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- 8

**The Dubinin–Radushkevich equation and the underlying
**

microscopic adsorption description

C. Nguyen, D.D. Do*

Department of Chemical Engineering, The University of Queensland, St. Lucia, Qld 4072, Australia

Received 10 May 2000; accepted 4 September 2000

Abstract

**The Dubinin–Radushkevich (DR) equation is widely used for description of adsorption in microporous materials,
**

especially those of a carbonaceous origin. The equation has a semi-empirical origin and is based on the assumptions of a

change in the potential energy between the gas and adsorbed phases and a characteristic energy of a given solid. This

equation yields a macroscopic behaviour of adsorption loading for a given pressure. In this paper, we apply a theory

developed in our group to investigate the underlying mechanism of adsorption as an alternative to the macroscopic

description using the DR equation. Using this approach, we are able to establish a detailed picture of the adsorption in the

whole range of the micropore system. This is different from the DR equation, which provides an overall description of the

process. 2001 Elsevier Science Ltd. All rights reserved.

Keywords: A. Activated carbon; B. Adsorption; D. Microporosity

**1. Introduction However, very often the characteristic curve concept is
**

broadly assumed, and in extreme cases, it fails to describe

The Dubinin–Radushkevich (DR) equation is widely the experimental data [4]. Furthermore, there are issues

used to describe adsorption of sub-critical vapours in that are open for discussion, such as the pressure range in

microporous solids such as activated carbons and zeolites. which the equation is applicable, the question of com-

The utility of the equation lies in the fact that the pliance with the Henry law at low pressure, the derived

temperature dependence is reflected in the adsorption heat of adsorption at very low or very high pressures, etc.

potential A 5 2 RT ln (x) with x 5 p /p0 , that is, if the Originally the DR equation was developed as a semi-

adsorption data at different temperatures are plotted as the empirical tool to describe the adsorption isotherms of

logarithm of the amount adsorbed versus the square of microporous materials based on the Polanyi potential

adsorption potential, all the data points should fall into one theory of adsorption [5]. It is, however, possible to explain

curve. This curve is known in the literature as the the equation using some theoretical foundation, e.g., using

characteristic curve. statistical thermodynamics as illustrated in the work of

The existence of the characteristic curve has been Yang et al. [6].

proven in numerous cases by Dubinin and other workers. Recently, we introduced a new method to describe the

The success of the DR equation in describing adsorption of adsorption process in microporous carbonaceous materials

many subcritical fluids is undeniable. There are also with a pore size distribution [7]. It is a structure based

successful attempts to modify the equation to make it method, where emphasis is placed on the enhancement of

applicable to adsorption of supercritical adsorbates [1–3]. adsorption evaluated by means of molecular potential

calculations. This treatment allows the use of a single

*Corresponding author. Tel.: 161-7-3365-4154; fax: 161-7- mechanism for adsorption in pores of different sizes. In

3365-2789. this paper, we will use this technique to investigate the

E-mail address: duongd@cheque.uq.edu.au (D.D. Do). adsorption in carbon micropores in an attempt to shed

**0008-6223 / 01 / $ – see front matter 2001 Elsevier Science Ltd. All rights reserved.
**

PII: S0008-6223( 00 )00265-7

Nguyen. 1 shows the characteristic curves of nitrogen and 2. Nitrogen (solid) and benzene (open) characteristic curves with a slope 2 (RT /E)2 and an intercept log (W0 ). Do / Carbon 39 (2001) 1327 – 1336 Nomenclature C affinity coefficient of the BET equation Cm micropore capacity E potential of gas phase molecule P relative pressure Q heat of adsorption at zero loading R gas constant T temperature W volume adsorbed W0 micropore volume p pressure p0 vapour pressure DH isosteric heat of adsorption DHv ap vaporisation heat r pore size (radius or half width) ´ characteristic energy derived from DR equation s liquid surface tension r liquid density gm liquid molar volume s subscript referring to solid slab surface p subscript referring to micropore some light on the working mechanism behind the DR which the characteristic energy and the micropore volume equation. Description of the DR equation and our model of benzene adsorption onto two activated carbon (AC) sam- adsorption ples. This parameter is termed the simi- larity coefficient. the DR equation can be written as: the characteristic energy. . can be obtained. from for the Ajax AC (circle) and ACF (diamond) carbons. whereas that for benzene is 303 K. benzene was chosen by Dubinin and his co-workers to be the standard adsorbate for carbonaceous materials. The adsorption temperature for nitrogen is 77 K. The characteristic energy E for a given fluid–solid system can be further expressed using a scaling factor J as follows: E 5 b E0 (2) where E0 is the characteristic energy of a ‘standard’ adsorbate with respect to the given solid. This is to test the suitability of the equation and / or to determine its range of applicability. Similar results would be obtained from a direct 5 exp[2(RT ln (x) /E)2 ] (1) fitting of the DR equation to the experimental data using a with x 5 p /p0 . Fig. D. Results of such calculations are shown in W/W0 5 exp[2(A /E)2 ] or W/W0 Table 1. from which an effective pore size can be estimated. the plot would be a straight line Fig. 1. For example. This is probably due to the similarity between the benzene ring and the hexagonal arrangement of carbon atoms in the graphite basal planes. and it is a function of the adsorbate properties only. The DR equation equation of the straight lines describing the linear section of the plots is used to calculate the micropore volume and In its basic form.D. If the equation is applicable.1. The 2. As an illustration of the applicability of the DR equa- tion.1328 C. Ajax AC and ACF. The characteristic curve of a system is established by plotting the logarithm of the amount adsorbed W versus log 2 (1 /x).

and the statistical thickness of the adsorbed layer can be described by means of a BET equation. This is difference between the adsorption potential energy in a considered to be another advantage of the DR equation. C. molecules occluded within the pore. this difference is expected to 2. the coefficient is a function of the difference between the heats results calculated from the adsorption data of different of adsorption.2. pore and that on a surface. This average potential is a function of the pore size.2.80 5.9 0. As seen in Table 1.D. The potential energies (in In our approach [7]. 2. adsorption in enhancement effect on the occluded molecules.68 13. the average potential energy of the occluded molecules. the micropore volume of Ajax assumed to be similar for those two situations.80 2. since other energy contributing Table 1 also indicates that although the mean micropore factors such as the vibrational and rotational energies. Because of this Based on the concepts presented above. the pore pressure can be estimated as overlapped potential forces. The adsorption layering is also enhanced. there is a difference between the sum of these energies of the fluid and adsorbed phases.66 Benzene 303 89. Once inside. the fluid pores can be pictured as a process whereby gas phase phase pressure within the pore.65 Benzene 303 89. (K) r (cc / mol) Cms (mmol / g) W0 (cc / g) E (kJ / mol) r (nm) ACF Nitrogen 77 34. If the enhanced pressure is follows: S pp (r) 5 p exp 2 kE gp (r)l ]]] RT D (3) with kE gp l. Cp . we shall use the potential energy at zero loading as that in the calculation of the difference in heats 2. as follows: SQ p (r) 2 Q s Cp (r) 5 Cs exp ]]] . The enhancement is ac- counted for through the proper use of the BET coefficient for the pore. Even when AC is about two times larger than that of the ACF sample.53 0. Nguyen. These energies are determined from the feature in our approach is the allowance for the enhance- pair-wise summation of a benzene molecule with all atoms ment in adsorption induced by the overlapping of the on the walls of the carbon pore.68 6. Do / Carbon 39 (2001) 1327 – 1336 1329 Table 1 Parameters calculated from nitrogen and benzene data using the DR equation Temp. pp . is different from the molecules are drawn into the pore interior. The principal carbon pores. are sizes are about the same.66 Ajax Nitrogen 77 34. This difference is contributed mainly by the probe molecules are consistent with each other. but also the gas phase layers [8]. Adsorption mechanism of adsorption in Eq. irrespective of their sizes.0 0.23 18. bulk pressure p. D. With this assumption.47 17. RT D (4) Fig.48 7.1. The carbon pore wall is potential fields of opposite pore walls. (4) means that the enhanced adsorption affinity and our method.24 6. . and it will be approximated as the potential energy at the pore center E gp . we adopt a common mechanism for an absolute sense) at zero loading corresponding to the the adsorption process occurring in carbonaceous pores as well depth and at the center of the pore are plotted in Fig.34 0.8 0.67 non-linear optimisation routine. a sequence of surface layering followed by condensation 2 as a function of pore size for benzene adsorption in (or pore filling).9 0. This enhancement assumed to have a structure similar to the stack of graphite not only affects the adsorbed phase.95 0. which is related to the BET coefficient for a flat surface having the same surface chemistry and structure. (4) (Q p (r)).1 0. According to the Boltzmann distribution they are further pressed against each other as a result of the of molecules. Potential energy of adsorption used in the DR equation Eq. Potential enhancing adsorption model be smaller than the change in the potential energy.

D. Nitrogen single-pore isotherm at 77 K for carbon slit-like pores of half widths of 1.26. 17. D. Single pore isotherms isotherms in our technique to calculate the pore size The statistical thickness of the adsorbed layer t is distribution (PSD) of the subject solid. The liquid–solid contact angle is phase turns into liquid (albeit compressed liquid). 3. The mathematical therefore.3. 2. p0 and a 2 t .54. This liquid filling The thickness of the adsorbed layer a process progresses to pores larger in size as the bulk (0 # a # r) pressure increases.1330 C. Do / Carbon 39 (2001) 1327 – 1336 beyond the corresponding vapor pressure. in contrast to the macroscopic description r if pp $ p0 available from the Dubinin theory [1.24. Nguyen. adsorption occurs as a surface layering process. and to some extent even the HK approach [9].2. liquid even at low bulk pressures. The extracted PSD is as presented in the form of a histogram. the sm g sample is a microporous material with a majority of pores r k 5 ]]] (6) RT ln (x p (r)) falling into the micropore range (by IUPAC definition Fig. carbonaceous pores of different size. Parallel to this. 0. assumed to be zero for simplicity.2. 4. As shown. The threshold half sample are shown in Fig. 3 for nitrogen adsorption at 77 K in slit-like mesopores this is termed capillary condensation).74. As seen. and 5 5 t if pp . 0. 1. understood that in some narrow pores. 5.17. the adsorbed with x p (r) 5 pp (r) /p0 . This is a picture of the micropore filling process in detail. . 3. r k r if pp .66.2. which takes the procedure involved is presented elsewhere [11]. the fitting is excellent width r k when the pore filling by pore condensation occurs at both low and high pressures. 8. PSD of the ACF sample from nitrogen adsorption at 77 K x p (r)Cp (r) t(r) 5 t m ]]]]]]]] (5) The model is tested against adsorption data of nitrogen (1 2 x p (r))(1 2 x(r) 1 x p (r)Cp (r)) at 77 K for a microporous carbon sample (Takeda ACF).82 nm (bottom).06. Results of the model fitting and the extracted PSD of the with t m being the monolayer thickness.65 (top) and 0. The optimisation evaluated using the BET equation [10].46. in larger pores. the adsorbed phase exists as then be written as follows.38. (reading from left to right). These single pore isotherms are used as the local 2. Examples of these single pore isotherms are value or the conditions for pore filling are satisfied (for shown in Fig. following form when variables are allowed to bear depen- dence on the pore size: 2. p0 and a 2 t # r k (7) this layer will grow with pressure until a stage is reached The adsorption isotherm can thus be generated for pores of when the enhanced pressure reaches the vapor pressure any size.2]. It is. 0. due to the interpretation of the arguments in the previous section can very large enhanced pressures.

The contributions of each sequential adsorption individual pore size. pores are empty or completely filled with the liquid adsorbate.39. 2. As illustrated in the progresses to pores of larger size when the pressure figure. i. Progress of adsorption contributions of adsorption in different pore ranges at three levels of reduced pressure. The dominance of adsorption in pore walls. For example. A 5 RT ln (x). a fractional loading means that all pores narrower increases. the DR theory does not provide in the smallest micropores. the than a certain size are filled with adsorbate molecules. the contribution of micropore . Such information is important in the overall capacity at this pressure is 3. when the pore volume is instanta- width of 1. This is different from Dubinin’s Table 2. Here we and heat of adsorption with loading. 6. 4. 5. to distinguish pores the free energy.98310 22 . are presented in Fig. the fractional loading in the DR 0. all pores having half pore being dependent on the pore size. compared better understanding of the variation of adsorption affinity to 3. 4. is equal to the characteristic already filled to their maximum capacity.588 nm are filled. the fractional loading is 0. As presented above. each characterised by a nominal pore in micropores only. and Strictly speaking.D. The division allows more sub-ranges to be in the larger pores to the uptake must be removed from the micropore region to reflect the microporous nature of the experimental data before they are used with the DR ACF. According to the HK mechanism.266 nm. especially at low pressures.32 nm). there is no half full status for pores.37.39.3310 25 . the half width. Nitrogen isotherm fitting and the resulting PSD of sample ACF. which appear in the PSD shown in Fig. 2 nm).e. The than the larger ones.98310 22 . In the table. At in all pores simultaneously. and the thickness of the adsorbed layer is a micropores.3310 25 . Furthermore. adsorbate molecules. Furthermore. we divide the pore spectrum equation defined as u 5 W( p) /W0 accounts for adsorption into 24 sub-ranges. Volume filling of micropore theory versus adsorption in pores of all sizes. neously filled by the adsorbate liquid. Let us first study meaning 37% of the micropore volume is occupied by the the adsorption at the low relative pressure of 6. is obvious from function of the pore size. The overall adsorption on the ACF is a summation of 3. D.04 mmol / g. see that besides the overall capacity. our approach provides Our approach models adsorption as a process occurring a detailed dispersion of this adsorption of 3. When the relative pressure increases from 6. 2r . the amounts energy of the system.1. For example. pore volume and equation.06 mmol / g calculated using the DR equation. with the amount adsorbed in a a relative pressure of 2. In the case of the ACF. adsorbed in these pores are printed bold. which while in larger pores. Nguyen. threshold pore size for complete filling is 1.33 theory. Since all carbonaceous solids have a Column 3 of Table 2 shows that adsorption occurs mainly distribution of pore sizes.98310 22 to 0. Table 2 summarises the 3.66 nm (or a pore until a critical pressure. C. when the change in for easier reference. One would expect small pores to be filled more larger pores are layered with adsorbate molecules.04 mmol / g. The first three pore sub-ranges information on the individual fractional filling for each are filled completely with adsorbate (bold italic) while pore size. This means that the contribution of size. adsorption layer is built up on the is in the mesopore range. Do / Carbon 39 (2001) 1327 – 1336 1331 Fig. 6. the DR equation gave for traditional HK method.39. and also from the mechanism assumed in the 10 25 to 2. at a reduced pressure of 0. This pore filling schematically illustrated in Fig. where adsorption in a pore is zero this sample a mean pore half width of 0. This mechanism is width less than 0. the DR equation provides only the adsorption data relating to micropores are shown in italics macroscopic information.

5. D. Nguyen.1332 C. 6. . Table 2) of the ACF sample.D. Progress of adsorption in pores of three different sizes. Do / Carbon 39 (2001) 1327 – 1336 Fig. Nitrogen isotherms in different pore sub-ranges (cf. Fig.

3667 5.01 0.1256 4.772 0.03 3.09 – 7.0003 0.24 0.7 10.74 2.030 0.0278 0.9 4.01 0.002 0.843 0.2 0.0208 0.7 13.320 0.9 to 97.0085 0.0258 0.8 0.0011 0.004 0.10 46. D.2 – – 0.1 0.4 0.8 1.98310 22 6. C.3 – – 8.01 0.0161 0.09 1.090 0.23 9.32 2.1 0.683 0.4 0.8267 10.2 – – 2.9 0.39 – 6.2 – – 2.958 0.0674 1.439 0.7624 9.0465 0.1 1.912 0.66 6. unable to deal with mesopores.0155 0.2 0.8551 13.0 – – 0.002 0.7 1.4 0. The difference is more significant at the higher [12.0 0.1 0.6021 9.0126 0.5 – – 0.0 0.805 0.1 – – 0.7 0.0367 1.2 – – 0.0001 0.0134 0.0159 0.1 1.11 7.0002 0.2 – – 0.0 – – 0.0 – – 0.4 0.04 3.2 1.0066 0.1 1.74 3.31 1.0018 0.006 0.2410 7.0144 0.00 5.55 1.0328 0.7 1.1340 1.7 0. underpre.1256 2.83 3.0010 0.36 6.0 0.01 0.99 8. r5] (8) E0 dicts the data at high relative pressures.1141 1.2 1.7 4.2 0.2 1.1914 39.0 – – 0.2653 4.3 – – 6.1 0.0002 0.7 1.001 0.D.0003 0.382 100 – – 7.6021 7.7 0.0 0.0241 0.5 0.534 0.7 0.63 7.99 7.3 13.006 0.308 3.0069 0.0 0.0 – – 0. The amount adsorbed (or E0 ).5 2.0002 0.98 3 10 22 x 5 0.5 – – 1.706 0.8 13.7 0.3 – – 0. the calculated using the DR equation is by and large equal to dependence of the characteristic energy on the size of the the sum of the amounts adsorbed in all pores using our carbon slit pore is found by Dubinin and co-workers technique.04 2.38 0.27 3.1 0.0117 0.005 0.32 2.0637 0.005 0.2.240 97. This is because k the DR equation.0516 0.42 0.5%.9 7.645 0.84 16.12 3.1256 1.9 0.03 10. By investigating a large number of systems.87 – Overall 0.0 – – 0.0240 0.2069 2.10 19.6 0.266 0.0219 0.7 3.5 0.3611 44.0001 0. where adsorption in mesopores following approximate form: occurs in addition to that in micropores.1914 18. This equation is Table 3 Nitrogen adsorption onto ACF sample at three relative pressures calculated using our method and the DR equation Relative Overall capacity Micropore capacity pressure (mmol / g) (mmol / g) – Experimental Our method DR eq.444 0.27 4.8 – – 1.31 .0012 0.4 0.0 0.6 0.0003 0.2 2.042 99.7 0.1 0. Our method 25 6.286 0.0002 0.219 0.044 100 – – 6.12 0.007 0.3611 21.919 0.39 width volume Loading Energy Loading Energy Loading Energy nm cc mmol % J % mmol % J % mmol % J % 0.37 2.24 10. Potential energies of adsorption 95.1382 1.5 63.1 – – 0.0490 0.318 95. with k being a constant (12 kJ nm / mol).24 12.9 28.3 0.397 0.12 1.9 6.4 – – 3.6 0.3 1.1 – – 0.5 10.014 0.5144 6.2069 3.38 6.0155 0.005 0.0 – – 0.5 1.0136 0.6 0.4 7.2653 3.34 2.006 0.0 – – 0.0 7.3 0.3310 3.0 0.8267 13.20 0.0 – – 0.009 0.1688 2.4 0.6 1.006 0. Nguyen.39 7.0 0.2 – – Micropore 0.10 23.3 3 10 25 x 5 2.047 1.4 – – 9.32 4.03 12.8 0.8551 11.3611 17.8 7.0 0.029 0.9 2.021 0.8 55.007 0.004 0.19 6.18 0.40 0.214 0.3 – – 4.041 1.6 0.9 0.3 0.11 0.84 19.009 0. Table 3 presents the results of the nitrogen adsorption The only parameter concerning the solid properties onto the ACF sample at three pressure levels calculated appearing in the DR equation is the characteristic energy E using the DR and our method.0071 0.1914 15.0 1.8 and then 3.2 – – 0.2249 3.0288 0.026 0. while our tech- nique describes well the data at all pressure levels.25 6.0 – – 0.1 10.13].0 1.2 – – 0.663 100 – – adsorption decreases slightly from 99.3 0. and independently by Stoeckli [14] to take the end of the pressure range. Do / Carbon 39 (2001) 1327 – 1336 1333 Table 2 Nitrogen adsorption onto ACF at 77 K at three relative pressures (per gram of sample) Half Fraction x 5 6.485 0.018 0.357 0.002 0.2 7.7 0.84 38.4 4.0007 0.0118 0.3 0.588 0.1663 2.8 0.5 0.3 1.0144 0.254 3.361 0.06 0.

the quantity. Isosteric heat versus fractional loading for nitrogen curves. It is obvious solid–fluid collision diameter. which. A com- . Nguyen. For adsorption in micropores. is an approximation of the average adsorption potential energy. i.e. 2 for comparison with the potential energies used in our approach. Our at any stage of adsorption can thus be estimated. and would follow the two curves when they unite adsorption onto ACF. The heat released from individual micropores for pore size approaching zero. For example. and the cumulative heat is 56. majority of adsorption takes place in micropores.3. the equation lated using the above method and the results are presented for the isosteric heat is given below: in Table 2.24 J (an average of |9 kJ / mol). (kJ / mol) is the heat released at a given loading Cm .D. the decrease in the potential energy collision diameter (i. Knowing that the sorption. 7. adsorption occurring in that pore range. it would lie between those two Fig. Energies curves. The DR characteristic curve. The isosteric heat of adsorption where d is the coefficient of expansion of liquid adsorbate. Since the ACF sample dimension. 2. Do / Carbon 39 (2001) 1327 – 1336 used to estimate the average pore size of a porous carbon once the characteristic energy E (or E0 ) is known from the adsorption isotherm data. due to a of adsorbate molecules is the principal source of heat distribution of pore sizes in the ACF sample. 7 shows the plot of the is the incremental heat produced per mole when the isosteric heat of adsorption of nitrogen at 77 K onto the loading is incrementally increased from Cm to Cm 1 DCm ACF sample. (DCm < Cm ). 7. If a plot representing the average adsorption po- tential energy is drawn. The difference between the potential curves is has a distribution of pores mostly having half widths less the main cause for our and the DR equation to give than 0. which is not the case. can be taken as the first approximation for the heat of essentially a hyperbola gives an infinite potential energy adsorption. Fig. There is a big difference fluid–fluid interaction. D. Despite the convenience and simplicity.983 10 22 . as discussed above.38 nm). More complex equations are also introduced to describe the relationship between the charac- teristic energy and the pore size [15]. The potential energy curves used in our approach represent two extreme energy levels for a molecule residing inside a pore. i. However. One can expect heat will be less than this theoretical maximum value. which is between our and the DR curves at the lower end of the calculated using the Lennard-Jones potential energy equa- pore size range.2 zero loading.e. Eq. at smaller pore sizes. Heat of adsorption at any overall loading (Cm ) by adding up the differential heats. on the other hand. The results are shown in Fig. Here we argue that this is the case of the DR characteristic energy plot shown in Fig. isosteric heats calculated using the DR equation and our sorption with loading would mimic the variation of this technique are quite different. we get an estimation of the total heat released 3. the potential change. The (9) suffers from the fact that the isosteric heat is infinite at maximum possible isosteric heat for nitrogen is |16. By using Clapeyron’s equation.38 mmol of nitrogen is loaded on 1 g S D 1 2 DH 5 DHvap 1 E ln ] u 1/2 Ed T 1] 2 Sln ]u1 D 21 / 2 (9) of the ACF sample. where the solid– difference in potential energy curves could be a reason for fluid interaction is much more significant compared to the the difference in isosteric heats of adsorption. show a maximum potential generated by nitrogen adsorption in pores of different sizes energy (in an absolute sense) for a pore size equal to the of the ACF sample are presented in Table 2. 0.40 nm.1334 C. the potential energy at the pore centre and the minimal potential energy a molecule may have within the pore interior. The potential for adsorption that the energy released is larger in smaller pores and is decreases as the pore size is lowered beyond that threshold proportional to the pore volume. The cumula- for the isosteric heat of adsorption to be calculated tive heats for the three relative pressure levels are calcu- analytically. it which is very small [16].e. The plot of the r–E0 relationship for benzene is pre- sented in Fig. and that adsorption in micropores produces more heat than in the larger pores. The therefore that the changing pattern of the heat of ad. at a relative pressure of 2. as will be discussed further below. It is known that those two potential levels coalesce for very narrow pores. the isosteric released during the adsorption process. an amount of 6. which is tion. This is the cumulative heat produced when the Another advantage of the DR equation is that it allows amount of Cm is loaded into a clean sample. kJ / mol if all pores have widths equal to the nitrogen As discussed above. the bulk of the actual energy is generated by different average pore sizes and isosteric heats of ad. As discussed before.

dotted line. As seen. regarding the application range of the DR equation. It is also possible to prove that samples having allows the assessment of details such as how much of the very skewed PSDs may not comply with the DR equation. solid lines. solid circle).214 nm) of the ACF sample into 44 therms presented in the form of a log (Cm ) versus log n sub-ranges. This explains why the DR equation is not applicable to all microporous In this section we will try to address the question materials. D. sample.286 to 9. and by combining processes occurring in individual pore that a distribution of pore sizes is a prerequisite for the DR ranges using our method of analysis. 8. Thus. and 3. we Several techniques for analysis of adsorption in micro- get the overall isotherm shown as the dotted line in Fig. adsorption capacity and the heat released is contributed by Fig. Conclusions single pore isotherms can be considered to be a straight line. while the later can be used to extract information for the existence of a DR characteristic curve.4. isotherm. Here the isotherms are shown for a relative pressure interval ranging from 1310 24 to 1310 21 . 8 shows the isotherms of nitrogen ad. by adding up the individual isotherms. the Dubinin–Astakhov equation [17]. The method also equation. A linear approximation of The former is by and large a means to fit the experimental the overall isotherm plotted in this mode is an explanation data. PSD and the applicability of the DR equation the distribution must not be very skewed. none of the 4. sorption in these sub-ranges.D. we sub-divide the pore spectrum (half widths can also be explained similarly by considering the iso- from 0. regarding the PSD. However. The DR equation as well as our which is practically a straight line. curve. Fig. It is clear that the overall isotherm of this sample ments of the isosteric heats. Nitrogen isotherms plotted in a log (Cm ) versus log 2 (1 /x) mode (single pore isotherms. which is the pressure interval where the DR equation is normally investigated. for the DR equation to be applicable. Nguyen. 8. Do / Carbon 39 (2001) 1327 – 1336 1335 parison between the methods and / or a justification of the overall nitrogen isotherms for such a hypothetical carbon suitability can be made based on experimental measure. C. the porous solid must have a distribution of micropores. . It is found that the overall adsorption It is then understood that the DR equation is not behaviour as expressed by the DR equation can be derived applicable for adsorbents having a single pore size. (1 /x) plot. the experimental data very well. overall isotherm. To A more general equation of the volume filling of increase the smoothness (resolution) of the simulated micropores theory. Fig. This line is seen to fit technique are capable of describing the adsorption data. but these results are not does not support the concept of an adsorption characteristic available at this stage. pores are presented. 9 shows the PSD together with the individual and the individual pore ranges. experimental.

Nauk SSSR. [2] Dubinin MM.6:183. Adsorption. Langmuir 2000. Langmuir 1999. 9. D. Trans Faraday Soc 1932. The overall isotherm (dotted line) does not comply with the DR equation principle. Stoeckli HF. Nguyen.10:4244. Astakhov BA. 1999. Adsorption 1997. [15] Dubinin MM.28:316.16:1319. 1971. Introduction to carbon science. Plavnik GM.28:728. Acknowledgements [7] Nguyen C. London: Academic Press. Izv. . Zaverina ED. London: Academic Press. Cornwall: Butter- Support from the Australian Research Council is grate. Carbon 1966. Khim. Sing K. Yang R. fully acknowledged. [10] Greg SJ. J Colloid Interface Sci [4] Rouquerol F. Rouquerol J.25:593. and porous solids. Murata K. 1982. DR equation from statistical thermo.75:34. 1989. Do DD. J Chem Eng Japan 1983. Akad. worths. Chem Rev 1960.D. [9] Horvath G. Carbon [1] Dubinin MM. [17] Dubinin MM. Chimia 1974. [11] Nguyen C. Kawazoe K. dynamic Langmuir 1994. [14] Stoeckli HF.60:235. An arbitrary PSD (left) and the nitrogen isotherms in pore sub-ranges (right). 5. Adsorption by powders 1980. Do / Carbon 39 (2001) 1327 – 1336 Fig. References [12] Dubinin MM. Carbon 1978.2:261. Do DD. [8] Marsh H. [16] Wang K. Sing KSW. [3] Kaneko K.1336 C. [5] Polanyi M.3:197. Do DD. 1964.13:6226. surface area and porosity. [13] Dubinin MM.16:470. Plavnik GM.15:3608. Ser [6] Chen SG. Langmuir 1997.

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