A study of the Drotschmann activity test as applied to chemically prepared manganese dioxide
by James R Thurston
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 James R Thurston (1956)
Abstract:
Because of the long time required for determining the battery activity of manganese dioxide by
standard drain test methods, the Drotschmann Activity Test was investigated as a method of predicting
the efficiency of manganese dioxide samples intended for use in dry cells This thesis presents the
original procedure as used by the Signal Corps; revisions made in the original procedure, and results
obtained with the revised procedure as applied to the manganese dioxide produced by chemical
syntheses at Montana State College* A. study of the original Signal Corps procedure has revealed that
the following details caused variation in activity numbers obtained for the same manganese dioxide
sample, 1) Shaking rate 2) Reaction time 3) Particle size The results obtained with the revised
procedure show that the activity number does not show any correlation with the following (a) high or
low drain tests, (b) phase structure, (c) manganese content, (d) available oxygen content, (e) apparent
density, (f) pH, (g) water content, (h) manganese oxide content, (i) water of hydration content, and (j)
bobbin weights.
At present there is no apparent correlation of activity number with any of the characteristics of battery
active manganese dioxide; therefore, it is concluded that the Drotschmann Activity Test as outlined by
the Signal Corps is of little use in quality control for the production of manganese dioxide. A STUDY OF THE DROTSCHMANW ACTIVITY
TEST AS APPLIED TO' CHEMICALLY
PREPARED MANGANESE DIOXIDE
by
JAMES R . THURSTON
A THESIS
S u b m itte d t o t h e G r a d u a te F a c u l t y
in
p a r t i a l f u lf il lm e n t o f th e r e q u ir e m a its
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 h e m ic a l E n g i n e e r in g
at
M o n tan a S t a t e . C o lle g e
A p p ro v ed :
H e a d , M a jo r D e p a r tm e n t
D e a n ,''G rad u a
.v i s i o n
B o z o n a n , M ontana
J u l y , 1956
M3 7?
-2 -
' XAZl s
TABLE OF CONTENTS
Oc^>- V
A b s t r a c t ........................
In tro d u c tio n
.
,
M ethods a n d P r o c e d u r e
D is c u s s io n o f R e s u lts
Summary .............................
L i t e r a t u r e C ite d . . .
A p p e n d ix .............................
11S%28
/
V 3-
ABSTRACT
B e c a u s e o f t h e lo n g t im e r e q u i r e d f o r d e te r m i n in g t h e b a t t e r y
a c t i v i t y o f m an g a n e se d i o x i d e b y s t a n d a r d d r a i n t e s t m e th o d s , t h e
D ro tsc h m a n n A c t i v i t y T e s t was i n v e s t i g a t e d a s a m eth o d o f p r e d i c t i n g t h e
e f f i c i e n c y o f m an g a n e se d i o x i d e s a m p le s i n t e n d e d f o r u s e i n d r y c e l l s *
T h is t h e s i s p r e s e n t s t h e o r i g i n a l p r o c e d u r e a s u s e d b y t h e S i g n a l
C o r p s ; r e v i s i o n s made i n t h e o r i g i n a l p r o c e d u r e , and r e s u l t s o b t a i n e d
w i t h t h e r e v i s e d p r o c e d u r e a s a p p l i e d t o t h e m an g a n e se d i o x i d e p ro d u c e d
b y c h e m ic a l s y n t h e s e s a t M ontana S t a t e C o lle g e *
A. s t u d y o f t h e o r i g i n a l S i g n a l C o rp s p r o c e d u r e h a s r e v e a l e d t h a t
t h e f o l l o w i n g d e t a i l s c a u s e d v a r i a t i o n i n a c t i v i t y n u m b ers o b t a i n e d f o r
t h e sam e m an g a n e se d i o x i d e s a m p le ,
,
1)
2)
3)
S h a k in g r a t e
R e a c t i o n tim e
P a r tic le s iz e
The r e s u l t s o b t a i n e d w i t h t h e r e v i s e d p r o c e d u r e show t h a t t h e
a c t i v i t y num ber d o e s n o t show a n y c o r r e l a t i o n w i t h t h e f o l l o w i n g
( a ) h ig h o r lo w d r a i n t e s t s ,
(b ) p hase s tr u c tu r e ,
( c ) m an g an ese
c o n te n t,
( d ) a v a i l a b l e o x y g en c o n t e n t ,
( e ) a p p a r e n t d e n s i t y , ( f ) pH,
(g ) w a te r c o n te n t,
( h ) m an g a n e se o x i d e c o n t e n t ,
( i ) w a te r o f
h y d r a t i o n c o n t e n t , a n d ( j ) b o b b in w e ig h ts *
A t p r e s e n t t h e r e i s n o a p p a r e n t c o r r e l a t i o n o f a c t i v i t y num ber w i t h
a n y o f t h e c h a r a c t e r i s t i c s o f b a t t e r y a c t i v e m anganese d i o x i d e ; t h e r e f o r e ,
i t i s c o n c lu d e d t h a t t h e D ro tsc h m a n n A c t i v i t y T e s t a s o u t l i n e d b y t h e
S i g n a l C orps i s o f l i t t l e u s e i n q u a l i t y c o n t r o l f o r t h e p r o d u c t i o n o f
m an g a n e se d io x id e *
INTRODUCTION
The p r e s e n t m eth o d o f d e te r m i n in g t h e b a t t e r y a c t i v i t y o f m anganese
d i o x i d e i s t o make t y p e A d r y c e l l s w i t h t h e m an g an ese d i o x i d e a n d t h e n
t o r u n d r a i n t e s t s on t h e c e l l s „
The tim e r e q u i r e d f o r f a b r i c a t i o n ,
a g i n g , a n d t e s t i n g o f t h e d r y c e l l s t a k e s a b o u t 10 t o 12 d a y s .
T h i s 't i m e
l a g i s t h e m a in d i s a d v a n t a g e o f t h i s m eth o d a s a c o m m e rc ia l q u a l i t y
c o n tro l t e s t .
I n t h e c o m m e rc ia l p r o d u c t i o n -o f m an g a n e se d i o x i d e i t w o u ld b e
d e s i r a b l e -bo 'h a v e a - c h e m ic a l t e s t w h ic h w o u ld g iv e a p r e d i c t a b l e r e l a t i o n - :
s h ip w ith d r a i n t e s t s .
W ith t ^ i s i n m ind m any e f f o r t s h a v e b e e n made a t
t h e c o r r e l a t i o n o f v a r i o u s c h e m ic a l an d p h y s i c a l f a c t o r s w i t h b a t t e r y
a c t i v i t y , b u t t h e s e c o r r e l a t i o n s h a v e f a i l e d t o p r o d u c e a n a d e q u a te con­
tro l te s t.
The c h e m ic a l a n d p h y s i c a l f a c t o r s w h ic h h a v e b e e n i n v e s t i ­
g a t e d a r e ( a ) m an g a n e se c o n t e n t , ( b ) a v a i l a b l e o x y g en c o n t e n t , ( c ) p h a s e
s t r u c t u r e , ( d ) d e n s i t y , ( e ) b o b b in w e i g h ts o f t h e c e l l s t e s t e d ^ a n d ( f )
im p u r itie s (3 ) ,
I t has n o t been p o s s ib le to
show a d i r e c t c o r r e l a t i o n
b e tw e e n b a t t e r y a c t i v i t y o f m an g a n e se d i o x i d e a n d t h e s e c h e m ic a l and
p h y s ic a l c h a r a c t e r i s t i c s , b u t th e f o llo w in g s p e c i f i c a t i o n s f o r th e s e
c h a r a c t e r i s t i c s h a v e b e e n e s t a b l i s h e d b y t h e U , S , S i g n a l C o rp s
T e c h n ic a l R e q u ire m e n ts 3 0 1 -3 1 7 5 » 28 J u l y 1955» e n t i t l e d M anganese
D io x id e , M i l i t a r y B a tte r y G ra d e :
S p e c ific a tio n s
A b so rb e d M o is tu r e a s % HgO
3% m ax,
A v a i l a b l e Oxygen a s % MhOg
83% m in .
-5 58% m in*
T o t a l M anganese a s % Mn
3% max®
T o ta l In s o lu b le s
pH
4 4 ) - 7 ,0
I r o n a s % Fe
0 .2 5 # max,
L ead a s % Pb
0 . 25 # max
T o t a l H eavy M e ta ls ( O th e r t h e n Fe a n d P b)
0.05% max,
T o t a l A l k a l i M e ta ls
0.5%
max,
T o ta l A lk a lin e E a r th M e ta ls ,
0.5%
max,
A p p a re n t D e n s i ty a s g m /in 3
18
m in,
S ie v e S i z e i n
100
T h ru 20 m esh
T h ru 6 0 mesh
P h a s e Type
9 8 .0
Gammajl' R h o j Gamma-Rho
S in c e n o n e o f t h e a b o v e c h e m ic a l o r p h y s i c a l f a c t o r s p an b e u s e d a s
a d i r e c t m e a s u re o f t h e b a t t e r y a c t i v i t y o f m an g a n e se d i o x i d e , i t wad
th o u g h t t h a t t h e D ro tsc h m a n n A c t i v i t y T e s t s h o u ld b e e v a lu a te d *
The
p r o c e d u r e u s e d b y t h e S i g n a l C orps w h ic h was o b t a i n e d fro m a n a r t i c l e b y ,
Von C# D ro tsc h m a n n ( l ) ,
e n title d
" D e te r m in a tio n o f t h e D e p o l a r i z a t i o n
In d e x o f P y r o l u s i t e f o r t h e B a t t e r y I n d u s t r y , " was s e n t t o D r. B erg
'I
upon re q u e s t*
T h is t h e s i s g i v e s t h e p r o c e d u r e , r e v i s i o n s , a n d r e s u l t s
o b t a i n e d w i t h t h i s p e th o d o f t e s t i n g t h e p o t e n t i a l o f b a t t e r y - a c t i v e
m an g a n e se d i o x id e *
METHODS' AND PROCEDURES
The D ro tse h m a n n A c t i v i t y Number i s t h e n u m e r ic a l.m e a s u r e m e n t o f t h e
r e a c t i o n r a t e o f m an g a n e se d i o x i d e w i t h h y d r a z i n e s u l f a t e u n d e r con­
t r o l l e d c o n d itio n s .
The m a g n itu d e o f t h e a c t i v i t y num ber i s d i r e c t l y
p r o p o r t i o n a l t o t h e am o u n t o f h y d r a z i n e s u l f a t e deco m p o sed b y t h e man­
g a n e s e d i o x i d e sa m p le i n a g i v e n l e n g t h o f t i m e .
The p r o c e d u r e u s e d f o r
t h e d e t e r m i n a t i o n o f a c t i v i t y num ber’ i s o u t l i n e d b y t h e S i g n a l C orps a s
f o llo w s '( 4 ) :
E x a c t l y 0 ,3 0 0 0 g r , o f m an g an ese d i o x i d e i s w e ig h e d i n t o a 3 0 0 m l
E rle n m e y e r f l a s k c o n t a i n i n g 25 m l o f 0»2N ammonium h y d r o x i d e , Tvrenty
f i v e m l o f an aqueous s o lu t i o n o f h y d r a z in e s u l f a t e (B g r / l ) a r e added
a n d t h e f l a s k s h a k e n f o r o n e m in u te a t f i f t e e n - m i n u t e i n t e r v a l s . A f t e r
tw o h o u r s , t h e o r e i s f i l t e r e d o u t an d t h e c a k e w ash ed t w i c e w i t h c o ld
d i s t i l l e d w a te r.
To t h e c l e a r f i l t r a t e , 20 m l o f 1 : 4 s u l f u r i c a c i d t o
w a t e r a r e a d d e d . The s o l u t i o n i s t h e n h e a t e d t o a t l e a s t 65°C and
t i t r a t e d w i t h 0 ,1 N p o ta s s iu m p e r m a n g a n a te . B e c a u se t h e end p o i n t i s
o b s c u r e ( r o s e t o b r i g h t v i o l e t ) , t h e s o l u t i o n i s d e l i b e r a t e l y over-r
t i t r a t e d b y a b o u t 0 ,5 m l o f t h e p e r m a n g a n a te . E x a c t l y 2 .0 0 m l o f OeIN
f e r r o u s ammonium s u l f a t e i s t h e n i n t r o d u c e d a n d t h e s o l u t i o n t i t r a t e d
t o an e x a c t e n d p o i n t w i t h t h e 0 .1 N p o t a s s i u m p e rm a n g a n a te
A b la n k i s r u n th ro u g h a l l s te p s o f th e p ro c e d u re w ith qach s e t
o f d e t e r m i n a t i o n s , o m i t t i n g o n l y t h e m a n g a n e se d i o x i d e s a m p le *
A c t i v i t y Number = KMnO^ e q u i v a l e n t o f b l a n k m in u s KMnO^
e q u i v a l e n t o f s a m p le ,
KMnOi1. e q u i v a l e n t o f b l a n k = m l 0 ,1 N KMnOi1 m in u s 0 .1 N KMnOi1
e q u i v a l e n t o f 2 m l f e r r o u s ammonium s u l f a t e s o l u t i o n ,
KMnOjh e q u i v a l e n t o f s a m p le = m l 0 ,1 N KMnOj^ m inus 0 .1 N KMnQjiji
e q u i v a l e n t o f 2 m l f e r r o u s ammoniuin s u l f a t e s o l u t i o n .
The c h e m ic a l r e a c t i o n f o r t h i s t e s t i s b e l i e v e d t o b e a s ' f o l l o w s :
MnO2 / 2N2Hi1^H2 S0i1E A 2 S , MnO /
N2
/ 3H20 / 2(NH^) RSOi1
The p r o o f s o f t h i s r e a c t i o n a r e ( a ) e x p e r i m e n t a l d e t e r m i n a t i o n tfy a t tw o
m o le s o f h y d r a z i n e s u l f a t e a r e d ecom posed p e r m ole o f m an g a n e se d i o x i d e
d e c o m p o se d , a n d (b ). d e t e r m i n a t i o n o f t h e g a s l i b e r a t e d fro m t h e r e a c t i o n *
-7 “
The p r o c e d u r e a s o u t l i n e d b y t h e S i g n a l C o rp s g a v e c o n s i d e r a b l e '
v a r i a t i o n i n t h e v a l u e s o f a c t i v i t y num ber o b t a i n e d f o r t h e same s a m p le »
T h is v a r i a t i o n was b e l i e v e d t o b e c a u s e d b y i p c o n s i s t e n c y i n d u p l i c a t i o n
o f th e c o n d itio n s o f th e re a c tio n *
The m ain s o u r c e s o f v a r i a t i o n w e re b e l i e v e d t o be ( a ) s h a k in g r a t e ,
( b ) r e a c t i o n t i m e , ( c ) p a r t i c l e s i z e , ( d ) w a s h in g , a n d ( e ) t e m p e r a t u r e .
I n t h e o r i g i n a l p r o c e d u r e , t h e r a t e o f s h a k in g t h e s a m p le i s en­
t i r e l y d ep en d en t upon th e a n a ly s t *
T h e refo re th e e f f e c t o f t h i s v a ria b le
u p o n t h e v a lu e s o f a c t i v i t y num ber c o u ld e a s i l y a c c o u n t f o r some o f t h e
v a r ia tio n in th e r e s u l ts o b ta in e d .
I n o r d e r .to e l i m i n a t e t h i s human
v a r i a t i o n i n s h a k in g r a t e , a m e c h a n ic a l s h a k e r . F i g u r e I , was con­
s t r u c t e d t o g i v e c o n s t a n t s h a k in g r a t e s .
The p u r p o s e o f t h i s s h a k e r
w as t o g i v e c o n t i n u a l c o n t a c t i n g o f t h e h y d r a z i n e s u l f a t e s o l u t i o n w i t h
t h e m a n g a n e se d i o x i d e sam ple*
The v a l u e s o f a c t i v i t y num ber o b t a i n e d
w i t h d i f f e r e n t r a t e s o f c o n s t a n t s h a k in g a n d r e a c t i o n t i m e a r e p r e s e n t e d
i n T a b le I .
A s h a k in g r a t e o f 70 o s c i l l a t i o n s p e r m in u te an d a r e a c t i o n
tim e o f ojie h o u r w ere c h o s e n a s s t a n d a r d o p e r a t i n g p r o c e d u r e ,
• A lth o u g h t h e s t a n d a r d i z a t i o n o f s h a k in g r a t e a n d r e a c t i o n tim e r e ­
d u c e d t h e s p r e a d i n d u p l i c a t i o n v a lu e s f o r t h e same s a m p le , t h e d e s i r e d
p r e c i s i o n was s t i l l n o t o b t a in e d *
T h is s p r e a d w as b e l i e v e d t o be c a u s e d
b y t h e v a r i a t i o n i n t h e p a r t i c l e s i z e s o f t h e 0*300 gram s a m p le s o f t h e
m an g a n e se d i o x i d e b e in g t e s t e d *
tic le
The r e s u l t s o f a n i n v e s t i g a t i o n o f p a r ­
s i z e s show ed t h e - 1 6 0 / 200 m esh p a r t i c l e s i z e t o b e s a t i s f a c t o r y
a s s ta n d a rd o p e ra tin g p ro c e d u re .
The w a s h in g o f t h e s a m p le s a f t e r b e in g f i l t e r e d w as th o u g h t t o b e
o f im p o r ta n c e i n t h e d u p l i c a t i o n o f v a l u e s , b u t t h e v a r i a t i o n c a u s e d byw a s h in g t e c h n i q u e was m in im iz e d b y u s i n g s e p a r a t e s i n t e r e d g l a s s s u c t i o n
f u n n e l s an d t h e sam e am ount o f w ash w a t e r f o r e a c h s a m p le »
The volum e o f
d i s t i l l e d w a t e r u s e d f o r w a s h in g w as a p p r o x i m a t e ly 2 5 0 m i l l i l i t e r s o r
f i v e t im e s t h e volum e o f o r i g i n a l s o l u t i o n a n d w as u s e d t o g i v e f i v e
c o n s e c u t i v e w a s h in g s o f a p p r o x i m a t e ly 50 m i l l i l i t e r s
each.
The t e m p e r a t u r e a t w h ic h t h e t e s t s w e re r u n was room t e m p e r a t u r e
o r a p p r o x i m a t e ly 25 d e g r e e s c e n t i g r a d e .
DISCUSSION OF RESULTS
An i n v e s t i g a t i o n o f t h e o r i g i n a l S i g n a l C orps p r o c e d u r e showed
t h a t v a r i a t i o n s c a u s e d b y s h a k in g r a t e , r e a c t i o n t i m e , a n d p a r t i c l e
s i z e w e re i m p o r ta n t i n d u p l i c a t i n g a c t i v i t y num bers f o r t h e same man­
g a n e s e d i o x i d e s a m p le »
The v a l u e s o f a c t i v i t y num ber o b t a i n e d w i t h d i f f e r e n t r a t e o f
s h a k in g a n d r e a c t i o n tim e a r e g i v e n i n T a b le I .
T h e se v a l u e s i n ­
d i c a t e d t h a t a s t h e r a t e o f s h a k in g i n c r e a s e d t h e a c t i v i t y num ber
a ls o in c re a s e d .
T h is i n c r e a s e i n a c t i v i t y num ber w as c a u s e d b y t h e
i n c r e a s e d a g i t a t i o n o f t h e h y d r a z i n e s u l f a t e s o l u t i o n w i t h t h e man­
g a n e s e d i o x i d e s a m p le .
The am ount o f m an g an ese d i o x i d e sa m p le
s e t t l e d a t t h e s h a k in g r a t e o f 50 o s c i l l a t i o n s p e r ,m i n u t e w as ob­
s e r v e d t o b e g r e a t e r t h a n t h e am ount s e t t l e d a t t h e s h a k in g - r a t e o f
70 o s c i l l a t i o n s p e r m in u t e .
A g r e a t e r p o r t i o n o f t h e m a n g a n e se
-9 d i o x i d e sa m p ld w as s u s p e n d e d i n t h e h y d r a z i n e s u l f a t e s o l u t i o n a t t he
s h a k in g r a t e o f 70 o s c i l l a t i o n s p e r m inute®
I t was a l s o o b s e rv e d t h a t a s
t h e s h a k in g r a t e was i n c r e a s e d a b o v e 70 o s c i l l a t i o n s p e r m in u te t h e
s o l u t i o n t e n d e d t o s p la s h t on t o t h e s i d e s o f t h e f l a s k .
T h is s p l a s h i n g
w as b e l i e v e d t o b e s e r i o u s , b e c a u s e t h e h y d r a z i n e s u l f a t e s o l u t i o n
,
w h ic h r e m a in e d on t h e s i d e s o f t h e f l a s k d i d n o t come i n c o n t a c t w ith
t h e m an g a n e se d i o x i d e s a m p le .
The r e s u l t s fro m T a b le I and F i g u r e 2 show t h a t a s r e a c t i o n tim e
i n c r e a s e d t h e a c t i v i t y num ber i n c r e a s e d ; h o w e v e r, t h i s was l o g i c a l , a s
m o st r e a c t i o n s t e n d t o a p p ro a c h c o m p le tio n a s r e a c t i o n tim e i s i n c r e a s e d .
As c a n b e s d e n fro m F i g u r e 2 , d e c o m p o s itio n r a t e d e c r e a s e d a s t h e r e ­
a c t i o n p r o g r e s s e d , a n d t h e m a g n itu d e o f t h e a c t i v i t y n u to b ers o f t h e
v a r i o u s s a m p le s t e n d e d t o re m a in i n t h e sam e o r d e r .
T h e r e f o r e i t was
c o n c lu d e d t h a t a r e a c t i o n tim e o f one h o u r was j u s t i f i a b l e a n d was u s e d
a s a m a t t e r o f c o n v e n ie n c e t o t h e a n a l y s t .
I n o r d e r t o d e te r m i n e t h e e f f e c t o f p a r t i c l e s i z e bn a c t i v i t y
n u m b er, t h e p a r t i c l e s i z e s o f / 8 0 , - 8 0 / 1 2 0 , - 1 2 0 / 1 6 0 , - 1 6 0 / 2 0 0 ,
- 2 0 0 / 3 0 0 , - 3 0 0 w e re t e s t e d .
The s a m p le s w h ic h w e re t e s t e d , T a b le I I ,
show ed no c o n s i s t e n t c o r r e l a t i o n b e tw e e n p a r t i c l e s i z e a n d a c t i v i t y
n u m b e r; h o w e v e r, a fe w s a m p le s show ed t h e a c t i v i t y num ber t o i n c r e a s e
as th e p a r tic le s iz e d e c re a se d .
A l s o , a s c a n b e se e n fro m T a b le I I I ,
t h e v a r i a t i o n b e tw e e n a c t i v i t y num bers f o r t h e -1 6 0 / ^200 p a r t i c l e s i z e
was l e s s t h a n t h e v a r i a t i o n f o r t h e c o m p o s ite m i x t u r e ' f o r t h e same
—10™=
m an g a n e se d i o x i d e s a m p le »
The - l 6 0 / 200 p a r t i c l e s i z e w as c h o se n
b e c a u s e i t gave th e b e s t p a r t i c l e c h a r a c t e r i s t i c s i n t h e h y d ra z in e s u l ­
f a te s o lu tio n .
The - 1 6 0 / 200 p a r t i c l e s i z e t e n d e d t o r e m a in i n s u s ­
p e n s io n w i t h no l a r g e p a r t i c l e s s e t t l i n g t o t h e b o tto m o f t h e f l a s k .
A
s m a l l e r p a r t i c l e s i z e w as n o t u s e d b e c a u s e o f t h e f o r m a t i o n o f c o l l o i d a l
c o n d itio n s .
The r e s u l t s o f t h e r e v i s i o n s o f t h e o r i g i n a l S i g n a l C orps p r o c e d u r e
a r e b e s t show n b y t h e c o m p a r is o n o f v a l u e s o b t a i n e d b y b o t h o r i g i n a l a n d
r e v i s e d p r o c e d u r e s f o r t h e sam e m an g a n e se d i o x i d e s a m p le .
T h e se v a l u e s s
T a b le TV, show ed t h e v a r i a t i o n o b t a i n e d i n d u p l i c a t e s a m p le s t o b e l e s s
f o r th e r e v is e d p ro c e d u re th a n f o r th e o r ig in a l, p ro c e d u re .
U s in g t h e r e v i s e d p r o c e d u r e , s e v e r a l s a m p le s o f m an g a n e se d i o x id e
w e re t e s t e d i n o r d e r t o show c o r r e l a t i o n , i f a n y , b e tw e e n a c t i v i t y
num ber and t h e f o l l o w i n g ( a ) h i g h a n d lo w d r a i n t e s t s ,
(b ) p h ase
s t r u c t u r e , ( c ) m an g a n e se c o n t e n t , ( d ) a v a i l a b l e o x y g e n c o n t e n t , ( e )
a p p a r e n t d e n s i t y , ( f ) pH , ( g ) w a t e r c o n t e n t , ( h ) m an g an ese o x id e con­
t e n t , ( i ) w a t e r o f h y d r a t i o n c o n t e n t , a n d ( j ) b o b b in w e ig h ts *
A lth o u g h
s l i g h t m o d i f i c a t i o n s w e re made i n r e a t i o n c o n d i t i o n s f o r t h e
v a r i o u s s a m p le s , t h e g e n e r a l r e a c t i o n f o r p r o d u c in g t h e s a m p le s was
a s f o ll o w s s
MnS04 / C lp /--ANaOH - ^ M n O p / 2N aC l / NapSO^
/ HpO
The s a m p le s w h ic h w e re m ade b y t h i s r e a c t i o n a r e r e p o r t e d a s M -S-C l
w i t h a num ber f o l l o w i n g t o i n d i c a t e t h e r e a c t i o n n u m b e r.
The s a m p le llW eco11 was o b t a i n e d fro m a c o m m e rc ia l p r o d u c e r o f
-1 1 m an g a n e se d i o x i d e , a n d t h e sa m p le S -A P -I w as p ro d u c e d b y t h e o x i d a t i o n
o f m an g a n e se s u l f a t e b y ammonium p e r s u l f a t e u n d e r c o n t r o l l e d c o n d i t i o n s
(2)*
T h e se s a m p le s w e re p ro d u c e d a s p a r t o f t h e r e s e a r c h i n t h e
c h e m ic a l s y n t h e s e s o f m an g a n e se d i o x i d e a t M ontana S t a t e C o l l e g e .
The
a n a l y t i c a l d a t a f o r t h e s a m p le s w e re o b t a i n e d b y f o ll o w i n g S i g n a l C orps
p ro ce d u re s ( 5) .
The a c t i v i t y nu m b ers o f v a r i o u s s a m p le s a r e p r e s e n t e d w i t h d r a i n
t e s t d a t a i n T a b le V,
g ra p h ic a lly .
F i g u r e s 3 and 4 show t h e same i n f o r m a t i o n
The a c t i v i t y nu m b ers f o r t h e s a m p le s M -S -C l 8 7 , 8 8 , 8 9 ,
an d 90 w e re 1 .7 1 0 , 1 .9 5 0 , 1 .8 4 0 a n d 1 ,8 4 0 r e s p e c t i v e l y .
The h ig h
d r a i n t e s t s w e re 7 * 1 , 8 . 4 , 7 .3 a n d 8 .6 h o u r s , a n d t h e lo w d r a i n t e s t s
w e re 1 3 6 , 1 1 1 , 1 1 2 , and 120 h o u r s .
As c a n b e s e e n fro m t h e f i g u r e s o r
t h e a b o v e d a t a t h e r e was no c o r r e l a t i o n b e tw e e n a c t i v i t y num ber and
e i t h e r h i g h o r lo w d r a i n t e s t s .
T h e refo re, i t
i s b e lie v e d t h a t a t th e
p r e s e n t t i m e t h e u s e o f t h e D ro tsc h m a n n A c t i v i t y T e s t a s a n e s t i m a t e
o f d r a i n p o t e n t i a l o f m an g a n e se d i o x i d e i s n o t f e a s i b l e .
A lth o u g h t h e r e was shown t o b e no c o r r e l a t i o n b e tw e e n a c t i v i t y
num ber a n d d r a i n t e s t s , i t w as th o u g h t t h a t t h e r a t e a t w h ich t h e man­
g a n e s e d i o x i d e w as r e d u c e d b y t h e h y d r a z i n e s u l f a t e m ig h t b e r e l a t e d
t o t h e p h a s e s t r u c t u r e o f t h e m an g a n e se d i o x i d e sa m p le b e in g t e s t e d .
The a c t i v i t y num bers and p h a s e s t r u c t u r e d a t a o f v a r i o u s s a m p le s a r e
p r e s e n t e d i n T a b le V .
The p h a s e s t r u c t u r e s o f t h e s a m p le s w e re d e t e r ­
m in ed b y t h e E a g l e - P i c h e r Company th r o u g h t h e u s e o f x - r a y d i f f r a c t i o n
-1 2 p a tte rn s „
The a c t i v i t y nu m b ers f o r t h e s a m p le s M -S -C l 3 6 , 5 $ a , 8 5 » an d
87 w e re 1 ,8 1 2 , 1 .8 1 9 , 1 ,7 1 5 and 1 ,7 1 0 r e s p e c t i v e l y .
The p h a s e s t r u c t u r e s '
w e re gamma a n d e p s i l o n , r h o a n d gamma, e p s i l o n , and r h o .
As can b e
s e e n fro m T a b le V o r t h e a b o v e d a t a t h e r e was no c o r r e l a t i o n b e tw e e n
a c t i v i t y num ber a n d p h a s e s t r u c t u r e *
B e c a u s e t h e r e was no c o r r e l a t i o n show n b e tw e e n a c t i v i t y .n u m b e r ' a n d
e i t h e r h ig h o r lo w d r a i n t e s t s o r p h a s e s t r u c t u r e , t h e r e l a t i o n s h i p ' of"
a c t i v i t y num ber w i t h m an g a n e se c o n t e n t , a v a i l a b l e o x y g e n c o n t e n t ,
a p p a r e n t d e n s i t y , pH, w a t e r c o n t e n t , m an g a n e se o x id e c o n t e n t , w a te r o f
h y d r a t i o n c o n t e n t , a n d b o b b in w e ig h ts was s t u d i e d .
The a c t i v i t y num ber
a n d a n a l y t i c a l d a t a o f v a r i o u s s a m p le s a r e p r e s e n t e d i n T a b le V,
As
c a n b e s e e n fro m T a b le 7 , t h e r e was no c o r r e l a t i o n b e tw e e n a c t i v i t y
num ber a n d t h e a n a l y t i c a l p r o p e r t i e s o f t h e m an g an ese d i o x i d e sam p les*
At p r e s e n t t h e r e i s n o a p p a r e n t c o r r e l a t i o n o f a c t i v i t y num ber
w i t h a n y o f t h e c h a r a c t e r i s t i c s o f b a t t e r y a c t i v e m an g a n e se d i o x id e *
It
i s t h e r e f o r e c o n c lu d e d t h a t t h e D ro tsc h m a n n A c t i v i t y T e s t a s o u t l i n e d b y
t h e S i g n a l C o rp s i s o f l i t t l e
u se i n q u a l i t y c o n tr o l f o r th e p ro d u c tio n
o f m an g a n e se d i o x i d e »
SUMMARY
I,
The r e v i s i o n s made i n t h e o r i g i n a l S i g n a l C orps p r o c e d u r e i n
o r d e r t o r e d u c e t h e v a r i a t i o n b e tw e e n a c t i v i t y num bers f o r t h e same
m an g a n e se d i o x i d e s a m p le a r e a s f o l l o w s ;
a)
A c o n s t a n t s h a k in g r a t e o f 70 o s c i l l a t i o n s p e r m in u te b y a
m e c h a n ic a l s h a k e r % .
-1 3 b ) A r e a c t i o n tim e o f o n e h o u r ,
e ) A d e f i n i t e p a r t i c l e s i z e o f t h e s i e v e r a n g e - 1 6 0 / 200«
2*
The a c t i v i t y num ber d o e s n o t show a n y c o r r e l a t i o n w i t h e i t h e r
h ig h o r lo w d r a i n t e s t s ,
3,
The a c t i v i t y num ber d o e s n o t show a n y c o r r e l a t i o n w i t h p h a s e
s tru c tu re *
4o
The a c t i v i t y num ber d o e s n o t show a n y c o r r e l a t i o n w i t h man­
g a n e s e c o n t e n t , a v a i l a b l e o x y g e n c o n t e n t , a p p a r e n t d e n s i t y ,- pH, w a te r
c o n t e n t , m an g a n e se o x id e c o n t e n t , w a t e r o f h y d r a t i o n c o n t e n t , and
b o b b in w e ig h ts *
5.
At p r e s e n t t h e r e i s no a p p r a e n t c o r r e l a t i o n o f a c t i v i t y num ber
w i t h a n y o f t h e c h a r a c t e r i s t i c s o f b a t t e r y a c t i v e m an g a n e se d i o x i d e ;
th e re fo re , i t
is
c o n c lu d e d t h a t t h e D ro tsc h m a n n A c t i v i t y T e s t a s o u t l i n e d
b y t h e S i g n a l C orps i s o f l i t t l e
d u c t i o n o f m an g a n e se d i o x i d e »
u s e i n ( q u a l i ty c o n t r o l f o r t h e p r o ­
LITERATURE CITED
(1 )
D ro tsc h n m n j V . C . , C hem iker Z e i t u n g ,
V o I. $ 6 , P g . 2 3 4 -6 ( 1 9 3 2 ) ,
(2 )
M ic k e ls o n j R e L e j Me S . T h e s i s j M ontana S t a t e C o lle g e (1952'}»
(3 )
S a d a g o p a c h a r i j R e j Me S e T h e s i s j M ontana S t a t e C o lle g e (1 9 5 3 )*
/
(4 )
S i g n a l C orps E n g in e e r in g ' L a b o r a t o r i e s , L e t t e r t o M ontana S t a t e
C o l l e g e , 26 J u l y 1955*
(5 )
Ue S e Army S i g n a l C o r p s , T e c h n ic a l R e q u ir e m e n ts , M anganese
D i o x i d e , M i l i t a r y B a t t e r y G r a d e , S C 1 -3 1 7 5 ■> 28 J u l y 1 9 5 5 ,
F o r t M onm outh, New J e r s e y ,
-1 5 APPENDIX
Page
T a b le I
T a b le I I
T a b le I I I
T a b le 17
T a b l e .V
F ig u re I
A c t i v i t y N um ber, S h a k e r R a t e , a n d R e & e tio n
Time D a ta ..................................................... ....
.
16
A c t i v i t y Number and P a r t i c l e S i z e D a ta a t a
R e a c t i o n Time o f One H our a n d S h a k e r R a te
o f 70 O s c i l l a t i o n s p e r M i n u t e ................... ; . . .
.
17
A c t i v i t y Num bers F o r t h e C o m p o site a n d - 1 6 0
/ 200 P a r t i c l e S i z e a t a R e a c ti o n Time o f
One Hour a n d S h a k e r R a te o f 70 O s c i l l a t i o n s
p e r M in u te ..................................................................................
. «
18
A c t i v i t y Num bers O b ta in e d b y B o th t h e O r i g i n a l
a n d R e v is e d P r o c e d u r e s
A c t i v i t y N um ber, D r a in T e s t s , P h a se S t r u c t u r e ,
a n d A n a l y t i c a l D a ta
. . . . . . . . . . . .
M e c h a n ic a l S h a k e r
19
7
20
. . . . .
................................
F ig u re 2
A c t i v i t y Number v s . R e a c t i o n Time
. . . . . . . .
22
F ig u re 3
A c t i v i t y Number v s . H igh D r a in T e s t D a ta . . . . .
23
F ig u r e 4
A c t i v i t y Number v s . Low D r a in T e s t D a ta
24
. . . . .
21
4 6TABLE I
ACTIVITY NUMBER, SHAKER RATE, A lp REACTION TIME DATA
S am ple
S h ak er Speed
(O s d illa tio n s per
m in u te )
M -S -C l 21 C o m p o site
N
21
M
21
I!
21
M -S -C l 26
26
26
26
Tl
Tl
TI
IT
M -S -C l 8 ? - 1 6 0 /2 0 0
Il
89
,1
1
90
IT
88
IT
92
,Tim e
(H o u rs )
A c t i v i t y Number
(A v e ra g e s o f D u p l i c a t e s )
50
50
70
70
I
2
I
2
1 .2 2 1
1 .4 0 1
1 .6 3 8
2 .1 1 5
50
50
70
70
I
2
I
2
1 ,0 7 7
1 .2 1 5
1 .4 2 0
1 .8 7 0
70
70
70
70
70
0 .2 $
0 .2 5
0 .2 $
0 .2 5
0 .2 5
1 .1 1 2
1 .2 2 8
1 .2 6 7
1 .3 2 7
1 .3 4 9
M -S -C l 81
89
90
88
92
II
II
Il
II
II
70
70
70
70
70
I
I
I
I
I
1 .7 4 5
1 .8 3 5
1 .8 4 0
1 .9 5 0
1 .9 5 2
M -S -C l 87
89
90
88
92
II
II
It
II
M
70
70
70
70
70
2
2
■2
2
2
2 .2 1 5
2 .2 6 7
2 .2 8 9
2 .2 9 5
2 .3 0 5
-17TABLE I I
ACTIVITY NUMBER AND PARTICLE SIZE DATE AT A REACTION
TIME OF ONE HOUR AND SHAKER RATE OF 70 OSCILLATIONS PER MINUTE
Sam ple
M -S -C l 61
P a r t i c l e S iz e
(m esh r a n g e )
/8 0
-8 0 / 120
- 1 2 0 / 160
-160 / 200
-2 0 0 / 300
A c t i v i t y Number
(a v e ra g e o f d u p lic a te s )
1 .4 1 8
1 .4 6 9
1 .4 5 5
1.450
1.457
1.475
,
-300
M -S -C l 6 l a
■/ 8 0
- 8 0 / 120
-1 2 0 / 160
- 1 6 0 / 200
- 2 0 0 / 300
1 .0 6 1
1 .1 2 8
1 .1 3 4
.
-3 0 0
M -S -C l 64
M -S -C l 70a
Weco
1 .0 9 0
1 .1 1 2
1 .2 8 4
/8 0
-8 0 / 120
- 1 2 0 / 160
- 1 6 0 / 200
-2 0 0 / 360
1 .5 3 1
1 .6 4 5
1 .7 9 0
-3 0 0
1:995
/8 0
-8 0 /
-1 2 0
-1 6 0
-2 0 0
1.915
1 .9 4 0
1 .8 0 8
120
/ 160
/ 200
/ 300
■>
I .,845
1.787
1 .7 7
1 .7 9 0
- 1 2 0 / 160
-1 6 0 / £ 0 0
1.530
-200 /,3 0 0
1.735
1.820
-3 0 0
'
1 .5 6 0
-1 8 )
TABLE I I I
ACTIVITY NPMBERS FOR THE COMPOSITE AND - 1 6 0 / 200 PARTICLE SIZE AT A
REACTION TIME OF ONE HOUR AND SHAKER RATE OF 70 OSCILLATIONS PER MINUTE
Sam ple
M -S -C l 90
M -S -C l 92
C o m p o site M ix tu r e
1 .7 9 1
1 .8 4 7
1 .8 7 0
1 .8 9 0
1 .9 0 3
1 .9 4 1
2 .0 1 2
2 .0 4 4
-1 6 0 / 200 S ie v e R ange
.0 9 9
1 .8 1 9
1 .8 3 0
1 .8 4 0
1 .8 4 0
-
.0 2 1
«141
1.929
1.939
1.972
1.982
d =
.0 5 3
-1 9 TABLE IV
ACTIVITY NUMBERS OBTAINED B I BOTH THE ORIGINAL AMD REVISED
PROCEDURES
Sam ple
M -S -C l 90
A c t i v i t y Number
( o r ig in a l p ro ce d u re )
A c t i v i t y Number
( r e v is e d p ro ce d u re )
1 .5 7 2
1 .5 8 9
1 .8 1 9
1 .8 3 0
1 .6 3 3
1 .8 4 0
„ 1.611
1.840
TABLE V
ACTIVITY NUMBER, DRAIN TESTS, PHASE STRUCTURE, AND ANALYTICAL DATA
1 .0 9 0
1 .3 0 0
1 .4 5 0
1 .4 9 0
1 .5 6 0
1 .6 2 1
M -S -C l6 la -l6 0 /2 0 0
ti
- !I
41
Il
it \
61
it
4 6 a TI
IT
Wec o'"
TI
M-S-CS10
11 ■
II
40
JT
TI
It
I!
63
8?
85
64
IT
" .
II
69
IT
Tl
• 79
Tl
IT
IT
' 140
136
4 .7
102
3 .9
152
6 .5
140
122
6 .0
1 .7 0 6
1 .7 1 0
1 .7 1 5
2.9
1 ,7 2 0
1 ,7 3 0
1 .7 3 3
.1.-745
1 .7 6 2
II.
84
if
II
68
36
55a
Tl
1.770
TI
1 .8 1 2
1 .8 1 9 '
''
.
4 .7
3 .6
1.695
67
Tl
’
•
- 5.2
IT
'I !
-
5.3
4 .7 5
4 .7
4. 2 .
5 .6
4 .3
1 .6
.
1 ,5
——
TI
1.830
Tl
It
90
IT
1 .8 4 0
1 .8 4 0
7^3
8.6
JT
66
Il
86
86 .
92
11 ■
1.845
1.871
1.930
1.939
4»8 -
IT
i|
Il
TI
8 .2
1 .5
R ho,, some R
Gamma, some Rho
-
116
91
136
115
117
124
114
106
115
106
143
7 .1 ‘
6 .5
S-AP n
i
M-S- C l 89
Il
P h a se '
S tru c tu re
A c t i v i t y H igh D r a in Low D r a in
Number
H rs.
Hrs-.
Sam ple
-
149.5
112
120
108
131
99
137
8.25
88
V
- 1 .9 5 0
8 .4
111
-^Sample o b t a i n e d fro m c o m m e rc ia l p r o d u c e r
TI
Gamma, some Rho
Gamma
. B e ta
.B e t a , some Gamme, R h o ,Sigma
R ho, Some R
Rho
. E p s ilo n
%
%
Mn
a s MnQp
59.2
59.7
58.5
57.8
63.1
57.4
60.0
60.8
5 9 .1
5 8 .1
57.8
58.1
6 l,l
Gamma an d E p s i l o n
A lpha
Rho a n d Gamma
62.0
58,0
5 9 .1
S , Some Sigm a
S
92.5
90.6
90.6
94.6
.
D e n s ity
g m /in 3
13.0
pH
1 4 .4
5 .7
7 .3
10.8
12;8
6.5
6.7
%
%
H g O
m
2 .5
0.8
B o b b in '
o f Hyd. w e ig h ts
^ - H g O
o
0 .8
3 .1
1 3 .4 .. 1 .5
0 .0
0 .7
6.7
6.3
7.9
5 .1
10.3
11.25
8.95
9.75
—
59 . 7 58.3
58.2
.
92
59.9
59.3
58.0
57.0
57.8
9 2 .4
12.2
7 .0
2.3
6 .1
1 ,5
86.8
93.6
89.8
82.22
1 0 .6 1 0 .4
7 .2
5 .8
5.8
1 .7
3 .2
10.0
2 .0
3 .0
1 .0
5 .1
,5 ,4
9 4 .0
90.9
84.6
90.6
85.03
90.1
86.0
89.1
82.2
86.7
91.7
86.4
81.4
81.4
83.0
1 3 .8
12.0
10.0
9 .7
• 10.7
9.3
7 .0
5.5
5 .8
7 .7
5 .7
4 ,8
1 ,0
3 .2
5*8
3 .3
1 1 .6
9 .4
6 .7
2 .7
5 .5
10.9
1 0.0
4 .2
0.3
6.2
5.9 - 1 .5
-----1 2 .5
1 1 ,8
1 0 .2
6 ,1
5i9
12*4
6.3
12.7
10.7
6 .1
7.2
6.2
3 .7
5 .7
3 .5
5 ,3
3 .4
2.6
2*9
2.7
3 .5
9.85
9.75
9 .8
9.3
8 .9
5U
9 .1 . 8 .7
0 .3
5.7
8.0
1 ,1
6.2
9.2
1 .1
8.3
5.2
9 .8
1.6 ' 8.3
8.6
5 .4
7.2
3 .7
—
1 0 .1
5.4
8.9
5,8
7.6
6.8
9 .0
8.8
9.5
8.8
9.5
9.3
9 .0
—
7 .7
2,-5
6 .0
8 .4
7 .2
9 .7
1 0 ,2
1 1 .4
1 0 ,2
—
9 .0
8.9
9 .7
9.1
8.3
9 .1
8.9
—21—
MOTOR
/ \ ! / \!/ \
F i g u r e I . M e c h a n ic a l S h a k e r
—22—
. . M - S - C L 92
. M—S —CL 88
M -S -C L 90
M - S - C L 89
ACTIVITY
NUMBER
M - S - C L 87
REACTION TIME - HOURS
F i g u r e 2 . A c t i v i t y Number v s . R e a c ti o n Time
IOOi
CO
CC
SPECIFICATIONS
B
SIGNAL CORPS
I
6
Z
I
<
CC
0
1
CD
I
F i g u r e 3» A c t i v i t y Number v s . H ig h D r a in T e s t D a ta
8.0
NUMBER
ACTIVITY
F i g u r e U. A c t i v i t y Number v s . Low D ra in T e s t D a ta
- tJZ180
NUMBER
ACTIVITY
762
0005225 5
i
-
cnp'.C
T h u rsto n ,
A
I
119223
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11922H