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 :

• Where’s the acid ?

• Where’s the base ?

• How the acid react with the base ?

 3 Significant molecular characteristics
effect acidity & basicity :

• The compound’s 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 : +NH -CH NO3-

4 3
 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)
 Arrhenius’s Acid
A substance that when added to water,
increases the concentration of hydronium
ions,H3O+ or hydrogen ions, H+ (proton)

Source of H+ ion
 Arrhenius’s 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 where’s the acid and base B-L in these reactions

1. HCl + NaOH NaCl + H2O

2. H2SO4 + NH3 HSO4- + +

NH4

3. HCl + CH3CH2NH2 Cl- + CH3CH2NH3

CH3 CH3
4. H2SO4 +
H2C C
HSO4- + H3C C+
CH3 CH3
 Solution 1

1. HCl + NaOH NaCl + H2O

acid base

2. H2SO4 + NH3 HSO4- + +

NH4
acid base

3. HCl + CH3CH2NH2 Cl- + CH3CH2NH3

acid base

CH3 CH3
4. H2SO4 +
H2C C
HSO4- + H3C C+
acid
CH3 CH3
base
 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
 Lewis’s 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..

Lewis’s 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 H + A H3CO + HA
acid base co. base 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
+ A H3C NH + HA
H3C N
H base co. base co. acid
acid
Solution 2c

CH3BH2 + A- ???
Solution 2c

CH3BH2 + A- ???

5B 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
+ A H3C B
H3C B A
H base
acid 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 + B A B

electrophile nucleophile bond formed

(acid) (base)

F H

BF3 + NH3 B N
F
H
electrophile nucleophile F H
(acid) (base)
bond formed
 All chemical reactions involve
orbital interaction
Acid base reaction of NH3 and BF3
F
H H F
N + B N B
H H
F
H F F H 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

H3O = 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 + H2O H3O + A
acid base co. acid co. base

H3O A
Ke =
HA H2O
 Acid dissociation constant (Ka)
Water as the solvent
H3O A
Ka = Ke H2O =
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. HCl H + Cl

B. NH3 H + NH2
Case 1

A. HCl H + Cl
strong acid weak co. base

B. NH3 H + NH2
weak acid strong co. base
Case 1

A. HCl H + Cl
strong acid weak co. base
(more stable)

B. NH3 H + NH2
weak acid strong co. base
(more stable)
Case 1

A. HCl H + Cl
strong acid weak co. base

The right side is favored

B. NH3 H + NH2
weak acid strong co. base

The left side is favored

Comparing Cl- and -NH2

Cl- is less reactive than –NH2

Cl- is more stable

Why..??
Case 2

A. CH3 + H CH4

B. NO3 + H HNO3
Case 2

A. CH3 + H CH4
strong base weak co. acid

B. NO3 + H HNO3
weak base strong co. acid
Case 2

A. CH3 + H CH4
strong base weak co. acid
(more stable)

B. NO3 + H HNO3
weak base strong co. acid
(more stable)
Case 2

A. CH3 + H CH4
strong base weak co. acid
The right side is favored

B. NO3 + H HNO3
weak base 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 Hard
 e pair acceptor atoms are  e pair acceptor atoms are
large small
 Have a low positive charge  Have a high positive charge
density density
 Contain unshared pairs of e  Contain no unshared pairs
in their valence shell (in the of e in their valence shell
p or d orbitals)  Have a low polarizability
 Have a high polarizability  Have a high EN
 Have a low EN
Ex. hydrogen ion
Ex. halogens, phosporus &
sulfur compounds
 BASE
Soft Hard
 The donor atoms are large  The donor atoms are small
(hold their valence e loosely) (hold their valence e tightly)
 Have a high polarizability  Have a low polarizability
 Have a low negative charge  Have a high negative charge
density density
 Have a low EN  Have a high EN

Ex. cyanide ion, iodide ion Ex. hydroxide ion

 List a few example of HSAB
Acids Type Bases

H+,Li+,+CH3,Na+,K+, Hard H2O, -OH, F-, Cl-, -

Mg2+,Ca2+,Al3+,BF3, CH3, -NH2,RCOO,
AlCl3,RCO+,CO2 CO32-,ROH,RO,
NH3,RNH2
Fe2+,Zn2+,Sn2+,Sb3+, Borderline C6H5NH2,N3-,Br-,
BR3,SO2,R3C+,NO+ NO2-,R-

Cu+,Ag+,Hg2+,BH3,I2, Soft RS-,I-,-CN,RCN,CO,

Br2,:CH2 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 CH3OH
(CH3)3C+ (CH3)3C- -SeH

(CH3)3N CH3NH2 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 Cl-

In 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

+ CN + Cl
soft base
H
chlorocyclohexane
 to be continued....

Organic Acids and Bases