Desalination 365 (2015) 343346

Contents lists available at ScienceDirect

Desalination

journal homepage: www.elsevier.com/locate/desal

Gibbs energy role in fresh and salt water mixing

Nikolai M. Bazhin
Institute of Chemical Kinetics and Combustion, Novosibirsk State University, Institutskaya 3, Novosibirsk 630090, Russia

H I G H L I G H T S

The energy of osmotic systems is produced due to thermal energy of the environment.
The reversible mixing of feed and draw solutions is followed by mixture cooling.
The friction in the membrane should not lead to work losses.
All theoretical calculations in terms of the Gibbs energy are still valid.

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

Article history: It is well-known that the process of mixing two solutions of different concentrations may produce energy. The
Received 17 November 2014 change in Gibbs energy upon mixing is believed to be the source of energy. However, the change in the Gibbs en-
Received in revised form 13 March 2015 ergy is independent of the way of mixing, i.e., irreversible (without work production) or reversible (with the
Accepted 14 March 2015
obligatory production of work). The Gibbs energy cannot be an energy source for producing work. The entropy
Available online 19 March 2015
of mixing solutions and the environment has been considered to elucidate the role of the Gibbs energy in the re-
Keywords:
versible process. It is shown that the environment takes active part in energy production. The Gibbs energy may
Ideal solution be a mathematical means for performing thermodynamic calculations.
Feed solution Published by Elsevier B.V.
Draw solution
Useful work
Gibbs energy

1. Introduction types are also the same [7]. It is well-known [7] that the irreversible
mixing (without work production) of two ideal solutions fails to cause
When mixing fresh and salt water, osmotic processes are taken as either heat emission or the change in volume. Hence,
promising for producing clean energy [16]. The energy produced
may be stored as a potential energy in the environment. It is widely H mixing 0; 1
held that the energy produced by mixing two solutions of different con-
centrations is due to the Gibbs energy [16]. The environment is not V mixing 0: 2
commonly considered. The goal of the present paper is to reveal the
role of the Gibbs energy in energy production upon solution mixing
Upon mixing, the entropy increases and the Gibbs energy decreases
with regard to the processes occurring in both solutions and the envi-
ronment. To this end, we consider the change in entropy upon mixing
SmixingN0; 3
for both the environment and solutions.

Gmixing H mixingTSmixing TSmixingb0: 4

2. Irreversible mixing
We consider only the mixing of ideal solutions which occurs at con-
stant temperature and pressure. In ideal solutions, all molecules are of
the same size and the interactions between the molecules of different
E-mail address: bazhin8999@kinetics.nsc.ru.
The absence of both heat emission and the change in volume upon
mixing indicates that the solutions of different concentrations have no
potential energy to perform work.
The decrease in the Gibbs energy upon mixing means that the Gibbs
energy is not conserved. Thus, it is not the true energy [810]. Therefore,
the role of the Gibbs energy in energy production upon mixing calls for
further studying.

http://dx.doi.org/10.1016/j.desal.2015.03.023
0011-9164/Published by Elsevier B.V.
344 N.M. Bazhin / Desalination 365 (2015) 343346
3. Reversible mixing
In this section, we are going to consider reversible processes as a
model to which the real processes, producing useful work, may tend.
Strictly speaking, there are no reversible processes. However, a series
of processes, in particular the osmotic ones, may produce useful work
with a fairly high efciency. It is worth noting that only the reversible
processes are always followed by production of the maximal, useful
work [11,12].
The work of reversible processes can be produced by special instru-
ments. In osmotic systems, the semipermeable membranes serve as
these. Using the semipermeable membranes in the system has no effect
on the change in volume, enthalpy, entropy, and the Gibbs energy upon
solution mixing. The change in these values is independent of process
character, reversible or irreversible, because all of these values are the
state functions.
The absence of the change in entropy for the environment and solu-
tions is an important characteristic of the reversible process
Smixed solutions environment
Smixed solutions Senvironment 0; 5 tions, related to the change in temperature upon mixing, are of no
since only the fulllment of condition (5) provides the reversibility of
the process. As follows from Eq. (5)
Senvironment Smixingb0: 6
As the temperature of the environment and solutions is uniform, the
entropy of the environment may change only upon thermal energy
transfer from the environment to the mixture of solutions
Senvironment H environment=Tb0: 7 vironment to water solutions is highly slow which allows one to esti-
Since the temperature of the mixture of solutions remains uniform
upon this transfer of thermal energy, in virtue of the law of energy con-
servation, the transferred thermal energy must produce work
0 among which there are n moles of ions. We assume that n 1.2 M [4].
H environment wuseful ; 8
where wuseful is the maximal useful work of the reversible process. From
Eqs. (4), and (6)(8) we nd that
0
wuseful Gmixing Henvironment: 9
Thus, the useful work of the osmotic, reversible process is equal to
the change in the Gibbs energy upon mixing but is performed due to
the thermal energy of the environment.
The useful work in the reversible, osmotic system is performed due
to the tendency of the system to the equilibrium state against the
applied pressure, equal to the osmotic one. To achieve equilibrium,
water from feed solution penetrates draw solution through a mem-
brane. As a result, the volume of draw solution increases and the work
is performed which is equal to the product of pressure difference by vol-
ume of penetrating solution. Work production requires energy sources.
However, the system has no sources other than the thermal energy of
solutions. Therefore, the water, performing work, is cooled upon pene-
tration into the draw solution and cools it. In this case, a minor differ-
ence appears in the temperatures of the draw solution and the
environment. Thereafter, the mixture temperature is restored due to
heat transfer from the environment. In the reversible system, the pro-
cesses are usually innitely slow. It is assumed then that in the com-
bined system (solutions + environment), the temperature is always
uniform. The environment serves as a thermostat of extremely large
heat capacity.
Note that this description of work production due to the heat of the
environment is in fair agreement with the second law of thermodynam-
ics. The law prohibits work production in the process which results only
in heat absorption from a reservoir and in complete conversion of this
absorbed heat into work [11, p. 94]. In reversible osmotic systems, the
absorption of heat from the environment (reservoir) is connected not
only with work production but also (which is of high importance)
with the process of concentration variations. Therefore, the second
law is not violated.
It might be surprising that the useful work is performed due to the
thermal energy of the environment whereas the amount of work is cal-
culated in terms of the change in the Gibbs energy upon solution mixing
without involvement of the environment. The point is that calculations
according to Eq. (9) use the thermodynamic parameters only of the ini-
tial and nal states of the system of solutions. A concrete realization of
the reversible process of mixing does not describe Eq. (9) and may be
realized by various methods including the active participation of the en-
vironment [13] (which is demonstrated above). No matter what is the
way the reversible process follows, the value of the maximal useful
work will be unambiguously calculated from Eq. (9). Therefore, the re-
sults of theoretical studies e.g., [16], using the Gibbs energy to carry
on thermodynamic calculations upon description of osmotic phenome-
na, cannot undergo substantial changes. Minor corrections in calcula-
essence because of a small change in temperature.
4. Estimation of temperature variations upon reversible mixing
Let us estimate the change in mixed water temperature due to the
reversible process of mixing which results in reversible work. Solutions
are taken as ideal. The reversible mixing is followed by the cooling of
mixed water whose temperature may increase to the ambient one
upon heat transfer. It is assumed then that the heat transfer from the en-
mate the maximal cooling. Therefore, only the resulting mixture of
draw and feed solutions is rst cooled.
Calculate now the change in temperature upon reversible mixing of
one liter of the draw solution with several moles (N1) of the feed solu-
tion. One liter of the draw solution contains 55.5 mol of (N0) molecules
The process of mixing causes the change in the Gibbs energy of both
water and dissolved ions.
Gmixing Gmixing; ions Gmixing; water: 10
It is worth noting that since the Gibbs energy is a state function, its
variations are independent of process character, i.e., reversible or irre-
versible, with or without work production.
For ions, the change in the Gibbs energy is of the form
Gmixing;

ions 

o n o n
n ions RT ln n ions RT ln ; 11
N0 N1 N0
where oions is a standard, chemical ion potential in water, N n
is a molar
0 N 1
fraction of ions in the formed mixture of draw and feed solutions, and Nn
0
is a molar fraction of ions in the initial draw solution. Assuming that
n N0, we get
Gmixing; ionsnRT ln ; 12
where is the coefcient of dilution equal to
N0 N1
: 13
N0
 N.M. Bazhin / Desalination 365 (2015) 343346 345

A similar method is used to consider the change in the Gibbs energy The change in H(mixed solutions), per one liter of the mixture ob-
for water. tained, equals H(mixed solutions)/. The change in temperature may

 be calculated from
o N n N1
Gmixing; water N0 n N 1 water RT ln 0

 N0 N1 nRT ln 1
N n ; T nRTxions 2 ; 20
o
N0 n water RT ln 0
o
N1 water C p Cp
N0
14 where Cp is the heat capacity of one liter of mixed solution. For heat ca-
pacity, we assume Cp = 4184 /(kgK), neglecting the inuence of
where owater is a standard, chemical potential of water, N0NnN
N is a molar
1 salts on its value. Then, for T = 298 K we get
0 1

fraction of water in the formed mixture of draw and feed solutions, and
ln 1
N 0 n
is a molar fraction of water in the draw solution. Assuming that T 0:71 0:0154 2 ; K: 21
N0
n N0, we get
The second term in Eq. (21) is 50100 times as small as the rst one
1 with varying from 1.1 to 10 and is of no essence. Fig. 1 plots the change
Gmixing; waternRTxions ; 15
in the temperature of mixed solutions vs dilution.
It is seen that after double dilution ( = 2) the cooling amounts to
where xions is a molar fraction of ions in the draw solution equal to n/N0. 0.24 K. The maximal cooling is attained at = 2.72 and equals 0.26 K.
Thus, the change in the Gibbs energy is Thus, the cooling is relatively small.

1 5. Application to PRO systems

GmixingnRT ln nRTxions : 16

5.1. Gibbs energy
The same result, i.e., Eq. (16), may be obtained discussing the change
in entropy (increase) upon mixing in the framework of statistic ap- As mentioned above, the Gibbs energy is not energy. It is a mathe-
proach. In the systems under study, an increase in entropy is assigned matical function. The Gibbs energy mathematically describes the maxi-
to the fact that when the feed solution penetrates the draw one, the mal useful work in reversible systems. The mixing of solutions does not
number of the congurational states of ions (or, what is equivalent, release free energy, but causes the change in the values of Gibbs energy.
the water molecule congurational states) increases. This change in en- The present paper reports that the work of the osmotic process is per-
tropy may be calculated from the formula formed not due to the Gibbs energy but due to the cooling of the
0 1 resulting water mixture and then of the environment. Taking into ac-
0 1 e
N0 e
N1 e
en C
n count that the efciency of energy production in PRO devices is usually
Ce B e C
B N e N C N0 e
S k ln @ 0 1 A k ln B C; less than unity, the cooling will decrease in proportion to the real ef-
N1
@ e A 17
Cen
e C
N0 en ciency and may pass unnoticed in operating instruments.
N0 e N0

5.2. Chemical water potential, osmotic pressure, water ow

where k is a Boltzmann constant, 0 is the total sum of water molecules
and ions in the draw solution in 1 l, 1 is the number of water molecules The chemical potential of water molecules in the feed solution ex-
added to 1 l of the draw solution, and, is the number of ions in the ceeds that in the draw solution
draw solution. The second term in Eq. (17) describes the change in the
number of the congurational states of dissolved ions, and the latter water; feed water; draw VPV; 22
one describes the change of the congurational states of the water
molecules. where is the osmotic pressure, P is the pressure applied to the draw
Using the Stirling's formula and expansion of logarithms in a series, solution, and V is the molar water volume. The greatest difference in
we get

1
SnR ln nRxions  ; 18

where n is the number of ion moles. Thus, a water ow through the

membrane is created by a spontaneous tendency of system to equilibri-
um which results in increasing entropy. No forces are needed to form
this water ow. However, the rate of mixing will depend on various pa-
rameters, e.g., membrane permeability, the value of pressure applied to
the draw solution.
Since upon mixing of ideal solutions the change in solution enthalpy
is zero, Eq. (1), then taking into account G = TS, for the change in
the Gibbs energy, we derive Eq. (16).
The thermal energy, dragged from the mixture of solutions upon re-
versible work production (H(mixed solutions)), is equal to the change
in the Gibbs energy upon mixing, Eq. (9)

1
H mixed solutions Gmixing nRT ln nRTxions : 19
Fig. 1. The change in solution temperature upon reversible dilution.
346 N.M. Bazhin / Desalination 365 (2015) 343346
chemical potentials is reached in the absence of the pressure applied to
the draw solution. Eq. (22) creates the impression that water moves
from the reservoir with feed solution to that with draw solution under
the action of pressure difference P. However, for P = 0 no
real pressure was applied either to the feed solution or the draw solu-
tion. However, the water ow was maximum. The osmotic pressure is
a calculated value and does not exist as a real physical value. Neverthe-
less, it is convenient to introduce this concept because comparing the
values of osmotic pressure with that of the pressure applied really to
the draw solution allows one to judge upon the direction of the process
in the osmotic system. A decrease in the chemical potential of water
molecules in the draw solution as compared with that in the feed solu-
tion, favors the penetration of the feed solution through the membrane
which is caused by entropic reasons rather than by force. The difference
in entropic factors provides a corresponding distinction in chemical po-
tentials (Eq. (22)). Therefore, despite the absence of force actions, the
water ow will be proportional to the difference in the chemical
water potentials in both of the solutions and, thus, to the pressure differ-
ence P.
5.3. Friction losses upon water passage through the membrane
The passage of water through the membrane was followed by fric-
tion [4] which should cause some heating of solutions. If the water
ow had been created due to the pressure drop on either side of the
membrane, this would have led to the loss of the part of the energy re-
leased. However, the penetration of water through the membrane is a
spontaneous process. The work, spent to overcome friction, is per-
formed due to the thermal energy of solutions, because of the absence
of another source of energy. Therefore, the heat emitted is compensated
by the cooling of the water. The friction in the membrane cannot de-
crease the work produced. It decreases the power of the device, but
the value of the produced work per unit volume of the mixed water
should be independent of friction in the membrane. The part of work,
interpreted as the work lost for friction [1], should be attributed to un-
utilized energy.
6. Conclusions
The maximal, useful work of the osmotic, reversible process is equal
to the change in the Gibbs energy upon mixing. The energy spent to
produce reversible work is provided by the thermal energy of the envi-
ronment. The cooling of solutions rather than the change in the Gibbs
energy is the source of energy at the initial stage of mixing in real sys-
tems. In real systems, the cooling should have a minor effect. All theo-
retical calculations, based on the Gibbs energy, e.g., [16], conserve
their signicance, because the value of useful work is calculated in
terms of the change in the Gibbs energy upon transition from the initial
to the nal state. The change in the Gibbs energy is independent of the
concrete realization of mixing. The Gibbs energy serves a mathematical
means for calculating useful work. The penetration of water molecules
from the feed solution through the membrane into the draw solution
is due to the gain in statistical distributions. The friction in the mem-
brane should not lead to work losses because the thermal energy of
the feed solution serves the source of energy spent to overcome friction.
References
[1] Shihong Lin, Anthony P. Straub, Menachem Elimelech, Thermodynamic limits of ex-
tractable energy by pressure retarded osmosis, Energy Environ. Sci. 7 (2014)
27062714.
[2] Wei He, Yang Wang, Mohammad Hasan Shaheed, Energy and thermodynamic anal-
ysis of power generation using a natural salinity gradient based pressure retarded
osmosis process, Desalination 350 (2014) 8694.
[3] Hongliang Qiana, Zheng Zhoua, Lingling Zhang, Fawen Wu, Quanxing Zhang,
Zhibing Zhang, Thermodynamic analysis on the theoretical energy consumption of
seawater desalination, Desalination 320 (2013) 7379.
[4] Ngai Yin Yip, Menachem Elimelech, Thermodynamic and energy efciency. Analysis
of power generation from natural salinity gradients by pressure retarded osmosis,
Environ. Sci. Technol. 46 (2012) 52305239.
[5] Andrea Achilli, Amy E. Childress, Pressure retarded osmosis: from the vision of Sid-
ney Loeb to the rst prototype installation review, Desalination 261 (2010)
205211.
[6] Kitty Nijmeijer, Sybrand Metz, Salinity gradient energy, Sustainability Science and
Engineering, vol. 2, Elsevier, 2010. 95139 (Chapter 5).
[7] I. Prigogine, R. Defay, Chemical Thermodynamics, Longman, London, 1954.
[8] S. Lover, Chem1 virtual textbook, http://www.chem1.com/acad/webtext/
virtualtextbook.html.
[9] L.E. Strong, H.F. Halliwell, An alternative to free energy for undergraduate instruc-
tion, J. Chem. Educ. 47 (1970) 347352.
[10] B. Crabtree, D.J. Taylor, Thermodynamics and Matter Exchange in Biochemical
Thermodynamics, in: M.N. Jones (Ed.), Elsevier, Amsterdam, 1979.
[11] P. Atkins, J. de Paula, Physical Chemistry, ninth ed. Oxford University Press, 2010.
[12] P. Atkins, The Elements of Physical Chemistry, 3rd ed. Oxford University Press,
Oxford, 2001.
[13] N.M. Bazhin, V.N. Parmon, Conversion of the chemical reaction energy into useful
work in the Van't Hoff equilibrium box, J. Chem. Educ. 84 (2007) 10531055.