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4-4-11
Organic Organic ChemistryChemistry
William H. BrownWilliam H. Brown
Christopher S. FooteChristopher S. Foote
Brent L. IversonBrent L. Iverson
William H. BrownWilliam H. Brown
Christopher S. FooteChristopher S. Foote
Brent L. IversonBrent L. Iverson
4-4-22
Acids Acids and and BasesBases
Chapter 4Chapter 4
4-4-33
Arrhenius Acids and BasesArrhenius Acids and Bases In 1884, Svante Arrhenius proposed these
definitions • acid:acid: a substance that produces H3O+ ions aqueous
solution• base: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) + H2O(l) H3O+(aq)Hydronium ion
4-4-44
Brønsted-Lowry DefinitionsBrønsted-Lowry Definitions Acid:Acid: a proton donor Base:Base: a proton acceptor
+
Proton donor
Protonacceptor
-O H
H
OH
H
O HH + +O H H
+
Protonacceptor
Protondonor
+O H
H
OH
H
N H
H
H
H
H
H + +N H H
: ::
: :
:
::
: :
::
4-4-55
Conjugate Acids & BasesConjugate Acids & Bases
• conjugate baseconjugate base: the species formed from an acid when it donates a proton to a base
• conjugate acid:conjugate acid: the species formed from a base when it accepts a proton from an acid
• acid-base reaction:acid-base reaction: a proton-transfer reaction• conjugate acid-base pair:conjugate acid-base pair: any pair of molecules or ions
that can be interconverted by transfer of a proton
HCl(aq) H2O(l) Cl-(aq) H3O+(aq)+ +WaterHydrogen
chlorideHydronium
ionChloride
ion(base)(acid) (conjugate
acid of H2O)(conjugate
base of HCl)
conjugate acid-base pair
conjugate acid-base pair
4-4-66
Conjugate Acids & BasesConjugate Acids & Bases
• Brønsted-Lowry definitions do not require water as a reactant
• consider the following reaction between acetic acid and ammonia
NH4+CH3COOH CH3COO-
NH3+ +
Acetic acid Ammonia
(acid)
conjugate acid-base pair
Acetate ion
Ammoniumion
(base) (conjugate baseacetic acid)
(conjugate acidof ammonia)
conjugate acid-base pair
4-4-77
Conjugate Acids & BasesConjugate Acids & Bases
• we can use curved arrows to show the flow of electrons in an acid-base reaction
CH3-C-OO
H N HH
H CH3-C-O -
OH-N-H
H
H+ +
Acetic acid(proton donor)
Acetate ion
:
:: ::
:: :: :
Ammonia(proton acceptor)
Ammoniumion
4-4-88
Conjugate Acids & BasesConjugate Acids & Bases 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?
CH3-C-O-H
O+ H2SO4 CH3-C-O-H
HO+
CH3-C-O-HH
O+
+ HSO4-or
A(protonation
on the carbonyl oxygen)
B(protonation
on thehydroxyl oxygen)
4-4-99
Conjugate Acids & BasesConjugate Acids & Bases 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
++
CH3-C-O-H
OH
CH3-C-O-H
OH
CH3-C
OH
++CH3-C-O-H
O
CH3-C=O-H
OH
CH3-C=O-H
OH+
A-1(C and O have
complete octets)
A-2(C has incomplete
octet)
A-3(C and O have
complete octets)
4-4-1010
Conjugate Acids & BasesConjugate Acids & Bases 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
CH3-C-O-H
O
H
+
B-1
CH3-C-O-H
O
H+
+
B-2(charge separation and
adjacent positive charges)
4-4-1111
Conjugate Acids & BasesConjugate Acids & Bases Problem 4.3Problem 4.3 Does proton transfer to an amide
group occur preferentially on the amide oxygen or the amide nitrogen?
CH3-C-N-H
H
O+ HCl
+
CH3-C-N-H
OH
H
H
CH3-C-N-H
H
O+
+ Cl -or
A(protonation
on theamide oxygen)
B(protonation
on theamide nitrogen)
Acetamide(an amide)
4-4-1212
Pi Electrons As Basic SitesPi 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 carbocationcarbocation, a species in which one of its carbons has only six electrons in its valence shell and carries a charge of +1
CH3-CH=CH-CH3 + H-Br CH3-C-C-CH3 + Br -
H
H
+
2-Butene sec-Butyl cation(a 2° carbocation)
H
4-4-1313
Pi Electrons As Basic SitesPi Electrons As Basic Sites Problem 4.4Problem 4.4 Draw Lewis structures for the two
possible carbocations formed by proton transfer from HBr to 2-methyl-2-butene
CH3-C=CH-CH3 + H-Br
2-Methyl-2-butene
CH3
4-4-1414
Acids & Base StrengthsAcids & 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
H3O+
+CH3CO-
OH2O+CH3COH
O
Acetic acid Water Acetateion
Hydroniumion
4-4-1515
Weak Acids and BasesWeak 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, KKaa, called an acid dissociation constantacid dissociation constant
HA + H2O
[H3O+][A
-]
[HA][H2O]Keq
A- + H3O
+
=
Keq[H2O]Ka[H3O+][A-]
[HA]= =
4-4-1616HI I-
HBr Br-
HCl Cl-
H2SO4 HSO4-
H2OH3O+
H3PO4 H2PO4-
C6H5COOH C6H5COO-
CH3COOH CH3COO-
H2CO3 HCO3-
H2S HS-
NH3NH4+
C6H5OH C6H5O-
HCO3-
CO32-
CH3NH2CH3NH3+
H2O HO-
CH3CH2OH CH3CH2O-
HC CH HC C-H2 H-NH3 NH2
-CH2=CH2 CH2=CH
-CH3CH3 CH3CH2
-Acid Formula pKa Conjugate BaseEthane
Ammonia
EthanolWater
Bicarbonate ionPhenol
Ammonium ion
Carbonic acidAcetic acid
3525
Benzoic acidPhosphoric acid
Sulfuric acidHydrogen chlorideHydrogen bromideHydrogen iodide
51
38
10.33
15.715.9
4.766.36
9.24
9.95
-5.2-7
-9-8
4.19
2.1-1.74Hydronium ion
Strongerconjugate
base
Weakerconjugate
base
Weaker acid
Stronger acid
Methylammonium ion 10.64
Hydrogen sulfide 7.04
AcetyleneHydrogen
Ethylene 44
4-4-1717
Acid-Base EquilibriaAcid-Base Equilibria Equilibrium favors reaction of the stronger acid
and stronger base to give the weaker acid and weaker base
CH3COOH NH3 CH3COO-
NH4++ +
Ammonia(stronger base)
Acetate ion(weaker base)
Acetic acidpKa 4.76
(stronger acid)
Ammonium ionpKa 9.24
(weaker acid)
pKeq = 4.76 - 9.24 = -4.48
Keq = 3.0 x 104
4-4-1818
Acid-Base EquilibriaAcid-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
CH3COH
OHCO3
- CH3CO-
O
H2CO3
Bicarbonate ion Acetate ionAcetic acidpKa 4.76
(stronger acid)
Carbonic acidpKa 6.36
(weaker acid)
+ +
4-4-1919
Molecular Structure and AcidityMolecular 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
4-4-2020
Molecular Structure and AcidityMolecular 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
CH
HH
NH
H
O H
EthanepKa 51
MethylaminepKa 38
MethanolpKa 16
i
Conjugate base
CH3 C –H
H
CH3 N –
H
CH3 O –
Methylamide ion
Methoxide ion
Ethyl anionCH3
CH3
CH3
Acid
4-4-2121
Molecular Structure and AcidityMolecular Structure and Acidity
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
S HCH3 CH3 O – CH3 S –O HCH3
MethanethiolpKa 7.0
(stronger acid)
Methoxide ion
(stronger base)
Methanethiolateion
(weaker base)
MethanolpKa 16
(weaker acid)
+ +
4-4-2222
Molecular Structure and AcidityMolecular 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
CH3CH2O-H H2O CH3CH2O - H3O++
An alcohol An alkoxide ion
+ pKa = 15.9
4-4-2323
Molecular Structure and AcidityMolecular Structure and Acidity
• ionization of a carboxylic acid gives a resonance-stabilized anion
• the pKa of acetic acid is 4.76
• carboxylic acids are stronger acids than alcohols as a result of the resonance stabilization of the carboxylate anion
equivalent contributing structures; the carboxylate anion is stabilized bydelocalization of the negative charge.
+CH3 C
O
O
C
O
O
CH3O H
C
O
CH3 H3O+
+ H2O
4-4-2424
Molecular Structure and AcidityMolecular Structure and Acidity
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
C-CH2O-H
H
H
H
C-CH2O-H
F
F
F
EthanolpKa 15.9
2,2,2-TrifluoroethanolpKa 12.4
CF3-CH2-OH CF3-CH2-CH2-OH CF3-CH2-CH2-CH2-OH
2,2,2-Trifluoro-ethanol
(pKa 12.4)
3,3,3-Trifluoro-1-propanol(pKa 14.6)
4,4,4-Trifluoro-1-butanol
(pKa 15.4)
4-4-2525
Molecular Structure and AcidityMolecular Structure and Acidity
• we also see the operation of the inductive effect in the acidity of halogen substituted carboxylic acids
Butanoic acid
pKa 4.82
4-Chlorobutanoicacid
pKa 4.52
3-Chlorobutanoicacid
pKa 3.98
2-Chlorobutanoicacid
pKa 2.83
OH
O
OH
O
OH
O
OH
O
Cl
ClCl
4-4-2626
Molecular Structure and AcidityMolecular Structure and Acidity
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)
CH3CH2-H CH3CH2–
CH2=CH-H CH2=CH–
H2N-H H2N–
HC C H HC C–
HO-H HO–
Weak Acid
Alkyne
Alkene
Alkane
Water
25
44
51
15.7
ConjugateBase pKa
Increasing acidity
Ammonia 38
4-4-2727
Lewis Acids and BasesLewis Acids and Bases Lewis acid:Lewis acid: any molecule of ion that can form a
new covalent bond by accepting a pair of electrons
Lewis base:Lewis base: any molecule of ion that can form a new covalent bond by donating a pair of electrons
Lewis base
Lewis acid
+ BA new covalent bondformed in this Lewisacid-base reaction
:+-
A B
4-4-2828
Lewis Acids and BasesLewis Acids and Bases
• examples
:
: :
Br -CH3-C C-CH3
H H
H
CH3-C C-CH3
H H
H Br
Bromideion
sec-Butyl cation(a carbocation)
2-Bromobutane
++
: :
::
+ -
Diethyl ether(a Lewis base)
Boron trifluoride (a Lewis acid)
O
CH3CH2
CH3CH2
F
F
O
CH3CH2
CH3CH2
B-F
F
F
+ B
A BF3-ether complex
F:: :
4-4-2929
Acids and Acids and BasesBases
End Chapter 4End Chapter 4