Modern Theories

of
Acids & Bases
The Arrhenius
and
Bronsted-Lowry Theories
From website produced at Charles W Baker High School
Baldwinsville, Onondaga County New York
 Acids & Bases
• Acids and bases are special kinds of
electrolytes. Like all electrolytes they
break up into charged particles.

• What sets them apart from each other,

and other electrolytes is the way that they
break up.
 Arrhenius Acids
Svente Arrhenius (who first proposed the
theory of ionization) identified acids as
substances that ionize in water to produce
hydronium ion.
For example:
HCl + H2O  H3O+ + Cl-
Any substance that ionizes in water to
produce hydronium ion can be classified as
an acid.
 H3O (aka H )
+ +

• The hydronium ion is also known as a hydrogen ion.

• This allows us to shorten the ionization reactions for

acids. The following equations represent the same
chemical change:
HCl + H2O  H3O+ + Cl-
and
HCl  H+ + Cl-
However, it should be understood that H+ is an
abbreviation for the hydronium ion. H+ ions DO NOT
exist in water solution but are snatched up by water
molecules to form hydronium ions.
 Arrhenius Base
Svente Arrhenius also identified bases as
substances that ionize in water to produce
hydroxide ion.
For example:
NaOH  Na+ + OH-

Any substance that ionizes in water to produce

hydroxide ion can be classified as a base.
 Properties of Acids
All acids have the following properties:
Neutralize bases to form a salt and water
Have a sour taste (example: citric acid,
vinegar)
React with metals to produce a salt plus
hydrogen gas.
Have pH’s less than 7 / Affect indicators

Why?
Because all acids have H3O+ ions present!
 Properties of Bases
All bases have the following properties:
Neutralize acids to form a salt and water
Have a bitter taste (example: unsweetened
chocolate, heroin)
Are slippery. React with fats/oils to form
soap (saponification)
Have pH’s greater than 7 / Affect indicators

Why?
Because all bases have OH- ions present!
 Salts
Ionic substances that break up in solution to
produce ions other than hydronium and
hydroxide ions.
NaCl (s)  Na+(aq) + Cl- (aq)
KNO3(s)  K+ (aq) + NO3- (aq)
Li2SO4 (s)  2 Li+ (aq) + SO42-(aq)
Salts are made up of positive (metal) and negative (non-
metallic or polyatomic) ions. The more familiar you
become with Table E, the easier it will be for you to identify
salts.
 Strong/Weak Acids
• Acids can be either strong electrolytes or weak
electrolytes.
• Strong acids (such as HCl) completely break up into
their ions:
HCl (aq)  H+(aq) + Cl-(aq)
• Weak acids (such as HC2H3O2) only partially break up
into their ions:
HC2H3O2  H+ (aq) + C2H3O2-(aq)
Weak acids don’t completely break up because they go to
equilibrium!
 Strong/Weak Bases
• Bases can be either strong electrolytes or weak
electrolytes.
• Strong bases (such as NaOH) completely break up into
their ions:
NaOH (aq)  Na+(aq) + OH-(aq)
• Weak bases (such as NH3) only partially break up into
their ions:
NH3 (aq) + H2 O  NH4+ (aq) + OH-(aq)
Weak bases don’t completely break up because they go to
equilibrium!
Bronsted-Lowry Acids &
Bases
Another theory of acids & bases
 Not everyone was happy with
Arrhenius’s definition

A major problem with the Arrhenius definition of

acids and bases is that it limits acids and bases
to water (aqueous) solutions.

Since an acid requires water to ionize and form

hydronium ions, there can be no Arrhenius acids
unless water is involved as the solvent.
 Relationship between the two
models

Bronsted-
Arrhenius Lowry
Acids/Bases only Acids/Bases
exist in water can exist
solutions. when no
water is
present

All Arrhenius acids and bases can also be classified as

Bronsted-Lowry acids and bases.
 Bronsted-Lowry Definitions
Bronsted and Lowry felt that this was too limiting, since
there are many non-aqueous systems (no water is
present).

They came up with the following definitions for acids and

bases.

An acid is a proton (H+ ion) donor

A base is a proton acceptor

Saying goes: “FOLLOW THE BOUNCING H+ “

 An example
In the reaction below there are no Arrhenius
acids or bases present (because no
hydronium ions or hydroxide ions are formed).

However, the HCl is acting as a Bronsted-

Lowry acid because it is giving a H+ ion to
the NH3 (which is acting as a H+ ion
acceptor - a base)
 Acid & Bases are Roles
In the Bronsted-Lowry definition, substances
are classified as acids or bases depending
on how they behave in a given situation.

This means that the same substance can

act as a acid in one reaction (by donating
a proton) while acting as a base in another
reaction
Conjugate Acid-Base Pairs

conjugates
acid2 base2
NH3 + H 2O NH41+ + OH-
base1 acid1

conjugates

NH3 + H 2O NH41+ + OH-

base acid CA CB

So to figure out conjugate pairs, look at how H+ moves

from reactant to product. As saying goes, Follow the
bouncing H+
Conjugate Acid-Base Pairs

conjugates
base2 acid2
HC2H3O2 + H2O H3O1+ + C2H3O2OH-
acid1 base1

conjugates

HC2H3O2 + H2O H3O1+ + C2H3O2OH-

acid base CA CB

So to figure out conjugate pairs, look at how H+ moves from

reactant to product. As saying goes, Follow the bouncing H+
 HCl as a proton donor
• Consider the following reaction:

• Since the HCl gives up a H+ ion to the water it is acting

as a Bronsted-Lowry acid. In the process of donating
the proton it also forms a hydronium ion, and that makes
it an Arrhenius acid as well.
 Water as a base
• But what does that make the water molecule?

• Since the water molecule is accepting the H+ ion, it is

acting as a Bronsted-Lowry base. Since there is no
hydroxide ion (OH-) formed, the water is not acting as an
Arrhenius base in this reaction.
 Ammonia as a base
• Let’s look at another example:

• Here the ammonia molecule is accepting a H+ ion and

therefore is acting as an Bronsted-Lowry base.
However, in the process of reacting with the water it is
also forming a hydroxide ion. That makes the ammonia
an Arrhenius base as well.
But what about the water?

Since the water is giving up a H+ ion, it is

acting as a Bronsted-Lowry acid. Since it
does not form hydronium ions, it is NOT
acting an Arrhenius acid.
 So is water an acid or a base?
• In one example, we said that water was acting as a
base, and in another example we said that it was acting
as an acid.

• Some of you may be confused by this because you are

thinking of acids and bases as being like boys and girls.
Boys are boys and girls are girls, and they can’t switch
back and forth. However, acids and bases are NOT
like this.
 Amphiprotic
• Sometimes a molecule can donate a proton (act as an
acid) and sometimes it can accept a proton (act as a
base).

• Molecules that have this ability to act as both an acid

and a base are called amphoteric or amphiprotic.

• Water is the most common example of an

amphoteric substance.
 Acid-base equilibrium
Many acid base reactions go to equilibrium, that is they
have both a forward and reverse reactions

For instance, acetic acid (HC2H3O2) reacts with water to

form hydronium ion and acetate ion.
 The reverse reaction
However, the acetic acid only partially ionizes because a
reverse reaction takes place preventing the forward
reaction from reaching completion.

In the reverse reaction, the Hydronium ion acts as an acid

(a proton donor) while the acetate ion acts as the base.
 Conjugate Acid-Bases
• When a substance donates a proton, the substance that
is left is its conjugative base:

• Notice that the conjugative base is accepting a proton in

the reverse reaction.
Every acid has a conjugative base
 Conjugative Acid-Base Pairs 2
• When a substance accepts a proton, the substance that
is formed is its conjugative acid:

• Notice that the conjugative acid is donating a proton in

the reverse reaction.
Every base has a conjugative acid
Identify the
amphoteric
substances in
this chart.
 Strong and weak acids
In predicting the type of salt it is helpful to remember the
three strong acids:

• HCl – hydrochloric acid

• HNO3 – nitric acid
• H2SO4 – sulfuric acid

Most other acids are weak. Acetic acid (HC2H3O2) is the

most common weak acid discussed in Regents
chemistry.
 Strong and Weak Bases
For bases, the Group I hydroxides are all strong bases.

LiOH – lithium hydroxide

NaOH – sodium hydroxide
KOH – potassium hydroxide

• Most other hydroxides can be considered as weak

bases. Ammonia or Ammonium hydroxide (NH3 or
NH4OH) is the most common weak base discussed in
Regents chemistry.
 Acid Strength and Ionization Constants
• For the ionization or dissociation equilibrium of an
acid in aqueous solution, such as:
HA(aq) + H2O  H3O+(aq) + A-(aq);
The ionization or dissociation constant is
expressed as follows:
[H 3O  ][A - ]
Ka 
[HA]
The values of Ka indicate the relative strength of the
acids. Strong acids have very large Ka, while weak
acids have small Ka’s (Ka << 1)
 Relative Strength of Acids and Their
Conjugate Bases
Acids Conjugate Bases
Very Strong Very Weak
Strong Weak
Weak Strong
Very Weak Very Strong
______________________________
• Strong acids lose protons very readily  weak
conjugate bases;
• Weak acids do not lose protons very readily  strong
conjugate bases.
Relative Strength of Acids and Their Conjugate Bases
 Acid-Base Properties of Water
• Auto-ionization of water:
2H2O  H3O+(aq) + OH-(aq)
Kw = [H3O+][OH-] = 1.0 x 10-14 at 25oC

• Water ionizes to produce both H3O+ and OH-, thus it

has both acid and base properties. Kw is called water
ionization constant.
• Pure water at 25oC: [H3O+] = [OH-] = 1.0 x 10-7 M
 Expressing Acidity in pH Scale
• pH = -log[H+] (note: [H+] = [H3O+])

• pOH = -log[OH-]
• pKw = -log(Kw); pKa = -log(Ka); pKb = -log(Kb)
• For water, Kw = [H3O+][OH-] = 1.0 x 10-14
• -log(Kw) = -log [H3O+] + (-log[OH-])
• pKw = pH + pOH = 14.00
• At 25oC, pOH = 14 – pH
 Acidity and pH Range

• Acidic solutions:
[H3O+] > 1.0 x 10-7 M;
pH < 7;
• Basic solutions:
[OH-] > 1.0 x 10-7 M or [H3O+] < 1.0 x 10-7 M
pH > 7;
• Neutral solutions:
[H3O+] = [OH-] = 1.0 x 10-7 M; pH = 7.00
Relationship between acidity of solution and pH
 [H3O+] and pH of Strong Acids

• Strong acids like HCl and HClO4 ionize completely in

aqueous solution:
HCl(aq) + H2O  H3O+(aq) + Cl-(aq);
HClO4(aq) + H2O  H3O+(aq) + ClO4-(aq);
• In solutions of strong monoprotic acids HA, such as
HCl and HClO4,
[H3O+] = [HA]0
• For example, in 0.10 M HCl, [H3O+] = 0.10 M, and
pH = -log(0.10) = 1.00
 -
[OH ] and pH of Strong Bases
• Like strong acids, strong bases also ionize completely in
aqueous solution.
• Examples: NaOH(aq)  Na+(aq) + OH-(aq);
Ba(OH)2(aq)  Ba2+(aq) + 2 OH-(aq);
• In a base solution such as 0.050 M NaOH,
[OH-] = [NaOH]0 = 0.050 M;
pOH = -log(0.050 M) = 1.30; pH = 14.00 - 1.30 = 12.70
• In a base solution such as 0.050 M Ba(OH)2,
[OH-] = 2 x [Ba(OH)2]0 = 0.10 M;
pOH = -log(0.10) = 1.00; pH = 14.00 - 1.00 = 13.00
 [H3O+] and pH of Weak Acids

• In weak acid solutions, [H3O+] < [HA]0;

• [H3O+] and pH can be calculated from the initial
concentration of the acid and its Ka value.

• For example, in 0.100 M acetic acid, CH3COOH, with

Ka = 1.8 x 10-5, [H3O+] and pH can be calculated
using the “ICE” table.
 ICE Table for Acetic Acid

• Ionization: CH3CO2H + H2O  H3O+ + CH3CO2-

 
• Initial [M] 0.100 0.00 0.00
• Change [M] -x +x +x
• Equilm. [M] (0.100 – x) x x
 
 
[H 3O ][CH 3CO 2 ] x2
Ka    1.8 x 10-5
[CH 3COOH] (0.100 - x )
 Calculating [H3O+] from initial concentration
and Ka by approximation method.
• Solving for x in the expression for Ka:
 
[H 3O ][CH 3CO 2 ] x2
Ka    1.8 x 10-5
[CH 3CO 2 H] (0.100 - x )
K a  [HA]0 (1.8 x 10-5  0.100)  x  0.100,
x2 x2
and (0.10 - x ) ~ 0.10. This makes ~  1.8 x 10-5 ;
(0.100 - x ) 0.100
x 2  (0.100)(1.8 x 10-5 )  1.8 x 10-6 ; and x  1.8 x 10-6  1.34 x 10-3 ;
[H 3O  ]  x  1.34 x 10-3 M; pH  - log(1.34 x 10-3 )  2.873
 [OH-] and pH of a Weak Base

• In a weak base, [OH-] < [Base]0;

• [OH-] and pH can be calculated from the initial
concentration of the base and its Kb value.

• For example, in 0.100 M ammonia, NH3, with Kb =

1.8 x 10-5, [OH-] and pH can be calculated using the
following “ICE” table.
 ICE Table for the Ionization of Ammonia

• Ionization: NH3 + H2O  NH4+ + OH-

 
• Initial [M] 0.100 0.00 0.00
• Change [M] -x +x +x
• Equilm. [M] (0.100 – x) x x
 

[NH 4 ][OH - ] x2
Kb    1.8 x 10 5
[NH 3 ] (0.100  x )
Calculate [OH-] from initial concentration and Kb
by approximation method.
• Solving for x in the expression for Kb:
[NH 4 ][OH - ] x2
Kb    1.8 x 10 5
[NH 3 ] (0.100  x )
K b  [B]0 (1.8 x 10 -5  0.100)  x  0.100, and
x2 x2
(0.100 - x ) ~ 0.100, which makes ~  1.8 x 10 -5 ;
(0.100 - x ) 0.100
x 2  (0.100)(1.8 x 10 -5 )  1.8 x 10 -6 , which yields x  1.34 x 10 -3 ;
[OH - ]  1.34 x 10 -3 M  pOH  2.873, and pH  11.127