C 2004 Barry Linkletter, UPEI

Acids
and
Bases
 C 2004 Barry Linkletter, UPEI

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
 C 2004 Barry Linkletter, UPEI

“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
 C 2004 Barry Linkletter, UPEI

Water Stabiles Chloride Ions

4
 C 2004 Barry Linkletter, UPEI

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
 C 2004 Barry Linkletter, UPEI

Hydronium ion stabilized by Water

6
 C 2004 Barry Linkletter, UPEI

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 lower • Strong bases are
in energy of they can lower in energy when
donate the proton protonated.
• Weak acids are higher • Weak bases are higher
in energy without the in energy when
proton protonated

7
 C 2004 Barry Linkletter, UPEI

Strong and Weak Acids

8
 C 2004 Barry Linkletter, UPEI

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
 C 2004 Barry Linkletter, UPEI

Arrhenius Acids and Bases

• In 1884, Svante Arrhenius proposed these
definitions
– acid: a substance that produces H3O+ 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

H+( aq) + H2 O( l) H3 O+( aq)

Hydronium ion
 C 2004 Barry Linkletter, UPEI

Brønsted-Lowry Definitions

• Acid: a proton donor

• Base: a proton acceptor
+ -
:

: :

:
H O H + :O H H O: + H O H

:
H H
Proton Proton
donor acceptor

H H
+ +
:
:

H O H + :N H H O: + H N H
H H H H
Proton Proton
donor acceptor
 C 2004 Barry Linkletter, UPEI

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
con jugate acid-bas e pair
con jugate acid-bas e pair

+
HCl(aq) + H2 O( l) Cl-( aq) + H3 O (aq)
Hyd rogen Water Chlorid e Hydronium
chloride ion ion
(acid ) (base) (conju gate (conjugate
b ase of HCl) acid of H 2O)
 C 2004 Barry Linkletter, UPEI

Conjugate Acids & Bases

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

conju gate acid -base p air

conju gate acid -base p air

CH3 COOH + NH3 CH3 COO- + NH4 +

A cetic acid Ammonia Acetate Ammonium
ion ion
(acid ) (base) (conju gate b ase (conjugate acid
acetic acid ) of ammonia)
 C 2004 Barry Linkletter, UPEI

Conjugate Acids & Bases

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

:O: H :O: H
: :

: :
CH3 -C-O H + :N H CH3 -C-O:- + H-N-H
H H
A cetic acid Ammonia Acetate ion Ammonium
(proton d on or) (p roton acceptor) ion
 Conjugate Acids & Bases
C 2004 Barry Linkletter, UPEI

• Many organic molecules have two or more

sites that can act as proton acceptors
u in this chapter, we limit our discussion to
carboxylic acids, esters, and amides
u in these molecules, the favored site of
protonation is the one in which the charge is
more delocalized
u question: which oxygen of a carboxylic acid is
protonated?
+ H
O O O
+ -
CH3 -C-O-H + H2 SO4 CH3 -C-O-H or CH3 -C-O-H + HSO4
H
A B
(p roton ation (p roton ation
on th e on the
carbonyl oxygen) h yd roxyl oxygen )
 Conjugate Acids & Bases
C 2004 Barry Linkletter, UPEI

u for protonation on the carbonyl oxygen, we can

write three contributing structures
u two place the positive charge on oxygen, one
places it on carbon
+ H H H
O O O
+ +
CH3 -C-O-H CH3 -C-O-H
-C CH3 -C=O-H
A-1 A-2 A-3
(C an d O have (C h as incomplete (C an d O have
comp lete octets) octet) comp lete octets)

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

because all atoms have complete octets
u the positive charge is delocalized over three
atoms with the greater share on the two
equivalent oxygens
 Conjugate Acids & Bases
C 2004 Barry Linkletter, UPEI

u for protonation on the hydroxyl oxygen, we can

write two contributing structures
O O
+ +
CH3 -C-O-H CH3 -C-O-H
+
H H
B-1 B-2
(ch arge sep aration an d
ad jacen t positive charges)
u B-2 makes only a minor contribution because of
charge separation and adjacent positive
charges
u therefore, we conclude that protonation of a
carboxylic acid occurs preferentially on the
carbonyl oxygen
 C 2004 Barry Linkletter, UPEI

Conjugate Acids & Bases

• Problem 4.3 Does proton transfer to an

amide group occur preferentially on the
amide oxygen or the amide nitrogen?

+ H
O O OH
+ -
CH3 -C-N-H + HCl CH3 -C-N-H or CH3 -C-N-H + Cl
H H H
A B
A cetamide (p rotonation (protonation
(an amid e) on the on th e
amide oxygen) amid e nitrogen)
 Pi Electrons As Basic Sites
C 2004 Barry Linkletter, UPEI

• Proton-transfer reactions occur with

compounds having pi electrons, as for
example the pi electrons of carbon-carbon
double and triple bonds
u the pi electrons of 2-butene, for example,
react with HBr by proton transfer to form a
new C-H bond
+ H -
CH3 -CH=CH-CH3 + H-Br CH3 -C-C-CH3 + Br
HH
2-Butene sec-Butyl cation
(a 2° carb ocation )
u 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
 C 2004 Barry Linkletter, UPEI

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

CH3
CH3 -C=CH-CH3 + H-Br
2-Methyl-2-buten e
 C 2004 Barry Linkletter, UPEI

Acids & Base Strengths

• The strength of an acid is expressed by an

equilibrium constant
u the acid dissociation of acetic acid is given by
the following equation
O O
- +
CH3 COH + H2 O CH3 CO + H3 O
A cetic acid Water Acetate Hyd roniu m
ion ion
 C 2004 Barry Linkletter, UPEI

Weak Acids and Bases

• We can write an equilibrium expression for

the dissociation of any uncharged acid, HA,
as: - +
HA + H2 O A + H3 O
+ -
+ - K a = Keq[ H2 O] = [H3 O ][A ]
Keq = [H3 O ] [A ]
[HA]
[ HA][ H2 O]

u water is a solvent and its concentration is a

constant equal to approximately 55.5 mol/L
u we can combine these constants to give a new
constant, Ka, called an acid dissociation constant
 C 2004 Barry Linkletter, UPEI

Acid Formula pK a Conju gate Bas e

-
Weaker Ethan e CH3 CH3 51 CH3 CH2 S tronger
acid - conju gate
Ethylene CH2 =CH2 44 CH2 =CH
- base
Ammonia NH3 38 NH2
Hyd rogen H2 35 H-
-
Acetylene HC CH 25 HC C
-
Ethan ol CH3 CH2 OH 15.9 CH3 CH2 O
-
Water H2 O 15.7 HO
+
Methylammon ium ion CH3 NH3 10.64 CH3 NH2
- 2-
Bicarbonate ion HCO3 10.33 CO3
-
Phen ol C6 H5 OH 9.95 C6 H5 O
+
Ammoniu m ion NH4 9.24 NH3
-
Hyd rogen su lfid e H2 S 7.04 HS
-
Carbonic acid H2 CO3 6.36 HCO3
-
Acetic acid CH3 COOH 4.76 CH3 COO
-
Benzoic acid C6 H5 COOH 4.19 C6 H5 COO
-
Phosp horic acid H3 PO4 2.1 H2 PO4
+
Hyd roniu m ion H3 O -1.74 H2 O
-
Sulfuric acid H2 SO4 -5.2 HSO4
-
Hyd rogen ch loride HCl -7 Cl
- Weaker
Stron ger Hyd rogen bromide HBr -8 Br conju gate
-
acid Hyd rogen iod ide HI -9 I base
 C 2004 Barry Linkletter, UPEI

Acid-Base Equilibria

• Equilibrium favors reaction of the stronger

acid and stronger base to give the weaker
acid and weaker base
-
CH3 COOH + NH3 CH3 COO + NH4 +
A cetic acid Ammon ia Acetate ion A mmonium ion
pK a 4.76 (stron ger bas e) (w eaker bas e) pK a 9.24
(stron ger acid ) (w eak er acid)
pK eq = 4.76 - 9.24 = -4.48
Ke q = 3.0 x 104
 Acid-Base Equilibria
C 2004 Barry Linkletter, UPEI

• Consider the reaction between acetic acid

and sodium bicarbonate
u we can write the equilibrium as a net ionic
equation
u we omit Na+ because it does not undergo any
chemical change in the reaction
O O
-
CH3 COH + HCO3 - CH3 CO + H2 CO3
Acetic acid Bicarb on ate ion Acetate ion Carbonic acid
pK a 4.76 pK a 6.36
(stron ger acid ) (weak er acid)

u equilibrium lies to the right

u carbonic acid forms, which then decomposes to
carbon dioxide and water
 C 2004 Barry Linkletter, UPEI

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
u the more stable the anion, the greater the
acidity of HA
• Ways to stabilize anions include having the
negative charge
u on a more electronegative atom
u on a larger atom
u delocalized through resonance
u delocalized by the inductive effect
u in an orbital with more s character
 C 2004 Barry Linkletter, UPEI

Molecular Structure and Acidity

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•c•i•d •C•o•n•j•u•g•a•t•e••b•a•s•e

•M•e•t•h•a•n•o•l •C•H•3 •O •H •C•H•3 •O•••– •M•e•t•h•o•x•i•d•e••i•o•n

•p•K•a•••1•6

•M•e•t•h•y•l•a•m•i•n•e •C•H•3 •N •H •C•H•3 •N•••– •M•e•t•h•y•l•a•m•i•d•e••i•o•n

•p•K•a•••3•8 •H •H
•H •H
•E•t•h•a•n•e •C•H•3 •C •H •C•H•3 •C• •– •E•t•h•y•l••a•n•i•o•n
•p•K•a•••5•1 •H •H
 Molecular Structure and Acidity
C 2004 Barry Linkletter, UPEI

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

– –
CH3 S H + CH3 O CH3 S + CH3 O H
Methan ethiol Meth oxid e Methan ethiolate Methanol
p Ka 7.0 ion ion p Ka 16
(stronger acid ) (stronger bas e) (w eaker base) (w eaker acid)
 C 2004 Barry Linkletter, UPEI

Molecular Structure and Acidity

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
+
CH3 CH2 O-H + H2 O CH3 CH2 O - + H3 O pK a = 15.9
An alcohol An alkoxide ion
 C 2004 Barry Linkletter, UPEI

Molecular Structure and Acidity

– ionization of a carboxylic acid gives a
resonance-stabilized anion
– the pKa of acetic acid is 4.76
O O O
+
CH3 C + H2 O CH3 C CH3 C + H3 O
O H O O
equ ivalen t contrib uting structu res ;
the carb oxylate anion is stab ilized by
delocalization of the n egative ch arge.

– carboxylic acids are stronger acids than

alcohols as a result of the resonance
stabilization of the carboxylate anion
Molecular Structure and Acidity
C 2004 Barry Linkletter, UPEI

D. Electron-withdrawing inductive effect

– the polarization of electron density of a covalent bond
due to the electronegativity of an adjacent covalent bond
H F
H C-CH2 O-H F C-CH2 O-H
H F
Ethanol 2,2,2-Tri fl uoroethano l
pK a 15.9 pK a 12.4
– stabilization by the inductive effect falls off rapidly
with increasing distance of the electronegative atom
from the site of negative charge

CF3 -CH2 -OH CF3 -CH2 -CH2 -OH CF3 -CH2 -CH2 -CH2 -OH
2,2,2-Trifluoro- 3,3,3-Trifluoro-1- 4,4,4-Trifluoro-1-
ethan ol prop anol butan ol
(pK a 12.4) (p Ka 14.6) (pK a 15.4)
Molecular Structure and Acidity
C 2004 Barry Linkletter, UPEI

– we also see the operation of the inductive

effect in the acidity of halogen substituted
carboxylic acids

O O Cl O O
Cl
OH OH OH OH
Cl
Bu tanoic 4-Ch lorob utan oic 3-Ch lorobutan oic 2-Chlorob utanoic
acid acid acid acid
pK a 4.82 p Ka 4.52 pK a 3.98 pK a 2.83
 Molecular Structure and Acidity
C 2004 Barry Linkletter, UPEI

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)

Weak Conjugate
Acid Bas e p Ka

Water HO-H HO– 15.7

Alk yn e HC C H HC C– 25
Ammonia H2 N-H H2 N– 38
–
Alken e CH2 =CH-H CH2 =CH 44
CH3 CH2 –

In

in

d
a
g
a
c
re
Alkan e 51

s
CH3 CH2 -H

it
ci
 Lewis Acids and Bases
C 2004 Barry Linkletter, UPEI

• 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 + :B A B •new covalent bond
Lewis •formed in this Lewis
Lewis base •acid-base reaction
acid
 Lewis Acids and Bases
C 2004 Barry Linkletter, UPEI

– examples

•:
•H •H •:•B•r•:
•+

•: •:
•C•H•3•-•C •C•-•C•H•3 •+ •:•B•r -
•C•H•3•-•C •C•-•C•H•3
•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 •C•H•3•C•H•2 •F
• Diethyl ether •Boron trifluoride •A BF•3•-ether complex
•(a Lewis base) • (a Lewis acid)
 Effect of Electronegativity on
C 2004 Barry Linkletter, UPEI

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

Chapter 1
 C 2004 Barry Linkletter, UPEI

Effect of Size on pKa

• 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
 C 2004 Barry Linkletter, UPEI

Effect of Resonance on pKa

• 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
 C 2004 Barry Linkletter, UPEI

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
 C 2004 Barry Linkletter, UPEI

Nucleophiles and Electrophiles

(Continued)

Chapter 1