Acid Strength and pKa

Acid strength is the tendency of an acid to donate a proton.

Acidity is measured by an equilibrium constant. When a

Brønsted–Lowry acid H–A is dissolved in water, an acid–base
reaction occurs, and an equilibrium constant Keq can be written
for the reaction.
 Equilibrio Químico

Inicio

bB-Y Equilibrio
cC
-

aA +
dD
+

Uz

[] E
R

R
&

4 -
st
v
vi Vz
=

It

de
Ley accion de masa
Eq.

Keq de E
=

Keq 1

Keq 1
Because the concentration of the solvent H2O is essentially
constant, the equation can be rearranged and a new equilibrium
constant, called the acidity constant, Ka, can be defined.

How is the magnitude of Ka related to acid

strength?
The stronger the acid, the further the equilibrium
lies to the right, and the larger the Ka.
Ácido Frete
H -
kaS77
-
-
8 A8ka
+

[]27]
=
=

ka2
Ácidos
débiles

For most organic compounds, Ka is small, typically 10-5

to 10–50. This contrasts with the Ka values for many
inorganic acids, which range from 100 to 1010. Because
dealing with exponents can be cumbersome, it is often
more convenient to use pKa values instead of Ka
values.
How does pKa relate to acid strength?
Understanding acid strength is the first step to understanding
base strength (and vice versa), because an inverse
relationship exists between acidity and basicity.

• A strong acid readily donates a proton, forming a weak

conjugate base.
• A strong base readily accepts a proton, forming a weak
conjugate acid.
Predicting the Outcome of Acid–Base Reactions

Equilibrium always favors formation of the

weaker acid and base.
A
-
D
B,
+
c +
 ix 10

+. He
*
H C C H C 28 iiH,
+

A B BC AC

pka=25 38
(AF) BF BD (AP)

13
IX10

L
&Hz H20 HC1+
AC
-

A B BC AC B A BC

50 15.7 16 -

7
Bi BF AF BC BI
AD AD AF

*)
5
X H ⑦ -
t H
xxx H2
+

-
H H

A B Viniluro (BC) (ACI

Eteniluro

pka=44 (BD) 35(AF)

AD BF
-
9
/X 10
How can we know if a particular base is strong enough to
deprotonate a given acid, so that the equilibrium lies to
the right? The pKa table readily gives us this information.

7 I BF BD AD
+ H
H
H H
-

t
15.7
25

25 15.7

H H H H
-

25 15.7
BD BF
AD A
F
An acid can be deprotonated by the conjugate base of any acid having
a higher pKa.
 O H2 35
0
11 Ic=c-

- H
- =
-
H25
Or
c,0 ->
HC1 -

7
pka =

4.8 ⑦
OH H20 15.7

CH300-CH3OH 15.5

HC0,0 -> HICOs 6.4 -

Factors That Determine Acid Strength
Acidez de una molecula (libera un Ht) depende de la
Estabilidad de la base
conjugadas

HCl (pKa < 0) is an extremely strong acid. Water (pKa = 15.7) is

moderate in acidity, and CH4 (pKa = 50) is an extremely weak
acid. How are these differences explained? There is one
general rule.

• Anything that stabilizes a conjugate base A: – makes the starting

acid H – A more acidic.
For now we will concentrate on how structural differences
between molecules can profoundly affect acidity.

Four factors affect the acidity of H–A:

[1] Element effects El átomo al que estáunido el H
[2] Inductive effects Presencia de átomos electronegativos
[3] Resonance effects
[4] Hybridization effects

No matter which factor is discussed, the same procedure is

always followed. To compare the acidity of any two acids:
• Always draw the conjugate bases.
• Determine which conjugate base is more stable.
• The more stable the conjugate base, the more acidic the
acid.
Element Effects—Trends in the Periodic Table

The most important factor

Comparing Elements in
determining the acidity of H–A is
the Same Row of the
the location of A in the periodic
Periodic Table
table.

⑳ ⑳
The enormity of this effect is evident by noting the
approximate pKa values for these bonds. A C–H bond is
approximately 1047 times less acidic than H–F.
Caso
hipotético

3
HF

H21

H Br
electronegatividad
It I
Comparing Elements Down a Column of the
Periodic Table

Now examine acidity trends down a column of the periodic table

by comparing H–F and H–Br.
Once again, first draw both conjugate bases and then determine
which is more stable.

There are two important differences between F– and Br-

electronegativity and size. In this case, size is more important than
electronegativity. The size of an atom or ion increases down a column
of the periodic table, so Br– is much larger than F–, and this stabilizes
the negative charge.
 HF Her

Positive or negative charge is stabilized when it is spread

over a larger volume.
 H20.
CGH106 +02 - -a +

>
*
do
t,
>FADHz
Inductive Effects

A second factor affecting the acidity of H-A is

the presence of electronegative atoms.
Efecto electrónico a través de enlaces + (electro negatividad
• More electronegative atoms stabilize regions of high
electron density by an electron withdrawing inductive
effect.
• The acidity of H – A increases with the presence of
electron-withdrawing groups in A.
 :
OH 16

Y,
Cl
P
OH 14
di
·

e
en

CI Cl

↑
C
Or 15-8(I .
I
en or 17
Cl

Cl
 Resonance Effects

Resonancia

o o

• The acidity of H – A increases when the conjugate base A:– is

resonance stabilized.
Electrostatic potential plots of
CH3CH2O– and CH3COO–
 >Carbonilos
iP
Hidógenosal
pka
1 =

50 pka= a carbonilo

H Son
=

411
0
acidos
-

-
1
Base
conjugada
pocol nada . VO
estable I

Enolato
Hybridization Effects

The final factor affecting the acidity of H – A is the

hybridization of A. To illustrate this phenomenon, compare
ethane, ethylene and acetylene, three different compounds
containing C – H bonds.
 Los orbitales"s"
sem más

electronegativos. que
los
"

The higher the percent s-character of the

hybrid orbital, the more stable the conjugate
base.

The acidity of H–A increases as the percent s-

character of the A:– increases.
Electrostatic potential plots
of three carbanions
Common Acids and Bases

Several organic reactions are carried out in the presence of

strong inorganic acids, most commonly HCl and H2SO4. These
strong acids, with pKa values <0
Strong bases have weak conjugate acids with
high pKa values, usually > 12.
Strong bases have a net negative charge, but not all
negatively charged species are strong bases. For example,
none of the halides, F–, Cl–, Br–, or I–, is a strong base. These
anions have very strong conjugate acids and have little
affinity for donating their electron pairs to a proton.

Carbanions, negatively charged carbon atoms, are

especially strong bases. Perhaps the most common example
is butyllithium.
 Estereoquímica C Estereoisomerial

Composición igual/Conectividad diferente

Composicion igual /Conectividall Igual

Estereoisómeros
>Isómeros conformacionales

>Enantiómeros
->
Diastereómeros 3 Isómeros ópticos

Proyecciones moleculares
>Cram ~Caballete
H

↓ H
H ·

. H

H1111" H
H H
↓
1 H

H
~Caballete
>Newman
H

" H H

H H H

H
H
H H
H

↳
H
Propano
H H
H H H H
H

* H
↓

CH3 CH3

Butano Proyección C, -

C2

H
H
CHICHy 4 CHaC
H

H H -H
H H

Proyección Cz-C
CHy
CH3
H H
H H
H
H
H
H

CHy
CHs
 Conformations of Acyclic Alkanes

Let’s now take a closer look at the three-

dimensional structure of alkanes. The
threedimensional structure of molecules is called
stereochemistry. We examine the
effect of rotation around single bonds.
I

sómeros
conformacionales

Conformations are different arrangements of atoms that

are interconverted by rotation about single bonds.
 to
amien
calips

↓4 H

H H
+ H

4 H H
H

Geometria Molecular
diedro(0)
Ángulo
P

-- E cambio
Alternada
Cambio la

-
·

.
en
energia
"s01200 molecular

⑧
Por lo tanto se habla de

1."H
moléculas diferentes
de enlace
enhibridación
Gloritual de e
·

la

eclipsada.
Draw the staggered and eclipsed conformations that result from
rotation around the C–C bond in CH3 –CH2Br.

The staggered and eclipsed conformations of ethane

interconvert at room temperature, but each conformation is
not equally stable.
The staggered conformations are more stable (lower in energy)
than the eclipsed conformations.

Más energéticas (menos estables)

Comparadas con las alternaclas
The difference in energy between the staggered and eclipsed
conformations is 12 kJ/mol (2.9 kcal/mol), a small enough difference
that the rotation is still very rapid at room temperature, and the
conformations cannot be separated. Because three eclipsed C – H bonds
increase the energy of a conformation by 12 kJ/mol, each eclipsed C –
H bond results in an increase in energy of 4.0 kJ/mol (1.0 kcal/mol).
The energy difference between the staggered and eclipsed
conformations is called torsional energy. Thus, eclipsing introduces
torsional strain into a molecule.
Graph: Energy versus dihedral angle
for ethane Butano CyHio (C2 -C)

H ~*n /
↑

H
H

13
H

4t↓

H
Barrera Conformacional
H
H a H
M

H
I H

H H

↓
Draw an energy versus rotation diagram similar to Figure
4.8 for rotation around a C– C bond in propane.

The torsional energy in propane is 14 kJ/mol (3.4

kcal/mol). Because each H,H eclipsing interaction is worth
4.0 kJ/mol (1.0 kcal/mol) of destabilization, how much is
one H,CH3 eclipsing interaction worth in destabilization?
Conformations of Butane

Butane and higher molecular weight alkanes have several

carbon–carbon bonds, all capable of rotation.
 H H

d CHy

l
M
13 H

casL I
H H 1
r 4
H CHy H
608 608
H
>
>
H H
I CH3

CHy
4) CH3
cot
1645/mol
gauche
+

+ 3.8
k5/mo
606

V
H H

H,60H↓'2 -
4 r
My CH - H
660 - -

2
4
H3 Me

dig CH3
Hy

+16k5/mo) +

3.8
+
1945/mod
60°
V

cH3

M -
H

de
Cycloalkanes
Besides torsional strain and steric strain, the conformations of
cycloalkanes are also affected by angle strain.

Angle strain is an increase in energy when tetrahedral bond

angles deviate from the optimum angle of 109.5°.

Originalmente se pensaba en cicloalcanos como anillos

planos, con los ángulos de enlace entre átomos de carbono
determinado por el tamaño del anillo. Por ejemplo, un anillo
de ciclopropano plana tendría ángulos de enlace internos de
60°, un anillo de ciclobutano plano tendría ángulos de 90°, y
anillos planos grandes tendrían muy grandes ángulos. Se
supuso que los anillos con diferentes ángulos de enlace por
lo que desde el ángulo de enlace tetraédrico serían muy
tensos y muy reactivos. Esto se conoce como la teoría de la
tensión de Baeyer.
 Bre Br
>
~Br
caly

banana
bond

Br

Brz Br
>

ccly

Resulta, sin embargo, que los cicloalcanos con más de tres

átomos de carbono en el anillo no son moléculas planas. Se
plegaron para reducir la tensión, tanto la tensión angular como
la tensión torsional. Los ciclos de tres y cuatro unidades aún
poseen una considerable tensión angular, pero el plegamiento
reduce los ángulos de enlace internos en los anillos más grandes,
reduciendo así la tensión angular.
 Benzaldehid
H

I -*,
- -
-
x

Conformaciones

Compuesto: n-botano

2 estructuras diferentes
>

Isómeros conformacionales

-,
firme el sit
11
- H
I -
tte b
H , - #

>
I --
Al 13 2

H
I
7.3

I
- RF
9.0
⑩ i lo
⑭-
-
-
- I
H ⑧ -

- ·
I - HETCOR
H
12 0

por-1 ↓ I

**.
⑧

200pp.

do es por
Cyclohexane

Let’s now examine in detail the conformation of

cyclohexane, the most common ring size in naturally
occurring compounds.

The Chair Conformation

The chair conformation is so stable because it eliminates
angle strain (all C–C–C bond angles are 109.5°) and
torsional strain (all hydrogens on adjacent carbon atoms
are staggered, not eclipsed).

In cyclohexane, three C atoms pucker up and

three C atoms pucker down, alternating around
the ring. These C atoms are called up C’s and
down C’s.