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caracterizao
de porosidade em slidos. A equao de Langmuir baseia-se nos seguintes
pressupostos:
1. durante um processo de adsoro inteira s adsoro de monocamada
ocorre.
2. o processo de adsoro localizado com interaes no adsorbateadsorbate.
3. o calor de adsoro independente de cobertura de superfcie, ou seja,
tem o adsorvente
uma superfcie homognea energeticamente.
In reality, none of the above assumptions apply to activated carbon, even approximately,
so it comes as a surprise that the Langmuir equation can be used to linearize adsorption
isotherms. In fact, assumptions 2 and 3 probably compensate for each other, as adsorbateadsorbate
interactions increase with increasing coverage at the same time as enthalpies of
adsorption decrease with increasing coverage.
as causas.
The area assigned to an adsorbed molecule is the area of projection on to a flat surface as
illustrated in Figure 4.9. When adsorbate molecules occupy such sites as are modeled in
Figure 4.3, the unreality of the concept of "surface area" becomes that much more apparent.
The concept is essentially one of quantitatively describing comparative adsorption
capacities (without providing further details of where the adsorption takes place), to satisfy
the requirements of human awareness.
Areas covered by adsorbate molecules, as commonly used, are listed in Table 4.1. It has
to be emphasized that such values of area do not reflect the actual area of projection
within porosities. The problems of part filling of porosity and of volume filling have
already been explained in terms as shown in Figure 4.3. Further, the packing density of
adsorbate molecules is not constant under all conditions but is a function of the dimensions
of the porosity into which it is adsorbed. The areas in Table 4.1 are then of an empirical
nature, and are indicative
para ser enfatizado que esses valores de rea no refletem a real rea de
projeo
dentro de porosidades. Os problemas de parte da porosidade e do volume
de enchimento de enchimento
J foi explicado em termos como mostrado na Figura 4.3. Alm disso, a
densidade de embalagem de
molculas de adsorbate no constantes em todas as condies, mas
uma funo das dimenses
da porosidade em que ele adsorvido. As reas na tabela 4.1 so em
seguida de uma emprica
natureza e so indicativos
Often, from the same isotherm, the three adsorption equations, described above, predict
different values of n^. It is not a matter of debate as to w^hich equation is the correct one.
It is that different parts of the isotherm give different informations. A further complication,
for the same adsorbent, is that different adsorbates provide different isotherms and
so provide different values of n^. The ansv^er to these problems is the same, namely that
the carbon is exhibiting a surface area for adsorbate Al and a different surface area for
adsorbate A2 because surface coverage and/or pore filling mechanisms are different.
There is no right or wrong in this issue.
In the DR plots log V (or log W or log n^) is plotted against lo^plp^, as shown in Figure 4.12
(right). To the left of Figure 4.12 are experimentally determined isotherms. To the right of
Figure 4.12, these curves are redrawn in the coordinates of the DR equation and show differences
between them. In interpreting these DR plots, it is the extrapolation of the linear
portion of the DR plot (from right to left) to the zero value of log^p/p^ which gives the micropore
volume (how expressed depends on the units used). It is not, definitely not, appropriate
to make extrapolations of the data obtained at higher relative pressures (values oflog^p/p^
<~2) because this is where pore filling and capillary condensation occur in porous adsorbents,
and multilayer coverage in non-porous adsorbents.
Further, Figure 4.13 illustrates how the DR plot can be used to detect adsorptions which are
not fitting a statistical distribution curve, that is, the isotherms cannot be linearized over the
entire experimental range of lo^plp^. Such a totally linearized isotherm is rare; indeed
none may exist, simply because the nitrogen adsorbate (or whatever adsorbate is used)
Alm disso, a Figura 4.13 ilustra como a trama do DR pode ser usada para
detectar adsorptions, que so
no cabendo uma curva de distribuio estatstica, isto , as isotermas no
podem ser linearizadas sobre o
toda a gama experimental de loplp. Tal uma isoterma totalmente linear
rara; na verdade
nada pode existir, simplesmente porque o adsorbate do nitrognio (ou
qualquer adsorbate usado)
cannot reach the smallest of pores at high values of logpp. Also, most
microporous carbons
contain some mesoporosity. Figure 4.13(a) is a totally linear DR plot for all
values of
logpp with a complete Gaussian distribution curve (rare). Figure 4.13(b-e)
show deviations
from linearity; (b) indicates that the pores at the wider end of the
distribution range