Chapter 2 Acids and Bases Arrhenius Acid and Base Theory

• A significant amount of chemistry can be • In 1884, Svante Arrhenius proposed these

described using different theories of acids and definitions:
bases. • Acid: A substance that dissolves in water to produce
• We’ll consider three different acid-base theories hydronium ions (H3O+). H+ + H2O  H3O+
(listed in order of increasing sophistication) • We’ll use hydronium ion interchangably with hydrogen ion
1. Arrhenius theory • Base: A substance that dissolves in water to produce
2. Brønsted-Lowry theory hydroxide ions (OH–).
3. Lewis theory • In an Arrhenius acid – base reaction, hydrogen ion
reacts with hydroxide ion to form water.

Brønsted-Lowry Acid and Base Theory • When an acid donates a proton, the substance
(missing a hydrogen ion) turns into a base.
• Johannes Brønsted and Thomas Lowry proposed
these definitions: • In the same way, when a base accepts a proton, the
• Acid: A substance that donates a hydrogen ion (proton substance (with an extra hydrogen ion) turns into an
donor). acid.
• Base: A substance that accepts a hydrogen ion (proton • Pairs of substances that are different only by a
acceptor). hydrogen ion are called conjugate acid-base pairs.
• In a Brønsted-Lowry acid-base reaction, a hydrogen
moves from acid to base. (proton transfer).
• All Arrhenius acid-base reactions are Brønsted-
Lowry acid-base reactions (not vice versa).

• Conjugate base: The species formed from an • Conjugate acid: The species formed from a
acid when an acid donates a proton to a base. base when a base accepts a proton from an acid.

Acid  Conjugate base Base  Conjugate acid

HCl  Cl- OH-  H2O
HC2H3O2  C2H3O2- C3H5O3-  HC3H5O3
HCO3-  CO32- HCO3-  H2CO3
NH4+  NH3 NH3  NH4+
H2O  OH- NH2-  NH3

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 Brønsted-Lowry Acid-Base reaction Brønsted-Lowry Acid-Base reaction
• An acid gives a hydrogen ion to the base. • Conjugate acid-base pairs are connected via the
• I.e., The reaction is a proton transfer reaction proton transfer reaction.
where the proton is transferred from the acid to • An acid turns into a base and a base turns into
the base. an acid.

• Brønsted-Lowry definitions mean that an acid-base Acid and Base Strength

reaction does not need to involve water.
• Strong acids completely dissociate into
hydrogen (hydronium) ion and conjugate base.
HBr (aq) + H2O (l)  Br- (aq) + H3O+ (aq)
H2SO4 (aq) + H2O (l)  HSO4- (aq) + H3O+ (aq)
• Memorize list of strong acids
• HCl, HBr, HI
• HNO3, H2SO4
• HClO3, HClO4

• Weak acids partially dissociate into hydronium • The smaller an acid’s Ka, the weaker the acid.
ion and conjugate base. • Often we use an acid’s pKa to describe its
HCH3CO2 (aq) + H2O (l)  CH3CO2- (aq) + H3O+ (aq) strength; thus, the larger the pKa, the weaker
the acid. (This can be confusing!)
• In a weak acid, an equilibrium exists between
the acid, the conjugate base and the hydronium pK a   logK a   log 1.8  10 5   4.74
ion.
• The degree of dissociation (the acid’s strength) Acid Ka pKa
is described using the acid-dissociation H3PO4 7.110-3 2.15
constant, Ka. HC3H5O3 1.410-4 3.86
HCH3CO2 1.810-5 4.74
H O  CH CO 
 

Ka   3   3  1.8  105
2
NH4+ 5.510-10 9.26
HCH3CO2 

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• Commonly the strong bases are considered to • Weak bases partially reaction with water to form
be the soluble hydroxides; but, in organic conjugate acid and hydroxide ion to form an
chemistry, we’ll need to extend our definition as equilibrium similar to a weak acid.
the conjugate bases of acids that are weaker
NH3 (aq) + H2O (l)  NH4+ (aq) + OH- (aq)
than water.
• Strong bases completely dissociate into anion F- (aq) + H2O (l)  HF (aq) + OH- (aq)
and cation. • The degree of reaction (base dissociation) is
NaOH (aq)  Na+
(aq) + OH-
(aq) described using the base-dissociation constant,
Kb.
KOCH3 (aq)  K+ (aq) + OCH3- (aq)
• I.e., Kb, is the measure of how well a base
RbNH2 (aq)  Rb+ (aq) + NH2- (aq)
accepts a proton.
• Strong bases completely react with water to
HF OH 
form conjugate acid and hydroxide ion. Kb   1.5  10 4
CH3O- (aq) + H2O (l)  CH3OH (aq) + OH- (aq)
F 

• The smaller a base’s Kb, the weaker the base. • The strength of an acid and the strength of its
• Or the larger the pKb, the weaker the base. conjugate base are deeply connected.
• The pKa of an acid and the pKb of its conjugate
pK b   logK b   log 1.5  1011   10.83 base adds to equal 14.
Base Kb pKb pK a HF   pK b F   14
C5 H5 N 5.610-5 4.25 3.17  10.83  14.00
pK a NH4   pK b NH3   14
NH3 1.810-5 4.74
F- 1.510-10 9.83
C3 H5 O 3 - 7.110-11 10.14 9.26  4.74  14.00

• Thus, as an acid’s strength increases, the • Understanding the strengths of acids (even
strength of its conjugate base decreases. extremely weak ones), aids in understanding of
proton transfer reactions.

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 Acid-Base Equilibria • Equilibrium in the following acid-base reaction
lies to the right, on the side of the weaker acid
• To determine the position of equilibrium in an and the weaker base.
acid-base reaction:
• Identify the two acids in the equilibrium; one on the
left and one on the right.
• Use the information in a table of pKa’s (Table 2.2) to
determine which is the stronger acid and which is the
weaker acid.
• Remember that the stronger acid gives the weaker
conjugate base, and the weaker acid gives the
stronger conjugate base.
• The stronger acid reacts with the stronger base to
give the weaker acid and weaker base.
• Equilibrium lies on the side of the weaker acid
and the weaker base.

Structure and Acidity • Electronegativity of the atom bearing the

negative charge.
• The most important factor in determining the
relative acidity of an organic acid is the relative • Within a period
stability of the anion, A–, formed when the acid, • The greater the electronegativity of the atom bearing
the negative charge, the more strongly its electrons
HA, transfers a proton to another base. are held.
• We consider these four factors: • The more strongly electrons are held, the more stable
1. The electronegativity of the atom bonded to H in the anion A–.
HA. • The more stable the anion A–, the greater the acidity
2. Resonance stabilization of A–. of the acid HA.
3. The inductive effect.
4. The size and delocalization of charge in A–.

• The greater the resonance stabilization of the

• Resonance delocalization of the charge on A–
anion, the more acidic the compound.
• Compare the acidity of a carboxylic acid and an
alcohol, both of which contain an –OH group. • There is no resonance stabilization in an
• Carboxylic acids are weak acids. Values of pKa for
alkoxide anion.
most unsubstituted carboxylic acids fall within the • We can write two equivalent contributing
range of 4 to 5. structures for the carboxylate anion; the negative
charge is spread evenly over the two oxygen
atoms.
• Alcohols are very weak acids. Values of pKa for most
alcohols fall within the range of 15 to 18.

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• When the carboxylate anion is near groups that • Inductive polarization of electron density
have double bonds, resonance effects increase transmitted through covalent bonds is caused by
the acidity of the molecule. a nearby atom of higher electronegativity.
• Resonance allows the “delocalization” of the • The greater the inductive effect, the greater the
negative charge which increases stability of the acidity.
anion (and increases the acidity of the
molecules.

• The closer an electronegative atom is to the • A group of atoms that attracts electron density to
acidic hydrogen, the more acidic the molecule is. itself is known as an electron-withdrawing
group (EWG).
• A group of atoms that pushes electron density
away from itself is known as an electron-
donating group (EDG).
• Groups can be electron-withdrawing and
electron-donating in two ways.
• Inductive polarization (via electronegativity)
• Resonance (via delocalization of charge)
• These groups can be divided into four
classifications.

• Groups that have electronegative atoms, no • Groups that are simply hydrocarbon branches
neighboring lone pairs of electrons, but has a (alkyl groups).
carbon involved with multiple bonds. • These groups are electron-donating groups via
• These groups are electron-withdrawing induction.
groups via induction and via resonance. • The more branching at the carbon, the more
O electron donating.
O
• aldehyde
C H
• ketone O C R
O
• carboxylic acid
• ester C O H
C O R
• nitrile O

• nitro (best!) C N
N • Note that more electron-donating groups make the the O – H
bond stronger; thus, making the molecule less acidic.
O

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• Groups that have electronegative atoms but no • Groups that have electronegative atoms and
neighboring lone pairs of electrons or multiple neighboring lone pairs of electrons.
bonds. • These groups are electron-withdrawing
• These groups are electron-withdrawing groups via induction and electron-donating
groups via induction only. via resonance.

F • halogen X

• trifluoromethyl C F
• alcohol O H
F

H • amino N H

• ammonium N H H

• Groups that have carbon – carbon double bonds. • The larger the volume over which the charge on
• These groups can be electron-withdrawing or an anion (or cation) is delocalized, the greater
electron-donating groups via resonance. the stability of the anion (or cation).
• Whether these groups withdraw or donate • When considering the relative acidities of the
electron density depends on the rest of the hydrogen halides, (HI > HBr > HCl > HF), we need to
consider the relative stabilities of the halide ions.
molecule.
• Recall from general chemistry that atomic size is a
• These groups are excellent at distributing charge. periodic property.
(Molecules with these types of groups may have • For main group elements, atomic radii increase going
multiple resonance structures.) down a group and increase going across a period.
H
• vinyl C CH2

• phenyl

• For the halogens, iodine has the largest atomic radii, Lewis Acid and Base Theory
fluorine has the smallest I > Br > Cl > F.
• Gilbert Lewis proposed these definitions:
• Anions are always larger than the atoms from which they
• Acid: A substance that accepts an electron pair
are derived. For anions, nuclear charge is unchanged
(electrophile).
but the added electron(s) introduce new repulsions and
the electron clouds swell. • Base: A substance that donates an electron pair
(nucleophile).
• Among the halide ions, I– has the largest atomic radius,
and F– has the smallest atomic radius. • In a Lewis acid-base reaction, an base donates an
• Thus, HI is the strongest acid because the negative electron pair to an acid to form a bond.
charge on iodide ion is delocalized over a larger volume • All Brønsted-Lowry acid-base reactions are Lewis
than the negative charge on chloride, etc. acid-base reactions (not vice versa).
• A larger electron cloud has weaker bond overlap with
hydrogen’s 1s orbital.

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 • Curved arrow notation
• To show the flow of electrons in a Lewis acid-base H O + H Cl H O H + Cl
reaction, we regularly use “curved arrows”. H H
• The proper use of curved arrows allows us to see the Hydronium ion
bond breaking and bond making in a chemical
reaction more easily. CH3 O + H Cl CH3 O H + Cl
- + H H
A + :B A B new covalent bond Methan ol An oxoniu m
Lewis Lewis formed in this Lewis ion
acid acid-base reaction
base • Note that in both examples, the first arrow illustrates
• A “curved arrow” will always start at a source of the formation of a new bond.
electrons, a lone pair or a covalent bond. • The second arrow illustrates the electrons in a covalent
• A “curved arrow” will end on an atom (to show a lone bond moving to become a lone pair on chlorine atom.
pair or the formation of single bond) or between atoms (These arrows are not drawn very well! They should
(to show the formation of double or triple bond). better point to the chlorine atom.)

• Lewis acid-base definitions mean that an acid-base • Note that the curved arrows illustrating electron
reaction does not need to involve water (or transfer help show bond breaking and bond
hydrogen!). formation.

bromine uses a lon e

pair of electrons to form
a new b on d to carbon

+ Br
CH3 -CH-CH3 + Br CH3 -CH-CH3
An organic cation Bromide ion 2-Bromobutan e
(a Lewis acid) (a Lewis bas e)

• Examples of stronger Lewis acids B. Carbocations: CH3+, (CH3)3C+, etc.

A. Neutral compounds containing group III elements: • Similar to the group III elements involved in three
BF3, BH3, AlCl3 covalent bonds, carbocations also have an empty p-
orbital.
• Group III elements cannot have a filled octet without • Since they are in group IV, having just three bonds
having a formal charge of –1. (Not likely for an (and no lone pair electrons) results in a formal charge
electropositive element.) of +1 on the carbon (in addition to the empty orbital).
• Thus, neutral boron and aluminum compounds have an • Thus, these are very strong electrophiles that often
empty p-orbital that can accept a pair of electrons. cannot be isolated, but instead are reactive
intermediates.
Empty p-orbital
H
Empty p-orbital
B H H
H
C
+ H
H

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C. Sources of H+, i.e. strong acids: H2SO4, HCl, HBr, etc. D. Electronegative atoms sharing electrons:

• A proton, H+, is a hydrogen atom with an empty 1s orbital • O3 (ozone);

and a formal positive charge. Therefore, it is a strong Lewis • elemental forms of the halogens F2, Cl2, Br2, I2;
acid. • compounds containing O-O single bonds, e.g., peroxides.
• In solution, an uncomplexed proton rarely exists. Instead, it
is bound to some other element (often the solvent).
• Nonetheless, we can consider strong acids as sources of H+. +
- O
O O H-O-O-H
ozone hydrogen peroxide

• Examples of weaker Lewis acids B. Carbons bonded to electronegative atoms

A. Transition metal cations: Zn2+, Hg2+
• Examples include CH3Br, H2C=O
• Since transition metals cations are larger than second • A carbon bonded to an electronegative atom will
row cations, their formal charge is spread over a larger have a  (partial) positive charge.
area. • This carbon is referred to as an electrophilic carbon
• These are often referred to as “soft” electrophiles or since it is electron deficient.
“soft” Lewis acids. • Electrophilic carbons can react with nucleophiles
• “Hard” electrophiles have a positive charge (Lewis bases) in substitution or addition reactions.
concentrated in a small area, e.g. H+, CH3CH2+. H H
_ _
+
• Soft electrophiles will often complex to a lone pair of HO H C Br -
HO C H + Br
substitution
electrons located on a Lewis base. H H
2+ Lewis base Lewis acid
H H Zn
H C O H H C O H _ -
O
Zn2+ _ O
H H HO C H H C H
H + addition
Lewis base Lewis acid Lewis acid-base complex OH
Lewis base Lewis acid

• Examples of Lewis bases B. Weaker Lewis Bases

• Compounds that contain  bonds can act as Lewis

A. Stronger to Moderate Lewis Bases
bases,
• Donation of a pair of  electrons results in the loss of an
• Generally, the same structural features that make a
octet for one of the atoms involved in the double bond.
strong Brønsted base also lead to making a strong
• Thus, the -electrons are not donated as readily as lone
Lewis base.
pair electrons.
• In general, an atom will be more willing to donate a pair
of electron if:
a) the lone pair electrons are on a atom of low
electronegativity, and/or
b) the lone pair electrons are close to the nuclei, i.e. a
small atom, where the charge is more concentrated.
_ _ _
R S R O H C H
H

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• More examples of Lewis bases

Halid e Water, alcohols, Ammonia Hyd roxide an d A mid e

ions and ethers and A min es alkoxide ions ions
Cl H O H H N H H O H N
H H
Br CH 3 -O-H CH 3 -O
CH3 N H CH3 N
I CH 3 -O-CH3 H H

CH3 N H CH3 N
CH3 CH3

Very w eak Weak Strong Stronger Very Strong