Acid-Base Reactions

Volhardt: 2-1, 2-2, 8-3, 9-1, 13-2, 19-4

Read section 2-1 not covered in notes

Bronsted-Lowry acid substance that can donate a hydrogen ion (H+) Bronsted-Lowry base substance that can accept a hydrogen ion (H+)

CH3COOH
acid

+ OH
base

CH3COO
conjugate base

H2O
conjugate acid

Lewis acid substance that can accept a pair of electrons

Lewis base substance that can donate a pair of electrons

FeBr3 + Br2 Lewis acid Lewis base FeBr4 Lewis base + Br + Lewis acid

Acid-base movie
Sec.4 - Acid-base 1

pH = -log[H+]

Review

pOH = -log[OH]

Brnsted-Lowry acids and bases

kw = [H+][OH] = 1 x 10-14 pH + pOH = 14 neutral solution [H+] = [ OH] = 1 x 10-7 pH = 7 acidic solution [H+] > 1 x 10-7 pH range 0 to 7 basic solution [H+] < 1 x 10-7 pH range 7 to 14

General formula for an acid HA; for a base B HA ka = [H+][A] [HA] taking the log of both sides Henderson-Hasselbalch equations pH = pka + log[A] [HA] pOH = pkb + log[B+H] [B] H+ + A B + H2O B+H + OH kb = [OH][B+H] [B]

strong acid [H+] , ka , pka weak acid [H+] , ka , pka

strong base [OH] , kb , pkb weak base [OH] , kb , pkb

ka x kb = kw =1 x 10-14 pka + pkb = 14 Sec.4 - Acid-base 2

relationship between conjugate acid base pairs

Lewis Acids and Bases

Makes you think about the electrons and how bonds are formed arrow show bond breaking arrow show bond formation

gained two electrons and becomes negatively charged

new bond

Sec.4 - Acid-base

Opposite Charges Attract and React

BF3 has substantial positive charge on the boron
NH3 has substantial negative charge localized at the lone pair

-ve goes to +ve

Sec.4 - Acid-base

The base donates its electrons that occupy the HOMO to the LUMO of the acid to produce a new sigma bond

BF3 is hybridized The LUMO (Lowest Unoccupied Molecular Orbital) is shown to the right. Most of the volume of the LUMO corresponds to the empty p orbital

sp2

NH3 is sp3 hybridized. The HOMO (Highest Occupied Molecular Orbital) is shown to the left and is where the nonbonding lone pair resides.

The van der Waals surface electron density is indicated by the mesh

Sec.4 - Acid-base

The first step to organic reactions is understanding acids and bases

Why do acids have different acidities? What makes a strong acid a strong acid? An acid is strong if its conjugate base is stable. If the base is not stable it is reactive and will react with a proton and shift the equilibrium to the left in the following equilibrium.

HA

A + H+

Acidity increases with increasing anion stability

Hence the strength of an acid is inversely related to the strength of its conjugate base. What makes the base stable? You must look at the structure of the molecule. What is the hybridization of the atom? Is the charge on an electronegative atom? Is the electronegative atom large so that the charge is spread over a larger area? Can the charge be delocalized throughout the molecule? All of these must be considered

Sec.4 - Acid-base

1. What atom is the charge on?

Acidity increases with increasing anion stability

HA

A + H+

The more electronegative an atom, the greater its ability to carry a negative charge. Remember, electronegativity is the measure of an elements affinity for an electron or its ability to accept an electron. 1. (CH3)3C-H 2. (CH3)2N-H 3. CH3O-H 4. H-F

(CH3)3C + H+

(CH3)2N + H+

CH3O + H+

F + H+

increasing electronegativity of the underlined atom; increasing acid strength increasing stability of anion shifts equilibrium to products
A) B) C) D) 1>2>3>4 4>3>2>1 4>2>3>1 1>4>3>2
B 2.0 Al 1.5 Ga 1.8 C 2.5 Si 1.8 Ge 2.0 N 3.0 P 2.1 As 2.2 O 3.5 S 2.5 Se 2.6 Te 2.1 F 4.0 Cl 3.0 Br 2.8 I 2.5

B) HF > CH3OH > CH3)2NH > (CH3)2CH

Sec.4 - Acid-base

1. What atom is the charge on?

HA

A + H+

A larger anion can disperse the negative charge over a larger volume and thus increases the stability of the conjugate base which is more important than electronegativity when comparing elements down a column in the periodic table. 1.
conjugate base

H-F F

2. H-Cl Cl

3. H-Br Br

4. H-I I

increasing size of halogen increasing acid strength increasing stability of anion decreasing electronegativity of halogen
A) B) C) D) E) 1>2>3>4 4>2>1>3 4>2>3>1 1>4>3>2 4>3>2>1
B 2.0 Al 1.5 Ga 1.8 C 2.5 Si 1.8 Ge 2.0 N 3.0 P 2.1 As 2.2 O 3.5 S 2.5 Se 2.6 Te 2.1 F 4.0 Cl 3.0 Br 2.8 I 2.5

E) HI > HBr > HCl > HF

Thus use electronegativity when comparing atoms in the same row and size when comparing atoms in the same column
Sec.4 - Acid-base 8

Can also look at bond strength

The electrostatic potential maps show all the hydrohalic acids are polar. The variation in polarity is less significant than the bond strength which decreases from 567 kJ/mol for HF to 299 kJ/mol for HI.

For binary acids in the same group, HA bond strength decreases with increasing size of A, so acidity increases.

For binary acids in the same row, HA polarity increases with increasing electronegativity of A, so acidity increases
Sec.4 - Acid-base 9

Which of the hydrogens shown in the following molecule would be most acidic? H 1) O A) 1 B) 2
N 2) H

B 2.0 Al 1.5 Ga 1.8

C 2.5 Si 1.8 Ge 2.0

N 3.0 P 2.1 As 2.2

O 3.5 S 2.5 Se 2.6 Te 2.1

F 4.0 Cl 3.0 Br 2.8 I 2.5

Order the following compounds in decreasing acidity. (most acid to least acidic) 1) CH3OH 2) CH3SH 3) CH3CH3

A) B) C) D) E)

1>2>3 3>2>1 2>3>1 2>1>3 1 > 3 >2

Sec.4 - Acid-base 10

2. The proximity of an electronegative atom to an acidic atom can help stabilize the conjugate base. (Induction) HA A + H+
Inductive effects: Electronegative atoms pull electron density through the sigma bond from adjacent carbons making the carbon more positive. If the carbon is close to the anion this carbon can then pull electron density from the region that has the negative charge to make it more stable.
O Cl OH OH OH Cl O Cl O O

OH

pka

4.83

4.52

4.05 increasing acidity increasing anion stability

2.86

H3COH pka 15.5

ClCH2CH2OH 14.3 increasing acidity increasing anion stability

F3CCH2OH 12.4

Sec.4 - Acid-base

11

2. The proximity of an electronegative atom to an acidic atom can help stabilize the conjugate base. (Induction)

HA

A + H+

A) B) C) D)

1>2>3>4 4>2>1>3 4>2>3>1 2>4>3>1

Sec.4 - Acid-base

12

d-

Cl Cl

O
d+

d- Cl d+ d- Cl

d- Cl

-1

ddThe chlorines make the adjacent carbons electron poor. The carbon can then pull electron density from the region that has the negative charge, and this effect will stabilize the negative charge How about these hydrogens Do the electronegative atoms help stabilize the conjugate base

Cl

This is destabilizing. The lone pairs on the electronegative atom and the lone pair on the carbon repel each other.

d- O

+ H+

These protons are not very acidic

H F

Take out

d-

+ H+
13

Sec.4 - Acid-base

What effect do alkyl groups

Which compound is more acidic?
H3 C C H3 C C OH O H3C C H3C C O O
+ H+

CH3
O

CH3
O

+ H+
O

more acidic

H3C

C OH

H3C

more stable conjugate base

hyperconjugation through C-H sigma bond. This is not resonance. We will talk more about this later.

H
sp3

O C C sp2 O

sp2

sp2

only one C-H s bond shown

Resonance
14

Sec.4 - Acid-base

Order the following acids from most acidic to least acidic?

A) B) C) D) E) 1>2>3>4 4>2>3>1 2>3>1>4 3>2>1>4 1>4>2>3

Alkyl and aryl groups are electron donating through hyperconjugation or inductive effects which makes the anion A) less stable. B) more stable

hyperconjugation through C-H sigma bond.

H
C H H

H C

O H

C
H H H
15

Sec.4 - Acid-base

Which of the hydrogens shown in the following molecule would be most acidic? 1) HO F A) 1 B) 2

B 2.0 Al 1.5 Ga 1.8

C 2.5 Si 1.8 Ge 2.0

N 3.0 P 2.1 As 2.2

O 3.5 S 2.5 Se 2.6 Te 2.1

F 4.0 Cl 3.0 Br 2.8 I 2.5

2) HO

Which of the hydrogens shown in the following molecule would be most acidic?
1)

H N
2)

A) 1 B) 2

NH2

Sec.4 - Acid-base

16

3. Resonance Stabilization
List the following compounds in order of decreasing acidity (Most acidic to least acidic) 1) 2) 3)
A) B) C) D) 1>2>3 1>3>2 3>2>1 2>3>1

Two resonance structures with the negative charge on two electronegative atoms (oxygen) is more stabilizing than 3 resonance structures with the negative charge on carbons.
Sec.4 - Acid-base

17

pKa = 15.5

CH3OH

CH3O + H+
O O O

C6H5OH
pKa = 9.92

+ H+

O
O

CH3CO2H
pKa = 4.74

H3C

H3C

+ H+

Phenol has more resonance structures than acetic acid but acetic acid is more acidic, why? Which atom is able to handle a negative charge better, carbon or oxygen? Oxygen can. Thus resonance onto two oxygens is more stabilizing than three carbons

Sec.4 - Acid-base

18

Which of the hydrogens shown in the following molecule would be most acidic?
H H 2)
H2N
1)

A) 1 B) 2

NH
2)

A) 1 B) 2
H 1)

N N H H

CH3

H H

CH3 H

CH3 H H
Sec.4 - Acid-base 19

H H

H 2)

A) 1 B) 2
H
1)

H 2)

O H

H H
1)

2)

H
1)

Sec.4 - Acid-base

20

4. Hybridization
Order the following compounds from strongest to weakest acid 1) (CH3)3CH 2) CH2=CH2 3) HCCH 4) NH3

1) (CH3)3C + H+ pka > 70

2) CH2=CH + H+ 44

3) HCC + H+ 26

4) NH2 + H+ 38

sp3 C

sp2 C

sp3 N

sp C

A) B) C) D) E)

1>2>3>4 4>3>2>1 2>3>1>4 3>4>2>1 1>4>2>3

The sp3 negatively charged nitrogen atom is a weaker base than a negatively charged sp3 carbon because it is more electronegative. It is also a weaker base than a sp2 carbon. However it is a stronger base than a sp hybridized carbanion because the sp hybridization of the carbanion has a greater stabilizing effectSec.4 - increasing electronegativity in this case. 21 than Acid-base

Which of the hydrogens shown in the following molecule would be most acidic? A) 1 B) 2
1)

H 2)

H H

Sec.4 - Acid-base

22

Order the following compounds from strongest to weakest acid

1)

Cl

OH

2)

OH

3) CH3SH

4) CH3OH

A) B) C) D)

1>2>3>4 4>3>2>1 4>2>3>1 1>4>3>2

Sec.4 - Acid-base

23

Bases Strength of Amines

The concept of base strength can become confusing when we look at a series of amines in which the base strength varies because of the relative stability of the free amine and its conjugate acid. R3N + H2O R3NH+ + HO conjugate base

Free amine (base) acid

conjugate acid

From the above equation we can see that anything that stabilizes the free amine (base) relative to the conjugate acid makes the base less basic (shifts the equilibrium to the left). Anything that stabilizes the conjugate acid makes the base more basic and will shift the equilibrium to the right. Remember that amines are weak bases; there are many other stronger bases for example RO is a much stronger base.

Sec.4 - Acid-base

24

Order the following compounds from strongest to weakest base

pKb = 9.85

pKb = 13

pKb = 9.37

pKb = 3.3 A) B) C) D) 1>2>3>4 4>3>1>2 4>2>3>1 1>4>3>2

Sec.4 - Acid-base

25

Order the bases from strongest to weakest.

O NH2 1 2 NH2 N H 3 4 NH 5 Cl NH2

A) B) C) D) E)

4>3>2>5>1 1>3>2>5>4 3>2>5>1>4 2>3>1>4>5 5>3>2>4>3

Sec.4 - Acid-base

26

Amides
O
pkb = 13.37

O C NH2 H3C
+

O dC H3C
d+

C H3C
H+ d- O

NH2

NH2

Very weak bases because of resonance onto electronegative oxygen atom. Destabilizing

H3C

d+ C

NH3

In fact the oxygen is protonated with a strong acid not the nitrogen
H O H3 C C NH2

H O H3 C C NH
pka = 0.6
27

resonance stabilized

Sec.4 - Acid-base

Order the bases from strongest to weakest

d+
1)

d-

Cl

d+

A) B) C) D)

1>2>3>4 4>3>2>1 4>2>3>1 1>4>3>2

N H
H2O

d2)

O
d+

N H
H2O d+

3)

4)

H2O

dCl

H2O d+

H N H

H N H
+ HO

d- O

H
+ HO

+ HO

d+ + HO Destabilizing

Destabilizing

pkb = 2.88

pkb = 5.67

pkb = 8.75

pkb = 11.45

Sec.4 - Acid-base

28

Predict which way the equilibrium is shifted in the following reactions. Also show the flow of electrons in the acid-base reaction
H H
+ HO CH3CH2O +

A) Left B) Right

CH3CH2O

O H

O O
A) Left B) Right

O O
+

O H

H O

A) Left B) Right

H3CH2C HC C H
+

H3CH2C N HC C
+

N H3CH2C

H3CH2C

O
A) Left B) Right

O H + CH3CH2 H
Sec.4 - Acid-base 29
+ CH3CH3

H3C

C H

Predict which way the equilibrium is shifted in the following reactions. Also show the flow of electrons in the acid-base reaction
O Cl3C
A) Left B) Right

H
+

O H3C CH3 Cl3C

O
+

OH CCl3 H3C CH3

CCl3

O H O
A) Left B) Right
+

S S

O O
+

S SH

O H
A) Left B) Right

O O
+

O O O
+

O H3C S O OH

H3C

S O

Sec.4 - Acid-base

30

If one equivalence of NaOH is added to a solution containing the compound which proton would predominately be removed?
1)

OH
3)

Cl

OH

Cl OH
2)

A) 1 B) 2 C) 3

If one equivalence of LiCH3 is added to a solution containing the compound which proton would predominately be removed?

H N
1)

2)

Sec.4 - Acid-base

31

Order the bases from strongest to weakest.

H N NH2 N
A) B) C) D) 1>2>3 1>3>2 3>2>1 2>3>1

Sec.4 - Acid-base

32

H N

NH2

Strongest base

A)

B)

Strongest base

NH2

A)

B)

H N H3C C C

Strongest base
1) 2)

3)

A) B) C) D)

1>2>3 1>3>2 3>2>1 2>1>3

Strongest base

A) CH3CH2OH

B) CH3CH2O

Strongest acid

A) CH3CH2OH

B) CH3CH2OH2
Sec.4 - Acid-base 33

Strongest to weakest base. 1) CH3ONa 2) CH3SNa 3)CH3OH

A) B) C) D)

1>2>3 1>3>2 3>2>1 2>1>3

Strongest to weakest acid. 1) CH3SH 2) HI 3) CH3NH2

A) B) C) D)

1>2>3 1>3>2 3>2>1 2>1>3

Strongest to weakest acid.

1) H2SO4

2) C6H5OH

3) CH3CO2H

A) B) C) D)

1>2>3 1>3>2 3>2>1 2>1>3

Sec.4 - Acid-base

34

We are always looking at an equilibrium and which way it is shifted in a specific environment

G -RT lnKeq
G = -ve value the reaction favors the formation of products and if smaller than 13 kJ mol-1 the is said to go to completion (>99% converted) G = +ve value the reaction favors the reactants and the formation of products is unfavorable.

HA

A + H+

G = H - TS
Exothermic reaction H is -ve Endothermic reaction H is +ve S is +ve - Change from a more ordered system to less a ordered system S is -ve - Change from a less ordered system to a more ordered system Sec.4 - Acid-base We will come back to this when we look at reactions 35