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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
Sr(OH)2 Sr + 2OH
strontium hydroxide
Ca(OH)2 Ca2+ + 2OH
calcium hydroxide
(note: other group II elements are insoluble in water)
pOH = log[OH]
[OH] = 10pOH
nitric acid
periodic acid
sulphuric acid
chloric acid
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
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:
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]
The acid dissociation constant can also be expressed as pKa where pKa = log(Ka) or K a 10
Bases:
pKa
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]
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.
[ H 3O ][ F ]
Ka
[ HF ]
ex.
[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)
ex. Complete the following acidbase equilibria. Identify the conjugate acidbase pairs and write a Ka or Kb expression.
(1) HOBr (aq) + 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+]
changein concentration
x100%
initial concentration
0.027
x100% 2.7%
1.0
(therefore the approximation is valid)
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
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]
changein concentration
x100%
initial concentration
0.0042
x100% 0.42%
1.0
(therefore the approximation is valid)
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
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+]
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)
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)
K a Kb K w
Kw = 1.0x1014 (at 25 C), Ka is the acid dissociation constant, and Kb is the base dissociation constant
Ka
[ H 3O ][ F ]
= 7.2x104
[ HF ]
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 ]
[OH ][C5 H 5 NH ]
=1.7x109
Kb
[C5 H 5 N ]
Note:
Kb xK a
K w 1.0 x1014
Ka
5.9 x109
9
Kb 1.7 x10
Ka
[ H 3O ][C5 H 5 N ]
= 5.9x109
[C5 H 5 NH ]
Kb
K w 1.0 x1014
2.3x108
7
K a 4.3x10
Ka = 1.0x107
K = 1/5.6x1010 = 1.8x109
__________________________________________________________
Kb = 1.8x105
K = 1/1.0x107 = 1.0x107
______________________________________________________
(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.
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
_______________________________________________________________________
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.
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.
+
2
HCO3 + H2O (l)
H3O (aq) + CO3 (aq)
Ka2 = 5.6x1011
_______________________________________________________
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.
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
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)
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
[ A ]
pH pK a log
[ HA]
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)
(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.
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)
0.0030 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)
0.0050 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)
HCl H + Cl
therefore, [H+] = 0.100 M
pH = log[H ]
= log(0.100)
= 1.000
initial
mol
initial
mol
change
in mol
final
mol
= (0.100M)
(0.1000 L)
= 0.0100 mol
H+ is the EXCESS
reactant
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 = 1.85
OH (aq)
= (0.100M)
(0.1000 L)
= 0.0100 mol
0.0100 mol
0.0100 mol
=0
=0
initial
mol
change
in mol
[OH ]
H+ (aq) +
= (0.100M)
(0.1000 L)
= 0.0100 mol
H2O (l)
final
mol
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
pH = 12.30
pH = 12.43
The pH values for each volume of NaOH added can be graphed to create a titration curve.
pH
25
50
75
100
125
150
175
200
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.
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+]
pH = log[H3O+]
= log(0.0018)
= 2.75
(2) 25.00 mL of NaOH has been added
pH = 3.72
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
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 = 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
OH (aq) +
H2O (l)
HC7H5O2 (aq)
Kb
0.025
x
0.025 x
0.025
assume x
is small
+x
+x
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
pH =12.13
pH
25
50
75
100
125
150
175
200
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.
H2O (l)
OH (aq) +
0
NH4+ (aq)
0
NH3 (aq) +
0.100
+x
+x
0.100 x
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
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
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]
OR
HendersonHasselbalch Equation:
[ NH 4 ]
pOH pKb log
[ NH 3 ]
0.020
pOH log(1.8x105 ) log
0.060
pH = 9.26
pH = 8.77
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
[ 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
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
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 = 1.70
pH = 1.56
The pH values for each volume of HCl added can be graphed to create a titration curve.
pH
25
50
75
100
125
150
175
200
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.
[ H 3O ][ A ]
From the Ka expression: K a
[ HA]
Ka [ H 3O ]
[ A ]
pH pK a log
[ HA]
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).
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
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
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.
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.
For a triprotic (H3A) acid, there would be three different equivalence points, one for each proton.