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

F. Mhiria and A. Jemnib a ´ paratoire aux Etudes d’Inge ´ nieurs de Monastir, Rue Inb El Jazzar, 5019 Monastir, Institut Pre Tunisie; Ribat005@yahoo.fr (for correspondence) b ´ nieurs de Monastir, Rue Inb El Jazzar, 5019 Monastir, Tunisie Ecole Nationale d’Inge
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 (transportation phenomenon), the diffusion, and the fluctuations of the energy and the adsorbed matter quantity. These studies assume that the links between the different fluctuations are constant. In this article, we propose a new model of theses links based on the probabilistic-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 existing general theory of the actual statistical probability, the experiment and the scientific logic. A good agreement between the theoretical results and the measurements is obtained, which confirms the efficiency of the proposed model. Ó 2010 American Institute of Chemical 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 knowledge of the transfers of heat and mass in the adsorbent mediums [1]. Consequently, the determination of the parameters which control these transfers and
Ó 2010 American Institute of Chemical Engineers

especially the adsorption kinetics have a great interest [2] in several fields: Chemistry, Biology, Pharmacochemistry, 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 enables to plot some characteristics which provide an easy method for the adsorption kinetic study. Nevertheless, the interpretation of many data shows some unavoidable difficulties. In fact, there are many different 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 literature, there are some empirical models the parameters of which are not explicitly defined from a physical 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 desorption 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. Both remarks are responsible for the fluctuation of the adsorbed quantity in the elementary volume of the microporous solid. This study doesn’t propose any experimental approach and doesn’t consider the heat and mass fluctuations either. The needed time to reach this equilibrium ensures the existence of fluctuations during the adsorption. t Þ þ Bðr . from the study of Brownien’s movement (Langevin equation) we show that both phenomena don’t have the same speed. THEORETICAL STUDY Figure 1. 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. Generally. t Þ þ b nðr . the adsorption 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 adsorption kinetic approach from Fick’s law [30] needs the modification of this law and the consideration of the fluctuation. [25] and Mhiri and Jemni [26]. No. t Þ ¼ D Dnðr . The differential equation which describes the adsorbed quantity during the time results from a matter balance in an adsorbent elementary volume [25. t Þ ¼ D Dnðr . this assumption.t) 5 b n(r.1002/ep . 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: @ n ðr . t Þ þ Z ðt ÞR ðr Þ @t (2) where A(r. However. yields a good approximation only in reduced intervals of the plots.t) is Z(t) R (r) where Z(t) is the function which describes the deep link between October 2011 295 Environmental Progress & Sustainable Energy (Vol. the diffusion with a chemical reaction (production and dissipation of molecules) or the balance in a nuclear thermal reactor. From a microscopic point of view. A recent study based only on mathematical results [31] proposes a modification of the Fick’s law. 2: diffusion. In conclusion. and the exchange of the adsorbed matter due to fluctuation (see Figure 1). deduced from the chemical kinetics [28]. the experiment shows that the adsorption of a gas in a microporous solid is due to two phenomena: the transport and the diffusion [15. in the same study the variations of the differential heat with respect to the adsorbed matter quantity illustrate the fluctuations of this heat. 16. Physical model 1: direct adsorption (trans- portation phenomenon). Moreover. the model chosen for B(r. Equation 2 has been solved using the variable separation method. the main physical aspects of these phenomena are described by the Fick’s law. there is a tendency that makes the diffusion take place. These fluctuations 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 dissipation theorem [23. For example. Thus. 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.3) DOI 10.t) with b a constant in the isobar case as it depends only on the pressure and on the adsorbent’s active surface [25]. t Þ @t (1) In a spherical symmetry case and from [25]. Some researchers have tried to linearize the plots of the adsorption kinetics [27]. The fluctuation phenomena have been observed by other authors [18] who introduce the correction function in the equation of Dubinin-Astakhov and on the adsorption and desorption energies. In the ideal case. These theorems have been used by Mhiri et al. 3: fluctuation.30. t Þ þ Aðr . 26]. yield equations more intricate than those of Fick’s [32]. 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. 29] which introduces another complexity in the study of the adsorption kinetics. Besides. This property is the feature of a transportation phenomenon [32]. The authors using Fick’s law without considering the fluctuation and the difference between the transport and the diffusion have to define up to five diffusivities [11]. this equation is written as: @ n ðr . these phenomena obey some equations more complicated than Fick’s law which can be considered only a first approximation. the matter diffusion inside the adsorbent.5 h is required for each measurement [13–17]. in a microscopic way. 24]. This tendency has to be con- 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]. In fact.

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. we will model Z(t) for two purposes: Provide the general solution of Eq. Correlation Z(t) To have the solution given by Eq. 8. the problem consists in determining the correlation between Z and the time t. 26]: dY þ x2 Y ¼ Z ðt Þ dt (6) The function Z(t) can be a general form and without any additional hypothesis. 296 October 2011 Environmental Progress & Sustainable Energy (Vol. 7. the solution is:   nðr c . 0 Þ ¼ n0 . nðrc . In the isotherm case. 6 if Y(t) has to be finite for each t and has to converge when t goes to infinity. The deduction of the corresponding empirical equation which links both variables can be split into two steps: With x2 a positive constant in the isotherm case.1002/ep . No.30. t Þ 9 Àx2 t 3 r À r c cosðar c Þ ¼ d3 1 À e 3 n1 2 c a2      a 4 9 2 18 2 À À r c þ r c À 3 sinðar c Þ þ id3 1 À e Àx t 2 2a a      a 4 9 2 18 3 3 9 r À r þ 3 cosðar c ÞÀ r c À 2 r c sinðar c Þ 2 c 2 a c a3 2 a (4) This expression has been designed by other Àt authors in the form 1 À H e k with k the relaxation time and H is a constant [12] when Z(t) isn’t constant. For t0 5 0. Z is a random variable too and since Z is function of n. This implies that n(t) is a random variable as many noncontrollable phenomena may affect its values. In this article Z(t) will be considered as the dependence factor between the fluctuation and the dissipation. Eq. The study by applying a statistical probabilistic one described here has confirmed the hypothesis of an influence of the fluctuations on the adsorption speed. one has to determine Z(t). In this study. 1Þ ¼   @n ¼ 0 and n1 @ r r ¼0 Minimize the computing errors Equation 6 is a first order linear differential equation with constant coefficients the solution of which is [33]: Àx2 ðt Àt 0 Þ Àx2 ðt Àt 0 Þ Zt t0 nð r c . matter fluctuation-energy fluctuation. t Þ 3 3 9 r À r c cosðar c Þ ¼ Y ðt Þ3 n1 2 c a2    a 4 9 2 18 À À r c þ r c À 3 sinðar c Þ þ i Y ðt Þ 2 2a a      a 4 9 2 18 3 3 9 r À r þ 3 cosðar c ÞÀ r c À 2 r c sinðar c Þ 2 c 2 a c a3 2 a (5) where Y(t) is given by the differential equation [25. 2 without any approximation. t Þ ¼ n00 Y ðt Þ ¼ Y ðt 0 Þe þe Z ðuÞe Àx ðt 0 ÀuÞ d u 2 (7) is given by nðrc . Z is function of n and n is function of t so that Z 5 Z(t). To determine this factor. the function Z defines the deep link between fluctuation of matter and energy dissipation. With Eq. we add the following hypothesis: the interactions energy fluctuation-dissipation. Therefore. we have to assume some hypothesis for which the representation may have more flexible mathematical forms. to quantify the influence of Z on n and to formulate the imposed conclusions? [34]. t Þ ¼ 4p Y ðt Þ ði a Þ e À i a ð j ! Þ ð j þ 1Þ ð j þ 1 Þ ! j ¼1  j X ð À 2 i a Þ j À gÀ 1 j À gþ 3 3 rc 2 g ! ½ ð j À g Þ ! Š ð j À g þ 1 Þ g¼ 0 2j 1 X j þ j Àg þ 3 j Àgþ2 ðj Àg þ 3Þðj Àg þ 2Þ j Àgþ1 rc þ rc ia ðiaÞ2  ð j À g þ 3Þ ! 2ðj Àg þ 3Þ! þ ÁÁÁÁÁÁ þ rc þ ð 3Þ ð i aÞ j À gþ 2 ðiaÞj Àgþ3 A first order development (j 5 1) in the case of Z(t) is constant gives:    3 nðr c . 2 with the following limit conditions n ð r . The solution of Eq. Equation 7 is a physically-acceptable solution of Eq. we have to answer the following questions: À How to determine correctly the sense of the studied dependence? À Does it exist a dependence between the studied variables and how do we measure the degree of such a link? À How to obtain the correct form of the dependence Z on n or t which enables in the given case. it is difficult to precise the properties of the system described by such an application. 7 becomes: Àx 2 t Àx2 t Zt 0 Y ðt Þ ¼ Y ð0Þe þe Z ð uÞ e x u d u 2 (8) Which satisfies the causality. and energy dissipationmatter fluctuation vary linearly.3) DOI 10.

In the isotherm case. If there’s no adsorbat in the adsorbent. No. our study handles the kinetics and it is irrelevant to express all functions with respect to the same variables. Study of g(t) In the beginning of the adsorption. which enables to chart acterize the energy fluctuation by the function eÀs . which leads to a reduction of the energy fluctuation. these dependences can be formulated as linear ones via the variable change. The dependence which describes our experiments is the exponential one. However. À When the system goes to saturation. Moreover. Once the solid moicropores are filled. the available volume for the adsorbed molecules is big. The most effective interaction on the adsorption speed are: the interaction between the energy dissipation and the matter fluctuation and the interaction between the matter fluctuation and the energy fluctuation.t) are functions of time.À Establishment of the general form of the sought functional relation. this function tends to be a constant. Moreover. the available volume for the movement of molecules decreases as well as their free movement degree. Only some properties can be described from the experiment. There’s no volume available for the matter fluctuation and the heat diffusion permanent regime is established. The most used and studied dependences are the linear regression and parabolic regression. it isn’t measurable because of its random behavior. exponential. the heat conduction by the microporous solid tends to the steady state. À Initially (t 5 0) this function has to be null and its first derivative should be finite. Mathematically. or of power. À The limit of the first derivative exists for any value of t.3) DOI 10. Theoretical evolution of Z correlation with times in isotherm case. we have to try other dependence forms such as hyperbolic.t). on the volume available at time instant t and on the temperature. Study of the Function Z(t) This function expresses the deep link between the fluctuation and the energy and matter dissipation. which enables an easy movement of molecules: the matter fluctuation is important. À Its first derivative is finite for any adsorbed matter quantity. From these mathematical properties. these regressions don’t provide the wished precision degree. In the case of the study of the adsorption kinetics and for the dependences between the fluctuation and the dissipation.30. 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 fluctuation. It’s to be noted that the first step is less familiar than the second as no resolution methods are available in the literature [34]. there’s no fluctuation. À It is finite for any quantity of the adsorbed matter. Moreover. the form Z 5 Z(t) in the isotherm case is given by Figure 2. the adsorbent solid is close to saturation and the volume available for the free moving of molecules is so small that the matter fluctuation is near zero. In our case. So. Study of h(t) At the start of the adsorption (t small). the mean value of the fluctuation October 2011 297 Environmental Progress & Sustainable Energy (Vol. this function must be null. the energy fluctuation has to be important because of the high number of hits between the molecules of the adsorbat and the adsorbed molecules and the microporous solid edges since the available volume is relatively big and the molecules have a high degree of movement freedom. À Computing of parameter estimates of the equation which fit as most as possible the experience data. in the isotherm case these properties are: À The limit of Z(t) exists for any value of t. À It goes to a constant value once t goes to infinity and its first derivative goes to zero. This function is mathematically-inaccessible. the function Z(t) can be written Figure 2. which enables us t to write h(t) as: t hðt Þ ¼ E ð1 À eÀs Þ where ð1 À eÀs 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. À Initially. at the end of adsorption (t big). when the microporous solid is empty of adsorbat.1002/ep . In such a case. there is no mathematical study which enables to determine its expression. The function Z 5 Z(n) and n 5 n(rc. In the isotherm case. adsorption Z(t) satisfies the following properties: À It depends on the adsorbed molecule number n(rc. we can express Z as a function of time Z 5 Z(t).

195 T 5 1008C 0. The product of the two exent from unity if n 1 ðT Þ 2 ponential terms in the expression of Y(t) is familiar in adsorption kinetic theories [5. Values of speed fluidization according to the temperature. 35].3 to 0. The function Z(t) is written as: Z ðt Þ ¼ Fe Às ð1 À eÀx t Þ þ E ð1 À e Às Þ t 2 t Table 2.8–0. 1: filter. Characterization of activated carbon NC 60.T Þ 1 h .3 kg.210 T 5 758C 0.30.3) DOI 10. 2: Mass volumetric regulator. 8. We prove that this term is differnðt . 298 October 2011 Environmental Progress & Sustainable Energy (Vol.55 cm g21 Oxidation temperature Volumic mass Specific heat — 2038C 1.1002/ep . the function Y(t) is written as the product of two functions as: Y ðt Þ ¼ C ð1 À e Às Þð1 À e Àx t Þ t 2 2 The measurements are collected at high National School of industrial technique and mines of Nantes (France) within the Department of energetic and environment Engineering. 8: Thermocouple K. T 5 308C 0.4 g cm23 0. The grain radius ranges from 0. 4) where (12e2x t) characterizes the adsorbed quantity during the time and F the percentage of molecules whose positions are fluctuated because of the energy fluctuation. the bed height is 0.6 mm. Origin Activation Specific surface Porous volume Coconut ` 9008C) CO21H2O (a 1240 m2 g21 0. the physicochemical characteristics are presented in Table 1. (10) Experimental Condition The measurements of the adsorbed mass are realized in a fluidized bed in isotherm conditions (see Figure 3). the interactions between the different fluctuations are linear and from Eq.12 m and the reactor diameter is 100 mm.9 J g21 K21 — of the 2 matter due to the energy 2 fluctuation is F(12e2x t) (see Eq. 4: fluidized bed reactor. This result can be proved theoretically (Annex I). Table 1. Representative diagram of the installation utilized for the experimental tracing of isotherms. 5: Conical float rotameter. the bed mass is 0. The used adsorbent is the activated carbon PIC AN C60. 7: Detector with ionization of flame. All the The term (12e2x t) describing the links between the matter and energy dissipations and fluctuation and from previous reasoning has an effect only on small concentrations.23 T 5 508C 0. No. 6: Exchanger with cool water. 3: Wash-bottle.18 (9) EXPERIMENTAL STUDY By hypothesis.Figure 3.

631 39.666 3 3 3 3 10 1023 1023 1023 24 a (m21) ‘‘Mhiri F. 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. Experimental values of constants from Equations (5) and (10). 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.454 9. C T(8C) 30 50 75 100 Ethanol 10.500 x2 (s21) ‘‘Mhiri F.947 41. The speed minimal of fluidization measured according to the temperature Umf is given in Table 2. adsorbed in activated-carbon (—) theoretical curves (Eq. 1 experimental points.330 0. Jemni A (2010)’’ Ethanol 9. The steam saturated air flow is generated by the pinching of a dry air flux in a liquid solvent.81-W power allows to heat the gas at the input for an isotherm functioning.247 0.3) DOI 10. tests are carried out with a solvent concentration at the input of 30 gm23. 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 carbon bed.550 9. An air temperature control is achieved in a wind box of the column by a PID generator (Eurotherm 2132) acting on the uphill power. we can write the following relation: Input 2 output 5 accumulation: G 0 ðX 0 ÀX Þ ¼ M bed With X ¼ We deduce n X 0G0 n¼ M bed t ¼t f Z dn dt x¼ C 0 RT M P x 1Àx and ð1 À t ¼0 X Þdt X0 Environmental Progress & Sustainable Energy (Vol.750 78.556 2.000 80.191 0. Jemni A (2010)’’ Ethanol 0. This flux saturated in the solvent is diluted in a wind box by a pure air current. () experimental curves.666 37. The reactor has been dimensioned by taking into account the physical properties and the minimal speed of the particle fluidization of the activated carbon. Evolution of relative quantity of ethanol adsorbed in activated-carbon (—) theoretical curves (Eq.Table 3. () experimental curves. 7). No.218 0. All tests performed at a U0 speed 5 2 Umf.645 52. Evolution of relative quantity of acetone Figure 4. The tubular oven with 0.30.117 2.255 0.499 2.473 s(S) Ethanol Acetone 93.819 3 3 3 3 Figure 5.700 4.443 39. 7).000 10.279 10. The cold water exchanger enables to evacuate the yielded energy during the adsorption. O: 75 and D at 100. ^: 50. The pinching system is thermostat to avoid the concentration fluctuation of the saturation of the ambient temperature.435 Acetone 0. 1 308C.059 1.721 9.418 12.540 Acetone 9. 1 experimental points.295 10 1023 1023 1023 23 Acetone 1.195 1.1002/ep October 2011 299 . 1 308C. O: 75 and D at 100. ^: 50.192 0.

we have S ¼ K ½n1 ðT Þ lnðn1 ðT ÞÞ À nðt . This is due to the fact that the studied adsorptions are free and not forced. establishes the link between the entropy and X as S 5 f(X) where f is a universal function. NOMENCLATURE A 1 b C C0 D G0 I K m Mbed M N n(rc.1002/ep . we have proposed a theoretical approach of the correlation between matter and energy fluctuations and dissipations. to which Plank has given its final form. T ÞÞ lnðn1 ðT Þ À nðt .t) P R r rc t T X0 1 x accumulation due to direct adsorption (mol kg21 s21) relaxation time relative to pressure in isobar condition (s) integrate constant mass concentration of the solvent at the column input (g m23) diffusion constant of micro pores (m2 s21) model flow of inert gas (mol s21) 2 Complex number i 5 21 proportionality constant mass of adsorbed particles (kg mol21) mass of activated carbon bed2 (kg) molar mass of solvent (g mol 1) number of adsorbed molecules by volume unit (mol m23) Number of adsorbed molecules in (mol kg21) by spherical volume of rc radius at time t average density of particles in point at time t (mol kg21) pressure (Pa). 10 for each isotherm. This result is expected as the initial speed is very high and the measurements during the time interval [0. the pressure variations are very small and can be neglected. Annex I In statistical thermodynamics. t From this study the term ð1 À e s Þ which links the nðt .T Þ 1 h. The relative error between practice and theory is less than 10% at any instant over 10 s.t) n(r. From the previous studies and the present one. No. the term ð1 À es Þ is set to unity. the cell number of the corresponding space at a thermodynamical state. so that: S ¼ K ln X In the case of the adsorption of a gas in a microporous solid. APPLICATION OF THE THEORETICAL MODEL the adsorbed molecules over the total number of the receiver sites n1 ðT Þ: X¼ n1 ð T Þ ! nðt . 10.By integrating the previous equation we obtain the value of n. The computing results of constants C and s are summarized in Table 3 and the evolution of the experimental and theoretical adsorbed quantities are plotted in Figures 4 and 5. On the basis of the conjugate gradient identification technique. T ÞÞ þ lnðn1 ðT Þ @n In this article. we have estimated the constants C and s of expression Eq. T ÞÞ ¼ 0 ) nðt . T Þ lnðnðt . T ÞÞ! To experimentally illustrate the proposed theoretical model we have exploited the real part of Eq. T Þ ¼ n12 . T Þ!ðn1 ðT Þ À nðt . fluctuations to dissipations has an effect once n 1 ðT Þ 2 t 1 If this ratio equals 2. T Þ ¼ n1 ð T Þ 2 The function S 5 f(n) has a maximum for ðT Þ nðt . The unique solution of this equation is f(X) 5 K ln X.30. This theory takes into account all the internal system values because of the use of the statistical theory and the random function while solving the established differential equation. CONCLUSION With Stirling formula. we can affirm that the adsorption of a gas in a microporous solid is the result of three phenomena: a transportation phenomenon followed by a diffusion phenomenon and both phenomena are accompanied by a fluctuation. the Boltzman postulate. 5 where Y(t) is replaced by its expression given in Eq. X is the number of possibilities to arrange 300 October 2011 À nðt . In spite of the assumption that the adsorption is isobar. 10 s] are less assured. This approach as well as its theoretical limit (annex I) are confirmed experimentally. the concordance between the theory and the experiment is very satisfactory. T ÞÞ Àðn1 ðT Þ À nðt . the entropy S decreases as we have a negative temperature. the entropy is defined as a value which measures the degree of a system disorder in a microscopic level. 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 nonhomogeneity of the systems and the fluctuation observed experimentally. T Þފ The maximum of the entropy is : S @ð K Þ ¼ 0 ) À lnðnðt . assumed to be constant perfect gas constant instantaneous particle position in spherical coordinates (m) radius of spherical grain of adsorbent (m) time (s) temperature (8K) relaxation time relative to temperature (s) the partial molar fraction of initial solvent in the air Environmental Progress & Sustainable Energy (Vol.3) DOI 10. If X is the number of microstates.

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