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Correlation Between Fluctuation and Dissipation in the Case of the Adsorption of Acetone and Ethanol

Correlation Between Fluctuation and Dissipation in the Case of the Adsorption of Acetone and Ethanol by the Activated Carbon

F. Mhiri a and A. Jemni b

a Institut Pre´paratoire aux Etudes d’Inge´nieurs de Monastir, Rue Inb El Jazzar, 5019 Monastir, Tunisie; Ribat005@yahoo.fr (for correspondence) b Ecole Nationale d’Inge´nieurs de Monastir, Rue Inb El Jazzar, 5019 Monastir, Tunisie

Published online 23 July 2010 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.10475

The previous studies have shown that the gas adsorption process in a microporous solid is due to three phenomena: the direct adsorption (transporta- tion phenomenon), the diffusion, and the fluctua- tions of the energy and the adsorbed matter quantity. These studies assume that the links between the differ- ent fluctuations are constant. In this article, we pro- pose a new model of theses links based on the proba- bilistic-statistical properties of correlations and on the micropore filling theory. Currently, there is no result leading to the establishment of the general form of the correlation which is based essentially on the exist- ing general theory of the actual statistical probability, the experiment and the scientific logic. A good agree- ment between the theoretical results and the measure- ments is obtained, which confirms the efficiency of

the proposed model. 2010 American Institute of Chemi- cal Engineers Environ Prog, 30: 294–302, 2011

Keywords: kinetics, adsorption, microporous solid, fluctuation, Fik’s

INTRODUCTION

The development of the industrial applications of the adsorption phenomenon, requires a good knowl- edge of the transfers of heat and mass in the adsorb- ent mediums [1]. Consequently, the determination of the parameters which control these transfers and

2010 American Institute of Chemical Engineers

especially the adsorption kinetics have a great interest [2] in several fields: Chemistry, Biology, Pharmaco- chemistry, applications in the environment and the separation of the molecules (molecular sieves). Generally, the adsorption speed is controlled by the adsorbed mass and the resistance to the heat transfer instead of the adsorption intrinsic kinetics [3]. A direct measurement on an adsorbent sample ena- bles to plot some characteristics which provide an easy method for the adsorption kinetic study. Never- theless, the interpretation of many data shows some unavoidable difficulties. In fact, there are many differ- ent resistances to the transfer of mass and heat, which limits the adsorption speed. The influence of the thermal resistance on the kinetic has been studied by Valentina et al. [4]. Since 1950 many theories of the adsorption kinetics have been developed. Some lead to equations barely-applicable as they integrate many factors which depend on the physico-chemical properties of the adsorbents and adsorbats [3]. Others are applied only by concentration intervals [5]. In lit- erature, there are some empirical models the parame- ters of which are not explicitly defined from a physi- cal point of view [5, 6]. Moreover, in these proposed models, the number of constants experimentally determined is generally greater than three [7–11]. The irreversibility of the adsorption and the de- sorption phenomena have been proved by many authors [12]. It has been shown that the irreversibility depends on the temperatures and to reach the ther-

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Environmental Progress & Sustainable Energy (Vol.30, No.3) DOI 10.1002/ep

mal equilibrium 1.5 h is required for each measure- ment [13–17]. The needed time to reach this equilib- rium ensures the existence of fluctuations during the adsorption. Besides, in the same study the variations of the differential heat with respect to the adsorbed matter quantity illustrate the fluctuations of this heat. The fluctuation phenomena have been observed by other authors [18] who introduce the correction func- tion in the equation of Dubinin-Astakhov and on the adsorption and desorption energies. These fluctua- tions or the adsorption oscillations are explained and confirmed by the theory of the thermodynamics of systems out of equilibrium [19–21] by incorporating the Onsager theorem [22] or the fluctuation dissipa- tion theorem [23, 24]. These theorems have been used by Mhiri et al. [25] and Mhiri and Jemni [26]. Some researchers have tried to linearize the plots of the adsorption kinetics [27]. However, this assump- tion, deduced from the chemical kinetics [28], yields a good approximation only in reduced intervals of the plots. From a microscopic point of view, the experi- ment shows that the adsorption of a gas in a micro- porous solid is due to two phenomena: the transport and the diffusion [15, 16, 29] which introduces another complexity in the study of the adsorption kinetics. In fact, from the study of Brownien’s move- ment (Langevin equation) we show that both phe- nomena don’t have the same speed. The adsorption kinetic approach from Fick’s law [30] needs the modification of this law and the con- sideration of the fluctuation. The authors using Fick’s law without considering the fluctuation and the dif- ference between the transport and the diffusion have to define up to five diffusivities [11]. A recent study based only on mathematical results [31] proposes a modification of the Fick’s law. This study doesn’t pro- pose any experimental approach and doesn’t con- sider the heat and mass fluctuations either.

THEORETICAL STUDY

General Theoretical Study The adsorption of a gas in a microporous solid is a matter transfer with a movement quantity from one environment to another. This property is the feature of a transportation phenomenon [32]. In the ideal case, the main physical aspects of these phenomena are described by the Fick’s law. Generally, these phe- nomena obey some equations more complicated than Fick’s law which can be considered only a first approximation. For example, the diffusion with a chemical reaction (production and dissipation of mol- ecules) or the balance in a nuclear thermal reactor, yield equations more intricate than those of Fick’s

[32].

The transportation phenomenon which occurs between the ambient gas around the microporous solid and the solid itself is followed by a diffusion inside the solid in the direction of the decreasing concentrations and tends to uniform the molecular distribution of the diffusing substance in all the allowed space. Thus, there is a tendency that makes the diffusion take place. This tendency has to be con-

makes the diffusion take place. This tendency has to be con- Figure 1. Physical model 1:

Figure 1. Physical model 1: direct adsorption (trans- portation phenomenon); 2: diffusion; 3: fluctuation.

sidered in a statistical or microscopic way as it may have some fluctuations which are created for short periods of time due to the molecular flow reverse in some places [32]. Moreover, the adsorption of a gas in a microporous solid is an exothermic phenomenon as the overheating of a solid region may cause the transfer of a matter quantity to the less hot region. Both remarks are responsible for the fluctuation of the adsorbed quantity in the elementary volume of the microporous solid. In conclusion, in a microscopic way, the adsorp- tion process in elementary volume results from the succession of three phenomena which occur during the time: the direct adsorption of the exterior to the adsorbant (transportation phenomenon), the matter diffusion inside the adsorbent, and the exchange of the adsorbed matter due to fluctuation (see Figure 1). The differential equation which describes the adsorbed quantity during the time results from a mat- ter balance in an adsorbent elementary volume [25,

26].

The adorbat accumulation is equal to the gain per diffusion inside the adsorbent plus the quantity directly adsorbed from out side plus the matter exchange due to fluctuations:

@nðr; tÞ

@t

¼ D Dnðr; tÞ þ Aðr; tÞ þ Bðr; tÞ

(1)

In a spherical symmetry case and from [25], this equation is written as:

@nðr; tÞ

@t

¼ D Dnðr; tÞ þ b nðr; tÞ þ ZðtÞRðrÞ

(2)

where A(r,t) 5 b n(r,t) with b a constant in the isobar case as it depends only on the pressure and on the adsorbent’s active surface [25]. Equation 2 has been solved using the variable separation method, the model chosen for B(r,t) is Z(t) R (r) where Z(t) is the function which describes the deep link between

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the fluctuations and the dissipations of the matter and energy and R(r) is the function that describes the matter distribution with respect to coordinates. The solution of Eq. 2 with the following limit conditions

nðr; 0Þ ¼ n 0 ;

is given by

nðr c ; 1Þ ¼

@n

n 1

r¼0

@r

¼ 0

and

nðr c ; tÞ ¼ n 0

0

1

nðr c ; tÞ ¼ 4p YðtÞ X

j¼1

ðiaÞ j

2 j ðj þ 1Þ! e ia ðj!Þðj þ 1Þ

j

3 X

g¼0

ð 2iaÞ j g 1 g!½ðj gÞ! 2 ðj

g

þ 1Þ r j gþ3

c

þ j g þ 3 ia

c

ðj g þ 3Þðj g þ 2Þ

r j gþ1

ðiaÞ 2 r c þ 2ðj g þ 3Þ!

c

ðiaÞ j gþ3

r j gþ2

þ

þ þ ðj g þ 3Þ!

ðiaÞ j gþ2

ð3Þ

A first order development (j 5 1) in the case of Z(t) is constant gives:

1 e x 2 t 3

¼

d3

3

n

1

a r 4 þ

9

2

c

a

2

4

r

c

2a r

9

r

2a

2

c

2

18

2 18

c

a

3

þ

18

a

3

nðr c ;tÞ

3

2 r

3

2

cos ð ar

1 e

x

2

Þ

c

t

3

r

c

9

a

2

r

c

3

c

9

a 2 r c

sin ar

ð

cos ð ar

c

c

Þ þ id3

Þ

sin ð ar

c

Þ

This

expression

has

been

t

 

(4)

designed

by

other

authors in the form 1 H e k with k the relaxation time and H is a constant [12] when Z(t) isn’t constant,

the solution is:

nðr c ;tÞ

3

2 r

9

a 2 r c

¼YðtÞ3

3

n

1

a r 4 þ

9

2

a

2

r

c

4

c

2a r

9

r

2a

2

c

18

2

c

þ

3

a

18

a

3

3

c

sin ar

ð

ð

cos ar

cos ð ar

c

Þ

c

c

Þ þi YðtÞ

Þ

3

2

3

r

c

9

a

2

r

c

sin ð ar

c

Þ

(5)

where Y(t) is given by the differential equation [25,

26]:

dY

dt

þ

x 2 Y ¼ ZðtÞ

(6)

With x 2 a positive constant in the isotherm case. In this study, we will model Z(t) for two purposes:

Provide the general solution of Eq. 2 without any approximation;

Minimize the computing errors Equation 6 is a first order linear differential equa- tion with constant coefficients the solution of which is [33]:

YðtÞ ¼

t

Yðt 0 Þe x 2 ðt t 0 Þ þ e x 2 ðt t 0 Þ Z

t 0

ZðuÞe x 2 ðt 0 uÞ du

(7)

The function Z(t) can be a general form and with- out any additional hypothesis, it is difficult to precise the properties of the system described by such an application. Therefore, we have to assume some hy- pothesis for which the representation may have more

flexible mathematical forms. Equation 7 is a physi-

cally-acceptable solution of Eq. 6 if Y(t) has to be fi- nite for each t and has to converge when t goes to in-

finity. With Eq. 7, we add the following hypothesis: the interactions energy fluctuation-dissipation; matter fluctuation-energy fluctuation, and energy dissipation- matter fluctuation vary linearly. For t 0 5 0, Eq. 7 becomes:

t

YðtÞ ¼ Yð0Þe x 2 t þ e x 2 t Z ZðuÞe x 2 u du

0

Which satisfies the causality.

(8)

Correlation Z(t) To have the solution given by Eq. 8, one has to determine Z(t). In this article Z(t) will be considered as the dependence factor between the fluctuation

and the dissipation. To determine this factor, we have to answer the following questions:

How to determine correctly the sense of the stud- ied dependence? Does it exist a dependence between the studied variables and how do we measure the degree of such a link? How to obtain the correct form of the depend-

ence Z on n or t which enables in the given case, to quantify the influence of Z on n and to formu-

late the imposed conclusions? [34].

The study by applying a statistical probabilistic one described here has confirmed the hypothesis of an influence of the fluctuations on the adsorption speed. In the isotherm case, Z is function of n and n is function of t so that Z 5 Z(t), the function Z defines the deep link between fluctuation of matter and energy dissipation. This implies that n(t) is a ran- dom variable as many noncontrollable phenomena may affect its values. Z is a random variable too and since Z is function of n, the problem consists in determining the correlation between Z and the time t. The deduction of the corresponding empirical equation which links both variables can be split into two steps:

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Establishment of the general form of the sought functional relation; Computing of parameter estimates of the equation which fit as most as possible the experience data. It’s to be noted that the first step is less familiar than the second as no resolution methods are avail- able in the literature [34]. The most used and studied dependences are the linear regression and parabolic regression. In our case, these regressions don’t provide the wished pre- cision degree. So, we have to try other dependence forms such as hyperbolic, exponential, or of power. In the case of the study of the adsorption kinetics and for the dependences between the fluctuation and the dissipation, these dependences can be formulated as linear ones via the variable change. The depend- ence which describes our experiments is the expo- nential one.

Study of the Function Z(t)

This function expresses the deep link between the fluctuation and the energy and matter dissipation, it isn’t measurable because of its random behavior. Moreover, there is no mathematical study which ena- bles to determine its expression. This function is mathematically-inaccessible. Only some properties can be described from the experiment. In the iso- therm case, adsorption Z(t) satisfies the following properties:

It depends on the adsorbed molecule number n(rc,t), on the volume available at time instant t and on the temperature. It is finite for any quantity of the adsorbed matter. Its first derivative is finite for any adsorbed matter quantity. When the system goes to saturation, this function tends to be a constant. There’s no volume avail- able for the matter fluctuation and the heat diffu- sion permanent regime is established. Initially, when the microporous solid is empty of adsorbat, this function must be null. If there’s no adsorbat in the adsorbent, there’s no fluctuation. The function Z 5 Z(n) and n 5 n(rc,t) are func- tions of time, we can express Z as a function of time Z 5 Z(t). Moreover, our study handles the kinetics and it is irrelevant to express all functions with respect to the same variables. Mathematically, in the isotherm case these properties are:

The limit of Z(t) exists for any value of t. The limit of the first derivative exists for any value of t. It goes to a constant value once t goes to infinity and its first derivative goes to zero. Initially (t 5 0) this function has to be null and its first derivative should be finite. From these mathematical properties, the form Z 5 Z(t) in the isotherm case is given by Figure 2. The most effective interaction on the adsorption speed are: the interaction between the energy dissi- pation and the matter fluctuation and the interaction between the matter fluctuation and the energy fluctu- ation. In such a case, the function Z(t) can be written

ation. In such a case, the function Z ( t ) can be written Figure 2.

Figure 2. Theoretical evolution of Z correlation with times in isotherm case.

as: Z(t) 5 h(t) 1 g(t) where h(t) is the function that characterizes the link between the energy dissipation and the matter fluctuation and g(t) characterizes the link between the matter fluctuation and energy fluc- tuation.

Study of h(t)

At the start of the adsorption (t small), the avail- able volume for the adsorbed molecules is big, which enables an easy movement of molecules: the matter fluctuation is important. However, at the end of adsorption (t big), the adsorbent solid is close to sat- uration and the volume available for the free moving of molecules is so small that the matter fluctuation is near zero, which enables us to write h(t) as:

hðtÞ ¼ Eð1 e s Þ where ð1 e s Þ characterizes the mean values of matter fluctuation with respect to time and E is a constant (in isotherm case) which characterizes the mean dissipation of energy.

t

t

Study of g(t)

In the beginning of the adsorption, the energy fluctuation has to be important because of the high number of hits between the molecules of the adsor- bat and the adsorbed molecules and the microporous solid edges since the available volume is relatively big and the molecules have a high degree of move- ment freedom. Once the solid moicropores are filled, the available volume for the movement of molecules decreases as well as their free movement degree, which leads to a reduction of the energy fluctuation. Moreover, the heat conduction by the microporous solid tends to the steady state, which enables to char- acterize the energy fluctuation by the function e s . In the isotherm case, the mean value of the fluctuation

t

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Figure 3. Representative diagram of the installation utilized for the experimental tracing of isotherms. 1:

Figure 3. Representative diagram of the installation utilized for the experimental tracing of isotherms. 1: filter; 2:

Mass volumetric regulator; 3: Wash-bottle; 4: fluidized bed reactor; 5: Conical float rotameter; 6: Exchanger with cool water; 7: Detector with ionization of flame; 8: Thermocouple K.

Table 1. Characterization of activated carbon NC 60.

Origin

Coconut

Oxidation temperature

2038C

Activation

CO 2 1H 2 O (a` 9008C) 1240 m 2 g 21 0.55 cm g 21

Volumic mass

1.4 g cm 23 0.8–0.9 J g 21 K 21

Specific surface

Specific heat

Porous volume

of the matter due to the energy fluctuation is F(12e 2x 2 t) (see Eq. 4) where (12e 2x 2 t) characterizes the adsorbed quantity during the time and F the per- centage of molecules whose positions are fluctuated because of the energy fluctuation. The function Z(t) is written as:

ZðtÞ ¼ Fe s ð1 e x 2 t Þ þ Eð1 e s Þ

t

t

(9)

By hypothesis, the interactions between the differ- ent fluctuations are linear and from Eq. 8, the func- tion Y(t) is written as the product of two functions as:

YðtÞ ¼ Cð1 e s Þð1 e x 2 t Þ

t

(10)

The term (12e 2x 2 t) describing the links between the matter and energy dissipations and fluctuation

and from previous reasoning has an effect only on small concentrations. This result can be proved theo- retically (Annex I). We prove that this term is differ-

ent from unity if

ponential terms in the expression of Y(t) is familiar in

adsorption kinetic theories [5, 35].

h 2 1 . The product of the two ex-

nðt;TÞ

n 1 ðTÞ

Table 2. Values of speed fluidization according to the temperature.

T 5 308C

T 5 508C

T 5 758C

T 5 1008C

0.23

0.210

0.195

0.18

EXPERIMENTAL STUDY

The measurements are collected at high National School of industrial technique and mines of Nantes (France) within the Department of energetic and environment Engineering.

Experimental Condition The measurements of the adsorbed mass are real- ized in a fluidized bed in isotherm conditions (see Figure 3). The used adsorbent is the activated carbon PIC AN C60, the physicochemical characteristics are

presented in Table 1. The grain radius ranges from 0.3 to 0.6 mm; the bed mass is 0.3 kg; the bed height is 0.12 m and the reactor diameter is 100 mm. All the

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Environmental Progress & Sustainable Energy (Vol.30, No.3) DOI 10.1002/ep

Table 3. Experimental values of constants from Equations (5) and (10).

C

s(S)

x 2 (s 21 ) ‘‘Mhiri F. Jemni A (2010)’’

a (m 21 ) ‘‘Mhiri F. Jemni A (2010)’’

T(8C)

Ethanol

Acetone

Ethanol

Acetone

Ethanol

Acetone

Ethanol

Acetone

30

10.418

9.721

80.645

93.750

9.059 3 10 24 1.499 3 10 23 2.700 3 10 23 4.666 3 10 23

1.195 3 10 23 1.556 3 10 23 2.117 3 10 23 2.819 3 10 23

0.192

0.191

50

12.000

9.550

52.631

78.947

0.247

0.218

75

10.279

9.454

39.443

41.666

0.330

0.255

100

10.540

9.000

39.473

37.500

0.435

0.295

100 10.540 9.000 39.473 37.500 0.435 0.295 Figure 4. Evolution of relative quantity of ethanol

Figure 4. Evolution of relative quantity of ethanol adsorbed in activated-carbon (—) theoretical curves (Eq. 7), () experimental curves, 1 experimental points; 1 308C, ^: 50, O: 75 and D at 100.

tests are carried out with a solvent concentration at the input of 30 gm 23 . All tests performed at a U 0 speed 5 2 U mf . The speed minimal of fluidization measured according to the temperature U mf is given in Table 2. The activated carbon particles are washed with distilled water then placed in a drying oven at 1058C during 24 h before fluidizing them to wash them and remove the fine impurities. The reactor has been dimensioned by taking into account the physical properties and the minimal speed of the particle fluidization of the activated car- bon. The tubular oven with 0.81-W power allows to heat the gas at the input for an isotherm functioning. An air temperature control is achieved in a wind box of the column by a PID generator (Eurotherm 2132) acting on the uphill power. The cold water exchanger enables to evacuate the yielded energy during the adsorption. It’s composed of 18 copper spirals and a PID regulator which allows to regulate the water flow depending on the temperature in the activated car- bon bed. The steam saturated air flow is generated

car- bon bed. The steam saturated air flow is generated Figure 5. Evolution of relative quantity

Figure 5. Evolution of relative quantity of acetone adsorbed in activated-carbon (—) theoretical curves (Eq. 7), () experimental curves, 1 experimental points; 1 308C, ^: 50, O: 75 and D at 100.

by the pinching of a dry air flux in a liquid solvent. The pinching system is thermostat to avoid the con- centration fluctuation of the saturation of the ambient temperature. This flux saturated in the solvent is diluted in a wind box by a pure air current. By considering the variation of the partial molar flow of the adsorbate between the column input and output equivalent to the adsorbed adsorbate quantity per unit of time, we can write the following relation:

Input 2 output 5 accumulation:

dn

dt

and

G 0 ðX 0 XÞ ¼ M bed

With X ¼

x x

1

We deduce n

x ¼ C M 0

n

¼ X 0 G 0

M bed

t¼t f

Z

t¼0

ð1 X 0 Þdt

X

RT

P

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By integrating the previous equation we obtain the value of n.

APPLICATION OF THE THEORETICAL MODEL

To experimentally illustrate the proposed theoretical model we have exploited the real part of Eq. 5 where Y(t) is replaced by its expression given in Eq. 10. On the basis of the conjugate gradient identifica- tion technique, we have estimated the constants C and s of expression Eq. 10 for each isotherm. The computing results of constants C and s are summar- ized in Table 3 and the evolution of the experimental and theoretical adsorbed quantities are plotted in Fig- ures 4 and 5.

CONCLUSION

In this article, we have proposed a theoretical approach of the correlation between matter and energy fluctuations and dissipations. This approach as well as its theoretical limit (annex I) are confirmed experimentally. The proposed approach is a continuation of the previous works where an adsorption kinetic theory has been developed. The main advantage of this theory is that it takes into account the nonhomogene- ity of the systems and the fluctuation observed exper- imentally. This theory takes into account all the internal sys- tem values because of the use of the statistical theory and the random function while solving the estab- lished differential equation. From the previous studies and the present one, we can affirm that the adsorption of a gas in a micropo- rous solid is the result of three phenomena: a trans- portation phenomenon followed by a diffusion phe- nomenon and both phenomena are accompanied by a fluctuation. In spite of the assumption that the adsorption is iso- bar, the concordance between the theory and the experiment is very satisfactory. This is due to the fact that the studied adsorptions are free and not forced; the pressure variations are very small and can be neglected. The relative error between practice and theory is less than 10% at any instant over 10 s. This result is expected as the initial speed is very high and the measurements during the time interval [0, 10 s] are less assured.

Annex I In statistical thermodynamics, the entropy is defined as a value which measures the degree of a system dis- order in a microscopic level. If X is the number of microstates, the cell number of the corresponding space at a thermodynamical state; the Boltzman postu- late, to which Plank has given its final form, establishes the link between the entropy and X as S 5 f(X) where f is a universal function. The unique solution of this equation is f(X) 5 K ln X, so that:

S

¼ K ln X

In the case of the adsorption of a gas in a micropo- rous solid, X is the number of possibilities to arrange

the adsorbed molecules over the total number of the receiver sites n 1 ðTÞ:

X ¼

n 1 ðTÞ!

nðt; TÞ!ðn 1 ðT Þ nðt; T ÞÞ!

With Stirling formula, we have

S ¼ K½n 1 ðT Þ lnðn 1 ðT ÞÞ nðt;

T Þ lnðnðt; T ÞÞ

ðn 1 ðT Þ nðt; T ÞÞ lnðn 1 ðT Þ nðt; T ÞÞ

The maximum of the entropy is :

@ð

S K Þ

@n

¼ 0 ) lnðnðt; T ÞÞ þ lnðn 1 ðTÞ

nðt; T ÞÞ ¼ 0 ) nðt; T Þ ¼ n 1 ðTÞ

2

has a maximum for

nðt; TÞ ¼ n 1 ðTÞ , the entropy S decreases as we have a

f(n)

The

function

2

S

5

negative temperature. From this study the term ð1 e Þ which links the fluctuations to dissipations has an effect once nðt;TÞ h

.

If this ratio equals 2 , the term ð1 e s Þ is set to unity.

t

s

t

1

n 1 ðTÞ

2

1

NOMENCLATURE

A accumulation due to direct adsorption (mol kg 21 s 21 )

1

b relaxation time relative to pressure in

isobar condition (s)

integrate constant mass concentration of the solvent at the column input (g m 23 )

D diffusion constant of micro pores

C 0

C

(m 2 s 21 )

model flow of inert gas (mol s 21 )

G

I Complex number i 2 5 21

K proportionality constant

m

0

M bed

mass of adsorbed particles (kg mol 21 ) mass of activated carbon bed (kg)

M molar mass of solvent (g mol 21 )

number of adsorbed molecules by vol- ume unit (mol m 23 ) Number of adsorbed molecules in (mol kg 21 ) by spherical volume of r c radius at time t average density of particles in point at time t (mol kg 21 )

n(r,t)

P pressure (Pa), assumed to be constant

R perfect gas constant

r instantaneous particle position in spheri-

cal coordinates (m) radius of spherical grain of adsorbent

(m)

r c

t time (s)

T temperature (8K)

relaxation time relative to temperature

n(r c ,t)

N

1

x

X 0

(s)

the partial molar fraction of initial sol-

vent in the air

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Environmental Progress & Sustainable Energy (Vol.30, No.3) DOI 10.1002/ep

X the partial molar fraction of solvent at time instant t

D Laplatian operator

a integrate constant (m 21 )

Index

summation index

g summation index

j

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