Separation and Purication Technology 34 (2004) 165176

Study of isosteric heat of adsorption and activation energy for surface diffusion of gases on activated carbon using equilibrium and kinetics information
Kean Wang1 , Shizhang Qiao2 , Xijun Hu
Department of Chemical Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong

Abstract Pure component adsorption equilibria and kinetics of ethane and propane were measured on two activated carbon samples at various temperatures. The isosteric heat of adsorption was derived from the equilibrium information using the Clapeyron equation, while the activation energy for surface diffusion was derived from the surface diffusivity, which was extracted from the kinetics data using the macropore and surface diffusion (MSD) model. Two isotherm models, Unilan and Toth equations are used in the analysis of equilibrium and kinetics data. It is found that the choice of adsorption isotherm has a signicant inuence on the calculated values of isosteric heat of adsorption, but has less inuence on the activation energy for surface diffusion. The ratio of activation energy to isosteric heat of adsorption is found between 0.25 and 0.6 for ethane and propane on the two carbons, depending on the choice of isotherm equation. This ratio is a weak function of surface loading. 2003 Elsevier B.V. All rights reserved.
Keywords: Adsorption; Heat of adsorption; Activation energy; Surface diffusion; Equilibrium, Kinetics

1. Introduction Activated carbon is a highly microporous material with large surface area (>1000 m2 /g). In the adsorption process of gases/vapors on such adsorbents, surface diffusion can make signicant contribution to the overall mass transfer of strongly adsorbed species inside the carbon particle. Surface diffusion is very
Corresponding author. Tel.: +85-2-2358-7134; fax: +85-2-2358-0054. E-mail address: kexhu@ust.hk (X. Hu). 1 Present address: School of Mechanical Production Engineering, Nanyang Technological University, Singapore. 2 Present address: Department of Chemical Engineering, University of Queensland, Brisbane 4072, Australia.

complicated in nature, but has been known to be an activated process with surface diffusivity presenting a strong dependence on surface loading [1,2] and following an Arrhenius-type temperature dependence [3]. Studies also revealed that the activation energy for surface diffusion is related to and is a fraction of the energy of adsorption [4,5]. Literature on surface diffusion showed that the ratio of the activation energy for surface diffusion to the energy of adsorption could range from 0.33 to 1 [1]. Sladek et al. [6] pointed out that, for the diffusion of physically adsorbed species, this ratio can be 1 or 1/2. Although one would expect that this ratio should be dependent on local adsorption energy, it has been treated as a constant in many studies, e.g. Kapoor and Yang [79] investigated the effect

1383-5866/$ see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/S1383-5866(03)00190-4

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Nomenclature a a0 b Cb Cp Cp0 C C0 Cs Dp D D0 D Ea E0 a f H JP J km MSD qst q0 st r s t M ratio of activation energy for surface diffusion to adsorption energy ratio of activation energy for surface diffusion to adsorption energy at zero surface loading adsorption isotherm parameter (per kPa in eq.4, kPat in eq.5) bulk phase concentration in adsorber (kmol/m3 ) gas phase concentration in macropore (kmol/m3 ) initial gas phase concentration in macropore (kmol/m3 ) adsorbed phase concentration (kmol/m3 ) initial adsorbed phase concentration (kmol/m3 ) saturation adsorption capacity (kmol/m3 ) pore diffusivity (m2 /s) apparent surface diffusivity or Fickian diffusivity (m2 /s) surface diffusivity at zero loading (m2 /s) surface diffusivity at zero energy level (m2 /s) activation energy for surface diffusion (kJ/mol) activation energy for surface diffusion at zero surface loading (kJ/mol) fugacity (kPa) Henrys law constant (kmol/m3 per kPa) diffusion ux in macropore (kmol/m2 per s) diffusion ux in adsorbed phase (kmol/m2 per s) mass transfer coefcient of lm (1/s) macropore and surface diffusion (model) isosteric heat at a given specic loading (kJ/mol) isosteric heat of adsorption at zero loading (kJ/mol) particle coordinate (mm) isotherm parameter (eq. 4) geometric factor of particle, 0, 1, 2 for slab, cylinder and sphere, respectively isotherm parameter (eq. 5), time (s) surface coverage chemical potential (kJ/mol) porosity of adsorbent particle

of surface heterogeneity on adsorption kinetics with this ratio being taken as 0.5 or 1. Do and co-workers [1013] used the value of 0.5 for this ratio in most of their studies of adsorption kinetics on activated carbon. The isosteric heat of adsorption for pure gas and gas mixture is a critical parameter for adsorptive separation processes. Dunne et al. [1416] pointed out that, for binary mixture, the isosteric heats are directly related to the temperature coefcient of selectivity at xed loading. They measured the heat of adsorption with a calorimeter (calorimetric heat) and the isotherm simultaneously for a series of gas adsorbates on a series of adsorbents, which present different

heterogeneity. Their results showed good agreement between the heat of adsorption measured and the isosteric heat of adsorption calculated using the Clapeyron equation. Sircar [17,18] and Dunne et al. [16] investigated the isosteric heat of adsorption of binary gas mixtures on heterogeneous adsorbent and found that the isosteric heat for a component in gas mixture can be very much different from that of a pure species. The isosteric heat of adsorption can be conveniently calculated from the Clapeyron equation with the assumption of an isotherm, Valenzuela and Myers [19] derived isosteric heat of adsorption for many adsorbateadsorbent systems using two isotherm

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equations: Unilan and Toth. Their results revealed that the isosteric heat versus surface loading is very sensitive to the choice of the isotherm equation as well as the pressure range of the equilibrium data. Dunne et al. [14] pointed out that the difference between the isosteric heats of adsorption at the limit of zero loading reported by different investigators might vary by a large margin (up to 40%). Pan et al. [20] employed the non local density function (NLDF) to generate isotherms at different temperatures and examined the two assumptions used in the Clapeyron equation for the calculation of the heat of adsorption, i.e. (1) ideal bulk gas phase and (2) a negligible adsorbed phase molar volume. They concluded that these two assumptions are reasonable at the low-pressure region but may have a signicant effect on the result at high relative pressure region or for heavy adsorbates. This article will study the activation energy for surface diffusion and the isosteric heat of adsorption for two adsorbates, ethane and propane, on two activated carbon samples (Ajax, and Norit). These two important parameters will be derived from pure component adsorption equilibrium and kinetic data, respectively. The effect of the adsorption isotherm on the calculation of these two parameters will also be investigated.

adsorbateadsorbent system. By substituting eq. (2) into eq. (1), the isosteric heat of adsorption at zero loading limit, q0 , can be expressed in terms of Henrys st law constant as: ln H 0 qst = RT2 (3) T The isosteric heat of adsorption calculated from Clapeyron equation is sensitive to the choice of the isotherm equation [1719]. Two frequently used isotherm equations, Unilan and Toth, are employed in this article to calculate qst . The Unilan isotherm takes the form of: 1 + bes Cp Cs C = (4a) ln 2s 1 + bes Cp where Cs is the adsorption saturation capacity, b and s are the afnity and the heterogeneity parameters of the adsorbent. The Henrys law constant for Unilan equation is: H = Cs b es es (4b) 2s The Toth isotherm equation is in the form of: Cp C = Cs (5a) t (b + Cp )1/t where t is the degree of the heterogeneity of the adsorbent. The Henrys law constant for Toth equation is: H = Cs b1/t (5b)

2. Theory 2.1. Isosteric heat of adsorption The isosteric heat of adsorption of a pure gas, qst , at a given specic surface loading, C , can be calculated from the adsorption isotherms of that adsorbate at different temperatures using the Clapeyron equation: qst = RT2 ln f T (1)
C

2.2. Adsorption kinetics and activation energy for surface diffusion Surface diffusion is an activated process and the temperature dependence of surface diffusivity can be correlated by an Eyring equation: Ea D = D exp (6) RT where Ea is the activation energy for surface diffusion. D is the surface diffusivity at zero energy level. With the driving force for surface diffusion being taken as the gradient of chemical potential, , the surface ux can be written as: 0 0 d ln Cp C J = D C = D r d ln C r C (7) = D r

where R is the gas constant, T is temperature, and f is the fugacity, which is equal to the pressure, Cp , for an ideal gas. At the low pressure (Henrys Law) region, the isotherm should be linear, i.e.: C = H Cp (2)

where H is Henrys law constant. Since H is a function of temperature only, the isosteric heat of adsorption of a species will represent a characteristic of the

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where D0 is the surface diffusivity at zero loading, r is the coordinate of the diffusion path, and D is the apparent surface diffusivity, which is strongly concentration dependent, represented by the Darken relationship:
0 D = D

where the pore diffusivity, Dp , is the combination of the Knudsen and molecular diffusivity [24]. The boundary and initial conditions for Eq. (10a) are described in the reference [2] and are briey re-introduced here as: t = 0, Cp = Cp0 , C = C0 , Cb = Cb0 r = 0, M JP + (1 M )J = 0 (10c) (10d)

d ln Cp d ln C

(8)

When a Langmuir isotherm is used, Eq. (8) reduces to the HIO model [21], which has been widely used in the past to correlate D and D0 : D =
0 D

r = R, M JP + (1 M )J = km (CP Cb ) (10e) Using the MSD model, where the concentration dependence of surface diffusivity is described by the Darken relationship (Eq. (8)), we can analyze the kinetic data of an adsorbateadsorbent system at different bulk concentrations simultaneously and derive D0 . With D0 at different temperatures, the activation energy for surface diffusion at zero surface loading, E0 , is then derived from the slope of the plot of ln(D0 ) a against 1/T. Taking q0 as the heat of adsorption at st zero surface loading, the ratio of activation energy for surface diffusion to heat of adsorption at zero surface loading, a0 , can be calculated as:
0 0 a0 = Ea /qst

(9)

where is the fractional surface loading. Modications of this relation are also seen in the literature, e.g. Yang et al. [22] modied the HIO model with the consideration of the second layer adsorption. Hu et al. [2] found that the concentration dependence of the surface diffusivity is much stronger than that predicted by the Darken relationship and later Do [23] proposed a theory to explain that observation. In this study, the Darken relationship will be used as the approximation for the concentration dependence of surface diffusivity. Since the structure of activated carbon particle is generally bi-dispersed, the macropore and surface diffusion or MSD model [2] is a reasonable choice for the simulation of adsorption kinetics on such an adsorbent. With the MSD model, however, the adsorbent is treated as being effectively homogeneous and the derived kinetics parameters will represent some kind of average kinetic behavior of the system. The overall mass balance over a particle with geometric factor of s (0, 1, 2 for slab, cylinder, and sphere, respectively) can be expressed in term of MSD model as: M Cp C + (1 M ) t t 1 = s [M rs JP + (1 M )r s J ] r r

(10)

Meanwhile, the effect of isotherm equation on this ratio can also be examined.

3. Experimental The pure component adsorption equilibrium of ethane and propane were measured on Ajax activated carbon and Norit activated carbon, respectively, using volumetric method. For Ajax carbon, the isotherm of each species were measured at three temperatures: 283, 303, and 333 K [11] while for Norit carbon, the isotherm of each species were measured at 303, 333, and 363 K [25,26]. The pure component adsorption kinetics of ethane and propane on each carbon sample were measured using a differential adsorbed bed (DAB) rig. The kinetics data of each adsorbate were measured on Ajax carbon in 4.4-mm full-length slab particles at the temperatures of 283, 303, and 333 K [11], respectively. At each temperature, sorption kinetics at three bulk phase molar fractions: 5, 10, and 20% were measured, at a total pressure of 1 atm balanced by nitrogen. The adsorption kinetics on Norit

(10a)

where M is the macroporosity of the adsorbent, and Cp is the bulk phase concentration. Jp is the diffusion ux in the bulk phase, which is described by the Ficks law: CP JP = DP (10b) r

K. Wang et al. / Separation and Purication Technology 34 (2004) 165176 Table 1 Experimental equilibrium and kinetics conditions of ethane and propane on two activated carbons Equilibrium Ethane Ajax Norit
a

169

Kineticsa Propane 283, 303, and 333 K 303, 333, and 363 K Ethane 5, 10, and 20% 2, 5, and 10% Propane 5, 10, and 20% 2, 5, and 10%

283, 303, and 333 K 303, 333, and 363 K

At each molar fraction the data were measured for the corresponding three temperature used in equilibrium.

carbon was recently measured on 8.82-mm full-length slab particles at 303, 333, and 363 K, respectively [25]. The bulk phase molar fractions of each species are 2, 5, and 10% for each temperature, also at a total pressure of 1 atm but balanced by high purity helium (99.999%). Thus, we have twelve isotherm curves and 36 kinetic uptake curves in total for this study. The experimental conditions for the equilibrium and kinetic data are listed in Table 1. The detailed experimental procedures can be found in the related references.

4. Results and discussion 4.1. Isosteric heat of adsorption The pure component experimental equilibrium data of ethane and propane collected on two carbon samples at different temperatures are rst employed, respectively, to optimize the parameters of each isotherm equation. The relative average error (ARE) between the model tting and the experimental data is used as the objective function for optimization. Fig. 1a and b show the experimental data of ethane and propane on Norit carbon (symbols), respectively. Also shown in these two gures are the model ttings of Unilan equation (dashed lines) and Toth equation (solid lines). It is seen that either isotherm can adequately t the experimental data, but the Toth equation ts the data slightly better. Fig. 2a and b present the experimental data (symbols) of ethane and propane on Ajax carbon. The model ttings from the Unilan and Toth equations are presented in these two gures as dashed and solid lines, respectively. It is seen again that both models t the data well. Table 2 lists the isotherm parameters derived from Unilan equation for ethane and propane on the two carbons. With these parameters, the Henrys law constant, H, of each adsorbate is calculated for each

temperature using Eq. (4b) and is tabulated in Table 2. By plotting ln(H) against 1/T, the isosteric heat of adsorption at zero loading, q0 is derived from the slope. st Fig. 3a shows the ln(H) 1/T plot for each species on Norit carbon as an example. The same good linearity of the plot is also observed on Ajax carbon although the plot is not shown here, to save space. The derived q0 is listed in Table 2. The order of q0 for the two st st species is in the range of 2440 kJ/mol, which is comparable to the value reported by Valenzuela and Myers [19] for the two adsorbates on Nuxit carbon, that is, q0 st is approximately 25 kJ/mol for ethane and 38 kJ/mol for propane (derived with Unilan equation). Some

Fig. 1. Adsorption equilibrium data and model ttings on Norit carbon. (--- Unilan isotherm, Toth isotherm).

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Table 2 Adsorption isotherm parameters for ethane and propane on two carbons derived from the Unilan equation Sample T (K) Cs (mmol/g) C2 Norit 303 333 363 283 303 333 6.41 4.71 3.50 10.3 9.01 7.37 C3 6.45 6.38 5.36 8.34 7.74 7.01 b (per kPa) C2102 1.07 1.00 0.867 0.701 0.544 0.420 C3102 2.85 1.17 0.953 5.62 3.66 2.08 s C2 4.03 3.20 2.57 4.36 3.85 3.36 C3 4.83 4.60 4.46 5.70 4.73 3.83 H (mmol/g per kPa) C2 0.478 0.180 0.0768 0.646 0.300 0.133 C3 2.38 0.810 0.496 12.3 3.40 0.876 q0 (kJ/mol) st C2 27.9 C3 24.1

Ajax

24.7

40.6

abnormality is also observed in the value of q0 on st Norit carbon, that is, ethane has slightly higher isosteric heat than propane. A possible reason could be that Norit carbon has some smaller pores, which present strong adsorption afnity for ethane but are inaccessible to propane due to its larger molecule size [26]. To study the effect of isotherm equation on the calculation of q0 , the Henrys law constants of the st two adsorbates are then derived from Toth isotherm (Eq. (5b)). The plot of ln(H) 1/T on Norit carbon is

shown in Fig. 3b as an example. The plot on Ajax carbon presents similar linearity but is not shown here. The derived q0 for each adsorbateadsorbent system st are listed in Table 3. Comparing with the related values in Table 2, it can be seen that Toth equation gives slightly higher values of q0 than Unilan equation. The st values of q0 for ethane and propane on Ajax carbon st are also very close to those obtained on Nuxit carbon

Fig. 2. Adsorption equilibrium data and model ttings on Ajax carbon. (--- Unilan isotherm, Toth isotherm).

Fig. 3. Plot of Clapeyron equation, ln(H) 1/T; (a) with Unilan isotherm, (b) with Toth isotherm.

K. Wang et al. / Separation and Purication Technology 34 (2004) 165176 Table 3 Adsorption isotherm parameters for ethane and propane on two carbons derived from the Toth equation Sample T (K) Cs (mmol/g) C2 Norit 303 333 363 283 303 333 9.27 10.5 10.6 13.1 13.2 14.4 C3 6.47 5.29 5.28 9.03 9.32 11.8 b (kPat ) C2 1.66 2.75 4.41 1.91 2.35 4.36 C3 0.840 1.51 1.75 0.490 0.697 1.06 t C2 0.314 0.328 0.350 0.340 0.335 0.368 C3 0.331 0.415 0.383 0.267 0.278 0.264 H (mmol/g per kPa) C2 1.87 0.480 0.153 1.97 1.02 0.262 C3 10.9 1.96 1.25 11.6 4.02 1.07

171

q0 (kJ/mol) st C2 38.2 C3 33.9

Ajax

31.7

41.1

with Toth equation (i.e. 31 kJ/mol for ethane and 42 kJ/mol for propane, by Vanlenzuela and Myers [19]). The q0 derived on Norit carbon for ethane is again st slightly higher than that of propane. The isosteric heats of adsorption at other surface loadings, qst , are calculated using Eq. (1) with Unilan or Toth isotherm, which are plotted in Fig. 4. With the Toth isotherm, the maximum adsorption capacity (Cs ) ranges from 9.27 to 10.6 mmol/g for ethane,

and 5.28 to 6.47 mmol/g for propane, in Norit carbon at different temperatures between 303 and 363 K. That is, the difference in Cs is not signicant for different temperatures. This is also true for Ajax carbon. Therefore, when Toth isotherm is used, as expected, the value of qst decreases as surface loading increases, for both ethane and propane on both Norit and Ajax carbons. However, when Unilan isotherm is used, because Cs decreases signicantly as temperature increases, e.g. from 3.50 at 303 K to 6.41 mmol/g at 363 K (83% increase) for ethane in Norit carbon, qst increases as surface loading increases. The change of Cs with temperature is less severe for Ajax carbon, so the isosteric heat of adsorption changes only marginally as surface loading increases for Ajax carbon, when Unilan isotherm is applied. 4.2. Adsorption kinetics The adsorption kinetics is simulated by the MSD model, which employs Unilan or Toth equation to describe the equilibrium isotherm. The pore diffusivity of the two adsorbates are listed in Tables 4 and 5, respectively, which are temperature and adsorbent dependent but concentration independent [24]. With those parameters dened, we are ready to study the surface diffusivity at zero loading, D0 , for each adsorbateadsorbent system at different temperatures. First, the adsorption kinetics of ethane on Norit carbon is studied. Fig. 5a shows the experimental data (symbols) of ethane on Norit carbon in 8.82 mm full-length slab particles at the temperature of 303 K. The experimental bulk phase molar fractions of ethane are 2, 5, and 10%, respectively, at a total pressure of 1 atm. All data in Fig. 5a were employed simultaneously to optimize the surface diffusivity at

Fig. 4. Isosteric heat of adsorption as a function of surface loading.

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Table 4 Diffusivities and activation energy of ethane and propane on Norit activated carbon T (K) Dp 106 (m2 /s) 303 Ethane Propane 2.12 1.75 333 2.26 1.86 363 2.38 1.97 D0 108 (m2 /s) 303 1.55 1.32 0.641 0.597 333 2.33 1.92 0.943 0.846 363 3.24 2.80 1.12 1.02 11.3 11.4 8.70 8.36 Unilan Toth Unilan Toth 0.40 0.30 0.36 0.25 E0 (kJ/mol) a a0

zero coverage of the MSD model using the Unilan isotherm. The optimal model ttings are shown in Fig. 5a as dashed lines. It is seen that the Darken type concentration dependence for surface diffusivity is adequate for the MSD model to describe the uptake of ethane on Norit carbon. The derived surface diffusivity at zero loading, D0 , is listed in Table 4. Toth isotherm is then used in the MSD model to study the above kinetic data of ethane again. The model ttings are shown in Fig. 5a as solid lines while the derived D0 is listed in Table 4. It can be seen that, contrary to what we saw in the calculation of q0 , the st two isotherm equations have similar tting goodness for the kinetic data and give similar values of D0 , in dicating that the Unilan and Toth isotherms have the similar capability in simulating the adsorption kinetics in the MSD model, because both are able to t the isotherm data well. Next, the above procedures are applied in the study of the adsorption kinetics of ethane on Norit carbon at two other temperatures, 333 and 363 K. The bulk phase molar fractions are again 2, 5 and 10% for each temperature. Fig. 5b and c show graphically the experimental data (symbols) and the model ttings (solid lines for MSD model with Toth isotherm and dashed lines for MSD model with Unilan isotherm) at those two temperatures, respectively. It can be seen that the

ttings are reasonably good. The derived D0 with the two isotherms are listed in Table 4. Having obtained D0 for ethane on Norit carbon at three different temperatures, we are ready to calculate its activation energy for surface diffusion at zero surface loading, E0 . Fig. 6 shows the plot of ln(D0 ) a against 1/T. Good linearity of the plot is observed, supporting the consistency of D0 derived with the MSD model. The value of E0 for ethane is found to be 11.3 a kJ/mol with Unilan isotherm and 11.4 kJ/mol with Toth isotherm. We note that the choice of isotherm equation does not have a signicant inuence on the value of E0 . However, since q0 is highly isotherm dea st pendent, the value of a0 (E0 /q0 ) is also isotherm dea st pendent. The value of a0 for ethane on Norit carbon is found to be 0.4 for Unilan isotherm and 0.3 for Toth isotherm. The adsorption kinetics of propane was also measured on Norit carbon under the same experimental conditions as those of ethane. Thus the procedures discussed above are repeated to derive D0 and E0 of a propane on Norit carbon. Fig. 7 shows the experimental data (symbols) and the model ttings (solid lines for MSD model with Toth isotherm and dashed lines for MSD model with Unilan isotherm) of the adsorption kinetics of propane on Norit carbon at 303, 333, and 363 K, respectively. The agreement between model

Table 5 Diffusivities and activation energy of ethane and propane on Ajax activated carbon T (K) Dp 106 (m2 /s) 283 Ethane Propane 1.51 1.20 303 1.68 1.30 333 1.96 1.56 D0 109 (m2 /s) 283 2.37 2.16 0.761 0.778 303 3.21 2.71 0.950 0.868 333 5.88 5.07 1.78 1.48 14.4 13.6 13.4 10.3 Unilan Toth Unilan Toth 0.58 0.43 0.33 0.25 E0 (kJ/mol) a a0

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Fig. 6. Plot of ln(D0 ) 1/T of ethane on Norit carbon.

Fig. 5. Adsorption kinetics data and model ttings for ethane on Norit carbon at various temperatures. (--- with Unilan isotherm, with Toth isotherm).

ttings and experimental data is good. Fig. 8 presents the plot of ln(D0 ) against 1/T for propane. The derived kinetics parameters, D0 and E0 are listed in Table 4. a Since propane is more bulky than ethane, the surface diffusivity is smaller for propane. The value of a0 for propane in Norit carbon is found to be 0.36 for Unilan isotherm and 0.25 for Toth isotherm. Finally, the adsorption kinetics of the two adsorbates on Ajax carbon was studied. The pure component adsorption kinetics of ethane and propane were measured on Ajax carbon in 4.4 mm full-length slab

Fig. 7. Adsorption kinetics data and model ttings for propane on Norit carbon at various temperatures. (--- with Unilan isotherm, with Toth isotherm).

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Fig. 8. Plot of ln(D0 ) 1/T of propane on Norit carbon.

particles at three temperatures: 283, 303, and 333 K, respectively. The bulk phase molar fractions of each adsorbate are 5, 10, and 20% for each temperature, at a total pressure of 1 atm. These data were then employed to optimize D0 with respect to the MSD model using either Unilan or Toth isotherm. The procedures of driving D0 and E0 for each adsorbate are the same a as those described for Norit carbon. Fig. 9 shows the kinetic data (symbols) and the ttings of MSD model (solid lines for MSD with Toth and dashed lines for MSD with Unilan isotherm) for

Fig. 9. Adsorption kinetics data and model ttings for ethane on Ajax carbon at various temperatures. (--- with Unilan isotherm, with Toth isotherm).

Fig. 10. Adsorption kinetics data and model ttings for propane on Ajax carbon at various temperatures. (--- with Unilan isotherm, with Toth isotherm).

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ethane on Ajax carbon at 283, 303, and 333 K, and Fig. 10 shows the data (symbols) and model ttings (lines) of propane on Ajax carbon. The agreement between experimental data and the model ttings are again good for both adsorbates under various experimental conditions, which seems to support the use of Darken relation in the experimental bulk molar fraction range (520%). The derived D0 of each species are listed in Table 5. The plots of ln(D0 ) against 1/T for ethane and propane on Ajax carbon present same good linearity as those on Norit carbon and hence are not shown here. The derived Ea of each adsorbate on Ajax carbon are tabulated in Table 5. The value of a0 on Ajax carbon ranges from 0.43 to 0.58 for ethane and 0.25 to 0.33 for propane. With D0 obtained, the surface diffusivities at other surface loadings, D , are calculated according to the Darken relationship, Eq. (8), for both Unilan and Toth isotherms at three temperatures. The results are show in Fig. 11 for Norit carbon and Fig. 12 for Ajax

carbon. As expected, the surface diffusivity increases as surface loading increases, for both adsorbates in both carbons, and for both Unilan and Toth isotherms. The derived surface diffusivity at any surface loading at various temperatures is then used to compute the activation energy at that surface loading, using Eq. (6). The obtained activation energy, together with the isosteric heat of adsorption shown in Fig. 4, are then used to calculate the ratio of activation energy of surface diffusion to the heat of adsorption, a = Ea /qst , at any surface loading, which is plotted in Fig. 13. Although both qst and D are functions of surface loading (Figs. 4, 11 and 12), the ratio of activation energy of surface diffusion to the heat of adsorption, a, does not change much with surface loading. This supports the constant value of a used in various previous studies [10,11,13,2628]. In general, for the same species the value of a from Unilan isotherm is larger than that from Toth isotherm, while for differ-

Fig. 11. Surface diffusivity of ethane and propane in Norit activated carbon as a function of surface loading.

Fig. 12. Surface diffusivity of ethane and propane in Ajax activated carbon as a function of surface loading.

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sorption kinetics of the two adsorbates on the two carbons under the experimental conditions investigated.

Acknowledgements Financial support from the Croucher Foundation, and the Research Grants Council of Hong Kong (Project No. HKUST6114/97P) is greatly acknowledged. References
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Fig. 13. Ratio of activation energy of surface diffusion to the heat of adsorption as a function of surface loading.

ent species, the a for ethane is larger than that for propane.

5. Conclusions The isosteric heat of adsorption, qst , and the activation energy for surface diffusion, Ea , of ethane and propane are derived from their equilibrium and kinetics information measured on two activated carbons. It is found that the choice of adsorption isotherm has a signicant inuence in the calculation of qst , but has less inuence on Ea . The value of a (Ea /qst ) is found between 0.25 and 0.60 for the two adsorbates on the two carbons and this ratio depends on the choice of the kinetics as well as isotherm models. It is shown that Toth isotherm resulting in a smaller value of a than Unilan isotherm. The pore and surface diffusion model with a Darken type concentration dependence for surface diffusivity is found adequate to describe the