pH, strong/weak

acid and base.

 An aqueous solution that is a good
conductor of electricity is a strong
electrolyte.
 An aqueous solution that is a poor
conductor of electricity is a weak
electrolyte.
 The greater the degree of
ionization or dissociation, the
greater the conductivity of the
solution.
 Water is able to conduct, even in a
small amount, electricity. 2
 The properties of water
Water is the most common substance known to man, as
well as the most important. In vapor, liquid or solid
form, water covers more than seventy percent of the
Earth’s surface, and is a major component of the
atmosphere. Water is also an essential requirement
for all forms of life. Most living things are largely
made up of water. Human beings, for example, consist
of about two-thirds water. Pure water is a clear,
colorless, and odorless liquid that is made up of one
oxygen and two hydrogen atoms.
Ion Product Constant of Water
 Water molecules are in continuous motion, even at lower
temperatures. When two water molecules collide, a
hydrogen ion is transferred from one molecule to the other
becomes a negatively charged hydroxide ion.
 The water molecule that gains the hydrogen ion becomes a
positively charged hydronium ion. This process is commonly
referred to as the self ionization of water.
  
H 2O  H  OH

 
2 H 2O  H 3O  OH
 In a chemical reaction, chemical equilibrium is the state
in which both reactants and products are present at
concentrations which have no further tendency to
change with time.

 Usually, this state results when the forward reaction

proceeds at the same rate as the reverse reaction.
 I2 + H2  2HI
 The equilibrium constant, K, is an
expression that gives us a ratio of the
concentration of products and
concentration of reactants of a reaction.
 An equilbrium constant expression is based
on a reaction that is at equilibrium.
 [H3O+] + [OH-]

 Kc = constant of equilibrium

Kc= [H3O+]x [OH-] / [H2O] 2 = 3,264 x 10-18

Even very pure water conducts electricity
to a very small extent due to self
ionisation.

H2O = 1 molecule dissociated in

555.000.000 molecules.

n= 1000g = 55.5 moles

18g/mol

 The concentration of water molecule is

constant, as it stays the same before and
after the process of autoionization.
 2H2O(l) D H3O+(aq) + OH-(aq)

 Applying the equilibrium law at fixed t

 [H3O+(aq)][OH-(aq)] = Kc = 3,26x 10-18
 [H2O(l)]2

 Because the degree of ionisation is so small that it is

virtually all unionised then [H2O] in water = 1000/18 =
55.6 mol dm-3 and a constant.

 Then:
 Kc[H2O] 2 = [H+][OH-] = new constant Kw
 Kw = Kc x [H2O] 2= [H3O+] x [OH- ]

Kw = 3,264x10-18 x (55,5) 2 M = 10 -14M 2

Kw =[H3O+] x [OH- ]= 10 -14 M 2
[H3O+]= [OH- ] = √10 -14 = 10-7 moles/L at
25°C

This equilibrium constant is very important because it applies to all

aqueous solutions
 Kw =[H3O+] x [OH- ]= 10 -14 M 2

The product of the hydrogen and hydroxide

ions is always equal to:
1 x 10 -14 (mol/L) 2.
Therefore, if the concentration of one ion
increases by a factor of 10, then the
concentration of the other ion must decrease
by a factor of 10. Since this relationship is
constant, it is given the symbol Kw, which is
called the ion-product constant for water.
Pure water contains small, but equal amounts of
ions: H3O+ and OH-
H2O + H2O H3O+ + OH-

[ H3O+] =1 x 10-7 M
H3O+ OH-
[ OH-] = 1 x 10-7 M
1 A change in [H3O+] causes an inverse change in
[OH-] and viceversa.

Higher [H3O+] Lower [OH- ]

Higher [OH-] Lower [H3O+]

From Le Chatelier’s principle:

If a chemical system at equilibrium experiences a change in
T,V or Po; then the equilibrium shift to counteract the
imposed change and a new equilibrium is established.
 Aqueous solutions that have a hydrogen ion
concentration greater than the hydroxide ion
concentration are called acidic solutions.

When the hydroxide ion concentration is greater

than the
hydrogen ion concentration, the solution is called
basic or alkaline.
2 Both ions are present in all acqueous systems.

All acidic solutions contain a low concentration of

[OH] ions.
All basic solutions contain a low concentration of
[H3O+] ions.

This allows us to define “acidic” and “basic”

solutions.
Kw = [H3O+ ] [OH- ]

[H3O+] = Kw
[OH-]

[OH- ] = Kw
[H3O+ ]
 Increase H3O+
 More [H3O+] in water > 1 x 10-7M
 As H3O+ increases, OH- decreases
[H3O+] > [OH-]

H3O+
OH-
Increase the hydroxide ions (OH-)

More [OH-] in water, [OH-] > 1 x 10-7M

 When OH- increases, H3O+ decreases
[OH] > [H3O+]

OH-
H3O+
NEUTRAL

 Acidic and basic are two extremes that

describe a chemical property of chemicals.
A substance that is neither acidic nor basic is
neutral.

[H3O+] = [OH-]
 pH term was introduced in 1909 by
Sorensen.

 A pH (potential of Hydrogen) measurement

reveals if a solution is acidic or alkaline
(also base or basic).

 pH is defined as the negative log of the

hydronium ion concentration.
pH= -log (H3O+)
pH= -log₁₀ [H₃O⁺]

pOH= -log₁₀[OH¯]
If we apply the operator “p” to the expression of
the ionic product of water (Kw= [H₃O⁺] x [OH¯]=
10¯¹⁴)

-log₁₀Kw= -log₁₀ {[H₃O⁺] x [OH-]}= -log₁₀ 10-14

pKw= p{[H₃O⁺] x [OH-]}= 14

pKw= pH+ pOH= 14

A solution is acidic if pH<7

A solution is neutral if pH=7

A solution is basic if pH>7

 10-1
pH = 3 pH = 11
concentration (moles/L)

H3O + OH-

pH = 7
10-7
H3O + OH-

OH- H3O +

10-14
[H3O+] > [OH-] [H3O+] = [OH-] [H3O+] < [OH-]
acidic neutral basic
solution solution solution
 The pH scale measures how acidic
or basic a substance is.
 The pH scale ranges from 0 to 14.
 A pH of 7 is neutral.
 A pH less than 7 is acidic.
 A pH greater than 7 is basic.

7
acid
base

0
14
pH = -log (H3O+ )= -log 10 -2 = 2
neutral solution: [H3O+] = [OH-] = 10 –7 M pH = 7.0

acidic solution: [H3O+] > 10-7 M pH < 7.0

basic solution: [H3O+] < 10-7 M pH > 7.0

 The pH scale is logarithmic and as a result,
each whole pH value below 7 is ten times more
acidic than the next higher value.

 For example, pH 4 is ten times more acidic than

pH 5 and 100 times (10 times 10) more acidic
than pH 6.
 The same holds true for pH values above 7,
each of which is ten times more alkaline
(another way to say basic) than the next lower
whole value.

 For example, pH 10 is ten times more alkaline

than pH 9 and 100 times (10 times 10) more
alkaline than pH 8.
THE IMPORTANCE OF pH

Measurement of pH is one of the

most important and frequently
used procedures in biochemistry.
The pH affects the structure and
activity of biological
macromolecules.
“An acid is a substance with H in
its formula that dissociates in
water to yield H₃O⁺”
“A base is a substance with OH
in its formula that dissociates to
yield OH⁻”
 Bronsted
and Lowry found a
new definition that expands
the meaning of “Base”
 “A base is a proton
acceptor, any species
that accepts an H⁺ ion”

This means that it must

contain a lone pair of
electrons to bind the ion.
Arrhenius Bases
 “An acid is a proton
donor, any species that
donates an H⁺ ion”.

These acids must

contain H in their
formula, so they’re
basically Arrhenius
acids.
 Yet, even this definition does
not explain many reactions
involving molecules that do not
have H in their formula.

A new definition was needed, to include molecules

with polar double bonds, metal ions and
electron-deficient atoms.
 “An acid is any species that accepts an electron
pair to form a bond.”

A Lewis acid must therefore have a vacant

orbital!
 Lewis
Acids
Eg. Compunds of
Aluminium and Boron;
Metal cations
Bronsted-Lowry
acids
• An acid is any species that donates an H+ ion or that
accepts an OH- ion.

• A base is any species that accepts an H+ ion or that

donates an OH-.

• The only requirement for an acid-base reaction is

that one species donates a proton and another
species accepts it: an acid-base reaction is a proton-
transfer process.
• In other words, one species behaves as an acid and
the other species behaves as a base simultaneously.
Even when an acid or a base merely dissolves in
water, an acid-base reaction occurs because water
acts as the other partner.
• This definition provides a new way to look at acid-
base reactions because it focuses on the reactants
and the products.

• For example, let’s examine the reaction between

hydrogen sulfide and ammonia:

• In the forward reaction, H2S acts as an acid by

donating an H+ to NH3, which acts as a base by
accepting. The reverse reaction involves another
acid-base pair. The ammonium ion, NH4+, acts as an
acid by donating an H+ to the hydrogen sulfide ion,
HS-, which acts as a base. Notice that the acid,
H2S, becomes a base, HS-, and the base, NH3,
becomes an acid, NH4-.
 Ex: H₂O + NH₃ HO⁻ + NH₄⁺
Acid Base

2 kinds of pairs: acid-base pair (an acid does

exist just because there is a base able to accept
its proton) and acid-conjugate base pair (exist a
pair acid-base-conjugate and viceversa)
 Ex: H₂O + NH₃ HO⁻ + NH₄⁺
Acid Base

2 kinds of pairs: acid-base pair (an acid does

exist just because there is a base able to accept
its proton) and acid-conjugate base pair (exist a
pair acid-base-conjugate and viceversa)
 A “conjugate base” is the remainder of the
original acid, after it donates it’s hydrogen
ion
 A “conjugate acid” is the particle formed
when the original base gains a hydrogen ion
 Thus, a conjugate acid-base pair is related
by the loss or gain of a single hydrogen ion.
BRONSTED - LOWRY THEORY

conjugate conjugate
acid base base acid

HA + B- A- + BH
-H+
+H+

HA + B: A:- + BH+
acid = proton donor
Everything is defined
base = proton acceptor in terms of the proton,
the only recognized type
of acid in B-L theory.
• Whatever is left of the acid after the proton is
donated is called its conjugate base.
• Similarly, whatever remains of the base after it
accepts a proton is called a conjugate acid.
• Conjugate acid-base pairs differ by only one
proton.
Examples: HCl(aq) + H2O(l)  H3O+(aq) + Cl−(aq)
acid base conjugate acid conjugate base

NH3 (aq) + H2O(l)  NH4+(aq) + OH−(aq)

base acid conjugate acid conjugate base

• H+ and H3O+ are pretty much the same thing…(H2O + H+  H3O+)

• H3O+ is called the hydronium ion.
 General equation is:
HA(aq) + H2O(l) ↔ H3O+(aq) + A-(aq)
 Acid + Base ↔ Conjugate acid + Conjugate base
 NH3 + H2O ↔ NH41+ + OH1-
base acid c.a. c.b.
 HCl + H2O ↔ H3O1+ + Cl1-
acid base c.a. c.b.
 Amphoteric – a substance that can act as both
an acid and base- as water shows
 An amphoteric substance is a substance
which can behave as either an acid or a base.
eg. HNO3 (aq) + H2O (l) D H3O+(aq) + NO3- (aq)
NH3 (aq) + H2O (aq) D NH4+ (aq) + OH- (aq)

To be amphoteric, a substance must have a hydrogen ion

to donate. Most amphoteric substances are negatively
charged.
(e.g. HCO3- , H2PO4- etc…)
• The movement of electrons in reactions can be illustrated
using curved arrow notation. Because two electron pairs are
involved in this reaction, two curved arrows are needed.
• Loss of a proton from an acid forms its conjugate base.
• Gain of a proton by a base forms its conjugate acid.
• A double reaction arrow is used between starting materials
and products to indicate that the reaction can proceed in the
forward and reverse directions. These are equilibrium
arrows.
Conjugate Acid-Base Pairs
 The relative strenght of acids and bases
depends on their ability to dissociate.
 Strong acids completely ionize (100%) in aqueous
solutions.
HCl + H2O H3O+ + Cl- (100 % ions)
Strong bases completely (100%) dissociate into ions
in aqueous solutions.
NaOH Na+ (aq) + OH-(aq)
(100 % ions)
Strong acids dissociate completely into ions in water:
Weak acids dissociate very slightly into ions in water:
 Acids and Bases are classified acording to
the degree to which they ionize in water:
◦ Strong are completely ionized in
aqueous solution; this means they
ionize 100 %
◦ Weak ionize only slightly in aqueous
solution
 Strength is very different
from Concentration
 Strong – means it forms many
ions when dissolved (100 %
ionization)
 Mg(OH)2 is a strong base- it
falls completely apart (nearly
100% when dissolved).
◦But, not much dissolves- so it
is not concentrated
 The words concentrated and dilute
tell how much of an acid or base is
dissolved in solution - refers to the
number of moles of acid or base in a
given volume
 The words strong and weak refer to
the extent of ionization of an acid or
base
 Is a concentrated, weak acid
possible?
 Hydrochloric acid, HCl
 Nitric acid, HNO3
 Hydrobromic acid, HBr
 Hydroiodic acid, HI
 Sulfuric acid, H2SO4
(only the first H+ dissociates strongly)
FACTORS THAT INCREASE ACIDITY

STABILIZATION OF A CONJUGATE BASE

We will study the factors that lead STABILIZATION
to lower energy (stabilization) in FACTORS
the conjugate base.
1 Resonance
B
-
2 Electronegativity
stabilization 3 Size of Atoms
4 Hybridization
A-
5 Inductive Effects
6 Charge
7 Solvation
Stabilization of the
HA conjugate base 8 Steric Effects*
Or makes the acid
HB Stronger HA > HB. * usually destabilize
EVALUATION OF ACID STRENGTH

HA + H2O H3O+ + A-
In water, all acids form hydronium ion,
the important factor of difference is
the conjugate base.
The difference between a strong acid
and a weak acid is in the stability of
the conjugate base.
B- WEAK ACID has
strong conj. base
E (=higher energy)

A-
N
E STRONG ACID has
R weak conj. base
ionization (=lower energy)
G easier
Y HA
or HB HA <HB
Which molecule is the stronger acid, ethanol
or acetic acid? Ka

CH3CH2OH CH3CH2O + H 10-16

ethanol

O O
CH3 C CH3 C + H 10-4.74
O H O
more stable anion
acetic acid
because of
the stronger O resonance and
acid
CH3 C inductive effects
O
Resonance in the conjugate bases of
carboxylic acids stabilizes the base and
makes the conjugate acid more acidic.
 Delocalization of the negative charge on
the conjugate base will stabilize the anion,
so the substance is a stronger acid.
 More resonance structures usually mean
greater stabilization.

O O
CH3CH2OH < CH3C OH < CH3 S OH
O
=>
 PHENOLATE ION RESONANCE
_
O O O O
_
-
_
_ More structures,
but not better
O O than acetate.

Non-equivalent structures
charge on carbon and oxygen
 ELECTRONEGATIVITY

When comparing two acids in the same period ...

placing the negative charge on a

more electronegative element in the
conjugate base leads to a stronger acid
As the bond to H becomes more polarized, H
becomes more positive and the bond is
easier to break.

=>
 Acids and Bases
Factors that Determine Acid Strength
Element Effects—Trends in the Periodic Table.

Across a row of the periodic table, the acidity of H—

A increases as the electronegativity of A increases.

Positive or negative charge is stabilized when it is spread

over a larger volume.
 Acids and Bases
Factors that Determine Acid Strength
Element Effects—Trends in the Periodic Table.

• Down a column of the periodic table, the acidity of H—A

increases as the size of A increases.

• Size, and not electronegativity, determines acidity down a

column.
• The acidity of H—A increases both left-to-right across a
row and down a column of the periodic table.
• Although four factors determine the overall acidity of a
particular hydrogen atom, element effects—the identity of
A—is the single most important factor in determining the
acidity of the H—A bond.
 As size increases, the H is more loosely held
and the bond is easier to break.
 A larger size also stabilizes the anion.

When comparing two acids in the same group ...

placing the negative charge on a larger atom
in the conjugate base leads to a stronger acid.
Predict whether trifluoroacetic acid will be a
stronger or weaker acid than acetic acid.
Ka
H O H O
H C C H C C + H 10-4.74
H OH H O

acetic acid

F O F O
F C C F C C + H 10-0.23
F OH F O
Fluorine is more electro-
trifluoroacetic acid
negative than hydrogen. Anion
more acidic acid is more stable.
 Acids and Bases

Factors that Determine Acid Strength—Inductive

Effects

• An inductive effect is the pull of electron density through  bonds

caused by electronegativity differ-ences between atoms.
• In the example below, when we compare the acidities of ethanol
and 2,2,2-trifluoroethanol, we note that the latter is more acidic
than the former.
For a series of oxyacids, acidity increases
with the number of oxygens.
 Acids and Bases
Factors that Determine Acid Strength—Hybridization
Effects Summary of the factors that
determine acidity
 A sample of Hydrochloric acid has a
concentration of 1.22 x 10-3 mol dm-3.
 What is its pH?
 [H+(aq)] = [HCl(aq)] = 1.22 x 10-3 mol dm-3
 pH = -log[H+(aq)]
 =-log(1.22 x10-3)
 = 2.91
 A sample of Nitric Acid has a pH of 5.63
 What is the concentration of the nitric acid?
 [H+(aq)] = 10-pH = 10-5.63 = 2.34 x 10-6 mol dm-3
 HNO3 is a strong acid
 so [HNO3(aq)] = [H+(aq)]
 = 2.34 x 10-6 mol dm-3
 Strong bases are completely dissociated.
 NaOH + aq →Na+(aq) + OH-(aq)
 In an alkaline solution of a strong base the [OH-(aq)] is
the same as the concentration of the alkali.
 The [H+(aq)] depends on Kw, the ionic product of water.
 Kw= [H+(aq)] [OH-(aq)] = 1.00 x 10-14 mol2dm-6 at 25oC
 So log [H+(aq)] + log [OH-(aq)] =-14
 - log [H+(aq)] +- log [OH-(aq)] =14
 pH + POH = 14
 So pH=14-pOH
 A polyprotic acid is Polyprotic acids
one that has more dissociate “stepwise”:
than one H+ to e.g. Sulfuric Acid:
donate:
H2SO4 + H2O D H3O + HSO4-
+

Monoprotic acids:
HF, HCl, HNO3 HSO4- + H2O D H3O+ + SO42-
Diprotic acids:
H2SO4, H2CO3 Write the 3 steps in the dissociation
Triprotic acid: of phosphoric acid! Write the Ka
expression for each step!
H3PO4
pKa1, pKa2, pKa3 describe the dissociation of the first, second, and third
ionizable protons.

H2CO3 (aq) = HCO3- (aq) + H+ (aq) Ka1 = 4.3 x 10-7

HCO3- (aq) = CO32- (aq) + H+ (aq) Ka2 = 5.6 x 10-11
• The equilibrium expression for the dissociation of a
general weak acid HA in water is:

• We simplify the equilibrium expression by

multiplying [H2O] by Kc to define a new equilibrium
constant, the acid-dissociation constant (or acid-
ionization constant), Ka:
Ka is a quantitative measure of the
strength of an acid in solution. It is the
equilibrium constant for chemical reaction
known as dissociation in the context of
acid-base reactions.
 If Ka >> 1 STRONG ACID
The equilibrium position lies to the right

If Ka < 10-4 WEAK ACID

The equilibrium position lies to the left

If Kb >>1 STRONG BASE

The equilibrium position lies to the right.

If Kb < 10-4 WEAK BASE

The equilibrium position lies to the left.
• Like any equilibrium constant, Ka is a number whose
magnitude is temperature dependent and tells how
far to the right the reaction has proceeded to reach
equilibrium. Thus, the stronger the acid, the higher
the [H3O+] at equilibrium, and the larger the Ka:

• Thus, for solutions of the same initial HA

concentration, the smaller the Ka, the lower the
percent dissociation of HA:
 The stronger the acid, the larger the Ka and
the smaller the pKa: stronger

HNO2 (aq) = NO2- (aq) + H+ (aq) Ka = 4.6 x 10-4

pKa = 3.34

CH3COOH (aq) = CH3COO- (aq) + H+ (aq) Ka = 1.76 x 10-5

pKa = 4.75

HCN (aq) = CN- (aq) + H+ (aq) Ka = 6.17 x 10-10

pKa = 9.21
weaker
Relationship Between Ka and Kb for
Conjugate Base Pairs
HX + H2O  H3O+ +X- X- + H2O  OH- + HX

  -
[H
O ][X
(aq) ]
(aq) [HX][OH ]
(aq) (aq)
K
a 3
K
b -
[HX ]
(aq) [X ]
(aq)

 - -
[H
O]
[X ][HX
3(aq)
]
(aq)[OH]
(aq)

(aq)
K a x Kb x -
[HX
]
(aq) [X]
(aq)

Kw   
[HO
3 ][OH
(aq) ]
(aq)

Recall: Autoionization of water

H2O(l) + H2O(l) <-- > H3O+(aq) + OH-(aq)
Kw=1.00x10-14 **must remember this value**
Consider the dissociation of HF and its conjugate base in
water:

HF + H2O D H3O+ + F- F- + H2O D HF + OH-

[ H 3O  ][ F  ] [ HF ][OH  ]
Ka  Kb 
[ HF ] [F  ]
[ H 3O  ][ F  ] [ HF ][OH  ]  
K a ·K b  · 
 [ H 3O ][OH ]  Kw
[ HF ] [F ]

Ka · Kb = Kw
 Relationship Between Ionization
Constants for Conjugate Base Pairs

 For acids and bases whose chemical formulas differ by only one
hydrogen (conjugate pairs) the following apply:

Kw = KaKb Kb =Kw/Ka Ka = Kw/Kb

• Therefore if only the Ka value is available in the

table, we can determine the conjugate pairs Kb by
using the above equations

Note: these equations show the larger the Ka the smaller the Kb
• The stronger the acid, the weaker
the conjugate base.
• H+ is the strongest acid that can
exist in equilibrium in aqueous
solutions.
• OH− is the strongest base that can
exist in equilibrium in aqueous
solutions.
• In every acid-base reaction, the
position of the equilibrium favors
the transfer of a proton from the
stronger acid to the stronger base.
• Notice CH4…it cannot donate H+ so
it is not an acid.
Important Concepts Between
Conjugate Pairs
 pH of a weak acid may be calculated from the acid
dissociation constant, Ka ,the equilibrium constant
expression and the concentration of the acid solution.
 HA(aq) D H+(aq)+ A-(aq)
 Ka = [H+(aq)] [A-(aq)]
 [HA(aq)]

 We simplify this:
 We assume that
 [H+(aq)] = [A-(aq)] and that [HA] = the concentration
of the acid used since degree of dissociation is so
small in dilute solutions.
 Ka now becomes :
 [H+(aq)]2 mol dm-3
 [HA(aq)]
 Although some molecules of acid will have
dissociated the proportion is such that it will
not affect the calculated value of the pH
until the third decimal place – which is fine at
this level.
 Since Ka = [H+(aq)]2 mol dm-3
 [HA(aq)]
 Then [H+(aq)]2 = Ka [HA(aq)]
  [H+(aq)] =√(Ka [HA(aq)])
 And pH = -log [H+(aq)] as before
 Calculate the pH of a 0.1 molL-1 ethanoic acid
solution. Ka = 1.74 x 10-5
Step 1: Write a Ka expression for the dissociation of the weak acid.

CH3COOH + H2O D CH3COO- + H3O+

Ka = [H3O+][CH3COO-]
[CH3COOH]

Step 2: Make 2 assumptions

1. That the amount of dissociation is so small it is insignificant.

Therefore [CH3COOH] = 0.1 molL-1 in this example
2. That [H3O+] = [CH3COO-] (we will call this X)
Step 3: Substitute the values in and solve for X

Ka = [H3O+][CH3COO-]
[CH3COOH]

1.74 x 10-5 = [X][X]

[0.1 molL-1]

X2 = 1.74 x 10-5 x 0.1 molL-1

X = √ 1.74 x 10-5 x 0.1 molL-1

[H3O+] = 1.32 x 10-3 molL-1

Step 4: Calculate the pH in the usual way

pH = -log [H3O+]
= -log (1.32 x 10-3) = 2.88
This law is a relationship between the

dissociation constant and the degree of

dissociation of a weak electrolyte (acids,bases)

For example if we have a monoprotic weak
acid
HA with a Ca concentration in a water
solution,
the number of moles during the equilibrium
changes according to this scheme:
 HA + H₂O ↔ A¯ + H₃O⁺
Initial n
Dissociate nα
Final n-nα nα nα

α= ndissociated/ntot
So the indissociated number of mole=n-nα
Ka=[A¯] x [H₃O⁺]/ [HA]

We know that [A¯]= [H₃O⁺], so

Ka=[(nα/V)²]/[(n-nα)/V]
Ka=nα²/V(1-α²)
Ka= Ca x [α²/(1-α)]

If we decreases the Ca (dilute), the value

of α increases (Ca→0, α →1)
 Ka= Ca x [α²/(1-α)]

Ka=dissociation constant
Α=degree of dissociation
Ca=concentration
 From these results we can deduce that as the
initial acid concentration decreases, the
percent dissociation of the acid increases.
 Weak acids in medicine: dissociated and
un-dissociated forms.
 The role of basic and acid ambience
during digestion.
 When the pH = pKa, half the conjugate acid/base pair
is in the protonated form,
half is de-protonated.

If the pKa = 4.7 (as for acetic acid):

At pH 4.7 [CH3COO-] / [CH3COOH] = 1 (equal)

pH 5.7 [CH3COO-] / [CH3COOH] = 10 (mostly de-protonated)
pH 3.7 [CH3COO-] / [CH3COOH] = 0.1 (mostly protonated)
 For example, the value of the Ka of a particular drug gives
us some important indications about his composition in the
different ambience (basic or acid). Thanks to this we can
derivate important information about the pharmacological
functional features of the molecule.
 An example is the acetylsalicylic acid (aspirin): it’s a weak
acid which is AsaH in the undissociated form an Asa- in the
dissociated form according to the equilibrium AsaH + H2O
Asa- + H3O+.
 The undissociated AsaH, which is not charged, is able to
pass easily through plasmatic apolar membranes and in this
form it’s able to exert his pharmacological activity. On the
contrary, the dissociated form Asa- is not able to pass
through the membrane because it’s electrically charged.
 A reaction between an
acid and a base is called
neutralization. An acid-
base mixture is not as
acidic or basic as the
individual starting
solutions.
 Reaction occurs
regardless the strenght
of the reagents and is
always strongly
exotermic.
Neutralization reaction occurs when acid reacts with a
base to form a salt
General formula:

Acid + Base  Salt + Water

E.g. HCl + NaOH  NaCl + HOH

Which type of reaction is it?

- Double displacement
1. 2HCl + Ca(OH)2 

2. HBr + KOH 

3. HF + NaOH 
1. 2HCl + Ca(OH)2  CaCl2 + 2H2O

2. HBr + KOH  KBr + H2O

3. HF + NaOH NaF + H2O

 acid + base salt + water

HNO3 + KOH KNO3 + H2O

HF + NaOH NaF + H2O

HCOOH + Na(OH) HCCONa + H2O

Titolations are ALWAYS (that is regardless the
strengh of the reactants, weak and/or strong)
complete and strongly exotermic reactions.
 Some important reactions of neutralization can be
found in our organism during digestion and in
particular when the cud reaches the stomach. The
digestion occurs thanks to particular proteolytic
enzymes secreted by the stomach as the pepsin but
mostly by the secretion of HCl by parietal cells.
When the chyme leaves the stomach through the
pyloric sphincter to reach the intestine it is a
strongly acid pulp. For this reason in the first portion
of the intestine that is the duodenum, particular
glands, called Brunner glands secrete a strongly
alkaline mucus which is used to neutralize the acidity
of the chyme and to protect intestinal mucosa from
the autodigestion.
Hydrolysis: an acid-base reaction between
water and the ion(s) of the dissolved salt.

Preliminary consideration:

1. Water is neutral and amphoteric:

H2O  H+ + OH-

2. Dissolved salts exist in ionized form:

NaCl  Na+ + Cl- and any single ion can react with
water
3. If any of the ions in solution has acid-base
character (i.e. is a conjugate acid/base of a weak
base/acid), it will affect the self-ionization
equilibrium of the solvent.
4. Cations of strong bases have no acid-base character
while those of weak bases are acidic.
K+ + H2O = N. R.
NH4+ + H2O  NH3 + H3O+

5. Anions of strong acids have no acid-base character

while those of weak asids are bases.

SO42- + H2O = N. R.
CN- + H2O  HCN + OH-
1. No hydrolysis: Salts of strong acids and strong
bases are neutral in solution.
(NaCl, K2SO4, CaCl2….)

2. Anion-hydrolysis: Salts of weak acids and strong

bases are basic in solution.

Dissolution: KCN  K+ + CN-

Hydrolysis: CN- + H2O  HCN + OH-
3. Cation-hydrolysis: Salts of strong acids and weak
bases are acidic in solution.

Dissolution: NH4Cl  NH4+ + Cl-

Hydrolysis: NH4+ + H2O  NH3 + H3O+
4. Cation-anion hydrolysis: Salts of weak acids and
weak bases can be acidic, basic or neutral in
solution, owing to the hydrolysis of both ions. The
reaction depends on relative acid-base strengths.

Dissolution: NH4CN  NH4+ + CN-

Cation-Hydrolysis: NH4+ + H2O  NH3 + H3O+
Anion-hydrolysis: CN- + H2O  HCN + OH-
Two equilibria coexist in aqueous solutions of
hydrolyzable salts.

1. Self ionization of water:

H2O  H+ + OH- Kw = [H+] [OH-]

2. Hydrolysis of a cation (C+) or an anion (A-)

a) C+ + H2O  COH + H+

[COH] [H+] [COH] Kw Kw

Ka(cation) = = = K
[C+] [C+] [OH-] b

[H+] = Kh[C+] and pH = - log Kh[C+]

2. Hydrolysis of a cation (C+) or an anion (A-)

b) A- + H2O  HA + OH-

[HA] [OH-] [HA] Kw Kw

Kb(anion) = = = K
[A-] [A-] [H+] a

[OH-] = Kh[A-] and pH = 14- pOH

 strong acid weak acid

strong
HCl + NaOH CH3COOH + NaOH
base
neutral salt basic salt
weak NaCl CH3COONa
base
HCl + NH3 Depends on the
strengths of the weak
acidic salt
acid and weak base
NH4Cl
 A buffer is a solution characterized by the
ability to resist changes in pH when limited
amounts of acid or base are added to it.

Buffers contain either a weak acid and

its conjugate base or a weak base and
its conjugate acid.
Thus, a buffer contains both an acid
species and a base species in equilibrium.
 Buffers must contain relatively large
concentrations of either
◦ An acid, HA and its conjugate base A-
◦ A base, B, and its conjugate acid (BH+)
 A buffer is a solution characterized by the
ability to resist changes in pH when limited
amounts of acid or base are added to it.

Consider a buffer with equal molar

amounts of HA and its conjugate base A-
.
When H3O+ is added to the buffer it
reacts with the base A-.

H 3O  ( aq )  A ( aq )  HA( aq )  H 2O (l )
 A buffer is a solution characterized by the
ability to resist changes in pH when limited
amounts of acid or base are added to it.

Consider a buffer with equal molar

amounts of HA and its conjugate base A-
.
When OH- is added to the buffer it
reacts with the acid HA.
OH  (aq )  HA(aq )  H 2O( l )  A  (aq )
 When H+ is added, it reacts essentially to
completion with the weak base present
H+ + A-  HA or

H+ + B  BH+
 When OH- is added, it reacts essentially to
completion with the weak acid present
OH- + HA  H2O + A-

OH- + BH+  H2O + B

 OH- H2O

Acetic acid HAc Ac- Acetate

(CH3COOH) (CH3COO-)

H+
13
3
NH4+ to react with OH-
NH3 to react with H+
 The acetic acid – acetate pair as a buffer system

This system is
capable of
absorbing either
H+ or OH-

Buffering occurs due to

the simultaneous
balancing of water &
buffer dissociation
reactions as governed by
the constants
Kw and Ka.
 How does a buffer work?

At the pKa, [HAc] = [Ac-] so the system is able to absorb the addition
of HO- or H+. If we add HO- near the pH where [Hac] = [Ac-] (ie pH ~=
pKa) then HAc can release H+ to offset the HO- added but the ratio of
HAc to Ac- does not change much. If we add H+ then Ac- can absorb H+
to form HAc. Hence, the pH does not change much.
If a small amount of hydroxide is added to an
equimolar solution of HF in NaF, for example, the
HF reacts with the OH− to make F− and water.
Similarly, if acid is added, the F− reacts with it to form
HF and water.
Henderson-Hasselbalch Equation
 For acids:  [A  ]  When [A-] = [HA],
pH  pK a  log  
 [HA] 
 pH = pKa

For bases: pH  pK a  log

[B] pKa applies
[BH ] to this acid

Kb
B + H2O 
 BH+ + OH-
Ka
base acid acid base

Derivation:
[H ][A  ]
Ka 
[HA]
Consider the equilibrium constant expression
for the dissociation of a generic acid, HA:

HA + H2O H3O+ + A−

[H3O+] [A−]
Ka =
[HA]
Rearranging slightly, this becomes

[A−]
Ka = [H3O+]
[HA]
Taking the negative log of both side, we get

−log Ka = −log [H3O+] + (− log)[A−] base

[HA]
pKa
acid
pH
  So
[base]
pKa = pH − log
[acid]
• Rearranging, this becomes
[base]
pH = pKa + log
[acid]
• This is the Henderson–Hasselbalch equation.
…it is safe to assume that all of the strong
acid or base is consumed in the reaction.
1. Determine how the
neutralization reaction affects
the amounts of the weak acid
and its conjugate base in
solution.
2. Use the Henderson–
Hasselbalch equation to
determine the new pH of the
solution.
 Enzymes do not work efficiently at
different pHs, reactions shift and
the concentration of electrolyres
changes. Many cells, expecially
neural and muscle cells, would be
damaged.
 The following values are determined by blood
gas analyzer:
 pH 7.35 – 7.45
 PCO2 35 – 45 mm Hg
 H2CO3 2.4 mmoles/L of plasma
 HCO3- 24 mmoles/L of plasma
 PO2 80 – 110 mm Hg
15
1
15
2
 Excess acid (H3O+) in the body is neutralized by
HCO3-
 H2CO3 + H2O ← H3O+ + HCO3-
 Equilibrium shifts left
 Excess base (OH-) reacts with the carbonic
acid (H2CO3)
 H2CO3 + OH- → H2O + HCO3-
 Equilibrium shifts right
Carbon dioxide - carbonic acid - bicarbonate buffer

If blood pH drops due to metabolic

production of H+ then [H2CO3]
increases by protonation of HCO3-,
H2CO3 rapidly loses water to form
CO2(aq), which is expelled as CO2(g).

If the blood pH rises, [HCO3-]

increases by deprotonation of H2CO3,
then breathing rate changes and
CO2(g) is converted to CO2(aq) and
then to H2CO3 in the capillaries in the
lungs.

What happens to blood pH when you hyperventilate?

What happens to blood pH when you hypoventilate?
 The phosphate buffer system (HPO42-/H2PO4-
) plays a role in plasma and erythrocytes.
 H2PO4- + H2O ↔ H3O+ + HPO42-
 Any acid reacts with monohydrogen
phosphate to form dihydrogen phosphate
dihydrogen phosphate monohydrogen phosphate
 H2PO4- + H2O ← HPO42- + H3O+
 The base is neutralized by dihydrogen phosphate
dihydrogen phosphate monohydrogen phosphate
 H2PO4- + OH- → HPO42- + H3O+

15
5
 Proteins contain – COO- groups, which, like acetate
ions (CH3COO-), can act as proton acceptors.
 Proteins also contain – NH3+ groups, which, like
ammonium ions (NH4+), can donate protons.
 If acid comes into blood, hydronium ions can be
neutralized by the – COO- groups
 - COO- + H3O+ → - COOH + H2O
 If base is added, it can be neutralized by the – NH3+
groups
 - NH3+ + OH- → - NH2 + H2O
 Symptoms: Failue to ventilate, suppression of
breathing, disorientation, weakness, coma
 Causes: Lung disease blocking gas diffusion
(e.g., emphysema, pneumonia, bronchitis, and
asthma); depression of respiratory center by
drugs, cardiopulmonary arrest, stroke,
poliomyelitis, or nervous system disorders
 Treatment: Correction of disorder, infusion
of bicarbonate
 Symptoms: Increased rate and depth of
breathing, numbness, light-headedness,
tetany
 Causes: hyperventilation due to anxiety,
hysteria, fever, exercise; reaction to drugs
such as salicylate, quinine, and antihistamines;
conditions causing hypoxia (e.g., pneumonia,
pulmonary edema, and heart disease)
 Treatment: Elimination of anxiety producing
state, rebreathing into a paper bag
 Symptoms: Increased ventilation, fatigue,
confusion
 Causes: Renal disease, including hepatitis and
cirrhosis; increased acid production in
diabetes mellitus, hyperthyroidism,
alcoholism, and starvation; loss of alkali in
diarrhea; acid retention in renal failure
 Treatment: Sodium bicarbonate given orally,
dialysis for renal failure, insulin treatment
for diabetic ketosis
 Symptoms: Depressed breathing, apathy,
confusion
 Causes: Vomiting, diseases of the adrenal
glands, ingestions of access alkali
 Treatment: Infusion of saline solution,
treatment of underlying diseases
Methods for Measuring the pH of an
Aqueous Solution

(a) pH paper (b) Electrodes of a pH meter

 What are Indicators?
A molecule whose conjugate acid or
conjugate base has a different
color.

Used to mark a certain pH level.

Used to detect the endpoint of a

titration.
 HIn + H2O H3O+ + In-

Acid-base indicators are weak acids or

bases.
The molecular form has a different color
than the ionic form.
Increase the concentration of H3O+ Decrease the concentration of H3O+

HIn + H2O H3O+ + In- HIn + H2O H3O+ + In-

Or

HIn + H2O H3O+ + In- HIn + H2O H3O+ + In-

1) HIn  10  show the color of HIn
In 

pH  pK HIn - 1

2) In  

 10 
show the color of In -
HIn pH  pK HIn  1

3)
HIn  In  

 combinatio n of the color of HIn & In -

 We’ll be using
phenolphthalein and
bromocresol green.
 The useful pH range for indicator is
pKHIn ± 1

encompass the pH at equivalence point
(titration curve)

Not all indicators change color at the same pH.

The equilibrium between solids and ions is different from
the equilibrium between gases
The equilibrium between solids and ions is a “phase”
equilibrium (e.g. NaCl(aq))

Na+(aq) + Cl-(aq)

NaCl(s)
Ksp deals with a phase equilibrium: (s)  (aq)
An equilibrium can exist between a partially soluble substance and its
solution:
1) solubility: quantity of a substance that dissolves to
form a saturated solution
2) molar solubility: the number of moles of the solute
that dissolves to form a liter of saturated solution
3) Ksp (solubility product): the equilibrium constant for
the equilibrium between an ionic solid and its
saturated solution
A solid always dissolves until no more can dissolve - called
molar solubility (mol/L or M)
An equilibrium is established when the amount dissolving
equals the amount precipitating
This can only be true if there is some solid (thus, we can
usually see if there is an equilibrium)
A solution with solid remaining (I.e. in equilibrium) is called
“saturated”
Note: adding more solid will not affect equilibrium
• If we dissolve in water a substance that gives rise to
enough ions in a solution to obtain a saturated
solution in the presence of the solid undissolved, an
equilibrium is established between the solid
substance and the ions in the solution.
• Consider for example the dissolution of AgCl in the
reaction:
AgCl(s) D Ag+ + Cl-

• An equilibrium is established which is set by the

constant:
Ksp = [Ag+] [Cl-]
• The equilibrium constant is called solubility product
and as all the constants of equilibrium is a function of
temperature only. In the expression of the equilibrium
constant the solid phase, AgCl, does not appear
similarly to what happens in the equilibrium involving a
solid and a gas: in fact the amount of the solid, if
present, do not affect the position of equilibrium.

• In general, for a substance AxBy which result in a

solubility equilibrium of this type:
AxBy D xAy+ + yBx-

• the expression of the solubility product is:

Ksp = [Ay+]x [Bx-]y
 Chemical Equilibrium
Solubility Product

2.) If an aqueous solution is left in contact with excess solid, the

solid will dissolve until the condition of Ksp is satisfied
 Amount of undissolved solid remains constant
 Excess solid is required to guarantee ion concentration is
consistent with Ksp

3.) If ions are mixed together such that the concentrations exceed
Ksp, the solid will precipitate.

4.) Solubility product only describes part of the solubility of a salt

 Only includes dissociated ions
 Ignores solubility of solid salt
• The solubility product Ksp can be defined as follows:

in a saturated solution of a slightly soluble ionic

compound, the product of the molar concentrations of the
ions, each raised to a power equal to the stoichiometric
coefficient with which it appears in the solubilization
equation, is constant at any given temperature.
For solids dissolving to form
aqueous solutions.
Bi2S3(s)  2Bi3+(aq) + 3S2 (aq)

Ksp = solubility product constant

and
Ksp = [Bi3+]2[S2 ]3
The solutions of acids and bases are not tolerated
by the tissues of our body.
It’s not possible to administered this solutions for
therapeutic purposes.
For this reason, for the treatment of gastric
hyperacidity the chemical species used are poorly
soluble: they work only in the stomach
 Antacids
Stomach cells secrete hydrochloric acid
(0.155 M HCl) to digest the food.
Generation of too much acid  “heartburn”.
Antacids neutralize the excess HCl.
This reaction then is an Acid/Base reaction.
Would a little bit of NaOH be equally effective???

HCl + NaOH  H2O + NaCl

Antacids are formulated to reduce acidity while

avoiding physiological side-effects.
Commercial Antacids Use A Variety of Chemicals
Calcium-based antacids: Tums, Rennies

CaCO3 + 2HCl  CaCl2 + H2CO3

H2CO3  H2O + CO2

Magnesium-based antacids: Mylanta, Milk of Magnesia

Mg(OH)2 + 2HCl  MgCl2 + 2H2O

Aluminum-based antacids: Maalox, Mylanta

Al(OH)3 + 3HCl  AlCl3 + 3H2O

Bicarbonate-based antacids: Alka Seltzer

NaHCO3 + 1HCl  NaCl + H2CO3

For example
Mg(OH)₂ (Kps=1,1x10-11M3; s=1,4x10-4) or
[Al(OH)₃ x 3H2O] (Kps=4x10-13M4; s=3,5x10-4)

Both the salts are poorly soluble, so are not

dangerous for the tissue of the body, since they
release few OH- ions
PbI2(s) Pb2+(aq) + 2I–(aq)

Common ion: “The ion in a mixture of ionic

substances that is common to the formulas of at
least two.”

Common ion effect: “The solubility of one salt is

reduced by the presence of another having a
common ion”
 Common Ion Effect
The shift in equilibrium that occurs because of
the addition of an ion already involved in the
equilibrium reaction. This effect makes a
solution of NaF and HF less acidic than a
solution of HF alone.

AgCl(s)  Ag+(aq) + Cl-(aq)

adding
 
NaCl( aq ) shifts equilibrium position
 Chemical Equilibrium

Common ion effect – a salt will be less soluble if one of its

constituent ions is already present in the solution.

Decrease in the solubility of MgF2 by

PbCl2 precipitate because the
the addition of NaF
ion product is greater than Ksp.
 PbCl2(s) Pb2+(aq) + 2Cl–(aq)

A+B Explanation
1 Cloudy / precipitate Cl– causes shift left

2 No reaction (oily) No Cl or Pb

3 Cloudy / precipitate Pb causes shift left

4
Common ion: “The ion in a mixture of ionic substances that is common to the
formulas of at least two.”
Common ion effect: “The solubility of one salt is reduced by the presence of
another having a common ion”