Progress in

Oceanography
Progress in Oceanography 74 (2007) 515539
www.elsevier.com/locate/pocean

A GibbsPitzer function for high-salinity

seawater thermodynamics
Rainer Feistel
a

a,*

, Giles M. Marion

Leibniz-Institut fur Ostseeforschung, Warnemunde, Seestrasse 15, 18119 Rostock, Germany

b
Desert Research Institute, Reno, NV, USA

Received 8 December 2005; received in revised form 19 March 2007; accepted 14 April 2007
Available online 5 May 2007

Abstract
A high-salinity Gibbs function for seawater is derived from Pitzer equations of the sea salt components, in conjunction
with the 2003 Gibbs function of seawater for low salinities. Various properties, computed from both formulations by thermodynamic rules, are compared with each other, and with high-salinity measurements. The new GibbsPitzer function
presented in this paper is valid in the range 0110 g kg1 in absolute salinity, 7 to +25 C in temperature, and 0
100 MPa in applied pressure. The formulation is expressed in the International Temperature Scale 1990 (ITS-90), and
is consistent with the International Standard for Fluid Water (IAPWS-95), and with the 2005/2006 equations of state
of ice Ih.
 2007 Elsevier Ltd. All rights reserved.
Keywords: Seawater; High salinity; Thermodynamic properties; Gibbs function; Pitzer equations

1. Introduction
Concentrated seawater solutions are found in exceptional natural waters like the Western Australian
Shark Bay, in salt works and desalination plants, and particularly in the brine pockets of very cold sea
ice. Only very few experimental investigations of high-salinity seawater are known to the authors (Higashi
et al., 1931; Bromley et al., 1967, 1970; Bromley, 1968; Connors, 1970; Grunberg, 1970) and a comprehensive equation of state is not available. There is an apparent description gap between the thermodynamic
formulations of seawater and sea ice properties by (i) the Gibbs function of seawater (Feistel and Hagen,
1998; Feistel and Wagner, 2005; Feistel et al., 2005) on the one hand, and (ii) the brine chemistry models
(Marion and Farren, 1999; Marion et al., 1999; Marion, 2001) which are based on so-called Pitzer equations
for the osmotic and activity coecients, on the other hand. The rst one is highly accurate for absolute
salinities up to 50 g kg1 at atmospheric pressure, corresponding to brine salinity of sea ice down to about
*

Corresponding author. Tel.: +49 381 5197 152; fax: +49 381 5197 4818.
E-mail addresses: Rainer.Feistel@io-warnemuende.de (R. Feistel), giles.marion@dri.edu (G.M. Marion).

0079-6611/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pocean.2007.04.020

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R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

3 C, and is restricted to standard sea salt composition, while the latter one covers much higher salinities
and even varying salt compositions.
The present work exploits the Pitzer equations of brine chemistry for medium and high salinities, extending
them into the form of a GibbsPitzer function of seawater (abbreviated furtheron as GP), which can be used
as a thermodynamic potential similar to the Gibbs function of seawater at lower salinities (Feistel, 2003 abbreviated as F03 in the following), and studies the thermodynamic properties of the resulting high-salinity
formulation.
A particular problem of this crossover formulation is a joint measure of the salt concentration. In
oceanography, salinity is usually expressed as a dimensionless practical salinity on the scale of 1978,
PSS-78. This scale is undened for salinities higher than 42. On the other hand, even at high concentrations Pitzer models permit the computation of the absolute salinity from the concentrations and atomic
weights of the dissolved species, but absolute salinity, in turn, is not well-dened for standard ocean seawater (Jackett et al., 2006). A quantitative relation between both measures is estimated (Section 2, Eqs.
(2.14) and (2.15)) within an uncertainty sucient for the accuracy requirements of this paper. For this
reason we formally dene here the specic unit psu by 1 psu  1.004867 g kg1, approximately expressing
practical salinity in terms of absolute salinity units, or vice versa. This way all salinity values can be written in units of either psu or of g kg1 over the full range of concentrations considered in this paper. We
have chosen psu for this purpose for strict numerical consistency with the highly accurate oceanographic
data and formulas.
The extension procedure from the Pitzer equations to the Gibbs potential relies on the fact that the lowest
order terms of the power expansion of the Gibbs function g(S, t, p) of seawater with respect to ion concentration, or salinity, S,
gS; t; p g0 g1 S ln S g2 S g3 S 3=2 g4 S 2   

1:1

have clear physical meanings. The coecients gi are functions of temperature t and pressure p. The intercept
g0(t, p) describes pure water properties and will be taken here from F03 in its zero-salinity limit, which is consistent with the scientic pure water standard IAPWS-95 (Wagner and Pru, 2002) over the Neptunian range
of temperatures and pressures. The linear term g2(t, p) is determined by ionsolvent interaction at innite dilution, describing, e.g. molar volumes and entropies, and will be combined from both the Pitzer model and
experimental data of seawater at low and high concentrations. The ideal-solution term g1 and the DebyeHuckel term g3 are supposed to be the same for both the F03 Gibbs function and the Pitzer equations, and can in
principle be taken from either of them, but practically should be chosen consistently with the Pitzer terms. All
higher-order terms g4 . . . are strongly inuenced by ionion interactions, and will be adopted here entirely
from the Pitzer equations.
In Section 2, we introduce the fundamental denitions and quantities required for mixed electrolytes
and seawater. In Section 3, we dene a single activity potential function of seawater, derived from the
GibbsDuhem equation, which comprises all information on ionion interaction forces of the electrolyte.
In Section 4, the Pitzer equations available for the particular chemical constituents of sea salt are briey
explained. At various Stp points, the values of the activity potential are computed from these equations
and an activity potential function is tted to these points. In Section 5, this seawater activity potential is
combined with Pitzer functions for the molar volumes, the Gibbs function F03 for pure water properties,
and heat capacity measurements, to form the new GibbsPitzer function GP for high-salinity seawater.
The required mathematical relations are given. In Section 6, various thermodynamic properties derived
from GP are compared with F03 for medium salinities, and the behaviour at higher salinities and the
agreement with available measurements is discussed. In the Appendix, tables of various constants and
coecients are given.
The GibbsPitzer function presented in this paper is valid in the range 0110 psu in practical salinity (PSS78, Unesco, 1981) or its high-salinity equivalent, 7 to +25 C in temperature, and 0100 MPa in applied
pressure, relative to normal pressure. The new function is expressed in the International Temperature Scale
1990 (ITS-90, Preston-Thomas, 1990) and is consistent with the international standard for uid water,
IAPWS-95 (Wagner and Pru, 2002) and the Gibbs potential of ice Ih in its rst and second, slightly improved
version (Feistel and Wagner, 2005, 2006; IAPWS, 2006).

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

517

2. Basic terms and denitions

We consider a mixed electrolyte solution consisting of N0 solvent molecules and N1, . . . , NX dissolved particles of X dierent chemical species, written in compact form as particle number vector N = {N0, . . . , NX}, at
absolute temperature T and absolute pressure P. The particle numbers N can be expressed by molalities
m = {m0, . . . , mX} (moles of solvent or solute per mass of solvent), as
ma

Na
;
N 0M 0

a 0; . . . ; X

2:1

Ma are the molecular weights of the species a = 0, . . . , X. The total molality m of the solute in the solution is
X
X

2:2

ma :

a1

The concentration, c, is dened as the mass of dissolved salt per mass of solution as
PX
N aM a
c Pa1
X
a0 N a M a

2:3

the mole fractions x = {x1, . . . , xX} of the solute as

Na
x a PX

b1 N b

ma
;
m

a 1; . . . ; X

2:4

and the mass fractions wa of the solute as

N aM a
;
wa PX
b1 N b M b

a 1 ...X:

2:5

The total mass M of the solution sample is then given by (NA is Avogadros number),
M

X
1 X
N aM a:
N A a0

2:6

We dene the total number N of dissolved particles in the sample as

N

X
X

2:7

N a:

a1

Inserting Na from (2.4) and M from (2.6), and introducing the average molecular weight of the solute
hMi

X
X

2:8

xa M a

a1

we get for N from Eq. (2.3),

N cM

NA
hMi

2:9

and the individual particle numbers, from (2.9) and (2.4),

N a xa N xa cM

NA
;
hMi

a 1; . . . ; X :

2:10

If za is the valence of the dissolved ion a, the electro-neutrality of the solution requires
0

X
X
a1

x a za :

2:11

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R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

The valence factor z2 of the electrolyte is given by

X
X
z2
xa z2a

2:12

a1

and its ionic strength I as

I

X
1X
1
ma z2a mz2 :
2 a1
2

2:13

In the case of standard seawater, the chemical composition of the solute is assumed to be given by xed
values of its mole fractions xa, valences za, and molecular weights Ma. Practical salinity S, as introduced
by the Practical Salinity Scale 1978 (PSS-78, Lewis and Perkin, 1981; Unesco, 1981) is dened by the conductivity of specic natural ocean water samples in such a way that a linear relation between salt concentration c
(i.e. absolute salinity) and S (i.e. practical salinity) can be assumed (Millero and Leung, 1976; Feistel, 2003;
Jackett et al., 2006)
c n  S:

2:14

There are several proposals for the composition of sea salt in the literature which we refrain from discussing
here; unfortunately, there is no such common standard specied yet. If a composition is chosen as given in
Table A.2 for the seawater model used by Feistel (2003), and S is expressed in the practical salinity scale,
the factor evaluates to
n c=S 1:004867 g kg1 psu1 1:004867  103 psu1 :

2:15

Introducing the number of dissolved sea salt particles NS per psu and kg seawater
NS n

NA
;
hMi

2:16

which takes the value NS = 1.926845 1022 kg1 psu1 for the composition model of Feistel (2003) we nally
have Na expressed by S, M, and the composition x as
N a xa N S SM;

a 1; . . . ; X :

2:17

Summing up these numbers, we nd for the total number N of dissolved particles in the given sample
N

X
X

N a N S SM:

2:18

a1

Now we derive the corresponding expression for the remaining number of water molecules, N0. We write Eq.
(2.6) in the form
MN A N 0 M 0 N hMi N 0 M 0 N S SMhMi

2:19

and get for N0

N0 M

N A  N S ShMi MN A

1  nS:
M0
M0

2:20

Note that c = nS < 1 is the mass fraction of salt in the seawater sample, while 1  nS = 1000 g kg1  c is the
samples mass fraction of water. For the solute molalities we have
Na
NS
S
; a 1; . . . ; X
2:21
ma
xa
N 0M 0
N A 1  nS
for the total molality we get
m

NS
S
N A 1  nS

and for the ionic strength

2:22

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

z2 N S
S
:
2 N A 1  nS

519

2:23

Quantitatively, we nd from Table A.1 for the ratios NS/NA = 31.99601 mmol kg1 psu1 and
9:91980 mmol kg1 psu1 .
In principle, the molality of mixed strong electrolytes like seawater can be dened in dierent ways. For
example, a solution with 12 1023 ions of Na+, 12 1023 ions Cl, 6 1023 ions Mg2+, and 6 1023 ions
SO2
4 , contains 2 + 2 + 1 + 1 = 6 mol of ions in our notation (2.2). It terms of neutral molecules, however,
there is no unique total molality. Depending on which compounds are supposed to be originally dissolved,
it contains 2 mol of NaCl and 1 mol of MgSO4, i.e. 3 mol of salt, or 1 mol of MgCl2 and 1 mol of Na2SO4,
i.e. 2 mol of salt, or any combination in between. This way, computed from Eq. (2.22), standard seawater
with S = 35 psu has the molality m = 1.16068 mol kg1, in agreement with Grassho et al. (1999, p. 568), but
contrary to m = 0.58052 mol kg1 calculated from formula (4.61) of Millero (2001, p. 253), and
m = 0.60597 mol kg1 reported by Millero (2006, p. 62).
The various quantities introduced in this section, describing the concentration and the composition of the
electrolyte seawater, are required for the thermodynamic relations considered in the following parts.

1 2
z N S =N A
2

3. GibbsDuhem equation
The thermodynamic properties of a given electrolyte can be derived by thermodynamic rules from its Gibbs
function G, i.e. its Gibbs energy or free enthalpy, expressed in terms of temperature T, pressure P, and particle
numbers N = {N0, . . . , NX}:
GN; T ; P

X
X

N a la N; T ; P

3:1

a0

Here, la are the molecular chemical potentials of the components, which can be written by means of practical
activity coecients, ca(m, T, P), as (Falkenhagen et al., 1971)
la l0a T ; P kT lnma ca ;

a 0; . . . ; X :

3:2

Here, k is the Boltzmann constant (Table A.1). The activity of the solvent is usually expressed by the practical
osmotic coecient /, in the form (Falkenhagen et al., 1971)
/

lnm0 c0
;
M 0m

3:3

and the activity of the solute by the mean activity coecient, c as

ln c

X
X
X
1 X
ma ln ca
xa ln ca :
m a1
a1

3:4

At constant temperature and pressure, the fundamental dierential of G is

dGN; T ; P

X
X

la dN a ;

3:5

a0

which, together with (3.1), leads to the GibbsDuhem equation

0

X
X

N a dla N; T ; P

3:6

a0

Next, we reformulate this equation in terms of osmotic and activity coecients. Inserting (3.2) into (3.6) at
constant T and P, we obtain
0 N 0 d lnm0 c0

X
X
a1

N a d lnma ca ;

3:7

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R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

This equation can be rearranged eventually into the well-known Bjerrum relation
dm1  / m d ln c 0

3:8

If the composition of the solute is xed, as in the case of sea salt, and its total concentration is variable,
expressed by salinity S, molality m, or ionic strength I, it is useful to introduce an activity potential
function w,
wm; T ; P 1  / ln c

3:9

which vanishes for ideal solutions, / = 1, c = 1. We call w a potential function since osmotic and activity coefcients can be obtained from it by partial derivatives, as follows from (3.8):
 
 
 
ow
ow
ow
I
S1  nS
3:10
/1m
om x;T ;P
oI x;T ;P
oS x;T ;P






omw
oIw
2 oSw=1  nS
ln c

1  nS
3:11
om x;T ;P
oI
oS
x;T ;P
x;T ;P
The fact that the osmotic and the activity coecient are not independent functions, but can be derived from a
single function by Eqs. (3.10) and (3.11), is thus a direct consequence of the GibbsDuhem Eq. (3.6). The pressure derivative of w is related to the excess volume, Eq. (5.15), which we shall consider later, and its temperature derivative to the excess entropy and the mixing heat, Eq. (6.9).
The non-ideal behavior of the solution seawater is thus entirely described by only its activity potential
function w, which we are going to determine quantitatively in the following section.
4. Activity potential of seawater
To estimate the seawater activity potential function, Eq. (3.9), it is necessary to calculate the osmotic coefcient (/) and the activity coecients (c) of individual species, Eq. (3.4). In the Pitzer approach, the osmotic
coecient is given by



XX
X
2
A/ I 3=2 X X
/  1 P

mc ma B/ca ZC ca
mc mc0 U/cc0
ma Wcc0 a
1=2
mi 1 bI


 XX
X
XX
XXX
XX
/
mn mc knc
mc Wcaa0
mn ma kna
mn mc ma fn;c;a

ma ma0 Uaa0
4:1

The activity coecient for a cation M is given by

X
X
X
XX
ma 2BMa ZC Ma
mc 2UMc
ma WMca
ma ma0 WMaa0
lncM z2M F
XX
X
XX
mc ma C ca 2
zM
mn knM
mn ma fnMa

4:2

Similarly, the activity coecient for an anion X is given by

X
X
X
XX
mc 2BcX ZC cX
ma 2UXa
mc WcXa
mc mc0 Wcc0 X
lncX z2X F
XX
X
XX
jzX j
mc ma C ca 2
mn knX
mn mc fncX

4:3

And nally, the activity coecient for a neutral species N is given by

X
X
XX
mc 2kNc
ma 2kNa
mc ma fNca
lncN

4:4

In these equations, F is dened as

XX
XX
XX
F fc
mc ma B0ca
mc mc0 U0cc0
ma ma0 U0aa0

4:5

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

521

where
f c A/

I 1=2
2
ln1 bI 1=2
1=2
b
1 bI

Z is dened as
X
Z
mi jzi j

4:6

4:7

and I (the ionic strength) is dened in Eq. (2.13).

In these equations, n, c, and a refer to neutral, cation, and anion species, A/ is the DebyeHuckel parameter
(Archer and Wang, 1990) and B, C, U, W, k, and f are interaction parameters among the various solutes. For a
more complete description of these relationships, see Pitzer (1991, 1995). For the specic interaction parameters actually used in the implementation of the Pitzer approach (FREZCHEM model), see Spencer et al.
(1990); Marion and Farren (1999); Marion (2001, 2002) and Marion et al. (2005).
To fully implement the GibbsPitzer function requires a model that can estimate / and c as functions of
temperature and pressure. The Pitzer interaction parameters (B, C, r, W, k, and f) are written as functions
of temperature (see the above references). The pressure dependence of equilibrium constants, activity coecients, and the activity of water [aw = f(/)] must be specied to estimate the pressure eect on seawater thermodynamics. The pressure dependence of equilibrium constants (K) is given by
 P
2
K
DV 0r P  P 0 DK 0r P  P 0

;
4:8
ln

0
RT
2RT
KP
where R is the gas constant
X
DV 0r
V 0i nV 0H2 O  V 0MX cr ;
and
DK 0r

K 0i nK 0H2 O  K 0MX cr :

4:9

4:10

In these equations, V 0i and K 0i are the molar volumes and compressibilities of chemical species involved in a
reaction (r).
The pressure dependence of the activity coecient (c) is estimated by
!
cPi
V i  V 0i P  P 0
;
4:11
ln P 0
RT
ci
where V i  V 0i is calculated for cations (M) and anions (X) using the following equations:
X

i
X h
XX


0
V M V 0M z2M f 2RT
ma BvMa
mc zc C vMa RT
mc ma z2M Bvca zM C vca
X

i
X h
XX


0
V X V 0X z2X f 2RT
mc BvcX
mc zc C vcX RT
mc ma z2X Bvca jzX jC vca
The volumetric interaction parameters in these equations are dened as


dBca
v
Bca
dP
and
C vca



dC ca

dP

4:12
4:13

4:14

4:15

Finally, the pressure dependence of the activity of water is given by


ln

aPw
0
aPw

V w  V 0w P  P 0
RT

4:16

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R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

where

P


Mw
1000 g kg1 mi M i X

mi V i
Vw
q
1000 g kg1
P


1 mi M i X
Mw

mi V i
q
P
P
1000 g kg1 mi M i
1 mi M i
P
q

;
P
ex
0
1000g kg1
mi V 0i V ex vw mi V i V
w

4:17

h
X
 i
XX
V ex
Av 1
ln1 bI 1=2 2

mc ma Bvca
mc zc C vca
RT
RT b

4:19

4:18

and

In Eqs. (4.16)(4.19), Mi is the molecular weight, q is the seawater density, and qw is the density of pure water.
In principle, the mean molar volume of sea salt in (4.18)
1 X
mi V 0i
V0
4:20
m
should be independent of salinity, however, there is a slight salinity dependence in the FREZCHEM model.
For example, the FREZCHEM values at S = 35 psu and S = 70 psu (P = 100 MPa and t = 25 C) are
V 0 10:1761 cm3 kg1 and V 0 10:1726 cm3 kg1 . This dependence arises because of the way bicarbonate
and carbonate species are distributed. At S = 70 psu, the alkalinity (equivalents/kg) increases twofold compared to S = 35 psu. The ionic strength is dierent between 35 and 70 psu and therefore the activity coecients are dierent. Consequently, so is the molal distribution of HCO3, CO3, CaCO03 , and MgCO03 because
this distribution is based on equilibrium constants. In estimating the density, the denominator summation
term of (4.18) does not include CaCO03 and MgCO03 .
Given the activity aw and the molecular weight Mw of water (Table A.2), the osmotic coecient is calculated with the Eq. (3.3):
/

lnaw
lnaw
55:50844 mol kg1 P
Mw  m
mi

4:21

For a more complete description of these pressure calculations, see Marion et al. (2005).
The implementation of the Pitzer approach is through the FREZCHEM model (Marion and Farren, 1999;
Marion, 2001, 2002; Marion et al., 2003, 2005). The molalities of seawater constituents (mi) were estimated by
Eq. (2.4)
m i xi m

4:22

where xi is the mole fraction (Table A.2) and m is the seawater molality (m = 1.16072 mol kg1 at S = 35 psu).
These calculated molalities are identical to the seawater molalities given by Millero and Sohn (1992) for
S = 35 psu. The seawater molalities at S = 35 psu were multiplied by S/35 psu to estimate molalities at S.
There are several minor seawater species that are not part of the FREZCHEM model including Sr2+, Br,


F , BOH4 , and H3 BO03 (Table A.2). In applying the FREZCHEM model to simulate seawater properties,

2
we lumped Sr2+ with Ca2+, Br and F with Cl, and BOH4 with alkalinity HCO
3 2CO3


0
OH BOH4 . The neutral H3 BO3 species was included with other neutral species such as CO2(aq).
In addition to lumping constituents, there are several other dierences in how the Gibbs model (F03)
and the Pitzer model (FREZCHEM) handled compositions. The FREZCHEM model explicitly recognizes
the ion-pairs, CaCO03 and MgCO03 , while the F03 model only deals with stoichiometric (total) concentrations. This dierence leads to minor dierences in calculated ionic strengths. For example, at S = 35 psu,
the F03 model gives I = 0.7226 mol kg1, while the FREZCHEM model gives I = 0.7223 mol kg1. Using
the FREZCHEM seawater model requires a specication of the partial pressure of carbon dioxide (P CO2 ),
which in our simulations was assigned a constant value of 36 Pa. Solution equilibrium with CO2(g) leads
to CO2(aq), which is a minor species that is explicitly included in the FREZCHEM model, but is missing
from the F03 model (Table A.2).

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

523

In none of the simulations reported in this work were solid phases allowed to precipitate. Carbonate mineral equilibria were excluded from the FREZCHEM simulations to prevent carbonate precipitation from normally supersaturated seawater. The lower temperature limit in our simulations was set by the freezing point of
seawater (ice formation). The upper concentration limit (S = 110 psu) is where gypsum starts to precipitate.
In principle, the activity potential w for xed chemical composition x,
wS; t; p 1  /m  x; T ; P

X
X

xa ln ca m  x; T ; P

4:23

a1

is given this way as an analytical function of molality, temperature, and pressure, but this function proved to
be too complicated for practical use in oceanography. Therefore, regular grid points (S, T, P) were computed
numerically, and a polynomial
X
wS; t; p
Qijk xi y j zk
4:24
i;j;k

p
was tted to these points, using the dimensionless variables x S=40 psu, y = t/40 C, and z = p/100 MPa.
Here, t is Celsius temperature, and p is gauge pressure, relative to normal pressure. The coecients Qijk of the
t are given in Table A.5 in Appendix. The rms of the t was 9 105.
5. Gibbs function of seawater
Now that we have an activity potential w of seawater quantitatively available for salinities up to 110 psu, we
need to build this function into the Gibbs potential of seawater in a suitable way to be able to compute arbitrary thermodynamic equilibrium properties from it. For this purpose, we start from the specic Gibbs energy,
given by Eqs. (3.1) and (3.2)
gS; t; p

X
1
1 X
GN; T ; P
N a l0a T ; P kT lnma ca m; T ; P 
M
M a0

5:1

After substituting particle numbers by molar fractions and salinity, and separating the solvent term, this equation becomes
gS; t; p

X
X
NA
1  nSl00 T ; P  N S SkT /m; T ; P N S S
xa l0a T ; P kT lnma ca m; T ; P 
Mw
a1

Rearranging the terms, we obtain the nal formula



S
w
wS; t; p ;
gS; t; p g t; p SCt; p N S SkT ln
1  nS

5:2

5:3

where we have introduced the Gibbs function of pure water,

gw t; p

NA 0
l T ; P ;
Mw 0

and a function C(t, p), collecting all remaining linear salinity terms,


X
X
NS
Ct; p N S kT ln
 1  ngw t; p N S
xa l0a kT ln xa :
NA
a1

5:4

5:5

Both these functions describe properties of seawater at innite dilution, and are independent of the activity
potential function. The Gibbs function of pure water can be obtained from the IAPWS-95 standard (Wagner
and Pru, 2002), or from the Gibbs function of seawater in the zero-salinity limit, which is consistent with
IAPWS-95 in the Neptunian range of t and p, as
gw t; p g0; t; p:

5:6

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R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

The second function, C(t, p), is related to the molar entropy and molar volume of sea salt. It can in principle be
obtained from the linear salinity terms of the Gibbs function F03, which has the form,
(
)
X
X
gF03 S; t; p 1 J=kg 
g0jk g1jk x2 ln x
gijk xi y j zk
5:7
j;k

i>1

p
expressed in dimensionless variables x S=40 psu, y = t/40 C, and z = p/100 MPa. Due to Plancks theory
of ideal solutions, its coecients g1jk vanish for j > 1 and k > 0, thus being consistent with Eq. (5.3). Then,
C(t, p) can be computed from Eq. (5.3) as
Ct; p lim
S!0

gS; t; p  g0; t; p  N S kTS ln S

:
S

5:8

The function C(t, p) we determined from (5.7) and (5.8) showed that the F03 and GP models are fairly consistent formulations. In particular for heat capacity and density, however, the GP results could be improved
signicantly by an alternative derivation of C(t, p), described below.
We rst consider the density formula (4.18),
P
vw mi V 0i V ex
P
v
:
5:9
1 mi M i
We want to compare this expression, seen as a power series in S, with the density formula which follows from
the GibbsPitzer equation of state (5.3)
 
og
oCt; p
owS; t; p
N S SkT
:
5:10
vw t; p S
vS; t; p
op S;t
op
op
We rewrite the denominator of (5.9) as
X
NA
1
1
mi M i 1 mhMi 1 mn

N S 1  nS

5:11

and get from (5.9) using Eq. (4.20)

v 1  nSvw mV 0 V ex :

5:12

Assuming that v and V 0 do not depend on S, we obtain the series expansion



NS 0
v vw S
V  nvw 1  nSV ex :
NA

5:13

Thus we get, comparing equal powers of S from (5.13) with those from (5.10),
oCt; p N S 0

V  nvw
op
NA
owS; t; p 1  nS ex
V ex

V
;
op
N S SkT
mRT

5:14
5:15

with thePgas constant R = NAk. We have determined V 0 as a tp polynomial, tted to regular grid points of
V 0 m1
mi V 0i computed with the FREZCHEM model at S = 45 psu. Upon integration of (5.14) over pressure, we nd eventually for C(t, p) the expression,
Z
NS p 0
w
Ct; p Ct; 0 ng t; 0
V dp  ngw t; p
5:16
NA 0
The remaining unknown function, C(t, 0), which is related to the normal-pressure molar entropy of sea salt,
can be obtained from experimental data of heat capacity. We have tted 3 coecients of its temperature
polynomial to 93 measurements of Bromley et al. (1967) for La Jolla seawater with salinities up to
117.4 psu and temperatures up to 25.5 C (scale 1948), resulting in an rms of 6 J kg1 K1, and to 36 measurements of Millero et al. (1973) with salinities up to 40 psu and temperatures up to 25 C (scale 1968) with an

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

525

rms of 7 J kg1 K1. Millero et al.s (1973) data were converted from chlorinities Cl to salinities by the
formula S/psu = 1.80655 Cl/(g kg1), taken from Lewis and Perkin (1981).
The corresponding tp polynomials for gw and C derived by means of Eqs. (5.6) and (5.16), and the t to
heat capacities, are given in Tables A.3 and A.4. This way, the desired Gibbs function, Eq. (5.3), is entirely
determined. Both functions gw and C are depending on arbitrary linear functions of temperature which represent the absolute energy and the absolute entropy of water and of salt. These four numbers cannot be determined from measurements and can either be specied at some tp reference state at practical convenience, or
derived from additional theorems like the Third Law (Fofono, 1962; Feistel, 2003; Feistel and Wagner,
2006). The pure water function gw taken from F03 automatically obeys these IAPWS-95 reference state properties at the triple point. In order to be consistent with F03, the related two coecients, R00 and R10 in Table
A.4, of C were computed from the reference state conditions at the standard ocean, which read
g35; 0; 0 0;

h35; 0; 0 0:

5:17

Supposed the Gibbs function to be given, we mention that the osmotic coecient expresses the dierence
between the chemical potentials of pure water, gw, and of water in seawater, lw = g  S (og/oS)t,p as
gw t; p lw S; t; p mRT /S; t; p:
Hence, / can be computed from the Gibbs function g of seawater by means of the formula:


1  nS
o
gS; t; p  g0; t; p  S gS; t; p ;
/
N S SkT
oS

5:18

5:19

which follows directly from (5.18), or equivalently, from solving Eq. (5.3) for w and taking the S-derivative
(3.10). Because of Eq. (5.18), / is the responsible quantity for the determination of equilibria between seawater
and the dierent phases of water.
6. High-salinity properties of seawater
With the formulas derived in the previous sections, the quantitative properties of seawater at high salinities
can now be discussed again here. For this purpose, we will compare in this section the newly derived Gibbs
Pitzer function (GP) of this paper with the 2003 Gibbs function (F03) in the validity range of F03, up to
50 psu at normal pressure and 40 psu at higher pressures. To quantify this comparison, we report the root
mean square (rms) deviation between both formulas over an Stp test cube covering 540 psu, 025 C,
and 0100 MPa for the parameters selected, separately for the normal pressure slice and the entire cube. Supposed F03 being more accurate than GP in the low-salinity range, these rms values can be considered as an
uncertainty estimate of GP in this range. In the salinity range up to 40 psu (high pressure) and 50 psu (normal
pressure), Feistel (2003) had compared the F03 formulation with 2050 points from 20 dierent groups of data;
this extensive data set will not be discussed repeatedly here. For higher salinities, we will compare both functions in order to see how well F03 may be extrapolated beyond its assumed validity limits, which are marked
by solid vertical lines in the gures.
Only few experimental data sets for thermodynamic properties of high-salinity seawater are known to the
authors. Grunberg (1970) had measured, among other quantities, vapour pressure of natural seawater, and
density and heat capacity of articial, Ca-free seawater. The composition of the latter is given in Table
A.2. Grunbergs (1970) data were plotted into the corresponding diagrams below with their original temperature and salinity values without conversion to modern scales.
Bromley et al. (1967) had measured heat capacities of La Jolla seawater, Table A.2. His salinity factor is
reported as c/S = 34.45 g kg1/(34.3 psu) = 1.004373 g kg1 psu1. We have converted his calories to Joules
by the factor 4.184 J cal1 (Bromley et al., 1970). The same factor was applied to the enthalpy data of Bromley
et al. (1970). Enthalpy of seawater is depending on an arbitrary linear function of salinity (Feistel, 2003)
expressing the absolute enthalpy of water and of salt. Hence, for comparability, Bromley et al.s (1970) data
need an adjustment to the reference state used for F03 and GP, in the form
h hBromley A BS:

6:1

526

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

Since measured enthalpy data are not available for the triple point of pure water, we have computed the oset
A = 61 J kg1 by adjusting (6.1) to the F03 absolute enthalpy at a nearby point, namely at normal pressure,
t = 0 C, and S = 0 psu. Interpolating Bromley et al.s (1970) data table for S = 35 psu, we then have determined B = 4.6 J kg1 psu1 to meet the condition (5.17).
The mixing heat measurements reported by Bromley (1968) and Connors (1970) do not need adjustments to
any reference state.
Density data of Higashi et al. (1931) were converted from chlorinities Cl to salinities by the formula (Lewis
and Perkin, 1981) S/psu = 1.80655 Cl/(g kg1), and their vapour pressure values by the factor (ISO, 1993)
133.3224 Pa/mmHg.
Density, q, and specic volume, v, are obtained from
 
1
og
v
:
6:2
q
op S;t
Fig. 1 shows good agreement between F03 and GP densities up to very high salinities, in particular at low
pressures. Moreover, both agree well with Grunbergs (1970) data for articial seawater at 20 C, their rms
is 0.3 kg m3 for F03 and 0.6 kg m3 for GP. With respect to Higashi et al.s (1931) data at 0 C and
25 C, their rms is 0.6 kg m3 for F03 and 0.8 kg m3 for GP. Thus, F03 can be applied to salinities even
beyond 40 psu, but with increasing uncertainty. The rms deviation between both density formulas over the
Stp test cube is 0.06 kg m3, or 60 ppm, at normal pressure, and 0.4 kg m3, or 400 ppm, for all pressures.
The uncertainty of F03 density itself is estimated to 4 ppm at normal pressure and 11 ppm for all pressures
(Feistel, 2003).
Specic entropy, r, is obtained from
 
og
r
6:3
ot S;p
and is displayed in Fig. 2. The rms deviation between the F03 and GP entropy formulas over the Stp cube
is 0.3 J kg1 K1 at normal pressure, and 0.5 J kg1 K1 for all pressures.
Specic enthalpy, h, is obtained from
 
og
h g Tr g  T 
6:4
ot S;p
and is shown in Fig. 3. The rms deviation between the F03 and GP enthalpy formulas over the Stp cube is
0.09 kJ kg1 at normal pressure, and 0.15 kJ kg1 for all pressures. The rms deviation of Bromley et al.s

Density
E
e
D

Density /(kg m-3)

h
H
h
H
h
H

A
ah B
bHC
c

h G
GH
hG
H
G

10

20

30

40

50

60

70

80

90

1130
1120
1110
1100
1090
1080
1070
1060
1050
1040
1030
1020
1010
1000
990

100 110

Salinity S/psu

Fig. 1. Density of seawater computed from Eq. (5.3) (AE) and from F03 (ae) at t = 0 C, p = 0 MPa (A, a), at t = 20 C, p = 0 MPa
(B, b), at t = 25 C, p = 0 MPa (C, c), at t = 0 C, p = 40 MPa (D, d) and at t = 0 C, p = 80 MPa (E, e). Measured data points at normal
pressure are of Grunberg (1970) for articial seawater at 20 C (G), and of Higashi et al. (1931) at 0 C (h) and 25 C (H).

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

Specific Entropy

527

300
250

Specific Entropy /(J kg -1K-1)

200
150

100

50
0
a
d

A
D

-50
-100

10

20

30

40

50

60

70

80

90

100 110

Salinity S/psu

Fig. 2. Specic entropy of seawater computed from Eq. (5.3) (AD) and from F03 (ad) at t = 0 C, p = 0 MPa (A, a), at t = 10 C,
p = 0 MPa (B, b), at t = 20 C, p = 0 MPa (C, c) and at t = 0 C, p = 80 MPa (D, d).

Specific Enthalpy

Specific Enthalpy h /(kJ kg -1)

10

20

30

40

110
100

6F

90

80
70

e 5E

d 4D

50
40

g G
c 3C

b 2B

60

50

60

70

80

90

a 1A

30
20
10
0
-10

100 110

Salinity S/psu

Fig. 3. Specic enthalpy of seawater computed from Eq. (5.3) (AH) and from F03 (ah) at t = 0 C, p = 0 MPa (A, a), at t = 5 C,
p = 0 MPa (B, b), at t = 10 C, p = 0 MPa (C, c) , at t = 15 C, p = 0 MPa (D, d), at t = 20 C, p = 0 MPa (E, e), at t = 25 C, p = 0 MPa
(F, f), at t = 0 C, p = 50 MPa (G, g) and at t = 0 C, p = 100 MPa (H, h). Data points (16) are from Bromley et al. (1970) for natural
seawater, readjusted to the F03 reference points.

(1970) readjusted natural seawater data at normal pressure, t = 025 C, and S = 0110 psu is 0.09 kJ kg1
from F03, and 0.02 kJ kg1 from GP. The rms deviation of F03 from Bromley et al.s (1970) data up to
50 psu is only 0.02 kJ kg1.
The temperature rise Dt due to adiabatic mixing of two seawater samples with equal volumes, with salinities
S1 and S2 at temperature t and normal pressure, follows from the mass conservation and the enthalpy balance,
Eq. (6.4). The nal salinity S is
S

S 1 qS 1 ; t; 0 S 2 qS 2 ; t; 0
;
qS 1 ; t; 0 qS 2 ; t; 0

6:5

and the enthalpy conservation yields

qS 1 ; t; 0hS 1 ; t; 0 qS 2 ; t; 0hS 2 ; t; 0
hS; t Dt; 0  hS; t; 0 cp  Dt;
qS 1 ; t; 0 qS 2 ; t; 0

6:6

528

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

Values computed from Eq. (6.6) with F03 and with GP are reported in Table 1 and displayed in Fig. 4, in
comparison to mixing heat measurements of Connors (1970). The rms deviation from the experimental values
is 3.2 mK for F03 and 6.6 mK for GP, the rms deviation between F03 and GP is 6.4 mK.
Mixing heats Q due to adiabatic mixing of two La Jolla seawater samples with the masses m1 and m2 at
25 C and normal pressure with initial salinities S1 and S2, were reported by Bromley (1968). The computation
with F03 and GP follows from the mass conservation and the enthalpy balance, in analogy to Eq. (6.5). The
results are listed in Table 2 and shown graphically in Fig. 5. The rms deviation from the experimental values is
14 J for F03 and 92 J for GP, the rms deviation between F03 and GP is 88 J. The mixing heat
Q m1 m2 hS  m1 hS 1  m2 hS 2

6:7

with nal salinity S,

S

m1 S 1 m2 S 2
m1 m2

6:8

depends only on the eective ionion interaction, expressed by the temperaturesalinity properties of the activity potential w, as follows from Eqs. (6.4) and (5.3),
Q N S kT 2

o
m1 S 1 wS 1 m2 S 2 wS 2  m1 m2 SwS;
oT

6:9

and is independent of the way we determined the function C(t, p), Eqs. (5.16) and (5.8).
Specic Gibbs energy (free enthalpy) of seawater, g(S, t, p), is shown in Fig. 6. The rms deviation between
the F03 and GP free enthalpy formulas over the Stp cube is 0.005 kJ kg1 at normal pressure, and
0.021 kJ kg1 for all pressures.
Isobaric specic heat capacity, cP, is obtained from
 
 
 2 
or
oh
og

T
6:10
cP T
ot S;p
ot S;p
ot2 S;p
and shown in Figs. 7 and 8. The rms deviation between the F03 and GP heat capacity formulas over the
Stp cube is 9 J kg1 K1 at normal pressure, and 15 J kg1 K1 for all pressures. The rms deviation of

Table 1
Temperature increase Dt and nal salinity S due to seawater mixing of equal sample volumes with initial salinities S1 and S2, computed
from Eqs. (6.5) and (6.6) with F03 and with GP, in comparison to measurements (exp) of Connors (1970)
S1 (psu)

S2 (psu)

t (C)

S(F03) (psu)

S(GP) (psu)

Dt (F03) (mK)

Dt (GP) (mK)

Dt (exp) (mK)

10.0
10.0
15.0
15.0
15.0
20.0
20.0
24.8
24.8
10.24
10.24
10.24
10.24
10.24
10.24
10.24
10.24
10.24
10.24

60.0
60.0
54.6
54.6
54.6
49.6
49.6
45.4
45.4
60.5
60.5
60.5
60.5
60.5
60.5
60.5
60.5
60.5
60.5

1.93
1.90
2.05
2.02
2.86
2.00
1.99
2.08
2.03
25.3
24.6
21.4
20.0
15.0
14.2
9.15
3.10
2.75
2.00

35.487
35.487
35.105
35.105
35.105
34.971
34.971
35.183
35.183
35.836
35.836
35.839
35.840
35.844
35.845
35.851
35.860
35.861
35.862

35.489
35.489
35.106
35.106
35.106
34.971
34.971
35.183
35.183
35.836
35.836
35.839
35.841
35.846
35.847
35.853
35.862
35.863
35.864

62.43
62.50
39.09
39.13
38.05
21.91
21.92
10.60
10.62
27.39
28.16
31.83
33.54
40.21
41.37
49.36
60.66
61.37
62.93

69.83
69.87
43.40
43.43
42.69
24.12
24.13
11.59
11.60
30.84
32.23
38.40
41.02
49.95
51.33
59.61
68.72
69.22
70.28

67.0
63.7
41.1
39.9
40.6
21.3
22.1
10.9
10.5
25.5
25.7
28.8
29.3
37.5
38.6
49.1
66.6
68.5
67.7

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

Computed Temperature Difference t /mK

Mixing Heat, Connors (1970)

0
-10

cCC
c

-20

cc
CC
c
c
ccc c
c
CCC
c

cc
C
C

-30

C
C

-40
-50

CC

c cc c
c

529

-60

CCCC C

-70
-80

-80

-70

-60

-50

-40

-30

-20
-10
Measured Temperature Difference t /mK

Fig. 4. Temperature increase Dt due to seawater mixing, computed from Eqs. (6.5) and (6.6) with F03 (c) and with GP (C), in comparison
to measured Dt of Connors (1970), compare Table 1.

Table 2
Mixing heat Q and nal salinity S due to seawater mixing at 25 C and normal pressure of samples with initial salinities S1 and S2, and
masses m1 and m2, computed from Eqs. (6.7) and (6.8), with F03 and with GP, in comparison to measurements (exp) of Bromley (1968)
S1 (psu)

m1 (kg)

S2 (psu)

m2 (kg)

S (psu)

Q (F03) (J)

Q (GP) (J)

Q (exp) (J)

33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
33.4
3.0
10.3
100.2
65.9
23.9
54.8
106.2
101.2
0.0
75.2
107.5
33.6
0.0

0.2715
0.2698
0.2938
0.2804
0.2710
0.2920
0.2734
0.2943
0.2455
0.2512
0.2560
0.2610
0.2756
0.2850
0.2790
0.2706
0.2772
0.2836
0.2832
0.2640
0.2530
0.3010
0.2620
0.2501
0.2400
0.2600
0.2680
0.1715
0.2722
0.2812
0.2425
0.2350
0.2776

0.00
2.12
4.11
6.11
7.90
11.12
13.85
15.11
0.00
1.93
0.00
2.00
3.87
5.71
7.52
9.18
10.67
12.11
13.65
14.97
0.00
0.00
0.00
0.00
0.00
0.00
0.00
33.60
99.80
0.00
33.60
100.38
33.04

3.9892
3.9807
4.0022
4.0071
3.9677
4.0170
4.0112
4.0335
4.0027
4.0055
3.9890
4.0163
4.0163
4.0279
4.0226
4.0321
4.0001
4.0145
4.0275
4.0181
4.0987
4.0095
4.0140
4.1265
4.0244
4.0370
4.0473
4.1423
4.0790
4.0555
4.1276
3.9943
4.1126

2.128
4.105
6.113
7.895
9.530
12.630
15.097
16.354
1.930
3.787
2.014
3.916
5.766
7.540
9.199
10.703
12.143
13.515
14.948
16.106
0.174
0.719
6.139
3.766
1.345
3.316
6.596
36.288
93.557
4.876
37.701
96.669
31.288

27.02
1.26
10.32
13.10
13.62
14.06
11.53
11.36
26.39
0.39
26.63
0.25
8.89
12.88
13.92
13.65
13.56
13.13
12.08
10.34
4.26
18.39
257.9
55.15
27.85
16.16
301.74
132.49
324.71
117.87
208.59
103.56
29.51

36.45
49.71
52.26
45.12
38.64
31.62
22.60
21.02
31.81
46.06
33.70
47.96
49.60
46.94
40.86
34.93
31.39
27.99
23.87
19.30
2.86
7.08
480.28
184.67
7.39
127.31
557.93
144.72
531.85
278.84
244.59
215.80
62.15

22.55
1.63
7.78
14.56
10.29
11.92
8.08
8.12
25.94
3.64
24.56
3.81
10.38
13.68
13.64
17.78
13.47
13.10
9.12
10.67
6.07
18.33
220.66
53.76
27.74
13.56
283.68
106.61
351.58
96.57
168.95
132.47
31.67

530

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

Mixing Heat, Bromley (1968)
600
B

550

Computed Mixing Heat Q/ J

500

450
400
350

300

b
B
B
B

250

200

B
B

150

B
b
b

100

B b
BBBBB
BB BBBBB b
B
B bBbbbbbb
B
bbbb

50
0

50 100 150 200 250 300 350 400 450 500 550 600

Measured Mixing Heat Q/ J

Fig. 5. Mixing heat Q due to seawater mixing at 25 C and normal pressure, computed with F03 (b) and with GP (B), in comparison to
measurements of Bromley (1968), compare Table 2.

Specific Gibbs Energy

90

Specific Gibbs Energy g /(kJ kg -1)

80
70
60
50

40
30
20
a

10
0
-10

10

20

30

40

50

60

70

80

90

100 110

Salinity S/psu

Fig. 6. Specic Gibbs energy of seawater computed from Eq. (5.3) (AD) and from F03 (ad) at t = 0 C, p = 0 MPa (A, a), at t = 20 C,
p = 0 MPa (B, b), at t = 0 C, p = 40 MPa (C, c) and at t = 0 C, p = 80 MPa (D, d).

Grunbergs (1970) articial seawater data at 0 C and 20 C is 10 J kg1 K1 from F03, and 11 J kg1 K1
from GP (Fig. 7). The rms deviation of Bromley et al.s (1967) natural high-salinity seawater data at
S = 50.1, 66.7, 83.2, 99.6 and 101 psu is 10 J kg1 K1 from F03, and 4 J kg1 K1 from GP (Fig. 8). The
uncertainty of F03 heat capacity is estimated as 12 J kg1 K1 below 50 psu and at normal pressure, while
the rms deviation of F03 from Bromley et al.s (1970) data below 50 psu is only 0.5 J kg1 K1 (Feistel, 2003).
Adiabatic lapse rate, C, is obtained from
 
ot
o2 g=otopS
 2
6:11
C
op S;r
o g=ot2 S;p
and displayed in Fig. 9. The rms deviation between the F03 and GP lapse rate formulas over the Stp cube is
0.6 mK MPa1 at normal pressure, and 0.9 mK MPa1 for all pressures.
The isobaric thermal expansion coecient, a, is obtained from
 
1 ov
o2 g=otopS

6:12
a
v ot S;p
og=opS;t

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

Specific Isobaric Heat Capacity

4300

Specific Heat Capacity c p /(J kg -1K-1)

g
G

4200
4100

g
G
G
g

4000

G
g

3900

G
g

3800

G
g
G
g

531

10

20

30

40

50

60

70

80

90

3700

B
A

3500

3400

3600

100 110

Salinity S/psu

Fig. 7. Specic isobaric heat capacity of seawater computed from Eq. (5.3) (AD) and from F03 (ad) at t = 0 C, p = 0 MPa (A, a), at
t = 20 C, p = 0 MPa (B, b), at t = 0 C, p = 40 MPa (C, c) and at t = 0 C, p = 80 MPa (D, d) Measured data points are of Grunberg
(1970) for articial seawater at 0 C (g) and 20 C (G) at 0 MPa.
Isobaric Specific Heat Capacity
Specific Heat Capacity c p /(J kg -1K-1)

3900

3950

3850
3800

4
5

C c

3750
4

4 55

45 5

45

D
E 45 d
e

3700
3650
3600

10

15

20

25

Temperature T/K

Fig. 8. Specic isobaric heat capacity of seawater at p = 0 MPa, computed from (e5.3) (AE), from F03 (ae), and experimental data (15)
of Bromley et al. (1967) at S = 50.1 psu (A, a, 1), at S = 66.7 psu (B, b, 2), at S = 83.2 psu (C, c, 3), S = 99.6 psu (D, d, 4), and S = 101 psu
(E, e, 5).
Adiabatic Lapse Rate
b

25

20

Lapse Rate /(mK MPa

-1

D
C

15
10
5
0
-5

10

20

30

40

50

60

70

80

90

100 110

Salinity S/psu

Fig. 9. Adiabatic lapse rate of seawater computed from Eq. (5.3) (AD) and from F03 (ad) at t = 0 C, p = 0 MPa (A, a), at t = 20 C,
p = 0 MPa (B, b), at t = 0 C, p = 40 MPa (C, c) and at t = 0 C, p = 80 MPa (D, d).

532

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

and is shown in Fig. 10. The rms deviation between the F03 and GP thermal expansion formulas over the
Stp cube is 9 ppm K1 at normal pressure, and 11 ppm K1 for all pressures. The uncertainty of the thermal
expansion coecient of F03 is estimated as 0.6 ppm K1 (Feistel, 2003).
Isothermal compressibility, jT, is obtained from
 
o2 g=op2 S;t
1 ov

6:13
jT 
v op S;t
og=opS;t
and is shown in Fig. 11. The rms deviation between the F03 and GP compressibility formulas over the Stp
cube is 10 ppm MPa1, or 3%, at normal pressure, and 6 ppm MPa1, or 2%, for all pressures.
Adiabatic compressibility, jS, and sound speed, U, is obtained from
 
2
o2 g=otopS  o2 g=ot2 S;p o2 g=op2 S;t
1 ov
v

6:14
jS 
v op S;r U 2
og=opS;t o2 g=ot2 S;p
Sound speed is shown in Fig. 12. The rms deviation between the F03 and GP sound speed formulas over the
Stp cube is 16 m s1, or 1%, at normal pressure, and 10 m s1, or 0.7%, for all pressures. The uncertainty of
F03 sound speed is estimated as 0.05 m s1.
Isobaric Thermal Expansion Coefficient
Expansion Coefficient /(ppm K -1 )

300

d
c
a

350

D
C
A

250
200
150
100
50
0
-50
-100

10

20

30

40

50

60

70

80

90

100 110

Salinity S/psu

Fig. 10. Isobaric thermal expansion coecient of seawater computed from Eq. (5.3) (AD) and from F03 (ad) at t = 0 C,
p = 0 MPa (A, a), at t = 20 C, p = 0 MPa (B, b), at t = 0 C, p = 40 MPa (C, c) and at t = 0 C, p = 80 MPa (D, d).

Isothermal compressibility
525

Compressibility T/(ppm MPa-1)

500
475
450
A

a
b
c

425
400
375

350

325
300

10

20

30

40

50

60

70

80

90

100 110

Salinity S/psu

Fig. 11. Isothermal compressibility of seawater computed from Eq. (5.3) (AD) and from F03 (ad) at t = 0 C, p = 0 MPa (A, a), at
t = 20 C, p = 0 MPa (B, b), at t = 0 C, p = 40 MPa (C, c) and at t = 0 C, p = 80 MPa (D, d).

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

Sound Speed

533

1700
D

1675
1650
1625

Sound Speed U /(ms-1)

d
b
c

1600
1575
1550
1525
1500

1475
1450
1425
1400
0

10

20

30

40

50

60

70

80

90

100 110

Salinity S/psu

Fig. 12. Sound speed of seawater computed from Eq. (5.3) (AD) and from F03 (ad) at t = 0 C, p = 0 MPa (A, a), at t = 20 C,
p = 0 MPa (B, b), at t = 0 C, p = 40 MPa (C, c) and at t = 0 C, p = 80 MPa (D, d).

The isothermal haline contraction coecient, b, is obtained from

 
1 ov
o2 g=opoSt

b
v oS t;p
og=opS;t

6:15

and is shown in Fig. 13. The rms deviation between both haline contraction formulas over the Stp cube is
3 ppm psu1, or 0.5%, at normal pressure, and 21 ppm psu1, or 2.5%, for all pressures.
Potential temperature, h(S, t, p, pr), for reference pressure pr, is implicitly given by the equation
rS; t; p rS; h; pr

6:16

and displayed in Fig. 14 for normal pressure as reference pressure. The rms deviation between the F03 and
GP potential temperature formulas over the Stp cube is 42 mK for all pressures. The uncertainty of potential temperature computed from F03 is estimated as 3 mK.
Freezing temperature, tf(S, p), is implicitly given by the equation
gIh tf ; p gS; tf ; p  S

o
gS; tf ; p;
oS

6:17

in conjunction with the equation of state of ice Ih (Feistel and Wagner, 2006; IAPWS, 2006) and is shown in
Fig. 15. The rms deviation between the F03 and GP freezing point formulas over the Stp cube is 2 mK at
Isothermal haline contraction coefficient

840

Contraction Coefficient /(ppm psu-1)

820
800
780
B
A

760

740

b
c
d

720
C

700
680
660

640
620

10

20

30

40

50

60

70

80

90

100 110

Salinity S/psu

Fig. 13. Isothermal haline contraction coecient computed from Eq. (5.3) (AD) and from F03 (ad) at t = 0 C, p = 0 MPa (A, a), at
t = 20 C, p = 0 MPa (B, b), at t = 0 C, p = 40 MPa (C, c) and at t = 0 C, p = 80 MPa (D, d).

534

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

Potential Temperature

0.2

Potential Temperature / C

0
a

-0.2
-0.4

-0.6

b
C
c

-0.8
-1

D
d
E

-1.2
-1.4
-1.6

10

20

30

40

50

60

70

80

90

-1.8

100 110

Salinity S/psu

Fig. 14. Potential temperature for reference pressure pr = 0, computed from Eq. (5.3) (AE) and from F03 (ae) at t = 0 C, p = 20 MPa
(A, a), at t = 0 C, p = 40 MPa (B, b), at t = 0 C, p = 60 MPa (C, c), at t = 0 C, p = 80 MPa (D, d) and at t = 0 C, p = 100 MPa (E, e).

Freezing Point

0
-2
-4

Temperature t/ C

b
c

-6
A
B

-8

d
C

-10

-12

e
f
E

-14
-16

-18
0

10

20

30

40

50

60

70

80

90

100 110

Salinity S/psu

Fig. 15. Freezing temperature, computed from Eq. (5.3) (AF) and from F03 (af) at p = 0 MPa (A, a), at p = 20 MPa (B, b), p = 40 MPa
(C, c), p = 60 MPa (D, d), p = 80 MPa (E, e) and at p = 100 MPa (F, f). Values computed in conjunction with the equation of state of ice
Ih, Feistel and Wagner (2006).

normal pressure, and 21 mK for all pressures. The uncertainty of F03 freezing points is estimated as 2 mK at
normal pressure. For pure water, the agreement of F03 with accurate high-pressure measurements is within
30 mK, while the uncertainty is estimated by 2% of the melting pressure (Feistel and Wagner, 2006).
Vapour pressure, Pvap, of seawater under pressure p, is computed from the formula
gvap T ; P vap gS; t; p  S

o
gS; t; p;
oS

6:18

in conjunction with the IAPWS-95 formulation for water vapour, gvap(T, P), Wagner and Pru (2002) and
shown in Fig. 16 for normal pressure as applied pressure. The rms deviation between the F03 and GP vapour
pressure formulas over the Stp cube is 0.09 Pa at normal pressure, and 0.15 Pa for all pressures. The rms
deviation from Grunbergs (1970) natural seawater data at 20 C is 25 Pa for F03, and 10 Pa for GP. The
rms deviation from Higashi et al.s (1931) data at 25 C is 63 Pa for F03, and 33 Pa for GP.
The osmotic coecient can be computed from the formula (5.19)


1  nS
o
6:19
/
gS; t; p  g0; t; p  S gS; t; p
N S SkT
oS

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

Vapour Pressure
H

535

3200

3000

HE

2800

Pressure P / Pa

2600
G

2400

G G

2200

2000
1800
c

1600

1400
b

1200
1000

10

20

30

40

50

60

70

80

90

800

100 110

Salinity S/psu

Fig. 16. Vapour pressure, computed from Eq. (5.3) (AE) and from F03 (ae) at t = 5 C, p = 0 MPa (A, a), at t = 10 C, p = 0 MPa
(B, b), at t = 15 C, p = 0 MPa (C, c), at t = 20 C, p = 0 MPa (D, d) and at t = 25 C, p = 0 MPa (E, e). Values computed in
conjunction with the IAPWS-95 formulation for vapour. Experimental data at 20 C (G) from Grunberg (1970) for natural seawater,
at 25 C (H) from Higashi et al. (1931).

Osmotic Coefficient

1.02

Osmotic Coefficient

D
C
3
2
1
3
2

3210

32
1
0

321
0

32
1
0

10

20

30

40

0.98
0

0.96

0.94

0.92

0.90
a b cd

1.00

1
32
1

3
2

50

60

70

0.88
80

90

100 110

Salinity S/psu

Fig. 17. Osmotic coecient, computed from Eq. (5.3) (AD) and from F03 (ad), in comparison to data (03) reported by Bromley
et al. (1974) at t = 0 C, p = 0 MPa (A, a, 0), at t = 10 C, p = 0 MPa (B, b, 1), at t = 20 C, p = 0 MPa (C, c, 2) and at t = 25 C,
p = 0 MPa (D, d, 3).

and is shown in Fig. 17. The rms deviation between the F03 and GP formulas for the osmotic coecient over
the Stp cube is 0.003 at normal pressure, and 0.005 for all pressures.
7. Conclusion
For high-salinity seawater, neither a fundamental equation of state nor a comprehensive set of experimental
data was available by now. We have used data of the numerical FREZCHEM model, based on Pitzer equations for the constituents of articial seawater, in combination with pure water properties from the 2003 Gibbs
function (F03) of seawater, and experimental data of seawater heat capacities, to construct a new high-salinity
GibbsPitzer function (GP) of seawater, depending on salinity, temperature, and pressure. This equation is
given in Eq. (5.3), with coecients listed in Appendix A, Tables A.3A.5.
We emphasize that the FREZCHEM model was never explicitly designed for, nor adjusted to, any seawater
properties, in contrast to F03, which was almost exclusively determined by regression to a large number of

536

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

highly accurate seawater data. Under these circumstances, the good agreement between both approaches,
which are so dierent conceptionally and with respect to their data background, is a surprising result on its
own. This is the rst comprehensive intercomparison of F03 with a rather independent formulation, with
excellent results.
Another quite unexpected nding is that the mere extrapolation of F03 to high salinities, which was neither
intended nor systematically studied before, yields reasonable results in most cases, sometimes even more accurate than the new GP formulation itself.
The extended and systematic comparison between GP, F03, and available experimental data has revealed
that
In colligative properties (osmotic coecient, freezing point, vapour pressure), F03 is restricted to the lowsalinity range up to 4050 psu, and shows signicant deviations with increasing salinity, while GP covers
the entire salinity range in a stable and accurate way.
In thermal properties (enthalpy, entropy, Gibbs energy, heat capacity), but also in density, both formulations describe the high-salinity region rather well.
In higher derivatives of the Gibbs function (mixing heat, compressibility, thermal expansion, saline contraction, sound speed) both formulations exhibit substantial deviations, and lacking measurements do not
allow decisive nal conclusions. Particularly in those cases where GP already at lower salinities signicantly deviates from F03, the latter one appears more reliable. This conclusion is supported by the dierent
agreement of both with the mixing heat data of Bromley, Fig. 5.
In general, the high-salinity range is described with only lower accuracy than is the low-salinity range by
F03.
For many practical applications, either GP or F03 should be suciently accurate formulations, both being
in good agreement with the scarce experimental basis. It must be decided on the particular needs which of both
is to be preferred for a particular purpose.
Acknowledgement
The authors are grateful to H.-J. Kretzschmar for providing literature on industrial high-salinity seawater
measurements. They thank A. Schroder and B. Sievert for making literature sources available. This paper contributes to the tasks of the SCOR/IAPSO Working Group 127 on Thermodynamics and Equation of State of
Seawater.
Appendix A
Tables A.1A.5 are given for important general constants, the composition of seawater, and the coecients
of the new GibbsPitzer equation of state, Eq. (5.3).

Table A.1
Physical constants and special values (maximum seven digits given)
Quantity

Symbol

Value

Unit

Source

Celsius zero point

Normal pressure
Boltzmann constant
Avogadro number
Molar gas constant
Salinity number
Salinity factor
Valence factor

T0
P0
k
NA
R = kNA
NS
n
z2

273.15
101 325
1.380651 1023
6.022142 1023
8.314472
1.926845 1022
1.004867
1.245143

K
Pa
J K1
mol1
J K1 mol1
kg1 psu1
g kg1 psu1

Preston-Thomas (1990)
ISO (1993)
Mohr and Taylor (2005)
Mohr and Taylor (2005)
Mohr and Taylor (2005)
Feistel (2003)
Feistel (2003)
Feistel (2003)

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

537

Table A.2
Seawater composition model F03 (Feistel, 2003), Grunbergs (1970) articial calcium-free seawater, and major constituents of Bromley
et al.s (1967) La Jolla seawater
Kind (a)

za

Ma (g mol1)

F03 (xa/ppm)

F03 (wa/ppm)

Grunberg (wa/ppm)

Bromley (wa/ppm)

Na
Mg
Ca
K
Sr
Cl
SO4
HCO3
Br
CO3
B(OH)4
F
H3BO3
H2O

+1
+2
+2
+1
+2
1
2
1
1
2
1
1
0

22.98977
24.305
40.078
39.0983
87.62
35.453
96.0626
61.016 84
79.904
60.0089
78.84036
18.9984032
61.83302
18.01528

418791.8
47163.7
9181.5
9115.1
81.0
487445.1
25213.1
1661.5
751.3
173
74.6
54.6
293.8

306563.3
36499.9
11716.8
11347.7
225.9
550257.7
77120.1
3228.0
1 911.5
330.5
187.3
33.1
578.4

320606
38182

306531
36865
11611
11030
290
550943
76923
4064
1742

10303
575455
53212
2121

909

F03 components and mass fractions from Millero (1982), mole fractions recomputed with IUPAC 99 mol masses (Coplen, 2001), with
sodium re-adjusted to obey electro-neutrality (2.11). Molecular weights are computed as sums over their atomic parts. z: ion charge, M:
molecular weight, w: mass fraction, x: mole fraction.
Table A.3

j
k
P
Coecients of the polynomial gw t; p 1 J=kg j;k g0jk 40 t C 100 pMPa , adopted from Feistel (2003)
j

0
0
0
0
0
0
0
1
1
1
1
1
1
2

0
1
2
3
4
5
6
0
1
2
3
4
5
0
a

g0jk
a

101.342743139672
100015.695367145
2544.5765420363
284.517778446287
33.3146754253611
4.20263108803084
0.546428511471039
5.90578348518236a
270.983805184062
776.153611613101
196.51255088122
28.9796526294175
2.13290083518327
12357.785933039

g0jk

g0jk

2
2
2
2
2
3
3
3
3
3
3
4
4
4

1
2
3
4
5
0
1
2
3
4
5
0
1
2

1455.0364540468
756.558385769359
273.479662323528
55.5604063817218
4.34420671917197
736.741204151612
672.50778314507
499.360390819152
239.545330654412
48.8012518593872
1.66307106208905
148.185936433658
397.968445406972
301.815380621876

4
4
5
5
5
5
5
6
6
6
6
7
7

3
4
0
1
2
3
4
0
1
2
3
0
1

152.196371733841
26.3748377232802
58.0259125842571
194.618310617595
120.520654902025
55.2723052340152
6.48190668077221
18.9843846514172
63.5113936641785
22.2897317140459
8.17060541818112
3.05081646487967
9.63108119393062

Rjk

4
4
4
4
5
5
5
5
6
6
6
7

1
2
3
4
1
2
3
4
1
2
3
1

15.9962143132307
12.1313726431745
6.11748445900278
1.06012816233918
7.82262071741483
4.84428915717733
2.22165262174357
0.260538164823501
2.55282014468568
0.895928633531926
0.328414870190056
0.387118226644059

Coecients subject to the IAPWS-95 reference state.

Table A.4

j
k
P
Coecients of the polynomial Ct; p 401 J=kg psu j;k Rjk 40 t C 100 pMPa
j

0
0
0
0
0
0
0
1
1
1
1
1
1

0
1
2
3
4
5
6
0
1
2
3
4
5
a
b

Rjk

j
a

9188.35355278883
3297.02334038811
364.670193748859
9.26449928889693
0.542487256726294
0.168923411741451
0.0219635191614547
1455.8851627253a
537.251238518538
238.818607352217
7.89875909865436
1.1648278639506
0.0857312665419243

2
2
2
2
2
2
3
3
3
3
3
3
4

k
0
1
2
3
4
5
0
1
2
3
4
5
0

Rjk
b

782.557453641887
290.637800851481
122.903854303638
10.9924275136023
2.23323275518327
0.174613998930967
77.6208956815076b
27.0312351410255
20.0716311136508
9.62844791114828
1.96155070208747
0.0668466091579295
22.5314914279383b

Coecients subject to the seawater reference state, Eq. (5.17).

Determined by tting heat capacity data of Bromley et al. (1967) and Millero et al. (1973).

538

R. Feistel, G.M. Marion / Progress in Oceanography 74 (2007) 515539

Table A.5

i=2
j p k
P
t
Coecients of the seawater activity potential wS; t; p i;j;k Qijk 40 Spsu
100 MPa
40  C
i

Qijk

Qijk

1
1
1
1
1
1
1
1
2
2
2
2

0
1
0
2
1
0
2
1
0
1
2
1

0
0
1
0
1
2
1
2
0
0
0
1

0.846695845492505
0.0292799909322037
0.0545572421409309
2.70139691642315E-02
5.62425549804373E-02
2.78949824990802E-02
2.86229058798891E-02
5.36572370382561E-02
0.716405257060217
0.122350343818045
7.58665998986371E-03
2.23235728210619E-02

2
2
3
3
3
4
4
4
4
4
5
6

0
1
0
1
0
0
1
0
1
0
0
0

2
2
0
0
2
0
0
1
1
2
0
0

0.0589935338374668
0.0201443233092579
0.505444436474932
6.51948412073269E-02
4.43446365464315E-02
0.256279228917379
1.52253322852328E-02
2.17154948499942E-03
8.17932310592732E-03
5.58378653215539E-03
7.57370458886726E-02
1.02824932834835E-02

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