DOCUMENT NO,

HW-5l65^
(CLASSIFICATION)

S E R I E S AND COPY N O ,

GENERAL^ELECTRIC A= / ^
DATE
HANFORD A T O M I C PRODUCTS OPERATION - RICHLAND, WASHINGTON
July 19, 1957
TITLE
R E S T R I C T E D D A T A
•ffTlS D O C U M E N T C O N T A I N S R E S T R I C T E D D A T A A S OXIDATION OF PLUrONIUM(lIl)
DEFINED I N T H E A T O M I C E N E R G Y A C T O F 1954. W SODIUM NURrCE
I T S T R A N S M I T T A L OR T H E D I S C L O S U R E O F I T S
CONTENTS IN ANY MANNER TO AN UNAUTHORIZED
PERSON I S P R O H I B I T E D .

• OTHER O F F I C I A L C L A S S I F I E D
THIS MATERIAL CONTAINS INFORMATION AFFECTING
INFORMATION
AUTHOR

A, Brunstad
THE NATIONAL DEFENSE OF THE UNITED STATES
W I T H I N THE MEANING OF THE ESPIONAGE LAWS,
T I T L E 18, U . S . C , S E C S . 793 A N D 794, T H E T R A N S - AUG 6 SBT
M I S S I O N OR R E V E L A T I O N O F W H I C H I N A N Y M A N N E R
TO AN U N A U T H O R I Z E D PERSON I S P R O H I B I T E D BY
LAW.

T H I S D O C U M E N T M U S T N O T BE L E F T U N A T T E N D E D OR W H E R E A N U N A U T H O R I Z E D P E R S O N M A Y H A V E A C C E S S
TO I T . W H E N N O T I N U S E , I T M U S T BE S T O R E D I N A N A P P R O V E D L O C K E D R E P O S I T O R Y W I T H I N AN APPROVED
GUARDED AREA. W H I L E I T I S YOUR P O S S E S S I O N A N D U N T I L Y O U H A V E O B T A I N E D A S I G N E D R E C E I P T F R O M
CLASSIFIED FILES, I T I S YOUR R E S P O N S I B I L I T Y TO K E E P I T AND I T S CONTENTS W I T H I N T H E L I M I T S OF
T H I S PROJECT AND F R O M ANY U N A U T H O R I Z E D P E R S O N . I T S T R A N S M I T T A L T O , A N D S T O R A G E A T YOUR P L A C E
OF RESIDENCE IS P R O H I B I T E D . I T I S NOT T O BE D U P L I C A T E D . IF ADDITIONAL C O P I E S ARE R E Q U I R E D ,
O B T A I N T H E M FROM T H E R E L A T E D I S S U I N G F I L E . A L L PERSONS READING T H I S DOCUMENT ARE REQUESTED
TO S I G N I N T H E S P A C E P R O V I D E D B E L O W .
F I L E S ROUTE
ROUTE T O : PAYROLL NO. LOCATION DATE SIGNATURE AND DATE

C-x^ C—T—*t—

,v«*"
^» <tA

••^^t I.
 DISCLAIMER

This report was prepared as an account of work sponsored by an

agency of the United States Government. Neither the United States
Government nor any agency Thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal
liability or responsibility for the accuracy, completeness, or
usefulness of any information, apparatus, product, or process
disclosed, or represents that its use would not infringe privately
owned rights. Reference herein to any specific commercial product,
process, or service by trade name, trademark, manufacturer, or
otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or any
agency thereof. The views and opinions of authors expressed herein
do not necessarily state or reflect those of the United States
Government or any agency thereof.
 DISCLAIMER

Portions of this document may be illegible in

electronic image products. Images are produced
from the best available original document.
 'V-
'.gfc'i ki'- IM»51655

This document classified by

A. Brunstad This document c o n s i s t s
of 12 pages. Copy No. /^f
of 19 copies. Series

OXIDATION OF PLUTONIUM(III) BI SODIUM NITRTTE

By

A. Brunstad

23ii.-5 Development Operation M^-

Research and Engineering Operation &y i^^^P~M±.Hj!sJ^

July 17, 1957

HANFORD ATOMIC PRODUCTS OPERATION

RICHLAND, WASHINGTON

Operated for the Atomic Energy Commission by the

General Electric Company under Contract #W-31-109-Eng-52

PORT

This report was prepared only for use within General Electric
Company in the course of work under Atomic Energy Commission
Contract W-31-109-Eng-52. Any views or opinions expressed in
the report are those of the authors only.

t'"i Ci*tii *'

o ^s-- /
 HW-=5i655
%*,

INTERNAL DISTRIBUTION

Copy Number

1 \ A. Brunstad
2 \ K. M. Harmon
3 \ M. K. Harmon
ii No. F. H i l l
5 HL H. Hopkins, Jr.
6 E \ R . Irish
7 W. ^ . Reas ^ ' ' • ^

8 R. BS. R;tchards
9 R, E.\anith
10 R. E. )romlinson
11 J. H,/Warren
12 » 15 ExtrA \
16 300 yFilesS.
17 Recyords Cetoter

EXTERNAL DISTRIBUTIo/ \

Copy Number \
18 - 19 Savannah River Laboratory

w.
 CONFIDENTIAL ^3- HW==5l655

OXIDATION OF PLUTONIUM(III) BY SODIUM NITRITE

I. INTRODUCTION

The o x i d a t i o n of p l u t o n i x i m ( l l l ) t o plutonium(lV) by n i t r i t e . h a s been s t u d i e d

by s o l v e n t e x t r a c t i o n methods and found t o be very r a p i d , ^•^•' ^^^ ^-^^ The speed
of t h e r e a c t i o n h a s discouraged a t t e m p t s t o measure t h e r e a c t i o n v e l o c i t y con-
s t a n t by means of spectrophotometry and s p e c i f i c v a l u e s of t h i s c o n s t a n t were
not ai'-ailable p r e v i o u s l y . I n t e r e s t h e r e i s i n t h e k i n e t i c s of t h e o x i d a t i o n of
Plutonium ( I I I ) t o p l u t o n i u r a ( I 7 ) i n n i t r i c a c i d s o l u t i o n c o n t a i n i n g f e r r o u s s u l -
f a m a t e . The f e r r o u s sulfamate y i e l d s s u l f a t e i o n s Tiihen oxidized by t h e n i t r i t e .
The e l e c t r o c h e m i c a l p o t e n t i a l s i n d i c a t e o x i d a t i o n of p l u t o n i u m ( I 7 ) t o be complete
i n t h e p r e s e n c e of s u l f a t e . (3) The v e l o c i t y r a t e c o n s t a n t for t h e o x i d a t i o n of
Plutonium ( I I I ) i n t h i s system h a s been determined t o p r o v i d e information for t h e
design of equipment employing t h i s r e a c t i o n .

II. SUl^lMAHI

The r e a c t i o n v e l o c i t y c o n s t a n t f o r t h e o x i d a t i o n of p l u t o n i u r a ( I I I ) by n i t r i t e
i n n i t r i c a c i d s o l u t i o n c o n t a i n i n g f e r r o u s sulfamate i s g i v e n . The r e a c t i o n r a t e
was found t o be measurable by means of s p e c t r o p h o t o m e t r y . The d a t a i n d i c a t e t h e
r e a c t i o n t o be a pseudo f i r s t - o r d e r r e a c t i o n i n t h e r e g i o n of n i t r i c a c i d and
n i t r i t e c o n c e n t r a t i o n of i n t e r e s t . The r e a c t i o n v e l o c i t y c o n s t a n t , e x p r e s s e d as
a f i r s t - o r d e r r e a c t i o n w i t h r e s p e c t t o p l u t o n i u m , was found f o r s e v e r a l v a l u e s
of n i t r i c a c i d and n i t r i t e c o n c e n t r a t i o n s . The n i t r i c a c i d - r e a c t i o n v e l o c i t y
constant r e l a t i o n s h i p i s given.

The o x i d a t i o n of t h e f e r r o u s s i i l f a m a t e - p l u t o n i u m ( I I I ) s o l u t i o n proceeds
s u c c e s s i v e l y through t h e s u l f a m a t e , f e r r o u s , and p l u t o n i u m ( l l l ) i o n s . An a u t o -
c a t a l y t i c mechanism i s a s s o c i a t e d w i t h t h e o x i d a t i o n of both f e r r o u s and p l u -
tonium ions -fciiich o b v i a t e s t h e p o s s i b i l i t y of simple c a l c u l a t i o n s of c o n s t a n t s
based on n i t r i t e c o n c e n t r a t i o n . An e m p i r i c a l r e l a t i o n s h i p between t h e r e a c t i o n
v e l o c x t y c o n s t a n t and t h e (added) n i t r i t e c o n c e n t r a t i o n i s g i v e n .

III. DISCUSSION

The Beckman DK-2 r a t i o r e c o r d i n g spectrophotometer was used t o f o l l o w t h e

course of t h e r e a c t i o n , A 1.6 M NaN02 s o l u t i o n was used t o o x i d i a e t h e f e r r o u s
s u l f a m a t e " p l u t o n i u m ( I I l ) s o l u t i o n . The s t a r t i n g f e r r o u s sulfamate c o n c e n t r a t i o n
was 0.021; M i n a l l e x p e r i m e n t s . The sodium n i t r i t e s o l u t i o n was i n t r o d u c e d i i t o
t h e reduced plutonium s o l u t i o n i n t h e spectrophotometer c e l l and immediately
s t i r r e d w i t h a p i p e t t e . Care was t a k e n n o t t o i n t r o d u c e a i r vdaile s t i r r i n g .
Absoibence r e a d i n g s were t a k e n a t l / 2 or 1 minute i n t e r v a l s u n t i l near com-
p l e t i o n of t h e r e a c t i o n . The 600 m^ p l u t o n i u m ( l l l ) absorbence peak was xised t o
measure t h e r e a c t i o n r a t e j however, s e v e r a l checks were made by measuring t h e
growth of t h e 1;75 m.}! plutoniura(I7) p e a k . Only t h i s p a r t of t h e spectrum was
scanned.

The r e a c t i o n r a t e was determined a t s e v e r a l a c i d i t y v a l u e s w i t h i n t h e range

0.1; M t o 2 . 0 M HNO3. S t a r t i n g c o n c e n t r a t i o n s from O.Ol; M t o 0 . 1 M were employed
in determining the n i t r i t e concentration e f f e c t .

^^33 :i~
^ag^ggMflAJ>->-— - ' -U- HW-51655

Timing of the spectrum scanning was done such that the indicated time
lapse r e f e r s to the period from addition of the n i t r i t e to the time indicated
by the top of the 600 mji plutonium(III) peak. Approximate plutonitim(lll) con-
centrations were calculated from absorbence at t h i s wave length. Simultaneous
values for plutonium(IV) formed in the oxidation were obtained by difference
betx>reen the plutonium ( I I I ) values and s t a r t i n g ( t o t a l ) plutonium concentration.
These plutonium(lV") concentrations and established plutonium( 17) molar absorb-
ence values at 600 m:ji were then used t o c a l c u l a t e the contribution due t o
plutonixjm(IV) at the 600 mp, plutonium(IIl) peak. This plutonium(IV) c o n t r i -
b i t i o n subtracted from the f i r s t plutonium(III) estimate gave the plutonium(III)
concentration figures used in subsequent p l o t s and c a l c u l a t i o n s . Semilog p l o t s
of these data (C vs t ) are shown. Convenient points were taken from these l i n e s
to calculate the r a t e constant k.

The disappearance (oxidation) of plutonium(III) i s represented by the s t a t e -

ment for a unimolecular reactions

•-d ^Miii)], k U ( i i i ) ]
Values of k were calculated from the integrated form?

Constant values of k indicated the above expression t o be s a t i s f a c t o r y .

This i s also evident from the s t r a i g h t l i n e s shown in semi-log p l o t s . Figures h
and 6. The effect of n i t r i c acid v a r i a t i o n s i s shown by sample spectra in
Figures 1, 2, and 3 . Figure 1 i l l u s t r a t e s the delay period found at low acid-
i t y . The high general absorbence during the f i r s t three to four minutes i s due
t o the continued l i b e r a t i o n of nitrogen gas during the sulfamate oxidation,
HN02 + NH2SO3- ^ N 2 + HSO^- + H2O
At higher a c i d i t i e s , t h i s gas evolution i s nearly instantaneous and i s
complete before scanning i s s t a r t e d . I t may be seen t h a t t h e height of the
600 mja plutoniura(lll) peak, above general absorbence, does not diminish nor
i s there a growth of the 1;75 Tnp- plutonium(IV) peak u n t i l l i b e r a t i o n of gas i s
complete. Concentrations of plutonium(III) calculated from the spectra sub-
sequent t o gas l i b e r a t i o n are shown at the r i g h t with a separate time axis in
Figure 1;, The f i r s t point does not f a l l on the s t r a i g h t l i n e , indicating a
slower reaction r a t e at f i r s t and a r a t e dependency on factors other than p l u -
tonium(III) concentration. Figure 5 i s a p l o t of k vs n i t r i c acid concentration.
The n i t r i c acid dependency of t h e reaction i s linear in t h e range 0,5 M t o 2,0 M
acid and may be expressed?
k = 0.009 + 0.006 H+
Generalization of this expression beyond the conditions and range indicated
are probably not warranted.

Figure 6 is a plot of data from the spectra shown in Figures 9 to 13 in-

clusive. The reaction at O.OU M NaN02, Figure 8, is not measurable. The curves

'73,3 3
'">*»>,
rOHMmML.. '' -5- HW-51655

representing t h e four highest n i t r i t e concentrations again showed t h e r a t e t o

be mainly dependent on plutonium concentration. The shape of t h e curve r e p r e -
senting oxidation with 0.053 H NaN02 would i n d i c a t e t h a t t h e specific r e a c t i o n
r a t e increased during t h e r e a c t i o n . This i s similar t o t h e phenomena observed
at low a c i d i t y . Both are explained on the bases of t h e a u t o c a t a l y t i c mechanism
of oxidation of iron and plutonium. Nitrogen dioxide has been shown t o be the
effective o x i d a n t . w ) (5) (6)

The concentration of NO2 i s c o n t r o l l e d by the following r a p i d l y r e v e r s i b l e

reaction?

2HN02^N02 + NO + H2O

That the oxidation of plutonium(III) t o plutonium(17) a c t u a l l y r e s u l t s i n

an increase in oxidant may be seen from t h e following r e a c t i o n s :

P u ( l I I ) + N02->Pu(I7) + NO2-

H+ + N02"-^HN02

HNO2 + H+ + NO3-—>2N02 + H2O

Thus each plutonium atom oxidized adds one NO2 molecule.

The reaction with iron and with plutonium are taken to be of identical
mechanism. The above mechanism provides oxidant at high enough concentration
to make the oxidation of plutonium appear dependent only on its own concentra-
tion. However, at low nitric acid and at low sodium nitrite concentrations
there is a delay in establishing this condition, but even under these condi-
tions, the reaction rate appears to become plutonium concentration dependent
only.

The O.02U M ferrous sulfamate requires an 0.0l;8 M concentration of sodium

nitrite for oxidation of the sulfamic acid only. The O.Ol; M NaN02, Figure 8,
is, therefore, insufficient to oxidize the sulfamic acid, and oxidation of iron
and plutonium is not accomplished. The 0.053 M added nitrite. Figure 9, is
sufficient to oxidize the sulfamate and part of the iron, thus starting the auto-
catalytic mechanism, and effecting oxidation of iron and plutonium. The shape
of the curve representing this concentration of added nitrite. Figure 6, in-
dicates increasing reaction velocity during the first one and one-half minutes,
which may be explained by the build-up of oxidant by the autocatalytic mechanism.
The last three points of this curve form a nearly straight line. Indicating the
reaction has become mainly plutonium concentration dependent. The higher con-
centrations of added sodium nitrite. Figure 6, yielded unchanging values for
the reaction velocity constant throughout the course of each reaction.

The values of k found at various added nitrite concentrations (Mt©) produced

a straight line when plotted on semilog paper (Figure 7). This graph is most
convenient an evaluating the effect of added nitrite concentration on the
reaction velocity. This graph indicates the reaction velocity constant may be
related to the starting nitrite concentration by an expression of the types

'GONFIDMTIAL

-V 3 3 Cf
a.fla^iDMT.iAir -6= HW-51655

j ^ - ^ ^^bC(NalI02)

The slope and intercept of the l i n e was used to obtain the expression
Log k = 6.Ill (NaN02) + log O.OOl;
xdiere k i s in sec"-^.

17. BIBLIOGRAPHY

1. Thomas, J. R. and H. ¥. Crandall, The Chelate Process, TID-10002,

December 12, 19U6 (Unclassified)5 pp. 30-3ii.

2. Wilson, A. S. and T. L. Swanson, A Continuoas Process for the Oxidation

of the Purex IBP Stream, HW-23301, January 17, 1952 (Secret),

3. Eeilly, V. J., Purex Process Plutonium Oxidation and Reduction, August 10

bo November 10, 1951^ CF-gl-ll-ll;0 (SecretjT

1;. Zebroski, E., and R. C. Feber, Sulfamic Acid In The Redox Process,
KAPL-89 (Confidential),

5. Tost, D, M. and H. Russell, Jr., Sustematic Inorganic Chemistry. New

York? Prentice-Hall, Inc., 19li6, pp. 58-61.

6. Connick, R. E., Oxidation Statesg Potentials, Equilibria, and Oxidation-

Reduction Reactions of~l^lutoriium. National Nuclear Energy Series I7-li)A
McGraw-Hill Book Con^iany, Inc., 1951i, p 272.

CONFIDENTIAL

y ^
01 0) si (S
 • • • " " * " "
... — ^~ ...-!-.. ' .... - "T"! lE-n
':: n z: :z .—.1
z*r: !z:::. . ' _ ' r -7-HI r ;_." - r r_"i'_ : r i : r .11 - ^ 1 1 . ;.zr-: ;:r.:- s.zz:- T j r r z m _t£;i zzzz 'ZZZ ZZZZ -~~ :rir:; iirr -; zzzz zzzz .:::TUin zz z\ :.:. : . ; ; • ; • E E ' . l ''-ZZ\Z 11 mi^
- -f- - —-.-7— f Ar-^
:":.:ir.:'.: ::::. : : : : :r*: . m z zz~r :::;- .::Ln zzz zzzz --Z zzzzz zzzz zzzzzz zzz -r.-rr :::..: i r : . : : ' ~ 7 7 zzzz 'ZZZZZ LE_' _— r ; —11 Uir-i
J.::-:
— (—
-zr~ ^
^EE
• 1 *-
m
;::.: :::_ : : : r .;--: -.-L- —z -:: -zzzz zzzz zzzzzz rz- zzzzz -zzzz .:rr_r -zzzz zzz:^zzz =ZE^ - m i l --t—-
\ pi
— {Tj
— : • - ' •
Ti.--t:v.:_ j:::,:f-:": ::;i tr— ZZZiZZ. ~—
zzizA - — r . ; - : i ; ZZZZ- zzz'-z.zzzz\zzzz Z..ZZZZ -r;- - - p - - - zzzzz:
:::.-.: zzzz -'— zzzzz ^
^:.:- - • - •
~--h— imzr. I —
— •
- ^ i
• ^
: r;-;!;_;;. .'.! r p ; . „ ; r.^ ; -
----;- . : : ' .
'Zzi
-;-J-.^:r 1 ? ..-.-1^ zzzz ^ EE EE: —1-
t_ 1 -. - ,
:... I • - • i - •
i: iteaction_ velocity uonstant oeu — ;
^ Z! z ; ri:;.: ..zjz.:; zii 1 Z ."L _ - : i _ --— K xi l l xu
C-!—." _ "-'_*- r . ~ I;L.,_ T^rr, zzzzzz h 1 1 1 : . - m : -z:zz.]
::' :i;.:..; prr-r
— _ _ . _ ^ „ . , _
— -.-r.^ =r-.-.i^t - - — •
'. i~.'. I'.'.'.'. ... , — :;;i_- z r : T . ^ - -zzzz -ZZZ- zzzz — _;_Z-" zzzz ::;::: zzzz — i : zzzzz zzzz zzzz.
::.. 1.:.; 0 - - Urr.. rx3 •—J
• 1 — —
- 1 - • - . - - zzr '-" 'ZZZZ .zzzz: i 1
:: ; : i : z ; CO:: ^ - „ - - •?>il zzz OS;:
m'l zz'E Ezz: — - r E "~ Z-ZZZZ i:r.i
0
T ~ 1-3
:;S -111
i::-. zrrr. irirz ".'.'.'. zzzz zzzzz zzzzzz 1 M
• - - - - - •zzz^. zzzz - -— -ZZZ.Z
^ '" — \ — _ _ _.___
: : : Lt i i ; ; 1
....
rr— TTE- TE^ — ^zzztrrzz.
::::: :.:i: :_-- .r:;: " ~ ^ :-i- z:=. fE :::; - - - z zzz zzzz l l n : —
—
:;-;; : - r j;r: -:i- —1
w yz zm ::.:.: :zz: :-:: :::: -IT • - -

i^7^ — _ii=
h^
i 1
zzzz
=1-4^
: ^ , _ „ . . _ . .
::.::J:M: r.— ^11 zzzz Tr:r — zzzz ^ ^ T r:ii —._
M r
• - • -

:::z :r:r — ~ :.—:J ZZZ- .7"Z :-::- 5^ • — - r:;: -zzzz zzzzz — •-111: Q zzz — ,
----
_. 1 . . . _ ^
---- - 1 ^._.
:::-: :.:r_: v i r r zr_H : i i : z : zzz.z : : •Er- zzzz zzzzz'zzzz — ^ zzzz

- --. * ^._^ .—
:r::-7 r - r —r ZZ-- zzzz - ^ rr:_- zzz z zzzz zzzz zzzz\ ;ii:r.
1
t;»^;i;
•^
- —
LCID DEPENDED[CY

.::: ::"^ r . . r z^z pEE zzzz .:::z: zzzz zzzz :z: :::! 11.: ZZZ z^z ri:ii zzzz rin-
1 F" M \—
: - :.— zrrr — ~ z - z - : r zzzz rrr.: " ^ ;.::: :r:_:; zzzz — TIT-
— —
\ •
::: CD
k- i~E:-_ "t"A
:trrr — ""
:::: -;:— ::z:s r.rzz — -iz.-. zzzz ^ zzzzz — 11.-1^ El —
... |_i.
... c<- r Z"Z - - - • _
— ^ ^ — --^ ;—- --=^.
_-z_:z EE- -=z z—: ETfe ^ k : ni: 1 - ; : /^ZZZ^-Z.
CO
t-S
H
r
— rr-^ 1
ZZZZ : : : : ' • : : :
vn- t-J ;:.r:
-:=:-
zrr: I=r- U-L„^ __._ ^ _ _ zzzz 11- ^ =J— ZZZ- E3
—^^ — _— — 1 —-1 1
. NITRITE OX]:DATION OF PU(III;

• --i h> ^ F v-^ ...1111

',- a^ ::::- I'.-I-— 1^ Vi/ uw .._— — X—_ :—u
s 2 S sr^ — ' f p —
CD
o X- 1 SVl O O 3 — — — — — — --.-.[.--^
:--.- " z rrrr i r - ^ i r :i-_il •1111-
- ^ s^
1
9 a
te^
' • • ' 1 \''::: :.::z .zrr; UT. -J .----— —: -ZZZZ E i : ":zz
ro ; „ -J V - • - 1
—- _ _„___:_ 3>:>k-:
TO TO —^ I
O zzz: zzzz. -— ^ r- - ... .-^-^ . ~;:~ zzzzz — -ZZZZZ ri:: VJT. —
•-d >r} --Y . . . 1 • • - 1 M - -
M .,__ < : > • , •
rrr: —^ — E E -zzz :-:: ' . . '. vn, -
z'zrz zzzzz zzzzz - r E : zzzz. vn. 1
!
EI.T-E • Z'.ZZZ _ • ; "
;^^ ; / • . • • ----- zrzm ..— "_~'. ;ZZZZ '-
- • - • - --f- — zzzz
:;:; i1 i zzzzz f-- rirr ztx:. zi:.zz l E E i:.E "::iii 'EE
 » ^ — n ^ i ^ i - t - i ' M 1 1 1 1 1 j 1 11 1 1 1 1 1 1 1 1 1 1 H M 1 1 f-i 1 1 1 1 1 1 1 1 1 1 1 1 f f j 1 j r F J i T T n - ' T 1 l E i e i J
•*>«. ^ ^ i l l 1J1 1
>£rWFIDLKTTIAL | I t ] -10- 1 | f mJ_^l6SS I E
1 I I I 1 1 '' 11 1 ] 4i N 1 tlf~rT1—"^1" I ' T T E J"
i ' N 1 M rJ 11 r 1 14
€?<* I1 M"^ J_l 1 l1 1i ! 1f 1 tl ] i FTGTfRE
• -—
'^ H H 1
L 1—' J j j_L 1 1 1

[""' f i l l \'P OXIDATION OF P u ( I I I ) BY NaN02 TL | J 4 t 1

\ \ \ \ 1 1 |4 H - EFFECT OF NITRITE CONCENTRATION 4 ^ ^ J-EH
( uV iN. I'SJJE ill
i ' \ \ \ \ ' rf*sJ 1 H^i^I~l'l M i II i"I 1 t l HE 1 1 1 t 1 M 1 1 Et h Ef 1 1 H~T~t"l 1 l^h H M i
<7 A
iRv K \ l mi>l
1 1 *" r \ \ \ \11 Mrs. r
11ll 1[M 1rr I \r\v\ HIM
M M l M T l~l
Em+m 1m 1
H i T M r HP H H E t H i
h h X W T\ vj \ 1 H ^ m w1 1i^ \\h\
1 _[ J |\ V 1
[ H 1H M r HE H H 1
H 4 14
l l l ' I \ \ \ \ i ' ' l l l ' ' ^V ' 1' 1 1 1 11 i 1 1' 1111 1' 11! 1 1

1
M I T \\ !\\ 1 A.'\r H T E H
'^^ \
1 rkJ
iN.
iM IT hi HE r i H HE I I H I M1 HE HE H I 1
nsr ^11 -)i^^mimFHf t r r mu Tr|+ H 1 H + KHTHtFH R F H ] I t H
iJi^MEM ' \ \ ' 1 X r t r HI t llpaFE H 1 TM l-ME HTErf ET E M [-M-T M
R-MtTf^
11 —l1
' \ ' \ E \\ NL-^E
H 1\i \ i\j
F IirF
H i
iPx1 f'k
1 HI n FhFFEl H F THF"MHE4HHEr rTi E H
H H 1 i~ 4~ H i
F^4
1 H— [
1—1———1 —1 — \ \ M —iVi— \ 1 1 —— 1 1 ^vi 1 — i— 1————I— 1^ ~ l — — — — — ———\T \ r \ \ — 1 —r~ 1
1 H 1 H H H \'' \ II 1 \ H J I I i 1 i~H4 I I H t r V1 H 1 1 I I H I 1 H 1 H Ff-H I I 11 H 1 11 -1 H
1 1 1 i 1 *'|\| |M PJ \ H I rJ H I
if*A i H 'HFFl F
J1 H
^^^ 1V
\
\Ft tH\\ ^ \f~f
jJv
H H Hi 4l r l rz-\ Ix
i\
i F 1 FH H F1 Ff HH F H t^FHFFI F I 1[ H
1
1 Ml'-11 r F i 1 \ ' \ 1 H Pv! 1 \ n H ITI Hi F M l-'\t 11 H Hi 1 H l~t FIE H l~FH-l HE H T
Ili {——
j' 1 [—
H1 1—ii 1 1—
\ j j—|\l
i M j \1 | \ |
[\ 1—— \\ 1—1 1 1 j—j—( 1—[ j—i 1—1 [i \[ \ 1 1—1—1——j 1——j —
I 1—1—1——
\ 1—1—1—1——
j —
I 1—1—1——
j 1——
j ——1——
[ \ I1
i l_. L_L 1 V..J \ 1 11 1,3 \ H' H H ix J H1
j i 1 1 \1 J Iv 1\ H i QJ
l i l t i i i i i i i i i v i n i i i i i x i \ i i i i i i i i i i i i i i i n . i i i i i i i i i i i i i i i i i i i i i i i i i i [ i i
1H H M E" H \ n \ 1 1 N ( \
H"hn
i
1
1
1 IF H~l FhF"^H
M ri \^ \NFM
H
1 \1
4 \i~l
\\ ^J 1 HH H hin11\
J\ III
n i r r J r rr \ H 1 1N X HE \
/»? 1 1 ^H I V LH H I \ \ 1
!1 n E l iH \\ r \N M \ \ M \\ H \
rJ.
1 1' r \H \ n^ \
1 r, u HEEE"! ET M\ •* H \ rK [
H <D E - H 1 H 1 i \ n^ \ \ \
l! l 1 -^^ { | | M H| | | M
' H M I \ i | \ l\ | i | | | \ |\ { l \\ M | M | M | | | | | | | \ | \| | | | | | | | | l | | | | | | | | | | |
1 r >-i E inT 1 El 1 N \ N 1X \ H
! 1 \ 1 H\ \ EM)
1 H^ \ \ IN \ 1T
1
H ' 1a,^i H E ii H 1 \^\ FJ \ A N\
MJ*^ iNJ
>
iti - lETr H T rrH"rV XEM T\ \
lI iM
s. w"|-H
H_LH
, H
H'L r r HE
11 H
k l\W
\ X
\
F H\\\ \N
H \
J J J LJJ_L i 1FH
U_j HJ.
t - j - 4 - j - i ( . J J - U I 4 1 1 1 i_j_i I_I_L
i 1 i^H 11 1 i 11 1 1 11 1 11 1 H IVi 1 1 \ 1 H 11 1 1 i\l 1 HNl 1 H 1 11 11 i 1 i 1 T J
H H \ N \ \ A Legend:
#* ! ' H H11 EFE
H \ 1 \| \ l l 1 11 1 \1 1 \NT1 l l \ 1 I I 1 I I 1 1 11
N
F^' 1\ \ \ \ ' W ^^''-WOo k
a
1 '"' H E i 1 H TT " N
\ K
\ F\\ \N 1 ^
HF< N N \ N • ® °''^53 0.0091
1
1 !
! i M \
\ \
1 \x\
rV^
\r i A n rtlo r\r\TnO
1 • r \ sc \ Mj U.0(<:! O.Ollo
M 1
N\ F N
K
\ \
l.-n
' L?-l 0.080 0.0128
1
1 H II II II 11 II H II 11 I I I H H 1 \ 1 l\l H 11 H H \ H H 1 U m \ 'H Fh K 0 nop. 0 oi 7^
1
1
\\ MJ N
\
\N • ri n nv r\ ni or"
1 H"1 HN \ r \ H / u.iuf u.uxyi)
1 1\ \ \ A, , , , , , , , , - • 1
1 N IN F T I Ml Mi
Tl 1m
T 1 iJ 1T T 1 In
MT Tr n H Mr r H r n r l-i-H J
a.i 1' 111111 H H ! H H H H H H H H H H H H H H H H H H H H H H l.F,l H H II1
5#Ll^i i^''rwi .;_
'7 CC 9
"iLL ^6
 h^' uu '\J >,MS .3SsslED

^^a>ri^
TT"" \ \'\\\ i"H 1 H l i F i 11 H H H H 1 H H 1 i11 i ' 1 I 1 f i I 1 rn T I I I I i 11 ' ' ' 1 1! 11111I I

r t l f l l l l l t i M l l l t i l i l i l l i i i l i l l i l i i l

1 1 ' JmJL^ ISXA^MKM \Jt'*ti^ht<te'\^'f\ iJriT >M<£«'k^. f r I i'U/iiifi^i'V! n HH

11 i 1 111H H 11 1H1 n 1 li H Hi
^ IJlFtlJltrMMftfflttM
(III|[ W\~ 1111111111111F
Li 1 11 1 H M H 1 ! i M 1 ,L-Ll . j 1 1 H i 1 H-1 1 1444- rr F 1 1 11 rlH-yil
^ FIGURE 1 1 -j-|—1 1 1 1 1 1 1 FIGUrIE i.(L !e\yi\iVi)£i I J TT\

tr it !, 1 \- \ • H \-X\
1T1 I 11I 1 1
TT 1 n . n f t n M NaNOo II 11 111II 11 /-> /-inn M NaNOo H n 107 M NaNfVi l-J. 1
+t-F
• -T—•* rri H M H H
1 I 11 1 1 1 1 1 H
1 Ml
I >]
ft* ' 111 11 11 1 1 1I
tr 1 1 ' ! , 1. 1
TnTiffiTiriivrnni FF-I HIH
LUJjiii 1 |_m H m i H ^ 4—1—1-4——I—1—|—^—j—1—1———1—1—[--1———1——1—1—\—1—1——I——1—f—j———1— 1
1 1 ' 1
'" 1 1 1-| 1 14 H - i J H H H 1 [.A^wl/in. 1 1 H H 1 H 1 ! I Jr L F 1 H
i I T t i l l ' J ^ ^ * \ H i ' <J'''^*f*ffl 11 r T r I I I I H <W~K 1 I Ll |K|P 4?f'• T 1 1 H ]_ H 1 H •r'H L1 1
! L1 ^L r l ^1 I l l l l ^ ^Tv 1 i/# w^ f l I n iS l i
' 1 ' M 1/ ^ \ \ / in. Tl H I 1 / •• i\ J1 \ I I ' / 1\ / \ ' r 1 111
' 1^ H I i^^i' "^^ r\ 1 / A ^ H i l l w^ "^^^ \ l i ' \ 111] H l H I l A^' "i^'lv, \ / \ I 1 1 ] 11 1
11 'M 'F^^S^^^K \ ^ •'r 1 11 1 1t J^lf>Z^ ^ i jL l/^v \ t 1 H ' H 1 r t t ^S^' —"c f. ^^ \ / \ H H 1 1
1 MB\ ^ ^ « ? I P V » - •>/'~^\\ 1 1 F t ! 1 ' ' - " ^ ^ ^ ^ i S s x k r <• J. N\ ' U ^ ^ ^ ^ 3 ! S i ^ S . ' \ ^ ^ / 'X.x 1
I Jmr\\ T a^o^_y>^t^^!^^ ' ^ 1 1 ^J^f\ ^ ^ ^ ^ s v Lt / ^ p s A \ [ A \J^ T , ^ ^ ^ ^ X V /y''"N\y H 1I
ijSKr LzL..^ 1 1 l*I^S^»^T<fe?^^^^Pd I i 1 \J^^ I I M i K vr^r t r r T M r i mSr\\ 1 1 ^^JsSvjkF-V^n. . J 11
' »^ 11 H 1 1 1 ^^^^r ' 1 \Mr\ H TTS* HPT'^^^H' "43^ 1 ^^^^-"•'f^^'^'T*!''! 1
' 1H 1t H 1H M 11 M 1 I N H 1 In TH 1 1 1 i T l 1 1 1 H ^^SC*^ 1 L I1
Ht-i 11 1 1 H M t-1 t 1 r n i 1 1 1 t I I 1 j ] | |J j | j
rcc II