Journal o f Solution Chemistry, Vol. 7, No.

1, 1978

Thermodynamics of Electrolytes. IX. Rare Earth Chlorides, Nitrates, and Perchlorates

Kenneth S. Pitzer, 1 John R. Peterson, ~ and Leonard F. Silvester 1
Received August 16, 1977 The extensive data for the osmotic coefficients, heats of dilution, and densities of aqueous solutions of rare earth chlorides, nitrates, and perchlorates are fitted to a single type of equation found satisfactory for many other solutes Good agreement is obtained. The various parameters do not show simple trends with cation radius. While there are some plausible explanations of these complexities, the total picture is far from clear.

KEY WORDS: Rare earth salts; lanthanides; osmotic coefficient; activity coefficient; heat of dilution; apparent molal volume; density, 1. I N T R O D U C T I O N

In a very extensive series of papers (1-1~ Spedding and associates have presented various thermodynamic data for the nitrates, chlorides, and perchlorates of most of the rare earths. 2 While excellent comparative treatments of the results for any one series are given in these papers, it seemed to us to be of some interest to fit a general array of these data to a single type of equation. We have considered the osmotic coefficient, the heat of dilution, and the volumetric data for all the chlorides, perchlorates, and nitrates. Thus, in effect, we consider the Gibbs energy and its temperature and pressure derivatives. Activity coefficients may be calculated from these results. The equation selected is that used extensively in this series of papers311-14) It was hoped that the trends of the parameters along the rare earth series would yield more reliable and interesting structural information than were 1 Department of Chemistry and Lawrence Berkeley Laboratory, Berkeley, California 94720. 2 Additional data are given in earlier papers cited in refs. 1-10.
45
0095-978217810100-0045505.0010 9 1978 Plenum Publishing Corporation

46

Pitzer, Peterson, and Silvester

obtained by Spedding and his associates in their direct examination of the original data. Our results in this respect are discussed below. The parameters obtained are also useful for various thermodynamic calculations and will be especially valuable for mixtures where the other components have been treated in the same system. The equations for mixtures are given in papeis IV (~3~ and V (~4~ of this series.
2. E Q U A T I O N S

The theoretical background for these equations was given in paper I (11; and in a recent review. (15~ In addition to a term for the long-range electrostatic effects treated by Debye and Hiickel, the equation contains second and third virial coefficients representing the effects of short-range forces (hydration effects, etc.) between ion pairs and triplets. As indicated in the theory presented elsewhere, an ionic strength dependence is expected for the second virial coefficient. For the osmotic and activity coefficients of pure electrolytes, one obtains

r - l = IzMzxlf ~ + m(2VMVx/v)B~Mx + m2[2(VMVX)312/v]CCMx (1)

In 7~ =

IzMzxlF + m(2vMVxlv)B~x + m2[2(vMvX)3'21v]C{~x

(2)

where VMand ~'x are the numbers of M and X ions in the formula and ZM and Zx give their respective charges in electric units; also v = v + "x and m is the molality. The other quantities are further defined

f ~ = -Ar fT = _Am [

+ b1112)

(3) (4) (5) (6)

(7)

I I'~ 2 ] 1 + bI ~12 +bIn(1 + b I ~/~)

B~x = fl~x +/3~)x e x p ( - ~ I 1/2) B~x = .~/-sMX')O(~+ (2/3(~)x/a2I) [1 - (1 + aI 1/2 - 1/2a2I) exp(-aI~/2)]
C ~ x = ~CMx 3

where I is the ionic strength, 89 2, and 14 is the Debye-Htickel coefficient for the osmotic function [89 which has the value 0.391 for water at 25~ The general parameters are given the values b = 1.2 and ~ = 2.0 throughout this and most other work with these equations. The specific parameters for each solute ,,,.o~o~Mx,~(~ t ~MX,~and C~x, and it is convenient to report them as multiplied by the preceding coefficients in Eqs. (1) and (2); thus for 3-1 electrolytes we report ~fl(o~, ~/3(~, and (33J~/2)C*. The appropriate equations for the enthalpy and the volume are obtained from temperature and pressure derivatives of the excess Gibbs energy per mole of solute G~ = vRT(1 - r + InT:~) (8)

Thermodynamics of Electrolytes. IX

47

This derivation has been given in some detail (l~ for the enthalpy and yields for the apparent relative motal enthalpy
% = ~lZMZxl(A~/3b)ln(1 + bI lt2) - 2VMvxRT2(mB~x + m2C~kx)

(9)

where Br~x = (a/3Mx/aT),,p(~ + (~(~)x/~T),,v(2/a2i)[1 - (1 + a1112)e x p ( - aP/2)] (10)

C~x = k(,~,~x)*'2(~C~x/aT),,,,
and Aa is the Debye-Htickel coefficient for enthalpy,

(tl)

AH/RT = - 9 A , [ 1 + T(~ In D/er)p + Taw~3]

(12)

with C,w = (9 In V/OT)p the coefficient of thermal expansion of the solvent. In this derivation the general parameters b and a are held constant with respect to temperature; the same assumption will be made with respect to pressure. The value (l~ of An/RT is 1.177 for water at 25~ For the volumetric properties the derivation is similar and will not be given in detail. The measured property, however, is the density rather than the heat of dilution, and this yields the absolute rather than the relative apparent molal volume. The additional term, the partial molal volume of the solute at infinite dilution V ~ must be evaluated. One has, then,

*V = F~ + vlzyzxl(Av/3b) ln(1 + bI ~/2) - 2VMvxRT(mBVx + m2CVx) (13) where BVx = (~)x/~P)~,r + (~i3~)x/OP)m.(2/a2I)[1 - (1 + aP/2) exp(-TaI~J~')] (14) CVx = 89 OC~x/OP )z,r
(15)

The density is related to the apparent molal volume by the expression 1000 + M2m d = (1000/do) + ~ Vm (16)

where do is the density of the pure solvent and 3/2 the molecular weight of the solute. The Debye-Hiickel parameter for volume is

Av = - 3A,RT[3(O In D/OP)r + (0 In V~,/~P)r]

(17)

where the last term is the negative of the compressibility of the solvent. This definition differs from that of Redlich and Meyer (~7~and others by the factor 23.(and the square root of the density of water). The equations for the volume and the dielectric constant for water which were adopted in paper VIII (~~ were used to calculate A~. The value of A~ is 2.626 cma-kg~/2-mole~/2 for water at 25~

48 3. E V A L U A T I O N OF P A R A M E T E R S

Pitzer, Peterson, and Silvester

The specific parameters for each rare earth salt were evaluated by least squares from the original data of Spedding et al., (1-1~ together with any other published data (18) (see also the papers cited in refs. 1-10) which was judged to be of comparable accuracy. For the chlorides, good fits were obtained up to the highest concentrations, frequently saturation. For the perchlorates and especially for the nitrates, it was possible to get good fits only up to about 2 M, and the final calculations were based only on data up to this maximum molality for these salts. For each function the square of the deviation in the measured quantity was minimized, i.e., the osmotic coefficient, the heat of dilution, or the density. These data were given unit weight up to I = 4 and then weights (4/I) 2. Since the parameter fi(1) and its derivatives have an important effect only for very dilute solutions, we explored the significance of differences in this parameter for various salts. For ~(1) itself, which is obtained from osmotic data, it appeared that the variation among salts for the same anion was random and not significant. Hence averaged values of 8.4, 7.7, and 9.8 were used for fi(~) for the chlorides, nitrates, and perchlorates, respectively. Somewhat to our surprise, the corresponding differences in efi(z)/~T appeared to be significant, and the results based on individual values of ~(1)/OT for each salt are reported. Apparently in dilute solutions the heat-of-dilution experiment is sufficiently more precise than that for the osmotic coefficient to yield this difference. Since the enthalpy involves only Ofl(1)/OT and not tim, the apparent inconsistency in this procedure is not serious, and it yields the most reliable values for other parameters. The parameters for the osmotic or activity coefficients and for the apparent molal enthalpies are given in Tables I, II, and III, respectively, for the chlorides, nitrates, and perchlorates. For the volumetric data the V ~ values obtained by Spedding and his associates (7-9) were first considered. These molal volumes at zero concentration must be additive for the ions present. Thus, the difference in V ~ for a pair of anions must be the same regardless of the cation. For most perchlorate and chloride pairs the difference in volume (V ~ was very nearly the same, and the average 78.77 cm a was adopted. The small differences were allocated equally to the individual chlorides and perchlorates to yield the results shown in Table IV. The data for the nitrates were somewhat less concordant; the average difference, nitrate less chloride, was 34.37 cm 3, and this was added to the adjusted chloride values to obtain individual V ~ values for the nitrates. The volumes for the chlorides are given in Table IV; those for the nitrates and perchlorates can be obtained from the differences given above. The least-squares regression with V ~ fixed at these adjusted values yielded the results for the pressure derivatives of fi(o), fi(~), and C ~ given in

Thermodynamics of Electrolytes. IX

49

Table I. Osmotic and Activity Coefficients and Enthalpies of Rare Earth Chlorides
3 Offo)
Rare earths La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Y 3-(o) 2/~ 0.8334 0.9072 0.8835 0.8784 0.9000 0.9115 0.913o 0.9220 0.9290 0.9375 0.9285 0.9262 0.9235 0.9228 0.9367 3/3(~ ) 2 8.40 8.40 8.40 8.40 8.40 8.40 8.40 8.40 8.40 8.40 8.40 8.40 8.40 8.40 8.40 3512 C ~ ~ -0.061o - 0.0745 -0.0549 -0.0495 - 0.0535 -0.0547 -0.0494 - 0.0468 - 0.0455 - 0.0450 -0.0389 -0.0362 -0.0335 -0.0332 -0.0407 20T x 104 3.790 3.622 3.715 2.279 0.237 -0.897 - 1.872 - 1.765 - 1.635 -1.731 - 1.438 -0.878 -1.965 --

30~ m 2 ~T 102
1.197 -1.327 1.335 1.271 1.275 1.25o 1.285 1.22o 1.28o 1.304 1.314 1.30o 1.28o --

3 aj2 0C ~ 2 OT x 104
-9.65 --9.10 -8.93 - 8.79 -8.348 -8.29 - 8.54 - 8.51 - 8.46 -8.16 --7.98 -8.14 --7.195 --

Table II. Osmotic and Activity Coefficients and Enthalpies of Rare Earth Nitrates
3 (9~(~ Rare earths La Pr Nd Sm Gd Tb Dy Ho Er Tm Yb Lu 3 ~ fro) 0.740 0.737 -0.701 0.776 0.838 --0.938 0.952 0.948 -3 -(~) 2/~ 7.70 7.70 -7.70 7.70 7.70 --7.70 7.70 7.70 -35/2 2 C* 20T x I0 a 2.592 2.439 2.364 2.152 2.181 1.807 1.988 1.681 1.724 1.835 1.895 1.927 3 ~/3a) 3~ ~C ~

2 c3T
x 102 1.648 1.854 2.068 2.535 2.002 1.585 1.630 1.631 1.65o 1.66o 1.685 1.705

OT

x 10 a - 1.172 - 1.121 -1.114 -1.003 - 1.053 - 1.012 -- 1.049 - 1.01o - 1.105 1.20e - 1.235 - 1.209

-0.199 -0.188 --0.131 - 0.170 --0.202 ---0.226 - 0.222 -0.208 --

50
Table III. Osmotic

Pitzer, Peterson, and Silvester

and Activity Coefficients and Enthalpies Earth Perchlorates 3 Sff ~ 2 ST x 103 2.27a 2,408 2.39~ 2.26a 2.011 -1.892 -1.999 --1.902 3 ~ff~ 2 8T x 102 2,254 2.27o 2.311 2.25o 2.17B -2.206 -2.175 --2.304 33/2 ~C ~ 2 ST x 10 a 1.74o 1,742 1,701 1.611 1.657 -- 1,71a -- 1.794 -- 1.657 of Rare

Rare earths La Pr Nd Sm Gd Tb Dy Ho Er Tm Yb Lu

flco) 1.15a 1.132 1.131 1.146 1.17a 1.19a 1.201 1.19o 1.202 1.1% 1.206 1.18o

3 ~1) ~fl 9.80 9.80 9.80 9.80 9.80 9.80 9,80 9.80 9.80 9.80 9.80 9.80
i

3at2 __ C~ 2 0.001o 0.016a 0.0194 0.014o 0.014o 0.0129 0.0142 0.0132 0.0144 0.0245 0.0137 0.0290

Table IV. V o l u m e t r i c

Data a for

Rare

Earth

Chlorides 3 Sff ~ 2 OP F~ 14.73 11.25 10.28 11.5o 12.4a 13.3o 13.41 12.86 11.88 10.94 9.6a 9.49 7.85 13.35 x 105 3.466 3.451 3.292 2.502 2.196 2.407 2.84z 3.023 3.076 3.14o 3.077 3.206 2.991 2.998 3 a ~ 1) 2 OP x 104 - 2.4o -2.82 - 2.73 -2.89 -2.3o -2.74 --2.87 -2.95 -- 2.88 -2.67 - 2.5a - 3,39 - 2,2~ -3.43 39/2 SC ~ 2 8P x 106 - 5.3o -3.94 - 2.95 -3.30 0.04 -1.36 -3.07 -3.49 -- 3.28 -3.45 - 2.8a - 3.22 - 2.17 -3.0~

Rare earths La Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Y
n

U n i t s are cubic c e n t i m e t e r s for V ~ a n d a r m -1 for o t h e r quantities.

Thermodynamics of Electrolytes, IX
Table

51

V. Volumetric D a t a ~ for Rare E a r t h Nitrates a n d Perchlorates Nitrates Perehlorates 33~2 ~C~ 2 aP x l0 s -10.12 - 3.66 14.76 6.49 -3.99 3 ~/3 <~ 2 8P x 105 4.138 3.989 3.795 2.835 2.320 2.009 2.180 2.48z 2.577 2.72s
2.909

Rare earths La Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
=

3 Offo~ 2 ~P x 10~ 5.544 4.461 1.879 2.437 -2.659 2.503 2.397 3.113 2.442
--

3 9B(1~ 2 ~P x104 -0.72 2.63 5.24 2.42 -- 1.65 - 2.6~ -2.69 -3.23 - 3.0o
--

3 913 (1~ 2 aP x 104 -4.91 - 5.61 - 4.73 - 5.76 - 5.05 - 5.27 -- 4.42 -4.04 -4.5s - 4.84
4.84

3312 OC~ 2 OP x 106 -6.25 - 4.99 - 4.40 - 2.58 -- 1.82 - 1.4o - 2.62 -4.14 -3.44 - 3.69 - 4.24 -4.72 -4.98

7.27
8.76 4.79 12.22
--

2.993 2.549

-4.34 -2.29

8.25 9.76

3.10o 3.133

-5.92 -4.96

Units are atm-x.

Tables IV a n d V. The significance of differences in (Ofl(l~/8p) for the different salts o f a given a n i o n is doubtful. The accuracy of fit is good t h r o u g h o u t , with s t a n d a r d deviations usually less t h a n 0.0001 for densities, 0.006 for osmotic coefficients, a n d 10 cal for heats of dilution. M a x i m u m deviations are roughly three times these values except for a few heats of dilution o f c o n c e n t r a t e d chlorides where deviations rise to 100 cal. Spedding a n d associates report n o data for cerium salts. The values in Table I are based o n the earlier data reported by R o b i n s o n a n d Stokes. (la~ Similar data for other chlorides are included in our calculations along with the more recent measurements, a n d the agreement is quite good. The small differences between the parameters for CeCla from those for LaC13 a n d PrCla are p r o b a b l y n o t significant, however.

4. D I S C U S S I O N
It is interesting to note the m a g n i t u d e of the temperature a n d pressure derivatives in relation to the p a r e n t functions. F o r the i m p o r t a n t parameters 3fl(0~, which is of the order unity, the temperature derivative is less t h a n 0.0004OK-1. Consequently, a 25 ~ change in temperature causes less t h a n 1~o change in fl(0> or 2~o change in 7 at 1 M. The pressure derivative is less t h a n

52

Pitzer, Peterson,

and Silvester

0.00006 atm-1; hence a 160-atm change causes less than 1% change in/3 (~ The Debye-Hfickel coefficient is somewhat more sensitive to temperature, with 25 ~ causing a 4% change, but is even less sensitive to pressure. Thus, the properties of these solutions do not change rapidly with temperature or pressure, and the dominant effect is the change of Debye-Hiickel parameter with temperature. The more significant parameters are shown as a function of the ionic radius of the positive ion in Fig. 1-5. The radii of Templeton and Dauben ~19) are used for the rare earths. For yttrium the radius is derived from the structure of Y203 determined by Paton and Maslen. ~2~ For the other ions in Fig. 3 the radii of Zachariasen ~21)were used. Many of these figures show the S-shaped curves noted before by Spedding and others and often attributed to a change in the inner-sphere hydration number of the cation. It is assumed that the inner sphere contains nine water molecules from La to Nd and eight water molecules from Tb to Lu with a transition between Nd and Tb. It is not entirely clear to us why a reduction in hydration number should lead to an actual increase in volume from Nd to Tb (see Fig. 1), but we have no better explanation. The trend with radius of the primary parameter for short-range

Yb Er Dy Gd LuITmI ~o I TbI E~uSm Nd Pr

,,I,I~l,I

Lo

95 90
85

5C _o 45 V 4C
I

I
0.9
I

I0 5 0.8 1.0
I

I.I

Fig. 1. The partial molal volume at zero molality for rare earth salts as a function of cation radius.

Thermodynamics of Electrolytes. IX
Yb Er Dy Od

53

Lu Tm I;10 Tb I Eu,Sm !d Pr
I I I
1.2

Lo
I

DDD

DD

[]

[] []
[] DD

C104 D

I,

-_o
(NI -.. 0.~ 1,3

AA ~0 O0 O0

O0
0 o 0

CI-

0.8-

NO;
A 0.7 0.8 I 0.9 A I 1.0

r/.~ Fig. 2. The pairwise short-range interaction parameter tim)as a function of cation radius for rare earth salts. Chlorides are shown as circles, nitrates as triangles, and perchlorates as squares.

pairwise interaction fl(o) is shown in Figs. 2 and 3. The larger absolute value for perchlorates than chlorides indicates a more repulsive interaction for the perchlorate anion. The trend over a wider range of radii in Fig. 3 indicates that fl(0) decreases with increase in radius. Thus, the trend from Tb to Nd appears to be normal, and the regions Lu to Dy and Pr to La appear to be anomalous. This is in contrast to the explanation for F ~ values where the middle group of rare earths Tb to Nd was said to be the anomalous region. The rare earth nitrates show more tendency toward inner-shell complex formation at high concentration than the chlorides (or perchlorates), and this would be expected to yield lower values of the interaction parameters. This is most apparent in the relatively large negative values of the triple interaction parameter C a (see Table II). The pairwise interaction parameter rico) also shows somewhat lower values for the nitrates of the larger cations but not for the smaller cations (as compared to the chlorides). Presumably this indicates

54
I I

Pitzer, Peterson, and Siivester

I

-a
O3

1.0
A

0.9 I 0.6

A 0o 0

0.4

O.8

1.0

I.

r/~
Fig. 3. The pairwise short-range interaction parameter fl(o)for a series of + 3 ion chlorides as a function of cation radius. The current results are shown as circles; previous results (ref. 13) as triangles.
Tm No Tb Eu

LuYb D l Y l ErI 2.5

Gd Sml Ndr ,I P

Eft

9
A A

2.0
m3 O x A

NO~
9 C104 oCI-

0.4 0.2 0
0 0 0 0

-0,2
0.8

o ~

o o o I
0.9

I
1.0 I.I

r/~ Fig. 4. The enthalpy-of-dllution parameter (a#(~ as a function of cation radius.

Thermodynamics of Electrolytes. IX
Yb Er Dy Gd Lu Tm Ho Tb
4 oDD ~ DD [] 0 o 0 [] ClLa

55

[]

L~ 0 X
O0 0
Oo o

0 0 0 0

cio~

6 5 4
/x

NO~

0.8

0.9 r/~

1.0

I.I

Fig. 5. The voIumetric parameter (Oflt~ as a function of cation radius. Chlorides are shown as squares except a solid triangle for yttrium, perchlorates as circles, and nitrates as open triangles. that a nitrate ion can compete with water for a place in the inner shell of a large cation such as La +a but not for a smaller + 3 ion. The interpretation of the temperature a n d pressure derivatives of/3 (0), shown in Figs. 4 and 5, is even more uncertain. Figure 4 shows the familiar s-shaped curves. The trends in figure 5, while not closely linear, are better described as showing a dip in the middle region near Gd for the chlorides and perchlorates at least. Our primary conclusion is just that these parameters do not show smooth trends with ionic radius. When one recalls the considerable success of simple models based on radius in explaining ionic properties for other sets of ions, this behavior for the rare earth series is indeed anomalous and deserves further study by a wider variety of techniques.
ACKNOWLEDGMENT

This research was sponsored by the Energy Research and Development Administration.

56 REFERENCES

Pitzer, Peterson, and Silvester

1. F. H. Spedding, H. O. Weber, V. W. Saeger, H. H. Petheram, J. A. Rard, and A. Habenschuss, J. Chem. Eng. Data 21, 341 (1976). 2. J. A. Rard, H. O. Weber, and FL H. Spedding, J. Chem. Eng. Data 22, 187 (1977). 3. J. A. Rard, L. E. Shiers, D. J. Heiser, and F. H. Spedding, J. Chem. Eng. Data 22, 337 (1977). 4. F. H. Spedding, J. L. Derer, M. A. Mohs, and J. A. Rard, J. Chem. Eng. Data 21,474 (1976). 5. F. H. Spedding, C. W. DeKock, G. W. Pepple, and A. Habenschuss, J. Chem. Eng. Data 22, 58 (1977). 6. F. H. Spedding, M. A. Mohs, J. L. Derer, and A. Habenschuss, J. Chem. Eng. Data 22, 142 (1977). 7. F. H. Spedding, V. W. Saeger, K. A. Gray, P. K. Boneau, M. A~ Brown, C. W. DeKock, J. L. Baker, L. E. Shiers, H. O. Weber, and A. Habenschuss, J. Chem. Eng. Data 20, 72 (1975). 8. F. H. Spedding, L. E. Shiers, M. A. Brown, J. L. Derer, D. L. Swanson and A. Habenschuss, J. Chem. Eng. Data 20, 81 (1975). 9. F. H. Spedding, L. E. Shiers, M. A. Brown, J. L. Baker, L. Guitierrez, L. S. McDowell and A. Habenschuss, J. Phys. Chem, 79, 1087 (1975). 10. F. H. Spedding, J. A. Rard, and A. Habenschuss, J. Phys. Chem. 81, 1069 (1977). 11. K. S. Pitzer, J. Phys. Chem. 77, 268 (1973). 12. K. S. Pitzer and G. Mayorga, J. Phys. Chem. 77, 2300 (1973). 13. K. S. Pitzer and J. J. Kim, J. Am. Chem. Soc. 96, 570i (1974). 14. K. S. Pitzer, J. Solution Chem. 4, 249 (1975). 15. K. S. Pitzer, Ace. Chem. Res. 10, 371 (1977). 16. L. F. Silvester and K. S. Pitzer, J. Phys. Chem. 81, 1822 (t977). 17. O. Redlick and D. M. Meyer, Chem. Rev. 64, 221 (1964). 18. R. A. Robinson and R. M. Stokes, Electrolyte Solutions, 2nd revised ed. (Butterworths, London, 1965). 19. D. H. Templeton and C. H. Dauben, J. Am. Chem. Soc. 76, 5237 (1954). 20. M. G. Paton and E. N. Maslen, Aeta Crystallogr. 19, 307 (1965). 21. W. H. Zachariasen in The Actinide Elements, G. T. Seaborg and J. J. Katz, eds. (McGraw-Hill, New York, 1954), p. 769.