Organic Chemistry

For Biology Students

Lecture 2 : Acids bases

Dr. Doan Duy Tien

 Acids and Bases
• A Brønsted acid is a proton donor.
• A Brønsted base is a proton acceptor.
• H+ = proton

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 Acids and Bases
Reactions
• A 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 H—A loses a proton, leaving the electron pair in the
H—A bond on A.

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 Acids and Bases
Reactions
• The movement of electrons in reactions can be illustrated using
curved arrow notation.
• 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:

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Acids and Bases
 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 Brønsted-Lowry acid H—A is dissolved in water, an
acid-base reaction occurs, and an equilibrium constant can
be written for the reaction.

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 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.

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 Acids and Bases
Acid Strength and pKa

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 Acids and Bases
Factors that Determine Acid Strength
• Anything that stabilizes a conjugate base A:¯ makes the
starting acid H—A more acidic.
• Four factors affect the acidity of H—A. These are:
Element effects
Inductive effects
Resonance effects
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. 9
 Acids and Bases
Factors that Determine Acid Strength
Element Effects—Trends in the Periodic Table.
Across a row of the periodic table, the acidity of H—A
increases as the electronegativity of A increases.

Positive or negative charge is stabilized when it is spread

over a larger volume.

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 Acids and Bases
Factors that Determine Acid Strength
Element Effects—Trends in the Periodic Table.
• Down a column of the periodic table, the acidity of H—A
increases as the size of A increases.

• Size, and not electronegativity, determines acidity down a

column.
• The acidity of H—A 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 effects—the identity of
A—is the single most important factor in determining11 the
acidity of the H—A bond.
 Acids and Bases
Factors that Determine Acid Strength—Inductive Effects
• An inductive effect is the pull of electron density
through  bonds caused by electronegativity differ-
ences between 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.

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 Acids and Bases
Factors that Determine Acid Strength—Inductive Effects
• The reason for the increased acidity of 2,2,2-
trifluoroethanol is that the three electronegative
fluorine atoms stabilize the negatively charged
conjugate base.

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 Acids and Bases
Factors that Determine Acid Strength—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 H—A increases with the presence of electron
withdrawing groups in A.

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 Acids and Bases
Factors that Determine Acid Strength—Resonance 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.

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 Acids and Bases
Factors that Determine Acid Strength—Resonance
Effects
• Resonance delocalization makes CH3COO¯ more
stable than CH3CH2O¯, so CH3COOH is a stronger acid
than CH3CH2OH.

• The acidity of H—A increases when the conjugate

base A:¯ is resonance stabilized.
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 Acids and Bases
Factors that Determine Acid Strength—Resonance
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¯.

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 Acids and Bases
Factors that Determine Acid Strength—Hybridization
Effects
• The final factor affecting the acidity of H—A is the
hybridization of A.
Let us consider the relative acidities of three different
compounds containing C—H 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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 Acids and Bases
Factors that Determine Acid Strength—Hybridization
Effects

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 Acids and Bases
Factors that Determine Acid Strength—Hybridization
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 in organic
reactions. Two examples are acetic acid and p-toluene-
sulfonic acid (TsOH).

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

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 Acids and Bases
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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 Acids and Bases:
electrophile- nucleophile

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
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 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
Consider the Lewis acid-base reaction between
cyclohexene and H—Cl. The BrØnsted-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 H—Cl 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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