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ORGANIC CHEMISTRY
Chemistry 31 Second Sem 2009-2010

Acid- Base Theories

1. Arrhenius Concept
classifies solutes according to their behavior in H 2O
solute which produces OHion when dissolved in H 2O example: NH3 + H2O
base

Acidity
and

solute which produces H3O+ ion when dissolved in H 2O example: HCl + H2O
acid

Basicity
UNIVERSITY OF THE PHILIPPINES MANILA Padre Faura, Ermita, Manila A.Y. 2009 2010, Second Semester Ms. Anjelyn del Rosario
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H3O+ + Cl-

NH4+ + OH-

H2SO4 (aq) + H2O(l) HSO4- (aq) + H3O+(aq) HSO4- (aq) + H2O(l) SO42- (aq) + H3O+(aq)

+ KOH(aq) (aq) + K (aq) CO32- (aq) + H2O(l) OH- (aq)

OH-

+ HCO3- (aq)

HA (aq) + H2O(l) A- (aq) + H3O+(aq)

MOH (aq) M+ (aq) + OH-(aq)

Acid- Base Theories

2. Brnsted-Lowry Concept
based on the behavior of a substance during proton (H+) transfer; H+ (aq) + H2O(l) H3O+(aq)

Acid- Base Theories

2. Brnsted-Lowry Concept

a proton donor binary acids <H nX>, oxyacids <(HO)nXOm>, aquocomplexes of metal ions,

a proton acceptor chemical species that has an atom with an available electron for pairing

Proton donors and acceptors. H+ or H3O+ = a proton

Acid- Base Theories

2. Brnsted-Lowry Concept
Conjugate acid-base pair
a pair of substances that are related through the loss or gain of a proton; in any acid-base reaction we can identify two sets of conjugate acid-base pairs.

Acid- Base Theories

Explanation of Acid Strength
1. Positivity of H: The more positive H is, the more acidic it is, the higher the acid strength. RCOOH > H-O-H > R-O-H 2. Stability of the conjugate base: the more stable the resulting conjugate base, the more willing the acid is to donate its proton, the higher the acid strength RCOOH > phenol > HOH > ROH

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ACID and BASE strength

Structural Effects on Acidity and Basicity In the Bronsted-Lowry Concept: ACID strength proton-donating ability BASE strength proton-accepting ability Factors Affecting Acidity and Basicity 1. Direction of polarity of H-X bond 2. Strength of the H-X bond 3. Stability of the conjugate base 4. Type of solvent
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Factors Affecting Acidity and Basicity

1. Direction of polarity of H-X bond The H in an H-X bond should be partially positive. The more polar the bond, the stronger the acid. 2. Strength of the H-X bond Stronger bonds are less easily dissociated than weaker bonds. 3. Stability of the conjugate base In general, the more stable the conjugate base, the stronger the acid.
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ACID strength
3. Stability of the conjugate base
Anything that stabilizes a conjugate base A: makes the starting acid HA more acidic.

ACID strength
3. Stability of the conjugate base
No matter which of these factors is discussed, to compare the acidity of any two acids:
o Always look at the conjugate bases. o Determine which conjugate base is more stable. o The more stable the conjugate base, the more acidic the acid. The strengths of a conjugate acid and its conjugate base are inversely related. A strong conjugate base has a weak conjugate acid. A weak conjugate base has a strong conjugate acid.
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Four other factors affect the acidity of HA. These are:

Element effects (trends in periodic table) Inductive effects (electronegativity) Resonance effects (multiple resonance structures) Hybridization effects (sp, sp2, sp3)

Factors that determine ACID strength

Element EffectsTrends in the Periodic Table.
Across a row of the periodic table, the acidity of HA increases as the electronegativity of A increases.

Factors that determine ACID strength

Element EffectsTrends in the Periodic Table.
Positive or negative charge is stabilized when it is spread over a larger volume.

Down a column of the periodic table, the acidity of HA increases as the size of A increases.

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Size, and not electronegativity, determines acidity down a column. The acidity of HA increases both left-to-right across a row and down a column of the periodic table. Although four factors determine the overall acidity of a particular hydrogen atom, element effectsthe identity of Ais the single 12 most important factor in determining the acidity of the HA bond.

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Factors that determine ACID strength

Inductive Effects
An inductive effect is the pull of electron density through bonds caused by electronegativity differences between atoms. In the example below, when we compare the acidities of ethanol and 2,2,2-trifluoroethanol, we note that the latter is more acidic than the former.

Factors that determine ACID strength

Inductive Effects
The reason for the increased acidity of 2,2,2trifluoroethanol is that the three electronegative fluorine atoms stabilize the negatively charged conjugate base. This effect is limited to a three bond distance.

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Factors that determine ACID strength

Resonance Effects
Electron delocalization Resonance structures Individual Lewis structures in cases where two or more Lewis structures are equally good descriptions of a single molecule. ethanol vs. acetic acid

Factors that determine ACID strength

Resonance Effects
When the conjugate bases of the two species are compared, it is evident that the conjugate base of acetic acid enjoys resonance stabilization, whereas that of ethanol does not.

Resonance delocalization makes CH 3COO more stable than CH3CH2O, so CH3COOH is a stronger acid than CH 3CH2OH.

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Factors that determine ACID strength

Hybridization Effects
The final factor affecting the acidity of HA is the hybridization. Let us consider the relative acidities of three different compounds containing CH bonds.

Factors that determine ACID strength

Hybridization Effects

Figure. Electrostatic Potential plots

The higher the percent of s-character of the hybrid orbital, the closer the lone pair is held to the nucleus, and the more stable the conjugate base.
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Factors that determine ACID strength

Summary of the factors that determine acidity

Factors that determine ACID strength

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Factors that determine ACID strength

Exercise: For each of the following compounds, indicate which is the stronger acid: Exercise:

Factors that determine ACID strength

For each of the following compounds, indicate which is the stronger base:

Hard acids and bases have low polarizability. Their orbitals do not change their shapes, so the interaction is mostly driven by electrostatic forces. Soft acids and bases have high polarizability. Their orbitals change their shapes and drive the interaction.

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Aromaticity and acidity

Compound
A Benzoic Acid o-methylbenzoic Acid o-chlorobenzoic acid

acidity
pKa1
4.20 3.91 2.94

pKa2

Struct. Effects

o-tertbutylbenzoic acid
o-nitrobenenzoic acid B O-hydroxybenzoic acid 2,6-dihydroxybenzoic acid C Pthalic Acid Isophthalic Acid

3.46
2.17 2.98 2.30 2.98 3.46 5.28 4.46

STERIC and POLAR

Intramolecular H-Bond

H-bond and Polar

Terephthalic Acid

3.51

4.82

acidity
Compound
Compound
D p-methoxybenzoic acid p-cyanobenzoic acid p-methylbenzoic acid p-nitrobenzoic acid 4.47 3.55 4.34 3.44 Electron delocalization

acidity
Ka
1 .0 x 10-18 1.2 x 10-10 6.8 x 10-8 pKa2 Structural Effects Ethanol Phenol o-nitrophenol

pKa1

m-nitrophenol
p-nitrophenol 2,6-dinitrophenol 2,4-dintrophenol 2-nitroresorcinol 4-nitroresorcinol

5.0 x 10-9
7.0 x 10-8 1.0 x 10-4 5.6 x 10-4 1.59 x 10-6 1.04 x 10-6

Basicity
Strength of Organic Bases when Acid is a Proton Compound
Ammonia Methylamine Dimethylamine Trimethylamine Ethylamine Diethylamine Aniline N-methyl aniline

pKb
4.75 3.36 3.23 4.20

Compound
o-methylaniline m-methylaniline p-methylaniline

pKb
9.62 9.33 9.00

o-nitroaniline
3.33 3.07 9.38 9.60 p-methoxyaniline p-hydroxyaniline triethylamine m-nitroaniline p-nitroaniline

14.28
11.55 13.02 8.71 8.50 3.42