Journal of Solution Chemistry, Vol. 28, No.

4, 1999

Determination of the Glass Electrode Parameters

by Means of Potentiometric Titration of Acetic
Acid in Aqueous Sodium or Potassium Chloride
Solutions at 25°C+
Jaakko I. Partanen,* Pekka M. Juusola, and
Pentti O. Minkkinen
Received July 15, 1998; revised December 2, 1998

Single-ion activity coefficient equations are presented for the calculation of stoichio-
metric (molality scale) dissociation constants Km for acetic acid in aqueous NaCl or
KCl solutions at 25°C. These equations are of the Pitzer or Huckel type and apply
to the case where the inert electrolyte alone determines the ionic strength of the acetic
acid solution considered. Km for a certain ionic strength can be calculated from the
thermodynamic dissociation constant Ka,by means of the equations for ionic activity
coefficients. The data used in the estimation of the parameters for the activity coefficient
equations were taken from the literature. In these data were included results of
measurements on galvanic cells without a liquid junction (i.e., on cells of the Harned
type). Despite the theoretical difficulties associated with the single-ion activity coeffi-
cients, Km can be calculated for acetic acid in NaCl or KCl solutions by the Pitzer
or Huckel method (the two methods give practically identical Km values) almost
within experimental error at least up to ionic strengths of about I mol-kg-1. Potentio-
metric acetic acid titrations with base solutions (NaOH or KOH) were performed in
a glass electrode cell at constant ionic strengths adjusted by NaCl or KCl. These
titrations were analyzed by equation E = Eo + k(RT/F) ln[m(H+)], where m(H+) is
the molality of protons, and £ is the electromotive force measured. m(H+) was
calculated for each titration point from the volume of the base solution added by
using the stoichiometric dissociation constant Km obtained by the Pitzer or Huckel
method. During each base titration at a constant ionic strength, Eo and k in this
equation were observed to be constants and were determined by linear regression
analysis. The use of this equation in the analysis of potentiometric glass electrode
data represents an improvement when compared to the common methods in use for
two reasons. No activity coefficients are needed and problems associated with liquid
junction potentials have been eliminated.

Department of Chemical Technology, Lappeenranta University of Technology, P.O. Box 20,

F1N-53851 Lappeenranta, Finland.
+We dedicate this paper to the memory of Professor Kenneth S. Pitzer in recognition of his
many invaluable contributions to solution chemistry.
413
0095-9782/0400-04123$16.00/0© 1999 Plenum Publishing Corporation
414 Partanen, Juusola, and Minkkinen

KEY WORDS: Ionic activity coefficients; stoichiometric dissociation constant;

acetic acid; glass electrode.

1. INTRODUCTION
In practical studies of electrolyte solutions, e.g., in biochemistry and
analytical chemistry, the stoichiometric dissociation constants of weak acids
(i.e., the dissociation constants on the molality or molarity scale, Km or Kc,
respectively) are in common use. They are, for example, needed when the
amount of a weak acid is determined by a potentiometric glass electrode
titration where the results of the titration are analyzed by an appropriate
linear representation (see, for example, Ingman and Still (1) )• Often the ionic
strength Ic of the weak acid solution titrated is adjusted to be constant by an
inert electrolyte, e.g., by NaCl. It has been observed that Kc for the weak
acid remains also constant during such a titration. It is, in addition, well
known that even in a very dilute salt solution (even at a concentration
of 0.01 mol-dm -3 ), Kc often differs considerably from the thermodynamic
dissociation constant Ka. Usually the latter value, therefore, cannot be used
in the quantitative analysis based on potentiometric titration data. In practice,
for most cases, even at the present day, Kc (or Km) must first be experimentally
determined from separate titration data for these analyses.
In the present study, two methods (called below the Pitzer and Huckel
methods) are given for the calculation of Km at different ionic strengths from
Ka for acetic acid in aqueous NaCl or KCl solutions at 25°C. The Huckel
method is based on semiempirical equations for ionic activity coefficients.
These equations originate partially from Debye-Huckel theory. The Pitzer
method is based on the Pitzer formalism for the thermodynamic treatment
of mixed electrolyte solutions (see, e.g., Pitzer(2)). This formalism has proved
to be very useful on many occasions, and, therefore, has become widely
accepted. The Pitzer formalism also permits, after ignoring the nondetermin-
able part of a single-ion activity coefficient equation that cancels when the
equations are combined to give mean activity coefficients, the calculation of
ionic activity coefficients in weak acid solutions.
In the previous studies,(3,4) the activity coefficient equations for the Pitzer
and Hiickel methods were determined for the calculation of the molality
scale dissociation constants km of acetic acid from the literature results for
appropriate galvanic cells containing a hydrogen electrode and a silver-silver
chloride electrode in acetic acid solutions (i.e., Harned cells). The data mea-
sured on cells of this kind were used in these parameter estimations instead
of data measured on glass electrode cells to avoid the problems associated
Determination of Glass Electrode Parameters 415

with the latter (for example, with the assymmetry potentials, liquid junction
potentials, and calibrations). Both the Pitzer method and the Huckel method
predict practically the same Km values for acetic acid at different ionic
strengths for NaCl or KCl solutions up to a salt molality of about 1 mol-kg -1 .
In the present study, the Km values calculated by the Pitzer or Huckel
method are used in the analysis of potentiometric titrations of acetic acid
carried out in aqueous NaCl or KCl solutions at 25°C. In the literature, several
methods have been presented for the calibration of the type of glass electrode
cells considered in this study. For this purpose, a cell of this kind can be
written as follows:

where S and X refer to aqueous solutions of standard and unknown pH,

respectively. The pH is defined by

where aH, mH, and yH refer to the activity, molality, and activity coefficient
of protons, respectively. For the electrometric method for the assessment of
the unknown pH, the electromotive forces Es and Ex are measured for solutions
S and X, respectively. From these results, the operational pH value for solution
X can be calculated from

pH(S) values for the reference solutions have been recommended by IUPAC,(5)
and have been assigned from electromotive force (emf) measurements on
cells without a liquid junction, i.e., on Harned cells of the type

where / is the fugacity. The quantity that can be experimentally obtained

from the electromotive forces E measured on cells of Type II is — log(aHycl).
It can be calculated by

where E° is the standard emf. Its value can be obtained by measuring the
emf for the cell of Type II, where the standard solution is replaced by a 0.01
mol-kg -1 solution of HCl, and calculating this quantity from the measured
E value and the recommended values(6) for y± = (y H Y c l ) 1 / 2 for this solution.
The quantity — log(aHycl) is calculated from measured E values for each of
416 Partanen, Juusola, and Minkkinen

several molalities of chloride ions mc1. It is then plotted against mc1 and
extrapolated to mc1 = 0. Finally, pH(S) is calculated from

where yc1 is obtained from the Bates-Guggenheim convention

where a is the Debye-Huckel limiting slope. For the most recent values, see
Archer and Wang.(7) According to IUPAC,(5) the reference value pH standard
is a 0.05 mol-kg -1 solution of potassium hydrogen phthalate (at 25°C pH =
4.005), and the primary pH standards are the following solutions: at 25°C
saturated potassium hydrogen tartrate, pH = 3.557; 0.1 mol-kg -1 potassium
dihydrogen citrate, 3.776; 0.025 mol-kg - 1 disodium hydrogen phosphate +
0.025 mol-kg- 1 potassium dihydrogen phosphate, 6.865; 0.03043 mol-kg-1
disodium hydrogen phosphate + 0.008695 mol-kg-1 potassium dihydrogen
phosphate, 7.413; 0.1 mol-kg-1 disodium tetraborate, 9.180; 0.025 mol-kg-1
sodium hydrogen carbonate + 0.025 mol-kg-1 sodium carbonate, 10.012.
Another calibration method has been mentioned in the IUPAC recom-
mendations (5) It is the bracketing procedure, which is used as follows. The
electromotive force E(X) is measured by cell of Type I and, likewise, the
electromotive forces E(S1 and E(S2) are measured on this cell for standard
solutions S1 and S2. The standard solutions should be chosen in such a way
that E(S1) and E(S2) are on either side of, and as near as possible to, E(X).
The pH of solution X is obtained by assuming linearity between pH and E,
that is to say:

The purpose of the bracketing procedure is to compensate for deficiencies

in the electrodes and measuring system.
The measured emf for cells of Type I can be divided into four parts in
the following way as shown, for instance, by May et al.(8)

where Er is the contribution of the reference electrode potentials (this contribu-

tion is independent on the composition of the test solution S or X) and Ey
is the liquid junction potential. (It has been demonstrated that Eij depends
on the concentrations of the species in the test solution and the reference-
electrode solution, and some mathematical expressions are also available to
take into account this effect. This potential was assumed to be constant during
each acetic acid titration considered here. The ionic strength of the solution
titrated did not appreciably change during this titration, and the proton concen-
Determination of Glass Electrode Parameters 417

tration was always small in the solution titrated.) E°g is the standard glass-
electrode potential (including the assymmetry potential) and k is a constant,
which has a value of k = 1 for glass electrodes, that completely obey the
Nernst equation.
Equation (7) is the starting point for the calibration method suggested
by May et al.(8) It is based on a strong acid vs. strong base titration in the
approximate pH ranges 2.3-2.9 or 10.8-11.3 in such a solution where the
ionic strength remains constant during titration. During this titration the
following equation is valid

where CH represents the concentration of protons and Eo,c is defined by

The activity coefficient of protons (on the concentration scale) y C,H also
remains constant during the titration as well as Eo,c. The glass electrode
parameters can be estimated by the following equations from the results of
these titrations in the acid and base regions [see Fiol et al.(9)]. For the
acid region

For the base region

In Eqs. (10) and (11) ca is the concentration of the strong acid in the salt
solution titrated, cb the concentration of the strong base solution used as
titrant, x - V/V0, where V is the added base volume and V0 the initial volume
of the strong acid solution, COH is the concentration of hydroxyl ions, and
Kw is the ionization constant of water in the solution titrated. Equation (10)
or (11) represents an equation of a straight line. The independent variables
of these equations are ln(cH) ( Eq. 10), or ln(c oH ) (Eq. 11), and the values of
these variables can be straightforwardly calculated from the titration data, as
shown in Eqs. (10) and (11). The response variable in these equations is the
emf E. The glass electrode parameters can be determined by means of these
equations using linear regression analysis.
Fiol et al.(9) suggest an improved method for the calibration of a glass
electrode cell by means of strong acid and base solutions. They recommend
that volumes V of these solutions are successively added directly to the
solution of the initial background electrolyte (volume V0) without any titra-
418 Partanen, Juusola, and Minkkinen

tions. In this case, the following equations are valid in the acid and base
regions. For the acid region

For the base region

Equations (12) and (13) are used as Eqs. (10) and (11), respectively. The
advantage of the use of Eqs. (12) and (13) is that the systematic errors in ca
and cb do not affect the slopes of the straight lines.
In the present study, the same idea as that of May et al.(8) and Fiol et
(9)
al. is used for the determination of glass electrode parameters. Instead of
a strong acid vs. strong base titration, the calibration titration here is an acetic
acid vs. strong base titration at a constant ionic strength. The results of this
titration are presented as molalities instead of molarities used by the two
previous research groups. For the acetic acid titration on cells of Type I, the
following equation [corresponding to Eq. (8)] can be used.

The molality of protons mH can be calculated for each titration point from
titration data and the stoichiometric dissociation constant Km calculated by
the Pitzer or Huckel method for the ionic strength in question (see above).
Equation (14) is used by the least-squares method in the same way as, for
example, Eq. (8) for the determination of glass electrode parameters E0 and k.

2. EXPERIMENTAL
Potentiometric acetic acid titrations were made in aqueous NaCl and
KC1 solutions at 25°C. For the measurements, the following solutions were
prepared in RO-filtered water (Millipore), conductivity less than 1.0 uS-
cm-1: 0.160, 0.240, 0.320, 0.400, 0.500, 0.700, and 1.350 M NaCl solutions
(pro analysi, Merck); 0.080, 0.160, 0.240, 0.320, 0.400, and 0.500M KCl
solutions (pro analysi, Merck); 0.01064 and 0.05000M acetic acid solutions
(pro analysi, Riedel de Haen and Fixanal, Riedel de Haen, respectively);
0.100M NaOH (Fixanal, Riedel de Haen); and 0.500M KOH solution (Fixanal,
Riedel de Haen). In the NaCl titrations, the 0.01064M acetic acid solution
was used to prepare the solutions titrated and the titrant was the 0.100M
NaOH solution. In the KCl titrations, the 0.05000M acetic acid solution was
Determination of Glass Electrode Parameters 419

used and the titrant was the 0.500M KOH solution. During the titrations, the
electromotive forces were measured by means of an N62 combination electode
and a CG841 pH meter, both manufactured by Schott-gerate. The accuracy
of reading was 0.1 mV. The titrant was added in increments of 0.050 cm3
by a Dosimat (Metrohm).
For NaCl solutions, two series of titrations were performed: the calibra-
tion series (cNaCl, see Table I) and the test series (tNaCl, see Table II). In
the calibration series, each titration was performed in the following way: A
volume of 10.00 cm3 of the 0.01064M acetic acid solution, 100.0 cm3 of a

Table I. Results of Titrations of Acetic Acid in NaCl Solutions at Different Ionic Strengths
Im with a NaOH Solution at 25°C— Series cNaCl.a

Im 0.1191 0.1789 0.2388 0.2988 0.3741 0.5251 1 .0222

c
V(cm3)b E (mV)

0.05 149.1 149.1 150.0 150.7 152.1 154.5

0.10 144.5 145.2 145.2 146.1 147.0 148.4 150.5
0.15 140.6 141.3 141.3 142.3 143.1 144.5 146.6
0.20 136.5 137.4 137.3 138.3 139.1 140.5 142.7
0.25 132.5 133.4 133.4 134.5 135.1 136.6 138.8
0.30 128.5 129.5 129.4 130.5 131.2 132.6 134.6
0.35 124.5 125.4 125.3 126.5 127.2 128.7 130.7
0.40 120.5 121.3 121.4 122.4 123.2 124.6 126.8
0.45 116.4 117.4 117.3 118.4 119.2 120.5 122.7
0.50 112.2 113.2 113.3 114.2 115.2 116.5 118.5
0.55 107.9 108.9 109.1 110.2 110.8 112.2 114.2
0.60 103.4 104.5 104.5 105.6 106.4 107.9 109.7
0.65 98.8 100.0 99.8 101.1 101.6 103.2 104.9
0.70 93.9 95.0 94.9 95.8 96.6 98.1 99.8
0.75 88.5 89.6 89.4 90.4 91.0 92.6 94.1
0.80 82.5 83.6 83.2 84.3 84.8 86.4 87.7
0.85 75.7 76.7 76.0 77.3 77.6 79.3 80.1
Symbol cNaCI2 cNaC13 cNaCI4 cNaCl5 cNaC16 cNaCI7 cNaCl8

(Vo/cm3)d 135 135 135 135 135 135 135

105km(H)e 2.88 3.03 3.13 3.19 3.24 3.26 3.02
105km(P)f 2.88 3.03 3.13 3.20 3.24 3.28 3.08
(104n1/mol)g 1.050 1.049 1.038 1.042 1.035 1.040 1.017
a
NaOH solution, c = 0.100 mol-dm -3 .
b
V is the volume of titrant added.
c
The measured emf.
d
The initial volume of the solution titrated.
e
Calculated by the Huckel method (i.e., by Eq. 18 with the value of ka = 1.758X 10 -5 ).
f
Calculated by the Pitzer method (i.e., by Eq. 29 with the value ka = 1.758X10-5).
g
The amount of acetic acid in the titration vessel, see text.
420 Partanen, Juusola, and Minkkinen

Table II. Results of Titrations of Acetic Acid in NaCl solutions at Different Ionic
Strengths Im with a NaOH Solution at 25°C— Series tNaCla

Im 0.1174 0.1802 0.2370 0.3034 0.3686 0.5291 1.0145

V(cm3)b E(mV)c

0.05 150.4 146.3 151.8 146.6 153.2 150.0 156.7

0.10 146.9 142.2 148.2 142.2 149.8 145.8 153.0
0.15 143.4 138.0 144.6 137.6 146.5 141.6 149.5
0.20 139.8 133.6 140.9 133.0 143.0 137.5 145.6
0.25 136.4 129.3 137.2 128.2 139.6 133.2 142.1
0.30 132.9 125.0 133.6 123.4 136.2 128.8 138.4
0.35 129.3 120.5 129.9 118.6 132.8 124.5 134.6
0.40 125.9 116.1 126.2 113.5 129.4 120.0 131.0
0.45 122.5 111.5 122.5 108.2 126.0 115.5 127.2
0.50 119.0 106.7 118.8 102.7 122.6 110.7 123.4
0.55 115.5 101.9 115.0 96.7 119.1 105.5 119.7
0.60 111.9 96.7 111.0 90.0 115.6 100.1 115.6
0.65 108.3 90.8 107.0 82.3 112.1 94.4 111.6
0.70 104.6 84.5 102.9 108.5 87.6 107.3
0.75 100.9 76.9 98.6 104.5 79.6 102.7
0.80 96.9 93.9 100.5 97.9
0.85 92.7 88.7 96.3 92.4
0.90 88.0 83.0 91.7 86.3
0.95 83.1 76.5 86.6
1.00 77.4 80.8
1.05 71.0 74.1
Symbol tNaC12 tNaC13 tNaC14 tNaCl5 tNaCI6 tNaCI7 tNaCl8

(Vo/cm3)d 137 134 136 133 137 134 136

105km(H)e 2.87 3.03 3.13 3.20 3.23 3.26 3.03
1 0 5K m( P ) f 2.87 3.03 3.13 3.20 3.24 3.28 3.09
(104n1/mol)g 1.255 0.934 1.160 0.836 1.245 0.916 1.121

a-gSee footnotes to Table I.

NaCl solution, and 25.00 cm3 of water were mixed (for further details, see
Ref. 10). The resulting solution was titrated by the NaOH solution. After
each calibration titration, a test titration was performed in the same way at
approximately the same ionic strength. However, the following volumes of
the acetic acid solution were used to prepare the solutions titrated: 8.00,
9.00, 11.00, and 12.00 cm3 (see Table II). For KCl solutions, only a series
corresponding to the calibration series for NaCl was measured (Table III).
Standard buffer solutions of pH = 4.005 and 6.865 (Ref. 5) were used to
check the stability of measuring system between the titrations. The pH meter
usually reproduced the same reading within 0.2 mV in these buffer solution tests.
Determination of Glass Electrode Parameters 421

Table III. Results of Titrations of Acetic Acid in KC1 Solutions at Different Ionic
Strengths Im with a KOH Solution at 25°C— Series KCla

Im 0.0595 0.1193 0.1792 0.2393 0.2997 0.3755

V(cm)b E(mV)c
0 174.0 174.8 175.0 175.4 175.3 175.7
0.05 165.7 167.0 167.2 167.7 167.7 168.1
0.10 157.7 159.4 159.6 160.3 160.2 160.9
0.15 150.4 152.4 152.5 153.4 153.1 153.8
0.20 143.7 145.8 146.1 147.1 146.7 147.7
0.25 137.6 139.9 140.2 141.1 140.7 141.9
0.30 132.0 134.3 134.8 135.7 135.3 136.4
0.35 126.8 129.1 129.5 130.5 130.0 131.1
0.40 121.6 124.1 124.6 125.3 124.9 126.1
0.45 116.6 119.3 119.7 120.6 119.9 121.2
0.50 111.6 114.5 114.8 115.6 114.9 116.4
0.55 106.6 109.5 109.9 110.8 109.9 111.6
0.60 101.5 104.4 104.9 105.7 104.9 106.6
0.65 96,2 99.4 99.7 100.5 99.6 101.5
0.70 90.6 93.9 94.1 95.0 93.6 95.9
0.75 84.3 87.8 88.0 88.9 87.4 90.2
0.80 77.2 81.2 81.3 82.1 80.3 83.3
0.85 68.7 73.2 73.1 73.9 71.7 75.5
Symbol KCl1 KCl2 KCl3 KCl4 KCl5 KCl6
(Vo/cm3)d 135 135 135 135 135 135
10k m (H) e 2.61 2.86 3.00 3.09 3.14 3.17
105km(P)f 2.61 2.86 2.99 3.08 3.12 3.15
(l0 4n1 /mol) g 5.03 5.10 5.08 5.07 5.01 5.11

aKOH solution, c = 0.500 mol-dm3.

bSee footnotes to Table I.

3. RESULTS
In the Huckel method, the following equation is used for the activit;
coefficient of a univalent ion i on the molality scale:

where Im is the ionic strength on the molality scale and a is the Debye-Huckel
parameter at 25°C equal to 1.17444 (mol-kg - 1 ) - 1 / 2 [see Archer and Wang(7)].
Bi and bi,Mcl are the parameters that are dependent on ion i and bi,Mcl is, in
addition, dependent on the salt MCl present in the system. In the previous
studies,(3,4) the following parameters have been suggested for this equation:
BH = 1.25(mol-kg-1)-1/2,.BA = 1.6 (mol-kg-1)-1/2,bH,Nacl =0.238,bH,KCl = 0.178,
b A,Nacl = 0-189, and bA,KCl = 0.308, where A refers to acetate ions (CH3COO-).
422 Partanen, Juusola, and Minkkinen

The thermodynamic dissociation constant Ka for acetic acid (CH3COOH

= HA) is given by

where

For acetic acid at 25°C K, Ka is 1.758X10 -5 . This value was determined by

Harned and Ehlers(11) on the basis of measurements on galvanic cells without
a liquid junction and by MacInnes and Shedlovsky(1,2) on the basis of conduc-
tivity measurements (see also Ref. 3). In the Huckel method, it is assumed
that GHA = 1 The following equation can be derived for the stoichiometric
dissociation constant, Km (Eq. 17), of acetic acid for NaCl and KCl solutions
by using Eqs. (15) and (16)

where MCl refers to the NaCl or KCl solutions. This equation is used in
this study for the calculation of Km values for acetic acid titrations by the
Huckel method.
In the Pitzer method, the following equations can be used for the activity
coefficients of the species existing in the aqueous mixtures of acetic acid,
sodium acetate, and chloride (see, e.g., Refs. 4, 13, 14, 15, and 16)

where

In Eqs. (19-23) Na refers to Na+ ions and the following symbols have
been used
Determination of Glass Electrode Parameters 423

where ap = a/3 = 0.3915 (mol-kg -1 ) - 1/2, M refers to a cation, and X to an

anion. For titrations of acetic acid in the NaCl solutions, whose ionic strength
is the nearly the same as the salt molality, the following equation can be
derived for the stoichiometric dissociation constant Km from Eqs. (16, 19,
21, 22, and 23).

where

These Pitzer equations apply also to aqueous mixtures of acetic acid, potas-
sium acetate, and chloride. In this case, Na+ must simply be replaced in those
by K+. In the present Pitzer calculations, the parameter values given in Table
IV were used as suggested by Partanen.(4)
The parameters E0 and k in Eq. (14) were determined by linear regression
analysis for all titration sets shown in Tables I (series cNaCl), II (series
Table IV. Interaction Parameters for the Pitzer Equations (Eqs. 19-22) at 25°C

(B0)a (B 1 ) a 0 Lc

H+,cl- 0.1775 0.2945

K+,cl- 0.04835 0.2122
K+,AcO- 0.1587 0.3251
Na+,Cl- 0.0765 0.2664
Na+,AcO- 0.1426 0.3237
H+,K+ 0.005*
H+,Na+ 0.036*
cl-.Aco- 0c
H+,AcOH 0.08
K+,AcOH 0.044
Na+,AcOH 0.087
Cl - .AcOH 0
AcO - ,AcOH -0.09
AcOH,AcOH -0.06

aDetermined by Pitzer and Mayorga (Ref. 17).

bDetermined by Pitzer and Kim (Ref. 18).
c Determined in Ref 4.
424 Partanen, Juusola, and Minkkinen

Table V. Results of the Linear Regression Analysis Obtained by Eq. (14) from the
Titration Data Presented in Table I (Series cNaCl)

Data set (Im)a E 0 (mV) T(Eo)b k T(k)c nl(mmol)d T(n1)e

cNaCI2 0.1191 375.82 0.24 0.9773 0.0009 0.1050 0.0002

cNaCl3 0.1789 375.69 0.16 0.9770 0.0006 0.1049 0.0002
cNaCI4 0.2388 374.24 0.20 0.9723 0.0008 0.1038 0.0002
cNaC15 0.2988 376.15 0.28 0.9777 0.0010 0.1042 0.0002
cNaC16 0.3741 375.97 0.21 0.9742 0.0008 0.1035 0.0002
cNaC17 0.5251 378.10 0.19 0.9782 0.0007 0.1040 0.0002
cNaCl8 1.0222 375.10 0.21 0.9500 0.0008 0.1017 0.0002

a mol-kg -1 .
bThe standard deviation for Eo„
cThe standard deviation for k.
dThe mean of the n1, values calculated from the titration points by means of Eqs. (33) and (34)
with the Eo„ and k values obtained.
eThe standard deviation for the mean value presented in the preceding column.

Table VI. Results of the Linear Regression Analysis Obtained by Eq. (14) from the
Titration Data Presented in Table II (Series tNaCl).

Data set (Im)a Eo,(mV) <r(E0)b k v(k)c n1,(mmol)d ff(n1)e

tNaCI2 0.1174 373.62 0.15 0.9709 0.0006 0.1255 0.0002

tNaC13 0.1802 373.84 0.18 0.9734 0.0007 0.0934 0.0001
tNaCl4 0.2370 377.88 0.15 0.9831 0.0006 0.1160 0.0002
tNaCl5 0.3034 377.90 0.13 0.9849 0.0005 0.0836 0.0001
tNaCI6 0.3686 374.23 0.11 0.9678 0.0004 0.1245 0.0002
tNaCI7 0.5291 374.84 0.25 0.9651 0.0009 0.0916 0.0002
tNaCl8 1.0145 376.38 0.23 0.9519 0.0009 0.1121 0.0003

a-eSee footnotes to Table V.

Table VII. Results of the Linear Regression Analysis Obtained by Eq. (14) from the
Titration Data Presented in Table III (Series KCl)

Data set (Im)a E0(mV) ff(E0)b k o-(k)c n1(mmol)d <r(n1,)e

KCll 0.0595 380.22 0.17 0.9893 0.0006 0.5029 0.0011

KCl2 0.1193 378.84 0.18 0.9847 0.0007 0.5099 0.0013
KCl3 0.1792 378.54 0.18 0.9859 0.0007 0.5080 0.0014
KCl4 0.2393 378.37 0.19 0.9841 0.0007 0.5069 0.0015
KC15 0.2997 379.53 0.21 0.9904 0.0008 0.5009 0.0012
KCl6 0.3755 378.47 0.23 0.9854 0.0009 0.5109 0.0018

a-eSee footnotes to Table V.

Determination of Glass Electrode Parameters 425

Fig. 1. The difference between the observed and predicted emf values eE in Eq. (32), as a
function of the titrant volume in the titrations of acetic acid solutions with the base (NaOH or
KOH) solutions. Graphs A and B show the results of the titrations obtained for NaCl solutions
(series cNaCl, A, and tNaCl, B), and graph C shows those obtained for KCl solutions (series
KCl). The predicted emf was calculated by means of Eqs. (14, 18, and 31) with the parameter
values given in the text and in Tables V, VI, and VII. Symbols of the different data sets are
shown in the legends of the graphs (see Tables I, II, and HI).

tNaCl), and III (series KCl). For each point in these data sets, the molality
of hydrogen ions for Eq. (14) was calculated by

where mt is the total molality of acetic acid and mb (= cbVlw1, where cb is

the concentration of the base in the titrant and W1 the mass of water) the
analytical molality of sodium or potassium acetate in the solution of the
titration point in question. The determination of glass electrode parameters
for Eq. (14) from each titration data sets requires that the amount of acetic
acid nt in the titration vessel to be known very accurately. In the present
study, the following method was used for this quantitative analysis: n, was
426 Partanen, Juusola, and Minkkinen

Fig. 1. Continued

slightly varied around the analytical value and, for each value, the least-squares
fit by means of Eq. (14) was carried out using the data of the set considered.
The value of n1, was then chosen that gives the smallest value for the standard
deviation of residuals s and this value is regarded below as the real amount of
acetic acid in this data set. The standard deviation is always a very sensitive
function of n, as the following results obtained, for instance, from data set cNaCl3
(see Table I) illustrate: n1, = 0.103 mmol, s = 0.203 mV; 0.104, 0.104; 0.105,
0.055; 0.106, 0.117; 0.107, 0.199; and 0.108, 0.279.
The parameters nt, k, and E0 obtained in this way for the different sets
in Tables I-III are shown in Tables V-VII. The residuals defined by

for the points of each titration were also calculated; they are given as a
function of the volume V of the titrant added in graphs A (series cNaCl), B
(tNaCl), and C (KCl) of Fig. 1. The estimate of the amount of acetic acid
was also calculated from the points of all titrations by equations
Determination of Glass Electrode Parameters 427

In Eq. (33), the parameter values determined by the linear regression analysis
(those shown in Tables V-VII) were used. The deviation of these estimates
from the real amount of acetic acid, i.e., the error defined by

is shown graphically in graphs A (cNaCl), B (tNaCl), and C (KCl) of Fig.

2 as a function of the base volume (V) added. The mean of the nt, estimates
for each data set (which is equal to that obtained by the least-squares determi-
nation; see above) and the standard deviation for this value are also given
in Tables V-VII.
The calibration parameters k and E0 obtained from the calibration series
cNaCl (see Tables I and V) were used to predict the results of the test series
tNaCl (see Tables II and VI). According to Tables V and VI, the least-squares
428 Partanen, Juusola, and Minkkinen

Fig. 2. The difference between the real amount of acetic acid and the amount estimates
calculated from the titration points, e(nt,) in Eq. (35), as a function of the titrant volume in the
titrations of acetic acid solutions with the base (NaOH or KOH) solutions. Graphs A and B
show the results of the titrations obtained for NaCl solutions (series cNaCl, A, and tNaCl, B),
and graph C shows those obtained for KCl solutions (series KCl). The amount estimates of
acetic acid for the different points was calculated by means of Eqs. (18, 33, and 34) with the
parameter values given in the text and in Tables V, VI, and VII. Symbols of the different data
sets are shown in the legends of the graphs (see Tables I, II, and III).

estimates of E0 for the corresponding sets in these two tables do not agree
well with each other; therefore, the E0 value obtained for a particular calibra-
tion data set cannot be used when the results of the corresponding test data
set are analyzed. The k parameters for the calibration and test data sets agree
better with each other in these tables. The k parameter obtained for a particular
calibration data set was, therefore, used to predict the results of the correspond-
ing test data set. The best value of E0 for the test data set, containing N titration
points, was obtained from the experimental emf values, E, by simultaneously
solving the following equations:
Determination of Glass Electrode Parameters 429

The E0 values obtained in this way are shown, together with the k values
used, in Table VIII. The E0 value for each data set was then used to calculate
the amount estimates for acetic acid from all titration points of this set by
Eqs. (33) and (34). The deviation of these estimates from the real amount
430 Partanen, Juusola, and Minkkinen

Fig. 2. Continued

of acetic acid, the error e(nt), defined by Eq. (35), is presented in Fig. 3 for
the different data sets as a function of base volume added. The mean of the
acetic acid amount estimates was also calculated for each set and this value,
together with its standard deviation, are given in Table VIII.

4. DISCUSSION
According to Fig. 1, the potentiometric data presented in Tables I-III
can be predicted almost within experimental error by the Eq, (14), where the
Km values predicted by the Pitzer or Huckel method are used in the calculation
of the molality of protons, mH. All errors in the graphs of this figure are
about the same order as the accuracy of the meter and form, for most cases,
a random pattern.
According to Fig. 2, the estimates of the amount of acetic acid calculated
from each point of each titration set presented in Tables I-III always agree
well with the mean of these estimates of the set. In all cases shown in this
figure, the relative error of this amount is appreciably less than 1%. The
Determination of Glass Electrode Parameters 431

Table VIII. Results of the Analysis of the Titration Data of Series tNaCl (Table II) by
Eq. (14) where A(tNaCl) = k(cNaCl)a

Data set (Im)b E 0 (mV) kc n t (mmol) d npred(mmol)e a(n pred ) f

tNaC12 0.1174 375.06 0.9773 0.1255 0.1261 0.0003

tNaC13 0.1802 374.67 0.9770 0.0934 0.0937 0.0001
tNaC14 0.2370 375.45 0.9723 0.1160 0.1151 0.0002
tNaC15 0.3034 376.26 0.9777 0.0836 0.0831 0.0001
tNaCI6 0.3686 375.66 0.9742 0.1245 0.1251 0.0002
tNaC17 0.5291 377.82 0.9782 0.0916 0.0925 0.0003
tNaC18 1.0145 375.93 0.9500 0.1121 0.1119 0.0003

"For each data set the same value of k was used as that obtained from the corresponding
calibration data set in Series cNaCl (see Tables I and V) and the value of E0 was calculated
by Eqs. (36-41) from data of this set.
b In mol-kg -1 .
cTaken from Table V.
dTaken from Table II.
eThe mean of the n1 estimates obtained from the titration points by means of Eqs. (33) and
(34) with the Eo and k values shown in this table.
fThe standard deviation for the mean value presented in the preceding column.

error plots of Fig. 2 show, in addition, that the precision for the determination
of n1, from the titration points depends on the volume V of the base solution
added, and the most precise estimates for this amount are obtained from the
last points.
Figure 3 shows the results where the slope parameter k is determined
for an acetic acid titration by a separate calibration titration carried out at
nearly the same ionic strength as this titration (the test titration). The amount
estimates for acetic acid were calculated for this figure from the different
points of the test titration by using the value of the other calibration parameter
E0 that gives the best agreement between the observed and predicted emf
(see Eqs. 36-41). The results of this figure are very encouraging. Despite
the constant systematic errors observed for all data sets, the errors shown in
this figure are very small. The relative errors for almost all titration points
are less than 1%. In addition, the constant systematic errors for the different
data sets seem to lay randomly around zero in this figure.
We believe that the most important conclusion of this preliminary study
is the following: Titrations of acetic acid solutions at different ionic strengths,
adjusted by NaCl or KCl, can be analyzed almost within experimental erro r
by means of stoichiometric dissociation constants calculated for this acid by
the Pitzer or Huckel equations for ionic activity coefficients. The parameters
for these equations were not determined from glass electrode data but from
data measured on Harned cells. According to the preliminary results presented
in this study, it seems to be true that this new method of data analysis
432 Partanen, Juusola, and Minkkinen

Fig. 3. The difference between the real amount of acetic acid and the amount estimates
calculated from the titration points, e(n1,) in Eq. (35), as a function of the titrant volume in the
titrations of acetic acid solutions of series tNaCl (Table II) by the base (NaOH) solution. The
amount estimates were calculated from the different points of each data set by means of Eqs.
(18, 33, and 34) with the k parameter taken from Table V (determined from the corresponding
calibration data set), with the E0„ parameter calculated by Eqs. (36-41) (see Table VIII) and
with the values of the other parameters given in the text. Symbols of the different data sets
are shown in the legend of the figure (see Table II).

of potentiometric titrations allows the direct determination of composition

variables (molalities or concentrations) of species instead of activities.

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