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Problem Set 5 Solution

The document summarizes solutions to problems sets related to catalysis. Problem 1 discusses differentiating between first and second order desorption kinetics using two methods. It also proposes two reasons for unexpected statistical mixing of H2 and D2 observed during coadsorption. Problem 2 analyzes TPD spectra of H2CO and H2 desorption following CH3OD adsorption. It identifies the nature of different desorption states and proposes they originate from the same surface intermediate in a surface reaction limited step. Problem 3 presents TPRS data and XPS evidence from CH3OH adsorption on Fe(100). It proposes a mechanism involving low-temperature H2 desorption and high-temperature CO and H

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39 views

Problem Set 5 Solution

The document summarizes solutions to problems sets related to catalysis. Problem 1 discusses differentiating between first and second order desorption kinetics using two methods. It also proposes two reasons for unexpected statistical mixing of H2 and D2 observed during coadsorption. Problem 2 analyzes TPD spectra of H2CO and H2 desorption following CH3OD adsorption. It identifies the nature of different desorption states and proposes they originate from the same surface intermediate in a surface reaction limited step. Problem 3 presents TPRS data and XPS evidence from CH3OH adsorption on Fe(100). It proposes a mechanism involving low-temperature H2 desorption and high-temperature CO and H

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 Catalysis, Fall 2020

EChE , UNIST

Solution to PROB SET #5


(Due November 12)

1. Please refer to TPD spectrum of hydrogen from W(100)

(a) The β2 peak was interpreted as the second order desorption of dissociatively adsorbed
H atoms. However, this peak could correspond to the first order desorption with
varying activation energy. Recommend two methods to differentiate the two
possibilities.
(1) Plot ln(C0 Tp2) vs. 1/Tp.
If the plot is linear, the desorption is 2nd order.
(2) Desorption rate isotherm method

C’s

T1T1 T2T2 T3T3 T4T4

The slope should be n=2.

(b) The coadsorption of H2 and D2 leads to complete statistical mixing for both β1 and β
2 states. Propose two possible reasons for this unexpected results for the β1 state.

(1) and may be from a single adsorbed state with heat of adsorption decreasing with
coverage in a sigmoidal pattern due to adsorbate-adsorbate interaction.
(2) Interconversion between and by an equilibrium.

Desorption Equilibrium
 

That is, parts of species in state (isotope mixing) convert to  upon heating and desorbs
as state

2. TPD spectrum in Fig. 1 was obtained following CH3OD adsorption at 180 K on a Cu(110)
surface that was predosed with 2 Langmuirs of 18O2 at 295 K. The CH3OD dose was 100s.
Figs. 2 and 3 are TPD spectra as a function of CH3OD exposure for H2CO and H2. The
exposures were (a) 1, (b) 5, (c) 12, (d) 25, and (e) 50 s.

(a) Discuss the nature of β2 and β3 states in Fig. 2 and 3.


In both cases (Fig. 2 and 3), state is filled first, and saturated at low exposires of
methanol. The peak becomes dominant at higher exposures of methanol, and most
of H2CO and H2 desorb from this state. Therefore, state appeas to be due to a small
number of sites with a stronger binding energy, but with similar nature in comparison
with state.

(b) What are the orders of H2CO and H2 desorption.


The invariance of peak temperature with methanol exposure and asymmetric peak
shape demonstrate that the surface reaction-limited step producing H2CO and H2 is a
first order process.

(c) Propose a mechanism of CH3OH decomposition on Cu(110) which is consistent with


1 1 1
TPD data. CH3OH + 2 Oa → H2CO + 2 H2 + 2 H2O

From the first D2O peak,


CH3OD + O  CH3O* + OD*
CH3OD + OD*  D2O + CH3O* + *
Or
CH3OD  CH3O* + D*
2D* + O*  D2O + 2*

H2CO and H2 peaks appear at the same temperature with the same peak shape (both first order).
This suggests that both H2 and H2CO originate from the same surface intermediate
(CH3O*) in the surface reaction limited step.
CH3O*  H2CO + H* (rds)
2H*  H2 + 2*

The second step should be almost instantaneous, otherwise it would have shown the second
order behavior.

3. The following TPRS spectrum was obtained subsequent to CH3OH adsorption at 200 K on
Fe(100). Additional XPS evidence showed that molecular CO was not formed below 400 K.
Give and support mechanism which account for the data. Additional figures for H2/H2 and
CO/CO are attached. The tabulated XPS data are also given.

Table 1
Methanol Adsorption on Fe(100)

Coverage
(Monolayers)
θC θO
a) Clean Surface 0.03 -

b) CH3OH adsorbed at 200 K 0.40 0.35

c) Heated to 300 K 0.33 0.29

d) Heated to 500 K 0.12 0.13

e) Heated to 900 K - 0.02


Low temp. event:
CH3OH + 2*  CH3O* + H*
2 H*  H2 + 2 *
- Low T H2 peak

High temp event:


CH3O* + 4 *  C* + 3H* + O*
C* + O*  CO + 2H*
2H*  H2 + 2*

- NO molecular CO on the surface


- Peak shape indicates 2nd order desorption for both CO and H2
- The ratio of C andremain constant always.

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