Chemistry, The Central Science, 10th edition AP edition

Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten

Chapter 16: Acid-Base Equilibria (part I)

John D. Bookstaver, St. Charles Community College, St. Peters, MO,
 2006, Prentice Hall, Inc.

(ppt modified for our requirements)

Acids
and
Bases
Ch. 16 Acids-Base Resources and Activities
Equilibria • Textbook - chapter 16 & ppt file
• Online practice quiz
Sections 16.1-16.5 - Review
• Lab activities
Relationship between Ka and Kb • POGIL activities
• Chem Guy video lecture series on
Acid-Base properties of Salt solns Acids-Bases (many)
http://www.cosmolearning.com/video-lectures/acids-
Acid-Base behavior and and-bases-i-properties-of-molecular-neutral-ionic-
solutions/
molecular structure
• Chemtour videos from Norton
Lewis Acids and Bases • http://www.wwnorton.com/college/c
hemistry/gilbert2/contents/ch16/stu
Ch. 17 Additional Aspects dyplan.asp
of Aqueous • For titrations and indicator choices:
Equilibria • http://www.avogadro.co.uk/chemeq
m/acidbase/titration/phcurves.htm
Acids
and
Bases
Ch. 16 Acids-Base Resources and Activities
Equilibria • Textbook - chapter 17 & ppt file
• Online practice quiz
s
• Lab activities
• POGIL activities
Ch. 17 Additional Aspects
• Chem Guy video lecture series on
of Aqueous Acids-Bases (many)
Equilibria http://www.cosmolearning.com/video-lectures/acids-
and-bases-i-properties-of-molecular-neutral-ionic-
solutions/
• Common Ion effect, • Chemtour videos from Norton
• Buffered solutions,
• Acid-Base Titrations, • http://www.wwnorton.com/college/c
• Solubility Equilibria, hemistry/gilbert2/contents/ch16/stu
• Factors that affect dyplan.asp
solubility, • For titrations and indicator choices:
• Precipitation and • http://www.avogadro.co.uk/chemeq
Separation, m/acidbase/titration/phcurves.htm
• Qualitative Analysis for
Acids
Metallic Elements and
Bases
 Activities and Problem set for chapter 16 (due date_______)

Lab activities: Chapter 16 reading guide and

Titration of Weak Acid (wet lab) practice problems packet
Virtual labs from Independent work - students to view animations
& interactive activities (8 in total from
Norton) and write summary notes on each.
http://www.chem.iastate.edu/gro These summaries are to be included in your
up/Greenbowe/sections/projectfo portfolio. Some of these will be previewed in
class.
lder/animationsindex.htm
Norton Animations :
POGILS (5) : (Acid rain, acid-base ionization pH scale,
self-ionization of water, acid strength and
Introduction to Acids and Bases, molecular structure, buffers, strong acid-
strong base titration, titrations of weak
pH scale, acids)
Acid-Base Titrations,
Weak Acid-Base Equilibria, http://www.wwnorton.com/college/chemistry/gilbert
2/contents/ch16/studyplan.asp
Buffer Solutions.

Acids
Online practice quiz ch 16 due and
by_____ Bases
 Outline
Acids and Bases
• acids & base defn’s of Arrhenius,
Properties of Salt solutions
BrØnsted-Lowry, and Lewis; conjugate • BrØnsted-Lowry -Lowry acid-
acids and bases base properties of ions of a
• autoionization of water; salt
• pH scale and calculations;
• strong acids and bases;
• weak acids and bases
Structure and acid-base
behavior
Equilibrium Constants
• Factors affecting acid strength
• Acid-dissociation constant Ka for a weak
acid
• Kb for a weak base Lewis acids and bases
• Relationship between Ka and Kb and Kw
• Using Ka and Kb values to calculate
equilibrium concentrations, pH, %
ionization Acids
and
• Polyprotic acids Bases
 Some Definitions
• Arrhenius Acid: Substance that, when dissolved in water,
increases the concentration of hydrogen ions.
• Arrhenius Base: Substance that, when dissolved in water,
increases the concentration of hydroxide ions.

• Brønsted–Lowry Acid: Proton donor so it must have a

removable (acidic) proton.
• Brønsted–Lowry Base: Proton acceptor so it must have a
pair of nonbonding electrons.

Acids
and
Bases
If it can be either…

...it is amphiprotic.

HCO3−
HSO4−
H2O
Acids
and
Bases
What Happens When an Acid
Dissolves in Water?
• Water acts as a
Brønsted–Lowry base
and abstracts a proton
(H+) from the acid.
• As a result, the
conjugate base of the
acid and a hydronium
ion are formed.
Acids
and
Bases
 Conjugate Acids and Bases:

• From the Latin word conjugare, meaning “to

join together.”
• Reactions between acids and bases always
yield their conjugate bases and acids.

Acids
and
Bases
Acid and Base • Strong acids are
completely dissociated in
Strength water.
 Their conjugate bases are
quite weak.
• Weak acids only
dissociate partially in
water.
 Their conjugate bases are
weak bases.
• Substances with
negligible acidity do not
dissociate in water.
 Their conjugate bases are
exceedingly strong Acids
and
Bases
 Acid and Base Strength

In any acid-base reaction, the

equilibrium will favor the reaction that
moves the proton to the stronger base.

HCl(aq) + H2O(l)  H3O+(aq) + Cl−(aq)

H2O is a much stronger base than Cl−, so the

equilibrium lies so far to the right K is not
measured (K>>1). Acids
and
Bases
 Acid and Base Strength

HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2−(aq)

Acetate is a stronger base than H2O, so the

equilibrium favors the left side (K<1).

Acids
and
Bases
 Autoionization of Water

• As we have seen, water is amphoteric.

• In pure water, a few molecules act as
bases and a few act as acids.

H2O(l) + H2O(l) H3O+(aq) + OH−(aq)

• This is referred to as autoionization. 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
 pH

pH is defined as the negative base-10

logarithm of the hydronium ion
concentration.

pH = −log [H3O+]

Acids
and
Bases
• In pure water,

Kw = [H3O+] [OH−] = 1.0  10−14

• Because in pure water [H3O+] = [OH−],

[H3O+] = (1.0  10−14)1/2 = 1.0  10−7

• Therefore, in pure water,

pH = −log (1.0  10−7) = 7.00 Acids
and
Bases
 pH
• Therefore, in pure water,
pH = −log (1.0  10−7) = 7.00
• An acid has a higher [H3O+] than pure water,
so its pH is <7
• A base has a lower [H3O+] than pure water, so
its pH is >7.

Acids
and
Bases
 pH

These are
the pH
values for
several
common
substances.

Acids
and
Bases
 Other “p” Scales

• The “p” in pH tells us to take the

negative log of the quantity (in this case,
hydrogen ions).
• Some similar examples are
pOH = −log [OH−]
pKw = −log Kw

Acids
and
Bases
 Watch This!
Because
[H3O+] [OH−] = Kw = 1.0  10−14,
we know that

−log [H3O+] + −log [OH−] = −log Kw = 14.00

or, in other words,

pH + pOH = pKw = 14.00 Acids
and
Bases
How Do We Measure pH?
• For less accurate
measurements, one
can use
 Litmus paper
• “Red” paper turns
blue above ~pH = 8
• “Blue” paper turns
red below ~pH = 5
 An indicator

Acids
and
Bases
 How Do We Measure pH?

For more accurate

measurements, one
uses a pH meter,
which measures the
voltage in the
solution.

Acids
and
Bases
 Strong Acids
• You will recall that the seven strong acids are
HCl, HBr, HI, HNO3, H2SO4, HClO3, and
HClO4.

• These are, by definition, strong electrolytes

and exist totally as ions in aqueous solution.

• For the monoprotic strong acids,

[H3O+] = [acid].
Acids
and
Bases
 Strong Bases

• Strong bases are the soluble hydroxides,

which are the alkali metal and heavier
alkaline earth metal hydroxides (Ca2+, Sr2+,
and Ba2+).

• Again, these substances dissociate

completely in aqueous solution.

Acids
and
Bases
 Dissociation Constants

• For a generalized acid dissociation,

HA(aq) + H2O(l) A−(aq) + H3O+(aq)
the equilibrium expression would be
[H3O+] [A−]
Kc =
[HA]
• This equilibrium constant is called the
acid-dissociation constant, Ka. Acids
and
Bases
 Dissociation Constants

The greater the value of Ka, the stronger the

acid.

Acids
and
Bases
 Calculating Ka from the pH

• The pH of a 0.10 M solution of formic acid,

HCOOH, at 25°C is 2.38. Calculate Ka for
formic acid at this temperature.

• We know that
[H3O+] [COO−]
Ka =
[HCOOH]
Acids
and
Bases
 Calculating Ka from the pH

• The pH of a 0.10 M solution of formic acid,

HCOOH, at 25°C is 2.38. Calculate Ka for
formic acid at this temperature.
• To calculate Ka, we need the equilibrium
concentrations of all three things.
• We can find [H3O+], which is the same as
[HCOO−], from the pH.

Acids
and
Bases
Calculating Ka from the pH

pH = −log [H3O+]
2.38 = −log [H3O+]
−2.38 = log [H3O+]

10−2.38 = 10log [H3O+] = [H3O+]

4.2  10−3 = [H3O+] = [HCOO−]

Acids
and
Bases
 Calculating Ka from pH

Now we can set up a table…

[HCOOH], M [H3O+], M [HCOO−], M

Initially 0.10 0 0

Change −4.2  10-3 +4.2  10-3 +4.2  10−3

At 0.10 − 4.2  10−3 4.2  10−3 4.2  10−3

Equilibrium = 0.0958 = 0.10
Acids
and
Bases
Calculating Ka from pH

[4.2  10−3] [4.2  10−3]

Ka =
[0.10]

= 1.8  10−4

Acids
and
Bases
Calculating Percent Ionization
[H3O+]eq
• Percent Ionization =  100
[HA]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

Calculate the pH of a 0.30 M solution of acetic

acid, HC2H3O2, at 25°C.

HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2−(aq)

Ka for acetic acid at 25°C is 1.8  10−5.

Acids
and
Bases
 Calculating pH from Ka

The equilibrium constant expression is

[H3O+] [C2H3O2−]
Ka =
[HC2H3O2]

Acids
and
Bases
 Calculating pH from Ka

We next set up a table…

[HC2H3O2], M [H3O+], M [C2H3O2−], M

Initially 0.30 0 0
Change −x +x +x
At Equilibrium 0.30 − x  0.30 x x

We are assuming that x will be very small

Acids
compared to 0.30 and can, therefore, be ignored. and
Bases
 Calculating pH from Ka

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

pH = −log [H3O+]
pH = −log (2.3  10−3)
pH = 2.64

Acids
and
Bases
 Polyprotic Acids

• Have more than one acidic proton.

• If the difference between the Ka for the first
dissociation and subsequent Ka values is
103 or more, the pH generally depends only
on the first dissociation.

Acids
and
Bases
 Weak Bases

Bases react with water to produce hydroxide ion.

Acids
and
Bases
 Weak Bases

The equilibrium constant expression for

this reaction is

[HB] [OH−]
Kb =
[B−]

where Kb is the base-dissociation constant.

Acids
and
Bases
 Weak Bases

Kb can be used to find [OH−] and, through it, pH.

Acids
and
Bases
 pH of Basic Solutions

What is the pH of a 0.15 M solution of NH3?

NH3(aq) + H2O(l) NH4+(aq) + OH−(aq)

[NH4+] [OH−]
Kb = = 1.8  10−5
[NH3]

Acids
and
Bases
 pH of Basic Solutions

Tabulate the data.

[NH3], M [NH4+], M [OH−], M

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

Ka and Kb are related in this way:

Ka  Kb = Kw
Therefore, if you know one of them, you can
calculate the other. 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:

X−(aq) + H2O(l) HX(aq) + OH−(aq)

Acids
and
Bases
Reactions of Cations with Water

• Cations with acidic protons

(like NH4+) will lower the pH
of a solution.
• Most metal cations that are
hydrated in solution also
lower the pH of the solution.

Acids
and
Bases
Reactions of Cations with Water
• Attraction between nonbonding
electrons on oxygen and the
metal causes a shift of the
electron density in water.
• This makes the O-H bond more
polar and the water more acidic.
• Greater charge and smaller size
make a cation more acidic.
Acids
and
Bases
Effect of Cations and Anions

1. An anion that is the

conjugate base of a strong
acid will not affect the pH.
2. An anion that is the
conjugate base of a weak
acid will increase the pH.
3. A cation that is the
conjugate acid of a weak
base will decrease the pH.

Acids
and
Bases
 Effect of Cations and Anions

4. Cations of the strong

Arrhenius bases will not
affect the pH.
5. Other metal ions will
cause a decrease in pH.
6. When a solution contains
both the conjugate base
of a weak acid and the
conjugate acid of a weak
base, the affect on pH
depends on the Ka and Kb
values. Acids
and
Bases
 Factors Affecting Acid Strength

• The more polar the H-X bond and/or the weaker

the H-X bond, the more acidic the compound.
• Acidity increases from left to right across a row and
from top to bottom down a group. Acids
and
Bases
Factors Affecting Acid Strength
In oxyacids, in which
an OH is bonded to
another atom, Y, the
more
electronegative Y is,
the more acidic the
acid.

Acids
and
Bases
Factors Affecting Acid Strength

For a series of oxyacids, acidity increases

with the number of oxygens.
Acids
and
Bases
Factors Affecting Acid Strength
Resonance in the conjugate bases of
carboxylic acids stabilizes the base and
makes the conjugate acid more acidic.

Acids
and
Bases
 Lewis Acids

• Lewis acids are defined as electron-pair

acceptors.
• Atoms with an empty valence orbital can be Lewis
acids. Acids
and
Bases
 Lewis Bases

• Lewis bases are defined as electron-pair donors.

• Anything that could be a Brønsted–Lowry base is
a Lewis base.
• Lewis bases can interact with things other than
protons, however. Acids
and
Bases