Fresenius J Anal Chem (1999) 363 : 174 178

Springer-Verlag 1999

O R I G I N A L PA P E R

K. Meyer P. Klobes

Comparison between different presentations of pore size distribution in porous materials

Received: 15 May 1998 / Revised: 8 October 1998 / Accepted: 10 October 1998

Abstract The different presentations of the pore size distribution derived from the gas adsorption method and the mercury porosimetry are connected with some problems. This concerns especially the use of the logarithmically differential pore volume distribution. The incorrect application of this distribution to bimodal pore systems involves the danger of an apparent overemphasizing of larger pores. This effect may also occur using the incremental pore size distribution in case the experimental point spacing considerably increases towards the larger pore radii. The pore volume density distribution defined as the linear derivative of the cumulative pore volume curve with respect to the pore radius has been found the most convenient form among the various kinds of pore volume distribution presentations. It has been shown that the direct comparison between this distribution and the logarithmically differential pore volume distribution is not allowed. Nevertheless, there is a clear connection between these definitions for the pore size distribution so that they are completely equivalent.

mass, various definitions for the pore size distribution are used. As will be shown below, this impedes comparisons between results of authors with different chosen definitions for the pore size distributions. Therefore, the aim of this paper is to point to some problems connected with expressing pore size distribution using some of the definitions employed in practice.

2 Experimental background
Gas adsorption measurements and mercury porosimetry are classical methods for the characterization of pores in a variety of materials such as catalysts, industrial adsorbents, pigments, fillers, building materials, rocks, and other materials [2]. Pore analysis by means of gas adsorption is based on the physisorption of inert gases (e.g. N2, Ar, Kr) on solids. The primarily experimental data are adsorption / desorption isotherms from which all the other parameters of pores up to a width of about 50 nm (micro- and mesopores) are calculated. In the case of mercury porosimetry mesoand macropores in the range between about 3.5 nm and 500 m are investigated by using pressurized mercury as nonwetting fluid. Information on the pore system of the sample is obtainable by the analysis of the intrusion curve up to pressures of the order of 400 MPa. In spite of the different physical principles on which the two methods are based, their common feature consists in the stepwise determination of pore volume increments Vi that are assigned to the particular pore width intervals. Since for the following considerations simple cylindrical pores will be assumed, the pore width can be expressed by the pore radius r. The sum of all the pore volume increments represents the total pore volume given by the method used. The partial sums of the pore volume increments only up to an pore radius ri plotted in dependence on the pore radius is called the cumulative pore volume curve. Vcum(ri) = iVi (1) In mercury porosimetry as well as in the case of analyzing the desorption branch of a physisorption isotherm (gas desorption porosimetry) the summation in Eq. (1) starts at the larger pore radii since in mercury porosimetry the larger pores are filled first and in gas desorption the larger pores are emptied first. For this reason the cumulative pore volume Vcum decreases as ri increases. Because of the opposite direction of pore filling in gas adsorption (small pores first), iVi of course increases with increasing ri. An experimental example for a cumulative pore volume curve calculated from the desorption branch of the nitrogen isotherm of TaC gel [3] at 77 K is shown in Fig. 1 a and 1 b. The abscissa in Fig. 1 a

1 Introduction
Despite the development of a variety of modern methods for solid state and surface characterization [1], gas adsorption experiments and mercury porosimetry have remained very important methods for investigating porous materials. Both methods provide such parameters as the specific surface area, the specific pore volume, and the pore size distribution. Whereas the specific surface area or the specific pore volume are unambiguously defined as total surface area or total pore volume divided by sample

Dedicated to Professor Dr. Gnter Marx on the occasion of his 60th birthday K. Meyer ( ) P. Klobes Federal Institute for Materials Research and Testing (BAM), D-12200 Berlin, Germany

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3 Pore size distributions

An important aim of the porosity analysis is the determination of the pore size distribution of the sample under investigation. For the simple reason that two equal pore volume increments at two pore radii are associated with rather different numbers of pores even if the radius difference is only small (see Fig. 2), the experimental pore volume increments cannot give any information (in the sense of pore numbers or pore population) about the frequency of the pores different by size without any detailed knowledge of the real pore shape. The pore shape assumed for the calculations in Fig. 2 was a cube with one opened side and with an edge a = 2r and a volume V(r) = 8 r3. Then the number (r) of pores per cm3 at radius r is given by the ratio V /V(r) where V is the volume increment of 0.1 cm3, here assumed to be constant. Because of these difficulties, the pore size distribution is usually expressed in the form of a pore volume distribution in dependence on the pore radius. Since the changes in slope of the cumulative pore volume curve together with its general shape show some details of the pore volume distribution of the sample, this curve may be considered as an example of a presentation of the pore volume distribution and should here be denoted as D0 (see Eq. (2)). D0(ri) = Vcum(ri) = iVi (2)

Fig. 1 a Cumulative pore volume Vcum = iVi (TaC gel, N2 at 77 K, linear r-axis); b Plots of i) Vcum (ri) = iVi calculated from data of Fig. 1 a. log10 spaced r-axis (abscissa at the bottom of the diagram); ii) Vcum (lgri) = i Vi calculated from data of Fig. 1 a, logarithmically transformed coordinates (abscissa at the top of the diagram) is linear whereas in Fig. 1 b two kinds of r-axes are used. The axis at the bottom of the diagram is a logarithmically spaced abscissa. In general, a logarithmically spaced abscissa using the common logarithm lg (log10) or the natural logarithm ln is preferred for presenting the cumulative pore volume curve in a wide range of pore radii, for instance in mercury porosimetry with a measuring range over several magnitudes of r (from about 2 nm up to 200 m) [4]. It should be noted that the use of a log10 spaced abscissa does not mean a real coordinate transformation in the sense of ri lgri and consequently Vcum(ri) Vcum(lgri) since it only serves for another presentation of the plot. In other words, it is necessary to distinguish clearly between the numerical values and the kind of coordinate spacing (linear or logarithmic). Choosing only a logarithmically spaced axis instead of a linear one leaves the ri-values unchanged. In contrast, the consequence of a coordinate transformation consists in a numerical change of the abscissa values (now lgri, see the abscissa at the top of the diagram). As it is evident from Fig. 1 b, the plot of Vcum(ri) on a logarithmically spaced abscissa and the plot of Vcum(lgri) on a linearly spaced abscissa coincide despite their different mathematical characters. Sometimes, a logarithmically spaced r-axis has also been used to present results of gas adsorption / desorption measurements [5, 6]. The specific surface area using gas adsorption methods may be obtained by the BET method [7] or from pore wall areas [8]. In mercury porosimetry, the Rootare-Prenzlow model [9] has often been applied for this purpose.

Fig. 2 a Assumed pore volume increments of 0.1 cm3/g at r = 10 nm and r = 30 nm; b From values in Fig. 2 a calculated numbers (r) of pores per cm3 at r = 10 nm and r = 30 nm

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Fig. 3 a Incremental pore volume distribution D1(ri), calculated from data of Fig. 1 a; b Incremental pore volume distribution D1(ri) from Fig. 3 a as bar graph plot

corresponding ri which leads to the distribution D2 as another kind of a differential pore volume distribution. D2(ri) = Vi/ri (4) The physical unit of D2 is cm3/g/nm, which may be interpreted as a pore volume density (the pore volume in the pore radius interval of 1 nm). The advantage of the distribution D2 consists of the fact that the division by ri compensates the effects of irregular point spacing. This may be regarded as a form of a normalization so that all values of D2 over the whole r-axis are comparable with each other. The plot of D2 versus ri calculated from the cumulative pore volume curve of Fig. 1 is shown in Fig. 4. The pore volume in a wider pore radius range is given by the area under the curve if a linear r-axis is used. Note that in case of using a logarithmically compressed r-axis the peak areas on the plotted curve of D2 are not proportional to total volumes. Therefore, correct results are only available using a numerical integration. The values of D2 represent the slopes of the cumulative pore volume curve in the corresponding ri ranges. The pore volume distribution D2 is identical to the pore size distribution recommended by the International Union for Pure and Applied Chemistry (IUPAC) [11]. Dividing D2 by the total pore volume VP (maximum value of the cumulative pore volume curve) gives an alternative way to present the pore size distribution as a probability density function D2a (see Eq. (5)) with a phys-

The character of D0 as an integral distribution follows from its definition as a sum. It is obvious that in ranges with a steep cumulative pore volume curve more pore volume is concentrated than in flatter ones. However, it should be considered that as seen from Fig. 1 a and 1 b the slopes of D0 and hence its plotted shape depend on the kind of the plot, especially on the chosen spacing of the xaxis. Another very simple possibility of showing some features of the pore volume distribution consists in plotting the pore volume increments Vi versus the pore radius, here denoted as distribution D1 (incremental pore volume distribution, see Eq. (3)). The distribution D1 is an example of a differential pore volume distribution. D1(ri) = Vi (3)

The minus sign on the right side of Eq. (3) results from the continuously decreasing character of our cumulative curve, i.e. it is necessary because the differences Vi = Vi Vi1 are negative. Two examples for the distribution D1 are shown in Fig. 3. The bar graph plot in Fig. 3 b is often used in mercury porosimetry. For an example see ASTM D 4404-84 [10]. The unit of the y-axis is cm3/g (like a specific pore volume) in each of the two plots of D1 shown in Fig. 3 a and 3 b. That means D1 is a real pore volume distribution depending on the pore radius. A disadvantage of the distribution D1 consists in the fact that the ordinate values are dependent upon experimental point spacing since more pore volume will be accumulated by summation in a larger pore radius interval than in a smaller one, even in case of rather evenly distributed pore volume. As a result of that, an apparent overemphasis of larger pores may occur in the plot. In order to reduce that effect, an interpolation (linear interpolation or cubic spline) between widely spaced experimental points in the cumulative pore volume curve and a renewed calculation of the Vi should be carried out. It is obvious that a way to avoid such a dependence on point spacing may consist in the division of Vi by the

Fig. 4 Differential pore volume distribution D2(ri) = -Vi/ri (pore volume density), calculated from data of Fig. 1 a

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ical ordinate unit 1/nm and hence with other numerical ordinate values [12, 13]. D2a(ri) = 1/Vp(Vi/ri) (5) However, the shapes of the curves of D2 and D2a are exactly the same because Vp is a constant quantity. A further differential pore size distribution frequently used in some papers is based on the logarithmic differentiation Vi/lgri [5, 1417]. The plots of this quantity calculated from the values of Fig. 1 are shown in Fig. 5. In the same way as in Fig. 1 b, the Fig. 5 also contains two plots completely coinciding. Compared with D2, the plot of Vi/lgri on the log10 spaced r-axis has a different shape and implies a different interpretation of the pore system of the investigated sample. The distribution in Fig. 5 exhibits two nearly equal maxima at about 2 nm and at about 30 nm whereas the distribution D2 in Fig. 4 clearly shows the domination of the smaller pores. How could the contradictions between these two distributions be interpreted? From a physical joint of view, a direct comparison of the distribution D2 and the logarithmically derived one plotted on the log10 spaced r-axis is not allowed because they have not the same units (see ordinates in Fig. 4 and Fig. 5). From a mathematical point of view, however, there is a clear relationship between these two distributions. According to the rules of differential calculus, the derivative Vi/ri is connected with Vi/lgri by
lgri Vi Vi = ri lgri ri

which corresponds to the coordinate transformation ri lgri. This indicates that Vi/lgri must be interpreted as the derivative of the curve D0(lgri) in Fig. 1 b instead of D0(ri) leading to the definition D3(lgri) = Vi/lgri (7) Therefore, the correct abscissa for the plot of Vi/lgri is the linear axis at the top of the diagram in Fig. 5. The Eq. (7) is equivalent to the definition of Lowell and Shields [18]. They have proposed the distribution D(lnri) = Vi/lnri using the natural logarithm to compress the data since the distribution D2(ri) may scale over several orders of magnitude, particularly in the case of mercury porosimetry. With Eqs. (6) and (8)
V V = 2.303 r r lgr the relationship in Eq. (9) is available:

(8) (9)

D3(lgri) = 2.303 ri D2(ri)

(6)

Fig. 5 Differential pore size distributions i) D3(ri) = -Vi/lgr1 calculated from data of Fig. 1 a, log10 spaced r-axis (abscissa at the bottom of the diagram); ii) D3(lgr1) = -Vi/lgri calculated from data of Fig. 1 a, logarithmically transformed coordinates (abscissa at the top of the diagram) Table 1 Summary of definitions for pore size distributions Distribution Cumulative pore volume Vcum(ri) Incremental pore volume Differential pore volume Probability distribution log differential pore volume

Therefore, the presentation of D3 over a log10 spaced abscissa sometimes found in literature [5, 15, 16] is misleading because it implies that the difference between D2 and D3 only consists in multiplying by 2.303ri, which may be interpreted as a special kind of weighting. This weighting would explain the emphasis of pores at higher pore radii using the distribution D3 but this is an artificial effect without any physical basis. Since the distributions D2(ri) and D3(lgri) have different physical units and are related to different kinds of coordinates, a direct comparison between their shapes is not allowed. Nevertheless, D3(lgri) contains the same information as D2(ri) which can be seen after the correct coordinate transformation lgri ri. Although the distributions D1 and D3 have the same unit cm3/g, these distributions are not directly comparable, too. This would be evident by a plot in one common diagram regardless of their relation to different kinds of coordinates (ri and lgri). The comparison between the ordinate values in Fig. 3 a and Fig. 5 indicates that at all pore radii the distribution D3 would exceed the pore volume experimentally found. Moreover, the value of D3 at about 1.9 nm even exceeds the total pore volume (maximum value of the distribution D0, see Fig. 1). Therefore, the use of the distribution D3 for the discussion of a bimodal pore size distribution may lead to a non-realistic picture of the pore size distribution in some cases. All the definitions of pore size distribution used in this paper are summarized in Table 1.

Definition D0(ri) = iVi D1(ri) = -Vi D2(ri) = -Vi/ri D2a(ri) = -1/Vp(Vi/ri) D3(Igri) = -Vi/Igri

Units cm3/g cm3/g cm3/(gnm) 1/nm cm3/g

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4 Conclusions
All the presentations for the pore size distribution based on the analysis of gas adsorption or desorption isotherms and on mercury porosimetric measurements are different kinds of the pore volume distribution with reference to the pore radius. The use of these presentations may be partly connected with some problems. In addition to the dependence of the ordinate values of the incremental pore size distribution D1 on the experimental point spacing, this concerns especially the use of the pore volume distribution D3 based on the logarithmic derivation of the cumulative distribution D0. The distribution D3 is related to lgri instead of ri coordinates. Ignoring this fact leads to an incorrect application of the distribution D3 which in the case of bimodal pore systems causes an apparent overemphasizing of larger pores. Therefore, a direct discussion of the shape of this distribution should be avoided. The difficulties with the distribution D3 can be overcome by taking into account that D3 represents the logarithmically transformed distribution D2 (linear derivative of the cumulative pore volume curve with respect to the pore radius). This means that the distribution D3 may be turned into the pore volume distribution D2 by the coordinate transformation lgri ri. After that transformation a reasonable discussion of the pore size distribution of the sample under investigation should be possible. Compared with the other definitions considered in this paper the distribution D2 is connected with the least number of problems for practical use. Therefore, the pore volume density distribution D2 seems to be the most convenient definition among the various kinds for presenting the pore size distribution.
Acknowledgement The authors wish to express their thanks to the Fonds der Chemischen Industrie (FCI) for financial support of this work.

References
1. Rouquerol J, Avnir D, Fairbridge CW, Everett DH, Haynes JH, Pernicone N, Ramsay JDF, Sing KSW, Unger KK (1994) Pure & Appl Chem 66 : 17391758 2. Meyer K, Lorenz P, Rhl-Kuhn B, Klobes P (1994) Cryst Res Technol 29 : 903930 3. Preiss H, Schultze D, Klobes P (1997) J Europ Ceramic Soc 17 : 14231435 4. Allen T (1997) Particle Size Measurement. vol 2. Surface area and pore size determination. Chapman & Hall, London, 5th edn, pp 169185 5. Smith DM, Gallegos DP (1988) In: Unger KK, Rouquerol J, Sing KSW, Krahl H (eds) Studies in Surface Science and Catalysis, vol 39. Elsevier, Amsterdam, pp 391400 6. Mendioroz S, Daza L, Pajares JA (1988) In: Unger KK, Rouquerol J, Sing KSW, Krahl H (eds) Studies in Surface Science and Catalysis, vol 39. Elsevier, Amsterdam, pp 589599 7. Brunauer S, Emmett PH, Teller E (1938) J Am Chem Soc 60 : 309319 8. Gregg SJ, Sing KSW (1982) Adsorption, Surface Area and Porosity. Academic Press, London, 2nd edn 9. Rootare HM, Prenzlow CF (1967) J Phys Chem 71 : 27332736 10. ASTM D 4404-84 (1985) In: Annual Book of ASTM Standards, vol 04.08, American Society for Testing and Materials, Philadelphia, pp 860867 11. Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Pure & Appl Chem 57 : 603619 12. McEaney B, Mays TJ (1995) In: Patrick JW (ed) Porosity in Carbons. Edward Arnold, London, pp 100101 13. Rudakoff G, Vogelsberger W, Sonnefeld J (1983) Z Phys Chemie (Leipzig) 264 : 225234 14. Amano E, Kitano R, Kondo S (1988) In: Unger KK, Rouquerol J, Sing KSW, Krahl H (eds) Studies in Surface Science and Catalysis, vol 39. Elsevier, Amsterdam, pp 635641 15. Kartel NT, Puzy AM, Strelko VV (1991) In: RodrguezReinoso F, Rouquerol J, Sing KSW, Unger KK (eds) Studies in Surface Science and Catalysis, vol 62. Elsevier, Amsterdam, pp 439447 16. Lecloux A, Blacher S, Kessels P-Y, Marchot P, Merlo J-L, Noville F, Pirard J-P (1991) In: Rodrguez-Reinoso F, Rouquerol J, Sing KSW, Unger KK (eds) Studies in Surface Science and Catalysis, vol 62. Elsevier, Amsterdam, pp 659668 17. Bautista MC, Rubio J, Otelo JL (1994) In: Rouquerol J, Rodrguez-Reinoso F, Sing KSW, Unger KK (eds) Studies in Surface Science and Catalysis, vol 87. Elsevier, Amsterdam, pp 449455 18. Lovell S, Shields JE (1991) Powder Surface Area and Porosity, Chapman & Hall, London, 3rd edn, p 110