Fuel 171 (2016) 101–107

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Water desorption isotherms and net isosteric heat of desorption

on lignite
Keji Wan a,b, Qiongqiong He a,b, Zhenyong Miao a,b,⇑, Xuejing Liu a, Shaomeng Huang a,b
a
School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221000, Jiangsu, China
b
National Engineering Research Center of Coal Preparation and Purification, China University of Mining and Technology, Xuzhou 221000, Jiangsu, China

h i g h l i g h t s

Desorption isotherms were applied to investigate the behaviour of water on coal.

For a description of desorption process, the GAB model provided a good fit.

The BET theory was used to calculate the net isosteric heat.

There was interaction among adsorbed water molecules at the monolayer region.

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

Article history: Water vapor desorption isotherm studies were performed on lignite at the temperature 30, 40 and 50 °C
Received 25 June 2015 to investigate the behavior of water on coal. For a description of desorption process, a Guggenheim–An
Received in revised form 6 December 2015 derson–de-Boer (GAB) model provided a good fit. At the monolayer region, the overlapping isotherms
Accepted 24 December 2015
at different temperatures could not provide valid data to calculate the isosteric heat by applying the
Available online 31 December 2015
Clausius–Clapeyron equation, and hence the isosteric heat was only determined at the moisture content
from 0.125 to 0.280 mg/mg dry coal. Then, the Brunner–Emmet–Teller (BET) theory was applied to cal-
Keywords:
culate the isosteric heat at the moisture content below 0.125 mg/mg dry coal. Net isosteric heat of des-
Lignite
Desorption
orption determined from the isotherms increases from 1.88 kJ/mol in the capillary water to 8.17 kJ/mol at
Isotherm the monolayer region. This increase is most likely that the forces from coal surface act on all types of
BET water in raw lignite, and as the moisture content decreases, the forces are becoming stronger. Besides,
Isosteric with the effect of the interaction among adsorbed water molecules and the bonding force between water
Heat molecules and active sites, at the monolayer region, a maximum energy peak appears on the curve of
isosteric heat.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction is important to dehydration in two respects. Firstly, the heat of

Determining the sorption isotherms is the most fruitful single
method of investigating sorption systems. It gives not only a quan-
titative record of the variation of sorbed material with sorbate
pressure, but can also yield information on the thermodynamics
of the sorption processes [1]. This method, using both desorption
and adsorption isotherms, has been applied to investigate the
coal–water system [2–4].
Thermodynamic parameters, especially heat of sorption, are
needed both for the design of drying equipment and for an under-
standing of coal–water interactions. Knowledge of heat of sorption
⇑ Corresponding author at: School of Chemical Engineering and Technology,
China University of Mining and Technology, Xuzhou 221000, Jiangsu, China.
Tel./fax: +86 0516 83884289.
E-mail address: zymiao@cumt.edu.cn (Z. Miao).
sorption yields a figure for the theoretical minimum amount of
energy required to remove a given amount of water from coal. Sec-
ondly, knowledge of heat of sorption can provide insights into the
microstructure associated with a coal, as well as theoretical inter-
pretations for the physical phenomena occurring at coal–water
interfaces. Allardice and Evans [1] determined water sorption iso-
therms, the standard sigmoid shape, on the Yallourn brown coal at
the temperature of 30, 40, 49 and 60 °C. They found that enthalpy
of sorption calculated from the isotherms increases progressively
up to 14 kcal/mol over the multilayer and monolayer regions,
because of hydrogen bonding of water in the monolayer. This pat-
tern of behavior has also been reported for bituminous coals [4].
Staszczuk [5] using programmed thermal desorption techniques
found a similar pattern of progressively increasing heats of sorp-
tion at lower moisture contents for hard Polish coals.

http://dx.doi.org/10.1016/j.fuel.2015.12.054
0016-2361/Ó 2015 Elsevier Ltd. All rights reserved.
102 K. Wan et al. / Fuel 171 (2016) 101–107

The differential heat of sorption can be estimated through two
different methods. The most common method is the application
of Clausius–Clapeyron equation to the sorption isotherms at differ-
ent temperatures [1,6–8]. Although not always true the assump-
tion that isosteric heat of sorption is invariant with temperature
has often been accepted, it provides a rapid computational proce-
dure. The second method estimates the heat of sorption by means
of calorimetric techniques [9,10]. In some cases, depending on the
high precision calorimetric measurement, the method could gener-
ate a series of experimental data which is more accurate. However,
for the lignite with high volatile matter content, directly determin-
ing the heat of sorption by calorimetric measurement cannot avoid
the large error caused by rupture of weak chemical bonds in the
temperature programmed desorption. According to Allardice and
Evans [11], due to the effects of the thermal decomposition of func-
tional groups in the coal, the amount of water which could be des-
orbed after prolonged evacuation to a constant weight increased
with increasing temperature. Furthermore, Chen [12] calculated
the thermal properties by equations that were derived directly
from isotherm model equations by the Clausius–Clapeyron ther-
modynamic theory, and he summarized that the isosteric heat,
expressed as a function of temperature and moisture content,
showed good agreements with the values calculated by the above
two methods. Nevertheless, semi-empirical or empirical model of
sorption is applied to formula transformation, and this method
may be not always accurate. Therefore, the Clausius–Clapeyron
theory would be better suitable for lignite.
However, we must stress that the lignite from Inner Mongolia of
China has particular sorption nature, dramatically different from
the typical brown coal or lignite such as famous Victorian brown
coal, and particular properties of sorption also make the Clau-
sius–Clapeyron equation being not always applicable in full mois-
ture content range to calculate the isosteric heat of sorption.
The aim of this study is (1) to measure desorption of water on
Inner Mongolia lignite and to describe the process with an appro-
priate desorption isotherm model, (2) to determine the isosteric
heat of desorption in new ways and (3) to analysis coal–water
interactions during desorption process.
(P/P0) [2]. To eliminate the possible effect of irreversible changes
and maintain the sample as close as possible to the original
as-mined coal, approximately 100 mg of fresh sample without
vacuum degassing was directly used for each measurement. The
relative humidity was increased/decreased to a fixed value, and
water uptake versus time was recorded under isothermal condi-
tions until equilibrium, which was assumed to be established when
there was no weight change of more than 1 lg over a period of
5 min. This process was repeated at 96%, 90%, 80%, 70%, 60%, 50%,
40%, 30%, 20%, 15%, 11%, 8%, 6%, 4%, 2% and 0% relative humidity.
Measurements were performed at temperatures of 30, 40 and
50 °C, respectively. The experiments were repeated three times
in order to verify the results.
2.3. Methods
2.3.1. Water desorption isotherm models
This paper reported on the application of eight models to fit the
isotherms of water vapor desorption on lignite, and the models
were also recommended for other similar porous media such as
foods and woods. The corresponding equations included two or
three parameters except modified Halsey model involved four
parameters as in Table 2. These parameters were identified by
non-linear least square regression analysis. The optimal fitting
model was chosen according to the minimum residual sum of
squares (RSS), the minimum mean relative deviation (MRD), and
the maximum degrees of freedom adjusted correlation coefficient
square (Adj. R2) that Adj. R2 > 0.98 was considered here to be a rea-
sonable fitting [6].
X
n
RSS ¼ ^ i Þ2
ðyi  y
i¼1
RSSðn  1Þ
Adj: R2 ¼ 1 
SSTðv Þ
X
n
SST ¼  i Þ2
ðyi  y
i¼1

N  
2. Materials and methods 100 X ^
yi  yi 
MRD ¼
N i¼1 yi 

2.1. Sample characterization
where yi was the experimental data, y ^i was the fitted values, SST
Shengli (SL) raw lignite from Inner Mongolia of China was used i was the mean of experimental
was the total sum of squares, and y
for the present study. All samples were ground to obtain a grain data.
size below 0.15 mm and then sealed in a plastic bag to protect
against moisture loss. The basic qualitative parameters of the sam- 2.3.2. Brunner–Emmet–Teller (BET) theory
ple are presented in Table 1. An important characteristic of the BET equation was that it pro-
vided a simple method to estimate the heat of sorption and the
2.2. Dynamic vapor sorption (DVS) analyzer monolayer value of coverage, both parameters were important in
thermodynamic calculation. The classical BET equation [20] was
Water desorption measurements were conducted using Aqua- given by:
dyne DVS supplied by Quantachrome Ins, USA. It was a very useful
m0 Cx
means of determining accurate sorption isotherms at different M¼ ð1Þ
ð1  xÞð1  x þ CxÞ
temperatures and using a range of pre-set relative humidity values

Table 1
Proximate and ultimate analysis of the sample.

Moisture (wet basis, %) Proximate analysis (wt.% dba) Ultimate analysis (wt.% dafb)
Ash yield Volatile mater Fixed carbon C H S N Oc
28.68 22.28 32.41 45.32 65.71 4.92 2.42 1.26 25.69
a
Db: dry basis.
b
Daf: dry ash free basis.
c
By difference.
 K. Wan et al. / Fuel 171 (2016) 101–107 103

Table 2
Mathematical models for fitting the desorption isotherms of SL lignite.

Models Mathematical expression Parameters Reference

Guggenheim–Anderson–de-Boer (GAB) M¼ m0 CKx m0 ; C; K Iglesias and Chirife [13]
ð1KxÞð1KxþCKXÞ
 
Halsey x ¼ exp A A, B Halsey [14]
RTM B
 
Modified Halsey x ¼ exp A  expðB  C  TÞ  M D A, B, C, D Shigehisa et al. [15]

Henderson B A, B Henderson [16]

x ¼ 1  expðA  T  M Þ
 
Modified Henderson x ¼ 1  exp AðT þ CÞM B A, B, C Shigehisa et al. [15]

Dubinin–Astakhov  1C A, B, C Do [17]

ln M ¼ A þ B  ln x
 
Chung–Pfost x ¼ exp ART  exp ðB  M Þ
A, B Chung and Pfost [18]
Oswin  x B A, B Chen [19]
M ¼ A  1x

M: equilibrium moisture content. x: relative humidity.

where x represented the relative humidity, M was the amount of

water, m0 was the monolayer capacity, and C was an energetic con-
stant, which could be estimated for each temperature. An alterna-
tive procedure was to use an Arrhenius-like temperature function:
 
E1  EL
C ¼ C 0 exp ð2Þ
RT
where E1 was the interaction energy between the solid and mole-
cule of the first layer, EL was the heat of liquefaction, T was the
absolute temperature and R the gas constant. C0 was pre-
exponential which could be either greater or smaller than unity
and it was often assumed as unity without any theoretical
justification.

2.3.3. Heats of sorption

The isosteric heat of sorption for each adsorbate was calculated
by applying the Clausius–Clapeyron equation on isotherm at differ-
ent temperatures,
Fig. 1. Desorption isotherms for SL lignite at 30, 40 and 50 °C.
@ lnðPÞ Q st
¼ 2 ð3Þ
@T RT
therefore roughly divided into three zones, namely monolayer
where P was the partial absolute pressure at a given loading. Eq. (3) water, multilayer water and capillary water [1]. Temperature
was based on the assumption that isosteric heat of adsorption (Q st ) makes a small difference to the isotherms in a relative humidity
was invariant or varies very little with temperature. From that range of (P/P0 > 0.20), and the effects are negligible at P/P0 < 0.20
equation, applied to pure water, the following was obtained: where the isotherms at different temperatures are almost coinci-
@ lnðP=P0 Þ qnst dent. This may be due to that, with temperature increasing, the
¼ 2 ð4Þ water molecule movement is enhanced, which results in that par-
@T RT
tial water molecules have enough energy to get rid of intermolec-
where P 0 was the saturation pressure of water vapor at temperature ular attraction forces between sorptive sites and water vapor. The
T, qnst was the net isosteric heat of sorption representing the differ- escaped water molecules decrease moisture content at the equilib-
ence between the isosteric heat and pure water vaporization rium relative humidity. However, because of the overlapping iso-
energy. Thus, the integrated form of Eq. (4) was expressed by Eq. therms in the range of P/P0 < 0.20, this interpretation is invalid. It
(5): is probably that there is some stronger binding energy to keep
qnst 1 the water molecules being tightly bound to coal surface, and the
lnðP=P 0 Þ ¼   þf ð5Þ increased molecular energy due to higher temperature cannot
R T
overcome the energy barrier. The BET theory, which will be dis-
where f was the constant term. According to Eq. (5), qnst could be cussed in the sections that follow, shows that water content in
calculated by plotting the sorption isotherms as lnðP=P0 Þ at a given the range of P/P0 < 0.20 is approximate the monolayer water. These
moisture content vs 1=T and measuring the slope. results indicate that some strong forces between coal surface and
water molecules result in the high energy barrier. Moreover, the
3. Results and discussion oxygen-containing functional groups and minerals (e.g., quartz
[21]) in the surface of SL lignite, which can provide the binding
3.1. Desorption isotherms of samples sites of water molecules, may be relevant to these forces.

The desorption isotherms for SL lignite at 30, 40 and 50 °C are

shown in Fig. 1. The desorption isotherms have the sigmoidal-
shaped profile according to the BET classification [20]. As seen in
the figure, the equilibrium moisture content increases with relative
humidity at constant temperature. Two bending regions are noted,
one around 0.15–0.20 and another at 0.60–0.70. The isotherm is
3.2. Curve fitting by equations in Table 2
The desorption experiments, at different temperatures, were
repeated three times, and the data showed that the deviation
was unacceptable at the relative humidity of 95%. Thus, all the
104 K. Wan et al. / Fuel 171 (2016) 101–107

Table 3
Predicted parameters of the fitted models to the experimental data for the water desorption isotherm of coal at 30, 40 and 50 °C.

Goodness of fit indexes Model coefficient

2
Model type Temperature (°C) Adj. R RSS MRD (%) A (m0) B (K) C D
GAB 30 0.999 0.00002 2.664 0.097 0.867 6.303 –
40 0.999 0.00007 3.704 0.094 0.861 6.679 –
50 0.999 0.00006 2.920 0.082 0.894 7.729 –
Halsey 30 0.912 0.0126 53.761 2.998 1.670 – –
40 0.927 0.0097 52.458 2.794 1.706 – –
50 0.939 0.0080 44.422 3.291 1.600 – –
Modified-Halsey 30 0.976 0.0242 33.622 3.315 9.580 0.454 1.210
40 0.979 0.0216 32.771 7.411 10.185 0.377 1.228
50 0.982 0.0183 30.296 5.463 7.867 0.250 1.221
Henderson 30 0.993 0.0010 3.588 0.337 1.403 – –
40 0.995 0.0007 4.355 0.267 1.410 – –
50 0.995 0.0007 8.603 0.198 1.337 – –
Modified-Henderson 30 0.998 0.0027 4.877 0.319 1.366 0.164 –
40 0.997 0.0029 5.822 0.258 1.383 0.158 –
50 0.997 0.0037 7.069 0.211 1.371 0.879 –
Dubinin–Astakhov 30 0.995 0.0007 4.770 0.725 1.497 0.651
40 0.997 0.0004 4.889 0.714 1.541 0.616 –
50 0.996 0.0005 5.603 0.554 1.773 0.535 –
Chung–Pfost 30 0.990 0.0117 30.317 471.750 10.492 – –
40 0.990 0.0123 29.606 493.218 10.917 – –
50 0.989 0.0133 29.113 510.842 11.540 – –
Oswin 30 0.969 0.0044 25.859 0.138 0.448 – –
40 0.975 0.0034 23.772 0.134 0.445 – –
50 0.984 0.0023 16.703 0.129 0.477 – –

equilibrium moisture content at this relative humidity point would

be removed before model fitting.
The results of the non-linear regression analysis of desorption
isotherms of SL lignite, at various temperatures, are shown in
Table 3. For all the models tested, the adjusted correlation coeffi-
cient square, residual error and mean relative deviation are
reported as a comparison criterion to evaluate the fit quality by
the lowest values of RSS and MRD and highest values of Adj. R2.
Examination of the results in Table 3 indicates that Guggenheim–
Anderson–de-Boer (GAB) model is best to describe the experimen-
tal desorption data for SL lignite, and the residual plots for GAB
model at different temperatures are depicted in Fig. 2 that show
a good fitting effect. The fitted GAB model at three temperatures
are shown in Fig. 3, and it will be used to calculate the heat change
of desorption.

Fig. 3. The fitted GAB model at three different temperatures.

3.3. Isosteric heat of desorption

The isosteric heat of desorption is defined as the difference

between the partial molar enthalpies in the gas or vapor and
adsorbed phases. It is a measurement of the energy or intermolec-
ular bonding between water molecules and coal surfaces.

3.3.1. Isosteric heat of desorption determined by Clausius–Clapeyron

Fig. 2. Residual plots for GAB model at different temperatures.
equation
The isosteric heat of desorption is deduced from the slope of the
plots lnðP=P 0 ) against 1=T for a given moisture content according to
Eq. (5), and the desorption isosteric curves of SL lignite are shown
in Fig. 4. This method, by applying Clausius–Clapeyron equation, is
based on the assumption that net isosteric heat (qnst Þ is indepen-
dent of temperature and requires measurement of the desorption
isotherms at more than two temperatures. However, because
 K. Wan et al. / Fuel 171 (2016) 101–107 105

Table 4
The values of the constants C and m0 of BET equation at different temperatures.

Temperature R2 Fitting m0 C E1  EL
(°C) range (mg/mg) (kJ/mol)
30 0.999 0.04–0.4 0.083 6.873 4.858
40 0.999 0.04–0.4 0.077 8.042 5.428
50 0.999 0.04–0.4 0.074 8.159 5.640

given in Table 4 against T, and the Adj. R2 is 93%. Iglesias and Chirife
[25] also reported similar linear relation. According to Eq. (6), the
correlation coefficient for monolayer capacity with temperature is
calculated as 0.00045, and the magnitude is approximates to zero.
Hence, the value of m0 can be expected to be independent of the
temperature within the range from 30 °C to 50 °C, and it can be
expressed by Eq. (7),

@ ln m0
¼0 ð7Þ
Fig. 4. Desorption isosteric curves of SL lignite. @T

Because the m0 is related to the number of sorption sites available

of the overlapping isotherms in the low relative humidity
(P/P0 < 0.20) and high humidity (P/P0 > 0.9) range (in Fig. 3), only
one isotherm is available, and hence the Clausius–Clapeyron’s
equation cannot be used to calculate the isosteric heat at these
regions. Finally, the net isosteric heat of desorption is only
obtained at the moisture content from 0.125 to 0.280 mg/mg dry
coal, which is shown in Fig. 5.
3.3.2. Isosteric heat of desorption determined by BET theory
The equilibrium data of SL lignite are analyzed according to Eq.
(1), which is made for all isotherms at different temperatures in
the range of 0.04 < P/P0 < 0.4. The values of energy constant (C)
and monolayer capacity (m0) are given in Table 4.
As temperature increases from 30 to 50 °C, the monolayer value
slightly decreases in desorption processes. This phenomenon has
been ascribed to a reduction in the number of active sites due to
physical and chemical changes induced by temperature [22–24].
Although the exact form of the variation cannot be determined
precisely, it is found that for the range of temperatures from 30
to 50 °C, m0 may be approximately represented by the equation:
m0 ¼ 0:00045T þ 0:21892
where T is the absolute temperature. The equation is identified by
linear least square regression analysis from the plot of the m0 values
on the coal surface, it can be assumed that the temperature has
no effect on the structural characteristics of coal surface.
In Eq. (2), the authors of the BET theory assumed that the pre-
exponential factor (C0) was taken as unity [20]. This simplifying
assumption has been a source of considerable discussion, and nota-
bly different values of C0 are reported in the literature, ranging
from 0.02 [26] to greater than unity [27]. Kemball and Schreiner
[28] summarized that the C0 may vary from 105 to 10, depending
on the entropy changes accompanying the sorption process. How-
ever, with the assumption that the C0 is unity, the simplified
expression for C has been used in the literature to evaluate the
net BET heat of desorption (E1  EL) in the first layer. The values
of E1  EL determined in this manner, the so-called net BET heats
of desorption, have generally been found to be much lower than
calorimetric or isosteric heats [29]. Nevertheless, it will be still
on the same order of magnitude as isosteric heat.
In this paper, it is also assumed that C0 is taken as unity. How-
ever, the proper way to calculate the isosteric heat of desorption is
by computing d ln(P/P0)/d ln(1/T) at a constant moisture content
from the BET equation directly instead of equating E1  EL with
ð6Þ the isosteric heat [30]. Differentiating Eq. (1) at a constant mois-
ture content, the expression, where P=P 0 is represented by x, is
given by

ðC  1Þx2 þ 1
 d ln x ¼ d ln C þ d ln m0 ð8Þ
ð1  xÞð1  x þ CxÞ

therefore,

½ðC  1Þx2 þ 1 @ ln x @ ln C @ ln m0
 ¼ þ ð9Þ
ð1  xÞð1  x þ CxÞ @T @T @T
The assumption that E1  EL is invariant with temperature is
acceptable [17]. Thus, the differentiating Eq. (2) is given by

@ ln C 1
¼ 2 ðE1  EL Þ ð10Þ
@T RT

Substituting Eqs. (4), (7) and (10) into (9), we obtained the expres-
sion of isosteric heat which is given by

ðE1  EL Þð1  xÞð1  x þ CxÞ

qnst ¼ ð11Þ
½ðC  1Þx2 þ 1

Fig. 5. Net isosteric heat of desorption in function of equilibrium moisture content

The isosteric heat of desorption determined by differentiating BET
and illustration of desorption process of SL lignite (the shaded water molecules equation (11) is shown in Fig. 5 in the moisture content range of
represent different layers of water). 0.02–0.125 mg/ mg.
106 K. Wan et al. / Fuel 171 (2016) 101–107
C Shrinkage
Lignite
Fig. 6. Monolayer water in pore during desorption process.
3.3.3. Sorption behavior derived from isosteric heat of desorption
The isosteric heat of desorption on SL lignite is presented in
Fig. 5 as function of the moisture content of coal. The net isosteric
heat is given as a positive quantity, which illustrates that the
endothermic character of desorption and that the energy of bind-
ing between the sorption sites and the water molecules is higher
than the energy holding the molecules of pure water in the liquid
phase. According to the trend of curve, the isosteric heat is approx-
imately equal to the heat of vaporization of pure water at the mois-
ture content down to 0.40 mg/mg dry coal, although we can’t get
the exact experimental data. The heat in this moisture region also
illustrates that the water being desorbed is not bound to the coal in
any way, but is merely the water from the spaces between coal
particles [1]. In the region between 0.28 and 0.23 mg/mg dry coal,
the isosteric heat of desorption increases from 1.30 to 1.88 kJ/mol,
as the moisture content decreases. The phenomenon can be attrib-
uted to the desorption of water from the capillaries or pores within
the coal particles, and thus the water in this region is classified as
capillary water. Below moisture contents of 0.23 mg/mg dry coal,
the isosteric heat increases steeply from 1.88 kJ/mol to about
7.59 kJ/mol at 0.077 mg/mg dry coal. The abrupt change can be
attributed to the desorption of multilayer and monolayer water
that is progressively more strongly bound to the coal surface with
the moisture content decreasing. There is a clear-cut boundary
between the multilayer and monolayer water shown in Table 4
to be 0.077 mg/mg dry coal, but the transition in the isosteric heat
data from capillary to multilayer is indistinct. In the monolayer
region, the water is tightly bound to the coal surface, correspond-
ing with high interaction energy. It can be concluded that, for the
whole process of desorption, the forces from coal surface act on
all types water in raw lignite, and as the moisture content
decreases, the forces are becoming stronger. In addition, the inte-
gral of net isosteric heat provides the extra theoretical minimum
amount of energy required to remove a given amount of water
from coal. According to the integral value at different moisture
regions in Fig. 5, it will consume extra energy of 27.0 J/g dry coal
and 29.3 J/g dry coal, which does not include the latent heat of
vaporization of pure liquid water, to take out the multilayer mois-
ture (in the range of 0.077–0.23 mg/mg dry coal) and monolayer
moisture (in the range of 0.02–0.077 mg/mg dry coal) from the
coal, respectively. Finally, according to the study results, a sketch
of desorption process is also shown in Fig. 5.
With moisture content increasing, the net isosteric heat (in
Fig. 5) shows an increase at very low moisture content, and the
maximum net isosteric heat (qnst = 8.17 kJ/mol) is achieved at
0.054 mg/mg dry coal. An initial increase of the net isosteric heat
of sorption was found in the adsorption process of other materials
C
Lignite
[31,32], and the increase had been explained that the sorption of
water on the dry matrix leaded to swelling of the material, which
resulted in the exposure of sorption sites of higher binding ener-
gies not previously available. Nevertheless, there is few report on
this increase found for desorption process. Only Maskan and
Göğüsß [32] found that the isosteric heat of desorption of mulberry
appeared similar phenomenon, and the swelling explanation of the
material was hardly convincing in the case of desorption. In gen-
eral, the pore surface of coal is roughness and the adsorbed water
molecules are not uniform distribution on the surface. Hence, there
may be interaction between adsorbed water molecules, when the
moisture coverage of coal surface is high. During desorption at
the monolayer region, the binding force of the water molecules
on the coal surface is strengthened by attractive forces between
the water molecules [22]. More specifically, the energy required
to remove the water molecule a in Fig. 5 from the coal surface will
be larger than for the molecule b. In the process of desorption, the
water molecules are dispersed gradually from all over of the rolling
coal surface to sparseness, and the attractive forces between water
molecules will gradually vanish, which results in the decrease of
net isosteric heat of desorption at lower moisture contents.
Furthermore, in monolayer region, the shrinkage and collapse of
pores during desorption results in the formation of smaller diameter
pores, and the monolayer water c in the pores may be gathered and
transformed into multilayer water, as shown in Fig. 6. Hence, the
corresponding isosteric heat will be weakened.
4. Conclusion
(1) Water desorption isotherms for SL lignite have the
sigmoidal-shaped profile according to the BET classification.
Temperature effects are observed for the coal at the multi-
layer and capillary region, but the effects are negligible at
monolayer region.
(2) The GAB model is shown to be suitable for describing the
desorption isotherms of water on SL lignite with maximum
value of Adj. R2 and minimum value of RSS and MRD.
(3) The isosteric heat of desorption is given as a positive quan-
tity, illustrating the endothermic character of desorption.
At the region of moisture content above 0.077 mg/mg dry
coal, the net isosteric heat increases with decreasing of
moisture content. At the region below 0.077 mg/mg dry coal,
with the effect of the interaction among adsorbed water
molecules and the bonding force between water molecules
and active sites, the net isosteric heat curve appears a max-
imum energy peak.
 K. Wan et al. / Fuel 171 (2016) 101–107
Acknowledgments
This research was supported by the National Key Basic Research
Program of China (Grant No. 2012CB214902), the Fundamental
Research Funds for the Central Universities (2014XT05), A Project
Funded by the Priority Academic Program Development of Jiangsu
Higher Education Institutions, the National Nature Science Founda-
tion of China (Grant No. 51574239) and 111 Project (12030) for
which the authors express their appreciation.
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