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Determination of The Acid Dissociation Constant by Potentiometric Titration

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 Titration Application Note
Determination of The Acid Dissociation
Note

Constant by Potentiometric Titration

Titration Application

Introduction Sample preparation and procedures

Motivation:
The determination of the acid dissociation
constant Ka is an important step in the
development of new pharmaceutical products
since this physico-chemical parameter can affect
the efficacy of the product.
Definition of pKa:
What are the characteristic properties of an acid?
When dissolved in water, H2O, the acid HA
+ head to avoid CO2-intake by the solution.
dissociates by releasing a hydrogen ion, H :
Acids have different dissociation strengths. For
example, hydrochloric and nitric acid are stronger
than acetic acid because they are completely
dissociated. The extent of dissociation is
described by the equilibrium constant K:
+ -
where ax are the activities of H3O , A , HA and
H2O. In dilute solutions, activities are to a good
approximation equal to the concentrations [X].
Moreover, the water concentration remains
constant compared to those of the other reaction
partners. Therefore, its value can be included in K:
Note:
The acid dissociation constant Ka is dependent on
temperature, pressure and on ionic strength.
 Electrode adjustment (HNV - Quick procedure):
1. The pH sensor is adjusted with pH 4.01,
7.00 and 9.21 buffer solutions.
2. Each buffer solution is poured into a
thermostatable beaker.
3. Nitrogen gas is flowing in the titration
4. Before measurement, the solutions are
gently stirred to achieve thermal
equilibrium with the surroundings.
 Electrode adjustment (Pot. Methods I and II):
1. The water product Kw is determined by
acid/base titration in aqueous salt
solution of known acid concentrations
(Details: see "Remarks").
 Acid sample titration:
1. 5 mL 0.1 M CH3COOH in 0.1 KNO3 is
added in the thermostatable beaker.
2. The sample is diluted with 50 mL 0.1 M
KNO3 solution.
3. Nitrogen gas is flowing in the titration
head to avoid CO2-intake by the solution.
4. Before starting titration, the solution is
gently stirred to achieve thermal
equilibrium with the surroundings.

Ka characterizes the acid strength of acid HA, and

in general, its negative logarithm is used:

Experimental determination:
Titration is a powerful technique for the accurate
determination of acid dissociation constants [1].
In this application note, the pKa determination of
acetic acid by acid/base titration is described, and
three different approaches named HNV-quick
procedure, potent. method I and II are compared.

METTLER TOLEDO Page 1 of 10

M760 v1.0
 Chemistry Results
Titration Application Note

CH3COOH, M = 60.05 g/mol, z = 1

pK pK pK pK
- -
CH3COOH + OH → CH3COO + H2O (HNV) Potent. Potent. Potent.
Method Method Method
Solutions and Reagents Ia Ib II
 Titrant: 0.1 KNO3
Potassium hydroxide in 0.1 KNO3, KOH, 1 4.662 4.555 4.556 4.548
c(KOH) = 0.1 mol/L 2 4.663 4.559 4.560 4.552
3 4.662 4.557 4.558 4.548
 Chemicals:
4 4.556 4.559 4.547
- Potassium nitrate, KNO3
Mean 4.662 4.556 4.558 4.549
- 0.1 M KNO3
s 0.001 0.002 0.002 0.002
- Deionized water
srel 0.021% 0.043% 0.043% 0.044%
- pH buffer 4.01, 7.00 and 9.21
Deionized water
 Standard: 1 4.699 4.633 4.635 4.626
Potassium hydrogen phthalate, KHP, 80 mg 2 4.674
3 4.673
Instruments and Accessories 4 4.670
 Titration Excellence T7/T9 Mean 4.679 4.633 4.635 4.626
or T5 Package (30252672) s 0.013
 T7/T9: 10 mL Glass burette DV1010 srel 0.287%
(51107501)
1 4.773 4.742
 T7/T9: Compact Stirrer (51109150) 2 4.760
 100 mL Thermostatable beaker (23517) 3 4.755
Mean 4.763 4.742
s 0.009
srel 0.189%

1 4.808
2 4.807
3 4.798
Mean 4.804
s 0.006
srel 0.125%

Reference value: pKa = 4.756, 25°C, pure water

The pKa value of acetic acid CH3COOH has been

 External water bath circulator (third party)
 Gas inlet for nitrogen purging (23721)
 DGi111-SC pH combined electrode
(51109500)
 DT1000 Temperature probe (51109828)
 LabX software
 XP205 Analytical balance (11106027)
 Spatula
determined by three different titration techniques in
0.1M KNO3 as well as in deionized water:
1. Half-neutralization value (HNV)
2. Potentiometric Method I
o I a: [A-]/[HA] = [OH-INC]/([HA0]EQP-[OH-INC])
o I b: [A-]/[HA] = OH-INC/( VEQ-OH-INC)
3. Potentiometric Method II
(Details: see "Remarks").

METTLER TOLEDO Page 2 of 10

M760 v1.0
 Remarks
Titration Application Note

 The determination of the exact values of the

pKa [1] of an acid by titration with a strong
base can be a demanding and time-
consuming task. The correct procedure
requires in particular

1. the value of the reference potential Eo in the

Nernst equation, E = E0 - spH, where s is
the adjustment slope in mV/pH.  The half-neutralization value HNV can be
automatically determined by defining in the
2. activities a rather than concentrations c (a
calculation function the raw data parameter
= *c, : activity coefficient),
EHNV as a result, i.e. R = EHNV. By using a
3. the exact ionic product of water due to the previously adjusted pH electrode the result
+ -
dissociation of water, Kw = [H3O ][OH ]. gives directly an estimation of the pKa-value:
 Electrode parameters such as the reference
potential E0 have to be first determined under
controlled conditions [1] i.e. at specific
temperature, pressure, ionic strength and
under inert atmosphere using e.g. nitrogen
gas. Inert gas is needed to avoid CO2 intake
from the air which leads to carbonate
formation in alkaline solutions.

 Therefore, it is of interest to use techniques

which simplify and speed up the pKa value
determination by potentiometric titration.

Here, the three methods used are presented.

1) Half-neutralization value (HNV)

 A straightforward way to rapidly estimate the
pKa value of a weak monoprotic acid HA in
aqueous solution is to determine the so-called
Half-Neutralization Value, HNV [2].
 This value corresponds to half of the titrant
consumption needed for complete
neutralization in an acid-base titration i.e. up
to the equivalence point VEQ/2.
 The HNV-value between 4 and 10 represents
 When 50% of the weak acid has been an excellent approximation of the pKa value.
neutralized, the concentration [HA] of Outside these limits,
undissociated acid HA is approx. equal to the
-
concentration [A ] of the dissociated form, i.e. 1. the HNV value gives an overestimate of the
[A-]  [HA]. pKa for strong acids i.e. for pKa < 4,
whereas
 Hence, pKa = pH + log([A-]/[HA]), and thus
pKa= pH + log(1) = pH , i.e. the pKa is the pH 2. for weak acids (pKa > 10) the determined
value at half-neutralization VEQ/2. HNV gives a too low pKa [2].

METTLER TOLEDO Page 3 of 10

M760 v1.0
 2) Potentiometric method I
Titration Application Note
 A step towards a more accurate pKa
determination is achieved with Method I. Here,
the stoichiometry of the neutralization reaction
and the dependence on the ionic strength are
considered for the calculation.
 The sensor is calibrated by determining the
real ionic product of water Kw. Briefly, it is
obtained by titrating a strong acid (base) with
a strong base (acid) to get the reference
potentials E0 in the acid and basic regions.
This will compensate for the different ionic
strengths of the pH buffers used for calibration.
Details are given in Application M759 [3].
 Setup:
Calibration and titration are both performed in
a thermostated beaker connected to a water
bath circulator where the temperature is
usually set to 20 or 25°C, and at constant
ionic strength of e.g. 0.1 M KNO3. Nitrogen is
blown in the solution to avoid CO2 absorption.
 Titration method:
Increments of e.g. dV=0.2 mL are added, and
the potential is measured at fixed time intervals
of e.g. t =45 s to achieve a stable signal.
 Evaluation:
The pKa is calculated at e.g. 10 different points
in the acidic buffer region of the titration curve
i.e. in the flat part of the curve from pKa = pH-
- -
log[A ]/[HA]. In this region, [HA] > [OH ] and
the potential change between the measured
points is very small.
Thus, an average pKa can be calculated from
e.g. 10 single measured points [1,4] using
the following approximations:
EQP -
- [HA]  [HA]0 – [OH ]add,
- -
- [A ]  [OH ]add,
EQP
where [HA]0 represents the determined
initial concentration of the weak acid HA, and
- -
[OH ]add is the concentration of the strong base
in the solution after each titrant addition.
 Calculation:
Finally, the data are exported into an Excel
spreadsheet for calculation.
METTLER TOLEDO
M760 v1.0
3) Potentiometric method II
 This method represents a more detailed
approach to pKa determination. In fact, the
concentrations of the different components (i.e.
+ - -
HA, H , A , OH ) vary during titration, and the
chemical equilibrium shifts continuously.
Moreover, the pH value is not only determined
by the added titrant, but also by the acid, HA,
and the ionic product of water, KW. Thus, it is
necessary that the equilibrium concentrations
- +
[OH ] and [H ] are also taken into account.
 First, the sensor is calibrated by determining
the real ionic product of water Kw, as indicated
in Method I. A procedure is given in
Application M759 [3]. The setup and the
titration method are as described in Method I.
 Evaluation:
The pKa is calculated at e.g. 10 different points
in the acidic buffer region of the titration curve
-
from pKa = pH-log[A ]/[HA]. In this region,
-
[HA] > [OH ] and the potential change is very
small. Thus, an average pKa can be calculated
from e.g. 10 single measured points [1,4]
taking into accounts the following points:
- The sum of all electrical charges is always
0. In particular, during titration
- - + +
[A ] + [OH ] = [K ] + [H ]
- The amount of substance of each
compound involved in the reaction is
constant (mass conservation law) i.e. the
total concentration of the weak acid HA is
EQP -
[HA] = [HA]0 + [A ]
Therefore:
- + + -
- [A ] = [K ] + [H ] - [OH ] =
+ -
= [KOH] + [H ] - [OH ]
EQP -
- [HA] = [HA]0 - [A ] =
EQP + -
= [HA]0 - [KOH] - [H ] + [OH ]
where [KOH] is the added titrant (KOH:
+
complete dissociate), [H ] is the free acid due
to protons dissociating from HA, and OH is
the added base which has not reacted
 Calculation:
Finally, the data are exported into an Excel
spreadsheet for calculation.
Page 4 of 10
 Potentiometric Method I – Excel spreadsheet for calculation
Titration Application Note

A B C D E F G H I J
1
pKa Determination
of acetic acid
2

4 C0 CH3COOH 0.10161
T 25.0
(mol/L) (°C)
Sample
5 5
s 25°C 59.16
size m0 (mV/pH)
(mL)
Sample
6 0.50805
I KNO3 0.1
size m0 (mol/L)
(mmol)
Titration
7 vol. V0 50
(mL)
8
Titrant
9 conc. c KOH 0.09125
(mol/L)
EQP
10 (Q/mmol), 0.503 5.518
(VEQ/mL)
11 pKW 13.69

12
E0H 409.574 E0OH -400.490
(mV) (mV)
13

14

-
[A ] = [HA] = Method Ia Method Ib
OH-INC OH-INC*c VTOT E pH = [H+] pKa = pKa =
15 [OH-INC] [HA0]EQP-[OH-INC]
(mL) (mmol) (mL) (mV) (E0-E)/s (mol/L) pH – pH -
(mol/L) (mol/L) -
log ( [A ]/[HA] ) log ( INC /(VEQ - INC) )

E16 - E16 –
16 0.000 A16*C9 C7 + A16 215.100 (C12-D16)/G5 POWER(10; - E16) B16/C16 (B10/C16) - G16
log10(A16/(C10-A16))
log10(G16/H16)
E17 - E17 –
17 0.250 A17*C9 C7 + A17 203.600 (C12-D17)/G5 POWER(10; - E17) B17/C17 (B10/C17) - G17
log10(G17/H17) log10(A17/(C10-A17))
E18 - E18 –
18 0.500 A18*C9 C7 + A18 193.200 (C12-D18)/G5 POWER(10;- E18) B18/C18 (B10/C18) - G18
log10(G18/H18) log10(A18/(C10-A18))
E19 - E19 –
19 0.750 A19*C9 C7 + A19 184.400 (C12-D19)/G5 POWER(10; - E19) B19/C19 (B10/C19) - G19
log10(G19/H19) log10(A19/(C10-A19))
E16 - E20 –
20 1.000 A20*C9 C7 + A20 177.000 (C12-D20)/G5 POWER(10; - E20) B20/C20 (B10/C20) – G20
log10(G20/H20) log10(A20/(C10-A20))
21 1.250 … … … … … … … 4.574 4.575

22 1.500 … … … … … … … 4.567 4.567

23 1.750 … … … … … … … 4.561 4.562

24 2.000 … … … … … … … 4.558 4.559

25 2.250 … … … … … … … 4.556 4.557

26 2.500 … … … … … … … 4.555 4.556

27 2.750 … … … … … … … 4.552 4.553

28 3.000 … … … … … … … 4.551 4.552

29 3.250 … … … … … … … 4.550 4.551

30 3.500 … … … … … … … 4.548 4.549

31 3.750 … … … … … … … 4.548 4.550

32 4.000 … … … … … … … 4.549 4.550

33 4.250 … … … … … … … 4.549 4.551

E34 - E34 –
34 4.500 A34*C9 C7 + A34 54.500 (C12-D34)/G5 POWER(10; - E34) B34/C34 (B10/C34) – G34
log10(G34/H34) log10(A34/(C10-A34))
E35 - E35 –
35 4.750 A35*C9 C7 + A35 54.750 (C12-D35)/G5 POWER(10; - E35) B35/C35 (B10/C35) – G35
log10(G35/H35) log10(A35/(C10-A35))
E36 - E36 –
36 5.000 A36*C9 C7 + A36 55.000 (C12-D36)/G5 POWER(10;- E36) B36/C36 (B10/C36) – G36
log10(G36/H36) log10(A36/(C10-A36))
E37 - E37 –
37 5.250 A37*C9 C7 + A37 55.250 (C12-D37)/G5 POWER(10; - E37) B37/C37 (B10/C37) – G37
log10(G37/H37) log10(A37/(C10-A37))
E38 - E38 –
38 5.500 A38*C9 C7 + A38 55.500 (C12-D38)/G5 POWER(10; - E38) B38/C38 (B10/C38) – G38
log10(G38/H38) log10(A38/(C10-A38))
E16 - E39 –
39 5.740 A39*C9 C7 + A39 55.750 (C12-D39)/G5 POWER(10; - E39) B39/C39 (B10/C39) – G39
log10(G39/H39) log10(A39/(C10-A39))

METTLER TOLEDO Page 5 of 10

M760 v1.0
 Potentiometric Method II – Excel spreadsheet for calculation
Titration Application Note

A B C D E F G H I J
1
pKa Determination
of acetic acid
2

4 C0 CH3COOH 0.10161
T 25.0
(mol/L) (°C)
Sample
5 5
s 25°C 59.16
size m0 (mV/pH)
(mL)
Sample
6 0.50805
I KNO3 0.1
size m0 (mol/L)
(mmol)
Titration
7 vol. V0 50
(mL)
8
Titrant
9 conc. c KOH 0.09125
(mol/L)
EQP
10 (Q/mmol), 0.503 5.518
(VEQ/mL)
11 pKW 13.69

12
E0H 409.574 E0OH -400.490
(mV) (mV)
13

14

[HA]
- [A-] = Method II
[OH ] = =
OH-INC OH-INC*c VTOT E pH = [H+] [OH-INC] - [OH-]
15 10-(pKw - pH) [HA0]EQP - [OH-INC]
(mL) (mmol) (mL) (mV) (E0-E)/s (mol/L) + [H+] pKa =
(mol/L) + [OH-] - [H+]
(mol/L) pH-log([A-]/[HA])
(mol/L)
POWER POWER (B16/C16) (B10/C16)-(B16/C16) E16 -
16 0.000 A16*C9 C7 + A16 215.100 (C12-D16)/G5
(10; - E16) (10; -(C11-E16) ) - G16 + F16 + G16 - F16 log10(H16/I16)
POWER POWER (B17/C17) (B10/C17)-(B17/C17) E17 -
17 0.250 A17*C9 C7 + A17 203.600 (C12-D17)/G5
(10; - E17) (10; -(C11-E17) ) - G17 + F17 + G17 - F17 log10(H17/I17)
POWER POWER (B18/C18) (B10/C18)-(B18/C18) E18 -
18 0.500 A18*C9 C7 + A18 193.200 (C12-D18)/G5
(10;- E18) (10; -(C11-E18) ) - G18 + F18 + G18 - F18 log10(H18/I18)
POWER POWER (B19/C19) (B10/C19)-(B19/C19) E19 -
19 0.750 A19*C9 C7 + A19 184.400 (C12-D19)/G5
(10; - E19) (10; -(C11-E19) ) - G19 + F19 + G19 - F19 log10(H19/I19)
POWER POWER (B20/C20) (B10/C20)-(B20/C20) E20 -
20 1.000 A20*C9 C7 + A20 177.000 (C12-D20)/G5
(10; - E20) (10; -(C11-E20) ) - G20 + F20 + G20 – F20 log10(H20/I20)
21 1.250 … … … … … … … … 4.551

22 1.500 … … … … … … … … 4.550

23 1.750 … … … … … … … … 4.549

24 2.000 … … … … … … … … 4.549

25 2.250 … … … … … … … … 4.548

26 2.500 … … … … … … … … 4.549

27 2.750 … … … … … … … … 4.547
28 3.000 … … … … … … … … 4.546

29 3.250 … … … … … … … … 4.546

30 3.500 … … … … … … … … 4.545

31 3.750 … … … … … … … … 4.546
32 4.000 … … … … … … … … 4.546

33 4.250 … … … … … … … … 4.546
POWER POWER (B34/C34) (B10/C34)-(B34/C34) E34 -
34 4.500 A34*C9 C7 + A34 54.500 (C12-D34)/G5
(10; - E34) (10; -(C11-E34) ) - G34 + F34 + G34 – F34 log10(H34/I34)
POWER POWER (B35/C35) (B10/C35)-(B35/C35) E35 -
35 4.750 A35*C9 C7 + A35 54.750 (C12-D35)/G5
(10; - E35) (10; -(C11-E35) ) - G35 + F35 + G35 – F35 log10(H35/I35)
POWER POWER (B36/C36) (B10/C36)-(B36/C36) E36 -
36 5.000 A36*C9 C7 + A36 55.000 (C12-D36)/G5
(10;- E36) (10; -(C11-E36) ) - G36 + F36 + G36 – F36 log10(H36/I36)
POWER POWER (B37/C37) (B10/C37)-(B37/C37) E37 -
37 5.250 A37*C9 C7 + A37 55.250 (C12-D37)/G5
(10; - E37) (10; -(C11-E37) ) - G37 + F37 + G37 – F37 log10(H37/I37)
POWER POWER (B38/C38) (B10/C38)-(B38/C38) E38 -
38 5.500 A38*C9 C7 + A38 55.500 (C12-D38)/G5
(10; - E38) (10; -(C11-E38) ) - G38 + F38 + G38 – F38 log10(H38/I38)
POWER POWER (B39/C39) (B10/C39)-(B39/C39) E39 -
39 5.740 A39*C9 C7 + A39 55.750 (C12-D39)/G5
(10; - E39) (10; -(C11-E39) ) - G39 + F39 + G39 – F39 log10(H39/I39)

METTLER TOLEDO Page 6 of 10

M760 v1.0
 Half neutralization value - Measured values
Titration Application Note

Half neutralization value

0.1 M KNO3 - 1st sample
pKa as HNV = 4.662
14

12

10

8
pH value

0
0 1 2 3 4 5 6 7 8 9 10
Titrant consumption/mL

Table of measured values

Time Volume Increment Signal Change 1st derivative EQP
min:s [mL] [mL] [pH] [pH] [pH/mL]
1:00 0.000 3.375
2:00 0.200 0.2 3.534 0.159 0.797
3:00 0.400 0.2 3.685 0.15 0.752
4:00 0.600 0.2 3.816 0.131 0.657
5:00 0.800 0.2 3.930 0.114 0.568
6:00 1.000 0.2 4.031 0.101 0.507
7:00 1.200 0.2 4.121 0.09 0.451
8:00 1.400 0.2 4.203 0.081 0.407
9:00 1.600 0.2 4.280 0.077 0.384
10:00 1.800 0.2 4.351 0.071 0.357
11:00 2.000 0.2 4.420 0.069 0.345
12:00 2.200 0.2 4.486 0.066 0.329
13:00 2.400 0.2 4.550 0.065 0.323
14:00 2.600 0.2 4.614 0.064 0.318
15:00 2.800 0.2 4.675 0.061 0.306
16:00 3.000 0.2 4.739 0.064 0.318
17:00 3.200 0.2 4.804 0.066 0.329
18:00 3.400 0.2 4.870 0.066 0.329
19:00 3.600 0.2 4.939 0.069 0.345
20:00 3.800 0.2 5.013 0.074 0.368
21:00 4.000 0.2 5.091 0.078 0.39
22:00 4.200 0.2 5.174 0.084 0.418
23:00 4.400 0.2 5.259 0.085 0.423
24:00 4.600 0.2 5.363 0.104 0.518
25:00 4.800 0.2 5.500 0.137 0.685
26:00 5.000 0.2 5.673 0.174 0.869
27:00 5.200 0.2 5.923 0.25 1.248
28:00 5.400 0.2 6.429 0.506 2.529
29:00 5.600 0.2 9.951 3.522 17.609 EQP
30:00 5.800 0.2 10.578 0.627 3.136
31:00 6.000 0.2 10.834 0.256 1.281

... ... ... ... ... ...

49:00 9.600 0.2 11.778 0.021 0.106

50:00 9.800 0.2 11.798 0.020 0.100
51:00 10.000 0.2 11.817 0.019 0.095

METTLER TOLEDO Page 7 of 10

M760 v1.0
 pKa – Determination by potentiometric Methods I & II
Titration Application Note

Potentiometric Methods
0.1 M KNO3 - 1st sample

pKa - Method Ia: 4.555

pKa - Method Ib: 4.556
pKa - Method II: 4.548
300

200

100
Potential/mV

0
0 1 2 3 4 5 6 7 8 9 10
-100

-200

-300
Titrant consumption/mL

Table of measured values

Time Volume Increment Signal Change 1st derivative EQP
min:s [mL] [mL] [mV] [mV] [mV/mL]
1:00 0.000 215.1
2:00 0.250 0.25 203.6 -11.6 -46.3
3:00 0.500 0.25 193.2 -10.4 -41.6
4:00 0.750 0.25 184.4 -8.7 -34.9
5:00 1.000 0.25 177.0 -7.4 -29.7
6:00 1.250 0.25 170.5 -6.5 -26.1
7:00 1.500 0.25 164.7 -5.8 -23.0
8:00 1.750 0.25 159.4 -5.4 -21.5
9:00 2.000 0.25 154.4 -5 -19.9
10:00 2.250 0.25 149.6 -4.8 -19.1
11:00 2.500 0.25 144.9 -4.7 -18.6
12:00 2.750 0.25 140.4 -4.5 -18.1
13:00 3.000 0.25 135.8 -4.6 -18.4
14:00 3.250 0.25 131.1 -4.7 -18.9
15:00 3.500 0.25 126.3 -4.8 -19.4
16:00 3.750 0.25 121.1 -5.2 -20.7
17:00 4.000 0.25 115.5 -5.6 -22.5
18:00 4.250 0.25 109.3 -6.2 -24.8
19:00 4.500 0.25 102.0 -7.2 -29.0
20:00 4.750 0.25 93.2 -8.9 -35.4
21:00 5.000 0.25 81.2 -12 -47.8
22:00 5.250 0.25 61.6 -19.6 -78.3
23:00 5.500 0.25 -14.3 -75.9 -303.7
24:00 5.750 0.25 -196.7 -182.4 -729.7 EQP
25:00 6.000 0.25 -217.1 -20.4 -81.7
26:00 6.250 0.25 -228.4 -11.2 -45.0
27:00 6.500 0.25 -236.1 -7.8 -31.0
28:00 6.750 0.25 -241.9 -5.8 -23.3
29:00 7.000 0.25 -246.8 -4.8 -19.4
30:00 7.250 0.25 -250.7 -3.9 -15.8
31:00 7.500 0.25 -254.1 -3.4 -13.4

... ... ... ... ...

39:00 9.500 0.25 -271.5 -1.6 -6.2

40:00 9.750 0.25 -273.0 -1.5 -5.9
41:00 10.000 0.25 -274.4 -1.4 -5.7

METTLER TOLEDO Page 8 of 10

M760 v1.0
 Comments
Titration Application Note
 All methods gives very good results in pure
water, with values varying between 4.626 ±
0.017 (Pot. II) up to 4.804 ± 0.006 (HNV),
and thus showing a very good agreement
with the reference value of 4.756 at 25°C.
 The pKa value measured in 0.1 M KNO3 is
lower than the one in pure water, with results
varying between 4.547 and 4.560. This is a
clear indication of the impact of different
ionic strength due to the presence of
dissolved salt.
 The pKa determination by potentiometric
methods I and II require a pH sensor
calibration by strong acid/strong base
titration, and not by standard adjustment
with pH buffer solutions.
 However, the use of pH buffer solutions is a
much quicker and practical way of adjusting
a pH electrode. The outcome of this
alternative shows that the values obtained
are also in very good agreement with the
reference value of 4.756, giving pKa-values
ranging from 4.736±0.006 to 4.743±0.012
for pure water. In 0.1 M KNO3 aqueous
solution the pKa of acetic acid has been
determined several time leading to values
from 4.660±0.004 up to 4.678±0.007 that
are again in good agreement with the other
results.
 For this reason, it may be considered to use
pH buffer solutions to adjust the pH sensor
for a good estimation of the pKa value
whenever time is a constraint.
 The use of nitrogen gas allows to avoid
absorption of carbon dioxide from the air. In
this way, carbonate formation is avoided,
and thus no shift of the chemical equilibrium
of the acid/base reaction will take place.
 Whenever possible, use the same kind of
ions in order to reduce the influence of
different ions on the results. For instance, if
the salt used is KCl or KNO3, then use KOH
as a base, and KCl as a reference electrolyte.
On the other hand, when using NaCl or
METTLER TOLEDO
M760 v1.0
NaNO3 as inert electrolyte, then use NaOH as
an alkaline titrant.
 The titrations have been performed by using
fixed titrant increments of 0.2 or 0.25 mL, in
order to comply with standard procedures as
indicated in the literature. However, also the
dynamic titrant addition with increments
varying between 0.02 mL and 0.2 mL, in
combination with the equilibrium controlled
measured signal acquisition can be used. In
this way, time can be additionally saved.
 Recommendations:
1. HNV-determination:
use dynamic titrant addition (DYN)
since the accurate determination of the
equivalence point is the relevant step.
2. Potentiometric Methods I and II:
use fixed titrant increment addition
(INC) since the accurate determination
of the measured points is the relevant
step.
Waste disposal and safety measures
After neutralization dispose the solution as
aqueous waste.
References
[1] A. Albert, E.P. Serjeant, “The Determination of
Ionization Constants: A Laboratory Manual”,
rd
3 Edition, 1984, Chapman and Hall.
[2] “Titration Fundamentals”, METTLER TOLEDO
Publication ME-51725311, 09/2010.
[3] "Determination of The Ionic Product Kw of
Water ", Titration Application Note M759.
[4] US Environmental Protection Agency, EPA
Products Properties Test Guidelines, “OPPTS
830.7370 Dissociation constants in water”,
EPA-712-C-96-036, August 1996.
Further information
http://www.mt.com/global/en/home/products/Labo
ratory_Analytics_Browse/Product_Family_Browse_
titrators_main/Titration_Excellence.html
Page 9 of 10
 pKa by Half-Neutralization Value Potentiometric Methods I & II
Titration Application Note

001 Title 001 Title

Type General titration Type General titration
Compatible with T5/T7/T9 Compatible with T5/T7/T9
ID M760A ID M760B
Title pK by HNV Title pK by pot. Methods I & II
… …
002 Sample 002 Sample
Number of IDs 1 Number of IDs 1
ID 1 0.1 M acetic acid ID 1 0.1 M acetic acid
Entry type Fixed volume Entry type Fixed volume
Volume 5.0 mL Volume 5.0 mL
… …
003 Titration stand (Manual stand) 003 Titration stand (Manual stand)
Type Manual stand Type Manual stand
Titration stand Manual stand 1 Titration stand Manual stand 1
004 Stir 004 Stir
Speed 30 % Speed 30 %
Duration 120 s Duration 120 s
005 Titration (EQP) [1] 005 Titration (EQP) [1]
Titrant Titrant
Titrant KOH Titrant KOH
Concentration 0.1 mol/L Concentration 0.1 mol/L
Sensor Sensor
Type pH Type pH
Sensor DG111-SC Sensor DG111-SC
Unit pH Unit mV
Temperature acquisition Temperature acquisition
Temperature sensor DT1000 Temperature sensor DT1000
Temperature unit °C Temperature unit °C
Stir Stir
Speed 30 % Speed 30 %
Predispense Predispense
Mode None Mode None
Wait time 0s Wait time 0s
Control Control
Control User Control User
Titrant addition Dynamic Titrant addition Incremental
dE(set value) 8.0 mV dV 0.2 mL
dV(min) 0.02 mL Meas. val. acquisition Fixed time
dV(max) 0.2 mL dt 60 s
Meas. val. acquisition Equilibrium controlled Evaluation and recognition
dE 0.5 mV Procedure Standard
dt 1s Threshold 300 mV/mL
t(min) 15 s Tendency Negative
t(max) 30 s …
Evaluation and recognition Termination
Procedure Standard At Vmax 10 mL
Threshold 3 pH/mL …
Tendency Positive 006 Calculation R1
…
Result Content
Termination
Result unit mol/L
At Vmax 10 mL
Formula R1 = Q*C/m
…
Constant C = 1/z
006 Calculation R1 M M[acetic acid]
Result Half-Neutralization Value HNV Z z[acetic acid]
Result unit pK(HNV) Decimal places 3
Formula R1 = EHNV ...
Constant C=1 007 Calculation R2
...
Result Consumption
Decimal places 3
Result unit mL
...
Formula R2 = VEQ
007 Calculation R2 ...
Result Consumption Decimal places 3
Result unit mL ...
Formula R2 = VEQ 008 Calculation R3
...
Result Consumption
Decimal places 3
Result unit mmol
...
Formula R3 = Q
008 Calculation R3 ...
Result Consumption Decimal places 3
Result unit mmol ...
Formula R3 = Q 009 End of sample
...
Decimal places 3
...
009 End of sample

METTLER TOLEDO Page 10 of 10

M760 v1.0

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