J. Chem.

Thermodynamics 37 (2005) 743–753

www.elsevier.com/locate/jct

The error analysis of the determination of the activity

coefficients via the isopiestic method
a,*
Jun Zhou , Qi-Yuan Chen a, Zheng Fang a, Yi-Zeng Liang a,
Shi-Jun Liu a, Yong Zhou b
a
Institute of Physical Chemistry in the College of Chemistry and Chemical Engineering, Central South University, Lushan South Road 154,
Changsha, Hunan 410083, China
b
Huaihua Radio Administrative Office, Yingfeng Eastern Road 102, Huaihua, Hunan 418000, China

Received 9 May 2004; received in revised form 4 November 2004; accepted 18 November 2004
Available online 22 January 2005

Abstract

Error analysis is very important to experimental designs. The error analysis of the determination of activity coefficients for a
binary system via the isopiestic method shows that the error sources include not only the experimental errors of the analyzed mol-
alities and the measured osmotic coefficients, but also the deviation of the regressed values from the experimental data when the
regression function is used. It also shows that the accurate chemical analysis of the molality of the test solution is important,
and it is preferable to keep the error of the measured osmotic coefficients changeless in all isopiestic experiments including those
experiments on the very dilute solutions. The isopiestic experiments on the dilute solutions are very important, and the lowest molal-
ity should be low enough so that a theoretical method can be used below the lowest molality. And it is necessary that the isopiestic
experiment should be done on the test solutions of lower than 0.1 mol Æ kg
1. For most electrolytes solutions, it is usually preferable
to require the lowest molality to be less than 0.05 mol Æ kg
1. Moreover, the experimental molalities of the test solutions should be
firstly arranged by keeping the interval of the logarithms of the molalities nearly constant, and secondly more number of high mol-
alities should be arranged, and we propose to arrange the experimental molalities greater than 1 mol Æ kg
1 according to some kind
of the arithmetical progression of the intervals of the molalities. After experiments, the error of the calculated activity coefficients of
the solutes could be calculated from the actually values of the errors of the measured isopiestic molalities and the deviations of the
regressed values from the experimental values with our obtained equations.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Error analysis; Determination of activity coefficients; Isopiestic method; Experimental designs

1. Introduction determination of activity coefficients via the isopiestic

Error analysis is very important to science researches,
especially to experimental researches. It will provide
much fundamental information for experimental designs.
However, there is almost no error analysis about the
*
Corresponding author. Tel.: +86 731 8877364 (laboratory); fax:
+86 731 8879616 (college office).
E-mail addresses: zhouj_csu@163.com, zhouj_cn2003@yahoo.com
(J. Zhou).
method so far. As a result, it is not clear that how many
kinds of error sources there are in isopiestic experiments
which will finally influence the determined activity coeffi-
cients of solutes; and what kind of precision should be re-
quired in isopiestic experiments; and down to what kind
of low molality of test solutions isopiestic experiments
should be done from the high molality of test solutions;
and how to arrange the experimental molalities of test
solutions in isopiestic experiments; and what kind of
relationship there is between the error of the determined

0021-9614/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2004.11.014
744 J. Zhou et al. / J. Chem. Thermodynamics 37 (2005) 743–753
activity coefficient and various errors existing in isopiestic
experiments, and so on. The solutions of all these prob-
lems mentioned above are based on the error analysis. Be-
low we will make an error analysis on the determination of
activity coefficients of the solute in a binary system via the
isopiestic method.
2. Determination of activity coefficients via the isopiestic
method
Many activity coefficients of solutes are determined
via the isopiestic method. However, the measured quan-
tities for test solutions in isopiestic experiments are the
osmotic coefficients of test solutions, namely the activities
of the solvents in the test solutions, and the molalities of
test solutions. And the activity coefficients of the solutes
in the test solutions are obtained by calculation from the
osmotic coefficients according to Gibbs–Duhem equa-
tion. For a binary system of the test solution composed
of solvent (S) and solutes (i), the activity coefficients of
the solute, ci, is calculated by the following equations:
Z mi

ln ci ¼ ð1
UÞ þ ð1
UÞ  d ln mi ; ð1Þ
0
U ¼
ðmS  ln aS Þ=ðmi  mi Þ; ð2Þ
where U is osmotic coefficients, and mS is the molality of
solvent S, and mi is the molality of solute i, and mi is the
number of ions in one formula units of solute i, and aS is
the activity of the solvent in the test solution, which is
also equal to the activity of the solvent in the standard
reference solution (R) in isopiestic equilibrium experi-
ments. It is clear from equation (1) that isopiestic exper-
iments must be made down to as low molalities as
possible and must be spaced closely enough to permit
accurate evaluation of the integral [1].
3. The error sources of the calculated activity coefficients
of solutes in isopiestic experiments
3.1. The error sources derived from the measurement of
the experimental data
In isopiestic experiments, the molalities and the os-
motic coefficients for test solutions are experimental
quantities. They are expressed as mi,anal and Umeas,
where the subscript ‘‘anal’’ indicates the quantities are
obtained by the chemical analysis method, and the sub-
script ‘‘meas’’ indicates that the quantities are obtained
essentially by isopiestic measurements. Of course, there
are experimental errors existing in them, and these
errors are expressed as r(ln mi,anal) = d(ln mi,anal
ln
mi,accur) and r(Umeas) = (dUmeas
Uaccur), where mi,accur
and aS,accur are theoretical accurate values in isopiestic
experiments. It is easy know that r(ln mi,anal) is relevant
to the chemical analyses of the molalities of test solu-
tions. However, according to equation (2), we know that
r(Umeas) is not only related to the measurements of the
activity of the solvent via isopiestic experiments, but also
related to r(ln mi,anal). Therefore, though the osmotic
coefficients are usually used by many chemists in science
research, for the error analysis it is more suitable to base
on the experimental quantities of the activities of the sol-
vents of the test solutions, which are the directly mea-
sured quantities, and of which the errors are
independent to r(ln mi,anal). The errors of the activities
of the solvent in the test solution are expressed as
r(ln aS,meas) = d(ln aS,meas
ln aS,accur), where ln aS,accur
are theoretical accurate values in isopiestic experiments.
It is obvious that r(ln mi,anal) and r(ln aS,meas) are two
important error sources for the calculated activity coef-
ficients of solute i, which is expressed as ci,cal.
As we know, the values of aS,meas are calculated from the
measured values of the molalities of the standard reference
solution (R), mR,meas, in isopiestic measurements. It is
obvious that r(ln aS,meas) should be determined by the error
of the measured molality of the standard reference solution
r(ln mR,meas) in the isopiestic experiment. According to
Gibbs–Duhem equation we have the following equation:
mS  d ln aS;meas ¼
ðmR  mR;meas Þ  d lnðcR  mR;meas Þ ¼

ðmR  mR;meas Þ  ðd ln cR =d ln mR;meas þ 1Þ
d ln mR;meas ; ð3Þ
where mR and cR are analogous to mi and ci, but are the
values for the standard reference solution. We can then
obtain:
mS  rðln aS;meas Þ ¼
ðmR  mR;meas Þ  ðd ln cR =d ln mR;meas þ 1Þ
rðln mR;meas Þ: ð4Þ
This equation shows that r(ln mR,meas) is one of impor-
tant error sources which will determine the quantity of
r(ln aS,meas). Moreover, we should keep it in the mind
that r(ln mR,meas) comprises not only the experimental
error in the chemical analysis of the molality of the stan-
dard reference solution but also the experimental error
in the isopiestic measurement of the solvent activity of
the test solution.
In fact r(ln aS,meas) is not only related to r(ln mR,meas)
but also related to the accuracy of the formula used in
the calculation of aS,meas from mR,meas. However, the
accuracies of the used formula are not essential in the er-
ror analyses of the isopiestic measurements, and they can
be improved outside of the isopiestic experiments. In
addition, for some standard reference solutions the accu-
racies of the formula used in the calculations are usually
good enough, for example the data given by Clarke and
co-workers [2] and Archer [3]. Therefore, the errors de-
rived from the formula used in the calculations of aS,meas
from mR,meas are not considered in this paper.
 J. Zhou et al. / J. Chem. Thermodynamics 37 (2005) 743–753
Though r(ln mi,anal) = d(ln mi,anal
ln mi,accur) and
r(ln aS,meas) = d(ln aS,meas
ln aS,accur) are independent
errors, they do not influence the error of the calculated
activity coefficients, r(ln ci,cal), respectively. According
to thermodynamic theory, for the test solution system
aS should be the theoretical function of mi under the
constant temperature T and pressure p, which is ex-
pressed as follows:
ln aS ¼ ln aS ðmi Þ: ð5Þ
And for the theoretical accurate values, aS,accur and
mi,accur, they should satisfy that theoretical function ex-
actly, and there is:
ln aS;accur ¼ ln aS ðmi;accur Þ: ð6Þ
We should keep it in mind that the factor which will
finally and actually influence r(ln ci,cal) is the deviation
of the relationship of the experimental values, mi,anal
and aS,meas, from the theoretical relationship, namely
from equation (5). It is to say, however great are the
values of r(ln mi,anal) and r(ln aS,meas), as long as mi,anal
and aS,meas happen to satisfy equation (5), r(ln mi,anal)
and r(ln aS,meas) will have no influence on the errors of
calculated values of ci,cal. Therefore, r(ln mi,anal) and
r(ln aS,meas) should be integrated into the deviation of
the relationship of mi,anal and aS,meas from equation
(5). This deviation can be expressed as d{ln aS,meas

ln aS(mi,anal)}, where ln aS(mi,anal) is the theoretical value
corresponding to mi,anal on basis of equation (5) with the
assumption that mi,anal be an ‘‘accurate’’ value. Accord-
ing to equation (6), this deviation can be expressed as
follows:
dfln aS;meas
ln aS ðmi;anal Þg ¼
dfln aS;meas
ln aS;accur þ ln aS ðmi;accur Þ
ln aS ðmi;anal Þg ¼
dfln aS;meas
ln aS;accur g
dfln aS ðmi;anal Þ
ln aS ðmi;accur Þg:
ð7Þ
Moreover, according to Gibbs–Duhem equation, for
a binary system we can obtain the following equations:
mS  d ln aS ðmi;anal Þ ¼
ðmi  mi;anal Þ  d lnðci  mi;anal Þ ¼

ðmi  mi;anal Þ  ðd ln ci =d ln mi;anal þ 1Þ
d ln mi;anal : ð8Þ
mS  dfln aS ðmi;anal Þ
ln aS ðmi;accur Þg ¼

ðmi  mi;anal Þ  ðd ln ci =d ln mi;anal þ 1Þ
dðln mi;anal
ln mi;accur Þ: ð9Þ
By introduction of equations (4) and (9), equation (7)
becomes
mS  dfln aS;meas
ln aS ðmi;anal Þg ¼

ðmR  mR;meas Þ  ðd ln cR =d ln mR;meas þ 1Þ  rðln mR;meas Þþ
ðmi  mi;anal Þ  ðd ln ci =d ln mi;anal þ 1Þ  rðln mi;anal Þ:
ð10Þ
745
This equation shows that the deviation of the relation-
ship of mi,anal and aS,meas from the theoretical relation-
ship, d{ln aS,meas
ln aS(mi,anal)}, comprises both of
r(ln mi,anal) and r(ln mR,meas) and then should be consid-
ered as a type of total error source which will finally and
actually influence the calculated values of ci,cal. Since
this total error is derived on the basis of the assumption
that mi,anal be a ‘‘accurate’’ value, this total error is then
expressed as rT(ln aS,meas) without the appearance of
mi,anal in it, and of course, there is
rT ðln aS;meas Þ ¼ dfln aS;meas
ln aS ðmi;anal Þg: ð11Þ
Because r(ln mi,anal) and r(ln mR,meas) are random errors,
it is not certain whether their values are positive or neg-
ative. Therefore, according to the theory of the propaga-
tion of the random errors we can obtain the following
equation basing on equations (10) and (11):
m2S  r2T ðln aS;meas Þ ¼ ðmR  mR;meas Þ2  ðd ln cR =d ln mR;meas þ 1Þ2 
r2 ðln mR;meas Þ þ ðmi  mi;anal Þ2 
ðd ln ci =d ln mi;anal þ 1Þ2  r2 ðln mi;anal Þ:
ð12Þ
We have mentioned before that the reason why
r(Umeas) is not used in preceding part is because that
r(Umeas) is not only related to r(ln aS,meas), but also re-
lated to r(ln mi,anal), and it is not convenient to use
r(Umeas) in error analysis. However, since the total er-
ror rT(ln aS,meas) is based on the assumption that mi,anal
be a ‘‘accurate’’ value, then we can also introduce the
corresponding total error of the measured osmotic
coefficients for the test solution expressed as rT(Umeas),
which is also based on the assumption that mi,anal be a
‘‘accurate’’ value. And there are the following
equations:
rT ðUmeas Þ ¼
mS =ðmi  mi;anal Þ  rT ðln aS;meas Þ ¼

mS =ðmi  mi;anal Þ  dflnaS;meas
ln aS ðmi;anal Þg ¼
dfUmeas
Uðmi;anal Þg; ð13Þ
2
r2T ðUmeas Þ ¼fðmR  mR;meas Þ=ðmi  mi;anal Þg 
2
ðd ln cR =d ln mR;meas þ 1Þ  r2 ðln mR;meas Þþ
2
ðd ln ci =d ln mi;anal þ 1Þ  r2 ðln mi;anal Þ: ð14Þ
In equation (13), U(mi,anal) is the theoretical value
corresponding to mi,anal on basis of equation (5) with
the assumption that mi,anal be an ‘‘accurate’’ value. It
is obvious that rT(Umeas) is the deviation of the relation-
ship of mi,anal and Umeas from the theoretical relation-
ship which also comprises both of r(ln mi,anal) and
r(ln mR,meas) and should be considered as one of error
sources of the calculated values of ci,cal. In the following
discussion, we will base on the osmotic coefficients of the
test solution, which can simplify the expression and can
be more easily understood by the readers.
746 J. Zhou et al. / J. Chem. Thermodynamics 37 (2005) 743–753

We have to emphasize that rT(Umeas) is not a physical 0; mi;anal ð1Þ; . . . ; mi;anal ðkÞ; . . . ; mi;anal ðlÞ
quantity as the normal definition about the error of the
osmotic coefficients. The normal definition of the errors 1; Umeas ð1Þ; . . . ; Umeas ðkÞ; . . . ; Umeas ðlÞ
of the osmotic coefficients is as follows:
0; mR;meas ð1Þ; . . . ; mR;meas ðkÞ; . . . ; mR;meas ðlÞ
2 2 2
r ðUmeas Þ ¼ fmS =ðmi  mi;anal Þg  r ðln aS;meas Þþ According to equation (1), there is
2 2
fðmS  ln aS;meas Þ=ðmi  mi;anal Þg  r ðd ln mi;anal Þ: Z mi;anal ð1Þ

ln ci;cal ðlÞ ¼ f1
Umeas ðlÞg þ ð1
Umeas Þ
ð15Þ 0
l Z
X mi;anal ðkÞ
d ln mi;anal þ ð1
Umeas Þ
3.2. The error sources derived from the regression of the k¼2 mi;anal ðk
1Þ
experimental data
d ln mi;anal : ð16Þ
There is another error source of the calculated activ-
ity coefficients of solute in isopiestic experiments. In 4.1. The analysis on the error of the calculated values of
practice, people usually make use of some kind of func- the activity coefficients caused by rT(Umeas)
tion of mi with unknown parameters to regress the
experimental data of Umeas, and the regressed function Since rT(Umeas) is a type of random error, according
with known parameters is then used to calculate ci,cal. to the theory of the propagation of the random errors
In this case, the deviation of the regressed function from and equation (16), we can obtain the error of the calcu-
the experimental data Umeas will also have influence on lated values of the activity coefficients caused by
the final calculated value of ci,cal, and it is expressed as rT(Umeas), which is expressed as rmeas(ln ci,cal), can be
d{Ureg(mi,anal)
Umeas}, where Ureg(mi,anal) is the re- calculated by the following equation:
gressed value corresponding to mi,anal. If the function
used to regress experimental data is theoretically abso- r2meas flnci;cal ðlÞg ¼ r2T fUmeas ðlÞgþ
lutely rigorous, d{Ureg(mi,anal)
Umeas} will be essen-
Z mi;anal ð1Þ 2
tially caused by the random errors of the experimental rT ðUmeas Þ  d lnmi;anal þ
0
data, rT(Umeas). Therefore, for many experimental data (Z )2
the influence of those deviations, d{Ureg(mi,anal)
X
l mi;anal ðkÞ

Umeas}, on the calculated values of ci,cal will cancel out
each other because of the random characteristics. And
the total influence will be very small. However, in most
cases the used regression function is not absolutely rig-
orous, and d{Ureg(mi,anal)
Umeas} will be not only
caused by the random errors of the experimental data
but also caused by the deviation of the used regression
function from the theoretically rigorous function. As a
result, the error source derived from d{Ureg(mi,anal)

Umeas} is also one of very important error sources for
the calculated values of ci,cal, and should be take into ac-
count in any cases.
There are also many other error sources in the deter-
mination of activity coefficients via isopiestic experi-
ments, such as the purity of the chemical reagent, the
precision of the temperature control. The discussions
on those factors can be found in Zhou et al. [4], Zhou
[5], and Chen et al. [6].
4. The error analysis of the calculation of the activity
coefficients in isopiestic experiments
We take there are ‘‘l’’ number of experimental points
of molality in isopiestic experiments, namely there will
be
rT ðUmeas Þ  d lnmi;anal :
k¼2 mi;anal ðk
1Þ
ð17Þ
In fact, the last sub-term in the sum and the first main
term on the right side of equation (17) are not indepen-
dent quantities. However, the dependence between these
two quantities is omitted. When the number of the
experimental molalities is more than five, this omission
should be acceptable.
1. We first examine the first main term on the right
side of equation (17).
According to equation (14), there is
r2T fUmeas ðlÞg ¼ fdlni =d ln mi;anal ðlÞ þ 1g2  r2 fln mi;anal ðlÞgþ
½mR  mR;meas ðlÞ=fmi  mi;anal ðlÞg2 
fd ln mR =d ln mR;meas ðlÞ þ 1g2 
r2 fln mR;meas ðlÞg: ð18Þ
It is obvious that rT{Umeas(l)} is determined by
r{ln mi,anal(l)} and r{ln mR,meas(l)}. Some values of
d ln ci/d ln mi for NaCl and CaCl2 and NaOH solutions
are listed in table 1.
According to table 1, we can know that the values of
d ln ci/d ln mi usually approach zero in the range of low
molality and begin to change into greater as the molality
increases in the concentrated range. For most solutions,
 J. Zhou et al. / J. Chem. Thermodynamics 37 (2005) 743–753 747

TABLE 1 solution will be greater than those of the test solution in

Some values of d ln ci/d ln mi for NaCl, CaCl2, and NaOH solutions at isopiestic equilibrium, and as a result the values of
T = 298 K
(d ln cR/d ln mR + 1) Æ (mR/mi) will have small deference
m NaCla CaCl2b CaCl2c NaOHd from those of (d ln ci/d ln mi+1). When the values of
0.03
0.0547
0.153
0.1480
0.0627 (d ln cR/d ln mR + 1) are greater than those of the test
0.1
0.0644
0.151
0.1447
0.0787 solution, the situation is similar. It is to say the compar-
0.5
0.0475 0.0252 0.0196
0.0578
0.8
0.0287 0.198 0.198
0.0258
ison magnitudes of the two main terms in the right side
1.0
0.0151 0.329 0.334
0.0007 of equation (18) are mainly determined by the values of
1.2
0.0005 0.472 0.478 0.0269 r{ln mi,anal(l)} and r{ln mR,meas(l)}. According to the
1.5 0.0231 0.702 0.708 0.0729 error theory, if we want to keep r{ln mi,anal(l)} have neg-
2.0 0.0676 1.12 1.11 0.1604 lectable influence on the result, it should be controlled to
3.0 0.177 1.99 1.97 0.370
4.0 0.319 2.83 2.86 0.620
be at least less than 1/3 of r{ln mR,meas(l)}. In practical
5.0 0.502 3.40 0.906 isopiestic experiments, r{ln mR,meas(k)} is usually from
6.0 0.737 3.44 1.224 0.3 percent to 0.1 percent, and the higher molality of
7.0 2.95 1.575 the test solution the higher less value of r{ln mR,meas(k)},
8.0 2.49 1.957 then r{ln mi,anal(l)} maybe required to be less than from
a
The values are calculated according to the equations given by 0.1 percent to 0.03 percent. Though 0.03 percent is very
Archer [3]. difficult for the chemical analysis of the test solution,
b
The values are calculated according to the equations given by
Rard et al. [7].
0.05 percent may be still necessary in most cases. It
c
The values are calculated according to the equations given by shows that the accurate chemical analysis of the molality
Phutela and Pitzer [8]. of the test solution is important to the determination of
d
The values are calculated according to the equations given by the activity coefficients via isopiestic experiments. When
Simonson et al. [9]. r{ln mi,anal(l)} is always controlled to be less than 1/3 of
r{ln mR,meas(l)}, r{ln mi,anal(l)} could be neglected and
the biggest values of d ln ci/d ln mi are usually less than equation (18) could be changed into
2.5 (the biggest value of 3.5 for CaCl2 is very large in
2
comparison the most other solutions). And some values r2T fUmeas ðlÞg  ½mR  mR;meas ðlÞ=fmi  mi;anal ðlÞg 
of the several quantities in isopiestic equilibrium for 2
fd ln cR =d ln mR;meas ðlÞ þ 1g 
NaCl and CaCl2 and NaOH solutions are listed in table
2, where NaCl and CaCl2 are reference standard solu- r2 fln mR;meas ðlÞg: ð19Þ
tions, and NaOH is the test solution.
According to table 2, we can find that, in general We have mentioned that for most solutions the values of
speaking when the values of (d ln c/d ln m + 1) of the ref- d ln ci/d ln mi are usually in the range from ±0 to 2.5, and
erence standard solution (R) are smaller than those of the deference between (d ln cR/d ln mR+1) Æ (mR/mi)
the test solution, the molalities of the reference standard and (d ln ci/d ln mi+1) in isopiestic equilibrium is small;

TABLE 2
Some values of the several quantities in isopiestic equilibrium for (NaCl and CaCl2) (reference standard solutions) and NaOH (test solution) systema
m(NaOH) (d ln c/d ln m + 1) m(NaCl) (d ln c/d ln m + 1) m(NaCl)/m(NaOH) m(CaCl2) (d ln c/d ln m + 1) 3 Æ m(CaCl2)/{2 Æ m(NaOH)}
(NaOH) (NaCl) (CaCl2)
0.1 0.921 0.1003 0.936 1.003 0.07285 0.842 1.093
1 0.999 1.012 0.986 1.012 0.6637 1.115 0.996
2 1.160 2.046 1.072 1.023 1.218 1.485 0.914
4 1.620 4.216 1.355 1.054 2.197 2.286 0.824
6 2.224 6.548 1.892 1.091 3.140 3.116 0.785
8 2.957 4.116 3.911 0.772

m(NaOH) {(d ln c/d ln m + 1)(NaCl)} Æ [{(d ln c/d ln m + 1)(CaCl2)}Æ3Æm(CaCl2)/{2 Æ m(NaOH)}]/

{m(NaCl)/m(NaOH)}/{(d ln c/d ln m + 1)(NaOH)} [(d ln c/d ln m + 1)(NaOH)]
0.1 1.019 0.999
1 0.999 1.112
2 0.945 1.170
4 0.882 1.163
6 0.928 1.100
8 1.021
a
The isopiestic molality ratios are calculated basing on the osmotic coefficient equations for NaCl, CaCl2 and NaOH solutions given by Archer
748 J. Zhou et al. / J. Chem. Thermodynamics 37 (2005) 743–753
therefore, the values of (d ln cR/d ln mR+1) Æ (mR/mi) for
most isopiestic measurements would be in the range
from 1 to 3.5. For some solutions with small values of
d ln ci/d ln mi, to further simplify the situation, we can
even omit the term of [mR Æ mR,meas(l)/{mi Æ mi,anal (l)}]2 Æ
{d ln cR/d ln mR,meas(l)+1}2 in equation (19), and equa-
tion (19) further becomes a more approximate equation
as follows:
r2T fUmeas ðlÞg  r2 fln mR;meas ðlÞg: ð20Þ
According to equation (17), the first main term shows
that rmeas{ln ci,cal(l)} is relevant to rT{Umeas(l)} directly,
and it further indicates that in all molality range each
rmeas{ln ci,cal(k)} will also relevant to each rT{Umeas(k)},
respectively. It is to say if the error of one of the mea-
surements of the osmotic coefficients is much larger than
the others, the error of the corresponding value of
rmeas(ln ci,cal)} will also be much larger than the others.
Therefore, if we intend to obtain the calculated values
of ci,cal with the similar errors in all molality range, it
is preferable to keep rT{Umeas(k)} changeless in all isopi-
estic experiments including those experiments on the
very dilute solutions. According to equation (19) we
can then design the values of r{ln mR,meas(k)} before
isopiestic experiments to prevent rT{Umeas(k)} from
changing too much for all different molalities, and
r{ln mR,meas(k)} should be controlled smaller in the
range of high molalities than in the range of low molal-
ities in isopiestic experiments. Moreover, after isopiestic
experiments we can calculate the actual values of
rT{Umeas(k)} from the actual values of r{ln mR,meas(k)}
on the base of equation (19). According to equation
(20), in some rough cases, we can simply control
r{ln mR,meas(k)} changeless and roughly consider
rT{Umeas(k)} equal to r{ln mR,meas(k)}.
2. We then examine the second main term on the right
side of equation (17).
If we assume that rT(Umeas) keep constant during the
integrating process from 0 to mi,anal(1), we will find that
the total error of this term will become infinite however
small is the value of rT(Umeas). This indicates that:
Firstly, the isopiestic experiments on the dilute solutions
are very important to the determination of the solute
activity coefficients. And the isopiestic experiments
should be done not only at as low molalities as possible
but also with as high precision as possible; Secondly, at
however low molalities the isopiestic experiments can be
made, it is still necessary to require a theoretical method
to calculate the osmotic coefficients from 0 mol Æ kg
1 to
the lowest molality mi,anal(1); Thirdly the lowest molality
mi,anal(1) should be low enough so that the theoretical
method can be used and the errors of the calculated os-
motic coefficients by that theoretical method from 0 to
mi,anal(1) will decrease as the molality lower, for example
is in reciprocal proportion to the molality. This kind of
errors of the osmotic coefficients can ensure that the
integral of the second main term in equation (17) be a
finite value.
Since many advanced theoretical method have been
established which can be applied in concentrated solu-
tions, some workers begin to incline to pay less and less
attention on the dilute solution in isopiestic experiments.
However, the calculated values of the osmotic coeffi-
cients for the low molalities by the theoretical method
just basing on the experimental data for the high molal-
ities will be not reliable, and the experiments on the di-
lute solution is still necessary to reliably determine the
experimental parameters corresponding to the low mol-
alities in the theoretical method. Thereafter, the osmotic
coefficients at the low molalities can be calculated reli-
ably by the theoretical method.
As we know, Debye–Huckel equation is a pure theo-
retical method which can be only applies to very dilute
solutions, and the extended Debye–Huckel equation
with one experimental parameter will be applied to
broader range of molalities. For a single electrolyte,
MX, the extended Debye–Huckel equation with one
experimental parameter can be expressed as follows:
U
1 ¼
jzM  zX j  AU  I 1=2 =ð1 þ b  I 1=2 Þþ
B  m  ð2  mM  mX =mMX Þ; ð21Þ
ln c ¼
jzM  zX j  AU  fI 1=2 =ð1 þ b  I 1=2 Þþ
2=b  lnð1 þ b  I 1=2 Þg þ 2  B  m  ð2  mM  mX =mMX Þ;
ð22Þ
where AU is the Debye–Huckel parameter, and b is a
universal parameter with the known value, and I is the
ionic strength, and mM and mX are the numbers of cations
and anions in the formula MX, and zM and zX are the
charges on ions of M and X, respectively. And B is
the only experimental parameter which is specific to
the solute MX, and it can be determined by the experi-
mental osmotic coefficient of the molality of mi,anal(1).
For most theoretical methods, the extended Debye–
Huckel equation is usually included in and various
forms of higher order terms of the molality are added
in. It is obvious that the experimental parameter B is
corresponding to the low molalities in most theoretical
methods. Therefore, whether equation (21) or equation
(22) is valid in the range from 0 to mi,anal(1) with enough
precision is a criterion to decide down to what kind of
low molality the isopiestic experiments should be done
on the electrolyte solutions in the determination of the
activity coefficient of solution. Moreover, the errors of
the calculated osmotic coefficients for the molality form
to mi,anal(1) by equation (21) basing on the experimental
data may be in reciprocal proportion to the molality.
equations (21) and (22) are in fact equivalent to the
equations proposed by Guggenheim and Turgeon [10].
As Guggenheim and Turgeon
s statement their equa-
tions represent the facts with a useful degree of accu-
 J. Zhou et al. / J. Chem. Thermodynamics 37 (2005) 743–753
racy, at least for uni-univalent, bi-univalent, and uni-
bivalent electrolytes up to an ionic strength of about
0.1 [10,11]. Therefore we consider that it is necessary
that the isopiestic experiment should be done on the test
solutions of lower than 0.1 mol Æ kg
1; and it is prefera-
ble to require as low molalities as less than 0.5
mol Æ kg
1, up to which we think equation (21) could
be valid with enough accuracy for most electrolyte solu-
tions, and the higher is the valence of the electrolytes,
the lower is the molality of the test solution.
On the base of equation (21), we can obtain the fol-
lowing equation:
Z mi;anal ð1Þ
ðUmeas
1Þ  d ln mi;anal ¼

0 On the basis of equations (26), equations (25) should
jzM  zX j  AU  ð2=bÞ  lnð1 þ b  I 1=2 Þþ
B  mi;anal ð1Þ  ð2  mM  mX =mMX Þ: ð23Þ
Since the first main terms in the right side of equa-
tions (21) and (23) are pure theoretical values and will
be accurate, the error of the experimental osmotic coef-
ficient of the molality of mi,anal(1) will only influence the
value of the specific experimental parameter B. There-
fore, basing on equations (21) and (23), we could deduce
that the error of the second main term of equation (17)
as follows:
Z mi;anal ð1Þ
rT ðUmeas Þ  d ln mi;anal ¼
0
rfB  mi;anal ð1Þ  ð2  mM  mX =mMX Þg ¼
rT fUmeas ð1Þg: ð24Þ
3. We continue to examine the third main term on the
right side of equation (17).
We assume that rT(Umeas) keep constant and the
same as that at the end point during the integration in
each integral term included in the sum in equation
(17). Then the third main term would be change into
the following form:
(Z )2
X l mi;anal ðkÞ
rT ðUmeas Þ  d ln mi;anal ¼
k¼2 mi;anal ðk
1Þ
X
l
r2T fUmeas ðkÞg
2
 fln mi;anal ðkÞ
ln mi;anal ðk
1Þg :
k¼2
ð25Þ
It is preferable to require that each term included in the
sum in equation (25) have the equal influence on the cal-
culated activity coefficients according to equation (17),
namely rT{Umeas(k)} Æ {ln mi,anal(k)
ln mi,anal(k
1)}
should be kept equal for each term in the sum. It is obvi-
ous that if one of term is much larger than the others,
the total result will be determined by that term and
the other terms will be valueless. Since rT{Umeas(k)}
should be also kept nearly changeless for all different
molalities in isopiestic experiments as stated in part 1
749
of section 4.1, we then naturally deduce that the exper-
imental molalities of the test solutions should be ar-
ranged approximately according to the following rule:
ln mi;anal ðkÞ
ln mi;anal ðk
1Þ ¼
fln mi;anal ðlÞ
ln mi;anal ð1Þg=ðl
1Þ: ð26Þ
Namely
1=ðl
1Þ
mi;anal ðkÞ=mi;anal ðk
1Þ ¼ fmi;anal ðlÞ=mi;anal ð1Þg :
ð27Þ
This rule shows that the experimental molalities
should be very closely spaced for the dilute solutions
and very widely spaced for the concentrated solutions.
forward to become
(Z )2
Xl mi;anal ðkÞ
rT ðUmeas Þ  d ln mi;anal ¼
k¼2 mi;anal ðk
1Þ
2
r2T fUmeas ðkÞg  fln mi;anal ðlÞ
ln mi;anal ð1Þg =ðl
1Þ:
ð28Þ
According to equations (17) and (28) it is easy to find
that the more number of the experimental molalities is,
the less error of the calculated activity coefficients would
be. For a practical example, mi,anal(1) and mi,anal(l) are
taken to be 0.03 mol Æ kg and 15 mol Æ kg
1, respectively,
and in the same time the values of rT{Umeas(k)} are kept
in nearly changeless for all different molalities in isopies-
tic experiments. If we want to reduce the value of the
third main term on the right side of equation (17) and
to make it less than 1/10 of the value of the other main
terms, according to equations (17) and (24) and (28) the
number of the experimental molalities should be about
387. And in this case, the error of the calculated activity
coefficient will be approximately related to rT{Umeas(k)}
only.
4.2. The analysis on the error of the calculated values of the
activity coefficients caused by d{Ureg(mi,anal)
Umeas}.
Below we will discuss the influence of the deviation of
the regressed function from the experimental data,
namely d{Ureg(mi,anal)
Umeas}. On the base of equation
(16), we can obtain the error of the calculated values of
the activity coefficients caused by d{Ureg(mi,anal)

Umeas}, which is expressed as rreg(ln ci,cal), can be calcu-
lated by the following equation:
rreg fln ci;cal ðlÞg ¼d½Ureg fmi;anal ðlÞg
Umeas ðlÞgþ
Z mi;anal ð1Þ
dfUreg ðmi;anal Þ
Umeas g
0
l Z
X mi;anal ðkÞ
d ln mi;anal þ dfUreg ðmi;anal Þ

k¼2 mi;anal ðk
1Þ
Umeas g  d ln mi;anal ð29Þ
750 J. Zhou et al. / J. Chem. Thermodynamics 37 (2005) 743–753
We also assume that d{Ureg(mi,anal)
Umeas} keeps
constant and the same as that of the end point during
the integration in each integral term included in
the sum in equation (29). Similar to the deduction in
section 4.1, we can obtain that the relative error
of the calculated activity coefficients caused by
d{Ureg(mi,anal)
Umeas} can be calculated by the follow-
ing equation:
rreg fln ci;cal ðlÞg ¼ d½Ureg fmi;anal ðlÞg
Umeas ðlÞþ
d½Ureg fmi;anal ð1Þg
Umeas ð1Þþ
X l
d½Ureg fmi;anal ðkÞg
Umeas ðkÞ
k¼2
fln mi;anal ðkÞ
ln mi;anal ðk
1Þg:
According to the regression theory the magnitude
of d{Ureg(mi,anal)
Umeas} will be related to not only
the form of the used function but also related to the
way of the arrangement of the experimental data,
namely the arrangement of the molalities of the test
solutions in isopiestic experiments. In generally speak-
ing, for a linear regression function, d{Ureg(mi,anal)

Umeas} will be less in the region where the experimental
molalities are arranged closely than those in the region
where the experimental molalities are arranged more
widely. If we increase the number of the experimental
molalities in one region, the values of d{Ureg(mi,anal)

Umeas} in this region will be reduced. In most cases,
the used regression function is series power function of
molality, namely m, m2, m3,. . ., and the unknown
parameters are essentially linear coefficients with re-
spect to those series power terms of ‘‘m’’. When the
experimental molalities are arranged according to
equation (26) or equation (27), namely very closely
for dilute solutions and very widely for concentrated
solutions with respect to the series power terms of
‘‘m’’, the deviation d[Ureg {mi,anal(k)}
Umeas(k)]
would be much greater in the range of high molalities
than those in the range of low molalities according to
the theory of regression. As a result, the values of the
hind terms included in the sum in equation (30) would
be much greater than those of the fore terms and
would have much greater influence on the result. If
we want to reduce the influence of the hind terms,
we should arrange the more number of experimental
molalities in the range of high molality than that ar-
ranged according to equation (26) or equation (27).
According to the practical experience, we proposed
to arrange the experimental molalities, mi,anal(k 0 ),
which are greater than 1 mol Æ kg
1, according to the
following rule:
mi;anal ðk 0 þ 1Þ
mi;anal ðk 0 Þ ¼
ðk 0
k 0 þ 1Þ  fmi;anal ðk 0 Þ
mi;anal ðk 0
1Þg;
where mi,anal(k0) is the first experimental molality which
is greater than 1 mol Æ kg
1. And the experimental mol-
alities would be spaced more closely than those ar-
ranged according to equation (26) or equation (27).
In practical experiments, we could first arrange the
experimental molalities according to equation (26) or
equation (27), and then adjust those experimental mol-
alities which are greater than 1 mol Æ kg
1 according to
equation (31).
4.3. The calculation of the error of the calculated activity
coefficients in isopiestic experiments
On the base of equations (17) and (24) and (25), we
ð30Þ can calculate the errors of the activity coefficients
rmeas{ln ci,cal(l)} caused by rT{Umeas(k)} with the follow-
ing equation:
r2meas fln ci;cal ðlÞg ¼
X
l
r2T fUmeas ðlÞg þ r2T fUmeas ð1Þg þ r2T fUmeas ðkÞg
k¼2
2
fln mi;anal ðkÞ
ln mi;anal ðk
1Þg ; ð32Þ
where rT{Umeas(k)} can be calculated by equation (18)
or equation (19) with r{ln mi,anal(k)} and r{ln mR,meas(k)},
sometimes can be estimated by equation (20) with
r{ln mR,meas(k)}. On the base of equation (30) we can
also calculate another kind of errors rreg{ln ci,cal(l)}
caused by d[Ureg{mi,anal(k)}
Umeas(k)]. And the total
relative error of the determined activity coefficients,
rT{ln ci,cal(l)}, which is calculated by the regressed
function corresponding to the molality mi,anal(l), should
consist of rmeas{ln ci,cal(l)} and rreg{ln ci,cal(l)} and could
be calculated by the following equation:
r2T fln ci;cal ðlÞg ¼ r2meas fln ci;cal ðlÞg þ r2reg fln ci;cal ðlÞg:
ð33Þ
According to these equations, we will find that the
higher is the molality mi,anal(l) the greater is the error
rT{ln ci,cal(l)}.
Regarding to the errors of calculated activity coeffi-
cients by the regressed function, rT{ln ci,cal(mi)}, corre-
sponding to the molalities mi which are different from
these experimental molalities mi,anal(l), we can also
calculate them by the following steps. Firstly, we can esti-
mate the total errors of the measured osmotic coefficients
corresponding to mi,rT{Umeas(mi)}, by rT{Umeas(l 0
1)}
and rT{Umeas(l 0 )}, the molalities of which mi,anal(l 0
1)
and mi,anal(l 0 ) are located two sides of mi. Secondly,
we can calculate the errors of the activity coefficients
caused by the measurements, rmeas{ln ci,cal(mi)}, by the
ð31Þ following equation:
 J. Zhou et al. / J. Chem. Thermodynamics 37 (2005) 743–753 751

r2meas fln ci;cal ðmi Þg ¼ r2T fUmeas ðmi Þg þ r2T fUmeas ð1Þgþ
X
l0
1
r2T fUmeas ðkÞg  fln mi;anal ðkÞ

k¼2
2 determined by both of r{ln mi,anal(k)} and
ln mi;anal ðk
1Þg þ r2T fUmeas ðmi Þg
2 r{ln mR,meas(k)} according to equation (18) and
fln mi
ln mi;anal ðl0
1Þg :
Thirdly, we can also estimate the regression deviation
from measured osmotic coefficients corresponding to mi,
d{Ureg(mi)
Umeas} by d[Ureg{mi,anal(l 0
1)}
Umeas
(l 0
1)] and d[Ureg{mi,anal(l 0 )}
Umeas(l 0 )]. Fourthly,
we can calculate the errors of the activity coefficients
caused by the regression deviation from the experimen-
tal data, rreg{ln ci,cal(mi)}, by the following equation:
rreg fln ci;cal ðmi Þg ¼ d½Ureg fmi g
Umeas  þ d½Ureg fmi;anal ð1Þg

X
l0
1
Umeas ð1Þ þ d½Ureg fmi;anal ðkÞg

k¼2
Umeas ðkÞ  fln mi;anal ðkÞ

ln mi;anal ðk
1Þgd½Ureg fmi g
Umeas 
fln mi
ln mi;anal ðl0
1Þg:
And rT{ln ci,cal(mi)} could be calculated by the fol-
lowing equation:
r2T fln ci;cal ðmi Þg ¼ r2meas fln ci;cal ðmi Þg þ r2â fln ci;cal ðmi Þg:
4.4. A practical example of the determination of activity
coefficients via isopiestic experiments
The electrolyte is taken to be uni-univalent, and the
total relative error of the determined activity coeffi-
cients, namely rT(ln ci,cal), are attempted to be obtained
about 2.1 percent from 0 mol Æ kg
1 to 15 mol Æ kg
1.
(1) On the base of the analyses in part 2 of section 4.1,
for the uni-univalent electrolyte solutions in the
range of molality below 0.03 mol Æ kg
1 the activity
coefficients are able to be calculated by the extended
Debye–Huckel equation with enough accuracy.
Therefore, the isopiestic experiments can be made
from 0.03 mol Æ kg
1 to 15 mol Æ kg
1.
(2) If we assume that the error of the activity coefficient
rmeas{ln ci,cal(l)} caused by rT{Umeas(k)} is equal to
the error rreg{ln ci,cal(l)} caused by d[Ureg
{mi,anal(k)
Umeas(k)}] in equation (33), we can
obtain that rmeas{ln ci,cal(l)} and rreg{ln ci,cal(l)}
should be controlled to be about 2.1/21/2 = 1.5 per-
cent, respectively.
(3) As discussed in part 1 of section 4.1, rT{Umeas(k)} is
ð34Þ should be controlled nearly changeless in all isopi-
estic experiments. In practical isopiestic experi-
ments, r{ln mi,anal(l)} is kept less than 0.05 percent
and therefore would have neglectable influence on
rT{Umeas(k)}. If we assume that d ln ci/d ln mi,anal(k)
for the test solution change from 0 to 2.5, we can
then adjust r{ln mR,meas(k)} between 0.3 percent
to 0.1 percent and the higher molality of the test
solution the higher less value of r{ln mR,meas(k)}
according equation (19) to make rT{Umeas(k)} to
be about 0.5 percent in all molality range.
(4) The discussion in part 3 of section 4.1 shows that
the experimental molalities of the test solutions
should be arranged approximately according to
equation (26) or equation (27). If we attempt to
ð35Þ obtain rmeas{ln ci,cal(l)} to be about 1.5 percent,
according to equations (25) and (28) and (32) the
number of the experimental molalities could be esti-
mated to be 7, and the experimental molalities
could be arranged as table 3.
(5) In order to reduce the deviation of the regression
ð36Þ
values of the osmotic coefficients from the experi-
mental values in the range of high molalities, the
experimental molalities greater than 1 mol Æ kg
1
are adjusted according to equation (31) as discussed
in section 4.2. And the experimental molalities are
finally arranged as showed in table 4.
(6) After isopiestic experiments, we can calculate actual
values of rT{Umeas(k)} by equation (19) with the
actual experimental data of r{ln mR,meas(k)}. Then
we can forward calculate the actual values of
rmeas{ln ci,cal(l)} by equation (32). When the exper-
imental osmotic coefficients are regressed by a the-
oretical model, we can also calculate another kind
of errors rreg{ln ci,cal(l)} caused by the actual values
of d[Ureg{mi,anal(k)
Umeas(k)}] on the base of
equation (30). And the total relative error of the
determined activity coefficients, rT(ln ci,cal), could
be calculated by equation (33).
The experimental design on the basis of the error
analysis has been applied in our research. The research

TABLE 3
The experimental molalities from 0.03 mol Æ kg
1 to 15 mol Æ kg
1 arranged according to equation (26)
k 1 2 3 4 5 6 7
mi(k) 0.03000 0.08452 0.2381 0.6708 1.890 5.324 15.000
ln mi(k)
3.5066
2.4708
1.4350
0.3993 0.6365 1.6723 2.7081
752 J. Zhou et al. / J. Chem. Thermodynamics 37 (2005) 743–753
TABLE 4
The experimental molalities from 0.03 mol Æ kg
1 to 15 mol Æ kg
1
arranged according to equations (26) and (31)
k mi(k) ln mi(k) mi(k + 1)
mi(k)
1 0.03000
3.5066
2 0.08452
2.4708
3 0.2381
1.4350
4 0.6708
0.3993 1.2191
5 1.890 0.6365 1.2191
6 3.109 2.438
7 5.547 3.657
8 9.204 4.876
9 14.080 6.095
10 20.176
is presented in Zhou et al. [12], and the satisfied results
have been obtained.
5. Conclusion
On the basis of the error analysis of the determina-
tion of activity coefficients via the isopiestic method,
we could conclude the following views:
(1) The experimental error is one of important error
sources of the determination of the activity coeffi-
cients via the isopiestic method.This kind of error
includes the experimental errors of the molalities
and the activities of the solvent for the test
solution, namely r(ln mi,anal) and r(ln aS,meas),
and r(ln aS,meas) is determined by the error of
the measured molality of the standard reference
solution r(ln mR,meas) in the isopiestic experi-
ment. In fact, the factor which will finally and
actually influence r(ln ci,cal) is the deviation of
the relationship of the experimental values, mi,anal
and aS,meas, from the theoretical relationship,
d{ln aS,meas
ln aS(mi,anal)}, which comprises both
of r(ln mi,anal) and r(ln mR,meas) and could be con-
sidered as a type of total error source expressed as
rT(ln aS,meas). This total error source can be equiv-
alently expressed in the deviation of the relation-
ship of mi,anal and Umeas from the theoretical
relationship rT(Umeas) = d{Umeas
U(mi,anal)},
which is not an error as normal definition.When
a theoretical method is used to regress the exper-
imental data, the deviation of the regression func-
tion from the experimental data, d{Ureg
(mi,anal)
Umeas}, is also one of important error
sources of the determination of the activity coeffi-
cients via the isopiestic method.
(2) The accurate chemical analysis of the molality of
the test solution is important to the determination
of the activity coefficients via isopiestic experi-
ments. In most isopiestic experiments it requires
r(ln mi,anal) less than 0.05 percent to made
r(ln mi,anal) have neglectable influence on the
result.If so, rT(Umeas) could be determined only
by r(ln mR,meas) according to equation (19) in most
cases.In more roughly situation, rT(Umeas) could
be considered to equal to r(ln mR,meas) according
to equation(20). In all isopiestic experiments, it is
preferable to keep rT(Umeas) changeless including
those experiments on the very dilute solutions. In
accordance, r(ln mR,meas) should be controlled
smaller in the range of high molalities than in
the range of low molalities in isopiestic
experiments.
(3) The isopiestic experiments should be done at as
low molalities as possible. And in any cases it is
still necessary to require a theoretical method to
calculate the osmotic coefficients from 0 to the
lowest molality. The lowest molality should be
low enough so that the theoretical method can
be used and the errors of the calculated osmotic
coefficients by that theoretical method from 0 to
the lowest molality will decrease as the molality
lower. And it is necessary that the isopiestic
experiment should be done on the test solutions
of lower than 0.1 mol Æ kg
1. For most electro-
lytes solutions, it is usually preferable to require
the lowest molality to be less than 0.05
mol Æ kg
1.
(4) In all isopiestic experiments, the experimental mol-
alities of the test solutions, mi, should be firstly
arranged approximately according to the rule
which is to keep ln mi,anal(k + 1)
ln mi,anal(k)
nearly constant, and the more number of the exper-
imental molalities is, the less error of the calculated
activity coefficients would be. Secondly, to reduce
the deviation d[Ureg{mi,anal(k)}
Umeas(k)] in the
range of high molalities, more number of high mol-
alities should be arranged according to practical sit-
uation. We propose to arrange the experimental
molalities greater than 1 mol Æ kg
1 according to
mi,anal(k 0 + 1)
mi,anal(k 0 ) = (k 0
k0 + 1) Æ {mi,anal
(k0)
ln mi,anal(k0
1)}, where mi,anal(k0) is the first
experimental molality which is great than 1
mol Æ kg
1.
(5) After isopiestic experiments, we can calculate
actual values of rT{Umeas(k)} by equation (19)
with the actual experimental data of
r{ln mR,meas(k)}. Then we can forward calculate
the actual values of rmeas{ln ci,cal(l)} by equation
(32). When the experimental osmotic coefficients
are regressed by a theoretical model, we can also
calculate another kind of errors rreg{ln ci,cal(l)}
caused by the actual values of d[Ureg{mi,anal(k)

Umeas(k)}] on the base of equation (30). And the
total relative error of the determined activity
coefficients, rT(ln ci,cal), could be calculated by
equation (33).
 J. Zhou et al. / J. Chem. Thermodynamics 37 (2005) 743–753
Acknowledgements
We express our great thanks to the anonymous
reviewers and the editor professor J.P. Martin Trusler
for their thorough reviews and useful comments. Their
work has given me a great help in preparing the final
version. We should also express our sincere thanks to
Xia Zhou for her kindly help in editing. This research
is supported by the National Priority Development
Project Fundamental Research (Project number:
G1999064902) and China Postdoctoral Science Founda-
tion in Central South University.
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JCT 04-105