00 positive Bewertungen00 negative Bewertungen

13 Ansichten9 SeitenJun 06, 2013

© Attribution Non-Commercial (BY-NC)

PDF, TXT oder online auf Scribd lesen

Attribution Non-Commercial (BY-NC)

Als PDF, TXT **herunterladen** oder online auf Scribd lesen

13 Ansichten

00 positive Bewertungen00 negative Bewertungen

Attribution Non-Commercial (BY-NC)

Als PDF, TXT **herunterladen** oder online auf Scribd lesen

Sie sind auf Seite 1von 9

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

_{t}_{h}_{e} _{p}_{r}_{o}_{p}_{o}_{s}_{e}_{d} _{m}_{o}_{d}_{e}_{l}_{.} 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-

294 October 2011

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-

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

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

October 2011

295

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} _{ð}_{j} _{þ} _{1}_{Þ}_{!} e ^{} ^{i}^{a} 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

_{ð}_{i}_{a}_{Þ} j gþ3

_{r} j gþ2

_{þ}

þ þ ^{ð}^{j} ^{} ^{g} ^{þ} ^{3}^{Þ}^{!}

_{ð}_{i}_{a}_{Þ} j gþ2

^{ð}^{3}^{Þ}

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

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} ^{ð}^{t} ^{} ^{t} ^{0} ^{Þ} þ e ^{} ^{x} ^{2} ^{ð}^{t} ^{} ^{t} ^{0} ^{Þ} Z

t 0

ZðuÞe ^{} ^{x} ^{2} ^{ð}^{t} 0 ^{} ^{u}^{Þ} 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:

296 October 2011

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

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

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

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

October 2011

297

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 |
Volumic mass |
1.4 g cm |

Speciﬁc surface |
Speciﬁc heat |
||

Porous volume |
— |

of the matter due to the energy ﬂuctuation is F(12e ^{2}^{x} ^{2} t) (see Eq. 4) where (12e ^{2}^{x} ^{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 ^{2}^{x} ^{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

298 October 2011

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 ^{2}^{1} ) ‘‘Mhiri F. Jemni A (2010)’’

a (m ^{2}^{1} ) ‘‘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 |
1.195 3 10 |
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 |

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 ^{2}^{3} . All tests performed at a U _{0} speed 5 2 U _{m}_{f} . The speed minimal of ﬂuidization measured according to the temperature U _{m}_{f} 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

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 _{b}_{e}_{d}

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

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

October 2011

299

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} ^{ð}^{T}^{Þ}

2

has a maximum for

nðt; TÞ ¼ ^{n} ^{1} ^{ð}^{T}^{Þ} , 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 ^{n}^{ð}^{t}^{;}^{T}^{Þ} 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 ^{2}^{1} s ^{2}^{1} )

1

_{b} relaxation time relative to pressure in

isobar condition (s)

integrate constant mass concentration of the solvent at the column input (g m ^{2}^{3} )

D diffusion constant of micro pores

C _{0}

C

(m ^{2} _{s} ^{2}^{1} )

model ﬂow of inert gas (mol s ^{2}^{1} )

G

I Complex number i ^{2} 5 21

K proportionality constant

m

0

M bed

mass of adsorbed particles (kg mol ^{2}^{1} ) mass of activated carbon bed (kg)

M molar mass of solvent (g mol ^{2}^{1} )

number of adsorbed molecules by vol- ume unit (mol m ^{2}^{3} ) Number of adsorbed molecules in (mol kg ^{2}^{1} ) by spherical volume of r _{c} radius at time t average density of particles in point at time t (mol kg ^{2}^{1} )

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

300 October 2011

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 ^{2}^{1} )

Index

summation index

g summation index

j

LITERATURE CITED

1. Vinod, K.G., Suresh, K.S., & Dinesh, M. (1997). Equilibrium uptake, sorption dynamics, process optimization, and column operations for the re- moval and recovery of malachite green from wastewater using activated carbon and activated slag, Industrial and Engineering Chemistry Research, 36, 2207–2218.

2. Vinod, K.G., Srivastava, S.K., & Renu, T. (2002). Design parameters for the treatment of phenolic wastes by carbon columns (obtained from fertilizer waste material), Water Research, 34, 1543–1550.

3. Douglas, M.R. (1984). Principles of adsorption and adsorption processes (Chapter 6), New York:

Wiley.

4. Valentina, V.P., Ruslan, H.M., & Jiri, H. (1999). Inﬂuence of heat transfer on the kinetic process involved during the adsorption of soluble organic substances on to porous polymeric sorbents, Adsoption Science and Technology, 17, 161–171.

5. McEwen, J.-S., Payne, S.H., Kreuzer, H.J., Kinne, M., Denecke, R., & Steinru¨ck, H.P. (2003). Adsorption and desorption of CO on Pt(111):

A comprehensive analysis, Surface Science, 545,

47–69.

6. Javier Rivas, F., Fernando, B., Olga, G., Benito, A., & Fatima, C. (2003). Stabilized leachates:

Ozone-activated carbon treatment and kinetics,

Water Research, 37, 4823–4834.

7. Nitin, K., Alexander, C., & Charles, M. (2003). Measurement of the kinetic rate constants for the adsorption of superspreading trisiloxanes to an air/aqueous interface and the relevance of these measurements to the mechanisim of superspread- ing, Journal of Colloid and Interface Science, 267,

272–285.

8. Jingtian, H., Duanling, Y., Qi, K., & Dazhong, S. (2003). Estimation the kinetics parameters for non-speciﬁc adsorption of ﬁbrinogen on quartz surface from the response of an electrode-sepa- rated piezoelectric sensor, Sensors and Actuators

B, 96, 390–398.

9. Fan, X., Parker, D.J., & Smith, M.D. (2003).

Adsorption kinetic of ﬂuoride on low cost materi- als, Water Research, 37, 4929–4937. 10. Mikko, S.L., Petri, A.R., Outi, A., & Krause, I. (2003). Liquid-phase hydrogenation kinetics of isooctenes on Co/Si _{2} , Applied Catalysis A, 259,

73–81.

11. Xiaojun, C., Marc, B.R., & Gregory, D. (2004). Selective transport of CO _{2} , CH _{4} and N _{2} in coals:

Insights from modeling of experimental gas adsorption data, Fuel, 83, 293–303. 12. Budinski-Pet Kovie´, L.J., & Tosie´, T. (2003). Adsorption, desorption and diffusion of extended

objects on a square lattice, Physica A, 329, 350–

356.

13. Terzyk, A.P., & Rychlicki, G. (1999). Calorimetric

investigation of molecular interactions in the ad- sorbate/microporous activated carbon system. Towards the mechanism of adsorption in micro- pores, Adsorption Science and Technology, 17,

323–373.

14. Vinod, K.G., Jain, C.K., Imran, A., Chandra, S., & Agarwal, S. (2001). Removal of lindane and mala- thion from wastewater using bagasse ﬂy ash-a sugar industry waste, Water Research, 36, 1483–

2490.

15. Gupta, V.K., Ali, I., & Saini, V.K. (2004). Re- moval of chlorophenols from wastewater using red mud: An Aluminum industry waste, Envi-

ronmental Science and Technology, 38, 4012–

4018.

16. Gupta, V.K., Suhas, Imran, A., & Saini, V.K. (2004). Removal of rhodamine B, fast green, and methylene blue from wastewater using red mud, an aluminium industry waste, Industrial

and Engineering Chemistry Research, 43, 1740–

1747.

17. Jain, A.K., Gupta, V.K., Bhatnagar, A., & Suhas.

(2003). Utilization of industrial waste products as adsorbents for the removal of dyes, Journal of Hazardous Materials, 101, 31–42.

18. Mhiri, F., Jemni, A., & El golli, S. (1996). Etude de l’e´nergie de de´sorption des substances polaires, Revue ge´ne´rale de thermique, 35, 39–47.

19. Kazymyr, P., Lyubov, P., & Oleg, T. (2000). Oscil- latory adsorption as the determination of the ﬂuc- tuating behaviour of different heterogeneous sys- tems, Adsorption Science and Technology, 18,

15–25.

20. Prigogine, I. (1955). Introduction to thermody- namics of irreversible processes. In C.C. Thomas (Ed.), Springﬁeld, IL.

21. Nicolis, G., & Prigogine, I. (1977). Self-organiza- tion in non equilibrium systems. From dissipative structure to order through ﬂuctuation, New York:

Wiley.

22. Onsager, L. (1931). Reciprocal relations in irre- versible processes, Physique Revue, 38, 2265–

2279.

23. Landau, L., & Lifchitz, E. (1984). Physique The´o- rique-Physique Statistique (p. 420), Paris: Ellipses

(traduit du russe) Edition Mir.

24. Ngoˆ, C., & Ngoˆ, H. (1995). Physique statistique a` l’e´quilibre et hors (2nd Edition, Chapter 13), France: Masson.

25. Mhiri, F., Jemni, A., & Ben Nasrallah, S. (2009). Kinetic adsorption of water and carbon Dioxide in zeolites, Journal of Porous Media, 12, 563–

571.

26. Mhiri, F., & Jemni, A. (2010). Kinetic study for the adsorption of acetone and ethanol on activated

carbon, Journal of Porous Media, 13, 295–305.

27. Anne-Claire, T., Yves, A., & le Cloirec, P. (1999). Selective biosorption of lanthanide (La, Eu, Yb) ions by pseudomonas aeruginosa, Environmental Science and Technology, 33, 489–495.

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

October 2011

301

28. Vinod, K.G., Imran, A., & Vipin, K.S. (2007). Adsorption studies on the removal of vertigo Blue 49 and Orange DNA13 from aqueous solu- tions using carbon slurry developed from a waste material, Journal of Colloid and Interface Science, 315, 87–93.

29. Ajay, K.J., Vinod, K.G., Shubhi, J., & Suhas. (2004). Removal of chlorophenols using industrial wastes, Environmental Science and Technology, 38, 1195–1200.

30. Chavanis, P.-H. (2006). Hamiltonian and Brown- ian systems with long-range interaction: II. Ki- netic equations and stability analysis, Physica A, 361, 81–123.

31. Francisco, J., Valdes-Parada, J., Ochoa-Tapia, A., & Alvarez-Ramirez, J. (2007). Effective medium equation for fractional Fik’s in porous media, Physica A, 373, 339–353.

32. Marcelo, A., & Edward, J.F. (1977). Physique Ge´n- e´rale, Tomme II. Champs et Ondes (Chapter 24), Paris: Inter Editions.

33. Aı¨vazian, S. (1978). Etude statistique des de´pend- ances (2nd Edition; Chapters 2, 4, 5, 6), Moscou:

Editions MIR.

34. Blanc-Lapierre, A., & Picinbono, B. (1981). Fonc- tions ale´atoires (Chapter 4), Paris: Edition Masson.

35. Adamson, A.W. (1990). Physical chemistry of surfa- ces (5th Edition, Chapter 17), New York: Wiley.

302 October 2011

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

## Viel mehr als nur Dokumente.

Entdecken, was Scribd alles zu bieten hat, inklusive Bücher und Hörbücher von großen Verlagen.

Jederzeit kündbar.