Acids and Bases

Brnsted-Lowry Acids and Bases

A Brnsted-Lowry acid is a proton donor.
A Brnsted-Lowry base is a proton acceptor.
H+ = proton

Acids and Bases

Brnsted-Lowry Acids and Bases
Some molecules contain both hydrogen atoms and lone
pairs and thus, can act either as acids or bases,
depending on the particular reaction. An example is the
addictive pain reliever morphine.

Acids and Bases

Reactions of Brnsted-Lowry Acids and Bases
A Brnsted-Lowry acid base reaction results in the transfer of
a proton from an acid to a base.
In an acid-base reaction, one bond is broken, and another
one is formed.
The electron pair of the base B: forms a new bond to the
proton of the acid.
The acid HA loses a proton, leaving the electron pair in the
HA bond on A.

Acids and Bases

Reactions of Brnsted-Lowry Acids and Bases
The movement of electrons in reactions can be illustrated using
curved arrow notation. Because two electron pairs are involved in
this reaction, two curved arrows are needed.
Loss of a proton from an acid forms its conjugate base.
Gain of a proton by a base forms its conjugate acid.
A double reaction arrow is used between starting materials and
products to indicate that the reaction can proceed in the forward
and reverse directions. These are equilibrium arrows.
Examples:

Acids and Bases

Acid Strength and pKa
Acid strength is the tendency of an acid to donate a proton.
The more readily a compound donates a proton, the stronger an acid
it is.
Acidity is measured by an equilibrium constant
When a Brnsted-Lowry acid HA is dissolved in water, an acidbase reaction occurs, and an equilibrium constant can be written for
the reaction.

Acids and Bases

Acid Strength and pKa
Because the concentration of the solvent H2O is essentially constant,
the equation can be rearranged and a new equilibrium constant, called
the acidity constant, Ka, can be defined.

It is generally more convenient when describing acid strength to use

pKa values than Ka values.

Acids and Bases

Acid Strength and pKa

Acids and Bases

Factors that Determine Acid Strength
Anything that stabilizes a conjugate base A: makes the
starting acid HA more acidic.
Four factors affect the acidity of HA. These are:
o Element effects
o Inductive effects
o Resonance effects
o Hybridization effects
No matter which factor is discussed, the same procedure is
always followed. To compare the acidity of any two acids:
o Always draw the conjugate bases.
o Determine which conjugate base is more stable.
o The more stable the conjugate base, the more acidic the
acid.

Acids and Bases

Factors that Determine Acid Strength
Element EffectsTrends in the Periodic Table.
Across a row of the periodic table, the acidity of HA
increases as the electronegativity of A increases.

Positive or negative charge is stabilized when it is spread

over a larger volume.

Acids and Bases

Factors that Determine Acid Strength
Element EffectsTrends in the Periodic Table.
Down a column of the periodic table, the acidity of HA
increases as the size of A increases.

Size, and not electronegativity, determines acidity down a

column.
The acidity of HA increases both left-to-right across a row
and down a column of the periodic table.
Although four factors determine the overall acidity of a
particular hydrogen atom, element effectsthe identity of
Ais the single most important factor in determining the
acidity of the HA bond.

Acids and Bases

Factors that Determine Acid StrengthInductive Effects
An inductive effect is the pull of electron density
through bonds caused by electronegativity
differences in atoms.
In the example below, when we compare the acidities
of ethanol and 2,2,2-trifluoroethanol, we note that the
latter is more acidic than the former.

Acids and Bases

Factors that Determine Acid StrengthInductive Effects
The reason for the increased acidity of 2,2,2trifluoroethanol is that the three electronegative
fluorine atoms stabilize the negatively charged
conjugate base.

Acids and Bases

Factors that Determine Acid StrengthInductive 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.

Acids and Bases

Factors that Determine Acid StrengthResonance Effects
Resonance is a third factor that influences acidity.
In the example below, when we compare the acidities of
ethanol and acetic acid, we note that the latter is more acidic
than the former.

When the conjugate bases of the two species are compared, it

is evident that the conjugate base of acetic acid enjoys
resonance stabilization, whereas that of ethanol does not.

Acids and Bases

Factors that Determine Acid StrengthResonance
Effects
Resonance delocalization makes CH3COO more stable
than CH3CH2O, so CH3COOH is a stronger acid than
CH3CH2OH.

The acidity of HA increases when the conjugate

base A: is resonance stabilized.

Acids and Bases

Factors that Determine Acid StrengthResonance
Effects
Electrostatic potential plots of CH3CH2O and CH3COO
below indicate that the negative charge is
concentrated on a single O in CH3CH2O, but
delocalized over both of the O atoms in CH3COO.

Acids and Bases

Factors that Determine Acid StrengthHybridization
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.

Acids and Bases

Factors that Determine Acid StrengthHybridization
Effects

Acids and Bases

Factors that Determine Acid StrengthHybridization
Effects

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Acids and Bases

Commonly Used Acids in Organic Chemistry
In addition to the familiar acids HCl, H2SO4 and HNO3, a
number of other acids are often used on organic
reactions. Two examples are acetic acid and p-toluenesulfonic acid (TsOH).

Acids and Bases

Commonly Used Acids in Organic Chemistry
Common strong bases used in organic reactions are
more varied in structure.

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Acids and Bases

Commonly Used Acids 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.

Acids and Bases

Lewis Acids and Bases
The Lewis definition of acids and bases is more general
than the Brnsted-Lowry definition.
A Lewis acid is an electron pair acceptor.
A Lewis base is an electron pair donor.
Lewis bases are structurally the same as Brnsted-Lowry
bases. Both have an available electron paira lone pair or
an electron pair in a bond.
A Brnsted -Lowry base always donates this electron pair
to a proton, but a Lewis base donates this electron pair to
anything that is electron deficient.

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Acids and Bases

Lewis Acids and Bases
A Lewis acid must be able to accept an electron pair, but
there are many ways for this to occur.
All Brnsted-Lowry acids are also Lewis acids, but the
reverse is not necessarily true.
o Any species that is electron deficient and capable of
accepting an electron pair is also a Lewis acid.
Common examples of Lewis acids (which are not BrnstedLowry acids) include BF3 and AlCl3. These compounds
contain elements in group 3A of the periodic table that can
accept an electron pair because they do not have filled
valence shells of electrons.

Acids and Bases

Lewis Acids and Bases
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 electronpoor 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.

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Acids and Bases

Lewis Acids and Bases
A Lewis acid is also called an electrophile.
When a Lewis base reacts with an electrophile other
than a proton, the Lewis base is also called a
nucleophile. In this example, BF3 is the electrophile and
H2O is the nucleophile.

electrophile

nucleophile

Acids and Bases

Lewis Acids and Bases
Two other examples are shown below. Note that in each
reaction, the electron pair is not removed from the
Lewis base. Instead, it is donated to an atom of the
Lewis acid and one new covalent bond is formed.

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Acids and Bases

Lewis Acids and Bases
In some Lewis acid-base reactions, one bond is formed
and one bond is broken. To draw the products of these
reactions, keep in mind the following steps:
o Always identify the Lewis acid and base first.
o Draw a curved arrow from the electron pair of the
base to the electron-deficient atom of the acid.
o Count electron pairs and break a bond when needed
to keep the correct number of valence electrons.

Acids and Bases

Lewis Acids and Bases
Consider the Lewis acid-base reaction between
cyclohexene and HCl. The Brnsted-Lowry acid HCl
is also a Lewis acid, and cyclohexene, having a bond,
is the Lewis base.

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Acids and Bases

Lewis Acids and Bases
To draw the product of this reaction, the electron pair in
the bond of the Lewis base forms a new bond to the
proton of the Lewis acid, generating a carbocation.
The HCl bond must break, giving its two electrons to
Cl, forming Cl.
Because two electron pairs are involved, two curved
arrows are needed.

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