Chemical synthesis of battery active manganese dioxide
by William E Domning
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Master of Science in Chemical Engineering
Montana State University
© Copyright by William E Domning (1955)
Abstract:
A study of the battery activity of the manganese dioxide produced by the oxidation of manganese
sulfate by potassium permanganate is presented.
It was the purpose of this work to produce a manganese dioxide from this reaction that would ipeet
drain specifications and to investigate the commercial possibilities of the reaction, A discussion of the
sample preparation and performance of the- manganese dioxide produced by this synthesis is given.
Chemical analyses,which includes total manganese, available oxygen, moisture content, and pH,are
tabulated for each manganese dioxide sample as are apparent density, bobbin weight and initial drain
test performance, A cost analysis of a proposed ten ton per day plant to produce manganese dioxide by
the above synthesis is included.
Heat treating of the manganese dioxide made by the above reaction will produce a manganese dioxide
that will meet low drain specifications, A suggested method of preparation of a sample by the above
procedure is; purification of a technical grade manganese sulfate by the addition of 10 grams of zinc
oxide per 124 grams of manganese sulfate, adjustment of the volume of the manganese sulfate solution
until the concentration is 88.6 grams per liter, addition, at the rate of 26.25 grams per hour per 124
grams manganese sulfate, of potassium permanganate of a concentration of 52.5 grams per liter. The
reaction is to be run at the boiling point. After, washing, filtering and drying the product, it is to be
heated for 6 hours at 220 degrees centigrade.
Material meeting both high drain and low drain specifications was produced from technical grade
manganese sulfate and potassium permanganate. The conditions of a successful reaction were; aeration
of the reaction mixture; the concentration of the manganese sulfate was 0.1 mole per liter; a solution
containing one equivalence, based on one mole of manganese sulfate, per 2 liters of solution was added
to the boiling manganese sulfate at the rate of 26.25 grams per hour per mole of manganese sulfate; the
reaction mixture was held at the boiling point for 3 hours after the final addition of jihe permanganate.
Successful adaptation of this synthesis to a continuous reaction "basis is indicated by the results of this
investigation. CHEMICAL SYNTHESIS OF BATTERY ACTIVE
MANGANESE DIOXIDE
. WILLIAM E o ' DOMNING
/
A THESIS
S u b m itte d to th e G ra d u a te F a c u lty
in
p a r t i a l f u l f i l l m e n t o f th b re q u ire m e n ts
f o r th e d e g re e o f
M a s te r o f S c ie n c e i n C hem ical E n g in e e rin g
at
M ontana S t a t e C o lle g e
A pproved:
H ead; M ajor Departmep4, "
lean? G r a d u ^ e D iv is io n
Bozeman, M ontana
• Augus t j 1955
M3 If
' p ' l Mr O
Ofrjj5 2—
—2—
TABLE OF CONTENTS
A b s tr a c t
3
In tro a u c tio n
4
S p e c ific a tio n s
5
M a te r i a ls and M ethods
7
D is c u s s io n o f R e s u lts
16
Summary
38
L i t e r a t u r e C ite d
41
A cknow ledgem ent
41
A ppendix
42
114699
-3 -
ABSTRACT
A s tu d y o f th e b a t t e r y a c t i v i t y o f th e m anganese d io x id e p ro d u ced by
th e o x id a tio n o f m anganese s u l f a t e by p o ta s s iu m p erm a n g an ate i s p r e s e n te d .
I t was th e purpose-' o f t h i s work to p ro d u c e a m anganese d io x id e from
t h i s r e a c t i o n t h a t w o u ld ipeet d r a in s p e c i f i c a t i o n s and t o i n v e s t i g a t e th e
com m ercial p o s s i b i l i t i e s o f th e r e a c t i o n ,
A d is c u s s io n o f th e sam ple p r e p a r a t i o n an d p e rfo rm a n c e o f the- mangan­
e s e d io x id e p ro d u ced by t h i s s y n th e s is i s g iv e n , C hem ical a n a ly se s,.' w hich
in c lu d e s t o t a l m anganese, a v a i l a b l e o x y g en , m o is tu r e c o n t e n t , and pH,' a r e
t a b u l a t e d f o r - eac h m anganese d io x id e sam ple a s a r e a p p a r e n t d e n s i t y , b o b b in
w e ig h t and i n i t i a l d r a in t e s t p e rfo rm a n c e ,
A c o s t a n a l y s i s o f a p ro p o s e d te n to n p e r day p l a n t to p ro d u ce mangan­
e s e d io x id e by th e above s y n t h e s i s i s in c lu d e d .
H eat t r e a t i n g o f th e m anganese d io x id e made by th e ab o v e r e a c tio n w i l l
p ro d u c e a m anganese d io x id e t h a t w i l l m eet low d r a in s p e c i f i c a t i o n s , A su g­
g e s te d m ethod o f p r e p a r a t io n o f a sam ple by th e above p ro c e d u re i s ; p u r i f i ­
c a tio n o f a t e c h n i c a l g ra d e m anganese s u l f a t e by th e a d d i t i o n o f 10 grams o f
z in c o x id e p e r 1 2 4. gram s o f m anganese s u l f a t e , a d ju s tm e n t o f th e volume o f
th e m anganese s u l f a t e s o l u t i o n u n t i l th e c o n c e n tr a tio n i s 8 8 ,6 grams p e r
l i t e r , a d d i t i o n , a t th e r a t e o f 2 6 ,2 5 gram s p e r h o u r p e r 124 grams mangan­
e s e s u l f a t e , o f p o ta s s iu m p erm an g an ate o f a c o n c e n tr a tio n o f 52„5 gram s p e r
lite r.
The r e a c t i o n i s t o be ru n a t th e b o i l i n g p o i n t . A f t e r , w ash in g , f i l ­
t e r i n g and d r y in g th e p r o d u c t, i t i s to be h e a te d f o r 6 h o u rs a t 220 d e g re e s
c e n t ig r a d e .
M a te r i a l m e e tin g b o th h ig h d r a in an d low d r a in s p e c i f i c a t i o n s was p r o ­
duced from t e c h n i c a l g ra d e m anganese s u l f a t e and p o ta s s iu m perm anganate-'. The
c o n d itio n s o f a s u c c e s s f u l r e a c t i o n w ere; a e r a t i o n o f th e r e a c t i o n m ix tu r e ;
th e c o n c e n tr a tio n o f th e m anganese s u l f a t e was 0 ,1 mole p e r l i t e r ; a s o l u t i o n
c o n ta in in g one e q u iv a le n c e , b a s e d on one m ole o f m anganese s u l f a t e , p e r 2'
l i t e r s o f s o l u t i o n was ad d ed t o th e b o i l i n g m anganese s u l f a t e a t th e r a t e o f
2 6 ,2 5 grams p e r h o u r p e r m ole o f m anganese s u l f a t e ; th e r e a c t i o n ' m ix tu re
was h e ld a t th e b o i l i n g p o i n t f o r 3 h o u rs a f t e r th e f i n a l a d d i t i o n o f jihe
p erm a n g a n a te .
S u c c e s s f u l a d a p t a ti o n o f t h i s s y n t h e s i s to a c o n tin u o u s r e a c t i o n 'b a s i s
i s i n d i c a t e d by th e r e s u l t s o f t h i s i n v e s t i g a t i o n .
-4 -
INTRODUCT IOK
The l a r g e s t co n su m p tio n o f - m anganese d io x id e i s in. th e m a n u fa c tu re
o f d ry c e l l s , in w hich i t a c t s a s a d e p o l a r i z i n g a g e n t „
N a tu r a l s o u r c e s
o f s u p p ly o f t h i s m a t e r i a l a r e th e U .S .S .R = , I n d i a , B r a z i l ,. and"W est
A fric a .
I t i s e v id e n t t h a i d u r in g a w ar a t r a n s p o r t a t i o n p ro b lem i s en­
c o u n te re d in th e s u p p ly o f t h i s v i t a l m a t e r i a l .
B ecause o f th e l a r g e
am ount o f m o b ile e l e c t r o n i c eq u ip m en t u s e d by th e Army, th e demand f o r
*
l a r g e q u a n t i t i e s o f d r y c e l l s i s g r e a t d u r in g a p e r i o d / o f em ergency.
The Army, th ro u g h th e S ig n a l C o rp s, h a s sp o n so re d s e v e r a l r e s e a r c h
p ro g ram s to p ro d u c e , i n th e U n ite d S t a t e s , a m anganese d io x id e o f s u i t ­
a b l e d e p o l a r iz i n g p r o p e r t i e s .
The f i r s t s u c c e s s f u l p r o c e s s w a s ' p ro d u c tio n
by th e e l e c t r o l y s i s o f a m anganous s u l f a t e s o l u t i o n .
T h is p r p c e s s ,
;-
th o u g h e f f e c t i v e , h a s th e d is a d v a n ta g e s o f a h ig h o p e r a t i o n a l co st" and
h ig h pow er co n su m p tio n s
(Power co n sum ption c o n t r i b u t e s to th e h ig h op­
e r a t i o n a l c o s t , b u t . more, im p o r ta n t , th e u s e o f pow er i s c r i t i c a l d u rin g
w a r).
S in c e m anganese d io x id e may be p r e c i p i t a t e d by c h e m ic a l r e a c t i o n s
th e Army S ig n a l C orps i n s t i t u t e d a r e s e a r c h p ro g ra m " a t M ontana -S ta te
C o lle g e t o f i n d a s u i t a b l e c h e m ic a l s y n th e s is .'
The r e s u l t s o f th r e e / y e a r s
J-
o f r e s e a r c h have been r e p o r te d in w orks - by B e rg , e t a l . ( I ) , N ic k e ls o n ,-(6) ,
D avidson ( 2 ) , F a h lg re n ( 3 ) , M oore ( $ ) , S ad o g o p a c h a ri (7) ," a n d K l e i p f e l d a r
(4 ).
A f t e r th e c o n c lu s io n o f th e S ig n a l C orps c o n t r a c t ; th e " E n g in e e rin g
' -5 -
E x p erim en t S t a t i o n " a t M ontana S t a t e C o lle g e d e c id e d to c o n tin u e r e s e a r c h
in th e f i e l d .
The u l t i m a t e o b j e c t o f such r e s e a r c h was to be th e i n t e ­
g r a t i o n o f a ch e m ic a l s y n th e s is , w ith in an e x i s t i n g c h e m ic a l p l a n t .
A
s u rv e y o f th $ c h e m ic a l i n d u s t r y d i s c l o s e d 'a number o f s y n th e s e s -th a t
.could p o s s i b l y be u s e d . . F u r th e r s tu d y o f th e more a t t r a c t i v e s y n th e s e s ,
w hich in c lu d e d econom ic e v a l u a t i o n s , i n d i c a t e d t h a t one o f t h e m o st
f a v o r a b l e s y n th e s e s was th e p r o d u c tio n o f m anganese d io x id e by "the
o x id a tio n o f m a n g a n e s e .s u lf a te in aq u eo u s s o lu ti o n by th e s im u lta n e o u s .
r e d u c tio n o f p o ta ss ip m p e rm a n g a n a te , w hereby th e m anganese content"' o f
b o th compounds i s r e c o v e re d a s b a t t e r y a c t i v e m anganese d io x id e .
The .work r e p o r t e d in t h i s t h e s i s in c lu d e s i n v e s t i g a t i o n o f m ethods w hereby a s p e c i f i c a t i o n
'm a t e r i a l c o u ld be p ro d u ced by t h i s s y n t h e s i s .
P r e v io u s w ork had i n d i c a t e d v e ry p o o r b a t t e r y p e rfo rm a n c e f o r m a t e r i a l
p ro d u ced from th e ab o v e - S ta r t in g m a t e r i a l , b u t th e v e r y f a v o r a b le
econom ic c lim a te i n d i c a t e d t h a t a more th o ro u g h i n v e s t i g a t i o n m ig h t bein O rb q r.
A few l a r g e s c a l e r e a c t i o n s a r e r e p o r te d in t h i s w ork.
SPECIFICATIONS
■■ S in c e th e l a r g e s t m a rk e t f o r d ry c e l l s i s th e m i l i t a r y , th e .s p e c ­
i f i c a t i o n s e s t a b l i s h e d by th e Army S ig n a l-C o rp s, f o r a c c e p ta b l e s y n th e t ic
m anganese d io x id e " -h a v e ‘"b een -u sed in .th e e v a lu a tio n o f th e sam p les p ro ­
duced in t h i s i n v e s t i g a t i o n i, ' The f o llo w in g s p e c i f i c a t i o n s a r e from
B u l l e t i n SCL-3117-D (S) d a t e d - 18 March 1 9 5 2 .
-6 -
Cfaemical C o m position
A v a ila b le oxygen a s MnO2
■Total m anganese a s Mn
A bsorbed m o is tu re , a s H2O
I r o n a s Fe ( s o l u b l e i n HCl)
S i l i c o n a s $iC>2
'
T o ta l a l k a l a i an d a l k a l i n e
e a r t h m e ta ls
T o ta l heavy m e ta ls
( o t h e r th a n F e, Pb)
L e a d .a s Pb
pH
8 5 - 0% m in 0
5 8 „0% min 0
3 «0% max0
0 <>3 % max.
0.5% max.
1 , 0% max.
0 =3% max.
0 , 2% max.
A00—8 ,0
A p p a re n t D e n s ity
The s y n t h e t i c m anganese d io x id e s h a l l have an a p p a r e n t d e n s i t y be­
tw een 2 0 -3 0 grams p e r c u b ic in c h .
P a r t i c l e S iz e
The s y n t h e t i c m anganese d io x id e s h a l l be o f su ch s i z e t h a t a t
l e a s t 65 p e r c e n t o f th e m a t e r i a l s h a l l p a s s th ro u g h " a ' D. S 0 S ta p d a rd
S ie v e Mo, 200 and a t l e a s t 90 p e r c e n t th ro u g h a U0 .8 » S ta n d a rd S ie v e No,
IOO0
C r y s t a l l i n e P h ase
From c r y s t a l l o g r a p h i c and m i c r o s t r u c t u r a l a n a l y s e s p red o m in an ce o f
th e i m p e r f e c t ly c r y s t a l l i z e d p h a se known a s gamma m anganese d i o x i d e ■
•t
'
s h o u ld be e v i d e n t, .
P a r t i c l e M orphology
I
The p a r t i c l e s h a l l p r e s e n t i r r e g u l a r sh a p e s w ith
no e v id e n c e o f
c le a v a g e ( t h a t i s , w ith n o n - r e c t i l i n e a r p r o f i l e s h a v in g n e b u lo u s - r a t h e r
■than s h a r p , w e ll - d e f in e d ed g es) when exam ined a t d i r e c t m a g n if ic a tio n
from 5 ,0 0 0 to 2 0 ,0 0 0 d ia m e te r s 0
->
—7—
X-Elay D i f f r a c t i o n P a t t e r n
The X-Elay d i f f r a c t i o n p a t t e r n s h a l l be c h a r a c t e r i z e d by th e d i f f u s e
l i n e p a t t e r n o f gamma m anganese d io x i d e .
S i g n i f i c a n t l i n e s , d , o f ’ gamma
m anganese d io x id e an d t h e i r r e s p e c t i v e r e l a t i v e i n t e n s i t i e s , I , f o r i r o n
.
.
.
: !
'
•
i r ­
r a d i a t i o n a r e a s f o llo w s :
d
:
I
A .0 0 '
2 .6 5
2 .1 6
5
7
7
10
5
3
1.65
1 .6 0
1 .0 6
F ig u r e 3> in th e A ppendix, shows th e v a r io u s d i f f r a c t i o n p a t t e r n s o f
th e sev en ty p e s o f m anganese d io x id e .
B a tte ry L ife
I:
The s p e c i f i c a t i o n s fo p d is c h a r g e o f s ta n d a rd .A s i z e d r y 'c e l l s a r e
: '
.
:
:
a s f o ll o w s :
.
.
Type o f d is c h a r g e
D is c h a rg e r e s i s t a n c e
End v o lt a g e
■'
T em p eratu re
R e la tiv e H u m id ity •
B a t te r y L i f e
Low -D rain
H ig h -D rain
c o n tin u o u s
166- 2 /3 ohms
1 . 13- v o l t s '
70°Fo
c o n tin u o u s
16- 2 /3 ohms
1 .0 0 v o l t s
70°F .
50%
5 .5 h o u rs
130 h o u rs
MATERIALS AHD METHODS
EQUIPMENT
The s m a ll r e a c t i o n s w ere ru n i n s ta n d a r d l a b o r a t o r y g la s s eq u ip m en t.
r
Those p i e c e s o f eq u ip m en t t h a t have been c o n s id e r e d u n iq u e a r e d e s c r ib e d in
a f o llo w in g s e c t i o n :
SYNTHESES.• •
In o r d e r to ru n r e a c t i o n s , w here th e volume w ould be in -,excess o f
?
th e l i m i t e d s iz e o f g l a s s b e a k e r s , a 20- g a l l o n r e a c t i o n v e s s e l wa'S" p u t
in to u se ,
A Haveg l i n e d ta n k was m o u n te d ^ s u f f ic ie n t d i s t a n c e above" th e
f l o o r to f a c i l i t a t e p r o d u c t re m o v a l.
A g ita tio n was p ro v id e d , by a 1 /3
h , p , m o to r b e l t e d to a s h a f t and b e a r in g mount l o c a t e d o v e r th e c e n t e r o f
'
th e ta n k ,
A 6- i n c h wooden im p e ll e r an d 3 / 4 - i n c h wooden d r i v i n g s h a f t
w ere c o u p le d td t h e s h a f t in th e b e a r in g m ount.
was h e a te d by a-’ steam s p a r g e r .
The r e a c t i o n m ix tu re
The p r o d u c t was removed e i t h e r by
s ip h o n in g o r th ro u g h a b o tto m b u n g .
B ecause th e r e a c t i o n s w ere ru p a t th e b o i l i n g p o i n t , a c o n d e n se r
,
was p ro v id e d to rem ove e f f l u e n t S teanu
1 0 - in c h g a lv a n iz e d ir o n f u r n a c e p i p e ,
The c o n d e n s e r was c o n s tr u c t e d o f
A s e c t i o n o f 1 0 - in c h p ip e ro s e
d i r e c t l y above th e ta n k to an elbow w hich c o n ta in e d a b lo w e r,' W h ic h rd is c h a rg e d i n t o
6 f e e t o f 7 - in c h g a lv a n iz e d ir o n p i p e .
downward to a f l o o r d r a i n .
The 7 - in c h p ip e le d
The downcoming p ip e was p ack ed w ith 12 in c h e s
o f R ash ig r i q g s an d was c o o le d by two i n t e r n a l w a te r s p r a y s ,
' ’
B ecause th e q u a n t i t y o f p r o d u c t t h a t was made i n th e ab o v e r e a c tio n '
vessel
was l a r g e r th a n o r d in a r y l a b o r a t o r y - s i z e f i l t e r s c o u ld h a n d le , a
l a r g e s u c ti o n - ty p e f i l t e r was c o n s t r u c t e d .
m oving a s q u a re p o r t i o n o f th e to p o f a
The f i l t e r was made b y /r e ­
3 0 - g a llo n o i l drum.
The-"removed
p o r t i o n o f th e drum was r e p l a c e d - w i t h : a p ie c e o f f i l t e r c l o t h - h e l d in
p la c e by b o l t e d wooden c l e a t s ,
d r a in v a l v e ,
to p ,
A
The b o tto m o f th e drum was - f i t t e d w ith a
h o le was c u t i n th e s id e o f th e drum 12 in c h e s from t h e -
A p ie c e o f l / 2 in c h p ip e was b r a z e d in t h i s h o le a n d was c o n n e c te d
-9 -
to a Hash "H y to r" vacuum pump.
'I n o p e r a t i o n , a s l u r r y i s p o u re d on th e
c l o t h and i s f i l t e r e d by vacuum.
R eag e n ts
S in c e th e g o a l o f t h i s i n v e s t i g a t i o n was t o d e v e lo p - a p r o c e s s t h a t
c o u ld be i n t e g r a t e d i n a com m ercial p l a n t , b o th D . P . g ra d e and T ech,
g ra d e c h e m ic a ls -w e re -u sed .
The ChP. g ra d e
c h e m ic a ls w ere u s e d w here i t
was d e s i r e d to p ro d u c e an o x id e o f h ig h p u r i t y f o r b a t t e r y e v a l u a t i o n .
: ■
The T ech , g ra d e c h e m ic a ls w ere u s e d w here i t was d e s i r e d to d e te rm in e
th e e f f e c t of. th e i m p u r i t i e s on th e b a t t e r y l i f e o f th e p r o d u c t," a n d i n
th e l a r g e r s c a l e r e a c t i o n s .
No w ork was done w ith n a t u r a l o r e s b e c a u se
th e m ain p l a n t was e x p e c te d to s u p p ly b o th r e a g e n ts o f T ech, g ra d e - p u r ity .
S y n th e s e s
The
m ethod o f p r e p a r a t io n o f sam p les d is c u s s e d in- t h i s t h e s i s a r e
shown in T a b le I I o f th e A p pendix.
The s te p s f o r th e p r e p a r a t io n o f a
sam ple a r e a s f o llp w s ;
1.
S o lu tio n s o f th e r e a c t a n t s w ere made.
2.
The m anganous s u l f a t e s o l u t i o n was h e a te d to th e b o i l i n g p o i n t
i n e i t h e r a 20 l i t e r P y re x j a r o r in th e l a r g e - r e a c t i o n -v p sp e l.
3-„
The 'KMnO^ s o l u t i o n was ad d ed to th e h o t iMnSO^ s o lu ti o n a t th e
d e s ire d r a t e .
4„
The r e a c t i o n m ix tu re was a llo w e d to a g i t a t e f o r a d e s ir e d
le n g t h o f tim e a f t e r th e co m p leted a d d i t i o n o f thetKMnO^.
The te m p e r a tu r e may h av e been m a in ta in e d a t th e b o i l i n g : p o i n t
o r th e s o l u t i o n may h av e been a llo w e d to c o o l.
5.'
D e c a n ta tio n o f th e r e a c t i o n e f f l u e n t an d s u b se q u e n t " a d d itio n s
an d d e c a n ta t io n s o f wash w a te r was c a r r i e d o u t . The sam ple was
w ashed u n t i l th e pH o f th e e f f l u e n t w ash w a te r re a c h e d 6 . $ - - 7 .0 .
-IG 6.
' 7=
The sam ple was f i l t e r e d an d t r a n s f e r r e d to a d r y in g o v en ,
The d r y in g tim e , a t a te m p e r a tu r e o f 105 to -IlO 0G., ^ was
a p p r o x im a te ly 48 h o u rs fo r. eac h sam p le,
:
80
The sam ple was n e x t b a l l - m i l l e d f o r 2 h o u rs in a 3o5 g a llo n
s i z e p o r c e l a in p e b b le m i l l r e v o lv in g a t 60 r e v , / p i n , and
c h a rg e d w ith a p p r o x im a te ly 5 ,5 l b , o f f l i n t p e b b le s o f a b o u t
o n e - in c h d ia m e te r e a c h ,
9»
Upon rem o v al from th e b a ll^ m j.1 1 ,’ th e "sam ple was s c re e n e d
th ro u g h a TI, S , S ta n d a rd S ip v e h o . 4 0 , th e ^4Q mesh p o r tio n
b e in g r e t a i n e d an d s t o r e d f o r t e s t i n g .
10» The n e c e s s a r y a n a l y t i c a l t e s t s w ere c a r r i e d o u t on th e s a p p le .
(S ee T a b le I in th e A p p e n d ix ).
.
1 1 . "A" s i z e c e l l s w ere f a b r i c a t e d o u t o f th e sam p le.
1 2 . The f a b r i c a t e d c e l l s w pre t p s t e d . a t eac h s p e c i f i e d r e s i s t a n c e .
The number o f c p l l s t h a t werp t e s t e d on e a c h 'r e s i s t a n c e va’i i e d .
Enough c e l l s w ere t e s t e d su ch t h a t a t l e a s t two c e l l s had ap ­
p r o x im a te ly e q u a l d r a in l i v e s .
N otes f o r s te p s 2 - 4 :
th e r e a c t i o n m ix tu r e i s u n d e r c o n s ta n t
m e c h a n ic a l a g i t a t i o n ; th e r e a c t i o n i s m a in ta in e d a t c o n s ta n t volume by th e
a d d i t i o n o f h o t HgO; th e P y re x v e s s e l was h e a te d by an e l e c t r i c Im m ersion
:
- f
h e a t e r an d a h o t p l a t e ; th e l a r g e r e a c t i o n v e s s e l was h e a te d by sp a rg e d
s team ,
>
■
Those sam p les whose num bers a r e S U ffix p d by th e sy m b o l' "H", w ere made
by h e a t in g t h e sam ple i n an e l e c t r i c o v e n . a t th e d e s ir e d te m p eratu re- an d
f o r th e d e s i r e d le n g t h o f tim e .
The m ain v a r i a b l e s e n q o u n te re d i n t h i s i n v e s t i g a t i o n a r e :
concen­
t r a t i o n o f r e a c t a q t s , tim e o f r e a c t i o n , e f f e c t o f e x t e r n a l a g e n t s ; 'a n d
p u rity o f re a c ta n ts .
T hese v a r i a b l e s a r e c o r r e l a t e d w ith " b h t t e r y a c t i v i t y
i n th e d i s c u s s i o n s e c ti o n o f t h i s t h e s i s .
C om plete s t u d i e s o f e a c h - o f th e
-1 1 -
above v a r i a b l e s have n o t been made.
B ecau se o f th e n a t u r e
o f th e p ro b le m ,
a s o u t l i n e d i n th e i n t r o d u c t i o n , th e r e s e a r c h was p la n n e d so .t h a t a'.-change
o f v a r i a b l e s w ould p ro d u c e a s i g n i f i c a n t ch an g e in th e b a t t e r y I i f e i - V iA ll
r e a c t i o n s , e x c e p t o n e , w ere b a tc h r e a c t i o n s , th e one e x c e p tio n b e in g run
:
■ _
'
v
on a s e m i-c o n tin u o u s b a s i s ,
'" ‘
B a t te r y F a b r ic a tio n an d T e s tin g
From 5 to . 10 stan d ard -; mAh s i z e d ry c e l l s w ere c o n s tr u c t e d i n a c ­
co rd a n c e w ith
s p e c ific a tio n s
c e l l a sse m b ly te c h n iq u e s o u t l i n e d - i n Army S ig n a l Corps
B u l l e t i n SCh-3117-D ( 8 ) ,
A m ix tu re c o n t a in in g SG p e r c e n t
by w e ig h t o f th e m anganese d io x id e sam p le, 8 p e r c e n t S h aw in ig an carbon
b la c k , and 12 p e r c e n t BH^Cl was b le n d e d in a p e b b le m i l l f o r 20 m in u te s
to a s s u r e u n ifo rm c o n s is te n c y ,'. T h is m ix tu re was dampened w ith a y w e ttin g
s o lu ti o n ccn sisb ih g o f ^ ,S -'p e rc e n ’t BH^Cl by w eig h t," 8^6 p e r c e n t ' ZhClg, 'an d
8'5 ,6
p e r c e n t H^O u n t i l m a t e r i a l a c c e p ta b l e f o r tam ping was o b ta in e d .
From th e m ix tu re d e s c r ib e d a b o v e , b o b b in s w ere t&mped in ah a p p a r a tu s
w hich i s d q a g ra m m a tic a lly shown in F ig u r e I o f th e A ppendix,;
D u eito th e
c o r r o s iv e n e s s o f th e m ix tu r e u s e d in b o b b in m aking, s t d l l i t e and m etha­
c r y l a t e p l q s t i c w ere u t i l i z e d f o r th e p a r t s o f th e a p p a r a tu s w hich-w ould
c o n ta c t th p m ix tu r e ,
■
A f t e r ta m p in g , th e b o b b in s w ere w rapped in c o tto n g a u z e , " tie d - w ith
c o tto ti th r q a d , an d s e t i n z in c c a n s w ith a c o ld p a s t e e le c tr o ly te " " c o n ­
ta in in g - a " r a t i o - of-- 5Q m l. o f a s o lu ti o n c o n s i s t i n g o f 2 3 ,7 p e r c e n t BH^Cl,
2 2 ,3 p e r c e n t ZnClps 0 . 1 p e r c e n t HgClp, an d 5 3 .9 p e r c e n t HpO to 1 0 ,7 gm„ o f
—1 2 —
I
a m ix tu re c o n ta in in g 74°7 p e r c e n t c o r n s t a r c h an d 25=3 p e r c e n t f l o u r ,
A p a p e r w ash er was p la c e d aro u n d th e carb o n r o d , a b r a s s cap was p r e s s e d
on th e r o d , and th e n th e b o bbin was s e a le d in th e can w ith wax.
A f t e r a p e r io d o f f i v e d a y s , th e c e l l s w ere s c re e n e d f o r open
v o lt a g e and th e n from 4 to 6 c e l l ? w ere d is c h a r g e d th ro u g h th e p r e ­
v io u s ly s p e c if ie d r e s is ta n c e s .
F ig u r e 2 o f th e A ppendix s c h e m a tic a lly
shows a p o r ti o n o f th e t e s t r a c k .
The t e s t r a c k c o n s is te d o f 'e ig h tI 6 ,6 7
ohm r e s i s t a n c e s , tw e n ty - f o u r 1 6 6 ,7 ohm r e s i s t a n c e s , and an open v o lta g e
c i r c u i t th ro u g h th e v o lt m e t e r .
The t e s t r a c k was p la c e d in an i n s u l a t e d '
box w here th e te m p e r a ty r e was c o n t r o l l e d a t 7 0 ^2 °F , - The i n s u l a t e d box
)
a l s o s e rv e d a s a s to r a g e p la c e f o r a l l u n t e s t e d c e l l s , '
End v o lta g e s - f o r
th e d r a in t e s t s w ere 1 ,1 3 v o l t s f o r th e 166=7 ohm r e s i s t a n c e , c a l l e d low
d r a in (L =D ,) ; an d 1 ,0 0 v o l t s f o r th e 1 6 ,6 7 ohm r e s i s t a n c e , c a lle d - h ig h
d r a in . (H ,D ,) ,'
T h e .;v o ltm e te r i n th e t e s t r a c k c o n s is te d o f a Simpson 50 m icro ­
am pere am m eter in s e r i e s w ith a 3 3 0 ,0 0 0 ohm carb o n r e s i s t o r an d a 1 0 ,0 0 0
ohm v a r i a b l e r e s i s t o r .
By a d ju s tm e n t o f th e v a r i a b l e r e s i s t o r , i t was
p o s s i b l e to c a l i b r a t e th e am m eter,, a g a i n s t a s ta n d a r d v o lt m e t e r , su ch t h a t
v o lt a g e s betw een 1 ,0 0 an d 1 ,2 0 c o u ld be r e a d d i r e c t l y from th e m e te r 's
s c a le .
The m e te r c o u ld be r e a d to an a c c u r a c y o f ^ ,005 v o l t s s
The c a l i ­
b r a t i o n o f th e am m eter, u s e d a s a v o lt m e t e r , was t e s t e d p e r i o d i c a l l y by
m e a su rin g th e v o lta g e - o f - a - s ta n d a r d c e l l on th e open v o lta g e c i r c u i t . was fo u n d t h a t th e c a l i b r a t i o n o f th e am m eter rem a in ed c o n s ta n t .
It
The u s e
-1 3 -
o f an
am m eter a s a v o ltm e te r h a s th e i n h e r e n t a d v a n ta g e o f d raw in g
o n ly a s m a ll am ount o f c u r r e n t from th e t e s t c e l l w henever a v o lta g e
r e a d in g was made.
A f t e r a p e r io d o f t h r e e m o n th s, from one to th re e - c e l ls , o f a p a r t i ­
c u l a r sam ple w e r e - t e s t e d " f o r low d r a i n l i f e ,
The th re e -m o n th s d r a i n - l i f e
o f th e c e l l s i s an i n d i c a t i o n b f' th e s a m p le 's s h e l f l i f e .
The Army
S ig n a l C orps s p e c i f i c a t i o n o f th e th re e -m o n th s d r a in l i f e i s t h a t th e
c e l l s on th e th re e -m o n th s t e s t w i l l g iv e 85 p e r c e n t o r g r e a t e r p f th e
i n i t i a l d r a in l i f e .
Oxygen A n a ly s is
A v a ila b le oxygen d e te r m in a tio n s w ere made in a c c o rd a n c e w ith S ig n a l
C orps m eth o d s'-as s t a t e d I n B u l l e t i n SCL-3H 7-D ( 8 ) ,
made a s f o ll o w s J
The d e te r m in a tio n , was
'
A sam ple o f d r i e d o r e ( a p p r o x im a te ly 0 ,2 -g m ,) was w eighed a c c u r a t e l y
i n t o a 600 .ml, b e a k e r f i t t e d w ith a c l o s e f i t t i n g w atch glass=;'
50 m l, o f
tra tio n
E x a c tly
a s to c k s o l u t i o n o f f e r r o u s ammonium s u l f a t e o f known, co n ce n ­
(a p p ro x im a te ly 0 ,2 N) w ere ad d ed from a p i p e t t e , ' In a s i m i l a r
b e a k e r t h e r e was p la c e d e x a c tly 50 m l, o f th e f e r r o u s ammonium s to c k
s o lu tio n
to s e rv e a s a c o n t r o l . B o th .th e o r i g i n a l an d c o n tro l- sam ple
■
w ere d i l u t e d t o - 150 m l, w ith d e io n iz e d w a te r and d i g e s t e d on a stdam b a th
w ith o c c a s i o n a l s t i r r i n g u n t i l s o l u t i o n o f th e p re was e f f e c t e d , - The
s o l u t i o n s w ere a llo w e d to c o o l and th e volum es a d j u s t e d to a b o u t 200 m l.
The sam p les w ere th e n t i t r a t e d w ith a s o lu ti o n o f p o ta s s iu m d ic h ro m a te o f
known c o n c e n tr a tio n (a p p ro x im a te ly 0 , 2N) u s in g th e p o te n tio m e tr ic m ethod
-1 4 -
f o r d e t e c t i o n o f end p o i n t .
T o t a l M anganese
A n a ly s is
A sam ple o f d r ie d o r e (a p p ro x im a te ly 0 .1 -g m .) was "w eighed a c c u r a t e l y
i n t o a 600 m l. b e a k e r f i t t e d w ith a w atch g l a s s . Ten m l. o f d i s t i l l e d
w a te r and 5 m l. o f c o n c e n tr a te d h y d r o c h lo r ic a c i d w ere ad d ed an d th e
sam ple was d is s o lv e d ^ b y .h e a tin g .to d r y n e s s an d c o o le d .
The s o l u t i o n w a s -e v a p o ra te d
a lm o s t
T w e n ty -fiv e n£L. o f c o n c e n tr a te d - s u l f u r i c an d 10
m l. o f c o n c e n tr a te d n i t r i c a c i d w ere ad d ed an d th e s o l u t i o n was h e a te d
s t r o n g l y u n t i l th e r e , was no f u r t h e r e v o lu tio n o f brown fu m es.
A f t e r c o o lin g , 2 7 5 -3 0 0 m l. d e io n iz e d w a te r and 3 gm'. o f "sodium
b is m u th s t e w ere a d d e d .
The m ix tu re was s t i r r e d f o r f i v e m in u te s and
f i l t e r e d , w ith s u c t i o n , th ro u g h a f i n e s i n t e r e d - g l a s s f i l t e r f u n n e l i n t o
a o n e - l i t e r s id e arm f l a s k .
The f i l t e r f u n n e l, c o n ta in in g e x c e ss b i s -
m u th a te , was w ashed s e v e r a l tim e s w ith d e io n iz e d w a te r to a s s u r e rem o v al
o f th e m an g an ate i o n .
F i f t y m l. o f spdium o x a la te s o l u t i o n (a p p ro x im a te ly
0 .2 N) a n d 100 m l. o f 10% s u l f u r i c a c i d w ere ad d ed to th e s o lu tio n .-
T h is
s o l u t i o n was h e a te d a lm o s t to b o i l i n g and th e e x c e ss o x a l a te was t i t r a t e d
w ith 0 .1 N
p o ta ss iu m p e rm a n g a n a te .
pH D e te rm in a tio n
A one gram sam ple o f th e d r i e d o r e was a c c u r a t e l y w eighed i n t o a 250
m l. E rle n m e y e r f l a s k an d a q u a n t i t y o f d e io n iz e d w a te r . e q u a l to e x a c tly
100 tim e s th e w e ig h t o f sam ple was a d d e d -.
was th e n m arked a t t h i s l e v e l .
The o u ts id e w a l l - o f th e f l a s k
The c o n t e n ts o f th e f l a s k w ere "b o iled
a c t i v e l y f o r f i f t e e n m in u te s , th e w a te r l o s t by e v a p o r a tio n was r e p l a c e d .
-1 5 -
a n d t h e m ix tu re was a g a in b ro u g h t to b o ilin g =
The f l a s k was 't h e n " f i t t e d
w ith d r y in g tu b e s c o n t a in in g a s c a r i t e an d th e m ix tu r e a llo w e d t o '^cool
to room te m p e ra tu re =
T he..,eontenhS'-w ere' .--tra n s fe rre d t o - a s u i t a b l e
b e a k e r and th e pH was th e n d e te rm in e d on th e s l u r r y by means o f Ja Beckman
pH m e te r .
D u rin g th e pH .m easurem ent, th e b e a k e r c o n ta in in g th e 'pdm ple
was s t i r r e d to o b ta in a u n ifo rm s u s p e n s io n o f th e s o l i d s .
A p p a re n t D e n s ity
.
.
.
:
A p p a re n t d e n s i t y was d e te rm in e d by ru n n in g a p o r ti o n o f th e -4 0
mesh b a l l - m i l l e d sam ple th ro u g h " a; S c o tt v o lu m e te r i n t o a c u b i c - in c h
c o n ta in e r.
The a p p a r e n t d e n s i t y was r e p o r te d a s grams p e r c u b ic in c h .
M o is tu re C o n te n t
'
A sam ple w eighing, from two to t h r e e grams was d r i e d - f o r 16 h o u r s
at
a te m p e r a tu r e o f 1 0 5 -1 1 0 ° .0,
The l o s s in w e ig h t was ta k e n a s ^the
f r e e m o is tu r e c o n s e n t,
X-Ray and S o e c tro c h e m ic a l A n a ly se s
X-Rajr a n d s p e c t r o c h e m ic a l a n a ly s e s o f th e sam ples w ere done a t
i
I
.
:
th e S ig n a l C orps E n g in e e rin g L a b o r a to r ie s , F o r t M onm outh,.H ew -Jersey ,
::
The m ethods u s e d , a s d e s c r ib e d by them , a r e a s ; f o l l o w s ; .
X-Ray d i f f r a c t i o n s
'X -R ay d i f f r a c t i o n pow der p a t t e r n s o f p o r ti o n s o f
v
th e sam p les w ere p r e p a r e d u s in g ir o n K a l p h a - r a d i a t i o n i n - a D eb y e-ty p e
cam era y i e l d i n g a d i s p e r s i o n o f one d e g re e o f two t h e t a p e r m i llim e te r , o f
film .
S p e c tro c h e m ic a l a n a l y s i s s
The sam ple was b u rn ed to co m p le tio n in a
■
—
_L6)-~
D. C. a r c an d th e r e s u l t a n t s p e c tr a p h o to g ra p h e d .
A s p e c ia lly s e le c te d
sp ectru m l i n e o f each o f th e v a r io u s c o n s t i t u e n t e le m e n ts was m easured
f o r i n t e n s i t y and com pared w ith th e i n t e n s i t y o f th e manganese- i n t e r n a l
s ta n d a r d l i n e .
T h is d a t a was u sp d to d e te rm in e th e p e r c e n ta g e s o f th e
e le m e n ts p r e s e n t , u s in g p r e v io u s l y e s t a b l i s h e d w orking c u r v e s .
The
am ounts o f sodium and p o ta s s iu m w ere d e te rm in e d by a m o d ifie d method
w hereby l i t h i u m was th e i n t e r n a l s ta n d a r d l i n e i n s t e a d o f th e m anganese
lin e .
,
:
DISCUSSION OF RESULTS
C o st
A n a ly s is o f th e P r o c e s s
• v •
As was m e n tio n ed in th e i n t r o d u c t i o n , t h i s p r o c e s s h a s th e a d v a n ta g e •
o f a f a v o r a b l e econom ic c l i m a t e .
To f u r t h e r i l l u s t r a t e t h i s p o i n t / a
condensed c o s t a n a l y s i s o f th e r e a c t i o n scheme is._ g iy en . b elo w .
The r e a c t i o n i s : 3M nS 0^(aq,J +2KMnO^(aq. ) -f^HpO( I ° ) —£ -> 5M n^.xH ^D [s.)4K2S0i/k( a q . )+-2H2 S0^ ( a q . J .
The p r o c e s s to be u s e d i s th e b a tc h w is e a d d i tio n
o f KMnO^ to -MnSO4 a t th e b o i l i n g p o i n t . - ZnO- w i l l bfe ad d ed to ih e MnSO^
fo r p u rific a tio n .
The r e a c t i o n m ix tu re w i l l be a e r a t e d b u t
m e c h a n ic a l
a g i t a t i o n w i l l a l s o be u s e d . - F a s h in g w i l l r e q u i r e a t h r e e s ta g e co u p t-erc u r r e n t d e c a n ta t io n u n i t .
The p r e c i p i t a t e d p r o d u c t w i l l be f i l t e r e d qn a
r o t a r y drum f i l t e r an d d r ie d i n a k i l n - t y p e d r y e r .
d r i e d p r o d u c t ■w i l l be done w ith p o r c e l a in e q u ip m e n t.
P e b b le - m il lin g o f th e
The n e c e s s a r y " a n a ly s e s
and t e s t s ' w i l l be p erfo rm e d on th e p r o d u c t b e f o r e s a l e .
-1 7 -
I t w i l l be assum ed t h a t th e main p l a n t w i l l be a b l e to S upplyi th e
m anganese d io x id e p r o c e s s w ^ th -MnSO^ an d KMnO^o
Mo c r e d i t w i l l b e ■ta k e n
f o r th e s e c o n d a ry r e a c t i o n p r o d u c t s . ' R ecovery o f m anganese w i l l be a s sumed t o b e 95 p e r c e n t o f i n p u t .
B p ild in g s , la n d , and n e c e s s a r y rdockage
r
f a c i l i t i e s w i l l n o t b e c o n s id e r e d a s p a r t o f th e r e q u ir e d in v e s tm e n t.
H an d lin g a n d ." tr a n s p o r ta tio n l o s s e s w i l l b e ig n o r e d b e c a u se h y d r a tio n o f
•
'
'
I
th e p r o d u c t MnOg w ill , m ate up f o r such l o s s e s .
M ark et s t u d i e s , by th e Army S ig n a l C o rp s, have shown - th a t th e —b a t t e r y
i n d u s t r y w ould buy a b o u t 10 to n s p e r day o f a s a l a b l e p r o d u c t: 'a t $0 .2 5 p e r
pound.
The
c o s t o f th e r e a g e n t s .a r e th o s e p r i c e s fou n d in th e "rep en t
'
"y
i s s u e s o f rlC hem ical an d ..E n g in e e rin g , Mewsa .
i
T h is s tu d y i s d iv id e d i n t o th e f o llo w in g s e c tio n s :
e r a t i n g c o s t , an d in v e s tm e n t.
p la n tc o s t,-, op'f
Each o f t h e s e - s e c t i o n s ' shows t h e n ecessary -
c a l c u l a t i o n s p e r t i n e n t to th e .d e s i r e d r e s u l t .
A ■sum m ary-of th e co m p lete
a n a l y s i s i s g iv e n a t th e end o f th e s tu d y .
P l a n t C o s t:
I Two m ix in g t a n k s , wood, 2000 g a l l o n s .
Two r e a c t i o n v e s s e l s , a s p h a l t l i n e d
wood t a n k s , 1 0 ,0 0 0 g a l lo n s w ith
h e a t in g c o i l s an d a g ita tio n 'e q u ip m e n t=
$ 4 ,0 0 0
1 2 ,0 0 0
C o u n te r c u r r e n t d e c a n ta t io n u n i t ,
/ 3 th i c k e n e r s an d 3 s l u r r y t a n k s .
1 2 , 00Q
R o ta ry f i l t r a t i o n eq u ip m en t, 200
i sq« f t . o f - f i l t e r i n g a r e a .
1 2 ,0 0 0
R o ta ry p r o d u c t d r y e r .
5,000
-1 8 -
A P e b b le - m il l arid c l a s s i f i e r
^ rJ T o ta l eq u ip m en t c o s t .
57,0 0 0
^ I n s t a l l a t i o n o f eq u ip m en t, $0
( ^ p e r c e n t o f eq u ip m en t c o s t .
$ 28,500
P ip in g , pum ping an d t r a n s p o r t a t i o n
eq u ip m en t, 30 p e r c e n t o f eq u ip m en t
' c o s t.
1 7 ,1 0 0
q Ma t e r i a l s h a n d lin g eq u ip m en t.
y ^ T o ta l c o s t o f p l a n t . e q u ip m en t.
_
1 0 .0 0 0
I -I I S t OQG)-
46^ ,541
O p e ra tin g C o s ts ;
;1 3 ,3 1 0
day
87 l b . MnQg
5
x 2
5
47,f t / / k
R eag e n t"
MnS0'4 .
KMnO^
ZnO
day
55- l b . Mn.
x 157 l b . , KMnO/,
55 l b . Mn.
x I l b . ZnO =
50 l b . InSO 4
2 2 ,0 0 0
day
0 .9 5
lb ./d a y
2 2 ,0 0 0
1 5 ,2 0 0
440
: 1 5 ,2 0 0 l b . KMnO;,
d ay
400
C o st l / l b .
I 0 .0 1 CS,OS
0 .1 5 Ov?T
0 .1 5 O lH S
l b ; ZnO
■ ' d ay
T o ta l c o s t/ d a y
I
220
2 ,280
$ -2-5-566
-/Oj SS1U
R eagent c o s t p e r pound o f f i n i s h e d p r o d u c t:
I 2 5 6 6 /d ay
=
2 0 ,0 0 0 l b . / d a y
I 0.1281 / l b .
^ o lH _
% O , S3
P r o c e s s E n erg y C q st:
T here a r e 2 3 6 ,3 0 0 l b . o f aq u eo u s r e a c t i o n m ix tu re to- be
h e a te d p e r d a y .
The h e a t c a p a c it y o f th e m ix tu re w i l l be
assum ed a p p ro x im a te ly e q u a l to 0 .9 B . t . u .
Ib= o f
)i0 °
135SP
a® 5
iM, -sa ?
p .,
-1 9 -
2 3 6 ,3 0 0 x 0 .9 ( 2 1 2 - 6 2 ) =
3 1 ,9 0 0 ,0 0 0 B . t . u .
Ten p e r c e n t o f th e above h e a t w i l l have to b e r e p la c e d in
th e sy stem b e c a u s e o f h e a t l o s s e s . • S ix ty p e r c e n t h e a t t r a n s ­
f e r w i l l be a t t a i n e d .
3 1 .9 0 0 .QQQ x 1 .1 =
0.6
5 8 ,5 0 0 ,0 0 0 B . t . u . / d a y
I t w i l l b e assum ed t h a t th e f i l t e r cake w i l l c o n ta in 20
p e rc e n t, m o i s tu r e .
T h is w i l l n e c e s s i t a t e th e rem o v al o f
'5 ,0 0 0 l b . w a te r p e r t^ay.
H e a t o f v a p o r iz a ti o n e q u a l s "1000
B . t . u . / l b / HgO*
5 0 0 0 .x 1000
8,350,000 B.-t.u ./day
0.6
T o ta l h e a t r e q u i r e d , p e r d ay , i s (6 6 ,8 5 0 ,OQQ^B...t.u .
&
//a c ?
C o st o f h e a t i s $ 0 .8 9 5 /1 .0 5 x 1 0 ° B . t . u .
-4
6 6 , 8 5 0 ,0 0 0 ■xr-fv.0-.895x
I ■ = f 0 , 0029/ 11». 1 .0 5 x i o b . 2 0 ,0 0 0
1.
Vb ^
The c o s t ,o f . e l e c t r i c i t y w i l l b e in c lu d e d in th e m is c e lla n e o u s
c o s t s , w h ich w i l l b e s e t a t $ 0 .0 1 p e r p o u n t o f f i n i s h e d
p r o d u c t.
Summary o f r e a g e n t an d p r o c e s s in g c o s t s p e r 'p o u n d " o f MnOg.
R eag en ts
H eat
M is c e lla n e o u s
T o ta l
$ 0 .1 2 8 1
0.0020
0 .0 1 ■■
*I,
' $ 0 . 1410/ i b .
I,
0.53
c> 1QM
-2 0 -
F ix e d O p e ra tin g C o s t:
D i r e c t L ab o r:
9
4
3
I
3
C o s t/d a y
O p e r a to r s - $ 2 . 5 0 / h r .
L a b o re rs $ 1 . 7 5 / h r .
M ain ten an ce $ 2 .7 5 /h r .
C hem ist $385/m o.
T e c h n ic ia n s $>3Q0/mo.
la , A
KLd
1%,$)
I SoO
A -StOO
$ IS O .OO
' 5 6 .0 0
6 6 .0 0
1 3 .0 0
30 .0 0
$ 3 4 5 .0 0
' 4 5 .0 0
3 9 0 .0 0
Employee b e n e f i t s (13%)
T o ta l d i r e c t l a b o r
36 I
7Q
£7
"5.731
3 SS
E x p en ses:
I C hem ical E n g in e e r $ 4 5 0 /mo.
2-S oo
StQ QO
I S alesm an $ l 0 , 0 0 0 / y r .
O f f ic e an d A d m in is tr a tiv e ex p en se,
D e p r e c ia tio n (Tg y e a rs ).
R e p a ir m a te r ia ls .
B u ild in g r e n t .
Burden I . ,
■Total e x p e n s e s (120% d i r e c t la b o r) .
T o ta l f ix e d o p e r a t i n g c o s t.
$ 858/ day_________
2 0 ,0 0 0 I b /d a y
1 5 .0 0
2 8 .0 0
1 6 5 .0 0
4 5 .0 0
'"'-1 0 . 0 0 '
■.
1 9 5 .0 0
^ 6 8 .0 0
K °1
35
SCVa
HZ
Io
6 ©O
ISl^ ■
I 8 5 8 .0 0
$ 0 . 0/ 29/ l b .
Ox^ 3 0 |
T o ta l m a n u fa c tu rin g c o s t e q u a ls th e sum o f th e m a t e r i a l , l a b o r and
ex p en se c o s t s /
M a te r i a l c o s t
L abor an d ex p an se
T o ta l m a n u fa c tu rin g p o s t
F re ig h t
f
T o ta l c o st* F . 0 .' B.
b a tte ry fa b ric a tio n
p l a n t , p e r I)).
$ .0-r-ir/iO
■ 0 .0 4 2 9
Q l OS oJ i
' ( C /1839 /
-I.
Qf-Ol - ■ , -fi),. i.O »2. S
. & 0 .1 9 3 9
^7- S
3
,? ^
2,1 '
' G ross p r o f i t e q u a ls s e l l i n g p r i c e l e s s c o s t .
go'
:
S e l l i n g p r i c e $ 0 . 2 5 / l b . - $ Q 1 . 9 3 9 / l b . - $ 0 .0 5 6 1 /l b .
I 0
B urden c o n s i s t s o f u n f o r e s e e n expenses.,, l o c a l ,ta x e s an d c o n tr ib u ­
t i o n s f o r th e s u p p ly o f u t i l i t i e s .
-
$ 0 .0 5 6 1 / l b ,
21
-
x 7 ,3 0 0 ,0 0 0 I b . / y r . =
G ross p r o f i t
■Less-:
P r o p e r ty t a x (3^)
Incom e t a x e s •(52%)
Met p r o f i t p e r y e a r
I 4 0 1 ,0 0 0 /y r„
$ 4 0 1 ,0 0 0
4 .3 6 8
$ 3 9 6 .6 3 2
2 0 9 .0 0 0
.$ 1 8 7 ,6 3 2
In v e s tm e n t:
L i s t e d below i p th e e s tim a te d i n i t i a l in v e s tm e n t re q u ire m e n t f o r a
te n to n p e r day p l a n t .
T ix e d a s s e t s ( P l a n t c o s t)
D evelopm ent
2 0 ,0 0 0
I n v e n to r y :
MnSO^
KMn04
ZnO
F in is h e d Goods
$ 2 ,0 0 0
1 5 ,0 0 0
1 ,0 0 0
1 5 .0 0 0
A cco u n ts R e c e iv a b le
A cco u n ts P a y a b le
$ 1 1 2 ,6 0 0
'
Cash
T o ta l in v e s tm e n t r e q u ir e d
3 3 .0 0 0
1 5 0 ,0 0 0
5 0 ,0 0 0
50 ,0 0 0
: ■ I 4 1 5 .6 0 0
The r e tu r f i on th e . r e q u ir e d in v e s tm e n t f o r a s e l l i n g p r i c e o f
$ -0 .2 5 p e r pound i s :
1 . 1 8 7 .6 3 2 -X-.-IOQv = 4.5 p e r c e n t.
$ 4 1 5 ,6 0 0
Summary:
The- a c t u a l c o s t o f a p l a n t t h a t w ould p ro d u c e 10 to n s p e r - d a y o f
b a t t e r y a c t i v e m anganese d io x id e by th e p o ta s s iu m p e rm a n g a n a te -o x id a tio n
-2 2 -
o f m anganese s u l f a t e i s $ 1 1 2 ,6 0 0 .
I t w i l l c o s t a b o u t •$> 0 .1 9 3 9 p e r
pound to p ro d u c e b a t t e r y a c t i v e m anganese d io x id e by t h i s s y n th e s is and
d e l i v e r i t to a b a t t e r y f a b r i c a t o r .
The n e t p r o f i t p e r y e a r w i l l be
i n th e o r d e r o f $ 1 8 7 ,6 3 2 an d w i l l r e p r e s e n t 45 p e r c e n t o f an e s tim a te d
c a p i t a l - re q u ire m e n t o f $ 4 1 5 , 6 00.
•-
■—
r"
-■
. . .
-
*
.
.
a
The P o ta s s iu m P erm an g an ate O x id a tio n o f Manganous G n lia te
M ethods o f p r e p a r a t io n and a n a l y t i c a l and t e s t d a t a f o r th e man­
g a n e se d io x id e sp ecim en s p ro d u ced in t h i s s tu d y a r e shown in th e A p p en d ix ,
T a b le I and T a b le I I . . Ar code was u s e d to d e s ig n a te d i f f e r e n t sampf’e s ,
th e f i r s t - l e t t e r . , S, d e n o te s m anganese s u l f a t e , th e seco n d g ro u p , KPj
d e n o te s .p o ta s s iu m p e rm a n g a n a te , an d th e num ber d i f f e r e n t i a t e s th e r e a c t i o n s .
The
s u f f i c i n g , o f th e l e t t e r , H, a f t e r th e number i n d i c a t e s h e a t t r ^ h t -
m ent o f a p o r t i o n o f th e sam p le, th e l e t t e r s > HS, d e n o te s hy d ro g en s u l f i d e
tr e a tm e n t^ w h ile th e a d d i t i o n o f lo w e r c a s e l e t t e r s d i f f e r e n t i a t e s
Sub­
s e q u e n t tr e a t m e n t s .
T h is study was term ed t h e 'S-KF
S y n th e s is ;-
The
e q u a tio n i s : 3MnS0^ ( a q . ) J+ 2KMn0^ ( a q .) 4- 2 H p P l(Io )
K2SO4 ( a q .) + 2h 2S° 4 ( a q . ) . _
g e n e r a l chem ical> SMnQjxHpQ ( s . ) +
'
Thee, r e a c t i o n s o f t h i s s y n th e s is w ere c a r r i e d o u j i n th e mapner,
d e s c r ib e d in th e s e c t i o n , " M a te r ia ls an d M eth q d s."'
F r e t i o u s work r e p o r t e d by B erg e t a l „
( I ) , and H e in f e ld e r ( 4 ) ,
i n d i c a t e d t h a t thte p r o d u c t o f an S-KP r e a c t i o n gave an u n f a v o r a b le d r a in
life ,
K l e i n f e l d e r (4) i n d i c a t e d t h a t s p e c i f i c a t i o n m anganese d io x id e
-2 3 -
couI d n o t be p ro d u c e d from t h e -S-ItP r e a c t i o n a t c o n c e n tr a ti o n s ' o f from
0 .0 6 2 5 to 1 .0 m o les o f m anganese s u l f a t e p e r l i t e r o f r e a c t i o n volum e.
T h is in fo rm a tio n s u g g e s te d tr e a tm e n t o f th e p r o d u c t m anganese d io x id e to
u p g ra d e i t s d r a in l i f e .
One tr e a tm e n t known to be o f v a lu e ,.was th e low
te m p e r a tu r e h e a t i n g o f m anganese d io x i d e .
T h is tr e a tm e n t was' t r i e d on -
th e re m a in in g p r o d u c t o f r e a c t i o n S-KP-5 and d e s ig n a te d sam ple S-K P-5H.
T h is sam ple had 2 .2 5 h r .- H . D. an d 146. h r . - L . D.
S in c e sam ple S-KP-5 waq made by K le ir if e ld e r ( 4 ) , i t s m ethod o f
p r e p a r a t i o n i s g iv e n b elo w .
" D is s o lv e d 160 gm. MnSO^iIfeO in I l i t e r Hgp; h e a te d to 8 5 ° C ,;
h d d ed , d ro p w is e , o v e r a 2 .2 5 h r ; p e r io d , 105 gm.. KMnO^ in 2 { l i t e r s 'HgO.
R e a c tio n volume was m a in ta in e d a t I l i t e r .
R e a c tio n tim e was 6 h r . a t
arid a v e ra g e te m p e r a tu r e o f 85°C . The r e a c t i o n m ix tu re was c o o le d ,' y /ith
a g i t a t i o n , • f o r 16 h r . b e f o r e w a sh in g . The p r o d u c t was b a l l - m i l l e d f o r
2 h r . a f t e r , d r y ip g ."
..Because o f th e s u c c e s s o f sam ple S-K P-5H i t wa.s d e c id e d to i n v e s t i ­
g a te f u r t h e r , th e r e a c t i o n v a r i a b l e s and h e a t t r e a t i n g o f sa m p le s.
R e a c tio n •C o n c e n tr a tio n S tudy
K l e i n f e l d e r (4 ) r e p o r t s " f i v e r e a c tio n s " in " w h ic h th e c o n c e n tr a tio n s
o f th e r e a c t a n t s w ere v a r ie d .,
T hese r e a c tio n s - ( S - K P - l, 2 a , .3 , 4 ,- and 5)
o f h i s w i l l be u s e d i n t h i s s tu d y a lo n g w ith - .r e a c tio p s S-K P-6 , 7," 8 ,, 1 5 ,
1 6 , and 1 7 .
’
T a b le I I I an d F ig u r e 4 i s th e
r e a c t i o n volume =
'
'
i
A ppendix ' show th e e f f e c t
of tp ta l
The cu rv e in F ig u r e 4 i n d i c a t e s t h a t a d i l u t e s o lu tio n
o f m anganese s u l f a t e should be u s e d .
A lth o u g h none p f th e sam p les met
I
s p e c i f i c a t i o n s , d r a i n v a r ia n c e was from 1 .0 to 4 -4 h r .- H , D. and 50 to
—24—
124 h!r.' L 4 D.
The t o t a l -rea-ction volum e was v a r ie d from one Iite jp i to
40 l i t e r s p e r m ole o f m anganese s u l f a t e .
The f a c t t h a t a b e t t e r d r a ip t e s t a ris e s ! from th e u s e o f a d i l u t e
s o l u t i o n o f m anganese s u l f a t e i s shown in T a b le IV and F ig u r e 5 in th e
A p p en d ix ,
The above t a b l e an d f i g p r e show th e e f f e c t o f c o n c e n tr a tio n o f
m anganese s u l f a t e a t c o n s ta n t,.c o n c e n tr a tio n o f p o ta s s iu m p e rm a n g a n a te .
T h e --b a s is - f o r co m p ariso n h a s been ta k e n a s one e q u iv a le h C e o f p o ta ss iu m
perm anganate p e r m o le o f qiaganese s u l f a t e p e r two l i t e r s d f s o l u t i o n ,
: :
1
Sample- S-KE-17» having a c o n c e n tr a tio n o f 0 ,0 2 5 mole o f m anganese s u l f a t e
p e r l i t e r o f s o l u t i o n , shqws th e b e s t d r a in t e s t w ith 4 -0 h r . -EJ„ D* rand
106 h r . - L., D,
T a b le V and F ig u r e 6 in t h e
A ppendix show th e e f f e c t o f th e con­
c e n t r a t i o n o f p o ta s s iu m p erm an g an ate b a s e d on a c o n c e n tr a ti o n o f -JAani
'
,
■
gapede d p l f a t e d f o|ie moj.e p e r seven l i t e r s of- s o l u t i o n . Two concen­
t r a t i o n s o f p o ta s s iu m p e rm a n g a n a te , 0 /5 7 a n d '1 .1 3 0 5 m ole e q u iv a le n ts
(b a s e d op one m ole o f m anganese s u l f a t e ) , w ere u se d f o r t h i s - s t u d y .
The p r o d u c t o f th e m ore ■C o n c e n tra te d s o l u t i o n h ad th e b e t t e r d r a ip t e s t
( 1 ,9 h r , H. D ,, 55 h r . L . p. v s . 0 .9 h r . H.
42 h r . L , D. ) . ' The
q u a n t i t y and scope o f th e d a te p r e s e n te d in t h i s s tu d y p r e v e n t th e
p o s tu la tio n o f a p r in c ip le .
The
/
sttid y o f th e e f f e c t o f th e c o n c e n tr a tio n o f th e r e a c t a n t s
h a s shown t h a t , w h ile ho s p e c i f i c a t i o n m a t e r i a l was p ro d u c e d , th e b e s t
d r a i n t e s t s o c c u r r e d a t th e more d i l u t e c o n c e n tr a ti o n s on m anganese
s u l f a t e e . g. a b o u t 0 .0 2 5 m oles p e r l i t e r .
A lth o u g h a c o n c e n tr a tio n
-2 5 -
o f 1 .1 3 0 5 m ole e q u i v a le n t s p e r l i t e r o f p o ta s s iu m p erm a n g an ate w as;-the
b e t t e r o f th e ^wo c o n c e n tr a ti o n s chosen- f o r s tu d y , th e d a ta i s to d l i m i t e d to w a r r a n t a d e f i n i t e c o n c lu s io n .
R e a c tio n Time S tu d y
R e a c tio n s S-K P.-l, 8 , 9 , an d IQ w ere u s e d to s tu d y r e a c t i o n tim e .
The c o n c e n tr a tio n o f m anganese s u l f a t e was h e ld c o n s ta n t a t one mole p e r
16 l i t e r s .
The b a s i s f o r co m p ariso n o f th e d r a in d a te f o r th e ajDove-
r e a c t i o n s w i l l be ta k e n a s th e tim e r e q u ir e d to add 105 grams o f p o ta s ­
sium
p erm a n g an ate to th e r e a c t i o n .
A 2 .5 h r . a d d i tio n tim e gave a d r a in
t e s t o f 2 .0 h r . H. D. and 78 h r . 'L . D. w h ile a Lr h r . a d d i t i o n tim e gave
a d r a i n t e s t o f £ . 4 h r . H. D. an d 124 h r . - L . D.- An
a d d i t i o n tim e o f 10
h r . , gave a d r a i n t e s t o f 4 .0 h r . H. D. an d 106 h r . L. D. w h ile a 1 5 h r .
a d d itio n
tim e gave a d r a in t e s t o f 4«3 h r . H. D. and 90 h r ^ L . D.
T h is l i m i t e d s tu d y $ 10ws t h a t th e tim e o f a d d i tio n o f p o ta ss iu m
p e rm a n g an ate
ra te s
i s c r i t i c a l i f i t s r a te o f a d d itio n i s r a p id .
o f a d d i t i o n , n o t t o o - g r e a t an e f f e c t i s e v id e n t.
F o r slp w er
W ith in p ie
l i m i t a t i o n s o f t h i s s tu d y , th e optimum r a t e o f a d d i tio n a p p e a r s to be
2 6 .2 5 grams Of p o ta s s iu m p erm a n g an ate p e r h o u r p e r m ole o f m anganese
s u lfa te .
, R e a c tio n s S-KP-2$ and 19 w ere ru n w i t h 't h e same c o n c e n tr a ti o n s o f
r e a c ta n ts ;
0 .6 m ole m anganese s u l f a t e p e r g a llo n o f s o l u t i o n and 52.5
gram s o f p o ta s s iu m p erm a n g an ate p e r - l i t e r o f s o l u t i o n .
The r a t e o f
a d d i t i o n p f th e p erm an g an ate f o r r e a c t i o n 8-K P -I9- w a s .2 6 .2 5 g ram s-p er
h o u r ^per:vmo-l®-v:of^manganetse.rsulfa t e ;: -T h e rra te •:of " a d d it io n . :of - p erm an g an ate
-2 6 -
to r e a c t i o n S-EP-28 w as-3 5 . grams: p e r rhour p e r m o le :o f m a n g a n e s e - s u lf a te .
The d is c r e p a n c y i n th e d r a in t e s t s o f th e two s a m p l e s 'i s a p p a r e n t;
S-KP-19 (2 6 .2 5 gm. p e r h r . jp er m ole MnSO^. ) had d r a in t e s t s o f 1 .7 5 h r .
H. D, and 76 h r . L. D. w h ile th e d r a in t e s t s f o r S-KP-2S (35 gm. p e r
hr., p e r m ole MnSO ) w ere 0 ,8 1 h r . H. D. an d 58 h r . L. D.
T hese two
r e a c t i o n s i n d i c a t e t h a t th $ b e s t r a t e o f a d d i t i o n o f p o ta s s iu m p erm an g an ate
i s 2 6 .2 5 gram s p e r h o u r p e r m ole o f m anganese s u l f a t e . .
O th e r R e a c tio n V a r ia b le s
The v a r i a b l e o f te m p e r a tu r e was n o t e v a lu a te d b e c a u se w ork done by
p r e v io u s i n v e s t i g a t o r s , B erg e t a l . ( I ) , h ad shown t h a t i n a c t i v e m a t e r i a l
had been forned when t h e 'r e a c t i o n was run a t te m p e r a tu r e s lo w e r th a n th e
b o i l i n g p o ^ n t.
The tim e o f b a l l - m i l l i n g o f th e m anganese d io x id e was n o t i n v e s t i ­
g a te d b e c a u se w ork done by K l e i n f e l d e r ( I ) h ad shown th e p e r c e n t' in c r e a s e
i n d ra fn l i f e to be s m a ll f o r an in c r e a s e d b a l l - m i l l i n g tim e o v e r 2 h r .
R e a c tio n S -K P -Il was ru n t o d e te rm in e th e e f f e c t o f e n la r g in g th e
■T e a c tio n rs lz re -"'on"~fche"drain.l i f e o f th e p r o d u c t.
u n d e r c o n d i tio n s i d e n t i c a l to S -K P -3.
R e a c tio n .S -K P -Il was ru n
Tw ice th e amount q f r e a g e n ts w ere
u s e d i n S -K P -Il a s w ere u s e d i n r e a c tio n S -K P -3 •
The c o n c e n tr a tio n o f mangan
e s e s u l f a t e was one m ole p e r two- l i t e r s o f s o l u t i o n , t h e c o n c e n tr a tio n o f
p o ta ss iu m p erm a n g an ate was one e q u iv a le n c e (b a s e d on ope m ole o f' m anganese
s u l f a t e ) p e r two l i t e r s o f s o l u t i o n .
The r a t e o f a d d i t i o n o f th e perm angan­
a t e was 5 2 .5 gram s p e r h o u r p e r m ole o f m anganese s u l f a t e . . . The resu lt,® o f
S -K P -Il ( 1 .4 h r . H.D. an d 60 h r . L .D .) w ere e s s e n t i a l l y
th e
same a s
-2 7 -
fc-KP-3 (1 -5 h r . H- D- and 44 h r . L- D -)-'
T h is i n d i c a t e s t h a t th e l a r g e r
r e a c t i o n s i z e d o es n o t hav e an e f f e c t on th e produc-jp o f th e r e a c tio n
p ro v id e d a l l v a r i a b l e s a r e th e same in each i n s t a n c y H e a t T r e a tin g S tu d y
The h e a t t r e a t i n g o f th e p r o d u c ts o f th e S-KP s y n th e s is was- i n ­
i t i a t e d w ith s a m p le ' S-KP-5H.
a t 310°C.
The c o n d itio n s f o r th ^ h e a t in g w ere 9. h r .
The s u c c e s s o f sam ple S-KP^5H ( 2 .2 5 h r . H. D ., I 46 h r . -L', D.
v s . 0 -3 h r . ' H. D ., 20 h r . L . D. fo p S-KP-5) p rom pted h e a t t r e a t i n g o f
s u b s e q u e n t sam p les a t c o n d i tio n s s i m i l a r to th o s e o f S-KP-5H.
o f su c c e e d in g r e a c t i o n s was h e a t t r e a t e d .
A' p o r tio n
The h e a t t r e a t i n g o f sam ples
o f r e a c t i o n s S-KP- 6 th ro u g h 2 1 , w ith th e e x c e p tio n o f r e a c t i o n s S-KP-13,
and 19 , was c a r r i e d o u t f o r 9 h r . a t 3 1 0 °C.
M ost o f th e sam p les made
by t r e a t i n g m anganese d io x id e in t h i s A anper d id n o t g iv e aq a p p r e c ia b ly
im proved d r a in t e s t o v e r th e o r i g i n a l p r o d u c t.
o r n e a r l y m et s p e c i f i c a t i o n ^ w i l l be n o te d .
•
Those sam p les w hich met
Sample S-KP-8H m et th e low
d r a i n s p e c i f i c a t i o n w ith a d r a i n t e s t o f 134 h r ;
Sample S-KP-8 was made
w ith a c o n c e n ty a tio p o f 0 .0 7 2 4 m ole m anganese s u l f a t e p e r l i t e r o f s o l u t i o n ,
p o ta s s iu m p erm a n g an ate o f th e c o n c e n tr a ti o n , 0 .3 8 mole p e r l i t e r o f s o l u t i o n ,
wap added a t a r a t e o f 2 6 .2 5 gram s p e r h o u r p e r mole o f m anganese s u l f a t e .
S -K P -5,
whose h e a t t r e a t e d a n a lo g s m et th e low d r a in s p e c i f i c a t i o n ,
was made from manganese- s u l f a t e of. a c o n c e n tr a tio n o f one m ole p e r l i t e r
o f s o lu tio n .
P o ta sb iu m p erm a n g an ate f o r th e fo r e g o in g r e a c t i o n -was o f
th e c o n c e n tr a tio n 0 .3 3 2 m ole p e r l i t e r o f s o lu ti o n an d was atiged a t a
r a t e o f 42 grams p e r h o u r p e r m ole o f m anganese s u l f a t e .
Sample S-KP-8
-2 8 -
d i f f e r e d from sam ple 8-K P-5 w ith r e s p e c t to c o n c e n tr a tio n o f a l l f e a e t a n t s
and r a t e o f a d d i t i o n o f p o ta ss iu m p e rm a n g a n a te ^
D e s p ite .th e d if f e r e p c e ,
.
th e h e a t t r e a t e d p o r t i o n s o f each r e a c t i o n m et th e low d r a in s p e c i f i c a t i o n
Sam ples S-K P-S, 1 3 , ah d 14 w ere made in th e fo llo w in g m anner; .. TM
c o n c e n tr a tio n o f m anganese s u l f a t e was 0 .0 7 2 4 mole p e r - l i t e r , p o ta s S t™ ■
p erm a n g an ate vjas ad d ed a t a r a t e o f 2 6 .2 5 grams p e r h o u r p e r m ole 'o f
m anganese s u l f a t e , th e c o n c e n tr a tio n o f th e p erm a n g an ate was O.3 8 m ole
p e r l i t e r o f s o lu tio n .
S in c e sam p les S-KP-SH and 14H w ere p re p a re d
"by h e a t i n g . a p o r ti o n o f tfye a n a lo g o u s o x id a tio n r e a c t i o n p r o d u c t f o r 9 h r .
a t 310° C ., t£ e d f a in t e s t s f o r th e s e sam p les sh o u ld be in c lo s e a g re e m e n t,
^he d r a i n t e s t s f o r S-KP-14H w ere 3 .5 h r .r H . D. and 128 h r.--L ? D. w hich
C lo s e ly a p p ro a c h e s th e d r a in l i f e o f S^KP-SH (4 °0 h r . H . D.> 134 h r . L .D .)
Sample S-KP-13 was made w ith t e c h n i c a l g ra d e c h e m ic a ls and sam ple S-KP-13H
was made by h e a t in g a p p o r tio n o f sample" S'-KP-1 3 f o r 2 0 - h r .
a t 310° 0 .
The d r a i n t e s t s f o r sam ple S-KP-13 w ere 3 .6 h r . Hk D0. an d 35 h r.' L j, D.
R e a c tio n S-KP-19 was made by co m b in in g p o ta ss iu m p erm an g an ate o f a
c o n c e n tr a ti o n o f 5 2 .5 gram s p e r l i t e r o f s o lu ti o n w ith m anganese s u l f a t e
o f a c o n c e n tr a tio n o f 0 .6 m ole p e r g a llo n o f s o lu ti o n a t a r a t e o f 2 6 .2 5
grams p e r h o u r p e r m ole o f m anganese s u l f p t e .
The p r o d u c t o f r e a c tio n
S-KP-19 was d iv id e d i n t o n in e 70 gram p o r t i o n s , each o f w hich was givpn a
- O if f e r e n r t- - M a t"t r e a t m e n t .
T a b le V I^ an ti-P ig u r e 7" in : t h e -Appendix -shpw th e
e f f e c t o f th e te m p e r a tu r e o f h e a t in g on th e d r a in l i f e o f S -K P-19.
te m p e r a tu r e s ch o sen w ere 2 3 0 , 2 6 5 ,. 310, and 355°C .
The
The te m p e r a tu r e o f
230°C . damaged th e o r i g i n a l p r o d u c t l e a s t ( 4 .0 h r . H .D .,
77 h r . L. D. v s .
•
r29:
4 =75 h r . H . - D . , 76 h r . L= D. f o r S -K P -1 9 )=
T ab le V II and F i g u r e ' 8, in- th e
A ppendix shpw th e r e s u l t s o f a v a r ie d h e a t in g tim e on sam ple S-KP-19.
H e a tin g tim e s o f 3» 6 , 1 5 , a nd 24 h o u rs w ere t r i e d .
O Q pstant a t 305oC.
The te m p e ra tu re was
As b e f o r e none o f th e h e a t t r e a t e d sam p les showed
im provem ent o v e r th e o r i g i n a l l i f e o f S -K P -19.
The h e a t i n g tim e o f s i x
h o u rs y ie ld e d a p r o d u c t whose d r a in t e s t c l o s e l y approached t h a t o f th e
o r i g i n a l p r o d u c t (4=6 h r . H= D=, 62 h r . L= D= y s . 4=75 h r . H. D ., 76 h r .
L.D.).
To t e s t th e r e s u l t s o f th e above s t u d i e s , sam ple S-KP-19Hi .was m ade.
T h is sam ple was h e a te d a t a te m p e r a tu r e o f 238°C . f o r 6 h r .
In com parison
w ith sam ple S -K P -19, sam ple S-KP-19Hi had a t e s t o f 0 .2 5 h r . l e s s
on h ig h
d r a in and a low d r a in t e s t o f 5 h r . lo n g e r t h a t S-KP-19 =
A lth o u g h th e r e s u l t s o f th e f o r e g o in g s tu d y w ere n o t d e f i n i t e l y con­
c l u s i v e , a h e a t in g tim e o f 6 h r . and a te m p e ra tu re o f 220°C . was chosen f o r
a l l re m a in in g h e a t t r e a t m e n t s .
Sam ples S-KP-29H and 30H s h o u ld have had
low d r a in t e s t s m e e tin g o r n e a r l y m e e tin g low d r a in s p e c i f i c a t i o n s .
T pese
two r e a c t i o n s d u p l i c a t e d th e m ethod o f p r e p a r a t io n o f s u c c e s s f u l r e a c t i o n s
S-K P-8H an d 14H.
(The c o n d itio n s f o r th e s e r e a c t i o n s a r e g iv e n b e lo w .)
The d r a in t e s t s f o r r e a c t i o n S-KP-29H w ere 1 .0 h r . H. D= an d 44 h r . L. D.
w h ile t h e d r a in t e s t s f o r S -KP-30H w ere 1 .5 h r . H= D. an d 166 h r ; ,L ' D.
6
An u n p u r i f i e d m anganese s u l f a t e was u se d f o r r e a c tio n S -K P -2 9 .
The p o o r
!
p e rfo rm a n c e o f S-KP-29H i n d i c a t e s th e n e c e s s i t y o f p u r i f i c a t i o n o f th e
m anganese s u l f a t e b e f o r e o x id a tio n f o r th e p ro d u c tio n o f s p e c i f i c a t i o n
g ra d e m a t e r i a l .
I t may be co n c lu d e d t h a t a m ethod o f p ro d u c in g b a t t e r y a c t i v e
-3 0 -
m anganese d io x id e t h a t w i l l m eet low d r a in s p e c i f i c a t i o n s h a s been
d e v e lo p e d .
The s u g g e s te d p ro c e d u re is - t h a t f o r S-KP-30H , and
i s as
. fo llo w s :
R eac tan ts-: T e c h n ic a l g rad e m anganese s u l f a t e and p o ta s s iu m perman­
g a n a te . ,The m anganese s u l f a t e i s to be p u r i f i e d by th e
a d d i t i o n o f 10 gm„ z in c o x id e p e r 124 gm. p u re m anganese
s u lfa te .
C o n c e n tr a tio n : M anganese s u l f a t e - 8 8 .6 gm. p e r l i t e r . P o ta ssiu m
p e rm a n g a n a te - 5 2 .5 gm, p e r l i t e r .
A d d iti o n : 2 6 ,2 5 gm. p o ta s s iu m p erm a n g an ate p e r h o u r p e r 124 gm.
pg?0 m anganese s u l f a t e .
^
T e m p e ra tu re : A p p ro x im a te ly " 9 0 °C.
C o o lin g ; tib o l, w ith a g i t a t i o n , f o r 16 h r . b e fo re f i l t e r i n g .
W ashing: Wash u p t i l th e pH o f th e e f f l u e n t wash w a te r i § betw een
6 .8 - 7 . 0 .
.D ry ip g: Dry p r o d u c t a t - I l O 0C. f o r 48 h r .
H e a tin g : M o rta r th e d r i e d p r o d u c t, t r e a t th e -4 0 m esh m a t e r i a l in
a m u ffle f u r n a c e f o r 6 h r . a tv 2 2 0 °C .
I t s h o u ld be p o in te d o u t t h a t th e te m p e r a tu r e u se d f o r t r e a t i n g th e
sam ples is - t h a t te m p e r a tu r e in th e f r e e sp a c e o f th e m u f f le f u r n a c e r in
w hich h e a t t r e a t i n g o f th e above sam ples to o k p la c e .
The tim e o f h e a t in g ,
s u g g e s te d a b o v e , i s t h a t tim e found to b e m ost f a v o r a b le f o r a 70 .gm,
sam p le.
I t i s s u g g e s te d t h a t th e tim e o f h e a t in g and th e 't e m p e r a tu r e o f
h e a t in g f o r d i f f e r e n t s iz e d sam p les may be d i f f e r e n t th a n th e r e s u l t s o f
t h i s s tu d y .
A d a p ta tio n o f C om m ercial R eag e n ts to th e R e a c tio n
T e c h n ic a l g rad e' r e a g e n ts w ere u s e d in t h r e e r e a c t i o n s i n an a tte m p t to
e v a lu a te th e co m m ercial a d a p t a b i l i t y o f th e r e a c t i o n .
The r e a c tio n s u se d
f o r t h i s s tu d y w ere S-KP-12,^, 1 3 , and 1 4 . ' S-KP-12 had th e follow ingre a c tio n r e n d i t i o n s t h e
c o n c e n tr a tio n o f m anganese s u l f a t e was one m ole
p e r two l i t e r s o f s o l u t i o n , th e c o n c e n tr a tio n o f p o ta s s iu m 'p erm an g ap ate
-3 1 -
was one e q u i v a le n t (b a s e d on one m ole o f m anganese s u l f a t e ) p e r two l i t e r s o f
s o lu tio n .
The r a te .of a d d i t i o n o f th e p erm a n g an ate was 5 2 .5 grams p e r h o u r
p e r m ole o f m anganese s u l f a t e .
T hese c o n d itio n s a r e th e same c o n d itio n s
s p e c i f i e d f o r .,r e a c tio n s S -K P -Il and 3 .
The above , r e a c t i o n c o n d itio n s w ere
p ic k e d b e c a u se S -K P -Il h ad been a c lo s e d u p l i c a t i o n " o f S-KP-3 a n a th e r e b y , th e
d r a in t e s t o f S-KP-12 c o u ld be p r e d i c t e d .
S-KP-12 had. a d r a in t e s t o f 2 .5
h r . H. D. and 42 h r . L. D ., w hich com pared c l o s e l y w ith S - K P - I l w ith a d p .in
t e s t o f 1 .4 h r . H , D, an d bO. h r . . L- D.
The p r o x im ity o f th e . above v a lu e s ' o f
th e d r a in t e s t s i n d i c a t e d t h a t thte i m p u r i t i e s in th e m anganese s u l f a t e
s u p p lie d by th e G arus C hem ical Co. o f L a S a lle , I l l i n o i s , w ere n o t d e t r i ­
m e n ta l to b e t t e r y l i f e .
To f u r t h e r i n v e s t i g a t e t h i s h y p o th e s i s , r e a c t i o n s S -^ P -1 3 and 14 w ere
■>
ru n .
.
'
'
■
The c o n d itio n s f o r th e s e two r e a c t i o n s w ere th e same a s th o s e f o r
r e a c tio n . S-K P-S.
They a r e a s f o llo w s : C o n c e n tra tio n o f 0 .0 7 2 4 mole rnanr-
g an ese s u l f a t e p e r l i t e r o f s o l u t i o n , 0 .3 8 m ole p e r l i t e r o f s o lu ti o p o f
p o ta s s iu m p erm a n g a n a te , ad d ed a t a r a t e o f 2 6 .2 5 grams p e r h o u r p e r molp o f
•manganese s u l f a t e .
R e a c tio n S-KP-S was made u s in g C. P . g ra d e c h e m ic a ls ;
r e a c t i o n S-KP-13 u s e d t e c h n i c a l g ra d e r e a c t a n t s ; r e a c t i o n S-KP-1 4 u se d a
p u r i f i e d t e c h n i c a l g ra d e m anganese s u l f a t e and t e c h n i c a l g ra d e p o ta ss iu m
p e rm a n g a n a te .
Z inc o x id e was chosen a s th e p u r i f i c a t i o n a g e n t b e c a u se any
i o n i c z in c compounds form ed d u rin g th e p u r i f i c a t i o n w ould a c t a s a c a t a l y s t
to th e o x id a tio n r e a c t i o n , B erg e t a l .
(I).
As would be e x p e c te d , th e sam ple made from p u r i f i e d m anganese s u l f a t e
had a s l i g h t l y h ig h e r d r a in l i f e , e . g . S-K P-13> 4 .2 5 h r . H. D ., H O h r . L . D .,
S-KP- 1 4 , 4 . 6 h r . EL D ., 122 h r . -L. D.
B o th r e a c t i o n s p ro d u ced sam p les t h a t
had d r a in l i v e s c l o s e to t h a t o f sam ple S-KP-8 ( 4 . 4 h r . -H. D., 124 h r ; L. D. j .
R e a c tio n S-KP-14 th e n becom es a d u p l i c a t i o n o f r e a c t i o n S-KP-8 , w h ile th e
r e s u l t s o f r e a c t i o n S-K-Pt-IS show t h a t p u r i f i c a t i o n o f th e m anganese s u l f a t p i s
u n n e c e ssa ry .
........ - - -
I t i s p o s s i b l e - t o c o n c lu d e , from t h i s b r i e f s tu d y , t h a t th e p u r i ­
f i c a t i o n o f com m ercial g ra d e m anganese s u l f a t e i s n o t n e c e s s a r y to ijiake. s p e c i f i c a t i o n b ettery -aetisy e^ m au g an B S e d io x id e ;- ... (B ased on m anganese s u l f a t e
m a n u fa c tu re d by th e C aru s C hem ical Co.)
O th e r M ethods
• From th e f o r e g o in g s t u d i e s , i t i s e v id e n t t h a t o n ly one m ethod o f
p ro d u cin g '^ , s p e c i f i c a t i o n b a t t e r y a c t i v e m anganese d io x id e h a s b<s_e%- fo p n d .
A lth o u g h a f u l l i n v e s t i g a t i o n o f r e a c t i o n v a r i a b l e s was n o t co m p lete d , i t
was f e l t t h a t enough w ork h ad been done to s u b s t a n t i a t e th e h y p o th e s is t h a t
in o r d e r to make s p e c i f i c a t i o n b a t t e r y a c t i v e m anganese d io x id e by th e S-KP
r e a c t i o n , i t s h a l l be n e c e s s a r y to in t r o d u c e an a d d i t i o n a l s te p i n t o th e
r e a c t i o n se q u e n c e . ,
The v a r io u s m ethods t r i e d a r e l i s t e d below .
H ydrogen S u lf id e A d s o r p tio n - D e s o rp tio n
'
' ' -
Sample S-K P-6H-HS wap made t o - d e te rm in e th e e f f e c t o f a d s o r b in g and
th e n d e s o rb in g h y d ro g en s u l f i d e g as on m anganese d io x id e .
T h is sam ple was
p r e p a r e d by su sp e n d in g 100 grams o f sam ple S-K P-6h in 3 l i t e r s o f w a te r and
30 c c . o f p h o s p h o ric a c i d ( s i r u p y ) .
Hydrogen s u l f i d e g as was b u b b le d i n t o
th e m ix tu re u n t i l an a p p r e c ia b le c o l o r change was n o te d .
The sam ple was
-3 3 -
f i l t e r e d and p la c e d in a m u f f le f u r n a c e a t 3Q0°C. f o r 2 h r .
B ecau se th e
d r a in t e s t , a f t e r t r e a t i n g was n o t g r e a t l y im proved o v e r sam ple S-KlMbH,, no
more sam p les werd made by t h i s p r o c e s s .
\
H y d ro c h—lor, ric A cid —f
L each
.
B erg e t a l .
( I ) l i s t s a m ethod o f t r e a t i n g m anganese d io x id e y d th
h y d r o c h lo r ic a c i d , w hereby th e b a t t e r y l i f e o f th e m anganese d io x id e ' i's im­
p ro v e d ..
U sin g th e ab o v e m ethod o f l e a c h i n g , two sam p les w ere made; S -K P -Ila
and 1 2 a .
The d r a in l i f e o f each o f th e s e sam ples was I e s a th a n t h a t o f th e
o r i g i n a l sam ple and f o r t h i s r e a s o n , f u r t h e r work was n o t u n d e r ta k e n .
Ammonium H ydroxide D ig e s tio n
~
• ■
If-;'
D ig e s tio n o f sam ple S-KP-16 in ammonium h y d ro x id e was t r i e d .
A p p ro x im a te ly 200 gram s o f S-KP-16 was d ig e s t e d in a s o l u t i o n o f 1 0 0 'c c .
bone, ammonium h y d ro x id e in 3 l i t e r s w a t e r ,
T h is d i g e s t i o n p ro v ed d e t r i ­
m e n ta l to b o th h ig h d r a i n an d low d r a in b a t t e r y l i f e , r e l a t i v e t o ' th e
o r i g i n a l sam p le.
I n c o r p o r a t io n o f an A cid in th e R e a c tio n M ix tu re
Four
r e a c t i o n s w ere run in t h i s s e r i e s ; two r e a c t i o n s u s in g ,h y ­
d r o c h l o r i c a d d and two r e a c t i o n s u s in g n i t r i c a c i d .
S -K P -20, 2 1 , 2 2 , an d 2 3 .
They a r e r e a c t i o n s
The c o n c e n tr a tio n o f m anganese s u l f a t e ' (.one m ole
p e r 2 I t e r s o f s o l u t i o n ) and p o ta s s iu m p erm an g an ate (o n e e q u iv a le n c e p e r ■
m ole o f m anganese s u l f a t e p e r 2 l i t e r s o f s o lu ti o n ) was c o n s ta n t th ro u g h o u t
t h i s s e r i e s , a s was th e m ethod o f p r e p a r a t i o n .
O n e -te n th , m ole anci 0 .2 5 m ole
o f h y d r o c h lo r ic a c i d p e r mole o f m anganese s u l f a t e , w ere ad d ed to r e a c t i o n s
S-KP-20 and 21 r e s p e c t i v e l y .
The d r a in t e s t s f o r th e s e two r e a c t i o n s a r e :
—3 4 —
S-K P-20, 1 ,0 5 h r ; HoD., 37 h rv L .D .J S -K P -21, 2 .3 h r . H .D ., 50 h r . L .D .
0 n e - t6 n th m ole an d 0 .2 5 m ole o f n i t r i c a c i d p e r mole o f'm a n g a n e se s u l f a t e ,
w ere added to r e a c t i o n s S-K P-22 and 23 r e s p e c t i v e l y ;
th e s e two r e a c t i o n s 'a r e : S -K P -22, 2 .3 h r .
The d r a i n t e s t s f o r
H .D ., 8? h r .
L .D .j S-K P-23, 1 .0
h r . H .D ., 38 h r ; L .D .
Hope o f . t h e sam p les had d r a i n t e s t s w hich m et s p e c i f i c a t i o n s ;
'F u r th e r
s tu d y was n o t m ade.
C o n v ersio n o f th e M anganese 'S u l f a t e to M an g an ese. C h lo rid e
K le i n f e ld ^ r (4 ) was s u c c e s s f u l i n p r o d u c in g s p e c i f i c a t i o n b a t t e r y
a c t i v e m anganese d io x id e u sin g - m anganese c h l o r i d e an d p o ta s s iu m "perm anganate „
R e a c tio n S-KP-31 was ru n by o x id i z in g m anganese c h lo r id e (made by t r e a t i n g
m anganese s u l f a t e w ith c a lc iu m c h l o r i d e ) w ith p o ta ss iu m perm anganate" by a
.1
>
,
m ethod o u t l i n e d by K l e i n f e l d e f (4 )» The d r a in t e s t o f sam ple S -K P -^ l'.was 1 . 0
h r . H.D. an d 57 h r ; L .D .
S in c e th e u s u a l S-KP s y n t h e s i s c o n ta in s one l e s s s t e p , th e '.process''':in­
v o lv in g th e c o n v e rs io n o f th e s u l f a t e to th e c h l o r i d e h o es . n o t a p p e a r a s
i
f a v o r a b l e a s th e d i r e c t o x id a tio n from th e econom ic s t a n d p o i n t.
I n c o r p o r a t io n o f "C arbon"B lack■I n th e R e a c tio n "M ixture
In an a tte m p t to e v a lu a te th e e f f e c t o f s u r f a c e on th e fo rm a tio n o f
ganpa p h a se m anganese d io x i d e , carb o n b la c k was ad d ed to re a c tio n -'S -K P -3 2 .
E x c e p t f o r th e a d d i t i o n . o f th e carb o n b la c k , r e a c t i o n S-KP-32 i s a d u p l i c a t e
o f r e a c t i o n Sr-KP-8.
One e q u iv a le n c e ( p e r m ole o f m anganese s u l f a t e ) o f
p o ta s s iu m p erm a n g an ate i n two l i t e r s o f s o l u t i o n was ad d ed -to ' one.:.mole'-'of
m anganese s u l f a t e i n 16 I q t e r s o f s o l u t i o n .
F i f t e e n gram s o f c a rb o n " b la c k
-3 5 -
w ere su sp en d ed in th e m anganese s u l f a t e s o lu tio n ,,
D e s p ite th e f a c t t h a t
th e carh o n b la c k was n o t rem oved b e f o r e - 'f a b r i­
c a t io n o f th e sam ple i n t o c e l l s , th e d r a in l i f e o f 2„5 hr-. H„D, an d 111; h r 0
L.D o, f o r sam ple S -K P -32, c l o s e l y a p p ro a c h e s th e d r a in l i f e o f S-KP-^S;'(4o4
h r o' HoDo, 124 h r ; LoDo)
A e r a tio n o f th e R e a c tio n .M ix tu re
In o r d e r to a g i t a t e a ,r e a c tio n m ix tu r e - ( S-KP^lS ), a i r was ‘b u b b le d
i n t o th e r e a c t i o n , S a m p l e ■'S-KP-18 was p r e p a r e d in a r e a c t i o n ,’v e s s e l" c o n - '
t a i n in g. 8000 grams o f f l i n t p e b b le s ,.
The c o n c e n tr a tio n o f r e a c ta n ts " was 0 ,1
m ole m anganese s u l f a t e p e r l i t e r o f s o l u t i o n g, one e q u iv a le n c e (KM,rC%) p e r m ole o f
m anganese- s u l f a t e p e r 2 . l i t e r s o f s o l u t i o n .
a te
The r a t e p f p o ta s s iu m perm angan­
a d d i t i o n was 70 grams p e r h o u r p e r m ole o f m anganese s u l f a t e ; ' T h e^ re­
a c t i o n m ix tu re was a i r a g i t a t e d .
The p r o d u c t from t h i s r e a c t i o n , when",fab­
r i c a t e d i n t o c e l l s an d t e s t e d , had a d r a in l i f e o f 5»51 h r ; H.D, and 12$ h r ,
!,D o
Becaupe sam ple S-KP-18 m et th e h ig h d r a i n s p e c i f i c a t i o n and wap."only
5 h r , s h o r t o f th e low d r a in s p e c i f i c a t i o n , r e a c t i o n S-K P-24 was fo rm u la te d
t o t r y to d e te rm in e th e e f f e c t o f a e r a t i o n on th e b a t t e r y a c t i v i t y o f "mangan­
e s e d io x id e p ro d u ced by th e S-KF
s y n th e s is .
The r e a c tio n c o n d itio n s ’ f o r
S-K P-24 w ere i d e n t i c a l to th o s e o f S-KP-18 e x c e p t f o r th e p r e s e n c e o f th e
p e b b le s.
The d r a in l i f e o f th e p r o d u c t o f t h i s r e a c tio n was 5 „ 4 .h r ; HoD,
and. 126 h r ; L„D,
The b a t t e r y t e s t s , o f S-K P-24 d u p l i c a t e t h e t e s t s : o f r e ­
a c t i o n S-KP-18=,
F ro p t h i s i n f o r m a t i o n . i t was assum ed t h a t th e presence-"-of
a i r in th e r e a c t i o n m ix tu re i s b e n e f i c i a l to th e d r a in l i f e o f m anganese
d io x id e p ro d u ced by th b S-KP s y n t h e s i s .
-
36
-
B ecause th e ab o v e two sam ples- d id n o t m eet b o th d r a in s p e c i f i c a t i o n s ,
an d
e a r l i e r w ork had i n d i c a t e d th e im p o rta n c e o f m anganese c o n c e n tr a ti o n , a
s e r i e s o f t h r e e r e a c t i o n s ; S-K P-25, 2 6 , an d 27 w ere ru n a t c o n c e n tr a tio n s o f
one mole o f m anganese s u l f a t e p e r 2 , 6 , an d 1 4 l i t e r s o f w a te r r e s p e c t i v e l y
w h ile th e c o n c e n tr a tio n o f p erm a n g an ate was c o n s ta n t a t one e q u i v a le n c e 'p e r
m ole o f m anganese" s u lf a t e - ' p e r two l i t e r s o f s o l u t i o n .
I t was ' th e " p u rp o s e
o f t h i s s e r i e s to d e te rm in e th e f u n c ti o n o f m anganese c o n c e n tr a tio n i n th e
a e ra te d r e a c tio n .
The b a t t e r y d r a in t e s t s f o r th e above - r e a c tio n s " a r e a s
f o llo w s : - S-K P-25, 4 .5 h r ; H . D . 6 l h r . L 0B ,; S-KP-2 6 , 4 .7 h r . H.B.. ,r-1 1 8 -h r.
L .D .; S-K P-27, 5 .0 h r ; H .D ., 150 h r ; L-=D. Sample S-KP-27 exceeded-' th e - low
■
d r a in s p e c i f i c a t i o n by 20 h r .
I t i s e v id e n t from t h i s s tu d y t h a t - t h e " conpen--
t r a t i o n o f m anganese p u l f a t e , one m ole p e r 14 l i t e r s o f s o l u t i o n ,/ u s e d i n "r e ­
a c t i o n S-tKP-2 7 , i s th e m ost f a v o r a b l e c o n c e n tr a tio n u s e d ;
th is
s tu d y i s i n a c c o r d w ith a s i m i l a r s tu d y
The •;c o n c lu s io n to
p r e s e n te d in a n ■■S a r l i e n vs e c ­
tio n o f t h i s th e s i s .
. .
The e f f e c t; o f i m p u r i t i e s in th e manganfese s u l f a t e was s tu d ie d -by- r e ­
a c t i o n s S-KP-29 and 3 0 .
The - p r e p a r a tio n o f b o th sam p les i s i d e n t i c a l to
th e p r e p a r a t i o n o u t l i n e d f o r r e a c t i o n S-K P-27;
Sample S-KP-29 was made ..from
t e c h n i c a l g rad e m angapese s u l f a t e s u p p lie d by th e C a m s'C h e m ic a l C o . , 'w h ile
I
1
sam ple S-KP-30 was made from p u r i f i e d ( z in c o x id e m ethod) m anganese s u l f a t e .
The d r a i n t e s t s f o r th e s e r e a c tio n 's a r e ? S-K P-29, 4 .5 h r.;..H0D ., 1 1 4 -.h r;‘ L.D ..;
S-K P-30, 3 .7 5 h r ; H .D ., 96 h r . L oD0
The sam ple p r e p a r e d from the-'-impure-’man­
g a n e se s u l f a t e gave th e g r e a t e r d r a in ' t e s t .
In th e l i g h t o f s t u d i e s made on th e a e r a t i o n o f th e r e a c t i o n m ix tu re
-3 7 and th e r e s u l t s o f f o r e g o in g s t u d i e s r e p o r te d i n t h i s . t h e s i s , , i t . w a s v d e e id e d to in c o r p o r a te th e fo llo w in g c o n d i tio n s -in to a . l a r g e r e a c t i o n s ^ I 0
T h is r e a c t i o n was to p ro d u ce' o ne-pound o f m a t e r i a l .
v e s s e l w ould be u s e d .
3o The r e a c t i m m ix tu re would be a e r a t e d ; m e c h a n ic a l
a g i t a t i o n would a l s o be u s e d .
be u s e d ,
2= The l a r g e r e a c t i o n
(C a m s C h e p ic q l-C o .)
4° T e c h n ic a l g ra d e m anganese .su lfate-,.w o u ld
B ecause th e r e a c t i o n v e s s e l i s h e a te d
by s p a rg in g steam d i r e c t l y i n t o th e r e a c t i o n m ix tu re ,, th e re b y c a u s in g an
.Z
'
i n c r e a s e in volume a s th e r e a c t i o n p r o g r e s s e s , th e i n i t i a l c o n c e n tr a tio n
o f th e m anganese s u l f a t e was- to be one m ole p e r 10 l i t e r s o f s o lu tio n .-
6b
The c o n c e n tr a tio n o f p o ta s s iu m p erm a n g an ate was to be one e q u i v a le n t ;- b a s e d
on one m ole o f m angapese s u l f a t e , p e r 2 l i t e r s o f s o l u t i o n .
i
tim e f o r th e p erm a n g an ate was to be 4 h r .
7« The a d d i tio n
8 . The r e a c t i o n m ix tu re- was to
be h e ld a t th e b o i l i n g p o q n t f o r 3 h r . a f t e r f i n a l a d d i t i o n o f the- perm an­
g a n a te .
These c o n d i t i o n s , from t h e i n t e r p r e t a t i o n o f th e 'm ea g er-d ata
a v a i l a b l e w ere th o u g h t to be s a t i s f a c t o r y , an d m a t e r i a l a p p ro a c h in g s p e c i f i ­
c a t io n s h o u ld be p ro d u c e d .
The r e a c t i o n w hich was ru n a t th e ab o v e c o n d itio n s was "S-KP-33,-.
T h is
r e a c t i o n met. b o th d r a in s p e c i f i c a t i o n s w ith a d r a in l i f e o f 6o2. h r . '. H.D. an d
131 h r . L .p .
The sam ple d e s ig n a te d S-KP-33a- was a p o r tio n o f th e p r o d u c t o f r e a c t i o n
S-K P-33o
The r e a c t i o n was sam pled when a p p ro x im a te ly 0 .3 o f th e .p o ta s s iu m
p erm a n g an ate h ad been ad d ed to r e a c t i o n m ix tu r e -S-KP-33-= ' S&mple.'S-KP-~3‘3 ’a had
a d r a in l i f e o f 3 . 4 h r » H«;D. an d 130 h r ; L .D .
T h is i n d i c a t e s t h a t the- lo n g e r
h o ld in g tim e i n th e r e a c t i o n v e s s e l i s n e c e s s a r y f o r t h e p r o d u c t to -m e e t
-3 8 -
h ig h d r a in s p e c i f i c a t i o n s .
B ecause sam ple S-KP-33& m et one s p e c i f i c a t i o n , i t was p o s t u l a t e d
t h a t th e S-KP r e a c t i o n c o u ld be ru n by com bining two flo w in g s tr e a m s , w ith
a i r in tr o d u c e d a t th e j u n c t i o n , f o llo w e d by a s h o r t ( o n e " h r ,) r e a c tio n - 'tim e
an d th e n f i l t r a t i o n p f th e - p r o d u c t.
I
'
,
The c o n d i tio n s chosen- f o r - ;.a :.tr ia l r e -
'
a c t i o n on th e ab o v e c o n tin u o u s b a s i s w ere a s .-:i!d e n tie a i to th o s e o f r e a c t i o n
S-KP-33 a s
p o s s i b l e w ith t h e e x c e p tio n o f an ad d ed p u r i f i c a t i o n .s te p .'f o r
t h e m anganese s u l f a t e ; . t h i s r e a c t i o n was d esig n ated rS -K P ~ 3 4 o
Ttie d r a in l i f e o f sam ple. S_Kp_34 was. 4=0 h r ; HoD, an d 117 hr.;-^l,,D =
A lth o u g h th e sam ple d o es n o t m eet s p e c i f i c a t i o n s , th e . r e s u l t s . - show -th at'"-the
ab o v e ty p e o f c o n tin u o u s r e a c t i o n scheme i s f e a s i b l e ,
:
1,
•.
■•
SUMMARY
The. economics of the S-KP synthesis are in d u stria lly favorablb; - A -45
p e r c e n t r e t u r n on an i n i t i a l c a p i t a l o u tl a y o f 'f 4 1 5 ,6 0 0 i s to be e x !
p e c te d p e r y e a r .
a r e b a se d on a p l a n t c a p a c it y o f 10'
■
:■
to n s p e r..d a y an d a s e l l i n g p r i c e o f $ 0 ,2 5 p e r pound o f - f in is h e d p r o d u c t,
2,
T hese f i g u r e s
A lth o u g h a d ju s tm e n t o f r e l a t i v e c o n c e n tr a tio n o f r e a c t a n t s " f a i l e d i t o p r o y--- duce a s p e c i f i c a t i o n m a t e r i a l , a c o n c e n tr a tio n o f m anganese 's u l f a t e o f
I
a b o u t 0 ,0 2 5 m o les p e r l i t e r seemed b e s t ,
iI
I,
The r a t e o f a d d i t i o n o f p o ta s s iu m p erm an g an ate to m anganese s u l f a t e ■h a s
_
3,
an e f f e c t - on th e b a t t e r y a c t i v i t y o f th e p r o d u c t;
A s a tis fa c to ry ira te
I
o f a d d i tio n seem s to be 2 6 ,2 5 gram s o f p o ta s s iu m p erm a n g an ate p er-jh o u r
p e r m ole o f m anganese s u l f a t e ,
■4,
.E nlargem en t o f th e r e a c t i o n s i z e d o e s n o t hav e a d e t r i m e n t a l § f f e c t on
s . v
—39~
th e d r a i n l i f e o f th e r e a c t i o n p r o d u c t,
5»
H eat t r e a t i n g o f p o r t i o n s o f th e r e a c t i o n p ro d u c t h a s d is c l o s e d a
m ethod w hereby a m a t e r i a l m e e tin g low d r a in s p e c i f i c a t i o n s m ig h t be
I
'
!
I
p r o d u c e d ,- The c o n d i tio n s f o r su ch a r e a c t i o n a r e s u g g e s te d ; . P u r i f i 5
c a t io n o f th e m anganese s p l f a t e by th e a d d i tio n o f 10 g m „-zinc o x id e
p e r 124 .gm, m anganese s u l f a t e .
C o n c e n tra tio n o f m anganese . s u l f a t e
i s t o be 8 8 ,6 gm, p e r l i t e r .'and th e c o n c e n tr a tio n o f th e p erm an g an ate
to be 5 2 ,5 gm, p p r l i t e r .
The p erm a n g an ate i s . to be ad d ed a t th e r a t e
o f 2 6 ,2 5 gm, p e r h o u r p e r 124 gm, m anganese s u l f a t e .
A f t e r w ashing*
f i l t r a t i o n an d d r y in g o f th e p r o d u c t, i t i s to be h e a te d a t a te m p era­
t u r e o f a b o u t 220oC, f o r 6 h r ,
6,
.
Com m ercial r e a g e n ts w ere r e a d i l y a d a p t a b le to th e s y n t h e s i s d - P u r i f i ­
c a t io n o f t e c h n i c a l g ra d e m apganese s u l f a t e and p o ta s s iu m perm angan­
a t e was n o t n e c e s s a r y to p ro d u ce s p e c i f i c a t i o n m a t e r i a l ,
7,
Seven o th e r m ethpds o f tr e a tm e n t o f th e p r o d u c t o f r e a c t i o n w ere t r i e d .
Of th e s e seven m e th o d s, o n e, th e a e r a t i o n o f th e r e a c t i o n m ix tu r e , p r o ­
duced a m a t e r i a l t h a t m et b o th h ig h d r a in and low d r a i n s p e c i f i c a t i o n s .
The c o n d itio n s f o r th p s u c c e s s f u l r e a c t i o n w ere; A e r a tio n o f th e r e a c t i o n
m ix tu re ..
C o n c e n tr a tio n o f u n p u r i f i e d T ech, g rad e m anganese s u l f a t e was
0 ,1 m ole p e r l i t e r o f s o l u t i o n ,
A s o l u t i o n c o n ta in in g one e q u iv a le n t
(b a s e d on ope mole o f m anganese s u l f a t e ) o f p o ta s s iu m p erm a n g a n a te , p e r
. '
f
2 l i t e r s o f s o l u t i o n was' ad d ed a t a r a t e o f 2 6 ,2 5 gm, p e r h o u r p e r m ole o f
m anganese s u l f a t e .
R e a c tio n was ru n a t th e b o i l i n g p o i n t , -SV0Gi
The
R e a c tio n was h e l d a t th e b o i l i n g p o i n t f o r 3 h r , a f t e r th e f i n a l a d d i t i o n
•
:
.
—
40
.
™
• o f p e rm a n g a n a te o
B„
From th e one c o n tin u o u s r e a c t i o n scheme t h a t was t r i e d , r e s u l t s in
d i c a t e s u c c e s s f u l a d a p t a ti o n o f th e S-KP -s y n th e s is to a c o n tin u o u s
re a c tio n b a s is .
z
/
-4 1 —
I
LITERATURE CITED
( 1 ) i B e rg , e t a l„ ', ' C hem ical S y n th e s is o f B a t te r y G rade M anganese .D io x id e .
F i h a l R e p o r t, Army S ig n a l C orps C o n tr a c t DA -36-039 s c - 5579„
E h g in e e r i n g '/E xpefim ent S t a t i o n , M ontana S t a t e C o lle g e , Bozeman, 1 9 5 4 ,
(2 )
D a v id so n ,
J , A ., M, 8 , T h e s is , M ontana S t a t e C o lle g e , 1 9 5 2 ,
(3)
F a h lg r e n , C. E ,,,'M , S . T h e s is , M ontana S t a t e C o lle g e , 1953.
(4 )
K l e i n f e l d e r , E. 0 » , 'M, 8 . T h e s is , M ontana S ta t e C o lle g e ,. 1954»
(5)
M o o r e ,' I . G ., M. S . T h e s is , M ontana
(6)
M c k e ls o n , R. L . , M. S . T h e s is , M ontana S t a t e C o lle g e , 1952.
(7 )
S a d a g o p a c h a ri, R ., M. S. T h e s is , M ontana S t a t e C o lle g e , 1953»
(S)
U . S . Army S ig n a l C o rp s, T e n ta tiv e S p e c i f i c a t i o n s , M anganese
D io x id e S y n t h e t i c ; SCL-3117-D. 18 M arch, 1952,. F o r t Monmouth,.
S t a t e C o lle g e , 1953»
Kew Jersey, 1952.
ACKKOWLEDGEMEKT
The a u t h o r w ish e s to th a n k th e E n g in e e r in g E x p erim en t S t a t i o n ,
M ontana S t a t e C o lle g e , s p o n so r o f t h i s r e s e a r c h p r o j e c t ;
The C arus
C hem ical Company, L a S a l le , I l l i n o i s , f o r th e d o n a tio n o f c h e m ic a ls ;
D r. L lo y d B erg , p r o j e c t d i r e c t o r ; and th e a u t h o r j s c o -w o rk e rs ,
F red. P . Baughman and W illia m .G. M oore, f o r t h e i r s u p p o r t o f " t h i s
re se a rc h
-4 2 APPENDIX
pag e
T a b le I
A n a l y t i c a l an d ,T est D ata
T a b le I I '
M ethods' o f P r e p a r a t io n
T ab le I I I
R e a c tio p Volume D rain D ata
T a b le IV..
E f f e c t o f O o n c e n tr a tio n ^ o f MnSO^ a t
C o n s ta n t'C o n c e n tr a tio n o f KMnO^ »
T ab le V
T a b le VIT ab le V II
9
O
O
O
O
‘0
0
0
O
O
O
' 0
O
O
O
0
0
O
O
O
O
O
0
O
O
9
O
O
0
46
0
O
O
O
43
54
55
O
o
o
o
o
o
57
. E f f e c t 'o f ' Time . o f' H e a tin g on -D rain L if e
o f-S -K P -1 9 « , C o - .
O
O
O
O
O
O
O
58
O
O
O
59
o
60
O
O
S ch em atic D iagram o f B a t t e r y T e s t Rack
F ig u re . 3
R efere n ce'-C h art"-fo r- X-Ray d i f f r a c t i o n
P a t t e r n p 'f o r V a rio u s Types o f M anganese
0 9
"0 0 0 0 0
D io x id e .
O
O
O
O
o
O
0
0
O
O
0
O
0
R e a c tio n Volume V s0 H igh D rain an d Low
D ra in L i f e o o o o o
O
C o n c e n t r a ti o n . O ffMnSOz
Low D ra in L i f e . .
O
O
O
O
O
O
O
O
O
o
0
O
O
o
0
O
O
o
O
o
O
o
o
o
o
0
0
9
0
0
0
0 6l
O
O
O
O
O
O
.
0
0
0
0
0
0 63
62
V s, H ig h -D ra in and
0
0
0
0
0
0
0
C o n c e n tra tio n "' o f "KMnO^ Vs . H igh D rain and
Low D ra in L if e O O O O O O O O O O O O O O O O O O O O
0 64
T em p eratu re o f H e a tin g V s. H igh D rain and
Low D rain . „ „ . ,
0 65
0
F i g u r e ■8'
O
O
0
0
E f f e c t o f T em p eratu re o f h e a t i n g on fira in
o
o
o
o
L llfe o f S-KP-X9 o o o e o e o o
F ig u re 2
F ig u re 7
O
0
0
56
Bobbin Tamping A p p a ra tu s
F ig u r e 6
0
O
O
F ig u re I
F ig u r e 5
0
0
E f f e c t o f C o n c e n tr a tio n o f 'KMnO^. a t
C o n s ta n t- C o n c e n tr a tio n o f MnSC/ 0 0 0 9 0 0 0 0 0 0 0 0
O
F ig u r e 4
0
0
9
0
0
0
0
0
0
0
0
0
0
9
Time' o f H e a tin g .Vs0 H igh D ra in and-Low D ra in
0
L
i f e
0
0
0
0
0
9
0
0
,
0
0
0
0
0
0
O
O
O
O
0
O
0
O
0
' O
0
O
O
0 66
TABLE I
ANALYTICAL AND TEST DATA
Code
S-KP-5H
S-KP-6:
S-KP-6H
S-KP-6H-HS
S-KP-7. - .
S-KP-TH
s-K P -a
S-KP-SH
S-KP-9S-KP-9H
S-KP-10.
S-KP-IOH
S-KP-Il '
S-KP-Ha
S-KP-IlH
S-KP-12.
S-KP-12a
S-KP-12H
S-KP-13- 1
S-KP-13H
S-KP-14S-KP-IZ1H
S-KP-15S-KP-15H
S-KP-16
S-KP-16a
S-KP-l6aH
S-KP-16H
S-KP-IT
S-KP-18
Mn
% Oz
..as
Mh02
%
86%5
9 0 .0
9 0 .2
58.7
5 9 .8
58.5
56*5 '
86,5
9 1 .0
92.5
9 5 .9
95.5
9 6 .6
97.-1
8 7 .8
9 0 .6
8 9 .4
8 3 .8
.8 9 .4
88 .9
7 3 .9
9 2 .4
91 .9
9 2 .6
91.1
9 2 .0
86.4
8 7 .0
8 7 .8
8 6 .1
8 6 .1
8 8 .4
7 8 .0
• . 9 0 .0
%
H2O
pH
. .
■ 60,6
5 8 .9
5 9 .4
60,1
58.7
59.5
59.6
6 0 .9
57.3
56.5
57.9
57.6
5 6 .2
5 8 .1
6 0 ,6
61,7
59.5
.6 0 .2 .
56.6
54.7
55.7
5 5 .4
54.9
. 5 6 .4
5 5 .8
5 5 .1
G m ./-
cu» in .
0 .0
0 .8
0 .0
0 .0
0 .3
0 .0
1.0
.0 .0
1.2
0.0
0 .7
0 .0
1 .8
1 .0
0 .0
0 .2
1.5'
0 .0
0 .9
0 .0
0 .9
0 .0
2 .5
0 .0
2 .0
1.9
0 .0
0 .0
2 .0
2 .1
Bobbin wfc« I n i t i a l Drain
Tests
gm.
H.D*.
L.D,
7 .3
5 .9
6 .0
11.1
9 .3
1 3 .8
9.4
11.7
5 ,1 .
1 3 ,1
1 3 .2
.9 ,5
9 ,5
8 .9
6 .3
5,6
6.4
6,6
6 .3
6 .9
6 .5
6 .5
36.6
14.4
1 4 .0
13.7
3-4.6
10.2
33 .5
9 .8
1 0 .0 ■
9 .2
6.4
14.0
11.3
' 11.1
11.7
5 .0
10 .6
4.6
10,0
11.0
5,1
5 ,8
5 .1
6.5 . 1 3 .2
6*0
. 6 ,1
6 .1
4 .8
5 .5
4.9
6,8
6.6
5 .1
6 .3
6 .2
9*4
9 .7
10 .0
10.3
1 3 ,0
1 4 .0
14.7
11.7
11.9
1 0 .0
10.0
1 0 .8
11.2
12.3
32 .5
9*4
9,7
9 .5
9 .3
9 .0
9 .6
9 .7
9 .5
9*9
9 .0
8 .8
9 .0
9 .2
9 .4
9 .4
2 .2 5
2 .7 5
3 l0
4.0
1.9
3 .7 5
4 .4
4.0
4 .0
3*6
4.3
3 .6
1.4
1.2
2 .1
2 ,5
1,64
3 .1
■ 146
93
75
64
55 •
64
124 ■
134
106
3-Month
33
• 66
114
■36
45
64
120
116
73
78
90
.80
60
33
60
42
62
60
64
20
26
25
34
26
29
93
29
HO
35
122
101
51
74
3 .5
128
1 .1
. 81
55
48 '
53
20
32
26
12
4 .2 5
3 .6
4.6
3 .8 5
2 .3 5
0.0
38
0 .5
36
44
9*4
4.0
4,0
40
79
106
9 .8
5 .5 1
125
H6
86
TABLE I (c o n t'd .)
.ANALYTICAL AND TEST DATA
Code
S-KP-IBH
S-K P-19
S-K P-19Ha
S-K P-19Hb
S-K P-19H c'
S-K P-19Hd
S-K P-19He
S-K P-19Hf
S-K P-19Hg
S-KP-19Hh
S-K P-19Hi
S-K P-20
S-KP-20H
S-K P-21
S-K P-21H
S-K P-22
S-KP-22H
S-K P-23
S-KP-23H
S-KP-24
S-KP-24H
S-KP-25
S-KP-25H
S-KP-26.
S-KP-26H
S-KP-27.
S-K P -2?H
S-KP-28.
S-KP-28H
S-K P-29-
^ Oz
as
IfciOg
# Mn
92i0
8 5 .0
8 3 .4
8 1 .7
82 .5
8 1 .7
7 0 .4
7 5 .5
7 4 .9
6 9 .2 .
7 6 .0
80.3
8 1 .9
8 2 .8
8 3 .1
8 1 .0
8 1 .4
80 .5
8 2 .8
8 7 .1 ,
88 .3
8 3 .5
8 2 .4
85.3
88.7
8 6 .9
88.5
8 1 .5
8 4 .8
8 7 .6
6 0 .0
56.2
5 3 .1
5 5 .4
5 4 .1
53.5
54*1
5 2 .1
5 0 .9
4 8 .9
5 0 .0
55.5
5 7 .0
5 8 .1
56.5
56.0
56.2
5 6 .1
5 6 .0
59.0.
5 8 .1
5 8 .0
55.5
57.5
. 59.0
59 .0
58.0
57.6
55.6
5 6 .0
% H2O
pH
0 .0
1 .5
.0 .0
0 .0
0 .0
0 .0
0 .0
0 .0
0 .0
0 .0
0 .0
2 .9
0 .0
2 .5
0 .0
2 .3
0 .0
2 .8
0 .0
2 .0
0 .0
2 .3
0 .0
2 .8
0 .0
1 .5
' 0 .0
2 .5
0 .0
1 .8
6 .8 - 1 3 .4
5 .5
1 1 .9
5*6
1 2 .5
1 1 .9
5 .9
5 .0
1 2 .4
1 2 .4
4 .9
] 2 .3
5 .5
4 .7
1 1 .5
1
2 .6
5 .4
1
2 .2
5 .3
4 .6
1 1 .9
6 .0
1 1 .4
5 .7 ' 1 1 .9
5 ,8
1 1 .4
5 .4 ■■ 1 0 .9
9 .6
5t7
5 .9
1 1 .7
5 .7
1 0 .4
5 .1
1 1 .4
1 3 .7
6 .3
1 3 .1
5 .4
1 1 .2
5 .9
-1 2 .4
5 ,9
1 2 .7
6 ,4
5 .6
12.3
14 .6
6 .5
4*-9
1 4 .1
6 .7
1 0 .4
1 3 .0
6 .2
1 3 .1
6 .7
.
(S i./
cu* i n
-
.
B obbin wb, I n i t i a l D ra in
T e s ts
gm.
H.D* __ L.D.
9 .8
9 .4
9 .8
9 .6
9 .7
9 .5
9 .6
1 0 .2
1 0 .1
1 0 .1 .
9 .9
1 0 .2
9 .8
9 .6
9 .7
9 .2
1 0 .1
:'9 .5
9 .8
1 0 .1
1 0 .0
9 .3
• 1 0 .0
10 .1
9 .8
9 .9
1 0.0
9 .2
9 .8
1 0 .0
4 .2 3
4 .7 5
4 .1 5 '
1 .3
3 .2
4 .0
4 .6
4 .2
1.2 7
3 .0
4 .5
1.0 5
3 .5
2 .3
2 .5
2 .3
0 .0
1 .0
1 .6
5 .4
4 .1
4 .5 .
1.9 5
4 .7
1 .6
5 .0
4 .5
0 .8 1
2 .2 5
4 .5
80
76
42
32
39
77
62
64
53 48
81
37
45
50
45
87
I
38
■45
126
85
61
48
118
67
150
88
58
56
114
3 - Month
106
70
5'8
39
. 60
61
51.
58
40
No t e s t .
96
3
36
42
36
50
0
30
55
TAEEE I .(C o n ttCl)
ANALYTICAL, AND •TEST. DATA
Code
% H2O
pH
Gm./ '
cu. in .
B obbin wt* I n i t i a l D ra in
T e s ts
gnu
H.D.
L .D ,
0 .0
1 .8
0 .0
3 ,2
1 .2
1 .9
2 .1
1 .3
6 ,7
5 .7
5 ,8
6 ,8
6 .4
6 .5
4 .4
6 .7
1 3 .4
1 3 .0
" 9 .4
1 0 .6
1 0 .7
1 3 .0
12 .7
1 3 .1
1 0 .4
1 0 .0
9 .3
9.6 5
9.45
9.75
10.05'
1 0 .0
as
NhOg
S-K P-29H
S-K P -30S-KP-30H
S-K P-31
S-K P-32
S-KP-33
S-K P-33a
S-K P-34
91.5
. 9 1 .2
9 3 .1
84,3
8 1 .0
S3 .2
8 5 .1
90.5
56.8
5 7 .4
5 8 .4
5 6 .0
51.6
52.2
‘
56 .2
55.9
'
1 .0
3 .7 5
1 .5
"1 .0
2 .5
6 .2
3 .4
4 .0
44
96
166
57
111
131
130
' 117
3-M onth
—. — — —
M M aaan
■ ■ ■ « »
mmtmmta*
4i
—4*6—
TABLE TI
METHODS- OF: PREPARATION
P r e p a r a tio n .
Code
S-KP-5H
R em aining p r o d u c t / o f S-KP-5 was h e a te d f o r 9g h r . a t 310°C .
S-HP- 6
H eate d a s o l u t i o n o f. 676. gm. M c S D i n 14 l i t e r s
to .8 7 ° 'C .; added,, drogmise.,-.. .420..gm...KMnO.^ in 7 l i t e r s HgO
o v e r a 5 h r . p e r io d . R e a c tio n volume was m a in ta in e d a t
14 l i t e r s - a n d t o t a l . r e a c t i o n tim e was. 8 h r . The r e ­
a c tio n . m ix tu re-w as- n o t" a llo w e d to . c o o l B e fo re d e c a n ta tio n
o f' t h e . . f i l t r a t e . •
S-K P-6H
The p r o d u c t o f S-KP- 6 m in u s;vone. .h u n d red ,.gram s, h e a te d f o r
h r . a t 3IO0-C. dr IO0C.
9
S-KP- 6H-HS
Suspended. 100 gm. o f. sam ple - S-KP-6H > in• 3 l i t e r s HgO and
30 cc.. H3PO4 ( c o n e .).. T r e a te d s l u r r y w ith HgS ( g .) f o r
10 m in u te s . The r e s u l t a n t . p r o d u c t was f i l t e r e d and h e a te d
a t 310° C. f o r 6 h r .
S-K P-7
D is s o lv e d 338 gnu MnSO-^.EhpO in 14 l i t e r s E2O; h e a te d to
87°C . 3 a d d e d , d ro p w is e , 210 gm. KMnO4 in 3o5 l i t e r s -ffaO. ■
R e a c tio n volum e was m a in ta in e d a t 14 l i t e r s . Ttie KMriO^
s o lu tio n - was"'added- o v e r a 4 .5 h r . p e r io d ; 87° d . te m p e ra tu re
m a in ta in e d f o r .3 .5 h r .
R e a c tio n m ix tu r e was c o p ie d f o r
.
15 h r . , w ith a g i t a t i o n , b e f o r e f i l t e r i n g .
S-KP-7H
H a lf th e p r o d u c t o f S-K P-7 was heated, f o r 12 h r . a t 3 1 0 °C.
S-KP-S
S-K P-Sff'
S-KP-9
D is s o lv e d 169 gm. MnSO^.HgO i n 14 l i t e r s H2 O; h e a te d to
■ 8 7 ° C .; a d d e d , d ro p w is e , 105 gm. KMnO^ i n 1 . 75'" l i t e r s If2 O.
R e a c tio n yolume m a in ta in e d a t 14 l i t e r s . The KMnOlZk
s o l u t i o n was ad d ed o v e r a 4 h r . p e r io d ; S7°C. te p p .
m a in ta in e d f o r 4 .4 h r . R e a c tio n m ix tu re was c o o le d f o r
15 h r . , w ith a g i t a t i o n , b e f o r e f i l t e r i n g .
’ " .
H a lf th e p r o d u c t o f S-KP-S w a s - h e a te d - f o r 9 h r . a t 3 1 0 °C.
D is s o lv e d I 69 gm. MnS04.H2 O in 16 l i t e r s H20, h e a te d to
- to 87°.C ., ad d ed d ro p w is e , 105 gm. KMn04 i n 9 li t e r s H f e O „
R e a c tio n vofume was m a in ta in e d a t 16 l i t e r s .
T he-PIhO^
s o l u t i o n was ad d e d o v e r a 10 h r . p e r io d . R e a c tio n ip ix - ■
t u r e was c o o le d f o r 4 h r 4 , w ith a g i t a t i o p , b e fo re
fflte rfn g .
X.
-4 7 '
TABLE I I ( c o n ’ t )
■P r e p a r a t io n
Code
S-KP-9H
H a lf th e p r o d u c t o f S-KP-9 was h e a te d f o r .9 h r . at:31Q°C<,
S-KP-IO
D is s o lv e d 169 gm. MnSOA = HgO in 16 l i t e r s HgO? h e a te d to
SyoC ., ad d ed d ro p w ise,, 105 gm, *KPiInO/ in 16 l i t e r s HgO'.
R e a c tio n - volum e ^ a s m a in ta in e d a t I o l i t e r s , ; The' KMnO^
s o l u t i o n wag added o v e r a 15 h r . p e r i o d . R e a c tio n .!m ix tu re
was c o o le d f o r 5 - h r ^ w ith a g i t a t i o n , b e f o r e f i l t e r i n g .
S-KP-10H
H a lf th e p r o d u c t o f S-KP.-10 was h e a te d f o r 9' h r . a t 310° C.
;
'v
S -K P -Il
D is s o lv e d 338 gmi MnSO^ . HgO in 4 l i t e r s HgO, h e a te d to
87°C „, ad d ed -d ro p w is e , 210 gm. KMnOA in A l i t e r s 'HgO1=
R e a c tio n volum e was m a in ta in e d a t A l i t e r s .
The KMnO^
s o l u t i o n w as-ad d ed o v e r a 3 h r . p e r io d ; 87°C . tem p.
• m a in ta in e d f o r 3 h r . R e a c tio n m ix tu re was c o o le d - f o r
1 8 . h r . , w ith a g i t a t i o n , b e f o r e f i l t e r i n g .
S -K P -Ila
L each ed 120 gm; S -K P -Il i n 1200 ec„ HgO w ith 5 c c . co n e.
HCl f o r 2 h r . - a t 8 2 °C.
S-K P-IlH
H eate d 90 gm. S -K P -Il f p r 9 h r . a t 3 1 0 °C.
S-KP-12
D is s o lv e d 398 gm. T ech . MnSO^ ( C arus 77-81%) in A l i t e r s
HgO; h e a te d to Sd0C .; a d d e d , d r o p w i s e ,o v e r a 3 h r . p e r i o d ,
220 gm. T ech 0-KMnO^ in A l i t e r s HgO.' R e a c tio n volum e'w as
.m a in ta in e d a t A l i t e r s ; r e a c t i o n te m p e r a tu r e w as'l87? C .;
- t o t a l r e a c t i o n tim e was 6 h r . fo llo w e d by a g i t a t i o n ’ f o r
18 h r . , to c o o l, b e f o r e w a sh in g .
-
S-KP-12a
L eached 160 gm. S-KP-12 in 1600 c c . HgO 'w ith 8 c c . c o n e.
HCl fibr 2 h r . a t i830C.
S-KP-12H
H eatpd 90 gm; S-KP-12 f o r 9 h r . a t 310°G .
,.
1
S-KP-13
D is s o lv e d 196 gm. T ech. MnSO/
( C arus 77^81%) in IA
l i t e r s HgO; h e a te d to 8 0 °C .; a d d e d , d ro p w ise ,' o v e r a-A h r .
p e r i o d , H O gm. T ech. KMnO^ i n 2 l i t e r s HgO. R e a c tio n
volum e was m a in ta in e d a t IA l i t e r s ; r e a c t i o n te m p e ra tu re
was ' 9 0 ° C . t o t a l r e a c t i o n tim e was,-? h r . fo llo w e d by
a g i t a t i o n f o r 16 h r . , t o c o o l, b e f o r e w a sh in g . '-
S-KP-13H
H eate d 75 gm. S-KP-13 f o r 20 h r . a t a te m p e ra tu re .b e tw e e n
3 1 0 °C0 a n i'3 4 0 ° C .
( il0 ° G .) .
■
-4 8 TABLE I I fc o n t'd )
Code
P r e p a r a t io n
S-K P-14
D is s o lv e d 196 gm. T ech. 'MnSO4_(C arus 77-81%) I n ,1 l i t e r
HgO; h e a te d to about".60°C . an d ad d ed a s l u r r y o f ,20"gm. '
4nO! in '150 c c . HgO) c o n tin u e d to h e a t " fo r 20 m in u te s w ith
a g i t a t i o n ,. R e a c tio n m ix tu r e f i l t e r e d - f r e e ''0'f -ZnOland
p r e c i p i t a t e d i m p u r i t i e s , d i l u t e d t o . 14 l i t e r s / and h e a te d
t o SOpC .; a d d e d , d ro p w is e , o v e r a 4 h r . " p e r io d ,•'H O gin.
T ech. KMnO4 i n 2 l i t e r s -HgO. R e a c tio n .volume, was ,main­
ta i n e d a t 14 l i t e r s ; r e a c t i o n te m p e r a tu r e ^was 90° C. ;
t o t a l r e a c t i o n tim e was 7 h r . f o llo w e d .b y a g i t a t i o n / f o r
16 h r * , t o c o o l, b e f o r e w a sh in g .
S-KP-H H
H eate d 70 gm. S -K P -H f b r 20 h r . . a t 3 1 9 °H
S-KP-1-5
. TrDissotwd--SO?- Tgmr5MnSO/ .B-^O I n 3 l i t e r s . HgO; h e a te d to
90°C . an d a d d e d , d ro p w is e , a s o lu ti o n o f 315 gm* KMnO4
in 3 l i t e r s HgO o v e r a
h r . p e r io d ; R e a c tio n volume
was m a in ta in e d betw een 3 and 3 5 l i t e r s -;- r e a c t i o n tem p er­
a t u r e was 9 3 ° G .; to t ,a l r e a c t i o n tim e was 6 h r . fo llo w e d
b y a g i t a t i o n f o r 16 h r . , to c o o l, b e f o r e w a sh in g .
S-KP-IdH
H eate d 70 gm.- .Sr-KP-15 f o r 9 h r . a t 3 1 0 3 2 0 ° C.
StK P -I^
D is s o lv e d 507 gm. MnSQ^.HgO in 3 l i t e r s XHgO; h e a te d to
90°C . an d a d d e d , d ro p w is e , a . s o lu tio n ., o f ..31-5 gm^-.pin0 4
in ^ 4 l i t e r s HgO o v e r a 4 h r . p e r io d . R e a c tid n ' volume was
m a in ta in e d betw een 3 an d 3 g l i t e r s ; r e a c t i o n te m p e ra tu re
was 93° 0 . ; t o t a l r e a c t i o n tim e was 6 h r . , fo llo w e d by
a g i t a t i o n f o r 16 h r . , to c o o l , b e fo re -.w a sh in g .
S- KP—16,0.
A f te r w ash in g sam ple S -K P -I6 , th e sam ple was d iv id e d i n t o
two p a r t s ap d
was d i g e s t e d a t 90°C. in a s o lu ti o n o f
100 c c . o f -HH/pH ( c o n e .) in I l i t e r HgO f o r I - hr."
S—KP-1 6jaH
H e a te d 70 gm.. S -K P -Id a f o r 9 h r . a t -310°C.
S-KP-16H
H e a te d 70 gm; S-KP-16 f o r 9 h r . a t 310°C.
S -K P -I7
D is s o lv e d 1 69 gm. MnSO^.HgO in 40 l i t e r s HgO (/ta p ),
. h e a te d to B .P . by s p a r g in g w ith steam ; Added,-, d ro p w ise ,
105 gm. KMnO^ in 2 l i t e r s HgP o v e r a 2 j h r . - p e r io d .
R e a c tio n volum e in c r e a s e d d u e ,t d condensed ste&m and
p r o d u c t rem o v al was s t a r t e d a f t e r 3a h r . ; r e a c t i o n
—■49—
TABLE I I
( c o a t 'd )
P r e p a r a tio n
Code
S-KP-17
(c o n tin u e d )
te m p e r a tu r e was "88° G ,; t o t a l r e a c tio n tim e w a s ‘5 h r .
S-KP-18
D is s o lv e d 169 gm, MnSO^.H^O in 10 l i t e r s H gO 'in a r e a c t i o n
v e s s e l w ith 8000 gm, o f f l i n t p e b b le s i n th e b o tto m , ■
R e a c tio n m ix tu r e was a g i t a t e d ( a i r ) an d h e a t e d ' to B .P ,
Added, d ro p w is e , 105 gm. KMnO^ in 2 l i t e r s H2O o v e r a
Lg h r . p e r i o d . R e a c tio n volume was m a in ta in e d a t 10 l i t e r s ;
r e a c t i o p te m p e r a tu r e was;-.870G ,; t o t a l r e a c t i o n ,tim e.,w as.-1.
6| h r . .
S-KP-IBH
Heatec^ 70 gm. o f'S -K P -1 8 f o r 9 h r , a t.- 3 1 0 °C0
I
D is s o lv e d 1284 gm. ,Tech.- MnSO^ ( C aru s 7 7-81$) in 6
l i t e r s H2O and p r e c i p i t a t e d i m p u r i t i e s w ith a , s l u r r y o f
66 gm. o f ZnO in 900 ce* HgO. F i l t e r e d , d i l u t e d to 10
g a l l o n s , an d h e a t e d 't o B .P . by s p a r g in g w ith steam . A dded,
d ro p w is e ;; a .s o lu tio n -o f 660 gm, KMnOd in 12 l i t e r s o f '
-HpO o v e r a 4 h r . p e r io d . R e a c tio n volum e m a in ta in e d a t
20 g a l l o n s ; T o t a l r e a c t i o n tim e was 6 h r ..; r e a c t i o n . rtem - 1
p e r a t ^ r p was 85°C .
-V '
CO
S-KP-19
f o r 9 h r . a t 310°C.
S-KP-19Ha
H eate d 70 gnu
S-KP-19Hb
H e a te d .70 gm. S-KP-1 9 f o r 9 h r . a t ‘355°C.
S-KP-19HC
H eate d 70 giju S-KP-1 9 f o r 9 h r . a t -265° C.
S-KP-19Hd
H e a te d 70 gm. S-KP-1 9 f o r 9 h r . a t 236°C.
S-KP-19He
S-KP-19Hf
H eatp d 70 gJ?u S-KP-1 9 f o r 6 h r . a t '3 0 5 ° C.
f' ■ '■
H eate d 70 gm. S-KP-1 9 f o r 3 h r . a t .305°G°
S -IC P ^ H g
H ea te d 70 gm, S-KP-19 f o r 15 h r . a t;3 0 5 ° C .
S-KP-19Hh
H ea te d 70 gm. S-KP-19 f o r 24 h r . a t 3 0 5 °C.
S-KP-19H1 x .
H ea te d 70 gm, S-KP-19 f o r 6 h r , a t ■-238°C.
S-K P-20
D is s o lv e d 196 gm, Tech-MnSOd ( Chrus 7,7-81$) o f I . l i t e r
HpO an d p r e c i p i t a t e d i m p u r i t i e s w ith a s l u r r y o f 20 gm.
o f ZnO in I l i t e t HpQ; F i l t r a t e heated * t o "B .P . and
0 .1 m ole HCl ad d ed to s o l u t i o n . Added, d ro p w ise ,:"H O
-5 0 -
TABLE I I
Code
( c o n t 'd )
P r e p a r a t io n
S-KB-20
( continued")
gm. T e c h .- KMnO^ in 2 l i t e r s HgO o v e r a 2 h r . p e r io d .
R e a c tio n volum e m a in ta in e d a t 2 l i t e r s ; t o t a l r e a c tio n
tim e was 6 h r . ; r e a c t i o n te m p e ra tu re was 9 2 ° C. R eactio n
m ix tu r e was a g i t a t e d f o r 16 h r . w h ile c o o lin g .
S-KP-20H
H e a te d 70 gm. o f S-KP-20 f o r 9 h r . a t 31p°C .
S-KP-21
D is s o lv e d 196 gm. Tech. MnSO^ ( C arus 77-81%) i n I l i t e r
HgO and p r e c i p i t a t e d i m p u r i t i e s w ith a s l u r r y o f 20 gm.
o f ZnO in I l i t e r HgO. F i l t r a t e h e a te d to B .p . and
0 .2 5 m ole HCl ad d ed to s o l u t i o n . Added., d ro p w is e , 100 gm,
T ech . KlljInO^ in 2 l i t e r s Hgp o v e r a I h r I p e r i o d . R eac tio n
volum e m a in ta in e d a t 2 l i t e r s ; t o t a l r e a c t i o n tim e was 6
h r . ;• r e a c t i o n te m p e r a tu r e was 93°C , R e a c tio n m ix tu re was
q uenched And w ashed im m e d ia te ly .
S-KP-21H
H e a te d 70 gm. S-KP-21 f o r 20 h r 6 a t a te m p e r a tu r e betw een
3 1 0 °C. and 355°C .
'—
S-KP-22
D is s o lv e d 196 gm. T ech. MnSO^ ( C arus 77-81%) i n I l i t e r HgQ a n d - p r e c j ip i ta te h i m p u r i t i e s w ith a s l u r r y o f 20 gm."
o f ZnO in I l i t e r HgO. F i l t r a t e h e a te d , to B .P . and 0 .1 p o le
HMO3 ad d ed to s o l u t i o n . A dded, d ro p w is e , H O gm. T ech.
KMnOz in 2 l i t e r s ' HgO o v e r a 2' h r . p e r i o d . R e a c tio n volum e
m a in ta in e d a t 2 l i t e r s ; t o t a l r e a c tio n .tim e was 6 j a r . ; . :i .
r e a c t i o n te m p e ra tu re was 9 3 ° 0 . R e a c tio n m ix tu re whs
quenched an d 'w a sh e d im m e d ia te ly .
S-KP-22H
H eate d 70 gm. S-KP-22 f o r 6 h r . a t 305°C°
S-KP-23
D is s p lv e d 196 gm. Tech'. MnSO.^ ( C arus 77-81%) in I l i t e r
HgO and p r e c i p i t a t e d i m p u r i t i e s w ith a s l u r r y o f 20 gm, jb f
;Zn0.in I lite r-'H g 0 ..i " " F i 'i t r a t 'e - h e a t e d "to B« P . and 0 .2 5
m o le ,HHO^ ad d ed to s o l u t i o n . Added, d ro p w is e , H O ■gm.
T e c h . KMnOi^ in 2 l i t e r s HgO o v e r a - 2 h r . p e r i o d . R eac tio n
volum e m a in ta in e d a t 2 l i t e r s ; t o t a l r e a c t i o n tim e wad 6
h r . ; r e a c t i o n te m p e ra tu re was 93°G. R e a c tio n m ixture,;v/as
q uenched an d w ashed im m e d ia te ly .
S-KP-23H
H ea te d 70 gm. S-KP-23 f o r 6 h f . a t 2 20°C.
S-KP-24
D is s o lv e d 169 gm. MnSO^ .HgO in 10 l i t e r s H^D; h e a te d to
-5 1 -
"TABLE I I
Code
(c o a t'd ).
P r e p a r a t io n
S-KP-24
(C o n tin u e d )
B .P . Add(=d, d ro p w is e , 105 gm. KMnO^ in 2 l i t e r s HgO
o v e r a 2 h r . p e r io d . R e a c tio n m ix tu re was a i r a g i t a t e d .
R e a c tio n volume was m a in ta in e d a t 10 l i t e r s ; t o t a l r e a c t i o n
tim e was 6 .5 I i r i ; r e a c t i o n te m p e r a tu r e was 87°C.' R e a c tio n
m ix tu r e was a llo w e d to c o o l, w ith a g i t a t i o n , f o r 16 h r .
b e fo re , w ash in g .
S-KP-24H
H e a te d 70 gm; S-K P-24 f o r 6 . h r , ■a t'2 2 Q ° C .
S-KP-25
D is s o lv e d -.1 6 9 .gm. MnSO^.HgO in 2 l i t e r s H2O ;'h e a t e d to
B .P . A dded, d ro p w is e , 1 0 5 gm. KfflnO^ in 2 l i t e r ' s 1^ O
o v e r a 2 h r , p e r io d . R e a c tio n m ix tu re was a i r a g i t a t e d .
R e a c tio n volume was m a in ta in e d a t 2 l i t e r s ; t o t a l - r e a c t i o n
tim e was 5 .5 h r . ; r e a c t i o n te m p e ra tu re was 87°C. R e a c tio h
m ix tu r e was a llo w e d to c o o l, w ith a g i t a t i o n , f o r 16 h r .
b e f o r e w ash in g .
S-KP-25H
H ea te d 70 gm. S-KP-25 f o r 6 h r . a t 2 2 0 °0 .
S-KP-26
D is s o lv e d 169 gm. MnSO^. HgO in 6 l i t e r s HgO; h e a te d to
B .P . A dded, d ro p w is e , 105 gm. KMnO^ in 2 l i t e r s HgO o v e r
a 2 h r . p e r io d . R e a c tio n m ix tu re was a i r a g i t a t e d . Re­
a c t i o n volume was m a in ta in e d a t 6 l i t e r s ; t o t a l r e a c tio n
ti m e - was 5 .5 h r . ; r e a c t i o n te m p e ra tu re was 87°C° R eac tio n
m ix tu r e was a llo w e d to c o o l, ,,with a g i t a t i o n , f o r 16 h r .
b e f o r e w a sh in g .
S-KP-26H
H eated 70 gm. S-KP-26 f o r 6 h r . a t 220°C .
. S-KP-27
D is s o lv e d 1 69 gm. InSO^ .H^D in 14 l i t e r s HgO; h e a te d to
B. P . Added, d ro p w is e , 105 gm. KMn04 in 2 l i t e r s HgO
o v e r a 2 h r . p e r io d . R e a c tio n m ix tu re was a i r a g i t a t e d
R e a c tio n volum e was m a in ta in e d a t 14 l i t e r s ; t o t a l r e a c t i o n
tim e was 6 h r . ; r e a c t i o n te m p e ra tu re was 9 3 °C. R eac tio n
m ix tu r e was a llo w e d to c o o l, w ith a g i t a t i o n , f o r 16 h r .
b e f o r e w ash in g .
S-KP-27H
H eate d 70 gm. S-KP-27 fo p 6 h r , a t 2 2 0 °C.
v
S-K P-28
D is s o lv e d 1284 gm, T ech. MnSO^ ( C arus 77-81%) in 6 l i t e r s
HjO; t r e a t e d w ith a s l u r r y o f 60 gm. ZnO to p r e c i p i t a t e
i m p u r i t i e s . F i l t r a t e was d i l u t e d to 10 g a l lo n s ; h e a te d
-5 2 TABLE.T I ( c o a t 'd )
Code
S-KP-28
....
( contim dtid)
S-KP-28H
P r e p a r a t io n
... to B.Po by a p a r g in g w ith Steam 0. Added,, .d ropw ise,, 660
.. gm0. i'KlnO^ i n 6 l i t e r s HgO o v e r a 3 h r 0 . p e r io d # - R e a c tio n
volujne wag m a in ta in e d a t 12 g a l l o n s ; t o t a l r e a c tid n - 'tim e
was 6 h r oI r e a c t i o n ■te m p e ra tu re was '-SV0G0 R e a c tio n :"to£3cture
was a llo w e d to c o o l, w ith a g i t a t i o n , f o r 6 h r 0-■b e f o r e 1'
w a s h in g ,
'
H e a tp d 70 gmw S-K P-28 f o r 6 h r 0 a t :220oGp
'
=
D is s o lv e d 153 gm0 T ech ; MnSQ^ (C a m s 77-81%) in 14
l i t e r s HgQ; - h e a te d T o B0P 0 Added, d ro p w is e ;. IlO ^gm 0
T ech0 "KMn04 in 2 l i t e r g HgO..over a. 2 ; 5 . h r ; - p e r i o d ; R e a c tio n
volum e was m a in ta in e d a t 14 l i t e r s ; . t o t a l r e a c t i o n "tim e
w as. 6 ,5 h r , ; r e a c t i o n . te m p e ra tu re w as"90°G , R e a c tio n ■mix­
t u r e ' was ^ llo w e d to c o o l , w i t k a g i t a t i o n , f o r T 6 h r ,
b e f o r e w agh|.ng.
R e a c tio n was a i r a g i t a t e d .
.
S-KP-29
S-KP-29H
H eate d 70 gm, S-KP-29 f o r 6 h r , at"22Q P 0,
S-KP-30
D is s o lv e d 153 gm, T ech; MnSO4 (Capus -77-81%) in 50$ c c ,
H^oj t r e a t e d w ith 10 gm,. ZnO to . p r e c i p a t a t e i m p u r i t i e s .
F i l t r a t e was d i l u t e d to 14 l i t e r s ; 'H e a te d vt o r B0PI' ' ’Added,"
d ro p w is e , H O gm, T ech 0 vKMnO^ , in 2 l i t e r s ' HgO o v e r a ■
2 h r . p e r i o d . R e a c tio n volum e was m a i n t a i n e d - a t ; 14 l i t e r s ;
t o t a l r e a c t i o n tim e .was 6 h r , ; .r e a c t i o n te m p e ra tu re - was
90 * 0 , - R e a c tio n m ix tu r e was a llo w e d t o - Coo^ w i t h - a g i t a t i o n ,
f o r 1 6 h r , b e f o r e w a sh in g . R e a c tio n was a i r a g i t a t e d , ■
S-KP-30H
H eate d 70 gm, S-KP-30
f o r 6 h r , a t '„220°C0
_
S-KP-31
S-K P-32
. ^ :
D is s o lv e d 153 gm,- T e c h t"MnSO I ( C a m s '77-81% ) i n 5Q5-. CC0
HgOj h e a te d , ad d ed 111 gm: CaClg d is s o lv e d "in 'I. I i t e r r 1HgO,
P r e c i p i t a t e d " CaSO^. rem oved by f i l t r a t i o n ; D ilu te d - f i l ­
t r a t e to" 2 l i t e r s ; 1h e a te d to B ,P , A dded, d ro p w is e /. H O '
gm, T e c h , KMnO^. in 1 ,5 l i f e r s HgO o v e r a '2 h r ," ’p e r io d .
R e a c tio n volume was m a in ta in e d a t 2 l i t e r s ; . t o t a l 'r e a c tio n
tim e w a s '6 h r , ; R e a c tio n t e m p e r a tu r e waS ivS1T10G., R e a c t i o n :
m ix tu r e was a llo w e d t o - c o o l , w ith a g i t a t i o n , f o r T ^ - h r ,
b e f o r e w a sh in g ,
'
r-A
. .
D is s o lv e d .169 .gm;. -MnSO4 ,■ H2O in 16 l i t e r s '.H2O; added 1 0 5
:v. ■
. .gm-, '’.'fflnO ./'ln v 2 \ i i t e r s -H2O o v e r a 3 ,5 h r , p e r io d ;. . -R e a c tio n
-5 3 TABLE I I ( c o n t 'd )
Code
■ P r e p a r a tio n
Sr-KP-32
(poD txntied)
■volume was m a in ta in e d a t 16 l i t e r s ; t o t a l r e a c t i o n tim'e
was 8 h r . ; r e a c t i o n te m p e r a tu r e was 92°C . R eac tio n
m ix tu r e was a llo w e d to c o o l, w ith a g i t a t i o n , f o r ' l 6 h r .
b e f o r e w a sh in g .
S-KP-33
D is s o lv e d 6?6 gm. Tech/.' MnSO^ ( C arus 77-81%) in 10 g a l­
lo n s H2O; h e a t e d / t o 'B . P . A dded, d ro p w is e , 420 gm / T ech.
KMnO^ in 8 l i t e r s HgG o v e r a 4 h r . p e r io d s -R e a c tio n
m ix tu re- wqts a i r a g i t a t e d . A p o r ti o n o f th e " p r o d u c t -was
w ithdraw n/w hen 0 .3 o f th e KMnO, had been a d d e d . .R eaction
volum e was m a in ta in e d a t 10 g a l lo n s ; ■ t o t a l re a c tio n -.'tim e
was 7 h r . ; r e a c t i o n te m p e r a tu r e w as-87°G . R e a c tio n .f ix ­
t u r e was q u en ch ed and w ashed Im m e d ia te ly ,
S-KP-33a
Sample w ith d raw n from r e a c t i o n S-KP-33 =
S-KP-34
P u r i f i e d w ith ZnO, 20 g a l lo n s o f a s o l u t i o n .co n tain in g I 69 gm. Tsch.,/MnSO^ ( C arus 77-81%) p e r 100 cc.„ o f s o lu ­
t i o n . D ilu te d 100 c c . o f MnSO^ s o lu ti o n to 1 2 g a llo n s
arid S e a te d to B .P .
A dded, d ro p w is e , a s o l u t i o n co n ta in ip g -. 5 2 .5 gm. T ech. "KMnO^ p e r l i t e r o f s o l u t i o n ; . ' Re­
a c t i o n p r o d u c t rem o v al begun when s to i c h i o m e t r i c am ount
o f KMnO^ had been a d d e d . Combined re m a in in g MnSO^''
s o lu ti o n an d KMnO, ' s o l u t i o n a t a s to i c h i o m e t r i c I r a t e ,
b a se d on a r a t e o f 200 c c . o f MnSO^ s o l u t i o n p e r h r . ,
w ith c o n s ta n t rem o v al o f p r o d u c t; R e a c tio n m ix tu re .;^ras
a i r a g ita te d ;
r e a c tio n volum e was 12 g a l l o n s ; r e a c tio n
tim e was I h r . ; r e a c t i o n te m p e ra tu re was :187°C . T o ta l 'tim e
o f o p e r a tio n was 6 h r . P r o d u c t was w ashed on :f i l t e r - .
(S ee abo.ye.)
-5 4 -
TABLE I I I
REACTION VOLUME - DRAIN DATA' S-KP- SERIES
Code
I:
T o ta l Volume
L i t e r SVzMol e-Mn SOy,
S-KP-15
I
1 .1
S-KP-16
I
2.35
S—
.KP-4.
2
0 .6
S -K P -Il
2
1 .4
S-K P-3 ..
4
1 .5
20
1 .2 5
81
50
48
£
0 .3
$
I
S-K P-5
V
I n i t i a l ! D rain T e s t (H ours)
"High '■ Ave-.1 Low
-Ave.
1 .0
60
’ 44,
2 .1 3
69
S-KP- 6
4
2 .7 5
93
S-KP-7
8
1 .9
55
S-KP- 8
16
4=4
124'
Sl-KP-IV
40
4 .0
-10 6
v.
.
-5 5 TABLE IV
x
'
E f f e c t o f .'C o n c e n tra tio n o f MnSOA a t C o n s ta n t C o n c e n tra tio n ' o f 'EMnOA
I e q u iv a le n c e p e r 2 l i t e r s .
C o n c e n tr a tio n o f 'KMnOA =
■" Code
. I
' MnSOa ConCo
■’.M o le /L ite r
■ I n i t i a l D rain T e s ts (.Hours)
. H igh ■• Ave.; . Low , Ave.
S-K P-17
0 .0 2 5
4 .0
106
S -K P -I
01072A
2 .0
78
S-KP-3
0 .5
1 .5
44
46
1 .0 5 '
S-KP-A
0 .5
S-K P -5
1 .0
■
0 .6
48
0 .3
20
-5 6 —
TABLE V
E f f e c t 'of. C o n ceirtrati'o n ':of KMnO^: a t C o n s ta n t C o n c e n tr a tio n o f 'MnSO/
C o n c e n tr a tio n " o f 'i MnSO^====1 I Mole .per 7 l i t e r s «
Code
.-KMnO^ Con Co
M ole ecu I L i t e r
I n i t i a l D ra in ^ T e s ts ‘(Hours.)
H ieh
Low
S-KP-Za
0 .5 7
0 .9
42
S -K P -7 ,
1 .1 3 0 5
1 .9
55
-5 7 TABLE VI '
E f f e c t, o f T em p eratu re o f H eatirig- on D rain L i f e :o f S-KP-19.
I
Time o f h e a t = 9 h o u rs
Code
T em p eratu re
I n i t i a l Dhain T e s ts
H igh
(H ours) Low
S-K P-19H d•
2 3 0 °C.
.4 =0
77
S-KP-19HC
265°C o
3 .2
39
S-KP-ISHa '
3 1 0 °C„
4 ,1 5
42
S-KP-19Hb
355°G .
1 .3
'32
- 58 TABLE ¥ 1 1
E f f e c t o f Time o f K e a tin g on D rain L i f e o f S-KP-19
T e m p e ra tu re ‘o f H eat = '3 0 5 oC«
;
Time
'
I n i t i a l D rain T e s ts
(H o u rs)
v
H ig h • (H o h rs)
Low
.
Code
.
S-KP-19Hf
3
4 .2
64
S-KP-19He
6
4 .6
62
S-KP-19Hg
15
1 ,2 7
53
S-KP-19Hh
24
3 .0
48
-5 9 -
r/T T
NOT TO SCALE
METHACRYLATE
STELLITE
/ / / /
A
I 'i
EJECTOR LEVER
!"u re
Bobbin
*r g .L pparrtvs
VOLTMETER
BATTERY
CONTACTS
FijTire 2.
Schcm tic Diayram of Dattory Toct -ack
—6 l —
MANGANESE DIOXIDE PHASE T Y P E S
XRD
T H
I i 1 I
1
3
r
2
1.5
IA
M I C R O - O P T I C A L SECTIONS. C.E.L.
IO e 6 5 4
CHART —
PRELI MINARY.
±U__l__l
I
WORKING
I I II
Il
I
I
R
I
I
Il
I____1 1 1 1 I I I
108 6 5 4
•'ig u re 3 .
I
N 17
3
illILlI I Il l l i
I
I
2
I
■
I
.
I
L5
I
F5
I illil il «111
,
,
____________________________
I
lT
.:a f r e n c e C h a rt f o r -r?:.y I f f r at 'o r Z a t t e r r s for- V c ric u s
Types o f Z iangarese D io x id e
LIFE HR.
HR.
LOW DRAIN
HIGH DRAIN LIFE
TOTAL REACTION VOLUME ( LITERS) PER MOLE OF Mn SO4
F ig u r e k
R e a c tio n Volume V s. High D ra in and Low D rain L i f e .
LIFE HR.
HR.
LOW DRAIN
HIGH DRAIN LIFE
M n SO4 CONCENTRATION, MOLE PER LITER
F ig u r e 5
C o n c e n tr a tio n o f MhSO^ V s. High D rain and Low D ra in L ife
LIFE HR 1
HR.
LOW DRAIN
HIGH DRAIN LIFE
KMn O 4 CONCENTRATION MO LE E Q. PER LITER
K'
C
Cr
CO
F ig u r e 6
C o n c e n tr a tio n o f KMnO^ V s. High D rain and Low D rain L i f e .
IOO
40
20
O
275
300
325
3
TEMPERATURE OF HEATING ( 0 C)
F ig u r e 7
T em p e ra tu re o f H e a tin g V s. High D rain and Low D rain L ife
LIFE HR.
HIGH DRAIN LIFE
60
LOW DRAIN
HR.
80
LOW DRAIN LIFE HR.
HR.
HIGH DRAIN LIFE
T I M E OF HEATING (HR.)
Figure 8 Time of Heating Vs. High Drain and Low Drain Life.
-
M O N T A N A S T A T E U N I V E R S IT Y L IB R A R I E S
762 10013580 3
114899
Chemical synthesis of b a t t e r y
g tiv e. manganese dioxide,
MAR 27 * 4
114899