Arrhenius acid-base theory

In 1884, Swedish chemist Svante August

Arrhenius (1859-1927)

- proposed that acids and bases be defined in

terms of the chemical species they form when
they dissolve in water.
 Arrhenius acid-base theory
Arrhenius acid
-is a hydrogen-containing compound
that, in water produces hydrogen ions (H +
ions)
Arrhenius base
-is a hydroxide-containing compound
that, in water produces hydroxide ions
(OH-- ions)
 Arrhenius acid-base theory
H2O

HNO3(l) H+ (aq) + NO3-- (aq)

H2O

HCl(g) H+ (aq) + Cl-- (aq)

 Arrhenius acid-base theory
H2O

NaOH(s) Na+(aq) + OH--(aq)

H2O

KOH(s) K+ (aq) + OH- (aq)

 Arrhenius acid-base theory
Ionization Dissociations
(no ions initially present) (ions initially present)

H+ A- M+ OH_
H A OH_ M+

Hydrogen negative Arrhenius positive Hydroxide

Arrhenius acid Ion (acidic Ion base (MOH Ion Ion (basic
(HA molecule) species) molecule) species)
 Arrhenius acid-base theory
Ionization
-Is the process in which individual positive and negative
ions are produced from a molecular compound that is
dissolved in solution.

Dissociation
-Is the process in which individual positive and negative
ions are released from an ionic compound that is dissolved
in solution.
 Arrhenius acid-base theory
Arrhenius acid
-have sour taste
-change blue litmus paper to red
-corrosive to many materials

Arrhenius base
-have bitter taste
-change red litmus paper to blue
-slippery to touch
React with the oils in the skin
 Arrhenius acid-base theory
Although it is widely used, Arrhenius acid-base
theory has some shortcomings. It is restricted to
aqueous solutions, and it does not explain why
compounds like ammonia (NH3), which do not
contain hydroxide ion, produce a basic water
solution.
 Bronsted-lowry acid-base theory
In 1923,
Johannes Nicolaus Bronsted (1879-1947), a Danish
chemist and Thomas Martin Lowry (1874-1936), a
British chemist
- proposed a broadened definitions for acids and
bases-definitions that applied in both aqueous and
nonaqueous solutions and that also explained
how some nonhydroxide- containing substances ,
when added to water produce basic solutions.
 Bronsted-lowry acid-base theory
Bronsted-Lowry acid
- Is a substance that can donate a proton (H+ ion) to
some other substance.
- Is a proton donor (or hydrogen ion donor)

Bronsted-Lowry base
- is a substance that can accept a proton (H+ ion)
from some other substance.
- Proton acceptor (or hydrogen ion acceptor)
 Bronsted-lowry acid-base theory
The terms hydrogen ion and proton are used
synonymously in acid-base discussions.

Why?

The predominant isotope 1H1, is unique in that no

neutrons are present; it consist of a proton and an
electron. Thus the ion 1H1+ ,a hydrogen atom that
has lost its only electron, is simply a proton.
Bronsted-lowry acid-base theory

Any chemical reaction that involve a Bronsted-

Lowry acid must also involve a Bronsted-Lowry
base. Proton donation (from an acid) cannot
occur unless an acceptor (a base) is present.
Bronsted-lowry acid-base theory
This theory also includes the concept that hydrogen
ions in aqueous solution do not exist in free state but
rather, react with water to form hydronium ions.

The attraction between a hydrogen ion and and polar

water molecules is sufficiently strong to bond the
hydrogen ion to a water molecule to form hydronium
ion (H3O+)

+
H+ + :O H H:O:H
HH
 Bronsted-lowry acid-base theory
When gaseous hydrogen chloride dissolve in
water, it forms hydrochloric acid;
H2O(l) + HCl(g) H3O+(aq) + Cl – (aq)
( base: ( acid:
H+ acceptor) H+ donor)

The hydrogen chloride behaves as an acid

donating a proton to a water molecule. Because
the water molecule accepts the proton, to
become H3O+, it is the base.
 Bronsted-lowry acid-base theory
-It is not necessary that a water molecule be
one of the reactants in the Bronsted-Lowry
acid –base reaction, the reaction does not
have to take place in the liquid state.
-it can be use to describe gas-phase reaction.
NH3(g) + HCl (g) NH4+ (g) + Cl – (g)
( base: ( acid:
H+ acceptor) H+ donor)
 Conjugate Acid-Base Pair

For most Bronsted-Lowry acid-base

reaction, 100% proton transfer does not
occur. Instead, an equilibrium situation is
reached in which a forward and reverse
reaction occur at the same rate.
 Conjugate Acid-Base Pair

The equilibrium mixture for a Bronsted-Lowry

acid-base reaction always has two acids and
two bases present. Consider the reaction
involving hydrogen fluoride and water.

HF(aq) + H2O(l) H3O+(aq) + F – (aq)

 Conjugate Acid-Base Pair

For the forward reaction, the HF molecules

donate proton to water molecules. Thus, the
HF is functioning as an acid, and the H2O is
functioning as a base.

HF(aq) + H2O(l) H3O+(g) + F – (g)

Acid Base
 Conjugate Acid-Base Pair

For the reverse reaction, the H3O+ functioning as

an acid (by donating proton) and F – behaves
as a base(by accepting a proton).

H3O+(g) + F – (g) HF(aq) + H2O(l)

Acid Base
 Conjugate Acid-Base Pair
The two acids and two bases involved in a Bronsted-Lowry acid-
base equilibrium mixture can be grouped into two conjugate
acid-base pairs.
A conjugate acid-base pair is two species, one an acid and one a
base, that differ from each other through the loss or gain of a
proton (H+ ion).

HF(aq) + H2O(l) H3O+(g) + F – (g)

Acid Base
 Conjugate Acid-Base Pair
Every Bronsted-Lowry acid has a conjugate base and every
Bronsted-Lowry base has a conjugate acid. In general terms,
these relationships can be diagrammed as follows:

HA + B HB+ + A–
Acid Base conjugate acid conjugate base
 Conjugate Acid-Base Pair
For any conjugate acid-base pair,

 The acid-base pair always has one more H atom

and one fewer negative charge than the base.

 The base is an acid-pair always has one fewer H

atom and one more negative charge than the
acid.
 Conjugate Acid-Base Pair
Conjugate acid
-Is the species formed when a proton (H+ ion) is
added to a Bronsted-Lowry base

Conjugate base
- Is the specie that remains when a proton (H+
ion) is removed from a Bronsted-Lowry acid.
 Conjugate Acid-Base Pair
Write the chemical formula of each of the
following:

a. The conjugate base of HSO4-

b. The conjugate acid of NO3-
c. The conjugate base of H3PO4
d. The conjugate acid of HC2O4-
 Conjugate Acid-Base Pair
Solution:
1. SO42-
2. HNO3
3. H2PO4-
4. H2C2O4
 AMPHIPROTIC SUBSTANCES
AMPHIPROTIC SUBSTANCE
-is a substance can be either lose or accept a proton
and thus can function as either a Bronsted-Lowry
acid or a Bronsted-Lowry base.
- Example is water.
HNO3(aq) +H2O(l) H3O+(aq) + NO3-(aq)
Acid base

NH3(aq) + H2O(l) NH4+ (aq) + OH-(aq)

Base acid
 Mono-, di-, and triprotic acids

Monoprotic acid -is an acid that supplies one

proton (H+ ions) per molecule during acid-base
reaction. Example, HCl, HNO3

Diprotic acid- is an acid that supplies two

protons (H+ ions) per molecule during an acid-
base reaction. Ex. H2CO3
H2CO3(aq) + H2O(l) H3O+ + HCO3-(aq)
HCO3-(aq) + H2O(l) H3O+ + CO32-(aq)
 Mono-, di-, and triprotic acids

Triprotic acid- is an acid that supplies three protons (H+ ions)

per molecule during an acid-base reaction. Ex. H3PO4

H3PO4(aq) + H2O(l) H3O+ + H2PO4-(aq)

H2PO4-(aq) + H2O(l) H3O+ + HPO42-(aq)
HPO42-(aq) + H2O(l) H3O+ + PO43-(aq)

Polyprotic acid- is an acid two or more protons

(H+ ions) during an acid-base reaction. Both diprotic and
triprotic acids are examples of polyprotic acids.
Strengths of acids and bases

Strong Acid- is an acid that transfers 100%,

or very nearly to 100%, of its protons (H+
ions) to water in aqueous solution.

Weak Acid-is an acid that transfers only a

small percentage of its protons (H+ ions) to
water in an aqueous solution.
Strengths of acids and bases

Commonly encountered strong Acids

HCl hydrochloric acid
HBr hydrobromic acid
HI hydroiodic acid
HNO3nitric acid
HClO3 chloric acid
HClO4 perchloric acid
H2SO4 sulfuric acid
Strengths of acids and bases

The difference between a strong acid and a

weak acid can also be stated based on the
equilibrium position,

For strong acids;

HA + H2O H3O+ + A-

For weak acids;

HA + H2O H3O+ + A-
 strengths of acids and bases

Strong acid • Weak Acid

HA H2O
H3O+ A- HA H2O

H3O+ A-
Before
Before After proton After proton
proton
proton transfer transfer
transfer
transfer
Strengths of acids and bases

Commonly encountered strong Bases

LiOH NaOH
KOH RbOH
CsOH Ca(OH)2
Sr(OH)2 Ba(OH)2

Fairly encountered weak base

NH3
Ionization constants for acids and bases

For an acid with the general formula HA, the acid

ionization constant is obtained by writing the
equilibrium constant expression for the reaction
HA (aq) + H2O(l) H3O+(aq) + A-(aq)
Which is

H3O+ A-
Ka=
HA
Ionization constants for acids and bases

Note the following relationships among acids

strength, percent ionization, and Ka magnitude.

1. Acid strength increases as the percent

ionization increases.
2. Acid strength increases as the magnitude
of Ka increases.
3. Percent ionization increases as the
magnitude of Ka increases.
Ionization constants for acids and bases

The concentration of water is not

included in the equilibrium
constant because water is pure
liquid. The symbol Ka is used to
denote an acid ionization constant.
Ionization constants for acids and bases

Name Formula Ka Percent Ionization

Phosphoric acid H3PO4 7.5 x10-3 8.3
Hydrofluoric acid HF 6.8 x 10 -4 2.6
Nitrous acid HNO2 4.5 x 10 -4 2.1
Acetic acid HC2H3O2 1.8 x 10 -5 0.42
Carbonic acid H2CO3 4.3 x 10 -7 0.065
Dihydrogen H2PO4- 6.2 x 10 -8 0.025
phosphate ion

Hydrocyanic acid HCN 4.9 x 10 -10 0.0022

Hydrogen HCO3- 5.6 x 10 -11 0.00075
carbonate ion
Hydrogen HPO42- 4.2 x 10 -13 0.000065
phosphate ion
Calculating the acid Ionization constants for an acid when given
its concentration and percent ionization

A 0.0100 M solution of an acid, HA, is 15 % ionized.

Calculate the acid ionization constant for this acid.
To calculate Ka, for the acid we need the molar
concentrations of H3O+, A- and HA in the aqueous solution. The
concentration of H3O+ will be 15 % of the original HA
concentration. Thus, the concentration of H3O+ is

H3O+ = (0.15 ) x ( 0.0100 M) = 0.0015 M

The ionization of a monoprotic acid produces hydronium ions

and the conjugate base of the acid (A- ions ) in a 1:1 ratio. Thus
the concentration of A- will be the same as that of hydronium
Calculating the acid Ionization constants for an acid when given
its concentration and percent ionization

The concentration of HA is equal to the original concentration

diminished by that which ionized (15 % or 0.0015 M):
HA = 0.0100 M – 0.0015 M= 0.0085M

Substituting these values in the equilibrium expression gives

H3O+ A-
Ka =
HA

(0.0015) (0.0015)
= = 2.6 X 10 -4
(0.0085)
Calculating the acid Ionization constants for an acid when given
its concentration and percent ionization

A 0.100 M solution of an acid, HA is 6.0% ionized. Calculate the

acid ionization constant for this acid.

Answer.

Ka = 3.8 x 10 -4
Calculating the acid Ionization constants for an acid when given
its concentration and percent ionization

The dissociation of a polyprotic acid occurs in a stepwise

manner. In general. Each successive step of proton transfer for
a polyprotic acid occurs to a lesser extent than the previous
step.

H2CO3 (aq) + H2O(l) H3O+ + HCO3-

HCO3- (aq) + H2O(l) H3O+ + CO3-

The second proton is not easily transferred as the first because

it must be pulled away from a negatively charged particle,
HCO3- . (remember that particles with opposite charge attract
with one another). Accordingly, HCO3- is a weaker acid than
H2CO3 .
Calculating the acid Ionization constants for a base when given
its concentration and percent ionization

A base ionization constant is the equilibrium constant for the

reaction of a weak base with water. The general expression for
Kb is

BH+ OH-
Kb=
B

where the reaction is

B (aq) + H2O(l) BH+(aq) + OH-(aq)
Calculating the acid Ionization constants for a base when given
its concentration and percent ionization

For the reaction,

NH3 (aq) + H2O(l) NH4+(aq) + OH-(aq)

The base ionization constant is

NH4+ OH-
Kb=
NH3

The Kb value for ammonia, the only common weak

base is 1.8 x 10 -5
 salt
SALT is an ionic compound containing a metal or
polyatomic ion as the positive ion and a nonmetal or
polyatomic ion (except hydroxide) as the negative ion .

* All common soluble salt are completely dissociated into

ions in a solution so the term weak and strong is not
applicable.
 Acid-base neutralization chemical
reaction
Acid-base neutralization chemical reaction
-Is the chemical reaction between an acid and a
hydroxide base in which a salt and water are the
products.
From double-replacement viewpoint
AX + BY AY + BX
We have, for HCl-KOH neutralization,
HCl + KOH HOH + KCl
acid base water salt
 Acid-base neutralization chemical
reaction
From a proton transfer viewpoint, the formation of water
results from the transfer of protons from H3O+ ions to OH-
ions.

Anytime an acid is completely reacted with a base,

neutralization occurs. It doesn’t matter whether the acid
or base is strong or weak.
 Balancing acid-base neutralization
equations
Balance the following equations:

a. 2H+ + OH- H2O

b. H2SO4 + KOH K2SO4 + H2O

 Self-ionization of water

Water
-Polar covalent compound
-Extremely small percentage of water interact with one another to form ions,
a process called self-ionization.
H2O + H2O H3O+ + OH-
-The net effect of this transfer is the formation of equal amounts of
hydronium and hydroxide ion.
-At any given time, the number of H3O+ and OH- present in the sample is
always extremely small.
- At equilibrium and 240C, the H3O+ and OH- concentrations are 1.0 x 10-7
M (0.000000100 M)
 Ion product constant for water
Ion product constant for water
-is the numerical value 1.00 x 10-14, obtained by multiplying the
molar concentrations of H3O+ ion and OH- ion present in pure
water at 240C.

H3O+ OH-
Ion product constant for water=
= (1.00 X 10-7)(1.00 x 10-7)
= 1.00 x 10-14
 Ion product constant for water

To know the concentration of the ions,

H3O+ OH-
1.00 x 10 -14
=

1.00 x 10-14
H3O+ =
OH-
 Acidic, basic, neutral solutions

Acidic solution
-is an aqueous solution in which the concentrations of H3O+ is
higher than that of OH- ion.
Basic solution
-is an aqueous solution in which the concentrations of H3O+ is
lower than that of OH- ion
Neutral solution
- is an aqueous solution in which the concentrations of H3O+ is
equal to OH- ion
 Acidic, basic, neutral solutions
Type of solution Relationship Between

Neutral solution
H3O+ = OH- = 1.00 x 10 -7

Acidic solution
H3O+
is greater than 1.00 x 10 -7
H3O+ OH- is less than 1.00 x 10 -7
OH-

Basic solution
H3O+
is less than 1.00 x 10 -7

OH-
H3O+
OH- is greater than 1.00 x 10 -7
 The pH Concept
pH Scale
-is a scale of small numbers that is used to specify molar
hydronium ion concentration in an aqueous solution.
pH
-is the negative logarithm of an aqueous solution’s molar
hydronium ion concentration.

pH = -log H3O+
 The pH Concept
Integral pH Values
For any hydronium ion concentration expressed in exponential
notation in which the coefficient is 1.0, the pH is given directly by
the negative of the exponent value of the power of 10.

H3O+ = 1.0 x 10 –x
pH = x
 The pH Concept
Non-integral pH Values
1. enter number whose log is desired.
2. using calculator, press the LOG
3. for pH change the sign

pH = -log H3O+