MODULE TITLE

LINEAR FREE ENERGY RELATIONSHIP (HAMMETT-TAFT

EQUATION)

MODULE NUMBER

COURSE USED

CHM3103 CHEMICAL KINETICS

MODULE CODE

UPM/FS/CHM3103-C1

VERSION

VERSION 4.0

LEARNING RESOURSES
1. Laidler, K. J. (1997). Chemical Kinetics. 3rd edition. New
York: Addison-Wesley Pub Co.
2. Mortimer, M. & Taylor, P. G. (2002). Chemical Kinetics and
Mechanism. Milton Keynes: The Open University.
3. Espenson, J. H. (2002). Chemical Kinetis and Reaction
Mechanisms. 2nd edition. New York: McGraw Hill.
4. Hammett, L.P. Some Relations between Reaction Rates and
Equilibrium Constants. Chem. Rev. 1935. 17(1): 125136.
5. Hansch, c., Leo, A., Taft, R.W. A Survey of Hammett
Substituent Constants and Resonance and Field Parameters.
Chem. Rev. 199l. 97:165-195.
6. http://en.wikipedia.org/wiki/Hammett_equation#cite_note-3
7. Any organic chemistry books.

BACKGROUND KNOWLEDGE
Reaction rates; Chemical equilibrium; Role of substituent in the
chemistry of aromatic compounds
TERMS TO KNOW (TERMINOLOGY)
Gibbs free energy; Equilibrium constant; m- & p-substitution;
Inductive effect
LEARNING OUTCOMES
On completion of this module student should be able to:
1. Explain The Hammett-Taft Equation Using The Linear Free
Energy Concept.
2. Relate the electronic effects of substituent on the strengths of
m- and p-substituted benzoic acids as an example & apply that.

COURSE CONTENTS
The term linear free energy relationship (LFER) applies to a
variety of relationships between kinetic and thermodynamic
quantities that are very important in both organic and inorganic
chemical reactions. The Hammett equation which was developed
in 1937 relates the dissociation constants of substituted benzoic
acid to benzoic acid. This equation shows the linear relationship
between the change in free energy and the product of .

Equation 1

Equation 2
The Hammett equation was originally used to explain the
electronic effects of substituent on the strengths of m- and psubstituted benzoic acids. For example, if the group X is electron
withdrawing, the acidity of the -COOH group is increased and is
positive. Conversely, the values are negative for electron
releasing group.
Note that this equation is satisfactory if the reactive site is
sufficiently removed from the substituent so that steric factors do
not enter into the rate-determining step. If the reaction involves a
series of substituents that greatly alter the way in which either the
reactant or the transition state is solvated, the relationship may be
less satisfactory.
While the original Hammett LFER was applied to aromatic
compounds but it can be extended to aliphatic compounds as well.
The approach was taken by Taft is similar to that of Hammet;

Equation 3
Where * is a constant related to polar substituents effects and *
is a reactant constant like the case before, and Es is a steric energy
term.
For a given series of reactants, Es is frequently considered to be
zero because for any pair of similar species subtraction of two
equations having the above equation form. So, Taft equation is
written as;

Equation 4
The Taft and Hammett equations are the same, but Taft used
constants that are also appropriate to aliphatic and restricted
aromatic materials.
ASSIGNMENTS
1. Explain the two constants of "sigma" and "rho" in the
Hammett-Taft equation.
2. The Hammett-Taft equation is used only for substituent at para
and meta positions not for ortho. Explain why.
3. The values of for m-NH2 & p-NO2 have been reported as 0.71 & +0.78. The values are so small compared to pKa value
of benzoic acid. Explain why.
4. The base-catalysed hydrolysis of ethyl m-nitrobenzoate is 63.5
times faster than the unsubstituted ester under the same
conditions; what is the comparable rate of hydrolysis of ethyl
p-methoxybenzoate? [ m-NO2= +0.71 and p-MeO= -0.27]
5. Using equation 3 shows that which of the following reactions is
faster?
i.

CCl3CO2Et + H2O

CCl3CO2H + EtOH

(Es= -0.07; *= -0.10)

ii.

C2H5CO2Et + H2O

C2H5CO2H + EtOH

(Es= -2.06; *= +2.65)

6. The linear free energy relationships are very useful in organic
and inorganic chemistry. Explain why.

EVALUATION
In a group manner (refer to the grouping list), you must submit the
module by 23/10/2013 by group discussion and doing the
assignment.
COPYRIGHT
Dr. ROGHAYEH ABEDI KARJIBAN
roghayeh@upm.edu.my
03-89467487
Date Created: 31 March 2013

Grouping CHM3103 Semester 2 2013/2014

Group 1
1

'

Group 2
7

Group 3
1

'

Group 4
1

Group 5
2

'

Group 6
3

Group 7
3

Group 8
4