LECTURE 2 REEN 3001

JAN 2020
LAST CLASS
We learned how to:
First assume a sequence of steps in the reaction (a mechanism!)
Write rate laws for each step assuming each one is reversible
TODAY
Learn about RLS
Postulate a RLS
Use the other steps to eliminate all coverage dependent terms
RATE LIMITING STEP
In steady state:
-rA= rAD =rS = rD
But one step is usually slowest: RLS (rate limiting step)
1. First assume a sequence of steps in the reaction (a mechanism!)
2. Write rate laws for each step assuming each one is reversible
3. Postulate a RLS
4. Use the other steps to eliminate all coverage dependent terms
SYNTHESIS OF RATE LAW
Cumene  benzene + propylene

C+ S  C.S
C.S  B.S + P(g)
B.S  B + S
WHAT IS THE RATE-LIMITING STEP?
To find out what step is the RLS, usually pick one, make it rate-limiting, derive rate
law and see if it is consistent w/ experimental data/observation.
How do we do this?
Choose one step to be the RLS
Whichever step is chosen as the RLS, we are saying that the reaction rate constant (k)
is much smaller than the than the others. It also means that the others are relatively
large, especially compared to r, thus
r/k ~0
WHAT IS THE RATE-LIMITING STEP?
Since
r/k ~0
We can use this identity with the other steps to mathematically define things that
cannot be easily measured
SITE BALANCE
Total sites = vacant sites + occupied sites
NOW, WE HAVE A METHOD:
1. Propose a mechanism (if one is not given)
2. Find rate laws for each step in the mechanism
3. Decide rate-limiting step
4. Define immeasurables and solve for them (reminder: you cannot use the RLS to
define your immeasurables)
5. Define Cv using site balance
6. Plug everything into the rate law of the rate limiting step
CLASS EXERCISE
Find rate law assuming each step is the rate limiting step
IF ADSORPTION IS RLS
IF SURFACE RXN IS RLS
IF DESORPTION IS RLS
EXPERIMENTAL OBSERVATION
NOTE WELL!
Just because the mechanism and the RLS fit the rate data does not imply the
mechanism is correct! Spectroscopic measurements are necessary to confirm a
mechanism!
METHOD FOR COMPLETING QUESTIONS
1. Define mechanism.
2. Find rate laws for each step of the mechanisms.
3. Decide rate limiting step.
4. Define immeasurables.
5. Define Cv.
6. Plug everything in.
EXAMPLE
1-Butyl alcohol (TBA) is an important octane enhancer that is used to replace lead
additives in gasoline [Ind. Eng. Chem. Res., 27. 2224 (1988)]. t-Bu alcohol was
produced by the liquid-phase hydration (W) of isobutene (I) and an Amberlyst- 15
catalyst. The system is normally a multiphase mixture of hydrocarbon, water and solid
catalysts. However, the use of co solvents and excess TBA can achieve reasonable
miscibility.
The reaction mechanism is believed to be:
I+S ↔ I.S
W + S ↔ W.S
W.S + I. S → TBA.S + S
TBA.S ↔ TBA + S
EXAMPLE, CONT.
Derive a rate law assuming:
The surface reaction is rate-limiting.
EXAMPLE, CONT.
Derive a rate law assuming:
The reaction follows Eley-Rideal kinetics.
EXAMPLE, CONT.
Derive a rate law assuming:
Isobutene (I) and water (W) are adsorbed on different sites:
I + S1 ↔ I.S1
W + S2 ↔ W.S2
and TBA is not on the surface, and the surface reaction is rate-limiting.
EXERCISE
The formation of proponal on a catalytic surface is believed to proceed by the
following mechanism.
O2 +2S ↔ 2O·S
C3H6 + O·S → C3H5OH·S
C3H6OH·S ↔ C3H5OH + S
Suggest a rate-limiting step and derive a rate law.