I

UNITED S T A T E S ATOMIC ENERGY COMMISSION

KAPL - 1041

INFRARED SPECTRUM OF UFa AT ELEVATED

TEMPERATURES

BY
N. J. Hawkins
H. C. Mattraw
D. R. Carpenter

February 1, 1954

Knolls Atomic Power Laboratory

Schenectady, New York

L
- Technical I n f o r m a t i o n Service, O a k Ridgo, T o n n o r r o e

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ABSTRACT

The infrared spectrum of UF6 was studied from 2-23 microns with a
double beam spectrometer a t temperatures up t o 100°C. Six new- bands were
obtained. All of the available UF6 bands were assigned and discussed. 1

Values for the fundamental frequencies agreed very well w i t h a recent

study by Gaunt. 3 ..-
.'

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INFRARFD SPECTRUM OF UF6 AT ELEVATED TEMPERATURES
' .
N. J. Hawkins, H. C. Mattraw, and D. R . Carpenter

ImTRODUCTION

The.infrared spectrum of UF6 has been studied by several investigators.

Bigeleisonl studied the' infrared' spectrum from 2-17 with a single beam
spectrometer. Later Burke, Smith, and Nielson,2 extending the range from
2-40 p with a double-beam spectrometer, studied the gas a t room temperature
(- 125 mm vapor p r e s s e e ) i n c e l l s of 10 cm and 1 meter length. Recently
Gaunt3 studied UF6 a t room temperature from 2-25 p i n c e l l s up t o 180 cm path
length with single -beam optics .
Since UF6 sublimes t o one atmosphere of pressure a t 57",4 it seemed 0;
i n t e r e s t t o heat a pressurized c e l l containing UF6 t o f i n d what new bands
m i g h t be obtained and t o increase the i n t e n s i t y of the "weak" bands.

EXPERIMENTAL
"he infrared spectrograph employed was the Baird double-beam model AB2-195.
N a C l and KBr optics were used t o study the region from 2-23 p . The c e l l w a s
10 cm i n length and constructed of copper. The body of the c e l l was i n t h e
form of a 5-cm-OD screw. AgCl windows were s e t i n t o the end caps and screwed
t o vacuum tightness against t e f l o n gaskets. The uF6 was condensed from an a l l -
metal vacuum system i n t o a side-arm t r a p attached d i r e c t l y t o t h e infrared c e l l .
Ribbon-type heaters were wrapped around the c e l l as well a s around the attached
gas-condensing assembly. To operate, the gas-condensing assembly w a s heated t o
drive the gas i n t o t h e c e l l body a t room temperature. The c e l l w a s then preheated
t o t h e temperature t o be studied while t h e side arm was heated t o a higher temper-
ature. Immediately before t h e run the l a s t remnants of s o l i d o r l i q u i d UF6 were
removed from t h e windows by heating them f o r several minutes with an infrared
lamp. It was noted i n f i n a l blank background studies t h a t there was no noticeable
, e f f e c t i n the transmissive properties of the A g C l windows even a f t e r several UF6
runs i n which the inside c e l l temperature was close t o 1 0 0 ° C where the vapor
pressure of UFO was approximately 3000 mm. 4
c. 3
The W6 was obtained froln two sources. Some was prepared a t KAPL by the
reactions between (1)U308 and CoF3 and (2) UF4 and &F2. I n these preparations
SiF4 was En impurity which was d i f f i c u l t t o remove completely. L2ter, u"6 w a s
obtained from the K-25 Iaboratories a t Oak Ridge. This material was found do
contain HF, which was removed by a KF bed, and C02, which w a s removed by d i s t i l -
l a t i o q a t dry ice temperatures. All preparations, p u r i f i c a t i o n s , and material
t r a n s f e r s were carried out urC.er high vacuum conditions. None of the above
impurities, i n s m l l amounts, i n t e r f e r e with the r e s u l t s reported. I n f a c t , t h e
S I F 4 band a t 1032 cm-l was an excellent guide f o r determining which bands
increased i n i n t e n s i t y only as a r e s u l t of pressure broadening.

The recorded spectra were c a l i b r a t e d w i t h polystyrene i n the N a C l region

and 1, 2, 4 -
trichlorobenzene i n the KBr region.

1
 .. ..~ --
1

2 3

The i n t e n s i t i e s observed on the Baird charts f o r a t y p i c a l run i n which

the c e l l w a s heated beyond t h e point where there was d e f i n i t e l y l i q u i d uF6 ,
present are presented i n !Bible I along w i t h comparable i n t e n s i t i e s obtained
a t room temperature. Charts made f r o m t h e recorded spectra are a l s o included
i n t h i s report. It is t o be noted that bands considered %eak" a t room temper-
a t u r e are "strong" a t the higher temperature. A l l of the bands reported by
. P

Smith e t a12 i n t h e 2-23 p region are present. Gaunt3 found the bands a t .
755 cm-1 and 571 cm-1 which were not observed by Smith. However, we do not i

find Gaunt's band a t 547 cm-1, and while we suspect there i s a band a t 587 cm-1 '

we were not able t o "develop" it suf'ficiently t o be sure it was present because

of the broadness of the v 3 . I n view of Gaunt's long path technique, t h e
587 cm-1 band i s probably real. Completely new bands were observed a t 1869,
1808, 1684, 1337, 533, and 479 cm-1. The 53 cm-l represents the peak of a
4
r a t h e r broad band extending from 530-545 cm' , and may be due t o more than
one uF6 ternarx. I n addition, there are indications of w e a k bands between
1400 and 1500 cm-l which are e a s i l y explainable but dc not warrant further
cons iderat ion.
 Observe+

3 1

1684
1337

1288
u59
8%
825
755
n5
672
Q3
571
533 1

1
479

2
350
I
2
279
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I

Wbeervcr
-
1gAPL this et*
2 Burke e t al
3 t3mn.t
a beferred d u e
 4
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 DETERMINATION OF 'lTHE FUNDAMENTAL FREQ.?JENCIES
. .
Molecules of type YX6 which belong t o t h e 0, point group possess six funda-
mental vibration frequencies;. d e l y , , one- nondegenerate Ag, one doubly degener-
a t e Eg, and four frequencies which axe t r i p l y degenerate of species Flu, FgU,
.r. F (Table 11) The symmetry of the dipole moment can only be Flu.5 Thus o n l y
f
t& bands containing the Flu component, that i s , only t h e v 3 and v 4 fundamentals,
a r e active i n t h e infrared. The "4, while infrared active, i s beyond t h e l i m i t
of observation of most o p t i c a l systems. However, there a r e several observable
binary and ternary conibination bands from which values of t h e other fundamentals
can be obtained.

Vibrations of type Aig, Eg, and F2 5 a r e active i n the Raman spectrum

which has been observed by Bigeleisen ef a l e 1 The Raman data, t h a t i s , +he
V1, V2, and v , were obtained f r o m l i q u i d UF6 and a solution of UF6 i n
To account* fo? t h e combination bands i n t h e infrared spectrum of the molecu!?;
i n t h e gaseous s t a t e , it i s necessary t o assume t h a t t h e r e a r e no perturbing
e f f e c t s caused by intermolecular interactions on t h e normal vibrations. Thus,
we consider the Raman frequencies as an a i d i n assigning the binary combination
bands, b u t take our "adjusted" fundamentals as those obtained from t h e binary
combination bands e

TABLE I1
FUNDAMEWTAL VIBRATION FREQUENCIES OF m6&
Fundamental Smith e t a1 Gaunt -
KAPL Symlnetxy

'1 656 cm-1 668 c m - l 665 c m - l *1g

"2
532 536 E€3
V
3 640 626 623 Flu .
200 186
. . . .:.v,- . .... . .... . . . . . .
, ,
.I
,
1 . .: '.' ..' : 200" . . '
r
' .2'02::, .. ....... ,202,' . . . .
. . . . .
Il
-
: :. ' ,. . .".
. . . . . . . .- .. ..
F2g
. ~ # .( ,.%.)
, ..,. , '

The fundamental v 3 was taken t o be t h e observed value of 623 cm-1. W e

ha.ve additional. confidence ir, the value of "3 because of the band foimd-at
1869 c m - l which we assign as 3v3. 'Ithe v a l u e s , f o r vl, V2, and v5 a r e obtained
im%diatel.y from.,&heirbibry'band,i' id'combination
._. with v3.- !Be ~6 w a s ' calcu- .,'

lated fk&':the $om%ination band. v:i' +''y,6:. The value of: 'v4 was taken t o be
186 cm--l, t h e . averdge if' 'SLX bands which were. th,oGht t o be' conibikations i n -
'

volving v 4 . These data a r e summarized i n Bbl ' It.is. t o ' b e noted 'that the
peak of the band observed a t 571 cm-1 i s probably d i s t o r t e d by v 3 . The t r u e
value i s probably somewhat lower than the value observed.
1

6 7
TABU I11

COMBINATIONS INVOLVING V4

Wobs Assignment / V 4 calc

852 cm'l + v4 187 cm-1

715 2
' + v4 179
479 - v4 186

392 v4 + v5 190

350 v2 - '4 186

571 3v4 190

It i s t o be noted i n Table I1 t h a t the RAPL values f o r the fundamentals

are i n good agreement with those obtained by Gaunt.3

THERMODYCMMIC PROPERTIFS

Gaunt has calculated the thermodynamic properties of uE6 from h i s s p e c t r a l

data. The value of the U-F distance w a s taken t o be 2.00 8 . There would be
only minor charges i n the vibrational p a r t i t i o n function which would be obtained
from our values of t h e fundamentals. It is t o be hoped t h a t solneday b e t t e r data
f o r the internuclear distances i n spherical tops can be obtained because even
small changes i n t h i s value would introduce large e r r o r s i n the r o t a t i o n a l par-
t i t i o n function.

ASSIGNMENT OF NEW BANDS

In Table I the a s s i nment of all t h e observed bands of UF6 a r e summarized.

For the band a t 1808 cm-f, v1 + v 2 + v referred because v 1 -
v2 + v3 i s
the only possible assignment of the 75 band consistent with OUT fundamentals.
For the 350 c m - 1 band observed by Smith and coworkers2 we prefer v2 - v 4 because
v 5 + v 6 i s not observed in MoF6 and WF6. It might be possible, however, that I

v2 - v 4 i s present i n t h e shoulders of stronger l i n e s i n Smith's t r a c e s of the

MoF6 and WF6 spectra.

FURTHER STUDY

When CaF2 windows become available, an attempt w i l l be made t o study f u r t h e r

t h e important band a t 1869 cm-1, assigned as 3 ~ 3 . It seems probable that t h e
presence of t h i s band leads t o the preference f o r a set of fundamentals more i n
agreement w i t h Gaunt than with Smith.

I
 7.
/

REFERENCES

1. Bigeleisen, J., Mayer, M. G., Stevenson, P. C., and Turkevich, J.,

"Vibrational Spectrum and Thermodynamic Properties of Uranium
Tj - 442-445 (1948).
Hexafluoride Gas," J. Chem. Phys. 16,

2. .Burke, T. G., Smith, D. F., and Nielsen, A. H., "The Molecular Structure
-,
of MOFG, WF6, and UF6 from Infrared and Raman Spectra," J. Chem. Phys. 20
447-454 (19521
3. Gaunt, J., "Infrared Spectra and Molecular Structure of Some Group 6
- 1122-1131 (1953).
Hexafluorides , P a n s . Far. SOC. 49,

4. MDDC-1295, "The Vapor Pressure of Uranium Hexafluoride," by R. H. CVist

and B e Weinstock, Columbia University, September 25, 1947.

5 e Herzberg, G., Infrared and Raman Spectra. New York: D. Van Nostrand Co. Inc .,
1945, P - 253-

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