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# 14.

## An equation on state known as the ideal-lattice-gas equation8 has been devel-oped

specifically for an adsorbet:

𝓂 𝓃
𝒵= − 𝑙𝑛 (1 − )
𝓃 𝓂

Where 𝓂 is a constant. This equation is based on the presumtions that the surface of the
absorbate is a two-dimensional lattice of energenetically equivalent sites, each of wich may
bind an adsorbatbe molecule, and that the bound molecules do not interact wich other. The
validity of this model is therefofe limited to no more than monolayer coverage. Substitutions
of this equation into Eq. (14.49) and integration leads to the langmuir isoterm:9

𝓂− 𝓃
𝓃= ( ) 𝜅𝑃
𝓂

## Solution for 𝓃 yields

𝓂𝑃
𝓃= 𝓂 (14.50)
+𝑃
𝜅

Alternatively

𝜅𝑏𝑃
𝓃= (14.51)
𝑏+𝑃

Where b = 𝓂/𝜅, and 𝜅 is henry’s constant. Note than when P → 0, 𝓃/𝑃 properly approaches
𝒦. At the other extreme, where Ρ → ∞, 𝓃 approaches 𝓂, the saturation value of the specific
amount absorbed, representing full monolayer coverage.

## Based on the same assumptions as for ideal-lattice-gas equation, langmuir in 1918

derived Eq. (14.50) by noting that at equilibrilium the rate of adsorption of gas molecules
must the equal to the rate of desorption of adsorbed molecules.10 occupied 𝜃 an the fraction
vacant 1 – 𝜃. By definition,

𝔫 𝓂− 𝓃
𝜃≡ and 1-𝜃=
𝔪 𝓂

Where 𝓂 is the value of 𝓃 for full monolayer coverage. For the assumed conditions, the rate
of adsorption is proportional to the rate at wich molecules strike the surface, wich in turn is
propotional to the pressure, and also propotional to the fraction 1 – 𝜃 of surface sites not
occupied by adsorbed molecules. The rate of desorption is proportional to the occiuped
fraction 𝜃 of sites equating the two rates gives

𝑚−𝑛 𝑛
𝜅𝑃 = 𝑘1 𝑚
𝑚

Where k and k1, are proportionality (rate) constans. Solving for n and rearranging gives\

𝑘𝑚𝑃 𝑚𝑃
𝑛= = 1
𝑘𝑃+𝑘 1 +𝑃
𝐾

Where K ≡ k/k1, the ratio of the forward and reverse adsorption rate constan, is the
conventional adsorption equilibrium constan. The secont equality in this equation is
equivalent to Eq. (14.50), and indicates that the adsorption equilibrium canstan is equal to
hendry’s constan divided by m, i.e., K = k/m.

Since the comtions upon wich it is based are fulfilled at low surface coverage, the
langmuir isoterm is always valid as 𝜃 → 0 an as n → 𝜃. As surface coverage increases, these
assumtions become increasingly unrealistik. Never the however, it does not lead to
reasonable values for m.

𝐴𝑑𝐼𝐼
= 𝑛 𝑑 ln 𝑃
𝑅𝑇

## Integration at constant temperature from P = 0 (where II = 0) to P = P and II = II yiels

𝐼𝐼𝐴 𝑃𝑛
= ∫0 𝑑𝑃 (14.52)
𝑅𝑇 𝑃

This equation provides the only means for evaluation of sprading pressure. The integration
may be carried out numerically or graphically with experimental data or the data may be fit to
an equation for an isoterm. For example, if the integration n/P is given by Eq. (14.51), the
langmuir isoterm, then

𝐼𝐼𝐴 𝑃+𝑏
= 𝑘𝑏 ln = (14.53)
𝑅𝑇 𝑏

## An equation valid for n → 0.

No equation of state is known that leads to and adsorption isoterm wich integral fits
experimental data over the entire range of n from zero to full monolayer coverage. Isoterms
that find practical use are often 3-parameter empirical extensions of the langmuir isoterm. An
example is the toth equation:11

Wich reduces to the langmuir equation for t = 1. When the integrand of Eq. (14.52) is
expressed by the toth equation and most other 3-parameter equation, its integration requires
numerical methods. Moreover, the empirical element of such equations often introduces a
singularity that makes them behave improperly in the limit as P → 0. Thus for the toth
equation (t < 1) the second derivative d2n/dP2 approches - ∞ in this limit, making values of
hendry’s constant as calculated by this equation too large. Nevertheless, the toth equation
finds frequent practical use as an adsorption isoterm. However, it is not always suitable, and a
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number of other adsorption isoterms are in use, as discussed by suzuki. among them, the
fruendlich equation,

𝑛
𝜃= = 𝛼𝑃1/𝛽 (𝛽 > 1) (14.55)
𝑚

Is a 2-parameter (𝛼 𝑎𝑛𝑑 𝛽) isotherm that often successfully correlates experimental data for
low and intermediate values of 𝜃.

Example 14.8 our purpose here is to illustrate numerically the concepts devel-oped
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for pure-gas adsorption. Nakahara et al. report data for ethylene adsorbed on a
carbon molecular sieve (A = 650 m2 g-1) at 500C. The data, shown as filled circles on
fig. 14.16, consist of pairs of values (n, P), where n is moles of adsorbate per kg of
adsorbent and P is the equilibrium gas pressure in kPa. Trends shown by the data are
typical for phsycal adsorption on a betergeneous adsorbent at low-to-moderate surface
coverage. The solid line on fig. 14.16 represents a curve-fit to the data by F4 (14.54).
the toth equation, with parameter values as reported by valenzuela and mayers (loc.
Cit.).

m = 4. 7087

b = 2. 1941

t = 0. 3984

## Thes imply an apparent value of Hendry’s constant:

𝑛 𝑛 𝑚
k(Toth) = lim 𝑃 = lim = 𝑏1/𝑡 = 0. 6551 mol 𝑘𝑔−1 kP𝑎−1
𝑃→0 𝑛→0 𝑃

Although the overall quality of the fit is excellent, the value of hendry’s constant is to
large, as we will show.

## Extraction of hendry’s constant from an adsorption isotherm is facilitated

when n/P (rather than n) is considered the dependent variable and n (rather than P) the
independent variable. The data plotted in this form are shown by fig. 14.17. On this
plot, hendry’s constant is the extrapolated intercept:

𝑛
k = lim 𝑃 = lim
𝑃→0 𝑛→0

12
M. Suzuki, Adsorption engineering, pp. 35-51, Elsevier, Amsterdam, 1990.

13
T. Nakahara, M. Hirata, And H. Mori, J. Chem. Eng. Data, vol. 27, pp. 317-320,
1982.
Figure 14.16: Adsorption isotherm for ethylene on acarbon molecular sieve at 500C. Legend:
experimental data; Toth equation; − − − Langmuir equation for n → 0; – ● – ● –
hendry’s law.

Wher the second equality follows from the first because n → 0 as P → 0. Evaluation
of the intercept (and hence of k) is done in this case by fitting all of the n/P data by a
cubic plynomial in n:

𝑛
= 𝐶 0 + C1 + C2n2 + C3n3
𝑃

C0 = 0. 4016

C1 = -0. 6471

C2 = 0. 4567

C3 = -0. 1200

Whence

## k = C0 = 0. 4016 mol kg – 1 kPa – 1

Representation of n/P by the cubic polynomial appears as the solid curve on fig.
14.17, and the extrapolated intercept (C0 = k = 0. 4016) is indicated by an
Figure 14.17: plot of n/P vs. n for ethylene on a carbon molecular sieve at 500C. Legend:
experimental data; cubic polynomial fit of n/P vs. n; – – – Langmuir equation for n →
0; – ● – ● – Hendry’s law; ● ● ● ● ● Toth equation for small n.

Open circle. For comparison. The dotted line is the low-n portion of the n/P curve
given by the Toth equation. Hre it is apparent that the extrapolated intercept k(Toth),
off-scale on this figure, is unreasonably high. The Toth equation cannot provide an
accurate representation of adsorption behavior at very low values of n or P.

The Langmuir equation, on the opther hand, is always suitable for sufficiently
small n or P. Rearrangement of Eq. (14.51) gives

𝑛 1
= k - 𝑏𝑛
𝑃

Wich shows that the Langmuir equation implies a linier variation of n/P with n. Hence
the limiting tangent to the “true” isotherm on a plot of n/P vs. n represents the
langmuir approximation to the isotherm for small n, and is shown by the dashed line
on figs. 14.16 and 14.17. it is given by the equation

𝑛
= 0. 4016 − 0. 6471𝑛
𝑃

Or, equivalently, by

0.6206𝑃
n = 1.5454+𝑃

figures 14.16 and 14.17 show that hendry’s law (represented by the dot-dash lines)
and the limiting form of the Langmuir equation provide, respectively, in this example
upper and lower bounds for the actual isotherm. The langmuir isotherm when fit to all
the exeperimental data yields a curve in fig. 14.16 that fits the data reasonably well,
but not so well as the 3-parameter Toth expression.