NOTES

Limnol.
Oceanogr., 33(2), 1988, 269-274
0 1988, by the American Society of Limnology

The dissociation

and Oceanography,

Inc.

of hydrogen sulfide in seawater

potentiometric titrations of dilute NaHS solutions (0.005 m) with 1.0 M HCl. Titrations were made in a 250-cm3, water-jacketed closed cell used in previous studies
(Thurmond and Miller0 19 82). HCl was delivered by an automatic buret (Metrohm
E535). The titration system is fully automatic and controlled with a computer (Apple II). The electromotive force of the glass
(Corning) and double-junction
reference
electrode (Orion) was measured with a pH
meter (Metrohm). The outer filling solution
of the reference electrode was 3 M KCl. The
Ag, AgCl reference electrode used in our
earlier work (Thurmond and Miller0 1982;
Miller0 and Thurmond 1983; Hershey et al.
1986) could not be used due to interference
by HS-.
The emf of the electrode system is related
to the total concentration of the proton [H] T
bY

Abstract-The
pK,* for the dissociation of H,S
has been measured in artificial seawater as a function of salinity (S = 5-40) and temperature (Y25C). Results have been fitted to an equation of
the form
pK,* = pK, + AS + BS
where pK, is the value at infinite dilution given
by
pK, = -98.080 + 5,765.4/T + 15.0455 In T
A = -0.1570
B = 0.0135
(V = 0.033 in pK*, mol kg- seawater). The results
at S = 35 show a 0.08 shift in pK* from the
results in the literature, as was also found in 0.7
m NaCl solutions. The results are in good agreement with the apparent pK, results when adjusted to the same pH scale. Using values for the
apparent activity coefficient of the proton, we
combined our results with those results to derive
the consensus values of
A = -0.1498
B = 0.0119

(u = 0.028 in pK,*).

E = E* - (RT/F)ln[H+],
In our studies (Hershey et al. 1988) of the
pK,* for the dissociation of H,S in NaCl
solutions, we found that our measured results at 0.7 m were 0.08 lower than the results of Almgren et al. (1976) at 5 and 25C.
The published results for the pK,* in seawater adjusted to the same pH scale also
show that the results of Almgren et al. (1976)
are 0.08 higher than the results of Goldhaber and Kaplan (1975) and Savenko
( 1977). We were unable to account for these
differences in a simple manner, so we decided to remeasure the pK,* of H2S in seawater as a function of salinity and temperature.
Values of pK,* for the ionization of H,S
in seawater media were determined from
l This work was supported by the Office of Naval
Research (NO001 4-87-G-O 116) and the Oceanographic Section (86-00284) of the National Science Foundation.

(1)

where E* is an apparent standard potential

in the ionic media (and includes liquid junction effects). Values of E* and the pK1* =
-log K,*,
K, = [H+],- [HS-],/[H,S],

(2)

were determined from the titrations with a

nonlinear, least-squares program (Arena et
al. 1979). Values of K,* for the ionization
of water were obtained from the equations
of Miller0 (1979, 198 1) which are based on
the experimental
work of Dyrssen and
Hansson (197 3), Culberson and Pytkowicz
( 197 3) and Dickson and Riley ( 19 79).
Seawater solutions were made by weight
with reagent grade NaCl, Na,SO,, MgCl,,
and CaCl, according to the composition of
artificial seawater from Khoo et al. (1977).
Concentrations of the MgCl, and CaCl, stock
solutions were determined from density
measurements. Solutions of NaHS were

269

270

ivotcs

Table 1. The pK,* for the dissociation

seawater.
Temp (C)

Sallnltl

(S?

5.0
10.0
20.0
35.0

15

25

40.0
1.0
5.2
5.5
9.6
19.5
33.0
34.2
38.9
39.2
5.0
10.0
20.2
30.0
35.0
40.0

pK,*

of H,S in

(mol kg SW)

7.012
7.014
6.982
6.905
6.949
6.897
6.872
6.834
6.969
6.784
6.793
6.756
6.740
6.688
6.654
6.657
6.675
6.627
6.676
6.648
6.648
6.596
6.589
6.534
6.536
6.549
6.554
6.556
6.508

631
01234567
G
Fig. 1. Values of pK,* for the dissociation
in seawater as a function of salinity.

made by dissolving weighed crystals of

NazS. 9H,O in degassed, ion-exchanged
water. HS concentrations were determined
by iodometric titrations. Stock solutions of
NaHS were kept under nitrogen to prevent
oxidation. Diluted seawater solutions were
prepared by weight with ion-exchanged
water.
Temperature of the titration cell was controlled to +O.O2C with a Forma bath. Temperatures were set with a quartz crystal thermometer calibrated with a Pt resistance
thermometer and G-2 Mueller bridge.
Values of pK, * for the dissociation of H,S
obtained in this study at various salinities
and temperatures are given in Table 1. The
effect of salinity is shown in Fig. 1. As with
other acids (Miller0 1979, 198 l), the salinity dependence can be accounted for with
an equation of the form
pK,* = pK, + AS + BS
where pK, is the dissociation

constant

(3)
at

of H,S

infinite dilution, and *4 and B are temperature-dependent parameters.

The effect of temperature on the pK,* for
HS is shown in Fig. 2. The heats of ionization, AH* = R7-(d In K*IdT), are nearly
independent of salinity. Values of AH* =
6.6kO.3, 6.4kO.2, and 6.2kO.2 kcal mol l
were obtained at S = 0, 10, and 40. The
value at S = 35 (AH* = 6.2-t0.2 kcal mol-l)
can be compared to AH* = 7.4kO.1,
6.O-tO. 1, and 6.1 +O. 1 kcal mol- obtained
by Almgren et al. (1976) Goldhaber and
Kaplan ( 19 7 5) and Savenko ( 19 7 7) over the
same temperature range. The agreement is
quite reasonable. The large differences between the various studies and the work of
Almgren et al. cannot be easily explained.
Since they made their measurements only
at 5 and 25C, part of the difference could
be due to the limited temperature range
studied. The effect of temperature on the
pK, in pure water from 0 to 300C can be
obtained from (Hershey et al. 1988)
pK, = -98.080 + 5,765.4/T
+ 15.0455 In T

(4)

(a = 0.05). The higher temperature data are

derived from thermodynamic data (Barber0
et al. 1982) and the low temperature data
(O-45C) are based on new measurements
(Hershey et al. 1988). The differentiation of
this equation with respect to temperature
yields a AH, for the dissociation that is temperature-dependent (AH, = 7.2 and 5.9 kcal
mol-l at 5 and 25C).
Since the thermodynamic
values are re-

Notes

271
K, = a,[HS-],/[H,S],.

(5)

The measurements made by Almgren et al.

(1976) and for our study were made on the
total proton scale (Hansson 1973):
K1* = [H+],.[HS-],/[H,S],.

(6)
The two pH scales are related by (Dickson
1984)

4I = LIw+17631
3.3

34

35
( VT)103

3.6

Fig. 2. Values of pK,* for the dissociation of H,S

in seawater as a function of temperature (TK).

liably known, we have determined the temperature coefficients of Eq. 3 by subtracting

the value of pK, at a given temperature calculated from Eq. 4. The least-squares fit of
these differences (pK,* - pK,) gives A =
-0.1570 and B = 0.0135 (g = 0.033 in
PC).
The measurements of Savenko (1977) and
Goldhaber and Kaplan (1975) were made
with the National Bureau of Standards (NBS)
pH scale (Bates 1973) where
Table 2.

Comparison

of our pK,* results with the values of Almgren

25

7.112
7.046
6.990
6.974
6.979
6.982

0.069
0.082
0.096
0.103
0.109
0.109
Avg 0.095 kO.0 1

20
30
35
40

6.766
6.697
6.619
6.548
6.526
6.524
6.527

6.805
6.739
6.698
6.644
6.617
6.60 1
6.596

0.039
0.042
0.079
0.096
0.09 1
0.077
0.069
Avg 0.07iO.02

m (NaCl)
0.4
0.7

7.015
6.989

7.138
7.078

0.123
0.089
Avg O.llkO.01

6.655
6.675

6.734
6.729

0.079
0.054
Avg 0.07 kO.0 1

2.5

10

25

b Equations

0.4
0.7
3 and 4 wth

et al. 1976.

7.043
6.964
6.894
6.871
6.870
6.873

5
10
20
30
35
40

A = ~ 0.1570

and B = 0.0135

(7)

wheref, is the apparent activity coefficient

of the proton. This value includes effects of
liquid junctions, the definition of the NBS
scale, and the activity coefficient of the proton (Dickson 1984). Since different reference electrodes give different values of&,
it is not possible to determine its value from
first principles.
A comparison of our results for pK,* with
the earlier measurements of Almgren et al.
(1976) is shown in Table 2. At 5C our seawater results are O.lO+O.O 1 lower than
theirs; at 25C our results are 0.07 kO.02
lower. Measurements made in NaCl solutions between 0.4 and 0.7 m also show a
similar difference (Table 2). We have no
logical explanation for this offset. Since the

Notes

272
0 05

:..;:i.
0

IO

15

20

25

30

005
0

0
-0.05

IO

20

30

40

50

Fig. 3. Residuals of errors for the fit of pK, with

the data of Goldhaber and Kaplan 1975 (0) and Savenko 1977 (0).

differences show up as an offset in both seawater and NaCl, they could arise from a
systematic error in the electrode system or
the method of calculating pK1*.
A comparison of the apparent constants
for the pK, of H,S was made with the fitted
equation of Miller0 (1986~~) based on the
work of Goldhaber and Kaplan (1975).
Table 3. Comparison

These comparisons demonstrate that the

pK, results of the two studies agree to kO.02
in pK with a maximum error of 0.05. The
combined data for pK, have been fitted to
Eq. 3 where A = 0.0057 - 19.9WTand B =
0.0028 (c = 0.019 in pK,). Examination of
the residuals between the measured and calculated results shown in Fig. 3 demonstrates
that the two studies are in good agreement
and that the electrode systems gave similar
values offH. The earlier fit (Miller0 1986~1)
of the data of Goldhaber and Kaplan (1975)
is in agreement with the combined fit to
within the experimental error (0.02 in pK,).
The lower standard error for the fit of pK,
(compared to our pK,* data) is probably
related to the experimental techniques of
Goldhaber and Kaplan. They determined
pK, with a spectroscopic method that responds to changes in HS- and is not strongly
affected by various polysulfide species that
may influence the pH titration techniques
we used.
A comparison of our pK,* values with
the apparent pK, calculated from Eq. 3 and
4 is shown in Table 3. The differences in
pK,* - pK, = ApK can be related to the
apparent activity coefficient of the proton

fH= 10 T(APK).

The values offH shown in Table 3 are compared to measurements made by Mehrbach
et al. (1973), Culberson and Pytkowicz

of the pK,* and pK, values of H,S in seawater and estimates off.

fHS

p&t
s

Temp (C)

-A PK,

This study

35

5
10
15
20
25
30
25

6.870
6.772
6.682
6.599
6.524
6.455
6.527
6.524
6.526
6.533
6.548
6.575
6.619
6.697

6.965
6.875
6.792
6.717
6.648
6.586
6.633
6.648
6.666
6.687
6.711
6.741
6.778
6.832

0.095
0.103
0.110
0.118
0.124
0.131
0.106
0.124
0.140
0.154
0.163
0.166
0.159
0.135

0.80
0.79
0.78
0.76
0.75
0.74
0.78
0.75
0.72
0.70
0.69
0.68
0.69
0.73

0.79
0.77
0.75
0.72
0.69
0.66
0.69
0.69
0.68
0.68
0.68
0.67
0.67
0.67

0.79
0.78
0.76
0.74
0.7 1
0.69
0.72
0.71
0.70
0.70
0.70
0.70
0.71
0.72

40
35
30
25
20
15
10
5

(8)

t l--Values
of pK,* from Eq. 3 and 4 wth A = -0.1570
B = 0.0028.
$3-Mehrbach
et al. 1973; 4-Culberson
and Pytkowcz

and B = 0.0135.

Z-Values

1973, 5-Mlllero

19866.

of pK, from Eq. 3 and 4 wth

A = -0.0057

0.72
0.70
0.7 1
0.71
0.71
0.72
0.73
0.74
- 19,98/Tand

Notes
(1973), and Miller0 (1986b). At 25C the
values of fH are nearly independent of salinity. Our average results of& = 0.73 LO.04
can be compared to 0.68 -to.02 by Mehrbath et al., 0.71 +O.Ol by Culberson and
Pytkowicz, and 0.72+0.01 by Millero. The
effect of temperature on the values of fH
calculated in Table 3 are also in good agreement with the measured values of Mehrbath et al. and Culberson and Pytkowicz.
The comparisons in Table 3 clearly demonstrate
that our experimental
pK,*
meaurements are in good agreement with
the results of Goldhaber and Kaplan (1975)
and Savenko (1977) if adjusted to the same
pH scale. To develop a consensus equation
for the pK,* of H,S, we have used values
of& from Mehrbach et al. (1973) Culberson and Pytkowicz (1973), and Miller0
(19863) to convert the pK, data
pK,* = PK, + log.&,.

(9)
To determine fH as a function of salinity
and temperature (FK), we have fitted the
experimentally derived values of Mehrbach
et al., Culberson and Pytkowicz, and Millero to the equation

fH = 0.739 AI 3.07 x 1o-2 s

+ 7.94 x 1o-5 s2
+ 6.443 x 1O-5 T
- 1.17 X lop4 TS

273

-000

25

20

30

OC

0 00
A
004
APK;

0
.

0.

2
A

:.

.A
A8

D l f3
A

-004-

d
00
.A
&,

AA

I
A

r'O

dI

A.

A*
0

A
-0.00

4
IO

20

30

40

Fig. 4. Residuals of errors for the fit of pK,* with

the adjusted data of Goldhaber and Kaplan 1975 (0)
and Savenko 1977 (0) and the results of our study (a).

used to determine the pK,* of H2S in seawater solutions from S = O-40 and T = O35C. The residuals shown in Fig. 4 demonstrate that the three studies are in good
agreement when adjusted to the same pH
scale.

(10)

(a = 0.006). It should be pointed out that

the 25 and 35C data of Mehrbach et al.
have not been used because of large differences (0.02-0.04) with the work of Culberson and Pytkowicz and Millero. Equations
9 and 10 were used to adjust the results of
Goldhaber and Kaplan (1975) and Savenko
(1977) to the total proton pH scale. These
pK,* results agree on the average with those
of this study to kO.02 for Goldhaber and
Kaplan and +0.03 for Savenko. These converted values of pK, * have been added to
the measurements made in our study to derive a consensus equation.
The total data set consists of 72 values:
8 from Savenko ( 1977); 3 5 from Goldhaber
and Kaplan (1975); 29 from this study. A
least-squares fit of these data gives A =
-0.1498 and B = 0.0 119 (a = 0.028 in
pK,*). We feel these parameters should be

15

IO

Frank J. Millero
Tinka Plese
Marino Fernandez
Rosenstiel School of Marine
and Atmospheric Science
University of Miami
4600 Rickenbacker Causeway
Miami, Florida 33 149

References
ALMGREN,
T., D. DYRSSEN. B. ELGQUIST, AND 0.
JOHANSSON.
1976. Dissociation of hydrogen sul-

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S. SAMMARTANO,
AND C.
RIGANO.
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BARBERO, J.A.,K.G.
MCCURDY,AND
P.R. TREMAINE.
1982. Apparent molal heat capacities and volumes of aqueous hydrogen sulfide and sodium hydrogen sulfide near 25C: The temperature depen-

Notes

274

dence of H2S ionization. Can. J. Chem. 60: 18721880.

BATES, R. G. 1973. Determination
of pH: Theory
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CULBERSON, C., AND R. M. PYTKOWICZ.
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AND J. P. RILEY.
1979. The estimation of
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Mar. Chem. 7: 8999.
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apparent dissociation constants of hydrogen sulfide in chloride solutions. Mar. Chem. 3: 83-104.
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MILLERO.
1986. The ionization of boric acid in
NaCl, Na-Ca-Cl and Na-Mg-Cl solutions at 25C.
Geochim. Cosmochim. Acta 50: 137-148.
-,
T. PLESE, AND F. J. MILLERO.
1988. The pK,*
for the dissociation of H,S in various ionic media.
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KHOO,

Submitted: 22 April 1987

Accepted: 21 June 1987
Revised: 15 December 1987

1988, 274-280

0 1988,by the American Society of Limnology and Oceanograph),

Inc

Laboratory studies on core sampling with application

subtidal meiobenthos collection
Abstract -Three
aspects of subtidal meiobenthic sampling were examined through laboratory simulation experiments with Sephadex gel
beads as an epibenthic meiofaunal mimic. Results indicate that corer diameter (i.d. from 2.6
to 10.5 cm) does not affect sampling efficiency if
slow corer penetration takes place. Disturbance
in cores mimicking conditions during retrieval
by a diver resulted in a bias when these cores
were subsampled after collection. Such effects may
also be present in larger (e.g. box) corers when a
distinct flocculent layer is present. A dramatic
effect on vertical profile was found when cores
were preserved by fast-freezing. Cores should be
of a size that can be analyzed in their entirety,
subsampled as a homogenate, or subsampled with
a device in place as the corer enters the sediment.

to

An awareness of the ecological importance of meiofauna has heightened the need

for adequate field sampling. Unbiased population estimates are necessary to underpin
virtually all meiofaunal studies, including
those on pollution effects, community structure, and ecosystem function. As a consequence, many sampling techniques have
been used in the field to attempt quantitative sampling (McIntyre
and Warwick
1984). Unfortunately,
the proliferation
of
techniques has not been accompanied by a
program of testing and evaluation. Only a
few studies (McIntyre 197 1; Elmgren 1973;