Ch 3 :

Acids 4 Bases
H
'
:-O * conservation
H fi E o :
-
: + : +

+, µ
H
- IH of charge
acid base
( donor) ( acceptor)

•
Label acid base , ,
CA h CB :

?
¥ :O:O +

H
E
o
-
HI + H
µ
.
.

base acid Cong acid .

conj base .

•
Draw reasonable products for the following acid l base reactions :
H

jN t
't
? .o
-
H
E H N' - H + ? H
,
.
.

base acid TH
lone pair attacks proton
at same time push e
-

Base too acid

←
⑦ → a -0
curved arrows : B: + HI -
A E B -
H + : A
↳ show actual movement of e- ( reaction mechanism)

acetic acid base attacks acid

•
Consider :
vinegar :O
:
:O
:

° → It
Heo::
: at +
HYE .
→ +
.

0
,
t

base acid

"

\
: : :

.
. . #
.
' -

"
:-.
:
. .
? .
. .
.

base
acid conj base Cong acid
base
.

acid
.

Cong acid .
Cong base .

← D

acid
base
 Quanitative strength analysis :
use pKa values
Qualitative strength analysis : compare stability of molecules

Quant attire Analysis of Acidity

ka :
equilibrium constant for the rxn between an acid 4 water .

HA HN E A H,Ot Kia [HsOt] CAT

-

=
t t

[ HAT
* Ka quantifies how strong tweak an acid is pKa =

log (ka)
-

?
each pKa unit is in order of
magnitude

-8

* be Hao has a lower pKa ( stronger acid -

-
dissociates more) ,
rxn will go towards left

pKa to analyze equilibria : subtract 50 -

15.7 =
34.3

Qualitative Analysis of
Acidity
most stable side of equilibrium will dominate
"

compare structural stability

"
* →

atom
electronegative
Which
on
•
is stronger acid 4 why ? *

b) compare :-O ~'t

cons base stability
:
.
us

NH happy
not
HCl vs .

Cl is more stable so HCl Is stronger acid

a) draw relevant reaction :
→
:c :-O F- Hit
H .
→
H %! :
-
E H, t
! H .
H +

- -
Steps to analyze cells stronger acid :

I . draw acid l base equilibrium

2 . See which side has more stable conj base .

4 that will give stronger acid

•
Identify 4 most acidic protons in the compound

9
most acidic

P
least acidic
out of the 4

•
Determine equilibrium
*
compare acid 4 conj acid
.

pKa - 25 pka - 38

be acetylene has lower pKa

acid T conj . acid Fwd reaction is favored

Factors affecting Stability of the Negative Formal Charge ( ARIO)

°
Type of atom that carries the charge

°
Resonance °
Induction 0
type of orbital where charge resides

Atom
↳ more
electronegative atoms are better at stabilizing charge

ex .
Which is more NH NO - H ←
more acidic bc oxygen
acidic ? butane propanol wants e
-

① Remove proton . .
① ① ←
oxygen is more electronegative ,

from each N ~ it is okay having extra e -

T
more stable
 Resonance :
stabilizes a formal t) charge
'
'

O
- .

Which is 1.0 .
-
H
or
't ←
more acetic
.

more acetic ?
: .
.

ethanol acetic acid

①Remove proton to ¥
←
to
resonance stabilizes
" "
①
* A does not n :O :O , C-I
charge =
more
.

help here stable conj base

"
bc
"
same so , next is R .

Induction stabilizes C I charge by -

spreading it out ( through O bonds)

'
'
'

NOT IT bonds like resonance

O
.

O C'
Which IS Il "
"
more acidic ? o! c, O? .
←
more acetic
Cl

acetic acid trichloroacetic acid

to ta
both have more stable
p, up,
①
←
i : resonance
Igf?
"
←
dipoles help spread
the charge H
out
molecule
(1 in

Orbital 25 sp sp
'
mores character =
closer to nucleus

④ BE =
more stable

a-

H H
H H
H = H
#
←
it
most acetic
-

ex
-

. H

H H H H
to
± to
H H
H H -0
H = :
bc
¥-0 stable
it
-
←
it
"
more
"
H ¥ H P
Sp orbital
closer to nucleus
Sps orbital sp orbital
'

Exceptions to ARLO :

H -
CEC - H :
NH ,

-0
CE C :-O
.
.

H -
CEC -
H t :
NH , -0
H -
t i.
NH,

pKa
-
-
25 pka = 38
 •
Plank labeled protons in order of
increasing acidity
:

fo"
k Ha Hein ③
② ( bc
He
resonance)
① j y
N * .

.
-

:
① A A #
I 40 -
Ha ll t
o #l
a
F
most
acetic
y
I
③ Ha
F
:-O ② R
Hb ④
.

N
.

Hb
#
-

bc one pair would go on

Sp
'
vs Hb would put it * so far we've seen acids as neutral
on Sps 4 -0
conj base C )-

° Sometimes acids are ( t) →

conj base becomes neutral
still use AKIO to figure out
stability but of Ct) charge
H H H induction destabilizes Ctl
① ③ ②
qty
'

¥10
ttcharge
rank order
ION opposite when
-

in
-

,
Of there acidity
: ,
acing F
q q
* less stable Ct) less happy to 2nd most acidic less

charge means more have Ct) charge stable than -

I -

acetic than Nbc O is

more electronegative
↳ bc wants to get
most acidic rid of It to get neutral charge

Leveling Effect :
if solvent can act as acid or base ,
It will restrict
accessible pKa values

Hao stronger than HN cannot be

: '
ex .
acids used in water
bases stronger than Ho cannot be used water
-

in

O O H
H BT " l
m -0
H H =
'

O S O O H O s O O
'

- - -
-
t -
- -
t

II µ 11 / ④t
+,
O O H H

pKa 9 * all Hzsoy pKa 1.7

-

Is used in
reacting w/ water
-
=
up
=

{ only acid left is Hit w/ pKa =

-
1.7

* can't be used in water

•
Can water be used as a solvent in
following acid l base reactions ?

°
+ € it 1- : H can be used in water
µ a
T H ,Ot pKa I -7 =
-

pka
-
-
15.7 pka -
5 * bc neither acid or cont acid .
are more

acidic than Hoot ,

it cane be used in water .

acid conj base.

HIT + -
o

⑦
ET t Ivi NI be water is
,

than the acid 4 cons .

acid
more

the
acetic

pKa
-
-
25 ←
less acidic than pKa
-
-

35 bases will instead react w/ water

water =
can't use water

as solvent water pKa = 15.7

* If water is not a good solvent ,

choose a solvent w/ less acidic protons like :

o -

W or l--l

Solvation effects in acidity ( when ARLO cannot be explained)

1-
¥ it
H ¥
1- I:O
What
of
can stabilize the conj base
ethanol more than tert butanol -
.

tert Butanol :O ethanol

g- I
-

18 PKa
-

16 Solvent bc it bulkier 4 fit

pKa is can
-

=
bulkier base :

less stable
less solvent molecules around It
* Solvent can stabilize c-I charge of the conj .
base

⑥
Bigger ,
bulkier groups are poorly solvated =
less acidic bc cons .
base is less stable

( bulk" 55M)
"
* solvent is always at HUGE excess over reagents water ~

Additional Acid / Base Notes

H

In
'

-
:-O
"

H
-
HA + N- F- H - +
pka
-
-
38
µ H "

H H
pka
-
-
15.7 p

this lone pair came from

another reason -0
base lone pair IS
it di
more stable on 0 than N
SO right side is favored