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Chapter 16au
Chapter 16au
Chapter 16
Acids and Bases
Acids
and
Bases
Some Definitions
• Arrhenius
Acid: Substance that, when dissolved in
water, increases the concentration of
hydrogen ions.
Base: Substance that, when dissolved in
water, increases the concentration of
hydroxide ions.
Acids
and
Bases
HCl is an Arrhenius Acid.
HCl gas is a molecular compound
It is very soluble in water and producs
H+ ions
Concentrated acid is 37% by mass and
12M in concentration.
NaOH is an Arrhenius Base
It is an ionic compound
It is soluble in water and produces OH-
ions Acids
and
Bases
Some Definitions
• Brønsted–Lowry
Acid: Proton donor
Base: Proton acceptor
Acids
and
Bases
Certain substances can be
either…
...it is amphiprotic.
HCO3 −
HSO4−
H2O
Acids
and
Bases
A Brønsted–Lowry acid…
A Brønsted–Lowry base…
Acids
and
Bases
• NH3 is a Lowry base
Acids
and
Bases
H+ ion in water
Acids
and
Bases
• (a) What is the conjugate base of each of the following acids: HClO4,
H2S, PH4+, HCO3– ?
• (b) What is the conjugate acid of each of the following bases: CN–,
• SO4 2– , H2O, HCO3– ?
Acids
and
Bases
Acid and Base Strength
• Strong acids are
completely dissociated in
water.
Their conjugate bases are
quite weak.
• Weak acids only
dissociate partially in
water.
Their conjugate bases are
weak bases.
Acids
and
Bases
Acid and Base Strength
• Substances with
negligible acidity do not
dissociate in water.
Their conjugate bases are
exceedingly strong.
Acids
and
Bases
Acid and Base Strength
Acids
and
Bases
SAMPLE EXERCISE 16.3 Predicting the Position of a Proton-Transfer Equilibrium
For the following proton-transfer reaction, use Figure 16.4 to predict whether the equilibrium lies predominantly
to the left (that is, Kc < 1) or to the right (Kc > 1):
Acids
and
Bases
PRACTICE EXERCISE
For each of the following reactions, use Figure 16.4 to predict whether the equilibrium lies predominantly to the
left or to the right:
Acids
and
Bases
• About Amphoteric and Amphiprotic
Acids
and
Bases
Auto ionization of Water
Acids
and
Bases
Ion-Product Constant
The equilibrium expression for this process
is
Kc = [H3O+] [OH−]
This special equilibrium constant is
referred to as the ion-product constant
for water, Kw.
At 25°C, Kw = 1.0 × 10−14
Acids
and
Bases
At 25°C,
Kw = [OH-] [H3O+]
Remember H3O+ and H+ both can be used
interchangeably
= [OH-] [H+]
=1.0 × 10−14
Acids
and
Bases
SAMPLE EXERCISE 16.4 Calculating [H+] for Pure Water
Calculate the values of [H+] and [OH–] in a neutral solution at 25°C.
PRACTICE EXERCISE
Indicate whether solutions with each of the following ion concentrations are neutral,
acidic, or basic:
(a) [H+] = 4 × 10–9 M; (b) [OH–] = 1 × 10–7 M; (c) [OH–] = 7 × 10–13M.
Acids
and
Bases
pH
pH = −log [H3O+]
Acids
and
Bases
pH
• In pure water,
Acids
and
Bases
pH
These are
the pH
values for
several
common
substances.
Acids
and
Bases
• If the pH is say, 3.76
• pH = - log [H+] = 3.76
log [H+] = -3.76
[H+] = 10 -3.76 = 1.7 x 10-4
Acids
and
Bases
Other “p” Scales
Acids
and
Bases
Since
[H3O+] [OH−] = Kw = 1.0 × 10−14
Acids
and
Bases
How Do We Measure pH?
Acids
and
Bases
Strong Acids
• You will recall that the seven strong acids are
HCl, HBr, HI, HNO3, H2SO4, HClO3, and
HClO4.
Acids
and
Bases
Dissociation Constants
Acids
and
Bases
SAMPLE EXERCISE 16.10 Calculating Ka and Percent Ionization from
Measured pH
A student prepared a 0.10 M solution of formic acid (HCHO2) and measured its pH
using a pH meter. The pH at 25°C was found to be 2.38. (a) Calculate Ka for formic
acid at this temperature. (b) What percentage of the acid is ionized in this 0.10 M
solution?
Acids
and
Bases
SAMPLE EXERCISE 16.10 Calculating Ka and Percent Ionization from
Measured pH
A student prepared a 0.10 M solution of formic acid (HCHO2) and measured its pH
using a pH meter. The pH at 25°C was found to be 2.38. (a) Calculate Ka for formic
acid at this temperature. (b) What percentage of the acid is ionized in this 0.10 M
solution?
Acids
and
Bases
SAMPLE EXERCISE 16.10 Calculating Ka and Percent Ionization from
Measured pH
A student prepared a 0.10 M solution of formic acid (HCHO2) and measured its pH
using a pH meter. The pH at 25°C was found to be 2.38. (a) Calculate Ka for formic
acid at this temperature. (b) What percentage of the acid is ionized in this 0.10 M
solution?
Acids
and
Bases
SAMPLE EXERCISE 16.10 Calculating Ka and Percent Ionization from
Measured pH
A student prepared a 0.10 M solution of formic acid (HCHO2) and measured its pH
using a pH meter. The pH at 25°C was found to be 2.38. (a) Calculate Ka for formic
acid at this temperature. (b) What percentage of the acid is ionized in this 0.10 M
solution?
Acids
and
Bases
SAMPLE EXERCISE 16.10 Calculating Ka and Percent Ionization from
Measured pH
A student prepared a 0.10 M solution of formic acid (HCHO2) and measured its pH
using a pH meter. The pH at 25°C was found to be 2.38. (a) Calculate Ka for formic
acid at this temperature. (b) What percentage of the acid is ionized in this 0.10 M
solution?
Acids
and
Bases
Acids
and
Bases
We can now insert the equilibrium concentrations into the expression for Ka :
Check: The magnitude of our answer is reasonable because Ka for a weak acid is usually between 10–3 and
10–10.
Acids
and
Bases
PRACTICE EXERCISE
Niacin, one of the B vitamins, has the following molecular structure:
A 0.020 M solution of niacin has a pH of 3.26. (a) What percentage of the acid is ionized in this solution?
(b) What is the acid-dissociation constant, Ka, for niacin?
Acids
and
Answers: (a) 2.7%, (b) 1.5 × 10–5 Bases
Calculating Ka from the pH
• We know that
[H3O+] [HCOO−]
Ka =
[HCOOH]
Acids
and
Bases
Calculating Ka from the pH
Acids
and
Bases
Calculating Ka from the pH
pH = −log [H3O+]
2.38 = −log [H3O+]
−2.38 = log [H3O+]
Acids
and
Bases
Calculating Ka from pH
Initially 0.10 0 0
= 1.8 × 10−4
Acids
and
Bases
Calculating Percent Ionization
[H3O+]eq
• Percent Ionization = [HA] × 100
initial
• In this example
[H3O+]eq = 4.2 × 10−3 M
[HCOOH]initial = 0.10 M
Acids
and
Bases
Calculating Percent Ionization
4.2 × 10−3
Percent Ionization = × 100
0.10
= 4.2%
Acids
and
Bases
Calculating pH from Ka
Acids
and
Bases
Calculating pH from Ka
[H3O+] [C2H3O2−]
Ka =
[HC2H3O2]
Acids
and
Bases
Calculating pH from Ka
Initially 0.30 0 0
Change −x +x +x
At Equilibrium 0.30 − x ≈ 0.30 x x
Now,
(x)2
1.8 × 10−5 =
(0.30)
(1.8 × 10−5) (0.30) = x2
5.4 × 10−6 = x2
2.3 × 10−3 = x
Acids
and
Bases
Calculating pH from Ka
Now
pH = −log [H3O+]
pH = −log (2.3 × 10−3)
pH = 2.64
Acids
and
Bases
• Percent ionization of HC2H3O2
= 0.0023M x 100 = 0.77%
0.30
Acids
and
Bases
Something Very Important
Acids
and
Bases
• The percent ionization of the weak acid
decreases as the concentration increases.
Acids
and
Bases
SAMPLE EXERCISE 16.12 Using Ka to Calculate Percent Ionization
When we try solving this equation using the approximation 0.10 – x = 0.10 (that is, by neglecting the
concentration of acid that ionizes in comparison with the initial concentration), we obtain
Acids
and
Bases
SAMPLE EXERCISE 16.12 continued
Because this value is greater than 5% of 0.10 M, we should work the problem without the approximation, using
an equation-solving calculator or the quadratic formula. Rearranging our equation and writing it in standard
quadratic form, we have
Of the two solutions, only the one that gives a positive value for x is chemically reasonable. Thus,
Acids
and
Bases
SAMPLE EXERCISE 16.12 continued
Acids
and
Bases
It is what we would expect from Le Châtelier’s principle. • There are
more “particles” or reaction components on the right side of the
equation than on the left. Dilution causes the reaction to shift in the
direction of the larger number of particles because this counters the
effect of the decreasing concentration of particles.
Acids
and
Bases
Polyprotic Acids
Acids
and
Bases
Ascorbic Acid
H2C6H6O6
Citric Acid
H3C6H5O7
Acids
and
Bases
Weak Bases
Acids
and
Bases
Weak Bases
[NH4+] [OH−]
Kb =
[NH3]
Acids
where Kb is the base-dissociation constant. and
Bases
Weak Bases
Acids
and
Bases
pH of Basic Solutions
[NH4+] [OH−]
Kb = = 1.8 × 10−5
[NH3]
Acids
and
Bases
pH of Basic Solutions
Initially 0.15 0 0
At Equilibrium 0.15 - x ≈ 0.15 x x
Acids
and
Bases
pH of Basic Solutions
(x)2
1.8 × 10−5 =
(0.15)
(1.8 × 10−5) (0.15) = x2
2.7 × 10−6 = x2
1.6 × 10−3 = x2
Acids
and
Bases
pH of Basic Solutions
Therefore,
[OH−] = 1.6 × 10−3 M
pOH = −log (1.6 × 10−3)
pOH = 2.80
pH = 14.00 − 2.80
pH = 11.20
Acids
and
Bases
Ka and Kb
(b) Kb for NH3 is listed in Table 16.4 and in Appendix D as Kb = 1.8 × 10–5. Using Equation 16.40, we can
calculate Ka for the conjugate acid, NH4+:
Acids
and
Bases
Acid-Base properties of salt
solutions
Acids
and
Bases
• About the discussion on Monday at
11:30!
Acids
and
Bases
Reactions of Anions with Water
• Anions are bases.
• As such, they can react with water in a
hydrolysis reaction to form OH− and the
conjugate acid:
Acids
and
Bases
• If the anion is a base
of a strong acid then
it will be a weak
base and will have
little tendency to
abstract proton from
water.
• Consequently it will
not affect the pH of
the solution.
Acids
and
Bases
• If the anion belongs
to a weak acid it will
consequently be a
relatively strong
base and will
release the OH – ion
from water making it
basic
Acids
and
Bases
Reactions of Cations with Water
• Cations with acidic protons
(like NH4+) will lower the pH of
a solution, by donating a
proton to the water molecule.
Acids
and
Bases
Effect of Cations and Anions
Acids
and
Bases
Binary Acids
• Binary acids are acids between a proton
and one more element.
• In general the H-X bond strength is the
most important factor in determining the
acid strength between the binary acids
of the same group of the periodic table.
Acids
and
Bases
• Bond strength decreases and so acidity increases
down a group.
• Across a group the bond strength does not change
much, so the bond polarity is the factor determining
the acidity across a row.
Acidity increases as the electro negativity increases.
Acids
• Acidity increases from left to right across a row and and
from top to bottom down a group. Bases
Oxyacids
O
H-O -S- O-H
O
H2SO4
In oxyacids, the Y is a
nonmetal and the more
electronegative Y is, the
more acidic the acid.
.
Acids
and
Bases
This happens because:
a. the electron density is drawn towards Y
and it makes the O-H bond weaker.
b. The conjugate base of the acid is an
anion and its stability increases as the
electronegativity of Y increases.
Acids
and
Bases
Factors Affecting Acid Strength
Acids
and
Bases
Lewis Acids