Autooxidation autocatalytic process and it is an

oxidation that converts alkanes into alkyl peroxides

R H O2 ROOH

R H R H ,
R O2 ROO
ROO R H ROOH R

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Lab safety :

Organic chemicals will react with oxygen in the air

at room temperature in chain reactions

Hence forming organic peroxides (fuel /C & H

atoms in the compounds)

Consequences : spontaneous react, explosion upon

shaking or opening the cap

Organic peroxide have very exothermic heats of

decomposition

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

The reactions can only occur if oxygen is present

The reaction depends crucially on the initiation steps,

and different molecules have vastly different
capabilities of dissociation

The reaction depends crucially on the initiation steps,

and different molecules have vastly different
capabilities of dissociation

The initiation step can be photoinduced. If a bottle is

sitting in sunlight, UV photons can cause photo
dissociation to initiate the chain reaction much faster
than in the dark

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Organic molecule (R-H) where R could be an alkyl or
any fragment containing C, H and O atoms

In the presence of O2, this molecule undergo auto

oxidation reaction :

R H O2 ROOH

The chain reactions proceeds at high temperature to

break the R-H strong bond (>80 kcal/mole)

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Consider the chain reaction sequence :

R H C H , initiation

R O2 ROO, oxidation

ROO R H ROOH R, radical transfer

__________________________
R H O2 ROOH

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Chemical autocatalysis reactions accelerates
chemically such as in enzyme-promoted fermentation,
or chain branching reaction

Enzyme reaction nearly isothermal but combustion

processes are both chain branching and auto thermal

Autocatalysis reactive intermediate or heat can act

as catalyst to promote the reaction

Catalyst is generated by the reaction, by adding

promoters or heat to initiate the and accelerate the
process

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Chemical autocatalysis reactions accelerates
chemically such as in enzyme-promoted fermentation,
or chain branching reaction

Enzyme reaction nearly isothermal but combustion

processes are both chain branching and auto thermal

Autocatalysis reactive intermediate or heat can act

as catalyst to promote the reaction

Catalyst is generated by the reaction, by adding

promoters or heat to initiate the and accelerate the
process

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Produce more than one free radical species in
propagation step. Thus, the propagation steps increase
the concentration of radical species and destabilize the
kinetics.

Example:

ROOH R O OH

Rapid rise in the

concentration of radical
species can accelerate the
reaction and possibly a chain-
branching explosion.

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Consider the reaction of :

A BC

The mechanisms are:

A R, ri ki C A
A R B C R , rp k p C AC R
RX rt kt C R

ki C A
CR
kt ( 1)k p C A

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING

Chemical industry is the safer industry compare to the
risk if you drive on the road

Some example of disaster:

Texas City disaster I and II

Flixborough & Philips polyethylene plane explosion

Bhopal incident

CPE624: ADVANCED CHEMICAL REACTION ENGINEERING