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Acids and Bases 21

C
Chhaapptteerr 22:: A
Acciiddss aanndd B
Baasseess

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mppaarriissoonn ooff B
BrrnnsstteeddLLoow
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wiiss aacciiddss aanndd bbaasseess

Type Definition Structural feature Examples


BrnstedLowry acid proton donor a proton HCl, H2SO4, H2O,
(2.1) CH3COOH, TsOH
BrnstedLowry base proton acceptor a lone pair or a bond
OH, OCH3, H, NH2,
(2.1) CH2=CH2
Lewis acid (2.8) electron pair a proton, or an unfilled BF3, AlCl3, HCl,
acceptor valence shell, or a partial CH3COOH, H2O
(+) charge
Lewis base (2.8) electron pair a lone pair or a bond
OH, OCH3, H, NH2,
donor CH2=CH2

A Acciiddbbaassee rreeaaccttiioonnss
[1] A BrnstedLowry acid donates a proton to a BrnstedLowry base (2.2).
H
Example H O H + H N H H O + H N H

acid base conjugate base conjugate acid


proton donor proton acceptor

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

CH3 CH3
Example CH3 C + Br CH3 C Br
CH3 CH3
Lewis acid Lewis base
electrophile nucleophile

Electron rich species react with electron poor ones.


Nucleophiles react with electrophiles.

IIm
mppoorrttaanntt ffaaccttss
Definition: pKa = logKa. The lower the pKa, the stronger the acid (2.3).

NH3 versus H 2O
pKa = 38 pKa = 15.7
lower pKa = stronger
acid
Chapter 22

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

increasing pKa
increasing pKa of the conjugate acid
CH2 CH2 CH3COOH HCl
Cl CH3COO CH2 CH
pKa = 44 pKa = 4.8 pKa = 7
increasing basicity
increasing acidity

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

H C C H + NH2 H C C + NH3

pKa = 25 pKa = 38
stronger acid Equilibrium favors
weaker acid
the products.
unequal equilibrium arrows

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

Acid p Ka Conjugate base


CH3COOH 4.8 CH3COO
CH3CH2OH 16 CH3CH2O These bases
HCCH 25 HCC can deprotonate
HH 35 H CH3COOH.
higher pKa
than
CH3COOH

FFaaccttoorrss tthhaatt ddeetteerrm


miinnee aacciiddiittyy ((22..55))

[1] Element effects (2.5A) The acidity of HA increases both across a row and down a
column of the periodic table.
C H N H O H H F

increasing electronegativity
increasing acidity

H F H Cl H Br H I

increasing size
increasing acidity
Acids and Bases 23

[2] Inductive effects (2.5B) The acidity of HA increases with the presence of electron
withdrawing groups in A.

CH3CH2OH CH3CH2O
weaker acid No additional electronegative
atoms stabilize the conjugate base.

-
F H
- +
CF3CH2OH F C C O
stronger acid F - H

CF3 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.

CH3CH2O H CH3CH2O
ethanol ethoxide
conjugate base
only one Lewis structure

O O O
CH3 C CH3 C CH3 C
OH O O
acetate
acetic acid conjugate base
more acidic
two resonance structures

[4] Hybridization effects The acidity of HA increases as the percent s-character of


(2.5D) the A: increases.

CH3CH3 CH2=CH2 H C C H
ethane ethylene acetylene
pKa = 50 pKa = 44 pKa = 25

increasing acidity