Research: Science and Education
Free Radical Halogenation, Selectivity, and Thermodynamics:
The Polanyi Principle and Hammond’s Postulate
Alfred A. Scala
Department of Chemistry and Biochemistry, Worcester Polytechnic Institute, Worcester, MA 01609; aascala@wpi.edu
The free radical halogenation of hydrocarbons, although
often the first reaction covered in organic chemistry courses
and texts, is usually not discussed in any depth because of
the pressure to get into the more interesting and important
reactions involving functional groups. Interestingly, this re-
action is often only superficially examined precisely because
it is described as being unselective.1 In the traditional, per-
haps unrealistic, organic chemical definition of selectivity, that
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is, regioselectivity or “giving a single product”, the free radi-
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cal halogenations are unselective. In fact when examined in
depth, this reaction has the potential to be the most conve-
nient and possibly the best vehicle for a realistic discussion
of selectivity, as well as many other topics, that are impor-
tant to organic chemistry, but also transcend organic chem-
istry because of their significance to all of chemistry. These
topics include mechanisms, kinetics, reaction-coordinate dia-
grams, transition states, relative rates (selectivity), and the
effect of thermodynamics on reaction rates and equilibria.
A previous article, describing an undergraduate labora-
tory experiment, reported student results for the gas-phase
chlorination and bromination of propane, butane, and isobu-
tane (1). The results were close to the expected product ra-
tios for the various isomeric products, if the reactivity ratios
for 1⬚, 2⬚, and 3⬚ carbon–hydrogen bonds were 1:3.8:5 for
chlorination, and 1:82:1600 for bromination. These are the
usually quoted gas-phase reactivity ratios in the few organic
text books that go into the topic in detail.1 The objective of
this article is to present the topic of selectivity in a broader
context and to suggest liquid-phase experiments that can serve
as the basis for further in-depth analysis and discussion. Stu-
dent results for the liquid-phase chlorination of isopentane
are also presented.
If selectivity is defined in terms of the relative rate con-
stants for competing reactions, the basis for the observed se-
lectivities is a difference in the free energies of activation of
the competing reactions, which in turn results from the ther-
modynamics of the competing reactions, and is described by
the Polanyi principle (PP), later reincarnated and qualitatively
refined as Hammond’s postulate (HP) (2, 3). Linear free en-
ergy relationships (LFER) that deal with equilibria as well as
reaction rates are similarly based, although they often rely
on empirical measurements for an independent variable rather
than the fundamental thermodynamics. This is largely a mat-
ter of convenience and utility that allows the wide applica-
tion of the LFER to a broad range of reactions, even while
ignoring some of the details, and does not change the ulti-
mate thermodynamic origin of these effects, as their name
implies (4). It is not the purpose here to discuss LFER but
rather to discuss the underlying ideas of the PP and HP in
relation to the simple free radical halogenation reactions and
their selectivity. One might be tempted to imply that the ap-
proach presented by the Polanyi principle and Hammond’s
postulate demonstrates the basis for all LFERs.
www.JCE.DivCHED.org • Vol. 81 No. 11 November 2004
The central idea, which is beautifully expressed in
Hammond’s postulate, is that the transition state will have a
structure and therefore an energy that is characteristic of both
the reactants and the products. The relative contributions of
reactant and product properties to the properties of the tran-
sition state depend upon whether the transition state is of
low energy and is achieved “early” or of high energy and
achieved “late” along the reaction coordinate. This difference
is usually a function of the reactivity of the system, which in
turn is a function of the thermodynamics of the reactions.
Very exothermic reactions are frequently very reactive, while
endothermic reactions are quite unreactive. Here very reac-
tive and unreactive refer to the magnitude of the rate con-
stant and derive from the fact that exothermic reactions
usually have low energies of activation. The more exother-
mic the reaction, the lower the energy of activation and ear-
lier the transition state; endothermic reactions have energies
of activation at least as large as the enthalpy of reaction and
later transition states (5). It is essential to keep in mind that
this discussion applies only to a comparison of similar reac-
tions. This idea is graphically illustrated in Figure 1 using
schematic reaction-coordinate diagrams.
Methane Reaction
It needs to be emphasized that the reactions being com-
pared must be similar because, at least for the moment, we
are neglecting the entropy. Figure 1 could be a comparison
of any three similar reactions, but is in fact a comparison of
methane halogenation with fluorine, chlorine, and bromine.
The thermodynamics are different because the bond ener-
gies of the HX molecules are different: HF, HCl, and HBr
bond dissociation energies are 568, 431, and 366 kJ兾mol,
respectively (6). The products are methyl radical and HX.
The early transition state is achieved for the most exother-
mic case of X = F and the late transition state is achieved for
Fluorination: Chlorination: Bromination:
early intermediate late
transition state transition state transition state
CH4 + F CH3 + HBr
CH4 + Cl CH + HCl
H°
3
CH3 + HF CH4 + Br
Reaction Reaction Reaction
Coordinate Coordinate Coordinate
Figure 1. Methane halogenation, thermodynamics, and schematic
reaction coordinate.
• Journal of Chemical Education 1661
 Research: Science and Education

the most endothermic case of X = Br. The case for chlorine Table 1. Thermodynamics of Methane Halogenation
is intermediate. The enthalpies of these reactions, 1a, along ∆H° of Eq 1a/ ∆H° of Eq1b/
with the subsequent propagation step, 1b, are presented in X
(kJ/mol) (kJ/mol)
Table 1.
F ᎑140 ᎑303

CH4 + X2 CH3X + HX net reaction (1) Cl ᎑4.2 ᎑100

Br +62.7 ᎑89.9
CH4 + X CH3 + HX (1a) I +134 ᎑79.4
mechanism
CH3 + X2 CH3X + X (1b)

The later the transition state, the more the formation of the Chlorination: Bromination:
H⫺X bond and the cleavage of the C⫺H bond contribute early transition state late transition state
to its energy. The weakest bond, H⫺Br must be formed to a (small β) (large β)
greater extent and the C⫺H bond must be broken to a greater
extent in order to achieve the transition state for bromina- ‡
∆∆G = β∆∆H°
tion, compared to the H⫺F bond, which is so strong it only [C-----H--Br]‡
[C--H-----Cl]‡
barely forms, and the C⫺H bond is barely stretched when
the transition state for fluorination is achieved. Unrestricted 1°-C3H7 + HBr
∆∆H°
Hartree–Fock SCF calculations using Gaussian-98 and the

H°
C3H8 + Cl
2°-C3H7 + HBr
3-21G basis set indicate that the C⫺H bond distances in
the transition states for fluorination, chlorination, and bro- ∆∆H°
1°-C3H7 + HCl

mination of methane are 1.31, 1.50, and ≈1.66, respectively
(7). The length of the H⫺X bonds that are forming also show
that the H⫺Br bond is almost totally formed, only 6% ex-
tension, in the transition state. The extension in the H⫺Cl
and H⫺F bonds are 12 and 32% respectively.2,3
In reaction 1a, because bromination has a late transi-
tion state, the energy of the transition state has a significant
contribution from the energy of the products, that is, me-
thyl radical and HBr. The opposite is true for the fluorina-
tion reaction, which has an early transition state whose energy
is characteristic of the reactants, methane and fluorine atom.
Chlorine is an intermediate case. The stability of the carbon
radical, or alternatively the strength of the C⫺H bond that
is broken, is therefore most important in the bromination
reaction and least important in the fluorination. Since the
mechanism of fluorination is complicated and hydrogen ab-
straction by fluorine atom is so indiscriminate and difficult
to control without special precautions such as dilution, it will
not be considered further. The remainder of the discussion
will contrast chlorination with bromination of hydrocarbons
that have more than a single site for reaction.
Propane Reaction
When the hydrocarbon is methane there is no selectiv-
ity to speak of; the product is the methyl radical. If on the
other hand one considers another hydrocarbon, for example,
propane, then the question of selectivity becomes significant.4
If the halogenation of propane with either chlorine or bro-
mine is considered, then it is possible for either of two dif-
ferent hydrogen atoms to be abstracted from propane. The
C3H7• radical may have the radical center on either the pri-
mary or the secondary carbon. It is the relative rates of these
reactions that determine the relative yields of 1-Xpropane and
2-Xpropane and consequently the selectivity of the reaction:
C3 H8 + X CH3CH2CH2 + HX (primary) (2)
CH3CHCH3 + HX (secondary) (3)
2°-C3H7 + HCl C3H8 + Br
Figure 2. The schematic reaction-coordinate diagrams for H-atom
abstraction from propane by chlorine and bromine.
The previous discussion of methane halogenation should
and does lead to the conclusion that propane bromination,
the reaction whose transition state should be late and involve
more of the radical structure that is equivalent to more of
the C⫺H bond cleavage, should be more selective than the
chlorination, which is characterized by an earlier transition
state with less C⫺H bond cleavage. The origin of the differ-
ence in the two competing reactions lies in the fact that it is
more difficult to break the primary C⫺H bond (410 kJ兾mol)
than it is to break the secondary C⫺H bond (395 kJ兾mol)
(6). The chlorination should be less selective because there is
less of the C⫺H bond broken in the transition state for chlo-
rination. The schematic reaction-coordinate diagrams for
these competing reactions for both chlorination and bromi-
nation are shown in Figure 2.
Thermodynamic and Kinetic Considerations
The thermodynamic, ∆H ⬚, and kinetic, Ea, data for these
reactions are presented in Table 2. The origin of the PP兾HP
formulation of this idea is expressed in the Eyring equation:
kB T −∆G ‡
k = exp (4)
h RT
∆G = ∆H − T ∆S (5)
These equations, while expressing the idea well, are obviously
not meant for the calculation of absolute rate constants. How-
ever the application of these equations to two competing re-
actions is ideally suited to the measurement and prediction

1662 Journal of Chemical Education • Vol. 81 No. 11 November 2004 • www.JCE.DivCHED.org

 Research: Science and Education

Table 2. Thermodynamics of H-Atom Abstraction activity ratios, that is, k1兾k2 from a standard compound such
from Propane By Chlorine and Bromine (6, 8) as isopentane, which contains primary, secondary, and ter-
Primary H/ Secondary H/ tiary C⫺H bonds.
(kJ/mol) (kJ/mol) A closer look at the data presented in Table 2 provides
Compound further insight to the principles being elucidated here. First
∆H° Ea ∆H° Ea
of all, since the ∆∆H ⬚ is the same, 14.6 kJ兾mol, for both
Cl2 ᎑20.9 4.1 ᎑35.5 02.8 chlorination and bromination (because it originates in the
a
C⫺H bond strengths) an examination of the energies of ac-
Br2 +43.9 53. +29.3 42.4
tivation, which are much smaller for the chlorinations, im-
a
The Ea for the reaction of bromine with the primary hydrogen of mediately suggests that β is smaller for the chlorination. This
propane has been estimated from the measured Ea for the secondary is equivalent to saying that the chlorination reactions have
reaction 42.4 kJ/mol and the selectivity ratio of 82:1. The selectivity
ratio is assumed to be entirely due to the difference in the energies of
earlier transition states. If the difference in the reactivity, per
activation, that is ∆Ea. site available, is attributed entirely to a difference in the en-
ergies of activation, then the value of β may be calculated
both from the experimental Ea data and also from the selec-
of relative rates of similar reactions. The ratio of two such tivity ratio. For propane chlorination, the difference in the
equations, which represents a competition, then becomes (9), measured Ea’s, 1.3 kJ兾mol, and that calculated from the re-
activity ratios, 3.3 kJ兾mol, are not very different and indi-
k1 ∆∆S ‡ −∆∆H ‡ cate values for β of 0.09 and 0.23, respectively. Realizing the
= exp exp (6) errors inherent in the absolute measurement of energies of
k2 R RT
activation, it would seem that for the present purpose the
value of β derived from the reactivity ratio would be more
∆G ‡ = f ∆G ° ( ) (7) reliable. In any case a β of about 0.2 would be indicative of
early transition states for the more exothermic reactions, chlo-
where the free energy of activation in the Eyring equation is rination. Bromination is a slower, more endothermic reac-
a function of ∆G⬚, the free energy of reaction: tion, which would be expected to have a later transition state
and be more selective. The only data available here are the
relative reactivity data, which indicates that a secondary C⫺H
( ) (
∆∆G ‡ = β ∆∆G ° = β ∆∆H ° − β T ∆∆S ° (8) ) ( ) bond is 82 times more reactive than a primary C⫺H bond.
The experimental measurement of the Ea for the secondary
The function that relates the free energies of activation reaction, 42.4 kJ兾mol, is a preliminary indication of a large
to the enthalpies and entropies of reaction, given in eq 8, is β, but does not permit a calculation because the Ea for the
a constant, β, multiplied by the difference in the enthalpies reaction at the primary site has not been measured. If the
and entropies of reaction for the two competing reactions. β reactivity ratio is used to calculate the ∆Ea, then the result-
has values between 0 and 1. As the reactions 1 and 2 have ing value of 11.0 kJ兾mol indicates a value of β = 0.75, defi-
rate constants k1 and k2, the terms ∆∆H ⬚ and ∆∆S ⬚ refer to nitely a late transition state (10).
the difference in the enthalpies and entropies of reactions 1 These ideas are fraught with problems if one attempts
and 2, that is, (∆H ⬚1 − ∆H ⬚2) and (∆S ⬚1 − ∆S ⬚2). In the to apply them to even slightly dissimilar reactions, for ex-
PP兾HP formalism small β applies to an “early”, reactant-like, ample, comparing the rate of an SN2 reaction with the cor-
transition state and large β indicates a “late”, product-like, responding E2 reaction for the same reactants; however,
transition state. The equation may be further simplified by applied to similar reactions, they constitute the essence of
normalization to a per-reactive-site basis by including the our understanding of selectivity in reactions. In fact the in-
number of sites available for each reaction. verse relationship between selectivity and reactivity may have
universal applicability not only in chemistry, but also in ar-
eas of human activity beyond physical science. These ideas
k1
=
N1
e xp
(
β ∆∆S ° ) exp
(
−β ∆∆H ° )
(9)
present the opportunity to stress the importance of thermo-
k2 N2 R RT dynamics to all students, but especially those who view them-
selves as organic or biochemists, that is, those with more
qualitative inclinations.
For similar, almost identical, reactions it is not unreasonable
to assume that the entropy of reaction would be the same Isopentane Reaction
and the exponential term exp[β(∆∆S ⬚)兾R] reduces to 1, re-
sulting in eq 10: Over the course of three terms, students in the organic
laboratory course at WPI have been measuring the selectiv-
k1
=
N1
exp
−β ∆∆H ° ( ) ity of the liquid-phase chlorination and bromination of
isopentane5 (11). Because bromine is so selective, essentially
k2 N2 RT (10)
one product is formed from the abstraction of the tertiary
hydrogen of isopentane. Since the chlorination reaction is less
Equation 10 enables the plot of enthalpy in Figure 2. The selective as discussed above, it is possible to determine reac-
normalization allows the simple prediction of product yields tivity ratios for the chlorination of isopentane in the liquid
for any hydrocarbon from its structure and the measured re- phase. The reactivity ratios determined by three different

www.JCE.DivCHED.org • Vol. 81 No. 11 November 2004 • Journal of Chemical Education 1663

 Research: Science and Education
Table 3. Results for the Selectivity of the Liquid Phase
Chlorination of Isopentane with Chlorine
Relative Reactivity per H-Atom (Standard Deviation)
Number
of Exp
1°Aa 1°Ba 2° 3°
21 1.00 1.08(0.083) 3.06(0.116) 3.86(0.307)
14 1.00 1.04(0.081) 2.97(0.117) 3.73(0.307)
28 1.00 1.03(0.053) 2.91(0.171) 3.50(0.076)
a
The primary hydrogen atoms labeled A are the six hydrogens on the
iso-methyl groups and the primary hydrogen atoms labeled B are the
three hydrogens on the methyl group next to the secondary carbon.
classes during three different terms, involving 63 individual
experiments and analyses, are presented in Table 3.
The results indicate that chlorine atom is slightly less
selective in the liquid phase, compared to the gas phase. The
1⬚B primary hydrogens appear to be slightly more reactive
than the 1⬚A primary hydrogens. Although the difference is
quite small, and may not be statistically significant, it might
suggest a minor steric interaction in the transition state. The
measured average reactivity of the secondary and tertiary hy-
drogens are 2.97 and 3.67, respectively, compared to the gas-
phase values of 3.8 and 5.0 (1). The liquid phase6 apparently
reduces the selectivity of the chlorine atom by slowing the
reaction at the secondary and tertiary sites compared to the
primary site. This is consistent with a steric–solvent effect
on the already structurally more crowded transition states for
the reactions at the secondary and tertiary sites. Extensive
speculation on this point is not justified by the data. Russell
and coworkers, as well as others, have studied solvent effects
in the selectivity of free radical reactions extensively (12, 13).
Summary
The reactions presented here are amenable to the col-
lection of more (student) data, for chlorination and bromi-
nation reactions, which may elucidate other influences on
selectivity (14). These experiments may utilize both intramo-
lecular and intermolecular competitions. Discussions simi-
lar to those above serve as a vehicle for introducing students
to some of the ways in which professional chemists think
about chemistry and some of the subtleties of what makes
chemical reactions behave as they do. Invariably students
come away from these discussions with a finer appreciation
of reaction dynamics and many contributions for other se-
lectivity experiments, which they cannot wait to investigate.
Acknowledgments
I thank WPI for support of this work and Ladislav H.
Berka for his meticulous review of this manuscript.
Notes
1. Most current texts do not treat this topic in the depth pre-
sented here. The one exception to this statement is the compre-
hensive treatment of this subject in all of the editions of Morrison,
R. T.; Boyd, R. N. Organic Chemistry; Allyn and Bacon Inc.: Boston.
2. The bond extension is defined here as the bond length in
the transition state, minus the equilibrium bond length, all divided
by the equilibrium bond length.
3. A reviewer has suggested that using a less expensive calcu-
1664 Journal of Chemical Education • Vol. 81 No. 11 November 2004
lation method such as AM1 might make an interesting project for
students in a computational chemistry course.
4. In functional group organic chemistry propylene may be
converted to either 2-bromopropane or 1-bromopropane by choos-
ing conditions referred to as Markovnikov or anti-Markovnikov,
respectively. The anti-Markovnikov reaction occurs by a free radi-
cal chain mechanism that operates because the thermodynamics of
both propagation steps are exothermic. This is not true for HCl,
which does not give the anti-Markovnikov reaction.
5. Chlorinations generate chlorine by treating aqueous sodium
hypochlorite with aqueous HCl and extracting the chlorine into the hy-
drocarbon with everything in the same centrifuge tube. Brominations
use either neat bromine or an aqueous solution (~3%) of bromine.
6. The solvent is assumed to be isopentane because the reaction
clearly occurs in the isopentane. Although not studied, the effect of
the presence of the aqueous phase it is thought to be insignificant.
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