Thermal Cracking Reactions

The first step in cracking is the thermal decomposition of hydrocarbon molecules to two free radical fragments. This initiation step can occur by a homolytic carbon-carbon bond scission at any position along the hydrocarbon chain. The following represents the initiation reaction:

The radicals may further crack, yielding an olefin and a new free radical. Cracking usually occurs at a bond beta to the carbon carrying the unpaired electron.

Further β bond scission of the new free radical R˙ can continue to produce ethylene until the radical is terminated.

Free radicals may also react with a hydrocarbon molecule from the feed by abstracting a hydrogen atom. In this case the attacking radical is terminated, and a new free radical is formed. Abstraction of a hydrogen atom can occur at any position along the chain. However, the rate of hydrogen abstraction is faster from a tertiary position than from a secondary, which is faster than from a primary position.

The secondary free radical can crack on either side of the carbon carrying the unpaired electron according to the beta scission rule, and a terminal olefin is produced.

Free radicals, unlike carbocations, do not normally undergo isomerization by methyl or hydrogen migration. However, hydrogen transfer (chain transfer) occurs when a free radical reacts with other hydrocarbons.  There are two major commercial thermal cracking processes, delayed coking and fluid coking. Flexicoking is a fluid coking process in which the coke is gasified with air and steam. The resulting gas mixture partially provides process heat.