CHM 001

The Chemistry of Acids and

Bases

Dr. (Mrs.) Ndukwe Nelly Acha

 Acid-Base Concepts
 Acids and bases are among the most familiar and important
of all chemical compounds. We encounter them each and
everyday even in human systems

 For example Vinegar- acteic acid, lemon juice - citric acid,

milk of magnesium - magnesium hydroxide, there is even HCl
in your stomach to digest food

 Antoine Lavoisier was one of the first chemists to try to

explain what makes a substance acidic.
2
 Acid-Base Concepts
In 1777, he proposed that oxygen was an essential
element in acids. There is one definition involving oxygen
(Lux Flood) but many other ways more useful and we will
discuss those.

The actual cause of acidity and basicity was ultimately

explained in terms of the effect these compounds have
on water by Arrhenius in 1884.

3
 Definitions of Acids and Bases

• Several concepts of acid-base theory including:

– The Arrhenius concept

– The Bronsted Lowry concept
– The Lewis concept

4
 The Arrhenius Definition
 According to the Arrhenius concept of acids and bases, an
acid is a substance that, when dissolved in water,
increases the concentration of hydronium ion (H3O+)
(produces H+).

 Chemists often use the notation H+(aq) for the H3O+

(aq) ion, and call it the hydrogen ion.

 Remember, however, that the aqueous

hydrogen ion is actually chemically bonded to
5
water, that is, H3O+.
Arrhenius Concept of Acids and Bases

 The H3O+ is shown here

hydrogen bonded to
three water molecules.

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Arrhenius Concept of Acids and Bases

A base, in the Arrhenius concept, is a substance

that, when dissolved in water increases the
concentration of hydroxide ion, OH-(aq)
(produces OH-).

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Arrhenius Concept of Acids and Bases
 In the Arrhenius concept, a strong (100%) acid is
a substance that ionizes completely in aqueous
solution to give H3O+(aq) and an anion.

 An example is perchloric acid, HClO4.

 
HClO4 (aq)  H 2O(l )  H 3O (aq)  ClO4 (aq)
 
HClO4 (aq)  H (aq)  ClO4 (aq)
 6 strong acids include HCl, HBr, HI, HNO3 , HClO4, and
H2SO4. Must memorize; work future problems
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 Arrhenius Concept of Acids and Bases
In the Arrhenius concept, a strong (100%) base is a
substance that dissociates completely in aqueous
solution to give OH-(aq) and a cation.

 An example is sodium hydroxide, NaOH

(ionic).
NaOH (s ) HO Na  (aq )  OH  (aq )
2

 6 strong bases include NaOH, LiOH,

KOH, Ca(OH)2, Sr(OH)2, and Ba(OH)2.
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 Arrhenius Concept of Acids and Bases

 Rest of acids and bases (NH3, NH2-, NH-, anions) that you
encounter are weak. They are not completely ionized
and exist in reversible reaction with the corresponding
ions.
– An example is acetic acid, HC2H3O2.
HC 2 H 3O 2 (aq )  H 2O( l ) 
H 3O (aq)  C2 H 3O 2 (aq)

– Ammonium hydroxide, NH4OH, is a weak base.

 
NH 4OH (aq ) NH 4 (aq )  OH (aq ) 10
 Arrhenius Concept of Acids and Bases
 The Arrhenius concept is limited in that it looks at acids and
bases in aqueous solutions only involving H+ and OH-.
 There are many substances with acid/base properties that
do not involve these and cannot be classified by this
theory.
 In addition, it singles out the OH- ion as the source
of base character, when other species can play a
similar role

 There are broader definitions of acids and bases which

we will cover.
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 The Brønsted-Lowry Definition
• According to the Brønsted-Lowry concept, an acid
is the species donating the proton in a proton-
transfer reaction.
• A base is the species accepting the proton
in a proton-transfer reaction.
– In any reversible acid-base reaction, both forward and reverse
reactions involve proton transfer .

– notice this theory is only considers the proton not the hydroxide.
This theory is useful in aqueous solution
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Brønsted-Lowry Concept of Acids and Bases

Consider the reaction of NH3 and H20. Based

on Arrhenius theory (produces OH-) therefore
NH3 is a base in water.

 
NH 3 (aq )  H 2O(l ) NH 4 (aq )  OH (aq )

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Brønsted-Lowry Concept of Acids and Bases
• What is it by Bronsted-Lowry?
 
NH 3 (aq )  H 2O(l ) NH 4 (aq )  OH (aq )
base acid

H+

 In the forward reaction, NH3 accepts a proton from

H2O. Thus, NH3 is a base and H2O is an acid.
Same conclusion without looking at OH-
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Brønsted-Lowry Concept of Acids and Bases

NH 3 (aq )  H 2O(l ) NH 4 (aq )  OH  (aq )
acid base

H+
 Since this is a reversible reaction, there is also
acid/base components on the reverse rxn. NH4+
donates a proton to OH-.

 The NH4+ ion is the acid and OH- is the base.

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Brønsted-Lowry Concept of Acids and Bases
 
NH 3 (aq )  H 2O(l ) NH 4 (aq )  OH (aq )
base acid acid base

 The species NH4+ / NH3 and H2O / OH- are

conjugate acid-base pair.

 A conjugate acid-base pair consists of two species

in an acid-base reaction, one acid and one base, that
differ by the loss or gain of one proton.
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Brønsted-Lowry Concept of Acids and Bases
 
NH 3 (aq )  H 2O(l ) NH 4 (aq )  OH (aq )
base 1 acid 2 acid 1 base 2

 NH4+ is the conjugate acid of NH3 and NH3 is the

conjugate base of NH4+ (NH4+ /NH3). H2O is the
conjugate acid of OH- and OH- is the conjugate base of
H2O (H2O/OH-).

 The Brønsted-Lowry concept defines a species as an

acid or a base according to its function in the proton-
transfer reaction. 17
Brønsted-Lowry Concept of Acids and Bases
 Some species can act as an acid or a base . An amphoteric species
is a species that can act either as an acid or a base (it can gain or
lose a proton).
– For example, HCO3- acts as a proton donor
(an acid) in the presence of OH
2
-

HCO3 ( aq )  OH ( aq )  CO3 ( aq )  H 2O (l )
acid base

H+

–HCO3- acid and CO32- conj base

–OH- base and H2O conj acid
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Brønsted-Lowry Concept of Acids and Bases
– Alternatively, HCO3- can act as a proton acceptor (a base)
in the presence of HF. Proton accepter and base in this
reaction. HCO3- base, H2CO3 conj acid, HF acid, F- conj
base 
HCO3 ( aq )  HF ( aq )  H 2CO3 (aq )  F (aq )


base acid

H+
–HCO3- base and H2CO3 conj acid
–HF acid and F- conj base

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Brønsted-Lowry Concept of Acids and Bases
• The amphoteric characteristic of water is important in the
acid-base properties of aqueous solutions.
– Water reacts as an acid with the base NH3.

 
NH 3 ( aq )  H 2 O (l )  NH 4 ( aq )  OH (aq )
base acid

H+
–NH3 base and NH4+ conj acid
–H2O acid and OH- conj base
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Brønsted-Lowry Concept of Acids and Bases
– Water can also react as a base with the acid HF.
 
HF ( aq )  H 2 O (l )  F (aq )  H 3O (aq )
acid base
–H2O base and H3O+ conj acid
–HF acid and F- conj base
H+
 What dictates if the species will be an acid or base? The other substance.
The better acid will be the acid and the amphoteric species will be the base
and if the other species is a better base than the amphoteric species will be
the acid.
 For the most part, water and polyatomic ions containing protons and charges
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are the amphoteric species you should be concerned with.
Consider the Following. Amphoteric in H2O or Not?
H2SO4 No, always strong acid in water
HSO4- yes

SO42- No, always base in water

conj acid conj base
HF F-
HSO4- SO42-
H2SO4 HSO4-
NH4+ NH3
H2O OH-

H3O+ H2O 22
Brønsted-Lowry Concept of Acids and Bases
• In the Brønsted-Lowry concept:

1. A base is a species that accepts protons; OH- is only one

example of a base.

2. Acids and bases can be ions as well as molecular substances.

3. Acid-base reactions are not restricted to aqueous solution but most
of what we do will be.
4. Some species can act as either acids or bases depending on what
the other reactant is. Molecular species that we call acids and bases
23
will always be that in water; water will be the other.
 The Lewis Definition of Acids and Bases
The Lewis concept defines an acid as an electron
pair acceptor and a base makes available electron
pair.

 This concept broadened the scope of acid-base theory

to include reactions that did not involve H +.

 The Lewis concept embraces many reactions that we might

not think of as acid-base reactions. Most useful definition.
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 Lewis Concept of Acids and Bases
The reaction of boron trifluoride with ammonia is an
example.

:
:F : H :F : H
: :

: :
:F B + :N H :F B N H
:F : H :F : H
:

:
 Boron trifluoride accepts the electron pair, so it is a Lewis
acid. Ammonia makes available the electron pair, so it is
the Lewis base. 25
 Acids and Bases Strengths
 The Brønsted-Lowry concept introduced the idea of conjugate
acid-base pairs and proton-transfer reactions. We consider such
acid-base reactions to be a competition between species for
hydrogen ions.
– The stronger acids are those that lose their hydrogen ions more
easily than other acids; donate proton quicker. From this point of
view, we can order acids by their relative strength as hydrogen
ion donors.
Key Points:
– Similarly, the stronger bases are those that hold The easier to give up proton,
onto hydrogen ions more strongly than other stronger the acid. While the harder
bases; harder to lose proton. to give up proton, stronger the
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base.
 Relative Strength of Acids and Bases
– If an acid loses its H+, the resulting anion is
now in a position to reaccept a proton, making
it a Brønsted-Lowry base.

– If an acid is considered strong, its conjugate base (that

is, its anion) would be weak, since it is unlikely to accept
a hydrogen ion.

– It wants to donate proton as soon as it accepts a proton.

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 Relative Strength of Acids and Bases

• The stronger the acid, the weaker the conjugate

base.

 Hence the following statement :

• The stronger the conj acid is an acid, the weaker its conj
base is a base. The stronger the conj base is a base, the
weaker its conj acid is an acid.
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 Relative Strength of Acids and Bases

– HCl + H2O --> H3O+ + Cl-

– strong acid extremely weak base, non-existent
– HCN + H2O <--> H3O+ + CN-
– weak acid stronger base than Cl
– HCl stronger acid than HCN; therefore, CN- stronger base
than Cl-
– Easy to determine strength between classes (one strong,
one weak)
29
 Strengths of Binary Acids, Oxoacids, and Polyprotic
Acids
 How do we determine the strength of acids/bases that are in the
same class (all strong or weak). Two factors are important in
. determining the relative acid strengths. One is the polarity of the
bond to which the hydrogen atom is attached
– The H atom has a partial positive charge:

d+ d-
H X

– The more polarized (larger EN difference) the bond,

the more easily the proton is removed and the
greater the acid strength. 30
Molecular Structure and Acid Strength
– The second factor is the strength of the bond or, in
other words, how tightly the proton is held.
– This depends on the size, d, of atom X.
d+ d-
H X
– The larger atom X, the weaker the bond and the greater
the acid strength. (less attraction between atoms,
easier to pull off proton).
Larger EN difference and size of anion,
stronger the acid (easier to pull proton off)

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Molecular Structure and Acid Strength
• Consider a series of binary acids from a
given column of elements.
– Let’s predict the following order of acidic strength.
– As you go down the column of elements, the radius
increases markedly and dictates result (adding shell
further away) and the H-X bond strength decreases.
smaller radius, harder larger radius, easiest
ionize, weakest acid ionize, strongest acid
HF < HCl < HBr < HI
Aqueous soln:
HF < HCl = HBr = HI
strong acids
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 Molecular Structure and Acid Strength
• As you go across a row of elements, the polarity of the
H-X bond becomes the dominant factor.
– As electronegativity increases going to the right, the polarity of
the H-X bond increases by large amount as compare to change
in size and the acid strength increases .
– Let’s predict the following order of acidic strength.
smaller EN diff, harder larger EN diff, easiest
ionize, weakest acid ionize, strongest acid

H3N < H 2O < HF

– note: ammonium typically base in water

33
 Molecular Structure and Acid Strength

• Consider the oxoacids. An oxoacid has the structure:

H O Y
– The acidic H atom is always attached to an O atom

– Bond polarity is the dominant factor in the relative

strength of oxoacids.
– This, in turn, depends on the electronegativity of the
atom Y.

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Molecular Structure and Acid Strength

H O Y
– If the electronegativity of Y is large, then the O-H
bond is relatively polar and the acid strength is
greater. Easier to remove proton, stronger acid
– Let’s predict the following order of acidic strength.

HOCl > HOBr > HOI

Larger EN , easiest smallest EN diff, hardest
ionize, strongest acid ionize, weakest acid

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Molecular Structure and Acid Strength
– With each additional O atom, Y becomes
effectively more electronegative.

H O Y
– As a result, the H atom becomes more acidic
as more O are on the species.
– The acid strengths of the oxoacids of chlorine
increase in the following order.
HClO < HClO 2 < HClO3 < HClO 4
weakest strongest
– another way to look at it is charge on Y gets higher stronger pull on
O and weakens O-H bond, easier to remove

36
Molecular Structure and Acid Strength
• Consider polyprotic (more than one
ionizable proton) acids and their
corresponding anions.
– Each successive H atom becomes more difficult to remove
(species is negatively charged therefore harder to pull positive
proton off).
– Therefore the acid strength of a polyprotic acid and
its anions decreases with increasing negative charge.
2 
HPO 4 < H 2 PO4 < H 3 PO4
weakest strongest

code: acid
HW 25 37
 Autoionization of Water
• Self-ionization is a reaction in which two like molecules react to
give ions (amphiprotic therefore can react with self). In the case of
water, the following equilibrium is established.

H 2O( l )  H 2O( l ) H 3O  (aq )  OH  (aq )

– The equilibrium-constant expression for this
system is:  
[H 3O ][OH ]
Kc  2
[ H 2O ]
38
 Self-ionization of Water
– The concentration of ions is extremely
small (equil lies to far left), so the
concentration of H2O remains essentially
constant. This gives:
2  
[H 2O] K c [H 3O ][OH ]
constant
and fact pure liquid activity 1 in K

39
 Self-ionization of Water
H 2O( l )  H 2O( l ) H 3O  (aq )  OH  (aq )
– We call the equilibrium value for the ion product
[H3O+][OH-] the ion-product constant for water,
which is written Kw.
 
K w [H 3O ][OH ]
– At 25 oC, the value of Kw is 1.0 x 10-14.
– Like any equilibrium constant, Kw varies with
temperature. Kw means water + water and basis
of acid/base scale in aqueous solutions

40
 Self-ionization of Water
– Because we often write H3O+ as H+, the ion-
product constant expression for water can be
written:  
K w [H ][OH ]
– Using Kw you can calculate the concentrations of
H+ and OH- ions in pure water.

H 2O( l )  H 2O( l ) H 3O  (aq )  OH  (aq )

x x
   14
K w [ H 3O ][OH ] ( x )( x ) 1.00 x10
41
 Self-ionization of Water
• These ions are produced in equal numbers in
pure water, so if we let x = [H+] = [OH-]
 14 2 o
1.0 10 x at 25 C
 14 7  
x  1.0 10 1.0 10 M [ H 3O ] [OH ]
– Thus, the concentrations of H+ and OH- in pure
water are both 1.0 x 10-7 M. Baseline for what we
call a neutral solution with water as solvent.
– If you add acid or base to water they are no longer
equal but the Kw expression still holds. One goes
up other goes down to keep product equal to Kw
42
 Solutions of Strong Acid or Base

• In a solution of a strong acid you can normally ignore the self-

ionization of water as a source of H+(aq). You have the self
ionization equil and the strong acid ionization; however one drop of
strong acid ionizes 100% and typically produces far greater amount
of hydronium ion than that produced from water itself.

– The H+(aq) concentration is usually determined by

the strong acid concentration.

– However, the self-ionization still exists and is

responsible for a small concentration of H3O+ ion
but we typically neglect it. 43
 Solutions of Strong Acid or Base
• By dissolving substances in water, you
can alter the concentrations of H+(aq)
and OH-(aq).
– In a neutral solution, the concentrations of H+(aq)
and OH-(aq) are equal, as they are in pure water.
[ H 3O  ] [OH  ] 1.0 10  7 M
– In an acidic solution, the concentration of H+(aq) is
greater than that of OH-(aq). [ H 3O  ]  1.0 10  7 M  [OH  ]

– In a basic solution, the concentration of OH-(aq) is

greater than that of H+(aq). [ H O  ]  1.0 10  7 M  [OH  ]
3

44
 Solutions of Strong Acid or Base
• At 25°C, you observe the following
conditions.
– In an acidic solution, [H+] > 1.0 x 10-7 M.
– In a neutral solution, [H+] = 1.0 x 10-7 M.
– In a basic solution, [H+] < 1.0 x 10-7 M.

Realize these definitions for acid/base/neutral

solutions is based as water as solvent. If
different solvent or temperature, the
concentration would be different.

45
 pH
• Although you can quantitatively describe the acidity of a solution by its
[H+], it is often more convenient to give acidity in terms of pH (power of the
hydrogen ion). Easier to see larger value: 10-7 vs 10-8
– The pH of a solution is defined as the negative
logarithm of the molar hydrogen-ion concentration.

– Basically changing 1.0 x 10-7 M to log scale.

1.0 number indicates where between the 10-6 and
10-7 --> 7.00 
pH  log[ H ]

46
 The pH of a Solution
• For a solution in which the hydrogen-ion
concentration is 1.0 x 10-3 M, the pH is:
3
pH  log(1.0 10 ) 3.00
– Note that the number of decimal places in
the pH equals the number of significant
figures in the hydrogen-ion concentration.

note: [H3O+] pH

47
 The pH of a Solution
• In a neutral solution, whose hydrogen-ion
concentration is 1.0 x 10-7 M, the pH = 7.00.

• For acidic solutions, the hydrogen-ion concentration is greater

than 1.0 x 10-7 M, so the pH is less than 7.00.
• Similarly, a basic solution has a pH greater than 7.00.

• Realize pH scale is greater than 14 and less than 0 and that it is dependent on solvent
being water; different solvent different scale; not necessarily neutral equal 7 with different
solvent. Also lower pH more acidic solution not necessarily stronger acid. Strength is
based on ionization not pH although pH affected by strength. Weaker acid can have
lower pH if have much higher conc.

48
Figure : The pH Scale

Ebbing, D. D.; Gammon, S. D. General

Chemistry, 8th ed., Houghton Mifflin, New 49
York, NY, 2005.
 A Problem to Consider
• A sample of orange juice has a hydrogen-ion
concentration of 2.9 x 10-4 M. What is the
pH?

pH  log[ H ]
4
pH  log( 2.9 10 )
pH 3.54

50
 A Problem to Consider
• The pH of human arterial blood is 7.40. What is
the hydrogen-ion concentration?
• calculator 2nd function log
[H+] = 10-pH

[ H ] anti log(  pH )

[ H ] anti log(  7.40)
  7.40 8
[H ] 10 4.0 10 M

51
HYDROXIDE ION CONCENTRATION - pOH
• A measurement of the hydroxide ion concentration,
similar to pH, is the pOH.
– The pOH of a solution is defined as the
negative logarithm of the molar hydroxide-
ion concentration.

pX  log[ X ]

pOH  log[OH ]
  pOH
[OH ] 10 52
 The pH of a Solution
– Using Kw = [H+][OH-] = 1.0 x 10-14 at 25 oC, we can show
another important eq
K w 1.0 x10  14 [ H  ][OH  ]
log K w log1.0 x10  14 log[ H  ][OH  ] log[ H  ]  log[OH  ]
 14  
 log K w  log1.0 x10  log[ H ]  ( log[OH ])
pK w 14.00  pH  pOH [ H  ] 10  pH

[OH  ] 10  pOH

pH  log[ H  ]
pOH  log[OH  ]
K w [ H 3O  ][OH  ] 1.00 x10  14 53
 A Problem to Consider
• An ammonia solution has a hydroxide-ion concentration of
1.9 x 10-3 M. What is the pH of the solution?

You first could calculate the pOH:

pOH  log(1.9 10  3 ) 2.72
Then the pH is: pH 14.00  2.72 11.28
Optional way:

M
HW 26
code: ph 54
 The pH of a Solution

• The pH of a solution can accurately be

measured using a pH meter.

– Although less precise, acid-base indicators are often used to

measure pH because they usually change color within a
narrow pH range.

55
 pH of Strong Acids or Bases
• Calculate the [ H3O+],[OH- ], pH, and pOH in 0.10
M HCl.
0.10 M

56