E17 ACID IONISATION-CONSTANT from titration-curve

INTRODUCTION
(1) Self-ionising solvents
Water is the most important member of the self-ionising solvents. Like other members it has a
slight but measurable electrical conductivity, arising from the presence of very small and equal
proportions of positive and negative ions. These ions are derived from a pair of solvent
molecules by transfer of a single particle, which in water, ammonia, acetic acid and many other
liquids, is a proton. The equilibria can be shown as follows:
2H2O

H3O+ + OH

2NH3

NH4+ + NH2

2CH3COOH

CH3C(OH)2+ + CH3CO2

In a proton-transfer reaction, the entity donating the proton is called a protonic (or Brnsted)
acid, and the entity accepting the proton is a protonic base. Two entities that differ by a single
proton are called a conjugate acid/base pair. H3O+ is thus the conjugate acid of H2O and
conversely H2O is the conjugate base of H3O+. Similarly, H2O is the conjugate acid of OH and
OH is the conjugate base of H2O. Note that there is no conjugate acid/base relationship
between H3O+ and OH as they differ in formula by two H+.
The extent to which a solvent is ionised is a function of temperature. At 298 K, 1.00 litre of
water is found to contain 107.00 mole of H3O+ and 107.00 mole of OH.
The formulas of the species appearing in 1, 2, and 3 are a simplification as all ions in solution
are solvated by the molecules of solvent. For example, the oxonium ion, H3O+, can be
considered as a hydrated proton, H+(H2O). It is often convenient to ignore the solvation and
simply write H+ or H+(aq), but it is important to remember that H+ does not then refer to the
extremely reactive free proton, which is never present in liquids, but to H3O+.
(2) Ionic-product-constant
One or other of the ions characteristic of a self-ionising solvent may be a constituent of a
substance which is soluble in the solvent. For example, sodium hydroxide is composed of OH
and Na+ ions and dissolves in water, greatly increasing the concentration of OH ions. This
concentration expressed in mole litre1 is represented by [OH]. Since OH is the conjugate base
of H2O, NaOH is classified as a base. In a similar way, hydrogen perchlorate is composed of H+
and ClO4 ions and dissolves in water greatly increasing the concentration of H3O+ ions. This
molar concentration is represented by [H+] or [H3O+]. Since H3O+ is the conjugate acid of H2O,
HClO4 is classified as an acid.

E17-1

E17-2

An important observation shows that although we can increase [H+] or [OH] in a watersolution, it is impossible to obtain a solution containing only one of these ions: both are always
present. Furthermore, their concentrations are linked according to the equation:
[H+] [OH] = a constant

A similar equation holds for solutions in other self-ionising solvents. The constant in each case
is known as the ionic-product-constant. In the case of water, the ionic-product-constant is
represented by Kw. Its value under standard conditions at 25 C is measured to be
Kw = 1014.00

Raising the temperature from 298 to 308 K increases the observed value of Kw by a factor of 2.
The following table shows [H+] and [OH] for a range of dilute water-solutions at 25 C.
[H+]/M

101

104

1010.0

107.5

101.00

107.01

[OH]/M

1013

1010

104.0

106.5

1013.00

106.99

Note how increasing [H+] results in a decrease of [OH] and vice versa.
(3) Strong acids and bases
A 1.00 M solution of HClO4 dissociates virtually completely in water to give a solution with
[H+] = 1.00 M.
HClO4(l) + H2O H3O+(aq) + ClO4(aq)
Compounds with this property are termed strong acids. The other strong acids encountered in
this course are hydrogen chloride, hydrogen bromide, hydrogen iodide (all gases), nitric acid
and sulfuric acid (both liquids). All of these dissociate in water virtually completely.
HCl(g) + H2O H3O+(aq) + Cl(aq)
HBr(g) + H2O H3O+(aq) + Br(aq)
HI(g) + H2O H3O+(aq) + I(aq)
HNO3(l) + H2O H3O+(aq) + NO3(aq)
H2SO4(l) + H2O H3O+(aq) + HSO4(aq)
A 1.00 M solution of NaOH dissociates virtually completely in water to give a solution with
[OH] = 1.00 M. There are also compounds that do not contain OH ions, but react with water
so completely that every mole of solute produces a mole (at least) of OH ions. The main
examples of these bases are oxide ion (O2) and amide ion (NH2). Such species, along with
OH, are known as strong bases.
NaOH OH(aq) + Na+(aq)
Li2O + H2O 2OH(aq) + 2Li+(aq)
NaNH2 + H2O OH(aq) + NH3(aq) + Na+(aq)

E17-3

(4) pH and pOH

At concentrations greater than about 1 M Equation 4 breaks down to a marked degree (a
deviation which can be accounted for in terms of interactions of ions). Hence it is necessary
here to restrict attention to solutions of concentration 1 M or less. Since within this range all
concentrations may be expressed as negative powers of ten, it is convenient to express the
acidity of a solution by the symbol pH, which is defined as the negative logarithm to base 10 of
[H+], that is, pH = log10[H+]. In a similar fashion, pOH is defined as the negative logarithm to
base 10 of [OH], that is, pOH = log10[OH].
In a 1.00 M solution of HCl, [H+] = 1.00 M = 100.00 M and [OH] = 1014.00 M.
So, pH = log10[H+] = log10[100.00] = 0.00 and pOH = log10[OH] = log10[1014.00] = 14.00.
In a 1.00 M solution of NaOH, [OH] = 1.00 M = 100.00 M and [H+] = 1014.00 M.
So, pOH = log10[OH] = log10[100.00] = 0.00 and pH = log10[H+] = log10[1014.00] = 14.00.
Pure water has pH = 7.0 and pOH = 7.0. Acidic solutions have pH less than 7.0 and basic
solutions have pH greater than 7.0. As an acidic solution is diluted, its pH approaches 7.0 from
below. As a basic solution is diluted, its pH approaches 7.0 from above.
Again, because of the failure of Equation 4 at high concentrations, the useful range of the pH
scale is about 0 to about 14.
A direct consequence of Equations 4 and 5 is that

pH + pOH = 14.00

(5) Weak acids and bases

Many substances are acidic, but only weakly so; even though every molecule contains one or
more acidic protons, only a proportion of molecules are able to transfer a proton to a solvent
molecule. These are classified as weak acids. One such is acetic acid, CH3COOH, which reacts
incompletely with water to establish an equilibrium thus:
CH3COOH(aq) + H2O

CH3CO2 (aq) + H3O+

Similarly, NH3 is an example of a weak base, and reacts incompletely with water thus:
NH3(aq) + H2O

NH4+(aq) + OH(aq)

A molecule acts as a protonic acid only when it actually transfers a proton to an acceptor
molecule; the acidic nature of the donor molecule is not absolute, but dependent on the nature
of its acceptor partner. Water is thus a base in its reaction with CH3COOH, and an acid in its
reaction with NH3.
(6) Equilibria in water-solutions of acetic acid
When acetic acid is added to water, it dissolves completely to give a solution which consists
mainly of solvated acetic acid molecules, CH3COOH(aq). The main reaction that occurs in this
solution is:
CH3COOH(aq) H+(aq) + CH3CO2(aq)
Measurements of electrical conductivity show that in dilute solutions the proportion of
CH3COOH molecules that have dissociated is very small; for example, in 1 M CH3COOH the
proportion is only 1 in 250. Conversely, if solutions of HCl and NaCH3CO2 are mixed, H+ and
CH3CO2 ions will tend to combine:
CH3CO2(aq) + H+(aq) CH3COOH(aq)

E17-4

Each process comes to rest in an equilibrium that lies very much on the CH3COOH side and can
be represented by:
H+(aq) + CH3CO2(aq)

CH3COOH(aq)

An important observation shows that the concentrations of the three species in Equation 6 are
not independent, but are linked as follows:

[H + ] [CH 3 CO 2 ]
= a constant
[CH 3 COOH]

This constant is known as the acid-ionisation-constant, and is represented by Ka. In the case of
acetic acid, the value of Ka = 1.8 105 M. The upper factors represent the right-hand side of
Equation 6 and the lower factor represents the left-hand side; Ka is thus linked to Equation 6.
Ka is a particular kind of equilibrium-constant: to have any meaning, every equilibrium-constant
must be linked to an equilibrium equation.
Addition of CH3CO2(aq) ions or H+(aq) ions to the CH3COOH solution will push the position
of equilibrium in Equation 6 to the left, in accordance with Le Chateliers principle.
(7) Multiple proton-transfer
Some molecules have more than one ionisable proton, eg H2SO4 and H2CO3. With water, the
electrically neutral molecule H2SO4 acts as an acid according to the equation:
H2SO4(l) + H2O H3O+ + HSO4(aq)
In addition, the conjugate base of H2SO4 also acts as an acid, according to the equation:
HSO4(aq) + H2O

H3O+ + SO42(aq)

Since the conjugate base of H2SO4 carried a negative charge, removal of this second proton is
more difficult than removal of the first proton from H2SO4. Hence H2SO4 is a stronger acid than
HSO4. The acid-ionisation-constant associated with the first of these reactions is called Ka1 and
the constant associated with the second reaction is called Ka2. In general, for any multiprotic
acid, Ka1 > Ka2 > Ka3, etc.
(8) Titration-curves
Equation 7 can be rearranged to give:
[H+] = Ka

[CH 3 COOH ]

[CH 3 CO 2 ]
If a dilute solution of CH3COOH is titrated with a dilute solution of NaOH, the following
reaction occurs:
CH3COOH + OH CH3CO2 + H2O
Throughout the titration there will be a continuously changing value for the ratio
[CH3COOH]/[CH3CO2] in Equation 8, and consequently a continuously changing value for
[H+] and thus of pH.
In this experiment, for each of a number of different titrations, the pH is plotted against the
volume of added reactant. This graph is called a titration-curve.

E17-5

In Experiment 1, 0.1 M CH3COOH (a weak acid) is titrated with 0.1 M NaOH (containing the
strong base OH). From the titration-curve the value of Ka for CH3COOH is obtained.
In Experiment 2, 0.1 M NH3 (a weak base) is titrated with 0.1 M HCl. From the titration-curve
the value of Ka for NH4+, the conjugate acid of NH3, is obtained.
(9) pH measurement
pH values can be determined roughly and over a very limited pH range by use of an acid/base
indicator, and over a wider range with a mixed indicator [see Appendix A5 (3)]. To construct a
titration-curve, more precise values, over an extended range, are required. For this purpose a
pH meter is used. In Experiment 1, an indicator (although superfluous) is added to the titration
mixture. This experiment establishes both the titration-curve and the effective pH range of the
indicator.
(10) Experimental aspects
It is usual in acid/base titrations to place the acidic solution in the burette, since basic solutions
tend to impair the operation of the tap. However, Ka is most easily obtained from a titrationcurve when the strong acid or base is added from the burette. Also, strongly basic solutions
tend to damage the glass-electrode. Hence in Experiments 1 and 2 the basic solution is placed
in the burette. After base has been used in a burette extensive washing is necessary.

LAB WORK

20

The pH-meter is a delicate instrument. Treat it with great care.

The pH-electrode is extremely fragile. Treat it with even greater care as it doubles in
these experiments as a stirring rod. All stirring must be done very slowly and gently,
taking the utmost care not to hit the walls or bottom of the beaker with the electrode.

In this exercise students work in pairs, entering their results jointly, but carrying out their
calculations independently.

Experiment 1: Titration of 0.1 M acetic acid with 0.1 M sodium hydroxide

(1.1) Using two clean, dry containers, collect approximately 80 mL of Solution E17ACH3COOH and approximately 200 mL of Solution E17B-NaOH.
(1.2) Rinse the burette with Solution E17B-NaOH and then fill it with the same solution. Take
great care to remove any air bubbles below the tap. Adjust the level to 0.00 mL.

E17-6

(1.3) The approximate end-point of the titration should be checked as follows. Carefully titrate
25.00 mL of the acidic solution in a conical flask with phenolphthalein as indicator. The
volume of base required for your end-point is

mL.

The pH at equivalence point is that of a 0.05 M NaCH3CO2 solution, ie., 8.7.

You should appreciate that when you carry out the titration using the pH-meter, a considerable
time will elapse, and there will be significant run-down of solution from the walls of the
burette. There may also be carbon dioxide absorbed from the air. Thus you will probably find
that the equivalence-point determined from your titration-curve will differ slightly from the endpoint obtained by the simple titration. Any indicator 'error' would also cause a discrepancy.
(1.4) Refill the burette, adjust to 0.00 mL and mount it over a 250 mL beaker, which will be
used as the titration vessel.
(1.5) Calibrate the pH-meter as shown by your demonstrator.
(1.6) Add 25.00 mL of Solution E17A-CH3COOH and 25 mL of water to the titration vessel.
Also add 2 drops of phenolphthalein indicator. Carefully rinse the electrode with deionised
water and then very gently use it to mix the solution. Observe and record the pH.
Add 0.50 mL of the solution from the burette, again very gently stirring the solution with the
electrode before observing and recording the pH. Repeat this procedure using the volume
increments shown in the table, and record the results for pH and colour of the solution. Plot the
titration-curve (Figure E17-1) as you proceed; this will provide an immediate check on the
accuracy of your experiment.
Near the equivalence point (marked by a very rapid increase in pH), let the pH determine the
titration interval, according to the following guide.
pH range

Increment

< 6.00

1.0 mL

6.00 - 7.00

0.2 mL

7.00 - 9.00

0.1 mL

9.00 - 10.50

0.2 mL

> 10.50

1.0 mL

This should avoid problems caused by the effects already mentioned. It is likely that the
equivalence point will occur at a slightly different volume to the end-point obtained in (1.3). If
the difference exceeds 0.4 mL, you should consult your demonstrator immediately; do not
proceed further with the readings if such a discrepancy is found.
(1.7) Remount the burette away from the titration vessel, then rinse the electrode in deionised
water and place it in the pH = 4 buffer solution.

E17-7

Volume of NaOH
added (mL)
0.00
0.50
1.00
5.00
10.00
12.00
13.00
14.00
15.00

30.00
35.00
40.00
45.00
50.00

pH

Colour of solution
(phenolphthalein)

E17-8

Figure E17-1 Titration-curve

0.1 M CH3COOH with 0.1 M NaOH
13

11

pH

10

20
30
0.1 M OH added (mL)

40

50

(1.8) The equivalence-point is the point in the titration where the amount of OH added is
exactly equal to the amount of CH3COOH initially present. It can be readily identified from the
titration curve as it is the position where the pH changes most rapidly - the mid-point of the
vertical rise in the graph.
Volume of 0.1 M NaOH solution required to reach the equivalence point.

mL

pH at the equivalence point.

(1.9) The useful range of an acid/base indicater is the pH range over which the colour changes.
Useful pH range of phenolphthalein indicator.

E17-9

(1.10) Ka for CH3COOH can be found from the titration curve.

Just as log[H+] can be represented as pH, so log10Ka can be represented as pKa.
The relationship

[H+] = Ka

[CH 3 COOH ]

was derived in the Introduction.

[CH 3 CO 2 ]
When the value of the ratio [CH3COOH]/[CH3CO2] = 1, [H+] =

and pH =

If the volume of NaOH solution required to reach the equivalence point, as estimated from your
titration curve, was

mL , then the volume required to reach the point where

[CH3COOH] = [CH3CO2] was

Hence the pKa of CH3COOH was found to be

mL . At this volume the pH was

, and Ka =

Demonstrator's
Initials

E17-10

Experiment 2: Titration of 0.1 M ammonia with 0.1 M hydrochloric acid

The plot of the titration-curve in this case is more difficult because of loss of ammonia from
solution. This means that the concentration of this solution decreases with time. Consequently
no check titration will be performed. From your experience of the previous titration, you should
be able to make any necessary adjustment of the end-point figure as you see the developing
shape of your plotted titration-curve.
(2.1) Collect approximately 80 mL of Solution E17C-HCl
and approximately 40 mL of Solution E17D-NH3.
(2.2) The acidic solution is placed in the burette. Rinse and
fill the burette with Solution E17C-HCl, then adjust the level
to 0.00 mL.
(2.3) Add 25.00 of Solution E17D-NH3 and 25 mL of water
to the titration vessel. Repeat the procedure of Experiment 1
for the volume increments shown in the results table and
record your results. Plot the titration curve (Figure E17-2) as
you proceed. Note the advice given above.

Volume of HCl
added (mL)
0.00
0.50
1.00
5.00
10.00
11.00
12.00
13.00
14.00

(2.4) After all experimental work is completed, switch off the

pH meter, wash the electrode with deionised water and store
it in the special electrode-storage-solution.

15.00

30.00
35.00
40.00
45.00
50.00

pH

E17-11

Figure E17-2 Titration-curve

0.1 M NH3 with 0.1 M HCl
13

11

pH

10

20
30
0.1 M H+ added (mL)

40

50

Volume of 0.1 M HCl solution required to reach the equivalence point.

mL

pH at the equivalence point.

(2.5) When NH3 solution is titrated with HCl, the conjugate acid of NH3, which is

is produced. The equilibrium expression for the ionisation of the conjugate acid of NH3
(corresponding to Equation 6 in the Introduction) is:

E17-12

The expression corresponding to Equation 7 for the conjugate acid of NH3 is:

The expression corresponding to Equation 8 for the conjugate acid of NH3 is:

When the pH was equal to the pKa of the conjugate acid (ie, at the point where [NH3] = [NH4+])
the volume of added HCl solution was

Hence the pKa of

was found to be

mL and the pH was

, and Ka =

Demonstrator's
Initials

E17-13

POST-WORK
Titration curves in volumetric analysis
Consider your titration curves. Describe the common feature in each curve at its equivalence
point.

Complete the following table.

Titration

pH at
equivalence
point

Suitability as indicator.
Write yes or no.

Suitable indicators
(from the table in A5(5))

methyl-red
CH3COOH/NaOH
phenolphthalein

HCl/NaOH

7.00

NH3/HCl

Define the terms end-point and equivalence-point.

Demonstrator's
Initials