Acid–Base Equilibria

1006727 General Chemistry

01006708 Chemistry

Brown Chemistry:The Central Science

13th Edition Chapter 16 (c) 2014
 Acids

• The Swedish physicist and

chemist S. A. Arrhenius defined
acids as substances that
increase the concentration of
H3O+ when dissolved in water.

• Both the Danish chemist J. N.

Brønsted and the British
chemist T. M. Lowry defined
them as proton (H+) donors.

2
 Bases
• Arrhenius defined bases
as substances that
increase the concentration
of OH− when dissolved in
water.

• Brønsted and Lowry

defined them as proton
acceptors.

3
 Some Definitions
1. Arrhenius Acid/Base
– An acid is a substance that, when dissolved in water, increases
the concentration of hydrogen ions.
– A base is a substance that, when dissolved in water, increases
the concentration of hydroxide ions.
Acid Base
2. Brønsted–Lowry Acid/Base 1. HA +H2O→ A- + H3O+
– An acid is a proton donor. 2. HA + X → A- + HX+
– A base is a proton acceptor.
3. XAn + Z → A:n-1 + XZ+

3. Lewis Acid/Base
– An acid is an electron pair acceptor (i.e. will give a proton)
– A base is an electron pair donator (i.e. wan accept a proton)

4
 What Is Different about Water?

• Water can act as a Brønsted–Lowry base and accept a

proton (H+) from an acid, as on the previous slide.
– It can also donate a proton and act as an acid, as is
seen below.
– This makes water amphiprotic.

5
 Conjugate Acids and Bases
• The term conjugate means “joined together as a pair.”
– Reactions between acids and bases always yield their
conjugate bases and acids.

6
 Acids & Bases
• (a) What is the conjugate base • (b) What is the conjugate acid
of HClO4, H2S, PH4+, HCO3- ? of CN-, SO42-, H2O, HCO3- ?

– ClO4- – HCN
– HS- – HSO4-
– PH3 – H3O+
– CO32- – H2CO3

7
 Acids & Bases
• The hydrogen sulfite ion
(HSO3-2) is amphiprotic. Write
(a) HSO3-(aq) + H2O(l) → SO32-(aq) + H3O+(aq)
an equation for the reaction
with water Acid Base conjugate base conjugate acid

• (a) in which the ion acts as an

acid and (b) in which the ion
acts as a base. (b) HSO3- (aq) + H3O+(l) → H2SO3(aq) + H2O(aq)
Base Acid conjugate acid conjugate base

• In both cases identify the

conjugate acid–base pairs.

8
 Relative Strengths of Acids
and Bases
• Acids above the line
with H2O are strong
acids; their conjugate
bases do not act as
bases in water.

• Bases below the line

with H2O are strong
bases; their
conjugate acids do
not act as acids in
water.

9
 Proton Transfer
• Predict whether the
equilibrium lies to the left
or right for the following:
HSO4-(aq) + CO32-(aq) ⇌ SO42- (aq) HCO3-(aq)
Acid Base conjugate base conjugate acid

• Which is the strongest Acid HSO4- or HCO3-

• The reaction will equilibrium will lie to the right.

HSO4- is a stronger acid than HCO3-.

10
 Strong or Weak?
• Strong acids completely dissociate in water; weak acids
only partially dissociate.
• Strong bases dissociate to metal cations and hydroxide
anions in water; weak bases only partially dissociate to
produce hydroxide anions.

11
 Acid and Base Strength
• In every acid–base reaction, equilibrium favors
transfer of the proton from the stronger acid to the
stronger base to form the weaker acid and the
weaker base.

– H2O is a much stronger base than Cl, so the equilibrium

lies far to the right (K >> 1).

HCl(aq) + H2O(l) → H3O+(aq) + Cl(aq)

– Acetate is a stronger base than H2O, so the equilibrium

favors the left side (K < 1).

CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO–(aq)

12
 Autoionization of Water
• Water is amphoteric. In pure water, a few
molecules act as bases and a few act as acids.
• This is referred to as autoionization of water.

13
 Ion Product Constant
• The equilibrium expression for this process is (note
[H2O] is constant so does not appear).

Kc = Kw = [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

• FYI 1 L of water ~1000g at STP. MWT water = 18
g/mol, so 1 L of water =55.5 mol.

14
 Aqueous Solutions Can Be
Acidic, Basic, or Neutral
• If a solution is neutral, [H+] = [OH–].
• If a solution is acidic, [H+] > [OH–].
+ –
• If a solution is basic, [H ] < [OH ].

15
 [H+] Calculation
• Calculate the values of [H+]
and [OH-] in a neutral aqueous
solution at 25 °C.

+ - -14

2 -14

-7

16
 [H+] Calculation
• Calculate the concentration of
[H+] at 25 °C in: [H+][OH-] = 1.0x10-14

• (a) a solution in which [OH-] is (a)

0.010 M [H+][0.010 M] = 1.0x10-14

1.0x10−14 M
[H+]= =1.0x10 -12
0.010 M
• (b) a solution in which [OH-] is
1.8x10-9 M.
basic solution

(b)
[H+][1.8x10-9 M] = 1.0x10-14

1.0x10−14 𝑀
[H+]= 1.8x10−9 M =5.6x10-6

Acidic solution

17
 pH

• The pH scale is
a method of
reporting [H+]
• pH = –log[H+]
– Neutral pH = 7.00.
– Acidic pH is < 7.00.
– Basic pH is > 7.00.

18
 Other “p” Scales
• The “p” in pH tells us to take
the –log of a quantity (in this
case, hydrogen ions).

[H3O+][OH] = Kw = 1.0  1014

Calculate pH of basic Soln

• we can take the -log to give • Calculate the pH of a solution

of a solution containing 2x10-3
mol of NaOH.
–log[H3O+] + –log[OH] =
–log Kw = 14.00
pH + pOH = pKw = 14.00

• which results in pOH = -log(2x10-3) = 2.69

pH = 14.00 - 2.69
pH + pOH = pKw = 14.00 = 11.30

19
 pH and pOH
• Calculate the pH values for the • A sample has a pOH=10.24.
following solutions. Calculate [H+].
a. [H+]= 1.0x10-12
b. [H+]= 5.6x10-6

pH = -log[H+]
pH = -log[H+] = 14.00 - pOH
a. pH = -log[1.0x10-12]= 12
pH = 14.00 - 10.24 = 3.76

b. pH = -log[5.6x10-6]= 5.3 [H+] = 10-3.76 = 1.7x10-4 M

20
 How Do We Measure pH?
• Indicators, including
litmus paper, are used for
less accurate
measurements of pH; an
indicator is one color in its
acid form and another
color in its basic form.
• pH meters are used for
accurate measurement of
pH; electrodes
indicate small
changes in voltage
to detect pH.

21
 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; e.g.,

HA + H2O → H3O+ + A–

• For monoprotic strong acids,

[acid] = [H3O+]

22
 Weak Acids
• For a weak acid, the equation for its dissociation is

HA(aq) + H2O(l) H3O+(aq) + A–(aq)

• Since it is an equilibrium, there is an equilibrium constant

related to it, called the acid-dissociation constant, Ka

• The greater the value of Ka,

the stronger is the acid.
• Weak acids/bases only
partially dissociate.

Ka = [H3O+][A–] / [HA]

23
 Acid Strength
• The strength of an acid
depends on how easily
the proton, H+ , is lost or
removed from an H-X
bond in the acid species.
• Two factors are important
in determining relative
acid strengths.
– One is the polarity of the
bond to which the H atom
is attached. T
– The second factor
determining acid strength is
the strength of the bond

24
 Ionization & Bond Strength

• If the electronegativity of • For a series of oxoacids

atom Y is large, the H-O below, the acid strength
increases with the number of
bond is relatively weak O atoms bonded to Cl.
and the acid strength is
strong.
– HClO, HBrO, and HIO, The
electronegativity of Group
VIIA elements decreases
going down the column of
elements Cl > Br > I.
– The order of acid strengths
is HIO < HBrO < HClO

25
 Acid Strength
• Going down a column of
elements of the periodic table,
the size of atom X increases.
– The HX bond strength
decreases, the strength of the
acid increases.

• Going across a row of

elements of the periodic table,
the electronegativity increases
– The HX bond polarity increases,
and the acid strength increases.

26
 Binary Acids
• Binary acids consist of
H and one other element.

• Within a group, H-A bond

strength is generally the
most important factor.

• Within a period, bond

polarity is the most
important factor to
determine acid strength.

27
 Carboxylic Acids

• Carboxylic acids are organic acids containing

the -COOH group.
• Factors contributing to their acidic behavior:
Other O attached to C draws electron density
from O-H bond, increasing polarity.
Its conjugate base (carboxylate anion) has
resonance forms to stabilize the anion.

28
 Strong vs. Weak Acids -
Another Comparison
• Strong Acid: [H+]eq = [HA]init
• Weak Acid: [H+]eq < [HA]init

• This creates a difference in conductivity and in

rates of chemical reactions.

29
 Calculations
• A 0.10 M solution of formic acid, HCOOH, at 25 C has a pH=2.38.
Calculate Ka for formic acid at this temperature.

[H3O+][HCOO–]
Ka = pH=-log[H+]
[HCOOH]

• We need the equilibrium [conc] of all three entities.

– [H3O+] = [HCOO–] = 10–2.38 = 4.2 × 10–3

[HCOOH], M [H3O+], M [HCOO], M

Initially 0.10 0 0
Change 4.2  103 +4.2  103 +4.2  103

0.10  4.2  103

At equilibrium 4.2  103 4.2  103
= 0.0958 = 0.10
30
 Calculating Ka from pH

• This allows us to calculate Ka by putting

in the equilibrium concentrations.
[4.2  103][4.2  103]
Ka = [0.10]

= 1.8  104

[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 equilibrium 0.10 4.2  103 4.2  103

31
 Calculating Percent Ionization
[H3O+]eq
• Percent ionization = [HA]initial
x 100

• In this example:

[H3O+]eq = 4.2  103 M

[HCOOH]initial = 0.10 M

4.2 x 10-3 x 100 = 4.2%

• Percent ionization =
0.1

32
 % ionization
• Calculate the percentage of the
acid that is ionized in a 0.250 M
solution of acid has a pH of 1.89.

pH=-log(H+)

10-1.89 = 0.0129 M

[ ] 0.0129M
%ionization= = *100= 8.6%
[ ] 0.150 M

33
 Method to Calculate pH Using Ka

1) Write the chemical equation for the ionization

equilibrium.
2) Write the equilibrium constant expression.
3) Set up a table for Initial/Change in/Equilibrium
concentration to determine equilibrium
concentrations as a function of change (x).
4) Substitute equilibrium concentrations into the
equilibrium constant expression and solve for x.
(note, you can make assumptions if H+<< HA)

34
 Example
• Calculate the pH of a 0.30 M solution of acetic
acid, HC2H3O2, at 25 C.
HC2H3O2 + H2O H3O+ + C2H3O2–
Ka = [H3O+][C2H3O2–] / [HC2H3O2]

CH3COOH (M) H3O+ (M) CH3COO– (M)

Initial
0.30 0 0
Concentration (M)

Change in
–x +x +x
Concentration (M)

Equilibrium
0.30 – x x x
Concentration (M)

35
 Example (concluded)
Ka = [H3O+][C2H3O2–] / [HC2H3O2] = 1.8 × 10–5
= x2 / (0.30 – x) = 1.8 × 10–5

1. We can solve quadratic eqn (x2 + 1.8x10-5x - 5.4x10-5) OR

2. Since, acetic acid is a weak acid x << 0.30, so eqn can simplify.

Ka = x2 / 0.30 = 1.8 × 10–5

x2 = 5.4 × 10–6
x = 2.3 × 10–3

x = [H3O+], so pH = –log(2.3 × 10–3) = 2.63

36
 Calculation of pH from Ka
• Calculate the pH of a 0.20 M solution
of HCN. Ka =
[ ]
Ka= =
[ ] [ . ]
- +
x << 0.2 so can neglect it (if not solve
quadratically)
[ ]
K a= =
[ ] [ . ]

HCN CN- H+

Initial M 0.20 M 0 0

Change M -x +x +x

Final M 0.20 - x x x

37
 Polyprotic Acids
• Polyprotic acids have more than one acidic proton.
• It is always easier to remove the first proton than
any successive proton.
• If the factor in the Ka values for the first and second
dissociation has a difference of 3 or greater, the pH
generally depends only on the first dissociation.

38
 Ionization of Polyprotic Acids
• The solubility of CO2 in water at 25 °C and 0.1 Ionization 1
atm is 0.0037 M. Assume that all the dissolved
CO2 is in the form of carbonic acid. H2CO3 is Ka1=
[ ]
= = 4.3𝑥10
Ka1=4.3x10-7, Ka2=5.6x10-11. What is the pH of a [ ] ( . )

0.0037 M solution of H2CO3? As Ka1 is small, we simplify by assuming x is small

CO2(aq) + H2O(l) → H2CO3(aq) 𝑥2

= 4.3𝑥10
(0.0037)
H2CO3(aq) ⇌ HCO3- (aq) + H+(aq) x = (4.3𝑥10 ) (0.0037) =4.0x10-5
HCO3-(aq) ⇌ CO3-2 (aq) + H+(aq)
pH=-log[H+]=-log(4.0x10−5)= 4.40

[ ]
Ionization 1 H2CO3 HCO3- H+ %ionization = [ ]
*100=(4.0x
.
)
*100 = 1.1%

Initial M 0.0037 M 0 0
Ionization 2
Change M -x +x +x [ ]
Ka2=
[ ]

Final M 0.0037M - x x x
we simplify by assuming x is small

[ ] ( . )
Ka2= = = 5.6𝑥10
Ionization 2 HCO3 - CO3-2 H+ [ ] ( . )

y= 5.6𝑥10 = [CO32-]
Initial M 4.0x10-5 0 4.0x10-5

Change M -y +y +y Second ionization is negligible

Final M 4.0x10-5 - y y 4.0𝑥10 +y

39
 Strong Bases
• Strong bases are the soluble hydroxides - alkali
metals and heavier alkaline earth metal hydroxides
(Li+, Na+, K+, Ca2+, Cs+, Sr2+, and Ba2+).

• Again, these substances dissociate completely in

aqueous solution; e.g.,

MOH(aq) → M+(aq) + OH–(aq)

M(OH)2(aq) → M2+(aq) + 2 OH–(aq)

• For monoprotic strong bases,

[base] = [OH-]

40
 Weak Bases

• Ammonia, NH3, is a weak base.

– Like weak acids, weak bases have an
equilibrium constant called the base
dissociation constant.
– Equilibrium calculations work the same as for
acids, using the base dissociation constant
instead.

41
Base Dissociation Constants

42
 Relationship between Ka and Kb

• For a conjugate acid–base pair, Ka and Kb are

related in this way:
Ka × Kb = Kw = 1x10-14
• Therefore, if you know one of them, you can
calculate the other.
– Sometimes only one or the other is available.

43
 Additional Calculation
• Determine dissociation constants
for (a) F-, the conjugate base of
HF, and (b) NH4+, the conjugate
acid of NH3.
– HF, Ka = 6.8x10-4.
– NH3, Kb = 1.8x10-5.

𝑤
•
.

•
.

44
 Types of Weak Bases
Two main categories

1) Neutral substances with

an atom that has a
nonbonding pair of
electrons that can accept
H+ (i.e. amines)

2) Anions of weak acids

(conjugate bases).

45
 Example

What is the pH of 0.15 M NH3 Kb= 1.8 × 10–5?

NH3 + H2O NH4+ + OH–

Kb = [NH4+][OH–] / [NH3] = 1.8 × 10–5

NH3 (M) NH4+ (M) OH– (M)

Initial
Concentration (M)
0.15 0 0

Change in
Concentration (M)
–x +x +x

Equilibrium
Concentration (M)
0.15 – x x x
46
 Example (completed)
Substituting the values into the equilibrium expression:

Kb = 1.8 × 10–5 = x2 / (0.15 – x)

1. We can solve the quadratic equation OR

2. Since x << 0.15, the equation simplifies to:

Kb = 1.8 × 10–5 = x2 / 0.15

x2 = 0.15*1.8 x 10–5
x = 1.6 × 10–3

pOH = -log([OH-]) = 2.80

pH = [14.00 – pOH] = 11.20

47
 % ionization from Ka
• Calculate the pH and percentage
[ ]
of HF molecules ionized in a 0.10 Ka=
[ ]
=( . )
= 6.8𝑥10

M HF solution. Ka = 6.8x10-4.
* X is not negligible compared to [HF]

- + x2= 6.8𝑥10 (0.10-x)

x2+ 6.8𝑥10 x - 6.8𝑥10

−6.8𝑥10 ± (6.8𝑥10 ) −4(1)(6.8𝑥10 )

𝑥=
2(1)

. ± .
𝑥= = 7.9𝑥10

HF F- H+
pH=-log[H+]=-log(7.9𝑥10 )= 2.10
Initial M 0.10 M 0 0
[ ] ( . )
%ionization = *100= ( . *100=7.9%
Change M -x +x +x [ ] )

Final M 0.10M - x x x

48
 Additional Calculations
• Calculate the concentration of OH- in a
0.15 M solution of NH3. kb NH3= 1.8x10-5
[ ]
Kb=
[ ]
=( . )
= 1.8𝑥10
NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH-(aq)

As Kb is small, we can simplify by assuming x is small

𝑥2
= 1.8𝑥10
(0.15)

x = (1.8𝑥10 ) (0.15) = 1.6𝑥10 𝑀 = [𝑂𝐻 ]

NH3 NH4+ OH-

Initial M 0.15 M 0 0
%ionization =
[ ]
*100=(1.6x. )
*100 = ~1%
[ ]

Change M -x +x +x

Final M 0.15 - x x x

49
 Lewis Acid/Base Chemistry
• Lewis acids are electron
pair acceptors.
• Lewis bases are electron
pair donors.

• All Brønsted–Lowry acids

and bases are also called
Lewis acids and bases.

• There are compounds

which do not meet the
Brønsted–Lowry
definition which meet the
Lewis definition.

50
 Acid Base Properties of
Salt Solutions
• A salt may be regarded • The hydrolysis of an ion
as an ionic compound is the reaction of an ion
obtained by a with water to produce the
neutralization reaction in conjugate acid and
aqueous solution. hydroxide ion or the
– The resulting salt solution conjugate base and
may be neutral, but often it hydronium ion.
is acidic or basic – CN- ion hydrolyzes to give
the conjugate acid and OH-
– NH4+ hydrolyzes to give the
conjugate base H3O+

51
 Summary of Salts
1. A salt of a strong base and a strong acid.
– The salt has no hydrolyzable ions and so gives a neutral
aqueous solution. An example is NaCl.
2. A salt of a strong base and a weak acid.
– The anion of the salt is the conjugate of the weak acid. It
hydrolyzes to give a basic solution. An example is NaCN.
3. A salt of a weak base and a strong acid.
– The cation of the salt is the conjugate of the weak base. It
hydrolyzes to give an acidic solution. An example is NH4Cl.
4. A salt of a weak base and a weak acid.
– Both ions hydrolyze. Whether the solution is acidic or basic
depends on the relative acid–base strengths of the two ions.
– You need to compare the Ka of the cation with the Kb of the
anion. If the Ka is larger, the solution is acidic. If the Kb is larger,
it is basic.

52
 Additional Calculations
• A 2L solution of hypochlorite
(NaClO) has a pH of 10.50. pOH = 14.00 - pH = 14.00 - 10.50 = 3.50

Calculate the number of moles of [OH-] = 10-3.50 = 3.2x10-4 M

NaClO added to the water.
Kb=3.3x10-7.
[ ] .
Kb= =( = 3.3x10
ClO-(aq) + H2O(l) ⇌ HClO(aq) + OH-(aq) [ ] . )

.
x= ( . )
+ 3.2𝑥10 =0.31 M

ClO- HClO OH- 0.31 mol/L * 2 L

0.62 moles must be added
Initial M x 0 0

Change M - 3.2x10-4 +3.2x10-4 +3.2x10-4

Final M x - 3.2x10-4 3.2x10-4 3.2x10-4

53
 Hydrated Cations
• Transition and post-transition metals form hydrated
cations in solution.
• The water attached to the metal is more acidic than free
water molecules, making the
hydrated ions acidic.

54