Fluid Phase Equilibria 158160 1999.

557563

A new classification of isotherms for Gibbs adsorption of gases on solids

M.D. Donohue ) , G.L. Aranovich
Chemical Engineering Department, The Johns Hopkins Uniersity, 3400 North Charles Street, Baltimore, MD 21218, USA Received 12 April 1998; accepted 25 January 1999

Abstract A systematic analysis of adsorption behavior has been performed. The results are presented here as a new classification of isotherms for fluidrsolid equilibria. q 1999 Elsevier Science B.V. All rights reserved.
Keywords: Gassolid equilibria; Lattice theory; Gibbs adsorption; Classification of isotherms

1. Introduction The first systematic attempt to interpret adsorption isotherms for gasrsolid equilibria was introduced by S. Brunauer, L.S. Deming, W.E. Deming and E. Teller BDDT. in 1940 w1x. These authors classified isotherms into five types. The BDDT classification became the core of the modern IUPAC classification of adsorption isotherms w2,3x. Type I isotherms characterize microporous adsorbents. Types II and III describe adsorption on macroporous adsorbents with strong and weak adsorbateadsorbent interactions, respectively. Types IV and V represent adsorption isotherms with hysteresis. Type VI has steps. The BDDT and IUPAC classifications have two deficiencies: they are incomplete and they give the incorrect impression that adsorption isotherms are always monotonic functions of pressure. Here, we present a brief summary of a comprehensive analysis of adsorption behavior. This analysis is based on experimental results, molecular simulations, and lattice theory concepts proposed by Ono and Kondo w4x in 1960. The OnoKondo approach was derived to describe density gradients at a vaporliquid interface and it has become a classical part of molecular theory for liquid surfaces w5x. This theory has been developed for gassolid and liquidsolid equilibria w611x.
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Corresponding author. Tel.: q1-410-516-7761; fax: q1-410-516-5510; e-mail: mdd@jhu.edu

0378-3812r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 8 - 3 8 1 2 9 9 . 0 0 0 7 4 - 6

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M.D. Donohue, G.L. Aranoich r Fluid Phase Equilibria 158160 (1999) 557563

2. OnoKondo equations Here we consider lattice theory for a one-component adsorbate with being the energy of interaction between nearest neighbors, and s being the energy of interaction between surface and adsorbate molecule in the first layer. Consider taking an adsorbate molecule at a layer i and moving it to an empty site in an infinitely distant layer. This is equivalent to the exchange of a molecule with a vacancy w7x, Mi q V` Vi q M`

1.

where M is the adsorbate molecule, and V is the vacancy that it fills and vice versa. . If this exchange occurs at equilibrium, then: D H y TD S s 0

2.

where D H and D S are the enthalpy and entropy changes, and T is the absolute temperature. The value of D S can be represented in the form: D S s k B ln W1 y k B ln W2

3.

where W1 is the number of configurations where site in the layer i is occupied by an adsorbate molecule and the site in the infinitely distant layer is empty, and W2 is the number of configurations where the site in the infinitely distant layer is occupied by an adsorbate molecule and site in the layer i is empty, and k B is Boltzmanns constant. If the overall number of configurations for the system is W0 , then: W1rW0 s x i l y x` . and W2rW0 s x` l y x i .

4. 5.

where x i is the fraction of sites occupied by molecules in layer i , and x` is the fraction of sites occupied with fluid molecules in the bulk. Substituting Eqs. 4. and 5. into Eq. 3. we obtain D S s k BT ln x i l y x` . r l y x i . x`

6.

The change in enthalpy can be calculated by considering the number of neighboring sites that are occupied near the surface compared to the bulk: D H s y z 1 x iq 1 q z 2 x i q z 1 x iy 1 y z x` .

7.

where z is the volume coordination number, z 2 is the monolayer coordination number, and z 1 s z y z 2 .r2. From Eqs. 2., 6. and 7. it follows that for i G 2: ln x i l y x` . r l y x 1 . x` 4 q rk B T . z 1 x iq 1 y x` . q z 2 x i y x` . q z 1 x iy 1 y x` . s 0 8. For i s 1, Eq. 7. must be modified to include the effect of the interface. Therefore, D H s y z 2 x 1 q z 1 x 2 y z x` . q s Combining Eqs. 2. , 6. and 9. , we obtain: ln x 1 l y x` . r l y x 1 . x` 4 q rk B T . z 2 x 1 q z 1 x 2 y z x` . q srk B T s 0

9. 10.

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3. Analysis of adsorption isotherms 3.1. Monolayer adsorption Eqs. 8. and 10. represent a set of coupled equations. For monolayer adsorption we have x i s x` for i G 2. In the low concentration limit, Eq. 10. gives x 1 s x` expysrk B T . which is Henrys law. When there are no adsorbateadsorbate interactions, s 0, it follows from Eq. 10. that x 1 s x`rw x` q 1 y x` .exp srk B T .x which is analogous the Langmuir isotherm. If x` < x 1 then Eq. 10. gives x 1 s x`rw x` q 1 y x` .exp srk B T q z 2 x 1 rk B T . x. This is similar to the Frumkin adsorption isotherm. 3.2. Multilayer adsorption . The Gibbs adsorption for multilayer adsorption is G x`. s ` is 1 x i y x` . Calculation of isotherm from Eqs. 8. and 10. shows that increasing srk BT leads to an increase in the Henrys constant and a convex shape of the isotherm at small densities. This is a characteristic feature of Type II and IV isotherms in the IUPAC classification w2,3x. For small srk BT , the isotherm becomes concave at small densities. This behavior is known for Type III and Type V isotherms in the IUPAC classification. For low temperature calculations, Eqs. 8. and 10. exhibit steps in the isotherms resulting from two-dimensional phase transitions. This kind of isotherm is considered Type VI in the IUPAC classification w2,3x. 3.3. Adsorption at supercritical conditions Fig. 1 illustrates the behavior of the Gibbs adsorption near and above the critical temperature. Fig. 1a gives theoretical predictions obtained from Eqs. 8. and 10. . Fig. 1b shows experimental

Fig. 1. Isotherm of the Gibbs adsorption in a wide range of conditions. a. Theoretical isotherms for different sets of parameters: 1for r kT sy0.7 and s r kT sy5.2; 2for r kT sy2r3 and s r kT sy5.2; 3for r kT sy2r3 and s r kT sy2r3; 4for r kT sy0.6 and s r kT sy2r3; b. Experimental isotherms for ethylene on carbon black at different temperatures: 1263 K, 2273 K, 3283 K, 4285 K, 5288 K, 6293 K, 7303 K, 8313 K, and 9 323 K. Data from Ref. w12x.

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adsorption isotherms of ethylene on carbon black for temperatures from 263 K to 323 K data from w12x.. As can be seen from Fig. 1b, adsorption isotherms for subcritical ethylene are Type II in the IUPAC classification. However, for supercritical ethylene, the adsorption isotherms show maxima that range from being very pronounced to rather weak. Subcritical isotherms are monotonically increasing functions of the density. Supercritical isotherms have maxima, and at a higher density the Gibbs adsorption goes down as the density goes up. Subcritical isotherms show a singularity at the saturation conditions. The remnants of this singularity lead to the peak at near-critical temperatures curves 2 and 3 in Fig. 1a. . Supercritical isotherms do not have steps. Fig. 1 demonstrates the theoretical roots and experimental evidence for those types of adsorption isotherms which are beyond the current IUPAC classification. In particular, curve 1 in Fig. 1a is for subcritical conditions mean-field critical point is at rk BT s 2r3.. Curve 2 in Fig. 1a is at critical conditions, and at high affinity to the surface. Curve 3 in Fig. 1a is at the same bulk conditions but for low affinity to the surface. Curve 4 in Fig. 1a illustrates the adsorption behavior at the well supercritical temperature and low affinity to the surface. Fig. 1b shows experimental data for subcritical, near-critical, and supercritical conditions. As seen from Fig. 1a and b, at subcritical conditions we have standard BET-like adsorption isotherms. However, near the critical temperature these isotherms change dramatically to non-monotonic behavior showing sharp maxima, and further increase in temperature leads to isotherms with smooth maxima. These types of behavior are predicted theoretically and observed in experiment, but not included in the IUPAC classification.

4. Adsorption in pores and adsorption hysteresis When there is adsorption in porous adsorbents, there is a limit to the number of adsorbed layers. In slit-like pores with n layers there are two surfaces. For n G 3 equations of equilibrium can be represented in general form:
n

ln x i 1 y x` . r 1 y x i . x` q rk B T .

A i k x i y Bk x `
is 1

q Ck srk B T s 0

11.

where 1 F k F n. Eq. 11. indicates the possibility of having stepped isotherms for microporous adsorbents. Such steps have been observed experimentally in high resolution measurements for argon and nitrogen on microporous adsorbents w13x. The current IUPAC classification of adsorption isotherms w2,3x does not include this type of behavior. Eq. 11. also has multiple solutions at low temperatures. When this occurs, a particular bulk density can be in equilibrium with two densities in adsorbed phase. However, this does not lead to hysteresis in the adsorption isotherm. Rather, the requirement that phases in equilibrium have equal spreading pressures results in steps in the adsorption isotherm w14x.

5. New classification of adsorption isotherms The current IUPAC classification of adsorption behavior for gasrsolid equilibria w2,3x reflects the ideas of Brunauer w15x based on knowledge in the 1930s1940s. Though not stated explicitly in the

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Fig. 2. New classification of adsorption isotherms.

IUPAC publications, the IUPAC classification is limited to condensable vapors w16x. However, many important gasrsolid systems fall outside this classification for example, nitrogen, oxygen, fluorine, hydrogen, carbon dioxide, carbon monoxide, nitric oxide, methane, ethylene, some freons at a room temperature.. Moreover, this restriction is ambiguous because gases can be non-condensable in the bulk, but condensable in pores of an adsorbent. In our opinion, the current IUPAC classification w2,3x is obsolete. Fig. 2 shows a new classification of adsorption isotherms. While general, the classification shown in Fig. 2 is meant to be qualitative and does not show all possible details. In this classification, Type I shows adsorption isotherms on microporous adsorbents for subcritical, near critical and supercritical conditions. At supercritical conditions, the isotherm is not monotonic. Types II and III give adsorption isotherms on macroporous adsorbents with strong and weak affinities, respectively. For low temperatures these Types have steps, but increasing temperature transforms them into the smooth monotonic curves which are like those in Types II and III of the IUPAC classification. However, near the critical temperature these isotherms change dramatically to non-monotonic behavior showing sharp maxima, and further increase in temperature leads to isotherms with smooth maxima. Types IV and V characterize mesoporous adsorbents with strong and weak affinities, respectively. For lower temperatures they show adsorption hysteresis. We also have included supercritical isotherms for mesoporous adsorbents which are predicted by lattice theory and the logic of this classification scheme. However, we are not aware of any experimental data showing the disappearance of hysteresis for mesoporous systems at supercritical temperatures.

6. Discussion Many advances have been made over the last sixty years in understanding adsorption behavior. Of particular note are advances that have been made using density functional theory w17,18x, self-consistent field theory w19x, molecular dynamics w20x, and Monte Carlo simulations w21,22x. . Here, we have presented an analysis made by a much simpler theoretical approach. We have shown that the

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OnoKondo model is simple, flexible with respect to various boundary conditions, and able to predict different adsorption behavior in a systematic way. OnoKondo lattice theory is able to predict all known types of adsorption behavior including steps in the isotherms w9x, scaling behavior near saturation conditions w7x, supercritical behavior w8x, and adsorption hysteresis w6x. By changing two energetic parameters energies for adsorbateadsorbate and adsorbateadsorbent interactions., one can obtain smooth or stepped multilayer adsorption isotherms for macroporous adsorbents. By adopting appropriate boundary conditions, it is possible to describe adsorption on microporous adsorbents w11x. The monolayer version of the theory gives all known types of isotherms for monolayer adsorption of gases on solids w23x. Three-dimensional equations allow one to predict adsorption on heterogeneous surfaces w10x and to analyze adsorption hysteresis w6x. However, it should be noted that the new classification of adsorption isotherms shown in Fig. 2 is not based entirely on the model. Rather, we have used this simple model to organize a wide spectrum of experimental results in a logical and systematic way. This could have been done using any of several different approaches. Our conclusion from this analysis is that the IUPAC classification is obsolete. In particular, experiments and calculations shown in Fig. 1 demonstrate isotherms with maxima at supercritical conditions which is forbidden in the framework of the current IUPAC classification w2,3x.. Monte Carlo simulation at these conditions confirms this type of adsorption behavior w22x. This kind of behavior is beyond the current IUPAC classification, and it is included in the new classification shown in Fig. 2.

7. List of symbols kB M n T V W0 W1 W2 xi x` z z2 z1 G DH DS s Boltzmanns constant Adsorbate molecule Number of adsorbed layers Absolute temperature Vacancy Overall number of configurations Number of configurations where site in the layer i is occupied by an adsorbate molecule and the site in the infinitely distant layer is empty Number of configurations where the site in the infinitely distant layer is occupied by an adsorbate molecule and site in the layer i is empty Fraction of sites occupied by molecules in layer i Fraction of sites occupied with fluid molecules in the bulk Volume coordination number Monolayer coordination number z y z 2 .r2 Gibbs adsorption Enthalpy change Entropy Energy of interaction between nearest neighbors Energy of interaction between surface and adsorbate molecule in the first layer

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Acknowledgements MD would like to acknowledge support by the Division of Chemical Sciences of the U.S. Department of Energy, under Contract DE-FG02-87ER13777.

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