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    Asap 1

    Uploaded by

    Cristiane Nunes

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    of 10
    ADSORPTION OF NITROGEN BY POROUS AND NON-POROUS CARBONS P.J.M. Carnot, R. A. Roserts and K. 8. W. Sino Departmen 6¢ Chemistry, Brel University. Uxbridge, Middlesex, UBS SPH. ‘United Kingdom (meceved 27 aren 1300) Abstract—Nitrogen iotherms have been determined 3177 K ona number of carbon blacks and ro: fpnowsearbuny Appietion vf the Dubiin-Rauuabaevidt (DR) inetd tes swt tat nea plo Ee given by both nonporous and microporous samples. The range of nearly is considerably redaced by resin the mropore siz, wi rapisation of onprewscaron eds the fomaton of wo int linet wegios, Avpikationu ew weilaal polensiungerRcave fr (wu sages mie upure cahanced advroate-adsorbent interactions and (6) 2 secondary process which the result of cooperative effects asocated withthe fling of wider mictopores Key Words—Nirogen adsorption, carbon black, microporous carbon, a, method, DR equation 1. astropuctioy the alfinity (4G, the differential free energy of ‘The mechanisms involved in the filling of micropores adsorption). ie. are stil far from clear. [tis known that the enhance- ‘ment of adsorption energy in very fine pores leads to the filling ofthe pore volume at low iclative pres sures, but the upper limit of this micropore filling effect is uncertain{I]. According to the TUPAC clas- sification of pore size(2], micropores are defined as pores with widths not exceeding 2 nm. Theoretical Sakewlativus[3} and eaperinicntal surements of adsorption energies[4] have revealed, however, that the enhancement in the gas-solid in- teraction energy becomes quite small as the pore Width is increased to more than a few molecular di- sameters (Le. 0.7-0.8 umn for uiogen adsorption). These findings indicate that pore filling ofthe larger micropores (termed "'supermicropores” by Dubi- 1in[5,6]) must take place at higher relative pressures by a different adsorption mechanism. The limited sanwount of evidenve available indicates that hig is cooperative process involving the interaction be- tween adsorbate molecules{7} In view of the complexity of physisorption in mi- ‘cropores, it s not surprising that there is no current theory which can provide & general mathematical description ofthe pore filling processes. An approach. pioneered by Dubinin and his co-workers(5.6.8.9] was to combine the Polyani concept of the charac teristic curve with the theory of volume filling of miciopures. For the simplest case of a microporous, carbon containing fairly narrow distribution of pore size. it was proposed[8] that the characteristic curve could be expressed in the form: WIV, ~ expl-(ArEy], a where V is the volume of gas adsorbed at o/p* and V, the volume required to fill the micropores. A is 9 A RT in(p"’p) ° and B is the characteristic fee energy of adsorption for the given system 'A more general expression was in and Astakhow 10: put forward by Dy WIV, = expl-(A/E)| @) which contain the additional parameter m and is ap- plicable toa wide range of microporous carbons and zeolites. Revently, Steck and his eo-workers{11] have developed an alternative generalized treatment for the volume filing of « heterogeneous collection of micropores which is based on the summation of the contributions fom individual pore groups, each roup giving rise wits own characteristic curve in the form of eqa (1), Although eqns (1) and (3) have been found appii- cable on an empirical basis to certain systems over a wide range of temperature and pressure(12], it stiould be noted thatthe parameters & and mate not amenable t independent calculations or experimen- talverification, Furthermore. valuesof Vas assessed by the application of eqa (1) are often found to be of doubtful valdity(1 13). Another serious limitation of Dubinia’s approach w micropore ings tha the characteristic curve concept docs not readily allow for differences in the nature of the gas-olid inter- actions which may affect the course of the isotherm at low surface coverage (or pore filling)[14). Te is evident that wore work is vequited (o establish the degree of usefulness of eqns (1) and (3). Analternativeanproach fr the study of micropore filing is provided by the application of the a, © PJM. CaRnorr eval method[15]. This is an unashamedly empirical ‘method of adsorption isotherm analysis. To apply ‘the method it is necessary to select an appropriate standard isotherm obtained on a nonparens refer- cence adsorbent having a similar surface structure to the microporous solid under investigation. With car- onaceous materials this requirement presents a problem because in general their surface chemical structures are not as well defined as in the case of oxides(16). Four different microporous carbons were chosen {or the present investigation, ‘The main objective of the work was to extend and confirm the previous [roliminary ctndy[12] af the twa stages af mierapaare filling and, in particular, explore the usefulness of the DR and o, methods of isotherm analysis. t was, also considered appropriate to undertake mea- surements, especially at low pressures, on various {graphiticed and ungraphitised carbon blacks. In ad- dition, the a, method has been applied to nitrogen isotherms determined on a mixed microporous ‘mesoporous carbon both before and after the pre adsorption of n-nonane. In this manner it was hoped to obtain new information on the scope and limita tions of the two methods of isotherm analysis as ap- plied to nitrogen adsorption on carbonaceous ad- sorbents. 2. EXPERIMENTAL Four microporous carbons were selected as rep- resentative examples of carbon adsorbents with dif- ferent pore structures. Carbosieve it a polymer- based molecular sieve carbon manufactured by Supelco and supplied by Bioscan, Canvey Island, ‘AX21 is a petroleum pitch-based active carbon of very high adsorption capacity manufactured and sup- plied by the Anderson Development Co., Michigan, ‘Two samples of charcoal cloth were specially pre- pared from viscose rayon cloth by carbonisation in N, at 83U'C tollowed by activation in CO, atthe same temperature{17].JF00S isa low burn-off cloth known ‘to possess only pores of molecular dimensions, while the conditions under which JF517 was prepared were designed to produce a charcoal cloth with a much wider range of pore sizes. In addition a sample of charcoal cloth, XR602, which contains both micro- pores and mesopores wat propared{18}. ‘Three ungraphitised carbon blacks, Spheron6, Valean3 and Elftex120 were supplied by Cabot Car- bon Ltd, llesmere Port. Three graphitised carbon blacks were also studied. Graphon was supplied by Cabot Carbon Ltd., while Vulean3G and Sterling FT were obtained from the National Physical Labora- tory, Teddington. For the purposes of comparison the data of Pierce tor Sterling S (ungraphitised)|19] and Sterling MT (graphitised)[20] have been in- cluded in the study. Sooty Silica is a well-characterised nonporous ad- sorbent made by depositing a carbon layer on the surface of silia[21). It was supplied by ICI ple, Run- Nitrogen isotherms at77 K were determined using 1 Carlo-Erha Series 1800 Sorptomatic. For certain samples (notably Sooty Silica) the isotherms were repeated using a manual volumetric apparatus of the type designed by Harns and Sing|22). For the mea- surement of pressures below 40 mm Hg a Datamet rics type 565.91 Rarocel transcicer was employed. Samples were outgassed at 250°C (140°C for Sooty Silia) for 16 h toa residual pressure <10-* mm Hig 3. RESULTS AND DISCUSSION 3.1 Adsorption isotherms Representative nitrogen isotherms obtained with the microporous carbons are shown in Fig. 1. ‘The predominant character ofall these isotherms is type 1, hut it ig evident thar their precise shape varies significantly from one adsorbent to another. Ina few cases (notably Carbosieve and charcoal cloth JF00S) there isa steep uptake of gas at very low p/p", while with other samples (e.g. AX21 and charcoal cloth TESI7) there is « more gradual approach ta a rather ill-defined plateau located at higher p/p*. In the case of JFSI7 the appearance of the small hysteresis loop 's indicative of the existence of some mesoporosiy. ‘The isotherms in Fig. 2 are representative of those obtained with the various graphitised and ungraphi- tised carbon blacks. The type-II character of these isotherms indicates that the degree of microporosity and mesoporosity was relatively low. Graphitisation cf Vulcan3 has resulted in a slight change in shape of the ieotherm with a sharpening of the first knee and the development of a step at p/p? ~ 0.2. A sim- xr change has been found with Graphon and Ster- ling FT. 4.2. Dubinin-Redushkevich plots By combining eqns (1) and (2) we obtain the Du- binin-Radushkevich (DR) equation(8|: VV, = expl~BITIB}I0g(p'Ip)), (4) where B is the so-called structural constant and ® is a scaling factor (or “similarity coefficient”). Reat= rangement of eqn (8) lead tothe DR equation ints linear form, log¥ = lonV, ~ Diog\p"p), (5) where D = BIB): ‘The DR plots in Figs. 3 and 4 were constructed in the usual way, ie. a logY against log'(p"/p), from the isotherms in Figs. 1 and 2, respectively. It is apparent thatthe DR plots on the microporous car- bons (Fig. 3) areal linear at low p/p". The range ot linearity is most extensive with Carbosieve and char- coal cloth JPDIS, but even in these eases it dws nat extend above pip’ ~ 0.05. The other DR plots in Fig. 3 are linear only up to pip* ~ 0.005. Adsorption of nitrogen According to eqn (5), the intercept of the linear DK plot should equal logV,, where Vi the volume of gas required to fil the micropores” The values of V, 90 obtained by back extrapolation ofthe lear sections of the DR plots have been converted into mieropore volumes (v? in Table 1) by assuming that the poreshave been filled with iquidnitrogen (taking its density as 0,808 cm"), We shal return later to the question ofthe validity ofthe values of vP Tehas been noted previously] that some nonpo- cous solids give linear DR plots and tis therefore of Interest to establish whether this isthe case with the carbon blacks tudiedin the present work. Inspection of Fig. revens that whereas Spheroné, Sooty Silica and Elftex120 all give nearly linear DR plots over & vide range of low p/p", Graphon and Sterling FT bBve DR plots of quite diferent character, having ‘wo separite linear branches alow p/p. These di 02 0-4 6 ferences evidently reflect the marked change in iso- therm shape produced by graphitsation. Dubinin and Stoeckli[12] have pointed out that ‘eqn (1) can be applied tothe majority of microporous carbons which possess a fairly narrow distribution of pores of molecular dimensions. Our work confirms that the simple DR equation is indeed applicable to such systems—at least up to p/p? ~ 0.05, On the ‘other hand, iis evident that linearity of the DR plots provides only the first stepin any attempt to establish the validity of the Dubinin theory of micropore fill- ing. 3.3 plow Recent work{21} has shown that certain samples cf carbon coated silica (Sooty Silica) give reduced nitrogen isotherms which are almost identical in shape to the standard isotherms determined previ- 06 0-8 p/p® Fig. 1. Adsorption isotherms on microporous carbons. Open symbols, adsorption: closed symbols,

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