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Thermodynamic Cycle for a Proton Gain Reaction

▪ Proton gain can be thought of as the outcome of 3 steps:

(1)

(2)

(3)

▪ ΔpgHo of A− is the sum of these enthalpy changes:

▪ Therefore, the proton affinity of A− is:

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Thermodynamic Cycle for a Proton Gain Reaction

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Factors Governing the Strengths of Acids and Bases
▪ The dominant factor in the variation in proton affinity across a period is the trend in
electron affinity of A, which increases from left to right and hence lowers the proton
affinity of A−.

▪ Increasing electron affinity correlates with increasing electronegativity,

▪ As the electronegativity of A increases, the proton affinity of A− decreases.


Therefore, the gas-phase acidity of HA increases across a period.

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Factors Governing the Strengths of Acids and Bases
▪ The dominant factor when descending a group is the decrease in the H−A bond
dissociation enthalpy (as the size of the element increases), which lowers the proton
affinity of A− and therefore results in an increase in the gas-phase acidity of HA down
the group.

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Periodic Trends in the Strength of Binary Acids

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Effect of Solvation on Proton Affinity
▪ Gibbs energy of solvation of an ion is the energy involved in transferring the anion A-
from a vacuum into a solvent. It is given by the Born equation:

z = charge number of ion


r = effective radius of ion, which includes part of the radii of solvent molecules
NA = Avogadro’s constant
ε0 = vacuum permittivity
εr = relative permittivity (dielectric constant) of solvent

▪ Because z2/r = ξ, the electrostatic parameter of the ion, this expression becomes

▪ ΔsolvGo is proportional to ξ. Therefore, small, highly charged ions are stabilized in


polar solvents.

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Effect of Solvation on Proton Affinity
▪ The interaction of the charged ion with the polar solvent molecules stabilizes the
conjugate base A− relative to the parent acid HA. As a result, the proton affinity of A- is
lower in solution than in gas phase and acidity of HA is enhanced by a polar solvent.

▪ On the other hand, the proton affinity of a neutral base B in solution is higher than
in the gas phase because the conjugate acid HB+ is stabilized by solvation. Because
cationic acids, such as NH4+, are stabilized by solvation, their proton affinity in solution
is higher than in gas phase and their acidity is lowered by a polar solvent.

▪ Effective Proton Affinity: It is the proton affinity in presence of a solvent.

▪ In presence of a solvent, the gas-phase process A–(g) + H+ (g) → AH(g) becomes

▪ The negative of the accompanying proton-gain enthalpy is called effective


proton affinity, Ap’, of A–(aq).