Limnology Oceanography - March 1974 - Pytkowicz - Bicarbonate and Carbonate Ion Pairs and A Model of Seawater at 25 C1

19395590, 1974, 2, Downloaded from https://aslopubs.onlinelibrary.wiley.com/doi/10.4319/lo.1974.19.2.0223 by Nri For Chemistry And, Wiley Online Library on [30/01/2023].
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Bicarbonate and carbonate ion-pairs and a
model of seawater at 25°C
R. M. Pytkowicx and J. E. Hawley

School of Oceanography, Oregon State University, Corvallis 97331
Abstract
The apparent (stoichiometric) association constants for the formation of ion-pairs be-
tween bicarbonate and carbonate and the major cations of seawater at 25°C were dctcr-
mined experimentally. The results wcrc used, in conjunction with earlier data on sulfate
ion-pairs, to calculate the concentrations of the major species present in scawatcr.
Here we measured the apparent (stoi- tion. The effect of interactions on activity
chiometric) association constants for the coefficients can be successfully accounted
formation of bicarbonate and carbonate by two approaches; the specific interaction
ion-pairs with sodium, calcium, and mag- model of Br@nstcd ( 1922) and Guggen-
nesium ions at 25°C and 0.72 ionic strength. heim ( 1935)) in which interaction terms
The results were used, in conjunction with of an unspecified nature arc measured in
the sulfate association constants determined bi.nary solutions and are applied to sea-
by Kester and Pytkowicz ( 1969)) to detcr- water ( Leyendclkers 1972; Robinson and
mine the major ionic species present in sea- Wood 1972; Whitfield 1973) and the ion-
water at 25°C and 34.8z0 salinity. We will pair concept of Bjerrum, which was intro-
show later that the proportions of ion-paired duced to oceanography by Carrels and
and free species are insensitive to the Thompson (1962), and in which associ-
salinity. ation constants are determined and applied
Activity coefficients are lower and solu- to seawater. The two methods differ in
bility products higher in some mixed elcc- their algebra but have much in common bc-
.trolyte solutions such as seawater than in cause they both require measurements in
chloride solutions ( Kester and Pytkowicz simple solutions and their application to
1969). This is usually attributed to ionic seawater by the use of an extended ionic
interactions, which can range from the for- strength principle, namely, that interaction
mation of ion-pairs (outer sphere interac- coefficients and association constants are
tions due to electrostatic attraction) to that independent of the medium composition at
of true complexes (inner sphere bonds with a given ionic strength. The validity of this
loss of water of hydration). Partial molal principle was tested successfully (Pytko-
volume data (Kestcr 1969) and results from wicz and Kcster 1969; Kcster and Pytko-
Raman spectra (Daly et al. 1972) suggest wicz 1969; ILeyendekkers 1972; Robinson
that the major ions of seawater may form and Wood 1972; Whitfield 1973) because
ion-pairs, although the potentiometric species distributions and activity coeffi-
method we used does not distinguish be- cients calculated from measurements in
tween ion-pairs and complexes. binary solutions agreed with results in sea-
Ionic interactions are important because, water, and because apparent association
by affecting the charge distribution of constants were found to be independent of
solutes, they influence properties such as composition at a given ionic strength. Both
electrical conductivity, osmotic pressure, methods are compatible with Harned’s rule
solubility of minerals, and sound attenua- (Pytkowicz and Kester 1969) and lead to
successful predictions of activity coeffi-
‘This work was supported by National Science cients (Leyendekkers 1972; Whitfield 1973).
Foundation Grants GA-17011 and (X-36057X and
by Office of Naval Research Contract N00014-07- It should be emphasized that, although
A-0369-0007. apparent association constants can be mea-
LIMNOLOGY AND OCEANOGRAPHY
223 MARCH 1974, V. 19(2)
19395590, 1974, 2, Downloaded from https://aslopubs.onlinelibrary.wiley.com/doi/10.4319/lo.1974.19.2.0223 by Nri For Chemistry And, Wiley Online Library on [30/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
224 Pytkowicx and Ha&e y
sured in simple binary solutions and ap- ate ions, changes in the dissociation equi-
plied to seawater, resulting total activity libria of carbonic acid with composition at
coefficients and species distributions are constant ionic strength provide the ion.-
functions of the medium composition. The- pairing information.
oretical grounds for the invariance of stoi- We have used reference electrodes with
chiometric constants and the concepts of salt bridges and assumed that liquid junc,-
free versus total activity coefficients were tion potentials, to a first approximation,
discussed by Pytkowicz (1969) and by are independent of composition at a given
Kester ( 1969). ionic strength rather than avoiding salt
Main features of the model estimated by bridges and having to make assumptions
Garrels and Thompson (1962) have been about the activity coefficient of chloride
confirmed (Berner 1965; Thompson 1966; ions. Either approach has to be viewed
Thompson and Ross 1966; Pytkowicz and with caution and the results considered
Gates 1968; Pytkowicz and Kester 1969; tentative until confirmed by other inde-
Kester and Pytkowicz 1968, 1969) but pendent methods. Our assumption about
there are significant differences for several liquid junction potentials appears justified,
species concentrations, especially anionic within the precision of the method, because
ones. This occurs because Garrels and the association constants that we deter-
Thompson used estimated singIe ion ac- mined for sulfate ion-pairs (Pytkowicz and
tivity coefficients which are uncertain, Kester 1969) and for bicarbonate ion-pairs
especially in the case of sulfate ions, as ( this work) are independent of composi-
these are associated in all solutions that tion and lead to a successful prediction of
could be used for the mean salt method, the activity coefficients of cations (Kester
and because they assumed, as a result of and Pytkowicz 1969). In the case of ca:c-
the scarce data available at the time, that bonates we are forced to invoke triple ions
the activity coefficients of charged ion- to explain the measurements although the
pairs were equal to those of bicarbonate experimental results may reflect changing
while those of ion-pairs with zero net liquid junction potentials. Still, the rela-
charge were the same as those of nonelec- tive strength of the several triple ions will
trolytes, even though ion-pairs are dipolar be justified from an energetics viewpoint
entities. and the extent of carbonate association
We avoided questionable assumptions shown to be compatible with data on car-
about activity coefficients in our choice of bonic acid dissociation and on calcium
experimental methods as far as possible. carbonate solubility. Earlier workers did
In the earlier sulfate work we used ratios not find triple ions because they did not
of activity coefficients of cations, thus can- measure the concentration dependence of
celing errors in part, and at no time did the association.
we have to resort to estimating activity The ion-pair concept is used in preference
coefficients of anions and of ion-pairs. The to the specific interaction model because
difficulty of estimating such coefficients data on sound attenuation (Fisher 1967)
accurately makes it difficult to apply the and from Raman spectroscopy (Daly et
thermodynamic association constants deter- al. 1972) indicate that ion-pairs may indeed
mined by Hostetler (1963), Nakayama exist. Still, the specific interaction model
( 1971), and Reardon and Langmuir (in
is a valuable tool for the study of multi-
prep.) to seawater.
In the sulfate work chloride solutions electrolyte solutions.
were used as reference solutions (in which Details of experimental and calculation
association does not occur) and cation activ- procedures not presented here are avail-
ities were compared in chloride and seawa- able in Hawley ( 1973).
ter to determine the extent of ion-pairing. We thank C. Culberson and S. Ingle for
In this work on bicarbonate and carbon- assistance in this work and. S. Williams for
Bicarbonate and carbonate ion-pairs 225
typing and proofing the many versions of related to yIIco,, the free activity coefficient
the manuscript. which applies only to the nonassociated
ions, by (Pytkowicz et al. 1966; Pytkowicz
Theoretical 1969)
The methods used to determine the ap- aII00, = ~IICO,(HCOs-) = fmo,( HCOa-) T; (2)
parent ( stoichiometric) association con-
stants are based on the variation of K’1 and ( HC03-) and ( HC03-) T are the molal con-
K’2, the apparent dissociation constants of centrations of the fret and the total (free
carbonic acid ( Lyman 1956)) with the plus ion-paired) bicarbonate ions. (I-ICOS-)T
major ion composition of the test solutions is given by
at constant ionic strength. ( HCOa-)T = ( IIC03-) + ( NaHCOSO)
The equations presented below were + (MgI-ICOs+) + ( CaHC03+). (3)
used to derive the working relation for the
determination of the association constants. The apparent association constant for a
The first apparent dissociation constant is generic ion-pair MHCOSC-l, where c is the
related to the first thermodynamic disso- charge of the cation MC, is
ciation constant, K1, by
(MHCO$-l)
K’ I = kf~o,a&G/f-tI~o,; (1) K” MIICO, =
(M”)(HCOa-)
k is the correction in aII, the hydrogen ion
= yMyI-Ico3 K YIIco,.
activity, which results from pH measure- YMIICO,
(4)
ments in concentrated solutions ( Hawley

and Pytkowicz 1973)) fee, is the activity Equation 5 in Table 1, the relation used
coefficient of molecular COa, arI,o is the by us to determine K*~~rree3, was obtained
activity of water, and frrcc, is the total ac- from equations 1 through 4. ZV1 = kK1/
tivity coefficient of bicarbonate. fIIeO, is levee, was determined experimentally as
Table 1. Equations referred to in the text.
’
K1
* = KI/1 1 t K” (Nat) + K*Mg,Ico (W2’) + K*CaHCO ( Ca2+) (5)
NaHC03
3 3 I
aH20f CO2
K;K’2
= K’;KN 1 tK* NaCo (Nat) + K*Mgco (Ms2+) t K*caco lCa2’) (6)
* 2
3 3 3 I
aH20E CO2
= KP;K/Z 1 t KxcNaCO (Nat) t K* MgGO Ws2? +

3 3
*
K CaCO (Ca2f) + K*Mg co (Mg2+)’ t
3 2 3
K*
Ca CO (Ca2t)2 ’ K*MgCaCO (Mg2’)( Ca2+) (8)
2 3 3 I
226 Pytkowicx and Hawley
will be shown below. Equation 6 in Table

1, the working relation for the determina-
tion of K*dlCO, was obtained from a set of
equations similar to 1 through 4 but with
the use of K’lK’z instead of just K’, . K”l K”z
in equation 6 is kSKIKz/yco,.
The values of K*;lIITTCOy,K”,, K*cc,, and
K”lK”2 were determined by measuring K’1
and K’,K’2 in a series of solutions of vary-
ing composition but the same ionic strength.
This led to a system of equations such as
5 and 6 which could be solved for the de-
LY!5r&d+
0 0.20 0.:!4
Magnesium Concenlrotion , mold
sired quantities, although the solution of
Fig. 1. K’JuH,o~co~as a function of magne-
the equations for K*c,,-,, required extra sium concentration in NaCl-MgCb solutions at
terms. K’l and K’lK’2 were obtained by the 25°C and 0.72 ionic strength.
methods used by Kester and Pytkowicz
(1967) for the apparent dissociation con-
stants of phosphoric acid. In essence, K’1 this assumption. For ASW, fco, was cal-
was determined by titrating the solutions culated from the solubility data of Murray
with I-ICI and using the equation and Riley ( 1971). aiI,o was obtained from
osmotic coefficient data ( Robinson and
TC02 K’l Stokes 1968 ) and the additivity relation of
~ - Kfl
ar1 = -CA Robinson and Bower ( 1965).
It can be shown that, in the absence of
where CA = ( HC0,7-) T + 2( COcj2-) Il is the triple ions, K’~/aI120f~0, should vary linearly
carbonate alkalinity. TC02, the total dis- with the concentration of cations. This
solved inorganic carbon, was held con- can be proven by introducing the ionic
stant by filling the cell completely with strength relationship into equation 5 for
solution. K’1 remains constant as long as binary solutions and eliminating all ion
the major ion composition of the solutions concentrations but one. A linear relation-
remains essentially constant ( Weyl 1961; ship was indeed found in the case of bicar-
Kester and Pytkowicz 1967; Pytkowicz bonate association, as illustrated in Fig. 1
1969). K’lK’2 was obtained by adjusting for a NaCl-MgC12 solution, This did not
the solution to a ~1-1 that was invariant to happen, however, for carbonate association,
the addition of NaHC0,7. The relation as the corresponding plots were curved.
pH = 0.5 ( PK’~ + PK’~) is valid when this We were led therefore to add triple-ion
pH is obtained. terms to equation 6, as is shown in equation
f co, was calculated from the relation 8 (Table 1). Triple ions involving (COs2-)2
fco = So/S, in which So and S are the solu- were not required because the concentra-
bihties of CO2 in distilled water and in the tion of carbonate ions was much lower than
test solution, and the solubility data of those of the cations, rendering the prob-
Markham and Kobe ( 1941). We assumed ability of such triple ions negligible. Also,
that the activity coefficient of CO2 in the the data fit equation 8 better without the
solutions was the same as that in a NaCl term K*C112c;o,(Ca2+) 2, as was expected be-
solution of the same ionic strength and cause the concentration of calcium ions
tested this assumption in NaCl-MgCl2 solu- was kept low relative to those of the other
tions. WC found ftJo, = 1.20 2 0.04 in 0.72 cations to prevent precipitation of calcium
m NaCl, 1.20 * 0.04 in 0.36 m NaCl-0.12 carbonate.
m MgClz, and 1.14 c 0.04 m in 0.24 m The fitting of the measured values of K’1
MgC12. Also, as will be shown later, the and K’lK’3 to the systems of equations such
results for bicarbonate are compatible with as 5 and 8 was done by solving for K”‘1,
Table 2. Composition of the test solutions in molal units.
Test (NaHC03)TQ
solution
numbe r (Na2S04)T (CaC12JT x 103
0.3702 ---- --.,- w--- 5. 00

2 ---- 0.7200 ---- ---- 5. 00
3 ---” 0.4800 0.0800 ---- 5.00
4 ---- 0.2400 0.1600 ---- 5. 00
5 ---- ----
0.2400 ---- 5. 00
6 ---- 0. 6300 ---- 0.0300 5. 00
7 --se 0.4800 ---- 0.0800 5.00
8 -m-w ---- 0.1900 0.0500 5. 00
9 0.1400 0.1000 5. 00
10 ---- 0.6000 0.0400 ---- 5.00
11 ---- 0.5700 -m-w 0.0500 5.00
12 ---- -m-m 0.2200 0.0200 5.00
ASW 0.0315 0.4659 0.0597 0.01195 5. 00
hk
Added as Na2C03 but expressed as NaHC03 because of the c:onversion of C032- to HC03 -
due to the reaction with C02. When the solutions were used for the study of carbonate ion-
pairs, varying amounts of NaHCO were added to find the pH which was invariant to further
3
additions.
K”lK”2, and the association constants, with by the Mohr titration (Blaedcl and Meloche
the condition that these quantities had to 1957). The standard Na&03 solution was
be positive. prepared by weight from Mallinckrodt pri-
The calculation procedures used to deter- mary standard Na2COs (99.96% pure)
mine the distribution of species were simi- which had been dried for 2 hr at 280°C
lar to those of Kester and Pytkowicz ( 1969). an d cooled in a vacuum desiccator. The
A system of equations of the type I-ICI titrant was standardized by potentio-
(Na+)T = (Na+) + (NaS04-) metric titration of primary standard
Na2C0s.
+ ( NaHCOso) + ( NaC03-) (9)
Electrode potentials were measured us-
(NaSOd-) ing a potentiometric circuit similar to the
K* (10) one described by Kester and Pytkowicz
Nas04= (Na-‘)(S(-&2-)
( 1967). The sensitivity of the system was
extended to all the species present was within ~O.OI mV.
solved for the concentrations of free ions, Titrations for the determination of K’1
ion-pairs, and triple ions. were performed in the cell shown in Fig. 2,
constructed from a 200-ml Berzelius beaker
Experimental procedures fitted with a water jacket to allow tempera-
The compositions of the test solutions ture control of +O.O3”C. The barrel of a
are shown in Table 2. The solutions were 5-ml ground glass syringe was cut off and
prepared by weight, corrected to weight mounted horizontally in the cell with epoxy
in vacuum. Reagent grade NaCl and cement. The piston of the syringe was dis-
NagSO4 were dried and weighed as solid placed as titrant was added, eliminating the
salts while MgC12, CaCl2, and Na2C03 were need for an air space to take up the titrant
added from stock solutions standardized volume; it displaced about 4 ml of test solu-
Thermomeier
TO
E/et fronfcs
GiUSS
E/ecrook
0
‘1 ,.=; , I )
I 2 3 5
I/CA
Fig. 3. UH versus l/CA from the titration of
Ground G/ass a 0.7200 m NaCl and 0.005 m NaHCO, solution
syringe with HCl.
from a calibrated syringe buret. Finally,

Fig. 2. Water-jacketed titration cell. pH elec- the electrodes were returned to the buffe:r
trodc, Sargent S-30050-15C; reference electrode, solution and the amount of test solution
Sargent S-30080-15C; syringe buret, Gilmont titrated was determined by weight. The
s 1200.
electrodes were thoroughly rinsed with the
new solution when they were transferred.
tion and was lubricated by a thin film of The linearity of a rI versus I./CA, expected
solution. A pH electrode, a reference elec- from equation 7, is shown in Fig. 3.
trode having a porous ceramic plug liquid For the determination of K’,KIZ the cell
junction, and a thermometer were fitted was completely filled with ,test solution to
tightly into a rubber stopper which had avoid exchange of CO:! and the pH was
been machined to fit into the beaker. A adjusted to about 0.5( pK1 -t p&) by ad-
small hole in the stopper held the syringe dition of a few hundredths of a milliliter of
needle of the titration buret and allowed 0.02 N N&OS. This brought the alkalinity
for overflow of test solution upon filling to about 0.005 meq liter-‘. Then lo-15 mg
of the cell. Electrode potentials in a stan- of reagent grade NaHCOs ‘were placed in
dard buffer solution were the same in the a dry, gastight, 2.5-ml IIamilton syringe
titration cell as in an ordinary thermostated and about 0.3 ml of COZ-free distilled water
beaker. was pulled into the syringe to dissolve the
The titration procedure was as follows. salt. The NaIICOs was injected slowly into
First, the pH electrode pair was standard- the test solution. The solution was stirred
ized in buffer solution (National Bureau for 5 min and the electrode potential was
of Standards buffer 185d having an as- then recorded for 5 min in the absence of
signed pH of 4.008 at 25°C). Next, the ti- stirring. At least five additions of NaHC03
tration cell was completely filled with test were made to establish that a constant pH
solution and the electrodes were allowed had been obtained. The final total alka-
to equilibrate until the potential changed Iinity was about 3.5 meq liter-‘. The con-
by less than 0.1 mV per hour. Then, the stancy of the pH, within the experimental
solution was titrated with standard HCl precision of kO.003 pH units, was aster-
Table 3. Measured values of K’1 and K’s, calculated values of aIt,0 and fCOZ, and values of K’I and
Kpa calculated from equations 5 and 8 and the speciation model.
Test Measured Calculated

solution / / 16 16
K’l x106 KlK2xlO aH20 fC02 K’l x 106 K’lK;xlO
number
1 1.161 2.070 0.983 1. 292 1.160 2. 06

1.161 2. 041
1.072 2.245 0.972 1.178 1.089 2.26
1.084 2. 239
1.085
1.140 8.120 0.977 1.178 1.152 8.12
1.160 7.860
4 1.199 16.79 0.981 1,178 1.211 16. 8
1.243 17.01
1.244 16.65
5 1. 250 28.16 0.986 1.178 1.274 28. 3
1. 278 28.54
6 1.145 6.390 0.974 1.178 I. 122 6.71
7 1.170 0.977 1.178 1.176
8 1.290 34.52 0.986 1.178 1.290 34. 0
9 1.307 0.986 1.178 1.302
10 5.030 4. 84
11 9.840 9.70
12 29.61 29.7
ASW 1.094 8. 02 7. 87”
1.140
1.136
1.143
This is the value calculated from the model which agrees within 3 percent with the average
of the measured values.
Table 4. Values of the apparent (stoichiometric) association constants determined in this work 1(l),
those based on the work of Garrels and Thompson (1962) (2), and those measured by Butler and IIuston
(1970) (3) and by Dyrssen and Hansson (1973) (4).
(1) (2) (3) (4)

Ionic Strength 0072 0. 66 0. 5 1.0
NaH C03’ 0.280 o. 26 0. 39 0.21
MgHC03+ 1.62 5.22 1.04
CaHC03+ 1.96 5.10 1.04
NaC03- 4. 25 4.16 1.38 1.86
MgC03’ 112 160 32.5

2-k
W2C03 387
CaC03’ 162 78 32. 5

2t
MgCaC03 1,040
Table 5. Chemical model for the major species in seawater at 25°C calculated from the sulfate
association constants @ester and Pytkowicx 1969) and the bicarbonate and carbonate association c(?n-
stants (this work: Table 4). The constants for magnesium and calcium fluoride association were taken
from Elgquist (1970). The number of significant figures is used for mass balance purposes and does
not reflect the accuracy which is unknown because of the assumptions made.
=
2f
N2 Mg Ca2 I- d
-
Total molality 0.4822 0. 05489 0. 01063 0.01062

“/c Free metal 97.70 89.11 88.35 100.00
% MS04 2.25 10.35 10.87
7’0 MHC03 0.05 0.24 0. 29
Yc MC03 0.01 0.17 0.41
‘-30Mg2C03 0.03
% MgCaC03 0.01 0.07
% MF 0.07 0.02
-
so42- HC03- cog2- F

-
Total molality 0.02906 0. 00213 0.000171 0. 000080

“/c Free anion 39.19 81.33 7.99 51.04
% NaX 37.29 10.73 15.99
% MgX 19.55 6.44 43.86 46.94
“/c CaX 3.97 1.50 20.96 2.02
% Mg2C03 7.39
% MgCaC03 3.82
-
tained after correction for dilution. The for KS04- is added to the calculations. This
pH = 0.5( pK’1 + pE2) ranged from 7.231 constant should, however, be measured.
to 7.845 in going from MgQ-CaC12 to
NaCI solutions. Discussion
The electrodes ( Fig. 1) were standard- The validity of the model was tested by
ized with NBS buffers 185d (pH = 4.008 at measuring K’, K’ 2 in a solution (ASW in
25°C) and 186-l-b and 186-11-b (pH =7.413 Table 3) with the cation composition of
at 25°C). seawater and comparing it to K’,K’2 calcu-
lated from equation 8, used in conjunction
Results with the association constants determined
Values of K’l, K’JX’Z, aE120,and fee, are in the simpler test solutions. The measured
shown in Table 3. The values of the ap- value was 8.02 X lo-l6 while the calculated
parent association constants are presented value was 7.87 x 10-l”; the two agree within
in Table 4. The percentages of the ions 3%. In addition, the value of KllK’2 r’e-
present as free and as associated species are ccntly measured in seawater by Mehrbach
shown in Table 5. The calculations were et al. (1973) at 25°C and 35s0 salinity was
made at pH 8.0 and 8.1 with no significant 7.68 x 10-‘6. A model including Ca2CO:12+
difference in the results. In Table 6 we yielded 8.13 X lo- Is; thus, it did not agree
present the model if an association constant as well with measurements and, as the cal-
Table 6. Chemical model of Table 5 modified when an association constant for KHSO?, based on
the results of Garrels and Thompson (1962), is added to the calculations. The values in parentheses are
theirs.
2-b Ca2+ K+
Nat Mg
$J Free metal 97.71 (99) 89.15 (87) 88.39 (91) 98.85 (99)
70 MS04 2.24 (1.2) 10.31 (11) 10.82 (8) 1.15 (1)
7’0 MHC03 0.05 (0.01) 0.24 (1) 0.29 (1)
% MC03 0.01 ( ) 0.17 (0.3) 0.41 (0.2)
% Mg2C03 0.03
% MgCaC03 0.01 0.07
% MF 0.07 0.02
so4z- HC o3 - co3z- F-
% Free anion 39.01 (54) 81.33 (69) 7.98 (9) 51.03

% NaX 37.13 (21) 10.73 (8) 15.98 (17)
% MgX 19.47 (21.5) 6.45 (19) 43.86 (67) 46.95
$3 CaX 3.96 (3) 1.50 (4) 20.96 (7) 2.02
% Kx 0.42 (0.5)
% Mg2C03 7.39
% MgCaC03 3.82
cium concentration was kept low to prevent kg-I120-2; Ingle et al. present it in units
precipitation of CaCOs, was rejected. of moles kg-SW-“.
Another test of the validity of the model The agreement between the calculated
is that it can be used to explain the solu- and measured results is fair considering
bility of calcium carbonate in seawater. the uncertainties in the model and in the
The apparent solubility product of calcium measurement of solubility products in sea-
carbonate, K’sIJ is related to the thcrmo- water. Still, the differences suggest, when
dynamic solubility product, KxIJ, by the the data of Ingle et al. are used, that the
equation K’ w = &dfc,fco,. ye the free percent free carbonate may be closer to
ion activity coefficient obtained by the 9.1% than to 8. This is a slight difference
mean salt method, is 0.255 as calculated which could be resolved, for instance, if
by C. Culberson in our laboratory. The the extent of MgCOao association were off
use of an equation such as 2 for carbonate by only 2% of its value.
ions yields fen= 0.225 as 88.35% of the cal- The model of Garrels and Thompson
cium ions are free. f,&k2 = (KlKJK’lK’g) ( 1962), although it yields a percent free
an,0f co, = 0.031 according to the ion asso- carbonate of 9, does not lead to a satis-
ciation model. KNgp= 3.98 X 10-O (Lang- factory prediction of KfBP. They reported
muir 1968) and, thus, we calculate K’gp an d used yea = 0.28 and ycoI = 0.20 which,
= 5.67 x 10-7. The experimental values of in conjunction with their model, yields for
Kgp are 5.4 X 1O-i ( MacIntyre 1965) and the total activity coefficients fCn= 0.91
4.93 X 10d7 (Ingle et al. in press). The x 0.28 = 0.255 and fCO, = 0.09 x 0.20 = 0.018
last value is expressed here as moles and results in Kap = 11.1 X 1O-7 instead of
a value near 5 X 10-7. The error appears evaluated because they did not examine
to arise because they used a rough estimate all the possible pairs. It may be, however,
of YCO~, the free activity coefficient, by that their results are low because ours ex-
Walker et al. (1927). ‘Our value of ycos plain the apparent dissociation constants
is fco,( CO&/( C03) = 0.388. of carbonic acid and the apparent solu-
Our association constant for NaEIC030 bility of calcium carbonate. We found less
is in good agreement with those of Garrels MgCOsO ion-pairing and considerably more
and Thompson (1962) and of Butler and CaCOsO ion-pairing than was the case in
Huston (1970) but the constants for the model of Garrels and Thompson (Ta-
MgHCOs+ and CaHCOs+ differ from those ble 6).
of Garrels .and Thompson ( 1962) and Dyrs- Our model is not complete. Ca2C0,7:!+
sen and Hansson ( 1973). Our results sug- triple ions were not detected because the
gest that calcium associates more strongly concentration of calcium was kept low to
than magnesium with bicarbonate, in con- prevent precipitation of CaC03. In addi-
trast to those based on the estimates by tion, triple ions involving sodium may oc-
Garrels and Thompson (1962), and that cur but were not necessary to explain our
the extent of association for both cations is results, in part because of the composition
slighter than they predicted. Greenwald’s of the test solutions and in part because the
( 1941) calculations also indicate that cal- association of sodium is weaker than those
cium .association with bicarbonate is of magnesium and calcium.
stronger than magnesium association, and The association reactions possible when
TKester and Pytkowicz (1969) found that triple ions form are of the following charge
pK*cnso, was slightly larger than K*MgSO,. types :
The relative strengths of magnesium and
2NA+ + COs2- = Na2C0,0; (11)
calcium association probably reflect the
radii of the hydrated cations, as was sug- Na+ + Mg2+ + COs2- = NaMgC03+; (12)
gestcd by Nancollas (1966). Robinson
2Mg”’ + COs2- = Mg2C03”+. (13)
and Stokes (1968) presented hydration
numbers and ion size parameters for MgC12 The important factor in determining the
b and CaC12, derived from the hydration relative stability of triple ions is their tota.
theory activity coefficients. These param- interaction energy. Consider Na2C030 with
eters suggest that the hydrated radius of a linear Na+-CO 32--Na-b configuration and
calcium ions is smaller than that of mag- with the centers of the ions separated by
nesium ions and, therefore, that calcium the distance r. Assuming point charges for
ions should interact more strongly than rough estimates, the interaction energy is
magnesium with anions, as we found to
be the case. Again, we found K*C,C03 to 2ZmZcop2 &&&”
Ah,,co, = - + (14)
be larger than KQAIgOO,in contrast to the Dr 2Dr ’
constants based on the results of Garrels
and Thompson (1962). The concentration where ZNn and Zco, are the valence charges,
of MgCO,O is larger than that of CaCOs”, e is the electronic charge, and D is the di-
but this is because there is more magne- electric constant. Thus, AUN~,CO, = -7e2,/
Dr. The interaction energies for all the pos-
sium than calcium in seawater.
Our value for K*NaCO:,agrees with that sible triple ions, taking the values of r in
based on Garrels and Thompson (1962) centimeters, based on the effective hy-
but is larger than that of Butler and Huston drated ionic diameters presented by Stumm
( 1970). Our values for K*MgCO,and K*c~co, and Morgan ( 1970)) are listed in Table 7.
indicate significantly more ion association The free energy AF is AH-TAS which
than those of Dyrssen and Hansson ( 1973). is approximately AU-TAS. If it is assumed
The results of Butler and Huston and of that the entropy charge AS is roughly the
Dyrssen and Hansson cannot be definitively same for all triple ions then, as AF = -RT
Table 7. Interaction energies for triple ions constants of ion-pairs that have yet to be
calculated as explained in text. D is the dielectric explained.
constant and e is the electronic charge.
An alternative theory to ion-pair forma-
tion, the specific interacTion theory of Br@n-
Triple ion Interaction energy x lo8 D/e2 sted and Guggenheim, provides results com-
Na2C03 -0.83
parable to those of the ion-pair theory. Both
approaches are equally valuable numer-
NaMgC03 -1.29
ically; although sound attenuation and
NaCaCO3 -1.44
Raman spectra data indicate the actual
MgCaC03 -1.70
existence of ion-pairs.
Mg 2C03 -1.54
Ca2C03 -1.87 References
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bicarbonate, carbonate and calcium ions in
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947-965.
values of the interaction energy will have
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solubility of gases in distilled water and in Accepted: 30 November 1973

Limnology Oceanography - March 1974 - Pytkowicz - Bicarbonate and Carbonate Ion Pairs and A Model of Seawater at 25 C1

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Limnology Oceanography - March 1974 - Pytkowicz - Bicarbonate and Carbonate Ion Pairs and A Model of Seawater at 25 C1

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19395590, 1974, 2, Downloaded from https://aslopubs.onlinelibrary.wiley.com/doi/10.4319/lo.1974.19.2.0223 by Nri For Chemistry And, Wiley Online Library on [30/01/2023].

R. M. Pytkowicx and J. E. Hawley

ments in concentrated solutions ( Hawley

Table 1. Equations referred to in the text.

= KP;K/Z 1 t KxcNaCO (Nat) t K* MgGO Ws2? +

will be shown below. Equation 6 in Table

Table 2. Composition of the test solutions in molal units.

0.3702 ---- --.,- w--- 5. 00

from a calibrated syringe buret. Finally,

Test Measured Calculated

1 1.161 2.070 0.983 1. 292 1.160 2. 06

(1) (2) (3) (4)

NaH C03’ 0.280 o. 26 0. 39 0.21

MgHC03+ 1.62 5.22 1.04

CaHC03+ 1.96 5.10 1.04

NaC03- 4. 25 4.16 1.38 1.86

MgC03’ 112 160 32.5

CaC03’ 162 78 32. 5

Total molality 0.4822 0. 05489 0. 01063 0.01062

so42- HC03- cog2- F

Total molality 0.02906 0. 00213 0.000171 0. 000080

% Free anion 39.01 (54) 81.33 (69) 7.98 (9) 51.03

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