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Acids and Bases 2–1

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CCh

C

2

A

nnd

a

dd BBa aas sse ees ss

B

♦♦ AA cco

A c

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oom

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B

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L

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a

nnd

a

b

dd bba aas sse ees ss

Type

Definition

Structural feature

Examples

Brønsted–Lowry acid

(2.1)

Brønsted–Lowry base

(2.1)

proton donor

proton acceptor

a proton

a lone pair or a π bond

HCl, H 2 SO 4 , H 2 O, CH 3 COOH, TsOH

OH, OCH 3 , H , NH 2 , CH 2 =CH 2

Lewis acid (2.8)

electron pair

a

proton, or an unfilled

BF 3 , AlCl 3 , HCl,

acceptor

valence shell, or a partial (+) charge

CH 3 COOH, H 2 O

Lewis base (2.8)

electron pair

a

lone pair or a π bond

OH, OCH 3 , H , NH 2 ,

donor

CH 2 =CH 2

♦♦ AAc cci iid dd––b bba aas sse ee rre eea aac cct tti iio oon nns ss

A

r

[1] A Brønsted–Lowry acid donates a proton to a Brønsted–Lowry base (2.2).

Example

H

a proton to a Brønsted–Lowry base (2.2). Example H H + O HNH H O H

H

+

O
O

HNH

H O
H
O

H

+ HNH

acid

proton donor

base

proton acceptor

conjugate base

conjugate acid

[2] A Lewis base donates an electron pair to a Lewis acid (2.8).

Example

CH 3 CH 3 C + Br CH 3 Lewis acid Lewis base electrophile nucleophile
CH 3
CH 3
C
+ Br
CH 3
Lewis acid
Lewis base
electrophile
nucleophile

CH 3

CH 3 C Br CH 3
CH 3
C
Br
CH 3

Electron rich species react with electron poor ones.

Nucleophiles react with electrophiles.

♦♦ IIm

oor rrt tta aan nnt tt ffa aac cct tts ss

I

mmp

ppo

f

Definition: p K a = −−−−logK a . The lower the pK a , the stronger the acid (2.3).

NH 3 p K a = 38

versus

H 2 O p K a = 15.7 lower pK a = stronger acid

Chapter 2–2

The stronger the acid, the weaker the conjugate base (2.3).

increasing p K a

the weaker the conjugate base (2.3). increasing p K a CH 2 CH 2 CH 3

CH 2

CH 2

CH 3 COOH

HCl

p K a = 44

p K a = 4.8

p K a = –7

COOH HCl p K a = 44 p K a = 4.8 p K a =

increasing acidity

increasing pK a of the conjugate acid Cl CH 3 COO CH CH 2
increasing pK a of the conjugate acid
Cl
CH
3 COO
CH
CH
2
pK a of the conjugate acid Cl CH 3 COO CH CH 2 increasing basicity •

increasing basicity

In proton transfer reactions, equilibrium favors the weaker acid and weaker base (2.4).

H C C H + NH 2 HCC pK a = 25 stronger acid unequal
H
C
C
H
+ NH 2
HCC
pK a = 25
stronger acid
unequal equilibrium arrows

+

NH 3

pK a = 38 weaker acid

Equilibrium favors the products.
Equilibrium favors the products.

Equilibrium favors the products.

Equilibrium favors the products.

An acid can be deprotonated by the conjugate base of any acid having a higher p K a (2.4).

Acid

p K a

Conjugate base

CH 3 COO–H

4.8

CH 3 COO

CH 3 CH 2 O–H

16

CH 3 CH 2 O

These bases

HCCH

25

HCC

can deprotonate

H–H

35

H

CH 3 COO–H.

higher pK a than CH 3 COO–H

 

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F

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5

[1] Element effects (2.5A)

The acidity of HA increases both across a row and down a column of the periodic table.

C
C

H

N
N

H

OH

HF

increasing electronegativity

periodic table. C H N H OH HF increasing electronegativity increasing acidity H F H Cl

increasing acidity

H

F

H

Cl

H

Br

H

I

increasing size

H OH HF increasing electronegativity increasing acidity H F H Cl H Br H I increasing

increasing acidity

Acids and Bases 2–3

[2] Inductive effects (2.5B)

The acidity of HA increases with the presence of electron withdrawing groups in A.

CH 3 CH 2 OH

weaker acid

CF 3 CH 2 OH

stronger acid

CH 3 CH 2 O

No additional electronegative atoms stabilize the conjugate base.

F

δ -

H

δ - δ + F C C
δ -
δ +
F
C
C

F δ

-

H

O

CF 3 withdraws electron density, stabilizing the conjugate base.

[3] Resonance effects (2.5C)

The acidity of HA increases when the conjugate base A: is resonance-stabilized.

CH 3 CH 2 O H CH 3 CH 2 O ethanol ethoxide conjugate base
CH 3 CH 2 O
H
CH 3 CH 2 O
ethanol
ethoxide
conjugate base

only one Lewis structure

O CH 3 C OH acetic acid
O
CH 3
C
OH
acetic acid

more acidic

CH 3

O O C CH 3 C O O acetate conjugate base
O
O
C
CH 3
C
O
O
acetate
conjugate base

two resonance structures

[4] Hybridization effects

(2.5D)

The acidity of HA increases as the percent s -character of the A: increases.

CH 3 CH 3

ethane

pK a = 50

CH 2 =CH 2

HCCH

ethylene

acetylene

pK a = 44

pK a = 25

CH 2 =CH 2 HCCH e t h y l e n e acetylene p K

increasing acidity