Acid-Base Equilibria

Chapter 3 1
Acids and Bases:
• Acid: vị chua, làm thuốc nhuộm đổi màu
• Bases: vị đắng, cảm giác nhớt.
• Arrhenius: acids làm tăng [H+], bases làm tăng
[OH-] trong dung dịch.
• Arrhenius: acid + base  salt + water.
• Problem: định nghĩa này chỉ áp dụng được
trong dung dịch nước

Chapter 3 2
Brønsted-Lowry Acids and Bases
The H+ Ion in Water
• The H+(aq) ion is simply a proton with no
electrons. (H has one proton, one electron, and
no neutrons.)
• In water, the H+(aq) form clusters.
• The simplest cluster is H3O+(aq). Larger
clusters are H5O2+ and H9O4+.
• Generally we use H+(aq) and H3O+(aq)
interchangeably.

Chapter 3 3
Brønsted-Lowry Acids and Bases
The H+ Ion in Water

Chapter 3 4
Brønsted-Lowry Acids and Bases
Proton Transfer Reactions
• Focus on the H+(aq).
• Brønsted-Lowry: acid donates H+ and base accepts H+.
• Brønsted-Lowry base does not need to contain OH-.
• Consider HCl(aq) + H2O(l)  H3O+(aq) + Cl-(aq):
– HCl donates a proton to water. Therefore, HCl is an
acid.
– H2O accepts a proton from HCl. Therefore, H2O is a
base.
• Water can behave as either an acid or a base.
• Amphoteric substances can behave as acids and
bases.
Chapter 3 5
Brønsted-Lowry Acids and Bases
Proton Transfer Reactions

Chapter 3 6
Brønsted-Lowry Acids and Bases
Conjugate Acid-Base Pairs
• 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.
• Consider HA(aq) + H2O(l) H3O+(aq) + A-(aq)
– After HA (acid) loses its proton it is converted into
A- (base). Therefore HA and A- are conjugate acid-
base pairs.
– After H2O (base) gains a proton it is converted into
H3O+ (acid). Therefore, H2O and H3O+ are conjugate
acid-base pairs.
• Conjugate acid-base pairs differ by only one proton.
Chapter 3 7
Brønsted-Lowry Acids and Bases
Relative Strengths of Acids
and Bases
• The stronger the acid, the
weaker the conjugate base.
• H+ is the strongest acid that
can exist in equilibrium in
aqueous solution.
• OH- is the strongest base
that can exist in equilibrium
in aqueous solution.

Chapter 3 8
Brønsted-Lowry Acids and Bases
Relative Strengths of Acids and Bases
• Any acid or base that is stronger than H+ or OH-
simply reacts stoichiometrically to produce H+
and OH-.
• The conjugate base of a strong acid (e.g. Cl-)
has negligible acid-base properties.
• Similarly, the conjugate acid of a strong base
has negligible acid-base properties.

Chapter 3 9
The Autoionization of Water
The Ion Product of Water
• In pure water the following equilibrium is
established
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
• at 25 C 
[H 3O ][OH ]-
Kc 
[H 2O]2

2 
K c [H 2O]  [H 3O ][OH ]-

 -
K w  [H 3O ][OH ]  1.0  10 14

• The above is called the autoionization of water.

Chapter 3 10
The pH Scale
• In most solutions [H+(aq)] is quite small.
• We define pH = -log[H+] = -log[H3O+]. Similarly
pOH = -log[OH-].
• In neutral water at 25 C, pH = pOH = 7.00.
• In acidic solutions, [H+] > 1.0  10-7, so pH < 7.00.
• In basic solutions, [H+] < 1.0  10-7, so pH > 7.00.
• The higher the pH, the lower the pOH, the more
basic the solution.
• Most pH and pOH values fall between 0 and 14.
• There are no theoretical limits on the values of
pH or pOH. (e.g. pH of 2.0 M HCl is -0.301)
Chapter 3 11
The pH Scale

Chapter 3 12
The pH Scale
Other “p” Scales
• In general for a number X,
pX   log X
• For example, pKw = -log Kw.
• Since  -  14
K w  [H 3O ][OH ]  1.0  10
 
pK w   log [ H 3O  ][OH - ]  14.00
  log[ H 3O  ]  log[OH - ]  14.00
pH  pOH  14.00

Chapter 3 13
The pH Scale
Measuring pH
• Most accurate method to measure pH is to use a
pH meter.
• However, certain dyes change color as pH
changes. These are indicators.
• Indicators are less precise than pH meters.
• Many indicators do not have a sharp color
change as a function of pH.
• Most indicators tend to be red in more acidic
solutions (two exceptions: phenolphthalein and
alizarin yellow R are both red in base).

Chapter 3 14
The pH Scale
Measuring pH

Chapter 3 15
Strong Acids and Bases
Strong Acids
• The strongest common acids are HCl, HBr, HI,
HNO3, HClO3, HClO4, and H2SO4.
• Strong acids are strong electrolytes.
• All strong acids ionize completely in solution:
HNO3(aq) + H2O(l)  H3O+(aq) + NO3-(aq)
• Since H+ and H3O+ are used interchangeably, we
write
HNO3(aq)  H+(aq) + NO3-(aq)

Chapter 3 16
Strong Acids and Bases
Strong Acids
• In solutions the strong acid is usually the only
source of H+. (If the molarity of the acid is less
than 10-6 M then the autoionization of water
needs to be taken into account.)
• Therefore, the pH of the solution is the initial
molarity of the acid.
Strong Bases
• Most ionic hydroxides are strong bases (e.g.
NaOH, KOH, and Ca(OH)2).

Chapter 3 17
Strong Acids and Bases
Strong Bases
• Strong bases are strong electrolytes and
dissociate completely in solution.
• The pOH (and hence pH) of a strong base is
given by the initial molarity of the base. Be
careful of stoichiometry.
• In order for a hydroxide to be a base, it must be
soluble.
• Bases do not have to contain the OH- ion:
O2-(aq) + H2O(l)  2OH-(aq)
H-(aq) + H2O(l)  H2(g) + OH-(aq)
N3-(aq) + H2O(l)  NH3(aq) + 3OH-(aq)
Chapter 3 18
Weak Acids
• Weak acids are only partially ionized in solution.
• There is a mixture of ions and unionized acid in
solution.
• Therefore, weak acids are in equilibrium:
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
HA(aq) H+(aq) + A-(aq)
[H 3O  ][A - ] [H  ][A - ]
Ka  or Ka 
[HA] [HA]

• Ka is the acid dissociation constant.

Chapter 3 19
Weak Acids

Chapter 3 20
Weak Acids
• Note [H2O] is omitted from the Ka expression.
(H2O is a pure liquid.)
• The larger the Ka the stronger the acid (i.e. the
more ions are present at equilibrium relative to
unionized molecules).
• If Ka >> 1, then the acid is completely ionized
and the acid is a strong acid.
Using Ka to Calculate pH
• Weak acids are simply equilibrium calculations.
• The pH gives the equilibrium concentration of
H+.
Chapter 3 21
Weak Acids
Using Ka to Calculate pH
• Using Ka, the concentration of H+ (and hence the
pH) can be calculated.
– Write the balanced chemical equation clearly showing
the equilibrium.
– Write the equilibrium expression. Find the value for Ka.
– Write down the initial and equilibrium concentrations
for everything except pure water. We usually assume
that the change in concentration of H+ is x.
• Substitute into the equilibrium constant
expression and solve. Remember to turn x into
pH if necessary.

Chapter 3 22
Weak Acids
Using Ka to Calculate pH
• Percent ionization is another method to assess
acid strength.
• For the reaction
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
[H  ]eqm
% ionization   100
[HA ]0
• Percent ionization relates the equilibrium H+
concentration, [H+]eqm, to the initial HA
concentration, [HA]0.

Chapter 3 23
Weak Acids
Using Ka to Calculate pH
• The higher percent ionization, the stronger the
acid.
• Percent ionization of a weak acid decreases as
the molarity of the solution increases.
• For acetic acid, 0.05 M solution is 2.0 % ionized
whereas a 0.15 M solution is 1.0 % ionized.

Chapter 3 24
Weak Acids
Using Ka to Calculate pH

Chapter 3 25
Weak Acids
Polyprotic Acids
• Polyprotic acids have more than one ionizable
proton.
• The protons are removed in steps not all at once:
H2SO3(aq) H+(aq) + HSO3-(aq) Ka1 = 1.7 x 10-2

HSO3-(aq) H+(aq) + SO32-(aq) Ka2 = 6.4 x 10-8

• It is always easier to remove the first proton in a
polyprotic acid than the second.
• Therefore, Ka1 > Ka2 > Ka3 etc.
• Most H+(aq) at equilibrium usually comes from the
first ionization (i.e. the Ka1 equilibrium).
Chapter 3 26
Weak Acids
Polyprotic Acids

Chapter 3 27
Weak Bases
• Weak bases remove protons from substances.
• There is an equilibrium between the base and
the resulting ions:
Weak base + H2O conjugate acid + OH-
• Example:
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
• The base dissociation constant, Kb, is defined as
[NH 4 ][OH - ]
Kb 
[NH 3 ]

Chapter 3 28
Weak Bases
• The larger Kb the stronger the base.

Chapter 3 29
Weak Bases
Types of Weak Bases
• Bases generally have lone pairs or negative
charges in order to attack protons.
• Most neutral weak bases contain nitrogen.
• Amines are related to ammonia and have one or
more N-H bonds replaced with N-C bonds (e.g.,
CH3NH2 is methylamine).
• Anions of weak acids are also weak bases.
Example: OCl- is the conjugate base of HOCl
(weak acid):
ClO-(aq) + H2O(l) HClO(aq) + OH-(aq) Kb = 3.3 x 10-7

Chapter 3 30
Relationship Between Ka and Kb
• We need to quantify the relationship between
strength of acid and conjugate base.
• When two reactions are added to give a third,
the equilibrium constant for the third reaction is
the product of the equilibrium constants for the
first two:
Reaction 1 + reaction 2 = reaction 3
has
K1  K2 = K3.

Chapter 3 31
Relationship Between Ka and Kb
• For a conjugate acid-base pair
Ka  Kb = Kw
• Therefore, the larger the Ka, the smaller the Kb.
That is, the stronger the acid, the weaker the
conjugate base.
• Taking negative logarithms:
pKa + pKb = pKw

Chapter 3 32
Acid-Base Properties of Salt Solutions
• Nearly all salts are strong electrolytes.
• Therefore, salts exist entirely of ions in solution.
• Acid-base properties of salts are a consequence
of the reaction of their ions in solution.
• The reaction in which ions produce H+ or OH- in
water is called hydrolysis.
• Anions from weak acids are basic.
• Anions from strong acids are neutral.
• Anions with ionizable protons (e.g. HSO4-) are
amphoteric.

Chapter 3 33
Acid-Base Properties of Salt Solutions
• To determine whether a salt has acid-base
properties we use:
– Salts derived from a strong acid and strong base are
neutral (e.g. NaCl, Ca(NO3)2).
– Salts derived from a strong base and weak acid are
basic (e.g. NaOCl, Ba(C2H3O2)2).
– Salts derived from a weak base and strong base are
acidic (e.g. NH4Cl, Al(NO3)3).
– Salts derived from a weak acid and weak base can be
either acidic or basic. Equilibrium rules apply!

Chapter 3 34
Acid-Base Behavior and Chemical Structure

Factors That Affect Acid Strength

Consider H-X. For this substance to be an acid we
need:
• H-X bond to be polar with H+ and X- (if X is a
metal then the bond polarity is H-, X+ and the
substance is a base),
• the H-X bond must be weak enough to be
broken,
• the conjugate base, X-, must be stable.

Chapter 3 35
Acid-Base Behavior and Chemical Structure

Binary Acids
• Acid strength increases across a period and
down a group.
• Conversely, base strength decreases across a
period and down a group.
• HF is a weak acid because the bond energy is
high.
• The electronegativity difference between C and
H is so small that the C-H bond is non-polar and
CH4 is neither an acid nor a base.

Chapter 3 36
Acid-Base Behavior and Chemical
Structure
Binary Acids

Chapter 3 37
Acid-Base Behavior and Chemical Structure

Oxyacids
• Oxyacids contain O-H bonds.
• All oxyacids have the general structure Y-O-H.
• The strength of the acid depends on Y and the
atoms attached to Y.
– If Y is a metal (low electronegativity), then the
substances are bases.
– If Y has intermediate electronegativity (e.g. I, EN =
2.5), the electrons are between Y and O and the
substance is a weak oxyacid.

Chapter 3 38
Acid-Base Behavior and Chemical Structure

Oxyacids
– If Y has a large electronegativity (e.g. Cl, EN =
3.0), the electrons are located closer to Y than
O and the O-H bond is polarized to lose H+.
– The number of O atoms attached to Y
increase the O-H bond polarity and the
strength of the acid increases (e.g. HOCl is a
weaker acid than HClO2 which is weaker than
HClO3 which is weaker than HClO4 which is a
strong acid).

Chapter 3 39
Acid-Base Behavior and Chemical
Structure
Oxyacids

Chapter 3 40
Acid-Base Behavior and Chemical Structure

Carboxylic Acids
• These are organic acids which contain a COOH
group (R is some carbon containing unit):
O
C
R OH

Chapter 3 41
Acid-Base Behavior and Chemical Structure

Carboxylic Acids
• When the proton is removed, the negative
charge is delocalized over the carboxylate
anion:
O O
C C
R O R O

• The acid strength increases as the number of

electronegative groups on R increases.
Chapter 3 42
Lewis Acids and Bases
• Brønsted-Lowry acid is a proton donor.
• Focusing on electrons: a Brønsted-Lowry acid
can be considered as an electron pair acceptor.
• Lewis acid: electron pair acceptor.
• Lewis base: electron pair donor.
• Note: Lewis acids and bases do not need to
contain protons.
• Therefore, the Lewis definition is the most
general definition of acids and bases.

Chapter 3 43
Lewis Acids and Bases
• Lewis acids generally have an incomplete octet
(e.g. BF3).
• Transition metal ions are generally Lewis acids.
• Lewis acids must have a vacant orbital (into
which the electron pairs can be donated).
• Compounds with p-bonds can act as Lewis
acids:
H2O(l) + CO2(g)  H2CO3(aq)

Chapter 3 44
 Lewis Acids and Bases
Hydrolysis of Metal Ions
• Metal ions are positively charged and attract
water molecules (via the lone pairs on O).
• The higher the charge, the smaller the metal ion
and the stronger the M-OH2 interaction.
• Hydrated metal ions act as acids:
Fe(H2O)63+(aq) Fe(H2O)5(OH)2+(aq) + H+(aq) Ka = 2 x 10-3
• The pH increases as the size of the ion
increases (e.g. Ca2+ vs. Zn2+) and as the charge
increases (Na+ vs. Ca2+ and Zn2+ vs. Al3+).

Chapter 3 45