J Solution Chem (2007) 36: 891–900

DOI 10.1007/s10953-007-9156-z
O R I G I N A L PA P E R

Electrical Conductance Studies in Aqueous Solutions

with Glutamic Ions

Alexander Apelblat · Emanuel Manzurola ·

Zoya Orekhova

Received: 28 November 2006 / Accepted: 22 January 2007 /

Published online: 8 May 2007
© Springer Science+Business Media, LLC 2007

Abstract Conductivity measurements in dilute aqueous solutions of L-glutamic acid, DL-

glutamic acid, sodium-L-glutamate and magnesium-L-glutamate, were performed in the
288.15 to 323.15 K temperature range. The limiting molar conductivities of glutamic an-
ions, λo (HGlu− , T ) and the dissociation constants of glutamic acid, K2 (T ) were derived
by the use of the Debye–Hückel equation for the activity coefficients and the Onsager, and
Quint and Viallard conductivity equations.

Keywords L-glutamic acid · DL-glutamic acid · Sodium-L-glutamate ·

Magnesium-L-glutamate · Limiting molar conductivities · Dissociation constants

1 Introduction

Glutamic acid is critical material for proper cell function but it is not considered as an es-
sential nutrient because the human body can manufacture it from simpler compounds. This
dicarboxylic amino acid is present in a wide variety of foods and is an important molecule in
the metabolism of sugars and fats. Glutamic acid is one of building blocks in protein synthe-
sis [1]. Contrary to the biological specificities of amino acids, biochemical and nutritional
aspects, which were widely investigated in the literature, their physicochemical, especially
dynamic and thermodynamic properties, are noticeably less documented.
Dicarboxylic amino acids are amphoteric electrolytes and they may exist as a mixture
of variously charged and uncharged forms. Depending on concentration, considering that
the basic amino groups can be protonated and the carboxylic acidic groups deprotonated,
the aqueous solutions consist of different proportions of the hydrogen and amino acid ions,
the undissociated molecules and the dipolar ions (zwitterions) [1, 2]. The dissociation of

A. Apelblat () · E. Manzurola · Z. Orekhova

Department of Chemical Engineering, Ben Gurion University of the Negev, Beer Sheva, 84105,
Israel
e-mail: apelblat@bgu.ac.il
892 J Solution Chem (2007) 36: 891–900

glutamic acid can be represented by:

H3 A+  H+ + H2 A, K1 (T )
+ −
H2 A  H + HA , K2 (T ) (1)
−
HA  H+ + A2− , K3 (T )

where H3 A+ represents HOOCCH(NH+ 3 )CH2 CH2 COOH, H2 A denotes the zwitterion

H2 A+− or undissociated glutamic acid and A2− is − OOCCH(NH2 )CH2 CH2 COO− . The
equilibrium constants of these dissociation reactions are known in the literature but lie within
rather wide limits (4.8 × 10−3 < K1 < 8.0 × 10−3 ; 3.1 × 10−5 < K2 < 8.5 × 10−5 and 11 ×
10−10 < K3 < 3.4 × 10−10 , for example at 298.15 K [3–8], in the Martell and Smith com-
pilation of dissociation constants K1 = (5.55 ± 0.88) × 10−3 ; K2 = (3.80 ± 0.78) × 10−5
and K3 = (1.12 ± 0.03) × 10−10 [9]). Electrical conductance measurements of glutamic
acid or its salts were performed at 273.15 K by Hoskins et al. [10]; at 298.15 K by Mehl and
Schmidt [11], and Rajeswari [12]. Unfortunately, in the last investigation results are reported
only in graphical form.
In this work results of systematic electrical conductivity measurements are presented
in dilute aqueous solutions of L-glutamic acid, DL-glutamic acid, sodium-L-glutamate and
magnesium-L-glutamate in the 288.15 to 323.15 K temperature range. The limiting molar
conductivities of glutamic anions, λo (HGlu− , T ), the second dissociation constants of glu-
tamic acid, K2 (T ) and the standard thermodynamic functions of the dissociation process
were determined by the use of the Debye–Hückel equation for the activity coefficients and
the Onsager, and Quint and Viallard conductivity equations.

2 Experimental

L-Glutamic acid and DL-glutamic acid (mass fraction ≥ 0.99); sodium-L-glutamate mono-
hydrate and magnesium-L-glutamate tetrahydrate (mass fraction ≥ 0.99) were from Fluka
and were used in experiments without further purification.
A detailed description of the electrical conductivity measurements is described else-
where [13–15].

3 Results and Discussion

3.1 Limiting Equivalent Conductivities of the Glutamate Anion

The equivalent conductivities of sodium-L-glutamate, L-NaGlu and magnesium-L-

glutamate, L-Mg(Glu)2 , are presented in Table 1 as a function of concentration c and tem-
perature T . In agreement with our observation for sodium-L-glutamate, Hoskins et al. [10] at
T = 273.15 K and Rajeswari [12] at T = 298.15 K found that L-NaGlu behaves as a strong
electrolyte. This is also true in the case of magnesium-L-glutamate (Fig. 1). The limiting
behavior of strong electrolytes is described by the Onsager conductivity equation [16]
 
2.801 × 106 qo |z+ ||z− | 41.248 √
 = o − √ + I,
(DT )3/2 (1 + q) η(DT )1/2
(2)
|z+ ||z− |(λo+ + λo− )
q=
(|z+ | + |z− |)(|z− |λo+ + |z+ |λo− )
J Solution Chem (2007) 36: 891–900 893

Table 1 Experimental
equivalent conductivities of c × 103    
sodium-L-glutamate and
magnesium-L-glutamatea L-NaGlu
T 288.15 293.15 298.15 303.15
0.25 63.16 71.77 80.27 89.66
0.51 62.94 70.78 78.72 87.33
0.76 62.42 70.29 79.02 87.39
1.01 62.08 70.39 78.41 86.98
2.53 60.37 68.03 76.23 84.75
5.07 59.18 66.94 74.27 82.69

T 308.15 313.15 318.15 323.15

0.25 98.58 108.05 117.61 127.54
0.51 96.59 105.73 115.16 125.06
0.76 96.47 105.60 115.50 125.16
1.01 96.05 105.25 115.15 125.06
2.53 93.86 102.77 111.85 121.81
5.07 91.21 100.26 109.52 118.84

L-Mg(Glu)2
T 288.15 293.15 298.15 303.15
0.10 64.20 71.95 80.69 89.27
0.25 62.90 70.60 79.33 88.23
0.50 60.18 68.33 76.68 85.36
0.63 59.52 66.81 75.35 83.79
1.00 58.39 65.93 74.48 82.63
2.50 55.27 62.17 69.85 77.78
5.00 51.98 58.53 65.87 73.26

T 308.15 313.15 318.15 323.15

0.10 98.02 108.34 117.62 128.05
0.25 97.56 107.27 117.38 127.64
0.50 94.50 104.34 113.42 123.32
0.63 92.82 102.36 112.16 121.70
1.00 92.05 100.99 110.82 120.39
2.50 86.13 94.69 103.79 112.98
a Units: T , K; c at 298.15 K,
5.00 81.32 89.34 97.82 105.95
mol·dm−3 ; , S·cm2 ·mol−1

where zi denotes the charges of the ions and I is the ionic strength of the solutions. Sodium-
L-glutamate is a 1 : 1 type electrolyte and magnesium-L-glutamate is a 2 : 1 type electrolyte.
The properties, viscosity, η, dielectric constant of pure water, D, and the limiting equiva-
lent conductivities λo (H+ ), λo (Na+ ) and λo (1/2Mg2+ ) [6, 16] used in the calculations are
presented in Table 2.
The optimization procedure which satisfies the Onsager equation (Eq. 2) together with
the Kohlrausch law of the independent migration of ions at infinite dilution

o = λo (1/z+ Mez+ ) + λo (HGlu− ) (3)

894 J Solution Chem (2007) 36: 891–900

Fig. 1 Equivalent conductivity

 at 298.15 K of
sodium-L-glutamate (•) and
magnesium-L-glutamate (◦)

Table 2 Viscosities, dielectric constants of pure water and the limiting equivalent conductivities of ionsa

T η·103 D λo (H+ ) λo (Na+ ) λo (1/2Mg2+ )

288.15 1.1382 82.039 300.74 39.72 41.52

293.15 1.0020 80.176 325.52 44.81 47.16
298.15 0.8903 78.358 349.85 50.15 53.05
303.15 0.7975 76.581 373.66 55.72 59.21
308.15 0.7195 74.846 396.90 61.35 65.72
313.15 0.7194 73.151 419.15 67.34 72.36
318.15 0.6783 71.511 441.40 73.73 79.28
323.15 0.6531 69.910 462.20 80.30 86.38
a Units: T , K; η, Pa·s; λo , S·cm2 ·mol−1

leads to the limiting conductivities of glutamic anions λo (HGlu− ) as a function of tem-

perature T (Table 3). As can be observed, both salts give similar values of λo (HGlu− )
and the Hoskins et al. [10] result at 273.15 K is consistent with those reported here for
higher temperatures (Fig. 2). In contrast, the Rajeswari [12] value at 298.15 K λo (HGlu− ) =
12.1 S·cm2 ·mol−1 is considerably lower than that determined in this work, λo (HGlu− ) =
(28.16 ± 0.89) S·cm2 ·mol−1 , and there is no satisfactory explanation for a such large dif-
ference. The observed Walden product is almost constant, λo (HGlu− , T )η(T ) = (2.624 ±
0.040) × 10−2 S·cm2 ·mol−1 ·Pa·s.
From the Eyring theory of the transition state, when it is applied to the movement of
individual ions [17], it is possible to obtain the change of λo (HGlu− , T ) with temperature:
  =  
∂ ln λo (HGlu− , T ) Hλ 2 ∂ ln ρw (T )
=− − (4)
∂T P RT 2 3 ∂T P

=
where Hλ is the partial molar enthalpy of activation associated with the process and ρw (T )
=
denotes the density of pure water [6]. If it is assumed that the partial molar enthalpy, Hλ ,
J Solution Chem (2007) 36: 891–900 895

Table 3 Limiting equivalent conductivities of the glutamate ion λo (HGlu− ) as derived from conductivities
of sodium-L-glutamate and magnesium-L-glutamate and the Walden productsa

T λo (HGlu− )Na λo (HGlu− )Mg λo (HGlu− )ave. ηλo (HGlu− )ave.

288.15 24.42 23.02 23.72 ± 0.99 0.02699

293.15 27.52 25.50 26.51 ± 1.43 0.02656
298.15 30.57 28.71 29.64 ± 1.32 0.02638
303.15 33.99 31.79 32.89 ± 1.56 0.02625
308.15 37.53 34.99 36.26 ± 1.80 0.02607
313.15 41.25 38.66 39.96 ± 1.83 0.02609
318.15 44.78 42.12 43.45 ± 1.88 0.02590
323.15 48.40 45.63 47.02 ± 1.96 0.02572

a Units: T , K; λo , S·cm2 ·mol−1 ; ηλo , S·cm2 ·mol−1 ·Pa·s

Fig. 2 Limiting equivalent

conductivity λo (HGlu− ) as a
function of temperature T .
(◦)—from Ref. [11] and
(•)—this work

Fig. 3 Values of
ln[λo (HGlu− , T )ρw (T )] as a
2/3
function of 1/T . The average
values for sodium-L-glutamate
and magnesium-L-glutamate
(Table 3)
896 J Solution Chem (2007) 36: 891–900

is independent of T , then the integral form of Eq. 4 is

=
Hλ
ln[λo (HGlu− , T )ρw2/3 (T )] = − + const. (5)
RT
This is actually observed for the glutamate anion (Fig. 3) and we have
1798.9
ln[λo (HGlu− , T )ρw2/3 (T )] = 9.416 − (6)
(T /K)
R 2 = 0.9981
=
with Hλ = 14.96 kJ·mol−1 .

3.2 Conductivities and Dissociation Constants of Glutamic Acid

In Table 4 are presented the molar conductivities, , of L-glutamic acid and DL-glutamic
acid as a function of concentration c and temperature T . As can be observed in Fig. 4, the 
values of the stereoisomers with and without optical activity are practically undistinguish-
able. The conductivities determined by us at T = 298.15 K are in a very good agreement
with those of Mehl and Schmidt in 1935 [11].
In the investigated concentration interval 10−4 < c < 5 × 10−3 , the second dissociation
reaction in Eq. 1 is the only reaction of importance and in the analysis of electrical conduc-
tivities, glutamic acid can be considered as a monobasic acid
[H+ ][HA− ] cα 2
K2 (T ) = F= F
[H2 A] 1−α
(7)
fH+ fHA−
F=
fH 2 A
where α is the degree of dissociation, fH+ and fHA− are the activity coefficients of the ions
and the activity coefficient of the undissociated acid is assumed to be unity, fH2 A = 1. The
activity coefficients were approximated in dilute solutions by the Debye–Hückel equation
√
A I
log10 fi = − √
1 + ai B I (8)
i = H+ , HA−
where I = cα is the ionic strength, ai are the size parameters, A and B are constants de-
pending on temperature and dielectric constants of pure water [6]. The size parameters,
a(H+ ) = 9.0 Å and a(HA− ) = 6.0 Å, were adopted using the Kielland [18] and Harris [19]
recommendations. These parameters are assumed to be independent of temperature.
The molar conductivities, , are the sum of the ionic contributions

 = α[λ(H+ ) + λ(HA− )] (9)

where the individual contributions, λi , i = H+ , HA− , are represented by

√
λi = λ0i − Si I + Ei I ln I + J1i I − J2i I 3/2
(10)
I = cα.

Detailed expressions for the coefficients, Si , Ei , J 1i and J 2i are available from the Quint–
Viallard theory [20, 21] (see also [22, 23]).
J Solution Chem (2007) 36: 891–900 897

Table 4 Experimental and calculated molar conductivities of L-glutamic acid and DL-glutamic acida

c × 103 exp calc exp calc exp calc exp calc

L-Glu
T /K 288.15 288.15 293.15 293.15 298.15 298.15 303.15 303.15
0.101 148.73 149.13 161.61 162.79 175.12 175.85 187.03 188.92
0.254 107.22 105.34 117.57 115.27 126.16 124.57 136.38 133.88
0.506 80.27 79.10 88.02 86.47 95.05 93.46 102.60 100.64
0.632 71.92 71.86 79.24 78.56 85.57 84.92 92.28 91.42
1.010 57.91 58.41 63.53 63.88 68.78 69.05 74.43 74.24
2.540 35.70 38.31 39.22 41.99 42.63 45.39 46.30 48.81
5.060 23.92 27.72 26.34 30.32 28.82 30.32 31.25 35.32
σ () 2.10 2.35 2.22 2.50
T /K 308.15 308.15 313.15 313.15 318.15 318.15 323.15 323.15
0.101 199.24 201.58 209.10 212.51 219.60 224.04 230.95 235.25
0.254 146.00 143.12 153.41 150.75 161.44 158.51 169.39 166.42
0.506 109.58 107.52 116.02 113.20 122.35 118.89 128.28 125.04
0.632 98.67 97.66 104.62 102.88 110.36 108.02 115.61 113.56
1.010 79.70 79.26 84.59 83.42 89.33 87.90 93.93 92.28
2.540 49.57 52.21 52.74 54.94 55.85 57.72 58.73 60.60
5.060 33.59 37.75 35.91 39.72 38.04 41.69 40.17 43.85
σ () 2.69 2.90 3.28 3.21
DL-Glu
T /K 288.15 288.15 293.15 293.15 298.15 298.15 303.15 303.15
0.223 109.43 110.87 119.31 121.33 129.12 131.05 138.74 140.81
0.445 82.44 83.49 90.46 91.27 97.98 98.68 105.59 106.14
0.557 76.01 75.90 82.88 82.98 89.98 89.71 96.92 96.49
0.891 60.58 61.81 66.44 67.60 72.52 73.03 77.97 78.54
2.230 37.87 40.67 41.75 44.58 45.48 48.17 49.14 51.78
4.450 25.67 29.43 28.41 32.20 31.06 34.83 33.58 37.48
σ () 2.31 2.38 2.28 2.33
T /K 308.15 308.15 313.15 313.15 318.15 318.15 323.15 323.15
0.223 147.68 150.55 156.43 158.63 164.89 166.79 173.39 175.07
0.445 112.69 113.33 119.10 119.46 125.82 125.46 132.02 131.78
0.557 103.46 103.10 109.65 108.64 115.99 114.06 121.73 119.88
0.891 83.38 83.94 88.42 88.45 93.47 92.87 97.96 97.55
2.230 52.69 55.40 56.11 58.31 59.40 61.26 62.42 64.29
4.450 36.20 40.03 38.59 42.16 40.86 44.25 43.07 46.48
σ () 2.50 2.17 2.14 2.08
Glu [11]
T /K 298.15 298.15b
0.10 180.00 176.46
0.20 138.50 136.66
0.50 93.80 93.94
1.00 68.00 69.36
2.00 47.40 50.61
5.00 30.40 32.97
10.00 18.80 23.70
20.00 12.10 16.97
σ () 3.43

a Units: T , K; c at 298.15 K, mol·dm−3 ; , S·cm2 ·mol−1

b Calculated with the parameters of our model
898 J Solution Chem (2007) 36: 891–900

Since viscosities η(T ) and dielectric constants of pure water, D(T ), the size parameters
ai and the limiting conductivities λo (H+ , T ), λo (HA− , T ) = λo (HGlu− , T ) are known, in an
optimization procedure it is possible to evaluate calc = f (c; T ) and the second dissociation
constant K2 (T ) [14, 15, 22–25]. The comparison between experimental exp and calculated
calc values of conductivities shows very reasonable agreement (Table 4). The calculations
were extended also to the Mehl and Schmidt [12] conductivities at 298.15 K (Table 4).
The “goodness” of the fit of the determined conductivities is expressed by the mean value
deviation 
N
i=1 (i,exp. − i,calc. )
2
σ () = (11)
N −1

Fig. 4 Molar conductivity  of

L-glutamic acid and DL-glutamic
acid at 298.15 K. L-Glu (
◦)—Ref. [12] and ()—this
work; DL-Glu (•)—this work.
Continuous curve was calculated
using the Quint–Viallard
conductivity equation

Table 5 Limiting molar conductivities of L-glutamic acid, coefficients of the Quint–Viallard conductivity
equations and dissociation constantsa

T 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

o 324.48 352.01 379.43 406.58 433.09 459.15 484.86 509.43
S 120.38 133.85 147.79 162.19 176.93 192.10 207.63 223.47
E 58.65 64.12 69.73 75.46 81.24 87.12 93.08 98.96
J1 792.7 871.7 952.9 1035.9 1120.0 1205.7 1292.9 1380.1
J2 2015.7 2221.3 2433.3 2651.4 2873.3 3100.8 3333.1 3566.9
S1 91.45 100.97 110.69 120.61 130.71 140.91 151.39 161.92
E1 57.27 62.62 68.05 73.57 79.16 84.75 90.50 96.15
J11 697.1 763.5 830.8 898.9 967.6 1036.3 1106.6 1176.2
J12 1775.2 1948.1 2124.0 2302.9 2484.5 2666.7 2854.1 3040.4
S2 28.93 32.88 37.10 41.58 46.22 51.19 56.25 61.56
E2 1.38 1.50 1.67 1.89 2.07 2.37 2.58 2.81
J21 95.59 108.22 122.09 137.04 152.33 169.43 186.21 203.87
J22 240.5 273.20 309.30 348.4 388.8 434.10 478.90 526.4
K2 × 105 3.92 3.99 4.01 4.04 4.06 4.00 3.94 3.93

a Units: T , K; o , S·c1/2 , Ec, J c, J c3/2 , S·cm2 ·mol−1 , K , mol·dm−3 . 1—H+ , 2—HA−

1 2 2
J Solution Chem (2007) 36: 891–900 899

where N is the number of conductivity-concentration pairs.

The coefficients of the Quint–Viallard conductivity equations (Eq. 10) and derived the
dissociation constants K2 (T ) are reported in Table 5. The dissociation constants in the in-
vestigated temperature range are very weakly dependent on temperature (Table 5) and can
be assumed to be constant, K2 (T ) = (3.99 ± 0.05) × 10−5 mol·dm−3 . This value agrees very
well with the Partanen et al. [8] result, K2 (298.15 K) = 4.57 × 10−5 mol·dm−3 , derived from
the electromotive (Emf) measurements. Partanen et al. compiled many values of K2 from
the literature, most of them support the 4–5 × 10−5 mol·dm−3 value, but in the old papers
a K2 of about 8 × 10−5 mol·dm−3 is more common. The observed large differences in the
dissociation constants are usually attributed to the fact that measurements are performed at
different ionic strengths and if introduced, the activity coefficients have different functional
form.
In the case of L-glutamic acid, the Gibbs energy of the dissociation process, Go (T ) =
−RT ln K2 (T ), can be linearly correlated with temperature, Go (T )/kJ·mol−1 =
−0.1133 + 0.0846 (T /K), R 2 = 0.9990 and Go (T ) ≈ −T So (T ), i.e., basically the dis-
sociation process is controlled by the entropic term only.

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