Deep-Sea Research I 65 (2012) 146–156

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Deep-Sea Research I
journal homepage: www.elsevier.com/locate/dsri

(p,r,T) properties of seawater: Extensions to high salinities

J. Safarov a,n, S. Berndt b, F. Millero c, R. Feistel d, A. Heintz e, E. Hassel a
a
Lehrstuhl für Technische Thermodynamik, Universität Rostock, Albert-Einstein-Str.2, D-18059 Rostock, Germany
b
Lehrstuhl für Kolbenmaschinen und Verbrennungsmotoren, Universität Rostock, Albert-Einstein-Str.2, D-18059 Rostock, Germany
c
Rosenstiel School of Marine and Atmospheric Science, University of Miami, 4600 Rickenbacker Causeway, 33149 Miami, FL, USA
d
Sektion Physikalische Ozeanographie und Messtechnik, Leibniz-Institut für Ostseeforschung, Seestr. 15, D-18119 Warnemünde, Germany
e
Abteilung für Physikalische Chemie, Universität Rostock, Hermannstr.14, D-18051 Rostock, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Measurements of (p,r,T) properties of seawater with absolute salinity SA ¼ (31.684, 33.507, 37.372,
Received 16 December 2011 37.969, 40.164, 41.825, 44.811, 46.119, 48.600, 50.232, 52.449 and 55.529) g kg  1, temperature
Received in revised form T¼ 273.15–468.15 K and pressures, p, up to 140 MPa are reported with the reproducibility of the
23 March 2012
density measurements observed to be in the average percent deviation range Dr/r ¼ 70.01–0.03%.
Accepted 23 March 2012
Available online 5 April 2012
The measurements are made with a new set up vibration-tube densimeter which is calibrated using
double-distilled water (Wagner and Pruß, 2002), methanol [(de Reuck and Craven, 1993), (Osada et al.,
Keywords: 1999) and (Yokoyama and Uematsu, 2003)] and aqueous NaCl solutions [(Archer, 1992) and (Hilbert,
Seawater 1979)]. Based on these measurements, an empirical expression for the density of seawater at high
Salinity
salinities has been developed as a function of salinity, pressure and temperature. The results can be
Density
used to extend the present equation of state of seawater to higher temperatures for pressure up to
Vibration tube densimeter
Equation of state 140 MPa.
& 2012 Elsevier Ltd. All rights reserved.

1. Introduction emerges at incredibly high temperatures – up to T¼473.15–

The majority of water on earth is seawater, a solution of salts of
nearly constant composition (Millero et al., 2008) dissolved in
water. The variable concentration of salts is represented by the
mass fraction of dissolved salt in solution, referred to as absolute
salinity, SA. The density of seawater is changing in dependence on
the depth below sea surface. The pressure range found in oceanic
seawater goes from approximately 0.1 MPa at the sea surface to
about 108.6 MPa at the deepest known place, the Mariana Trench
(11022 m), over 1000 times the standard atmospheric pressure at
sea level. For oceanography and marine technology or desalination
industry it is important to know the density and other properties
of seawater at high pressures, temperatures and salinities.
Most of the water in the deeper layers of the oceans is very
cold. The known temperature range, which occurs in natural
seawater, goes from the freezing point to a maximum at approxi-
mately T¼303.15–313.15 K, and only rarely beyond that. As a
result, even beneath the hottest tropical regions the water at a
depth of 2000–3000 m almost never rises above T¼ 277.15 K –
with one dramatic exception. In some places along the oceanic
ridge systems, extremely hot seawater gushes out of fissures in
the underlying rocks. The water from these hydrothermal vents
n
Corresponding author. Tel.: þ49 381 4989415; fax: þ49 381 4989402.
E-mail address: javid.safarov@uni-rostock.de (J. Safarov).
673.15 K, close to the critical temperature of water. Because of
the vast mass of surrounding cold water, the temperature drops
rapidly to the normal T¼276.15–277.15 K within some meters of
the vent opening. The thermal expansibility of seawater is
important to be known for these hot processes and is requisite
to be available from the constructed equation of state.
Comprehensive information about seawater properties are
available (Millero, 1982, 1983, 1996). The density of seawater
generally increases with decreasing temperature, increasing sali-
nity, and increasing depth in the ocean; at the surface of the ocean
it varies in the r ¼ 1020–1029 kg m  3 interval. Highest densities
are found in the deepest parts of the oceans with values as high as
r ¼1050 kg m  3.
For scientific investigations and design of many natural and
technical processes which use seawater, it is of great importance
to have a reliable base of thermodynamic data. The most recent
standard formulation (IAPWS, 2008) for seawater is restricted in
its range of applicability due to a lack of density measurements at
higher temperatures and elevated pressures (IAPWS Certified
Research Need 16, 2007, www.iapws.org). The present work
therefore fills an essential data gap. In particular, it provides
important information for evaporating tropical estuaries and
technical applications such as those associated with desalination
plants.
Until 2009, the international standard for the representation of
the properties of seawater was the 1980 International Equation of

0967-0637/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dsr.2012.03.010
 J. Safarov et al. / Deep-Sea Research I 65 (2012) 146–156 147

State of Seawater (EOS-80), released by the Joint Panel on
Oceanographic Tables and Standards (JPOTS) and published by
Millero et al. (1980). It was based on the temperature scale IPTS-
68 and on the Practical Salinity Scale 1978, PSS-78 (Lewis and
Perkin, 1981).
In 2005, as a successor of JPOTS, the Working Group 127
(WG127) was established by the International Association for the
Physical Sciences of the Oceans (IAPSO) and the Scientific Com-
mittee on Oceanic Research (SCOR). Its main objective was an
updated evaluation of the standards for seawater thermody-
namics and, if necessary, the recommendation of improved
formulations. Among the reasons for this revision is the need
for consistency between seawater properties and the more
accurate recent international standards for temperature (ITS-90)
and for properties of pure water (IAPWS-95) (Wagner and Pruß,
2002). As a result, the International Association for the Properties
of Water and Steam (IAPWS) in cooperation with WG127
endorsed a new joint seawater formulation on the occasion of
its 15th International Conference on the Properties of Water and
Steam in September 2008 in Berlin (IAPWS, 2008). For oceano-
graphy, this formulation, the International Thermodynamic Equa-
tion of Seawater 2010 (TEOS-10, IOC et al., 2010) was adopted
internationally in Paris 2009 by the International Oceanographic
Commission (IOC) of UNESCO and in Melbourne 2011 by the
International Union of Geodesy and Geophysics (IUGG, 2011).
It is noteworthy that, since the evaluation of EOS-80, there
have been only few additional experimental (p,r,T) measure-
ments made available (Feistel, 2003, 2008; Feistel, 2010a;
Millero and Huang, 2009, 2011; Sharqawy et al., 2010) for the
calculation of the thermodynamic properties of seawater at high
temperatures, pressures and salinities.
The present experimental investigations of (p,r,T) of seawater
at high salinities can be used to extend the current thermody-
namic equation of state of seawater to higher pressures and
temperatures. This new equation will be useful for modeling and
industrial process applications involving seawater at high tem-
peratures and pressures.
This work is the continuation of our earlier research work
(Safarov et al., 2009). We have measured the (p,r,T) properties of
seawater with absolute salinity SA ¼0–55.529 g kg  1 (total 7616
experimental points in 34 various salinities) during the last four
years and here we describe the (p,r,T) properties of high-salinity
seawater at SA ¼(31.684, 33.507, 37.372, 37.969, 40.164, 41.825,
44.811, 46.119, 48.600, 50.232, 52.449 and 55.529) g kg  1, tem-
peratures T¼273.15–468.15 K and pressures, p, up to 140 MPa on
the new Reference-Composition Salinity Scale (Millero et al.,
2008) which extends the current Practical Salinity Scale PSS-78
to temperatures higher than T¼313.15 K and salinities higher
than 42 g kg  1.
The most important works of Bradshaw and Schleicher (1970),
Bradshaw and Schleicher (1976), Caldwell (1978), Crease (1962),
Duedall and Paulowich (1973), Ekman (1908), Emmet and Millero
(1974), Fabuss et al. (1966), Fabuss and Korosi (1968), Grunberg
(1970), Hampel (1950), Hara et al. (1932), Isdale and Morris
(1972), Lepple and Millero (1971), Lewis and Randall (1961),
Millero et al. (1976), Millero (2000), Newton and Kennedy (1965),
Pitzer (1979), Poisson et al. (1980), Poisson and Gadhoumi (1993),
Tait (1888), Wilson and Bradley (1965), Wilson and Bradley
(1968) found in previous years in the literature were analyzed
in our earlier publications (Feistel, 2010a; Feistel et al., 2010),
(Safarov et al., 2009), (Chen and Millero, 1978) and are reported in
Table 1. We review here only a few of the most recent papers.
Feistel (2008) determined the specific Gibbs energy of sea-
water at T¼267.15–353.15 K and SA ¼0–120 g kg  1 using the
experimental heat capacity, freezing point, vapour pressure and
mixing heat values at atmospheric pressure. Combined with the
pure-water properties (IAPWS-95), and the densities from the
2003 Gibbs function of seawater, a new saline part of the Gibbs
function is developed for seawater that has an extended range of
validity including elevated temperatures and salinities. The new
Gibbs function is expressed in terms of the temperature scale ITS-
90. Its input variable for the concentration is absolute salinity,
available from the new Reference-Composition Salinity Scale
of 2008.

Table 1
Summary of reported experimental density data for sea water.

First author Year Method Property Temperature, T/K Pressure, p/MPa Salinity, SA/g kg  1 Uncertainty

Tait 1888 k 273.15–288.15 0.101–50

Ekman 1908 Compr. 273.15–293.15 0.101–60 31.13, 38.53%
Hara 1932 OSP r 273.15–448.15 0.101 29.568–268.739
Hampel 1950 IM r,T,S 295.65–361.45 0.101 32.111–138.982 7 14  10  4 g cm  3
Crease 1962 p,v,T 273.15–303.15 0.101–100 5–37 7 3  10  6 cm3 g  1
Newton 1965 HPV p,v,T 273.15–298.15 0.101–130 0–41.224 7 7  10  5 cm3 g  1
Fabuss 1966, 1968 LP r,T,S 298.15–423.15 0.101 35.178–175.889 7 0.02%
Wilson 1966, 1968 DT p,v,T 273.15–313.54 0.101–100 0–40.560 7 1  10  5 cm3 g  1
Bradshaw 1970 D ap 271.15–303.15 0.8–100.1 30.644, 35.165, 39.686 7 3  10  6 cm3 g  1 deg  1
Grunberg 1970 BGD r,T,S 293.15––453.15 0.101 0–160 7 0.02%
Lepple 1971 PA kT 273.15–313.24 0.101–2.579 6.169–39.184 7 0.05  10  6 bar  1
Isdale 1972 BGD r,T,S 293.15–453.15 0.101 10–150 7 0.05%
Duedall 1973 BTDC kT 288.15 0–90.12 35.165 7 0.07  10  6 bar  1
Emmet 1974 MFD p,v,T 271.15–313.15 0–99.533 35.165 7 11  10  6 cm3 g  1
Bradshaw 1976 QD kT 283.15 0.156–100.058 30.850, 35.056, 39.067 7 15  10  6 cm3 g  1
Chen 1976 MFD p,v,T,kT,ap 273.15–313.15 0–100 5.493–40.052 7 4  10  6 cm3 g  1
Millero 1976 MFD r,T,S 273.15–313.15 0.101 0.5–40.189 7 3  10  6 g cm  3
Caldwell 1978 PB p,T, rmax 267.07–276.99 0.101–38.09 0–29.981 0.2 bar in p
Chen 1978 MFD p,v,T,kT,ap 273.15–313.15 0–100 35.165 7 4  10  6 cm3 g  1
Poisson 1980 VT r,T,S 273.15–303.15 0.101 5.045–42.058 7 1.4  10  4 g cm  3
Poisson 1993 VTD r,T,S 288.148–303.155 0.101 34.472–50.258 7 1.4  10  4 g cm  3
Millero 2009 VTD r,T,S 273.13–363.15 0.101 4.147–70.871 7 0.003 kg m  3
Safarov 2009 VTD p,r,T 273.13–468.15 0.101–140 35.159 7 1–3  10  4 g cm  3

r, density; v, specific volume; p, pressure; T, temperature; SA, salinity; kT, isothermal compressibility; I, ionic strengths; ap, isobaric thermal expansibility; OSP, Ostwald-
Sprengel’s Pyknometer; IM, inorthodox method; HPV, high-pressure volumetry; LP, Lipkin pycnometer; DT, differential transformet; D, dilatometer; PA, piezometer
apparatus; BGD, Borosilicate glass dilatometer; BTDC, bellows-type differential compressimeter; MFD, magnet flow densimeter; QD, quartz dilatometer; PB, pressure
bomb; VD, vibration densimeter; VTD, vibration tube densimeter.
148 J. Safarov et al. / Deep-Sea Research I 65 (2012) 146–156
Millero et al. (2008) determined a Reference Composition con-
sisting of the major components of Atlantic surface seawater using
earlier chemical analysis data. Reference Seawater is defined as any
seawater that has the Reference Composition and a new Reference-
Composition Salinity SR is defined to provide the best available
estimate of the Absolute Salinity of both Reference Seawater and the
Standard Seawater that was used in the measurements of the
physical properties. The new independent salinity variable SR is
intended to be used as the concentration variable for future
thermodynamic functions of seawater, as an SI-based successor of
Practical Salinity.
Safarov et al. (2009) reported the experimental (p,r,T) values
of standard seawater (SA ¼35.159 g kg  1) at T¼273.14–468.06 K
and pressures, p, up to 140 MPa with the reproducibility of
the density measurements observed to be in the range
Dr/r ¼ 70.01–0.03%. The measurements were made with a high
pressure vibration-tube densimeter. Based on these and previous
measurements, an empirical expression for the density of stan-
dard seawater has been developed as a function of pressure and
temperature. This equation was used to calculate other volu-
metric properties including isothermal compressibility, isobaric
thermal expansibility, differences in isobaric and isochoric heat
capacities, the thermal pressure coefficient, internal pressure and
the secant bulk modulus.
Millero and Huang (2009) carried out new seawater density
measurements as a function of temperature T¼273.15–363.15 K
and salinity SA ¼5–70 g kg  1, which were used to extend the
equation of state to high temperatures and salinities. The seawaters
used in this study were Standard Seawater (SP ¼35.00) and surface
Gulf Stream seawater (SP ¼36.10). Solutions at low salinities were
obtained by adding ion exchange water by weight and the high
salinities by slowly evaporating the samples. The salinities of the
evaporated samples are estimated to be accurate to 70.003 g kg  1.
The densities were measured on an Anton-Paar 500 vibrating tube
densimeter at a fixed temperature (70.003 K) determined with a
Platinum thermometer in the instrument and the average uncer-
tainty of measurements was Dr ¼ 70.003 kg m  3.
Sharqawy et al. (2010) critically reviewed the correlations and
data for the thermophysical properties of seawater. The density,
specific heat capacity, thermal conductivity, dynamic viscosity,
surface tension, vapour pressure, boiling point elevation, latent
heat of evaporation, specific enthalpy, specific entropy and
osmotic coefficient were examined. Results were presented in
terms of regression equations as functions of temperature and
salinity. The available correlations for each property were sum-
marized. Best fitted new correlations were obtained from avail-
able data for density, dynamic viscosity, surface tension, boiling
point elevation, specific enthalpy, specific entropy and osmotic
coefficient after appropriate conversion of temperature and sali-
nity scales to the most recent standards. In addition, a model for
latent heat of vaporization was suggested.
Feistel et al. (2010) presented the background information and
equations required for the determination of the properties of
single phases and components as well as of phase transitions and
composite systems as implemented in the SIA library of TEOS-10.
All results are based on rigorous mathematical methods applied
to the primary standard equations of the constituents, formulated
as empirical thermodynamic potential functions, endorsed as
formulations of the IAPWS.
These are the most important publications together with the
literature review in Safarov et al. (2009), where it is possible to
find the main thermodynamic properties of seawater at various
temperatures, pressures and salinities. Also, from Table 1 it is to
be seen that the main research works were done for very
restricted intervals in temperature, pressure and salinity. The
salinity intervals in Table 1 are shown in absolute salinities
SA/g kg  1 (SA ¼ 1.00471543 g kg  1  Sp; Millero et al., 2008). Here,
Sp is unit-less practical salinity.
This review demonstrates the importance of having reliable
thermophysical properties of seawater as a function of pressure,
temperature and salinity over a wider range of conditions. In this
respect, the purpose of our investigations was to carry out:
 A thorough literature evaluation of the thermodynamic prop-
erties of seawater.
 (p,r,T) measurements of seawater at high salinities over the
extended parameter range of interest.
 The construction of a comprehensive and accurate thermo-
dynamic equation of state over a well-specified range of
parameters which are of interest in oceanographic research,
underwater technology and land-based industrial plants run-
ning on seawater.
2. Experimental
The (p,r,T) measurements were carried out using a recently
developed high pressure – high temperature Anton-Paar DMA
HPM vibrating tube densimeter (Safarov et al., 2009; Guliyev
et al., 2009 and Nabiyev et al., 2009). Density measurements with
a vibrating tube are based on the dependence of the period of
oscillation of a unilaterally fixed U-tube (Hastelloy C-276) on its
mass. This mass consists of the U-tube material and the mass of
the fluid filled into the U-tube.
The temperature in the measuring cell was controlled using a
thermostat (F32-ME Julabo, Germany) to 710 mK using a (ITS-
90) Pt100 thermometer (Type 2141) with an experimental uncer-
tainty of 715 mK. Pressure was measured using a pressure
transmitter P-10 (WIKA Alexander Wiegand GmbH & Co., Ger-
many) with a relative uncertainty of 0.1%.
The specifications of Anton Paar company and our calibrations
indicate the reproducibility of the density measurements for
temperatures T¼273.15–468.15 K, pressures to 140 MPa and
salinities at SA ¼31.684–55.529 g kg  1 within Dr ¼ 70.1–
0.3 kg m  3 or Dr/r ¼ 70.01–0.03%.
The density measurements at ambient pressure were carried
out using the Anton-Paar DMA 4500 vibrating tube densimeter
with an uncertainty in temperature of 70.01 K. The DMA 4500
density meter measures the temperature with a high-precision
Platinum thermometer. The overall uncertainty of the experi-
mental density measurements at ambient pressure was better
than 71  10  4 g cm  3.
The samples were prepared with commercially available standard
seawater samples (Sp ¼34.994, SA ¼35.164 g kg  1, k15 ¼0.99997,
29th July 2010, OSIL Laboratory, UK) and double-distilled pure water.
Seawater samples with salinities SA o35.164 g kg  1 were prepared
by adding known amounts of double-distilled pure water.
For the preparation of seawater samples with SA 4
35.16404 g kg  1, it is necessary to weight-evaporate the standard
seawater. The electronic scale Sartorius ED224S with 0.0001 g
uncertainty is used for the preparation of seawater solutions with
salinities higher than those of the standard seawater batches. The
absolute salinity of prepared samples was determined using the
density measurements in DMA 4500 vibration tube densimeter
and the Practical Salinity measurements with three significant
digits in ‘‘Autosal’’ Laboratory Salinometer (Model 8400B).
3. Results and discussion
The (p,r,T) properties of seawater samples with absolute salinities
SA ¼(31.684, 33.507, 37.372, 37.969, 40.164, 41.825, 44.811, 46.119,
 J. Safarov et al. / Deep-Sea Research I 65 (2012) 146–156 149

Table 2
Values of the coefficients aij, bij and cij in Eqs. (1)–(4) for the seawater solutions.

aij bij cij

a10 ¼ 16.8260119036 b00 ¼ 1780.94028549 c00 ¼  1197.00357946

a11 ¼  0.0141313351238
a12 ¼ 0.247406490575  10  3
a20 ¼  0.174551209401
a21 ¼ 0.336290751342  10  4
a22 ¼  0.102404029138  10  5
a30 ¼ 0.590549251552  10  3
a31 ¼ 0
a32 ¼ 0
a40 ¼  0.843286627505  10  6
a41 ¼ 0
a42 ¼ 0.482122273652  10  11
a50 ¼ 0.444848916045  10  9
a51 ¼  0.346870313329  10  13
a52 ¼  0.534550469142  10  14
b01 ¼  8.44625953277
b02 ¼  0.0203022580799
b10 ¼  23.9619103076
b11 ¼ 0.0616367739239
b12 ¼ 0
b20 ¼ 0.123588063860
b21 ¼  0.115367580107  10  3
b22 ¼ 0
b30 ¼  0.230808294277  10  3
b31 ¼ 0
b32 ¼ 0
b40 ¼ 0.142119761663  10  6
b41 ¼ 0
b42 ¼ 0.534482054293  10  12
c01 ¼ 8.48513299409
c02 ¼ 0
c10 ¼ 11.7622451237
c11 ¼  0.0571254359702
c12 ¼ 0
c20 ¼  0.0402338524280
c21 ¼ 0.958997239703  10  4
c22 ¼ 0.185255385513  10  6
c30 ¼ 0.418262515254  10  4
c31 ¼ 0
c32 ¼ 0
c40 ¼ 0
c41 ¼ 0
c42 ¼  0.986850131470  10  12

48.600, 50.232, 52.449 and 55.529) g kg  1 were measured at tem- 140

peratures T¼273.15–468.15 K and pressures, p, up to 140 MPa. The
temperature and pressure steps in the experiments were in the 130
ranges T¼5–20 K and p¼5–10 MPa, respectively. All the resulting
120
values of are listed in the Appendix I.
The set of 7616 measured (p,r,T) values of seawater with
110
absolute salinity SA ¼0–55.529 g kg  1 at 34 different salinities as
a function of pressure, temperature and salinity were used to fit 100
the coefficients of the equation of state (1) (Safarov et al., 2009):
90
ðp=MPaÞ ¼ Aðr=g cm3 Þ2 þ Bðr=g cm3 Þ8 þ Cðr=g cm3 Þ12 : ð1Þ

First the coefficients of EOS (1) were fitted together in the 80

dependence of temperature and salinity:
p/MPa

70
X
5 X
2
A¼ T i
aij SjA , ð2Þ 60
i¼1 j¼0

50
X
4 X
2
B¼ Ti bij SjA , ð3Þ 40
i¼0 j¼0

30
X
4 X
2
C¼ T i
cij SjA : ð4Þ 20
i¼0 j¼0

10
The coefficients aij, bij and cij Eqs. (1)–(4) are given in Table 2.
For the salinity analysis, densities of pure water (IAPWS-95)
0
(Wagner and Pruß, 2002 were used. For the fitting, the percent 900 920 940 960 980 1000 1020 1040 1060 1080
(PD, %) and average percent deviations (APD, %) between the /kg m-3
measured and fitted density values are calculated as:
! Fig. 1. Plot of pressure p of seawater (SA ¼37.372 g kg  1) vs density r: ~,
rexp req 273.15 K; ’, 278.15 K; m, 283.15 K; K, 293.15 K; ., 298.15 K;  , 313.17 K; B,
PD,% ¼ 100 , ð5Þ 333.15 K; &, 353.15 K; W, 373.15 K; J, 393.15 K; X, 413.16 K; , 433.14 K; %,
rexp
453.15 K; $, 468.08 K; ___ calculated by Eqs. (1)–(4).
 
100 X rexp req 
APD, % ¼  , ð6Þ
n  rexp 
determined density of seawater in high salinities and rcal is the
where rexp is the measured density of seawater; req is the density value determined from Eqs. (1)–(4).
obtained as the result of fitting, n is the number of fitted points. Calculated thermal properties using Eqs. (1)–(4) along with the
Eqs. (1)–(4) describe the experimental (p,r,T) results (7616 derived equations (Safarov et al., 2009), such as isothermal
points) of seawater with absolute salinity SA ¼(0 to compressibility kT  106 MPa  1, isobaric thermal expansibility
55.529) g kg  1 within Dr/r ¼ 70.0078% average percent, corre- ap  106 K  1, differences in isobaric and isochoric heat capacities
sponding to Dr ¼0.09 kg m  3 absolute standard deviation. (cp–cv) /Jkg  1 K  1, thermal pressure coefficient g MPa K  1 and
Figs. 1–3 show plots of the pressure p of seawater internal pressure pint MPa are presented in Appendix I.
(SA ¼37.372 g kg  1) vs density r, the density r of seawater Figs. 4–8 show plots of the isothermal compressibility kT 
(SA ¼41.825 g kg  1) vs temperature T calculated by Eqs. (1)–(4), 106 MPa  1 of seawater (SA ¼31.684 g kg  1), of the isobaric thermal
and the percent deviations (rexp–rcal)/rexp of high salinity sea- expansibility ap  106 K  1 of seawater (SA ¼44.811 g kg  1), of the
water (p,r,T) results vs pressure, where rexp is the experimentally difference in isobaric and isochoric heat capacities (cp–cv)/J kg  1 K  1
150 J. Safarov et al. / Deep-Sea Research I 65 (2012) 146–156

1100 820
1090 800

1080
780
760
1070
740
1060
720
1050 700
1040 680

1030
660
640
1020
620
1010
600
/kg m

10 /MPa
1000 580
990 560
980
540
520
970
500
960
480
950 460
940 440
930 420
400
920
380
910
360
900 340
273.15 293.15 313.15 333.15 353.15 373.15 393.15 413.15 433.15 453.15 473.15
T/K
320
300
Fig. 2. Plot of density r of seawater (SA ¼41.825 g kg  1) vs temperature T 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140
calculated by Eqs. (1)–(4): ~, 0.101 MPa (after T¼373.15 K—ps of water); ’, p/MPa
5 MPa; m, 10 MPa; K, 20 MPa; ., 30 MPa;  , 40 MPa; B, 50 MPa; &, 60 MPa;
W, 70 MPa; J, 80 MPa; X, 90 MPa; , 100 MPa; %, 110 MPa; $, 120 MPa; Fig. 4. Plot of isothermal compressibility kT of seawater (SA ¼31.684 g kg  1) vs
þ , 130 MPa; x, 140 MPa. pressure p: ~, 273.16 K; ’, 278.17 K; m, 283.17 K; K, 293.16 K; ., 298.15 K;  ,
313.17 K; B, 333.13 K; &, 353.14 K; W, 373.15 K; J, 393.14 K; X, 413.15 K; ,
433.15 K; %, 453.16 K; $, 468.87 K.
0.07

0.06 1300
1250
0.05 1200
1150
0.04
1100
0.03 1050
1000
0.02 950
900
0.01 850
)/

800
0.00
750
10 (

-0.01 700
10 /K

650
-0.02 600
550
-0.03 500
450
-0.04
400
-0.05 350
300
-0.06 250
200
-0.07 150
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140
100
p/MPa
50
Fig. 3. Plot of deviations of experimental density rexp of the investigated seawater 0
samples [J, SA ¼ 0, 31.684–55.529 g kg  1] from the values calculated density.req 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140
obtained from Eqs. (1)–(4) vs pressure p at T¼ 273.15–468.15 K. p/ MPa

Fig. 5. Plot of isobaric thermal expansibility ap of seawater (SA ¼44.811 g kg  1) vs

of seawater (SA ¼48.600 g kg  1), of the thermal coefficient of pres- pressure p: ~, 273.17 K; ’, 278.15 K; m, 283.16 K; K, 293.18 K; ., 298.15 K;  ,
sure g/MPa K  1 of seawater (SA ¼50.232 g kg  1) and of the internal 313.15 K; B, 333.11 K; &, 353.15 K; W, 373.14 K; is, 393.15 K; X, 413.17 K; ,
pressure pint/MPa of seawater (SA ¼55.529 g kg  1) vs density r. 433.19 K; %, 453.16 K; $, 467.95 K.
 J. Safarov et al. / Deep-Sea Research I 65 (2012) 146–156 151

1050 800
1000
950
700
900
850
800
600
750
700
650 500
600
(c -c )/Jkg K

550

P /MPa
500 400

450
400
300
350
300
250
200
200
150
100 100
50
0
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140
p/ MPa p/ MPa

Fig. 6. Plot of difference in isobaric and isochoric heat capacities (cp  cv) of Fig. 8. Plot of internal pressure pint of seawater (SA ¼ 55.523 g kg  1) vs pressure p:
seawater (SA ¼48.600 g kg  1) vs pressure p: ~, 273.16 K; ’, 278.20 K; m, ~, 273.14 K; ’, 278.16 K; m, 283.16 K; K, 293.15 K; ., 298.15 K;  , 313.18 K;
283.16 K; K, 293.14 K; ., 298.15 K;  , 313.15 K; B, 333.16 K; &, 353.14 K; B, 333.15 K; &, 353.15 K; W, 373.17 K; J, 393.16 K X, 413.14 K; , 433.15 K;
W, 373.14 K; J, 393.14 K; X, 413.16 K; , 433.14 K; %, 453.16 K; $, 468.11 K. %, 453.15 K; $, 467.96 K.

2.0
4200

4000
1.8
3800

3600
1.6
3400

1.4 3200

3000
1.2 2800
K/MPa

2600
/ MPa K

1.0
2400

2200
0.8
2000

1800
0.6
1600

0.4 1400

1200
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140
0.2 p/MPa

Fig. 9. Plot of calculated values of secant bulk modulus K of seawater at high

0.0 salinities vs pressure p at various temperatures T.
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140
p/ MPa
The secant bulk modulus of seawater (Safarov et al., 2009),
Fig. 7. Plot of thermal coefficient of pressure g of seawater (SA ¼ 50.232 g kg  1) vs
pressure p: ~, 273.15 K; ’, 278.18 K; m, 283.14 K; K, 293.12 K; ., 298.15 K;  ,
K MPa, at high salinities is shown as a function of pressure in
313.13 K; B, 333.11 K; &, 353.12 K; W, 373.15 K; J, 393.14 K; X, 413.11 K; , Fig. 9 and given in Appendix II. The secant bulk modulus for
433.17 K; %, 453.16 K; $, 468.03 K. seawater is approximately a linear function of pressure after
152 J. Safarov et al. / Deep-Sea Research I 65 (2012) 146–156

p ¼5–10 MPa. Values near ambient pressures are unreasonable
due to problems in taking the numerical derivative. More reliable
values of K at low pressures can be determined from compressi-
bilities determined from sound speed measurements.
Another important parameter for assessing the quality of the
empirical equation of state is the fit of apparent molar volume
and compressibility of seawater to the Pitzer equation, the
analysis of Debye–Hückel limiting slopes for the sea salts and
the evaluation of the infinite-dilution apparent molar volume of
sea salt. Since the thermodynamic properties of seawater diluted
with pure water can be used to determine the properties of lakes
and rivers (Millero, 1975, 2000; Millero et al., 1976), it is useful to
fit these properties to equations that approach pure water as the
salinity decreases.
In their earlier studies, Millero and colleagues (Millero et al.,
1973; Duer et al., 1976; Millero and Leung, 1976) examined the
thermochemical properties of seawater using an extended
Debye–Hückel equation, which was an extension of the

22
21
20
19
18
17
16
V /cm3 mol-1

15
14
13
12
11
10
9
8
7
6
273.15 293.15 313.15 333.15 353.15 373.15 393.15 413.15 433.15 453.15 473.15
T/K

Fig. 10. Plot of calculated values of apparent molar volumes Vf of seawater (SA ¼ 40 g kg  1) vs temperature T at various pressures p: ~, 0.101 MPa (after T¼373.15 K—ps
of water); ’, 5 MPa; m, 10 MPa; K, 20 MPa; ., 30 MPa;  , 40 MPa; B, 50 MPa; &, 60 MPa; n, 70 MPa; J, 80 MPa; ,, 90 MPa; , 100 MPa; %, 110 MPa; $, 120 MPa; þ ,
130 MPa;  , 140 MPa.

0.00

-0.01

-0.02

-0.03

-0.04

-0.05
/MPa-1 mol-1

-0.06

-0.07

-0.08

-0.09

-0.10

-0.11

-0.12

-0.13
273.15 293.15 313.15 333.15 353.15 373.15 393.15 413.15 433.15 453.15 473.15
T/K

Fig. 11. Plot of calculated values of apparent molar compressibility kf of seawater (SA ¼48 g kg  1) vs temperature T at various pressures p: ~, 0.101 MPa (after
T¼ 373.15 K—ps of water); ’, 5 MPa; m, 10 MPa; K, 20 MPa; ., 30 MPa;  , 40 MPa; B, 50 MPa; &, 60 MPa; W, 70 MPa; J, 80 MPa; X, 90 MPa; , 100 MPa; %,
110 MPa; $, 120 MPa; þ, 130 MPa;  , 140 MPa.
 J. Safarov et al. / Deep-Sea Research I 65 (2012) 146–156 153

Guggenheim equation (Guggenheim, 1935) as formulated by
Lewis and Randall in 1961. This equation was not used for the
fitting of the (p,r,T) properties (Millero, 1982; Millero and
Schreiber, 1983). More recently Pierrot and Millero (2000) have
used the (1979) Pitzer equations to fit the (p,r,T) properties of
seawater. These equations allow one to extrapolate the properties
of seawater to pure water that can be compared to estimates of
mixtures of electrolyte solutions of the major components of
seawater. Our new measurements allow us to extend the Pitzer
equations for seawater to a wide range of temperatures, pressures
and salinity. The purpose of this paper is the presentation the
high-salinity (p,r,T) measurement results of seawater and the
calculation of derived apparent molal properties. In a subsequent
publication we will use the (p,r,T) properties of seawater already
measured by our group at low salinities for their fitting to Pitzer
equations and for the analysis of properties at infinite dilution.
The apparent molar volume of seawater solutions, Vf, is given by
V f ¼ ðVn1 V 01 Þ=n2 ,
where n1 and n2 are the number of moles of pure water and total
salts in seawater, respectively, and V 01 is the molar volume of pure
water. Using the density values of seawater at various salinities and
that of pure water at high temperatures and pressures, the apparent
molar volume Vf and the compressibility kf of sea salt in water will
be defined by Eqs. (8) and (9):
V f ¼ ðrw rsw Þ=ðmrsw rw Þ þ M=rsw , ð8Þ
kf ¼ ðbswT rw bwT rsw Þ=ðmrsw rw Þ þ bswT =rsw , ð9Þ
where rw and rsw are the densities of pure water and seawater
at a various salinities, respectively, m is the molality of sea salt
in seawater, M is the molar mass of the dissolved sea salt
(M ¼62.807 g mol  1, Millero et al., 2008), bswT and bwT are the
isothermal compressibilities of seawater and water, respec-
tively. As mentioned above, we are treating seawater as a
solution composed of a single ’’sea salt’’. From the average
composition of seawater, (Pierrot and Millero, 2000) the mol-
ð7Þ ality m of sea salt can be calculated as a function of salinity

0.026
0.024
0.022
0.020
0.018 0.008
0.016
0.014 0.006
0.012
0.004
0.010
0.008 0.002
0.006
0.004 0.000
0.002
0.000 -0.002
-0.002
-0.004
-0.004
-0.006 -0.006
-0.008
-0.010 -0.008
0 10 20 30 40 50 60 70 80 90 100 30 32 34 36 38 40 42 44 46 48 50 52 54 56
p/MPa SA/g kg-1

0.06
0.05
0.04
0.03
0.02
0.01
0.00
-0.01
-0.02
-0.03
-0.04
-0.05
-0.06
0 10 20 30 40 50 60 70 80 90 100
p/MPa

Fig. 12. Deviation of various measured density values of other workers from the empirical correlation Eqs. (1)–(4) of this paper: (a) Equation of state EOS 1980 (Millero
et al., 2008), [B, SA ¼ 31.684–55.529 g kg  1, T¼ 273.15–313.15 K and p ¼0.101–100 MPa]. (b) Millero and Huang, 2009 [B, SA ¼ 31.837–54.936 g kg  1, T¼ 273.148–
363.152 K and p ¼0.101 MPa]. (c) Data points computed from the TEOS-10 equation of state [~, SA ¼ 31.684; &, SA ¼33.507; m, SA ¼37.372; W, SA ¼ 37.969; B,
SA ¼ 40.164) g kg  1, at T¼ 273.15–313.15 K and p ¼ 0.101–100 MPa].
154 J. Safarov et al. / Deep-Sea Research I 65 (2012) 146–156

(Millero et al., 2008) by: with Millero and Huang (2009). These literature results are
mostly smaller than our values and their average deviation from
m ¼ 15:921617USA =ð1000SA Þ ð10Þ our measurements is Dr/r ¼ 70.0033%. The maximum deviation
in this comparison is Dr/r ¼0.0068% at T¼ 273.148 K and
SA ¼31.837 g kg  1 (Fig. 12(b)).
The calculated values of apparent molar volumes Vf and the
The 424 experimental density values for seawater in the tem-
compressibility kf of sea salt in water for the various salinities are
perature range T¼273.15–313.15) K, salinities SA ¼(31.684, 33.507,
shown in Figs. (10) and (11).
37.372, 37.969 and 40.164) g kg  1 and for pressures up to 100 MPa
The measured (p,r,T) results of seawater at high salinities were
were compared with calculated results using the TEOS-10 (IOC, SCOR,
compared with the calculated results of EOS-80 (Millero et al.,
IAPSO, 2010 and IAPWS, 2008) equations of state. The TEOS-10
1980), of Millero and Huang (2009) and of TEOS-10 (IOC, SCOR,
properties of seawater are all derived from a Gibbs function (by
IAPSO, 2010; IAPWS, 2008) at the state parameters’ interval of
mathematical processes such as differentiation) and so are totally
TEOS 10. The good agreement obtained is discussed below.
consistent with each other (in contrast to the now obsolete EOS-80
The 2268 (p,r,T) results calculated from EOS-80 (Millero et al.,
approach where separate polynomials were provided for each
1980) for water and seawater at S¼3.141–40.189, T¼273.15–
thermodynamic variable and they were not fully mutually consis-
313.15 K and pressure up to 100 MPa were compared with our
tent). The average deviation between calculated TEOS-10 results and
results. The average deviation of these values from our measure-
our measurements is Dr/r ¼ 70.0136% (Fig. 12(c)). The maximum
ments is Dr/r ¼ 70.008%. The density results of Millero et al.
difference of (p,r,T) results in (IOC, SCOR, IAPSO, 2010; IAPWS, 2008)
(1980) are smaller than ours for pressures up to about 50 MPa
from our results is Dr/r ¼ 0.0535% at T¼283.13 K, p¼39.976 MPa
and larger above this pressure. The maximum uncertainty of
and SA ¼39.969 g kg  1.
(p,r,T) results of Millero et al. (1980) is Dr/r ¼0.03% at
The calculated thermal coefficients were compared with the
T¼273.15 K, p ¼0 MPa (Fig. 12(a)).
available literature results (mostly values of isothermal compres-
We compared 230 of our density results for seawater at high
sibility kT and isobaric thermal expansibility ap). Calculated values
salinities at SA ¼31.837–54.936 g kg  1, T¼273.148–363.152 K
for isothermal compressibility kT (99 points) and for isobaric
thermal expansibility ap (99 points) are presented by Chen and
4 Millero (1976). The results of comparison are the following: the
average deviation kTlit–kTcal between the isothermal compressi-
3 bility results is 71.15  10  6 MPa  1 and the maximum deviation
of kTlit–kTcal is 3.4  10  6 MPa  1 at T¼273.15 K and p¼40 MPa.
2 The average deviation aplit–apcal between the isobaric thermal
expansibility results is ap ¼ 76.12  10  6 K  1 and the maximum
1 deviation aplit–apcal is Dap ¼16  10  6 K  1 at T¼273.14 K and
p¼100 MPa (Fig. 13(a) and (b)).
0 Calculated values of the secant bulk modulus were compared
with the related results of Millero et al. (1980). The differences
-1 Kcal–Klit between the calculated values are:

-2
SA ¼0, T¼ 273.15 K, p ¼100 MPa, Kcal–Klit ¼ 71.991 MPa
SA ¼35.16504 g kg  1, T¼273.15 K, p ¼100 MPa,
-3
Kcal–Klit ¼ 714.157 MPa
SA ¼0, T¼ 298.15 K, p ¼100 MPa, Kcal–Klit ¼ 76.556 MPa
-4
0 10 20 30 40 50 60 70 80 90 100 SA ¼35.16504 g kg  1, T¼298.15 K, p ¼100 MPa,
p /MPa Kcal–Klit ¼ 70.096 MPa

20
4. Conclusions

15 This study presents new (p,r,T) measurements for seawater with

absolute salinities SA ¼31.68370–55.52861 g kg  1 at temperatures
10 T¼273.15–468.15 K and pressures, p, up to 140 MPa. The results are
used to derive an equation of state that is valid for higher
temperatures, pressures and salinities than previously available.
5 The temperature dependence of the (p,r,T) values and of the
calculated thermal properties of the investigated seawater sam-
0
ples have similar anomalies to those of pure water (Appendix I, II
and Figs. 2). This is not very surprising since the major mass
fraction of seawater (appr. 96.5%) is pure water. In a typical liquid
-5 the compressibility decreases as the structure becomes more
compact due to lowered temperature. In water and all aqueous
salt solutions in which the concentration of water is very high, the
-10
0 10 20 30 40 50 60 70 80 90 100 cluster equilibrium shifts towards a more open structure (for
p /MPa example, expanded structure—ES) as the temperature is reduced
due to preference for a more ordered structure [that is, DG for
Fig. 13. Deviation of calculated thermal properties of seawater (SA ¼35.164 g kg  1)
between literature values of Chen and Millero (1976) and of this work at
ES$CS (collapsed structure) becomes more positive] (Chaplin,
T¼273.15–313.15 K and p¼ 0.101–100 MPa. (a) isothermal compressibility kT. 2009). As the water structure is more open at these lower
(b) isobaric thermal expansibility ap. temperatures, its capacity to be compressed increases (Kell,
 J. Safarov et al. / Deep-Sea Research I 65 (2012) 146–156
1975). Since the compressibility depends on fluctuations in the
specific volume, these will be largest where water molecules have
a more open structure. At high pressures (for example,
200 MPa) this compressibility anomaly, although still present,
is far less apparent (Kanno and Angell, 1979).
Acknowledgment
The German Research Foundation (DFG) appreciate for the
financial support of this investigations (HA2226/12-1, -2 and
HE1199/16-1, -2). FJM wishes to acknowledge the support of
the National Science Foundation and the National Oceanic and
Atmospheric Administration Office.
Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at http://dx.doi.org/10.1016/j.dsr.2012.03.
010.
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