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CATALYZED

REACTIONS
Suhadi Ibnu

Catalyst:

A species which increases the


rate of reaction but is not consumed in the
reaction. (It is involved in reaction but will
be released as its initial form at the end of
reaction).
Catalyst creates another way
(mechanism) of reaction with lower
activation energy.

Catalyst

From

their homogeneity with their medium,


catalyst can be divided into two groups:
Homogeneous Catalyst: Acid-base catalysts, other
than acid-base catalists.
Heterogeneous Catalyst: Various metal powder

Besides

Acid-Base and metal-powder


catalysts enzymes are also effective catalysts
for certain reactions.

Catalyst

Catalist

changes the mechanism of reactions.


Examples:
(1) CO + O2 CO2 (without catalist).
With

catalist (NO2): CO + NO2 CO2 + NO,


then NO + O2 NO2

(2)

Decomposition of acethaldehyde with Iodium as


catalist

Non Acid-Base Catalists

I2

2I.

(with k1 and k-1 as the constants)

I.

+ CH3CHO CH3CO. + HI (k2)


CH3CO. CH3. + CO (k3)
CH3. + I2 CH3I + I. (k4 and k5)
CH3I + HI CH4 + I2 (k6)
The

overall constant is as follows:

k = (k1/2k-1)1/2 k2

Non Acid-Base Catalist

Acid-Base

Catalysts consists of

General Acid-base catalyst: any acid or base can


act as a catalyst.
Specific Acid-base catalyst: only certain acids or
bases can act as a catalyst. For example
formation of esters from acids and alcohols can
only be catalyzed by H3O+ or OH Protons produced from the acids or OH- from the
bases will influence the electronic structure of the
reactants so that they are more ready to react.

Acid-Base Catalysts

kkat

= k0 + kH+[H3O+] + kOH- [OH-] +


kHA[HA] + kA-[A-]

The

above formula applies alternately for


general acid or base catalist.
For specific acid-base catalist only [H3O+] or
[OH-] which will be considered.

k Statement for General Acid-base


Catalist

Cu,

Ni, Mo, and zeolite powder(s) are


intensively used as heterogeneous
catalysts, especially in industry.
Just like protons and hydroxyl ions, the
active hills and valleys of the metal
surfaces will influence the electronic
structure of the reactants.

Metal Powder Catalyst

Mechanism

of Reaction: diffusion,
adsorption, reaction, desorption, diffusion.
The most important step is reaction on the
surface of the metal, which has lower
activation energy than reaction without a
catalyst.
This reaction is influenced by the partial
pressure (pA) of the gas and the fraction of
the surface closed by reactant molecules ().

Reactions of Gas on Metal


Surfaces

Rate

of adsorption of the gas by the


surface is proportional to the open fraction
of the surface (1 - ) and the partial
pressure of the gas pA
When N positions are occupied by
reactant molecules, the Adsorption Rate is
= kads N(1 - )

Reactions of Gas on Metal


Surfaces

Rate

of desorption is proportional to
closed fraction of the surface (N)
Rate of desorption = kdes N
At equilibrium adsorption rate =
desorption rate

kads N(1 - ) = kdes N , and

= pA/pA + K, di mana K = kdes/ kads

Reactions of Gas on Metal


Surfaces

Reaction

rate = k = kpA/(pA + K)

Jika

pA >> K (tekanan parsial tinggi), maka


Kecepatan reaksi = k (K diabaikan terhadap pA),
reaksi adalah orde 0 terhadap A.

Jika

pA << K (tekanan parsial rendah)


Kecepatan reaksi = kpA/K (reaksi orde 1 terhadap A)

Reactions of Gas on Metal


Surfaces

Jika ada reaktan lain (B) bereaksi dengan


A yang telah diserap di permukaan,
kecepatannya tergantung pada tekanan
parsial B dan jumlah A yang telah terserap
di permukaan.
Kecepatan reaksi = kpApB/(pA + K)
Dan jika tekanan parsial A tinggi maka
Kecepatan reaksi = kpB (reaksi orde 1
terhadap B)

Reactions of Gas on Metal


Surfaces

Penggandaan

kecepatan reaksi dengan


penambahan katalis heterogen dapat
dihitung dengan rumus

khet/khom = exp(-Eahet/RT)/exp(-Eahom/RT)
(Show

example(s) at this point)

Reactions of Gas on Metal


Surfaces

Kind of Catalists

Decomp.

R Surface Ehet* Ehom *

HI
Au
Pt 14.0

25.0

44.0

N2O
Au
Pt 32.5

29.0

58.5

NH3
Mo

W 39.0
80
Os
47.0
32-42

CH4

Pt 55-60 80

* In k.cal mol

-1

Factors Influencing Catalyzed


Reactions by Solids

Kind

of solid catalists
The strenghth of the adsorption of the
reactant (s) by the surface
Temperature

Factors Influencing Catalyzed


Reactions by Solids

The

adsorption of the reactant (s) by the


surface (According to Langmuir Isotherm)

Weakly

absorbed: First Order for Unimolecular


Reactions . 2nd order for bimolecular reactions.

Moderately

1)

Strongly

Obsorbed: The order is a fraction (<

absorbed: 0th order leads to poisoning.

Factors Influencing Catalyzed


Reactions by Solids

Temperature
Orders

of reaction usually change because


of temperature, example.
In the decomposition of SbH3 on the
surface of Sb the order changes from 0.6
at 250C to close to 1 at higher
temperatures.

Factors Influencing Catalyzed


Reactions by Solids

Reaksi

terkatalisis enzym terjadi ddalam


tiga tahap:

1:

E + S ES d(ES)/dt = ka(E)(S)
2: ES E + S -d(ES)/dt = ka(ES)
3: ES P + E d(P)/dt = -d(ES)/dt =
kb(ES)

Enzym sebagai Katalis

Dengan

pendekatan steady state:

d(ES)/dt
Penurunan

= ka(E)(S) - kb(ES) - ka(ES) = 0


matematik lebih lanjut menghasilkan:

d(P)/dt
k

= k (E)0, di mana

= kb(S)/{(S) + Km}

Di

mana Km = ka + kb/ka

Km

disebut konstanta Michaelis-Menten.

Enzym sebagai Katalis