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C
Chhaapptteerr 22:: A
Acciiddss aanndd B
Baasseess
AA ccoom
mppaarriissoonn ooff B
BrrnnsstteeddLLoow
wrryy aanndd LLeew
wiiss aacciiddss aanndd bbaasseess
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
CH3 CH3
Example CH3 C + Br CH3 C Br
CH3 CH3
Lewis acid Lewis base
electrophile nucleophile
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).
[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
CH3CH3 CH2=CH2 H C C H
ethane ethylene acetylene
pKa = 50 pKa = 44 pKa = 25
increasing acidity