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LEARNING OUTCOMES
Candidates should be able to:
(a) show understanding of, and apply the BronstedLowry theory of acids and bases, including
the concept of conjugate acids and conjugate bases
(b) explain qualitatively the differences in behaviour between strong and weak acids and bases in
terms of the extent of dissociation
(c)
explain the terms pH; Ka; pKa; Kb; pKb; Kw and apply them in calculations, including the
relationship Kw = KaKb
(d) calculate [H+(aq)] and pH values for strong acids, weak monobasic (monoprotic) acids, strong
bases, and weak monoacidic bases
(e) explain the choice of suitable indicators for acidbase titrations, given appropriate data
(f)
describe the changes in pH during acidbase titrations and explain these changes in terms of
the strengths of the acids and bases
(g) (1) explain how buffer solutions control pH
(2) describe and explain their uses, including the role of H2CO3/HCO3 in controlling pH in
blood
(h) calculate the pH of buffer solutions, given appropriate data
CONTENT
1
Buffer Solutions
Buffer action
pH of buffer solutions
Blood as a buffer system
Acidbase Titrations
pH indicators
Titration curves
REFERENCES
1.
2.
Peter Cann & Peter Hughes (2002). Chemistry for Advanced Level. John Murray. Chapters 6 & 12.
Martin S. Silberberg (2006). Chemistry The Molecular Nature of Matter & Change,
4th Edition. McGraw Hill. Chapters 18 & 19.
__________________________________________________________________________________________________
Cheng ML/ Soh SK/ Tan CS/ Teo ME
1
1.1
(b)
(c)
(d)
Lewis acidbase
definition
1.2
CH3CO2
conjugate base
H2O
base
H3O+
conjugate acid
base 2
base 1
acid 2
EXERCISE 2
Identify the conjugate acidbase pairs in each of the following reactions:
(a)
(b)
(c)
(d)
1.3
HCl
strong acid
H2O
Cl
conjugate base
H3O+
The conjugate base of a strong acid has a very low tendency to accept a proton.
So the reverse reaction is negligible singleheaded arrow ().
Other examples of strong acids: HNO3, HBr, HI, HClO3, HClO4, H2SO4
A weak acid is one that dissociates partially in water to give H3O+. It gives up a proton less readily
compared to the H3O+ ion.
e.g.
CH3CO2H
weak acid
H2O
CH3CO2
conjugate base
H3O+
NaOH
Na+ + OH
Other examples of weak bases: hydrazine N2H4, amines such as CH3NH2, C6H5NH2
The strength of an acid (or base) is different from the concentration of the acid (or base).
Concentration of an acid (or base) = No. of moles of acid (or base) dissolved in 1 dm3 of solution.
EXERCISE 3
Match each acid on the left with the correct description on the right.
0.001 mol dm3 HNO3
2.1
A)
pH and pOH
The concentration of H+ and OH in an aqueous solution is usually quite small. A convenient
indication of the concentration of H+(aq) is to express it in terms of its negative logarithm to base 10.
pH = lg [H+(aq)]
Hence,
[H+(aq)] = 10pH
E.g. for 0.01 mol dm3 HCl, [H+(aq)] = 102 mol dm3 and pH = 2.
Note:
pH is a measure of the (total) concentration of H+ in a solution. It is not a measure of the strength of
the acid unless the two acids being compared have the same initial concentration (see Section 2.6).
Similarly, a convenient indication of the concentration of OH(aq) is to express it in terms of its
negative logarithm to base 10.
pOH = lg [OH(aq)]
and
[OH(aq)] = 10pOH
E.g. for 0.01 mol dm3 NaOH, [OH(aq)] = 102 mol dm3 and pOH = 2.
B)
H3O+(aq)
H2O(l)
OH(aq)
H+(aq)
OH(aq)
Kc
[H+][OH]
[H2O]
Since the extent of ionisation is very small, [H2O] is almost constant (at 55.6 mol dm3).
Therefore,
Kc x [H2O] = [H+][OH]
Kw = [H+][OH]
or
pKw = pH + pOH = 14
C)
H2O(l)
OH(aq)
Thus, an acidic solution contains a few hydroxide ions, and an alkaline solution contains a few
hydrogen ions.
The product of [H+] and [OH] always equals Kw since Kw is an equilibrium constant and its numerical
value is only affected by temperature.
When
Acidic
> 1.0 x 10
Basic
< 1.0 x 10 7
pH
pOH
= 1.0 x 10
= 7.00
= 7.00
< 1.0 x 10
< 7.00
> 7.00
> 7.00
< 7.00
> 1.0 x 10 7
Kw / mol2 dm6
0
10
25
40
60
1.5 1015
3.0 1015
1.0 1014
3.0 1014
9.5 1014
[H+] = [OH] =
K w / mol dm3
3.9 108
5.5 108
1.0 107
1.7 107
3.1 107
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(viii)
2.2
Similarly,
and
and
Note: If the concentration of the acid or base is 107 mol dm3 or lower, the contribution of H+ or OH
from autoionization of H2O becomes significant. We will need to include it in the calculation.
EXERCISE 5
(a)
An aqueous solution contains 1.0 105 mol dm3 of hydrogen iodide (a strong acid). Calculate
the concentration of H+ in mol dm3, and hence the pH of this solution at 25 oC.
Ans: [H+] = 1.00 105 mol dm3, pH = 5.00
+
(b)
An aqueous solution contains 0.10 mol dm3 of calcium hydroxide (a strong base). Calculate
the concentration OH in mol dm3, and hence the pH of this solution at 25 oC.
Ans: [OH] = 0.200 mol dm3, pH = 13.3
Ca(OH)2(aq) Ca2+(aq) + 2OH(aq)
[OH] = 2 [Ca(OH)2] = 0.200 mol dm3
pOH = lg [OH] = lg 0.2 = 0.699
pH = 14 pOH = 14 0.699 = 13.3
(c)
An aqueous solution contains 0.010 mol dm3 of Ba(OH)2 (a strong base) and 0.050 mol dm3
of KOH. Calculate the pH of this solution at 25 oC.
Ans: pH = 12.8
Ba(OH)2(aq) Ba2+(aq) + 2OH(aq)
KOH(aq) K+(aq) + OH(aq)
Total [OH] = 20.010 + 0.050 = 0.070 mol dm3
pH = 14 pOH = 14 + lg 0.070 = 12.8
8
(d)
Solution X contains HCl, it has pH 2.2. Solution Y has the same volume as solution X, it contains
HNO3 and has pH 1.6. The two solutions are mixed. Calculate the pH of the acid mixture.
Ans: 1.80
2.2
10 1.6 = 0.0157 mol dm3
Total [H+] = 10
pH = lg 0.0157 = 1.80
(e)
An aqueous solution contains 1 x 108 mol dm3 of HNO3. Calculate the pH of this solution.
Ans: 6.96
+
Hence,
2.3
Dissociation Constants
A)
H2O
H3O+
In dilute aqueous solution, [H2O] is almost constant (at 55.6 mol dm3). The equilibrium constant may
be written as:
Ka
and
[H+]eqm[A]eqm
[HA]eqm
mol dm3
pKa = lg Ka
For strong acids e.g. HCl, Ka is very large and not used.
Like other equilibrium constants, the value of Ka depends only on temperature.
The value of Ka indicates the extent to which the weak acid dissociates in water at the specified
temperature.
To compare the strength of two weak acids, compare their Ka values.
At the same temperature, larger Ka (smaller pKa) stronger acid.
B)
Equilibrium reaction
Ka /mol dm3
1.8 X 105
1.8 x 104
6.5 x 105
HCN + H2 O CN + H3O+
4.9 x 1010
BH+
H2O
OH
In dilute aqueous solution, [H2O] is almost constant (at 55.6 mol dm3). The equilibrium constant may
be written as:
Kb
and
[BH+]eqm[OH]eqm
[B]eqm
mol dm3
pKb = lg Kb
For strong bases e.g. NaOH, Kb is very large and not used.
The value of Kb depends only on temperature.
The value of Kb indicates the extent to which the weak base dissociates in water at the specified
temperature.
To compare the strength of two weak bases, compare their Kb values.
At the same temperature, larger Kb (smaller pKb) stronger base.
Kb /mol dm3
NH3 + H2 O NH4+ + OH
1.8 X 105
CH3NH2 + H2 O CH3NH3+ + OH
4.4 x 104
HS + H2 O H2S + OH
1.8 x 104
CO32 + H2 O HCO3 + OH
1.8 x 104
In aqueous solution, the two large classes of weak bases are nitrogencontaining molecules such
as NH3 and the amines (e.g. CH3CH2NH2), and the anions or conjugate bases of weak acids (e.g.
ethanoate ion, CH3CO2).
10
C)
[CH3CO2][H+]
[CH3CO2H]
(1)
[CH3CO2H][OH]
[CH3CO2]
(2)
Ka x Kb = [H+] [OH] = Kw
(1) X (2),
Hence, we can determine the value of Ka, given the Kb value of its conjugate base and vice versa.
From Ka x Kb = Kw , we see that for a conjugate acidbase pair,
as the strength of the acid decreases (smaller Ka), the strength of its conjugate base increases (larger
Kb) and vice versa.
E.g. CH3CO2H is a weak acid (Ka of CH3CO2H = 1.80 x 105 mol dm3), its conjugate base CH3CO2 is a
stronger base than water. Hence CH3CO2 has a tendency to accept a proton from water.
However, CH3CO2 is still a weak base (Kb of CH3CO2 = 5.56 x 1010 mol dm3).
2.4
Degree of Dissociation
The fraction of molecules which is ionised into ions in water is called the degree of dissociation, .
For an acid,
In general,
amount ionised
initial amount
[acid]dissociated
[acid]initial
is close to 1
<< 1
11
2.5
Ka
x = [H+] =
H+
HA
0.1
x
0.1 x
[H+][A]
+x
x
[HA]
x2
0.1 x
+x
x
x2
0.1
(b)
Note:
The assumption (x << 0.1) is valid since a weak acid only dissociates partially.
Check: x = 1.3325 x 103 (by solving quadratic equation) << 0.1
Solving quadratic equations is not required at A Level.
Generally, for a weak monobasic acid,
Ka
[H+] =
[H+]eqm[A]eqm
[HA]eqm
[H+]eqm2
[HA]eqm
[H+]eqm2
[HA]initial
[HA]initial Ka
12
EXERCISE 7
The pH of a weak acid, HA, of concentration 0.100 mol dm3 was found to be 3.0. Calculate the pKa of
the acid.
Ans: 5.00
HA(aq) H+(aq) + A (aq)
Since pH = 3.0,
Ka
[H+]eqm[A]eqm
(103) (103)
[HA]eqm
0.1 103
1.01 x 105
mol dm3
pKa = lg Ka = 5.00
Note:
If [H+]eqm is known, the assumption [H+] << [HA] is not required in the calculations.
EXERCISE 8
Caffeine, C8H10N4O2, a stimulant found in coffee and tea, is a weak base.
C8H10N4O2 + H2O (C8H11N4O2)+ + OH
At 25 oC, a 0.020 mol dm3 caffeine solution has a pH of 11.5.
(a)
(b)
(a)
Kb = [C 8H11N4 O 2 ][OH ]
[C 8H10N4 O 2 ]
(b)
(3.162 10 3 )2
0.020 3.162 10 3
3
= 3.162 10
= 0.158
0.020
13
2.6
degree of dissociation, : .
Now, find (a) the pH and (b) the degree of dissociation of ethanoic acid of concentration 0.001 mol
dm3. How have the pH and been affected by the dilution?
(a)
(b)
Since pH and degree of dissociation of an acid (or base) will change with change in concentration,
they are not reliable indicators of acid (or base) strength.
Hence, the values of pH, and Ka for a weak acid at a constant temperature will vary with dilution
(i.e. volume of water increases) as follows:
pH
Ka
Volume of water
(pH 7 as dilution )
Ka
Volume of water
Volume of water
( 1 as dilution )
Ka does not vary with concentration. It is a constant at constant temperature. Therefore Ka is the
best indicator of the strength of a weak acid.
14
NH3(aq)
weaker base
H2O(l)
weaker acid
NH4+(aq)
stronger acid
OH(aq)
stronger base
Kc = 3.2 107
Kc is very small, this suggests that the position of equilibrium lies very much to the left.
So NH4+ is a better proton donor than H2O, OH is a better proton acceptor than NH3.
(b)
C6H5O
stronger base
CH3CO2H
stronger acid
C6H5OH
weaker acid
CH3CO2
weaker base
Kc = 1.3 106
Kc is very large, this suggests that the position of equilibrium lies very much to the right.
So CH3CO2H is a better proton donor than C6H5OH, C6H5O is a better proton acceptor than
CH3CO2.
Note:
In part (a), NH3 is a weak base (Kb = 1.80 x 105 mol dm3) so its conjugate acid NH4+ is a stronger acid
than water. Recall from Section 2.3C, Ka x Kb = Kw.
However, NH4+ is still a weak acid (Ka of NH4+ = 5.56 x 1010 mol dm3).
From part (b), we see that the stronger acid is able to protonate the conjugate base of the weaker
acid.
Strong acids (e.g. HCl) are often used to liberate the weak acids (e.g. CH3CO2H) from their salt (e.g.
CH3COONa+).
HCl(aq)
+ CH3CO2(aq) Cl(aq) + CH3COOH(aq)
stronger acid
salt
weaker acid
2.7
A)
H2O(l)
NH3(aq)
H3O+(aq)
B)
H2O(l)
CH3CO2H(aq)
OH(aq)
C)
D)
H
+
H
+
Figure shows [Al(H2O)6]3+ acting as an acid, donating a proton to another H2O molecule
Hydrated ion
[Fe(H2O)6]3+(aq)
[Cr(H2O)6]3+(aq)
[Al(H2O)6]3+(aq)
Note:
In the presence of a base stronger than water e.g. OH, further abstraction of protons can occur.
[Al(H2O)5(OH)]2+(aq) + H2O(l) [Al(H2O)4(OH)2]+(aq) + H3O+(aq)
17
EXERCISE 11
State whether the following solutions are acidic, alkaline or neutral. Write an equation, including
state symbols, for any hydrolysis reaction.
(a)
KBr(aq)
neutral, no hydrolysis reaction
(b)
NaCN(aq)
alkaline
CN(aq) + H2O(l) HCN(aq) + OH(aq)
(c)
CH3NH3+Cl (aq)
acidic
CH3NH3+(aq) + H2O(l) CH3NH2(aq) + H3O+(aq)
(d)
(e)
(1)
(2)
(f)
FeCl3(aq)
acidic
Fe(H2O)63+(aq) + H2O(l) Fe(OH)(H2O)52+(aq) + H3O+(aq)
18
Initial conc
Eqm conc
Kb (CH3CO2)
CH3CO2
0.10
0.10 x
CH3CO2H
x
Kw
Ka (CH3CO2H)
5.56 x 1010
x2/(0.10 x)
x2/0.10
OH
x
BUFFER SOLUTIONS
3.1
19
3.2
A)
Acidic buffer
E.g. CH3CO2H and CH3CO2Na+
Ethanoic acid is a weak acid and dissociates partially.
CH3CO2H CH3CO2 + H+
(1)
Adding sodium ethanoate (completely soluble in water) to this solution adds a lot of extra ethanoate
ions.
CH3CO2Na+ CH3CO2 + Na+
According to Le Chatelier's Principle, the position of equilibrium (1) shifts further to the left (i.e. the
dissociation of ethanoic acid is suppressed).
Concept Check: What happens to the pH of the solution when sodium ethanoate is added to ethanoic
acid?
The solution now contains the following:
large reservoir of unionised ethanoic acid;
large reservoir of ethanoate ions from the sodium ethanoate;
and can act as an acidic buffer solution.
Action of Acidic Buffer
(i)
When a small amount of H+ is added to this buffer, the H+ ions react with the large reservoir of
the CH3CO2 (conjugate base):
CH3CO2 + H+ CH3CO2H
The added H+ ions are removed and pH remains almost constant.
(ii)
When a small amount of OH is added to this buffer, the OH ions react with the large
reservoir of the unionized CH3CO2H molecules:
CH3CO2H + OH CH3CO2 + H2O
The added OH ions are removed and pH remains almost constant.
Note:
Buffer action equations are written with single (nonreversible) arrows.
In (i), after the reaction, [CH3CO2H] increases slightly and [CH3CO2 ] decreases slightly.
In (ii), after the reaction, [CH3CO2H] decreases slightly and [CH3CO2 ] increases slightly.
As the original amounts of CH3CO2H and CH3CO2 are large compared to the amount of H+ or OH
ions added, the ratio [CH3CO2H] / [CH3CO2 ] remains almost constant,
and [H+] = Ka [CH3CO2H] / [CH3CO2 ] remains almost constant, so pH remains almost constant.
20
B)
Alkaline buffer
E.g. aqueous NH3 and NH4+Cl
Ammonia is a weak base and dissociates partially.
NH3(aq) + H2O(l) NH4+(aq) + OH (aq)
(2)
Adding ammonium chloride (completely soluble) to this solution adds a lot of extra ammonium ions.
NH4+Cl NH4+ + Cl
According to Le Chatelier's Principle, the position of equilibrium (2) shifts further to the left (i.e. the
dissociation of NH3 is suppressed).
Concept Check: What happens to the pH of the solution when ammonium chloride is added to
ammonia?
The solution now contains the following:
large reservoir of unionised ammonia;
large reservoir of ammonium ions from the ammonium chloride;
and can act as an alkaline buffer solution.
Action of Alkaline Buffer
(i)
When a small amount of H+ is added to this buffer, the H+ ions react with the large reservoir of
the NH3 (weak base):
NH3 + H+ NH4+
The added H+ ions are removed and pH remains almost constant.
(ii)
When a small amount of OH is added to this buffer, the OH ions react with the large
reservoir of the NH4+ (conjugate acid) from the salt:
NH4+ + OH NH3 + H2O
The added OH ions are removed and pH remains almost constant.
Note:
As the original amounts of NH3 and NH4+ are large compared to the amount of H+ or OH ions added,
the ratio [NH3] / [NH4+ ] remains almost constant,
and [OH] = Kb [NH3] / [NH4+ ] remains almost constant, pOH and thus pH remains almost constant.
21
3.3
pH of Buffer Solutions
A)
Acidic buffer
In a buffer consisting of HA and its salt A, the following equilibrium exists:
HA(aq) + H2O(l) H3O+(aq) + A (aq)
and
Ka
[H+]eqm[A]eqm
[HA]eqm
+
[A ]eqm [Na A ]initial
(since [A] from HA is very small)
therefore
and
Ka
[H+]
[H+]eqm[A]initial
[HA]initial
Ka
[H+]eqm[salt]
[acid]
[acid]
[salt]
Recall
[H ] = [A ] if the solution contains only the weak acid HA.
Alternatively, to find pH of a buffer, take lg on both sides of boxed equation,
lg[H ] lgKa lg
pH pKa lg
[acid]
[salt]
[s alt]
[acid]
HendersonHasselbalch Equation
It is important to use the correct concentrations in the numerator and denominator of the last term
in the equation.
B)
Alkaline buffer
In a similar manner as above, the pOH and pH of an alkaline buffer can be found using:
and
[OH ]
Kb
[base]
[salt]
22
Ka
1.8 x 10
[CH3CO2H]
[H+] (0.02)
[H+]
pH
3.28/82
[H+][CH3CO2 ]
0.010
5.05
EXERCISE 15
Calculate the change in pH when 1 cm3 of a 1.00 mol dm3 NaOH is added to 1 dm3 of
(a)
water;
(b)
the buffer in Exercise 14
Ans: +4 units; +0.05 units
(a)
[OH] =
pOH = 3
1
= 9.99 x 104 mol dm3
1.001
1
1000
pH = 11
Change in pH = 11 7 = +4 units
(b)
Ka
[H+]
pH
1.8 x 10
3.4
A)
[acid]
or
[salt]
[base]
or
pOH = pKb
This buffer is said to have the maximum buffer capacity and it can most effectively resist a change in
pH in either direction (i.e. when either acid or base is added).
B)
[a ci d]
[s a l t]
[H+] = Ka
[OH] = Kb
[ba s e]
[s a l t]
24
EXERCISE 16
Which of the following acids would be the best choice to combine with its sodium salt to make a
solution buffered at pH 4.25?
For your choice, calculate the ratio of the salt (conjugate base) to the acid concentrations required to
attain the desired pH.
Acid
chlorous acid (HClO2)
nitrous acid (HNO2)
methanoic acid (HCO2H)
hypochlorous acid (HClO)
pKa
1.95
3.34
3.74
7.54
The best choice is methanoic acid because its pKa lies closest and within 1 unit of the desired pH.
Ka
10
3.5
3.74
=
[salt]
[acid]
[H+][salt]
[acid]
104.25 [salt]
[acid]
=
3.24
26
3.6
27
ACIDBASE TITRATIONS
4.1
HIn(aq)
red
red
colourless
H+(aq)
In(aq)
blue
yellow
pink
At different pH values, the proportion of HIn to In is different, giving rise to different colours.
For litmus:
In acidic solutions, [H+] is high. The position of equilibrium lies on the left. Predominant form of
litmus is HIn so the solution will appear red.
In alkaline solutions, [OH] is high so [H+] is low. The position of equilibrium lies on the right.
Predominant form of litmus is In hence the solution will appear blue.
4.2
KIn
[H+][ In]
[HIn]
pH
pKIn + lg
[ In]
[HIn]
For litmus:
If the ratio of [In]/[HIn] 10/1, i.e. pH pKIn + 1, the solution appears blue.
If the ratio of [In]/[HIn] 1/10, i.e. pH pKIn 1, the solution appears red.
Therefore, the litmus changes from red to blue over a pH range of
pH = pKIn 1
to
pH = pKIn + 1
That is, the working range of an indicator (i.e. pH range where a marked colour change occurs) is
approximately
pKIn 1
.
28
EXERCISE 17
At low pH, the colour of bromocresol green is yellow, and at high pH, the colour is blue. Calculate the
pH at which the colour of bromocresol green (KIn = 1.58 x 105) is green.
HIn(aq)
yellow
H+(aq)
In(aq)
blue
4.3
pH = pKIn = 4.80
Choice of Indicators
During an acidbase titration, one solution is run into the other in the presence of an indicator.
Endpoint: the point in a titration at which the indicator changes colour when 1 drop of excess
titrant is added.
Equivalence point: the point in a titration at which the exact number of moles of acid and base
react completely.
The endpoint coincides with the equivalence point only when a suitable indicator is used.
The indicator must have a distinct colour change.
The working range of the indicator must coincide with the rapid pH change for the titration.
The rapid pH change for the titration depends on the strengths of acid and alkali used. Either the
acid or the alkali, or both, may be strong or weak, so that there are four possible combinations.
Type
strong acid strong alkali
strong acid weak alkali
weak acid strong alkali
weak acid weak alkali
suitable indicator
methyl orange or phenolphthalein
methyl orange
phenolphthalein
no suitable indicator
29
4.4
(A)
Equivalence
point, pH = 7
At VNaOH = 25 cm3
Equivalence point is reached.
pH = 7 as the salt formed does not undergo
hydrolysis.
30
Homework 1
Determine the pH of the solution in the conical flask at the point when each of the following
volumes of NaOH is added.
(a)
0.00 cm3
Ans: 1.00
(b)
Ans: 1.48
(c)
24.90 cm3
Ans: 3.70
(d)
25.00 cm3
Ans: 7.00
(e)
25.10 cm3
Ans: 10.3
(f)
50.00 cm3
Ans: 12.5
31
B)
X
buffer region
Equivalence
point, pH > 7
1. Once the NaOH is added and some acid is neutralized, the solution contains a mixture of weak
acid and its salt a buffer solution forms.
2. The pH at the initial part of the titration curve and the part immediately before
complete neutralisation changes more sharply as these lie outside the effective buffer range
of the buffer.
3. The maximum buffer capacity occurs when half of the number of moles of acid is neutralized
at VNaOH = 12.50 cm3 (where [acid] = [salt]). At this point, pH = pKa of the weak acid.
At VNaOH = 25 cm
Equivalence point is reached. pH > 7 as the anion undergoes hydrolysis to produce OH:
CH3CO2(aq) + H2O(l) CH3CO2H(aq) + OH(aq)
Suitable indicator: phenolphthalein
The sharp change in pH in the curve near equivalence point occurs over a smaller pH range
compared to the previous strong acidstrong base titration.
At VNaOH > 25 cm
There is excess NaOH present in the solution. As NaOH is a strong base, [OH] is high and hence
pH is high (exact value depends on [NaOH] in excess).
Homework 2
Determine the pH of the solution in the conical flask at the point when each of the following
volumes of NaOH is added. (Ka of CH3CO2H = 1.8 105 mol dm3)
(a) 0.00 cm3
Ans: 2.87
3
(b) 12.50 cm (halfneutralisation point)
Ans: 4.74
3
(c)
25.00 cm (see Section 2.7, Exercise 12)
Ans: 8.72
32
C)
Equivalence
point, pH < 7
Equivalence point is reached. pH < 7 as the cation undergoes hydrolysis to produce H3O+:
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
Suitable indicator: methyl orange
At Vweak base > 25 cm
There is excess weak base present. The solution contains a mixture of weak base and its salt a
buffer solution forms.
What is the Vweak base and pH at which the buffer with maximum capacity occurs?
Ans: 50 cm3, 9.26
Homework 3
Determine the pH of the solution in the conical flask at the equivalence point.
(Kb of NH3 = 1.8 105 mol dm3)
Ans: 5.28
33
D)
Once the weak base is added and some acid is neutralised, the solution contains a mixture of
weak acid and its salt a buffer solution forms.
At Vweak base = 25 cm
Equivalence point is reached. There is no sharp change in pH, hence no suitable indicator can be
used, a pH meter may be used to help detect the equivalence point.
Both the cation and anion undergo hydrolysis (see Section 2.7C).
At Vweak base > 25 cm
There is excess weak base present in the solution together with its salt another buffer region is
formed.
34
4.5
In a titration of H2SO3, we can assume that all the H2SO3 molecules will lose one H+ ion before any of
the HSO3 ions loses its H+.
OH
OH
H2SO3 > HSO3 > SO32
35
(1)
(2)
The first rapid change in pH for reaction (1) occurs at pH = 8.5. Therefore a suitable indicator for the
first equivalence point is phenolphthalein.
The second rapid change in pH for reaction (2) occurs at pH = 4. Therefore a suitable indicator for the
second equivalence point is methyl orange.
To observe the two endpoints separately, phenolphthalein is first added. Methyl orange is added
only after the equivalence point is reached.
If methyl orange is used at the start of the experiment, only one endpoint is observed and the titre
obtained is twice that obtained with phenolphthalein.
EXERCISE 18 (Double indicator titration)
A 25.0 cm3 portion of a solution containing sodium carbonate and sodium hydrogencarbonate
needed 22.50 cm3 of a solution of hydrochloric acid of concentration 0.100 mol dm3 to decolourise
phenolphthalein. On addition of methyl orange, a further 28.50 cm3 of the acid was needed to turn
this indicator orange. Calculate the concentration of sodium carbonate and sodium
hydrogencarbonate in the solution.
Ans: 0.0900 mol dm3; 0.0240 mol dm3
With phenolphthalein indicator:
Na2CO3(aq) + HCl(aq) NaHCO3(aq) + NaCl(aq) (1)
No of moles of HCl used = 0.100 x 0.0225 = 2.25 x 103
No of moles of Na2CO3 = 2.25 x 103
[Na2CO3] = 2.25 x 103/0.025 = 0.0900 mol dm3
With methyl orange indicator:
NaHCO3(aq) + HCl(aq) NaCl(aq) + H2O(l) + CO2(g)
(from original NaHCO3 and
the NaHCO3 formed in (1))
Application
X = 10
H + A
+
HA
Ka =
[H ] eqm [A ] eqm
[HA] eqm
To calculate the pH of a
2
weak acid, Ka [H ] eqm
[HA] initial
buffer, Ka
BH + OH
+
To calculate the pH of a
[OH ] 2 eqm
weak base, Kb
[B] initial
buffer, Kb
CH3CO2 + H2O
CH3CO2H + OH