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CONTENT
3 Buffer Solutions
Buffer action (Independent Learning – Section 3.2 )
pH of buffer solutions
Blood as a buffer system (Independent Learning – Sections 3.5, 3.6)
4 Acid–base Titrations
pH indicators (Independent Learning – Sections 4.1, 4.2)
Titration curves
REFERENCES
1. Peter Cann & Peter Hughes (2002). Chemistry for Advanced Level. John Murray. Chapters 6 & 12.
2. 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
Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
A Bronsted–Lowry acid–base reaction involves the transfer of a proton from an acid to a base.
Acid–base reactions do not only occur in aqueous solutions. They can also occur between gases, in
non–aqueous solutions and in heterogeneous mixtures.
EXERCISE 1
Identify the Bronsted acid and base in each of the following (forward) reactions:
H2O is amphoteric (can act as an acid or a base, depending on the other substance present).
Note:
In aqueous solution, H+ (a ‘bare’ proton) does not exist on its own. Instead, it forms a dative bond
with a water molecule to form H3O+, called hydronium, hydroxonium or oxonium ion. Chemists
often use H+(aq) and H3O+(aq) interchangeably to refer to the solvated H+ ion.
Lewis acid–base Acids are species that accept an electron pair, e.g. AlCl3
definition Bases are species that donate an electron pair e.g. NH3
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
In general,
conjugate acid–base pair
EXERCISE 2
(a) HNO3 + NH3 NO3− + NH4+ HNO3 / NO3− and NH3 / NH4+
(b) HNO3 + H2O H3O+ + NO3– HNO3 / NO3− and H2O / H3O+
(c) NH3 + H2O ⇌ NH4+ + OH– NH3 / NH4+ and H2O / OH−
(d) HNO3 + H2SO4 H2NO3+ + HSO4– HNO3 / H2NO3+ and H2SO4 / HSO4–
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
A strong acid is one that dissociates completely in water to give H3O+. It gives up a proton more
readily compared to the H3O+ ion.
The conjugate base of a strong acid has a very low tendency to accept a proton.
So the reverse reaction is negligible single–headed 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.
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.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
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)]
E.g. for 0.01 mol dm–3 HCl, [H+(aq)] = 10–2 mol dm–3 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).
E.g. for 0.01 mol dm–3 NaOH, [OH(aq)] = 10–2 mol dm–3 and pOH = 2.
Pure water conducts electricity slightly. This indicates the presence of trace concentrations of ions
which arise from the very slight self–ionisation or autoionisation of water.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
[H+][OH–]
Kc =
[H2O]
Since the extent of ionisation is very small, [H2O] is almost constant (at 55.6 mol dm–3).
Experimentally, at 25oC, Kw = 1.0 x 10–14 mol2 dm–6 (value is given in the Data Booklet)
pKw = pH + pOH = 14
In pure water as well as any aqueous solution, the following equilibrium exists:
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.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
(viii) In pure water, the concentration of H+(aq) is higher than that of OH–(aq) at F
60 oC.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
Note: If the concentration of the acid or base is 10–7 mol dm–3 or lower, the contribution of H+ or OH–
from auto–ionization of H2O becomes significant. We will need to include it in the calculation.
EXERCISE 5
(a) An aqueous solution contains 1.0 10–5 mol dm–3 of hydrogen iodide (a strong acid). Calculate
the concentration of H+ in mol dm–3, and hence the pH of this solution at 25 oC.
Ans: [H+] = 1.00 10–5 mol dm–3, pH = 5.00
HI(aq) H (aq) + I (aq)
+ –
(b) An aqueous solution contains 0.10 mol dm–3 of calcium hydroxide (a strong base). Calculate
the concentration OH– in mol dm–3, and hence the pH of this solution at 25 oC.
Ans: [OH–] = 0.200 mol dm–3, pH = 13.3
(c) An aqueous solution contains 0.010 mol dm–3 of Ba(OH)2 (a strong base) and 0.050 mol dm–3
of KOH. Calculate the pH of this solution at 25 oC.
Ans: pH = 12.8
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
(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
Total [H+] = 10 10 1.6 = 0.0157 mol dm–3
2
pH = – lg 0.0157 = 1.80
(e) An aqueous solution contains 1 x 10–8 mol dm–3 of HNO3. Calculate the pH of this solution.
Ans: 6.96
HNO3 (aq) H (aq) + NO3 (aq)
+ –
HA + H2O A + H3O+
In dilute aqueous solution, [H2O] is almost constant (at 55.6 mol dm–3). The equilibrium constant may
be written as:
[H+]eqm[A–]eqm
Ka = mol dm–3
[HA]eqm
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.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
In dilute aqueous solution, [H2O] is almost constant (at 55.6 mol dm–3). The equilibrium constant may
be written as:
[BH+]eqm[OH–]eqm
Kb = mol dm–3
[B]eqm
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.
In aqueous solution, the two large classes of weak bases are nitrogen–containing molecules such
as NH3 and the amines (e.g. CH3CH2NH2), and the anions or conjugate bases of weak acids (e.g.
ethanoate ion, CH3CO2–).
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
Consider the weak acid, CH3CO2H, and its conjugate base, CH3CO2.
CH3CO2H ⇌ CH3CO2 + H+
[CH3CO2][H+]
Ka = –––––––––––––––––––– (1)
[CH3CO2H]
[CH3CO2H][OH]
Kb = –––––––––––––––––––– (2)
[CH3CO2]
Ka x Kb = Kw
Hence, we can determine the value of Ka, given the Kb value of its conjugate base and vice versa.
E.g. CH3CO2H is a weak acid (Ka of CH3CO2H = 1.80 x 10–5 mol dm–3), 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 10–10 mol dm–3).
The fraction of molecules which is ionised into ions in water is called the degree of dissociation, .
For an acid,
amount ionised [acid]dissociated
= =
initial amount [acid]initial
Since weak acids and weak bases dissociate partially in water, [H+] or [OH−] in the solution will be
less than the concentration of the weak acid or weak base.
EXERCISE 6
Find (a) the pH and (b) the degree of dissociation of a solution of ethanoic acid, CH3COOH, of
concentration 0.1 mol dm–3. [Given: Ka of CH3COOH = 1.8 x 10–5 mol dm–3]
Ans: 2.87; 1.34 10–2 or 1.34 %
(a)
HA H+ + A
Initial conc 0.1
Change x +x +x
Eqm conc 0.1 – x x x
[H+][A] x2 x2
Ka = = (assume x << 0.1)
[HA] 0.1 – x 0.1
Note:
The assumption (x << 0.1) is valid since a weak acid only dissociates partially.
Check: x = 1.3325 x 10–3 (by solving quadratic equation) << 0.1
EXERCISE 7
The pH of a weak acid, HA, of concentration 0.100 mol dm–3 was found to be 3.0. Calculate the pKa of
the acid.
Ans: 5.00
pKa = – lg Ka = 5.00
Note: If [H+]eqm is known, the assumption [H+] << [HA] is not required in the calculations.
EXERCISE 8
(a) Write the Kb expression of caffeine and calculate its value at 25 oC.
(b) Calculate the degree of dissociation, for caffeine at 25 oC.
Ans: 5.94 10–4 mol dm–3; 0.158 or 15.8 %
(a) Kb = [C 8H11N4 O 2 ][OH ]
[C 8H10N4 O 2 ]
3
(b) = 3.162 10 = 0.158
0.020
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
Are pH or degree of dissociation, α, reliable indicators of the strength of an acid (or base)?
EXERCISE 9
In Exercise 6 (p.12), the pH and the degree of dissociation of a solution of ethanoic acid of
concentration 0.1 mol dm–3 were found to be:
Now, find (a) the pH and (b) the degree of dissociation of ethanoic acid of concentration 0.001 mol
dm–3. How have the pH and α been affected by the dilution?
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, α and Ka for a weak acid at a constant temperature will vary with dilution
(i.e. volume of water increases) as follows:
pH α Ka
7 1 Ka
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.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
Each of the following reactions contains two Bronsted acids and two Bronsted bases. Suggest with
brief reasoning which is the stronger acid and which is the stronger base.
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.
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 10–5 mol dm–3) 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 10–10 mol dm–3).
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
An ionic salt may be prepared from a reaction between an aqueous acid and an aqueous base.
E.g. KCl may be prepared from KOH(aq) and HCl(aq).
Salt hydrolysis is a reaction in which ions react with water to produce OH– or H3O+ ions.
Salts derived from a strong acid and a strong base (e.g. NaCl, KNO3) do not undergo salt hydrolysis.
Hence the resulting solution is neutral pH = 7 at 25 oC.
However, ions in salts derived from weak acids/bases (in particular, the anions of weak acids, and
cations of weak bases), as well as metal cations with high charge density, could undergo hydrolysis
to result in solutions of pH greater/less than 7 (at 25 oC).
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
NH3 is a weak base so its conjugate acid NH4+ is a stronger acid than water. NH4+ undergoes
hydrolysis forming H3O+ ions.
Note:
NH4+ is a stronger acid than water (see Ex 10(a)) so is able to donate a proton to water.
However, it is still a weak acid (Ka of NH4+ = 5.56 x 10–10 mol dm–3). Hence a reversible arrow ⇌ is
used in the salt hydrolysis equation.
The anion Cl– (derived from strong acid HCl) is a weaker base than water so does not hydrolyse.
CH3CO2H is a weak acid so its conjugate base CH3CO2– is a stronger base than water. CH3CO2–
undergoes hydrolysis forming OH– ions.
Consider the ionic compound, aluminium nitrate Al(NO3)3. When it dissolves in water, the Al3+ and
NO3– ions are separated and is hydrated by water molecules.
Note:
The hydrated cations are coordinated to water molecules through dative (co–ordinate) bonds to
form complexes. E.g. [Al(H2O)6]3+, [Fe(H2O)6]3+, [Cr(H2O)6]3+
The Al3+ ion is small and highly charged, it has high charge density. It withdraws sufficient electron
density from the O–H bonds of the coordinated H2O molecules, weakening the O–H bonds. When
one O–H bond breaks, a proton is released:
We call this a hydrolysis reaction. Since [H3O+] > [OH–], Al3+(aq) is acidic, pH < 7.
+
+
H
–
O
–
H
+
+
Figure shows [Al(H2O)6]3+ acting as an acid, donating a proton to another H2O molecule
Note:
In the presence of a base stronger than water e.g. OH–, further abstraction of protons can occur.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
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)
(b) NaCN(aq)
alkaline
CN–(aq) + H2O(l) ⇌ HCN(aq) + OH–(aq)
acidic
CH3NH3+(aq) + H2O(l) ⇌ CH3NH2(aq) + H3O+(aq)
(e) NH4HS(aq), given: Kb of NH3 = 1.8 10–5 mol dm–3 H2S is a weak diprotic acid
Ka1 of H2S = 9 10–8 mol dm–3 Ka1 : H2S(aq) ⇌ HS–(aq) + H+(aq)
Ka2 : HS–(aq) ⇌ S2–(aq) + H+(aq)
Since Kb of HS– > Ka of NH4+, (2) occurs to a larger extent than (1).
Thus, resultant [OH–] > [H3O+]. The salt solution is alkaline.
(f) FeCl3(aq)
acidic
Fe(H2O)63+(aq) + H2O(l) ⇌ Fe(OH)(H2O)52+(aq) + H3O+(aq)
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
Kw
Kb (CH3CO2–) = = 5.56 x 10–10
Ka (CH3CO2H)
= x2/(0.10 – x)
≈ x2/0.10 (assuming 0.10 >> x)
pH = 14−pOH = 8.87
3 BUFFER SOLUTIONS
A buffer solution is one that is able to resist pH changes upon addition of a small amount of acid or
base.
So a buffer (usually) consists of two solutes – one provides a weak Bronsted acid and the other
provides a weak Bronsted base. Together, they form a conjugate acid–base pair.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
A) Acidic buffer
E.g. CH3CO2H and CH3CO2Na+
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?
(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
(ii) When a small amount of OH is added to this buffer, the OH ions react with the large
reservoir of the un–ionized CH3CO2H molecules:
The added OH ions are removed and pH remains almost constant.
Note:
Buffer action equations are written with single (non–reversible) 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.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
B) Alkaline buffer
E.g. aqueous NH3 and NH4+Cl
Adding ammonium chloride (completely soluble) to this solution adds a lot of extra ammonium ions.
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?
(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+
(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:
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.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
A) Acidic buffer
In a buffer consisting of HA and its salt A, the following equilibrium exists:
[H+]eqm[A]eqm
and Ka =
[HA]eqm
[H+]eqm[A]initial [H+]eqm[salt]
therefore Ka =
[HA]initial [acid]
[acid]
and [H+] = Ka
[salt]
Note:
When the ratio [acid]/[salt] remain almost constant, [H+] and therefore pH will remain almost
constant (see Section 3.2A).
[s alt]
pH pKa lg Henderson–Hasselbalch Equation
[acid]
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:
[base]
and [OH ] = Kb
[salt]
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
What is the pH of a buffer solution made by adding 3.28 g of sodium ethanoate (M r = 82) to 2 dm3 of
0.010 mol dm–3 ethanoic acid? (Ka of ethanoic acid = 1.8 x 10–5 mol dm–3)
Ans: 5.35
3.28/82
Concentration of ethanoate ions, [CH3CO2– ] = = 0.02 mol dm–3
2
[H+][CH3CO2– ]
Ka =
[CH3CO2H]
–5
[H+] (0.02)
1.8 x 10 =
0.010
EXERCISE 15
Calculate the change in pH when 1 cm3 of a 1.00 mol dm–3 NaOH is added to 1 dm3 of
(a) water; (b) the buffer in Exercise 14
Ans: +4 units; +0.05 units
1
1
(a) [OH–] = 1000
= 9.99 x 10–4 mol dm–3
1.001
pOH = 3 pH = 11
Change in pH = 11 – 7 = +4 units
–5
[H+] (0.04 + 0.001)
Ka = 1.8 x 10 =
0.010 – 0.001
The capacity of a buffer is the quantity of H3O+ or OH– it can remove before its pH changes
drastically.
A buffer should have high [HA] and [A–], or high [B] and [BH+], to provide a large reservoir of the
relevant components.
The more concentrated the components of a buffer, the greater the buffer capacity.
The more similar the concentrations of the buffer components, the greater the buffer capacity.
[salt] [salt]
It can be shown that the most effective buffer has = 1 or = 1
[acid] [base]
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).
The further the buffer–component concentration ratio is from 1, the less effective the buffering
action (i.e., lower buffer capacity).
In practice, a buffer is no longer effective when [salt]/[acid] or [salt]/[base] > 10/1 or < 1/10.
[a ci d]
for an acidic buffer, [H+] = Ka effective buffer pH range = pKa 1
[s a l t]
[ba s e]
for an alkaline buffer, [OH] = Kb effective buffer pOH range = pKb 1
[s a l t]
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
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 pKa
chlorous acid (HClO2) 1.95
nitrous acid (HNO2) 3.34
methanoic acid (HCO2H) 3.74
hypochlorous acid (HClO) 7.54
The best choice is methanoic acid because its pKa lies closest and within 1 unit of the desired pH.
[H+][salt]
Ka =
[acid]
10–4.25 [salt]
–3.74
10 =
[acid]
[salt]
= 3.24 Check: Ratio is between 0.1 and 10 (effective range)
[acid]
The pH of our blood must be kept constant at about 7.4 since enzymes operate only within a narrow
pH range.
The most important buffer system in blood plasma involves the weak acid H2CO3 (an aqueous
solution of CO2) and its conjugate base, HCO3 ions.
Read the article on the following page for an elaboration on this buffer system.
If blood pH rises above about 7.45, you can suffer from a condition called
alkalosis. This can arise from hyperventilation or oxygen deficiency at high
altitude. It can lead to over excitability of the central nervous system, muscle
spasms and death. One way to treat alkalosis is to breath into a paper bag.
The CO2 exhaled is recycled into the body. Can you explain how that helps?
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
Injections and drips into a patient’s body must be carefully buffered so that the pH of body fluids
does not change much.
The pH of many industrial processes must also be carefully controlled, e.g. electroplating and
manufacture of dyes and leather.
Although most buffer systems consist of two separate species that react with H+ or OH–, the
HCO3– ion is an example of a single ion that is able to serve both functions:
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
4 ACID–BASE TITRATIONS
An indicator is a weak acid, whose acid form, HIn, is a different colour from its ionised form, In–.
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.
For most indicators, the predominant form must be at least 10 times more concentrated than the
other form for its colour to be distinguished from the other coloured form.
[H+][ In]
KIn =
[HIn]
Taking –lg on both sides and rearranging,
[ In]
pH = pKIn + lg
[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.
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 .
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
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 10–5) is green.
During an acid–base titration, one solution is run into the other in the presence of an indicator.
End–point: 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 end–point 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.
A titration curve (a graph of pH against the volume of the titrant added) shows how the pH changes
during a titration. It can be obtained by measuring the pH of the solution using a pH meter.
Four types of acid–base titration curves are shown on the following pages. Note that in all of them,
the acid is in the conical flask while the base is added from the burette.
E.g. addition of 0.10 mol dm3 NaOH to 25.0 cm3 of 0.10 mol dm3 HCl
At VNaOH = 25 cm3
Equivalence point is reached.
pH = 7 as the salt formed does not undergo
hydrolysis.
Volume of NaOH added / cm3
Suitable indicator:
Note for teachers: methyl orange or phenolphthalein
Graph is not given in the students’ notes. Students will
sketch the titration curve during the lecture. Note the sharp pH change near equivalence
point (see Homework 1, parts (c) and (e)).
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
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.
(b) 12.50 cm3 (This is called the half–neutralisation or half–equivalence point.) Ans: 1.48
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
E.g. addition of 0.10 mol dm3 NaOH to 25.0 cm3 of 0.10 mol dm3 CH3CO2H
Equivalence
X
point, pH > 7
buffer region
3
At 0 <VNaOH < 25 cm
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.
3
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)
3
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 10–5 mol dm–3)
(a) 0.00 cm3 Ans: 2.87
3
(b) 12.50 cm (half–neutralisation point) Ans: 4.74
3
(c) 25.00 cm (see Section 2.7, Exercise 12) Ans: 8.72
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
E.g. addition of 0.10 mol dm3 NH3 to 25.0 cm3 of 0.10 mol dm3 HCl
Equivalence
X
point, pH < 7
3
At 0 < Vweak base < 25 cm
pH gradually rises as increasing amount of H+ is neutralized by added weak base. However, no
buffer is formed as there is no weak base present in excess in the conical flask.
3
At Vweak base = 25 cm
Equivalence point is reached. pH < 7 as the cation undergoes hydrolysis to produce H3O+:
NH4+(aq) + H2O(l) ⇌ NH3(aq) + H3O+(aq)
3
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 10–5 mol dm–3) Ans: 5.28
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
E.g. addition of 0.10 mol dm3 NH3 to 25.0 cm3 of 0.10 mol dm3 CH3CO2H
3
At 0 < Vweak base < 25 cm
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.
3
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).
3
At Vweak base > 25 cm
There is excess weak base present in the solution together with its salt another buffer region is
formed.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
Polyprotic acids have more than one ionisable proton. The successive Ka values may differ by several
orders of magnitude. This means the first H+ is lost more easily than subsequent ones.
E.g. H2SO3(aq) + H2O(l) ⇌ HSO3–(aq) + H3O+(aq) Ka1 = 1.4 x 10–2 mol dm–3
HSO3–(aq) + H2O(l) ⇌ SO32–(aq) + H3O+(aq) Ka2 = 6.5 x 10–8 mol dm–3
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–
Note that the titration curve has two steep portions, which corresponds to two equivalence points.
A similar curve is also obtained for a titration involving a mixture of two acids with an appreciable
difference in Ka values (or a mixture of 2 bases with an appreciable difference in Kb values).
In practice, we can observe the two separate end–points with the proper choice and use of two
different indicators. Consider the titration of sodium carbonate with dilute HCl.
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
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 end–points 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 end–point is observed and the titre
obtained is twice that obtained with phenolphthalein.
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 dm–3 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 dm–3; 0.0240 mol dm–3
No of moles of HCl used for NaHCO3 formed from Na2CO3 = 2.25 x 10–3
No of moles of HCl used for original NaHCO3 = 2.85 x 10–3 – 2.25 x 10–3 = 0.60 x 10–3
[NaHCO3] in the original solution = 0.60 x 10–3/ 0.025 = 0.0240 mol dm–3
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Hwa Chong Institution 2013 H2 Chemistry – Acid–Base Equilibria
Concept Application
pX = log10X X = 10
pX
To define quantities such as pH, pOH, pKw, pKa and pKb
Kw = [H ][OH] = 1 x 1014 (at 25C) To calculate [H ] or [OH] given the value of the other.
+ +
Kw shows the relationship between [H ] and [OH] in any In pure water, [H ] = [OH] = 1 x 107 (at 25C)
+ +
aqueous solutions.
For any conjugate acid–base pair, To calculate Ka from Kb, or vice versa.
Ka x Kb = Kw You use this equation when you need one of these K
o
pKa + pKb = pKw = 14 (at 25 C) values but have the other.
H + A
+
HA To calculate the pH of a
2
weak acid, Ka [H ] eqm
[H ] eqm [A ] eqm [HA] initial
Ka =
[HA] eqm [H ] eqm [ salt] initial
buffer, Ka
[acid] initial
BH + OH
+
B + H2O To calculate the pH of a
[OH ] 2 eqm
weak base, Kb
[BH ] eqm [OH ] eqm [B] initial
Kb =
[B] eqm [OH ] eqm [salt] initial
buffer, Kb
[base] initial
Salt hydrolysis – a reaction in which ions react with To explain why the pH of a salt derived from
water to form acidic or alkaline solutions strong acid and weak base (e.g. NH4Cl) is < 7
+ +
e.g. NH4 + H2O NH3 + H3O weak acid and strong base (e.g. CH3CO2Na) is > 7
CH3CO2 + H2O CH3CO2H + OH
Using the above, can you sketch a titration curve, and mark the various key points on the curve (initial pH, equivalence
point, buffer with maximum capacity)?
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