Phys Chem Minerals (2000) 27: 342346
ORIGINAL PAPER
J. Li B. Li S. Gao
Calculation of thermodynamic properties of hydrated borates
by group contribution method
Received: 23 November 1998 / Accepted: 11 October 1999
Abstract General equations to correlate and predict the
thermodynamic properties of hydrated borates were
developed based on the experimental results according
to their structural types. The thermodynamic properties
(DH0f and DG0f ) of a hydrated borate phase are the sum
of the contributions of the cations in aqueous solution,
the borate polyanions, and the structural water to the
corresponding thermodynamic properties. This method
is called the group contribution method, and it is ex-
tensively used to calculate the thermodynamic properties
of many kinds of inorganic compounds, such as silicates
and clay minerals.
Key words Thermodynamic properties Hydrated
borates Group contribution
Introduction
Borates are one type of inorganic compounds that are
found widespread in nature and synthesized in labora-
tory. There have been many studies on their structures
(Christ and Clark 1977; Heller 1986), their aqueous so-
lution chemistry (Farmer 1982), and their thermody-
namic properties (Li et al. 1997a, b, 1998a, b; Bassett
1976). Thermodynamic properties of hydrated borates
play a very important role in scientic research and in-
dustrial applications. However, it is impossible to obtain
the thermodynamic properties of each borate by cal-
orimetric measurements. Empirical and theoretical ap-
proaches must be developed to correlate and predict
J. Li (&) B. Li S. Gao
Xi'an Branch, Institute of Salt Lakes,
The Chinese Academy of Sciences,
Road Xiying 6, Xi'an,
Shaanxi Prov. 710043, P. R. China
e-mail: julin@ihw.com.cn
Fax: +86-029-5520341
Springer-Verlag 2000
these thermodynamic properties of hydrated borates.
Many empirical and theoretical approaches have been
developed to correlate and predict thermodynamic
properties of compounds. The concept of group contri-
bution has been widely accepted for this purpose.
Chemists have used additive methods (Benson et al.
1969) to calculate the standard molar enthalpy and free
energy of formation, as well as the heat capacity, of
organic substances. Mineralogists and geochemists have
used a polyhedral contribution model to calculate the
thermodynamic properties of silicates (Chermak and
Rimstidt 1989), carbonate minerals (La Iglesia and Felix
1994), and clay minerals (Sposito 1986). Additive
methods and polyhedral contribution models can be
called group contribution methods. The most extensive
correlation of solid inorganic salts following the concept
of group contributions was given by Mostafa et al.
(1995), who tested a large number of solid inorganic
salts and gave the values for the group contributions to
DH0f and DG0f for cations, anions, and ligand molecules.
Moreover, many empirical relations have also been
found for inorganic compounds (Hisham and Benson
1985, 1987, 1988; Vieillard and Jenkins 1986a, b, c). For
hydrated borates, Bassett (1976) and Mattigod (1983)
suggested several methods to estimate the standard
molar Gibbs free energies of formation of borates. One
of Bassett's methods that involved structural consider-
ations provided more accurate estimates of DG0f values
compared with the values computed from the solubility,
but this method can work only when the Gibbs free
energy contributions from dierent types of borate
polyanions can be computed from existing DG0f or sol-
ubility data. Mattigod developed the structural method
according to a general reaction of formation with only
one parameter, the number of boron atoms in the borate
polyanion. The present authors (Li et al. 1998b) also
gave a simple correlation for DH0f of hydrated
borates. In this work, we will develop further our former
method to correlate and predict the thermodynamic
properties of hydrated borates by the group contribu-
tion method.
 343

Where, x, y, z, a, and n are the stoichiometric coecients of boron,

Method oxygen, hydroxyl, cation, and structural water in the borate, m+ is
the valence of metal cation, and ma = 3x ) 2y ) z. From the DH0f or
The studies of structures of hydrated borates have revealed that the DG0f of hydrated borates and of cations in aqueous solution, one
cations retain partially or fully hydrated spheres, and that the bo- may obtain the contributions of the borate polyanions and the
rate polyanions can be isolated groups, innite chains, sheets, or structural water to the corresponding thermodynamic quantities of
three-dimensional networks formed by corner-sharing of triangular hydrated borates by using multiple linear regress technique (with
or tetrahedral boron-oxygen moieties or both, and polymerization. the constant in the regressions being set to zero).
The cations of partially or fully hydrated spheres connect the bo-
rate polyanions by metal-oxygen bonds and hydrogen bonds. Hy-
drated borates are commonly called monoborates, diborates, Results
triborates, tetraborates, pentaborates, hexaborates, etc., according
to their borate polyanions. Therefore, the enthalpy dierence and
free energy dierence between a cation in aqueous solution and the The experimental and calculated DH0f and DG0f of hy-
same cation in a hydrated borate should be minimal. Following the drated borates are listed in Tables 1 and 2. The average
concept of the group contribution method, the DH0f or DG0f of a relative errors for DH0f and DG0f are 0.23 and 0.16%,
hydrated borate phase should be the sum of the contributions of respectively. The second column and the third column in
corresponding cations in aqueous solution, of borate polyanions,
and of structural water. For a borate Ma[BxOy(OH)z] nH2O, Table 3 list the regressed DH0f and DG0f values of borate
polyanions and structural water. The DH0f and DG0f of
DH0f borate a DH0f Mm ; aq DH0f Bx Oy OHz the cations in aqueous solution used for calculation were
n DH0f H2 O 1 taken from NBS tables (Wagman et al. 1982). These
values are listed in Table 4. The correlation coecients
DG0f borate a DG0f Mm ; aq DG0f Bx Oy OHz in the regressions are all 0.99. The last two columns in
n DG0f H2 O 2 Table 3 list standard molar entropies of formation DS0f

Table 1 Experimental and cal-

culated standard molar en- Borate Structural formula DH0f (exp) DH0f (calc) Error
thalpies of formation of )1 )1
hydrated borates (kJ mol ) (kJ mol ) (%)

Monoborate
CaB2O4 4H2O Ca[B(OH)4]2 )3228.07a )3233.93 )0.18
CaB2O4 6H2O Ca[B(OH)4]2 2H2O )3811.13a )3814.77 )0.09
NaBO2 2H2O NaB(OH)4 )1581.5b )1585.9 )0.28
NaBO2 4H2O NaB(OH)4 2H2O )2175.7b )2166.58 0.42
Triborate
Inderite MgB3O3(OH)5 5H2O )9631.90c )9663.90 )0.33
Kurnakovite MgB3O3(OH)5 5H2O )9626.48c )9663.90 )0.39
Mg2B6O11 17H2O MgB3O3(OH)5 6H2O )10272.06c )10245.96 0.25
Ca2B6O11 5H2O CaB3O4(OH)3 H2O )6939.58d )6939.58 0
Ca2B6O11 9H2O CaB3O3(OH)5 2H2O )8056.25a )8073.41 )0.21
Ca2B6O11 13H2O CaB3O3(OH)5 4H2O )9294.34d )9235.44 0.64
Ca2B6O11 7H2O CaB3O3(OH)5 H2O )7492.22
Tetraborate
Li2B4O7 3H2O Li2B4O6(OH)2 2H2O )4290.86e )4292.05 )0.03
Na2B4O7 4H2O Na2B4O6(OH)2 3H2O )4507.4b )4506.21 0.03
Na2B4O7 5H2O Na2B4O5(OH)4 3H2O )4802.4b )4816.4 )0.29
Na2B4O7 10H2O Na2B4O5(OH)4 8H2O )6288.5b )6268.5 0.32
K2B4O7 4H2O K2B4O5(OH)4 2H2O )4568.77f )4549.58 0.42
MgB4O7 9H2O MgB4O5(OH)4 7H2O )5939.21c )5964.39 )0.42
Pentaborate
LiB5O8 5H2O LiB5O6(OH)4 3H2O )5130.25e )5139.70 )0.18
NaB5O8 5H2O NaB5O6(OH)4 3H2O )5099.77f )5101.57 )0.03
KB5O8 4H2O KB5O6(OH)4 2H2O )4834.19f )4822.95 0.23
Hexaborate
MgB6O10 5H2O MgB6O7(OH)6 2H2O )6007.00
MgB6O10 6H2O MgB6O7(OH)6 3H2O )6294.70c )6297.57 )0.05
MgB6O10 7H2O MgB6O7(OH)6 4H2O )6588.78c )6587.99 0.01
MgB6O10 7.5H2O MgB6O7(OH)6 4.5H2O )6735.29c )6733.20 0.03
CaB6O10 4H2O CaB6O9(OH)2 3H2O )5819.09a )5819.09 0
a
Li et al. 1997b
b
Wagman et al. 1982
c
Li et al. 1997a
d
Gurevich and Sokolov 1976
e
Li et al. 1998b
f
Li et al. 1998a
344

Table 2 Experimental and cal-

culated standard molar Gibbs Borate Structural formula DG0f (exp)a DG0f (calc) Error
free energies of formation of )1 )1
hydrated borates (kJ mol ) (kJ mol ) (%)

Monoborate
LiBO2 8H2O LiB(OH)4 6H2O )2873.80 )2876.85 )0.11
CaB2O4 6H2O Ca[B(OH)4]2 2H2O )3366.10 )3347.84 0.54
NaBO2 2H2O NaB(OH)4 )1415.20 )1421.76 )0.46
NaBO2 4H2O NaB(OH)4 2H2O )1888.24 )1896.32 )0.43
SrB2O4 4H2O Sr[B(OH)4]2 )2896.32 )2879.18 0.59
Triborate
Inderite MgB3O3(OH)5 5H2O )8497.91 )8499.59 )0.02
Kurnakovite MgB3O3(OH)5 5H2O )8499.59
MgCaB6O11 6H2O MgCa[B3O4(OH)3]2 3H2O )6465.95 )6462.69 0.04
MgCaB6O11 11H2O MgCa[B3O3(OH)5]2 6H2O )7650.36 )7649.20 0.02
Ca2B6O11 5H2O CaB3O4(OH)3 H2O )6320.89 )6321.15 )0.05
Ca2B6O11 13H2O CaB3O3(OH)5 4H2O )8223.02 )8222.50 0.01
Ca2B6O11 7H2O CaB3O3(OH)5 H2O )6798.82
Ca2B6O11 9H2O CaB3O3(OH)5 2H2O )7273.38
Tetraborate
(NH4)2B4O7 4H2O (NH4)2B4O5(OH)4 2H2O )3724.60 )3729.26 )0.13
Na2B4O7 10H2O Na2B4O5(OH)4 8H2O )5516.60 )5518.01 )0.03
K2B4O7 4H2O K2B4O5(OH)4 2H2O )4135.05 )4137.07 )0.05
MgB4O7 9H2O MgB4O5(OH)4 7H2O )5219.87 )5211.75 0.16
Pentaborate
NH4B5O8 4H2O NH4B5O6(OH)4 2H2O )4173.14 )4175.66 )0.06
NaB5O8 5H2O NaB5O6(OH)4 3H2O )4589.28 )4595.46 )0.13
KB5O8 4H2O KB5O6(OH)4 2H2O )4388.24 )4379.55 0.20
Hexaborate
MgB6O10 5H2O MgB6O7(OH)6 2H2O )5495.64
MgB6O10 6H2O MgB6O7(OH)6 3H2O )5732.92
MgB6O10 7H2O MgB6O7(OH)6 4H2O )5970.20
MgB6O10 7.5H2O MgB6O7(OH)6 4.5H2O )6088.84 )6088.84 0
CaB6O10 4H2O CaB6O9(OH)2 3H2O )5366.86 )5366.86 0
a
Bassett (1976)

Table 3 Thermodynamic properties of borate polyanions and Table 4 The standard molar thermodynamic properties of cations
structural H2O molecule in aqueous solution and liquid watera

Species DH0f DG0f DS0f S0 Cation DH0f DG0f

kJ mol)1 kJ mol)1 J K)1 mol)1 J K)1 mol)1 (kJ mol)1) (kJ mol)1)

B(OH) )1345.46 )1159.87 )622.47 54.66 Li+ )278.48 )293.30

4
)2912.86 )2608.59 )1027.23 137.07 Na+ )240.12 )261.89
B3O3(OH)2
5 K+ )252.38 )283.26
B3O4(OH)2
3
)2636.37 )2371.26 )889.18 42.03 NH )79.37
4
B4O5(OH)2
4
)3464.46 )3095.99 )1235.85 )28.41 Mg2+ )466.85 )454.80
B4O6(OH)2
2
)3154.27 Ca2+ )542.83 )553.54
B5O6(OH) )3989.97 )3621.73 )1235.08 80.78 Sr2+ )559.44
4
)4959.31 )4566.28 )1318.23 441.66 H2O )285.83 )237.18
B6O7(OH)2
6
B6O9(OH)2
2
)4404.83 )4101.07 )1017.44 276.27 a
Wagman et al. (1982)
H2O )290.42 )237.28 )178.23 54.86

K2MgB6O11 9H2O given by Gode et al. (1981). The

0 structural formula of this compound is
and standard molar entropies S of the borate polya-
K2Mg[B3O3(OH)5]2 4H2O. The calculated value of
nions and the structural water which are calculated from
)7959.01 kJ mol)1 agrees very well with the experi-
thermodynamic relationship, respectively. The standard
mental result of )8012.36 kJ mol)1.
molar entropies of the elements used were also taken
from the NBS tables.
In order to test the accuracy of the model, we com- Discussion and conclusion
pared the calculated values with the experimental data.
The only measured value found calorimetrically, which From Tables 1 and 2, it can be seen that the calculated
had not been used for regression is DH0f of results are close to the experimental values. The

calculated DH0f and DG0f values of the structural water
are close to those regressed by Mostafa et al. (1995)
from a large number of inorganic salts, and comparable
with those for liquid water.
As also shown in Table 3, the S0 values of
B4 O5 OH24 and B5 O6 OH 4 calculated from the
thermodynamic relationship happen to be too small. It
seems that the DG0f values of the tetraborates and pen-
taborates are more negative. One reason is the source of
DG0f : all DG0f values of the hydrated borates were cal-
culated by Bassett from solubility data in water, apply-
ing the revised Davis equation to calculate the activity
coecients of ions. The Davis equation is suitable for
the calculation of the activity coecients of ions in
aqueous solutions of lower ion strength, while alkali
metal tetraborates and pentaborates are more soluble.
Another reason is the precision of chemical analysis.
Early methods of determining the concentration of bo-
ron in aqueous solutions are of lower precision. The
standard molar entropies of borate polyanions listed in
Table 3 are for rough estimation only. We could also
obtain the entropy contributions of borate polyanions to
standard molar entropies of hydrated borates by ap-
plying the group contribution method if the S0 values of
hydrated borates were available. Chermak and Rimsidt
(1989) indicated that the two sets of values obtained
from thermodynamic relationships and polyhedral con-
tributions had much larger associated errors, and they
considered that the standard molar entropies were more
sensitive to coordination than enthalpy and free energy.
The technique of Holland (1989) for estimating S0 of
silicates may be used to give a more accurate estimation
of S0 of hydrated borates, and produce an internally
consistent set of DH0f , DG0f , and S0 values.
The present technique can be used to predict the
thermodynamic properties of a hydrated borate phase
when its structural type is known. An example is illus-
trated here for predicting DH0f of MgB6O10 5H2O
(aksaite). According to its formula MgB6O7(OH)6 2H2O
and Eq. (1),
DH0f aksaite DH0f Mg2 ; aq DH0f B6 O7 OH6 2 Holland TJB (1989) Dependence of entropy on volume for silicate
2DH0f H2 O
466:85 4959:31 2  290:42
6007:00 kJ mol1
The same technique was used to predict DG0f of aksaite.
The predicted DH0f and DG0f for other borates are listed
in Tables 1 and 2.
In conclusion, the group contribution method is ap-
plicable to the calculation of thermodynamic properties
of hydrated borates. The thermodynamic properties
(DH0f and DG0f ) of a hydrated borate phase are the sum
of the contributions of the cations in aqueous solution,
the borate polyanions, and the structural water, to the
corresponding thermodynamic properties. The only data
needed for calculation are the structural formula of a
hydrated borate. Although this method seems to give
345
reliable results, it is only used when the thermodynamic
properties of a hydrated borate are unknown. It should
also be noted that experimentally determined thermo-
dynamic data are more accurate than the estimated and
predicted values.
Acknowledgements This work was supported by the Special
Foundation of the Director, and partially by the Key Project
Foundation, Chinese Academy of Sciences.
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