Journal of

~Y5
AND C O M ~ O ~ D 5

ELSEVIER J o u r n a l of Alloys a n d C o m p o u n d s 225 (1995) 271-273

Mean molal activity coefficients of rare earth halides in aqueous

solutions at 25.0 °C
Koichi Iwamoto, Takayuki Takamatu, Yukiko Nishimura, Yasuo Suzuki *
Department of Industrial Chemistry, Meiji University, Higashi-mita, Tama-ku, Kawasaki 214, Japan

Abstract

Mean molal activity coefficients and water activities of rare earth chlorides and bromides at 25 °C were determined in
aqueous solutions from dilute to concentrated. The mean molal activity coefficients of the rare earth bromides are larger than
those of the chlorides, whereas the water activities of the bromides are smaller than those of the chlorides. These trends are
discussed in terms of the ionic radii of the catonic and anionic species, ionic interactions and hydration. The osmotic coefficients
of the rare earth bromides are fitted to the Pitzer equation. The Pitzer parameters for the rare earth bromides were evaluated
by comparison with those for the chlorides.

Keywords: Rare earth halides; Aqueous solutions; Mean molal activity coefficients

1. Introduction 2. Experimental and calculation

The experimental details of the measurements on

The m e a n molal activity coefficients for the rare earth the rare earth bromides were described in previous
chlorides have been published, except for scandium [1] papers [3-5]. Values of the mean molal activity coef-
and some rare earth bromides in dilute solutions [2],
ficients and water activities of the rare earth chlorides,
by Spedding and co-workers. We reported previously except for scandium, were taken from the p a p e r by
the coefficients for the rare earth bromides [3,4] and
Spedding et al. [1].
some scandium compounds [5]. We concluded that the
The osmotic coefficients of the rare earth bromides
rare earth bromides in aqueous solutions and also the were fitted to the following equations [6]:
rare earth chlorides and perchlorates would be outer-
sphere complexes. Both chlorine and bromine have - 1 = ~ZMZxIf*+ m(2VM VX/V)B~Mx
similar chemical properties, and the ionic radius of
+ m2[(2VM Vx)3/Zlv]CO~x (1)
bromide (195 pm) is larger than that of chloride (181
pm). In this paper, the m e a n molal activity coefficients In Y+ = ~ZMZxLfV+m(ZVM Vx/v)B~x
and water activities of the rare earth bromides are + rn2[(2vMvx)3/z/v]C~x (2)
compared with those of the rare earth chlorides. The
osmotic coefficients of the rare earth chlorides, per- where vM and Vx are the numbers of M and X ions
chlorates and nitrates have been fitted to the Pitzer in the formula, ZM and Zx are the respective charges
equation by Pitzer et al. [6]. A comparison of the Pitzer in electric units, v = UM+ VX and m is the molality of
p a r a m e t e r between the rare earth bromides and chlo- the solute. The other quantities are defined by the
rides was made in order to obtain a theoretical ex- following equations:
planation. This comparison will provide further infor- (3)
f* = - A , I m / ( 1 + bI~a)I ~a
mation on the interionic interactions.
i f = -A,[P/2/(1 + bP/2) + (2/b) In(1 + 1)11/2) (4)
* Corresponding author.
B ~x -- ~r~xa(°)-a-~xa°) exp( - a1112) (5)

0925-8388/95/$09.50 © 1995 Elsevier Science S.A. All rights reserved

SSDI 0 9 2 5 - 8 3 8 8 ( 9 4 ) 0 7 1 2 9 - 2
272 K. lwamoto et al. / Journal o f Alloys and Compounds 225 (1995) 271-273

"r -- (o) (i) 2 Nd Gd Dy Er Yb

BMx- La Pr Sm Eu Tb H o T m L u Sc

I I I I IIllll(ll
× [1 - (1 + oar'a - 1/2.2/) exp( - aP/2) (6) 2.4- []

3' -- 4'
C MX - 3/2C Mx (7)
2.3- []
[]
where I is the ionic strength andA4" is the Debye-H~ickel [] ~ 0 0 D
coefficient for the osmotic function, which has a value -~ 2.2
of 0.391 for water at 25 °C. The general parameters c-
o
are given the values b = 1.2 and a = 2.0. The values of ._¢
o
,m 2.1 0
the specific parameters, 3/2/3(°), 3/2/3°) and (33/2/2)C4", Q) 0 o
[]

are given in Table 1. o

o 2.0
0

o
E 1.9 oO0 ~°
U~ o
3. R e s u l t s and discussion o 0 L] :Br

o 0 :Cl
0
1.8- ©
In a previous paper [5], we compared the mean molal []
(3
activity coefficients of the rare earth chlorides and
bromides and used the ionic radii of six coordination 1.7
I I I I I
for the lanthanide ions. It is well known that the 110 100 90 80
120
hydration numbers of the lanthanide ions vary from 9
to 8 between neodymium and terbium. Therefore, ionic Ionic radius / pm
radii of nine coordination from lanthanum to samarium Fig. 1. Osmotic coefficientsof the rare earth chloride and bromide
and eight coordination from europium to lutetium were solutions at 2.0 mol kg-1 and 25.0 °C.
employed throughout. The values for scandium chloride
and bromide were included. The ionic radius of six Nd Gd Dy E r Y b
coordination was used for scandium. La Pr Sm Eu Tb H o T m L u Sc
I I I r Illlll]l]
The osmotic coefficients, mean molal activity coef- 1.1
ficients and water activities of the rare earth chlorides
1.0
and bromides at 2.0 mol kg-1 are plotted versus ionic
radii of the rare earth ions in Figs. 1-3. The osmotic L 0.9 q~
p,.
coefficients and mean molal activity coefficients of the - 0.8 ~0 0

rare earth bromides are higher than those of the e.

® 0.7
chlorides, whereas the water activities of the bromides
[] 13
are lower than those of the chlorides. Both the trends E-
o
0.6 El

of an increase and decrease with decreasing ionic radius, o

o 0.5 _ O
G
O
similar to those for the chlorides, also appeared with []
> 0.4
the bromides. The values for the bromides show greater °~
o
scatter than those for the chlorides. Slight temperature ~ 0.3
~ 0.2 oc~:P
0
Table 1 E o
Pitzer p a r a m e t e r s of lanthanide bromides = 0.1 []:Br
r0 ©

0.0 0 0 :CI
Ln 3/2/3 (0) 3 / 2 / 3 (1) (33/2/2)C ~ S.D. a o
-0.1 -- OO
0
La 0.971 8.71 -0.028 1.165 X 10-
-0.2
Pr 0.942 9.50 - 0.015 1.843 x 10- z I 1 I I I
Nd 0.951 9.39 - 0.013 1.383 × 10-1
120 110 100 90 80
Sm 1.026 9.48 - 0.036 2.087 × 10-1
Eu 0.972 9.63 - 0.017 2.286 × 10-1 Ionic r a d i u s / pm
Gd 0.992 9.31 - 0.021 1.893 × 10-1
Fig. 2. M e a n m o l a l activity coefficients o f the r a r e e a r t h c h l o r i d e
Tb 1.083 8.17 - 0.037 2.658 × 10- t
a n d b r o m i d e solutions a t 2.0 m o l k g - 1 a n d at 25.0 °C.
Dy 1.071 8.52 - 0.028 1.440 × 10- i
Ho 1.046 9.00 - 0.020 1.598 × 10-
Er 1.053 8.68 - 0.018 1.767 X 10-1 fluctuations might result in erratic equilibrium con-
Tm 1.072 8.25 - 0.022 1.354 × 10- centrations. The fact that the coefficients for the bro-
Yb 1.062 8.22 - 0.025 1.671 X 10- t mides were higher than those for the chlorides may
Lu 1.007 8.61 - 0.011 1.924 X 10-
be interpreted by the difference in the interionic in-
S.D. = s t a n d a r d d e v i a t i o n . teractions. Since the surface charge density of a bromide
 K. lwamoto et al. /Journal of Alloys and Compounds 225 (1995) 271-273 273

Nd
La Pr Sm
Gd Dy Er Yb
Eu Tb HoTraLu Sc
ion is apparently smaller than that of a chloride ion,
f1[11[111 the ionic interactions in the rare earth bromides would
0.78J- ~ i r r
be weaker than those in the chlorides. Although the
/
0.77 [
o
° o
o
LJ : Br interactions are weaker in the bromides, the hydration
© O:CI of the rare earth ions could be stronger, and conse-
© quently the water activities would decrease.
©
0.76[ © The osmotic coefficients and water activities of scan-
dium chloride and bromide are close to the extrapo-
,~>' 0.75[ lations from the lighter rare earths. However, the
hydration number of scandium ion has not been exactly
©
determined and might be seven [7]. If the ionic radius
0.74 ~- uI
of seven-coordinate scandium ion were evaluated, fur-
! []
ther discussions with regard to the trends with the
0.73 [ scandium ion could possibly be made.
[] 1~c3[]
M
The Pitzer parameters, 3/2fl(°), 3/2fl(1) and (33/2/2)C•,
0.72 [ []
of the rare earth bromides are listed with standard
deviations in Table 1. The pairwise short-range inter-
0.71 I- I
action parameters 3/2# (o) of the rare earth chlorides
[ I 1 I [6] and bromides versus ionic radius are shown in Fig.
120 110 1 O0 90 80 4. These curves have similar shapes. The larger absolute
Ionic radius / pm
value for the bromides than the chlorides indicates
that the rare earth bromides have a more repulsive
Fig. 3. Water activities of the rare earth chloride and bromide ionic interaction. For the triple interaction parameter
solutions at 2.0 mol kg-~ and at 25.0 °C.
C +, the values for the bromides are larger than those
for the chlorides. These results indicate that the rare
earth bromides show a greater tendency than the chlo-
Gd Dy E r Yb rides towards outer-sphere complex formation. Further
La Pr Nd Sm Eu Tb Ho T m L u discussions will be given after studying the iodides of
the rare earth elements.

Acknowledgement

The authors express their sincere gratitude to Dr.

J.A. Rard, Lawrence Livermore National Laboratory,
1.00 University of California, for his kind advice.

References
0.95
[1] F.H. Spedding, H.O. Weber, V.W. Seager, H.H. Petheram,
J.A. Rard and A. Habenschuss, Y. Chem. Eng. Data, 21 (1952)
341.
f [2] F.H. Spedding and I.S. Yaffe, Jr. Am. Chem. Soc., 74 (1952)
0.90 4751.
[3] K. Fukushi, A. Mutoh, K. Ishikawa and Y. Suzuki, J. Alloys
Comp., 192 (1993) 290.
[4] K. Fukushi, K. lwamoto, K. Kobayashi, K. Ishikawa and Y.
0.85 I I I I I Suzuki, J. Alloys Comp., 207/208 (1994) 468.
120 115 110 105 100 [5] Y. Suzuki, R. Yoshino, H. Saitoh, K. Fukushi and Y. Sonehara,
J. Alloys Comp., 180 (1992) 383.
[6] K.S. Pitzer, J.R. Peterson and L.F. Silvester, J. Solut. Chem.,
Ionic radius / pm 7 (1978) 45.
Fig. 4. Pairwise short-range interaction parameters/3 (o) as a function [7] H. Kanno, T. Yamaguchi and H. Ohtaki, J. Phys. Chem., 93
of ionic radius of the rare earth ions. (1989) 1695.