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    The Hammett Equation by C.D Johnson

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    Desy Wijayanti
    The Hammett Equation aims to quantify inductive and resonance effects on free energy changes through equilibrium constants and reaction rates. It specifically examines how substituents on the benzene nucleus affect the acidity of benzoic acid, measured by pKa values. Electron-donating groups lower the pKa and decrease acidity, while electron-withdrawing groups raise pKa and increase acidity. The substituent constant σ is a measure of these electronic effects. Plots of substituent constants against equilibrium or reaction constants show substituents have consistent inductive or resonance effects across different reactions.

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    The Hammett Equation by C.D Johnson

    Uploaded by

    Desy Wijayanti
    1K views2 pages
    The Hammett Equation aims to quantify inductive and resonance effects on free energy changes through equilibrium constants and reaction rates. It specifically examines how substituents on the benzene nucleus affect the acidity of benzoic acid, measured by pKa values. Electron-donating groups lower the pKa and decrease acidity, while electron-withdrawing groups raise pKa and increase acidity. The substituent constant σ is a measure of these electronic effects. Plots of substituent constants against equilibrium or reaction constants show substituents have consistent inductive or resonance effects across different reactions.

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    The Hammett equation in physical organic chemistry

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    The Hammett Equation by C.D Johnson.docx

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    The Hammett Equation aims to quantify inductive and resonance effects on free energy changes through equilibrium constants and reaction rates. It specifically examines how substituents on the benzene nucleus affect the acidity of benzoic acid, measured by pKa values. Electron-donating groups lower the pKa and decrease acidity, while electron-withdrawing groups raise pKa and increase acidity. The substituent constant σ is a measure of these electronic effects. Plots of substituent constants against equilibrium or reaction constants show substituents have consistent inductive or resonance effects across different reactions.

    Copyright:

    © All Rights Reserved
    Download as DOCX, PDF, TXT or read online from Scribd
    Download as docx, pdf, or txt
    1K views2 pages

    The Hammett Equation by C.D Johnson

    Uploaded by

    Desy Wijayanti
    The Hammett Equation aims to quantify inductive and resonance effects on free energy changes through equilibrium constants and reaction rates. It specifically examines how substituents on the benzene nucleus affect the acidity of benzoic acid, measured by pKa values. Electron-donating groups lower the pKa and decrease acidity, while electron-withdrawing groups raise pKa and increase acidity. The substituent constant σ is a measure of these electronic effects. Plots of substituent constants against equilibrium or reaction constants show substituents have consistent inductive or resonance effects across different reactions.

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    © All Rights Reserved
    Download as DOCX, PDF, TXT or read online from Scribd
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    The Hammett Equation

    The Basic aim of the Hammett Equation is to evaluate the degree of inductive and resonance
    interaction consistency in quantitative terms. This involves elucidating the contribution of
    inductive and resonance effects to free energy changes on going from one side to other of an
    equilibrium or from the ground state to the transition state of a reaction. Such free energy
    changes will be proportional to the logarithms of rate equilibrium constants.
    The Hammett Equation. The effect of substituent in the benzene nucleus in the benzene nucleus
    on the acidity of benzoic acid expressed in terms of pKa, and the explanation of such effects in
    terms of induction and resonance, forms a specific example of the ideas generally expressed
    above. It is also particularly convenient in that, for m- and p- substituted benzoic acids,
    electronic factors are very unlikely to be complicated by steric interaction between substituent
    and reaction site. A quantitative measure of these electronic effects is thus given by the
    difference between the pKa value of substituted benzoic acid and that of benzoic acid itself.
    A parameter , the substituent constant, which is a measure of the size of such effects for a given
    substituent in this case. K is equilibrium constant for the substituted benzoic acid and Ko is the
    equilibrium constant for benzoic acid.

    Electron-withdrawing groups, such as NO2, increase the equilibrium constant K of [1.1] because
    they stabilize the carboxylate anion; thus the pKa is numerically smaller than that for benzoic
    acid and is consequently positive. Electron-donating groups, CH3 for example, decrease the
    equilibrium constant, so their values are negative.

    The linearity of these plots for the remaining substituent reveals that the dissociation benzoic
    acids, the dissociation of phenylphosphonic acids, and the alkaline hydrolysis of ethyl benzoates
    respond in the same manner to influence of m- and p- substituent. The slope of the correlation
    line, 0.76 and 2.54 for the latter two respectively is referred to as , the reaction constant. It is a
    measure of the sensitivity of the reaction or equilibrium to electronic substituent effects, being by
    definition 1.00 for the dissociation of benzoic acids in water at 25oC. In both of the examples
    chosen, is also positive. This mean, for the acid-anion equilibrium, that electron-donating
    decrease the extent of dissociation, while electron-withdrawing groups increase, it as can be
    readily argued from their effect on stability of the anion. Similarly, electron donor substituent
    retard the rate of the hydrolysis reaction, while electron acceptors accelerate it; the carbon atom
    of the carbonyl group of an ester will become more reactive towards nucleophiles with electronwithdrawing group present.

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