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ARGONNE NATIONAL LABORATORY V,

P . O. Box 299
Lemont, Illinois

ABSORPTION SPECTRA O F URANYL COMPOUNDS

IN SOLUTION

by

Eugene Rabinowitch

INFORMATION DIVISION

D e c e m b e r 1953

This p a p e r will be published as p a r t of The


C h e m i s t r y of U r a n i u m , P a r t II, Nationals-Nu-
c l e a r E n e r g y S e r i e s Division VIII. It is issued
at this t i m e to p e r m i t review and c o m m e n t
p r i o r to publication and to m a k e the inforn^a-
tion available to other Atomic Energy C o m -
mission laboratories promptly.

Operated by The U n i v e r s i t y of Chicago


under
Contract W-31-109-eng-38
DISCLAIMER

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1

• / •

TABLE OF CONTENTS

Page

1. A b s o r p t i o n Spectra of the F r e e (Hydrated) Uranyl Ion and of 2


the P r o d u c t s of Its Hydrolysis ,

2. A b s o r p t i o n Spectra of Uranyl Ions Com-plexed with Acid Anions . . 15


2.1 Effect of Inorganic Anions on U r a n y l Spectrurn in Solution. . . 15
2.2 Complexing with Organic Ions 23

3. A b s o r p t i o n Spectya of Uranyl Compounds in Organic Solvents. . . . 45

4. Rannan S p e c t r u m and Infrared S p e c t r u m of Uranyl Salt Solutions. . 66


2

1. ABSORPTION SPECTRA OF THE F R E E ( H Y D R A T E D ) URANYL ION


AND O F THE PRODUCTS OF ITS HYDROLYSIS

F r e e U"*"^ ions do not occur in solution; if a compound derived from


this ion, such a s UF^, c o m e s in contact with w a t e r , it is immediately h y d r o -
lyzed, i.e., a s s o c i a t e d with the anions of w a t e r , even at the lowest a c c e s s i b l e
pH v a l u e s . The f i r s t step in this hydrolysis can be w r i t t e n a s :

U+^ + 4 0 H " —UOt+ + 2H2O, or

U+6 + 20"" ^UOj+

and leads to the divalent u r a n y l ion, which is stable over a c o n s i d e r a b l e


pH r a n g e . F u r t h e r hydrolysis o c c u r s in non-complexed solutions at about
pH 2, and ends in precipitation; c e r t a i n anions, such as the c i t r a t e ion, can
p r e v e n t their p r e c i p i t a t i o n up to pH 10 by forming soluble complexes with
u r a n y l ions (see Section 2).

Most of the solid U(Vl) compounds a r e salts derived from the divalent
u r a n y l ion. T h e i r dissolution in w a t e r produces solutions whose s p e c t r u m is
the r e s u l t of s u p e r p o s i t i o n of the s p e c t r u m of free (hydrated) u r a n y l ion
T U02"'"j"aq (perhaps UO^"*" • 6H2O) and of the s p e c t r a of complexes of this
ion with the anions p r e s e n t in solution. In addition to sijmple complexes of
the type n U02^"'"X~^ r , complexes containing two or naore uranyl ions
bridged by divalent anions nnay o c c u r . The stepwise hydrolysis of u r a n y l
ions, in p a r t i c u l a r , probably involves the formation of two polyuranyl c o m -
p l e x e s , {(U02)20]-++ (=U20^+) and {(U02)302}^"^ (=U30|+). A p r e c i s e and
s y s t e m a t i c study of the extinction c u r v e s of solutions of varying c o m p o s i -
tions, c o n c e n t r a t i o n , acidity and ionic s t r e n g t h is needed for r e l i a b l e i n t e r -
p r e t a t i o n of the a b s o r p t i o n s p e c t r u m of a given uranyl salt.

To obtain the s p e c t r u m of the free (hydrated) u r a n y l ion, one has to


u s e s a l t solutions that contain no c o m p l e x e s with the anions of water and of .
a c i d s . F o r this p u r p o s e strongly acid p e r c h l o r a t e solutions a r e best, b e c a u s e
ClO^ is the anion with the l e a s t tendency for complexing; Sutton (l947) found
that adding sodium p e r c h l o r a t e to a 0.04M U02(C104)2 solution caused no
change in s p e c t r u m up to a total concentration of 3M ClO^. The p r e s e n c e of
e x c e s s p e r c h l o r i c acid is the b e s t m e a n s to prevent a s s o c i a t i o n of U02^ c a t -
ions with the anions of w a t e r without introducing complexing with the anions
of the acid.

Absorption c u r v e s of u r a n y l p e r c h l o r a t e solutions w e r e f i r s t r e p r o -
duced by von Kiss and c o - w o r k e r s (l942a,b); but they do not a g r e e with the
c u r v e s obtained in the m o r e r e c e n t a n d c a r e f u l m e a s u r e m e n t s bySuttonand Ahrland.
The change in the a b s o r p t i o n c u r v e of a u r a n y l p e r c h l o r a t e s o l u -
tion in p e r c h l o r i c acid with d e c r e a s i n g concentration of the latter is shown
in F i g u r e 2.1 (after Sutton). This figure indicates a strong i n c r e a s e in
a b s o r p t i o n throughout the s p e c t r u m at pH values above 2.5 ( c f . F i g u r e 2.2,
which shows 2 at 416 mjU as function of pH). Sutton attributed this change to
a s t e p w i s e h y d r o l y s i s , beginning with the formation of the polyuranyl c o m -
p l e x e s , (U02)20"'""'' and (U02)302''""*" . This type of complexing can be r e p r e -
sented in s e v e r a l ways : as a substitution r e a c t i o n of U02"^ ions with H2O
m o l e c u l e s or OH" i o n s , or a s an a s s o c i a t i o n with 0 ~ " ions. (The concen-
t r a t i o n of the l a t t e r is e x t r e m e l y low so that hydrolysis is unlikely to
p r o c e e d t h r o u g h t h e i r i n t e r m e d i a r y ; but, fo-rmally, polyuranyl complexes
of this type a r e m o s t easily u n d e r s t o o d a s products of a s s o c i a t i o n of 0~~
anions with UO2"'*' cations.) The t h r e e a l t e r n a t i v e i n t e r p r e t a t i o n s a r e
r e p r e s e n t e d by the following p a i r s of e q u a t i o n s :
Exchange r e a c t i o n s with w a t e r m o l e c u l e s :
2UO^+ + H2O _ ^ [ ( U 0 2 ) 2 0 } + + (=U20^+) + 2H+ (1)
{(U02)20}++ + UO2++ + H2O ^ § 2 ^ {(U02)302]++ (= (U308}++)+2H+(2)
Exchange r e a c t i o n s with hydroxyl i o n s :
2UO^"^ + 2 0 H " :^==^ f_(U02)20J+'^ + H2O (3)
| ( U 0 2 ) 2 0 J + + + UOt^ + 2 0 H " ^ = - [(U02)302}++ + H2O (4)
A s s o c i a t i o n s with 0~~ i o n s :
2UO++ + O " : ^ = ^ {(U02)20]++ (5)
{(U02)20]++ + UO++ + O " ^ = ^ {(U02)202}++ (6)

Sutton c a l c u l a t e d the a b s o r p t i o n c u r v e s (Figure. 2.3) of the t h r e e


p o s t u l a t e d ionic s p e c i e s using the following equilibriunn constants d e r i v e d
f r o m pH m e a s u r e m e n t s :
Ki = 1.24 X 10"^ (7)
K2 = 2.5 X 10"'' (8)
( T h e s e c o n s t a n t s a r e , of c o u r s e , strongly dependent on ionic strength.)

The choice of equilibria (l) and (2), in p r e f e r e n c e to the s i m p l e r


hydrolytic equilibria involving one u r a n y l ion only:
UO^+ + H2O ; i = ^ U 0 2 0H+ + H+ (or UO^+ + OH" ;;iii: UO2OH+) (9)
UOzOH"*" + H2O :^=i: U02(OH)2(=U03-H20) + H"*" (or UOzOH"*" + O H "
^=^U02(OH)2) (10)
w a s f i r s t proposed by Maclnnes and L o n g s w o r t h (1942), whp found that
Equation (l) with Kj = 1.35 x 10" accounted well for the r e s u l t s of p H m e a s -
u r e m e n t s on s t o i c h i o m e t r i c UO2CI2 [or U02(N03)2] solutions, as well as for
t h o s e of pH and conductance m e a s u r e m e n t s on UO3 solutions in h y d r o c h l o r i c
"t

100
z
o 90

0) 80

70
CO
z 60
<
a:
I-
I- 50 -STRONGLY
ACID 'ii I
z )H 2 . 5 9 ' / .
UJ
o 40
/ / •
2.84
Q:
UJ 30
Q.
20 3.20

10
3-5' r 4.01/
±
i20 340 360 380 400 420 440 460 480 500
WAVE LENGTH, m/i

FIG. 2.1-VARIATION OF ABSORPTION OF URANYL PERCHLORATE


WITH pH (after Sutton, 1947).
^

0)
0)
z
0)
z<I
tt:
I-

UJ

o
Q:
LLI
Q.

pH

FIG. 2.2 —PER CENT TRANSMISSION vs. pH FOR URANYL


PERCHLORATE SOLUTIONS AT X = 416.
IONIC STRENGTH = 0.17226.
•(Zl76l'uo4ins jauD ) SNOI lANVdO X31dlAI00 dO Vai03dS NOIlddOS9V-C'2'SU

Ti'uj H19N3"! 3AV/V\


COS 081? 0917 Of7l7 03t7 OOt? 082 09£ Ot7£ 03 £
I %^—k 0 0

1 03

3 Ofr

£ 09

i? 08

Q 001
I
-\9 031

w \
2. Ot7l
[2o£{3on)] \ \
8 091

6 08!
\
01 003
1
Co3(2on)]
c" 0 3 3

.°0 *
+ Ofr3
rr\
o S>

i»+ o+

**-•
7
acid, while Equation (9) could be used to r e p r e s e n t the second but not the
f i r s t type of data. The second h y d r o l y s i s s t e p , too, they thought m o r e likely
to be of type (2) than of type (3), among other r e a s o n s , because the second
a l t e r n a t i v e would have r e q u i r e d UO3 to be soluble in w a t e r , which is not
the c a s e . Sutton (1947) pointed out that a further a r g u m e n t in favor of r e -
action sequence (l) (2) can be d e r i v e d f r o m the fact that UjOs, r a t h e r than
UO3, is deposited on the cathode in the e l e c t r o l y s i s of u r a n y l solutions.

Robinson and L i m (1951) found that the vapor p r e s s u r e lowering of


u r a n y l p e r c h l o r a t e solutions i n c r e a s e s when e x c e s s UO3 is added. This
a g r e e s with the a s s u m p t i o n that t h e s e solutions contain U2O5"'" r a t h e r than
UO2OH+ i o n s .

The extinction c u r v e of | U02"^l ^^ was derived by Sutton from the


e m p i r i c a l a b s o r p t i o n c u r v e of u r a n y l p e r c h l o r a t e at pH <2.5, a region w h e r e
the c o n c e n t r a t i o n s of the c o m p l e x ions a r e negligible; that of [ (1102)30 | ^^
was computed f r o m the a b s o r p t i o n s p e c t r u m at pH 2.5-3.0, w h e r e the t h i r d
ionic s p e c i e s can be n e g l e c t e d . The extinction curve of this t h i r d s p e c i e s ,
((1102)302! aq , was e s t i m a t e d r a t h e r roughly f r o m the e m p i r i c a l absorption
c u r v e s at pH >3.

A c c o r d i n g to F i g u r e 2.2, the complex ion j(U02)20laq ^^^ ^ s o m e -


what s t r o n g e r a b s o r p t i o n in the visible region than does the simple ion
[1102] ^q ; its a b s o r p t i o n is relatively w e a k e r in the region 360-410 mju, and
again b e c o m e s s t r o n g e r below 360 m ^ . The ion f (U02)302] ^^g is m u c h m o r e
intensely c o l o r e d than the o t h e r two; its absorption peak at 435 m/i r e a c h e s
an e s t i m a t e d height of e^nax ~ ^^^ > w h e r e a s ^ m a x ~ ^ ^ ° ^ ^^^ * ^ ° other s p e c i e s
(at 418 mju for [UO2] ^q > ^ " ^ ^^ ^25 mjLt for {(U02)20] ++ , r e s p e c t i v e l y ) .

T h e wave lengths of the peaks of the a b s o r p t i o n bands of the t h r e e


ionic s p e c i e s postulated by Sutton, t a k e n f r o m the c u r v e s in F i g u r e 2.3,
a r e l i s t e d in Table 2.1 .

C o m p a r i s o n of the wave length table given by P r i n g s h e i m (1937) for


a 0.05M u r a n y l sulfate solution (without added acid) with Table 2.1 indicates
that the s p e c t r u m obtained by P r i n g s h e i m m u s t have been that of a p a r t l y
hydrolyzed solution containing the ions UO2 and U2O5 . The s a m e applies
to M c B r a d y and L i v i n g s t o n ' s (1946) a b s o r p t i o n c u r v e of a 0.0IM solution of
u r a n y l sulfate. Sutton gave T a b l e 2.2 for the a b s o r p t i o n coefficients of a
s t o i c h i o m e t r i c u r a n y l p e r c h l o r a t e solution. The values in this table a r e
a v e r a g e s of m e a s u r e m e n t s in the c o n c e n t r a t i o n range 0.01 to 0.2M, the pH
being kept below 2.0 to avoid h y d r o l y s i s . B e e r ' s law was found to be valid,
under t h e s e conditions, up to at l e a s t 3M.
8

T a b l e 2.1

A B S O R P T I O N BANDS O F U R A N Y L IONS AND T H E I R C O M P L E X E S


W I T H W A T E R IONS A T R O O M T E M P E R A T U R E (After Sutton)

1"°^}:^ (pH<2.0) {(U02)20}+ + {(U02)302}^5 (pH>3)


Band
No.
mjU cm 1 m/Lt
^ ^-1*
cm 11 ^
m jU, c m•^-1 1

1 (350) (2857o) - - - -

2 • 360 2778o 363 2755o - -

3 370 2703o - - 372 26880


4 (381) (2625o) 377 2653o 383 26II0
5 392 2551o 388 2577o 396 2525o
6 404 2475o 405 2469o 407 2457o
7 416 2404o 415 2410o 420 2381o
8 425 2353o 430 2326o 432 2315o ,
9 (438) (2283o) 443 2357o 441 22680
10 450 2222o - - 448 2232o
11 457 2188o 456 2193o 458 2183o
12 472 2119o 472 2119o \ 478 2092o
13 489 2045o 487 2053o 1 492 2033o

In a s e c o n d p a p e r , S u t t o n (1949) g a v e e x t i n c t i o n c u r v e s of u r a n y l
p e r c h l o r a t e s o l u t i o n s f o r pH v a l u e s up t o pH 9 . 3 . T h e s e c u r v e s a r e r e p r o -
d u c e d in F i g u r e 2 . 4 . D u r i n g t h e m e a s u r e m e n t s t h e s o l u t i o n s s h o w e d , n o
p r e c i p i t a t i o n o r f o r m a t i o n of a T y n d a l l c o n e . H o w e v e r , a f t e r s e v e r a l h o u r s '
standing, a yellow precipitate formed.

It w i l l b e n o t e d t h a t in t h e m a i n b a n d r e g i o n ( 4 0 0 - 4 5 0 mjLi) a b s o r p t i o n
a s a f u n c t i o n of pH p a s s e s t h r o u g h a m a x i m u m s o m e w h e r e in t h e r e g i o n of
pH 6 - 7 a n d t h e n d e c l i n e s a g a i n . (On b o t h s i d e s of t h i s r e g i o n a b s o r p t i o n i n -
c r e a s e s s t e a d i l y w i t h pH.) S u t t o n i n t e r p r e t e d t h i s c h a n g e in t h e a b s o r p t i o n
t r e n d a s e v i d e n c e t h a t t h e t h i r d a n d s u b s e q u e n t s t e p s of h y d r o l y s i s a r e
different f r o m the first two; he suggested that they o c c u r r e d by the addition
of h y d r o x y l i o n s t o t h e t r i u r a n y l c o m p l e x :

U3ot"^ + OH":^=^U3080H+ (11)

U3O8OH+ + O H " I : ; ^ U 3 0 8 ( O H ) 2 , e t c . (12)


Table 2.2

THE MOLAR ABSORPTION COEFFICIENTS OP STOICHIOMETRIC


URANYL PERCHLORATE SOLUTION (0.01 TO 0.2M)*

X.rafj. ^UO+ + \,m/Lt %o+-^ X.,m/i, euo++ X.,m/x 'uor


230 1175 300 59.5 370 2.82| 440 3.02
2 1115 2 58.0 2 2.75* 2 2.89 t
4 1055 4 56.2 4 2.54 4 2.65
6 1000 6 53.2 6 2.43 6 2.36
8 945 8 52.6 8 2.58 8 2.05
40 875 10 51.7 80 2.81 50 1.76
2 810 2 49.0 2 3.02 2 1.57
4 745 4 46.5' 4 3.16t 4 1.42
6 685 6 45.3 6 3.40 6 1.34 1
8 620 8 42.9 8 3.86 8 L19
50 565 20 40.6 90 4.38 60 1.02
2 505 2 37.5 ' 2 4.88 2 0.91
4 461 4 34.9 4 5.04 4 0.855
6 415 6 31.9 6 5.07' 6 0.835
8 378 8 27.3 . 8 5.36 8 0.855
60 338 30 22.5 ' 400 5,97 70 0.890
2 299 2 19.9 2 6.69 2 0.90 I
4 270 4 17.6 4 6.99+ 4 0.745+
6 248 6 14.2 6 6.91' 6 0.500
8 229 8 10.531 8 6.58 8 0.300
70 208 40 8.42 10 6.60 80 0.215
2 190 2 7.23 2 6.96 2 0.175
4 171 4 5.88 4 7.51 4 0.185
6 159 6 4.42' 6 7.82+ 6 0.230
8 144 8 3.44 8 7.51I" 8 0.310
80 130 50 3.07 20 6.72 90 0.315 +
2 120 2 2.80 2 6.07 2 0.220 1
4 108 4 2.44 4 5.88 4 O.llO
6 99 6 2.36 6 5.96 6 0.053
8 89 8 2.76 8 6.09 + 8 0.039
90 80 60 3.05t$ 30 5.861" 500 0.018
2 73.5 2 2.86 2 5.20
4 68.2 4 2.47 4 4.48
6 64.5 6 2.40 6 3.80
8 61.8 8 2.63 8 3.31

Error limits: ' Bands are indicated in these positions


in 0.05M UO SO solution according to
± 0.5% at 230 m^. Pringsheim (1937).
+ 1.0% at 270 m/i
± 0.3% from 320 to 450 m/x + Peaks
+ 0.5% at 460m/Li,
± 1.0% at 470 m/i,
±3.0% at 480 m/x
+ 5.0% at 500 m/i
AVERAGE EXTINCTION COEFFICIENT, £

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The a s s u m p t i o n that U2O5 and UsOg a r e the f i r s t products of h y -
d r o l y s i s of 1102(0104)2 is c o n f i r m e d , according to Sutton, by cryoscopic
m e a s u r e r n e n t s . T h e s e show that dissolution of solid UO3 in a 002(0104)2
solution o c c u r s without i n c r e a s e in the n u m b e r of osmotically active p a r t i c l e s :

XJot^ + UOj^i^:^ U2 0^+ (13)

Sutton's second a s s u m p t i o n - that the formation of polyuranate


cornplexes linked by O b r i d g e s stops at UjOl"*" , and that further c o m p l e x -
ing o c c u r s by a s s o c i a t i o n with OH~ ions - was b a s e d p r i m a r i l y on n o n -
s p e c t r o s c o p i c evidence, such a s the shape of the pH t i t r a t i o n c u r v e s .
T r a n s f e r e n c e e x p e r i m e n t s confirm the a p p e a r a n c e of u r a n i u m - b e a r i n g
anions at alkaline pH v a l u e s . Sutton's a n a l y s i s of the s e v e r a l inflection
points on the pH t i t r a t i o n c u r v e of u r a n y l p e r c h l o r a t e indicated the s u c -
c e s s i v e f o r m a t i o n of UzO^^, \JjOt^, U3O8OH+, U308(OH)2 , U308(OH)J , and
U308(OH)4— .

The r e l a t i v e amounts of t h e s e s p e c i e s in the u r a n y l solutions used


in Sutton's s p e c t r o s c o p i c s t u d i e s a r e i l l u s t r a t e d by F i g u r e 2,5 . According
t o t h i s f i g u r e , s p e c t r u m II in F i g u r e 2.4 c o r r e s p o n d s to a m i x t u r e of U3O8OH
with s o m e U308(OH)2 and a s m a l l amount of U308(OH)^; s p e c t r u m III, to a
m i x t u r e of about equal amounts of U308(OH)3 and U308(OH)4 ; and s p e c t r u m I V ,
to a solution containing twice a s many divalent as monovalent anions.

Independently of Sutton's m e a s u r e m e n t s , , data on the h y d r o l y s i s of


u r a n y l s a l t s and its s p e c t r o s c o p i c effects have been c ollected by other i n -
v e s t i g a t o r s . The review a r t i c l e by Bounce, F l a g g , F a n t a , Tishkoff, and
L a n (1949) gives some such data (obtained in connection with toxicological
studies) on u r a n y l a c e t a t e s o l u t i o n s . In 0.2M acetate buffer (HAc + NaAc)
the a b s o r p t i o n s p e c t r u m of u r a n y l a c e t a t e shows a change with i n c r e a s i n g
pH. A c u r v e is given, showing a rapid i n c r e a s e of the r a t i o £44£,j-nu • %40mu
between pH 3.0 and pH 4 . 5 . Two absorption c u r v e s for the visible region,
one obtained at pH 3.5 and one at pH 4 . 7 , indicate that at the higher pH, a
new, or strongly enhanced, band a p p e a r s with a peak at 446m/,i, It can be
tentatively indentified with the 443m/i band of U2O5 in Table 2,1 .

(The a u t h o r s d i s c u s s e d t h e s e r e s u l t s in r e f e r e n c e to f o r m a t i o n of
u r a n y l a c e t a t e c o m p l e x e s , but they a r e m o r e likely to be due to h y d r o l y s i s . )

Neuman, Havill, and F e l d m a n (1949) mentioned that the h y d r o l y s i s


of UO2 (which they i n t e r p r e t e d a s f o r m a t i o n of UO2OH ) can be detected
p o l a r o g r a p h i c a l l y only at pH >^4.2 . The difference between this r e s u l t and
Sutton's data (pH_>2.5 , cf. F i g u r e 2.2) m a y be due in p a r t to the u s e of
m o r e dilute u r a n y l salt solutions (5 x 10*"^ M in polarography v s . >0.1 M in
s p e c t r o p h o t o m e t r y ) ; according to Equation (l) , the p e r c e n t hydrolysis should
i n c r e a s e in the r e g i o n of low h y d r o l y s i s proportionally to [UO2 1 [H"*"]^ ,
I I

10-

<0

'5 UgOeCOH)-
o>
a

o £
;; O
5 .S w

o 2 o
X X

c
u
c
o
O

FIG. 2 . 5 - D l S T R I B U T l O N OF MOLECULAR AND IONIC SPECIES IN URANYL


SOLUTIONS IN THE PRESENCE OF SODIUM HYDROXIDE (after Sutton, 1949)

t\)
13

13
The absorption s p e c t r u m of u r a n y l p e r c h l o r a t e solutions was m e a s -
u r e d a l s o by Ahrland (1949). The c u r v e s he gave a r e v e r y s i m i l a r to those
of Sutton (Figure 2.1); they show the p r a c t i c a l independence of e upon pH
between pH 0.1 and pH 2.7 over the range 240 to 440 mjU. In the region
240-320 mjU (not studied by Sutton) the a b s o r p t i o n r i s e s with d e c r e a s i n g
wave length, reaching e £^ 30 at X= 240 mjU (cf. F i g u r e 2,3). Shoulders a r e
indicated at 310, 275, and p e r h a p s a l s o at 240 m ^ .

At pH 4.1 a b s o r p t i o n c u r v e was m e a s u r e d by Ahrland only above


300 m/i; it is s i m i l a r to Sutton's curve for pH 4.0 in F i g u r e 2.1 .

Ahrland then p r o c e e d e d to make pH m e a s u r e m e n t s in u r a n y l p e r -


c h l o r a t e solutions (2 X 10"^ to 6 X 10"^M) and calculated f r o m t h e m the
a v e r a g e n u m b e r , n , of complexly bound OH" ions per u r a n y l ion at different
u r a n y l salt c o n c e n t r a t i o n s and a c i d i t i e s . He concluded, from the shape of
n = f(pH) c u r v e s , that polyuranyl c o m p l e x e s a r e involved in hydrolysis even
when the total salt c o n c e n t r a t i o n is a s low as 5 x 10~^M. By extrapolating
ii to 1 / [ H ] = 0 at different total u r a n y l c o n c e n t r a t i o n s , and plotting the r e -
sult (no) against this c o n c e n t r a t i o n , a c u r v e no= f [UO2 ]o was c o n s t r u c t e d . Its
e x t r a p o l a t e d value at [UOj ]o = 0 was used to calculate the complex d i s s o c i -
ation constant, Kj, for the f i r s t m o n o u r a n y l complex (UO2 OH~); f r o m its
initial slope, it was p o s s i b l e to calculate the complex dissociating constant,
Kj ', of the f i r s t diuranyl c o m p l e x , p r e s u m a b l y UO2 O ~ UO2 . The s o -
c a l c u l a t e d values w e r e as follows;

Ki = 2(t0.4) X 10-5

Ki' = 4(±1) X 10"^

Ahrland thus a g r e e s with Sutton in postulating e a r l y f o r m a t i o n of


d i u r a n y l c o m p l e x e s , but a s s u m e s an effective competition by monov).ranyl
c o m p l e x e s , w h e r e a s a c c o r d i n g to Sutton, addition of OH" ions begins to play
a role only after UO2 has been complexed to U3O8 •

The low value of the extinction coefficients of UO2 (^rnax — ^> £!• above)
i n d i c a t e s a p r o h i b i t e d " e l e c t r o n i c t r a n s i t i o n [cf. Kasha, (1949)]; the p r o h i b i -
tion a p p a r e n t l y b e c o m e s l e s s s t r i c t in the U30^"*' complex, w h e r e the extinction
coefficient ( r e f e r r e d to one g a t o m u r a n i u m ? ) r e a c h e s 240 (even this is low
conapared to a v e r a g e extinction coefficients in bands c o r r e s p o n d i n g to
" p e r m i t t e d " t r a n s i t i o n s , which a r e of the o r d e r of 10'* , or even 10^). The
n a t u r a l m e a n lifetime of an excited s t a t e c o r r e s p o n d i n g to an absorption
band covering the r a n g e 400-500 m/i, with an a v e r a g e decadic naolar e x t i n c -
tion coefficient e , i s :

1.05 X 10^^ , 2 _ 2.1 X 10^° _ 1.4 X lO""*


'^'- feydv ^ ° = e x 1,5 xlO^^ = e
or
To = 1-4 X 10"* for e = 1 (cf. F i g u r e 2.2) (14)
14
If
The " a c t u a l " lifetime, r , a s d e r i v e d f r o m fluorescence m e a s u r e m e n t s , is
somewhat longer - about 5 x IQ-* sec - in u r a n y l solutions as well as in
solid u r a n y l s a l t s (cf. Table 3.1). Since r is r e l a t e d to the " n a t u r a l " lifetime
TQ , (to which Equation 14 r e f e r s ) by the equation

T=0To (15)

w h e r e 0, the quantum yield of f l u o r e s c e n c e , is < 1, T should be s h o r t e r than


To. This paradox m a y be due to the fact that e, e s t i m a t e d f r o m the a b s o r p -
t i o n s p e c t r u m , includes t r a n s i t i o i j s to s e v e r a l e l e c t r o n i c s t a t e s , while an
e value c o r r e s p o n d i n g to the t r a n s i t i o n to the F state only should be p r o p e r l y
used in Equation (14).

In any c a s e , it s e e m s that the yield of fluorescence in u r a n y l salt


solutions m u s t be high. No 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 of this yield h a s
been m a d e , but a rough e s t i m a t e of 0 for solid p o t a s s i u m u r a n y l suKate
h a s in fact indicated a value of the o r d e r of 1. This m e a n s in,ci-
dentally, that in u r a n y l salt c r y s t a l s , too, the n a t u r a l life t i m e of excitation
could not be m u c h longer than 5 x lO"'* s e c , which is two o r d e r s of rnagni-
tude l e s s than the lifetime calculated by Dieke f r o m intensity m e a s u r e m e n t s
of single a b s o r p t i o n lines at low t e m p e r a t u r e s . This discrepancy was pointed
out in C h a p t e r 1.
15

is
2. ABSORPTION SPECTRA OF URANYL IONS
COMPLEXED WITH ACID ANIONS

2,1 Effect of Inorganic Anions pn Uranyl Spectrum in Solution - F o r a


long t i m e o b s e r v a t i o n s had indicated that the s p e c t r u m of aqueous solutions
of u r a n y l salts of s t r o n g inorganic acids - n i t r i c , h y d r o c h l o r i c , sulfuric, etc. -
is affected by the anions p r e s e n t in solution. However, the data have been
neither p r e c i s e nor s y s t e m a t i c enough to tell whether these differences indi-
cated the formation of definite c o m p l e x e s , (Thus, m a r k e d s p e c t r a l changes
could o c c u r , without the formatipn of c o m p l e x e s , in consequence of the i n -
fluence of ions on the bulk p r o p e r t i e s of the medium, such as its d i e l e c t r i c
constant; or as a r e s u l t of l o n g - r a n g e p r d e r effects; or, in concentrated
solutions, a s a r e s u l t of t r a n s i e n t i n t e r a c t i o n between ions during their e n -
counters.) More r e c e n t l y , the s p e c t r a of chloride, sulfate and n i t r a t e solu-
tions have been studied with b e t t e r p r e c i s i o n and i n t e r p r e t e d in terrns of
complex formation.

Many of the older o b s e r v a t i o n s dealt only with the position of band


p e a k s ; o t h e r s , in a qualitative w^ay, with changes ip the intensity of different
b a n d s . The following is a brief r e v i e w of the r e s u l t s of t h e s e s t u d i e s .

The e a r l i e s t m e a s u r e m e n t s w e r e a s s e m b l e d and converted to i n t e r -


national wave length s c a l e by K a y s e r , in Vol. 3 of his "Handbook of S p e c t r o s -
copy" (1905, p . 418). Absorption band peaks a r e given t h e r e for aqueous
solations of u r a n y l a c e t a t e c h l o r i d e , fluoride, n i t r a t e , (mono)phosphate» arid
sulfate. As an example, Table 2.3 gives the (corrected) values of the band
peaks o b s e r v e d by Morton and Bolton (1873). It shoves that, with few e x c e p -
tions, the bands of the n i t r a t e a r e located at the s h o r t e s t w a v e s , followed by
t h o s e of chloride, sulfate, a c e t a t e , fluoride and phosphate.

Table 2,3

ABSORPTION PEAKS OF URANYL SALTS IN AQUEOUS SOLUTION,


AT ROOM T E M P E R A T U R E , AFTER MORTON AND BOLTON (1873)
CORRECTED BY KAYSER (1905)

]Band No
1 2 3 4 5 6 7

Nitrate 488 472 455 440 428 416 404


Chloride - 475 457 440 429 - -

Sulfate 495.5 475 457 443.5 431.5 420 408


Acetate 489 476 461 444 432 420 405
Fluoride - 478 462 446 433 419.5 405.5
Monp -pho sphat e 506 477.5 461.5 448 434.5 424 -
16
Ii
F o r the i n t e r p r e t a t i o n of t h e s e shifts, the effects of the concentration
of anions, and of t e m p e r a t u r e a r e significant.

Concentration of the anions can be changed in two ways: either by


i n c r e a s i n g the concentration of the u r a n y l salt, or by adding another c o m -
pound of the s a m e anion, such as an alkali salt, or free acid. These studies
a r e best c a r r i e d out by substitution, keeping constant the total ionic strength
and the acidity. Also, c a r e should b e taken to u s e the pH r a n g e w h e r e u r a n y l
ions do not undergo any of the hydrolytic changes d e s c r i b e d in Section 1. No
such p r e c a u t i o n s have been taken in the e a r l y m e a s u r e m e n t s with which we
a r e dealing now.

Concentration Effects - Knoblauch (1891) found that the positions of


the two e x t r e m e long wave bands of u r a n y l n i t r a t e did not change in the con-
c e n t r a t i o n r a n g e of U02(N03)2 f r o m IM to 3 x 1 0 " ' M ; the s a m e was found
for a 1 to 450 change of concentration of u r a n y l acetate and a 2500 to 1 change
of concentration of u r a n y l c h l o r i d e . However, Knoblauch found t h e s e bands to
b e r e l a t i v e l y s t r o n g e r in dilute solution (indicating a deviation f r o m B e e r ' s
law).

Jones and Strong (1910a) r e p r o d u c e d photographs of the absorption


s p e c t r a of aqueous solutions of the following s y s t e m s :

UO2CI2 (1; 0.75; 0.5; 0.33; 0.25, O.I6 and 0.125N)

UO2CI2 (0.2N) + AICI3 (2.43N)

UO2Cl2(0.2N) + ZnCl2 (saturated)

UO2Cl2(0.2N) + HCl (concentrated)

The l a s t t h r e e s y s t e m s w e r e investigated to o b s e r v e the effect of a


high concentration of Cl~ ions at constant concentration of UO2 . The a b -
sorption bands b r o a d e n e d with i n c r e a s i n g UO2CI2 concentration (the product
concentration t i m e s cell depth being constant). The u l t r a v i o l e t band m e r g e s
with the n e a r e s t violet band.

The positions of the o b s e r v e d band c e n t e r s (which do not shift signifi-


cantly with concentration) a r e shown in Table 2.4. In addition, v e r y n a r r o w ,
weak bands w e r e noted at 518,5, 520, 600, 602, 604 and 607 m/i. Addition of
c a l c i u m chloride caused all bands to b r o a d e n . The effect of aluminuni c h l o -
r i d e was even s t r o n g e r ; the bands shifted to the red by up to 3 m/i; some
i n c r e a s e d c o n s i d e r a b l y in intensity. Zinc chloride and concentrated h y d r o -
c h l o r i c acid p r o d u c e d s i m i l a r changes, but the red shift was l e s s pronounced
with zinc chloride than with a l u m i n u m chloride or h y d r o c h l o r i c acid.

S i m i l a r l y , c o n c e n t r a t e d n i t r i c acid was found to i n c r e a s e the intensity


of U 0 2 ( N 0 3 ) 2 b a n d s , but the band shift caused by this acid was toward the
violet.
17
n
Table 2.4

ABSORPTION BANDS OF UO2CI2 (0.2N SOLUTION) A F T E R


JONES AND STRONG (I9IO)

1 U02C12 c»
402.5 417 431.5 446 456 474 492
+ ZnClz (sat.) - 411.5 424.5 - 440 460 477 493
diff.
+ AICI3 (2N) 401 413.5 427 442 448 462 479 495
+ HCl (cone.) 401.5 415 428 442 448 463.5 480 495

Von K u r e l e c (1927) m e a s u r e d the shift of the peaks of the f i r s t two


a b s o r p t i o n bands of u r a n y l n i t r a t e (3.454 g U02(N03)2 in 14 cc H2O), caused
by addition of an i n c r e a s i n g quantity of sulfuric acid, and foixnd that at
[H2SO4] / [HNO3] = 1.2, the bands a s s u m e d the positions c h a r a c t e r i s t i c of
u r a n y l sulfate. This m a y indicate r e p l a c e m e n t of n i t r a t e ions in association
with u r a n y l cations by sulfate i o n s .

Table 2.5

SHIFT OF UO2 (N03)2 ABSORPTION BANDS BY SULFURIC ACID


(AFTER VON KURELEC, 1927)

Band
1 [H2SO4], g / 1 4 cc solution
I II

0 487,0 470.0
0.473 489.7 473.5
0.788 489.6 473.6
0.867 489.7 473.7
0.946 489.9 473.9
1.576 490.3 474.4

UO2SO4 in H2O 490.4 474.2

No shift w a s o b s e r v e d when 0.47 g HNO3 was added to a solution of


4.57 g UO2SO4 in 14 cc H2O. Addition of n i t r i c acid to UO2CI2 solution a l s o
w a s ineffective. T h i s a g r e e s with the assumption that the tendency of u r a n y l
ions for complexing is s m a l l e r with NO3 than with C I ' and SO4- i o n s .
18
ir
a% Only when nitric acid was added to UO2CI2 solution in large excess
and the nnixture heated until gas evolution and brown coloration occurred,
did the U02'''"'" bands shift to positions characteristic of a nitrate solution.

When hydrochloric acid was added to uranyl nitrate, a shift similar


to that caused by sulfate was observed. At about [HC1]/[HN03] = 1, the
band reached a position close to that in pure UO2CI2 solution.

Pierce (1929) found that chloride in low concentrations has no marked


effect on the absorption spectrum of uranyl salt solution,but that saturated
potassium chloride changes the spectrum almost as strongly as O.OIM
oxalic acid, indicating the formation of complexes, (it will be noted
that quenching of uranyl fluorescence by chloride ions sets in at much lower
.concentrations and therefore cannot be attributed to complex formation.)

Pringsheim (1937) found similar evidence of interaction of uranyl


ions with iodide ions at potassium iodide concentrations of the order of
0.01-O.lM. The absorption coefficient of 0.05M UO2SO4 at 365 m/u was in-
creased by a factor of 4 by the addition of O.IM KI,

The temperature effect on the absorption bands of simple uranyl salts


in aqueous solution was first noted by Bremer (1890) [cf. Bremer (1892) and
Kayser (1905, p,419)]. He found that with UO2SO4 as well as with U02(N03)2
solution, heating shifts the band peaks towards the red (by 1.2-1.6 m/i be-
tween 20° and 80°C), Morton and Bolton (1873) found the same rule to be
followed by several double salts.

Jones and Strong (l910a,b, 1911 a) photographed the spectrum of uranyl


chloride (IN) at 6°, 18°, 34°, 52°, 68° and 82°C, With increasing temperature,
the ultraviolet absorption limit moved toward the visible, from 356 to 370m/i;
the strong blue-violet band shifted at the same time fronn 400-445 m/i to
395-460 m/i. In more dilute (0O0156N) solution, the temperature effect was
much less pronounced. In uranyl nitrate solutions in water (IN and 0.0156N),
the results were similar, with the ultraviolet absorption edge shift
(343 — > 355 m/i) being the most prominent effect. The blue-violet band ex-
tended, at 79°C, from 390 to 445 m/i.

In uranyl sulfate solutions in water (IN and 0.0156N), the ultra-violet


edge advanced between 5° and 84°C from 350 to 360 m/i. The blue-violet band
extended at low temperature from 390 to 440 m/i (in concentrated solution) or
395 to 445 m/i (in dilute solution) and at high temperature from 385 to 445 m/i
or 390 to 450 m/i, respectively. Other bands also were shifted by heating:
from 457, 473 and 491 m/i, to 459, 474.5 and 492,5 m/i, respectively, in IN solu-
tion; and from 472 and 489,5 m/i to 473.5 and 491,5 m/i, respectively, in N / 6 4
solution.

Jones and Strong.(1911 b, 1912) reproduced the spectra of uranyl nitrate


in nitric acid, of uranyl chloride in hydrochloric acid, and of uranyl sulfate in
water and in sulfuric acid, at temperatures from 10°C to 70-80°C. The shifts
19
/?
in acid solutions w e r e in the s a m e d i r e c t i o n (i.e., t o w a r d s longer wave lengths)
a s in p u r e w a t e r , but w e r e m u c h l e s s extensivCj by about 1 m/i in the c a s e of
n i t r a t e in n i t r i c acid, and 1,5 mjU in that of chloride in hydrochloric acid.
Sulfate in sulfuric acid showed a m a r k e d shift only in the blue-violet band.

Jones and Guy (1913b) r e p r o d u c e d absorption s p e c t r a of 0,2N and


0 , 0 2 N u r a n y l n i t r a t e solutions in w a t e r , at t e m p e r a t u r e s fronn 20 to 120°C
and f r o m 20 to 165°C, r e s p e c t i v e l y . The s p e c t r p g r a m shows g e n e r a l band
widening and shift of the c e n t e r s of s o m e bands t o w a r d s longer waves with
i n c r e a s i n g t e m p e r a t u r e . Broad and diffuse bands appear at the higher t e m -
p e r a t u r e s - i n 0,02N solution at 510, 560 and 620 m/i.

S i m i l a r s p e c t r o g r a m s w e r e given for 0,166 and 0,2N uranyl sulfate


in w a t e r at 20°-185°C and 20*-l65®C» I'SspeCtively, The c e n t e r s of the bands
at 477,5 and 432.5 m/i moved by a s m u c h a s 2,5 na/i upon heating, while that of
the 475,0 m / i r e m a i n e d in i t s o r i g i n a l position. The weak and diffuse bands at
510, 560 and 620 m/i seemed in t h i s c a s e to be unaffected by t e m p e r a t u r e .
T h e s e e x p e r i m e n t s indicated that only v e r y weak complexing o c c u r s between
u r a n y l and n i t r a t e ions and t h a t a s s o c i a t i o n is somewhat s t r o n g e r with sulfate,
and still s t r o n g e r with chloride ions,

Betts and Michels (1949) m a d e the f i r s t m o r e p r e c i s e s p e c t r o p h o t o -


m e t r i c study of solutions of u r a n y l sulfate and uranyl n i t r a t e . They pointed
out that definite complex formation with sulfate ions i s indicated, in addition
to e a r l i e r p o l a r o g r a p h i c studieSj by the observation that isotopic exchange
of u r a n i u m between u r a n y l ions, U"^ ions and U"*" ions is much m o r e rapid
in sulfate than in p e r c h l o r a t e solutions. The absence of complexing in the
l a t t e r solution, shown by Sutton's s p e c t r o p h o t o m e t r i c study (p, 2) was c o n -
f i r m e d by B e t t s and M i c h e l s , who extended the range in which the s p e c t r u m
shows no changes a t t r i b u t a b l e to complexing, to [UOj ] = 0,02-0.5M and
[HCIO4] = 2-6M (at [H+] = 2M),

In sulfate solutions (also at [H+J = 2 M ) 5 with a total ionic s t r e n g t h


oi T] = 2.65 (sulfuric acid being t r e a t e d a s a monobasic acid), c o m p a r i s o n
of a b s o r p t i o n c u r v e s of solutions with a constant value of ([UO2"'"] + [HSO4 ])
(= 0 , 2 4 0 M ) , but v a r i a b l e r a t i o [UOa"*"]/[HSO4], r e v e a l e d an i n c r e a s e of a v e r -
age m o l a r extinction coefficients (in the range 420-450 m/i) with i n c r e a s i n g
p r o p o r t i o n of u r a n y l ions, x = [UO-|+]/([UOt'*"] + [HSO4]), reaching a peak
at the r a t i o x = 0,5 and d e c r e a s i n g at x > 0 , 5 . According to Job, this i n d i -
c a t e s the formation of a o n e - t o - o n e u r a n y l bisulfate complex. The effect of
H+ concentration on the r e s u l t s indicated that the complexing r e a c t i o n i s :

UOt"*" + HS03=:z::U02S04 + H+ ,

r a t h e r than:,

U0t+ + H S 0 4 = ^ U 0 2 H S O t
20

^0
The s p e c t r u m of the s p e c i e s UO2SO4, derived from these e x p e r i m e n t s ,
i s shown in F i g u r e 2.6, The e q u i l i b r i u m constant i s :

K(U02S04)= ([U02S04]/[UOt+][HS04]) = 2.50 t 0.17 ( m o l e / i ) ~ \

for 7] = 3.48. T h i s value w a s d e r i v e d frona the s p e c t r a of two solutions,


both 0.02M in HSO4 ; it was confirmed by calculating extinction values for
other m i x t u r e s of s a m e ionic strength and acidity, and comparing t h e m with
experimental values.

A s i m i l a r study of the u r a n y l n i t r a t e s y s t e m led to F i g u r e 2.7 for the


s p e c t r u m of the s p e c i e s UO2NO3, and to an equilibrium constant

K(U02N0t) = — ^ — = 0.21 t 0.01 (mole/X)"* (16)


tuoj"^] [NOf]
at [H+] = 2.00, and T) = 5.38 (equilibrium constant calculated from the s p e c t r a
of two solutions with [UOt"*"] = 0.0605M, and [NOi] = 1.28 and 2.56M, r e s p e c -
tively; checked by conaparing calculated and observed s p e c t r a of other splutions
of s a m e acidity and ionic s t r e n g t h ) .

In looking for higher n i t r a t e c o m p l e x e s at the higher c o n c e n t r a t i o n s ,


B e t t s and M i c h e l s found only slight deviations of observed from the calculated
s p e c t r a at 7) = 7.05 [K(U02N0t) = 0,270 t 0.007]. These deviations w e r e in
the d i r e c t i o n of s t r o n g e r a b s o r p t i o n , a s expected for a higher complex but
they w e r e so snaall that B e t t s and Michels c o n s i d e r e d t h e m to be due to slight
v a r i a t i o n s of K with [UO'I"''] (at constant 7] ), r a t h e r than to the formation of
d e e p e r - c o l o r e d higher c o m p l e x e s .

According to a note by A r d e n (1949), potentiometric and conductonaetric


m e a s u r e m e n t s indicate the formation of the following complexes in u r a n y l
sulfate solutions:

UO2SO4; U30t+; (U020H)2S04; U3O8OH+; U02(0H)2 ; U308(OH)2

The formation of a t r i n i t r o complex from u r a n y l n i t r a t e and c o n c e n -


t r a t e d n i t r i c acid in c e r t a i n organic solvents will be d e s c r i b e d in Section 3
of t h i s c h a p t e r .

Ahrland(1951c) m e a s u r e d extinction c u r v e s of 0.033M (or 0.015M)


U02(C104)2 solutions in 0.25M (or O . I O M ) HCIO4, t o which NaCl (0.25-0.75M),
N a B r (0.75M) or NaNOs ( 0 , 7 5 M ) w a s added, the ionic strength being adjusted
to r^ = l.O by NaC104. The c u r v e s showed slight, but r e a l differences, i n -
dicative of weak complexing. A s s u m i n g a 1-1 complex only, its e q u i l i b r i u m
constant could be calculated, for u r a n y l chloride, a s

Ki = ^^^^^^ ^ • = 0.5 t 0.3 ( m o l e / j t ) " ^ (20°C)


[UOt+] [C1-] "^
21

UJ
O
UL
Ii.
CiJ
o
o

O ft _
o
z
h-
X
UJ

cc
o

340 360 380 400 420 440 460 480 500


WAVE L E N G T H , m/i

FIG. 2.6 — A B S O R P T I O N SPECTRUM OF THE COMPLEX


UO2SO4 (after Betts and Michels, 1949).
1 1

340 360 380 400 420 440 460 480 500


WAVE LENGTH, m/x

FIG. 2.7 - A B S O R P T I O N SPECTRUM OF UOgNOj.


23

:i3
F o r all t h r e e s a l t s , the f i r s t complexing constant at 20°C was d e t e r m i n e d
potentionaetrically; the r e s u l t i n g v a l u e s w e r e 0.8, 0.5, and 0.5 (- 0.2)
( m o l e / i , ) ^ for the c h l o r i d e , b r o m i d e , and n i t r a t e , in this p r d e r . The l a s t
value can be c p m p a r e d with B e t t s and M i c h e l s ' r e s u l t (0.21 I 0.01 at r] =
5.38 and 25°C).

A s i m i l a r study pf sulfate (Ahrland, 1951b) gave F i g u r e 2.8A for the


a b s o r p t i o n s p e c t r a at different sulfate c o n c e n t r a t i o n s , and F i g u r e 2.8B for
the m o l a r a b s o r p t i o n coefficient at 310 m/i a s function of [sulfate] and t h r e e
different [uranyl] v a l u e s . Again, only monouranyl conaplexes of UO2 with
S O " a r e indicated, with the a s s o c i a t i o n constants

Ki = 56 ± 6 ( m o l e / £ ) " * K2 = 450 t 50 {mole/l)'^

The f i r s t constant, valid at 20°C and T] = 1.0, can be c o m p a r e d with Betts


and M i c h e l s ' value of 59.5 1 4 ( m o l e / j t ) " ^ . (Ahrland m a k e s objections
a g a i n s t the method used by B e t t s and Michels.)

The a s s o c i a t i o n c o n s t a n t s d e r i v e d from potentiometric methods w e r e :

Ki = 50 ± 10 ( m o l e / i )•*
K2 = 350 1 150 ( m o l e / i )"2
T-r ornrv + ^ r\r\r\ I «i« I li \~^

A s s o c i a t i o n c o n s t a n t s of mixed a c e t a t e - s u l f a t e c o m p l e x e s , UO2 A c ' S O " and


UO2 Ac2~SO^~, a l s o w e r e estinaated potentionaetrically.

2.2 Complexing with Organic Ions - The s p e c t r o s c o p i c evidence of


u r a n y l ion complexing with anions of o r g a n i c a c i d s i s much s t r o n g e r than in
the c a s e of m i n e r a l a c i d s but h e r e , too, older data a r e insufficient for s a t i s -
factory quantitative a n a l y s i s , and new s y s t e m a t i c m e a s u r e m e n t s , under
controlled conditions of acidity and ionic strength, a r e needed.

E a r l y data on the a b s o r p t i o n s p e c t r u m of u r a n y l acetate in the visible


r a n g e w e r e mentioned on p . 15(cf. Table 2.3). Jones and Strong (1910 a, 1911b)
noted that the long-wave edge of the b l u e - v i o l e t absorption band of a 0.04M
solution of t h i s salt moved from 450 mju at 6°C to 460 mju at 75°C.

H e n r i and Landau (1914) m e a s u r e d the absorption coefficients of


s e v e r a l u r a n y l salt solutions in the m e d i u m u l t r a v i o l e t (236-330 m/i). The
r e s u l t s a r e shown in Table 2.6. A substantial i n c r e a s e in absorption is caused
by the addition of oxalate or a c e t a t e . H e n r i an3>Landau sa"w in this an example
of " p h o t o c h e m i c a l exaltation"; a c c o r d i n g to this concept, the absorption of
light by a m i x t u r e of m o l e c u l a r s p e c i e s that can r e a c t with each other p h o t o -
c h e m i c a l l y i s s t r o n g e r than the s u m of the absorption of the c o m p o n e n t s .
24

iS^*f~-

3.5 - . 1 1 1 1 1 ^
•«. ^
^
- ^ : - .
3.0 -N

2.5

T. 2.0
W

CP
o 1 \ **
1.5
3100 Ny^ \ \
1.0 ••"

0.5 ^

rv 1 1 1 1 1 '
2500 3000 3500 4000 4500 I

Figure 2.8A

MOLAR DECADIC EXTINCTION CURVES OF URANYL SULFATE COMPLEXES


(AFTER AHRLAND, 1951b). SOLID LINE: URANYL IONS (FREE). DASHED
LINES: [U0++]o = O.OIM; [SULFATEJQ = 0.05M (LOWER CURVE), 0.2M
(UPPER CURVE). [U0++]j, = TOTAL CONCENTRATION OF FREE AND
BOUND URANYL. [SULFATE]O= TOTAL CONCENTRATION OF SULFATE USED
(URANYL SULFATE + SODIUM SULFATE). A SMALL CORRECTION IS MADE
FOR ASSOCIATION OF SO4" IONS WITH H+ IONS (ENOUGH PERCHLORIC
ACID IS ADDED TO SUPPRESS HYDROLYSIS OF URANYL IONS). IONIC
STRENGTH T) - 1.0 ADJUSTED BY NaClO^.
25

I I I L.
0 100 200 300
C/x, m M / l .

Figure 2.8B

AVERAGE MOLAR DECADIC EXTINCTION COEFFICIENT AT 310 m^i IN


URANYL + SULFATE SOLUTION AS FUNCTION OF TOTAL SULFATE
CONCENTRATION C^ (FREE SULFATE IONS + SULFATE IONS COM-
PLEXED WITH URANYL). O [U0++]o = 0.030M. V [U0 + +]o = G.OIOM.
n [ u 0 2 " ^ ] o = 0.003M. HORIZONTAL LINES CUT THE SEVERAL CURVES
AT POINTS CORRESPONDING TO CONSTANT CONCENTRATION OF FREE
ANIONS.
26

Table 2 . 6

EFFECT OF DffFERENT ANIONS ON THE ABSORPTION COEFFICIENTS OF


URANYL IONS IN ULTRAVIOLET (AFTER HENRI AND LANDAU. 1914)
l o g i o d o / l ) s £cd
c in mole U/liter. Acid concentration not specified.

Wavelength, nijU
Solution Contains
236 243.5 251.0 259.2 272.4 289.5 300.1 307.6 318.6 330.6

U02(N03)2 2020 1350 675 540 295 160 125 108 65 27

UO2SO4 1350 1000 720 545 375 200 108 81 54

UOgClg 1050 890 540 490 320 275 170

UOsCCHgCOOfe 2200 1825 1575 1300 970 810 630 500 320 210

U02(N03)2 + H2C204 2480 1950 1390 780 540 440 300

UO2SO4 + H2C2O4 3225 2850 2445 2030 1440 640 410 280 190

UO2CI2+H2C2O4 1610 1380 1010 585 370 260 180

U02(CH3COO)2
+ H2C2O4 3160 2670 2280 1840 1230

UO2G2O4 2770 2380 1990 1690 1230 580 435 290 165 120

Oxalic A c i d * 88 64 57 49 22 5 2 - -

Figures in this row show how much light oxalate alone would have absorbed at the different wave
lengths. Henri and Landau noted that e (oxalate), added to £ (U02(N03)2) (top row in Table 2. 6) is
smaller than e of the mixture (U02(N03)2 + oxalate), and considered this difference as "photo-
chemical exaltation"; we interpret it as evidence of complex formation.

A parallelisnn between enhanced a b s o r p t i o n and photochemical r e -


activity i s in fact p o s s i b l e , but the l a t t e r cannot be c o n s i d e r e d a s cause of
the f o r m e r . What is e s s e n t i a l i s that the two components form a nnore or
l e s s stable complex. Light a b s o r p t i o n can then cause the t r a n s f e r of an e l e c -
t r o n f r o m one p a r t of the c o m p l e x (e.g., the anion), to another p a r t (e.g., the
cation); the a b s o r p t i o n band i s an "electron t r a n s f e r band." Such a t r a n s f e r
is equivalent t o an i n t e r n a l oxidation-reduction; the complex may then - but
does not need to - d i s s o c i a t e into an oxidized and a reduced product (e.g., i n -
to a r e d u c e d u r a n y l ion and an oxidized oxalate ion). If the anion-cation
e l e c t r o n t r a n s f e r band l i e s in the s a m e region as the absorption bands of one
(or both) of the s e p a r a t e ions, the effect of complexing will be to enhance
a b s o r p t i o n in t h i s r e g i o n . Whether or not, the lifting of the e l e c t r o n into the
27

t r a n s f e r band will lead to a photochemical change depends on the amoiont of


v i b r a t i o n a l e n e r g y of a c e r t a i n type r e q u i r e d for this change and the p r o b a -
bility of c o n v e r s i o n of e l e c t r o n i c excitation energy into v i b r a t i o n a l energy of
t h i s kind. This probability naay be l a r g e or s m a l l , both in photochemically
unstable and in photochemically stable connplexes.

The change of absorption s p e c t r u m observed by H e n r i and Landau


upon mixing of u r a n y l s a l t s with acetic or oxalic acid s e e m s to c o n s i s t in a
strong g e n e r a l enhancement of a b s o r p t i o n , r a t h e r than a shift of the a b s o r p -
tion band; this is a r e a s o n for attributing it to a new excited s t a t e , not
p o s s e s s e d by the s e p a r a t e i o n s . Often, however, the absorption bands of
c o m p l e x e s a r e not m u c h m o r e intense than those of the non-complexed ions,
but only a p p e a r so b e c a u s e they shifted t o w a r d s longer w a v e s , thus enhancing
the a b s o r p t i o n in the visible and n e a r u l t r a v i o l e t . In this c a s e , one does not
need to postulate a new e l e c t r o n i c level in the complex, but can a s s u m e that
complexing m e r e l y l o w e r s the e n e r g y of an excited state belonging to one of
the free i o n s . In f u r t h e r developing the p i c t u r e , we note that "free i o n s , " in
the c a s e of aqueous solutions, m e a n s hydrated ions; some of t h e i r strong
u l t r a v i o l e t a b s o r p t i o n bands m a y be (and probably a r e ) due to the t r a n s f e r of
an e l e c t r o n f r o m the hydration s p h e r e to the c e n t r a l cation, or vice v e r s a .
(The much w e a k e r bands in the visible and n e a r ultraviolet, on the other hand,
a r e likely to b e caused by prohibited t r a n s i t i o n s within the ion itself.) The
effect of complexing with an anion i s to introduce the l a t t e r into the hydration
s p h e r e of the cation. This m a y m e r e l y make the electron t r a n s f e r to or from
the w a t e r envelope e a s i e r (thus shifting the absorption band t o w a r d s longer
w a v e s ) ; or it m a y p e r m i t a new kind of t r a n s f e r , in which the e l e c t r o n o r i g i -
n a t e s (or ends), not in the hydration s p h e r e , but in the anion. This new
e l e c t r o n i c t r a n s i t i o n p r o d u c e s a g e n e r a l enhancement of absorption in the
region of the new e l e c t r o n t r a n s f e r band.

With t h e s e g e n e r a l r e m a r k s concerning enhanced absorption of c o m -


plex ions (compared to that of n o n - c o m p l e x e d , hydrated ions) prompted by
H e n r i and L a n d a u ' s "photochemical exaltation" concept, we r e t u r n to the
e x p e r i m e n t a l data obtained with u r a n y l ions and organic a c i d s .

Somewhat m o r e s y s t e m a t i c m e a s u r e m e n t s than those of H e n r i and


Landau w e r e c a r r i e d out by Ghosh and Mitter (1928). They observed the
e n h a n c e m e n t of u l t r a v i o l e t a b s o r p t i o n of 5 x lO'^M ajid 10 x 10~*M u r a n y l
solutions by t h e addition of v a r i o u s organic acids (0.005M to 1 M ) , and found
effects which they attributed to the formation of 1-1 complexes between
u r a n y l ions and the acid, with an e q u i l i b r i u m constant K^,:

[UOt+ A] [C]
Kc ='- 5 ^ = -— (17)
[UOt+][A] ([U]o-[C])([A]o-[C])
w h e r e [C] i s the concentration of the complex, and [U]Q and [A]o a r e the total
c o n c e n t r a t i o n s of u r a n y l salt and acid, r e s p e c t i v e l y .
28

-2'
S p e c t r o s c o p i c evidence of the formation of a uranyl t a r t r a t e complex
w a s obtained by H a k o m o r i (1927); he noted that i n c r e a s e d addition of Rochelle
salt to 0..02N u r a n y l sulphate solution c a u s e s the ultraviolet absorption to
move f r o m 335 to 360 mju, when a 1:1 r a t i o i s r e a c h e d , and then to r e c e d e
again.

In analogy with the h y d r o l y s i s equilibria d i s c u s s e d in Section 1, the


p o s s i b i l i t y of formation of polyuranyl ions should not be forgotten. However,
Ahrland (1949, 1951) found, with s e v e r a l inorganic (HCl, HBr, HNO3, H j S O j
and organic ( a c e t i c , naonochloracetic, thiocyanic) a c i d s , no evidence of c o m -
plexes containing m o r e than one u r a n y l ion. Even considering 1-1 complexes
only. Equation (17) i s u n s a t i s f a c t o r y , b e c a u s e [A] denotes total acid, no
distinction being raade between acid anions and n e u t r a l acid m o l e c u l e s . Even
if r e l a t i v e l y few f r e e ions a r e p r e s e n t in weak a c i d s at AQ ^ O.IM, the m o s t
i m p o r t a n t complex s p e c i e s m a y still be that containing anions, e.g.,

UOt"*" + H C 0 0 - ^ ^ ^ U 0 2 H C 0 0 + . (18)

Equation (17) m u s t , t h e r e f o r e , be r e p l a c e d by one involving the dissociation


constant of the acid, D, in addition to the complexing constant K:

[UOt+ A-] /[H+] \ , ,


K = i 1 i=Kcih + 1] (19)
[UOt+] [A-] "" V D /
When acid d i s s o c i a t i o n i s p r a c t i c a l l y complete (i.e., when D » [H"*"]) we have:

and Ghosh and M i t t e r ' s p r o c e d u r e b e c o m e s a d m i s s i b l e (leaving out "second


o r d e r " effects, such a s the - g e n e r a l l y quite c o n s i d e r a b l e - dependence of the
complexing constant on ionic s t r e n g t h ) . In the c a s e of weak dissociation
([H+] » D ) , on the other hand, we have

[H+l KD ,_
KnidKc ,orKc-^ _ ^i:4 K / (20)
D [H+]

and thus see that Ghosh and M i t t e r ' s "constant^" K^. cannot r e m a i n constant
except in buffered solutions ([H'''] = const.), while in the absence of a buffer,
the o b s e r v e d v a l u e s of the "constant" Kc will d e c r e a s e with i n c r e a s i n g c o n -
c e n t r a t i o n of the acid. In the region of v e r y weak dissociation, K^, will be
i n v e r s e l y p r o p o r t i o n a l t o ^A^ .

Ghosh and M i t t e r ' s Kj, c a l c u l a t i o n s could have thus given a c o r r e c t


p i c t u r e of the r e l a t i v e s t r e n g t h of complexing with different a c i d s only if
t h e i r m e a s u r e m e n t s would have been made in the region of a p p r o x i m a t e l y
complete d i s s o c i a t i o n ; in fact, h o w e v e r , they w e r e made m o s t l y in the region
29

of weak d i s s o c i a t i o n , w h e r e the a p p a r e n t "complexing c o n s t a n t s , " K^, a r e


s m a l l e r the w e a k e r the acid. With v e r y weak dissociation, when Equation (20)
is valid, K^^/K will be p r o p o r t i o n a l to jTi at any given concentration of the
added acid; in other w o r d s , of two a c i d s with equal t r u e complexing c o n s t a n t s ,
K ' a n d K'"', the one with the higher dissociation constant, D, will appear to
f o r m m o r e stable c o m p l e x e s :

(21)

One can imagine the acid anions a s having a choice of complexing,


e i t h e r with H"*" ions or with UO2 ions. The tendency for complexing with
hydrogen ions is generally g r e a t e r than that for complexing with u r a n y l ions
( K i s s m a l l e r than l / D !). The n u m b e r of H+ ions available (i.e., in p r a c t i c e ,
in unbuffered solution, the total acid concentration, [A]Q) was in Ghosh's
e x p e r i m e n t s m u c h higher than the total n u m b e r of available u r a n y l i o n s .
T h e r e f o r e , the c o n c e n t r a t i o n of free acid anions was d e t e r m i n e d mainly or
exclusively by [A]o and D, and the concentration of uranyl complexes was in
its t u r n d e t e r m i n e d by the concentration of free acid anions.

S i m i l a r l y , the u r a n y l ions have a choice of association either with the


acid anions or with the anions of w a t e r (OH~ and 0 " ~ ) .

Improved calculation should take into consideration also the h y d r o l y s i s


e q u i l i b r i a of the u r a n y l ion, d e s c r i b e d in Section 1, which become important
at pH > 2. F i n a l l y , the e q u i l i b r i u m c o n s t a n t s depend on ionic strength, so
that m e a s u r e m e n t s should be made at known and constant ionic strength.

When Equation (17) i s valid, the complexing constant, K^., can be


calculated, together with the a b s o r p t i o n coefficient, e^,, of the complex
[UO2 A ] , by m e a s u r i n g the a b s o r p t i o n coefficient e (the average m o l a r a b -
sorption coefficient r e f e r r e d to the total u r a n y l content) at a given wave length,
\ , with two different c o n c e n t r a t i o n s of total added, acid, AQ.

E a c h m e a s u r e d value of e can be e x p r e s s e d by an equation

[C] (ec - eu) + [U]o ^u , ,


e = — (22)

with two unknowns: [C] = concentration of complex, and e^, = absorption


coefficient of complex, while eu. the absorption coefficient of non-complexed
u r a n y l ions, can be p r e s u m e d to be known from m e a s u r e m e n t s made without
added acid. Two such equations, t o g e t h e r with two equations of type (17) for
the two c o n c e n t r a t i o n s AQ, provide four equations with four unknowns, which
can be solved.

Ghosh ajid M i t t e r tabulated K^ v a l u e s (Table 2.7) and the absorption


coefficients, Gc (Table 2.8) calculated in this way for the s e v e r a l acids they
have studied. However, c l o s e r s c r u t i n y r e v e a l s , in the f i r s t place, that the
30

v a l u e s designated by t h e m a s a b s o r p t i o n coefficients of the complex" (i.e.,e„)


a r e not t h e s e coefficients, but differences between t h e m and the absorption
coefficients of free u r a n y l ions, ( i . e . , e j , - e^, cf. Equation (22)). This e r r o r
h a s been c o r r e c t e d in Table 2.8. F u r t h e r m o r e , no indication can be found in
the p a p e r of Ghosh and M i t t e r a s to whether t h e i r absorption coefficients
w e r e b a s e d on decadic or n a t u r a l l o g a r i t h m s . Since in some later p a p e r s
f r o m G h o s h ' s l a b o r a t o r y , n a t u r a l l o g a r i t h m s w e r e specified, we p r e s u m e
that the s a m e w a s t r u e of the v a l u e s of Ghosh and M i t t e r a s well.

Table 2. 7

COMPLEXING CONSTANTS OF URANYL IONS WITH ORGANIC ACIDS


(AFTER GHOSH AND MITTER. 1928)

K^(mole/i)-l = tcomplex] ^ D= i i ! l L £ l (mole/If^


[ free uranyl] x f free acid] [ AH J

Acid Formula Kc(mole/i.)'^ D x 10* V^x 102 ^ (mole/i)- 1

Formic HCOOH 10 176 13 77

Acetic CH3COOH 6 17.5 4.2 143*

Propionic CH3CH2COOH 4 14 3.7 108

Oxalic HOOC COOH 115 65,000 254 45

Ma Ionic HOOC CH2 COOH 80 1,600 40 200

Succinic HOOC CH2 CH2 COOH 50 66 8.2 610

Glycolic CH2OH COOH 15 - - -

Lactic CH3 CHOH COOH 20 - - -

Tartaric 1 HOOC CHOHCHOH COOH 20 1,100 33 60

Mandelic CgHs CHOH COOH 50 - - -

Ahrland (1951a) calculated K = 240 ( m o l e / ^ ) " for the first association constant of uranyl with acetate
ions at 20°C, T) = 1 . 0 .

Rana Char (1942) calculated K^. ^ 10 from optical rotation measurements; cf. Chap. 4,

The a b s o r p t i o n coefficients given by H e n r i and Landau (Table 2.6)


a r e g e n e r a l l y lower than those given by Ghosh and Mitter; this nnay be due to
the fact that the (unspecified c o n c e n t r a t i o n s of the acids used by H e n r i and
Landau probably w e r e not high enough to achieve complete complexing. (The
v a l u e s of Ghosh and M i t t e r w e r e extrapolated to connplete complexing, but
e x t r a p o l a t i o n m u s t have been u n r e l i a b l e b e c a u s e of d i s r e g a r d of changes in
31

acid dissociation with the concentration of the acid in unbuffered solution.)


The s a m e c r i t i c i s m applies to the value in the l a s t column given by Ghosh,
B a n e r j e e and Bhatta (1936) for the absorption coefficient of uranyl ions at
366 m/i in O.IM succinic acid.

Table 2. 8

EFFECT OF COMPLEXING ON ABSORPTION SPECTRUM OF URANYL IONS IN AQUEOUS SOLUTION

(AFTER GHOSH AND MITTER. 1928)

e = logio(Io/I)/cd

c = total concentration of uranium in mole/£

d = light path in cm

1
Wavelength, mjLt
1 Complex with
250.7 254.5 260.0 272.2 277.0 296.1 327.4 336.4 343.5 366.0

None 304.3 260.9 239.1 130.4 108.7 65.2 «43.5) - -

Formate 565.2 391.3 396.6 - 152.2 91.3 - - - -

Acetate - 608.7 513.0 360.9 287.0 152.2 - - - -

Propionate 908.7 808.7 780.4 - 395.7 213.0 - - - -

Oxalate - - - - - 534.8 239.1 117.4 63.0 -

Malonate - - 934.8 521.7 408. 7 165.2 (52.2) - -

Succinate 630.4 491.3 469.6 221.7 156.5 (78. 3) - 7.39^

Glycolate - 760.9 595.7 421.7 287.0 139.1 156. 5) - -

Lactate - 782.6 673.9 - 369.6 195.7 (91. 3) - -

Tartrate - 956.5 752.2 - 360.9 256.5 (195. 7) | 1 3 0 . 4) - -

Mandelate - - - 630.4 421.7 273.9 -((130. 4) (104. 3) (65.2) . t


Uranyl nitrate solution 5 x 10"*M (cf. p . 46 about complexing with nitrate).

I Ghosh, Banerjee, and Bhatta (1936).


+ See d a t a of Ghosh, Naraganmuoti and Ray in Table 4. 22; a n e value of 15 is given there for
X436 mjU.
32

3X.
The a p p r o x i m a t e p r o p o r t i o n a l i t y between the values of K^ and »/D in
Table 2.7 s u p p o r t s the hypothesis that a s s o c i a t i o n o c c u r s mainly between
cations and anions (and not between cations and n e u t r a l acid m o l e c u l e s ) , and
that the " c o n s t a n t s " K^, of the w e a k e r a c i d s m e a s u r e their acid strength
r a t h e r than the stability of t h e i r u r a n y l c o m p l e x e s .

Some figures for the effect of oxalic acid on the absorption s p e c t r u m


of u r a n y l sulfate in the visible and the n e a r ultraviolet (above 346 mfi) w e r e
given a l s o by P r i n g s h e i m (1937). They a r e shown in Tables 2.9 and 2.10.

Table 2.9

E F F E C T OF OXALATE ON AVERAGE ABSORPTION COEFFICIENTS


OF URANYL SULFATE (AFTER PRINGSHEIM, 1937)

e = logxo(lo/l)/cd; c in mole u / l i t e r .

X (mju) 346.6 361.2 365.0 404.7 435.8

UO2SO4 (0.05M)* 67 5.3 2.2 8.5 6


s a m e + H2C2O4 (0.005M) 200 20 11 10.5 7.5

'^According to p . 7, t h e s e v a l u e s c o r r e s p o n d to a product of h y d r o l y s i s ,
r a t h e r than to free UO2 i o n s .

Table 2.10

AVERAGE ABSORPTION COEFFICIENT OF URANYL IONS ( 0 . 0 2 M )


AT 365.0 mjLt, AS FUNCTION OF CONCENTRATION OF ADDED
OXALIC ACID (AFTER PRINGSHEIM, 1937)

e = logio(Wl)/cd ; c in mole u / l i t e r .

[H2C204]
[U02S04] 0 1/I6 1/8 1/4 1/2 1 2

e (365.0 mjLt) 2.2 2.9 3.7 4.9 7.2 11.1 12.4

Table 2.10 shows that complexing is not complete even when m o r e


than one molecule of H2C2O4 (0.02M) a r e p r e s e n t p e r molecule of uranyl
sulfate; t h i s i n d i c a t e s that the f i g u r e s in Table 2.9 m u s t be much lower than
the t r u e a b s o r p t i o n coefficients of the u r a n y l oxalate complex.
33

A s y s t e m a t i c s p e c t r o s c o p i c study of uranyl complexes in solution has


been undertaken by A h r l a n d . His f i r s t p a p e r (l949a) dealt with h y d r o l y s i s
(cf. Section l ) . He then (l949b) p r o c e e d e d to study the complexing of UOt"*^ ions
by m o n o c h l o r a c e t i c acid, using t h e r a n g e below pH 3, w h e r e hydrolysis is i n -
significant. P o t e n t i o m e t r i c m e a s u r e m e n t s indicated that no polyuranyl c o m -
p l e x e s w e r e formed; the s p e c t r o s c o p i c data w e r e i n t e r p r e t e d correspondingly.
The spectruna of a 10"^M solution of u r a n y l p e r c h l o r a t e showed, in the
p r e s e n c e of O.IM c h l o r o a c e t a t e buffer, a g e n e r a l enhancennent of absorption
between 300 and 450 m/i.. No exact s p e c t r a l c u r v e s w e r e determiiied, but
a b s o r p t i o n at 313 mjUwas studied a s fvinction of concentration. The r e s u l t
could be explained by a s sunning a sequence of t h r e e complexing steps (in the
r a n g e from [A] = 0.02M to [A] = 0.4M; the t h r e e complex dissociation
c o n s t a n t s (for 20°C and Tj = l) w e r e calculated with the following r e s u l t s :

UOt+A- Ki = 24 t 3 ( m o l e / e )"^
Uot'^'A"" K2= 160 1 40 (mole/Z )"^
UOf^Al"" K3= 350 t 150 ( m o l e / ^ )"^

P o t e n t i o m e t r i c m e a s u r e m e n t s gave, for the s a m e constants, the values 27.5,


195 and 625, r e s p e c t i v e l y .

Ahrland (l949c) studied in the s a m e way UO'|+ complexes with


thiocyanate i o n s . F i g u r e 2.8C shows the effect of thiocyanate (0.03 to 0,16M)
on the a b s o r p t i o n s p e c t r u m of 0.03M u r a n y l p e r c h l o r a t e . Again, no poly-
n u c l e a r connplexes w e r e found; dissociation constants of t h r e e monouranyl
c o m p l e x e s w e r e derived f r o m extinction m e a s u r e m e n t s at 366 mjLi. The
following v a l u e s (for 20°C and T) = l) w e r e obtained:

UOt''"A- Ki = 5..7 ( m o l e / / ) - ^
UOt+Az" K2 = 5.5 (mole/.£ ) - ^
UOt+A"" K3 = 15 (mole//)"^

Ahrland (l951a) then m a d e a s i m i l a r p o t e n t i o m e t r i c and s p e c t r o s c o p i c


m e a s u r e m e n t on u r a n y l a c e t a t e . F i g u r e 2,8D shows the s p e c t r a between
250 mju and 500 mju of u r a n y l solution in different a c e t a t e buffers. The wave
length 260 mjU w a s chosen for the calculation of a c e t a t e complexing c o n s t a n t s ,
since atX >260 na^u, the h y d r o l y s i s effect on the s p e c t r u m b e c a m e significant
(as shown by the d i v e r g e n c e of c u r v e s 2 - 6 ) . By plotting the m o l a r extinction
coefficient a s a function of a c e t a t e concentration, for t h r e e different uranyl
c o n c e n t r a t i o n s . F i g u r e 2.8E w a s obtained. F o r each value ofe (horizontal lines
in the figure), the v a l u e s of [acetate] a r e found to b e linear functions of the
c o r r e s p o n d i n g v a l u e s of [uranyl], indicating that only mononuclear conmplexes
a r e f o r m e d . The following a s s o c i a t i o n constants w e r e calcqlated:
34

J^
30
. 1 1 1 1 1 1_

30 lOQ 250 600
* ^v H-
r • ^V
%

4
20
• ^K
^ ""^ V K
••
o •

1 •
r •• 3I30N
o " J ^ ^ V
t ' X \ X \
X \ \ \
1 •t X ^ ^» V
UI 10 ^—
- • X \ ^» X



o 1 • /4050 \ \ \ ^ \
r ' /^ \ V \ \ ^ •

• 3660 4360"


0 - ••
••
1 1 1 1 1
1 •
2500 3000 3500 4000 4500 5000 A

Figure 2.8C

MOLAR DECADIC EXTINCTION CURVES OF URANYL THIOCYANATE COMPLEXES


(AFTER AHRLAND, 1949c). SOLID LINE: URANYL IONS (FREE). DASHED LINES:
[ U 0 j + ] o = 0.0331M; [THIOCYANATE] „ = 0.030, 0.100, 0.250 AND 0.600M, RESPEC-
•JVELY. DOTTED LINE: THIOCYANATE ALONE, e^ = (LOG I Q / I ) / [ T H I O C Y A N A T E ] QD.

_UO^"^]o = TOTAL CONCENTRATION OF URANYL (COMPLEXED AND FREE).


T H I O C Y A N A T E ] 0 = TOTAL CONCENTRATION OF THIOCYANATE (IN O.IMHCIO^ TO
AVOID HYDROLYSIS OF URANYL; NO CORRECTION FOR INCOMPLETE DISSOCIATION
OF THIOCYANIC ACID NEEDED; CONSTANT IONIC STRENGTH t) = 1.0 ADJUSTED
BY NaClO^).
35

.itj I 1 1 1
2500 3000 3500 4000 4500 A

Figure 2.8D

MOLAR EXTINCTION CURVES OF URANYL ACETATE SOLUTIONS (AFTER AHRLAND,


1951a). CURVE 1: URANYL ION. CURVE 2: SAME, PARTIALLY HYDROLYSED
[uOj^Jo = 0.033M, pH 4.1). CURVES 3, 4, 5: URANYL ACETATE COMPLEXES
WITH [UOjTo = O.OIOM, [ A C E T A T E ] 0 = 0.030M, IN ACETIC ACID-ACETATE
BUFFERS 5:1, 2:1, AND 0.5:1, RESPECTIVELY. CURVE 6: SAME, WITH
[U02'*']o = O.OIOM, [ A C E T A T E ] 0 = 0.060M, IN ACETIC ACID-ACETATE BUFFER 2:1.
CURVES 7, 8: ACETIC ACID-ACETATE BUFFERS 5:1 AND 0.5:1, RESPECTIVELY.
UOz^lo ^ TOTAL CONCENTRATION OF FREE AND COMPLEXED URANYL;
A C E T A T E ] 0 = TOTAL CONCENTRATION OF ACETATE USED (A SMALL CORREC-
TION MUST BE MADE FOR THE EFFECT OF ACETIC ACID ON THE CONCENTRA-
TION OF FREE ACETATE IONS). COMPLEXING OF URANYL WITH ACETATE STRONG
ENOUGH TO PREVENT HYDROLYSIS IN ABOVE BUFFERS. IONIC STRENGTH 7; = 1.0
ADJUSTED BY NaClO^.
1600

1400

1200

1000

800

Figure 2.8E

MOLAR DECADIC EXTINCTION COEFFICIENTS OF URANYL ACETATE COMPLEX


SOLUTIONS AS FUNCTION OF TOTAL CONCENTRATION OF ACETATE C^
(FREE + COMPLEXED WITH URANYL). ^ , 0 : [UO+^JQ = 0.00075M;
• , V : Cu0++]o = 0.0025M; # , 0 : [U0++]o = 0.0075M. OPEN SIGNS:
[ACETIC ACID]: [ A C E T A T E ] = 5; FULL SIGNS: [ACETIC A C I D ] :
[ A C E T A T E ] = 2. DASHED LINES EXTRAPOLATED TO [ H + ] = oo (NO HYDROL-
YSIS). THE POINTS IN WHICH A HORIZONTAL e^^ = CONST. CROSSES THE
SEVERAL CURVES CORRESPOND TO THE SAME CONCENTRATION OF FREE
ANIONS.
37

37
Kj = 240 ( m o l e / ^ )-^
K2 = 2.3 x 10* ( m o l e / ^ ) " ^
K3 = 2.2 x 10^ {mo\e/l)'^
for 20°C and ionic s t r e n g t h 1.0.

Table 2.10A s u m m a r i z e s the complexing constants d e r i v e d by


Ahrland (1949. 195l) for m o n o n u c l e a r u r a n y l ions, with s e v e r a l inorganic
and organic i o n s .

Table 2.10A

SPECTROSCOPICALLY DETERMINED EQUILIBRIUM CONSTANTS


O F REACTIONS UOt"*" + n A " = UOt A^^ A F T E R AHRLAND
(1949, 1951). 20°C; ionic strength 1.0.

n = 1 n = 2 n = 3
A"
(mole/^)-^ (mole/^)"^ (mole//)-^

OH" 2 X 10^* •
ci- 0.5 ( t 0,3)
SO4 56 (+ 6) 450 (1 50)
CH3COO" 240 ( t 10) 2.3 X 10* ( t 0.2) 2.2 X 10^ ( t 0 3)
CH2ClCOO~ 24 (± 3) 150 (± 40) 350 ( t 150)
CNS" 5,7 (t 0.3) 5.5 (1 1) 15 (t 5)

*Ahrland gives 2 x 10"^ m o l e / ^ for [UOt"*'OH~][H"'']/[UOt"''] (cf. p . U ) ;


a s s u m i n g [H+][OH~]-^ 10^*, we calculate [UOt"'"OH-]/[UOt"*"] [OH"]
= 2 X 10' ( m o l e / ^ ) - ^

F o l e y and A n d e r s o n (1949) o b s e r v e d the effect of sulfosalicylic acid


on the s p e c t r u m of an aqueous solution of u r a n y l a c e t a t e . F i g u r e 2.9 shows
the a b s o r p t i o n c u r v e s of a 5 x 1 0 ~ ' M solution of UO2AC2 (pH 4.5) (curve l)
and of a 7.5 x 10"*M solution of UO2AC2 to which 4.25 x 10~^M sulfosalicylic
acid h a s been added (pH 4,65)(curve II). Although the added acid does not
a b s o r b in the v i s i b l e , and the concentration of UO"^"^ i s lower by a factor of
6.7, a b s o r p t i o n c u r v e II l i e s m u c h higher than c u r v e I. The a c e t a t e c u r v e
p r o b a b l y c o r r e s p o n d s to a solution containing hydrolyzed u r a n y l ions
([(^02)302] according to Sutton's F i g u r e 2.3) and uranyl a c e t a t e c o m p l e x e s .
According to T a b l e s 2.6 and 2.8, the u r a n y l acetate complexes a b s o r b
strongly in the far u l t r a v i o l e t ; but t h e i r formation does not affect significantly
3r

400 450 500 550


WAVE LENGTH, m/i

Figure 2.9

EFFECT OF SULFOSALICYLIC ACID ON ABSORPTION SPECTRUM OF URANYL IONS


(AFTER FOLEY AND ANDERSON, 1949) CURVE I : 5 x I Q - ^ M U O / c j . CURVE I I :
7.5 X lO-^MUO-Ac, + 4.25 x lO-^M SULFOSALICYLIC ACID.
39

J2-
the visible and n e a r u l t r a v i o l e t s p e c t r u m , which r e m a i n s s i m i l a r to that of
n i t r a t e . The sulf©salicylate complex, on the other hand, a b s o r b s strongly in
the v i s i b l e and n e a r u l t r a v i o l e t . F o l e y and Anderson noted that addition of
i n c r e a s i n g a m o u n t s of a c e t a t e buffer caused absorption in the visible region
to b e c o m e w e a k e r , indicating competition of acetate with sulf©salicylate for
uranylions.

By plotting the difference between the optical density, at selected wave


lengths, of the m i x t u r e and of an equal annount of u r a n y l salt without sulfo-
s a l i c y l i c acid, a s a function of the r a t i o x = [UO^+]/([UOt+] + [SSA]), Foley
and A n d e r s o n obtained, for X = 400, 420, 440 and 46& rrijU, s y m m e t r i c a l c u r v e s
with p e a k s at x = 0.5. A s f i r s t pointed out by Job, this i s a proof of formation
of a 1:1 complex. The s a m e r e s u l t was obtained at pH 4,6, 5.1 and 6 . 1 . The
optical density was highest at pH 4 . 5 - 4 . 7 , and declined at both lower and
higher pH v a l u e s . The decline at low pH values was considered a s indicating
that the complex fornnation o c c u r r e d with the divalent anion of the sulfosali-
cylic acid (pK = 2.86); the decline at high pH values was a s c r i b e d to h y d r o l y s i s .

The extinction coefficients of the connplex w e r e d e t e r m i n e d by using a


solution containing a 9:1 e x c e s s of the complexing anions; they w e r e
e = 403 at 440 ncijU and e = 432 at 460 m^. Using t h e s e v a l u e s , the c o n c e n t r a -
tion of the complex was calculated in different m i x t u r e s , and thence the d i s -
sociation constant was d e r i v e d :

[UOt+] [R]
K = = (1.3 t 0.8) X 10~* ( m o l e / ^ ) " ^ (23)
[UOt+ R]

c o r r e s p o n d i n g to a complexing constant of between 5,000 and 20,000. An


i m p r o v e d method of calculation, using solution p a i r s of constant ionic s t r e n g t h ,
with the s a m e complex c o n c e n t r a t i o n , but different r a t i o s of the components,
led to a m o r e p r e c i s e v a l u e :

K = (1.93 t 0.08) X 10-* (25°C)

or l / K i : ^ 5 2 0 0 . T h i s c o r r e s p o n d s to a f r e e energy of a s s o c i a t i o n

A F = -5.06 kcal (25°C)

Raising the t e m p e r a t u r e i n c r e a s e s t h e connplexing, but the i n c r e a s e i s slight,


indicating a s m a l l negative h e a t of formation.

C o n c e n t r a t i o n [R] in Equation (23) r e f e r s to total acid, which at the


pH of m a x i m u m color depth ia completely d i s s o c i a t e d into R and 2H'''. A
c o m p l e x of a divalent anion and a divalent cation (UO2 ) is n e u t r a l as a
•whole, but F o l e y and A n d e r s o n suggested that the uranyl sulfosalicylate
connplex i s a 'zwitterion,'"' +UO2R-.
40
^0
F o l e y and A n d e r s o n found that addition of 0.18M a c e t a t e to 0.002M
sulfosalicylate r e d u c e s the optical density at 460 na)i from 0,643 to 0.242;
t h i s i n d i c a t e s a r a t i o of a s s o c i a t i o n constants of the o r d e r of 10^, i.e., an
a c e t a t e conmplexing constant of the o r d e r of 50, This can be compared with
the value of 240 ( m o l e / € )-^ d e r i v e d by Ahrland (for 20*^0 and T) = l.O), and
a l s o with the value of YL^j v D given in the l a s t column of Table 2.7. If it
is a s s u m e d that the l a t t e r c o r r e s p o n d s to an a v e r a g e acetic acid c o n c e n t r a -
tion of KQC±. O.IM (it was calculated f r o m m e a s u r e m e n t s between 0.005 and
1 M ) , the c o r r e s p o n d i n g value of K i s

K = ^ c / ^ ^ 4 0 (rnole/e)-^

Since complexing of u r a n y l ions with organic acids i s of g r e a t i m -


p o r t a n c e for the behavior of u r a n i u m in the living organisnn, it h a s been
a l s o studied by t o x i c o l o g i s t s . E l e c t r o c h e m i c a l methods (polarography,
t r a n s f e r e n c e , e t c ) have been used by t h e m , and only a few s p e c t r o s c o p i c
o b s e r v a t i o n s have been m a d e . The r e s u l t s obtained up to 1947 w e r e s u m -
m a r i z e d by Dounce et a l . (1949). One i m p o r t a n t g e n e r a l r e s u l t of e l e c t r o -
c h e m i c a l studies is that they indicated, in all s y s t e m s studied, the formation
of higher c o m p l e x e s in addition to the 1:1 complexes whose existence appeared
sufficient to explain the above-de s c r i b e d s p e c t r o s c o p i c r e s u l t s of other i n -
v e s t i g a t o r s . F o r e x a m p l e , in a c e t a t e buffers (NaAc + HAc) a n e u t r a l
complex, probably UO2 A c 2 - , was indicated at [Ac"] > 0.025M by t r a n s -
ference m e a s u r e m e n t s at 20°C, and at[Ac-l, > 0 . 0 5 M b y polarographic
m e a s u r e n n e n t s at 25°C. An anionic u r a n y l acetate complex, probably
UO2 AC3 , a l s o w a s o b s e r v e d in t r a n s f e r e n c e e x p e r i m e n t s . Its r e l a t i v e
c o n c e n t r a t i o n was independent of the concentration of n e u t r a l acetic acid
m o l e c u l e s and only dependent on that of the A c " ions, as expected for a c o m -
plex in whose formation only a c e t a t e ions take p a r t .

Absorption changes o b s e r v e d in 0.2M a c e t a t e buffers with varying pH,


d e s c r i b e d in the s a m e r e v i e w , probably r e f e r to h y d r o l y s i s r a t h e r than
formation of u r a n y l a c e t a t e c o m p l e x e s (as a s s u m e d by the review). They have
been t h e r e f o r e d e s c r i b e d in Section 1 of t h i s c h a p t e r ,

P o l a r o g r a p h i c studies have been continued by the R o c h e s t e r t o x i c o -


logical group with other o r g a n i c a c i d s , such as pyruvic, m a l i c , and p a r t i c u l a r l y
c i t r i c , by Neuman et a l , [Neuman and Havill (1948), R o d g e r s and Neuman (1948),
and Neuman, Havill and F e l d m a n (1949)]. They led to the conclusion that d i -
carboxylic a c i d s g e n e r a l l y have a s t r o n g e r tendency for a s s o c i a t i o n with uranyl
ions than a c e t i c acid, even when - a s in the c a s e of succinic acid - t h e i r
-dissociation constant i s not h i g h e r than that of a c e t i c acid. It w a s s u r m i s e d
that complexing with d i b a s i c acids involves formation of 5 -j6 - or 7 - m e m b e r e d
r i n g s with both c a r b o x y l s . In fact mixing uranyl n i t r a t e (pH 2,8) with oxalic
acid (pH 1,6) lowered the pH to 1.3, indicating that uranyl ions displaced a
second proton from the m o n o b a s i c oxalic acid anion.
41
H-l
A further complication of the connplexing m e c h a n i s m was foiind in
t h e s e s t u d i e s : it w a s deduced that t h e 1:1 u r a n y l c i t r a t e connplex f o r m s a
r a t h e r stable dinner. The formation of the d i m e r was described by Neuman
et a l . (1949) in the following way:

UOt"*" + H2Cit ^ U O t + H C i t = + H+

2 |uot"^HCit=| -|(UOt+)2H+(Cit*)2|+ H+ ( = dimer" + H+)


giving for the d i s s o c i a t i o n constant the e x p r e s s i o n

K [UOt"^] [HzCit-] (24)


[H+]3/2 [ d i m e r ' ] ^/2

A value of 0.18 t 0.08 w a s calculated for K^j at pH 2 . 9 - 3 . 6 and a


t o t a l u r a n y l c o n c e n t r a t i o n of 5 x 10-*M.

The u r a n y l c i t r a t e s y s t e m was further studied s p e c t r o s c o p i c a l l y by


F e l d m a n , Neunnan and Havill (1949). F i g u r e 2.10A r e p r e s e n t s the optical
density of u r a n y l salt solutions with and without added c i t r i c acid,in the
alkaline region (pH 7.5) and in the acid region (pH 3.75). The steep change
of a b s o r p t i o n (at 320 mju) a s a function of pH in the regions < 3 and 6-7
( F i g u r e 2.10B) i n d i c a t e s s u c c e s s i v e formation of two complexes; the second
one i s stable up to pH 11 (while non-complexed u r a n y l n i t r a t e solution of the
s a m e c o n c e n t r a t i o n p r e c i p i t a t e s above pH 4.5).

The complex that is stable at pH 3.85 h a s the composition 1 UO"!"*" :


1 c i t r a t e , a s shown by the plot of a b s o r p t i o n coefficients (at 320, 330 or
350 mju) a s function of [UOt"*"] / ([UOt''"] + [ c i t r a t e ] } (Figure 2.10C). The
a u t h o r s assunne, on t h e b a s i s of previously d e s c r i b e d e l e c t r o c h e m i c a l r e s u l t s ,
that t h i s connplex i s p r e s e n t mainly as a dinner, and calculated its d i s s o c i a -
tion constant a c c o r d i n g to Equation (24). The K^j values obtained w e r e 0.04
for 1 X 10-*M u r a n y l solution (pH 3 . 1 6 - 3 . 6 9 ) and 0.065 for 5 x 10-*M
solution (pH 3.03). The agreennent with the previously given p o t e n t i o m e t r i c
value ( K = 0.18) i s only in the o r d e r of naagnitude; it is suggested that the
spectroscopic values a r e more reliable.

The natujre of the m o r e strongly colored connplex p r e s e n t at pH 7.5


h a s not been c l a r i f i e d , but it s e e r a s to involve a u r a n y l : c i t r a t e r a t i o > l ,
p e r h a p s 1.5.

The a b s o r p t i o n c u r v e s of aqueous solutions of a nunnber of complex?


u r a n y l s a l t s (mainly of the aldinnine s e r i e s ) have been m e a s u r e d by von K i s s
and c o - w o r k e r s in t h e i r extensive study of the s p e c t r a of such connplexes
[see von K i s s and N y i r i (l942b), and von K i s s , Csokan and N y i r i (l942a)].

S p e c t r a of u r a n y l s a l t s complexed with organic b a s e s (or t h e i r salts)


in o r g a n i c solvents will be d i s c u s s e d in the next section. Some p a r t -
aqueous s y s t e m s , such a s the systenn u r a n y l n i t r a t e and t e t r a b u t y l a m m o n i u m
n i t r a t e and c o n c e n t r a t e d n i t r i c acid, will b e included in t h i s d i s c u s s i o n .
42

^X
1 1 1 1
\

0.7 —

0.6 —

0.5
>
1-
cn Curves obtained from the
z following solutions were
LJ 0.4 adjusted according to Beer*s
O Low to the equivalent of
5 X IO~^M uranium:
-I
Curve U02(N03)2 Citric Acid KCI PH
O
0.3 \ 1 2.5 X 10"* M — O.IM 3.88 J
Q. \ 2 2.0 X I 0 - * M O.IM O.IM 3.75
o 3 5.0 X 10"* M O.IM 7.50
\ 3
\
0.2 - \

\2 \

0.1

n n
V v^^tr
320 360 400 ] 440 480
WAVE LENGTH, mfi

FIG. 2 . l O A - A B S O R P T I O N SPECTRA OF URANYL


CHLORIDE AND URANYL CITRATE.
43

^J

FIG. 2 . I 0 B - T H E EFFECT OF pH ON ABSORPTION OF


URANYL SOLUTIONS.
<^M^

Theoretical Maximum
for 1:1 Combining Ratio
0.3

0.2

lO

0.1 -

0.0
0.2 0.4 0.6 0.8

INITIAL
[UO2] + [CITRIC ACID]

FIG. 2.10 C — A P P L I C A T I O N OF J0B*S METHOD OF


CONTINUOUS VARIATIONS TO THE STUDY
OF THE URANYL CITRATE COMPLEX AT
pH 3.85±0.03.
3. ABSORPTION SPECTRA OF URANYL COMPOUNDS
IN ORGANIC SOLVENTS

Most c o m p a r i s o n s of u r a n y l salt s p e c t r a in different solvents suffer


f r o m the lack of information concerning the n a t u r e of m o l e c u l a r species -
n e u t r a l or ionized - p r e s e n t in solution.

The f i r s t extensive c o m p a r i s o n s of this type w e r e made by Deussen


(1898). He m e a s u r e d the positions of ten uranyl bands (486-369 rnju) in
w a t e r , m e t h a n o l , ethanol, a c e t o n e , g l y c e r o l , amylol, acetic e s t e r and e t h e r .
Addition of 50% C2H5OH to w a t e r was found to shift all bands t o w a r d s the
r e d , but the directioii of the shift was r e v e r s e d in 80% and 100% ethanol.
Addition of g l y c e r o l to w a t e r c a u s e d a shift of all bands towards the r e d ;
t h i s shift i n c r e a s e d - w i t h the amount of g l y c e r o l .

J o n e s and Strong (l910a) photographed the absorption s p e c t r a and


e s t i m a t e d the positions of the band peaks of u r a n y l chloride and u r a n y l
n i t r a t e , in w a t e r , m e t h a n o l , ethanol, g l y c e r o l , acetone, and in b i n a r y m i x -
t u r e s of t h e s e solvents and a l s o of u r a n y l acetate in w a t e r and in nnethanol.

They noted that the absorption bands w e r e considerably s t r o n g e r in


m e t h a n o l than in w a t e r ; the band peaks w e r e s h a r p e r and w e r e generally
shifted t o w a r d s the r e d . B e e r ' s law was found to hold between 0.06 N and
0.25 N solutions of u r a n y l chloride in ethanol. Addition of calciunn qhloride
had a l m o s t no effect on the a b s o r p t i o n s p e c t r u m of u r a n y l chloride in
m e t h a n o l (in c o n t r a d i s t i n c t i o n to the behaviour of the s a m e compound in
aqueous solution).

A s u m r n a r y of the band positions of u r a n y l chloride in different s o l -


v e n t s , including those above-rr^entioned, and a l s o some investigated in a s u b -
sequent study by Jones and Strong (1912), is given in Table 2.11 .

The s a m e a u t h o r s o b s e r v e d the effect of t e m p e r a t u r e on the a b s o r p -


tion s p e c t r a of u r a n y l c h l o r i d e in acetone (22-195°), of uranyl n i t r a t e in
propanol (20°-145°C), and of both t h e s e s a l t s in isobutanol (20'-115°C) and
m e t h y l sulfate.

Von Kurelec (1927) m a d e a c o m p a r i s o n of the positions of the four


lowest frequency bands of u r a n y l n i t r a t e in 44 organic solvents^ 13 aliphatic
alcohols and glycols, 7 aliphatic a l d e h y d e s , 8 aliphatic a c i d s , 9 e s t e r s of
s u c h a c i d s , 4 n i t r i l e s , e t h e r , a c e t o n e , and c i t r o n e l l a l .

In all s o l v e n t s , ionizing and non-ionizing, the position of the a b s o r p ^


tion bands of u r a n y l n i t r a t e w a s a p p r o x i m a t e l y the s a m e . F o r e x a m p l e , the
c e n t e r of the f i r s t band lay in aqueous solutions between 483 m/.i (cone. HNO3)
and 493 m/i ( c o n e HCl) and in organic solvents betweep 483.4 m/i (glacial
a c e t i c acid) and 490.4 nnjii (glycol). S i m i l a r l y , the c e n t e r of the second band
lay between 468 and 478 mju in aqueous solutions, and between 466.6 and
472.9 m/i in organic s o l u t i o n s .
Table 2,11

ABSORPTION BANDS OF URANYL CHLORIDE


IN D I F F E R E N T SOLVENTS
(after Jones and Strong 1910a, 1912)

Band Cente r s (n:^)


Solvent 1
1 2 3 4 5 6 7

H2O 492 474 456 446 431.5 417 402.5


CH3OH 493 476 459 446,5 434.5 422 409
C2H5OH 490 475 458 440 - 425 410
C3H7OH 491 475 458 458 446.0 423 410
i-C3H70H " 475 456 436 - 425 410
C4H9OH 497 - 475 456 439 424 410
i-C4H90H 490 - 472 456 440 - -

(C2H5)20 - - 463 444 430 416 404


CH3OOCH3 492 479 462 444 428 416 403
Glycerol 505 472 454 440 426 414 402.5
Formamide 484 - 465 445 - -

Within a homologous s e r i e s (e.g., the s e r i e s of s a t u r a t e d s t r a i g h t


chain a l c o h o l s , f r o m CH3OH to C8HX7OH), a "red shift" could be o b s e r v e d
with i n c r e a s e d index of r e f r a c t i o n of the solvent (cf. Table 2.12). (No
s i m i l a r r e g u l a r i t y is noticeable in Table 2,11.)

In m i x e d organic s o l v e n t s , e a r l y o b s e r v a t i o n s indicated p r e f e r e n t i a l
a s s o c i a t i o n of u r a n y l s a l t s (or t h e i r ions) with one of the components. T h u s ,
H a r t l e y (1903) concluded f r o m s p e c t r o s c o p i c evidence that when hydrated
u r a n y l n i t r a t e is dissolved in e t h e r the s p e c t r u m r e m a i n s that c h a r a c t e r i s t i c
of u r a n y l ions in w a t e r .

Jones and Strong (1910a) noted that addition of as little as 8% w a t e r


to a u r a n y l chloride solution in m e t h a n o l caused the uranyl bands to sh^ft
a p p r e c i a b l y t o w a r d s t h e i r position in aqueous solution. S i m i l a r l y , addition
of 10% g l y c e r o l to m e t h a n o l caused the s p e c t r u m of u r a n y l chloride t o
a s s u m e the c h a r a c t e r of that in p u r e g l y c e r o l .
^7
Table 2,12

SHIFT OF AN ABSORPTION BAND OF U02(N03)2


IN A SERIES OF SOLVENTS
(von K u r e l e c , 1927)

Solvent mjLt -n
CH3OH 465.0 1.3326
C2H5OH 465.8 1.3614
C3H7OH 466,3 1.3859
C4H9OH 467.9 1.3991
C5H11OH 467,2 1.4078
CIH17OH 467.4 1.4314

J o n e s and Strong (1912) and Jones (l913a) a s s e r t e d that the b r o a d e n e d


and shifted bands o b s e r v e d in u r a n y l salt solutions in methanol upon addition
of w a t e r can be i n t e r p r e t e d a s the r e s u l t of mutual superposition of " m e t h a -
nolate b a n d s " and " h y d r a t e b a n d s , " a conclusion which they used a s a^rgument
supporting the solvate t h e o r y of solutions. To t e s t this theory was the m a i n
motivation of the long s e r i e s of s t u d i e s devoted to a b s o r p t i o n s p e c t r a of i n -
organic s a l t s by Jones and c o - w o r k e r s , and s u m m a r i z e d in Jones and Strong's
m o n o g r a p h s in 1910 and 1911 . (The m o s t convincing examples of the c o -
e x i s t e n c e of bands c h a r a c t e r i s t i c of individual solvents in a mixed solvent
w e r e found by Jones in solutions of U(lV) s a l t s , such a s UBr4.)

MuUer (1940) o b s e r v e d that the u l t r a v i o l e t absorption edge of u r a n y l


n i t r a t e is shifted t o w a r d s the longer w a v e s , and the absorption a p p e a r s s t r o n g e r
when e t h e r is substituted for w a t e r a s solvent. The effect is s t r o n g e r the m o r e
dilute the u r a n y l s o l u t i o n s .

M a t h i e s o n (1949) studied the a b s o r p t i o n s p e c t r a of u r a n y l n i t r a t e in


two k e t o n e s : acetone and m e t h y l ethyl ketone, and, for c o m p a r i s o n , in
diethyl e t h e r and w a t e r . He found, in ketonic solutions, a s h a r p enhancement
of the long-wave a b s o r p t i o n p e a k s , and a g e n e r a l i n c r e a s e in absorption i n -
t e n s i t y above 330 mju. He a t t r i b u t e d t h e s e s p e c t r a l changes to connplex f o r m a -
tion. Stable c r y s t a l l i n e connplexes with the composition U02(N03)2MezCO'3H20
and U 0 2 ( N 0 3 ) 2 MeEtCO-3H20 could in fact be c r y s t a l l i z e d f r o m t h e s e solutions.
A sinnilar complex, U02(N03)2 EtjO'SHzO was obtained f r o m ethyl e t h e r .

A s i m i l a r study w a s c a r r i e d out by Kaplan, Hildebrandt and Ader (1950a),


who m e a s u r e d the s p e c t r a of u r a n y l n i t r a t e solutions in methyl isobutyl ketone
("hexone"), cyclohexanone, and acetone. Since n i t r a t e s of organic bc^ses a r e
48

^r
known to enhance the e x t r a c t a b i l i t y of u r a n y l n i t r a t e into methyl isobutyl
ketone, the effect of t h e s e compounds on the uranyl s p e c t r u m also was,
investigated.

F i g u r e 2.11 shows that the absorption s p e c t r a of u r a n y l n i t r a t e


(hexahydrate ?) a r e v e r y s i m i l a r in the t h r e e k e t o n e s . B e e r ' s law is followed
(in hexone) at least up to 0.1 M. Addition of t e t r a b u t y l a m m o n i u m n i t r a t e ,
NBU4NO3J (as well as that of tributylamnnonium n i t r a t e , pyridinium n i t r a t e
or m e t h y l isobutyl k e t a z i n i u m n i t r a t e ) produces a striking s p e c t r a l change.
F o u r bands in the long-wave p a r t of the s p e c t r u m become strongly enhanced,
without a p p a r e n t change in t h e i r p o s i t i o n s . The i n c r e a s e of the a b s o r p t i o n
coefficient in this p a r t of the spectrunn i s a linear function of concentration
of the added t e t r a b u t y l a m m o n i u m n i t r a t e ; the i n c r e a s e c e a s e s abruptly when
a m o l e c u l a r r a t i o [U02(N03)2] : NBU4NO3 = 1 is reached. This points to the
f o r m a t i o n of a 1 : 1 complex, for which the following composition is suggested:

U02(N03)2 + N03-^z:^U02(N03)3~

The m e t h o d of continuous v a r i a t i o n s (comparison of s p e c t r a of m i x t u r e s with


constant t o t a l amount of the two n i t r a t e s , but varying proportion, x, of u r a n y l
n i t r a t e ) showed the a v e r a g e a b s o r p t i o n coefficient (at 455 and 470 nnju) to r i s e
with X up to X = 0,5, and then to d e c r e a s e - as expected for a 1 : 1 complex
whose a b s o r p t i o n is s t r o n g e r than that of the two components (Figure 2,12).
The l i n e a r i t y of the change, and the consequent e x t r e m e s h a r p n e s s of the
peaks at X = 0.5, indicate that the complex is v e r y s t a b l e .

Kaplan et al. point out that the a r g u m e n t does not depend on the extent
of the ionic d i s s o c i a t i o n of u r a n y l n i t r a t e in the organic solvent in the a b -
s e n c e of NBU4NO3 ; the m a x i m u m in F i g u r e 2,11 c o r r e s p o n d s to t h r e e n i t r a t e
r a d i c a l s p r e s e n t per one u r a n y l g r o u p .

A s i m i l a r s p e c t r a l change can be produced by the addition of n i t r i c


acid (instead of NBU4NO3) to a solution of u r a n y l n i t r a t e in hexone. However,
even at a n i t r i c acid c o n c e n t r a t i o n of 0.78 M, the absorption between 420 and
480 m/i is i n c r e a s e d only about one-half as rauch as it is in 0.02 M NBU4NO3 .
The a u t h o r s suggest that n i t r i c acid addition leads to an e q u i l i b r i u m

• U02(N03)2 + HNO, - i ^ H U O ? ( N Q 3 ) 3 ,

and that the n e u t r a l c o m p l e x HU02(N03)3 has p r a c t i c a l l y the s a m e spectrunn


a s the c o m p l e x ion U02(N03)^ . With t h e s e two a s s u r a p t i o n s , they calculated:

[HU02(N0,)3]
•^-'•^^°-^'[UO.(NO,).]lHNO,L ("'

The c l o s e a g r e e m e n t they find between K values calculated f r o m two a b s o r p -


tion v s . n i t r i c acid c o n c e n t r a t i o n c u r v e s (at 454 and 469 m / i , respectively)
by using for the complex ion the (previously determined) extinction coefficients
of the complex m o l e c u l e , is quoted by them a s confirmation of the postulated
identity of the two s p e c t r a .
^f
= I 1 1 1 1 1 1 1 1 1 1 1. 1 1 1 1 -
30 ^

-
5 *

** •
25 — .
-

-
_ ; :: :

20 " • " •
;I • ••
• ••
•t it * • ••
*• • * * • •• —
- (
: •:i•
1 * • * * . *

o - •• • •
_ 11•* *•• ••* •" •, •• • "

z
V- 15 - • •, •• •• •• *•• *•• t• •*
** —
X \
« • • • • •

LJ ; • : : t • •• *• ••
- \ • •
: •
• •
• •
* *
• •
*
• •
Q: _ I t .' *; J *. • :* •: • -
<i 1r • » • " *
• « •
_i \ -
o
_
'\ -^P^ : • ^
10
-
'i ^>r^^fc^ : , • «
__„

" ^ • * ~
1 •
— V. :\r\ / '.' T- -V —
-. _
UI V-^/--- %}k \^ i i
5 — \\. : : —

" \ \ ^ i \ : • "

— \ i *, -
^,
_ »v. _
n 1 1 1 1 1 .1 1 1 1 1 1 1 1 1 - , • • • . . • ;

350 400 450 500


WAVE LENGTH, m/*

FIG.2.I1-ABS0RPTI0N SPECTRA OF URANYL NITRATE IN


SOME KETONIC SOLVENTS.
0 . 0 2 M URANYL NITRATE IN ACETONE
0.02M URANYL NITRATE IN METHYL ISOBUTYL KETONE
0.02M URANYL N I T R A T E IN CYCLOHEXANONE
0 . 0 2 M URANYL NITRATE, 0.02M TETRABUTYLAMMONIUM
NITRATE IN ACETONE.
So
""•^rn—I—\—\—r~i \ \ f

FIG.2.I2-REACTION BETWEEN URANYL NITRATE AND


TETRABUTYLAMMONIUM NITRATE IN
METHYL ISOBUTYL KETONE.
O 4 5 5 m/i
A 4 7 0 mfi
51

Of
Adding NBU4NO3 to a UO2NO3 solution containing l a r g e e x c e s s of n i t r i c
acid c a u s e s a f u r t h e r s h a r p r i s e of the absorption b a n d s , even if the amount
of o r g a n i c n i t r a t e added ( ' ^ 0.1 M) is s m a l l c o m p a r e d to that of the n i t r i c acid
a l r e a d y p r e s e n t {-^ 1 M). The effect of NBU4NO3 is not quite a s strong in the
p r e s e n c e as in the a b s e n c e of n i t r i c acid, and the final s p e c t r u m , obtained
u p o n . " s a t u r a t i o n " with NBU4NO3 , is the s a m e with and without acid. Kaplan
et a l . pointed out that the addition of a c e r t a i n amount of strong n i t r i c acid
a l s o i m p l i e s the addition of 1.6 m o l e c u l e s of w a t e r per molecule of added
n i t r i c acid; apparently the p r e s e n c e of this amount of w a t e r does not affect
significantly the s p e c t r u m of the u r a n y l t r i n i t r a t e complex.

C o m p a r i s o n of the action of s e v e r a l n i t r a t e s shows NBU4NO3 and


NPr4N03 ( P r = n-propyl) to be equally effective (in acetone as solvent); with
a t e r t i a r y amine ( 2 - n - h e x y l p y r i d i n e ) , complexing is l e s s complete (88% in
0.02 M U02(N03)2 + 0.02 M hexylpyridinium n i t r a t e ) . This cannot be a s c r i b e d
to an a c i d - b a s e d i s s o c i a t i o n of HNC11H17NO3 ( . " HNO3 + NCuHiy), since
addition of n i t r i c acid does not affect the absorption. Rathey, one has to
a s s u m e a r e l a t i v e l y low complexing constant of the t e r t i a r y amine ('i^Sx lO' ,
a s against >10^ with the q u a t e r n a r y a m m o n i u m s a l t s ) . In hexone solution,
t o o , p y r i d i n i u m n i t r a t e p r o v e s to be a l e s s effective complexing agent than
the q u a t e r n a r y a m m o n i u m n i t r a t e s . This (as well as the still l e s s e r effect
of n i t r i c acid) m a y be r e l a t e d to the s t r o n g e r complexing action of NOJ ions
c o m p a r e d to RNO3 m o l e c u l e s . (The l a r g e r size of the anion U02(N03)J ,
c o m p a r e d to NOJ, ought to make the ionization tendency of the complex
RU02(N03)3 s t r o n g e r than that of the molecule RNO3,)

The nnolecule U02(N03)2 i s , according to the estinaate of Kaplan et al.,


p r a c t i c a l l y non-ionized in ketonic s o l v e n t s , such a s acetone or hexone, in the
c o n c e n t r a t i o n s u s e d , while m o l e c u l e s such as NBU4NO3 m a y be 40 or 70%
d i s s o c i a t e d in t h e s e s o l v e n t s . Consequently, the significant complexing p r o c -
e s s e s a r e t h o s e coupling the n e u t r a l m o l e c u l e s U02(N03)2 with the m o l e c u l e s
RNO3 and the ions NO^ , The complexing is m o r e stable the s t r o n g e r the
d i s s o c i a t i o n RNO3—^R"^ + NO^ .

The n e u t r a l c o m p l e x RU02(N03)3 itseK undergoes ionic d i s s o c i a t i o n


into R"*" and U02(N03)^ , while the n e u t r a l m o l e c u l e s U02(N03)2 d i s p r o p o r t i o n -
ate into UO2NO3 and U 0 2 ( N 0 3 ) ^ , T r i n i t r a t o u r a n y l anions can thus a r i s e in
t h r e e different w a y s : by a s s o c i a t i o n of u r a n y l n i t r a t e with NOJ ions, by
a s s o c i a t i o n of the s a m e s a l t with organic n i t r a t e s followed by ionic d i s s o c i a -
tion, and by d i s p r o p o r t i o n a t i o n .

A s mentioned b e f o r e , the a u t h o r s a s s u m e the s p e c t r o s c o p i c a l differ-


ence between ionized and non-ionized c o m p l e x e s , U02(N03)J and RU02(N03),
to be insignificant; if this is s o , then the concentration r a t i o of t h e s e two
f o r m s cannot be d e r i v e d f r o m s p e c t r o s c o p i c o b s e r v a t i o n s .

F u r t h e r evidence for the formation of the t r i n i t r a t o - u r a n y l complex


i s adduced by Kaplan et a l . f r o m solubility and solvent distribution m e a s u r e -
m e n t s , and ionic t r a n s f e r e n c e o b s e r v a t i o n s .
52

The s a m e i n v e s t i g a t o r s (Kaplan, Hildebrandt and Ader, 1950b) a l s o


m e a s u r e d the s p e c t r a of uranyl n i t r a t e in dioxane, pyridine, propanol, c h l o r o -
f o r m and other solvents, with and without addition of t e t r a b u t y l ammonium
n i t r a t e , or of t e r t i a r y a m m o n i u m n i t r a t e s .

In s o m e of the solutions studied, a darkening of color and turbidity


a p p e a r e d after s e v e r a l h o u r s standing, indicating slow reaction of uranyl
n i t r a t e with the solvent. In cellosolve and dibutyl carbitol, the reaction
o c c u r r e d within a few m i n u t e s , making a c c u r a t e spectroscopic m e a s u r e -
ments impossible.

All s p e c t r a had in common a broad band extending (in 0.02 M solution)


fronn about 380 to 500 mpt, with a peak around 425 m/i. The most important
difference between the v a r i o u s s p e c t r a i s in the four m a x i m a between 420
and 480 mjU, whose enhancement by organic n i t r a t e s was first noted in k e -
t o n e s ( F i g u r e 2.11). The s a m e strong effect of organic n i t r a t e s - attributed
above to the formation of a t r i n i t r o complex - was noted in some other s o l -
vents, while in o t h e r s only a m i n o r effect was o b s e r v e d .

F i g u r e 2.13 shows the s p e c t r a of uranyl n i t r a t e in water, in dilute


(0.5M) and strong (l6M) n i t r i c acid. The somewhat s t r o n g e r absorption in
water c o m p a r e d to dilute nitric acid m u s t be due to p a r t i a l hydrolysis
(cf. Section l ) . The effect of c o n c e n t r a t e d nitric acid in enhancing the long-
wave p e a k s , p r e s u m a b l y by t r i n i t r a t e complex formation, was mentioned
above.

The s i m i l a r effect of acetone, ? l s o mentioned above (see F i g u r e 2.11)


i s r e p r e s e n t e d in F i g u r e 2,14 in r e l a t i o n to the water content of the acetone,
and the addition of t e t r a b u t y l a m m o n i u m n i t r a t e .

The absorption s p e c t r u m of U02(N03)2 in dioxane (Figure 2.15) i s


r a t h e r s i m i l a r to that in w a t e r , but the m a x i m a in the 400-430 rjqj. region
a r e somewhat flattened, while the s t r u c t u r e at longer waves is somewhat
b e t t e r r e s o l v e d . It i s , however, much l e s s pronounced than in acetone, even
in the p r e s e n c e of NBU4NO3, P r e s e n c e of up to 20% w^ater c a u s e s a g e n e r a l
enhancement of the a b s o r p t i o n c u r v e , without significant change in shape,
but at 40% water the s p e c t r u m a c q u i r e s the shape typical of aqueous solu-
t i o n s . NBU4NO3 cannot be added to p u r e dioxane solution without causing
p r e c i p i t a t i o n ; addition of 2-hexylpyridinium n i t r a t e c a u s e s a m a r k e d e n -
h a n c e m e n t of the long-wave b a n d s , but the effect is much weaker than in
ketonic s o l v e n t s .

The absorption c u r v e s in ethanol and propanol (Figure 2.16) a r e


s i m i l a r to those in dioxane above 430 m^, but the absorption is s t r o n g e r .
Addition of 0.04 M NBU4NO3 to propanol solution, or of 0,04 M HNEtsNOs to
ethanol solution, r a i s e s the a b s o r p t i o n somewhat, but c a u s e s no selective
enhancement of the long-wave b a n d s .
53

S3
15 1 1 1—I [—I—I 1—I 1—I—r

2,0
o
z
UJ

on
<
-J
o

i_L J L J L J L 1 i_:i±•"•»
350 400 450 500
WAVE LENGTH, m/i

FIG.2.I3-ABS0RPTI0N SPECTRA OF URANYL NITRATE IN


SOME AQUEOUS SOLUTIONS.
0.02 M U02(N03)2 IN H2O
0.00974 M U02(N03)2 IN 0.514 M HNO3
0.02M U02(N03)2 IN I6M HNO3
54

' I I I I I I l__l I I I I \ ll Cll:


350 400 450 500
WAVE LENGTH, m/x

FIG. 2.14 ABSORPTION SPECTRA OF URANYL NITRATE IN


SOME ACETONE SOLUTIONS.
U02(N03)2 • 6 H 2 0 = 0.02M
DRY ACETONE
1 0 % WATER, 9 0 % ACETONE
20%WATER, 8 0 % A C E T 0 N E
4 0 % WATER, 6 0 % ACETONE
DRY ACETONE, 0 . 0 2 M IN NBU4NO3
IT)
IT)

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57

67
In c h l o r o f o r m (containing about 0.7% alcohol), U02(N03)2 • 2H2O is
a p p r e c i a b l y soluble, so that solutions 0.015 M in u r a n y l nitrate could be
p r e p a r e d . Its s p e c t r u m (Figure 2.17) is s i m i l a r to the solution of uranyl
n i t r a t e hexahydrate in dioxane. NBU4NO3 i n c r e a s e s the solubility m a r k e d l y ,
and the r e s u l t i n g solution has the same type of s p e c t r u m as is found in strongly
complexed ketonic solutions.

In pyridine, the a b s o r p t i o n s p e c t r u m of u r a n y l nitrate is quite differ-


ent f r o m that in other solvents (Figure 2.18). Addition of NBU4NO3 c a u s e s a
g e n e r a l i n c r e a s e in absorption above 380 mjJL, and a shift of the peak to longer
w a v e s , but produces no s e l e c t i v e enhancement of the bands above 410 mjU.

F i g u r e 2.19 shows the s p e c t r a of U02(N03)2 • 6H2O dissolved in n i t r o -


e t h a n e , ethyl a c e t a t e , g l a c i a l acetic acid, and tetraethylene glycol dibutyl e t h e r .
They a r e r a t h e r s i m i l a r to that in acetone, and in all of them, with the e x c e p -
tion of that in acetic acid, addition of an organic n i t r a t e produces the sanne
selective enhancement, although not always in equally e x t r e m e f o r m . In
a c e t i c acid, the changes a r e m o r e complex, probably indicating complexing
with acetate ions.

F o r c o m p a r i s o n , the s p e c t r u m of u r a n y l p e r c h l o r a t e solutions in
m e t h y l isobutyl ketone (with and without NBU4NO3) was also m e a s u r e d (Fig-
u r e 2.20). The changes a r e s i m i l a r to those d e s c r i b e d above for n i t r a t e
solutions.

T a b l e s 2.12A and 2.12B sunnmarize the a b o v e - d e s c r i b e d r e s u l t s . In


d i s c u s s i n g the a b s o r p t i o n c u r v e s in F i g u r e s 2.13 - 2.19, Kaplan et al. note
that the spacing of the bands is approximately the s a m e (710-746 cm~^ ;
a v e r a g e 727 cm~^) in all six solvents where it could be naeasured (the bands
in pyridine a r e too diffuse).

The m o s t r e m a r k a b l e r e s u l t is the s h a r p n e s s of the bands a s c r i b e d


to the t r i n i t r o u r a n y l complex. The a u t h o r s c o m p a r e this s p e c t r u m (above
380 m/i) with that of solid u r a n y l c e s i u m n i t r a t e . (For the sake of this c o m -
p a r i s o n , the s h a r p lines of the c r y s t a l , a s m e a s u r e d by Dieke et al. (of Chap-
t e r 1) at 20°K, a r e " s m e a r e d out" over a 2 mjU range to simulate the effect
of t e m p e r a t u r e . The lines of the " m a g n e t i c " s e r i e s a r e omitted b e c a u s e they
a r e known to disappear with r i s i n g t e m p e r a t u r e . ) Kaplan et al. find a r e -
m a r k a b l e s i m i l a r i t y between the two s p e c t r a (Figure 2.21), and conclude
that the position of the t h r e e NOJ ions in r e s p e c t to the 1102"*" ion m u s t be
s i m i l a r in both c a s e s , [in U02Rb(N03)3 , where this position is known from
X - r a y a n a l y s i s , the t h r e e n i t r a t e groups a r e a r r a n g e d s y m m e t r i c a l l y around
the O-U-O a x i s . ]
58

Table2.12A

THE EFFECT OF ADDED NITRATES, RNQg, ON THE ABSORPTION OF


URANYL NITRATE IN ORGANIC SOLVENTS

HgO (RNOg) e 455-6448(3) ^441"^434(a)


Solvent R ^470"^464(^)
M

Acetone 0 0 1.6 2.1 0.5


0 NBu4^<i) 0. 02(g) 15.8 24.9 16.6
10 NBU4('^) 0.02 2.9 4.3
20 NBu^Cd) 0.02 0.7 1.0

Nitroethane 0 0 2.4 3.3 1.9


0 HNEtg(e) 0. 02(g) 13.8 22.2 14.9

Chloroform^'^) NBU4<«^) 0.02(g) 12.3 18.7 12.9

Ethyl acetate 0 0 0.7 1.3 0.4


0 HNEtg(^) 0.02 10.3 15.9 11.4

Ci6H3405('=) ' 0 0 0.7 0.8 0.5


0 HNEtg(e) 0.02 9.2 13.5 9.5
0 HNEtg^^) 0.04 10.6 17.3 13.0

Dioxane 0 HNCiiHi?^^) 0.02 3.2 5.1 2.7


0 HNCiiHi/) 0.04 5.2 8.3 5.4
0 HNCiiHi7^'' 0.08 6.5 10.8 7.5
5 NBU4(°) 0.02 0.5 1.3 0.4
5 NBU4<<^) 0.04 0.8 1.7 1.3

(^)e-\ = Molar extinction coefficient at X mji. Wave lengths of the maxima vary by + 1 mjli among
the different solvents; minima vary by + 2 m^U. Extinctions given are those at tne actual maxima
and minima in the particular solvent.

( )containing 0. T^o ethanol.

(*^)Tetraethylene glycol dibutyl ether.

(d)

Tetra-n-butylammonium.

^ 'Triethylammonium.

^ '2-n-Hexylpyridinium.
(a)
° Further increase in the nitrate concentration caused no appreciable increase in the peak heights.

I •^
^ T
Table 2.12B

SPACING OF THE ABSORPTION BANDS IN


URANYL NITRATE SOLUTIONS

No. of Bands Average Spacing Average Deviation


Solution
Measured cm~^ cm-i

Water 11 725 110


Acetone 10 735 80
U02(N03)3" in
acetone 10 722 80
Nitroethane 4 710 27
Dioxane 10 722 110
Propanol 10 746 91
Mean 727 + 9 83

In d i s c u s s i n g the m o l e c u l a r s p e c i e s which m a y be p r e s e n t in the


v a r i o u s solutions studied, Kaplan et al. noted that a p a r t from the striking
c h a r g e c a u s e d by f o r m a t i o n of the t r i n i t r o u r a n y l complex, other s p e c t r o -
scopic changes observed w e r e s m a l l , and thus difficult to analyze quantita-
tively. However, they thought to recognize six s p e c t r a l t y p e s :

Type A - Sharp peaks at 426, 4 4 1 , 456, 470 m^u (typical e x a m p l e :


uranyl solution in acetone + NBU4NO3).

Type B - Distinct, but w e a k e r peaks in s a m e positions


[e.g., U02(N03)2 in acetone without NBU4NO3J.

Type C - No m a r k e d peaks >380 m ^ , except for one broad m a x i m u m


a t ' ^ 420 mL;Lt [e.g., U02(N03)2 in dioxane].

Type D - V e r y little s t r u c t u r e >430 mfi; t h r e e peaks between 400 and


430 m/i[e.g., U 0 2 ( N 0 3 ) 2 in w a t e r ] .

Type E - S i m i l a r to type C above 440 mjU, but absorption s t r o n g e r .


T h r e e peaks in the region 410-440 mjit; s t r o n g e r absorption
<400 mjLi than in types A to D; [e.g., U 0 2 ( N 0 3 ) 2 in propanol].

Type F - Diffuse a b s o r p t i o n [U02(N03)2 in pyridine].


o
O
1—I—I—r O
•T"T in

UJ ro
1- o
<
Q: z*
1- 3
OQ
z Z
o 2
in _j CJ
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CD O CJ •
Z
UJ
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o
CJ z
^UJ o z<
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Q. 1 -
§5-
cn UJ s =
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^ s
z
o •
«s
o o
d d
1-
Q. oi j
Q:
o
in
o zQ:
cn
ro CD o
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lO o lO » .
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NI0I10NI1X3 dVlOW u. o
61

^/
c^
oO • • 1 1 1 1 1 1 1 1 i < i 1

• •

«
/
50 — « \

/
• 1

40
/ / VIli
. /
/ / \\
• 1 \ •
1;

1
o
z 30
LJ

-
<
_j
o • /
20
\
_
\\ \
\ \ '^
/ /
If
if
v\
V\
\\
1/
1/
V\»
\\ y vl
10

I 1 1 1 L_ 1 1 1 1 1 1 1 1 1 ! 1
350 400 450 500
WAVE LENGTH, m/^

FIG. 2.18 —ABSORPTION SPECTRA OF URANYL NITRATE IN


PYRIDINE. U02(N03)2 • 6 H2O = 0.02M
NO ADDED REAGENT
O.lM NBU4NO3
0.8M NBU4NO3
62

d>X.
15
I 1 1 1 1 1 1 1 1 1 1 1 1 ' 1 1 1

u -

•^./'^ ,\
u / -^ \ -

5 ,0
I-
o

Av^vW —

'\- -
I-
X ;-.
UJ f* *R
\ ). A'
h- -
/
on

< 5 - »'
iA'^V .•
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o k \

«'l. A''
• • -

M
— -
i
.. <y ^\,• .

r . 1 1 1 1 1 i 1 1 1 1 1 1 1 1 1
350 400 450 500
WAVE LENGTH, m/i

FIG. 2.19-ABSORPTION OF URANYL NITRATE IN VARIOUS


SOLVENTS. U02(N03)2 * 6 HgO = 0.02M
GLACIAL ACETIC ACID
ETHYL ACETATE
TETRAETHYLENE GLYCOL DIBUTYL ETHER
NITROETHANE
63
4vJ

30
T—I—r T—r
T7T — I — I — r - = i
II
:i

I
!i
II
i
li
25 •: ••
il I!
• •
t:
:!
I!
:i
li 1: il
•« .'I :i
II
li li !!
O
!i
I- !\ 11
II
o i!
11
UJ
• « •
ii
^/^/ i • i -I
< I
• ••• • , • •
• :i • ' i: !I
^•1 i::» ! ;
::v; \\ ; \
y - ' c l •V'l
\.'"iA\'- •••

J L 1 1 J L
350 400 450 500
WAVE LENGTH, m^

FIG. 2.20.—ABSORPTION SPECTRA OF METHYL ISOBUTYL


KETONE SOLUTIONS CONTAINING URANYL
PERCHLORATE. U02(CI04)2 = 0.02M

NO ADDED REAGENT
0 . 0 2 M NBU4NO3
0.03M NBU4NO3
0.04M NBU4NO3
0.06M NBU4NO3
UJ

O
t-
U)
o
<

z
10
o
z .-«,
^ *-
3 a>
2m
o>
4. 5CJ «
(A
E O '-'
OJ o _l
<
cJ + t-( 0
CD
z UJ CJ >
IT
UJ on l<) O
_l => o
CD z,_^ lO
U. CJ to
UJ
> o o
<t z> z
^^
5 s OJ
CJ o
3
o M
O
o•

(siiNn AMvaiiQMV) NOllddOSav


65

^5
The a u t h o r s i n t e r p r e t e d s p e c t r a of the types A, B, C, and D a s
indicative of a diminishing n u m b e r of NO3 ions in association with the
UO2 ion. Type A was a s c r i b e d above to the U 0 2 ( N 0 3 ) 3 ion [or the
H U 0 2 ( N 0 3 ) 3 m o l e c u l e ] . Type B m a y then indicate a d i n i t r a t e complex,
U 0 2 ( N 0 3 ) 2 , type C, a mononitrocomplex, U02N0'3 , and type D (exhibited,
e.g., by u r a n y l n i t r a t e in w a t e r ) the non-complexed ion UO"^"''. The e x i s -
tence of a dinitrocomplex i s made plausible by quantitative analysis of
the five c u r v e s in F i g u r e 2.20. If t r i n i t r a t e w e r e the only complex fornned,
its concentration in the five solutions would have had to be 0, 0.0067, 0.01,
0.013, and 0.02M, r e s p e c t i v e l y ; if, in addition to the t r i n i t r a t e , only a (stable)
m o n o n i t r a t e w e r e formed, the t r i n i t r a t e concentrations would have had to be
0, 0, 0.005, 0.01, and 0.02M. With a (stable) dinitrate complex, the t r i n i t r a t e
c o n c e n t r a t i o n s would be z e r o in the f i r s t four solutions and 0.02M in the l a s t
one. The actual t r i n i t r a t e c o n c e n t r a t i o n s , calculated from the c u r v e s on the
a s s u m p t i o n that the enhancement of absorption in the four peaks is caused
by t r i n i t r a t e alone, a r e a s follows: 0, 0.0016, 0.0024, 0.0052, and 0.02M. A
plausible i n t e r p r e t a t i o n of t h e s e n u m b e r s is that a d i n i t r a t e complex does
exist, and h a s absorption bands in the s a m e positions a s those of the t r i n i -
t r a t e , but considerably w e a k e r than the l a t t e r . If this hypothesis is c o r r e c t ,
then the d i n i t r a t e complex p r e d o m i n a t e s in 0.02M solutions of uranyl n i t r a t e
in the following solvents: 16M HNO3, acetone, methyl isobutyl ketone, ethyl
a c e t a t e , n i t r o e t h a n e and glacial acetic acid. Because of the low d i e l e c t r i c
constant of solvents, such a s dioxane, which show type C s p e c t r a (Figure 2.15),
the m o n o n i t r a t e complex - v^hich v^e a s s u m e d p r o d u c e s t h e s e s p e c t r a -
cannot be p r e s e n t in t h e m as a free cation. The a u t h o r s suggest that it is
solvated and then a s s o c i a t e d with a solvated n i t r a t e anion, thus:

Within a given s p e c t r a l type, minor differences occur that can be


attributed to solvation by different s o l v e n t s . In the c a s e of solvent m i x t u r e s
containing w a t e r , p a r t i a l h y d r o l y s i s a l s o nnust be taken into consideration.

The p e c u l i a r effect of pyridine (type F spectrum) can be tentatively


attributed to coordination of UO^''' with the nitrogen atoms in pyridine m o l e -
cules (in all the other c a s e s , the only coordination taken into account was
that with oxygen a t o m s ) .

The solvation of u r a n y l ions by alcohols m u s t be p a r t i c u l a r l y strong


to account for the type E s p e c t r a exhibited by solutions in t h e s e solvents.
Addition of NR4NO3 leads to the formation of the t r i n i t r a t e complex in acetone,
methyl isobutyl ketone, ethyl a c e t a t e , nitroethane and chloroform, but not in
a c e t i c acid, dioxane, pyridine, or a l c o h o l s .

Some of t h e s e i n t e r p r e t a t i o n s appear speculative, but they a r e quite


s i m i l a r to those suggested independently by other o b s e r v e r s for the e x -
planation of the s p e c t r a of other n i t r a t e s in mixed solvents.
44
4 . RAMAN SPECTRUM AND INFRARED SPECTRUM
OF URANYL SALT SOLUTIONS

P r i n g s h e i m and Yost (1929) f i r s t o b s e r v e d the Raman s p e c t r u m of a


c o n c e n t r a t e d u r a n y l sulfate solution (in sulfuric acid) and found a single
frequency of 870 cm~^i obviously c o r r e s p o n d i n g to the main vibrational f r e -
quency of the ground s t a t e of UO2 , r e v e a l e d by the f l u o r e s c e n c e s p e c t r u m .

Conn and Wu (1938) investigated the Raman s p e c t r u m of s a t u r a t e d


solutions of u r a n y l n i t r a t e , chloride and sulfate, and found two vibrational
frequencies (cf. Table 2.14), According to (Chap,. 1), these a r e the
s y m m e t r i c and the bending frequency, r e s p e c t i v e l y , of the UO2 group.
However, since the bending frequency should be " R a m a n - i n a c t i v e " in linear
m o l e c u l e s , Conn and Wu p r e f e r r e d an angular model of the uranyl ion, in

which the " s y m m e t r i c " vibration Q >•—^-^^—O b e c o m e s

and the "bending" v i b r a t i o n O ® O b e c o m e s XJ f ^ J 1 with the r e -


suit that both a r e now p e r m i t t e d in the Rannan s p e c t r u m .

S a t y a n a r a y a n a (1942) used a s a t u r a t e d solution of u r a n y l chloride in


w a t e r , adding p o t a s s i u m b r o m i d e to quench f l u o r e s c e n c e . After 24 hr expo-
s u r e , with the m e r c u r y line 546.1 mjit as exciting line, he was able to m e a s -
u r e five R a m a n frequencies (Table 2.13).

Table 2,13

RAMAN FREQUENCIES OF UOzClz IN WATER


(SATYANARAYANA, 1942)

R a m a n frequency (cm"') 197 226 853 865 909


Intensity 2 2 0 10 1
n 1 It 1
Interpr etation ^b ^b ^s Va

Table 2.13 shows, in addition to the double bending and s y m m e t r i c


vibration f r e q u e n c i e s , a single a n t i s y m m e t r i c frequency, Va,» 3-^ 909 mjU,
Similarly to Conn and Wu, Satyanarayana c o n s i d e r e d the o c c u r r e n c e of
R a m a n f r e q u e n c i e s other than Vs evidence of non-linear s t r u c t u r e ; he cal-
culated (by m e a n s of the P e n n - S u t h e r l a n d theory) a value of 140° for the
O...^ <^~\_^0 angle. As a tentative explanation of the doubling of the f r e -

quencies VXJ and Vg, he suggested p a r t i a l ionization, with some photons


s c a t t e r e d by u r a n y l ions and some by u n d i s s o c i a t e d u r a n y l chloride mol-
e c u l e s , Satyanarayana a l s o found that the 865 c m " Rannan line was strongly
polarized.
67

Ll
C r a n d a l l ( 1 9 4 7 , 1949) m e a s u r e d t h e R a m a n l i n e s of u r a n y l c h l o r i d e
s o l u t i o n s of d i f f e r e n t c o n c e n t r a t i o n s , a n d c o m p i l e d T a b l e 2 . 1 4 , w h i c h i n c l u d e s
t h e e a r l i e r r e s u l t s of Conn a n d Wu, a n d of S a t y a n a r a y a n a .

Table 2 . 1 4

RAMAN FREQUENCIES IN URANYL SALT SOLUTION (AFTER CRANDALL)

Chloride

Saturated 1. 2M UO2CI2
Perchlorate (sat.) Nitrate Sulfate
Frequency
(Crandall) l.OM'I'HCl (sat.) (sat.)
(Conn, (Conn,
(Conn, Wu) (Satyanarayana) 1. 2M"^ NH4CI Wu) Wu)
(Crandall)

Vg (symmetric) 880 860 865. 8 5 3 * 864 863 860

V a (asymmetric) - - 909* - - -

Vj, (bending) 199'^ 210 226, 197 204 210 210

*Weak lines

C r a n d a l l c o n s i d e r e d t h e d i f f e r e n c e b e t w e e n t h e f r e q u e n c i e s in u r a n y l
p e r c h l o r a t e s o l u t i o n and in t h e s o l u t i o n s c o n t a i n i n g o t h e r a n i o n s a s an i n -
d i c a t i o n of c o m p l e x i n g (of w h i c h i n c o m p l e t e d i s s o c i a t i o n , s u g g e s t e d b y S a t -
y a n a r a y a n a , i s a s p e c i a l c a s e ) . T h e d o u b l e t s t r u c t u r e found in S a t y a n a r a y -
a n a ' s e x p e r i m e n t s c a n t h e n b e i n t e r p r e t e d a s i n d i c a t i n g t h e p r e s e n c e of two
t y p e s of c o m p l e x e s , C r a n d a l l s u g g e s t e d t h a t c o m p l e x i n g m a y b e r e s p o n s i b l e
for a n a n g u l a r s t r u c t u r e (if t h e o c c u r r e n c e of p r o h i b i t e d R a m a n l i n e s i s to
b e c o n s i d e r e d a s p r o o f t h a t t h e UO2 i o n , w h i c h is l i n e a r in c r y s t a l s , b e -
c o m e s a n g u l a r in s o l u t i o n ) o r , a l t e r n a t i v e l y , for the v i o l a t i o n of e x c l u s i o n
r u l e s t h e o r e t i c a l l y v a l i d for l i n e a r s t r u c t u r e s (if t h e UO2 ion i s a s s u m e d
t o r e m a i n l i n e a r in s o l u t i o n ) ,

C r a n d a l l ' s e x p e r i m e n t s w e r e n n a d e in c o n n e c t i o n w i t h O^® e x c h a n g e
studies between u r a n y l ions and w a t e r . These studies indicated that the non-
complexed ion has s i m p l e s t r u c t u r e
•VZ
[O - +U+ = O]

with four covalent bonds, and m a d e unlikely the s t r u c t u r e

HO OH"
(U+^)
'HO OH"

T+6 •
w i t h f o u r i o n i c b o n d s b e t w e e n a c e n t r a l U^" ion and four O H " a n i o n s , (If t h e
s e c o n d m o d e l w e r e c o r r e c t , a f a s t i s o t o p i c e x c h a n g e of u r a n y l o x y g e n w i t h
w a t e r could be expected.)
63
Lt
The question of the shape of the UO2 ion in solution was again taken
up by Sutton (1952), He c o m p a r e d the Raman s p e c t r a of the following s o l u -
t i o n s : (a) UO2CI2, s a t u r a t e d , in w a t e r , (b) s a m e , s a t u r a t e d with hydrochloric
acid, (c) s a m e , s a t u r a t e d with c a l c i u m chloride, (d) s a m e , s a t u r a t e d with
UO3; and (e) U02(N03)2. s a t u r a t e d . F i g u r e s 2 , 2 2 A - E w e r e obtained with the
m e r c u r y line 546,1 mjU in 2-8 hr e x p o s u r e .

The " p r o h i b i t e d " Vg, frequency (about 980 c m ' ) is not recognizable
in (A), but a p p e a r s c l e a r l y in (B) and (C), w h e r e Cl~ ions w e r e p r e s e n t in
l a r g e e x c e s s , Sutton c o n s i d e r s this evidence of formation of complexes of
UO2 with C r , in which the e n t r a n c e of CI" ions into the hydration s p h e r e s
of the cations: UO2 •6H2O + CI"—^U02 C r ' 5 H 2 0 , c r e a t e s an a s y m m e t r i c
e l e c t r i c field that m a k e s the prohibited t r a n s i t i o n p o s s i b l e , (Using the
UO2F2 c r y s t a l s t r u c t u r e as a model, Sutton postulated that water nnolecules
^OH2
f o r m a p u c k e r e d ring around the O-U-O a x i s , with an 0-U*=—-^—O angle of
about 73°,)

The even m o r e pronounced a p p e a r a n c e of the Va frequency in u r a n y l


c h l o r i d e solution s a t u r a t e d with UO3 (Figure 2,22 D) can be attributed to the
f o r m a t i o n of complex polyuranyl ions

uo^"*" -h UO3 —^juo^+ - 0 - - - UO^+J ~ (=U20^+)


(cf. Section 3), in which the 0"~ ion in the " b r i d g e " e x e r c i s e s a s i m i l a r (but
s t r o n g e r ) a s y m m e t r i c e l e c t r i c influence on the linear UO^"*" ions as does the
CI ion in the c h l o r i d e c o m p l e x e s .

The o c c u r r e n c e in n i t r a t e solution (Figure 2.22 E) of the v^ frequency,


with an intensity i n t e r m e d i a t e between those in F i g u r e s 2,22 B,C on the one
hand, and F i g u r e 2.22 D on the o t h e r , is taken by Sutton as confirmation of
the conclusion of Betts and Michels (1949) that the u r a n y l ion has a s t r o n g e r
tendency to c o m p l e x with NOf ions than with CI" ion (for contradictory evi-
d e n c e , see Section 2,1). In this c a s e (Sutton suggests) two adjacent water
m o l e c u l e s in the hydration s p h e r e can b e r e p l a c e d by two n i t r a t e oxygens
(UOj'''-6H20 + NO3-—«-UOt+ N03--4H20).

The Vb frequency is not s e p a r a t e d f r o m the m e r c u r y line in F i g -


u r e s 2,22 A - E b e c a u s e of insufficient d i s p e r s i o n ; however, its p r e s e n c e is
r e v e a l e d by the d i s t o r t i o n of the shape of this line, which is least pronounced
in c u r v e (A) and s t r o n g e r in c u r v e s ( B - E ) .

Sutton suggested that if the above a r g u m e n t is c o r r e c t , the prohibited


lines can b e expected to be w e a k e r in complex ions of higher s y m m e t r y , such
as the t r i n i t r a t o u r a n y l ion, which is formed, according to Kaplan et a l .
(1950 a,b), in u r a n y l n i t r a t e solutions in organic solvents in the p r e s e n c e of
quaternary ammonium nitrates,.
69

4?

Incident
Light

6 6 5 cm"'

FIG. 2 . 2 2 A - R A M A N SPECTRUM OF UO«CI


2^'2
70

7o

HCI sat'd.
UO2CI2 + HCI

FIG.2.22B-RAMAN SPECTRUM OF UOgClg SATURATED WITH HCI.


71

FIG.2.22C-RAMAIM SPECTRUM OF UOgClg SATURATEP WITH CaClg.


72

IX

FIG 2 . 2 2 D - R A M A N SPECTRUM OF UO2CI2 SATURATED WITH UO3


73

7J

FIG. 2.22E —RAMAN SPECTRUM OF URANYL NITRATE.


74

7/
Infrared Absorption S p e c t r u m - Data on the infrared absorption
s p e c t r u m of u r a n y l intake solutions a r e included in Table 1,4 (ANL-5122) by
Sevchenko and Stepanov (1949).
75

Is
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