Acids and Bases

1. Conjugate acid-base pairs differ by one H+. SO3 and HSO3- differ by H-. D

2. The mineral acids, HNO3, H2SO4 and HClO4, and the hydrohalic acids, HCl, HBr and B
HI, are the only strong acids.

3. The titration starts off with pH > 7 so a base must be present. At the equivalence point,
E
the solution is acidic indicating that the base has all been converted into a weak
conjugate acid. The base therefore must itself be a weak base.

4. At the equivalence point, all of the weak base has been converted into its conjugate
C
acid. This corresponds to the addition of 50 mL of strong acid. After addition of 25 mL
of strong acid (the “1/2 equivalance point”), half of the weak base has been converted
into its conjugate acid and [base] = [acid]. When this ratio is equal to 1, the
Henderson-Hasselbalch equation shows that pH = pKa. From the graph, the pH after
the addition of 25 mL of strong acid is equal to 9.3

5. If pH = 2.0 then [H+(aq)] = 10-2.0 M = 0.01 M. Only strong acids have [H+(aq)] equal
D
to the concentration of acid. HClO4 is the only strong acid listed.

6. For a triprotic acid like H3PO4, it is much easier to remove the first H+ (i.e. H3PO4 à
H+ + H2PO4-) than the second (i.e. H2PO4- à H+ + HPO42-). It is much easier to A
remove the second H+ than the third (i.e. HPO4- à H+ + PO43-)

7. HNO3 is a strong acid. For the weak acids, the smaller the value of pKa, the stronger
the acid is. B

8. NaOH is a strong base. A solution of NaCN contains CN-. This is the conjugate base of
a weak acid (HCN) so CN- is a weak base and the solution is basic. A solution of NaC
contains Cl-. This is the conjugate base of a strong acid (HCl) so Cl- is a not a base and E
the solution is neutral. CH3COOH is a weak acid. HCl is a strong acid.
CHEM1102 2009-J-5 June 2009
Marks
• Solution A consists of a 0.020 M aqueous solution of propionic acid, C3H6O2, at 8
25 °C. Calculate the pH of Solution A. The pKa of propionic acid is 4.87.

As C3H6O2 is a weak acid, [H+] must be calculated by considering the

equilibrium:

C3H6O2 C3H5O2 – H+
initial 0.020 0 0
change -x +x +x
final 0.020 – x x x

The equilibrium constant Ka is given by:

!! !! !! ! [! ! ] !!
Ka = =
[!! !! !! ] (!.!"!!!)

As pKa = 4.87, Ka = 10 4.87. Ka is very small so 0.020 – x ~ 0.020 and hence:

−

x2 = 0.020 × 10–4.87 or x = 0.000519 M = [H ] +

Hence, the pH is given by:

pH = −log10[H ] = −log10[0.000519] = 3.28

+

Answer: pH = 3.28

At 25 °C, 1.00 L of Solution B consists of 2.24 g of potassium propionate (KC3H5O2)

dissolved in water. Calculate the pH of Solution B.

The molar mass of KC3H5O2 is:

molar mass = (39.10 (K) + 3×12.01 (C) + 5×1.008 (H) + 2×16.00 (O)) g mol-1
= 112.17 g mol-1

Thus, 2.24 g corresponds to:

!"## !.!"!!
number of moles = =! = 0.0200 mol
!"#$%!!"## !!".!"!!!!"!!!

If this is dissolved in 1.0 L, [C3H5O2-]initial = 0.0200 M.

As C3H5O2- is a weak base, [C3H5O2-] must be calculated by considering the

equilibrium:

ANSWER CONTINUES ON THE NEXT PAGE

CHEM1102 2009-J-5 June 2009

C3H5O2- H2O C3H6O2 OH-

initial 0.0200 large 0 0
change -y negligible +y +y
final 0.0200 – y large y y

The equilibrium constant Kb is given by:

!! !! !! [!" ! ] !!
Kb = =
[!! !! !! ! ] (!.!"!!!!)

For an acid and its conjugate base:

pKa + pKb = 14.00

pKb = 14.00 – 4.87 = 9.13

As pKb = 9.13, Kb = 10--9.13. Kb is very small so 0.0200 – y ~ 0.0200 and hence:

y2 = 0.0200 × 10–9.13 or y = 0.000000385 M = [OH-]
Hence, the pOH is given by:
pOH = -log10[OH-] = log10[0.000000385] = 5.41
Finally, pH + pOH = 14.00 so
pH = 14.00 – 5.41 = 8.59
Answer: pH = 8.59

Solution B (1.00 L) is poured into Solution A (1.00 L) and allowed to equilibrate at

25 °C to give Solution C. Calculate the pH of Solution C.

Combining the two solutions will double the overall volume, to 2.00 L. As a
result, the concentration of both the acid and base will halve: [acid] = 0.010 M
and [base] = 0.0100 M.

The solution contains a weak acid and its conjugate base. The pH of this buffer
solution can be calculated using the Henderson-Hasselbalch equation:
[!"#$] !.!"!!
pH = pKa + log = 4.87 + log = 4.87
[!"#$] !.!"!

Answer: pH = 4.87

If you wanted to adjust the pH of Solution C to be exactly More base is

equal to 5.00, which component in the mixture would you needed: add
need to increase in concentration? KC3H5O2
CHEM1102 2006-J-6 June 2006
Marks
• Buffer systems are frequently used in chemistry. What is a buffer system and how 4
does it function? Use equations where appropriate.

Buffer systems resist changes in pH: a buffer will maintain a relatively constant
pH when acid or base is added.

They consist of mixtures of a weak acid (HA) and its conjugate base (A-) in high
concentration.

If acid is added, the system can respond by removing it using A-:

H+(aq) + A-(aq) ! HA(aq)

If base is added, the system can respond by removing it using HA:

OH-(aq) + HA(aq) ! H2O(l) + A-(aq)

What ratio of concentrations of acetic acid to sodium acetate would you require to
prepare a buffer with pH = 4.00? The Ka of acetic acid is 1.8 × 10–5 M.

The pH of a buffer system made from a mixture of the weak acid (HA) and its
conjugate base (A-) is described by the equation:
[A - (aq)]
pH = pKa + log
[HA(aq)]

For acetic acid, Ka = 1.8 × 10-5 or pKa = -log(Ka) = 4.74. To obtain pH = 4.00:

[A - (aq)] [A - (aq)]
4.00 = 4.74 + log and so = 10-0.74 = 0.18
[HA(aq)] [HA(aq)]

[HA(aq)] 1
Alternatively, -
= = 5.56
[A (aq)] 0.18

Answer: 5.56: 1
CHEM1102 2007-J-4 June 2007
Marks
• Solution A consists of a 0.20 M aqueous solution of formic acid, HCOOH, at 25 °C. 8
Calculate the pH of Solution A. The pKa of HCOOH is 3.75.

The reaction table is:

HCOOH(aq) H2O(l) HCOO-(aq) H3O+(aq)

start 0.20 large 0 0
change -x -x +x +x
equilibrium 0.20-x large x x

As pKa = -log10(Ka) = 3.75, Ka = 10-3.75 and:

[HCOO − (aq)][H 3O + (aq)] (x)(x) x2

Ka = = = = 10−3.75
[HCOOH(aq)] (0.20 − x) (0.20 − x)

As Ka is very small, x is tiny and 0.20 – x ~ x. Hence,

x2
Ka ~ = 10−3.75 or x2 = (0.20) × (10-3.75) so x = [H3O+(aq)] = 6.0 × 10-4 M
(0.20)

As pH = -log10([H3O+(aq)]:

pH = -log10(6.0 × 10-4) = 2.22

Answer: 2.22
ANSWER CONTINUES ON NEXT PAGE
CHEM1102 2007-J-4 June 2007

At 25 °C, 1.00 L of Solution B consists of 13.6 g of sodium formate, NaHCO2,

dissolved in water. Calculate the pH of Solution B.

The molar mass of NaHCO2 is

(22.99 (Na)) + (1.008 (H)) + (12.01 (C)) + (2 × 16.00 (O)) = 68.008
mass 13.6
The solution thus contains = = 0.200mol
molar mass 68.008

As this is dissolved in 1.00 L, the concentration is 0.200 M. The reaction table is

now:

HCOO-(aq) H2O(l) HCOOH(aq) OH-(aq)

start 0.200 large 0 0
change -y -y +y +y
equilibrium 0.200-y large y y

As pKa + pKb= 14.00, pKb = 14.00 - 3.75 = 10.25, Kb = 10-10.25 and:

[HCOOH(aq)][OH − (aq)] (y)(y) y2

Kb = −
= = = 10−10.25
[HCOO (aq)] (0.200 − y) (0.200 − y)

Again Kb is very small, y is tiny and 0.200 – y ~ y. Hence, y2 = (0.200) × (10-10.25)

so y = [OH-(aq)] = 3.35 × 10-6 M and pOH = -log10([OH-(aq)] = 5.47
As pH + pOH = 14.00, pH = 14.00 – 5.47 = 8.52

Answer: 8.52

Solution B (1.00 L) is poured into Solution A (1.00 L) and allowed to equilibrate at

25 °C to give Solution C. Calculate the pH of Solution C.

After mixing solution A (1.00 L) and solution B (1.00 L), the total volume is 2.00
L. This halves the concentration of the both the acid and the base.

0.20 0.200
[acid] = = 0.10 M and [base] = = 0.100 M
2 2
Solution C contains a weak acid (HCOOH) and its conjugate base (HCOO-). It
is a buffer and the pH can be calculated using the Henderson-Hasselbalch
equation can be used:
 [base]   0.100 
pH = pKa + log10   = 3.75 + log10   = 3.75
 [acid]   0.10 

Answer: 3.75

If you wanted to adjust the pH of Solution C to be exactly

[HCOOH] would be
equal to 3.00, which component in the mixture would you
increased (the acid)
need to increase in concentration?
CHEM1102 2006-N-5 November 2006
Marks
• Solution A consists of a 0.25 M aqueous solution of hydrazoic acid, HN3, at 25 °C. 8
Calculate the pH of Solution A. The pKa of HN3 is 4.63.

As pKa = -log(Ka) = 4.63, Ka = 10-4.63 = 2.34 × 10-5. The reaction table is:

HN3(aq) H+(aq) N3-(aq)

t=0 0.25 0 0
change -x +x +x
equilibrium 0.25 – x x x

[H + (aq)][N 3- (aq)] (x)(x) x2

Hence, Ka = = = = 2.34 × 10-5
[HN 3 ] (0.25-x) (0.25-x)

As Ka is very small, very little HN3 dissociates and x is tiny so (0.25 – x) ~ 0.25

x2
Hence, = 2.34×10-5 or x = [H+(aq)] = 2.42 × 10-3 M
(0.25)

As pH = -log[H+(aq)]:

pH = -log(2.42 × 10-3) = 2.62

Answer: 2.62
(ANSWER CONTINUES ON THE NEXT PAGE)
CHEM1102 2006-N-5 November 2006

At 25 °C, 1.00 L of Solution B consists of 13.0 g of sodium azide (NaN3) dissolved in

water. Calculate the pH of Solution B.

The relevant reaction is now: N3-(aq) + H2O(l) HN3(aq) + OH-(aq)

As N3- is the conjugate base of HN3, the equilibrium constant for this reaction is
Kb where pKa + pKb = 14.00.

Hence, using pKa from above:

pKb = 14.00 – 4.63 = 9.37 or Kb = 10-9.37 = 4.27 × 10-10.

The molar mass of NaN3 is (22.99 (Na)) + (3 × 14.01 (N)) = 65.02. The number of
moles in 13.0 g is therefore:

mass 13.0
number of moles = = = 0.200 mol
molar mass 65.02

number of moles 0.200

As this is dissolved in 1.00 L, [N3-(aq)] = = = 0.200 M
volume 1.00

The relevant reaction table is now:

N3-(aq) H2O(l) HN3(aq) OH-(aq)

t=0 0.200 0 0
change -x +x +x
equilibrium 0.200 – x x x

[NH 3 (aq)][OH - (aq)] (x)(x) x2

The equilibrium constant Kb = = =
[N 3- (aq)] (0.200-x) (0.200-x)

Kb is small so the amount of N3-(aq) which is protonated is tiny and hence

0.200 – x ~ 0.200.

x2
Hence, = 4.27×10-10 or x = [OH-(aq)] = 9.24 × 10-6 M
(0.200)

As pOH = -log[OH(aq)] = -log(9.24 × 10-6) = 5.03

As pH + pOH = 14:

pH = 14 – 5.03 = 8.97

Answer: 8.97
CHEM1102 2006-N-5 November 2006

Solution B (1.00 L) is poured into Solution A (1.00 L) and allowed to equilibrate at

25 °C to give Solution C. Calculate the pH of Solution C.

Solution C is a buffer system as it contains both a weak acid (HN3) and its
conjugate base (N3-(aq). The pH can be obtained from the Henderson-
Hasselbalch equation:

[A - (aq)]
pH = pKa + log
[HA(aq)]

Using pKa = 4.63, [HA(aq)] = [HN3(aq)] = 0.25 M and [A-(aq)] = [N3-(aq)] =

0.200 M:

(0.200)
pH = (4.63) + log = 4.53
(0.25)

Answer: 4.53

If you wanted to adjust the pH of Solution C to be exactly To lower the pH,

equal to 4.00, which component in the mixture would you the acid
need to increase in concentration? concentration
(HN3) is increased