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Chapter 2

Acids & Bases

Brnsted-Lowry

Acid : Any species that can donates a


proton.
Base : Any species that can accept a proton.
Most important principle: Conjugate acidbase pairs.

O
CH3

C OH

acid

O
+ CH3

NH2

base

CH3

C O

conjugate
base

CH3

NH3

conjugate
acid

Lewis Acids and Bases


Acids accept electron pairs => electrophile
Bases donate electron pairs => nucleophile

Any reaction in which one species donates an electron


pair to another species is a Lewis acid-base reaction.
In a Lewis acid-base reaction, a Lewis base donates an
electron pair to a Lewis acid.

Lewis acid-base reactions illustrate a general pattern in


organic chemistry. Electron-rich species react with
electron-poor species.
In the simplest Lewis acid-base reaction one bond is
formed and no bonds are broken. This is illustrated in
the reaction of BF3 with H2O. H2O donates an electron
pair to BF3 to form a new bond.

Acid and Base Strength

Acid dissociation constant, Ka


Base dissociation constant, Kb
For conjugate pairs, (Ka)(Kb) = Kw
Spontaneous acid-base reactions proceed
from stronger to weaker.
O
CH3

C OH

pKa 4.74

O
+ CH3

NH2

pKb 3.36

CH3

C O

pKb 9.26

CH3

NH3

pKa 10.64
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Structural Effects on Acidity


Electronegativity
Size
Resonance stabilization of conjugate
base
Hybridization
Inductive effect

Electronegativity
As the bond to H becomes more polarized, H
becomes more positive and the bond is easier
to break.

Size
As size increases, the H is more loosely
held and the bond is easier to break.
A larger size also stabilizes the anion.

Resonance Stabilization
Delocalization of the negative charge on the
conjugate base will stabilize the anion, so the
substance is a stronger acid.
More resonance structures usually mean greater
stabilization.
O
CH3CH2OH

<

CH3C OH

O
<

CH3

OH

O
Acidity increases
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Inductive Effects
When electron density is pulled away from the negative
charge through bonds by very electronegative atoms, it is
referred to as an electron withdrawing inductive effect.

More electronegative atoms stabilize regions of high electron


density by an electron withdrawing inductive effect.
The more electronegative the atom and the closer it is to the
site of the negative charge, the greater the effect.
The acidity of HA increases with the presence of electron
withdrawing groups in A.

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Hybridization Effects
The final factor affecting the acidity of HA is the
hybridization of A.
Let us consider the relative acidities of three different
compounds containing CH bonds.

The higher the percent of s-character of the hybrid


orbital, the closer the lone pair is held to the nucleus,
and the more stable the conjugate base.
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Commonly Used Bases in Organic Chemistry


It should be noted that:
Strong bases have weak conjugate acids with high pKa
values, usually > 12.
Strong bases have a net negative charge, but not all
negatively charged species are strong bases. For example,
none of the halides F, Cl, Br, or I, is a strong base.

Carbanions, negatively charged carbon atoms, are especially


strong bases. A common example is butyllithium.
Two other weaker organic bases are triethylamine and
pyridine.

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(a) The following compound can become protonated on any


of the nitrogen atoms. However, one of these nitrogen
atoms is much more basic than the others.
H3C

..
NH

..
NH

: NH2

(i) Draw the important resonance forms of the products of


protonation on EACH of the three nitrogen atoms (include
the formal charge when necessary)
(ii) Determine which nitrogen atom is the most basic. Give
reason for your choice.
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Rank the following protons in order of increasing acidity. Explain


your answer.

1
H

H
2
H
H
3

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