Introduction

Free-Radical substitution gives us insight to the relative relativities of different types of hydrogen
atoms toward chlorine and bromine radicals. This method transforms alkanes to alkyl chlorides
and bromides. Alkenes are chemically unreactive toward most reagents, but free-radical chain
mechanism pathways allow for the introduction of certain functional groups into an alkane.
Chlorination using sulfuryl chloride has three distinct stages: initiation, propagation, and
termination.
In the first step, initiation, a catalytic amount of an initiator (In-In) is used to generate chlorine
atoms from molecular chlorine under mild conditions. Homolysis of a molecule occurs upon
irradiation or gentle heat to give free radicals (Equation 1).

Equation 1
The free radicals react with molecular chlorine (Equation 2) to produce In-Cl and a chlorine
atom.

Equation 2
The hemolysis of 1,1-azobis (cyclohexanenitrile), ABCN, is the first step for initiating the free
radical chain reaction. It forms nitrogen and a free radical (Equation 3).

Equation 3
The next step is propagation, it includes the abstraction of a hydrogen atom from the
hydrocarbon by a chloride atom to produce a new free radical, R (Equation 4).

Equation 4
The radical attacks sulfuryl chloride (Equation 5) which produces the alkyl chloride and the
radical SOCl 2 (Equation 6). In the final step of propagation, the SOCl2 turns into SO 2
and a chlorine atom (Equation 7).

Equation 5

Equation 6

Equation 7
In the last step, termination, the various radicals combine to give molecules. (Equations 8-10)

Equation 8

Equation 9

Equation 10
To determine the products that will be formed at the end of free-radical halogenation the step
where the hydrogen atom is abstracted is the mechanistic step (Equation 4), and for the
bromination the mechanistic step involves the abstraction of a hydrogen atom by the bromium
radical determines the products that will be formed (Equation 11). Bromination is much more
selective than chlorination. Measuring the relative reactivitys of the hydrocarbons toward
bromine radical is easily determined because molecular bromine is colored, so the progress of
bromination can be observed as the disappearance of color as the bromine is consumed.

Equation 11
Data and Observations
-Mass loss during first heating period: 2.0781 g
-No second period of heating was necessary because about 90% of mass was lost in the first
heating period.
-Final Amount of Material: 3.7617 g
Discussion
Using the intiator is an advantage for the radical reaction because the intiator gives free radical
upon irradiation or gentle heat and the reacts with molecular chlorine to produce In-Cl. (Reaction
1). The reaction will also proceed under milder conditions.

Reaction 1
In this lab sulfuryl chloride is used instead of molecular chloride for safety and convenience.
All possible products of this reaction are:

Molar Percentage from 1H NMR:

1-chlorobutane: 16%; (.496 g)
1, 2-dichlorobutane: 20%; (.62 g)
1, 3-dichlorobutane: 29%; (.90 g)
1, 4-dichlorobutane: 35%; (1.085 g)
1, 1-dichlorobutane: inconclusive because its almost invisible in the spectrum

Average Molar Mass of the Mixture: 121.5 g

Moles of Components of the Mixture: .031 moles

Chromatogram from the book, and the one we obtained are very similar. Four easily
distinguishable compounds are found.

Molar Percentages from Peaks:

Peak 1: 12% (1, 1)
Peak 2: 40% (1, 2)
Peak 3: 43% (1, 3)
Peak 4: 5% (1, 4)

Yield: 46%
Conclusion
Functionalization of alkanes through a radical substitution reaction can tell us about its reactivity
with free radicals. It can also tell us of the carbons are primary, secondary, or tertiary, but it is not
so good at assigning functional groups or detail analyzes of a compound. I believe the
chromatogram revealed the best possible results because the compounds were more clearly
separated, and I believe that less guesswork is involved in GC analysis.