Renewable and Sustainable Energy Reviews 45 (2015) 600609

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Renewable and Sustainable Energy Reviews

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

A review on the equations of state for the working pairs used

in adsorption cooling systems
H.Z. Hassan a,n, A.A. Mohamad b, Y. Alyousef c, H.A. Al-Ansary d
a
Department of Mechanical Engineering, College of Engineering, Alfaisal University, Takhassusi St., PO Box 50927, Riyadh 11533, Saudi Arabia
b
Mechanical and Manufacturing Engineering, Centre for Energy and Environment, Research and Education, Schulich School of Engineering, University of
Calgary, Calgary, AB, Canada
c
King Abdullaziz City for Science and Technology, Institute of Water and Energy Research, PO Box 6086, Riyadh 11442, Saudi Arabia
d
Mechanical Engineering Department, The College of Engineering, King Saud University, Riyadh, Saudi Arabia

art ic l e i nf o a b s t r a c t

Article history: Adsorption cooling machines are thermally driven systems. Solar radiation, waste energy, as well as
Received 26 February 2014 geothermal energy can be used to power these systems. Theoretical study and simulation work of
Received in revised form adsorption-based cooling systems require the knowledge about the adsorption pair characteristics and
28 December 2014
capacities at different conditions of working pressures and temperatures. This information is obtained
Accepted 6 February 2015
Available online 25 February 2015
from the adsorbateadsorbent equation of state. Various models and formulas represent the adsorption
pair equation of state for different combinations of adsorbate and adsorbent can be found in the
Keywords: literature. Furthermore, these state equations include some coefcients which are determined experi-
Adsorption pair mentally for each combination of the adsorption pair. The present work introduces a review of various
Cooling
adsorption equations of state which have been adopted by different researchers in their study. Moreover,
State equation
the corresponding experimentally evaluated coefcients, which are found in the literature, for each
Adsorption equilibrium
model and for a variety of working pairs are reported as well.
& 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
2. Characteristics of the adsorbentadsorbate pairs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
3. Adsorption dynamic equilibrium and kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
4. Adsorption equilibrium models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
4.1. Dubinin equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
4.2. Langmuir equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
4.3. Freundlich equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
4.4. Toth equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
5. Activated carbon state equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
6. Silica gel state equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
7. Zeolite state equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608

1. Introduction

Sorption phenomenon has been known for long time and is

n increasingly used in many applications including separation,
Corresponding author. Tel.: 966 1215 7790; fax: 966 12157751.
E-mail addresses: hzahmed@alfaisal.edu, purication, and thermally driven cold production technologies
zoheir_hasan@yahoo.com (H.Z. Hassan). [1]. The term sorption refers to both absorption and adsorption

http://dx.doi.org/10.1016/j.rser.2015.02.008
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
 H.Z. Hassan et al. / Renewable and Sustainable Energy Reviews 45 (2015) 600609
which are fundamentally different processes. A part of a gas is
taken up by a solid when both the gas and the solid are brought in
contact. Gas or vapour molecules which disappear from the gas
phase may interpenetrate the solid volume, a process called
absorption, or accumulated on the surface of the solid and remain
attached to it, a process called adsorption [2]. Absorption process
is a volumetric phenomenon in which a substance in a gas or
vapour state (absorbate) interpenetrates and incorporates into
another substance (absorbent). Both two phases show a strong
afnity to form a solution or a mixture. This process can be
reversed and the absorbed phase can be released from the
absorbent by applying heat to the mixture. The commonly used
and mature absorbentabsorbate working pairs are the ammonia
water [3,4] and waterlithium bromide [57]. The adsorption
process is a surface phenomenon. The heart of an adsorption
process is usually a porous solid medium which provides a very
large surface area and large pore volumes and therefore large
adsorptive capacity [810]. Depending on the nature of the
adsorption, there are two types. The rst type is the physical
adsorption (or physisorption) and the second type is the thermo-
chemical adsorption (or chemisorption) [9].
The chemisorption process involves valency forces arising from
sharing of electrons between the adsorbent and the adsorbate
atoms. This results in forming a complex surface compound due to
a chemical reaction. Examples of commonly used thermo-
chemical working pairs are ammoniacalcium chloride, ammo-
niastrontium chloride, and ammonialithium nitrate [9]. In the
physisorption process, the adsorbate molecules are attracted to the
adsorbent surface by the weak Van der Waals force. There is no
change in the chemical composition of the adsorption pair. More-
over, physical adsorption is nonspecic and takes place between
any adsorbentadsorbate system. Physical adsorption working
pairs include activated carbonmethanol [1115], activated car-
bonethanol [16,17] activated carbonammonia [1823], silica
gelwater [2430], and zeolitewater [3133]. In this study, the
term adsorption is used to refer only to the physical adsorption
type. In both types of adsorption as well as absorption processes,
Fig. 1. Classications of the adsorption based cooling system.
601
the uptake process is exothermic whereas the desorption process
is endothermic. From the thermodynamics point of view, adsorp-
tion process of a gas or a vapour on a solid adsorbent is a
spontaneous process during which the free energy of the system
decreases. In addition, the adsorbed phase has fewer degrees of
freedom than the gas phase and consequently the entropy
decreases during the adsorption process. As a result, the adsorp-
tion heat is negative and therefore the process of adsorption is
exothermic and is accompanied by the evolution of heat. The
process of desorption is endothermic and accompanied by absorp-
tion of heat. This characteristic is used to produce the cooling
effect in the refrigeration and air conditioning applications
[9,34,35].
Recently, hundreds of research papers on the adsorption cool-
ing eld can be found in the literature. These studies include
experimental as well as theoretical investigations for various
system designs, different working pairs, and operating conditions.
Moreover, considerable varieties of operating schemes and mod-
ied thermodynamic cycles have been introduced. Based on the
previous work, adsorption cooling systems can be classied in to
open and closed systems, Fig. 1. Open systems are gassolid
desiccant systems that are only used in air conditioning and
dehumidication applications, whereas closed type systems are
used for freezing, chilling, and air conditioning. Closed systems are
sub categorized, based on the operating thermodynamic cycle,
into the basic one-bed system, the adsorption cooling tube (ACT)
system, and the advanced multi-bed schemes. The multi-bed
schemes are enhancements on the basic one-bed system to
increase the performance and to provide quasi-continuous opera-
tion. These enhancements include the mass recovery, the heat
recovery, the combined mass and heat recovery, the thermal wave,
the convective thermal wave, the cascading, and the multi-staging
schemes, Fig. 1.
Adsorption cooling systems have the advantage of being
powered by any low quality thermal energy. In other words, a
low temperature driving heat source, with temperature as low as
50 1C, could be used. Therefore, solar radiation, waste heat, as well
602 H.Z. Hassan et al. / Renewable and Sustainable Energy Reviews 45 (2015) 600609
as geothermal energy can be used to power these systems. Using
solar energy, as a free and renewable type of energy, to drive
adsorption cooling systems is considered an attractive option as
well as a focal point of interest. This is because the peak of cold
requirements coincides most of the time with the availability of
the solar radiation. Moreover, using solar radiation can benet the
environment and reduce the impact raised from using other
conventional thermal energy sources like coal, gas, and oil. Solar
radiation was extensively used to drive the adsorption cooling
systems in the literature [57,9,11,1315,20,23,28,36,37]. The
simplest design of the system consists of an adsorption reactor
integrated inside a at plate solar collector, as illustrated in Fig. 2.
The reactor conguration could be a tubular type [12] or a simple
at type [38,39]. Furthermore, the parabolic trough as well as the
evacuated tube solar collectors can be used to power the adsorp-
tion cooling system [13].
It is well known that the knowledge about the equation of state
for the adsorption pair used in the cooling system under study is of
great importance in theoretical and simulation work. These
equations are based on adsorption equilibrium models and include
some coefcients which depend on the pair. These coefcients are
determined by experimental work and differ from adsorption pair
to another. The literature is abundant with such valuable equa-
tions of state for different working pairs. However, to the best of
our knowledge, there is no database which records these impor-
tant equations. Also, there is no study that collects and reports
these experimental data. From this motivation, and due to the
importance of this point, it is decided to devote this study to
report the adsorption pairs equations of state which are intro-
duced in the literature. This paper will help researchers to easily
nd the suitable equation which represents the adsorption pair
used in their system. Moreover, a researcher will be aware of the
existing and non-existing equations for state. This helps to avoid
repeating experimental work and encourage formulation of equa-
tions for other new pairs.
2. Characteristics of the adsorbentadsorbate pairs
The performance of the adsorption cooling system depends
mainly on the working pair used. Since each pair differs from the
other in terms of physical and thermodynamic properties, the choice
of the working pair has a great effect on the system performance.
A well system should have the characteristics of large adsorption
capacity and a strong afnity of the absorbent for the refrigerant
under consideration. In addition, a large change of adsorption
capacity with temperature and pressure variations is also required.
This helps in reducing the size of the adsorption reactor and
decreasing the sensible heat losses and consequently improves the
system performance. Moreover, the refrigerant should have a large
Fig. 2. Illustration of the solar-powered adsorption cooling system.
latent heat of vaporization in order to increase the refrigeration
capacity [40]. Furthermore, the refrigerant should not form a solid
phase over the expected range of pressure and temperature to
which it will be subjected. Another important factor is the refriger-
ant chemical and thermal stability to avoid the deterioration and
corruption of the refrigerant. Moreover, no toxicity, no ammability,
and moderate operating pressure are important requirements for
the pair. High pressure requires heavy-walled equipment whereas
low pressure requires large-volume equipment [41]. The most
widely used working pairs which closely meet the aforementioned
requirements are activated carbonmethanol, activated carbon
ethanol, activated carbonammonia, silica gelwater, and zeolite
water.
The solid adsorbent is a type of porous media that has cavities,
channels or interstices, which are deeper than they are wide. The
large surface area of the adsorption media is mainly due to the
micropore and mesopore internal structure, Fig. 3. Porous materi-
als may be one of two types; agglomerates or aggregates [42].
Agglomerates are rigid and consolidated porous material which
consists of assemblage of macroscopic particles whose dimensions
exceed those of the pores by many orders of magnitude, like silica
gel. Aggregates are loose and unconsolidated assemblage of
individual particles, like powders [43,44]. The pores are classied
into three types according to their size. As recommended by the
International Union of Pure and Applied Chemistry (IUPAC) these
types of pores include the micropores (diameters less than 2 nm),
mesopores (diameters between 2 and 50 nm), and macropores
(diameters greater than 50 nm) [45], Fig. 3.
A good solid adsorbent must have relatively large surface area
and micropore volume and therefore the pore size should be small
with a reasonable porosity. This means that the adsorbent solid
must have a combination of the micropores and the macropores.
Besides, the solid must have a large pore network for transporting
the gas molecules to the interior of the adsorbent [8]. The total
void space within an element of the adsorbent consists of three
components; the interparticle voids, the open pore voids, and the
closed pore voids. The open pore type of void spaces is due to
the contribution of both the inter-crystalline macropores and the
intra-crystalline micropores void spaces as well as the mesop-
ore spaces. The total porosity of any porous material is dened as
the ratio between the total void spaces within the solid porous
material and the material bulk volume [42]. The bulk volume of a
material includes the contribution of skeletal volume, pore void
volume, and interparticle space volume [46].
3. Adsorption dynamic equilibrium and kinetics
As a solid surface is subjected to a gas phase, the gas molecules
strike the surface of the solid. Some of the striking molecules stick
to the surface and become adsorbed, while others rebound.
Fig. 3. Schematic representation of pore structure of an adsorbent material.
 H.Z. Hassan et al. / Renewable and Sustainable Energy Reviews 45 (2015) 600609
The rate of adsorption is large at the beginning of this process
because the whole surface is uncovered. Then the rate of adsorp-
tion starts to decrease because more and more of the solid surface
is being covered by the adsorbate molecules [42]. The desorption
rate increases due to escaping of the gas phase molecules from the
covered surface. When the rate of adsorption is equal to the rate of
desorption, equilibrium is obtained and the gassolid system is
said to be in dynamic equilibrium because the number of mole-
cules sticking to the surface is equal to the number of molecules
rebounding from the surface [10], Fig. 4. Furthermore, multi-layers
of the adsorbate phase may be formed. Two types of thermal
energy are liberated; the latent heat of evaporation of the
adsorbed liquid and the additional heat of wetting which is due
to the electrostatic forces involved in the physical adsorption
process. The combined latent heat and heat of wetting are
transformed into sensible heat and dissipated into the adsorbent
causing an increase in its temperature [42,47]. Adsorption char-
acteristics of a certain pair depend on the adsorbate nature, the
adsorbent nature, the surface area, the reactivity of the surface,
and the temperature and the pressure at which adsorption process
takes place. The bulk uid ow through the adsorbent bed pores is
generally little, and the adsorbate transport is controlled mainly by
the diffusion mechanism [48]. The diffusion process of the gas
phase in to the micropores and macropores of the adsorbent
porous media is very slow process which offers a resistance to the
gas phase motion and therefore limits the uptake rate. The
diffusional mass transfer resistance occurs in both the micropores
as well as the macropores diffusion levels. From the experimental
and theoretical results of Scholl [49], the intra-particle pore mass
transport is the rate limiting and is the effective resistance which
controls the overall kinetics in adsorption as well as desorption.
Therefore, the mobile gas phase and the solid phase could not
attain equilibrium instantaneously, but after a certain period
of time.
4. Adsorption equilibrium models
Adsorption equilibrium of a certain pair represents the upper
limit and maximum capability for the solid to adsorb the gas. In
order to reach this limit, the gas is kept in contact with the solid
for enough period of time. The quantity of adsorbate uptake at
equilibrium is determined by the adsorption capacity W, or the
adsorbate concentration ratio X. The adsorption capacity is the
volume of adsorbate per unit mass of the adsorbent solid. The
adsorbate concentration ratio is determined as the mass of
adsorbate phase per unit mass of the adsorbent. It is noteworthy
that the amount of adsorbate uptake at equilibrium for a certain
adsorption pair is a bivariant property which depends upon the
pressure of the gas P as well as the temperature T of the adsorbent
at which the adsorption process takes place, i.e. X and W are
f P; T.
Adsorption equilibrium can be expressed through three differ-
ent ways: adsorption isotherm, X f P at T con, adsorption
Fig. 4. Schematic representation of the adsorption dynamic equilibrium.
603
isobar, X f T at P con, and adsorption isostere, P f T at
X con. Adsorption experimentations are usually performed in
the adsorption isotherms instead of adsorption isostere or adsorp-
tion isobar. This is because it is easy and convenient to investiga-
tion the adsorption process at a constant temperature.
There are many adsorption equilibrium theories which have
been extensively introduced and discussed in the literature to
describe the thermodynamic equilibrium of adsorption. These
various state equations correlate the temperature T, the pressure
P and the concentration of the adsorbed phase X in a formula such
that f T; P; X 0: The commonly used theories of adsorption
isotherm include Henrys law, Langmuirs theory, Gibbs theory,
and the adsorption potential theory [50,51]. Henrys law is valid
for low concentrations and Langmuirs theory takes into account
adsorption in monomolecular layers. Moreover, Gibbs theory is
based on the perfect gas equation, in which the adsorbate is
treated in microscopic and bi-dimensional form. The adsorption
potential theory is based on a purely thermodynamic approach
which is suitable for adsorption in microporus materials.
The commonly used equilibrium adsorption equations in the
eld of adsorption based refrigeration systems include Dubinin
equations, Langmuir equation, Freundlich equation, and Toth
equation [10]. In these equations, there are some coefcients
which are to be evaluated experimentally for every adsorption
pair. The resulting nal relation between the adsorbate concentra-
tion, the system pressure, and the temperature is known as the
adsorption pair equation of state. In the following subsections, the
commonly used adsorption equilibrium equations in adsorption
cooling systems are outlined.
4.1. Dubinin equations
The description of the adsorption equilibrium is based on the
fundamental work of Dubinin and his co-workers. Dubinin equa-
tions for adsorption are based on the theory of volume lling in
micropores by Polanyi which was published in 1947 [52]. In
Dubinin theory, the fraction of micropore volume which is
occupied by the adsorbate phase is chosen to have a functional
form of the Weibull distribution. According to Dubinin model, the
amount of uptake W (volume of adsorbate per unit mass of the
adsorbent) is expressed as follows
 
 
RT P s T n
W W o exp  ln 1
E P
The constant W o in the above equation is the maximum
adsorption capacity (which equals to the volume of pores), R is
the adsorbate phase gas constant, and E is the characteristic
energy of adsorption. The pressure P s T is the adsorbate satura-
tion pressure corresponding to the adsorbent temperature T, and n
describes the surface heterogeneity of the adsorbent. The para-
meter n 2 was rst suggested by Dubinin and Radushkevich and
the resulting adsorption equation is called DubininRadushkevich
(DR) equation.
The DR equation for adsorption has been widely used to
describe adsorption equilibrium for various uids on activated
carbons. This equation is written as follows
( 
 )
RT P s T 2
W W o exp  ln 2
E P
One of the mostly used adsorption equilibrium models is the
DubininAstakhov (DA) equation [5355]. This equation was
introduced in 1971 as a generalized form of the DR equation.
The DA equation has been developed mainly to describe adsorp-
tion of gases in microporus adsorbents particularly appropriate for
activated carbon with a large pores heterogeneousness. This model
604 H.Z. Hassan et al. / Renewable and Sustainable Energy Reviews 45 (2015) 600609

is known to be better than other models due to its thermodynamic 4.3. Freundlich equation
character [42]. According to the DA model, the amount of uptake
W is expressed as follows Freundlich equation is just an empirical equation that has been
 
  extensively used by Freundlich to describe equilibrium data. This
P s T n equation has the following form
W W o exp  D T ln 3
P
1=n
P
The coefcient of afnity D is a function of the adsorbent X Xo 9
P s T
microstructure. The DA constants D and n depend not only on the
adsorbateadsorbent pair but also on the brand and type of the A modied version of the Freundlich model was used by Saha
adsorbent. The DA equation is modied to suit the assumption et al. [2] to give a more precise tting of the experimental data and
that the density of the adsorbed phase is constant over the to consider the variations of X o and n with temperature. In this
temperature range. Therefore, the DA equation can be written form, the constant X o and the exponent 1=n in Eq. (9) were
in terms of adsorbate mass concentration as follows [56] replaced by functions of the adsorbent temperature, AT and
 
  BT, respectively. This modied model is named by Miyazaki et al.
P s T n [60] as the SBK equation. The SBK equation is given as
X X o exp  D T ln 4
P
BT
P
X AT 10
In this equation, X o is the maximum possible concentration P s T
ratio of the adsorbate (kg/kg).
where
A simple equation of adsorption state has been proposed by
Critoph [57,58]. This equation is a modied form of the DA iX
3 jX
3

equation and has a wide eld of application in the literature. The AT Ai T i and BT Aj T j
i0 j0
overall behaviour of the adsorption system will not be greatly
affected if assuming the refrigerant behaves as a perfect gas [21]. The coefcients Ai and Bj are calculated based on the
In this case, the concentration can be calculated from a modied experimental data.
DA equation. This adsorption equation of state has the following
form [19] 4.4. Toth equation
  n 
T
X X o exp  K 1 5 At low and high ends of the pressure range, the Freundlich
T s P
equation is not valid. Another empirical equation which satises
In this equation, T s P is the adsorbate phase saturation the condition of pressure limits is the Toth equation [60]. This
temperature corresponding to the system pressure P and K; n equation is suitable for systems with sub-monolayer coverage and
are an experimental constants. When n 2, Eq. (5) will be a has correct limits when P approaches either zero or innity [8].
modied DR equation [21,59] Toth equation can be written as
(  2 ) P
T X Xo 1= 11
X X o exp  K
T s P
1 6 1 P

In this equation, the parameters and depend on the

adsorption pair. Also, the parameter
 is temperature dependant
and it takes the form o exp Q sh =RT . Where, Q sh is the heat
4.2. Langmuir equation
of adsorption and R is the gas constant for the gas phase. There-
fore, Eq. (11) becomes
The Langmuir theory is the rst theoretically developed
adsorption isotherm and still retains an important position in o exp Q sh =RTP
X Xo
 1= 12
physisorption as well as chemisorption. Langmuir isotherm equa- 1 o exp Q sh =RTP
tion is based on a kinetic point of view and the principle of
adsorption dynamic equilibrium at which the rate of adsorption In the following sections, the state equations for different
equals the rate of desorption. Moreover, this equation is also based adsorption pairs are being reported and discussed based on the
on thermodynamic and statistical approaches [8,10,48]. Further- adsorption equilibrium model used.
more, Langmuir model was originally developed to represent the
behaviour of monolayer adsorption. This isotherm equation also
5. Activated carbon state equations
has been formulated for multilayer adsorption process. The multi-
layer Langmuir isotherm is given by
Charcoal has often been used since as early as 1600 B.C., by
iX
X oi i P
n Egyptians as an adsorbent for medicinal purposes and to cure a
X 7
i1
1 i P variety of ailments including poisoning as well as a purifying agent
[61]. Activated carbon is the most commonly used adsorbent in
In this equation, n is the number of sets of surface sites. X oi and adsorption cooling systems due to its large inter-particulate surface
i are temperature dependent parameters. The three terms multi- area, universal adsorption effect, high adsorption capacity, high
layer Langmuir equation (i3) has been extensively used in the degree of surface reactivity and favourable pore size. It is made by
literature. The parameters X oi and i are given by the following thermal decomposition of a carbonaceous material and is activated
equations [59] with carbon dioxide or steam at high temperatures, 7001100 1C, to
open the pores [48]. The activation process results in producing a
jX
3

aj;i Ei large internal surface that may be as high as 1200 m2/g [8]. The heat
X oi and i b0;i exp 8
j0 Tj T of adsorption for activated carbon is lower than that for other types
of physical adsorbents [62]. Methanol, ethanol, R134a, R32, butane,
where aj;i , b0;i , and Ei are experimentally determined factors. and ammonia as refrigerants are commonly used with activated
 H.Z. Hassan et al. / Renewable and Sustainable Energy Reviews 45 (2015) 600609 605

carbon. Many equations of states have been evaluated experimen-
tally for activated carbon adsorption pairs.
The DA model, Eq. (3) has been extensively used by research-
ers and many adsorption pairs equations of state were based on
this model by determining the coefcients experimentally. Values
of these coefcients for different types of activated carbon as
adsorbent and methanol as adsorbate from different studies [63
66] are summarized in Table 1.
In their work, Zhao et al. [60] tested Calgon activated carbon
WS-480 with methanol as an adsorption pair in their Lab. The
values found for X o , D, and n were 0.269, 9.08  10  6, and 1.781,
respectively. A conceptual design and performance of a dual-
purpose solar continuous adsorption system for domestic refrig-
eration and water heating is described by Alghoul et al. [67].
Malaysian type granular activated carbon (AC-5060) and methanol
are used as the adsorbentadsorbate pair. The values used in this
study for the parameters in Eq. (3) are taken as 0.363  10  3,
0.00002067, and 1.599 for W o , D, and n, respectively [67].
In the study presented by Askalany et al. [68], the experimental
adsorption and desorption characteristics of granular activated
carbon and R134a pair were investigated. The authors of this paper
have introduced an adsorption equation of state for the granular
carbon and R134a pair in the form of Eq. (1). The values of the
coefcientsW o , E, and n were found to be 1.68 kg/kg, 9.575 kJ/mol,
and 1.83, respectively. After modication, the authors presented
the equation as follows
( 
 ) introduced the following parameters for Eq. (4): X o 0:284,
P s T 1:83
X 1:68 exp  0:000868  T  ln kg=kg
P powering the convective thermal wave chillers with low-grade
are chosen have different bases, ranging from the coconut shell
based sample G32-H to the steam activated, acid washed and
extruded carbon Norit RX 3 Extra with a very high purity and low
ash mass. The samples CarboTech A35/1 and C40/1 are de-ashed
black coal based carbons [73]. Using the DubinineAstakhov
method, the micropore volume Wo, the exponential parameter n,
and specic adsorbent energy E in Eq. (1) have been determined
for methanol and nitrogen as adsorbates. These parameters are
shown in Table 3, [73].
Three different activated carbon types were tested by Critoph
[57]. The rst is Sutcliffe Speakman 208C, which is the coconut-
shell-based gas adsorption carbon. The second, referred to simply
as monolithic is based on a 208C precursor which has been
compressed with a binder and red. The third is the PVDC-based
sample which can be compressed into shape and carbonised
without cracking or deforming. The parameters of the adsorption
equation of state for these types of carbon and three adsorbents
(ammonia, R32, and butane) have been determined according to
Eq. (5) by Critoph [57]. The results are summarized in Table 4. The
coefcients of the modied DA equation, Eq. (5), for activated
carbon (YKAC, 1420 mesh, produced from coconut shell) with
ammonia and methanol are given by Wang et al. [74] as follows;
for methanol: X o 0:45; K 13:38; n 1:5 and for ammonia:
X o 0:29; K 3:57; n 1:38.
For Shanghai YK (coconut shell type activated carbon) and
methanol pair, Wang et al. [75,76] and Yong and Sumathy [77]
K 10:21, and n 1:39. Tierney [78], in his investigation of

Saha et al. [69] presented the results of an investigation on the Table 2

performance of combined adsorption refrigeration cycles. In their Experimental values for W o , E, and n in Eq. (1) for various types of charcoal and
proposed combined cycle, activated carbonR507A pair is used in HFC-134a pairs.
the bottoming cycle and activated carbonR134a pair is used in
Charcoal specimen W o [m3/kg] E [kJ/mol] n
the topping cycle. The cycle simulation is based on the experi-
mentally conrmed adsorption isotherms, data for R134a and Chemviron 0.279  10  3 14.870 1.60
R507A on highly porous based activated carbon of type Maxsorb Fluka 0.449  10  3 8.897 0.95
III. These data are the numerical values of the parameters W o , E, Maxsorb-II 1.548  10  3 8.269 1.50
and n in Eq. (1) which are found to be 1.17  10  3 m3/kg, 1.47, and
58.04 kJ/kg, respectively for the Maxsorb III activated carbon
R507A pair [69]. Saha et al. [70] also measured these parameters Table 3
for Maxsorb III activated carbonR134a pair and found these Experimental values for the parameters in Eq. (1) for various types of activated
values to be 1.66  10  3 m3/kg, 1.3, and 82.9 kJ/kg, respectively. carbon as adsorbent with methanol and nitrogen as adsorbates.
Banker et al. [71] presented a thermodynamic analysis for a two
Carbon sample Methanol Nitrogen
stage thermal compression process for an adsorption refrigeration
cycle with HFC-134a as the working uid and activated carbon as 3
W o [cm /g] E [kJ/mol] n W o [cm3/g] E [kJ/mol] n
the adsorbent. They used the values of parameters in Eq. (1) which
were introduced experimentally by Akkimaradi et al. [72] and are G32-H 0.482 19.22 2.59 0.469 6.486 1.7
Norit R 1 Extra 0.519 17.38 2.27 0.530 6.161 1.4
presented in Table 2.
RUTGERS CG1-3 0.535 14.26 1.80 0.545 5.059 1.2
Six different activated carbons, supplied by Norit, Rutgers and Norit RX 3 Extra 0.551 16.89 2.06 0.576 6.119 1.2
CarboTech are characterized and evaluated for the use in thermally CarboTech C40/1 0.633 12.46 1.85 0.695 4.366 1.1
driven adsorption chillers by Henninger et al. [73]. These samples CarboTech A35/1 0.786 11.72 1.76 0.772 4.119 1.2

Table 1
Experimental values of the DA equation of state coefcients, W o , D, and n, for
various types of activated carbonmethanol pair. Table 4
Experimental values for X o , K, and n in Eq. (5) for various types of charcoal and
Carbon type W o [m3/kg] D n adsorbate pairs.

3 5
207E4 0.365  10 14.962  10 1.34 Carbon Adsorbate X o [kg/kg] K n
Chinese LSZ30 0.405  10  3 31.97  10  5 1.26
Thai MD6070 0.988  10  3 88.98  10  5 1.12 208C Ammonia 0.290 3.1853 1.0957
LH 0.860  10  3 25.74  10  5 1.32 208C R32 0.476 2.4634 1.3880
DEG 0.534  10  3 19.60  10  5 1.31 208C Butane 0.259 1.2895 1.1428
PKST 0.258  10  3 96.56  10  5 2.00 Monolithic Ammonia 0.270 4.3772 1.1965
AC-35 0.427  10  3 50.2  10  5 2.15 Monolithic R32 0.461 2.6729 1.3326
BPL 0.414  10  3 61.57  10  5 1.45 Monolithic Butane 0.237 1.3693 1.3921
NORIT RB 0.415  10  3 11.4  10  5 2.00 PVDC-based Ammonia 0.232 4.6342 1.8065
606 H.Z. Hassan et al. / Renewable and Sustainable Energy Reviews 45 (2015) 600609

heat, used Eq. (5) with the parameters X o 0:356, K 32:65, where the pressure P is in mbar and the temperature T is in K.
and n 2:0 for activated carbon pellets and methanol pair. For iX
3 jX
3
activated carbon cloth (ACC) and methanol pair, these parameters aX ai X i and bX bj X j 14
are X o 0:602, K 1:272, and n 8:8135. i0 j0
Wang et al. [79] presented an experimental work to evaluate
The coefcients ai and bj are calculated based on the experi-
the adsorption characteristics of a new type consolidated compo-
mental data. These coefcients have been evaluated for the
site activated carbon with ammonia. The composite was developed
activated carbonmethanol pair as shown in Table 6.
with a host matrix of expanded natural graphite treated with
sulphuric acid (ENGTSA). The adsorption performance for com-
posite activated carbon and granular activated carbon were eval-
6. Silica gel state equations
uated by tting experimental data with the modied equilibrium
DubininAstakhov equation, Eq. (5), as follows [79]
Another type of adsorbents is silica gel which has a strong
(  0:81 ) afnity especially towards water, adsorbs up to 0.4 kg of water
T
X 0:4655 exp  4:282 1 ; vapour per kg at 27 1C [85]. Depending on the conditions of
T s P
preparation, silica gel can have a range of surface area from about
200 m2/g to as high as 900 m2/g and a total porosity ranging from
Granular activated carbon
0.5 to 0.65. The high end of surface area is achievable but the pore
(  0:89 ) size is very small, mean pore diameter is 22 nm, Duong [8]. When
T the particles become saturated, they do not suffer any change in
X 0:4703 exp  5:551 1 ;
T s P size or shape, and even when completely saturated the particles
seem to be perfectly dry [47]. The most attractive feature of silica
Composite adsorbent ofactivated carbon
gelwater pair is its ability to work at low temperatures [85]. This
pair can be driven with a heat source at 50 1C [86].
Two types of monolithic activated carbons are investigated by
The coefcients of DA model, Eq. (4) for silica gel (with
Tamainot and Critoph [80] with the intention of designing a high
average particle size of 6 mm and pore size varying between
performance generator for sorption refrigeration systems and heat
1.5 nm and 3.0 nm) and water pair are given as 0.35, 9.08  10  6,
pumps using ammonia as refrigerant. This paper is mainly focused
1.7 for X o , D, and n, respectively [87]. In the work reported by Thu
on the experimental procedures and results. Typical values of the
et al. [87], three types of commercially available silica gels were
parameters in Eq. (5) obtained for the LM127 carbon sample were
investigated to be selected in the adsorption desalination cycles.
X o 0:3629, K 3:6571, and n 0:94 and those for LM128
These types are Type-RD 2560 (manufactured by Fuji Silysia,
were X o 0:3333, K 3:6962, and n 0:99. The modied DR
Japan), Type-A5BW (Manufactured by KD Corporation, Korea),
equation, Eq. (6), has been used to express the adsorption of
and Type-A (Mayekawa, Japan). These three types of silica gel
ammonia in the Sutcliffe Speakman activated carbon 208C [21,81].
were investigated using a surface characteristic analyser and their
The values of parameters X o , and K are 0.247, and 10.29, respec-
thermo-physical properties were evaluated using several analysis
tively. Turner [81] introduced the parameters in the modied DA
methods. The water vapour uptake analysis which was carried on
Eq. (5) and the modied DR Eq. (6) for carbon and ammonia pair,
by the authors resulted in the values of W o , E, n which are in
Table 5.
Eq. (3). The values of these coefcients are summarized in Table 7.
Cacciola et al. [82] assumed that the difference in the heat
Di et al. [88] presented theoretical and experimental work of a
capacity of the adsorbate and gas phases can be neglected.
silica gelwater adsorption chiller, which is developed in Shanghai
Therefore, the enthalpy of adsorption is independent of tempera-
Jiao Tong University (SJTU). They used the following values for the
ture and the equilibrium conditions can be represented by a set of
parameters in the modied DA adsorption equation of state,
isosteres. Under these conditions, the isosteres on the lnP versus
Eq. (5), X o 0:346, K 5:6, n 1:6. However, there is no
1=T plot are straight lines with slopes which are proportional to
knowledge regarding the source of these values although Solmu
the enthalpy of adsorption. Thus the equilibrium conditions of an
adsorbent and adsorbate pair are represented by the following
Table 6
equation adsorption equation of state [83,84]:
Coefcient of Eq. (14).

aX bX
lnP 13 Parameter Activated carbonmethanol
T
a0 20.3305
Table 5 a1 65.3035  10  3
Values for X o , K, and n in Eq. (4) and X o , Kin Eq. (6) for various types of charcoal and a2  1.66841  10  3
ammonia pairs. a3 5.23793  10  5
b0  6003.58
Carbon DR Eq. (6) DA Eq. (4) b1 63.1516
b2  2.60587
Xo K Xo K n b3 40.5379  10  3

208C1 0.249 10.758 0.252 8.572 1.832

208C2 0.234 5.985 0.246 4.058 1.498
208C3 0.216 6.398 0.24 4.321 1.464 Table 7
BPL 0.204 10.062 0.277 5.674 1.281 Experimental values for W o , E, and n in Eq. (3) for various types of silica gel
SC11 0.254 9.495 0.283 6.936 1.312 water pairs.
AS12 0.317 10.06 0.318 10.226 1.99
AX21 0.555 8.866 0.605 6.095 1.607 Silica gel type W o [cm3/g] E [kJ/mol] n
AX31 0.451 12.294 0.465 12.416 1.9
CC200 0.282 7.984 0.304 4.611 1.468 Type-A5BW 0.455 3.585 1.25
CC250 0.295 8.395 0.315 5.569 1.602 Type-RD 2560 0.327 4.384 1.35
CC700 0.261 7.677 0.275 5.23 1.637 Type-A 0.489 3.804 1.35
 H.Z. Hassan et al. / Renewable and Sustainable Energy Reviews 45 (2015) 600609
Table 8
Coefcients of Eq. (10) for two types of silica gel and water pairs.
Parameter RD silica gel and water pair Silica gel and water pair
A0  6.5314 kg 31.198 kg
A1 0.072452 kg/K  0.2665 kg/K
A2  0.23951  10  3 kg/K2 0.769  10  3 kg/K2
A3 0.25493  10  6 kg/K3  0.73898  10  6 kg/K3
B0  15.587 41.581
B1 0.15915 K  1  0.35435 K  1
B2  0.50612  10  3 K  2 0.10199  10  2 K  2
B3 0.5329  10  6 K  3  0.97034  10  6 K  3
et al. [89] have recently used these values in their study. The
adsorption equilibrium of water on a composite adsorbent com-
posed of lithium chloride in silica gel has been tested [87].
Furthermore, DubininAstakhov equation is used to t the experi-
ment data with values of the parameters in Eq. (5) are X o 0:489,
K 0:342, n 1:604 [9092]. Sakoda [93] and Chihara [94] have
used the Freundlich equation, Eq. (9), to represent the equation of
state for the silica gel and water adsorption pair with X o 0:346,
and n 1:6 determined from experiments [95]. Cho and Kim [96]
represented the adsorption equilibrium of the Fuji RD-type silica-
gel and water pair by Eq. (9) with Xo 0.552 kg/kg and n 1:6.
Miyazaki et al. [60] have used the SBK equation, Eq. (10), and the
correlated experimental data presented by Saha et al. [2] for the
RD silica gel and water pair. Also, Saha et al. [86] used the same
equation for another type of silica gel and water pair. The numerical
values of the parameters A and B are summarized in Table 8.
For the Fuji Davison Type RD silica gelwater pair, the coef-
cients of Toth empirical equation, Eq. (12), were calculated by Chua
et al. [97,98]. These coefcients are given as 0.45 kg/kg, 7.3 
10  4 Pa  1, 2.693  106 J/kg, 12 for X o , o , Q sh , and , respectively.
The corresponding coefcients for the SWS-1L (mesoporous silica
gel impregnated with CaCl2) and water pair are given as 0.8 kg/kg,
2  10  12 Pa  1, 2.76  106 J/kg, 11, respectively. Also, those for
silica gel Type A and water pair are 0.4 kg/kg, 4.65  10  13 Pa  1,
2.71  106 J/kg, 10, respectively [99].
7. Zeolite state equations
A third solid adsorbent is zeolite which is a type of microporous
crystalline aluminosilicate mineral which can be found naturally
or made synthetically. Although articially synthesized zeolites are
have good heat transfer performance. There are many types of
articially synthesized zeolites, such as type A, X, Y, ZSM, morde-
nite, and pentasil zeolite [62,87]. Zeolite framework consists of an
assemblage of SiO4 and AlO4 jointed together in various regular
arrangements. This forms an open crystal lattice containing pores
of molecular dimensions into which adsorbate molecules can
penetrate. This micropore structure of zeolite crystal lattice results
in a precisely uniform pore size, the unique feature that distin-
guishes zeolite from other traditional microporous adsorbent [48].
The pore size of zeolites determines the selectivity for different
adsorbates, thus the zeolites are also named as zeolite molecular
sieve. The main types of zeolite molecular sieves that are used for
adsorption refrigeration include 4A, 5A, 10X and 13X types [62].
Water is commonly used with zeolite as a working pair.
In the numerical investigation of an adsorption heat pump
accomplished by Sun et al. [100], the zeolite NaXammonia pair
was used. The manipulated equation of state for this pair is similar
to Eq. (1) and has the following form
( 
 )
P s T 2
W 221:2 exp  1:916  10  7  T  ln kg=m3
P
607
For zeolitewater adsorption pair, Douss and Meunier [99]
presented the coefcients of DA Eq. (3) as W o 0:269
10  3 m3 =kg, D 1:8  10  7 , and n 2.
The parameters in the modied DA equation, Eq. (5), for
zeolite (48 mesh, grain diameter of 2.384.75 mm) and water are
given by Lu et al. [101] as X o 0:261; K 5:36; n 1:73. In
another study by Waszkiewicz et al. [102], the parameters used in
their analysis of adsorption refrigeration system using zeolite and
methanol pair were X o 0:17472; K 1065:185; n 4:11538.
However, the authors havent stated the source or reference for
these values nor the type of zeolite they used.
In the paper introduced by Zhang and Wang [103], combined
solid adsorption-ejector refrigeration and heating hybrid system
driven by solar energy was proposed. In this system, zeolite 13X
water working pair was chosen. The authors used the modied D
A model to represent the equation of state for the selected
adsorption pair. The parameters used in this equation, Eq. (5),
were X o 0:27, K 5:63, n 1:73. However, there is no knowl-
edge regarding the source of these values. The work introduced by
Adell [104] is based on X o 0:269, K 4:33, n 2 for anhy-
drous zeolite and water pair.
The equilibrium adsorption capacity of water on a natural
zeolite has been experimentally determined at different zeolite
temperatures and water vapour pressures for use in an adsorption
cooling system by Solmu et al. [88]. Natural zeolite (8895%
klinoptilolit) with 0.5 mm grain size supplied by the ROTA mining
company was used in these experiments. The modied Dubinin
Astakhov adsorption equilibrium model, Eq. (5), was tted to
experimental data. Two separate correlations were obtained for
adsorption and desorption processes as well as a single correlation
to model both processes. The values of parameters in the equation
of state, Eq. (5), from their work are given as follows;
For the adsorption process: X o 0:1219; K 5:052; n 1:4.
For the desorption process: X o 0:1249; K 3:620; n 1:2.
For the average: X o 0:1233; K 4:268; n 1:3.
Powdered zeolite CBV901 particles (15.9 mm mean diameter)
and methanol as working pair was investigated by Waszkiewicz
et al. [105]. The adsorption equilibrium data for this pair was
formulated in the form of Eq. (5). The calculated parameters are
reported as: X o 0:218, K 28:4788, n 1:7. The form of the
adsorption equation of state presented by Cacciola et al. [83], Eq.
(13) has been used many times in the literature. Zhang and Wang
[106,107] investigated the performance of an adsorption cooling
system that uses zeolite 13Xwater pair. The values of the
coefcients ai and bj are taken from [102] for zeolite 13Xwater
and zeolite 4Awater pairs, as summarized in Table 7. Also Douss
et al. [108] presented these coefcients for the zeolite NaX and
water pair, Table 9.
Sun et al. [109] introduced a numerical study on coupled heat
and mass transfers in a zeolite 13-X absorbent. They used the three
terms multilayer Langmuir equation, Eq. (7), to express the
Table 9
Coefcients of Eq. (13) for three types of zeolite and water pairs.
Parameter Zeolite 4Awater Zeolite 13Xwater Zeolite NaXwater
a0 14.8979 13.4244 8.9
a1 0.95408 1.10854  9.54  10  4
a2  63.666  10  3  73.176  10  3 4.52  10  7
a3  1.8488  10  3  1.6448  10  3  4.48  10  11
b0  7698.85  7373.78 3400
b1 214.981 67.2292 0.55344
b2  18.4589 0.562447  1.69  10  4
b3 0.152605  3.4867  10  3 1.66  10  8
608 H.Z. Hassan et al. / Renewable and Sustainable Energy Reviews 45 (2015) 600609

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