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C. J.

COETZEE : Volumetric Det ermi nat i on of Chlorate wi t h AgNO 3


Vol umetri c Determi nati on of Chlorate wi t h Silver
Nitrate after Reducti on wi t h Ni tri te or Disulfite
245
C. J . CO~TZ~
Depar t ment of Chemistry, Uni versi t y of t he Orange Fr ee St at e
Bloemfontein, Sout h Africa
Received September 27, 1967
Summary. The use of ni t ri t e and disulfite as reducing agents in t he volumetric
det ermi nat i on of chlorate was investigated. The chloride formed was det ermi ned
by direct t i t r at i on wi t h silver solution using either dichlorofiuorescein or po-
tassium chromate as indicator. I n t he range of 100--500 nag of chlorate errors of
about q- 0.2~ were obtained.
Ch l o r a t e ma y be d e t e r mi n e d v o l u me t r i c a l l y b y o x i d i me t r i c [ 1 , 3 a , 4 - - 6 ,
8, 9, 13a ] , i o d o me t r i c [ 12, 13b] , i n d i r e c t c o mp l e x o me t r i c [10] a n d a r g e n t o -
me t r i c [ 2, 3b, 7, 11, 14] t i t r a t i o n me t h o d s .
Amo n g t h e a r g e n t o me t r i c d e t e r mi n a t i o n s s u l p h u r di oxi de [3 b, 11 ], i r on ( I I )
[2, 14] a n d n i t r i t e [7] a r e u s e d as r e d u c i n g a g e n t s f ol l owe d b y a Vo l h a r d
t y p e t i t r a t i o n .
I n mo s t of t h e k n o wn v o l u me t r i c me t h o d s f or c h l o r a t e d e t e r mi n a t i o n a
b a c k - t i t r a t i o n i s us e d. I n t hi s wo r k t h e p o s s i b i l i t y of a d i r e c t t i t r a t i o n of
c hl or i de wi t h s i l ver s ol ut i on, a f t e r r e d u c t i o n of c h l o r a t e b y n i t r i t e or
di s u] f i t e wa s i n v e s t i g a t e d . I n e a c h cas e t wo t i t r a t i o n p r o c e d u r e s wer e
f ol l owed, t h e f i r s t e mp l o y i n g di ehl or of l uor cs cei n, a n d t h e s e c ond p o t a s -
s i um c h r o ma t e as i n d i c a t o r .
Ex p e r i me n t a l
Bl a n k s wer e r u n i n al l d e t e r mi n a t i o n s . Th e me a n r e s ul t s r e p o r t e d a r e t h e
a v e r a g e of a t l e a s t f i ve d e t e r mi n a t i o n s i n e a c h case.
Reagents
Standard Chlorate Solutions. These were prepared from potassium chlorate (Merck)
and st andardi sed gravi met ri cal l y as silver chloride [13c].
Indicator Solutions. Pot assi um dichromate, 5~ solution in wat er; Dichloro-
fluorescein, 0.S~ solution in 70~ ethanol.
Reduction and Ti t rat i on Procedures
Reduction with Sodium Nitrite. To t he sample solution (containing 100--500 mg
of chlorate) 20 ml of 1 M sodium ni t ri t e solution and 5 ml of 3 N nitric acid are
added. The solution is heat ed t o t he boiling poi nt and boiled for at l east 2 min.
246 C. & COETZEE:
a) Titration with Adsorption Indicator. 20 ml of 50/0 sodi um hydr ogen car bonat e
sol ut i on are added, t he mi xt ur e cooled and one t o t wo drops of dichlorofluorescein
i ndi cat or sol ut i on added. Ni t r i c aci d is now added unt i l t he fluorescence of t he
i ndi cat or j ust disappears. 20 ml of 1 M sodi um acet at e and 5 ml of 2~ dext r i n
sol ut i on are added and t he sol ut i on t i t r at ed wi t h a st andar d si l ver sol ut i on (0.1
or 0.05 M) t o a pi nk end-poi nt .
b) Mohr Titration. The sol ut i on is neut r al i zed wi t h cal ci um carbonat e powder,
cooled and 1 ml of pot assi um chr omat e 1 i ndi cat or sol ut i on is added. The sol ut i on
is t hen t i t r at ed in t he usual manner.
Reduction with Sodi um Disul/ite. To t he sampl e sol ut i on (cont ai ni ng 100--500 mg
of chlorate) 20ml of 10~ sodi um di sul fi t e sol ut i on is added and t he mi xt ur e
boi l ed for at l east 2 rain, wher eupon 5 ml of 3 N ni t ri c aci d is added and t he sol ut i on
boi l ed unt i l no more sul phur di oxi de evol ved.
a) Titration wi t h Adsorption Indicator. The procedure is exact l y t he same as in
t he ni t r i t e case.
b) Mohr Titration. The procedure is t he same as i n t he ni t r i t e case except t ha t
addi t i onal wat er has t o be added wi t h addi t i on of cal ci um car bonat e t o pr event
pr eci pi t at i on of cMcium sul phat e.
Tabl e 1. Argentometric determination o/chlorate after reduction by sodium nitrite
Wei ght of KCIO a t aken
mg
KCIO 8 f ound as per cent age of t ha t t aken, using
a) dichlorofluorescein
b) pot assi um chr omat e as i ndi cat or
a) b)
123.4 100.1 4- 0.2 100.1 4- 0.2
246.9 100.2 4- 0.1 - -
247.4 - - 100.0 4- 0.1
494.9 99.98 4- 0.03 99.97 4- 0.04
Tabl e 2. Argentometrlc determination o/chlorate after reduction by sodium disul/ite
Wei ght of KCIO 3 t aken
mg
KC108 f ound as per cent age of t ha t t aken, usi ng
a) diehlorofluorescein
b) pot assi um chr omat e as i ndi cat or
a) b)
123.7 100.1 -t- 0.04 99.95 4- 0.12
247.4 100.1 4- 0.1 100.0 4- 0.04
494.9 100.1 4- 0.1 100.1 4- 0.1
Discussion
T h e r e s u l t s s h o w t h a t a n y o n e o f t h e t wo r e d u c t i o n me t h o d s , f o l l o we d b y
a n y o n e o f t h e t i t r a t i o n p r o c e d u r e s ma y b e u s e d wi t h c o n f i d e n c e f or t h e
v o l u me t r i c d e t e r mi n a t i o n o f c h l o r a t e . T h e f o l l o wi n g i o n s h o we v e r s h o u l d
b e a b s e n t a s t h e y mi g h t i n t e r f e r e d u r i n g t h e s e d e t e r mi n a t i o n s : a l l a n -
I f t he amount of KC103 is i n t he 500 mg r ange doubl e t he vol ume ma y be added.
Volumetric Det ermi nat i on of Chlorate wi t h AgNO 8 247
i ons who gi ve s p a r i n g l y s ol ubl e s i l ver s a l t s a n d al l c a t i o n s whi c h gi ve
s p a r i n g l y s ol ubl e c h r o ma t e s , c hl or i de s or s u l p h a t e s ( s ul pha t e i s f o r me d
d u r i n g t h e di s ul f i t e r e d u c t i o n ) a n d whi c h gi ve h i g h l y c ol our e d s ol ut i ons .
The a d v a n t a g e of t he s e me t h o d s i s t h a t o n l y one s t a n d a r d s o l u t i o n i s
n e e d e d f or t h e d e t e r mi n a t i o n .
Zusammenfassung
Zu r v o l u me t r i s c h e n Ch l o r a t b e s t i mmu n g wi r d di e Re d u k t i o n mi t Ni t r i t
ode r Di s ul f i t u n d anschl i el ~ende Ti t r a t i o n mi t Sf l ber l Ss ung gegen Ka l i u m-
c h r o ma t o d e r Di c hl or f l uor e s c e i n al s I n d i c a t o r e mpf ohl e n. I m Be r e i c h y o n
1 0 0 - - 5 0 0 mg Ch l o r a t wu r d e n Fe h l e r y o n e t wa 4- 0, 2~ e r ha l t e n.
Re f e r e nc e s
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Dr. C. J. COETZEE
c/o Depar t ment of Chemistry
The Uni versi t y of Arizon~
Tucson, Arizona 85721 (USA)