Chemical Exergy Evaluation

Energy 31 (2006) 33103326
Standard chemical exergy of elements updated

R. Rivero
, M. Garas
Instituto Mexicano del Petroleo, Grupo de Exergia, Eje Central Lazaro Cardenas 152, 07730, Mexico, D.F., Mexico
Abstract
The chemical exergy of a substance is the maximum work that can be obtained from it by taking it to chemical
equilibrium with the reference environment at constant temperature and pressure. This exergy is normally taken or
calculated from tabulated values obtained for standard conditions, i.e. an ambient temperature of 298.15 K, an
atmospheric pressure of 1 atm, and a model of reference species which considers the concentration of the most common
components of the atmosphere, the oceans and the Earths crust. The model proposed by Szargut for the calculation of the
standard chemical exergy of elements and organic and inorganic substances has been revised. As a result of this revision,
updated values of standard chemical exergy of elements are presented and compared with the ones estimated by Szargut.
Because of some anomalous behaviour in the chemical exergy when a different salinity of seawater is assumed, some
different reference species than those used in the latest version of the Szargut model were proposed for the following
elements: silver, gold, barium, calcium, cadmium, copper, mercury, magnesium, nickel, lead, strontium and zinc.
A complete set of updated values of chemical exergies of elements for the standard conditions (298.15 K and 1 atm) is
tabulated.
r 2006 Published by Elsevier Ltd.
Keywords: Standard chemical exergy; Elements; Reference species; Environment.
1. Introduction
The exergy of a system is a measure of the quality of the energy which it contains and of its distance from
the environment since it is dened as the minimum work necessary to produce a substance in a specic state
from the species present in the environment by means of reversible processes in which heat and mass are
interchanged only with the surroundings.
The exergy of a substance can be separated into physical and chemical. Physical exergy is the work that can
be obtained by taking the system to the temperature and pressure conditions of the environment at constant
composition. Otherwise, chemical exergy (Ex
q
) is the work that can be obtained by taking a substance to
chemical equilibrium with the environment at constant temperature and pressure. The chemical exergy has
two contributions: reactional exergy, resulting from the chemical reactions necessary to produce species
existing as stable components in the environment, from the initial composition of the substance; and
ARTICLE IN PRESS
www.elsevier.com/locate/energy
0360-5442/$ - see front matter r 2006 Published by Elsevier Ltd.
doi:10.1016/j.energy.2006.03.020
Corresponding author. Tel.: +52 55 91 75 84 27; fax: +52 55 91 75 80 00.

E-mail address: rrivero@imp.mx (R. Rivero).
ARTICLE IN PRESS
Nomenclature
Ex exergy
T absolute temperature [K]
P pressure
DG Gibbs free energy
n number of moles
R ideal gas constant
x mole fraction
P
o
vapour pressure
j number of reference ions derived from one molecule of the element under consideration
z charge, in electric units, of the reference ion present in seawater
b
y
number of molecules of the additional element y present in a molecule of the reference species in
seawater
pH negative logarithm of the hydrogen ion concentration
m molal concentration or molality mol=kgH
2
O
I total ionic strength mol=kgH
2
O
S conventional seawater salinity [%: parts per thousand]
w mass fraction
PM molecular mass
c
i
fraction of the element appearing in a reference species i
PA atomic mass
K thermodynamic equilibrium constant of a reaction
k stoichiometric constant of a reaction
lng
el
DebyeHu ckel term
X term that is in function of the second and third virial coefcient in Pitzers equations, as well as of
molal concentration and charge of the ions in solution
B second virial coefcient in Pitzers equations
C third virial coefcient in Pitzers equations
A
f
DebyeHu ckel constant for the osmotic coefcient
l
i
number of atoms of the element in the molecule of the reference species i present in the
lithosphere
n
o
mean molar concentration in the external layer of Earths crust
M
o
mean molecular mass of the external layer of Earths crust
Greek symbols
f relative humidity of atmospheric air
g activity coefcient (molal scale)
b
HSO
4
stoichiometric association constant of the bisulfate ion
n number of ions
Superscripts
0 standard state
Subscripts
q chemistry
n normal conditions of temperature (298.15 K), pressure (101.325 kPa) and concentration of the
species
R. Rivero, M. Garas / Energy 31 (2006) 33103326 3311
concentrational exergy, which results from the necessary processes to match the chemical concentration of the
produced species to their chemical concentration in the environment [1].
Then, the chemical exergy quantity depends on the environmental model that is selected as reference.
According to Van Gool [2], Szargut [3], and Wepfer and Gaggioli [4], the model of the reference environment,
besides being practical from a technical point of view, should be as close as possible to the natural
environment and should be capable of providing an economic indicator for the exergy values, this is,
substances abundant in nature should have lower exergies than scarce ones.
There are different models of reference environment proposed for the determination of exergy; some of
them (Ahrendts model [5], and Van Gools model [6]) are in thermodynamic equilibrium but their
composition and parameters differ distinctly from the natural environment. Others, however, consider the
species that are in abundance in the real environment, which is not in thermodynamic equilibrium, as
reference. This is the case of Szarguts model [3,7], which gives adequate and consistent results according to the
study performed by Mun oz and Michaelides [8], who showed the impact of the different models in the exergy
analysis of a power plant.
According to Szargut [3,7], to calculate chemical exergy of a substance, reference species should be chosen
as the most probable products of the interactions between the considered substance and the components of the
natural environment. Reference species can be either gaseous components from the atmosphere, or species
dissolved in seawater, or solid compounds present on the Earths surface. In order to simplify, Szargut
suggests that the chemical exergy obtained in the standard state at normal temperature and pressure
conditions (T
n
and P
n
), should be considered as a standard chemical exergy Ex
0
q
, taking into account the
conventional mean concentrations of the reference species in the environment. Knowing the standard chemical
exergy values of elements, the standard chemical exergy of any chemical compound can be determined by
means of an exergy balance of its formation reaction, this is,
Ex
0
q
DG
0
f

el
n
el
Ex
0
qel
. (1)
In Fig. 1 the Periodic Table of the Elements is shown, indicating the environment for the reference species
recommended by Szargut in 1983 [9], for the chemical exergy estimation of each element. The crossed element
means that there was not information on the environment composition or thermodynamic properties of the
reference species of the element under consideration. In 1988, Szargut et al. [7] preferred to choose reference
species from the hydrosphere for the standard chemical exergy calculation of bismuth, molybdenum and
wolframium, instead of reference species in the lithosphere. However, in the case of magnesium, cobalt and
phosphorous, he selected reference species present in the Earths crust (Fig. 2).
Szargut [3], in 1989, corroborated the choice of the reference species for the calculation of chemical exergy,
indicating the ones to be recommended and those that may not be, establishing besides, that reference species
dissolved in seawater should be preferred, because they give a relatively higher accuracy in the calculations.
However, a reference species in the hydrosphere should not be accepted if it leads to a negative value for the
chemical exergy of a compound containing common elements besides the element under consideration.
Furthermore, Szargut indicated that when the chemical exergy value of an element obtained from a solid
ARTICLE IN PRESS
f reaction of formation
el element
i species or component of a mixture
y additional reacting species in the reference reaction
TOT total
M cation
X anion
a anion
c cation
reference species is greater (420 kJ/gmol) than that calculated using a reference species dissolved in seawater,
the solid species should be preferred.
Thus, in Fig. 3, the Periodic Table of the Elements with the environment of the reference species
recommended as rst choice, according to the latest Szarguts paper is shown [3]. In this gure, it can be
observed that Szargut selected reference species in the Earths crust for calcium, strontium, barium, gold and
uorine instead of the species in seawater that he had previously considered as references for these elements,
and come back to his rst reference species selection for phosphorous, this is, a reference species contained in
the hydrosphere.
Valero et al. [10], in 2002, showed updated standard chemical exergy values of the elements, considering the
environmental model of Szargut, but using more precise data of the concentration of elements in the Earths
crust in accordance with the review performed by Ranz in her doctoral thesis [11]. Valero et al., point out that
the effect on chemical exergy of elements present in lithosphere is less than 10 kJ/gmol when Ranzs values of
concentration are used instead of those considered by Szargut.
Besides, Valero et al., adopted the reference species proposed by Szargut except for elements: aluminium,
arsenic, beryllium, calcium, zirconium, chromium, cobalt, uorine and magnesium (see Fig. 4). Some of these
reference species are recommended by Szargut as second choices, this is the case of Ca
2+
(hydrosphere), ZrO
2
(lithosphere) and Mg
2+
(hydrosphere), or as rejected references because they do not render good results in the
estimation of chemical exergy: Al
2
O
3
, AsO
5
, BeO, Cr
2
O
3
, Co
3
O
4
and CaF
2
(species present in the Earths
crust). Valero et al., indicate that the chemical exergy values of some updated elements are quite different that
those given by Szargut, especially aluminium, arsenic, beryllium, cobalt, chromium and uorine (1092 kJ/
gmol). However, Valero et al., compare the chemical exergy values of these elements to the values obtained
from reference species that Szargut recommends in rst place.
ARTICLE IN PRESS
H
2
He
Li Be B C N
2
O
2
F
2
Ne
Na Mg Al Si P S Cl
2
Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br
2
Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I
2
Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw
Atmosphere Hydrosphere Lithosphere
Fig. 2. Reference species media for elements according to Szargut [7].
H
2
He
Li Be B C N
2
O
2
F
2
Ne
Na Mg Al Si P S Cl
2
Ar
2
Kr
Rb Sr Y Wr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I
2
Xe
Fr Ra Ac
Within this context, a detailed revision of the Szarguts methodology for the chemical exergy calculation of
elements as well as of the adequate choice of reference species is performed in this work. Furthermore, the
chemical exergy values of elements obtained from this revision at normal conditions of temperature and
pressure are shown and compared to Szarguts estimation.
2. Standard chemical exergy of elements present in the atmosphere
Considering that species in atmospheric air follow the ideal gas behaviour, their standard chemical exergy
can be evaluated by
Ex
0
qi
RT
n
ln
P
n
P
in
RT
n
ln
1
x
in
. (2)
The partial pressure of water in air, P
H
2
O
, is obtained from the relative humidity denition, this is,
f
P
H
2
O
P
o
H
2
O
, (3)
where, P
o
H
2
O
is the vapour pressure of water at air absolute temperature, T
n
. The effect of temperature on the
vapour pressure of water follows the Antoines expression [12, Eq. (4)]. At 298.15 K, P
o
H
2
O
is equal to 3.14 kPa.
ln P
o
H
2
O
18:3036
3816:44
T 46:13
; P
o
H
2
O
mmHg and TK. (4)
ARTICLE IN PRESS
H
2
He
Li Be B C N
2
O
2
F
2
Ne
Na Mg Al Si P S Cl
2
Ar
2
Kr
2
Xe
Fr Ra Ac
H
2
He
Li Be B C N
2
O
2
F
2
Ne
Na Mg Al Si P S Cl
2
Ar
2
Kr
2
Xe
Fr Ra Ac
Fig. 4. Reference species media for elements according to Valero et al. [10].
3. Standard chemical exergy of elements dissolved in the hydrosphere
The Ex
0
q
values of elements, whose reference species are dissolved in seawater, are obtained by means of Eq.
(5), which is derived from the model proposed by Morris et al. [7].
Ex
0
qel
jDG
0
fi

1
2
jz
i
Ex
0
qH
2
j
y
b
y
Ex
0
qy
2:303RT
n
jz
i
pH jRT
n
lnm
in
g
i
. (5)
The activity coefcient of the species dissolved in seawater depends mainly on the ionic strength of the
solution, which is related to the concentration and electric charge of all species dissolved in seawater, as it is
pointed out in its denition:
I
1
2
i
m
i
z
2
i
. (6)
Szargut assumes a pH value of 8.1 for seawater and for the species activity coefcients, values of 0.6, 0.2, 0.1
and 1.0 for heavy monocharged ions, simple bicharged ions, complex bicharged ions, and non-ionic
compounds, respectively, since there is not experimental data available. In this work, pH and g
i
values are
calculated as a function of seawater salinity and temperature.
3.1. Calculation of parameters for standard chemical exergy of elements of which reference species is in the
oceans
3.1.1. Molality of the species dissolved in seawater
Chemical exergy of an element present in the hydrosphere, depends on the seawater salinity (S), this is, its
salt content. In this study, the concentration of the elements contained in seawater that Szargut reports is
considered [7]; they were based on Goldberg, Turekian, and Dyrssen and Wedborg data. The molal
concentration (moles per kilogram of water) of each species (m
i
) present in the hydrosphere, from its mass
fraction (w
i
) and seawater salinity, is given by
m
i
w
i
1
PM
i
_ _
1000
1 S=1000
_ _
. (7)
The third factor on the right-hand side of Eq. (7), corresponds to the relation between kilograms of seawater
and kilograms of water. The mass fraction estimation of each species is carried out from the total mass
fraction of the element (w
el
) under consideration and the fraction of the element appearing in the form of the
species (c
i
); to give
w
i
w
el
PM
i
PA
el
_ _
c
i
, (8)
The value of c
i
is taken from Dyrssen and Wedborg [13], who determined the proportion among most of the
species dissolved in seawater for a salinity value of 35% and pH equal to 8.12, using complex formation
constants for the main constituents of seawater at 298.15 K and stability constants for species in lower
concentration. Most of the fraction c
i
values considered in this work for each species are equivalent to those
that Szargut chooses, except for the case of the species that contains arsenic. Szargut assumes that 50% of the
arsenic element presents in seawater as the HAsO
4
2
ion (reference species of arsenic), and the rest as H
2
AsO
4
and AsO
4
3
species (Szarguts personal communication with the authors). However, from dissociation
constants at 298.15 K of each acid-base par [14], this is,
H
3
AsO
4
2H
H
2
AsO
4
; K
1
6 10
3
;
H
2
AsO
4
2H
HAsO
4
2
; K
2
10:5 10
7
;
HAsO
4
2
2H
H2AsO
4
3
; K
3
3 10
12
;
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a percentage of 93.23, 6.736 and 0.037 for HAsO
4
2
, H
2
AsO
4
and AsO
4
3
ions is obtained , respectively,
considering a pH of 8.12. Nevertheless, considering a different fraction value for the arsenic appearing as
HAsO
4
2
, with respect to the value that Szargut proposes, produces a minimum difference (0.3%) on the value
of the standard chemical exergy of arsenic.
Considering all species dissolved in seawater and, from molality and electric charge of each species, a total
ionic strength (Eq. (6)) of 0:6782 mol=kg
H
2
O
(0.670 mol/L) is obtained which is similar to 0:6745 mol=kg
H
2
O
(0.666 mol/l) that Dyrssen and Wedborg predicted [13], assuming a salinity value of 35%.
3.1.2. Seawater pH determination
In the open ocean, the pH of seawater is mostly in the range 7.88.2 [15,16] and its variation is controlled
chiey by the carbon dioxide system with minor contributions from boric acid [15,17,18]. The reactions
involved and stoichiometric constants of dissociation that described their equilibrium are:
CO
2
system:
CO
2
gas ! CO
2
dissolved
CO
2
H
2
O ! H
2
CO
3
H
2
CO
3
! H
HCO
3
; k
1C
H
HCO
3
=H
2
CO
3
(9)
HCO
3
! H
CO
3
2
; k
2C
H
CO
3
2
=HCO
3
(10)
Boron system:
H
3
BO
3
H
2
O ! H
BOH
4
; k
B
H
BOH
4
=H
3
BO
3
: (11)
The square brackets in the expressions of the equilibrium constants indicate the species concentration which
is given in mol per kilogram of seawater (mol/kg
sw
). The total concentration of HCO
3
, CO
3
2
and B(OH)
4
,
includes the concentration of both the free ion and the species formed by association with others ionic
species dissolved in sea water, such as Mg
2+
and Ca
2+
.
At present, there are different scales to report seawater pH measurements [19]. In the present study, the total
hydrogen ion concentration scale is used, developed by Hansson [20,21] in which pH is obtained by means of
electrodes calibrated in buffer solutions prepared in synthetic seawater. Hansson obtained acidity constants
for carbonic acid and boric acid at different salinity and temperature values. Now, the equilibrium constants
k
1C
, k
2C
and k
B
are determined by the Almgrens correlations [22] (Eqs. (12)(14)) that he obtained from
Hanssons results. These correlations are valid in the salinity range 2040%, and temperature range
278.15303.15 K.
pk
1C
841=T 3:272 0:0101S 0:0001S
2
, (12)
pk
2C
1373=T 4:854 0:01935S 0:000135S
2
, (13)
pk
B
1026=T 5:527 0:0158S 0:00016S
2
. (14)
Owing to the fact that sulphate present in seawater is protonated by hydrogen ion to form bisulphate,
Hansson considers that the total hydrogen ion concentration [H
+
]
TOT
of Eqs. (9)(11), comprises free
uncomplexed hydrogen ion and HSO
4
, this is,
H
TOT
H
HSO
4
H
b
HSO
4
H
SO
2
4
. (15)
The association constant for bisulphate ion bHSO
4
is obtained by the expression proposed by Khoo et al.
[23] (Eq. (16)), which is a function of temperature and ionic strength and is valid only if temperature is between
278.15 and 313.15 K and salinity is in the range of 20 to 40%.
log b
HSO
4
647:59=T 6:3451 0:019085T 0:5208I
1=2
. (16)
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Solving Eq. (15) for free hydrogen ion concentration [H
+
] and applying the negative logarithm to each term,
the following expression is found, that allows nding seawater pH at a salinity and temperature given:
pH pH
TOT
log 1 b
HSO
4
SO
2
4

_ _
. (17)
The value of pH
TOT
is found selecting anyone of the expressions of the dissociation constants k
1C
, k
2C
and
k
B
. When salinity and temperature are 35% and 298.15 K, respectively, pH is equal to 8.12, an amount very
similar to the value used by Szargut and Morris in their calculations.
3.1.3. Activity coefcients of the species dissolved in seawater
The activity coefcients of the species present in the hydrosphere are calculated by means of the Pitzers
model for electrolyte mixtures [24], which combines the DebyeHu ckels electrostatic theory for long-range
forces with a virial type expansion for short-range forces between species. Assuming that the ionic interactions
take place only between two ions of opposite charge sign at a time, the activity coefcient of the cation M and
anion X is given by
ln g
M
z
M
=z
X
ln g
0
el
2
a
m
a
X
a

a
m
c
m
a
z
2
M
B
0
ca
2z
M
C
ca
, (18)
ln g
X
z
X
=z
M
ln g
0
el
2
c
m
c
X
c

a
m
c
m
a
z
2
X
B
0
ca
2z
X
C
ca
, (19)
where
ng
0
el
A
f
z
M
z
X
j j I
1=2
=1 1:2I
1=2
1:6667n1 1:2I
1=2
_ _
. (20)
The expressions X
a
, X
c
, B
ca
, C
ca
are dependent on the molal concentration and electric charge of the ions;
on the interaction parameters between the different cations and anions in solution; and on the molal total ionic
strength. S
a
and S
c
indicate summation of the properties of all anions and cations, respectively. The constant
A
f
is equal to 0.392 for water at 298.15 K. In Table 1, single-ion activity coefcients of the cations and
anions present in seawater, obtained in this work by Pitzers equations, are shown when salinity has the value
of 35%.
In general, Pitzers model gives reasonable results. In Table 2, the single-ion activity coefcient values
estimated are compared to those found experimentally in solutions with a similar ionic strength of seawater at
35% salinity. However, this is not valid in the case of carbonate ion, as there is only information on the
interaction parameters of carbonate ion with the cations Na
+
and Mg
2+
that, although being the major
seawater constituents, they are not the only ones that carbonate ion interacts with. It is worthwhile to mention
that, values obtained for activity coefcients of the single ions are the same that those found by Whiteld [25],
who used the Pitzers equations and included trace components in seawater.
ARTICLE IN PRESS
Table 1
Single-ion activity coefcients (molal base) from Pitzers model for the hydrosphere I 0:678 mol=kg
H
2
O
Cations Anions
H
+
0.722 Hg
2+
0.075 OH
0.625 IO
3
0.523
Ag
+
0.523 K
+
0.614 Cl
0.703 MoO
4
2
0.075
Au
+
0.523 Li
+
0.729 HAsO
4
2
0.138 HPO
4
2
0.120
Ba
2+
0.189 Mn
2+
0.224 H
2
AsO
4
0.554 H
2
PO
4
0.503
BiO
+
0.523 Na
+
0.653 AsO
4
3
0.015 PO
4
3
0.014
Ca
2+
0.211 Ni
2+
0.221 B(OH)
4
0.385 SeO
4
2
0.075
Cd
2+
0.077 Pb
2+
0.196 SO
4
2
0.128 WO
4
2
0.075
Co
2+
0.217 Rb
+
0.600 Br
0.730
Cs
+
0.570 Sr
2+
0.209 HCO
3
0.559
Cu
2+
0.189 UO
2
2+
0.253 CO
3
2
0.045
Mg
2+
0.236 Zn
2+
0.203 F
0.576
In Table 1, it is observed that, as Szargut pointed out, there is a correspondence between ion type and value
magnitude of the activity coefcient. This is, the activity coefcient is more than 0.6 for simple monocharged
ions, while the value of g
i
is in the range of 0.50.6 for heavy monocharged ions. Furthermore, the g
i
value is
around 0.2 for simple bicharged ions, 0.1 for complex bicharged ions and, around 0.01 for complex ions with
an electric charge equal to three. Therefore, the activity coefcient values of the ions Cd
2+
and Hg
2+
obtained
from Pitzers model, are not adequate since the estimated value (o0.1) is less than 0.2, the expected value for
this kind of ions, result, which is due to the fact that in the activity coefcient calculation, interactions are not
included between the former cations and chloride ion, the main anion in seawater, because there was not
information on the interaction parameters of their salts.
The mean ion activity coefcient of every electrolyte can be calculated by using Eq. (21), where n n
M
+n
X
.
The g
i
values of the electrolytes HgCl
4
2
, AgCl
2
and AuCl
2
are desired to be known. At salinity of 35%,

activity coefcient of the HgCl
4
2
results in 0.45, which is so different, regards to 0.1 considered by Szargut and
estimated by Pitzers equations for complex bicharged ions; so it is here considered that the value of g
i
of
HgCl
4
2
ion, is the same as the value obtained for HAsO
4
2
ion. The activity coefcient of the ions AgCl
2
and
AuCl
2
, when salinity is 35%, is 0.637, value slightly high for this type of ion, but reasonable.
g
MX
g
nM
M
g
nX
X
_ _
1=n
. (21)
The activity coefcient of the boric acid, non-ionic compound and reference specie of boron element, is
found from thermodynamic equilibrium constant (K
B
) of the ionization reaction and activity coefcients of
the hydrogen and borate ions which are evaluated with Pitzers model; this is
g
BOH
3

k
B
K
B
g
H
g
BOH
4
, (22)
where k
B
is given by Eq. (14) in molar base (mol/kg
sw
). Hershey et al. [26], point out a pK
B
value of 9.237 at
298.15 K for ionization reaction of the boric acid. It is supposed that this equilibrium constant is given in
molal base mol=kg
H
2
O
. At 35%, it is therefore obtained an activity coefcient for B(OH)
3
of 1.22 (in molal
base). This value is close to 1.1 that Millero and Schreiber [27] estimate for non-ionic salts formed from
monocharged cations and anions, using the ion pairing model for the activity coefcient calculation and
assuming an ionic strength of 0.7 molal.
In the case of PbCl
2
species, the reference reaction is its formation and, in the same way that in the boric
acid case, its activity coefcient is calculated by means of the thermodynamic equilibrium constant denition
of the reaction (Eq. (23)). Millero and Byrne [28] determined experimentally a value of 2.03 for log K
PbCl
2
at
298.15 K and estimated a value of 14.53 (in molal base) for K
PbCl
2
in a seawater solution with an ionic strength
of 0.723 molal. If salinity is 35% (I 0.678 molal), activity coefcient obtained for PbCl
2
is 0.714, value
similar to that Millero and Byrne estimated of 0.745 in a seawater solution (I 0.723 molal). Because of the
lack of equilibrium constant information on the formation reaction of the cadmium chloride, it is assumed
ARTICLE IN PRESS
Table 2
Comparison between experimental and calculated activity coefcients of the single ions (Salinity 35%)
Ion Experimental data
a
I 0:7 mol=kg
H
2
O
Pitzers model
I 0:678 mol=kg
H
2
O
Porcentual error
Na
+
0.68 0.653 4
Mg
2+
0.23 0.236 3
Ca
2+
0.21 0.211 1
K
+
0.64 0.614 4
Cl
0.68 0.703 3
SO
4
2
0.11 0.128 16
HCO
3
0.55 0.559 2
CO
3
2
0.02 0.045 125
a
Values taken from Szarguts book [7].
that its activity coefcient is equal to the lead chloride value.
g
PbCl
2

K
PbCl
2
k
PbCl
2
g
Pb
2g
2
Cl
. (23)
3.2. Abnormal behavior of the standard chemical exergy of some elements changing salinity
Szargut in 1988, recommended as reference species for elements gold, barium, calcium, magnesium
and strontium, the species AuCl
2
, Ba
2+
, Ca
2+
, Mg
2+
and Sr
2+
, respectively, that are contained in seawater.
But, in 1989, he recommended the former species as reference in second or third choice. This is because,
in the case of calcium magnesium and barium, their Ex
0
q
values obtained from reference species dissolved
in seawater, give negative Ex
0
q
values for compounds that contained these elements; or the obtained values
of standard chemical exergy are too small for solid species that are scarce in the environment and contain
some of these elements (i.e. BaSO
4
and SrCO
3
). In the case of gold, Szargut recommended the solid
element Au as reference species, since using it, the Ex
0
q
value for gold is higher than the value obtained from
AuCl
2
ion.
In the present work, it was calculated the Ex
0
q
values of elements whose reference species are dissolved in
seawater and that Szargut recommended as rst choice in 1988 [7], at 298.15 K and salinity of 35% and
including seawater pH and activity coefcients estimated rigorously. These values of Ex
0
q
match with those of
Szarguts.
When an increment in seawater salinity from 35 to 40% is considered (Fig. 5), e.g. Red Seas salinity, the
standard chemical exergy value is incremented for the elements whose reference species either contained
chlorine (Ag, Au, Cd, Hg and Pb) or are simple bicharged cations (Ba, Ca, Cu, Mg, Ni, Sr and Zn), showing a
larger deviation with regards to the value of Ex
0
q
at S 35%, in the case of the elements whose reference
species contained chlorine. This result must be incorrect, as the maximum work obtained to change species
concentration from pure substance to that in the environment (concentrational exergy) decreases with
increasing the species concentration of the environment, of course, if the considered formation reaction of the
reference species is the same. It is important to mention that in the standard chemical exergy calculation at
different salinities, the change in pH and g
i
values was considered and that the proportion among all species
dissolved in seawater remains constant for any seawater salinity.
ARTICLE IN PRESS
As
Ag
Au
B
Ba
Bi
Br
2
Ca
Cd
Cl
2
Cu
Cs
Hg
I
2
K Li
Mg
Mo
Na
Ni
P
Pb
Rb
S
Se
Sr
W
Zn
-1.12
-0.42
0.28
0.98
1.68
2.38
3.08
3.78
P
o
r
c
e
n
t
u
a
l

d
e
v
i
a
t
i
o
n

r
e
g
a
r
d
s

t
o

S

=

3
5
Fig. 5. Effect in the Ex

o
q
value of the elements contained in the hydrosphere by increasing salinity to 40%.
The term of Eq. (5) that represents the change in concentration of the hydrogen ion from a one-molal
solution to the concentration that it has in the environment, given by pH, is affected by the electric charge of
the species. If it was considered that a change in seawater pH, in the case of elements whose reference species
are simple bicharged cations, the effect in the Ex
0
q el
value is twice greater than in the Ex
0
q
of other elements,
this be incorrect; because when salinity is increased, the Ex
0
q
of sulphur falls. The reference species of sulphur is
SO
4
2
, complex bicharged anion. Although, in the case of elements whose reference species are complex
bicharged anions, the Ex
0
q
value of the additional elements present in the reference species also inuences the
Ex
0
q el
value.
The chemical exergy of chlorine modies when salinity varies, which does not happens with the chemical
exergy of hydrogen and oxygen, contained in some species dissolved in seawater, but whose references are the
gaseous species. In the case of elements where their reference species in the hydrosphere contain chlorine, when
salinity grows to 40%, the variation by the Ex
0
q Cl
diminution has higher effect on the chemical exergy
calculation of the element under consideration (Eq. (5)) than the variation by an increase on the reference
species concentration; which gives as result that the chemical exergy of these elements increases.
If others species dissolved in seawater were selected for elements whose reference species contain chlorine,
the incorrect behaviour in the standard chemical exergy variation would happen, considering a salinity
change. In the case of silver and gold, the only species present in seawater that contain chlorine are AgCl
2
and
AuCl
2
, respectively. Furthermore, the rest of the species dissolved in seawater that contain mercury are,
besides of others chlorides, mercury bromides. Choosing some of the mercury bromides as reference species is
not reasonable because, besides they are much less abundant than the HgCl
4
2
ion, the chemical exergy of
bromine would need to be determined from the Br
ion present in seawater, and this would lead to the same

problem encountered in the HgCl
4
2
ion case. In the case of cadmium and lead, others species in the
hydrosphere that can be selected as reference are Cd
2+
and Pb
2+
, but they are simple bicharged ions.
Szargut recommends, in his last publication [3], as rst choice, the ions Cu
2+
, Ni
2+
and Zn
2+
for the
elements copper, nickel and zinc, respectively. In the case of copper and zinc, there are others species present in
the hydrosphere that may be used as reference (i.e. CuCO
3
and ZnCO
3
), instead of the simple bicharged ions,
however, their concentration is very low (6 10
9
gmol=kg
H
2
O
on average). The only species dissolved in
seawater, that contains nickel and where there is enough information, is the simple bicharged ion.
The unsatisfactory results on the variation of the chemical exergy of some elements when salinity changes,
could justify the case of those elements whose reference species are in low concentration in seawater, since they
are not stable in this environment; however, in the case of calcium, magnesium and strontium, there is not
logical explanation because their reference species (Ca
2+
, Mg
2+
, Sr
2+
) are in high concentration. Therefore, it
is suggested to choose species as reference from Earths crust, for the standard chemical exergy calculation of
the elements Ag, Au, Ba, Ca, Cd, Cu, Hg, Mg, Ni, Pb, Sr and Zn.
4. Standard chemical exergy of the elements contained in the lithosphere
Szargut [3,7] proposes that the solid reference species in the environment possesses the properties of the
components of an ideal solution and formulates a composition for this homogeneous ideal solution with the
species that are in more abundance in the external layer of Earths crust. Besides, he establishes that standard
chemical exergy of the species in that environment can be determined by means of the following expression:
Ex
0
q
i
RT
n
ln x
in
, (24)
where
x
in

1
l
i
n
oel
c
i
M
o
. (25)
Szargut determines a M
o
value of 135.5 kg/kgmol for the composition of the solid environment that he
considers. The mean molar concentration of the element (n
o el
) in Earths crust and the fraction of the element
appearing as the reference species (c
i
), used in this work for the standard chemical exergy of the reference
species present in the lithosphere, are the same values that Szargut had used [3].
ARTICLE IN PRESS
5. Calculation sequence of standard chemical exergy of elements
The sequence for the calculation of standard chemical exergy of elements, according to the medium
(atmosphere, hydrosphere or lithosphere) in which the reference species is found, is shown in Fig. 6. The
ARTICLE IN PRESS
Ar
C
H
2
D
2
He
Kr
N
2
Ne
O
2
Xe
As
B
Bi
Br
2
Cl
2
Cs
I
2
K
Li
Mo
Na
P
Rb
S
Se
W
Ag
Ba
Ca
Cd
Ce
F
2
Fe
Ga
Gd
Ge
Hf
Al
Au
Be
Co
Cr
Cu
Dy
Er
Eu
Hg
Ir
Lu
Mg
Mn
Pr
Pt
Pu
Ra
Re
Rh
Ho
In
La
Nb
Nd
Ni
Os
Pb
Pd
Ru
Si
Sn
Sr
Ta
U
V
Y
Yb
Zn
Zr
Sb
Sc
Sm
Tb
Te
Th
Ti
Tl
Tm
Fig. 6. Route for the standard chemical exergy calculation of elements.
standard chemical exergy value of most of the elements depends on the value of Ex
0
q
of oxygen and hydrogen.
Besides, the standard chemical exergy values of uorine and magnesium are the most dependent on the
chemical exergy of other elements (three). Due to the fact that the elements calcium, iron and silicon, are
contained in the reference species of elements uorine, cobalt, aluminium, beryllium, magnesium and
zirconium, the standard chemical exergy of those should be calculated before the one of these.
6. Standard chemical exergy of elements
In Table 3, the estimated standard chemical exergies of elements are shown, considering normal conditions
of temperature and pressure (T
n
298.15 K and P
n
101.325 kPa), relative humidity of 0.7, concentration of
CO
2
equal to 345 ppm in volume and seawater salinity of 35%. Also, the reference species recommended by
the authors and the percentage deviation to the value of Ex
0
q
of elements that Szargut estimated using the same
reference species, are presented in Table 3. It is important to mention that the standard normal free energy
values at 298.15 K used by Szargut for the formation reaction of the reference species, were compared with
ARTICLE IN PRESS
Table 3
Standard chemical exergy of the elements
Chemical
element
a
Reference species Ex
o
q
of the element, kJ/gmol Deviation %
b
Chemical formula
a
x
in
, m
in
DG
f
o
i
kJ/mol As determined in
this work
Szargut [3]
Ag
(s)
AgCl
(s)
x 1.00E09 109.8 99.3 99.4 0.1
Al
(s)
Al
2
SiO
5 (s)
x 2.07E03 2,440.99 795.7 888.2 10.4
Ar
(g)
Ar
(g)
x 9.13E03 11.64 11.69 0.4
As
(s)
HAsO
4
2
(aq)
m 3.87E08 714.7 492.6 494.6 0.4
Au
(s)
Au
(s)
x 1.36E09 50.6 50.5 0.2
B
(s)
B(OH)
3 (aq)
m 3.42E04 968.84 628.1 628.5 0.1
Ba
(s)
BaSO
4 (s)
x 4.20E06 1361.9 775.4 775.1 0.0
Be
(s)
Be
2
SiO
4 (s)
x 2.10E07 2033.3 604.3 604.4 0.0
Bi
(s)
BiO
+
(aq)
m 9.92E11 146.4 274.8 274.5 0.1
Br
2 (l)
Br
(aq)
m 8.73E04 103.97 101.0 101.2 0.2
C
(s)
CO
2 (g)
x 3.37E04 394.38 410.27 410.26 0.0
Ca
(s)
CaCO
3 (s)
x 1.40E03 1129.00 729.1 729.1 0.0
Cd
(s)
CdCO
3 (s)
x 1.22E08 669.4 298.4 298.2 0.1
Ce
(s)
CeO
2 (s)
x 1.17E06 1024.8 1054.7 1054.6 0.0
Cl
2 (g)
Cl
(aq)
m 0.5658 131.26 123.7 123.6 0.1
Co
(s)
CoFe
2
O
4 (s)
x 2.85E07 1032.6 313.4 312.0 0.4
Cr
(s)
K
2
Cr
2
O
7 (s)
x 1.35E06 1882.3 584.4 584.3 0.0
Cs
(s)
Cs
+
(aq)
m 2.34E09 282.23 404.6 404.4 0.0
Cu
(s)
CuCO
3 (s)
x 5.89E06 518.9 132.6 132.5 0.1
D
2 (g)
D
2
O
(g)
x 3.37E06 234.63 263.9 263.8 0.0
Dy
(s)
Dy(OH)
3 (s)
x 4.88E08 1294.3 976.0 975.9 0.0
Er
(s)
Er(OH)
3 (s)
x 4.61E08 1291.0 972.8 972.8 0.0
Eu
(s)
Eu(OH)
3 (s)
x 2.14E08 1320.1 1003.8 1003.8 0.0
F
2 (g)
CaF
2
3Ca
3
(PO
4
)
2 (s)
x 2.24E04 12985.3 505.8 504.9 0.2
Fe
(s)
Fe
2
O
3 (s)
x 6.78E03 742.2 374.3 374.3 0.0
Ga
(s)
Ga
2
O
3 (s)
x 2.98E07 998.6 515.0 514.9 0.0
Gd
(s)
Gd(OH)
3 (s)
x 9.21E08 1288.9 969.0 969.0 0.0
Ge
(s)
GeO
2 (s)
x 9.49E08 521.5 557.7 557.6 0.0
H
2 (g)
H
2
O
(g)
x 2.17E02 228.59 236.12 236.09 0.0
He
(g)
He
(g)
x 4.89E06 30.31 30.37 0.2
Hf
(s)
HfO
2 (s)
x 1.15E07 1027.4 1063.1 1062.9 0.0
Hg
(l)
HgCl
2 (s)
x 5.42E10 178.7 107.9 108.0 0.1
Ho
(s)
Ho(OH)
3 (s)
x 1.95E08 1294.8 978.7 978.6 0.0
I
2 (s)
IO
3
(aq)
m 5.23E07 128 175.7 174.7 0.6
ARTICLE IN PRESS
Table 3 (continued )
Chemical
element
a
Reference species Ex
o
q
of the element, kJ/gmol Deviation %
b
Chemical formula
a
x
in
, m
in
DG
f
o
i
kJ/mol As determined in
this work
Szargut [3]
In
(s)
In
2
O
3 (s)
x 2.95E09 830.9 436.9 436.8 0.0
Ir
(s)
IrO
2 (s)
x 3.59E12 185.6 247.0 246.8 0.1
K
(s)
K
+
(aq)
m 1.04E02 282.44 366.7 366.6 0.0
Kr
(g)
Kr
(g)
x 9.78E07 34.30 34.36 0.2
La
(s)
La(OH)
3 (s)
x 5.96E07 1319.2 994.7 994.6 0.0
Li
(s)
Li
+
(aq)
m 2.54E05 294 392.7 393.0 0.1
Lu
(s)
Lu(OH)
3 (s)
x 7.86E09 1259.6 945.8 945.7 0.0
Mg
(s)
Mg
3
Si
4
O
10
(OH)
2 (s)
x 8.67E04 5543 626.9 626.1 0.1
Mn
(s)
MnO
2 (s)
x 2.30E05 465.2 487.7 482.0 1.2
Mo
(s)
MoO
4
2
(aq)
m 1.08E07 836.4 731.3 730.3 0.1
N
2 (g)
N
2 (g)
x 0.7634 0.67 0.72 6.9
Na
(s)
Na
+
(aq)
m 0.4739 262.048 336.7 336.6 0.0
Nb
(s)
Nb
2
O
3 (s)
x 1.49E07 1766.4 899.7 899.7 0.0
Nd
(s)
Nd(OH)
3 (s)
x 5.15E07 1294.3 970.1 970.1 0.0
Ne
(g)
Ne
(g)
x 1.76E05 27.14 27.19 0.2
Ni
(s)
NiO
(s)
x 1.76E06 211.71 242.6 242.5 0.0
O
2 (g)
O
2 (g)
x 0.2054 3.92 3.97 1.3
Os
(s)
OsO
4 (s)
x 3.39E13 305.1 368.4 368.1 0.1
P
(s)
HPO
4
2
(aq)
m 4.86E07 1089.3 861.3 861.4 0.0
Pb
(s)
PbCO
3 (s)
x 1.04E07 625.5 249.2 249.3 0.0
Pd
(s)
PdO
(s)
x 6.37E11 82.5 138.7 138.6 0.1
Pr
(s)
Pr(OH)
3 (s)
x 1.57E07 1285.1 963.9 963.8 0.0
Pt
(s)
PtO
2 (s)
x 1.76E11 83.7 141.2 141.0 0.1
Pu
(s)
PuO
2 (s)
x 8.40E20 995.1 1100.1 1100.0 0.0
Ra
(s)
RaSO
4 (s)
x 2.98E14 1364.2 824.2 823.9 0.0
Rb
(s)
Rb
+
(aq)
m 1.46E06 282.4 388.7 388.6 0.0
Re
(s)
Re
2
O
7 (s)
x 3.66E12 1067.6 559.6 559.5 0.0
Rh
(s)
Rh
2
O
3 (s)
x 3.29E12 299.8 179.7 179.7 0.0
Ru
(s)
RuO
2 (s)
x 6.78E13 253.1 318.6 318.6 0.0
S
(s)
SO
4
2
(aq)
m 1.24E02 744.63 609.3 609.6 0.0
Sb
(s)
Sb
2
O
5 (s)
x 1.08E10 829.3 438.2 438.1 0.0
Sc
(s)
Sc
2
O
3 (s)
x 3.73E07 1819.7 925.3 925.2 0.0
Se
(s)
SeO
4
2
(aq)
m 1.18E09 441.4 347.5 346.5 0.3
Si
(s)
SiO
2 (s)
x 0.407 856.7 855.0 854.9 0.0
Sm
(s)
Sm(OH)
3 (s)
x 1.08E07 1314 993.7 993.6 0.0
Sn
(s)
SnO
2 (s)
x 4.61E07 519.6 551.8 551.9 0.0
Sr
(s)
SrCO
3 (s)
x 2.91E05 1140.1 749.8 749.8 0.0
Ta
(s)
Ta
2
O
5 (s)
x 7.45E09 1911.6 974.1 974.0 0.0
Tb
(s)
Tb(OH)
3 (s)
x 1.71E08 1314.2 998.5 998.4 0.0
Te
(s)
TeO
2 (s)
x 9.48E12 270.3 329.3 329.2 0.0
Th
(s)
ThO
2 (s)
x 2.71E07 1169.1 1202.7 1202.6 0.0
Ti
(s)
TiO
2 (s)
x 1.63E04 889.5 907.2 907.2 0.0
Tl
(s)
Tl
2
O
4 (s)
x 1.49E09 347.3 194.9 194.9 0.0
Tm
(s)
Tm(OH)
3 (s)
x 7.59E09 1265.5 951.8 951.7 0.0
U
(s)
UO
3
H
2
O
(s)
x 1.49E08 1395.9 1196.6 1196.6 0.0
V
(s)
V
2
O
5 (s)
x 1.83E06 1419.6 721.3 720.4 0.1
W
(s)
WO
4
2
(aq)
m 5.64E10 920.5 828.5 827.5 0.1
Xe
(g)
Xe
(g)
x 8.81E08 40.27 40.33 0.1
Y
(s)
Y(OH)
3 (s)
x 1.00E06 1291.4 965.6 965.5 0.0
Yb
(s)
Yb(OH)
3 (s)
x 4.61E08 1262.5 944.3 944.3 0.0
Zn
(s)
ZnCO
3 (s)
x 7.45E06 731.6 344.7 344.7 0.0
Zr
(s)
ZrSiO
4 (s)
x 2.44E05 1919.5 1083.0 1083.4 0.0
a
State: solid (s), gaseous (g), liquid (l) and aqueous (aq).
b
With respect to Szarguts value [3].
other publications [2934]. In this comparison, no substantial differences were found, except for sillimanite
(Al
2
SiO
5
). If a DG
f
o
value of 2,440.9 kJ/gmol [30,32] for sillimanite is used, Ex
0
q
of aluminium results of
795.7 kJ/gmol; however, when DG
f
1 is equal to 2,625.9 kJ/gmol (Szarguts consideration), Ex
0
q
of aluminium
is 888.2 kJ/gmol. Now, when Ex
0
q
of Al
2
O
3
, solid compound present in Earths crust, is calculated by means of
Eq. (1) (DG
o
f Al
2
O
3
1; 582:4kJ=gmol) and using both Ex
0
q Al
values, considerable discrepancy is found. This
is, Ex
0
q Al
2
O
3
results of 15 kJ/gmol using a Ex
0
q Al
value of 795.7 kJ/gmol, whereas Ex
0
q Al
2
O
3
is equal to 199.9 kJ/
gmol (thirteen times larger) when Ex
0
q Al
is 888.2 kJ/gmol. Using Eq. (24), standard chemical exergy of Al
2
O
3
is
equal to 17 kJ/gmol, value close to that obtained when Ex
0
q
of aluminium and DG
f
1 for sillimanite are 795.7
and 2440.9 kJ/gmol, respectively [35]. Hence, in this work, a DG
f
1 value of 2,440.9 kJ/gmol for sillimanite is
used, instead of Szarguts consideration; although the calculated standard chemical exergy of aluminium is
10.4% lower than that of Szargut.
The difference between the standard chemical exergy values obtained in this work for nitrogen and oxygen
compared to Szarguts estimation is 6.9% and 1.3%, respectively. This is because Szargut considers a mean
total pressure of 99.31 kPa instead of 101.325 kPa for the calculation of the atmospheric air composition. For
the rest of the elements, the small deviation between the Ex
0
q
value determined and that predicted by Szargut is
due to the fact that Ex
0
q
values of additional elements and references species found in this work are used for
calculations and not the Szarguts values. An example of this is the case of manganese . There is a difference of
27% on Ex
0
q
of MnO
2
(reference species of manganese) between the value found (26.5 kJ/gmol) and that of
Szargut (20.8 kJ/gmol), which produces a deviation of 1.2% on the standard chemical exergy of manganese.
This could be a lecture mistake since the molar fraction of the species obtained is 2.3 10
5
and Szarguts
estimation is 2.3 10
4
. If x
MnO
2
values were equal to 2.3 10
4
, manganese concentration on the layer
Earths crust would have been of 1.7 10
4
, which is different from the value considered in this study and that
used by Szargut of 1.7 10
5
. Other authors [15,3638] agree with manganese concentration value used by
Szargut; so molar fraction and standard chemical exergy values of manganese dioxide estimated in this work
are considered true.
7. Summary
Figs. 1, 2, 3, 4 and 7 show the historical evolution of the selection of reference species for the Szargut model
since 1983.
In 1988, the reference species of elements bismuth, molybdenum and wolframium were changed from the
lithosphere to the hydrosphere, whereas for the case of magnesium, cobalt and phosphorous, reference species
from the Earths crust were selected instead of the hydrosphere. In 1989, reference species in the Earths crust
were selected for calcium, strontium, barium, gold and uorine instead of the species in seawater; but for
phosphorous, a reference species dissolved in seawater was preferred. In 2002, a reference species of the
lithosphere was preferred for arsenic instead of from the hydrosphere, while species contained in the
hydrosphere were selected as reference for calcium and magnesium. Finally, in the present work, a reference
ARTICLE IN PRESS
H
2
He
Li Be B C N
2
O
2
F
2
Ne
Na Mg Al Si P S Cl
2
Ar
2
Kr
2
Xe
Fr Ra Ac
Fig. 7. Reference species media for elements recommended in this work.
species dissolved in seawater is used for arsenic rather than one of the lithosphere, and reference species of
elements calcium, magnesium, nickel, copper, zinc, silver, cadmium, mercury and lead are changed from the
hydrosphere to the lithosphere.
8. Conclusions
There are no important differences between standard chemical exergy values of elements estimated by
Szargut and those obtained by a very detailed revision of his methodology, except for nitrogen and
aluminium. In the case of nitrogen, the variation of 7% on Ex
0
q
is due to the fact that Szargut considers a mean
pressure less than 101.325 kPa for the atmospheric air composition, which has a high repercussion on Ex
0
q
of
nitrogen as the main constituent of the atmosphere. Since the Gibbs free energy value for the formation
reaction of sillimanite is different, the standard chemical exergy of aluminium changes 10.4% compared to
Szarguts estimation.
Besides, species from Earths crust are recommended as references for the calculation of the standard
chemical exergy of elements: silver, gold, barium, calcium, cadmium, copper, mercury, magnesium, nickel,
lead, strontium and zinc; because, if a species dissolved in seawater is considered, an incorrect behaviour on
the variation of the standard chemical exergy of these elements is obtained, when a different seawater salinity
is assumed.
From the analysis carried out, updated chemical exergies and adequate reference species of most of the
elements of the Periodic Table are shown. Furthermore, this study allows to evaluate the effect of
environmental conditions on the standard chemical exergy of elements and compounds.
In fact, the computer infrastructure developed allows the updated, accurate, and real-time calculation of the
standard chemical exergy of elements and compounds at any atmospheric temperature, pressure, humidity
and CO
2
concentration, and at any hydrospheric salinity.
A very extensive set of standard chemical exergy values for inorganic and organic substances will be
published in the near future.
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Energy 31 (2006) 33103326

Standard chemical exergy of elements updated

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are desired to be known. At salinity of 35%,

Fig. 5. Effect in the Ex

ion present in seawater, and this would lead to the same

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