ACID – BASE

EQUILIBRIUM

“There is nothing in the Universe but alkali and acid, from

which Nature composes all things.”- Otto Tachenius [1671]
 ACIDS BASE
◦ taste sour ◦ taste bitter
◦ cause dyes to change ◦ feel soapy
color
 ARRHENIUS
ACID BASE
◦ An acid is a substance ◦ A base is a substance
that, when dissolved in that, when dissolved in
water, increases the water, increases the
concentration of concentration of
hydrogen ions hydroxide ions

NaOH Na+ + Cl-

The Arrhenius concept of acids and bases, while useful, is rather limited.
For one thing, it is restricted to aqueous solutions.
 Brønsted–Lowry
Brønsted Acid Brønsted Base
◦ a substance that donates ◦ a substance that
a proton (H+) accepts a proton (H+)

Their concept is based on the fact that acid–base reactions

involve the transfer of H+ ions from one substance to another
 Brønsted–Lowry
Brønsted Acid Brønsted Base
◦ a substance that donates ◦ a substance that
a proton (H+) accepts a proton (H+)

The transfer of a proton always involves both an acid (donor) and a base
(acceptor). In other words, a substance can function as an acid only if
another substance simultaneously behaves as a base. To be a Brønsted
acid, a molecule or ion must have a hydrogen atom it can lose as an H+.
To be a Brønsted base, a molecule or ionmust have a nonbonding pair of
electrons it can use to bind the H+.

Their concept is based on the fact that acid–base reactions

involve the transfer of H+ ions from one substance to another
 Brønsted–Lowry Acid and Base

Because the emphasis in the Brønsted–Lowry

concept is on proton transfer, the concept also
applies to reactions that do not occur in
aqueous solution. In the reaction between gas
phase HCl and NH3, for example, a proton is
transferred from the acid HCl to the base NH3.

Their concept is based on the fact that acid–base reactions

involve the transfer of H+ ions from one substance to another
Brønsted–Lowry Acid and Base
Let’s consider another example that compares the
relationship between the Arrhenius and Brønsted–Lowry
definitions of acids and bases—an aqueous solution of
ammonia, in which we have the equilibrium:

Ammonia is a Brønsted base because it accepts a proton from H2O.

Ammonia is also an Arrhenius base because adding it to water leads
to an increase in the concentration of OH- (aq).
Water as a Proton Acceptor
◦ When a hydrogen ion is
formed in water, it does
not exist alone for long!
◦ H-bonds form with water
- (forming hydronium ion)
 HCl(g) + H2O(l) Cl -(aq) + H+(aq)

HCl(g) + H2O(l) Cl -(aq) + H3O+(aq)

It is acceptable to represent the proton in aqueous solution either as H+ or as

H3O+. The formula H+ is less cumbersome in calculations involving hydrogen
ion concentrations and in calculations involving equilibrium constants,
whereas H3O+ is more useful in a discussion of Brønsted acid-base properties.
Definition ACID BASE

Arrhenius increases [H+] increases [OH-1] when

when dissolved in dissolved in solution
solution

Bronsted-Lowry H+ donor H+ acceptor

Checking Understanding 3.1:
Identify the acids and bases in the given equations:

1. N2H4 + H2O N2H5+ + OH-

2. C5H5N + H2O C5H5NH+ + OH-
3. CH3COOH + H2O CH3COO- + H3O+
4. HNO2 + H2O H3O+ + NO2-

Answer this first before moving to the next page!

Checking Understanding 3.1 :
Identify the acids and bases in the given equations:

1. N2H4 + H2O N2H5+ + OH-

Base Acid

2. C5H5N + H2O C5H5NH+ + OH-

Base Acid

3. CH3COOH + H2O CH3COO- + H3O+

Acid
Base
4. HNO2 + H2O H3O+ + NO2- What did you
Acid Base
notice about
H2O?
 What Is Different about Water?
◦ Water can act as a Brønsted base and accept a proton
(H+) from an acid.

Acid Base
◦ It can also donate a proton and act as an acid.

o This makes water amphiprotic and amphoteric.

An amphiprotic/amphoteric substance acts as a base when combined with something more strongly acidic
than itself and as an acid when combined with something more strongly basic than itself.
 Difference between amphiprotic and amphoteric

Amphiprotic Amphoteric

◦ An amphiprotic (‘amphi’ – means ◦ Amphoteric means that a

both; ‘protic’ – refers to the substance has reactions as both
proton) substance is one which acid and base
can both donate hydrogen ions
(protons) and also accept them

All amphiprotic substances are also amphoteric.

Not all amphoteric are amphiprotic (there are amphoteric substances
which don't either donate or accept hydrogen ions when they act as acids or bases)
 Conjugate Acids and Bases
In any acid–base equilibrium, both the forward reaction (to the right)
and the reverse reaction (to the left) involve proton transfer.

For example,

Acid Base Conjugate Base Conjugate Acid

An acid and a base such as HA and A- that differ only in the presence
or absence of a proton are called a conjugate acid–base pair
Conjugate Acids and Bases
◦ Two formula that differ by H+ are called a
conjugate acid–base pair.
◦ Reactions between acids and bases always
yield their conjugate bases and acids.

acid: HNO2 – conjugate base: NO2-

base: H2O – conjugate acid: H3O+
Conjugate Acids and Bases
Likewise,

base: NH3 – conjugate cid: NH4+

acid: H2O – conjugate base: OH-
 Identify the conjugate acid-base pairs
in the reaction between ammonia and
hydrofluoric acid in aqueous solution

NH3 (aq ) +HF(aq ) NH+4 (aq ) +F – (aq )

Remember!
Conjugate base of an acid has one fewer H+ .
Conjugate acid of a base has one more H+ .
Conjugate acid-base pairs differ by a matter of one H+
 Identify the conjugate acid-base pairs
in the reaction between ammonia and
hydrofluoric acid in aqueous solution
NH3 (aq ) +HF(aq ) NH+4 (aq ) +F – (aq )

base: NH3 – conjugate cid: NH4+

acid: HF – conjugate base: F-

Remember!
Conjugate base of an acid has one fewer H+ .
Conjugate acid of a base has one more H+ .
Conjugate acid-base pairs differ by a matter of one H+
Relative Strengths
of Acids
and Bases
• the stronger an
acid, the weaker
its conjugate
base, and
• the stronger a
base, the
weaker its
conjugate acid.
Prentice Hall © 2003
Checking Understanding 3.2:
Identifying conjugate acids and conjugate bases.

Answer this first before moving to the next page!

Checking Understanding 3.2:
Identifying conjugate acids and conjugate bases.

(a)
(b)
acid: HClO4 – conjugate base: ClO4
base: CN – conjugate acid: HCN
acid: H2S – conjugate base: HS
base: SO4 – conjugate acid: HSO4
acid: PH4 – conjugate base: PH3
base: H2O – conjugate acid: H3O
acid: HCO3 – conjugate base: CO3
base: HCO3 – conjugate acid: H2CO3
Acid-Base Properties of Water
H2O(l ) H+ (aq ) + OH– (aq )
autoionization of water

conjugate
base acid
H2O + H2O H O + OH–
3
+

acid conjugate
base
© McGraw-Hill Education. 15-23
 Autoionization of Water
◦ Water is amphoteric
◦ In pure water, a few molecules act as
bases and a few act as acids.
◦ This is referred to as autoionization

conjugate
base acid
H2O + H2O H O + OH–
3
+

acid conjugate
base
 In the study of acid-base reactions, the hydrogen ion concentration is key; its value indicates the acidity or
basicity of the solution. Because only a very small fraction of water molecules are ionized, the concentration of
water, [H2O], remains virtually unchanged.

Therefore, the equilibrium constant for the autoionization of water is

Kc = [H3O+][OH-]
Because we use H+(aq) and H3O+(aq) interchangeably to represent the hydrated proton, the equilibrium constant
can also be expressed as
Kc = [H+][OH-]
To indicate that the equilibrium constant refers to the autoionization of water, we replace Kc with
Kw = [H3O+][OH-] = [H+][OH-]
In pure water at 25°C, the concentrations of H+ and OH- ions are equal and found to be [H+] = 1.0x10-7 M and
[OH-] = 1.0x10-7 M. Thus, at 25°C
Kw = (1.0x10-7 )(1.0x10-7) = 1.0x10-14
Whether we have pure water or an aqueous solution of dissolved species, the following relation always holds at 25°C
Kw = [H+][OH-] = 1.0x10-14
 Ion Product Constant (Kw)
◦The equilibrium expression for this process is
Kc = [H3O+][OH−] or Kc = [H+][OH−]

◦This special equilibrium constant is referred to as

the ion product constant for water, Kw.
◦At 25 °C, Kw = 1.0  10−14
Kw = [H3O+][OH−] = 1.0  10−14

The ion-product constant (Kw) is the product of the molar

concentrations of H+ and OH− ions at a particular temperature.
Aqueous Solutions Can Be Acidic, Basic, or Neutral
◦ If a solution is neutral, [H+] = [OH–].
◦ If a solution is acidic, [H+] > [OH–].
◦ If a solution is basic, [H+] < [OH–].
Checking Understanding 3.3:
The concentration of OH− ions in a certain
household ammonia cleaning solution is
0.0025 M. Calculate the concentration of
H+ ions.

Answer this first before moving to the next page!

Checking Understanding 3.3:
The concentration of OH− ions in a certain household
ammonia cleaning solution is 0.0025 M. Calculate the
concentration of H+ ions.

Kw = [H+][OH−]

K W 1.0 10 –14

[H ] =
+
= = 4.0  10 –12
M
[OH ] 0.0025
– Give it a thought:
Is the solution acidic,
neutral, or basic?
 Calculating pH and pOH
◦ pH is a method of reporting hydrogen ion concentration
◦ It is a measure of the molar concentration of H+ in an
aqueous solution
pH = – log H 
+

As pH  , H+  

When the pH value of a solution is given and asked to calculate the H+ ion concentration,
take the antilog of the above equation

[H+] = 10 -pH
 Calculating pH and pOH

Neutral pH is 7.00. : [H+] = 1.0  10-7

Acidic pH is below 7.00 : [H+] > 1.0  10-7
Basic pH is above 7.00 : [H+] < 1.0  10-7
 Calculating pH and pOH
◦ pOH is a method of reporting hydroxide ion concentration
◦ It is a measure of the molar concentration of OH- in an
aqueous solution

pOH = - log [OH-]

As pOH , [OH-]
When the pOH value of a solution is given and asked to calculate the OH- ion concentration,
take the antilog of the above equation

[OH-] = 10 -pH
Relationship between pH and pOH

pOH = – log OH 

–

H+  OH–  = Kw = 1.0  10 –14

 +
 
– log H  – log OH  = 14.00
–

pH + pOH = 14.00
1. The concentration of H+ ions in a bottle of wine is
3.20×10−4 M right after the cork was removed. Only
half of the wine was consumed. Calculate the pH of
the wine.
pH = – log H+ 

pH = - log (3.2×10−4 M)
pH = 3.49 (acidic)

© McGraw-Hill Education. 15-35

2. The pH of rainwater collected in a certain region of
the northeastern United States on a particular day
was 4.82. Calculate the H+ ion concentration of the
rainwater.
[H+] = 10 -pH

[H+] = 10 -4.82
[H+] = 1.51x10-5

© McGraw-Hill Education. 15-36

 3. In a NaOH solution OH–  is 2.9  10 –4 M.
Calculate the pH of the solution.
Step 1:
pOH = – log OH– 
(
= – log 2.9  10 –4 )
= 3.54
Now we useStep 2:
Equation (15.9):

pH + pOH = 14.00
pH = 14.00 − pOH
14.00 − 3.54 = 10.46 (basic)

© McGraw-Hill Education. 15-37

 How Do We Measure pH?
◦ One way to measure pH is with a pH
meter. Another method is with indicators.
They give less accurate, but quick
◦ pH meters are used for accurate measurements.
measurement of An indicator is a compound that
pH; electrodes indicate small has one color in its acid form and
changes in voltage to detect pH. another color in its basic form.
 Notice that a change in [H+] by a factor
of 10 causes the pH to change by 1.
Thus, the concentration of H+(aq) in a
solution of pH 5 is 10 times the H+(aq)
concentration in a solution of pH 6.

Give it a
thought:
Which is
more acidic
black coffee
or wine?

Concentrations of H+ and OH− , and pH and pOH values of some common substances at 25 °C.
Checking Understanding 3.4:
1.
2.