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Problem Set 4 Solution

1. The document discusses adsorption isotherms and enthalpies of ethylene and ethane on ZnO. The curves show ethylene has a stronger interaction and lower temperature sensitivity. The Clausius-Claypeyron equation relates the isotherm and enthalpy data. 2. Nitrogen adsorption on a catalyst is used to calculate its specific surface area of 11.3 m2/g using the BET method. 3. The Kelvin equation for condensation on cylindrical walls is derived, with the surface area change being twice that of a sphere of the same radius.

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48 views

Problem Set 4 Solution

1. The document discusses adsorption isotherms and enthalpies of ethylene and ethane on ZnO. The curves show ethylene has a stronger interaction and lower temperature sensitivity. The Clausius-Claypeyron equation relates the isotherm and enthalpy data. 2. Nitrogen adsorption on a catalyst is used to calculate its specific surface area of 11.3 m2/g using the BET method. 3. The Kelvin equation for condensation on cylindrical walls is derived, with the surface area change being twice that of a sphere of the same radius.

Uploaded by

Rod De Guzman
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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ACE43101 Introduction to EChE, UNIST

Catalysis
Fall 2020

Solution to Prob. Sst #4


(Due November 5)

1. Adsorption isotherms for ethylene and ethane on ZnO are shown in Fig. A and enthalphies of
adsorption of these compounds are shown in Fig. B.
(a) Discuss the curves in Fig. A (shape and trend of data with temperature).
-Ethylene has a stronger interaction with ZnO than ethane. Ethylene needs only ~0.03 atm to
reach a saturation coverage, while ethane requires >0.4 atm.
-Ethane adsorption is more sensitive to the temperature variation because of the weak
interaction.

(b) What principle of thermodynamics yields the data in Fig. B from the data in Fig. A?
Clausius-Claypeyron equation of the phase change is applied.

∂(lnP) ΔHst
=
∂(1/T) R
θ

2. Nitrogen adsorption at 77 K for 50.4 g of an ammonia synthesis catalyst gives following


data. What is the specific surface area of the catalyst?

P /mmHg 8 30 50 102 130 148 233 258 330 442


Va /cm3-STP
103 116 130 148 159 163 188 198 221 270
(at 0 ℃, 1 atm)

From the data given, a BET plot of p/v(p0-p) vs. p/p0 can be made that gives the
intercept (I) and slope (s) of
I = 0.05 x 10-3 (cm3)-1
S = 7.5 x 10-3 (cm3)-1
Mass of the sample = 50.4 g;

1
vm = 1/(I + s) = (1/(0.05 + 7.55) x 10-3)(1/50.4) = 2.61 cm3/g of sample.
For N2 at -195℃, the projected area is about 16.2 Ǻ2/molecule.

Sg = (vmNo/V)(16.2) = [(2.61)(6.023 x 1023)/22,400] (16.1) =11.3 x 104 cm2/g


m2/g

3. In class, we derived Kelvin equation for a spherical drop at equilibrium. How the
equation should be modified to be applied for the condensation on cylindrical walls.
(Hint: The change in surface area on formation of an annular ring would be twice that
when forming a spherical drop of the same radius.)

Work done in enlarging a cylindrical liquid,


ds = d(2aL) = 2Lda
= work done in adding molecules to the interior of the drop,
= (0-)dn
0=*+ RT lnp0
 = * + RT lnp

Increase in volume
Vldn = 2aLda = 2aL x (0-dn/2L

0-= Vl/a
RT ln(p/p0) = -Vl/a acyl = Vl / RT ln(p/p0)
Cf. asph = 2Vl / RT ln(p/p0)

4. The following adsorption and desorption isotherms of N2 at 77 K and the scanning


electron micrograph were obtained for α-MoC1-x powders with surface area of 160
m2/g (Lee et al., J. Catal., 1988, 112, 44).

(a) Discuss the shape and the size of the pores present in the sample based on the shape
of the isotherm (Hint: It could be a mixture of two types of isotherm.)
The isotherms can be viewed as a combination of Type 1 (micropores) and Type IV
(mesopores). The shape of the adsorption-desorption hysteresis loop represents Type B (slit-
shaped pores between plate-like particles).

(b) What are the origins of micropores and mesopores (respectively) present in the
sample?

2
In order for the sample possess the surface area of 160 m2/g, which corresponds to
the particle size of 3-4 nm (dp = 6/Sg), the platelike particles of micrometer size
seen by SEM cannot be single crystals. It must consist of 3-4 nm particles and the
space between these tiny nanoparticles must ne the origin of the micropores. The
mesopores of type B hysteresis represents slit-shaped pores between plate-like
particles, which should originate from the space between the micrometer size
platelike particles seen by SEM.

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