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Derivation of isosteric heat of adsorption for

non-ideal gases
ARTICLE in INTERNATIONAL JOURNAL OF HEAT AND MASS TRANSFER MAY 2015
Impact Factor: 2.52 DOI: 10.1016/j.ijheatmasstransfer.2015.05.018

2 AUTHORS:
Ahmed Askalany

Bidyut Baran Saha

Sohag University

Kyushu University

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Retrieved on: 20 August 2015

International Journal of Heat and Mass Transfer 89 (2015) 186192

Contents lists available at ScienceDirect

International Journal of Heat and Mass Transfer

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

Derivation of isosteric heat of adsorption for non-ideal gases

Ahmed A. Askalany a, Bidyut B. Saha b,c,
a

Mechanical Engineering Department, Faculty of Industrial Education, Sohag University, Sohag 82524, Egypt
Interdisciplinary Graduate School of Engineering Sciences, Kyushu University Program for Leading Graduate School, Green Asia Education Center, Kyushu University, 6-1
Kasuga-Koen, Kasuga-Shi, Fukuoka 816-8580, Japan
c
International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Japan
b

a r t i c l e

i n f o

Article history:
Received 10 July 2014
Received in revised form 2 December 2014
Accepted 5 May 2015

Keywords:
Adsorption
Activated carbon
Cooling
HFC
Isosteric heat
Non-ideal gas

a b s t r a c t
This paper presented a theoretical framework for precise determination of the isosteric heat of adsorption
for non-ideal gases. The derived equation had been applied for various adsorbentrefrigerant pairs.
Highly porous activated carbon powder, namely Maxsorb III and activated carbon ber of type (A-20)
were used as adsorbents with HFC-134a and HFC-410a as refrigerants. The isosteric heat of adsorption
data showed lower values comparing to the isosteric heat of adsorption without the consideration of
non-ideality of gases. An empirical formula to perceive the isosteric heat of adsorption of HFCs gases
on to activated carbons had been extracted. Effect of the proposed isosteric heat of adsorption on the performance of adsorption cooling system based on activated carbon powder/HFC-134a had also been discussed in detail.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
A review of literature reveals that the experimental investigations and theoretical analysis on adsorption cooling and heat pump
systems have been extensively investigated by many researchers
around the world [112] due to its ability to utilize environmentally benign refrigerants and energy conservative potential.
However, the validity of the theoretical adsorption system models
has not been conrmed by experimental data for most of the studied cases. The isosteric heat of adsorption of an adsorbentrefrigerant pair is one of the key thermodynamic variables for the design
of adsorption cooling, heat pump and gas storage systems
[1318]. Moreover, the accuracy of the adsorption system
modeling largely depends on the precise value of the isosteric heat
of adsorption of the assorted working pair. A simplied but not
capturing the quantitative isosteric heat of adsorption data is the
popular ClapeyronClausius equation [19]. The assumption of ideal
gas behavior as given by the ClapeyronClausius equation is valid
only at low pressures and may not be applicable in higher pressure.
From the above viewpoint, this study presents an empirical formula to detect accurately the isosteric heat of adsorption for
Corresponding author at: Interdisciplinary Graduate School of Engineering
Sciences, Kyushu University Program for Leading Graduate School, Green Asia
Education Center, Kyushu University, 6-1 Kasuga-Koen, Kasuga-Shi, Fukuoka 8168580, Japan. Tel.: +81 92 583 7903; fax: +81 92 583 8909.
E-mail address: saha.baran.bidyut.213@m.kyushu-u.ac.jp (B.B. Saha).
http://dx.doi.org/10.1016/j.ijheatmasstransfer.2015.05.018
0017-9310/ 2015 Elsevier Ltd. All rights reserved.

HFCs on to activated carbons. The effect of using isosteric heat of

adsorption for non-ideal gases formula on the performance of activated carbon powder/HFC-134a based adsorption cooling system
has been determined.
2. Mathematical derivation
Isosteric heat of adsorption considers one of the tting parameters at half-loading in Tth equation (Eq. (1) below) [20]. Hence,
isosteric heat of adsorption has a xed value irrespective of the
adsorption temperature, pressure and uptake capacity.

6
6
6
C C06
6
4

H 
7
st
7
Pb0 e RT
7
17
!

H  t t 7
5
st
1 Pb0 e RT

where C is the absolute adsorption in kg/kg, C0 is the maximum

adsorption in kg/kg, P is the pressure in kPa, T is the temperature
in K, R is the universal gas constant in kJ/kg  K, Hst denotes the isosteric heat of adsorption in kJ/kg  K, b0 is the adsorption afnity at
innite temperature in kPa1 and t is the micropore distribution
parameter.
ClapeyronClausius equation is commonly used to estimate the
heat of adsorption at constant concentration which is given by Eq.
(2) [21];

187

A.A. Askalany, B.B. Saha / International Journal of Heat and Mass Transfer 89 (2015) 186192

Hst CC Rg

@lnP
@1=T

DubininAstakhov (DA) equation which could be written as

Eq. (3), below:

 
1
E
Cv a n
lnP lnPs 
ln
RT
W0


@lnPs 
@1=TC

By differentiating DA equation with respect to 1/T we can get

[22];

Hst CC

The form of Eq. (5) which has been derived from the DA equation and the ClapeyronClausius equation has been widely used to
govern the isosteric heat of adsorption. Since ClapeyronClausius
equation deals with the assumption of ideal gas [23], it may contains a specic percentage of error in determining the isosteric
heat of adsorption for the real gases.
The following section presents a mathematical formalism for
the derivation of isosteric heat of adsorption for non-ideal gases.
Here we choose the DA isotherm equation because it is derived
from the micropore lling model. Therefore, one needs to consider
the role of adsorbed phase volume on the elucidation of the temperature and pressure dependence of adsorption uptake which is
given by the DA equation [21] as shown below;


 n

RT
Ps
w0 exp 
ln
E
P

Cv a

va

A  BT 

 
1 )
Ps
E
Cv a n
ln
exp 
RT
P
W0

hfg
dPs

dT
T Dv fg

10

where Dvis = vv  va and Dvfg = vg  vf.

where vg and vf is the specic volumes at vapor and liquid saturation phases in m3/kg respectively. By differentiating Eq. (8) with
respect to T one can get,
dP 
s

dT

 Ps
P2

dP
dT

Ps
P

where ag is thermal expansion coefcient in the gas phase in K1.

2
2
33
 
PDv is hfg
Ps 4
aT 55
4
1
 Hst PDv is ln
P s Dv fg
P
nln C v a

""

14

w0

2
2
33
 
P Dv is
Ps 4
a
T
1 4  55
Hst
hfg Pv is ln
Ps Dv fg
P
nln w0

15

Cv a

To indicate the difference between Eq. (15) and isosteric heat of

adsorption which is driven by ClapeyronClausius, (Eq. (5))
has been written in the form of Eq. (16). By comparing Eq. (16)
with Eq. (15), a relationship between isosteric heat of adsorption
for real gas and isosteric heat of adsorption has been presented
in Eq. (17).

Hst CC

2
2
33
 
Ps 4
aT 55
4
 
1
hfg RTln
P
nln w0

16

Cv a

Hst

PDv is
Hst CC
RT

17

Eq. (17) can be driven by comparing Eq. (2) with Eq. (9). This
outage formula can be driven starting by initial equation presented
by Chakraborty et al. [19] as below;

   


dP
@P
dC
@lnP
P

dT
@C T dT
@T

Hst T Dv is

18

##
 
 1 # "
 
11
Cv a n
E
C v a n 1 dv a
ln
ln

nRT
w0
w0
v a dT
RT 2
E

11

@P
@C

 
  
RT 2 Dv is @lnP
dC
@T

vg
T dT

19

From the ClapeyronClausius equation

Hst T Dv is

@P
@C

  
dC
Dv is Hst cc

dT
vg
T

Therefore, if we proved that

format Hst

@P
@C

From the Clapeyron equation [24],

dP
Hst

dT T Dv is

13

From the Clapeyron equation, one can write

vv



1 @v a
ag
va B 
v a @T
vv

where a

1

where va, vv are the adsorbed phase and gas phase specic volume,
respectively, in cm3/g at the equilibrium pressure and temperature,
A and B are tting parameters.
With simple mathematical arrangement, the DA equation
could be rewritten as;

w0

12

 
1
 
1n
n
W 0 n ET a
W0
hfg E ln

ln
Cv a
n
Cv a

2
2
33

 
 
hfg
Ps Hst
Ps 4 1
Ps
P
a
s
 55
4ln


 ln
T
PDT v fg P2 T Dv is
P
P
P nln C v a

where; Ps is the saturation pressure in kPa, va is the adsorbed phase

specic volume in cm3/g, W0 is the maximum volumetric adsorption capacity in cm3/g, E is the characteristic energy in kJ/kg and n
is a tting parameter.
From the denition of the heat of vaporization (hfg), it can be
expressed as,

hfg R

Using Eqs. (9) and (10), Eq. (11) could be expressed as;

Dv is Hst cc

vg

@P  dC 
@C T dT

20
0 that means, our new

is true. Using the DA equation we can get;

PE 1n1
L
CnRT

21

 
where L ln CWv0a

dC

dT


 



R
Ps
RT @lnP s @lnP
C dv a

Cnyn1 ln

E
E
@T
P
@T
v a dT

22

 
where y RT
ln PPs , L yn and from the ClapeyronClausius
E
equation




dC
y hfg Hst cc
Ca
CnLy1


dT
T ET
ET
va
where a v1a ddT

@P
@C

 
T

dC
dT



PE 1n 1 y hfg Hst cc
PE 1n1


Ly
L a
RT
T ET
nRT
ET

23

24

188

A.A. Askalany, B.B. Saha / International Journal of Heat and Mass Transfer 89 (2015) 186192
1

1n
n

Since Hst cc hfg  ELn  ETna L

  


@P
dC
PE 1
PE 1 PE a 1n
PE 1n1
  2 Ln 2 Ln
L a zero
Ln
@C T dT
RT n
nRT
RT
RT

Comparing Eq. (15) with Eq. (5), it is clear that Eq. (5) expresses
isosteric heat of adsorption as a function of concentration only
[25,26], while the proposed equation, Eq. (15) considers the effect
of the adsorption pressure relative to the saturation pressure.

25
Thus;

Hst T Dv is

@P
@C

  


dC
@lnP
Dv is Hst cc
T Dv is P
0
dT
@T
vg
T
26

Eq. (15) characterizes the isosteric heat of adsorption for real

gases.

Hst A1 A2
where

A1

P Dv is
hfg
P s Dv fg

27

2
2
33
 
Ps 4
aT 55
4
1
A2 P Dv is ln
P
nln w0

28

Cv a

Table 1
Constant parameters of DA equation for various adsorption pairs.
Parameter

W0, cm3/kg

E, kJ/kg

ACP/HFC-134a
ACP/HFC-410a
ACF/HFC-134a
ACF/HFC-410a

3.947
5.963
2.45
3.254

5370
4325
7544
5260

1.04
1.17
1.32
1.43

3. Calculations procedure
In order to clarify using of the new formula, isosteric heat of
adsorption of four various adsorption pairs has been determined
based on the derived formula (Eq. (15)). A highly porous activated
carbon powder (ACP), namely Maxsorb III and activated carbon
ber (ACF) of type (A-20) are used as adsorbents with HFC-134a
and HFC-410a as refrigerants.
The parameters of Eqs. (5) and (15) (W0, E and n) of the various
studied adsorbent/refrigerant pairs have been extracted from
experimental work and have been furnished in Table 1.
Numerical values of ag, hfg, vf, vg and vv have been determined using
REFPROP [27].
Eqs. (5) and (15) have been applied and compared together for
ACP/HFC-134a, ACP/HFC-410a, ACF/HFC-134a and ACF/HFC-410a.
Eq. (15) has been employed to simulate the adsorption cooling system performance based on ACP/HFC-134a pair. The schematic diagram of the simulated single bed adsorption cooling system is
shown in Fig. 1. Table 2 depicts the design parameters of the studied adsorption cooling system.
4. Results and discussion
The isosteric heat of adsorption data in view of the non-ideality
of HFC gases have been discussed. Figs. 25 present a comparison

Fig. 1. Single bed adsorption cooling system employing ACP/R134a adsorption pair.

189

A.A. Askalany, B.B. Saha / International Journal of Heat and Mass Transfer 89 (2015) 186192

350

Table 2
Designing parameters of ACP/HFC-134a adsorption cooling system.

25 C
35 C
45 C
55 C
65 C
75 C
Non-ideal gas

300
Unit

Value

m_hw
cpw
cpac
Mac
(UA)bed
(UA)con
(UA)eva

kg/s
kJ/kg K
kJ/kg K
kg
W/K
W/K
W/K

0.5
4.18
1.4
1
60
100
100

250
Hst, kJ/kg

Parameter

200
150
100
50

300
25 C
35 C
45 C
55 C
65 C
75 C
Non-ideal gas

250

Hst, kJ/kg

200

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Cva/W0
Fig. 4. Hst with ideal and non-ideal gas considerations of ACF/HFC-134a.

150
400
350

100

300

10 C

20 C

30 C

40 C

50 C

Non-ideal gas

0
0

0.2

0.4

0.6

0.8

Cva/W0

Hst, kJ/kg

50
250
200
150
40 C
50 C

100

Fig. 2. Hst with ideal and non-ideal gas considerations of ACP/HFC-134a.

10 C

30 C

50
0
0

400
10 C
20 C
30 C
40 C
50 C
Non-ideal gas

350

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Cva/W0

Fig. 5. Hst with ideal and non-ideal gas considerations of ACF/HFC-410a.

250
200

300

150

40 C 30 C

A1

250

50 C

100

A2

Hst

200

50
0
0

0.2

0.4

0.6

0.8

Cva/W0
Fig. 3. Hst with ideal and non-ideal gas considerations of ACP/HFC-410a.

A1, A21 and Hst, kJ/kg

Hst, kJ/kg

300

0.1

150
100
50
Cva/W0
0

between isosteric heat of adsorption for ideal and non-ideal gases

for
ACP/HFC-134a,
ACP/HFC-410a,
ACF/HFC-134a
and
ACF/HFC-410a pairs, respectively. These gures have been presented based on the relative adsorption capacity. It is clear from
Figs. 25 that Hst values for non-ideal gases are always higher than
Hst values for ideal gases at the same adsorption uptake capacity.
However, with decreasing temperature the difference in Hst values
for ideal and non-ideal gas assumptions minimizes, which ensure
the dimness of temperature effect on isosteric heat of adsorption.
Figs. 69 show the relation between A1, A2 and Hst on the Y-axis
and Cva/W0 on the X-axis for ACP/HFC-134a, ACP/HFC-410a,
ACF/HFC-134a and ACF/HFC-410a, respectively. It is clear from
these gures that A1 has positive values and it is slightly decreased
by the increase in relative adsorption capacity. Such decrease is
reasonable as A1 is a function in the gas phase specic volume that

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

-50
-100
Fig. 6. A1, A2 and Hst with non-ideal gas consideration of ACP/HFC-134a.

decreases intensely with the increase of pressure as shown in

Fig. 10.
Fig. 11 shows the dependence of Hst of non-ideal gases onto the
relative loading (Cva/W0) for the assorted adsorbent/adsorbate
pairs. From this gure it is evident that the exponential function
expresses the relation between Hst and Cva/W0. This empirical relation can be written in general form as shown below;

Hst Hst0 exph  C v a=W 0

29

190

A.A. Askalany, B.B. Saha / International Journal of Heat and Mass Transfer 89 (2015) 186192

400

400
350

A1

A2

ACP/HFC-134a

Hst

ACF/HFC-134a
ACP/HFC-410a

350

250

ACF/HFC-410a

200
150
300

100
50

Cva/W0

0
-50

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Hst, kJ/kg

A1, A2 and Hst, kJ/kg

300

250

-100
Fig. 7. A1, A2 and Hst with non-ideal gas consideration of ACP/HFC-410a.

200

350
150

300

A1

A2

Hst

A1, A2 and Hst, kJ/kg

250
200

100
0

150

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Cva/W0

100
Fig. 10. Hst of non-ideal gas in kJ/kg as a function of relative load.

Cva/W0

50
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

900

1.1

-50

ACP/HFC-134a

800

-100

ACF/HFC-134a

700

vv, cm3/g

400

ACP/HFC-410a

600

Fig. 8. A1, A2 and Hst with non-ideal gas consideration of ACF/HFC-134a.

ACF/HFC-410a

500
400
300

350

A1

A2

Hst

200

A1, A2 and Hst, kJ/kg

300

100

250

0
0

200

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

P/P0

150
Fig. 11. Gas phase specic volume with respect to relative adsorption pressure.

100
50

Cva/W0

0
-50

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.1

-100
Fig. 9. A1, A2 and Hst with non-ideal gas consideration of ACF/HFC-410a.

where Hst0 in kJ/kg is the isosteric heat at zero load and h is a tting
parameter. Values of Hst0 and h have been determined for the studied working pairs and are furnished in Table 3.
In order to reveal the effect of the proposed formula, a simulation code has been developed using Eq. (29) to govern the performance of an adsorption cooling system. Figs. 1215 show the
performance of the simulated system using the traditional isosteric
heat (Eq. (5)) versus the proposed formula (Eq. (27)). Fig. 12 shows
the temperature proles of various components of the adsorption
cooling system. This gure indicates that adoption of Eq. (29)
instead of Eq. (5) the requirement of cycle time to achieve same
temperature prolonged. Fig. 13 shows the inuence of regeneration

Table 3
Values of Hst0 and h.
Adsorbent/adsorbate

Hst0 (kJ/kg)

ACP/HFC-134a
ACF/HFC-134a
ACP/HFC-410a
ACF/HFC-410a

297.06
333.12
365.43
383.98

0.835
1.01
0.862
0.85

temperature on cycle time at different evaporator temperatures of

ACP/HFC-134a adsorption cooling system for both ideal and
non-ideal gas considerations.
The effect of employing Eq. (29) on coefcient of performance
(COP) and specic cooling power (SCP) of the simulated system
has been presented in Figs. 14 and 15, respectively. These gures
show that the use of isosteric heat of adsorption with non-ideal
gases assumption decreases the theoretical COP and SCP at different evaporator and regeneration temperatures.
The increase in cycle time and the decrease in COP and SCP are
for the reason that the Hst of Eq. (29) is always higher than that of

191

A.A. Askalany, B.B. Saha / International Journal of Heat and Mass Transfer 89 (2015) 186192

0.4

375

0.35

Regeneration Temp.

355

Bed Temp. non-ideal gas

345

Bed Temp. ideal gas

335

Cooling Temp.

0.3

Chilled water non-ideal gas

325

Chilled water ideal gas

315

SCP, kW/kg

Temperature, K

365

0.25
0.2
0.15

305

0.1

295

0.05

285
275
0

200

400

600

800

1000

Time, s

Fig. 12. Temperature proles of simulated ACP/HFC-134a adsorption cooing system

with Hst for ideal and non-ideal gas considerations.

0
345

350

355
360
365
Regeneration temperature, K

370

Fig. 15. Effect of regeneration temperature on SCP at different evaporator temperatures of ACP/HFC-134a adsorption cooling system for ideal and non-ideal gas
considerations. Legend: solid lines Hst of Eq. (29); dashed lines Hst of Eq. (5)
symbols; s evaporator temperature 285 K; D evaporator temperature 277 K,
and h evaporator temperature 265 K.

1100

Eq. (5) at any pressure and loading conditions due to the requirement of prolonged desorption time in case of the proposed Hst.

1000

Cycle time, s

900

5. Conclusions

800
700
600
500
400
345

350

355

360

365

370

Regeneration temperature, K
Fig. 13. Effect of regeneration temperature on cycle time at different evaporator
temperatures of ACP/HFC-134a adsorption cooling system for ideal and non-ideal
gas considerations. Legend: solid lines Hst of Eq. (29); dashed lines Hst of Eq. (5)
symbols; s evaporator temperature 285 K; D evaporator temperature 277 K,
and h evaporator temperature 265 K.

A mathematical framework for the derivation for isosteric heat

of adsorption for non-ideal gases has been proposed. The resulting
isosteric heat equation has been applied on experimental adsorption isotherms data of four different activated carbon based adsorbent/refrigerant pairs. The effect of using the proposed isosteric
heat equation has been studied in the simulated performance of
adsorption cooling cycle employing ACP/HFC-134a pair. The
adsorption system performance results have been compared using
the innovative isosteric heat of adsorption equation and conventional isosteric heat of adsorption equation. The simulated results
show that the COP and SCP of the adsorption system employing
the newly developed isosteric heat of adsorption have been
increased in comparison with those of employing the conventional
isosteric heat of adsorption data.
Conict of interest
None declared.

0.4
0.35

References

0.3

COP

0.25
0.2
0.15
0.1
0.05
0
345

350

355

360

365

370

Regeneration temperature, K
Fig. 14. Effect of regeneration temperature on COP at different evaporator
temperatures of ACP/HFC-134a adsorption cooling system for ideal and non-ideal
gas considerations. Legend: solid lines Hst of Eq. (29); dashed lines Hst of Eq. (5),
symbols; s evaporator temperature 285 K; D evaporator temperature 277 K,
and h evaporator temperature 265 K.

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