A-264

J. Chm. Thrmwdwumics 1982. 14. 613-638

Thermodynamics of aqueous carbonate

solutions including mixtures of
sodium carbonate, bicarbonate, and
chloride
J. CHRISTOPHER PEIPER and KENNETH S. PITZER
Department of Chemistry and Lawrence Berkeley Laboratoty,
University qf California, Berkeley, CA 94720, U.S.A.

(Received 2X May I981 ; in revised form 30 September 1981)

Recently the authors examined electrochemical-cell data leading to values of the activity
coefficient for aqueous sodium bicarbonate. Since that preliminary analysis, new experimental
measurements have been published which contribute signifmantly to the overall thermodynamic
understanding of (sodium carbonate + sodium bicarbonate + carbonic acid). In this more
extensive examination we consider a wide variety of measurements leading to activity
coefficients of Na,CO, and NaHCO, from 273 to 323 K and to relative molar enthalpies and
heat capacities at 298.15 K. Tables of thermodynamic quantities at selected temperatures are
included.

1. Introduction
Measured thermodynamic properties of aqueous solutions of Na,CO, and NaHCO,
cannot be interpreted in the samestraightforward manner applicable to simple strong
electrolytes. The presence of the equilibria :

CO:-(aq)+H,O(l) = HCO;(aq)+OH-(aq),
(1)
2HCO;taq) = CO:-(aq)+CO,(g)+H,O(l),
requires that even stoichiometrically single-solute solutions be treated as mixed
electrolytes. In addition, the presence of doubly and singly charged anions implies
that the electrostatic effects of asymmetric mixing be incorporated into any complete
analysis of experimental results. Thus, a full interpretation of the carbonate system
becomesquite complex.
While the aqueous solutions of sodium carbonate and bicarbonate themselves are
of considerable importance, naturally occurring solutions include these ions among a
wider array of other ions.(1.2) Chloride is especially common and is included in this
study. But sulfate, magnesium, potassium, and calcium are often present with smaller
concentrations of other species.The parameters of this study are determined within a
general formalism which is applicable to mixed electrolytes of unlimited complexity.
Thus, the present results for sodium carbonate and bicarbonate may be combined
with corresponding parameters for other ions to predict the properties of a wide range
of natural and artificial solutions.
614 J. C. PEIPER AND K. S. PITZER

A further objective of this study is to demonstrate the modeling of a complex

mixture of weak and strong electrolytes within the framework of Pitzer’s ion
interaction theory. (3’ This theory was originally formulated for single-solute solutions
of strong electrolytes at 298.15 K.‘4’ and at high temperature,‘“’ but was subsequently
expanded to include mixtures of strong electroiytes,‘h’ and higher-valence-type
electrolytes. (‘.*i Aqueous H,P04,‘9) and H,S04,“o’ were successfully treated as
solutions with a single ionization equilibrium. The carbonate solutions considered
herein are more complex in having two reactions at equilibrium. Also, we self-
consistently treat enthalpies and heat capacities as well as measurements leading to
activity and osmotic coefficients.
The experimental data here considered include the e.m.f. measurements of Harned
and Davis” ‘) and Harned and Bonner t12, which formed the basis of our earlier report
on sodium bicarbonate.‘13’ These concern the cell:

WW2k), C02kWaCUml L NaHCWm2)3 CO,(m,)lAgCl(s)lAg(s), (21

with reaction :
fH,(g)+AgCl(s)+HCO;(aq) = Cl-(aq)+Ag(s)+H,O(l)+CO,(g). (3)
Recently, Roy et al. ‘14) have made additional measurements for the same
electrochemical cell but at significantly higher molalities of NaHCO, and NaCl.
The activity coefficient of Na,CO, is obtainable at low molalities from the work of
Harned and Scholes,“5’ who measured the potentials of similar cells with solutions
containing NaCl, NaHCO,, and Na,CO,, and without CO,(g). The cell reaction for
these measurements is
fH,(g)+AgCl(s)+CO:-(aq) = Cl-(aq)+HCO;(aq)+Ag(s). (4)
Robinson and Macaskillo6’ have recently measured the activity of water above
sodium carbonate solutions at 298.15 K and to 3.0 mol.kg-’ by an isopiestic
method. Their determinations are supplemented by similar measurements on (sodium
carbonate + sodium chloride) by White and Bates.“”
For the enthalpies of these systems we adopt the recent results of Berg and
Vanderzee.‘r8i These authors measured the enthalpy of dilution of sodium carbonate
and sodium bicarbonate solutions at 298.15 K, and corrected their measurements for
enthalpic effects arising from equilibrium (1). Heat capacities for these solutions have
been measured by Perron, Desnoyers, and Miller0 ‘19’ at 298.15 K, who report results
for other systems as well.
Older data for aqueous sodium carbonate are listed and evaluated by Goldbergtzo’
in his review. It did not appear to us that any of these data would contribute
significantly to our analysis; hence for simplicity they were omitted. Goldberg’s
analysis for sodium carbonate ignored the hydrolysis equilibrium above.

2. Equations
We adopt the ion interaction or virial coefficient equations for mixed electrolytes
introduced by Pitzer and Kim. (6) These authors were able to represent quite
 THERMODYNAMICS OF AQUEOUS CARBONATE SOLUTIONS 615

accurately the experimental activity and osmotic coefficients for some 60 aqueous
solutions with and without a common ion. Recently, Harvie and WeareJ2” in an
extensive study of complex seawater-related mixed-electrolyte solutions have also
found these equations to be very satisfactory.
It is convenient to begin with the excess Gibbs energy G’” divided by the mass u’, of
solvent, GeX/w,; equation (5) is written in the form used in a recent review,‘22’ but is
equivalent to the expressions of Pitzer and Kim and of Harvie and Weare.
G’“Iw,RT = f+2 1 m,m,{B,~,+(Cmz)C,,,j

+‘~m,m,,(e,,,,+~~m,~,,,,,~)+ C m,m,,(e,,,,+fCm,ll/,,,.,.), (5)

c. c’ a a.a’ c
where
f= - (41/b& ln( 1 + bl”‘),
B = jf$~~+flc!~(2/a2Z){ 1 -(I +Cr11.‘2)exp(-Ct11’2)),
c::: = q?,/2~z,41~~.
The quantities B,,, and C,,, are the second and third virial coefficients for the
electrolyte ca, fis the appropriate DebyeeHtickel function with parameter A, (of SI
unit: kg”’ .mol- 1’2), and w, is the mass of water in the solution. The empirical
parameters b and M have the values 1.2 kg”‘. mol -“2 and 2.0 kg112 .rnol ‘j2,
respectively, for all solutions here considered. The summations are over all cations
(c, c’) and anions (a, a’) with the quantity (Emz) = Cm,z, = CmaJzal, where mi and zi
represent the ionic molality and charge. The 8i.j are second virial coefficients
representing the difference in averaged interactions of unlike ions with charges of the
same sign from the appropriate average for like ions. The ~i,j,k are third virial
coefficients similarly defined but for three ions with charges not all of the same sign.
These terms are discussed more fully by Pitzer and Kim. Finally 1 represents the
molality-based ionic strength, and R, T retain their usual meanings.
Equation (5) defines a Gibbs energy in excess of that for an ideal solution of the
same composition. Ordinarily one obtains the ideal solution by a simple dilution
process; in this case the equilibria (1) must be frozen during the dilution. Otherwise,
for the real solution, this process involves the interconversion of some small amount
of solute due to the composition dependence of (1). Our analysis for a carbonate
solution always involves determination of the equilibrium composition and
subsequent evaluation of a non-ideality term related to equation (5).
In anticipation of the activity-coefficient ratios required in the analysis of e.m.f.‘s
from the laboratories of Harned and of Roy, we present equations (6) and (7).
Equation (6) is merely equation (17) of Pitzer and Kim’s report, rewritten here in
explicit form for solutions containing Na,CO,, NaHCO,, NaOH, and NaCl.
Equation (7) may be derived from equation (15) of Pitzer and Kim by appropriate
combination of mean ionic activity coefficients.

= 2 In YNCI - 2 In YN~HCO,
= 2mNa(BNa, cl - BNa. HCO, )+ 2m&(CNa. Cl - cNa. HCO, )
616 J. C. PEIPER AND K. S. PITZER

+w,i-0, -mCl)6HC0,.CI +*Na@HCO, - %)+N:,. HCO,.CI

+2mC0,(eC0,.Cl -~CO,.HCO,)+nlNamCO,(rl/N,.CO,.CI -~~N.I.CO,.HCO,)

+2mO,~eOH,C,-8HCO,,,~,,~+mN,mOH~~N,.,,H.,,-~N,.,,CO,.,,~,~~ (6)

1n(~HCO&/~‘C03)

= 2 In YN~HCO, + 2 In YNaCl - 3 In ?Na,CO

= 24{1”‘/(1 +b1”‘)+(2/b)ln(l +b1’12)1
+ 2mNa(BNa. HCO, + BNa. Cl - BNa. CO3 )+ 2n1ki(CN,. HCO, + cNa, Cl - cN,, CO,)

- 2mNci(mC0,BNa,C0, +mHCO,gNa, HCO, +mO”BNa,OH + mC,BNa,Cl)

+2~~C0,~~C0,.HC0,+eCO~.Cl~+n~NamC0,~~Na.C0,. HCO,+ +Na.CO,.CI)

+ 2mHC0,(eHC0,. Cl -‘CO,, HCO,)+n*Nan*HCO,(~Na. HCO,,CI - @Nd.COt. HCO,)

+ 2mOH(8HC0,. OH + ‘OH.Cl - ‘CO,. OH)

+ mNamOH(+Na. HCO,. OH + +Na. OH, Cl - Ic/Na. CO,.OH)

+ 2mCl(eHC0,. CI - ‘CO,. Cl) + mNa%(I(/Na. HCO,. Cl - +Na. CO,. Cl)

-2mC03(mHC03+mOH+mC~)t~2.1~ 17)

The charge has been omitted from all ionic species appearing as subscripts in these
equations. The final term of equation (7) is explained below. Also,

EC,, = --~~.~(2/a*~){l -(l +al”*+ol*l/2)exp( -al”*)!.

The activity of water may be obtained directly from equation (11) of Pitzer and
Kim@’ by the definition:
In a, = -~M,/(g~mol-‘)}~Cmi/(mol~kg~l))~/lOOO.
wherein M, represents the molar mass of water (taken as 18.01533 g. mol- r ), C mi
the sum of molalities of all ionic and neutral species when the solution is at
equilibrium with respect to (l), and $J the osmotic coefficient of the solution.
As noted in the introduction, carbonate solutions must be discussed within the
framework of asymmetric-mixing theory since at equilibrium the doubly charged
CO:- species coexists with singly charged HCO; and OH- ions. Pitzer(23) derived
the additional electrostatic terms, first noted by Friedman,‘24) arising from
asymmetric mixing. He found that inclusion of these terms is, from the standpoint of
modeling experimental e.m.f. measurements, required for 3 1 and higher charge type
electrolyte mixtures, but for many 2-l and l-2 mixtures the experimental results may
be adequately represented without them. Harvie and Weare found the full
electrostatic formulation essential for accurate treatment of CaSO, solubility in
aqueous NaCl. Employing the notation of Pitzer,
e,,,, = E~c,c.+S~c.c..
(8)
PC.&.= Esc,c.+sf&y

wherein EOE.C.and E6&. represent the higher-order electrostatic effects of asymmetric

mixing. These terms may be calculated a priori and are complex functions of the
charges on ions c and c’, the ionic strength and temperature ; if the charges on c and c’
are equal, these terms vanish. sQc,.c,and ‘(II&. represent the effect of short-range
interactions between ions c and c’, and must be evaluated empirically. It has been
 THERMODYNAMICS OF AQUEOUS CARBONATE SOLUTIONS 617

found in previous investigations (6-1o) that the ‘0; c terms are negligible; hence they
are omitted in this analysis. The remaining non-vanishing terms in EQc,,. may be
collected as indicated in equation (7) with the subscript indicating only the
magnitude of charge on each of the ions c = CO:- and c’ = HCO,. OH -, and Cl
The excess enthalpy L and heat capacity J of the solution are obtained from
temperature derivatives of equation (5) in the usual manner. If all 0 and $ parameters
are assumed to have vanishing temperature derivatives, one obtains
L/w, = (A,Z/b)ln(l+6Z”2)-2RT2~m,m,(B~~a+(I:m~)C~a~. (9)
c.a
J/u, = (A,I/b)ln( 1+ bZ”2)- 2RT2 2 mcmai Bzi + (C m=)CT,i), (10)
c.a
B:a = @L/W,: B;,; = (~2B,~,/8T2),+(2/T)(SB,,,j?T),.

CL = w-,.m-),~ CT; = (~2C,,3/~T2),+(2/T)(~C,.,I~T),.

The DebyeeHtickel slopes A, and A, are defined in accordance with the results of
Bradley and Pitzer,‘25’ who give values for a wide range of temperatures and
pressures, and have SI units: J.kg”“.moll’ 2 and J.kg1’2~mol-1’2.K-‘.
The enthalpy of dilution for a mixture of electrolytes from some set of initial ionic
molalities m’ = (ml, rni, . . .) to a final set of ionic molalities m’ = (m:, m\. .) is
AH, = L(m’)-L(m’)+AH (d, m’). (11)
The last term of this formula represents the ideal enthalpy change accompanying the
interconversion of the appropriate amount of substancerequired to shift the solution
composition from m’ to m’; for the carbonate system the reactions governing this
interconversion are given in (1). Berg and Vanderzee (is) discuss this effect in some
detail.
The enthalpy of solution of a salt (or mixture of pure solid salts) with net
composition m” in a solution of equilibrium composition m’, giving a solution with
equilibrium composition m’ is
AH, = AH:(m”)+AH’(m’, m’+m”)+L(d)-L(m’), (12)
wherein AH: represents the ideal enthalpy of solution.
Equations (11) and (12) are applicable only to processesin which the temperature
remains constant. The more general form of (11) may be found by integrating the
total differential of the enthalpy
dH = (i?H/aT), dT + @H@n), dm, (13)
from (T, m’) to (?;, m’). The enthalpy of solution may be formed by adding to this
result the ideal enthalpy of solution. AH,(&) and correcting the ideal enthalpy
change AH to include ms as in (12).
The heat capacity of a solution with some or all ionic speciesobeying a set of
equilibria such as (1) includes the heat-capacity effect due to the change of
equilibrium composition with temperature. This effect arises from the last term of
(13), and was overlooked by Perron, Desnoyers, and Millero.‘i9’ but was included by
618 J. C. PEIPER AND K. S. PlTZER

Woolley and Hepler (26’ for some other systems. It is assumed in the following
discussion that the kinetics of these equilibria are fast in comparison to the time
required to measure the heat capacity. For some flow microcalorimeters the latter
may be less than 1 s. In the present case, the hydrolysis of CO:-, equation (1). attains
equilibrium essentially instantaneously. However, it is widely known that the
interconversion of CO,(g) and carbonic acid is slow, and thus the disproportionation
of HCO;, equation (1). may not attain equilibrium within the time span of a heat-
capacity measurement. Fortunately the enthalpy of disproportionation is small so
that the error incurred in this analysis by assuming that equilibrium has been
achieved is also small. Our calculations indicated that this error contributes
negligibly to the heat capacity.
In determinations of the solution heat capacity one commonly measures the small
but finite rise in temperature AT accompanying the addition, usually ria an electrical
resistor, of an amount of work Q under rigorously controlled conditions. The
experimental heat capacity is then taken as the finite difference approximation Q/AT
For systems which obey a set of temperature-dependent interconversion equilibria
one must observe that contributions arising from these reactions are included in
Q/AT If the solution is initially at temperature T with equilibrium composition mi
and during the course of a heat-capacity determination the temperature rises to
Tr = (T+AT). causing a displacement in equilibrium composition to m’, then
C,=Q/AT= ‘,H(T,.m’)-H(T,m’)j/AT

wherein H represents the total enthalpy of the solution.

Separation of the direct effect of the temperature rise upon the solution enthalpy
from its indirect effect (through the change in equilibrium composition) may be
achieved by forming the total differential of the enthalpy (13). Division by dT and
slight rearrangement yields

C, = dH/dT = @HIaT),,, + 1 (aH/aa&,. da,/dT (14)

k

The set of parameters ot indicate the degree to which the interconversion equilibria are
displaced from the initial composition mi to yield the final composition mf ; a* is written
simply to indicate that all parameters with the exception ofa, are held constant ; further.
the ai are dimensionless.
The first term on the right in equation (14) may be identified as the heat capacity at
constant composition C,,,(m) with which Q/AT is normally equated. This quantity
may be separated into idea1 and non-idea1 terms

C,,,(m) = C;(m)+J(m), (15)

where J(m) is given by equation (10). The remaining partial derivatives in equation
(14) may be seenasequivalent to the enthalpy changesof the interconversion reactions.
For reaction k,
@H/auk IT me = AHk(m).
 THERMODYNAMICS OF AQUEOUS CARBONATE SOLUTIONS 619

As for the heat capacities, this quantity may be partitioned into ideal and non-ideal
contributions, thus
AH,(m) = AH; +AL,(m). (16)
Substitution of (15) and (16) into (14) yields
C,(m) = C;(m) + J(m) + c AH;; da,/dT + 1 AL,(m) du,/dT.
k k

Although entirely correct, this last expression is cumbersome since equations for the
temperature derivatives of the c(~are complicated, e.g. equation (22) of Pitzer, Roy.
and Silvester.“” However, if the equilibrium composition of the solution over a range
of temperature (‘&, K + AT) is known to sufficient accuracy, it is possible numerically
to calculate the finite difference quantity A&/AT With this substitution, the
summation in the final term may be evaluated explicitly to give
1 AL,(m)Aa, = L(d)- ,!@I’),
k

wherein L is the relative enthalpy given by equation (9). Note that these enthalpies
derive from the constant-temperature partial derivatives of the solution enthalpy. Thus
our final equation for the heat capacity is
C,(m) = C;(m) + J(m) + 1 A&Auk/AT + (L(d) - L(m’);/A7: (17)
k

All enthalpies and heat capacities appearing in this equation are evaluated at T, which
may be taken as the mid-point of the temperature interval of experimental
measurement. All thermodynamic quantities in equations (1) through (17) are for an
unspecified quantity of solution but they can be interpreted more easily for a solution
containing unit mass of water.

3. Method of calculation
Before discussing in detail the method used in the present analysis it is convenient to
explain all manipulations and conversions performed prior to that analysis.
Harned and Davis, (11) Harned and Banner,“” and Roy et .1.(14 measured
potentials for cell (2) which are given by

E = c&cl -(RT/~){ln(~l~s)+lnl~~fco,l(~~~~~)1~2i
+ln(~crl’c,/~~co,;‘~co,)). (18)
The measurements of Harned and Scholes” ‘) yield potentials according to
E = G&cl - W7~)fln{~2tp”/fH,) 1’2j +~nf~,,~,,,~,Y,c*,/~co,Yco,~ ;’ (191
In these equations EiglAgC, is the standard half-cell potential for the (silver + silver
chloride) electrode; K,, K,, and KS are the first and second ionization constants of
carbonic acid and the Henry’s law constant for solution of CO,, respectively : u, and
fi: are the activity of water and the fugacity of gaseous species i ; mj, ‘Jj are the molality
and activity coefficient of ionic species j when the solution is at equilibrium with
respect to (1); and pG = 101.325 kPa and wi‘ = 1 mol. kg- ‘. R, T, and F retain their
620 J. C. PEIPER AND K. S. PITZER

usual meanings; values for R and F, as well as other physical constants used in this
analysis, were taken from the work of Cohen and Taylor.“”
The e.m.f. measurementsof Roy et ~11. were used without manipulation. However.
the older measurements from Harned’s laboratory were based upon the
“international volt” in use at that time. We have converted these potentials to the
modern definition of the volt by multiplying Harned’s measurements by the factor
1.00033. Also, Bates and Macaskill’28’ and Bates et ~1.‘~~’have found that (silver +
silver halide) electrodes are extremely sensitive to slight variations in preparative
technique, and that, if high precision is desired, a standardization of the (silver +
silver halide) electrode should be carried out. In brief, the difference (E- E’ ) is more
reproducible from laboratory to laboratory than the absolute potential E. Therefore,
in this analysis we have used the AglAgCl standard-cell potentials of Harned and
Ehlerst3’i in interpreting measurements from Harned’s laboratory and the similar
measurementsincluded in the report of Roy er al. in interpreting their own e.m.f.‘s.
The isopiestic determinations of Robinson and Macaskill’16’ and White and
Bates”” were performed using sodium chloride reference solutions. Our analysis of
theseresults involves converting this reference molality into an activity of water using
the known properties of NaCl solutions at 298.15 K.‘4. 5,
The enthalpies of dilution reported by Berg and Vanderzee”” could be
incorporated into the present analysis through equation (11) in a comprehensive
simultaneous treatment of all experimental results. However, these authors have
already corrected their apparent molar enthalpies for the effects of equilibria (l), with
a treatment based largely upon the e.m.f. work of Harned and co-workers. Although
the first method is preferable in terms of self-consistency of the calculation, the
additional complexity seemshardly justified since our corrections would not differ
significantly from those made by Berg and Vanderzee. Therefore, we determined the
Na,CO, and NaHCO, coefficients of equation (9) riu independent least-squaresfits

TABLE 1. Ion interaction parameters at 298.15 K

NaJO, NaHCO, NaOH NaCl

/r”‘/(kg~mol-‘) 0.0362 ~O.OOG3 0.028 + 0.003 0.0864” 0.0765 ”

fl”/(kg.mol-‘) 1.51*0.03 0.044 + 0.009 0.253 u 0.2664 ’
C@/(kg’~mol~‘) 0.0052 + 0.0002 0.0044” 0.00127 ‘I
(103a~~o’/aT)/(kg~mol~‘~K~‘) 1.79 * 0.04 1.oo * 0.03 0.7 l’ 0.7159 h
(lo’ag”‘/a~)/(kg~mol-l.K-‘) 2.05 + 0.07 1.10+0.06 0.134h 0.7005 *
(lo3ac/aq/(kg2 mol -z. K 1) -0.1894h -0.1054*
(105a2flo)jaqj(kg mol- ’ K -l) -4.22kO.03 -2.6kO.2 -2.00+0.008 - I.498 @
(10Sa2~1’/aT2)/(kg-mol-‘~K~‘) -16.8&0.3 -4.3kO.8 - 2.1 TO.4 0.2143 ‘
(10Sa2C~aTZ)~(kgZ~moI-z~K~2) 0.29 i 0.02 0.1454’
CJR - 27.48 _+0.08 -1.35_+0.10 -11.63iO.07

- (0.0359~0.0010) kg.mol ’ ; - - 0.050 kg. mol. 1id

t,bNa~~~~::::= -(0.0143~0.0010) kg’,mol-‘; I),,“~::~~ = -0.006 kg2.molF2:”
s&o, c, = - (0.053 + 0.002) kg. molt 1’

’ Pitzer and Mayorga. W’ b Silvester and Pitzer.‘Jg’ ’ If higher-order electrostatic terms are omitted.
eco,,c, = -0.092 kg.mol- ’ d Pitzer and Kim.‘6’ * Silvester and Pitzer.“’
 THERMODYNAMICS OF AQUEOUS CARBONATE SOLUTIONS 621
to the corrected enthalpies of Berg and Vanderzee. The results of those calculations
are given in table 1 with other results.
The heat capacities of Perron, Desnoyers, and Millero”9’ were incorporated into
the present analysis in the following manner: Perron et al. measured solution heat
capacities using a flow microcalorimeter and vibrating-tube densimeter. These
instruments directly determine the difference in volumetric heat capacity and density,
respectively, between an aqueous electrolyte solution and pure water. Unfortunately,
their measurements were later found to be slightly in error by Desnoyers, de Visser.
Perron and Picker,t3” due to experimental difficulties with the microcalorimeter, but
were also found to be correctable. That correction involves multiplying the difference
in volumetric heat capacity, Aa in Perron’s formalism, by the factor 1.02. The
corrected measurements of Perron et al. were converted to total heat capacities for a
solution containing 1 kg of water.
In calculating the activity of water it is necessary to know the molality of dissolved
but unionized carbon dioxide, which requires an approximate knowledge of Ks alone.
This information may be taken from the work of Harned and Davis.“” Their
measurements of CO, solubility as a function of temperature and ionic strength may
be reproduced within experimental error by an equation of the form adopted by
them :
ln KS = q1WIT)+q2+q.J~/K). (20)
We found that the composition dependence of each parameter could be
represented by
qj = aj+bj(Z/Z )+c;expldj(l/l’)‘.“I. (21)
The coefficients aj, bj, cj, and dj are given in table 2; 1’~= 1 mol. kg- ‘.
The equilibrium constant for the self-ionization of water:
H,O(l) = H+(aq)+OH -(aq),
is also required. Grenthe, Ots, and Ginstrup’32’ reported precise measurements of the
enthalpy of ionization in the 273 to 323 K range, and fitted their results to an
equation which may be integrated to yield
In K, = -32.234+50103.2 K {(T- T,)/TT,j -330.089 ln(T/T,)
+0.8457096(T-T,)/K-3.801538 x 10-4(T2- 7.,2)/K’, (22)
with T, = 298.15 K. The value of K, at 298.15 K was taken from the report of
Guggenheim and Turgeon, (33) who thoroughly re-analyzed the e.m.f. determinations
of Harned and his students.‘34-36’ Recently, Olofsson. and Olofsson’37’ and Olofsson
and Heplerc3”’ reviewed the available information concerning the ionization of water :

TABLE 2. Parameters for CO, solubility. equation (21 I

i ‘iI bi L’J d,
1 5652.1 +0.4 - 653.3 + 0.2 ~ 155.3+0.2 - 2.504 f 0.010
2 - 33.473 + 0.003 3.9398f0.0014 1.1695_+0.0012 - 2.276+0.010
3 0.037177~0.000006 -0.006491 +_O.O00002 -0.001981 ~OOOOOO2 -2.163kO.010
622 J. C. PEIPER AND K. S. PITZER

however, these authors were primarily interested in temperatures above those 01

interest in this report. In the region of overlap, 298 to 323 K, their “best” values agree
very well with values of K, and its temperature derivatives calculated from the
equation above.
A non-linear least-squares procedure was used to evaluate the unknown virial
parameters. However, due to equilibria (1). this approach is somewhat complicated
since the preceding equations require a knowledge of the detailed ionic composition.
Given estimates of the unknown parameters, ionic molalities may be calculated by an
iterative procedure from the usual activity expressions for (I). The activity-coefficient
ratios for these expressions are readily derived from the equations in reference 6 or 22.
The resulting equations are similar to equations (6) and (7) above and involve the
same parameters. The calculation of ionic molalities must be performed in a manner
which allows no material to be expelled from or taken into the system, with the
exception of measurements made under a constant and known pressure of CO,. Since
the higher-order electrostatic contributions E8, and EO’ depend upon the solution
ionic strength, these must also be recalculated. At this point the normal least-squares
calculation may proceed for that iteration, and the entire process be repeated as
necessary for convergence.
The quantities which were determined viu the iterative least-squares process include
the product K, K,, K,, the heat capacities at infinite dilution of Na,CO, and
NaHCO,, C;(Na,CO,) and C;I(NaHCO,), and the minimal number of virial
coefficients and ion interaction parameters required to reproduce measurements to
within experimental error. Of the pure-electrolyte parameters (fl”‘, fll). and C@‘)only
the third virial C@for NaHCO, was not needed. The temperature dependence of ,!$“’
and /l(l) was recognized in all cases. For NaOH, these temperature derivatives as well
as that for C” are independently available from Silvester and Pitzer’39’ and from fits of
Perron, Desnoyers, and Millero’s”” heat capacities. In no case was it necessary to
recognize the temperature dependency of the virial coefficients for mixing ions of the
same sign, 0 and $. In all there are 12 parameters for mixing ions of the same sign of
which 2 were known independently, 3 were evaluated from the present data, and 7
were not needed.
Weighting for the least-squares calculation was based principally upon the
uncertainty of the data; specifically, the weight was inversely proportional to the
square of the uncertainty. The measurements of Harned and Davis were observed to
be very precise near room temperature, exhibiting approximately 0.2 mV of scatter at
298.15 K, which worsened to 0.4 mV at either temperature extreme. Those of Harned
and Bonner showed similar behavior across the temperature range, but appeared to
have an additional 0.1 mV uncertainty. Harned and Scholes measured e.m.f.‘s with
an uncertainty of 0.3 mV, which showed no variation with temperature. The
measurements of Roy et al. exhibit an uncertainty of 0.4 mV, with no apparent
variation with temperature. We found that the isopiestic determinations of Robinson
and Macaskill yielded a standard error of 0.002 in the osmotic coefficient, which
corresponds to an error of less than 0.0001 in the water activity at an ionic strength of
1.0 mol .kg-‘. White and Bates’ results appear to be somewhat less precise,
exhibiting an uncertainty of 0.0002 in the activity of water at the same ionic strength.
 THERMODYNAMICS OF AQUEOUS CARBONATE SOLUTIONS 623

The heat capacities of Perron et ~1. exhibit a precision better than

0.00005 J. g- ’ . K - ’ in the specific heat capacity.

4. Results and discussion

Table 1 presents the results of least-squarescalculations with inclusion of the higher-
order electrostatic terms due to asymmetric mixing. Neglect of these terms yields
results not significantly different from those of table 1. with the exception of ‘8coq,,,.
This quantity then has the value - (0.092 + 0.002) and may be relabelled &o,,c, since
it is the only non-zero term in equation (8). Inclusion of terms required in the full
electrostatic treatment lowers the standard error of fit slightly, as it should. but the
difference is small. Therefore, on the basis of reproducing the experimental
measurementshere considered, it appears that these terms may be neglected without
serious error. However, in treating certain properties of complex mixed-electrolyte
solutions such as natural waters, these terms may be more important; hence the full
electrostatic treatment should be used if maximum accuracy is desired.
The values of parameters given in table 1 yield thermodynamic quantities which
reproduce experimental measurements to within the above-cited errors, with the
following exceptions. All e.m.f.‘s at 273.15 and 323.15 K showed a small but
consistent deviation which we interpret to be the result of taking the solution heat
capacity to be constant for this range of temperature. Even so, the deviations at the
temperature extremes were rarely in excess of 1.0 mV. The newer e.m.f.
measurementsof Roy et u/.(*~’ were satisfactorily reproduced to within 0.8 rnV, even
at saturation of NaHCO,. The most dilute measurements of Robinson and
Macaskill’16’ appear to conflict with Harned and Scholes’s” 5’ e.m.f. measurements.
but the discrepancy is small (approximately 0.0002 in the water activity). White and
Bates’s”” isopiestic measurementswere reproduced with an uncertainty of 0.0003 in
the activity of water, with the exception of those measurements on solutions with
highest solute mole fraction of Na,CO,. These measurements,in conflict with those
of Robinson and Macaskill, exhibit a worst-case deviation of 0.002 in the water
activity. The specific heat capacities were reproduced to within 0.0001 J. K ’ g ’ at
all solution compositions.
The virial parameters /I’“‘, /?(I’, and C@’for Na,CO, have been given previously by
Pitzer and Mayorgaf4’ and by Robinson and Macaskill.‘16’ In the earlier report of
Pitzer and Mayorga the parameters for Na,CO, are based primarily upon the cell
e.m.f.‘s of Taylor, (40’which we suspect may be slightly in error due to irreversibilities
in or contamination of the AgjAg,CO, electrode. Robinson and Macaskill’s values
for the virial parameters agree reasonably well with the present values, particularly in
light of the closecoupling between the parameters. Differences between the two setsof
values can be explained by our recognition of hydrolysis and use of Harned and
Scholes’s results. The only published values of /I”’ and fi”’ for NaHCO, and of
HnCO,.c, are given in our previous report. (’ ” The present values of /?‘“’ and I?” agree
with those results well within the indicated uncertainties; indeed, agreement is nearly
exact. The earlier value of the anion mixing parameter O,,,,:c, was quite uncertain
becauseof the limited composition range of the data then available. The much wider
6’4 J. C. PEIPER AND K. S. PITZER

range of data from Roy er LI/.‘~” makes it possible to determine fjHCO,,-., more
accurately and to obtain a value for the corresponding third virial parameter
It is not surprising that the old estimate of tJHCo,.C, differs considerably
t!&HZ2’ffiw value.
One further cautionary note concerning the effects of asymmetric mixing: in this
study temperature derivatives of the higher-order electrostatic terms were omitted,
even though they are in principle known. Our calculations indicate that for the
presently available measurements, contributions of these derivatives to the enthalpy
and heat capacity are negligible. Therefore, it seems pointless to include the rather
complex expressions required to obtain these contributions purely in the interest of
formal completeness. However, one must be cautious in using the results of table 1 in
calculating enthalpies or heat capacities for solutions,with ionic strength greater than
1.5 mol. kg- ’ and approximately equal molalities of univalent and divalent anions.
An expanded discussion of the temperature derivatives of the electrostatic effects of
asymmetric mixing is being prepared.‘41’
The standard-state thermodynamics of the ionization equilibria of carbonic acid
were represented with equations of the form suggested originally by Clarke and
Glew’42’ ’dnd recommended by Bezboruah, Camoes, Covington, and Dobson.(43) Due
to the lack of heat capacities at temperatures other than 298.15 K, we were forced to
use an equation which yields a temperature-independent standard-state heat capacity
of reaction, an assumption which Pitzer and Silvester(*’ found barely tenable for
sodium chloride solutions at temperatures below 323 K.
Of course. the heat capacity of reaction for an aqueous electrolyte solution is
related in a precise manner to the heat capacities at infinite dilution of the several
electrolytes involved. The first and second ionization equilibria of carbonic acid may
be written in the forms:
CO,(g)+H,O(l)+NaCl(aq) = NaHCO,(aq)+HCl(aq),
NaHCO,(aq)+NaCl(aq) = Na,CO,(aq)+HCl(aq).
The corresponding heat capacities of reaction are then

AC,., c, = C,(NaHCO,)+C’;(HCl)-C,(CO,)-CJH,O)-C,(NaCl).
AC,. 2 = C;(Na2C0,)+CJHCl)-CJNaHCO,)-C&NaCI).
At 298.15 K the heat capacities at infinite dilution of NaCl and HCl are (C,/R)(NaCl)
= ~ 10.15 and (CJR)(HCl) = - 15.27, respectively.‘31’ The heat capacities of H,O
and CO, were taken from Stimson’44’ and Rossini,‘45) respectively, who give
(CG/R)(H,O) = 9.0556 and (Ci/R)(CO,) = 4.4650. Including the values of
C;(Na,CO,) and Cp(NaHC0,) taken from table 1, we find AC;;, 1+$ = - 19.99R and
AC,. 2 = - 31.25R.
Berg and Vanderzee” ‘) give values for the standard enthalpies of the above
ionization reactions : AH r +,/R = - 1274 K and AH;/R = + 1768 K. The equilibrium
constants for ionization of carbonic acid may be written as

lnWIWT = ln(Kl&,)298.15 K - 1274j(T/K)-298.15;/(298.157-/K)

- 19.99((298.15 K/T)- 1 +ln(7’/298.15 K);, (23)
 THERMODYNAMICS OF AQUEOUS CARBONATE SOLUTIONS 625

ln(K2h = lnW2),,,.,, K +1768{(T/K)-298.15)/(298.15T/K)

-31.25[(298.15 K/T)- 1 +ln(T/298.15 K);. (24)
Table 3 presents a summary of the standard-state thermodynamics of carbonic acid
at 5 K intervals based upon these equations. The values of ln(K, KS) and In k’? agree
reasonably well with the original interpretation of Harned and co-workers, who found
- 17.995 and -23.758 at 298.15 K. respectively. However, the heat capacities of
reaction at 298.15 K differ substantially from Harned’s values: this analysis relies
heavily upon the measurements of Perron et ul. whereas Harned’s values were
derived from the temperature dependence of their e.m.f. work.
Table 4 presents our results for the heat capacities of Na,CO, and NaHCO,
solutions at 298.15 K and finite molalities. In table 4(a) we compare the
measurements of Perron et ctl. with our optimized values, and give also a breakdown
of contributions to the total heat capacity, equation (17). It may be seen that for
solutions of Na,CO, at low molalities. the contribution from the next-to-last term of
( 17) is very significant. Figure 1 indicates the magnitude of corrections which must be
applied to the apparent molar heat capacity. @C,.The uppermost curve presents the
authors’ fit of experimental measurementsfor pure Na,CO, solutions at equilibrium
with respect to (1). The central curve gives contributions from the first two terms of
(17), C, +J(m). The remaining curve presents the heat capacity for an hypothetical
non-hydrolysed solution of Na,CO,. Adding a small amount of NaOH to these
solutions has the effect of reducing the contributions (AH +AL) (equation 17) as
Perron rt ul. had observed, but do not diminish them to the point of negligibility.
Figure 2 shows the effect that various small amounts of NaOH have upon $C,,.
The apparent molar heat capacity for a mixed electrolyte is not readily defined. For
single-solute solutions @C,is a molar excessquantity of solute. Extending this idea,
we suggestthat the apparent molar heat capacity of one component in an electrolyte
mixture may be defined as the total solution heat capacity in excess of that for the
solution if the component were not present, divided by the molality of the component.
Unfortunately, this definition of @C,may be applied only to solutions with single
common cation or a single common anion. Also, the apparent molar heat capacities

TABLE 3. Standard-state thermodynamics of ioniz.ation of carbonic acid

T AH,+, AH, lc‘, 2

K
MK, KS)
RK RK R

273.15 - 17.694 -- 774 ~ 24.46X 2549

278.15 - 17.748 - 874 - 24.305 2393
283.15 - 17.807 -974 -24.158 2237
288.15 - 17.870 -1074 - 24.026 2080
293.15 - 17.936 -1174 ~ 23.907 1924
29X.15 - 18.006 -1274 - 19.99 - 23.802 1768 31.25
303.15 - 18.079 -1374 - 23.708 1612
308.15 - 18.156 - 1474 ~ 23.626 1456
313.15 - 18.235 ~ 1574 - 23.555 1299
318.15 - 18.316 -1674 ~ 23.493 1143
323.15 - 18.400 - 1774 - 23.442 987
TABLE 4. A comparison of experimental and smoothed heat capacities for solutions of sodium carbonate and bicarbonate at 298.15 K. A solution with nominal
composition given in the first three columns has an equilibrium composition given in columns 4 through 7. The experimental results of Perron, Desnoyers. and
Millero”” are given in the final column of part (a) of the table. Columns 8 through 12 may be identified with terms of equation (17). All quantities in columns 8 through
13 are for a solution containing 1 kg of water

m(nominal) m(equilibrium) iC,(m)-C,(H20)I;x~,

J.K-'.kg-l
mol.kg-’ mol.kg-’ ~C,(m)-CpW20))/~~, J(m)lw, AH /AT\v, AL/AT\\,,
J.K-'.kg-' J.K-!,kg-' J:K-l.kg-l J.K-‘.kg-’
Na,CO, NaHCO, NaOH co: HCO, H&O, OH- eqn (17) ref. 19

(a)
0 0.0081 0 O.WOl 0.0079 0.0001 0 -0.09 0.03 0.01 0.00 -0.06 -0.08
0 0.0141 0 0.0002 0.0137 0.0002 0 -0.16 0.07 0.01 0.00 ~ 0.08 - 0.06
0 0.0231 0 o.c003 0.0226 0.0003 0 - 0.26 0.15 0.01 0.00 -0.10 - 0.08
0 0.0350 0 0.0004 0.0341 0.0004 0 -0.39 0.28 0.01 0.00 -0.09 0.06
0 0.0644 0 O.OOB8 0.0628 O.ooO8 0 -0.72 0.75 0.02 0.00 0.06 0.14
0 0.1272 0 0.0016 0.1240 0.0016 0 - 1.42 2.26 0.04 0.01 0.89 0.80
0 0.1880 0 0.0025 0.1831 0.0025 0 - 2.10 4.27 0.06 0.01 2.24 2.30
0 0.2701 0 0.0036 0.2629 0.0036 0 - 3.01 7.71 0.09 0.02 4.80 4.85
0 0.3189 0 0.0043 0.3103 o.oB43 0 - 3.56 10.11 0.11 0.03 6.68 6.70
0 0.5285 0 0.0072 0.5 140 0.0072 0 -5.89 23.10 0.19 0.06 17.45 17.43
0 0.7740 0 0.0107 0.7526 0.0107 0 -8.63 43.20 0.29 0.11 34.97 35.06
0.0086 0 0 0.0075 0.0011 0 0.0011 -1.83 0.15 1.14 -0.01 -0.55 - 0.50
0.0397 0 0 0.0376 0.0022 0 0.0022 - 8.81 1.69 2.39 -0.04 -4.78 -4.52
0.0652 0 0 0.0625 0.0027 0 0.0027 - 14.58 3.70 2.98 -0.06 - 7.97 - 7.66
0.1552 0 0 0.1513 0.0039 0 0.0039 ~ 34.99 14.31 4.27 -0.12 ~ 16.53 - 16.46
0.2414 0 0 0.2368 0.0046 0 0.0046 - 54.60 28.28 5.07 -0.17 -21.42 - 21.39
0.2960 0 0 0.2911 0.0049 0 OS049 -67.04 38.65 5.45 -0.19 - 23.12 ._ 23.05
0.4325 0 0 0.4270 0.0056 0 0.0056 -98.15 68.89 6.19 - 0.23 - 23.30 - 23.07
0.5831 0 0 0.5771 0.0061 0 0.0061 - 132.50 108.46 6.76 - 0.26 ~ 17.54 - 16.57
0.9839 0 0 0.9772 0.0069 0 0.0069 - 224.00 240.67 7.67 -0.29 24.05 ‘3.91
0.0354 0 0.0100 0.0350 0.0004 0 0.0104 -9.01 1.67 0.91 - 0.02 - 6.46 - 6.83
0.0709 0 0.0100 0.0702 o.oLW7 0 0.0107 - 17.07 4.60 1.54 -0.04 ~ 10.97 - 11.12
0.0227 0 0.0050 0.0221 0.0005 0 0.0055 -5.60 0.80 1.09 -0.02 -3.73 - 3.74
0.0401 0 0.0050 0.0392 O.OBO8 0 0.0058 -9.54 1.86 1.62 -0.03 ~ 6.08 - 5.97
0.0628 0 0.0050 0.0617 0.0012 0 0.0062 - 14.70 3.67 2.17 - 0.05 - 8.90 -x.79
0.0846 0 0.0050 0.0832 0.0014 0 O.OOt4 - 19.64 5.78 2.59 -0.06 ~~ I I .32 - I I.10
0.0862 0 0.0050 0.0847 0.0014 0 0.0064 - 20.00 5.95 2.62 - 0.06 - 11.49 - II.41
0.1844 0 0.0050 0.1820 0.0023 0 0.0073 - 42.32 19.03 3.93 -0.12 ~ 19.48 -- 19.62
0.2399 0 0.0050 0.2372 0.0027 0 0.0077 - 54.97 28.42 4.45 -0.15 - 22.25 72.67
0.3195 0 0.0050 0.3164 0.0031 0 0.0081 - 73.10 43.90 5.03 -0.18 24.34 24.62
0.5091 0 0.0050 0.5053 0.0039 0 0.0089 -116.34 88.86 5.99 -0.23 -21.72 -21.65
0.7539 0 0.0050 0.7495 0.0045 0 0.0095 172.20 160.99 6.75 -0.27 -~472 -394
0.9682 0 0.0050 0.9635 0.0048 0 0.0098 -221.14 235.64 7.18 -0.27 21.41 21.08

(b)
0 0.0010 O.OOOtl 0.0010 0.0000 0 - 0.01 0.00 0.00 0.00 -0.01
0 0.0020 O.oooO 0.0020 0.0000 0 - 0.02 0.00 0.01 0.00 -0.01
0 0.0050 0.0001 0.0049 0.0001 0 -0.06 0.01 0.01 0.00 - 0.04
0 0.0100 o.caO1 0.0098 0.0001 0 -0.11 0.04 0.01 0.00 - 0.07
0 0.0200 0.0002 0.0195 o.coO2 0 - 0.22 0.12 0.01 0.00 -0.10
0 0.0500 O.OCM 0.0488 0.0006 0 - 0.56 0.50 0.02 0.00 -0.04
0 O.laxl 0.0013 0.0975 0.0013 0 - 1.12 1.53 0.03 0.00 0.45
0 0.2cmO 0.0026 0.1947 0.0026 0 - 2.23 4.72 0.06 0.01 2.57
0 0.4000 0.0054 0.3891 0.0054 0 - 4.46 14.64 0.14 0.04 10.35
0 0.6Wl 0.0082 0.5835 0.0082 0 - 6.69 28.44 0.22 0.07 22.04
0 0.8ooO 0.0110 0.7778 0.01 IO 0 - 8.92 45.61 0.30 0.12 37.11
0 l.OCMl 0.0139 0.9720 0.0139 0 -11.15 65.87 0.40 0.17 55.29
0.0010 0.0010 0.0009 0.0011 0 0.0001 -0.22 0.01 0.24 0.00 0.03
0.0020 0.0020 0.0019 0.0022 0 0.0002 - 0.46 0.03 0.29 0.00 -0.15
0.0050 0.0050 0.0049 o.OOs2 0 0.0002 - 1.18 0.11 0.32 0.00 - 0.76
O.OlcKl 0.0100 OS@99 0.0101 0 o.cclO1 - 2.38 0.32 0.31 0.00 - 1.75
0.0200 0.0200 0.0199 0.0201 0 0.0001 - 4.78 0.96 0.29 0.00 -3.53
0.0500 0.0500 0.0499 O.OSOl 0 O.Oml -11.97 4.08 0.25 -0.01 -7.64
O.lwO O.lalO 0.0999 0.1001 0 0.0001 - 23.96 12.16 0.22 ~ 0.01 - 11.59
0.2000 0.2mO 0.2OfXl 0.2000 0 o.Om -47.93 35.93 0.19 -0.01 - 11.82
0.4000 0.4OW 0.4000 0.4OMl 0 0.0001 -95.87 105.65 0.14 0.00 9.92
0.6000 0.6000 0.6001 0.5998 0 O.Oml - 143.81 199.14 0.12 0.00 55.45
0.8OCN 0.8000 0.8001 0.7998 0 0.0001 - 191.75 313.69 0.10 0.00 122.05
l.WXJ 1.0000 l.iXlOl 0.9997 0 0.0000 - 239.69 448.14 0.09 0.01 208.55
0.0010 0 0.0007 0.0004 0 O.WO4 -0.19 0.00 0.31 0.00 0.13
0.0020 0 0.0015 o.Om5 0 o.ooo5 -0.40 0.01 0.50 0.00 0.11
0.0050 0 0.0042 0.0008 0 O.ooO8 - 1.04 0.06 0.86 -0.01 -0.13
0.0100 0 0.0088 0.0012 0 0.0012 -2.15 0.19 1.24 -0.01 -0.73
0.0200 0 0.0184 0.0016 0 0.0016 -4.38 0.57 1.74 - 0.02 - 2.09
0.0500 0 0.0476 0.0024 0 0.0024 -11.13 2.43 2.65 ~ 0.05 -6.11
0.1000 0 0.0968 0.0032 0 0.0032 - 22.46 7.22 3.57 -0.09 ~ 11.76
0.2000 0 0.1958 0.0043 0 0.0043 -45.19 21.18 4.72 -0.15 - 19.43
0.4ooo 0 0.3946 0.0054 0 0.0054 - 90.74 61.18 6.04 0.22 - 23.75
0.6ooo 0 0.5939 0.0061 0 0.0061 -- 136.36 113.27 6.82 - 0.27 -- 16.54
0.8OCNI 0 0.7935 0.0066 0 0.0066 -- 182.01 175.43 7.33 ~ 0.29 0.47
1.0000 0 0.9932 0.0069 0 0.0069 - 227.67 246.72 7.69 -0.29 26.45
628 J. C. PEIPER AND K. S. PJTZER

I I I

0.5 1.0 I.5

{ I/(mol*kg-‘))“2

FIGURE 1. The effect of hydrolysis upon Na,CO, heat capacity. The points are those of Perron,
Desnoyers, and Millero. (19’ The uppermost curve represents the authors’ optimized values of Na,CO, heat
capacity ; see the text for explanations of the remaining curves.

I I I

0.5 1.0 1.5

(3 m(CO,)/(mol.kg-‘)}“z

FIGURE 2. The effect upon Na,CO, heat capacity of the addition of a small amount of NaOH. The
points are those of Perron, Desnoyers, and Millero: (‘% 0. Na,CO,: 0. Na,CO,+O.O05 mol.kg-’
NaOH ; A, Na,CO, +O.OlO mol. kg- r NaOH. The lowest curve represents a hypothetical non-
hydrolyzed solution of Na,CO,.
 THERMODYNAMICS OF AQUEOUS CARBONATE SOLUTIONS 629
for the various components of a mixture are not easily combined to give a total
solution heat capacity, equation (10). It appears, then, that these quantities will be of
little utility, and are used here only for demonstrative purposes.
Enthalpies of dilution at 298.15 K are presented in table 5. These have been
calculated for a solution at an initial stoichiometric molality of 1 mol ‘kg-’ in
Na,CO, or NaHCO,. The various contributions to equation (11) are detailed : as
with the heat capacities, contributions stemming from the last term of (1 I ) are
important for dilute solutions of Na,C03.
Lastly, table 7 presents the activity of water and various activity coefficients for
Na,CO, and NaHCO, solutions at 278.15,288.15,298.15, 308.15, and 318.15 K. In
general, all activities and activity coefficients are believed accurate to the number of
figures given ; however, those near the extremes of the temperature range are certainly
less accurate than values at 298.15 K.
Also presented in these tables for nominally single-solute solutions are
stoichiometric activity and osmotic coefficients. These may be defined in terms of the

TABLE 5. Enthalpies of dilution at 298.15 K, calcuhited for a solution at an initial nominal molahty of
I mol. kg’. A quantity of this solution containing 1 kg of water is diluted by the mass WI of water in
column 7 to give a solution with the equilibrium composition in columns 3 through 6. Columns 8 through
IO represent terms of equation (1 I). Enthalpies are for a solution containing 1 kg of water

m(nominal) m(equilibrium)
--
mol.kg ’ mol.kg-* m(H,O) AH /ww ALJrv, AH,wU
Na,CO, NaHCO, co: - HCO; HzC0, OH- kg J.kg-’ J.kg ’ J,kg ’

0 0.001 0.0000 0.0010 O.COOO 0 999.00 -77 67X 602

0 0.002 0.0000 0.0020 0.0000 0 499 .oo -17 701 624
0 0.005 0.0001 0.0049 0.0001 0 199.00 -77 741 665
0 0.010 0.0001 0.0098 0.0001 0 99.00 -76 7X1 705
0 0.020 0.0002 0.0195 0.0002 0 49.00 -76 X26 751
0 0.050 0.0006 0.0488 0.0006 0 19.00 -74 XX5 812
0 0.100 0.0013 0.0975 0.0013 0 9.00 -70 906 X36
0 0.200 0.0026 0.1947 0.0026 0 4.00 -62 X66 804
0 0.400 0.0054 0.3891 0.0054 0 I so -47 691 644
0 0.600 0.0082 0.5835 0.0082 0 0.67 -31 475 443
0 0.800 0.0110 0.7778 0.0110 0 0.25 -16 241 226
0 l.ooo 0.0139 0.9720 0.0139 0 0.00 0 0 0
0.001 0 o.ooo7 o.o@M 0 0.0004 999.00 - 268 840 512
0.002 0 0.0015 0.0005 0 o.ooo5 499.00 - 261 953 b92
0.005 0 0.0042 0.0008 0 0.0008 199.00 - 248 1163 914
0.010 0 0.0088 0.0012 0 0.0012 99.Gu - 235 1373 1138
0.020 0 0.0184 0.0016 0 0.0016 49.00 -216 1626 1409
0.050 0 0.0476 0.0024 0 0.0024 19.00 -183 1993 IX10
0.100 0 0.0968 0.0032 0 0.0032 9.00 -150 2229 2079
0.200 0 0.1958 0.0043 0 0.04M3 4.00 - 108 2300 2193
0.400 0 0.3946 0.0054 0 0.0054 1.50 -59 1966 1907
0.600 0 0.5939 0.0061 0 0.0061 0.67 -31 1403 1372
0.800 0 0.7935 0.0066 0 0.25 -12 733 721
1.000 0 0.9933 0.0069 0 0.00 0 0 0
630 J. C. PElPER AND K. S. PITZER

equilibrium quantities by the formulae :

4” = C mi$/mS’, (25)
$ = (mx/m;)li~y+ (26)
wherein the superscript ” indicates the stoichiometric quantity and v the number of
ions generated upon complete dissociation of an electrolyte: 11= 2 for NaHCO, and
v = 3 for Na,CO,. For the activity coefficient only the anion molality appears since
the molality of Na+ is unaffected. It may be noted that at low molalities of Na,CO,
4 = 1 but 6’ z 1.33, and ;‘+ = 1 but ?;; z 0. For solute molalities below
approximately lo- 5 mol. kg- ’ ,- the meaning of stoichiometric properties becomes
ambiguous due to the self-ionization of water.
For nominally more than single-solute solutions, there is no simple definition of
such stoichiometric quantities, a severe disadvantage of that formulation. However, if
one wishesto calculate activities only for single-solute solutions, these stoichiometric
quantities will yield accurate Gibbs energy relations with a minimum of effort. a
distinct advantage over the complex equilibrium formulation.
The stoichiometric activity and osmotic coefficients at 298.15 K in table 6 may be
compared with published values. For Na,CO, the values of Goldberg”” and of
Robinson and Macaskill(i6’ may be considered. Since the osmotic coefficients at
moderate and high molalities were based in all treatments on Robinson and
Macaskill’s results, they agree. Also the hydrolysis equilibrium (1) has little effect in
this range. In view of the characteristics of a Gibbs--Duhem integration, the activity
coefficients in the same molality range may differ only by a constant factor. For
Goldberg’s results that factor is significantly less than unity (0.97,); the fact that he
ignored the hydrolysis reaction (1) yet attempted to fit the freezing temperatures of
Loomis’46’ for dilute solutions is a sufficient explanation. Robinson and Macaskill
simply fitted the Pitzer-type of virial-coefficient equation to their own results without
further guidance below 0.3 mol. kg-‘. It is probably fortuitous that their results agree
almost exactly with the present values. For NaHCO, our earlier results agree very
well with those in table 6.
Lastly, we note that a few additional measurements would improve
thermodynamic understanding of the carbonate system. Although accurate
thermodynamic information beyond 323 K is severely lacking, there is a need to
measure the heat capacity of aqueous Na,CO, and NaHCO, solutions and their
mixtures with NaCl and other salts at molalities in excessof 1 mol. kg-’ at 298.15 K
and at all molalities at temperatures other than 298.15 K. In combination with a few
additional measurements of the enthalpy of dilution at 298.15 K for solutions in
excess of 1 mol. kg- ‘, extremely accurate thermodynamics for this system will be
obtained.
In familiar pK units our results are, at 298.15 K, pl<, = 6.355, pK2 = 10.337. Since
for the former the basic quantity determined was KiK,, one can substitute a slightly
different value of KS if it seemsbetter, and the resulting K, will be valid. In particular.
the use of KS = 0.03408 from Weiss’47’yields pK, = 6.352. The simpler treatment by
Roy et al. (14) of their results yielded pK, = 6.360. Berg and Vanderzee” *) selected
from various sources the value pK, = 6.351 and adopted the result of Harned and
Scholes(15ifor pK, = 10.329. These various results are in good agreement.
TABLE 6. Osmotic and activity coefficients for sodium carbonate and bicarbonate solutions at temperatures between 278.15 and 318.15 K. A solution with
nominal composition given in the first two columns has an equilibrium composition given in columns 3 through 6, and an equilibrium vapor pressure of CO2
given in column 7. See the text for definitions of stoichiometric properties. (X = CO,. Y = HCO,. and Z = OH)

m(nominal) m(equilibrium)
mol.kg-‘- mol,kg’ P(CO,)
Na,X NaY X2- Y- HJ Z- lOsPa a, 4 ;‘Na,X ;‘NaY ;‘NaZ

(a) 278.15 K
0 0.001 O.OOC@ 0.0010 0.0000 0 0.000 0.99996 0.988 0.931 0.965 0.966 0.989
0 0.002 0.0000 0.0020 0.0000 0 0.000 0.99993 0.984 0.906 0.952 0.952 0.984 0.956
0.942 l
0 0.005 O.cmOl 0.0049 O.oWl 0 0.001 0.99982 0.975 0.858 0.926 0.928 0.975 0.917
0 0.010 0.0001 0.0098 0.0001 0 0.002 0.99965 0.966 0.810 0.900 0.902 0.966 0.890 E
0 0.020 o.tmO2 0.0196 0.0002 0 0.004 0.9993 1 0.954 0.752 0.865 0.870 0.954 0.856
0 0.050 0.0006 0.0489 0.0006 0 0.009 0.99832 0.933 0.658 0.805 0.815 0.933 0.796 $j
0 0.100 0.0011 0.0977 0.0011 0 0.019 0.9967 1 0.913 0.579 0.749 0.766 0.913 0.740
0 0.200 0.0024 0.1951 0.0024 0 0.040 0.99360 0.891 0.498 0.685 0.712 0.890 0.676 $
0 0.400 0.0050 0.3901 o.cmo 0 0.087 0.98760 0.866 0.417 0.614 0.658 0.865 0.606
0 0.600 0.0075 0.5850 0.0075 0 0.138 0.98179 0.850 0.371 0.571 0.627 0.850
0 0.800 0.0100 0.7799 0.0100 0 0.194 0.97610 0.840 0.339 0.540 0.607 0.839 0.564
0.534 3v,
0 1.ooo 0.0125 0.9748 0.0125 0 0.255 0.97050 0.831 0.315 0.517 0.593 0.831 0.510 0
0.001 0.001 0.0010 0.0010 0.0000 0.0000 0.000 0.99991 0.966 0.876 0.934 0.935 %
0.002 0.002 0.0020 0.0021 O.OOW 0.0001 0.000 0.99983 0.954 0.833 0.910 0.911
Ls
0.005 0.005 0.0050 0.005 1 O.MlOO 0.0001 O.OW 0.99958 0.932 0.761 0.867 0.870
0.010 0.010 0.0100 0.0100 O.OOW O.OOlXl 0.04M 0.99918 0.912 0.696 0.825 0.831 5
0.020 0.020 0.0200 0.0200 O.COOO 0.0000 0.000 0.99840 0.890 0.623 0.775 0.785 2
0.050 0.050 0.0500 0.0500 0.0000 O.OCW 0.000 0.99615 0.855 0.520 0.696 0.717
0.100 0.100 0.1000 O.lOcm O.MOCl 0.0000 0.000 0.99259 0.826 0.441 0.629 0.662 i5
0.200 0.200 0.2ooo 0.2000 O.OMKl 0.0000 0.001 0.98588 0.789 0.361 0.555 0.606
0.400 0.400 0.4ooo 0.3999 0.0001 0.0000 0.001 0.97365 0.741 0.282 0.477 0.552 5
0.600 0.600 0.6001 0.5999 O.MlOl O.OCQO 0.002 0.96244 0.708 0.237 0.430 0.527 ?
0.800 0.800 0.8001 0.7998 0.0001 0.003 0.95184 0.685 0.207 0.399 0.516 v,
1.000 1 .ooo 1 .oool 0.9998 0.0041 0.005 0.94160 0.668 0.186 0.375 0.514
0.001 0.0008 0.0002 0 0 0.99994 0.968 0.894 0.944 0.944 1.036 0.826
0.002 0.0017 0.0003 0 0 0.99989 0.955 0.855 0.922 0.923 1.003 0.810
0.005 0.0045 0.0005 0 0 0.99974 0.931 0.790 0.883 0.886 0.961 0.764 m
0.010 0.0093 0.0007 0 0 0.99950 0.909 0.729 0.845 0.849 0.929 0.712 LJ
 TABLE &continued

m(nominal) m(equilibrium)
mol ‘kg-’ mol.kg-’ P(CW
Na,X NaY X2- Y- Z- IO5 Pa a, .,SI .,I$
HP 4 ;'Na,X ?NaY YNaZ v i Na,X I NaY

0.020 0 0.0191 O.OCQ9 0 0.0009 0 0.99903 0.883 0.659 0.799 0.806 0.897 0.649
0.050 0 0.0487 0.0014 0 0.0014 0 0.99770 0.846 0.559 0.725 0.740 0.853 0.554
0.100 0 0.0982 0.0018 0 0.0018 0 0.99558 0.814 0.481 0.662 0.686 0.819 0.479
0.200 0 0.1976 0.0024 0 0.0024 0 0.99161 0.777 0.402 0.591 0.629 0.780 0.401
0.400 0 0.3970 0.0031 0 0.0031 0 0.98440 0.725 0.321 0.514 0.571 0.721 0.321
0.600 0 0.5966 0.0035 0 0.0035 0 0.97792 0.687 0.275 0.466 0.538 0.688 0.274
0.800 0 0.7964 0.0037 0 0.0037 0 0.97194 0.657 0.242 0.432 0.517 0.658 0.242
1.000 0 0.9962 0.0039 0 0.0039 0 0.96630 0.634 0.219 0.406 0.503 0.634 0.218

(b) 288 .15 K

0 0.001 0.0000 0.0010 0.0000 0 0.000 0.99996 0.988 0.931 0.965 0.965 0.989 0.955
0 0.002 O.OCQO o.cQ20 O.OOW 0 0.001 0.99993 0.984 0.904 0.951 0.952 0.984 0.942
0 0.005 O.oml o.cw9 O.oool 0 0.001 0.99982 0.975 0.856 0.926 0.927 0.97s 0.916
0 0.010 O.oool 0.0098 0.0001 0 0.002 0.99965 0.966 0.808 0.899 0.901 0.966 0.889
0 0.020 o.cm2 0.0196 0.0002 0 0.005 0.99931 0.954 0.749 0.864 0.868 0.954 0.854
0 0.050 0.0006 0.0488 0.0006 0 0.013 0.99832 0.933 0.656 0.805 0.814 0.933 0.795
0 0.100 0.0012 0.0976 0.0012 0 0.027 0.99671 0.914 0.578 0.749 0.765 0.914 0.740
0 0.200 0.0025 0.1950 0.0025 0 0.058 0.99359 0.893 0.498 0.687 0.713 0.893 0.678
0 0.400 0.0052 0.3896 0.0052 0 0.125 0.98753 0.871 0.420 0.619 0.661 0.871 0.61 I
0 0.600 0.0078 0.5843 0.0078 0 0.200 0.98162 0.858 0.376 0.5-79 0.632 0.858 0.571
0 0.800 0.0105 0.7789 0.0105 0 0.281 0.97579 0.850 0.346 0.551 0.615 0.850 0.544
0 1.000 0.0132 0.9735 0.0132 0 0.369 0.97003 0.845 0.323 0.530 0.603 0.844 o:s23
0.001 0.001 0.0009 0.0011 0.0000 0.0001 0.000 0.99991 0.961 0.874 0.934 0.934
0.002 0.002 0.0019 0.0021 0.0000 0.0001 O.OC@ 0.99983 0.954 0.831 0.909 0.911
0.005 0.005 0.0049 0.0051 O.oooO O.ocal O.ooO 0.99958 0.932 0.759 0.866 0.869
0.010 0.010 o.cm9 0.0101 0.0000 0.0001 O.ooO 0.99918 0.912 0.693 0.824 0.830
0.020 0.020 0.0199 0.0201 O.OWO O.ooOl 0.000 0.99840 0.889 0.621 0.774 0.784
0.050 0.050 0.0499 0.0501 0.0000 0.0001 O.OCKl 0.99615 0.857 0.519 0.697 0.717
0.100 0.100 O.looo 0.1000 O.WOO O.oool 0.000 0.99256 0.829 0.442 0.632 0.663
0.200 0.200 0.2000 0.2ooo 0.0000 0.0000 0.001 0.98575 0.797 0.365 0.562 0.610
0.400 0.400 0.4000 0.3999 o.ooo1 0.0000 0.002 0.97309 0.757 0.289 0.490 0.563
0.600 0.600 0.6001 0.5998 O.oool 0.0000 0.004 0.96118 0.733 0.247 0.449 0.543
0.800 0.8CHl 0.8001 0.7998 0.0001 0.0000 0.005 0.94960 0.718 0.220 0.423 0.536
1.04Ul 1.000 1.0001 0.9997 O.oool 0.0000 0.007 0.93810 0.709 0.201 0.404 0.539
0.001 0 o.OOa7 0.0003 0 0 0.99994 0.970 0.893 0.944 0.944 1.058 0.803
0.002 0 0.0016 O.OCQ4 0 0 0.99989 0.956 0.854 0.922 0.923 1.020 0.794
0.005 0 0.0044 O.OW6 0 0 0.99974 0.932 0.788 0.883 0.885 0.972 0.753
0.010 0 o.ca91 0.0009 0 0 0.99949 0.910 0.727 0.844 0.848 0.937 0.704
0.020 0 0.0188 0.0012 0 0.0012 0 0.99903 0.884 0.657 0.798 0.805 0.902 0.643
0.050 0 0.0482 0.0018 0 0.0018 0 0.99769 0.847 0.558 0.725 0.740 0.857 0.551
0.100 0 0.0976 0.0024 0 0.0024 0 0.99556 0.817 0.481 0.663 0.687 0.823 0.477
0.200 0 0.1968 0.0032 0 0.0032 0 0.99154 0.782 0.403 0.596 0.632 0.786 0.401
0.400 0 0.3959 0.0041 0 0.0041 0 0.98416 0.736 0.326 0.523 0.577 0.739 0.325
0.600 0 0.5954 0.0047 0 0.0047 0 0.97739 0.703 0.281 0.479 0.547 0.705 0.281
0.800 0 0.7951 0.0050 0 0.0050 0 0.97100 0.679 0.251 0.448 0.530 0.681 0.251
I .ooo 0 0.9949 0.0052 0 0.0052 0 0.96481 0.662 0.229 0.426 0.519 0.663 0.229

(c) 298 .I5 K i

0 0.001 0.0000 0.0010 0.0000 0.000 0.99996 0.988 0.930 0.964 0.965 0.989 0.954
0 0.002 0.0003 0.0020 O.OMlO 0.001 0.99993 0.983 0.903 0.95 1 0.951 0.984 0.941 ;
VI
0 0.005 0.0001 0.0049 0.0001 0.002 0.99982 0.974 0.855 0.925 0.926 0.975 0.915 0
0 0.010 0.0001 0.0098 0.0001 0.003 0.99965 0.965 0.806 0.898 0.900 0.965 0.888 -n
0 0.020 o.mo2 0.0195 0.0002 0.007 0.99931 0.953 0.747 0.863 0.867 0.953 0.853 >
0 0.050 0.0006 0.0488 0.0006 0.018 0.99832 0.933 0.653 0.803 0.812 0.933 0.793 g
0 0.100 0.0013 0.0975 0.0013 0.038 0.9967 1 0.914 0.576 0.748 0.763 0.914
0 0.200 0.0026 0.1947 0.0026 0.081 0.99358 0.894 0.496 0.687 0.712 0.894 0.678
0.739 s
0 0.400 0.0054 0.3891 0.0054 0.174 0.98748 0.874 0.420 0.622 0.661 0.874 0.613 v,
0 0.600 0.0082 0.5835 0.0082 0.278 0.98150 0.864 0.378 0.584 0.635 0.864
0 0.800 0.0110 0.7778 0.0110 0.391 0.97557 0.858 0.349 0.558 0.619 0.858 0.550
0.576 g
0 l.ooO 0.0139 0.9720 0.0139 0.514 0.96969 0.854 0.327 0.539 0.609 0.854
0.001 0.001 O.OC@ 0.0011 0.0000 0.000 0.99991 0.967 0.873 0.933 0.934 0.531 5
0.002 0.002 0.0019 0.0022 0.0000 0.000 0.99983 0.954 0.829 0.908 0.910
0.005 0.005 0.0049 0.0052 O.OCW 0.000 0.99958 0.932 0.756 0.865 0.868 5
0.010 0.010 0.0099 0.0101 O.oooO 0.000 0.99918 0.911 0.690 0.822 0.828 5
0.020 0.020 0.0199 0.0201 O.WOO O.CQO 0.99840 0.889 0.617 0.773 0.782
z
0.050 0.050 0.0499 0.0501 O.OOMl 0.000 0.99615 0.856 0.516 0.696 0.715
ti
0.100 0.100 0.0999 0.1001 0.0000 0.001 0.99254 0.831 0.440 0.633 0.663
0.200 0.200 0.2ooo 0.2000 O.OOMl 0.001 0.98566 0.801 0.365 0.566 0.612 tz
r/7
0.400 0.400 0.4om 0.3999 O.ooOl 0.003 0.97269 0.768 0.293 0.500 0.569
0.600 0.600 0.6001 0.5998 O.MJOl o.oooo 0.005 0.96024 0.751 0.254 0.464 0.553
0.800 0.800 0.8001 0.7998 0.0001 0.0000 0.008 0.947X9 0.743 0.229 0.441 0.550
I .ooo I .ooa l.ooOl 0.9997 0.0002 0.0000 0.01 1 0.93539 0.742 0.213 0.427 0.556
0.001 0 0.0007 0.0004 0 0.0004 0 0.99994 0.97 1 0.x97 0.944 0.944 I 0x3 0.775
0.002 0 0.0015 0.0005 0.0005 0 0.99989 0.957 0.x53 0.922 0.923 1.039 0.774
 TABLE &continued

m(nominal) m(equilibrium)
mol. kg-’ mol.kg-’ P(CW
Na,X NaY X2- Y- HJ z- ~10’ Pa a,

0.005 0 o.cKM2 0.0008 0 0.0008 0 0.99973 0.933 0.786 0.882 0.884 0.985 0.740
0.010 0 0.0088 0.0012 0 0.0012 0 0.99949 0.910 0.724 0.843 0.847 0.945 0.695
0.020 0 0.0184 0.0016 0 0.0016 0 0.99902 0.884 0.654 0.797 0.803 0.908 0.636
0.050 0 0.0476 0.0024 0 0.0024 0 0.99768 0.847 0.554 0.724 0.738 0.860 0.545
0.100 0 0.0968 0.0032 0 0.0032 0 0.99554 0.817 0.478 0.663 0.685 0.826 0.473
0.200 0 0.1958 0.0043 0 0.0043 0 0.99150 0.784 0.402 0.598 0.632 0.790 0.399 L
0.400 0 0.3946 0.0054 0 0.0054 0 0.98399 0.743 0.327 0.529 0.580 0.746 0.326
0.600 0 0.5939 0.0061 0 0.0061 0 0.97700 0.715 0.285 0.488 0.553 0.717 0.284 ?
0.800 0 0.7935 0.0066 0 0.0066 0 0.97029 0.696 0.256 0.460 0.538 0.698 0.256
0.235 2
1.ooo 0 0.9933 0.0069 0 0.0069 0 0.96369 0.683 0.236 0.440 0.530 0.684
0.220 G
1.200 0 1.1931 0.0071 0 0.007 1 0 0.95708 0.675 0.221 0.425 0.527 0.676
1.400 0 1.3930 0.0072 0 0.0072 0 0.95036 0.672 0.209 0.414 0.528 0.673 0.209 z
1.600 0 1.5929 0.0073 0 0.0073 0 0.94348 0.672 0.200 0.405 0.533 0.673
0.200 s!
1.800 0 1.7929 0.0073 0 0.0073 0 0.93636 0.675 0.193 0.399 0.540 0.676 0.193 w
2.000 0 1.9930 0.0073 0 0.0073 0 0.92898 0.681 0.188 0.394 0.550 0.682 0.188
0.184 x
2.200 0 2.1930 0.0073 0 0.0073 0 0.92129 0.689 0.184 0.390 0.563 0.689
2.400 0 2.3931 0.0072 0 0.0072 0 0.91327 0.699 0.181 0.388 0.578 0.699 0.180 ”
2.600 0 2.5932 0.0072 0 0.0072 0 0.90489 0.710 0.179 0.387 0.595 0.711 0.178 2
2.767 0 2.7603 0.0071 0 0.0071 0 0.89760 0.722 0.177 0.387 0.611 0.722 0.177 F;3
2.800 0 2.7933 0.0071 0 0.0071 0 0.89613 0.724 0.177 0.387 0.615 0.725 0.177 E
3.000 0 2.9934 0.0070 0 0.0070 0 0.88699 0.739 0.177 0.387 0.637 0.740 0.176

(d) 308 .15 K

0.001 0.0000 0.0010 0.0000 0 0.001 0.99996 0.988 0.928 0.964 0.964 0.989 0.953
0.002 O.oooO 0.0020 0.0000 0 0.001 0.99993 0.983 0.901 0.950 0.950 0.984 0.939
0.005 O.oool 0.0049 0.0001 0 0.002 0.99982 0.974 0.852 0.923 0.925 0.974 0.913
0.010 0.0001 0.0098 0.0001 0 0.004 0.99965 0.965 0.803 0.896 0.898 0.965 0.886
0.020 0.0002 0.0195 0.0002 0 0.009 0.9993 1 0.953 0.743 0.861 0.865 0.953 0.850
0.050 O.OW6 0.0487 0.0006 0 0.024 0.99832 0.932 0.649 0.801 0.809 0.932 0.791
0.100 0.0013 0.0974 0.0013 0 0.05 1 0.9967 1 0.914 0.571 0.747 0.761 0.914 0.737
0.200 0.0028 0.1945 0.0028 0 0.108 0.99357 0.895 0.493 0.686 0.709 0.895 0.676
0.400 0.0057 0.3886 0.0057 0 0.233 0.98745 0.876 0.417 0.622 0.660 0.876 0.613
z 0 0.600 0.0087 0.5826 0.0087 0 0.373 0.98142 0.867 0.376 0.586 0.634 0.867 0.577
0 0.800 0.0117 0.7765 0.0117 0 0.525 0.97544 0.863 0.348 0.561 0.619 0.863 0.553
0 1.000 0.0147 0.9704 0.0147 0 0.690 0.96946 0.861 0.328 0.543 0.610 0.861 0.535
0.001 0.001 0.0008 0.0012 0.0000 0.0002 0.000 0.99991 0.968 0.872 0.933 0.933
0.002 0.002 0.0018 0.0022 0.0000 0.0002 0.000 0.99982 0.954 0.827 0.907 0.909
0.005 0.005 0.0048 0.0052 0.KKK.l 0.0002 0.000 0.99958 0.931 0.753 0.863 0.866
0.010 0.010 0.0098 0.0102 O.oooO 0.0002 OMKI 0.99918 0.910 0.686 0.820 0.826
0.020 0.020 0.0198 0.0202 0.0000 0.0002 0.000 0.99840 0.887 0.612 0.770 0.779
0.050 0.050 0.0498 0.0502 0.0000 o.ooo2 0.000 0.99615 0.855 0.511 0.694 0.712
0.100 0.100 0.0999 0.1001 0.0000 o.ooo2 0.001 0.99255 0.830 0.435 0.632 0.660
0.200 0.200 0.1999 0.2001 0.0000 O.Oc@l 0.002 0.98563 0.803 0.362 0.567 0.611
0.400 0.400 0.4OCQ 0.3999 0.0001 0.0001 0.005 0.97245 0.775 0.293 0.504 0.570
0.600 0.600 0.6001 0.5998 o.cm1 o.ooo1 0.008 0.95961 0.763 0.256 0.472 0.557
0.800 0.800 0.8001 0.7997 o.ooo2 O.Oml 0.012 0.94669 0.760 0.234 0.453 p.558
l.OMl l.ooO 1.0001 0.9997 o.caI2 0.0001 0.016 0.93345 0.764 0.219 0.443 0.567
0.001 0 0.0006 O.OMkl 0 0.0004 0 0.99994 0.972 0.892 0.944 0.944 1.110 0.742
0.002 0 0.0014 0.0006 0 0.0006 0 0.99989 0.959 0.852 0.921 0.922 1.061 0.750
0.005 0 0.0040 0.0011 0 0.0011 0 0.99973 0.934 0.784 0.881 0.883 1 .ooo 0.725
0.010 0 0.0085 0.0015 0 0.0015 0 0.99948 0.911 0.721 0.842 0.846 0.956 0.683
0.020 0 0.0179 0.0021 0 0.0021 0 0.99901 0.884 0.650 0.795 0.801 0.914 0.627
0.050 0 0.0469 0.0031 0 0.0031 0 0.99767 0.846 0.549 0.722 0.735 0.864 0.538
0.100 0 0.0958 0.0042 0 0.0042 0 0.99553 0.817 0.473 0.662 0.683 0.828 0.466
0.200 0 0.1945 0.0055 0 0.0055 0 0.99148 0.785 0.398 0.597 0.630 0.792 0.394
0.400 0 0.393 1 0 0.0070 0 0.98390 0.746 0.325 0.531 0.580 0.751 0.323
0.600 0 0.5922 0 0.0079 0 0.97676 0.722 0.284 0.493 0.555 0.725 0.283
0.800 0 0.7917 0 0.0085 0 0.96983 0.706 0.258 0.468 0.542 0.709 0.257
I .ooo 0 0.9913 0.0089 0 0.0089 0 0.96292 0.697 0.239 0.450 0.535 0.699 0.238

(e) 318.15 K
0 0.001 O.WOO 0.0010 0.0000 0.001 0.99996 0.988 0.927 0.963 0.963 0.990
0 0.002 O.OCOO 0.0020 0.0000 0.001 0.99993 0.983 0.900 0.949 0.949 0.984 0.938 3
0 0.005 0.0001 0.0049 0.0001 0.003 0.99982 0.974 0.850 0.922 0.923 0.974 0.911 5
0 0.010 0.0001 0.0098 0.0001 0.006 0.99965 0.964 0.800 0.894 0.896 0.964 0.883 5
0 0.020 O.OCQ? 0.0195 0.0003 0.012 0.9993 I 0.952 0.739 0.859 0.862 0.952 0.848
0 0.050 0.0007 0.0487 0.0007 0.03 1 0.99832 0.931 0.644 0.798 0.806 0.931 0.788
0 0.100 0.0014 0.0972 0.0014 0.065 0.99672 0.913 0.566 0.743 0.757 0.913 0.733
0 0.200 0.0029 0.1942 0.0029 0.139 0.99358 0.894 0.487 0.683 0.705 0.894 0.673
0 0.400 0.0060 0.3880 0.0060 0.303 0.98745 0.876 0.412 0.620 0.656 0.876 0.610 o
0 0.600 0.0092 0.5X16 0.0092 0 0.484 0.98140 0.868 0.371 0.584 0.631 0.868 0.575 z
 TABLE &continued

m(nominal) m(equilibrium)
mol.kg-’ mol.kg-’ P(CW
.,st .,st
Na,X NaY X2- Y- HJ Z lo5 Pa Qw $ ;‘Na,X YNaY )‘NaZ i Na,X iNaY
__v
0 0.800 0.0123 0.7751 0.0123 0 0.682 0.97538 0.865 0.344 0.561 0.616 0.865 0.522
0 1.000 0.0156 0.9686 0.0156 0 0.898 0.96936 0.864 0.324 0.544 0.608 0.864 0.535
0.001 0.001 0.0007 0.0013 0.0000 o.OcKI3 0.000 0.99991 0.969 0.871 0.932 0.933
0.002 0.002 0.0017 0.0023 0.0000 0.0003 O.ooO 0.99982 0.955 0.825 0.906 0.908
0.005 0.005 0.0046 0.0054 0.0000 0.0004 O.OC@ 0.99957 0.931 0.749 0.861 0.864
0.010 0.010 0.0096 0.0104 O.oooO 0.0004 O.ooO 0.99918 0.909 0.681 0.818 0.823
0.020 0.020 0.0197 0.0204 0.0000 O.OCQ4 0.000 0.99840 0.886 0.606 0.767 0.776
0.050 0.050 0.0497 0.0503 0.0000 0.0003 0.001 0.99616 0.853 0.504 0.691 0.708
0.100 0.100 0.0998 0.1002 0.0000 0.0003 0.001 0.99257 0.828 0.429 0.628 0.655
0.200 0.200 0.1998 0.2001 0.0001 0.0002 0.003 0.98565 0.802 0.356 0.565 0.606
0.400 0.400 0.3999 0.4000 O.oool o.oLmI2 0.006 0.97237 0.777 0.289 0.505 0.568
0.600 0.6CKl 0.6000 0.5998 0.0001 0.0001 0.011 0.95930 0.769 0.254 0.475 0.556
0.800 0.800 0.8001 0.1997 0.0002 0.0001 0.017 0.94602 0.770 0.234 0.459 0.558
1.000 1.000 1.0001 0.9996 o.ooo2 O.OcKIl 0.023 0.93229 0.778 0.220 0.45 1 0.569
0.001 0 0.0005 o.ooo5 0 0.0005 0 0.99994 0.974 0.892 0.944 0.944 1.138 0.704
0.002 0 0.0012 0.0008 0 O.ooO8 0 0.99988 0.960 0.851 0.921 0.922 1.085 0.722
0.005 0 0.0037 0.0013 0 0.0013 0 0.99973 0.936 0.782 0.880 0.882 1.017 0.706
0.010 0 0.0081 0.0019 0 0.0019 0 0.99948 0.912 0.717 0.840 0.844 0.968 0.669
0.020 0 0.0174 0.0026 0 0.0026 0 0.99900 0.884 0.645 0.792 0.799 0.922 0.615
0.050 0 0.0461 0.0039 0 0.0039 0 0.99766 0.845 0.543 0.719 0.732 0.867 0.528
0.100 0 0.0947 0.0053 0 0.0053 0 0.99553 0.815 0.466 0.658 0.678 0.829 0.458
0.200 0 0.1931 0.0070 0 0.0070 0 0.99148 0.783 0.391 0.594 0.625 0.792 0.387
0.400 0 0.3912 0.0089 0 0.0089 0 0.98388 0.746 0.320 0.529 0.576 0.752 0.317
0.600 0 0.5901 0.0100 0 0.0100 0 0.97667 0.724 0.280 0.493 0.552 0.728 0.279
0.800 0 0.7894 0.0107 0 0.0107 0 0.96961 0.711 0.255 0.469 0.540 0.714 0.254
1MKl 0 0.9890 0.0112 0 0.0112 0 0.9625 1 0.704 0.237 0.453 0.535 0.707 0.236
 THERMODYNAMICS OF AQUEOUS CARBONATE SOLUTIONS 637
5. Final comment
The success of this general procedure for (bicarbonate + carbonate + chloride)
solutions with sodium ion suggests similar studies with other cations. The extension
to potassium or other alkali ions is self-evident. But (bicarbonate -t chloride)
solutions with Ca’+, Mg2+, and other cations could also be investigated with cell (2)
and equation (3) would apply. Equation (6), as appropriately modified, would yield
the parameters determining the activity coefficients of Ca(HCO,),, Mg(HCO,),, etc.
This information would be valuable in interpreting the properties of various natural
waters and the solubility therein of CaCO,, MgCOJ, etc.

This work was supported by the Director, Office of Energy Research, Office of Basic
Energy Sciences, Division of Engineering, Mathematics, and Geosciences of the U.S.
Department of Energy under Contract No. W-74055ENG-48. We thank Professor
Roy and his associates for making their results available in advance of publication.

REFERENCES
I. Millero. F. J. The Sea, Vol. 5. Goldberg, E. D.: editor. Wiley: New York. 1974, p. 3
2. Davison, W.; Whitfield. M. J. Electroanal. Chem. 1977, 75. 763.
3. Pitzer. K. S. J. Phvs. Chem. 1973, 71, 268.
4. Pitzer, K. S.; Mayorga, G. J. Phys. Chem. 1973, 77, 2300.
5. Silvester. L. F. : Pitzer. K. S. J. Phvs. Chem. 1977. 81. 1822.
6. Pitzer, K. S.; Kim, J. J. J. Am. &em. Sot. 1974, 96, 5701.
7. Pitzer, K. S.; Mayorga, G. J. Solution Chem. 1974, 3. 539.
8. Pitzer, K. S.; Silvester, L. F. J. Phys. Chem. 1978, 82, 1239.
9. Pitzer. K. S.; Silvester, L. F. J. Solution Chem. 1976, 5, 269.
10. Pitzer, K. S.; Roy, R. N.; Silvester, L. F. J. Am. Chem. Sot. 1977, 99. 4930.
11. Harned, H. S.; Davis, R., Jr. J. Am. Chem. Sot. 1943, 65. 2030.
12. Harned, H. S.; Bonner. F. T. J. Am. Chem. Sot. 1945, 67, 1026.
13. Pitzer. K. S.; Peiper, J. C. J. Phys. Chem. 1980, 84, 2396.
14. Roy, R. N. ; Gibbons, J. J.; Trower. J. K.; Lee, G. A.; Hartley, J; Mack. G. J. Chem. Thermo&wzmics
1981, 14. 473.
15. Harned. H. S.; Scholes, S. R., Jr. J. Am. Chem. Sot. 1941, 63, 1706.
16. Robinson, R. A.; Macaskill, J. B. J. Solution Chem. 1979, 8, 35.
17. White, D. R.. Jr.; Bates, R. G. Aust. J. Sci. 1980, 33. 1903.
18. Berg, R. L.; Vanderzee, C. E. J. Chem. Thermo&amics 1978, 10, 1049; 1978, 10. 1113.
19. Perron, G.; Desnoyers, J. E.; Millero, F. J. Can. J. Chem. 1975. 53. I 134.
20. Goldberg, R. N. J. Phys. Chem. Ref. Data 1981, 10, 671.
21. Harvie. C. E.; Weare, J. H. Geochim. Cosmochim. Acta 1980. 44. 981.
22. Pitzer, K. S. Activity Coefficients in Electrolyte Solutions, Vol. 1. Pytkowicz. R. M.: editor, CRC
Press: Boca Raton, Florida. 1979, p. 7.
23. Piper, K. S. J. Solution Chem. 1975, 4, 249.
24. Friedman, H. L. Ionic Solution Theory. Interscience: New York. 1962.
25. Bradley, D. J. ; Pitzer. K. S. J. Phys. Chem. 1979, 83, 1599.
26. Woolley. E. M.; Hepler, L. G. Can. J. Chem. 1977, 55. 158.
27. Cohen, E. R.; Taylor, B. N. J. Phys. Chem. RefI Data 1973, 2, 663.
28. Bates, R. G.; Macaskill. J. B. Pure Appl. Chem. 1978, 50. 1703.
29. Bates, R. G. ; Guggenheim, E. A. ; Harned. H. S. ; Ives. D. J. G. ; Janz. G. J.; Monk. C. B.; Prue, J. E.;
Robinson, R. A.; Stokes, R. H.; Wynne-Jones. W. F. K. J. Chem. Phys. 19%. 25. 361; 1957, 26.
222.
30. Harned. H. S.; Ehlers, R. W. J. Am. Chem. Sot. 1932, 54, 1350; 1933. 55. 3179.
31. Desnoyers, J. E.; de Visser. C.; Perron. G.; Picker. P. J. Solution Chem. 1976, 5. 605.
32. Grenthe. 1.; Ots, H.; Ginstrup, 0. Acta Chem. Stand. 1970. 24. 1067.
33. Guggenheim, E. A.; Turgeon, J. C. Trans. Faraday Sot. 1955, 51. 757.
638 J. C. PEIPER AND K. S. PITZER

34. Harned. H. S.; Gear). C. G. J. Am. Chem. Sot. 1937. 59. 2032.
35. Harned. H. S. ; Owen, B. B. The Physical Cltentistrr c~f E(ecrrolt,re Solurions. 3rd edition, Reinhold :
New York. 1958.
36. Robinson, R. A.; Stokes, R. H. Electrolyte Solurions. 2nd edition, revised. Butterworths: London.
1965.
37. Olofsson, G.; Olofsson. I. J. Chem. Thermodynamics 1973, 5. 533.
38. Olofsson. G. ; Hepler. L. G. J. Solution Chem. 1975, 4. 127.
39. Silvester. L. F.: Pitzer. K. S. J. Solution Chem. 1978, 7, 327.
40. Taylor. C. E. J. Am. Chem. Sot. 1955, 59. 653.
41. Peiper. J. C.; Pitzer. K. S. In preparation.
42. Clarke, E. C. W.: Clew, D. N. Trans. Faraday Sot. 1966, 62, 539.
43. Bezboruah, C. P.: Camoes. M. F.; Covington, A. K.: Dobson. J. V. J. Chem. Sot. Farada?) Trarls. I
1973, 69. 949.
44. Stimson. H. F. Am. J. Phyr. 1955, 23. 622.
45. Rossini, F. D. Nat/ But-. Stand. (U.S.) Circ. 500. 1952.
46. Loomis, E. H. Phvs. Rev. 18%. 3, 270; Ann. Phjas. (Leipzig) 1896, 57. 495.
47. Weiss, R. F. Marine Chem. 1974, 2, 203.