS . . w ere required ,

X1 9
= mil s of oxygen .

It is convenient to o perat e upon mil of hy drog en dioxid 1

solution Th en each mil of potassium p erm angan ate V S

. . .

us ed will represent 0 57 mil of avail abl e oxygen and is meces

.

sary only to multiply the numb er of mils by this factor to

fi nd the volum e of avail abl e oxyg en .

If any oth er qu antity than mil of dioxid b tak en for I e

an alysis it will be n ec essary aft r mul t ip lying by 57 t o

,
e 0 .

divi de the r esult by the qu antity of dioxid soluti on tak en in ,

order to fi nd volum e str ength .

Hydrogen dioxid solution may al so be volum etri c ally

ass ayed by K ing ett s m ethod whi ch is d escrib ed under
’
z ,

Io dom etry .

The gasom etric estim ati on is also d escrib ed furth er on .

162 THE E SSE N T AL S OF VOL I U ME TRI C AN AL Y SI S
B
Bari um Di oxi d ( ari um P erox i d) (BaO z
= T his
subs tanc is assay ed by tr eat ing it wi th an acid and
e ,
then
estim at ing the lib erat ed hydr og en di oxid as follows , :

Weigh off gms of the c oars e p owder put it in a porcel ain

2 .
,

capsul e add ab out 1 mils of i ce col d water th en

,
0 mils -
,

of p h os p h oric aci d (85 p er c ent) and suffi ci en t i ce c ol d w at er

,
-

to m ak e 5 mils
2 Stir and break up the par t icl es wi t h the end
.

of the stirr er until a cl ear or n early cl ear solution is ob t ain ed

and all th at is s olubl e is diss olved .

Five mils of this s olu t i on (which corr esp onds to gm .

of b arium dioxi d) is m easur ed off for ass ay .

D ro p into this from a bur ett e wi t h constan t s t irring deci , ,

n ormal potassium p erm anganate until a final dr op gives the

solution a p erm anent pink tint .

Ab out 4 mils of the decinorm al p erm ang anate shoul d be

0

required to pro duce this result .

In this proc ess the first step is the form ation of hydrog en
,

dioxid by tr eating the b arium dioxid wi th phosphoric aci d ,

as illustr at ed by the following equ ation :

H3 P O 4 BaHP O 4 H2 0 2 .

1 6 9-3 7 34

The hydrogen dioxid is th en estim at ed with d ecinorm al

p erm angan at e as d escrib ed above
,
.

5033 0 2) SH2 O 2 2 K MII O 4 3H2 S O 4

I 6 06
1 00 ) 3 .

gm s =
.
gm s . cc . r
p e m an g anate .

K2 S O 4 2 MI I S O 4
'
‘
l SH2 O
"
0
5 2 .

S odi um P erborate (N aB0 3 D issolve an

accurately w eigh ed qu an ti ty (about gm ) of the sal t in .

a mix t ure of 5 mils of dis till ed water and 0 mils of diluted

0 1

sul phuric acid and titrate the solution with ten th norm al
,
-
164 THE E SSE N TI AL S OF VO LU ME TRI C AN AL Y SI S
It is customary t o add the nitrite solu t ion to a measured
vol um of warm acidul ated stan dard p erm anganate soluti on
e

an d t h en to t i trat e the exc ess of p erm angan at e wi t h stan dar d

oxalic acid s olut ion .

ssay is conduc ted as follows To 50 mils I potassium

The a :
G
perm angan ate V S add 1 00 mils of distill ed water and 5 mils
. .

of sul phuric aci d Tot his Solu t ion add by m eans of a pip ette
.

10 mils of a s olu tion of s odium n itri t e ( gm in 1 mils) 1 . 00 .

I n adding the s odium nitri t e solu t i on imm ers e the tip of the

ppi ett been eat h the sur f ac e of the p erm angan at e mix ture Warm .

the liqui d to 4 C allow it to stan d for fi e minut es and then

°
0 .
,
v

N
ti trat e wi th ID oxalic acid V S until the c ol or of the p erman . .

a na t e s olu t i on is just discharg ed Subtr act the numb er of

g .

mils of the oxalic acid solution used from the numb er of mils
of p ermanganat e solution taken and multiply the remaind er
, ,

by 5 gm .

5N 3 N 0 2 2 K Mn O 4 3112 80 4
=
5X 9
6 -
0 1 34 5-os

5N aN 0 3 K 2 80 4 Z MII SO 4 + 3H2 O .

Each mil of p otassium p e rmanganat e VS . . corresp on ds

to 5 gm of N a N O .
z .

The A ssay o H
f ypophos hi tes ma
p y be mad e by the sam e
m etho d .

ccurat ely w eigh ed qu antity of hypophosphorous acid

An a

or its salt is dissolved in water the solution strongly acidulated ,

wi th sul phuric acid and then a m easured excess of t

B
, p o as

sium p ermangan ate solution added The mixture is boil ed .

for fi fteen minutes to hasten and facilitate the oxidation and

 AN AL YSI S BY OXI D ATION AN D RE D U CTI ON 16 5

th en the exc ess of p erm anganat e solution titrated with

oxalic acid V S . .

E x ample hree gms of the acid are dilut ed with wat er

. T .

to m ak e 60 mils O f this s oluti on 6 mils (r epr es enting

.

gm of the acid) a e carefully removed wi th a pipet te and

. r

intro duced into a flask Three mils of sulphuric acid are added
.

N
and then 50 mils of 6 potassium p ermanganat e solution and
1
,

the mixtur e boil ed for fift een minut es .

The p otassium p erm angan at e in the pres enc e of sulphuric ,

aci d oxidiz es the hyp ophosphorous acid to phosphoric as

, ,

the equ ation shows

5HPH2 0 2 6H2 5 0 4 2 (2K M H O4 )

1 00 )3I 6 . 06

n .
gms . or 1 00 0 mil s VS
. .

5H3 P O 4 OH2 O 2 K 2 80 4 4 MII SO 4 .

E ach mil of the d ecinormal V S repres ents gm . . .

of absolute hypophos phorous acid The quanti ty of per .

manganat e solution direct ed to be added is slightly in ex

cess The excess is th en asc er tain ed by retit ation wi th
. r

decinorm al oxalic aci d E ach mil of ox alic aci d r equir ed or

. c

r esp onds to I mil of decinormal p ermanganate which has

b een add ed in exc ess of the qu antity actually required for the
oxidation .

The exc ess of p erm angan at e colors the s olution red and ,

the oxalic aci d V S is th en ad ded until the red color just

. .

disapp ears which indicat es that the exc ess of p erm angan at e
,

is decomposed .

If mils of d ecinorm al oxalic acid are required it in di ,

cates that 5 mils 0mils = 4 5 3 m ils of decinorm al p erman .

16 6 THE E S SE N TI AL S OF VOL UME TRI C AN AL YS I S
ganate were actually us ed up in oxidizing the hypophosphorous
a cid; th erefore
gm .

of absolute hypophosphorous acid , HPHzO z , or

p er cent .

In this proc ess boiling facilitates the oxidation but if the ,

aci d is boil ed b efor e suffici ent p erm ang an at e has b een added

to com p l et ely oxi di e i t dec om p ositi on will tak e p l ac e

z , Henc e .

dir ect titr ation wi t h p erm angan at e is impossibl e and the r si du al e

m et ho d must be resor ted to .

b . ME THODS I N VOLVI N G A P R E CI P I TATI ON BY OXALI C ACID AN D THE TI TRA

TI ON OF THE E XCE S S OF THE LATTE R WI TH STAN DA RD PE RMAN GAN ATE .

Assay of Cal cium Carbonate and S olubl e Calc um S alts i .

D issolve an accurately w eighed qu an t ity of c alcium c arb onat e

to gm ) in 0 mils of dis till ed water and
. 1 mils of 10

dilut ed hy dr ochloric acid and boil the s olu t ion to exp el all ,

carbon dioxid Transfer this solution to a 00 mil graduated

. 2 —

flask add 00 mils of IO oxalic acid V S ren der it alkalin e wit h

,
1 . .
,

amm oni a w at er shake w ell and all ow it to stand for three

,

hours at from 6 to 70 C or overnigh t at room t emp erature

0
° °
. .

Cool the mixture if n ec ess ary dilut e wi t h dis t ill ed w at er t o the

,

200 mil m ark mix it w ell fil t er t hrough a d y fil t er in t o a dry

-
, ,
r

flask r ej ect the first 2 0 mils of filtr at e and proc eed as follows
, , :

To 0 mils of the filtrat e (

10 repr esen t ing half of the calcium
carbonate tak en) add diluted sul phuric acid unt il of acid
reaction th en add 2 5 mils more of the s am e acid warm the
, ,

solution to 60
°
01 70
°
C .
, an d ti trat e wi th p o t ssium
a p er
168 THE E S SE N TIAL S OF VO LUME TRI C AN A L Y SI S
The 50 mils of s olution r epresent 5 mils of norm al oxalic
aci d, which is equival en t to 5 mils of decin orm al oxalic acid
.

0 ,

so that whatever n umb er of mils of decinormal p ermanganate

s olu t ion is requir ed in th ti trat ion t hat qu an t ity is to be
e ,

d duc t ed from 5 mils and the di ff r enc e mul t i p li ed by the

e 0 e

10
factor for c alcium chl orid to fi nd the quantity of pure
CaCl pres ent in
z gm .

If 4 mils of IO permanganat e are emp l oyed t hen 1 4 from

1 ,

50 mils l av es 36 mils the qu an t ity of decin orm al oxalic acid

e ,

s olu t ion which c ombin ed wi th the gm of calcium chlori d . .

Th n e

gm .
gm .
,

the quanti ty of p ure CaC1 pres ent in the gm or

2 .
,

per c en t .

Calcium s al t s to be es t imat ed by this m etho d must be

tol erably pure and free at l east from imp uri t i es which woul d
,

react with oxalic acid or which w oul d reduc e p ermanganate .

Many of the l ess solubl e calcium s al t s may be estim at ed

by this m thod but th ey m us t be subj ect ed to longer treat
e ,

m ent wi t h the oxalic acid .

G old and l ead s al t s m ay als o be es t im at ed by the sam e

m ethod .

E stim atio n of Lead in th e Acetat e an d S ubace tate Tak e .

for ass ay gm of th sal t or gms of the sol ut ion in a

. e 2 .

b ak er an d add
e mils of r c en t ly b oil ed dis t ill ed w ater
20 e .

Pour t his sl owly an d wi t h c ons t ant sh aking int o a gradu at ed

cylinder c on taining 50 mils of oxalic acid V S Wash the 10

. .

b eak er wi t h small portions of dis till ed water and add the

washings to the c on t en t s of the cylinder Then dilute the .

mixtur e to 1 0 mil s and t asi de to all ow th precipitat e to

0 se e
 AN AL Y SI S BY O XI DATI ON AN D R E D U CTI ON [ 69

settl e Remove 2 0 mils of the cl ear liquid (repr es entin g

.

gm of the salt or
. gm of the solu tion) for titration Add . .

5 mils of (1 0 ) sulphuric aci d w arm to 80

1 C an d ti tr at e ,
°
.
,

N
with I O p erm anganat e until a final drop imp arts a p erm an ent
pal e pin k tint .

The r eactions are r epr es en t ed by the following equ ations

Pb(C2 H3 0 2 ) 2 H2 C2 0 4 '
Z H2 O
Lea da cet at e

PhC 2 O 4 2 HC2 H3 0 2
Pb2 O (C2 H3 O 2 ) 2 2 H2 C2 O 4 -2 H2 O
L ea d su ba cet at e

2 X 1 2 6 05 .

2 PbC 2 0 4 2 HC2 H3 0 2 SH2 0 .

Ea ch mi] of 10
oxalic acid repr es ents gm of .

Pb(C 2 H 0 ) or
3 2 2 gm of Pb O (C H30 2 ) 2
.
g 2 , 01 55
gm of Pb
. .

Calcul at e as describ ed und er assay of c alcium c arbon at e .

The U S F I X M etho d is ess enti ally the s am e as the for e

. . .

going I t is as follows
.

A ssay of L ead A cetate D iss olve an accurat ely w eigh ed .

qu antity of l ead ac etat e (say 5 gms ) in su ffi cient recently .

boil ed distill ed wat er to m ake 1 0 mils of solution Mix '

0 .

1 0 mils of this solution with 5 mils of ten th normal oxalic

'

0 -

aci d V S in a 2 0 mil m easuring fl ask

. . agitat e the mixtur e
0 -
,

thoroughly for five minutes th en fill the flask to the 2 00 mil ,

-

m ark wi t h distill ed water ; filter and titrat e 1 00 mils of the ,

filtrate (repres enting one tw enti eth of the amount of lead —

ac et at e origin ally t ak en ) with t en th norm al p otassium p er -

m anganate V S the fil trate b eing previously acidul ated with

. .
,

1 0 mils of sulphuric aci d and w arm ed to 80

°
C .
17 0 THE E SSE N TIAL S OF V OL U ME TRI C AN A Y S S L I
f
A ssay o issolv
Lead Ox i d
e about D
gm of l ead oxid in 4 mils of ac etic acid and 5 mils of r ecently
. 2

boil ed distill ed wat er Add 5 mils of t en th normal oxalic . 0 —

aci d V S an d dilu t e wi t h distill ed wat er to m ak e

. . 0 mils of 20

fluid Mix w ell and fil t er Coll ect

. mils of fil trat e A idu . 1 00 . c

l ate it wi th 2 mils of dilu t ed sul phuric acid warm the solu tion
0 ,

C and titr at e wi t h t en t h n orm al p ot assium p erm an

°
to 80 .
-

e V S as in pr ec eding assay
'

g a n at . . .

E ach mil of the ox alic aci d V S c orr es pon ds to z .

gm of PbO. .

c . ME T H OD S I N VO L VI N G A R
E DU C T I ON BY M E AN S OF O X AL I C A C I D , AN D

RE TI TR A TI O N OF TH E E XCE S S OF TH E LA T T E R WI H PO T TA S S I U M PE R

t m ati on of Man gan ese Di ox i d (Mn O ) The estima

Es i g .

t i on of m angan es e di oxid dep en ds up on the fac t th at wh en

i t is boil ed with oxalic acid in the p r es enc e of sulphuric acid
d efinite r eacti on tak es p l ac e as the eq uati on Sh ows ,

Mn 0 2 + H2 C2 0 4 H2 SO 4 MII S O 4 Z COQ 2 112 0 .

In the estimation a m easured exc ess of oxalic aci d solu

tion is added t og eth er wi t h s om e sulphuric aci d and the
, ,

mixtur e h eat ed until solution is compl et e .

The exc es s of oxalic aci d is th en f ound by reti trati on with

standard p erm angan at e solution It is w ell to use a norm al .

oxalic acid solution and a d ecinorm al p ermanganat e solu t i on .

0 5 gm .of the dioxid is a conv eni en t quanti ty to op erat e

.

upon E ach mil of decinorm al s ol ut i on r epr es en ts

.

gm of Mn O
.
z .

E x ampl gm of Mn O is tr at ed wi th 3 mil s of sul

e . .
z e

huri aci d an d 0 mils of n ormal oxalic a ci d s ol ut i on which

c 1
p ,

is equival ent to mils of d cinorm al oxalic acid solu tion

100 e ,

the mixtur e is h eat ed in a wat er b at h to 8 C and t h en tr eat d

°
- 0 . e
17 2 THE E SSE N TIAL S OF VOL UME TRI C AN AL Y SI S
a greed th at in ord er to attain res ults of su ffi ci ent precision
the estim ation sh ould be don e in the p r es enc e of hy dr ochl oric
aci d only In using hydrochloric acid h owev er wh ere the
.
, ,

titrations a e to be m ad e with p ermanganat e c ertain precau

r ,

tions (previously m enti on ed) m ust be obs erved b ecaus e of ,

the evolution of chlorin which will oth erwis e t ak e pl ac e and

spoil the analysis This may be obvi at ed by addi ng to the
.

solu ti on to be titrat ed an exc ess of m angan es e sulphat e .

The N O whi ch is produc ed during the r eaction must be

removed by boiling b efore titration with p erm angan at e is
b egun Air must be absolut ely exclud ed d urin g the entir e
.

proc ess to pr ev ent oxidation of f errous s alt by the atmosph eric

oxyg en ,as w ell as to pr ev ent oxid ati on of N O to HN O 3,

whi ch will oxidiz e mor e f erro us salt The exclusion of air .

may be p arti ally affect ed by the use on the fl ask of a Buns en

valv e stopp er (see Fig but the b est m ethod is to employ
.

an app aratus so arr ang ed th at a const ant str eam of C 0 or 2

H gas may be p ass ed through it (see Fig .

T his m ethod although th eor etic ally p erf ect is in prac t ic e

, ,

liabl e to great irr egul ariti es and will giv e fairly good r esults
,

only if the dir ections es p eci ally thos e as to exclusi on of ai

, r,

FI G 4 4
. .

are faithfully c arri ed out The m ethod of Kj el dahl is to be

.

p r ef err ed .

To cond uct the pr oc ess w eigh accurat ely

,
gin s of fl ow er .
 AN AL Y SI S BY OX DA I TI ON AN D R E D U CTI ON 17 3

wire free from rust (the iron cont ent of which is kn own ) ,

pl ac e i t an E rl enm ey er flask which is provid ed wi th a doubl e

p erfor at ed stopp er fitt ed wi t h t wo gl ass t ub es on e of which ,

sh oul d r each just to the surfac e of the liquid in the flask wh en

in p l ac e and the oth er which is the outl et t ub e sh oul d r each
, , ,

n o l ow er th an the bottom of th s t opp er The first of th es e

e .

t ub es is c onn ect ed with an app arat us gen erating c arb on dioxid

or hy dr og en whil the outl et t ub s erv es to c onvey the gas
,
e e

into the ai or into an oth er fl ask c on taining wat er o an alka

r r

lin e s ol ution 30 to 4 mils of p ur f uming hydr ochloric acid

. 0 e

are ad ded to the iron wir e in the fl ask g en t l e h eat is ap p li ed , ,

and a str eam of ei t h er C O o H p ass ed through th fl ask an d

Q r e

m aintain ed t hroughout the entire proc ess Wh en the iron is .

comp l et ely diss olved the s t opp er is rais ed just l ong enough
,

t o introduc e a small gl ass tub e Op en at one end and con

taining the nitrat e to be estimat ed The q uan tity or nitrate .

tak en must be equival en t to not more t h an gm of HN O .

g .

The sto pp er is t h en r eins ert ed h eat app li ed and gr adu ally, ,

incr eas ed un til the r eac t ion is c ompl et e The free hydro .

chl oric aci d lib erat es nitric aci d from the ni trat e an d oxi dati on
of a p orti on of th iron is ff ect ed Th f errous chlorid is
e e . e

oxidiz ed to f erric ch lori d as the equ ati on S hows , an d the ,

s ol ut i on b ec om es at first dark brown through the pres enc e

of N O . As the h eat is incr eas ed the d ark brown color of ,
-

the s oluti on is gradu ally ch ang ed to y ellow as f erric chlori d ,

is form ed and increas es in int ensity until the r eaction is

,

c ompl et e t h en the c ol or r emains station ary and in dic at es com

,

leti on of oxi dat ion T h e soluti on is n ow all owed to c ool

p .
,

but the str eam of C 0 o H gas is m aintain ed F or ty mils of

2 r .

a s ol ut ion of m angan es e sul p h at e a e n ow add ed (this is not r

n ec ess ary if s ulphuric acid is us ed inst ead of hydrochloric) ,

0 fin e p i ano fo
1 -
rt e wi r e,
 N
an d titration with TO p ot assium permanganat e s ol ut ion b egun ,

in order to determi ne the q uan ti ty of unal tered ferrous salt

remaining in the soluti on Assuming that 89 mils w ere re .

quired the calcul ation is m ade as f oll ows :

,

Sinc e on e m ol ec ul e of HN 0 3 r eac t s wi th thr ee

at oms of ir on the q uan t i ty of ir on f oun d to h av e

b een oxi diz ed if m ul t ip li d by 6 6 will giv th quan t i ty

,
e ’
e e
74 1

of ni t ric aci d p r es en t .

E x ampl e5
. gms of iron
1 .wir e p e c en t F e =
=. gms ,
r .

of ir on ) is diss olv ed in hy dr ochl oric aci d as ab ov e describ d

, ,
e ,

and gm of p otassi um nitrat e K N 0

. added , 3 .

Aft er oxidat ion 98 mils of decin orm al p erm ang an at e w r e

, e

r equir ed E ach mil of N K Mn O gm = 0 00

558 2 of Fe
I;
.
4 . . .

5 7
4 gm o f oxi diz ed ir on . .

of ir on w er e origin ally t ak en .

Th er efor e,

gm .
= the quantity of iron ox idiz ed .

Th en

gm . of HN O g ,

which equ als

X 63 0 1 X I
gm KN O
.

—
O
57 I Of S,
67
’ .

or p c n t p ure
er e .

N
It is us ually advis abl e t o u se an
—
ins t ead o f an
7 —
K Mn O 4
5 1 5
solu tion .
17 6 THE E SSE N T AL S OF V OL I UME TRI C AN AL Y SI S
manganate V S repr es ent . . the chlorate which reacted with
the f errous sulphat e .

X X 10 0
p er ce nt .

Chro mi c Aci d r omates Chromic acid oxidiz es

an d Ch .

ferr ous s al t s in the s am e m ann er as nitric acid do es The reac .

tion is thus express ed :

OFCSO 4 l OH2 S O 4 ‘‘ 2 CI 9 3 CI 2 (S O 4 ) 3 + 3F€2 (S O 4 ) 3 OH2 O .

F = 2
s e 334 9

Toccurat ely w eigh ed quantity of ferro us ammonium

an a

sulphat e (Mohr s s alt) ’

(the
p er

manganat e tit er of which is kno wn ) which is dissolved in a

su ffi ci ent quantity of dilut ed s ulphur c aci d in an E rl enm eyer i

flask * add a w eigh ed qu antity of the chromat e or chromic

,

acid in a conc entrat ed aqu eous solution Warm the mixtur e .

on a wat er b ath und er a constant stream of c arbon dioxid

-
,

until the liquid assum es a cl ear green color This occurs in .

a few minut es and indic at es compl et e r eduction of the chrom at e

, .

N ow allow the solu t ion to cool continuing the p ass ag e ,

of c arbon dioxid through the flask and transfer the cold ,

solution to a l arg e b eak er and aft er dil uting it to ab out 300 ,

cc and strongly aci difying it with sul phuric acid titrat e it

.
,

for unoxi diz ed ferro us s alt by m eans of p o t a ssium p er t

m angan at e .

It is usu ally suffi cient to mix the s oluti ons ool d but it ,

is b et t er to employ h eat aft er mixing A l arg e exc ess of .

Thi s fl sk sh ld b p r vid d wi th st pp r h vi g tw p rf r ti s
a ou e o e a o e a n o e o a on

thr gh whi h gl ss t b s
ou cp ss d f th s
a whi h s rv s t
u e vy are a e , on e o e e, c e e o con e

carb di id g sh ld r h l s t th s rf
on ox as, f th li q i d th
ou th r eac c o e o e u ace o e u , e o e

t b sh ld d j st b l w th st pp r d s rv
u e ou en uth tl t t b S
e o e o e an e e as e ou e u e . ee

Fig 4 4 . .
 AN AL Y SI S I
BY OX DAT ON AN D RE D U CT ON I I 17 7

ferrous s al t is unn ec ess ary It is imp erative to dilu t e the .

solu t i on highly b efore t i trat i on as th en only an the end color ,

c

poin t be accurat ely d et ermin ed in the gr een s ol ut ion The .

use of an exc ess of sul p huric aci d b ef or e t i t rat i on is lik ewis e

d em an ded A vi ol et red color m arks the end poin t and unl ess
.
- -
,

too gr eat a qu an t ity of chrom at e be taken or the soluti on be ,

insuffi ci en t ly dilut ed it can be easily r ecogniz ed This m etho d

,
‘
.

is app lic abl e not only to free chromic acid and s olubl e chro
m at es but als o to chr omat s which
,
e ar e insolubl in w ater
e * .

It can th erefore be employ ed for the indirect estimation of

such b as es as are pr ecipitabl e by chromic acid out of n eutral , ,

ammoni ac al or ac etic acid solutions as for inst anc e l ead , ,

bismuth and b arium .

Fin ally the m ethod may be employ ed for the estim ation
,

of chromic o xids The solution of the latter is tr eat ed with

.

an exc ess of sodium c arbon at e bromi n e wat er add ed and , ,

h eat appli ed until a cl ear s olution r esults Thi s soluti on .

,

which contains all of the chrom um i n the form of sodium i

chromat e is evaporat ed the residu e diss olv ed in dilut e ac etic

, ,

acid and the chromium compl et ely pr ecipit at ed by m eans of

l ead ac etat e The p recipitated l ead chromate is th en treated

.

as abov e .

The c alcul ation is m ad e with r ef erenc e to the equ ation ,

in which it is sho wn th at one mol ecul e 1 00 of chromic oxi d ,

( C 1 0 3) is e,
quiv al ent to thr ee mol ecul es of m etallic

1 00
iron The qu anti ty of iron oxidiz ed multipli ed by
. ,

gives the w eight of chromic oxid pres en t and from this i t s ,

equival ent in pot assium sodium l ead bismuth or b arium , , ,

chr O mate is c alc ul at ed .

I thn s f i s l bl hr m t s th s lt i sh k dir tly wi th th

e ca e o n o u e c o a e e a s a en ec e

f rr s s l ti
e ou o ud th mi t r m r hig hly dil t d
on , an d m r str gly
e x u e o e u e , an o e on

h t d th
ea e ,
i th s f s l bl s lts
an n e ca e o
. ou e a .
17 8 THE E SSE N T AL S OF V OL I U ME TRI C AN AL Y SI S
In the c as e of potassium dichromate (K 2 C1 2 0 7 ) mole
one

cul e is equival en t to six at oms of m etallic

iron . quan t ity of iron oxidiz ed is multipli ed by - 2
The
334 9
E x ample To gi n s of ammonio ferrous sulphat e (con
. .
-

taining gm Fe) add gm of K C1 0 7 (mol ecul ar

. .
2
'

w eight an d af t er compl et e oxid ation titrat e the solu ,

ti on with O K Mn O to det ermin e the quanti ty of un chang ed

I
4

ferrous sal t Thirt en mils a e required E ach mil repres ents

. e r .

gm of Fe . .

Thus 8 m = 0 7 5 gm the qu antity of iron

3 , 5I g 0 2 . . 2 .
,

which was not oxidiz ed by the dichromat e This d educted .

,

from the quantity of iron originally ad ded 5

= 0 14 I 7
.
gives the quantity which was oxidiz ed .

Th en ,

gm of C1 0 3 .

X
2
334 9
-

E x ample gi ns of ammonio ferrous sulphat e (con

. To .
-

t aining gm of Fe) add the precipitat e of b arium

.

chromat e obtain ed from gm of BaC1 + H O (molec .

2 2 o

ul ar w eight and aft er compl et e oxid ation titrat e wi h

i ,

rmanganate
p e mils are c onsumed thus
.
5 8 2 ,

53 gm th e qu anti t y of un oxi diz ed ir on pr es ent

.
T h en .

gm of iron oxidiz ed by the barium .

chromate .
180 THE E SSE N TI AL S OF VO LU ME TRI C AN AL Y SI S

P r eparat i on of D eci n ormal Po tassium Di ch r omat e

N
10
gms in
—
000 m i ls) . 1 .

gms of pur e p otassium dichromat e which has

.

b een p ulveriz ed and dri ed at 0 C is dissolv ed in suffi 12

°
.

ci en t wat er to m ak e 00 0 mils of solu t ion 1 .

1
It will be notic ed th at 5 of the m ol ecul ar w eight of the 5
"

di chr omat e (express ed in grams) is tak en in the prep aration

of 1 000 mils of t his solution The r eas on fo this is that one . r

mol ecul e of potassium dichromat e wh en treat ed with an acid

yi elds three at oms of n asc ent oxygen which are avail abl e for
oxi dizing p urp os es thus ,

K 2 CI 2 O 7 + 4 H2 S O 4
‘
K 2 80 4 1 CI 2 (S O 4 ) 3 + 4 H2 O
““ 03;

an d sinc e each atom of oxygen is equival ent to two atoms

of hydrog en one m ol ecul e of the dichromate must be equiv
,

alent to six atoms of hy dr og en Henc e a n orm al solution of .

p ot a ssium d i C
h romate wh en us ed as an oxidizing ag ent should
, ,

contain one sixth of the mol ecul ar w eigh t express ed in grams

-
, ,

in 00 0 mils (see d efinition for n orm al solution ) an d its d eci

1

normal solution s a l

I f a st and ar d solution of potassium dichrom at e is to be

mad e for use as precipi t an t as in the t itration of b arium , ,

on e fourth of the mol ecul ar w eight is to be tak en for

-
000 1

mils of the norm al solution as explain ed in Chapter III , .

S t an dard solu t ion of potassium dichrom at e is som etim es

used as a n eutralizing solu tion for estim ating alkalies phenol ,

p hth a l ein b eing us ed as in dicat or .

Wh en us ed for t his purpos e the normal solution con

tains gms in liter (one half the mol ecular weight
. 1 -

P t ss i m di hr m t f
o a u c o i v l m tri
a e lysi s s h ld r s p d
or use n o u e c ana ou e on

to a ll th t sts f
e e p r i ty g i v
or ui th i t s h ld b r ryst lli d
en n e or ou e ec a ze

s v r l tim s d th dri d
e e a e an en e .
 AN A Y S S BY L I O XI D ATI ON AN D R E D U CTION 18 1

in grams) . I t is th en the x c t quival en t

e a e of any normal
acid V S . .

2 K OH K 2 C1 2 0 7
’

2 K 2 CI O 4 ’

H2 0 .

2)

g s
in .
gm s .
,
or 1 0 0 0 mil s no rm al VS
. .

D ecinorm al p ot assium dichrom at e may also be us ed in

conjuncti on wi t h p o t ass i um io di d and s ulph uricacid for

s t an dardizing s odi um thi os ulphat I odin is lib erat ed from e .

p otassi um iodi d in this reaction ; The reaction is expr ess ed

by the equat i on
K 2 C1 2 0 7
‘
OK I 7 H2 S O 4 4 K 2 S O 4 CI 2 (S O 4 3 7 H2 0 + 1
3 2 .

Th us on e m ol ec ul e of the dichromat e will lib erate S ix

atoms of i odin t heref or e a n ormal s ol ut i on sh ould contain
,

on e six t h of th
-
mol ecul ar w eigh t and a d cin ormal s olu t i on
e ,
e

1
33 in 1 00 mils 0T h s o lution.is h enc e ofe the s am e strength
as th at which is us ed for oxi dizing p urp os es If the d eci .

n ormal s oluti on c ontaining gms in lit er is us ed it . 1 ,

gN
has the eff ect of a sol ut on
ig i .

The decin orm al s olu t i on which is us ed as an oxidizing

ag ent is ch emic ally equiv al en t to decin orm al p ot assium e
p r

m angan at e Wh en us ed fo the p urp os e of lib erating io din

. r

from p ot assium i odi d it is the equival ent of an equal volum e

,

of d ecin ormal so dium thi os ulphat e .

St an dar d p otassium dichr om at e may be ch eck ed in the

sam e way a s tan dard permang anat e wi th pur iron wir e
s , e .

E S TI MA TI ON OF FE RRO U S S A LTS WI TH P OTA S S I U M D I CH R OMA TE

F or ti trati ng f errous cinorm al solu tion of di chr o

salts the de
m at e is us ed in the foll owing m ann er :

Mak e an aqu eous s olu ti on of the ferrous salt introduc e ,

182 THE E SSE N TIALS OF V OL UME TRI C AN AL Y SI S
it in to a flask and acidul ate it with sulphuric or hydrochloric
'

a cid . N ow ad d gr ad u ally fr om a b u r ett e th e de cin orm al

potassi um dichr omat e un t il a drop taken out upon a white
sl ab no l onger Shows a blu e color with a drop of freshly
prep ared potassium ferri cyanid T S N ot e the num b er of . .

mils of the stan dard solution us ed multiply this numb er by ,

the f actor and thus obtain the qu antity of pur e s alt in the
,

s ampl e tak en .

Ferrous s alts strik e a blu e color with p otassium ferricyanid ,

but as the quantity of ferrous s alt gradually diminishes during

the titration the blu e b ecom es som ewh at turbid acquiring
, ,

fir st a gr een th en a gray and l astly a brown sh ad e

, ,
The , .

proc ess is fin ished wh en the greenish blu e tint has entir ely -

dis ap p eared .

The r eaction of pot ass um dichr om at e with f errous s alts

i

alw ays t ak es pl ac e in the p r es enc e of fr ee sulphuric or hydro

chloric acid at ordin ary t emp eratur es N itric acid should not .

be us ed .

If it is d esired to estim ate ferric s alts by this standard

solution it is n ec essary to first reduc e th em This may be .

don e by m etallic m agn esium su lphurous acid the alkali sul , ,

p h i tes or
, by st annous chl o ri d .

O ne mol ecul e of p otassium dichrom at e yi el ds un der favor ,

abl e circumst anc es 3 atoms o i oxyg

, en T his is shown by .

the following equ ation

K 2 Cr2 0 7 Crzoa K zO 03 .

Hereit is s een that the three lib erat ed atoms of oxygen

combin e at onc e with the f errous oxid converting i t into
,

ferric oxid :
6FeO O3 Fe6 0 9 or 3F e2 0 3 .

In the oxidation of a ferrous s alt , the r eaction takes plac e

only in the pres enc e of an acid .
184 THE E SSE N TIAL S O F VO LUME TRI C AN AL Y SI S
Th er efor e,sinc e one mol ec ul e of K C O wi ll give up z rz 7

for oxi dizing p urp os es thr ee at oms of oxyg en which a e eq uiva , r

l ent ch mic ally to si at oms of hydrog en one si th of the

e x ,
-
x

mol ecul ar w eight in grams of the dichr omat e dissolved in ,

suffi ci en t wat er to mak e one li t er c ons t i t ut es a normal s olu tion

, ,

and on e t en t h of t his q uan t i t y of K C

-
O 7 in a li t er a deci z rz ,

normal s olu t i on .

Th us the estim ation oi f err ous s al t s i s eff ec t d by oxi dizing e

them to ferric wi th an oxi dizing agen t of kn own p ow er the ,

streng t h of the f errous salt b eing d et ermin ed by the quantity

of the oxidizing ag en t r equir ed to c onv er t i t to ferric .

Sa cch ar at ed F err ou s Ca r bon at e ( F C 0 = O ne C 3

gm of s acch arat ed f errous c arb onat e is dissolved in mils of

. 10

dilut ed sulphuric aci d an d the s olu t i on dilu t ed wi t h w at er

t o about 00 mils The decin orm al p otassium dic hr omate is
1 .

c ar efully added un t il a dr o p of the s olu t ion taken out and

,

brought in contac t wi th a drop of freshly prepared solution

of potassium ferricyanid ceas es to give a blu e c ol or .

The numb er of mils of the dichr om at e solu t ion is r ead off

and the foll owing equ at i ons ap p li d e

OF eC O 3 6112 80 4 OFCSO 4 OH2 O OCO z ;

OFCSO 4 + K 2 CI 2 0 7 7 11 80
’

2 4
6 ) 9 I I 34 .

10 ) 1 5I . 89

gms .
gms .
, or 1 0 0 0 K2 C 1 2 0 7 V . S .

K 2 50 4 Cl ‘
z (5 0 03 7 H2 0 + 3F 6 2 (5 0 03 .

N
Thus each mil of IO K 2
‘
CI 2 0 7 represents gm of .

p ur e f errous c arbon at e or 5582

gm of m et
.al lic iron .
 AN AL Y SI S BY OXI D ATI ON AN D R E D U CTI ON 185

If strong sulphuric acid is add ed to s accharated f errous

c arbon at e it will char the sugar and a bl ack m ass of b urn t
,

sugar is obtain ed This may be p r ev ent ed by addin g water

.

first and th en sl owly the sul phuric acid

, , ,
.

Instead of sulphuric acid hydrochloric acid may be us ed

, .

FI G 4 5 . .

This will no t char the sugar but the f errous chlorid which
,

is th en form ed is too r eadily oxidiz ed by the air .

It has also b een sugges t ed th at as hydrochloric acid so

rapidly conv erts ordin ary sugar into inv ert sugar as to rend er
it easily at tack ed by the dic hr om at e it should be c autiously
,

us ed if at all Phosp horic acid has n on e of th es e disad

,
.

vantages and may be employ ed wi th good results

,
.

In m aking estimations of f errous salts with potassium

dichrom at e c ar e sh oul d be t ak en t o av oi d at m os p h eric oxida
,

t ion It is good prac t ic e to c alculat e approximat ely how

.

much of the standard solution will prob ably be r equired to

186 THE E SSE N TIAL S O F V OL U ME TRI C AN AL Y SI S
compl et e the oxidation and th en add almost enough of the
,

s tandard soluti on at onc e inst ead of adding it sl owly

, .

A whi t e p orc el ain sl ab is th en got r eady an d p l ac ed ,

al ongsid e of the fl ask in whi ch the titrat ion is to be p erform ed .

U p on this sl ab are pl ac ed a numb er of drops of the fr eshly

prep ar ed solution of potassium ferricyanid and at int ervals ,

during the titrat ion a drop is t ak en from the flask on a gl ass

rod and br ough t in c ont act with on e of the dr op s on the

sl ab The gl ass rod should always be dipp ed in cl ean wat er

.

af t er h aving b een brought in cont act with a dr op of the

indicator See Fi g 4 5
. . .

Wh en a drop of the solution c eas es to giv e a blu e color

on contact with the indic at or the r eac t i on is compl et e , .

Pills of f errous c arbon at e and m ass of f err ous c arbon at e

are assay ed by the s am e proc ess :

Ferr ous Sulphat e (FeSO 7 H O D issolv e

4 a bout z

on e gr am of cryst alliz ed f errous sul p h at e in a littl e w at er ,

add a good exc ess of sul p huric or hydrochloric acid titrat e ,

wi t h the d ecinormal potassium dichromat e as dir ect ed und er ,

F errous Carbon at e and app ly the foll owing equ ati on :

,

K 2 CI 2 O 7 '

7 11 2 5 0 4

N
gm s .
,
o r 1 00 0 mil s BK C 2 1 2 07 VS
. .

T hus each mil of the TO K Cr O 7 V S represents z z . .

gm of crystalliz ed ferrous sul phat e or

.
anhy drous .

If gm of the salt is taken and dissolved as above it shoul d

1 .
,

requir e about 37 mils of the standard solution equival en t ,

to about 00 per c ent

1 .
188 THE E SSE N T AL S OF VOL I UME TRI C AN AL Y SI S
AS 2 0 3 H2 O Z 2 12 AS 2 O5 + 4 H1 ;
H2 S O3 + H2 O I2 Z HI H2 SO4 .

h erefore i odin is said to b an in direc t oxi diz er and

T e
,

may b us ed fo the s t imat i on of a gr eat v ari ety of subs t anc es

e r e

wi t h extreme acc uracy .

Wh n i odin is br ought in con tac t wi t h c erta n o diz abl e

e i xi

subs t anc es i t is dec ol oriz ed This dec ol oriz at i on occurs as .

long a s ome of the oxi dizabl e subs tanc e is p res en t and c eas es
s ,

wh en oxidat i on is c omp l et e Henc e wh en the y ell ow col or .

of i odin sh ows i t s elf in the s ol ution b eing analyz ed the r eaction

is kn own to be at an end In m ost c as es a m ore d elicat e .

en d r eac t i on is ob t ain ed by using s t arch s olu t i on a an in dic at or

—
s .

This giv es a distinc t and unmis t akabl e blu e c olor wi t h the

slight est exc ess of i odin .

In making an an alysis wi th stan dard i odin s olution the ,

substanc e und er examin at ion is brought in t o dilut e s olution

(usu ally a lk alin e) th e s t arch solution added , an d th en the ,

iodi n in the fd m of a s tan dard sol ut i on is deliv ered in from

,
r ,

a bur ett e s t irring or sh aking c onst antly until a fin al drop

, ,

colors the sol ut ion blu e a S ign t h at a slight exc ess of iodin —

has b een ad ded .

P reparat i o n of Decin ormal I odin 10

VS . .

gms p er li t er) D issolve

'

. gms of r iodi n . .
p u e *

I f p r i di b u et t h d i t m y b p r p r d fr m th
o n e no mm r i l
a an ,
a e e a e o e co e c a

a rti l f ll ws
c e as o o

P wd r th i di
o e d h t i it
e p r l i di s h p l
o n an d v r w t rea n a o ce a n ace o e a a e

b th sti rri g
a ,
st tly wi th gl ss d f tw ty mi t s A y dh ri g
n con an a a ro or en nu e . n a e n

m i st r t g th r wi th
o u e, o e
y y g i did d m st f th i di br mid
e an c ano en o , an o o e o n o

an d i di ohl ri d i th s v p ri d
n c o , s u a o ze .

Th tri t r t th i di wi th b t 5 p
en u a e t f i t w ight f p r d y p t
e o n a ou er cen o s e o u e, r o as
si m i did Th i di br mi d d hl rid th r by d mp s d p t ssi m
u o . e o n o an c o are e e eco o e , o a u

br mi d
o d hl rid b i g f rm d
an c d i di li b r t d fr m th p t ss i m i di d
o e n o e an o n e a e o e o a u o .

Th mi t r i th
e r t r ed t th p r l i di sh v r d wi th l gl ss
x u e s en e u n o e o ce a n , co e e a c ean a

f
unne l dh t d
, an s d b th A p r r s blim d i di i th bt i d
ea e on a an -
a . u e e u e o n s en o a ne .
 AN ALY S S BY O I XI D ATI ON AN D R E D U CTI ON 189

in 300 mils of dis till ed wat er con taining 8 gms of pure potas 1 .

sium iodid Th en add enough wat er t o m ake the solution

'

m easur e at 5 C exactly 00 0 mils

2
°
. 1 .

The s oluti on sho uld be k p t in sm all g lass s t opp er ed vials e -

,

in a dark p l ac e .

The p ot assium iodid us ed in t his s ol ut i on acts m er ely as

a solv ent for the i odin .

If pure i odin is us ed in m akin g t his s ol ut i on th ere is no ,

n ec essi ty for ch ecking (stan dardizing ) i t .

But if desir ed the soluti on m ay be ch eck e d against pur e

ars enous acid o sodium thi osulph at e I t th ere is aby do ub t
r .

as t o the puri t y of the iodin it is b es t to t ak e a l arg er qu antity , ,

say 1 4 gms inst ea d.of the gms d ir ec t ed abov e an d .

,

t hen dil ut the r esulting s oluti on to the p rop er streng t h after

e

stan dardizin g .

S t a n d a r d i z a ti on f I
o od i n VS
. . by M ea n s f
o a D e ci n o r

m a l S odi um Th i os u lp h a te S o l u ti o n .
5 mils2of the io din
solution are a ccurately m easured off into a b eaker and then ,

from a burett e the T thiosulphate is delivered until the solu O

tion is of a p al e y ellow color ; two or thr ee drops of starch solu

tion are th en added and the titration with the thiosulphat e ,

solution continu ed until the blu e color of starch iodid is dis

charged .

I i the io din solution is ex actly d ecinorm al the 2 5 mils will ,

requir e 5 mils of decinorm al sodium thiosul ph ate to exactly

2

comp l ete the r eac t ion .

If on the oth er h and more than 5 mils of thiosulph ate 2

solution is r equired it indic ates that the iodin solution is too

,

concen trat ed and must be diluted so as to correspond with

,

the thiosulph at e solution volum e for volum e , .

E x ample Assuming th at in the above titr ation

.
7 mils of , 2

the thi osul ph at e solution w ere us ed th en each 2 5 mils of the ,

190 THE E S SE N TIALS OF V OL UME TRI C AN AL Y SI S
iodin solution must be diluted with w ater t o make 2 7 mils in
order t o c onver t the iodin solu t ion in to a stric t ly decinormal
solution I f how ever the io din s olu t ion is found to be w eak er
.
, , ,

as e vid enc ed by its using

l ess than its own volum e of TO
up

thiosulphate its rel ative strength shoul d be noted on the l ab el

,

of the contain er .

Thus if only mils of the thiosulphate solution are

2 5
used up then mil of the l atter equ als
,
1 mils or
mils of the iodin s olution .

O ne mil of this io din solution is equival ent to mil

of
E thiosulphate which is ,
the sam e as saying 1 mil = 0 .
992
10

N
m1] of 1 i odi n or expressed i n anoth er way mi l of thi s
—

0
, , 1

iodin solution contains gm of io din . .

Such an io din solution may be us ed as an empiric al solu

tion and in any assay the qu an tity of it (in mils) which is
,

consum ed is divi ded by or multipli ed by or by

2
5
and th en multiplied by the d ecinorm al factor for the sub
stanc e analyz ed Anoth er way is to multiply the mils of this
.

iodin s olution us ed by the w eight of iodin contain ed in each

mil and th en by a fraction in which the num erator repr es ents
,

the qu antity of the substanc e an alyz ed equ al to an atom of

iodin and the denominator is the atomic weight of iodin
,
.

E x ample gm of ars enous acid consum es 2 0 mils of

. .

this empiric al solution How much absolute Asa do es it

.

contain ? The factor for AS 2 O3 is gm .

Method (a) gm ,
192 THE E SSE N TIAL S OF V OLU ME TRI C AN AL Y SI S
gm of AS .
2 03 will r equire

mils of a tru e i odin VS

. .

A ssuming that in the above t i tration mils of the io din

solution w ere us ed th en the iodin solu t ion is too concen trat ed
,

and must be dilu t ed so th at each mils will be m ade up to

mils .

Af t er dilut ing in t his way a n ew tri al sh ould be m ade .

It is a good p l an to m ak e a decinormal solution of the

ars eno us oxi d by dissolving g s o f the p u r e oxi d a n di rl .

3 0 gms of s odium bic arbon at e in suffi ci ent w at er to m ak e

.

1 0 00 mils at 5 C a nd t
1o t i t°
r ate t his wi t h the i odin solution
. .

2 5 mils of this solution shoul d r equir e fo com p l et e oxi dation r

exactl y 5 mils of the io din s oluti on if the l att er is stri ctly of

2 ,

d ecinorm al str eng th .

Th e S tar ch S oluti on This solution which is us ed as an

.
,

indicator in iodom etric det erminations is m ade as follows ,

O n e gm of s t arch (potat o arrowr oot or corn starch ) is tri

.
, ,

turated with mils of c ol d water until a smooth mixture is

10 ,

obtain ed then sufficient boilin g water is added with constant

, ,

s t irring to make 00 mils of a thin transl ucent fluid If the

,
2 , .

s olu t i on is not t ransl uc en t i t shoul d be b oil ed for ab out three

minu t es th en all ow ed to c ool and filt er ed This solu ti on
, , .

do es not k eep v ery l ong in f ac t i t b ecom es us el ess af t er,

s tanding one day t h erefore it sho ul d be freshly prep ared

,

wh en required .

This in dic at or is v ery s ensi t iv e to io din i t will d et ect —

one p art of i odin in If the s olu t i on is not cl ear ,

or con t ains fl ocks of ins olubl e starch the charact eris t ic ,

b eautiful blu e c ol or is not obtain ed with i odin ; inst ead a ,

gr eenish or brownish color is produc ed and the insolubl e ,

 AN AL S S BY O Y I XI D ATI ON AN D RE D U CTI ON 193

p ar t icl es are v n col ored bl ack

e e and ar e dec ol oriz ed with
di ffi cul t y .

The blu e c ol or which starch giv es wi t h i odin c onstitut es

a v ery delic at indic ati on of the slight es t exc ess of iodin
e .

This color is us ually r egarded as b eing due t o the form ati on

of a com p oun d of st arch an d io din c all ed iodi d of starch , .

I t is a comp oun d of v ery unstabl e charact er and of doub t ful

c ompositi on .

Sodium t hiosulp hat e b eh av es tow ar ds io did of st arch

ex actly as it do es tow ard fr ee io din i t t ak es up the iodin —

and thus disch arg es the blu e col or .

I odid of s t arch dissoci at es up on h eating but r eunit es ,

up on cooling h enc e it is advisabl e to av oi d h eat in estim ations

,

wh ere starch is used as an indic at or .

In order to prev ent the det eri oration of t his solution a

.

few drop s of chlorof orm may be ad ded; this will p r es erv e

it for a long tim e Oil of c assi a is als o r ec omm en ded as a
.

pr es ervat iv e Mo erk adds 2 mils of the oil to a lit er of the

.

c ool ed s t arch sol ut ion Z inc chl orid or i odid ad ded to the
.

boiling starch solution will prev ent i t s dec ompositi on for a

l ong tim e A st arch solution so made however Sh ould no t
.
, ,

be us ed in titrat ions of sulphi ds b ec aus e zinc r eacts with ,

sulphids .

In the c as e of solutions containing c arb on at es the pre ,

ci pi tate of zinc c arb on at e is so sm all in amount t h at it do es

n ot in t rf er e in the l east with the r eco gni t i on of the en d

e

r eac ti on t int M ercuric i odid is also a very v aluabl e preserva

.

t ive.

gm of m ercuric iodid i n a lit er of the starch solution

.

is quit e suffi ci ent A v ery s atisfactory indicator is the com

.

mercial solubl e st arch which is m ad e by heat ing p ot ato s t arch

wi t h glyc erin and precipitating the starch by rep eated treat
ment wi th alc ohol T his starch dissolv es readily in hot water
.
,
194 THE E SSE N TIAL S OF V OL UME TRI C AN AL Y SI S
forming a cl ear solution which giv es a v erydelic at e r eac t ion
,

wi t h i odin It is b est pres erv ed un d er alcohol the l at t er

.
,

b eing rem ov ed by filtrat ion and evaporation wh en the starch ,

is want ed for making a s olu t i on .

In m aking s t arch solution for use as an in dic at or long ,

con t inu ed boiling should be avoid ed as this c onverts s om e ,

of the starch in t o dex trin .

On the U se of Sodi um Bi carbo nat e in Ti trat i ons w i th

I odin In th es e ti trati ons an exc ess of alkali is n ec ess ary in
.

ord er to n eutraliz e the hydri odic aci d form ed .

AS 2 0 g j
"
2 H2 O 2 12 AS 2 O 5 + 4 HI .

If the hydriodic acid is not removed by n eutralizati on it

will react with the ars enic oxi d (As O ) reducing it to ars enous z 5 ,

oxi d (An ) and lib erat e io din e as sh own by the following

g ,

eq uafi on

4 HI + AS2 O 5 AS 2 0 3 2 H2 O 2 12 .

Sodium bic arbon at e is usually emp l oy ed to n eut raliz e the

HI and S houl d be us ed in sligh t exc ess .

Alkali hy dr oxids or c arb on at es c ann ot be us ed for t his

p pur os e b ec
,
aus e t h ey r eact with fr ee i odin o ev n wi t h r e

s t arch i odid Bic arb on at es ordin arily hav e no such ac t i on

.
,

and th er efor e s odium bic arb on at e is usu ally direc t ed to be

add ed in exc ess to the s oluti on to be ti t rat ed wi t h iodin .

I t is well known that s odium hydroxid s oluti on r eacts

with free i odin with formati on of hypoiodit e and i odid
, .

2 N aO H I2 N aI O N aI l 112 0 ,
“ "

the hyp oiodit e quickly f orming io dat e .

3N aI O 2 N aI N aI O g .

It is als o n ow a rec ogniz ed fact that sodium c arbon at e

196 THE E SSE N TI AL S OF V O LU ME TRI C AN AL Y SI S
pr ess ur e of the C 0 ab ov e is equal to the p ressure of the gas 2

in the s ol ut on i un t il q uilibrium has b een r ach ed In

i ,
. e .
,
e e .

c onc n trat d s olut i ons of N aHC0 the am ount hy drol yz d is

e e 3 e

m uch gr eat r t h an in dil ut e s ol ut i ons An el vati on of t emp er

e . e

at ur e m at eri ally incr eas es th abs orp t i on of io din e .

L ess i odin is l ost wh n sm all er fl asks a e us ed p r ovi ded e r ,

the g lass s t op p r c omp l et ely sh u t s off c omm unic at i on with

e

the atm os p h er T he C O will esc ap e from the solu t i on

e .
2

un t il i t s p r essur in the s ol ut i on is qual to t h at of the gas

e e

ab ov e T h us sinc e a l arg er v ol um e of air is c ont ain ed in

.
,

a l arg r fl ask m or
e C 0 p ass es from the li q uid b ef or equi
,
e 2 e

libri um is es t ablis hed h nc m or N aHC 0 is decomp os d ,

e e e 3 e ,

an d m or i odin in c on s q u nc bs rb d
e a o * e e e
e .

R as oning fr om the ab ov
e obs rv at i ons i t ma
y be s ai d e e

th at : th ough s uffi ci en t s odi um bic arb on at e be us ed to

I ,

m ore th an n eutraliz th hydri odic acid f orm ed the s olution e e ,

t i trat ed h oul d be w ell dil ut ed ; 2 that the t i trat i on sh oul d

S ,

be don c ol d ; 3 t h at th t i t rat ion s hou l d be don e in sm all

e ,
e

s t op p ered flasks and 4 i t Sho ul d be don e quickly , ,

.

Es i t mat i on of A r sen ous Com pou nds

Th es e comp oun ds are estimat ed by means of i odin in a
m ann er im il ar to t hat describ ed un d r s t an dardiz at i on of
S e

i odin s ol ut i on by m eans of arsen ous oxid The m et h od is .

as f oll ows

Ar sen ous O x i d (Ar enou Aci d Arsenous A n hyd i d A r n i s s ,

r ,
se c

T i ox i d)
r Wh en ars en ous acid is brough t in
c on tac t wi t h i odin in the pres enc e of w at er and an alkali ,

For fu he rt r st dy f q u o e ui lib ri um , see the wo rk of Dr H . . N . McCoy ,

Am Ch . .
J .
,
vol XXI V 4 3 7
.
,
 Y I
AN AL S S BY OX D AT ON AN D R E D I I U CTI ON 197

i t is oxidiz ed in t o ars enic acid an d the iodi n is decoloriz ed .

The r eacti on is :

AS 2 O 3 2 12 2 H2 O AS 2 0 5 4 HI ;

N aHC0 3 HI N aI Hg O l C 0 2 -
.

The lkali shoul d be in suffi ci ent quan t ity to combin e

a

wi th the hydriodic acid form ed and m us t be in the form of ,

p o t assium or s odium bic arbon at e .

The hydroxids o c arbon at es sho ul d n ot be us ed

r S t arch .

s ol uti on is us ed as the in dicator a blu e c ol or b eing form ed ,

as s oon as the ars en ous acid is entir ely oxi diz ed into ars enic

aci d
.

D issolve about gm of ars enous acid accurat ely w eighed

.
,

in 2 0 mils of boilin g distill ed wat er by the gradu al addition

of so dium hydroxid T S un t il comp l et e s olution r esul t s . . .

N eutr aliz e this soluti on wi t h a dilut ed sulph uric acid V S . .

,

using p henol phthal ein T S as indicat or cool dissolve in it . .

, ,

2 gms of so dium bicarb onat e an d titrat e the mix t ur e with

.

decin orm al io din V S using starch T S as in dic at or sh ak

. .
, . .
,

ing or s tirrin g the mixture constantly un til a permanen t blu e

col or is produc ed The following equ ation illustrates the
.

reaction
AszO 3 2 H2 0 2 12 4 HI An s .

-9 2 -6 8

I o )49 48 .
92
N
gm s . 12 . 6 92 gm s . or 1 0 0 0 mil s I VS . .

N
Thus ea ch mi l of I VS . . repres ents gm . of
10

p ur e A s o2 g .

So lutio n of Ar seno us A ci d and S o lu t i o n of P otassium

Ar seni te are assay ed in the m ann er above describ ed Tw enty .

mils are tak en fo the ass ay gm of S o dium bicar bonate

'

r , 1 .
198 THE E SSE N T ALS OF VOL I UME TRI C AN AL Y SI S
added, s olution diluted to 1 00 mi ls and titrated with the
the ,

decin ormal i odin solution N o in dic ator is r equir ed th ough .

s tarch may be us ed .

In the cas e of soluti on of p otassi um ars enit e it is advisabl e ,

to slightly aci dify with hydr ochloric acid th en to m ak e the ,

sol ut i on alkalin e wi t h sodium bicarb on at e b efore ti trating .

T he hvdrochlori c acid is employ ed her e in ord er to n eu t raliz e

any p ot assi um hydroxi d which may h av e b een f orm ed t hrough

hydrolysis of the potassium bic arbonat e cont ain ed in the

soluti on .

Ar seno us Io di d (As1 = 4 5 This s alt is estim at ed in 3

the s am e way as d escrib ed for ars enous ox i d The r eaction .

is illustrat ed by the following equation

2 AsI 3 5Hg O 2 12 As2 0 5 10 HI .

4 ) 9 H -4 4

gm s = . 1 00 0 mils I VS. .

The D i rect Percen tage Assay of Ar senous Co mpounds .

A qu anti t y of ars enous acid is t ak en which is eq ual to the ,

weight of p ure AS 0 3 oxi diz ed by 00 mils of decinormal

2 , 1

iodin i e , . gm .
, .

If gm of the sam pl e be taken then each mi of T

. l
O
.

I V S will repres ent fi m of this q uanti ty or 1 per c ent of

. .
l ~

p ur e A S 0 In th e
2 c as e3of w
. eak solutions of a rs enic as ,

liquor acidi ars nosi liquor potassii arseniti s etc which

e , ,
.
,

c ontain only one per c ent of arsenous acid A much l arger .

quantity S houl d be taken for analysis oth erwise the quantity ,

of s t an dard io din s olution us ed will be so sm all as to dim inish

the accuracy of the t est .

Thus if only , gm of either of the above solutions .

2 00 THE E SSE N TI AL S OF VOL UME TRI C AN AL Y SI S
i odin s ol ut i on This Sh oul d be don imm ediat ely Th
. e . e

app earanc e of a p rm an ent blu e c ol or m arks the en d oint

e -
p ,

s tarch b eing us d a in dic at or e s .

S b2 0 3 Z H2 O 2 12 4 HI Sb2 0 5 .

92
Ni
gm s . 12 . 6 9 2 gm s . or 1 00 0 m il s I O
VS . .

O n e mil of i odin r ep r es en t s gm of Sb2 0 3

0
. .

The s olu t ion of the oxi d may be m ade by m eans of hydro

chloric aci d and aft er adding a p ort i on of t ar taric and dil ut ing
,

wi th wat er so di um bicarb on at e is add ed and the t itrat i on

,

c on duc t ed as ab ov e .

O th er c om p oun ds of antim ony m ay b estim at ed in the e

s am e way An tim onic c omp oun ds are r educ ed to antim on ous

.

sulphi d (Sb 8 ) by precip i tat ing with hydrog en sul phi d and
2 3 ,

aft er th or oughly washing the p r eci p i t at e disso lvin g i t in hydr o ,

~

chloric aci d; th us a solu t i on of an t imonous chl ori d i s obtained

from which all trac es of hydrog en sul p hi d a e exp ell ed by r

b oiling Thi s s ol ut ion is diluted wi th w at er tartaric aci d

.
,

add ed and fi n ally aft er m aking alk alin e with s odium bic ar
, ,

b on at e titrat ed with the st andard i odin s ol uti on as above

,

describ ed .

Antimony and P otassium Tar trate (Tartar E m etic )

O ne gm of the s alt is .

dissolved in su ffi ci ent wat er to m ak e 0 0 mils 30 mils 1 .

of this soluti on repr es en ting gm of the salt are t aken

0 m
, .
,

fo ass ay
r . ils of a c ol d saturat d solution of so dium
2 e

bicarbonate are added th en a littl e s tarch solution and the , ,

mixture titrated wi th odin until i a p erm anent blu e col or

ap pears .

The c alc ul ati on is as foll ows :

 AN A L Y SI S BY O XI D ATI ON AN D R E D U CTI ON 2 01

2 K (SbO) C4 H 1 0 6 + H2 O l
‘"
2 12 H
3 20
-7

N
gm s m s = mi ls I VS
.
g . 1 00 0 . .

I O

4 HI 2 K HC4 H4 O G 2 HSb0 3 .

N
of 1Odin repr es ents
1 mil —

10
gm of K (SbO ) C H 0 6 .
4 4

+ 4H 0 (crys t alliz ed tar tar em eti c)

-
2 .

K (SbO ) C H 0 6 (anhy drous tartar em etic)

4 4
34
-

gm s = 1 0 00 mi l
. s VS . .

N
Thus 1 mi l of 10
i od i n repres ents gm of anhydrous
.

tartar emetic .

t t o n of S ulphurous Acid and S ulphites

E s i ma i

Th es subs tanc es may be accurat ly estim at ed by m eans

e e

of a s t an dar d solu t i on of i odin Wh en sul phurous acid o

. r

on e of i t s s alts is br ough t in c ont act wi t h io din a c m p l et e

o ,

oxidation takes pl ace The sulphurous acid is oxidiz ed to

.

sul phuric acid and the s ulphi t e to a s ulp hat e as the equations ,

S how
'

H2 80 3 + H2 O I2 2 HI + H2 SO 4 ,

N aHS O :, + H2 O + 12 Z HI + N 3 HSO 4 .

T h ere
t wo m etho ds which may be empl oy ed In one
are .

meth od the substanc e is brought int o s olution in wat er an ,

exc ess of sodium bic arbon at e is add ed an d th en the s t an dard ,

i odi n solution is run in until a fain t y ellow c olor of free i odin

2 02 THE E SSE N TI ALS O F V OL UME TRI C AN AL YSI S
mark s r eaction I f starch solution is us ed as indic ator
the .
en d -
.

the end point is the pro duction of a blu e col or

-
The oth er .

m et hod is that of G il es and Sh earer who in a v ery v oluable , ,

s eri es of exp erim en ts d etail ed in the J S C I III 97 and . . .

, ,
1 ,

I V 30 3 suggest the foll owin g modific ati on

, ,

The weigh ed sulphurous acid or the sulphit e (in fi ne

powd er) is added to an a cc urat ely m easured exc ess of

10

i odin W i thout diluting wi th wat er Aft er the mixt ure has

,
.

b een allow ed to stan d for ab ou t on e h our with fre qu ent ,

‘

sh aking the oxidation is c ompl et e and the exc ess of iodin

, ,

is asc er tain ed by t i trating b ack wi t h E) s odium thiosulp hat e .

The quan t ity of the l atter d educt ed from the qu antity

of _

IO
iodin s olution ad ded will give the qu antity of , the a l tt er
which r eact ed with the sulphit e .

The n eutral and acid sulphit es of the alk ali es alkali earths , ,

and ev en zinc and aluminum may be accurat ely estimat ed ,

in this mann er The l ess solubl e s alts r equirin g of cours e

.
, ,

mor e tim e and shaking to insure th eir compl et e oxidation , .

The l att er is the U S P m ethod . . . .

Sulphur ous Acid T his is an aqu eous soluti on of sulphur

.

dioxi d
Sulph urous acid wh en brought in cont act with iodin i s
oxidiz ed into sulphuric the iodin b eing d ecol oriz ed b ecaus e of
,

its union wi t h the hydrog en of the accomp anying wat er ,

forming hydriodic acid .

Two grams of sul p hurous acid are t ak en and dilut ed with

distill ed wat er (r ec en t ly boil ed and co ol ed to about 2 5
“R tly b il d i s r s bs
ecen o e f i th yg
n u e f whi h w ld
a ence o a r, e ox en o c ou

pa rt i ally i dioxt h s lp h
ze r s ei d u d l d i d
u oui r t d t v id l ss
ac , an coo e
”
s ec e o a o o

o f 5 0 whi h w ld
2, c r if h t w t r w r s d
ou occu o a e e e u e .
2 04 THE E SSE N T ALS or I VOLU ME TRI C AN AL S S Y I
N
50 m i ls of I od n O
i i added, and mul tip ly the d f i fer enc e by the

N
10
factor for .
80 2 , which is 00 0 20
3 35 gm . T his will give the

weight of 80 in the quan tity of acid tak en fo analysis

2 r .

Wh en a s olu t i on containing sul p hur dioxid is to b m easured e

by m eans of a pip et t e i t is n ever advisabl e to fill the ins t um ent

,
r

by suc t ion in the usual mann er as this woul d ,

caus e a l oss of the gas A b etter p l an is to fill .

the p i p et t e by p ress ur by the use of an e

arr ang em ent simil ar to t h at S h own in F i g 4 6 . .

The s olu t i on con t aining s u l phur dioxi d or

ot h er vol at il e substanc e is p our ed in t o a fl ask

which is provi ded wi t h a s t opper through

which tw o gl ass t ub s p ass ; on of t h es ee e

t ubes reac hes n early to the b ottom of the flask

and the ot h r p r oj ec t s ab ou t on e half an inch
e -

b el ow the s t opp er and is b ent ou tward above .

To the up p er en d of the f orm er the p i p ett e is

attach ed by m eans of a p i ec e of rubb er t ubing .

By bl owing in t o the fl ask t hr ough the s hort er

t ub e the liquid is c aus ed to ris e and fill the
p pi ett e which m ay t h en b easily p ull ed out of
,
e

the rubb er t ub e conn ec t i on .

S odium S ulphite (N fi S O 7 11 2 0 z g

T ak e gm of the fin ely powdered crystals

.
,

N
FI G 4 6
. .

5 mi l s of io
add to
T
O
din co ntain ed
0 in a ,

10 0 - mil gl ass stopp ered flask and allow to stand for one
-
,

N
hour (shaking frequ ently) ; then ti trate W i th I O sod um i It

sulphate until the color is discharged .

r
The ea c t i on is x p r ess d as f oll ows
e e :
 AN AL Y SI S BY O XI D ATI ON AN D R E D U CTI ON 2 05

N a2 so3 7 112 0 12 Z HI N a2 80 4 OH2 O .

gms .
gms . or 1 000 mil s —

1 5 i odi n V S
. .

T hus each mil of the s tan dard solu tion repr esen t s
gm of crys t alliz ed sodium sulphite
. .

If gm of the s alt is tak en to fi nd the p erc entage mul ti

1 .
,

pyl the f act or by the numb er o f mils of st and ar d solu tion

consum ed and the r esult by 1 0
,
0 .

Potassium S ulphi t e ( 80 +
K H O = O p erat e 2 3 2 Z

u pon 05 gm in the s am e m ann er as for s odium sul phi te

. . .

K 2 80 3 Z H2 O I2 2 HI K 2 SO 4 H2 0 .

37
-

10 )
g s
in . or 1 000 mil s of st anda rd V S
. .

N
Ea ch mil of the 15 iodin represen t s gm of crys
—
.

talli ed p ot assium sulphit e

’

z .

S o di um Bi sulphi t e O p erat e upon

ab ou t 5 gm in th e s am e m ann er as for sodium sul hit
.
p e,

an d ap p ly the following equ at i on

N 3 HS O 3 + 12 + H2 O 2 HI N aHS O 4 .

S odi um o sul phat e (Sodium Hyposulphit e) (N 3 8 0 3

Thi 2 2

T his s alt wh en br ought in c on t ac t wi t h ,

i odin s conver t ed into sodium i odid and s odium t et rathi onat e

,
i .

The r eacti on is exp r ss ed by the eq uat i on e

2 N a2 S 2 O 3 + 12 2 N aI N a2 S 4 0 6 .

It is es t im at ed as follows : 1 gm of . the s alt is dissolved

2 06 THE E SSE N T AL S OF I VOLUME TRI C Y SI S
”

’
AN AL

in 20 mils of w ater , a rop s of starch solution

few d are ad e dd ,

an d th en the
ID
i od in is deliv er ed in from a buret t e un t il
,

the a p ea ap r nc e of blue st arch iodid indic at es an e xc ess of

iodin .

Hydr ogen Sulphi d (HzS Wh en iodin and hydrog en

sulphid are brought togeth er in s olu t ion the fo llowing reaction
occurs :

H2 S + 2 I = 2 HI + 8 .

The r eaction is not r egul ar how ev er wh en p erform ed in , ,

an aci d solu t i on but in the pres enc e of alkali bic arbon at es

,

the r esults are cons t ant The m ethod may be employ ed for
.

the estim ation of alkali sul p h at es .

The proc ess m ay be c onduct ed as follows

Into 30 mils of a cold saturated solution of sodi um bi
carbonate contain ed i n a 500 mil flask m easure a sui tabl e
,
—
,

qu antity of the solution of hy drogen sul phid stop p er the ,

flask and mix contents by Shaking Dilute the solution .

with about 300 mils of water add starch solution and titrate ,

With 13 iodin V S until a distinct . . and p erm anent blu e color

ap p ears .

E ach mil of i odin r epr es ents

—
gm of H 8
10 5 .
2 .

The residu al m ethod may also be e mployed . A sui tabl a

N
volum e of the sampl e is added to an excess of 10 iodin V S . .

mixed with som e sodium bicarbonate solution the solution is ,

N
thoroughly shak en , and th en titrated with —

10
thiosulphate ; the

N
q u an tity of the l atter d educted from
, the qu antity of —

15
iodin
2 08 THE E SSE N T ALS or I V OLU ME TRI C AN AL S S Y I

TA B LE O F S UB STAN C E S W HI C H M AY BE E ST I M AT E D BY M E AN S
O F S T AN D A R D I O D I N S O L U T I O N

l Mo l ec u l E F a c tor
N am e . F orm u a .

W gh ei t
ar
. 10
.

Acid, s ulp hu o u r s H ZS O 4
An tim ono u s o x id Sb2 0 3
An ti m o n y and po t as
’
m rr
t a t ate 2 l HZO
--

A r seno u si odi d A sl 3
o xi d A szO 3
C yano en g CN
rg s
Hyd o en ulp hi d HzS
r
I o n (m etalli c ) F e2
Me r ri hl ri d
cu c c o HgC l2
Me r r s hl rid
cu o u c o HgC l
P t s i m y id
o a s u c an KCN
s lp hit ( hydr s)
u e an ou K ZS O - o
.

( ryst lli d) c a ze K 2 8 0 3 + 2 HZO

S di m bi s lp hi t
o u u e N aH S O 3
s lp hi t ( hydr s)
u e an ou . N a2 S 0 3
( ryst lli d) c a ze N a2 SO s + 7 HzO
thi s lp h t o u a e N a2 S 2 0 3 + 5 HZO
S lp h r di i d
u u ox . SO,
Ti i s t
n n s m p ds
anno u co o un Su z
Z i nc Z uz

Es i t m ati on of Subs tan ces Readil y R educed .

Any subs t anc e which r eadily yi el ds oxyg en in a defini t e

quantity or is s usc ep t ibl e of an eq uival en t ac t ion whic h

, ,

involves its r eduction to a l ow er q uan t ival enc e may be q uan; ,

ti tati v ely t es t ed by asc er t aining how much of a r educing ag en t

of known p ow er is required by a gi en q uan ti ty of the sub v

st anc e for i t s c omp l ete reduc ti on .

The princip al r educing ag ents which may be em p l oy ed

in volum etric an alysis a e odi um thi o ulphat s ulp h urous aci d r s s e, ,

ars en ous aci d ox alic aci d m et allic zinc an d m agn esi um

, , , .

The s odi um t hi os ul p h at e is the only on e which is emp l oy ed

ofli ci ally in the U S P in the form of a volum etric s oluti on
. . . .
 AN AL Y S I S BY OXI D ATI ON AN D R E D U CTI ON 2 09

I t is us ed in the es tim at i on of fr e i odin and in dir c t ly of e , e

ot h r fr ee h al og ens
e o c omp ounds in which the halog en is
,
r

easily lib er at ed as in the hy p ochl ori t es etc

, , .

Es i t m at i on s Involv i n g the U se of S odi um Thi o sulphat e VS

. .

(I odom et ry )

Wh en so dium t hi os ul p hat e ac t s u p on i odin s odium t etra ,

t hi onat e and s odi um i odid are form ed and the s olu t ion is ,

dec ol oriz ed .

‘
his r eac t i on t ak es p l ac e in defini t e prop or t ions : on e
T
mol ecul ar w eight of the t hios ul phat e absorbs on e atomic w eight
of iodin .

2 N a2 S 2 0 3 + 12 2 N aI + N a2 s4 o e .

Chl orin
c annot be directly ti trated wi t h the thiosul ph at e ,

but by adding to the solu t i on c ontaining free chlorin an exc ess

of p ot assi um i odi d the i odin is lib er at ed in e xact p roportion
,

to the qu antity of chl orin p r es ent at om for at om , .

C 12 2 KI 2 K C 1+ 12 .

h en by es timating the iodin the quantity of chlorin is

T ,

asc ertain ed All bodi es whi ch contain avail abl e chlorin or

.

br omin o which wh en treated wi th an aci d evolve chlor i t

,
r

o br omin m a be es t im at ed by this m etho d

r
y , .

Also bo di es which cont ain av ai lable ox ygen and whic h

, ,

when b oil ed with hydrochl oric aci d evolve chlorin such as ,

manganate ch omates pe ox i d etc may be es tim at ed in thi s

s, r ,
r s, .
,

way .

olu t ions of ferri c salts wh en aci dul at ed and boil ed wi th

S ,

an exc ess of p o t assium i odi d lib erat e io din in ex act propor

,

tion to the qu an t i ty of ferric iron present .

2 10 THE E SSE N TI ALS OF VO LU ME TRI C AN AL Y SI S
A rsenates c opp er sal t s and oth ers als o lib erate iodin from
, ,

p o t assium i odid q uan t i t at ively

, .

Thus s odium t h iosul p h at e may be us ed in th s tim at i on e e

of a great vari ety of subst anc es wi t h ex t r em e acc urac

y .

Prepar atio n of D ecinormal S odi um Thi osulp hat e (Hy p o

sul phi te) contains gi ns in .

1 li t r) Sodi um thiosulph at e is a s alt of thiosul phuric aci d

e .

in which two at oms of hydr ogen h av e b een r ep l ac ed by s odium ;

i t th erefore s eems that a n ormal s olu t i on of this s al t shoul d
c on t ain one h alf the m ol ec ul ar w eigh t in grams in one lit er
-
.

But this s alt is us ed chi efly for the es t im at i on of iodin ,

and as st at ed b ef or e on e f ull m ol ec ul ar w eigh t r ea

, ,
cts with
and decoloriz es on e at omic w eigh t of i odin an d S inc e one ,

at om of iodin i s chemi cally eq uiv al en t to on e at om of hy dr og en

. .

a full mol ecul ar w eight of s odium thi osul p h at e m ust be con

tain ed in a lit er of its n orm al s olu t ion .

So dium thi osul ph at e is easily ob t ain ed in a pur e st at e ,

an d th er efor e the pro p er w eight of the s al t r educ ed to pow der ,

and dri ed b etw een sh eets of bl otting p ap er m ay be diss olv ed —

,

dir ec t ly in w at er and m ad up t o on e li t er
,
e .

A strong er s olu t i on t h an decin orm al is usu ally m ad e its ,

ti t er found and then the s ol ut i on dilut ed to the prop er m eas ure

,
.

Thi r ty gms of s el ec t ed crys t als of the s alt are diss olv ed in

.

enough w at er to m ak e at o n ear 2 C 0 0 mils

°
5 ,
r .
,
10 .

This c onc en trat ed solu t ion is th e n stan dardiz ed by one of

the foll owing m t h ods e

N
a S ta d a d i a ti n by M a
. n r f 7 6 I di n
z o Transf er 1 e ns o o . 0

mils of this s oluti on in t o a flask or b eaker add a f w dr ops of ,

e

starch T S and th en gradu ally deliver into it from a bli rette

. .
,

decinorm al io din s ol ut i on in sm all p or t i ons at a tim e sh aking

, ,

the fl ask aft er ach addi t i on and r egul at ing the flow to dro p s
e ,

t ow ar d the end of the o erat i on As soon a s a blu e color is

p .
2 12 THE E SSE N TI AL S O F VOL U ME TRI C AN A L Y SI S
iodid (free from i odate) and mils of wat er Acidul ate the 100 .

s olu tion wi th 5 mils of c onc en trated hydr ochl oric or sul phuric
aci d c ov r the b eak r and l t stan d for about fi e minu t es
, e e , e v ,

th en ti trat e wi th the thi os ulphat e s olu t ion to b s tan dardiz ed e

( using s t arch a s an in d ic at or ) u n t il th bl u e c o l or is j u st e

disch arg ed The c alc ul at i on is t h n m ade as foll ows

. e

K 2 CI 2 O 7
’

OK I I 4 H C 1= 2 CI C I3 8K C l 7 H2 O 1
3 2 .

T hus gms of p otassi um dichromat oxi diz

. e es

gms of .
p ot assi um i odid an d lib erat es t h er efrom
7 6 1 .
5
2 gms .

of i odin .

The p o a t ssi um iodid must be in exc ess ; in fact for each

at m
o of odi in lib erat ed one m ol ec ul of p otassi um iodid m us t e

be p r es ent at the c omp l et i on of the r eac t ion in order to k eep

the i odin in s oluti on and t h us pr ev en t l oss by vol at iliz at i on
,
.

If gms of p otassi um dichromat e lib erat e 7 6 5 gms

. 1 . 2 .

of i odin gm will lib erate

,
.

7 6 5 X

1
1 0 2
-
0 .
51 73 gm . of i odin .

2 9 4
N
gm of i odl n = 1 mi l of th i osul ph ate
IO
. .

N
mi ls of TO thi osul ph ate .

T h erefore if in the above ass ay mils of the thiosul

p h a t e V S w er
. e consum
. ed it must b e dilut ed so th at each ,

mils will m easure mils in order to convert the thio

‘

sul phate soluti on into a tru e decinorm al solu t ion A new .

trial shoul d then be m ade with the diluted s olu tion to see if
-

i t s stren gth is corr ect .

It is usually more conveni ent t o use a decinorm al dichro

 I
AN ALYS S BY OX D AT ON AN D RE D UC T ON I I I 2 13

mate V S for standardizing decinormal thiosu l ph ate V S

. . . .

This may be don e as foll ows :

D issolve two grams of pure p otassium io did in a sm all
qu an t i ty ( 0 to 1 5 mils) of sul p huric acid ( o) Pl ac e this
1 I —
I .

into a 5 0 mil flask and add to i t very S lowly 2 5 mils (accu

0 —

ratel
y m easur ed) of d ecinorm al pot assium dichrom at e V S . .
,

mix w ell and let stan d for fi e minut es the fl ask b eing k ept
.
v ,

cl osed The thi osul phat e solution to be standardiz ed is then

.

run in from a buret t e in sm all p ortions shaking after each ,

addi t ion until the solution is a p al e y ellow c olor Two mils .

of starch solution a e th en added and the ti tration continu ed

r

dro p by dr o p until the blu e color of st arch io did is just dis

charged .

Sever al tri als a e m ade and fr om an averag e of t hr ee or

r ,

four cl osely agreeing resul t s the qu anti ty of w at er requ red i

for dilu t ion to decin orm al strength is readily c alculated .

E x ample Assuming th at in the above tr i al

. mils of
the t hi osul p h at e soluti on w er e r equir ed to r eact with the io din
lib erated by 5 mils of decin orm al dichrom at e th en the thio
2 ,

sul ph ate must be diluted with distill ed w at er so that each

2 3 8 mils will m ea sur e 5 mils A f t er dilu t ion
2 a n ew tri al .

shoul d be m ade in which 5 mils of d cinorm al dichrom at e

,
2 e

shoul d require wh en tr eat ed as above describ ed exactly 2 5 mils

of the thiosul ph at e .

c. S ta n d a r d i z a ti o n by M ea n s of P o ta s s i u m B i -i o d a te .

This m et h od dep en ds upon the fact th at wh en p otassium i odid

an d bi i odat e are brought t og eth er in the pr es enc e of a sm all
—

quan t i ty of an acid an equival ent am ount of i odin is set free

, .

The r eac t i on is illustrat ed by the eq uat i on

K H (I O g) 2 IO KI I I HC l 12 1 I I K Cl OH2 0 .

)
I 2 38 9 94.

N
gm s .
gms . or 1 00 0 mil s IOV S . .
2 14 THE E SSE N TI AL S O F VOL U ME TRI C AN AL Y SI S
Thus it is seen that one mol ecul e of iodat e causes h
t e bi -

the lib erat i on of 2 atoms of io din against whic h the t hio

1 ,

sul phat e solution is standardi ed z .

In order not to use up too l arge a qu an t ity of the thio

sul phate solu t ion in the titrat ion a very sm all qu an t i ty of ,

the bi io dat e must be tak en an d since a sm all error in w eighing

-
,

this w oul d entail a r el ati vely large error in th results i t is e

b est to use the bi iodat e in the form of a solu t ion of kn own

-

s trength and thus obviate the difficulty .

A decin orm al s olu t i on of the bi i odat e i e one c ontaining -

,
. .
,

in mils
1 0 00 gms of the salt may b us d to advan tage
. e e .

Such a s oluti on will k eep unch anged fo y ars and m ay be r e ,

em p l oy ed as f oll ows for the st an dar diz ation of so dium thio

sulphate solu t i on
Into a gl ass s t op pered fl ask of 5 mils c apaci ty intr oduc e
-
2 0

10 mils of a 5 p er c en t s olution of p o tassium i odid * mil ,

1

of diluted hy dr ochloric acid and exac t ly 5 mils of th ab ove 2 e

potassium bi iodate solu tion -

.

This brownish yellow s olution is now titrat d wi t h the

~
e

sodium thiosul phat e s olu t ion which is sl owly delivered

from a burette until the solution b ecom es pal e y ellow in
col or ; a few drops of starch s olution are now added and ,

the t itrat i on c on t inu ed (the fl ow b eing r educ ed to dr op s )

until the blu e color is just disch arg ed D uring the ti tr a .

tion the flask Shoul d be frequ en t ly s t oppered and vigorously

,

S h ak en .

Wh en the blu e c ol or is disch arg ed n ot e the numb er of ,

mils us ed If an exac t ly decinorm al thiosul phate solution is

.

tak en 5 mil s will be r equired to r ac t wi t h the 2 5 mils of

,
2 e

potassium bi iodate s olu ti on under the above conditions If

-
, .
,

The p ota i um i odid mu

*
ss be i n uffi ci en st s t quanti ty not only to react
t t tt tv
wi h the bi -i oda e q uan i a i ely, as hown i n the s equat i on but al s o to di ss olv e
,

the i odi n whi ch i s lib r t d

e a e .
2 16 THE E S SE N TI AL S OF V OL U ME T R I C AN AL S S Y I
I2 2 N
( a2 82 0 3
‘"
l SH2 O ) N 3 2 S4 0 6 l
‘ ‘
2 N aI ‘‘
l IO H2 0 .

10 )
N
g s in . gms . or 1 0 00 mil s IO V S . .

Ea ch mil of I O thiosulphate represents gm of .

iodin .

If in the ab ove assay 39 mils of so dium thiosulphate

were c ons um ed then ,

X 39 gm .

1 00
99 p er c en t .

o s S olut i on This is an aqueous soluti n of iodin

Lug l ’
. o

and pot assium i odid .

I t is es t imat ed for i odin in the s am e way as the f or egoing .

The p otassium iodi d acts m er ely as a s olv ent for fr ee io din ,

an d do es n ot é n te in t o the r eaction r .

Ten or tw elv e gr ams of the s oluti on is a c onv eni ent qu antity

to op erat e upon Starch s olution is the in dic ator
. .

Tin ctur e of Io din An alcoholic s olution of fr ee iodin

.

must be dil ut ed with a s olution of p o tassium iodid b efore ,

ti trat ion in order to prevent the precip itat ion of io din which
, ,

w oul d r esult upon the addition of the aqueous stan dard solu;
tion The U S F tinctur e of iodin contains potassium i odid
. . . .

and th er ef or e may be t i t rat ed as i t is .

Indirect Io dometri c E sti m ati ons The titration m ethods .

p r eviously d escrib ed in which io d in is us ed as a st an dard

,

s olu tion and the estimation of free iodin by m eans of so dium

thiosul phate a e cl ass ed as di ct i odom tri m thods The
,
r re e c e .

foll owing m eth ods in which the s treng th of the substanc e

,

under analysis is det ermined by the qu antity of io din which

 AN AL Y SI S BY OXI DATI ON AN D R E D U CTI ON 2 17

it lib erat es from an iod d are known as i ndi e t i odom t i i r c er c

methods . Pot assium i odi d s added in exc ess to an acidu lat edi

solution of the substance and the lib erated iodin estim ated ,

by m eans of s t an dard t hi osul p h at e T h es e m et ho ds are .

am ong th e mos t acc urat e of all v olum et ric an alys es and ,

tak e in a v ery l arg e cl ass of substanc es Among the sub .

stanc es whi ch may be analyz ed by this m ethod are chlorin

and bromin and all subst anc es which r eadily lib er at e thes e

el em en t s : f erric s alts m angan at es chromat es m etallic p ero

, , ,
x

i ds an d oth er subst anc es from which oxyg en can be easily

,
.

lib erat ed .

Fr ee Chl orin or Br om i n Fr ee chl orin acts u p on p otas .

sium iodid lib erating iodin as p er the equati on

, ,

C 12 2 KI 2 K C 1+ 12 .

Thus
it is s een that each atom of chl orin will lib erat e one
atom of iodin h enc e by det ermining the quanti ty of iodin
,

by m eans of a st and ard thi osul p h at e s olution the qu antity

of chl orin pr es ent is easi ly asc ertain ed gms of .

I= gms of C1) The s am e appli es to free bromin

. .
,

on e atom of bromin will lib erat e one atom of iodin

1 00 0 mils of so dium thi o
10

sulph at e is equi val ent to gi ns of iodin .

,
an d h enc e to
gms of chlorin or
. gms of bromin
. .

T mil of 10 so dium t hi osulph at e is eq uival ent to

hus 1
—

gm of io din ; . gm of chl orin ; .

gm of bromin
. .

C hlori n c ann ot be di r ectly titrat ed with sodium thi osul

*
V
The i odid sh ould be i n sufli c en t i ex ce ss to k eep the li be a edrt i odin in
s luti
o on as KI I . .
2 18 THE E SSE N TI AL S OF V OL UME TRI C AN AL S S Y I

p h at e b ec aus e ins t ead of the t et rat hi onat

,
b eing f orm ed as e

with iodin s ul ph uric aci d is produc ed; f ur th erm or th ere is

,
e

no r eadily obs ervabl e end p oin t as th er e is wi th io din

-
.

Chl orin Wat er This i s an aqu eo us s olu t i on of chlorin

.
,

C l = c ontaining at l east p er c e n t of th e gas .

The estim at i on of chl orin is effect ed in an in dir ct way e ,

n am ely by det ermining th q uan ti ty of i odin which i t lib erat es

,
e

from p ot assium i odi d .

A definit e q uan t i ty of chl orin will lib rat e a defin i t e q uan e

ti ty of i odin from an i odid ; th es e quan t i t i es a e in exact r

prop or ti on to th eir at omic w igh t s as the equati on S h ows

e ,

C 12 2 KI 2 K C1 12 .

gm s .

Th us it 1S s een that by es t im ating the lib erat ed i odin the

quanti ty of chl orin m ay be det erm in ed wi th acc uracy .

Ten g amS is a c onv ni n t q uan t i ty to op erat e up on

r e e To .

this ab ou t h alf a gram of p otassi um i odi d is added A li t tl e .

starch soluti on is th en in troduc ed and the titration is b g un , e

with d ecinormal s odium t hi os ul p hat e .

Wh en the bl ue c ol or of s t arch i odi d has n t ir ly disapp eared e e

the r eaction is finish d e .

The r eacti on b et w een i odin and s odium thi osul p h at e i s

illustrat ed by the foll owing quat i on e

I2 2 ( 2 82 0 3
N a SH2 O ) 2 N aI + N a2 s4 o e IO H2 O .

N
gm s . m
g s . or 1 0 0 0 mil s I O
VS . .

N
T hus we see that 1 0 00 mils of
IO
N 3 2 82 0 3 SH2 O . r ep res ent
 220 THE E SSE N T ALS O F I V OLU ME TRI C AN AL YSI S
s en t ing gm of the sam p l e) a e r em oved by m eans of
. r

a p p i tt e a
e n d tr eat ed wi t h 1 gm of p ot a ssium i odi d l an d .
’<

5 mils of ac et ic aci d and in t o the r esul t ing r eddish brown

,
-

liqui d the T s odium thi osul ph ate is d livered from a burette

0
e .

T owards the end of the t i trat i on wh en the br ownish c ol or ,

of the liquid is very fain t a few drop s of s tarch solu t ion a e , r

added and the titrat i on c on t inu ed un t il the bluish o gr eenish r

color pro duced by the s tarch has en tirely disappeared N ot .

l ess than 3 mils of the volum etr ic s oluti on sould be required

0

to pro duce this result .

The r eac t i ons which t ak e p l ac e i n t his pr oc ss are illus . e

t ated by the foll owing equat i ons

r

01
'

C21 (0 C1) C 1 2 HC2 H3 0 2 Ca (C 2 H3 0 2 ) 2 H2 O C12 ,

C12 Z KI 2 K CI + 12 .

2 )

gm s .
gm s .

12 l
‘ ‘
2 N
( & 2 S 2 0 3 511 2 0 ) 2 N aI ‘
l N a2 S4 O a l
' ‘ ‘
TO H2 O .

i
N
gm s . 1 00 0 mil s IOthi s o ulp ha e t VS . .

I t is th us s een that I mil of the decinorm al s odium thio

sul ph at r epr es n t s
e egm of i odin which in t urn i .
, s

eq uiv al en t to 0 0 3 54 6 gm of chlorin
0 . .

Th n e

54 6 X 3 gm 0 .

0 ro 63 e
p er c en t of avail abl e chl orin .

In o rd re to a ss um e a sufi ci en t exce ss of po t ssi

a um i odi d, t k
a e twi ce

as much of i t as of the bleachi n gp -

owde r .
 AN AL Y SI S BY OX DA I TI ON AN D R E D U CTI ON 22 1

T his is a very rapid m etho d for estimating chlorin ; but

when calcium chlorate is pr es ent in the bl eaching p ow der .
-

(a n d it of t en is through
, im p erf ec t m anuf ac t ur e ) the chlorin

from it is r ec orded as w ell as that from the hyp ochlorit e

, ,

the chlorat e b eing decom p os ed int o chlorin etc by hydr o , .

,

chl oric aci d (which is som et im es used) The chl orat e h ow ever .
, ,

is of no valu e in bl eaching ; its chl orin is not avail abl e Henc e .

,

unl ess th p ow der is known to be free from chl orat e the anal
e ,

y si s sh oul d b e m ade by m eans of ars en ous aci d solu t i on o -

, r

by using ac t ic aci d ins tead of hydrochl oric and thus avoid

e ,

lib erating chl orin from the chl orat e which may be pres en t
The vari ous bl eaching p r ep arat i ons of the m ark et w hi ch
dep en d up on t h eir avail abl chl orin a all s al t s of hyp ochl orous
e re

aci d ( HCl O ) o s olu t i ons of s uch s al t s

r .

E au de Jav ell e (Jav ell e s Wat er) is a s olution of p otas

’

sium hypochl orit e and p otassium chl orid A s oluti on of mag .

n esi um hypochlori t e is known i n c omm erc e as Ramsay

- ’
or s

G ou lle s Bl a chi ng F lui d The s olution known as Wi lson s

’ ’
r ve e .

Bl a hi ng F lui d con t ains aluminum hypochlorit e

e c .

S ol ut i on of Chl orin at ed S o da (L ab arr aqu e s Soluti on )

’
.

This is an aqu eous s ol uti on of s ev eral chl ori n compoun ds

of s odium , p rincip a lly so d i um chlori d an d h y p ochlori t e c on ,

t aining at l east p e r c en t by w eigh t of avail abl e chlorin .

In this soluti on as in chlorinated lime it is the avail abl

, , e

chl orin which is estimated The chlorin is fir st lib erated with

.

hydrochloric or acet ic acid; this th en lib erates iodin from ‘

p ot a ssium io did a, n d t he fr ee io din is th en det ermin ed by

s tandard so dium t hiosul phate .

Seven gr ams of chl orinat ed so da solution are mix ed W i t h

50 mils o f w a t er 2 ,gms of .
p o t assium i od i d a n d 1 0 mils of ,

ac etic acid are t h en added tog eth er with a few drops of st arch
,

solution Into this mixture the decinorm al so dium thiosul

.

phate is d elivered from a burett e un t il the blu e or greenish

2 22 THE E SSE N TIAL S OF VOLU ME TRI C AN AL Y SI S
N
t in t of the liquid is just discharged Each mil of thi osul
E
.

p h at e us ed up r ep r es en t s gm of av ail abl e chl orin . .

The p otassi um i odi d s houl d alw ays be added b efore the ac etic
aci d so t h at the chl orin has p otassium io di d to act upon as
,

it is lib erat ed and thus l oss of chlorin is obviated

, .

Bromin Wat er or any subs t anc e con t aining fr ee bromin

,

may be ass ayed in ex ac t ly the s am e m ann er as th at describ ed

for chl orin w at er Fr ee chlorin mus t how ever be abs ent
.
, , .

N
ch mil of B th osulphate s olution represen t s
Ea l gm .

of bromin .

Assay of Hydr ogen D i ox i d The io dom etric

m et od which origin t d wi th Kingzett is b as ed up on th
h ,
a e *
, e

fact t h at i odin is lib erat ed from p otassium i odi d by hydrog en

di o i d in the p r es enc of s ul p huric aci d an d th at t his lib era
x ,
e ,

t i on of i odin is in direc t p rop or ti on to the avail abl e oxyg en

c on tain d in the dioxi d
e .

Th en by d t ermining th am ount of i odin lib erat ed the

'

e e ,

av ail ab l oxyg en is r eadi ly f oun d

e .

Hz O z HQ S O 4 2 KI K 2 80 4 Z HQ O 12 .

1
7
= I v
a ai lable 0 = 8

T his shows th at gms of i odin are lib erat ed by 1 7 .

gms of abs ol ut e di o i d which are equ val ent to 8 gms of

. x , i .

av ail abl e o yg en x .

N
Thus I O OO mils of so dium thiosul phate V S which . .
,
10

absorb and cons equ en t ly r ep r es ent gms of io din a e .

,
r

equival ent to gms of H 0 or gm of avail abl e oxyg en

.
2 2 . .

J . Chem Soc . .
,
1 880 , Vol 3 7 p 7 92
.
, . .
22 4 THE E SSE N TI ALS OF V OL U ME TRI C AN A Y S S L I
The sulphuric aci d us ed in this ass ay m us t b fr from e ee

s ul phurous acid ars en ous acid and ni tric aci d an d th p otas

, ,
e

sium i odid mus t c on tain n o i odat e .

D i st ill at i on Met h ods M ang an at es chrom at s m etallic

.
, e ,

p er oxi d s ,
a n d a gr at v ari
e et y o f s ubs t anc s c on t aining oxyg en e
,

incl uding an timonic oxid and arsenic pentoxid will wh n , , e

h at ed wi t h c onc en trat ed hydr ochl oric lib erat e an equival en t

e ,

am oun t of chl orin This is illustrat ed by the foll owing equ ati on
.

Mn 0 2 + 4 H C1= Mn C lz 2 H2 0 C12 .

The chl orin which is ev olv d is p ass ed in t o a s ol ut i on of

e ,

p ot assi u m i odi d an d lib rat s an eq uiv al en t of i odin

e e which ,

l atter subs tanc e is t h en es t imat ed by ti trat i on wi th s odium

thi os ul p hate sol ut i on The quan t i ty so fo un d is ther fore
. e

a m as ur e of the origi n al s ubs t anc e an d of i t s o yg n c on t ent

e x e .

Th p r oc ess m ay be c arri d out by m eans of th app arat u

e e e s

FI G .
48 .

devis ed by Buns en Fi g 4 8 or by that of Fr es eni us Fi g 4 9

,
.
, , .
,

o M ohr Fi g 5
r ,
. 0 .

An acc ur at ely w eigh ed q uantity of the s ubst anc e to be

an alyz ed is in t r oduc ed into the roun d bo tt om ed fl ask a Fi g -
, .

4 8 .Th e fl a sk is t h n fill ed toeabout two t hir ds i t s c ap aci t y -

wi th c onc en trat ed hydrochl oric aci d and quickly conn ct ed , e

by m eans of a short rubb er tub e with a long bulb ed d elivery -

 AN AL S S BY O Y I XI D ATI ON AN D R E D U CTI ON 225

t ub e b which is introduc ed in t o and ex t ends to the b ottom of

, ,

an inv ert ed bulb ed r et ort c The l arg er bulb of th r et or t is

, . e

filled to two thi rds of its c ap acity wi th a p e c en t s ol ut ion

-
10 r

of p otassium iodid Heat is app li ed to the flask and the chlorin

.
,

distils ov er into the p otassium iodi d s oluti on whi ch b ec om es ,

brownish red thr ough lib erat ion of iodin The dis tillat i on
-
.

is c on tinu ed un t il about one third of the acid flui d has pass d

-
e

over or until a p eculi ar cracki ng sound indic at es the absorp tion

of hot hy drochloric acid vap or .

The fl ask t og eth er wi t h i t s deliv ery t ub e is t h en sl owly

, ,

r moved the h eat ing how ev er is c ontin ued un t il the t ub

e , , , e

FI G 4 9
. .

is entirely wi thdrawn in ord er to prev ent the io did soluti on

,

b eing drawn ov er into the flask The r etort is th en shaken .

so that any trac es of chl orin which may h ave escap ed abso p r

tion are t ak en up and the cont ents of the r etort poured into
,
226 THE E SSE N T AL S OF I VOLU ME TRI C AN AL YSI S
a b eaker ; the r etort and the d eliv ery tub e a e then rins ed wi th r

wat er and the rinsings add ed to the fl uid in the b eaker and ,

titrat i on with s t an dard s odium t hi os ul phat e b egun imm ediat ely .

I t is imp or tan t t h at the quan t i ty of p otassium iodi d is suffi '

ci ent to k eep the lib rat ed i odin in s olut ion and the p otas
e ,

sium iodid free from iodate and the titrat i on s tar t ed wi th ,

out d el ay to av oi d lib erat i on of i odin t hr ough action of the

air upon the strongly aci d pot assium i odi d s ol ut i on Wh en .

all the chlorin has p ass ed ov er and hy drochl oric acid gas

b egins t o distil the liqui d in the r etort is apt to be drawn b ack

,

into the flask b ecaus e of the great affini ty which hydrochl oric
acid gas has for w at er an d the r esult ant con dens ati on in the
,

flask This regurgit ati on may be avoid ed by in t rod ucing

. .

into the g en erating fl ask a small p i ec e of m agn esite whi ch ,

slowly dissolv es in the aci d s olu t ion and so k eep s up a constant

flow of carbon dioxid which by its pressure prev ents b ack fl ow
,
-

of the fluid The bulbs in the r etort and d eliv ery tub e a e
. r

also c alcul ated to p r ev ent this r eg urgit ati on .

The Fr es enius ap p aratus is illustrat ed in Fi g 4 9 In this . .

the pot assium i odid soluti on is c ont ain ed in two j oin ed U sh ap ed —

tub es The delivery tub e from the distilling fl ask ent ers one
.

of the U t ub es through a p araffi n so ak ed cork (which fits

- -

tigh t ly) and t ermin at es jus t ab ov e the p otas si um i odid s olu

,

tion In op erati on the U tub es shoul d be k ep t in ice wat er

.
-
,

an d all the fi tt ings sho uld be air tight Parafli n c ov er ed c ork

- —
.

stopp ers onl y shoul d be us ed .

Aft er all the chl orin has p ass ed ov er or wh en a b ou t on e t hird -

of the acid has distill ed ov er the apparatus is all ow ed to s t and

,

for a few minutes to p ermit all trac es of chl orin to b ec ome

,

absorb ed ; the ap p lic ation of a suction p ump to the r ear ou t l et

tub e will h elp to bring about this r esult .

Mohr s app arat us shown in Fi g 5 is of v ery simp l e con

’
,
. 0,

struction and easy to use .

228 THE E SSEN TIAL S OF V OL UME TRI C AN AL Y SI S
conn ec t ed wi t hout d l ay wi th the v ess l c ontaining the p otas
e e

si um i odid s ol ut i on Th flask is th n gradually h eat ed o

. e e s

t hat a s t ady c urr en t of chl orin p as s ov e in to the p otassi um

e se r

iodid s ol uti on Wh en th evol ut i on of chl orin ga b egins to

. e s

diminish th heat is sl owly rais ed to b oiling and c on t in ued

,
e ,

at t his p oin t un t il ab out on e t hird of the aci d liq ui d has di s

-

till d ov er The deliv ry tub e is then rem ov d an d rins ed a

e . e e ,
s

p r evi ou sly d scrib d and the lib rat ed i odin ti t rat d by m eans
e e ,
e e

of s odi umthi os ulphat s ol uti on e of which we will as sum e

T
o
,

60 mils were c onsumed .

The r eac t i ons a as f oll ows re

()
a Mn O z + 4 HC1= Mn Clz 2 HzO C IZ .

b
()

()
C 12 2 N 3 2 82 0 3 5HQ O °
2 N aI N azS4 0 6 IO HzO .

N
gm s .
gm s = . 1 000 mil sE )
VS. .

N
gm . I mil —
VS. .

I o

Th es e qu ations sh ow that
e gms of s odium thiosul .

phat e will d ec ol oriz e g m s o f i od in which 2 q u anti t y is .

,

lib erat d by
e gms of chl orin which is i t s elf lib erat ed .
,

from hydrochl oric acid by 3 gm s o f m a ng a n es e di oxid '

. .

T h er efor e mil of a decinorm al solution of so dium thi0

I

sul phat e (containing gm s in 00 0 mils ) is e quiv a l ent . 1

to 00 12 69 gm of I ; 2 gm of Cl ;
. gm of . .

MnO ; z gm of O (avail abl e) . .

The 60 mils of the thi osul ph at e solu t ion us ed in this ass ay

will th erefore represen t 43 5
4 6 X 6 0 = 2 60 8 g m of pur
0 00. e 0 . .

M nO z or , p e c ent r .
 AN AL Y SI S BY OXI DATI ON AN D RE D U CTI ON 22 9

1 00
p er c en t .

This is the m ethod which sh oul d be used for the assay of

n ative m anganese di oxid The freshly pr ecipitat ed mangan ese
.

dioxi d of the Ph arm acop oei a may be ass ay ed by th mor e e

easily p erf orm ed dig esti on m et ho d describ ed on p ag e 2 33 .

E st i mat i o n of Chromi c Aci d an d Chrom at es Chromic .

anhydrid ,
chromium trioxid (Cr O = wh en h eat ed with g

c oncentrated hydrochloric acid lib erates chlorin as p er the ,

equ ation ,

CI O 3
’

OHCl Cl Clg
'

3H2 0 C13 .

46
-

One hundred p arts of Cr 0 lib erat es 3 X p arts of 3 Cl ,

h enc e one atomic w eight of chlorin p art s repres ents , ,

N
+ p arts of Cr 0 3 Or I mil of B sodium thiosulphat e repre
.

s ents gm of Cr O g . .
,

E st im atio n of Pot assium D i chr om at e

Thi s s alt as expl ain ed in a pr evi ous ch apt er has th ee atoms
, ,
r

of oxygen avail abl e for oxidation A mol ecul e of this sal t is .

th erefor e equival ent to six atoms of c hlorin and wh en b oil ed ,

with hydrochloric acid will lib erat e six atoms of chl orin as ,

the equ ation sh ows .

K 2 Cr2 0 7 I 4 H C 1= 2 K Cl 2 Cr C 13 7 Hz O C
3 21 .

-4 6

Thus on eat om of lib r t d chl orin will repres en t one sixt h

e a e —

of which is p arts of potassium dichrom at e Then .

N
1 mil of 5 sodium thi osulph at e will r epres ent gm .

of K 2 CI O 7 In the s am e way all oth er chromates may be

Q .

treated but th es e compounds will wh en treat ed with hydro

, ,

chloric acid lib erat e chlorin at on ce and with out the app lic a
,
2 30 THE E SSE N TIAL S O F VOL U ME TRI C AN AL Y SI S
t ion of much h eat h enc e som e chl orin is ap t to be l ost b efore
,

the dis t ill ation fl ask can be c onn ect ed wi t h the ap parat us and ,

th er efore it is m ore con v enient to emp loy the digestion m ethod

.
'

l at er describ ed .

The r eac t ion in the c as e of n eu tr al p o tassi um chr om at e is

as f oll ows

K 2 CI O 4
‘
8H C1 2
= K C1+ 4 H2 O Cr C 13 C 13 .

L ead p eroxi d PbO ; c ob al tic oxi d C0 0 ; nickel o

, z xid, 2 3 ,

N i 0 as w ell as m any oth er s ubs t anc es may be ass ay ed by

2 3, ,

this dis till ation m eth od .

E st im at i on of Al k al i I odi ds by the D i st ill at i on Met hod .

This m ethod is b as ed up on the fact that m etallic iodi ds wh en ,

tr eat ed wi t h f erric s al t s in aci dul at ed solu tion yi eld , up all of

th eir io din As sh own in the equ ation
.

F G (S O )
Q Z KI K S O
4 3 FC S O
Q 1 4 Z 4 2 .

The i odin t hus set free is di s t ill ed into a sol ution of p otassium
iodid and its quantity d etermin ed by titration with s odium
thiosu lph at e in the usu al m ann er .
2 32 THE E SSE N TIAL S OF V OL UME TRI C AN AL Y SI S
10
p c ent pot assium io di d s olu t ion and aft er conn ections a e
er , r

m ade tigh t h eat is gradu ally appli ed to the dis tilling flask
,
.

Af t er most of the io din has p ass ed ov er the h eat is rais ed to ,

boiling and continu ed at this temp eratur e un til about one

,

fourth of the liquid has p ass ed over and the s ol uti on in the ,

distilling fl ask is no long er of a brown col or .

Wh en the r ec eiving v ess el has s uffi ci ently cool ed it is dis ,

conn ect ed and its cont ents titrated wi t h d ecin ormal sodium
t hi osul phat e using s t arch as in dic ator Befor b egi nning
, . e

t i tration h ow ever it is n ec ess ary to rins e the low er extremity

, ,

of the t ub e and the stopp er into the solution in the r ec eiving

v ess el in order that every trac e of i odin be coll ected

,
.

The c alcul ation is th en m ad e as fOllOWS ‘

()
a F ez (80 4 ) 3 (N I 102 80 4 .
—
Z KI
33 2 -
0 4
Ks 4 (N H4 ) Q S O 4 2 FC S O 4 l 12 ‘ ‘
.

2 53 84
-

b
() 12 2 N a2 S 2 0 3 SHz o 2 N aI N a2 S 4 0 6 IO HzO .

N
gm s . 1 00 0 mil s VS. .

N
gm = 1 mi l VS
;0
. .

Ref erring to the abov e equations we see that 2 gms .

of i odin a lib erat ed from

re gms of p otassium iodid; .

thus gms of iodin r epres ent .

gm s f o f pot assium
iodid and th erefore 1 mil of decinorm al sodium thiosul ph ate
,

s olution repres en ting

,
gm of iodin will at the sam e .
,

tim e r epres en t gm of KI . .

If in the above assay 9 mils of $6 sodium thiosulphate 2

a e
r c o nsum ed w e mul t i p ly the ,f ac t or for K I = 0 1 6 60 2 gm . 0 .

by 9 t his gives
2 , g m th e qu an t i t y of pu re KI in.the,

0 5 gm tak en which is ab ou t 96 per c ent

. .
, .
 AN AL YSI S BY OXI D ATION AN D R E D U CTION 2 33

i
D gesti n M e h ds o
t o
The d .istill at ion m ethods above de
s crib
ed m ay be a ded voi a in m ny cas es and the mor e easily
perform ed digestion proc ess used For inst ance freshly pre .
,

cip i tated m ang an es e di oxi d l ead p er oxi d c hr omic aci d chlor

, , ,

at es brom at es
,
i od at es f erric s al t s and a great m any oth er
, , ,

substanc es may be ass ay ed by m ere dig s t ion wi th hydro

,
e

chloric aci d at a sligh t ly el evat ed t emp erat ure .

The digestion is p erf orm ed in a s t r ong gl ass b ot tl e p r ovid ed ,

with an accurat ely fittin g groun d gl ass s t opp er which is tied

-

down by m eans of wir e or s ecur ed bv a

cl amp See Fig 52 . . .

Bef or e using the bottl e for this op era

tion i t sh ould be t es t ed by s ecurely tying
d own the stopp er and immersing the
bottl e ntirely in hot water to see if the
e

stop p er fits su ffi ci ently tight If it do es .

n ot bubbl es of air will escap e from

,

insid e and the bottl e is us el ess for the

,

purpos e mtended In that event the .

stopp er must be r eground into the neck

of the bottl e with a littl e v ery fin e em ery

and wat er The c ap acity of the bottl e may v ary from 50 to

.

1 0 mils
5 .

The P rocess The subst anc e is accurat ely w eigh ed and

‘
.

introduc ed into the b ottl e t ogeth er wi th a small quantity of

coars ely p owd ered gl ass or small pure flint p ebbles (to prev ent
c akin g esp ecially in the c as e of ins olubl e powd ers) A suffi
, .

ci ent exc ess of p otassium iodid s olu t i on is th en added followed ,

by som e pur e conc entrat ed hydrochloric acid The stop p er .

is th en quickly ins ert ed firmly s ecur ed by wire or a clamp

, ,

and the bottl e p l ac ed in a wat er b at h and the w at er gradu ally ,

h eated to boiling ; this temp erat ure b ein g c ontinu ed until

d ecomposition is compl et e which is usually in about half an
,
hour The bottl e is t h en all ow ed to c ool sl owly and its con
.

tents em p tied int o a b eak er Th en aft er washing the b ot t l e

.
,

and adding the w ashings t o the c on t n t s of the b eak er the

e ,

liberat ed io din is estim ated by t i trati on wi t h sodium thio

sulph ate .

The pot assium io did us ed in this pr oc ess must be absolut ely

free from io date .

N
O ne mil of T sod um th osulphat e
S
i i IS e qu val n t to
i e

K C10 3

Es i t m at i o n of Chl orat es Brom at es and Io dates The

, .

estim at ion of t h es e s alts is b as ed up on the f act th at in each

c as e one equi val ent of the acid o i t s monob asic salt lib erat es
r

six equival ents of chl orin and c ons equently six equiv al ents
of iodin wh en d ec omp os ed by the dig es tion m ethod .

This is illustrat ed by the equ ations

() 0 K C10 3 6HC1= 3H2 0 K C1+ C 16 ;

5
() K Br 03 + 6H C 1=
3H 2 0 + K Br + C 16;

() c K I O 3 + 6HC1= 3112 0 KI C16 .

d
() C16 6KI = 6K C1+ I G .

In the dist ill ati on proc ess h ow ev er bromat es and io dat es

, ,

lib erate only fo ur equival ents of iodin whil e bromous chlorid

,
2 36 THE E S SE N TIALS O F V OL U ME TRI C AN AL Y SI S
E x ample . E sti mati on f
o gm of
P otassi um Bromate . .

the s alt is dissolved in 1 5 mils of wat er 4 gms of o t assium

p , .

iodid are added follow ed by 4 mils of concentrated hydro

,

chloric acid The bottl e is securely closed as in the fore

.
,

going assay and h eated for half an hour at 50 C Th en

,
°
.
,

af t er dec om p osi t ion t i trat ion wi th s odium thiosul h at

1
,
p e
0

solution is b egun each mil of whi ch r epresents

, gm .

of pure K Br0 3 .

If T153“1
; of one six t h of the mol ecul ar w eight of eith er s alt
-

be t ak en for ass ay each mil of the , thiosulphate solution

us ed will in dic at e p er c ent puri ty 1 .

E st im at i on of F err i c S al t s Wh en a f erric s alt in an .

aci dul at ed sol uti on is dig es t ed wi t h an exc ess of p o t assium

i odidZ the s alt is r ed uc ed t o the f err ous st at e an d i odin is set free ,

.

F€ C16 Z KI Z FC Cl 2 K C1+ 1 z 2 2 .

O ne tom of iodin is lib erat ed for each atom of iron in

a

the f erric stat e The lib erat ed i odin is th en det er min ed by

.

so dium thiosul phat e in the usual way gms of iodin . .

5 gms of m.et allic ir on .

The m etho d is ex emplifi ed in the following ass ay

F err i c Chl or i d (F e C1 or F C C l ) 5 of
2 t
6he dry s alt g . 0 .

accurat ely w eigh ed is put into a 1 00 mil gl ass st o p er ed b ottl e -

p
-
,

15 mils of w at er are added to diss olve the s al t and t h en

3 ,

mils of concen trated hydrochloric acid and 2 gms of pur e .

p ot assium io di d a e in tr oduc ed Trhe bo t tl e is s ecur ely clos ed

.

and its cont ents h eat ed t o 4 C ( 0 4 F ) for h alf an hour

° °
0 . 1 . .

A high er t emp eratur e must be avoi ded o t h erwis e iodin will ,

be vol atiliz ed The liquid is t h en cool ed and the lib erat ed

.

N
iodin titrated with 13 sodium thiosul phate until the color is
just discharged Starch may used as indicator
. .
 AN AL S S Y I BY OXI DATI ON AN D R E D U CTI ON 2 37

N
ch m l of E th osulphate s olut on used represen t s
Ea l 1 i
5582

gm of m etallic iron or
. gm of pure ferric chlorid . .

The f oll owin g equ ations ill ustrat e the r eac t i ons

F e C1 KI 2 F eC1 K Cl
6 I 2 2 2 2
84
-

Th en
12 2 N 3 2 82 0 3 .
5H2 0 = 2 N aI N a2 S 4 0 6 IO HzO .

N
gm s = . 10 00 mi l s T VS6
. .

The ss ay of o th er f rric s al t s is prac tically

a e the s ame as

that describ ed ab ov e .

Ea ch mil of . s odium t hi osulphate is e qui al ent to v

Fe rrum F e , gm .

F erric ammoni um sulphate Fe , 2 (8 0 4 ) (

3 N H4 ) 2 8
. 0 4 0 02 66
Ferric chl ori d, Fe C1 2 6

F e2 C16 + 1 2 HgO . .

nitrat e F€ (N O )
, 2 3 6

oxi d F e 0
, 2 3

sulph at e Fe (SO ) , 2 4 3

In the c as e of the sc al e s alts of iron which a e mostly of , r

in defini t e and variabl e c omp osi t i on it is the qu an t i ty of m et allic ,

iron pres en t which is det ermined .

The solu t i ons of f erric s alts are estim at ed in the s am e man

n er . It is the rul e t o tak e to 2 gms of the s olution for ass ay 1 . .

Assay of Chromi c Aci d Chromates and D i chromates , .

D iss olve abou t g m o f the subs t anc s accur at ely w eigh ed in

1 . e

a s t op p er ed w ighing b ott l e in suffi ci ent dis t ill ed w ater to

e ,

measur e 1 00 mils .

To 1 5 mils of thi s Solu t i on add 3 mils of hy drochlori c aci d

2 38 THE E SSE N TI AL S OF VO LU ME TRI C AN AL YSI S
and 2 gms of p otassium iodi d in a gl ass stop p ered contain er
.
-
,

shak e the mix tur all ow i t to s tand for fi e minu t es t h n

e, v ,
e

dilu t e wi t h dis t ill ed w at er to m easur e mils and t i trate wi th 100 ,

t enth norm al s odium thi osul phat V S using starch T S as

- e . .
, . .

i ndic at or .

E ach mil of the t hi osu l p h at e V S us ed corr espon ds to . .

gm of Cl O .
‘
g .

See equ at i ons on p age 9 2 2 .

Assay of Ars eni c O x i d (As aO ) and Ars en at es A l o anti s . s

moni compound
c D iss olv ab ou t s
gm . of th subs t anc e e . e

accurat ely w igh ed in 2 5 mils of distill ed w at r h eat the s olu

e e ,

tion to 8 C and add 1 mils of hydrochl oric and 3 gms of

0
o
. 0 .

potassium i odid A ll ow the mix tur to s t an d for fif t een minu t es

. e

at 8 0
0
C t h en c ool and t i trat wi th t en th norm al s odium
.
,
e -

thi osul phate V S using s tarch as in dicat or The solu t ion mus t
. .
,
.

be d ci dedly aci d in r eac t i on

e The func t i on of the acid is .

expr ess ed by the equ ati on

KI + HC1= K Cl + HI .

The HI th en reac t s wi th the AS O 5 r educing it Q , to ASzO 3

and lib erat ing i odin as the f oll owing equ ati on shows ,

AS zO s + 4 HI A s o3
z Q HQ O 2 12 .

Ea ch mil ten th norm al thiosulphate V S corre

of the -
. .

sp onds to 57 4 8 gm of A s o ,or gm of N a H As O .
z g .
g 4

(so dium ars en at e ) .

Assay of Co pper This m eth od dep en ds u p on the r eaction

.

b etw een copper s al t and pot assium io did in which iodin is ,

quantitat ively lib erat ed .

2 CHSO 4 + 4 KI CU Q I Q 2 K 2 80 4 IQ .

2 X 1 59 64 . 2 X 1 2 6 92 .

The solu ti on of the copper sul phate should be w eakly acid .

Ac eti c acid is usu ally us ed All io din lib eratin g subst anc es .
240 THE E SSE N TIAL S OF V OL U ME TRI C AN ALY S SI
The xcess of iodin is t h en t i trat d wi th sodium thiosul
e e

phate starch b eing used as in dicat or

,
.

The P rocess O ne gm of the s al t accur at ely w eigh ed is

. .
, ,

h eat ed with mils of dis till ed water 5 mils of t en t h normal

10 , 0 -

iodin V S and 5 gms of p otassium i odi d The flask is s t oppered

. . . .
,

and the mixture all ow ed to stand wi t h occasi onal agitat ion , ,

until com p l ete s olution has tak en p l ac e The excess of iodin .

18 th en titr at ed as abov e describ ed .

N
mil of T iodin V S us ed corresponds to
E ach
0
. .

gm of HgCl or 0 3 75 gm of HgI
. 0 2 2 . .

Reducti on Metho ds
I nvolving th e U se of S tandard Arsenous
Aci d S o luti on (Chl or om etry)

As previously describ ed ars enous oxi d wh en brought in ,

contact with io din in an alkaline solution results in an oxida ,

t i on of the form er to ars enic oxid and a c onversion of the ,

iodin to hydrio dic acid as shown in the equ at ion ,

AS 2 O 3 Z H2 O I4 AS 2 O 5 4 HI .

Adv an t ag e is tak en of this reaction for the es t im ati on not ,

only of arsenous and antimon ous compoun ds but als o of iodin ,

and the oth er h alog ens chlorin an d bro min as w ell as of all
, ,

t hos e bodi es which wh en h eat ed with hydrochl oric acid evolve

, ,

c hlorin as for ins t anc e the p eroxids

A

, .

The r eac t i on wi t h chl orin is as foll ow s

C 14 Z H2 O + AS 2 0 3 4 H cl l AS Q O 5
‘ ‘
. .

T his r eac t i on is r eally an oxi dat i on o fa as the format ion ,

s r

of ars enic oxid (AS O ) is c onc ern ed but th er e is no accom

Q 5 ,

p anying reduction The c onv ersion of the hal ogen to an

.

h aloid acid is not stric t ly a r educ t i on in the acc ept ed s ens e

 AN AL S SY I BY OXI DATI ON AN D R E D UCTI ON 24 1

of the word N ev erth el ess fo obvi ous r eas ons we sp eak

.
,
r ,

of an alys es don e by m eans of ars en ous acid as reduc t ion

m et hods .

The chi ef val ue of this m eth od is found in the es t im ation

of fr ee chlorin as in chlorin w at er and the av ail abl e chlorin
, ,

exis t ing in hypochlorit es or th at evolv ed from hydr ochloric

aci d by h eating with p eroxids Henc e the d esign ation chlor

.

ometry .

In c arrying out this m ethod free alkali must be pres ent

t o c ombin e with the h aloid acid which is form ed The alkali .

mus t be in the form of bicarbon ate N ormal c arbon at es or .

hydroxids a e not suitabl e (see page

r

The soluti ons r equir ed are :

D ecin orm al iodin (see p ag e 1 88)
D ecinorm al ars enous acid ;
St arch solution (see p ag e or io dized starch t est p ap er .

N
Preparati on of i o
D ec n rmal —
~

I 0
Arsenous Aci d (A52 0 3

N
IS
gms in li t er)
. 1 gms of the
. .

p ur est su blirned ar senou s an hydrid ( A S2 0 3 ) ar e diss o lv ed in a

minimum of conc entrated sodium hydroxid solu t ion When .

c ompl ete solution is effected add 1 00 mils of dis t ill ed water and
n eutraliz e the excess of alkali with diluted sul phuric acid ,

using ph en ol ph thal ein as indicator Add to this .

g m s i of 20

p ur e s od ium bic arb on at e diss olved in 50 mils of dis t ill ed w at er

0 ,

and fin ally dilut e to 0 mils at stan dard t em perat ur e I t is

10 0 .

then st andardi ed with decinormal i odin usin g s tarch as in di

z ,

cator D ecin ormal ars enous acid solution shoul d correspond

.
,

volum e for volume with decinorm al iodin solution

, .

If this solution is m ade from pure ars enous acid it will ,

hol d its titer for years but if any sul phur is pres ent th ere wil l
,

be an absorption of oxyg en from the air and a cons equ ent

24 2 THE E SSE N T AL S OF I VOLU ME TRI C AN AL YS I S
oxidation to ars enic oxid If the pr es enc e of s ulphur is sus
.
~

t ed the s olution should be t est ed wi t h silv er nitrat e wh en

p ec , ,

its pres enc e will be indicat ed by the formation of a reddish

precipitat e .

I odized S tarch Test Paper A portion of starch solution

.

i s mix ed with a few dr ops of pot assium iodid solution and

in thi s are so ak ed strips of pur e whit e filt ering pap er Thi s .

t est p ap er is us ed in the damp state ; it is th en far more

s ensitiv e .

E stimat i o n of Fr ee Hal o gens The estim ation of chlorin

.
,

bromin or iodin by the Chlorom etr ic m ethod d ep ends as ,

b efor e stat ed upon th eir pow er of oxidizing ars enous acid

, .

Wh en a free h alog en is brought in contact in alkalin e soluti on

with ars enous acid the l att er is oxidized to ars enic acid whil e
, ,

the h alog en is transform ed into a h aloid acid as p er equ ations ,

C14 4 H cl
4 HB1
BI 4
‘
+ 2 E 20 + A8 2 0 3
= A5 2 0 5 + ‘
.

I4 4 HI

The stimation may be carri ed out in two w ays : I st by

e ,

dir ec t titrat ion with a s t andard ars enous oxid s oluti on using ,

iodiz ed s tarch t est p ap er as in dicator ; 2 d by residual titra ,

tion an exc ess of the standard ars enous oxi d b eing tak en and
, ,

th en retitratin g with st an dard i odin solution using starch as ,

indicator The r esidual t i trati on m ethod n eed not be employed

.

for free iodin as this can be titrat ed direct with the ars enous
,

oxid solution using starch as indic ator Furth ermore i odin

,
.
,

n eed not be brought in t o s olution to be titrated by thi s m ethod .

The estim ati on of fr ee h alog ens by the dir ect Chlorom etric
m ethod is as follows
An acc urat ely w eigh ed quantity of subst anc e mad e al ka
lin e by the addition oi sodium bicarbon ate is titrat ed with
decinormal ars enous acid solution and from tim e to tim e ,
2 44 THE E S SE N TIAL S O F VOL UME TRI C AN AL Y SI S
mils of the l atter w ere requir ed then , 4 from 2 6 mils l eaves
2 2 mils the quan ti ty of the 1 arsen ous acid solution which
,
—

reacted wi th the chlorin Th calcul ation is the sam e as in . e

E xamp l e I .

The r eac t i on is as follows

C14 2 H2 O A5 2 0 3 4 H c l i “ ‘
1 35 2 0 5 .

4) I 4 84
I - -9 2

N
gm s = .
gm s . 1000 mil s VS . .

N
gm s I mi l VS
5
. . .

t
E s ima i t on r in Bleachin g Pow der
of A vailabl e Chl o in .

Thre e and on e h alf gms of the bl eaching p ow d r (chl orin

—
. e

at ed lim e) are triturat ed thor oughly with 50 mils of w at er ,

and the mixtur e tr ansf err ed to a gradu at ed v ess el tog eth er ,

with the rinsings and m ad e up to 000 mils with water ,

1 .

This is th oroughly sh ak en mils of it (r epres enting . 1 00

gm of the s amp l e) is removed by m eans of a pip ette and

.

t i trated wi th decin orm al ars enous acid solution as d escrib ed ,

in the foregoing assay using eith er the i odiz ed starch test ,

N
p a e pr as indicator or reti trati n g the excess of E rsenous
a

a cid solution added by m eans of i odin solution .

N
ch m il of
Fa
10
A5 2 0 3 V S . . repres ents
av ail abl e c hl orin .

‘
C a (O Cl) C l 4: AS 2 0 g AS 2 O 5 2 Cd C l2 .

4 ) r4 r . 84

N
gm s . m
g s . or 1 000 mil s I O
VS
. .

s een by r eferring
As to the a o b ve equ at ion t his proc ess
d et ermin es the valu e of the chlorinat ed lim e by m eas uring
 AN AL YS I S BY O XI D ATI ON AN D R E D U CTI ON 245

the a moun t of ars en ous acid which th oxyg en p r s ent in e e

the ac t iv e c ons t i t u en t is c ap abl e of oxi dizing .

In the f ormul a of thi s c omp oun d t h ere are two at om s of

chl orin and one at om of oxygen Th erefor e the quan t i ty of .

bl eachi ng p owder which yi elds p t

a r s of av ail abl e chlorin
will also sup p ly 8 p ar t s of oxygen ; this may th er efore be
taken as the m eas ure of the chl orin The s am e m et h od m ay .

be em p l oy ed for the ass ay of all ot h er s olu t ions cont ai ning

av ail abl e chl orin .

Assay of Man gan ese D i ox id (Chl or om etric ) The chl oro .

m etric ass ay of mangan es e di oxid as w ell as that of all oth er , ,

bodi es which lib erat e chl orin wh en h eat ed wi t h hydrochloric

acid may be m ade in simil ar mann er to t h at describ ed for
,

the i odom etric ass ays of th es e subst anc es the s am e ap p arat us , ,

etc. b eing us ed
,
.

N
The lib erat ed chl orin is how ev er ti t rat ed with ars enous
,
E ,

acid sol ut i on .

The chl orin may be dis t ill ed into a s olu t i on of sodium

1

c arbonat e and this s ol uti on is t h n t trat ed wi t h

,
e i
—

Io
rs enous
a

acid or the c hl orin m ay be distill ed dir ec t ly int o a m easur ed

N
vol um e of a rs n ous acid s ol ut i on
e an d the l at t er th en titrat ed

with is
i odin s ol ut i on u sing st arch
, as indic at or , the differ enc e
b etween the volum e of i odin solu t i on us ed and th at of the
ars enous acid s olu t i on t ak en is the m easur e of the l att er which

r eact ed with the chlorin .

It is a good pl an in each cas e to divid e the s olu t ion into

two or t hr ee equ al p arts and to t i t rat e each s ep arat ely .
246 THE E SSE N TIAL S OF VOL U ME TRI C AN A LYSI S
Reducti on M ethods tannous Chl ori d
I nv olving the U se of S
S t anno us chlorid (Sn Cl ) is a v ery p ow erf ul r educ i ng
z

ag ent . Its action in this r esp ect dep en ds npon i t s affini ty

for chl orin which it readily abstracts from most oth er chl ori ds .

In i t s action upon m ercuric chlorid a p ortion of the l att er

is always r educ ed to the m etallic stat e .

This r educing action of stann ous chlorid is utiliz ed in

c ertain volum etric proc ess es esp eci ally in the estimation of
,

iron In this c as e it poss ess es an advantage ov er p erm an

.

g an a t e in ,
th a t the ir on must b e in the f erric st at e in which ,

con di ti on it is most usually found whil e if p erm angan ate ,

is us ed a prelimin ary r eduction to the ferrous st ate is n ec essary

,

b efore titrating The gr eat dis advantage how ever is in the

.
, ,

fact th at ev en short contact with air will quickly oxidiz e it ,

and thus s p oil i t s tit er In c ons equ enc e of this it must be

.

frequ ently t est ed and can be us ed only in the form of empiric al

,

solutions .

It is p articul arly us eful in the titration of ferric s alts ,

which s alts can be accurat ely estim at ed by dir ect ti trat ion
.

with it the end point b eing r ec ogniz ed by the dis ap p earanc e

,
—

of the y ellow c ol or of the f erri c s olu t ion Th es e s alts may .

als o be estim at ed r esidually by ad ding an exc ess of s t ann ous

chl ori d s olu t i on of known streng t h and retit ating the exc ess r

by m eans of s t andard i odin using starch as indic at or

, .

The r eac t i ons a re

F e2 C16 a l2 2 F e C 12 Sn Cl4

a l2 2 HCl 12 SH Cl 4 QE I .

The Est im at i on
ro n by Mean s of Stann ous Chl ori d
of I
S olut i o ns may be accurat ely affect ed by the foll owing pro
cedure as sugg est ed by Fr es enius
, The solutions n ec ess ary .

are
248 THE E SSE N TI ALS O F V OL U ME TRI C AN A L Y SI S

3d T .h e ass ay .

The r el ation b etw een the t in s olu tion and the iodin s olu ti on
is foun d as foll ows :

Two mils of the t in s olu t i on a e put in t o a b eak er a lit t l e

r ,

s tarch solution added and the i odin s olution th en delivered in

,

from a bur ette until th blu e c ol or occurs If 4 mils are us ed

e .
,

then each 2 mils of iodin s olu t ion r pres en t s mil of t in s olu t ion
e 1 .

The r el ation b etw een the tin s olu t i on and the ir on solu t i on
is found as foll ows :
F if ty mils of the ir on s oluti on (r epres en t ing 5 gm of ir on 0 . .
,

are p ut in t o a sm all fl ask t og et h er wi t h a li tt l e hy dr ochloric aci d

and h eat ed to g en t l e boiling The t in s oluti on is t h en deliv ered

.

from a buret te un t il the y ell ow c ol or of the iron s olu ti on is n early

disch arg ed . It is th en added c ontinu ously drop by drop un t il , ,

the c olor is entir ely g on e A ssuming t h at 35 mils w er e re

.

quired then each 35 mils of tin s olution a e equival en t to 5 gm

,
r 0 . .

of p ure iron If the end p oin t is not cl early r ec ogniz ed and an

.
-

exc ess of the ti n s oluti on was added the s olu t i on shoul d be quickly
,

cool ed a few drops of s tarch soluti on added and the excess

, ,

estim at ed by titr ating wi t h the i odin s olu t i on each mil of which ,

r epres ents 5 mil of the tin s olu t ion The exc ess so found de
0 . .
,

duct ed fr om the t ot al qu an t i ty of tin soluti on added gives the , .

qu an t ity of the l at ter which corresponds to 5 gm of iron

,
0 . . .

Having det ermin ed t h es e dat a the an alyst can r eadily ,

es t im at eany unkn own qu an t i t y of ir on in s ol ut i on in th f erric e

s t at e
.

If the iron is p ar t ly or wholly in th f errous s tat e i t may e

be oxi diz ed by adding s om e p otassmm c hlorat e an d b oiling

to exp el exc ess of chl orin .

Th A ay A s ol ut i on of ir on t ak en for an alysis r equir ed

e ss .
,

2 4 mil s of the tin solu t ion The qu antity of ir on pres ent is

.

c alcul ated by proporti on as follows :

35 mils mil x ; x =
34 gm : 0 . .
 AN AL Y SI S BY OXI D ATION AN D R E D U C TI ON 249

To s ec ure accurat e r es ul t s the iron s olut ion ass ay ed mus t

b e f a irly c o nc en t r a t d
e ,
b ec a u s t hee n t h e e n d r ea c t i on is more
—

r eadily s een and als o b ec aus e the gr eat er the diluti on th

,
e

l arger the am ount of t in s olu t ion will be r equired It is go od .

o li cv t o use v ery lit t l e exc ess of the tin soluti on so th at on ly

p ,

a v e ry sm a l l qu an t ity o f i o din s o lu t i o n is r e quir e d .

E st im at i on of Mer cur i c Sal t s (L ab orde) This dep en ds.

upon the fact that st ann ous chl orid s ol ut i on added to a solut i on
o af m e rc u ric s alt r d
e uc e s th e l a tt e r fi rst to m e rcurous chlorid
( c a l o m e l ) a n d fin ally the c al om l to m et allic m ercury
e T h e .

reducti on t o c alom el r s ul t s in the f ormat i on of a white pre

e

i
c p i ta te ,
an d wh e n th e m e rcuric s al t is c om p l e t e ly r educ ed
the st ann o us chl o rid a cts u p o n a n d r educ e s th e c al o m el t o

m etallic m ercury which r es ul t s in th producti on of a ch ar

,
‘
e

acteri sti c br ownis h c ol or .

The r eac t i ons ar e as f oll ows

Sn Cl2 2 Hn Sn Cl , 2 HgCl ;

SD Cl2 2 HgCl SD Cl4 HgQ .

ccording to L aborde the tin solution is m ade by dissolving

'

A
8 gms of pur e tinf oil by m eans of h eat in 1 00 mils of pur e
.

hydrochl ori c ac d and diluting to liters

1 2 .

T his tin s olu t i on is ch eck ed against a solution of m ercuric

chlorid containing 0 gms per li t er To counteract the hin
1 . .

dering eff ect of the hy drochl oric aci d the soluti on un der an al
y si s
, c on t aining g m o f m ercuric chlori
. d is mix ed with 5 ,

mils of a solution c on taining 0 gms of amm onium ac etate 10 .

and 00 mils of ac etic aci d to the lit er

1 The ac etic aci d pro .

mot es the disappearanc e of the brown c olor which occurs at

the poin t wh er e the tin s olu t ion is in exc ess but b efor e reduc ,

t ion is compl et e The titr ati on with the t in s olution is con

.

tinued until a p erm an ent brown color occurs .

2 50 THE E SSE N TIAL S OF V OL UME TRI C YSI S
AN AL

If the brown color is too dark from overstepping of the

end point the ad dition of 1 mil of the m ercuric chlori d soluti on
-
,

will rend er the solution white again and the titration can
,

th en be c arri ed furth er
.

This m ethod which is conv eni ent rapid and v ery accurat e
, , , ,

can be employ ed in m any c as es If the m ercuric solution

.

contains any free min eral aci ds the l atter must be n eutralized
,

with ammonia (in the pres enc e of ammonium ac et ate to ,

prevent formation of ammoniated m ercury) .

The pr es enc e of alkali and alk ali earth s alts or most s alts
of oth er m etals (exc ept iron gold and pl atinum) do not
'

, ,

in the l east int erfere with the accuracy of the r esults The .

s ame is true of organic aci ds eith er free or in combinati on

,

wi th al kali .
 Spart ein e m et in e and ea e di aci d alk al oi ds ; most of r

the ot h ers a e m on aci d b as es

r .

E x ampl M on aci d alkal oi ds

es .

C2 0H2 4 N 2 0 2 Hcl C 2 0H2 4 N 2 0 2 Hcl ;

Q u in i ne

oah + H2 80 4 = (C 1 7 H1 9N 0 3 ) 2 H2 5 0 4 ;
C
fi fi
( l i le .

or p me

C o h + H 50 C H 0 -H2 50 4 ;
)
sy gi
( zi z z z 2 4 ( 2 1 2 2 N 2 2 2
tr e n ne

D iacid alkal oids

C 1 5 H2 6 N 2 2 I I Cl
‘
C 1 5 H2 6 N 2 (HC 1) 2
S p ar tei n e

C 3 0H4 0N 2 0 5 H2 50 4 C 3 0H4 0N 2 0 5 112 5 0 4 .

E m e t i n e (K u n z )

The q uantity of alkal oi d pres en t in the substanc e

c alcul at ed as illustrat ed by thi s equation :
,

C 2 0H2 4 N 2 0 2 Hcl C 2 0H2 4 N 2 0 2 Hcl .

Q ui n i n e

gms .
gms = 1 00 0 mi l
. s VS ;

N
1 00 0 mil s —

I O
VS. .

N
T hus 1 mil of I 6
gm . of quinine .

C 1 5 H2 6N 2 2 HC1= C 1 5 H2 6 N 2 (HC1) 2
S p art ei n e

gms .
gm s = 1 00 0 mil
. s T VS ;

1 00 0 mil s E VS
10
. .

N
O ne m l of 1
O

1
—

0
VS . . h nce e= 0 0 1 1 1
7 . gm . of S pa rtei ne .

N
T hus 1 000 mils of
IS
hy drochloric aci d will combin e wi th
 ES TI MAT I O N L
O F A KA O D S L I 2 53

1
1 6 of mol ecul ar w eight in grams of a mon aci d alkal oid
the ,

or of the m ol ecul ar w eight of a diacid alkal oid .

In the c as e of drugs wh er e two or m or e a lkal oids are

pres en t accurat e r esults can only be obtain ed by d et erminin g
,

how much of each alkaloid is p res ent by a s ep arat e assay .

But oft en it is assum ed th at the alk aloids are pr es ent in equ al

quantiti es , and the m ean of th eir mol ecul ar w eights is t aken
as the b asis for the c alcul at ion .

It mus t be born e i n mi nd how ev er th at in titrating al ka , ,

loids the greatest care must be ex ercis ed and all pr ecautions

clos ely obs erv ed in ord er to att ain any d egr ee of accur acy .

The volum etric soluti ons must be pr ep ar ed with the gr eat est
care and must be absolu t ely accurat e The eye must be .

t rain ed (as it can only be through prac t ic e) to dis t inguish ,

the en d colors of the indic ators employ ed a m att er of som e

-
,

di fli culty F urth ermor e all m easuring instrum ents us ed must

.
,

be accurat e or th ey should be c ar efully c alibrat ed in ord er

,

to find the n ec ess ary factor for corr ecti on .

The V o lum etr i c S o lu t i o ns usu ally employ ed in titrating

N N N N N
alkal oids ar e an d The w eak er soluti ons
10 20 2
5 5 0 1 00

give more accurat e r esults , as will be un d erstood if we rem em

ber th at a
I
is 10 >< strong er than a an d 1 00 >< strong er
N
VS Th en 1f solutl on be us ed on e drop may
7
.
,
.

1 00

v rst ep
o e the n eutral point whil e if , the s am e s olu t ion w ere
N
treat ed wi t h B s oluti on 5 drops would be required to n eutraliz e ,

N
which is eq ul v alent to us ng one half
1 a drop of —

I
solut1on . A

N
1 00
soluti o n will of course be cap abl e of ev en more d elic at e
2 54 THE E SSE N TIAL S O F VO LUME TRI C AN AL YSI S

work In the c as e just m ention ed 4 5 drops of the 1 00 may

.

ex actly n eutraliz e the solution h enc e l ess th an h alf a drop ,

of I and b etween 4 and 5 drop s of 1 0 are r epres ent ed

-
.

Th er efor e in all d elic at e alk al oi dal ti t rations w ak stand ard e

soluti ons shoul d be us ed in fact in all titrations wh ere great

-
,

accur acy is r eq ui r ed .

If the alkaloi d be from a r nt x tra ti on and is in theece e c

form of a free alkal oid i t is diss olv ed in a m easur ed volum e

,

N
of E) acid solution and the exc ess of a cid s olution th en d eter
min ed by residual titration with a lkali solution .

In this the sulp huric acid s olution is preferr ed ,

xc ept
e

N
in the c as e of quin in e or cinchonin e in whi ch 17> hydr ochloric ,

aci d giv es b et ter r esults .

The proc ess in d et ail is as follows : Pl ac e 2 gms of the .

N
a lkaloid into a b eaker add 7 5 mils of T6 sul phuric acid solu
,

tion and warm on a w ater b at h un t il the alkaloid is com

,
'
-

p l etely dissolv ed Th e solution

. is th e n allow ed to cool and
diluted to 00 m ils 1 .

Ten mil s of the solution (contain in g gm of the alkaloid .

l
and 7 5 mils of.
E sulphuric acid solution) are removed by
10

N
m eans of a 1 ette and ret1trated
pp W 1th
1 00
p otass1um hydrox1d

N
solution . O e e
n -
t nth of the qu antity of the
1 00
alkali used
N
is deducted from the 7 5 m
.ils of the —

16
ci d solution
a , and the
2 56 THE E SSE N TIAL S O F VO LUME TRI C L I
AN A Y S S

A ci d . Alk a i l .

Haem ato xyli n Bl ue

P rp li s h
u d -
re

Y e llowi h-red s P rp li s h
u

R ed Bl ue

Y e llow Rs d o e -re

o o o o o o o o o o o o o o o o R ed Bl ue
0 G r ee n fl uo resce nce fl uoresc .
, s
ye l lo wi h
Bl
0 0 0 0 0 0 0 0 0 0 0 0 0

ue R ed
M ethyl-o rang e R ed S tr aw -ye llow

Pheno lp hthalein C o lo le r ss R ed

TAB LE SH OW I N G T H E FA C T O R FO R VA R I O U S AL K A L O I D S
N
W HE N TI TRAT I N G W I TH ACI D O R A LK A LI

M ‘
la gfiggf
c r
N am e F or m u F ac t or
v
. . .

A co n i ti ne
Atr o p i ne

Br u ci ne

C ep hae li n e
C in chon a k
al aloi d s( co m bi n ed)
C i n chon i n e C 19H22 N 2 0
C i n cho ni di n e C s zN zO
C oc ai n e C 1 1H21N O 4
C odei ne C 18H2 1N 0 3
C oni in e C SHH N
(G len a d) r
E metine C 30H 4 0N 2 0 5 (K un z )
C mHl O z (U S P ) . . .

r st
Hyd a i ne Ce e O o
s
Hyo ci ne C 17H2 1N O 4
s
Hyo cyam i ne C 17H23N 0 3
I pecac k
al aloi d s( co m bi ned)
M orp hine
N i coti ne
P hy s stigm i
o ne

Pi loca rp i ne

Q ui ni ne
r
Sp a tein e
r
St ychni ne L
 ES TI MATIO N O F A KA O D S L L I

’
G ORD I N S MO D I F I E D AL KA LI ME TR I C ME TH O D , U SI N G P HE N O L

P H THA I E IN AS I N D I C ATO R

The a lkal oidal resi du e o b t ain ed by any of the e x trac t i on

N
m ethods I n use 13 d1ssolv ed m a m eas ur ed exc ess of
55
hydro
chloric acid solution Wagn er s or May er s r eagent is th en
.
’ ’

add ed , a littl e at a tim e with frequ ent sh aking until the , ,

al kaloids ar e compl et ely pr ecipit at ed The mixtur e is th en .

diluted with wat er to 1 mils and sh ak en until the doubl e 00

salt of the alk aloid an d r eag ent compl et ely s ep arat e Wh en .

allow ed to stand a few minut es the sup ernatant liquid

should be cl ear and if Wagn er s r eagent has b een us ed this
,
’
,

will be of a dar k ed col or The liquid is now fi lt er ed and

-
r .
,

5 mils
0 of th e fil trat e (
r ep r es enting on e h alf of the alk aloi d) -

is tr eat ed with a 1 0 p er c ent s olution of s odium thiosulphat e

add ed drop by drop
,
un t il the col or of the free iodin dis
,

app ears This discol oriz ation is not n eeded if May er s r eag ent
’
.

has b een us ed A few drops of the in dic at or p h enolphth al ein

.

ar e now introduc ed and the exc ess of acid estim at ed by r eti

,

trati on wi t h 2 5 p o t assi u m hy dr oxi d s ol uti on . T his ,

deduct ed

from on e-
h alf of the volum e of the stand ard acid solution
em p l oyed in dicates the numb er of mils of
, hydrochlori c 2
0 r

aci d s olution which combin ed with the alkal oid in 50 mils

,

of the s olu t ion This numb er m ultip li ed by two and th en

.
,

by the factor for the alkaloid pres ent gives the total qu antity ,

of alkaloid .

E x ample An alkaloi dal r esi du e consisting of morphine

.

was d issolved in 30 mils of HCl V S Th en Wagn er s reagent . .

’

was added in exc ess as describ ed and the mixtur e m ad e up ,

2 58 THE E SSE N TI ALS O F VOL UME TRI C AN AL YS I S
to 1 00 mils with wat er . F ifty mils of this w ere filtered off,

d ecoloriz ed as directed and titrated with ; K O H V S Ten

,
g . .

mils were r equired which correspon ds to 2 0 mils for the en ti r e

,

quantity . T h en 20 mils deducted from the 30 mils of 2 0

HCl V S . . added, l eaves 0 mils the qu antity requir ed to neu

1 ,

N
tra11z e the m orphme . The factor for morphin e
20

gm . r in ) multip li ed by
, Go d , gm th
.e qu
, an tity of

alkaloid in the residu e exam in ed .

The fac t or for morp hin e h ere given is som ewhat l ower
IS
than the th eoret ic al equival ent It was asc ert ain ed by exp er .

m ent with a s amp l e of the anhydrous alkaloid .

The following factors (by G ordin ) w er e obt ain ed by com

p aring th eir mol ecul ar weights with that of morphin e which ,

fac t or Was det ermin ed by exp erim ent

Morphi n e
Hy drastin e
I
I

rychnin e
St
Caff ein cryst
e,

Coc ain e
Atrop in e
2 60 THE E S SE N TIALS or V O LU ME TRI C AN AL Y SI S
a lcohol and ammonia Petrol eum b enzin has of l ate b een .

r ecomm ended .

Prollius flui d or s om e m odific ati on of i t is v ery s at is

’
, ,

fac tory .

Prolli us Flui d con sis ts of eth er 3 5 mils alcoh ol 2 5 mils

’
2 , ,

and c onc entrat ed ammoni a wat er mils -

10 .

Modifi d P rolli us F lui d c onsists of et h er 50 mil s chloro

e
’
2 ,

form 80 to 0 0 mils alcohol 2 5 mils c oncentrated ammonia

1 , ,

wat er mils10 .

The S epar at i on of the Alk al o i ds an d the U se of I m m i sci bl e

So l vent s. Th S haki ng O ut e P oc M os t alkal oi ds are
—
r ess .

insolubl e in wat er bu t a e r eadily sol ubl e in c ertain v ol at il e

r

solvents s uch as alc oh ol eth er chl oroform amyl alcohol

”
, , ,

b enz en e p etrol eum b enzin ac etic eth er etc but not in

, , ,
.
,
'

c arb on t etrachl orid Th os alkal oidal s olv ents which do not

. e
“
mix r eadily wi th w at er ar kn own as the immiscibl e sol e

v ents .
”
Salts of alk al oi ds on the oth er h an d a e as a r ul e r

sol ubl e in wat er but practically ins ol ubl e in the immiscibl e

,

s olv en t s This prop erty of the alk al oi ds mak es i t p ossibl e

.

to s ep arat e th em from t h eir n at ural s ourc es .

The alk al oi d in s ol uti on in an immiscibl e s olv en t m ay be

“
s ep arat ed by sh aking out with a dil ut e aci d the alkal oid ”
,

is th ereby c onv er t ed into an alkaloidal s al t which r eadily

diss olves in the aqueous aci d sol ut ion Conv ers ely an aqueous .
,

solution of an alkal oidal s alt wh en t reat ed wi th an alkali tp

set fr ee the alk aloi d an d sh ak en wi t h an immiscibl e solv ent

g iv es u p its alk al oi d in a pur e s t at e to the l att er T he

p roc ess .

of ass ay by t his sh aking out p roc ess is c arri ed out by —

tr eatin g the liq uid ex t racts (af t er h aving b een fr eed from
alcoh ol ) wi t h an immiscibl e s olv ent and a slight exc ess of

an alk ali The alkal oi d is t h us diss olv ed in the immiscible

.

solvent which is t h en s eparat ed from the aqu eous liquid

, ,

and tr ansf err ed to an ot h er v ess el in w hi ch i t is sh ak en w ith an

 V O LU ME TRI C A S SAY N I G O F VE G E TA B L E D RUGS 261

c ss of acid l arg ely diluted wi th wat er The acid c ombin es

ex e .

wi t h the alkal oi d and forms an alkal oi dal s alt whi ch l eaves ,

the immiscibl e s olv ent an d en t ers the aqu eous soluti on

,
If .

the alkal oi dal soluti on so obt ain ed is s t ill c ol or ed the sh aking ,

out is r ep eat ed until a p ure alk al oi dal s olution in the immis

cibl e s olvent is obtain ed The ap .

p ar at us us ed in this sh aking out -

Op erat i on is kn own as a s ep ar at or .

S ee Fi g 54 . .

S ep arators c onic al or p ear

are

shap ed ; the n eck is provided with

a w ell gro un d gl ass sto p p er an d the
-

outl et t ub e or st em at the b ottom

with an acc urat elyfi tting gl ass st op
-

c ock The s olvents usually us ed

.

in alk al oi dal dr ug ass ayin g are

alc oh ol chl or oform eth er an d v ari
, ,

ous mixtures of t h es e containing at

l east 7 5 p er c ent of eth er Wh en .

chloroform is us ed it will c oll ect at F IG

54
the bottom of the s ep arat or an d can
. .

be easily drawn off ; but if eth er o eth er chl or oform mixtur e is

, r —

us ed i t will form the upp er l ay er in the s ep arator and may be

, ,

syph on ed off or the l ow er aqu eous l ay er drawn off and the

, ,

eth er eal l ay er t h en transf err ed to an oth er s e arator V i l nt

p o e .

sh aking of the cont en t s of the s ep arator is to be avoid ed ,

g en t l e sh aking or rotating is quit e su ffi ci ent to br ing about the

d esired transf er of alkaloid E xc essiv e shaking will c aus e
.

the form ati on of an emulsi on of the w at er an d s olv ent which ,

is oft en h ard to break up .

The fin al op erat ion sh oul d always be the c oll ecti on of the

free alkaloid by m eans of a p ort i on of the immiscibl e solv ent .

This s oluti on is drawn off into a b eak er the solv ent evap ,
2 62 THE E SSE N TIAL S O F VOL UME TRI C AN AL YSI S
or t d ov er a w t r b ath usin g g entl e h eat and the dry
a e a e —
, ,

r esidu e in the b eak er diss olv ed in a m easured quanti ty of

standard acid V S The exc ess of acid V S is th en titrat ed
. . . .

with a standard al kali V S in the pres enc e of a suitabl e . .

indic ator .

In conn ecti on with this att ention is call ed to the fact that
, ,

som e of the most imp ort ant m ethods of isol ating alkaloids
in drug assays and in toxic ological investigations d ep end upon
the solubility of the fr ee alkal oi ds in et h er chloroform b enz en e , , ,

etc.
,and the r el ativ e insolubility of alk aloid al s alts in the

sam e solvents Th ere are howev er a numb er of exceptions

.
, ,

t o thi s rul e and sp eci al att en tion is c all ed to the fact th at in

,

m any c ases alkaloids p ass from d ecid edly acid aqu eous solu
tions (in which th ey c ertainly occur as alkaloidal s alts) into
chloroform and eth er in the shaking out m ethods Whil e ,
-
.

the amoun t of alk aloid so dissolv ed by th es e solv ents is n ev er

very great still the qu antity is an appr eciabl e one Thi s
,
.

behavi or occurs in the c as e of c aff ein e colchicin e and n arco , ,

tine ; and un d er c ertain con ditions also in the c as e of strychnin e ,

at ropin e v eratrin e and oth er b as es

,
This transf er of alk aloid .

to chl oroform occurs more p articul arly in the c as e of alka

loids of w eak b asic charact er and wh en the solution is n eutral ,

or only feebly acid or wh en the alkaloid is in combin at ion

,

with a comp aratively w eak acid as citric tart aric etc Fur , , , .

t h erm or e som e alk

,
al oid al s alts not ably thos e of w eak b as es , ,

are t r ansf err ed as such to chloroform esp eci ally the s alts of ,

hydrochloric acid hydrobromic acid and ni tric acid In the

, ,
.

cas e how ever of the sulph at es phosphat es t artrat es and

, , , , ,

citrates of strongly b asic al kaloids no transfer occurs or at , ,

most only min ute quantiti es of the alkaloids p ass ov er In

,
.

ord er to prevent a transfer of al kaloid or alkaloidal s alt out

of an aqu eous sol ution to an immiscibl e solvent the use of ,

sulph uric acid is to be r ecomm end ed and in all toxicologic al ,

2 64 THE E SSE N TI AL S OF VO LU ME TRI C AN AL S S Y I
off the a qu eous solu t i on in to a s ec on d s eparatory funn el .

Repeat this op erat i on wi t h two m or e p or t i ons of 5 mils of 1

aci dul at ed wat er N ow r en der the con tents of the s eparat ory
.

funn el alkaline by adding ammonia water This lib erates the -

.

alkaloi ds which are th en s eparated by tr eatm en t with a mix

,

t ure of chloroform t hr ee parts (by volum ) an d eth er one

, e , ,

p art ,
using t hr ee succ essiv e por t i ons first 2 mils t h en twic e ,
0 ,

1
5 mils .

The chloroform eth er s ol uti on is h eat ed on a wat er b ath

- -

until the solven t is evaporat d and th en the varnish lik e

. e ,
-

residu e treated twic e with 8 mils of eth er and again evaporat ed .

The r esi du e is th en diss olved in 5 mils of alcoh ol wat er 1 ,

add d to sligh t p er m an ent turbi di t y and th en the indic at or

e , .

Titrat e in us ual way wi t h decin orm al aci d and c en t in orm al

alk ali .

A s eri ous obj ecti on to t his m et ho d li es in the t aking of a

so c all ed aliqu ot p ar t : F irs t
-
b ec aus e of the w ell kn own solu ,
-

bili ty of et h er in w at er an d c onv ers ely of w at er in eth er as, ,

a r esul t of whi ch the v ol um e of the et h er eal s t r at um is m at eri ally

ch ang ed Fur t h erm ore c ommerci al eth er c on t ains variabl e

.
,

qu an t i t i es of alc oh ol h enc e the chang e in vol um e will not

,

alw ays be the s am e .

An ot h er s ourc e of err or in the aliq uot p art is found in

the v ol atil e n at ur e of the s olv en t s us ed In warm w eath er .

i t is impossibl e to avoid l oss by vol atiliz ati on h enc e the aliquot ,

p ar t t ak en is too l arg e .

W A Puck n er has describ ed a modific ation of the

. .

K ell er m ethod whi ch avoi ds the use of the aliquot p art He .

us es only one h alf of the eth ereal s olv ent for the mac erati on
-
,

an d aft er the usu al m ac eration transf ers the drug to a sm all

p e rco la tor in which af t er the eth er eal solu t ion has b een w ell
,

Ph R ev XVI ,
. . 1 80
,
an d XX
, 4 57 .
 V O LU ME TRI C ASSA YI N G O F VE G E T AB L E D R UGS 2 65

drain ed off the m arc is p ercol at ed with the s am e m enstruum

,

to compl et e exh austion The qu antity of et h ereal s olv nt . e

requir ed is not mat eri ally gr eat er than in the K ell er m eth od ,

whil e the quantity of alkaloid obtain ed for w eighing or ti t rating

is l arger b ecaus e it r epres ents the whol e of the s ampl e t ak en
for the ass ay In the c as e of drugs cont aining a v ery s mall
.

proportion of alkaloid this is an important advant ag e .

The obj ection to this pl an is th at the transf er of the m ass

from the flask in which the m ac eration has b een conduct ed
to a suitabl e p ercol ator whi ch should not be more th an 3 cm , .

in diam et er r equir es v ery d extrous m anipul ation or it will

,
!
,

be att end ed with loss of al k aloid .

Assay of Gal en i cal P r eparat io ns .

J . U . Ll oyd s ’
Met ho d
solid extract which . O ne gm . of a

has b een di ss olved in 5 to 8 mils of an alcoholic m enstruum or

a c orr es p on ding vol um e of the tinctur e evaporat ed to this

bu lk o 5 mils of the flui d extract in a fl at bot t om ed p orc l ain

,
r —
e

mortar a e mix ed with mils of a s olu t ion of p erchl oride of

,
r 2

iron To this is added so dium bic arb onat e wi th cons tan t

.

tri tu ration until a s t i ff m agma r esul t s E xtract this magma .

by repeated tri turation wi t h chloroform using first 2 0 mils ,

and th en t hr ee p ortions of 0 mils each dec an ting th em s ev erally 1 ,

by m eans (if a guiding rod b eing c areful th at no susp ended -

,

p o r tions o f the m agm a a e dr awn off In or der to m ak e sur e r .

that all of the alkaloid has b een extract ed add 5 mils more of ,

chl oroform draw it off evaporate on a watch glass dissolve

, ,
-
,

The fe i c hyd rr r oxid r ss s rv s t

whi ch i s p r oduced i n the abo e v p oce e e o

attr t m
ac f th t
o st t s g ms v g t bl ids d l ri g m tt rs
o e anna e , u ,
e e a e ac , an . co o n a e ,

whi l th
e ss f s di m bi rb t lib r t s th lk l ids whi h th
e ex ce o o u ca on a e e a e e a a o , c are en

di ss lv d by th
o e hl r f rm I f th fl i d
e ctr t i str gly l h li th
o o o . e u ex ac s on a co o c e

chl r f rm will
o o o t s p r t sily i whi h s th dditi f f w mils
no e a a e ea ,
n c ca e e a on o a e

of w t r
a e t i i g v ry littl gl s Will
con a n n ash rp s p r tio
e e uco e cause a a e a a n.
2 66 THE E SSE N TIAL S O F VOL U ME TRI C AN A L Y SI S
residu e in dilut e sulphuric acid and t est f or alkal oids by ,

Wagn er s or May er s r eag ent

’ ’
.

The mix ed chloroformic extracts are c oll ec t ed and may be

estim at ed v olum etric ally as foll ows

ME TH OD A To be us ed if the chl orof ormic extract is not

.

colored .

The chl orof ormic so l uti on is evap orat ed to dryn ess in a

flask plac ed on a wat er b ath To t his r esidu e i s add ed an -
.

a ccurat ely m easured exc ess of 5 sulp huric V S . . an d the s olution

3
dilut ed with a littl e wat er , the n i dic ator adde d an d the e xc ess
of standard acid solution esti m at ed by titrating with p otas
50

sium hydroxid VS . . The numb er of mils of the

£5 alkali
l
VS . .

l
us
VS .
ed, divided

originally add ed will give the

.
by
e
2 and

,the
subtracted from the
;volume of
numb r of mils of
a
a cid

lat ter requir ed for the alkaloid This number multiplied by .

,

the prop er factor will give the total alk aloi d pr es ent in the
,

fluid extract .

E x ample The chloroformic resi du e obtain ed from 5 mils

.

of a fluid extract of hyoscyamus was dissolved in 1 2 mils of

—
a cid VS. .
, the solution titrat ed with a lkali VS . .

5 5
mils of the l atter w ere used .

N
ml ls of VS
. . IS the eq ul val en t of m1ls of
50 2
5
N
VS . . mils sub tracted from 12 mils , the a mount of a cid
2
5
originally ad ed, d l eaves mils , the qu antity of
53
ci d VS a . .

which was required for the a lkaloid . This multipli ed by the

,
2 68 THE E SSE N T AL S OF I V OLU ME TRI C AN AL Y SI S
in that it enabl es one t o rapidly and accurat ely es t imate the
alk al oi ds in a pr eparat i on wi thou t the n ec essi ty of app l ying

h eat for any purpos e whatever during the process The assay .

m ay be m ade in fr om one to t hr ee h ours T w enty fi e mils of .

-
v

the tinctu re of an alc oh olic s t ren g t h of ab out 4 5 p er c en t are

plac ed in a separatory funnel mil of a 33 pe c ent s olu tion , 1 r

of soda added and the mixtur e shak en for fi ve minutes wi th

,

5 0 mils of e th er an d set asi de until the liquids h ave com

,

p letely s e
p ar at ed in t o t wo l ay ers T h e low e r d ark c ol o r ed .
-

aqu eous l ayer is dr awn O ff int o a b eak er The eth ereal l ay er

'

which b esides the alkal oid has tak en up most of the alcoh o l
, ,
‘

and som e col oring m att er is sh ak en up wi t h 3 mils O f w at er,

which after s eparat ing is drawn O ff and added t o the first

, ,

aqu eous liquid The eth er eal liquid is th en p our ed int o a

.

suitabl e flask whil e the combined aqu eous liquid is further

,

tr eated with two p ortions of ether (2 5 mils each ) the eth er to

contain ab out 0 p e c en t of alcoh ol Th es e eth ereal extrac ti ons
1 r .

are w ash ed each with 5 mils of w at er ; t

1h e. fi rst ext ra c tion
aft er w ashing may be added t o the origin al eth er eal soluti on ,

whil e the s econ d is r es erved and l at er on emp l oyed for washing

the flask The et h er eal s olution which contains still s om e
.
,

trac es of aqu eous fluid containing alkali is dehydrat ed by ,

t r eatm ent with or 3 gms 2 of exsicc at ed c alcium s ul p hat e

.
,

and fin ally filt er ed in to a gl ass s t op p er ed fl ask c on tainin g 50

mils of water .

Ti t rat ion by m eans of aci d V S is emp l oy ed using . .

,
1 00

alcholic soluti on ( ) in dic

of ator
i odeosin 1 —
2
50 as .

Th Method as ab ov e d escrib ed is Obviously ap plic abl e

e

only to such alkaloids as are r eadily solubl e in et h er If an .

estim at ion of alkaloids insolubl e or only sligh t ly s olubl e in

eth er but solubl e in chloroform is to be m ad e the m ethod

, , ,

is modifi ed as follows
 V OLU ME TRI C ASSA YI N G OF VE
.
~
GE TAB LE D R UGS 2 69

T wenty five mils of the tinc tur e of 4 5 pe c en t alcoholic

- r

strength a e vigorously shak n for fi m inutes wi th 30 mils

r e v e.

of a mixture of part of chloroform and 2 parts of eth er The

1 .

solution so obtain ed is washed wi t h 3 mils of a 3 per cen t 0

s olu t ion of so dium chl orid This op erati on is repeated twic e

. .

using each tim e 5 mils of the eth er chl oroform mixture and
1 -

washin g with 5 mils of so dium chlori d solu t ion

1 . .

I f th S parati on of the aqu eous an d et h er eal liqui ds is not

e e

distinct an addi t ion al or 3 gms of s odi um chl ori d may be

2 .

us ed This p r e ents the emulsification which if p ur wat er

. v , ,
e

wer e mp l oy ed woul d occ ur

e ,
.

I f th Ti n tu
e to be ass ay ed c on t ains m or
c re th an 4 5 p er e

c ent Of alc oh ol i t is n ec ess ary to add wat er to r educ e i t to 4 0

or 5 p e c ent
0 r .

Ti n tur
c con tai ni ng C hlorophyll o
es fat or fat t y aci ds must r

fi rst be dep riv ed of t hes e constitu ents as th es e subst anc es , ,

poss essing acid prop er t i es inferi or to th at of i odeosin will act ,

the p art O f an alk ali tow ard i t an d thus be r ec orded as alk aloid .

To move the C hlo ophyll and f atty aci ds acidul at e a

re r ,

mixt ur e of eq ual p arts of the t inctur e and wat er wi t h a few

drops of s ul ph uric acid shak e wi t h t alcum during s ev eral
,

hours and aft er s ubsi denc e of the l att er filt er O f this

, , , .

fi ltr at e 5 gms (not mils on accou n t of the admixture of alco

2 .
,

hol and wat er c ausing chang e of volum e) a e tak en and the r

alk aloi d estimat ed in the m ann er alr eady describ ed aft er

’

first removing if nec essary the l ast trac es of fat by a singl e

, ,

shaking of the acid solution with p etrol eum eth er .

F or the A ssay of extracts to gms are dissolved in I .

from 4 0 to 50 mils of 4 5 per c ent alcohol t o m ake a sol ution "

containing l ess than 3 per c ent extractive For the assay of .

fluid extracts 0 mils are taken

1 .

For details of s p ecial assays see the author s Manu al of

’
,

V olum etric Analysis .

2 70 THE E SSE N TIAL S OF V O L UME TRI C AN AL Y SI S
The I n fl uence of r
rt i V olat il e Solvents
the P esence of Ce a n
upon the accuracy of alkaloidal titrati ons must be borne in
mind Alcohol in may instanc es influ enc es the col or changes
.

of the in dicat ors to the ext ent of r end erin g th em indistin ct

or entir ely unr eliabl e; whil e eth er or chloroform mat erially
diminish es the s ensitiv en ess of m any of our m ost valued
indicators am ong them ph enolphthal ein rosalic acid congo
, , ,

red and luteol

,
On the oth er h and fl uorescein and g all ein
.
,

may be m ention ed as b eing more s ensitiv e in the p resen e of c /

alcohol or ev en of eth er It is advis abl e th erefore in m ost

.
, ,

cas es to p erform the titration without the pres enc e of the

,

abov e n amed solv ents

-
.

I ndi cat or s V ary in thei r Degr ee of Sensi ti venn ess to the

same Alk al oi d h enc e the choic e of an indic ator in a p articul ar
,

cas e is a m att er of importanc e The following tabl e b as ed .

,

upon th at of Ki ppenberger will s erve as an aid in the s el ection , .

The small est qu antity which will procur e a distin ct tint should
be t ak en .

Atr op in e Lacmoi d F luorescei n I odeosin Haematoxylin

.
, , , .

Bru cin e C ochi neal I odeosin Haem atoxylin

.
, , .

Cocain e Lacmoi d F luor esc ein Cochin eal Haem atoxylin

.
, , , .

Con i in e C o hi neal Lacmoi d I odeosin Haematoxylin

. c , , , .

Codeine I od osi n Lacmoi d Haem atoxylin

. e , , .

E metin e I odeosi n Cochin eal

.
,
.

Morphine H oematox yli n Cochi neal L acm oid

.
, , .

Q u in in e H. wm a tox yli n A z oli tmi n F luor esc ein , , .

S try chn in e Azoli tmi n I odeosin Haem atoxylin

.
, , .

Spart eine H cematoxyli n Azolitmin

.
, .
2 72 T HE E S SE N TIAL S O F VO LU ME TRI C L
AN A Y S S I
1
solution and continu e th t i trat ion wi t h
,
ethios ulp hat e V S
2
E
. .

until the blu e c olor disapp ears .

N ot e the numb er of mils of th s odium thiosulphat e e

5
thus us ed ,
an d dil ut e the bromin s ol ut i on so that equal volumes
of it an d the
2 s odi um thi os ulphat wi ll exac t ly corr esp on d
e

to each oth r un der eab ov m en t i on d c on di t i ons

the e
-
e .

E x ample Assuming th at the 2

. mils of bromin s olution 0

N
r quir ed
e mils of the T thi osul phate to c om pl etely absorb
2
O

the io din the br omin s oluti on must be dilu t ed in the p o

,
r

p ortion of 0 to 2 th at is each
2 mils must b e dilut ed t o
,
20

make 2 mils .

Thus if 850 mils a e l eft t h ey must be dilut ed to m ak e

r ,

1 7
0 mils and the s olu tion is decino m al
1 ,
r .

A n ew t ri al S h oul d always be m ade af t er dil ut ing an d ,

the bromin s ol ut i on sh ould c orr esp on d v ol um e fo v ol um e ,

r ,

with the de i normal so dium thiosulphat e

c .

The fir st st ep in the pr ep ar ati on of this soluti on is to

dissolv e the s alts ; th en hy drochl oric aci d is added which ,

lib erat es a defin it e quanti ty of bromin as the equat i on illus ,

trat es
5N aBr N aBr 0 3 6 HC l 6N aC l + 3Br2 + 3H2 0 .

Thest opp er shoul d be ins er t ed i nto the b ott l e as soon

as the hy drochloric aci d has b een added in or der t h at no ,

bromin vapor escap e and the bottl e rotat ed so as to mix the

,

acid thor oughly wi t h the liquid .

The n ext st ep is t o det ermin e the qu an t ity of bromin

which a definit e vol ume of solu t i on will lib erat e The bromin .

s olution should be of such strength that 00 0 mils of it will 1

 ES TI MATI O N O F PHE N O L 2 73

con tain gms of avail abl e bromin Bromin lik e chl orin
. .
, ,

lib erat es i odin from p otassi um i odid and is es t imat ed in ,

the s am e m ann er .

O n e at omic w eight of i odin is lib erat ed by on e atomic

w eight of bromin :
Brz 2 KI 2 K Br + I 2 .

Thus
by determining the quan t i ty of i odin lib erated the
quantity of bromin is foun d .

N
The io din is det ermin ed by the sod um th osul hate
p 1 1 ,
10

on e lit er of which repr es ents gms of i odin which is

.
,

equiv al ent to gms of br omin .

,
as shown by the foll owing

equ ation :

B
( z)
r 12 ‘‘
l 2 ( 2 S2 O 3
N 3 SH2 O )
20 ) I 59 84
.

N
m
g s .
gm s . m
g s . or 1 0 0 0 mi l s I O
VS . .

2 N aI N a2 s4 oe IO H2 O .

The Assa y of Phenol D iss olve gm of the s amp l e i n . 1 .

sufficient w at er to m ak e 5 mils of solution at the standard 00

t em peratur e Tw en ty mils of this solution containing

. gm .

O f the s am p l e a e transf err ed to a gl ass st opp er ed b ot t l e h aving

r -
,

a c ap acity of about mils 2 00 .

T o t his 30 mils of decinorm al bromin foll ow ed by 5 mils

, ,

of hy dr ochloric acid a e add ed and the bottl e imm ediately

,
r ,

stopp ered and shak en repeat edly during half an hour

, .

T h en the st opp er is r emov ed just sufli ci ently to intro duc e

5 mils of a p e c en t a qu
20 eous s olution
r o f p ot assium io di d ,

b eing c areful that no bromin escap e .

T he bottl e is th en t h oroughly sh ak en and th n eck rins ed e

with a li ttl e wat er the washings b eing allow ed to flow in t o the

,

b ottl e th en mil O f chloroform is added the mixture thoroughly

,
I ,
2 74 THE E SSE N TIAL S OF VOL U ME TRI C AN AL Y SI S
shaken and t i tration with decin ormal sodium thiosul phat e
,

V S b egun starch b eing us ed as indic at or un t il the blu e color

. .
, ,

is just discharged .

The preci pi tated tribrom ph enol interfer es som ewhat with

the end reac t i on wh en st arch is us ed an d frequ ently with
-
,

old ph en ol s oluti ons the pr eci p itat e p oss ess es a bluish color

which is not rem oved by an exc ess of so dium thi osul phate and
which m akes the end reaction diffi cult This difficul ty is over
-
.

c om e by the use of a sm all qu antity of chloroform which dissolves

the tribr om ph en ol and adm its of a very sh arp end r eaction -
.

Wh en chl oroform is al on e used the end reaction is very ,

-

cl early defined and is known by a colorl ess aqu eous solution

,

and the chl oroform b eing fr ee from any t ing e of pink due to ,

trac es of iodin .

N
N ot e the numb er of mils of t hi osulph at e us ed ; deduct
IO
this numb er fr om 30 mils (the qu antity of 10
bromin originally
N
added ) , and the q uant1t
y of
IO
bromm whl ch went 1nto com ‘

bin ation with the phenol is obtained .

ch mil of
Ea bromin repres ents gm of pure
.

p h enol .

E x ample ssuming that 6 mils of sodium thiosulphate

. A

w ere r equired to discharge the color of the starch iodid this ,

deducted from 30 mils l eaves 2 4 mils the quantity which ,

combin ed with the phenol .

gm .

X 1 00
p er cent of pure ph enol .

F . X . Moerk ,
A .
J . Ph .
, 1 90 4 , 4 75 .
2 76 THE E SSE N TI ALS O F VO LU ME TRI C AN AL Y SI S
The hydrochl oric acid used in the above estimation mus t
contain no free chl orin The potassium iodid mus t be fr ee .

from iodate The starch T S shoul d not be added un til

. . .

most of the free iodin has b een tak en up and the color Of ,

the solution has diminish ed to light y ellow .

The c arbolic acid should be dilut ed with w at er b efore

titration and should n ever be stronger than
,
gm in 2 5 mils . .

Resorcinol C H (O H) 1 3 , 6 4D issolve about 2

gm accurately w eighed in suffi ci ent distill ed water to m easure

.
,

500 mi l s T r.ansf e r 2
5 mils of this solution (r epr es entin g 5
gm ) to a 50 mil gl ass stopp ered flask add 50 mils of d eci
. 0- ,

normal bromin V S and dilut e with 5 mils of distill ed wat er

. .
, 0 .

Th en add 5 mils of hy drochloric acid and at onc e stopp er

the fl ask sh ak e w ell dilu t e it with 0 m 1ls of di still ed wat er
, ,
2
,

add 5 mils of
p o t assiu m io di d T S l et stan d fi v e minut e s and . .
, ,

th en titrat e the lib erated io din wi th d ecin orm al sodium thi o

sulphate V S using s tarch as indicator
. .
, .

Calcul at e as in pr ec eding ass ay E ach mil of d ecinorm al .

bromin correspon ds to gm of C 6H (O H) .
4 2 .

Phenyl sulphonates S ulphocarbolates D issolve about

,
5 .

gm of the salt accurat ely w eigh ed in 50 mils of distill ed

.
, ,

water add 5 mils of decin orm al bromin V S and 5 mil s of

, 0 . .
‘

hydrochloric acid Allow the mixtur e to stan d for fifteen

.

minutes th en add 2 gms of potassium i odid dissolved in 5

, .

mils of wat er and titrate the lib erat ed iodin with decinorm al
,

so dium thiosul phat e V S using starch as indicator . .

, .

E ach mil of decinorm al bromin V S us ed corresp onds to . .

gm of N aCsHsO SO g
. . .
 C HAPTE R XI V

SO M E T E CHN I CAL EXAMI N ATI O N ME T HO D S FO R FA TS,

O I L S A N D W AXE S

The Ac d i
or Pro p orti o n of Free Fatty Aci ds This
V alue .

in dicat es the numb er of milligrams of K O H r equired to n eutral

i e the fr ee fatty aci ds in 1 gm of oil fat or w
z a This st an dard
.
,
x .

a lkali us ed is in alcoholic soluti on and m ay be or w eak er ,

2
5
dep ending up on
n ature of the fat Ph enolphth al ein is the
the .

in dic ator The fat is dissolv ed acc ording to G eissl er in eth er

.
, , ,

but alcohol or puri fi ed m ethyl at ed s p irit chl oroform or a mix , :

ture of alcohol and eth er m ay be us ed The s olvent wh ich ever .

,

is us ed must be free from acidity and sh ould be n eutraliz ed

, ,

N
wi t h IO
a lkali if n ec essary .

The P rocess gms of the oil a e acc urat ely w eigh ed

. Ten . r

int o a flask and ab ou t 5 mils of s olvent added A f ew drops

'

0 .

of p h en olphth al ein are th en ad ded an d the ti t r ation with

N
alc oh olic -
p o t assium hy dr o xi d s ol u ti o n b eg un sh aking , con
2

stantly until the first app earanc e of a pink c ol or Care must .

be t ak en not to add too gr eat an exc ess of the alk ali oth er ,

wis e sap onifi cation will occur A small exc ess m ay how ever .
, ,

be add ed and r eti trated with st and ard acid ; a m or e distinct

en d p oint is th en obt ain ed
-
In the c as e of waxes or s olid
.

fat s the solv ent is added h eat appli ed until i t boils and the
, , ,

titration at onc e start ed .

2 78 THE E SSE N T AL S OF V OL I U ME TRI C AN AL Y SI S

O ne mil of K O H = 0 0 2 80 5 gm of K O H or . mgms .
.

The numb er of mils us ed multi p li ed by ,

and th en

divid ed by the w eigh t of oi l t ak en giv es the milligrams of ,

K O H n eut raliz d by the fr ee f atty acids of the oil i e the

e , . .
,

aci d val ue .

The Sapon i fi cati on V alue (K ottstorfer T his

in dic at es the n umb er of milligr ams of K O H required fo the r

c ompl et e sap onification of one gram of fat or Oil Reag ents .

required are :
A lcoholi c P otassi um H ydrox i d S oluti on m ad e by dissolvi ng ,

4 0 gms .of p o t assiu m hydr oxi d in li t er of 95 p er c ent a lcohol

1 .

H alf N ormal H ydrochlori c A ci d S oluti on E ach mil of

-
.

which = 2 8 0 5 mgms of K O H
. . .

I ndi cator Ph enolphth al ein 1 gm in 1 00 mils of 95 per

. .

c ent alcohol .

The P rocess Into an E rl enm eyer flask capabl e of hol din g

.

2 00 mils accur at ely w eigh abou t 1 gms of the fat ( p r eviously

, 5 . .

p urifi ed a n d fi l t er ed ) R u n in
. to this from a bur ett e 2 5 mils
of the alcoholic potassium hydroxid solution Th en ins ert .

into the n eck of the flask a p erforated stop per prov ided with
a gl ass tub e 70 to 80 cm in l ength and from 5 to 8 mm in
'

. .

diam et er and set it in a wat er b ath for half an hour or unti l

,
-

the fat is entir ely saponi fi ed The op erat ion is facilitat ed

.

by occasional agitation The flask is th en removed its con

.
,
~

t ents cool ed and t itrated with the half norm al hydrochloric -

acid using ph en ol p hth al ein as indic ator

, The alcoholic p otas . a

sium hydroxi d solution is stan dardiz ed by conducting a blan k

exp erim ent simil ar in ev ery detail to the above wi th the exc eptio n

that the fat is omitted .

J . KOttstorfer, 1 87 9, Z ei tschr . anal . Chem .

, XVI I I , 1 99 .
2 80 THE E S SE N TIAL S OF VOL U ME TRI C AN AL Y SI S
of 80 per c ent alcohol and the whol e digest ed on a water bath
,
-

(rotating the flask fr equ ently) until sap onifi cation is com p l et e
.

an d the alcoh ol all r emoved mils f w t r then added

5 0 o . a e a e r ,

and 0 mils of dilu t e sul huric aci d

2 a d th mix t ur
p n e e

distill ed The dis till at e is coll ect ed in a 50 mil flask into

. -

which is set a funn el with a wett ed filter to coll ect any insolubl e
fat aci d The fir st 0 or 0 mil s of distill at e are r eturn ed to
. 1 2

the fl ask an d the 5 mils distill ed

, 0 This is tr eat ed wi t h a few
.

drops of ph en olph t hal ein and t h en t itrat ed with decin orm al

p ota ssium h ydr oxi d T h

.e numb er of mils consumed is the
Reich ert N umb er .

In the Meissl modification (the Reich ert Meissl m ethod) -

5 gms of
. th e fat ar e t ak en an d a mor e com l et e distill at ion
p
of the vol atil e acids effect ed The m ethod is p articul arly
.

us eful in d et ermining the g en uin en ess and purity of butter .

The R ei chert Mei ssl N u m ber

- This is un d oubt edly the
.

b est proc ess for d et ecting the admixture of forei gn fats with
butt er This proc ess dep ends up on the fact th at butt er con
.

t ains c ertain constitu ents which wh en approp riat ely treat ed , ,

yi eld vol atil e acids in much l arg er quantity than is obtain ed

from any of the prac t ic abl e substitut es for b utt er Th es e .

acids are princip ally butyric an d c aproic The proc ess con .

sists in s aponifying the fat with an alk ali th en s ep arating ,

the fatty aci ds by n eutraliz ation and distilling off the vol atil e
,

acids for titrat ion with st an dar d alk ali .

The op erations involv ed in this pr oc ess do not admi t of

any arbitr ary v ari at i on an d r eli abl e and comp ar abl e r esults
,

can only be obt ain ed by strictly adh ering to the pr escrib ed ,

d etails .

The following p r oc ess is adopt ed by the Associ ation of

O ffi ci al Agric ultural C h emists The solutions r equir ed are :
.

S odi um H ydrox i d S oluti on One hundr ed gms Of sodi

. .

hydroxid are dissolved in 00 mils of distill ed wat er The

1 .
 TE CHN I CAL E XAMIN ATI ON ME THOD S T
FOR FA S 2 81

a lkali shoul d be as free as possibl e from the carbonates and ,

be pr es er ved out of con t act with the air .

P ota si um H ydrox i d S oluti on

s O ne hun dr ed gms of the . .

p ur e st p ot assium h y droxi d are dissolv ed in

58 mils of hot d i s

till ed wat er co ol ed in a sto p p er ed v ess el and the cl ear liquid

, ,

dec an t ed and pr es erved out of cont act with the air .

S ulphuri c A ci d Mix 0 0 mils of the strongest acid with

. 2

1 000 mils of w at er .

A l ohol of ab out 95 p er c ent r edistill ed from c austic s oda

c , .

S tanda d Ba i um H yd ox i d S oluti on accurat ely stan dard

r r r ,

i ed ap pr oximat ely decin orm al

z ,
.

I n di cator D iss olve gm of phenol phthal ein in 0 0 mils

. 1 . 1

of 95 per c ent alcohol .

The proc ess :

W i ghi ng th Butter The butt er to be examin ed should
e e .

be m el t ed and k ep t in a d y warm pl ac e at about 60 C for

0
r , .

two or three hours un til the w at er and curd h ave entirely

,

s ettl ed out The cl ear sup ern atant fat is poured Off and
.

filt ered through a dry fi lter p ap er in a j ack et ed funn el con —

t aining b oiling wat er Shoul d the filt er ed fat in a fus ed stat e

.

not be p erf ectly cl ear it must be filtered a s econd tim e This

, .

is to r em ov e all foreign m att er and any trac e of moisture .

The sap onificati on fl asks are pr ep ar ed by thoroughly w ashin g

with wat er alcohol and eth er wiping p erfectly dry on the
, ,

outsid e and h eating for one hour at the t emp eratur e of boiling
,

wat er The flasks should th en be pl ac ed in a tray by the

.

side of the b al anc e and cover ed with a silk h an dkerchi ef until

th ey are p erfectly cool Th ey must not be wip ed with a sil k .

h andkerchi ef within fif t een or tw enty min ut es of the tim e

th ey are w eigh ed The w eight of the flasks h avin g b een
.

accurat ely d et ermin ed th ey are ch arg ed with the m elted fat

,

I n the foll owing way:

A pip ett e with a long st em mark ed to d eliver mils , ,

2 82 THE E S SE N TI AL S OF V OL U M E T RI C AN AL Y SI S
is warm ed to a temp erature of about 50 C The fat h aving °
.
,

b een p oured b ack and for th onc e o twic e into a dry b eaker r

in order to t horoughly mix i t is th en tak en up in the pip ett e

,

and the nozzl e of the p i p et t e c arri ed n early to the b ottom of the

flask ha ing been previ ously wip ed to r emove any adhering

, v

fat and
,
mils of fat are allow ed t o flow into the flask .

Aft er the fl asks h av e b een ch arg ed in thi s way th ey should

be r ecov er ed with the silk h an dk erchi ef all ow ed to st and ,

fift een or tw enty minut es and again w eigh ed , .

Th S aponifi cati on
e Thr ee m eth ods may be employed
.

1 .U nde P r su
r wi th A lcohol
es re T en mils of 95 p er c ent
.

alc ohol are added to the fat in

the fl ask and th en 2 mils of the ,

c austic soda solution A soft .

cork st opp er is now ins ert ed in

the fl ask an d ti ed do wn with
a pi ec e of twin e The s aponi .

fi cati on is th en compl et ed by
pl acing the flas k upon the
wat er or st eam b ath (see Fig .

The fl as k during the

sap oni fi cati on which should ,

l ast one hour should be ,

g ently ro tat ed from tim e to

tim e b eing c ar eful not to pro
,

e so ap for an dist n c '

j ect t h y a e

up its sid es At the end of .

an hour the fl ask aft er h aving ,

b een c ool ed n early to room

F 55 IG . .

t emp erature is op ened , .

2 Under P ressure wi thout the Use of A lcohol

.
Pl ac e 2 .

mils of the potas sium hydr oxid in the flask contain ing the fat ,

which must be roun d bot tom ed and m ade of w ell ann eal ed
- -
2 84 THE E SSEN TI ALS OF VOLU METRI C ANALYSI S

was used in the sto

saponi ficati on
) p p er as in,
the m etho d of
sap on i fi ation
c and h eat on the wat er b ath u nt il the fat ty
,
-

aci ds f orm a cl ear transparen t l ayer on top of the water

, .

This may tak e s everal ho urs Cool to r oom t em peratur

. e,

add a few p i ec es of p umic e s t on e an d conn ect wi t h a gl ass

,

con denser as in Fig 56

,
. .

Heat sl owly wi t h a n ak ed fl am e until ebullition b egins ,

an d distil r egul atin g the fl am e in suc h a way as to coll ec t

,
1 10

mils Of dis t ill ate in as n early t hir ty minut es as possibl e .

Mix this distill at e fil t er t hrough a d y fi lt er and ti trat e

,
r ,

100 mils with the stan dar d b arium hy droxi d s olu t ion using ,

FI G 5 6
. .

0 5.mi ] of p h en ol p h t h al ein as in dic at or T h r ed c ol or s hou l d

. e

r emain unchanged for two o three minut es r .

Increas e the n umb er of c ubic c en tim et ers of t en th n orm al -

alk ali us ed by on e t en t h -
divid e by the w eight of fat t ak n
,
e

an d mul t ip ly by fi e to Ob t ain the R ich er t M issl n umb er

v e -
e .

C orr ec t th r es ul t by the figur e obtain ed in a bl ank e p er

e x

imcnt .

Wh en tr eat ed as ab ov describ ed 5 gms of g en uin b utt er

e ,
. e

n ev er yi el ds l ess acidity th an is repres en t ed by 2 4 mils of

 TE CHNI CAL E XAMI N ATI ON M E THOD S F O R FA TS 2 85

alkali It is true however th at the bu t ter m ade from the

.
, ,

milk of a singl e cow especially towar ds the end of her p eriod ,

of l actation has b een known to fall slightly b el ow this figure

, ,

but the average bu t ter as pro duced from the mixed milk of ,

a h erd usu ally r equir es 2 7 mil s or m ore

, O l eom argarin e . r

quires about mil of b eef fat and l ard about the sam e Cacao
1 -
, .

butter requires about 7 mils .

The p erc entag e of butter fat in a mixture of fats -

,

5 gms b eing t ak en .
(
n 16
3 5 p erc e nt ag e of t ru e :

butter fat -
.

I odin Absorptio n N umber of Fat s and Oil s (Hubl s N um

’

T his is the p erc ent ag e of i odin abs orb ed by a fat

or an oil under c ertain c onditions In oth er words it is the .

numb er of parts of i odin abs orb ed by 00 parts of an oil 1 .

gents requ ired

Rea

()
a H u bl s Iod in S olution D iss o lv ’
e 5 gms of pur e io di n . 2 .

in 500 mils of alcohol and mix this solution with 500 mils of ,

alcohol containing 30 gms of p ur e m ercuric chlori d an d set .

,

asi de for tw enty four hours The m ercuric chl ori d solu t ion
- .

shoul d be filtered if n ec essary b efore it is mixed with the

alcoholic io din solution This s olution los es i t s str ength .

rapidly and shoul d therefore be tested b efore using

,
.

b
() D e cinorm a l so d ium thiosul p h at e .

()
c P ot a ssium io d i d soluti on gm s in 1 mils , 20 . 00 .

d
() S ta rch p ast e in dic ator .

The P rocess . To bout a m

g 1 of the fat o oil accu .
'

r ,

rately weighed and dissolved in mils of chloroform con 10 ,

D ingl er
’
s Poly ou t J r
. .
,
1 884 ,J r VI 85
2 81 ; Am C h . . ou .
, ,
2 .

TI n the ca s
e of d yin r g i ls whi h h v
o v ry hi gh bs rb t p w r
c a e a e a o en o e ,
as

li n s eed oil , use fr om t o m

g ; f il f t h br m nd s imil r f ts
. or o o eo o a a a a

use gm ,
2 86 THE E SSE N TIAL S OF V OL U ME T R I C AN AL Y SI S
tained in a gl ass st opp ered b ottl e of 5 mils capacity add 2 5
-
2 0 ,

mils of th i odin s olu tion Stopp er the bo tt l e securely and

e .

p l ac e in a co o l dark p l ac e,fo fo ur hours * A t the expirat i r

on .

of this tim e the mix t ur , must s till p oss ess a brown col or ; if
e

it do es not a furth r m easured qu an t i ty of the iodin solution

,
e

must be added and the mixture again set aside Finally . 20

mils of the p otassium i odid solution a e added t ogeth er wi th r

50 mils of w at er and the mixtur e t it at ed with the decinorm al

,
r
s odium thi osulph at e until the c ol or is almost discharg ed ,

when a few drops of s tarch in dic at or a e add ed and the r

t i tration con t inu ed until the s olu t i on is c ol orl ess .

The S tandardizati on of the I odi n S oluti on is eff ect ed by

subj ecting it to the s am e treatmen t as in the assay but with , .

the oil omitt ed and at the end of four hours titrating with
,

the decin orm al thi osul p h at e .

The diff er enc e b etw een the numb er of mils of thiosul p h at e

s ol uti on us ed in the bl ank t est and the numb er us ed in the
actu al ass ay is multip li ed by
,
an d this divid ed by 3 ,

giv es the io din valu e of the oil und er an alysis .

Wh en the qu antity of the oil or fat tak en is not 0 3 gm . .

,

th en the p roduct is not divid ed by 3 but by the figure corr e ,

sp on din g to the qu anti t y t ak en ; t hus if gm are tak en .

the p r oduct is divi ded by 5 I . .

Anoth er way of m aking the c alcul ation is as foll ows

The di ff r enc e b etw een the mils Of t hi osul ph at e us ed in
e

the bl ank t es t and the mils us ed in the an alysis is mul t i p l i d , e

by th en by and the p r oduc t divi ded by the

1 00 ,

w eight in grams of the oi l tak en for analysis .

The ti m e allowed doe s n ot giv

t i di bs rp ti p w r
e the comp le e o n a o on o e

of an oil or fat an d cann o t b mp r d wi th d t rmi ti s i whi h i t

e co a e e e na on n c s x o

t w lv h rs h v b
e e ou a e een u e s d I t giv s h w v r v ry s tisf t ry mp r tiv
. e , o e e ,
e a ac o co a a e

r s lts b t th ti m
e u ,
u e e fac t r m t b v ry l ly b rv d
o us e e c ose O se e .
2 88 THE E S SE N TIAL S O F VO LU ME TRI C AN A Y S S L I
for the absorption As above describ ed four h ours are requir ed
.
, ,

but this is not sufli i ent tim e to allow of com p l et e absorption

c

of the iodin I t is how ever a goo d practic e to have a fix ed

.
, ,

time limit ; the proc ess th en gives v ry satisfact ory c om parative e

results .

I odin Absorpti o n N umber The Hanus M e tho d * This . .

m ethod is conduct ed lik the foregoing It di ff ers in the com e .

p osition Of the i odin s oluti on us ed T his is pr e ar ed as fol

p .

l ows : Dissolve gms of pow dered io din in 1 0 mils of . 00

p ur e gl aci a l a c etic aci d wi t h the ai d of g en tl e h eat if n ec essary ,

to facilitate soluti on C ool to 5 C and det ermin e the i odin

. 2
0
.

content in 0 mils of the s ol ut ion by m eans of decinorm al

2

sodium thiosul ph at e V S ; th en add to the sol uti on a qu antity . .

Of bromin mol ecul arly eq uival ent to th at of the io din pr es ent

,

(3 mils is th e usu a l ap p roxi m at e amount ) K eep the solution .

in gl ass s toppered bottl es protected from light

-
.

The P ro ss In troduc e ab out

ce . gm of a solid fat or .

gm of .an oil accur at ely w eigh ed in to a gl ass s t opper ed

, ,
-

b ottl e of 2 5s mils capaci ty D iss olve i t in 0 mils of chloro . 1

form add 2 5 mils of the i odin s olu t i on s t opper the bottl e

, ,

s ecurely and all ow th mix tur e to s tan d fo half an hour

,
e r

in a cool dark p l ac e A ft er this time it must still retain a

,
.

brown col or ; if i t is not br own a new t est shoul d be started ,

using a small r qu an ti ty of the fat o oil Th en add in the

e r .

order nam ed 3 mils of potassium i odi d T S 00 mils of

,
0 . .
, 1

dis t ill ed w at er and d cin orm al s odium thi osul ph at e V S i n

,
e . .

small succ essive p ortions shaking thoroughly aft er each addi ,

tion until the c ol or of the mix ture b ecom es quite p al e Then

,
.

add a few dro p s of st arch s olu t ion and continu e the addition

of the thiosul phat e V S until the blu e col or is discharged . . .

T h en m ak e a bl ank t est by mixing ex ac t ly the s am e qu an t i t i es

Z ei tschr N ah . r . u Genus
. .
91 3 .
 I
TE C HN CAL E XAM N A I TI ON ME THOD S FOR FA S T 2 89

Of the iodin solution and chloroform and t i trating the free ,

iodin with thi osulphate V S as dir ect ed above The dif . . .

ferenc e in the numb er of mils of the thiosulphate V S con . .

sum ed in the bl ank test and the actu al test mul t ip lied by ,

and divi ded by the w eight of the fat or oil t ak en giv es the io din

numb er .

In the cas e of oils which have a high io din absorbing -

power sm all er qu an t i t ies of the oils shoul d be us ed

, to .

gm for linseed oil and about

. gm for cod liver Oil . .

T he tim e allow ed for absorption in the c as e of c astor Oil and

lins eed oil shoul d be one hour .

The cons ensus of opinion am ong ch emists is that the Hanus

m ethod is the most satisfactory I ts principal advantag e over .

the H ii bl m ethod li es in the facts (a) that the Hanus io din

s olution is much m ore stabl e (b) th at the tim e required for ,

the r eacti on is c om paratively much short er .

TABLE SHO WI N G I OD I N B R T A SO P I ON N UMB E R FOR SOME

COMM ON O I L S

Almond oil (exp ress ed)

B tt r u e

C st r
a o oil

Cocoanu t il o

C d liv r il
o e o

C tt s d il
o on ee o

L rd il
a O

Li s d i l
n ee o

M st rd il
u a o

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
2 90 THE E SSE N T AL S OF I VOL U ME TRI C AN AL Y SI S
i
The Ac d N u be m r for Resins This is the numb er of .

mi lligrams of potassium hy dr oxid r quired to n eu traliz e e 1

gm of a resin ous subs tanc e

. .

The P rocess . About gms of the r esinous substanc e

2 .
,

accurat ely w eigh ed is diss olved in alcoh ol

, and the s oluti on,

ti trated wi th half n orm al p otassium hydr oxid V S using ph enol

-
. .
,

p hth a l ein as in dic at or T he numb er of mils of the h alf

.

norm al alkali V S r equired for n eutraliz at i on wh en multip li ed

. .

by 5 an d t he pro duct divi ded by the w eight giv es the ,

aci d numb er of the r sin e .

2 92 THE E SSE N T AL S OF I VOLU ME TRI C AN AL S S Y I
Ten mils of the mixed Fehling s solution is equival ent to ’

G luc ose gm
Maltos e
Inverted can e sugar -

Inver t ed starch
L act os e .

E sti mati on of R educing S ugar s (G lu co se M al tos e I n .

, ,

v rted C an su ar L ctos d I t d S t h 0 5 gm or ‘
e
g e
-
a an ,
nver e a re
c . . .

l ess of the sugar is diss olved in 00 mils of distill ed wat er 1 ,

and p ut int o a bur ett e T en mils of the mix ed Fehlin g s solu

’
.

tion accurat ely m easured is put int o a 00 mil E rl enm eyer

, ,
1 -

flask or in a white p orc el ain dish diluted with 4 0 mils of

, ,

distill ed w at er and rap i dly h eat ed to boilin g

, The solution .

S houl d r em ain p erf ectly cl ear and r etain its blu e color If .

it do es not it should be rej ec t ed .

The hot cl ear blu e solution 15 I mm ediat ely titr at ed with

,

the sug ar solution which shoul d be added in sm all p ortions at

,

a tim e boiling aft er each addition until the copp er is com

,

p l etely pr ecipit a t ed a n d th e blu e color of th e solution is entir ely

destroy ed The solution is th en boil ed about two minut es
.

longer and the amount of the sugar solution us ed is read Off

,
.

The Calculati on T en mils of Fehling s solution are always

’
.

taken ; and what ever the qu antity of glucos e or oth er sugar

solution is requir ed to effect its com pl et e reduction th at ,

quantity contains the equival ent of 1 0 mils of Fehling s solu ’

!

tion as shown in the tabl e above

,
.

T hus if mils of the sugar solution w ere required to reduce

12

0 mils of Fehling s solution the 1 2 mils contain gm of

’
1 , .

glucos e or gm of m altos e etc O ne hundred mils of

.
, .

the solution th er efor e cont ain x gm of glucos e . .

5 X 0 10
 ES TIMATI O N OF S UG AR S 2 93

ord er to obtain reliabl e results it is important that the

In
proc ess be c arri ed out exactly as l aid down in the abov e
di r ections and th at the qu antity of sug ar pr es ent in solution
,

be no gr eat er th an one p er c ent The d egr ee of h eat and .

the tim e occupi ed in the proc ess as w ell as the conc entrati on ,

of the Fehling s solution h av e a v ery important b earing upon

’
,

the acciI racy of the r esults .

It is advisabl e to compl ete the titration in as short a tim e

as possibl e A pr elimi n ary t est should alw ays be m ad e in
.
,

which the approximate quantity of the solution r equired is

found ; th en a s econd and more accurat e ti tration can be
don e in whi ch the sugar solution may be add ed more boldly ,

and the t im e of boiling and exposur e of the copp er solutio n

to the air much l ess ened The compl ete reduction of the .

copp er (usin g un diluted Fehling s ) after the addition of the ’

,

requisit e quantity of sugar do es not take plac e instantly ,

“

The tim e r equir ed vari es som ewh at with the differ ent sugars .

For instanc e with glucos e inv ert sugar and l ev ulos e the
, , ,

r ed uction is not compl ete until after h eating two minut es ;

with m altos e four minut es and wi th l act os e six minut es are
,

req uired .

If the sugar to be ex a mi ned be ei ther glucose, maltose, or

lactose,it may be titrated directly ; but if it it be sugar cane,

-

must first be inverted This is don e by dissolving the sugar

.

( 5
0 gm
.
) in about
. mils of w a t er adding
1 00
3 or 4 dro p s O f ,

strong hydrochloric acid and boiling briskly for ten or fift een
,

minutes This is th en all ow ed to cool n eutraliz ed with potas

.
,

sium hydroxid and made up to 0 0 mils with wat er

, 1 .

The sugar in uri ne may be esti mated by thi s process . The

urin e is pl aced in the burett e and run into the boilin g Fehling s ’

solution in the usual m anner If it contain a l arge qu antity .

of sugar it must be dilu t ed two or three tim es

, .

In estim ating with Fehling s solution it is w ell to attach a ’

294.
THE E SSE N TIAL S O F VO LUME TRI C AN A L YSI S
rubb er tub e eight to tw elv e inch es in l ength to the l ow er end
of the bur et t e so th at the b oiling n eed not be don e dir ectly
,

und er the burette and t h us caus e incorrect readings thro ugh

,

the exp ansion O f the liqui d t h er ein .

Det erm i nat i on of the E nd p oi nt It is always somewh at-

.

diffi c ul t t o d etermin e the exact point at which th blue c ol or e

dis app ears owing t o the pr es enc e of the pr ecip it at ed s uboxid

,

of copp er Thi s di ffi culty may be ov ercom e by the addition

.

of som e subst anc e which will pr ev ent the p r eci p it at ion of

the cuprous oxid such as ammonium hydroxid or pot assium

,

ferrocyani d Wh en the l atter is us ed the disapp earanc e of

.

the blu e color can th en be r eadily s een as the solution r em ains ,

cl ear to the end turning from blu e to gr een and fin ally brown
, , ,

which in di c at es the end of the r eaction .

Prof essor Bartl ey r eports thi s m ethod as accurat e r eli abl e , ,

and r apid provid ed the solution be not b oil ed during the

'

r eduction He r ecomm ends adding to the Fehling s s olution

.
’

in the p orc el ain b asin 0 mils of a p er c ent freshly prepared

1 10

s olu t ion of po tassium ferrocyanid and 3 mils of wat er The

°

0 .

ferrocyani d do es no t p r ecipit at e the copp er in alk alin e solution .

L Beulaygue (Comp t r end

.
3 5 )
8 sugg ests
. the following
.
,
1 ,
1

m ethod for d etermining the end r eacti on wh en titrating s ugar -

solution in the usu al m ann er with Fehling s reagent using ’

,

s olution of sodium monosulphid as the indicator Wh en the .

end of the r eaction is n ear a littl e of the hot s olution is ap p li ed

,

by m eans of a gl ass rod to two sup erimp os ed whi t e fil t er ,

p a p e rs . T h e upp er on e acts as a filt er r et aining the

p ar ,

ti cles of cu p rous oxid The low er p ap er is wi t hdrawn and the

.
,

m oist sp ot t ouch ed with a drop of the sodium monosulphid

reag en t w ,
h en an imm ediat e bl ack stain of cupric sulphid
is form ed if the reac t i on is not comp l et e By succ essive .

s p ot t ing out and tes t in g in thi s m ann er a v ery accurate r eading ,

Of the end r eaction may be obt ain ed

-
I t is imp ort ant wh en .
,
2 96 THE E SSE N TIAL S OF VOLU ME TR I C AN AL S S Y I
for fift een minutes ; the solution is then cool ed and dilu t ed to ,

abo ut 2 00 mils E ighteen mils of strong hy dr ochloric acid

.

are th en added an d the solu t ion h eat ed un der a r eturn con

,

dens er for two or t hr ee hours The s olution is th en cool ed .

,

n eutraliz ed with potassium hydroxid and diluted to 2 50 mils .

This is put int o a bur ette and titrat ed into 1 0 mils of Fehling s
’

solution as describ ed ab ove under reducing sugars

, ,

In estimating the starch in b aking powder 2 to 5 gms , .

of the p owder a e intro duced into an E rl enm eyer flask 5

r , 1 0

to 00 mils of a 4 p er c ent solution of hydrochl oric acid a

2 re

added and the sol ution g ently b oil ed for four hour s aft er
‘

which the flask and c onten t s are cool ed n eutraliz ed by adding ,

sodium hy dr oxid and m ade up to a definite volume It is

, .

th en ready for t es t ing wi th Fehling s solution ’

.

Ten mils of Fehling s soluti on is the equival ent of

’
5

gm of inv ert s t arch

. .

E st im at i on of S t ar ch af t er Inv er si on by Mean s in Diast ase

The tr eatm ent of st arch with m alt infusi on or p ur e di ast as e
at a t emp erat ur e not ab ov e 70 C r eadily c onv erts the s t arch
°
,
.

into malt os e but the solu t i on also contains b esid es maltos e

, , ,

vario us d extrins in proportions varying with the t emp erature

'

at which the di ast as e acts The dig estion may vary from .

fift een minu t es to fift een hours Compl ete conversion of the .

starch may be d et ermin ed by t esting occasion ally with iodin .

A blank exp erim ent should be m ad e esp eci ally if the dig estion ,

is c arri ed on b eyond half an hour A like quantity of the .

s am e diastas e solution should be digest ed at the s ame tem

erature and for the s am e tim e and the amount of sug ar
p ,

foun d d educt ed from the total quantity found in the analysis .

Faul enb ach m ak es use of the foll owing solution of diastas e

Cr ush 3 5 kil os of fr esh gr een m al t tr eat with a mix t ur e of
.
,

two li t ers of w at er and f our li t ers of glyc erin and let st an d

Z i
e h f p hysi l C h m VI I 5 ;
t sc r . . o .d C h m C t lh
e . 883 63
, ,
10 an e . en ra .
, 1 , 2.
 ES TI MATI O N OF S U G AR S 297

for one w eek stirring occ asion ally ; th en express and filter
, .

This solu t ion is v ery st abl e F iv e drop s of it will dissolv e

.

I gm of s t arch ; 5 drops of it c ont ain a quantity of c arbo

. 1

hy drat e = 0 00 1 gm of glucos e
. . .

A qu an t i ty of the substanc e to be t est ed (cont aining about

2 gms of starch) is boil ed to g el atiniz e the starch Fift een
. .

drop s of the diastas e solution are th en add ed and the mix ,

ture dig est ed at 63 C It is then fi lt ered to s ep arat e the

°
.

undissolved c ellulose etc and h eated wi th , mils of hydro

.
, 20

chloric acid in a wat er b ath for three hours The acidi ty -

.

is th en just d estroyed by means of c austic soda the glucos e ,

d etermin ed gm d educted and the starch c alcul ated

,
.
,

from the glucos e .

employs pur e di ast as e prep ared as foll ows

’
O S ulli an v ,

Pour sufli ci en t w at er ov er 2 or 3 kilos of fi n ely crush ed

p al e mal t to just cover it L et stand for three or four hours
.
,

th en express and filt er the solution Add alcoh ol (sp gr . . .

until the li q uid abov e the fl occulent pr ecipi tat e b ec om es o pal

escent C oll ect the pr ecipitat e w ash it with alcohol (sp gr
.
, . .

to th en with absolut e alcohol and press it b etw een

linen Fin ally dry it in a vacuum ov er sulp huric acid
. .

E stimatio n of the D i ast asi c V al ue of Mal t E x tr act The .

di astasic v alu e of m alt extracts m ay also be det ermin ed by

estim ating the amoun t of m altos e produc ed by a giv en amount

of the extract in a giv en tim e wh en brought in contact with ,

an exc ess of g el atiniz ed st arch solution It is always n ec ess ary .

to estim at e the copp er r educing p ow er of the extracts with

-

F ehling s solution upon a s ep arat e s ampl e and to d educt this

’
,

from the tot al reducing power found aft er tr eatment with

the st arch .

The proc ess is bri eflv as follows : A d efinit e quantity (say

3 0mils ) o f g el atiniz ed s t arch m ad e from the b est Bermud a ,

J r Ch m S ou X L
. V e . oc .
, 1 .
2 98 THE E SSE N TI AL S OF VO LU ME TRI C AN AL Y SI S
ar rowroot of 3 pe cent str ng th is p l ac ed in a flask and
,
r e ,

h eat ed to 4 C A w eigh ed am oun t of the mal t ex trac t (say

0
°
.

2 0 mils of a 1 p er c ent s olu t i on ) is t h n added and the t emp er

e ,

atur e k ept at 4 0 C for exactly h alf an h our At the end of

°
. .

this time some sodium hydroxid s oluti on is added in ord er

to ch eck the fur t h er action of the di ast as e upon the starch

(h ea ting to 1 00 C accomplish
°
. es the s am e r esult
) T he solu t ion .

is th en dilut ed to a defin ite volum e with wat er and the maltos e

pro duc ed es timated by Fehling s solution in the usual mann er
,
’
.

The qu an t i t y of r educing sugar originally p r es en t in the s amp l e

m ust be previously det ermin ed and this amount d educt ed,

from the to tal amo unt foun d aft er treatm ent wi t h starch ,

an d the r em ain der c alc u l at ed as m al t os T n m ils of F ehling s ’

e . e

soluti on is the equival ent of gm of maltos e . .

300 THE E SSE N TIAL S O F VO LUME TRI C AN A Y S S L I
The reaction is repres ented as follows
OCH2 O 4 N H3 CH
( 2 ) 6N 4 6H2 0 .

4 ) 1 80 4) Hexam ethylen etetram i n

N
gm s .
gm s . or 1 0 0 0 mil s2 VS

gm .
gm . or 1 mil s

Assuming that 22 mil s of sulphuric acid w ere employed

2
in the titration 2 2 mils of the ammonia solution must have
,
—

b een in excess h enc e 2 8 mils of the l at ter w ent into combina

,

tion with the formal dehyd e Thus the 2 mils of form al dehyde .

solution contain ed 2 8 gm .

A G Craig
. . s ays that the chi ef difli culty in using the
L egl er m ethod is the vol atility of the ammoni a The di ffi culty .

is not so much the loss of str ength in the standard solution ,

but the loss during the d etermin ation He propos es the follow .

ing sch em e by whi ch this error is r emov ed .

Pr ep ar e a norm al solution of sulphuric acid Mak e up an .

appro xi m at ely norm al solution of ammoni a the exact str ength ,

b ein g immat eri al Procur e s everal three oun c e prescription

.
-

bottl es with smooth sid es and clos e fitting soft rubb er stopp ers -
.

Pr ep ar e a m ethyl orang e solution Pr ocur e a boil er in which .

the bottl es may be imm ers ed to the n ec k without ups etting

(a l arg e b eak er will do ) Ta k e as much of the s ampl e.as

will contain 0 5 gm of formald ehyd e Measur e with the

. . .

pip ett e 2 5 mils of the ammonia solution into each of the bottl es
, ,

and to h alf Of th em add a s ampl e of form ald ehyd e ; stopp er

tightly I f the n ec ks of the bottl es are small the stopp ers

.
,

n eed not be ti ed do wn Pl ac e the bottl es in the boil er add

.
,

cold wat er to the n ec ks and h eat to boiling Boil for one , .

J . A C S . . .
,
X XI I I ,
64 2
 ES TIMATI O N O F FO R MALD E HYD E 301

hour and cool by running in cold water slowly b eing careful

, ,

not to allow the col d w at er to touch the hot bottl es T itrat e .

with sulphuric acid and m ethyl orange to the fi st i ndi cati on r

of a color cha nge T a k e the differ enc e b etw een the r eadings
.

for the blanks and those for the sampl es as the ammonia ,

consumed in normal mils O f this di ff erenc e 1 mil = o 0 60 1 .

,
.

gm of form aldehyd e
. .

The L egl er m ethod is als o li abl e to error b ec aus e the

compoun d form ed is a w eak b as e and as such combin es ,

with acid whil e at the s am e tim e i t is liabl e to d ecomp os e

,

into ammonia and formald ehyde and thus giv e an ind efinit e
end point wh en the r esidu al ammoni a is titr at ed with acid
-
.

E rror is also liabl e to be introduc ed through the pr es enc e of ,

c arb onic acid in the ammonia wat er whi ch with the indicator , ,

rosolic aci d gives no sharp end reac tion

,
-
.

The Amm o n ium Chl ori d Met ho d In thi s m ethod a solu .

tion of ammonium chlorid is us ed from which ammonium ,

is evolv ed by treatm ent with sodium hydroxid The exc ess of

,
.

alk ali is th en d et ermi n ed by titr ation wi t h st and ard solution

of sulphuric acid T h s m thod as d vis d by H Schifl

i e e e .
*
, .
,

and Modifi ed by C A Mal e t is as follows : . .

,

Introduc e 2 gms n eutral ammonium chlorid dissolved in .

,

2 0 mils of w at er into a fl ask or bottl e of about 2 00 mils c ap acity

, ,

having a w ell fi tting stopp er D ilut e 0 mils of the formald ehy de

-
. 1

solution to 1 0 mils with water and n eutraliz e with sodium

0 ,

hydroxid solution as the form al dehyd e solution gen erally con

,

tains varying qu antiti es of formic acid Add 2 0 mils of this .

n eutraliz ed solution to the ammonium chlori d solution th en ,

N
2
5 m1] s of N aO H, and I mm edI ately stopp er the flask , and

Chem Z tg , . XXVI I
.
, 14

TPharm ou . J r J .
, une, 1
90 5, 844 . S ee al so r
Ca l E . Smi h, A t .
J . Ph , .

LXX , 86,
302 THE E S SE N TIAL S O F VO LUME TRI C AN A Y S S L I
l eave for one h our . A f t erwards det ermi n e the e xc ess of a lkali
N
wi t h H2 $ O 4 ,
using ros olic acid or litmus s ol uti on as in di
2

cator b ot h of which giv e up a sharp

,
r c t ion The en d- ea .

r eacti on and c alcul at ion is b as ed up on the following equation :

2 N H4 C l + 3CHZ O 2 N aO H = N 2 (CH2 ) 3 2 N aCl H
5 zO .

I mi l is equival ent to
N aO H gm of formic al dehyd e . .

Thi s modi fi ed m ethod is quit e as simpl e and giv es r esults ,

practically id entical with that of Romij n .

Oxi datio n by Hy dro gen D iox i d (Bl an k and Finkenbein er)

This m ethod d ep ends upon the use of hydrog en dioxid for
O xidizing form ald ehyd e into formic acid in alk alin e solution , .

The formic acid so p roduc ed n eutraliz es a portion of the alk ali ,

and the exc ess of the l att er is th en d et ermin ed by ti trati OI

with standard acid The m ethod gives good results and can .

be v ery rapidly c arri ed out .

T hree mi ls of the form al dehyd e solution are p l ac ed into a 1 0 0

mil E rl enm eyer flask the l atter closed with a w ell fi tting stopp er
,
-
,

and the w eight O f the solution c ar efully t ak en 5 mils of . 0

normal N aO H V S are then add ed and follow ed imm ediately

. .
, ,

but slowly through a small funn el by 5 mils of a 3 p er c ent

, ,
0

hydr ogen dioxid solution pr eviously neutraliz ed with norm al ,

N aO H V S using a dr op of litmus so lution

. .
, The solution is .

allow ed to st an d about minut es or until t h e r eaction h a

5 s 1 ,

ceas ed The fu nn el and the sides of the vess el are th en

.

rins ed with distill ed water a few drop s of litmus solution ,

add ed and the unconsum ed alk ali titrat ed wi t h norm al H S0 2 4

V S The mils of the l att er deduct ed from the 50 mils of nor

. .

mal N aO H V S origin ally t ak en giv s the qu an t i ty of the

. . e

B ri ht d Ch m G XXXI 979
e c e . e d A J Ph . 899 4 86
es .
, ,
2 an . . .
,
1 , .
304 THE E SSE N TIAL S O F VO LU ME TRI C AN A L Y SI S
sulphuric aci d a e added r ,
an d t h en the ex e c ss of iodin ti trat ed
with de cin ormal t hiosul p hat e s olu t ion . Ea ch mil of IO
i odin
solution consum ed corr esp on ds to gm formald ehyde . .

A bl ank titration shoul d always be m ade .

A solution containing as much as 5 p er c ent may be

accurat ely estim at ed by this m etho d provi ded not mor e th an ,

2 gms be tak en The m ethod is howev er not accurat e in

. .
, ,

the pr es enc e of other ald ehyd es F O comm enting . . .

upon thi s m ethod s ays that it is quit e s atisfactory bu t th at

, ,

the qu antiti es of form ald ehyd e an d r eag ents us ed are unnec

essari ly l arg e an d cumb ersom e an d the m et ho d is h enc e m odi ,

fi ed by him as follows :
From a w eighi ng b ottl e consist i ng of a sm all E rl enm ey er
,

flas k fi tt ed with a p erforated rubb er stopp er t hrough which

,

passes a dropp er and containing about 2 5 or 30 mils of the

,

form ald ehyde sol ut ion weigh out accurately about 0 gms
, 1 .

of the solution into a stopp ered 500 mil flask and fill this to -

the m ark with distill ed wat er For titration r emove 5 mils of .

this solution corr espondin g to

, gm of the w eigh ed quan .

tity of form aldehyd e and put into a 2 00 mil E rl enm ey er flask

,
-
.

Into anoth er flask put 5 mils of wat er for a bl ank titration .

To both now add 2 0 mils of norm al N aO H and th en 2 0 mils

of an a pproximately 75
10 di n solution whose exact str ength ,

n eed not be known and , let stand for fi ve or tenminutes for

the entir e compl etio n of the r eaction . N ow add 2 5 mils of

N
normal H SO and titrate the exc ess O f iodin with IE N a 8 0
2 4 2 2 3 .

The di ffer enc e b etw een the mils of thiosulph at e us ed on the

N
a ssay and the mils of the bl ank is the numb er of mils of iodin
B ull . Ph .
,
Aug .
, 1 90 3 , 32 3 .
 ES TI MATI ON OF FORMALD E H D E Y 305

consum ed by the formal dehyde E ach mil of I o din so .

us ed equals gm of CH O .
Q .

The Pot assi um Cyan id M et hod * T his m et ho d is es p eci ally .

applic abl eto s olutions c on tainin g small quantiti es of form al

ep ends up on the f act th at pot assium cyani d and

combin e to form an addition p roduct in which ,

on e m ol ec ul e of p ot assi um cy ani d c ombin es with one mol ecul e

of formald ehyd e as shown by the following equation

,

CH2 O K CN NE C —
C —
O —
K .

In the estimation the formald ehyd e is mixed with a kn own

,

quantity of potassium cyanid (in exc ess ) the exc ess of the ,

l at t er b ein gdet ermin ed by the use of s t andard silv er nitr at e

s ol uti on and th us the quan t ity of p otassium cyanid which
, ,

c ombin ed wi t h f orm ald ehyde is found and from this the ,

qu an t ity of formald ehyde is c alculated .

N
The process i s f 1
carri ed mils of out as ollows :
‘
Ten
10

silver nitrat e are treat ed with 6 dro p s of 50 per c ent nitric

aci d in a 50 mil fl ask Ten mils of a solution of p otassium
'
- -
. -

cyanid (containing gm of K CN in 50 0 mils of water) are

1 .

th en added and w ell shaken An aliquot p art of the fi ltrate .

,

say 2
5 mils is th en titr at ed by V olh ar d s m ethod wi t h
,
’

ammonium sulphocy an at e for exc ess of silver .

Anoth er mils of silver nitrate solution is then acidified

10

Ri Z it h
o l Ch m XXXVI
n, e sc 8 4 r . ana . e .
, ,
1 —
2

fB d H Smi t h J A C S XXV
ernar .
3 ,
. . . .
, ,
10 2
306 THE E SSE N TIAL S OF V O LU ME TRI C AN AL Y S S I
wi th nitric acid and treated wi t h 1 0 mils of the po tassium
cyanid solu t ion to which has b een added a m easured quan t i ty
of dil ut e form al dehy de s olu t i on The whol e is m ade up to .

50 mils an d th en filt er ed 2
5 mils of the filtr at e ar e titr at ed .

N
wi th 10
mmonium sul pahocy an at e for exc ess of silv er as

The di fferenc e b etween th es e two results multiplied by .

2 gives the amount of pot assium cyani d which was us ed by

the formal dehyde in t erms Of , sul phocyanate .

N
Each mil of 10 V S repres ents 0 00 3 gm Of formal dehyde
. . . . .

The b est r esul t s by this m ethod are ob tain ed if the s ol u ,

tion Of formald ehyde is dilu t ed to b elow 1 per c ent Wi th .

1 p er c ent s olutions it is n ec ess ary to u se 1 5 mils of the silv er

solution In estimating very dilute solutions it is ad isabl e

.
, v

to use a 0 0 mil flask and to tak e 1 mils of the filtrate for

2 -
00

the titr ati on It is possibl by this m ethod to determin e

. e

with accuracy one p art in

Paraformaldehyde (CH O ) This is a p olym eric f orm of z 3 .

form al dehyde and m ay be assay ed by the sam e m ethods The .

U S P I X r ec omm en ds th proc ss in which hy drog en dioxi d

. . . e e

is used the proc edure b ing prac tic ally the same
,
e .

E ach mil of n orm al alk ali hy droxid V S corr esp on ds to . .

gm Of (CH O ) .
z 3 .

Acetone (D im ethyl k eto ne) This

-

may be assay ed by the io dom etric m etho d us ed for formalde ,

hyde O ne mil of ac et on e is accurat ely w ei gh ed in a s t opp ered

.

w eighi ng flask tared tog th er with som e dis till ed water Thi s I s e .

transferred to a mil flask and diluted to the mark with

1000 -

di still ed w at er T w enty fi mils of norm al p otassium hydroxi d

.
-
ve

V S are pl ac ed in a 5 mil gl ass s t op p er ed flask and to t his

. . 2 0- -
 CHAP TE R X V II
ES TI MATI O N O F AL C O HO L I N TI N C T U R E S AN D
BE V E RA G E S

THE quantity of alcoh ol con tain ed in di lute spi ri t which ,

l eaves no residu e up on vaporati on may be asc ert ain ed by e ,

taking the sp gr and r eferring to the alc oh ol tabl e Wh en

. . .

taking the sp ecific gravi ty the t emp erat ur of the liquid , e

sho ul d be 53 C (60 F ) 1
°
.
°
.

I n Win es Beer Tin ctu res and oth er alc oh olic liquids
, ,

containing vegetabl e matt er the sp gr of th samp l is tak en , . . e e

at 5
1 3 C ( 6
°
0 F ) an
. d not ed A c er
°
t ain qu.an t ity ( y
sa .

1 00 mils) is m easur ed off and ev aporat ed to on h alf or unti l e ,

all odor of alc ohol has p ass ed Off the evap orat i on b eing con ,

duct ed without ebullition in ord er that p articl es of the materi al

,

may not be c arri ed off by the st eam The liqui d l eft is .

th en dilut ed with distill ed water cool ed to 60 F and made ,

°
.

up to the o rigin al volum e ( 00 mils) and the sp gr taken 1 , . . .

L astly we c alcul at e : the sp gr b efor e evaporat in g is divid ed

‘
. .
,

by the sp gr after evap orating and the quoti ent will be the
. .
,

sp gr of the wat er and alcohol only of the liquor Th en

. . .

by r eferring to the alc ohol tabl e the p erc entage of alcoho l

contain ed in the liquor is obtain ed .

E x ample The liquor b efor e ev aporat ing had a sp gr

. . .

of aft er evap oration and dilution to 1 00 mils the sp gr . .

was found to be

-99SI
09 87 , the sp gr . . Of the con ta med sp I rl t .
 AL COHOL I N TI N CTU RE S AN D B E VE RA GE S 309

TAB LE F O R AS C E RTA I N I N G THE P E RC E N TA G E S RE S PE C T I VE LY

O F A LC O H O L BY W E I G H T BY V O LU M E A N D A S P R O O F , ,

S P I R I T F R O M T H E S P E C I F I C G RA VI T Y
,
.

C d s d fr m h
on en e ll t A l h l T bl s f M
o t e e x ce en H b r i th co o a e o r . e ne n e

A lyst l v p p 4 3 63
na ,
”
vo . . .
—
.

p
S ec i fi c
b l b l
A so u t e A s o u t e
f
P roo p
S eci fi c
Ab lso u te A b ll
so u te
P ro o f
y
G ra v i t
b
A lc h l
tp q
A C ll l
ig fi
'
g l t by r l r e
'
p
S i ri t . G rav i t y by
Al h
vi g IIt
c
g r
l
bé g
dlfi
l
’
r
l
p
S i ri t .

g
e
P e r cen t P er cen t
e r c en t P er c en t P er c en t P er c en t
. .

. . . .
3 10 THE E SSE N TI AL S OF VO LU ME TRI C AN A LY S I S

S p e nfic
A b l A b l1
so u t e
P
so u t e
roo f S p ec rfi c
b l b l
A so u t e A s o u te
l
G ’ a ’i t y
o
l
’ k
r
i ’i
v }531 32 P
bi l iii b fg t
3
.
S p .
i ri t
e r c en t
G ra t
I
vi y b tf ii 953 33 P
Al l
'
g t 13
3
S
1
p i i
.
r t
er c e nt
P er P
c en t. er c en t .
.
S ~S e r cen t Per cen t
. .
.

A b l
s o u te A l h
co o l .
312 THE E S SE N TIALS OF VOL UME TRI C AN AL Y SI S
vol atil e acids and volatil e b as es are present n eutraliz e firs t ,

with dilute sulphur ic acid and distil ab out 5 mils th en n u 0 , e

traliz e the distill at e with s odium hy droxi d T S and ag ain dis t il.

to Obtain 5 mils of distillate

0 .

If aceton e camphor chloroform eth er glycerin (3 p r

, , , , 0 e

cent or over) volatil e Oils or other volatil e products are sus

p ect ed to be pr es ent transf er the fir st dis t ill a
, t e to a s ep ar ator ,

s aturate it with so dium chlorid add 5 mils of p etrol eum

, 1

b enz in (boiling point 4 0 5 C ) and shake for one or two

-
0
°
.

minutes After the liquids have completely sep arated draw

.
,

off the low er alcoholic s alt s olution into a s econ d s ep arat or

and r ep eat the extr action with 1 5 mils of p etrol eum b enzin .

Ag ain draw of the low er alcoholic s alt solution Introduce .

this into a 2 00 mil distilling fl ask Wash the combined b enzin

-
.

solutions with about 5 mils of saturat ed s odium chlori d s olu

2

tion and add the washings to the dis tilling flask and dist il ,

about 4 5 or 4 8 mils bring to the origin al t em p eratur e dilut e

, ,

with water of the sam e t em p erature to 5 mils determin e 0 ,

sp ecifi c gravity and alcohol per c ent as dir ected above .

 PA RT III

A F E W GA S OM E TRI C A N A L YS E S

CHA PT E R X V III
THE N ITRO ME TE R
FOR gen eral gas analysis and fo the rap i d es t im ati on of ,
r

such s ubs tanc es as et hyl ni tri t hy drog en dioxid ur a bl eaching

'
e, , e ,

p o w de r m a
,
ng an es e di oxi d etc an ins t rum ent c all ed the , .
,

ni t om t
r is us d
e er e .

Th app ar at us in i t s simp l est form is shown in Fi g 5

e
7 . .

It c onsis t s of a m eas uring t ub e a of 5 or , ,

0

100 - mils capaci ty and graduated in tenths ,

of a mil This is c onnec ted by m eans of a

.

stout rubb er t ub e wi th an op en equilibrium

“
tub e b als o c all ed con t rol tub e “ pres -
”
, , ,

s ure tub e or l evel tub e Both tub es are

-
,
”
-
.
”

pr eferably provided wi t h a globul ar exp an

sion n ear the low er end and are held by ,

s ui tabl e cl amps up on a stan d in such a ,

mann er th at eith er tub e may be r eadily and

quickly cl amp ed at a high er or lower l evel .

The m easuring tub e is fitt ed at the top

with a stop c ock c and a graduat ed gl ass
-
, ,

tub e or cup d Som e ni tr om et ers are pro

, .
~

v i ded with a thr e way stop cock so e- -

,

arr ang ed th at acc or ding to the way it is

‘

F
turn ed i t will discharg e the c ontents of the
57 IG . .

cup eith er into the m easurin g t ub e b elow or out into the ,

313
3 14 THE E SSE N TI AL S O F VO LUME TRI C AN A Y S S L I
wast e op ening whi ch is usu ally pl ac ed at or i t will discharge c,

the con t ents of the m easuri n g tub e into the w as t e op ening .

With t his ap paratus gas es can be rapidly and accurat ely

m easured at defini t e t emp eratur e and pr essur e .

In m easuring the gas the i nstrumen t is fill ed wi th some

liquid in which the gas is ins olubl e g en erally m ercury In —
.

m any c as es a s aturat ed soluti on or salt may be us ed .

S up p os e we fill the instrum en t wi t h m ercury in s uch qu an

tity t hat wh en the stop c ock is op en ed and the c on t rol t ub e
- -

rais ed the m ercury will ris e as far as the top and ab out two
, ,

inch es in the control tub e -

.

The top is now clos ed the control tube l ow er ed and a ,

a

littl e c arbonic acid gas admitt ed t hrough Th top is e . e

th en ag ain cl os ed and the i n strum ent all ow ed to stan d un til

,

its cont ents hav e acquir ed the t emp eratur e of the room A .

c enti grad e th ermometer susp end ed to the stand will th en give

the t emp er atur e of the gas .

The control tub e is now r ais ed or low er ed so as to m ak e

-

the l ev el of the liquid in both t ub es the s am e This m ak es .

the pr essur e in the tub e the s am e as the atmos p h eric p r essur e

outsid e and by r eferring to a b arom et er stan ding n ear this
, , ,

pressur e is asc ert ain ed .

We now h av e a d efinit e volum e O f the gas at a known

temp eratur e and pressur e .

It now only r em ains to read off the volum e of the gas ,

and corr ect it to the norm al t emp er atur e and pr essur e by

Charl es and Boyl e s l aws r esp ectiv ely

’ ’
,

The norm al t emp eratur e and p r essur e is 0 C and 7 60

°
.

mm pressure Although the U S F adopts a standard tem

. . . . .

e of 2 5 C
°
’

p era tur .

The w eight of the gas in grams may th en be calcul at ed from its

volum e by multi plying the numb er of mils at the norm al temp era
ture and pr essur e by the w eight of I mi] of the gas in grams
, ,
316 THE E SSE N T AL S OF I VOLU ME TRI C AN AL Y SI S
m easures mils 20 . What will it m easur e at 7 60 mm .
(
t he nor
m al pr essur e) ?

7 50 X 2 0 mils
6
mils . A ns .

7 0

us take an exampl e in which b oth l aws are involved

N ow let .

A given v olum e of oxyg en at 5 C subj ec t d to a pressur e

°
1 . e

of 7 50 mm m easures 2 mils What will it m easur e at the

. 0 .

n ormal t emp eratur e and pressure C and 7 60 mm 0

°
. .

In the fir s t exam p l e we fi nd t hat mils of oxyg en at 1 5 20

°

C will m easur e at
. C 5 mils T h en 0
°
. .

750 X mils
6
mils A ns . .

7 0

N owto fi nd the w eight Of this vol um e of o xygen , we pro

c eed as follows :

1 mi l Of H weighs gm .

1 mil of O w eighs m
g ; .

mils Of O 8 70
= 1 .
gm .
, or gm .

In the U S Ps tan dard for temp eratur e and pressure

. . . the
is 5 C and 76 mm and h ence all p harm ac eu tical assays
2
°
. 0 .

should be made in accordanc e wi th this s t andard and all gas es ,

m easured at this t emp erature and pressur e or c orr ec t ions m ade ,

by calcul ation .

E x ample A volum e of gas m easur es mils at 1 5 C °

. 20 .

What will i t m easur e at 2 5 C ? °

° 0 ml ls .

1
5 + 2 73 2 88

following tabl es from the U nited S tates Pharm a

The
COpoei a IX will be foun d v ery us eful for m aki n g t em eratur e
p
and pr essur e corr ections .
 THE N I TROME TE R 317

T R
FA C O S FOR TE MPE RATURE CO RRE CTI ON S
(N or m l T mp
a e erat u re . 2 5
°
C)
.

Tem p er at u re . F act or . Tem p er at ur e . F act or . Tem p er at ur e . F act or .

E x ample . Assuming
that the volum e of a gas read off
was 4 mils at 30 C and it is desir ed to asc ertain the c orr
°
1 . e

spondin g volum e at th n h mils mus t multi li°

5 C e t e 4 1 be 2
p ed .
,

by The r esult will be mils as the equival ent volum e

°
Of gas at 2
5 C .

T R
FAC O S FOR CO RRE CTI ON FOR B AROME TRI C PRE SSURE
(N m l B
or m 6 mm )
a aro et er , 7 0 .

B A R O M E TE R R E ADI N G . B R A R O M E TE R E AD I N G .
F act or . F act or
M m I h 1111 e te rs. nc es .
.

E x ample ssuming that the volume of gas read off was

. A
41 mils a t 590 mm b arom etric p r ess ur e and it is d
.
esir ed to ,

asc ert ain the corr espon ding vol um e at norm al pr essur e ( 60
7
th en the 4 mils must be multipli ed by 1 Th e

r esult will be mils .

 C HAPT E R XI X

A S SAY O F N ITRIT E S

r t of N i tr ous E ther This is an alc oh olic s ol uti on of

Spi i .

et hyl ni t ri t e yi el ding wh en freshly p re ,

p ar ed an d t es t ed in the ni t r om et er n ot l ess th an 1 1 tim es its ,

own volum e of nitr og n di xi

e o d (N O =

Wh en ni t rit es are mixed with an exc ess of KI and acid

ulated with H S O io din is lib erat ed and all the nitrogen
z 4, ,

of the nitri t e is ev olv ed in the f orm of N O as sh own in the ,

eq uat i on

2 C 2 H5 N 0 2 + 2 K I + 2 H2 80 4 2 C 2 H5 O H 2 K HS O 4 12 2 NO .

The p roc ss is c ond uc t ed as foll ows

e

n
O p e the st op c ock of the m easuring t ub e rais e the control
—
,

t ub e and pour into the l atter a s aturat ed s oluti on of N aCl

,

un til the m easuring tub e including the bore of the stop cock ,
-
,

is c ompl et ely fill ed Then clos e the stop c ock and fix the
.
-

c ontrol tub e at a lower l evel N ow i ntroduc e in t o the funn el

-
.

at the top of the m easuring t ub e a w eigh ed q uantity ( ab out

4 gms ) . of s p irit of ni t r ous eth er ; op en the st op cock a n d -

all ow the spirit to run in t o the nitrom et er b ein g c ar eful th at ,

It i i t t t k 5 mils
s conv en n en r t ly m s r d d l l t i t
o a e accu a e ea u e , an ca cu a e s

w ight by m l tiplyi g by th s p i fi gr vi ty b t b tt r t t k
e u n e b t 4
ec c a , u e e o a e a ou 0

mil s f th spi ri t w igh i t

o e r t ly d th dd fii i t l h l t m k
,
e accu a e , an en a su c en a co o o a e

exac tly mil

1 00 Thi s i mi d th r ghl y d mi ls f th s l ti t k
s . s xe o ou an 10 o e o u on a en

f
or ana lysi s .
32 0 THE E SSE N T AL S OF I VOL UME TRI C AN AL Y SI S
What per cent of ethyl nitrite is presen t in the a s mpl e ?
X 55 X 1 0 0
3
. 7 2
Per c ent .

Amyl N itri t e is a liquid containing about 80 per c ent of

amyl ni trit e ( princip ally iso amyl nitrite) C5 H N 0 = 7 9
-
, 11 2 I I . 0 ,

together with vari abl e quantiti es of undet ermin ed com p ounds .

The ass ay is as follows T ak e about 3 mils of the amyl

:

nitrite which has b een previously shaken with 5 gm of

, 0 . .

potassium bicarbonate and carefully decanted Put into a .

tared 1 00 mil m easuring flask and w eigh it acc urately ; add

-
,

alcohol to bring the vol um e to ex actly 00 mils Ten m ils 1 .

of this alcoholic solution are in troduced into the nitrom eter

as dir ect ed for s p irit of nitrous eth er ; 1 0 mils of pot assium

iodid solution (2 0 p er c ent) and 1 mils of 1 H SO V S 0 z 4 . .

are th en added and the volum e of N O g en er at ed m easur ed

, ,

at the ordinary indoor t em p eratur e (2 5 C o 7 7 shoul d °

. r
°

be about 4 mils 0E ach mil at this t emp eratur e r epr es ents

.

m of p ur e amyl nitrit e
g . .

S o dium N itrit e This lik e the oth er ,

nitrit es m ention ed wh en tr eat ed with p ot assium i odi d and

,

sulphuric acid is d ecompos ed and N O is giv en off The

, ,
.

reaction is h ere illustrat ed

2 N aN O z + 2 K I + 2 HgS O 4
K 2 80 4 l N a2 $ O 4
‘‘
2 H2 0 2 N O l IQ ‘"
.

A mol ecul e of N aN O evolv es zwh en prop erly ,

treat ed one mol ec ul e of N O

,

The ass ay proc ess is as follows Weigh out gm of : .

N aN O d issolv
g, e it in ab out 5 mils of w a t er an d intr oduc e ,

the solution into a nitrom et er This is follow ed by a solution

.
 ASSA Y OF N ITRITE S 32 1

1
of gm of KI in 6 mils of water and 5
1 . H 80 1 mils of ; 2 4 .

The gas which is lib erat ed shoul d m easur e not l ess th an 5 0

mil s at 5 C (59 F ) or
1
°
mils at 5 C (77
.
°
. corr e 2
°
.
°

sp ondi n g to n ot l ess th an p er c ent of the p ur e s a l t E ach .

mil at 5 C represents
2
°
. gm and at 0 C .
°
.

gm of .
p ur e N aN 0 2 .

N i tr i c Aci d i n N i trat es Thi s m ay als o be eff ec t ed by the .

use of the nitr om et er .

Wh en a nitrat e is shak en up with an exc ess of sulp huric

acid and m ercury the nitrat e is d ecompos ed and N O is evolv ed
, ,

as s een in the following equ ation :

2 K N 0 3 + 4 H2 80 4 + 3Hg H
3 gSO 4 K 2 80 4 ZN O + 4 H2 0 .

Thus ea ch mol ecul e of the nitrat e radic al N O3 giv es off a

mol ecul e of N O .

N ot more th an gm of nitrat e should be taken for .

an alysis sinc e if thi s quantity is exc eed ed the vol um of

, , ,
e

ga s e v olv ed wi lll be gr eat er th an the instrum ent can c ouv e

ni en tly h old In this estimation the ni tr om et er is fill d wi t h

. e

m ercury inst ead of brin e ; the nitrat e is diss olved in 5 cc .

of wat er introduc ed into the nitrom et er and foll ow d by

.
, ,
e

exc ess of strong sulphuric acid The instrum en t is w ell .

sh ak en for some tim e and wh en action has c eas ed and the ,

cont en t s hav e cool ed down to the t emp eratur e of th room e ,

the l ev el is adjust ed and the volum e of N O r ead off an d cal

culated in the usu al way .
NO 1 li ter at 0
°
C . and 7 60 mm .
= gms .

at 2
5 C
°
. and 7 60 mm .
= gms .

ON E MI LLI LI TE R OF N I TROGE N D I OXI D I S THE E Q UI VALE N T 0

° °
At 0 C . an d At 2 5 C . an
760 mm .
7 60mm .

G r am . G ra m .

tr g
N i o en di oxi d, N O =
tr t
Amyl ni i e, CsHu N Oz 11

t tr t
E hyl ni i e, C2 H5 N 0 2
tr t
Sodi um ni i e, N aN Oz
324 THE E SSE N TIAL S O F VO LUME TRI C AN A Y S S L I
The l arger flask is fill ed with water or b ett er a solution , ,

of so di um sulp hate ; the conn ection is th en made by means

of the rubb er tub e and the gen erating bottl e tipp ed ov er and
,
-

agit at ed so th at the liquids will mix and the r eaction tak e

pl ac e.

The lib erat ed oxyg en then p ass es into the l arg er bottl e ,

disp l acing an eq ual v ol um of w at r which is c oll ect ed and

e e ,

m easured Half of thi s volum e repres ents the volume str ength
.

Of theH2 0 2 .

A n I mprov i sed N i tromeler may be us ed The author has .

found the following in strum ent convenient :

To the bottom of an ordin ary 50 mil bur ett e is attach ed -

a suit abl e l ength of rubb er tubing to the oth er end of which

,

is attach ed anoth er burette or ungraduated tub e which s erves ,

as a control tub e -
.

Into the top of the bur ett e is fi tted a rubb er stopp er ,

through which p ass es a short gl ass tub e which is conn ected ,

by m eans of a rubb er tub e to a g enerating bottl e similar to -

th at us ed with S qui bb s Urea Apparatus Into the control

’
.

tub e is poured the solution of sodium s ul p hat e sufli cient to ,

fill the burett e t o the z ero m ark and hav e the surfac e of the
liquid in bo th tub es on a l evel .

About 30 mils of strong p erm anganat e solu t ion acidul ated

with sulphuric acid are now pl aced in the generat ing bo t tl e -
,

and th en the sm all t est tub e or hom eo pat hic vi al

-
c ontaining ,

ex actly 1 mil of hy drog en dioxid is pl ac ed in The gen er

,
.

ating bottl e is th en st op p ered and agitat ed the ev olved gas ,

p ass es ov er an d
,
forc es down the liqui d in the bur ett e ; the

control tub e is th en low ered so as to bring the surfaces of

-

the liquid in both t ub es on a l ev el .

The r eading is th en tak en .

E ach mil of gas repres en t s one half volum e of oxygen -

evolv ed from the dioxid if 1 mil of the l at t er is us ed E ach mil .

 HYD ROG E N D I OXI D 32 5

of oxygen evolved from 1 mil of the dioxid repres ents also

gm of absolu te H O or
. z gm of avail abl e oxygen
z, . .

Thus if from 1 mil of the solution of hy drog en dioxid 2 0

mils of gas are evolved it is a so call ed ten volum e solu t ion

,
- -

an d cont ains gm of absolut e H 0 or .

2 2,

gm of avail abl e oxygen

. .

According to N aylor and D y er (Trans Brit Ph C onf . . . .

,

1 90 1 ,339) th e g asom etric p erm angan at e m ethod is unr eli abl e ,

b ec aus e und er the conditions of the t est sulphuric acid ad ded

to the brin e solution in the nitromet er n aturally lib erat es a
littl e hydroc hl oric acid and this in the pres enc e of p erm an
,

g an a te b ecom es to som e ext ent d ecompos ed into chlorin It .

is the unc ertainty as to the ext ent to which the chlorin is

absorb ed by the w at er which r end ers the accuracy of the
,

m ethod doubtful The r esults of this m ethod are uniformly

.

too high wh eth er the gas be coll ect ed over m ercury over
, ,

saturated magn esium sulphate or ov er brin e and in the , ,

l att er c as e consid erably high er But wh en the dichromat e .

V S is us ed (without acid ) clos ely concord ant r esults are

. .
,

obtain ed wh eth er the gas be coll ect ed over m ercury or the

, ,

oth er solutions The evolution of oxyg en by the l att er

.

m ethod is slow er than wh en p erm angan at e is us ed but the ,

oxyg en obtain ed r epres ents the volum e avail abl e in the sampl e .

In the Hypo chl ori te Met ho d the nitrom eter is fi ll ed with ,

a s aturat ed solution of so dium chlori d Two mils of the hydro .

g e n d ioxid are ad mitt ed into th e m easuring tub e the funn el ,

tub e fill ed with a littl e water and this also let in th en 2 mils of
, , 0

the chlorinat ed lim e solution introduc ed From this point the .

procedure is the sam e as in the gasom etric p erm anganate m ethod .

C& (Cl0 ) 2 2 H2 0 2 04 CaC12 2 H2 0 .

presence of pres ervatives excep t inorganic ones gives

The , ,

low results .
32 6 THE E SSE N TIAL S O F VO LUME TRI C L I
AN A Y S S

The Hyp obro m i t e Method W M D ehn (J A C S . . . . . . .

,

XXI X 3 5) d escrib
1 es
1 an acc ur at e an d r api d det ermin at i on
of hydrogen dioxid by m eans of sodium hypobromite using ,

a ureom et er The r eaction involv ed is

.

H2 0 2 N aBr O N aBr Hg O O

The pp arat us is sh own in Fi g 58 The f oll owing descrip

a . .

ti on of the m etho d is by D ehn from the

J o urn al of the A m e ric an C h emic a l S oci ety . ,

The stop cock E is op en ed an d the s t op

-

cocks D and F are clos ed ; t h en the s olu t ion of

sodium hypobromite is poured in at the top
of C un t il it fills the tub es A and C to som e
p o int abov e the stop coc k E -
.

“The stop cock E is th en cl os ed and the -

s t op cock F is op en ed so th at the hyp ob o

-
,
r

mit e in C may run down to the c onstric t ed

p or t ion ; the soluti on in A is th en sustain ed
by atmosph eric pr essure The st0p c ock D .
-

( a rr a ng ed so a s to d eliv er only in th e two

directions of a right angl e tri angl e) is turn ed -

from the position shown in the fi gure and is

so controll ed th at B may fi rst be w ash ed with

a littl e of the hydrog en p ero xid an d th en be

F m 58 .
fill
.
ed wi t h the s am e to a r ead abl e h eight on

the sc al e U pon turning D so as to admi t a

.

regul at ed volum e of the hydrog en p eroxid solution ani mm ediat e

evalu ation of oxyg en r esults Aft er admi t ting most of the hyp o
.

bromit e h eld abov e E and l etting stand for a minu t e or two

,

so as to drain prop erly the columns of hyp obromite in A

,

Thi s s l ti i p r p r d
o u on s e a e as di rected unde r E stim atio n o f U rea ,
excep t
th t i t i fi
a s lly di l t d with
na u e an e qua l v me
o lu o fw t r a e .
 C HAPTE R XXI

ES TI MATI O N O F SO LU B L E CARB O N AT E S BY T HE U SE O F
THE N ITR O M E T E R

TH E ni trom eter may be us ed for estimatin g ammonium

carbon at e in aro mat i c S pir i t of amm o nia .

The nitrom et er in thi s c as e must be ch arg ed wi t h m ercury ,

as the lib erat ed C0 is solubl e in aqu eous liq uids

2 .

A giv en volum e of the sp irit is in t roduc ed in t o the nitrom et er

follow ed by an exc ess of dilut e HCl and the evolv ed gas th en ,

r ead off; and from i t s qu antity the prop or t i on of amm onium

c arbon at e may be c alcul at ed by app lying the equati on
(N H4 ) 2 C O 3 2 HCl 2 N H4 C 1+ E z o J
r C0 2 .

* *
96 44

The vol um e of gas lib erat ed must first be reduc ed to i t s

corresp on ding volum e at 0 C °
.

E ach mil of C 0 at 0 C w eighs gm N ow if

°
2 . .

44 gms of .C 0 5 r epr es ent 96 gms of n orm al ammonium car .

b on at e how much ammonium carbon at e do es

,
gm .

of C 0 r epr es ent ?
2

x = 0 0 0 4 89 gm . 2 .

hus each mil of

T C0 2 n ormal pressur e and
at 0
°
C .

repres en t s gm . of (N H ) C 0 app roxim at ely

4 2 3, .

The atom i c g s
wei ht are app o xim ater .
 CHAPTE R XXI I

‘
ES TI MATI O N OF UR E A IN U RI N E

TH E d termination of urea is b as ed u p on the fact th at

e

wh en urea is dec omp os ed by an alkalin e hyp ochl orite or

hypobromite c arb on dioxid and ni trogen a e giv en off as
,
r ,

the equ at i on sh ows :

C O (N H2 ) 2 3N aBrO 3N aBr CO z N2 2 Hz O .

The lib erat ed N may be m easur ed and from its quantity ,

the am oun t of ur ea c alcul at ed The oth er products of the

.

d ec omposi t ion go into solution .

The hypobromit e solution is pr ep ar ed as follows : 1 00

gms N aO H are dis solved in 2 50 mils of water and wh en this
.
,

solu t ion has b ecom e col d 2 5 mils of bromin are added and ,

the soluti on k ept col d This solu tion con tains so dium hypo
.

bromite bromat e and hydr oxid It readily undergo es decom

,
.

position and shoul d therefor e always be freshly pr ep ared

,

wh en wanted for use To 1 5 mils of the N aO H solution add

.

1 mil of bromin .

The s olution of sodium hypochlorit e 1s g en erally pr eferr ed

to the hypobromit e b ecause it is more stabl e just as effica
, ,

cious an d the dis agr eeabl e h an dlin g of bromin is obvi at ed

, .

V arious forms of app aratus h ave b een devis ed for the

qu antitative estimation of ur ea .

The D or emus Ureometer (Fi g 59) is the simpl est of th es e

. .

The long arm of the ureometer is fill ed with the hypobromit e

solution and th en 1 mil of the urin e is intro duced by the aid
,

of the pip et te The pip ette is intro duc ed through the bul b
.

32 9
330 THE E SSE N TIAL S O F VO LUME TRI C L I
AN A Y S S

as far i t will go in the b end and the nipp l e is th en gen t ly

as ,

but steadily c ompress ed b eing c areful that no air is adm tt ed

,
i .

The vol um e of the lib erat ed gas is r ead off aft r the fr oth e

has s ubsid ed .

The ur eom et r in dic at es acc ording to i t s gradu ati on ei t h er

e , ,

milligrams of urea in 1 mil or grains of urea p er fluid ounc e

of urin e .

It als o in dicat es by the signs N and . wh eth er the ,

F I G 59
. . F I G 60
. .

ur ea is pres ent in an increased n ormal or decreas ed quanti ty

, .

E i t h er Kn op s or S q uibb s solu t i on or L iquor Sod a: Chlo atae

’ ’
, r

U S P may be us ed in this instrum ent Knop s solution is ’

. . . .

that d escrib ed above Squibb s s olution con t ains potassium

.
’

bromid as w ell as bromin It is prepared by taking an equal

.

w eight of bromin and of p otassium bromid and addin g eight ,

tim es as many cc of wat er as th ere were grams of bromin

.

t ak en For use mix equ al volum es of this solution wi th the

.

sodium hydroxid solu tion above d escrib ed .

 V OLUMETRI C T
57 5 "

I
9
f

332 THE E SSE N T AL S or AN A Y SI S

to the shor t gl ass tub e in the rubb er sto pp er of the small er

or g en erat in g b ot tl e B
- In the gen erating bot t l e is a small
.
-

t est tub e A
-
.

Into the test tub e A is p l ac ed 5 mils of urine and into the

—
,

small er b ottl e B is put 2 mils of the hypobromite solution

0 ,

or strong li q uor soda e chlorata e The t es t tub e is th en pl ac ed

.
-

in the g en erat ing bottl e B b eing c areful that the urin e and
-
,

the r eag en t do not com e in c ont act The larger bottle C is

’

now fill ed with wat er and the two bottl es conn ec t ed by the
rubb er tub e the l arger b ottl e b eing pl ac ed on its S id e up on
,

a block and wh en all conn ecti ons are tight

,
the g en erating ,

bot t l e is S hak en so that the urin e will mix with the r eag ent .

D ecomp osi t ion t ak es pl ac e and the g en er at ed gas p ass es

,

into the bot t l e C disp l acing water which is c augh t in a grad

, ,

uated cylin der or other m easuring v ess el The volum e of .

wat er displ ac ed is equi val ent to the volume of gas evolv ed .

E ach mil of ni tr ogen gas evolved at 0 C and norm al

°
.

p r essur e r ep r es en ts gm of ur ea T h en by multi
. .

pyl ing the n u mb er of mils ev olv ed by this numb er the qu a ntity

of urea in the 5 mils o f urin e taken is asc ertained .

The volum e of gas obt ain ed wh en the op erat on con i 15 ~

duct ed at ordinary t emp eratures S h ould always be r duc ed e

to its corresp onding v olum e at 0 C and 7 60 mm °

. .

The fac t or is foun d in the follo wing m ann er

1 0 00 mi ls of H at 0 °
C . w eigh m
g ; .

100 0 mils of N at 0 °
C . weigh n .

quation it is s een th at
By the e gms . of urea evolve
when d ecompos ed gms of N . .

C O (N H2 ) 2 3N aBr O 3N aBr C0 2 N2 2 Hz O .
 1 2
.
55 gms.of N = 1 0 00 mils .

mils gm s . mi ls
x 2 2 32 6 .

Thus gins of ur ea evolve 2 2 3 6 mils of

. 2

mil of N thus represents gm of urea . .

 A PPE N D I X

D E SC RI PTI O N or I N D I C AT O R S
TH E foll owing lis t includes the m or r eliabl e indicators in e

c omm on us arranged al ph ab et ically

e, .

Al i zar m
alk ali es Red
aci d s Y ell ow

T his dye was firs t f oun d in the ro ots of m add er

ti nctori um) bu t is now also obt ain ed synth et ic ally . A h alf
p e r c ent soluti on in alcoh ol is em p loy ed as an indic ator .

Az ol i tm m
al k ali e s Bl ue
aci d s Red

This is the color p rincipl e to which litmus ow es i t s value

as an indic at or I t s extraction is expl ain ed und er litmus
. .

I t is a hi gh p ric ed articl e and is in cons equ enc e s eldom us ed

-
,

the purifi ed litmus tinctur e b eing pr ef err ed .

Braz rl W ood o
S l uti on al k ali es P urpl i sh-red
aci d s = Y ell ow

Boil 5 0 gms of
.
y cut B
fi nelr azil
—
woo d (the h ea rt wo-
od -

of P ellopkorum dubi um (Spreng el ) Briton nat ord Legumznosce) , . .

’

with 50 mils of water during half an hour repl acing from

2 ,

tim e to time Allow the mix ture to cool ; strain ; wash the
.

contents of the strain er with water until 1 00 mils of strain ed

liquid are obtained; add 2 5 mils of alcohol and filter .

Thi s indicator is esp ecially s erviceabl e for the titration of

334
336 THE E S SE N TIAL S O F VO LUME TRI C AN A L Y SI S
a nhydr id and two p arts of pyrogallol and fin ally rec ys , r

talli ing in a simil ar way to ph en olph t h al ein

z .

It is d escrib ed as a dark reddish crystallin e s olid p oss essing

’

‘
,

a gr eenish lus t er It is n early ins olubl e in wat er but r eadily

.
,

sol ubl e in alcohol In comm erc e it is fr equ en t ly foun d as a

.

p ast e mixed wi th wat er

,
.

It forms a r ed coloration wi t h alkali es which is changed ,

to y ellowish brown on ad di t ion to an acid in exc ess

-
.

It is said to be m or e d elic at e toward alkali es than p h enol

~
“

p hth al ein ,
an d m ay b e us ed in its st ead for t itr ating m any

of the alkal oids I t may be us ed in the pres enc e of ammonia

.

or i t s s al t s I t in dic ates sh arply with the organic aci ds A

. .

solution in rectified spiri t 1 1 00 0 is g en erally emp loy ed —

.

m atox yl m
al k alies Vi ol et
aci d s Y ellow to or ange

A p eculiar principl e obtain ed from logw ood h aving the ,

composition C H O G and crystallizing with one or th ee

16 14 , r

mol ecul es of w at er It is an effl o escent yell owish ros c ol ored

. . r -
e

substanc e but wh en pure is said to be colorl ess r eddening

, ,

on exp osur e to light .

It is solubl e in hot w at er or alcohol Its alcoh olic s oluti on .

is l argely us ed as an indic ator in the titrat ion of alkaloids ,

for which it is consid er ed the indicator p ar exc ell enc e .

The Soluti on is pr ep ar ed by dissolving 0 3 gm of the w ell . .

crystalliz ed mat erial in 00 mils of alc ohol In ti trating us e

1 .

about t hr ee dro p s of this solution .

Its color r eaction wi t h c arbonat es and bic arbon at es is

int eresting Wh en add ed to a solu t ion of alkali bicarbonat e
.
-

the r eaction r equir es m any s econds and r esults in a gradu ally ,

d eep ening c armin e red whi ch is p erman ent whil e in the c as e

—
,

of solubl e c arbonat es the r eaction is instantan eous a purpl e ,

red which ch ang es rap idly through ch erry eosin red to orange ,
-
.
 D E SC RIPTI O N OF I N D I C AT O R S 337

The r eaction wi t h amm onium c arb on at is simil ar to that e

with bic arbon at e

lk li s R d a a e ose-r e
i ds Y ll w ac e o

Tetra i odo fluorescei n E rythros n B Thi s in dic ator is use

'

- - z .
.

ful for mi nu t e quan t i ti es of alkali as for instanc e such as , ,

may be dissolv ed ou t from gl ass on cont act with wat er It .

is us ed in c onn ec t i on wi t h highly dilut e standard solutions

only The i odeosin solu t ion is mad e by dissolvi ng
. gm .

of the indicat or in 000 mils of pure eth er Titration with this

1 .

in dicat or is carried out by introducing 5 t o 0 mils of the 0 10

liquid to be titrat ed into a s t o pp ered b ottl e and adding 1 0 to

20 mils of the eth ereal indicator solution and s etting asid e
aft er S h aking The ether eal l ay er as w ell as the fluid will
.

be c olorl ess if the l att er is n eutral but if trac es of alkali are,

pres ent the ros e ed tint p ass es into the aqu eous liquid l eaving
-
r

the eth er col orl ess If the fluid is acid the eth ereal l ay er is
.
,

y ell ow . If p r ef err ed 4 or 5 drops ,

of a a lcoholic 1

s olution of the in dicat or may be add ed to the liquid and ,

eth er th en add ed I odeosin is p ar t ic u l arly us eful in titration

.

of alkaloids esp eci ally thos e of w eak b asicity as emetin e

, , ,

atropin e morp hin e etc

, , .

gart er
Lac m o i d

L acmoid is som ewh at alli ed to litmus but diff ers from ,

i t in many resp ects It is a product of r esorcin and may

.
,

be p r ep ar ed by h eating gr adu ally to 1 1 0 C a mixtur e of °

.

1 0 0 p arts of r es orcin 5 p arts of S odium nitrit e and p arts

, 5 ,

of w at er Aft er the v iol ent r eaction mod erat es it is h eat ed

.

to 1 2 0 C until ammonia c eas es to be evolv ed The r esidu e

°
. .

is th en dissolved in w arm wat er and the l acmoid precip itat ed

th erefrom by HCl ; the free acid is th en removed by washing
an d the r esidu e dri ed .
338 THE E SSE N TI AL S O F VO LUME TRI C L I
AN A Y S S

T his consti t utes the comm ercial l acmoid which is not in ,

a su ffi ci en t ly pur e st at e to be us ed as an in dic at or ; i t s p uri

fi cation is effec t ed according to F orst er by tr eat ing the powd er

wi t h boiling wat er and acidul ating the r esulting blue solution
with hydrochloric acid After a few hours the precipitat e is
.

coll ected and wash ed with a littl e cold wat er and careful ly
dri ed or it is dissolv ed in alcohol and the s olu t ion evaporat ed
,
.

E v en aft er c areful puri fic ation l acmoid soluti on may still

,

exhibit a viol et ting e which is a disturbing f ac t or in accur at e

,

work To r em edy this d efect Forster suggests the addi t ion

.
,

of 5 gms of b eta naphthol gr een to 3 gms of purifi ed l acmoid

.
-
.

dissolved in 700 mils of w at er an d 300 mils of alcohol A .

sam pl e of l acmoi d which is only s p aringly solubl e in wat er

S hould be r ej ect ed The pur er the articl e the mor e r eadily

.

do es it dissolve in wat er A good T S may be m ade by

. . .

dissolving 1
p art in 12
p arts of 2 0 p er c ent alcohol filt ering ,

and evaporating in vacuo ov er sul p hur ic acid O f the r esi du e .

obtained in this way gm is dissolved in 00 mils of alcohol

. 1 .

L acmoid p ap er is p r ep ar ed by dippin g slips of c al end ered

unsiz ed p ap er into the blu e or red solution and drying th em .

L acmoid is S lightly affect ed by c arb onic acid gas I t may-

.

be us ed cold for the alkalin e and earthy hydroxi ds ars eni t es , ,

and borat es and the min eral acids The c arbon at es and
.

bicarbonat es of the al kali es and al kali earths are titrat ed

hot with th is indic ator .

Many of the m etallic s alts such as the sulphat es ari d

,

chlorids of iron copp er and zin c whi ch are more or l ess

, ,

acid to litmus are n eutr al to l acmoid ; th er efor e fr ee acids

,

in such solutions may be es t imat ed by its aid .

L acmoid p ap er r eacts alkalin e with the chromat es of p otas

sium or sodium but n eutral wi t h the dichromat es so that
, ,

a mixtur e of the two or of chromic acid and dic hr omat e may

be titrat ed by its ai d .
34 0 THE E SSE N TIAL S O F VO LUME TRI C L I
AN A Y S S

the gr eat er portion of erythr olitmin and erythrol ein which ,

are s ol ubl e in alcohol T h en by t r eating the r esi du e with

.

wat er a l arg er proportion of azoli t min is dissolv ed and the ,

soluti on is c ontamin at ed wi th v ery li tt l e of the oth er two

princip l es .

L itmus t est solu t i on shoul d be of such str ength th at 3 .

drops added to 5 mils of wat er will im part to the l at t er a

0

N
distinct c ol or . If 16
ci d or alk ali s ol ut i on be
on e drop of
—
a

add ed to this the col or S hould ch ang e to red or bl ue .

L itmus m ay be us ed in a v ery l arg e numb er of titr ati ons .

I t is of valu e in the titration of most min eral acids an d of a

few organic acids e g b enzoic and oxalic
,
. . It is also us eful
,
.

in the titrat i on of alkalin e hydroxi ds wh en the l atter are free

from c arb on at es .

But for c arbon at es bicarbon at es etc a r eli abl e en d reaction

, ,
.
,
-

can only be obt ain ed by boiling th s ol uti on during the titra e

tion in order t o disp el the lib erat ed C 0

, 2 .

Fr ee C O has an aci d r eac t i on with litmus and int erf er es

z ,

very much with the fin ding of the end r eaction -

.

L itmus may be us ed for amm oni a and for borax I t is .

of no use for ph osph oric or ars en ic acid nor for sul p hur ous ,

acid ,
phosph at es or ars en at es b ecaus e the change of tint
, ,

is too gradual .

It is uns atisfactory in t itrating m any organic aci ds e g , . .

,

t ar taric and citric but may be us ed for oxalic o b n oi é

, r e z ,

as b ef or e st at ed .

Som etim es i t is r equir ed to p erform a titrati on wi t h li t m us

at night . G as or l amp light is not adapt ed for showing the
-

r eaction s atisfactorily but by using a monochromatic ligh t

, ,

such as the s odium fl am e a v ery sharp lin e of d emarc at ion ,

may be f ound .

The op eration S hould be conduct ed in a d ark room using ,

 D E SC RI PTI O N OF IN D I CAT O R S 34 1

a pi ec e of pl atinum foil sp rinkl ed wi t h s alt o a pi ec e of pumic e r

ston e s at urat ed with a solution of s alt h eat ed in a Buns en ,

flame .

The red color th en app ears p erf ectly colorl ess whi l e the ,

blu e app ears lik e a mixtur e of ink and wat er .

al k ali es Y ellow
Luteol aci d s C olorl ess

Ch emic ally it is an oxy chlor diph enyl quinoxalin It was - — -

.

suggest ed as an indic ator by Autenri eth .

The solution for the purpos e of an indic ator is pr ep ar ed

by dissolving 1 p art in 1 00 p arts of alcohol O f this four .
,

drop s are su ffi ci ent for 5 mils of flui d to be t itrat ed 0 .

In s ensitiven ess luteol exc eeds both li tmus and ph en ol

,

p h t h al ein It is mor
. e s ensi t iv e toward a mmon ia th an N essl er s
’

solu tion Ten mils of a solution containing one drop of am

.

moni a wat er per lit er is colored y ellow imm ediat ely upon add
,

ing luteol wh er eas with N essl er s solution it t akes quit e som e

,
’

time b efor e a r eaction is obtain ed .

Methyl O ra nge
alk ali es Y ell ow
aci ds = Red

O rang e I I I , Trop aeolin D , Heli anthin , Mand arin

’
Poirri er s

orang e Para sulpho

,
methylanili n
- -
b z e az o di
en n e -
.

Thi s is pr ep ar ed by the actio n of di azo sulph anilic aci d -

upon dimethylanilin ; the acid so form ed is conv ert ed into

a sodium or ammo nium s alt puri fi ed by r epr ecipit ation with ,

HCl and ag ain conv ert ed into a sodium or ammonium s al t

, . .

I f pr ep ar ed c ar efully and from the pur est m at eri als it is a ,

bright orange ed powd er p erfectly solubl e in wat er and

-
r ,

slightly in alcohol ; but it is oft en found in comm erc e as a

dull orange brown powd er oft en not compl etely solubl e in
-
,

w at er Many conflicting stat em ents h ave b een made by op era

.
34 2 THE E SSE N TIAL S O F VO LUME TRI C AN A L Y SI S
tors as to the valu e of m ethyl orang e as an indicator which ,

hav e t end ed to bring this in dic ator into disr ep ut e .

Sutton has examin ed m any sp ecim ens but has not found ,

any in which the impur iti es s ensibly aff ect ed its delic at e action .

He cl aims t h at the common error is the use of too much

indicator and that som e ey es are more s ensitive to a chang e
,

of tint than ot h ers .

Methyl orang e is n o doubt a v ery good in di c ator but ,

,

practic e with i t mus t be had in order to obtain good r esults .

The author has foun d on e s ampl e which had a b eautiful

orange color but which was absolut ely us el ess as an indicator
, .

A H All en d escrib es the ch aract ers and t ests of a good

. .

articl e as follows :

I Aqu eous solution not pr ecipitat ed by al kali es

.
, ( O rang e .

I b ecom es red brown ; orang e I I bro wnish red )

- -
.

2 .Hot conc entrat ed aqu eous s olu t ion yi elds Wl th HCl

microscopic acicul ar crystals of the free sulphonic acid soon ,

ch anging to small lustrous pl at es or prisms h avin g a vi ol et

.

reflection (O range I gives y ellow brown color or flocculent

.
-

precipitat e ; orange I I brown y ellow precipitate ) -

.

3 .D issolv es in conc entrat ed H SO with a r eddish or z 4

y ell owish brown color which on dilution b ecom es fine red

-
, .

4 .Ba C l yi e l ds a zpr ecipit at e .

5 .Ca C l yi elds no pr eci p i t at e

z (O r ang e I giv es a re d .

pr ecipitat e ) .

6 Pb(C H3 0 ) 2 yi elds an orang e y ellow pr ecipitat e

.
2 2
-
.

7 .M gS O in dilut e solutions
4 pr ecipit at es th e coloring
matt er in microsc opic crystals .

Methyl orange T S is m ade by dissolving gm of m ethyl

—
. . 1 .

orange in 1 000 mils of water Add to i t carefully diluted sul .

p h u r i c a cid in drops until th e li q uid t urns red and just c eas es

t o be transp arent Th en fi lter . .

The gr eat v alu e of this indicator consists in the fact that

34 4 I
THE E SSE N T AL S OF VOL U ME TRI C AN AL Y SI S

k ali carb o n ate s Red

Phe nac et l o in al
hydr s
o xi d Y ellow
s aci d

Thi s indic ator is pr epar ed by h eating tog eth er for s ev eral

hours equal mol ecul ar w eights of ph enol gl acial ac etic acid , ,

an d sulphuric acid in a v ess el provid ed with a r eflux con

d ens er The product is th en thoroughly wash ed with wat er

.

to r emov e exc ess of acid and dri ed for use It is only very .

slightly solubl e in wat er but dissolves readily in alcohol

, ,

forming a gr eenish brown solution

-
.

The soluti on yi elds with alk ali hydroxids a sc arc ely p er

cep tible p al e y ell ow bu
,
t with norm al c arbon at es of the alkali es ,

sulphi ds and wi t h ammonia i t giv es a d ecided pink color ;

,

wi t h bic arbon at es a mor e int ens e pink whi l e wi th acids a ,

gold en yellow .

This in dic at or is us eful for estim ating the amount of alkali

or alkali earth hydroxids in the pres ence of carbonate unl ess ,

the hy droxi d is p r es ent in too sm all a qu antity Ammonia .

must not be pres en t The ti tration is carri ed out by adding

.

the aci d until a faint r ed c olor ap p ears ; this indicat es that

‘

the alkali hy droxi d or the lim e has b een n eutraliz ed The .

furth er ad di tion of the acid in t ensifies the red un til the car
bon at e pres en t in the mixture is n eutraliz ed wh en a gold en ,

y ellow color app ears The proportion of alkali hydro xid must
.

be far in exc ess of the c arb on at e in ord er to obtain r eli abl e

res ults ; f ur t h ermore consid erabl e practic e is r equired in the
,

use of this indic ator in order to accust om the eye to the color

changes .

A conv eni ent str ength of s olution is in alcohol .

 D E SC RI PTI ON OF I N D I CATO R S 34 5

alk ali eS = Red

o
Phen lp hthalei n (C 2 0H 1 4 O 4)
aci d s C olorl ess

P reparati on . ive p arts of p hthalic anhydrid (C H 0 )

F 8 4 3 ,

1 0 p ar t s of p h enol an d 4 p arts of H 80 are 2 4

h eat ed togeth er at 0 to 30 C for s everal hours The

12
°
1
°
. .

pro duct is th en boil ed with wat er and the r esidu e which , ,

consists of impur e p h enolp hthal ein is diss olved in dilu t e ,

soda solution and fi ltered By n eutralizing this solution the

.

ph enol phthal ein is precipitated and may be purified by crys

talli ati on from alcohol ; or the alcoholic soluti on m ay be
z

boil ed with animal charcoal fi lter ed and the ph enolphthal ein

, ,

reprecipi tated by boiling w at er .

Uses. Ph enolphth al ein is a v ery valu abl e indic ator ; is

extr em ely s ensitiv e and exhibits a w ell m ark ed and promp t
-
,

chang e from colorl ess to pink and v i ce versa A few drops ,

.

of the solution of the indic at or S how no col or in n eutral or

aci d liqui ds but the fain t est exc ess of alk ali pro duc es a sudd en
“

ch ange to red .

It may be emp l oy ed in the titration of min eral and organic

acids an d most alk ali es but it is not suit ed for the titr ati on
,

of ammoni a or i t s s alts It is v ery s ensitiv e to C0 and

.
2,

th er efor e in estimatin g c arbon at es the liquid must be boil ed ,

as with litmus It is in applic abl e for borax exc ep t in the

.
,

pres enc e of glyc erin b ec aus e the color gradually fad es away
,

as the acid is add ed O ne gr eat advantag e which ph en o l

.

phth al ein poss ess es is that its indic ations may be cl early
read in many colored liquids ; anoth er is that it may be us ed
in alcoholic liquids or in mixtur es of alcohol and eth er and ,

th erefore m any org anic acids which are insolubl e in water

mav be accurat ely titrat ed by its h elp .

Ph enolphth al ein T S is a one p er c ent solution in alcohol

. . .
34 6 THE E SSE N TIAL S OF VO LU ME TRI C AN AL Y SI S
c arbo n ate s = Bl ue
Ponrr l er Bl ue (C 4 B) al k ali hyd r o xi ds = Red
aci d s Bl ue

Thisindic ator which is cl os ely alli ed to G entian Blue in

,

prop erti es is obtain ed by the ac t ion of sulp huric acid on

,

trip henylr osani lin I t is a blu e powder wi th a cop p ery luster

. .

It dissolves in w at er and in alcohol yi elding blu e solutions ,

~
.

K O H and N aO H ch ang e the color to red but ammoni a ,

d ecoloriz es it It is em ployed as an indic ator in aqueous

.

solution This in dic ator is exc eedingly s ensitiv e to

acids Borax and boric acid giv e a blu e color ; in the titra
.

tion of boric acid the red color do es not app ear until the acid
is compl etely n eutraliz ed Thi s indic ator is recomm end ed
.

for the titration of hydrocyanic acid toward whi ch it is esp ecially ,

s ensiti ve the alkaline cy anids are alkaline in r eaction to most

,

indicators but C B do es not Show an alkalin e reaction un til

, 4

the HCN is compl et ely n eutr aliz ed and a minut e exc ess of ,

the al kali hydroxid has b een add ed G B is of the ch ar act er .

of a w eak acid and its s alts are very unstabl e ; th ey are decom ~

pos ed by wat er alon e wh en in v ery great diluti on th er efor e ,

the indic ator must be us ed in sufli ci en t qu an t ity The addi t ion .

of a few dr ops of alcohol f acilitat es the color ch ang e which ,

is indeed a v ery sharp one .

al k ali es Bl ue
Res az u r m aci d s = Red

This
is a new in dic ator for alkalimetry propos ed by Cri smer , .

It is prep ared as follows : D issolve 4 gms of r esorcin in 300 .

mils of anhydrous ether and add 4 to 4 5 drop s of nitric acid 0

sp
( g r . s at
.ur at ed with nitrous anhydrid A llow the .

mix ture to stand in a cold pl ac e for two d ays wh ereupon ,

a d eposit of bl ac kish cryst als h aving a r eddish brown refl ec

,
-

tion will be formed in the bottom of the v ess el The sup er

, .
34 8 THE E SSE N TI AL S OF V O LU ME TRI C AN AL Y SI S
C0 2, an d H2 0 imm
.
e di t
The C O
a ely r eac t s wi t h the p h enol

and forms rosolic aci d as th e foll owing ,

e qu at i on sh ows :

3 C 6 H 5 O H Z CO C 2 0H1 4 0 3 2 H2 0 .

C omm erci al rosolic acid is a mixt ur e of s ev eral derivatives ,

m
a o ng t h em th e a bov e m et hy la uri n
,
C H 6 0 a n d o t h ers 20 1 3 .

C omm e rci a l p o eo n i n (also kn own a s A urin R )[chi efly C H 0 ] . 19 14 3

may be us ed in pl ac e of r osolic acid .

Rosolic acid is solubl e in dilut ed alcoh ol Its c olor is .

p al e yellow not ch anged by acid but t urns vi ol et ed wi t h

, ,
—
r

alk ali es .

It is an exc ell en t in dic at or for the min ral aci ds and strong e

b as es w eak ammoniac al s oluti ons oxalic aci d and o th er or

, ,

gamic acids exc ep t ac etic

,
.

The t est solution is made by dissolving 1 gm of the com ,

.

m er ci al r o s o lic a ci d in mils o
10f dilut e d alc ohol an d t h en adding
enough w ater to m ak e mils 1 00 .

k alies
TI O P&
'
01 1 " (0 0 ) al
aci d s ‘
Y ellow
Y ellow i sh-red

Thisis us ed in the form of a s olution c ontaining 5 gm 0 . .

to 000 mils of alcohol

1 .

Tur mer i c Tin ct ur e D ig est any conv eni ent qu antity of

.

groun d c urcuma ro ot (from C ur uma longa L inn é nat ord

—
c , .
,
.

S i tami neae) r ep eat edly wi t h sm all qu antiti es of w at er and

c ,

throw t his liq uid away Th en dig est the dri ed r esidu e for
.

s ev eral days with six t imes i t s w eight of alcohol and filt er .

Turm er i c Pap er Impr egnat e white unsiz ed p ap er wi t h

.
,

the tinct ur e an d dry it .

The color principl e of turm eric is curcumin It is s el dom .

us ed in vol um etric an alysis exc ept in the form of turm eric ,

p ap er For high colored s olutions curcumin gives no r eaction

.
-
us el ess in that it is indifferent to alkali es ; i t is solubl e in wat er
,

an d extr act ed by dig estion with w at er aft er which the cur

,

cumin is dissolved out wi t h alcohol .

T urm eric p ap er is esp ecially us eful b ec aus e of its p eculiar

,

r eaction with boric acid with which i t d ev el op s a brown c ol or

,

aft er dryin g ,
and w hi ch col or , wh en touch ed with caustic
soda solution is changed to d ark green .
35 2 IN DE X

numbe r of r si s e n

oxalic

and oxala e ts
decino m al r
s
p ho p ho i c r

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 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 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O

of fa ts an d oil s
Acidime y tr
and alk alim e y tr
s st
Acid , e i ma ion of, by t n eu tr aliz a ti on

o rg ani c .

quanti ty to be tak en for assay

g g of f ss
wei hi n ,
or a ay .

v l til
oa e .

Alco h l i ti t r s
o ,
n nc u e and be vrgse a e

Alco h l m tri t bl
o o e c a e

Alk ali bi ca bona r ts e and ca rb on a e t s mi xe d

carb ona e ts
hydr oxi d an d ca rb t mi d ona e xe .

hydr ox i d st d rd s l ti
, p r s rv ti
an a o u on , e e a on of

hydr ox i ds stim ti , e a on . .

i odid s . .

st rd s l ti s p r p r t i
anda o u on ,
e a a on of

Alk li
a rth hydr ids
ea ox .

d rb t s mi d
an ca ona e xe

s ltsa . .

earths rg i s lts f , o an c a o

org i s lts f
an c a o

Alk lim try

a e . .

and i dim t y
ac e r

Alk l ids stim ti

ao f,
e a on o
 353

Alkal oid s ,
ex tr tiac on of

An h tr acen e vi l t
oe

An tim oni c comp ound s

An tim onou s oxi d

An tim s
ony comp oun d

d p t ss i m t rtr t
an o a u a a e

Ap p r t s l
a a u i g f , c ean n o

s d i v l m tri
u e n lys i s o u e c ana

use of

Ars ts
ena e .

Ars i id
en c ox

Ars i t ri i d
en c ox

Ars i t
en f p t ss i m s l ti
e o o a u ou on

Ars s id
enou ac .

s l ti o u on .

d i rm l V S ec no a .

VS f i r d ti
. .
, use o n e uc on

hydri d
an

mp
co ds oun

di r t p r t g ss y
ec e cen a e a a of

oxi d .

st rdi ti
anda za on of iodin wi h t . .

At mi w ights
o c e

m l t ip l s f u e o

B ria um chlo ri d
di oxid .

hydroxid V S .

pe r oxi d .

B t
enz oa e, ammoniu m
B is ulp hi e, t s odi um .

B ri id
o c ac

B yl s L w
o e
’
a . .

t st s l ti
e o u on

Br o m t s a e

Br o m t p t ss i
a e, o a um

Br o mi ds
Br o mi fr n ee

Bu r tt
e e, au om a t
ti c

connec e t d with r s rv i r e e o

clamp s .

holde r .

Mo hr s
’
.

B r tt s
u e e upp o rts
B tt r
u e , ex a mi t i na on of

Cacodyla t s e, odi um

C al ci u m rbca ona e t

s s lts f
olubl e a o

Ca cu l l ti g r s l ts
a n e u

Ca libr ti
a on o nf i str umen ts
Calx chlori nata .

Cane s g r i v rt d
u a ,
n e e

Ca rb t mm i m
on a e, a on u
356 IN DE X

Cyanid p o t ssi a um

Cyano g en .

Cylinde r gr,
adua ed t
D ecino mal
'

r s l ti s
o u on

D ich r oma e, t po a t ssi um

sis by m s f
analy ean o

r
p p r t i f V S
e a a on o .

D ig sti
e m th ds on e o .

D i id hydr g
ox ,
o en

m g s
an ane e

Di r t p r
ec t g stim ti s
e cen a e e a on

t bl f q titi s f r a e o uan e o

D i ss i tioc a th ry on eo

D i st ill ti m th ds
a on e o

D bl
ou r m l s l ti s
e no a o u on

E au de Jav elle .

E lemen ts list f ,
o .

E mp i ri l p rm ca e angan a e t s l ti s
o u on , use of

s l ti s
o u on

E dr
n -
ti eac on

r
E dmann
’
sfl t oa

Fa ts ,
waxe s an d oil s
F ehli n g s s l ti ’
o u on

dp i t
en -
o n .

Fe rri l m s l ti
c au o u on

c hl ri d o

s lts
a

Fe rr s mm i m s lph t
ou a on u u a e

ca rb t s h r t dona e acc a a e

i di d syrup f
o ,
o .

s l ts stim ti by di hr
a ,
e a on c om a e t
Fe um rr reductu m
 IN D E X 35 7

Fla sk s titr ti ,
a on

Fluo rs i e ce n .

Ga s ome tri c analy ess

Gay Lussac
-
’
m th d f
s e o or haloi d s lts a

G ener lm a yi e th ds f ss
o o a a n g dr gs u

G r l p ri ipl
ene a nc es .

Gluco es
Gly r ph sp h t s di m
ce o o a e, o u .

G di
or m di fi d lk lim tri
n s
’
o e a a e c

G r vi m tri m th d
a e c e o ,

p i p tt
’
G th
re an s e e .

bl hi g fl i d
’
Grouv e ll e s eac n u

Halo g s fr
en ,
ee

e stim ti a on of t
wi h ch r om a e as ant tr
i ndi ca o

Hanu numbe s ’
r . .

Helian hin t .

Hot way i a ion t tr t s

Hii bl s numbe
’
r

ac ti on of, on p e man r g an a e t .

no rm l a . .

Hyd r y i id
oc an c ac

Hyd r g di id
o en ox

Hyd r g s lphi d
o en u .

Hyd r i d d rb t
ox an ca ona e of alk ali mix ed .

f lk li
o rths mi
a a ea ,
x ed .
35 8 IN DE X

Hyd r oxi d s ,
k
al ali , e stim ti a on
—
of alk ali earths . .

s odi um and t ssi m mi po a u x ed .

Hyp o br mi t s l ti
o f r e o u on or u ea e stim tia on

Hyp oc hl ri t o e .

Hyp op ho p hi e s ts
s r s
Hyp op ho p ho ou aci d
s t s
Hyp o ulp hi e, odi um .

I m mi s ibl s lv ts
c e o en

In di t r
ca o

In di t rs l ss i fi ti
ca o ,
c a ca on

d s rip t i
e c f i di v i d l on o n ua
—
g id f
u th s l t i
e or e e ec on

In di t r r q i r m ts f g
ca o ,
e u e en o a ood

s sitiv ss t lk l ids
en ene o a ao .

t h ri s feo e o . .

In di r t i d ti
ec ox lys i s by a on ana

I no rg i ids an c ac

In str m ts libr ti f
u en ,
ca a on o

In tr d ti
o uc on

In v rt d
e e sgr can e u a

Io d t s
a e .

I odeosin .

I odid, rs sa en ou

f rr s s yrup
e ou of

I odl ds

I odin , r f ee

p ri fi ti
u f ca on o

ti t r
nc u e .

ti tr ti s a f s di m bi rb
on , use o o u ca t
on a e in

Io di ne a bs rp ti mb r o on nu e

V S p r p r ti
. . f e a a on o . .

Io di d st r h t st p p r
ze a c e a e .
360 IN DE X

Manganates
M anganes e di oxi d
M anganous s ulp hat e ,
use of i n pe rm g an ana e t ti tr ti s a on

M er curi c s alts
s lp h t
u a e, use of, i n p e man r g ana e t titr ti s a on

M r r s s lts
e cu ou a

M thyl r g
e o an e .

Mohr s ’
bu r tt e e

s lta

N eu tr ti
aliz a lys i s on an a

o f idsac .

N i tr t s ilv r V S
a e, e .

N i tr t s
a e i tri id i
,
n c ac n

P l u m th d
e o ze e o

N i tri id
c ac

N i tri t myl
e, a

e thyl

o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
o o o

s l ti s
ou on

Or g m thyl
an e, e

Oil s f ts
,
dw a s an axe

i dio bs rp ti
n a o on numbe r of

—
table showing i odi n absorp ti on nu mber of . .
 36 1

of the al ali e k s t ,
abl e of fac t rs f
o or

—
of alkali earths

Oxali c acid

rm l s l ti
no a o u on

st d rdi ti f p rm g
an a za on o e an ana e t by
Ox id ,
tim
an on ous .

a rs s enou

Ox i d ti
a d r d ti
on an e uc on

i di r t
n lys i s by
ec ana .

Ox y hl r dip h yl q i li u noxa n
-
-c o -
en

Pa r f rm
a o aldehyde

Parani trop henol

r rt s
Pe bo a e, odium

Percarbonates .

Per t g r l s f dir t stim ti s

cen a e u e or ec e a on

P rm g
e t ti f hydr hl ri id
an ana e, ac on o oc o c ac on

p t ssi m V S
o a u . .

s l t i s m p i ri l
ou on ,
e ca

titr ti wi th i p r s
a on f hydr hl ri id n e ence o oc o c ac

typi l lysi s with

ca ana

v l m tri
ou ly i by m
e f c ana s s ean s o .

P r i ds
e ox

Ph t li
enace o n .

i stim ti g mi d lk li hydr id d rb t
n e a n xe a a ox an ca ona e

Phenol
Phenolph halein t
s
Pho p ha e, odium t s
Phenylsulp honates
s
Pho p ho i c r aci d

Pi noh cock s .

Pip e tt s e .

Po i rri r bl
e ue

Poi rri er r g’
s o an e I I I

Po t ssi m t t
a u ace a e

a rs i t s l ti
en e o u on
36J2 IN D E X

Po t ssium b
a d t
i -I o a e, ad an a e v tgs of for st anda rdi i g V S
z n . .

r
bi tatra
te

hyd r oxid

alcoholi c

perm g t V S
an ana e . . .

s di m t rtr t
o u a a e .

s lphit
u e

t rtr t
a a e .

Pr ip i t ti
ec a on analy si s
Pr p r ti
e a a on of n o rm l li a oxa c aci d s l ti
o u on .

—
of standard ac i d s l ti s o u on . .

Puckner s m e hod
’
t . .

Py rg o allo l p hth l i
- ae n

R ms y s bl hi g fl id
a a
’
eac n u

R di g f i str m ts
ea n o n u en

R d d stim ti f s bst
e uce ,
e a on o u ance sr eadily

R duci g g ts
e n a en

sug rs a

R d ti
e uc d id ti
on an lys i s ox a on ana

meth ds i v lvi g th
o ,
f rs n o n e use o a enou s aci d VS
. .

4 st s hl rid annou c o

R i hert n mb r
e c u e . .

R i hert
e c

R s z ri
e a u n

R sidul titr ti
e a a on .
364 IN D E X

thi so ulp ha e t
VS . .
, p r p r ti
e a a on of

Spi irt of ammoni a .

r ti
a oma c .

f i tr s th r
o n ou e e

S q ibb s hyp br mi t s l ti
’
u o o e ou on

S t d rd s l ti s
an a ou on .

t mp r t r
e e a u e .

S ta nnou s hl rid stim ti f i r

c o ,
e a on o on by mean s of

s l ti p r p r t i f
ou on , e a a on o .

u f i r d ti
se o m th ds n e uc on e o

as an in di ca o tr
t r i v rsi
af e n e on

i v rs i
n e by di st son a a e

i di d t st p p r
o ze ,
e a e

s l ti
ou on .

S t ti g r s l ts
a n e u .

S tr tium s li yl t
on a c a e

S b tt l d
u ace a e, ea

S g rs
u a

S g ri
u a ri
n u ne

Sulp hid s i s l bl ,
n o u e

Sulp h ri u id c ac

rm l
no a .

Sulphi t p t ss i m
e, o a u

s di m
o u

Sulp hi t s e .

Sulphocarbolates

S ulphocyana t e VS . .
,
a ss
ay of S il e v r i tr t
n a e by
Sulphu r us a id
o c
 36 5

T bl a e, alcoholome tri c .

for rr tico l m f th t mp r tur

ec on o fv o u e or e e e a e

f
or co rr ti f p r ss r ec on o e u e

o f l m ts
e e en . .

o f f t rs f rg i s lts f th
ac o lk li s
o o an c a o e a a e .

o f rm l f t rs f
no i ds lk li s
a d lk li rth
ac o or ac ,
a a e an a a ea s .

o f rm l f t rs f ids t
no a ac o or ox ,
e c . .

o f m l tip l s u e .

o fq titi s f di r t p r t g stim ti s
uan e or ec e cen a e e a on

o f s bst u s stim t d by st d rd i di s l ti
ance e a e an a o n ou on

p r ip i t t i ec a on

p r m g t d diehr m t an ana e an c o a e

sh wi g l r h g s f i di t rs
o n co o c an e o n ca o

i odi n ab o s rp t i on numbe r of oil s

sap onifi cati on nu mbe r
T rt r r m f
a a , c ea o

m ti e e c .

T rt ri id
a a c ac .

T rtr t tim
a a e, an ony and po t ssi
a um

T mp r t r st d rds f
e e a u e, an a o

T st mi r
e xe .

T tr i d fl
e i
a- o o- uoresce n

Th ri s f i di t rs
eo e o n ca o

Th ry hr m ph ri
eo ,
c o o o c

i i ti on za f i di t rs on o n ca o

f Ost w ld
o a

Thi s lph t s di m
o u a e o u

VS stim ti s i v lvi g
. .
, e a on n o n use of

p r p r ti f e a a on o

standardiz ati on of i odi n wi th . .

VS . .
,
st anda rdi ti za on of by di ch r oma e t
o f by p t ss i o a um bi i oda—
t e

of by p e m an r g ana e t
Ti tr ta e, to .

Ti trated soluti on
366 I NDEX

PAG E

Titr ti
a on , infl uence of concentration of V S . .

r sidu l
e a .

Tri hl r ti
c o ace c acid

ti t rnc u e

tim ti f by D r m s r
es a on o o e u
’
u eom e e tr
Ur m t r D r m s
eo e e ,
o e u
’

Hi ds D r m s
n - o e u
’

Uri s g r i
ne, u a n

Vegetable drugs assayi ng of ,

Vi olet anthracene
,

tt v
fa y aci d, alue .

s v ts
ol en , i n fl uen ce of i n
lk l a a oi dal a ss ys
a

V lh rd s m th d f h l ids
o a
’
e o or a o .

s l ti
o u on

V l m str gth f hydr g di

o u e en o o en oxi d

V l m tri m th d th
o u e c e o ,
e

st d rd s l ti s
or an a o u on

W ighi g b ttl
e n o e .

Wils s bl hi g fl ui d
on
’
eac n

o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o