DP

- 653

CHEMICAL SEPARATIONS PROCESSES FOR PLUTONIUM AND URANIUM (TID-4500, 16th Ed.)

PHYSICAL PROPERTIES OF URANIUM PROCESS SOLUTIONS

by

Robert S. Ondrejcin 0ctobe.r 1961

E. I. du Pont de Nemours & Co. Explosives Department Atomic Energy Division Technical Division - Savannah River Laboratory

Printed for The United States Atomic Energy Commission -1 Contract A.T (07-2)

Approved by H. M. Kelley, Research Manager Analytical Chemistry Division

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.

ABSTRACT

Integral diffusion coefficients, viscosities, d e n s i t i e s , and s u r f a c e t e n s i o n s were measured f o r t h e aqueous u r a n y l n i t r a t e - n i t r i c acid aluminum n i t r a t e system. The v a r i a t i o n o f t h e uranium d i f f u s i o n c o e f f i c i e n t was d e t e r mined as a f u n c t i o n of uranium c o n c e n t r a t i o n , n i t r i c a c i d c o n c e n t r a t i o n , and t e m p e r a t u r e .

c
2 -

CONTENTS

Page Introduction Summary Discussion Apparatus

P r o c e du r e s

4
5
6
7

Results I n t e g r a l D i f f u s i o n C o e f f i c i e n t s and C e l l C o n s t a n t s V i s c o s i t i e s , D e n s i t i e s , and S u r f a c e Tensions

B i b 1 o graphy i

11

a a

12
LIST OF TABLES AND FIGURES

Table
I

C a l i b r a t i o n of D i f f u s i o n C e l l s I n t e g r a l D i f f u s i o n C o e f f i c i e n t s and V i s c o s i t i e s D e n s i t y and S u r f a c e Tension

I1
I11

9
12

Figure
1

Diffusion C e l l

6 10 11

D i f f u s i o n C o e f f i c i e n t of Uranyl N i t r a t e i n Water v s . Temperature D i f f u s i o n C o e f f i c i e n t o f 0.200M Uranyl N i t r a t e v s . N i t r i c Acid C o n c e n t r a t i o n at; 25OC

PHYSICAL PROPERTIES OF URANIUM PROCESS SOLUTIONS

I NTRODUCTlON
The p r o c e s s o f s o l v e n t e x t r a c t i o n of uranium from an aqueous phase

i n v o l v e s a d i f f u s i o n mechanism. Data on t h e d i f f u s i o n c o e f f i c i e n t s of uranium s a l t s are l i m i t e d i n number and t h e c o n c e n t r a t i o n s r e a r e f r e q u e n t l y lower t h a n t h o s e of i n t e r e s t i n t h e s e p a r a t i o n s p r o c e s s e s . F o r a g i v e n s e t of c o n d i t i o n s , t h e d i f f u s i o n c o e f f i c i e n t s quoted i n t h e l i t e r a t u r e v a r y by as much as a f a c t o r of two. Since a r a t i o n a l i n t e r p r e t a t i o n of mass t r a n s f e r i n t u r b i n e c o n t a c t o r s was d e s i r e d , a more p r e c i s e s e t o f v a l u e s had t o be obt a i n e d o v e r t h e c o n c e n t r a t i o n range of i n t e r e s t .

The work d e s c r i b e d h e r e c o v e r s the measurement o f d i f f u s i o n c o e f f i c i e n t s o f u r a n y l n i t r a t e , n i t r i c a c i d , and aluminum n i t r a t e i n t h e concent r a t i o n range normally e n c o u n t e r e d i n t h e s e p a r a t i o n s p r o c e s s e s f o r n a t u r a l and e n r i c h e d uranium. Measurements were made by means of a ( 4 9 5 ) porous diaphragm c e l l w i t h magnetic s t i r r i n g i s e x p r e s s e d i n t h e S t o k e s - E i n s t e i n r e l a t i o n s h i p and has been t r e a t e d by o t h e r s ( 6 1 ; t h e r e f o r e , measurements o f v i s c o s i t y ( p ) were made on a l l s o l u t i o n s p r i o r t o d i f f u s i o n . Measurements of d e n s i t y ( p ) and s u r f a c e t e n s i o n were a l s o made because t h e d a t a would be u s e f u l i n d e s i g n i n g e x t r a c t i o n equipment. With t h e a v a i l a b l e i n f o r m a t i o n t h e Schmidt group (p/p D ) can be determined f o r u s e i n c a l c u l a t i o n s of f l u i d flow and mass t r a n s f e r where t h e d i f f u s i o n c o e f f i c i e n t i s seldom used a l o n e .
SUMMARY
The v a r i a t i o n of d i f f u s i o n ( D ) a s a f u n c t i o n of s o l u t i o n v i s c o s i t y

Measurements of t h e i n t e g r a l d i f f u s i o n c o e f f i c i e n t s , v i s c o s i t i e s , d e n s i t i e s , and s u r f a c e t e n s i o n s were made on s o l u t i o n s of u r a n y l n i t r a t e , n i t r i c a c i d , and aluminum n i t r a t e . The r a n g e o f c o n c e n t r a t i o n s i n c l u d e d t h o s e n o r m a l l y found i n t h e s e p a r a t i o n s p r o c e s s e s f o r i r r a d i a t e d n a t u r a l and e n r i c h e d uranium.
Graphs are p r e s e n t e d showing v a r i a t i o n s i n the d i f f u s i o n c o e f f i c i e n t of uranium n i t r a t e w i t h changes i n t e m p e r a t u r e and n i t r i c a c i d

concentration.

- 4 -

DISCUSSION
The d i f f u s i o n c o e f f i c i e n t s t h a t a r e p u b l i s h e d f o r uranium s a l t s are based on two d i f f e r e n t t y p e s of measurements. The f i r s t type i s t h e measurement of t h e s e l f - d i f f u s i o n o r d i f f e r e n t i a l d i f f u s i o n c o e f f i c i e n t , normally based on t h e c a p i l l a r y tube t e c h n i q u e f i r s t developed by Anderson and S a d d i n g t ~ nI' . I n th:Ls method r a d i o i s o t o p e s are used and ~ t h e d i f f u s i o n o f an i s o t o p e , i n th:Ls c a s e uranium ( l Y 2 ) , i s measured i n the absence of a c o n c e n t r a t i o n g r a d i e n t . The second type of measurement i n v o l v e s a c o n c e n t r a t i o n g r a d i e n t . The v a l u e o b t a i n e d i s an a v e r a g e f o r t h e e o n c e n t r a t i o n s t u d i e d and i s known as t h e i n t e g r a l d i f f u s i o n c o e f f i c i e n t . The change i n c o n c e n t r a t i o n i s n o r m a l l y measured by l i g h t r e f r a c t i o n o r i n t e r f e r e n c e ('I, conductance, o r chemical means a f t e r d i f f u s i o n through a d i a ~ h r a g m ' ~ ) The diaphragm c e l l is a c l o s e d . g l a s s tube s e p a r a t e d i n t o two compartments by a s i n t e r e d g l a s s f r i t . D i f f u s i o n o c c u r s through t h e f r i t f'rom a s o l u t i o n o f h i g h c o n c e n t r a t i o n t o a s o l u t i o n of lower c o n c e n t r a t i o n . Most o f t e n t h e s a l t s a r e d i f f u s e d i n t o some i n i t i a l l y p u r e s o l v e n t .
The a v e r a g e l e n g t h o f t h e d i f f u s i o n . p a t h i s determined by the a v e r a g e p o r e s i z e , the t h i c k n e s s o f the f r i t , and t h e l a m i n a r l a y e r formed on e i t h e r s i d e o f t h e f r i t . P h y s i c a l measurement of t h i s p a t h l e n g t h is not p r a c t i c a l ; therefore, the c e l l i s calibrated w i t h a standard of

known d i f f u s i o n c o e f f i c i e n t .

Much of t h e e a r l y work i s u n r e l i a b l e because of t h e problem o f p r o v i d i n g a d e q u a t e a g i t a t i o n i n t h e c e l l . E a r l y measurements were based on d e n s i t y s t i r r i n g . The s o l u t i o n w i t h t h e h i g h e s t d e n s i t y was p l a c e d i n t h e upper compartment and allowed t o d i f f u s e downward. Bulk s t r e a m i n g o c c u r r e d i f the f r i t had a few l a r g e p o r e s , and t h e t h i c k n e s s of the l a m i n a r l a y e r v a r i e d depending on the v i s c o s i t i e s of the l i q u i d s i n t h e compartments. I n a n o t h e r methold of s t i r r i n g , s o l i d b o d i e s were used") t h a t sank as t h e c e l l was r o t a t e d . S e v e r a l p a p e r s have system, one magnetized bar r e s t s on the f r i t i n t h e t o p compartment and a n o t h e r f l o a t s a g a i n s t t h e bottom of t h e f r i t i n t h e bottom compartment. The bars a r e moved by a r o t a t i n g magnetic f i e l d . T h i s method e l i m i n a t e s t h e f o r m a t i o n of .laminar l a y e r s . D i f f u s i o n c o e f f i c i e n t s of e l e c t r o l y t e s i n s i m p l e systems u s u a l l y a g r e e w e l l w i t h t h e o r y a t c o n c e n t r a t i o n s below 0 . O l M ( 1 3 I, b u t of t e n d e p a r t r a d i c a l l y at higher concentrations. In theoretical calculations the d i f f u s i o n c o e f f i c i e n t i s a f u n c t i o n of such q u a n t i t i e s as t r a n s f e r e n c e numbers c o n d u c t i v i t y , e l e c t r o p h o r e t i c c o n t r i b u t i o n s , and concent r a t i o n 'I4). Consequently, i n t e g r a l d i f f u s i o n c o e f f i c i e n t s must be measured a t c o n c e n t r a t i o n s above 0.01M o r when more t h a n two components are p r e s e n t .
appeared i n which m a g n e t i c s t i r r i n g w a s
'12 )

W i t h this

- 5 -

APPARATUS
A t y p i c a l c e l l i s shown i n F i g u r e 1. The c e l l compartments were made o f "Pyrex" g l a s s o f 28-mm OD. The compartments were approximately 50 m l i n volume and were s e p a r a t e d by a f r i t 25 mm i n diameter w i t h a 4-5.5 micron nominal maximum p o r e s i z e . The upper and lower compartments were c l o s e d w i t h a 10/30 % s t o p p e r and a "Teflon" s t o p c o c r e s p e c t i v e l y . The s t i r r e r s were "Teflon"-coated magnetic s t i r r i n g bars a t t a c h e d t o g l a s s s h a f t s by means o f s p e c i a l "Teflon" c o l l a r s . T h i s arrangement p r e v e n t e d t h e s t i r r e r s from rubbing a g a i n s t t h e f r i t , as o f t e n o c c u r s i n t h i s t y p e of d e s i g n (10,11,12)

Magnetized Stirring Ear

4
I

FIG. 1 DIFFUSION CELL

The s o l u t i o n was s t i r r e d by DC m a g n e t i z a t i o n and d e m a g n e t i z a t i o n of f o u r s u c c e s s i v e p a i r s of c o i l s , which produced a r o t a t i n g magnetic f i e l d . The f i e l d could be v a r i e d from 40 t o 200 rpm by c o n t r o l l i n g t h e speed of t h e s w i t c h i n g motor. The c o i l s were mounted on a m e t a l r i n g and were l a r g e enough t o o p e r a t e b o t h t h e upper and lower s t i r r e r s . Each s e t o f c o i l s was e n c a p s u l a t e d i n "Kold-Weld"* r e s i n , s o t h a t t h e c o i l s could be immersed i n a water b a t h r e g u l a t e d a t 25, 40 and 55OC t o +O.O5OC. V i s c o s i t i e s were measured a t t h e s e t e m p e r a t u r e s w i t h a s e r i e s of A Cannon-Fenske v i s c o m e t e r s a c c o r d i n g t o ASTM method D445-53T. C h r i s t i a n Becker s p e c i f i c g r a v i t y b a l a n c e , Model SG-1 and a Cenco-Du Nouy t e n s i o m e t e r w i t h a 6-em p l a t i n u m r i n g were used t o measure s p e c i f i c g r a v i t y and s u r f a c e t e n s i o n , r e s p e c t i v e l y , i n a s p e c i a l c e l l through which w a t e r from t h e w a t e r b a t h was c i r c u l a t e d a t the s p e c i f i e d temperatures.
PROCEDURES

P r i o r t o t h e p r e p a r a t i o n o f multicomponent s o l u t i o n s , a s o l u t i o n of each component was s t a n d a r d i z e d . Uranium s o l u t i o n s were p r e p a r e d from u r a n y l n i t r a t e and a n a l y z e d by t i t r a t i o n a g a i n s t a s t a n d a r d i z e d c e r i c s o l u t i o n . N i t r i c a c i d was analyzed by a c i d - b a s e t i t r a t i o n and t h e aluminum n i t r a t e s o l u t i o n was analyzed by p r e c i p i t a t i o n w i t h 8-hydroxyquinoline. The analyzed s o l u t i o n s were then q u a n t i t a t i v e l y combined and d i l u t e d t o produce t h e d e s i r e d f i n a l s o l u t i o n s . A f t e r e a c h d i f f u s i o n experiment, uranium was analyzed by t h e same method t h a t was used p r i o r t o d i f f u s i o n . The t o t a l a c i d i t y o f t h e samples c o n t a i n i n g uranium o r aluminum was determined p o t e n t i o m e t r i c a l l y . Potassium f l u o r i d e was used as a complexing a g e n t f o r uranium and aluminum i n t h e s e samples. Aluminum was determined as p r e v i o u s 1 d e s c r i b e d a f t e r i t was s e p a r a t e d f:rom uranium by i o n exchange(15

7.

B e f o r e t h e d i f f u s i o n c e l l was f i l l e d , a l l s o l u t i o n s were degassed and brought t o t h e temperature of t h e w a t e r b a t h . Dissolved g a s e s can form b u b b l e s i n the f r i t and p a r t i a l l y b l o c k t h e p o r e s d u r i n g d i f f u s i o n . Expansion o r c o n t r a c t i o n of t h e s o l - u t i o n s i n t h e d i f f u s i o n c e l l would cause b u l k s t r e a m i n g through the f r i t . The lower compartment was i n i t i a l l y f i l l e d by p a r t i a l l y e v a c u a t i n g t h e e n t i r e c e l l , opening t h e stopcock, and drawing i n s o l u t i o n u n t i l t h e f r i t was f i l l e d . Some s o l u t i o n was allowed t o e n t e r t h e upper compartment t o d r i v e any e n t r a p p e d gases from t h e p o r e s of t h e f r i t . Excess s o l u t i o n on t h e f r i t was removed w i t h a small p o l y e t h y l e n e t u b e under vacuum. The upper compartment was t h e n f i l l e d w i t h a q u a n t i t y of p u r e s o l v e n t e q u a l t o t h e volume o f t h e lower compartment.

* Product o f P r e c i s i o n Dental Mfg. Co.

- 7 -

After t h e f i l l e d c e l l was immersed i n the water, a c o n c e n t r a t i o n g r a d i e n t was allowed t o develop i n t h e f r i t ( 3 ) . T h i s r e q u i r e d a b o u t f o u r h o u r s . The c e l l was t h e n removed, the s o l u t i o n i n the u p p e r compartment was emptied w i t h a p o l y e t h y l e n e tube under vacuum, and t h e compartment was r i n s e d and f i l l e d w i t h new s o l v e n t . The s o l u t i o n i n the lower compartment was withdrawn i n the same manner and r e p l a c e d w i t h new s t a n d a r d s o l u t i o n . During these o p e r a t i o n s i t was n e c e s s a r y t o e x e r c i s e c a r e t o p r e v e n t d i s t u r b i n g the c o n c e n t r a t i o n g r a d i e n t i n the f r i t . T h i s procedure reduced u n c e r t a i n t i e s i n t h e i n i t i a l c o n c e n t r a t i o n s i n t h e lower compartment and allowed a d e t e r m i n a t i o n o f t h e e x a c t s t a r t i n g time.

A i n i t i a l r u n was made t o d e t e r m i n e t h e l e n g t h of time r e q u i r e d f o r n 2O-25$ of t h e s o l u t e molecules t o d i f f u s e . The r u n s used f o r measurement were t h e n made, and t h e s o l u t e c o n c e n t r a t i o n was measured o n l y a t t h e end of t h e r u n . A d i f f u s i o n r u n normally l a s t e d from 72-240 h o u r s .
RESULTS
I N T E G R A L D I F F U S I O N COEFFICIENTS AND CELL CONSTANTS
( The i n t e g r a l d i f f u s i o n c o e f f i c i e n t can be e x p r e s s e d by Equation (1) 3 ~ 1 6 )

D=-ln-

Bt

Act
ACo

where heo = c o n c e n t r a t i o n d i f f e r e n c e between compartments at time 0 Act

=

c o n c e n t r a t i o n d i f f e r e n c e between compartments a t time t integral diffusion coefficient

t = time B = a diffusion c e l l constant

I n d i f f u s i o n measurements a l l s o l u t i o n s must be analyzed a c c u r a t e l y because smal e r r o r s i n c o n c e n t r a t i o n produce a l a r g e change i n the k Ct v a l u e of I n The l i m i t i n g f a c t o r i n t h e v a l u e o f 5 i s t h e

-.
0

a c c u r a c y of t h e d e t e r m i n a t i o n of s o l u t e c o n c e n t r a t i o n s .
The v a l u e of 6 i s w e l l known f o r o t a s s i u m c h l o r i d e a t 2 5 O C when 25% of a 0.200M s o l u t i o n diffuses. The d i f f u s i o n c e l l s were c a l i b r a t e d w i t h t h i s s t a n d a r d . The K C 1 s o l u t i o n s were analyzed by t i t r a t i o n w i t h s t a n d a r d i z e d s i l v e r n i t r a t e and d i c h l o r o f l u o r e s c e i n

indicator.

- 8 -

It has been r e p ~ r t e d o ) t h a t t h e c e l l c o n s t a n t w i l l v a r y w i t h l~ s t i r r i n g speed u n t i l l a m i n a r l a y e r f o r m a t i o n is d e s t r o y e d on b o t h s i d e s o f t h e f r i t . O b s e r v a t i o n s showed t h a t the v a l u e of 5 f o r potassium c h l o r i d e appeared t o v a r y u n t i l a s t i r r i n g speed o f 70-90 rprn was reached. V a r i a t i o n s i n t h e speed n e c e s s a r y t o r e a c h a c o n s t a n t 6 were p r o b a b l y dependent upon s l i g h t v a r i a t i o n s i n the s u r f a c e s o f t h e f r i t s . prom the minimum s t i r r i n g speed r e q u i r e d f o r a c o n s t a n t 5 v a l u e t o 150 rpm, t h e r e was no v a r l . a t i o n i n the v a l u e o f 6. D i f f u s i o n s were made w i t h s t i r r e r speeds o f 125-130 rpm.

Table I shows t y p i c a l r e s u l t s from c a l i b r a t i o n s of c e l l s w i t h 0.200M potassium c h l o r i d e .

TABLE - I C a l i b r a t i o n of Diffusion C e l l s c e l l. C o n s t a n t , -ern-' Run I1 Avg.

No. Run I - - _ _ 1
2

, B

0.0395 0.0762 0.0640

0.0399 0.0758

3 4

0.0626 0.0506

0.0397 0.0760 0.0633 0.0508

0.0511

The d i f f u s i o n c o e f f i c i e n t s quoted in Table I1 a r e f o r t h e m u l t i p l e

component systems and n o t f o r s i n g l e components in a s o l v e n t u n l e s s s p e c i f i e d as such.

The a v e r a g e c o e f f i c i e n t of v a r i a t i o n of uranium d i f f u s i o n c o e f f i c i e n t s is 4.8%. The v a l u e o f n v a r i e d from 2 t o 4 .

TAB15 - I1 I n t e g r a l D i f f u s i o n C o e f f i c i e n t s and V l s c o s l t l e s uranyl Nitrate, M

0.0200

M M OC - --

Nitric Acid.

Aluminum Nitrate,

Temp.,

Viscosity.

mil1iDoisc:s

D i f f u s i o n C o e f f i c i e n t , cm2/sec Uranyl N i t r a t e N i t r i c Acid Aluminum N i t r a t e

25.0 25.0 25.0

0.200 2.00 0.200 0.200

0.200

10.1

9.15

7.8
8.3

x 10-4 x 10-6 x 10-6

9.5
10.2 10.3

8.4

0.100
1.00 3.00

25.0 25.0 25.0 0.500

1.00

6.1 x

lo-

9 . 5 x io- 4.0 x lo-

3.8
10-~

11.3

4.6 x 4.4 x 10-6 9.6 x

10.2 x 10-6

0.200
0.200

25.0 25.0 25.0 25.0 25.0 25.0

40.0

14.6
22.2 15.0

0.200
0.200

1.00 1.00

0.500
1.00

23.6

0.200
0.200

3.00
3.00

0.500
1.00

16.7
26.4 6.78 7.43 5.21 5.76

8.9 x 10-6 11.6 x lo- 9.9

x 10-6

7 . 8 x io- 9.9 lo-* 4.5 x

9.4

9.2 x lo-
x

8 . 9 x 10-6

lo-

4.8 x 7.0 x 4.4 5.3

x 10-6 x 10-

0.0200

13.0 x

lo-

5.2 x lo-

0.200
0.0200

40.0

13.6
13.8

x
x

55.0 55.0

0.200

1 4 . 8 x lo-

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The d i f f u s i o n c o e f f i c i e n t s of uranium n i t r a t e i n the absence of aluminum n i t r a t e d e c r e a s e d w i t h i n c r e a s e d n i t r i c a c i d c o n c e n t r a t i o n , which i n d i c a t e s complex i o n f o r m a t i o n . Aluminum n i t r a t e i n c r e a s e d the d i f f u s i o n c o e f f i c i e n t of uranium i n t h e absence of n i t r i c a c i d . I n the c o n c e n t r a t i o n r a n g e s s t u d i e d , the aluminum n i t r a t e t a k e n a l o n e was more e f f e c t i v e i n i n c r e a s i n g the d i f f u s i o n c o e f f i c i e n t of uranium t h a n t h e n i t r i c a c i d was i n d e c r e a s i n g t h e d i f f u s i o n c o e f f i c i e n t of uranium. With t h e i n t r o d u c t i o n of aluminum n i t r a t e o r n i t r i c a c i d t o t h e d i f f u s i o n s o l u t i o n s , the d i f f u s i o n c o e f f i c i e n t s d i d n o t c o n t i n u e t o f o l l o w the o r i g i n a l t r e n d s c o n s i s t e n t l y . F i g u r e 2 shows the i n c r e a s e i n d i f f u s i o n c o e f f i c i e n t a t 0.0200 and 0.200M uranium n i t r a t e w i t h t e m p e r a t u r e . The r e l a t i o n s h i p of t h e d i f f u s i o n c o e f f i c i e n t of 0.2M uranium n i t r a t e and the c o n c e n t r a t i o n o f n i t r i c a c i d from 0.001 t o 3M i s shown i n F i g u r e 3. The small i n c r e a s e s of t h e i n t , e g r a l d i f f u s i o n c o e f f i c i e n t a t 2 5 O C w i t h i n c r e a s i n g uranium n i t r a t e c o n c e n t r a t i o n o v e r a r a n g e of 0.02 t o 2M a r e shown i n Table 11.

6'

20

30

Temperature,

40

OC

50

60

t
1

Nitric Acid,

FIG. 2 DIFFUSION COEFFICIENT OF URANYL NITRATE IN WATER VS. TEMPERATURE

FIG. 3 DIFFUSION COEFFICIENT OF 0.200M URANYL NITRATE VS. NITRIC ACID CONCENTRATION AT 25OC

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VISCOSITIES, DENSITIES, AND SURFACE TENSIONS The problem o f c o r r e l a t i o n of d i f f u s i o n c o e f f i c i e n t s w i t h v i s c o s i t i e s can be approached i n two d i f f e r e n t manners. The c l a s s i c a l method u s e s t h e S t o k e s - E i n s t e i n r e l a t i o n s h i p , which assumes t h a t t h e medium i s c o n t i n u o u s and t h e d i f f u s i n g mol.ecule i s l a r g e . I n an a l t e r n a t i v e approach t h a t depends on t h e a b s o l u t e r e a c t i o n r a t e t h e o r y , d i f f u s i o n and v i s c o u s flow a r e c o n s i d e r e d t o be v e r y s i m i l a r . The assumption i s made t h a t t h e d i f f u s i n g molecules and t h e medium have a p p r o x i m a t e l y t h e same dimensions. Theore t i c a l t r e a t m e n t o f t h e s e methods o f approach i s a v a i l a b l e i n the l i t e r a t u r e ( l4

Table I11 shows t h e v a l u e s of t h e d.ensity and s u r f a c e t e n s i o n f o r t h e s o l u t i o n s of u r a n y l n i t r a t e , n l . t r i c a c i d , and aluminum n i t r a t e .

TABLE - I11 Density and Surface Tension Uranyl Nitrate, Nitric Acid, Aluminum Nitrate, Temp.,
OC

0.0200 0.200 2.00 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.0200 0.200 0.0200 0.200

0.100 1.00

3.00

1.00 1.00 3.00 3.00

a/ml
1.004 1.062
1.067 1.096 1.162

Density,

Surface Tension, dyne s/cm

25.0 25.0 25.0 25.0 25.0

1.641

73 73

77
70 70 70

25.0

0.500 1.00 0.500

0.500 1.00

1.oo

25.0 25.0 25.0 25.0 25.0 25.0 40.0 40 .O

1.143
1.218 1.254 1.238

1.175

1 313
1.000 1.056

75 74 45 45 48 49
70

55.0
55.0

0.993

64
67

1.051

60

These v a l u e s w i l l be u s e f u l f o r detlermining the d i m e n s i o n l e s s Schmidt number and the Reynolds number' l7 I . The Schmidt number i s o f t e n used i n c a l c u l a t i o n s i n v o l v i n g t u r b u l e n t f l o w and t h e Reynolds number i s used i n approximations of f l u i d flow.
R. S. O n d r e j c i n A n a l y t i c a l Chemistry D i v i s i o n

8.s. o +

11

BIBLIOGRAPHY

1. Saddington, K. The Self-Diffusion of Uranium Ions in Solution. Atomic Energy Research Establishment, Harwell, Berkshire, England. Research and Development Report AERE-C/R-626, 13 pp. (December 1950).
2 .

Hahn, H. T. Self-Diffusion of Uranyl Ion and the Uranium Tributyl Phosphate Complex. Hanford Atomic Products Operations, Richland, Wash. AEC Research and Development Report HW-31803, 20 pp. (July 1954). Coefficients Using an Improved Diaphragm Cell. Atomic Energy Research Establishment, Harwell, Berkshire, England, Research and Development Report AERE CE/R-1120, 16 pp. (November 1954). Mixtures

3 Lewis, J. B. Some Determinations of Liquid Phase Diffusion .

4. Hammond, B. R. and R. H. Stokes. "Diffusion in Binary Liquid

Part 2". Trans. Faraday SOC. 51, 1641-9 (1955).

5. Hammond, B. R. and R. H. Stokes. "Diffusion in Binary Liquid Mixtures - Part 3". Trans. Faraday SOC. 52, 781-6 (1956).
6. Glasstone, S., et al. The Theory of Rate Processes. 1st Ed.
New York: McGraw-Hill, pp. 477-551 (1941).

7. Anderson, J. S. and K. Saddington. "The Use of Radioactive

Isotopes in the Study of the Diffusion of Ions in Solution". J. Chem. SOC. (London) 1949, pp. s381-6. Interference Diffusion Studies". Rev. Sci. Instr. 20, 209-15

8. Gosting, L. G., et al. "Equipment and Experimental Methods for (1949) * 9. Huizenga, J. R., et al.
"Electrolytic Properties of Aqueous Solutions of Polyacrylic Acid and Sodium Hydroxide. 11. Diffusion Experiments Using Radioactive Sodium". J. Am. Chem. - 72, 4228-32 (1950). SOC.

10. Nielsen, J. M., et al. "The Self-dif]fusionCoefficients of the Ions in Aqueous Sodium Chloride and Sodium Sulfate at 25". J. Am. Chem. SOC. 2, 446-51 (1952). 11. Smith, I E. and J. A. Storrow. "Diffusion Coefficients of . Ethanol in Aqueous Solutions". J. Appl. Chem. 2, 225-35 (1952).

12. Stokes, R. H. "An Improved Diaphragm-cell f o r Diffusion Studies, and Some Tests of the Method". J. Am. Chem. SOC.72, 763-7 (1950)

12

13. Langsworth, L. G., et al. "The Diffusion of Electrolytes and 46, Macromolecules in Solution". Ann. N. Y. Acad. Sci. - 211-346
(1945)

14. Stokes, R. H.
15.

"Electrophoretic Contributions to the Diffusion 2533-4 (1953). of Electrolytes". J. Am. Chem. SOC. B,

MacDonald, C . M. Precise Determination of Uranium in Uranyl Nitrate-Aluminum Nitrate Solctions. E. I. du Pont de Nemours & Co., Savannah River Laboratory, Aiken, S. C. AEC Research and Development Report DP-503, 8 pp. (July 1960).

16. Cole, A. F. W. and A. R . Gordon.

- 733-7 (1936). 40J

"The Diffusion of Copper Sulfate in Aqueous Solutions 'of Sulfuric Acid". J. Phys. Chem.

17. Chemical Engineers' Handbook. J. H. Perry, ed. 3rd Ed. New York: McGraw-Hill, pp. 375, !543,1224-7 (1950).

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