Acids and Bases

C 2004 Barry Linkletter, UPEI
Acids
and
Bases
Acids and Bases

• Bronstead
– Anything that can give
up a proton is an acid
– Anything that can
accept a proton is a
base
• Lewis
– Anything that can
accept an electron pair
can be an acid
– Anything with an
electron pair can be a
base
2
“Naked” H + Does Not Exist

• Heterolytic cleavage
of HCl in a vacuum is
nearly impossible
– Homolytic cleavage is
the only observed
product
• In Water, we get
complete dissociation
of HCl. Why?
3
Water Stabiles Chloride Ions
4
Water Coordinates Proton

• Water has two
electron pairs than
can accept the proton
• In this case, water is
the Lewis base and
proton is the Lewid
acid.
• The resulting
hydronium ion is a
Brönstead acid
5
Hydronium ion stabilized by Water
6
Acids Need Bases

• If a molecule is an • If a molecule can
acid, it can donate a accept a proton from
proton to a base. an acid, it is a base.
• Strong acids are • Strong bases are
lower in energy of lower in energy when
they can donate the protonated.
proton • Weak bases are
• Weak acids are higher higher in energy when
in energy without the protonated
proton
7
Strong and Weak Acids
8
Rules of Thumb
• The acid with the higher pKa value is the

stronger base in its basic form.
• pKa is the affinity value for the acid and
the proton
– High - acid holds proton tightly
– Low - acid easily gives up proton
• A given proton will go to the base whose
acid form has the higher pKa value
9
Arrhenius Acids and Bases

• In 1884, Svante Arrhenius proposed these
definitions
– acid: a substance that produces H 3O+ ions
aqueous solution
– base: a substance that produces OH- ions in
aqueous solution
– this definition of an acid is a slight
modification of the original Arrhenius
definition, which was that an acid produces H +
in aqueous solution
– today we know that H+ reacts immediately with
a water molecule to give a hydronium ion
Brønsted-Lowry Definitions
• Acid: a proton donor

• Base: a proton acceptor
Conjugate Acids & Bases

– conjugate base: the species formed from an
acid when it donates a proton to a base
– conjugate acid: the species formed from a
base when it accepts a proton from an acid
– acid-base reaction: a proton-transfer reaction
– conjugate acid-base pair: any pair of molecules
or ions that can be interconverted by transfer
of a proton

– Brønsted-Lowry definitions do not require
water as a reactant
– consider the following reaction between acetic
acid and ammonia

– we can use curved arrows to show the flow of
electrons in an acid-base reaction

• Many organic molecules have two or more
sites that can act as proton acceptors
● in this chapter, we limit our discussion to
carboxylic acids, esters, and amides
● in these molecules, the favored site of
protonation is the one in which the charge is
more delocalized
● question: which oxygen of a carboxylic acid is
protonated?
● for protonation on the carbonyl oxygen, we can

write three contributing structures
● two place the positive charge on oxygen, one
places it on carbon
● A-1 and A-3 make the greater contribution

because all atoms have complete octets
● the positive charge is delocalized over three
atoms with the greater share on the two
equivalent oxygens
● for protonation on the hydroxyl oxygen, we can

write two contributing structures
● B-2 makes only a minor contribution because of

charge separation and adjacent positive
charges
● therefore, we conclude that protonation of a
carboxylic acid occurs preferentially on the
carbonyl oxygen
• Problem 4.3 Does proton transfer to an

amide group occur preferentially on the
amide oxygen or the amide nitrogen?
Pi Electrons As Basic Sites
• Proton-transfer reactions occur with

compounds having pi electrons, as for
example the pi electrons of carbon-carbon
double and triple bonds
● the pi electrons of 2-butene, for example,
react with HBr by proton transfer to form a
new C-H bond
● the result is formation of a carbocation, a

species in which one of its carbons has only six
electrons in its valence shell and carries a
charge of +1
Pi Electrons As Basic Sites
• Problem 4.4 Draw Lewis structures for the

two possible carbocations formed by
proton transfer from HBr to 2-methyl-2-
butene
Acids & Base Strengths
• The strength of an acid is expressed by an

equilibrium constant
● the acid dissociation of acetic acid is given by
the following equation
Weak Acids and Bases
• We can write an equilibrium expression for

the dissociation of any uncharged acid, HA,
as:
● water is a solvent and its concentration is a

constant equal to approximately 55.5 mol/L
● we can combine these constants to give a new
constant,K a, called an acid dissociation constant
Acid-Base Equilibria
• Equilibrium favors reaction of the

stronger acid and stronger base to give
the weaker acid and weaker base
Acid-Base Equilibria
• Consider the reaction between acetic acid

and sodium bicarbonate
● we can write the equilibrium as a net ionic
equation
● we omit Na+ because it does not undergo any
chemical change in the reaction
● equilibrium lies to the right

● carbonic acid forms, which then decomposes to
carbon dioxide and water
Molecular Structure and Acidity

• The overriding principle in determining the
relative acidities of uncharged organic
acids is the stability of the anion, A -,
resulting from the loss of a proton
● the more stable the anion, the greater the
acidity of HA
• Ways to stabilize anions include having the
negative charge
● on a more electronegative atom
● on a larger atom
● delocalized through resonance
● delocalized by the inductive effect
● in an orbital with more s character
A. Electronegativity of the atom bearing the

negative charge
– within a period, the greater the electronegativity of the
atom bearing the negative charge, the more strongly its
electrons are held, the more stable the anion is, and the
stronger the acid
• ••A
• ci d • ••C••
o•n•
ju
••g••
at•e•b
•ase
• –
• ••
M••e•th •a•no• l• C
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• H ••C • 3 ••O
• H • ••
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• • •p•••
K•a 16
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• ••
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M• •e•t•
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• • •p•••
K•a 38 • H • H
• H • H
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•• C E•th•••yl••a•
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• i
• • •p•••
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•
•
B. Size of the atom bearing the negative charge

– within a column of the Periodic Table, acidity is related
to the size of the the atom bearing the negative charge
– atomic size increases from top to bottom of a column
– the larger the atom bearing the charge, the greater its
stability
C. Resonance delocalization of charge in A-

– the more stable the anion, the farther the
position of equilibrium is shifted to the right
– compare the acidity alcohols and carboxylic
acids
– ionization of the O-H bond of an alcohol gives
an anion for which there is no resonance
stabilization

– ionization of a carboxylic acid gives a
resonance-stabilized anion
– the pK a of acetic acid is 4.76
– carboxylic acids are stronger acids than

alcohols as a result of the resonance
stabilization of the carboxylate anion
D. Electron-withdrawing inductive effect

– the polarization of electron density of a covalent bond
due to the electronegativity of an adjacent covalent bond
– stabilization by the inductive effect falls off rapidly

with increasing distance of the electronegative atom
from the site of negative charge
– we also see the operation of the inductive

effect in the acidity of halogen substituted
carboxylic acids
E. Hybridization
– for anions differing only in the hybridization of the
charged atom, the greater the %s character to the
hybrid orbital of the charged atom, the more stable the
anion
– consider the acidity of alkanes, alkenes, and alkynes
(given for comparison are the acidities of water and
ammonia)
Lewis Acids and Bases
• Lewis acid: any molecule of ion that can

form a new covalent bond by accepting a
pair of electrons
• Lewis base: any molecule of ion that can
form a new covalent bond by donating a
pair of electrons
- +
A + : A B • new covalent bond
B
Lewis • formed in this Lewis
Lewis • acid-base reaction
base
acid
Lewis Acids and Bases
– examples
• :
• H •• •:B• r :
• H
• •: :
• +
••3 -C• ••C•- C• H3 • +•• •:B r
• • C• H -
• • C• H
••3 -C• ••C•- C• H3
• H• H • H• H
• sec-
• Butyl cation • Bromide • 2-Bromobutane
• (a carbocation) • ion
• • C• H
• 3• C• H 2 • F • • C• H
• 3• C• H 2 • F
• + • -
•• •:O: • + • B
• F •• :O• ••B - F
• • C• H
• 3• C• H 2 • F • 3• C• H 2 • F
• • C• H
• Diethyl • Boron • A •BF3 • -ether
• (a Lewis etherbase)• (atrifluoride
Lewis acid) complex
Effect of Electronegativity on
K
p a
• As the bond to H becomes more polarized, H becomes
more positive and the bond is easier to break.
Chapter 1
Effect of Size on pK a
• As size increases, the H is more loosely

held and the bond is easier to break.
• A larger size also stabilizes the anion.
Chapter 1
Effect of Resonance on pK a
• If the negative charge on an atom can be delocalized over two

or more atoms, the acidity of that compound will be greater
than when the negative charge cannot be delocalized.
• The ethoxide anion is less acidic than the acetate ion simply
because the acetate ion can delocalize the negative charge.
• Methanesulfonic acid can delocalize the charge in three
different resonance forms, making it more acidic than the
acetate ion.
Chapter 1 38
Nucleophiles and Electrophiles

• Nucleophile : Donates electrons to a
nucleus with an empty orbital.
• Electrophile : Accepts a pair of electrons.
• When forming a bond, the nucleophile
attacks the electrophile, so the arrow
goes from negative to positive.
• When breaking a bond, the more
electronegative atom receives the
electrons.
Chapter 1
Nucleophiles and Electrophiles

(Continued)
Chapter 1

Acids and Bases

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Acids and Bases

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C 2004 Barry Linkletter, UPEI

Acids and Bases

“Naked” H + Does Not Exist

Water Stabiles Chloride Ions

Water Coordinates Proton

Hydronium ion stabilized by Water

Acids Need Bases

Strong and Weak Acids

• The acid with the higher pKa value is the

Arrhenius Acids and Bases

• Acid: a proton donor

Conjugate Acids & Bases

Conjugate Acids & Bases

Conjugate Acids & Bases

Conjugate Acids & Bases

● for protonation on the carbonyl oxygen, we can

● A-1 and A-3 make the greater contribution

● for protonation on the hydroxyl oxygen, we can

● B-2 makes only a minor contribution because of

Conjugate Acids & Bases

• Problem 4.3 Does proton transfer to an

• Proton-transfer reactions occur with

● the result is formation of a carbocation, a

Pi Electrons As Basic Sites

• Problem 4.4 Draw Lewis structures for the

Acids & Base Strengths

• The strength of an acid is expressed by an

Weak Acids and Bases

• We can write an equilibrium expression for

● water is a solvent and its concentration is a

• Equilibrium favors reaction of the

• Consider the reaction between acetic acid

● equilibrium lies to the right

Molecular Structure and Acidity

Molecular Structure and Acidity

A. Electronegativity of the atom bearing the

B. Size of the atom bearing the negative charge

Molecular Structure and Acidity

C. Resonance delocalization of charge in A-

Molecular Structure and Acidity

– carboxylic acids are stronger acids than

D. Electron-withdrawing inductive effect

– stabilization by the inductive effect falls off rapidly

– we also see the operation of the inductive

• Lewis acid: any molecule of ion that can

• As size increases, the H is more loosely

• If the negative charge on an atom can be delocalized over two

Nucleophiles and Electrophiles

Nucleophiles and Electrophiles

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