Acids and Bases

Different Definitions of Acids and Bases

Arrhenius definitions for aqueous solutions. acid: a substance that produces H+ (H3O+) ions aqueous solution base: a substance that produces OH- ions in aqueous solution H+( aq) + H2 O( l) H3 O+( aq) Hydroniu m ion
Bronsted-Lowry definitions for aqueous and non-aqueous solutions. Conjugate acid base pair: molecules or ions interconverted by transfer of a proton. acid: transfers the proton. base: receives the proton.

Lewis Acids and Bases

Focuses on the electrons not the H+.

An acid receives electrons from the base making a new bond.

Acid electron receptor. Base electron donor.
acid
H O H H

H+
O H H

base

Types of electrons: lone pairs

Energy sigma bonding electrons

pi bonding electrons

Basicity

Acid Base Eqilibria

The position of the equilibrium is obtained by comparing the pKa values of the two acids. Equivalently, compare the pKb values of the two bases.

Acid Base Eqilibria

Same equilibrium with electron pushing (curved arrows).

Lone Pair acting as Base.

Note the change in formal charges. As reactant oxygen had complete ownership of lone pair. In product it is shared. Oxygen more positive by 1. Similarly, B has gained half of a bonding pair; more negative by 1.

An example: pi electrons as bases

Bronsted Lowry Base

Bronsted Lowry Acid

For the moment, just note that there are two possible carbocations formed. The carbocations are conjugate acids of the alkenes.

Sigma bonding electrons as bases. Much more unusual!!

A very, very electronegative F!! A very positive S!! The OH becomes very acidic because that would put a negative charge adjacent to the S.

Super acid

Trends for Relative Acid Strengths

Totally unionized in aqueous solution

Aqueous Solution

Totally ionized in aqueous solution.

Example
Recall
OH

CH3CH2OH

pKa = 9.95
Stronger acid H2O + PhOH
phenol, PhOH ethanol, EtOH

pKa = 15.9
Weaker acid H3O+ + EtO-

H3O+ + PhO-

H2O + EtOH

Ka = [H3O+][PhO-]/[PhOH] = 10-9.95

Ka = [H3O+][EtO-]/[EtOH] = 10-15.9

Ethanol, EtOH, is a weaker acid than phenol, PhOH. It follows that ethoxide, EtO-, is a stronger base than phenolate, PhO-. For reaction PhOH + EtOStronger base K= PhO- + EtOH where does equilibrium lie? Weaker base. 10-9.95 / 10-15.9 = 106.0

Query: What makes for strong (or weak) acids?

What affects acidity?

1. Electronegativity of the atom holding the negative charge. Increasing acidity.
CH3OH CH3NH2 CH3CH3 CH3O - + H+ CH3NH - + H+ CH3CH2- + H+

Increasing Increasing basicity electronegativity of of anion. atom bearing negative charge. Increasing stability of anion.

2. Size of the atom bearing the negative charge in the anion. Increasing acidity.
CH3OH CH3SH CH3O - + H+; pKa = 16 CH3S - + H+; pKa = 7.0

Increasing Increasingsize basicity of atom of anion. holding negative charge. Increasing stability of anion.

What affects acidity? - 2

3. Resonance stabilization, usually of the anion.
OH
O

phenol, PhOH

Increasing resonance basicity of stabilization. the anion. Increased anion stability.

CH3CH2O - + H+

Acidity

CH3CH2OH ethanol, EtOH

No resonance structures!!

Note that phenol itself enjoys resonance but charges are generated, costing energy, making the resonance less important. The more important resonance in the anion shifts the equilibrium to the right making phenol more acidic.

OH

OH

etc.

 Two different bases or two sites in the same molecule may compete to be protonated (be the base).
Acetic acid can be protonated at two sites.
H

An example: competitive Bases & Resonance

O
H
+

Pi bonding electrons converted to non-bonding. Non-bonding electrons converted to pi bonding.

H O

H+

acetic acid

H O

Which conjugate acid is favored?

H

The more stable one! Which is that? Recall resonance provides additional stability by moving pi or non-bonding electrons.

No valid resonance structures for this cation.

An example: competitive Bases & Resonance

Comments on the importance of the resonance structures. All atoms obey octet rule!
H O

H+

acetic acid

The carbon is electron deficient 6 electrons, not 8. Lesser importance

H

H O

All atoms obey octet rule!

O H

What affects acidity? - 3

4. Inductive and Electrostatic Stabilization.
H3CCH2O - + H+

Acidity.

H3CCH2OH

d+
F3CCH2OH

d+
F3CCH2O - + H+

Increasing anion Increasing anion stability. basicity.

Due to electronegativity of F small positive charges build up on C resulting in stabilization of the anion. Effect drops off with distance. EtOH pKa = 15.9

What affects acidity? - 4

Note. The NH2-. 5. Hybridization of the atom bearing the charge. H-A H+ + A:is more basic than the RCCsp3 sp2 sp ion. More s character, more stability, more electronegative, H-A more acidic, A:- less basic.

Know this order.

Increasing Basicity of A-

Increasing Acidity of HA

Example of hybridization Effect.

terminal alkyne

RCCH + LiCH2CH2CH2CH3 base acid RCCH + AgNO3 non-terminal alkyne RCCR + LiCH2CH2CH2CH3 RCCR + AgNO3 NR

HCH2CH2CH2CH3 + RCCLi

AgCCR (ppt)

No Reaction

What affects acidity? - 5

O H H

H O H

6. Stabilization of ions by solvents (solvation).

H O O R R

Solvation provides stabilization.

Comparison of alcohol acidities.

OH OH OH
O H

pKa = 15.9
ethanol

17
propan-2-ol

18

2-methylpropan-2-ol

Crowding inhibiting solvation (CH3)3CO -, crowded

Solvation, stability of anion, acidity

Example
Para nitrophenol is more acidic than phenol. Offer an explanation

OH

+ H

The lower lies further to the right.

OH

Why? Could be due to destabilization of the unionized form, A, or stabilization of the ionized form, B.
+ H

N O O O

N O

Examine the equilibrium for p-nitrophenol. How does the nitro group increase the acidity?
O
OH

+ H

Examine both sides of equilibrium. What does the nitro group do? First the unionized acid.

N
N O O

OH

OH

OH

OH

Note carefully that in these resonance structures charge is created: + on the O and in the ring or on an oxygen. This decreases the importance of the resonance. Structure D occurs only due to the nitro group. The stability it provides will slightly decrease acidity.

N O O O

N O O

N O O

N O

Resonance structures A, B and C are comparable to those in the phenol itself and thus would not be expected to affect acidity. But note the + to attraction here

Now look at the anion. What does the nitro group do? Remember we are interested to compare with the phenol phenolate equilibrium.
O
OH

+ H

N
N O O

In these resonance structures charge is not created. Thus these structures are important and increase acidity. They account for the acidity of all phenols. Structure D occurs only due to the nitro group. It increases acidity. The greater amount of significant resonance in the anion accounts for the nitro increasing the acidity.

N O O O

N O O

N O O

N O

Resonance structures A, B and C are comparable to those in the phenolate anion itself and thus would not be expected to affect acidity. But note the + to attraction here

Sample Problem

3. (3 pts) Which is the stronger base and why?

vs
HN HN O

H2N

H2N

H2N