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IV.

Acids and Bases


Properties of Acids and Bases
Acids
pH<7.0
taste sour
react with metals to produce hydrogen gas
pH paper turns red/pink
phenolphthalein colourless
bromothymol blue yellow

Bases
pH>7.0
taste bitter
feel slippery
pH paper turns blue/green
phenolphthalein pink
bromothymol blue blue

pH and pOH
pH (power of hydrogen) is a measure of the acidity of a solution: the lower the pH, the more acidic the solution is and the
higher the pH, the more basic the solution is. A solution is acidic when pH<7 and [H+]>[OH]. A solution is basic when pH>7
and [H+]<[OH].
pOH is a measure of the basicity (or alkalinity) of a solution: the lower the pOH, the more basic the solution is and the higher
the pOH, the more acidic the solution is.
pH or pOH = 7.0 indicates a neutral solution.
The pH Scale

Arrhenius Concept
Acid: substance that will dissociate to give H+ ions.
Base: substance that will dissociate to give OH ions.
The Ahhrenius concept provides a good description of strong acids and bases
Strength of Acids and Bases
The strength of acids and bases is a measure of the degree of dissociation/ionization; a strong acid or base will completely
dissociate in water.
Strong Acids:
HCl H+ + Cl
HBr H+ +Br
HI H+ + I
HClO4 H+ + ClO4

hydrochloric acid
hydrobromic acid
hydroiodic acid
perchloric acid

HNO3 H+ + NO3
HIO4 H+ + IO4
H2SO4 H+ + HSO4
HClO3 H+ + ClO3

Strong Bases:
LiOH Li+ + OH
NaOH Na+ + OH
KOH K+ + OH
RbOH Rb+ + OH
CsOH Cs+ + OH

lithium hydroxide
sodium hydroxide
potassium hydroxide
rubidium hydroxide
cesium hydroxide

Ba(OH)2 Ba2+ + 2OH


barium hydroxide
2+

Sr(OH)2 Sr + 2OH
strontium hydroxide
Ca(OH)2 Ca2+ + 2OH
calcium hydroxide
(note: other group II elements are insoluble in water)

Calculations for Strong Acids and Bases


pH = log[H+]
[H+] = 10pH
pH + pOH =14.00
1.0x1014 = [H+] [OH]

pOH = log[OH]
[OH] = 10pOH

nitric acid
periodic acid
sulphuric acid
chloric acid

pH, pOH, and Significant Figures


For pH and pOH, only the digits after the decimal place are significant.
(ie, pH= 10.20 has two significant digits since there are two numbers after the decimal place; pOH = 1.384 has three significant
digits since there are three numbers after the decimal place)
ex. A solution has an [H+] of 0.040 M, calculate the pH.

pH = log[H+] = log(0.040) = 1.40

ex. A solution has an [OH] of 6.5x105 M, calculate the pOH.

pOH = log[OH] = log(6.5x105) = 4.19

ex. acid rain has a pH of 4.80, calculate the [H+].

[H+] = 10pH = 104.80 = 1.5x105 M

ex. ammonia has a pOH of 3.78, calculate the [OH]

[OH] = 10pOH = 103.78 = 1.7x104 M

ex. calculate the [H+], pH, pOH, and [OH] of 0.0020 M HCl
HCl H+ + Cl
therefore, [H+] = 0.00200 M

pH = log[H+]
= log(0.0020)
= 2.70

pH + pOH = 14.00
2.20 + pOH = 14.00
pOH = 11.30

[H+][OH] = 1.0x1014
(0.0020) [OH] = 1.0x1014
[OH] = 5.0x1012 M

pH + pOH = 14.00
pH + 1.70 = 14.00
pH = 12.30

[H+][OH] = 1.0x1014
[H+][0.020] = 1.0x1014
[H+] = 5.0x1013 M

ex. calculate the [OH], pOH, pH, and [H+] of 0.010 M Sr(OH)2
Sr(OH)2 Sr2+ + 2OH
therefore, [OH] = 2(0.010 M)
= 0.020 M

pOH = log[OH]
= log (0.020)
= 1.70

The Ahhrenius Concept does not adequately describe some compounds that exhibit acidic or basic properties, so a more general
definition is required.
BronstedLowry Model
Acid: a proton (H+) donor
Conjugate acid: has one more proton

Base: a proton (H+) acceptor


Conjugate base: has one few proton

Acid/Base Equilibria
A weak acid or base is one that does not completely dissociate in water; instead it forms an equilibrium with water.
Acids:

H3O+ (aq) + A (aq)


conjugate
conjugate
acid
base

HA (aq) + H2O (l)


acid
base

note: The proton is donated by the acid (HA) and accepted by the base (H2O). The conjugate acid of water is the hydronium ion
(H3O+) which has one additional proton and the conjugate base of HA is A which has one fewer proton..
The equilibrium expression for this reaction can be written as follows:

Ka

[ H 3O ][ A ]
[ HA]

Where Ka is the acid dissociation constant.

The acid dissociation constant can also be expressed as pKa where pKa = log(Ka) or K a 10
Bases:

B (aq) + H2O (l)


base
acid

pKa

OH (aq) + BH+ (aq)


conjugate
conjugate
base
acid

note: The proton is accepted by the base (B) and donated by the acid (H2O). The conjugate base of water is the hydroxide ion
(OH) which has one fewer proton and the conjugate acid of B is BH + which has one additional proton.
The equilibrium expression for this reaction can be written as follows:

Kb

[OH ][ BH ]
[ B]

Where Kb is the base dissociation constant.

The base dissociation constant can also be expressed as pKb where pKb = log(Kb) or Kb 10

pKb

Ka/pKa values for Common Acids. The higher the Ka/pKa value, the stronger the acid.
pKa
Acid
Formula
Ka
iodic acid
HIO3
0.17
0.77
2
oxalic acid
H2C2O4
5.9x10
1.23
sulphurous acid
H2SO3
1.5x102
1.82
hydrogen sulphate ion
HSO4
1.2x102
1.92
2
chlorous acid
HClO2
1.2x10
1.92
phosphoric acid
H3PO4
7.5x103
2.12
hydrofluoric acid
HF
7.2x104
3.14
4
nitrous acid
HNO2
4.0x10
3.40
hydrogen oxalate ion
HC2O4
6.1x105
4.21
HC2H3O2 (or
acetic acid
1.8x105
CH3COOH)
4.74
carbonic acid
H2CO3
4.3x107
6.37
hydrogen sulphite ion
HSO3
1.0x107
7.00
hydrosulphuric acid
H 2S
1.0x107
7.00
dihydrogen phosphate
H2PO4
6.2x108
ion
7.21
hypochlorous acid
HOCl
3.5x108
7.46
hypobromous acid
HOBr
2.0x109
8.70
hydrocyanic acid
HCN
6.2x1010
9.21
10
boric acid
H3BO3
5.8x10
9.24
ammonium ion
NH4+
5.6x1010
9.25
hydrogen carbonate ion HCO3
5.6x1011
10.25
2
13
hydrogen phosphate ion HPO4
4.8x10
12.32
hydrogen sulphide ion
HS
1.3x1013
12.89
Kb/pKb values for Common Bases. The higher the K b//pKb value, the stronger the base.
Base
Formula
Conjugate Acid
Kb
diethylamine
C4H10NH
C4H10NH2+
1.3x103
ethylamine
C2H5NH2
C2H5NH3+
5.6x104
+
methylamine
CH3NH2
CH3NH3
4.4x104
+
triethylamine
C6H15N
C6H15NH
4.0x104
ammonia
NH3
NH4+
1.8x105
+
+
hydrazine
H2NNH2 (or N2H4)
H2NNH3 (or N2H5 )
3.0x106
+
+
hydroxylamine HONH2 (or ONH3)
HONH3 (or ONH4 )
1.1x108
pyridine
C5H5N
C5H5NH+
1.7x109
+
aniline
C6H5NH2
C6H5NH3
3.8x1010
ex.

HF (aq) + H2O (l)


acid
base

H3O+ (aq) + F (aq)


conjugate
conjugate
acid
base

[ H 3O ][ F ]
Ka
[ HF ]

ex.

NH3 (aq) + H2O (l)


base
acid

OH (aq) + NH4+ (aq)


conjugate
conjugate
base
acid

[OH ][ NH 4 ]
Kb
[ NH 3 ]

pKb
2.89
3.25
3.36
3.40
4.74
5.52
7.96
8.77
9.42

ex. Write a Ka or Kb expression for the following acid-base equilibria. Identify the conjugate acidbase pairs.
(As a general guideline: For acids, the hydrogen is typically taken away from the beginning of the formula; for bases, the
hydrogen is typically added at the end of the formula)
(1) HC2H3O2 (aq) + H2O (l)

H3O+ (aq) + C2H3O2 (aq)

(2) CH3NH2 (aq) + H2O (l)

OH (aq) + CH3NH3+ (aq)

ex. Complete the following acidbase equilibria. Identify the conjugate acidbase pairs and write a Ka or Kb expression.
(1) HOBr (aq) + H2O (l)

(2) C6H5NH2 (aq) + H2O (l)

Hydrated Metal Ions


Certain metal ions (particularly transition metal ions and aluminum) when in solution will form hydrated complexes that may act
as acid.
ex. When Al3+ is in solution, it forms [Al(H2O)6]3+, the acid equilibrium for this complex is as follows: (Ka = 1.4x105)
[Al(H2O)6]3+ (aq) + H2O (l)
H3O+ (aq) + [Al(H2O)5OH]2+ (aq)
ex. When Fe3+ is in solution, it forms [Fe(H2O)6]3+. Complete the acid equilibrium for this complex. (Ka = 6.0x103)
[Fe(H2O)6]3+ (aq) + H2O (l)

Calculations for Weak Acids and Bases


The equilibrium concentration of the hydronium ion or hydroxide ion must be determined using an ICE table.
ex. Determine the pH and pOH of 1.0 M solution of HF (K a = 7.2x104).
H2O (l)

H3O+ (aq) +
0

F (aq)
0

HF (aq) +
1.0

+x

+x

1.0 x

[ H 3O ][ F ]
[ HF ]
x2
7.2 x104
1.0
Ka

x = 0.027 M = [H3O+]

assume x is small 1.0 x 1.0

changein concentration
x100%
initial concentration
0.027

x100% 2.7%
1.0
(therefore the approximation is valid)

percent changein concentration

pH = log[H+]= log[H3O+]
= log(0.027)
= 1.57
(H3O+ is equivalent to H+ for pH calculations)
pH + pOH = 14.00
1.57 + pOH = 14.00
pOH = 12.43

ex. Determine the pOH and pH of a 1.0 M solution of NH 3 (Kb = 1.8x105).

NH3 (aq) +
1.0

H2O (l)

1.0 x

OH (aq) +
0

NH4+ (aq)
0

+x

+x

[OH ][ NH 4 ]
Kb
[ NH 3 ]

x2
1.8 x10
1.0
5

x = 0.0042 M = [OH]

assume x is small 1.0 x 1.0

changein concentration
x100%
initial concentration
0.0042

x100% 0.42%
1.0
(therefore the approximation is valid)

percent changein concentration

pOH = log[OH]
= log(0.0042)
= 2.38
pH + pOH = 14.00
pH + 2.38 = 14.00
pH = 11.62

ex. The pH of a 0.650 M solution of citric acid (H 3C6H5O7) is 1.63. Determine Ka and pKa.

ex. The pOH of a 0.020 M solution of toluidine (C7H7NH2) is 5.35. Determine Kb and pKb.

Percent Dissociation (also called percent ionization)


The percent dissociation of a compound is a measure of the degree of dissociation.
For strong acids and bases, the percent dissociation is 100% (since the compound completely dissociates into its constituent
ions). For weak acids and bases, the percent dissociation can be calculated using an ICE table and according to the following
equation:

Percent dissociation

amount dissociated
x 100%
initial concentration

amount dissociated = x

ex. Calculate the percent dissociation for a 0.22 M solution of C2H5NH2 (Kb = 5.6x104).

ex. A 0.1000 M solution of lactic acid (HC3H5O3) is 3.7% dissociated at equilibrium. Calculate the Ka value for lactic acid.

Comparing the pH of a strong acid and a weak acid with the same concentration
A solution of a strong acid will have a much lower pH that a solution of a weak acid with the same initial concentration.
ex. (a) What is the pH of a solution with [HCl] = 0.10 M
(b) What is the pH of a solution with [HC2H3O2] = 0.10 M
(a) For 0.10 M HCl, the HCl completely dissociates.
HCl H+ + Cl
pH = log[H+]
+
therefore, [H ] = 0.10 M
= log(0.10)
= 1.00
(b) Since HC2H3O2 does not completely dissociate, the pH must be found using an ICE table.
HC2H3O2 (aq) +

H2O (l)

H3O+ (aq)

C2H3O2 (aq)

0.10

+x

+x

0.10x

Ka

[ H 3O ][C2 H 3O2 ]
[ HC2 H 3O2 ]

1.8 x105

x2
0.10

x = 0.0013 M = [H3O+]

assume x is small 0.10 x 0.10

pH = log[H3O+]
= log(0.0013)
= 2.87
The pH of a solution of the strong acid HCl with a concentration of 0.10 M (1.00) is much lower/more acidic than the pH of a
solution of the weak acid HC2H3O2 with an initial concentration of 0.10 M (2.87).
Comparing the concentration of a strong acid and a weak acid with the same pH
A solution of a strong acid will have a much lower concentration that a solution of a weak acid with the same pH.
ex. (a) What is the concentration of a solution of HCl with a pH of 2.00?
(b) What is the concentration of a solution of HNO2 with a pH of 2.00?
pH = 2.00, therefore [H+] (or [H3O+]) = 10pH = 102.00 = 0.010 M
(a) If [H+] = 0.010 M, since HCl completely dissociates, [HCl] = 0.010 M
(b) Since HNO2 does not completely dissociate, the concentration of HNO 2 must be found using an ICE table. The equilibrium
concentration of HNO2 can be defined as "x". The equilibrium concentration of [H 3O+] = 0.010 M and will be equal to the
equilibrium [NO2]. The initial concentration of HNO2 will therefore be x + 0.010.
HNO2 (aq) +

H2O (l)

H3O+ (aq)

NO2 (aq)

x + 0.010

0.010

+0.010

+0.010

0.010

0.010

Ka

[ H 3O ][ NO2 ]
[ HNO2 ]

4.0 x104

(0.010)2
x

x = 0.25 M
therefore, the initial
[HNO2] = 0.25 + 0.010
= 0.26 M

The initial concentration of a solution of the strong acid HCl with a pH of 2.00 (0.010 M) is much lower that the initial
concentration of a solution of the weak acid HNO2 with a pH of 2.00 (0.26 M).

Amphoteric Compounds
Amphoteric: A compound that can act as either an acid or a base.
ex. Water has been shown to act like both an acid (when in solution with a weak base) and as a base (when in solution with a
weak acid). Pure water will also undergo autoionization (self-ionization) such that some water molecules will act as acids and
some water molecules will act as bases according to the following reaction:
H2O (l) + H2O (l)

H3O+ (aq) + OH (aq)

note: The autoionization of water produces both hydronium ions hydroxide ions at equal concentrations ([H+] = [OH]) so the
resulting solution is neutral.
The equilibrium expression for this reaction is as follows:

K w [ H3O ][OH ] , where Kw is called the dissociation constant of water. Kw = 1.0x1014 (at 25 C) or pKw = 14
Neutral Solutions at Non-Standard Temperatures
In order for a solution to be neutral, the requirement is that [H 3O+] = [OH]. (Not that pH = 7)
At 25 C, since Kw = 1.0x1014, [H3O+] = [OH] = 1.0x107 which results in a pH (and pOH) of 7.0.
The autoionization of water is an endothermic process such that at higher temperatures the equilibrium shifts right and the value
of Kw increases. Since the dissociation constant of water (Kw) increases with temperature, [H+] and [OH] in a neutral solution
will increase with temperature and as a result, the pH of a neutral solution will decrease with temperature.
ex. At 40 C, Kw = 2.9x1014
At this temperature, [H3O+] = [OH] = 1.7x107 M, so neutral, pure water will have a pH (and pOH) of 6.78
ex. At 10 C, Kw = 2.9x1015
At this temperature, [H3O+] = [OH] = 5.4x108 M, so neutral, pure water will have a pH (and pOH) of 7.27.
(note: pH + pOH = 14 only applies for solutions at 25 C, the more general equation is that pH + pOH = pKw)

Relationship between Ka and Kb


For a weak acid, if the Ka value is known, then the Kb value of its conjugate base can be calculated. For a weak base, if the K b
value is known, then the Ka value for its conjugate acid can be calculated. This relationship is described according to the
following equation:

K a Kb K w

Kw = 1.0x1014 (at 25 C), Ka is the acid dissociation constant, and Kb is the base dissociation constant

This equation can also be written as pKa + pKb = 14.00


ex. Hydrofluoric acid, HF has Ka = 7.2x104
HF (aq) + H2O (l)
H3O+ (aq) + F (aq)
acid
conjugate base

Ka

[ H 3O ][ F ]
= 7.2x104
[ HF ]

Calculate Kb for F. Give the equilibrium reaction and Kb expression.

Since F is the conjugate base of HF,


F (aq) + H2O (l)

K w 1.0 x1014
Kb

1.4 x1011
4
K a 7.2 x10

OH (aq) + HF (aq)

Kb

[OH ][ HF ]
= 1.4x1011
[F ]

[ H 3O ][ F ] [OH ][ HF ]
x
[ H 3O ][OH ] K w
Note: K a xKb

[ HF ]
[F ]

ex. Pyridine, C5H5N has Kb = 1.7x109


C5H5N (aq) + H2O (l)
OH (aq) + C5H5NH+ (aq)
base
conjugate acid

[OH ][C5 H 5 NH ]
=1.7x109
Kb
[C5 H 5 N ]

Calculate Ka for C5H5NH+. Give the equilibrium reaction and Ka expression.


+

Since C5H5NH is the conjugate acid of C5H5N,


C5H5NH+ (aq) + H2O (l)

Note:

Kb xK a

K w 1.0 x1014
Ka

5.9 x109
9
Kb 1.7 x10

H3O+ (aq) + C5H5N (aq)

Ka

[ H 3O ][C5 H 5 N ]
= 5.9x109
[C5 H 5 NH ]

[OH ][C5 H 5 NH ] [ H 3O ][C5 H 5 N ]


x
[ H 3O ][OH ] K w
[C5 H 5 N ]
[C5 H 5 NH ]

Strength of a Conjugate Acid or Base


The stronger the acid, the weaker its conjugate base and the stronger the base, the weaker its conjugate acid.
ex. (a) Which of the following substances is a stronger acid, HF or HCN?
(b)Which of the following substances is a stronger base, F or CN?
(a) HF has Ka = 7.2x104 and HCN has Ka = 6.2x1010. Since Ka for HF is greater than Ka for HCN, HF is a stronger acid than
HCN.
(b) F has Kb = 1.0x1014/7.2x104 = 1.4x1011 and CN has Kb = 1.0x1014/6.2x1010 = 1.6x105. Since Kb for CN is greater than
Kb for F, CN is a stronger base than F.
HF is a stronger acid than HCN, so CN is a stronger base that F

ex. (a) Which of the following substances is a stronger base, NH 3 or C5H5N?


(b)Which of the following substances is a stronger acid, NH 4+ or C5H5NH+?
(a) NH3 has Kb = 1.8x105 and C5H5N has Kb = 1.7x109. Since Kb for NH3 is greater than Kb for C5H5N, NH3 is a stronger base
than C5H5N.
(b) NH4+ has Ka = 5.6x1010 (given on Ka table) and C5H5NH+ has Ka = 1.0x1014/1.7x109 = 5.9x109. Since Ka for C5H5NH+ is
greater than Ka for NH4+, C5H5NH+ is a stronger acid than NH4+.
NH3 is stronger base than C5H5N, so C5H5NH+ is a stronger acid than NH4+.

Amphoteric Compounds and Ka/Kb


In addition to water, there are many other amphoteric substances including the hydrogen carbonate ion (HCO 3), the hydrogen
sulphate ion (HSO4), the hydrogen sulphite ion (HSO3), the dihydrogen phosphate ion (H2PO4), the hydrogen phosphate ion
(HPO42), the hydrogen sulphide ion (HS) etc.
Comparing Equilibria for Amphoteric Compounds
ex. the hydrogen carbonate ion, HCO3 can act as an acid (donating a proton) or a base (accepting a proton)
reaction as an acid: HCO3 (aq) + H2O (l)
reaction as a base: HCO3 (aq) + H2O (l)

H3O+ (aq) + CO32 (aq)


OH (aq) + H2CO3 (aq)

Ka = 5.6x1011 (from Ka chart)

Kb

K w 1.0 x1014

2.3x108
7
K a 4.3x10

(Note: Ka for H2CO3 is used since


H2CO3 is the conjugate acid HCO3)
Since Kb>Ka, a solution containing hydrogen carbonate would have a basic pH (since [OH] will be greater than [H3O+])

Acid Base Reactions


Weak acids can react with weak bases and result in an acid/base equilibrium.
Consider the following reactions:
HS (aq) + NH4+ (aq)
conjugate conjugate
base
acid

(1) NH3 (aq) + H2S (aq)


base
acid

Calculating K for an acidbase reaction:


Consider the equilibria for the compounds acting as acids in the reaction:
H2S (aq) + H2O (l)
H3O+ (aq) + HS (aq)
Ka = 1.0x107
NH4+ (aq) + H2O (l)
H3O+ (aq) + NH3 (aq)
Ka = 5.6x1010
Note, if the second equilibrium is reversed (and the reciprocal of the equilibrium constant is taken), the two equilibria can add up
to give the overall equilibrium (and the K for the equilibrium can be obtained by multiplying K for each of the reactions)
H2S (aq) + H2O (l)
H3O+ (aq) + NH3 (aq)

H3O+ (aq) + HS (aq)


NH4+ (aq) + H2O (l)

Ka = 1.0x107
K = 1/5.6x1010 = 1.8x109

__________________________________________________________

NH3 (aq) + H2S (aq)


HS (aq) + NH4+ (aq)
K =1.0x107 x 1.8x109 = 1.8x102
+
(note: H3O (aq) and H2O (l) are cancelled when the equilibria are added)
An important result is that K>1. This is significant since H 2S is a stronger acid than NH4+, therefore the equilibrium position is
driven to the right, favouring the products.
This same result could be derived by considering the equilibria for the compounds that act as bases in the reaction:
NH3 (aq) + H2O (l)
OH (aq) + NH4+ (aq)
Kb = 1.8x105

HS (aq) + H2O (l)


OH (aq) + H2S (aq)
Kb = 1.0x1014/1.0x107 = 1.0x107
Note, if the second equilibrium is reversed (and the reciprocal of the equilibrium constant is taken), the two equilibria can add up
to give the overall equilibrium (and the K for the equilibrium can be obtained by multiplying K for each of the reactions)
NH3 (aq) + H2O (l)
OH (aq) + H2S (aq)

OH (aq) + NH4+ (aq)


HS (aq) + H2O (l)

Kb = 1.8x105
K = 1/1.0x107 = 1.0x107

______________________________________________________

NH3 (aq) + H2S (aq)

HS (aq) + NH4+ (aq)

K =1.8x105 x 1.0x107 = 1.8x102 (as determined above)

(note: OH (aq) and H2O (l) are cancelled when the equilibria are added)
The result that K>1 also correspond to the fact that NH 3 is a stronger base than HS, therefore the equilibrium position is driven
to the right, favouring the products.

(2) HOCl (aq) + C6H5NH2 (aq)

OCl (aq) + C6H5NH3+ (aq)

Consider the equilibria for the compounds acting as acids in the reaction:
HOCl (aq) + H2O (l)
H3O+ (aq) + OCl (aq)
Ka =3.5x108
C6H5NH3+ (aq) + H2O (l)
H3O+ (aq) + C6H5NH2 (aq)
Ka = 1.0x1014/3.8x1010 = 2.6x105
HOCl (aq) + H2O (l)
H3O+ (aq) + OCl (aq)
C6H5NH2 (aq) + H3O+ (aq)
C6H5NH3+ (aq) + H2O (l)

Ka =3.5x108
K = 1/2.6x105 = 3.8x104

_______________________________________________________________________

HOCl (aq) + C6H5NH2 (aq)

OCl (aq) + C6H5NH3+ (aq) K = 3.5x108 x 3.8x104 = 1.3x103

An important result is that K<1. This is significant since C6H5NH3+ is a stronger acid than HOCl, therefore the equilibrium
position is driven to the left, favouring the reactants.
(again, the K value could also be calculated by considering the compounds acting as bases)
Mixtures of Acids

In general, only the strongest acid will significantly contribute to the concentration of hydronium ions.
(1) Strong Acid/Weak Acid
ex. Calculate the pH of a mixture containing 0.50 M HCl and 0.50 M HOCl.
Since HCl is a strong acid and HOCl is a weak acid, the HOCl will not significantly contribute to the H + concentration, so the pH
can be calculated from the HCl concentration.
HCl H+ + Cl
0.50 M 0.50 M

[H+] = 0.50 M
pH = log[H+] = log(0.50) = 0.30

(if an ICE table were shown to determine [H3O+] contribution from 0.50 M HOCl, the value obtained be 0.00013 M. This would
not change the value obtained for pH.)
(2) Two Weak Acids
ex. Calculate the pH of a mixture containing 0.10 M HNO 2 (Ka = 4.0x104) and 0.10 M HCN (Ka = 6.2x1010)
Since Ka for HNO2 >> than Ka for HCN, only the HNO2 will significantly contribute to [H3O+]. An ICE table can then be used
to determine pH.
HNO2 (aq)

H2O (l)

H3O (aq) +

NO2

0.10

x
0.10 x 0.10
assume x
is small

+x

+x

(aq)

[ H 3O ][ NO2 ]
Ka
[ HNO2 ]

x2
4.0 x10
0.10
4

[H3O+] = x = 6.3x103 M
pH = log[H3O+] = log(6.3x103) = 2.20

Mixtures of Bases
In general, only the strongest base will significantly contribute to the concentration of hydroxide ions.
(1) Strong Base/Weak Base
ex. Calculate the pOH of a mixture containing 0.20 M Sr(OH)2 and 0.20 M NH3.
Since Sr(OH)2 is a strong base and NH3 is a weak base, the NH3 will not significantly contribute to the OH concentration, so the
pOH can be calculated from the Sr(OH)2 concentration.
Sr(OH)2 Sr2+ + 2OH
0.20 M
2(0.20 M)
= 0.40 M

[OH] = 0.40 M
pOH = log[OH] = log(0.40) = 0.40

(if an ICE table were shown to determine [OH ] contribution from 0.20 M NH3, the value obtained be 0.0019 M. This would not
change the value obtained for pOH.)
(2) Two Weak Bases
ex. Calculate the pOH of a mixture containing 0.50 M C6H5NH2 (Kb = 3.8x1010) and 0.50 M NH3 (Kb = 1.8x105)
Since Kb for NH3 >> than Kb for C6H5NH2, only the NH3 will significantly contribute to [OH]. An ICE table can then be used
to determine pOH.

NH3 (aq)

H2O (l)

OH (aq) +

NH4+

0.50

x
0.50 x 0.50
assume x
is small

+x

+x

(aq)

[OH ][ NH 4 ]
Kb
[ NH 3 ]

x2
1.8 x10
0.50
5

[OH] = x = 3.0x103 M
pOH = log[OH] = log(3.0x103) = 2.52

*When in question about if a substance in a mixture will contribute significantly to [H+] or [OH], it is always possible to
calculate the [H3O+] contribution from both acids and then add to determine the total [H 3O+] and use this value calculate pH OR
to calculate the [OH] contribution from both bases and then add to determine the total [OH] and use this value to calculate pOH
and then pH.

Solutions of Acids or Bases Containing a Common Ion of the Conjugate Base/Acid


An ICE table can be used to determine pH/pOH, where the initial concentration of the conjugate ion is not zero.
ex. A solution contains 1.0 M HF and 1.0 M NaF, Calculate the pH of the resulting solution.
How does this pH compare to a 1.0 M solution of HF?
NaF Na+ + F (note: NaF is a soluble salt)
1.0 M
1.0 M the initial [F]

HF (aq)

H2O (l)

H3O (aq) +

F (aq)

1.0

1.0

x
1.0 x 1.0
assume x
is small

+x

+x
1.0 + x 1.0
assume x
is small

[ H 3O ][ F ]
Ka
[ HF ]
x(1.0)
7.2 x104
1.0

[H3O+] = x = 7.2x104 M
pH = log[H3O+] = log(7.2x104) = 3.14

The pH of 1.0 M HF in water is 1.57 (calculated earlier this unit); the pH of 1.0 M HF in 1.0 M NaF is 3.14
Note : the pH of 1.0 M HF containing a common ion (F) is higher than the pH of 1.0 M HF in water.
Increasing [F] shifts the equilibrium to the left, thereby decreasing [H 3O+], making the solution LESS acidic and increasing pH.
ex. A solution contains 1.0 M NH3 and 1.0 M NH4Cl, Calculate the pH of the resulting solution.
How does this pH compare to a 1.0 M solution of NH3?
NH4Cl NH4+ + Cl (note: NH4Cl is a soluble salt)
1.0 M 1.0 M the initial [NH4+]

NH3 (aq)

H2O (l)

OH (aq) +

NH4+

1.0

1.0

x
1.0 x 1.0
assume x
is small

+x

+x
1.0 + x 1.0
assume x
is small

(aq)

[OH ][ NH 4 ]
[ NH 3 ]
x(1.0)
1.8 x105
1.0
Kb

[OH] = x = 1.8x105 M
pOH = log[OH] = log(1.8x105) = 4.74
pH = 14.00pOH = 14.00 4.74 = 9.26

The pH of 1.0 M NH3 in water is 11.62 (calculated earlier this unit); the pH of 1.0 M NH 3 in 1.0 M NH4Cl is 9.26
Note : the pH of 1.0 M NH3 containing a common ion (NH4+) is lower than the pH of 1.0 M NH3 in water.
Increasing [NH4+] shifts the equilibrium to the left, thereby decreasing [OH ], making the solution LESS basic and decreasing
pH.

Number of Acidic Protons/Hydrogen atom


monoprotic acids: have only one acidic hydrogen atoms (ex. HCl, HNO2, and HC2H3O2)
(Some compounds have formulas with more than one hydrogen atom; however, only one hydrogen atom can actually be donated
easily in an acid equilibrium. This proton is sometimes referred to as the "labile" proton.)
diprotic acids: have two acidic hydrogen atoms (ex. H2SO4 and H2C2O4)
polyprotic acids: have three or more acidic hydrogen atoms (ex. H3PO4)
(diprotic and polyprotic acids have more than one labile proton.)
ex. Successive ionization of carbonic acid (H2CO3).
H2CO3 + H2O (l)
H3O+ (aq) + HCO3 (aq)
Ka1 = 4.3x107

+
2
HCO3 + H2O (l)
H3O (aq) + CO3 (aq)
Ka2 = 5.6x1011
_______________________________________________________

H2CO3 + 2H2O (l)

2H3O+ (aq) + CO32 (aq)

K = Ka1 x Ka2 = 4.3x107 x 5.6x1011 = 2.4x1017

For a diprotic acid generally, Ka1>Ka2. (The first proton is more easily lost than the second proton.)
AcidBase Properties of Salts
The cation or anion of a salt may hydrolyze (react with water) and produce an acidic or basic solution.
Cations
Cations found in strong bases will not hydrolyze.
Cations that are the conjugate acids of weak bases will hydrolyze to produce acidic solutions.
Anions
Anions found in strong acids will not hydrolyze.
Anions that are the conjugate bases of weak acids will hydrolyze to produce basic solutions.
ex. Determine if the pH of the following solutions will be acidic, basic, or neutral.
(1) NaCl
NaOH is a strong base so Na+ will not hydrolyze
HCl is a strong acid so Cl will not hydrolyze
Since neither the cation or anion hydrolyze, the solution will be neutral
(2) NaC2H3O2
NaOH is a strong base so Na+ will not hydrolyze
C2H3O2 is the conjugate base of the weak acid HC2H3O2, so C2H3O2 will hydrolyze:
C2H3O2 (aq) + H2O (l)
OH (aq) + HC2H3O2 (aq)
The resulting hydrolysis reaction produces hydroxide ions so the solution is basic.
(3) NH4Cl
HCl is a strong acid so Cl will not hydrolyze
NH4+ is the conjugate acid of the weak base NH 3, so NH4+ will hydrolyze:
NH4+ (aq) + H2O (l)
H3O+ (aq) + NH3 (aq)
The resulting hydrolysis reaction produces hydronium ions so the solution is acidic.
(4) NH4NO2
NO2 is the conjugate base of the weak acid HNO2, so NO2 will hydrolyze:
NO2 (aq) + H2O (l)
OH (aq) + HNO2 (aq)
NH4+ is the conjugate acid of the weak base NH 3, so NH4+ will hydrolyze:
NH4+ (aq) + H2O (l)
H3O+ (aq) + NH3 (aq)
Since both ions hydrolyze, the Ka and Kb values for the resulting equilibria must be compared.
HNO2 has Ka = 4.0x104, therefore, NO2 has Kb = 2.5x1011
NH4+ has a Ka = 5.6x1010
Since Ka > Kb, the hydrolysis of NH4+ will favour the products more than the hydrolysis of NO 2, as a result there will be more
hydronium ions than hydroxide ions and the solution will be acidic.

Calculations for Salts


ex. Calculate the pH and pOH of a 0.20 M solution of NaF.
The concentration of each ion can be found from dissociation (since NaF is a soluble salt)
NaF Na+ + F
0.20 M 0.20 M 0.20 M
NaOH is a strong base so Na+ will not hydrolyze.
F is the conjugate base of the weak acid HF, so F will hydrolyze:
F (aq) + H2O (l)
OH (aq) + HF (aq) Kb = Kw/Ka = 1.0x1014/7.2x104 = 1.4x1011
An ICE table can be used to determine the pOH of the solution.
F (aq) +

H2O (l)

OH (aq) +

HF (aq)

0.20

x
0.20 x
0.20
assume x
is small

+x

+x

[OH ][ HF ]
[F ]
x2
1.4 x1011
0.20
Kb

[OH] = x = 1.7x106 M
pOH = log[OH] = log(1.7x106) = 5.77
pH = 14.00pOH = 14.00 5.77 = 8.23

ex. Calculate the pH and pOH of a 0.015 M solution of NH 4Br.


The concentration of each ion can be found from dissociation (since NH4Br is a soluble salt)
NH4Br NH4 + + Br
0.015 M 0.015 M 0.0150 M
HBr is a strong acid so Br will not hydrolyze.
NH4+ is the conjugate acid of the weak base NH 3, so NH4+ will hydrolyze:
NH4+ (aq) + H2O (l)
H3O+ (aq) + NH3 (aq)
Ka = 5.6x1010 (from Ka chart)
An ICE table can be used to determine the pH of the solution.
NH4+ (aq) +

H2O (l)

H3O+ (aq) +

NH3 (aq)

0.015

x
0.015 x
0.015
assume x
is small

+x

+x

Ka

[ H 3O ][ NH 3 ]
[ NH 4 ]

5.6 x1010

x2
0.015

[H3O+] = x = 2.9x106 M
pH = log[H3O+] = log(2.9x106) = 5.54
pOH = 14.00pH = 14.00 5.54 = 8.46

ex. Calculate the pH and pOH of a 0.12 M solution of ethylammonium nitrite (C2H5NH3NO2).
The concentration of each ion can be found from dissociation (C 2H5NH3NO2 is a soluble salt)
C2H5NH3NO2 C2H5NH3 + + NO2
0.12 M
0.12 M
0.12 M
NO2 is the conjugate base of the weak acid HNO2, so NO2 will hydrolyze:
NO2 (aq) + H2O (l)
OH (aq) + HNO2 (aq)
Kb = Kw/Ka = 1.0x1014/4.0x104 = 2.5x1011
C2H5NH3+ is the conjugate acid of the weak base C2H5NH2, so C2H5NH3+ will hydrolyze:
C2H5NH3+ (aq) + H2O (l)
H3O+ (aq) + C2H5NH2 (aq)
Ka = Kw/Kb = 1.0x1014/4.4x104 = 2.3x1011
Since both ions hydrolyze, and ICE table must be used to determine the [OH ] resulting from the hydrolysis of NO 2 and the
[H3O+] from the hydrolysis of C2H5NH3+. The ion in excess can then be used to calculate the pH/pOH of the solution.

NO2 (aq) +

H2O (l)

OH (aq) +

HNO2 (aq)

0.12

x
0.12 x 0.12
assume x
is small

+x

+x

[OH ][ HNO2 ]
[ NO2 ]

2.5 x1011
x

x2
0.12

[OH] = x = 8.2x106 M

C2H5NH3+ (aq) +

H2O (l)

H3O+ (aq) +

C2H5NH2 (aq)

0.12

x
0.12 x 0.12
assume x
is small

+x

+x

Kb

Ka

[ H 3O ][C2 H 5 NH 2 ]
[C2 H 5 NH 3 ]

2.3x1011

x2
0.12

[H3O+] = x =1.6x106 M

Since Kb for NO2 >Ka for C2H5NH3+, this results in [OH]>[H3O+]. The OH and H3O+ will partially neutralize each other,
forming water (OH + H3O+ 2H2O) with H3O+ as the limiting reactant and OH as the excess reactant. The amount of excess
OH is found by subtracting the amount of the limiting reactant H 3O+.
[OH] = 8.2x106 M 1.6x106 M = 6.6x106 M
pOH = log[OH] = log(6.6x106) = 5.18
pH = 14.00pOH = 14.00 5.18 = 8.82
Neutralizations Reactions
To give the net ionic equation for a neutralization reaction, the spectator ions must be determined. Only strong acids, strong
bases, and soluble salts will dissociate completely to form ions. Weak acids, weak bases, and water will remain undissociated.
There are three types of neutralization reactions that will be considered that will each result in a different form of net ionic
equation.
(1) A Strong Acid with a Strong Base
ex. A solution of hydrobromic acid is reacted with a solution of potassium hydroxide.
HBr (aq) + KOH (aq) H2O (l) + KBr (aq)
H+ (aq) + Br (aq) + K+ (aq) + OH (aq) H2O (l) + K+ (aq) + Br (aq) (the spectator ions are K+ and Br)
H+ (aq) + OH (aq) H2O (l)
The reaction between all strong acids and bases will have the net ionic equation: H + (aq) + OH (aq) H2O (l)
(2) A Weak Acid with a Strong Base
ex. A solution of hydrofluoric acid is reacted with a solution of sodium hydroxide
HF (aq) + NaOH (aq) H2O (l) + NaF (aq)
HF (aq) + Na+ (aq) + OH (aq) H2O (l) + Na+ (aq) + F (aq) (the spectator ion is Na+)
HF (aq) + OH (aq) H2O (l) + F (aq)
The reaction between all weak acids and strong bases will have the general net ionic equation:
HA (aq) + OH (aq) H2O (l) + A (aq)
(3) A Weak Base with a Strong Acid
ex. a solution of nitric acid reacts with a solution of ammonia. For this type of reaction, it is easiest to consider the strong acid as
equivalent to hydronium, H3O+ (When HNO3 is present in solution, it dissociates completely to H+ and NO3. Nitrate, NO3, is a
spectator ion, but the hydrogen ion, H+, will combine with H2O and result and form hydronium, H3O+. This is why the hydrogen
ion and hydronium ion are considered to be equivalent). The weak base in the reaction (i.e. NH3) will accept a proton from H3O+
to produce water.
NH3 (aq) + H3O+ (aq) H2O (l) + NH4+ (aq)
The reaction between all weak bases and strong acids will have the general net ionic equation:
B (aq) + H3O+ (aq) H2O (l) + BH+ (aq)

Buffers
Buffer: a solution that resists changes in pH.
A buffer contains a weak acid (HA) and (a salt of) its conjugate base (A).
HA (aq) + H2O (l)
H3O+ (aq) + A (aq)
OR a weak base (B) and (a salt of) its conjugate acid (BH +)
B (aq) + H2O (l)
OH (aq) + BH+ (aq)

Examples of Buffer Solutions:


(1) Example of an acidic buffer: HC2H3O2 and NaC2H3O2 (provides C2H3O2)
equilibrium: HC2H3O2 (aq) + H2O (l)
H3O+ (aq) + C2H3O2 (aq)
(2) Example of a basic buffer: NH3 and NH4Cl (provides NH4+)
equilibrium: NH3 (aq) + H2O (l)
OH (aq) + NH4+ (aq)
Examples of Solutions that are NOT Buffers
(1) HCl and NaCl
Since HCl is a strong acid this solution would not act as a buffer. Only weak acids and their conjugate bases (or weak bases and
their conjugate acids) make good buffers. Strong acids (and bases) do not make good buffers. It takes much more base to change
the pH of a weak acid solution because there is a large amount of undissociated weak acid.
(2) H2SO3 and Na2SO3
Since SO32 is not the conjugate base of H2SO3 this solution would not act as a buffer. In order to prepare a buffer using H 2SO3,
the solution would need to contain HSO 3. A buffer solution could be prepared by combining H2SO3 and NaHSO3.

Buffer Calculations
Buffer calculations are equivalent to those for solutions with a common ion and can be solved using an ICE Table.
ex. A solution contains 0.50 M HC2H3O2 and 0.50 M NaC2H3O2. Calculate the pH of the solution.
HC2H3O2 (aq) +

H2O (l)

H3O+ (aq)

C2H3O2 (aq)

0.50

0.50

x
0.50 x
0.50
assume x
is small

+x

+x
0.50 + x
0.50
assume x
is small

[ H 3O ][C2 H 3O2 ]
[ HC2 H 3O2 ]
x(0.50)
1.8 x105
0.50
Ka

[H3O+] = x = 1.8x105 M
pH = log[H3O+]
= log(1.8x105)
= 4.74

The HendersonHasselbalch Equation


Determining the pH of any solution containing a weak acid and its conjugate base can be simplified using the HendersenHasselbalch equation:

[ A ]
pH pK a log

[ HA]

where: pKa = log Ka

Determining the pOH of any solution containing a weak base and its conjugate acid can be simplified using the following
equation:

[ BH ]
pOH pKb log
where: pKb = log Kb
[ B]

ex. A buffer solution contains 0.50 M HC2H3O2 and 0.50 M NaC2H3O2. Calculate the pH of the solution.

[C H O ]
pH pK a log 2 3 2
[ HC2 H 3O2 ]
0.50
pH log(1.8 x105 ) log

0.50
pH 4.74 (as previously calculated using an ICE table)
note: When [HA] = [A] (in this case, [HC2H3O2] = [C2H3O2]), then pH = pKa.
ex. A buffer solution contains 0.50 M HC2H3O2 and 0.10 M NaC2H3O2. Calculate the pH of the solution.

[C H O ]
pH pK a log 2 3 2
[ HC2 H 3O2 ]
0.10
pH log(1.8 x105 ) log

0.50
pH 4.05
note: When [HA] > [A] (in this case, [HC2H3O2] > [C2H3O2]), then pH < pKa.
ex. A buffer solution contains 0.10 M HC2H3O2 and 0.50 M NaC2H3O2. Calculate the pH of the solution.

[C2 H 3O2 ]
pH pK a log

[ HC2 H 3O2 ]
0.50
pH log(1.8 x105 ) log

0.10
pH 5.44
note: When [HA] < [A] (in this case, [HC2H3O2] < [C2H3O2]), then pH > pKa.
ex. A solution contains 0.25 M NH3 and 0.30 M NH4Cl . Calculate the pH of the solution.

[ NH 4 ]
pOH pKb log

[ NH 3 ]
0.30
pOH log(1.8 x105 ) log

0.25
pOH 4.82
pH = 14.00 pOH = 14.00 4.05 = 9.18

The mechanism of a buffer upon addition of acid or base can be explained using the HendersonHasselbalch Equation

[ A ]
pH pK a log

[ HA]
Consider an the following buffer: HA (aq) + H2O (l)

H3O+ (aq) + A (aq)

(1) If a base, OH, is added to the buffer, the base will react with the acidic component of the buffer:
HA (aq) + OH (aq) H2O (l) + A (aq)
As a result, [A] will increase and [HA] will decrease (and the ratio of [A]/[HA] will increase). Therefore, the addition of base
results in an overall slight increase in pH.
(2) If an acid, H3O+, is added to the buffer, the acid will react with the basic component of the buffer:
A (aq) + H3O+ (aq) H2O (l) + HA (aq)
As a result, [HA] will increase and [A] will decrease (and the ratio of [A]/[HA] will decrease). Therefore, the addition of acid
results in an overall slight decrease in pH.

Buffer Capacity
Buffer Capacity: the amount of an acid or base that can be added to a specific volume of a buffer solution before its pH changes
significantly (usually defined as an increase or decrease of one pH unit).
A buffer is most effective at resisting change in pH near its pK a value. If a buffer has pH = pKa the ratio [A]/[HA] = 1. If too
much acid or base is added to the buffer, the ratio of [A]/[HA] will be altered such that the pH will change significantly. When
base is added, the ratio can be increased such that [A]/[HA] changes to 10 and the pH will increase by one; when acid is added,
the ratio can be decreased such that [A]/[HA] changes to 0.10 and the pH will decrease by one.
Buffer capacity is also determined by the amount of acid and of conjugate base. The more moles of each that are present, the
higher the buffer capacity. For buffers of equal volume, the greater the concentrations of both HA and A, the greater the
buffering capacity since more acid or base would need to be added in order to change the ratio of [A]/[HA] to a value that
would significantly change the pH. A solution with high [HA] and [A] will be able to more effectively resist changes in pH.
For buffers of equal concentrations of HA and A, the higher the volume, the greater the buffer capacity. The more volume, the
more moles of both HA and A that would be present and the more acid or base would need to be added in order to change the
ratio of [A]/[HA] to a value that would significantly change the pH.
Preparing Buffers
In order to calculate the pH of a buffer, the pKa (or pKb) must be known along with the concentration of weak acid and conjugate
base (or the concentration of weak base and conjugate acid).
ex. Calculate the pH of a buffer made by adding 0.75 g of sodium fluoride to 200 mL of 0.10 M hydrofluoric acid. Assume the
volume of the solution remains constant.

ex. Determine the mass of methylammonium chloride (CH3NH3Cl) that should be added to 300 mL of 0.20 M methylamine
(CH3NH2) in order to make a buffer with a pH of 10.60. Assume the volume of the solution remains constant.

Biological Applications: The Blood Buffer


The body maintains the pH of blood between 7.35 and 7.45. If the pH level changes just a few tenths of a pH unit, serious health
consequences can result. A decrease in blood pH is called acidosis, an increase is called alkalosis.
The most important buffer in the blood consists of a buffer between carbonic acid (H 2CO3) and hydrogen carbonate (HCO3, also
called bicarbonate)
H2CO3 (aq) + H2O (l)
H3O+ (aq) + HCO3 (aq)
In addition, there is a phosphate buffer (H2PO4/HPO42) as well as the buffering ability of some proteins in plasma (since they
have a carboxylic acid/amine i.e. a weak acid/base component) that are available to maintain blood pH.

Titrations
Titration: An analytical procedure in which the concentration of a known solution is used to determine the concentration of an
unknown solution.
Acid Base Titrations
Acid base titrations involve neutralization reactions. For an experiment, the objective is to determine the volume of a solution
with known concentration that is required to titrate (i.e. exactly react with or neutralize) a given volume of solution with an
unknown concentration. The solution with known concentration is called the titrant. The solution with the unknown
concentration is called the titrate or the analyte. The higher the concentration of the titrate/analyte, the more of the titrant that
will be required in order to complete the neutralization reaction. Usually several trials are performed and the average volume
is used for calculations. Chemical indicators (i.e. phenolphthalein or bromothymol blue) can be used to monitor when the
reaction is complete and has reached its equivalence point.

Titration Calculations
Determine the balanced chemical equation for the neutralization reaction. Titration calculations are solution stoichiometry
problems. Use the concentration and volume given to determine the moles of titrant used in the experiment. Determine the
moles of titrate/analyte using the mole ratio in the reaction. Determine the concentration of the titrate/analyte from the volume.
ex. What is the concentration if 12.00 mL of HCl requires 15.00 mL of 0.20 M NH 3 to react completely?
H3O+ (aq) +

NH3 (aq)

0.0030

0.0030

volume (L)

0.01200

0.01500

Molarity (M)
molar mass
(g/mol)

0.25

0.20

moles (mol)

H2O (l) +

mass (g)

= = (0.20 M) (0.01500 L) = 0.0030 mol NH 3

0.0030 mol NH 3 x

= [ HCl ]

1 mol H 3O
0.0030 mol H 3O 0.0030 mol HCl
1 mol NH 3

0.0030 mol
0.25 M
0.01200 L

NH4+ (aq)

ex. What is the concentration if 5.00 mL of HF requires 25.00 mL of 0.10 M Ba(OH) 2 to react completely?
Ba(OH)2 Ba2+ + 2OH
therefore, [OH] = 2(0.10 M) = 0.20 M

HF (aq) +

OH (aq)

0.0050

0.0050

volume (L)

0.00500

0.02500

Molarity (M)
molar mass
(g/mol)

1.0

0.20

moles (mol)
mass (g)

= = (0.20 M) (0.02500 L) = 0.0050 mol OH

0.0050 mol OH x

[ HF ]

1 mol HF
0.0050 mol HF
1 mol OH

0.0050 mol
1.0 M
0.00500 L

H2O (l) +

F (aq)

Titration Curve Calculations


In a titration experiment, the pH of the solution at incremental points in the titration experiment can be determined and graphed
to create a titration curve.
Strong Acid/ Strong Base Titration
ex. A 0.100 M solution of NaOH is used to titrate 100.0 mL of a 0.100 M HCl solution.
Determine the pH at the following intervals in the experiment.
(1) No NaOH has been added pH = 1.000
The pH of the solution can be calculated from the [HCl]
+

HCl H + Cl
therefore, [H+] = 0.100 M

pH = log[H ]
= log(0.100)
= 1.000

initial
mol

(2) 25.00 mL of NaOH has been added pH = 1.22


The acid and base will partially neutralize each other and the
pH of the resulting solution can be determined from the
concentration of the excess reactant.
H+ (aq) +

initial
mol

change
in mol
final
mol

= (0.100M)
(0.1000 L)
= 0.0100 mol
H+ is the EXCESS
reactant

(5) 100.0 mL of NaOH has been added

OH (aq)
= (0.100 M)
(0.02500 L)
= 0.00250 mol
OH is the
LIMITING
reactant

0.00250 mol

0.00250 mol

= 0.0075 mol

= 0 (since OH is
the limiting
reactant, it is
completely
consumed)

H2O (l)
It is not
necessary
to calculate
the moles
of water
produced

0.0075 mol
[H ]
0.060M
0.1250 L

change
in mol
final
mol

pH = log[H+] = log(0.060) = 1.22


pH = 1.48

(4) 75.00 mL of NaOH has been added

pH = 1.85

OH (aq)
= (0.100M)
(0.1000 L)
= 0.0100 mol

0.0100 mol

0.0100 mol

=0

=0

(6) 125.0 mL of NaOH has been added

initial
mol

change
in mol

[OH ]

(3) 50.00 mL of NaOH has been added

H+ (aq) +
= (0.100M)
(0.1000 L)
= 0.0100 mol

H2O (l)

Since only H2O is present, the solution is neutral with pH =


7.00. This point is call the equivalence point because moles
H+ = moles OH (moles acid = moles base)

final
mol

(note: the total volume of the solution is


0.1000 L + 0.02500 L = 0.1250 L)

pH = 7.00

pH = 12.04

H+ (aq) +
= (0.100M)
(0.1000 L)
= 0.0100 mol
H+ is the
LIMITING
reactant

OH (aq)
= (0.100 M)
(0.12500 L)
= 0.01250 mol
OH is the
EXCESS
reactant

0.0100 mol

0.0100 mol

= 0 (since H+ is the
limiting reactant, it
is completely
consumed)

H2O (l)

= 0.0025 mol

0.0025 mol
0.011M
0.2250 L

(note: the total volume of the solution is


0.1000 L + 0.12500 L = 0.2250 L)
pOH = log[OH] = log(0.011) = 1.96
pH = 14.00 pH = 14.00 1.96 = 12.04
(7) 150.00 mL of NaOH has been added
(8) 175.0 mL of NaOH has been added

pH = 12.30
pH = 12.43

(9) 200.0 mL of NaOH has been added. pH = 12.52


Note that there are four regions to be considered in titration curve calculations where a strong base is added to a strong acid:
(1) Before any base is added- pH is calculated directly from the concentration of acid.
(2) Before the equivalence point- pH is calculated from the excess concentration of acid.
(3) At the equivalence point- since moles H+ = moles OH, pH = 7
(4) After the equivalence point- pOH (and then pH) is calculated from the excess concentration of base.

The pH values for each volume of NaOH added can be graphed to create a titration curve.

pH

Strong Acid Strong Base Titration


14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
0

25

50

75

100

125

150

175

200

Volume NaOH added (mL)

If a strong acid is added to a strong base, the four regions to be considered in titration curve calculations are as follows:
(1) Before any acid is added- pOH (and then pH) is calculated directly from the concentration of base.
(2) Before the equivalence point- pOH (and then pH) is calculated from the excess concentration of base.
(3) At the equivalence point- since moles acid (H+) = moles base (OH), pH = 7
(4) After the equivalence point- pH is calculated from the excess concentration of acid.

Conductivity in Titrations
A titration can also be performed by measuring the conductivity of the solution (the solution being titrated will conduct
electricity due to the presence of ions). This is called a conductometric titration.
Strong Acid/Strong Base (i.e. HCl and NaOH)
As NaOH is added, the concentration of H + ions decreases (H+ + OH H2O)
and the concentration of Na+ ions is increased. There is a constant amount of
Cl ion in the solution since it is a spectator ion. The total charge of the
solution is zero. Although the positive charge of the H + ions is replaced by
Na+ ions, the conductivity of an H+ ion is greater than that of an Na+ ion, so the
overall conductivity of the solution decreases. At the equivalence point, all of
the H+ and OH have been consumed, so the conductivity of the solution is at a
minimum (since the solution contains only Na + and Cl). After the equivalence
point, if additional NaOH is added, the conductivity increases due to the
relatively higher conductivity of the OH ions in solution.

Strong Base/Weak Acid


ex. A 0.050 M solution of NaOH is used to titrate 100.0 mL of a 0.050 M benzoic acid (HC 7H5O2, Ka = 6.3x105) solution.
Determine the pH at the following intervals in the experiment.
(1) No NaOH has been added pH = 2.75
Before any base has been added, the pH can be calculated using an ICE table.
H2O (l)
HC7H5O2 (aq) +
H3O+ (aq) +
C7H5O2 (aq)
I

0.050

+x

+x

0.050 x

Ka

[ H 3O ][C7 H 5O2 ]
[ HC7 H 5O2 ]

6.3x105

x2
0.050

x = 0.0018 M = [H3O+]

assume x is small 0.050 x 0.050

pH = log[H3O+]
= log(0.0018)
= 2.75
(2) 25.00 mL of NaOH has been added

pH = 3.72

(3) 50.00 mL of NaOH has been added pH = 4.20


The added base will partially neutralize the acid. Determine moles/molarity of excess acid and conjugate base produced in the
reaction. The pH of the solution can be found using an ICE table OR using the HendersonHasselbalch Equation.
OH (aq)

HC7H5O2 (aq) +

H2O (l)

C7H5O2 (aq)

initial
mol

= (0.050M)
(0.1000 L)
= 0.0050 mol
HC7H5O2 is the
EXCESS reactant

= (0.050M)
(0.0500 L)
= 0.0025 mol
OH is the LIMITING
reactant

change
in mol

0.0025 mol

0.0025 mol

+ 0.0025 mol

= 0.0025 mol

= 0 (since OH is the
limiting reactant, it is
completely consumed)

= 0.0025 mol

final mol

[ HC7 H 5O2 ]

0.0025 mol
0.017 M
0.1500 L

It is not
necessary
to calculate the
moles of water
produced

[C7 H 5O2 ]

0
(initially, there is no
conjugate base present)

0.0025 mol
0.017 M
0.1500 L

(note: the total volume of the solution is 0.1000 L + 0.05000 L = 0.1500 L)


HC7H5O2 (aq) +

H3O+ (aq)

H2O (l)

C7H5O2 (aq)

0.017

0.017

x
0.017 x
0.017
assume x
is small

+x

+x
0.017 + x
0.017
assume x
is small

[ H 3O ][C7 H 5O2 ]
[ HC7 H 5O2 ]
x(0.017)
6.3x105
0.017
Ka

x = 6.3x105 M = [H3O+]
pH = log[H3O+]
= log(6.3x105)
= 4.20

OR
HendersonHasselbalch Equation

[C H O ]
pH pK a log 7 5 2
[ HC7 H 5O2 ]
(4) 75.00 mL of NaOH has been added

0.017
pH log(6.3x105 ) log

0.017
pH = 4.68

pH = 4.20 (as with the ICE table)

(5) 100.0 mL of NaOH has been added

pH = 8.30
OH (aq)

HC7H5O2 (aq) +

H2O (l)

C7H5O2 (aq)

It is not
necessary
to calculate the
moles of water
produced

initial
mol

= (0.050M)
(0.1000 L)
= 0.0050 mol

= (0.050M)
(0.1000 L)
= 0.0050 mol

change
in mol

0.0050 mol

0.0050 mol

+ 0.0050 mol

=0

=0

= 0.0050 mol

final mol

0
(initially, there is no
conjugate base present)

This is the equivalence point in the titration because moles acid = moles base.
The only substance present at the equivalence point is the conjugate base.

[C7 H 5O2 ]

0.0050 mol
0.025M
0.2000 L

(note: the total volume of the solution is 0.1000 L + 0.1000 L = 0.2000 L)


For a Weak Acid/Strong Base Titration, the solution is NOT neutral at the equivalence point. The conjugate base will form an
equilibrium with water and the pOH (and then the pH) can be calculated using an ICE table.
C7H5O2 (aq) +

OH (aq) +

H2O (l)

HC7H5O2 (aq)

Kb

[OH ][ HC7 H 5O2 ]


[C7 H 5O2 ]

0.025

x
0.025 x
0.025
assume x
is small

+x

+x

(the Kn expression and constant is used


since there is a base equilibrium)

Kb

K w 1.0 x1014

1.6 x1010
5
K a 6.3x10

1.6 x10

10

x2

0.025

x = 2.0x106 M = [OH]
pOH = log[OH] = log(2.0x106) = 5.70
pH = 14.00 pOH = 14.00 5.70 = 8.30
(6) 125.0 mL of NaOH has been added
(7) 150.00 mL of NaOH has been added

pH = 11.74
pH = 12.00
OH (aq)

HC7H5O2 (aq) +

initial
mol

= (0.050M)
(0.1000 L)
= 0.0050 mol
HC7H5O is the
LIMITING reactant

= (0.050M)
(0.1500 L)
= 0.0075 mol
OH is the EXCESS
reactant

change
in mol

0.0050 mol

0.0050 mol

final mol

=0
(since HC7H5O2 is the
limiting reactant, it is
completely consumed)

H2O (l)

It is not
necessary
to calculate the
moles of water
produced

= 0.0025

C7H5O2 (aq)
0
(initially, there is no
conjugate base present)
+ 0.0050 mol

= 0.0050 mol

The solution contains a mixture of excess strong base (OH ) and conjugate base (C7H5O2). The pOH (and then the pH) can be
calculated from the molarity of strong base because the weak conjugate base will not significantly contribute to [OH].

[OH ]

0.0025 mol
0.010 M
0.2500 L

pOH = log[OH] = log(0.010) = 2.00

(note: the total volume of the solution is 0.1500 L + 0.1000 L = 0.2500 L)

pH = 14.00 pOH = 14.00 2.00 = 12.00

(8) 175.0 mL of NaOH has been added

pH =12.13

(9) 200.0 mL of NaOH has been added. pH = 12.22


The pH values for each volume of NaOH added can be graphed to create a titration curve.

pH

Weak Acid Strong Base Titration


14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
0

25

50

75

100

125

150

175

200

Volume NaOH added (mL)

If a strong base is added to a weak acid, the four regions to be considered in titration curve calculations are as follows:
(1) Before any base is added- pH is calculated from the concentration and Ka of the acid using an ICE table.
(2) Before the equivalence point- pH is calculated from the remaining concentration of acid and produced concentration of
conjugate base using an ICE table OR using the Henderson-Hasselbalch equation.
(3) At the equivalence point- pOH (and then pH) is calculated from the concentration of conjugate base using an ICE table and
Kb.
(4) After the equivalence point- pOH (and then pH) is calculated from the excess concentration of base.

Strong Acid/Weak Base


ex. A 0.100 M solution of HCl is used to titrate 100.0 mL of a 0.100 M NH3 (Kb = 1.8x105) solution.
Determine the pH at the following intervals in the experiment.
(1) No HCl has been added pH = 11.11
Before any acid has been added, the pOH (and then the pH) can be calculated using an ICE table.

H2O (l)

OH (aq) +
0

NH4+ (aq)
0

NH3 (aq) +
0.100

+x

+x

0.100 x

assume x is small 0.100 x 0.100

Kb

[OH ][ NH 4 ]
[ NH 3 ]

1.8 x105

x2
0.100

x = 0.0013 M = [OH]
pOH = log[OH] = log(0.0013) = 2.89
pH = 14.00 pOH = 14.00 2.89 = 11.11

(2) 25.00 mL of HCl has been added pH = 9.73


The added acid will partially neutralize the base. Determine moles/molarity of excess base and conjugate acid produced in the
reaction. The pOH (and then pH) of the solution can be found using an ICE table OR using the HendersonHasselbalch
Equation.
NH3 (aq) +

H3O+ (aq)
= (0.100M)
(0.02500 L)
= 0.00250 mol
H3O+ is the
LIMITING
reactant

H2O (l) +
It is not
necessary
to calculate
the moles
of water
produced

NH4+ (aq)

initial
mol

= (0.100M)
(0.1000 L)
= 0.0100 mol
NH3 is the
EXCESS reactant

change
in mol

0.0025 mol

0.0025 mol

+ 0.0025 mol

= 0.0075 mol

= 0 (since H3O+ is
the limiting
reactant, it is
completely
consumed)

= 0.0025 mol

final
mol

[ NH 3 ]

0.0075 mol
0.060M
0.1250 L

[ NH 4 ]

0
(initially, there is
no conjugate acid
present)

0.0025 mol
0.020M
0.1250 L

(note: the total volume of the solution is 0.1000 L + 0.02500 L = 0.1250 L)


ICE TABLE

I
C
E

NH3 (aq) +
0.060
x
0.060 x
0.060
assume x is
small

OH (aq) +
0

NH4+ (aq)
0.020

+x

+x

0.020 + x
0.020

H2O (l)

[OH ][ NH 4 ]
[ NH 3 ]
x(0.020)
1.8 x105
0.060
Kb

x = 5.4x105 M = [OH]

pOH = log[OH] = log(5.4x105) = 4.27


pH = 14.00 pOH = 14.00 4.27 = 9.73

OR
HendersonHasselbalch Equation:

[ NH 4 ]
pOH pKb log

[ NH 3 ]

0.020
pOH log(1.8x105 ) log

0.060

(3) 50.00 mL of HCl has been added

pH = 9.26

(4) 75.00 mL of HCl has been added

pH = 8.77

pOH = 4.27 (as with the ICE table)

(5) 100.0 mL of HCl has been added


NH3 (aq) +

pH = 5.28

H3O+ (aq)

H2O (l) +

NH4+ (aq)
0
(initially, there is
no conjugate acid
present)

initial
mol

= (0.100M)
(0.1000 L)
= 0.0100 mol

= (0.100 M)
(0.1000 L)
= 0.0100 mol

change
in mol

0.0100 mol

0.0100 mol

+ 0.0100 mol

=0

=0

= 0.0100 mol

final
mol

This is the equivalence point in the titration because moles acid = moles base.
The only substance present at the equivalence point is the conjugate acid.

[ NH 4 ]

0.0100 mol
0.0500M
0.2000 L

(note: the total volume of the solution is 0.1000 L + 0.1000 L= 0.2000 L)


For a Weak Base/Strong Acid Titration, the solution is NOT neutral at the equivalence point. The conjugate acid will form an
equilibrium with water and the pH can be calculated using an ICE table.

[ H 3O ][ NH 3 ]
[ NH 4 ]

NH4+ (aq) +

H2O (l)

H3O+ (aq) +

NH3 (aq)

0.0500

x
0.0500 x
0.0500
assume x
is small

+x

+x

(the Ka expression and constant is used since


there is an acid equilibrium)

5.6 x1010

initial
mol

change
in mol
final
mol

x2
0.0500

x = 5.3x106 M = [H3O+]
pH = log[H3O+] = log(5.3x106) = 5.28

(6) 125.0 mL of HCl has been added


NH3 (aq) +
= (0.100M)
(0.1000 L)
= 0.0100 mol
NH3 is the
LIMITING
reactant

Ka

pH = 1.95

H3O+ (aq)

H2O (l) +

= (0.100 M)
(0.1250 L)
= 0.0125 mol
H3O+ is the
EXCESS reactant

NH4+ (aq)
0
(initially, there is
no conjugate acid
present)

0.0100 mol

0.0100 mol

+ 0.0100 mol

= 0 (since NH3 is
the limiting
reactant, it is
completely
consumed)

= 0.0025 mol

= 0.0100 mol

The solution contains a mixture of excess strong acid (H 3O+) and conjugate acid (NH4+). The pH can be calculated from the
molarity of strong acid because the weak conjugate acid will not significantly contribute to [H3O+].

[ H 3O ]

0.0025 mol
0.011 M
0.2250 L

pH = log[H3O+] = log(0.011) = 1.95

(note: the total volume of the solution is 0.1250 L + 0.1000 L = 0.2250 L)


(7) 150.00 mL of HCl has been added
(8) 175.0 mL of HCl has been added

pH = 1.70
pH = 1.56

(9) 200.0 mL of HCl has been added. pH = 1.30

The pH values for each volume of HCl added can be graphed to create a titration curve.

pH

Strong Acid Weak Base Titration


14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
0

25

50

75

100

125

150

175

200

Volume HCl added (mL)

If a strong acid is added to a weak base, the four regions to be considered in titration curve calculations are as follows:
(1) Before any acid is added- pOH (and then pH) is calculated from the concentration and K b of the base using an ICE table.
(2) Before the equivalence point- pOH (and then pH) is calculated from the remaining concentration of base and produced
concentration of conjugate acid using an ICE table OR using the Henderson-Hasselbalch equation.
(3) At the equivalence point- pH is calculated from the concentration of conjugate acid using an ICE table and K a.
(4) After the equivalence point- pH is calculated from the excess concentration of acid.

Halfway to the Equivalence Point in a Titration Experiment


Weak Acid/Strong Base
In a titration experiment between a weak acid and a strong base, when the amount of base added is half the volume required to
reach the equivalence point, the contents of the solution are the cation of the strong base (i.e. Na+), unreacted weak acid (HA),
conjugate base (A) that has been produced, and a small amount H3O+ from the acid equilibrium with water. At this point in the
titration, the total positive charge is equal to the total negative charge so the overall charge of the solution is (approximately)
zero. The added OH has consumed half of the HA in the original solution by reacting to produce H2O and A. The number of
moles of the acid (HA) remaining will be equal to the number of moles of the conjugate base (A) produced. In a given volume,
the concentration of acid will be equal to the concentration of the conjugate base ([HA] = [A ]). Consider both the Ka
expression and the Henderson-Hasselbalch Equation at this point.

[ H 3O ][ A ]
From the Ka expression: K a
[ HA]

(since [HA] = [A])

Ka [ H 3O ]

From the Henderson-Hasselbalch Equation:

[ A ]
pH pK a log

[ HA]

pH = pKa + log (1)


(since [HA] = [A ], log 1 = 0)

pH = pKa

If the pH halfway to the equivalence point is determined, the [H 3O+] can be calculated, and therefore Ka can be found, or
equivalently, the pH of a solution halfway to the equivalence point will be equal to pK a.
Consider STEP 3 of the previous example (benzoic acid/sodium hydroxide). The volume of NaOH required to reach the
equivalence point was 100.0 mL, therefore, half the volume required to reach the equivalence point was 50.00 mL. At this point
in the titration, the number of moles of HC7H5O2 (acid remaining) was 0.0025 mol and the number of moles of C 7H5O2
(conjugate base produced) was also 0.0025 mol. The [HC7H5O2] = [C7H5O2] = 0.017 M. Since both the acid and the conjugate
base have the same concentration, pH = pKa (i.e. pH = log(6.3x105) = 4.20).

Summary of Titration Curves


nearing the
equivalence point

Titration

Initial pH

Strong
Acid added
to
Strong
Base

very
high
(only
strong
base is
present)

Strong
Base added
to
Strong
Acid

very
low
(only
strong
acid is
present)

steady increase

Strong
Acid added
to
Weak Base

medium
high
(weak
base is
present)

more gradual
decrease
(buffer region
with weak base
and conjugate
acid )

Strong
Base added
to
Weak Acid

medium
low
(weak
acid is
present)

more gradual
increase
(buffer region
with weak acid
and conjugate
base )

steady
decrease

Change in pH around
the equivalence point

At the
equivalence point

Final pH

extreme pH
change

pH = 7
(water is
present)

very low
(only
strong
acid is
present)

extreme pH
change

pH = 7
(water is
present)

very
high
(only
strong
base is
present)

more moderate
pH change

pH<7
(conjugate
acid is
present)

very low
(primari
ly strong
acid is
present)

more moderate
pH change

pH>7
(conjugate
base is
present)

very
high
(primari
ly strong
base is
present)

Titration Curve

Strength of an acid and shape of the titration curve


The overall shape of a titration curve is determined by the strength (i.e. K a value) of the acid. The stronger an acid, the lower its
initial pH; the weaker an acid the higher its initial pH. The stronger an acid, the lower the pH halfway to the equivalence point
(since the pKa is lower); the weaker an acid, the higher the pH halfway to the equivalence point (since the pKa is higher).
Stronger acids will have a more gradual initial increase in pH and then a more extreme increase in pH near the equivalence point;
weaker acids will have a more noticeable initial increase in pH and then a less drastic increase in pH near the equivalence point.
At the equivalence point, for stronger acids, the pH is lower (since the conjugate base is relatively weak); for weaker acids, the
pH is higher (since the conjugate base is relatively strong). After the equivalence point, the pH for both stronger acids and
weaker acids will be very similar since there is excess strong base in both cases.
Titration of 50.0 mL a 0.10 M solution of weak acid with 0.10 M NaOH

Ka

102
104
106
108
1010

pKa

Initial pH of 0.10 M
solution

pH at volume
halfway to
equivalence point
(25.0 mL NaOH
added)
note: pKa = pH

2
4
6
8
10

1.6
2.5
3.5
4.5
5.5

2
4
6
8
10

pH at equivalence
point
(50.0 mLNaOH
added)

7.35
8.35
9.35
10.35
11.35

Acid/Base Indicators
The equivalence point in an acid base titration is monitored using an acid base indicator. An indicator is a weak acid that
changes colour depending on whether it is in its acidic form or its basic form.
ex. HInd (aq) + H2O (l)
acidic form

H3O+ (aq) + Ind (aq)


basic form

The point in a titration at which the indicator changes colour is called the endpoint. Every indicator changes colour at a specific
pH value called its pKa value. When pH<pKa for the indicator, the indicator will be in its acidic form (HInd) and will display the
colour of the acidic form. When pH>pK a for the indicator, the indicator will be in its basic form (Ind ) and will display the
colour of the basic form. An indicator is selected for a given titration because its pKa value is close to the pH at the equivalence
point.
ex. Bromothymol blue is yellow in its acidic form and blue in its basic form. Bromothymol blue has a pK a value of 7.0 and
would be useful for a titration with an equivalence point around 7 (i.e. a strong acid and a strong base)
ex. Phenolphthalein is colourless in its acidic form and pink in its basic form. Phenolphthalein has a pK a value of 9.3 would be
useful for a titration with an equivalence point around 9 (i.e. a weak acid and a strong base)
ex. Methyl red is red in its acidic form and yellow in its basic form. Methyl red has a pKa value of 5.1 and would be useful for a
titration with an equivalence point around 5 (i.e. a strong acid and a weak base)
ex. Acidic and Basic forms for Phenolphthalein

Indicators and the pH range of colour change. The middle of the range is the pKa for the indicator.

Equivalence Point vs. Endpoint


An important distinction must be made between the equivalence point of a titration and the endpoint of a titration.
The equivalent point, also called the stoichiometric point, is where the moles of acid are equal to the moles of base. At this point
of the experiment, the reaction is complete. The analyte is said to be titrated at this point.
The endpoint of a titration is where the acid/base indicator is observed to change colour. The careful selection of an appropriate
indicator is to ensure that the pKa of the indicator will be very close to the pH at the equivalence point (i.e. that the volume
required to reach the equivalence point is a close as possible to the volume required to reach the endpoint).

Diprotic Titration
If a strong base is titrated with a weak diprotic acid, there will be two equivalence points as shown in the following titration
curve.

Consider the weak acid H2A


The first equivalence point involves the reaction of
the first proton in the acid with the added base.
H2A + OH H2O + HA
The second equivalence point involves the reaction of
the second proton in the acid with the added base.
HA + OH H2O + A2
The total volume of base required to reach the second
equivalence point is twice the volume required to
reach the first equivalence point.

For a triprotic (H3A) acid, there would be three different equivalence points, one for each proton.

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