Organic Chemistry

Chapter 5
Acid Base Theory (1)
by Richard F. Daley & Sally J. Daley
www.ochem4free.com
presented by
Rachmawati Ningsih

ACID - BASE
Chemical reactions
in Organic Chemistry

Nearly all of them can be classify

in to acid base reactions

So...
Key to understanding
organic chemical reaction

Knowledge of acids & bases

3 Questions
in considering a reaction :
Wheres the acid ?
Wheres the base ?
How the acid react with the base ?

3 Significant molecular characteristics

effect acidity & basicity :
The compounds primary functional group
The inductive effect caused by the
presence of additional functional group
The delocalization / resonance effects of
the e in a molecule

Note 1 : Showing charges on atoms

In organic chem, it is important to know
which atom is an ion bears the charge.
Ex. the hydroxide ion, written as OH
(to remind u that the O has the negative charge)

Others :

NH4

CH3

NO3-

Svante Arrhenius (1884)

Acid Base Theory
proposed in his doctoral dissertation
so revolutionary that he was almost
denied his Ph.D.
received The Nobel Prize in Chemistry for
acid base theory (1903)

Arrheniuss Acid
A substance that when added to water,
increases the concentration of hydronium
ions,H3O+ or hydrogen ions, H+ (proton)

Source of H+ ion

Arrheniuss Base
A substance that when added to water,
increases the concentration of hydroxide
ions, -OH

Source of -OH ion

remember this..

Acid Base Arrhenius

ONLY
in Aqueous Solution

The Arrhenius acid-base theory provided

a good start toward understanding
acid-base chemistry..
BUT..
It proved much too limited in its scope.

Johannes N. Bronsted & Thomas M.

Lowry (1923) Acid-Base Theory
Independently of each other
Acid-base reaction is a reaction a proton
transfer between reactants.

Acid-Base of Bronsted-Lowry
Acid :
any molecules or ion that donates a
proton to another molecules or ion
(= proton donor)
Base :
any molecules or ion that receives
that proton (= proton acceptor)

helping hint..

Acid-Base of Bronsted-Lowry (B-L) :

a proton transfer between reactants
donor & acceptor proton

Only remember the acid..

Acid Bronsted-Lowry :
proton donor

Exercise 1
Determine wheres the acid and base B-L in these reactions
1.

HCl

NaOH

2.

H2SO4

NH3

3.

HCl

4.

H2SO4

NaCl

HSO4-

CH3
H2C

C
CH3

H2O

+
Cl-

CH3CH2NH2

NH4
CH3CH2NH3
CH3

HSO4-

H3C

C+
CH3

Solution 1
1.

HCl
acid

NaOH
base

NaCl

2.

H2SO4
acid

NH3
base

HSO4-

3.

HCl
acid

4.

H2SO4
acid

Cl-

CH3CH2NH2
base
CH3
H2C

base

CH3

H2O

NH4

CH3CH2NH3
CH3

HSO4-

H3C

C+
CH3

An equilibium reactions
When..
an acid & a base react with each other

the reactants & products are in equilibrium

with each other

It means :
The reactants on the left side of the
equation are reacting & forming product
and
the products on the right side are also
reacting & forming the starting reactants

Conjugate acid & base

Eq. reaction :
Acid and base on the right side of the
equation are the conjugate acid and the
conjugate base.
ex.
H2SO4 + NH3
HSO4- + +NH4
acid

base

co. base

co. acid

Gilbert Newton Lewis (1916)

Acid-Base Theory
There are a number of reactions that look
like acid-base reactions but do not involve
the transfer of proton
Instead, they involve the interaction of a
pair of non bonding e

Lewiss Acid-Base
Acid :
a molecule that forms a covalent bond by
accepting a pair of e (= e pairs acceptor)
Base :
a molecule that forms a covalent bond by
donating a pair of e (= e pairs donor)

helping hint..

Lewiss Acid-Base :
e pairs transfer between reactants
donor & acceptor e pairs

Only remember the acid..

Lewis Acid :

electron pairs acceptor

Note 2 : Reconcilling The Acid-Base

Theories
Keep in mind that although all 3 definitions
consider the same concepts, they do so
from different view points.
Arrhenius & B-L proton transfer
Lewis e pairs transfer
ex. H+ : proton donor & e pairs acceptor

Exercise 2
The following compounds can act either as
B-L acid or Lewis acid. Show the reactivesite in
each compound and the structure of the
conjugate base that results from a reaction with
base, A-. Determine whether the compound is
a B-L acid or Lewis acid.
a. CH3OH

b. CH3NH2

c. CH3BH2

Solution 2a

CH3OH + A-

???

Solution 2a

CH3OH + A-

???

O and C have full valence shell

O is more EN than C
negative charge on O is more stable than C
O-H bond is the reactive site and stronger B-L
acid than C-H bond

Solution 2a

CH3OH + A-

???

Result :

H3C

O
acid

H3CO

base

co. base

HA
co. acid

Solution 2b

CH3NH2 + A-

???

Solution 2b

CH3NH2 + A-

???

C and N have full valence shell

N is more EN than C
negative charge on N is more stable than C
N-H bond is the reactive site and stronger B-L
acid than C-H bond

Solution 2b

CH3NH2 + A-

???

Result :

H
H3C

N
acid

A
base

H3C
co. base

NH

HA
co. acid

Solution 2c

CH3BH2 + A-

???

Solution 2c

CH3BH2 + A-

???

B is e deficient with only 6 e in its valence shell

B will react before any bonds to H are broken

B is the reactive site and it acts as a Lewis acid

Solution 2c

CH3BH2 + A-

???

Result :
H

H
H3C

B
acid

A
base

H3C

A
H

Electrophile & Nucleophile

Lewis acid-base
Electrophile = lover of e
Nucleophile = lover of nuclei
(donates e to nucleus with an empty orbital)

Nucleophile seeks a nucleus (+ charge)

Electrophile seeks electrons (- charge)

Lewis acid-base & E-N

A

electrophile
(acid)

B
nucleophile
(base)

bond formed

BF3
electrophile
(acid)

NH3
nucleophile
(base)

H
B

F
F

N
H
H

bond formed

All chemical reactions involve

orbital interaction
Acid base reaction of NH3 and BF3
F

H
N

H
H

B
F

F
N

H
F

B
F
F

Can u determine the orbital hybridisation of atom N

in NH3 and atom B in BF3...??

Exercise 3

Show the orbitals involved in the

acid-base reaction of hydrogen
ion with a hydroxide ion.

Acid and Base Strength

Depends on the extent to which it ionizes
in water
Chemists use the AUTOIONIZATION of
pure water to determine the values for the
concentration of acidic and basic
solutions.

Autoionization :
the reaction of 2 molecules of water with each other
to give a hydronium ion and a hydroxide ion.
H2O

H2O

H3O

OH

The amount of autoionization at 25oC = 10-7 M

H 3O

OH = 10 -7 M

Chemist call this a neutral solution

It means :
If u add a compound that is more acidic
than water, u increase conc. of H30+ and
make the solution acidic.
If u add a compound that is more base
than water, u increase conc. of OH and
make the solution basic.

Autoionization constant (Kw)

Autoionization at 25oC
Kw =

H3O

OH = 1,00 x 10 -14

In neutral solution : conc. H30+ = conc. OH

H3O

OH = 1,00 x 10 -7 M

Kw is constant, when one conc. increases the

other must be decrease, by whatever amount is
necessary for the product of the 2 conc. to still
equal 10-14.

Strong-Weak Acid & Base

To determine the relative strength of an acid or a
base, you need to find out how much the acid or the
base ionizes or dissociates in water at equilibrium.
Strong acids & bases ionize completely in water
Weak acids & bases ionize only partly in water

Equilibrium constant (Ke)

HA
acid

H2O

H3O

base

co. acid

Ke

H3 O
HA

A
H2 O

A
co. base

Acid dissociation constant (Ka)

Water as the solvent
Ka = Ke

H2O

H3O

HA

Strong acid Ka

or Ka ??

pKa or pKa

??

Exercise 4
Using the pKa value given the each acid,
calculate the pH of its aqueous solution.
a) 0,1 M CH3COOH (pKa = 4,8)
b) 0,1 M H2S (pKa = 7,0)
c) 0,1 M CH3CH2SH (pKa = 10,6)
d) 0,1 M HCOOH (pKa = 3,7)

Direction predict of a reaction

Case 1
A.

B.

HCl

NH3

Cl

NH2

Case 1

A.

HCl

strong acid

B.

NH3
weak acid

Cl
weak co. base

NH2
strong co. base

Case 1

A.

HCl

strong acid

Cl
weak co. base
(more stable)

B.

NH3
weak acid
(more stable)

NH2
strong co. base

Case 1

A.

HCl

strong acid

Cl
weak co. base

The right side is favored

B.

NH3
weak acid

The left side is favored

NH2
strong co. base

Comparing Cl and NH2

-

Cl- is less reactive than NH2

Cl- is more stable

Why..??

Case 2

A.

CH3

B.

NO3

CH4

HNO3

Case 2

A.

CH3

strong base

B.

NO3
weak base

CH4
weak co. acid

HNO3
strong co. acid

Case 2

A.

CH3

strong base

B.

NO3
weak base
(more stable)

CH4
weak co. acid
(more stable)

HNO3
strong co. acid

Case 2

A.

CH3

strong base

CH4
weak co. acid
The right side is favored

B.

NO3
weak base

HNO3

strong co. acid

The left side is favored

Conclution...
The position of equilibrium is on the
side of the weaker member of the
acid conjugate base pair or base
conjugate acid pair

Hard Soft Acids and Bases

(HSAB)
Direction of the reaction & the stability of the
products, depend on :
the strength of acid & base
the hardness or softness of acid & base
(qualitative measure)

Still remember this..??

An Acid :
has an empty orbital &
an unfilled valence shell
A Base :
has in its valence shell a pair of non
bonding e that is available for donation

Now understand this...

Charge density :
is the volume of space occupied by a charge
A large ion has a lower charge density than a small
ion does
Polarizability :
the ability of an atom to have a distorted
distribution of electron

Get It....????

ACID
Soft
e pair acceptor atoms are
large
Have a low positive charge
density
Contain unshared pairs of e
in their valence shell (in the
p or d orbitals)
Have a high polarizability
Have a low EN

Hard
e pair acceptor atoms are
small
Have a high positive charge
density
Contain no unshared pairs
of e in their valence shell
Have a low polarizability
Have a high EN
Ex. hydrogen ion

Ex. halogens, phosporus &

sulfur compounds

BASE
Soft

Hard

The donor atoms are large

(hold their valence e loosely)
Have a high polarizability
Have a low negative charge
density
Have a low EN

The donor atoms are small

(hold their valence e tightly)
Have a low polarizability
Have a high negative charge
density
Have a high EN

Ex. cyanide ion, iodide ion

Ex. hydroxide ion

List a few example of HSAB

Acids
H+,Li+,+CH3,Na+,K+,

Type
Hard

Bases

Mg2+,Ca2+,Al3+,BF3,

H2O, -OH, F-, Cl-,

CH3, -NH2,RCOO,

AlCl3,RCO+,CO2

CO32-,ROH,RO,
NH3,RNH2

Fe2+,Zn2+,Sn2+,Sb3+,
BR3,SO2,R3C+,NO+
Cu+,Ag+,Hg2+,BH3,I2,
Br2,:CH2

Borderline C6H5NH2,N3-,Br-,
NO2-,RSoft

RS-,I-,-CN,RCN,CO,
C6H6,-SH,H-

Exercise 5
Classify each of the following chemical
spesies as a hard, soft or borderline acid or
base.
(CH3)3B
CH3CH2O(CH3)3Al
AsH3

FeCl3

(CH3)3C+

(CH3)3C-

(CH3)3N

CH3NH2

CH3OH
SeH

SnCl2

HSAB Principle
Hard acids prefer to bond with hard bases
Soft acids prefer to bond with soft bases

helps to predict the outcome of

an acid-base reaction

Example
Acyl group (RCO+) is a hard Lewis, forms
stable combinations with hard bases,
such as : -NH2, RO- and ClIn contrast, it forms marginally stable or
even unstable compounds with soft bases,
such as : RS- and I-

Exercise 6
According to the HSAB Principle, which of
following chemical compounds would u expect to
be stable (or only moderately reactive) & which
would u expect to be unstable (or very reactive) ?
AlI3

CH3COSH

NaH

Mg(SH)2

Hg(OH)2

CH3Cl

AgF

CuCH3

CuI

HgCO3

CsOH

KCH3

Base vs Nucleophile
HSAB Principle help to determine
whether a particular compound will act as
a base or as a nuclepohile
A soft base is a good nucleophile
A hard base is a better base

Remember this..
A Nucleophile :
generally reacts with a positive or
partially positive carbon
A Base :
generally reacts with a positive or
partially positive hydrogen

H+ is much harder acid than C+

Cl

OH

H2O

+ Cl

hard base
H
chlorocyclohexane

Cl

CN

+
H
chlorocyclohexane

CN
soft base

Cl

to be continued....

Organic Acids and Bases