SW - 8 Acidity and Basicity of Organic Compounds

BrnstedLowry Acids and Bases Lewis Acids and Bases Acidity constant Ka and pKa Acid strength - resonance - inductive effect - electronegativity - atomic size Organic acids and bases

Essential Organic Chemistry, Paula Bruice, Chapter 2

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BrnstedLowry Acids and Bases

An acid is a proton donor A base is a proton acceptor

HBr
acid

+ H2O
base

Br + H3O

NH3 + H2O base acid

NH4 + OH

Note that water can act as an acid or a base

H Br
acid

Br

O H H

base

conjugate base

conjugate acid

1st pair 2nd pair The remaining species after H+ has been donated is the conjugate base. The resulting species after H+ has been accepted is the conjugate acid. Every acid-base reaction involving proton transfer has 2 conjugate acid base-pairs.
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Lewis Acids and Bases A Lewis acid is an electron pair acceptor. A Lewis base is an electron pair donor.

F F B F + CH3CH2 O CH2CH3
F

F F
Electron rich Lewis base NH3 H2O Cl-

CH2CH3 CH2CH3

B O

Electron deficient Lewis acid e.g. Fe3+ AlCl3

Adduct

The Acidity Constant, Ka The strength of an acid is represented by its ionization constant (acidity constant), Ka

HA + H2O
Ka =
A
H 3O

A + H3O
HA

Since the Ka values for various acids have such a wide range, a more manageable way to discuss acidity is to use pKa

pKa = log (Ka)

Compare pKa and Ka Values

strong acids pKa

weak acids

-2 102

2 10-2

6 10-6

10 10-10

12

14 10-14

Ka

The smaller the value of the pKa the stronger the acid.
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Will the following reactions take place in the direction indicated?

(i)

HCN + CH3CO2 Na (9.2)

NaCN + CH3CO2H (4.72)

(ii)

CH3CH2OH + NaCN (16.0)

CH3CH2O + HCN (9.2)

pKa values given in brackets

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Acid Strength The difference between a strong acid and a weak acid can be described by the stability of the conjugate base. Compare 2 conjugate bases A1 and A2

E N E R G Y

A1A2

Higher energy a stronger conj.base from a weaker acid Lower energy a weaker conj. base from a stronger 8 acid

HA

ionization easier

Acid Strength explained An acid will give up its H+ readily if the conjugate base which forms upon acid dissociation can be stabilised. So consider structure of conjugate base of the acid to see if there are any factors that can stabilise it.

1. 2. 3. 4. 5.

Resonance Inductive effects Electronegativity Atomic Size Hybridization

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1.

Resonance Effects - influence the stability of the conjugate base Resonance stabilisation = extra stability a compound gains from having delocalised electrons. The greater the number of relatively stable resonance contributors, or the more stable the resonance contributors are, the greater is the resonance stabilization. Resonance results in the electrons and the charge being dispersed. A stable base is a weak base and will not share its electrons readily.
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Example 1 Explain using appropriate equations & resonance structures, why ethanoic acid (pKa=4.72) is a stronger acid than ethanol (pKa = 16.00).

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O H3C C O H

H2O
H3C C

O O

O H3C C O

acetate ion acetic acid

H3O+
The ethanoate ion has 2 resonance stabilized equivalent structures (charges on different oxygens).
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Example 2 Explain using appropriate equations and resonance structures, why phenol (pKa =10) is a stronger acid than cyclohexanol (pKa = +/- 17).

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The phenolate ion can be resonance stabilized.

More resonance structures, but not more stable than acetate. Non-equivalent structures (note charges on carbon and oxygen).
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2. The Inductive effect - influences the stability of the conjugate base The Inductive effect is a permanent polarisation which results from electronegativity differences between 2 bonding atoms. - electronegative elements,F, Cl, Br, O, N, pull electron density away from C. Cl helps to stabilize carboxylate anion by withdrawing electrons from the carbonyl carbon. This makes the carbonyl carbon slightly positive which stabilizes the ve charge.
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Cl

+ C

Cl

+O C O

Inductive effect diminishes with distance - it extends for about 3 bonds

+ + + Cl C C C

O O

Remember, the inductive effect works through the bond system, while the resonance effect works through the pi system.
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Example 3 Explain using appropriate equations & resonance structures, why 2-chloroacetic acid (pKa =2.85) is a stronger acid than acetic acid (pKa =4.72).

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3.

Electronegativity influences the stability of the conjugate base The following slide shows 3 sets of molecules. Each set consists of an analogous class of molecules, differing in elements in period 2. Consider the conjugate base of each molecule. The conjugate base will have a ve charge. Placing the -ve charge on a more electronegative element (from the same period) in the conjugate base leads to a stronger acid. Why?

(i)

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increasing electronegativity IV Set 1 V VI VII

CH4
>45

NH3
34

H2O
16

HF
3.5

Set 2

RCH3
45

RNH2
35

ROH
18

O
Set 3

O RCNH2
15

O RCOH
5

RCCH3
20

pKa values given for each molecule

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4.

Atomic Size Placing the ve charge on a larger atom (same group) in the conj base leads to a stronger acid.

Increasing size

pKa

con base

ionic radii

HF HCl HBr HI

3.5 -7 -9 -10

FClBrI-

1.36 1.81 -1.95 -2.16

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Organic Bases

Basicity of amines: General reaction of amines with acids: N amine + H A acid N H + salt A

Bases are characterized by their Kb or pKb values: (Note that pKa + pKb = pKw = 14) RNH2 + H2O RNH3 + OH
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Kb

[R =
Base

H 3 [ OH ] [R H 2 ]
+

pKb = log Kb

stronger base [RNH2] smaller Kb larger pKb smaller weaker base [RNH2] larger Kb smaller pKb larger
pKb 3.06 3.21 3.25 3.36 4.74 stronger base

(CH3CH2)2NH (CH3CH2)3N CH3CH2NH2 CH3NH2 NH3

NH2
O H3C C

9.37

14.5

NH2

weaker base
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Why is aniline a weak base?

Consider resonance forms of aniline:

NH2

NH2

NH2

NH2

The non-bonding electron pair on N can be delocalized into the ring as shown above. This means the electron pair is less available to be donated to a proton.
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Why is ethanamide a very weak base?

In ethanamide (acetamide) the nitrogen is adjacent to an electron withdrawing carbonyl group. The non-bonding pair of electrons on the nitrogen can be delocalized towards the carbonyl pi system and are therefore not available for donation to an acid.

O C H3C NH2 H3C

O C NH2

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